supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

wn2424 scheme

Acta Cryst. (2011). E67, o926    [ doi:10.1107/S1600536811008944 ]

2-[(4-Chlorophenyl)(hydroxy)methyl]-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one

C. Wang, H. Peng and H. He

Abstract top

In the title compound, C12H16ClO4P, the phosphonate ring adopts a chair conformation. In the crystal, intermolecular O-H...O hydrogen bonds link the molecules into chains propagating along the b axis.

Comment top

Acyclic alpha-hydroxyphosphonates and cyclic alpha-hydroxyphosphonates can be used as very convenient intermediates. They are also an attractive class of biologically active compounds (Peng et al., 2007; Liu et al., 2006). In our research work aimed at searching for novel agrochemicals, we have attempted to synthesize hydroxyphosphonate derivatives using literature procedures. Here we report the crystal structure of the title compound (Fig. 1). The bond lengths (Allen et al., 1987) and angles show normal values. The crystal structure is stabilized by intermolecular O—H···O hydrogen bonds (Table 1, Fig. 2).

Related literature top

For the synthesis of hydroxyphosphonates, see: Zhou et al. (2008). For the synthesis and biological activity of hydroxyphosphonate derivatives, see: Peng et al. (2007); Liu et al. (2006). For standard bond lengths, see: Allen et al. (1987).

Experimental top

The title compound was prepared according to literature procedures (Zhou et al. 2008). 4-Chlorobenzaldehyde (10 mmol) was added to a solution of 5,5-dimethyl-1,3,2-dioxaphosphinane (10 mmol) in triethylamine (10 mmol). The mixture was stirred at room temperature for 20 h. Pure title compound was afforded by column chromatography on silica gel (acetone/petroleum ether 1:2). Recrystallization from ethyl acetate over a period of one week gave colourless crystals of the title compound.

