Metal derivatives of heterocyclic thioamides: Synthesis and crystal structures of copper complexes with 1-methyl-1,3-imidazoline-2-thione and 1,3-imidazoline-2-thione

Article abstract of DOI:10.1002/zaac.200800161

Reactions of copper(I) halides (Cl, Br, I) with 1-methyl-1, 3-imidazoline-2-thione (mimzSH) in 1 : 2 molar ratio yielded sulfur-bridged dinuclear [Cu₂X₂(μ-S-mimzSH)₂(η ¹-S-mimzSH)₂] (X = I, 1, Br, 2; Cl, 3) complexes. Copper(I) iodide with 1,3-imidazoline-2-thione (imzSH₂) and Ph ₃P in 1 : 1 : 1 molar ratio has also formed a sulfur-bridged dinuclear [Cu₂I₂(μ-S-imzSH₂) ₂(PPh₃)₂] (4) complex. The central Cu(μ-S)₂Cu cores form parallelograms with unequal Cu-S bond distances {2.324(2), 2.454(3) A} (1); {2.3118(6), 2.5098(6) A} (2); {2.3075(4), 2.5218(4) A} (3); {2.3711(8), 2.4473(8) A} (4). The Cu...Cu separations, 2.759-2.877 A in complexes 1-3 are much shorter than 3.3446 A in complex 4. The weak intermolecular interactions {H ₂CH...S^# (2); CH...Cl^# (3); NH...I^# (4)} between dimeric units in complexes 2-4 lead to the formation of linear 1D polymers.

Full text of DOI:10.1002/zaac.200800161

DOI: 10.1002/zaac.200800161
Metal Derivatives of Heterocyclic Thioamides: Synthesis and Crystal Structures
of Copper Complexes with 1-Methyl-1,3-imidazoline-2-thione and
1,3-Imidazoline-2-thione
Tarlok S. Lobanaa,*, Renu Sharmaa, Rekha Sharmaa, and Ray J. Butcherb
a Amritsar / India, Department of Chemistry, Guru Nanak Dev University
b Washington DC / USA, Department of Chemistry, Howard University
Received February 6th, 2008; accepted April 17th, 2008.
˚
{2.3711(8), 2.4473(8) A} (4). The Cu···Cu separations,
Abstract. Reactions of copper(I) halides (Cl, Br, I) with 1-methyl-
1, 3-imidazoline-2-thione (mimzSH) in 1 : 2 molar ratio yielded
sulfur-bridged dinuclear [Cu2X2(μ-S-mimzSH)2(η1-S-mimzSH)2]
(X ϭ I, 1, Br, 2; Cl, 3) complexes. Copper(I) iodide with 1,3-imida-
zoline-2-thione (imzSH2) and Ph3P in 1 : 1 : 1 molar ratio has also
formed a sulfur-bridged dinuclear [Cu2I2(μ-S-imzSH2)2(PPh3)2]
(4) complex. The central Cu(μ-S)2Cu cores form parallelograms
˚
˚
2.759Ϫ2.877 A in complexes 1Ϫ3 are much shorter than 3.3446 A
in complex 4. The weak intermolecular interactions {H2CH···S# (2);
CH···Cl# (3); NH···I# (4)} between dimeric units in complexes 2Ϫ4
lead to the formation of linear 1D polymers.
˚
with unequal CuϪS bond distances {2.324(2), 2.454(3) A} (1);
Keywords: Copper; 1,3-Imidazoline-2-thione; 1-Methyl-1,3-imida-
zoline-2-thione
˚
˚
{2.3118(6), 2.5098(6) A} (2); {2.3075(4), 2.5218(4) A} (3);
Introduction
Heterocyclic thioamides bearing the functional groups such
as ϪN(H)ϪC(ϭS)Ϫ ↔ ϪNϭC(ϪSH)Ϫ or ϪN(H)ϪC(ϭ
S)ϪN(H)Ϫ ↔ ϪN ϭ C(ϪSH)ϪN(H)Ϫ, have shown di-
verse bonding properties both in the neutral and in anion
forms (after losing ϪNH hydrogen ). These ligands have
formed monomers, dimers, oligomers and polymers
[1Ϫ12a]. The five membered ring ligand, namely, 1-methyl-
1,3-imidazoline-2-thione (mimzSH, I) has formed
monomeric and dimeric complexes with CuI, viz.
