(1-Oxo-2,6,7-trioxa-1-phosphabicyclo­[2.2.2]octan-4-yl)methyl 4-methyl­benzene­sulfonate

Xu-Feng Hou; Jin-Long Yan

doi:10.1107/S1600536812016674

. 2012 Apr 21;68(Pt 5):o1473. doi: 10.1107/S1600536812016674

(1-Oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octan-4-yl)methyl 4-methylbenzenesulfonate

Xu-Feng Hou ^a,^*, Jin-Long Yan ^b

PMCID: PMC3344584 PMID: 22590346

Abstract

In the title compound, C₁₂H₁₅O₇PS, the P atom has a distorted tetrahedral environment. The P—O—C—C torsion angles deviate significantly from zero [average = 12.0 (3)°], indicating that the bicyclic OP(OCH₂)₃C cage is strained. In the crystal, weak C—H⋯O interactions consolidate the packing.

Related literature

For related structures, see: Miu et al. (1991 ▶); Sheng & He (2006 ▶); Guo & Zang (2007 ▶). For applications of caged bicyclic phosphates and p-toluenesulfonates, see: Li et al. (2000 ▶); Yachi et al. (1989 ▶); Spungin et al. (1992 ▶).

Experimental

Crystal data

C₁₂H₁₅O₇PS
M _r = 334.27
Monoclinic,
a = 5.8884 (17) Å
b = 19.440 (5) Å
c = 12.469 (4) Å
β = 100.614 (4)°
V = 1402.8 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.929, T _max = 0.956
17318 measured reflections
3353 independent reflections
2808 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.095
S = 1.03
3353 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.36 e Å⁻³

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: CrystalStructure (Rigaku/MSC, 2005 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812016674/cv5286sup1.cif

e-68-o1473-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016674/cv5286Isup2.hkl

e-68-o1473-Isup2.hkl^{(164.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812016674/cv5286Isup3.cml

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
C7—H7A⋯O5ⁱ	0.98	2.59	3.288 (2)	128
C8—H8A⋯O1ⁱⁱ	0.99	2.38	3.180 (2)	138
C10—H10A⋯O7ⁱⁱⁱ	0.99	2.27	3.211 (2)	158
C10—H10B⋯O2^iv	0.99	2.44	3.348 (2)	152

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

Acknowledgments

This work was supported by the Natural Science Foundation of Henan Province, China (grant No. 082300420110) and the Natural Science Foundation of Henan Province Education Department, China (grant No. 2007150036).

supplementary crystallographic information

Comment

Caged bicyclic phosphates are widely used as flame retardants or pesticides (Li et al., 2000). They have been studied in the context of hydrogen-bond patterns (Guo & Zang, 2007). p-Toluenesulfonates are also used in monitoring the merging of lipids (Yachi et al., 1989), studying membrane fusion during acrosome reaction (Spungin et al., 1992). We report here the crystal structure of the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related compounds (Miu et al., 1991; Sheng & He, 2006; Guo & Zang, 2007). The P—O—C—C torsion angles deviate significantly from zero [averaged -12.0 (3)°] indicating that bicyclic OP(OCH₂)₃C cage is strained. In the crystal, weak C—H···O interactions (Table 1) consolidate the packing.

Experimental

The title compound was obtained in the reaction of 4-(hydroxymethyl)-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide (5 mmol) and 4-toluenesulfonyl chloride(4.7 mmol) in refluxing acetonitrile (50 ml). The solvent was evaporated in vacuo. The title compound was recrystallized from ethanol and single crystals of (I) were obtained by slow evaporation.