Two polymorphs of (2-carboxyethyl)(phenyl)phosphinic acid, C9H11O4P, crystallize in the chiral P212121 space group with similar unit-cell parameters. They feature an essentially similar hydrogen-bonding motif but differ slightly in their detailed geometric parameters. For both polymorphs, the unequivocal location of the hydroxy H atoms together with the expected differences in the P-O bond lengths establish unequivocally that both forms contain the S isomer; the protonated phosphinic acid and carboxy O atoms serve as hydrogen-bond donors, while the second phosphinic acid O atom acts as a double hydrogen-bond acceptor and the remaining carboxy O atom is not involved in hydrogen bonding. Thus, an undulating two-dimensional supramolecular layer aggregate is formed based on an R43(20) ring unit. Such polymorphism derives from the rotation of the C-C single bonds between the two hydrogen-bond-involved carboxy and phosphinic acid moieties.
Supporting information
CCDC references: 833413; 833414
For both compounds, data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Bruker, 2008).
Crystal data top
C9H11O4P | F(000) = 448 |
Mr = 214.15 | Dx = 1.395 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1796 reflections |
a = 5.4948 (1) Å | θ = 3.8–25.9° |
b = 8.6830 (1) Å | µ = 0.26 mm−1 |
c = 21.3724 (4) Å | T = 296 K |
V = 1019.71 (3) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.20 × 0.10 mm |
Data collection top
CCD area detector diffractometer | 2326 independent reflections |
Radiation source: fine-focus sealed tube | 2089 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
φ and ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −5→7 |
Tmin = 0.673, Tmax = 0.746 | k = −11→11 |
5497 measured reflections | l = −27→27 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0436P)2 + 0.0664P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2326 reflections | Δρmax = 0.24 e Å−3 |
133 parameters | Δρmin = −0.24 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 893 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.09 (10) |
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 | x | y | z | Uiso*/Ueq | |
P1 | 0.32891 (10) | 0.68214 (5) | 0.41950 (2) | 0.02644 (14) | |
C1 | 0.2968 (4) | 0.6999 (2) | 0.33649 (9) | 0.0316 (5) | |
C2 | 0.4618 (5) | 0.6304 (3) | 0.29583 (9) | 0.0429 (6) | |
H2A | 0.5972 | 0.5793 | 0.3117 | 0.051* | |
C3 | 0.4240 (6) | 0.6374 (3) | 0.23175 (11) | 0.0586 (8) | |
H3A | 0.5309 | 0.5884 | 0.2045 | 0.070* | |
C4 | 0.2270 (6) | 0.7173 (4) | 0.20876 (12) | 0.0694 (10) | |
H4A | 0.2027 | 0.7227 | 0.1657 | 0.083* | |
C5 | 0.0661 (6) | 0.7893 (4) | 0.24807 (12) | 0.0717 (9) | |
H5A | −0.0642 | 0.8447 | 0.2318 | 0.086* | |
C6 | 0.0988 (5) | 0.7790 (3) | 0.31248 (11) | 0.0507 (7) | |
H6A | −0.0123 | 0.8252 | 0.3394 | 0.061* | |
C7 | 0.2012 (4) | 0.5020 (2) | 0.44335 (10) | 0.0330 (5) | |
H7A | 0.2125 | 0.4936 | 0.4885 | 0.040* | |
