Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013008/ob1072sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013008/ob1072Isup2.hkl |
CCDC reference: 195601
The crude product of (I) was prepared by dissolving V2O5 (2.0 g, 0.011 mmol) in a 10% aqueous solution of Et4NOH (35 ml, 0.022 mmol), stirring the solution for 18 h, evaporating it to dryness under vacuum, dissolving the resulting solid in warm acetonitrile (100 ml), filtering off a small amount of insoluble material, adding diethyl ether (800 ml) to the filtrate, collecting by filtration the white precipitate that formed, and drying it under vacuum for 8 h (yield 73%, 3.8 g, 4.0 mmol). Crystals of (I) suitable for X-ray diffraction were obtained by dissolving the crude product (0.10 g) in warm acetonitrile (7 ml), adding m-xylene (5 ml) with stirring, and allowing the mixture to stand at ambient temperature overnight. The crystals gave a satisfactory elemental analysis; analysis calculated (found) for C32H84N4V4O14: C 40.59 (40.33), H 8.79 (8.89), N 5.78 (5.88), V 21.6 (21.4)%.
Water H atoms were located from difference Fourier syntheses and no refinements were applied. The H atoms in the tetraethylammonium cations were treated by constrained refinements, with C—H distances in the range 0.98–0.99 Å. Is this added text OK?
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996).
(C8H20N)4[V4O12]·2H2O | F(000) = 1016 |
Mr = 952.79 | Dx = 1.372 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4000 reflections |
a = 14.0187 (3) Å | θ = 1.0–30.5° |
b = 10.5729 (2) Å | µ = 0.85 mm−1 |
c = 16.0212 (4) Å | T = 90 K |
β = 103.836 (1)° | Plate, colourless |
V = 2305.7 (1) Å3 | 0.40 × 0.30 × 0.02 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 7001 independent reflections |
Radiation source: Rigaku Ultrax-18 rotating anode | 3962 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.114 |
ω scans | θmax = 30.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→20 |
Tmin = 0.631, Tmax = 0.983 | k = −14→15 |
22145 measured reflections | l = −21→22 |
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) = 0.141 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0673P)2] where P = (Fo2 + 2Fc2)/3 |
7001 reflections | (Δ/σ)max < 0.001 |
244 parameters | Δρmax = 0.72 e Å−3 |
0 restraints | Δρmin = −0.87 e Å−3 |
(C8H20N)4[V4O12]·2H2O | V = 2305.7 (1) Å3 |
Mr = 952.79 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.0187 (3) Å | µ = 0.85 mm−1 |
b = 10.5729 (2) Å | T = 90 K |
c = 16.0212 (4) Å | 0.40 × 0.30 × 0.02 mm |
β = 103.836 (1)° |
Bruker SMART CCD area-detector diffractometer | 7001 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3962 reflections with I > 2σ(I) |
Tmin = 0.631, Tmax = 0.983 | Rint = 0.114 |
