The title compound, triammonium cis-diaqua-cis-dioxo-trans-disulfatovanadate 1.5-hydrate, was obtained by oxidizing VIV to VV in a 2 M sulfuric acid solution of vanadyl sulfate and adding ammonium sulfate. Here, the V atom is sandwiched by two sulfate groups by corner-sharing to form a discrete [VO2(SO4)2(OH2)2]3- anion. The water molecules occupy cis positions in the equatorial plane of the vanadium octahedron.
Supporting information
An appropriate amount of vanadyl sulfate, VOSO4, was dissolved in sulfuric acid, and water was added to achieve the concentration of 2 M for both VOSO4 and H2SO4. Then VIV was electrolytically oxidized to VV. To a 4 ml portion of this solution, (NH4)2SO4 (3.3 g, 25 mmol) was added and the mixture was heated to 323 K to dissolve the ammonium sulfate. The resulting solution was kept at 301 K for 3 d to obtain the orange tabular crystals.
All H atoms were fixed at the positions obtained from differential Fourier maps.
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.
Triammonium
cis-diaqua-
cis-dioxo-
trans-disulfatovanadate hemitrihydrate
top
Crystal data top
(NH4)3·[VO2(SO4)2(OH2)2]·1.5H2O | Z = 2 |
Mr = 392.24 | F(000) = 406 |
Triclinic, P1 | Dx = 1.903 Mg m−3 |
a = 7.748 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 14.164 (3) Å | Cell parameters from 25 reflections |
c = 6.268 (2) Å | θ = 17.4–17.5° |
α = 91.54 (2)° | µ = 1.10 mm−1 |
β = 95.30 (2)° | T = 293 K |
γ = 88.25 (2)° | Plate, orange |
V = 684.4 (3) Å3 | 0.60 × 0.50 × 0.20 mm |
Data collection top
RIGAKU AFC-5R automated four-circle diffractometer | 7201 independent reflections |
Radiation source: normal focus rotating anode | 6049 reflections with F2 > 2.0σ(F2) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 3 pixels mm-1 | θmax = 37.5°, θmin = 2.6° |
ω–2θ scans | h = −13→13 |
Absorption correction: ψ scan TEXSAN (Molecular Structure Corporation, 1995) | k = −23→23 |
Tmin = 0.576, Tmax = 0.802 | l = −10→0 |
7201 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters not refined |
wR(F2) = 0.100 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo2) + (0.0539P)2 + 0.245P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
7201 reflections | Δρmax = 0.90 e Å−3 |
179 parameters | Δρmin = −0.81 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0052 (17) |
Crystal data top
(NH4)3·[VO2(SO4)2(OH2)2]·1.5H2O | γ = 88.25 (2)° |