H7B | 0.0301 | 0.5002 | 0.4322 | 0.040* | |
C8 | 0.3268 (5) | 0.3637 (2) | 0.41376 (10) | 0.0361 (5) | |
H8A | 0.3263 | 0.3759 | 0.3686 | 0.043* | |
H8B | 0.4951 | 0.3611 | 0.4274 | 0.043* | |
C9 | 0.2073 (5) | 0.2134 (2) | 0.43020 (9) | 0.0342 (5) | |
O1 | 0.6099 (3) | 0.67442 (18) | 0.42966 (6) | 0.0382 (4) | |
H1A | 0.644 (5) | 0.679 (3) | 0.4666 (5) | 0.046* | |
O2 | 0.2054 (3) | 0.81281 (14) | 0.45275 (6) | 0.0345 (4) | |
O3 | 0.0050 (3) | 0.20158 (19) | 0.45074 (8) | 0.0536 (5) | |
O4 | 0.3510 (4) | 0.09573 (15) | 0.41730 (8) | 0.0520 (5) | |
H4B | 0.285 (5) | 0.020 (2) | 0.4328 (12) | 0.062* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0347 (3) | 0.0224 (2) | 0.0222 (2) | 0.0002 (2) | 0.0013 (2) | −0.00030 (19) |
C1 | 0.0395 (13) | 0.0297 (9) | 0.0257 (9) | −0.0067 (10) | 0.0002 (9) | 0.0024 (8) |
C2 | 0.0515 (16) | 0.0456 (12) | 0.0314 (11) | −0.0014 (12) | 0.0055 (11) | 0.0012 (9) |
C3 | 0.071 (2) | 0.0767 (18) | 0.0277 (11) | −0.0137 (16) | 0.0124 (13) | −0.0038 (12) |
C4 | 0.074 (2) | 0.106 (2) | 0.0278 (12) | −0.031 (2) | −0.0075 (14) | 0.0136 (14) |
C5 | 0.0596 (19) | 0.111 (3) | 0.0448 (15) | −0.005 (2) | −0.0156 (15) | 0.0257 (17) |
C6 | 0.0435 (15) | 0.0698 (17) | 0.0388 (13) | 0.0056 (14) | −0.0030 (11) | 0.0086 (12) |
C7 | 0.0428 (14) | 0.0245 (8) | 0.0319 (10) | −0.0001 (10) | 0.0068 (10) | 0.0015 (7) |
C8 | 0.0511 (14) | 0.0241 (8) | 0.0332 (10) | −0.0007 (10) | 0.0078 (12) | 0.0005 (7) |
C9 | 0.0524 (15) | 0.0248 (9) | 0.0256 (9) | −0.0024 (10) | 0.0023 (10) | 0.0008 (7) |
O1 | 0.0380 (9) | 0.0475 (8) | 0.0291 (7) | −0.0019 (7) | −0.0034 (7) | −0.0042 (7) |
O2 | 0.0486 (10) | 0.0242 (6) | 0.0306 (7) | 0.0031 (8) | 0.0066 (7) | −0.0017 (6) |
O3 | 0.0547 (12) | 0.0374 (9) | 0.0685 (12) | −0.0094 (9) | 0.0153 (10) | 0.0013 (8) |
O4 | 0.0725 (13) | 0.0230 (7) | 0.0605 (11) | 0.0012 (9) | 0.0217 (11) | 0.0025 (7) |
Geometric parameters (Å, º) top
P1—O2 | 1.5010 (14) | C5—H5A | 0.9300 |
P1—O1 | 1.5605 (16) | C6—H6A | 0.9300 |
P1—C7 | 1.788 (2) | C7—C8 | 1.523 (3) |
P1—C1 | 1.7896 (19) | C7—H7A | 0.9700 |
C1—C6 | 1.385 (3) | C7—H7B | 0.9700 |
C1—C2 | 1.393 (3) | C8—C9 | 1.502 (3) |
C2—C3 | 1.387 (3) | C8—H8A | 0.9700 |
C2—H2A | 0.9300 | C8—H8B | 0.9700 |
C3—C4 | 1.377 (4) | C9—O3 | 1.200 (3) |
C3—H3A | 0.9300 | C9—O4 | 1.321 (3) |
C4—C5 | 1.370 (4) | O1—H1A | 0.814 (10) |
C4—H4A | 0.9300 | O4—H4B | 0.818 (10) |
C5—C6 | 1.391 (3) | | |
| | | |
O2—P1—O1 | 114.47 (9) | C1—C6—C5 | 120.0 (3) |
O2—P1—C7 | 110.40 (9) | C1—C6—H6A | 120.0 |
O1—P1—C7 | 108.12 (10) | C5—C6—H6A | 120.0 |
O2—P1—C1 | 111.08 (9) | C8—C7—P1 | 113.17 (15) |
O1—P1—C1 | 103.83 (10) | C8—C7—H7A | 108.9 |
C7—P1—C1 | 108.61 (10) | P1—C7—H7A | 108.9 |
C6—C1—C2 | 119.7 (2) | C8—C7—H7B | 108.9 |
C6—C1—P1 | 119.16 (17) | P1—C7—H7B | 108.9 |
C2—C1—P1 | 121.12 (17) | H7A—C7—H7B | 107.8 |
C3—C2—C1 | 120.0 (2) | C9—C8—C7 | 112.94 (18) |
C3—C2—H2A | 120.0 | C9—C8—H8A | 109.0 |
C1—C2—H2A | 120.0 | C7—C8—H8A | 109.0 |
