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Acta Cryst. (2007). E63, m3012    [ doi:10.1107/S1600536807056784 ]

catena-Poly[[chloridodimethyltin(IV)]-[mu]-thiophene-2-acetato-[kappa]2O:O']

H. Wang, H. Yin and D. Wang

Abstract top

The title compound, [Sn(CH3)2(C6H5O2S)Cl]n, forms an extended one-dimensional chain structure which propagates along the a-axis direction. The two independent SnO2C2Cl centres have distorted trigonal-bipyramidal environments with the coordinated O atoms in the axial positions. Both thiophene groups are disordered over two sites, with approximate occupancies of 0.5:0.5 and 0.78:0.22.

Comment top

A series of new triorganotin(IV) pyridinedicarboxylates were synthesized by the reaction of trimethyltin(IV), triphenyltin(IV) or tribenzyltin(IV) chloride with 2,6(3,5 or 2,5)-H2pdc (pdc = pyridinedicarboxylate) (Ma et al.,2006). The title compound, (I) (Fig. 1), has an extended one-dimensional chain structure formed from Sn—O bridges to the ligand with Sn—O distances close to those in reported organotin carboxylates (Ma et al., 2006). The two independent Sn atoms are in distorted trigonal-bipyramidal coordination geometries, with the O atoms in axial positions and atoms C13/C14/Cl1 and C15/C16/Cl2 in equatorial positions. The sum of the equatorial angles at Sn1 and Sn2 of 357.2 and 356.2° indicate approximate coplanarity for the atoms involved.

Related literature top

For related literature, see: Ma et al. (2006)

Experimental top

The reaction was carried out under N2. 2-Thiopheneacetic acid (1 mmol) and sodium ethoxide (1.2 mmol) were added to the solution of benzene(30 ml) in a Schlenk flask and stirred for 0.5 h. Dimethyltin dichloride (1 mmol) was then added to the reactor and the reaction mixture was stirred for 12 h at 313 K. The resulting clear solution was evaporated under vacuum. The product was crystallized from a mixture of dichloromethane/methanol (1:1).(yield 80%; m.p. 472 K). Analysis calculated (%) for C16H22Cl2O4S2Sn2 (Mr = 650.74): C, 29.53; H, 3.41. found: C, 29.47; H, 3.52.

