Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110051425/gz3188sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110051425/gz3188Isup2.hkl |
CCDC reference: 813471
For related literature, see: Alberti et al. (1996); Allen (2002); Bernstein et al. (1995); Cao et al. (1992); Clearfield (1998); Hirao et al. (1981); Li et al. (2008); Svoboda et al. (2005, 2008); Zima et al. (2007, 2009).
All chemicals were obtained commercially, with the exception of 4-carboxyphenylphosphonic acid, which was prepared according to the published procedure of Hirao et al. (1981). The title compound was synthesized by mixing 4-carboxyphenylphosphonic acid (30 mg, 0.15 mmol) dissolved in diethylamine (20 µl) and ethanol (1 ml) with cobalt(II) chloride (19 mg, 0.15 mmol) dissolved in ethanol (0.5 ml). A navy-blue solution was obtained and this was kept at room temperature to allow slow evaporation of the solvent. After one week, pink parallelepiped crystals of (I) of sufficient quality for X-ray diffraction measurements were obtained.
Spectroscopic analysis, FT–IR (KBr, cm-1). Internal vibrations of the functional groups: νC═O 1687 (vs), 1628 (sh); δ(C)O—H and νC—OH 1427 (s), 1400 (m), 1375 (m), 1323 (s); νPO3 1172 (s, sh), 1143 (vs), 1115 (vs), 1090 (m, sh), 1029 (vs), 1013. PO3 deformation vibrations: 580 (s, n), 546 (s, n), 518 (s, n), 460 (s, n), 448 (s, n). νOH of the hydrogen bonds: strong absorption in the region 3600–1800 cm-1, with maxima at 3530 (s, b), 3408 (b, vs), 3095 (vb, vs), 2995 (vb, vs), 2895 (vb, vs), 2840 (vb, vs), 2676 (s, b), 2560 (s, b). Internal vibrations of the aromatic ring: νC—C 1560 (m, n), 1503 (vw), 1471 (vw). Out-of-plane ring deformations: 862 (m, n), 819 (w), 805 (w), 632 (w). Ring torsions 767 (m), 719 (n, vs), 646 (s, n).
Difference Fourier map plots showed a prolate shaped peak between O12 and O22 and while a two H-atom disorder model for this site was considered it was decided that nothing significant would obtained by doing so; the maximum was labelled as H22O and assigned unit occupancy. That position and those of the other H atoms bonded to O atoms, also located from difference Fourier maps, were refined with Uiso(H) = 1.5Ueq(O). The H atoms of the aromatic rings were located in geometric positions and refined as rigid, with C—H = 0.93 Å [Please check added text] and with Uiso(H) = 1.2Ueq(C).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
[Co(H2O)6](C14H13O10P2)2·2H2O | F(000) = 1042 |
Mr = 1009.43 | Dx = 1.654 Mg m−3 Dm = 1.65 Mg m−3 Dm measured by flotation |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1265 reflections |
a = 21.053 (4) Å | θ = 3.0–28.5° |
b = 7.2030 (14) Å | µ = 0.68 mm−1 |
c = 13.370 (3) Å | T = 295 K |
β = 92.00 (1)° | Parallelepiped, pink |
