Investigation on the coordination modes: Syntheses, characterization and crystal structures of diorganotin (IV) dichloride with 4(5)- imidazoledithiocarboxylic acid

Article abstract of DOI:10.1016/j.ica.2005.03.053

A series of diorganotin (IV) complexes of the types of R ₂SnCl(SSCC₃H₃N₂) (R = CH₃ 1, ⁿBu 2, C₆H₅ 3 and C₆H ₅CH₂ 4), R₂Sn(SSCC₃H ₃N₂)₂ (R = CH₃ 5, ⁿBu 6, C₆H₅ 7 and C₆H₅CH₂ 8) and R₂Sn(SSCC₃H₂N₂) (R = CH₃ 9, ⁿBu 10, C₆H₅ 11 and C₆H ₅CH₂ 12) have been obtained by reactions of 4(5)-imidazoledithiocarboxylic acid with diorganotin (IV) dichlorides in the presence of sodium ethoxide. All complexes are characterized by elemental, IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectra analyses. Also, the complexes 1, 7 and 9 are characterized by X-ray crystallography diffraction analyses, which reveal that the complex 1 is monomeric structure with five-coordinate tin (IV) atom, the complex 7 is monomeric structure with six-coordinate tin (IV) atom and the complex 9 is one-dimensional chain with five-coordinate tin (IV) atom.

Full text of DOI:10.1016/j.ica.2005.03.053

Inorganica Chimica Acta 358 (2005) 3084–3092
www.elsevier.com/locate/ica
Investigation on the coordination modes: Syntheses,
characterization and crystal structures of diorganotin (IV)
dichloride with 4(5)-imidazoledithiocarboxylic acid
a,b,
a
a
Chunlin Ma
*, Yinfeng Han , Rufen Zhang
a
Department of Chemistry, Liaocheng University, Liaocheng 252059, PeopleÕs Republic of China
b
Taishan University, Taian 271021, PeopleÕs Republic of China
Received 1 December 2004; accepted 26 March 2005
Available online 4 May 2005
Abstract
A series of diorganotin (IV) complexes of the types of R2SnCl(SSCC3H3N2) (R = CH3 1, nBu 2, C6H5 3 and C6H5CH2 4),
R2Sn(SSCC3H3N2)2 (R = CH3 5, nBu 6, C6H5 7 and C6H5CH2 8) and R2Sn(SSCC3H2N2) (R = CH3 9, nBu 10, C6H5 11 and
C6H5CH2 12) have been obtained by reactions of 4(5)-imidazoledithiocarboxylic acid with diorganotin (IV) dichlorides in the
1
presence of sodium ethoxide. All complexes are characterized by elemental, IR, H, 13C and 119Sn NMR spectra analyses. Also,
the complexes 1, 7 and 9 are characterized by X-ray crystallography diffraction analyses, which reveal that the complex 1 is mono-
meric structure with five-coordinate tin (IV) atom, the complex 7 is monomeric structure with six-coordinate tin (IV) atom and the
complex 9 is one-dimensional chain with five-coordinate tin (IV) atom.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Diorganotin (IV); 4(5)-Imidazoledithiocarboxylic acid; Crystal structure; Coordination modes
1. Introduction
on the chemical, structural, and spectroscopic properties
of a series of similar organotin (IV) compounds and
characterized by different coordinating properties [7].
As an extension of this research program and in connec-
tion with our current interest in the coordination chem-
istry of organotin compounds with heterocyclic ligands,
we chose another fascinating ligand: 4(5)-imidazoledi-
thiocarboxylic acid.
This ligand is interesting because of its potential mul-
tipledentate coordinate possibilities. Owing to the exis-
tence of a deprotonated thiol and more than one
coordinative active nitrogen atom, the coordination
modes of these novel ligands might bond which takes
place either from nitrogen atoms and the deprotonated
thiol sulfur or from the dithiocarboxylic moiety. As
exhibited in Scheme 1, at least five bonding modes be-
tween this ligand and tin are conceivable although no-
body investigated its actual coordination mode until
Increasing investigation of organotin (IV) complexes
has been focused on acquiring well-defined solid-state
structures to learn the nature of their versatile coordina-
tion chemistry [1–5]. Especially, organotin compounds
react with the ligands with nitrogen atoms, yielding
products characterized by Sn–N bonds [6]. The fact
has led to considerable effort being devoted to character-
izing model compounds obtained from the ligands that
have other donor atoms or group, such as sulfur. A
characteristic feature of these complexes in the solid
state is that the ligands chelate the tin atom through S
and N atoms. In our previous work, we have reported
*
Corresponding author. Tel.: +86 538 6715686; fax: +86 538
6715521.
E-mail address: macl@lctu.edu.cn (C. Ma).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.03.053

C. Ma et al. / Inorganica Chimica Acta 358 (2005) 3084–3092
3085
Sn
Sn
H
H
S
S
Sn
S
S
S
S
N
N
N
N
N
S
S
Sn
Sn
N
HN
HN
N
N
S
S
E
C
D
B
A
Scheme 1.
now. For example, organotin complexes with chelation
by both N and S atoms (modes A and B) have been re-
ported [8,9] and the S, S chelations (modes C and D) are
commonly observed in organotin dithiocarboxylates
[10,11]. In addition, bridging between different mole-
cules via the heterocycles (modes B, D and E) rather
than chelation is possible.
