J. inorg nuc|. Chem., 1977, Vol. 39, pp. 1797-1801. Pergamon Press.

Printed in Great Britain

SUBSTITUTED 1,2,4-TRIAZOLES AS COMPLEXING LIGANDS--I

Ni(II), Co(II), Cu(II), Zn(II), Pd(II), Cd(II) A N D Pb(II)
COMPLEXES WITH 4-AMINO-3,5-DIMERCAPTO-I,2,4-TRIAZOLE

B. K. SINHA, RAJESHWAR SINGH and J. P. SRIVASTAVA*

Chemistry Department, Magadh University, Bodh-Gaya, India

and

L. K. MISHRA
Chemistry Department, Science College, Patna, India

(Received 15 November 1976)

Abstract--The complexes of 4-amino-3,5-dimercapto-l,2,4-triazole(H2-AMT)with some bivalent metal ions of the

formula [M(I-I-AMT)2](M= Zn, Cd or Pb), [M(H-AMT)2(H20)2] (M = Ni or Co)-and M(AMT)nH20 (where
M = Cu, Ni, Co, Zn, Cd or Pd; n -- 0, 1, 2 or 4) have been prepared and characterised by UV, IR and magnetic
susceptibility measurements. The ulckel(H) complex has been isolated in two different colours ~havingthe same
composition, [Ni(H-AMT)2(H20)2].The spectral parameters 10D~, B' and fl of the octahedral complex, [Co(H-
AMT)2(H20)2] have been calculated.

INTRODUCTION Ni(II), Co(II), Cu(II), Zn(II), Pd(II), Cd(II) and Pb(II)

The coordination complexes of transition metal ions with
1,2,4-triazole derivatives containing thione, amino and
alkyl (or aryl)groups at 3 or 5 position have been widely
investigated[l-3]. Complexes of various 4-amino-3,5-di-
substituted 1,2,4-triazoles have been studied in solution
as well as in the solid states by Adamek and Cee [4]. The
complexes of 4 - amino - 3,5 - dimercapto - 1,2,4-
triazole (Hr-AMT) has not been studied hitherto. The
ligand is interesting since it has six donor atoms and is
expected to exist in the forms (a), Co) or (c).
N N N NH
-, I complexes separated. The mixture was digested on a steam bath
H---NH2 H---NH2
(a) Co)
HN NH
I /o
HN--H
(c)
It is generally found that tertiary cyclic thioureides,
capable of thione-thiol tautomerism, preferentially exist
in the thione form[5].
Here the IR spectral studies on the ligand in a KBr
disc also indicated the predominance of species CO) and
(c) (i,e. thione ftrm) in the solid state. However, com-
plexes of deprotonated species CO) are only formed in
neutral solution. Sometimes the neutral and even acidic
solution of the ligand tautomerise to form (a) for coor-
dination with Pd(II) ion and the complexes of the de-
protonated species (a) only is formed (class "b" metal).
In alkaline medium, species (a) exists in pure form and
polymeric chain structure complexes of bivalent metals
are formed by deprotonation of both the thiol protons.
In the present communication the synthesis and prob-
able structures of the complexes of bivalent metal ions
with H2-AMT are reported. The bonding of the ligand
with metal ions has been suggested from IR spectral
studies.
EXPF~RIMENTAL
All chemicals and solvents used were either E. Merck extra
pure or B.D.H.(AR) quality and used without further purification.
The ligand was prepared as described elsewhere[5].
Preparation of complexes
Complexes of the type [M(H-AMT)2(H20)~](M = Co or Ni;
n = 2 and M= Zn, Cd or Pb; n = OF.An aqueous solution of the
metal chloride oi acetate (0.01M in 60ml water) was slowly
added to a hot aqueous ethanolic solution of the ligand (0.02M in
100ml 30% ethanol) when the floculant precipitate of metal
for about 1 to 2 hr to obtain a granular precipitate. The complex
was filtered, washed thoroughly with hot Water and ethanol and
then dried at 60-70°C.
The yellow variety of' the Hi(H) complex, [Ni(H-
AMT)2(H20)2]was isolated when alcohoficsolutions of the metal
chloride and ligand were mixed. The complex was filtered im-
mediately, washed with ethanol and dried in a desiccator over
anhydrous CaCI2.
Complexes of the type M(AMT)nH20 (M = Ni or Co, n - 4;
M = Cu or Zn, n = 2; M =Pd or Cd, n = 1). An aqueous am-
moniacal solution of the ligand (0.01M in 50% ammonia) was
treated with a filtered aqueous ammoniacal solution of the metal
chloride (0.01Mi with constant stirring. The insoluble complex
either separated immediately or on standing. The product was
filtered, washed thoroughly with hot water and ethanol and dried
in air. The Cobalt(H) complex was prepared under a N2 at-
mosphere. The diaquo complexes [M(AMT)(I-120)d(M = Co or
Ni) were obtained by dehydration of the tetraquo complexes
M(AMT).4H20 at 60-70~C.The anhydrous complexes [M(AMT)]
(M = Co or Ni) were obtained by heating the tetraquo complexes
at 160-170°C.
The colour and analytical results for the complexes are recor-
ded in Table 1.
Physical measurements
The magnetic moments, electronic reflectance and IR spectra
and electrical conductance valffes of the complexes were
measured as described elsewhere[6]. The UV mull spectra were
recorded on Cary-14UV spectrophotometer at B.H.U., Varanasi.

