The crystal structure of the title compound, (NH4)2[Ni(H2O)6]2V10O28·4H2O, comprises centrosymmetric [V10O28]6- anions that are linked via hydrogen bonding by two NH4+ cations, two [Ni(H2O)6]2+ cations, and four water molecules into a three-dimensional structure. The compound is isotypic with other members of the [M(H2O)6]2(NH4)2V10O28·4H2O series (M = Mg and Co).
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (i-O)= 0.002 Å
- R factor = 0.024
- wR factor = 0.060
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
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Datablock: I
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A mixture of NH4VO3 (Shanghai Chemical Reagents) and Ni(Ac)2·4H2O (Shanghai Chemical Reagents) in a 1:0.2 molar ratio was acidified to pH 5 and hydrothermally treated for 10 h at 398 K. The resulting filtrate was kept at room temperature and after some days a yellow polycrystalline powder precipitated from the solution which was subsequently filtered off. Yellow single crystals of (I) of up to 3 mm in length and of mostly block-like habit formed after 20 d from this solution.
All H atoms were found in a difference Fourier map. Their positions were refined freely using the same isotropic displacement parameter for all H atoms.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 2002); data reduction: Crystal Structure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: SHELXL97.
Crystal data top
(NH4)2[Ni(H2O)6]2V10O28·4H2O | Z = 1 |
Mr = 1399.12 | F(000) = 692 |
Triclinic, P1 | Dx = 2.588 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7728 (18) Å | Cell parameters from 7874 reflections |
b = 10.923 (2) Å | θ = 3.4–27.5° |
c = 11.114 (2) Å | µ = 3.64 mm−1 |
α = 65.18 (3)° | T = 173 K |
β = 73.12 (3)° | Block, yellow |
γ = 70.64 (3)° | 0.20 × 0.20 × 0.20 mm |
V = 897.6 (4) Å3 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 4056 independent reflections |
Radiation source: fine-focus sealed tube | 3602 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −14→14 |
Tmin = 0.471, Tmax = 0.483 | l = −14→12 |
8845 measured reflections | |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0185P)2 + 1.7228P] where P = (Fo2 + 2Fc2)/3 |
4056 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
Crystal data top
(NH4)2[Ni(H2O)6]2V10O28·4H2O | γ = 70.64 (3)° |
Mr = 1399.12 | V = 897.6 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.7728 (18) Å | Mo Kα radiation |
b = 10.923 (2) Å | µ = 3.64 mm−1 |
c = 11.114 (2) Å | T = 173 K |
α = 65.18 (3)° | 0.20 × 0.20 × 0.20 mm |
β = 73.12 (3)° | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 4056 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3602 reflections with I > 2σ(I) |
Tmin = 0.471, Tmax = 0.483 | Rint = 0.021 |
