New triorganotin(IV) complexes of polyfunctional S,N,O-ligands: Supramolecular structures based on π?π and/or C-H?π interactions

Article abstract of DOI:10.1016/j.jorganchem.2005.12.054

A series of new triorganotin(IV) complexes with 4-hydroxy-2-mercapto-6- methylpyrimidine (L¹H₂), 4-hydroxy-2-mercapto-pyrimidine (L²H₂), 2,4(1H,3H)-pyrimidinedithione (L³H ₂) (Scheme 1) of the type R₃SnLSnR₃ (R = Me 1, 4, 7; R = Ph 2, 5, 8; R = PhCH₂ 3, 6, 9) have been synthesized by reactions of triorganotin(IV) chloride and corresponding ligands. All complexes are characterized by elemental analyses, IR spectra and NMR spectra analyses. Among them, complexes 2, 5 and 8 are also characterized by X-ray crystallography diffraction analyses. Significant π?π stacking, C-H?π interactions and intramolecular hydrogen bonds stabilize these structures.

Full text of DOI:10.1016/j.jorganchem.2005.12.054

Journal of Organometallic Chemistry 691 (2006) 2014–2022
www.elsevier.com/locate/jorganchem
New triorganotin(IV) complexes of polyfunctional
S,N,O-ligands: Supramolecular structures based on pÁ Á Áp and/or
C–HÁ Á Áp interactions
a,b,
a
a
Chunlin Ma
*, Guangru Tian , Rufen Zhang
a
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
b
Taishan University, Taian 271021, PR China
Received 23 October 2005; received in revised form 19 December 2005; accepted 26 December 2005
Available online 20 February 2006
Abstract
A series of new triorganotin(IV) complexes with 4-hydroxy-2-mercapto-6-methylpyrimidine (L1H2), 4-hydroxy-2-mercapto-pyrimi-
dine (L2H2), 2,4(1H,3H)-pyrimidinedithione (L3H2) (Scheme 1) of the type R3SnLSnR3 (R = Me 1, 4, 7; R = Ph 2, 5, 8; R = PhCH2
3, 6, 9) have been synthesized by reactions of triorganotin(IV) chloride and corresponding ligands. All complexes are characterized
by elemental analyses, IR spectra and NMR spectra analyses. Among them, complexes 2, 5 and 8 are also characterized by X-ray crys-
tallography diffraction analyses. Significant pÁ Á Áp stacking, C–HÁ Á Áp interactions and intramolecular hydrogen bonds stabilize these
structures.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Triorganotin(IV); 4-Hydroxy-2-mercapto-6-methylpyrimidine; pÁ Á Áp stacking; Crystal structure
1. Introduction
tions [10]. In addition to the aforesaid applications,
organotin(IV) compounds are also of interest in view of
the considerable structural diversity they possess. This
aspect has been attracting the attention of a number of
researchers and a multitude of structural types have been
discovered [11].
We have reported some organotin(IV) complexes with
pyrimidine ligands before, such as 2-mercaptopyrimidine,
4-amino-2-mercaptopyrimidine [12a,12b] and 2-mercapto-
4-methylpyrimidine [12c]. As an extension of this aspect,
here, we report the syntheses and crystal structures of
new polymeric triorganotin(IV) complexes of polyfunc-
tional S,N,O-ligands involving pÁ Á Áp and/or C–HÁ Á Áp inter-
actions. We obtained nine new complexes by reaction of
triorganotin(IV) chloride and corresponding substituted
pyrimidine ligands in the presence of sodium ethoxide.
Determinations by elemental analyses, IR and NMR spec-
tra analyses of all the complexes are given. Among them,
complexes 2, 5 and 8 are also characterized by X-ray crys-
tallography diffraction analyses.
The construction of sophisticated inorganic–organic
hybrid [1,2] supramolecular networks [3] based on orga-
nized strong covalent interactions [4] and extensive lateral
weak non-covalent forces like hydrogen bonding [5],
pÁ Á Áp stacking [6] is an area of great activity due to fabrica-
tion of functional materials [7] utilizing the wide variety in
properties associated with each suitably tailored compo-
nent. An analysis of complexes with aromatic nitrogen het-
erocycles as ligands reveals that such a pÁ Á Áp stacking is
usually an offset or slipped facial arrangement of the rings,
i.e., edge- or point-to-face C–HÁ Á Áp interactions [8,9]. A
near face-to-face alignment of the rings is extremely rare.
In recent years many organotin(IV) compounds have been
the topic of interest for their potential practical applica-
*
Corresponding author. Tel.: +86 635 8258579; fax: +86 538 6715521.
E-mail address: macl@lctu.edu.cn (C. Ma).
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.12.054

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 2014–2022
2015
ture (298 K) unless otherwise specified; 13C NMR spectra
are broadband proton decoupled. The chemical shifts were
reported in ppm with respect to the references and were sta-
ted relative to external tetramethylsilane (TMS) for 1H and
13C NMR, and to neat tetramethyltin for 119Sn NMR. Ele-
mental analyses (C, H, N) were performed with a PE-
2400II apparatus. Mass spectral data were measured on a
MAT 8500 Finnigan 70 eV mass spectrometer (Germany)
and m/z values were calculated assuming H = 1, C = 12,
Sn = 120, O = 16, N = 14 and S = 32.
Y2
Y1
Y2
Y3
CH3
H
4
L1H2
L2H2
SH
SH
SH
OH
OH
SH
5
6
N 3
2
Y1
L3H2
Y3
N
1
H
Scheme 1.
2.2. Synthesis
2. Experimental section
2.1. Materials and measurements
The general route of synthesis is shown in the
following. The reaction was carried out under nitrogen
atmosphere with use of standard Schlenk technique.
Pyrimidine (4-hydroxy-2-mercapto-6-methylpyrimidine, 4-
hydroxy-2-mer- capto-pyrimidine, 2,4(1H,3H)-pyrimidin-
edithione) ligands and the sodium ethoxide were added
to the solution of methanol, the mixture was stirred for
30 min, and then added triorganotin(IV) chlorides to the
mixture, continuing the reaction about 12 h at 40 °C. After
cooling down to room temperature, the mixture was fil-
tered. The solvent of the filtrate was gradually removed
by evaporation under vacuum until solid product was
obtained. The solid was then recrystallized from methanol.
