Diethyl [hydr­oxy(phen­yl)meth­yl]phospho­nate

An, L.-T.; Gong, G.-X.; Liu, X.; Xia, M.; Zhou, J.-F.

doi:10.1107/S1600536808018424

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1320

doi:10.1107/S1600536808018424

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Diethyl [hydroxy(phenyl)methyl]phosphonate

Li-Tao An,^a ^* Gui-Xia Gong,^b Xing Liu,^c Min Xia ^a and Jian-Feng Zhou ^a

^aJiangsu Key Laboratory for the Chemistry of Low-dimensional Materials, Department of Chemistry, Huaiyin Teachers College, Huaian 223300, Jiangsu Province, People's Republic of China, ^bKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215123, People's Republic of China, and ^cDepartment of Chemistry and Biology, Yulin Normal University, Yulin 537000, People's Republic of China
^*Correspondence e-mail: annleet@126.com

(Received 16 June 2008; accepted 17 June 2008; online 21 June 2008)

Molecules of the title compound, C₁₁H₁₇O₄P, are linked into chiral helical chains along the crystallographic b axis via O—H⋯O hydrogen bonds between the hydroxy group and an O atom of the phosphonate group. One ethyl group is disordered over two positions; the site occupancy factors are ca 0.7 and 0.3.

Related literature

For related literature, see: Fang et al. (2006a ,b ,c , 2007 ); Kaboudin (2000 ); Maier & Diel (1994 ); Stowasser et al. (1992 ).

Experimental

Crystal data

C₁₁H₁₇O₄P
M_r = 244.22
Monoclinic, P 2₁ /n
a = 9.2361 (6) Å
b = 8.0719 (5) Å
c = 17.4599 (13) Å
β = 95.096 (5)°
V = 1296.54 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 (2) K
0.30 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ) T_min = 0.940, T_max = 0.959
10679 measured reflections
2345 independent reflections
1723 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.174
S = 1.07
2345 reflections
168 parameters
48 restraints
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.90	2.716 (3)	174
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2001 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018424/rk2099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018424/rk2099Isup2.hkl

checkCIF report

Comment top

The α–hydroxyphosphonic esters and their derivatives have attracted considerable interest owing to their interesting biological activities, such as inhibition of inositol monophosphatase (Maier & Diel, 1994) and HIV protease (Stowasser et al., 1992). These compounds are generally synthesized from aldehydes and phosphites via the base–catalyzed Pudovik reaction, as exemplified by diisopropyl (hydroxyphenylmethyl)phosphonate (Fang, et al., 2006a), dimethyl [hydroxy(phenyl)methyl]phosphonate (Fang, et al., 2006b), diphenyl (hydroxyphenylmethyl)phosphonate (Fang, et al., 2006c) and diethyl hydroxy(4–methoxyphenyl)methylphosphonate (Fang, et al., 2007). As an extension of these studies, we report herein on the structure of C₁₁H₁₇O₄P, (I), (Fig. 1).

In I, the C10 and C11 atoms are disordered over two sets of sites with occupancies of 0.727 (7) and 0.273 (7). All bond distances and bond angles of I are normal and call for no further comment.

There exist a strong intermolecular H-bonding between O1—H1···O2ⁱ (symmetry code: (i) 1/2-x, 1/2+y, 1/2-z) in I. Molecules of I are linked into chiral helical chains by this H–bonding, running parallel to the b axis (Fig. 2). But these chains are aligned in an antiparallel fashion to form inversion centers in the crystal, thus the whole structure is achiral (Fig.3).

Related literature top

For related literature, see: Fang et al. (2006a,b,c; 2007); Kaboudin (2000); Maier & Diel (1994); Stowasser et al. (1992).

Experimental top

All chemicals were obtained from commercial sources and used directly without further purification. Magnesium oxide (2 g) was added to a stirred mixture of diethyl phosphite (0.02 mol) and aldehyde (0.02 mol) at room temperature. After 2 h the mixture was washed by dichloromethane (50 ml) and dried with CaCl₂; evaporation of the solvent gave the crude product. The products were crystallized from n–hexane (Kaboudin, 2000).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A molecular structure of I with the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability level. Only major part of disoprdered moiety are presented. The H atoms are drawn as a small spheres of arbitrary radius.
	Fig. 2. The chiral helical chain constructed by O—H···O H–bonds.
	Fig. 3. Part of the crystal structure of I, showing chiral helical chains aligned in an antiparallel fashion. The H atoms not involved in H–bonds are omitted for clarity.

