E LS EV I E R lnorganicaChimicaActa280 (1998) 30-38

Iron and manganese complexes of benzothiazoiylformazans

David A. Brown a,,, H. B6gge b, G.N. Lipunova c, A. Miiller b, W. Plass b, K.G. Walsh .~,t
~'Departmentof Chemistry.. UniversityCollege, Belfield. Dublhz4. Ireland
hLehrstuhlftirAnorganische Chemie!, Fakultiitfiir Chemic, Uaiversiti~tBielefeld, Universitiitstrasse25, Pos~'ach100131, 33501 Bielefeld. Germany
cDepartmentof Organic Chemistry. Urals State Technical University, 62002 Ekaterinburg, Russia
Received22 July 1997;receivedin revisedform5 September1997;accepted 16October1997
Dedicatedto the memoryof ProfessorMark Vot'pin

Abstract

A series of Iron (Fe(II)) and manganese (Mn(II)) complexes of 1,3-substituted 5-(2-benzothiazolyl ) formazans are reported. The crystal
structures of the Fe (II) and Mn(II) complexes of 1,3-diphenyl-5-(2-benzothiazolyi) formazan are very similar and both contain a coordination
sphere of four five-membered rings involving the N ~and N-anitrogen atoms of the fommzan chain and the N-"of the heterocyle resulting in a
distorted octahedral structure in both cases. The distortions arise primarily from the spatial requirements of the bulky phenyl substitutents.
© 1998 Elsevier Science S.A. All rights reserved.

Ke)words: Ironcomplexes:Manganesecomplexes;Formazanderivativecomplexes

1. Introduction
Formazans which contain the azohydrazone system of con-
jugated double bonds (Fig. 1) were first reported over a
century ago [1,2] as both the 1,5-diphenyl and 1,3,5-tri-
phenyl derivatives. An extensive series of 3 (meso) substi-
tuted formazans occur. Initial applications of these
compounds included the dye industry and histochemistry
where their ease of oxidation to the corresponding tetrazolium
salt accompanied by distinctive cotour changes was invalu-
able in cell staining [ 3 ]. The first hetarylformazan containing
a pyridine ring in the five position was reported in t951 [41
and since then a wide range of hetarylformazans have been
reported together with detailed structural investigations and
studies of their metal complexation properties, notably by
Lipunova and co-workers [5,6]. Formazans are both tauto-
mericaUy and conformationally labile and a particular hetar-
ylformazan can exist in chelate, semi-open and open forms
with the 3 (meso) substituent being particularly effective at
determining conformation, with increasing size of the 3-sub-
stituent favouring the chelate (closed) form (Fig. 1). For
example, 3-ethyl-1,5-diphenyl formazan forms both the open
(anti, s-trans) form and the semi-open (syn, s-trans) forms
whereas bulkier 3-substituents such as Bu t result in formation
* Correspondingauthor.Tel.: + 353-1-7062297;fax: + 353-1-7062127.
PresentAddress:Universityof Uppsala.Sweden.
of only the closed chelate tbrm [7]. In the case of hetaryl-
formazans, if the hetero substituent contains a nitrogen in its
ring then further tautomerism can occur with formation of an
irrtino-form. In general, metal complexation occurs by depro-
tonation of the formazan (HL), especially in polar solvents,
although in aprotic solvents it is possible to isolate complexes
of the form [MX,, (xHL)] (X=halide) 181. Frequently,
octahedral complexes are formed by hetarylformazans
involving normal N coordination (N~ and N4) and a ring
nitrogen atom as in the reporte,+ crystal structure of the nickel
complex of l-(4-butylphenyl)-3-butyl-5-(2-benzothiazol-
yl)formazan and the cobalt complex of 1-(4-butylphenyl)-
3-phenyl-5-(2-benzothiazolyl)formazan 191 and related
complexes [ 10]. In the present paper we report the synthesis
of a series of 1,3-substituted 5-(2-benzothiazolyl) formazans
and their complexes with iron and manganese together with
related spectroscopic and structural studies.
2. Results and discussion
2.1+ Synthesis and characterisation of hetarylformazans
The following hetarylformazans (1-VII) were synthesised
by the reaction of the appropriate benzothiazole hydrazone
with the appropriately substituted phenyl diazonium chloride.
For simplicity we refer to a 1,3,5-substituted 5-(2-benzo-

0020-1693/98/$ - see front matter © 1998 ElsevierScience S.A. All rights reserved.
Pil S0020-1693( 98 )00050-4
 DA. Brown et al. /Inorganica Chimica Acta 280 (1998) 30-38 31

Table I
Selected data for helarylformazansand metal complexes

Compound UV spectra ~ Infrared frequencies" {cm ') Effectivemagnetic

(A,,~, (nm))
(¢(lmol-~cm t)) v(NH) v(CO) v(C=N) /z., (B.M.)

