The novel title compound, poly[octa-
-aqua-octaaqua-
-decavanadato-hexalithium], contains [V
10O
28]
6- polyanions with 2/
m symmetry linked by centrosymmetric [Li
6(H
2O)
16]
6+ cation chains. The [V
10O
28]
6- polyanions form a two-dimensional network with [Li
6(H
2O)
16]
6+ chains
via O-polyanion-Li-chain coordination, with Li-O bond lengths in the range 2.007 (5)-2.016 (5) Å. The hexalithium hexadecahydrate chain is composed of a centrosymmetric pair of LiO
6 octahedra and four distorted LiO
4 tetrahedra. Hydrogen bonds occur between the polyanion and the Li-based chains, and within the Li-based chains.
Supporting information
The compound was prepared by hydrothermal treatment of NH4VO3 and LiOH (in a 1:0.6 molar ratio) acidified to pH 4.5. The reaction mixture was heated for 10 h at 393 K·The filtrate was kept at room temperature and orange single crystals formed after 15 d.
The coordinates of all H atoms were determined from a difference Fourier map. H atoms were included in the final cycles of refinement in a riding model, with O—H = 0.8013–0.9510 Å and Uiso(H) = 1.2Ueq(carrier atom).
Data collection: PROCESS-AUTO (Rigaku Corporation, 2002); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: CrystalStructure.
poly[octa-µ-aqua-ocataqua-µ-decavanadato-hexalithium]
top
Crystal data top
Li6(H2O)16V10O28 | F(000) = 1264.00 |
Mr = 1287.29 | Dx = 2.546 Mg m−3 |
Orthorhombic, Pnnm | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2 2n | Cell parameters from 16740 reflections |
a = 17.6164 (2) Å | θ = 2.3–27.5° |
b = 10.3189 (1) Å | µ = 2.79 mm−1 |
c = 9.2348 (3) Å | T = 273 K |
V = 1678.72 (6) Å3 | Block, orange |
Z = 2 | 0.39 × 0.31 × 0.26 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 1611 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.021 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (Higashi, 1995) | h = −22→22 |
Tmin = 0.391, Tmax = 0.484 | k = −13→13 |
16609 measured reflections | l = −11→11 |
2044 independent reflections | |
Refinement top
Refinement on F2 | 5 restraints |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.072 | w = 1/[0.001Fo2 + σ(Fo2)]/(4Fo2) |
S = 1.03 | (Δ/σ)max < 0.001 |
1611 reflections | Δρmax = 0.33 e Å−3 |
160 parameters | Δρmin = −0.42 e Å−3 |
Crystal data top
Li6(H2O)16V10O28 | V = 1678.72 (6) Å3 |
Mr = 1287.29 | Z = 2 |
Orthorhombic, Pnnm | Mo Kα radiation |
a = 17.6164 (2) Å | µ = 2.79 mm−1 |
b = 10.3189 (1) Å | T = 273 K |