The synthetic experiments of complexes 1–9 were shown in
Scheme 2.
Trimethyltin chloride, triphenyltin chloride and 4-
hydroxy-2-mercapto-6-methylpyrimidine, 4-hydroxy-2-mer-
capto-pyrimidine, 2,4(1H,3H)-pyrimidinedithione were
commercially available, and they were used without further
purification. Tribenzyltin chloride was prepared by a stan-
dard method reported in the literature [13]. The melting
points were obtained with Kofler micro melting point
apparatus and were uncorrected. 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 acquired at room tempera-
R
OH
O
N
Sn
R
R
N
N
EtONa
R3SnCl
+
(R=Me 1, Ph 2, PhCH 3)
2
CH3OH
N
S
H3C
SH
H3C
R
Sn
R
R
R
OH
N
O
N
Sn
R
R
N
N
EtONa
R3SnCl
+
(R=Me 4, Ph 5, PhCH 6)
2
CH3OH
S
SH
R
Sn
R
R
R
SH
N
S
Sn
R
R
N
N
EtONa
R3SnCl
+
(R=Me 7, Ph 8, PhCH 9)
2
CH3OH
N
S
SH
R
Sn
R
R
Scheme 2.

2016
C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 2014–2022
2.2.1. Me3Sn(C5H4N2OS)SnMe3 (1)
2.2.4. Me3Sn(C4H2N2OS)SnMe3 (4)
Complex 1 was synthesized by adding 4-hydroxy-2-
mercapto-6-methylpyrimidine (0.142 g, 1 mmol), sodium
ethoxide (0.136 g, 2 mmol) and trimethyltin chloride
(0.398 g, 2 mmol) to the solution of methanol.
Complex 4 was synthesized by the same procedure as 1
with 4-hydroxy-2-mercapto-pyrimidine (0.128 g, 1 mmol),
sodium ethoxide (0.136 g, 2 mmol) and trimethyltin chlo-
ride (0.398 g, 2 mmol).
m.p. 116–118 °C. Yield, 0.374 g, 80%. Anal. Calc. for
C11H22N2OSSn2: C, 28.24; H, 4.74; N, 5.99. Found: C,
28.27; H, 4.71; N, 6.01%. IR (KBr, cmÀ1): 1583 (C@N),
560 (Sn–C), 458 (Sn–N), 307 (Sn–S), 467 (Sn–O). 1H
m.p. 119–122 °C. Yield, 0.354 g, 78%. Anal. Calc. for
C10H20N2OSSn2: C, 26.47; H, 4.44; N, 6.17. Found: C,
26.49; H, 4.41; N, 6.18%. IR (KBr, cmÀ1): 1582 (C@N),
565 (Sn–C), 459 (Sn–N), 306 (Sn–S), 469 (Sn–O). 1H
2
2
NMR (CDCl3): d 0.90 (s, JSn,H = 68.6 Hz, 18H), 1.34 (s,
NMR (CDCl3): d 0.90 (s, JSn,H = 68.8 Hz, 18H), 7.48 (s,
ring-CH3, 3H), 7.44 (s, ring-C5-H, 1H). 13C NMR
(CDCl3): d 8.2, 10.6 (Sn–CH3), 24.7 (ring-CH3), 172.4
(C2), 179.1 (C4), 132.1 (C5), 164.4 (C6). 119Sn NMR
(CDCl3): À135, À95 ppm. MS (m/z, ion, intensity): (470)
[Me3Sn(C5H4N2OS)SnMe3]+ M+ (2), (455) [Me3Sn(C5H4-
N2OS)SnMe2]+ (45), (305) [Me3Sn(C5H4N2OS)]+ (100),
(165) [Me3Sn]+ (80), (120) [Sn]+ (5).
ring-C5–H, 1H), 8.80 (s, ring-C6–H, 1H). 13C NMR
(CDCl3): d 8.12, 10.5 (Sn–CH3), 172.4 (C2), 179.1 (C4),
132.1 (C5), 157.2 (C6). 119Sn NMR (CDCl3): À137,
À95 ppm. MS (m/z, ion, intensity): (456) [Me3Sn(C4H2-
N2OS)SnMe3]+ M+ (2), (441) [Me3Sn(C4H2N2OS)SnMe2]+
(45), (291) [Me3Sn(C4H2N2OS)]+ (100), (165) [Me3Sn]+
(80), (120) [Sn]+ (5).
2.2.2. Ph3Sn(C5H4N2OS)SnPh3 (2)
2.2.5. Ph3Sn(C4H2N2OS)SnPh3 (5)
Complex 2 was synthesized by the same procedure as 1
with 4-hydroxy-2-mercapto-6-methylpyrimidine (0.142 g,
1 mmol), sodium ethoxide (0.136 g, 2 mmol) and triphenyl-
tin chloride (0.770 g, 2 mmol).
Complex 5 was synthesized by the same procedure as 1
with 4-hydroxy-2-mercapto-pyrimidine (0.128 g, 1 mmol),
sodium ethoxide (0.136 g, 2 mmol) and triphenyltin chlo-
ride (0.770 g, 2 mmol).
m.p. 185–187 °C. Yield, 0.672 g, 76%. Anal. Calc. for
C41H34N2OSSn2: C, 58.61; H, 4.08; N, 3.33. Found: C,
58.56; H, 4.11; N, 3.35%. IR (KBr, cmÀ1): 1576 (C@N),
560 (Sn–C), 467 (Sn–N), 311 (Sn–S), 469 (Sn–O). 1H
NMR (CDCl3): d 7.36–7.81 (m, Sn–C6H5, 30H), 1.33 (s,
ring-CH3, 3H), 7.45 (s, ring-C5–H, 1H). 13C NMR
(CDCl3): d 24.7 (ring-CH3), 172.5 (C2), 179.2 (C4), 132.5
(C5), 164.4 (C6), 137.5 (o-C), 128.8 (m-C), 129.3 (p-C),
142.6 (i-C). 119Sn NMR (CDCl3): À173, À135 ppm. MS
(m/z, ion, intensity): (842) [Ph3Sn(C5H4N2OS)SnPh3]+
M+ (2), (765) [Ph3Sn(C5H4N2OS)SnPh2]+ (45), (491)
[Ph3Sn(C5H4N2OS)]+ (100), (351) [Ph3Sn]+ (80), (120)
[Sn]+ (5).