8845 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.47 e Å−3 |
4056 reflections | Δρmin = −0.43 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 | |
Ni | 0.77935 (4) | 0.73559 (3) | 0.78156 (3) | 0.00754 (8) | |
V1 | 0.69104 (5) | 0.73612 (4) | 0.23549 (4) | 0.00725 (9) | |
V2 | 0.38279 (5) | 0.77454 (4) | 0.44976 (4) | 0.00630 (9) | |
V3 | 0.36396 (5) | 0.71898 (4) | 0.20208 (4) | 0.00716 (9) | |
V4 | 0.32299 (5) | 0.49313 (4) | 0.48397 (4) | 0.00576 (9) | |
V5 | 0.35210 (5) | 0.54994 (4) | 0.72996 (4) | 0.00609 (9) | |
O1 | 0.8279 (2) | 0.82194 (19) | 0.14635 (18) | 0.0116 (4) | |
O2 | 0.2878 (2) | 0.88984 (18) | 0.51839 (18) | 0.0099 (3) | |
O3 | 0.2513 (2) | 0.79399 (19) | 0.08874 (18) | 0.0118 (4) | |
O4 | 0.2035 (2) | 0.38655 (18) | 0.59565 (17) | 0.0085 (3) | |
O5 | 0.2202 (2) | 0.42913 (17) | 0.80454 (17) | 0.0076 (3) | |
O6 | 0.4792 (2) | 0.35668 (17) | 0.41068 (17) | 0.0067 (3) | |
O7 | 0.2524 (2) | 0.66600 (18) | 0.79654 (18) | 0.0097 (3) | |
O8 | 0.5082 (2) | 0.44277 (17) | 0.83646 (17) | 0.0077 (3) | |
O9 | 0.5624 (2) | 0.83814 (17) | 0.34111 (17) | 0.0076 (3) | |
O10 | 0.5403 (2) | 0.79892 (18) | 0.12541 (17) | 0.0088 (3) | |
O11 | 0.2762 (2) | 0.82728 (17) | 0.31027 (17) | 0.0082 (3) | |
O12 | 0.2309 (2) | 0.58745 (18) | 0.34623 (17) | 0.0077 (3) | |
O13 | 0.4863 (2) | 0.40223 (17) | 0.62168 (16) | 0.0065 (3) | |
O14 | 0.2559 (2) | 0.63212 (17) | 0.56256 (17) | 0.0065 (3) | |
O15 | 0.9447 (3) | 0.8545 (2) | 0.6688 (2) | 0.0228 (4) | |
O16 | 0.6622 (2) | 0.81476 (19) | 0.61938 (18) | 0.0121 (4) | |
O17 | 0.9093 (2) | 0.5669 (2) | 0.7265 (2) | 0.0192 (4) | |
O18 | 0.5903 (2) | 0.63802 (18) | 0.89135 (17) | 0.0102 (3) | |
O19 | 0.9122 (2) | 0.6542 (2) | 0.93409 (18) | 0.0144 (4) | |
O20 | 0.6350 (2) | 0.89580 (18) | 0.85052 (18) | 0.0111 (4) | |
O21 | −0.0096 (2) | 0.9454 (2) | 0.87664 (19) | 0.0167 (4) | |
O22 | 0.9237 (2) | 0.8325 (2) | 0.3987 (2) | 0.0156 (4) | |
N | 0.3278 (3) | 0.9151 (2) | 0.7615 (2) | 0.0112 (4) | |
H15A | 0.9685 | 0.8916 | 0.7168 | 0.050* | |
H15B | 1.0487 | 0.8167 | 0.6261 | 0.050* | |
H16A | 0.7339 | 0.8371 | 0.5421 | 0.050* | |
H16B | 0.6107 | 0.7563 | 0.6146 | 0.050* | |
H17A | 0.8746 | 0.5193 | 0.6981 | 0.050* | |
H17B | 1.0128 | 0.5222 | 0.7384 | 0.050* | |
H18A | 0.5579 | 0.6109 | 0.9756 | 0.050* | |
H18B | 0.5825 | 0.5766 | 0.8655 | 0.050* | |
H19A | 0.8731 | 0.6268 | 1.0198 | 0.050* | |
H19B | 1.0085 | 0.6662 | 0.9084 | 0.050* | |
H20A | 0.6063 | 0.8735 | 0.9323 | 0.050* | |
H20B | 0.6561 | 0.9732 | 0.8074 | 0.050* | |
H21A | −0.0576 | 1.0296 | 0.8712 | 0.050* | |
H21B | −0.0455 | 0.9007 | 0.9577 | 0.050* | |
H22A | 1.0249 | 0.8305 | 0.3806 | 0.050* | |
H22B | 0.9294 | 0.7555 | 0.3794 | 0.050* | |
H23A | 0.3216 | 0.9019 | 0.6803 | 0.050* | |