2.2. Syntheses
2.2.1. (CH3)2SnCl(SSCC3H3N2) (1)
The reaction is carried out under nitrogen atmo-
sphere. The 4(5)-imidazoledithiocarboxylic acid (0.144
g, 1 mmol) and sodium ethoxide (0.068 g, 1 mmol) were
added to the solution of dry benzene (20 ml) in a
Schlenk flask and stirred for 0.5 h. After the dimethyltin
dichlorides (0.219 g, 1 mmol) were added to the reactor,
the reaction mixture was stirred for 12 h at 40 ꢁC and
then filtrated. The solvent is gradually removed by evap-
oration under vacuum until solid product is obtained.
The solid is then recrystallized from ethyl ether and
the red crystal complex 1 is formed. Yield: 79%. M.p.
108–110 ꢁC. Anal. Calc. for C6H9ClN2S2Sn: C, 22.01;
H, 2.77; N, 8.56. Found: C, 22.25; H, 2.70; N, 8.52%.
IR (KBr, cmÀ1): 3256, 1614, 1258, 1020, 553, 448, 358.
Therefore, we design a series of experiments of diorg-
anotin (IV) dichlorides with 4(5)-imidazoledithiocarb-
oxylic acid in the presence of sodium ethoxide. When
using a 1:1:1 molar ratio of R2SnCl2:HSSCC3H3N2:
EtONa, we obtain four monomeric complexes 1–4 of
n
the type of R2SnCl(SSCC3H3N2) (R = CH3 1, Bu 2,
C6H5 3 and C6H5CH2 4). Using a 1:2:2 molar ratio of
R2SnCl2:HSSCC3H3N2:EtONa, we obtain four mono-
meric complexes 5–8 and the general formula is
R2Sn(SSCC3H3N2)2 (R = CH3 5, nBu 6, C6H5 7 and
C6H5CH2 8). With 1:1:2 ratio of R2SnCl2:HSSCC3-
H3N2:EtONa, another four one-dimensional polymeric
complexes 9–12 of the type of R2Sn(SSCC3H2N2)
1H NMR (CDCl3–D2O, ppm):
d
0.97(s, 6H,
2JSnH = 87.2), 7.03(d, 1H), 7.82(d, 1H), 13.20(d, 1H).
13C NMR (CDCl3, ppm): d 11.3(1J119Sn–13C), 521
Hz), 122.1, 124.3, 136.3, 222.3. 119Sn NMR (CDCl3,
ppm): À141.9.
n
(R = CH3 9, Bu 10, C6H5 11 and C6H5CH2 12) were
obtained.
2.2.2. (nBu)2SnCl(SSCC3H3N2) (2)
2. Experimental
The solidis obtainedfromethyl ether. Yield: 84%. M.p.
143–145 ꢁC. Anal. Calc. for C12H21ClN2S2Sn: C, 35.02; H,
5.14; N, 6.81. Found: C, 35.21; H, 5.31; N, 6.67%. IR
2.1. Materials and measurements
1
(KBr, cmÀ1): 3245, 1603, 1260, 1024, 560, 459, 371. H
Dimethyltin dichlorides, di-n-butyltin dichlorides,
diphenyltin dichlorides and 4(5)-imidazoledithiocarb-
oxylic acid are commercially available, and they are used
without further purification. Dibenzyltin dichlorides
were prepared by a standard method reported in the
literature [12]. The melting points were obtained with
Kofler micro-melting point apparatus and were uncor-
rected. Infrared-spectra were recorded on a Nicolet-460
spectrophotometer using KBr discs and sodium chloride
optics. 1H, 13C and 119Sn NMR spectra were recorded on
Varian Mercury Plus 400 spectrometer operating at 400,
100.6 and 149.2 MHz, respectively. The spectra were ac-
quired at room temperature (298 K) unless otherwise
specified; 13C spectra are broadband proton decoupled.
The chemical shifts were reported in ppm with respect
to the references and were stated relative to external tet-
ramethylsilane (TMS) for 1H and 13C NMR, and to neat
tetramethyltin for 119Sn NMR. Elemental analyses
(C, H, N) were performed with a PE-2400II apparatus.
NMR (CDCl3–D2O, ppm): d 1.08(t, 6H), 1.50–1.79(m,
12H), 7.01(d, 1H), 7.36(d, 1H), 13.04(d, 1H). 13C NMR
(CDCl3, ppm): d 27.2, 26.5, 26.1, 13.7, 122.4, 124.3,
135.7, 223.1. 119Sn NMR (CDCl3, ppm): À137.2.
2.2.3. (Ph)2SnCl(SSCC3H3N2) (3)
The solid is obtained from ethyl ether. Yield: 82%.
M.p. 171–173 ꢁC. Anal. Calc. for C16H13ClN2S2Sn: C,
42.56; H, 2.90; N, 6.20. Found: C, 42.38; H, 3.04; N,
6.39%. IR (KBr, cmÀ1): 3275, 1623, 1262, 1026, 561,
459, 382. 1H NMR (CDCl3–D2O, ppm): d 7.31–
7.83(m, 10H), 7.18(d, 1H), 7.67(d, 1H), 13.23(d, 1H).
