Monoclinic polymorph of chlorido-(dimethyl sulfoxide-κO)tri-phenyl-tin(IV).

The crystal structure of the title tin complex, [Sn(C6H5)3Cl(C2H6OS)], (I), has been reported with one mol-ecule in the asymmetric unit in an ortho-rhom-bic cell [Kumar et al. (2009 ▸). Acta Cryst. E65, m1602-m1603]. While using SnPh3Cl as a starting material for a reaction for which the products were recrystallized over a very long time (six months) from dimethyl sulfoxide (DMSO), a new polymorph was obtained for (I), with two independent mol-ecules in the asymmetric unit of a monoclinic cell. The coordination geometry of the Sn centres remains unchanged, with the Cl- ion and the DMSO mol-ecule in the apical positions and the phenyl C atoms in the equatorial positions of a trigonal bipyramid. The main difference between the polymorphs is the relative orientation of the phenyl rings in the equatorial plane, reflecting a degree of free rotation of these groups about their Sn-C bonds. In the crystal, mol-ecules are linked into [010] chains mediated by weak C-H⋯O inter-actions.

Chemical context

The Dakar research group and others worldwide have been focusing for a long time on the study of inter­actions of ammonium salts of oxyacids with metallic halides, to obtain adducts and complexes in which the oxyanion behaves as a ligand through its O atoms (Diassé-Sarr & Diop, 2011 ▸; Pouye et al., 2014 ▸; Toure et al., 2016 ▸; Sarr et al., 2016 ▸; Ng & Hook, 1999 ▸). The main advantage of this general strategy is the high solubility of the ammonium salts in common organic solvents, which facilitates the development of traditional synthetic methods in solution. The well-known flip side is that separation and purification procedures are almost always necessary, and that such syntheses are not in line with the principles of Green Chemistry, since solvent is an intrinsic waste.

However, from time to time, when the recrystallization is the method of purification, as-yet undiscovered polymorphs of unreacted materials, products or by-products, are emerging. In such instances, the involved chemistry may be of little inter­est, while the chemical crystallography of the unexpected polymorph(s) may be of significant inter­est, even in borderline cases like the disappearing polymorphs (Bučar et al., 2015 ▸). Actually, the propensity of a given mol­ecule to crystallize in various polymorphic forms is still difficult to predict (Price, 2009 ▸), and, for example, Ostwald’s ‘law of stages’ that states it is the least stable polymorph that crystallizes first, is of limited inter­est for concrete crystallizations (Threlfall, 2003 ▸). The current situation is thus that a significant number of new polymorphs are still obtained serendipitously, using a technique that could be coined as crystallization by oblivion. The herein reported title compound, (I), a new monoclinic polymorph of a frequently used starting material in tin chemistry, was obtained in this way: in one of our research programs, we have initiated the study of the inter­actions between [CH3NH2(CH2)2NH2CH3]SO4 and SnPh3Cl in a mixture of CH2Cl2 and dimethyl sulfoxide (DMSO) as solvent. One of the products obtained in an attempt of crystallization carried out over a very long time was the adduct obtained by addition of DMSO to the starting material SnPh3Cl, to form [SnPh3Cl(DMSO)]. The crystal structure of this compound has been reported previously, in space group P212121 (Kumar et al., 2009 ▸; CSD refcode: RUGYOI, Groom et al., 2016 ▸). In that case, crystals were obtained by dissolving SnPh3Cl in hot DMSO, affording fine colourless crystals by solvent evaporation over three days.

Structural commentary

Instead of the known ortho­rhom­bic structure of the title compound, we crystallized a monoclinic polymorph, in space group P21, with two mol­ecules in the asymmetric unit (Fig. 1 ▸).

Figure 1

The asymmetric unit for the new monoclinic phase of the title compound, with displacement ellipsoids at the 30% probability level. The inset is a fit between independent mol­ecules, based on all non-H atoms (Macrae et al., 2008 ▸), evidencing the rotation of one phenyl ring.

