Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102012386/fg1653sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102012386/fg1653IIIasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102012386/fg1653IIIbsup3.hkl |
CCDC references: 193453; 193454
The synthesis of the title compounds was based on the addition of two equivalents of tris(trimethylsilyl)phosphite to the corresponding acid chlorides, (I), to yield the tetrakis(trimethylsilyl) ester of 1-aryl-1-trimethylsiloxymethane-1,1-bisphosphonic acid, (II) (not isolated). Direct methanolysis afforded the title substituted [hydroxy(aryl)methylene]diphosphonic acids, (IIIa) with R = H and (IIIb) with R = NO2, in nearly quantitative yields (Scheme). Compound (IIIa) was obtained as a white powder in 91% yield, and was crystallized by slow evaporation of a solution in a mixture of ethanol and water (90:10) at room temperature. Spectroscopic analysis: 31P NMR (D2O, δ, p.p.m.): 16.0 (s); 1H NMR (D2O, δ, p.p.m.): 7.08–7.13 (m, 4H, C6H5), 7.46 (t, 3J = 5 Hz, 1H, C6H5); 13C NMR (D2O, δ, p.p.m.): 78.76 (t, 1J = 145.75 Hz, COH), 128.9, 130.8, 131.2, 138.6 (C6H5). Compound (IIIb) was obtained as a yellowish powder in 85% yield, and was crystallized by slow evaporation of a solution in tetrahydrofuran at room temperature. Spectroscopic analysis: 31P NMR (D2O, δ, p.p.m.): 15.3 (s); 1H NMR (D2O, δ, p.p.m.): 7.89 (d, 2H, 3J = 8.5 Hz, C6H4), 8.15 (d, 2H, 3J = 8.5 Hz, C6H4); 13C NMR (D2O, δ, p.p.m.): 75.28 (t, 1J = 149 Hz, COH), 124.67, 128.15, 146.13, 148.35 (C6H4).
For compound (IIIa), all H atoms but four (on the O1W and O2W molecules) were located in difference Fourier maps. They were kept in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 and O—H = 0.82 Å, and Uiso(H) = 1.2Ueq(C). For compound (IIIb), all H atoms were located in successive difference Fourier maps and freely refined; the C—H distances were in the range 0.92 (3) to 1.06 (3) Å. Please clarify - in CIF, H22A, H22B, H32A and H32B were all fixed.
Data collection: PHIL (local program; author, 1980) for (IIIa); KappaCCD Server Software (Nonius, 1997) for (IIIb). Cell refinement: PARAM (local program; author, 1995) for (IIIa); DENZO-SMN (Otwinowsky & Minor, 1997) for (IIIb). Data reduction: PHIL for (IIIa); DENZO-SMN for (IIIb). For both compounds, program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PLATON.
C7H10O7P2·H2O | F(000) = 586 |
Mr = 286.10 | Dx = 1.668 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 8.42 (2) Å | θ = 8–25° |
b = 23.05 (1) Å | µ = 3.81 mm−1 |
c = 5.91 (2) Å | T = 293 K |
β = 97.7 (2)° | Rod-shaped prism, colourless |
V = 1137 (6) Å3 | 0.5 × 0.2 × 0.2 mm |
Z = 4 |
Philips PW 1100 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 65.8°, θmin = 5.3° |
Graphite monochromator | h = −9→9 |
θ/2θ scans | k = −23→24 |
3430 measured reflections | l = 0→6 |
3430 independent reflections | 3 standard reflections every 130 reflections |
2875 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0356P)2 + 1.8431P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.098 |
3430 reflections | Δρmax = 0.27 e Å−3 |
311 parameters | Δρmin = −0.29 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 1421 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.18 (5) |
C7H10O7P2·H2O | V = 1137 (6) Å3 |
Mr = 286.10 | Z = 4 |
Monoclinic, P21 | Cu Kα radiation |
a = 8.42 (2) Å | µ = 3.81 mm−1 |
b = 23.05 (1) Å | T = 293 K |
c = 5.91 (2) Å | 0.5 × 0.2 × 0.2 mm |
β = 97.7 (2)° |
Philips PW 1100 diffractometer | Rint = 0.000 |
3430 measured reflections | 3 standard reflections every 130 reflections |
3430 independent reflections | intensity decay: 3% |
2875 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.096 | Δρmax = 0.27 e Å−3 |