13C NMR (CDCl3, ppm): d 129.0, 129.3, 137.8, 122.4,
124.1, 135.9, 225.2. 119Sn NMR (CDCl3, ppm): À176.9.
2.2.4. (PhCH2)2SnCl(SSCC3H3N2) (4)
The solid is obtained from ethyl ether. Yield: 79%.
M.p. >220 ꢁC (dec.). Anal. Calc. for C18H17ClN2S2Sn:
C, 45.07; H, 3.57; N, 5.84. Found: C, 45.16; H, 3.71;

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C. Ma et al. / Inorganica Chimica Acta 358 (2005) 3084–3092
N, 5.71%. IR (KBr, cmÀ1): 3302, 1614, 1263, 1030, 574,
448, 360. H NMR (CDCl3–D2O, ppm): d 3.09(s, 4H),
7.21–7.64(m, 10H), 7.08(d, 1H), 7.81(d, 1H), 13.24 (d,
1H). 13C NMR (CDCl3, ppm): d 38.1, 127.4, 129.6,
141.5, 122.6, 123.1, 136.7, 225.2. 119Sn NMR (CDCl3,
ppm): À157.2.
7.73(s, 1H). 13C NMR (CDCl3, ppm):
d
1
10.2(1J119Sn–13C), 467 Hz), 122.5, 124.1, 136.2, 220.5.
119Sn NMR (CDCl3, ppm): À77.4.
2.2.10. (nBu)2Sn(SSCC3H2N2) (10)
The solid is obtained from ethyl ether. Yield: 85%.
M.p. 152–154 ꢁC. Anal. Calc. for C12H20N2S2Sn: C,
38.42; H, 5.37; N, 7.47. Found: C, 38.31; H, 5.41; N,
7.38%. IR (KBr, cmÀ1): 1611, 1253, 1020, 547, 451,
365. 1H NMR (CDCl3, ppm): d 1.15(t, 6H), 1.56–
1.78(m, 12H), 7.01(s, 1H), 7.80(s, 1H). 13C NMR
(CDCl3, ppm): d 27.5, 26.8, 26.3, 13.6, 122.9, 124.2,
135.8, 223.3. 119Sn NMR (CDCl3, ppm): À72.1.
2.2.5. (CH3)2Sn(SSCC3H3N2)2 (5)
The solid is obtained from ethyl ether. Yield: 81%.
M.p. 176–178 ꢁC. Anal. Calc. for C10H12N4S4Sn: C,
27.60; H, 2.78; N, 12.87. Found: C, 27.52; H, 2.61; N,
12.72%. IR (KBr, cmÀ1): 3261, 1601, 1260, 1021, 551,
1
450, 359. H NMR (CDCl3–D2O, ppm): d 0.93(s, 6H),
7.01(d, 2H), 7.89(d, 2H), 13.24(d, 2H). 13C NMR
(CDCl3, ppm): d 11.7, 122.5, 124.0, 136.2, 223.4. 119Sn
NMR (CDCl3, ppm): À201.7.
2.2.11. (Ph)2Sn(SSCC3H2N2) (11)
The solid is obtained from ethyl ether. Yield: 82%.
M.p. >220 ꢁC (dec.). Anal. Calc. for C16H12N2S2Sn: C,
46.29; H, 2.91; N, 6.75. Found: C, 46.18; H, 3.04; N,
6.59%. IR (KBr, cmÀ1): 1608, 1257, 1024, 551, 449,
380. 1H NMR (CDCl3, ppm): d 7.35–7.78(m, 10H),
7.18(s, 1H), 7.81(s, 1H). 13C NMR (CDCl3, ppm): d
129.1, 129.7, 137.5, 122.7, 123.5, 135.9, 225.0. 119Sn
NMR (CDCl3, ppm): À85.7.
2.2.6. (nBu)2Sn(SSCC3H3N2)2 (6)
The solid is obtained from ethyl ether. Yield: 90%. M.p.
141–143 ꢁC. Anal. Calc. for C16H24N4S4Sn: C, 37.00; H,
4.66; N, 10.79. Found: C, 36.85; H, 4.51; N, 10.63%. IR
1
(KBr, cmÀ1): 3296, 1598, 1257, 1021, 561, 454, 370. H
NMR (CDCl3–D2O, ppm): d 1.10(t, 6H), 1.51–1.82(m,
12H), 7.02(d, 2H), 7.80(d, 2H), 13.36(d, 2H). 13C NMR
(CDCl3, ppm): d 27.0, 26.5, 25.8, 13.4, 122.1, 123.3,
136.8, 224.2. 119Sn NMR (CDCl3, ppm): À198.3.
2.2.12. (PhCH2)2Sn(SSCC3H2N2) (12)
The solid is obtained from ethyl ether. Yield: 86%.