22145 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.72 e Å−3 |
7001 reflections | Δρmin = −0.87 e Å−3 |
244 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 | 0.11611 (4) | 0.14752 (5) | 0.03933 (3) | 0.01153 (13) | |
V2 | 0.06027 (4) | −0.05252 (5) | −0.13271 (3) | 0.01176 (13) | |
O1 | 0.16926 (18) | 0.2866 (2) | 0.03968 (14) | 0.0178 (5) | |
O2 | 0.19662 (17) | 0.0456 (2) | 0.09524 (14) | 0.0167 (5) | |
O3 | 0.00201 (17) | −0.0213 (2) | −0.23230 (13) | 0.0167 (5) | |
O4 | 0.16905 (17) | −0.1148 (2) | −0.13378 (15) | 0.0178 (5) | |
O5 | 0.07585 (17) | 0.0937 (2) | −0.07161 (14) | 0.0153 (5) | |
O6 | 0.01091 (17) | 0.1636 (2) | 0.08590 (13) | 0.0151 (5) | |
O7 | 0.32751 (18) | −0.0695 (2) | 0.01205 (16) | 0.0230 (6) | |
H1 | 0.2822 | −0.0320 | 0.0393 | 0.034* | |
H2 | 0.2808 | −0.1174 | −0.0381 | 0.034* | |
N1 | 0.3428 (2) | 0.1750 (2) | 0.33564 (16) | 0.0130 (5) | |
C1 | 0.2362 (2) | 0.1484 (3) | 0.29060 (19) | 0.0156 (6) | |
H1A | 0.2341 | 0.1111 | 0.2335 | 0.019* | |
H1B | 0.2097 | 0.0848 | 0.3244 | 0.019* | |
C2 | 0.3965 (3) | 0.0502 (3) | 0.3373 (2) | 0.0206 (7) | |
H2A | 0.3861 | 0.0192 | 0.2775 | 0.025* | |
H2B | 0.3660 | −0.0120 | 0.3693 | 0.025* | |
C3 | 0.3874 (3) | 0.2768 (3) | 0.2900 (2) | 0.0175 (7) | |
H3A | 0.4564 | 0.2900 | 0.3218 | 0.021* | |
H3B | 0.3517 | 0.3569 | 0.2926 | 0.021* | |
C4 | 0.3515 (3) | 0.2252 (3) | 0.42608 (19) | 0.0171 (7) | |
H4A | 0.3240 | 0.3119 | 0.4219 | 0.021* | |
H4B | 0.4220 | 0.2312 | 0.4554 | 0.021* | |
C5 | 0.1705 (3) | 0.2637 (4) | 0.2785 (2) | 0.0256 (8) | |
H5A | 0.1035 | 0.2392 | 0.2493 | 0.038* | |
H5B | 0.1950 | 0.3265 | 0.2438 | 0.038* | |
H5C | 0.1706 | 0.3001 | 0.3348 | 0.038* | |
C6 | 0.5061 (3) | 0.0530 (4) | 0.3772 (3) | 0.0378 (11) | |
H6A | 0.5335 | −0.0319 | 0.3751 | 0.057* | |
H6B | 0.5178 | 0.0807 | 0.4372 | 0.057* | |
H6C | 0.5379 | 0.1119 | 0.3451 | 0.057* | |
C7 | 0.3860 (3) | 0.2499 (4) | 0.1964 (2) | 0.0218 (7) | |
H7A | 0.4162 | 0.3207 | 0.1728 | 0.033* | |
H7B | 0.3179 | 0.2394 | 0.1635 | 0.033* | |
H7C | 0.4230 | 0.1723 | 0.1928 | 0.033* | |
C8 | 0.2999 (3) | 0.1459 (3) | 0.4817 (2) | 0.0194 (7) | |
H8A | 0.3093 | 0.1851 | 0.5385 | 0.029* | |
H8B | 0.3278 | 0.0604 | 0.4879 | 0.029* | |
H8C | 0.2296 | 0.1412 | 0.4544 | 0.029* | |
N2 | 0.3596 (2) | 0.2502 (3) | 0.87870 (17) | 0.0171 (6) | |
C9 | 0.4009 (3) | 0.2293 (3) | 0.9744 (2) | 0.0197 (7) | |
H9A | 0.3559 | 0.2687 | 1.0060 | 0.024* | |
H9B | 0.4022 | 0.1373 | 0.9861 | 0.024* | |
C10 | 0.2550 (3) | 0.1984 (3) | 0.8593 (2) | 0.0200 (7) | |
H10A | 0.2203 | 0.2374 | 0.8998 | 0.024* | |
H10B | 0.2583 | 0.1062 | 0.8704 | 0.024* | |
C11 | 0.4217 (3) | 0.1843 (4) | 0.8257 (3) | 0.0292 (9) | |
H11A | 0.3910 | 0.1987 | 0.7640 | 0.035* | |
