PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o233.
Published online 2007 December 12. doi:  10.1107/S1600536807057674
PMCID: PMC2915293

(2-Chloro­phen­yl)(diphenyl­phosphor­yl)methanol

Abstract

The title compound, C19H16ClO2P, was obtained by the reaction of diphenyl­phosphine oxide with 2-chloro­benzaldehyde. The mol­ecule has a tetra­hedral structure at the P atom. The dihedral angle between the phenyl rings attached to the P atom is 80.4 (1)°. The mol­ecules are linked together by inter­molecular O—H(...)O and C—H(...)O hydrogen-bonding inter­actrions. The crystal studied was an inversion twin.

Related literature

For general background, see: Clark et al. (2002 [triangle]). For related structures, see: Dankowski et al. (1979 [triangle]); Liu et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o233-scheme1.jpg

Experimental

Crystal data

  • C19H16ClO2P
  • M r = 342.74
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o233-efi1.jpg
  • a = 9.0943 (4) Å
  • b = 10.9172 (6) Å
  • c = 18.0657 (12) Å
  • V = 1793.64 (17) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.31 mm−1
  • T = 293 (2) K
  • 0.57 × 0.20 × 0.10 mm

Data collection

  • Bruker APEX area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; (Bruker, 2001 [triangle]) T min = 0.844, T max = 0.970
  • 8361 measured reflections
  • 3466 independent reflections
  • 2494 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.084
  • S = 0.91
  • 3466 reflections
  • 208 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.26 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1437 Friedel pairs
  • Flack parameter: 0.55 (8)

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807057674/xu2343sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807057674/xu2343Isup2.hkl

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

Acknowledgments

The authors thank the Technical Project of the Department of Education of Jiangxi Province, China, and the Key Technical Project of Yichun Municipality, China, for supporting this work.

supplementary crystallographic information

Comment

The title compound is an analog of (diphenylphosphinoyl)phenylmethanol, which was employed as a ligand in the rhodiumcatalyzed hydroformylation of alkenes, with good conversions and regioselectivities (Clark et al., 2002).

The molecular structure is shown in Fig. 1. Bond lengths and angles are in agreement with those reported for similar compounds (Dankowski et al., 1979; Liu et al., 2007). The dihedral angle between the C8-phenyl and C14-phenyl planes is 80.4 (1)°. The O—H···O and C—H···O hydrogen bonds (Table 1) involving the hydroxyl group link the molecules into a supra-molecular structure.

Experimental

To a solution of 2-chlorobenzaldehyde (0.28 g, 2.0 mmol) and diphenylphosphine oxide (0.41 g, 2.0 mmol) in tetrahydrofuran (10 ml) at 273 K was added dropwise triethylamine (0.30 ml, 2.0 mmol). The cooling bath was removed and the mixture warmed to ambient temperature for 2 h. The solvent was concentrated under vacuum and the crude product was purified by column chromatography (petroleum ether-ethyl acetate, 1:1) to give the title compound as a white solid in 85% yield. Single crystals were obtained by slow evaporation of a methanol solution.

Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å (aromatic), 0.98 Å (methine), O—H = 0.82 Å, and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O). The absolute structure was not determined.

Figures

Fig. 1.
The molecular structure of (I), showing 50% probability displacement ellipsoids (arbitrary spheres for H atoms).

Crystal data

C19H16ClO2PF000 = 712
Mr = 342.74Dx = 1.269 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3220 reflections
a = 9.0943 (4) Åθ = 2.5–32.6º
b = 10.9172 (6) ŵ = 0.31 mm1
c = 18.0657 (12) ÅT = 293 (2) K
V = 1793.64 (17) Å3Plate, colorless
Z = 40.57 × 0.20 × 0.10 mm

Data collection

Bruker APEX area-detector diffractometer3466 independent reflections
Radiation source: fine-focus sealed tube2494 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 293(2) Kθmax = 26.0º
[var phi] and ω scansθmin = 2.5º
Absorption correction: multi-scan(SADABS; (Bruker, 2001)h = −11→10
Tmin = 0.844, Tmax = 0.970k = −13→13
8361 measured reflectionsl = −22→19

