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

Wang, C.; Peng, H.; He, H.

doi:10.1107/S1600536811008944

organic compounds

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Volume 67| Part 4| April 2011| Page o926

doi:10.1107/S1600536811008944

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

Chubei Wang,^a Hao Peng ^a and Hongwu He ^a ^*

^aKey Laboratory of Pesticide and Chemical Biology, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China.
^*Correspondence e-mail: he1208@mail.ccnu.edu.cn

(Received 4 March 2011; accepted 9 March 2011; online 19 March 2011)

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.

Related literature

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

Crystal data

C₁₂H₁₆ClO₄P
M_r = 290.67
Monoclinic, P 2₁ /c
a = 12.8965 (11) Å
b = 9.4449 (8) Å
c = 11.6425 (10) Å
β = 98.630 (1)°
V = 1402.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 298 K
0.23 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
10123 measured reflections
3463 independent reflections
3141 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.154
S = 1.15
3463 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O3ⁱ	0.82	1.89	2.705 (3)	172
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008944/wn2424sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008944/wn2424Isup2.hkl

checkCIF report

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.

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

	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.
	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

C₁₂H₁₆ClO₄P	F(000) = 608
M_r = 290.67	D_x = 1.377 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.8965 (11) Å	Cell parameters from 4935 reflections
b = 9.4449 (8) Å	θ = 2.7–28.2°
c = 11.6425 (10) Å	µ = 0.39 mm⁻¹
β = 98.630 (1)°	T = 298 K
V = 1402.1 (2) Å³	Block, colourless
Z = 4	0.23 × 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 tube	R_int = 0.071
Graphite monochromator	θ_max = 28.3°, θ_min = 2.7°
ϕ and ω scans	h = −13→17
10123 measured reflections	k = −9→12
3463 independent reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0581P)² + 0.7742P] where P = (F_o² + 2F_c²)/3
3463 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₂H₁₆ClO₄P	V = 1402.1 (2) Å³
M_r = 290.67	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.8965 (11) Å	µ = 0.39 mm⁻¹
b = 9.4449 (8) Å	T = 298 K
c = 11.6425 (10) Å	0.23 × 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 reflections	R_int = 0.071
3463 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.15	Δρ_max = 0.72 e Å⁻³
3463 reflections	Δρ_min = −0.28 e Å⁻³
166 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.2944 (2)	0.3005 (3)	0.5354 (2)	0.0543 (6)
H1A	0.2923	0.3256	0.6150	0.081*