S = 1.12 | Δρmin = −0.29 e Å−3 |
3430 reflections | Absolute structure: Flack (1983), with 1421 Friedel pairs |
311 parameters | Absolute structure parameter: 0.18 (5) |
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. |
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 | ||
P1 | 0.88450 (15) | 0.23466 (5) | 0.1837 (2) | 0.0269 (3) | |
P2 | 0.65186 (15) | 0.14613 (6) | 0.3620 (2) | 0.0272 (3) | |
O1 | 0.9098 (4) | 0.26948 (16) | 0.4003 (5) | 0.0320 (8) | |
O2 | 1.0351 (4) | 0.23296 (17) | 0.0580 (6) | 0.0334 (8) | |
H21 | 1.1103 | 0.2187 | 0.1421 | 0.040* | |
O3 | 0.7506 (5) | 0.25647 (18) | 0.0005 (6) | 0.0420 (10) | |
H31 | 0.6982 | 0.2815 | 0.0555 | 0.063* | |
O4 | 0.6528 (4) | 0.17542 (15) | 0.5883 (5) | 0.0288 (8) | |
O5 | 0.5164 (5) | 0.1659 (2) | 0.1736 (6) | 0.0465 (11) | |
H51 | 0.4566 | 0.1885 | 0.2285 | 0.070* | |
O6 | 0.6335 (5) | 0.07893 (17) | 0.3700 (6) | 0.0374 (9) | |
H61 | 0.6775 | 0.0667 | 0.4929 | 0.056* | |
O7 | 0.7989 (4) | 0.13214 (17) | 0.0088 (5) | 0.0327 (9) | |
H71 | 0.7591 | 0.1563 | −0.0836 | 0.049* | |
C1 | 0.8353 (6) | 0.1590 (2) | 0.2318 (8) | 0.0323 (12) | |
C2 | 0.9771 (6) | 0.1303 (2) | 0.3644 (9) | 0.0326 (13) | |
C3 | 1.0611 (7) | 0.0870 (3) | 0.2660 (9) | 0.0390 (13) | |
H3 | 1.0239 | 0.0750 | 0.1182 | 0.047* | |
C4 | 1.1970 (7) | 0.0614 (3) | 0.3787 (10) | 0.0418 (14) | |
H4 | 1.2486 | 0.0318 | 0.3106 | 0.050* | |
C5 | 1.2549 (7) | 0.0809 (3) | 0.5964 (10) | 0.0461 (15) | |
H5 | 1.3503 | 0.0664 | 0.6733 | 0.055* | |
C6 | 1.1681 (8) | 0.1220 (3) | 0.6957 (10) | 0.0458 (16) | |
H6 | 1.2022 | 0.1335 | 0.8451 | 0.055* | |
C7 | 1.0300 (6) | 0.1468 (2) | 0.5771 (7) | 0.0256 (10) | |
H7 | 0.9747 | 0.1751 | 0.6472 | 0.031* | |
P1' | 0.33318 (16) | 0.27646 (6) | 0.5223 (2) | 0.0270 (3) | |
P2' | 0.56673 (14) | 0.36521 (6) | 0.3454 (2) | 0.0255 (3) | |
O1' | 0.3137 (4) | 0.24395 (16) | 0.2966 (6) | 0.0296 (8) | |
O2' | 0.1883 (4) | 0.28018 (16) | 0.6471 (6) | 0.0339 (8) | |
H2P | 0.1078 | 0.2712 | 0.5602 | 0.051* | |
O3' | 0.4617 (5) | 0.25226 (14) | 0.7047 (6) | 0.0283 (9) | |
H3P | 0.5102 | 0.2261 | 0.6498 | 0.042* | |
O4' | 0.5634 (4) | 0.33683 (15) | 0.1205 (6) | 0.0297 (8) | |
O5' | 0.7042 (4) | 0.34501 (17) | 0.5285 (6) | 0.0389 (10) | |
H5P | 0.7652 | 0.3238 | 0.4693 | 0.058* | |
O6' | 0.5784 (5) | 0.43272 (16) | 0.3357 (7) | 0.0422 (10) | |
H6P | 0.5467 | 0.4439 | 0.2058 | 0.063* | |
O7' | 0.4147 (4) | 0.37970 (13) | 0.7040 (5) | 0.0245 (7) | |
H72 | 0.4908 | 0.3632 | 0.7783 | 0.037* | |
C1' | 0.3842 (6) | 0.3541 (2) | 0.4783 (8) | 0.0245 (11) | |
C2' | 0.2401 (7) | 0.3814 (3) | 0.3509 (9) | 0.0362 (13) | |
C3' | 0.1543 (6) | 0.4203 (2) | 0.4541 (8) | 0.0329 (12) | |
H3' | 0.1897 | 0.4323 | 0.6025 | 0.039* | |
C4' | 0.0091 (9) | 0.4430 (3) | 0.3348 (13) | 0.0579 (18) | |
H4' | −0.0538 | 0.4678 | 0.4095 | 0.070* | |
C5' | −0.0386 (7) | 0.4285 (3) | 0.1118 (10) | 0.0406 (14) | |
H5' | −0.1304 | 0.4451 | 0.0327 | 0.049* | |
C6' | 0.0455 (7) | 0.3914 (3) | 0.0102 (11) | 0.0564 (18) | |
H6' | 0.0118 | 0.3814 | −0.1411 | 0.068* | |
C7' | 0.1827 (7) | 0.3667 (3) | 0.1220 (11) | 0.0430 (15) | |
H7' | 0.2388 | 0.3399 | 0.0459 | 0.052* | |
O1W | 0.5302 (6) | 0.4803 (2) | −0.0653 (8) | 0.0599 (12) | |
O2W | 0.7012 (7) | 0.03416 (19) | 0.7769 (8) | 0.0656 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0261 (7) | 0.0222 (7) | 0.0322 (7) | 0.0020 (6) | 0.0029 (5) | −0.0084 (5) |
P2 | 0.0226 (6) | 0.0315 (7) | 0.0258 (7) | 0.0025 (6) | −0.0033 (5) | 0.0021 (5) |
O1 | 0.036 (2) | 0.040 (2) | 0.0181 (16) | 0.0022 (17) | −0.0008 (14) | −0.0149 (15) |
O2 | 0.0239 (19) | 0.045 (2) | 0.0328 (18) | −0.0047 (17) | 0.0080 (15) | 0.0003 (17) |
O3 | 0.022 (2) | 0.056 (3) | 0.043 (2) | 0.0100 (17) | −0.0133 (16) | −0.0125 (19) |