c = 9.2348 (3) Å | 0.39 × 0.31 × 0.26 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 2044 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 1611 reflections with F2 > 2σ(F2) |
Tmin = 0.391, Tmax = 0.484 | Rint = 0.021 |
16609 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.021 | 5 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.33 e Å−3 |
1611 reflections | Δρmin = −0.42 e Å−3 |
160 parameters | |
Special details top
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
V1 | 0.64709 (2) | 0.66201 (3) | 0.66489 (4) | 0.0141 (1) | |
V2 | 0.64143 (2) | 0.40100 (4) | 0.5000 | 0.0112 (1) | |
V3 | 0.5000 | 0.5000 | 0.67800 (5) | 0.0101 (1) | |
V4 | 0.49439 (2) | 0.23635 (4) | 0.5000 | 0.0127 (1) | |
O1 | 0.6977 (1) | 0.7148 (2) | 0.5000 | 0.0163 (5) | |
O2 | 0.57373 (7) | 0.7932 (1) | 0.6463 (1) | 0.0153 (3) | |
O3 | 0.69740 (8) | 0.7153 (1) | 0.7960 (2) | 0.0226 (4) | |
O4 | 0.68548 (8) | 0.4927 (1) | 0.6455 (1) | 0.0151 (3) | |
O5 | 0.5645 (1) | 0.5704 (1) | 0.5000 | 0.0113 (4) | |
O6 | 0.6876 (1) | 0.2667 (2) | 0.5000 | 0.0175 (5) | |
O7 | 0.55641 (7) | 0.3483 (1) | 0.6343 (1) | 0.0114 (3) | |
O8 | 0.43484 (7) | 0.4295 (1) | 0.7875 (1) | 0.0152 (3) | |
O9 | 0.5469 (1) | 0.1105 (2) | 0.5000 | 0.0204 (5) | |
O10 | 0.68872 (9) | 1.0026 (1) | 0.6689 (2) | 0.0232 (4) | |
O11 | 0.8336 (1) | 0.9689 (2) | 0.50000 (1) | 0.0230 (5) | |
O12 | 0.86619 (8) | 0.7062 (1) | 0.6573 (1) | 0.0213 (4) | |
O13 | 1.0207 (1) | 0.7409 (2) | 0.50000 (1) | 0.0313 (6) | |
O14 | 0.8557 (1) | 0.4521 (2) | 0.50000 (1) | 0.0340 (7) | |
O15 | 1.00000 (1) | 0.50000 (1) | 0.6672 (2) | 0.0251 (6) | |
Li1 | 0.7345 (3) | 1.0895 (5) | 0.5000 | 0.029 (1) | |
Li2 | 0.8057 (3) | 0.7794 (5) | 0.5000 | 0.024 (1) | |
Li3 | 0.9343 (3) | 0.6014 (5) | 0.5000 | 0.029 (1) | |
H1 | 0.6581 | 0.9471 | 0.6524 | 0.028* | |
H2 | 0.7289 | 0.9781 | 0.7234 | 0.029* | |
H3 | 0.8574 | 0.9938 | 0.5761 | 0.028* | |
H4 | 0.8479 | 0.6501 | 0.7116 | 0.026* | |
H5 | 0.8863 | 0.7583 | 0.7124 | 0.026* | |
H6 | 1.0375 | 0.7961 | 0.5760 | 0.039* | |
H7 | 0.8067 | 0.4489 | 0.5000 | 0.041* | |
H8 | 0.8846 | 0.3895 | 0.5000 | 0.041* | |
H9 | 1.0240 | 0.5600 | 0.7283 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
V1 | 0.0120 (2) | 0.0153 (2) | 0.0150 (2) | −0.0024 (1) | −0.0019 (1) | −0.0020 (1) |
V2 | 0.0083 (2) | 0.0110 (3) | 0.0144 (3) | 0.0008 (1) | 0.0000 | 0.0000 |
V3 | 0.0097 (2) | 0.0114 (2) | 0.0092 (2) | −0.0002 (1) | 0.0000 | 0.0000 |
