Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102015603/iz1023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102015603/iz1023Isup2.hkl |
V2O5 (0.4652 g, 0.0025 mol) and 6 M NaOH (5.0 ml, 0.03 mol) were added to water (ca 20 ml). The mixture was stirred in an ice bath, producing a clear yellow solution. The solution was adjusted to 25 ml by adding 30% H2O2 (0.5 ml), 6 M HNO3 (volume?) and water (volume?). This brought the pH of the solution to 4.10. An aqueous solution of 1 M Ni(NO3)2·6H2O (5 ml, 0.005 mol) was added to this solution, and then ethanol (7.5 ml). The final molar ratio of H2O2:V:Na:Ni was 1:1:3:1. Tabular green-orange crystals of (I) appeared in about 12 h, usually together with prismatic deep-orange crystals, which were most probably sodium decavanadate.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
[Ni(H2O)6]2[Na(H2O)3]2V10O28·4H2O | Z = 1 |
Mr = 1517.15 | F(000) = 752 |
Triclinic, P1 | Dx = 2.404 Mg m−3 |
a = 10.836 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 12.606 (2) Å | Cell parameters from 25 reflections |
c = 8.331 (1) Å | θ = 16.8–17.5° |
α = 93.19 (2)° | µ = 3.15 mm−1 |
β = 99.83 (2)° | T = 293 K |
γ = 109.65 (2)° | Prismatic, green-orange |
V = 1048.1 (3) Å3 | 0.50 × 0.18 × 0.05 mm |
Rigaku AFC-5R automated four-circle diffractometer | 6109 independent reflections |
Radiation source: normal focus rotating anode | 3399 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 3 pixels mm-1 | θmax = 30.0°, θmin = 2.9° |
ω/2θ scans | h = 0→15 |
Absorption correction: ψ scan TEXSAN (Molecular Structure Corporation, 1995) | k = −17→16 |
Tmin = 0.553, Tmax = 0.854 | l = −11→11 |
6109 measured reflections |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters not defined |
S = 1.07 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo2) + (0.0315P)2 + 9.2497P] where P = (Fo2 + 2Fc2)/3 |
6109 reflections | (Δ/σ)max = 0.001 |
301 parameters | Δρmax = 0.89 e Å−3 |
0 restraints | Δρmin = −0.81 e Å−3 |
[Ni(H2O)6]2[Na(H2O)3]2V10O28·4H2O | γ = 109.65 (2)° |
Mr = 1517.15 | V = 1048.1 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.836 (2) Å | Mo Kα radiation |
b = 12.606 (2) Å | µ = 3.15 mm−1 |
c = 8.331 (1) Å | T = 293 K |
α = 93.19 (2)° | 0.50 × 0.18 × 0.05 mm |
β = 99.83 (2)° |
Rigaku AFC-5R automated four-circle diffractometer | 6109 independent reflections |
Absorption correction: ψ scan TEXSAN (Molecular Structure Corporation, 1995) | 3399 reflections with I > 2σ(I) |
Tmin = 0.553, Tmax = 0.854 | Rint = 0.048 |
6109 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters not defined |
S = 1.07 | Δρmax = 0.89 e Å−3 |
6109 reflections | Δρmin = −0.81 e Å−3 |
301 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 | Occ. (<1) | |
Ni1 | 0.5000 | 0.0000 | 0.0000 | 0.0193 (3) | |
Ni2 | 0.0000 | 0.5000 | 0.0000 | 0.0225 (3) | |
V1 | 0.52589 (11) | 0.29325 (10) | 0.48469 (14) | 0.0161 (2) | |