H1B	0.3596	0.3312	0.5135	0.081*
H1C	0.2883	0.1996	0.5267	0.081*
C2	0.2096 (3)	0.5330 (3)	0.4720 (3)	0.0635 (8)
H2A	0.1547	0.5765	0.4188	0.095*
H2B	0.2764	0.5659	0.4561	0.095*
H2C	0.2014	0.5577	0.5501	0.095*
C3	0.2035 (2)	0.3720 (2)	0.4576 (2)	0.0407 (5)
C4	0.2059 (2)	0.3377 (2)	0.3303 (2)	0.0430 (5)
H4A	0.1519	0.3917	0.2823	0.052*
H4B	0.2733	0.3655	0.3099	0.052*
C5	0.09896 (19)	0.3251 (2)	0.4897 (2)	0.0429 (5)
H5A	0.0971	0.3465	0.5708	0.052*
H5B	0.0428	0.3773	0.4434	0.052*
C6	0.12155 (17)	−0.0698 (2)	0.36460 (19)	0.0359 (4)
H6	0.0632	−0.1171	0.3939	0.043*
C7	0.21964 (16)	−0.09498 (19)	0.44979 (18)	0.0330 (4)
C8	0.31652 (19)	−0.1076 (3)	0.4118 (2)	0.0432 (5)
H8	0.3212	−0.0978	0.3333	0.052*
C9	0.4058 (2)	−0.1346 (3)	0.4902 (3)	0.0550 (6)
H9	0.4705	−0.1435	0.4647	0.066*
C10	0.3983 (2)	−0.1482 (3)	0.6055 (3)	0.0554 (7)
C11	0.3035 (2)	−0.1347 (3)	0.6457 (2)	0.0509 (6)
H11	0.2996	−0.1430	0.7245	0.061*
C12	0.21483 (19)	−0.1088 (2)	0.5673 (2)	0.0422 (5)
H12	0.1505	−0.1004	0.5936	0.051*
Cl1	0.51070 (8)	−0.18286 (16)	0.70446 (9)	0.1062 (4)
O1	0.18909 (13)	0.18663 (16)	0.30702 (13)	0.0403 (4)
O2	0.08252 (12)	0.17262 (17)	0.46986 (13)	0.0402 (4)
O3	−0.00798 (14)	0.1404 (2)	0.26116 (16)	0.0537 (5)
O4	0.12788 (16)	−0.12340 (19)	0.25263 (15)	0.0526 (5)
H4	0.0926	−0.1957	0.2418	0.079*
P1	0.08858 (4)	0.11632 (6)	0.34372 (5)	0.03362 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0489 (14)	0.0561 (16)	0.0541 (14)	−0.0019 (12)	−0.0045 (11)	0.0008 (12)
C2	0.088 (2)	0.0332 (12)	0.0674 (17)	−0.0063 (13)	0.0042 (16)	−0.0104 (12)
C3	0.0505 (13)	0.0286 (10)	0.0416 (11)	−0.0025 (9)	0.0024 (10)	−0.0031 (8)
C4	0.0560 (14)	0.0298 (10)	0.0439 (12)	−0.0069 (10)	0.0099 (10)	0.0024 (9)
C5	0.0511 (13)	0.0373 (11)	0.0411 (11)	0.0065 (10)	0.0093 (10)	−0.0078 (9)
C6	0.0345 (10)	0.0291 (9)	0.0438 (11)	−0.0071 (8)	0.0048 (8)	−0.0022 (8)
C7	0.0356 (10)	0.0188 (8)	0.0442 (11)	−0.0014 (7)	0.0045 (8)	0.0004 (7)
C8	0.0402 (12)	0.0439 (12)	0.0463 (12)	−0.0019 (10)	0.0096 (10)	0.0011 (10)
C9	0.0366 (12)	0.0619 (17)	0.0668 (16)	0.0031 (11)	0.0087 (11)	0.0032 (13)
C10	0.0442 (14)	0.0571 (16)	0.0606 (16)	0.0052 (12)	−0.0060 (11)	0.0079 (13)
C11	0.0615 (16)	0.0483 (14)	0.0421 (12)	0.0045 (12)	0.0049 (11)	0.0084 (10)
C12	0.0419 (12)	0.0384 (12)	0.0476 (12)	0.0039 (9)	0.0114 (10)	0.0043 (9)
Cl1	0.0629 (6)	0.1541 (11)	0.0912 (7)	0.0175 (6)	−0.0221 (5)	0.0266 (7)
O1	0.0520 (9)	0.0310 (8)	0.0412 (8)	−0.0050 (7)	0.0175 (7)	−0.0022 (6)
O2	0.0435 (9)	0.0373 (8)	0.0423 (8)	0.0009 (7)	0.0150 (7)	−0.0016 (6)
O3	0.0485 (10)	0.0528 (10)	0.0546 (10)	0.0105 (8)	−0.0089 (8)	0.0022 (8)
O4	0.0622 (12)	0.0444 (10)	0.0503 (10)	−0.0086 (8)	0.0054 (8)	−0.0130 (8)
P1	0.0342 (3)	0.0304 (3)	0.0358 (3)	0.0021 (2)	0.0039 (2)	0.0004 (2)