Refinement top

C-bound H atoms and the O-bound H atom were geometrically positioned (C—H 0.93–0.97 Å, O—H = 0.82 Å) and refined as riding, with Uiso(H) =kUeq(C, O), where k = 1.5 for methyl H and OH and 1.2 for other H atoms.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, with displacement parameters drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.
[Figure 2] Fig. 2. Part of the crystal packing, showing the intermolecular hydrogen bonds as dashed lines.
2-[(4-Chlorophenyl)(hydroxy)methyl]-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one top
Crystal data top
C12H16ClO4PF(000) = 608
Mr = 290.67Dx = 1.377 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.8965 (11) ÅCell parameters from 4935 reflections
b = 9.4449 (8) Åθ = 2.7–28.2°
c = 11.6425 (10) ŵ = 0.39 mm−1
β = 98.630 (1)°T = 298 K
V = 1402.1 (2) Å3Block, colourless
Z = 40.23 × 0.16 × 0.12 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3141 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.071
graphiteθmax = 28.3°, θmin = 2.7°
φ and ω scansh = −13→17
10123 measured reflectionsk = −9→12
3463 independent reflectionsl = −15→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.0581P)2 + 0.7742P]
where P = (Fo2 + 2Fc2)/3
3463 reflections(Δ/σ)max < 0.001
166 parametersΔρmax = 0.72 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C12H16ClO4PV = 1402.1 (2) Å3
Mr = 290.67Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.8965 (11) ŵ = 0.39 mm−1
b = 9.4449 (8) ÅT = 298 K
c = 11.6425 (10) Å0.23 × 0.16 × 0.12 mm
β = 98.630 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3141 reflections with I > 2σ(I)
10123 measured reflectionsRint = 0.071
3463 independent reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.154Δρmax = 0.72 e Å−3
S = 1.15Δρmin = −0.28 e Å−3
3463 reflectionsAbsolute structure: ?
166 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2944 (2)0.3005 (3)0.5354 (2)0.0543 (6)
H1A0.29230.32560.61500.081*
H1B0.35960.33120.51350.081*
H1C0.28830.19960.52670.081*
C20.2096 (3)0.5330 (3)0.4720 (3)0.0635 (8)
H2A0.15470.57650.41880.095*
H2B0.27640.56590.45610.095*
H2C0.20140.55770.55010.095*
C30.2035 (2)0.3720 (2)0.4576 (2)0.0407 (5)
C40.2059 (2)0.3377 (2)0.3303 (2)0.0430 (5)
H4A0.15190.39170.28230.052*
H4B0.27330.36550.30990.052*
C50.09896 (19)0.3251 (2)0.4897 (2)0.0429 (5)
H5A0.09710.34650.57080.052*
H5B0.04280.37730.44340.052*
C60.12155 (17)−0.0698 (2)0.36460 (19)0.0359 (4)
H60.0632−0.11710.39390.043*
C70.21964 (16)−0.09498 (19)0.44979 (18)0.0330 (4)
C80.31652 (19)−0.1076 (3)0.4118 (2)0.0432 (5)
H80.3212−0.09780.33330.052*
C90.4058 (2)−0.1346 (3)0.4902 (3)0.0550 (6)
H90.4705−0.14350.46470.066*
C100.3983 (2)−0.1482 (3)0.6055 (3)0.0554 (7)
C110.3035 (2)−0.1347 (3)0.6457 (2)0.0509 (6)
H110.2996−0.14300.72450.061*
C120.21483 (19)−0.1088 (2)0.5673 (2)0.0422 (5)
H120.1505−0.10040.59360.051*
Cl10.51070 (8)−0.18286 (16)0.70446 (9)0.1062 (4)
O10.18909 (13)0.18663 (16)0.30702 (13)0.0403 (4)
O20.08252 (12)0.17262 (17)0.46986 (13)0.0402 (4)
O3−0.00798 (14)0.1404 (2)0.26116 (16)0.0537 (5)
O40.12788 (16)−0.12340 (19)0.25263 (15)0.0526 (5)
H40.0926−0.19570.24180.079*
P10.08858 (4)0.11632 (6)0.34372 (5)0.03362 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0489 (14)0.0561 (16)0.0541 (14)−0.0019 (12)−0.0045 (11)0.0008 (12)
C20.088 (2)0.0332 (12)0.0674 (17)−0.0063 (13)0.0042 (16)−0.0104 (12)
C30.0505 (13)0.0286 (10)0.0416 (11)−0.0025 (9)0.0024 (10)−0.0031 (8)
C40.0560 (14)0.0298 (10)0.0439 (12)−0.0069 (10)0.0099 (10)0.0024 (9)
C50.0511 (13)0.0373 (11)0.0411 (11)0.0065 (10)0.0093 (10)−0.0078 (9)
C60.0345 (10)0.0291 (9)0.0438 (11)−0.0071 (8)0.0048 (8)−0.0022 (8)
C70.0356 (10)0.0188 (8)0.0442 (11)−0.0014 (7)0.0045 (8)0.0004 (7)
C80.0402 (12)0.0439 (12)0.0463 (12)−0.0019 (10)0.0096 (10)0.0011 (10)
C90.0366 (12)0.0619 (17)0.0668 (16)0.0031 (11)0.0087 (11)0.0032 (13)
C100.0442 (14)0.0571 (16)0.0606 (16)0.0052 (12)−0.0060 (11)0.0079 (13)
