Benz­yl(phen­yl)phosphinic acid

Robert A Burrow; Rubia M Siqueira da Silva

doi:10.1107/S1600536811008245

. 2011 Apr 7;67(Pt 5):o1045. doi: 10.1107/S1600536811008245

Benzyl(phenyl)phosphinic acid

Robert A Burrow ^a,^*, Rubia M Siqueira da Silva ^a

PMCID: PMC3089092 PMID: 21754372

Abstract

The title compound, C₁₃H₁₃O₂P, crystallized as enantiomerically pure crystals; for the crystal measured, the P atom has R stereochemistry. The crystal structure displays O—H⋯O hydrogen bonding, which links individual molecules related by a 2₁ screw axis parallel to the crystallographic a-axis direction into continuous chains.

Related literature

For background to phosphinic acids, see: Beckmann et al. (2009 ▶); Burrow et al. (2000 ▶); Chen & Suslick (1993 ▶); Siqueira et al. (2006 ▶); Vioux et al. (2004 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). Geometrical analysis was performed with Mogul (Bruno et al., 2004 ▶).

Experimental

Crystal data

C₁₃H₁₃O₂P
M _r = 232.20
Orthorhombic,
a = 5.7326 (2) Å
b = 12.3430 (3) Å
c = 16.7794 (4) Å
V = 1187.27 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 295 K
0.65 × 0.34 × 0.22 mm

Data collection

Bruker X8 Kappa APEXII diffractometer
Absorption correction: gaussian (SADABS; Bruker, 2009 ▶) T _min = 0.880, T _max = 0.964
14337 measured reflections
3451 independent reflections
3119 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.108
S = 1.05
3451 reflections
148 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ▶), 1447 Friedel pairs
Flack parameter: 0.00 (11)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT (Bruker, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008245/zb2011sup1.cif

e-67-o1045-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008245/zb2011Isup2.hkl

e-67-o1045-Isup2.hkl^{(169.3KB, 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
O1—H1⋯O2ⁱ	0.93 (3)	1.58 (3)	2.4838 (18)	163 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Conselho Nacional de Desenvolvimento Científico (CNPq, Brazil; grants 485245/2007–8 and 479747/2009–1) and the Fundação de Amparo à Pesquisa (FAPERGS, Rio Grande do Sul) is gratefully acknowledged, as are fellowships from CNPq (RAB) and the Coordenação de Aperfeiçoamento de Pessoas de Nível Superior (CAPES, Brazil; RMSS). The diffractometer was funded by a CT-INFRA grant from the Financiadora de Estrutos e Projetos (FINEP, Brazil).

supplementary crystallographic information

Comment

Phosphinic acids have found use for the construction of coordination polymers [Siqueira et al., 2006; Beckmann et al., 2009] for a wide range of applications [Vioux et al., 2004; Chen & Suslick,1993]. Continuing our research on phosphinic acids [Burrow et al., 2000], we report the synthesis and crystal structure of the title compound, (I).

The crystal structure of (I) is from an enantiomerically pure crystal (Flack parameter = 0.00 (11); 1447 Friedel pairs; Flack & Bernardinelli, 2000] with the P atom possessing R stereochemistry. An analysis of the geometry of (I) by Mogul [Bruno et al., 2004] using the CSD. [Allen, 2002] shows no unusual features for the benzyl and phenyl groups. However, an unusually long P═O bond [P1═O2 = 1.5104 (13) Å; average in Mogul:1.484 (17) Å for 16 observations, |z score| = 1.568] and a wider C—P—C angle [C11—P1—C21 angle = 109.493 (9)°; average in Mogul: 106.9(2.0) °, |z score| = 1.281] are found.

The individual molecules of (I) related by a 2₁ screw axis parallel to the crystallographic a direction are joined by hydrogen bonding of the type OH···O=P—OH···O=P to form continuous chains. The short P—O···O=P distance of 2.4838 (18) Å indicates a strong hydrogen bond. This is slightly shorter than the average O···O interaction distance in the CSD. [2.51 (5) Å, 45 observations] for other phosphinic acids.

Experimental

To a solution of phenylphosphinic acid (2.0 g, 14.1 mmol) in dichloromethane, 30 ml diisopropylethylamine (5.16 ml, 29.6 mmol) and trimethylsilyl chloride (3.74 ml, 29.6 mmol) were separately added at 0 °C under argon. The reaction mixture was stirred at room temperature for 2–3 h, cooled to 0 °C and 1-(bromomethyl)benzene (1.84 ml, 15.5 mmol) was added. After further stirring at room temperature for 48 h, the solvent was removed under vacuum. The residue was suspended in hydrochloric acid (2 M, 20 ml) and filtered on a glass frit. The white solid was washed with acetone and dried giving a yield of 1.70 g (65%) of pure product. IR: 1494 (m), 1439 (s), 1242 (m), 1132 (versus), 1069 (s), 969 (versus), 845 (s), 787 (s), 751 (s), 734 (s), 701 (s), 585 (m), 524 (s), 477 (s), 466 (m) cm^-1. TGA: 310–361 °C: 99% loss. DTA: 181–193 °C & 310–361 °C endothermic peaks. Crystals suitable for single-crystal X-ray analysis were grown from an acetone solution in a desiccator with silical gel.