Refinement top

During the refinement both thiophene groups were found to be disordered over two sites corresponding to an approximate 180° rotation parallel to the ring plane. The ratio of the occupancy factors refined to 0.502 (9):0.498 (2) and 0.783 (8):0.217 (8) for atoms S1/C3—C6:S1'/C3'-6' and atoms S2/C9—C12:S2'/C9'-C12', repectively. H atoms were positioned geometrically, with C—H = 0.91–0.97 Å and constrained to ride on their parent atoms, with Uiso(H) = Ueq(C) where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity. The disorder is not shown.
[Figure 2] Fig. 2. The 1-D extended chain structure propagating along the a axis. H atoms have been omitted for clarity.
catena-Poly[[dichloridodimethyltin(IV)]-µ-thiophene-2-acetato-κ2O:O'] top
Crystal data top
[Sn(CH3)2(C6H5O2S)Cl]Z = 4
Mr = 325.37F000 = 632
Triclinic, P1Dx = 1.862 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.2189 (18) ÅCell parameters from 4001 reflections
b = 10.591 (2) Åθ = 2.3–28.1º
c = 12.226 (2) ŵ = 2.58 mm−1
α = 97.898 (2)ºT = 298 (2) K
β = 93.287 (2)ºBlock, colourless
γ = 99.948 (2)º0.53 × 0.42 × 0.38 mm
V = 1160.6 (4) Å3
Data collection top
Bruker SMART CCD
diffractometer		4020 independent reflections
Radiation source: fine-focus sealed tube3265 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.017
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.342, Tmax = 0.441k = −10→12
6038 measured reflectionsl = −11→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.086  w = 1/[σ2(Fo2) + (0.050P)2 + 1.0989P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
4020 reflectionsΔρmax = 0.53 e Å−3
289 parametersΔρmin = −0.87 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Sn(CH3)2(C6H5O2S)Cl]γ = 99.948 (2)º
Mr = 325.37V = 1160.6 (4) Å3
Triclinic, P1Z = 4
a = 9.2189 (18) ÅMo Kα
b = 10.591 (2) ŵ = 2.58 mm−1
c = 12.226 (2) ÅT = 298 (2) K
α = 97.898 (2)º0.53 × 0.42 × 0.38 mm
β = 93.287 (2)º
Data collection top
Bruker SMART CCD
diffractometer		4020 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3265 reflections with I > 2σ(I)
Tmin = 0.342, Tmax = 0.441Rint = 0.017
6038 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029289 parameters
wR(F2) = 0.086H-atom parameters constrained
S = 1.00Δρmax = 0.53 e Å−3
4020 reflectionsΔρmin = −0.87 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn10.62273 (3)0.74816 (3)0.10589 (2)0.03419 (11)
Sn21.14767 (3)0.81755 (3)0.23097 (3)0.03814 (12)
Cl10.79330 (14)0.67290 (15)−0.01443 (11)0.0558 (4)
Cl21.36682 (14)0.88314 (17)0.35067 (12)0.0627 (4)
O10.8452 (4)0.8005 (4)0.2392 (3)0.0470 (8)
O21.0249 (3)0.8696 (4)0.3698 (3)0.0466 (8)
