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Acta Cryst. (2009). E65, m238    [ doi:10.1107/S160053680900289X ]

Low-temperature redetermination of tribenzylchloridotin(IV)

S. W. Ng

Abstract top

Compared to the previous studies [Ng (1997). Acta Cryst. C53, 56-58; Yin et al. (2005). Huaxue Shiji, 27, 295-296], the redetermined structure of the title compound, [Sn(C7H7)3Cl], exhibits a doubled c unit-cell parameter. There are two molecules in the asymmetric unit, with both Sn and both Cl atoms having 3 site symmetry. The Sn atoms have distorted SnClC3 tetrahedral geometries and the molecules interact by way of short Sn...Cl bridges [Sn...Cl = 3.418 (2) and 3.475 (2) Å], thereby forming chains propagating in c.

Comment top

The room-temperature structure of tribenzyltin(IV) chloride, (I), has been described in the R3 space group but with the unique c-axis half as long [a = 16.942 (1), c = 5.9187 (4) Å] (Ng, 1997; Yin et al., 2005) as that found here. Presumably, the two independent studies missed the weak reflections along the c-axis. In the present low-temperature study of (I) (Fig. 1), the l = 2n + 1 reflections are generally weak but are unambiguously present. The crystal structure consists of [SnCI(C7H7)3] molecules (Tabl 1) linked axially by tin···chlorine bridges into a chain along the c-axis of the trigonal unit cell.

Related literature top

For the room-temperature structure of the title compoound described in the R3 space group but with the unique c axis half as long, see: Ng (1997); Yin et al. (2005). For the direct synthesis of the title compound from metallic tin and benzyl chloride, see: Sisido et al. (1961).

Experimental top

Tribenzyltin chloride was prepared from metallic tin and benzyl chloride in water (Sisido et al., 1961) and was recrystallized from ethanol to yield colourless prisms of (I).