V4 | 0.0112 (2) | 0.0096 (2) | 0.0173 (3) | −0.0004 (2) | 0.0000 | 0.0000 |
O1 | 0.0116 (9) | 0.0142 (9) | 0.023 (1) | −0.0020 (7) | 0.0000 | 0.0000 |
O2 | 0.0133 (6) | 0.0134 (6) | 0.0192 (7) | −0.0017 (5) | −0.0005 (5) | −0.0038 (5) |
O3 | 0.0178 (7) | 0.0260 (7) | 0.0239 (8) | −0.0032 (6) | −0.0055 (6) | −0.0068 (7) |
O4 | 0.0120 (6) | 0.0147 (6) | 0.0186 (7) | 0.0002 (5) | −0.0035 (5) | −0.0001 (5) |
O5 | 0.0097 (8) | 0.0110 (8) | 0.0132 (9) | 0.0004 (7) | 0.0000 | 0.0000 |
O6 | 0.015 (1) | 0.015 (1) | 0.022 (1) | 0.0038 (8) | 0.0000 | 0.0000 |
O7 | 0.0107 (6) | 0.0115 (6) | 0.0121 (6) | 0.0003 (5) | −0.0008 (5) | 0.0017 (5) |
O8 | 0.0147 (6) | 0.0183 (6) | 0.0127 (6) | −0.0007 (5) | 0.0024 (5) | 0.0007 (5) |
O9 | 0.017 (1) | 0.0133 (9) | 0.031 (1) | 0.0008 (7) | 0.0000 | 0.0000 |
O10 | 0.0226 (7) | 0.0224 (8) | 0.0246 (9) | −0.0036 (6) | −0.0026 (6) | −0.0008 (6) |
O11 | 0.024 (1) | 0.025 (1) | 0.020 (1) | −0.0021 (9) | 0.0000 | 0.0000 |
O12 | 0.0247 (7) | 0.0222 (7) | 0.0170 (7) | −0.0072 (6) | −0.0008 (6) | −0.0005 (6) |
O13 | 0.042 (1) | 0.026 (1) | 0.026 (1) | −0.014 (1) | 0.0000 | 0.0000 |
O14 | 0.029 (1) | 0.033 (1) | 0.040 (2) | −0.006 (1) | 0.0000 | 0.0000 |
O15 | 0.027 (1) | 0.027 (1) | 0.022 (1) | −0.0026 (9) | 0.0000 | 0.0000 |
Li1 | 0.033 (3) | 0.024 (3) | 0.029 (3) | 0.007 (2) | 0.0000 | 0.0000 |
Li2 | 0.023 (3) | 0.024 (2) | 0.023 (2) | −0.005 (2) | 0.0000 | 0.0000 |
Li3 | 0.029 (3) | 0.029 (3) | 0.029 (3) | −0.002 (2) | 0.0000 | 0.0000 |
Geometric parameters (Å, º) top
V1—O1 | 1.846 (1) | O14—Li3 | 2.072 (6) |
V1—O2 | 1.880 (1) | O14—Li3ii | 2.072 (6) |
V1—O3 | 1.598 (1) | O15—Li3 | 2.195 (4) |
V1—O4 | 1.882 (1) | O15—Li3ii | 2.195 (4) |
V1—O5 | 2.308 (1) | Li1—O6v | 2.007 (5) |
V1—O8i | 2.063 (1) | Li1—O10ii | 1.971 (4) |
V2—O4 | 1.817 (1) | Li1—O11 | 2.144 (6) |
V2—O4ii | 1.817 (1) | Li1—O11ii | 2.144 (6) |
V2—O5 | 2.212 (2) | Li2—O11 | 2.016 (5) |
V2—O6 | 1.607 (2) | Li2—O11ii | 2.016 (5) |
V2—O7 | 2.019 (1) | Li2—O12ii | 1.954 (4) |
V2—O7ii | 2.019 (1) | Li3—O12ii | 2.173 (4) |
V3—O5 | 2.126 (1) | Li3—O13 | 2.094 (6) |
V3—O5i | 2.126 (1) | Li3—O13ii | 2.094 (6) |
V3—O7 | 1.898 (1) | Li3—O14 | 2.072 (6) |
V3—O7i | 1.898 (1) | Li3—O14ii | 2.072 (6) |
V3—O8 | 1.694 (1) | Li3—O15 | 2.195 (4) |
V3—O8i | 1.694 (1) | Li3—O15ii | 2.195 (4) |
V4—O2i | 1.833 (1) | O10—H1 | 0.8013 |
V4—O2iii | 1.833 (1) | O10—H2 | 0.9045 |
V4—O5i | 2.248 (2) | O11—H3 | 0.8579 |
