Self-assembly syntheses and crystal structures of triphenyltin(IV) phenylphosphate: A 1D polymer and a dimer of 24-membered macrocycle

Article abstract of DOI:10.1016/j.inoche.2007.07.033

Two novel organotin(IV) complexes of the types [(Ph₃Sn)₄(O₃POPh)₂]_n 1 and [(Ph₃Sn)₆(O₃POPh)₃]₂ 2 have been prepared by treatment of phenylphosphoric acid and the Ph₃SnCl under different conditions. The complexes 1 and 2 were characterized by elemental analysis, IR and NMR (¹H,¹³C,¹¹⁹Sn) spectroscopy and X-ray crystallography diffraction analysis. The structure analyses reveal that complex 1 is an infinite 1D polymer and complex 2 is a dimer which contains two 24-membered macrocycles.

Full text of DOI:10.1016/j.inoche.2007.07.033

Available online at www.sciencedirect.com
Inorganic Chemistry Communications 10 (2007) 1330–1334
www.elsevier.com/locate/inoche
Self-assembly syntheses and crystal structures of triphenyltin(IV)
phenylphosphate: A 1D polymer and a dimer of 24-membered
macrocycle
a,b,
a
a
b
Chunlin Ma
*, Mingqing Yang , Rufen Zhang , Jikun Li
a
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
b
Taishan University, Taian 271021, PR China
Received 11 July 2007; accepted 24 July 2007
Available online 24 August 2007
Abstract
Two novel organotin(IV) complexes of the types [(Ph3Sn)4(O3POPh)2]n 1 and [(Ph3Sn)6(O3POPh)3]2 2 have been prepared by treat-
ment of phenylphosphoric acid and the Ph3SnCl under different conditions. The complexes 1 and 2 were characterized by elemental anal-
ysis, IR and NMR (1H,13C,119Sn) spectroscopy and X-ray crystallography diffraction analysis. The structure analyses reveal that
complex 1 is an infinite 1D polymer and complex 2 is a dimer which contains two 24-membered macrocycles.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Triphenyltin(IV); Phenylphosphoric acid; Crystal structures; Macrocycle
Metal-directed self-assembly has become a powerful tool
for the construction of systems possessing intrinsic physical
and chemical properties that are promising for the creation
of new materials and new metal-based drugs in recent years
[1]. Among them, organotin(IV) complexes are attracting
more and more attention because of their potential indus-
trial applications and interesting topologies [2,3]. A large
of organotin(IV) carboxylates have been prepared and
structurally characterized [4,5]. In contrast, a relatively less
clear picture on the structural coordination chemistry of
organotin(IV) phosphates was developed [6]. Comparing
with the carboxylate group, the phosphate group contains
three potential coordinating oxygen atoms. So the phos-
phate group can coordinate as dianionic group with the
tin atoms and give rise to various structural types such as
monomer, dimer, polymer and macrocyclic hexamer [7,9].
Herein, we synthesized two new organotin(IV) complexes
with the sodium salt of the phenylphosphoric acid and tri-
phenyltin(IV) chloride under different conditions (Scheme
1). The complexes 1 and 2 were characterized by elemental
analysis, IR and NMR (1H,13C,119Sn) spectroscopy and X-
ray crystallography diffraction analysis.
The main feature in the IR spectrum of complexes 1 and
2 is the absence of a band in the region between 3300 and
3550 cmꢀ1, where the v(O–H) vibration in the free ligand
appears, which indicates metal–ligand bond formation.
1
The H NMR spectrum of the complexes 1 and 2 shows
that the signal for the –OH proton in the spectrum of the
ligand is absent, thus indicating the removal of the –OH
proton and the formation of Sn–O bonds. They are consis-
tent with the IR data. The 119Sn NMR spectrum of com-
plexes 1 and 2 shows distinct resonances at 63.6, ꢀ125.8
and 62.8, ꢀ126.7 ppm, respectively. As reported in the lit-
erature, value of d(119Sn) in the ranges ꢀ210 to ꢀ400, ꢀ90
to ꢀ190 and 200 to ꢀ60 ppm has been associated with six-,
five- and four-coordinate tin centers, respectively [8]. On
this basis, we can conclude roughly that the tin atoms of
*
Corresponding author. Address: Department of Chemistry, Liaocheng
University, Liaocheng 252059, PR China. Tel.: +86 635 8230660; fax: +86
538 6715521.