V2 | 0.54232 (11) | 0.51351 (10) | 0.70205 (14) | 0.0135 (2) | |
V3 | 0.31139 (12) | 0.28671 (11) | 0.69173 (15) | 0.0198 (3) | |
V4 | 0.23279 (12) | 0.26101 (10) | 0.31599 (15) | 0.0190 (3) | |
V5 | 0.24935 (11) | 0.48117 (10) | 0.52379 (14) | 0.0155 (2) | |
Na1 | 0.7383 (3) | 0.1032 (3) | 0.3864 (4) | 0.0301 (7) | |
O1 | 0.6239 (5) | 0.2247 (4) | 0.4637 (7) | 0.0262 (12) | |
O2 | 0.4499 (5) | 0.2346 (4) | 0.6524 (6) | 0.0191 (10) | |
O3 | 0.3786 (5) | 0.2131 (4) | 0.3211 (6) | 0.0184 (10) | |
O4 | 0.3506 (4) | 0.5699 (4) | 0.3673 (5) | 0.0149 (9) | |
O5 | 0.4161 (5) | 0.5900 (4) | 0.6700 (6) | 0.0170 (10) | |
O6 | 0.5982 (4) | 0.5975 (4) | 0.4974 (6) | 0.0150 (9) | |
O7 | 0.4685 (5) | 0.4206 (4) | 0.8245 (6) | 0.0216 (11) | |
O8 | 0.6717 (5) | 0.6192 (4) | 0.8233 (6) | 0.0183 (10) | |
O9 | 0.2603 (5) | 0.2146 (5) | 0.8350 (7) | 0.0308 (13) | |
O10 | 0.1987 (5) | 0.2008 (4) | 0.5061 (6) | 0.0208 (10) | |
O11 | 0.2197 (5) | 0.3897 (4) | 0.6848 (6) | 0.0196 (10) | |
O12 | 0.1211 (5) | 0.1717 (5) | 0.1748 (7) | 0.0316 (13) | |
O13 | 0.1498 (5) | 0.5507 (4) | 0.5359 (7) | 0.0258 (12) | |
O14 | 0.1532 (5) | 0.3682 (4) | 0.3578 (6) | 0.0183 (10) | |
O15 | 0.6738 (5) | 0.1368 (4) | 0.0905 (7) | 0.0280 (12) | |
O16 | 0.5122 (5) | −0.0434 (4) | 0.2414 (6) | 0.0226 (11) | |
O17 | 0.3841 (6) | 0.0934 (5) | 0.0456 (6) | 0.0303 (13) | |
O18 | −0.0518 (5) | 0.4074 (5) | 0.1884 (6) | 0.0288 (12) | |
O19 | −0.1724 (5) | 0.3819 (5) | −0.1394 (7) | 0.0315 (13) | |
O20 | 0.1065 (6) | 0.3955 (5) | −0.0516 (7) | 0.0319 (14) | |
O21A | 0.914 (4) | 0.023 (3) | 0.383 (4) | 0.050 (8) | 0.30 |
O21B | 0.8811 (15) | 0.0220 (12) | 0.2953 (19) | 0.058 (4) | 0.70 |
O22 | 0.9216 (6) | 0.2515 (6) | 0.5481 (9) | 0.0494 (18) | |
O23 | 0.6994 (6) | 0.0209 (5) | 0.6312 (7) | 0.0324 (13) | |
O24 | 0.3706 (5) | 0.6672 (5) | 0.9513 (7) | 0.0294 (12) | |
O25 | 0.8820 (7) | 0.1568 (6) | −0.0816 (9) | 0.0492 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0246 (7) | 0.0165 (6) | 0.0183 (6) | 0.0090 (5) | 0.0048 (5) | 0.0029 (5) |
Ni2 | 0.0195 (6) | 0.0343 (8) | 0.0168 (6) | 0.0137 (6) | 0.0028 (5) | 0.0058 (6) |
V1 | 0.0164 (5) | 0.0116 (5) | 0.0211 (6) | 0.0070 (4) | 0.0019 (5) | 0.0014 (5) |
V2 | 0.0147 (5) | 0.0146 (5) | 0.0125 (5) | 0.0069 (4) | 0.0025 (4) | 0.0015 (4) |
V3 | 0.0200 (6) | 0.0189 (6) | 0.0222 (6) | 0.0070 (5) | 0.0065 (5) | 0.0087 (5) |
V4 | 0.0163 (6) | 0.0148 (6) | 0.0222 (6) | 0.0038 (5) | −0.0010 (5) | −0.0009 (5) |
V5 | 0.0134 (5) | 0.0161 (6) | 0.0194 (6) | 0.0074 (5) | 0.0043 (4) | 0.0032 (5) |
Na1 | 0.0321 (17) | 0.0282 (17) | 0.0319 (17) | 0.0120 (14) | 0.0087 (14) | 0.0044 (14) |
O1 | 0.023 (3) | 0.019 (3) | 0.039 (3) | 0.011 (2) | 0.006 (2) | 0.003 (2) |
O2 | 0.019 (2) | 0.012 (2) | 0.028 (3) | 0.0063 (19) | 0.003 (2) | 0.008 (2) |
O3 | 0.018 (2) | 0.017 (2) | 0.019 (2) | 0.0068 (19) | −0.0007 (19) | −0.0045 (19) |
