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The title compound, K
2[Co
II(H
2O)
6]
2[V
10O
28]·4H
2O, was obtained by reacting CoCl
2 with KVO
3 and it was found to crystallize in the triclinic system in space group
P. The V
V distances are in the range 3.050 (1)–3.291 (2) Å; the four types of V—O bond length are in the ranges 1.604 (3)–1.608 (3) (O
t), 1.902 (3)–2.006 (3) (O
c), 1.678 (3)–2.054 (3) (O
b) and 2.105 (3)–2.342 (3) Å (O
h).
Supporting information
Compound (I) was obtained by mixing hot aqueous solutions of KVO3 (0.5 g per 20 ml) and CoCl2 (0.1 g per 20 ml), and adjusting the pH to about 5.0 with 3 M HNO3. The solution was concentrated to about 20 ml by heating in a water bath. After a day, crystals of (I) were isolated at room temperature.
All H atoms were placed in calculated positions, with O—H distances ranging from 0.85 to 1.06 Å and O—H—O angles ranging from 85 to 170°. They were included in the refinement in riding-motion approximation, with Uiso(H) = 1.2Ueq(O). The highest peak in the difference map is 1.26 Å from H5b and the largest hole is 0.80 Å from V3.
Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.
Crystal data top
K2[Co(H2O)6]2[V10O28]·4H2O | Z = 1 |
Mr = 1441.72 | F(000) = 706 |
Triclinic, P1 | Dx = 2.692 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 10.762 (2) Å | Cell parameters from 28 reflections |
b = 11.122 (3) Å | θ = 9.5–10.4° |
c = 8.771 (2) Å | µ = 3.78 mm−1 |
α = 105.12 (2)° | T = 298 K |
β = 109.379 (18)° | Triclinic, pale brown |
γ = 65.112 (18)° | 0.13 × 0.10 × 0.09 mm |
V = 889.3 (4) Å3 | |
Data collection top
Stoe Stadi-4 diffractometer | 3403 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω/2–θ scans | h = −13→13 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1996) | k = −14→13 |
Tmin = 0.591, Tmax = 0.704 | l = 0→11 |
4092 measured reflections | 3 standard reflections every 60 min |
4092 independent reflections | intensity decay: 3.6% |
Refinement top
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0464P)2 + 0.7547P] where P = (Fo2 + 2Fc2)/3 |
4092 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.67 e Å−3 |
Crystal data top
K2[Co(H2O)6]2[V10O28]·4H2O | γ = 65.112 (18)° |
Mr = 1441.72 | V = 889.3 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.762 (2) Å | Mo Kα radiation |
b = 11.122 (3) Å | µ = 3.78 mm−1 |
c = 8.771 (2) Å | T = 298 K |
α = 105.12 (2)° | 0.13 × 0.10 × 0.09 mm |