Refinement top

The H atoms were placed in calculated positions [C—H 0.95–0.99 Å, Uiso(H) 1.2Ueq(C)], and were included in the refinement in the riding-model approximation.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I); displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius. Only symmetry-independent atoms are labeled.
tribenzylchloridotin(IV) top
Crystal data top
[Sn(C7H7)3Cl]Dx = 1.491 Mg m−3
Mr = 427.52Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 5172 reflections
Hall symbol: R 3θ = 2.4–28.3°
a = 16.7985 (2) ŵ = 1.48 mm−1
c = 11.6875 (2) ÅT = 100 K
V = 2856.23 (6) Å3Prism, colorless
Z = 60.40 × 0.08 × 0.06 mm
F(000) = 1284
Data collection top
Bruker SMART APEX
diffractometer		2737 independent reflections
Radiation source: fine-focus sealed tube2431 reflections with I > 2σ(I)
graphiteRint = 0.014
ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −21→21
Tmin = 0.589, Tmax = 0.917k = −21→21
9077 measured reflectionsl = −15→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)] = 0.026H-atom parameters constrained
wR(F2) = 0.074 w = 1/[σ2(Fo2) + (0.0515P)2 + 0.375P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2737 reflectionsΔρmax = 0.53 e Å−3
139 parametersΔρmin = −0.25 e Å−3
1 restraintAbsolute structure: Flack (1983), 1372 Fridel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.01 (4)
Crystal data top
[Sn(C7H7)3Cl]Z = 6
Mr = 427.52Mo Kα radiation
Trigonal, R3µ = 1.48 mm−1
a = 16.7985 (2) ÅT = 100 K
c = 11.6875 (2) Å0.40 × 0.08 × 0.06 mm
V = 2856.23 (6) Å3
Data collection top
Bruker SMART APEX
diffractometer		2737 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2431 reflections with I > 2σ(I)
Tmin = 0.589, Tmax = 0.917Rint = 0.014
9077 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.53 e Å−3
S = 1.07Δρmin = −0.25 e Å−3
2737 reflectionsAbsolute structure: Flack (1983), 1372 Fridel pairs
139 parametersFlack parameter: −0.01 (4)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.33330.66670.500000 (15)0.01587 (10)
Sn20.33330.66671.00289 (2)0.01945 (10)
Cl10.33330.66670.29532 (14)0.0388 (4)
Cl20.33330.66670.79730 (13)0.0364 (4)
C10.4692 (2)0.7751 (2)0.5415 (3)0.0231 (6)
H1A0.48050.77300.62420.028*
H1B0.51490.76590.49880.028*
C20.4812 (2)0.8672 (2)0.5120 (3)0.0214 (6)
C30.5272 (2)0.9129 (2)0.4134 (3)0.0353 (7)
H30.55240.88580.36460.042*
C40.5369 (3)0.9971 (2)0.3847 (3)0.0475 (9)
H40.56861.02720.31670.057*
C50.5008 (3)1.0378 (2)0.4544 (4)0.0438 (8)
H50.50701.09540.43440.053*
C60.4552 (2)0.9929 (2)0.5546 (4)0.0361 (8)
H60.43051.02040.60340.043*
C70.4456 (2)0.9089 (2)0.5831 (3)0.0283 (7)
H70.41460.87910.65160.034*
C80.4652 (2)0.7841 (2)1.0378 (3)0.0269 (7)
H8A0.48280.78151.11800.032*
H8B0.51190.78310.98710.032*
C90.4632 (2)0.8710 (2)1.0191 (3)0.0259 (6)
C100.4869 (2)0.9179 (2)0.9159 (3)0.0417 (8)
H100.50760.89570.85460.050*
C110.4811 (3)0.9968 (2)0.9002 (4)0.0531 (10)
H110.49661.02710.82810.064*
C120.4528 (2)1.0317 (2)0.9886 (4)0.0482 (9)
H120.45001.08630.97840.058*
C130.4288 (2)0.9860 (2)1.0914 (4)0.0401 (8)
H130.40911.00911.15270.048*
C140.4331 (2)0.9067 (2)1.1065 (3)0.0311 (7)
H140.41510.87561.17790.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.01588 (11)0.01588 (11)0.01586 (17)0.00794 (5)0.0000.000
Sn20.02122 (12)0.02122 (12)0.01592 (18)0.01061 (6)0.0000.000
Cl10.0498 (6)0.0498 (6)0.0167 (5)0.0249 (3)0.0000.000
Cl20.0470 (6)0.0470 (6)0.0152 (5)0.0235 (3)0.0000.000
C10.0191 (14)0.0214 (14)0.0274 (14)0.0092 (11)−0.0005 (11)0.0038 (11)
C20.0192 (13)0.0178 (13)0.0233 (13)0.0062 (11)−0.0037 (11)0.0006 (10)
C30.0457 (19)0.0255 (15)0.0277 (14)0.0125 (14)0.0090 (14)0.0008 (11)
C40.070 (2)0.0274 (16)0.0344 (19)0.0163 (18)0.0067 (16)0.0085 (13)
C50.055 (2)0.0231 (15)0.050 (2)0.0179 (17)−0.0140 (17)−0.0011 (14)