[CuBr(mimzSH)(Ph3P)2] [12b], [CuI(mimzSH)(Ph3P)2]
[12c], [Cu2(mimzSH)5]SO4 [13], [Cu(mimzSH)3](NO3) [14],
[Cu2(mimzSH)6]·2BF4 [15], [Cu2(mimzSH)4(CN)2] [16] and
[Cu2(mimzSH)4(SCN)2] [17]. As regards 1, 3-imidazoline-
2-thione (imzSH2, II), only a few mononuclear copper(I)
complexes have been reported from this laboratory [18].
Chart 1 displays various bonding modes of 1, 3-imidazo-
line-2-thione and its derivatives : (i) η1-S- terminal (mode
A) [12c], (ii) μ-S- bridging (mode B) [16], (iii) μ-N, S- bridg-
ing (mode C) [12d], and (iv) N, S- chelating (mode D) [12e].
Chart 1
As noted above there are only a few copper(I) halide
complexes
with
1-methyl-1,3-imidazoline-2-thione
(mimzSH, I), namely, mononuclear, [Cu(mimzSH)-
Br(Ph3P)2] [12b] and [Cu(mimzSH)I(Ph3P)2] [12c], and a di-
nuclear, [Cu2Cl2(mimzSH)4] [19]. Also there is no dimeric
complex of imzSH2 ligand with any coinage metal. In con-
tinuation of our interest in the metal coordination chemis-
try of heterocyclic thioamides [7, 8, 12], we are reporting in
this paper a series of dinuclear complexes of copper(I)
halides with 1-methyl-1,3-imidazoline-2-thione and
1,3-imidazoline-2-thione.
* Prof. Tarlok S. Lobana
Department of Chemistry,
Guru Nanak Dev University,
Amritsar-143 005 / India
Fax 91-183-2258820
Experimental Section
Email: tarlokslobana@yahoo.co.in
Materials and Techniques
The ligands, 1-methyl- 1, 3-imidazoline-2-thione, 1, 3-imidazoline-
2-thione, and triphenyl phosphine were procured from Aldrich
Sigma Ltd. Copper(I) halides were prepared by reducing an aque-
Supporting information for this article is available on the
WWW under http://www.wiley-vch.de/home/zaac or from the
author
Z. Anorg. Allg. Chem. 2008, 634, 1785Ϫ1790
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1785

T. S. Lobana, R. Sharma, R. Sharma, R. J. Butcher
Table 1 Crystal data for complexes 1Ϫ4
1
2
3
4
Empirical formula
Formula weight
T/K
C8H12CuIN4S2
418.78
293(2)
monoclinic
P21/c
10.7928(10)
8.1112(7)
15.7687(12)
90
105.775
90
1328.4(2)
4
2.094
4.261
C8H12BrCuN4S2
371.79
103(2)
monoclinic
P21/n
8.3490(9)
14.962(2)
10.3160(10)
90
98.811(5)
90
1273.59(2)
4
1.939
5.158
C8H12ClCuN4S2
327.33
103(2)
monoclinic
P21/n
8.3348(7)
14.6699(12)
10.2426(8)
90
100.4310(10)
90
1231.67(17)
4
1.765
2.306
C42H38Cu2I2N4P2S2
1105.70
103(2)
Crystal system
Space group
triclinic
¯
P1
˚
a/A
9.218(2)
9.415(2)
13.455(2)
90.690(2)
105.194(2)
111.309(2)
1042.5(3)
1
˚
b/A
˚
c/A
α/°
β/°
γ/°
3
˚
V /A
Z
Dcalcd /mg mϪ3
1.761
2.714
μ /mmϪ1
Reflections collected
Unique reflections, R(int)
Final R indices [I>2σ(I)]
R1
14011
3155, 0.0374
8216
3154, 0.0459
13720
3444, 0.0216
9351
3915, 0.0211
0.0692
0.1847
0.0269
0.0604
0.0235
0.0586
0.0270
0.0765
wR2
[Cu2Cl2(μ-S-mimzSH)2(η1-S-mimzSH)2] (3)
ous solution of CuSO4 ·5H2O using SO2 in the presence of NaX
(X ϭ Cl, Br, I) in water [20]. Elemental analysis for C, H and N
were carried out using a thermoelectron FLASHEA1112 analyser.
