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In the crystal structure of the title compound, C9H12ClO4P, the distorted tetra­hedral geometry around the P atom consists of three phospho­nate O atoms and one C atom of the benzyl group. The bond angles around phospho­rus are in the range 101.76 (15)-116.18 (17)°. The P-O single-bond lengths are nearly equal [1.569 (3) Å], while the P=O double-bond length is 1.469 (3) Å. There exists strong inter­molecular hydrogen bonding between the hydr­oxy group and an O atom of the phospho­nate group of a symmetry-related mol­ecule. Owing to inter­molecular hydrogen bonding, a one-dimensional polymeric network is formed, extending along the crystallographic b axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039499/bq2031sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039499/bq2031Isup2.hkl
Contains datablock I

CCDC reference: 662412

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.039
  • wR factor = 0.113
  • Data-to-parameter ratio = 9.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for P1 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 6
Alert level G ABSTY01_ALERT_1_G Extra text has been found in the _exptl_absorpt_correction_type field, which should be only a single keyword. A literature citation should be included in the _exptl_absorpt_process_details field. REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 26.27 From the CIF: _reflns_number_total 1314 Count of symmetry unique reflns 1361 Completeness (_total/calc) 96.55% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C7 = . R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

α-Hydroxy phosphonates are a subject of increasing interest because these compounds inhibit various enzymes like renin (Patel et al., 1990) and HIV protease (Stowasser et al., 1992).

To our surprise various samples of (I) obtained in different batches have had some optical activity indicating that either the mechanism favours one conformer, or, two optical isomers prefer to crystallize separately in unequal proportions. Hence, we determined the crystal structure.

As can be seen on ORTEP diagram (Fig. 1.) the crystal investigated contains only the R-isomer. The P-atom adopts a distorted tetrahedral configuration: the bond angles aroud it being in the range 101.76 (15)°-116.18 (17)°. These values are closer to ideal like reported earlier (Fang et al., 2006) than those of dimethyl[α-(benzylamino)-p-chlorobenzyl]phosphonate (Liu et al., 1995). The geometry about P-atom is exactly similar to (Fang et al., 2006), however, all the bond distances around P-atom are all larger. The bond distance P1—C7 [1.822 (3) Å] is smaller compared to the value [1.860 (4) Å], in our reported structure (Tahir et al., 1996). There exist a strong inter-molecular hydrogen bonding between O1—H1 (hydroxy group) and O2i(x + 1/2, -y + 1/2, -z). Another inter-molecular hydrogen bonding exists between C7—H7 and O1(x + 1/2, -y + 1/2, -z) which forms eight membered group (C7,O1,H1,O2i,P1i,C7i,O1i,H7). There also exists an intre-molecular hydrogen bonding between C7—H7···Cl1. Due to inter-molecular hydrogen bonding one-dimensional polymeric network is formed extending to crystallographic b axis (Fig. 2). The closest approach between polymeric chains is among C6 and C9 (x, y + 1, z) [3.387 (6) Å]. The Flack parameter -0.13 (17) [Flack, 1983] clearly indicates the R-configuration of the title compound.

Related literature top

For related literature, see: Fang et al. (2006); Liu et al. (1995); Patel et al. (1990); Stowasser et al. (1992); Tahir et al. (1996).

Experimental top

1.41 g (10 mmole) of o-chlorobenzaldehyde was disolved in an equivalent amount (1.10 g) of neat dimethylphosphonate in the presence of an equal mixture (2.5 g + 2.5 g) of KF and ψ-Al2O3. The mixture was kept at room temperature for 48 h. The product was extracted twice with 20 ml portions of a dichloromethane-methanol mixture (1:1). After the evaporation of the solvant on a rotary evaporator, the oily residue was redisolved in a mixture of diethyl ether and acetone (3:1) and recrystallized in this medium. M·P: (83–86 °C); yield: 40 percent %.

Refinement top

H atoms to the C-atoms of the phenyl ring were bonded geometrically 0.930 Å, while the H-atom attached to C7 is at a distance of 0.98 Å. Thermal parameter of all these H atoms was taken 1.2 times of the corresponding atoms. The thermal parameter of H-atoms geometrically bonded to CH3 groups [0.960 Å] and H-atom of OH [0.80 Å] was taken 1.5 times of the corresponding atom. Regarding data: Some reflections could not be recovered from flopy at back back home and also zero track of used hard disk damaged.

