Ethyl [1-(4-bromo­phen­yl)-1-hydr­oxy-3-oxobut­yl](phen­yl)phosphinate monohydrate

Sampak Samanta; Sandun Perera; Grant A Broker; Cong-Gui Zhao; Edward R T Tiekink

doi:10.1107/S160053681000437X

. 2010 Feb 10;66(Pt 3):o569. doi: 10.1107/S160053681000437X

Ethyl [1-(4-bromophenyl)-1-hydroxy-3-oxobutyl](phenyl)phosphinate monohydrate¹

Sampak Samanta ^a, Sandun Perera ^a, Grant A Broker ^a, Cong-Gui Zhao ^a,^‡, Edward R T Tiekink ^b,^*

PMCID: PMC2983684 PMID: 21580337

Abstract

In the title hydrate, C₁₈H₂₀BrO₄P·H₂O, a staggered conformation is found when the organic molecule is viewed down the central P—C bond, with the oxo and hydroxyl groups being diagonally opposite; each of the central P and C atoms has an S-configuration. The crystal structure features supramolecular double chains along the b axis mediated by O_hydroxyl–H⋯O_oxo, O_water–H⋯O_oxo, and O_water–H⋯O_water hydrogen bonds.

Related literature

For background to the enantioselective synthesis of the biologically significant R-hydroxyphosphinates, see: Samanta et al. (2010 ▶).

Experimental

Crystal data

C₁₈H₂₀BrO₄P·H₂O
M _r = 429.24
Monoclinic,
a = 10.140 (2) Å
b = 5.7779 (12) Å
c = 16.691 (3) Å
β = 104.79 (3)°
V = 945.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.28 mm⁻¹
T = 173 K
0.30 × 0.11 × 0.08 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.607, T _max = 1
6979 measured reflections
3568 independent reflections
3382 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.094
S = 1.06
3568 reflections
236 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ▶), 1408 Friedel pairs
Flack parameter: 0.015 (10)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681000437X/hb5328sup1.cif

e-66-0o569-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681000437X/hb5328Isup2.hkl

e-66-0o569-Isup2.hkl^{(174.9KB, 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—H1o⋯O2ⁱ	0.84	1.94	2.698 (4)	150
O1w—H1w⋯O2	0.84	2.03	2.855 (4)	168
O1w—H2w⋯O1wⁱⁱ	0.84	2.24	3.072 (6)	172

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

Acknowledgments

The authors thank the NIH-NIGMS (grant No. 1SC1GM082718-01 A1) for financial support of this research and the Welch Foundation (grant No. AX-1593) for financial support for preliminary aspects of this research.

supplementary crystallographic information

Comment

The title hydrate, (I), was investigated as a part of on-going studies on the enantioselective synthesis of the biologically significant R-hydroxyphosphinates (Samanta et al., 2010). The crystal structure analysis of diastereoisomer in (I), Fig. 1, confirms the stereochemistry of the C1 atom to be S and that of the P2 atom to be likewise S. There are significant hydrogen bonding interactions in the structure and the solvent water molecules play a pivotal role in the supramolecular aggregation. Direct links between molecules are found through the agency of O1_hydroxyl—H1o···O2_oxo hydrogen bonds, Fig. 2 and Table 1. Chains thus formed along the b direction are linked into double chains via a central zig-zag arrangement of hydrogen bonded water molecules that are connected to phosphorous-oxide atoms, Fig. 2 and Table 1. The combination of these O—H···O interactions leads to the formation of 13-membered {···O═ PCOH···O_oxo···HO_waterH···O_waterH···O_waterH} synthons. These chains are connected into layers in the ab plane via C–H···O interactions, Table 1, involving a methyl-H and carbonyl-O atoms, Fig. 3.

Experimental

The title compound was prepared as described in the literature (Samanta et al., 2010). Crystals were obtained by dissolving the diastereomeric products obtained in the cross aldol reaction in a minimum amount of ethyl acetate and then diluting with hexane. The solution was kept in the open to allow solvent slow evaporation, and colourless blocks of (I) were obtained after 24 h.