Low-temperature redetermination of tribenzyl­chloridotin(IV)

Ng, S.W.

doi:10.1107/S160053680900289X

metal-organic compounds

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Volume 65| Part 2| February 2009| Page m238

doi:10.1107/S160053680900289X

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Low-temperature redetermination of tribenzylchloridotin(IV)

Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 20 January 2009; accepted 23 January 2009; online 28 January 2009)

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.

Related literature

For the room-temperature structure of the title compound 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

Crystal data

[Sn(C₇H₇)₃Cl]
M_r = 427.52
Trigonal, R 3
a = 16.7985 (2) Å
c = 11.6875 (2) Å
V = 2856.23 (6) Å³
Z = 6
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 100 (2) K
0.40 × 0.08 × 0.06 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.589, T_max = 0.917
9077 measured reflections
2737 independent reflections
2431 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.074
S = 1.07
2737 reflections
139 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 1372 Friedel pairs
Flack parameter: −0.01 (4)

Table 1
Selected bond lengths (Å)

Sn1—C1	2.146 (3)
Sn1—Cl1	2.392 (2)
Sn2—C8	2.143 (3)
Sn2—Cl2	2.403 (2)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680900289X/hb2901sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680900289X/hb2901Isup2.hkl

checkCIF report

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).

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

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]	D_x = 1.491 Mg m⁻³
M_r = 427.52	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 5172 reflections
Hall symbol: R 3	θ = 2.4–28.3°
a = 16.7985 (2) Å	µ = 1.48 mm⁻¹
c = 11.6875 (2) Å	T = 100 K
V = 2856.23 (6) Å³	Prism, colorless
Z = 6	0.40 × 0.08 × 0.06 mm
F(000) = 1284

Data collection top

Bruker SMART APEX diffractometer	2737 independent reflections
Radiation source: fine-focus sealed tube	2431 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→21
T_min = 0.589, T_max = 0.917	k = −21→21
9077 measured reflections	l = −15→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0515P)² + 0.375P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2737 reflections	Δρ_max = 0.53 e Å⁻³
139 parameters	Δρ_min = −0.25 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1372 Fridel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (4)

Crystal data top

[Sn(C₇H₇)₃Cl]	Z = 6
M_r = 427.52	Mo Kα radiation
Trigonal, R3	µ = 1.48 mm⁻¹
a = 16.7985 (2) Å	T = 100 K
c = 11.6875 (2) Å	0.40 × 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)
T_min = 0.589, T_max = 0.917	R_int = 0.014
9077 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.074	Δρ_max = 0.53 e Å⁻³
S = 1.07	Δρ_min = −0.25 e Å⁻³
2737 reflections	Absolute structure: Flack (1983), 1372 Fridel pairs
139 parameters	Absolute structure parameter: −0.01 (4)
1 restraint