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035  w = 1/[σ2(Fo2) + (0.0482P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.084(Δ/σ)max < 0.001
S = 0.91Δρmax = 0.20 e Å3
3466 reflectionsΔρmin = −0.26 e Å3
208 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1437 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.55 (8)

Special details

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)

xyzUiso*/Ueq
P10.39075 (6)0.07346 (5)0.22300 (3)0.03563 (15)
Cl10.68961 (8)0.08726 (10)0.36635 (5)0.0874 (3)
C10.4310 (2)0.20391 (18)0.28358 (14)0.0371 (5)
H3A0.53400.22760.27640.045*
C20.4092 (3)0.1697 (2)0.36374 (14)0.0425 (6)
C30.5177 (3)0.1153 (3)0.40525 (16)0.0574 (7)
C40.4977 (4)0.0838 (3)0.47859 (18)0.0795 (9)
H26A0.57290.04680.50540.095*
C50.3652 (5)0.1080 (3)0.5109 (2)0.0929 (12)
H12A0.35010.08760.56030.112*
C60.2538 (4)0.1621 (3)0.4712 (2)0.0850 (11)
H27A0.16370.17750.49370.102*
C70.2752 (3)0.1935 (2)0.39825 (17)0.0616 (8)
H10A0.19980.23080.37180.074*
C80.4778 (2)0.1058 (2)0.13569 (14)0.0405 (6)
C90.5076 (3)0.0066 (3)0.09105 (16)0.0575 (7)
H8A0.4765−0.07110.10530.069*
C100.5824 (4)0.0211 (3)0.02620 (17)0.0771 (10)
H19A0.6024−0.0467−0.00330.093*
C110.6281 (4)0.1348 (3)0.00437 (18)0.0807 (10)
H21A0.67810.1442−0.04020.097*
C120.6006 (4)0.2345 (3)0.04770 (18)0.0818 (10)
H20A0.63250.31170.03310.098*
C130.5251 (3)0.2202 (3)0.11336 (17)0.0641 (8)
H11A0.50580.28810.14280.077*
C140.1961 (2)0.0688 (2)0.20812 (13)0.0421 (5)
C150.1179 (3)−0.0269 (3)0.23868 (18)0.0702 (8)
H13A0.1659−0.08520.26740.084*
C16−0.0321 (4)−0.0361 (4)0.2266 (3)0.0999 (12)
H33A−0.0845−0.10090.24710.120*
C17−0.1028 (4)0.0485 (4)0.1851 (2)0.0939 (11)
H22A−0.20380.04210.17800.113*
C18−0.0284 (3)0.1419 (3)0.1541 (2)0.0795 (10)
H17A−0.07800.19920.12530.095*
C190.1227 (3)0.1530 (2)0.16514 (16)0.0590 (7)
H14A0.17400.21730.14340.071*
O10.44309 (17)−0.04402 (12)0.25449 (9)0.0471 (4)
O20.34008 (16)0.30243 (12)0.26047 (10)0.0491 (5)
H2A0.39100.36300.25250.074*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0332 (3)0.0318 (3)0.0419 (3)0.0014 (3)0.0010 (3)0.0005 (3)
Cl10.0540 (4)0.1355 (7)0.0726 (5)0.0196 (5)−0.0150 (4)0.0185 (6)
C10.0298 (11)0.0323 (11)0.0493 (14)0.0003 (9)0.0007 (11)−0.0017 (11)
C20.0517 (14)0.0346 (12)0.0413 (14)−0.0059 (11)0.0048 (14)−0.0053 (11)
C30.0652 (17)0.0603 (18)0.0467 (16)−0.0005 (14)−0.0054 (15)−0.0049 (14)
C40.099 (2)0.089 (2)0.0506 (19)−0.005 (2)−0.0087 (18)0.0145 (18)
C50.140 (4)0.091 (3)0.0477 (18)−0.015 (3)0.024 (2)0.0091 (18)
C60.103 (3)0.078 (2)0.074 (2)0.005 (2)0.041 (2)0.0077 (19)
C70.0624 (17)0.0542 (16)0.068 (2)0.0005 (14)0.0213 (16)0.0022 (15)
C80.0352 (11)0.0436 (14)0.0427 (14)0.0033 (10)0.0008 (11)−0.0010 (12)
C90.0623 (18)0.0587 (17)0.0515 (17)0.0010 (14)0.0121 (15)−0.0047 (14)
C100.092 (3)0.081 (2)0.059 (2)0.0148 (19)0.0227 (19)−0.0111 (17)
C110.095 (2)0.091 (3)0.056 (2)0.014 (2)0.032 (2)0.0139 (18)
C120.106 (3)0.0631 (19)0.076 (2)−0.003 (2)0.032 (2)0.0198 (17)
C130.080 (2)0.0497 (17)0.062 (2)0.0061 (15)0.0202 (17)0.0086 (14)
C140.0349 (11)0.0469 (12)0.0446 (14)−0.0067 (12)0.0003 (10)−0.0040 (13)
C150.0531 (16)0.0746 (17)0.083 (2)−0.0208 (15)−0.0027 (17)0.0197 (16)
C160.060 (2)0.122 (3)0.117 (3)−0.044 (2)−0.001 (2)0.021 (3)
C170.0360 (14)0.143 (3)0.103 (3)−0.021 (2)−0.0043 (19)−0.006 (3)
C180.0530 (18)0.099 (2)0.086 (3)0.0122 (18)−0.0214 (18)0.001 (2)
C190.0388 (14)0.0696 (17)0.069 (2)−0.0036 (14)−0.0068 (14)0.0108 (14)
O10.0562 (10)0.0317 (8)0.0535 (10)0.0105 (7)0.0034 (9)0.0033 (7)
O20.0413 (8)0.0317 (8)0.0743 (13)0.0030 (6)−0.0005 (9)0.0047 (8)