C4—C3—C2 | 119.5 (3) | C9—C8—H8B | 109.0 |
C4—C3—H3A | 120.2 | C7—C8—H8B | 109.0 |
C2—C3—H3A | 120.2 | H8A—C8—H8B | 107.8 |
C5—C4—C3 | 121.2 (2) | O3—C9—O4 | 124.3 (2) |
C5—C4—H4A | 119.4 | O3—C9—C8 | 124.4 (2) |
C3—C4—H4A | 119.4 | O4—C9—C8 | 111.22 (19) |
C4—C5—C6 | 119.6 (3) | P1—O1—H1A | 111.3 (18) |
C4—C5—H5A | 120.2 | C9—O4—H4B | 106 (2) |
C6—C5—H5A | 120.2 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.81 (1) | 1.76 (1) | 2.5699 (18) | 177 (3) |
O4—H4B···O2ii | 0.82 (1) | 1.90 (1) | 2.6925 (19) | 162 (3) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x, y−1, z. |
Crystal data top
C9H11O4P | F(000) = 448 |
Mr = 214.15 | Dx = 1.330 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1679 reflections |
a = 6.1741 (15) Å | θ = 2.6–25.7° |
b = 8.7308 (19) Å | µ = 0.24 mm−1 |
c = 19.844 (4) Å | T = 296 K |
V = 1069.7 (4) Å3 | Block, colorless |
Z = 4 | 0.34 × 0.16 × 0.14 mm |
Data collection top
CCD area detector diffractometer | 2422 independent reflections |
Radiation source: fine-focus sealed tube | 1977 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −7→7 |
Tmin = 0.679, Tmax = 0.746 | k = −11→11 |
5593 measured reflections | l = −25→25 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0465P)2 + 0.0144P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2422 reflections | Δρmax = 0.18 e Å−3 |
133 parameters | Δρmin = −0.22 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 989 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.11 (11) |
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 | x | y | z | Uiso*/Ueq | |
P1 | 0.37137 (10) | 0.30994 (5) | 0.07762 (2) | 0.03642 (15) | |
C1 | 0.2943 (4) | 0.3038 (3) | 0.16448 (10) | 0.0424 (5) | |
C2 | 0.4255 (5) | 0.3675 (3) | 0.21432 (11) | 0.0573 (7) | |
H2A | 0.5568 | 0.4124 | 0.2026 | 0.069* | |
C3 | 0.3614 (6) | 0.3644 (4) | 0.28125 (12) | 0.0756 (9) | |
H3A | 0.4495 | 0.4071 | 0.3143 | 0.091* | |
C4 | 0.1681 (7) | 0.2984 (5) | 0.29860 (14) | 0.0897 (11) | |
H4A | 0.1255 | 0.2962 | 0.3435 | 0.108* | |
C5 | 0.0382 (6) | 0.2362 (5) | 0.25059 (16) | 0.1031 (13) | |
H5A | −0.0931 | 0.1924 | 0.2630 | 0.124* | |
C6 | 0.0992 (5) | 0.2372 (4) | 0.18286 (13) | 0.0735 (9) | |
H6A | 0.0099 | 0.1936 | 0.1504 | 0.088* | |
C7 | 0.2817 (4) | 0.4866 (2) | 0.03997 (11) | 0.0433 (5) | |
H7A | 0.3459 | 0.4959 | −0.0045 | 0.052* | |
H7B | 0.1257 | 0.4827 | 0.0343 | 0.052* | |
C8 | 0.3389 (4) | 0.6269 (2) | 0.08058 (10) | 0.0439 (5) | |
H8A | 0.4884 | 0.6185 | 0.0952 | 0.053* | |
H8B | 0.2488 | 0.6294 | 0.1206 | 0.053* | |
C9 | 0.3113 (4) | 0.7760 (2) | 0.04301 (11) | 0.0387 (5) | |
O1 | 0.6226 (3) | 0.31246 (18) | 0.08088 (7) | 0.0472 (4) | |
H1A | 0.685 (4) | 0.323 (3) | 0.0452 (7) | 0.057* | |
O2 | 0.2784 (3) | 0.17650 (16) | 0.03892 (7) | 0.0491 (4) | |
O3 | 0.3148 (3) | 0.79083 (17) | −0.01724 (7) | 0.0476 (4) | |
O4 | 0.2882 (4) | 0.89173 (16) | 0.08613 (8) | 0.0615 (5) | |
