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Cite this: Dalton Trans., 2011, 40, 7077

www.rsc.org/dalton PERSPECTIVE
Chemistry and applications of organotin(IV) complexes of Schiff bases
Mala Nath* and Pramendra K. Saini
Received 20th October 2010, Accepted 2nd February 2011
DOI: 10.1039/c0dt01426e
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

Schiff bases are the most widely used versatile ligands, able to coordinate many elements and to
stabilize them in various oxidation states. Recently, this class of compounds has been employed as
models for biological systems, and in control of stereochemistry in six-coordinate transition metal
complexes. Recently, the chemistry of organotin(IV) complexes of Schiff bases has also stemmed from
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their antitumour, antimicrobial, antinematicidal, anti-insecticidal and anti-inflammatory activities.

Furthermore, organotin(IV) complexes of Schiff bases present a wide variety of interesting structural
possibilities. Both aliphatic and aromatic Schiff bases in their neutral and deprotonated forms have
been used to yield adducts and chelates with variable stoichiometry and different modes of
coordination. This critical review (>155 references) focuses upon the chemistry and biological
applications of organotin(IV) complexes of Schiff bases reported in the past 15 years. Thermal behavior
of these complexes is also discussed.

1. Introduction design. A large number of Schiff bases have been synthesized

Schiff bases still play an important role in metal coordination
chemistry even after almost a century since their discovery.1–4 They
are considered “privileged ligands” and are the most widely used
due to their versatile synthesis, remarkable versatility and good
solubility in common solvents. Stereogenic centers or other ele-
ments of chirality (planes, axes) can be introduced in the synthetic
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee,
-247667, Uttrakhand, India. E-mail: malanfcy@iitr.ernet.in; Fax: +91-
01332-273560
and extensively studied because they have some characteristic
properties such as manifestations of novel structures, thermal
stability, relevant biological properties, high synthesis flexibility
and medicinal utility.5 Schiff base ligands are able to coordinate
many elements and to stabilize them in various oxidation states.
Recently, this class of compounds has been employed as models
for biological systems,6 and in control of stereochemistry in six-
coordinate transition metal (Ti and Zr) complexes which are used
as potential catalysts for alkene polymerization.7 Furthermore,
Schiff bases have been known to be used in the preparation

Mala Nath, born in 1955 in UP,
India, obtained her PhD (1979)
at Lucknow University with Prof.
T. N. Srivastava. She was a gold
medallist at the level of gradu-
ation and post graduation. She
worked as a CSIR-postdoctoral
fellow up to June 1981 at Luc-
know University. In 1981, she
joined University of Roorkee as
a Lecturer and rose through the
ranks to become a Professor in
2001 in Indian Institute of Tech-
Mala Nath nology Roorkee. She is a member
of the National Academy of Sciences (FNASc), Allahabad. Her
research objectives are centered on design, synthesis, structural
studies and therapeutic potential of organotin and organosilicon
derivatives
Pramendra Kumar Saini
Pramendra Kumar Saini did his
MSc at CCS University, Meerut,
and thereafter he joined as a
Project Fellow in 2002 under a
UGC sponsored research project,
and then joined as a CSIR-JRF
in 2003 and completed his PhD
in 2008 under the supervision of
Prof. Mala Nath at the Indian
Institute of Technology Roorkee.
In Nov. 2009, he joined as a
Lecturer in Ambala Institute of
Technology. At present he is As-
sistant Professor in Institute of
Technology and Management,
Meerut, India.

This journal is © The Royal Society of Chemistry 2011 Dalton Trans., 2011, 40, 7077–7121 | 7077
 View Online

of many potential drugs, and are known to possess a broad
spectrum of biological activities such as antiviral,8 antifungal,9
antiparasitic,10 antibacterial,11 anti-inflammatory,12 antitumor,13
antiHIV,14 anticancer,15 etc. When administered as their metal
complexes, the anticancer activity of these complexes is enhanced
in comparison to the free ligands.6,16 Moreover, it has been
reported that the Schiff base metal complexes derived from the
salicylaldehyde can cleave DNA.17–19
Organotin compounds show the most diverse range of appli-
cations ranging from all sorts of biological activity to industrial
catalysts for value-creating technical processes.20 They have found
diversified commercial applications, such as polyvinyl chloride
(PVC) stabilizers, industrial biocides, industrial catalysts, surface
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
1,2-phenylenediimine [H2 salpdi] and N,N¢-bis(2-hydroxy-1-
naphthaldehyde)-1,2-phenylenediimine [H2 nappdi] in 95%
ethanol as shown in eqn (1), and recrystallized from n-hexane.
SnCl 4 /R n SnCl 4−n ⎯left
⎯⎯⎯⎯⎯
95% ethanol
at RT overnight
→ SnCl 4 /R nSnCl 4−n ⋅ HL/H 2 L (1)
where, n = 0 or SnCl4 for HL = Hsalapi and Hnapapi, H2 L =
H2 salpdi and H2 nappdi; n = 1, R = n-Bu, n = 2, R = n-Bu and Ph,
n = 3, R = Ph for HL = Hsalapi, and n = 1, R = Me, n-Bu and Ph
for H2 L = H2 salpdi.38
A number of molecular adducts have been synthesized by
the reaction of SnX4 or Rn SnX4-n with bidentate N-substituted
salicylideneimines as shown in eqn (2).

curing agents,21–24 scintillation detectors for g- and X-rays,24 Rn SnX4-n + mHL/H2 L → Rn SnCl4-n ·m(HL/H2 L) (2)
ballistic additives for solid-rocket engine fuels,24 ionophores in
where, n = 2, m = 2, X = Cl, R = Me and Ph for HL = (o-
liquid membrane ion-selective electrodes, and so forth.25,26 Many
HOC6 H4 CH NC6 H4 CH3 -4) [Htsaldi] and R = Ph for HL =
organotin compounds have been reported to exhibit potent
(o-HOC6 H4 CH NC6 H4 (Cl-4/OMe-4)) in ethanol;39 n = 2, X =
anticancer activity,20,27,28 and the National Cancer Institute (NCI)
Cl, R = Me and n-Bu for H2 L = 2-{[(2-hydroxyphenyl)-
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has tested about 2000 tin-based compounds, the largest number

imino]methyl}phenol [H2 salop]40 in diethyl ether; n = 0, X = NCS
ever tested among metal complexes.20 In general, the biochemical
(i.e. Sn(NCS)4 ), m = 2; n = 1, R = Ph, X = NCS, m = 2; n = 2, R =
activity of organotin(IV) compounds is greatly influenced by the
Me and Ph, X = NCS, m = 2 for HL = Htsaldi41 in 96% ethanol.
stereochemistry of the compound and the coordination number
You et al.42,43 have synthesized two new organotin-Schiff
of the tin atom.6,20,27 Recently, the chemistry of organotin(IV) com-
base adducts of the formulae, C24 H25 Cl4 NO3 Sn·0.5C6 H6 and
plexes of Schiff bases has also stemmed from their antitumour,29–33
C28 H31 Cl3 NO4 Sn, from the reaction of (b-n-butoxycarbonylethyl)-
antimicrobial,33–36 antinematicidal,37 anti-insecticidal37 and anti-
tin(IV) trichloride with 2-hydroxy-1-naphthalidene-4-chloro-
inflammatory activities.35 Furthermore, organotin(IV) complexes
aniline42 /2-hydroxy-1-naphthalidene-4-methoxyaniline43 in ben-
of Schiff bases present a wide variety of interesting structural
zene. Diorganotin(IV) dichloride adducts, R2 SnCl2 ·L, have been
possibilities. Both aliphatic and aromatic Schiff bases in their
synthesized44 according to eqn (3).
neutral and deprotonated forms have been used to yield adducts
and chelates with variable stoichiometry and different mode of R2 SnCl2 + L → R2 SnCl2 ·L (3)
coordination.4
where, R = Me, Et, Vinyl, t-Bu, n-Bu and Ph, L = N-(2-
A review on organotin(IV) complexes of Schiff bases covering the
pyridylmethylene)arylamine.44
literature up to 1994 has been published by Nath et al.4 Thereafter,
Several Schiff bases45 derived from salicylaldehyde and 2-
a comprehensive review of the existing literature, available to the
aminopyridine have been found to coordinate with Me2 SnCl2 in
authors, on the organotin(IV) complexes of Schiff bases has been
1 : 1 and 1 : 2 (tin : Schiff base) molar ratio (eqn (4)) in diethyl ether
compiled in the following subsections with special reference to
to yield Me2 SnCl2 ·HL and Me2 SnCl2 ·2HL, respectively. These
their synthesis, spectral characterization, thermal behavior and
Schiff bases coordinate with Ph2 SnCl2 in a similar manner, but if
biological applications.
the reaction is carried out in chloroform or if the product formed
in ether is dissolved in chloroform, then colorless to pale yellow
2. Synthesis of organotin(IV) complexes of Schiff bases crystals of the ionic compounds, [H2 NpyNH+ ]2 [Ph2 SnCl4 ]2- are
formed as a result of an unusual cleavage of the C N bond of the
An overview of the methodology adopted for the synthesis of
Schiff base45 as shown in Scheme 1.
organotin(IV) derivatives of Schiff bases reveals that these deriva-
tives have been synthesized either as adducts of organotin(IV) Me2 SnCl2 + nHL → Me2 SnCl2 ·nHL (4)
moiety with Schiff bases, or by the substitution reaction of
where, n = 1 or 2, HL = Schiff bases derived from salicylaldehyde
organotin(IV) chlorides/oxides and Schiff bases.
and 2-aminopyridine45

2.1. Organotin(IV)-Schiff base adducts

In view of the highly hydrolysable nature of organotin(IV)

halides which are generally employed as starting materials, their
complexes have been prepared by carrying out the reaction in
anhydrous organic solvents such as n-hexane, benzene, acetone,
methanol, ethanol or 1,4-dioxane.
Teoh et al.38 have synthesized a series of molecular
adducts from the reaction of SnCl4 or organotin(IV)
chlorides with N-(2-hydroxybenzaldehyde)-1-amino-2-phenyl-
eneimine [Hsalapi], N-(2-hydroxy-1-naphthaldehyde)-1-amino-
2-phenyleneimine [Hnapapi], N,N¢-bis(2-hydroxybenzaldehyde)-
Al–Allaf et al. have reported46–49 a number of complexes
of general formula, R2 SnCl2 ·HL/L¢ (R = Me, n-Bu and Ph),
by the reaction of R2 SnCl2 with Schiff bases HL/L¢ derived
from the condensation of substituted/non-substituted 2- or 3-
aminopyridene46–49 or 2-aminotoluene with benzaldehyde49 or 2-
hydroxy-, 2-methoxy- or 2-hydroxy-3-methoxy-benzaldehyde46–49

7078 | Dalton Trans., 2011, 40, 7077–7121 This journal is © The Royal Society of Chemistry 2011

Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
Scheme 1 Reaction routes leading to the formation of the ionic
compounds.45
(eqn (5)) in a 1 : 1 molar ratio. The decomposition ionic products
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of Ph2 SnCl2 ·L, i.e., [H2 Npy(R)NH]2 [Ph2 SnCl4 ], where R = H, 3-
CH3 and 4-CH3 have also been reported.49
R2 SnCl2 + (HL/L¢) → R2 SnCl2 ·(HL/L¢)
where, R = Me, n-Bu and Ph, HL/L¢ =
Al-Allaf and Al-shama’a have also synthesized50 the corre-
sponding triphenyltin(IV) compounds according to eqn (6).
Ph3 SnX + HL/L¢ → Ph3 SnX·(HL/L¢)
where, X = OH, Cl, N3 , and NO3 , HL/L¢ are same as in eqn (5).
A series of molecular adducts of diorganotin(IV) dichlo-
rides with pyrrole-2-carbaldehyde-2-hydroxybenzoylhydrazone
(H3 pchbh) and pyrrole-2,5-dicarbaldehydebis(2-hydroxybenzoyl-
hydrazone) (H5 pdchbh) has been synthesized51,52 in absolute
ethanol at 60 ◦ C according to eqn (7).
R 2SnCl 2 + H n L ⎯absolute
⎯⎯⎯⎯ o
ethanol
→ R 2SnCl 2 ⋅ H n L⋅ x H 2O
60 C
where, R = Et and Ph, n = 3, x = 2; R = Ph, n = 3, x = 0;51 R = Et, n =
5, x = 3; R = Ph, n = 5, x = 052 for Hn L = H3 pchbh and H5 pdchbh.
Some diorganotin(IV) dichloride adducts of
arylfurfuralnitrone (L) derived from furfuraldehyde
This journal is © The Royal Society of Chemistry 2011
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substituted phenylhydroxylamine have been synthesized in dry
chloroform at room temperature53 according to eqn (8).
R2 SnCl2 + L → R2 SnCl2 ·L (8)
where, R = Me, Bu and Ph, X = H, COCH3 , F, Cl and Br; R = Me
and Ph, X = CH3 and OCH3 ,53
A large number of 1 : 1 and 1 : 2 molecular adducts of
organotin(IV) chlorides with thio-Schiff bases derived from
condensation of substituted/non-substituted aldehydes with
sulfanilamide, sulfamerazine,54 2-amino-5-(o-methoxyphenyl)-
1,3,4-thiadiazole,55 aniline N-thiohydrazide,56 2-ethylenediamino-
cyclopent-1-ene-1-methyldithiocarboxylate (H2 cdsalen)57 and var-
ious sulfa drugs58 have been reported (eqn (9)).
Rn SnCl4-n + m(HL/L/H2 L) → Rn SnCl4-n ·m(HL/L/H2 L) (9)
where, R = Me, n = 2, m = 1, HL = Schiff bases de-
(5)
rived from sulfanilamide or sulfamerazine and salicylaldehyde
(Hsalsfa or Hsalsfm)/o-hydroxynaphthaldehyde (Hnaphsfa or
Hnaphsfm)/o-hydroxyacetophenone (Hacsfa or Hacsfm);54 R =
Me and Ph, n = 3, m = 1; R = Ph, n = 2, m = 1, HL/L =
CH3 OC6 H4 N CR¢R¢¢ where, R¢ = H, R¢¢ = C6 H4 OH,
C10 H6 OH; R¢ = CH3 , R¢¢ = C6 H4 OH, C6 H5 CH2 , CH2 COCH3 ; R¢ =
H, R¢¢ = ;55 R = p-ClC6 H5 CH2 , n = 2 or 3, m = 1, L =
C6 H5 NHC(S)NHNH2 and C6 H5 NHC(S)NHN CHC6 H5 ;56 R =
Me, n = 2, m = 1; R = Ph, n = 2, m = 2, H2 L = H2 cdsalen;57 R =
Ph, n = 3, m = 1, HL = Schiff base derived from salicylaldehyde/2-
hydroxynaphthaldehyde and sulfa drugs e.g. sulfaguanidine, sulfa-
(6) anilamide, sulfadiazine or sulfamerazine.58
Recently, three new Schiff base adducts of the types,
[SnMe2 Cl2 (HL)], [Sn(n-Bu)2 Cl2 (HL)2 ] and [SnPh2 Cl2 (HL)2 ] have
been synthesized by the reaction of R2 SnCl2 with a new
Schiff base ligand, methyl-2-[2-(acetylacetoneimino)ethylamino]-
1-cyclopentene-1-dithiocarboxylate (HL) in benzene.59 The possi-
ble tautomeric forms of this new Schiff base ligand are shown in
Fig. 1.
Khoo et al. have prepared three new dinuclear tin complexes
(7)
[Me2 Sn(2-OC6 H4 CH N–CH{Pr¢}COO)]SnMe2 Cl2 , [Ph2 Sn(2-
OC10 H6 CH NCH2 COO)]SnPh2 Cl2 and [Me2 Sn(2-OC10 H6 -
CH NCH2 COO)]SnMe2 Cl2 by the reaction of diorganotin(IV)
dichloride (acceptor) and N-arylidene-a-aminoacidatotin(IV)
(donor) in benzene and toluene, respectively.60 Similarly,
diphenyltin(IV) complexes of N-(3,5-dibromosalicylidene)-a-
amino acid, Ph2 Sn[3,5-Br2 -2-OC6 H2 CH:NCH(R)COO] (R = H,
Me, i-Pr and Bz), and their 1 : 1 adducts with diphenyltin dichlo-
ride, Ph2 Sn[3,5-Br2 -2-OC6 H2 CH NCH(R)COO]·Ph2 SnCl2 , have
also been synthesized.61
Choudhary et al. have reported 1 : 1 adducts of triphenyltin chlo-
ride with oxovanadium(IV) tetradentate Schiff base complexes62
(eqn (10a) and eqn (10b)) in acetonitrile. They have also
N- synthesized the [VO(salen)] adduct of N-triphenylstannyl-1,2-
and benzisothiazol-3(2H)one-1,1-dioxide in ethanol.62
Dalton Trans., 2011, 40, 7077–7121 | 7079
 View Online

Fig. 1 Possible tautomeric forms of methyl-2-[2-(acetylacetoneimino)ethylamino]-1-cyclopentene-1-dithiocarboxylate (Hcdacacen).59

methoxide/ethoxide in anhydrous methanol/ethanol under nitro-

Ph 3SnCl + VOL ⎯⎯⎯ → Ph 3SnCl ⋅ VOL⋅ x CH 3CN
3 CH CN
(a)
(10) gen atmosphere.
Ph 3SnX + VOL ⎯⎯⎯⎯
→ Ph 3SnX ⋅ VOL
C2 H5 OH
( b) Pettinari et al.40 produced a series of complexes by the interac-
tion of Schiff base with tin and organotin(IV) acceptors as shown
where, H2 L = N,N¢-ethylenebis(salicylideneimine) (H2 salen),
in eqn (13(a)–(c)).
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

H2 L = N,N¢-ethylenebis(5-methoxysalicylideneimine)
[H2 salen(5-OMe)2 ], x = 0.5; H2 L = N,N¢-ethylenebis(3-
methoxysalicylideneimine) [H2 salen(3-OMe)2 ], x = 1; H2 L = H 2 L + 2NaOR/NaOR ⎯⎯
→ Na 2 L/NaHL + 2ROH/ROH (a)
N,N¢-ethylenebis(acetophenoneimine) (H2 acpen), x = 0.25; H2 L =
N,N¢-methylmethylenebis(salicylideneimine) (H2 sal-1,2-pn), where, R = Me or Et
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x = 0; H2 L = N,N¢-methylmethylenebis(acetophenoneimine)
(H2 acp1,2-pn), x = 2 for eqn (10a); H2 L = H2 salen, H2 acpen,
R 2SnCl 2 /R ′SnCl3 /R ′′3SnCl + Na 2 L/NaHL ⎯⎯
→
H2 sal-1,2-pn; X = 1,2-benzisothiazol-3(2H)one-1,1-dioxide for
eqn (10b).62 R 2SnL/R ′SnCl(L) ⋅ x/R ′′3Sn(HL) + 2NaCl/NaCl (b)
The binuclear adduct formation between R2 SnCl2 as acceptors,
and Ni(II) complexes of tetradentate Schiff base ligands ([NiL]) as where, R = Me, n -Bu, t -Bu, Vinyl
donors have also been reported63,64 as shown in eqn (11). and Ph; R ′ = Me, x = H 2O;
Ni(L) + R2 SnCl2  R2 SnCl2 ·Ni(L) (11) R ′ = n -Bu and Ph, x = CH 3OH; R ′′ = Me (13)
where, R = Me and n-Bu, H2 L = H2 salen, H2 salen(3-OMe)2 , N,N¢- and n -Bu 40 for H 2 L = H 2Salop.
ethylenebis(4-methoxysalicylideneimine) [H2 salen(4-OMe)2 ],
N,N¢-ethylenebis(5-methoxysalicylideneimine) [H2 salen(5- SnX 4 + Na 2 L ⎯⎯
→ SnX 2 L ⋅ x + 2NaX (c)
OMe)2 ], N,N¢-ethylenebis(5-chlorosalicylideneimine) [H2 Salen(5-
Cl)2 ], N,N¢-ethylenebis(5-bromosalicylideneimine) [H2 salen(5-
Br)2 ]63 in chloroform; R = Me, n-Bu and Ph, H2 L = H2 salphen, where, X = Cl and Br, x = H 2O and CH 3OH;
H2 salphen(3-MeO)2 , H2 salphen(4-MeO)2 , H2 salphen(5-MeO)2 in X = I, x = CH 3OH for H 2 L = H 2Salop.40
chloroform.64
Further, binuclear complexes, [M(3-MeO-sal-m-phen)(H2 O)]2
HL + NaH ⎯D⎯⎯
THF
→ NaL + H 2 (d)
[M = Ni, and Zn], have been reported65 to react with R2 SnX2 (R = reflux

Me, n-Bu, Ph and Bz; X = Cl, NO3 and NCS) (eqn (12)).
M(L) + R2 SnX2 →
(12)
{[R2 SnX2 ]·[M(L)]·xH2 O}2 /{[R2 SnX]·[M(L)X]·xH2 O}2
where, R = n-Bu, Ph and Bz, M = Ni and Zn, X = NCS, Cl and Br,
x = 0, 1 and 2, L = N,N¢-bis(3-methoxysalicylidene)benzene-1,3-
diamine (3-MeO-sal-m-phen) in acetonitrile; R = Me, n-Bu, Ph and
Bz, M = Ni and Zn, X = NO3 , x = 0 and 1, L = 3-MeO-sal-m-phen
in acetone; R = n-Bu, M = Ni, = NCS, x = 1, L = N,N¢-bis(3-
methoxysalicylidene)benzene-1,4-diamine (3-MeO-sal-p-phen) in
acetonitrile.65
2.2 Organotin(IV)-Schiff base chelates
The organotin(IV)-Schiff base chelates have been synthesized
using replacement reactions according to the following methods
discussed below.
2.2.1 By sodium salt of Schiff bases. A wide variety of
organotin(IV) derivatives of Schiff bases have been synthesized by
the addition of methanol–ethanol solution of the corresponding
organotin(IV) halide to a solution of sodium salt of Schiff base,
prepared in situ by the reaction of Schiff base with sodium
2 NaL + R 2SnCl 2 ⎯DTHF
⎯⎯
RT
→ R 2SnL 2 + 2NaCl (e)
where, R = CH3 and n-C4 H9 , HL = N-(3-tert-
butylsalicylidene)-2,3,4,5,6-pentafluoroaniline and N-(3-tert-
butylsalicylidene)aniline).66
A large number of mono-, di- and triorganotin(IV) derivatives
of hydrazones have also been synthesized by this method67–71
according to eqn (14).
xRn SnCl4-n + Na2 L/yNaHL/Na4 L →
(14)
xRn SnClm (L/HL)/(Rn Sn)x L
where, x = 1, n = 1 or 2, m = 1 or 0, R = Me, H2 L = Schiff base
derived from acylhydrazines and N-salicylidene (H2 achyd-sal)
or N-pyridoxylidene (H2 achyd-pyr, Fig. 2);67 x = 1, n = 3, R =
n-Bu and Ph, y = 1, m = 0; n = 2, R = Me and n-Bu, y = 1
or 2, m = 1 or 0, H2 L = N,N¢-hydrazinebis(salicylideneimine)
(H2 hyd-sal)68 or benzilmonohydrazone,69 which act as unidentate
ligand;68,69 x = 1, n = 2, R = n-Bu and Ph, m = 0, H2 L = (H2 hyd-sal)
acts as bidentate ligand;68 x = 2, n = 2, R = Me and n-Bu,
H4 L = [bis(2-hydroxybenzaldehyde)tetraphthalohydrazone] or
[bis(2-hydroxy-3-methoxybenzaldehyde)tetraphthalohydrazone]
or [bis(2-hydroxy-1-naphthaldehyde)tetraphthalohydrazone];70

7080 | Dalton Trans., 2011, 40, 7077–7121 This journal is © The Royal Society of Chemistry 2011

Fig. 2 Molecular structures of H2 achyd-sal and H2 achyd-pyr.67
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
x = 1, n = 2, R = Me, n-Bu, Ph and PhCH2 , m = 0, H2 L =
o-vanillin-2-thiophenoylhydrazone (H2 -o-Van-2-tph).71
Yin et al. have synthesized72,73 some organotin(IV) complexes of
hydrazones, viz. [R2 SnLY]2 and [R3 SnL]2 by using sodium salt of a
Schiff base prepared in situ and the corresponding diorganotin(IV)
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or triorganotin(IV) chloride according to eqn (15).
(15)
where, X = , R = n-Bu and Ph, Y = CH3 OH; R =
Me, Y = 0, in methanol with sodium methoxide of ligand;72 X =
, R = n-Bu and PhCH2 , Y = N2 , in a mixture of
ethanol and benzene (v/v: 1/3) with sodium ethoxide of ligand;72
X= , R = Me and n-Bu, in a mixture of ethanol and benzene
(v/v: 1/3) with sodium ethoxide of ligand.73
Diorganotin(IV) derivatives, viz. R2 SnCl(NŸ O) and R2 Sn(NˆO)2
(R = Me and Ph) have been synthesized74 by metal ion interaction
with monobasic bidentate ligands having NˆO donor set in 1 : 1 and
1 : 2 molar ratio, respectively, according to eqn (16a) and (16b).
R 2SnCl + N ^ O . Na ⎯MeOH/1:1
⎯⎯⎯ → R 2SnCl(N ^ O) + NaCl (a)
R 2SnCl + 2(N ^ O . Na) ⎯MeOH/1:2
⎯⎯⎯ → R 2Sn(N ^ O) 2 + 2NaCl (b)
(16)
where, R = Me and Ph,
Recently, reactions of the sodium salt of pyruvic acid
thiophenecarbonyl hydrazone (L1) or pyruvic acid 4-
hydroxybenzoylhydrazone (L2) with n-Bu2 SnCl2 or (o-
ClBz)2 SnCl2 in isopropyl alcohol or benzene or ethyl
alcohol have been reported75 to yield new organotin(IV)
compounds, {(n-Bu)2 Sn[2-S-C4 H3 CON2 C(CH3 )CO2 ](HOC3 H7 -
i)}2 , [{(n-Bu)2 SnCl(O)(n-Bu)2 Sn(O)[C6 H4 CON2 C(CH3 )CO2 ]Sn-
(n-Bu)2 (HOCH3 )}2 ]n and {(o-ClBz)2 Sn[4-HOC6 H4 CON2 C(CH3 )-
CO2 ](HO–C2 H5 )}2 .
Several di- and triorganotin(IV) derivatives of Schiff bases
derived from thiosemicarbazide have been synthesized76–79 by
reaction of the corresponding organotin(IV) chlorides with sodium
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salts of thiosemicarbazones in the desired molar ratio as shown in
eqn (17).
Rn SnCl4-n + Na2 L/Na(HL/H2 L)/NaL →
(17)
Rn SnLm /Rn SnClx (L/HL/H2 L)y
where, n = 2, x = 1, R = Me and Et; n = 1, x = 2, R = Me, HL =
2-formylpyridine thiosemicarbazone;76 n = 2, m = 1, R = Me and
n-Bu; n = 2, x = 0, y = 2, R = Me and n-Bu; n = 2, x = 1, y = 1, R = Me
and n-Bu; n = 3, x = 0, y = 1, R = n-Bu and Ph, H2 L = salicylaldehyde
thiosemicarbazone;77 n = 2 or 3, x = 0 or 1, y = 1, R = PhCH2 ,
NaHL = sodium salt of salicylaldehyde thiosemicarbazone, o-
vanillin thiosemicarbazone, o-hydroxyacetophenone thiosemicar-
bazone, NaH2 L = 2,4-dihydroxybenzaldehyde thiosemicarbazone
and 2,4-dihydroxyacetophenone thiosemicarbazone;78 n = 2, m =
2, R = Me and Ph, HL = 2-HSC6 H4 N CMeCH2 -i-Pr; n =
3, m = 1, R = Ph, HL = 2-HSC6 H4 N CMeCH2 -i-Pr and i-
PrCH2 C(Me) NNHC(S)NH2 ; n = 2, x = 1, y = 1, R = Me and
Ph, HL = i-PrCH2 C(Me) NNHC(S)NH2 .79
The reactions of triorganotin(IV) chloride and diorganotin(IV)
dichloride with sodium salts of Schiff bases derived from 2-amino-
5-phenyl (or o-anisyl)-1,3,4,-oxadiazole (or -thiadiazole) led to the
products80,81 according to the eqn (18).
Rn SnCl4-n + xNaL → Rn SnClm Ly + xNaCl (18)
where, n = 3, x = 1, m = 0, y = 1, R = Ph, HL = derived from
2-amino-5-phenyl-1,3,4-oxadiazole, i.e. X = O, R¢ = H and R¢¢ =
H;80 n = 2, x = 2, m = 0, y = 2, R = Ph; n = 3, x = 1, m = 0, y = 1,
R = Me and Ph, HL = Schiff bases derived from the condensation
of 2-amino-5-(o-anisyl)-1,3,4-thiadiazole with salicylaldehyde, 2-
hydroxynaphthaldehyde and 2-hydroxyacetophenone, i.e. R¢ = H
or CH3 , X = S, R¢¢ = OCH3 .81
Several organotin(IV) derivatives of Schiff bases derived from S-
benzyldithiocarbazates have also been synthesized82,83 according
to the same method using eqn (18) with n = 2, x = 1 or 2, m = 1 or
0, y = 1 or 2, R = Ph, HL = Schiff base of S-benzyldithiocarbazate
with heterocyclic aldehydes, using sodium methoxide in benzene,82
Similarly, di- and triorganotin(IV) derivatives of Schiff bases
derived from sulfonamide-imine have also been reported using
sodium methoxide in methanol and ligand with NˆN donor
system84 according to eqn (18), where n = 2, x = 1 or 2, m = 1
or 0, y = 1 or 2, R = Me and Ph; n = 3, x = 1, m = 0, y = 1, R = Ph,
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Organostannoxane-based multi-redox assemblies containing respectively, led to the formation of the complexes88 as shown
Schiff base-triazole ligand peripheries have been readily synthe- in Scheme 4.
sized by hydrolysis or solvothermal synthetic routes by Chunlin Di- and triphenyltin(IV) derivatives of Schiff bases derived from
Ma and co-workers.85 The reactions of diorganotin(IV) dichlo- the condensation of 2-hydroxy-1-naphthaldehyde/benzaldehyde
ride with Schiff base-triazole ligand afford the following types: with different a-amino acids (H2 L/HL¢) have been reported by
[(Me2 Sn)2 O2 (Ln )]2 (n = 1), [(Me2 Sn)2 O(RO)(Ln )]2 (R = Et, n = 2; Nath et al.89 using sodium salt method (eqn (19)).
R = Me, n = 3) and [(n-Bu2 Sn)2 O2 (Ln )]2 (n = 1, 2 or 3) (Scheme 2).
The same authors86 have also synthesized a Schiff base by refluxing H 2 L/HL′ + 2NaOMe/NaOMe ⎯⎯
→
a mixture of furfural and 3-amino-5-mercapto-1,2,4-triazole in Na 2 L/NaL′ + 2MeOH/MeOH (a)
ethanol. By using sodium methoxide in ethanol, an organotin(IV)- (19)
Ph 2SnCl 2 + Na 2 L ⎯⎯
→ Ph 2SnL + 2 NaCl (b)
Schiff base complex containing a novel Sn5 O5 hydrolysis ladder
and a disulfide group has been synthesized through a self-assembly Ph 3SnCl + Na 2Cl′ ⎯⎯
→ Ph 3SnL′ + NaCl (c)
reaction (Fig. 3).
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Fig. 3 Organotin(IV)-Schiff base complex containing a novel Sn5 O5

hydrolysis ladder.86
Similarly, diorganotin(IV) complexes, viz. [Me2 Sn(LH)2 ], of the
Schiff base derived from a non-protein amino acid90 have also been
Recently, eight new triorganotin complexes of the types, synthesized according to eqn (20).
[(R3 Sn)2 (C24 H16 N8 S2 )]Y (R = Ph, Y = 0; R = PhCH2 , Y =
2CH3 OH; R = n-Bu, Y = 0), [(R3 Sn)2 (C24 H16 N8 S2 )]n (R = Me), H 2 L + NaHCO3 ⎯⎯
→ LHNa + H 2CO3 (a)
[(R3 Sn)2 (C12 H6 N6 S4 )]Y (R = Ph, Y = CH2 Cl2 ; R = PhCH2 , Y = 0) Me 2SnCl 2 + 2LHNa ⎯⎯
→ Me 2Sn(LH)2 + 2NaCl (b)
and [(R3 Sn)2 (C12 H6 N6 S4 )] (R = n-Bu or Me) have been synthesized (20)
87
by the interaction of H2 L1 (H2 L1 derived from 4-amino-5-
phenyl-4H-1,2,4-triazole-3-thiol) or H2 L2 (H2 L2 derived from 5- where, H2 L = 4-[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)-
amino-1,3,4-thiadiazole-2-thiol) with triorganotin chloride in the amino]benzoic acid.90
presence of sodium ethoxide (Scheme 3). Recently, triorganotin(IV) derivatives of the type, [R3 Sn[O-
The interaction of R3 SnCl and R2 SnCl2 with the sodium 1,2-C6 H4 (3-C3 H4 N2 -kN2 -5)-1,4-C6 H4 X]] (R = Me, n-Pr, Ph; X =
salt of the Schiff base derived from the condensation of 2- H, Me, OMe, Cl) have been prepared by reaction of R3 SnCl
aminomethylbenzimidazole (ambmz) and salicylaldehyde abbre- with the sodium salt of 3-(2-hydroxyphenyl)-5-(4-X-phenyl)-1H-
viated as HL or Hsal-ambmz in a 1 : 1 and 1 : 2 molar ratio, pyrazolines (LX) in a 1 : 1 molar ratio in anhydrous benzene.91