β = 109.379 (18)° | |
Data collection top
Stoe Stadi-4 diffractometer | 3403 reflections with I > 2σ(I) |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1996) | Rint = 0.000 |
Tmin = 0.591, Tmax = 0.704 | 3 standard reflections every 60 min |
4092 measured reflections | intensity decay: 3.6% |
4092 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.54 e Å−3 |
4092 reflections | Δρmin = −0.67 e Å−3 |
262 parameters | |
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 | |
Co | 0.73135 (5) | 0.78797 (5) | 0.22397 (6) | 0.01776 (13) | |
V1 | 0.21943 (6) | 0.55217 (6) | 0.38463 (8) | 0.01514 (14) | |
V2 | 0.44893 (6) | 0.27453 (6) | 0.35229 (7) | 0.01450 (14) | |
V3 | 0.50332 (6) | 0.52219 (6) | 0.32330 (7) | 0.01313 (13) | |
V4 | 0.73705 (6) | 0.24400 (6) | 0.30740 (8) | 0.01748 (14) | |
V5 | 0.72672 (6) | 0.19784 (6) | 0.63300 (8) | 0.01756 (14) | |
K | 0.08436 (10) | 0.22436 (10) | 0.31861 (12) | 0.0319 (2) | |
Oh1 | 0.5993 (2) | 0.3789 (2) | 0.4847 (3) | 0.0136 (5) | |
Oc2 | 0.6429 (2) | 0.5906 (2) | 0.4773 (3) | 0.0143 (5) | |
Oc3 | 0.3624 (2) | 0.4455 (2) | 0.2592 (3) | 0.0142 (5) | |
Ob4 | 0.1578 (3) | 0.6545 (2) | 0.5641 (3) | 0.0175 (5) | |
Ob5 | 0.5692 (3) | 0.2033 (2) | 0.2210 (3) | 0.0179 (5) | |
Ob6 | 0.6089 (3) | 0.4152 (3) | 0.2034 (3) | 0.0172 (5) | |
Ob7 | 0.4039 (3) | 0.6627 (3) | 0.2322 (3) | 0.0178 (5) | |
Ob8 | 0.5611 (3) | 0.1637 (2) | 0.5078 (3) | 0.0173 (5) | |
Ob9 | 0.8046 (3) | 0.1282 (3) | 0.4564 (3) | 0.0193 (5) | |
Ob10 | 0.8375 (3) | 0.3037 (3) | 0.7200 (3) | 0.0186 (5) | |
Ot11 | 0.1026 (3) | 0.4849 (3) | 0.2944 (3) | 0.0237 (6) | |
Ot12 | 0.3274 (3) | 0.2140 (3) | 0.2596 (3) | 0.0225 (6) | |
Ot13 | 0.8226 (3) | 0.1603 (3) | 0.1711 (4) | 0.0270 (6) | |
Ot14 | 0.8068 (3) | 0.0789 (3) | 0.7410 (4) | 0.0294 (7) | |
Ow1 | 0.8948 (3) | 0.8571 (3) | 0.3700 (4) | 0.0244 (6) | |
H1a | 0.9824 | 0.8193 | 0.3454 | 0.029* | |
H1b | 0.8609 | 0.9497 | 0.3772 | 0.029* | |
Ow2 | 0.8227 (3) | 0.6302 (3) | 0.3619 (4) | 0.0253 (6) | |
H2a | 0.7779 | 0.6062 | 0.4049 | 0.030* | |
H2b | 0.8997 | 0.5556 | 0.3135 | 0.030* | |
Ow3 | 0.6271 (3) | 0.8983 (3) | 0.4051 (4) | 0.0319 (7) | |
H3a | 0.5560 | 0.8779 | 0.4187 | 0.038* | |
H3b | 0.6079 | 0.9957 | 0.4294 | 0.038* | |
Ow4 | 0.6568 (3) | 0.9393 (3) | 0.0825 (4) | 0.0290 (6) | |
H4a | 0.7213 | 0.9438 | 0.0371 | 0.035* | |
H4b | 0.5998 | 1.0206 | 0.0953 | 0.035* | |