O30.4573 (3)0.6910 (3)−0.0316 (3)0.0456 (8)
O40.3239 (4)0.7682 (4)0.0944 (3)0.0525 (9)
C10.8870 (5)0.8430 (5)0.3377 (4)0.0392 (11)
C20.7808 (6)0.8625 (5)0.4239 (4)0.0496 (13)
H2A0.68710.87140.38830.060*
H2B0.81900.94200.47410.060*
S10.6822 (9)0.7729 (8)0.6105 (6)0.094 (2)0.502 (9)
C30.7564 (6)0.7512 (6)0.4887 (4)0.0546 (14)0.502 (9)
C40.782 (6)0.628 (3)0.465 (3)0.090 (2)0.502 (9)
H40.82320.59870.40070.108*0.502 (9)
C50.742 (19)0.552 (14)0.544 (14)0.09 (2)0.502 (9)
H50.75190.46590.53900.107*0.502 (9)
C60.68 (2)0.617 (18)0.631 (17)0.10 (2)0.502 (9)
H60.65220.58110.69310.116*0.502 (9)
S1'0.7801 (14)0.5963 (7)0.4449 (7)0.090 (2)0.498 (9)
C3'0.7564 (6)0.7512 (6)0.4887 (4)0.0546 (14)0.498 (9)
C4'0.709 (4)0.750 (3)0.591 (3)0.094 (2)0.498 (9)
H4'0.68830.82340.63280.113*0.498 (9)
C5'0.69 (2)0.634 (17)0.630 (16)0.09 (2)0.498 (9)
H5'0.66330.62380.69930.111*0.498 (9)
C6'0.73 (2)0.535 (15)0.560 (15)0.093 (16)0.498 (9)
H6'0.72390.44970.57290.111*0.498 (9)
C70.3332 (5)0.7131 (5)−0.0002 (4)0.0383 (10)
C80.2003 (5)0.6627 (6)−0.0817 (4)0.0523 (13)
H8A0.18620.5688−0.09490.063*
H8B0.11390.6861−0.04830.063*
S20.3625 (3)0.7310 (4)−0.2599 (3)0.0613 (9)0.783 (8)
C90.2088 (6)0.7109 (5)−0.1905 (4)0.0457 (12)0.783 (8)
C100.094 (4)0.747 (4)−0.246 (3)0.069 (4)0.783 (8)
H100.00080.7441−0.21960.083*0.783 (8)
C110.129 (6)0.787 (5)−0.345 (3)0.087 (10)0.783 (8)
H110.06200.8143−0.39300.104*0.783 (8)
C120.272 (7)0.783 (7)−0.367 (6)0.081 (9)0.783 (8)
H120.31490.8060−0.43000.097*0.783 (8)
S2'0.063 (4)0.739 (4)−0.267 (3)0.069 (4)0.217 (8)
C9'0.2088 (6)0.7109 (5)−0.1905 (4)0.0457 (12)0.217 (8)
C10'0.318 (6)0.711 (6)−0.260 (5)0.0613 (9)0.217 (8)
H10'0.40200.6758−0.24610.074*0.217 (8)
C11'0.30 (2)0.77 (2)−0.35 (2)0.08 (4)0.217 (8)
H11'0.37320.7960−0.39410.091*0.217 (8)
C12'0.16 (2)0.777 (19)−0.378 (12)0.08 (3)0.217 (8)
H12'0.11620.8001−0.44280.100*0.217 (8)
C130.5429 (6)0.6015 (5)0.1980 (4)0.0505 (13)
H13A0.50260.63870.26290.076*
H13B0.62240.56000.21970.076*
H13C0.46720.53870.15350.076*
C140.6487 (6)0.9496 (5)0.1136 (5)0.0549 (14)
H14A0.59930.98440.17460.082*
H14B0.60680.96960.04580.082*
H14C0.75200.98700.12390.082*
C151.0898 (7)0.6159 (5)0.2174 (5)0.0594 (15)
H15A1.02520.59400.27350.089*
H15B1.17740.57970.22700.089*
H15C1.04030.58140.14560.089*
C161.1208 (7)0.9686 (6)0.1402 (5)0.0617 (15)
H16A1.06830.93270.06960.093*
H16B1.21601.01600.12910.093*
H16C1.06581.02590.18050.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.03134 (18)0.03700 (19)0.03505 (19)0.00966 (13)0.00292 (13)0.00393 (13)
Sn20.03394 (19)0.0430 (2)0.0377 (2)0.00999 (14)0.00003 (13)0.00405 (14)