Scheme 2 Reaction pathways for organostannoxane-based multi-redox assemblies.85

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Scheme 3 Synthetic routes of triorganotin(IV) complexes of Schiff bases derived from 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol or
5-amino-1,3,4-thiadiazole-2-thiol.87

2.2.2 By potassium salts of Schiff bases. Tian et al.92 have
synthesized diorganotin(IV) complexes of N-(5-halosalicylidene)-
a-amino acid by reaction of diorganotin(IV) dichloride with
potassium salts of Schiff bases according to eqn (21).
R¢2 SnCl2 + 5-X-2-HOC6 H3 CH NCHRCOOK + Et3 N →
(21)
R¢2 Sn(5-X-2-OC6 H3 CH NCHRCOO) + KCl + Et3 N·HCl
R' 2SnCl 2 + 3,5-Br2 -2-HOC6 H 2CH=NCHRCOOK ⎯⎯
→
R' 2Sn(3,5-Br2 -2-OC6 H 2CH=NCHRCOO) (A ) + KCl (a)
where, R = H, Me, i -Pr, i -Bu, s -Bu and CH 2 Ph,
(22)
R' = n -Bu, Ph and cyclo-C6 H11.

A + Ph 2SnCl 2 ⎯⎯
→
R' 2Sn(3,5-Br2 -2-OC6 H 2CH=NCHRCOO) ⋅ SnPh 2Cl 2 (b)

where, R = H, Me, i-Pr and CH2 Ph, R¢ = Ph.93

Furthermore, the reaction of Ph3 SnCl with potassium N-[3,5-
dibromo-2-hydroxyphenyl)methylene]valinate (HLK) yielded94 a
novel mixed organotin binuclear complex, Ph3 Sn(HL)·Ph2 SnL via
Similarly, they have also synthesized diorganotin(IV) com-
facile cleavage of the phenyl-tin bond as shown in eqn (23).
plexes of N-(3,5-dibromo)salicyledene-a-aminoacid, R¢2 Sn(HL)
(eqn (22a)), where R¢ = Ph, R = H, Me, i-Pr and CH2 Ph,
which reacts with an additional equiv. of Ph2 SnCl2 forming Ph 3SnCl + HKL ⎯-KCL
⎯⎯ → Ph 3Sn(HL) ⎯−⎯⎯
PhH
→ Ph 2SnL
(23)
⎯⎯⎯⎯→ Ph 3Sn(HL) ⋅ Ph 2SnL
Ph Sn(HL)
binuclear adducts with Schiff base ligand coordinated to the 3

second organotin moiety through its carboxylic oxygen as shown

in eqn (22b).93 where, HLK = 3,5-Br2 -2-HOC6 H2 CH NCH(i-Pr)COOK.94

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Scheme 4 Reaction pathways for di- and triorganotin(IV) complexes of
the Schiff base derived from 2-aminomethylbenzimidazole (ambmz) and
salicylaldehyde.88
Recently, amino acetate functionalized Schiff base organotin(IV)
complexes of the types, [Ph3 SnLH]n and [Ph2 SnL2 ], have been
synthesized95 by the reaction of potassium 2-{[(2Z)-(3-hydroxy-
1-methyl-2-butenylidene)]amino}-4-methylpentanoate (L1 HK)
or potassium 2-{[(E)-1-(2-hydroxyphenyl)alkylidene]amino}-4-
methyl-pentanoate (L2 HK/L3 HK) with Phn SnCl4-n (n = 2 or 3)
according to Scheme 5.
Chunlin Ma and co-workers85 have also synthesized
[(Me2 Sn)2 OL2 ]2 ·L¢ (L = Schiff base ligand; n = 2; L¢ = H2 O and
CH3 OH) by using the potassium salt of the ligand (Scheme 6).
Recently, reactions of potassium b-{[(E)-1-(2-hydro-
xyaryl)alkylidene]amino}propionates (LHK) and potassium b-
{[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)]amino}propionates
(L¢HK) with R3 SnCl (R = Ph and n-Bu) and n-Bu2 SnCl2 have
been reported to yield Ph3 SnLH, Ph3 SnL¢H, n-Bu3 SnLH and
{[n-Bu2 Sn(LH)]2 -O}2 , respectively.96
Triorganotin(IV) esters of 3- and 4-[1-pyridin-2-yl-methyli-
dene]benzoic acid and 3,5-bis[1-pyridin-2-ylmethylidene]benzoic
acids have recently been synthesized by the interaction of potas-
sium salt of Schiff base formed from potassium aminobenzoate
and pyridine-2-aldehyde in situ with appropriate R3 SnCl (R = Me,
n-Bu, Cy, Ph and Bz) in toluene.97
Barba et al.98 have synthesized binuclear tin compounds by
reaction of hexadentate Schiff bases having two sets of ONO
donor atoms with the corresponding diorganotin(IV) dichloride
in a 1 : 2 molar ratio. Potassium hydroxide is used as base for the
deprotonation of the ligand (Scheme 7).
A number of organotin(IV)-Schiff base complexes of the type,
Rn SnCl2-n (L), where R = Me, n-Bu and Ph, n = 2; R = Me, n-
7084 | Dalton Trans., 2011, 40, 7077–7121
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Bu and Ph, n = 1; H2 L = benzoylacetone isonicotinyl-hydrazone
have been synthesized by direct reaction of organotin(IV) halide(s)
with hydrazone ligand in the presence of KOH in 1 : 2 : 1
(metal : base : ligand) in absolute methanol.99
Tri(methyl/benzyl/phenyl)stannyl 2-(2-oxoindolin-3-ylidene-
amino)benzoates have been obtained from the interaction of
2-(2-oxoindolin-3-ylideneamino)benzoic acid and NaOH with
triorganotin chloride in methanol under nitrogen.100 Similarly, 1,3-
bis{2-(triethyl/tribenzyl/triphenylstannyloxy)benzylidene}urea
have been synthesized by direct reaction of NaOH, triorganotin
chloride and 1,3-bis(2-hydroxybenzylidene) urea in anhydrous
methanol–chloroform.101
2.2.3 By deprotonation with triethylamine. Organotin(IV)
chloride reacts with Schiff bases in the presence of triethylamine
on refluxing in appropriate solvent to yield the chelates, and HCl
formed during the reaction is removed as triethylamine hydrochlo-
ride. Several organotin(IV) derivatives have been synthesized102–106
by this method according to eqn (24).
R nSnCl 4-n + H 2 L/HL ⎯⎯⎯ → R nSnCl m L/R nSnL + Et 3 NHCl (24)
Et 3 N
where, n = 0, m = 2, H2 L = N,N¢-phenylene-bis(3,5-di-
tert-butylsalicylideneimine) [H2 salophen(t-Bu)], N,N¢-(4,5-dime-
thyl)phenylene-bis(3,5-di-tert-butylsalicylideneimine) [H2 salom-
phen(t-Bu)];102 n = 1, R = n-Bu, m = 1 or 2, H2 L = H2 salophen(t-
Bu), H2 salomphen(t-Bu) and HL = 3,5-di-tert-butylsalicylidene(1-
aminophenylene-2-amine) [Hphensal(t-Bu)],102 this reaction leads
to a mixture of more than one compound;102 n = 2,
R = Me, H2 L = (N-(2-carboxyphenyl)salicylideneimine), in
methanol at room temperature;103 n = 2, R = Me, n-Bu and
Ph, H2 L = N,N¢-phenylenebis(salicylideneimine) (H2 salophen),
N,N¢-phenylene-bis(3-methoxysalicylideneimine) (H2 vanophen),
1,3-propylene-bis(salicylideneimine) (H2 salpn), 1,3-propylene-
bis(3-methoxysalicylideneimine) (H2 vanpn), N,N¢-phenylene-
bis(1-phenyl-3-methyl-4-benzoyl-5-pyrazolideneimine) (H2 pmbp-
o-phd) and 1,3-propylene-bis(1-phenyl-3-methyl-4-benzoyl-5-
pyrazolideneimine) (H2 pmbp-pn), in refluxing benzene;104 n =
2, R = t-Bu, Ph, PhCH2 , o-ClC6 H4 CH2 , p-ClC6 H4 CH2 ,
m-ClC6 H4 CH2 , o-FC6 H4 CH2 , p-FC6 H4 CH2 , H2 L = sal-
icylaldehyde isonicotinylhydrazone (H2 salinh), in benzene
at room temperature;105 n = 3, m = 0, R = Ph,
PhCH2 , 2-ClC6 H4 CH2 , 4-FC6 H4 CH2 , 4-ClC6 H4 CH2 , H2 L = 2-
OHC6 H4 CH N-(C6 H4 )COOH.106
Recently, it has been reported75 that a mixture of salicylaldehyde
isonicotinylhydrazone and n-butyltin trichloride in the presence of
triethylamine yields a rarely reported zwitterionic organotin(IV)
compound, [(n-C4 H9 )SnCl2 ]- [4-NHC5 H4 CON2 CH(C6 H4 O-2)]+ .
Self-assembled diorganotin(IV) esters of Schiff base ligands
formulated as [R2 SnLY]2 , have been prepared by Yin et al.107,108
The complexes have been prepared through the reaction of pyruvic
acid isonicotinyl hydrazone (H2 painh) and pyruvic acid salicylhy-
drazone (H2 pasalh) with triorganotin(IV) chloride (Scheme 8).
Yin et al.72,73 have also synthesized some organotin(IV) com-
plexes of the type [R2 Sn(H2 L)Y]2 ,72 [R3 SnL]2 73 and [R(HL)Cl2 ]71
by the reactions of hydrazones and R2 SnCl2 , R3 SnCl and RSnCl3 ,
respectively, in a 1 : 1 molar ratio in ethanol in the presence of
triethylamine as shown in eqn (25).
Rn SnCl4-n + H3 L/H2 L + Et3 N → [Rn Sn(Hm L)Y]x +
(25)
Et3 NHCl
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Scheme 5 Synthetic routes for potassium salts (L1 HK–L3 HK) and their triphenyltin(IV) complexes (1–3); the structure of diphenyltin(IV) complex (4) is
also included.95

Scheme 6 Reaction route for synthesis of tetranuclear organotin-Schiff base complex.85

Scheme 7 Reaction route for binuclear organotin-Schiff base complex.98

where, n = 3, m = 2, x = 1, R = n-Bu, Me and Ph, H3 L = pyruvic bromosalicylaldehyde benzoylhydrazone (H2 -5-br-salbh), Y = 0,

acid 3-hydroxy-2-naphthoylhydrazone (H3 pa-3-hy-2-nth), acting
as unidentate ligand;72 n = 2, m = 0, x = 2, R = Me and n-Bu,
H2 L = pyruvic acid thiophene-2-carboxylic hydrazone (H2 patp-2-
ch), Y = CH3 OH;73 n = 2, m = 0, x = 1, R = Me, n-Bu and Ph, H2 L =
salicylaldehyde thiophene-2-carboxylic hydrazone (H2 saltp-2-ch),
Y = 0;73 n = 1, m = 1, x = 1, R = Me, n-Bu and Ph, H2 L = H2 -
o-van-2-tph, Y = Cl2 ;71 n = 2, m = 0, x = 1, R = Me, H2 L = 5-
in methanol.109
Recently, triorganotin(IV) (R = Me, Et, n-Bu, Ph and Bz)
derivatives of a Schiff base derived from salicylaldehyde and
adenine have also been synthesized by this method by Rehman
et al.110 They have also synthesized a number of diorganotin(IV)
complexes of the type, R2 SnL2 (where R = Me, Et, n-Bu, Ph
and Bz; HL = 2-[(9H-purin-6-ylimino)]phenol) by the reaction

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Scheme 8 Reaction pathways for self-assembled organotin(IV)-Schiff base complexes.

of Schiff base ligand with R2 SnCl2 and triethylamine in 2 : 1 : 2

molar ratio.111
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Recently, four new reddish-orange dimethyltin(IV) complexes

of N-(3-hydroxypyridine-2-yl)-salicylideneimine derivatives with
the general formula, [Me2 Sn(2-OArCH NC5 H3 NO)], where Ar =
C6 H3 (5-CH3 ) [Me2 SnL1 ], C6 H3 (5-NO2 ) [Me2 SnL2 ], C6 H2 (3,5-Cl2 )
[Me2 SnL3 ] and C6 H2 (3,5-I2 ) [Me2 SnL4 ] have been synthesized
by the interaction of appropriate Schiff base ligands with
Me2 SnCl2 in 1 : 1 molar ratio in presence of a few drops of
triethylamine in dry methanol.112 Similarly, SnPh2 (L1 ), SnPh2 (L2 )
and SnMe2 (L2 ) have also been synthesized by interaction
of either 2-{[N-(5-chloro-2-hydroxyphenyl)imino]methyl}pyrrole Fig. 4 Molecular structure of tripodal Schiff base ligand
(H2 L1 ) or 1-{[N-(5-chloro-2-hydroxyphenyl)imino]methyl}-2- [tren(4-Me-5-ImH)3 ].115
naphthol (H2 L2 ) with Ph2 SnCl2 /Me2 SnCl2 in the presence of 2.2.4 By the reaction of diorganotin(IV)/triorganotin(IV) oxides
triethylamine in 1 : 1 : 2 molar ratio in methanol.113 Furthermore, with Schiff bases. Diorganotin(IV) complexes of Schiff bases have
two new diorganotin(IV) complexes of the general formula, also been synthesized by the condensation of diorganotin(IV)
R2 Sn[Ph(O)C CH–C(Me) N–C6 H4 (O)] (where R = Ph, I; R = oxides and Schiff bases in a suitable solvent with azeotropic
Me, II) have been synthesized from the corresponding diorgan- removal of water.
otin(IV) dichlorides and the ligand, 3-(2-hydroxyphenylimino)- Yin et al. have synthesized the complexes of the type
1-phenylbutan-1-one in methanol at room temperature in the [R2 Sn(L)Y]2 73,108,117 and {[R2 Sn(L)Y]SnR3 }2 108,117 by the reaction
presence of triethylamine in 1 : 1 : 2 molar ratio.114 of di- and triorganotin(IV) oxides, respectively, with the corre-
Nath et al.115 have also synthesized some new tri- and sponding Schiff bases in a 1 : 1 molar ratio according to eqn (27)
diorganotin(IV) complexes of the general formula, R3 Sn(H2 L) and and (28).
R¢2 Sn(HL) [where R = Me, n-Pr, n-Bu and Ph; R¢ = Me, n-Bu and
Ph; H3 L = Schiff base (abbreviated as tren(4-Me-5-ImH)3 ) (Fig. 4) H2 L + R2 SnO → [R2 Sn(L)Y]2 (27)
derived from condensation of tris(2-aminoethyl)amine (tren) and
where, H2 L = H2 saltp-2-ch, R = Ph, Y = 0, in absolute ethanol;73
4-methyl-5-imidazolecarbaldehyde (4-Me-5-ImH)] from interac-
H2 L = H2 painh, R = n-Oct and Ph,108 R = n-Bu,117 Y = H2 O, in
tion of tri- and diorganotin(IV) chlorides with tripodal Schiff
benzene–ethanol (3 : 1).108,117
base ligand containing three imidazole arms in presence of
triethylamine in 1 : 1 : 2 molar ratio at room temperature according H2 L + (R3 Sn)2 O → {[R2 Sn(L)Y]SnR3 }2 + RH (28)
to eqn (25).
where, H2 L = H2 pasalh, R = n-Bu, Bz and p-CNBz, Y = OH;108
Sharma et al.116 have used homometallic complexes
H2 L = H2 painh, R = n-Bu, Bz and p-CNBz, Y = O.117
Al(L)(OGOH) as precursors in a reaction with Bu3 Sn(O-i-Pr) in
The reaction of (Bu3 Sn)2 O with tridentate Schiff bases (as shown
presence of Et3 N, to yield heteronuclear mixed ligand complexes,
in eqn (18)) proceeds smoothly, but slowly with the elimination of
Al(L)(OGO)SnBu3 (eqn (26)).
water, which is removed azeotropically with benzene80 (eqn (29)).

(Bu 3Sn) 2O + 2 HONN ⎯⎯⎯ → 2 Bu 3SnONN + H 2O

C H
Al(L)(OGOH) + Bu3 Sn(O-i-Pr) + Et3 N →
6 6 (29)
(26)
Al(L)(OGO)SnBu3 + Et3 N·iPrOH
where, HONN = tridentate Schiff base derived from condensation
of 2-amino-5-phenyl-1,3,4-oxadiazole with salicylaldehyde, 4-
where, L = OC6 H4 CH NCH2 CH2 O and OC10 H6 CH hydroxybenzaldehyde and 2-hydroxyacetophenone.80
NCH2 CH2 O, G = CMe2 CMe2 , CMe2 CH2 CHMe and Yu et al.118 have synthesized organotin(IV) complexes,
CMe2 CH2 CH2 CMe2 .116 viz. [(Bu2 Sn)2 O(EtO)(L)]2 , by the reaction of n-Bu2 SnO

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with 4-phenylideneamino-3-methyl-1,2,4-triazole-5-thione, 4-
furfuralideneamino-3-methyl-1,2,4-triazole-5-thione and 4-(2-
thienylideneamino)-3-ethyl-1,2,4-triazole-5-thione.
Singh et al. have adopted the same method for the synthesis
of complexes of the types, Bu2 SnL2 ,119,120,123 Bu2 SnL,121,124 and
Bu3 SnL119,122 (eqn (30)).
Bu 2SnO + 2HL/H 2 L ⎯⎯
→ Bu 2SnL 2 /Bu 2SnL + H 2O (a)
(30)
(Bu 3Sn) 2O + 2HL ⎯⎯
→ 2Bu 3SnL + H 2O (b)
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Equimolar reaction of di-n-butyltin(IV) oxide125 and 1 : 2 molar
ratio reaction of bis(tri-n-butyltin) oxide126 with Schiff bases
derived from amino acids led to formation of new series of
dibutyltin(IV) and triorganotin(IV) complexes of general formula,
n-Bu2 SnL125 and n-Bu3 SnL,126 respectively, using anhydrous ben-
zene and absolute alcohol in 3 : 1 ratio as solvent (eqn (31)).
n-Bu2 SnO/(n-Bu3 Sn)2 O + H2 L/HL →
(31)
n-Bu2 SnL/2(n-Bu)3 SnL + H2 O
Basu Baul and co-workers also synthesized n-dibutyltin(IV)
complexes of type, n-Bu2 Sn(LH)2 and {[n-BuSn(LH)]2 O}2 with
a Schiff base derived from a non-protein amino acid90 (eqn (32)).
n-Bu2 SnO + 2LH2 →
(32)
n-Bu2 Sn(LH)2 {n-Bu2 Sn(LH)2 ]O}2 ·xC7 H8 + H2 O
where, LH2 = 4-[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)ami-
no]benzoic acid, x = 0 in 1 : 1 molar ratio; LH2 = 4-[{(E)-1-(2-
hydroxyphenyl)methylidene}amino]benzoic acid, x = 0.5
in 1 : 1 molar ratio; LH2 = 4-[{(E)-1-(2-hydroxyphenyl)-
methylidene}amino]benzoic acid in 1 : 2 molar ratio.90
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Casas et al.127 have also reported [SnR2 (PLPM - 2H)] (R = Me,
Et, n-Bu and Ph; PLPM = Schiff base formed by condensation
of pyridoxal (PL) and pyridoxamine (PM)), by the reaction of
diorganotin oxides with Schiff bases in a 1 : 1 molar ratio in
refluxing 4 : 1 toluene–ethanol along with azeotropic removal of
water.
Several diorganotin(IV) derivatives of the types, R2 SnL128,129
and R2 SnL2 81 have been synthesized by the reaction of the
corresponding diorganotin(IV) oxides with Schiff bases in desired
molar ratio according to eqn (33).
R2 SnO + H2 L/2HL → R2 SnL/R2 SnL2 + H2 O (33)
where, R = n-Bu, HL = Schiff bases derived from the condensation
of 2-amino-5-(o-anisyl)-1,3,4-thiadiazole with salicylaldehyde, 2-
hydroxynaphthaldehyde and 2-hydroxyacetophenone;81 R = n-
Bu, H2 L = N,N¢-bis(salicylaldehyde)-2,6-diaminopyridine, N,N¢-
bis(2-hydroxy-1-naphthaldehyde)-2,6-diaminopyridine and N,N¢-
bis(benzoin)-2,6-diaminopyridine;128 R = Ph, H2 L = chiral Schiff
base;129
Recently, two dimeric complexes, {(n-C8 H17 )2 Sn[2-
HOC6 H4 CON2 C(CH3 )CO2 ](H2 O)}2 and {(n-C4 H9 )2 Sn[C6 H5 -
CON2 C(CH3 )CO2 ][HOSn(n-C4 H9 )3 ]}2 have been synthesized
by the reactions of pyruvic acid salicyloylhydrazone with di-
n-dioctyltin oxide in benzene–ethanol mixture (3 : 1, v/v) and
pyruvic acid benzoylhydrazone with bis(tri-n-butyltin) oxide in
benzene, respectively.75
A series of complexes of the type R2 SnL2 , where R = Me,
n-Bu and Ph; HL = N-tolyl-m-methoxybenzohydroxamic acid,
have been synthesized by the reaction of the free Schiff base and
appropriate diorganotin(IV) oxide in toluene in 2 : 1 molar ratio.130
Recently, Nath et al.88,115 have also synthesized two di-n-
octyltin(IV) complexes of Schiff bases (derived from condensa-
tion of 2-aminomethylbenzimidazole with salicylaldehyde88 and
from condensation of tris(2-aminoethyl)amine with 4-methyl-
5-imidazolecarbaldehyde)115 by the reaction of di-n-octyltin(IV)
oxide with appropriate Schiff base with azeotropic removal of
water.
2.2.5 By deprotonation with refluxing. Recently, in some
reports,131–135 organotin(IV) complexes of Schiff bases have been
synthesized by refluxing organotin(IV) acetate/halides with Schiff
bases in a suitable solvent as shown in eqn (34).
Rn SnX4-n + H2 L/HL → Rn SnL/Rn Sn(L)Xm (34)
where, n = 2, R = n-Bu, X = OAc, H2 L = 2,9-
diformylphenanthroline bis-benzoylhydrazone (H2 dfpbh)
in methanol;131 n = 2, R = Ph, X = Cl, HL = 2-
quinolinecarbaldehyde-S-methyldithiocarbazate (Hqaldsme) and
2-quinolinecarbaldehyde-S-benzyldithiocarbazate (Hqaldsbz),
m = 1 in a mixture of absolute ethanol and dichloromethane;132
n = 2, R = Me, n-Bu and Ph, X = Cl, H2 L = 2,6-
diacetylpyridine bis(S-methyldithiocarbazate) (H2 dapmdtc) and
2,6-diacetylpyridine bis(S-benzyldithiocarbazate) (H2 dapbdtc)
in methanol;133 n = 2, R = p-ClBz, X = Cl, m = 1, HL =
Dalton Trans., 2011, 40, 7077–7121 | 7087