V = 2026.3 (7) Å3 | 0.36 × 0.22 × 0.17 mm |
Z = 2 |
Kuma KM-4 diffractometer with a CCD area detector | 5087 independent reflections |
Radiation source: fine-focus sealed tube | 3294 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 28.5°, θmin = 3.0° |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | h = −28→27 |
Tmin = 0.843, Tmax = 0.899 | k = −9→9 |
26924 measured reflections | l = −16→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0351P)2] where P = (Fo2 + 2Fc2)/3 |
5087 reflections | (Δ/σ)max = 0.001 |
316 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
[Co(H2O)6](C14H13O10P2)2·2H2O | V = 2026.3 (7) Å3 |
Mr = 1009.43 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 21.053 (4) Å | µ = 0.68 mm−1 |
b = 7.2030 (14) Å | T = 295 K |
c = 13.370 (3) Å | 0.36 × 0.22 × 0.17 mm |
β = 92.00 (1)° |
Kuma KM-4 diffractometer with a CCD area detector | 5087 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | 3294 reflections with I > 2σ(I) |
Tmin = 0.843, Tmax = 0.899 | Rint = 0.052 |
26924 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.29 e Å−3 |
5087 reflections | Δρmin = −0.28 e Å−3 |
316 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 | ||
Co1 | 0.5000 | 0.5000 | 0.0000 | 0.02365 (10) | |
O1W | 0.47427 (7) | 0.36143 (19) | 0.13082 (11) | 0.0305 (3) | |
H1W1 | 0.4897 (10) | 0.259 (3) | 0.1399 (16) | 0.046* | |
H2W1 | 0.4372 (11) | 0.345 (3) | 0.1348 (16) | 0.046* | |
O2W | 0.41584 (7) | 0.4247 (2) | −0.07416 (12) | 0.0394 (4) | |
H1W2 | 0.3963 (11) | 0.492 (3) | −0.1234 (17) | 0.059* | |
H2W2 | 0.3900 (12) | 0.363 (3) | −0.0524 (19) | 0.059* | |
O3W | 0.54242 (8) | 0.2570 (2) | −0.04936 (13) | 0.0452 (4) | |
H1W3 | 0.5250 (13) | 0.179 (3) | −0.083 (2) | 0.068* | |
H2W3 | 0.5766 (12) | 0.216 (4) | −0.0402 (19) | 0.068* | |
O4W | 0.48215 (7) | 0.5071 (2) | 0.33196 (11) | 0.0358 (3) | |
H1W4 | 0.4416 (11) | 0.519 (3) | 0.3385 (17) | 0.054* | |
H2W4 | 0.4847 (11) | 0.474 (3) | 0.2752 (18) | 0.054* | |
P11 | 0.31695 (2) | 0.69294 (6) | 0.30785 (3) | 0.02222 (12) | |
O11 | 0.35444 (6) | 0.86621 (17) | 0.29064 (9) | 0.0280 (3) | |
O12 | 0.35542 (6) | 0.55568 (18) | 0.37189 (9) | 0.0327 (3) | |
O13 | 0.29499 (6) | 0.60691 (18) | 0.20704 (10) | 0.0323 (3) | |
H13O | 0.3155 (10) | 0.517 (3) | 0.1837 (16) | 0.048* | |
C11 | 0.24504 (8) | 0.7412 (2) | 0.37050 (13) | 0.0247 (4) | |
C12 | 0.24889 (9) | 0.8279 (3) | 0.46344 (14) | 0.0321 (5) | |
H12 | 0.2882 | 0.8653 | 0.4901 | 0.038* | |
C13 | 0.19492 (9) | 0.8591 (3) | 0.51634 (14) | 0.0333 (5) | |
H13 | 0.1977 | 0.9186 | 0.5781 | 0.040* | |
C14 | 0.13641 (9) | 0.8013 (3) | 0.47719 (15) | 0.0305 (5) | |
C15 | 0.13251 (9) | 0.7165 (3) | 0.38461 (15) | 0.0365 (5) | |
H15 | 0.0932 | 0.6792 | 0.3580 | 0.044* | |