E-mail address: macl@lcu.edu.cn (C. Ma).
1387-7003/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2007.07.033

C. Ma et al. / Inorganic Chemistry Communications 10 (2007) 1330–1334
1331
Ph
Ph
Ph
Ph
O
Sn
O
Ph
Sn
Ph
Sn
Ph
Ph
O
Ph
O
CH3CH2OH
P
O
O
P
O
4h, refluxing
O
Ph
Ph
Sn
Ph
n
Ph
Ph
O
Ph
Ph
O P
OH
Ph
Ph
O
+
+
Ph3SnCl EtONa
Sn
OH
O
Ph
Sn
Ph
Ph
Ph
Sn
Ph
P
O
O
Ph
Ph
Sn
O
Ph
O
O
O
Ph
Ph
O
P
Sn Ph
Ph
P
Ph
Ph
O
O
O
C6H6
Ph
Ph
Ph
Ph
24h, 25 oC
Sn Ph
O
Sn Ph
O
Ph
Sn
P
O
O
Ph
P
Ph
Ph
Sn
O
Ph
O
Ph
O
O
Sn
Ph
O
O
Ph
O
P
Ph
Ph
Ph
Sn Ph
Ph
Ph
Ph
O
Ph
Sn
Ph
Ph
Scheme 1.
the two complexes are four-and five-coordinated and this
can be confirmed by the X-ray crystal structures of com-
plexes 1 and 2.
The complex 1 forms an infinite coordination polymer
(Fig. 1). As shown in Fig. 1, the geometry of all the tin
atoms involved can be classed in two types, the five-coordi-
nate tin [Sn(1), Sn(2)] and the four-coordinate tin [Sn(3),
Sn(4)]. In the case of Sn(1), the tin atom exits in a distorted
trigonal bipyramidal environment with two oxygen atoms
and three phenyl groups, which exhibits a trans-R3SnO2
geometry. The axial positions are occupied by O(4) and
O(5) and axial angle is 176.7(2)ꢁ. The sum of the angles
subtended at the tin atom in the equatorial plane is
359.93ꢁ, so that the atoms Sn(1), C(43), C(49) and C(55)
Fig. 1. The 1D polymeric chain structure of complex 1. [The a-carbon of phenyl ring (Sn–Ph) is reserved, and the other carbons, which are omitted for
˚
clarity.] Selected bond lengths (A) and angles (ꢁ): Sn(1)–C(43) 2.120(8), Sn(1)–C(49) 2.124(9), Sn(1)–C(55) 2.125(8), Sn(1)–O(4) 2.240(5), Sn(1)–O(5)
2.215(5), Sn(2)–C(19) 2.120(8), Sn(2)–C(25) 2.117(8), Sn(2)–C(31) 2.122(9), Sn(2)–O(3) 2.210(5), Sn(3)–O(1) 1.986(5), Sn(3)–C(1) 2.131(9), Sn(3)–C(7)
2.115(9), Sn(3)–C(13) 2.115(11), Sn(4)–O(6) 1.985(6), Sn(4)–C(61) 2.108(12), Sn(4)–C(67) 2.115(10), Sn(4)–C(73) 2.109(6), P(1)–O(1) 1.538(6), P(1)–O(2)
1.572(7), P(1)–O(3) 1.469(5), P(1)–O(4) 1.471(5); C(43)–Sn(1)–C(49) 121.3(3), C(43)–Sn(1)–C(55) 118.5(3), C(49)–Sn(1)–C(55) 120.1(3), O(4)–Sn(1)–O(5)
176.7(2), C(19)–Sn(2)–C(31) 117.6(3), C(25)–Sn(2)–C(31) 123.2(3), C(25)–Sn(2)–C(19) 119.2(4), O(3)–Sn(2)–O(7)#1 177.46(18), C(7)–Sn(3)–C(1) 108.6(4),
C(13)–Sn(3)–C(1) 121.5(4), C(7)–Sn(3)–C(13) 111.7(4), C(61)–Sn(4)–C(67) 112.8(4), C(61)–Sn(4)–C(73) 111.1(3), C(73)–Sn(4)–C(67) 113.5(4), O(1)–P(1)–
O(2) 99.7(3), O(3)–P(1)–O(1) 108.6(3), O(4)–P(1)–O(1) 108.7(3), O(3)–P(1)–O(2) 112.5(3), O(4)–P(1)–O(2) 107.4(3), O(3)–P(1)–O(4) 118.2(3). #1 x+1, y, z.