m.p. 183–185 °C. Yield, 0.644 g, 78%. Anal. Calc. for
C40H32N2OSSn2: C, 58.15; H, 3.90; N, 3.39. Found: C,
58.10; H, 3.91; N, 3.35%. IR (KBr, cmÀ1): 1578 (C@N),
556 (Sn–C), 469 (Sn–N), 309 (Sn–S), 468 (Sn–O). 1H
NMR (CDCl3): d 7.36–7.79 (m, Sn–C6H5, 30H), 7.49 (s,
ring-C5-H, 1H), 8.81 (s, ring-C6–H, 1H). 13C NMR
(CDCl3): d 172.5 (C2), 179.2 (C4), 132.5 (C5), 157.3 (C6),
137.5 (o-C), 128.8 (m-C), 129.3 (p-C), 142.6 (i-C).
119Sn NMR (CDCl3): À171, À133 ppm. MS (m/z, ion,
intensity): (828) [Ph3Sn(C4H2N2OS)SnPh3]+ M+ (2),
(757) [Ph3Sn(C4H2N2OS)SnPh2]+ (45), (477) [Ph3Sn-
(C4H2N2OS)]+ (100), (351) [Ph3Sn]+ (80), (120) [Sn]+
(5).
2.2.3. (PhCH2)3Sn(C5H4N2OS)Sn(CH2Ph)3 (3)
Complex 3 was synthesized by the same procedure as 1
with 4-hydroxy-2-mercapto-6-methylpyrimidine (0.142 g,
1 mmol), sodium ethoxide (0.136 g, 2 mmol) and tribenzyl-
tin chloride (0.854 g, 2 mmol).
2.2.6. (PhCH2)3Sn(C4H2N2OS)Sn(CH2Ph)3 (6)
Complex 6 was synthesized by the same procedure as 1
with 4-hydroxy-2-mercapto-pyrimidine (0.128 g, 1 mmol),
sodium ethoxide (0.136 g, 2 mmol) and tribenzyltin chlo-
ride (0.854 g, 2 mmol).
m.p. 125–127 °C. Yield, 0.703 g, 76%. Anal. Calc. for
C47H46N2OSSn2: C, 61.07; H, 5.02; N, 3.03. Found: C,
61.04; H, 4.98; N, 3.07%. IR (KBr, cmÀ1): 1581 (C@N),
557 (Sn–C), 456 (Sn–N), 309 (Sn–S), 467 (Sn–O). 1H
NMR (CDCl3): d 7.46–7.79 (m, Sn–CH2–C6H5, 30H),
3.26 (s, CH2, 12H), 1.35 (s, ring-CH3, 3H), 7.43 (s, ring-
C5–H, 1H). 13C NMR (CDCl3): d 24.7 (ring-CH3), 172.4
(C2), 179.1 (C4), 132.1 (C5), 163.4 (C6), 23.6, 21.9 (s,
CH2), 127.3 (o-C), 127.4 (m-C), 128.2 (p-C), 124.2 (i-C).
119Sn NMR (CDCl3): À151, À101 ppm. MS (m/z, ion,
intensity): (926) [(PhCH2)3Sn(C5H4N2OS)Sn(CH2Ph)3]+
M+ (2), (835) [(PhCH2)3Sn(C5H4N2OS)Sn(CH2Ph)2]+ (45),
(533) [(PhCH2)3Sn(C5H4N2OS)]+ (100), (393) [(PhCH2)3-
Sn]+ (80), (120) [Sn]+ (5).
m.p. 123–125 °C. Yield, 0.692 g, 76%. Anal. Calc. for
C46H44N2OSSn2: C, 60.69; H, 4.87; N, 3.08. Found: C,
60.72; H, 4.88; N, 3.07%. IR (KBr, cmÀ1): 1581 (C@N),
559 (Sn–C), 458 (Sn–N), 306 (Sn–S), 464 (Sn–O). 1H NMR
(CDCl3): d 7.46–7.79 (m, Sn–CH2–C6H5, 30H), 3.25 (s,
CH2, 12H), 7.47 (s, ring-C5–H, 1H), 8.82 (s, ring-C6–H,
1H). 13C NMR (CDCl3): d 172.4 (C2), 179.1 (C4), 132.1
(C5), 157.3 (C6), 23.6, 21.9 (s, CH2), 127.3 (o-C), 127.4
(m-C), 128.2 (p-C), 124.2 (i-C). 119Sn NMR (CDCl3):
À158, À102 ppm. MS (m/z, ion, intensity): (912) [(PhCH2)3-
Sn(C4H2N2OS)Sn(CH2Ph)3]+ M+ (2), (821) [(PhCH2)3-
Sn(C4H2N2OS)Sn(CH2Ph)2]+ (45), (519) [(PhCH2)3Sn-
(C4H2N2OS)]+ (100), (393) [(PhCH2)3Sn]+ (80), (120) [Sn]+
(5).

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 2014–2022
2017
Table 1
2.2.7. Me3Sn(C4H2N2S2)SnMe3 (7)
Crystal data and structure refinement parameters for 2, 5 and 8
Complex
Empirical formula C41H34N2OSSn2 C40H32N2OSSn2 C40H32N2S2Sn2
Complex 7 was synthesized by the same procedure as 1
with 2,4(1H,3H)-pyrimidinedithione (0.144 g, 1 mmol),
sodium ethoxide (0.136 g, 2 mmol) and trimethyltin chlo-
ride (0.398 g, 2 mmol).
