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The crystal structure of the title compound, C6H7O2P, shows continuous hydrogen-bonding chains in the x direction, with a P-O...O=P distance of 2.513 (3) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009227/qa0333sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009227/qa0333Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270100009227/qa0333Isup3.pdf
Supplementary material

CCDC reference: 150398

Comment top

Phosphinic acids possess the ability to form strong hydrogen bonds in the solid state by virtue of the very electronegative O atoms bound to an electropositive P atom. Simple phosphinic acids in the gas phase show almost twice the dimerization enthalpy as the analogous carboxylic acids (Denisov & Tokhadze, 1994; González et al., 1998; Colominas et al., 1998). The title compound, (I), was investigated as part of our research into the effects of stong hydrogen bonding in phosphinic acid derivatives.

The title compound crystallizes in the non-centrosymmetric space group Pna21, but shows racemic twinning; the Flack x parameter refined to 0.60 (14). Selected bond lengths and angles are given in Table 1. Molecules of phenylphosphinic acid related by the a glide plane perpendicular to the c axis form infinite hydrogen-bonded chains of the type OH···OP—OH···OP. The very short P—O···OP distance of 2.513 (3) Å indicates a strong hydrogen bond. This arrangement is the more commonly found in the crystalline state for phosphinic or phosphonic acids; a dimeric form, forming an eight-membered ring, is also seen (Druyan et al., 1976; Reis et al., 1976). The PO and P—O distances are normal compared with averages found for related compounds, i.e. 1.489 and 1.560 Å respectively (Allen et al., 1987). The phenyl groups pack in a herring-bone-type arrangement along ab planes with the planes of the phenyl groups tilted 59.44 (6)° with respect to each other. A weak interaction is noted between atoms H15 and O2. Table 2 lists the hydrogen-bonding interactions.

Experimental top

Phenylphosphinic acid was prepared according to the procedure of Voight & Gallais (1953), using P(C6H5)Cl2 and CHCl3 in place of PCl3 and CCl4. The yield was quantitative, giving pure product as checked with 1H and 31P NMR spectroscopy. Crystals suitable for X-ray diffraction were grown by slow evaporation of a solution of the acid in acetone in a desiccator containing silica desiccant.

Refinement top

The H atom bound to the P atom and the H atom of the hydroxyl group were found in the difference Fourier map and allowed to refine with isotropic displacement parameters. The H atoms on the phenyl ring were constrained to positions bisecting the C—C—C angles and the C—H distance fixed to the default value for the program, 0.95 Å. The isotropic displacement parameters were set to be 20% larger than the those of the atoms to which the H atoms were bonded.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