(2-hydroxyphenylmethylene)hydrazinecarbodithioate, (phenylme-
thylene)hydrazinecarbodithioate, (1,3-benzodioxol-5-ylmethyl-
ene)hydrazinecarbodithioate in THF;134 n = 2, R = Me and Ph,
X = Cl, m = 0, HL = Schiff bases derived by the condensation
of thiosemicarbazide with 1H-indol-2,3-dione, 1,3-dihydro-3-
[2-(fluorophenyl)-2-oxo-ethylidene]-2H-indol-2-one and 1,3-
dihydro-3-[2-(4-fluoro-3-methylphenyl)-2-oxo-ethylidene]-2H-
indol-2-one;135 n = 1, R = Ph, X = Cl, HL = Hnapapi, m = 2;2 n =
2, R = Ph, X = Cl, H2 L = H2 nappdi;38 n = 2, R = Et and n-Bu,
X = Cl, HL = H2 pcph, m = 1, in ethanol;51 n = 2, R = Ph, X = Cl,
HL/H2 L = H5 pdchbh, m = 1/0 with 2H2 O/(CH3 )2 SO;16 n = 2, R =
Et and n-Bu, X = Cl, HL = H3 pdcph, m = 1 with 3H2 O/H2 O.52
Trimetallic and bimetallic complexes of types, [Sn3 -
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(Hpcph)(pcph)(C6 H5 )3 Cl6 ],51 [Sn2 (H2 pdcph)(C6 H5 )3 Cl4 ] and
{[Sn2 (Hpdcph)(C6 H5 CH2 )4 Cl2 ]·2H2 O}51 have also been reported.
Recently, PhSnCl2 (L) has been synthesized by reflux-
ing a solution of Ph2 SnCl2 and 1-{[N-(2-pyridinylmethyl)-
imino]methyl}-2-naphthol (HL) in benzene.113 Similarly, R2 SnL2
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(where, R = Me and Ph; H2 L = 4-bromo-2{[(2-hydroxyphenyl)-
imino]methyl}phenol) have also been reported by the reaction of
R2 SnCl2 with free Schiff base ligand.136
2.2.6 Template synthesis. Rivera and co-workers137,138 have
prepared organotin complexes of Schiff bases derived from a-
amino acids and salicylaldehyde using two different methods.
Direct interaction of Schiff bases with organotin oxides yielded the
products in low yield (10–15%), however, the sequential addition
of equimolar amounts of a-amino acids, salicylaldehyde and
diorganotin(IV) oxide to benzene–ethanol (4 : 1) or acetonitrile
followed by refluxing for 8–16 h yielded the same products in
75 to 94% yield (eqn (35)).
(35)
Reyes et al.139 have also adopted the above methodology for
the preparation of diorganotin(IV) complexes of the Schiff base
derived from 2-amino-5-nitrophenol and salicylaldehyde (eqn
(36)).
7088 | Dalton Trans., 2011, 40, 7077–7121
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(36)
where, R1 = OCH3 and NEt2 , R2 = n-Bu and Ph.139
The one-pot reaction involving 1 : 1 : 1 stoichiometric addition
of salicylaldehyde, b-amino alcohols and diorganotin(IV) oxide
to a 4 : 1 solvent mixture of toluene and butanol, followed by
refluxing for 8 h resulted in the formation of diorganotin(IV)
derivatives of salicylidene-b-amino alcoholates according to
eqn (37).140
(37)
Recently, template synthesis of 3-(2-oxo-phenylimino)-3H-
phenoxazin-2-oxo-dimethyltin and 3-(2-oxo-phenylimino)-3H-
phenoxazin-2-oxo-diphenyltin, involving di-tert-butylbenzo-
quinone, o-phenolamine, triethylamine and R2 SnCl2 in 95%
ethanol at 0 ◦ C followed by stirring at room temperature, has been
reported.141 One-pot synthesis of five- and seven-coordinated
tin complexes, prepared by the reaction of 2-amino-4-R-phenol
(R = H, Me, Cl and NO2 ), 2-pyridinecarbaldehyde, 2-picolinic
acid and dimethyl-, di-n-butyl- and diphenyltin oxides, has been
reported142 as shown in Scheme 9. The reaction of Schiff base
2 (derived from condensation of 2-amino-4-nitrophenol and
2-pyridinecarbaldehyde) with di-n-butyltin oxide led to the penta-
coordinated complex, 2h, through the addition of methanol to the
C N bond (Scheme 9). An usual reduction–oxidation took place
by the reaction of 2-amino-4-nitrophenol, di-n-butyltin oxide
and 2-pyridinecarbaldehyde, which produced the corresponding
amine, 3h, and the amide, 4h, tin(IV) derivatives as shown in
Scheme 9.
2.2.7 By the reaction of triphenyltin hydroxide with Schiff
base. Triphenyltin(IV) hydroxide reacts with 4-(3,5-di-tert-
butylsalicylideneamino)-3-ethyl-1,2,4-triazole-5-thione (HL) in
benzene yielding [Ph3 Sn(L)]·0.5H2 O (eqn (38)).118
Ph3 SnOH + HL → Ph3 SnL·0.5H2 O + 0.5H2 O (38)
2.2.8 By the reaction of organotin(IV) alkoxide with Schiff
bases. The interaction in a 1 : 1 molar ratio of Bu2 Sn(O-i-Pr)2
with Schiff bases yielded homometallic derivatives which on fur-
ther reaction with aluminium complexes afforded heterobimetallic
derivatives143 (eqn (39)).
n -Bu 2Sn(O-i -Pr) 2 + HL-1/HL-2 ⎯⎯
→
n -Bu 2Sn(O-i -Pr)L-1/L-2 + Pr i OH (a)
n -Bu 2Sn(O-i -Pr)(L-1/L-2) + Al(HL-3)/(HL-4) ⎯⎯
→ (39)
{n -Bu 2SnL-1[Al(L-3)/(L-4)}/
{n -Bu 2SnL-2[Al(L-3)/(L-4)} + i -PrOH (b)
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Scheme 9 Reaction routes for one-pot synthesis of five- and seven-coordinated tin complexes.142
where, HL-1 = HOC6 H4 CH NC6 H3 Me2 -2,6, HL-2 = HOC10 -
H6 CH NC6 H3 Me2 -2,6, Al(HL-3) = Al(OCHMeCH2 CMe2 O)-
(OCHMeCH2 CMe2 OH), Al(HL-4) = Al{(OCH2 CH2 )2 (C6 H5 )N-
(OCH2 CH2 (C6 H5 )NCH2 CH2 OH)}143
Stannylation of oxovanadium Schiff base complexes af-
forded the stannyl-substituted mono- and binuclear vanadium
complexes144 (eqn (40)).
Bu3 Sn(O-i-Pr) + [VO(L)(LH)] → [VO(L)(LSnBu3 ) +
(40)
i-PrOH
where, HL = 2-OC6 H4 CH NCH2 CH2 OH.144
2.2.9 Microwave-assisted green synthesis. Recently,
microwave-assisted synthesis of Schiff bases derived
from condensation of S-benzydithiocarbazate with 4-
nitrobenzanilide or 4-chlorobenzanilide in presence of
a few drops of ethanol has been reported.145 Trigonal-
bipyramidal and octahedral dimethyltin(IV) complexes of
4-nitrobenzanilide-S-benzydithiocarbazate, 4-chlorobenzanilide-
This journal is © The Royal Society of Chemistry 2011
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S-benzydithiocarbazate, 4-nitrobenzanilidebenzothiazoline and
4-chlorobenzanilidebenzothiazoline have also been synthesized
using microwave radiation.145 It has been observed that in
microwave method the reaction time has been drastically reduced
with improved yield as compared to the conventional thermal
method. The difference observed may be due to the strong
microwave effect, and the high enhancement of reaction rate.
No doubt the microwave-assisted synthetic process is easy,
convenient, eco-friendly and less time consuming.
2.3. Ionic organotin(IV)-Schiff base complexes
Teo et al.146 have reported the reactions of organotin(IV) chlo-
rides (Me2 SnCl2 , PhSnCl3 and n-BuSnCl3 ) with 6-methylpyridine-
2-carbaldehydephenylhydrazone (L) which resulted in anionic
organotin(IV)-Schiff base complexes, e.g. [LH+ ]2 [Me2 SnCl4 ]2- ,
[LH+ ]2 [PhSnCl5 ]2- and [LH+ ]2 [n-BuSnCl5 ]2- .
Dalton Trans., 2011, 40, 7077–7121 | 7089

3. Physical properties of organotin(IV) complexes of
Schiff bases
Most of the adducts and chelates of organotin(IV) moieties with
Schiff bases are non-volatile, crystalline solids which exhibit sharp
melting points.52,56,67,69,74,76,80,82,87,95,97,100,101,107,110–114,120,121,126,130,141,142,145
Tributyltin(IV) derivatives of Schiff bases derived from heterocyclic
ketones with glycine and isoleucine are semi-solids.126 The complex
from the reaction of H5 pdchbh with Sn(n-C4 H9 )2 Cl2 is obtained
as a lacquer-like solid.52 Molecular weight determination of
R3 SnL68,69,80,126 and R2 SnLn Cl2-n 68,69,82,84,120,110 (where L = Schiff base
ligand, n = 1 or 2) shows a monomeric nature of the complexes,
whereas, some of the complexes are dimeric108 as well as polymeric
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(supramolecular assembly) in nature.85,86,96 The [SnR2 (salop)] and
[SnR3 (salopH)] complexes in the presence of moisture slowly
hydrolyze even in CHCl3 solution, yielding R2 SnO and (R3 Sn)2 O
(oxide) or R3 SnOH (hydroxide).40 In such complexes hydrolysis is
very fast when R = n-Bu.40
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4. Structural and spectroscopic studies of
organotin(IV) complexes of Schiff bases
Structural aspects of the adducts as well as the chelates of
organotin(IV) moieties with Schiff bases have received much
attention. The electronic and multinuclear (1 H, 13 C and 119 Sn)
magnetic resonance spectral studies along with molecular weight
and conductance measurements have been carried out to throw
light on the structures of the complexes in solution. On the
other hand, infrared, 119 Sn Mössbauer and X-ray crystallographic
studies of a few representative complexes have, of course, been
made to elucidate the structures of these complexes in the
solid state. Conclusions drawn on the basis of these studies are
summarized below.
4.1 Molar conductance of organotin(IV) complexes of Schiff
bases
Molar conductance of the adducts and chelates of organotin(IV)
chlorides with unidentate, monofunctional bidentate, bifunctional
terdentate and bifunctional tetradentate Schiff bases have been
measured in different solvents depending upon the solubility of
the complexes, and its has been found that the complexes behave
as non-electrolytes.40,50,69,74,80–82,84,89,99–101,120,121,125,126,130,146 The molar
conductivities of the selected complexes, viz. [R2 SnLCl]+ Cl- ,
where, R = Me, n-Bu and Ph; L = bidentate Schiff bases derived
from substituted and non-substituted 2- or 3-aminopyridine and 2-
hydroxy- or 3-methoxy- or 2-hydroxy-3-methoxy-bezaldehyde46,47
revealed that ionic structures with a 1 : 1 ratio of cation to anion
are present in ethanol and DMF solution. The conductivity value
of [SnX2 (salop)(CH3 OH)] in DMSO has been found in accordance
with the partial ionic dissociation (eqn (41)).40
[SnX2 (salop)(CH3 OH)] + xDMSO 
[SnX2-n (salop)(DMSO)x ] + nX- + CH3 OH (n = 1 or 2; X = (41)
Br or I)
The conductance of Ph3 SnX·L (where L = Schiff base derived
from substituted and non-substituted 2- or 3-aminopyridine and
2-hydroxy- or 3-methoxybezaldehyde) in ethanol and DMF at
ambient temperature showed their non-ionic nature when X = OH
7090 | Dalton Trans., 2011, 40, 7077–7121
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and N3 , whereas, 1 : 1 ionic species occur when X = Cl and NO3 .50
The latter may be due to the fact that the negative ligands, Cl-
and NO3 - are readily released from the coordination sphere of the
complex in polar solvents to give the ionic species [Ph3 Sn·L]+ X- .
4.2 Electronic spectral studies of organotin(IV) complexes of
Schiff bases
Electronic spectra of adducts, Rn SnCl4-n ·L (L = Schiff base)
usually correspond with those of the free Schiff bases which
strongly suggest that ligands maintain their keto-amine hydrogen
bonded configuration in the complexes.40 On the other hand, the
spectra of the chelates of organotin(IV) moieties with different
Schiff bases are found to be quite different from those of the
free Schiff bases, suggesting the deprotonation of Schiff bases
in the chelates40,80,81,84,120,121,125,139 It has been reported that a
metal/metalloid is capable of forming dp–pp bonds with ligands
containing nitrogen as the donor atom. In the electronic spectra
of adducts as well as of chelates, new charge transfer bands in the
region 240–340 nm have also been reported.55,82,84,120,132,140,145 In the
electronic spectra of the Schiff bases and of their organotin(IV)
complexes, two bands are observed in the region 217–233 and
270–309 nm which may be assigned to p–p* transitions of the
benzenoid and of the >C N chromophore.40,55,80–82,84,89,120,121,132,145
The electronic absorption spectra of the dialkyltin(IV) complexes
[SnR2 (FPT)Cl] (R = CH3 and C2 H5 ) in non-polar solvents show
maximum absorption at ca. 340 and 375 nm, and in hydroxylic
solvents at 320 and 380 nm, which may be attributed to the
p–p* transitions of the FPT- anion. The recorded spectra on
successive dilution showed a fixed isosbestic point at 350 nm. This
behavior suggests the solvolysis of these organotin(IV) complexes
in hydroxylic solvents giving solvated ion pairs.76
Recently, electronic excitation spectra of 3- and 4-[1-
pyridin-2-ylmethylidene]aminobenzoic acid in methanol and
dichloromethane have been recorded by Tzimopoulos et al.97
which are shown in Fig. 5. There is an apparent existence of at least
five overlapping bands in every case, the position of which depends
on solvent and on ligand studied. The analysis of overlapping
bands has been carried out using the Peakfit program which
provided evidence for the occurrence of six bands in the recorded
region, on grounds of both intensity and band half-width, with a
significant difference between the ground and excited states. On the
basis of semi-empirical computations, they considered the single
electron excitations involving the four higher occupied and the four
lower occupied molecular orbitals, an approach incorporated into
the MOPAC2009 package. The orbitals are mainly localized on the
pyridine ring or bearing imino or carboxylate character as well,
whereas there also exist, especially in the case of 3-[1-pyridin-2-yl-
methylidene]aminobenzoic acid, delocalized orbitals. Analogous
computations have also been carried out for the methyl- and
phenyl-tin derivatives, though these are of only limited value due to
the assumption of only s and p orbitals for the main group metals.
Further, the observed findings revealed limited contribution by the
organotin fragment to the considered frontier MOs. There appears
to be only one occupied molecular orbital with Sn character, a
fact that is supported by the striking similarity of the electronic
excitation spectra of the organotin compounds with those of the
free ligands.97
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Fig. 5 Electronic excitation spectra of 3-[1-pyridin-2-ylmethylidene]aminobenzoic acid (A) and 4-[1-pyridin-2-ylmethylidene]aminobenzoic acid (B) in
dichloromethane.97 Individual excitations are Gaussian type curves shown as ordinary lines while the total spectrum is represented by a bold line.
4.3 Infrared spectral studies of organotin(IV) complexes of Schiff
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bases
Infrared spectra of the adducts as well as of the chelates of
organotin(IV) moieties provide valuable information regarding
the structures of the complexes in the solid state. Either an
increase or a decrease by a few wavenumbers in the frequency
of C N stretching vibration, which appears in the region
1585–1650 cm-1 in the spectra of free Schiff bases, has been
generally observed, and it has been inferred that the ligands
coordinate to the tin atom through the azomethine nitrogen
atom.38–43,46,47,50–53,55,56,63,64,68,70–76,80,82–89,93,98,102–104,108,110–113,117,120,121,126,127,
129,131–133,137,139,140,145
The shift to lower frequencies (compared
to that of free ligand) indicated donation of the lone pair of
azomethine nitrogen to Sn.46,47,50,55,70,82,87,93,98,102,104,110–113,129,132,145
In contrast, adduct formation results in shifting of n(C N)
to higher frequency.39,41,53,56,63,64,74,104,121,126,146 In some cases there
is no involvement of C N in complexation with tin, whereas
other groups present in ligands take part in complexation
with tin.59,83,85,86,96,97,106 Phenolic n(C–O) vibrations appearing at
~1280 cm-1 in the IR spectra of Schiff bases containing o-hydroxy
groups remain almost unaffected in the spectra of organotin(IV)
adducts, indicating its non-participation in coordination.51,52
However, in the spectra of organotin(IV) chelates, the phenolic
n(C–O) band is shifted to higher wavenumber indicating its
participation in coordination.38–43,57,63,64,68,81,110,120,121,125,127,129 A
strong band attributable to n(C N) which occurs at 1630 cm-1
in the ligand shifts to higher frequency (1650 cm-1 ) and it is
consistent with adduct formation and proton transfer from
the phenolic oxygen atom to the imine nitrogen atom42,57 In
the IR spectrum of an unsymmetrical Schiff base ligand,
methyl-2-[2-(acetylacetoneimino)ethylamino]-1-cyclopent-ene-1-
dithiocarboxylate, a band at 1562 cm-1 has been assigned59 as a
perturbed carbonyl stretching with the frequency lowering from
a free carbonyl ascribed to conjugation and hydrogen bonding
in ketoenamine form III as shown in Fig. 1. In the IR spectra
of adducts, this band shifts to a lower frequency at ~1540 cm-1
providing evidence of participation of oxygen in bonding with tin
and so weakening the C O bond.59
The IR spectra of organotin(IV) derivatives do not show
any band in the region 3400–3150 cm-1 that could be as-
signed to n(N–H) or n(O–H). This clearly indicates the de-
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protonation of the ligands as a result of complexation with
tin.70,71,73,84,92,98,105,112,113,118,120,121,125,127,129,130 A weak broad band in the
region 3250–2350 cm-1 has been assigned to intramolecularly
hydrogen bonded OH in the Schiff bases, and it is not observed
in the IR spectra of organotin(IV) complexes80,104,108,126 indicating
the replacement of phenolic hydrogen upon complexation. n(O–
H) in some organotin(IV) complexes is found at 3387–3478 cm-1 ,
and suggests that the oxygen atom of the phenolic hydroxyl group
does not participate in coordination to Sn.72,106,107
The IR spectra of organotin(IV) derivatives of Schiff bases
derived from amino acids or carboxylic acids provide use-
ful information concerning the coordination behavior of the
carboxylate group. In the complexes, n as (COO) and n s (COO)
appear at 1608–1622 and 1369–1453 cm-1 , respectively. The
magnitude of Dn [n as (COO) - n s (COO)] is 230–285 and 150–
190 cm-1 , indicate the presence of mono-72,73,75,92–94,97,107,108,121,125,126
or bidentate72,73,90,94,96,97,106 carboxylic groups, respectively. Recently,
Basu Baul et al.95 have assigned a strong band at ~1650 cm-1 as
n as (COO) for triphenyltin(IV) complexes and at 1685 cm-1 for a
diphenyltin(IV) complex of amino acetate functionalized Schiff
base, but the n s (COO) band could not be assigned owing to the
complex pattern of the spectra.
Routine IR spectral measurements of the complexes
revealed that coordination of Schiff bases had
taken place via N→Sn linkage and this is clear
from n(Sn–N), which appeared in the region 375–
495 cm-1 .46,47,50,55,56,68–70,74,75,80–82,84,85,87,102,104,105,107,108,110–113,117,120,121,125–127,
129,137
It has been reported that the cis form of the complexes
gives rise to two n(M–N) bands, whereas in the trans form only
one IR active n(M–N) band is observed.47 The IR bands in the
regions 315–375, 410–420 and 560–580 cm-1 have been assigned to
n(Sn–O) 46,47,59,70,71,74,92,93,100,101,104,105,108,110,111,113,116,121,126,129,130,137,139,146
and at 540–565 cm-1 is assigned to (Sn←O).39,43,69,75,107 A band in
the region 318–365 cm-1 has been assigned to n(Sn–S) in some
complexes where sulfur is involved in coordination.82,83,87
The IR bands at ca. 1464, 1288, 1106 and 813 cm-1 in
the spectrum of HFPT, which have a significant contribution
from n(C S), are shifted to lower frequency in spectra of its
organotin(IV) complexes. This behavior is consistent with expected
decrease in the C S double bond character resulting from the
coordination of thiol sulfur of the FPT- anion.20,39,45,69,82,83 In
organotin(IV) complexes48,69 containing a Schiff base derived from
Dalton Trans., 2011, 40, 7077–7121 | 7091

triazole, the frequency of n(S–H) is not observed at 3106 and
2925 cm-1 but a new band due to n(C S) occurs at about
1242 cm-1 , indicating the deprotonation of N–H of the thione
form. Similarly, n(S–H) at 2722 cm-1 observed in Schiff bases de-
rived from 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol/5-amino-
1,3,4-thiadiazole-2-thiol is not observed in complexes.87
The IR spectra of both N-salicylidene and N-pyridoxylidene
acylhydrazone show a series of bands in the regions 3180–3300,
1680–1670, 1600–1620, 1520–1515 and 1350–1375 cm-1 due to
n(N–H), amide I [n(C O), n(C C) + n(C N)], amide II [d(N–
H) + n(C–N)] and amide III [n(C–O)], respectively. The spectra
of corresponding organotin(IV) complexes lack any absorptions
attributable to n(N–H), and amide I. Instead the spectra show
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strong absorption within the 1600–1620 cm-1 region due to
n(C N–N C). This suggests that the deprotonated phenolic
oxygen, azomethine nitrogen and the deprotonated enolic amide
oxygen are involved in coordination with tin.67,70,72,74,105,107–109
The presence of both n s (Sn–C) and n as (Sn–C) in the IR spectra
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of dialkyltin(IV)/trialkyltin(IV) complexes at 520 ± 5 and 550 ±
15 cm-1 , respectively, and of diaryltin(IV)/triaryltin(IV) complexes
at 267 ± 7 and 229 ± 11, respectively, are consistent with a nonlinear
C–Sn–C configuration.55,57,59,81,84,113,120,121,125–127 Whereas the obser-
vation of only one Sn–C stretching frequency is consistent with a
trans arrangement of organic groups around tin.55,75,84,104,110,117
4.4 Multinuclear (1 H, 13 C and 119 Sn) magnetic resonance spectral
studies
1
In the H NMR spectra of organotin(IV) adducts and
chelates of various Schiff bases,40,54–56,63,64,66–68,71,72,74,80–82,
84,88,89,92–94,99,102,103,105,109,111–115,121,125–127,129–132,136,137,139,140
slightly
downward chemical shift values for –CH N– or –
C(CH3 ) N– protons may arise due to participation of
azomethine nitrogen in chelation. Disappearance of OH,
NH and SH signals of mono- or bifunctional Schiff
bases in the 1 H NMR spectra of their organotin(IV)
chelates indicates chelation of the ligand moiety through
deprotonated oxygen, nitrogen and sulfur atom, respective-
ly.38,40,66–69,71,73,74,75,80–82,84,85,87,88,100–105,109–113,117,120,121,125–127,130,132,133,136,137,145
Dey et al.39 have reported that the relative intensities in 1 H NMR
spectra of Me2 SnCl2 (HL)2 and Ph2 SnCl2 (HL)2 (where, HL = o-
HOC6 H5 CH NC6 H4 R-4; R = Me, Cl and OMe) are in agreement
with the formulation of the complexes as 1 : 2 adducts. In the 1 H
NMR spectra of free Schiff bases, the resonance of the phenolic
proton involved in intramolecular hydrogen bonding occurs at d
~ 13.0 ppm, and this signal is slightly broadened in the spectra of
the adducts, thus suggesting the presence of O ◊ ◊ ◊ H–N rather than
O–H ◊ ◊ ◊ N hydrogen bridge in complexes. Coordination through
oxygen of phenolic O–H is expected as this resulted in weakening
of the O–H bond and strengthening of C N ◊ ◊ ◊ H hydrogen bond,
or there are some exchange phenomena in solution in which the
phenolic hydrogen is localized near the imine nitrogen atom.39,42,57
This leads to the observed broadening of the peak due to phenolic
proton. The presence of a signal at 5.0 ppm (1H) corresponds
to the vinylic hydrogen and absence of a methylene signal
near 3 ppm (2H) indicates no participation of ketimine form I
of methyl-2-[2-(acetylacetoneimino)ethylamino]-1-cyclopentene-
1-dithiocarboxylate (as shown in Fig. 1) in solution.59 Further the
NH protons appear at low field due to intramolecular hydrogen
7092 | Dalton Trans., 2011, 40, 7077–7121
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bonding, and broadening of the signal at d 10.94 ppm, attributable
to the NH proton in the acetylacetone moiety, indicates the
weakening of the O–H bond and proton transfer to imine nitrogen
atom (tautomeric form III as shown in Fig. 1). The presence of
both NH protons in the corresponding organotin(IV) complexes
indicates that Schiff base is coordinated to tin in a neutral form.59
The signal attributable to the imine proton –CH N– in the
spectra of some complexes is not flanked by satellites, this is
reported as an indication that the N atom is not coordinated to the
organotin(IV) moiety.40–42,57,59,68,83,85,86,96,106 The lack of a downfield
shift in position of the signal attributable to S–CH3 (d 2.59 ppm in
free ligand) suggested little or no participation of the C S group
in bonding.59,133
The 1 H NMR spectra of SnMe2 Cl2 (H2 cdsalen) and
SnMe2 Cl2 (Hcdacacen) showed singlets at d 1.22 and 1.21 ppm
(6H) for CH3 –Sn, and the observed 2 J(119 Sn–1 H) value (71.0/76.5
Hz) 57,59 is typical of a penta-coordinated dimethyltin(IV) complex.
Substitution of the 2 J(119 Sn–1 H) value in the Lockhart–Manders
equation [∠Me–Sn–Me = 0.0161[2 J(119 Sn–1 H)]2 - 1.32[2 J(119 Sn–
1
H)] + 133.4]147 gives a value of 126.6◦ for the Me–Sn–Me angle.59
In SnPh2 Cl2 (H2 cdsalen) and SnPh2 Cl2 (Hcdacacen), a signal is
found with 3 J(119 Sn–1 H) value greater than that in SnPh2 Cl2
(81.7 Hz) which indicates the higher coordination number of
tin.57,59 Similar results have been reported for other diorgan-
otin(IV) complexes of tridentate ONO donor Schiff bases.113
Dimethyltin(IV) complexes of Schiff bases derived from 2-amino-
3-hydroxypyridine and various substituted salicylaldehydes have
been reported to exhibit 3 J(119/117 Sn–1 H) values of 48.6–50.5 Hz
for the imine proton which clearly indicates the coordina-
tion of the azomethine nitrogen to the tin atom.112 Similarly,
3
J(119/117 Sn–1 H) values of 76.0–55.0 Hz have also been reported for
other diorganotin(IV) complexes of tridentate ONO donor Schiff
bases.113 Further, the coupling constants, 2 J(119 Sn–1 H) and 1 J(13 C–
119/117
Sn) have been observed in the range 77.6–87.5 Hz112,113 and
629.6–658.6 Hz,111 respectively, which indicate a five-coordinate
environment around the tin. Using the observed 2 J(119 Sn–1 H)
values in the Lockhart–Manders equation,147 and 1 J(13 C–119/117 Sn)
values in the equation [1 J(13 C–119/117 Sn) = 10.7q - 778] 147,148 resulted
in Me–Sn–Me angles in the range 127.9–139.0◦ 112,113 and 131.6–
134.4◦ ,112 respectively.
The 1 H NMR spectra of organotin(IV) anionic complexes, viz.
[LH+ ]2 [Me2 SnCl4 ]2- , [LH+ ]2 [n-Bu2 SnCl5 ]2- and [LH+ ]2 [Ph2 SnCl5 ]2-
derived from the reaction of organotin(IV) chlorides
(Me2 SnCl2 , n-BuSnCl3 and PhSnCl3 ) with 6-methylpyridine-
2-carbaldehydephenylhydrazone showed diagnostic peaks at d
11.195 ± 0.565 ppm and 7.985 ± 0.155 ppm, which are assigned
to the azomethine (CH N) and hydrozonyl (NH) protons,
respectively.146 However, the peak due to the proton on the
endocyclic N atom is not observed, leading to the suggestion
that this proton is very mobile in organic solvent. Inspection of
13
C NMR data shows that a peak assignable to the azomethine
carbon in the Schiff base at d 137.05 ppm is shifted to d 143.885 ±
0.805 ppm upon complexation.146 The shift can be rationalized by
a long-range inductive effect wherein the p electron density on the
C N bond is essential for stabilizing the protonated endocyclic
N atom.
Labib et al.76 have studied organotin(IV) complexes with 2-
formylpyridine thiosemicarbazone (HFPT). 1 H and 13 C NMR
spectra of [Sn(CH3 )(FPT)Cl2 ] in DMSO-d 6 suggested the
This journal is © The Royal Society of Chemistry 2011