O4 | 0.0230 (18) | 0.038 (2) | 0.0227 (18) | 0.0040 (15) | −0.0065 (13) | −0.0074 (15) |
O5 | 0.026 (2) | 0.087 (3) | 0.0228 (19) | 0.008 (2) | −0.0087 (15) | −0.017 (2) |
O6 | 0.033 (2) | 0.038 (2) | 0.044 (2) | −0.0056 (16) | 0.0133 (17) | −0.0075 (17) |
O7 | 0.0269 (18) | 0.057 (3) | 0.0140 (16) | 0.0097 (17) | 0.0018 (13) | −0.0069 (15) |
C1 | 0.030 (3) | 0.035 (3) | 0.032 (3) | −0.010 (2) | 0.004 (2) | −0.003 (2) |
C2 | 0.027 (3) | 0.030 (3) | 0.038 (3) | 0.002 (2) | −0.005 (2) | −0.009 (2) |
C3 | 0.047 (3) | 0.039 (3) | 0.030 (3) | 0.011 (3) | −0.001 (2) | −0.001 (2) |
C4 | 0.024 (3) | 0.046 (4) | 0.057 (4) | 0.013 (3) | 0.008 (2) | 0.014 (3) |
C5 | 0.031 (3) | 0.060 (4) | 0.045 (4) | 0.012 (3) | −0.007 (3) | 0.014 (3) |
C6 | 0.055 (4) | 0.050 (4) | 0.030 (3) | −0.017 (3) | −0.001 (3) | 0.009 (3) |
C7 | 0.031 (3) | 0.026 (3) | 0.019 (2) | 0.002 (2) | 0.0019 (19) | −0.008 (2) |
P1' | 0.0285 (7) | 0.0323 (8) | 0.0185 (7) | 0.0031 (6) | −0.0027 (5) | 0.0043 (5) |
P2' | 0.0193 (6) | 0.0321 (7) | 0.0263 (7) | −0.0013 (5) | 0.0077 (5) | −0.0051 (5) |
O1' | 0.0196 (18) | 0.034 (2) | 0.0361 (18) | 0.0058 (15) | 0.0059 (14) | 0.0047 (15) |
O2' | 0.033 (2) | 0.025 (2) | 0.044 (2) | −0.0098 (17) | 0.0088 (16) | −0.0025 (16) |
O3' | 0.034 (2) | 0.0168 (17) | 0.0313 (19) | 0.0124 (14) | −0.0073 (16) | −0.0083 (14) |
O4' | 0.0299 (19) | 0.031 (2) | 0.029 (2) | 0.0086 (16) | 0.0080 (14) | 0.0056 (15) |
O5' | 0.024 (2) | 0.051 (3) | 0.043 (2) | 0.0096 (18) | 0.0058 (16) | −0.0036 (18) |
O6' | 0.046 (2) | 0.021 (2) | 0.059 (3) | −0.0104 (17) | 0.0074 (19) | 0.0088 (17) |
O7' | 0.0284 (19) | 0.0158 (19) | 0.0297 (18) | 0.0062 (13) | 0.0057 (14) | −0.0041 (13) |
C1' | 0.022 (2) | 0.027 (3) | 0.023 (2) | 0.007 (2) | −0.0018 (18) | 0.0024 (19) |
C2' | 0.041 (3) | 0.047 (4) | 0.022 (3) | 0.002 (3) | 0.011 (2) | 0.001 (2) |
C3' | 0.026 (3) | 0.047 (3) | 0.025 (3) | 0.001 (2) | 0.003 (2) | −0.001 (2) |
C4' | 0.068 (5) | 0.029 (3) | 0.080 (5) | 0.012 (3) | 0.022 (4) | 0.002 (3) |
C5' | 0.028 (3) | 0.045 (4) | 0.050 (4) | 0.002 (2) | 0.007 (3) | 0.018 (3) |
C6' | 0.035 (4) | 0.076 (5) | 0.054 (4) | 0.014 (3) | −0.010 (3) | −0.005 (3) |
C7' | 0.022 (3) | 0.041 (3) | 0.067 (4) | 0.013 (3) | 0.011 (3) | 0.017 (3) |
O1W | 0.065 (3) | 0.060 (3) | 0.055 (3) | −0.002 (3) | 0.007 (2) | 0.006 (2) |
O2W | 0.092 (4) | 0.033 (3) | 0.072 (3) | −0.006 (3) | 0.012 (3) | 0.000 (2) |
P1—O1 | 1.502 (6) | P1'—O1' | 1.520 (7) |
P1—O2 | 1.554 (5) | P1'—O2' | 1.511 (5) |
P1—O3 | 1.539 (6) | P1'—O3' | 1.527 (6) |
P1—C1 | 1.824 (5) | P1'—C1' | 1.866 (5) |
P2—O4 | 1.497 (7) | P2'—O4' | 1.478 (7) |
P2—O5 | 1.552 (6) | P2'—O5' | 1.547 (6) |
P2—O6 | 1.558 (4) | P2'—O6' | 1.561 (4) |
P2—C1 | 1.840 (7) | P2'—C1' | 1.836 (7) |
O2—H21 | 0.8200 | O2'—H2P | 0.8200 |
O3—H31 | 0.8200 | O3'—H3P | 0.8200 |
O5—H51 | 0.8200 | O5'—H5P | 0.8200 |
O6—H61 | 0.8201 | O6'—H6P | 0.8200 |
O7—C1 | 1.451 (8) | O7'—C1' | 1.450 (8) |
O7—H71 | 0.8200 | O7'—H72 | 0.8200 |
C1—C2 | 1.492 (8) | C1'—C2' | 1.480 (8) |
C2—C7 | 1.333 (9) | C2'—C3' | 1.347 (8) |
C2—C3 | 1.393 (8) | C2'—C7' | 1.415 (11) |
C3—C4 | 1.378 (8) | C3'—C4' | 1.427 (10) |
C3—H3 | 0.9300 | C3'—H3' | 0.9300 |
C4—C5 | 1.388 (10) | C4'—C5' | 1.366 (11) |
C4—H4 | 0.9300 | C4'—H4' | 0.9300 |
C5—C6 | 1.376 (10) | C5'—C6' | 1.309 (9) |
C5—H5 | 0.9300 | C5'—H5' | 0.9300 |
C6—C7 | 1.397 (8) | C6'—C7' | 1.374 (8) |
C6—H6 | 0.9300 | C6'—H6' | 0.9300 |
C7—H7 | 0.9300 | C7'—H7' | 0.9300 |
O1—P1—O3 | 115.6 (3) | O2'—P1'—O1' | 117.2 (3) |
O1—P1—O2 | 112.9 (3) | O2'—P1'—O3' | 102.6 (4) |
O3—P1—O2 | 103.9 (4) | O1'—P1'—O3' | 115.0 (3) |
O1—P1—C1 | 112.8 (3) | O2'—P1'—C1' | 103.3 (2) |
O3—P1—C1 | 105.2 (2) | O1'—P1'—C1' | 110.5 (3) |
O2—P1—C1 | 105.5 (2) | O3'—P1'—C1' | 107.1 (2) |