The melting points were determined with a Gallenkamp electrically
heated apparatus. The I.R spectra of the ligands and the complexes
were recorded in the range, 4000-200 cmϪ1 (using KBr pellets) on
the FTIR-SHIMADZU 8400 Fourier Transform Spectrophoto-
meter and on PyeϪUnicam SP-3-300 spectrophotometer. 1H NMR
spectra were recorded on a JEOL AL300 FT spectrometer at
300 MHz in CDCl3 with TMS as the internal reference. 31P NMR
spectra were recorded at 121.5 MHz with (CH3O)3P as the external
reference taken as zero position.
Yield, 0.028 g, 80 %, m.p. 140-142 °C. Anal. calcd for
C8H12CuClN4S2 (%): C, 29.36; H, 3.67; N, 17.12. Found: C, 29.43;
H, 3.59; N, 16.52.
IR (KBr, cmϪ1): ν(NϪH), 3219-3115(m-s); ν(CϪH)Me, 3016(m); ν(CϪH)ring
2939(m); ν(CϪN) ϩ δ(C-H), 1570(s), 1468(s); ν(CϭS), 916(m); δ(NϪCH3),
789(s). 1H NMR data (δ, CDCl3): 7.42 (1H, C4H), 6.82 (1H, C5H), 3.67
(3H, CH3).
,
[Cu2I2(μ-S-imzSH2)2(PPh3)2] (4)
To a solution of 1, 3-imidazoline-2-thione (0.025 g, 0.25 mmol) in
dry acetonitrile (12 mL) was added a solution of copper(I) iodide
(0.047 g, 0.25 mmol) in dry acetonitrile (12 mL), and after stirring
for 1 h, white precipitates were formed. To these precipitates, PPh3
(0.065 g, 0.25 mmol) was added and a clear solution was obtained.
White crystals are formed on slow evaporation at room tempera-
ture. Yield, 82 %, m.p. 205-212 °C. Anal. calcd. for C21H19Cu-
IN2P2S (%): C, 45.57; H, 3.44; N, 5.06. Found: C, 45.04; H, 3.59;
N, 4.94.
Synthesis of complexes
[Cu2I2(μ-S-mimzSH)2(η1-S-mimzSH)2] (1)
To a solution of 1-methyl-1, 3-imidazoline-2-thione (0.025 g,
0.22 mmol) in dry acetonitrile (10 mL) was added a solution of
copper(I) iodide (0.020 g, 0.11 mmol) in dry acetonitrile (10 mL).
The reaction was stirred for 30 minutes at room temperature. To
this reaction mixture was added chloroform (5 mL) and the con-
tents were stirred for a further period of 2 h. Light green crystals
were formed on slow evaporation at room temperature. Yield, 64 %,
m.p. 170-175 °C. Anal. calcd for C8H12CuIN4S2 (%): C, 22.91; H,
2.86; N, 13.36. Found:C, 23.18; H, 3.07; N, 13.66.
IR (KBr, cmϪ1): ν(NϪH), 3070(w); ν(CϪH)ring, 2950(s), 2897(s); ν(CϪN),
1577(s), 1468(s); ν(PϪCPh), 1093(s); ν(CϭS), 920(m). 1H NMR data (δ,
CDCl3: 7.25 (2H, C4,5H), 7.44-7.71(15H, PPh3). 31P NMR (CDCl3), δ ϭ
Ϫ78.35, Δδ ϭ 34.81.
IR (KBr, cmϪ1): ν(NϪH), 3221-3114(m-s); ν(CϪH)Me, 3028(m), 3018(m);
ν(CϪH)ring, 2939(m), 2910(w); ν(CϪN) ϩ δ(C-H), 1570(sh), 1468(s); ν(Cϭ
S), 915(m); δ(NϪCH3), 787(s). 1H NMR data (δ; CDCl3): 11.95 (s, 1H,N3H),
7.51 (m, 1H, C4H), 6.82 (m, 1H, C5H), 3.65 (3H, CH3).
X-ray crystallography
Compounds 2 and 3 were prepared similarly.
