Heterocyclic thioamide derivatives of coinage metals (Cu, Ag): Synthesis, structures and spectroscopy

Article abstract of DOI:10.1016/j.ica.2010.06.051

Heterocyclic thioamides, namely, imidazolidine-2-thione (imdzSH), 1-methyl-1, 3-imidazoline-2-thione (mimzSH), thiazolidine-2-thione (tzdSH) and 2,4-dithiouracil (dtucH₂) with silver(I)/copper(I) salts in presence of triphenyl phosphine (PPh

Full text of DOI:10.1016/j.ica.2010.06.051

Inorganica Chimica Acta 363 (2010) 3432–3441
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Heterocyclic thioamide derivatives of coinage metals (Cu, Ag): Synthesis,
structures and spectroscopy
a
b
c
Razia Sultana a, Tarlok S. Lobana a, , Renu Sharma , Alfonso Castineiras , Takashiro Akitsu ,
*
Kenichi Yahagi c, Yoshikazu Aritake c
a Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005, India
b Departamento de Quimica Inorganica, Facultad de Farmacia, Universidad de Santiago, 15782-Santiago, Spain
c Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-Ku, Tokyo 162-8601, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Heterocyclic thioamides, namely, imidazolidine-2-thione (imdzSH), 1-methyl-1, 3-imidazoline-2-thione
(mimzSH), thiazolidine-2-thione (tzdSH) and 2,4-dithiouracil (dtucH2) with silver(I)/copper(I) salts in
presence of triphenyl phosphine (PPh3) have yielded complexes of different nuclearity: mononuclear,
Received 12 February 2010
Received in revised form 22 June 2010
Accepted 28 June 2010
[Ag(
g
1-S-HL)(PPh3)2Cl] (HL = imdzSH 1, mimzSH 2, tzdSH 3), dinuclear, [Ag2(
g
1-S-tzdSH)2(
l-S-tzdSH)2-
Available online 31 July 2010
(PPh3)2](NO3)2 4, and polynuclear, {Cu(
l
-S,S-dtucH2)(PPh3)2X} (X = Cl 5, Br 6, I 7). All complexes have
been characterized using analytical data, IR and multinuclear NMR spectroscopy (1H, 13C and 31P) and sin-
gle crystal X-ray crystallography. The thio-ligands are bonded to the metal centers as neutral sulfur
donors. The geometry around each metal center is distorted tetrahedral. Complexes 5–7 represent first
examples of polymers of 2,4-dithiouracil in its coordination chemistry with metal salts. The hydrogen
bonding interactions lead to the formation of 1D (2, 3, 7) and 2D (1, 4–6) sheet structures.
Ó 2010 Elsevier B.V. All rights reserved.
Keywords:
Imidazolidine-2-thione
2,4-Dithiouracil
Thiazolidine-2-thione
Crystallography
Polymers
1. Introduction
dinuclear [23,24,35,36], trinuclear [25] and polynuclear complexes
[22,23,25,27,37,38]. Likewise, silver(I) halides and silver(I) nitrate
The interaction of heterocyclic thioamides, bearing the func-
tional groups, –N(H)–C(=S)– M –N=C(–SH)–, with transition metals
has been the subject of several investigations [1–26]. These thio-
ligands have biochemical significance and use as the medicinal
substances [3,7,8]. For instance, the thiouracils are minor compo-
nents of tRNA in both Escherichia coli and mammalian tissues
[9–11], and the interaction of tRNA with the metal ions is of impor-
tance in the protein synthesis and the cell growth [12,13]. Also, the
derivatives of 2-thiouracils are the drugs of choice in the treatment
of hyperthyroid conditions [14] and the thiouracil-containing
complexes are found to be effective antitumor and anti-arthritic
compounds in vivo [15]. Similarly, five membered heterocyclic
thiones have also shown various biological applications, e.g. the
imidazole group has played an important role in enzymes, such
as chymotrypsin, creatine kinase and carboxypeptidase A, etc. [16].
The presence of both nitrogen and sulfur donor atoms enables
these thio-ligands to bind to a metal in different ways, giving a rich
variety of the structural motifs [17–26]. The thio-ligands such as
imidazolidine-2-thione (imdzSH, I), 1-methyl-1, 3-imidazoline-2-
thione (mimzSH II) and thiazolidine-2-thione (tzdSH, III) (Chart 1)
with copper(I) halides have formed mononuclear [18,19,27–34],
with imdzSH, mimzSH and tzdSH have formed a few mononuclear
[Ag(imdzSH)3Cl)] [39], [Ag(imdzSH)2(NCS)] [40], [Ag(mim-
zSH)3](NO3) [41], dinuclear [Ag2(imdzSH)4Br2] [42] and other poly-
nuclear complexes [39,42–44]. Among five membered ring based
thio-ligands as shown in Chart 1, only one complex, namely,
[Ag(mimzSH)2(PPh3)]X (X = 4-benzoyl-3-methyl-1-phenylpyrazol-
5-olate) has been reported which contains PPh3 as coligand [45].
From this laboratory, recently a few mixed-ligand complexes of sil-
ver(I) containing pyridine-2-thione and tertiary phosphine as coli-
gand have been reported [46,47].
Coordination chemistry of 2,4-dithiouracil (dtucH2, IV) is limited
and there are only a few structurally characterized complexes,
namely, [Co(
[{Ti(
5-MeC5H4)2}2(dtuc)], [{Ru(L)(PPh3)}2(
only one with a coinage metal, namely, [CuBr(
1-S-dtucH2)]
{dppbz = 1,2-bis(diphenylphosphanyl)benzene}
[51].