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C. Ma et al. / Inorganic Chemistry Communications 10 (2007) 1330–1334
are almost in the same plane. The environment of Sn(2) is
also a distorted trigonal bipyramidal with two oxygen
atoms and three phenyl-C moiety [O(3)–Sn(2)–
O(7)#1 = 177.46(18)ꢁ]. For Sn(3), the coordination geome-
try about the tin atoms is best described as distorted tetra-
hedral geometry defined by three ipso-C atoms of the
phenyl groups and O(1) atom of the ligand. The coordina-
tion environment about the Sn(4) is the same to Sn(3). All
the oxygen atoms of the phosphate group coordinated to
the tin atoms. The bond lengths of Sn(1)–O(4), Sn(2)–
Snꢁ ꢁ ꢁSn and transannular Pꢁ ꢁ ꢁP distances, which are
˚ ˚
12.048–12.428 A and 14.027–14.301 A, respectively. Worth
mentioning here is that although the dimensions of the cav-
ity in this complex are ostensibly large enough to capture
guest molecules, they are almost completely occupied by
the phenyl groups on tin atoms.
To study the stability of complexes 1 and 2, thermo-
gravimetric analysis (TGA) was performed in the tempera-
ture range of 50–500 ꢁC under N2 atmosphere. The TGA
curves of complexes 1 and 2 exhibit one continuous weight
loss stages in the range of 170–300 ꢁC (Figs. 4 and 5). In
general, complexes 1 and 2 exhibit good thermal stability
[11].
From the experiments above we can conclude that dif-
ferent crystal structures were obtained when we use the
same reagent but change the experimental conditions. This
observation tells us that the experimental conditions are
important in view of the design of molecular structures,
so we can choose different experimental conditions in order
to obtain some valuable complexes with specific topologies
and applications [12].
˚
˚
O(3) and Sn(3)–O(1), are 2.240(5) A, 2.210(5) A and
˚
1.986(5) A, respectively [9]. The phosphorus atoms, of
which there is only one kind, are found at the center of a
distorted tetrahedron with four oxygen atoms as nearest
neighbors. Moreover, there exists a disordered phenyl ring
(C79-C84 and C790-C840) in complex 1.
For complex 2, the asymmetric unit contains two mono-
mers A and B (see Fig. 2), which are crystallographically
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 [10]. As can
be seen from Fig. 3, the molecule A is a 24-membered mac-
rocycle. The geometry of all the tin atoms involved can also
be classed in two types, the five-coordinate tin [Sn(1),
Sn(2), Sn(3)] and the four-coordinate tin [Sn(4), Sn(5)].