Prismatic crystals of complexes 1Ϫ4 were mounted on an auto-
matic Enraf-Nonius CAD-4 diffractometer equipped with a graph-
˚
ite monochromator, and Mo-Kα radiation (λ ϭ 0.71073 A). The
[Cu2Br2(μ-S-mimzSH)2(η1-S-mimzSH)2] (2)
unit cell dimensions and intensity data were measured at 293 K for
1 and 103 K for 2Ϫ4. The structures were solved by the direct
methods and refined by full matrix least square based on F2 with
anisotropic thermal parameters for non-hydrogen atoms using
XCAD-49 (data reduction), and SHELXL (absorption correction,
structure solution refinement and molecular graphics) [21]. The
crystallographic data are given in Table 1.
Yield, 75 %, m.p. 180-185 °C. Anal. calcd for C8H12CuBrN4S2 (%):
C, 25.84; H, 3.23; N, 15.07. Found: C, 26.38; H, 3.45; N, 15.12.
IR (KBr, cmϪ1): ν(NϪH), 3138-3115(m-s); ν(CϪH)Me, 3020(m); ν(CϪH)ring
2940(m); ν(CϪN) ϩ δ(C-H), 1570(s), 1462(s); ν(CϭS), 910(m); δ(NϪCH3),
779(s). 1H NMR data (δ; CDCl3: 7.34 (1H, C4H), 6.79 (1H, C5H), 3.64
(3H, CH3).
,
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Z. Anorg. Allg. Chem. 2008, 1785Ϫ1790

Metal Derivatives of Heterocyclic Thioamides
Scheme 1
Results and Discussion
Syntheses
Scheme 1 depicts formation of complexes 1Ϫ4. The
reactions of copper(I) iodide, bromide and chloride with
1- methyl-1, 3 imidazoline-2-thione (mimzSH) in 1 : 2
(M : L) molar ratio in CH3CN formed compounds of com-
position [Cu2X2(mimzSH)4] (X ϭ I, 1; Br, 2; Cl, 3), which
were crystallized from CH3CN/CHCl3 mixture. Complex
[Cu2Cl2(mimzSH)4] is reported in literature also [19].The li-
gand imzSH2 did not yield complexes similar to 1Ϫ3, and
Ph3P was necessary to obtain a stable and crystalline com-
plex. Thus reaction of copper(I) iodide with imzSH2 and
Ph3P in 1 : 1 : 1 (M : L : PPh3) molar ratio formed a com-
pound of composition [Cu2I2(imzSH2)2(Ph3P)2] (4). Other
copper(I) halides (Br, Cl) with imzSH2 and Ph3P did not
yield similar crystalline products. Compounds 1Ϫ4 are sol-
uble in chloroform, dichloromethane and acetonitrile and
are stable to air and moisture.
Figure 1 Structure of complex (1) with numbering scheme
Complexes 1Ϫ3 showed ν(N-H) bands in the range,
3114Ϫ3221 cmϪ1, whereas complex 4 showed this peak
at
3070 cmϪ1
(mimzSH,
3125Ϫ3157,
imzSH2,
3116Ϫ3150 cmϪ1). This showed that the ligands are coordi-
nating as neutral ones. The diagnostic ν(CϭS) band
appeared in the low energy region, 910Ϫ916 cmϪ1 vis-a-vis
the free ligands (mimzSH, 930; imzSH2, 930 cmϪ1). This
shift is attributed to the weakening of CϭS bond due to
coordination to the metal center via thione sulfur. A
characteristic ν(P-CPh) band at 1093 cmϪ1 showed the pres-
ence of Ph3P in complex 4 [13]. The single crystal x-ray
crystallography has been used to establish the crystal and
molecular structures of complexes.
Figure 2 Packing diagram of complex [Cu2I2(μ-S-mimzSH)2(η1-
S-mimzSH)2] (1)
Crystal structures of complexes
Dimeric complexes 1Ϫ3 crystallized in monoclinic system
with space groups P21/c (1), P21/n (2 and 3) and compound
4 crystallized in triclinic system with space group P1. The
atomic numbering schemes of compounds 1 and 4 are
shown in Figures 1 and 2 respectively (see supporting infor-
mation for 2 and 3). Dimer 1 consists of two terminally
bonded iodides and mimzSH ligands along with two sulfur-
bridged mimzSH ligands. The central Cu(μ-S)2Cu core is a
parallelogram with unequal CuϪS bond distances
˚
{2.324(2), 2.454(3) A} (1), which are longer than the ter-
˚
¯
minal CuϪS bond distance {2.301(3) A}. The core CuϪS
˚
distances are close to 2.358 and 2.459 A observed in
[Cu2(μ-S-mimzSH)2(η1-S-mimzSH)4](BF4)2 6 [15], or in
other similar heterocyclic thioamide complexes [16Ϫ18].