phenylphosphinic acid top
Crystal data top
C6H7O2PDx = 1.449 Mg m3
Mr = 142.09Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 4387 reflections
a = 7.6624 (6) Åθ = 2.7–27.5°
b = 5.5762 (4) ŵ = 0.34 mm1
c = 15.2489 (11) ÅT = 100 K
V = 651.54 (8) Å3Block, colourless
Z = 40.30 × 0.30 × 0.26 mm
F(000) = 296
Data collection top
Nonius KappaCCD
diffractometer
1364 independent reflections
Radiation source: fine-focus sealed tube1162 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
ψ and ω scans with κ offsetsθmax = 27.5°, θmin = 3.9°
Absorption correction: multi-scan (otwinski & Minor, 1997)
?
h = 99
Tmin = 0.906, Tmax = 0.918k = 77
4387 measured reflectionsl = 1919
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.038Calculated w = 1/[σ2(Fo2) + (0.0474P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.089(Δ/σ)max = 0.006
S = 1.06Δρmax = 0.22 e Å3
1364 reflectionsΔρmin = 0.23 e Å3
93 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.002 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 593 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.60 (14)
Crystal data top
C6H7O2PV = 651.54 (8) Å3
Mr = 142.09Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 7.6624 (6) ŵ = 0.34 mm1
b = 5.5762 (4) ÅT = 100 K
c = 15.2489 (11) Å0.30 × 0.30 × 0.26 mm
Data collection top
Nonius KappaCCD
diffractometer
1364 independent reflections
Absorption correction: multi-scan (otwinski & Minor, 1997)
?
1162 reflections with I > 2σ(I)
Tmin = 0.906, Tmax = 0.918Rint = 0.054
4387 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089Δρmax = 0.22 e Å3
S = 1.06Δρmin = 0.23 e Å3
1364 reflectionsAbsolute structure: Flack (1983), 593 Friedel pairs
93 parametersAbsolute structure parameter: 0.60 (14)
1 restraint
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
xyzUiso*/Ueq
P0.40757 (8)0.43127 (10)0.33664 (5)0.0289 (2)
H10.521 (4)0.619 (5)0.3566 (18)0.030 (7)*
H20.155 (5)0.443 (5)0.371 (2)0.042 (9)*
O10.4629 (3)0.1792 (3)0.35461 (12)0.0371 (5)
O20.2477 (3)0.5225 (3)0.38994 (12)0.0359 (5)
C110.3604 (3)0.4705 (4)0.22256 (17)0.0242 (5)
C120.2722 (4)0.6752 (5)0.19354 (16)0.0297 (6)
H120.24120.79780.23390.036*
C130.2302 (4)0.6980 (5)0.10532 (17)0.0311 (6)
H130.17000.83660.08550.037*
C140.2756 (3)0.5199 (4)0.04580 (17)0.0288 (6)
H140.24440.53500.01420.035*
C150.3674 (4)0.3184 (4)0.07481 (16)0.0271 (5)
H150.40030.19750.03420.033*
C160.4105 (3)0.2942 (4)0.16248 (16)0.0253 (5)
H160.47410.15790.18180.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P0.0306 (3)0.0366 (3)0.0195 (3)0.0083 (2)0.0000 (3)0.0005 (3)
O10.0346 (10)0.0449 (10)0.0316 (12)0.0015 (8)0.0014 (8)0.0103 (8)
O20.0404 (12)0.0431 (11)0.0243 (11)0.0074 (9)0.0034 (8)0.0084 (8)
C110.0255 (13)0.0271 (11)0.0200 (10)0.0046 (9)0.0027 (10)0.0009 (10)
C120.0324 (15)0.0278 (12)0.0290 (14)0.0016 (10)0.0064 (10)0.0038 (11)
C130.0291 (15)0.0293 (13)0.0348 (15)0.0040 (11)0.0004 (11)0.0071 (11)
C140.0275 (14)0.0362 (14)0.0226 (13)0.0031 (11)0.0015 (10)0.0050 (10)
C150.0296 (14)0.0282 (12)0.0237 (12)0.0009 (11)0.0011 (10)0.0045 (10)
C160.0255 (13)0.0223 (11)0.0281 (13)0.0011 (9)0.0011 (10)0.0003 (10)
Geometric parameters (Å, º) top
P—O11.4933 (19)C12—H120.9500
P—O21.556 (2)C13—C141.390 (4)
P—C111.790 (3)C13—H130.9500
P—H11.40 (3)C14—C151.397 (4)
O2—H20.88 (4)C14—H140.9500
C11—C161.398 (4)C15—C161.384 (4)
C11—C121.398 (4)C15—H150.9500
C12—C131.389 (4)C16—H160.9500
O1—P—O2115.82 (11)C12—C13—C14120.6 (2)
O1—P—C11110.53 (11)C12—C13—H13119.7
O2—P—C11107.98 (12)C14—C13—H13119.7
O1—P—H1119.3 (11)C13—C14—C15119.6 (2)
O2—P—H197.5 (11)C13—C14—H14120.2
C11—P—H1104.2 (11)C15—C14—H14120.2
P—O2—H2107 (2)C16—C15—C14120.3 (2)
C16—C11—C12120.0 (2)C16—C15—H15119.9
C16—C11—P119.71 (18)C14—C15—H15119.9
C12—C11—P120.3 (2)C15—C16—C11120.0 (2)
C13—C12—C11119.6 (2)C15—C16—H16120.0
C13—C12—H12120.2C11—C16—H16120.0
C11—C12—H12120.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.88 (4)1.64 (4)2.513 (3)168 (3)
C15—H15···O2ii0.952.663.383 (3)133
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x+1/2, y1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC6H7O2P
Mr142.09
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)100
a, b, c (Å)7.6624 (6), 5.5762 (4), 15.2489 (11)
V3)651.54 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.34
Crystal size (mm)0.30 × 0.30 × 0.26
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan (Otwinski & Minor, 1997)
Tmin, Tmax0.906, 0.918
No. of measured, independent and
observed [I > 2σ(I)] reflections
4387, 1364, 1162
Rint0.054
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.089, 1.06
No. of reflections1364
No. of parameters93
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.22, 0.23
Absolute structureFlack (1983), 593 Friedel pairs
Absolute structure parameter0.60 (14)

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
P—O11.4933 (19)P—H11.40 (3)
P—O21.556 (2)O2—H20.88 (4)
O1—P—O2115.82 (11)O2—P—H197.5 (11)
O1—P—H1119.3 (11)P—O2—H2107 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.88 (4)1.64 (4)2.513 (3)168 (3)
C15—H15···O2ii0.952.663.383 (3)133.4
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x+1/2, y1/2, z1/2.
 

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