Mr = 392.24 | V = 684.4 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.748 (2) Å | Mo Kα radiation |
b = 14.164 (3) Å | µ = 1.10 mm−1 |
c = 6.268 (2) Å | T = 293 K |
α = 91.54 (2)° | 0.60 × 0.50 × 0.20 mm |
β = 95.30 (2)° | |
Data collection top
RIGAKU AFC-5R automated four-circle diffractometer | 7201 independent reflections |
Absorption correction: ψ scan TEXSAN (Molecular Structure Corporation, 1995) | 6049 reflections with F2 > 2.0σ(F2) |
Tmin = 0.576, Tmax = 0.802 | Rint = 0.000 |
7201 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters not refined |
S = 1.05 | Δρmax = 0.90 e Å−3 |
7201 reflections | Δρmin = −0.81 e Å−3 |
179 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 | Occ. (<1) |
V1 | 0.41406 (2) | 0.232330 (13) | 0.46950 (3) | 0.01946 (5) | |
S1 | 0.14518 (4) | 0.37785 (2) | 0.23438 (6) | 0.02690 (7) | |
S2 | 0.74810 (3) | 0.098593 (18) | 0.58459 (4) | 0.01907 (5) | |
O1 | 0.55752 (13) | 0.31019 (7) | 0.42587 (18) | 0.02993 (18) | |
O2 | 0.38995 (14) | 0.17176 (8) | 0.24622 (17) | 0.0329 (2) | |
OW1 | 0.22757 (12) | 0.14909 (7) | 0.63305 (19) | 0.02893 (18) | |
OW2 | 0.41290 (14) | 0.30238 (7) | 0.79675 (17) | 0.03127 (19) | |
O11 | 0.19843 (12) | 0.31434 (7) | 0.42029 (17) | 0.02863 (18) | |
O12 | 0.13178 (16) | 0.31852 (9) | 0.0373 (2) | 0.0379 (2) | |
O13 | −0.02344 (14) | 0.42014 (9) | 0.2745 (2) | 0.0403 (3) | |
O14 | 0.27415 (17) | 0.45012 (9) | 0.2239 (3) | 0.0499 (4) | |
O21 | 0.57481 (11) | 0.14075 (7) | 0.63211 (15) | 0.02478 (16) | |
O22 | 0.72938 (15) | 0.04146 (7) | 0.38645 (17) | 0.03152 (19) | |
O23 | 0.86817 (12) | 0.17500 (7) | 0.5614 (2) | 0.0338 (2) | |
O24 | 0.80695 (13) | 0.04067 (7) | 0.76919 (17) | 0.03013 (19) | |
N1 | 0.00854 (17) | 0.13172 (9) | 0.1252 (2) | 0.0333 (2) | |
N2 | 0.8812 (2) | 0.36879 (10) | 0.6918 (2) | 0.0385 (3) | |
N3 | 0.6224 (2) | 0.49888 (12) | 0.2242 (4) | 0.0543 (5) | |
OW3 | 0.72234 (18) | 0.26757 (14) | 0.0540 (2) | 0.0547 (4) | |
OW4 | 0.5000 | 0.0000 | 0.0000 | 0.0435 (4) | |
H11 | 0.2449 | 0.0954 | 0.6185 | 0.060* | |
H12 | 0.1249 | 0.1579 | 0.6088 | 0.060* | |
H21 | 0.3351 | 0.2968 | 0.8714 | 0.060* | |
H22 | 0.5017 | 0.2938 | 0.8831 | 0.060* | |
H31 | 0.6830 | 0.2731 | 0.1738 | 0.110* | |
H32 | 0.8044 | 0.3106 | 0.1203 | 0.110* | |
H41 | 0.5735 | 0.0210 | 0.1079 | 0.090* | 0.50 |
H42 | 0.6051 | 0.0109 | −0.0352 | 0.090* | 0.50 |
H51 | −0.0432 | 0.1140 | 0.0217 | 0.070* | |
H52 | 0.0649 | 0.1761 | 0.1060 | 0.070* | |