O4 | 0.016 (2) | 0.016 (2) | 0.013 (2) | 0.0070 (19) | 0.0013 (18) | 0.0002 (18) |
O5 | 0.022 (2) | 0.019 (2) | 0.014 (2) | 0.013 (2) | 0.0056 (19) | 0.0020 (19) |
O6 | 0.017 (2) | 0.015 (2) | 0.014 (2) | 0.0068 (19) | 0.0035 (17) | 0.0028 (18) |
O7 | 0.023 (3) | 0.026 (3) | 0.021 (3) | 0.012 (2) | 0.007 (2) | 0.012 (2) |
O8 | 0.021 (2) | 0.018 (2) | 0.014 (2) | 0.0063 (19) | 0.0000 (19) | −0.0039 (19) |
O9 | 0.033 (3) | 0.030 (3) | 0.034 (3) | 0.011 (2) | 0.017 (2) | 0.017 (3) |
O10 | 0.021 (2) | 0.014 (2) | 0.028 (3) | 0.006 (2) | 0.005 (2) | 0.002 (2) |
O11 | 0.024 (2) | 0.020 (3) | 0.021 (2) | 0.012 (2) | 0.010 (2) | 0.009 (2) |
O12 | 0.025 (3) | 0.029 (3) | 0.036 (3) | 0.008 (2) | −0.004 (2) | −0.002 (3) |
O13 | 0.023 (3) | 0.023 (3) | 0.038 (3) | 0.015 (2) | 0.010 (2) | 0.005 (2) |
O14 | 0.017 (2) | 0.016 (2) | 0.023 (3) | 0.0078 (19) | 0.0012 (19) | 0.0033 (19) |
O15 | 0.033 (3) | 0.021 (3) | 0.028 (3) | 0.006 (2) | 0.007 (2) | 0.005 (2) |
O16 | 0.027 (3) | 0.022 (3) | 0.022 (3) | 0.010 (2) | 0.010 (2) | 0.008 (2) |
O17 | 0.044 (3) | 0.035 (3) | 0.020 (3) | 0.025 (3) | 0.005 (2) | 0.004 (2) |
O18 | 0.029 (3) | 0.042 (3) | 0.023 (3) | 0.019 (3) | 0.007 (2) | 0.011 (2) |
O19 | 0.027 (3) | 0.035 (3) | 0.031 (3) | 0.013 (3) | −0.003 (2) | 0.003 (3) |
O20 | 0.031 (3) | 0.053 (4) | 0.026 (3) | 0.031 (3) | 0.011 (2) | 0.011 (3) |
O21A | 0.05 (2) | 0.041 (16) | 0.06 (2) | 0.011 (14) | 0.028 (17) | 0.022 (17) |
O21B | 0.043 (8) | 0.028 (6) | 0.101 (12) | 0.003 (5) | 0.032 (9) | −0.005 (9) |
O22 | 0.030 (3) | 0.042 (4) | 0.075 (5) | 0.011 (3) | 0.011 (3) | 0.008 (4) |
O23 | 0.041 (3) | 0.027 (3) | 0.032 (3) | 0.014 (3) | 0.012 (3) | 0.006 (2) |
O24 | 0.030 (3) | 0.030 (3) | 0.033 (3) | 0.015 (2) | 0.009 (2) | 0.003 (2) |
O25 | 0.046 (4) | 0.036 (4) | 0.054 (4) | 0.000 (3) | 0.008 (3) | 0.004 (3) |
Ni1—O17 | 2.053 (5) | Na1—O23 | 2.377 (6) |
Ni1—O17i | 2.053 (5) | Na1—O1 | 2.395 (6) |
Ni1—O15i | 2.067 (5) | Na1—O21A | 2.44 (4) |
Ni1—O15 | 2.067 (5) | Na1—O15 | 2.544 (6) |
Ni1—O16i | 2.107 (5) | Na1—O16 | 2.564 (6) |
Ni1—O16 | 2.107 (5) | Na1—O17i | 4.003 (6) |
Ni2—O18ii | 2.050 (5) | Na1—O18vi | 4.326 (7) |
Ni2—O18 | 2.050 (5) | Na1—O17 | 4.328 (6) |
Ni2—O19ii | 2.062 (6) | O1—O22 | 3.079 (8) |
Ni2—O19 | 2.062 (6) | O2—O16iv | 2.746 (6) |
Ni2—O20ii | 2.092 (5) | O3—O17 | 2.697 (7) |
Ni2—O20 | 2.092 (5) | O3—O23iv | 2.853 (7) |
V1—O1 | 1.603 (5) | O4—O19ii | 2.714 (7) |
V1—O2 | 1.810 (5) | O5—O24 | 2.673 (7) |
V1—O3 | 1.856 (5) | O7—O24vii | 2.858 (7) |
V1—O4iii | 1.984 (5) | O8—O20iii | 2.865 (7) |
V1—O5iii | 2.022 (5) | O9—O17viii | 2.844 (7) |
V1—O6iii | 2.241 (5) | O9—O21Biv | 2.901 (16) |
V1—V5iii | 3.0734 (19) | O10—O21Aiv | 2.94 (3) |
V1—V3 | 3.1049 (18) | O10—O21Av | 3.10 (4) |
V2—O7 | 1.683 (5) | O11—O20viii | 2.702 (7) |
V2—O8 | 1.695 (5) | O11—O22v | 3.083 (8) |