1797
1798 B. K. SINHA et al.

Table 1

(%)C (%)H (%)N (%)M

Compound Colour Calcd. E x p . Calcd. E x p . Calcd. Exp Calcd. Exp.

[Ni(H-AMr)2(H20)~] Green 12.35 12.20 2.59 2.76 28.79 28.82 15.09 14.92
[Ni(H-AMT)2(H20)2] Yellowish green 12.35 12.18 2159 2.72 28.79 28.71 15.09 14.96
[Ni(AMT)(H20)2]2H20 YeUowish green 8.67 8.52 3.64 3.71 20.23 20.15 21.20 21.32
[Ni(AMT)(H20)2] Yellowishg r e e n . . . . 23.18 22.96 24.29 24.01
[Ni(AMT)I Yellowishbrown 11.72 11.65 0.98 1.21 27.35 27.42 28.65 28.72
[Co(H-AMT)2(H20)2] Pink 12.34 12.18 2.58 2.67 28.78 28.65 15.08 15.19
[Co(AMT)(H20)2]2H20 Reddishbrown 8.66 8.54 3.62 3.52 20.21 20.08 21.26 21.35
[Co(AMT)(H~O)2] Reddishb r o w n . . . . 23.16 22.92 24.35 24.12
[Co(AMT)] Brown 11.7l 11.82 0.98 0.88 27.32 27.16 28.72 28.96
Cu(AMT)'2H20 Dark Grey 9.77 9.85 2.46 2.60 22.80 22.72 25.85 25.71
Zn(H-AMT)2 White 13.35 13.21 1.68 1.75 31.15 30.92 17.98 17.82
Zn(AMT).2H20 White 9.70 9.52 2.44 2.60 22.63 22.42 25.59 25.70
Cd(H-AMT)2 White 11.81 11.95 1.48 1.36 27.54 27.72 27.63 27.45
Cd(AMT).H20 White 8.62 8.45 1.45 1.58 20.25 20.08 40.64 40.42
Pd(AMT).H20 Red 8.87 8.71 1.49 1.58 22.70 22.54 39.32 39.54
P b(H-AMT)2 Sharp yellow 9.58 9.42 1.25 1.36 22.34 22.06 41.31 41.52