2
5
8
M
Crystal system
Space group
840.14
Triclinic
826.12
Monoclinic
P21/n
9.3603(14)
39.169(3)
10.0495(16)
90.00
102.596(2)
90.00
842.24
Monoclinic
P21/a
15.0738(12)
12.6305(10)
19.1210(15)
90.00
92.6450(10)
90.00
m.p. 116–119 °C. Yield, 0.366 g, 78%. Anal. Calc. for
C10H20N2S2Sn2: C, 25.56; H, 4.29; N, 5.96. Found: C,
25.51; H, 4.31; N, 6.01%. IR (KBr, cmÀ1): 1581 (C@N),
ꢀ
P1
˚
a (A)
9.4989(18)
18.920(4)
21.781(4)
97.502(3)
96.252(3)
103.193(3)
3739.2(12)
4
˚
b (A)
˚
1
c (A)
564 (Sn–C), 459 (Sn–N), 307 (Sn–S). H NMR (CDCl3):
a (°)
b (°)
c (°)
2
d 0.90 (s, JSn,H = 69.2 Hz, 18H), 7.39 (s, ring-C5–H, 1H),
8.80 (s, ring-C6–H, 1H). 13C NMR (CDCl3): d 10.5 (Sn–
CH3), 172.4 (C2), 181.1 (C4), 134.1 (C5), 157.2 (C6). 119Sn
NMR (CDCl3): À131 ppm. MS (m/z, ion, intensity):
(472) [Me3Sn(C4H2N2S2)SnMe3]+ M+ (2), (457) [Me3Sn-
(C4H2N2S2)SnMe2]+ (55), (142) [(C4H2N2S2)]+ (80), (165)
[Me3Sn]+ (100), (120) [Sn]+ (5).
3
˚
V (A )
3595.8(8)
4
1.480
3636.6(5)
4
1.518
Z
l (mmÀ1
)
1.425
Reflections
collected
19872
18532
30718
Independent
reflections
Rint
13069
6316
8284
0.0284
0.998
0.0326
1.002
0.0364
0.991
2.2.8. Ph3 Sn(C4H2N2S2)SnPh3 (8)
Goodness-of-fit
on F2
Complex 8 was synthesized by the same procedure as 1
with 2,4(1H,3H)-pyrimidinedithione (0.144 g, 1 mmol),
sodium ethoxide (0.136 g, 2 mmol) and triphenyltin chlo-
ride (0.770 g, 2 mmol).
R1, wR2 [I > 2r(I)] 0.0441, 0.0784
R1, wR2 (all data) 0.0969, 0.0980
0.0543, 0.1543
0.0674, 0.1630
0.0309, 0.0652
0.0461, 0.0711
m.p. 176–180 °C. Yield, 0.657 g, 78%. Anal. Calc. for
C40H32N2S2Sn2: C, 57.04 H, 3.83; N, 3.33. Found: C,
57.01; H, 3.85; N, 3.35%. IR (KBr, cmÀ1): 1583 (C@N),
1000 CCD area-detector with graphite monochromated
˚
Mo Ka radiation (k = 0.71073 A).
A semi-empirical
1
557 (Sn–C), 467 (Sn–N), 307 (Sn–S). H NMR (CDCl3): d
absorption correction was applied to the data. The struc-
ture 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 posi-
tions. Crystal data and experimental details of the structure
determinations of 2, 5 and 8 are listed in Table 1.
7.36–7.79 (m, Sn–C6H5, 30H), 7.38 (s, ring-C5–H, 1H),
8.81 (s, ring-C6–H, 1H). 13C NMR (CDCl3): d 172.5 (C2),
181.2 (C4), 134.5 (C5), 157.3 (C6), 137.5 (o-C), 128.8 (m-C),
129.3 (p-C), 142.6 (i-C). 119Sn NMR (CDCl3): À175 ppm.
MS (m/z, ion, intensity): (844) [Ph3Sn(C4H2N2S2)- SnPh3]+
M+ (2), (773) [Ph3Sn(C4H2N2S2)SnPh2]+ (54), (142)
[(C4H2N2S2)]+ (80), (351) [Ph3Sn]+ (100), (120) [Sn]+ (5).
3. Results and discussion
2.2.9. (PhCH2)3Sn(C4H2N2S2)Sn(CH2Ph)3 (9)
Complex 9 was synthesized by the same procedure as 1
with 2,4(1H,3H)-pyrimidinedithione (0.144 g, 1 mmol),
sodium ethoxide (0.136 g, 2 mmol) and tribenzyltin chlo-
ride (0.854 g, 2 mmol).
3.1. Spectra
Comparing the IR spectra of the free ligand with com-
plexes 1–9, the bands at 2560–2430 and about 2300 cmÀ1
,
which appear in the spectra of the free ligand as the m(S–
H) and m(O–H) vibration, are absent in those of complexes
1–9, thus indicating metal–ligand bond formation through
these sites. In the far-IR spectra, the absorption about
310 cmÀ1 region for all complexes 1–9, which is absent in
the spectrum of the ligand, is assigned to the Sn–S stretch-
ing mode of vibration and all the values are located within
the range for Sn–S vibration observed in common organo-
tin derivatives of thiolate (300–400 cmÀ1) [14,15]. The
strong absorption appears at about 460–470 cmÀ1 in the
respective spectra of complexes 1–6, which is absent in
the free ligand, is assigned to the Sn–O stretching mode
of vibration. The m(C@N) band, occurring at about
1576–1583 cmÀ1 in the spectra of all complexes have been
assignable to m(C@N) according to the literatures [16], is
considerably shifted towards lower frequencies with respect
to that of the free ligand 1640–1650 cmÀ1, confirming the
coordination of the heterocyclic N to the tin, which indi-
cated the coordination of free ligand to these complexes
m.p. 119–122 °C. Yield, 0.704 g, 76%. Anal. Calc. for
C46H44N2S2Sn2: C, 59.64; H, 4.79; N, 3.02. Found: C,
59.68; H, 4.82; N, 3.03%. IR (KBr, cmÀ1): 1582 (C@N),
1
556 (Sn–C), 455 (Sn–N), 303 (Sn–S). H NMR (CDCl3): d
7.46–7.79 (m, Sn–CH2–C6H5, 30H), 3.12 (s, CH2, 12H),
7.39 (s, ring-C5–H, 1H), 8.82 (s, ring-C6–H, 1H). 13C NMR
(CDCl3): d 172.6 (C2), 181.3 (C4), 134.3 (C5), 157.1 (C6),
21.6 (s, CH2), 127.3 (o-C), 127.4 (m-C), 128.2 (p-C), 124.2
(i-C). 119Sn NMR (CDCl3): À153 ppm. MS (m/z, ion, inten-
sity): (928) [(PhCH2)3Sn(C4H2N2S2)Sn(CH2 Ph)3]+ M+ (2),
(837) [(PhCH2)3Sn(C4H2N2S2)Sn(CH2 Ph)2]+ (55), (142)
[(C4H2N2S2)]+ (80), (393) [(PhCH2)3Sn]+ (100), (120) [Sn]+
(5).