V2—O5 | 1.913 (5) | O12—O25v | 3.009 (9) |
V2—O4iii | 1.941 (5) | O12—O21Bv | 3.023 (16) |
V2—O6iii | 2.117 (5) | O13—O18ix | 2.785 (7) |
V2—O6 | 2.125 (5) | O13—O22iii | 2.934 (8) |
V2—V3 | 3.087 (2) | O14—O18 | 2.630 (7) |
V2—V4iii | 3.091 (2) | O15—O24iii | 2.702 (8) |
V3—O9 | 1.602 (5) | O15—O25 | 2.824 (9) |
V3—O10 | 1.826 (5) | O16—O2iv | 2.746 (6) |
V3—O11 | 1.879 (5) | O16—O23iv | 2.775 (7) |
V3—O2 | 1.897 (5) | O17—O9x | 2.844 (7) |
V3—O7 | 2.046 (5) | O18—O13ix | 2.785 (7) |
V3—O6iii | 2.323 (5) | O19—O4ii | 2.714 (7) |
V3—V4 | 3.0692 (18) | O19—O24ix | 2.796 (8) |
V3—V5 | 3.0964 (17) | O19—O20 | 2.929 (7) |
V3—O21Biv | 3.764 (15) | O19—O25v | 3.131 (9) |
V3—O21Aiv | 3.79 (4) | O20—O11x | 2.702 (7) |
V4—O12 | 1.602 (6) | O20—O8iii | 2.865 (7) |
V4—O10 | 1.834 (5) | O21A—O10iv | 2.94 (3) |
V4—O3 | 1.866 (5) | O21A—O22 | 3.09 (4) |
V4—O14 | 1.877 (5) | O21A—O10vi | 3.10 (4) |
V4—O8iii | 2.062 (5) | O21B—O9iv | 2.901 (16) |
V4—O6iii | 2.340 (5) | O21B—O12vi | 3.023 (16) |
V4—V2iii | 3.091 (2) | O22—O13iii | 2.934 (8) |
V5—O13 | 1.614 (5) | O22—O11vi | 3.083 (8) |
V5—O11 | 1.817 (5) | O23—O16iv | 2.775 (7) |
V5—O14 | 1.822 (5) | O23—O3iv | 2.853 (7) |
V5—O4 | 1.995 (5) | O23—O25viii | 2.868 (9) |
V5—O5 | 2.006 (5) | O24—O15iii | 2.702 (8) |
V5—O6iii | 2.219 (5) | O24—O19ix | 2.796 (8) |
V5—V1iii | 3.0734 (19) | O24—O7vii | 2.858 (7) |
V5—O18 | 3.725 (5) | O25—O23x | 2.868 (9) |
V5—O22v | 3.799 (7) | O25—O12vi | 3.009 (9) |
Na1—O21B | 2.323 (16) | O25—O19vi | 3.131 (9) |
Na1—O22 | 2.358 (7) | ||
O17—Ni1—O17i | 180.0 | V4—V3—O21Biv | 92.1 (2) |
O17—Ni1—O15i | 88.5 (2) | V2—V3—O21Biv | 162.3 (2) |
O17i—Ni1—O15i | 91.5 (2) | V5—V3—O21Biv | 135.1 (2) |
O17—Ni1—O15 | 91.5 (2) | V1—V3—O21Biv | 106.3 (2) |
O17i—Ni1—O15 | 88.5 (2) | O9—V3—O21Aiv | 56.5 (5) |
O15i—Ni1—O15 | 180.0 | O10—V3—O21Aiv | 49.1 (5) |
O17—Ni1—O16i | 89.6 (2) | O11—V3—O21Aiv | 114.3 (6) |
O17i—Ni1—O16i | 90.4 (2) | O2—V3—O21Aiv | 86.3 (6) |
O15i—Ni1—O16i | 86.6 (2) | O7—V3—O21Aiv | 152.4 (5) |
O15—Ni1—O16i | 93.4 (2) | O6iii—V3—O21Aiv | 128.4 (5) |
O17—Ni1—O16 | 90.4 (2) | V4—V3—O21Aiv | 81.0 (4) |
O17i—Ni1—O16 | 89.6 (2) | V2—V3—O21Aiv | 164.3 (6) |
O15i—Ni1—O16 | 93.4 (2) | V5—V3—O21Aiv | 125.3 (5) |
O15—Ni1—O16 | 86.6 (2) | V1—V3—O21Aiv | 103.0 (6) |
O16i—Ni1—O16 | 180.0 | O21Biv—V3—O21Aiv | 11.5 (4) |
O18ii—Ni2—O18 | 180.0 | O12—V4—O10 | 103.9 (3) |
O18ii—Ni2—O19ii | 84.7 (2) | O12—V4—O3 | 102.4 (2) |
O18—Ni2—O19ii | 95.3 (2) | O10—V4—O3 | 91.6 (2) |
O18ii—Ni2—O19 | 95.3 (2) | O12—V4—O14 | 102.6 (3) |
O18—Ni2—O19 | 84.7 (2) | O10—V4—O14 | 91.0 (2) |
O19ii—Ni2—O19 | 180.0 | O3—V4—O14 | 153.5 (2) |
O18ii—Ni2—O20ii | 87.9 (2) | O12—V4—O8iii | 100.2 (3) |
O18—Ni2—O20ii | 92.1 (2) | O10—V4—O8iii | 155.8 (2) |
O19ii—Ni2—O20ii | 89.7 (2) | O3—V4—O8iii | 84.9 (2) |
O19—Ni2—O20ii | 90.3 (2) | O14—V4—O8iii | 82.0 (2) |
O18ii—Ni2—O20 | 92.1 (2) | O12—V4—O6iii | 174.5 (3) |