Ow5 | 0.8480 (3) | 0.6640 (3) | 0.0553 (4) | 0.0333 (7) | |
H5a | 0.9014 | 0.6997 | 0.0595 | 0.040* | |
H5b | 0.8544 | 0.5802 | 0.0274 | 0.040* | |
Ow6 | 0.5635 (4) | 0.7279 (4) | 0.0932 (4) | 0.0449 (9) | |
H6a | 0.5012 | 0.7583 | −0.0167 | 0.054* | |
H6b | 0.5034 | 0.7166 | 0.1356 | 0.054* | |
Ow7 | −0.1544 (4) | 0.4081 (3) | 0.0684 (4) | 0.0417 (8) | |
H7a | −0.2510 | 0.4059 | 0.0725 | 0.050* | |
H7b | −0.1610 | 0.3573 | −0.0382 | 0.050* | |
Ow8 | 0.0784 (4) | 0.1119 (4) | −0.0022 (4) | 0.0465 (9) | |
H8a | 0.1225 | 0.1572 | −0.0361 | 0.056* | |
H8b | −0.0212 | 0.1474 | −0.0578 | 0.056* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co | 0.0183 (2) | 0.0171 (2) | 0.0192 (3) | −0.0066 (2) | 0.00568 (19) | 0.00332 (19) |
V1 | 0.0103 (3) | 0.0148 (3) | 0.0198 (3) | −0.0044 (2) | 0.0027 (2) | 0.0033 (2) |
V2 | 0.0127 (3) | 0.0136 (3) | 0.0180 (3) | −0.0058 (2) | 0.0044 (2) | 0.0011 (2) |
V3 | 0.0125 (3) | 0.0143 (3) | 0.0142 (3) | −0.0051 (2) | 0.0041 (2) | 0.0034 (2) |
V4 | 0.0146 (3) | 0.0171 (3) | 0.0209 (3) | −0.0046 (2) | 0.0079 (2) | 0.0007 (2) |
V5 | 0.0143 (3) | 0.0151 (3) | 0.0228 (3) | −0.0035 (2) | 0.0031 (2) | 0.0073 (2) |
K | 0.0255 (5) | 0.0412 (6) | 0.0339 (5) | −0.0148 (4) | 0.0127 (4) | 0.0018 (4) |
Oh1 | 0.0119 (11) | 0.0139 (12) | 0.0163 (12) | −0.0052 (9) | 0.0038 (9) | 0.0033 (9) |
Oc2 | 0.0122 (11) | 0.0143 (12) | 0.0177 (12) | −0.0047 (9) | 0.0041 (9) | 0.0042 (9) |
Oc3 | 0.0140 (11) | 0.0157 (12) | 0.0141 (12) | −0.0062 (10) | 0.0033 (9) | 0.0030 (9) |
Ob4 | 0.0130 (12) | 0.0175 (12) | 0.0228 (13) | −0.0045 (10) | 0.0071 (10) | 0.0027 (10) |
Ob5 | 0.0190 (12) | 0.0157 (12) | 0.0202 (13) | −0.0082 (10) | 0.0072 (10) | −0.0014 (10) |
Ob6 | 0.0164 (12) | 0.0183 (13) | 0.0174 (13) | −0.0048 (10) | 0.0069 (10) | 0.0025 (10) |
Ob7 | 0.0162 (12) | 0.0193 (13) | 0.0186 (13) | −0.0061 (10) | 0.0034 (10) | 0.0057 (10) |
Ob8 | 0.0169 (12) | 0.0137 (12) | 0.0225 (13) | −0.0055 (10) | 0.0052 (10) | 0.0045 (10) |
Ob9 | 0.0167 (12) | 0.0145 (12) | 0.0258 (14) | −0.0040 (10) | 0.0054 (11) | 0.0043 (10) |
Ob10 | 0.0157 (12) | 0.0183 (13) | 0.0220 (13) | −0.0062 (10) | 0.0028 (10) | 0.0057 (10) |
Ot11 | 0.0172 (13) | 0.0248 (14) | 0.0301 (15) | −0.0109 (11) | 0.0020 (11) | 0.0054 (12) |
Ot12 | 0.0198 (13) | 0.0251 (14) | 0.0255 (14) | −0.0135 (11) | 0.0051 (11) | 0.0003 (11) |
Ot13 | 0.0254 (15) | 0.0271 (15) | 0.0306 (16) | −0.0096 (12) | 0.0148 (13) | −0.0025 (12) |