O4—P2—O5 | 115.1 (3) | O4'—P2'—O5' | 114.7 (3) |
O4—P2—O6 | 114.2 (2) | O4'—P2'—O6' | 113.7 (3) |
O5—P2—O6 | 104.4 (2) | O5'—P2'—O6' | 106.3 (2) |
O4—P2—C1 | 113.4 (3) | O4'—P2'—C1' | 114.0 (3) |
O5—P2—C1 | 103.3 (4) | O5'—P2'—C1' | 104.4 (3) |
O6—P2—C1 | 105.4 (2) | O6'—P2'—C1' | 102.5 (2) |
P1—O2—H21 | 109.5 | P1'—O2'—H2P | 109.5 |
P1—O3—H31 | 109.5 | P1'—O3'—H3P | 109.5 |
P2—O5—H51 | 109.5 | P2'—O5'—H5P | 109.5 |
P2—O6—H61 | 109.5 | P2'—O6'—H6P | 109.5 |
C1—O7—H71 | 109.4 | C1'—O7'—H72 | 109.5 |
O7—C1—C2 | 110.2 (5) | O7'—C1'—C2' | 109.1 (4) |
O7—C1—P1 | 106.9 (4) | O7'—C1'—P2' | 106.3 (4) |
C2—C1—P1 | 108.9 (4) | C2'—C1'—P2' | 113.5 (4) |
O7—C1—P2 | 103.0 (4) | O7'—C1'—P1' | 106.2 (3) |
C2—C1—P2 | 111.5 (4) | C2'—C1'—P1' | 106.9 (4) |
P1—C1—P2 | 116.1 (3) | P2'—C1'—P1' | 114.5 (3) |
C7—C2—C3 | 118.3 (5) | C3'—C2'—C7' | 117.2 (5) |
C7—C2—C1 | 120.8 (5) | C3'—C2'—C1' | 120.3 (5) |
C3—C2—C1 | 120.9 (5) | C7'—C2'—C1' | 122.4 (5) |
C4—C3—C2 | 122.7 (6) | C2'—C3'—C4' | 119.7 (6) |
C4—C3—H3 | 118.7 | C2'—C3'—H3' | 120.1 |
C2—C3—H3 | 118.7 | C4'—C3'—H3' | 120.1 |
C3—C4—C5 | 118.4 (6) | C5'—C4'—C3' | 120.6 (6) |
C3—C4—H4 | 120.8 | C5'—C4'—H4' | 119.7 |
C5—C4—H4 | 120.8 | C3'—C4'—H4' | 119.7 |
C6—C5—C4 | 118.6 (5) | C6'—C5'—C4' | 119.7 (6) |
C6—C5—H5 | 120.7 | C6'—C5'—H5' | 120.2 |
C4—C5—H5 | 120.7 | C4'—C5'—H5' | 120.2 |
C5—C6—C7 | 121.4 (6) | C5'—C6'—C7' | 121.5 (7) |
C5—C6—H6 | 119.3 | C5'—C6'—H6' | 119.3 |
C7—C6—H6 | 119.3 | C7'—C6'—H6' | 119.3 |
C2—C7—C6 | 120.5 (5) | C6'—C7'—C2' | 121.2 (6) |
C2—C7—H7 | 119.8 | C6'—C7'—H7' | 119.4 |
C6—C7—H7 | 119.8 | C2'—C7'—H7' | 119.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O1′i | 0.82 | 1.92 | 2.583 (9) | 137 |
O2′—H2P···O1ii | 0.82 | 1.80 | 2.602 (9) | 164 |
O3—H31···O4′ | 0.82 | 1.78 | 2.592 (9) | 169 |
O3′—H3P···O4 | 0.82 | 1.75 | 2.549 (9) | 165 |
O5—H51···O1′ | 0.82 | 1.84 | 2.647 (9) | 169 |
O5′—H5P···O1 | 0.82 | 1.83 | 2.637 (9) | 167 |
O6—H61···O2W | 0.82 | 1.83 | 2.609 (9) | 160 |
O6′—H6P···O1W | 0.82 | 1.80 | 2.594 (9) | 163 |
O7—H71···O4iii | 0.82 | 2.07 | 2.805 (9) | 149 |
O7—H71···O3 | 0.82 | 2.36 | 2.894 (10) | 123 |
O7′—H72···O4′iv | 0.82 | 2.12 | 2.789 (9) | 138 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, y, z−1; (iv) x, y, z+1. |
C7H9NO9P2·2C4H8O | F(000) = 960 |
Mr = 457.30 | Dx = 1.474 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 78 reflections |
a = 14.0005 (9) Å | θ = 8–40° |
b = 6.0243 (2) Å | µ = 0.27 mm−1 |
c = 24.4427 (6) Å | T = 132 K |
β = 91.903 (3)° | Plate, pale yellow |
V = 2060.44 (16) Å3 | 0.20 × 0.20 × 0.05 mm |
Z = 4 |
Nonius KappaCCD are-detector diffractometer | 2986 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.000 |
Graphite monochromator | θmax = 25.5°, θmin = 2.9° |
ϕ and ω scans | h = 0→16 |
3734 measured reflections | k = 0→7 |
3734 independent reflections | l = −29→29 |
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)] = 0.045 | All H-atom parameters refined |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.025P)2 + 2.62P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.046 |
3734 reflections | Δρmax = 0.39 e Å−3 |
329 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0017 (6) |
C7H9NO9P2·2C4H8O | V = 2060.44 (16) Å3 |
Mr = 457.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.0005 (9) Å | µ = 0.27 mm−1 |
b = 6.0243 (2) Å | T = 132 K |
c = 24.4427 (6) Å | 0.20 × 0.20 × 0.05 mm |
β = 91.903 (3)° |
Nonius KappaCCD are-detector diffractometer | 2986 reflections with I > 2σ(I) |
3734 measured reflections | Rint = 0.000 |
3734 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.096 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.39 e Å−3 |
3734 reflections | Δρmin = −0.37 e Å−3 |
329 parameters |