The independent mol­ecules display different conformations, as a consequence of a degree of free rotation of the phenyl groups about their Sn—C bonds. An overlay between both mol­ecules gives deviations as high as 1.7 Å, and the rotation of one phenyl group is obvious (Fig. 1 ▸, inset). This conformational flexibility seems to be the reason why the compound has at least two stable polymorphs, even if the trigonal–bipyramidal geometry for the Sn centre is retained. The relative orientation of the phenyl rings in the observed conformers may be estimated using the dihedral angles formed by the rings in each mol­ecule. These angles span a large range, from 28.3 (4) to 87.2° (Table 1 ▸). As a consequence, the orientation of the DMSO mol­ecule with respect to the SnPh3 core is also variable. In the ortho­rhom­bic phase, the S—Me groups of DMSO are staggered with the Sn—C bonds; in the new monoclinic phase, one complex displays a similar conformation, while in the other the S—Me groups are eclipsed with the Sn—C bonds (Fig. 2 ▸). The resulting simulated powder diffraction patterns for each polymorph are, as expected, also very different (Fig. 2 ▸).

Table 1

Relative orientation (°) of the phenyl rings in the three conformers of the title mol­ecule

Rings are arbitrarily labelled φ (i = 1, 2, 3) to compute the dihedral angles δi. For (I), δi angles were calculated with SHELXL2016/6 (Sheldrick, 2015b ▸).

Dihedral angle	P212121 phasea	P21 phase, mol­ecule 1	P21 phase, mol­ecule 2
δ1 = φ1/φ2	63.5	65.1 (2)	53.6 (3)
δ2 = φ2/φ3	70.7	65.1 (2)	59.1 (3)
δ3 = φ1/φ3	87.2	28.3 (4)	39.2 (3)

Note: (a) Kumar et al., 2009 ▸.

Figure 2

A comparison of the observed conformers for the title compound, viewed down the Cl—Sn—O axis (top: the previously known polymorph; bottom: the new P21 polymorph). Note the different orientations observed for the apical DMSO mol­ecule. The calculated powder patterns displayed on the right show that both polymorphs are crystallographically very different. Patterns were calculated with Mercury (Macrae et al., 2008 ▸; 5 < 2θ < 40°, λ = 1.54056 Å, FWHM = 0.2°).

With such contrasting features for the dimorphic phases of [SnPh3Cl(DMSO)], obtained basically from DMSO solutions using short and long evaporation times, one could expect the apparition of other phases under different conditions of crystallization, for example by varying the solvent or the temperature of crystallization.

Supra­molecular features

In the extended structure of the ortho­rhom­bic phase, one methyl group in DMSO forms weak C—H⋯Cl and C—H⋯π inter­actions, and mol­ecules related by the 21 screw axis in the [010] direction feature π–π inter­actions between two phenyl rings, separated by 3.934 (3) Å (Kumar et al., 2009 ▸). In the monoclinic form, mol­ecules related through the 21 axis in space group P21 no longer form π–π inter­actions. The supra­molecular structure of (I) is based rather on weak C—H⋯Cl contacts involving, as in the first polymorph, the methyl groups of the DMSO mol­ecule as donor, with H⋯Cl separations ranging from 2.82 to 2.94 Å. The resulting supra­molecular one-dimensional structure is a zigzag chain of alternating Sn1 and Sn2 independent mol­ecules, running along the screw axis (Fig. 3 ▸). The absence of other stabilizing inter­molecular contacts may suggest a less thermodynamically stable crystal, compared to the ortho­rhom­bic crystal obtained by fast crystallization, in contradiction with Ostwald’s rule (Threlfall, 2003 ▸). However, the crystal structures are in agreement with the calculated densities for both polymorphs: 1.562 g cm−3 for the ortho­rhom­bic form and 1.514 g cm−3 for the less stable monoclinic form reported here.

Figure 3

Part of the crystal structure of the title polymorph, showing the supra­molecular network formed along the screw axis 21 in space group P21. Dashed bonds represent C—H⋯Cl inter­molecular contacts. [Symmetry codes: (i) −1 + x, y, −1 + z; (ii) 1 − x, − + y, 1 − z; (iii) −x, − + y, −z.]

Database survey

According to the CSD (V5.39; Groom et al., 2016 ▸), DMSO is a good coordinating solvent for tin: 64 hits may be recovered, in which the average value for the bond length Sn—O is 2.27 (11) Å for 105 instances. The bond length characterizing the coordination of DMSO in the monoclinic polymorph is very long compared to this average: the bond lengths Sn1—O1 and Sn2—O2 are 2.487 (4) and 2.368 (4) Å, respectively, reflecting a coordination of limited strength. Again, the ortho­rhom­bic form seems to be stabilized by comparison with the monoclinic form, as the DMSO is more tightly coordinated, with Sn—O(DMSO) = 2.311 (3) Å (Kumar et al., 2009 ▸).