H23B | 0.2190 | 0.9262 | 0.8164 | 0.050* | |
H23C | 0.4130 | 0.8364 | 0.8055 | 0.050* | |
H23D | 0.3681 | 0.9921 | 0.7208 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.00774 (15) | 0.00808 (15) | 0.00719 (15) | −0.00203 (12) | −0.00112 (11) | −0.00314 (12) |
V1 | 0.0087 (2) | 0.00641 (19) | 0.00648 (19) | −0.00295 (15) | −0.00033 (15) | −0.00194 (16) |
V2 | 0.00814 (19) | 0.00496 (19) | 0.00538 (19) | −0.00100 (15) | −0.00092 (15) | −0.00206 (16) |
V3 | 0.0090 (2) | 0.00638 (19) | 0.00564 (19) | −0.00099 (15) | −0.00227 (15) | −0.00178 (16) |
V4 | 0.00600 (19) | 0.00594 (19) | 0.00592 (19) | −0.00169 (15) | −0.00110 (15) | −0.00244 (16) |
V5 | 0.00729 (19) | 0.00537 (19) | 0.00574 (19) | −0.00144 (15) | −0.00086 (15) | −0.00238 (16) |
O1 | 0.0141 (9) | 0.0122 (9) | 0.0091 (8) | −0.0065 (7) | 0.0019 (7) | −0.0047 (7) |
O2 | 0.0122 (9) | 0.0079 (8) | 0.0094 (8) | −0.0006 (7) | −0.0025 (7) | −0.0040 (7) |
O3 | 0.0155 (9) | 0.0106 (9) | 0.0100 (9) | −0.0008 (7) | −0.0060 (7) | −0.0037 (7) |
O4 | 0.0085 (8) | 0.0080 (8) | 0.0097 (8) | −0.0024 (7) | −0.0019 (7) | −0.0033 (7) |
O5 | 0.0094 (8) | 0.0079 (8) | 0.0056 (8) | −0.0036 (7) | 0.0005 (6) | −0.0025 (7) |
O6 | 0.0074 (8) | 0.0052 (8) | 0.0078 (8) | −0.0006 (6) | −0.0023 (6) | −0.0026 (7) |
O7 | 0.0106 (8) | 0.0087 (8) | 0.0115 (9) | −0.0027 (7) | −0.0026 (7) | −0.0044 (7) |
O8 | 0.0100 (8) | 0.0076 (8) | 0.0064 (8) | −0.0023 (7) | −0.0015 (6) | −0.0034 (7) |
O9 | 0.0098 (8) | 0.0065 (8) | 0.0058 (8) | −0.0029 (7) | 0.0003 (6) | −0.0019 (7) |
O10 | 0.0108 (8) | 0.0071 (8) | 0.0080 (8) | −0.0015 (7) | −0.0017 (7) | −0.0027 (7) |
O11 | 0.0087 (8) | 0.0070 (8) | 0.0073 (8) | −0.0007 (7) | −0.0020 (7) | −0.0015 (7) |
O12 | 0.0069 (8) | 0.0085 (8) | 0.0084 (8) | −0.0012 (6) | −0.0017 (6) | −0.0040 (7) |
O13 | 0.0076 (8) | 0.0058 (8) | 0.0061 (8) | −0.0014 (6) | −0.0013 (6) | −0.0021 (7) |
O14 | 0.0068 (8) | 0.0060 (8) | 0.0068 (8) | −0.0012 (6) | −0.0023 (6) | −0.0018 (7) |
O15 | 0.0177 (10) | 0.0261 (11) | 0.0231 (11) | −0.0077 (9) | −0.0038 (8) | −0.0054 (9) |
O16 | 0.0141 (9) | 0.0130 (9) | 0.0104 (9) | −0.0053 (7) | −0.0034 (7) | −0.0030 (7) |
O17 | 0.0120 (9) | 0.0201 (10) | 0.0352 (12) | 0.0016 (8) | −0.0086 (8) | −0.0202 (10) |
O18 | 0.0140 (9) | 0.0100 (8) | 0.0084 (8) | −0.0059 (7) | −0.0012 (7) | −0.0031 (7) |
O19 | 0.0106 (9) | 0.0225 (10) | 0.0068 (8) | −0.0042 (8) | −0.0011 (7) | −0.0022 (8) |
O20 | 0.0160 (9) | 0.0079 (8) | 0.0095 (9) | −0.0028 (7) | −0.0033 (7) | −0.0027 (7) |
O21 | 0.0153 (10) | 0.0141 (9) | 0.0146 (9) | −0.0040 (8) | 0.0008 (8) | −0.0013 (8) |
O22 | 0.0133 (9) | 0.0176 (10) | 0.0177 (10) | −0.0045 (8) | −0.0003 (8) | −0.0090 (8) |
N | 0.0137 (10) | 0.0081 (10) | 0.0143 (11) | −0.0038 (8) | −0.0048 (9) | −0.0041 (9) |