2.3. X-ray structure analyses of 2, 5 and 8
Crystals were mounted in Lindemann capillaries under
nitrogen. Diffraction data were collected on a Smart–

2018
C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 2014–2022
Table 2
is through sulfur atoms via thiol form and oxygen atoms
via phenol form. The stretching frequency is 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 [17]. The weak- or medium-inten-
sity band in the region 455–469 cmÀ1 can be assigned to
Sn–N stretching vibrations. All these values are consistent
with that detected in a number of organotin(IV) derivatives
[18,19].
˚
Selected bond lengths (A) and bond angles (°) for 2
Sn(1)–C(12)
Sn(1)–C(18)
Sn(1)–N(1)
Sn(2)–C(36)
Sn(2)–C(30)
Sn(3)–C(53)
Sn(3)–C(59)
Sn(3)–N(3)
Sn(4)–C(77)
Sn(4)–C(65)
S(1)–C(1)
2.103(8)
2.146(6)
2.841(5)
2.119(6)
2.131(6)
2.114(7)
2.138(6)
2.853(5)
2.123(6)
2.127(6)
1.752(6)
Sn(1)–C(6)
Sn(1)–S(1)
Sn(2)–O(1)
Sn(2)–C(24)
Sn(2)–N(2)
Sn(3)–C(47)
Sn(3)–S(2)
Sn(4)–O(2)
Sn(4 )–C(71)
Sn(4)–N(4)
S(2)–C(42)
2.125(6)
2.4263(17)
2.071(4)
2.124(6)
2.721(5)
2.120(7)
2.4280(17)
2.076(4)
2.124(6)
2.756(5)
1.749(6)
1H NMR data showed that the signal of the –SH proton
in the spectrum of the ligand is absent in all of the com-
plexes, indicating the removal of the –SH proton and the
formation of Sn–S bonds. The absence of the OH proton
signals in the complexes 1–6 further supports the binding
of the tin center to ligand oxygen atoms through the
C(12)–Sn(1)–C(6)
C(6)–Sn(1)–C(18)
C(6)–Sn(1)–S(1)
117.1(3)
C(12)–Sn(1)–C(18)
C(12)–Sn(1)–S(1)
C(18)–Sn(1)–S(1)
C(6)–Sn(1)–N(1)
S(1)–Sn(1)–N(1)
O(1)–Sn(2)–C(24)
O(1)–Sn(2)–C(30)
C(24)–Sn(2)–C(30)
C(36)–Sn(2)–N(2)
C(30)–Sn(2)–N(2)
C(53)–Sn(3)–C(59)
C(53)–Sn(3)–S(2)
C(59)–Sn(3)–S(2)
C(47)–Sn(3)–N(3)
S(2)–Sn(3)–N(3)
O(2)–Sn(4)–C(71)
O(2)–Sn(4)–C(65)
C(71)–Sn(4)–C(65)
C(77)–Sn(4)–N(4)
C(65)–Sn(4)–N(4)
105.0(2)
106.4(3)
115.47(17)
85.4(2)
110.4(2)
100.40(18)
83.28(19)
59.39(11)
109.6(2)
93.8(2)
108.9(2)
85.34(18)
147.5(2)
107.4(3)
114.46(19)
99.59(17)
86.5(2)
C(12)–Sn(1)–N(1)
C(18)–Sn(1)–N(1)
O(1)–Sn(2)–C(36)
C(36)–Sn(2)–C(24)
C(36)–Sn(2)–C(30)
O(1)–Sn(2)–N(2)
C(24)–Sn(2)–N(2)
C(53)–Sn(3)–C(47)
C(47)–Sn(3)–C(59)
C(47)–Sn(3)–S(2)
C(53)–Sn(3)–N(3)
C(59)–Sn(3)–N(3)
O(2)–Sn(4)–C(77)
C(77)–Sn(4)–C(71)
C(77)–Sn(4)–C(65)
O(2)–Sn(4)–N(4)
C(71)–Sn(4)–N(4)
2
159.7(2)
109.12(18)
123.2(2)
108.2(2)
53.72(14)
85.64(18)
116.6(3)
105.1(2)
111.71(18)
82.2(2)
158.65(19)
112.6(2)
111.6(2)
117.8(2)
52.82(14)
143.96(19)
replacement of phenolic hydrogens. The JSn,H values of
trimethyltin derivatives 1, 4 and 7 (68.6, 68.8 and 69.2 Hz
respectively) are similar to those previously reported for
five-coordinated trigonal bipyramidal tin(IV) adducts [20].
The structural changes occurring in ligand upon deproto-
nation and coordination to the Sn atom should be reflected
by the changes in the 13C NMR spectra of our complexes.
The 13C NMR spectra of all complexes show a significant
downfield shift of all carbon resonance, compared with
the free ligand. The shift is a consequence of an electron
cloud transfer from the ligand to the acceptor.
59.16(10)
91.15(19)
111.33(19)
109.1(2)
85.6(2)
As reported in the literature [21], values of d (119Sn) in
the ranges À210 to À400, À90 to À190 and 200 to
À60 ppm have been associated with six-, five- and four-
coordinate tin centers, respectively. The 119Sn NMR data
of complexes 1–6 (from À95 to À173 ppm) show two sig-
nals and complexes 7–9 (from À131 to À175 ppm) show
only one signal, typical of five-coordinated tin complexes.
