Dimethyl­ammonium dichloridotriphenyl­stannate(IV)

Yaya Sow; Libasse Diop; Gabriele Kociok-Kohn; Kieran C Molloy

doi:10.1107/S1600536812028905

. 2012 Jun 30;68(Pt 7):m1015–m1016. doi: 10.1107/S1600536812028905

Dimethylammonium dichloridotriphenylstannate(IV)

Yaya Sow ^a, Libasse Diop ^a, Gabriele Kociok-Kohn ^b, Kieran C Molloy ^b,^*

PMCID: PMC3393250 PMID: 22807710

Abstract

The title salt, [(CH₃)₂NH₂][Sn(C₆H₅)₃Cl₂], was obtained as a by-product of the reaction between bis(dimethylammonium) oxalate and triphenyltin chloride. In the stannate anion, the trigonal–bipyramidal coordination environment of the Sn^IV atom is defined by the phenyl groups in equatorial and the Cl atoms in axial positions. The cations are connected to adjacent anions through N—H⋯Cl and C—H⋯Cl hydrogen-bonding interactions, leading to a chain motif parallel to [100].

Related literature

For background to organotin(IV) chemistry, see: Chee et al. (2003 ▶); Evans & Karpel (1985 ▶); Gielen et al. (1995 ▶); Ng & Kumar Das (1997 ▶); Zhang et al. (2006 ▶). For compounds containing the [Sn(C₆H₅)₃Cl₂]⁻ ion, see: Harrison et al. (1978 ▶); Ng (1995 ▶, 1999 ▶).

Experimental

Crystal data

(C₂H₈N)[Sn(C₆H₅)₃Cl₂]
M _r = 466.98
Monoclinic,
a = 7.9865 (1) Å
b = 17.5031 (3) Å
c = 14.9484 (3) Å
β = 105.406 (1)°
V = 2014.53 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 150 K
0.30 × 0.20 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.656, T _max = 0.749
16595 measured reflections
4569 independent reflections
4469 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.045
S = 1.07
4569 reflections
227 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.89 e Å⁻³
Absolute structure: Flack (1983 ▶), 2256 Friedel pairs
Flack parameter: −0.030 (12)

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812028905/wm2636sup1.cif

e-68-m1015-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028905/wm2636Isup2.hkl

e-68-m1015-Isup2.hkl^{(219.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sn—C7	2.152 (2)
Sn—C13	2.152 (2)
Sn—C1	2.160 (2)
Sn—Cl2	2.6098 (6)
Sn—Cl1	2.6153 (6)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H1A⋯Cl1	0.89 (3)	2.33 (3)	3.203 (2)	167 (3)
N—H1B⋯Cl2ⁱ	0.82 (3)	2.34 (3)	3.143 (2)	164 (3)
C2—H2⋯Cl2	0.95	2.67	3.309 (3)	125
C6—H6⋯Cl1	0.95	2.76	3.376 (2)	123
C8—H8⋯Cl1	0.95	2.70	3.344 (2)	126
C12—H12⋯Cl2	0.95	2.69	3.340 (2)	126

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Three [Sn(C₆H₅)₃Cl₂]^- stannate(IV) anion-containing compounds with 2,2'-iminodipyridinium (Ng, 1999), triphenyl(benzoylmethyl)arsonium (Harrison et al., 1978) and tetramethylammonium (Ng, 1995), have previously been reported. In our research of new organotin(IV) compounds, driven by the various applications found within this family (Chee et al., 2003; Evans & Karpel 1985; Gielen et al., 1995; Ng et al.,1997; Zhang et al., 2006), we have initiated here the study of the interactions between bis(dimethylammonium)oxalate and triphenyltin chloride which has yielded the title ionic product, [(CH₃)₂NH₂][Sn(C₆H₅)₃Cl₂], (I).

The [Sn(C₆H₅)₃Cl₂]^- anion has a trigonal-bipyramidal shape with the Sn(IV) atom in a trans-Cl₂C₃ environment (Fig. 1). The equatorial plane is defined by the three phenyl groups [Sn—C 2.152 (2), 2.152 (2) and 2.160 (2) Å] while the Sn—Cl distances are 2.6098 (6) and 2.6153 (6) Å. The latter distances are very close to those reported by Ng (1995, 1999), [2.598 (1) Å] but somehow longer and shorter than those reported by Harrison et al. (1978) [2.573 (7), 2.689 (6) Å] for the same kind of anion. The sum of the equatorial angles (360°) indicates a planar SnPh₃ residue, although the Cl—Sn—Cl angle deviates from linearity [174.94 (2)°].

The [SnPh₃Cl₂]^- anions are connected by the ammonium cations through a pair of similar N—H···Cl hydrogen bonds leading to an infinite chain structure parallel to [100] (Fig. 2), which is probably the origin of the Sn—Cl bond lengthening in comparison with [(CH₃)₄N][Sn(C₆H₅)₃Cl₂]. In the crystal packing C—H···Cl interactions are also observed (Table 1).

Experimental

All chemicals were purchased from Aldrich (Germany) and used without any further purification. When ((CH₃)₂NH₂)₂C₂O₄^.nH₂O (obtained as a powder on submitting a 2/1 ratio mixture of [(CH₃)₂NH₂][OH] and oxalic acid in water to evaporate at 333 K) is allowed to react while stirring with an excess of Sn(C₆H₅)₃Cl, both as ethanolic solutions, over 2 h, a precipitate is obtained. After filtering the precipitate, slow solvent evaporation from the filtrate afforded colourless crystals of the title complex suitable for X-ray work.