H53 | 0.0814 | 0.0903 | 0.1694 | 0.070* | |
H54 | −0.0488 | 0.1498 | 0.2257 | 0.070* | |
H61 | 0.8299 | 0.4166 | 0.7110 | 0.080* | |
H62 | 0.9573 | 0.3607 | 0.7914 | 0.080* | |
H63 | 0.8445 | 0.3244 | 0.6534 | 0.080* | |
H64 | 0.9354 | 0.3894 | 0.5880 | 0.080* | |
H71 | 0.7177 | 0.4646 | 0.2001 | 0.110* | |
H72 | 0.5388 | 0.4600 | 0.2383 | 0.110* | |
H73 | 0.6402 | 0.5061 | 0.3490 | 0.110* | |
H74 | 0.5985 | 0.5524 | 0.1314 | 0.110* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
V1 | 0.01595 (7) | 0.01890 (8) | 0.02329 (8) | 0.00197 (5) | 0.00110 (5) | 0.00121 (6) |
S1 | 0.02039 (12) | 0.02187 (12) | 0.03869 (16) | 0.00533 (9) | 0.00381 (10) | 0.00802 (11) |
S2 | 0.01539 (9) | 0.01541 (10) | 0.02601 (12) | 0.00138 (7) | 0.00016 (8) | 0.00099 (8) |
O1 | 0.0242 (4) | 0.0284 (4) | 0.0379 (5) | −0.0037 (3) | 0.0038 (3) | 0.0060 (4) |
O2 | 0.0321 (5) | 0.0344 (5) | 0.0303 (4) | 0.0061 (4) | −0.0021 (4) | −0.0074 (4) |
OW1 | 0.0198 (3) | 0.0206 (3) | 0.0466 (5) | −0.0001 (3) | 0.0037 (3) | 0.0031 (3) |
OW2 | 0.0309 (4) | 0.0310 (4) | 0.0323 (5) | −0.0010 (4) | 0.0064 (4) | −0.0055 (4) |
O11 | 0.0231 (4) | 0.0274 (4) | 0.0356 (5) | 0.0081 (3) | 0.0040 (3) | 0.0080 (3) |
O12 | 0.0362 (5) | 0.0422 (6) | 0.0354 (5) | 0.0077 (4) | 0.0046 (4) | 0.0058 (4) |
O13 | 0.0273 (5) | 0.0412 (6) | 0.0524 (7) | 0.0178 (4) | 0.0074 (4) | 0.0105 (5) |
O14 | 0.0351 (6) | 0.0270 (5) | 0.0892 (11) | −0.0024 (4) | 0.0081 (6) | 0.0184 (6) |
O21 | 0.0168 (3) | 0.0267 (4) | 0.0309 (4) | 0.0058 (3) | 0.0033 (3) | 0.0064 (3) |
O22 | 0.0388 (5) | 0.0252 (4) | 0.0295 (4) | 0.0045 (4) | 0.0004 (4) | −0.0051 (3) |
O23 | 0.0198 (4) | 0.0224 (4) | 0.0601 (7) | −0.0041 (3) | 0.0065 (4) | 0.0013 (4) |
O24 | 0.0301 (4) | 0.0270 (4) | 0.0316 (4) | 0.0078 (3) | −0.0053 (3) | 0.0059 (3) |
N1 | 0.0305 (5) | 0.0304 (5) | 0.0377 (6) | 0.0001 (4) | −0.0033 (4) | 0.0020 (4) |
N2 | 0.0452 (7) | 0.0302 (6) | 0.0387 (6) | −0.0011 (5) | −0.0027 (5) | −0.0047 (5) |
N3 | 0.0362 (7) | 0.0389 (7) | 0.0888 (14) | −0.0022 (6) | 0.0059 (8) | 0.0203 (8) |
OW3 | 0.0319 (6) | 0.0885 (12) | 0.0441 (7) | 0.0032 (6) | 0.0045 (5) | 0.0101 (7) |
OW4 | 0.0360 (8) | 0.0578 (11) | 0.0363 (8) | −0.0043 (7) | 0.0024 (6) | −0.0054 (7) |
Geometric parameters (Å, º) top
V1—O2 | 1.6206 (11) | O22—OW4 | 2.9263 (14) |
V1—O1 | 1.6352 (10) | O22—N1viii | 3.151 (2) |
V1—O21 | 2.0026 (10) | O23—OW1viii | 2.7939 (15) |