Geometric parameters (Å, º) top
Ni—O15 | 2.047 (2) | V4—V1i | 3.0713 (14) |
Ni—O19 | 2.054 (2) | V5—O7 | 1.6112 (18) |
Ni—O17 | 2.054 (2) | V5—O5 | 1.8179 (18) |
Ni—O16 | 2.057 (2) | V5—O8 | 1.8337 (19) |
Ni—O18 | 2.0688 (19) | V5—O14 | 1.9965 (18) |
Ni—O20 | 2.0848 (19) | V5—O6i | 1.9979 (19) |
V1—O1 | 1.6054 (19) | V5—O13 | 2.2328 (18) |
V1—O10 | 1.8303 (19) | O4—V1i | 2.061 (2) |
V1—O9 | 1.8407 (18) | O5—V1i | 1.8982 (18) |
V1—O5i | 1.8982 (18) | O6—V5i | 1.9979 (19) |
V1—O4i | 2.061 (2) | O6—V2i | 1.9997 (19) |
V1—O13i | 2.3093 (19) | O8—V3i | 1.8987 (18) |
V1—V4i | 3.0713 (14) | O13—V4i | 2.1180 (18) |
V1—V3 | 3.0725 (8) | O13—V2i | 2.2282 (18) |
V1—V2 | 3.0832 (13) | O13—V1i | 2.3093 (19) |
V2—O2 | 1.6136 (18) | O13—V3i | 2.3410 (19) |
V2—O9 | 1.8276 (18) | O15—H15A | 0.8909 |
V2—O11 | 1.8291 (18) | O15—H15B | 0.9442 |
V2—O14 | 1.9825 (19) | O16—H16A | 0.8974 |
V2—O6i | 1.9997 (19) | O16—H16B | 0.9209 |
V2—O13i | 2.2282 (18) | O17—H17A | 0.8725 |
V2—V5 | 3.0537 (14) | O17—H17B | 0.8954 |
V2—V3 | 3.1155 (8) | O18—H18A | 0.8448 |
V3—O3 | 1.5985 (19) | O18—H18B | 0.8609 |
V3—O10 | 1.8404 (19) | O19—H19A | 0.8680 |
V3—O11 | 1.8682 (18) | O19—H19B | 0.8453 |
V3—O8i | 1.8987 (18) | O20—H20A | 0.8190 |
V3—O12 | 2.0214 (19) | O20—H20B | 0.8313 |
V3—O13i | 2.3410 (19) | O21—H21A | 0.8592 |
V3—V4 | 3.0782 (14) | O21—H21B | 0.8469 |
V4—O4 | 1.6840 (19) | O22—H22A | 0.8460 |
V4—O12 | 1.7027 (19) | O22—H22B | 0.9345 |
V4—O14 | 1.9069 (17) | N—H23A | 0.9903 |
V4—O6 | 1.9442 (18) | N—H23B | 0.9723 |
V4—O13 | 2.1057 (19) | N—H23C | 0.9850 |
V4—O13i | 2.1180 (18) | N—H23D | 0.9065 |
| | | |
O15—Ni—O19 | 87.70 (8) | O13i—V3—V4 | 43.41 (5) |
O15—Ni—O17 | 95.55 (9) | V1—V3—V4 | 91.61 (4) |
O19—Ni—O17 | 87.93 (8) | O3—V3—V2 | 134.85 (7) |
O15—Ni—O16 | 89.45 (8) | O10—V3—V2 | 82.12 (6) |
O19—Ni—O16 | 175.84 (7) | O11—V3—V2 | 32.20 (6) |
O17—Ni—O16 | 89.33 (8) | O8i—V3—V2 | 122.89 (6) |
O15—Ni—O18 | 172.97 (8) | O12—V3—V2 | 81.57 (5) |
O19—Ni—O18 | 96.18 (8) | O13i—V3—V2 | 45.51 (4) |
O17—Ni—O18 | 90.46 (8) | V1—V3—V2 | 59.77 (3) |
O16—Ni—O18 | 86.97 (8) | V4—V3—V2 | 60.85 (2) |
O15—Ni—O20 | 89.29 (8) | O4—V4—O12 | 107.01 (9) |
O19—Ni—O20 | 91.17 (8) | O4—V4—O14 | 98.62 (8) |
O17—Ni—O20 | 175.04 (8) | O12—V4—O14 | 97.91 (8) |
O16—Ni—O20 | 91.83 (8) | O4—V4—O6 | 96.32 (8) |
O18—Ni—O20 | 84.79 (7) | O12—V4—O6 | 95.91 (8) |
O1—V1—O10 | 103.45 (9) | O14—V4—O6 | 155.69 (7) |
O1—V1—O9 | 102.66 (9) | O4—V4—O13 | 87.89 (8) |
O10—V1—O9 | 93.55 (8) | O12—V4—O13 | 164.99 (8) |
O1—V1—O5i | 101.28 (9) | O14—V4—O13 | 81.20 (7) |
O10—V1—O5i | 91.02 (8) | O6—V4—O13 | 80.30 (7) |
O9—V1—O5i | 153.82 (8) | O4—V4—O13i | 165.69 (8) |
O1—V1—O4i | 99.85 (9) | O12—V4—O13i | 87.17 (8) |
O10—V1—O4i | 156.59 (8) | O14—V4—O13i | 80.87 (7) |
