PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o481.
Published online 2009 February 6. doi:  10.1107/S1600536809004036
PMCID: PMC2968507

Dimethyl (1-hydr­oxy-1,2-diphenyl­ethyl)phospho­nate

Abstract

In the mol­ecule of the title compound, C16H19O4P, the coordination around the P atom is distorted tetra­hedral. The aromatic rings are oriented at a dihedral angle of 72.28 (11)°. Intra­molecular C—H(...)O hydrogen bonding result in the formation of five- and six-membered rings. In the crystal structure, inter­molecular C—H(...)O hydrogen bonds link the mol­ecules. There is also a weak C—H(...)π inter­action.

Related literature

For related structures, see: Hudson et al. (1993 [triangle]); Tahir et al. (2007 [triangle]); Wroblewski et al. (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o481-scheme1.jpg

Experimental

Crystal data

  • C16H19O4P
  • M r = 306.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o481-efi1.jpg
  • a = 6.0671 (12) Å
  • b = 17.0962 (11) Å
  • c = 15.0502 (12) Å
  • β = 95.0021 (11)°
  • V = 1555.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.19 mm−1
  • T = 296 K
  • 0.28 × 0.12 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.968, T max = 0.982
  • 2800 measured reflections
  • 2794 independent reflections
  • 1655 reflections with I > 2σ(I)
  • R int = 0.059
  • 3 standard reflections frequency: 120 min intensity decay: −1.3%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.159
  • S = 1.01
  • 2794 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004036/hk2619sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004036/hk2619Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The crystal structure of (R)-dimethyl [(2-chlorophenyl)hydroxymethyl]- phosphonate (Tahir et al., 2007), which is a member of α-hydroxy phosphonates, has been reported, previously. In continuation to the study of such organic compounds, we report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of (I), (Fig. 1) the coordination around the P atom is a distorted tetrahedral. The crystal structure of dimethyl α-chloromethyl-α -hydroxybenzylphosphonate, (II) (Hudson et al., 1993) and C24H26NO4P, (III) (Wroblewski et al., 2000) have also been reported, in which both of them have similar coordinations around the C-atom having α-hydroxy group. In (I), the benzene rings A (C1-C6) and B (C9-C14) are oriented at a dihedral angle of 72.28 (11)°. The intramolecular C-H···O hydrogen bonds (Table 1) result in the formations of five- and six-membered rings C (O1/C1/C6/C7/H6) and D (P1/O4/C1/C2/C7/H2), respectively, having planar and boat conformations.

In the crystal structure, intermolecular O-H···O and C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. There is also a weak C—H···π interaction (Table 1).

Experimental

For the preparation of the title compound, 2-phenylacetophenone (1.96 g, 10 mmol) was disolved in dimethylphosphonate (1.10 g, 10 mmol) at room temperature. Then, KF (2.5 g) and ψ-Al2O3 (2.5 g) were added partwise and the mixture was kept at room temperature for 72 h. The product was extracted twice with 50 ml portions of a dichloromethane/methanol mixture (1:1). After the evaporation of the solvent on a rotary evaporator, the residue was crystallized from a mixture of diethyl ether/acetone (3:1) (m.p. 414 K).