In this paper, a series of new mixed-ligand complexes of silver(I)
with imdzSH, mimzSH and tzdSH, namely, [Ag(
1-S-imdzSH)-
(PPh3)2Cl] 1, [Ag(
1-S-mimzSH)(PPh3)2Cl] 2, [Ag( 1-S-tzdSH)-
(PPh3)2Cl] 3, [Ag2( -S-tzdSH)2(PPh3)2](NO3)2 4, as
1-S-tzdSH)2(
well as that of 2,4-dithiouracil with copper(I) halides, namely,
{Cu( -S,S-dtucH2)(PPh3)X}n (X = Cl 5, Br 6, I 7), are reported. All
complexes have been characterized using analytical data, IR and
g
2-S,N-dtucH)(en)2](ClO4) (en = ethylenediamine),
g
l
-dtuc)]2+ [48–50] and
2-P,P-dppbz)-
g
(g
g
g
g
g
l
l
* Corresponding author. Fax: +91 183 2258820.
E-mail address: tarlokslobana@yahoo.co.in (T.S. Lobana).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.06.051

R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
3433
4.65; N, 3.81%. IR (KBr, cmꢁ1):
3020(w), 2894(w), (C–N) + d(C–H) 1570–1480(s),
1094(m),
m
(N–H) 3123(sh)-3045(m),
m
(C–H)
4
5
4
6
4
5
5
1
NH
5
m
m(P–CPh)
3
HN
1
3
HN
1
NH
1
3
S
m
(C@S) 910(s), d(N–CH3) 744(s). 1H NMR data (d, ppm;
NH
NMe
4
2
2
2
2
CDCl3): 13.13 (bs, 1H, NH), 6.75 (s, 1H, C4H), 6.64 (s, 1H, C5H),
3
N
H
3.55 (s, 3H, N-CH3), 7.26–7.49 (15H + 1H, PPh3, CHCl3). 31P NMR
S
S
S
S
S
(CDCl3): d = 5.46, 30.17 ppm,
Dd, 10.11, 34.87 ppm.
(IV)
(I)
(II)
(III)
2.2.3. [Ag(
g
1-S-tzdSH)(PPh3)2Cl] (3)
Chart 1.
Yield, 0.097 g, 71%, m.p. 190–193 °C. Anal. Calc. for
C
39H35AgClNP2S2: C, 59.46; H, 4.44; N, 1.77. Found: C, 60.02; H,
multinuclear NMR spectroscopy (1H, 13C and 31P) and single crystal
X-ray crystallography.
4.12; N, 1.62%. IR (KBr, cmꢁ1):
m
(N–H) 3100(br),
m(C–H) 2950(br),
m(C–N) + d(C–H) 1525–1450(s),
m
(P–CPh) 1102(m), m
(C@S) 1013(s).
1H NMR data (d, ppm; CDCl3): 10.54 (bs, 1H, NH), 3.36 (t, 2H,
J = 7.8, 8.1 Hz, C4H), 3.96 (t, 2H, J = 7.5, 8.4 Hz, C5H), 7.23–7.42
(15H + 1H, PPh3, CHCl3). 13C NMR data (d, ppm; CDCl3): 200.0
(C2, tzdSH), 51.8 (C5, tzdSH), 33.3 (C4, tzdSH), 133.9 (o-C,
J = 16.05 Hz, P-Ph), 133.3 (i-C, J = 19.72 Hz, P-Ph), 129.7 (p-C, P-
Ph), 128.6 (m-C, J = 8.62 Hz, P-Ph). 31P NMR (CDCl3):
2. Experimental
2.1. Materials and techniques
Silver(I) chloride was freshly prepared from AgNO3 and KCl in
water and dried in vacuo. Silver(I) nitrate was procured from Al-
drich Chemicals Ltd. and used as such. Copper(I) halides were
prepared by reducing an aqueous solution of CuSO4ꢀ5H2O using
SO2 in the presence of NaX (X = Cl, Br, I) in water [52]. The ligands
imidazolidine-2-thione, 1-methyl-1, 3-imidazoline-2-thione, thia-
zolidine-2-thione and 2,4-dithiouracil were procured from Aldrich
Chemicals Ltd. and used as such. C, H and N analysis were obtained
with Thermoelectron FLASHEA1112 CHNS analyzer. The IR spectra
were recorded using KBr pellets in the range 4000–200 cmꢁ1 on
Pye-Unicam SP-3-300 spectrophotometer. The melting points were
determined with a Gallenkamp electrically heated apparatus. 1H
NMR spectra were recorded on a JEOL AL300 FT spectrometer at
300 MHz in CDCl3 with TMS as the internal reference. 13C NMR
spectra of complexes were recorded on an AL – 300 FT JEOL spec-
trometer operating at a frequency of 75.45 MHz, using CDCl3 as
solvent, and TMS as internal reference. 31P spectra were recorded
on an AL – 300 FT JEOL spectrometer operating at a frequency of
121.5 MHz using CDCl3 with o-phosphoric acid as external refer-
ence taken as zero position.
d = 1.68 ppm,
D
d, 6.38 ppm.
2.2.4. [Ag2(
g
1-S-tzdSH)2(
l-S-tzdSH)2(PPh3)2](NO3)2 (4)
To a solution of AgNO3 (0.025 g, 0.14 mmol) in acetonitrile
(10 mL) was added a solution of thiazolidine-2-thione (0.035 g,
0.28 mmol) in acetonitrile (5 mL) followed by stirring for 1 h at
room temperature. To the precipitates formed was added PPh3
(0.038 g, 0.14 mmol) and a slow evaporation of solution at room
temperature formed yellow prismatic crystals of 4. Yield, 0.132 g,
67%, m.p. 163–165 °C. Anal. Calc. for C24H25AgN3O3PS4: C, 42.94;
H, 3.73; N, 6.26. Found: C, 43.06; H, 4.08; N, 6.41%. IR (KBr,
cmꢁ1):
1438(s),
m
(N–H) 3080(br),
m
(C–H) 2940(br),
m(C–N) + d(C–H) 1535–
m
(P–CPh) 1105(m),
m
(C@S) 1000(s). 1H NMR data (d,
ppm; CDCl3): 10.66 (bs, 1H, NH), 3.46 (t, 2H, J = 7.8, 8.1 Hz, C4H),
3.96 (t, 2H, J = 7.8, 8.4 Hz, C5H), 7.22–7.48 (15H + 1H, PPh3, CHCl3).