Synthesis and crystallization

[CH3NH2(CH2)2NH2CH3]SO4 has been synthesized on allowing CH3NH(CH2)2NHCH3 to react with H2SO4 in water in a 1:1 ratio. Slow evaporation of the resulting solution at 300 K gave after six weeks a yellowish viscous liquid supposed to be [CH3NH2(CH2)2NH2CH3]SO4 (L). When L (0.024 g, 0.130 mmol) dissolved in 50 ml of a 1:1 water/ethanol mixture was reacted with SnPh3Cl (0.100 g, 0.260 mmol) dissolved in a 1:1 di­chloro­methane/methanol mixture (50 ml), a slightly cloudy solution was obtained and filtered. The filtrate, when submitted to a slow solvent evaporation at 300 K over three days, produced a powder, which was redissolved in DMSO. Slow solvent evaporation at 300 K over six months afforded colourless blocks of (I) suitable for X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The C-bound H atoms were included in calculated positions (C—H = 0.93–0.96 Å) and refined as riding, with U iso(H) =1.5U eq(C-methyl) and 1.2U eq(C) for other H atoms. The absolute configuration was assigned on the basis of the refinement of the Flack parameter (Parsons et al., 2013 ▸).

Table 2

Experimental details

Crystal data
Chemical formula	[Sn(C6H5)3Cl(C2H6OS)]
M r	463.57
Crystal system, space group	Monoclinic, P21
Temperature (K)	297
a, b, c (Å)	8.81934 (18), 15.3698 (3), 15.4209 (3)
β (°)	103.294 (2)
V (Å3)	2034.31 (7)
Z	4
Radiation type	Mo Kα
μ (mm−1)	1.49
Crystal size (mm)	0.48 × 0.30 × 0.23
Data collection
Diffractometer	Rigaku OD Xcalibur Atlas Gemini
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2015 ▸)
T min, T max	0.880, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	133515, 14767, 10835
R int	0.051
(sin θ/λ)max (Å−1)	0.767
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.038, 0.083, 1.04
No. of reflections	14767
No. of parameters	437
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	1.48, −0.75
Absolute structure	Flack x determined using 4338 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	−0.039 (6)

Computer programs: CrysAlis PRO (Rigaku OD, 2015 ▸), SHELXT2014 (Sheldrick, 2015a ▸), SHELXL2016 (Sheldrick, 2015b ▸), XP in SHELXTL (Sheldrick, 2008 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018000439/hb4193sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018000439/hb4193Isup2.hkl

CCDC reference: 1815199

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Sn(C6H5)3Cl(C2H6OS)]	F(000) = 928
Mr = 463.57	Dx = 1.514 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 8.81934 (18) Å	Cell parameters from 28302 reflections
b = 15.3698 (3) Å	θ = 3.3–25.8°
c = 15.4209 (3) Å	µ = 1.49 mm−1
β = 103.294 (2)°	T = 297 K
V = 2034.31 (7) Å3	Block, colourless
Z = 4	0.48 × 0.30 × 0.23 mm

Rigaku OD Xcalibur Atlas Gemini diffractometer	14767 independent reflections
Radiation source: Enhance (Mo) X-ray Source	10835 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 10.5564 pixels mm-1	θmax = 33.0°, θmin = 3.0°
ω scans	h = −13→13
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2015)	k = −23→23
Tmin = 0.880, Tmax = 0.941	l = −23→23
133515 measured reflections