O18—Ni2—O20 | 87.9 (2) | O10—V4—O6iii | 81.53 (19) |
O19ii—Ni2—O20 | 90.3 (2) | O3—V4—O6iii | 77.83 (18) |
O19—Ni2—O20 | 89.7 (2) | O14—V4—O6iii | 76.48 (18) |
O20ii—Ni2—O20 | 180.0 | O8iii—V4—O6iii | 74.28 (17) |
O1—V1—O2 | 103.4 (2) | O12—V4—V3 | 136.9 (2) |
O1—V1—O3 | 100.9 (2) | O10—V4—V3 | 32.93 (16) |
O2—V1—O3 | 95.2 (2) | O3—V4—V3 | 84.61 (15) |
O1—V1—O4iii | 101.2 (2) | O14—V4—V3 | 83.34 (15) |
O2—V1—O4iii | 91.2 (2) | O8iii—V4—V3 | 122.86 (14) |
O3—V1—O4iii | 154.8 (2) | O6iii—V4—V3 | 48.60 (11) |
O1—V1—O5iii | 99.2 (2) | O12—V4—V2iii | 131.1 (2) |
O2—V1—O5iii | 155.9 (2) | O10—V4—V2iii | 124.91 (17) |
O3—V1—O5iii | 88.4 (2) | O3—V4—V2iii | 78.79 (15) |
O4iii—V1—O5iii | 76.31 (19) | O14—V4—V2iii | 78.14 (15) |
O1—V1—O6iii | 174.4 (2) | O8iii—V4—V2iii | 30.93 (13) |
O2—V1—O6iii | 81.72 (19) | O6iii—V4—V2iii | 43.37 (11) |
O3—V1—O6iii | 80.66 (19) | V3—V4—V2iii | 91.97 (5) |
O4iii—V1—O6iii | 76.20 (18) | O13—V5—O11 | 103.0 (2) |
O5iii—V1—O6iii | 75.42 (17) | O13—V5—O14 | 102.5 (2) |
O1—V1—V5iii | 90.66 (19) | O11—V5—O14 | 94.4 (2) |
O2—V1—V5iii | 130.72 (17) | O13—V5—O4 | 98.1 (2) |
O3—V1—V5iii | 128.51 (16) | O11—V5—O4 | 156.9 (2) |
O4iii—V1—V5iii | 39.55 (13) | O14—V5—O4 | 90.1 (2) |
O5iii—V1—V5iii | 40.09 (14) | O13—V5—O5 | 99.5 (2) |
O6iii—V1—V5iii | 84.23 (12) | O11—V5—O5 | 90.8 (2) |
O1—V1—V3 | 137.1 (2) | O14—V5—O5 | 155.6 (2) |
O2—V1—V3 | 34.01 (14) | O4—V5—O5 | 76.41 (19) |
O3—V1—V3 | 83.73 (15) | O13—V5—O6iii | 174.0 (2) |
O4iii—V1—V3 | 88.20 (14) | O11—V5—O6iii | 81.68 (19) |
O5iii—V1—V3 | 123.67 (13) | O14—V5—O6iii | 80.76 (19) |
O6iii—V1—V3 | 48.25 (12) | O4—V5—O6iii | 76.70 (18) |
V5iii—V1—V3 | 119.82 (5) | O5—V5—O6iii | 76.46 (18) |
O7—V2—O8 | 107.5 (2) | O13—V5—V1iii | 88.8 (2) |
O7—V2—O5 | 98.1 (2) | O11—V5—V1iii | 131.26 (17) |
O8—V2—O5 | 98.5 (2) | O14—V5—V1iii | 129.37 (16) |
O7—V2—O4iii | 96.5 (2) | O4—V5—V1iii | 39.29 (13) |
O8—V2—O4iii | 96.0 (2) | O5—V5—V1iii | 40.46 (13) |
O5—V2—O4iii | 155.2 (2) | O6iii—V5—V1iii | 85.24 (12) |
O7—V2—O6iii | 86.9 (2) | O13—V5—V3 | 136.5 (2) |
O8—V2—O6iii | 165.5 (2) | O11—V5—V3 | 33.74 (15) |
O5—V2—O6iii | 80.91 (19) | O14—V5—V3 | 83.38 (15) |
O4iii—V2—O6iii | 80.09 (18) | O4—V5—V3 | 125.13 (13) |
O7—V2—O6 | 164.7 (2) | O5—V5—V3 | 87.93 (14) |
O8—V2—O6 | 87.8 (2) | O6iii—V5—V3 | 48.45 (12) |
O5—V2—O6 | 80.46 (19) | V1iii—V5—V3 | 120.80 (5) |
O4iii—V2—O6 | 80.10 (19) | O13—V5—O18 | 63.0 (2) |
O6iii—V2—O6 | 77.80 (19) | O11—V5—O18 | 111.75 (18) |
O7—V2—V3 | 38.12 (18) | O14—V5—O18 | 40.77 (16) |
O8—V2—V3 | 145.59 (17) | O4—V5—O18 | 86.16 (15) |
O5—V2—V3 | 89.87 (15) | O5—V5—O18 | 153.49 (16) |
O4iii—V2—V3 | 89.47 (14) | O6iii—V5—O18 | 119.09 (16) |
O6iii—V2—V3 | 48.76 (13) | V1iii—V5—O18 | 115.63 (10) |
O6—V2—V3 | 126.56 (14) | V3—V5—O18 | 118.54 (10) |
O7—V2—V4iii | 146.19 (19) | O13—V5—O22v | 76.7 (2) |
O8—V2—V4iii | 38.71 (17) | O11—V5—O22v | 53.41 (19) |
