Low-temperature redetermination of tribenzyl­chloridotin(IV)

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.026
• wR factor = 0.074
• Data-to-parameter ratio = 19.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem...          Z

Alert level C
            Value of measurement temperature given =   100.000
            Value of melting point given =     0.000
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.08
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.46
           From the CIF: _reflns_number_total               2737
           Count of symmetry unique reflns         1462
           Completeness (_total/calc)            187.21%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1275
           Fraction of Friedel pairs measured     0.872
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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

Computing details

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

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)

Crystal data

[Sn(C7H7)3Cl]	Dx = 1.491 Mg m^−3
Mr = 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) Å^3	Prism, colorless
Z = 6	0.40 × 0.08 × 0.06 mm
F(000) = 1284

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0515P)^2 + 0.375P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2737 reflections	Δρmax = 0.53 e Å^−3
139 parameters	Δρmin = −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)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Sn1—C1^i	2.146 (3)	C5—C6	1.396 (5)
Sn1—C1	2.146 (3)	C5—H5	0.9500
Sn1—C1^ii	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—C8^i	2.143 (3)	C8—C9	1.494 (5)
Sn2—C8	2.143 (3)	C8—H8A	0.9900
Sn2—C8^ii	2.143 (3)	C8—H8B	0.9900
Sn2—Cl2	2.403 (2)	C9—C10	1.387 (4)
Sn2—Cl1^iii	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
C1^i—Sn1—C1	115.06 (6)	C5—C4—H4	119.8
C1^i—Sn1—C1^ii	115.06 (7)	C4—C5—C6	119.0 (3)
C1—Sn1—C1^ii	115.06 (6)	C4—C5—H5	120.5
C1^i—Sn1—Cl1	103.05 (9)	C6—C5—H5	120.5
C1—Sn1—Cl1	103.05 (9)	C7—C6—C5	120.5 (3)
C1^ii—Sn1—Cl1	103.05 (9)	C7—C6—H6	119.8
C1^i—Sn1—Cl2	76.95 (9)	C5—C6—H6	119.8
C1—Sn1—Cl2	76.95 (9)	C6—C7—C2	120.6 (3)
C1^ii—Sn1—Cl2	76.95 (9)	C6—C7—H7	119.7
Cl1—Sn1—Cl2	180.0	C2—C7—H7	119.7
C8^i—Sn2—C8	116.46 (6)	C9—C8—Sn2	110.7 (2)
C8^i—Sn2—C8^ii	116.46 (6)	C9—C8—H8A	109.5
C8—Sn2—C8^ii	116.46 (6)	Sn2—C8—H8A	109.5
C8^i—Sn2—Cl2	100.98 (9)	C9—C8—H8B	109.5
C8—Sn2—Cl2	100.98 (9)	Sn2—C8—H8B	109.5
C8^ii—Sn2—Cl2	100.98 (9)	H8A—C8—H8B	108.1
C8^i—Sn2—Cl1^iii	79.02 (9)	C10—C9—C14	117.0 (3)
C8—Sn2—Cl1^iii	79.02 (9)	C10—C9—C8	122.9 (3)
C8^ii—Sn2—Cl1^iii	79.02 (9)	C14—C9—C8	120.1 (3)
Cl2—Sn2—Cl1^iii	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
C1^i—Sn1—C1—C2	−41.4 (3)	C8^i—Sn2—C8—C9	−31.7 (3)
C1^ii—Sn1—C1—C2	−178.70 (16)	C8^ii—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)	Cl1^iii—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.