M.p. >220 ꢁC (dec.). Anal. Calc. for C18H16N2S2Sn: C,
48.78; H, 3.64; N, 6.32. Found: C, 48.66; H, 3.71; N,
6.21%. IR (KBr, cmÀ1): 1606, 1263, 1021, 561, 447,
2.2.7. (Ph)2Sn(SSCC3H3N2)2 (7)
The solid is recrystallized from ethyl ether and the red
crystal complex 7 is formed. Yield: 84%. M.p. >220 ꢁC
(dec.). Anal. Calc. for C20H16N4S4Sn: C, 42.95; H,
2.88; N, 10.02. Found: C, 42.79; H, 3.01; N, 9.86%. IR
1
369. H NMR (CDCl3, ppm): d 3.15(s, 4H), 7.30–
7.58(m, 10H), 7.07(s, 1H), 7.79(s, 1H). 13C NMR
(CDCl3, ppm): d 38.3, 127.2, 129.7, 141.0, 122.1, 122.9,
136.4, 224.5. 119Sn NMR (CDCl3, ppm): À79.2.
1
(KBr, cmÀ1): 3301, 1612, 1264, 1028, 562, 460 373. H
NMR (CDCl3–D2O, ppm):
d 7.34–7.81(m, 10H),
7.12(d, 2H), 7.76(d, 2H), 13.01(d, 2H). 13C NMR
(CDCl3, ppm): d 128.1, 130.7, 137.2, 122.7, 123.5,
136.3, 225.9. 119Sn NMR (CDCl3, ppm): À208.9.
2.3. X-ray crystallographic studies
Diffraction data were collected on a Smart CCD area-
detector with graphite monochromated Mo Ka radiation
˚
2.2.8. (PhCH2)2Sn(SSCC3H3N2)2 (8)
(k = 0.71073 A). A semiempirical absorption correction
The solid is obtained from ethyl ether. Yield: 76%.
M.p. 182–184 ꢁC. Anal. Calc. for C22H20N4S4Sn: C,
44.98; H, 3.43; N, 9.54. Found: C, 44.79; H, 3.58; N,
was applied to the data. The structure was solved by
direct methods using SHELXS-97 and refined against F2
by full matrix least-squares using SHELXL-97. Hydrogen
atoms were placed in calculated positions. Crystal data
and experimental details of the structure determinations
are listed in Table 1.
9.41%. IR (KBr, cmÀ1): 3322, 1604, 1267, 1031, 572,
1
445, 361.
H NMR (CDCl3–D2O, ppm): d 3.11(s,
4H), 7.28–7.61(m, 10H), 7.03(d, 2H), 7.84(d, 2H),
13.34 (d, 2H). 13C NMR (CDCl3, ppm): d 38.1, 127.5,
129.4, 141.5, 143.6, 123.1, 124.0, 136.5, 225.2. 119Sn
NMR (CDCl3, ppm): À191.0.
3. Results and discussion
2.2.9. (CH3)2Sn(SSCC3H2N2) (9)
3.1. Syntheses
The solid is recrystallized from ethyl ether and the red
crystal complex 9 is formed. Yield: 78%. M.p. >220 ꢁC
(dec.). Anal. Calc. for C6H8N2S2Sn: C, 24.77; H, 2.77;
N, 9.63. Found: C, 24.65; H, 2.70; N, 9.52%. IR (KBr,
cmÀ1): 1607, 1266, 1022, 558, 457, 361. 1H NMR
Reactions of diorganotin (IV) dichlorides with 4(5)-
imidazoledithiocarboxylic acid in 1:1 or 1:2 stoichiome-
try depending on the nature of the starting acceptor and
reaction condition afford air-stable complexes in good
yields. The syntheses procedures are shown in Scheme 2.
2
(CDCl3, ppm): d 0.89(s, 6H, JSnH = 64.6), 7.06(s, 1H),

C. Ma et al. / Inorganica Chimica Acta 358 (2005) 3084–3092
3087
Table 1
Crystal, data collection and structure refinement parameters for complexes 1, 7 and 9
Complex
1
7
9
Empirical formula
Formula weight
Temperature
C6H9N2S2Sn
327.41
298(2)
C20H16N4S4Sn
559.30
298(2)
C6H8N2S2Sn
290.95
298(2)
Crystal system
Space group
Unit cell dimension
monoclinic
P2(1)/c
monoclinic
C2/c
orthorhombic
Fdd2
˚
a (A)
12.757(5)
13.162(5)
22.94(3)
17.46(2)
20.434(10)
17.937(9)
19.299(9)
90
˚
b (A)
˚
c (A)
14.247(5)
103.057(5)
16.22(19)
135.00(2)
b (ꢁ)
Z
8
2.735
8
1.490
16
1.648
Absorption coefficient (mmÀ1
Crystal size (mm)
)
0.45 · 0.41 · 0.22
2.13–25.03
0.36 · 0.19 · 0.16
2.33–25.03
0.17 · 0.15 · 0.10
3.70–25.03
À17 6 h 6 24;
À20 6 k 6 21;
À22 6 l 6 22
8472
h Range for data collection (ꢁ)
Index ranges
À15 6 h 6 15;
À15 6 k 6 15;
À15 6 l 6 16
11743
À25 6 h 6 27;
À20 6 k 6 20;
À19 6 l 6 12
11201
Reflections collected
Unique reflections [Rint
]
4026 [0.0328]
4026/0/217
1.000
3984 [0.0980]
3984/0/263
0.903
3001 [0.1248]
3001/1/100
0.728
Data/restraints/parameters
S (goodness-of-fit) on F2
Final R indices [I > 2r(I)]
R indices (all data)
R1 = 0.0347, wR2 = 0.0917
R1 = 0.0618, wR2 = 0.1144
R1 = 0.0599, wR2 = 0.1289
R1 = 0.1100, wR2 = 0.1518
R1 = 0.0492, wR2 = 0.0788
R1 = 0.1669, wR2 = 0.0993
3.2. Spectroscopic studies
3.2.1. IR spectra