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sn1	0.3333	0.6667	0.500000 (15)	0.01587 (10)
Sn2	0.3333	0.6667	1.00289 (2)	0.01945 (10)
Cl1	0.3333	0.6667	0.29532 (14)	0.0388 (4)
Cl2	0.3333	0.6667	0.79730 (13)	0.0364 (4)
C1	0.4692 (2)	0.7751 (2)	0.5415 (3)	0.0231 (6)
H1A	0.4805	0.7730	0.6242	0.028*
H1B	0.5149	0.7659	0.4988	0.028*
C2	0.4812 (2)	0.8672 (2)	0.5120 (3)	0.0214 (6)
C3	0.5272 (2)	0.9129 (2)	0.4134 (3)	0.0353 (7)
H3	0.5524	0.8858	0.3646	0.042*
C4	0.5369 (3)	0.9971 (2)	0.3847 (3)	0.0475 (9)
H4	0.5686	1.0272	0.3167	0.057*
C5	0.5008 (3)	1.0378 (2)	0.4544 (4)	0.0438 (8)
H5	0.5070	1.0954	0.4344	0.053*
C6	0.4552 (2)	0.9929 (2)	0.5546 (4)	0.0361 (8)
H6	0.4305	1.0204	0.6034	0.043*
C7	0.4456 (2)	0.9089 (2)	0.5831 (3)	0.0283 (7)
H7	0.4146	0.8791	0.6516	0.034*
C8	0.4652 (2)	0.7841 (2)	1.0378 (3)	0.0269 (7)
H8A	0.4828	0.7815	1.1180	0.032*
H8B	0.5119	0.7831	0.9871	0.032*
C9	0.4632 (2)	0.8710 (2)	1.0191 (3)	0.0259 (6)
C10	0.4869 (2)	0.9179 (2)	0.9159 (3)	0.0417 (8)
H10	0.5076	0.8957	0.8546	0.050*
C11	0.4811 (3)	0.9968 (2)	0.9002 (4)	0.0531 (10)
H11	0.4966	1.0271	0.8281	0.064*
C12	0.4528 (2)	1.0317 (2)	0.9886 (4)	0.0482 (9)
H12	0.4500	1.0863	0.9784	0.058*
C13	0.4288 (2)	0.9860 (2)	1.0914 (4)	0.0401 (8)
H13	0.4091	1.0091	1.1527	0.048*
C14	0.4331 (2)	0.9067 (2)	1.1065 (3)	0.0311 (7)
H14	0.4151	0.8756	1.1779	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01588 (11)	0.01588 (11)	0.01586 (17)	0.00794 (5)	0.000	0.000
Sn2	0.02122 (12)	0.02122 (12)	0.01592 (18)	0.01061 (6)	0.000	0.000
Cl1	0.0498 (6)	0.0498 (6)	0.0167 (5)	0.0249 (3)	0.000	0.000
Cl2	0.0470 (6)	0.0470 (6)	0.0152 (5)	0.0235 (3)	0.000	0.000
C1	0.0191 (14)	0.0214 (14)	0.0274 (14)	0.0092 (11)	−0.0005 (11)	0.0038 (11)
C2	0.0192 (13)	0.0178 (13)	0.0233 (13)	0.0062 (11)	−0.0037 (11)	0.0006 (10)
C3	0.0457 (19)	0.0255 (15)	0.0277 (14)	0.0125 (14)	0.0090 (14)	0.0008 (11)
C4	0.070 (2)	0.0274 (16)	0.0344 (19)	0.0163 (18)	0.0067 (16)	0.0085 (13)
C5	0.055 (2)	0.0231 (15)	0.050 (2)	0.0179 (17)	−0.0140 (17)	−0.0011 (14)
C6	0.0319 (18)	0.0280 (15)	0.048 (2)	0.0150 (14)	−0.0070 (14)	−0.0085 (14)
C7	0.0225 (14)	0.0270 (15)	0.0302 (16)	0.0086 (12)	−0.0012 (11)	−0.0059 (12)
C8	0.0231 (15)	0.0284 (16)	0.0276 (15)	0.0116 (13)	0.0011 (12)	−0.0012 (12)
C9	0.0246 (14)	0.0281 (15)	0.0208 (12)	0.0100 (12)	−0.0025 (11)	−0.0030 (11)
C10	0.047 (2)	0.0328 (17)	0.0280 (15)	0.0066 (16)	0.0013 (14)	0.0007 (13)
C11	0.063 (2)	0.0353 (19)	0.0365 (19)	0.0064 (18)	−0.0148 (17)	0.0104 (15)
C12	0.049 (2)	0.0255 (16)	0.063 (2)	0.0138 (17)	−0.0256 (18)	−0.0023 (16)
C13	0.0374 (18)	0.0338 (18)	0.050 (2)	0.0181 (15)	−0.0076 (15)	−0.0067 (15)
C14	0.0300 (16)	0.0278 (15)	0.0299 (16)	0.0103 (13)	0.0012 (12)	−0.0008 (12)

Geometric parameters (Å, º) top

Sn1—C1ⁱ	2.146 (3)	C5—C6	1.396 (5)
Sn1—C1	2.146 (3)	C5—H5	0.9500
Sn1—C1ⁱⁱ	2.146 (3)	C6—C7	1.379 (5)
Sn1—Cl1	2.392 (2)	C6—H6	0.9500
Sn1—Cl2	3.475 (2)	C7—H7	0.9500
Sn2—C8ⁱ	2.143 (3)	C8—C9	1.494 (5)
Sn2—C8	2.143 (3)	C8—H8A	0.9900
Sn2—C8ⁱⁱ	2.143 (3)	C8—H8B	0.9900
Sn2—Cl2	2.403 (2)	C9—C10	1.387 (4)
Sn2—Cl1ⁱⁱⁱ	3.418 (2)	C9—C14	1.400 (4)
C1—C2	1.497 (4)	C10—C11	1.389 (5)
C1—H1A	0.9900	C10—H10	0.9500
C1—H1B	0.9900	C11—C12	1.383 (5)
C2—C3	1.387 (4)	C11—H11	0.9500
C2—C7	1.398 (4)	C12—C13	1.373 (5)
C3—C4	1.381 (4)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.381 (5)
C4—C5	1.383 (5)	C13—H13	0.9500
C4—H4	0.9500	C14—H14	0.9500