Ot14 | 0.0281 (15) | 0.0220 (14) | 0.0373 (17) | −0.0057 (12) | 0.0029 (13) | 0.0162 (13) |
Ow1 | 0.0156 (13) | 0.0184 (13) | 0.0364 (16) | −0.0058 (11) | 0.0043 (12) | 0.0031 (12) |
Ow2 | 0.0242 (14) | 0.0223 (14) | 0.0348 (16) | −0.0047 (12) | 0.0129 (12) | 0.0122 (12) |
Ow3 | 0.0385 (17) | 0.0217 (15) | 0.0473 (19) | −0.0139 (13) | 0.0297 (15) | −0.0055 (13) |
Ow4 | 0.0335 (16) | 0.0208 (14) | 0.0324 (16) | −0.0073 (13) | 0.0087 (13) | 0.0072 (12) |
Ow5 | 0.0393 (18) | 0.0296 (16) | 0.0314 (17) | −0.0096 (14) | 0.0174 (14) | −0.0011 (13) |
Ow6 | 0.049 (2) | 0.084 (3) | 0.0267 (17) | −0.052 (2) | −0.0029 (15) | 0.0161 (17) |
Ow7 | 0.047 (2) | 0.0389 (19) | 0.039 (2) | −0.0213 (17) | 0.0096 (16) | −0.0031 (15) |
Ow8 | 0.053 (2) | 0.057 (2) | 0.038 (2) | −0.0292 (19) | 0.0136 (17) | 0.0032 (17) |
Geometric parameters (Å, º) top
V1—V2 | 3.050 (1) | V2—Ob5 | 1.811 (3) |
V1—V3 | 3.142 (1) | V2—Ob8 | 1.836 (3) |
V1—V3i | 3.179 (1) | V2—Ot12 | 1.604 (3) |
V1—V4i | 3.084 (1) | V3—Oh1 | 2.105 (2) |
V1—V5i | 3.119 (1) | V3—Oh1i | 2.124 (2) |
V2—V3 | 3.133 (1) | V3—Oc2 | 1.933 (2) |
V2—V3i | 3.182 (1) | V3—Oc3 | 1.902 (2) |
V2—V4 | 3.121 (1) | V3—Ob6 | 1.678 (3) |
V2—V5 | 3.129 (1) | V3—Ob7 | 1.704 (3) |
V3—V3i | 3.291 (1) | V4—Oh1 | 2.304 (2) |
V3—V4 | 3.062 (1) | V4—Ob6 | 2.054 (3) |
V3—V5i | 3.081 (1) | V4—Ob4i | 1.841 (3) |
V4—V5 | 3.075 (1) | V4—Ob5 | 1.908 (3) |
V4—V1i | 3.084 (1) | V4—Ob9 | 1.832 (3) |
Co—Ow1 | 2.111 (3) | V4—Ot13 | 1.604 (3) |
Co—Ow2 | 2.092 (3) | V5—Oh1 | 2.342 (3) |
Co—Ow3 | 2.072 (3) | V5—Ob7i | 2.022 (3) |
Co—Ow4 | 2.076 (3) | V5—Ob8 | 1.892 (3) |
Co—Ow5 | 2.092 (3) | V5—Ob9 | 1.841 (3) |
Co—Ow6 | 2.066 (3) | V5—Ob10 | 1.870 (3) |
V1—Oh1i | 2.241 (2) | V5—OT14 | 1.594 (3) |
V1—Oc2i | 2.004 (3) | K—Ob4ii | 2.786 (3) |
V1—Oc3 | 1.973 (2) | K—Ow8 | 2.756 (4) |
V1—Ob4 | 1.826 (3) | K—Ot11 | 3.051 (3) |
V1—Ob10i | 1.832 (3) | K—Ot12 | 2.782 (3) |
V1—Ot11 | 1.608 (3) | K—Ot13iii | 2.984 (3) |
V2—Oh1 | 2.224 (2) | K—Ot14iv | 3.030 (3) |
V2—Oc2i | 2.006 (3) | K—Ow1i | 3.008 (3) |
V2—Oc3 | 1.992 (3) | K—Ow2i | 2.934 (3) |
| | | |
V2—V1—V4i | 119.88 (3) | Ot12—V2—Oh1 | 174.02 (12) |
V2—V1—V5i | 119.67 (3) | Ob5—V2—Oh1 | 80.86 (10) |
V2—V1—V3 | 60.76 (3) | Ob8—V2—Oh1 | 81.28 (10) |
V4i—V1—V3 | 90.18 (3) | Oc3—V2—Oh1 | 76.14 (10) |
V5i—V1—V3 | 58.94 (2) | Oc2i—V2—Oh1 | 75.88 (9) |
V2—V1—V3i | 61.39 (3) | Ob6—V3—Ob7 | 107.18 (13) |