(Ph-Ph-Bt) ' 467 1516

(5.64× liP)
[Fe(Ph-Ph-Bt 12] 513 686
(Z65× I0') ( 1.36× IO~) 1596 diamagnetic
l Mn( Ph-Ph-Bt ) 21 469 642 1483 2.98 (Evans)
~1.47 × 10"*) (5× I0 ~} 2.20 (Gouy)
(CaPhHpBt)" 430 3450 1610 1589
(6.90 x i0 ~) 3156
[ Fe (CaPhHpBt): ] 497 686 1697 1458 2.60 {Evans)
( 2.15 × 10~) ( 1.03× IO~) 1652 2.90 (Gouy)

[Mn{ CaPhHpBt)~l 484 622 1613 1494 3.10 (E~-ans)

(2.29× 1o~) ( 1.50× tift) 1588

"In EtOH
KBr.
1,3-Diphenyl-5-(2-benzothiazolyllformazan.
a I - ( 2-Carboxyphenyl)-3-heptyl-5-( 2-benzothiazolyl) formazan.

thiazolyl) formazan by shorthand notation for its substitutents iPr-Bt) (H); l-phenyl-3-butyl-5-(2-benzothiazolyl)form-
and hetem ring; thus 1,3-diphenyl-5-(2-benzothiazolyl)- azan ( P h - B u - B t ) ( H I ) ; l-phenyl-3-heptyl-5-f2-bonzo-
formazan is referred m as Ph-Ph-Bt (see Table 1). 1,3- thiazolyl)formazan ( P h - H p - B t ) ( I V ) ; l-phenyl-3-(3,4-
Diphenyl-5-{ 2-benzothiazolyl)formazan ( P h - P h - B t ) ( l ) ; dimethoxyphenyl-5-(2-benzothiazolyl) formazan (Plr-Dimet
l-phenyl-3-isopropyl-5-(2-benzothiazolyl) formazan ( P h - - B t ) (V); l-(2-carboxyphenyl-3-isopropyl-5-(2-benzo-
thiazolyl)formazan, (2-Car. ( P h - i P r - B O ) ( V I ) ; 1-(2 car-
H boxyphenyl)-3-heptyl-5-(2-bemothiazolyl)formazaa (2-
Car. ( P h - H p - B t ) ) ( V H ) were prepared and characterised
:',..~x II i ~x" I by elemental analysis, mass spectrometry, ~H and ~3C NMR,
n.,.l~N n.~,N IR and UV-Vis spectroscopy (see Table I and Section 4 for
R R data).
The hydrazones were prepared by the reaction of a partic-

-TI- 11 ular aldehyde with an alcoholic solution of 2-benzothiazole

hydrazine. A typical scheme is shown in Fig. 2, for the prep-
aration of 1,3-diphenyl-5-(2-benzothiazolyl)formazan. Full

' :
R
(~,>._:N.fN R
SH K2CO3l~
KCl

5mi elmaftm
E~Klt2o

ll
n H\.
IPh.~:l'C~" ~,,F"$ ~ ,
H EtOH ~c"
m

R
~ iIi
@
Fig. I. Isomers of hetarylfonnazans. Fig. 2. Synthesisof a hetatylforrr~an.
32 D.A. Brown et al. / lnorganica Chimica Acta 280 (1998) 30--38

S t II ~.~

N tsalon m/e=105

~ N)_N, H
S
m/e=252

m/e=149 N~ m/e=103

Fig. 3. Mass spectral fragmentation pattern of Ph-Ph-Bt (!).