Refinement

H atoms were positioned geometrically, with O-H = 0.82 Å (for OH), C-H = 0.93, 0.96 and 0.97 Å for aromatic, methyl and methylene H, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C16H19O4PF(000) = 648
Mr = 306.28Dx = 1.308 Mg m3
Monoclinic, P21/cMelting point = 83–86 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 6.0671 (12) ÅCell parameters from 15 reflections
b = 17.0962 (11) Åθ = 10.0–11.3°
c = 15.0502 (12) ŵ = 0.19 mm1
β = 95.0021 (11)°T = 296 K
V = 1555.1 (3) Å3Needle, colorless
Z = 40.28 × 0.12 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.059
ω/2θ scansθmax = 25.2°, θmin = 2.4°
Absorption correction: ψ scan (North et al., 1968)h = 0→7
Tmin = 0.968, Tmax = 0.982k = 0→20
2800 measured reflectionsl = −18→17
2794 independent reflections3 standard reflections every 120 min
1655 reflections with I > 2σ(I) intensity decay: −1.3%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.159w = 1/[σ2(Fo2) + (0.088P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2794 reflectionsΔρmax = 0.40 e Å3
191 parametersΔρmin = −0.35 e Å3
0 restraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
P10.79483 (14)0.12098 (5)−0.05193 (6)0.0416 (3)
O11.0479 (3)0.10996 (12)0.09544 (16)0.0460 (8)
O20.8463 (4)0.04357 (13)−0.08487 (15)0.0576 (9)
O30.9546 (5)0.18125 (15)−0.08944 (18)0.0659 (10)
O40.5517 (4)0.14911 (15)−0.07722 (15)0.0582 (9)
C10.7793 (5)0.21108 (17)0.1007 (2)0.0368 (10)
C20.5716 (5)0.24481 (19)0.0869 (2)0.0444 (11)
C30.5409 (6)0.3227 (2)0.1076 (2)0.0533 (12)
C40.7133 (7)0.3671 (2)0.1449 (3)0.0567 (14)
C50.9175 (7)0.3333 (2)0.1623 (3)0.0555 (14)
C60.9516 (6)0.25648 (18)0.1401 (2)0.0470 (11)
C70.8226 (5)0.12778 (17)0.0709 (2)0.0387 (10)
C80.6654 (5)0.06725 (18)0.1090 (2)0.0435 (11)
C90.6703 (6)0.06607 (17)0.2091 (2)0.0411 (10)
C100.8471 (6)0.03455 (19)0.2618 (2)0.0522 (12)
C110.8457 (7)0.0313 (2)0.3538 (2)0.0573 (14)
C120.6657 (8)0.0583 (2)0.3943 (3)0.0628 (14)
C130.4908 (8)0.0895 (2)0.3432 (3)0.0635 (16)
C140.4917 (6)0.0931 (2)0.2520 (3)0.0537 (12)
C150.9185 (9)0.2641 (2)−0.0979 (3)0.0863 (19)
C160.4445 (7)0.1432 (3)−0.1647 (3)0.0733 (16)
H11.067440.062720.090920.0552*
H20.452120.214950.063610.0534*
H30.401780.345180.096020.0636*
H40.691920.419530.158240.0679*
H51.033970.362540.189330.0666*
H61.091510.234580.151430.0565*
H8A0.515290.078190.084610.0520*
H8B0.704020.015570.088790.0520*
H100.968540.015290.235010.0623*
H110.966850.010830.388200.0688*
H120.663300.055200.455910.0750*
H130.369750.108600.370310.0764*
H140.370050.114010.218250.0644*
H15A1.042580.28789−0.122800.1294*
H15B0.902110.28613−0.040200.1294*
H15C0.786620.27362−0.136440.1294*
H16A0.296750.16336−0.165230.1095*
H16B0.438930.08928−0.182770.1095*
H16C0.525320.17277−0.205250.1095*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0398 (5)0.0398 (5)0.0458 (5)0.0101 (4)0.0066 (4)−0.0001 (4)
O10.0323 (13)0.0371 (12)0.0669 (15)0.0059 (10)−0.0053 (11)−0.0040 (11)
O20.0693 (17)0.0495 (15)0.0533 (14)0.0195 (13)0.0007 (12)−0.0048 (11)
O30.0681 (18)0.0571 (17)0.0766 (17)0.0082 (13)0.0295 (14)0.0097 (13)
O40.0503 (15)0.0781 (17)0.0450 (14)0.0233 (13)−0.0034 (11)−0.0082 (12)
C10.0363 (18)0.0357 (17)0.0389 (17)0.0016 (14)0.0064 (14)0.0009 (13)
C20.0339 (19)0.047 (2)0.053 (2)0.0006 (15)0.0075 (14)−0.0066 (15)
C30.051 (2)0.051 (2)0.060 (2)0.0171 (19)0.0163 (18)−0.0002 (17)
C40.071 (3)0.0351 (19)0.067 (2)0.0015 (19)0.024 (2)−0.0090 (17)
C50.057 (3)0.041 (2)0.069 (2)−0.0050 (18)0.0085 (19)−0.0118 (17)
C60.0391 (19)0.042 (2)0.059 (2)−0.0002 (15)0.0000 (16)0.0002 (16)
C70.0306 (18)0.0371 (17)0.0476 (18)0.0025 (14)−0.0013 (14)−0.0015 (14)
C80.0370 (19)0.0395 (18)0.053 (2)−0.0038 (14)−0.0009 (15)0.0002 (15)
C90.0426 (19)0.0294 (16)0.0501 (19)−0.0046 (14)−0.0022 (16)−0.0009 (14)
C100.054 (2)0.048 (2)0.054 (2)0.0105 (17)0.0010 (17)0.0012 (16)
C110.063 (3)0.053 (2)0.054 (2)0.0051 (19)−0.0051 (19)0.0080 (18)
C120.085 (3)0.059 (2)0.045 (2)−0.010 (2)0.009 (2)−0.0025 (18)
C130.062 (3)0.068 (2)0.063 (3)0.000 (2)0.019 (2)−0.004 (2)
C140.041 (2)0.055 (2)0.065 (2)−0.0028 (16)0.0034 (18)0.0010 (17)
C150.131 (4)0.050 (3)0.082 (3)−0.005 (3)0.032 (3)0.010 (2)
C160.061 (3)0.098 (3)0.059 (2)0.012 (2)−0.006 (2)−0.001 (2)