Diethyl [hydroxy(phenyl)methyl]phosphonate top

Crystal data top

C₁₁H₁₇O₄P	Z = 4
M_r = 244.22	F(000) = 520
Monoclinic, P2₁/n	D_x = 1.251 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.2361 (6) Å	θ = 2.3–25.2°
b = 8.0719 (5) Å	µ = 0.21 mm⁻¹
c = 17.4599 (13) Å	T = 296 K
β = 95.096 (5)°	Prism, colourless
V = 1296.54 (15) Å³	0.30 × 0.30 × 0.20 mm

Data collection top

Rigaku Mercury diffractometer	2345 independent reflections
Radiation source: Fine–focus sealed tube	1723 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.2°, θ_min = 2.3°
ω scans	h = −11→11
Absorption correction: multi-scan (Jacobson, 1998)	k = −9→8
T_min = 0.940, T_max = 0.959	l = −17→20
10679 measured reflections

Refinement top

Refinement on F²	Primary atom site location: Direct
Least-squares matrix: Full	Secondary atom site location: Difmap
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: Geom
wR(F²) = 0.174	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.1001P)² + 0.236P] where P = (F_o² + 2F_c²)/3
2345 reflections	(Δ/σ)_max = 0.001
168 parameters	Δρ_max = 0.38 e Å⁻³
48 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₁H₁₇O₄P	V = 1296.54 (15) Å³
M_r = 244.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.2361 (6) Å	µ = 0.21 mm⁻¹
b = 8.0719 (5) Å	T = 296 K
c = 17.4599 (13) Å	0.30 × 0.30 × 0.20 mm
β = 95.096 (5)°