The major mass spectral data of complexes 1–9 are given
along their synthesis in the experimental section. A molec-
ular ion peak of very low intensity was observed in com-
plexes 1–9, while the base peak of complexes 7–9
appeared at m/z = 165, 351 and 393, respectively, due to
the loss of the ligand. Fragments due to the loss of the R
groups from the molecular ion were observed in all com-
plexes. The base peak of complexes 1–3 appeared at
m/z = 305, 491 and 533, respectively, due to the loss of
the group R3Sn. Similarly, the base peak of complexes
4–6 appeared at m/z = 291, 477 and 519, respectively,
due to the loss of the group R3Sn. All the above analyses
are confirmed by X-ray diffraction.
87.84(19)
distorted trigonal bipyramidal geometry. The ligands
adopt its thiol sulfur atom and hydroxyl oxygen atom as
well as heterocyclic nitrogen atoms to coordinate to the
central tin atoms. For complex 2, the asymmetric unit con-
tains two monomers A and B (see Fig. 1), which are crys-
tallographically non-equivalent. The conformations of the
two independent molecules A and B are almost the same,
with only small differences in bond lengths and bond
angles(see Table 2). The primary bond lengths in 2 and 5
˚
˚
are: Sn(1)–S(1) 2.4263(17) A, Sn(1)–N(1) 2.841(5) A,
Table 3
˚
Selected bond lengths (A) and bond angles (°) for 5
Sn(1)–C(17)
Sn(1)–C(5)
Sn(1)–N(1)
Sn(2)–C(23)
Sn(2)–C(29)
S(1)–C(1)
2.134(8)
2.159(7)
2.693(6)
2.125(8)
2.138(8)
1.745(7)
Sn(1)–C(11)
Sn(1)–S(1)
Sn(2)–O(1)
Sn(2)–C(35)
Sn(2)–N(2)
2.135(7)
2.4684(19)
2.042(5)
2.128(8)
2.900(5)
3.2. Description of crystal structures
C(17)–Sn(1)–C(11)
C(11)–Sn(1)–C(5)
C(11)–Sn(1)–S(1)
C(17)–Sn(1)–N(1)
C(5)–Sn(1)–N(1)
O(1)–Sn(2)–C(23)
C(23)–Sn(2)–C(35)
C(23)–Sn(2)–C(29)
O(1)–Sn(2)–N(2)
C(35)–Sn(2)–N(2)
115.3(3)
C(17)–Sn(1)–C(5)
C(17)–Sn(1)–S(1)
C(5)–Sn(1)–S(1)
C(11)–Sn(1)–N(1)
S(1)–Sn(1)–N(1)
O(1)–Sn(2)–C(35)
O(1)–Sn(2)–C(29)
C(35)–Sn(2)–C(29)
C(23)–Sn(2)–N(2)
C(29)–Sn(2)–N(2)
106.9(3)
112.8(2)
98.8(2)
104.6(3)
116.21(18)
88.5(3)
158.4(2)
114.7(3)
117.7(3)
108.4(3)
50.82(18)
87.3(3)
3.2.1. Ph3Sn(C5H4N2OS)SnPh3 (2) and
Ph3Sn(C4H2N2OS)SnPh3 (5)
Selected bond lengths (A) and bond angles (°) for 2 and
5 are given in Tables 2 and 3, and its molecular structure
and network are shown in Figs. 1–4, respectively.
As shown in Figs. 1 and 3, complex 2 and 5 are both
monomers with one ligand coordinated to two triphenyltin
moiety. The central tin atoms are five-coordinated with
81.4(2)
˚
60.55(13)
106.3(3)
93.7(3)
113.7(3)
84.6(2)
143.7(3)

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 2014–2022
2019
˚
˚
Sn(1)–S(1) 2.4684(19) A, Sn(1)–N(1) 2.693(6) A, Sn(2)–
˚
˚
O(1) 2.042(5) A and Sn(2)–N(2) 2.900(5) A in 5. All these
Sn–N and Sn–S bond lengths are comparable with those
˚
found in Ph3Sn(SC5H5N2) (Sn(1)–S(1) 2.4228(16) A,
˚
Sn(1)–N(2) 2.907(4) A) [12c] and Ph3Sn(Hthpu) (H2thpu
˚
is 2-thio-6-hydroxypurine) (Sn(1)–S(1) 2.4661(17) A,
˚
Sn(1)–N(1) 2.653(5) A) [22]. And they lie in the range of
the sum of the covalent radii and the van der Waals radii
˚
˚
of Sn and S (2.42–4.0 A) [23] and Sn and N (2.15–3.74 A)
[24]. The Sn–O bond lengths are also comparable with
those in [SnMe2(Salop)] (H2salop is 2-{[(2-hydroxyphe-
˚
nyl)imino]methyl}phenol) Sn–O(1) 2.117(2) A, [SnVi2-
˚
(Salop)]
2.117(2) A,
[SnCl2(Salop)(CH3OH)]ÆCH3OH
˚
˚
(2.009(2) A and [SnBr2(Salop)(CH3OH)] (2.005(2) A [25].
The sum of equatorial angles of central tin atoms are
342.97° for Sn(1), 341.92° for Sn(2), 342.77° for Sn(3)
and 341.73° for Sn(4) in 2, and 346.31° for Sn(1) and
338.7° for Sn(2) in 5. The axial angles are C(18)–Sn(1)–
N(1) 159.7(2)° for Sn(1), C(30)–Sn(2)–N(2) 147.5(2)° for
Sn(2), C(59)–Sn(2)–N(3) 159.65(19)° for Sn(3), C(71)–
Sn(2)–N(4) 143.96(19)° for Sn(4) in 2, and C(5)–Sn(1)–
N(1) 158.4(2)° for Sn(1) and C(29)–Sn(2)–N(2) 143.7(3)°
for Sn(2) in 5. They deviate more or less from standard
360° and 180°, indicating the distortion of the geometry.