H11B | 0.4874 | 0.2245 | 0.8384 | 0.035* | |
C12 | 0.3602 (3) | 0.3897 (3) | 0.8552 (2) | 0.0232 (8) | |
H12A | 0.4290 | 0.4197 | 0.8676 | 0.028* | |
H12B | 0.3320 | 0.3991 | 0.7927 | 0.028* | |
C13 | 0.5035 (3) | 0.2820 (4) | 1.0096 (3) | 0.0281 (8) | |
H13A | 0.5245 | 0.2646 | 1.0714 | 0.042* | |
H13B | 0.5030 | 0.3736 | 1.0000 | 0.042* | |
H13C | 0.5493 | 0.2419 | 0.9801 | 0.042* | |
C14 | 0.1942 (3) | 0.2207 (4) | 0.7677 (2) | 0.0343 (10) | |
H14A | 0.1286 | 0.1843 | 0.7614 | 0.051* | |
H14B | 0.2265 | 0.1802 | 0.7268 | 0.051* | |
H14C | 0.1885 | 0.3117 | 0.7563 | 0.051* | |
C15 | 0.4350 (4) | 0.0436 (4) | 0.8406 (3) | 0.0418 (11) | |
H15A | 0.4757 | 0.0096 | 0.8040 | 0.063* | |
H15B | 0.3706 | 0.0020 | 0.8265 | 0.063* | |
H15C | 0.4672 | 0.0279 | 0.9011 | 0.063* | |
C16 | 0.3027 (3) | 0.4724 (3) | 0.9032 (3) | 0.0295 (9) | |
H16A | 0.3059 | 0.5606 | 0.8853 | 0.044* | |
H16B | 0.3311 | 0.4653 | 0.9652 | 0.044* | |
H16C | 0.2340 | 0.4448 | 0.8902 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0111 (3) | 0.0147 (3) | 0.0071 (2) | −0.0009 (2) | −0.00102 (19) | −0.0003 (2) |
V2 | 0.0111 (3) | 0.0162 (3) | 0.0070 (2) | 0.0007 (2) | 0.00013 (19) | 0.0000 (2) |
O1 | 0.0223 (14) | 0.0173 (12) | 0.0138 (11) | −0.0030 (10) | 0.0043 (10) | −0.0009 (9) |
O2 | 0.0174 (12) | 0.0185 (12) | 0.0115 (11) | 0.0026 (10) | −0.0020 (9) | −0.0002 (9) |
O3 | 0.0186 (13) | 0.0211 (12) | 0.0086 (11) | 0.0018 (10) | −0.0005 (9) | 0.0003 (9) |
O4 | 0.0127 (12) | 0.0245 (13) | 0.0156 (12) | 0.0018 (10) | 0.0023 (9) | 0.0007 (9) |
O5 | 0.0157 (12) | 0.0194 (11) | 0.0090 (10) | −0.0017 (10) | −0.0004 (9) | −0.0031 (9) |
O6 | 0.0143 (12) | 0.0200 (12) | 0.0104 (11) | 0.0006 (9) | 0.0015 (9) | 0.0012 (9) |
O7 | 0.0165 (13) | 0.0253 (14) | 0.0267 (14) | 0.0043 (11) | 0.0043 (11) | 0.0006 (11) |
N1 | 0.0127 (14) | 0.0148 (13) | 0.0091 (12) | 0.0001 (10) | −0.0022 (10) | −0.0017 (10) |
C1 | 0.0157 (16) | 0.0196 (16) | 0.0095 (14) | −0.0060 (14) | −0.0006 (12) | −0.0042 (13) |
C2 | 0.027 (2) | 0.0168 (16) | 0.0153 (16) | 0.0079 (15) | −0.0001 (14) | −0.0033 (14) |
C3 | 0.0144 (17) | 0.0219 (18) | 0.0144 (16) | −0.0056 (13) | −0.0001 (13) | −0.0013 (13) |
C4 | 0.0222 (18) | 0.0180 (17) | 0.0079 (14) | 0.0003 (14) | −0.0029 (13) | −0.0035 (12) |
C5 | 0.0151 (18) | 0.035 (2) | 0.0236 (19) | 0.0043 (16) | −0.0026 (14) | −0.0056 (16) |
C6 | 0.029 (2) | 0.043 (2) | 0.032 (2) | 0.018 (2) | −0.0122 (17) | −0.011 (2) |
C7 | 0.0193 (18) | 0.031 (2) | 0.0137 (16) | −0.0043 (16) | 0.0010 (13) | 0.0014 (14) |
C8 | 0.0254 (19) | 0.0194 (17) | 0.0122 (15) | 0.0033 (15) | 0.0021 (13) | 0.0023 (13) |
N2 | 0.0189 (15) | 0.0168 (14) | 0.0182 (14) | −0.0031 (12) | 0.0094 (12) | −0.0011 (11) |
C9 | 0.0197 (19) | 0.0192 (17) | 0.0204 (17) | −0.0021 (14) | 0.0053 (14) | 0.0001 (14) |