˚
The CuϪI bond distance, 2.6456(14) A (1), is much shorter
Ϫ
than the sum of ionic radii of Cuϩ and I , 2.97 A [22], and
˚
Z. Anorg. Allg. Chem. 2008, 1785Ϫ1790
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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1787

T. S. Lobana, R. Sharma, R. Sharma, R. J. Butcher
˚
is close to 2.6729(11) A observed in a tetrahedral complex
[Cu(η1-imzSH2)(PPh3)2I] [18]. Bond parameters of 2 and 3
are similar. The CϪS bond distances of bridging
˚
˚
˚
{1.722(9) A (1), 1.710(2) A (2), 1.7153(14) A (3)} as well
terminal mimzSH ligands {1.701(9) (1), 1.699(2) (2),
˚
1.7002(14) (3)} are longer than 1.684(2) A in free mimzSH
[23] indicating partial double bond character of CϭS in
complexes. It is pointed out here that the bond parameters
of the dimer 3 are similar to previously reported param-
eters [18].
Dinuclear complex [Cu2I2(μ-S-imzSH2)2(Ph3P)2] (4) con-
sists of two terminally bonded iodides, two sulfur-bridged
imzSH2 and two terminal Ph3P ligands with central Cu(μ-
S)2Cu core. The central Cu(μ-S)2Cu core is a parallelogram
with unequal CuϪS bond distances {2.3711(8),
˚
Figure
imzSH2)2(PPh3)2] (4)
4
Packing diagram of complex [Cu2I2(μ-S-
2.4473(8) A} and Ph3P ligands are in trans positions. The
bridging CuϪS bond distances are similar to that of com-
˚
plex 1. The CuϪI bond distance, 2.6211(5) A is close to
˚
2.6729(11) A in the mononuclear complex, [CuI(-
˚
bonded, the distance marginally increases to 3.003 A due to
the difference in electronegativity of halide / pseudohalide
groups [15]. The mixed-ligand complexes [CuX2L2(PPh3)2]
(4, 7 and 8) have longest Cu···Cu separations (3.3446-
imzSH2)(Ph3P)]2 [18]. The CuϪP distances are close to the
literature values [18, 24, 25]. The bridging CϪS distance of
˚
˚
1.694(3) A in 4 is longer as expected than 1.643(10) A in
[CuI(η1-S-imzSH2)(Ph3P)]2 [18].
˚
3.250 A). Further the angles at bridging sulfur and copper
The bond angles at each copper lie in the ranges,
99.02Ϫ119.70° (1), 101.461-115.574° (2), 106.298-115.057°
(3) and 92.10-116.15° (4), and reveal that copper has dis-
torted tetrahedral geometry.
atom vary in complementary fashion.
