Tetra­butyl­ammonium butyl­tetra­chlorido­stannate(IV)

Tidiane Diop; Arie van der Lee; Libasse Diop

doi:10.1107/S1600536813026172

. 2013 Sep 28;69(Pt 10):m562–m563. doi: 10.1107/S1600536813026172

Tetrabutylammonium butyltetrachloridostannate(IV)

Tidiane Diop ^a,^*, Arie van der Lee ^b, Libasse Diop ^a

PMCID: PMC3790365 PMID: 24098187

Abstract

In the title compound, [N(C₄H₉)₄][Sn(C₄H₉)Cl₄], the Sn^IV atom of the stannate anion has a trigonal-bipyramidal coordination sphere by two Cl atoms and one butyl chain in the equatorial plane and by two Cl atoms in the apical positions. Two of the four butyl chains of the tetrabutylammonium cation are partially disordered, each with refined site occupancies of 0.691 (6):0.309 (6). Weak C—H⋯Cl hydrogen-bonding interactions help to consolidate the crystal packing, as well as a short Cl⋯Cl interaction of 3.295 (2) Å.

Related literature

For general background to and applications of tin(IV) compounds, see: Evans & Karpel (1985 ▶); Davies et al. (2008 ▶). For related structures, see: Webster et al. (1976 ▶); Sow et al. (2010 ▶). For short Cl⋯Cl interactions in other chloridotin(IV) complexes, see: Brazeau et al. (2012 ▶); Cabon et al. (2010 ▶). For background to the weighting schemes used in the refinement, see: Prince (1982 ▶); Watkin (1994 ▶). graphic file with name e-69-0m562-scheme1.jpg

Experimental

Crystal data

(C₁₆H₃₆N)[Sn(C₄H₉)Cl₄]
M _r = 560.08
Triclinic,
a = 11.6933 (5) Å
b = 11.7463 (5) Å
c = 12.2301 (6) Å
α = 114.236 (5)°
β = 101.680 (4)°
γ = 104.123 (4)°
V = 1395.80 (14) Å³
Z = 2
Mo Kα radiation
μ = 1.30 mm⁻¹
T = 175 K
0.45 × 0.40 × 0.15 mm

Data collection

Agilent Xcalibur (Sapphire3, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.803, T _max = 1.000
18571 measured reflections
6635 independent reflections
5438 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.088
S = 0.97
6628 reflections
254 parameters
142 restraints
H-atom parameters constrained
Δρ_max = 1.32 e Å⁻³
Δρ_min = −1.00 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and VESTA (Momma & Izumi, 2011 ▶); software used to prepare material for publication: CRYSTALS.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813026172/wm2766sup1.cif

e-69-0m562-sup1.cif^{(28.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026172/wm2766Isup2.hkl

e-69-0m562-Isup2.hkl^{(415.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sn1—C6	2.129 (5)
Sn1—Cl2	2.3390 (12)
Sn1—Cl3	2.3494 (14)
Sn1—Cl4	2.4812 (14)
Sn1—Cl5	2.5051 (14)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H152⋯Cl4	0.96	2.81	3.752 (6)	167
C19—H191⋯Cl5ⁱ	0.96	2.88	3.837 (5)	171
C19—H192⋯Cl5ⁱⁱ	0.96	2.90	3.830 (5)	164

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

1. Comment

The interest in new organotin(IV) derivatives is related to their applications in different fields: stabilization of polyvinyl chloride, treatments for glass surface, homogeneous catalysts, textile treatments and fungicidal properties (Evans & Karpel, 1985; Davies et al., 2008).

The asymmetric unit of the title compound, (N(C₄H₉)₄)[Sn(C₄H₉)Cl₄], is illustrated in Fig. 1. It consists of a tetrabutylammonium cation and a tetrachloridobutylstannate(IV) anion. The Sn(IV) atom is five-coordinated in a distorted trigonal-bipyramidal arrangement with Cl4 and Cl5 in the apical positions. Major bond angle deviations with respect to the ideal trigonal-bipyramidal coordination geometry appear to be related to the different sizes of the butyl group and the Cl atoms. Thus in the equitorial plane, the C6—Sn1—Cl2 angle (125.04 (15)°) is larger than the Cl2—Sn1—Cl3 angle (112.46 (6)°). The angle Cl4—Sn1—Cl5 is 175.24 (6)°, indicating a slight deviation from linearity. The local geometry at the Sn(IV) position in the title compound is thus similar to that in (Ph₄As)[MeSnCl₄] (Webster et al., 1976). The Sn—Cl distances, [2.3390 (12), 2.3494 (14), 2.4812 (14) and 2.5051 (14) Å], are slightly outside the range of the Sn—Cl distances [2.369 (4) and 2.400 (4) Å] observed in (n-Pr₂NH₂)[Sn(C₂O₄)Cl₄] (Sow et al., 2010). The C—N—C angles of the cation are close to 109°, in agreement with the expected sp³ hybridization.

The packing of the structure is shown in Fig. 2. A short intermolecular Cl2···Cl2 interaction of 3.295 (2) Å is found between two SnBuCl₄^- anions related by an inversion center. Only two other non-disordered compounds containing chloridotin(IV) complexes have shorter Cl···Cl intermolecular interactions: 3.190 Å in [C₃₃H₂₅N₃SnCl₄]·CH₂Cl₂ (Brazeau et al., 2012); 3.288 Å in trans-[PdCl(SnCl₃(2-PyPPh₂)₂)] (Cabon et al., 2010). In the title compound, cations and anions stack along the a-axis and are connected via weak C—H···Cl hydrogen-bonding interactions (Fig. 2). The stacks themselves are connected via weak Cl···Cl interactions and another C—H···Cl interaction as to form sheets parallel to the ab plane.

2. Experimental

Ethanolic solutions containing (NBu₄)HSO₄ (1.26 g, 4 mmol) and SnBuCl₃ 2.25 g, 8 mmol) were mixed and stirred at room temperature for more than 1 h. After removing the precipitate, the filtrate was allowed to evaporate to give colourless crystals of the title compound. The idealized overall reaction is: (NBu₄)HSO₄ + 2 SnBuCl₃→ (NBu₄)[SnBuCl₄] + SnBuCl₂HSO₄