bidentate nature of the FPT - anion where the pyridine nitrogen
is not coordinated to central tin. However, the 1 H NMR spectrum
showed tin coupling satellites of the CH N proton (J = 56.0
Hz), indicating the coordination of the azomethine nitrogen. The
values recorded for 3 J(119 Sn–1 H) are within the range reported
for octahedral tin(IV) complexes, suggesting the expansion of the
coordination number of tin and formation of solvated species
(Fig. 6).
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
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Fig. 6 Structure of solvated [Sn(CH3 )(FPT)Cl2 ].76
The 119 Sn NMR spectra of a number of organotin(IV)
complexes40,57,68,70,73,82,84,90,107,108,111–113,121,125,126,129,133,139 show only one
sharp singlet indicating the formation of single tin species. On
the basis of the 1 H, 13 C and 119 Sn NMR spectral data, penta-
coordinated trigonal-bipyramidal and hexa-coordinated octahe-
dral geometries, respectively, have been suggested for 1 : 1 and 1 : 2
organotin(IV) derivatives of 2-acetylfuransulfaguanidine.74,84
Annunziata et al.66 have studied 1 H and 13 C NMR spectra of
organotin(IV) complexes of the general formula, L2 SnR2 (HL = N-
(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroaniline; R = CH3 ,
n-C4 H9 ) and L¢2 SnR2 (HL¢ = N-(3-tert-butylsalicylidene)aniline;
R = CH3 , n-C4 H9 ), which are compatible with the existence
of a single Sn C 2 -symmetric species in solution. The CH N
hydrogen atoms appear as a singlet at d 8.02 ± 4 ppm, with
3
J(119 Sn–1 H) values of 15.9 and 14.3 Hz.66 The 3 J(119 Sn–1 H)
values of 12.6 Hz for [n-BuSn(salophen(t-Bu))Cl] and 13.2 Hz
for [n-BuSn(salomphen(t-Bu))Cl];102 26.0 Hz for [Me2 Sn(PLPM
- 2H)], 25.0 Hz for [Et2 Sn(PLPM - 2H)], 36.0 Hz for [n-
Bu2 Sn(PLPM - 2H)] and 52.0 Hz for [Ph2 Sn(PLPM - 2H)];127
61.6 Hz and 41.2 Hz for n-butyl- and phenyltin(IV) complexes of
Schiff bases derived from amino acids;137 and in the range of 45.0–
60.0 Hz for n-butyl- and phenyltin(IV) complexes of Schiff bases
derived from the condensation of methoxysalicylaldehyde or 4-
diethylaminosalicylaldehyde with 2-amino-5-nitrophenol139 have
been reported. This indicates the coordination of the azomethine
N atom to the tin center.66,92–94,102,127,137,139 The 1 H NMR spectrum of
bis[N-(3-tert-butylsalicylidene)anilinato]dimethyltin(IV) exhibited
two sets of signals, attributable to two different isomeric species,
a C 2 -symmetric one and a C 1 -symmetric one, respectively, in
about 3 : 2 ratio.66 Diagnostic signals for the C 2 -symmetric isomer
are the singlet of the Sn–CH3 groups (6H, 2 J(119 Sn–1 H) = 68.12
Hz) at d 0.16 ppm, the t-Bu singlet (18 H) at d 0.97 ppm, and
the CH N singlet at d 8.11 ppm (3 J(119 Sn–1 H) = 30.8 Hz).66
According to the Nelson equation, the measured 2 J(119 Sn–1 H)
value is compatible with a structure showing the methyl groups
bound to Sn in mutually cis positions. For the C 1 -symmetric
isomer, instead, two signals belonging to the Sn–CH3 groups at
d 0.33 ppm (3H, 2 J(119 Sn–1 H) = 65.5 Hz) and d -0.21 ppm (3H,
This journal is © The Royal Society of Chemistry 2011
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2
J(119 Sn–1 H) = 65.9 Hz) and two signals (overlapped, 18H) for the
t-Bu groups at d 1.35 and 1.34 ppm 66 are observed.
Singh and Varshney82 have studied 1 H, 13 C and 119 Sn NMR spec-
tra of organotin(IV) complexes of bidentate Schiff bases prepared
by condensation of S-benzyldithiocarbazate (NH2 NHCS2 CH2 –
C6 H5 ) with heterocyclic aldehydes and suggested a trigonal-
bipyramidal and an octahedral geometry (Fig. 7) for Ph2 SnLCl
and Ph2 SnL2 , respectively. The downward chemical shifts in the
13
C signals due to the thionic (d -172.8 ppm) and the azomethine
(d -160.0 ppm) groups in the complexes indicate the involvement
of sulfur and nitrogen atoms in coordination. A sharp signal at
d -235.4 and -456.8 ppm in 119 Sn NMR spectra of Ph2 Sn(L)Cl
and Ph2 SnL2 , respectively, has been observed which strongly
supports five- and six-coordination around tin in a trigonal-
bipyramidal and distorted octahedral geometry, respectively.82
Similarly, the signals due to the carbon atoms attached to the
thionic and azomethine groups in 4-nitro-/4-chlorobenzanilide-S-
benzyldithiocarbazates (d 180–178 and 163–161 ppm) have been
reported to get shifted to around d 163 and 164 ppm, respectively,
in the corresponding dimethyltin(IV) complexes, indicating the
involvement of sulfur and nitrogen atoms in coordination.145
Fig. 7 Geometry of (A) Ph2 Sn(L)Cl and (B) Ph2 SnL2 .82
The 119 Sn NMR spectroscopic data of {(n-Bu)2 Sn[2-S-
C4 H3 CON2 C(CH3 )CO2 ](HOC3 H7 -i)}2 , [{(n-Bu)2 SnCl(O)(n-Bu)2 -
Sn(O)[C6 H4 CON2 C(CH3 )CO2 ]Sn(n-Bu)2 (HOCH3 )}2 ]n , {(o-
ClBz)2 Sn[4-HOC6 H4 CON2 C(CH3 )CO2 ](HOC2 H5 )}2 ,{(n-C8 H17 )2 -
Sn[2-HOC6 H4 CON2 C(CH3 )CO2 ](H2 O)}2 and {(n-
C4 H9 )2 Sn[C6 H5 CON2 C(CH3 )CO2 ][HOSn(n-C4 H9 )3 ]}2 75 show
one resonance signal in the range d -447 to -460 ppm
indicating seven-coordination. Besides, for [{(n-Bu)2 SnCl(O)(n-
Bu)2 Sn(O)[C6 H4 CON2 C(CH3 )CO2 [Sn(n-Bu)2 (HOCH3 )}2 ]n , there
also exist two signals, d = -177 and d = -196 ppm, which are
in the range of five-coordinate di-n-butyltin(IV) derivatives, thus
indicating the existence of another two different coordination
environments around the tin atoms for this complex. However, {(n-
Bu)2 Sn[C6 H5 CON2 C(CH3 )CO2 ][HOSn(n-Bu)3 ]}2 shows another
signal at d -107 ppm, which is in the range corresponding to a type
of four-coordinate tetrahedral tin atom, thus it can reasonably be
assumed that there is also one different coordination environment
around tin atom for this complex in solution. [(n-C4 H9 )SnCl2 ]- [4-
NHC5 H4 CON2 CH(C6 H4 O-2)]+ shows a signal at d -365 ppm
corresponding to the six-coordinate tin.75 Further, 119 Sn NMR
spectra of [(R3 Sn)2 (C24 H16 N8 S2 )]Y (R = Ph, Y = 0 (1); R = PhCH2 ,
Y = 2CH3 OH (2); R = n-Bu, Y = 0 (3)), [(R3 Sn)2 (C24 H16 N8 S2 )]n
(R = Me (4)), [(R3 Sn)2 (C12 H6 N6 S4 )].Y (R = Ph, Y = CH2 Cl2 (5);
Dalton Trans., 2011, 40, 7077–7121 | 7093

R = PhCH2 , Y = 0 (6)) and [(R3 Sn)2 (C12 H6 N6 S4 )] (R = n-Bu
(7), R = Me (8)) in CDCl3 show resonances between d - 53.5
and -76.7 ppm except compounds 2 and 4, which is typical of
four-coordinate environment around the tin atom in solution.87
The compounds 2 and 4 show resonances at d = -114.2 and
-123.7, -128.3 ppm, respectively, indicating the five-coordinate
environment around the tin atoms in solution.87
Nath et al.88 have investigated 1 H, 13 C and 119 Sn NMR spectra of
tri- and diorganotin(IV) complexes of Schiff base (Hsal-ambmz)
derived from 2-aminomethylbenzimidazole and salicylaldehyde.
The monobasic bidentate Schiff base exhibits a hydrogen-bonded
OH (phenolic) proton signal at d 12.83 ppm in DMSO-d 6 . The
absence of such signal in all of the organotin(IV) complexes
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
suggests the deprotonation of the phenolic OH of Schiff base
on complexation.88 In the 1 H NMR spectra of the complexes,
a signal at d 8.63 ± 0.04 ppm for triorganotin(IV) complexes
and d 8.72 ± 0.09 ppm for diorganotin(IV) complexes has been
assigned to the azomethine proton (–CH N–). It appears at low
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frequency in all of the studied complexes as compared to the
corresponding signal of uncoordinated Schiff base (8.69 ppm in
CD3 OD/8.96 ppm in DMSO-d6 ), indicating coordination of the
ligand to the tin via azomethine nitrogen (Sn←N). Two signals due
to both azomethine protons appear in the spectra of n-Bu2 Sn(sal-
ambmz)2 , n-Oct2 Sn(sal-ambmz)2 and Ph2 Sn(sal-ambmz)2 , but
not for Me2 Sn(sal-ambmz)2 where a broad unresolved signal is
obtained, indicating the presence of a non-equivalent magnetic
field around two ligand molecules. The signals due to NH group
could not be located in the d 0–15 ppm region, neither in the
spectra of Schiff base nor in the complexes. The signal due to
CH2 protons appears at d 5.05/5.06 ppm as a sharp singlet in
Schiff base while this signal in complexes is overlapped with those
of solvent and appears as a broad singlet in the range of d 4.82–
5.00 ppm. It is difficult to distinguish between the aromatic protons
attached to the tin atom and those of the Schiff base. The Sn–
CH3 protons in the spectra of Me3 Sn(sal-ambmz) appear as two
singlets at d 0.41 and d 0.07 ppm. This also indicates that all
the three methyl groups are not equivalent. The intensity of the
signal centered at d 0.41 is approximately twice of the second
signal at d 0.07 ppm. In the same way all the non-equivalent
alkyl/phenyl protons of the organic groups attached to tin are
also observed. The 2 J(1 H–119 Sn) and 3 J(1 H–119 Sn) values are 64.0,
54.7 Hz for Me3 Sn(sal-ambmz), 70.9, 56.5 Hz for n-Bu3 Sn(sal-
ambmz) and 63.6, 83.3 Hz for Ph3 Sn(L), respectively. Except for
83.3 Hz for Ph3 Sn(sal-ambmz), the 2 J(1 H–119 Sn) coupling constant
values correspond to a pentacoordinated, trigonal-bipyramidal
geometry. Among diorganotin(IV) complexes, the 2 J(1 H–119 Sn)
value has been determined only for Me2 Sn(sal-ambmz)2 (76.2 Hz)
which corresponds to octahedral geometry. The ∠C–Sn–C calcu-
lated by using Lockhart and Manders equation147 is in the range
109.38–120.79◦ for triorganotin(IV) complexes indicating also a
distorted trigonal-bipyramidal geometry. The n J(1 H–119 Sn) values
of Ph3 Sn(sal-ambmz) (83.3 Hz) and Me2 Sn(sal-ambmz)2 (76.2 Hz)
correspond to ∠C–Sn–C of 135.13 and 126.36◦ , respectively, which
clearly indicate a distorted cis-octahedral arrangement.88 In the
13
C NMR spectrum of the Schiff base in CD3 OD/DMSO-d6 the
signals corresponding to carbon atom attached to the phenolic
oxygen (C-1) and azomethine nitrogen (C-7) are observed at d
168.5/164.5 and 160.9/160.7 ppm, respectively, which are shifted
either toward high or low frequency (downfield or upfield) in all of
7094 | Dalton Trans., 2011, 40, 7077–7121
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the studied organotin(IV) complexes, indicating the coordination
of deprotonated Schiff base to tin via (O)phenolic attached to C-
1 and (N)azomethine attached to C-7 as shown in Scheme 4. These
chemical shifts are slightly shifted in organotin(IV) complexes
as compared to uncoordinated ligand because the extent of O–
H–N hydrogen bonding is greatly reduced upon complexation.
The alkyl carbon of the Schiff base is shifted towards higher
field, Dd 7.6 to 7.7 ppm, which also supports the coordination
of azomethine nitrogen to tin. In the most of the studied
organotin(IV) complexes, the satellites are resolved and observed
coupling constants 1 J(13 C–119 Sn) are 476 ± 10 Hz and 715 ± 36 Hz
for triorganotin(IV) and diorganotin(IV) complexes, respectively.
These values lie in the range of pentacoordinated (trigonal-
bipyramidal) and hexacoordinated (octahedral) arrangements.
Moreover, the calculated values of ∠C–Sn–C using observed
1
J(13 C–119 Sn) values in the equation given by Lockhart and
Manders [|1 J(117/119 Sn–13 C)| = 11.4q - 875]147,149 are in the range
of 117.55–119.39◦ for triorganotin(IV) complexes and 136.31–
142.51◦ for diorganotin(IV) complexes indicating a distortion in
their trigonal-bipyramidal and octahedral geometry, respectively.
The observed 119 Sn chemical shifts of the studied triorganotin(IV)
complexes (d -104 to - 472 ppm) are in the range of five-
coordinated tin compounds, whereas for the diorganotin(IV)
complexes (d -228 to -553 ppm), the observed 119 Sn chemical
shifts are in the range of six-coordinated tin compounds.88 The
119
Sn NMR spectrum of Ph3 Sn(sal-ambmz) shows two signals
at d -122.51 and - 471.63 ppm in CD3 OD and at -129.07 and
-392.99 ppm in CD2 Cl2 , which correspond to the presence of
five- and six-coordinate tin moieties, respectively, in 2 : 1 ratio
as indicated by their intensities. Therefore, the weak interaction
between the central tin and (N)imidazole may occur leading to an
octahedral species in solution. The broadness (±405 Hz) of the
119
Sn resonance at room temperature in CD2 Cl2 suggests the
existence of an equilibrium mixture of different species (Fig. 8),
which are also observed in 1 H (3 J(1 H–119 Sn) = 63.6, 83.3 Hz) and
13
C NMR (C-a = 139.7 ppm, a weak resonance at 141.4 ppm, which
becomes slightly more intense at 285 K). In Me3 Sn(sal-ambmz),
two resonances at d -10.65 and -103.57 ppm together with a
very weak signal at 0.56 ppm are observed in an approximate
intensity ratio of 40/40/5. The 2D 1 H–119 Sn HMQC spectrum
displays 2 J(1 H–119 Sn) coupling correlation between methyl proton
resonances and 119 Sn resonances at 0.56 ppm (54.7 Hz) due to
Me4 Sn and at -10.65 ppm (64.0 Hz) due to Me3 Sn(sal-ambmz).
The tin resonance at -103.57 ppm also correlates with methyl
resonances with an approximate 2 J(1 H–119 Sn) value of 76.0 ±
0.8 Hz. These results suggest the dissociation of Me3 Sn(sal-
ambmz) in nucleophilic solvent CD3 OD according to eqn (42),
HL = Hsal-ambmz:

2Me3SnL 
CD3OD
 
 Me 4Sn + Me 2SnL⋅ solvent (42)
The possible geometries around tin in tri- and diorganotin(IV)
complexes of (Hsal-ambmz) are distorted trigonal-bipyramidal
and octahedral, respectively, as shown in Scheme 4, in which the
Schiff base acts as a bidentate ligand and coordinates through the
phenolic oxygen (O) and azomethine nitrogen (N). The possible
structures of Ph3 Sn(sal-ambmz) are shown in Fig. 8.
Basu Baul et al.95 have observed 3 J(119/117 SnN CH)
coupling constant values of 57 Hz for di-/triphenyltin
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Fig. 8 (a) cis-Trigonal-bipyramidal (distorted) structure of Ph3 Sn(L) and
(b) octahedral (distorted) structure of Ph3 Sn(L) involving weak interaction
between tin and (N)imidazole .88
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
complexes of amino acetate functionalized Schiff base lig-
ands of the formula, [Ph3 SnLH]n and [Ph2 SnL], confirming
the presence of nitrogen–tin coordination. Further, [Ph2 Sn(2-
OC6 H4 C(H) NCHCH2 CH(CH3 )2 COO] displayed two sets of 1 H
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and 13 C NMR signals from the Sn–Ph groups since the italicized
proton in the complex is enantiotropic and causes the phenyl
groups bound to the tin, and the i-Bu group to be diastereotopic,
and thereby the two phenyl groups (SnPh2 ) experience different en-
vironments on the NMR time scale. Furthermore, triphenyltin(IV)
complexes exhibit a single sharp 119 Sn resonance (in CDCl3 )
in the range d -83 to -103 ppm, suggesting a four-coordinate
environment around the tin which is also unambiguously reflected
in the 1 J(13 C–119/117 Sn) coupling constants (662–654/634–627 Hz).
These results demonstrated that the polymeric structure with
five-coordinate tin atoms found in the solid state is lost upon
dissolution. On the other hand, [Ph2 SnL] displayed a 119 Sn
chemical shift at d = -340 ppm [1 J(13 C–119/117 Sn) = 994 Hz) which
corresponds to a five-coordinate environment around the tin atom
in solution.95
1
H and 13 C NMR spectral data of triorganostannyl esters of
the 3- and 4-[1-pyridin-2-ylmethylidene]- and 3,5-bis-[1-pyridin-2-
ylmethylidene]benzoic acids indicate that in CDCl3 solution there
is no participation of the imino nitrogen atom in the coordination
to tin since there are no appreciable changes in the imine proton
and carbon resonances between the free ligands and the organotin
compounds, whereas the carboxylate coordination is indicated
from the downward shift of the carboxylate carbon atom.97 The
coupling constants, 1 J(13 C–119 Sn) and 2 J(1 H–119 Sn) lie in the range
310–395 and 57–70 Hz, respectively, indicating the coordination
number of tin not exceeding five.97
Varshney et al.120 have investigated 119 Sn NMR spectra of
the hexacoordinated dibutyltin complexes, [Bu2 Sn(L)2 ] (where L
is the anion of Schiff bases derived by condensation of 2-
acetylfuran or 2-acetylthiophene with sulfaguanidine, sulfathia-
zole, sulfisoxazole and sulfadiazine). The observed 119 Sn chemical
shifts between d -275 ppm and -290 ppm are in good agreement
with values for hexa-coordination around tin atom. Similarly,
the 119 Sn chemical shifts in the range of d -210 to -440 ppm
for diorganotin(IV) complexes of 2-[(9H-purin-6-ylimino)]phenol
indicate a six-coordinate environment around the tin which is
supported by the observed values of 1 J(13 C–119 Sn) = 755–830 Hz
and 2 J(1 H–119 Sn) = 67–85 Hz.111 The 119 Sn chemical shifts in the
range of d -280 ppm to -321 ppm for diphenyltin(IV) complexes
and at d -140 ppm for dimethyltin(IV) complex of tridentate ONO
Schiff bases indicate a coordination number of five for tin, whereas
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the 119 Sn chemical shift at d -487 ppm in a diphenyltin(IV) complex
of a Schiff base derived from 2-hydroxynaphtaldehyde and 2-
(aminomethyl)pyridine indicates six-coordination for tin.113
The 1 H NMR spectra of (Ph2 /Me2 )Sn[Ph(O)C(10) C(9)H–
C(7)(Me) N–C6 H4 (O)] exhibits 2 J(13 C–119 Sn) values of 21.5 and
11.3 Hz with C(10) and C(7), respectively, and 3 J(13 C–119 Sn)
value of 32.3 Hz with C(9) indicating the coordination of the
enolic oxygen and nitrogen atoms of the ligand with tin.114
Further, 2 J(13 C–119 Sn) and 3 J(13 C–119 Sn) values of 13.0 and 12.0 Hz,
respectively, with C(1) and C(2) carbons of the phenyl ring
[C6 H4 (O)] indicates the coordination of phenolic oxygen atom
of the ligand with tin.114 The 1 J(13 C–119 Sn) value of 979.0 Hz
for diphenytin(IV) and 648.5 Hz for dimethyltin(IV) complex
indicates six-coordination of tin. Using the 1 J(13 C–119 Sn) value in
the equation, |1 J(13 C–119 Sn)| = (15.91 ± 0.72)q - (1164 ± 84),150 the
Cphenyl –Sn– Cphenyl angle has been found to be 134.2◦ [cf. 120.1(2)◦
in the X-ray study], whereas the Cmethyl –Sn– Cmethyl angle has been
found to be 133.3◦ using the equation [1 J(13 C–119/117 Sn) = 10.7q
-778] [cf. 141.7◦ in the X-ray study].114,148 Furthermore, by using
the observed 2 J(1 H–119 Sn) value of 77.1 Hz for the dimethyltin(IV)
complex in the Lockhart and Manders equation,147 the Cmethyl –Sn–
Cmethyl angle has been found to be 129◦ , yet this is lower than the
value as obtained from X-ray study. The X-ray crystal structure of
this complex showed that it forms a dimeric structure (discussed in
X-ray studies) through a long range coordinated phenolic oxygen
atom of a second molecule. There is an expansion of Cmethyl –Sn–
Cmethyl angle (141.7◦ ) angle to accommodate a sixth coordination
site. However, in solution this dimeric structure dissociates to
become a discrete five-coordinate tin complex which contributes
to the low Cmethyl –Sn– Cmethyl angle as estimated from NMR in
solution.114
119
Sn NMR spectra of tributyltin(IV) complexes of Schiff bases
derived by condensation of heterocyclic ketones and amino acids
showed signals at d -130 ± 10 ppm which are in good agreement
with values for five-coordination around tin atom. The following
structure (Fig. 9) has been suggested for these complexes.126
Fig. 9 Suggested structure of organotin(IV)-Schiff bases (derived from
amino acids).126
119
Sn NMR spectra of 3-(2-oxo-phenylimino)-3H-phenoxazin-
2-oxo-dimethyltin/-diphenyltin showed a resonance at d -
68.9/-243.6 ppm which correspond to pentacoordinated tin in
a square pyramidal geometry. The coupling constant, 1 J(13 C–
119/117
Sn) = 624/594 Hz, in 3-(2-oxo-phenylimino)-3H-phenoxazin-
2-oxo-dimethyltin also confirms five-coordinate environment
around tin.141
Recently, Nath et al.115 have studied 1 H, 13 C and 119 Sn NMR
spectra of tri- and diorganotin(IV) complexes of a tripodal Schiff
base ligand (H3 L) containing three imidazole arms. In the 1 H
NMR spectrum of H3 L, a resonance at d 8.23 ppm has been
assigned to the azomethine (–CH N–) protons. In most of the
Dalton Trans., 2011, 40, 7077–7121 | 7095

studied organotin(IV) complexes, three signals are observed in
the range d 8.87–7.33 ppm for azomethine protons, indicating
the non-equivalence of azomethine protons. Further, a large shift
is observed in two signals (Dd (0.64–0.05) and (0.24–0.04) ppm,
for azomethine protons) in most of the organotin(IV) complexes,
suggesting the participation of two azomethine nitrogens in coor-
dination. The proton signals of three (–N–CH2 –CH2 –N ) groups
(at positions 2–3, 2¢–3¢ and 2¢¢–3¢¢ as shown in Fig. 4) appear as a
broad singlet at d 3.70 ppm and a multiplet centered at d 2.86 ppm
in H3 L. In the organotin(IV) complexes, a number of resonances
with large downfield shifts are observed for these protons which
also support the participation of the azomethine nitrogen in
bonding to tin. The exchangeable NH imidazole proton has not
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
been observed up to d 15 ppm under experimental conditions in
both H3 L and its organotin(IV) complexes. The imidazole protons
( C–H)imidazole of the Schiff base appear as a sharp singlet at d
7.62 ppm, whereas in organotin(IV) complexes, the corresponding
protons appear as a number of signals, indicating non-equivalence
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of imidazole rings. The methyl protons attached to the imidazole
ring of H3 L appear as a sharp singlet at d 2.32 ppm. In most
of the studied organotin(IV) complexes, these methyl protons are
observed as more than one signal with downfield shift. The shifting
observed in the ( C–H)imidazole and CH3 indicates the participation
of imidazole ring nitrogen in coordination. Ph2 Sn(HL) shows more
than one resonance for Hg and Hd , and one broad doublet for Hb
protons of Sn–C6 H5 indicating the presence of more than one tin
species in solution. The 2 J(1 H–119 Sn) values are 76.0 and 80.0 Hz
for Me2 Sn(HL), 72.3 and 77.7 Hz for Me3 Sn(H2 L) and 84.8 Hz
for n-Bu3 Sn(HL), and 3 J(1 H–119 Sn) for Ph2 Sn(HL) is 75.7 Hz,
which lie in the range of a distorted octahedral arrangement.
In the studied complexes, the values of ∠C–Sn–C calculated by
using Lockhart and Manders147 equation are in the range 122.13–
137.18◦ , which also indicates the cis-organic group in a distorted
octahedral geometry around tin. In the 13 C NMR spectrum of
H3 L, carbons attached to three azomethine nitrogens, viz. C-5, C-
5¢ and C-5¢¢ are observed at d 152.86 ppm. However, in all of the
studied organotin(IV) complexes, two or three resonances due to
azomethine carbons are observed indicating the non-equivalence
of these groups. Further, in the 13 C NMR spectra of organotin(IV)
complexes, the signals of C(8, 8¢), C(10, 10¢), C(6, 6¢) and methyl
groups (C-11, 11¢ cf. Fig. 4) are shifted to downfield: 137.04 ± 1.17,
129.75 ± 1.61, 140.83 ± 3.68 and 12.14 ± 3.45 ppm, respectively,
as expected for a process involving deprotonation of N(9)–H
for triorganotin(IV) derivatives and N(9)–H and N(9¢)–H for
diorganotin(IV) derivatives. Moreover, the presence of more than
one signal for tin-phenyl carbons for Ph2 Sn(HL) also suggests that
these groups are present in magnetically different environments
of more than one tin species in solution. In all the complexes,
the satellites are resolved and observed 1 J(13 C–119 Sn) values are
in the range 690.56–759.86 Hz. These values lie in a typical
range for six-coordinated organotin(IV) complexes. Moreover,
the calculated values of ∠C–Sn–C using observed 1 J(13 C–119 Sn)
values in the equation given by Lockhart and Manders147,149 are
in the range of 137.3–143.4◦ , which are intermediate between the
corresponding values for cis-octahedral (∠C–Sn–C = 90◦ ) and
trans-octahedral (∠C–Sn–C = 180◦ ) organotin(IV) moieties. Thus,
the most plausible structure of these complexes is best described
by a highly distorted octahedral geometry with cis-organic groups.
The 119 Sn spectra of the studied di- and triorganotin(IV) complexes,
7096 | Dalton Trans., 2011, 40, 7077–7121
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except for Ph2 Sn(HL), exhibit only one signal which rules out the
possibility of two different tin species. The observed 119 Sn chemical
shift values in the range d -268.09 to -523.65 ppm suggest six-
coordination corresponding to octahedral geometry around tin.
The spectrum of Ph2 Sn(HL) shows two additional signals at d
-599.50 and -607.24 ppm, which may be due to a complex species
with higher coordination number viz., heptacoordinated tin. This
suggests either the presence of two or more types of different tin
environments or a fast interchange of two or more different species
in the solution. Therefore, 119 Sn NMR spectral data of Ph2 Sn(HL)
reveal that the weak interactions between central tin with central
nitrogen ((N-1) triethylamine) or a third azomethine nitrogen may
occur, or a solvent molecule may occupy a seventh coordination
site leading to the fast interchange of octahedral species to
pentagonal-bipyramidal species in the solution. The intensity ratio
of these three peaks is 7 : 2 : 1 indicating the heptacoordinated
species is the minor species in solution. The possible geometries
around tin in di- and triorganotin(IV) complexes of H3 L is best
described by a cis-distorted octahedral or skew trapezoidal-
bipyramidal configuration as shown in Fig. 10 and Fig. 11,
respectively, whereas in Ph2 Sn(HL), the structure is described
by the interchange of cis-distorted octahedral to pentagonal-
bipyramidal structures as shown in Fig. 12a–c.
Fig. 10 Plausible distorted cis-octahedral structure/skew trape-
zoidal-bipyramidal configuration of R2 Sn(HL) (R = Me, n-Bu, n-Oct and
Ph).115
Fig. 11 Plausible distorted cis-octahedral structure of R3 Sn(H2 L) (R =
Me, n-Pr, n-Bu and Ph).115
The evidence of heptacoordinated tin heterocyclic ring species
has been provided by 1 H, 13 C and 119 Sn NMR spectra of the
complexes as shown in Scheme 9.142 The 119 Sn chemical shifts
in the range d -425 to -582 ppm for the complexes 1a–1l of
Scheme 9 indicate a coordination number higher than six for
tin atom. Further, the C–Sn–C bond angles of 170.5◦ for 1a
and 1b, 170.3◦ and 169.8◦ for 1c and 1d have been calculated
by using the values of the coupling constants, 2 J(1 H–119 Sn) =
115.7, 115.7, 115.6 and 115.3 Hz, respectively, whereas for 1e
and 1f the coupling constants, 1 J(13 C–119 Sn) = 1130 and 1128 Hz
have been used which resulted in C–Sn–C bond angles of 175.9
and 175.7◦ , respectively.142 For complexes 1e and 1f the coupling
constants n J(13 C–119 Sn) (n = 1 to 4) have also been reported. The 1 H
This journal is © The Royal Society of Chemistry 2011

Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
Fig. 12 Plausible interchange of geometry in Ph2 Sn(HL) from distorted
octahedral/pentagonal-bipyramidal geometry through the extra bonding
modes of central tin to (a) central N-1 (triethylamine), (b) a third
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azomethine or (c) coordination of a solvent molecule.115
NMR data provided the evidence for the formation of a mixture
containing 1h, 2h and 3h (cf. Scheme 9) in a ratio of 1 : 12 : 1
when the reaction was carried out in one step with n-dibutyltin
oxide using a toluene–methanol (4 : 6) mixture as solvent and 8 h
of reflux in the absence of 2-picolinic acid. Additional evidence
for the formation of 1h, 2h and 3h has been provided by the
presence of three 119 Sn NMR signals at d -83, - 68 and -441 ppm.
Interestingly, the reaction of the Schiff base 2 (cf. Scheme 9) with
n-dibutyltin oxide using the aforementioned reaction conditions
led to the formation of the complex 2h. Its 1 H NMR spectrum
exhibited a singlet at d 6.37 ppm. corresponding to the proton of
the stereogenic carbon, and an additional singlet for the methyl
group was reported at d 2.86 ppm, whereas a signal at d 84.0 ppm
in the 13 C NMR spectrum has been assigned due to a tertiary
carbon, but no evidence of an iminic carbon has been reported.
This indicates the possibility that the C N center reacted with
a molecule of methanol, which might also explain the presence
of both the methoxy and the methylene signals in the spectrum,
additionally, using the Lockhart equation147,149 and the coupling
constant 1 J(13 C–119 Sn) = 560.7 Hz, a C–Sn–C bond angle of
125.9◦ was calculated. The 119 Sn NMR showed an intense singlet
at d -83 ppm, which was indicative of a pentacoordinated tin
species.142 Further, a different reactivity has been reported for the
reaction of 2-amino-4-nitrophenol with 2-pyridinecarbaldehyde
and n-dibutyltin oxide using benzene as solvent (cf. Scheme 9).
The NMR structural analysis indicated the formation of a mixture
of 1h, 2h and 4h in a ratio 1 : 2 : 1. The addition of methanol to
the mixture resulted in the precipitation of 1h as confirmed by its
NMR spectral data. The separation of the remaining products of
the reaction has been carried out by the addition of methanol to the
filtered solution, from which the major compound (4h) has been
crystallized and separated by filtration. Its 1 H NMR spectrum
showed three doublets for aromatic protons at d 6.81, 7.95 and
9.67 ppm due to H-11, H-12 and H-14, respectively, while the
pyridine ring exhibited four different and more complex signals
at d 7.79, 8.24, 8.38 and 8.59 ppm for the H-3, H-4, H-2 and
H-5, respectively.142 Its 13 C NMR spectrum showed a signal at d
162.6 ppm corresponding to the carbonyl group, and the coupling
constant 1 J(13 C–119 Sn) = 566.4 Hz, resulted in an C–Sn–C bond
This journal is © The Royal Society of Chemistry 2011
View Online
angle of 126.2◦ . After the separation of 4h, the remaining complex
present in the mother-liquor has been identified as complex 3h,
which showed the previously described chemical shifts and the
coupling constant 1 J(13 C–119 Sn) = 559.6 Hz, indicating a C–Sn–C
bond angle of 125.8◦ . The 13 C NMR spectra of 3h and 4h showed
signals at d -67.9 and d -122 ppm, respectively, which correspond
to pentacoordinate geometries.142
119
4.5 Sn Mössbauer spectral and X-ray crystallographic studies
119
Sn Mössbauer spectroscopy has been frequently employed to
throw light on the structure of organotin(IV) complexes. The struc-
tural inferences have been based mainly upon the magnitude of
quadrupole splitting (QS) and upon the temperature dependence
of Mössbauer effect. In general higher quadrupole splittings corre-
spond to higher coordination numbers, the accepted ranges being
2.0–2.4, 2.6–3.0 and around 3.5 mm s-1 for coordination numbers
four, five and six, respectively.97 Chelate ligands are expected to
affect the above ranges since they contribute significantly to the
asymmetry of the tin environment.151 Besides providing grounds
for polymeric network formation, in case of high coordination
numbers one may not exclude the participation of the amino
substitutent to the formation of the tin coordination sphere, a fact
that has generally received little attention. The isomer shift, and
the ratio r = QS/IS have been used to determine the coordination
number of tin and of the asymmetry in it, being directly or
indirectly related to the coordinating mode of the ligands present
in the tin coordination sphere.152
Nath et al. have used 119 Sn Mössbauer technique to elucidate
the structure of the adducts of diorganotin(IV)/triorganotin(IV)
chlorides with Schiff bases derived from condensation
of substituted/non-substituted aldehydes with 2-amino-5-(o-
methoxyphenyl)-1,3,4-thiadiazole55 as well as chelates, viz.
Ph2 SnL,89 Bu2 SnL 125 and Ph3 SnL¢89 (where L = anion of various
Schiff bases derived from the condensation of 2-hydroxy-1-
naphthaldehyde/acetylacetone (H2 L) 89,125 /benzaldehyde (HL¢)
with various amino acids).89,125 The adducts are six-coordinated
having neutral bidentate ligands which coordinate through the
azomethine nitrogen and thiadiazole ring sulfur atoms. The
119
Sn Mössbauer spectrum of Ph2 SnCl2 ·(L) (L = Schiff base
of 2¢-hydroxyacetophenone and 2-amino-5-(o-methoxyphenyl)-
1,3,4-thiadiazole)55 showed an isomeric shift value of 1.20 mm s-1
and quadrupole splitting of 3.45 mm s-1 which indicated a trans-
configuration of the phenyl groups in a distorted octahedral
geometry as shown in Fig. 13A.55 The observed quadrupole
splitting of 2.52–2.55 mm s-1 and isomeric shift value of 1.15–
1.32 mm s-1 for the complexes, R3 SnCl·L (R = CH3 , L = Schiff
base of benzyl methyl ketone; R = C6 H5 , L = Schiff base
of 2-hydroxy-1-naphthaldehyde/acetylacetone and 2-amino-5-(o-
methoxyphenyl)-1,3,4-thiadiazole)55 suggested the existence of
fac-cis-R3 Sn(IV) moieties in a distorted octahedral arrangement
around tin atom for these complexes (Fig. 13B). The gross
distortions in these octahedral structures may be due to the
asymmetry of the bidentate ligands with N and S donor atoms.55
Diorganotin(IV) derivatives111 of 2-[(9H-purin-6-ylimino)]-
phenol exhibit octahedral geometry on the basis of isomeric shift
value of 1.20–1.33 mm s-1 and quadrupole splitting of 3.70–
3.94 mm s-1 . Trimethyltin(IV) derivatives of 3-, and 4-[1-pyridin-2-
yl-methylidene]- and 3,5-bis-[1-pyridin-2-yl-methylidene]-benzoic
Dalton Trans., 2011, 40, 7077–7121 | 7097
 View Online

Fig. 13 (A) trans-Octahedral structure of Ph2 SnCl2 ·L and (B)

fac-cis-octahedral structure of R3 SnCl·L (R = Me or Ph) (L = bidentate
ligands with N and S donor atoms).55 Fig. 14 Structure of (a) R2 SnL (R = n-Bu,75 Ph;89 L = tridentate Schiff
bases derived from 2-hydroxy-1-naphthaldehyde and amino acids)89,125 and
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

(b) R3 SnL (R = Me or Ph, L = bidentate Schiff base with ON donor

acids (QS 3.05–3.50 mm s-1 and IS 1.23–1.33 mm s-1 ) and a site, derived from benzaldehyde and amino acids;89 from adenine and
tri-n-butyltin derivative of 3-[1-pyridin-2-yl-methylidene]benzoic salicylaldehyde110 ).
acid (QS 3.34, 3.38 mm s-1 and IS 1.36,1.88 mm s-1 ) are at the
borderline of being considered five-coordinated, a fact supported
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by the infrared spectra and the structure determination for one

of them.97 Tetrahedral environments have been assigned to the
tricyclohexyl-, tribenzyl-, tri-n-butyl derivatives of 4- and 3,5-
substituted benzoates and to the triphenyltin compounds (QS
1.70–3.54 mm s-1 and IS 0.78–1.60 mm s-1 ).97 The occurrence of
more than one signal for these compounds suggests a varying
degree of secondary interaction from the second carboxylate
oxygen in an intermolecular chelating or intramolecular bridging
fashion. The triphenytin ester of disubstituted acid resembles the
trimethyltin esters and is expected to be polymeric in nature. The
interesting finding is the existence of high coordination number for
the triphenyl- and tribenzyltin esters of the 3-substituted ligand,
where there appears to exist some coordination of the pyridine or
imino nitrogen to tin.97
The observed values of quadrupole splitting and iso-
meric shift of R2 SnL (H2 L = Schiff base) are in the 2.82–
2.38/2.07–3.09 mm s-1 and 1.23–1.06/1.01–1.34 mm s-1 range,
respectively.89,125 The geometry concluded is a distorted trigonal-
bipyramidal with phenyl groups in cis position as shown in
Fig. 14a.89,125 Whereas, in Ph3 SnL¢, Schiff bases (HL¢) act as mono-
functional bidentate and coordinate through azomethine nitrogen
and carboxylic oxygen. On the basis of 119 Sn Mössbauer data,
a trigonal-bipyramidal geometry with phenyl groups occupying
two equatorial and one axial site as shown in Fig. 14b has been
suggested.89
119
Sn Mössbauer data of trimethyltin(IV) and triphenyltin(IV)
chelates of monofunctional bidentate ligands (HL = Schiff
base derived from condensation of 2-amino-5-(o-anisyl)-1,3,4-
thiadiazole with salicylaldehyde, 2-hydroxynaphthaldehyde and 2-
hydroxyacetophenone,81 and from adenine and salicylaldehyde110
with ON donor site suggested a trigonal-bipyramidal geometry
with methyl/phenyl groups occupying two equatorial and one
axial site (Fig. 14b).81,110 Whereas, R2 SnL2 (R = C6 H5 or n-
C4 H9 ; L = anion of ligands), the existence of cis-R2 Sn(IV) moieties
in a distorted octahedral arrangement around tin atom has been
suggested as shown in Fig. 15.81
The 119 Sn Mössbauer spectrum of the trimethyltin(IV) derivative
of Schiff base derived from 2-aminomethylbenzimidazole exhibits
IS at 1.30 mm s-1 and QS at 2.80 mm s-1 showing that the
electric field gradient around tin nucleus is produced by the
inequalities in the tin–oxygen and tin–nitrogen bonds and is also
Fig. 15 Structure of R2 SnL2 (R = Ph or n-Bu, L = anion of Schiff base
derived from 2-amino-5-(o-anisyl)-1,3,4-thiadiazole with salicylaldehyde,
2-hydroxynaphthaldehyde and 2-hydroxyacetophenone).81
due to geometric distortions.88 The r (QS/IS) value of 2.15 clearly
indicates a coordination number greater than four in the solid state.
It has been reported153 that there are three conceivable (Fig. 16)
five-coordinate isomers of R3 SnXY (where X or Y = N/O/S;
XY are the donor sites of the bidentate ligand) have different
QS value ranges, for isomer (A) 1.70–2.30 mm s-1 ; for (B) 3.0–
3.90 mm s-1 ; and for (C) 3.50–4.10 mm s-1 . The observed value of
QS (2.80 mm s-1 ) in the trimethyltin(IV) derivative is higher than
that for isomer (A) (Fig. 16) and considered to be compatible with
a trans-structure which is the conventional one (following Bent’s
rule) found in organotin chemistry. However, the observed n as (Sn–
C) and n s (Sn–C) stretching vibrations in the IR spectra of all of
the studied triorganotin(IV) complexes as well as diorganotin(IV)
complexes indicate a non-planar SnC3 /SnC2 fragment and rule
out the possibility of trans-isomer (B) (Fig. 16). Therefore, the
most plausible structure for Me3 Sn(L) (10) is a highly distorted cis-
trigonal-bipyramidal as shown in Scheme 4, which is intermediate
between (A) (fac) and (C) (mer) (Fig. 16) cis-trigonal-bipyramidal
structures. Furthermore, a similar structure as shown in Scheme 4
has also been suggested for n-Bu3 Sn(L) and Ph3 Sn(L).
Fig. 16 Possible isomers for SnR3 XY (where XY = donor sites of the
ligand).153

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The119 Sn Mössbauer spectrum of a trimethyltin(IV) derivative tin atom is pentacoordinated with a distorted square-pyramidal
of a tripodal Schiff base ligand containing three imidazole arms environment (Fig. 18).
exhibits QS at 3.52 mm s-1 and IS at 0.91 mm s-1 , and r (QS/IS)
value of 3.87 which suggested the existence of fac-cis-R3 Sn(IV)
moieties in a distorted octahedral arrangement around the tin
atom (as shown in Fig. 13B) in these reported R3 Sn(IV) derivatives
of tripodal Schiff base.115 A gross distortion in octahedral structure
may be due to the asymmetry of multidentate ligand with different
N donor atoms.
Leigh et al. have studied 119 Sn Mössbauer spectra of 1 : 1 adducts
of triphenyltin chloride with oxovanadium(IV) tetradentate Schiff
base complexes.62 The quadrupole splitting shows that all the
adducts contain five-coordinate tin with three phenyl groups that
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

are bonded to tin lying in the trigonal plane and other two groups
in trans-apical positions. The structure of Ph3 SnCl·VO(salen) has
been further confirmed by X-ray crystallography with crystal data,
monoclinic, C2/c, a = 31.592(5), b = 11.582(9), c = 20.471(3) Å;
b = 121.53(1)◦ ; Z = 8, R1 = 0.036 for 445 reflections with I > 2s(I),
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wR2 = 0.085 (Fig. 17) which displayed an almost linear tin-oxygen-

vanadium unit [Sn–O–V = 172.7(2)◦ ; Sn–O = 2.382(2), V–O = Fig. 18 Crystal structure of SnMe2 (PLPM - 2H).127
1.614(3) Å].
Ma et al.83 have studied X-ray crystal structures of some
triorganotin(IV) complexes of the Schiff base derived from 6-
amino-2-mercaptobenzothiazole and thiophene-2-carbaldehyde
(Table 1). Weak intermolecular Sn ◊ ◊ ◊ N interactions [Sn(1)–N(1)
3.005 Å] have been observed in Me3 SnL (L = Schiff base derived
from condensation of thiophene-2-carbaldehyde with 6-amino-
2-mercaptobenzothiazole) which is longer than the sum of the
covalent radii of tin and nitrogen atoms (2.15 Å), but still lies
within the sum of the van der Walls radii of the two atoms (3.74 Å).
As the N atom of the heterocycle is involved in weak coordinative
interaction with tin along one of tetrahedral faces, the structure
distortion is described as a capped tetrahedron (Fig. 19), and the
complex crystallized in orthorhombic space group Pccn with a =
44.779(2), b = 10.786(3), c = 7.502(3) Å; a = b = g = 90◦ ; Z = 8.83

Fig. 17 Crystal structure of Ph3 SnCl·VO(salen).62

Casas et al. have investigated 119 Sn Mössbauer spectra of

diorganotin(IV) complexes of H2 PLPM {[SnR2 (PLPM-2H)] (R =
Me, Et, n-Bu and Ph; PLPM = pyridoxalpyridoximine)},127 and
found that there are nevertheless certain structural differences
between the complexes of PLPM-2H with the smaller organic
groups (R = Me and Et) and those with the bigger ones (R =
n-Bu and Ph). The isomer shift and quadrupole splitting values
are clearly larger in the former [IS (mm s-1 ) = 1.45 (Me) and 1.54
(Et); QS (mm s-1 ) = 3.64 (Me) and 3.63 (Et)] than in the latter
[IS (mm s-1 ) = 1.38 (n-Bu) and 1.17 (Ph); QS (mm s-1 ) = 2.87 (n-
Bu) and 2.58 (Ph)]. The complexes are pentacoordinated square-
pyramidal, and the structures of the complexes (R = Me and
Et) have been further confirmed by X-ray crystallography. Both
methyl-/ethyltin(IV) complexes crystallize in monoclinic space
group P21 and C2/c, respectively, with a = 8.6075(5)/12.844(5),
b = 13.3977(6)/12.4708(13), c = 8.6360(3)/26.022(3) Å; b =
97.579(5)/103.484(19)◦ ; Z = 2/8. It has been observed that
Fig. 19 Tetrahedral molecular structure of Me3 SnL (L = Schiff
base derived from 6-amino-2-mercaptobenzaothiazole and thiophene-
2-carbaldehyde).83
Recently, crystal structures of triorganotin(IV) derivatives
of the Schiff base derived from 4-amino-5-phenyl-
4H-1,2,4-triazole-3-thiol and p-phthalaldehyde, viz.
{[(PhCH2 )3 Sn]2 (C24 H16 N8 S2 )}·2CH3 OH and [(Ph3 Sn)2 (C12 H6 N6 -
S4 )]·CH2 Cl2 indicated that both the complexes are monomers with
one ligand coordinates to two tribenzyltin or two triphenyltin
moieties.87 The center tin atoms of the former complex are
five-coordinated with distorted trigonal-bipyramidal geometry
by coordinated thiol sulfur and additional methanol group
(Fig. 20), whereas the center tin atoms of the latter complex are
four-coordinated with distorted tetrahedron geometry because
no additional solvent molecule coordinates to the center tin

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Table 1 X-Ray crystallographic data of organotin(IV) complexes of Schiff bases having tetrahedral geometry

Compound Ligand donors Crystal system Space group Sn–N/Å Sn–C/Å Sn–Xa /Å C–Sn–C/◦ Ref.

Me3 SnLb S Orthorhombic Pccn 3.005 2.101 (Sn1–C15) 2.455 111.5, 82

(Sn1 ◊ ◊ ◊ N1) 2.131 (Sn1–C13) (Sn1–S2) 115.9,
2.143 (Sn1–C14) 111.8
Ph3 SnLb S Monoclinic P21 /n 3.381 2.120 (Sn1–C13) 2.4281 110.07, 82
(Sn1 ◊ ◊ ◊ N1) 2.124 (Sn1–C25) (Sn1–S2) 114.39,
2.130 (Sn1–C19) 108.73
Ph3 SnLc S Triclinic P1̄ 2.992 2.129 (Sn1–C13) 2.460 112.7, 82
(Sn1 ◊ ◊ ◊ N1) 2.135 (Sn1–C19) (Sn1–S2) 109.5,
2.133 (Sn1–C25) 112.6
Me3 SnLd S Monoclinic P21 /c 3.073 2.110 (Sn1–C16) 2.4877 118.1, 82
(Sn1 ◊ ◊ ◊ N1) 2.132 (Sn1–C17) (Sn1–S2) 114.99,
2.139 (Sn1–C15) 112.5
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Ph3 SnLd S Triclinic P1̄ 3.049 2.127 (Sn1–C27) 2.447 116.54, 82

(Sn1 ◊ ◊ ◊ N1) 2.143 (Sn1–C21) (Sn1–S2) 108.90,
2.143 (Sn1–C15) 110.21
(Bu3 Sn)2 (L)e S Triclinic P1̄ — 2.195 (Sn2–C33) 2.438 126.8, 86
2.241 (Sn2–C25) (Sn2–S4) 99.1,
2.211 (Sn2–C29) 92.0
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a
X = other atoms. HL = .bR= .cR= .dR= .

The molecular structure of trimethyltin(IV) derivative,

Fig. 20 Molecular structure of {[(PhCH2 )3 Sn]2 (C24 H16 N8 S2 )}·2CH3 OH.87
atoms (Fig. 21). The asymmetric unit of this complex has two
monomers which are crystallographically non-equivalent with
almost same conformations but with only small differences
in bond lengths and angles. Furthermore, co-crystallized
dichloromethane molecule is found in this complex, but it
does not have obvious interactions with the center tin atoms.
Both the complexes are crystallized in triclinic space group
P1̄ with a = 10.9460(15)/9.796(5), b = 11.3990(18)/10.066(5),
c = 13.931(2)/25.993(13) Å; a = 68.949(2)/88.933(6), b =
78.240(3)/86.821(6), g = 77.722(3)/69.974(6)◦ ; Z = 12 . Further,
the molecules of {[(PhCH2 )3 Sn]2 (C24 H16 N8 S2 )}·2CH3 OH are
connected via point-to-face C–H–p interactions and O–H–N
hydrogen bonds resulting in a 2D network supermolecular
structure. Two molecules of [(Ph3 Sn)2 (C12 H6 N6 S4 )]·CH2 Cl2 are
connected via offset p–p stacking interactions to give rise to a 1D
infinite chain supermolecular structure.87
[(Me3 Sn)2 (C24 H16 N8 S2 )]n , indicated that each tin atom is five-
coordinated and displays a trigonal-bipyramidal geometry
(Fig. 22A), sulfur and heterocyclic nitrogen atom occupying
the axial sites and methyl occupying the equatorial site,87 and
crystallizes in triclinic space group P1̄ with a = 10.8228(19), b =
12.053(2), c = 16.622(3) Å; a = 83.067(7), b = 82.897(7), g =
79.111(7)◦ ; Z = 2. The Sn–N and Sn–S bonds in this complex
lead to 1D infinite zigzag chain (Fig. 22B) containing the tin
centers and Schiff base groups, these chains are further interlinked
into forming a 2D network by intermolecular Sn–S bonding
interactions (Fig. 23A). The molecular structure of tributyltin(IV)
derivative of Schiff base derived from 5-amino-1,3,4-thiadiazole-
2-thiol and p-phthalalaldehyde, [(Bu3 Sn)2 (C12 H6 N6 S4 )], exhibited
tetracoordinated and pentacoordinated tin centers with a distorted
tetrahedral geometry involving three bonds with the butyl carbons
and one to the sulfur atom, and a distorted trigonal-bipyramidal
geometry with three bonds to the butyl carbons, one to the
sulfur atom and another to the nitrogen atom derived from the
adjacent Schiff base, respectively. The complex crystallizes in
triclinic space group P1̄ with a = 9.5031(11), b = 12.6776(17),
c = 20.433(2) Å; a = 96.747(2), b = 102.189(6), g = 105.692(3)◦ ;
Z = 2. The complex forms a 32-membered macrocyclic structure
(Fig. 23(B)) via intermolecular N→Sn interactions.87 The width
of the macrocycle is 14.643 ¥ 5.009 Å [transannular Sn(1)–Sn(1A)
and N(3)–N(3A)], Sn(1)–N(5) distance is 2.758 Å, which is greater
than the sum of the covalent radii of Sn and N (2.15 Å), but
considerably less than the sum of the van der Waals radii of Sn
and N (3.75 Å).
Dicyclohexyl[N-(3-methoxy-2-oxidobenzylidene)valinato-k3 O,
N,O¢]tin(IV) crystallizes in monoclinic space group P2I /c (a =
9.5354(5), b = 10.0011(6), c = 25.7662(15) Å; b = 94.345(1)◦ ,
Z = 4) with a distorted trigonal-bipyramidal geometry around
the tin atom with the O atoms in the axial positions.154 The
metal atom forms five- and six-membered chelate rings with the
O,N,O¢-tridentate ligand and two cyclohexyl groups bound to

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 View Online
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Fig. 21 Molecular structure of [(Ph3 Sn)2 (C12 H6 N6 S4 )]·CH2 Cl2 .87

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Fig. 22 Molecular structure of [(Me3 Sn)2 (C24 H16 N8 S2 )]n , (A) and its 1D zig-zag chain (B).87

Fig. 23 2D Network structure of [(Me3 Sn)2 (C24 H16 N8 S2 )]n , linked by intermolecular Sn–S bonds (A) and Macrocyclic structure of [(Bu3 Sn)2 (C12 H6 N6 S4 )]
(B).87

the tin atom adopt chair conformations, with the Sn–C distance
of 2.138(3) Å. Two triphenyltin(IV) derivatives (1 and 3) of
amino acetate functionalized Schiff bases (as shown in Scheme 5)
are all polymeric chain in which a single carboxylate ligand
bridges adjacent tin centers via its carboxylate and oxide O-
atoms.95 Further, compounds 1 and 3 of Scheme 5 in crystal are
enantiomerically pure and the stereogenic centre at C(2) in both
the compounds has the S-configuration expected for L-leucine.
The primary coordination sphere of the tin atom is trigonal-
bipyramidal with the phenyl groups in the equatorial plane and
the axial positions occupied by one O-atom from carboxylate
ligand and the oxide O-atom of the next carboxylate ligand in the

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chain (Fig. 24). Furthermore, the formal hydroxyl group in the
carboxylate ligand of 1 and 3 has lost its H-atom, so is negatively
charged. Instead the imine N-atom is protonated, thus leading
to a Zwitterionic ligand. The N+ –H group forms intramolecular
hydrogen bonds with the oxide O-atom.95
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Fig. 24 Three repeats of the crystallographically and chemically
unique unit in the polymeric [Ph3 SnL1 H]n chain structure of 1 of Scheme 5
(50% probability ellipsoids). The H-atoms and one of the disordered
conformations have been omitted for clarity.95
The aqua-trimethyltin ester of 3-[1-pyridin-2-ylmethylidene]
benzoic acid has been isolated in two conformational polymorphs,
designated as a and b forms, both belonging to the monoclinic
space group P2I /n with a = 6.5874(3) and 11.3719(3), b =
23.9532(19) and 8.3578(2), c = 11.425(3) and 18.3187(6) Å; b =
95.957(11) and 90.881(3)◦ ; Z = 4 and 4, respectively.97 Both
the forms have tin atoms in a distorted trigonal-bipyramidal
environment with the axial positions occupied by one carboxylate
oxygen atom and one water molecule whereas methyl groups
are located in the equatorial plane. In these polymorphs, the
pirydyliminobenzoate ligand shows different orientation of the
pyridylimine fragment as well as different orientation of the
carboxylate ester group as shown in Fig. 25. In both the structures
water molecules donate hydrogen bonds to the pyridine N atom
and the carboxylate non-coordinating O atom to form a two-
dimensional polymeric structure. The imine nitrogen atom which
generally should be a good acceptor since hydrogen bonding is
not easily accessible to this interaction as in the flattened ligand
conformation the electron pair occupying a sp2 orbital of the imine
Fig. 25 Molecular structure of aqua-trimethyltin ester of 3-[1-pyridin-2-yl-methylidene]benzoic acid (a) polymorph a and (b) polymorph b.97
7102 | Dalton Trans., 2011, 40, 7077–7121
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nitrogen atom is significantly shielded by the pyridine and benzene
hydrogen atoms.97
The coordination environment around the tin atom in [N-
(3-hydroxypyridine-2-yl)-3,5-dicholorosalicylideneiminato]dime-
thyltin(IV) is a distorted square-pyramid in which two carbon
atoms and two oxygen atoms constitute the square base and the
imino nitrogen atom occupies the apical position as shown in
Fig. 26A.111 It can be seen in Fig. 26B that the tin atom has
six-coordinate environment in a centrosymmetric arrangement
leading to a Sn2 O2 core connected by Sn–O bonds, and the O–Sn
bonding occurs with the oxygen atom at the five-membered ring.
Two molecules are linked into the dimer by weak intermolecular
interactions with Sn–O bonding. The larger C–Sn–C bond angle
allows the formation of Sn–O intermolecular interaction, giving
rise to a dimeric organization.112
The X-ray structural investigation of ligand, 3-(2-hydro-
xyphenylimino)-1-phenylbutan-1-one indicated that there are
three crystallographically independent molecules in the asymmet-
ric unit, and the enolic proton of the imino-enol form is abstracted
by the imine nitrogen atom forming a hydrogen bond with a car-
bonyl oxygen so that the ligand exists in amino-enone form.114 The
–NH–C(Me) CH–C( O)– portion of the ligand is planar in all
three molecules which differ in the relative orientations of the two
aromatic rings. There is a chain parallel to the c axis propagated
by OH–O hydrogen bonds involving the phenolic proton and the
carbonyl oxygen atom. Despite the presence of aromatic rings,
there is no sign of p–p stacking in the lattice. The X-ray struc-
tural investigations of Ph2 Sn[Ph(O)C CH–C(Me) NC6 H4 (O)]
and Me2 Sn[Ph(O)C CH–C(Me) NC6 H4 (O)] confirm that the
ligand behaves as in a tridentate fashion coordinating through the
imino nitrogen, enolic oxygen and phenolic oxygen atoms. The
diphenyltin(IV) complex crystallizes as discrete molecules with a
distorted trigonal-bipyramidal geometry whereas the dimethyltin
derivative forms centrosymmetric dimmers with weak Sn–O
interactions, and square-pyramidal geometry is dominant over
trigonal-bipyramidal in this complex, which is to be expected, with
the extension of the tin coordination sphere to include a sixth atom,
O(1A). This gives distorted octahedral coordination geometry
containing a square plane defined by N(1), O(1), O(2) and
O(1A) from which Sn(1) lies only 0.0609(10) Å out of this plane
towards N(1). Further, the five-membered chelate rings in both
complexes are nearly planar but the six-membered chelate ring in
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Fig. 26 Molecular structure of [N-(3-hydroxypyridine-2-yl)-3,5-dicholorosalicylideneiminato]dimethyltin(IV) (A) and its packing diagram.112
the diphenyltin(IV) complex possesses a half chair conformation,114
folded along the O–N vector by 35.5(3)◦ and the largest deviation
from the plane defined by the six atoms is -0.305(5) Å by O(8)
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and Sn(1) deviates from the plane by the same magnitude. In
the dimethyltin complex, the six-membered chelate ring is very
similar where the fold is 31.72(12)◦ and maximum deviation from
this plane is 0.272(1) Å for Sn(1) (Fig. 27).
Fig. 27 Molecular structure of Me2 Sn[Ph(O)C CH–C(Me) NC6 H4 -
(O)]. Ellipsoids are drawn from 40% probability level. The suffix A denotes
the symmetry operation 1 - x, 1 - y, -z.114
Carcelli et al.131 have investigated the crystal structure of [(n-
C4 H9 )2 Sn(dfphbh)] having eight-coordinated tin with the follow-
ing crystal data: monoclinic space group P21 /c; a = 18.793(6),
b = 9.939(3), c = 20.175(6) Å; b = 116.67(2)◦ ; Z = 4, R1 = 0.0443
for 9687 reflections with I > 2s(I), wR2 = 0.1260. The crystal
structure confirmed that the ligand is deprotonated, in accordance
with the spectroscopic data. The tin atom is bonded to the oxygen
atoms (Sn–O(1) 2.156(2); Sn–O(2) 2.168(2) Å), the imino nitrogens
(Sn–N(2) 2.696(2); Sn–N(5) 2.595(3) Å) and the carbon atoms of
two n-butyl chains, Sn(1)–C(29) 2.109(3), Sn(1)–C(33) 2.122(3) Å,
C(29)–Sn(1)–C(33) 157.7(1)◦ ; the Sn–N(3) and Sn–N(4) distances
are 3.130(1) and 3.061(1) Å, respectively (Fig. 28). The overall
geometry around tin has been best described as a distorted
hexagonal-bipyramid, with ligand in the equatorial plane and
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Fig. 28 Crystal structure of [(n-C4 H9 )2 Sn(dfphbh)].131
the organic groups in the apical positions; it is noteworthy that
this geometry is unusual, particularly for tin that results eight-
coordinated complex.131
3-(2-Oxo-phenylimino)-3H-phenoxazin-2-oxodimethyltin rep-
resents a rare example of a fused delocalized planar hexacyclic
system bearing a pentacoordinated tin and the ligand acts as tri-
dentate coordinating through the imine nitrogen and two phenolic
oxygen atoms.141 The angles around the tin atom indicate square-
pyramidal geometry. The molecule is not completely planar and
the dihedral angle between the phenoxazine rings and the tin
phenolamine ring (17.5◦ ) is probably due to a steric interaction
between the aromatic hydrogen atoms (Fig. 29).
The crystal structures of penta- and heptacoordinated organ-
otin(IV) complexes (viz. 1e, 1h, 2h, 3h and 4h complexes as shown
in Scheme 9) of Schiff bases derived from 2-amino-4-R-phenol
and 2-pyridinecarbaldehyde have been reported142 The molecular
structure of 1e and 1h revealed that both of them have pentagonal-
bipyramidal geometry with two oxygen and three nitrogen atoms
(the azomethine and the nitrogen atoms of the pyridine rings) in
the equatorial plane, whereas the axial positions are occupied by
the two butyl groups having disorder and form angles of 169.2(1)
and 170.8(1)◦ for 1e and 1h, respectively. Further, 1e and 1h
complexes crystallize in monoclinic crystal systems with space
group C2/c and P21 /c, respectively (a = 26.777(2), b = 12.937(1),
Dalton Trans., 2011, 40, 7077–7121 | 7103

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Fig. 29 Crystal structure of 3-(2-oxo-phenylimino)-3H-phenoxazin-2-oxodimethyltin and view of the intermolecular p–p stacking in the solid state.141
c = 16.426(1) Å; a = g = 90◦ , b = 102.202(1)◦ ; Z = 4 for 1e;
a = 14.517(2), b = 9.838(1), c = 20.984(2) Å; a = g = 90◦ , b =
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91.807(2)◦ ; Z = 4 for 1h). On the other hand, complex 2h has two
five-membered ring heterocycles with a pentagonal coordination
environment around the tin atom giving rise to distorted trigonal-
bipyramidal geometry with the oxygen and the nitrogen of the
pyridine ring occupying the axial positions and the nitrogen and
carbons of the butyl groups occupying the equatorial positions.142
The five-membered rings are not completely planar since the Sn
atom deviates by 0.109(7) and 0.086(7) Å from the mean plane
formed by the pyridine and the six-membered rings, respectively.
The unit cell of 3h complex consists of two chemically equivalent,
but crystallographically independent molecules. Similar to 2h,
the molecular structures of complexes 3h and 4h contain two
five-membered ring heterocycles with pentagonal coordination
environment around the tin atom where the amine or amide
nitrogen and the butyl groups occupy the equatorial positions
and the pyridinic nitrogen and the oxygen occupy the axial ones.
Complexes 2h and 3h crystallize in triclinic space group P1̄ with
a = 10.501(1), b = 10.792(1), c = 11.501(2) Å; a = 82.468(2), b =
81.355(2), g = 61.566(2)◦ , Z = 2 for 2h; a = 11.350(1), b = 12.165(2),
c = 16.728(2) Å; a = 70.251(2), b = 78.666(2), g = 86.249(2)◦ , Z = 4
for 3h. The butyl group of 3h (Fig. 30) and the carbonyl group of 4h
exhibit disorder in two positions. The two Sn–N bonds of the 3h/4h
Fig. 30 Perspective view of molecular structures of complex 3h (Scheme 9) (thermal ellipsoids at 30% of probability level with minor component of
disordered side chain drawn using open ellipsoids and broken lines).142
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complexes show significant differences, in which the Sn(1)–N(2)
bond length of 2.059(2)/2.086(4) Å is shorter than Sn(1)–N(1)
bond length of 2.319(4)/2.323(4) Å. In this geometry, the C(14)–
Sn(1)–C(18) bond angles of 122.5(2)/116.9(4)◦ and O(1)–Sn(1)–
N(1) 151.2(1)/150.9(2)◦ represent a high degree of distortion in the
molecule. The N(2)–C(7) bond length of 1.434(5) Å and the N(2)–
C(7)–C(6) bond angle of 111.0(3)◦ corroborate the formation of
the reduced complex, 3h. The complex 4h has monoclinic crystal
system with space group C2/c having a = 17.158(2), b = 16.566(2),
c = 16.262(2) Å; a = g = 90◦ , b = 113.587(2)◦ , Z = 8.
Di-n-butyltin(IV) pyruvic acid thiophenecarbonyl hydrazone–
isopropyl alcohol (1 : 2) crystallizes in monoclinic space group
P21 /c with a = 12.276(3), b = 9.3224(19), c = 20.601(4) Å;
a = g = 90◦ , b = 93.356(3)◦ , Z = 4. The O(1) atom of
the carboxylate residue also binds the other neighboring tin
atom generating a Sn2 O2 four-membered ring and leading to
a weakly bridged dimer with weak Sn–O interactions.75 The
coordination geometry of the tin center can also be described
as a trans-C2 SnO4 N pentagonal bipyramid with the two n-
butyl groups occupying trans positions (Fig. 31) and there
also exists intramolecular hydrogen bonding which contributes
to the crystal stability and compactness.75 [{(n-Bu)2 SnCl(O)(n-
Bu)2 Sn(O)[C6 H4 CON2 C(CH3 )CO2 ]Sn(n-Bu)2 (HOCH3 )}2 ]n con-
tains a central planar Sn2 O2 four-membered ring (Fig. 32) and
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Fig. 31 X-Ray single crystal structure of di-n-butyltin(IV) pyruvic acid
thiophenecarbonyl hydrazone–isopropyl alcohol (1 : 2) (thermal ellipsoids
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are drawn at 30% probability). All H atoms are omitted for clarity.75
crystallizes in triclinic space group P1̄ with a = 9.4653(10), b =
12.7335(132), c = 20.134(2) Å; a = 99.8510(10), b = 97.7370(10),
g = 103.51792)◦ , Z = 1. In the dimeric structure, the geometries
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of all the tin atoms can be classified into three types, of which
the geometry composed by two types of cyclic atoms is similar
to the 1,3-disubstituted distannoxane compound with the ‘ladder’
structure. The third type of tin center is weakly bridged by the
oxygen atom from the carboxylate group of the neighboring
dimer, this makes this compound present a weak-bridged 1D
supermolecular polymer in the lattice.75
{(o-ClBz)2 Sn[4-HOC6 H4 CON2 C(CH3 )CO2 ](HOC2 H5 )}2 and
(n-C8 H17 )2 Sn[2-HOC6 H4 CON2 C(CH3 )CO2 ](H2 O)}2 have the
similar weak-bridged dimeric structure (Fig. 33 and Fig. 34),
which also present the identical geometry of trans-C2 SnO4 N
pentagonal bipyramid with that of di-n-butyltin(IV) pyruvic
acid thiophenecarbonyl hydrazone–isopropyl alcohol (1 : 2) for
the central atom, except for the different coordinated solvent
molecule as well as the different alkyl groups.75 Both the complexes
crystallize in the monoclinic crystal system with space group
Fig. 32 Structure of segments of the 1D chain of [{(n-Bu)2 SnCl(O)(n-Bu)2 Sn(O)[C6 H4 CON2 C(CH3 )CO2 ]Sn(n-Bu)2 (HOCH3 )}2 ]n . Thermal ellipsoids are
shown at the 30% probability level (a); A perspective view of the 1D chain via the weak bridged interaction and intramolecular hydrogen bonds (b). All
H atoms are omitted for clarity.75
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Fig. 33 X-Ray single crystal structure of {(o-ClBz)2 Sn[4-
HOC6 H4 CON2 C(CH3 )CO2 ](HOC2 H5 )}2 (thermal ellipsoids are drawn at
30% probability). All H atoms are omitted for clarity.75
P21 /c and a = 12.086(10), b = 12.251(10), c = 18.133(15) Å; a =
g = 90◦ , b = 90.453(11)◦ , Z = 4 for o-chlorobenzyltin complex,
and space group C2/c with a = 26.8573(16), b = 11.6043(13), c =
21.129(2) Å; a = g = 90◦ , b = 116.953(2)◦ , Z = 4 for n-octyltin
complex. Both the complexes have intra- and intermolecular
hydrogen bonding with the O–H of coordinated solvent molecule
or ligand phenol group and the corresponding acceptor oxygen
or nitrogen atoms.75
The asymmetric unit of {(n-Bu)2 Sn[C6 H5 CON2 C-
(CH3 )CO2 ][HOSn(n-Bu)3 ]}2 consists of two different types
of tin atoms (Fig. 35), which are linked by the hydroxyl group
derived from the decomposition of the reactant ‘bis(tri-n-butyltin)
oxide’. The Sn(1) atom lies in a distorted pentagonal-bipyramidal
coordination environment, in which one tridentate hydrazone
ligand, two trans n-butyl groups, the hydroxyl oxygen atom
O(4), and the carboxylate O(1) from the neighboring molecule,
coordinate to the central Sn(1) atom.75 The coordination
configuration at Sn(2) is distorted tetrahedral as indicated
by bond angles of 104.3(6), 104.5(5), 111.7(7), 101.0(8),
113.0(6) and 120.0(5)◦ for O(4)–Sn(2)–C(19), O(4)–Sn(2)–C(23),
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Fig. 34 X-Ray single crystal structure of (n-C8 H17 )2 Sn-
[2-HOC6 H4 CON2 C(CH3 )CO2 ](H2 O)}2 (thermal ellipsoids are drawn at
30% probability). All H atoms are omitted for clarity.75
C(19)–Sn(2)–C(23), O(4)–Sn(2)–C(27), C(19)–Sn(2)–C(27) and
C(23)–Sn(2)–C(27), respectively. An intramolecular hydrogen
bond has also been observed between the bridging hydroxyl group
and the carboxylate oxygen atom.74 The complex crystallizes into
triclinic, space group P1̄with a = 9.6414(18), b = 9.6652(18), c =
20.176(2) Å; a = 77.533(2), b = 81.097(2), g = 85.681(3)◦ , Z = 2.
[(n-Bu)SnCl2 ]- [4-NHC5 H4 CON2 CH9C6 H4 O-2)]+ is a simple
monomeric but interestingly, for keep the neutral nature, it presents
in the form of zwitterions with the ionization of nitrogen atom
of pyridine cycle in the Schiff base ligand.75 It crystallizes into
monoclinic crystal system with space group P21 /c, and a =
Fig. 36 (a) Coordination environment around the tin(IV) atom in [(n-Bu)SnCl2 ]- [4-NHC5 H4 CON2 CH(C6 H4 O-2)]+ with hydrogen atoms omitted for
clarity (thermal ellipsoids are drawn at 30% probability); (b) 1D infinite linear chain structure in [(n-Bu)SnCl2 ]- [4-NHC5 H4 CON2 CH(C6 H4 O-2)]+ by
intermolecular hydrogen bonds between the chlorine atom and proton of the pyridyl ring, with the atom labeling scheme.75
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Fig. 35 X-Ray single crystal structure of {(n-Bu)2 Sn-
[C6 H5 CON2 C(CH3 )CO2 ][HOSn(n-Bu)3 ]}2 (thermal ellipsoids are
drawn at 30% probability). All H atoms are omitted for clarity.75
10.235(4), b = 14.945(5), c = 13.627(5) Å; a = g = 90◦ , b = 110.727◦ ,
Z = 4. The central tin atom is six-coordinated, being bound to one
n-butyl group, two chlorine atoms, as well as one nitrogen atom
and two oxygen atoms from the enolic hydrazone ligand, and the
geometry is distorted octahedral with two chlorine atoms being in
trans position with different bond lengths [Sn(1)–Cl(1) 2.60(3) and
Sn(1)–Cl(2) 2.437(4) Å. One of the chlorine atoms has a longer
bond length due to a N(3)–H(3)–C(11) hydrogen bonding inter-
action as shown in Fig. 36b. The units of this complex are linked
together through hydrogen bonds resulting in a 1D supermolecular
chain.75 The single-crystal X-ray structure of a dimethyltin(IV)
derivative of benzoylacetone isonicotinylhydrazone has also been
reported.99
Basu Baul et al.155 have investigated the crystal structure of
[n-Bu2 SnCl2 ·C6 H5 N CHC5 H4 N-2)] with following crystal data:
orthorhombic, space group P21 21 21 , a = 12.098(2), b = 18.830(2),
c = 9.731(2) Å; a = b = g = 90◦ ; Z = 4. The structure of the
complex has as an octahedral environment around the tin atom
which is coordinated with two butyl groups, two chloride atoms
and two chemically non-equivalent nitrogen donor atoms of the
ligand (Fig. 37).
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Fig. 37 Crystal structure of [n-Bu2 SnCl2 ·(C6 H5 N CHC5 H4 N-2)].155
The X-ray crystallographic data of a number of organ-
otin(IV) complexes of Schiff bases having tetrahedral, trigonal-
bipyramidal/square-pyramidal, octahedral and pentagonal-
bipyramidal geometry around tin are summarized in Tables 1,
2, 3 and 4, respectively.
4.6 Mass spectral studies of organotin(IV) complexes of Schiff
bases
The electron impact (EI) and fast atomic bombardment
(FAB) mass spectra of mono- and dimethyltin(IV) complexes
with N-salicylidene- and N-pyridoxylideneacylhydrazines show
a prominent peak corresponding to the mononuclear par-
ent molecular ion.67 The mass spectra of [Sn(CH3 )2 (FTP)Cl],
[Sn(C2 H5 )2 (FTP)Cl] and [Sn(CH3 )(FTP)Cl2 ] showed molecular
ion peaks at m/z 364, 392 and 385, respectively. The mass spectral
(EI) fragmentation scheme of [Sn(CH3 )2 (FTP)Cl] has also been
reported76 with molecular ion peaks (P+ ) and (P+ + 1) at m/z 364
and 365, respectively. The spectrum shows fragments due to (P+ -
CH3 ) and (P - Cl) resulting from the simultaneous expulsion of
either CH3 ∑ or Cl∑ from the molecular ion. Further elimination of a
methyl radical from (P+ - CH3 ) and (P - Cl) gave monochlorotin(II)
and the monomethyltin(II) radical ions, respectively. The spectrum
also shows fragments at m/z 286, 271, 256, 236 and 220 resulting
from the elimination of a pyridyl radical C5 H4 N from previous
fragments.76
In the first-order positive-ion ESI mass spectra96 of
triphenyltin(IV) complexes of b-{[(E)-1-(2-hydroxyaryl)-
alkylidene]amino}propionates (LH) and potassium b-{[(2Z)-(3-
hydroxy-1-methyl-2-butenylidene)]amino}propionates (L¢H) are
found adducts with SnPh3 group and with alkali metal ions, such
as [M + SnPh3 ]+ , [M + K]+ and [M + Na]+ . The presence of these
ions is reported in the use of the determination of molecular
weights of the analyzed compounds. Whereas, in the first-order
negative-mass spectra of the complexes, the ions observed are
[L - CO2 ]- and [M + L]- .
The mass spectrometric data of (R2 Sn)2 L (R = Me, n-Bu and
Ph; L = hexadentate Schiff base derived from condensation of 5,5¢-
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methylenebis(salicylaldehyde) with 2-aminophenol, 2-amino-4-
chlorophenol or 2-amino-4-tert-butylphenol)98 indicate the forma-
tion of binuclear bis-diorganotin(IV) complexes. For all reported
complexes, the molecular ion is detected and the base peaks
correspond to the ion resulting from a fragmentation involving one
of the organic groups directly attached to tin atoms [M - R]+ . The
ESI (electronspray ionization)-mass spectra of Schiff bases derived
from 2-amino-3-hydroxypyridine and different salicylaldehydes,
and their dimethyltin(IV) complexes have been reported to exhibit
the base ion peak [M + H]+ and the fragment ions with the charac-
teristic tin isotopes.112 As an example, the [M + H]+ ion peak with
the characteristic tin isotopes of [N-(3-hydroxypyridine-2-yl)-5-
methylsalicylideneiminato]dimethyltin(IV) have been determined:
m/z 377 [M(120 Sn) + H]+ , 375 [M (118 Sn) + H]+ , 373 [M (116 Sn) + H]+ ;
346 [M(120 Sn) + 2CH3 ]+ , 344 [M(118 Sn) + 2CH3 ]+ , 342 [M(116 Sn) +
2CH3 ]+ .
Mass spectra129 of Ph2 SnL (L = chiral Schiff bases pre-
pared from condensation of 4-(diethylamino)salicylaldehyde
with (1R,2S)-(+)-norephedrine, (R)-(-)-phenylglycinol, (R)-(-)-
1-amino-2-propanol and (1S,2R)-2-amino-1,2-diphenylethanol)
showed the molecular ion in low abundance, the main fragment
ion is M+ - RCHO. The presence of the tin atom is easily
detected due to the isotopic abundances of tin.129 The ESI
(positive electronspray ionization) spectra of Sn(qaldsbz)(Ph)2 Cl
and Sn(qalsme)(Ph)2 Cl displayed base peaks at m/z 610 and 534,
which are assigned to the [Sn(qaldbz)Ph2 ]+ and [Sn(qaldsme)Ph2 ]+
fragment ions, respectively. The simulated isotope patterns of
these ions match completely the experimental spectra, supporting
assignment of these base peaks to the [M - Cl]+ ions.132
The mass spectral fragmentation pattern of 2,2-di-n-butyl-
and 2,2-diphenyl-6-aza-1,3-dioxa-2-stannabenzocyclononen-
4-ones derived from amino acids indicate fragmentation of
n-butyl or phenyl substituents as well as decarboxylation of the
amino acid.137 In dibutyl-substituted complexes the base peak
corresponds to [M+ - CO2 ] and loss of C8 H17 is observed whereas,
in the diphenyl-substituted derivatives the base peak corresponds
to [M+ - CO2 ], and loss of C6 H5 is observed.
Recently, TOF-MS spectra using ESI mode of 3-(2-oxo-
phenylimino)-3H-phenoxazin-2-oxo-dimethyltin/-diphenyltin in-
dicated [M + H]+ 565.1505/689.1820 a.m.u. (Calcd. 565.1507/
689.1826 a.m.u.)141 The monomeric structure of heptacoordinated
diorganotin(IV) complexes of Schiff bases derived from 2-amino-
4-R-phenol and 2-pyridinecarbaldehyde (1a–1l of Scheme 9)
has been established by mass spectrometry, which showed the
molecular ions for all complexes.142 Fragment ions [M+ - R],
[M+ - PyCOO- ], which correspond to the base peak for the
complexes 1a–1h, and [M+ - PyCOO - 2R] have also been
reported.142
5. Thermal studies of organotin(IV) complexes of
Schiff bases
A survey of existing literature revealed that little work has
been done on the thermal decomposition of organotin(IV)-
Schiff base complexes. The thermal decomposition scheme
of Ph3 SnCl(FuFSCZ), Ph2 Sn(OHAcPhSCZ) and Ph3 Sn(4-
MeBenzTSCZ) have been reported by Nath et al. in the temper-
ature range 25–725 ◦ C using TG, DTG and DTA techniques.156
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Table 2 X-Ray crystallographic data of organotin(IV) complexes of Schiff bases having trigonal-bipyramidal/square-pyramidal geometry

Ligand Space
Compound donors Crystal system group Sn–O/Å Sn–N/Å Sn–C/Å Sn–Xa /Å C–Sn–C/◦ Ref.

Vin2 Sn(salop)b ONO Triclinic P1̄ 2.117 (Sn–O1), 2.125 (Sn–O2) 2.227 (Sn–N) 2.112 (Sn–C14), — 138.3 39
2.113 (Sn–C16)
[Sn(H3 dfps)(C6 H5 )2 ]· NNO Triclinic P1̄ 2.274 (Sn–O1) 2.164 (Sn–N1), 2.125 (Sn–C21), — 139.3 51
(CH3 )2 SOc 2.198 (Sn–N2) 2.112 (Sn–C27)
[Ph2 Sn(2-OC10 H6 CH O, NOO Monoclinic C2/c 2.068 (Sn1–O2), 2.188 (Sn1–O14A), 2.136 (Sn1–N1) 2.108 (Sn1–C21), 2.333 (Sn2–Cl1), 2.477 119.4 (Sn1), 59
NCH2 COO)]·SnPh2 Cl2 2.307 (Sn2–O14) 2.127 (Sn1–C31), (Sn2–Cl2) 135.6 (Sn2)
2.122 (Sn2–C41),
2.113 (Sn2–C51)
[Me3 SnL]2 d OO Monoclinic P21 /c 2.418 (Sn–O3), 2.188 (Sn–O1) — 2.053 (Sn–C11), — 135.9, 111.9, 111.2 72
2.100 (Sn–C10),
2.134 (Sn–C9)
Ph2 SnLe ONO Monoclinic P21 /c 2.071 (Sn–O1), 2.123 (Sn–O2) 2.140 (Sn–N1) 2.113 (Sn–C19), — 125.6 72

7108 | Dalton Trans., 2011, 40, 7077–7121

2.125 (Sn–C13)
(n-C4 H9 )3 SnL(H2 O)f O Monoclinic P21 /c 2.541 (Sn–O5) (H2 O), 2.152 — 2.08 (Sn–C19) — 123.3, 118.7, 116.3 71
(Sn–O1) (L)
[(n-C4 H9 )2 Sn]2 Lg ONO Monoclinic P21 /c 2.079 (Sn–O1), 2.162 (Sn–O2) 2.174 (Sn–N2) 2.126 (Sn–C12), — 131.8 69
2.113 (Sn–C16)
[(n-C4 H9 )2 Sn]2 Lh ONO Triclinic P1̄ 2.206 (Sn1–O1), 2.167 (Sn1–O3), 2.198 (Sn1–N2), 2.123 (Sn1–C25), — 151.6 (Sn1), 69
2.180 (Sn2–O2), 2.166 (Sn2–O5) 2.219 (Sn2–N3) 2.088 (Sn1–C29), 152.5 (Sn2)
2.106 (Sn2–C33),
2.116 (Sn2–C37)
[(CH3 )2 Sn]2 Li ONO Monoclinic P21 /c 2.117 (Sn–O1), 2.088 (Sn–O2) 2.154 (Sn–N2) 2.099 (Sn–C16), — 121.5 69
2.110 (Sn–C17)
[(n-C4 H9 )2 Sn]2 Li ONO Triclinic P1̄ 2.127 (Sn–O1), 2.091 (Sn–O2) 2.152 (Sn–N2) 2.130 (Sn–C16), — 126.8 69
2.108 (Sn–C20)
j
(n-C4 H9 )2 SnL ONO Monoclinic P21 /c 2.201 (Sn–O1) 2.227 (Sn–N1) Not given — 155.3 70
Ph2 SnLj ONO Monoclinic P21 /c 2.067 (Sn–O1) 2.152 (Sn–N1) Not given 128.9 70
[Me2 Sn(FTP)Cl]·0.5H2 Ok NS Monoclinic P21 /c — 2.359 (Sn–N3) 2.108 (Sn–C8), 2.672 (Sn–Cl1), 143.0 75
2.105 (Sn–C9) 2.478 (Sn–S1)
[(PhCH2 )3 Sn]2 (L)·2CH3 OHl SO Triclinic P1̄ 2.631 (Sn–O1) — 2.163 (Sn–C27), 2.559 (Sn–S1) 116.10, 119.10, 86
2.164 (Sn–C13), 118.23
2.167 (Sn–C20)
[(Me3 Sn)2 (L)]n l SN Triclinic P1̄ — 2.285 (Sn1–N3), 2.124 (Sn1–C1), 2.883 (Sn–S2) 127.0, 114.6, 117.5 86
2.281 (Sn2–N7) 2.104 (Sn1–C2), (Sn1), 121.3, 115.0,
2.125 (Sn1–C3), 122.3 (Sn2)
2.086 (Sn2–C16),
2.089 (Sn2–C17),
2.133 (Sn2–C18)
[Ph3 Sn]2 (L)·CH2 Cl2 m S Triclinic P1̄ — — 2.086 (Sn–C1), 2.482 (Sn–S1) 107.40, 112.0, 110.3 86
2.113 (Sn–C7),
2.145 (Sn–C13)
(Bu3 Sn)2 (L)m SN Triclinic P1̄ — — 2.110 (Sn1–C13), 2.583 (Sn1–S2), 114.7, 125.4, 113.9 86
2.100 (Sn1–C17), 2.438 (Sn2–S4) (Sn1) 126.8, 99.1,
2.190 (Sn1–C21), 92.0 (Sn2)
2.195 (Sn2–C33),
2.241 (Sn2–C25),
2.211 (Sn1–C29)
(n-C4 H9 )2 SnLn ONO Orthorhombic P21 21 21 2.103 (Sn–O1), 2.158 (Sn–O2) 2.164 (Sn–N1) 2.131 (Sn–C1), — 128.2 91
2.109 (Sn–C5)

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Table 2 (Contd.)

Ligand Space
Compound donors Crystal system group Sn–O/Å Sn–N/Å Sn–C/Å Sn–Xa /Å C–Sn–C/◦ Ref.

Ph2 SnLo ONO Monoclinic P21 2.128 (Sn–O1), 2.070 (Sn–O3) 2.158 (Sn–N1) 2.115 (Sn–C13), 2.105 — 121.5 91
(Sn–C19)
[Ph3 Sn(HL)]·Ph2 SnLp OO ONO Orthorhombic P21 21 21 2.069 (Sn1–O1), 2.150 (Sn1–O2), 2.152 (Sn1–N1) 2.107 (Sn1–C13), 2.110 — 123.9 (Sn1), 124.6, 93
2.435 (Sn2–O3), 2.165 (Sn2–O4) (Sn1–C19), 2.119 120.6, 111.9 (Sn2)
(Sn2–C37), 2.139
(Sn2–C43), 2.122
(Sn2–C49)
[Ph3 SnLH]n q OO Orthorhombic P21 21 21 2.151 (Sn–O1) 3.386 (Sn–O2), 2.352 — 2.136 (Sn–C11), 2.132 — 122.2, 119.8/111.8 94
(Sn–O3¢) (Sn–C17), 2.132 117.2/124.0
(Sn–C23a), 2.129
(Sn–C23b)
[Ph3 SnL]n r OO Monoclinic P21 2.197 (Sn–O1) 3.537 (Sn–O2), 2.242 — 2.124 (Sn–C14), 2.118 — 120.2, 109.7/120.2, 94
(Sn–O3¢) (Sn–C20), 2.135 129.5/119.5
(Sn–C26a), 2.143
(Sn–C26b)
(Ph2 Sn)2 Ls ONO Monoclinic P21 /c 2.079 (Sn1–O1)/(Sn2–O3), 2.094 2.191 (Sn1– 2.094 (Sn1–Ca)/ — 119.5 (Sn1)/(Sn2) 95
(Sn1–O2)/(Sn2–O4) N1)/(Sn2–N2) (Sn2–Ca¢¢), 2.114
(Sn1–Ca¢)/(Sn2–Ca¢¢¢)

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Me3 Sn(Ln ) (polymorph a) ONO Monoclinic P21 /n 2.187 (Sn–O2), 2.377 (Sn–OH2 ) — 2.111 (Sn–C14), 2.114 — 95.91, 90.95, 95.69 96
(Sn–C15), 2.123
(Sn–C16)
Me3 Sn(Ln ) (polymorph b) ONO Monoclinic P21 /n 2.166 (Sn–O2), 2.397 (Sn–OH2 ) — 2.106 (Sn–C14), 2.099 — 92.03, 95.10, 95.65 96
(Sn–C15), 2.107
(Sn–C16)
(Ph2 Sn)2 Lt ONO Monoclinic P21 /c 2.085 (Sn1–O1), 2.077 (Sn2–O3), 2.188 (Sn1–N1), 2.113 (Sn1–Ca), 2.102 — 121.0 (Sn1), 128.7 97
2.065 (Sn1–O2), 2.084 (Sn2–O4) 2.178 (Sn2–N2) (Sn2–Ca“), 2.128 (Sn2)
(Sn1–Ca‘), 2.108
(Sn2–Ca“‘)
t-Bu2 Sn(SalN)u ONO Monoclinic P21 /c 2.089 (Sn–O2), 2.163 (Sn–O1) 2.181 (Sn–N1) 2.159 (Sn–C18), 2.168 — 130.58 104
(Sn–C14)
Me2 SnLv ONO Triclinic P1̄ 2.074 (Sn–O1), 2.128 (Sn–O10) 2.176 (Sn–N8) 2.102 (Sn–C17), 2.097 — 127.3 108
(Sn–C18)
Me2 SnLw ONO Monoclinic P21 /n 2.179 (Sn–O1), 2.131 (Sn–O2) 2.213 (Sn–N1) 2.103 (Sn–C13), 2.095 — 141.28 111
(Sn–C14)
x
Ph2 Sn(L) ONO Monoclinic P21 /c 2.110 (Sn–O1), 2.115 (Sn–O8) 2.140 (Sn–N4) 2.130 (Sn–C111), 2.134 — 120.1 113
(Sn–C121)
Ph2 SnLy ONO Orthorhombic P21 21 21 2.121 (Sn–O1), 2.072 (Sn–O2) 2.143 (Sn–N1) 2.129 (Sn–Ci), 2.124 — 121.89 128
(Sn–Ci)
z
Ph2 SnL ONO Orthorhombic P21 21 21 2.115 (Sn–O1), 2.045(Sn–O2) 2.152 (Sn–N1) 2.133 (Sn–Ci), 2.127 — 119.73 128
(Sn–Ci)
Ph2 SnLaa ONO Monoclinic P21 2.123 (Sn–O1), 2.043 (Sn–O2) 2.157 (Sn–N1) 2.137 (Sn–Ci), 2.144 — 122.2 128
(Sn–Ci)
ab
Ph2 SnL ONO Monoclinic P21 2.107(Sn–O1), 2.065 (Sn–O2) 2.153 (Sn–N1) 2.146 (Sn–Ci), 2.160 — 119.3 128
(Sn–Ci)
n-Bu2 SnLac ONO Orthorhombic P21 21 21 2.158 (Sn–O1), 2.099 (Sn–O3) 2.154 (Sn–N1) 2.116 (Sn–C), 2.125 — 126.1 136
(Sn–C)
ac
n-Bu2 SnL ONO Orthorhombic P21 21 21 2.145 (Sn–O1), 2.112 (Sn–O3) 2.160 (Sn–N1) 2.108 (Sn–C), 2.122 — 125.1 136
(Sn–C)
Ph2 SnLad ONO Triclinic P1̄ 2.117 (Sn–O1), 2.071 (Sn–O3) 2.155 (Sn–N1) 2.115 (Sn–C), 2.124 — 125.9 136
(Sn–C)

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Table 2 (Contd.)