C10 | 0.0170 (18) | 0.0227 (18) | 0.0214 (18) | −0.0070 (14) | 0.0071 (14) | −0.0002 (14) |
C11 | 0.026 (2) | 0.034 (2) | 0.033 (2) | −0.0041 (17) | 0.0181 (18) | −0.0145 (17) |
C12 | 0.028 (2) | 0.0195 (17) | 0.0239 (19) | −0.0049 (15) | 0.0100 (16) | 0.0032 (14) |
C13 | 0.018 (2) | 0.027 (2) | 0.037 (2) | −0.0019 (16) | 0.0020 (16) | −0.0012 (17) |
C14 | 0.038 (3) | 0.045 (3) | 0.0162 (19) | −0.017 (2) | −0.0003 (17) | 0.0006 (17) |
C15 | 0.047 (3) | 0.040 (3) | 0.037 (2) | 0.018 (2) | 0.008 (2) | −0.010 (2) |
C16 | 0.035 (2) | 0.0201 (19) | 0.033 (2) | −0.0002 (16) | 0.0082 (18) | −0.0010 (16) |
V1—O1 | 1.648 (2) | C7—H7B | 0.98 |
V1—O2 | 1.659 (2) | C7—H7C | 0.98 |
V1—O6 | 1.813 (2) | C8—H8A | 0.98 |
V1—O5 | 1.822 (2) | C8—H8B | 0.98 |
V2—O3 | 1.643 (2) | C8—H8C | 0.98 |
V2—O4 | 1.665 (2) | N2—C9 | 1.521 (4) |
V2—O5 | 1.815 (2) | N2—C11 | 1.523 (4) |
V2—O6i | 1.815 (2) | N2—C12 | 1.523 (4) |
O6—V2i | 1.815 (2) | N2—C10 | 1.525 (4) |
O7—H1 | 0.94 | C9—C13 | 1.520 (5) |
O7—H2 | 1.04 | C9—H9A | 0.99 |
N1—C2 | 1.517 (4) | C9—H9B | 0.99 |
N1—C3 | 1.518 (4) | C10—C14 | 1.528 (5) |
N1—C4 | 1.520 (4) | C10—H10A | 0.99 |
N1—C1 | 1.521 (4) | C10—H10B | 0.99 |
C1—C5 | 1.512 (5) | C11—C15 | 1.511 (6) |
C1—H1A | 0.99 | C11—H11A | 0.99 |
C1—H1B | 0.99 | C11—H11B | 0.99 |
C2—C6 | 1.517 (5) | C12—C16 | 1.517 (5) |
C2—H2A | 0.99 | C12—H12A | 0.99 |
C2—H2B | 0.99 | C12—H12B | 0.99 |
C3—C7 | 1.521 (4) | C13—H13A | 0.98 |
C3—H3A | 0.99 | C13—H13B | 0.98 |
C3—H3B | 0.99 | C13—H13C | 0.98 |
C4—C8 | 1.526 (5) | C14—H14A | 0.98 |
C4—H4A | 0.99 | C14—H14B | 0.98 |
C4—H4B | 0.99 | C14—H14C | 0.98 |
C5—H5A | 0.98 | C15—H15A | 0.98 |
C5—H5B | 0.98 | C15—H15B | 0.98 |
C5—H5C | 0.98 | C15—H15C | 0.98 |
C6—H6A | 0.98 | C16—H16A | 0.98 |
C6—H6B | 0.98 | C16—H16B | 0.98 |
C6—H6C | 0.98 | C16—H16C | 0.98 |
C7—H7A | 0.98 | ||
O1—V1—O2 | 109.20 (12) | H7B—C7—H7C | 109.5 |
O1—V1—O6 | 109.07 (11) | C4—C8—H8A | 109.5 |
O2—V1—O6 | 110.73 (11) | C4—C8—H8B | 109.5 |
O1—V1—O5 | 108.44 (11) | H8A—C8—H8B | 109.5 |
O2—V1—O5 | 109.62 (11) | C4—C8—H8C | 109.5 |
O6—V1—O5 | 109.75 (10) | H8A—C8—H8C | 109.5 |
O3—V2—O4 | 108.26 (11) | H8B—C8—H8C | 109.5 |
O3—V2—O5 | 108.69 (11) | C9—N2—C11 | 111.4 (3) |
O4—V2—O5 | 110.50 (11) | C9—N2—C12 | 111.5 (3) |
O3—V2—O6i | 109.67 (11) | C11—N2—C12 | 105.5 (3) |
O4—V2—O6i | 110.10 (11) | C9—N2—C10 | 105.6 (2) |
O5—V2—O6i | 109.60 (10) | C11—N2—C10 | 111.8 (3) |
V2—O5—V1 | 139.57 (13) | C12—N2—C10 | 111.0 (3) |
V1—O6—V2i | 133.71 (13) | C13—C9—N2 | 114.8 (3) |
H1—O7—H2 | 101 | C13—C9—H9A | 108.6 |
C2—N1—C3 | 111.5 (3) | N2—C9—H9A | 108.6 |
C2—N1—C4 | 111.1 (2) | C13—C9—H9B | 108.6 |
C3—N1—C4 | 105.3 (2) | N2—C9—H9B | 108.6 |
C2—N1—C1 | 105.9 (2) | H9A—C9—H9B | 107.6 |