details are given in Section 3. The IR and ~H and ~3C NMR
spectIa are in full accord with the structures shown in
Fig. 1. For example for 1,3-diphenyl-5-(2-benzothiazolyl)-
formazan, the NH stretch is absent from the 3000-3500 cm-
region in accord with the formation of the chelate form (Fig.
1) which is further indicated by the v(CN) stretch occurring
at 1516 cm -z (Table 1) whereas an open form would be
expected to have a v(CN) stretch in the 1555-1580 cm-
region [ 11 ]. The El-MS spectrum shows a clear parent ion
peak at ride = 357 together with products formed by fission
of the C3-N 4 and C3-N 3 bonds indicating a chain strain prob-
ably due to the large phenyl substituents (Fig. 3). The ~H
NMR spectrum shows a multiplet at 8 7.95 ppm (4H)
assigned to the four protons of the heteroaromatic ring which
are deshielded by the N and S ring atoms. A second multiplet
at 8 7.50 ppm (5H) is assigned to the 5-phenyl ring in the
formazan chain whilst the multiplet at 8 7.25 ppm (5H) is
assigned to the 3-phenyl since this is attached to the carbon
atom and so is less deshielded than that attached to the N5
atom.
The chelate structure of (Ph-Ph-Bt) has been confirmed
by a crystal structure determination [ 12]. Similar arguments
apply to the other formazans herein reported (see Section 4).
mazan to the corresponding tetrazolium salt although the
latter was not isolated.
The corresponding Mn(II) complexes were prepared by
reacting manganese acetylacetonate Mn(acac)a with a solu-
tion of the appropriate formazan in methanol and refluxing
under nitrogen for several hours; however in this case tri-
ethylamine was required to deprotonate the formazan, HL, in
contrast to the iron series. Again it is proposed that complex-
ation is accompanied by oxidation of some of the formazan
to the corresponding tetrazolium salt with concomitant
reduction of Mn(IIl) to Mn(lI).
However, it should be noted that the iron complexes of
I -(2-carboxyphenyl) -3 - heptyl-5- ( 2- benzothiazolyl)form-
azan and l-(2-carboxyphenyl)-3-isopropyl-5-(2-benzo-
thiazolyl)formazan together with the manganese complex
of l-(2-carboxyphenyi)-3-heptyl-5-(2-benzothiazolyl)-
formazan retain the metal ion in the higher oxidation state,
i.e. Fe (III) and Mn (III) suggesting that the ortho carboxylate

2.2. Synthesis of iron and manganese complexes

The corresponding iron(II) complexes, FeL2 of the above tN1 y----~ClO

hetarylformazans, L, (I-VII) were prepared by stirring a
solution of the ligand L in alcohol with a solution of
FeCI3.6HzO in alcohol at room temperature for 1 h (see
Section 3).
The reaction involves loss of two NH protons from the
ligand, reduction of Fe(lll) to Fe(II) and its subsequent
coordination by two deprotonated ligand molecules. It is sug-
gested that the driving force of the reduction of Fe(lll) to
Fe(ll) is the accompanying oxidation of some of the for- Fig. 4. Crystal structure of [ Fe( Ph-Ph-Bt 1,.1.
 D.A. Brown et aL / Inorganica Chimica Acta 280 f 1998) 30-38 33

UV-Vis, IR, 'H and'3C NMR and FAB mass spectroscopy

4 (see Table 1 and Section 4) and in two cases by X-ray
CS : crystallography (Figs. 4 and 5).

2.3. Infrared spectra

Metal complexation (generally) results in shifts to higher

N1 C8
20 " ~--~2
Fig. 5. Crystal structureof [ Mn( Ph-Ph-Bt ): ].
group is also involved in metal coordination in these com-
plexes, a view which receives some support from spectro-
scopic studies below. All the iron and manganese complexes
prepared above were characterised by elemental analysis,
C10 frequencies of the ligand v(CN) modes suggesting the
ligands are locked into more rigid structures in the recta|
complexes as indicated by the two crystal structures (Figs. 4
and 5). However. the complexes of formazans with an o n h o
carboxylate group show two v~CN) stretches suggesting thai
only one ligand coordinates through its carboxylate group
and this is supported by the presence of two carbonyl peaks
( one free and one coordinated ) ( see Section 4). Very similar
arguments apply to the manganese series.
2.4. JH N M R spectra
These spectra showed good resolution for the Fe{ H) series
consistent with the presence of low spin F e ( l l ) as proven by
magnetic moment measurements (see below).

Table 2
Crystal data and measurementconditionstbr [Fe( Ph-Ph--Bt).,I (A) and [Mnt Ph-Ph--Bt)_,] ¢B)

A B

EmpiricalFormula Ca4,Hz~FeN,~S: C~.Hz,,MnN,,,S:

