Dibutyl­ammonium bis­(hydrogen methylphosphonato-κO)triphenylstannate(IV)

Tidiane Diop; Libasse Diop; Djibril Fall; Arie van Lee

doi:10.1107/S1600536812038445

. 2012 Sep 19;68(Pt 10):m1284–m1285. doi: 10.1107/S1600536812038445

Dibutylammonium bis(hydrogen methylphosphonato-κO)triphenylstannate(IV)

Tidiane Diop ^a,^*, Libasse Diop ^a, Djibril Fall ^b, Arie van Lee ^c

PMCID: PMC3470160 PMID: 23125604

Abstract

The asymmetric unit of the title organotin salt, (C₈H₂₀N)[Sn(C₆H₅)₃(CH₄O₃P)₂], contains two dibutylammonium cations and two stannate(IV) anions consisting each of two monodentately bonding methyl hydrogenphosphate groups attached to an Sn(C₆H₅) unit. The overall coordination environment of the two Sn^IV atoms is trigonal–bipyramidal defined by three phenyl C atoms in equatorial positions and two methyl hydrogenphosphate O atoms at the apical sites. In the crystal, the stannate(IV) anions are linked to each other via pairs of short O—H⋯O hydrogen bonds, leading to an infinite chain extending parallel to the b-axis direction. Neighbouring chains are linked by N—H⋯O hydrogen bonds involving the butylammonium cations, giving a two-dimensional structure parallel to the ab plane. The crystal under investigation was found to be twinned by reticular merohedry with twin fractions of 0.5342 (7):0.4658 (7).

Related literature

For general background to and applications of tin(IV) compounds, see: Davies et al. (2008 ▶); Gielen (2002 ▶); Molloy et al. (1984 ▶). For related structures, see: Adair et al. (2003 ▶); Chunlin et al. (2008 ▶); Diop et al. (2002 ▶, 2011 ▶); Gueye et al. (2011 ▶); Sow et al. (2012 ▶). For details of the use of constraints and restraints during the structure refinement, see: Cooper et al. (2010 ▶). For background to the weighting schemes used in the refinement, see: Prince (1982 ▶); Watkin (1994 ▶).

Experimental

Crystal data

(C₈H₂₀N)[Sn(C₆H₅)₃(CH₄O₃P)₂]
M _r = 670.28
Monoclinic,
a = 16.1963 (8) Å
b = 18.9088 (8) Å
c = 21.1989 (11) Å
β = 93.220 (4)°
V = 6482.0 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 175 K
0.30 × 0.25 × 0.10 mm

Data collection

Oxford Diffraction Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.961, T _max = 1.000
64843 measured reflections
26060 independent reflections
17225 reflections with I > 2σ(I)
R _int = 0.085

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.067
S = 0.99
17225 reflections
686 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 1.28 e Å⁻³
Δρ_min = −1.66 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 ▶); software used to prepare material for publication: CRYSTALS and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812038445/wm2676sup1.cif

e-68-m1284-sup1.cif^{(40.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038445/wm2676Isup2.hkl

e-68-m1284-Isup2.hkl^{(1.6MB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sn1—O101	2.175 (4)
Sn1—O106	2.188 (3)
Sn1—C111	2.128 (6)
Sn1—C117	2.137 (6)
Sn1—C123	2.125 (5)
Sn2—O201	2.188 (3)
Sn2—O206	2.169 (4)
Sn2—C211	2.125 (6)
Sn2—C217	2.126 (6)
Sn2—C223	2.134 (6)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O103—H1031⋯O109ⁱ	0.85	1.73	2.582 (10)	180 (1)
O108—H1081⋯O104ⁱⁱ	0.85	1.64	2.490 (10)	180 (1)
O203—H2031⋯O209ⁱⁱⁱ	0.85	1.63	2.478 (10)	180 (1)
O208—H2081⋯O204^iv	0.85	1.71	2.561 (10)	180 (1)
N10—H101⋯O209ⁱⁱⁱ	0.89	1.90	2.772 (10)	165 (1)
N10—H102⋯O109	0.90	1.92	2.777 (10)	160 (1)
N20—H201⋯O204^iv	0.89	1.95	2.780 (10)	154 (1)
N20—H202⋯O104	0.90	1.88	2.756 (10)	167 (1)