C1ⁱ—Sn1—C1	115.06 (6)	C5—C4—H4	119.8
C1ⁱ—Sn1—C1ⁱⁱ	115.06 (7)	C4—C5—C6	119.0 (3)
C1—Sn1—C1ⁱⁱ	115.06 (6)	C4—C5—H5	120.5
C1ⁱ—Sn1—Cl1	103.05 (9)	C6—C5—H5	120.5
C1—Sn1—Cl1	103.05 (9)	C7—C6—C5	120.5 (3)
C1ⁱⁱ—Sn1—Cl1	103.05 (9)	C7—C6—H6	119.8
C1ⁱ—Sn1—Cl2	76.95 (9)	C5—C6—H6	119.8
C1—Sn1—Cl2	76.95 (9)	C6—C7—C2	120.6 (3)
C1ⁱⁱ—Sn1—Cl2	76.95 (9)	C6—C7—H7	119.7
Cl1—Sn1—Cl2	180.0	C2—C7—H7	119.7
C8ⁱ—Sn2—C8	116.46 (6)	C9—C8—Sn2	110.7 (2)
C8ⁱ—Sn2—C8ⁱⁱ	116.46 (6)	C9—C8—H8A	109.5
C8—Sn2—C8ⁱⁱ	116.46 (6)	Sn2—C8—H8A	109.5
C8ⁱ—Sn2—Cl2	100.98 (9)	C9—C8—H8B	109.5
C8—Sn2—Cl2	100.98 (9)	Sn2—C8—H8B	109.5
C8ⁱⁱ—Sn2—Cl2	100.98 (9)	H8A—C8—H8B	108.1
C8ⁱ—Sn2—Cl1ⁱⁱⁱ	79.02 (9)	C10—C9—C14	117.0 (3)
C8—Sn2—Cl1ⁱⁱⁱ	79.02 (9)	C10—C9—C8	122.9 (3)
C8ⁱⁱ—Sn2—Cl1ⁱⁱⁱ	79.02 (9)	C14—C9—C8	120.1 (3)
Cl2—Sn2—Cl1ⁱⁱⁱ	180.0	C9—C10—C11	121.4 (3)
Sn2—Cl2—Sn1	180.0	C9—C10—H10	119.3
C2—C1—Sn1	111.2 (2)	C11—C10—H10	119.3
C2—C1—H1A	109.4	C12—C11—C10	120.5 (3)
Sn1—C1—H1A	109.4	C12—C11—H11	119.7
C2—C1—H1B	109.4	C10—C11—H11	119.7
Sn1—C1—H1B	109.4	C13—C12—C11	118.9 (3)
H1A—C1—H1B	108.0	C13—C12—H12	120.5
C3—C2—C7	118.4 (3)	C11—C12—H12	120.5
C3—C2—C1	120.9 (3)	C12—C13—C14	120.6 (3)
C7—C2—C1	120.7 (3)	C12—C13—H13	119.7
C4—C3—C2	121.1 (3)	C14—C13—H13	119.7
C4—C3—H3	119.5	C13—C14—C9	121.6 (3)
C2—C3—H3	119.5	C13—C14—H14	119.2
C3—C4—C5	120.5 (3)	C9—C14—H14	119.2
C3—C4—H4	119.8

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—C2	69.9 (2)	Cl2—Sn2—C8—C9	76.6 (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—C7	78.1 (3)	Sn2—C8—C9—C14	84.8 (3)
C7—C2—C3—C4	−0.7 (5)	C14—C9—C10—C11	0.1 (5)
C1—C2—C3—C4	178.8 (3)	C8—C9—C10—C11	177.7 (3)
C2—C3—C4—C5	0.0 (5)	C9—C10—C11—C12	1.2 (5)
C3—C4—C5—C6	0.6 (6)	C10—C11—C12—C13	−1.3 (5)
C4—C5—C6—C7	−0.5 (5)	C11—C12—C13—C14	0.2 (5)
C5—C6—C7—C2	−0.2 (5)	C12—C13—C14—C9	1.1 (5)
C3—C2—C7—C6	0.8 (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.

Experimental details

Crystal data
Chemical formula	[Sn(C₇H₇)₃Cl]
M_r	427.52
Crystal system, space group	Trigonal, R3
Temperature (K)	100
a, c (Å)	16.7985 (2), 11.6875 (2)
V (Å³)	2856.23 (6)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.40 × 0.08 × 0.06

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.589, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	9077, 2737, 2431
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.074, 1.07
No. of reflections	2737
No. of parameters	139
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.25
Absolute structure	Flack (1983), 1372 Fridel pairs
Absolute structure parameter	−0.01 (4)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Selected bond lengths (Å) top

Sn1—C1	2.146 (3)	Sn2—C8	2.143 (3)
Sn1—Cl1	2.392 (2)	Sn2—Cl2	2.403 (2)

Acknowledgements

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

References

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