H4B | 0.288 (5) | 0.9748 (18) | 0.0667 (13) | 0.074* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0497 (3) | 0.0264 (2) | 0.0331 (2) | 0.0026 (3) | −0.0043 (3) | 0.0007 (2) |
C1 | 0.0509 (13) | 0.0382 (10) | 0.0381 (10) | 0.0024 (13) | −0.0009 (10) | 0.0032 (9) |
C2 | 0.0620 (19) | 0.0698 (16) | 0.0400 (12) | −0.0073 (14) | −0.0060 (11) | 0.0006 (11) |
C3 | 0.092 (2) | 0.097 (2) | 0.0383 (12) | 0.004 (2) | −0.0095 (15) | −0.0004 (13) |
C4 | 0.103 (3) | 0.122 (3) | 0.0436 (13) | 0.012 (3) | 0.0166 (17) | 0.0046 (17) |
C5 | 0.081 (3) | 0.167 (4) | 0.0619 (18) | −0.029 (3) | 0.0227 (18) | 0.017 (2) |
C6 | 0.066 (2) | 0.101 (2) | 0.0538 (14) | −0.0212 (19) | 0.0009 (14) | −0.0004 (15) |
C7 | 0.0581 (15) | 0.0287 (9) | 0.0431 (11) | 0.0016 (11) | −0.0090 (11) | 0.0033 (9) |
C8 | 0.0669 (16) | 0.0269 (8) | 0.0379 (10) | 0.0007 (11) | 0.0022 (12) | 0.0042 (9) |
C9 | 0.0426 (13) | 0.0285 (10) | 0.0449 (11) | −0.0003 (10) | −0.0017 (10) | 0.0036 (8) |
O1 | 0.0486 (9) | 0.0542 (8) | 0.0388 (7) | 0.0079 (10) | 0.0014 (8) | 0.0004 (8) |
O2 | 0.0762 (12) | 0.0268 (7) | 0.0443 (8) | −0.0009 (8) | −0.0132 (8) | −0.0011 (6) |
O3 | 0.0595 (11) | 0.0418 (8) | 0.0414 (7) | −0.0004 (8) | −0.0027 (7) | 0.0068 (6) |
O4 | 0.1068 (16) | 0.0264 (7) | 0.0514 (9) | 0.0032 (9) | −0.0090 (10) | 0.0003 (7) |
Geometric parameters (Å, º) top
P1—O2 | 1.5087 (15) | C5—H5A | 0.9300 |
P1—O1 | 1.5527 (17) | C6—H6A | 0.9300 |
P1—C1 | 1.789 (2) | C7—C8 | 1.508 (3) |
P1—C7 | 1.801 (2) | C7—H7A | 0.9700 |
C1—C6 | 1.386 (4) | C7—H7B | 0.9700 |
C1—C2 | 1.394 (3) | C8—C9 | 1.510 (3) |
C2—C3 | 1.386 (3) | C8—H8A | 0.9700 |
C2—H2A | 0.9300 | C8—H8B | 0.9700 |
C3—C4 | 1.369 (5) | C9—O3 | 1.203 (2) |
C3—H3A | 0.9300 | C9—O4 | 1.331 (3) |
C4—C5 | 1.358 (5) | O1—H1A | 0.810 (10) |
C4—H4A | 0.9300 | O4—H4B | 0.821 (10) |
C5—C6 | 1.396 (4) | | |
| | | |
O2—P1—O1 | 114.33 (10) | C1—C6—C5 | 119.4 (3) |
O2—P1—C1 | 111.47 (10) | C1—C6—H6A | 120.3 |
O1—P1—C1 | 103.07 (10) | C5—C6—H6A | 120.3 |
O2—P1—C7 | 109.47 (9) | C8—C7—P1 | 113.70 (15) |
O1—P1—C7 | 108.19 (12) | C8—C7—H7A | 108.8 |
C1—P1—C7 | 110.09 (11) | P1—C7—H7A | 108.8 |
C6—C1—C2 | 119.0 (2) | C8—C7—H7B | 108.8 |
C6—C1—P1 | 119.83 (18) | P1—C7—H7B | 108.8 |
C2—C1—P1 | 121.12 (19) | H7A—C7—H7B | 107.7 |
C3—C2—C1 | 120.4 (3) | C7—C8—C9 | 114.20 (17) |
C3—C2—H2A | 119.8 | C7—C8—H8A | 108.7 |
C1—C2—H2A | 119.8 | C9—C8—H8A | 108.7 |
C4—C3—C2 | 119.9 (3) | C7—C8—H8B | 108.7 |
C4—C3—H3A | 120.1 | C9—C8—H8B | 108.7 |
C2—C3—H3A | 120.1 | H8A—C8—H8B | 107.6 |
C5—C4—C3 | 120.4 (3) | O3—C9—O4 | 124.01 (19) |
C5—C4—H4A | 119.8 | O3—C9—C8 | 125.54 (19) |
C3—C4—H4A | 119.8 | O4—C9—C8 | 110.42 (17) |
C4—C5—C6 | 120.9 (3) | P1—O1—H1A | 116.0 (19) |
C4—C5—H5A | 119.6 | C9—O4—H4B | 112 (2) |
C6—C5—H5A | 119.6 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.81 (1) | 1.77 (1) | 2.566 (2) | 169 (3) |
O4—H4B···O2ii | 0.82 (1) | 1.85 (1) | 2.658 (2) | 169 (3) |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x, y+1, z. |