˚
Table
2
Important bond lengths/A and bond angles/° in
Cu(μϪS)2Cu cores
Complex
CuϪS
CϪS
MϪSϪM SϪMϪS Cu···Cu
[Cu2I2(mimzSH)4]
(this work) 1
2.324(2), 1.722(9) 73.141(19) 109.51(8) 2.759(2)
2.454(3)
[Cu2Br2(mimzSH)4]
(this work) 2
2.3118(6), 1.710(2) 70.49(8)
2.5098(6)
106.85(2) 2.877(6)
[Cu2Cl2(mimzSH)4]
(this work) 3
2.3075(4), 1.715(2) 72.42(13) 107.57(1) 2.858(4)
2.5218(4)
[Cu2I2(imzSH)2(PPh3)2]
(this work) 4
2.371(8), 1.694(3) 87.90(2)
2.44(8)
92.10(2) 3.3446
[Cu2(SCN)2(mimzSH)4]
5 [17]
2.377,
2.457
Ϫ
72.6
95.9
2.861
3.003
[Cu2(mimzSH)6](BF4)2
6 [15]
2.358,
2.459
1.705
77.2
102.8
[Cu2I2(py2S)2(p-tol3P)2]
7 [24]
2.39(4),
2.42(4)
1.69(1) 85.25(1)
94.75(1) 3.263(4)
94.86(6) 3.250(2)
[Cu2Br2(py2S)2(p-tol3P)2] 2.389(2), 1.717(4) 85.14(6)
8 [12]
2.415(2)
H-bonding
Figure 3 Structure of complex 4 with atomic numbering scheme
The important H-bonding parameters of complexes 1Ϫ4
are given in Table 3. The NH- hydrogens of both the ter-
minal and bridging mimzSH ligands have only formed in-
tra-molecular H-bonds, {N1H(br.)···X, N1H(ter)···X} with
iodine, and there is no inter-dimer interaction in complex
1. The intra-molecular H-bonding in complexes 2 and 3 is
similar to that of 1. In complex 2, the two dimeric units are
interconnected via long intermolecular H-bonds (CH···S)
and (CH···X) to form a tetramer along a-axis (see sup-
Table 2 shows bond parameters of some dinuclear com-
plexes of mimzSH and pyridine-2-thione (py2SH) or
imzSH2 with tertiary phosphines as co-ligands. The central
cores in these complexes adopt shape of a parallelogram.
In complexes [CuX2L4] (X ϭ I, 1, Br, 2, Cl, 3, SCN, 5), the
Cu···Cu separations are less than or close to twice the sum
˚
of van der Waals radius of Cu atom (2.80 A) [22]. However,
the complex [Cu2L6]2ϩ (6) with all the sulfur ligands
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Z. Anorg. Allg. Chem. 2008, 1785Ϫ1790

Metal Derivatives of Heterocyclic Thioamides
plementary). Two such tetrameric units are interconnected
by a dimeric unit via weak interaction between methyl hy-
drogen and sulfur (H2CH···S) along b-axis. In complex 3,
the two dimeric units are interconnected by weak intermo-
lecular H-bonding, between CH of terminal mimzSH and
the chlorine atom, (CH···Cl), which is repeated along b-axis
to form a linear polymer (see supporting information).
line-2-thione formed neither polymers nor dinuclear com-
plexes, and the dimer [Cu2I2(imzSH2)2(Ph3P)2] 4 was ob-
tained only in the presence of Ph3P using a different reac-
tion ratio (1 : 1 : 1).
Supplementary material: Full details have been deposited with
the Cambridge Crystallographic Data Centre, CCDC: for
1Ϫ4 is 676823-676826. Copies of this information can be obtained
free of charge from The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: 44-1223-336-033; email:
deposit@ccdc.cam.ac.uk; or http:// www.ccdc.cam.ac.uk).
˚
Table 3 Hydrogen bonds/A for Complexes 1Ϫ4
Complex No. D-H···A
d(D-H) d(H···A) d(D···A)
<(DHA)
1
2
3
4
N(1A)-H(1AA)···I 0.86
N(1B)-H(1BA)···I 0.86
N(1A)-H(1AA)···Br 0.88
N(1B)-H(1BA)···Br 0.88
2.95
2.91
2.41
2.60
3.753(8)
3.706(8)
3.270(2)
3.433(2)
155.6
155.6
164.8
158.5
Acknowledgements. Financial assistance (RS) from CSIR (Scheme
no: 01(1695)/01/EMR-II), New Delhi is gratefully acknowl-
edged.The authors also thank Razia Sultana for her help.
N(1A)-H(1A)···Cl 0.83(2) 2.33(2) 3.1441(13) 169(2)
N(1B)-H(1B)···Cl
N(1)-H(1A)···I#2
N(2)-H(2B)···I
0.87(2) 2.50(2) 3.3272(13) 160.0(2)
0.88
0.88
References
2.91
2.84
3.705(2)
3.678(2)
150.3
160.4
[1] E. S. Raper, Coord. Chem. Rev. 1985, 61, 115.
[2] E. S. Raper, Coord. Chem. Rev. 1996, 153, 199.
[3] E. S. Raper, Coord. Chem. Rev. 1994, 129, 91.