strong absorption appearing in the region 350–400
cmÀ1, which is absent in the free ligand, is assigned
to the Sn–S stretching mode of vibration. All these
values are consistent with that detected in a number
of organotin (IV) derivatives [13,14]. The m(C@N)
band, occurring at about 1604 cmÀ1, is considerably
shifted towards lower frequencies with respect to that
of the free ligand, confirming the coordination of the
heterocyclic N to the tin. The stretching frequency is
The stretching frequencies of interest are those asso-
ciated with the acid CSS, Sn–C, Sn–S and Sn–N
groups. In the infrared spectra of all complexes the ab-
sence of the band at about 2590 cmÀ1, which appears
in the free-ligand as the m(S–H) vibration, indicates
metal–ligand bond formation through this site. While
R
Cl
Sn
S
R
N
NH
S
(R=CH3 1, nBu 2, C6H5 3, C6H5CH2 4)
RR
SH
S
Sn
S
S
S
S
NH
R2SnCl2
A
+
EtONa
C
+
N
N
N
N
N
H
H
B
(R=CH3 5, nBu 6, C6H5 7, C6H5CH2 8)
R
R
Sn
N
S
N
n
S
(R=CH3 9, nBu 10, C6H5 11, C6H5CH2 12)
(when A: B: C= 1: 1: 1, complexes1-4; A:B:C= 1: 2: 2, complexes 5-8;
A: B: C= 1: 1:2, complexes 9-12)
Scheme 2.

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C. Ma et al. / Inorganica Chimica Acta 358 (2005) 3084–3092
lowered owing to the displacement of electron density
from N to Sn atom, thus resulting in the weakening of
the C@N bond as reported in the literature [15]. So
that the weak- or medium-intensity bands in the re-
gion 445–470 cmÀ1 are assigned to Sn–N stretching
vibrations.
4. Crystal structures
4.1. Crystal structure of (CH3)2SnCl(SSCC3H2N2) (1)
For complex 1, the asymmetric unit contains two
monomers A and B (Fig. 1), which are different from
a crystallographic point of view. The conformations of
the two independent molecules A and B are almost the
same, with only small differences in bond lengths and
bond angles (Table 1). Tin forms four primary bonds:
two to the methyl groups, and one each to sulfur and
chlorine atoms. In addition, there exists a coordination
interaction between tin and nitrogen atoms. The Sn–N
3.2.2. NMR spectroscopic
1H NMR spectroscopy of the free ligand, single res-
onance is observed at 1.61 ppm, which is absent in the
spectra of the complexes, indicating the replacement of
the dithiocarboxylic acid proton by a diorganotin moi-
ety. In addition, the presence of the N–H proton sig-
nal in the complexes 1–8 reveals that the other N
atom does not coordinate to Sn, which further testifies
˚
˚
bond lengths are 2.357(5) A [Sn(1)–N(1)] and 2.319(5) A
[Sn(2)–N(3)]. All these values lie in the range recorded
in the Cambridge Crystallographic Database from 2.27
2
their formations. The JSnH of dimethyltin derivatives
˚
1 and 9 has a value of 87.2, falling in the range for
five coordinated trigonal bipyramidal tin (IV) adducts
[16].
to 2.58 A [19], but are considerably less than the van
˚
der waalÕs radii of the two atoms (3.74 A) [20], thus pro-
viding five-membered chelate rings with bite angles of
76.70(13)ꢁ for N(1)–Sn(1)–S(1) and of 76.69(14)ꢁ for
N(3)–Sn(2)–S(3). Including the tin–nitrogen interaction,
the geometry at tin becomes distorted cis-trigonal bipy-
ramidal with the nitrogen and chlorine atoms in axial
sites (Cl(1)–Sn(1)–N(1), 160.48(13)ꢁ and Cl(2)–Sn(2)–N(3),
The 13C NMR spectra of all complexes show a sig-
nificant downfield shift of all dithiocarboxylic reso-
nances, compared with the free ligand. The shift is a
consequence of an electron density transfer from the li-
1
gand to the acceptor. The JSnC value for 1 is 521 Hz,
similar to that of the five-coordinate compound, and
ˇ
ˇ
the calculated h (C–Sn–C) by the Holecek and Lycka
equation [16] are 122.5ꢁ, which are close to the angles
observed in the solid state for 1. So it can be reason-
ably assumed that the structure in solution of all these
complexes is likely similar to that observed in the solid
state.