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 | ||
P1 | 0.55465 (4) | 0.66665 (10) | 0.58375 (2) | 0.01872 (17) | |
O1 | 0.49584 (12) | 0.4582 (3) | 0.58560 (7) | 0.0245 (4) | |
O2 | 0.56520 (13) | 0.7910 (3) | 0.63979 (7) | 0.0288 (4) | |
H21 | 0.513 (3) | 0.808 (6) | 0.6577 (14) | 0.065 (5)* | |
O3 | 0.51952 (13) | 0.8351 (3) | 0.53926 (7) | 0.0275 (4) | |
H31 | 0.469 (3) | 0.814 (6) | 0.5242 (14) | 0.065 (5)* | |
P2 | 0.70353 (4) | 0.45461 (10) | 0.50407 (2) | 0.01808 (17) | |
O4 | 0.65329 (11) | 0.2339 (3) | 0.50446 (6) | 0.0209 (4) | |
O5 | 0.67212 (13) | 0.6113 (3) | 0.45586 (6) | 0.0237 (4) | |
H51 | 0.608 (3) | 0.589 (6) | 0.4440 (14) | 0.065 (5)* | |
O6 | 0.81622 (12) | 0.4285 (3) | 0.50194 (7) | 0.0232 (4) | |
H61 | 0.848 (3) | 0.533 (6) | 0.4894 (15) | 0.065 (5)* | |
C1 | 0.68405 (17) | 0.6179 (4) | 0.56779 (9) | 0.0189 (5) | |
O7 | 0.73139 (12) | 0.8296 (3) | 0.56021 (7) | 0.0216 (4) | |
H71 | 0.696 (3) | 0.907 (6) | 0.5385 (14) | 0.065 (5)* | |
C2 | 0.73415 (16) | 0.5004 (4) | 0.61681 (9) | 0.0180 (5) | |
C4 | 0.74655 (17) | 0.1842 (4) | 0.67865 (9) | 0.0220 (5) | |
H4 | 0.7270 (19) | 0.043 (5) | 0.6880 (11) | 0.029 (4)* | |
C3 | 0.70156 (17) | 0.2900 (4) | 0.63368 (9) | 0.0193 (5) | |
H3 | 0.648 (2) | 0.222 (4) | 0.6148 (11) | 0.029 (4)* | |
C5 | 0.82277 (17) | 0.2920 (4) | 0.70627 (9) | 0.0219 (5) | |
C7 | 0.81133 (17) | 0.6035 (4) | 0.64551 (10) | 0.0218 (5) | |
H7 | 0.8325 (19) | 0.747 (5) | 0.6341 (10) | 0.029 (4)* | |
C6 | 0.85602 (19) | 0.4998 (4) | 0.69080 (10) | 0.0246 (6) | |
H6 | 0.907 (2) | 0.565 (4) | 0.7089 (11) | 0.029 (4)* | |
N4 | 0.87190 (15) | 0.1800 (4) | 0.75356 (8) | 0.0289 (5) | |
O41 | 0.84879 (16) | −0.0120 (4) | 0.76432 (8) | 0.0473 (6) | |
O42 | 0.93419 (14) | 0.2852 (3) | 0.78042 (8) | 0.0414 (5) | |
O11 | 0.92447 (13) | 0.7322 (3) | 0.46287 (8) | 0.0335 (5) | |
C21 | 0.8821 (2) | 0.9534 (4) | 0.45821 (12) | 0.0295 (6) | |
H21A | 0.881 (2) | 1.009 (6) | 0.4946 (14) | 0.056 (3)* | |
H21B | 0.814 (2) | 0.938 (5) | 0.4458 (13) | 0.056 (3)* | |
C31 | 0.9452 (2) | 1.0794 (5) | 0.41805 (12) | 0.0336 (6) | |
H31A | 0.992 (2) | 1.188 (6) | 0.4375 (13) | 0.056 (3)* | |
H31B | 0.905 (2) | 1.157 (6) | 0.3907 (14) | 0.056 (3)* | |
C41 | 1.0075 (3) | 0.9009 (5) | 0.39057 (15) | 0.0455 (8) | |
H41A | 1.002 (2) | 0.910 (6) | 0.3516 (14) | 0.056 (3)* | |
H41B | 1.082 (2) | 0.914 (6) | 0.4001 (13) | 0.056 (3)* | |
C51 | 0.9700 (2) | 0.6830 (5) | 0.41096 (12) | 0.0345 (7) | |
H51A | 1.018 (2) | 0.571 (6) | 0.4177 (13) | 0.056 (3)* | |
H51B | 0.915 (2) | 0.631 (6) | 0.3875 (14) | 0.056 (3)* | |
O12 | 0.40979 (14) | 0.8747 (3) | 0.69089 (7) | 0.0362 (5) | |
C22 | 0.4222 (2) | 1.0604 (5) | 0.72818 (13) | 0.0486 (8) | |
H22A | 0.4893 | 1.0978 | 0.7329 | 0.058* | |
H22B | 0.3973 | 1.0242 | 0.7637 | 0.058* | |
C32 | 0.3683 (2) | 1.2484 (5) | 0.70312 (14) | 0.0493 (8) | |
H32A | 0.4079 | 1.3308 | 0.6784 | 0.059* | |
H32B | 0.3460 | 1.3486 | 0.7310 | 0.059* | |
C42 | 0.2835 (2) | 1.1382 (5) | 0.67178 (12) | 0.0362 (7) | |
H42A | 0.260 (2) | 1.233 (6) | 0.6406 (14) | 0.056 (3)* | |
H42B | 0.227 (2) | 1.109 (5) | 0.6949 (14) | 0.056 (3)* | |
C52 | 0.3276 (2) | 0.9221 (6) | 0.65306 (14) | 0.0460 (8) | |
H52A | 0.282 (2) | 0.785 (6) | 0.6541 (13) | 0.056 (3)* | |
H52B | 0.356 (2) | 0.937 (6) | 0.6173 (14) | 0.056 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0185 (3) | 0.0185 (3) | 0.0191 (3) | 0.0003 (2) | −0.0001 (2) | 0.0009 (3) |
O1 | 0.0222 (9) | 0.0229 (9) | 0.0283 (9) | −0.0022 (7) | 0.0002 (7) | 0.0058 (7) |
O3 | 0.0245 (10) | 0.0228 (9) | 0.0346 (10) | −0.0024 (8) | −0.0085 (8) | 0.0095 (8) |
O2 | 0.0235 (10) | 0.0374 (11) | 0.0255 (9) | 0.0031 (8) | 0.0009 (7) | −0.0086 (8) |