V3—V1—V3i | 62.75 (3) | Ob6—V3—Oc3 | 98.84 (12) |
V1—V2—V4 | 119.64 (3) | Ob7—V3—Oc3 | 97.50 (11) |
V1—V2—V5 | 119.72 (3) | Ob6—V3—Oc2 | 96.46 (12) |
V4—V2—V5 | 58.95 (3) | Ob7—V3—Oc2 | 96.41 (12) |
V1—V2—V3 | 61.07 (3) | Oc3—V3—Oc2 | 155.25 (10) |
V4—V2—V3 | 58.63 (2) | Ob6—V3—Oh1 | 87.87 (11) |
V5—V2—V3 | 90.13 (3) | Ob7—V3—Oh1 | 164.90 (11) |
V1—V2—V3i | 61.30 (3) | Oc3—V3—Oh1 | 80.97 (10) |
V4—V2—V3i | 88.81 (3) | Oc2—V3—Oh1 | 80.28 (10) |
V5—V2—V3i | 58.43 (3) | Ob6—V3—Oh1i | 165.58 (11) |
V3—V2—V3i | 62.82 (3) | Ob7—V3—Oh1i | 87.13 (11) |
V4—V3—V5i | 175.71 (3) | Oc3—V3—Oh1i | 80.58 (10) |
V5i—V3—V2 | 118.30 (3) | Oc2—V3—Oh1i | 79.78 (10) |
V4—V3—V1 | 118.59 (3) | Oh1—V3—Oh1i | 77.80 (10) |
V5i—V3—V1 | 60.16 (3) | Ot13—V4—Ob9 | 103.26 (14) |
V2—V3—V1 | 58.17 (2) | Ot13—V4—Ob4i | 102.36 (13) |
V4—V3—V3i | 87.84 (4) | Ob9—V4—Ob4i | 93.31 (12) |
V2—V3—V3i | 59.31 (3) | Ot13—V4—Ob5 | 101.55 (13) |
V1—V3—V3i | 59.17 (3) | Ob9—V4—Ob5 | 90.24 (12) |
V4—V3—V4i | 131.78 (3) | Ob4i—V4—Ob5 | 154.31 (11) |
V2—V3—V4i | 87.78 (3) | Ot13—V4—Ob6 | 99.96 (13) |
V1—V3—V4i | 44.38 (2) | Ob9—V4—Ob6 | 156.62 (11) |
V3—V4—V5 | 92.49 (3) | Ob4i—V4—Ob6 | 84.27 (11) |
V3—V4—V2 | 60.88 (3) | Ob5—V4—Ob6 | 82.49 (11) |
V5—V4—V2 | 60.66 (3) | Ot13—V4—Oh1 | 174.26 (13) |
V1i—V4—V2 | 91.57 (3) | Ob9—V4—Oh1 | 82.31 (10) |
V4—V5—V3i | 91.52 (3) | Ob4i—V4—Oh1 | 78.44 (10) |
V4—V5—V1i | 59.72 (3) | Ob5—V4—Oh1 | 76.84 (10) |
V4—V5—V2 | 60.39 (3) | Ob6—V4—Oh1 | 74.41 (9) |
V3i—V5—V2 | 61.64 (3) | Ot14—V5—Ob9 | 102.42 (14) |
V1i—V5—V2 | 90.76 (3) | Ot14—V5—Ob10 | 102.87 (14) |
V4—V5—V3 | 43.64 (2) | Ob9—V5—Ob10 | 90.62 (12) |
V3i—V5—V3 | 47.90 (3) | Ot14—V5—Ob8 | 102.06 (14) |
V1i—V5—V3 | 45.81 (2) | Ob9—V5—Ob8 | 90.61 (12) |
V2—V5—V3 | 44.97 (2) | Ob10—V5—Ob8 | 154.16 (11) |
Ow6—Co—Ow3 | 90.84 (14) | Ot14—V5—Ob7i | 102.00 (14) |
Ow6—Co—Ow4 | 90.92 (13) | Ob9—V5—Ob7i | 155.58 (11) |
Ow3—Co—Ow4 | 97.41 (12) | Ob10—V5—Ob7i | 84.68 (11) |
Ow6—Co—Ow5 | 90.44 (14) | Ob8—V5—Ob7i | 83.60 (11) |
Ow3—Co—Ow5 | 174.88 (13) | Ot14—V5—Oh1 | 176.47 (13) |
Ow4—Co—Ow5 | 87.52 (12) | Ob9—V5—Oh1 | 81.04 (10) |
Ow6—Co—Ow2 | 91.95 (13) | Ob10—V5—Oh1 | 77.68 (10) |
Ow3—Co—Ow2 | 86.36 (12) | Ob8—V5—Oh1 | 77.02 (10) |
Ow4—Co—Ow2 | 175.23 (11) | Ob7i—V5—Oh1 | 74.54 (9) |
Ow5—Co—Ow2 | 88.65 (12) | V3—Oh1—V3i | 102.20 (10) |
Ow6—Co—Ow1 | 175.99 (13) | V3—Oh1—V2 | 92.69 (9) |
Ow3—Co—Ow1 | 85.15 (12) | V3i—Oh1—V2 | 94.05 (9) |