Data collection top

Rigaku Mercury diffractometer	2345 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	1723 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.959	R_int = 0.030
10679 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	48 restraints
wR(F²) = 0.174	H-atom parameters constrained
S = 1.08	Δρ_max = 0.38 e Å⁻³
2345 reflections	Δρ_min = −0.34 e Å⁻³
168 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	Occ. (<1)
C1	0.0039 (3)	0.8100 (3)	0.27207 (16)	0.0699 (7)
C2	−0.1128 (4)	0.9141 (5)	0.2543 (2)	0.0945 (10)
H2	−0.1080	0.9916	0.2152	0.113*
C3	−0.2344 (5)	0.9061 (6)	0.2925 (3)	0.1194 (14)
H3	−0.3115	0.9773	0.2789	0.143*
C4	−0.2447 (5)	0.7966 (7)	0.3498 (3)	0.1225 (15)
H4	−0.3278	0.7927	0.3761	0.147*
C5	−0.1305 (5)	0.6901 (6)	0.3689 (2)	0.1170 (14)
H5	−0.1370	0.6138	0.4084	0.140*
C6	−0.0049 (4)	0.6957 (4)	0.3296 (2)	0.0888 (10)
H6	0.0716	0.6229	0.3423	0.107*
C7	0.1365 (3)	0.8216 (3)	0.22835 (17)	0.0700 (7)
H7	0.1517	0.9376	0.2146	0.084*
C8	−0.0806 (5)	0.7118 (5)	0.0237 (2)	0.1202 (15)
H8A	−0.0072	0.6701	−0.0078	0.144*
H8B	−0.1403	0.6191	0.0370	0.144*
C9	−0.1684 (5)	0.8298 (5)	−0.0188 (2)	0.1294 (16)
H9A	−0.2427	0.8689	0.0118	0.194*
H9B	−0.2128	0.7791	−0.0648	0.194*
H9C	−0.1093	0.9213	−0.0322	0.194*
C10	0.3970 (12)	0.693 (3)	0.1245 (10)	0.128 (2)	0.273 (7)
H10A	0.3922	0.6073	0.1630	0.153*	0.273 (7)
H10B	0.4512	0.7864	0.1477	0.153*	0.273 (7)
C11	0.4683 (18)	0.629 (2)	0.0560 (10)	0.131 (2)	0.273 (7)
H11A	0.4753	0.7168	0.0194	0.197*	0.273 (7)
H11B	0.4110	0.5404	0.0325	0.197*	0.273 (7)
H11C	0.5638	0.5889	0.0725	0.197*	0.273 (7)
C10'	0.3723 (5)	0.6344 (7)	0.0883 (5)	0.122 (2)	0.727 (7)
H10C	0.3621	0.5770	0.0394	0.147*	0.727 (7)
H10D	0.3777	0.5529	0.1293	0.147*	0.727 (7)
C11'	0.5025 (6)	0.7386 (9)	0.0942 (5)	0.136 (2)	0.727 (7)
H11D	0.4976	0.8149	0.0518	0.204*	0.727 (7)
H11E	0.5872	0.6700	0.0928	0.204*	0.727 (7)
H11F	0.5081	0.7992	0.1416	0.204*	0.727 (7)
O1	0.2648 (2)	0.7606 (3)	0.26977 (14)	0.0876 (7)
H1	0.3101	0.8380	0.2908	0.131*
O2	0.1031 (2)	0.5201 (2)	0.15362 (11)	0.0787 (6)
O3	−0.0104 (2)	0.7844 (3)	0.09335 (11)	0.0889 (7)
O4	0.2499 (3)	0.7456 (3)	0.09497 (16)	0.1077 (8)
P1	0.11894 (8)	0.69802 (9)	0.14126 (4)	0.0710 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0760 (17)	0.0661 (16)	0.0641 (15)	0.0012 (13)	−0.0139 (13)	−0.0117 (12)
C2	0.097 (2)	0.101 (2)	0.084 (2)	0.0294 (19)	0.0000 (18)	−0.0047 (17)
C3	0.100 (3)	0.146 (4)	0.111 (3)	0.030 (3)	0.002 (2)	−0.027 (3)
C4	0.107 (3)	0.144 (4)	0.119 (3)	−0.012 (3)	0.027 (3)	−0.048 (3)
C5	0.143 (4)	0.119 (3)	0.091 (3)	−0.029 (3)	0.022 (3)	−0.005 (2)
C6	0.102 (2)	0.080 (2)	0.082 (2)	−0.0091 (17)	−0.0077 (19)	0.0029 (16)
C7	0.0726 (16)	0.0543 (14)	0.0788 (17)	0.0010 (12)	−0.0172 (14)	0.0031 (12)
C8	0.125 (3)	0.118 (3)	0.108 (3)	0.018 (2)	−0.044 (3)	−0.014 (2)
C9	0.148 (4)	0.129 (3)	0.100 (3)	0.009 (3)	−0.050 (3)	−0.001 (2)
C10	0.093 (3)	0.113 (5)	0.179 (6)	0.013 (4)	0.031 (4)	0.015 (4)
C11	0.098 (4)	0.117 (5)	0.181 (6)	0.016 (4)	0.031 (4)	0.012 (4)
C10'	0.091 (3)	0.107 (4)	0.173 (6)	0.014 (2)	0.038 (3)	0.016 (3)
C11'	0.101 (3)	0.121 (4)	0.188 (6)	0.007 (3)	0.023 (3)	0.012 (4)
O1	0.0732 (12)	0.0743 (12)	0.1085 (16)	0.0046 (10)	−0.0301 (12)	−0.0079 (12)
O2	0.0826 (13)	0.0656 (12)	0.0845 (13)	0.0092 (9)	−0.0106 (10)	−0.0046 (9)
O3	0.1065 (16)	0.0916 (15)	0.0645 (11)	0.0306 (11)	−0.0157 (11)	−0.0027 (9)
O4	0.1062 (16)	0.0990 (16)	0.1221 (19)	0.0288 (14)	0.0325 (15)	0.0324 (15)
P1	0.0741 (5)	0.0677 (5)	0.0694 (5)	0.0125 (3)	−0.0035 (4)	0.0054 (3)