P2 | 0.0192 (3) | 0.0171 (3) | 0.0179 (3) | −0.0015 (2) | 0.0009 (2) | 0.0008 (2) |
O4 | 0.0239 (9) | 0.0176 (8) | 0.0210 (8) | −0.0026 (7) | 0.0001 (7) | −0.0002 (7) |
O5 | 0.0275 (10) | 0.0221 (9) | 0.0211 (9) | −0.0038 (7) | −0.0024 (7) | 0.0044 (7) |
O6 | 0.0215 (10) | 0.0205 (9) | 0.0278 (9) | −0.0004 (7) | 0.0035 (7) | 0.0009 (8) |
C1 | 0.0207 (13) | 0.0154 (11) | 0.0204 (11) | −0.0027 (9) | −0.0011 (9) | 0.0017 (9) |
O7 | 0.0248 (9) | 0.0143 (8) | 0.0255 (9) | −0.0045 (7) | −0.0013 (7) | 0.0036 (7) |
C2 | 0.0173 (12) | 0.0188 (12) | 0.0180 (11) | 0.0014 (9) | 0.0012 (9) | −0.0018 (9) |
C4 | 0.0253 (14) | 0.0203 (13) | 0.0206 (12) | 0.0018 (10) | 0.0017 (10) | 0.0009 (10) |
C3 | 0.0188 (13) | 0.0191 (12) | 0.0198 (11) | −0.0002 (10) | −0.0016 (9) | −0.0009 (10) |
C5 | 0.0214 (13) | 0.0259 (13) | 0.0183 (11) | 0.0056 (10) | −0.0021 (9) | 0.0017 (10) |
C7 | 0.0200 (13) | 0.0195 (13) | 0.0257 (12) | −0.0001 (10) | −0.0002 (10) | 0.0000 (10) |
C6 | 0.0228 (14) | 0.0262 (14) | 0.0245 (13) | 0.0001 (10) | −0.0044 (10) | −0.0037 (11) |
N4 | 0.0280 (12) | 0.0348 (13) | 0.0238 (11) | 0.0073 (10) | −0.0017 (9) | 0.0018 (10) |
O41 | 0.0548 (14) | 0.0385 (12) | 0.0476 (12) | −0.0057 (10) | −0.0157 (10) | 0.0221 (10) |
O42 | 0.0449 (13) | 0.0408 (12) | 0.0369 (11) | 0.0041 (10) | −0.0224 (9) | −0.0017 (9) |
O11 | 0.0331 (11) | 0.0223 (9) | 0.0460 (11) | 0.0013 (8) | 0.0138 (9) | 0.0055 (9) |
C21 | 0.0285 (16) | 0.0218 (13) | 0.0386 (15) | 0.0022 (11) | 0.0073 (12) | 0.0028 (12) |
C31 | 0.0418 (18) | 0.0229 (14) | 0.0366 (15) | −0.0010 (12) | 0.0074 (13) | 0.0051 (12) |
C41 | 0.056 (2) | 0.0323 (16) | 0.0501 (19) | 0.0049 (15) | 0.0281 (17) | 0.0074 (15) |
C51 | 0.0374 (17) | 0.0265 (15) | 0.0401 (16) | 0.0046 (13) | 0.0095 (13) | −0.0020 (13) |
O12 | 0.0362 (11) | 0.0425 (12) | 0.0299 (10) | 0.0092 (9) | 0.0022 (8) | −0.0086 (9) |
C22 | 0.051 (2) | 0.053 (2) | 0.0412 (17) | 0.0139 (16) | −0.0081 (15) | −0.0182 (16) |
C32 | 0.052 (2) | 0.0384 (17) | 0.057 (2) | 0.0014 (15) | −0.0035 (16) | −0.0036 (16) |
C42 | 0.0321 (17) | 0.0438 (18) | 0.0330 (15) | 0.0031 (13) | 0.0044 (12) | 0.0024 (13) |
C52 | 0.0305 (18) | 0.059 (2) | 0.0477 (19) | 0.0105 (15) | −0.0053 (14) | −0.0160 (17) |
P1—O1 | 1.5034 (17) | N4—O42 | 1.247 (3) |
P1—O2 | 1.5637 (18) | O11—C21 | 1.461 (3) |
P1—O3 | 1.5553 (18) | O11—C51 | 1.469 (3) |
P1—C1 | 1.889 (2) | C21—C31 | 1.542 (4) |
O2—H21 | 0.87 (4) | C21—H21A | 0.95 (3) |
O3—H31 | 0.80 (4) | C21—H21B | 0.99 (3) |
P2—O4 | 1.5044 (16) | C31—C41 | 1.551 (4) |
P2—O5 | 1.5615 (17) | C31—H31A | 1.03 (3) |
P2—O6 | 1.5881 (18) | C31—H31B | 0.98 (3) |
P2—C1 | 1.870 (2) | C41—C51 | 1.505 (4) |
O5—H51 | 0.94 (4) | C41—H41A | 0.95 (3) |
O6—H61 | 0.84 (4) | C41—H41B | 1.06 (3) |
C1—O7 | 1.452 (3) | C51—H51A | 0.96 (3) |
C1—C2 | 1.540 (3) | C51—H51B | 0.99 (3) |
O7—H71 | 0.86 (4) | O12—C22 | 1.450 (3) |
C2—C7 | 1.412 (3) | O12—C52 | 1.480 (3) |
C2—C3 | 1.414 (3) | C22—C32 | 1.481 (4) |
C4—C3 | 1.402 (3) | C22—H22A | 0.9700 |
C4—C5 | 1.403 (3) | C22—H22B | 0.9700 |
C4—H4 | 0.93 (3) | C32—C42 | 1.543 (4) |
C3—H3 | 0.96 (3) | C32—H32A | 0.9700 |
C5—C6 | 1.392 (4) | C32—H32B | 0.9700 |
C5—N4 | 1.487 (3) | C42—C52 | 1.518 (4) |
C7—C6 | 1.401 (3) | C42—H42A | 1.00 (3) |
C7—H7 | 0.96 (3) | C42—H42B | 1.00 (3) |
C6—H6 | 0.92 (3) | C52—H52A | 1.04 (3) |
N4—O41 | 1.232 (3) | C52—H52B | 0.98 (3) |
O1—P1—O3 | 113.91 (10) | C31—C21—H21A | 117 (2) |
O1—P1—O2 | 114.19 (10) | O11—C21—H21B | 108.5 (19) |
O3—P1—O2 | 108.57 (10) | C31—C21—H21B | 114.6 (19) |
O1—P1—C1 | 113.97 (10) | H21A—C21—H21B | 106 (3) |
O3—P1—C1 | 103.91 (10) | C21—C31—C41 | 106.1 (2) |
O2—P1—C1 | 101.07 (10) | C21—C31—H31A | 112.8 (18) |
P1—O3—H31 | 118 (3) | C41—C31—H31A | 106.1 (18) |
P1—O2—H21 | 116 (2) | C21—C31—H31B | 110 (2) |