V1—O11 | 2.0103 (10) | O23—N2 | 2.8450 (18) |
V1—OW1 | 2.2296 (11) | O23—N1viii | 3.074 (2) |
V1—OW2 | 2.2551 (12) | O24—N1i | 2.8536 (17) |
S1—O14 | 1.4591 (13) | O24—N1ix | 2.8994 (18) |
S1—O13 | 1.4608 (11) | O24—OW4iii | 2.9740 (14) |
S1—O12 | 1.4725 (14) | N1—O24i | 2.8536 (17) |
S1—O11 | 1.5107 (11) | N1—O24vi | 2.8994 (18) |
S2—O22 | 1.4622 (11) | N1—OW3ii | 2.902 (2) |
S2—O24 | 1.4665 (11) | N1—O23ii | 3.074 (2) |
S2—O23 | 1.4672 (10) | N1—O22ii | 3.151 (2) |
S2—O21 | 1.5045 (9) | N1—H51 | 0.7706 |
O1—OW2 | 2.6785 (17) | N1—H52 | 0.7942 |
O1—OW3 | 2.803 (2) | N1—H53 | 0.8362 |
O1—N2 | 3.006 (2) | N1—H54 | 0.8342 |
O1—N3 | 3.062 (2) | N2—O14iv | 2.857 (2) |
O2—OW1 | 2.8627 (18) | N2—O12ix | 2.862 (2) |
O2—OW4 | 2.9904 (12) | N2—O13viii | 2.899 (2) |
O2—N1 | 3.0488 (19) | N2—OW3iii | 3.087 (2) |
OW1—O21 | 2.6899 (14) | N2—O11viii | 3.181 (2) |
OW1—O22i | 2.7103 (15) | N2—H61 | 0.7869 |
OW1—O11 | 2.7180 (15) | N2—H62 | 0.8260 |
OW1—OW2 | 2.7617 (16) | N2—H63 | 0.7241 |
OW1—O23ii | 2.7939 (15) | N2—H64 | 0.8674 |
OW1—H11 | 0.7727 | N3—OW2iv | 2.825 (2) |
OW1—H12 | 0.8025 | N3—O13viii | 2.923 (2) |
OW2—O12iii | 2.7620 (17) | N3—O14vii | 3.101 (3) |
OW2—O11 | 2.7637 (17) | N3—H71 | 0.8939 |
OW2—O21 | 2.7957 (15) | N3—H72 | 0.8747 |
OW2—OW3iii | 2.8015 (19) | N3—H73 | 0.786 |
OW2—N3iv | 2.825 (2) | N3—H74 | 0.9709 |
OW2—H21 | 0.8035 | OW3—OW2v | 2.8015 (19) |
OW2—H22 | 0.8430 | OW3—N1viii | 2.902 (2) |
O11—N2ii | 3.181 (2) | OW3—N2v | 3.087 (2) |
O12—OW2v | 2.7620 (17) | OW3—O13viii | 3.171 (2) |
O12—N2vi | 2.862 (2) | OW3—H31 | 0.8368 |
O12—N1 | 2.923 (2) | OW3—H32 | 0.9536 |
O13—N2ii | 2.899 (2) | OW4—O22x | 2.9263 (14) |
O13—N3ii | 2.923 (2) | OW4—O24i | 2.9740 (13) |
O13—OW3ii | 3.171 (2) | OW4—O24v | 2.9740 (13) |
O13—N2iv | 3.212 (2) | OW4—O2x | 2.9904 (12) |
O14—N3 | 2.805 (2) | OW4—O21i | 3.1926 (12) |
O14—N2iv | 2.857 (2) | OW4—O21v | 3.1926 (12) |
O14—N3vii | 3.101 (3) | OW4—H41 | 0.8936 |
O21—OW4iii | 3.1926 (12) | OW4—H42 | 0.8822 |
O22—OW1i | 2.7103 (15) | | |
| | | |
O2—V1—O1 | 103.80 (6) | O2—N1—O23ii | 99.08 (5) |
O2—V1—O21 | 97.41 (5) | O24i—N1—O22ii | 81.91 (5) |
O1—V1—O21 | 97.72 (5) | O24vi—N1—O22ii | 81.89 (5) |
O2—V1—O11 | 97.06 (5) | OW3ii—N1—O22ii | 79.21 (5) |
O1—V1—O11 | 98.77 (5) | O12—N1—O22ii | 138.99 (6) |
O21—V1—O11 | 154.76 (4) | O2—N1—O22ii | 131.15 (6) |
O2—V1—OW1 | 94.74 (6) | O23ii—N1—O22ii | 45.21 (4) |
O1—V1—OW1 | 161.43 (5) | O24i—N1—H51 | 97.81 |