V4—O7 | 2.016 (1) | O11—H3ii | 0.8579 |
V4—O7ii | 2.016 (1) | O12—H4 | 0.8305 |
V4—O9 | 1.595 (2) | O12—H5 | 0.8197 |
O1—V1ii | 1.846 (1) | O13—H6 | 0.9510 |
O1—Li2 | 2.016 (5) | O13—H6ii | 0.9510 |
O2—V4i | 1.833 (1) | O14—H7 | 0.8638 |
O5—V1ii | 2.308 (1) | O14—H7ii | 0.8638 |
O5—V3iii | 2.126 (1) | O14—H8 | 0.8229 |
O5—V4i | 2.248 (2) | O14—H8ii | 0.8229 |
O6—Li1iv | 2.007 (5) | O15—H9 | 0.9385 |
O8—V1i | 2.063 (1) | H3—O11 | 0.8579 |
O10—Li1 | 1.971 (4) | H3—O11ii | 0.8579 |
O11—Li1 | 2.144 (6) | H6—O13 | 0.9510 |
O11—Li1ii | 2.144 (6) | H6—O13ii | 0.9510 |
O11—Li2 | 2.016 (5) | H7—O14 | 0.8638 |
O11—Li2ii | 2.016 (5) | H7—O14ii | 0.8638 |
O12—Li2 | 1.954 (4) | H8—O14 | 0.8229 |
O12—Li3 | 2.173 (4) | H8—O14ii | 0.8229 |
O13—Li3 | 2.094 (6) | H9—O15 | 0.9385 |
O13—Li3ii | 2.094 (6) | | |
| | | |
V1—O1—V1ii | 111.11 (9) | V3—O8—V1i | 110.05 (7) |
O2—V1—O1 | 92.51 (7) | O7—V4—O2i | 89.81 (5) |
O3—V1—O1 | 104.82 (7) | O7ii—V4—O2i | 154.64 (6) |
O4—V1—O1 | 91.27 (7) | O9—V4—O2i | 104.14 (6) |
O5—V1—O1 | 83.16 (6) | V4—O2i—V1i | 113.42 (7) |
O8i—V1—O1 | 157.70 (6) | O5i—V4—O2i | 81.12 (5) |
V1—O1—Li2 | 123.57 (5) | O2iii—V4—O2i | 95.00 (6) |
V1—O2—V4i | 113.42 (7) | O7—V4—O2iii | 154.64 (6) |
O3—V1—O2 | 101.68 (7) | O7ii—V4—O2iii | 89.81 (5) |
O4—V1—O2 | 155.11 (6) | O9—V4—O2iii | 104.14 (6) |
O5—V1—O2 | 78.55 (6) | O5i—V4—O2iii | 81.12 (5) |
O8i—V1—O2 | 84.19 (5) | V4—O2iii—V1iii | 113.42 (7) |
O4—V1—O3 | 101.10 (7) | V4—O5i—V3iii | 93.24 (5) |
O5—V1—O3 | 171.97 (6) | O7—V4—O5i | 75.04 (5) |
O8i—V1—O3 | 97.44 (7) | O7ii—V4—O5i | 75.04 (5) |
V1—O4—V2 | 113.60 (7) | O9—V4—O5i | 172.01 (8) |
O5—V1—O4 | 77.49 (6) | V4—O5i—V1i | 85.85 (5) |
O8i—V1—O4 | 83.04 (5) | V4—O5i—V2i | 169.70 (9) |
V1—O5—V1ii | 82.54 (6) | V4—O5i—V1iii | 85.85 (5) |
V1—O5—V2 | 86.41 (5) | O7ii—V4—O7 | 75.90 (5) |
V1—O5—V3 | 88.10 (1) | O9—V4—O7 | 98.75 (7) |
V1—O5—V4i | 85.85 (5) | V4—O7ii—V3iii | 108.64 (6) |
O8i—V1—O5 | 74.56 (5) | O9—V4—O7ii | 98.75 (7) |
V1—O5—V3iii | 170.63 (6) | O1—V1ii—O2ii | 92.51 (7) |
V1—O8i—V3 | 110.05 (7) | O1—V1ii—O4ii | 91.27 (7) |
O4ii—V2—O4 | 95.35 (6) | O1—V1ii—O5 | 83.16 (6) |
O5—V2—O4 | 81.39 (5) | Li2—O1—V1ii | 123.57 (5) |
O6—V2—O4 | 103.45 (6) | O1—V1ii—O8iii | 157.70 (6) |
O7—V2—O4 | 90.17 (6) | O1—V1ii—O3ii | 104.82 (7) |
O7ii—V2—O4 | 155.66 (6) | O1—Li2—O11 | 123.4 (3) |
V2—O4ii—V1ii | 113.60 (7) | O1—Li2—O12 | 112.8 (2) |
O5—V2—O4ii | 81.39 (5) | O1—Li2—O12ii | 112.8 (2) |