O4—P2—O5 | 114.76 (9) | C41—C31—H31B | 110.9 (19) |
O4—P2—O6 | 112.19 (9) | H31A—C31—H31B | 111 (3) |
O5—P2—O6 | 106.88 (10) | C51—C41—C31 | 104.7 (2) |
O4—P2—C1 | 112.24 (10) | C51—C41—H41A | 111 (2) |
O5—P2—C1 | 105.40 (10) | C31—C41—H41A | 111 (2) |
O6—P2—C1 | 104.60 (10) | C51—C41—H41B | 109.9 (18) |
P2—O5—H51 | 113 (2) | C31—C41—H41B | 114.6 (18) |
P2—O6—H61 | 119 (3) | H41A—C41—H41B | 105 (3) |
O7—C1—C2 | 107.74 (18) | O11—C51—C41 | 106.0 (2) |
O7—C1—P2 | 106.02 (14) | O11—C51—H51A | 108 (2) |
C2—C1—P2 | 109.34 (15) | C41—C51—H51A | 115 (2) |
O7—C1—P1 | 109.55 (15) | O11—C51—H51B | 102.3 (19) |
C2—C1—P1 | 109.03 (15) | C41—C51—H51B | 111.0 (19) |
P2—C1—P1 | 114.92 (12) | H51A—C51—H51B | 113 (3) |
C1—O7—H71 | 108 (2) | C22—O12—C52 | 108.6 (2) |
C7—C2—C3 | 119.9 (2) | O12—C22—C32 | 106.4 (2) |
C7—C2—C1 | 120.4 (2) | O12—C22—H22A | 110.5 |
C3—C2—C1 | 119.7 (2) | C32—C22—H22A | 110.5 |
C3—C4—C5 | 118.8 (2) | O12—C22—H22B | 110.5 |
C3—C4—H4 | 118.9 (17) | C32—C22—H22B | 110.5 |
C5—C4—H4 | 122.2 (17) | H22A—C22—H22B | 108.6 |
C4—C3—C2 | 119.7 (2) | C22—C32—C42 | 104.4 (3) |
C4—C3—H3 | 120.6 (16) | C22—C32—H32A | 110.9 |
C2—C3—H3 | 119.7 (16) | C42—C32—H32A | 110.9 |
C6—C5—C4 | 122.8 (2) | C22—C32—H32B | 110.9 |
C6—C5—N4 | 118.0 (2) | C42—C32—H32B | 110.9 |
C4—C5—N4 | 119.3 (2) | H32A—C32—H32B | 108.9 |
C6—C7—C2 | 120.7 (2) | C52—C42—C32 | 101.8 (2) |
C6—C7—H7 | 119.9 (16) | C52—C42—H42A | 112.8 (19) |
C2—C7—H7 | 119.4 (16) | C32—C42—H42A | 111.1 (19) |
C5—C6—C7 | 118.1 (2) | C52—C42—H42B | 110.9 (19) |
C5—C6—H6 | 121.2 (17) | C32—C42—H42B | 113.6 (19) |
C7—C6—H6 | 120.6 (17) | H42A—C42—H42B | 107 (3) |
O41—N4—O42 | 123.3 (2) | O12—C52—C42 | 107.0 (2) |
O41—N4—C5 | 118.3 (2) | O12—C52—H52A | 107.3 (18) |
O42—N4—C5 | 118.4 (2) | C42—C52—H52A | 114.5 (19) |
C21—O11—C51 | 107.6 (2) | O12—C52—H52B | 104 (2) |
O11—C21—C31 | 105.0 (2) | C42—C52—H52B | 112 (2) |
O11—C21—H21A | 106 (2) | H52A—C52—H52B | 111 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O12 | 0.87 (4) | 1.73 (3) | 2.594 (3) | 173 (3) |
O3—H31···O4i | 0.80 (4) | 1.85 (3) | 2.645 (3) | 175 (4) |
O5—H51···O1i | 0.94 (4) | 1.63 (3) | 2.564 (3) | 171 (4) |
O6—H61···O11 | 0.84 (4) | 1.74 (3) | 2.579 (3) | 174 (4) |
O7—H71···O4ii | 0.86 (4) | 2.21 (3) | 2.981 (3) | 150 (3) |
O7—H71···O3 | 0.86 (4) | 2.51 (3) | 2.993 (3) | 117 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z. |
Experimental details
(IIIa) | (IIIb) | |
Crystal data | ||
Chemical formula | C7H10O7P2·H2O | C7H9NO9P2·2C4H8O |
Mr | 286.10 | 457.30 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/c |
Temperature (K) | 293 | 132 |
a, b, c (Å) | 8.42 (2), 23.05 (1), 5.91 (2) | 14.0005 (9), 6.0243 (2), 24.4427 (6) |
β (°) | 97.7 (2) | 91.903 (3) |
V (Å3) | 1137 (6) | 2060.44 (16) |
Z | 4 | 4 |
Radiation type | Cu Kα | Mo Kα |
µ (mm−1) | 3.81 | 0.27 |
Crystal size (mm) | 0.5 × 0.2 × 0.2 | 0.20 × 0.20 × 0.05 |
Data collection | ||
Diffractometer | Philips PW 1100 diffractometer | Nonius KappaCCD are-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3430, 3430, 2875 | 3734, 3734, 2986 |
Rint | 0.000 | 0.000 |
(sin θ/λ)max (Å−1) | 0.591 | 0.605 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.096, 1.12 | 0.045, 0.096, 1.02 |
No. of reflections | 3430 | 3734 |
No. of parameters | 311 | 329 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.27, −0.29 | 0.39, −0.37 |
Absolute structure | Flack (1983), with 1421 Friedel pairs | ? |
Absolute structure parameter | 0.18 (5) | ? |
Computer programs: PHIL (local program; author, 1980), KappaCCD Server Software (Nonius, 1997), PARAM (local program; author, 1995), DENZO-SMN (Otwinowsky & Minor, 1997), PHIL, DENZO-SMN, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97 and PLATON.