Formulaweight 768.69 767.78
Crystal colour b~ack black
Crystal size (mm) 0.40×0.30× 0.15 0.7 x 0.40 × 0.30
Temperature ( K ) 294( 21 294! 2 )
Space group C2/c C2/c
Unit cell dimensions
a (A) 9.178(2) 9.17Oi2|
b (~) 19.61412) IO.652(9)
c (A) 19.762(3) 19.7~(8)
(°l 92.710110) 92.4013)
Volume ( A-~) 3553.51101 355212 )
Z 4 4
Density (calc.) (Mg m ~) !.,I.37 1.436
Absorptioncoefficient ( mm ~) 0.588 0.536
F(000) 1584 1580
0 Rangedata collection(°) 2.62-28.05 207-27.05
Index ranges 0_<h < I 1, 0_<k_<25, -26_<1_<26 O_<h_<II, 0 < k < ~ , - ~<1_<~
Reflectionscollected 4860 426 I
Independentreflections( R., ) 4310 ( 0.0321 ) 3882 I 0.OI53 )
Absoq~tioncorrection [ ~scan ~ semi empirical semi empirical
Max., mean transmission 0.216. O.180 0.283.0.~ I
Goodness-of-fiton F: 0.995 1.045
Reflections ( I > 2~r{I1 ) 2945 3129
RI " 0.0574 0.0498
wR2" 0.1073 0.1272
Diffractometerused SiemensR3m/V SiemensR3ra/V
Wavelength(,~l (graphite monochromatort 0.71073 0.71073
Standardreflection 3 of 100 measured 3 of 100 measured
Programsused SiemensSHELXTLplus/SHELXL-93 SiemensSHEL,VI'Lplus/SHELXL-93
Structurerefinement full-matrixleast-squareson F" full-matrixleast-squaresnn F"

"RI =El led - IF~.II/E IF,,t.

" w ~ = ( X;w(F,,-"- F;') :IEwF,-') ''-~.
_34 D,A. Brown et al. / hmrganica Chimica Acta 280 (1998130-38

Table 3 Table 4
Atomic coordinates ( x I&) and equivalent isotropie displacement param- Atomic coordinates (xl04) and isotropic displacement parameters
eters (A.-"× I03) forA (,~.-'x 10~) forB

x y z U,.,~" x y z U~q~'

Fe(I) 0 966(11 2500 37(I) Mn(1) 0 954(t) 2500 37(i)

S(I) 3371~!) -445(I) 1821(I 58(11 S(I) 3427(i) -453(I) 1837(11 58(I)
N(I) 1853(31 934(11 2957(I 40(I) N(I) 1864(21 923(I) 2968(I) 40(I)
N(21 992(3) 248(I) 1967(I 41(I) N(21 1053(21 254(I) 1973(i) 41(i)
N(~ -181(31 1678(i) 3171(1 39(I) N(3) -131(2) 1672(1) 3176(I) 40(I)
N(41 2890(3) 485(I) 278111 48(!) N(41 2928(2) 479(I) 2793(I) 47(I)
N(5) 953(3) 1797(1) 3575(1 43(1) N(5) 997(2) 1782(11 3594(t) 42(I)
C(11 -574(4) -202(2) 1001(21 54(I) C(I) -490(4) -200(2) 1004(2) 53(I)
C(2) -622(5) -642(2) 452(2) 63(2) C(21 -546(4) -644(2) 457(2) 61(I)
C(3) 556(5) - 1040(2) 296(2) 68(I) C(3) 635(4) -1040(31 306(2) 67(I)
C(41 1842(5} -1015(21 689(21 64(1) C(4) 1901(41 - 1020(21 703(2) 63(I)
C(5) 1902(41 -580(2) 1245{2) 49(I) C(5) 1965(31 -581(21 1257(21 51(I)
C[61 711(4) -168(2) 1403(2) 44(11 C(61 781(31 - 167(I) 1407(I) 44(I)
C(71 2335(4) 148{21 2235(2) 45(I) C(7) 2398(3) 149(21 2249(I) 45(I)
C(81 2082(3) 1358(21 3483(2) 41(I) C(8) 2111(31 1350(1) 3498(2) 41(!)
C(9) 4337(4) 866(2) 4061(21 75(I) C(9) 4353(5) 850(2) 4082(2) 72(I)
C(IO) 5487(5) 921(31 4536(2) 92(2) C(10) 5517(5) 909(2) 4544(2) 90(2)
C(ll) 5699(5) 1508(2) 49t0(2) 80(1) C(I1) 5747(4) 1493(2) 4905(2) 77(l)
C(121 4732(41 2031(21 4824(2) 65(11 C(12) 4793(4) 2029(2) 4811(21 67(I)
C(131 3568(4) 1982(21 4357(2) 51(I) C(131 3626(3) 1977(2) 4348(2) 54(i)
C(141 3356(3) 1400(2) 3961(21 46(11 C(14) 3394(3) 1386(21 3971(I) 46(I)
C(15) -919(41 286912) 3269(21 53(I) C(15) -858(3) 2859(2) 3278(2) 54(I)
C(161 -2011(51 3353(2) 3283(2) 67(I) C(161 -1949(41 3349(2) 3294(2) 67(I)
C(171 -3443(5) 3158(21 3237(2) 73(I) C(17) -3387(4) 3156(21 3236(2) 74(I)
C(18) -3818(4) 2482(2) 3180(2) 70(11 C(181 -3756(4) 2485(2) 3173(21 67(I)
C(19~ -2734(4) 1990(21 3153(21 56(I) C(I9) -2687(3) 1991(21 3149(21 55(I)
C(20) -1290(31 2186(21 3201(2) 42(I) C(201 -1237(31 2183(I) 3207(2) 42(I)
" U,.qis defined as one third of the orthogonalised U,~tensor. U,,qis defined as one third of the trace of the orthogonalised U0 tensor.

