Poly[diaqua­(μ4-carboxyl­atomethyl­phospho­nato)(μ4-carb­oxy­methyl­phospho­nato)penta­deca­methyl­penta­tin(IV)]

Mouhamadou Sembene Boye; Aminata Diasse-Sarr; Arnaud Grosjean; Philippe Guionneau

doi:10.1107/S1600536813000676

. 2013 Jan 19;69(Pt 2):m110–m111. doi: 10.1107/S1600536813000676

Poly[diaqua(μ₄-carboxylatomethylphosphonato)(μ₄-carboxymethylphosphonato)pentadecamethylpentatin(IV)]

Mouhamadou Sembene Boye ^a,^*, Aminata Diasse-Sarr ^a, Arnaud Grosjean ^b, Philippe Guionneau ^b

PMCID: PMC3569204 PMID: 23424406

Abstract

The central Sn^IV atom of the pentanuclear title complex, {[Sn(CH₃)₃]₃O₂C(CH₂)PO₃[Sn(CH₃)₃(H₂O)]₂HO₂C(CH₂)PO₃}, is located on a twofold rotation axis; due to symmetry, the H atom of the carboxyl group of the anion is disordered with a site occupancy of 0.5. The central Sn^IV atom is bonded to three methyl groups (one of which is disordered about the twofold rotation axis) and is symmetrically trans coordinated by two phosphonate groups with Sn—O = 2.2665 (12) Å while the other SnMe₃ residues are asymmetrically trans coordinated with Sn—O = 2.1587 (12) and 2.3756 (13) Å for one residue and Sn—O = 2.1522 (12) and 2.4335 (12) Å for the other; the Sn–O distances involving two O atoms trans to carboxylate are longer than those trans to phosphonate groups. The Sn—C distances lie in a very narrow range [2.112 (2)–2.133 (3) Å]. The oxyanion behaves as a tetra-coordinating ligand. The bridging mode of the latter leads to the formation of layers parallel to (001) that are interconnected by O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For applications of tin-based materials, see: Dutrecq et al. (1992 ▶); Basu Baul et al. (2011 ▶). For related structures, see: Zhang et al. (2010 ▶).

Experimental

Crystal data

[Sn₅(CH₃)₁₅(C₂H₂O₅P)(C₂H₃O₅P)(H₂O)₂]
M _r = 1130.01
Monoclinic,
a = 11.6939 (2) Å
b = 13.1689 (3) Å
c = 25.9575 (5) Å
β = 95.40 (1)°
V = 3979.61 (14) Å³
Z = 4
Mo Kα radiation
μ = 3.22 mm⁻¹
T = 150 K
0.32 × 0.15 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.426, T _max = 0.644
15302 measured reflections
7932 independent reflections
7236 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.054
S = 1.09
7932 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Data collection: COLLECT (Nonius, 2003 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(20.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000676/pv2611sup1.cif

e-69-0m110-sup1.cif^{(20.3KB, cif)}

Click here for additional data file.^{(380.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000676/pv2611Isup2.hkl

e-69-0m110-Isup2.hkl^{(380.4KB, 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
O6—H1O⋯O5ⁱ	0.89	1.83	2.693 (2)	164
O6—H2O⋯O1ⁱ	0.85	1.88	2.706 (2)	161
C9—H9A⋯O4ⁱⁱ	0.99	2.51	3.227 (2)	129

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

supplementary crystallographic information

Comment

Organotin(IV) compounds are involved in many applications in a large diversity of fields including agriculture, medicine and industry (Dutrecq et al., 1992; Basu Baul et al., 2011). Carboxylalkylphosphonate derivatives are interesting from the point of view of their structural tendency to form polymeric structures. The presence of carboxylate and phosphonate functions makes carboxylalkylphosphonate a polyfunctional ligand which can coordinate to the metal in all directions. The aim of combining organotin and carboxyalkylphosphonate is to exalte the biocidal activity in the resulting title complex. Only a few structures related to the title compound have been reported (Zhang et al., 2010).

The asymmetry unit of the title complex, [(SnMe₃)₃O₂C(CH₂)PO₃(SnMe₃.H₂O)₂HO₂C(CH₂)PO₃]_n, contains one half of the trimethyltin(IV) (SnMe₃) lying on a 2-fold axis linked to a [(SnMe₃)2.H₂O](PO₃CH₂CO₂H_0.5) fragment leading to the pentanuclear complex (Fig. 1) that forms the repeat unit of the polymer; the hydroxyl H-atom is disordered with 0.5 occupancy factor. The geometry of all tin atoms (Sn1, Sn2 and Sn3) is trigonal bipyramidal. The Sn—O distances in the title complex involving two O atoms trans to carboxylate [Sn3—O5ⁱⁱ = 2.4335 (12) Å] are longer than those trans to phosphonate groups [Sn3—O3 = 2.1522 (12) Å] (Table 1). The longest P—O bond [P1—O3 = 1.5156 (12) Å] is linked to the strongest Sn—O bond while, on the contrary, the shortest C—O bond [C8—O5 = 1.257 (2) Å] is linked to the weakest one. The values of O—Sn—O angles are in the range [176.51 (5)–176.84 (6)°] indicating a significant deviation from linearity. The C—Sn—C angles [115.13 (11)–124.85 (9)°] indicate almost planar Sn—C₃ groups. The crystal structure obtained is three-dimensional since, within the packing, each pentacoordinated tin atom is bonded to two oxygen atoms in axial positions and three methyl groups in equatorial positions. The SnC₃ residues are asymmetrically trans coordinated. The oxoanion behaves as a tetradentate ligand involving three oxygen atoms of the phosphonate and one of the carboxylate oxygen atom. Resulting chains are interconnected by O—H ···O hydrogen bonds which generate crystal lattice rectangular (Fig. 2 & Table 1).

Experimental

The title compound was synthesized by the reaction in ethanol (30 ml) of carboxymethylphosphonic acid (0.161 g, 1.13 mmol), KOH (0.229 g, 3.39 mmol) and trimethyltin(IV) chloride (0.675 g, 3.39 mmol) in a 1:3:3 ratio. The mixture was stirred around two hours at room temperature. Suitable crystals for X-ray diffraction were obtained after a slow evaporation of the solvent; m.p. 463–464 K.