13C NMR data (d, ppm; CDCl3): 199.9 (C2, tzdSH), 52.4 (C5, tzdSH),
33.5 (C4, tzdSH), 133.5 (o-C, J = 16.12 Hz, P-Ph), 131.4 (i-C,
J = 27.15 Hz, P-Ph), 130.2 (p-C, P-Ph), 128.8 (m-C, J = 9.90 Hz, P-
Ph). 31P NMR (CDCl3): d = 6.64 ppm,
Dd, 11.34 ppm.
2.2.5. [Cu(
To a solution of copper(I) chloride (0.025 g, 0.25 mmol) in ace-
tonitrile (10 mL) was added solution of 2,4-dithiouracil
l-S,S-dtucH2)(PPh3)Cl]n (5)
2.2. Synthesis of complexes
2.2.1. [Ag(
g
1-S-imdzSH)(PPh3)2Cl]ꢀ0.65H2O (1)
a
(0.036 g, 0.25 mmol) in methanol (5 mL) followed by stirring for
24 h at room temperature and to the orange precipitates formed
was added solid Ph3P (0.132 g, 0.50 mmol). The contents were stir-
red until a clear solution was obtained and slow evaporation of
solution at room temperature formed orange plates of 5. Yield,
0.030 g, 23.5%, m.p. 280–283 °C. Anal. Calc. for C22H19ClCuN2PS2:
C, 52.26; H, 3.76; N, 5.54. Found: C, 52.44; H, 3.57; N, 5.31%. IR
To silver(I) chloride (0.025 g, 0.17 mmol) suspended in acetoni-
trile (10 mL) was added solid PPh3 (0.091 g, 0.34 mmol) and the
contents were stirred for 24 h. The white solid formed was filtered
and dried in vacuo. To this solid suspended in chloroform (10 mL)
was added solid imdazolidine-2-thione (0.018 g, 0.17 mmol) and
the contents were stirred until a clear solution was obtained, which
was allowed to evaporate at room temperature. The solid obtained
was dissolved in dichloromethane and a layer of methanol was
spread over it. A slow evaporation of this solution resulted in block
colorless crystals of 1. Yield, 0.098 g, 72%, m.p. 169–172 °C. Anal.
Calc. for C39H37.30AgClN2O0.65P2S: C, 59.93; H, 4.77; N, 4.00. Found:
(KBr, cmꢁ1):
N) + d(C–H) 1590–1510(s),
Complexes 6 and 7 were prepared similarly.
m
(N–H) 3050(m),
m
(C–H) 2910–3010(w),
m(C–
m
(C@S) 1090(s),
m(P–CPh) 1075(sh).
C, 60.09; H, 5.05; N, 3.56%. IR (KBr, cmꢁ1):
3069(m), 3047(m), 2974–2893(m–s), d(N–H) 1632(s),
m
(N–H) 3209(s),
m
(C–H)
(C–N) +
(C–C) + d(C–H) 1537–1433(s), m(P–CPh) 1093(m), m(C@S) 916(m).
2.2.6. [Cu(l-S,S-dtucH2)(PPh3)Br]n (6)
m
Yield, 0.021 g, 22%, m.p. 290–294 °C. Anal. Calc. for C22H19
m
BrCuN2PS2: C, 48.03; H, 3.46; N, 5.09. Found: C, 48.32; H, 3.72; N,
1H NMR data (d, ppm; CDCl3): 3.79 (s, 4H, CH2), 7.23–7.42
(15H + 1H, PPh3, CHCl3). 13C NMR data (d, ppm; CDCl3): 45.5 (C4,
C5, imdzSH), 134.3 (o-C, J = 17.32 Hz, P-Ph), 134.2 (i-C, J = 9.07 Hz,
P-Ph), 130.1 (p-C, P-Ph), 129.1 (m-C, J = 8.62 Hz, P-Ph). 31P NMR
4.90%. IR (KBr, cmꢁ1):
m
(N–H) 3010(m),
m
(C–H) 2830–2925(w),
(P–CPh) 1085(sh).
m(C–N) + d(C–H) 1590–1525(m), (C@S) 1105(s), m
m
2.2.7. [Cu(
l
-S,S-dtucH2)(PPh3)I]nꢀCHCl3 (7)
(CDCl3): d = 4.5 ppm,
D
d = (dcomplex ꢁ dligand) = 9.2 ppm.
Yield, 0.016 g, 20.5%, m.p. 278–280 °C. Anal. Calc. for
Compounds 2 and 3 were prepared similarly.
C
23H20Cl3CuIN2PS2: C, 38.53; H, 2.79; N, 3.91. Found: C, 38.65; H,
2.91; N, 3.78%. IR (KBr, cmꢁ1):
m
(N–H) 3110(w), 3040(w),
m(C–H)
2.2.2. [Ag(
g
1-S-mimzSH)(PPh3)2Cl] (2)
2930–2990(w),
1125(s),
CHCl3 (2: 1) mixture.
m
(C–N) + d(C–H) 1625(s), 1555(m),
m
(C@S)
Yield, 0.094 g, 69%, m.p. 184–190 °C. Anal. Calc. for
m(P–CPh) 1110(sh). Crystals were grown from CH3CN–
C40H36AgClN2P2S: C, 61.42; H, 4.60; N, 3.58. Found: C, 61.32; H,

3434
R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
Ligand imdzSH data: IR (KBr, cmꢁ1):
m
(N–H) 3283–3248(m),
intensity data were measured at 100(2) (1, 5–7), 93(2) (2), 273 (3)
and 173 K (4). The data were processed (data collection, refine-
ment and reduction) with SMART and SAINT (1, 3, 4) [53] and APEX
m
(C–H) 3000–2881(m), m(C–N) + d(C–H) 1518(s), 1491(s), m(C@S)
920(s) [26]. 1H NMR data (d, ppm; CDCl3): 6.40 (bs, 2H, NH), 3.59
2
(4H, CH2).