Geometric parameters (Å, °)

P1—O21.457 (2)C12—C131.364 (6)
P1—O31.554 (3)C13—C141.374 (6)
P1—O41.567 (3)C2—H20.9300
P1—C71.845 (3)C3—H30.9300
O1—C71.418 (4)C4—H40.9300
O3—C151.437 (4)C5—H50.9300
O4—C161.420 (5)C6—H60.9300
O1—H10.8200C8—H8A0.9700
C1—C61.392 (5)C8—H8B0.9700
C1—C71.523 (4)C10—H100.9300
C1—C21.385 (4)C11—H110.9300
C2—C31.384 (5)C12—H120.9300
C3—C41.372 (5)C13—H130.9300
C4—C51.371 (6)C14—H140.9300
C5—C61.375 (5)C15—H15A0.9600
C7—C81.551 (4)C15—H15B0.9600
C8—C91.504 (4)C15—H15C0.9600
C9—C141.388 (5)C16—H16A0.9600
C9—C101.386 (5)C16—H16B0.9600
C10—C111.387 (4)C16—H16C0.9600
C11—C121.376 (6)
O1···O23.094 (3)C9···H16Bvi2.7600
O1···O33.045 (4)C10···H16Bvi2.9200
O1···C103.154 (4)C10···H13.0400
O1···O2i2.710 (3)C11···H5vii3.0600
O2···O1i2.710 (3)C12···H15Ciii3.0100
O2···O13.094 (3)C13···H15Ciii2.9500
O3···C16ii3.336 (5)C16···H15C3.0500
O3···O13.045 (4)H1···O22.8800
O4···C22.956 (4)H1···C103.0400
O1···H14ii2.5700H1···H8B2.3500
O1···H62.3000H1···H102.4400
O1···H102.7300H1···O2i1.9000
O1···H8Aii2.9100H2···O42.5200
O2···H16B2.8700H2···C82.8900
O2···H8Bi2.9100H2···H8A2.3900
O2···H10i2.8000H5···C11viii3.0600
O2···H1i1.9000H6···O12.3000
O2···H8B2.8600H8A···O1v2.9100
O2···H12.8800H8A···O42.7500
O3···H16Aii2.4700H8A···C22.8700
O4···H22.5200H8A···H22.3900
O4···H8A2.7500H8A···H142.3500
O4···H15C2.7500H8B···O22.8600
C1···C153.303 (5)H8B···H12.3500
C2···O42.956 (4)H8B···O2i2.9100
C2···C93.590 (4)H8B···H16Bvi2.4900
C3···C16iii3.574 (5)H10···O12.7300
C4···C16iii3.423 (6)H10···H12.4400
C6···C153.572 (5)H10···O2i2.8000
C9···C23.590 (4)H14···O1v2.5700
C10···O13.154 (4)H14···H8A2.3500
C11···C15iii3.592 (5)H15B···C12.6400
C12···C15iii3.399 (5)H15B···C22.9700
C15···C13.303 (5)H15B···C62.7500
C15···C11iv3.592 (5)H15C···O42.7500
C15···C12iv3.399 (5)H15C···C163.0500
C15···C63.572 (5)H15C···H16C2.5000
C16···O3v3.336 (5)H15C···C12iv3.0100
C16···C3iv3.574 (5)H15C···C13iv2.9500
C16···C4iv3.423 (6)H16A···O3v2.4700
C1···H15B2.6400H16B···O22.8700
C2···H8A2.8700H16B···C8vi2.9900
C2···H15B2.9700H16B···C9vi2.7600
C3···H16Ciii2.8300H16B···C10vi2.9200
C4···H16Ciii2.7000H16B···H8Bvi2.4900
C6···H15B2.7500H16C···H15C2.5000
C8···H16Bvi2.9900H16C···C3iv2.8300
C8···H22.8900H16C···C4iv2.7000
O2—P1—O3108.65 (15)C4—C3—H3120.00
O2—P1—O4114.93 (14)C3—C4—H4120.00
O2—P1—C7113.24 (14)C5—C4—H4120.00
O3—P1—O4108.19 (15)C4—C5—H5120.00
O3—P1—C7108.47 (14)C6—C5—H5120.00
O4—P1—C7103.05 (13)C1—C6—H6120.00
P1—O3—C15126.2 (3)C5—C6—H6120.00
P1—O4—C16123.3 (2)C7—C8—H8A109.00
C7—O1—H1109.00C7—C8—H8B109.00
C2—C1—C6118.1 (3)C9—C8—H8A109.00
C6—C1—C7120.3 (3)C9—C8—H8B109.00
C2—C1—C7121.6 (3)H8A—C8—H8B108.00
C1—C2—C3120.4 (3)C9—C10—H10119.00
C2—C3—C4120.8 (3)C11—C10—H10120.00
C3—C4—C5119.3 (3)C10—C11—H11120.00
C4—C5—C6120.6 (4)C12—C11—H11120.00
C1—C6—C5120.8 (3)C11—C12—H12120.00
P1—C7—C1110.6 (2)C13—C12—H12120.00
P1—C7—C8108.9 (2)C12—C13—H13120.00
O1—C7—C1108.2 (2)C14—C13—H13120.00
O1—C7—C8111.7 (2)C9—C14—H14119.00
C1—C7—C8112.8 (2)C13—C14—H14119.00
P1—C7—O1104.4 (2)O3—C15—H15A109.00
C7—C8—C9114.9 (3)O3—C15—H15B109.00
C8—C9—C10121.7 (3)O3—C15—H15C109.00
C10—C9—C14117.4 (3)H15A—C15—H15B109.00
C8—C9—C14120.9 (3)H15A—C15—H15C109.00
C9—C10—C11121.0 (3)H15B—C15—H15C109.00
C10—C11—C12120.2 (4)O4—C16—H16A110.00
C11—C12—C13119.3 (4)O4—C16—H16B109.00
C12—C13—C14120.7 (4)O4—C16—H16C110.00
C9—C14—C13121.4 (4)H16A—C16—H16B109.00
C1—C2—H2120.00H16A—C16—H16C110.00
C3—C2—H2120.00H16B—C16—H16C109.00
C2—C3—H3120.00
O2—P1—O3—C15158.6 (3)C2—C1—C7—C8−55.0 (4)
O4—P1—O3—C1533.2 (3)C6—C1—C7—P1−110.6 (3)
C7—P1—O3—C15−77.9 (3)C6—C1—C7—O13.2 (4)
O2—P1—O4—C16−47.0 (3)C6—C1—C7—C8127.3 (3)
O3—P1—O4—C1674.6 (3)C1—C2—C3—C4−2.3 (5)
C7—P1—O4—C16−170.7 (3)C2—C3—C4—C5−0.5 (6)
O2—P1—C7—O160.7 (2)C3—C4—C5—C62.1 (6)
O2—P1—C7—C1176.8 (2)C4—C5—C6—C1−0.9 (6)
O2—P1—C7—C8−58.8 (2)P1—C7—C8—C9180.0 (2)
O3—P1—C7—O1−60.0 (2)O1—C7—C8—C965.2 (3)
O3—P1—C7—C156.1 (2)C1—C7—C8—C9−56.9 (3)
O3—P1—C7—C8−179.5 (2)C7—C8—C9—C10−73.5 (4)
O4—P1—C7—O1−174.51 (18)C7—C8—C9—C14109.9 (3)
O4—P1—C7—C1−58.4 (2)C8—C9—C10—C11−177.6 (3)
O4—P1—C7—C866.0 (2)C14—C9—C10—C11−0.8 (5)
C6—C1—C2—C33.4 (4)C8—C9—C14—C13177.4 (3)
C7—C1—C2—C3−174.4 (3)C10—C9—C14—C130.6 (5)
C2—C1—C6—C5−1.8 (5)C9—C10—C11—C121.1 (5)
C7—C1—C6—C5176.0 (3)C10—C11—C12—C13−1.2 (5)
C2—C1—C7—P167.1 (3)C11—C12—C13—C141.0 (6)
C2—C1—C7—O1−179.1 (3)C12—C13—C14—C9−0.7 (6)