The 119Sn NMR data show 1 only one signal, typical
of a five-coordinate species, which have been found in
accordance with the structure of solid state [17]. The
chemical shift for 7 shows À208.9 ppm, which is almost
within the range corresponding to coordination number
6, À210 to À400 ppm [18]. However, the chemical shift
for 9 shows À77.4 ppm within the range corresponding
to coordination number 4, À60 to +200 ppm [18]. So it
can be reasonably assumed that the structure in solution
of 9 is likely different from that observed in the solid
state.
Fig. 2. The unit cell of complex 1.
Fig. 1. The molecular structure of complex 1.

C. Ma et al. / Inorganica Chimica Acta 358 (2005) 3084–3092
3089
159.11(14)ꢁ) and one sulfur and two methyl carbon
atoms occupying the equatorial plane (C(5)–Sn(1)–
C(6), 126.8(3)ꢁ and C(11)–Sn(2)–C(12), 125.7(3)ꢁ). The
sum of the angles subtended at the tin atom in the trigo-
nal plane is 358.6ꢁ for A and 359.5ꢁ for B, so that the
atoms Sn(1), C(5), C(6) and S(1) for A and Sn(2),
C(11), C(12) and S(3) for B are almost in the same plane.
octahedral coordination are partly because of the bond-
ing variety. The two sulfur atoms occupy trans positions
S(1)–Sn(1)–S(1)#1 157.42(1)ꢁ and S(3)#2–Sn(2)–S(3)
157.35(11)ꢁ, while the cases for the nitrogen bonding vary
and they occupy cis positions (N(1)–Sn(1)–N(1)#1,
76.6(3)ꢁ. Besides, on each side of the tin atom, the S and
N equatorial ligating atoms belong to the same moi-
ety (N(1)–Sn(1)–S(1) 75.43(18)ꢁ, N(1)–Sn(1)–S(1)#1
86.81(18)ꢁ, N(1)#1–Sn(1)–S(1) 86.81(18)ꢁ and N(1)#1–
Sn(1)–S(1)#1 75.43(18)ꢁ for A and N(3)–Sn(2)–S(3)
75.45(17)ꢁ, N(3)#2–Sn(2)–S(3) 86.78(18)ꢁ, S(3)#2–
Sn(2)–S(3) 157.35(11)ꢁ and N(3)#2–Sn(2)–S(3)#2
˚
The Sn–Cl bond length (Sn(1)–Cl(1), 2.484(2) A and
˚
Sn(2)–Cl(2), 2.480(2) A) lies in the range of the normal
˚
covalent radii (2.37–2.60 A) [19]. The Sn–S bond length
˚
(Sn(1)–S(2), 2.4798(18) A and Sn(2)–S(3), 2.4892(17) A)
˚
˚
is well within the range of 2.478–2.541 A reported for
dimethyltin dithiocarboxyl complexes [21,22], it is short-
˚
er than that of Me2Sn[(S2CN(CH2)4) 2.518(1) A [23] and
it is almost equal to that of Me2Sn(S2CNEt2)2
˚
˚
Me2Sn(S2CNMe2)2 2.47(1) A [24] and 2.488(1) A [25].
Finally, the Sn–C bond lengths are approximately equal
˚
(from 2.104(6) and 2.113(9) A), similar to the average
˚
value of 2.13 A [20].
4.2. Crystal structure of (Ph)2Sn(SSCC3H3N2)2 (7)
The molecular structure and unit cell are shown in
˚
Figs. 3 and 4. Selected bond lengths (A) and angles (ꢁ)
are listed in Table 3. For the complex 7, similarto the com-
plex 1, there exist two monomers in the asymmetric unit.
Both ligands chelate to one tin, bonding through one
dithiocarboxylate sulfur and the nitrogen atom. The com-
plex contains a hexa-coordinated tin atom and has a dis-
torted octahedral environment. Two carbons of phenyl
and two sulfur atoms of the two ligands are covalently
linked to the tin. The valence extension is preformed via
two nitrogen atoms. The carbons are situated in a cis po-
sition to each other C(17)–Sn(1)–C(18) 102.4(4)ꢁ and
C(15)–Sn(2)–C(15)#2 102.7(4)ꢁ. Distortions from strict
Fig. 4. The unit cell of complex 7.
Fig. 3. The molecular structure of complex 7.

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C. Ma et al. / Inorganica Chimica Acta 358 (2005) 3084–3092
˚
Table 2
within the sum of the van der Waals radii of 4.05 A
for tin and sulfur atom [28]. The Sn–N distances
Sn(1)–N(1) are longer than the sum of the covalent ra-
˚
Selected bond lengths (A) and bond angles (ꢁ) for complex 1
Molecule A
Molecule B
˚
dii of Sn and N (2.15 A), but all these values lie in the
range recorded in the Cambridge Crystallographic
Sn(1)–C(5)
Sn(1)–C(6)
Sn(1)–N(1)
Sn(1)–S(1)
Sn(1)–Cl(1)
Sn(1)–Cl(2)
2.104(6)
2.108(7)
2.357(5)
Sn(2)–C(11)
Sn(2)–C(12)
Sn(2)–N(3)
2.109(7)
2.113(9)
2.319(5)
2.480(2)
2.4892(17)
4.243(2)
˚
Database from 2.27 to 2.58 A [19].