O5—V2—V4iii | 89.12 (15) | O14—V5—O22v | 56.51 (19) |
O4iii—V2—V4iii | 89.69 (14) | O4—V5—O22v | 142.91 (18) |
O6iii—V2—V4iii | 126.93 (13) | O5—V5—O22v | 140.58 (18) |
O6—V2—V4iii | 49.13 (13) | O6iii—V5—O22v | 109.33 (16) |
V3—V2—V4iii | 175.69 (5) | V1iii—V5—O22v | 165.42 (11) |
O9—V3—O10 | 103.1 (3) | V3—V5—O22v | 71.17 (11) |
O9—V3—O11 | 102.6 (3) | O18—V5—O22v | 58.44 (14) |
O10—V3—O11 | 91.6 (2) | O21B—Na1—O22 | 91.0 (4) |
O9—V3—O2 | 101.3 (2) | O21B—Na1—O23 | 103.2 (4) |
O10—V3—O2 | 91.4 (2) | O22—Na1—O23 | 88.0 (3) |
O11—V3—O2 | 154.5 (2) | O21B—Na1—O1 | 167.3 (4) |
O9—V3—O7 | 100.9 (3) | O22—Na1—O1 | 80.7 (2) |
O10—V3—O7 | 155.9 (2) | O23—Na1—O1 | 86.3 (2) |
O11—V3—O7 | 84.2 (2) | O21B—Na1—O21A | 18.0 (7) |
O2—V3—O7 | 82.7 (2) | O22—Na1—O21A | 80.2 (9) |
O9—V3—O6iii | 174.7 (3) | O23—Na1—O21A | 88.4 (7) |
O10—V3—O6iii | 82.18 (19) | O1—Na1—O21A | 160.3 (9) |
O11—V3—O6iii | 77.62 (18) | O21B—Na1—O15 | 86.8 (4) |
O2—V3—O6iii | 77.78 (18) | O22—Na1—O15 | 115.1 (2) |
O7—V3—O6iii | 73.78 (18) | O23—Na1—O15 | 155.0 (2) |
O9—V3—V4 | 136.2 (2) | O1—Na1—O15 | 88.0 (2) |
O10—V3—V4 | 33.11 (16) | O21A—Na1—O15 | 104.4 (7) |
O11—V3—V4 | 84.46 (15) | O21B—Na1—O16 | 99.7 (4) |
O2—V3—V4 | 84.40 (16) | O22—Na1—O16 | 169.0 (2) |
O7—V3—V4 | 122.84 (14) | O23—Na1—O16 | 87.4 (2) |
O6iii—V3—V4 | 49.07 (12) | O1—Na1—O16 | 89.0 (2) |
O9—V3—V2 | 131.4 (2) | O21A—Na1—O16 | 109.6 (9) |
O10—V3—V2 | 125.44 (17) | O15—Na1—O16 | 68.19 (18) |
O11—V3—V2 | 78.81 (16) | O21B—Na1—O17i | 60.9 (4) |
O2—V3—V2 | 78.86 (15) | O22—Na1—O17i | 143.0 (2) |
O7—V3—V2 | 30.52 (13) | O23—Na1—O17i | 119.9 (2) |
O6iii—V3—V2 | 43.27 (12) | O1—Na1—O17i | 121.71 (18) |
V4—V3—V2 | 92.33 (5) | O21A—Na1—O17i | 77.2 (8) |
O9—V3—V5 | 135.0 (2) | O15—Na1—O17i | 45.67 (15) |
O10—V3—V5 | 82.39 (16) | O16—Na1—O17i | 47.02 (15) |
O11—V3—V5 | 32.48 (14) | O21B—Na1—O18vi | 87.5 (4) |
O2—V3—V5 | 123.40 (15) | O22—Na1—O18vi | 58.1 (2) |
O7—V3—V5 | 81.48 (14) | O23—Na1—O18vi | 144.9 (2) |
O6iii—V3—V5 | 45.62 (11) | O1—Na1—O18vi | 79.88 (17) |
V4—V3—V5 | 60.87 (4) | O21A—Na1—O18vi | 93.9 (8) |
V2—V3—V5 | 61.18 (4) | O15—Na1—O18vi | 56.95 (15) |
O9—V3—V1 | 133.5 (2) | O16—Na1—O18vi | 124.14 (16) |
O10—V3—V1 | 82.11 (16) | O17i—Na1—O18vi | 94.67 (13) |
O11—V3—V1 | 123.65 (15) | O21B—Na1—O17 | 118.7 (4) |
O2—V3—V1 | 32.25 (14) | O22—Na1—O17 | 133.6 (2) |
O7—V3—V1 | 80.58 (14) | O23—Na1—O17 | 115.43 (19) |
O6iii—V3—V1 | 46.03 (12) | O1—Na1—O17 | 62.83 (16) |
V4—V3—V1 | 60.83 (4) | O21A—Na1—O17 | 135.9 (8) |
V2—V3—V1 | 61.48 (4) | O15—Na1—O17 | 41.52 (15) |
V5—V3—V1 | 91.46 (5) | O16—Na1—O17 | 41.61 (14) |
O9—V3—O21Biv | 46.4 (3) | O17i—Na1—O17 | 58.91 (13) |
O10—V3—O21Biv | 60.6 (3) | O18vi—Na1—O17 | 86.52 (12) |
O11—V3—O21Biv | 118.7 (3) | V1—O1—Na1 | 169.0 (3) |
O2—V3—O21Biv | 84.5 (3) | V1—O1—O22 | 141.0 (3) |
O7—V3—O21Biv | 141.1 (3) | Na1—O1—O22 | 49.11 (18) |