C16 | 0.18640 (9) | 0.6865 (3) | 0.33120 (15) | 0.0324 (5) | |
H16 | 0.1833 | 0.6296 | 0.2688 | 0.039* | |
C17 | 0.07912 (10) | 0.8249 (3) | 0.53689 (16) | 0.0384 (5) | |
O14 | 0.08327 (7) | 0.8922 (2) | 0.62222 (11) | 0.0526 (4) | |
O15 | 0.02712 (8) | 0.7693 (3) | 0.49572 (13) | 0.0675 (6) | |
H15O | −0.0055 (15) | 0.768 (4) | 0.536 (2) | 0.101* | |
P21 | 0.31449 (2) | 0.33522 (6) | 0.58978 (3) | 0.02246 (12) | |
O21 | 0.34907 (6) | 0.16758 (17) | 0.62947 (11) | 0.0385 (4) | |
O22 | 0.30471 (7) | 0.32769 (17) | 0.47738 (9) | 0.0336 (3) | |
H22O | 0.3268 (10) | 0.438 (3) | 0.4289 (15) | 0.050* | |
O23 | 0.35217 (6) | 0.51426 (18) | 0.61278 (10) | 0.0328 (3) | |
H23O | 0.3562 (11) | 0.546 (3) | 0.6703 (16) | 0.049* | |
C21 | 0.23998 (8) | 0.3441 (2) | 0.64937 (13) | 0.0230 (4) | |
C22 | 0.24019 (9) | 0.3130 (2) | 0.75132 (13) | 0.0263 (4) | |
H22 | 0.2785 | 0.2921 | 0.7863 | 0.032* | |
C23 | 0.18423 (9) | 0.3126 (3) | 0.80159 (14) | 0.0308 (5) | |
H23 | 0.1847 | 0.2900 | 0.8701 | 0.037* | |
C24 | 0.12741 (9) | 0.3460 (3) | 0.74981 (14) | 0.0297 (4) | |
C25 | 0.12665 (9) | 0.3784 (3) | 0.64868 (15) | 0.0361 (5) | |
H25 | 0.0883 | 0.4010 | 0.6143 | 0.043* | |
C26 | 0.18278 (9) | 0.3775 (3) | 0.59750 (15) | 0.0324 (5) | |
H26 | 0.1822 | 0.3992 | 0.5289 | 0.039* | |
C27 | 0.06846 (10) | 0.3432 (3) | 0.80791 (17) | 0.0381 (5) | |
O24 | 0.07132 (7) | 0.2848 (2) | 0.89525 (12) | 0.0583 (5) | |
O25 | 0.01789 (7) | 0.4040 (3) | 0.76446 (13) | 0.0590 (5) | |
H25O | −0.0115 (13) | 0.401 (4) | 0.806 (2) | 0.088* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01961 (19) | 0.0257 (2) | 0.0256 (2) | 0.00138 (15) | 0.00114 (15) | 0.00295 (15) |
O1W | 0.0227 (7) | 0.0341 (8) | 0.0348 (8) | 0.0010 (6) | 0.0035 (7) | 0.0054 (6) |
O2W | 0.0283 (8) | 0.0481 (9) | 0.0412 (9) | −0.0102 (7) | −0.0080 (7) | 0.0198 (7) |
O3W | 0.0340 (9) | 0.0422 (9) | 0.0592 (11) | 0.0112 (7) | −0.0018 (8) | −0.0147 (7) |
O4W | 0.0294 (7) | 0.0405 (8) | 0.0377 (9) | 0.0000 (7) | 0.0023 (7) | −0.0034 (7) |
P11 | 0.0216 (3) | 0.0255 (3) | 0.0197 (3) | 0.00267 (19) | 0.0033 (2) | 0.00198 (19) |
O11 | 0.0280 (7) | 0.0324 (7) | 0.0237 (7) | −0.0036 (6) | 0.0011 (6) | 0.0008 (5) |
O12 | 0.0241 (7) | 0.0407 (8) | 0.0338 (8) | 0.0079 (6) | 0.0087 (6) | 0.0163 (6) |
O13 | 0.0340 (8) | 0.0331 (8) | 0.0297 (8) | 0.0049 (6) | 0.0002 (6) | −0.0105 (6) |
C11 | 0.0221 (10) | 0.0287 (10) | 0.0235 (10) | 0.0037 (8) | 0.0042 (8) | 0.0022 (8) |
C12 | 0.0241 (11) | 0.0441 (12) | 0.0282 (11) | −0.0023 (9) | 0.0032 (9) | −0.0055 (9) |
C13 | 0.0322 (11) | 0.0416 (12) | 0.0266 (11) | 0.0026 (9) | 0.0069 (9) | −0.0077 (9) |
C14 | 0.0216 (10) | 0.0388 (11) | 0.0315 (11) | 0.0025 (8) | 0.0068 (9) | 0.0018 (8) |
C15 | 0.0217 (11) | 0.0524 (13) | 0.0354 (12) | −0.0008 (9) | 0.0008 (9) | −0.0064 (10) |