O6—V2—O4ii | 103.45 (6) | O2—V4i—O2ii | 95.00 (6) |
O7—V2—O4ii | 155.66 (6) | O2—V4i—O5 | 81.12 (5) |
O7ii—V2—O4ii | 90.17 (6) | O2—V4i—O7i | 89.81 (5) |
V2—O5—V1ii | 86.41 (5) | O2—V4i—O7iii | 154.64 (6) |
V2—O5—V3 | 93.29 (5) | O2—V4i—O9i | 104.14 (6) |
V2—O5—V4i | 169.70 (9) | V4i—O5—V1ii | 85.85 (5) |
V2—O5—V3iii | 93.29 (5) | O5—V1ii—O2ii | 78.55 (6) |
O6—V2—O5 | 172.64 (8) | O5—V1ii—O4ii | 77.49 (6) |
O7—V2—O5 | 76.02 (5) | V3iii—O5—V1ii | 88.10 (1) |
O7ii—V2—O5 | 76.02 (5) | O5—V1ii—O8iii | 74.56 (5) |
O7—V2—O6 | 98.24 (6) | O5—V1ii—O3ii | 171.97 (6) |
O7ii—V2—O6 | 98.24 (6) | V4i—O5—V3iii | 93.24 (5) |
V2—O6—Li1iv | 173.9 (2) | O5—V3iii—O7ii | 80.65 (6) |
V2—O7—V3 | 107.27 (6) | O5—V3iii—O8iii | 87.29 (6) |
V2—O7—V4 | 100.29 (6) | O5—V3iii—O5i | 78.73 (5) |
O7ii—V2—O7 | 75.78 (5) | O5—V3iii—O7iii | 80.42 (6) |
V2—O7ii—V3iii | 107.27 (6) | O5—V3iii—O8ii | 166.03 (6) |
V2—O7ii—V4 | 100.29 (6) | O5—V4i—O2ii | 81.12 (5) |
V3—O5—V1ii | 170.63 (6) | O5—V4i—O7i | 75.04 (5) |
V3—O5—V4i | 93.24 (5) | O5—V4i—O7iii | 75.04 (5) |
O7i—V3—O5 | 80.42 (6) | O5—V4i—O9i | 172.01 (8) |
O8i—V3—O5 | 87.29 (6) | O8—V1i—O2i | 84.19 (5) |
V3—O5—V3iii | 101.27 (7) | O8—V1i—O4i | 83.04 (5) |
O7—V3—O5 | 80.65 (6) | O8—V1i—O5i | 74.56 (5) |
O5i—V3—O5 | 78.73 (5) | O8—V1i—O1i | 157.70 (6) |
O8—V3—O5 | 166.03 (6) | O8—V1i—O3i | 97.44 (7) |
O7i—V3—O5i | 80.65 (6) | O10—Li1—O10ii | 104.6 (3) |
O8i—V3—O5i | 166.03 (6) | O10—Li1—O11 | 94.0 (2) |
V3—O5i—V3iii | 101.27 (7) | O10—Li1—O6v | 104.3 (2) |
V3—O5i—V4 | 93.24 (5) | Li2—O11—Li1 | 111.4 (2) |
O7—V3—O5i | 80.42 (6) | O11—Li1—O10ii | 94.0 (2) |
V3—O5i—V1i | 88.10 (1) | O11—Li1—O6v | 149.8 (3) |
V3—O5i—V2i | 93.29 (5) | O11—Li2—O12 | 104.0 (2) |
O8—V3—O5i | 87.29 (6) | O12—Li2—O12ii | 96.1 (2) |
V3—O5i—V1iii | 170.63 (6) | Li3—O12—Li2 | 89.8 (2) |
O7i—V3—O7 | 155.43 (6) | O12—Li3—O12ii | 83.9 (2) |
O8i—V3—O7 | 97.26 (5) | O12—Li3—O14 | 90.0 (2) |
V3—O7—V4 | 108.64 (6) | O12—Li3—O13 | 93.4 (2) |
O8—V3—O7 | 97.33 (5) | O12—Li3—O15 | 93.33 (5) |
V3—O7i—V4i | 108.64 (6) | O13—Li3—O14 | 175.4 (3) |
O8i—V3—O7i | 97.33 (5) | O13—Li3—O15 | 86.8 (2) |
V3—O7i—V2i | 107.27 (6) | O14—Li3—O15 | 89.9 (2) |
O8—V3—O7i | 97.26 (6) | O15—Li3—O15ii | 89.4 (2) |
O8i—V3—O8 | 106.68 (7) | O15ii—Li3—O12ii | 93.33 (5) |
Symmetry codes: (i) −x+1, −y+1, z; (ii) x, y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y−1, z; (v) x, y+1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H2···O4vi | 0.90 | 1.94 | 2.804 (2) | 159 |