(2, 5–7) [54] and corrected for absorption using SADABS [55]. The
structures of 2–7 were solved by direct methods using the program
SHELXS-97 [56] and refined by full-matrix least-squares techniques
based on F2 using SHELXL-97 [56] and that of 1 using SHELXTL program.
All non-hydrogen atoms have been refined anisotropically. The
crystallographic data are given in Table 1.
Ligand mimzSH data: IR (KBr, cmꢁ1):
m
(N–H) 3125–3157(s),
m(C–
H) 3017(m), 2938(s),
m(C–N) + d(C–H) 1571(s), 1461(s), (C@S)
m
930(s), d(N-CH3) 770(m) [25]. 1H NMR data (d, ppm; CDCl3):
11.31 (bs, 1H, NH), 6.72 (d, 1H, C4H), 6.69 (d, 1H, C5H), 3.57 (s,
3H, CH3).
Ligand tzdSH data: IR (KBr, cmꢁ1):
3040–2920(br),
m
(N–H) 3150(br),
m(C–H)
m
(C–N) + d(C–H) 1540–1450(s),
m
(C@S) 980(s). 1H
3. Results and discussion
NMR data (d, ppm; CDCl3): 7.61 (1H, NH), 3.57 (septet, 2H,
J = 5.7–7.5 Hz, C4H), 4.00 (t, 2H, J = 7.8, 7.5, C5H).
Ligand dtucH2 data: IR (KBr, cmꢁ1):
m
(N–H) 3070(w),
m(C–H)
3.1. Comments on synthetic aspects
2895–2970(w),
m
(C–N) + d(C–H) 1605(s), 1560(m), (C@S) 1135(s).
m
In a recent investigation, it was found that a reaction of cop-
per(I) chloride with imdzSH (1:1 molar ratio) in acetonitrile
2.3. X-ray crystallography
formed a polymer, {Cu8(l3-imdzSH)4(l-imdzSH)4(g
1-Cl)8}n [26].
However, a similar reaction of this ligand with silver(I) chloride
in acetonitrile has formed an insoluble product of stoichiometry,
{AgCl(imdzSH)}, and thus no crystalline product similar to CuI
polymer mentioned above could be obtained [26]. The addition
of PPh3 to {AgCl(imdzSH)} product in acetonitrile did not yield
the expected product, [Ag(imdzSH)(PPh3)2Cl], rather a compound
The single crystals of compounds 1–7 were mounted on glass fi-
bers and data were collected using Bruker AXS SMART APEX CCD
(1), Bruker X8 Kappa APEXII (2, 5–7), and CCD area detector (3,
4) diffractometers, each equipped with a graphite monochromator
and Mo Ka radiation (k = 0.71073 Å). The unit cell dimensions and
Table 1
Crystal data for complexes 1–7.
1
2
3
4
Empirical formula
Formula weight
T (K)
C
39H37.30AgClN2O0.65P2S
C40H36AgClN2P2S
782.02
93(2)
C39H35AgClNP2S2
787.06
173
C48H50Ag2N6O6P2S8
1341.18
273
781.72
100(2)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
monoclinic
P21/n
monoclinic
P21/c
monoclinic
P21/c
monoclinic
P21/c
15.446(1)
11.960(1)
19.661(1)
97.485(1)
3601.4(4)
4
14.142(1)
10.285(1)
24.642(1)
91.208(1)
3583.3(4)
4
14.066(1)
10.275(1)
24.901(1)
94.408(1)
3588.2(4)
4
9.4450(6)
14.624(1)
19.657(1)
95.958(1)
2700.5(3)
2
b (°)
V (Å3)
Z
Dcalc (mg mꢁ3
)
1.442
0.813
1.450
0.816
1.457
0.871
1.649
1.147
l
(mmꢁ1
)
Reflections collected
8905
8730
7949
6319
Unique reflections, Rint
8074, 0.0454
7160, 0.0334
6550, 0.0319
5345, 0.0187
Final R indices
R1
wR2
0.0350
0.0906
0.0276
0.0587
0.0378
0.0954
0.0397
0.1411
R indices (all data)
R1
wR2
0.0385
0.0936
0.0404
0.0624
0.0497
0.1085
0.0479
0.1500
5
6
7
Empirical formula
Formula weight
T (K)
C
22H19ClCuN2PS2
C22H19BrCuN2PS2
549.93
100(2)
C23H20Cl3CuIN2PS2
716.29
100(2)
505.47
100(2)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
orthorhombic
Pbca
10.755(1)
17.369(1)
23.221(2)
90.00
4337.6(5)
8
1.548
orthorhombic
Pbca
10.8277(4)
17.5459(5)
23.4511(6)
90.00
4455.3(2)
8
1.640
orthorhombic
Pbca
14.321(3)
11.230(2)
33.452(6)
90.00
5379.9(18)
8
1.769
(°) = b(°) =
V (Å3)
Z
c(°)
Dcalc (mg mꢁ3
)
l
(mmꢁ1
)
1.408
3.045
2.488
Reflections collected
4443
4561
5500
Unique reflections, Rint
3103, 0.0439
3710, 0.0464
3703, 0.0479
Final R indices
R1
wR2
0.0431
0.0804
0.0296
0.0607
0.0432
0.1089
R indices (all data)
R1
wR2
0.0768
0.0930
0.0444
0.0654
0.0862
0.1432

R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
3435
Table 2
of composition {AgCl(Ph3P)} was formed. Thus the order of reac-
0
Bond lengths (AÅ) and angles (°) for compounds 1–7.