IR spectra in KBr disc were recorded on Perkin-Elmer 221 this band has been increased due to some tetragonal
spectrophotometer at F.R.I., Dhanbad. distortion. The 10Dq, B' and ~ values have been cal-
culated from the relations of Konig[7] utilising the ~3
RESULTS AND DISCUSSION and v2 bands and found to be 9,519cm -1, 896cm -1 and
The analytical results show complexes of the general 0.92, respectively. These values are characteristic of
formulae: octahedral Co01) complexes. The magnetic moment of
(a) [M(H-AMT)2(H20)2] (M = Ni or Co) [Co(AMT)(H20)2]2H20 seems to fall in the range of
Co) [M(H-AMT)2] (M = Zn, Cd or Pb) Co01) complexes displaying anomalous behaviour, i.e. in
(c) M(AMT).nHzO (M -- Ni or Co, n = 0, 2 or 4; M = thermal equilibrium between spin states [8] ~Ats and 3T2s.
Cu or Zn, n = 2; and M = Pd or Cd, n = 1). The AMT2- complexes of Co(II) display no distinct
It has been found that copper0I) ion is reduced to Cu(I) bands but showed two broad shoulders (Table 2) in
by the ligand in aqueous or alcoholic solution and thus octahedral field.
the H-AMT- complex of Cu0I) could not be isolated. The magnetic moment of the Cu(II) complex indicates
Two kinds of Nickel(II) complex, [Ni(H-AMT)2(IJ20)2] the absence of Cu--Cu interaction at room temperature
have been isolated. and falls in the range of values for planar or distorted
The complexes in general, are insoluble in water or octahedral Cu(II) ions. Its reflectance spectrum does not
common organic solvents, however, the H-AMT- com- show any clear d-d transition. It absorbs strongly over
plexes are slightly soluble in DMF. The insolubility of the whole visible region.
AM]"2- complexes indicates that they are polymeric in The magnetic moment values of the Ni(II) complexes
nature. The DMF solution of soluble complexes exhibit fall in the range 3.07-3.52 B.M. The higher value for the
negligible molar conductance values supporting their yellowish green variety than the green form of [Ni(I-I-
nonionic nature. AMT)2(H20)2] complexes clearly indicates that the for-
The diaquo complexes of the type (a) and (c) (where mer is either tetrahedral or possesses a fairly large
M = Co, Ni, Cu and Zn) do not lose water below 110-- tetragonal distortion of the octahedral field[9]. The mo-
120°C. However, the tetraaquo complexes of the type (c) ments for the AMT2- complexes of Ni(II) are similar to
(where M---Co, Ni) lose two molecules of water below those of common octahedral Ni(II) complexes. The solid
60-70°C with slight change in colour. The remaining two reflectance or mull absorption spectra of Ni(II)
water molecules are lost at 160-170°C. It is inferred that complexes display asymmetric and usually weak and
the water molecules of the diaquo and monoaquo com- broad bands. The band positions could only be explained
plexes are either coordinated or strongly bonded in the on the basis of D4h symmetry. The v~ and v2 transitions
crystal lattice. of almost all the complexes have been found to be either
In view of common coordination number four of Zn, split up due to tetragonal distortion or broaden probably
Cd and Pd, it is suggested that water molecules are due to spin orbit coupling. For the green variety, [Ni(H-
bonded strongly in the crystal lattices of the polymeric AMT)2(H202)], the tetragonal distortion D,, D, and 10Dq
complexes M(AMT).nH~O (n = 1 or 2). values have beeh calculated to be 193, 964 and 8264 cm -~,
respectively, characteristic of distorted octahedral
nickel(II) complexes[10]. For the yellowish green
Magnetic moments and electronic spectra variety, [Ni(H-AMT)2(H20)2], the value of D, was cal-
The magnetic moment values and spectral band posi- culated to be 150 cm-t. In AMT2- complexes of Ni(II) the
tions and probable assignments for the complexes are bands are weak and less asymmetric than for the H-
listed in Table 2. The complexes of Ni(II), Co01) and AMT- complexes, perhaps because tetragonal distortion
Cu(II) are paramagnetic, the others are diamagnetic. is less in the former complexes than the latter.
The magnetic moment f o r t h e [Co(H-AMT)r(I-I~O)~]
complex is similar to those of high spin octahedral Co(II) IR
complexes, Its reflectance spectrum, besides the two The major IR spectral bands of ligand and its metal
distinct bands, displays a shoulder at 25,000 cm-I due to complexes with tentative assignments are summarised in
spin orbit coupling in the 4Tts(P) state. The intensity of Table 3.
 Substituted 1,2,4-triazoles as complexing ligands--I 1799