#1
#1
#1
#1
1,
Ϫxϩ1,Ϫy,Ϫz; 2,
Ϫxϩ2,Ϫy,Ϫzϩ2; 3,
Ϫxϩ1,Ϫyϩ1,Ϫzϩ1; 4,
#2
Ϫxϩ2,Ϫyϩ1,Ϫz xϩ1,y,z
[4] E. S. Raper, Coord. Chem. Rev. 1997, 165, 475.
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[7] T. S. Lobana, R. Sharma, R. Sharma, S. Mehra, A. Casti-
neiras, P. Turner, Inorg. Chem. 2005, 44, 1914 and references
therein.
The H-bonding pattern is different in complex 4 due to
the presence of two NH moieties in imzSH2. One of the
imino hydrogens forms intra-molecular H-bond with the
iodine (NH···I) and second imino hydrogen is engaged in
intermolecular H-bonding (NH···I) and this leads to the
formation of a linear chain polymer.
[8] T. S. Lobana, R. Sharma, G. Hundal, R. J. Butcher, Inorg.
Chem. 2006, 45, 9402.
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Acta Cryst. 1996, C52, 1914; (d) W. McFarlane, P. D. Akrivos,
P. Aslanidis, P. Karagiannidis, C. Hatzisymeon, M. Numan, S.
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Solution Phase Behavior
Proton NMR spectrum of compound 1 showed a signal for
imino hydrogen, -NH- at 11.95 ppm, which is at low field
`
vis-a-vis that of the free ligand (11.31 ppm). This signal
could not be identified even in dmso-d6 and this is attri-
buted to broadening of ϪNH signals due to quadrupolar
relaxation (14N, I ϭ 1). The C4H and C5H protons of com-
plexes 1Ϫ3 in the range, 6.64-7.51 ppm showed a slight up-
field shift (mimzSH, 6.68-6.67 ppm). The methyl hydrogen
appeared in the range, 3.33-3.67 ppm, and remained almost
unchanged in these complexes (free ligand, 3.62 ppm). The
C4H and C5H protons of complex 4 appeared at 7.25 ppm
`
and are at low field vis-a-vis that of the free ligand
(6.64 ppm). The signals of phenyl hydrogens of Ph3P mol-
ecule in this complex lie in range, 7.26-7.71. The 31P NMR
spectrum of 4 showed a signal at Ϫ78.35 ppm with a coor-
dination shift, Δδ ϭ {δcomplex Ϫ δligand}, 34.81 ppm indicat-
ing a coordinated Ph3P in this complex [25].
[11] W. Su, M. Hong, J. Weng, Y. Liang, Y. Zhao, R. Cao, Z. Zhou,
A. S. C. Chan, Inorg. Chim. Acta 2002, 331, 8.
Conclusion
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P. Karagiannidis, P. Aslanidis, S. Papastefanou, D. Mentzafos,
A. Hountas, T. Terzis, Polyhedron 1990, 9, 981; c) D. Li, Y.-F.
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Acta 2000, 303, 12; e) W. S. Sheldrick, C. L. Landgrafe, Inorg.
Chim. Acta 1993, 208, 145.
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N. P. C. Walker, A. R. W. Jackson, Inorg. Chim. Acta 1985,
100, 285.
It may be interesting to compare the coordination chemis-
try of the title ligands with that of 1, 3- imidazolidine-2-
thione (imzdSH2). For instance, while reactions of copper(I)
halides (I, Br) with imzdSH2 in CH3CN- CHCl3 mixture in
1 : 2 molar ratio resulted in the formation of polymeric
materials [7, 8], the similar reactions with 1-methyl-1,3-
imidazoline-2-thione have formed rather dinuclear
[Cu2X2(mimzSH)4] complexes. However, the 1,3-imidazo-
Z. Anorg. Allg. Chem. 2008, 1785Ϫ1790
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1789

T. S. Lobana, R. Sharma, R. Sharma, R. J. Butcher
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Inorg. Chim. Acta 1989, 155, 77.
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1008.
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son, WI, USA, 1994.
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Principles of Structure and Reactivity, 4th ed., Harper Collins,
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Acta Crystallogr. 1983, B39, 355.
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4023.
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Butcher, A. Castineiras, Polyhedron 2007, 26, 2621.
1790
www.zaac.wiley-vch.de
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 1785Ϫ1790