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)] = 0.038	H-atom parameters constrained
wR(F2) = 0.083	w = 1/[σ2(Fo2) + (0.0301P)2 + 1.1572P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
14767 reflections	Δρmax = 1.48 e Å−3
437 parameters	Δρmin = −0.74 e Å−3
1 restraint	Absolute structure: Flack x determined using 4338 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 constraints	Absolute structure parameter: −0.039 (6)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
Sn1	0.34055 (4)	0.62754 (2)	0.81374 (2)	0.04086 (8)
Cl1	0.14377 (15)	0.71185 (10)	0.70653 (11)	0.0575 (3)
S1	0.6727 (2)	0.60605 (13)	0.98769 (13)	0.0760 (5)
O1	0.5508 (5)	0.5538 (3)	0.9246 (3)	0.0626 (10)
C1	0.6394 (12)	0.5930 (10)	1.0910 (6)	0.154 (7)
H1A	0.530448	0.600927	1.088428	0.232*
H1B	0.698577	0.635231	1.130756	0.232*
H1C	0.670287	0.535548	1.112350	0.232*
C2	0.8465 (9)	0.5461 (9)	1.0021 (7)	0.121 (3)
H2A	0.829588	0.488105	1.021127	0.182*
H2B	0.926307	0.573706	1.046403	0.182*
H2C	0.878378	0.543618	0.946699	0.182*
C3	0.3347 (6)	0.7082 (3)	0.9248 (3)	0.0440 (11)
C4	0.2591 (8)	0.6773 (4)	0.9877 (4)	0.0589 (15)
H4	0.209888	0.623450	0.978833	0.071*
C5	0.2546 (9)	0.7242 (5)	1.0634 (5)	0.0741 (19)
H5	0.202098	0.702700	1.104703	0.089*
C6	0.3290 (10)	0.8032 (6)	1.0764 (5)	0.084 (2)
H6	0.329355	0.834620	1.127994	0.101*
C7	0.4025 (9)	0.8362 (5)	1.0150 (6)	0.084 (2)
H7	0.449645	0.890623	1.023832	0.101*
C8	0.4066 (8)	0.7885 (4)	0.9395 (5)	0.0661 (16)
H8	0.458269	0.810722	0.898147	0.079*
C9	0.2087 (6)	0.5120 (3)	0.8110 (3)	0.0419 (11)
C10	0.2788 (9)	0.4313 (4)	0.8150 (4)	0.0579 (14)
H10	0.385218	0.426973	0.818618	0.070*
C11	0.1885 (11)	0.3558 (4)	0.8136 (4)	0.075 (2)
H11	0.236112	0.301569	0.816462	0.090*
C12	0.0321 (11)	0.3608 (5)	0.8082 (5)	0.080 (2)
H12	−0.026361	0.310414	0.808045	0.096*
C13	−0.0371 (9)	0.4402 (6)	0.8030 (5)	0.076 (2)
H13	−0.143832	0.443817	0.798711	0.091*
C14	0.0488 (7)	0.5163 (4)	0.8039 (4)	0.0578 (14)
H14	−0.000695	0.570040	0.799842	0.069*
C15	0.5039 (5)	0.6303 (4)	0.7325 (3)	0.0449 (10)
C16	0.6395 (7)	0.6785 (4)	0.7522 (5)	0.0625 (15)
H16	0.665734	0.709282	0.805463	0.075*
C17	0.7363 (8)	0.6816 (6)	0.6940 (7)	0.087 (2)
H17	0.825710	0.715735	0.707348	0.105*