O9—V1—O4i | 83.54 (8) | O6—V4—O13i | 79.93 (7) |
O5i—V1—O4i | 82.11 (8) | O13—V4—O13i | 77.89 (8) |
O1—V1—O13i | 174.03 (8) | O4—V4—V1i | 39.17 (6) |
O10—V1—O13i | 82.34 (7) | O12—V4—V1i | 146.16 (6) |
O9—V1—O13i | 78.15 (7) | O14—V4—V1i | 90.73 (6) |
O5i—V1—O13i | 76.95 (7) | O6—V4—V1i | 88.83 (6) |
O4i—V1—O13i | 74.31 (7) | O13—V4—V1i | 48.72 (5) |
O1—V1—V4i | 130.90 (7) | O13i—V4—V1i | 126.59 (6) |
O10—V1—V4i | 125.56 (6) | O4—V4—V3 | 144.76 (7) |
O9—V1—V4i | 79.19 (6) | O12—V4—V3 | 37.75 (6) |
O5i—V1—V4i | 77.22 (6) | O14—V4—V3 | 89.69 (6) |
O4i—V1—V4i | 31.06 (5) | O6—V4—V3 | 89.08 (6) |
O13i—V1—V4i | 43.25 (5) | O13—V4—V3 | 127.31 (5) |
O1—V1—V3 | 136.72 (7) | O13i—V4—V3 | 49.43 (5) |
O10—V1—V3 | 33.28 (6) | V1i—V4—V3 | 175.832 (18) |
O9—V1—V3 | 85.12 (6) | O7—V5—O5 | 101.40 (9) |
O5i—V1—V3 | 84.68 (6) | O7—V5—O8 | 102.33 (9) |
O4i—V1—V3 | 123.40 (6) | O5—V5—O8 | 95.86 (8) |
O13i—V1—V3 | 49.09 (5) | O7—V5—O14 | 99.59 (9) |
V4i—V1—V3 | 92.34 (4) | O5—V5—O14 | 89.38 (8) |
O1—V1—V2 | 135.24 (7) | O8—V5—O14 | 155.94 (7) |
O10—V1—V2 | 83.20 (6) | O7—V5—O6i | 101.32 (8) |
O9—V1—V2 | 32.67 (5) | O5—V5—O6i | 154.95 (7) |
O5i—V1—V2 | 123.04 (6) | O8—V5—O6i | 89.48 (8) |
O4i—V1—V2 | 81.94 (6) | O14—V5—O6i | 76.54 (7) |
O13i—V1—V2 | 46.10 (5) | O7—V5—O13 | 175.39 (8) |
V4i—V1—V2 | 61.99 (3) | O5—V5—O13 | 80.54 (7) |
V3—V1—V2 | 60.81 (2) | O8—V5—O13 | 81.54 (7) |
O2—V2—O9 | 103.10 (9) | O14—V5—O13 | 76.18 (7) |
O2—V2—O11 | 103.60 (9) | O6i—V5—O13 | 76.05 (7) |
O9—V2—O11 | 94.15 (8) | O7—V5—V2 | 90.87 (7) |
O2—V2—O14 | 98.91 (8) | O5—V5—V2 | 129.08 (6) |
O9—V2—O14 | 155.58 (7) | O8—V5—V2 | 129.69 (6) |
O11—V2—O14 | 90.83 (8) | O14—V5—V2 | 39.71 (5) |
O2—V2—O6i | 98.49 (8) | O6i—V5—V2 | 40.21 (5) |
O9—V2—O6i | 89.49 (8) | O13—V5—V2 | 84.69 (5) |
O11—V2—O6i | 156.15 (7) | V4—O4—V1i | 109.77 (9) |
O14—V2—O6i | 76.82 (7) | V5—O5—V1i | 114.28 (9) |
O2—V2—O13i | 173.59 (8) | V4—O6—V5i | 107.54 (8) |
O9—V2—O13i | 80.61 (7) | V4—O6—V2i | 106.95 (8) |
O11—V2—O13i | 81.17 (7) | V5i—O6—V2i | 99.62 (8) |
O14—V2—O13i | 76.56 (7) | V5—O8—V3i | 113.84 (9) |
O6i—V2—O13i | 76.17 (7) | V2—O9—V1 | 114.39 (9) |
O2—V2—V5 | 88.57 (7) | V1—O10—V3 | 113.65 (10) |
O9—V2—V5 | 129.65 (6) | V2—O11—V3 | 114.83 (9) |
O11—V2—V5 | 130.87 (6) | V4—O12—V3 | 111.20 (9) |
O14—V2—V5 | 40.04 (5) | V4—O13—V4i | 102.11 (8) |
O6i—V2—V5 | 40.17 (5) | V4—O13—V2i | 93.95 (7) |
O13i—V2—V5 | 85.05 (5) | V4i—O13—V2i | 92.37 (7) |
O2—V2—V1 | 135.89 (7) | V4—O13—V5 | 92.68 (7) |
O9—V2—V1 | 32.94 (5) | V4i—O13—V5 | 93.89 (7) |
O11—V2—V1 | 82.93 (6) | V2i—O13—V5 | 169.74 (9) |
O14—V2—V1 | 124.85 (6) | V4—O13—V1i | 88.03 (7) |
O6i—V2—V1 | 87.51 (6) | V4i—O13—V1i | 169.77 (9) |
O13i—V2—V1 | 48.31 (5) | V2i—O13—V1i | 85.59 (6) |
V5—V2—V1 | 120.23 (4) | V5—O13—V1i | 86.82 (6) |