C60.0319 (18)0.0280 (15)0.048 (2)0.0150 (14)−0.0070 (14)−0.0085 (14)
C70.0225 (14)0.0270 (15)0.0302 (16)0.0086 (12)−0.0012 (11)−0.0059 (12)
C80.0231 (15)0.0284 (16)0.0276 (15)0.0116 (13)0.0011 (12)−0.0012 (12)
C90.0246 (14)0.0281 (15)0.0208 (12)0.0100 (12)−0.0025 (11)−0.0030 (11)
C100.047 (2)0.0328 (17)0.0280 (15)0.0066 (16)0.0013 (14)0.0007 (13)
C110.063 (2)0.0353 (19)0.0365 (19)0.0064 (18)−0.0148 (17)0.0104 (15)
C120.049 (2)0.0255 (16)0.063 (2)0.0138 (17)−0.0256 (18)−0.0023 (16)
C130.0374 (18)0.0338 (18)0.050 (2)0.0181 (15)−0.0076 (15)−0.0067 (15)
C140.0300 (16)0.0278 (15)0.0299 (16)0.0103 (13)0.0012 (12)−0.0008 (12)
Geometric parameters (Å, °) top
Sn1—C1i2.146 (3)C5—C61.396 (5)
Sn1—C12.146 (3)C5—H50.9500
Sn1—C1ii2.146 (3)C6—C71.379 (5)
Sn1—Cl12.392 (2)C6—H60.9500
Sn1—Cl23.475 (2)C7—H70.9500
Sn2—C8i2.143 (3)C8—C91.494 (5)
Sn2—C82.143 (3)C8—H8A0.9900
Sn2—C8ii2.143 (3)C8—H8B0.9900
Sn2—Cl22.403 (2)C9—C101.387 (4)
Sn2—Cl1iii3.418 (2)C9—C141.400 (4)
C1—C21.497 (4)C10—C111.389 (5)
C1—H1A0.9900C10—H100.9500
C1—H1B0.9900C11—C121.383 (5)
C2—C31.387 (4)C11—H110.9500
C2—C71.398 (4)C12—C131.373 (5)
C3—C41.381 (4)C12—H120.9500
C3—H30.9500C13—C141.381 (5)
C4—C51.383 (5)C13—H130.9500
C4—H40.9500C14—H140.9500
C1i—Sn1—C1115.06 (6)C5—C4—H4119.8
C1i—Sn1—C1ii115.06 (7)C4—C5—C6119.0 (3)
C1—Sn1—C1ii115.06 (6)C4—C5—H5120.5
C1i—Sn1—Cl1103.05 (9)C6—C5—H5120.5
C1—Sn1—Cl1103.05 (9)C7—C6—C5120.5 (3)
C1ii—Sn1—Cl1103.05 (9)C7—C6—H6119.8
C1i—Sn1—Cl276.95 (9)C5—C6—H6119.8
C1—Sn1—Cl276.95 (9)C6—C7—C2120.6 (3)
C1ii—Sn1—Cl276.95 (9)C6—C7—H7119.7
Cl1—Sn1—Cl2180.0C2—C7—H7119.7
C8i—Sn2—C8116.46 (6)C9—C8—Sn2110.7 (2)
C8i—Sn2—C8ii116.46 (6)C9—C8—H8A109.5
C8—Sn2—C8ii116.46 (6)Sn2—C8—H8A109.5
C8i—Sn2—Cl2100.98 (9)C9—C8—H8B109.5
C8—Sn2—Cl2100.98 (9)Sn2—C8—H8B109.5
C8ii—Sn2—Cl2100.98 (9)H8A—C8—H8B108.1
C8i—Sn2—Cl1iii79.02 (9)C10—C9—C14117.0 (3)
C8—Sn2—Cl1iii79.02 (9)C10—C9—C8122.9 (3)
C8ii—Sn2—Cl1iii79.02 (9)C14—C9—C8120.1 (3)
Cl2—Sn2—Cl1iii180.0C9—C10—C11121.4 (3)
Sn2—Cl2—Sn1180.0C9—C10—H10119.3
C2—C1—Sn1111.2 (2)C11—C10—H10119.3
C2—C1—H1A109.4C12—C11—C10120.5 (3)
Sn1—C1—H1A109.4C12—C11—H11119.7
C2—C1—H1B109.4C10—C11—H11119.7
Sn1—C1—H1B109.4C13—C12—C11118.9 (3)
H1A—C1—H1B108.0C13—C12—H12120.5
C3—C2—C7118.4 (3)C11—C12—H12120.5
C3—C2—C1120.9 (3)C12—C13—C14120.6 (3)
C7—C2—C1120.7 (3)C12—C13—H13119.7
C4—C3—C2121.1 (3)C14—C13—H13119.7
C4—C3—H3119.5C13—C14—C9121.6 (3)
C2—C3—H3119.5C13—C14—H14119.2
C3—C4—C5120.5 (3)C9—C14—H14119.2
C3—C4—H4119.8
C1i—Sn1—C1—C2−41.4 (3)C8i—Sn2—C8—C9−31.7 (3)
C1ii—Sn1—C1—C2−178.70 (16)C8ii—Sn2—C8—C9−175.18 (15)
Cl1—Sn1—C1—C269.9 (2)Cl2—Sn2—C8—C976.6 (2)
Cl2—Sn1—C1—C2−110.1 (2)Cl1iii—Sn2—C8—C9−103.4 (2)
Sn1—C1—C2—C3−101.4 (3)Sn2—C8—C9—C10−92.7 (3)
Sn1—C1—C2—C778.1 (3)Sn2—C8—C9—C1484.8 (3)
C7—C2—C3—C4−0.7 (5)C14—C9—C10—C110.1 (5)
C1—C2—C3—C4178.8 (3)C8—C9—C10—C11177.7 (3)
C2—C3—C4—C50.0 (5)C9—C10—C11—C121.2 (5)
C3—C4—C5—C60.6 (6)C10—C11—C12—C13−1.3 (5)
C4—C5—C6—C7−0.5 (5)C11—C12—C13—C140.2 (5)
C5—C6—C7—C2−0.2 (5)C12—C13—C14—C91.1 (5)
C3—C2—C7—C60.8 (5)C10—C9—C14—C13−1.2 (5)
C1—C2—C7—C6−178.7 (3)C8—C9—C14—C13−178.9 (3)
Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z; (iii) x, y, z+1.
Table 1
Selected geometric parameters (Å) top
Sn1—C12.146 (3)Sn2—C82.143 (3)
Sn1—Cl12.392 (2)Sn2—Cl22.403 (2)
Acknowledgements top

The author thanks the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Ng, S. W. (1997). Acta Cryst. C53, 56–58.

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

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sisido, K., Takeda, Y. & Kinugawa, Z. (1961). J. Am. Chem. Soc. 83, 538–541.

Westrip, S. P. (2009). publCIF. In preparation.

Yin, H.-D., Li, K.-Z. & Hong, M. (2005). Huaxue Shiji, 27, 295–296, 310.