2. Magnetic moments? and electronic spectral data for the complexes

~t.a C.T. bands d-d transitions

Compound (B.M.) cm-' cm-' Assignments

[Co(I-I-AMT)~H=O)2] 4.94 26314 25000 sh

20615 "Tt, -"TI,(P)
17868 "Tt. -> 4A~(F)
[Co(AMTXH20)2]2H20 2.90 -- 22727 sh "Tt, ~'Tt,(P)
18200 sh "T,. - " A,.( F)
[Co(A.MT)] -- -- 23530 sh "T,, --,'T,,(P)
19591 sh "Tt, -~'A2,(F)
[Ni(H-AMT)2(H20)2] 3.34 29730 16393sh
Green 15504 (15400) 3B,, -' 3E,b
14706 sh
10753 (10526) 3Bts ~ SA2,
(8264) 3B,,--, ~B~g
(6576) SB,, ~,'F_~"
[Ni(H-AMT)=(H20)2] 3.52 25536 23810 sh (23529) SB~,--,'TI,(P)
Yellowish green. 15400 ( 1 5 6 2 5 ) 3BI,-*3E, b
10526 (9524) SB~, "-'~A~
(8333) 3BI, ~ 3B2g
(7018) 'BI, - ' SE,"
[Ni(AMTXH20)~]2H20 3.21 26316 23256 sh SA~--,'T~,(P)
20834 sh
15504 SA~. --,'TI,(F)
11905 3A~. ~ ' E /
[Ni(AMT)] 3.07 23810 sh 17857sh SA2, ~ 3TI,(P)
13889 3A2, --, 3T1,(F)
Co(AMT).2H20 1.82 25620 br
Pb(H-AMT)2 Dia. 28167 sh
23256 sh

sh, shoulder; br. broad.

?/t.~ at 304°K; Nujol mull band in parenthesis.

Table 3. Major IR spectral bands (cm-') with probable assignments of ligand (H2-AMT) and its representative complexes

M(H-AMT~(H20). M(AMT).nH20
M = Co, Ni, Zn, Cd or Ph; [Ni(H-AMT)2(H~O)2] M = Co, Ni, Cu, Zn, Cd or Pd,
(H~-AMT) n = 2 or 0 yellowish-green n = 1, 2 or 4 Assignments

-- 3430-+ 30 mb 3450 mb -- u(OH) of H=O mole

-- -- -- 3100-3450 sb u(NH2) + u(H=O)
3285 m sp 3290 +- 10 m 3285 m -- v(NH)
-- 3200-+ 15 m -- --
3110--2650 sb 3120 + 25 m 3120-2645 sb --
-- 2960-+ 25 ms -- -- u(NH=)
-- 2830-+ 15 w -- --
2110 wb -- -- -- u(S-H)
1608 s 1610 +- 10 sb 1612 sb 1612 -+8 sb 8(NH2) + B(H20)
1510 s 1510 +-5 ms 1508 sb -- 8(NH)
1472 sb 1454 +-6 ms 1455 mb 1450-+ 5 s ~C'"N + 8N-H
(Thioamtde band I)
1395 mb 1380 +-5 m 1382 mb 1375 +-5 m Ring stretch + vC-N
1325 m 1330+5 w 1330 mb 1340"*-5 m pCS+ uC'"N
1255 sb 1270 +- 10 s 1260 sb 1280+_ 5 s (thioamide band II)
l165wb ll70-15msp I165 vw -- p(NH2)
ll40wb -- ll16s --
1070 wb 1065 +_10 m sp 1070 vw -- ~o(NH2)

1018 s 1025 -+5 s 1018 w 1030 +_5 s 8(NCN) + u(NN) + uCS

(Thioamide band m )
940vs 960+_ 10 m 955 s -- u(CS)

(Thioamide band IV)

750 wh 735 -+5 wm 732 w 735 -+5 m v(C-S)
725 ms 715 +_5 ms 718 mb -- NH out-of-plane
bending vibration.
645 s 640 +- 10 wm 640 w 640 +_10 wm Ring Stretch.