O2—V2—V3 | 136.51 (7) | V4—O13—V3i | 170.72 (8) |
O9—V2—V3 | 84.05 (6) | V4i—O13—V3i | 87.16 (7) |
O11—V2—V3 | 32.97 (5) | V2i—O13—V3i | 85.94 (6) |
O14—V2—V3 | 87.27 (6) | V5—O13—V3i | 86.25 (6) |
O6i—V2—V3 | 124.69 (5) | V1i—O13—V3i | 82.70 (6) |
O13i—V2—V3 | 48.55 (5) | V4—O14—V2 | 107.50 (8) |
V5—V2—V3 | 119.90 (2) | V4—O14—V5 | 107.08 (8) |
V1—V2—V3 | 59.42 (2) | V2—O14—V5 | 100.25 (8) |
O3—V3—O10 | 103.42 (9) | Ni—O15—H15A | 111.6 |
O3—V3—O11 | 102.69 (9) | Ni—O15—H15B | 121.2 |
O10—V3—O11 | 90.86 (8) | H15A—O15—H15B | 103.5 |
O3—V3—O8i | 102.04 (9) | Ni—O16—H16A | 110.3 |
O10—V3—O8i | 90.32 (8) | Ni—O16—H16B | 115.4 |
O11—V3—O8i | 154.24 (8) | H16A—O16—H16B | 106.6 |
O3—V3—O12 | 100.88 (9) | Ni—O17—H17A | 128.7 |
O10—V3—O12 | 155.68 (8) | Ni—O17—H17B | 123.7 |
O11—V3—O12 | 84.84 (7) | H17A—O17—H17B | 107.2 |
O8i—V3—O12 | 83.57 (8) | Ni—O18—H18A | 127.8 |
O3—V3—O13i | 175.32 (8) | Ni—O18—H18B | 115.6 |
O10—V3—O13i | 81.25 (7) | H18A—O18—H18B | 106.3 |
O11—V3—O13i | 77.38 (7) | Ni—O19—H19A | 126.2 |
O8i—V3—O13i | 77.38 (7) | Ni—O19—H19B | 114.0 |
O12—V3—O13i | 74.45 (7) | H19A—O19—H19B | 118.4 |
O3—V3—V1 | 136.47 (7) | Ni—O20—H20A | 115.8 |
O10—V3—V1 | 33.07 (6) | Ni—O20—H20B | 116.3 |
O11—V3—V1 | 82.66 (6) | H20A—O20—H20B | 117.9 |
O8i—V3—V1 | 84.38 (6) | H21A—O21—H21B | 101.4 |
O12—V3—V1 | 122.65 (6) | H22A—O22—H22B | 99.3 |
O13i—V3—V1 | 48.21 (5) | H23A—N—H23B | 109.1 |
O3—V3—V4 | 131.92 (7) | H23A—N—H23C | 107.0 |
O10—V3—V4 | 124.66 (6) | H23B—N—H23C | 115.7 |
O11—V3—V4 | 78.98 (6) | H23A—N—H23D | 99.1 |
O8i—V3—V4 | 79.23 (6) | H23B—N—H23D | 115.7 |
O12—V3—V4 | 31.05 (5) | H23C—N—H23D | 108.6 |
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 |
O15—H15A···O21ii | 0.891 | 2.166 | 3.035 (3) | 165 |
O15—H15B···O2ii | 0.944 | 2.306 | 3.050 (3) | 135 |
O15—H15B···O14ii | 0.944 | 2.426 | 3.300 (3) | 154 |
O16—H16A···O22 | 0.897 | 1.947 | 2.819 (3) | 164 |
O16—H16B···O6i | 0.920 | 1.814 | 2.731 (2) | 175 |
O17—H17A···O12i | 0.872 | 1.980 | 2.847 (3) | 172 |
O17—H17B···O5ii | 0.895 | 1.951 | 2.830 (2) | 167 |
O17—H17B···O4ii | 0.895 | 2.510 | 3.083 (6) | 122 |
O18—H18A···O8iii | 0.846 | 1.881 | 2.726 (1) | 177 |
O18—H18B···O8 | 0.861 | 1.954 | 2.794 (3) | 165 |
O19—H19A···O5iii | 0.868 | 1.805 | 2.671 (3) | 176 |
O19—H19B···O7ii | 0.845 | 2.140 | 2.951 (3) | 161 |
O20—H20A···O10iv | 0.820 | 1.931 | 2.746 (3) | 173 |
O21—H21A···O3v | 0.858 | 2.215 | 3.030 (3) | 159 |
O21—H21B···O1vi | 0.847 | 2.034 | 2.869 (3) | 169 |
O22—H22A···O11ii | 0.846 | 2.108 | 2.948 (3) | 173 |
O22—H22B···O4i | 0.934 | 2.120 | 2.928 (3) | 144 |
N—H23A···O2 | 0.991 | 1.969 | 2.957 (3) | 174 |
N—H23B···O21 | 0.975 | 1.891 | 2.831 (3) | 162 |
N—H23C···O18 | 0.987 | 2.217 | 3.195 (3) | 170 |