Geometric parameters (Å, º) top

C1—C6	1.371 (4)	C9—H9B	0.9600
C1—C2	1.380 (4)	C9—H9C	0.9600
C1—C7	1.503 (4)	C10—O4	1.471 (8)
C2—C3	1.358 (5)	C10—C11	1.509 (10)
C2—H2	0.9300	C10—H10A	0.9700
C3—C4	1.344 (7)	C10—H10B	0.9700
C3—H3	0.9300	C11—H11A	0.9600
C4—C5	1.378 (7)	C11—H11B	0.9600
C4—H4	0.9300	C11—H11C	0.9600
C5—C6	1.401 (5)	C10'—O4	1.456 (5)
C5—H5	0.9300	C10'—C11'	1.464 (7)
C6—H6	0.9300	C10'—H10C	0.9700
C7—O1	1.420 (3)	C10'—H10D	0.9700
C7—P1	1.814 (3)	C11'—H11D	0.9600
C7—H7	0.9800	C11'—H11E	0.9600
C8—C9	1.418 (5)	C11'—H11F	0.9600
C8—O3	1.450 (4)	O1—H1	0.82
C8—H8A	0.9700	O2—P1	1.462 (2)
C8—H8B	0.9700	O3—P1	1.561 (2)
C9—H9A	0.9600	O4—P1	1.562 (3)

C6—C1—C2	118.6 (3)	H9A—C9—H9B	109.5
C6—C1—C7	121.2 (3)	C8—C9—H9C	109.5
C2—C1—C7	120.2 (3)	H9A—C9—H9C	109.5
C3—C2—C1	121.6 (4)	H9B—C9—H9C	109.5
C3—C2—H2	119.2	O4—C10—C11	105.9 (11)
C1—C2—H2	119.2	O4—C10—H10A	110.5
C4—C3—C2	120.9 (4)	C11—C10—H10A	110.5
C4—C3—H3	119.6	O4—C10—H10B	110.5
C2—C3—H3	119.6	C11—C10—H10B	110.5
C3—C4—C5	119.1 (4)	H10A—C10—H10B	108.7
C3—C4—H4	120.4	O4—C10'—C11'	106.2 (5)
C5—C4—H4	120.4	O4—C10'—H10C	110.5
C4—C5—C6	120.7 (4)	C11'—C10'—H10C	110.5
C4—C5—H5	119.6	O4—C10'—H10D	110.5
C6—C5—H5	119.6	C11'—C10'—H10D	110.5
C1—C6—C5	119.1 (4)	H10C—C10'—H10D	108.7
C1—C6—H6	120.5	C10'—C11'—H11D	109.5
C5—C6—H6	120.5	C10'—C11'—H11E	109.5
O1—C7—C1	113.6 (2)	H11D—C11'—H11E	109.5
O1—C7—P1	104.17 (19)	C10'—C11'—H11F	109.5
C1—C7—P1	112.03 (18)	H11D—C11'—H11F	109.5
O1—C7—H7	109.0	H11E—C11'—H11F	109.5
C1—C7—H7	109.0	C7—O1—H1	109.5
P1—C7—H7	109.0	C8—O3—P1	122.2 (2)
C9—C8—O3	111.1 (3)	C10'—O4—P1	122.1 (3)
C9—C8—H8A	109.4	C10—O4—P1	118.8 (8)
O3—C8—H8A	109.4	O2—P1—O3	115.86 (12)
C9—C8—H8B	109.4	O2—P1—O4	114.24 (13)
O3—C8—H8B	109.4	O3—P1—O4	101.79 (14)
H8A—C8—H8B	108.0	O2—P1—C7	114.79 (12)
C8—C9—H9A	109.5	O3—P1—C7	102.18 (12)
C8—C9—H9B	109.5	O4—P1—C7	106.42 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.90	2.716 (3)	174

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₇O₄P
M_r	244.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	9.2361 (6), 8.0719 (5), 17.4599 (13)
β (°)	95.096 (5)
V (Å³)	1296.54 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.940, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	10679, 2345, 1723
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.174, 1.08
No. of reflections	2345
No. of parameters	168
No. of restraints	48
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.34

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.899	2.716 (3)	173.49

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the Program for Excellent Talents in Huaiyin Teachers College (ETHYTC, 07QNZC010) and the Natural Science Foundation of the Education Committee of Guangxi Province.

References

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