C18	0.7026 (10)	0.6354 (7)	0.6177 (7)	0.099 (3)
H18	0.769586	0.637220	0.579073	0.119*
C19	0.5686 (12)	0.5852 (6)	0.5964 (6)	0.097 (3)
H19	0.546093	0.552816	0.544026	0.116*
C20	0.4687 (8)	0.5835 (4)	0.6535 (4)	0.0616 (15)
H20	0.377499	0.550909	0.638875	0.074*
Sn2	0.21662 (4)	0.54546 (2)	0.32336 (2)	0.04487 (8)
Cl2	−0.03762 (16)	0.62413 (13)	0.27444 (12)	0.0729 (4)
S2	0.52976 (17)	0.39472 (10)	0.33520 (9)	0.0526 (3)
O2	0.4552 (4)	0.4702 (3)	0.3724 (3)	0.0534 (9)
C21	0.7148 (10)	0.4347 (6)	0.3252 (8)	0.111 (4)
H21A	0.700502	0.475938	0.277182	0.166*
H21B	0.777566	0.387183	0.313190	0.166*
H21C	0.766040	0.462650	0.379761	0.166*
C22	0.5951 (9)	0.3236 (4)	0.4253 (5)	0.0731 (18)
H22A	0.651875	0.355947	0.475644	0.110*
H22B	0.661969	0.280355	0.408952	0.110*
H22C	0.507284	0.295784	0.440433	0.110*
C23	0.1457 (6)	0.4846 (4)	0.4317 (3)	0.0465 (11)
C24	0.1469 (7)	0.3946 (4)	0.4382 (4)	0.0604 (14)
H24	0.186122	0.361348	0.398009	0.073*
C25	0.0900 (9)	0.3541 (6)	0.5046 (5)	0.082 (2)
H25	0.087611	0.293635	0.507276	0.098*
C26	0.0380 (9)	0.4017 (8)	0.5655 (5)	0.091 (3)
H26	0.002901	0.374122	0.610813	0.109*
C27	0.0370 (9)	0.4904 (7)	0.5604 (5)	0.084 (2)
H27	0.000894	0.522937	0.602374	0.101*
C28	0.0893 (7)	0.5321 (5)	0.4932 (4)	0.0683 (16)
H28	0.086386	0.592521	0.489635	0.082*
C29	0.1821 (6)	0.4685 (4)	0.2058 (3)	0.0449 (11)
C30	0.2624 (8)	0.4840 (5)	0.1406 (4)	0.0627 (16)
H30	0.333652	0.529506	0.147514	0.075*
C31	0.2388 (10)	0.4330 (6)	0.0654 (5)	0.081 (2)
H31	0.292424	0.445230	0.021473	0.097*
C32	0.1357 (10)	0.3636 (6)	0.0544 (5)	0.083 (2)
H32	0.122027	0.328401	0.004200	0.099*
C33	0.0542 (9)	0.3475 (5)	0.1184 (5)	0.077 (2)
H33	−0.016318	0.301658	0.111762	0.093*
C34	0.0780 (7)	0.4004 (4)	0.1930 (4)	0.0608 (15)
H34	0.021684	0.389495	0.236020	0.073*
C35	0.3540 (6)	0.6620 (4)	0.3340 (4)	0.0477 (12)
C36	0.2896 (8)	0.7420 (4)	0.3393 (4)	0.0596 (15)
H36	0.184343	0.745718	0.339215	0.072*
C37	0.3757 (9)	0.8177 (4)	0.3449 (5)	0.0664 (17)
H37	0.329304	0.871349	0.349298	0.080*
C38	0.5283 (9)	0.8128 (5)	0.3439 (5)	0.0745 (19)
H38	0.586515	0.863655	0.347323	0.089*
C39	0.5983 (9)	0.7348 (5)	0.3381 (6)	0.087 (2)
H39	0.703561	0.732256	0.337942	0.104*
C40	0.5110 (8)	0.6591 (5)	0.3323 (6)	0.074 (2)
H40	0.557948	0.605751	0.327231	0.089*