O21—V1—OW1 | 78.73 (4) | O24vi—N1—H51 | 8.23 |
O11—V1—OW1 | 79.56 (4) | OW3ii—N1—H51 | 75.24 |
O2—V1—OW2 | 170.71 (5) | O12—N1—H51 | 106.77 |
O1—V1—OW2 | 85.45 (5) | O2—N1—H51 | 133.88 |
O21—V1—OW2 | 81.85 (5) | O23ii—N1—H51 | 126.99 |
O11—V1—OW2 | 80.55 (5) | O22ii—N1—H51 | 88.17 |
OW1—V1—OW2 | 76.02 (4) | O24i—N1—H52 | 116.89 |
O14—S1—O13 | 111.13 (8) | O24vi—N1—H52 | 120.40 |
O14—S1—O12 | 110.89 (9) | OW3ii—N1—H52 | 82.90 |
O13—S1—O12 | 110.92 (8) | O12—N1—H52 | 14.22 |
O14—S1—O11 | 109.56 (8) | O2—N1—H52 | 48.29 |
O13—S1—O11 | 106.40 (7) | O23ii—N1—H52 | 104.17 |
O12—S1—O11 | 107.78 (7) | O22ii—N1—H52 | 148.13 |
O22—S2—O24 | 111.37 (6) | H51—N1—H52 | 112.48 |
O22—S2—O23 | 109.61 (7) | O24i—N1—H53 | 14.25 |
O24—S2—O23 | 110.98 (7) | O24vi—N1—H53 | 104.50 |
O22—S2—O21 | 109.98 (6) | OW3ii—N1—H53 | 167.89 |
O24—S2—O21 | 105.69 (6) | O12—N1—H53 | 118.37 |
O23—S2—O21 | 109.13 (6) | O2—N1—H53 | 56.82 |
V1—O1—OW2 | 57.06 (4) | O23ii—N1—H53 | 95.85 |
V1—O1—OW3 | 112.45 (7) | O22ii—N1—H53 | 89.90 |
OW2—O1—OW3 | 164.99 (6) | H51—N1—H53 | 109.98 |
V1—O1—N2 | 130.75 (6) | H52—N1—H53 | 104.30 |
OW2—O1—N2 | 86.28 (5) | O24i—N1—H54 | 110.11 |
OW3—O1—N2 | 95.27 (6) | O24vi—N1—H54 | 114.43 |
V1—O1—N3 | 146.17 (6) | OW3ii—N1—H54 | 59.34 |
OW2—O1—N3 | 121.62 (6) | O12—N1—H54 | 95.68 |
OW3—O1—N3 | 73.25 (6) | O2—N1—H54 | 109.04 |
N2—O1—N3 | 79.27 (6) | O23ii—N1—H54 | 13.68 |
V1—O2—OW1 | 50.91 (4) | O22ii—N1—H54 | 44.68 |
V1—O2—OW4 | 146.38 (6) | H51—N1—H54 | 116.73 |
OW1—O2—OW4 | 119.18 (5) | H52—N1—H54 | 103.45 |
V1—O2—N1 | 110.71 (6) | H53—N1—H54 | 109.04 |
OW1—O2—N1 | 71.87 (5) | O23—N2—O14iv | 153.08 (7) |
OW4—O2—N1 | 91.25 (4) | O23—N2—O12ix | 89.03 (6) |
V1—OW1—O21 | 46.90 (3) | O14iv—N2—O12ix | 110.28 (7) |
V1—OW1—O22i | 116.59 (5) | O23—N2—O13viii | 91.00 (6) |
O21—OW1—O22i | 81.93 (5) | O14iv—N2—O13viii | 93.68 (6) |
V1—OW1—O11 | 46.67 (3) | O12ix—N2—O13viii | 122.79 (7) |
O21—OW1—O11 | 92.79 (4) | O23—N2—O1 | 63.91 (4) |
O22i—OW1—O11 | 147.86 (6) | O14iv—N2—O1 | 90.61 (6) |
V1—OW1—OW2 | 52.41 (3) | O12ix—N2—O1 | 145.21 (7) |
O21—OW1—OW2 | 61.69 (4) | O13viii—N2—O1 | 81.36 (5) |
O22i—OW1—OW2 | 137.70 (5) | O23—N2—OW3iii | 74.30 (6) |
O11—OW1—OW2 | 60.57 (4) | O14iv—N2—OW3iii | 95.61 (7) |
V1—OW1—O23ii | 123.01 (5) | O12ix—N2—OW3iii | 66.95 (5) |
O21—OW1—O23ii | 169.25 (6) | O13viii—N2—OW3iii | 162.78 (7) |
O22i—OW1—O23ii | 102.82 (5) | O1—N2—OW3iii | 84.08 (6) |