P1—O1 | 1.502 (6) | P1'—O1' | 1.520 (7) |
P1—O2 | 1.554 (5) | P1'—O2' | 1.511 (5) |
P1—O3 | 1.539 (6) | P1'—O3' | 1.527 (6) |
P1—C1 | 1.824 (5) | P1'—C1' | 1.866 (5) |
P2—O4 | 1.497 (7) | P2'—O4' | 1.478 (7) |
P2—O5 | 1.552 (6) | P2'—O5' | 1.547 (6) |
P2—O6 | 1.558 (4) | P2'—O6' | 1.561 (4) |
P2—C1 | 1.840 (7) | P2'—C1' | 1.836 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O1'i | 0.82 | 1.92 | 2.583 (9) | 137 |
O2'—H2P···O1ii | 0.82 | 1.80 | 2.602 (9) | 164 |
O3—H31···O4' | 0.82 | 1.78 | 2.592 (9) | 169 |
O3'—H3P···O4 | 0.82 | 1.75 | 2.549 (9) | 165 |
O5—H51···O1' | 0.82 | 1.84 | 2.647 (9) | 169 |
O5'—H5P···O1 | 0.82 | 1.83 | 2.637 (9) | 167 |
O6—H61···O2W | 0.82 | 1.83 | 2.609 (9) | 160 |
O6'—H6P···O1W | 0.82 | 1.80 | 2.594 (9) | 163 |
O7—H71···O4iii | 0.82 | 2.07 | 2.805 (9) | 149 |
O7—H71···O3 | 0.82 | 2.36 | 2.894 (10) | 123 |
O7'—H72···O4'iv | 0.82 | 2.12 | 2.789 (9) | 138 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, y, z−1; (iv) x, y, z+1. |
P1—O1 | 1.5034 (17) | P2—O4 | 1.5044 (16) |
P1—O2 | 1.5637 (18) | P2—O5 | 1.5615 (17) |
P1—O3 | 1.5553 (18) | P2—O6 | 1.5881 (18) |
P1—C1 | 1.889 (2) | P2—C1 | 1.870 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O12 | 0.87 (4) | 1.73 (3) | 2.594 (3) | 173 (3) |
O3—H31···O4i | 0.80 (4) | 1.85 (3) | 2.645 (3) | 175 (4) |
O5—H51···O1i | 0.94 (4) | 1.63 (3) | 2.564 (3) | 171 (4) |
O6—H61···O11 | 0.84 (4) | 1.74 (3) | 2.579 (3) | 174 (4) |
O7—H71···O4ii | 0.86 (4) | 2.21 (3) | 2.981 (3) | 150 (3) |
O7—H71···O3 | 0.86 (4) | 2.51 (3) | 2.993 (3) | 117 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z. |
Bisphosphonates belong to a relatively new class of drugs developed for the treatment of various pathologies in bone (Fleisch, 1999), but also for the treatment of cancer (Mundy, 1999; Brown & Coleman, 2002). We have previously described a one-pot method for the synthesis of aromatic 1-hydroxymethane-1,1-bisphosphonic acid compounds (Lecouvey et al., 2001). The aim of this paper is to analyze the structure of two new 1-hydroxymethane-1,1-bisphosphonic acids, hydroxy(phenyl)methylene]diphosphonic acid monohydrate, (IIIa), and [hydroxy(4-nitrophenyl)methylene]diphosphonic acid tetrahydrofuran disolvate, (IIIb), with an aromatic ring attached to the functional C atom. These crystallographic structures were also investigated to confirm the presence of the bisphosphonic acid group, because of a possible phosphono-phosphate rearrangement as a by-product of the synthesis, as previously mentioned by Fitch & Moedritzer (1962) and Kanaan & Burgada (1988). \sch
Hydroxy bisphosphonic acids are compounds with superacid properties, and they are able to complex with a large number of cations. As such, they have been widely investigated as detoxifying agents in heavy metal poisoning and also as carrier molecules for 99mTc delivery in scintillography. They are very difficult to crystallize as free dehydrated acids and only one example has been reported for the crystal structure of an anhydro hydroxybisphosphonic compound (Ohanessian et al., 1997). These acids are more easily crystallized as mono salts of sodium or potassium (Sylvestre et al., 2001), or better, dimethylammonium salts using the vapour-diffusion technique (Neuman et al., 2002). When crystals are obtained, they generally include solvent, to give well characterized solvates, as is the case for the two title compounds, (IIIa) and (IIIb).
Although (IIIa) is a racemic monohydrate, it crystallizes in the non-centrosymmetric space group P21 with the two (+) and (-) enantiomers facing each other, building a tight dimer around a local non-crystallographic centre of symmetry at (x,y,z) = (0.609, 0.255, 0.354). The content of the asymmetric unit corresponds to two molecules of (IIIa) and two molecules of water. The centrosymmetry is only broken by the hydration network.
Phosphonic acids are usually diprotonated in their free acid form. In (IIIa), the phosphonic H atoms are observed but not those of the two water molecules (Fig. 1); these are probably in a disordered exchange within the hydrogen-bond network. Nevertheless, O1W is 3.02 Å away from the symmetry-related O2W and is certainly hydrogen-bonded to it.
Details of the four hydrogen bonds responsible for the pairing are given in Table 2. In addition, infinite intermolecular hydrogen-bond networks are present along the a and c directions. Firstly, dimers are connected side by side to build infinite ribbons along the c direction (Fig. 2), and secondly, these ribbons are cross-linked perpendicularly (along a) through their O2—O1' and O2'-O1 atoms. The most significant distances are given in Table 2.
The crystals of (IIIb) are less stable than those of (IIIa), with a tendency to bleach and turn to powder upon standing in air at room temperature. The data were therefore recorded at 132 K. The structure is a tetrahydrofuran disolvate which crystallizes in the P21/c space group (Fig. 3). The bishydroxy phosphonate molecules also form strong dimers, linked by four hydrogen bonds as in (IIIa). However, the local centre of inversion in the dimer corresponds to a crystallographic centre of symmetry of the space group. All the phosphonic acid H atoms were located in difference maps. In (IIIb), the hydrogen-bond network also involves dimers, to build β-sheet-like ribbons (Fig. 4) similar to those observed in (IIIa) but running along the b axis. The two solvated tetrahydrofuran molecules form part of the network through their O ring atoms (Fig. 3). They connect locally the phosphonate O atoms that are not involved in the pairing (O2 and O6; Table 4). In a similar way, molecules of water connect the dimers in (IIIa). However, the tetrahydrofuran molecules are more bulky than the water molecules and fill more space between the ribbons, preventing them from coming close enough for cross-linking. This leads to weaker crystal cohesion in the direction perpendicular to the ribbons.