Tetra­kis[3,5-bis­(trifluoro­meth­yl)phenyl]tin(IV)

Daniel Foucher; Damion Miles; Alan J Lough

doi:10.1107/S1600536809019588

. 2009 Jun 6;65(Pt 7):m704. doi: 10.1107/S1600536809019588

Tetrakis[3,5-bis(trifluoromethyl)phenyl]tin(IV)

Daniel Foucher ^a, Damion Miles ^a, Alan J Lough ^b,^*

PMCID: PMC2969316 PMID: 21582650

Abstract

The title molecule, [Sn(C₈H₃F₆)₄], lies on a twofold rotation axis with the Sn^IV ion in a distorted tetrahedral coordination environment. Both –CF₃ groups attached to one of the unique benzene rings are disordered over two sets of sites, with the ratios of refined occupancies being 0.719 (14):0.281 (14) and 0.63 (5):0.37 (5).

Related literature

For synthesis of the title compound, see King et al. (1986 ▶). Additional preparative details of similar compounds are given by Lu & Tilley (2000 ▶). For related crystal structures, see: Young et al. (2005 ▶); Smith et al. (1994 ▶); Wharf & Simard (1997 ▶). For further details of geometric distortions in related compounds, see Charissé et al. (1998 ▶).

Experimental

Crystal data

[Sn(C₈H₃F₆)₄]
M _r = 971.11
Monoclinic,
a = 17.3506 (8) Å
b = 20.8038 (11) Å
c = 9.8944 (3) Å
β = 109.998 (3)°
V = 3356.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 150 K
0.28 × 0.24 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.798, T _max = 0.897
10930 measured reflections
3818 independent reflections
3142 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.097
S = 1.06
3818 reflections
314 parameters
211 restraints
H-atom parameters constrained
Δρ_max = 1.80 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019588/pk2165sup1.cif

e-65-0m704-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019588/pk2165Isup2.hkl

e-65-0m704-Isup2.hkl^{(187.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Sn1—C9	2.146 (3)
Sn1—C1	2.150 (3)

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C9—Sn1—C9ⁱ	109.73 (16)
C9—Sn1—C1	104.69 (11)
C9—Sn1—C1ⁱ	108.35 (11)
C1—Sn1—C1ⁱ	120.82 (17)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge NSERC Canada, the University of Toronto, the NSERC Discovery fund and the Dean’s Seed Fund Initiative (Ryerson University) for funding.

supplementary crystallographic information

Comment

The preparation of polymerizable dialkyl or diaryl tin monomers bearing either chlorine or hydride groups (Lu & Tilley, 2000) is accessed through the initial comportionation reactions involving the tetraalkyl- or tetraryltin(IV) compounds and tin(IV) tetrachloride. The incorporation of perfluorinated species in the backbone of polystannanes should by design impart an improved stability towards nucleophilic attack. Our interest in the distortions from tetrahedral geometry of other tin aryl compounds (Charissé et al., 1998), prompted us to determine the crystal structure of the title compound which was previously synthesized by King et al. (1986).

The title molecule (Fig. 1) lies on a twofold rotation axis. The Sn^IV ion is in a distorted tetrahedral coordination environment (Table 1). The angular disortion from the ideal values of 109.5° is most likely a consequence of the steric crowding caused by the 3,5 substitution of the bulky trifluoromethyl groups on the benzene rings. The Sn—C bond distances in the title compound are the same within experimental error and are comparable to those in the para-substituted and meta-substituted tetrakis[(trifluoromethyl)phenyl]stannane structures (Young et al., 2005; Smith et al., 1994) but are significantly longer than the Sn—C bonds in the related triaryltin(IV)chloride compounds (Wharf & Simard, 1997).

Experimental

The title compound was prepared from the refluxing Grignard reaction of 3,5-trifluoromethylphenyl magnesium bromide (12.5 mmol) in ether with anhydrous tin tetrachloride (3.125 mmol). The reaction mixture was refluxed overnight, cooled and filtered to remove salts. The crude compound was purified first by sublimation, and then recrystallization from ether to yield long large needles suitable for X-ray diffraction. Yield 1.33 g, 44%. m.p. 426 K (literature 436 K; King et al., 1986).