Geometric parameters (Å, °)

P1—O11.4816 (15)C9—H8A0.9300
P1—C141.792 (2)C10—C111.367 (4)
P1—C81.800 (3)C10—H19A0.9300
P1—C11.833 (2)C11—C121.364 (4)
Cl1—C31.741 (3)C11—H21A0.9300
C1—O21.420 (2)C12—C131.380 (4)
C1—C21.509 (3)C12—H20A0.9300
C1—H3A0.9800C13—H11A0.9300
C2—C31.374 (4)C14—C191.375 (3)
C2—C71.393 (3)C14—C151.379 (3)
C3—C41.381 (4)C15—C161.385 (4)
C4—C51.364 (5)C15—H13A0.9300
C4—H26A0.9300C16—C171.351 (5)
C5—C61.374 (5)C16—H33A0.9300
C5—H12A0.9300C17—C181.346 (5)
C6—C71.375 (4)C17—H22A0.9300
C6—H27A0.9300C18—C191.394 (4)
C7—H10A0.9300C18—H17A0.9300
C8—C91.378 (3)C19—H14A0.9300
C8—C131.380 (3)O2—H2A0.8200
C9—C101.364 (4)
O1—P1—C14110.54 (11)C10—C9—H8A119.7
O1—P1—C8111.42 (10)C8—C9—H8A119.7
C14—P1—C8107.99 (11)C9—C10—C11120.3 (3)
O1—P1—C1112.28 (10)C9—C10—H19A119.8
C14—P1—C1107.99 (10)C11—C10—H19A119.8
C8—P1—C1106.42 (11)C12—C11—C10120.2 (3)
O2—C1—C2113.15 (18)C12—C11—H21A119.9
O2—C1—P1107.26 (15)C10—C11—H21A119.9
C2—C1—P1110.76 (15)C11—C12—C13119.6 (3)
O2—C1—H3A108.5C11—C12—H20A120.2
C2—C1—H3A108.5C13—C12—H20A120.2
P1—C1—H3A108.5C12—C13—C8120.6 (3)
C3—C2—C7117.7 (2)C12—C13—H11A119.7
C3—C2—C1122.4 (2)C8—C13—H11A119.7
C7—C2—C1119.9 (2)C19—C14—C15118.8 (2)
C2—C3—C4122.4 (3)C19—C14—P1123.04 (18)
C2—C3—Cl1120.0 (2)C15—C14—P1118.1 (2)
C4—C3—Cl1117.5 (3)C14—C15—C16120.0 (3)
C5—C4—C3118.6 (3)C14—C15—H13A120.0
C5—C4—H26A120.7C16—C15—H13A120.0
C3—C4—H26A120.7C17—C16—C15120.4 (3)
C4—C5—C6120.7 (3)C17—C16—H33A119.8
C4—C5—H12A119.6C15—C16—H33A119.8
C6—C5—H12A119.6C18—C17—C16120.6 (3)
C5—C6—C7120.2 (3)C18—C17—H22A119.7
C5—C6—H27A119.9C16—C17—H22A119.7
C7—C6—H27A119.9C17—C18—C19120.1 (3)
C6—C7—C2120.4 (3)C17—C18—H17A120.0
C6—C7—H10A119.8C19—C18—H17A120.0
C2—C7—H10A119.8C14—C19—C18120.1 (3)
C9—C8—C13118.6 (3)C14—C19—H14A120.0
C9—C8—P1116.43 (19)C18—C19—H14A120.0
C13—C8—P1124.8 (2)C1—O2—H2A109.5
C10—C9—C8120.6 (3)