In general, downfield shifts are observed compared to the
free ligand values consistent with electron donation to the
metal ion on complexation. For example, [Fe( 1,3-diphenyl-
5-(2-benzothiazolyl) formazan) 2] shows 8 values of 8.69
ppm, 8.66 ppm for the protons of the heteroaromatic group
compared with ~ 7.95 ppm for the free !igand.
2.5. Co'sial structures
The crystal structures of the Fe(II) and Mn(I1) complexes
of 1,3-diphenyl-5(-2-benzothiazolyl)formazan (complexes
A and B) are shown in Figs. 4 and 5, respectively, and are
very similar both to each other and to that reportedpreviously
for the Fe(II) complex of l-phenyl-3-isopropyl-5- (2-benz-
oxazolyl)formazan [13|. Crystallographic data for both
complexes, A and B, is given in Table 2. The atomic coor-
dinates for non-hydrogen atoms for complexes A and B are
given in Tables 3 and 4, respectively, with selected bond
lengths and angles in Tables 5 and 6. In these three complexes
coordination occurs through the N 1and N 3 nitrogen atoms of
the formazan chain and the N" of the heterocycle producing
a coordination sphere of four five-membered rings. Both
ligands occupy planes which are nearly perpendicularto each
other resulting in a distorted octahedral structure in both
cases. For example in A, the N-'-Fe-N ~ angle deviates by
22.8 ° from 180° whilst in B the N2-Mn-N ~angle deviates by
25.8 ° from 180°. As discussed previously for the Fe ( II ) com-
plex of the analogous benzoxazolyl formazan, these distor-
tions from ideal octahedral coordination arise from the spatial
requirements of the bulky phenyi substitutents. The bond
lengths of the coordinated formazan ligands are consistent
with increased delocalisation along the chain although care
is required in making such conclusions. It appears that steric
effects dominate the structures of these Fe(ll) and Mn(lI)
formazan complexes as originally suggested [ 131.
2.6. FAB-MS
The FAB-MS of the iron and manganese series all showed
clear parent ion peaks but the fragmentation patterns varied.
In general, there is a tendency in the iron series for initial
fission of the N-'-N 3 bond and of the benzothiazole N-Fe
bond. In contrast, in the manganese series, there is a tendency
to lose the phenyl substituents as well as the benzothiazole
fragment. This general fragmentation pattern suggests a con-
siderable amount of steric strain in these complexes in accord
with the crystal structure data (Figs. 4 and 5). For example,
the fragmentation diagram of [Fe( 1,3-diphenyl-5-(2-ben-
zothiazolyi)formazan).,] (Fig. 6) shows initial loss of the
heteroaromatic moiety together with N3 of the forrnazan
chain rather than loss of any of the substituents reflecting the
weakness of the N2-N3 bond with the heteroaromatic frag-
 D.A. Brown et aL I laorganica Chimica Acta 280 (1998130--38

Table 5
Selected bond lengths ( A ) for A ( M = Fe) and B ( M = Mn)

A B A b

M( I )-N( I) 1.889121 1,909(21 M( ! )-N(31 1.938121 1.949121

M( I )-N(2) 2.003(21 1.998(2) S( I )-C(7) 1.732131 1.737(35
S( I )-C(5) 1.743(4) 1.74413) N( I 5-C( 81 1.340141 1.352(3)
N( I )-N(41 1.353(3) 1,364(31 N(2)-C( 71 1.333141 1.344(35
N(2)--C(6) 1.395(41 1.40313) N(3)-N(55 1.302131 1.315(31
N( 3 )~(20) 1.427(4) 1.430(3) N( 4)-C( 71 1.34714) 1.328(3)
N( 5 )-C(8 ) 1.366(4) 1.348(3 ) C( 1)-C( 65 1.393(4) 1.38514)
C( I )--C(21 1.385(5 ) 1,386(4) C( 2)-C(3) 1.380(61 1.377(5)
C(3).-12141 1.382151 1,374(51 C(41-C( 51 1.390151 1,391(41
C(5)-C(6) 1,406(5) 1.398(4} C(8)-C(14) t.471(4) !.47313}
C19)-(10) 1.384(5) 1.379(51 C(95-C( 145 1,389(51 1.384(41
C( 10}-C( I I ) 1.375(6) 1.363(5 ) C( I I )--C(12 ) 1.362(51 1,377(55
C(121..-12113) 1.382151 1.381(4) C( 131-C( 141 1.392141 1.392145
C( 15)~[2(201 1.386(4) 1.378(4) C( 151-C1161 1.382151 1,390(41
C( 16)-C( 175 1.367(61 1.372(5) C( 171-4=(181 1.37516) 1.366161
C( I g)-c(19) 1.38815 ) 1.382(41 C( 191-C(205 1.379141 !.383(4)