tion was reversed, wherein silver(I) chloride was first reacted with
triphenyl phosphine in 1:2 molar ratio in acetonitrile, and the
resulting dry solid was reacted with imdzSH thio-ligand in chloro-
form solvent. Slow evaporation of the reaction mixture yielded
1
2
3
Ag(1)–S(1)
Ag(1)–Cl(1)
Ag(1)–P(1)
Ag(1)–P(2)
S(1)–Ag(1)–Cl(1)
P(1)–Ag(1)–S(1)
P(2)–Ag(1)–S(1)
P(1)–Ag(1)–Cl(1)
P(2)–Ag(1)–Cl(1)
P(2)–Ag(1)–P(1)
2.6030(5)
2.6507(5)
2.4520(5)
2.4445(5)
103.6(1)
99.5(2)
104.0(2)
100.3(2)
112.2(2)
133.2(2)
2.6286(5)
2.5882(5)
2.4740(5)
2.4732(5)
104.43(2)
103.47(2)
117.21(2)
111.02(2)
98.40(2)
2.6629(8)
2.5631(8)
2.4725(8)
2.4617(8)
103.13(3)
111.46(3)
103.83(3)
101.43(3)
112.42(3)
123.07(3)
compound of stoichiometry, [Ag(
Similarly, other thio-ligands, namely, mimzSH and tzdSH, have
formed mononuclear complexes, [Ag(
1-S-mimzSH)(PPh3)2Cl] 2
and [Ag(
1-S-tzdSH)(PPh3)2Cl] 3. In literature, similar type of com-
g
1-S-imdzSH)(PPh3)2Cl] 1.
g
g
plexes are reported with copper(I) halides, namely, [Cu(imdzSH)
(dppb)Br] (dppb = diphenylphosphinobenzene) [19], [Cu(mim-
zSH)(PPh3)2I] [28] and [Cu(tzdSH)(PPh3)2Cl] [32]. Reaction of sil-
ver(I) nitrate with tzdSH ligand in acetonitrile in 1:2 molar ratio
did not yield the anticipated product, [Ag2(ONO2)2(tzdSH)4], rather
an insoluble product was formed, which after addition of PPh3
121.14(2)
4
*
Ag(1)–S(2)
Ag(1)–S(4)
P(1)–Ag(1)–S(2)
P(1)–Ag(1)–S(4)
S(2)–Ag(1)–S(4)
P(1)–Ag(1)–S(4)
2.489(1)
2.6728(8)
136.23(3)
114.32(3)
100.82(3)
98.36(2)
Ag(1)–S(4)
Ag(1)–P(1)
S(2)–Ag(1)–S(4)
S(4)–Ag(1)–S(4)
Ag(1)–S(4)–Ag(1)
2.8106(8)
2.4382(7)
114.41(4)
77.92(2)
yielded a dimeric complex, [Ag2(g l-S-tzdSH)2(PPh3)2]-
1-S-tzdSH)2(
(NO3)2 4 (Scheme 1).
Reaction of copper(I) chloride with 2,4-dithiouracil (1:1 molar
ratio) in acetonitrile gave insoluble product which reacted with
*
102.08(2)
5
6
7
2 mol of PPh3 and yielded the polymer {Cu(
(PPh3)2Cl}n 5, unlike the polymer {Cu8( 3-imdzSH)4(
1-Cl)8}n formed by imdzSH [26], or a monomer similar to com-
plexes 1–3. Copper(I) bromide and iodide have also formed similar
polymers, {Cu( -S,S-dtucH2)(PPh3)2X}n (X = Br 6, I 7) (Scheme 1).
l-S,S-dtucH2)
Cu1–S1
Cu1–S2
Cu1–P1
Cu1–Cl1
S1–Cu1–X1
P1–Cu1–S1
P1–Cu1–S2
P1–Cu1–X1
S2–Cu1–X1
S2–Cu1–S1
2.386(1)
2.279(1)
2.2341(9)
2.377(1)
105.39(3)
105.29(3)
120.48(4)
109.23(4)
112.27(3)
102.64(4)
2.3846(7)
2.2815(7)
2.2403(7)
2.5018(4)
106.58(2)
106.38(3)
119.59(3)
108.21(2)
112.55(2)
102.47(3)
2.335(2)
2.329(2)
2.262(2)
2.6143(9)
114.88(5)
110.04(6)
100.82(6)
113.47(5)
114.31(5)
101.87(6)
l
l-imdzSH)4
(g
l
However, from the reaction of silver(I) halides with 2,4-dithioura-
cil (dtucH2) in the presence of PPh3, no crystalline product could be
established. It is added here that the analogous thio-ligands,
namely, imdzSH and mimzSH, have also formed polynuclear com-
plexes, {Cu8(
l
3-imdzSH)4(
-imdzSH)4Cl2( -Cl)4}n [26],{Cu6(
-X)4}n (X = Br, I) [23] and {CuI(mimzSH)}n [25].
The IR spectra of complexes 1–7 reveal the presence of both the
thio-ligands and triphenyl phosphine (see Section 2). In complexes,
1–4, the
(N–H) peaks appear in the range 3045–3209 cmꢁ1, and re-
veal that the ligands are neutral. The diagnostic (C@S) peaks shift to
low energy region, 910–1013 cmꢁ1 relative to the ligands, and
l
-imdzSH)4(
g
1-Cl)8}n, {Cu6(
3-imdzSH)2( -imdzSH)4X2
l
3-imdzSH)2
*
Indicates centrosymmetric atoms.
(
(
l
l
l
l
l
support coordination to silver metals through sulfur atoms. The
presence of phosphine is supported by its characteristic (P–CPh
peaks in the range, 1093–1105 cmꢁ1. Similarly, the IR spectra of
dithiouracil complexes 5–7, display the (N–H), (C@S) and (P–
Ph) bands in the ranges, 3010–3050, 1090–1125 and 1075–
m
)
m
m
m
m
m
C
Cl
Ag
PPh
2
3
=
+
S
R
AgCl
HN
X
S
R
PPh3
PPh3
S
R
S
X = NH, 1;
X = NMe, 2
X = S, 3
R
R
S
S
Ph3P
2
PPh3
Ag
Ag
+
AgNO
4
(NO3)2
HN
2
S
3
S
R
PPh3
S
S
R
4
PPh3
Cu
HN
2n
PPh3
HN
n
n
CuX +
N
S
S
H
N
S
S
H
X
n
(X = Cl 5, Br 6, I 7)
Scheme 1.