C16 | 0.0255 (11) | 0.0451 (12) | 0.0267 (11) | −0.0021 (9) | 0.0021 (9) | −0.0072 (9) |
C17 | 0.0263 (12) | 0.0521 (14) | 0.0372 (13) | 0.0003 (10) | 0.0057 (10) | 0.0005 (10) |
O14 | 0.0332 (9) | 0.0873 (12) | 0.0380 (9) | −0.0013 (8) | 0.0120 (7) | −0.0176 (8) |
O15 | 0.0254 (9) | 0.1235 (16) | 0.0545 (12) | −0.0084 (10) | 0.0154 (8) | −0.0274 (11) |
P21 | 0.0232 (3) | 0.0233 (2) | 0.0214 (3) | −0.00051 (19) | 0.0079 (2) | 0.00185 (19) |
O21 | 0.0256 (8) | 0.0348 (8) | 0.0563 (10) | 0.0047 (6) | 0.0168 (7) | 0.0186 (7) |
O22 | 0.0443 (9) | 0.0361 (8) | 0.0209 (7) | −0.0142 (6) | 0.0083 (6) | −0.0011 (6) |
O23 | 0.0375 (8) | 0.0384 (8) | 0.0232 (7) | −0.0123 (6) | 0.0106 (7) | −0.0082 (6) |
C21 | 0.0251 (10) | 0.0225 (9) | 0.0219 (10) | −0.0003 (7) | 0.0069 (8) | 0.0009 (7) |
C22 | 0.0212 (10) | 0.0329 (10) | 0.0249 (10) | 0.0013 (8) | 0.0015 (8) | 0.0030 (8) |
C23 | 0.0310 (11) | 0.0378 (11) | 0.0241 (11) | −0.0028 (9) | 0.0093 (9) | 0.0028 (8) |
C24 | 0.0243 (10) | 0.0328 (11) | 0.0324 (11) | 0.0005 (8) | 0.0088 (9) | −0.0018 (8) |
C25 | 0.0254 (11) | 0.0455 (12) | 0.0374 (13) | 0.0043 (9) | −0.0002 (9) | 0.0007 (9) |
C26 | 0.0292 (11) | 0.0450 (12) | 0.0233 (10) | 0.0042 (9) | 0.0045 (9) | 0.0056 (9) |
C27 | 0.0260 (12) | 0.0469 (13) | 0.0419 (13) | 0.0007 (9) | 0.0098 (10) | 0.0022 (10) |
O24 | 0.0313 (9) | 0.1004 (13) | 0.0442 (10) | 0.0015 (9) | 0.0153 (7) | 0.0184 (9) |
O25 | 0.0269 (9) | 0.0986 (14) | 0.0522 (11) | 0.0101 (9) | 0.0135 (8) | 0.0107 (10) |
Co1—O2Wi | 2.0722 (15) | C14—C17 | 1.479 (3) |
Co1—O2W | 2.0722 (15) | C15—C16 | 1.378 (3) |
Co1—O3Wi | 2.0828 (15) | C15—H15 | 0.9300 |
Co1—O3W | 2.0828 (15) | C16—H16 | 0.9300 |
Co1—O1W | 2.1012 (14) | C17—O14 | 1.240 (2) |
Co1—O1Wi | 2.1012 (14) | C17—O15 | 1.273 (3) |
O1W—H1W1 | 0.81 (2) | O15—H15O | 0.89 (3) |
O1W—H2W1 | 0.79 (2) | P21—O21 | 1.4975 (13) |
O2W—H1W2 | 0.91 (2) | P21—O22 | 1.5107 (13) |
O2W—H2W2 | 0.77 (2) | P21—O23 | 1.5394 (14) |
O3W—H1W3 | 0.80 (3) | P21—C21 | 1.7852 (19) |
O3W—H2W3 | 0.78 (3) | O22—H22O | 1.14 (2) |
O4W—H1W4 | 0.86 (2) | O23—H23O | 0.80 (2) |
O4W—H2W4 | 0.80 (2) | C21—C22 | 1.381 (2) |
P11—O11 | 1.4988 (13) | C21—C26 | 1.389 (3) |
P11—O12 | 1.5225 (13) | C22—C23 | 1.377 (2) |
P11—O13 | 1.5398 (14) | C22—H22 | 0.9300 |
P11—C11 | 1.7896 (19) | C23—C24 | 1.382 (3) |
O12—H22O | 1.30 (2) | C23—H23 | 0.9300 |
O13—H13O | 0.84 (2) | C24—C25 | 1.372 (3) |
C11—C16 | 1.382 (3) | C24—C27 | 1.487 (3) |
C11—C12 | 1.391 (2) | C25—C26 | 1.386 (3) |
C12—C13 | 1.378 (3) | C25—H25 | 0.9300 |
C12—H12 | 0.9300 | C26—H26 | 0.9300 |
C13—C14 | 1.385 (3) | C27—O24 | 1.241 (2) |
C13—H13 | 0.9300 | C27—O25 | 1.273 (3) |
C14—C15 | 1.380 (3) | O25—H25O | 0.84 (3) |
O2Wi—Co1—O2W | 180.00 (10) | C15—C14—C17 | 120.71 (18) |
O2Wi—Co1—O3Wi | 89.85 (7) | C13—C14—C17 | 119.52 (18) |
O2W—Co1—O3Wi | 90.15 (7) | C16—C15—C14 | 120.63 (19) |
O2Wi—Co1—O3W | 90.15 (7) | C16—C15—H15 | 119.7 |
O2W—Co1—O3W | 89.85 (7) | C14—C15—H15 | 119.7 |
O3Wi—Co1—O3W | 180.00 (12) | C15—C16—C11 | 119.93 (18) |
O2Wi—Co1—O1W | 88.11 (6) | C15—C16—H16 | 120.0 |
O2W—Co1—O1W | 91.89 (6) | C11—C16—H16 | 120.0 |
O3Wi—Co1—O1W | 90.55 (7) | O14—C17—O15 | 123.57 (19) |
O3W—Co1—O1W | 89.45 (7) | O14—C17—C14 | 120.59 (19) |
O2Wi—Co1—O1Wi | 91.89 (6) | O15—C17—C14 | 115.84 (19) |
O2W—Co1—O1Wi | 88.11 (6) | C17—O15—H15O | 114 (2) |
O3Wi—Co1—O1Wi | 89.45 (7) | O21—P21—O22 | 111.79 (8) |
O3W—Co1—O1Wi | 90.55 (7) | O21—P21—O23 | 111.35 (8) |
O1W—Co1—O1Wi | 180.00 (8) | O22—P21—O23 | 106.27 (7) |
Co1—O1W—H1W1 | 116.2 (15) | O21—P21—C21 | 107.13 (8) |
Co1—O1W—H2W1 | 114.1 (16) | O22—P21—C21 | 110.72 (9) |
H1W1—O1W—H2W1 | 104 (2) | O23—P21—C21 | 109.61 (8) |
Co1—O2W—H1W2 | 124.4 (14) | P21—O22—H22O | 119.8 (10) |
Co1—O2W—H2W2 | 125.1 (19) | P21—O23—H23O | 117.9 (16) |
H1W2—O2W—H2W2 | 106 (2) | C22—C21—C26 | 119.57 (17) |
Co1—O3W—H1W3 | 124.9 (19) | C22—C21—P21 | 117.51 (14) |
Co1—O3W—H2W3 | 132 (2) | C26—C21—P21 | 122.91 (14) |
H1W3—O3W—H2W3 | 103 (3) | C23—C22—C21 | 120.58 (17) |
H1W4—O4W—H2W4 | 103 (2) | C23—C22—H22 | 119.7 |
O11—P11—O12 | 110.76 (8) | C21—C22—H22 | 119.7 |
O11—P11—O13 | 110.14 (7) | C22—C23—C24 | 119.72 (18) |
O12—P11—O13 | 111.62 (8) | C22—C23—H23 | 120.1 |
O11—P11—C11 | 111.64 (8) | C24—C23—H23 | 120.1 |
O12—P11—C11 | 107.75 (8) | C25—C24—C23 | 120.22 (17) |
O13—P11—C11 | 104.77 (8) | C25—C24—C27 | 122.42 (19) |
P11—O12—H22O | 120.3 (9) | C23—C24—C27 | 117.36 (18) |
P11—O13—H13O | 119.4 (15) | C24—C25—C26 | 120.35 (19) |
C16—C11—C12 | 119.42 (17) | C24—C25—H25 | 119.8 |
C16—C11—P11 | 121.71 (14) | C26—C25—H25 | 119.8 |
C12—C11—P11 | 118.79 (14) | C25—C26—C21 | 119.56 (18) |
C13—C12—C11 | 120.56 (18) | C25—C26—H26 | 120.2 |
C13—C12—H12 | 119.7 | C21—C26—H26 | 120.2 |
C11—C12—H12 | 119.7 | O24—C27—O25 | 123.97 (19) |
C12—C13—C14 | 119.71 (18) | O24—C27—C24 | 118.83 (19) |
C12—C13—H13 | 120.1 | O25—C27—C24 | 117.2 (2) |
C14—C13—H13 | 120.1 | C27—O25—H25O | 108 (2) |
C15—C14—C13 | 119.73 (18) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O4Wii | 0.81 (2) | 1.94 (2) | 2.752 (2) | 174 (2) |
O1W—H2W1···O21iii | 0.79 (2) | 1.86 (2) | 2.644 (2) | 172 (2) |
O2W—H1W2···O11iv | 0.91 (2) | 1.75 (2) | 2.654 (2) | 174 (2) |
O2W—H2W2···O22iii | 0.77 (2) | 2.31 (2) | 3.060 (2) | 168 (3) |
O2W—H2W2···O21iii | 0.77 (2) | 2.62 (2) | 3.178 (2) | 131 (2) |
O3W—H1W3···O4Wiii | 0.80 (3) | 1.96 (3) | 2.758 (2) | 179 (3) |
O3W—H2W3···O23ii | 0.78 (3) | 2.33 (3) | 2.972 (2) | 141 (2) |
O4W—H1W4···O12 | 0.86 (2) | 1.90 (2) | 2.761 (2) | 172 (2) |
O4W—H2W4···O1W | 0.80 (2) | 2.10 (2) | 2.886 (2) | 169 (2) |
O22—H22O···O12 | 1.14 (2) | 1.30 (2) | 2.435 (2) | 176 (2) |
O13—H13O···O21iii | 0.84 (2) | 1.68 (2) | 2.523 (2) | 174 (2) |
O15—H15O···O24v | 0.89 (3) | 1.69 (3) | 2.578 (2) | 173 (3) |
O23—H23O···O11vi | 0.80 (2) | 1.73 (2) | 2.528 (2) | 171 (2) |
O25—H25O···O14vii | 0.84 (3) | 1.82 (3) | 2.658 (2) | 171 (3) |
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) x, −y+3/2, z−1/2; (v) −x, y+1/2, −z+3/2; (vi) x, −y+3/2, z+1/2; (vii) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(H2O)6](C14H13O10P2)2·2H2O |
Mr | 1009.43 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 21.053 (4), 7.2030 (14), 13.370 (3) |
β (°) | 92.00 (1) |
V (Å3) | 2026.3 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.68 |
Crystal size (mm) | 0.36 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Kuma KM-4 diffractometer with a CCD area detector |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.843, 0.899 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26924, 5087, 3294 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.671 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.073, 1.00 |
No. of reflections | 5087 |
No. of parameters | 316 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.28 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
Co1—O2W | 2.0722 (15) | P11—O13 | 1.5398 (14) |
Co1—O3W | 2.0828 (15) | P21—O21 | 1.4975 (13) |
Co1—O1W | 2.1012 (14) | P21—O22 | 1.5107 (13) |
P11—O11 | 1.4988 (13) | P21—O23 | 1.5394 (14) |
P11—O12 | 1.5225 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O4Wi | 0.81 (2) | 1.94 (2) | 2.752 (2) | 174 (2) |
O1W—H2W1···O21ii | 0.79 (2) | 1.86 (2) | 2.644 (2) | 172 (2) |
O2W—H1W2···O11iii | 0.91 (2) | 1.75 (2) | 2.654 (2) | 174 (2) |
O2W—H2W2···O22ii | 0.77 (2) | 2.31 (2) | 3.060 (2) | 168 (3) |
O2W—H2W2···O21ii | 0.77 (2) | 2.62 (2) | 3.178 (2) | 131 (2) |
O3W—H1W3···O4Wii | 0.80 (3) | 1.96 (3) | 2.758 (2) | 179 (3) |
O3W—H2W3···O23i | 0.78 (3) | 2.33 (3) | 2.972 (2) | 141 (2) |
O4W—H1W4···O12 | 0.86 (2) | 1.90 (2) | 2.761 (2) | 172 (2) |
O4W—H2W4···O1W | 0.80 (2) | 2.10 (2) | 2.886 (2) | 169 (2) |
O22—H22O···O12 | 1.14 (2) | 1.30 (2) | 2.435 (2) | 176 (2) |
O13—H13O···O21ii | 0.84 (2) | 1.68 (2) | 2.523 (2) | 174 (2) |
O15—H15O···O24iv | 0.89 (3) | 1.69 (3) | 2.578 (2) | 173 (3) |
O23—H23O···O11v | 0.80 (2) | 1.73 (2) | 2.528 (2) | 171 (2) |
O25—H25O···O14vi | 0.84 (3) | 1.82 (3) | 2.658 (2) | 171 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) −x, y+1/2, −z+3/2; (v) x, −y+3/2, z+1/2; (vi) −x, y−1/2, −z+3/2. |
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The chemistry of metal organophosphonates has attracted considerable attention for a long time, due to the potential applications of these materials as ion exchangers, catalysts, proton conductors and sensors (Clearfield, 1998; Alberti et al., 1996; Cao et al., 1992). Recently, consideration has been devoted to metal arylphosphonates, in which an additional functional group, especially a carboxyl group, is attached to the aromatic ring. The multifunctional acids have been found to be better ligands, since they provide additional coordination sites and allow the formation of novel complexes with variable structures and versatile properties. In particular, 4-carboxyphenylphosphonic acid has been widely used to form inorganic–organic hybrid compounds with the transition metal ions Ni2+ (one compound), Cu2+ (eight) and Zn2+ (16), as well as with main group metals (12) or rare earth metal ions (three). It has also been used as a ligand in three oxovanadium– and seven oxomolybdenum–organophosphonate/secondary metal–organonitrogen ligand systems. A literature survey has revealed that the majority of the 50 metal 4-carboxyphenylphosphonate structures reported to date were studied during the last two years. The acid moieties in them appear in different forms, from intact acid up to fully deprotonated trianion, and the metal ions are coordinated by O atoms from the phosphonate or from both phosphonate and carboxylate functional groups. However, to the best of our knowledge, there are no metal ion compounds of 4-carboxyphenylphosphonic acid in which both the anion and cation appear in complex form. A search of the Cambridge Structural Database (CSD, Version 5.31; Allen, 2002) returned only 24 organophosphonate crystal structures in which the H atom is shared between two neighbouring phosphonate sites in order to form a complex anionic unit via very short linear hydrogen bonds (O···O distances 2.37–2.45 Å and O—H—O angles 176–180°). In all but three of those compounds the hydrogen bond is symmetry-constrained. Here, we report the crystal structure of the title compound, (I), where there is no symmetry restriction imposed on the shared H atom.
The asymmetric unit of (I) contains half a CoII ion, two acid moieties and four symmetry-independent water molecules (Fig. 1). The metal ion is six-coordinate with a slightly distorted octahedral geometry, and occupies a special position on the inversion centre at (1/2, 1/2, 0). Six water molecules, three of which are unique, fill the first coordination sphere of the CoII ion in order to form the [Co(H2O)6]2+ unit. Atoms O2W, O2Wi, O3W and O3Wi (symmetry code as in Table 1) act as equatorial ligands and create two pairs of similar bonds (Co1—O2W and Co1—O3W), whereas the axial ligands O1W and O1Wi form a somewhat longer bond (Co1—O1W) (Table 1).
The bond distances and angles observed in both acid moieties are within the usual ranges for carboxyl and phosphonic groups (Standard reference?), although the P11—O12 and P21—O22 bond distances are intermediate between single and double P—O bonds. This reflects the migration of the H atom from the formal phosphonic acid group to the phosphonate group of an adjacent moiety, in order to form a complex [H(HO3PC6H4COOH)2]- monoanion via a very short (P)O22···H22O···O12(P) hydrogen bond (Fig. 1). Nevertheless, in the crystal structure there is only one position for atom H22O. Despite the very short distance of 2.435 (2) Å between the O sites in the dimeric unit, the position of H22O is not confined by any symmetry elements and its environment is asymmetric. The hydrogen bond is almost linear, but the two O—H distances are somewhat different (Table 2). The acid residues on both sides of the hydrogen bond are symmetry-unique and one of the carboxyl groups is rotated by 11.45 (12)° relative to the plane of the phenyl ring to which it is bonded, whereas the second group is almost coplanar with the corresponding ring. The acid dimers are organized into a polar monolayer with the help of two other hydrogen bonds, O13—H13O···O21iii and O23—H23O···O11vi (symmetry codes as in Table 2), established between the different phosphonate sites. The (P)O—H···O(P) hydrogen-bonded network is two-dimensional, parallel to the crystallographic bc plane, and is characterized by large R66(24) motifs (Bernstein et al., 1995) which are arranged in a herringbone fashion (Fig. 2a). The aromatic rings of the monoanions are arranged on one side of the monolayer. The para-carboxyl groups connect neighbouring inversion-related monolayers via two different carboxyl–carboxyl hydrogen-bond interactions, O15—H15O···O24v and O25—H25O···O14vii (symmetry codes as in Table 2), in order to form a thick organic bilayer. The phosphonate sites of the complex monoanion create the outer surfaces of the bilayer, while the aromatic rings and the R22(8) synthons form its interior (Fig. 2b).
The [Co(H2O)6]2+ units are arranged between the anionic bilayers. The aqua ligands serve both to complete the coordination environment of the CoII ion and to cross-link the bilayers via water–phosphonate hydrogen bonds in order to construct the three-dimensional crystal structure. However, each hydrated CoII ion is surrounded by six phosphonate groups from two neighbouring bilayers. Five different hydrogen bonds are formed between the water molecules in the first coordination sphere and the phosphonate O atoms of the second (Fig. 3b). Four of these, O2W—H1W2···O11iv, O2W—H2W2···O21iii, O2W—H2W2···O22iii and O3W—H2W3···O23ii, are donated from the equatorial ligands, and the fifth, O1W—H2W1···O21iii, from the axial ligands. The small channels generated along the b axis are occupied by the solvent water molecules OW4, which serve both to fill the empty spaces of the structure and to connect the coordination units into a two-dimensional network. There are six solvent water molecules OW4 around the [Co(H2O)6]2+ unit, and each of them is used to mediate three cationic units via three different hydrogen bonds from or to the aqua ligands: O1W—H1W1···O4Wii, O3W—H2W3···O4Wiii and O4W—H2W4···O1W. Two types of water ring motifs, R44(10) and R42(12), are formed around the CoII ions, which tessellate in order to produce a two-dimensional hydrogen-bonded network of CoII ions (Fig. 3a). An additional O4W—H1W4···O12 bond is established between the solvent water and the organic monolayer.
In conclusion, the title compound, (I), demonstrates a layered structure with thick organic bilayers and inorganic monolayers, which cross-link the bilayers via multiple hydrogen bonds. De facto, the crystal packing of the compound generates hydrophobic and hydrophilic regions that alternate along the crystallographic a axis. However, the hydrophilic regions, arranged on both sides of the aromatic region, are different: one of them contains hydrogen-bonded R22(8) ring motifs formed by the carboxyl groups of the monoanions, and the other consists of the phosphonate groups and hydrated metal ions (Fig. 3b). In this view, the structure of (I) resembles the packing patterns of some other metal 4-carboxyphenylphosphonate compounds with divalent metal ions like calcium (Svoboda et al., 2005), strontium (Zima et al., 2007), barium (Svoboda et al., 2008) and copper(II) ions (Li et al., 2008; Zima et al., 2009). The major structural difference observed in these structures is a direct metal–phosphonate contact via M—O bonds, making the inorganic monolayer more compact.