Table 6
Selected bond angles (°) for A ( M = Fe) and B ( M = Mn )

A B A B

N( I )-M( i )-N( t )' 176.112) 176.38113) N( I )-M( I )-N( 35' 104.301i0) 105.89191
N( I )-M( I )-N(3) 78.55( 101 76.81 (9) N(3)'-M( I )-N(3 ) 87.84(14) 87.171131
N( I )-M( ! )-N(2) 78.83( 101 77.73(9) N(3)-M( I )-N(2) 157,231 I0) 154.16191
N( I )-M( I )-N(2) ~ 98.42(10) 95.61 (9) N(3)-M( i )-N(2)' 95.25(IO) 95.61191
N(2)-M( I )-N(2)' 90.57(14) 92.95(13) C(7)-S( I )-C(5) 89.1(2) 89.27(14)
C( 8 )-N( I )-N(4) 12t.I (2) 119,6(2) C(8)-N( I )-M( I ) 117.0(2) 118.1(21
N(4)-N( I )-M( I ) 121.8(2) 122.2(2) C(7)-N(21-C(6) 1i 1.3131 i 1 !.2(2)
C(7)-N(2)-M( I ) 109.3121 110.5(2) C(61-N(2 )-M( I ) 139.4121 138.3121
N(5)-N(3)-C(20) 113,6(2) 113.5121 N(5)-N(3)-M( I ) ! 17.112) 118.7121
C( 20)-N(3)-M( 1 ) 128,0(2) 127,0(2) C(7)-N(4)-N( l ) !06.4121 I06,0{20)
N(3)-N(5)-C(81 113.3(21 112.8121 C(6)-CI t )-(2(2) 118.1141 118.6(30)
C(3)-C(2)~( I ) 122.1(4) 121.413) C(4)-C131-C~ 21 120.8131 120.9(31
C(3)-C(41~-C15) I17.8(41 118.2(31 C(4)--C(5)-C(6) 121.8131 121.3131
C(4)-C(51-S(l) 127.613) 127,6(3) C(6)-C151-S(I) t 10.6121 111.1125
C( I )--C(6)-C(5) 119.413) 119.6(3) C( I )--C161-N12) 127.1131 126.9131
C(5)-C(6)-N(2) 113.4131 113.4(31 N(4)--C(7)-N(2) 123,613) I~.512)
N(4)-C(7)-S( I ) 120.9(2) 121.6(21 N(2)-C171-S( I ) i 15.5(2) 115.0121
N(5)--C(8)-N(I) 113.7(3) 113.4121 N(5)-C(8)-C( 141 !17.7131 I18,0(2)
N( 1)-C(8)-C(14) 128.6(3) 128.5(2) C( 10)-C(9)-C(14) 120.4(45 120,6(3)
C( I I )-C(10)-C(9) 120.9(4) 121.0(3) C( 10)4~( I I )-C(12) I t9.2(4) 119.4131
C( 11)-C( 12)-C(13) 120.7(4) 120.2(3) C( 12)-C( 13)-C(14) 121.0(3) 120.8131
C(9)-C( 14)-C(13) 117.8(3) 118.0(3) C(9)-C(14)-(2(8) 122.6(3) 123.4131
C( 13)-C(14)-C(8) 119.513) 118,6(2) C(20)42( 15)-C(16) 119.4(3) !19.5(3)
C( 17)-C( 16)-C(15) 120.2(4) 119.8(3) C( 18)-C'( 17)-C(16) 120.7(4) 120.5(3)
C( 17)--C(18)-C(19) 119.8141 120,513) C( 18)-C(19)-C(20) 119.5(4) 119.1(3)
C( 151-C(201-C( 191 120.4(3 ) 120.6131 C( 15 )--C(201-N( 3 ) 120.3(31 20.3(2)
C( 19}-.C(20)-N(3) 119.2(3) 119.113)

Symmetrywansformationsused to generateequivalentatoms: ' ~ -x, y, - z + I/2.