Ow4—Co—Ow1 | 89.58 (12) | V3—Oh1—V1i | 93.95 (9) |
Ow5—Co—Ow1 | 93.56 (12) | V2—Oh1—V1i | 169.85 (12) |
Ow2—Co—Ow1 | 87.82 (11) | V3—Oh1—V4 | 87.86 (9) |
Ot11—V1—Ob4 | 102.41 (13) | V3i—Oh1—V4 | 169.79 (12) |
Ot11—V1—Ob10i | 104.73 (13) | V2—Oh1—V4 | 87.13 (9) |
Ob4—V1—Ob10i | 93.80 (12) | V1i—Oh1—V4 | 85.46 (8) |
Ot11—V1—Oc3 | 99.93 (13) | V3—Oh1—V5 | 170.73 (12) |
Ob4—V1—Oc3 | 155.06 (11) | V3i—Oh1—V5 | 87.07 (9) |
Ob10i—V1—Oc3 | 91.10 (11) | V2—Oh1—V5 | 86.48 (8) |
Ot11—V1—Oc2i | 98.16 (13) | V1i—Oh1—V5 | 85.73 (8) |
Ob4—V1—Oc2i | 89.15 (11) | V4—Oh1—V5 | 82.88 (8) |
Oc3—V1—Oc2i | 76.79 (10) | V3—Oc2—V1i | 107.68 (11) |
Ot11—V1—Oh1i | 173.15 (12) | V3—Oc2—V2i | 107.71 (11) |
Ob4—V1—Oh1i | 80.43 (10) | V3—Oc3—V1 | 108.39 (12) |
Oc3—V1—Oh1i | 76.19 (9) | V3—Oc3—V2 | 107.14 (12) |
Ot12—V2—Ob5 | 103.42 (13) | V1—Oc3—V2 | 100.61 (11) |
Ot12—V2—Ob8 | 102.27 (13) | V1—Ob4—V4i | 114.48 (13) |
Ob5—V2—Ob8 | 95.51 (12) | V1—Ob4—Kii | 141.57 (13) |
Ot12—V2—Oc3 | 99.48 (13) | V2—Ob5—V4 | 114.05 (13) |
Ob5—V2—Oc3 | 90.42 (11) | V3—Ob6—V4 | 109.86 (13) |
Ob8—V2—Oc3 | 155.43 (11) | V3—Ob7—V5i | 111.25 (13) |
Ot12—V2—Oc2i | 99.24 (12) | V2—Ob8—V5 | 114.14 (13) |
Ob5—V2—Oc2i | 155.35 (11) | V4—Ob9—V5 | 113.71 (14) |
Ob8—V2—Oc2i | 88.97 (11) | V1i—Ob10—V5 | 114.83 (14) |
Oc3—V2—Oc2i | 76.30 (10) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
Ow1—H1b···Ob9v | 0.93 | 1.83 | 2.728 (4) | 163 |
Ow1—H1a···Ob10vi | 0.93 | 2.01 | 2.925 (4) | 166 |
Ow1—H1b···Ow4 | 0.93 | 2.79 | 2.950 (4) | 90 |
Ow1—H1a···Ow5 | 0.93 | 2.99 | 3.063 (4) | 86 |
Ow1—H1a···Ob4vii | 0.93 | 2.67 | 3.069 (4) | 107 |
Ow2—H2a···Oc2 | 0.85 | 1.85 | 2.685 (3) | 166 |
Ow2—H2b···Ow5 | 1.01 | 2.63 | 2.923 (4) | 97 |
Ow2—H2b···Ow7vii | 1.01 | 2.41 | 3.063 (4) | 122 |
Ow2—H2b···Ot11vii | 1.01 | 2.04 | 2.937 (4) | 147 |
Ow3—H3b···Ob8v | 0.99 | 1.73 | 2.702 (4) | 167 |
Ow3—H3a···Ob8i | 0.93 | 1.84 | 2.763 (4) | 167 |
Ow4—H4b···Ob5v | 0.86 | 1.99 | 2.749 (4) | 147 |
Ow4—H4b···Ow4viii | 0.86 | 2.59 | 3.041 (6) | 114 |
Ow4—H4a···Ow8ix | 0.93 | 2.08 | 2.949 (5) | 154 |
Ow4—H4a···Ot12ix | 0.93 | 2.76 | 3.060 (4) | 100 |
Ow5—H5b···Ow7vii | 0.88 | 2.08 | 2.889 (5) | 152 |
Ow6—H6b···Ob7 | 0.91 | 1.91 | 2.804 (4) | 170 |
Ow7—H7b···Ob10x | 0.96 | 2.04 | 2.958 (4) | 160 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (v) x, y+1, z; (vi) −x+2, −y+1, −z+1; (vii) x+1, y, z; (viii) −x+1, −y+2, −z; (ix) −x+1, −y+1, −z; (x) x−1, y, z−1. |