Structure description top

α-Hydroxy phosphonates are a subject of increasing interest because these compounds inhibit various enzymes like renin (Patel et al., 1990) and HIV protease (Stowasser et al., 1992).

To our surprise various samples of (I) obtained in different batches have had some optical activity indicating that either the mechanism favours one conformer, or, two optical isomers prefer to crystallize separately in unequal proportions. Hence, we determined the crystal structure.

As can be seen on ORTEP diagram (Fig. 1.) the crystal investigated contains only the R-isomer. The P-atom adopts a distorted tetrahedral configuration: the bond angles aroud it being in the range 101.76 (15)°-116.18 (17)°. These values are closer to ideal like reported earlier (Fang et al., 2006) than those of dimethyl[α-(benzylamino)-p-chlorobenzyl]phosphonate (Liu et al., 1995). The geometry about P-atom is exactly similar to (Fang et al., 2006), however, all the bond distances around P-atom are all larger. The bond distance P1—C7 [1.822 (3) Å] is smaller compared to the value [1.860 (4) Å], in our reported structure (Tahir et al., 1996). There exist a strong inter-molecular hydrogen bonding between O1—H1 (hydroxy group) and O2i(x + 1/2, -y + 1/2, -z). Another inter-molecular hydrogen bonding exists between C7—H7 and O1(x + 1/2, -y + 1/2, -z) which forms eight membered group (C7,O1,H1,O2i,P1i,C7i,O1i,H7). There also exists an intre-molecular hydrogen bonding between C7—H7···Cl1. Due to inter-molecular hydrogen bonding one-dimensional polymeric network is formed extending to crystallographic b axis (Fig. 2). The closest approach between polymeric chains is among C6 and C9 (x, y + 1, z) [3.387 (6) Å]. The Flack parameter -0.13 (17) [Flack, 1983] clearly indicates the R-configuration of the title compound.

For related literature, see: Fang et al. (2006); Liu et al. (1995); Patel et al. (1990); Stowasser et al. (1992); Tahir et al. (1996).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1992); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Version 1.70.01; Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. ORTEP drawing of the title compound with the atom numbering scheme. The thermal ellpsoids are drawn at the 30% probability level. H-atoms are shown by small circles of arbitrary radii.
[Figure 2] Fig. 2. The packing figure (PLATON: Spek, 2003) showing the mechanism of hydrogen bonding.
(R)-Dimethyl [(2-chlorophenyl)hydroxymethyl]phosphonate top
Crystal data top
C9H12ClO4PDx = 1.458 Mg m3
Mr = 250.61Melting point = 83–86 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 7.5670 (12) Åθ = 10.6–18.5°
b = 7.9230 (13) ŵ = 0.47 mm1
c = 19.0420 (12) ÅT = 295 K
V = 1141.6 (3) Å3Prism, colourless
Z = 40.25 × 0.2 × 0.15 mm
F(000) = 520
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.012
ω/2θ scansθmax = 26.3°, θmin = 2.8°
Absorption correction: empirical (using intensity measurements) via ψ scans (molEN; Fair, 1990)h = 09
Tmin = 0.885, Tmax = 0.954k = 09
1361 measured reflectionsl = 2323
1314 independent reflections3 standard reflections every 120 min
1119 reflections with I > 2σ(I) intensity decay: 2.5%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039 w = 1/[σ2(Fo2) + (0.0418P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.113(Δ/σ)max < 0.001
S = 1.10Δρmax = 0.40 e Å3
1314 reflectionsΔρmin = 0.24 e Å3
137 parametersAbsolute structure: Flack (1983), number of Friedel pairs?
0 restraintsAbsolute structure parameter: 0.13 (17)
Primary atom site location: structure-invariant direct methods
Crystal data top
C9H12ClO4PV = 1141.6 (3) Å3
Mr = 250.61Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.5670 (12) ŵ = 0.47 mm1
b = 7.9230 (13) ÅT = 295 K
c = 19.0420 (12) Å0.25 × 0.2 × 0.15 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
1119 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements) via ψ scans (molEN; Fair, 1990)Rint = 0.012
Tmin = 0.885, Tmax = 0.9543 standard reflections every 120 min
1361 measured reflections intensity decay: 2.5%
1314 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.113Δρmax = 0.40 e Å3
S = 1.10Δρmin = 0.24 e Å3
1314 reflectionsAbsolute structure: Flack (1983), number of Friedel pairs?
137 parametersAbsolute structure parameter: 0.13 (17)
0 restraints
Special details top