O6iii—V3—O21Biv | 138.2 (3) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z+1; (v) x−1, y, z; (vi) x+1, y, z; (vii) −x+1, −y+1, −z+2; (viii) x, y, z+1; (ix) −x, −y+1, −z+1; (x) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Ni(H2O)6]2[Na(H2O)3]2V10O28·4H2O |
Mr | 1517.15 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.836 (2), 12.606 (2), 8.331 (1) |
α, β, γ (°) | 93.19 (2), 99.83 (2), 109.65 (2) |
V (Å3) | 1048.1 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 3.15 |
Crystal size (mm) | 0.50 × 0.18 × 0.05 |
Data collection | |
Diffractometer | Rigaku AFC-5R automated four-circle diffractometer |
Absorption correction | ψ scan TEXSAN (Molecular Structure Corporation, 1995) |
Tmin, Tmax | 0.553, 0.854 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6109, 6109, 3399 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.152, 1.07 |
No. of reflections | 6109 |
No. of parameters | 301 |
H-atom treatment | H-atom parameters not defined |
Δρmax, Δρmin (e Å−3) | 0.89, −0.81 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Ni1—O17 | 2.053 (5) | V3—O10 | 1.826 (5) |
Ni1—O17i | 2.053 (5) | V3—O11 | 1.879 (5) |
Ni1—O15i | 2.067 (5) | V3—O2 | 1.897 (5) |
Ni1—O15 | 2.067 (5) | V3—O7 | 2.046 (5) |
Ni1—O16i | 2.107 (5) | V3—O6iii | 2.323 (5) |
Ni1—O16 | 2.107 (5) | V4—O12 | 1.602 (6) |
Ni2—O18ii | 2.050 (5) | V4—O10 | 1.834 (5) |
Ni2—O18 | 2.050 (5) | V4—O3 | 1.866 (5) |
Ni2—O19ii | 2.062 (6) | V4—O14 | 1.877 (5) |
Ni2—O19 | 2.062 (6) | V4—O8iii | 2.062 (5) |
Ni2—O20ii | 2.092 (5) | V4—O6iii | 2.340 (5) |
Ni2—O20 | 2.092 (5) | V5—O13 | 1.614 (5) |
V1—O1 | 1.603 (5) | V5—O11 | 1.817 (5) |
V1—O2 | 1.810 (5) | V5—O14 | 1.822 (5) |
V1—O3 | 1.856 (5) | V5—O4 | 1.995 (5) |
V1—O4iii | 1.984 (5) | V5—O5 | 2.006 (5) |
V1—O5iii | 2.022 (5) | V5—O6iii | 2.219 (5) |
V1—O6iii | 2.241 (5) | Na1—O21B | 2.323 (16) |
V2—O7 | 1.683 (5) | Na1—O22 | 2.358 (7) |
V2—O8 | 1.695 (5) | Na1—O23 | 2.377 (6) |
V2—O5 | 1.913 (5) | Na1—O1 | 2.395 (6) |
V2—O4iii | 1.941 (5) | Na1—O21A | 2.44 (4) |
V2—O6iii | 2.117 (5) | Na1—O15 | 2.544 (6) |
V2—O6 | 2.125 (5) | Na1—O16 | 2.564 (6) |
V3—O9 | 1.602 (5) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z+1. |
Several peroxovanadium complexes have attracted attention for their insulin-mimetic and enzyme-like activities (Tracy & Crans, 1998; Siegel & Siegel, 1995). In our attempt to prepare peroxovanadates, the title novel compound, (I), a nickel sodium decavanadate having no peroxo group, was obtained as green-orange crystals and its crystal structure is presented here. \sch
The structure of (I) consists of a decavanadate anion, three edge-shared octahedra of Ni and Na, an [Ni(H2O)6]2+ cation and four waters of crystallization (Fig. 1). The [V10O28]6- anions and [Na(H2O)3][Ni(H2O)6][Na(H2O)3]4+ trimeric cations are linked alternately to form a one-dimensional chain (Fig. 2).