Ligand Space
Compound donors Crystal system group Sn–O/Å Sn–N/Å Sn–C/Å Sn–Xa /Å C–Sn–C/◦ Ref.

Ph2 SnLae ONO Orthorhombic P21 21 21 2.140 (Sn–O1), 2.073 (Sn–O3) 2.148(Sn–N1) 2.109 (Sn–C), 2.119 — 118.68.. 136
(Sn–C)
Ph2 SnLae (racemic) ONO Orthorhombic P21 21 21 2.139 (Sn–O1), 2.083 (Sn–O3) 2.145 (Sn–N1) 2.116 (Sn–C), 2.116 — 122.63 136
(Sn–C)
Ph2 SnLaf ONO Monoclinic P21 /c 2.151 (Sn–O1), 2.083 (Sn–O3) 2.148 (Sn–N1) 2.113 (Sn–C), 2.113 — 122.61 136
(Sn–C)
ag
Ph2 SnL ONO Orthorhombic P21 21 21 2.134 (Sn–O1), 2.075 (Sn–O3) 2.165 (Sn–N1) 2.115 (Sn–C), 2.122 — 124.4 136
(Sn–C)
Ph2 SnLah ONO Orthorhombic Pcab 2.159 (Sn–O1), 2.078 (Sn–O3) 2.145 (Sn–N1) 2.118 (Sn–C), 2.102 — 123.83 136
(Sn–C)
ai
Ph2 SnL ONO Orthorhombic P21 21 21 2.121 (Sn–O1), 2.060 (Sn–O3) 2.157 (Sn–N1) 2.123 (Sn–C), 2.124 — 127.95 136
(Sn–C)

7110 | Dalton Trans., 2011, 40, 7077–7121

n-Bu2 SnLaj ONO Triclinic P1̄ 2.119 (Sn–O1), 2.137 (Sn–O3) 2.208 (Sn–N1) 2.122 (Sn–C14), — 140.8 138
2.146 (Sn–C14a)
Ph2 SnLaj ONO Monoclinic P21 /a 2.0943 (Sn–O1), 2.0879 (Sn–O3) 2.180 (Sn–N1) 2.118 (Sn–C14), — 122.01 138
2.110 (Sn–C14a)
Ph2 SnLak ONO Orthorhombic Pbca 2.106 (Sn–O2), 2.079 (Sn–O1) 2.155 (Sn–N1) 2.125 (Sn–C14), — 125.7 138
2.119 (Sn–C14a)
Ph2 SnLal ONO Triclinic P1̄ 2.107 (Sn–O1), 2.049 (Sn–O3) 2.186 (Sn–N6) 2.119 (Sn–C), 2.130 — 126.14 139
(Sn–C)
al
Ph2 SnL ONO Triclinic C2/c 2.100 (Sn–O1), 2.074 (Sn–O3) 2.175 (Sn–N6) 2.120 (Sn–C), 2.125 — 124.73 139
(Sn–C)
Me2 SnLan ONO — — 2.092 (Sn–O2), 2.116 (Sn–O8) 2.183 (Sn–N5) 2.121 (Sn–C33), — 121.1 140
2.120 (Sn–C34)
Bu2 SnLap ONO Triclinic P1̄ 2.114 (Sn–O1) 2.349 (Sn–N1), 2.114 (Sn–C14), — 124.4 141
2.062 (Sn–N2) 2.123 (Sn–C18)
Bu2 SnLap (molecule A) ONO Triclinic P1̄ 2.108 (Sn–O1) 2.319 (Sn–N1), 2.132 (Sn–C14), — 122.5 141
2.059 (Sn–N2) 2.125 (Sn–C18)
Bu2 SnLap (molecule A) ONO Triclinic P1̄ 2.118 (Sn2–O4) 2.357 (Sn2–N4), 2.130 (Sn2–C38), — 125.0 141
2.053 (Sn2–N5) 2.108 (Sn2–C34)
ap
Bu2 SnL ONO Monoclinic C2/c 2.104 (Sn–O1) 2.323 (Sn–N1), 2.120 (Sn–C14), — 116.9 141
2.113 (Sn–N2) 2.113 (Sn–C18)
Cy2 SnLaq ONO Monoclinic P21 /c 2.157 (Sn–O1), 2.108 (Sn–O3) 2.172 (Sn–N1) 2.142 (Sn–C1), — 121.20 153
2.135 (Sn–C7)
a
X = Other atoms. b salop = 2-{[(2-hydroxyphenyl)imino]methyl}phenol. c H3 dfps = Pyrrole-2,5-dicarbaldehyde bis(2-hydroxybenzoylhydrazone). d HL = Pyruvic acid thiophene-2-carboxylic hydrazone.
e
H2 L = Salicylaldehyde thiophene-2-carboxylic hydrazone. f H2 L = 3-HOC10 H6 -2-CONHNC(CH3 )COOH. g H4 L = Bis(2-hydroxybenzaldehyde)terephthalohydrazone. h H4 L = Bis(2-hydroxy-3-
methoxybenzaldehyde)terephthalohydrazone. i H4 L = Bis(2-hydroxy-1-naphthaldehyde)terephthalohydrazone. j L = o-Vanillin-2-thiophenoylhydrazone. k 2-Formylpyridine thiosemicarbazone. l Schiff
base derived from 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol and p-phthalaldehyde. m Schiff base derived from 5-amino-1,3,4-thiadiazole and p-phthalaldehyde. n 5-Cl-2-HOC6 H3 CH NCH(i-
Pr)COOH. o 5-Br-2-HOC6 H3 CH NCH(i-Pr)COOH. p 3,5-Br2 -2-HOC6 H2 CH NCH(i-Pr)COOH. q KL = Potassium 2-{[(2Z)-3-hydroxy-1-methyl-2-butenylidene)]amino]-4-methylpentanoate.
r
KL1 = potassium 2-{[(E)-1-(2-hydroxyphenyl)ethylidene)]amino]-4-methylpentanoate. s Potassium 2-{[(E)-1-(2-hydroxyphenyl)methylidene)]amino]pentanoate. t Schiff base derived from 5,5¢-
methylenebis(salicylaldehyde) and 2-aminophenol. u Salicylaldehyde isonicotinylhydrazone. v 5-Br-(2-OC6 H4 CH N–N C(O)Ph). w H2 L = N-(3-Hydroxypyridine-2-yl)-3,5-dichlorosalicylideneimine.
x
H2 L = C6 H5 (HO)C CH–C(Me) N–C6 H4 (OH). y Schiff base derived from 4-(diethylamino)salicylaldehyde and (1R,2S)-(+)-norephedrine. z Schiff base derived from 4-(diethylamino)salicylaldehyde
and (R)-(-)-phenylglycinol. aa Schiff base derived from 4-(diethylamino)salicylaldehyde and (R)-(-)-1-amino-2-propanol. ab Schiff base derived from 4-(diethylamino)salicylaldehyde and (1S,2R)-2-
amino-1,2-diphenylethanol. ac–ai Schiff base derived by a-amino acid (NH2 CH(R)COOH) and salicylaldehyde. ac R = CH(CH3 )CH3 . ad R = CH(CH3 )CH2 CH3 . p: (R = H). ae R = CH3 . af R = CH2 CH3 .
ag
R = CH(CH3 )CH3 . ah R = (CH2 )5 CH3 . ai R = C6 H5 . aj Schiff base derived from methoxysalicylaldehyde and 2-amino-5-nitrophenol. ak Schiff base derived from 4-diethylaminosalicylaldehyde and
2-amino-5-nitrophenol. al Schiff base derived from salicylaldehyde and b-amino alcohol (b-aminoethanol) am Schiff base derived from salicylaldehyde and b-amino alcohol (b-aminobutanol). an Schiff
base derived from 2-amino-4-nitrophenol and 2-pyridinecarbaldehyde C6 H3 (4-NO2 )(O)(N)CH(OCH3 )(C5 H4 N). ao C6 H3 (4-NO2 )(O)(N)CH2 (C5 H4 N). ap C6 H3 (4-NO2 )(O)(N)CH(O)(C5 H4 N). aq H2 L =
N-(3-Methoxy-2-oxidobenzylidene)valine.

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Table 3 X-Ray crystallographic data of organotin(IV) complexes of Schiff bases having octahedral geometry

Ligand Crystal Space

Compound donors system group Sn–O/Å Sn–N/Å Sn–C/Å Sn–Xa /Å C–Sn–C/◦ Ref.

Cl3 SnCH2 CH2 - O Triclinic P1̄ 2.054 (Sn1–O1), — 2.137 (Sn1–C18) 2.381 (Sn1–Cl1), — 41
COOBu·2-OH-naphth- 2.362 (Sn1–O2) 2.473 (Sn1–Cl2),
alideneaniline-4-Cl 2.439 (Sn1–Cl3)
Ph2 Sn·(NAPPDI)b OONN Tetragonal I41 cd 2.18 (Sn1–O1), 2.22 (Sn1–N1), 1.250 (Sn1–C1), — 141.0 37
2.13 (Sn1–O2) 2.20 (Sn1–N2) 2.180 (Sn1–C7)
Me2 Sn(NCS)2 · O Monoclinic P21 /n 2.208 (Sn1–O1), 2.270 (Sn1–N1), 1.605 (Sn–C2), — 180.0 40
[2HOBENZ-4Me]2 c 2.208 2.270 2.117 (Sn–C2A)
(Sn1–O1A) (Sn1–N1A)
[LH+ ]2 [Me2 SnCl4 ]2- d Ionic Triclinic P1 — — 2.060 2.642 180.0 145
species (Sn1–C0/C1) (Sn1–Cl1/Cl2),
2.639
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

(Sn1–Cl3/Cl4)
Me2 SnCl2 ·(OHC6 - O Triclinic P1̄ 2.244 (Sn1–O1), — 2.348 2.569 (Sn1–Cl1), 180.0 38
H4 CH NC6 H4 Me-4)2 2.256 (Sn2–O2) (Sn1–C1/C2), 2.581 (Sn2–Cl2)
2.264
(Sn2–C15/C16)
SnCH3 (Sal·p- ONO Triclinic P1 2.109 (Sn1–O1), 2.171 (Sn1–N2) 2.106 (Sn–C17) 2.425 (Sn1–Cl1) — 66
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CH3 OBzh)Cl]· 2.033 (Sn1–O2),

CH3 OHe 2.278 (Sn1–O4)
L2 Sn(CH3 )2 f ON Monoclinic P21 /c 2.083 (Sn1–O1), 2.397 (Sn1–N1), 2.124 (Sn1–C35), — 107.4 65
2.077 (Sn1–O2) 2.366 (Sn1–N2) 2.137 (Sn1–C36)
L2 Sn(CH3 )2 g ON Monoclinic P21 /n 2.086 (Sn1–O1), 2.349 (Sn1–N1), 2.143 (Sn1–C35), — 108.79 65
2.080 (Sn1–O2) 2.386 (Sn1–N2) 2.144 (Sn1–C36)
L2 Sn(n-C4 H9 )2 g ON Orthorhombic P21 21 21 2.092 (Sn1–O1), 2.378 (Sn1–N1), 2.157 (Sn1–C35), — 111.1 65
2.086 (Sn1–O2) 2.373 (Sn1–N2) 2.144 (Sn1–C39)
(n-C4 H9 )LSnCl2 h ONO Monoclinic P21 /c 2.053 (Sn1–O1), 2.236 (Sn1–N1) not given not given — 70
2.181 (Sn1–O3)
(n-C4 H9 )2 Sn(LH)2 i OOOO Monoclinic C2/c 2.573 (Sn1–O1), — 2.129 (Sn1–C25), — 137.10 89
2.099 (Sn1–O2), 2.127 (Sn1–C29)
2.094 (Sn1–O4),
2.564 (Sn1–O5)
Phensal(t-Bu)(n- ONN Monoclinic P21 /c 2.040 (Sn1–O1) 2.196 (Sn1–N1), 2.136 (Sn–C) 2.4675 (Sn1–Cl1), — 101
Bu)SnCl2 j 2.270 (Sn1–N2) 2.4781 (Sn1–Cl2)
(n Bu)2 Sn(Vanophen)k ONNO Triclinic P1̄ 2.235 (Sn1–O1), 2.266 (Sn1–N1), 2.139 (Sn1–C30), — 156.76, 103
2.237 (Sn1–O2), 2.2797 2.140 (Sn1–C34), 160.87
2.219 (Sn1–N2), 2.277 2.139 (Sn1¢–C30¢),
(Sn1¢–O1¢), (Sn1¢–N1¢), 2.140 (Sn1¢–C34¢)
2.237 2.280
(Sn1¢–O2¢) (Sn1¢–N2¢)
{[n-Bu2 Sn(LH)]2 O}2 l OOOO Triclinic P1̄ 2.020 (Sn1–O7), — 2.098 (Sn1–C33), — 137.2 105
2.200 (Sn1–O4), 2.10 (Sn1–C29), (Sn1),
2.263 (Sn1–O1), 2.083 (Sn2–C37), 143.3
2.863 (Sn1–O5), 2.098 (Sn2–C41) (Sn2)
2.040 (Sn2–O7),
2.151
(Sn2–O7A),
2.253 (Sn2–O2),
2.674
(Sn2–O4A)
syn-Sn(qaldsme)- NNS Monoclinic P21 /n — 2.670 (Sn1–N3), 2.151 (Sn1–C19), 2.519 (Sn1–Cl1), 153.87 131
Ph2 Clm 2.321 (Sn1–N2) 2.147 (Sn1–C13) 2.499 (Sn1–S1)
anti-Sn(qaldsme)- NNS Monoclinic P21 /n — 2.513 (Sn1–N3), 2.148 (Sn1–C19), 2.532 (Sn1–Cl1), 164.21 131
Ph2 Clm 2.322 (Sn1–N2) 2.151 (Sn1–C13) 2.525 (Sn1–S1)
(n-C4 H9 )2 SnCl2 ·Ln NN Orthorhombic P21 21 21 — 2.506 (Sn1–N1), 2.125 (Sn1–C21), 2.467 (Sn1–Cl1), 164.8 154
2.575 (Sn1–N2) 2.117 (Sn1–C31) 2.499 (Sn1–Cl2)
(n-C4 H9 )2 SnLo ONO Monoclinic P21 /c 2.234 (Sn2–O1), 2.244 (Sn2–N6) 2.116 (Sn2–C), — 145.89 139
2.087 (Sn2–O3), 2.122 (Sn2–C)
2.500
(Sn2 ◊ ◊ ◊ O3)
(n-C4 H9 )2 SnLp ONO Monoclinic P21 /c 2.268 (Sn2–O1), 2.237 (Sn2–N6) 2.138 (Sn2–C), — 151.90 139
2.100 (Sn2–O3), 2.120 (Sn2–C)
2.457
(Sn2 ◊ ◊ ◊ O3)

This journal is © The Royal Society of Chemistry 2011 Dalton Trans., 2011, 40, 7077–7121 | 7111
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Table 3 (Contd.)

Ligand Crystal Space

Compound donors system group Sn–O/Å Sn–N/Å Sn–C/Å Sn–Xa /Å C–Sn–C/◦ Ref.

{[n-BuSnCl2 ]- [4- ONO Monoclinic P21 /c 2.143 (Sn1–O1), 2.189 (Sn1–N1) 2.137 (Sn1–C14) 2.60 (Cl1), 2.437 — 74
NHC5 H4 CON2 CH- 2.056 (Sn1–O2) (Cl2)
(C6 H4 O-2)]+
Me2 Sn[Ph(O)CCHC- ONO Monoclinic P21 /c 2.110 (Sn1–O1), 2.176 (Sn1–N1) 2.100 (Sn1–C20), — 141.72 113
(Me)NC6 H4 (O)] 2.201 (Sn1–O2) 2.116 (Sn1–C21)
a
X = Other atoms. b NAPPDI = N,N¢-Bis(2-hydroxy-1-naphthaldehyde)-1,2-phenylenediimine. c HOBENZ-4Me = 1-[(4-Methylphenylimino)methyl]-
2-phenol. d LH = 6-Methylpyridine-2-carbaldehyde phenylhydrazone. e Sal·p-CH3 OBzh = N-Salicylidene-p-methoxybenzoylhydrazone. f L = N-
(3-tert-Butylsalicylidene)-2,3,4,5,6-pentafluoroaniline. g L = N-(3-tert-Butylsalicylidene)aniline. h L = o-Vanillin-2-thiophenoylhydrazone. i 4-[(2Z)-
(3-Hydroxy-1-methyl-2-butenylidene)amino]benzoic acid. j Phensal = 3,5-Di-tert-butylsalicylidene(1-aminophenylene-2-amine). k Vanophen = N,N¢-
Bis(3-methoxysalicylaldehyde)-1,2-phenylenediimine. l N-(4-Carboxyphenyl)salicylideneimine. m qaldsme = 2-Quinolinecarbaldehyde Schiff base of S-
methyldithiocarbazate. n L = C6 H5 N CHC5 H4 N-2. o HL = Schiff base derived from salicylaldehyde and b-aminopropan-1-ol. p HL = Schiff base derived
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

from salicylaldehyde and b-aminobutanol.

Table 4 X-Ray crystallographic data of organotin(IV) complexes of Schiff bases having pentagonal bipyramidal geometry
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Ligand Space Sn–Xa /

Compound donors Crystal system group Sn–O/Å Sn–N/Å Sn–C/Å Å C–Sn–C/◦ Ref.

Bu2 Sn(L)·2(OHC3 H7 -i)b ONO, 2O Monoclinic P21 /c 2.305 (Sn1–O1), 2.251 (Sn1–N1) Not given — 158.4 74
2.174 (Sn1–O3),
2.486 (Sn1–O4)
{Bu2 SnCl(O)Bu2 Sn(O)- ONO Triclinic P1̄ 2.169 (Sn1–O3), 2.166 (Sn1–N1) Not given — 162.0 74
(L)SnBu2 (HOCH3 )}2 ]n c 2.313 (Sn1–O1), (C11–Sn1–C15),
2.496 (Sn1–O6), 129.9
2.021 (Sn2–O5), (C23–Sn2–C19),
2.297 (Sn2–O4), 133.5
2.020 (Sn3–O5), (C27–Sn3–C31)
2.247 (Sn3–O4)
(o-ClBz)2 Sn(L)d ONO Monoclinic P21 /n 2.337 (Sn1–O1), 2.220 (Sn1–N1) Not given — 158.6 74
2.133 (Sn1–O3),
2.504 (Sn1–O5)
Oct2 Sn(L)(H2 O)]2 e ONO Monoclinic C2/c 2.386 (Sn1–O1), 2.296 (Sn1–N1) Not given — 163.8 74
2.185 (Sn1–O3),
2.378 (Sn1–O5)
Bu2 Sn(L)(HOSnBu3 )]2 f ONO Triclinic P1̄ 2.397 (Sn1–O1), 2.279 (Sn1–N1) Not given — 164.6 74
2.190 (Sn1–O3), (C11–Sn1–C15),
2.253 (Sn1–O4), 111.7
2.016 (Sn2–O4) (C19–Sn2–C23),
113.0
(C19–Sn2–C27),
120.0
(C23–Sn2–C27)
Ph2 SnL(H2 O)]2 g O3 N Orthorhombic P21 21 21 2.177 (Sn1–O3), 2.288 Not given — 172.7 (Sn1), 106
2.288 (Sn1–O7), (Sn1–N1), 174.2 (Sn2)
2.385 (Sn1–O1), 2.282 (Sn2–N4)
2.538 (Sn1–O4),
2.191 (Sn2–O6),
2.274 (Sn2–O8),
2.360 (Sn2–O4),
2.552 (Sn2–O1)
(PhCH2 )2 SnL(H2 O)]2 g O3 N Monoclinic C2/c 2.165 (Sn1–O3), 2.260 Not given — 168.5 (Sn1), 106
2.291 (Sn1–O4), (Sn1–N1), 167.5 (Sn2)
2.383 (Sn1–O1), 2.272 (Sn2–N4)
2.597 (Sn1–O5),
2.168 (Sn2–O7),
2.327 (Sn2–O8),
2.414 (Sn2–O5),
2.637 (Sn2–O1)
Ph(CH2 )2 SnL(CH3 OH)]2 h O3 N Monoclinic P21 /c 2.158 (Sn1–O3), 2.227 (Sn1–N1) Not given — 164.5 106i
2.296 (Sn1–O1),
2.403 (Sn1–O5),
2.816
(Sn1–O1#1)

7112 | Dalton Trans., 2011, 40, 7077–7121 This journal is © The Royal Society of Chemistry 2011
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Table 4 (Contd.)

Ligand Space Sn–Xa /

Compound donors Crystal system group Sn–O/Å Sn–N/Å Sn–C/Å Å C–Sn–C/◦ Ref.

Ph2 SnL(H2 O)]2 g O2 N2 /O3 N Not given Not

2.221 (Sn1–O3), 2.327 2.089 (Sn1–C19), — 176.8 (Sn1), 107
given
2.370 (Sn1–O7), (Sn1–N1), 2.135 (Sn1–C25), 169.9 (Sn2)
2.387 (Sn1–O1), 2.394 2.116 (Sn2–C31),
2.207 (Sn2–O4), (Sn1–N4#1), 2.136 (Sn2–C37)
2.210 (Sn2–O6), 2.249 (Sn2–N4)
2.388 (Sn2–O2),
2.594 (Sn2–O1)
(n-C8 H17 )2 SnL(H2 O)]2 g O3 N Not given Not 2.219 (Sn1–O3), 2.283 (Sn1–N1) 2.06 (Sn1–C18), — 164.4 (Sn1) 107i
given 2.340 (Sn1–O1), 2.09 (Sn1–C10)
2.354 (Sn1–O4),
2.715
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

(Sn1–O5#1)
(o-ClBz)2 SnL(H2 O)]2 g O3 N Not given Not 2.180 (Sn1–O3), 2.275 (Sn1–N1) 2.145 (Sn1–C17), — 165.0 107i
given 2.614 2.166 (Sn1–C10)
(Sn1–O1#1),
2.323 (Sn1–O4),
2.400 (Sn1–O1)
(o-ClBz)2 SnL- O3 N Not given Not 2.138 (Sn1–O3), 2.270 (Sn1–N1) Not given — 163.8 (Sn1) 107i
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(CH3 OH)]2 h given 2.331 (Sn1–O1),

2.394 (Sn1–O5),
2.647
(Sn1–O1#1)
n-Bu2 SnL(H2 O)]2 g O3 N Orthorhombic Pca21 2.182 (Sn1–O3), 2.306 2.112 (Sn1–C10), — 165.7 (Sn1), 116
2.369 (Sn1–O4), (Sn1–N1), 2.115 (Sn1–C14), 164.5 (Sn2)
2.370 (Sn1–O1), 2.288 (Sn2–N4) 2.116 (Sn2–C31),
2.634 (Sn1–O5), 2.134 (Sn1–C27)
2.181 (Sn2–O7),
2.371 (Sn2–O5),
2.372 (Sn2–O8),
2.646 (Sn2–O1)
Me2 Sn(dapmdtc)j SN4 S Orthorhombic Pmnb — 2.371 2.135 (Sn1–C8) 2.731 174.24 132
(Sn1–N3), (Sn1–S1a)
2.480
(Sn1–N2a)
Me2 Sn(dapbdtc)k SN4 S Monoclinic C2/c — 2.359 2.135 (Sn1–C15) 2.647 171.5 132
(Sn1–N1), (Sn1– S1)
2.427 (Sn1–N2)
Me2 Sn(dapbdtc)k SN4 S Monoclinic C2/c — 2.369 2.178 (Sn1–C1) 2.6353 171.5 132
(Sn1–N1), (Sn1–S1)
2.422 (Sn1–N2)
Bu2 Sn(L)l N3 O2 Monoclinic C2/c 2.177 (Sn1–O1), 2.538 2.119 (Sn1–C19), — 169.2 141
2.304 (Sn1–O2) (Sn1–N1), 2.115 (Sn1–C23) (C19–Sn1–C23)
2.383
(Sn1–N2),
2.423 (Sn1–N3)
Bu2 Sn(L)m N3 O2 Monoclinic P21 /c 2.243 (Sn1–O1), 2.538 2.128 (Sn1–C20), — 170.8 141
2.242 (Sn1–O2) (Sn1–N1), 2.137 (Sn1–C24) (C20–Sn1–C24)
2.436
(Sn1–N2),
2.382 (Sn1–N3)
a
X = Other atoms. b L = [2-SC4 H3 CON2 C(CH3 )CO2 ]. c L = [C6 H4 CON2 C(CH3 )CO2 ]. d L = [4-HOC6 H4 CON2 C(CH3 )CO2 ]. e L = [2-
HOC6 H4 CON2 C(CH3 )CO2 ]. f L = [C6 H5 CON2 C(CH3 )CO2 ]. g 4-NC5 H4 CON2 C(CH3 )CO2 . h 2-HOC6 H4 CON2 C(CH3 )CO2 . i Only one value provided due
to the mirror symmetry of the molecule. j 2,6-Diacetylpyridine-bis(S-methyldithiocarbazate). k 2,6-Diacetylpyridine-bis(S-benzyldithiocarbazate). l Schiff
base derived from 2-aminophenol, 2-pyridinecarbaldehyde and 2-picolinic acid. m Schiff base derived from 2-amino-4-nitrophenol, 2-pyridinecarbaldehyde
and 2-picolinic acid.

