Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009227/qa0333sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009227/qa0333Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270100009227/qa0333Isup3.pdf |
CCDC reference: 150398
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.
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.
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.
C6H7O2P | Dx = 1.449 Mg m−3 |
Mr = 142.09 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 4387 reflections |
a = 7.6624 (6) Å | θ = 2.7–27.5° |
b = 5.5762 (4) Å | µ = 0.34 mm−1 |
c = 15.2489 (11) Å | T = 100 K |
V = 651.54 (8) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.30 × 0.26 mm |
F(000) = 296 |
Nonius KappaCCD diffractometer | 1364 independent reflections |
Radiation source: fine-focus sealed tube | 1162 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ψ and ω scans with κ offsets | θmax = 27.5°, θmin = 3.9° |
Absorption correction: multi-scan (otwinski & Minor, 1997) ? | h = −9→9 |
Tmin = 0.906, Tmax = 0.918 | k = −7→7 |
4387 measured reflections | l = −19→19 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.038 | Calculated w = 1/[σ2(Fo2) + (0.0474P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.089 | (Δ/σ)max = 0.006 |
S = 1.06 | Δρmax = 0.22 e Å−3 |
1364 reflections | Δρmin = −0.23 e Å−3 |
93 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.002 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 593 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.60 (14) |
C6H7O2P | V = 651.54 (8) Å3 |
Mr = 142.09 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 7.6624 (6) Å | µ = 0.34 mm−1 |
b = 5.5762 (4) Å | T = 100 K |
c = 15.2489 (11) Å | 0.30 × 0.30 × 0.26 mm |
Nonius KappaCCD diffractometer | 1364 independent reflections |
Absorption correction: multi-scan (otwinski & Minor, 1997) ? | 1162 reflections with I > 2σ(I) |
Tmin = 0.906, Tmax = 0.918 | Rint = 0.054 |
4387 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.089 | Δρmax = 0.22 e Å−3 |
S = 1.06 | Δρmin = −0.23 e Å−3 |
1364 reflections | Absolute structure: Flack (1983), 593 Friedel pairs |
93 parameters | Absolute structure parameter: 0.60 (14) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
P | 0.40757 (8) | 0.43127 (10) | 0.33664 (5) | 0.0289 (2) | |
H1 | 0.521 (4) | 0.619 (5) | 0.3566 (18) | 0.030 (7)* | |
H2 | 0.155 (5) | 0.443 (5) | 0.371 (2) | 0.042 (9)* | |
O1 | 0.4629 (3) | 0.1792 (3) | 0.35461 (12) | 0.0371 (5) | |
O2 | 0.2477 (3) | 0.5225 (3) | 0.38994 (12) | 0.0359 (5) | |
C11 | 0.3604 (3) | 0.4705 (4) | 0.22256 (17) | 0.0242 (5) | |
C12 | 0.2722 (4) | 0.6752 (5) | 0.19354 (16) | 0.0297 (6) | |
H12 | 0.2412 | 0.7978 | 0.2339 | 0.036* | |
C13 | 0.2302 (4) | 0.6980 (5) | 0.10532 (17) | 0.0311 (6) | |
H13 | 0.1700 | 0.8366 | 0.0855 | 0.037* | |
C14 | 0.2756 (3) | 0.5199 (4) | 0.04580 (17) | 0.0288 (6) | |
H14 | 0.2444 | 0.5350 | −0.0142 | 0.035* | |
C15 | 0.3674 (4) | 0.3184 (4) | 0.07481 (16) | 0.0271 (5) | |
H15 | 0.4003 | 0.1975 | 0.0342 | 0.033* | |
C16 | 0.4105 (3) | 0.2942 (4) | 0.16248 (16) | 0.0253 (5) | |
H16 | 0.4741 | 0.1579 | 0.1818 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P | 0.0306 (3) | 0.0366 (3) | 0.0195 (3) | −0.0083 (2) | 0.0000 (3) | −0.0005 (3) |
