C. Ma et al. / Inorganica Chimica Acta 361 (2008) 380–386
381
In this paper, we report the syntheses, characterization
and crystal structures of the related triorganotin derivatives
1–4. All the complexes have been characterized by elemen-
2.2.2. Synthesis of (n-Bu)3Sn(SC2N3HNH2-3) (2)
The solid is obtained from ethyl ether. Yield: 81%.
m.p. 71–73 ꢁC. Anal. Calc. for C14H30N4SSn: C, 41.50;
H, 7.46; N, 13.83. Found: C, 41.38; H, 7.34; N,
13.81%. IR (KBr, cmÀ1): m(N–H) 3298, m(C@N) 1610,
mas(Sn–C) 528, ms(Sn–C) 500, m(Sn–N) 483, m(Sn–S) 308.
1H NMR (CDCl3, ppm): d 0.85–1.71 (m, 27H, Sn–
C4H9), 5.20 (s, 2H, C–NH2), 11.41 (s, H, N–H). 13C
NMR (CDCl3, ppm): d 165.3 (C–S), 143.2 (C–NH2),
13.5, 26.3, 27.5, 29.2 (n-Bu).
1
tal analysis, IR, H and 13C NMR spectra. The geometry
about Sn of complex 1 is distorted trigonal bipyramidal
and the supramolecular structures of complex 1 has been
found consist of 3D channels built up by intermolecular
N–HÁ Á ÁN hydrogen bonding. The geometry of tin atoms
in complexes 3 and 4 are distorted tetrahedron and 1D
polymers connected by intermolecular N–HÁ Á ÁN hydrogen
bonding or N–HÁ Á ÁN and N–HÁ Á ÁS hydrogen bonding.
2.2.3. Synthesis of Ph3Sn(SC2N3HNH2-3) (3)
2. Experimental
The solid is then recrystallized from ethyl ether and the
white crystal complex 3 is formed. Yield: 88%. m.p.
182–184 ꢁC. Anal. Calc. for C20H18N4SSn: C, 51.64; H,
3.90; N, 12.04. Found: C, 51.51; H, 3.89; N, 11.88%. IR
(KBr, cmÀ1): m(N–H) 3305, m(C@N) 1598, mas(Sn–C) 464,
ms(Sn–C) 429, m(Sn–N) 487, m(Sn–S)311. 1H NMR (CDCl3,
ppm): d 7.26–7.64 (m, 15H, Sn–C6H5), 5.00 (s, 2H, C–
NH2), 11.37 (s, H, N–H). 13C NMR (CDCl3, ppm): d
165.5 (C–S), 143.7 (C–NH2), 127.9 (m-C), 129.3 (p-C),
136.5 (o-C), 148.3 (i-C).
2.1. Materials and measurements
Trimethyltin chloride, tri-n-butyltin chloride, triphe-
nyltin chloride, 3-amino-5-mercapto-1,2,4-triazole are
commercially available, and they are used without fur-
ther purification. Tribenzyltin chloride was prepared by
a standard method reported in the literature [11]. The
melting points were obtained with Kofler micro-melting
point apparatus and were uncorrected. Infrared-spectra
were recorded on a Nicolet-5700 spectrophotometer
using KBr discs and sodium chloride optics. 1H and
13C NMR spectra were recorded on Varian Mercury Plus
400 spectrometer operating at 400 and 100.6 MHz,
respectively. The spectra were acquired at room temper-
ature (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
2.2.4. Synthesis of (C6H5CH2)3Sn(SC2N3HNH2-3) (4)
The solid is then recrystallized from ethyl ether and the
white crystal complex 4 is formed. Yield: 79%. m.p. 138–
140 ꢁC. Anal. Calc. for C23H24N4SSn: C, 54.46; H, 4.77;
N, 11.05. Found: C, 54.41; H, 4.62; N, 10.99%. IR (KBr,
cmÀ1): m(N–H) 3245, m(C@N)1603, mas(Sn–C) 450, ms(Sn–
C) 427, m(Sn–N) 483, m(Sn–S)307. 1H NMR (CDCl3,
ppm): d 3.51 (s, 6H, Sn–CH2C6H5), 7.19–7.34 (s, 15H,
Sn–CH2C6H5), 5.09 (s, 2H, C–NH2), 11.22 (s, H,
N–H).13C NMR (CDCl3, ppm): d 165.1 (C–S), 143.4
(C–NH2), 37.5 (CH2-Ph), 127.5 (m-C), 128.6 (p-C), 134.5
(o-C), 147.6 (i-C).
1
stated relative to external tetramethylsilane (TMS) for H
and 13C NMR. Elemental analyses were performed with
a PE-2400II apparatus.
2.2. Syntheses of the complexes 1–4
3. Results and discussion
The reaction was carried out under nitrogen atmosphere
with use of standard Schlenk techniques. The 3-amino-5-
mercapto-1,2,4-triazole and the sodium ethoxide were
added to the solution of benzene (20 ml), the mixture was
stirred for 0.5 h. and then added triorganotin(IV) chloride
to the mixture, continuing the reaction for 12 h at 40 ꢁC.
After cooling down to room temperature, filtered it. The
solvent of the filtrate was gradually removed by evapora-
tion under vacuum until solid product is obtained.
3.1. Syntheses
The synthesis procedure is shown in Scheme 1.
3.2. IR
The explicit feature in the infrared spectra of all com-
plexes is the absence of the band in the region of 2558–
2469 cmÀ1, which appears in the free-ligand as m(S–H)
vibration. For complexes 1–4, the N–H stretching fre-
quency reveal an upward shift 20–50 cmÀ1 relative to
the frequency of the free ligand in the solids, which is
indicative of the formation of an intermolecular N–
HÁ Á ÁN hydrogen bond. IR spectra appearing in the
region 272–283 cmÀ1 are assigned to the Sn–S stretching
mode of vibration, all of which are consistent with those
detected in a number of organotin(IV)–sulfur complexes
[12–14].
2.2.1. Synthesis of (CH3)3Sn(SC2N3HNH2-3) (1)
The colorless crystal complex 1 is formed from ethyl
ether. Yield: 76%. m.p. 124–126 ꢁC. Anal. Found: C,
21.41; H, 4.25; N, 19.90. Calc. for C5H12N4SSn: C, 21.53;
H, 4.34; N, 20.08%. IR (KBr, cmÀ1): m(N–H) 3321,
m(C@N)1607, mas(Sn–C) 530, ms(Sn–C) 502, m(Sn–N) 496,
m(Sn–S) 310. 1H NMR (CDCl3, ppm): d 0.73 (s, 9H,
2JSnH = 58 Hz), d 0.76 (s, 9H, Sn–CH3), 4.81 (s, 2H, C–
NH2), 11.50 (s, H, N–H). 13C NMR (CDCl3, ppm): d
165.2 (C–S), 143.6 (C–NH2), 8.09 (Me).