ment being stabilised by delocalisation of charge aroundthe
aromatic system. Subsequently there is loss of subtituents.
2.7. M a g n e t i c d a t a
With the exception of the two orrho-carhoxyl substituted
complexes, the iron(lI) series are all low spin diamagnetic
compounds measured at room temperature in holh the solid
slate (Gouy) [ 14] and solution (Evans) [15l. Complexes
of the ortho-carboxy ligands showed moments between 2.5-
2.9 B.M. measured by both methods (Table 11 which is
greater than low spin F e ( m ) (t:~ s) and suggests some fer-
romagnetic impurity since raising the temperature to 100°12
did not affect the moment although a small mixture of high
36 D.A. Brown et al, / blorganica Chimica Acta 280 (1998) 30-38

~ N I/N ,,=x
~1/ /=~ E-'~.,~ F~---.N ,,,/, = 663 a,,,,,
,,. Fe-'--. N --(x /) ~( 2" N. ~ ~.,~ - ~
(, "r-. \ ~ ,v._u x~,_.h N.d"
'~,s,~,.N-d -~,,,o,h~,o~ s ." "y
I v

lille = 767 ,imu

0

~/~N "P~"'IN'!~;~ ~-~ role = 498 ainu ~?N-Beflzolhiazole

I -Phenyl X ~1 -Phellyl I
role = 314 ainu
m/e ~ 412 dmtl
Fig. 6. Mass spectral fragmentation pattern of [ Fe(Ph-Ph-Bt) ~].

spin Fe(IlI) cannot be excluded. In the case of the Mn(II)
series, moments ranged from 2.2 to 2.7 B.M. with solution
moments being slightly higher (by ~ 0 3 B.M.) than the
corresponding solid state moments. The increased value over
the /z~o value of 1.73 B.M. is due to the orbital angular
contribution for a d -~metal ion.
The electron spin resonance spectrum of a chloroformsolu-
tion of [ Mn( 1,3 diphenyl-5-( 2-benzothiazolyi ) formazan) 2]
was recorded at room temperature and showed a g value of
2.03 with hyperfine structure of six lines (A = 70 cm- ' ) (Fig.
7 ) typical of low spin Mn (II) complexes with a coordination
sphere of nitrogen atoms [16,17]. Low spin Mn(II) com-
plexes are relatively rare. in the case of the much more com-
mon high spin complexes, Mn-N distances generally occur
in the range 2. I-2.3 A [ 18] and there is a marked contraction
in this distance upon spin pairing [ 19]. A similar contraction
occurs in the present series of low spin Mn(lI) complexes of
the hetarylformazans with the Mn-N distances in B lying in
the range i.909(2) to 1.998(2) A (Table 5).
2.& Electronicspectra
The free ligands show a broad intense band in the 450--
550 nm region assigned to a ('rr)-('rr)* transition of the
chelate form [20]. Complexation with Fe(II) gives shifts to
longer wavelengths of about 40 nm consistent with a decrease
in ('tr)-(~r)* energy due to interaction with the metal d
orbitals.
A second intense hand, centred at 680 nm (e',, 1500 I
mol -t cm -~) is assigned tentatively to a MLCT
(t,g)~'~(t2g) s (~r)* band. The electronic spectrum of
complex B, [ Mn (II) ( i ,3-diphenyl-5- ( 2-benzothiazolyl)-
formazan)2], is similar to that of its Fe(II) analogue with
two broad intense bands at 469 and 642 nm, respectively.
However, the other Mn(II) complexes show spectra with
similar broad bands but of reduced intensity and often with
shoulders. The reasons for this complexity are not clear but
may be related to different degrees of delocalisation affecting
(qr) orbital energies in the complexes due to differing steric
requirements of the various formazan substituents.