C110.0615 (16)0.0483 (14)0.0421 (12)0.0045 (12)0.0049 (11)0.0084 (10)
C120.0419 (12)0.0384 (12)0.0476 (12)0.0039 (9)0.0114 (10)0.0043 (9)
Cl10.0629 (6)0.1541 (11)0.0912 (7)0.0175 (6)−0.0221 (5)0.0266 (7)
O10.0520 (9)0.0310 (8)0.0412 (8)−0.0050 (7)0.0175 (7)−0.0022 (6)
O20.0435 (9)0.0373 (8)0.0423 (8)0.0009 (7)0.0150 (7)−0.0016 (6)
O30.0485 (10)0.0528 (10)0.0546 (10)0.0105 (8)−0.0089 (8)0.0022 (8)
O40.0622 (12)0.0444 (10)0.0503 (10)−0.0086 (8)0.0054 (8)−0.0130 (8)
P10.0342 (3)0.0304 (3)0.0358 (3)0.0021 (2)0.0039 (2)0.0004 (2)
Geometric parameters (Å, °) top
C1—C31.528 (3)C6—P11.816 (2)
C1—H1A0.9600C6—H60.9800
C1—H1B0.9600C7—C121.385 (3)
C1—H1C0.9600C7—C81.392 (3)
C2—C31.530 (3)C8—C91.382 (3)
C2—H2A0.9600C8—H80.9300
C2—H2B0.9600C9—C101.367 (4)
C2—H2C0.9600C9—H90.9300
C3—C51.518 (3)C10—C111.379 (4)
C3—C41.522 (3)C10—Cl11.742 (3)
C4—O11.463 (3)C11—C121.373 (3)
C4—H4A0.9700C11—H110.9300
C4—H4B0.9700C12—H120.9300
C5—O21.469 (3)O1—P11.5716 (16)
C5—H5A0.9700O2—P11.5748 (16)
C5—H5B0.9700O3—P11.4721 (18)
C6—O41.412 (3)O4—H40.8200
C6—C71.505 (3)
C3—C1—H1A109.5C7—C6—P1113.47 (14)
C3—C1—H1B109.5O4—C6—H6108.2
H1A—C1—H1B109.5C7—C6—H6108.2
C3—C1—H1C109.5P1—C6—H6108.2
H1A—C1—H1C109.5C12—C7—C8118.8 (2)
H1B—C1—H1C109.5C12—C7—C6120.54 (19)
C3—C2—H2A109.5C8—C7—C6120.7 (2)
C3—C2—H2B109.5C9—C8—C7120.4 (2)
H2A—C2—H2B109.5C9—C8—H8119.8
C3—C2—H2C109.5C7—C8—H8119.8
H2A—C2—H2C109.5C10—C9—C8119.4 (2)
H2B—C2—H2C109.5C10—C9—H9120.3
C5—C3—C4109.08 (19)C8—C9—H9120.3
C5—C3—C1110.8 (2)C9—C10—C11121.5 (2)
C4—C3—C1110.9 (2)C9—C10—Cl1119.5 (2)
C5—C3—C2107.2 (2)C11—C10—Cl1119.0 (2)
C4—C3—C2108.0 (2)C12—C11—C10118.9 (2)
C1—C3—C2110.6 (2)C12—C11—H11120.6
O1—C4—C3111.34 (17)C10—C11—H11120.6
O1—C4—H4A109.4C11—C12—C7121.1 (2)
C3—C4—H4A109.4C11—C12—H12119.4
O1—C4—H4B109.4C7—C12—H12119.4
C3—C4—H4B109.4C4—O1—P1117.87 (14)
H4A—C4—H4B108.0C5—O2—P1116.83 (14)
O2—C5—C3111.10 (17)C6—O4—H4109.5
O2—C5—H5A109.4O3—P1—O1114.12 (11)
C3—C5—H5A109.4O3—P1—O2113.65 (10)
O2—C5—H5B109.4O1—P1—O2105.62 (9)
C3—C5—H5B109.4O3—P1—C6113.27 (10)
H5A—C5—H5B108.0O1—P1—C6105.02 (9)
O4—C6—C7113.10 (18)O2—P1—C6104.20 (9)
O4—C6—P1105.57 (15)
C5—C3—C4—O1−57.7 (3)C10—C11—C12—C7−0.6 (4)
C1—C3—C4—O164.7 (3)C8—C7—C12—C11−0.1 (3)
C2—C3—C4—O1−173.9 (2)C6—C7—C12—C11178.7 (2)
C4—C3—C5—O258.9 (2)C3—C4—O1—P154.0 (2)
C1—C3—C5—O2−63.5 (2)C3—C5—O2—P1−56.2 (2)
C2—C3—C5—O2175.7 (2)C4—O1—P1—O380.51 (18)
O4—C6—C7—C12−151.46 (19)C4—O1—P1—O2−45.05 (18)
P1—C6—C7—C1288.3 (2)C4—O1—P1—C6−154.86 (16)
O4—C6—C7—C827.3 (3)C5—O2—P1—O3−79.99 (18)
P1—C6—C7—C8−92.9 (2)C5—O2—P1—O145.86 (17)
C12—C7—C8—C90.5 (3)C5—O2—P1—C6156.25 (16)
C6—C7—C8—C9−178.2 (2)O4—C6—P1—O356.16 (18)
C7—C8—C9—C10−0.3 (4)C7—C6—P1—O3−179.45 (15)
C8—C9—C10—C11−0.4 (5)O4—C6—P1—O1−69.01 (15)
C8—C9—C10—Cl1179.8 (2)C7—C6—P1—O155.38 (17)
C9—C10—C11—C120.8 (4)O4—C6—P1—O2−179.83 (14)
Cl1—C10—C11—C12−179.3 (2)C7—C6—P1—O2−55.44 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O3i0.821.892.705 (3)172
Symmetry codes: (i) −x, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O3i0.821.892.705 (3)172
Symmetry codes: (i) −x, y−1/2, −z+1/2.
Acknowledgements top

We gratefully acknowledge financial support of this work by the National Basic Research Program of China (2010CB126100) and the National Natural Science Foundation of China (Nos. 20772042, 21002037). This work was supported in part by the PCSIRT (No. IRT0953).

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bruker (2001). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Liu, H., Zhou, Y. G., Yu, Z. K., Xiao, W. J., Liu, S. H. & He, H. W. (2006). Tetrahedron Lett. 62, 11207–11217.

Peng, H., Wang, T., Xie, P., Chen, T., He, H. W. & Wan, J. (2007). J. Agric. Food Chem. 55, 1871–1880.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Zhou, X., Liu, X. H., Yang, X., Shang, D. J., Xin, J. G. & Feng, X. M. (2008). Angew. Chem. Int. Ed. 47, 392–394.