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

supplementary crystallographic information

Comment

Organotin(IV) complexes are extensively studied due to their industrial applications as well as for their biocidal properties (Molloy et al., 1984; Gielen, 2002; Davies et al., 2008). Our group has conducted research on SnMe₃ and SnPh₃ residues containing derivatives with mono- and polybasic oxyanions such as C₂O₄^2- (Gueye et al., 2011; Sow et al., 2012) and PhP(H)O^2- (Diop et al., 2011). Here we report the structure of the title compound, [(C₄H₉)₂NH₂]⁺[Sn(C₆H₅)₃(CH₃PO₂OH)₂]^-, (I).

The asymmetric unit of compound (I) is illustrated in Fig. 1. It consists of two dibutylammonium cations and two organotin complexes consisting of two monodentate MePO₃H^- anions bonded to SnPh₃; the Sn^IV atoms exhibit a trans trigonal bipyramidal coordination environment consisting of three phenyl carbon atoms and two MePO₃H^- oxygen atoms. The trigonal plane of the Sn atoms is defined by the three phenyl groups whereas the axial positions are occupied by oxygen atoms from the methyl hydrogenphosphate tetrahedra. A similar arrangement around tin(IV) has been observed in the crystal structure of {[(CH₃)₃Sn]₄(O₃PPh)₂}_n (Chunlin et al., 2008). The sums of the angles at the tin(IV) positions by the ipso-carbons atoms [119.9 (2)°, 121.2 (2)°, 118.8 (2)°, and 122.4 (2)°, 119.0 (2)° and 118.6 (2)° for the two Sn^IV entities] are 359.9° and 360.0°, respectively; the corresponding axial O101—Sn1—O106 and O201—Sn2—O206 angles are 174.71 (14)° and 174.15 (14)°, respectively, indicating a nearly perfect trans trigonal bipyramidal arrangement. The Sn—C bond lengths are almost identical within the experimental error (Sn1—C111: 2.128 (6) Å; Sn1—C117: 2.137 (6) Å; Sn1—C123 2.125 (5) Å; Sn2—C211: 2.125 (6) Å; Sn2—C217: 2.126 (6) Å; Sn2—C223 2.134 (6) Å] and lie in the range reported for related structures (Gueye et al., 2011). The two axial Sn—O distances, [Sn1—O101 2.175 (4) Å; Sn1—O106 2.188 (3) Å; Sn2—O201 2.188 (3) Å; Sn2—O206 2.169 (4) Å] are in the range of axial Sn—O distances (2.165 (4) and 2.434 (4) Å) observed in catena-trimethyltin(IV) methylphosphonate, [MePO₃HSnMe₃] (Diop et al., 2002), but are longer than the axial Sn—O distances [2.116 (2) Å and 2.132 (3) Å] observed in catena-(µ2-phenylphosphinato O, O')-chlorido-tin(II) (Adair et al., 2003). The geometry at the P sites is a distorted tetrahedron with bond angles ranging from 102.7 (3)° for O208—P207—C210 to 114.2 (2) for O201—P202—O204.

The stannate(IV) anions [(MePO₃H)₂SnPh₃]^- are linked by pairs of short O—H···O hydrogen bonds, involving the hydroxy group of the methyl hydrogenphosphate unit, and thus forming an infinite chain (Table 1, Fig. 2) along the b-direction. In the crystal, neighbouring chains are linked by N—H···O hydrogen bonds via the Bu₂NH₂⁺ cations, forming a supramolecular structure parallel to the ab plane.

Experimental

An ethanolic solution containing 0.30 g (1.20 mmol) of Bu₂NH₂MePO₃H (obtained from an aqueous mixture of dibutylamine and MeP(O)(OH)₂ in water in a 1:1 ratio) and triphenyltin(IV) chloride (SnPh₃Cl) 2.25 g (0.66 mmol) was stirred at room temperature for more than one hour. After 96 h of slow evaporation of the solution, colourless crystals of the title compound (yield: 78%; m.p: 250°) suitable for X-ray structure determination were obtained within the remaining solvent. The powder obtained after complete solvent evaporation has the formula Bu₂NH₂Cl according to its infrared spectrum.