O11—H3···O8vii | 0.85 | 2.01 | 2.851 (2) | 163 |
O12—H4···O10viii | 0.83 | 1.98 | 2.815 (2) | 174 |
O12—H5···O7vi | 0.82 | 1.97 | 2.777 (2) | 167 |
O13—H6···O8vi | 0.95 | 1.92 | 2.872 (2) | 171 |
O14—H8···O13ix | 0.82 | 2.14 | 2.952 (3) | 167 |
O10—H1···O2 | 0.79 | 2.18 | 2.969 (2) | 170 |
O14—H7···O4 | 0.86 | 2.56 | 3.312 (3) | 146 |
O15—H9···O2vii | 0.94 | 2.10 | 3.034 (2) | 175 |
Symmetry codes: (vi) −x+3/2, y+1/2, −z+3/2; (vii) x+1/2, −y+3/2, −z+3/2; (viii) −x+3/2, y−1/2, −z+3/2; (ix) −x+2, −y+1, z. |
Experimental details
Crystal data |
Chemical formula | Li6(H2O)16V10O28 |
Mr | 1287.29 |
Crystal system, space group | Orthorhombic, Pnnm |
Temperature (K) | 273 |
a, b, c (Å) | 17.6164 (2), 10.3189 (1), 9.2348 (3) |
V (Å3) | 1678.72 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.79 |
Crystal size (mm) | 0.39 × 0.31 × 0.26 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.391, 0.484 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 16609, 2044, 1611 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.072, 1.03 |
No. of reflections | 1611 |
No. of parameters | 160 |
No. of restraints | 5 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.42 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H2···O4i | 0.90 | 1.94 | 2.804 (2) | 159 |
O11—H3···O8ii | 0.85 | 2.01 | 2.851 (2) | 163 |
O12—H4···O10iii | 0.83 | 1.98 | 2.815 (2) | 174 |
O12—H5···O7i | 0.82 | 1.97 | 2.777 (2) | 167 |
O13—H6···O8i | 0.95 | 1.92 | 2.872 (2) | 171 |
O14—H8···O13iv | 0.82 | 2.14 | 2.952 (3) | 167 |
O10—H1···O2 | 0.79 | 2.18 | 2.969 (2) | 170 |
O14—H7···O4 | 0.86 | 2.56 | 3.312 (3) | 146 |
O15—H9···O2ii | 0.94 | 2.10 | 3.034 (2) | 175 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x+1/2, −y+3/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+2, −y+1, z. |
Recently polyoxometalates have received extensive attention because of their varied applications in many fields, such as clinical chemistry, catalysis, medicine, solid-state devices and materials science (Kozhevnikov, 1998; Müller, 1998; Rhule et al., 1998; Toshihiro, 1998). Polyoxovanadate clusters, an important class of polyoxometalates, have been studied deeply because of their fascinating structure and potential applications (Zhang & Chen, 2003). In this work, orange single crystals of hexalithium hexadecahydrate decavanadate, [Li6(H2O)16V10O28]n, (I), have been synthesized and their structure determined.