3436
R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
Fig. 1. Structure of [Ag(g
1-S-imdzSH)(PPh3)2Cl] 1 with numbering scheme.
1110 cmꢁ1, respectively. The diagnostic
in free dtucH2 ligand is significantly shifted to low energy region
in complexes and suggests coordination to copper metal centers
through sulfur atoms.
m
(C@S) peak at 1135 cmꢁ1
Fig. 2. Structure of [Ag(
g
1-S-mimzSH)(PPh3)2Cl] 2 with numbering scheme.
4.1. Mononuclear [Ag(
g
1-S-HL)(PPh3)2Cl] complexes (1–3)
4. Crystal structures
Figs. 1–3 depict molecular geometries of complexes 1–3 along
with their numbering schemes. In complexes 1–3, each silver atom
is bonded to two P atoms of Ph3P ligands, one S atom of a thio-li-
gand, and one chlorine atom. The Ag–S bond distances {2.6030(5)–
2.6629(8) Å} in complexes 1–3 are smaller than the sum of ionic
radii of silver and sulfur ions, 2.78 Å [58] (Table 2). It shows strong
The crystal data of complexes 1–7 are given in Table 1, and the
bond parameters are in Table 2. Compounds 1–4 crystallized in
monoclinic crystal system with space groups P21/n (1) and P21/c
(2–4). Compounds 5–7 crystallized in the orthorhombic crystal
systems with space group Pbca.
Fig. 3. Structure of [Ag(g
1-S-tzdSH)(PPh3)2Cl] 3 with numbering scheme.

R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
3437
interaction of neutral S atom of a thio-ligand with the silver(I) ion.
distances in analogous complexes [Ag2(
Hptsc)2(Ph3P)2](NO3)2ꢀCHCl3 (Hptsc = pyrrole-2-carbaldehyde
thiosemicarbazone) [60] and [Ag2( -S-py2SH)2(Ph3P)2X2] (X = Cl
g l2-S-
1-S-Hptsc)2(
The Ag–Cl bond distances, 2.5631(8)–2.6507(5) Å, are smaller than
the sum of the ionic radii of Ag+ and Clꢁ, 2.75 Å [58]. In these com-
plexes, the Ag–S bond distances vary in the order: 3 > 2 > 1, and as
expected the order is reverse for Ag–Cl bond distances: 1 > 2 > 3.
The Ag–P bond distances are almost similar in these complexes.
These bond distances are comparable to the literature values
[57,59]. The P2–Ag–P1 bond angles vary in the order: 1 > 2 ꢂ3,
however, the S–Ag–Cl bond angles are almost same in these com-
plexes. The lack of variation in the S–Ag–Cl angle is attributed to
the intramolecular hydrogen bonding of chlorine atom with the
imino hydrogen in its vicinity {N1–H1ꢀꢀꢀCl1, 2.42 Å; N1ꢀꢀꢀCl1,
3.255(2) Å 1; N1–H1ꢀꢀꢀCl, 2.20 Å; N1ꢀꢀꢀCl, 3.063(2) Å 2; N1–H1ꢀꢀꢀCl1,
2.20 Å; N1ꢀꢀꢀCl1, 3.077(3) Å 3}. Mononuclear complexes have dis-
torted tetrahedral geometries.
In complex 1, 1D linear chain is formed through both intermo-
lecular interaction of chlorine atom with the imino hydrogen {N2–
H2ꢀꢀꢀCl1#, 2.43 Å; N2ꢀꢀꢀCl1#, 3.211(2) Å} and participation of water
in formation of hydrogen bonds with sulfur and chlorine atoms
{O1–H1ꢀꢀꢀS1, 2.51(3) Å; O1ꢀꢀꢀS1, 3.274(2) Å; O1–H2ꢀꢀꢀCl1#,
2.28(2) Å; O1ꢀꢀꢀCl1#, 3.113(3) Å}. Water oxygen further forms C–
HPhꢀꢀꢀO hydrogen bonds between chains {C37–H37ꢀꢀꢀO1, 2.415 Å}
leading to the formation of 2D network in the ab plane (Fig. 4).
The intermolecular C–HPhꢀꢀꢀCl interactions in complexes 2 and 3
{C233–H23BꢀꢀꢀCl, 2.72 Å; C233ꢀꢀꢀCl, 3.518(2) Å 2; C9–H9ꢀꢀꢀCl1
2.767 Å; C9ꢀꢀꢀCl1 3.511(3) Å 3} lead to the formation of 1D chains
running parallel to b axis (see Table 3 in supplementary material).
8
l
9, Br 10) [59] indicate that the central core is a parallelogram in
all these complexes (Table 4). The terminal Ag1–S2 distance,
2.489(1) Å, is shorter than 2.526(1) Å observed in complex 8. The
*
bond angles of the central core {S4–Ag1–S4 , 77.92(2); Ag1–S4–
Ag1, 102.08(2) Å} are comparable to those in the related complex
8 {75.54(3) and 107.41(3) Å} [60]. The change of nitrate group by
halogen atom in 9 and 10 increases the angle at sulfur atom and
decreases that at silver atom (Table 4).