Geometric parameters (Å, º) top

C1—C3	1.528 (3)	C6—P1	1.816 (2)
C1—H1A	0.9600	C6—H6	0.9800
C1—H1B	0.9600	C7—C12	1.385 (3)
C1—H1C	0.9600	C7—C8	1.392 (3)
C2—C3	1.530 (3)	C8—C9	1.382 (3)
C2—H2A	0.9600	C8—H8	0.9300
C2—H2B	0.9600	C9—C10	1.367 (4)
C2—H2C	0.9600	C9—H9	0.9300
C3—C5	1.518 (3)	C10—C11	1.379 (4)
C3—C4	1.522 (3)	C10—Cl1	1.742 (3)
C4—O1	1.463 (3)	C11—C12	1.373 (3)
C4—H4A	0.9700	C11—H11	0.9300
C4—H4B	0.9700	C12—H12	0.9300
C5—O2	1.469 (3)	O1—P1	1.5716 (16)
C5—H5A	0.9700	O2—P1	1.5748 (16)
C5—H5B	0.9700	O3—P1	1.4721 (18)
C6—O4	1.412 (3)	O4—H4	0.8200
C6—C7	1.505 (3)

C3—C1—H1A	109.5	C7—C6—P1	113.47 (14)
C3—C1—H1B	109.5	O4—C6—H6	108.2
H1A—C1—H1B	109.5	C7—C6—H6	108.2
C3—C1—H1C	109.5	P1—C6—H6	108.2
H1A—C1—H1C	109.5	C12—C7—C8	118.8 (2)
H1B—C1—H1C	109.5	C12—C7—C6	120.54 (19)
C3—C2—H2A	109.5	C8—C7—C6	120.7 (2)
C3—C2—H2B	109.5	C9—C8—C7	120.4 (2)
H2A—C2—H2B	109.5	C9—C8—H8	119.8
C3—C2—H2C	109.5	C7—C8—H8	119.8
H2A—C2—H2C	109.5	C10—C9—C8	119.4 (2)
H2B—C2—H2C	109.5	C10—C9—H9	120.3
C5—C3—C4	109.08 (19)	C8—C9—H9	120.3
C5—C3—C1	110.8 (2)	C9—C10—C11	121.5 (2)
C4—C3—C1	110.9 (2)	C9—C10—Cl1	119.5 (2)
C5—C3—C2	107.2 (2)	C11—C10—Cl1	119.0 (2)
C4—C3—C2	108.0 (2)	C12—C11—C10	118.9 (2)
C1—C3—C2	110.6 (2)	C12—C11—H11	120.6
O1—C4—C3	111.34 (17)	C10—C11—H11	120.6
O1—C4—H4A	109.4	C11—C12—C7	121.1 (2)
C3—C4—H4A	109.4	C11—C12—H12	119.4
O1—C4—H4B	109.4	C7—C12—H12	119.4
C3—C4—H4B	109.4	C4—O1—P1	117.87 (14)
H4A—C4—H4B	108.0	C5—O2—P1	116.83 (14)
O2—C5—C3	111.10 (17)	C6—O4—H4	109.5
O2—C5—H5A	109.4	O3—P1—O1	114.12 (11)
C3—C5—H5A	109.4	O3—P1—O2	113.65 (10)
O2—C5—H5B	109.4	O1—P1—O2	105.62 (9)
C3—C5—H5B	109.4	O3—P1—C6	113.27 (10)
H5A—C5—H5B	108.0	O1—P1—C6	105.02 (9)
O4—C6—C7	113.10 (18)	O2—P1—C6	104.20 (9)
O4—C6—P1	105.57 (15)

C5—C3—C4—O1	−57.7 (3)	C10—C11—C12—C7	−0.6 (4)
C1—C3—C4—O1	64.7 (3)	C8—C7—C12—C11	−0.1 (3)
C2—C3—C4—O1	−173.9 (2)	C6—C7—C12—C11	178.7 (2)
C4—C3—C5—O2	58.9 (2)	C3—C4—O1—P1	54.0 (2)
C1—C3—C5—O2	−63.5 (2)	C3—C5—O2—P1	−56.2 (2)
C2—C3—C5—O2	175.7 (2)	C4—O1—P1—O3	80.51 (18)
O4—C6—C7—C12	−151.46 (19)	C4—O1—P1—O2	−45.05 (18)
P1—C6—C7—C12	88.3 (2)	C4—O1—P1—C6	−154.86 (16)
O4—C6—C7—C8	27.3 (3)	C5—O2—P1—O3	−79.99 (18)
P1—C6—C7—C8	−92.9 (2)	C5—O2—P1—O1	45.86 (17)
C12—C7—C8—C9	0.5 (3)	C5—O2—P1—C6	156.25 (16)
C6—C7—C8—C9	−178.2 (2)	O4—C6—P1—O3	56.16 (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—Cl1	179.8 (2)	C7—C6—P1—O1	55.38 (17)
C9—C10—C11—C12	0.8 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.82	1.89	2.705 (3)	172

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆ClO₄P
M_r	290.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.8965 (11), 9.4449 (8), 11.6425 (10)
β (°)	98.630 (1)
V (Å³)	1402.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.23 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10123, 3463, 3141
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.154, 1.15
No. of reflections	3463
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.28

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.82	1.89	2.705 (3)	172

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

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

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. CrossRef Web of Science Google Scholar
Bruker (2001). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, H., Zhou, Y. G., Yu, Z. K., Xiao, W. J., Liu, S. H. & He, H. W. (2006). Tetrahedron Lett. 62, 11207–11217. CrossRef CAS Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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