Experimental details
Crystal data |
Chemical formula | K2[Co(H2O)6]2[V10O28]·4H2O |
Mr | 1441.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 10.762 (2), 11.122 (3), 8.771 (2) |
α, β, γ (°) | 105.12 (2), 109.379 (18), 65.112 (18) |
V (Å3) | 889.3 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 3.78 |
Crystal size (mm) | 0.13 × 0.10 × 0.09 |
|
Data collection |
Diffractometer | Stoe Stadi-4 diffractometer |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 1996) |
Tmin, Tmax | 0.591, 0.704 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4092, 4092, 3403 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.096, 1.12 |
No. of reflections | 4092 |
No. of parameters | 262 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.67 |
Selected bond lengths (Å) topV1—Oh1i | 2.241 (2) | V3—Oc3 | 1.902 (2) |
V1—Oc2i | 2.004 (3) | V3—Ob6 | 1.678 (3) |
V1—Oc3 | 1.973 (2) | V3—Ob7 | 1.704 (3) |
V1—Ob4 | 1.826 (3) | V4—Oh1 | 2.304 (2) |
V1—Ob10i | 1.832 (3) | V4—Ob6 | 2.054 (3) |
V1—Ot11 | 1.608 (3) | V4—Ob4i | 1.841 (3) |
V2—Oh1 | 2.224 (2) | V4—Ob5 | 1.908 (3) |
V2—Oc2i | 2.006 (3) | V4—Ob9 | 1.832 (3) |
V2—Oc3 | 1.992 (3) | V4—Ot13 | 1.604 (3) |
V2—Ob5 | 1.811 (3) | V5—Oh1 | 2.342 (3) |
V2—Ob8 | 1.836 (3) | V5—Ob7i | 2.022 (3) |
V2—Ot12 | 1.604 (3) | V5—Ob8 | 1.892 (3) |
V3—Oh1 | 2.105 (2) | V5—Ob9 | 1.841 (3) |
V3—Oh1i | 2.124 (2) | V5—Ob10 | 1.870 (3) |
V3—Oc2 | 1.933 (2) | V5—OT14 | 1.594 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
Ow1—H1b···Ob9ii | 0.93 | 1.83 | 2.728 (4) | 163 |
Ow1—H1a···Ob10iii | 0.93 | 2.01 | 2.925 (4) | 166 |
Ow1—H1b···Ow4 | 0.93 | 2.79 | 2.950 (4) | 90 |
Ow1—H1a···Ow5 | 0.93 | 2.99 | 3.063 (4) | 86 |
Ow1—H1a···Ob4iv | 0.93 | 2.67 | 3.069 (4) | 107 |
Ow2—H2a···Oc2 | 0.85 | 1.85 | 2.685 (3) | 166 |
Ow2—H2b···Ow5 | 1.01 | 2.63 | 2.923 (4) | 97 |
Ow2—H2b···Ow7iv | 1.01 | 2.41 | 3.063 (4) | 122 |
Ow2—H2b···Ot11iv | 1.01 | 2.04 | 2.937 (4) | 147 |
Ow3—H3b···Ob8ii | 0.99 | 1.73 | 2.702 (4) | 167 |
Ow3—H3a···Ob8i | 0.93 | 1.84 | 2.763 (4) | 167 |
Ow4—H4b···Ob5ii | 0.86 | 1.99 | 2.749 (4) | 147 |
Ow4—H4b···Ow4v | 0.86 | 2.59 | 3.041 (6) | 114 |
Ow4—H4a···Ow8vi | 0.93 | 2.08 | 2.949 (5) | 154 |
Ow4—H4a···Ot12vi | 0.93 | 2.76 | 3.060 (4) | 100 |
Ow5—H5b···Ow7iv | 0.88 | 2.08 | 2.889 (5) | 152 |
Ow6—H6b···Ob7 | 0.91 | 1.91 | 2.804 (4) | 170 |