2.4798(18) Sn(2)–Cl(2)
2.484(2)
3.922(3)
Sn(2)–S(3)
Sn(2)–Cl(1)#1
4.3. Crystal structure of (CH3)2Sn(SSCC3H2N2) (9)
C(5)–Sn(21)–C(6) 126.8(3)
C(11)–Sn(2)–C(12)
C(11)–Sn(2)–N(3)
C(12)–Sn(2)–N(3)
C(11)–Sn(2)–Cl(2)
C(12)–Sn(2)–Cl(2)
N(3)–Sn(2)–Cl(2)
C(11)–Sn(2)–S(3)
C(12)–Sn(2)–S(3)
125.7(3)
94.7(3)
90.8(3)
The molecule structure is connected in polymeric
structures as shown in Fig. 5. Selected bond lengths
C(5)–Sn(1)–N(1)
C(6)–Sn(1)–N(1)
C(5)–Sn(1)–S(1)
C(6)–Sn(1)–S(1)
N(1)–Sn(1)–S(1)
88.4(2)
91.9(3)
˚
116.8(2)
115.0(2)
76.70(13)
97.3(2)
96.1(3)
(A) and angles (ꢁ) are listed in Table 4. Intermolecular
tin-nitrogen bonds (2.311(11) A) that are comparable
˚
159.11(14)
110.8(2)
123.0(2)
76.69(14)
83.06(7)
in strength to the intramolecular tin–nitrogen bonds
and close in length to the sum of the covalent radii of
˚
tin and nitrogen, 2.15 A [20], create a continuous poly-
meric chain.
C(5)–Sn(1)–Cl(1) 98.3(2)
C(6)–Sn(1)–Cl(1) 98.6(3)
N(1)–Sn(1)–Cl(1) 160.48(13) N(3)–Sn(2)–S(3)
S(1)–Sn(1)–Cl(1) 83.94(6) Cl(2)–Sn(2)–S(3)
C(5)–Sn(1)–Cl(2) 63.30(19)
C(6)–Sn(1)–Cl(2) 75.8(3)
C(11)–Sn(2)–Cl(1)#1 62.0(2)
C(12)–Sn(2)–Cl(1)#1 64.2(2)
For the complex, the ligand chelates to one tin, bond-
ing through one dithiocarboxylate sulfur and the nitrogen
atom, an additional intermolecular Sn–N interaction be-
tween the other nitrogen atom of the 4(5)-imidazoledi-
thiocarboxylic acid and the tin atom of a neighboring
molecule gives rise to the polymeric structure. Therefore,
the ligand is tridentate in the complex. The overall config-
uration at tin is best described as distorted trigonal bipy-
ramidal: tin and the bonded sulfur and carbon atoms are
nearly coplanar and deviate only slightly from regular dis-
N(1)–Sn(1)–Cl(2) 128.37(13) N(3)–Sn(2)–Cl(1)#1 103.58(13)
S(1)–Sn(1)–Cl(2) 153.79(6) Cl(2)–Sn(2)–Cl(1)#1 97.15(7)
Cl(1)–Sn(1)–Cl(2) 70.53(6) S(3)–Sn(2)–Cl(1)#1 172.83(6)
75.45(17)ꢁ for B, so their positions are fixed and the S–Sn–
N angles can only admit very little deformation.
Due to the symmetry operation, two Sn–S and Sn–
N bonds are identical, respectively. Both the Sn–S
˚
˚
bond lengths 2.596(3) A are greater than that in
torted geometry, mean deviation from plane is 0.0176 A
with N(1) and N(2)#1 (Àx + 1/4, y + 1/4, z + 1/4) occupy-
[Ph2Sn(S2COiPr)2] (Sn–S 2.482(1) A) [26] and
˚
[Ph2Sn(S2CC6H4CH3-4)2] (Sn–S 2.482(7) A) [27], but
˚
ing the axial sites, the axial-Sn-axial, N(1)–Sn–N(2)#1 is
Table 3
˚
Selected bond lengths (A) and bond angles (ꢁ) for complex 7
Sn(1)–C(5)
2.155(8)
2.155(8)
2.323(7)
2.323(6)
2.596(3)
2.596(3)
Sn(2)–C(15)
Sn(2)–C(15)#2
Sn(2)–N(3)#2
Sn(2)–N(3)
2.177(8)
2.177(8)
2.339(6)
2.339(6)
2.596(3)
2.596(3)
Sn(1)–C(5)#1
Sn(1)–N(1)#1
Sn(1)–N(1)
Sn(1)–S(1)#1
Sn(1)–S(1)
Sn(2)–S(3)#2
Sn(2)–S(3)
C(1)–S(1)
C(1)–S(2)
1.729(8)
1.674(8)
102.4(4)
161.1(2)
92.1(3)
C(11)–S(3)
C(11)–S(4)
1.722(8)
1.667(8)
102.7(4)
91.6(3)
C(5)–Sn(1)–C(5)#1
C(5)–Sn(1)–N(1)#1
C(5)#1–Sn(1)–N(1)#1
C(5)–Sn(1)–N(1)
C(5)#1–Sn(1)–N(1)
N(1)#1–Sn(1)–N(1)
C(5)–Sn(1)–S(1)#1
C(5)#1–Sn(1)–S(1)#1
N(1)#1–Sn(1)–S(1)#1
N(1)–Sn(1)–S(1)#1
C(5)–Sn(1)–S(1)
C(15)–Sn(2)–C(15)#2
C(15)–Sn(2)–N(3)#2
C(15)#2–Sn(2)–N(3)#2
C(15)–Sn(2)–N(3)
C(15)#2–Sn(2)–N(3)
N(3)#2–Sn(2)–N(3)
C(15)–Sn(2)–S(3)#2
C(15)#2–Sn(2)–S(3)#2
N(3)#2–Sn(2)–S(3)#2
N(3)–Sn(2)–S(3)#2
C(15)–Sn(2)–S(3)
C(15)#2–Sn(2)–S(3)
N(3)#2–Sn(2)–S(3)
N(3)–Sn(2)–S(3)
161.7(2)
161.7(2)
91.6(3)
92.1(3)
161.1(2)
76.6(3)