The Sn(1) atom exits in a distorted trigonal bipyramidal
environment with two oxygen atoms and three phenyl
groups. The axial positions are occupied by O(2) and
O(11) and axial angle is 177.5 (4)ꢁ. The sum of the trigonal
plane angles is 360ꢁ, which illustrates Sn(1), C(1), C(7) and
C(13) are coplanar. For Sn(5), the coordination geometry
about the tin atoms can also be described as distorted tet-
rahedral geometry defined by three ipso-C atoms of the
phenyl groups and O(3) atom of the ligand. The bond
lengths of Sn(1)–O(2), Sn(1)–O(11) and Sn(5)–O(3) are
Experimental section
Synthesis of complex 1. The phenylphosphoric acid
(0.087 g, 0.5 mmol) and EtONa (0.068 g, 1 mmol) were
added to the solution of dry ethanol (30 ml) in standard
Schlenk technique, and the mixture was stirred for
10 min. Triphenyltin(IV) chloride (0.386 g, 1 mmol) was
then added to the mixture, and the reaction was refluxed
for 4 h. The solution was filtered and the solvent of the fil-
trate was gradually removed by evaporation under vacuum
until solid product was obtained. The solid was then recrys-
tallized from dichloromethane to give colorless crystals of
complex 1. Yield: 62%. m.p. 188–190 ꢁC. Anal. Calc. for
C84H70O8P2Sn4: C 57.84, H 4.05; Found: C 57.41, H 4.22
%. IR (KBr, cmꢀ1): 3046, 1636, 1593, 1429, 1156, 1078,
1010, 693, 660, 530, 450.1H NMR (CDCl3, ppm): d 7.23–
˚
˚
˚
2.206(10) A, 2.201(11) A and 2.002(12) A, respectively,
which are almost the same to those of complex 1. The size
of cavity in this macrocycle can be evaluated from the
Fig. 2. Molecular structure of complex 2.

C. Ma et al. / Inorganic Chemistry Communications 10 (2007) 1330–1334
1333
Fig. 4. TGA curve of complex 1.
Fig. 3. The 24-membered macrocycle structure. [The a-carbon of phenyl
ring (Sn–Ph) is reserved, and the other carbons, which are omitted for
˚
clarity.] Selected bond lengths (A) and angles (ꢁ): Sn(1)–C(1) 2.147(16),
Sn(1)–C(7) 2.167(18), Sn(1)–C(13) 2.111(16), Sn(1)–O(2) 2.206(10), Sn(1)–
O(11) 2.201(11), Sn(2)–C(43) 2.144(18), Sn(2)–C(49) 2.116(19), Sn(2)–
C(55) 2.150(17), Sn(2)–O(4) 2.215(10), Sn(2)–O(5) 2.178(11), Sn(3)–C(85)
2.130(2), Sn(3)–C(91) 2.110(2), Sn(3)–C(97) 2.127(18), Sn(3)–O(8)
2.191(11), Sn(3)–O(9) 2.239(11), Sn(4)–C(109) 2.130(19), Sn(4)–C(115)
2.125(19), Sn(4)–C(121) 2.105(19), Sn(4)–O(10) 2.006(11), Sn(5)–C(25)
2.110(2), Sn(5)–C(31) 2.097(19), Sn(5)–C(37) 2.090(2), Sn(5)–O(3)
2.002(12), P(1)–O(1) 1.597(12), P(1)–O(2) 1.501(11), P(1)–O(3) 1.508(12),
P(1)–O(4) 1.473(10); C(1)–Sn(1)–C(7) 121.6(7), C(7)–Sn(1)–C(13) 121.0(6),
C(3)–Sn(1)–C(13) 117.4(7), O(2)–Sn(1)–O(11) 177.5(4), C(43)–Sn(2)–C(55)
120.8(7), C(49)–Sn(2)–C(55) 120.3(7), C(43)–Sn(2)–C(49) 118.9(7), O(4)–
Sn(2)–O(5) 177.3(4), C(91)–Sn(3)–C(85) 119.5(8), C(97)–Sn(3)–C(85)
118.8(7), C(91)–Sn(3)–C(97) 121.7(8), O(8)–Sn(3)–O(9) 178.9(5), C(115)–
Sn(4)–C(109) 109.9(7), C(121)–Sn(4)–C(109) 114.3(7), C(121)–Sn(4)–
C(115) 116.3(8), C(25)–Sn(5)–C(31) 110.3(8), C(25)–Sn(5)–C(37)
111.1(8), C(31)–Sn(5)–C(37) 118.4(8), O(1)–P(1)–O(2) 108.1(6), O(2)–
P(1)–O(3) 111.9(6), O(3)–P(1)–O(4) 110.7(7), O(3)–P(1)–O(1) 103.7(6),
O(1)–P(1)–O(4) 108.3(6), O(2)–P(1)–O(4) 113.6(6).