Symmetry codes: (i) −x+2, −y, −z; (ii) x+1, y, z; (iii) x, −y+1/2, z+1/2; (iv) x, −y+1/2, z−1/2; (v) x−1, y, z; (vi) −x+1, −y, −z; (vii) −x+2, y−1/2, −z+1/2; (viii) −x+2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.82001.90002.710 (3)172.00
C2—H2···O40.93002.52002.956 (4)109.00
C6—H6···O10.93002.30002.671 (4)103.00
C14—H14···O1v0.93002.57003.432 (5)154.00
C16—H16A···O3v0.96002.47003.336 (5)149.00
C15—H15B···CgA0.96002.72003.608 (5)154.00

Symmetry codes: (i) −x+2, −y, −z; (v) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2619).

References

  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Hudson, H. R., McPartlin, M., Matthews, R. W., Powell, H. R., Yusuf, R. O., Jaszay, Z. M., Keglevich, G., Petnehazy, I. & Toke, L. (1993). Phosphorus Sulfur Silicon Relat. Elem 79, 239–243.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Tahir, M. N., Acar, N., Yilmaz, H., Danish, M. & Ülkü, D. (2007). Acta Cryst. E63, o3817–o3818.
  • Wroblewski, A. E., Maniukiewicz, W. & Karolczak, W. (2000). J. Chem. Soc. Perkin Trans. 1, pp. 1433–1435.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography