Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107025395/bc3048sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107025395/bc3048Isup2.hkl |
The title compound was prepared by hydrothermal treatment of V2O5 (0.3861 g, 2.1 mmol) and NaOH (0.0672 g, 1.7 mmol) acidified to pH 5.8 with aqueous HCl. The reaction mixture was heated for 20 h at 393 K. The fitrate was kept at room temperature and block-shaped orange–yellow single crystals formed after one week. Compound (I) is air-stable both in the solid state and in solution at room temperature. The FT–IR spectrum of (I) shows two strong bands at 957 and 989 cm-1 that can be assigned to the stretching of the terminal V—O bonds. The antisymmetric modes of the V—O—V bridges possibly correspond to the bands at 750 and 848 cm-1, while the symmetric modes are probably at 558 and 605 cm-1. The broad band at 3467 cm-1 is due to the coordinated and solvent waters. Thermogravimetric analysis shows that the crystals lose 28.15 wt% in the temperature range 358–595 K. This is consistent with the number of coordinated and solvent water molecules in the molecular formula (28.28 wt%).
The coordinates of all H atoms were determined from a difference Fourier map. The H atoms were included in the final cycles of refinement with O—H and H···H distance restraints of 0.85 (1) and 1.39 (1) Å, respectively; Uiso(H) values were set at 1.5Ueq(O) for the coordinated water molecules and refined freely for the solvent molecules.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.
Na6(H2O)20(V10O28)·4H2O | Z = 1 |
Mr = 1527.72 | F(000) = 760 |
Triclinic, P1 | Dx = 2.249 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 10.5834 (3) Å | Cell parameters from 4336 reflections |
b = 11.3803 (3) Å | θ = 3.1–25.4° |
c = 11.6367 (3) Å | µ = 2.16 mm−1 |
α = 108.682 (4)° | T = 223 K |
β = 103.775 (2)° | Block, orange-yellow |
γ = 111.674 (3)° | 0.30 × 0.24 × 0.20 mm |
V = 1128.19 (5) Å3 |
Siemens SMART CCD area-detector diffractometer | 4088 independent reflections |
Radiation source: fine-focus sealed tube | 3529 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 25.4°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→11 |
Tmin = 0.542, Tmax = 0.649 | k = −13→13 |
11109 measured reflections | l = −14→14 |
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)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.070P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
4088 reflections | Δρmax = 0.48 e Å−3 |
379 parameters | Δρmin = −0.46 e Å−3 |
36 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0033 (8) |
Na6(H2O)20(V10O28)·4H2O | γ = 111.674 (3)° |
Mr = 1527.72 | V = 1128.19 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.5834 (3) Å | Mo Kα radiation |
b = 11.3803 (3) Å | µ = 2.16 mm−1 |
c = 11.6367 (3) Å | T = 223 K |
α = 108.682 (4)° | 0.30 × 0.24 × 0.20 mm |
β = 103.775 (2)° |
Siemens SMART CCD area-detector diffractometer | 4088 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3529 reflections with I > 2σ(I) |
Tmin = 0.542, Tmax = 0.649 | Rint = 0.028 |
11109 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 36 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.48 e Å−3 |
4088 reflections | Δρmin = −0.46 e Å−3 |
379 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 | ||
V1 | −0.13667 (6) | 0.00678 (6) | 0.70287 (5) | 0.01648 (18) | |
V2 | 0.11146 (6) | 0.02394 (5) | 0.92289 (5) | 0.01133 (16) | |
V3 | 0.34146 (6) | 0.03813 (6) | 1.15233 (6) | 0.01602 (17) | |
V4 | 0.20972 (6) | 0.24151 (5) | 1.22011 (5) | 0.01235 (17) | |
V5 | −0.02637 (6) | 0.22625 (5) | 0.99442 (5) | 0.01259 (17) | |
Na1 | −0.19844 (16) | 0.09634 (15) | 0.39963 (15) | 0.0308 (4) | |
Na2 | 0.36612 (15) | 0.52124 (14) | 0.89519 (13) | 0.0235 (3) | |
Na3 | 0.11756 (14) | 0.50494 (13) | 0.62998 (13) | 0.0229 (3) | |
O1 | −0.1418 (3) | 0.0162 (3) | 0.5682 (2) | 0.0257 (6) | |
O2 | 0.0067 (2) | −0.1797 (2) | 0.8522 (2) | 0.0135 (5) | |
O3 | 0.0430 (3) | 0.3962 (2) | 1.0724 (2) | 0.0197 (5) | |
O4 | 0.3182 (2) | 0.0216 (2) | 1.2985 (2) | 0.0192 (5) | |
O5 | 0.1942 (2) | 0.1864 (2) | 1.3486 (2) | 0.0160 (5) | |
O6 | 0.2755 (3) | 0.4111 (2) | 1.2974 (2) | 0.0192 (5) | |
O7 | 0.1036 (2) | 0.0068 (2) | 1.0977 (2) | 0.0133 (5) | |
O8 | 0.3737 (2) | 0.2237 (2) | 1.2220 (2) | 0.0159 (5) | |
O9 | 0.5064 (3) | 0.0620 (2) | 1.1742 (2) | 0.0242 (6) | |
O10 | −0.0410 (2) | 0.1976 (2) | 0.8272 (2) | 0.0168 (5) | |
O11 | 0.1619 (2) | 0.2148 (2) | 1.0325 (2) | 0.0125 (5) | |
O12 | 0.0738 (2) | 0.0279 (2) | 0.7751 (2) | 0.0166 (5) | |
O13 | 0.2850 (2) | 0.0441 (2) | 0.9744 (2) | 0.0152 (5) | |
O14 | −0.2245 (2) | 0.1595 (2) | 0.9525 (2) | 0.0168 (5) | |
O15 | 0.1828 (3) | 0.7554 (3) | 0.7216 (2) | 0.0233 (6) | |
H15A | 0.126 (3) | 0.763 (4) | 0.762 (3) | 0.028* | |
H15B | 0.2723 (14) | 0.815 (3) | 0.776 (3) | 0.028* | |
O16 | 0.1082 (3) | 0.4662 (3) | 0.8234 (3) | 0.0251 (6) | |
H16B | 0.074 (4) | 0.389 (2) | 0.829 (4) | 0.030* | |
H16A | 0.080 (4) | 0.520 (3) | 0.868 (3) | 0.030* | |
O17 | 0.3951 (3) | 0.4729 (3) | 1.0801 (3) | 0.0259 (6) | |
H17A | 0.330 (3) | 0.3915 (15) | 1.062 (3) | 0.031* | |
H17B | 0.395 (4) | 0.536 (2) | 1.143 (3) | 0.031* | |
O18 | 0.3619 (3) | 0.5449 (3) | 0.6982 (3) | 0.0252 (6) | |
H18A | 0.375 (4) | 0.479 (2) | 0.652 (3) | 0.030* | |
H18B | 0.437 (3) | 0.6246 (17) | 0.724 (3) | 0.030* | |
O19 | 0.2325 (3) | 0.2764 (3) | 0.7523 (3) | 0.0274 (6) | |
H19A | 0.176 (3) | 0.235 (4) | 0.783 (4) | 0.033* | |
H19B | 0.284 (4) | 0.239 (4) | 0.734 (4) | 0.033* | |
O20 | 0.0561 (3) | 0.2605 (2) | 0.5176 (2) | 0.0229 (6) | |
H20A | 0.1046 | 0.2522 | 0.4556 | 0.027* | |
H20B | 0.0984 | 0.2342 | 0.5836 | 0.027* | |
O21 | 0.4387 (3) | 0.7589 (3) | 1.0145 (3) | 0.0276 (6) | |
H21A | 0.365 (2) | 0.774 (4) | 1.008 (4) | 0.033* | |
H21B | 0.509 (3) | 0.828 (3) | 1.017 (4) | 0.033* | |
O22 | −0.1307 (3) | 0.4616 (3) | 0.5609 (3) | 0.0265 (6) | |
H22A | −0.201 (3) | 0.3763 (14) | 0.525 (3) | 0.032* | |
H22B | −0.152 (4) | 0.515 (3) | 0.614 (3) | 0.032* | |
O23 | −0.3455 (3) | 0.1806 (3) | 0.4916 (3) | 0.0387 (7) | |
H23A | −0.339 (4) | 0.211 (4) | 0.5703 (14) | 0.046* | |
H23B | −0.4360 (19) | 0.139 (4) | 0.437 (3) | 0.046* | |
O24 | −0.3936 (3) | −0.1357 (3) | 0.2880 (3) | 0.0340 (7) | |
H24A | −0.439 (3) | −0.169 (4) | 0.329 (3) | 0.041* | |
H24B | −0.451 (3) | −0.168 (4) | 0.2079 (15) | 0.041* | |
O1W | −0.2809 (3) | 0.3030 (3) | 0.7664 (3) | 0.0340 (7) | |
H1WA | −0.261 (5) | 0.245 (3) | 0.787 (4) | 0.061 (17)* | |
H1WB | −0.212 (4) | 0.3870 (16) | 0.817 (4) | 0.058 (16)* | |
O2W | 0.4468 (3) | 0.3331 (3) | 1.5892 (3) | 0.0333 (7) | |
H2WA | 0.387 (3) | 0.297 (4) | 1.5090 (17) | 0.043 (13)* | |
H2WB | 0.5351 (17) | 0.378 (5) | 1.598 (4) | 0.077 (19)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0162 (3) | 0.0168 (3) | 0.0144 (3) | 0.0054 (3) | 0.0051 (2) | 0.0085 (2) |
V2 | 0.0107 (3) | 0.0106 (3) | 0.0125 (3) | 0.0042 (2) | 0.0062 (2) | 0.0051 (2) |
V3 | 0.0109 (3) | 0.0156 (3) | 0.0198 (3) | 0.0055 (2) | 0.0053 (2) | 0.0078 (3) |
V4 | 0.0114 (3) | 0.0097 (3) | 0.0115 (3) | 0.0026 (2) | 0.0038 (2) | 0.0034 (2) |
V5 | 0.0117 (3) | 0.0097 (3) | 0.0155 (3) | 0.0049 (2) | 0.0049 (2) | 0.0055 (2) |
Na1 | 0.0305 (8) | 0.0241 (8) | 0.0307 (8) | 0.0068 (7) | 0.0096 (7) | 0.0140 (7) |
Na2 | 0.0222 (7) | 0.0212 (7) | 0.0259 (8) | 0.0089 (6) | 0.0081 (6) | 0.0122 (6) |
Na3 | 0.0218 (8) | 0.0234 (8) | 0.0255 (8) | 0.0120 (6) | 0.0101 (6) | 0.0117 (6) |
O1 | 0.0289 (14) | 0.0281 (14) | 0.0175 (13) | 0.0091 (12) | 0.0077 (11) | 0.0142 (11) |
O2 | 0.0126 (11) | 0.0102 (11) | 0.0159 (12) | 0.0045 (9) | 0.0069 (9) | 0.0044 (9) |
O3 | 0.0205 (13) | 0.0097 (11) | 0.0269 (13) | 0.0064 (10) | 0.0091 (11) | 0.0075 (10) |
O4 | 0.0161 (12) | 0.0181 (12) | 0.0193 (12) | 0.0053 (10) | 0.0030 (10) | 0.0105 (10) |
O5 | 0.0158 (12) | 0.0150 (12) | 0.0126 (11) | 0.0044 (10) | 0.0053 (9) | 0.0050 (9) |
O6 | 0.0189 (12) | 0.0127 (12) | 0.0197 (12) | 0.0043 (10) | 0.0078 (10) | 0.0041 (10) |
O7 | 0.0099 (11) | 0.0133 (12) | 0.0149 (12) | 0.0043 (10) | 0.0041 (9) | 0.0068 (10) |
O8 | 0.0119 (11) | 0.0134 (12) | 0.0184 (12) | 0.0038 (9) | 0.0040 (10) | 0.0068 (10) |
O9 | 0.0141 (12) | 0.0233 (13) | 0.0306 (14) | 0.0085 (11) | 0.0068 (11) | 0.0093 (11) |
O10 | 0.0160 (12) | 0.0151 (12) | 0.0199 (12) | 0.0055 (10) | 0.0071 (10) | 0.0110 (10) |
O11 | 0.0111 (11) | 0.0111 (11) | 0.0134 (11) | 0.0035 (9) | 0.0049 (9) | 0.0055 (9) |
O12 | 0.0162 (12) | 0.0161 (12) | 0.0147 (12) | 0.0038 (10) | 0.0077 (10) | 0.0076 (10) |
O13 | 0.0132 (12) | 0.0125 (11) | 0.0178 (12) | 0.0045 (9) | 0.0081 (10) | 0.0052 (9) |
O14 | 0.0130 (11) | 0.0148 (12) | 0.0223 (13) | 0.0077 (10) | 0.0068 (10) | 0.0070 (10) |
O15 | 0.0176 (13) | 0.0226 (14) | 0.0222 (13) | 0.0066 (11) | 0.0081 (11) | 0.0053 (11) |
O16 | 0.0286 (14) | 0.0253 (14) | 0.0355 (15) | 0.0169 (12) | 0.0216 (12) | 0.0188 (12) |
O17 | 0.0230 (14) | 0.0236 (14) | 0.0276 (15) | 0.0059 (12) | 0.0131 (12) | 0.0118 (12) |
O18 | 0.0175 (13) | 0.0175 (13) | 0.0311 (15) | 0.0028 (11) | 0.0079 (11) | 0.0086 (12) |
O19 | 0.0239 (15) | 0.0217 (14) | 0.0384 (16) | 0.0092 (12) | 0.0156 (12) | 0.0155 (12) |
O20 | 0.0259 (14) | 0.0230 (13) | 0.0230 (13) | 0.0125 (11) | 0.0122 (11) | 0.0114 (11) |
O21 | 0.0216 (14) | 0.0191 (14) | 0.0412 (16) | 0.0084 (11) | 0.0186 (13) | 0.0102 (12) |
O22 | 0.0255 (14) | 0.0256 (14) | 0.0294 (15) | 0.0127 (12) | 0.0135 (12) | 0.0117 (12) |
O23 | 0.0327 (16) | 0.0407 (17) | 0.0342 (16) | 0.0131 (14) | 0.0134 (13) | 0.0131 (14) |
O24 | 0.0271 (15) | 0.0320 (16) | 0.0362 (16) | 0.0095 (13) | 0.0093 (13) | 0.0162 (14) |
O1W | 0.0244 (15) | 0.0340 (17) | 0.0385 (17) | 0.0107 (14) | 0.0067 (13) | 0.0190 (15) |
O2W | 0.0217 (15) | 0.0347 (16) | 0.0259 (16) | 0.0037 (13) | 0.0022 (12) | 0.0111 (13) |
V1—O1 | 1.594 (2) | Na2—O17 | 2.366 (3) |
V1—O4i | 1.822 (2) | Na2—O18 | 2.385 (3) |
V1—O10 | 1.870 (2) | Na2—O16 | 2.420 (3) |
V1—O5i | 1.886 (2) | Na2—O17iv | 2.448 (3) |
V1—O12 | 2.076 (2) | Na2—Na3 | 3.4475 (18) |
V1—O7i | 2.327 (2) | Na2—Na2iv | 3.562 (3) |
V1—V3i | 3.0447 (8) | Na2—H16B | 2.67 (3) |
V1—V2 | 3.0965 (7) | Na3—O18 | 2.334 (3) |
V1—V5 | 3.1053 (8) | Na3—O22 | 2.361 (3) |
V1—V4i | 3.1184 (7) | Na3—O22ii | 2.397 (3) |
V2—O12 | 1.689 (2) | Na3—O20 | 2.408 (3) |
V2—O13 | 1.692 (2) | Na3—O16 | 2.445 (3) |
V2—O11 | 1.917 (2) | Na3—O15 | 2.447 (3) |
V2—O2 | 1.930 (2) | Na3—Na3ii | 3.369 (3) |
V2—O7i | 2.112 (2) | O2—V4i | 1.991 (2) |
V2—O7 | 2.123 (2) | O2—V5i | 2.005 (2) |
V2—V3 | 3.0689 (7) | O4—V1i | 1.822 (2) |
V3—O9 | 1.606 (2) | O5—V1i | 1.886 (2) |
V3—O4 | 1.833 (2) | O7—V2i | 2.112 (2) |
V3—O8 | 1.864 (2) | O7—V5i | 2.239 (2) |
V3—O14i | 1.883 (2) | O7—V1i | 2.327 (2) |
V3—O13 | 2.044 (2) | O12—Na1iii | 2.948 (3) |
V3—O7 | 2.301 (2) | O14—V3i | 1.883 (2) |
V3—V1i | 3.0447 (8) | O15—Na1ii | 2.508 (3) |
V3—V4 | 3.1082 (8) | O15—H15A | 0.857 (11) |
V3—V5i | 3.1103 (8) | O15—H15B | 0.849 (11) |
V4—O6 | 1.617 (2) | O16—H16B | 0.853 (11) |
V4—O5 | 1.816 (2) | O16—H16A | 0.855 (11) |
V4—O8 | 1.816 (2) | O17—Na2iv | 2.448 (3) |
V4—O2i | 1.991 (2) | O17—H17A | 0.843 (11) |
V4—O11 | 2.013 (2) | O17—H17B | 0.845 (11) |
V4—O7 | 2.238 (2) | O18—H18A | 0.849 (11) |
V4—V5 | 3.0713 (7) | O18—H18B | 0.852 (11) |
V4—V1i | 3.1184 (7) | O19—H19A | 0.842 (11) |
V5—O3 | 1.617 (2) | O19—H19B | 0.840 (11) |
V5—O14 | 1.820 (2) | O20—H20A | 0.9800 |
V5—O10 | 1.825 (2) | O20—H20B | 0.9800 |
V5—O11 | 1.998 (2) | O21—H21A | 0.855 (11) |
V5—O2i | 2.005 (2) | O21—H21B | 0.848 (11) |
V5—O7i | 2.239 (2) | O22—Na3ii | 2.397 (3) |
V5—V3i | 3.1103 (8) | O22—H22A | 0.854 (11) |
Na1—O24 | 2.328 (3) | O22—H22B | 0.850 (11) |
Na1—O20 | 2.348 (3) | O23—H23A | 0.844 (11) |
Na1—O23 | 2.393 (3) | O23—H23B | 0.851 (11) |
Na1—O1 | 2.455 (3) | O24—H24A | 0.833 (11) |
Na1—O15ii | 2.508 (3) | O24—H24B | 0.846 (11) |
Na1—O12iii | 2.948 (3) | O1W—H1WA | 0.845 (11) |
Na1—Na3 | 4.0313 (19) | O1W—H1WB | 0.843 (11) |
Na2—O21 | 2.320 (3) | O2W—H2WA | 0.848 (11) |
Na2—O19 | 2.352 (3) | O2W—H2WB | 0.846 (11) |
O1—V1—O4i | 104.20 (12) | O3—V5—V3i | 136.82 (9) |
O1—V1—O10 | 102.55 (12) | O14—V5—V3i | 33.50 (7) |
O4i—V1—O10 | 93.04 (10) | O10—V5—V3i | 84.08 (7) |
O1—V1—O5i | 101.57 (12) | O11—V5—V3i | 123.59 (6) |
O4i—V1—O5i | 91.57 (10) | O2i—V5—V3i | 86.66 (6) |
O10—V1—O5i | 153.49 (10) | O7i—V5—V3i | 47.61 (5) |
O1—V1—O12 | 99.81 (12) | V4—V5—V3i | 118.93 (2) |
O4i—V1—O12 | 155.93 (10) | V1—V5—V3i | 58.662 (18) |
O10—V1—O12 | 83.34 (10) | O24—Na1—O20 | 151.00 (12) |
O5i—V1—O12 | 81.88 (9) | O24—Na1—O23 | 91.49 (11) |
O1—V1—O7i | 173.52 (11) | O20—Na1—O23 | 111.43 (11) |
O4i—V1—O7i | 82.22 (9) | O24—Na1—O1 | 80.53 (10) |
O10—V1—O7i | 77.66 (8) | O20—Na1—O1 | 81.30 (9) |
O5i—V1—O7i | 77.13 (8) | O23—Na1—O1 | 91.56 (11) |
O12—V1—O7i | 73.74 (8) | O24—Na1—O15ii | 116.97 (11) |
O1—V1—V3i | 137.92 (10) | O20—Na1—O15ii | 82.00 (9) |
O4i—V1—V3i | 33.72 (7) | O23—Na1—O15ii | 89.50 (11) |
O10—V1—V3i | 85.29 (7) | O1—Na1—O15ii | 162.44 (10) |
O5i—V1—V3i | 84.18 (7) | O24—Na1—O12iii | 81.98 (10) |
O12—V1—V3i | 122.24 (6) | O20—Na1—O12iii | 78.92 (8) |
O7i—V1—V3i | 48.50 (5) | O23—Na1—O12iii | 166.07 (11) |
O1—V1—V2 | 130.58 (10) | O1—Na1—O12iii | 99.43 (9) |
O4i—V1—V2 | 125.20 (7) | O15ii—Na1—O12iii | 82.62 (8) |
O10—V1—V2 | 77.90 (7) | O24—Na1—Na3 | 172.40 (10) |
O5i—V1—V2 | 78.13 (7) | O20—Na1—Na3 | 32.51 (6) |
O12—V1—V2 | 30.78 (6) | O23—Na1—Na3 | 82.04 (8) |
O7i—V1—V2 | 42.98 (5) | O1—Na1—Na3 | 95.58 (7) |
V3i—V1—V2 | 91.48 (2) | O15ii—Na1—Na3 | 67.20 (7) |
O1—V1—V5 | 134.84 (9) | O12iii—Na1—Na3 | 105.18 (6) |
O4i—V1—V5 | 82.61 (7) | O21—Na2—O19 | 165.24 (11) |
O10—V1—V5 | 32.38 (7) | O21—Na2—O17 | 95.54 (10) |
O5i—V1—V5 | 123.09 (7) | O19—Na2—O17 | 89.78 (10) |
O12—V1—V5 | 81.72 (6) | O21—Na2—O18 | 92.29 (10) |
O7i—V1—V5 | 45.96 (5) | O19—Na2—O18 | 84.58 (10) |
V3i—V1—V5 | 60.752 (18) | O17—Na2—O18 | 168.83 (11) |
V2—V1—V5 | 61.152 (17) | O21—Na2—O16 | 89.89 (10) |
O1—V1—V4i | 133.45 (9) | O19—Na2—O16 | 75.59 (10) |
O4i—V1—V4i | 82.22 (7) | O17—Na2—O16 | 100.36 (10) |
O10—V1—V4i | 123.38 (7) | O18—Na2—O16 | 87.59 (9) |
O5i—V1—V4i | 31.92 (7) | O21—Na2—O17iv | 102.08 (10) |
O12—V1—V4i | 80.05 (6) | O19—Na2—O17iv | 92.11 (10) |
O7i—V1—V4i | 45.74 (5) | O17—Na2—O17iv | 84.54 (9) |
V3i—V1—V4i | 60.559 (17) | O18—Na2—O17iv | 86.04 (9) |
V2—V1—V4i | 61.003 (17) | O16—Na2—O17iv | 166.64 (11) |
V5—V1—V4i | 91.531 (19) | O21—Na2—Na3 | 89.55 (8) |
O12—V2—O13 | 106.75 (11) | O19—Na2—Na3 | 78.39 (8) |
O12—V2—O11 | 98.51 (10) | O17—Na2—Na3 | 145.26 (8) |
O13—V2—O11 | 97.46 (10) | O18—Na2—Na3 | 42.49 (7) |
O12—V2—O2 | 96.48 (10) | O16—Na2—Na3 | 45.17 (7) |
O13—V2—O2 | 96.51 (10) | O17iv—Na2—Na3 | 127.95 (8) |
O11—V2—O2 | 155.60 (10) | O21—Na2—Na2iv | 102.00 (9) |
O12—V2—O7i | 87.65 (10) | O19—Na2—Na2iv | 91.30 (8) |
O13—V2—O7i | 165.57 (10) | O17—Na2—Na2iv | 43.16 (7) |
O11—V2—O7i | 80.82 (9) | O18—Na2—Na2iv | 127.16 (9) |
O2—V2—O7i | 80.67 (9) | O16—Na2—Na2iv | 142.00 (9) |
O12—V2—O7 | 165.93 (10) | O17iv—Na2—Na2iv | 41.38 (6) |
O13—V2—O7 | 87.24 (9) | Na3—Na2—Na2iv | 165.53 (7) |
O11—V2—O7 | 80.64 (9) | O21—Na2—H16B | 104.0 (5) |
O2—V2—O7 | 80.16 (9) | O19—Na2—H16B | 62.4 (5) |
O7i—V2—O7 | 78.33 (9) | O17—Na2—H16B | 87.1 (6) |
O12—V2—V3 | 145.46 (8) | O18—Na2—H16B | 98.8 (7) |
O13—V2—V3 | 38.71 (7) | O16—Na2—H16B | 18.5 (4) |
O11—V2—V3 | 89.34 (7) | O17iv—Na2—H16B | 153.2 (4) |
O2—V2—V3 | 89.14 (7) | Na3—Na2—H16B | 58.4 (6) |
O7i—V2—V3 | 126.87 (6) | Na2iv—Na2—H16B | 125.4 (5) |
O7—V2—V3 | 48.53 (6) | O18—Na3—O22 | 179.26 (10) |
O12—V2—V1 | 38.97 (8) | O18—Na3—O22ii | 90.51 (10) |
O13—V2—V1 | 145.72 (8) | O22—Na3—O22ii | 89.86 (9) |
O11—V2—V1 | 89.63 (7) | O18—Na3—O20 | 83.78 (9) |
O2—V2—V1 | 90.01 (7) | O22—Na3—O20 | 95.57 (10) |
O7i—V2—V1 | 48.70 (6) | O22ii—Na3—O20 | 91.32 (9) |
O7—V2—V1 | 127.03 (6) | O18—Na3—O16 | 88.14 (10) |
V3—V2—V1 | 175.57 (2) | O22—Na3—O16 | 91.48 (10) |
O9—V3—O4 | 104.26 (12) | O22ii—Na3—O16 | 178.15 (10) |
O9—V3—O8 | 101.96 (11) | O20—Na3—O16 | 87.28 (9) |
O4—V3—O8 | 91.34 (10) | O18—Na3—O15 | 95.80 (10) |
O9—V3—O14i | 102.14 (11) | O22—Na3—O15 | 84.88 (9) |
O4—V3—O14i | 90.92 (10) | O22ii—Na3—O15 | 82.17 (9) |
O8—V3—O14i | 154.43 (10) | O20—Na3—O15 | 173.48 (10) |
O9—V3—O13 | 98.12 (11) | O16—Na3—O15 | 99.22 (10) |
O4—V3—O13 | 157.62 (10) | O18—Na3—Na3ii | 135.00 (10) |
O8—V3—O13 | 84.21 (9) | O22—Na3—Na3ii | 45.36 (7) |
O14i—V3—O13 | 84.06 (10) | O22ii—Na3—Na3ii | 44.50 (7) |
O9—V3—O7 | 173.01 (11) | O20—Na3—Na3ii | 94.84 (8) |
O4—V3—O7 | 82.72 (9) | O16—Na3—Na3ii | 136.83 (9) |
O8—V3—O7 | 77.32 (9) | O15—Na3—Na3ii | 80.83 (8) |
O14i—V3—O7 | 77.71 (9) | O18—Na3—Na2 | 43.64 (7) |
O13—V3—O7 | 74.90 (8) | O22—Na3—Na2 | 136.01 (8) |
O9—V3—V1i | 137.75 (9) | O22ii—Na3—Na2 | 134.12 (8) |
O4—V3—V1i | 33.49 (7) | O20—Na3—Na2 | 85.78 (7) |
O8—V3—V1i | 84.17 (7) | O16—Na3—Na2 | 44.58 (7) |
O14i—V3—V1i | 83.76 (7) | O15—Na3—Na2 | 98.43 (7) |
O13—V3—V1i | 124.13 (7) | Na3ii—Na3—Na2 | 178.46 (7) |
O7—V3—V1i | 49.23 (5) | O18—Na3—Na1 | 115.37 (8) |
O9—V3—V2 | 129.30 (9) | O22—Na3—Na1 | 63.98 (7) |
O4—V3—V2 | 126.44 (8) | O22ii—Na3—Na1 | 91.39 (7) |
O8—V3—V2 | 78.73 (7) | O20—Na3—Na1 | 31.59 (6) |
O14i—V3—V2 | 79.47 (7) | O16—Na3—Na1 | 88.05 (7) |
O13—V3—V2 | 31.19 (6) | O15—Na3—Na1 | 148.28 (8) |
O7—V3—V2 | 43.72 (5) | Na3ii—Na3—Na1 | 73.13 (5) |
V1i—V3—V2 | 92.95 (2) | Na2—Na3—Na1 | 107.99 (4) |
O9—V3—V4 | 133.83 (9) | V1—O1—Na1 | 154.17 (16) |
O4—V3—V4 | 82.35 (7) | V2—O2—V4i | 107.13 (10) |
O8—V3—V4 | 31.89 (7) | V2—O2—V5i | 107.89 (10) |
O14i—V3—V4 | 123.65 (7) | V4i—O2—V5i | 100.48 (10) |
O13—V3—V4 | 82.37 (6) | V1i—O4—V3 | 112.79 (12) |
O7—V3—V4 | 45.95 (5) | V4—O5—V1i | 114.77 (12) |
V1i—V3—V4 | 60.892 (17) | V2i—O7—V2 | 101.67 (9) |
V2—V3—V4 | 61.834 (17) | V2i—O7—V4 | 92.92 (8) |
O9—V3—V5i | 134.37 (9) | V2—O7—V4 | 93.37 (8) |
O4—V3—V5i | 82.31 (7) | V2i—O7—V5i | 92.92 (8) |
O8—V3—V5i | 123.24 (7) | V2—O7—V5i | 93.63 (8) |
O14i—V3—V5i | 32.24 (7) | V4—O7—V5i | 169.80 (11) |
O13—V3—V5i | 81.88 (6) | V2i—O7—V3 | 170.58 (11) |
O7—V3—V5i | 45.92 (5) | V2—O7—V3 | 87.75 (8) |
V1i—V3—V5i | 60.586 (18) | V4—O7—V3 | 86.41 (7) |
V2—V3—V5i | 61.960 (17) | V5i—O7—V3 | 86.47 (7) |
V4—V3—V5i | 91.63 (2) | V2i—O7—V1i | 88.32 (8) |
O6—V4—O5 | 102.96 (11) | V2—O7—V1i | 170.01 (11) |
O6—V4—O8 | 103.35 (11) | V4—O7—V1i | 86.14 (7) |
O5—V4—O8 | 94.37 (10) | V5i—O7—V1i | 85.68 (7) |
O6—V4—O2i | 99.70 (11) | V3—O7—V1i | 82.26 (7) |
O5—V4—O2i | 91.01 (10) | V4—O8—V3 | 115.28 (11) |
O8—V4—O2i | 154.46 (10) | V5—O10—V1 | 114.34 (11) |
O6—V4—O11 | 99.82 (10) | V2—O11—V5 | 107.38 (10) |
O5—V4—O11 | 155.46 (10) | V2—O11—V4 | 107.72 (10) |
O8—V4—O11 | 89.10 (10) | V5—O11—V4 | 99.95 (10) |
O2i—V4—O11 | 76.19 (9) | V2—O12—V1 | 110.25 (12) |
O6—V4—O7 | 174.61 (10) | V2—O12—Na1iii | 117.19 (11) |
O5—V4—O7 | 80.88 (9) | V1—O12—Na1iii | 122.48 (10) |
O8—V4—O7 | 79.94 (9) | V2—O13—V3 | 110.10 (11) |
O2i—V4—O7 | 76.30 (8) | V5—O14—V3i | 114.26 (11) |
O11—V4—O7 | 75.82 (8) | Na3—O15—Na1ii | 127.26 (11) |
O6—V4—V5 | 89.61 (9) | Na3—O15—H15A | 105 (2) |
O5—V4—V5 | 130.93 (7) | Na1ii—O15—H15A | 109 (3) |
O8—V4—V5 | 128.94 (7) | Na3—O15—H15B | 117 (2) |
O2i—V4—V5 | 39.92 (6) | Na1ii—O15—H15B | 89 (3) |
O11—V4—V5 | 39.84 (6) | H15A—O15—H15B | 108.4 (17) |
O7—V4—V5 | 85.01 (6) | Na2—O16—Na3 | 90.25 (9) |
O6—V4—V3 | 136.03 (9) | Na2—O16—H16B | 97 (2) |
O5—V4—V3 | 83.41 (7) | Na3—O16—H16B | 130 (2) |
O8—V4—V3 | 32.83 (7) | Na2—O16—H16A | 122 (3) |
O2i—V4—V3 | 123.89 (7) | Na3—O16—H16A | 110 (2) |
O11—V4—V3 | 86.53 (6) | H16B—O16—H16A | 107.9 (17) |
O7—V4—V3 | 47.65 (6) | Na2—O17—Na2iv | 95.46 (9) |
V5—V4—V3 | 119.11 (2) | Na2—O17—H17A | 113 (3) |
O6—V4—V1i | 136.07 (9) | Na2iv—O17—H17A | 110 (2) |
O5—V4—V1i | 33.31 (7) | Na2—O17—H17B | 110 (3) |
O8—V4—V1i | 82.74 (7) | Na2iv—O17—H17B | 117 (3) |
O2i—V4—V1i | 88.28 (6) | H17A—O17—H17B | 110.5 (18) |
O11—V4—V1i | 123.94 (6) | Na3—O18—Na2 | 93.87 (10) |
O7—V4—V1i | 48.13 (6) | Na3—O18—H18A | 116 (2) |
V5—V4—V1i | 120.53 (2) | Na2—O18—H18A | 106 (3) |
V3—V4—V1i | 58.548 (18) | Na3—O18—H18B | 123 (2) |
O3—V5—O14 | 103.46 (11) | Na2—O18—H18B | 106 (3) |
O3—V5—O10 | 102.49 (11) | H18A—O18—H18B | 109.1 (18) |
O14—V5—O10 | 94.98 (10) | Na2—O19—H19A | 109 (3) |
O3—V5—O11 | 99.28 (11) | Na2—O19—H19B | 115 (3) |
O14—V5—O11 | 155.10 (10) | H19A—O19—H19B | 111.9 (19) |
O10—V5—O11 | 89.86 (10) | Na1—O20—Na3 | 115.90 (11) |
O3—V5—O2i | 100.05 (11) | Na1—O20—H20A | 108.3 |
O14—V5—O2i | 89.83 (10) | Na3—O20—H20A | 108.3 |
O10—V5—O2i | 155.14 (10) | Na1—O20—H20B | 108.3 |
O11—V5—O2i | 76.22 (9) | Na3—O20—H20B | 108.3 |
O3—V5—O7i | 174.28 (10) | H20A—O20—H20B | 107.4 |
O14—V5—O7i | 80.64 (9) | Na2—O21—H21A | 112 (2) |
O10—V5—O7i | 80.94 (9) | Na2—O21—H21B | 126 (2) |
O11—V5—O7i | 76.02 (8) | H21A—O21—H21B | 108.5 (17) |
O2i—V5—O7i | 75.80 (8) | Na3—O22—Na3ii | 90.14 (9) |
O3—V5—V4 | 89.49 (8) | Na3—O22—H22A | 119 (2) |
O14—V5—V4 | 129.43 (7) | Na3ii—O22—H22A | 102 (2) |
O10—V5—V4 | 130.06 (7) | Na3—O22—H22B | 118 (2) |
O11—V5—V4 | 40.20 (6) | Na3ii—O22—H22B | 118 (3) |
O2i—V5—V4 | 39.60 (6) | H22A—O22—H22B | 108.7 (18) |
O7i—V5—V4 | 84.82 (6) | Na1—O23—H23A | 130 (3) |
O3—V5—V1 | 135.54 (9) | Na1—O23—H23B | 113 (3) |
O14—V5—V1 | 82.96 (7) | H23A—O23—H23B | 109.8 (18) |
O10—V5—V1 | 33.29 (7) | Na1—O24—H24A | 119 (3) |
O11—V5—V1 | 87.93 (6) | Na1—O24—H24B | 120 (2) |
O2i—V5—V1 | 124.15 (6) | H24A—O24—H24B | 111.5 (19) |
O7i—V5—V1 | 48.36 (6) | H1WA—O1W—H1WB | 110.6 (19) |
V4—V5—V1 | 120.52 (2) | H2WA—O2W—H2WB | 109.5 (19) |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | Na6(H2O)20(V10O28)·4H2O |
Mr | 1527.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 223 |
a, b, c (Å) | 10.5834 (3), 11.3803 (3), 11.6367 (3) |
α, β, γ (°) | 108.682 (4), 103.775 (2), 111.674 (3) |
V (Å3) | 1128.19 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.16 |
Crystal size (mm) | 0.30 × 0.24 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.542, 0.649 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11109, 4088, 3529 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.104, 1.01 |
No. of reflections | 4088 |
No. of parameters | 379 |
No. of restraints | 36 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.46 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXL97.
V1—O1 | 1.594 (2) | Na1—O23 | 2.393 (3) |
V1—O4i | 1.822 (2) | Na1—O1 | 2.455 (3) |
V1—O5i | 1.886 (2) | Na1—O15ii | 2.508 (3) |
V2—O12 | 1.689 (2) | Na1—O12iii | 2.948 (3) |
V2—O7i | 2.112 (2) | Na2—O21 | 2.320 (3) |
V3—O9 | 1.606 (2) | Na2—O19 | 2.352 (3) |
V4—O5 | 1.816 (2) | Na2—O16 | 2.420 (3) |
V5—O14 | 1.820 (2) | Na3—O18 | 2.334 (3) |
Na1—O24 | 2.328 (3) | Na3—O22ii | 2.397 (3) |
Na1—O20 | 2.348 (3) | Na3—O16 | 2.445 (3) |
O1—V1—O4i | 104.20 (12) | O24—Na1—O12iii | 81.98 (10) |
O1—V1—O10 | 102.55 (12) | O23—Na1—O12iii | 166.07 (11) |
O4i—V1—O5i | 91.57 (10) | O15ii—Na1—O12iii | 82.62 (8) |
O4i—V1—O12 | 155.93 (10) | O19—Na2—O18 | 84.58 (10) |
O5i—V1—O12 | 81.88 (9) | O21—Na2—O16 | 89.89 (10) |
O5i—V1—O7i | 77.13 (8) | O17—Na2—O16 | 100.36 (10) |
O24—Na1—O20 | 151.00 (12) | O19—Na2—O17iv | 92.11 (10) |
O20—Na1—O23 | 111.43 (11) | O16—Na2—O17iv | 166.64 (11) |
O20—Na1—O1 | 81.30 (9) | O22ii—Na3—O20 | 91.32 (9) |
O23—Na1—O1 | 91.56 (11) | O22ii—Na3—O16 | 178.15 (10) |
O20—Na1—O15ii | 82.00 (9) | O18—Na3—O15 | 95.80 (10) |
O23—Na1—O15ii | 89.50 (11) |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+2. |
Owing to their unusual topological properties and economically important applications in fields such as analytical chemistry, materials science and catalysis, nanotechnology, chemical sensing, luninescence, and medicine, polyoxometalates have aroused more and more attention in the past decade (Tanielian, 1998; Ouahab, 1998; Sadakane et al., 2000). Of the large polyoxometalate family, the most interesting class is polyoxovanadates, which are known to exhibit interesting physical and chemical properties with relevance to catalysis, biochemical processes and materials science (Zheng et al., 2005; Yang et al., 2003; Law et al., 2000). In recent years, a number of polyoxovanadate clusters exhibiting diverse topologies and interesting structural and electronic properties have been reported (Chen et al., 2005; Laye & McInnes, 2004). Although many compounds constructed from the [V10O28]6- polyoxoanion have been extensively studied, only a few complexes with three-dimensional frameworks have been reported (Zhang et al., 2004; Lee & Joo, 2003). In this communication, we describe a novel framework compound, Na6(H2O)20(V10O28)·4H2O, (I), prepared from V2O5, NaOH and HCl in solution.
The basic unit of (I) contains one [V10O28]6- polyanion with 2/m symmetry and two noncentrosymmetric [Na3(H2O)10]3+ cations (Fig. 1 and Table 1). The decavanadate anion is composed of ten VO6 octahedra combined via shared edges and shared corners. The bond lengths and angles of the [V10O28]6- anion are similar to those in the analogous compound Li6(H2O)16V10O28 (Xie & Ma, 2005). Bond valence sum calculations (Brown & Altermatt, 1985; O'Keeffe & Navrotsky, 1981) confirm that all the V atoms are in the +5 oxidation state (with bond valence sums in the 5.00–5.06 range).
There are three independent Na+ cations in (I). Atom Na1 is in a distorted octahedral coordination involving four O atoms (O20, O23, O24, O15B) from coordinated water molecules, one O atom (O1) from the [V10O28]6- anion and one µ2-O atom (O12B). Atoms Na2 and Na3 are both coordinated by six O atoms from water molecules that form distorted octahedral environments. Atoms Na2 and Na3 are linked by two µ2-O atoms (O16 and O18) to form dinuclear cations that are further linked to form [Na2(H2O)8]n chains in which the Na3···Na3A, Na2···Na2A and Na2···Na3 distances are 3.368 (3), 3.563 (3) and 3.448 (2) Å, respectively.
In the packing of (I), each [V10O28]6- anion acts as a µ4-bridge linking four Na1 cations through two terminal and two µ2-O atoms (Fig. 2). The decavanadate anions and the [Na2(H2O)8]n chains are linked to each other through Na1O6 octahedra to form a three-dimensional framework. To the best of our knowledge, a similar three-dimensional structure has not been described previously. In Na6V10O28.18H2O (Durif et al., 1980), decavanadate anions and trinuclear cations, [Na3(H2O)9]3+, link together to form a two-dimensional layer structure. In the related compound, K2Na4[V10O28].18H2O (Lee, 2006), chains of edge- and face-sharing [KO9] and [NaO6] polyhedra are interconnected by decavanadate anions to form a different three-dimensional network.