In this complex, the imino hydrogen (–NH) is not involved in
intramolecular hydrogen bonding, rather it forms intermolecular
hydrogen bonding through nitrate group. The nitrate group forms
hydrogen bonds through its oxygen atoms with imino hydrogen
atoms of two dimeric units {N1–H1ꢀꢀꢀO2, 2.50 Å, (N1ꢀꢀꢀO2,
3.153(5) Å; N1–H1ꢀꢀꢀO3, 1.91 Å (N1ꢀꢀꢀO3, 2.769(7) Å; N2–H2ꢀꢀꢀO3,
2.62 Å (N2ꢀꢀꢀO3, 3.047(7) Å; N2–H2ꢀꢀꢀO1, 2.03 Å (N2ꢀꢀꢀO1,
2.846(4) Å; C10–H10ꢀꢀꢀO1, 2.57 Å} resulting in formation of 1D
chain running parallel to a axis. The chains interact with each other
via weak CH–p interactions involving phenyl groups of two differ-
ent phosphines resulting in formation of 2D network in ac plane
{C19–H19ꢀꢀꢀC14, 2.807 Å} (Fig. 6).
4.3. Polymeric {Cu(l-S,S-dtucH2)(PPh3)2X} complexes (5–7)
Fig. 7 shows a part of polymer 5 along with its numbering
scheme. In this polymer, the copper atom is coordinated to two
S, one P, and one Cl atoms, forming a distorted tetrahedral geome-
try. The angles change from 102.64(4)° {S2–Cu1–S1} to 120.48(4)°
{P1–Cu1–S2} (Table 2). Due to bridging by the thio-ligand, it has
two Cl–Cu–S bond angles {105.39(3)°, 112.27(3)°} versus one bond
4.2. Dinuclear [Ag2(g l-S-tzdSH)2(PPh3)2](NO3)2 complex
1-S-tzdSH)2(
(4)
In compound 4, each silver(I) atom is terminally bonded to one
sulfur {Ag1–S2, 2.489(1) Å}, one PPh3 {Ag1–P1, 2.4382(7) Å}, and
two bridged S-donor atoms with unequal Ag–S distances of central
angle, 109.2(1)° as observed in mononuclear complex, [CuCl(g
1-S-
pySH)(PPh3)2] (pySH = pyridine-2-thione) [61]. Similarly, there is
Ag(
l-S)2Ag core {2.6728(8), 2.8106(8) Å} (Fig. 5). The Ag–S
one P1–Cu1–Cl1 bond angle {109.23(4)°} versus two {P–Cu–Cl,
Fig. 4. 2D network of [Ag(
g
1-S-imdzSH)(PPh3)2Cl] 1.

3438
R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
Fig. 5. Structure of [Ag2(g l-S-tzdSH)2(PPh3)2](NO3)2 4 with numbering scheme.
1-S-tzdSH)2(
Table 4
A comparison table.
Complex
Ag–S (Å)
Ag–S–Ag (°)
S–Ag–S (°)
AgꢀꢀꢀAg (Å)
4.265(2)
3.1871(7)
3.8425(8)
3.8211(4)
[Ag2(
[Ag2(
[Ag2(
[Ag2(
g
g
1-S-tzdSH)2(
l
-S-tzdSH)2(PPh3)2](NO3)2 (4)
2.6728(8), 2.8106(8)
2.5463(9), 2.6556(11)
2.5832(8), 2.7208(11)
2.6306(4), 2.6950(7)
77.92(2)
75.54(3)
92.81(2)
92.19(2)
102.08(2)
107.41(3)
87.19(2)
87.81(2)
1-S-Hptsc)(
l2-S-Hptsc)2(Ph3P)2](NO3)2ꢀCHCl3 (8)
l-S-py2SH)2(Ph3P)2Cl2] (9)
l-S-py2SH)2(Ph3P)2Cl2] (10)
Fig. 6. Polymeric 2D network of [Ag2(
g
1-S-tzdSH)2(
l
-S-tzdSH)2(PPh3)2](NO3)2 4.

R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
3439
Fig. 7. Structure of {Cu(l-S,S-dtucH2)(PPh3)Cl}n 5 with numbering scheme.
99.6(1)°, 111.6(1)°} as observed in [CuCl(
g
1-S-pySH)(PPh3)2] [61].
Cu1–S1 increase in the order: Cl < Br ꢃ I. The Cu–S bond distances
in complex 6 {2.3846(7), 2.2815(7) Å} are unequal but in complex
7, these bond lengths are almost same {2.336(2), 2.329(2) Å}. The
Cu–Br and Cu–I bond distances are less than the sum of the ionic
radii of Cu+ and Xꢁ (Cu+, Brꢁ, 2.73 Å; Cu+, Iꢁ, 2.97 Å) [58]. The
Cu1–P1 bond distances, {2.2403(7), 2.262(2) Å}, for complexes 6
and 7, respectively, are similar to that of 5 (Figs. 8 and 9).
The Cu–S/Cu–Cl bond distances {5, Cu–S, 2.386(1), 2.279(1) Å,
Cu–Cl, 2.377(1) Å} are comparable to the literature values [61].
The Cu1–Cl1 bond distance is less than the sum of the ionic radii
of Cu+ and Clꢁ, 2.58 Å [58]. The Cu1–P1 bond distance,
{2.2341(9) Å} is within the limits of the range expected for tetrahe-
drally coordinated CuI [57].
Bonding patterns in complexes 6 and 7 are similar to that of 5.
The bond angles around Cu lie in the ranges, 102.47(3)–119.59(3)°
and 101.87(6)–114.88(5)°, respectively, with S2–Cu1–S1 angles
being the smallest in both cases (Table 2). The bond angles X–
In the 1D helical chains of polymers 5–7, the halogen atom is
hydrogen bonded to two imino hydrogens of two adjacent thio-li-
gands {N2–H2AꢀꢀꢀCl1 2.43 Å (N2ꢀꢀꢀCl1 3.243(3) Å, N6–H6AꢀꢀꢀCl1
2.25 Å (N6ꢀꢀꢀCl1 3.096(3) Å 5; N12–H12ꢀꢀꢀBr1 2.53 Å (N12ꢀꢀꢀBr1
Fig. 8. Structure of {Cu(l-S,S-dtucH2)(PPh3)Br}n 6 with numbering scheme.

3440
R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
Fig. 9. Structure of {Cu(l-S,S-dtucH2)(PPh3)I}n 7 with numbering scheme.