Cl10.0422 (7)0.0801 (10)0.0466 (7)0.0228 (7)0.0089 (6)−0.0023 (6)
Cl20.0373 (7)0.0929 (11)0.0523 (8)0.0124 (7)−0.0067 (6)−0.0057 (7)
O10.0382 (18)0.062 (2)0.038 (2)0.0098 (16)−0.0044 (15)0.0012 (16)
O20.0342 (18)0.067 (2)0.0360 (18)0.0096 (16)0.0004 (14)−0.0022 (16)
O30.0340 (17)0.063 (2)0.0393 (19)0.0175 (16)−0.0030 (14)−0.0019 (16)
O40.043 (2)0.067 (2)0.047 (2)0.0147 (18)0.0086 (16)−0.0021 (18)
C10.038 (3)0.043 (3)0.039 (3)0.012 (2)0.000 (2)0.010 (2)
C20.044 (3)0.065 (4)0.046 (3)0.024 (3)0.009 (2)0.010 (3)
S10.119 (4)0.097 (4)0.086 (4)0.038 (3)0.063 (2)0.035 (3)
C30.048 (3)0.069 (4)0.049 (3)0.014 (3)0.007 (2)0.014 (3)
C40.146 (3)0.074 (5)0.057 (4)0.034 (4)0.014 (3)0.014 (3)
C50.12 (5)0.08 (3)0.08 (4)0.02 (3)0.00 (3)0.03 (2)
C60.11 (5)0.10 (4)0.10 (4)0.02 (3)0.04 (3)0.05 (3)
S1'0.146 (3)0.074 (5)0.057 (4)0.034 (4)0.014 (3)0.014 (3)
C3'0.048 (3)0.069 (4)0.049 (3)0.014 (3)0.007 (2)0.014 (3)
C4'0.119 (4)0.097 (4)0.086 (4)0.038 (3)0.063 (2)0.035 (3)
C5'0.10 (3)0.11 (5)0.09 (3)0.03 (4)0.04 (2)0.05 (4)
C6'0.12 (3)0.08 (4)0.08 (4)0.01 (3)0.01 (2)0.03 (2)
C70.033 (2)0.040 (3)0.042 (3)0.007 (2)0.002 (2)0.008 (2)
C80.031 (3)0.071 (4)0.055 (3)0.010 (2)0.002 (2)0.009 (3)
S20.072 (2)0.0661 (18)0.0522 (13)0.0244 (15)0.0142 (15)0.0144 (11)
C90.046 (3)0.042 (3)0.047 (3)0.011 (2)−0.006 (2)0.000 (2)
C100.059 (12)0.072 (5)0.075 (12)0.010 (7)−0.025 (7)0.015 (7)
C110.099 (18)0.083 (13)0.08 (2)0.012 (11)−0.033 (15)0.027 (17)
C120.12 (2)0.076 (18)0.049 (13)0.016 (15)−0.006 (17)0.017 (10)
S2'0.059 (12)0.072 (5)0.075 (12)0.010 (7)−0.025 (7)0.015 (7)
C9'0.046 (3)0.042 (3)0.047 (3)0.011 (2)−0.006 (2)0.000 (2)
C10'0.072 (2)0.0661 (18)0.0522 (13)0.0244 (15)0.0142 (15)0.0144 (11)
C11'0.10 (6)0.07 (6)0.06 (7)0.01 (4)0.00 (5)0.02 (4)
C12'0.10 (7)0.08 (4)0.06 (6)0.00 (4)−0.03 (5)0.02 (5)
C130.055 (3)0.048 (3)0.050 (3)0.009 (3)0.005 (2)0.011 (2)
C140.058 (3)0.043 (3)0.063 (4)0.009 (3)0.000 (3)0.012 (3)
C150.061 (4)0.046 (3)0.073 (4)0.015 (3)0.006 (3)0.010 (3)
C160.065 (4)0.063 (4)0.066 (4)0.022 (3)0.015 (3)0.027 (3)
Geometric parameters (Å, °) top
Sn1—C142.093 (5)C6'—H6'0.9300
Sn1—C132.098 (5)C7—C81.506 (7)
Sn1—O32.151 (3)C8—C91.490 (7)
Sn1—Cl12.3766 (13)C8—H8A0.9700
Sn1—O12.479 (3)C8—H8B0.9700
Sn2—C152.091 (5)S2—C91.690 (6)
Sn2—C162.109 (5)S2—C121.71 (6)
Sn2—O22.155 (3)C9—C101.36 (3)
Sn2—Cl22.3670 (14)C10—C111.38 (5)
Sn2—O4i2.463 (3)C10—H100.9300
O1—C11.241 (5)C11—C121.37 (8)
O2—C11.280 (6)C11—H110.9300
O3—C71.276 (5)C12—H120.9300
O4—C71.236 (6)S2'—C12'1.70 (16)
O4—Sn2ii2.463 (3)C10'—C11'1.4 (2)
C1—C21.497 (7)C10'—H10'0.9300
C2—C31.500 (7)C11'—C12'1.3 (3)
C2—H2A0.9700C11'—H11'0.9200