N—H23C···O20 | 0.987 | 2.478 | 3.044 (3) | 116 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+2; (iv) x, y, z+1; (v) −x, −y+2, −z+1; (vi) x−1, y, z+1. |
Experimental details
Crystal data |
Chemical formula | (NH4)2[Ni(H2O)6]2V10O28·4H2O |
Mr | 1399.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.7728 (18), 10.923 (2), 11.114 (2) |
α, β, γ (°) | 65.18 (3), 73.12 (3), 70.64 (3) |
V (Å3) | 897.6 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 3.64 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.471, 0.483 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8845, 4056, 3602 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.060, 1.09 |
No. of reflections | 4056 |
No. of parameters | 262 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.47, −0.43 |
Selected bond lengths (Å) topNi—O15 | 2.047 (2) | V3—O3 | 1.5985 (19) |
Ni—O19 | 2.054 (2) | V3—O10 | 1.8404 (19) |
Ni—O17 | 2.054 (2) | V3—O11 | 1.8682 (18) |
Ni—O16 | 2.057 (2) | V3—O8i | 1.8987 (18) |
Ni—O18 | 2.0688 (19) | V3—O12 | 2.0214 (19) |
Ni—O20 | 2.0848 (19) | V3—O13i | 2.3410 (19) |
V1—O1 | 1.6054 (19) | V4—O4 | 1.6840 (19) |
V1—O10 | 1.8303 (19) | V4—O12 | 1.7027 (19) |
V1—O9 | 1.8407 (18) | V4—O14 | 1.9069 (17) |
V1—O5i | 1.8982 (18) | V4—O6 | 1.9442 (18) |
V1—O4i | 2.061 (2) | V4—O13 | 2.1057 (19) |
V1—O13i | 2.3093 (19) | V4—O13i | 2.1180 (18) |
V2—O2 | 1.6136 (18) | V5—O7 | 1.6112 (18) |
V2—O9 | 1.8276 (18) | V5—O5 | 1.8179 (18) |
V2—O11 | 1.8291 (18) | V5—O8 | 1.8337 (19) |
V2—O14 | 1.9825 (19) | V5—O14 | 1.9965 (18) |
V2—O6i | 1.9997 (19) | V5—O6i | 1.9979 (19) |
V2—O13i | 2.2282 (18) | V5—O13 | 2.2328 (18) |
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 |
O15—H15A···O21ii | 0.891 | 2.166 | 3.035 (3) | 165 |
O15—H15B···O2ii | 0.944 | 2.306 | 3.050 (3) | 135 |
O15—H15B···O14ii | 0.944 | 2.426 | 3.300 (3) | 154 |
O16—H16A···O22 | 0.897 | 1.947 | 2.819 (3) | 164 |
O16—H16B···O6i | 0.920 | 1.814 | 2.731 (2) | 175 |
O17—H17A···O12i | 0.872 | 1.980 | 2.847 (3) | 172 |
O17—H17B···O5ii | 0.895 | 1.951 | 2.830 (2) | 167 |
O17—H17B···O4ii | 0.895 | 2.510 | 3.083 (6) | 122 |
O18—H18A···O8iii | 0.846 | 1.881 | 2.726 (1) | 177 |
O18—H18B···O8 | 0.861 | 1.954 | 2.794 (3) | 165 |
O19—H19A···O5iii | 0.868 | 1.805 | 2.671 (3) | 176 |
O19—H19B···O7ii | 0.845 | 2.140 | 2.951 (3) | 161 |
O20—H20A···O10iv | 0.820 | 1.931 | 2.746 (3) | 173 |
O21—H21A···O3v | 0.858 | 2.215 | 3.030 (3) | 159 |
O21—H21B···O1vi | 0.847 | 2.034 | 2.869 (3) | 169 |
O22—H22A···O11ii | 0.846 | 2.108 | 2.948 (3) | 173 |
O22—H22B···O4i | 0.934 | 2.120 | 2.928 (3) | 144 |
N—H23A···O2 | 0.991 | 1.969 | 2.957 (3) | 174 |
N—H23B···O21 | 0.975 | 1.891 | 2.831 (3) | 162 |
N—H23C···O18 | 0.987 | 2.217 | 3.195 (3) | 170 |