3.340(2) Å, N16–H16ꢀꢀꢀBr1 2.39 Å (N16ꢀꢀꢀBr1 3.219(2) Å 6; N12–
H12ꢀꢀꢀI1 2.79 Å (N12ꢀꢀꢀI1 3.617(5) Å, N16–H16ꢀꢀꢀI1 2.62 Å (N16ꢀꢀꢀI1
3.439(5) Å 7}. As expected, these interactions decrease in strength
with change in the electronegativity of halogen atoms. The chains
of 5 and 6 are further linked to each other through weak C–HPhꢀꢀꢀX
45.5 ppm) relative to free imdzSH ligand (d 44.6 ppm). The free
PPh3 shows 13C carbon signals at: 134.2 (o-C, J = 19.5 Hz), 132.5
and CH–
p
interactions {C13–H13ꢀꢀꢀCl1 2.634 Å 5; C25–H25ꢀꢀꢀBr1
2.819 Å 6; C22–H22ꢀꢀꢀC14(Ph) 2.797 Å 5; C36–H36ꢀꢀꢀC24(Ph)
2.812 Å 6} leading to formation of 2D network in ac plane
(Fig. 10), but in complex 7 there is no C–HPhꢀꢀꢀI interaction and
CH–
p
interaction is very weak {C32–H32ꢀꢀꢀC25 2.899 Å}. Table 3
and Figs. S1–S5 are placed in supplementary.
5. Solution phase studies – NMR spectroscopy (1H, 13C, 31P)
The mimzSH ligand shows proton NMR signals due to non-
equivalent C4H and C5H protons at d 6.72 and 6.69 ppm, respec-
tively, which remained almost unchanged (d 6.75 and 6.64 ppm)
in its complex 2. The NH proton signal of this ligand at d
11.31 ppm shifts to low energy region at d 13.13 ppm in this com-
plex. Complex 1 has shown one signal due to –CH2– protons at d
3.79 ppm which is at low field relative to the free imdzSH ligand
(d 3.59 ppm). However, the peak due to NH protons at 6.40 ppm
in free ligand is obscured by PPh3 in the complex. The C4H and
C5H protons of free tzdSH ligand appear at d 3.57 and 4.00 ppm,
respectively, which show small upfield shifts to d 3.36, 3.96 ppm,
respectively, in complex 3. The NH proton signal of this ligand at
d 7.61 ppm, shifts to low energy region at d 10.54 ppm in this com-
plex. Complex 4 showed changes for C4H, C5H and NH protons sim-
ilar to complex 3. The protons signals of PPh3 in complexes 1–4
appear as multiplets in the region, 7.22–7.49 ppm.
In complex 3, the coordination by thione sulfur of thiazolidine-
2-thione influences C2 carbon signal in its 13C NMR spectrum
which moves upfield to d 200.0 ppm relative to the ligand (d
202.0 ppm). Similarly, C4 carbon signal at d 33.3 ppm showed small
upfield shift (tzdSH, 33.7 ppm). The C5 carbon signal showed
downfield shift to d 51.8 ppm (tzdSH, 51.2 ppm). Complex 4
showed identical behavior (C2 199.9, C4 33.5, C5 52.4 ppm). The
C4,5 carbons of complex 1 showed marginally downfield shift (d
Fig. 10. H-bonded 2D sheet structure in {Cu(l-S,S-dtucH2)(PPh3)Cl}n 5.

R. Sultana et al. / Inorganica Chimica Acta 363 (2010) 3432–3441
3441
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J = 10.8 Hz) [57], which are not much affected in complexes 1, 3
and 4 (Section 2).
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Dd, 6.38–11.34 ppm. These shifts are
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weak signal with
is in equilibrium with its sulfur bridged dimer, [Ag2Cl2(
D
d = 34.9 ppm, and it suggests that monomer 2
-S-mim-
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zSH)2(PPh3)2], a phenomenon often exhibited by coinage metal ha-
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Coordination chemistry of silver(I) chloride with imdzSH is dif-
ferent from that of copper(I) chloride. While copper(I) chloride
formed a polymer, {Cu8(
silver(I) chloride did not yield a similar crystalline product, rather
it formed a mononuclear complex, [Ag(
1-S-imdzSH)(PPh3)2Cl] 1
with PPh3 as coligand. Other thio-ligands, namely, mimzSH and
tzdSH, also formed mononuclear complexes [Ag(
1-S-mim-
zSH)(PPh3)2Cl] 2 and [Ag(
1-S-tzdSH)(PPh3)2Cl] 3. These mixed-li-
l3-imdzSH)4(l-imdzSH)4(g
1-Cl)8}n [26],
g
g
g
gand complexes make new addition to silver(I) halide–heterocyclic
thioamide chemistry as only one mixed-ligand silver(I) complex,
[Ag(
date
tzdSH)2(PPh3)2](NO3)2 4 makes new addition to existing only two
mixed-ligand silver(I) dinuclear complexes [Ag2X2( -S-
g
1-S-pySH)(PPh3)2Cl] (pySH = pyridine-2-thione) is known to
[46].
Similarly,
complex
[Ag2(g l-S-
1-S-tzdSH)2(
l
pySH)2(PPh3)2] (X = Cl, Br) [47]. 2,4-dithiouracil did not yield any
crystalline product with silver(I) chloride and with copper(I) ha-
lides, it did not yield mononuclear complexes similar to 1–3, rather
it formed polymeric complexes (5–7). These complexes represent
first examples of polymers of 2,4-dithiouracil in its coordination
chemistry.
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Acknowledgment
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Financial assistance from UGC (SAP) (to RS) is gratefully
acknowledged. The authors thank Matthias Zeller of Youngstown
State University, USA for his contribution in X-ray crystallography.
Appendix A. Supplementary material
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CCDC 761991, 676827, 761992, 761993, 741296, 741297,
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tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.ica.2010.06.051.
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