7.40 (m, 10H, O–C6H5), 7.66–7.80 (m, 60H, Sn–C6H5). 13
C
Fig. 5. TGA curve of complex 2.
NMR (CDCl3, ppm): d 128.0–129.1 (O–C6H5), 135.8–136.8
(Sn–C6H5).119Sn NMR (CDCl3, ppm): d 63.6, ꢀ125.8.
Synthesis of complex 2. The phenylphosphoric acid
(0.087 g, 0.5 mmol) and EtONa (0.068 g, 1 mmol) were
added to the solution of dry benzene (30 ml) in standard
Schlenk technique, and the mixture was stirred for
10 min. Triphenyltin(IV) chloride (0.386 g, 1 mmol) was
then added to the mixture, and the reaction was allowed
to continue for 24 h at 25 ꢁC. The solution was filtered
and the solvent of the filtrate was gradually removed by
evaporation under vacuum until solid product was
obtained. The solid was then recrystallized from dichloro-
methane to give colorless crystals of complex 2. Yield:
67%. m.p. 218–220 ꢁC. Anal. Calc. for C252H210O24P6Sn12:
C 57.84, H 4.05; Found: C 57.56, H 4.31%. IR (KBr,
cmꢀ1): 3046, 1636, 1593, 1429, 1156, 1078, 1010, 693,
660, 530, 450.1H NMR (CDCl3, ppm): d 7.21–7.38 (m,
30H, O–C6H5), 7.68–7.83 (m, 180H, Sn–C6H5). 13C
NMR (CDCl3, ppm): d 127.4–128.5 (O–C6H5), 135.4–
137.1 (Sn–C6H5). 119Sn NMR (CDCl3, ppm): d 62.8,
ꢀ126.7.
X-ray crystallography. X-ray crystallographic data were
collected on a Bruker SMART CCD 1000 diffractometer with
˚
graphite monochromated Mo Ka radiation (k = 0.71073 A)
at 298(2) K. A semiempirical absorption correction 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 [13]. Hydrogen

1334
C. Ma et al. / Inorganic Chemistry Communications 10 (2007) 1330–1334
[2] (a) G. Prabusankar, R. Murugavel, Organometallics 23 (2004) 5644;
atoms were placed in calculated positions. Figures in this
paper were created by the X-Seed software packages [14,15].
Selected crystal data for complex 1: C84H70O8P2Sn4,
´
(b) R. Garcıa-Zarracino, J. Ramos-Quinones, H. Ho¨pfl, Inorg. Chem.
˜
42 (2003) 3835;
´
(c) R. Garcıa-Zarracino, H. Ho¨pfl, J. Am. Chem. Soc. 127 (2005)
˚
ꢀ
FW = 1744.10; Triclinic; P1; a = 12.369(7) A, b = 14.486(7)
3120.
˚
˚
A, c = 23.055(13) A, a = 74.496(10)ꢁ, b = 82.809(10)ꢁ,
[3] (a) C.L. Ma, Q.F. Zhang, R.F. Zhang, D.Q. Wang, Chem. Eur. J. 12
(2006) 420;
3
˚
c = 83.966(10)ꢁ; V = 3938.0(4) A , Z = 2, Dcalc = 1.471 mg/
m3, l = 1.347 mmꢀ1, F(000) = 1736; Crystal size = 0.18
· 0.12 · 0.10 mm3. 19,799 reflections collected for 2.10
to 25.01ꢁ, 13,670 independent reflections (Rint = 0.0195).