N—H23C···O20 | 0.987 | 2.478 | 3.044 (3) | 116 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+2; (iv) x, y, z+1; (v) −x, −y+2, −z+1; (vi) x−1, y, z+1. |
Recently, decavanadate double salts of nickel and alkali metals have been reported, viz. [Ni(H2O)6]2[Na(H2O)3]2[V10O28]·4H2O (Higami et al., 2002), NiNa4[HV10O28].23H2O (Sum et al., 2002) and [K(H2O)2Ni(H2O)6]2[V10O28] (Li et al., 2004). However, no double salt with nickel and ammonium has been reported up to now. We present here the crystal structure of the decavanadate [Ni(H2O)6]2(NH4)2V10O28·4H2O, (I), which is isotypic with other members of the series [M(H2O)6]2(NH4)2V10O28·4H2O where M = Mg (Avtamonova et al., 1990) and Co (Baudrin et al., 1997).
The structure of (I) consists of a centrosymmetric polyanion, [V10O28]6−, two nickel hexahydrate cations, [Ni(H2O)6]2+, two ammonium cations, NH4+, and four water molecules as single building units (Fig. 1). Each building unit is bonded to another unit via an extensive net of hydrogen bonds into a three-dimensional network. In this way, the [Ni(H2O)6]2+ cation is linked to the decavanadate polyanion and to an isolated water molecule, whereas the NH4+ group is connected to another water molecule and to the polyanion, so that all terminal O atoms of the [V10O28]6− anion are involved in hydrogen bonding (Fig. 2 and Table 2). The deviation from ideal values of the bonding angles in the water molecules of respectively 118.4 and 117.9° for H19A—O19—H19B and H20A—O20—H20B, and in the ammonium cation of 99.1 and 115.7°, is also explained by involvement in hydrogen bonding.
The Ni2+ cation in (I) is coordinated by six water molecules, forming a slightly distorted octahedron (Table 1) with the cis-O—Ni—O angles deviating by about 5° and the trans-O—Ni—O angles by about 7° from ideal values.
The decavanadate polyanion in (I) is composed of ten VO6 octahedra by edge- and corner-sharing. The arrangement of O and V atoms is very close to that in other decavanadates of composition Li6(H2O)16V10O28 (Xie & Ma, 2005) and [LiNa2(H2O)9]2V10O28 (Ma et al., 2005) reported previously. The V···V contacts within the polyanion in (I) range from 3.0537 (14) to 3.1155 (8) Å. The V—O bond-lenght distribution is correlated with the coordination number (CN) of the O atoms. Terminal O atoms with only one V—O bond have distances in the range 1.5985 (9) to 1.6136 (18) Å, whereas the other V–O distances increase with higher CN of the bridging O atoms. V—µ2-O distances are in the range 1.6840 (19) to 2.0214 (19) Å, V—µ3-O distances are 1.9069 (17)–1.9965 (18) Å, and V—µ6-O distances are 2.1057 (19)–2.3410 (19) Å. The bond lengths and angles of the [V10O28]6− polyanion are very similar than those observed in other decavanadates (Kamenar et al., 1996; Choi et al., 2003; Xie & Ma, 2005; Ma et al., 2005).