O1 | 0.0346 (10) | 0.0449 (10) | 0.0316 (12) | −0.0015 (8) | 0.0014 (8) | 0.0103 (8) |
O2 | 0.0404 (12) | 0.0431 (11) | 0.0243 (11) | −0.0074 (9) | 0.0034 (8) | −0.0084 (8) |
C11 | 0.0255 (13) | 0.0271 (11) | 0.0200 (10) | −0.0046 (9) | 0.0027 (10) | 0.0009 (10) |
C12 | 0.0324 (15) | 0.0278 (12) | 0.0290 (14) | −0.0016 (10) | 0.0064 (10) | −0.0038 (11) |
C13 | 0.0291 (15) | 0.0293 (13) | 0.0348 (15) | 0.0040 (11) | −0.0004 (11) | 0.0071 (11) |
C14 | 0.0275 (14) | 0.0362 (14) | 0.0226 (13) | −0.0031 (11) | −0.0015 (10) | 0.0050 (10) |
C15 | 0.0296 (14) | 0.0282 (12) | 0.0237 (12) | −0.0009 (11) | 0.0011 (10) | −0.0045 (10) |
C16 | 0.0255 (13) | 0.0223 (11) | 0.0281 (13) | −0.0011 (9) | −0.0011 (10) | 0.0003 (10) |
P—O1 | 1.4933 (19) | C12—H12 | 0.9500 |
P—O2 | 1.556 (2) | C13—C14 | 1.390 (4) |
P—C11 | 1.790 (3) | C13—H13 | 0.9500 |
P—H1 | 1.40 (3) | C14—C15 | 1.397 (4) |
O2—H2 | 0.88 (4) | C14—H14 | 0.9500 |
C11—C16 | 1.398 (4) | C15—C16 | 1.384 (4) |
C11—C12 | 1.398 (4) | C15—H15 | 0.9500 |
C12—C13 | 1.389 (4) | C16—H16 | 0.9500 |
O1—P—O2 | 115.82 (11) | C12—C13—C14 | 120.6 (2) |
O1—P—C11 | 110.53 (11) | C12—C13—H13 | 119.7 |
O2—P—C11 | 107.98 (12) | C14—C13—H13 | 119.7 |
O1—P—H1 | 119.3 (11) | C13—C14—C15 | 119.6 (2) |
O2—P—H1 | 97.5 (11) | C13—C14—H14 | 120.2 |
C11—P—H1 | 104.2 (11) | C15—C14—H14 | 120.2 |
P—O2—H2 | 107 (2) | C16—C15—C14 | 120.3 (2) |
C16—C11—C12 | 120.0 (2) | C16—C15—H15 | 119.9 |
C16—C11—P | 119.71 (18) | C14—C15—H15 | 119.9 |
C12—C11—P | 120.3 (2) | C15—C16—C11 | 120.0 (2) |
C13—C12—C11 | 119.6 (2) | C15—C16—H16 | 120.0 |
C13—C12—H12 | 120.2 | C11—C16—H16 | 120.0 |
C11—C12—H12 | 120.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.88 (4) | 1.64 (4) | 2.513 (3) | 168 (3) |
C15—H15···O2ii | 0.95 | 2.66 | 3.383 (3) | 133 |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) −x+1/2, y−1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H7O2P |
Mr | 142.09 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 100 |
a, b, c (Å) | 7.6624 (6), 5.5762 (4), 15.2489 (11) |
V (Å3) | 651.54 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.30 × 0.30 × 0.26 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Otwinski & Minor, 1997) |
Tmin, Tmax | 0.906, 0.918 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4387, 1364, 1162 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.089, 1.06 |
No. of reflections | 1364 |
No. of parameters | 93 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.23 |
Absolute structure | Flack (1983), 593 Friedel pairs |
Absolute structure parameter | 0.60 (14) |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.
P—O1 | 1.4933 (19) | P—H1 | 1.40 (3) |
P—O2 | 1.556 (2) | O2—H2 | 0.88 (4) |
O1—P—O2 | 115.82 (11) | O2—P—H1 | 97.5 (11) |
O1—P—H1 | 119.3 (11) | P—O2—H2 | 107 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.88 (4) | 1.64 (4) | 2.513 (3) | 168 (3) |
C15—H15···O2ii | 0.95 | 2.66 | 3.383 (3) | 133.4 |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) −x+1/2, y−1/2, z−1/2. |
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···O═P—OH···O═P. The very short P—O···O═P 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 P═O 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.