C3—N1—C1 | 111.9 (2) | N2—C10—C14 | 115.4 (3) |
C4—N1—C1 | 111.3 (2) | N2—C10—H10A | 108.4 |
C5—C1—N1 | 114.2 (3) | C14—C10—H10A | 108.4 |
C5—C1—H1A | 108.7 | N2—C10—H10B | 108.4 |
N1—C1—H1A | 108.7 | C14—C10—H10B | 108.4 |
C5—C1—H1B | 108.7 | H10A—C10—H10B | 107.5 |
N1—C1—H1B | 108.7 | C15—C11—N2 | 115.3 (3) |
H1A—C1—H1B | 107.6 | C15—C11—H11A | 108.5 |
N1—C2—C6 | 116.1 (3) | N2—C11—H11A | 108.5 |
N1—C2—H2A | 108.3 | C15—C11—H11B | 108.5 |
C6—C2—H2A | 108.3 | N2—C11—H11B | 108.5 |
N1—C2—H2B | 108.3 | H11A—C11—H11B | 107.5 |
C6—C2—H2B | 108.3 | C16—C12—N2 | 113.5 (3) |
H2A—C2—H2B | 107.4 | C16—C12—H12A | 108.9 |
N1—C3—C7 | 115.6 (3) | N2—C12—H12A | 108.9 |
N1—C3—H3A | 108.4 | C16—C12—H12B | 108.9 |
C7—C3—H3A | 108.4 | N2—C12—H12B | 108.9 |
N1—C3—H3B | 108.4 | H12A—C12—H12B | 107.7 |
C7—C3—H3B | 108.4 | C9—C13—H13A | 109.5 |
H3A—C3—H3B | 107.4 | C9—C13—H13B | 109.5 |
N1—C4—C8 | 115.1 (3) | H13A—C13—H13B | 109.5 |
N1—C4—H4A | 108.5 | C9—C13—H13C | 109.5 |
C8—C4—H4A | 108.5 | H13A—C13—H13C | 109.5 |
N1—C4—H4B | 108.5 | H13B—C13—H13C | 109.5 |
C8—C4—H4B | 108.5 | C10—C14—H14A | 109.5 |
H4A—C4—H4B | 107.5 | C10—C14—H14B | 109.5 |
C1—C5—H5A | 109.5 | H14A—C14—H14B | 109.5 |
C1—C5—H5B | 109.5 | C10—C14—H14C | 109.5 |
H5A—C5—H5B | 109.5 | H14A—C14—H14C | 109.5 |
C1—C5—H5C | 109.5 | H14B—C14—H14C | 109.5 |
H5A—C5—H5C | 109.5 | C11—C15—H15A | 109.5 |
H5B—C5—H5C | 109.5 | C11—C15—H15B | 109.5 |
C2—C6—H6A | 109.5 | H15A—C15—H15B | 109.5 |
C2—C6—H6B | 109.5 | C11—C15—H15C | 109.5 |
H6A—C6—H6B | 109.5 | H15A—C15—H15C | 109.5 |
C2—C6—H6C | 109.5 | H15B—C15—H15C | 109.5 |
H6A—C6—H6C | 109.5 | C12—C16—H16A | 109.5 |
H6B—C6—H6C | 109.5 | C12—C16—H16B | 109.5 |
C3—C7—H7A | 109.5 | H16A—C16—H16B | 109.5 |
C3—C7—H7B | 109.5 | C12—C16—H16C | 109.5 |
H7A—C7—H7B | 109.5 | H16A—C16—H16C | 109.5 |
C3—C7—H7C | 109.5 | H16B—C16—H16C | 109.5 |
H7A—C7—H7C | 109.5 |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H1···O2 | 0.94 | 1.85 | 2.792 (3) | 178 |
O7—H2···O4 | 1.04 | 1.91 | 2.853 (3) | 149 |
Experimental details
Crystal data | |
Chemical formula | (C8H20N)4[V4O12]·2H2O |
Mr | 952.79 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 90 |
a, b, c (Å) | 14.0187 (3), 10.5729 (2), 16.0212 (4) |
β (°) | 103.836 (1) |
V (Å3) | 2305.7 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.85 |
Crystal size (mm) | 0.40 × 0.30 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.631, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22145, 7001, 3962 |
Rint | 0.114 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.141, 0.92 |
No. of reflections | 7001 |
No. of parameters | 244 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72, −0.87 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996).