	U11	U22	U33	U12	U13	U23
Sn1	0.04052 (16)	0.03857 (15)	0.04383 (16)	−0.00402 (14)	0.01042 (12)	−0.00110 (15)
Cl1	0.0418 (6)	0.0626 (8)	0.0669 (8)	0.0044 (6)	0.0100 (6)	0.0178 (7)
S1	0.0559 (9)	0.0893 (13)	0.0750 (11)	0.0037 (8)	−0.0011 (8)	−0.0046 (9)
O1	0.065 (2)	0.055 (2)	0.057 (2)	0.007 (2)	−0.0088 (18)	0.000 (2)
C1	0.082 (6)	0.30 (2)	0.070 (5)	−0.013 (8)	−0.003 (5)	−0.019 (8)
C2	0.066 (5)	0.174 (10)	0.117 (7)	0.033 (6)	0.008 (5)	−0.025 (8)
C3	0.046 (3)	0.040 (2)	0.044 (3)	0.001 (2)	0.006 (2)	−0.003 (2)
C4	0.072 (4)	0.048 (3)	0.059 (4)	0.004 (3)	0.019 (3)	−0.002 (3)
C5	0.082 (5)	0.089 (5)	0.059 (4)	0.019 (4)	0.031 (4)	−0.005 (4)
C6	0.089 (5)	0.091 (5)	0.070 (5)	0.011 (4)	0.014 (4)	−0.033 (4)
C7	0.084 (5)	0.072 (5)	0.095 (6)	−0.016 (4)	0.021 (4)	−0.037 (4)
C8	0.069 (4)	0.061 (4)	0.068 (4)	−0.014 (3)	0.015 (3)	−0.015 (3)
C9	0.050 (3)	0.043 (3)	0.034 (2)	−0.008 (2)	0.010 (2)	0.0001 (19)
C10	0.076 (4)	0.048 (3)	0.049 (3)	0.004 (3)	0.013 (3)	−0.002 (2)
C11	0.124 (7)	0.041 (3)	0.059 (4)	−0.017 (4)	0.018 (4)	−0.005 (3)
C12	0.116 (7)	0.074 (5)	0.054 (4)	−0.049 (5)	0.026 (4)	−0.008 (3)
C13	0.070 (4)	0.103 (6)	0.059 (4)	−0.045 (4)	0.021 (3)	−0.011 (4)
C14	0.056 (3)	0.066 (4)	0.055 (3)	−0.012 (3)	0.021 (3)	−0.004 (3)
C15	0.034 (2)	0.049 (2)	0.052 (3)	0.005 (2)	0.0104 (18)	0.007 (3)
C16	0.043 (3)	0.067 (4)	0.076 (4)	−0.002 (2)	0.010 (3)	0.012 (3)
C17	0.046 (4)	0.094 (6)	0.130 (7)	0.007 (3)	0.038 (4)	0.029 (5)
C18	0.079 (5)	0.110 (6)	0.133 (8)	0.018 (5)	0.074 (5)	0.026 (7)
C19	0.128 (8)	0.101 (6)	0.074 (5)	0.036 (5)	0.047 (5)	0.001 (4)
C20	0.060 (4)	0.068 (4)	0.061 (4)	−0.002 (3)	0.023 (3)	−0.007 (3)
Sn2	0.03997 (16)	0.04791 (18)	0.04579 (17)	0.00040 (15)	0.00790 (13)	0.00084 (15)
Cl2	0.0441 (7)	0.0668 (8)	0.0983 (11)	0.0105 (8)	−0.0033 (7)	0.0098 (10)
S2	0.0523 (8)	0.0547 (7)	0.0489 (7)	0.0072 (6)	0.0076 (6)	−0.0020 (6)
O2	0.0425 (19)	0.056 (2)	0.059 (2)	0.0104 (17)	0.0079 (17)	−0.0024 (18)
C21	0.082 (5)	0.080 (5)	0.196 (11)	0.022 (4)	0.086 (7)	0.031 (6)
C22	0.081 (5)	0.070 (4)	0.070 (4)	0.020 (3)	0.020 (4)	0.015 (3)
C23	0.037 (2)	0.062 (3)	0.040 (2)	0.001 (2)	0.008 (2)	−0.002 (2)
C24	0.063 (4)	0.064 (3)	0.055 (3)	0.005 (3)	0.016 (3)	0.009 (3)
C25	0.085 (5)	0.087 (5)	0.073 (5)	−0.007 (4)	0.016 (4)	0.027 (4)
C26	0.062 (4)	0.163 (9)	0.050 (4)	−0.007 (5)	0.016 (3)	0.023 (5)
C27	0.071 (5)	0.139 (8)	0.050 (4)	−0.008 (5)	0.027 (3)	−0.019 (4)
C28	0.066 (4)	0.080 (5)	0.061 (4)	0.005 (3)	0.019 (3)	−0.011 (3)
C29	0.044 (3)	0.054 (3)	0.036 (2)	0.005 (2)	0.010 (2)	0.004 (2)
C30	0.060 (4)	0.078 (4)	0.055 (3)	0.002 (3)	0.023 (3)	0.012 (3)
C31	0.093 (5)	0.109 (6)	0.050 (4)	0.028 (5)	0.032 (4)	0.015 (4)
C32	0.104 (6)	0.088 (5)	0.050 (4)	0.026 (5)	0.005 (4)	−0.013 (4)
C33	0.089 (5)	0.076 (4)	0.057 (4)	−0.015 (4)	−0.004 (4)	−0.012 (3)
C34	0.062 (4)	0.070 (4)	0.051 (3)	−0.013 (3)	0.014 (3)	−0.007 (3)
C35	0.047 (3)	0.049 (3)	0.045 (3)	−0.003 (2)	0.007 (2)	−0.001 (2)
C36	0.059 (4)	0.060 (3)	0.057 (4)	0.003 (3)	0.007 (3)	−0.007 (3)
C37	0.080 (5)	0.049 (3)	0.063 (4)	0.000 (3)	0.003 (3)	−0.001 (3)
C38	0.084 (5)	0.059 (4)	0.078 (5)	−0.021 (4)	0.012 (4)	0.005 (3)
C39	0.065 (4)	0.066 (4)	0.137 (8)	−0.020 (3)	0.035 (5)	−0.003 (4)
C40	0.052 (4)	0.064 (4)	0.109 (6)	−0.001 (3)	0.026 (4)	−0.004 (4)