Experimental. the structure was solved by Patterson method using SHELX86. The whole molecule was recognized.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.56770 (15)0.23649 (19)0.17150 (7)0.0795 (4)
P10.17377 (12)0.01006 (12)0.04711 (5)0.0473 (3)
O10.1972 (4)0.3210 (3)0.00635 (13)0.0574 (7)
H10.27710.37220.01350.086*
O20.0201 (3)0.0013 (3)0.04521 (15)0.0598 (7)
O30.2678 (4)0.0579 (5)0.02068 (17)0.0851 (11)
O40.2591 (4)0.0924 (3)0.10882 (16)0.0677 (8)
C10.2247 (5)0.2842 (4)0.13248 (18)0.0435 (8)
C20.3483 (5)0.2960 (5)0.18634 (19)0.0503 (8)
C30.3055 (7)0.3590 (6)0.2521 (2)0.0681 (12)
H30.39090.36470.28710.082*
C40.1361 (7)0.4132 (6)0.2651 (2)0.0711 (13)
H40.10680.45750.30870.085*
C50.0103 (6)0.4015 (6)0.2133 (2)0.0678 (11)
H50.10510.43530.22260.081*
C60.0532 (5)0.3401 (5)0.1477 (2)0.0551 (9)
H60.03300.33570.11300.066*
C70.2690 (5)0.2188 (4)0.06033 (16)0.0442 (7)
H70.39770.21270.05500.053*
C80.1895 (8)0.1584 (7)0.0722 (3)0.0854 (15)
H8A0.27450.18320.10820.128*
H8B0.09110.09930.09240.128*
H8C0.14890.26180.05140.128*
C90.2136 (6)0.2659 (6)0.1212 (3)0.0752 (13)
H9A0.27860.30720.16100.113*
H9B0.24250.33180.08050.113*
H9C0.08920.27450.13050.113*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0526 (6)0.1012 (9)0.0848 (7)0.0123 (7)0.0213 (5)0.0012 (7)
P10.0411 (5)0.0440 (4)0.0568 (5)0.0009 (4)0.0001 (4)0.0005 (4)
O10.0495 (15)0.0652 (16)0.0574 (14)0.0111 (13)0.0051 (13)0.0206 (12)
O20.0424 (13)0.0495 (13)0.0875 (17)0.0030 (12)0.0028 (13)0.0068 (17)
O30.0605 (19)0.108 (3)0.087 (2)0.0166 (19)0.0124 (17)0.044 (2)
O40.0700 (19)0.0418 (13)0.0913 (19)0.0008 (14)0.0206 (16)0.0101 (13)
C10.0437 (19)0.0368 (15)0.0501 (17)0.0043 (14)0.0008 (15)0.0088 (14)
C20.050 (2)0.0448 (18)0.0564 (19)0.0040 (16)0.0059 (16)0.0091 (16)
C30.081 (3)0.069 (3)0.055 (2)0.009 (3)0.009 (2)0.0008 (19)
C40.092 (4)0.065 (2)0.057 (2)0.011 (3)0.011 (2)0.010 (2)
C50.061 (3)0.062 (2)0.081 (3)0.002 (2)0.016 (2)0.004 (2)
C60.048 (2)0.0504 (19)0.067 (2)0.0044 (17)0.0004 (19)0.0005 (17)
C70.0416 (17)0.0436 (16)0.0474 (17)0.0051 (15)0.0010 (14)0.0031 (15)
C80.084 (3)0.091 (3)0.081 (3)0.000 (3)0.008 (3)0.034 (3)
C90.066 (3)0.054 (2)0.106 (3)0.003 (2)0.002 (3)0.019 (2)
Geometric parameters (Å, º) top
Cl1—C21.748 (4)C3—H30.9300
P1—O21.469 (3)C4—C51.374 (7)
P1—O41.568 (3)C4—H40.9300
P1—O31.569 (3)C5—C61.379 (6)
P1—C71.822 (3)C5—H50.9300
O1—C71.417 (4)C6—H60.9300
O1—H10.8200C7—H70.9800
O3—C81.396 (5)C8—H8A0.9600
O4—C91.436 (5)C8—H8B0.9600
C1—C21.392 (5)C8—H8C0.9600
C1—C61.401 (5)C9—H9A0.9600
C1—C71.506 (5)C9—H9B0.9600
C2—C31.386 (6)C9—H9C0.9600
C3—C41.374 (7)
O2—P1—O4113.93 (18)C6—C5—H5119.7
O2—P1—O3114.62 (18)C5—C6—C1121.1 (4)
O4—P1—O3104.59 (19)C5—C6—H6119.4
O2—P1—C7116.18 (17)C1—C6—H6119.4
O4—P1—C7101.76 (15)O1—C7—C1112.3 (3)