V1—O1 | 1.648 (2) | V2—O3 | 1.643 (2) |
V1—O2 | 1.659 (2) | V2—O4 | 1.665 (2) |
V1—O6 | 1.813 (2) | V2—O5 | 1.815 (2) |
V1—O5 | 1.822 (2) | V2—O6i | 1.815 (2) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H1···O2 | 0.94 | 1.85 | 2.792 (3) | 178 |
O7—H2···O4 | 1.04 | 1.91 | 2.853 (3) | 149 |
Tetraalkylammonium salts of metavanadate, (R4N)[VO3], have been widely used as starting materials for the syntheses of polyvanadates in aprotic solvents since their first preparation (Abe et al., 1994; Abe, Akashi et al., 1996; Abe, Isobe et al., 1996; Akashi et al., 1991; Attanasio et al., 1993; Day et al., 1990; Hayashi et al., 2000, 2001; Kawanami et al., 2000; Nakano et al., 2001). However, (R4N)[VO3] itself has not been fully characterized to date. It is assumed to be a tetrameric compound with a ring structure, (R4N)4[V4O12], because it readily gives organometallic compounds that have a V4O12 ring, but this assumption has never been confirmed by an X-ray structure analysis. Trimeric (R4N)3[V3O9] has recently been isolated from an aged DMF solution, a solvent seldom used in the syntheses of polyvanadates (Hamilton et al., 2002). We have isolated the title metavanadate salt as a tetraethylammonium salt, (I), from an acetonitrile solution and found that the anion does have the expected V4O12 ring structure (Fig. 1). \sch
The V—O distances in (I) are all normal for a vanadate and compare well with those observed for other compounds that contain a V4O12 ring. The ring in (I) assumes a twisted-boat-chair conformation, similar to what is observed for {[(η3-C4H7)2Rh]2[V4O12]}2- (Akashi et al., 1991), [Zn(2,2'-bipy)3]2[V4O12].11H2O (2,2'-bipy is 2,2'-bipyridine; Zhang et al., 1997) and [Ni(2,2'-bipy)3]2[V4O12].11H2O (Yang et al., 1998), and not the twisted-chair conformation observed for {[(η-C8H12)Ir]2(V4O12)}2- (Day et al., 1990).
As can be seen in Fig. 1, two water molecules are attached to the [V4O12]4- anion through hydrogen bonds, one to each surface. Each water molecule bridges two terminal V═O O atoms. The [(V4O12)(H2O)2]4- anion is surrounded by C8H20N+ cations, and no other interactions between the anions and/or water molecules are observed (Fig. 2).
The structure of the [(V4O12)(H2O)2]4- anion as a whole very closely resembles that of {[(η3-C4H7)2Rh]2(V4O12)}2-, a vanadate-supported organorhodium complex. It is interesting to note that the V1—O2 [1.659 (2) Å] and V2—O4 [1.665 (2) Å] distances in (I) are virtually the same as those between the V and O atoms that bridge the V and Rh atoms in {[(η3-C4H7)2Rh]2(V4O12)}2- [1.652 (5) and 1.670 (5) Å].
The [(V4O12)(H2O)2]4- anion observed here can be viewed as a vanadate-supported water complex. In fact, the same adsorption geometry is proposed for water molecules adsorbed on V2O5 (Ranea et al., 2000). A similar vanadate-supported water complex can be found in [Zn(2,2'-bipy)3]2[V4O12].11H2O, although the [V4O12]4- anion in that compound is also hydrogen-bonded to many other water molecules.
The water molecules in (I) are bound relatively tightly onto the surface of the [V4O12]4- anion. The compound does not lose these water molecules even if it is dried under vacuum over P2O5 for more than 12 h. The TG-DTA (please define) of (I) gives a well defined peak at around 373 K that accounts for a 3.8% weight loss. This is consistent with the dissociation of two water molecules. The dissociation enthalpy was determined to be 103 kJ mol-1, which allows us to estimate the binding energy of a water molecule on the [V4O12]4- surface to be ~51 kJ mol-1.