C2—H2B0.9700C12'—H12'0.9500
S1—C31.678 (7)C13—H13A0.9600
S1—C61.7 (2)C13—H13B0.9600
C3—C41.36 (3)C13—H13C0.9600
C4—C51.37 (12)C14—H14A0.9600
C4—H40.9300C14—H14B0.9600
C5—C61.4 (2)C14—H14C0.9600
C5—H50.9300C15—H15A0.9600
C6—H60.9300C15—H15B0.9600
S1'—C6'1.69 (13)C15—H15C0.9600
C4'—C5'1.36 (19)C16—H16A0.9600
C4'—H4'0.9300C16—H16B0.9600
C5'—C6'1.3 (2)C16—H16C0.9600
C5'—H5'0.9100
C14—Sn1—C13140.1 (2)S1'—C6'—H6'126.9
C14—Sn1—O398.89 (18)O4—C7—O3120.8 (4)
C13—Sn1—O397.05 (18)O4—C7—C8122.5 (4)
C14—Sn1—Cl1108.22 (17)O3—C7—C8116.6 (4)
C13—Sn1—Cl1108.83 (15)C9—C8—C7115.2 (4)
O3—Sn1—Cl187.44 (9)C9—C8—H8A108.5
C14—Sn1—O184.14 (18)C7—C8—H8A108.5
C13—Sn1—O186.87 (17)C9—C8—H8B108.5
O3—Sn1—O1169.29 (12)C7—C8—H8B108.5
Cl1—Sn1—O181.85 (9)H8A—C8—H8B107.5
C15—Sn2—C16139.9 (3)C9—S2—C1292 (2)
C15—Sn2—O298.55 (19)C10—C9—C8124 (2)
C16—Sn2—O299.14 (19)C10—C9—S2111 (2)
C15—Sn2—Cl2107.45 (17)C8—C9—S2124.6 (4)
C16—Sn2—Cl2108.80 (19)C9—C10—C11113 (4)
O2—Sn2—Cl288.31 (9)C9—C10—H10123.4
C15—Sn2—O4i83.98 (19)C11—C10—H10123.4
C16—Sn2—O4i84.37 (19)C12—C11—C10113 (4)
O2—Sn2—O4i170.58 (12)C12—C11—H11123.6
Cl2—Sn2—O4i82.28 (9)C10—C11—H11123.6
C1—O1—Sn1142.4 (3)C11—C12—S2110 (4)
C1—O2—Sn2108.5 (3)C11—C12—H12124.8
C7—O3—Sn1109.3 (3)S2—C12—H12124.8
C7—O4—Sn2ii143.5 (3)C11'—C10'—H10'122.6
O1—C1—O2120.4 (4)C12'—C11'—C10'115 (10)
O1—C1—C2122.3 (4)C11'—C12'—S2'105 (10)
O2—C1—C2117.3 (4)Sn1—C13—H13A109.5
C1—C2—C3111.6 (4)Sn1—C13—H13B109.5
C1—C2—H2A109.3H13A—C13—H13B109.5
C3—C2—H2A109.3Sn1—C13—H13C109.5
C1—C2—H2B109.3H13A—C13—H13C109.5
C3—C2—H2B109.3H13B—C13—H13C109.5
H2A—C2—H2B108.0Sn1—C14—H14A109.5
C3—S1—C693 (6)Sn1—C14—H14B109.5
C4—C3—C2130.6 (19)H14A—C14—H14B109.5
C4—C3—S1110.9 (19)Sn1—C14—H14C109.5
C2—C3—S1118.4 (5)H14A—C14—H14C109.5
C3—C4—C5114 (7)H14B—C14—H14C109.5
C3—C4—H4123.1Sn2—C15—H15A109.5
C5—C4—H4123.1Sn2—C15—H15B109.5
C6—C5—C4113 (10)H15A—C15—H15B109.5
C6—C5—H5123.5Sn2—C15—H15C109.5
C4—C5—H5123.5H15A—C15—H15C109.5
C5—C6—S1110 (10)H15B—C15—H15C109.5
S1—C6—H6127.0Sn2—C16—H16A109.5
C5'—C4'—H4'121.9Sn2—C16—H16B109.5
C6'—C5'—C4'116 (10)H16A—C16—H16B109.5
C6'—C5'—H5'122.2Sn2—C16—H16C109.5
C4'—C5'—H5'124.00H16A—C16—H16C109.5
C5'—C6'—S1'106 (10)H16B—C16—H16C109.5
C5'—C6'—H6'125.8
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.
Acknowledgements top

The authors acknowledge financial support from the Shandong Province Science Foundation and the State Key Laboratory of Crystal Material, Shandong University, People's Republic of China.

references
References top

Ma, C., Li, J., Zhang, R. & Wang, D. (2006). J. Organomet. Chem. 691, 1713–1721.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.