O11—OW1—O23ii | 78.04 (4) | O23—N2—O11viii | 70.08 (5) |
OW2—OW1—O23ii | 116.91 (5) | O14iv—N2—O11viii | 129.63 (6) |
V1—OW1—O2 | 34.35 (3) | O12ix—N2—O11viii | 81.40 (5) |
O21—OW1—O2 | 58.89 (4) | O13viii—N2—O11viii | 45.79 (4) |
O22i—OW1—O2 | 92.49 (5) | O1—N2—O11viii | 106.90 (6) |
O11—OW1—O2 | 58.57 (4) | OW3iii—N2—O11viii | 132.16 (6) |
OW2—OW1—O2 | 86.75 (5) | O23—N2—H61 | 147.63 |
O23ii—OW1—O2 | 110.90 (5) | O14iv—N2—H61 | 5.47 |
V1—OW1—H11 | 111.48 | O12ix—N2—H61 | 114.21 |
O21—OW1—H11 | 78.59 | O13viii—N2—H61 | 94.26 |
O22i—OW1—H11 | 5.37 | O1—N2—H61 | 85.33 |
O11—OW1—H11 | 143.16 | OW3iii—N2—H61 | 93.65 |
OW2—OW1—H11 | 136.61 | O11viii—N2—H61 | 132.82 |
O23ii—OW1—H11 | 105.36 | O23—N2—H62 | 95.14 |
O2—OW1—H11 | 87.15 | O14iv—N2—H62 | 105.33 |
V1—OW1—H12 | 120.81 | O12ix—N2—H62 | 6.68 |
O21—OW1—H12 | 167.06 | O13viii—N2—H62 | 119.84 |
O22i—OW1—H12 | 104.14 | O1—N2—H62 | 151.67 |
O11—OW1—H12 | 75.95 | OW3iii—N2—H62 | 71.38 |
OW2—OW1—H12 | 116.06 | O11viii—N2—H62 | 81.02 |
O23ii—OW1—H12 | 2.22 | H61—N2—H62 | 109.57 |
O2—OW1—H12 | 108.95 | O23—N2—H63 | 21.12 |
H11—OW1—H12 | 106.53 | O14iv—N2—H63 | 131.97 |
V1—OW2—O1 | 37.48 (3) | O12ix—N2—H63 | 104.66 |
V1—OW2—O12iii | 125.70 (5) | O13viii—N2—H63 | 94.13 |
O1—OW2—O12iii | 152.04 (6) | O1—N2—H63 | 44.27 |
V1—OW2—OW1 | 51.58 (4) | OW3iii—N2—H63 | 68.93 |
O1—OW2—OW1 | 89.05 (5) | O11viii—N2—H63 | 86.76 |
O12iii—OW2—OW1 | 80.14 (5) | H61—N2—H63 | 126.5 |
V1—OW2—O11 | 45.85 (3) | H62—N2—H63 | 111.25 |
O1—OW2—O11 | 61.37 (4) | O23—N2—H64 | 98.49 |
O12iii—OW2—O11 | 91.19 (5) | O14iv—N2—H64 | 93.01 |
OW1—OW2—O11 | 58.93 (4) | O12ix—N2—H64 | 108.57 |
V1—OW2—O21 | 45.16 (3) | O13viii—N2—H64 | 15.96 |
O1—OW2—O21 | 60.27 (4) | O1—N2—H64 | 97.30 |
O12iii—OW2—O21 | 129.72 (5) | OW3iii—N2—H64 | 171.25 |
OW1—OW2—O21 | 57.89 (4) | O11viii—N2—H64 | 39.19 |
O11—OW2—O21 | 89.56 (5) | H61—N2—H64 | 95.07 |
V1—OW2—OW3iii | 112.34 (6) | H62—N2—H64 | 104.90 |
O1—OW2—OW3iii | 96.22 (5) | H63—N2—H64 | 106.09 |
O12iii—OW2—OW3iii | 111.64 (6) | O14—N3—OW2iv | 100.67 (7) |
OW1—OW2—OW3iii | 118.09 (6) | O14—N3—O13viii | 142.61 (7) |
O11—OW2—OW3iii | 156.57 (6) | OW2iv—N3—O13viii | 116.39 (7) |
O21—OW2—OW3iii | 72.06 (5) | O14—N3—O1 | 63.98 (5) |
V1—OW2—N3iv | 112.29 (7) | OW2iv—N3—O1 | 152.21 (9) |
O1—OW2—N3iv | 85.93 (6) | O13viii—N3—O1 | 80.04 (6) |
O12iii—OW2—N3iv | 84.49 (6) | O14—N3—O14vii | 113.62 (8) |
OW1—OW2—N3iv | 136.54 (6) | OW2iv—N3—O14vii | 74.10 (6) |