Ow7—H7b···Ob10vii | 0.96 | 2.04 | 2.958 (4) | 160 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) −x+2, −y+1, −z+1; (iv) x+1, y, z; (v) −x+1, −y+2, −z; (vi) −x+1, −y+1, −z; (vii) x−1, y, z−1. |
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The decavanadate anion, [V10O28]6−, is a very stable and typical isopolyanion species of vanadium. Since its crystal structure was reported by Evans (1966), structures of many salts have been characterized. Crystal structures of double salts, e.g. K2[Zn(H2O)6]2[V10O28]·4H2O (Evans, 1966), (NH4)2[Co2[V10O28].16H2O (Nowogrocki et al., 1997), [Na(H2O)3]2[Ni(H2O)]2[V10O28]·4H2O, (Higami et al., 2002), and Na4[Ni(H2O)6][[V10O28].17H2O (Sun et al., 2002), consisting of transition metal and alkali metal have been reported. The structure of the title compound, K2[CoII(H2O)6]2[V10O28]·4H2O, (I), is isostructural with K2[Zn(H2O)6]2[V10O28]·4H2O (Evans, 1966).
The configuration of the polyanion is shown in Fig. 1. The centrosymmetric polyanion consists of five independent [VO6] octahedra sharing edges with approximate D2 h symmetry. The O atoms in the anion can be divided into four groups by the environment of coordination, viz. Ot, Ob, Oc, and Oh, where Ot represents a terminal O atom bound to a V atom, Ob represents a doubly bridging O atoms bound to two V atoms, Oc represents a triply bridging O atoms bound to three V atoms, and Oh represents a central O atom coordinated to six V atoms. The V···V distances are in the range 3.050 (1)–3.291 (2) Å; four types of V—O bond length are in the ranges 1.604 (3)–1.608 (3) (Ot), 1.902 (3)–2.006 (3) (Oc), 1.678 (3)–2.054 (3)(Ob) and 2.105 (3)–2.342 (3) Å (Oh). The bond lengths and angles of [V10O28]6− shows the similar trends to those found in the reference literature. The framework of [V10O28]6− has been studied in detail previously (Evans, 1966; Nowogrocki et al., 1997).
Fig. 2 shows the crystal packing of (I) with the hydrogen-bonding interactions. All the O atoms of the anion, except Oh1, Oc3,Ob6, Ot13 and Ot14, form hydrogen bonds with water molecules. The [V10O28]6− and [Co(H2O)6]2+ ions are linked together by strong hydrogen bonds. The Co2+ ion is surrounded by six water molecules in the form of a regular octahedron, with distances ranging from 2.072 (3) to 2.111 (3) Å. The K+ ion is coordinated to eight O atoms, with distances in the range 2.756 (4)–3.030 (3) Å. A list of hydrogen-bond distances involving water molecules below 3.1 Å is given in Table 2.