Tetra­methyl­ammonium aqua­trichlorido­oxalatostannate(IV) monohydrate

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

doi:10.1107/S1600536813000895

. 2013 Jan 16;69(Pt 2):m106–m107. doi: 10.1107/S1600536813000895

Tetramethylammonium aquatrichloridooxalatostannate(IV) monohydrate

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

PMCID: PMC3569201 PMID: 23424403

Abstract

The Sn^IV atom in the title compound, [(CH₃)₄N][Sn(C₂O₄)Cl₃(H₂O)]·H₂O, obtained from the reaction between SnCl₄ and [(CH₃)₄N]₂C₂O₄·2H₂O, is six-coordinated by three Cl atoms, an O atom of a water molecule and two O atoms from an asymmetrically chelating oxalate anion. The environment around the Sn^IV atom is distorted octahedral. The anions are connected by the lattice water molecule through O—H⋯O hydrogen bonds, leading to a layered structure parallel to (010). The cations are located between these layers and besides Coulombic forces are connected to the anionic layers through weak C—H⋯O and C—H⋯Cl interactions.

Related literature

For background to halogentin(IV) chemistry, see: Hausen et al. (1986 ▶); Koutsantonis et al. (2003 ▶); Mahon et al. (2004 ▶); Patt-Siebel et al.(1986 ▶); Szymanska-Buzar et al. (2001 ▶); Tudela et al. (1986 ▶). For tin compounds containing an Sn—Cl bond in a cis- or trans-position, see: Fernandez et al. (2002 ▶); Hazell et al. (1998 ▶); Sow et al. (2010 ▶). For tin compounds containing carboxylate moieties, see: Ng & Kumar Das (1993 ▶); Xu et al. (2003 ▶).

Experimental

Crystal data

(C₄H₁₂N)[Sn(C₂O₄)Cl₃(H₂O)]·H₂O
M _r = 423.24
Monoclinic,
a = 7.2458 (1) Å
b = 22.2812 (2) Å
c = 9.6019 (1) Å
β = 98.015 (1)°
V = 1535.04 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.20 mm⁻¹
T = 150 K
0.15 × 0.15 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.734, T _max = 0.763
35849 measured reflections
4445 independent reflections
3855 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.062
S = 1.08
4445 reflections
175 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.79 e Å⁻³

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 (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Click here for additional data file.^{(16.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000895/wm2712sup1.cif

e-69-0m106-sup1.cif^{(16.3KB, cif)}

Click here for additional data file.^{(213.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000895/wm2712Isup2.hkl

e-69-0m106-Isup2.hkl^{(213.4KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H50A⋯O6	0.86 (2)	1.66 (2)	2.511 (2)	173 (3)
O5—H50B⋯O4ⁱ	0.85 (2)	1.78 (2)	2.6120 (19)	168 (3)
O6—H60B⋯O3ⁱⁱ	0.84 (2)	1.99 (2)	2.792 (2)	160 (3)
O6—H60A⋯O3ⁱⁱⁱ	0.84 (2)	1.95 (2)	2.7840 (19)	172 (3)
O6—H60B⋯O4ⁱⁱ	0.84 (2)	2.47 (3)	2.993 (2)	122 (3)
C6—H6B⋯O6ⁱ	0.98	2.54	3.411 (3)	148
C6—H6A⋯Cl3^iv	0.98	2.91	3.762 (3)	146

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

supplementary crystallographic information

Comment

Numerous crystal structures of SnX₄ adducts (X = halogen) containing tin(IV) in an octahedral environment have been reported up to date, e.g. Hausen et al. (1986); Koutsantonis et al. (2003); Mahon et al. (2004); Patt-Siebel et al. (1986); Szymanska-Buzar et al. (2001); Tudela et al. (1986). Our group has previously reported the crystal structure of ((n-C₃H₇)₂NH₂)₂[Sn(C₂O₄)Cl₄] which contains a chelating oxalate anion, and the environment of tin(IV) being likewise octahedral (Sow et al., 2010). In the context of our search for new SnX₄ adducts we report here the study of the reaction between ((CH₃)₄N)₂C₂O₄^.2H₂O and SnCl₄ which has yielded the title compound, ((CH₃)₄N)[Sn(C₂O₄)Cl₃(H₂O)]^.H₂O. While many SnX₄ adducts have been reported (see above), a complex with a [SnCl₃]-containing residue is reported here.

The octahedral geometry around the tin(IV) atom is defined by three Cl atoms, two oxygen atoms from the chelating oxalate anion and the oxygen atom of a water molecule (Fig. 1). The two oxygen atoms from the oxalate anion and two of the Cl atoms are in the equatorial plane while the remaining Cl atom and the oxygen atom of the H₂O molecule are in axial positions.

The [Sn(C₂O₄)Cl₃(H₂O)]^- anions are connected to the lattice water molecule through H—O—H···OH₂ hydrogen bonds. The water molecule bonded to the tin(IV) atom is also hydrogen-bonded to the O4 atom of a neighbour complex-anion. The lattice water molecule O6 is bonded to O3 and O4 of the same oxalate anion through a bifurcated hydrogen bond and to a O3 atom of a neighbouring oxalate anion, leading to a layered structure extending parallel to (010). The cations are located between the anionic planes (Figs. 2,3). In the crystal packing, C—H···O and C—H···Cl interactions between cations and anions are also observed (Table 1).

The angle O5—Sn—Cl3 [170.75°(5)] deviates from linearity. The two Sn—Cl bond lengths in the equatorial plane are very similar [Sn—Cl2 = 2.3598 (5), Sn—Cl1 = 2.3627 (5) Å], but different from the one trans to the water molecule [Sn—Cl3 = 2.3926 (5) Å], pointing to a weak trans-effect involving the latter. The Sn—O5 bond of 2.0781 (15) Å involving the water molecule is shorter than the Sn—O bonds distances involving the oxalate anion [Sn—O1 = 2.0980 (13); Sn—O2 = 2.1025 (13) Å], whereby these two last Sn—O distances are very close. The dimensions of Sn—O bonds and Sn—Cl bonds are in the range of Sn—O and Sn—Cl bonds reported for O₂SnCl₄ containing adducts with cis- or trans-geometry (Fernandez et al., 2002; Hazell et al., 1998; Sow et al., 2010).

The C—O distances [O1—C1 = 1.285 (2); O2—C2 = 1.288 (2) Å; O3—C1 = 1.219 (2) Å; O4—C2 = 1.223 (2) Å] are in the typical range of C—O and C═O bonds (Ng & Kumar Das, 1993; Xu et al., 2003).

Experimental

All chemicals were purchased from Aldrich (Germany) and used without any further purification. ((CH₃)₄N)₂C₂O₄^.2H₂O has been obtained on allowing ((CH₃)₄N)OH as a 20% water solution to react with oxalic acid in a 2:1 ratio. A powder is obtained after evaporation of water at 333 K. On allowing the oxalic acid salt to react with SnCl₄ in a 1:1 ratio in ethanol, a colorless solution is obtained, which gives, after slow solvent evaporation, crystals suitable for X-ray determination . The reaction equation of the title compound is: ((CH₃)₄N)₂C₂O₄^.2H₂O + SnCl₄→ ((CH₃)₄N)Cl + ((CH₃)₄N)[Sn(C₂O₄)Cl₃H₂O]^.H₂O