sp, sharp; m, medium; b, broad; ms, medium strong; w, weak; s, strong, wm, weak to medium; v, very. u, Stretching vibration: 8,
bending vibration; p, rocking vibration; ~0, wagging vibration.
1800
The NH stretching and bending modes as well as the
N-H out-of-plane bending vibration of the free ligand are
little affected in H-AMT- complexes but disappear in the
AM~- complexes indicating that at least one the nl-
%
trogen of the triazole ring is a free ) N - H group in the
H-AMT-~ complexes, In the region 3110-2650cm -~ the
ligand exhibits a very broad and strong absorption prob-
ably due to the inter or intramolecular hydrogen bonded
NH2 group. In H-AMT- complexes this broad band
splits up into two or three medium bands in the region
2850--3250cm-~ while in the AMT~- complexes only one
band is observed in the region 3100-3450 cm-~.
The weak and broad bands of the free ligand at 2110
and 750 cm-1, assignable to I,(S-H) and ~(C-S)vibrations
respectively are due to a small contribution from the
thiol form "b". The former disappears while the latter
S
HN--~c// H2 H O
N[=d N - - N " " ' ~ ~ M ~ S ~ -
H20
Fig. 1.
H~O
HN N t
, tt "--~./,~
S N S ; S S
NH2
Fig. 2.
H20
N ;
~ , ,t-------N/ ~ C - - S ~ , ~ / N
N--NH2
H20
shifts to 735-+5 cm-~ in the complexes due to coor-
dination through the thiol sulphur on deprotonation.
The NH2 bending mode of the free ligand observed at
1608 cm-1 is not affected appreciably but sometimes ap-
pears as a very broad and relatively strong band at
1605-1620 cm-I in the complexes due to the mixing of
8(H20) and 8(NH~) vibrations. Since the ligand ori-
ginates from thiocarbohydrazide and retains the "NH-
l
C - ~ - N H , grouping, the ligand and its complexes are
expected to display all the main thioamide bands (Table
3) of the original thiocarbohydrazide molecule[Ill. The
shift of band positions and intensities of the thioamide
bands indicate the bonding of the ligand in the com-
plexes. The weak and broad bands at 1165, ll4Oand
1070 cm-~ of the free ligand attributed to p(NH2) and
o~(NH2) vibrations became medium and sharp in H-
AMT- complexes due to cleavage of the hydrogen bond-
ing in the free ligand, but are much reduced in the
A M T 2- complexes because of their polymeric nature.
B. K. SINHA et al.
The strong band at 940cm-I, predominantly arising
from the z,(CS) vibration splits and appears with lowered
intensity at 960-+10cm-~ and 735±5cm -: in the H-
AMT- complexes. In AMT2- complexes only a weak or
medium o(CS) band appears at 735 ± 5 cm-~. The splitting
of the ~(CffiS) band in the H-AMT- complexes suggests
that only one sulphur of the (C=S) groups in the ligand is
utilised in coordination (Figs. ! and 2), while the com-
plete disappearance of the v(CS) vibration at 940cm-~ in
the AMT2- complexes is due to involvement of both (CS)
groups in coordination (Fig. 3),
The IR spectrum of the yellowish green form of
[Ni(H-AMT)2(H20)2], unlike the green form, displays
broad and less resolved bands at 1018, 1070 and
ll65cm -~ indicating a different type of bonding in this
complex (Fig. 2).
Thus on the basis of IR spectra possible structures are:
(M = Ni, Co; in case of
N M ffi Zn, Cd or Pb, H20 is absent).
- I
H2 ~-NH
S
N NH
t (Yellowish-green form
[Ni(H-AMTh(H2Oh]
NH2
N
/ "~C--S~, ~"
T S-- C N--NH2
Fig. 3.
(Bonded H20 molecules are present in the case of the
Cu(II), Ni(II) and Co(II) complexes only).
Acknowledgements--Thanks are due to Prof. J. N. Chatterjea,
Patna University and Dr. E. B. Singh, Head of the Dept. of
Chemistry, MagadhUniversityfor providinglaboratoryfacilities.
A research fellowshipof Magadh Universityto one of us (R.S.)
is thankfully acknowledged.
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 Substituted 1,2,4-triazolesas complexingligands---I 1801

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