Sn1—C15	2.115 (4)	Sn2—C29	2.127 (5)
Sn1—C9	2.118 (5)	Sn2—C23	2.130 (5)
Sn1—C3	2.125 (5)	Sn2—C35	2.147 (6)
Sn1—Cl1	2.4708 (14)	Sn2—O2	2.368 (4)
Sn1—O1	2.487 (4)	Sn2—Cl2	2.5061 (14)
S1—O1	1.505 (4)	S2—O2	1.510 (4)
S1—C1	1.697 (10)	S2—C22	1.757 (6)
S1—C2	1.758 (9)	S2—C21	1.784 (8)
C1—H1A	0.9600	C21—H21A	0.9600
C1—H1B	0.9600	C21—H21B	0.9600
C1—H1C	0.9600	C21—H21C	0.9600
C2—H2A	0.9600	C22—H22A	0.9600
C2—H2B	0.9600	C22—H22B	0.9600
C2—H2C	0.9600	C22—H22C	0.9600
C3—C4	1.381 (8)	C23—C28	1.378 (8)
C3—C8	1.383 (8)	C23—C24	1.386 (8)
C4—C5	1.379 (9)	C24—C25	1.388 (9)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.373 (11)	C25—C26	1.351 (12)
C5—H5	0.9300	C25—H25	0.9300
C6—C7	1.362 (12)	C26—C27	1.364 (13)
C6—H6	0.9300	C26—H26	0.9300
C7—C8	1.384 (9)	C27—C28	1.385 (10)
C7—H7	0.9300	C27—H27	0.9300
C8—H8	0.9300	C28—H28	0.9300
C9—C10	1.381 (8)	C29—C34	1.377 (8)
C9—C14	1.390 (8)	C29—C30	1.377 (8)
C10—C11	1.405 (9)	C30—C31	1.375 (10)
C10—H10	0.9300	C30—H30	0.9300
C11—C12	1.364 (11)	C31—C32	1.386 (12)
C11—H11	0.9300	C31—H31	0.9300
C12—C13	1.359 (12)	C32—C33	1.370 (11)
C12—H12	0.9300	C32—H32	0.9300
C13—C14	1.391 (9)	C33—C34	1.385 (9)
C13—H13	0.9300	C33—H33	0.9300
C14—H14	0.9300	C34—H34	0.9300
C15—C16	1.381 (8)	C35—C36	1.366 (8)
C15—C20	1.387 (8)	C35—C40	1.391 (8)
C16—C17	1.375 (10)	C36—C37	1.381 (9)
C16—H16	0.9300	C36—H36	0.9300
C17—C18	1.348 (13)	C37—C38	1.351 (10)
C17—H17	0.9300	C37—H37	0.9300
C18—C19	1.386 (13)	C38—C39	1.361 (11)
C18—H18	0.9300	C38—H38	0.9300
C19—C20	1.382 (10)	C39—C40	1.386 (9)
C19—H19	0.9300	C39—H39	0.9300
C20—H20	0.9300	C40—H40	0.9300
C15—Sn1—C9	116.8 (2)	C29—Sn2—C23	114.4 (2)
C15—Sn1—C3	127.7 (2)	C29—Sn2—C35	119.8 (2)
C9—Sn1—C3	112.9 (2)	C23—Sn2—C35	124.7 (2)
C15—Sn1—Cl1	93.59 (13)	C29—Sn2—O2	86.73 (16)
C9—Sn1—Cl1	97.39 (15)	C23—Sn2—O2	86.23 (17)
C3—Sn1—Cl1	95.16 (14)	C35—Sn2—O2	86.50 (18)
C15—Sn1—O1	85.09 (16)	C29—Sn2—Cl2	93.96 (14)
C9—Sn1—O1	87.17 (17)	C23—Sn2—Cl2	92.53 (14)
C3—Sn1—O1	82.21 (17)	C35—Sn2—Cl2	94.06 (16)
Cl1—Sn1—O1	175.36 (11)	O2—Sn2—Cl2	178.75 (11)
O1—S1—C1	107.0 (5)	O2—S2—C22	105.6 (3)
O1—S1—C2	105.9 (4)	O2—S2—C21	104.8 (3)
C1—S1—C2	98.8 (5)	C22—S2—C21	98.2 (4)
S1—O1—Sn1	120.6 (2)	S2—O2—Sn2	133.4 (2)
S1—C1—H1A	109.5	S2—C21—H21A	109.5
S1—C1—H1B	109.5	S2—C21—H21B	109.5
H1A—C1—H1B	109.5	H21A—C21—H21B	109.5
S1—C1—H1C	109.5	S2—C21—H21C	109.5
H1A—C1—H1C	109.5	H21A—C21—H21C	109.5
H1B—C1—H1C	109.5	H21B—C21—H21C	109.5
S1—C2—H2A	109.5	S2—C22—H22A	109.5