The complexes exhibit interesting intermolecular inter-
actions as shown in Figs. 2 and 4: the molecules of 2
and 5 are connected via offset pÁ Á Áp stacking interactions
of approximately parallel phenyl rings and pyrimidine
rings and edge- or point-to-face C–HÁ Á Áp interactions
(Table 4). In complex 2, pÁ Á Áp stacking interactions occur
between ring (C65–C70) and ring (C1–C4, N1, N2) (sym-
Fig. 1. Molecular structure of complex 2.
˚
metry codes: x, y, z) at a ring centroid distance of 3.811 A
Fig. 2. Perspective view of complex 2 showing pÁ Á Áp stacking interactions
(Cg(5): N(1)–C(1)–N(2)–C(2)–C(3)–C(4); ÆCg(6): C(65)–C(66)–C(67)–
C(68)–C(69)–C(70)) and edge- or point-to-face C–HÁ Á Áp interactions
(C(57)–H(57)Á Á ÁCg(1)) (Cg(1): C(59a)–C(60a)–C(61a)–C(62a)–C(63a)–
C(64a)).
(dihedral angle 6.0°). Evidence for a C–HÁ Á Áp interaction
is also found in the structure. The C(57)–H atom is direc-
ted towards the symmetry related (1 À x, 1 À y, 1 À z)
aromatic ring containing the C(59a)–C(64a) atoms. The
Fig. 3. Molecular structure of complex 5.
Fig. 4. Perspective view of complex 5 showing pÁ Á Áp stacking interactions
(Cg(7): N(1)–C(1)–N(2)–C(2)–C(3)–C(4); Cg(8): C(29a)–C(30a)–C(31a)–
C(32a)–C(33a)–C(34a)) and edge- or point-to-face C–HÁ Á Áp interactions
(C(38)–H(38)Á Á ÁCg(2)) (Cg(2): C(29b)–C(30b)–C(31b)–C(32b)–C(33b)–
C(34b)).
˚
˚
Sn(2)–O(1) 2.071(4) A, Sn(2)–N(2) 2.721(5) A, Sn(3)–S(2)
˚
˚
2.4280(17) A, Sn(3)–N(3) 2.853(5) A, Sn(4)–O(2) 2.076-
(4) A and Sn(4)–N(4) 2.756(5) A in complex 2, and
˚
˚

2020
C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 2014–2022
Table 4
pÁ Á Áp, C–HÁ Á Áp and intra-hydrogen bonds for 2, 5 and 8
˚
˚
˚
D–HÁ Á ÁA
D–H (A)
HÁ Á ÁA (A)
DÁ Á ÁA (A)
D–HÁ Á ÁA (°)
5
8
C(22)–H(22)Á Á ÁN(1)
C(36)–H(36)Á Á ÁN(2)
C(30)–H(30)Á Á ÁO(1)
C(6)–H(6)Á Á ÁN(2)
0.93
0.93
0.93
0.93
2.61
2.50
2.58
2.56
3.290
3.706
3.267
3.231
131
120
131
129
˚
˚
C–HÁ Á Áp
HÁ Á ÁCg (A)
CÁ Á ÁCg (A)
C–HÁ Á ÁCg (°)
2
5
8
C(57)–H(57)Á Á ÁCg(1)i
C(38)–H(38)Á Á ÁCg(2)ii
C(20a)–H(20a)Á Á ÁCg(3)iii
C(2a)–H(2a)Á Á ÁCg(4)iv
3.128
2.829
2.912
2.710
3.943
3.527
3.660
3.599
147.34
132.75
138.47
160.50
p(i)Á Á Áp(j)a
Dihedral angle (i,j) (°)
Centroid separation CgÁ Á ÁCgb (A)
3.811
Cg(i)Á Á Áperp (A)
3.4505
Cg(j)Á Á Áperpd (A)
3.5955
c
˚
˚
˚
2
5
Cg(5)Á Á ÁCg(6)v
6.0
16.2
Cg(7)Á Á ÁCg(8)vi
3.859
3.3018
3.6995
a
Where Cg(1), Cg(2), Cg(3), Cg(4), Cg(5), Cg(6), Cg(7) and Cg(8) are referred to the centroids of C(59a)–C(60a)–C(61a)–C(62a)–C(63a)–C(64a),
C(29b)–C(30b)–C(31b)–C(32b)–C(33b)–C(34b), C(11)–C(12)–C(13)–C(14)–C(15)–C(16), C(35)–C(36)–C(37)–C(38)–C(39)–C(40), N(1)–C(1)– N(2)–C(2)–
C(3)–C(4), C(65)–C(66)–C(67)–C(68)–C(69)–C(70), N(1)–C(1)– N(2)–C(2)–C(3)–C(4) and C(29a)–C(30a)–C(31a)—C(32a)–C(33a)–C(34a), respectively.
b
CgÁ Á ÁCg is the distance between ring centroids; symmetry transformation: (i) 1 À x, 1 À y, 1 À z; (ii) 2 À x, Ày, 1 À z; (iii) À1/2 + x, 3/2 À y, z; (iv) x, y,
z; (v) x, y, z and (vi) 1 À x, À y, Àz.
c
Cg(i)Á Á Áperp is the perpendicular distance of Cg(i) on ring j.
d
Cg(j)Á Á Áperp is the perpendicular distance of Cg(i) on ring i.
distance of C(57)Á Á ÁCg and H(57)Á Á ÁCg are 3.943 and
Complex 8 is also a monomer with one ligand coordi-
nated to two triphenyltin moiety. The central tin atoms
are five-coordinated with distorted trigonal bipyramidal
˚
3.128 A, respectively. The angle of C(57)–H(57)Á Á ÁCg is
147.34°. Similarly in complex 5, ring (C29a–C34a) and
ring (C1–C4, N1, N2) (symmetry codes: 1 À x, Ày, Àz)
˚
are stacked at a ring centroid distance of 3.859 A (dihe-
dral angle 16.2°). C–HÁ Á Áp interaction occurs between
C(38)–H and ring (C29b–C34b) (symmetry codes: 2 À x,
˚
Ày, 1 À z). The data are C(38)Á Á ÁCg 3.527 A,
˚
H(57)Á Á ÁCg 2.829 A, C(38)–H(38)Á Á ÁCg 132.75°. In addi-
tion to the mentioned p-interactions, the molecules of 5
are involved in weak intramolecular C–HÁ Á ÁN and C–
˚
HÁ Á ÁO hydrogen bonds (C(22)–H(22)Á Á ÁN(1) 3.290(12) A,
˚
131°; C(36)–H(36)Á Á ÁN(2) 3.267(11) A, 131°; C(30)–
˚
H(30)Á Á ÁO(1) 3.706(10) A, 120°). All the above weak but
significant interactions stabilize these crystal structures.