Compound (I) contains [V10O28]6− polyanions with 2/m symmetry and centrosymmetric [Li6(H2O)16]6+ cation chains (Fig. 1). The decavanadate anion, presenting a cage-like structure, is composed of ten [VO6] octahedra combined via shared edges and shared corners. Six octahedra are arranged in a (2 × 3) equatorial plane sharing edges with one another; the other four octahedra are distributed above and below the equatorial plane, connected by shared sloping edges with the central six octahedra. According to the coordinative conditions, the O atoms in the polyanion can be classified into four types, viz. eight terminal O atoms (O3, O9, O6 and symmetry-related atoms) lying on the outer corners, with V—O distances of 1.595 (2)–1.607 (2) Å; fourteen double-bridging O atoms (O4, O8, O2 and O1) with V—O distances of 1.694 (1)–1.882 (1) Å; four triply bridging O atoms (O7) lying on the surface of the [V10O28]6− cluster, with V—O distances of 1.898 (1)–2.019 (1) Å; and two six-coordinate O atoms (O5) in the centers of the [OV6] octahedra with V—O distances of 2.126 (1)–2.308 (1) Å. The bond lengths and angles of the [V10O28]6− anion show a similar trend to those found in the literature (Kamenar et al., 1996; Choi & Chang, 2003).
The hexalithium hexadecahydrate chain is composed of a centrosymmetric pair of edge-shared octahedra (Li3) extended from the symmetry center by an edge-shared tetrahedron (Li2) linked to a corner-shared tetrahedron (Li1). In the octahedra, the lengths of the Li—O bonds are in the range 2.072 (6)–2.195 (4) Å, the cis-O—Li—O angles are in the range 83.9 (2)–93.33 (5)° and the angles of trans-O—Li—O are in the range of 175.4 (3)–177.2 (2)°. In the tetrahedra, one oxygen is from the [V10O28]6− ion with Li—O lengths of 2.007 (5)–2.016 (5) Å, and three O atoms are from water molecules with Li—O lengths of 1.954 (4)–2.144 (6) Å, and O—L—O angles of 94.0 (2)–149.8 (5)°.
In the ab plane, [V10O28]6− clusters are linked through [Li6(H2O)16]6+ chains to form an extended two-dimensional array (Fig. 2). Atom Li2 in the [Li6(H2O)16]6+ chain is bonded to an axial terminal O atom (O1) of a neighboring [V10O28]6− anion, and atom Li1 is bonded to atom O6 of another [V10O28]6− anion.
Hydrogen-bonds occur between the polyanion and Li-based chain, and within the Li-based chain in the compound. The water molecules, except the two water molecules containing O15, form hydrogen bonds with O atoms of the decavanadate group; there are also OW—H···OW hydrogen-bond interactions. All of the O atoms on the surface of the decavanadate anion form hydrogen bonds with water except atoms O1, O3, O6 and O9. Atom O3 participates in no hydrogen-bond interactions. Hydrogen-bonds with a distance less than 2.95 Å are listed in Table 1.
TGA results show that the weight loss of the crystal is around 22.0% in the range 343–583 K. This is compatible with the content of water (22.4 wt%) resulting from the theoretical calculation in the molecular formula.