The framework of [V10O28]6- has been studied in detail previously (Evans, 1966; Nowogrocki et al., 1997). The decavanadate unit comprises ten edge-sharing VO6 octahedra with approximate D2h symmetry. The V—O distances and bond angles in the decavanadate unit of (I) are comparable with those in the literature (Evans, 1966).
In the trimeric cation of (I), the Na atoms are surrounded by one decavanadate O1 atom and five water molecules, and the Ni atom by six water molecules. The Ni octahedron is sandwiched between two Na octahedra. Atom Na1 coordinates directly to the decavanadate unit at O1. One of the terminal water molecules on the Na atom positioned trans to decavanadate atom O1 was refined as disordered over two positions (O21A and O21B). The occupancy factors of these atoms were refined in the course of the initial calculations and were then fixed to the refined values of 0.3 and 0.7, respectively, in the final calculation.
The O1—Na1—O21A and O1—Na1—O21B angles [160.3 (9)° and 167.3 (4)°, respectively] do not differ greatly, which does not conflict with the disordering. The Na—O bond distances have a wide range of values, from 2.331 (8) to 2.564 (4) Å. The Na—O distances to the terminal water molecules (Na1—O21A, Na1—O21B, Na1—O22 and Na1—O23) are 2.44 (4), 2.32 (2), 2.359 (8) and 2.376 (6) Å, respectively. The length of the Na1—O1 bond [2.395 (6) Å] is similar to these three, even though atom O1 also bonds to atom V1. The Na—O distances to the water molecules bridging to atom Ni1 [2.544 (6) Å for Na1—O15 and 2.564 (6) Å for Na1—O16] are longer than those of the other four Na1—O bonds.
Each [Na(OH2)3][Ni(OH2)6][Na(OH2)3]4+[V10O28]6- chain is connected via hydrogen bonds through the four waters of crystallization and the water molecules coordinated to Na and Ni, to form the overall three-dimensional structure. With regard to the two Ni atoms, Ni1 and Ni2, atom Ni1 is involved in the chain as mentioned above, whereas atom Ni2 is isolated from the chain and plays an important role in tying the chains together. The Ni1—O distances to the water molecules bridging to Na, Ni1—O15 and Ni1—O16, are 2.067 (5) and 2.107 (5) Å, respectively, and that to the terminal water molecule, Ni1—O17, is 2.053 (5) Å. The hydrogen-bonded O—O distances are in the range 2.630 (7)–3.131 (9) Å. H atoms were not identified in the difference Fourier maps and could not be determined.
A number of decavanadate compounds with transition metals, monovalent cations and [V10O28]6- anions in the ratio 2:2:1 have been reported so far (Wickham, 1972), two of which have been structurally analyzed. The two compounds, K2Zn2V10O28.16H2O (Evans, 1966) and (NH4)2Co2V10O28.16H2O (Nowogrocki et al., 1997), are isostructural. However, the overall structure of (I) differs from them. The structure of MI2MII2V10O28.16H2O consists of a [V10O28]6- anion, two isolated octahedral MII(H2O)62+ cation groups, two MI ions and four waters of crystallization. The cations and water molecules surround the polyanion, forming hydrogen bonds between them. Therefore, there is no direct connection between the cations and the polyanion, in contrast with (I), where the [Na(H2O)3][Ni(H2O)6][Na(H2O)3]4+ trimeric cation is bound directly to the decavanadate. This difference in structures may be caused by the difference in size and behaviour of the monovalent cations. It is noteworthy that the formula of (I) can be written as Na2Ni2V10O28.22H2O, whereas that of the compounds mentioned above is MI2MII2V10O28.16H2O; the different number of water molecules in the formula clearly plays an important role in the overall structural differences.