3.2.2. Ph3Sn(C4H2N2S2)SnPh3 (8)
˚
Fig. 5. Molecular structure of complex 8.
Selected bond lengths (A) and bond angles (°) for 8 are
given in Table 5, and its molecular structure and network
are shown in Figs. 5 and 6, respectively.
Table 5
˚
Selected bond lengths (A) and bond angles (°) for 8
Sn(1)–C(17)
Sn(1)–S(1)
Sn(2)–C(23)
Sn(2)–C(29)
S(1)–C(1)
2.118(3)
2.4444(7)
2.112(3)
2.136(3)
1.751(3)
Sn(1)–C(5)
Sn(1)–C(11)
Sn(2)–C(35)
Sn(2)–S(2)
S(2)–C(4)
2.136(3)
2.152(3)
2.125(3)
2.4495(8)
1.739(3)
C(17)–Sn(1)–C(5)
C(5)–Sn(1)–C(11)
C(5)–Sn(1)–S(1)
C(23)–Sn(2)–C(35)
C(35)–Sn(2)–C(29)
C(35)–Sn(2)–S(2)
116.94(11)
108.26(11)
118.73(8)
113.93(11)
110.84(10)
111.59(7)
C(17)–Sn(1)–C(11)
C(17)–Sn(1)–S(1)
C(11)–Sn(1)–S(1)
C(23)–Sn(2)–C(29)
C(23)–Sn(2)–S(2)
C(29)–Sn(2)–S(2)
108.93(11)
107.31(8)
93.99(7)
107.83(11)
116.57(8)
94.20(8)
Fig. 6. Perspective view of complex 8 showing edge- or point-to-face C–
HÁ Á Áp interactions (C(20a)–H(20a)Á Á ÁCg(3)) (Cg(3): C(11)–C(12)–C(13)–
C(14)–C(15)–C(16)) (C(2a)–H(2a)Á Á ÁCg(4)) (Cg(4): C(35)–C(36)–C(37)–
C(38)–C(39)–C(40)).

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 2014–2022
2021
geometry. The ligands adopt its thiol sulfur atom and het-
erocyclic nitrogen atoms to coordinate to the central tin
atoms. The equatorial plane are defined by S(1), C(5) and
C(17) for Sn(1), S(2), C(23) and C(35) for Sn(2) with the
sum of 342.99° (S(1)–Sn(1)–C(5) 118.73°, S(1)–Sn(1)–
C(17) 103.72°, C(17)–Sn(1)–C(5) 116.94°) and 342.09°
(S(2)–Sn(1)–C(35) 111.59°, S(2)–Sn(1)–C(23) 116.56°,
C(35)–Sn(1)–C(23) 113.94°). The axial positions are occu-
pied by C(11), N(2) for Sn(1), and C(29), N(1) for Sn(2)
with the angles of 153.35° and 151.92°. The Sn–S and
deposited with the Cambridge Crystallographic Data Cen-
ter as supplementary publication CCDC Nos. 257750,
257759, 274749, respectively. Copies of the data can be
obtained free of charge on application to the Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:
+44 1223 336033; e-mail: deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.ck). Supplementary data associ-
ated with this article can be found, in the online version,
at doi:10.1016/j.jorganchem.2005.12.054.
˚
Sn–N bond lengths are Sn(1)–S(1) 2.4444(7) A, Sn(2)–
References
˚
˚
S(2) 2.4495(8) A, Sn(2)–N(1) 2.926 A and Sn(1)–N(2)
˚
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˚
˚
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˚
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˚
Pymt) (2.835(7) A) [27], and still shorter than the sum of
˚
the van der Waals radii of tin and nitrogen (3.74 A).
The molecules of 8 associate via edge- or point-to-face C–
HÁ Á Áp interactions. The C(20a)–H atom is directed towards
the symmetry related (À1/2 + x, 3/2 À y, z) aromatic ring
containing the C(11)–C(16) atoms. The distance of
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Nonlinear Optics: Chemical Perspectives, ACS Symposium Series,
Washington DC, 1991;
˚
C(20a)Á Á ÁCg and H(20a)Á Á ÁCg are 3.660 and 2.912 A, respec-
tively. The angle of C(20a)–H(20a)Á Á ÁCg is 138.47°. Another
C–HÁ Á Áp interaction occurs between C(2a)–H and ring
(C35–C40) (symmetry codes: x, y, z). The data are
(c) O.R. Evans, W. Lin, Acc. Chem. Res. 35 (2002) 511;
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˚
˚
C(2a)Á Á ÁCg 3.599 A, H(2a)Á Á ÁCg 2.710 A, C(2a)–H(2a)Á Á ÁCg
160.50°. Further, intramolecular C–HÁ Á ÁN hydrogen bonds
˚
(C(6)–H(6)Á Á ÁN(2) 3.231(4) A, 129°) stabilize the structure.
4. Conclusions
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In summary, a series of triorganotin(IV) complexes
based on substituent pyrimidine ligands have been synthe-
sized and characterized. Detailed studies on the structures
of these complexes indicate that complexes 2, 5 and 8 exhi-
bit fascinating self-assembled structural topologies via
cooperative hydrogen bonds and offset pÁ Á Áp stacking inter-
actions and edge- or point-to-face C–HÁ Á Áp interactions.
Therefore, the understanding and utilization of the non-
covalent interactions including hydrogen bonds, pÁ Á Áp
stacking interactions and C–HÁ Á Áp interactions may cast
light on the further development of supramolecular chemis-
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Acknowledgement
The authors thank the National Natural Science Foun-
dation of China (20271025) for financial support.
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