89.0(2)
77.0(3)
104.4(2)
89.8(2)
105.2(2)
75.43(18)
86.81(18)
105.2(2)
89.0(2)
75.45(17)
86.78(18)
89.8(2)
C(5)#1–Sn(1)–S(1)
N(1)#1–Sn(1)–S(1)
N(1)–Sn(1)–S(1)
S(1)#1–Sn(1)–S(1)
S(1)–C(1)–S(2)
104.4(2)
86.78(18)
75.45(17)
157.35(11)
121.5(5)
86.81(18)
75.43(18)
157.42(11)
120.8(5)
S(3)#2–Sn(2)–S(3)
S(3)–C(11)–S(4)
Symmetry codes: #1 Àx + 1, y, Àz + 3/2; #2 Àx + 1, y, Àz + 1/2.

C. Ma et al. / Inorganica Chimica Acta 358 (2005) 3084–3092
3091
Fig. 5. The molecular structure of complex 9.
157.8(4)ꢁ. In such structures, the sum of angles between
the tin atom and the equatorial ligating atoms (two C
and one S in each case) is 359.9ꢁ, compared with the ideal
octahedral value of 360ꢁ.
the sulfur of dithiocarboxylate and two nitrogen atoms.
˚
The Sn–N bond lengths 2.206–2.260 A approach the
˚
sum of the covalent radii of Sn and N (2.15 A). So the li-
gand is tridentate and the coordinated number of tin
atom is five. However, monomeric complexes possess
five- or six-coordinate tin atoms and the ligand is biden-
˚
The average Sn–C bond lengths are 2.155 A, in good
agreement with the published values [19]. These values
also correspond well with the sum of the covalent radii
˚
(2.15 A) of tin and carbon [29]. The Sn–N distances,
˚
tate. The Sn–N bond lengths are 2.323 A. All these are
1
also confirmed by IR and H NMR spectra analyses.
See (Fig. 2 and Table 2).
˚
2.260(9) and 2.311(11) A, are slightly greater than the
˚
sum of the covalent radii of tin and nitrogen, 2.15 A
[20], but in keeping with those reported in Sn–N com-
pounds Me2SnCl(2-Pic) [30], Me2Sn(2-Pic)2 [31] and
{[nBu2Sn(2-Pic)]2O}2 [32]. Concerning the Sn–S bond
lengths, we may note that the complex 1 is slightly long-
5. Supplementary material
Crystallographic data (excluding structure factors)
for the structure analysis of complexes 1, 7 and 9 have
been deposited with the Cambridge Crystallographic
Data Center, CCDC Nos. 248294 1, 228114 7 and
223778 9. Copies of these information may be obtained
free of charge from The Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-
336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
˚
er than the sum of the atomic radii (2.44 A) [33], as the
˚
case is 2.454(3) A, similar to that reported in penta-coor-
˚
dinated organotin complexes (2.47 A) [34].
In summary,the 4(5)-imidazoledithiocarboxylic acid
has been shown to be able to form monomeric and
one-dimensional supramolecular complexes. The nucle-
arity and stoichiometry are found to depend on the nat-
ure of the starting acceptor and reaction condition.
When using a 1:1:2 molar ratio of R2SnCl2:HSSCC3H3-
N2:EtONa, four one-dimensional chain complexes were
obtained. The ligand chelates to the tin, bonding through
Acknowledgments
We thank the National Nature Science Foundation
of China (20271025) and the National Nature Science
Foundation of Shandong Province for financial support.
Table 4
˚
Selected bond lengths (A) and bond angles (ꢁ) for complex 9
Sn(1)–C(6)
Sn(1)–C(5)
Sn(1)–N(1)
Sn(1)–N(2)#1
2.092(16)
2.219(13)
2.260(9)
Sn(1)–S(1)
Sn(1)#2–N(2)
C(1)–S(1)
2.454(3)
2.311(11)
1.743(12)
1.671(14)
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2.311(11)
C(1)–S(2)
C(5)–Sn(1)–C(6)
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C(5)–Sn(1)–N(2)#1
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93.2(5)
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