O11—OW2—N3iv | 81.19 (6) | O13viii—N3—O14vii | 82.77 (6) |
O21—OW2—N3iv | 144.94 (6) | O1—N3—O14vii | 132.47 (8) |
OW3iii—OW2—N3iv | 105.37 (7) | O14—N3—H71 | 131.86 |
V1—OW2—H21 | 122.56 | OW2iv—N3—H71 | 125.49 |
O1—OW2—H21 | 155.66 | O13viii—N3—H71 | 18.95 |
O12iii—OW2—H21 | 10.78 | O1—N3—H71 | 77.45 |
OW1—OW2—H21 | 73.49 | O14vii—N3—H71 | 72.37 |
O11—OW2—H21 | 94.69 | O14—N3—H72 | 25.78 |
O21—OW2—H21 | 119.44 | OW2iv—N3—H72 | 125.93 |
OW3iii—OW2—H21 | 106.86 | O13viii—N3—H72 | 116.86 |
N3iv—OW2—H21 | 95.09 | O1—N3—H72 | 39.23 |
V1—OW2—H22 | 117.12 | O14vii—N3—H72 | 121.33 |
O1—OW2—H22 | 100.72 | H71—N3—H72 | 108.12 |
O12iii—OW2—H22 | 107.05 | O14—N3—H73 | 96.43 |
OW1—OW2—H22 | 119.73 | OW2iv—N3—H73 | 86.87 |
O11—OW2—H22 | 161.42 | O13viii—N3—H73 | 81.59 |
O21—OW2—H22 | 76.19 | O1—N3—H73 | 72.95 |
OW3iii—OW2—H22 | 4.89 | O14vii—N3—H73 | 146.66 |
N3iv—OW2—H22 | 103.61 | H71—N3—H73 | 98.71 |
H21—OW2—H22 | 102.64 | H72—N3—H73 | 92.0 |
S1—O11—V1 | 128.38 (6) | O14—N3—H74 | 95.02 |
S1—O11—OW1 | 155.87 (7) | OW2iv—N3—H74 | 34.21 |
V1—O11—OW1 | 53.78 (3) | O13viii—N3—H74 | 118.11 |
S1—O11—OW2 | 142.98 (7) | O1—N3—H74 | 157.09 |
V1—O11—OW2 | 53.60 (4) | O14vii—N3—H74 | 45.46 |
OW1—O11—OW2 | 60.50 (4) | H71—N3—H74 | 114.8 |
S1—O11—N2ii | 96.80 (5) | H72—N3—H74 | 118.46 |
V1—O11—N2ii | 134.69 (5) | H73—N3—H74 | 121.1 |
OW1—O11—N2ii | 87.10 (5) | OW2v—OW3—O1 | 91.03 (6) |
OW2—O11—N2ii | 89.44 (5) | OW2v—OW3—N1viii | 142.74 (8) |
S1—O12—OW2v | 118.90 (7) | O1—OW3—N1viii | 112.78 (6) |
S1—O12—N2vi | 119.24 (7) | OW2v—OW3—N2v | 82.67 (6) |
OW2v—O12—N2vi | 96.41 (6) | O1—OW3—N2v | 139.92 (8) |
S1—O12—N1 | 110.34 (7) | N1viii—OW3—N2v | 94.72 (6) |
OW2v—O12—N1 | 110.46 (6) | OW2v—OW3—O13viii | 126.94 (7) |
N2vi—O12—N1 | 99.25 (6) | O1—OW3—O13viii | 80.00 (6) |
S1—O13—N2ii | 110.71 (7) | N1viii—OW3—O13viii | 86.65 (5) |
S1—O13—N3ii | 163.89 (9) | N2v—OW3—O13viii | 72.84 (5) |
N2ii—O13—N3ii | 83.33 (6) | OW2v—OW3—H31 | 98.27 |
S1—O13—OW3ii | 101.17 (7) | O1—OW3—H31 | 9.27 |
N2ii—O13—OW3ii | 89.93 (6) | N1viii—OW3—H31 | 103.62 |
N3ii—O13—OW3ii | 70.07 (6) | N2v—OW3—H31 | 146.41 |
S1—O13—N2iv | 93.44 (7) | O13viii—OW3—H31 | 80.31 |
N2ii—O13—N2iv | 108.69 (6) | OW2v—OW3—H32 | 130.11 |
N3ii—O13—N2iv | 89.18 (6) | O1—OW3—H32 | 81.84 |
OW3ii—O13—N2iv | 150.57 (6) | N1viii—OW3—H32 | 83.17 |
S1—O14—N3 | 149.47 (8) | N2v—OW3—H32 | 72.78 |
S1—O14—N2iv | 109.07 (8) | O13viii—OW3—H32 | 3.51 |