The decomposition of the complexes takes place in two steps in
the temperature range 67–660 ◦ C, giving SnO2 or SnO + S as the
end product (Scheme 10).
Thermal gravimetric analysis of {(n-Bu)2 Sn[2-
SC4 H3 CON2 C9CH3 )CO2 ](HOC3 H7 -i)}2 revealed75 that the
decomposition of the hydrazone ligand occurs between 200
and 300 ◦ C along with the collapse of the whole structure and
the residue is SnO2 . Thermal decomposition of R3 SnCl(L),55
Ph2 Sn(L)2 ,81 (where R = Me and Ph; L = Schiff base derived from
condensation of 2-amino-5-(o-methoxyphenyl)-1,3,4-thiazole
with salicylaldehyde, 2-hydroxy-1-naphthaldehyde, benzyl methyl
ketone and acetyl acetone) and Ph3 Sn(L), Ph2 SnL and Ph2 SnL
(where L = Schiff base derived from condensation of benzaldehyde
or 2-hydroxy-1-naphthaldehyde with DL-valine, D-phenylalanine,
2-aminobutyric acid, L-leucine and DL-a-aniline)89 have also been
investigated by Nath et al. In each case the end product is either
SnO2 or mixture of SnO + S or SnS2 which has been confirmed
by X-ray determination.55,81,89

This journal is © The Royal Society of Chemistry 2011 Dalton Trans., 2011, 40, 7077–7121 | 7113

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Scheme 10 Proposed scheme for decomposition of Ph3 SnCl(FuFSCZ) (i), Ph2 Sn(OH–AcPhSCZ) (ii) and Ph3 Sn(4-MeBenzTSCZ) (iii).156
Scheme 11 Thermal decomposition routes of Me2 Sn(L)2 , Ph2 Sn(L)2 and n-Oct2 Sn(L)2 , where HL = Schiff base derived from 2-aminomethylbenzimidazole
and salicylaldehyde.88
Kaushik et al.56,134 have investigated thermodynamic parameters
for the decomposition step using TG-DTA curves of organotin(IV)
complexes of aniline-N-thiohydrazone, benzaldehydeaniline-
N-thiohydrazone56 and the Schiff base derived from
dithiocarbazate,134 and reported SnO2 as end product.56,134
Recently Yin et al.70 examined the thermogravimetic analysis
of (R2 Sn)2 L (where R = Me and n-Bu; L = diacylhydrazone) in
the temperature range 50–500 ◦ C under dry N2 atmosphere to
study the stability of synthesized complexes. The TGA curves
of complexes exhibit one continuous weight loss step in the
temperature range of 250–400 ◦ C.
Nath et al. have recently investigated thermal decomposition of
tri- and diorganotin(IV) complexes of the Schiff base derived from
2-aminomethylbenzimidazole and salicylaldehyde88 (Scheme 11),
and of the tripodal Schiff base ligand containing three imidazole
arms.115 All of the complexes decompose gradually in two or
7114 | Dalton Trans., 2011, 40, 7077–7121
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more than two steps with the formation of SnO2 , which has been
characterized by XRD spectral data. Thermal analysis data along
with species lost in all of the complexes are compiled in Tables 5
and 6.88,115 Thermal decomposition of organotin(IV) complexes
of 4-bromo-2-{[(2-hydroxyphenyl)imino]methyl}phenol has been
studied by Sedaghat and Shafahi 136 and the activation energy has
also been determined by the Horowitz–Metzger method.
6. Biological studies of organotin(IV) complexes of
Schiff bases
The organotin(IV) derivatives of Schiff bases are of
considerable interest as they have been proposed to
possess mild to good antitumor,44,45,47,61,92,94–96,111,125,140
antimicrobial,46,48,50,52,53,55,56,58,61,74,79–83,89,91,93,100,101,110–112,119–127,135,140,145
This journal is © The Royal Society of Chemistry 2011
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Table 5 Thermal analysis data of organotin(IV) complexes of HL in air (where HL = Schiff base derived from 2-aminomethylbenzimidazole and
salicylaldehyde [87])

Temp. range Peak temp. Peak temp. Enthalpy/ Mass lossa

Compound Step no. (TG)/◦ C (DTG)/◦ C (DTA)/◦ C mJ mg-1 (%) Species lost

Me3 Sn(L) I 100–125 114, 120 No sharp peak — 10.20 (10.89) C3 H9 (3 Me)
II 125–543 488 490 (exo) -3062 57.16 (57.58) C15 H12 N3
III 543–692 — 681 (exo) -138 4.37 Sublimation
n-Bu3 Sn(L) I 90–310 260 — — 32.22 (31.71) C12 H27 (3Bu)
II 301–510 455 355 (exo) -224 37.00 C15 H12 N3
463 (exo) -4117 (43.36)
III 670–850 776 776 (exo) -73.6 4.03 Sublimation
Ph3 Sn(L) I 100–434 153 80 (endo) 33.4 37.69 C18 H15 (3Ph)
180 285 (endo) 101 (38.53)
291
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

II 434–800 440 452 (exo) -2018.58 32.35 C15 H12 N3

449 469 (exo) -2761.42 (39.02)
455
Me2 Sn(L)2 I 100–210 207 185 (exo) -117 6.50 (4.63) C2 H6 (2 Me)
II 210–521 429 446 (exo) -8693 59.67 (63.84) C28 H22 N4
III 521–955 952 792 (endo) 16.1 8.32 (10.20) C2 H2 N2
n-Bu2 Sn(L)2 I 25–270 260 262 (exo) -14.2 17.30 (15.57) C8 H18 (2Bu)
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II 270–700 482 486 (exo) -3115 54.22 C28 H22 N4

667 (exo) -58.2 (56.51)
III 700–950 — — — 8.20 (7.36) C2 H2 N2
Ph2 Sn(L)2 I 100–325 234 258 (exo) -167 19.84 (19.94) C12 H10 (2Ph)
II 325–626 444 447 (exo) -7086 44.85 (49.70) C26 H16 N4
III 626–960 706 663 (exo) -260.74 17.48 C4 H8 N2
949 704 (exo) -179.26 (10.87)
789 (endo) 22.5
n-Oct2 Sn(L)2 (8) I 25–280 259 — — 26.72 (26.72) C16 H34 (2Oct)
II 280–528 486 498 (exo -5807 61.97 (55.41) C30 H24 N6
a
Calculated mass loss in parentheses.

antinematicidal,84 antiinsecticidal,81,84 antiherbicidal81
antiinflammatory 88,110,115 activities.
6.1 Antitumor studies
Ph2 Sn[3,5-Br2 -2-OC6 H2 CH NCH(R)COO]·Ph2 SnCl2 (R = H,
Me, i-Pr and Bz),61 R2 ¢Sn(5-X-2-OC6 H3 CH NCH(i-Pr)COO)
(R¢ = n-Bu, Ph and Cy, X = Cl and Br)92 and Ph3 Sn(HL)·Ph2 SnL
(L = 3,5-Br2 -2-OC6 H2 CH NCH(i-Pr)COO)93 have been found
to exhibit better cytotoxic activity against three human tumor cell
lines (HeLa, CoLo205 and MCF-7) than cis-platin, and the activ-
ity decreased in the order Cy > n-Bu > Ph for the R¢ group bound
to tin.92 The complexes, viz. {[n-Bu2 Sn(LH)]2 O}2 (LH = b-{[(E)-
1-(2-hydroxyphenyl)ethylidene]amino}propionate),96 R2 SnL (R =
n-Bu and Ph, H2 L = Schiff bases derived from condensation
of 2-hydroxy-1-naphthaldehyde with glycine or L-b-alanine, and
derived from condensation of acetyl acetone with L-luecine)125
and n-Bu3 SnL (HL = Schiff base derived from condensation
of salicylaldehyde and adenine)110 have shown quite promising
antitumor activity against WIDR, M19 MEL, A498, IGROV,
H226, MCF-7, EVSA-T96,125 ] and KB110 human tumor cell lines in
comparison to cis-platin96,110,125 and carboplatin.125
Recently, three triphenyltin(IV) and one diphenyltin(IV)
complexes of amino acetate functionalized Schiff bases95 have
been tested against seven human tumor cell lines, viz. WIDR,
M19 MEL, A498, IGROV, H226, MCF-7, EVSA-T. The
average ID50 (minimum concentration/dose to inhibit the
tumor cell growth by 50%) values in the range 33–96, 42–104
and and 31–38 ng mL-1 have been obtained for triphenyltin(IV) 2-
{[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)]amino}-4-methyl-
pentanoate, triphenyltin(IV) 2-{[(2E)-1-(2-hydroxyphenyl)-
methylidene]amino}-4-methylpentanoate and triphenyltin(IV)
2-{[(2E)-1-(2-hydroxyphenyl)ethylidene]amino}-4-methylpent-
anoate, respectively, whereas diphenyltin(IV) 2-{[(2Z)-(3-hydroxy-
1-methyl-2-butenylidene)]amino-4-methylpentanoate exhibit ID50
value in the range 199–987 ng mL-1 , across seven human tumor
cell lines.95 The most cytotoxic, triphenyltin(IV) 2-{[(2E)-1-(2-
hydroxyphenyl)ethylidene]amino}-4-methylpentanoate, has been
found to be more cytotoxic for all the cell lines studied than
the standard drugs, doxorubicin, cis-platin, 5-flurouracil and
etopside. The high cytotoxicity of triphenyltin(IV) complexes is
likely to be because of the non-involvement of the nitrogen atom
in the coordination with the tin atom (Scheme 5, complexes 1, 2
and 3), which allows easy dissociation of the complex so that it
can subsequently bind to DNA. This corroborates with the fact
that the diphenytltin(IV) complex (Scheme 5, complex 4) shows
lower activity, in which azomethine nitrogen also coordinates to
the tin atom.
The efficiency of bis(2-[(9H-purin-6-ylimino)]phenolate)
dimethyl-/diethyl-/dibutyl-/diphenyl/dibenzyl-tin(IV) complexes
as potential antitumor drugs has been tested in vitro on the KB
cell line, derived from a human epidermoid carcinoma by using
DMSO to solubilize the complexes prior to use in biological
experiments. Bis(2-[(9H-Purin-6-ylimino)]phenolate)diethyltin
complexes is the most potent, being even better than cis-platin,
under the same experimental conditions.111

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Table 6 Thermal analysis data of organotin(IV) complexes of tripodal Schiff base (H3 L) in air114

Temp. range Peak temp. Peak temp. Enthalpy/

Compound Step no. (TG)/◦ C (DTG)/◦ C (DTA)/◦ C mJ mg-1 Mass lossa (%) Species lost

Me2 Sn(HL) I 70–253 230 26.69 (26.56) C8 H13 N3

II 253–606 505 505 (exo) -1098.7 62.94 (52.59) C15 H21 N7 + Sn
sublimation & oxidation
557 560 (exo) -1917.3
Me3 Sn(H2 L) I 29–439 187 51.32 (51.67) C16 H26 N6
II 439–623 505 508 (exo) -2216.6 41.03 (28.94) C8 H12 N4 + Sn
sublimation & oxidation
549 550 (exo) -1973.4
n-Pr3 Sn(H2 L) I 199–502 250 258 (exo) -79.3 78.42 (82.12) C30 H49 N10 + Sn
sublimation & oxidation
462 469 (exo) -2498.7
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496 500 (exo) -2967.3

n-Bu2 Sn(HL) I 27–305 259 256 (endo) 43.9 37.53 (38.32) C15 H28 N3
II 305–602 551 465 (exo) -655.6 51.40 (43.51) C14 H18 N7 + Sn
sublimation & oxidation
509 (exo) -792.9
556 (exo) -1448.3
n-Bu3 Sn(H2 L) I 27–355 198, 224 239 (exo) -210 54.92 (54.32) C22 H38 N6
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II 355–601 522 523 (exo) -1972 41.64 (28.99) C11 H18 N4 + Sn

sublimation & oxidation
552 551 (exo) -1972
Ph2 Sn(HL) I 24–380 166, 250 259 (exo) -31.9 31.94 (30.75) C13 H15 N3
II 380–570 442 430 (exo) -913.1 46.32 (52.12) C20 H23 N7 + Sn oxidation
478 488 (exo) -1945.4
542 549 (exo) -1528.5
Ph3 Sn(H2 L) I 28–299 166, 168, 238 34.95 (35.30) C14 H20 N6
II 299–568 505 508 (exo) -2980 46.59 (49.31) C25 H24 N4 + Sn oxidation
n-Oct2 Sn(HL) I 25–363 149, 176, 196 233 (exo) -82.9 48.08 (47.35) C23 H44 N3
II 363–571 526 528 (exo) -4238 47.49 (37.14) C14 H18 N7 + Sn
sublimation & oxidation
a
Calculated mass loss in parentheses.

6.2 Antimicrobial studies
The complexes of the types, Rn SnCl4-n ·L (n = 3, R =
Me,54 Ph54 and p-Cl-Bz;55 n = 2, Me,46 n-Bu,46 Ph46,55
and p-Cl-Bz;56 L = Schiff bases derived from condensation
of 2-/3-aminopyridines with 2-hydroxy-, 2-methoxy- or 2-
hydroxy-3-methoxy-benzaldehyde;46 derived from 2-amino-5-(o-
methoxyphenyl)-1,3,4-thiazole and salicylaldehyde, 2-hydroxy-1-
naphthaldehyde, benzyl methyl ketone and acetyl acetone;55 de-
rived from N-thiohydrazone;56 Sn(H3 mfps)(C6 H5 )2 Cl2 ·2H2 O and
Sn(Hmfpp)(n-C4 H9 )2 Cl;51 R3 Sn(ONN) (R = n-Bu or Ph; ONN =
tridenate Schiff base);80 Rn SnLm (n = 3, m = 1, R = Me and Ph;
n = 2, m = 2, R = n-Bu and Ph; L = anion of Schiff bases de-
rived from condensation of 2-amino-5-(o-methoxyphenyl)-1,3,4-
thiazole with salicylaldehyde, 2-hydroxy-1-naphthaldehyde and 2-
hydroxyacetophenone);81 Ph2 SnLCl/Ph2 SnL2 (L = anion of Schiff
bases derived from condensation of S-benzyldithiocarbazate
with heterocyclic aldehydes);82 R2 SnL2 /R2 SnLCl (R = Me and
Ph; L = anion of 2-acetylfuransulfaguanidine);84 Ph2 SnL/n-
Bu2 SnL/Ph3 SnL¢/(L = anion of Schiff bases derived from con-
densation of amino acids with 2-hydroxy-1-naphthaldehyde, acetyl
acetone (H2 L) and benzaldehyde (HL¢));89,125 Ph3 Sn(HL)·Ph2 SnL
(L = 3,5-Br2 -2-OC6 H2 CH NCH(i-Pr)COO);93 Ph3 SnL (L = an-
ion of Schiff base derived from condensation of salicylaldehyde
and adinine);110 n-Bu2 SnL2 /n-Bu3 SnL (L = anion of Schiff bases
derived from condensation of heterocyclic ketone with sulfa drugs
or amino acids);120,121,124,126 SnR2 (PLPM - 2H) (PLPM - 2H =
anion of Schiff base derived from condensation of pyrodoxal
and pyridoxamine)127 and R2 SnL (R = n-Bu or Ph; L = anion of
Schiff bases derived from salicylaldehyde and b-aminoalcohols) 140
showed a remarkable activity towards bacterial species, e.g. Pseu-
domonas vulgaris,46 Pseudomonas aeruginosa,46,55,81,89,110,125,127,140
Pseudomonas cepacicola,84 Pseudomonas syringae,120,121,126 Es-
cherichia coli,51,55,81,82,84,89,93,110,120,121,124–127,140 Klebsiella pneumo-
niae,46,55,81,82,84,89,125 Salmonella typhimurium,46,110 Staphylococ-
cus aureus,46,51,55,81,82,84,89,93,110,120,121,124–127 Bacillus subtilis,46,110,126,127,140
Streptococcus faecalis,55,81,89,125 Proteus mirabilis,120,121,124 Bacillus
thuringiensis,81,120,124 Desulfovibrio longus140 and Desulfomicro-
bium aspheronum,140 and fungal species, e.g. Aspergillus fumiga-
tus,51,55,81,89,125 Aspergillus flavus,51,120 Aspergillus niger,82,84,120,124 Al-
ternaria tenuis,51 Alternaria alternate,84 Candida albicans,55,81,89,125
Fusarium spp.51 Fusarium oxysporum,84 Botrytis cinerea,51 Penicil-
lium spp.51 Pythium irregulare,51 Sclerotinia minor,51 Stemphylium
vesicarium,51 Cryptococcus neoformans,55,81,89,125 Sporotrichum
schenckii,55,81,89,125 Trichophyton mentagrophytes,55,81,89,125 Rhizocto-
nia bataticola,56 Rhizoctonia phaseoli,81,120 Penicillium crysogenes82
and Macrophomina phaseolina.84
Recently, Singh and Varshney reported82 that organotin(IV)
complexes of dithiocarbazates are more active for all mi-
crobial species than the corresponding semicarbazones and
thiosemicarbazones157 reported earlier, which indicates that sul-
fur compounds are more active than oxygen compounds. The
increased activity of organotin(IV) complexes may be due to the
coordination of Schiff bases to the central tin atom through

7116 | Dalton Trans., 2011, 40, 7077–7121 This journal is © The Royal Society of Chemistry 2011

the thioketo sulfur and azomethine nitrogen. The compounds
containing a halogen atom attached directly to the central tin atom
also showed moderate activity but the replacement of halogen by
another ligand moiety enhances the biochemical properties of the
whole molecules. It has been proposed that the mode of action
of organotin(IV) dithiocarbazates may involve the formation of
hydrogen bond through the (–N C–S) group with the active
centers of the cell constituents resulting in an interference with the
cell process.82 Triorganotin(IV) complexes of Schiff base derived
from indoline-2,3-dione and 2-aminobenzoic acid showed signifi-
cant activity against Staphylococcus aureus,100 and triorganotin(IV)
complexes of 1,3-bis(2-hydroxy-5-methylbenzylidene)urea have
been found to exhibit significant antibacterial activity against
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E
Staphylococcus aureus and Mycobacterium leprae,101 but their
activity is lower than the standard drug imipinem. The order
of increased antibacterial activity is: Me3 SnL < Ph3 SnL <
Bz3 SnL.100,101 Further, the triphenyltin(IV) complex of 1,3-bis(2-
hydroxy-5-methylbenzylidene)urea also showed significant anti-
Downloaded by University of Sussex on 18 June 2012
fungal activity against C. glocosporiodes, A. brassicicola and C.
capsici101 at 500 ppm dose, and the order of increased antifungal
activity is: Me3 SnL < Bz3 SnL < Ph3 SnL. It has been proposed
that the activity of these complexes might be due to the presence
of a hydroxyl and phenyl groups.
Diorganotin(IV) complexes of 2-[(9H-purin-6-ylimino)]phenol
have been screened against Gram positive bacteria, S. aureus and
B. subtilis, and Gram negative bacteria, P. aeruginosa, E. coli and
S. typhi, and it was found that the complexes are more active
towards Gram positive strains than Gram negative strains,111
which may be due to the difference in the structures of the cell
walls. The walls of Gram negative cells are more complex than
those of Gram positive cells. Further, it has been found that the
ligand showed low, and the complexes moderate to high activities
as compared to the standard drug (imipinem). The MIC values
against B. subtilis, S. aureus, E. coli, S. typhi and P. aeruginosa
are 128, 128, 64, 64 and 64 mg mL-1 for ligand; 64, 64, 32, 32
and 32 mg mL-1 for Me2 SnL2 ; 32, 64, 32, 32 and 32 mg mL-1
for Et2 SnL2 ; 16, 16, 32, 32 and 16 mg mL-1 for Bu2 SnL2 ; 8, 8,
16, 16 and 8 mg mL-1 for Ph2 SnL2 ; 32, 16, 16, 16 and 32 mg
mL-1 for Bz2 SnL2 , respectively.111 The results showed that the
diphenyltin(IV) complex exhibited potent activity as compared
to the other studied complexes. These complexes have also been
screened against fungi, Aspergillus niger, Fusarium oxysporum and
Aspergillus flavus and found that diphenyltin(IV) complex showed
excellent activity (22–27% growth inhibition) against all fungal
strains.
Dimethyltin(IV) complexes of Schiff bases derived from 2-
amino-3-hydroxypyridine and different substituted salicylaldehy-
des have been screened against bacteria, viz. S. aureus ATCC
25923, E. coli ATCC 25922, E. coli ATCC 35218, E. faecalis
ATCC 29212, S. epidermidis ATCC 12228, E. cloacae ATCC
23355, S. marcescens ATCC 8100, and P. aeruginosa ATCC
27853, and fungi, viz. A. niger, A. flavus, A. fumigatus and C.
albicans and found that the change of a substituent in the ligand
may lead to enhanced antibacterial and antifungal activities of
these dimethyltin(IV) complexes.112 [N-(3-hydroxypyridine-2-yl)-
3,5-dichlorosalicylideneiminato]dimethyltin(IV) displayed higher
activity against S. aureus than the standard drug gentamisin, and
it also showed more activity against all Aspergillus species than the
other complexes.112 Recently, dimethyltin(IV) complexes of Schiff
This journal is © The Royal Society of Chemistry 2011
View Online
bases derived from S-benzyldithiocarbazates/benzothiazolines
have been screened against Rhizoctonia phaseoli, Penicillum
chrysogenum, S. aureus, B. subtilis, P. aeruginosa and S. ty-
phi at different concentrations.145 Me2 Sn(L)2 (where HL =
4-nitrobenzanilidebenzothiazoline) showed the highest activity
among all the studied complexes.
The enhanced bactericidal activity of the ligand on com-
plexation with the organotin(IV) moiety may be explained by
chelation theory.158 It has been concluded that the chelation
considerably reduced the polarity of the metal ion because of the
partial sharing of its positive charge with the donor groups and
the p-electron delocalization over the whole chelate ring. Such
chelation could enhance the lipophilic character of the central
metal atom, which subsequently favors its permeation through
the lipid layer of the cell membrane. Furthermore, the enhanced
fungicidal activity of the organotin(IV) complexes as compared
to that of the parent Schiff bases may be due to the effect of
the central metal ion in the normal cell process. In general, the
antimicrobial activity of the Schiff bases and their organotin(IV)
complexes can be ascribed to hydrogen bond formation between
the (>C N) group of the compound and some bioreceptors in
the cells of microorganisms, which in turn block the synthesis
of protein by inhibiting the movement of ribosome along with
RNA. This inhibits the synthesis of DNA in the cell nucleus. The
greater toxicity of the complexes than the Schiff bases can also
be explained on the basis of greater lipophilic character of the
complexes.
6.3 Antinematicidal and anti-insecticidal studies
R2 SnL2 /R2 SnLCl (R = Me and Ph; L = anion of 2-
acetylfuransulfaguanidine) have also shown good antinematicidal
activity against Meloidogyne incognita and anti-insecticidal activ-
ity against Trogoderma granarium.84
6.4 Anti-inflammatory studies
The anti-inflammatory activity of the complexes, R3 SnL (R = Me,
Et, n-Bu, Ph and Bz; L = anion of Schiff base derived from salicy-
laldehyde and adenine) have been investigated by Rehman et al.110
The results obtained indicate the order of anti-inflammatory ac-
tivity as Ph3 SnL > Bz3 SnL > n-Bu3 SnL > Et3 SnL > Me3 SnL. Re-
cently, Nath et al. have studied anti-inflammatory activity of tri-
and diorganotin(IV) complexes of the Schiff base (HL) derived
from 2-aminomethylbenzimidazole and salicylaldehyde88 and of
tripodal Schiff base ligand (H3 L1 ) containing three imidazole
arms115 using the carrageenan-induced paw edema bioassay in
rats and phenylbutazone as a standard drug. It has been observed
that the diorganotin(IV) complexes (19.75–22.23%) of Schiff base
derived from 2-aminomethylbenzimidazole and salicylaldehyde
show better activity as compared with the triorganotin analogues.
n-Oct2 Sn(IV) complex showed good anti-inflammatory activity
(22.23% inhibition), which is higher than that of dimethyltin(IV)
(19.75% inhibition), n-dibutyltin(IV) (21.23% inhibition) and
diphenyltin(IV) (20.16% inhibition) analogues.88 Among triorgan-
otin(IV) complexes, the order of their percentage inhibition is
Me3 SnL < n-Bu3 SnL < Ph3 SnL (Table 7). Furthermore, it has
been observed that activity of diorganotin(IV) complexes increases
on increase in dose level. Organotin(IV) complexes of H3 L1
Dalton Trans., 2011, 40, 7077–7121 | 7117
 View Online

Table 7 Anti-inflammatory activity and toxicity data of Schiff base inflammatory activity of the studied complexes is influenced by
(HL),87 Schiff base (H3 L1 ),114 their organotin(IV) complexes, organotin(IV) the nature and number of organic groups attached to tin as well
chlorides/oxides and phenylbutazone87,114
as the coordinating environment of tin.88,115
Anti-inflammaory activity
6.5 Antifertility activity
Dose/mg kg-1 % Edema Acute toxicity
Drug p.o. inhibition LD50 mg kg-1 p.o Recently, dimethyltin(IV) complexes of Schiff bases derived from
S-benzyldithiocarbazates/benzothiazolines have been studied for
HL 40 2.67 > 400
Me3 Sn(L) 40 10.32 > 800 antifertility activity.145 It has been found that the motility and
n-Bu3 Sn(L) 40 14.66 > 800 count of sperm decreased after the administration of Schiff bases
Ph3 Sn(L) 40 17.86 > 800 and their dimethyltin(IV) complexes, and the spermatozoa and
Me2 Sn(L)2 40 19.75 > 800
n-Bu2 Sn(L)2 20 11.57 > 800
accessory sex organs were also affected in treated rats. The prostate
40 21.23 glands become swollen and effects did not become normal even
80 37.39 after 30 days of recovery showing the irreversible nature of the
Published on 14 April 2011 on http://pubs.rsc.org | doi:10.1039/C0DT01426E

Ph2 Sn(L)2 20 10.02 > 800 effects. A significant decrease (p £ 0.01) in mortility from 86.85
40 20.16
80 36.15 ± 3.8 to 26.27 ± 1.6 was observed in the animals treated with
n-Oct2 Sn(L)2 20 12.12 > 800 (4-nitrobenzanilide-S-benzyldithiocarbazato)dimehtyltin(IV) and
40 22.23 the count of sperm also decreased from 6.15 ± 0.52 to 0.71 ±
80 39.36
0.14 in testes and from 64.29 ± 2.9 to 23.47 ± 9.4 in cauda
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H3 L 1 40 5.21 > 400

Me2 Sn(HL1 ) 40 6.38 > 400 epididymis. A highly significant decline (p £ 0.001) in the mortility
Me3 Sn(H2 L1 ) 40 8.89 > 400 of sperms was observed in the case of Me2 Sn(L)Cl (where HL = 4-
n-Bu2 Sn(HL1 ) 40 12.28 > 800 nitrobenzanilide-S-benzyldithiocarbazate). The sperm count was
n-Bu3 Sn(H2 L1 ) 40 16.69 > 800
Ph2 Sn(HL1 ) 40 17.78 > 800 also found to decrease significantly in the treated animals. The
Ph3 Sn(H2 L1 ) 20 10.15 > 800 fertility percent varied between 98% positive to 96% negative
40 20.26 in these complexes and Schiff bases.145 These results may also
80 36.30 be correlated with the well-known fact that sulfur-containing
n-Oct2 Sn(HL1 ) 40 9.23 > 400
n-Pr3 Sn(HL1 ) 40 7.17 > 400 compounds produce infertility in male rats.159 Thus, it can be
Me2 SnCl2 40 2.97 > 400 concluded that coordination through sulfur atoms induces the
n-Bu2 SnCl2 40 5.35 > 400 sterilizing activity in the biological systems.
Ph2 SnCl2 40 4.65 > 400
n-(Oct)2 SnO 40 6.39 > 400
Me3 SnCl 40 9.89 > 400 6.6 Toxicity studies
n-Pr3 SnCl 40 5.13 > 400
n-Bu3 SnCl 40 4.89 > 400 The LD50 (mg kg-1 ) values of Schiff base (HL) derived from
Ph3 SnCl 40 7.29 > 400 2-aminomethylbenzimidazole and salicylaldehyde88 and tripodal
Phenylbutazone 20 12.67 — Schiff base (H3 L1 )115 and their tri- and diorganotin(IV) complexes
40 31.89 —
80 48.26 are given in Table 7, and it has been found that the organotin(IV)
complexes show greater LD50 values (>800 mg kg-1 ) than that
of Schiff base (HL)/(H3 L1 ) (>400 mg kg-1 ) and organotin(IV)
exhibited anti-inflammatory activity of varying degree (6.38– chlorides/oxides (>400 mg kg-1 ), suggesting the greater safety
20.26% inhibition), which are more active than Schiff base (H3 L1 ) margin of these derivatives because of their low toxicity.
(5.21% inhibition) (Table 7). It has also been observed that
organotin(IV) complexes show better activity as compared to the 7. Conclusions
starting organotin(IV) chloride/oxides (Table 7) with the exception
of Me3 SnCl (9.89% inhibition), which is slightly more active than Organotin(IV) complexes of a wide variety of Schiff bases are
that of its Schiff base complex, Me3 Sn(H2 L1 ) (8.89% inhibition). synthesized through different routes; among these more facile
Among the studied organotin(IV) derivatives of Schiff base (H3 L1 ), and commonly employed methods of their synthesis are sodium
phenyl derivatives are more active than the alkyl analogues. salt and azeotropical removal of water method. A number
Further, triorganotin(IV) derivatives are found to be more active of modern spectroscopic techniques, viz. multinuclear NMR
than diorganotin(IV) analogues, viz. Me3 Sn(H2 L1 ) (8.89% inhibi- especially 199 Sn NMR, 119 Sn Mössbauer and single-crystal X-
tion) > Me2 Sn(HL1 ) (6.38% inhibition), n-Bu3 Sn(H2 L1 ) (16.69% ray crystallography, are successfully applied to determine the
inhibition) > n-Bu2 Sn(HL1 ) (12.28% inhibition), and Ph3 Sn(H2 L1 ) wide variety of structural motifs of these complexes. Recently,
(20.26% inhibition) > Ph2 Sn(HL1 ) (17.78% inhibition), but they some organtin(IV)-Schiff bases complexes have been revealed to
are less active than phenylbutazone (31.89% inhibition). Among show interesting 2D networks, zigzag chains and macrocyclic
triorganotin(IV) complexes, the order of their percent inhibition is: metal–organic frameworks. Many of these complexes exhibit very
n-Pr3 Sn(H2 L1 ) < Me3 Sn(H2 L1 ) < n-Bu3 Sn(H2 L1 ) < Ph3 Sn(H2 L1 ). good antimicrobial, anticancer, anti-inflammatory and antifertil-
Furthermore, among diorganotin(IV) complexes, the order of ity activities. However, the action mechanisms of the organotin-
their percent inhibition is Me2 Sn(HL1 ) < n-Oct2 Sn(HL1 )< n- Schiff base complexes are not well known or not well studied,
Bu2 Sn(HL1 ) < Ph2 Sn(HL1 ) as shown in Table 7. The observed so new techniques need to be applied to understand how the
activity may be due to the easier formation of Ph3 Sn+ /Ph2 Sn2+ organotin-Schiff base complexes exert their biological activity.
moiety. The analysis of data of Table 7 indicates that the anti- The potential applications of organotin-Schiff base complexes

7118 | Dalton Trans., 2011, 40, 7077–7121 This journal is © The Royal Society of Chemistry 2011

justify a continuous development of new molecules to eliminate
the misconception that all organotin-containing molecules should
be banned due to their toxicity. More emphasis should be given by
motivated researchers to perform molecular design-based research
of organotin compounds to attain biological activities at ultra-
trace levels, moving from the selectivity to the specificity level,
with minimum undesirable side effects and low toxicity.
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