O3—P1—C7104.22 (17)O1—C7—P1105.5 (2)
C7—O1—H1109.5C1—C7—P1110.5 (2)
C8—O3—P1125.5 (3)O1—C7—H7109.5
C9—O4—P1121.3 (3)C1—C7—H7109.5
C2—C1—C6116.7 (3)P1—C7—H7109.5
C2—C1—C7123.1 (3)O3—C8—H8A109.5
C6—C1—C7120.2 (3)O3—C8—H8B109.5
C3—C2—C1122.2 (4)H8A—C8—H8B109.5
C3—C2—Cl1117.7 (3)O3—C8—H8C109.5
C1—C2—Cl1120.1 (3)H8A—C8—H8C109.5
C4—C3—C2119.6 (4)H8B—C8—H8C109.5
C4—C3—H3120.2O4—C9—H9A109.5
C2—C3—H3120.2O4—C9—H9B109.5
C5—C4—C3119.8 (4)H9A—C9—H9B109.5
C5—C4—H4120.1O4—C9—H9C109.5
C3—C4—H4120.1H9A—C9—H9C109.5
C4—C5—C6120.7 (4)H9B—C9—H9C109.5
C4—C5—H5119.7
O2—P1—O3—C816.2 (5)C4—C5—C6—C11.6 (7)
O4—P1—O3—C8109.3 (5)C2—C1—C6—C50.8 (6)
C7—P1—O3—C8144.3 (4)C7—C1—C6—C5179.5 (4)
O2—P1—O4—C951.0 (4)C2—C1—C7—O1134.9 (3)
O3—P1—O4—C974.9 (4)C6—C1—C7—O143.8 (4)
C7—P1—O4—C9176.8 (3)C2—C1—C7—P1107.6 (3)
C6—C1—C2—C30.2 (5)C6—C1—C7—P173.7 (4)
C7—C1—C2—C3178.9 (3)O2—P1—C7—O155.4 (3)
C6—C1—C2—Cl1177.7 (3)O4—P1—C7—O1179.7 (2)
C7—C1—C2—Cl11.0 (5)O3—P1—C7—O171.8 (3)
C1—C2—C3—C40.4 (6)O2—P1—C7—C166.3 (3)
Cl1—C2—C3—C4177.6 (4)O4—P1—C7—C158.1 (3)
C2—C3—C4—C51.1 (7)O3—P1—C7—C1166.6 (2)
C3—C4—C5—C61.7 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.821.932.743 (4)171
C7—H7···Cl10.982.573.100 (4)114
C7—H7···O1i0.982.563.494 (5)159
Symmetry code: (i) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC9H12ClO4P
Mr250.61
Crystal system, space groupOrthorhombic, P212121
Temperature (K)295
a, b, c (Å)7.5670 (12), 7.9230 (13), 19.0420 (12)
V3)1141.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.25 × 0.2 × 0.15
Data collection
DiffractometerEnraf–Nonius CAD-4
Absorption correctionEmpirical (using intensity measurements) via ψ scans (MolEN; Fair, 1990)
Tmin, Tmax0.885, 0.954
No. of measured, independent and
observed [I > 2σ(I)] reflections
1361, 1314, 1119
Rint0.012
(sin θ/λ)max1)0.623
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.113, 1.10
No. of reflections1314
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.24
Absolute structureFlack (1983), number of Friedel pairs?
Absolute structure parameter0.13 (17)

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1992), MolEN (Fair, 1990), SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Version 1.70.01; Farrugia, 1999).

Selected geometric parameters (Å, º) top
Cl1—C21.748 (4)O1—C71.417 (4)
P1—O21.469 (3)O3—C81.396 (5)
P1—O41.568 (3)O4—C91.436 (5)
P1—O31.569 (3)C1—C71.506 (5)
P1—C71.822 (3)
O2—P1—O4113.93 (18)O2—P1—C7116.18 (17)
O2—P1—O3114.62 (18)O4—P1—C7101.76 (15)
O4—P1—O3104.59 (19)O3—P1—C7104.22 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.821.932.743 (4)171
C7—H7···Cl10.982.573.100 (4)114
C7—H7···O1i0.982.563.494 (5)159
Symmetry code: (i) x+1/2, y+1/2, z.
 

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