i i i i i 3. Experimental
300 310 320 330 340 350 360 370
BI mT Solvents were freshly dried by standard methods. Reagents
Fig. 7. ESRspectrumof [Mn(Ph-Ph-Bt)2]in CHCI,. were used directly. Infrared spectra were measured as a KBr
 D.A. Brownet al. I lnorganicaChimicaActa 280 (1998130-38
disk on a Perkin-Elmer 1720 FT spectrometer linked to a
model 3700 data station. ~H and °C NMR spectra were
recorded on a JEOL GX270 spectrometer. Analyses were
performed by the Microanalytical Laboratory of the Chemical
Sciences Unit of University College, Dublin. El-mass spectra
were recorded in a Finnegan Matt lncos 50 mass spectrometer
with an integrated FCMS systems. FAB-MS were run in a
glycerol matrix on a VG7OE mass spectrometer with argon
as bombardment gas at 8 kV. Magnetic susceptibilities
(Gouy) were measured at room temperature on a Newport
Magnetic Balance using Hg[Co(NCS)4] as standard. In the
Evan's method, CDCI.~ solutions of the complexes (5 rag/
ml CDCI3) were employed and shifts of the TMS peaks were
recorded on the above NMR spectrometer. ESR spectra were
run in CHCI~ solutions at 293 K using the X-band (9.48
GHz) with a microwave power of 50 roW.
3.1. Synthesis of hetao'lfi~rmazans (I-VII)
The synthesis of 1,3-diphenyl-5-(2-benzothiazolyl)-
formazan (Ph-Ph-Bt) (!), is describedas a typicalpreparation.
3.1.1. Synthesis of 2-hydrazino-benzothiazole
An aqueous solution of KMnO4 (48 g/440 ml) at 80°C
was added to a well-stirred suspension of 2-mercaptobenzo-
thiazole ( 30 g) and K_,CO3( 15 g) in water ( 260 ml) at 50°C.
After stirring at room temperature for I h, the suspension was
filtered, the precipitate washed twice with warm water and
the washings added to the filtrate to which excess KCi was
then added. Filtration and drying of the product gave the
potassium salt of the benzothiazole suifonic acid (yield
93%). Reaction of this (53 g, 0.21 mol) with hydrazine
hydrate ( 120 ml, 0.38 mot) in ethanol (60 ml) and water
(60 ml) and heating with stirring at 80-90°C for 4 h, followed
by cooling, filtration and washing of the solid formed with
cold water and drying gave the required 2-hydrazino-benzo-
thiazole (yield 70%).
3.1.2. Synthesis of l-phenyl-3-(2-benzothiazole)hydrazone
Equimolar amounts of the 2-hydrazino-benzothiazole
(0.036 mol) in methanol (200 ml) were refluxed for 1 h.
Cooling, filtration and recrystallisation from methanol gave
the required hydrazone (yield 84%).
3. !.3. Synthesis of 1,3-diphenyi- 5-( 2-benzothiazol.vl )-
formazan
A cooled solution (0-5°C) of phenyl diazonium chloride
was added &opwise to a pre-cooled solution (0-5°C) of the
above benzothiazole phenyl hy&azone (5.6 g, 0.02 tool) in
ethanol (100 ml) and NaOH (31 ml, 2 M) and the pH
adjusted to between 9 and 9.5 by addition of 2 M NaOH.
After stirring for 2 h, the mixture was cooled overnight
in a refrigerator, filtered and the solid recrystallised from
methanol (yield 62% ).
37
3.2. Iron(ll) complexes
A typical preparation of [Fe(Ph-Ph-Bt)z] is as follows.
To a solution of 1,3-diphenyl-5-( 2-benzothiazolyi ) formazan
(0.50 g, !.4 retool) in hot ethanol (200 ml), ferric-chloride
hexahydrate (0.08 g, 5 mmol) in methanol (50 ml) wag
added. After stirring the solution for i h and reduction of
volume to 150 mt, it was cooled overnight in a refrigerator.
Subsequent filtration and recrystallisation from methanol and
air-drying gave [ Fe{ 1,3-diphenyl-5-( 2-benzothiazolyl)_,[
(yield 53%). The other Fe(ll) complexes were prepared
similarly.
3.3. Manganese (I!) complexes
A typical preparation is as follows. To a solution of 1,3-
diphenyl-5-( 2-benzothiazolyl Iformazan ( 1.35 g. 3.8 retool)
in the minimum required volume of methanol was added
triethylamine ( 0.6 ml, 4 mmol ) followed by Mn (Ill) ( acetyl-
acetonate) ~(0.45 g, !.2 retool) and refluxed under nitrogen
for 4 h. The dark blue solution was cooled overnight in the
refrigerator and filtered, Recrystallisation from methanol
gave dark blue crystals of [ Mn{ H) { 1,3-diphenyi-5-(2-benzo-
thiazolyl)formazan) 21 ( yield 62% ). The other Mn ( II ) com-
plexes were prepared similarly. Satisfactory analyses were
obtained for all the above ligands and complexes (see Table
I and Section 4).
Crystals of A and B suitable for crystallography were
obtained by diffusion of methanol to a saturated solution in
chloroform of each complex over a period of I week. The
crystals were dried in a gentle stream of nitrogen.
4. Supplementary material
Supplementary material including elemental analysis,
UV-Vis, IR, ~H and°C NMR and FAB mass spectroscopy
data is available from the authors upon ~quest.
Acknowledgement
We thank Peter Caplan of the Mass Spectrometry Labo-
ratory Chemical Services Unit, U.C.D. for mass spectra.
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