O1—P1—C1—O2−162.66 (13)C14—P1—C8—C1398.3 (2)
C14—P1—C1—O2−40.54 (17)C1—P1—C8—C13−17.4 (3)
C8—P1—C1—O275.19 (16)C13—C8—C9—C100.1 (4)
O1—P1—C1—C2−38.74 (18)P1—C8—C9—C10−175.5 (3)
C14—P1—C1—C283.38 (18)C8—C9—C10—C11−0.4 (5)
C8—P1—C1—C2−160.89 (15)C9—C10—C11—C120.7 (6)
O2—C1—C2—C3−153.6 (2)C10—C11—C12—C13−0.6 (6)
P1—C1—C2—C385.9 (2)C11—C12—C13—C80.3 (5)
O2—C1—C2—C726.2 (3)C9—C8—C13—C120.0 (4)
P1—C1—C2—C7−94.3 (2)P1—C8—C13—C12175.1 (3)
C7—C2—C3—C40.3 (4)O1—P1—C14—C19−165.4 (2)
C1—C2—C3—C4−179.9 (3)C8—P1—C14—C19−43.2 (2)
C7—C2—C3—Cl1−178.04 (19)C1—P1—C14—C1971.5 (2)
C1—C2—C3—Cl11.8 (3)O1—P1—C14—C1511.7 (2)
C2—C3—C4—C5−0.2 (5)C8—P1—C14—C15133.8 (2)
Cl1—C3—C4—C5178.2 (3)C1—P1—C14—C15−111.5 (2)
C3—C4—C5—C60.3 (5)C19—C14—C15—C16−0.8 (5)
C4—C5—C6—C7−0.5 (5)P1—C14—C15—C16−178.0 (3)
C5—C6—C7—C20.7 (5)C14—C15—C16—C17−0.2 (6)
C3—C2—C7—C6−0.6 (4)C15—C16—C17—C181.0 (6)
C1—C2—C7—C6179.6 (3)C16—C17—C18—C19−0.7 (6)
O1—P1—C8—C935.1 (2)C15—C14—C19—C181.1 (4)
C14—P1—C8—C9−86.4 (2)P1—C14—C19—C18178.1 (2)
C1—P1—C8—C9157.82 (19)C17—C18—C19—C14−0.4 (5)
O1—P1—C8—C13−140.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.821.822.602 (2)158
C1—H3A···O1i0.982.563.059 (2)111
C16—H33A···O2ii0.932.563.318 (3)139

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2343).

References

  • Bruker (2001). SAINT (Version 6.22), SMART (Version 5.625) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Clark, H. J., Wang, R. & Alper, H. (2002). J. Org. Chem.67, 6224–6225. [PubMed]
  • Dankowski, M., Praefske, K., Nyburg, S. C. & Wong-ng, W. (1979). Phosphorus Sulfur, 7, 275–279.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Liu, W.-Y., Huo, P., Gao, Y.-X., Liu, P. & Zhao, Y.-F. (2007). Acta Cryst. E63, o1008–o1009.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.

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