S1—C2—H2B	109.5	S2—C22—H22B	109.5
H2A—C2—H2B	109.5	H22A—C22—H22B	109.5
S1—C2—H2C	109.5	S2—C22—H22C	109.5
H2A—C2—H2C	109.5	H22A—C22—H22C	109.5
H2B—C2—H2C	109.5	H22B—C22—H22C	109.5
C4—C3—C8	118.0 (5)	C28—C23—C24	118.5 (6)
C4—C3—Sn1	118.1 (4)	C28—C23—Sn2	121.6 (5)
C8—C3—Sn1	123.9 (4)	C24—C23—Sn2	119.8 (4)
C5—C4—C3	121.8 (6)	C23—C24—C25	120.3 (7)
C5—C4—H4	119.1	C23—C24—H24	119.9
C3—C4—H4	119.1	C25—C24—H24	119.9
C6—C5—C4	118.7 (7)	C26—C25—C24	120.4 (8)
C6—C5—H5	120.7	C26—C25—H25	119.8
C4—C5—H5	120.7	C24—C25—H25	119.8
C7—C6—C5	121.0 (7)	C25—C26—C27	120.1 (7)
C7—C6—H6	119.5	C25—C26—H26	120.0
C5—C6—H6	119.5	C27—C26—H26	120.0
C6—C7—C8	119.7 (7)	C26—C27—C28	120.4 (7)
C6—C7—H7	120.1	C26—C27—H27	119.8
C8—C7—H7	120.1	C28—C27—H27	119.8
C3—C8—C7	120.7 (7)	C23—C28—C27	120.3 (7)
C3—C8—H8	119.6	C23—C28—H28	119.8
C7—C8—H8	119.6	C27—C28—H28	119.8
C10—C9—C14	118.8 (5)	C34—C29—C30	117.7 (5)
C10—C9—Sn1	120.9 (4)	C34—C29—Sn2	120.3 (4)
C14—C9—Sn1	120.3 (4)	C30—C29—Sn2	122.0 (5)
C9—C10—C11	119.7 (7)	C31—C30—C29	120.9 (7)
C9—C10—H10	120.2	C31—C30—H30	119.5
C11—C10—H10	120.2	C29—C30—H30	119.5
C12—C11—C10	121.1 (7)	C30—C31—C32	120.6 (7)
C12—C11—H11	119.5	C30—C31—H31	119.7
C10—C11—H11	119.5	C32—C31—H31	119.7
C13—C12—C11	119.2 (6)	C33—C32—C31	119.3 (7)
C13—C12—H12	120.4	C33—C32—H32	120.4
C11—C12—H12	120.4	C31—C32—H32	120.4
C12—C13—C14	121.2 (7)	C32—C33—C34	119.2 (7)
C12—C13—H13	119.4	C32—C33—H33	120.4
C14—C13—H13	119.4	C34—C33—H33	120.4
C9—C14—C13	120.1 (6)	C29—C34—C33	122.2 (6)
C9—C14—H14	120.0	C29—C34—H34	118.9
C13—C14—H14	120.0	C33—C34—H34	118.9
C16—C15—C20	118.6 (5)	C36—C35—C40	117.3 (6)
C16—C15—Sn1	123.7 (4)	C36—C35—Sn2	121.4 (4)
C20—C15—Sn1	117.7 (4)	C40—C35—Sn2	121.3 (5)
C17—C16—C15	120.8 (7)	C35—C36—C37	122.2 (6)
C17—C16—H16	119.6	C35—C36—H36	118.9
C15—C16—H16	119.6	C37—C36—H36	118.9
C18—C17—C16	120.5 (7)	C38—C37—C36	119.2 (7)
C18—C17—H17	119.8	C38—C37—H37	120.4
C16—C17—H17	119.8	C36—C37—H37	120.4
C17—C18—C19	120.3 (7)	C37—C38—C39	121.2 (7)
C17—C18—H18	119.8	C37—C38—H38	119.4
C19—C18—H18	119.8	C39—C38—H38	119.4
C20—C19—C18	119.6 (8)	C38—C39—C40	119.3 (7)
C20—C19—H19	120.2	C38—C39—H39	120.3
C18—C19—H19	120.2	C40—C39—H39	120.3
C19—C20—C15	120.2 (7)	C39—C40—C35	120.8 (7)
C19—C20—H20	119.9	C39—C40—H40	119.6
C15—C20—H20	119.9	C35—C40—H40	119.6

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl2i	0.96	2.83	3.555 (9)	134
C21—H21B···Cl1ii	0.96	2.82	3.716 (9)	156
C22—H22B···Cl1ii	0.96	2.94	3.813 (7)	153