R1 = 0.0580, wR2 = 0.1442 and S = 1.030 for observed
(b) C.L. Ma, Q. Jiang, R.F. Zhang, D.Q. Wang, J. Chem. Soc.,
Dalton Trans. (2003) 2975;
(c) C.L. Ma, J.F. Sun, J. Chem. Soc., Dalton Trans. (2004) 1785.
[4] (a) G.L. Zheng, J.F. Ma, Z.M. Su, L.K. Yan, J. Yang, Y.Y. Li, J.F.
Liu, Angew. Chem., Int. Ed. 43 (2004) 2409;
(b) C.L. Ma, Y.F. Han, R.F. Zhang, D.Q. Wang, Eur. J. Inorg.
Chem. (2005) 3024.
[5] (a) S.W. Ng, C. Wei, V.G. Kumar Das, J. Organomet. Chem. 345
(1988) 59;
reflections with I > 2r(I). Selected crystal data for complex
ꢀ
2:
C
252H210O24P6Sn12, FW = 5232.30; Triclinic; P1;
˚
˚
˚
a = 22.469(5) A, b = 23.867(5) A, c = 26.329(5) A, a = 100.
3
˚
81(3)ꢁ, b = 112.11(3)ꢁ, c = 101.09(3)ꢁ; V = 12294 (4) A ,
(b) S.W. Ng, J.M. Hook, Main Group Metal Chem. 22 (1999) 163;
(c) P.G. Harrison, K. Lambert, T.J. King, B. Majee, J. Chem. Soc.,
Dalton Trans. (1983) 363;
(d) G.K. Sandhu, S.P. Verma, E.R.T. Tiekink, J. Organomet. Chem.
393 (1990) 195.
Z = 2, Dcalc = 1.413 mg/m3, l = 1.295 mmꢀ1
,
F(000)
= 5208; Crystal size = 0.20 · 0.13 · 0.08 mm3. 60,271 reflec-
tions collected for 1.55 to 25.01ꢁ, 41,714 independent reflec-
tions (Rint = 0.0981). R1 = 0.0921, wR2 = 0.1887 and
S = 1.009 for observed reflections with I > 2r(I).
[6] (a) F. Ribot, C. Sanchez, M. Biesemans, F.A. Mercier, J.C. Martins,
M. Gielen, R. Willem, Organometallics 20 (2001) 2593;
(b) S.Y. Song, J.F. Ma, J. Yang, L.L. Gao, Z.M. Su, Organometallics
26 (2007) 2125.
[7] (a) V. Chandrasekhar, V. Baskar, A. Steiner, S. Zacchini, Organo-
metallics 21 (2002) 4528;
Supplementary material
CCDC 643928 and 644085 contain the supplementary
crystallographic data for 1 and 2. These data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
(b) V. Chandrasekhar, V. Baskar, R. Boomishankar, K. Gopal, S.
Zacchini, J.F. Bickley, A. Steiner, Organometallics 22 (2003) 3710;
(c) V. Chandrasekhar, V. Baskar, A. Steiner, S. Zacchini, Organo-
metallics 23 (2004) 1390.
[8] J. Holecek, M. Nadvornik, K. Handlir, A. Lycka, J. Organomet.
Chem. 315 (1986) 299.
[9] (a) K.C. Molloy, M.B. Hossain, D. Van der Helm, D. Cunningham,
J.J. Zuckerman, Inorg. Chem. 20 (1981) 2402;
(b) K.C. Molloy, F.A.K. Nasser, C.L. Barnes, D.V.D. Helm, J.J.
Zuckerman, Inorg. Chem. 21 (1982) 960.
Acknowledgement
[10] C.L. Ma, G.R. Tian, R.F. Zhang, J. Organomet. Chem. 691 (2006)
2014.
[11] C.L. Ma, G.R. Tian, R.F. Zhang, Inorg. Chem. Commun. 9 (2006)
882.
[12] C.L. Ma, J.K. Li, R.F. Zhang, D.Q. Wang, Inorg. Chim. Acta 358
(2005) 4575.
We thank the National Natural Science Foundation of
China for the financial support of this research (Grant
No. 20271025).
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