N3—O14—N2iv | 100.29 (7) | H31—OW3—H32 | 81.64 |
S1—O14—N3vii | 117.86 (10) | O22x—OW4—O22 | 180.0 |
N3—O14—N3vii | 66.38 (8) | O22x—OW4—O24i | 84.56 (4) |
N2iv—O14—N3vii | 94.72 (6) | O22—OW4—O24i | 95.44 (4) |
S2—O21—V1 | 131.12 (6) | O22x—OW4—O24v | 95.44 (4) |
S2—O21—OW1 | 156.26 (6) | O22—OW4—O24v | 84.56 (4) |
V1—O21—OW1 | 54.38 (3) | O24i—OW4—O24v | 180.0 |
S2—O21—OW2 | 143.24 (6) | O22x—OW4—O2 | 113.74 (3) |
V1—O21—OW2 | 52.99 (4) | O22—OW4—O2 | 66.26 (3) |
OW1—O21—OW2 | 60.42 (4) | O24i—OW4—O2 | 69.74 (4) |
S2—O21—OW4iii | 97.50 (4) | O24v—OW4—O2 | 110.26 (4) |
V1—O21—OW4iii | 129.72 (4) | O22x—OW4—O2x | 66.26 (3) |
OW1—O21—OW4iii | 76.08 (4) | O22—OW4—O2x | 113.74 (3) |
OW2—O21—OW4iii | 97.63 (4) | O24i—OW4—O2x | 110.26 (4) |
S2—O22—OW1i | 124.33 (7) | O24v—OW4—O2x | 69.74 (4) |
S2—O22—OW4 | 144.40 (6) | O2—OW4—O2x | 180.0 |
OW1i—O22—OW4 | 80.52 (4) | O22x—OW4—O21i | 109.45 (4) |
S2—O22—N1viii | 100.75 (6) | O22—OW4—O21i | 70.55 (4) |
OW1i—O22—N1viii | 108.67 (5) | O24i—OW4—O21i | 44.99 (3) |
OW4—O22—N1viii | 92.88 (4) | O24v—OW4—O21i | 135.01 (3) |
S2—O23—OW1viii | 122.36 (6) | O2—OW4—O21i | 93.56 (4) |
S2—O23—N2 | 134.88 (7) | O2x—OW4—O21i | 86.44 (4) |
OW1viii—O23—N2 | 92.63 (5) | O22x—OW4—O21v | 70.55 (4) |
S2—O23—N1viii | 104.00 (7) | O22—OW4—O21v | 109.45 (4) |
OW1viii—O23—N1viii | 72.39 (5) | O24i—OW4—O21v | 135.01 (3) |
N2—O23—N1viii | 114.01 (6) | O24v—OW4—O21v | 44.99 (3) |
S2—O24—N1i | 141.20 (7) | O2—OW4—O21v | 86.44 (4) |
S2—O24—N1ix | 117.49 (6) | O2x—OW4—O21v | 93.56 (4) |
N1i—O24—N1ix | 88.38 (5) | O21i—OW4—O21v | 180.0 |
S2—O24—OW4iii | 108.12 (5) | O22x—OW4—H41 | 171.02 |
N1i—O24—OW4iii | 95.57 (5) | O22—OW4—H41 | 8.98 |
N1ix—O24—OW4iii | 97.23 (5) | O24i—OW4—H41 | 101.01 |
O24i—N1—O24vi | 91.62 (5) | O24v—OW4—H41 | 78.99 |
O24i—N1—OW3ii | 160.04 (7) | O2—OW4—H41 | 62.55 |
O24vi—N1—OW3ii | 79.38 (5) | O2x—OW4—H41 | 117.45 |
O24i—N1—O12 | 131.11 (6) | O21i—OW4—H41 | 79.31 |
O24vi—N1—O12 | 115.00 (6) | O21v—OW4—H41 | 100.69 |
OW3ii—N1—O12 | 68.69 (5) | O22x—OW4—H42 | 109.79 |
O24i—N1—O2 | 70.49 (5) | O22—OW4—H42 | 70.21 |
O24vi—N1—O2 | 136.43 (6) | O24i—OW4—H42 | 165.224 |
OW3ii—N1—O2 | 127.78 (6) | O24v—OW4—H42 | 14.776 |
O12—N1—O2 | 61.90 (4) | O2—OW4—H42 | 106.02 |
O24i—N1—O23ii | 98.26 (5) | O2x—OW4—H42 | 73.98 |
O24vi—N1—O23ii | 123.17 (6) | O21i—OW4—H42 | 123.33 |
OW3ii—N1—O23ii | 72.74 (5) | O21v—OW4—H42 | 56.67 |
O12—N1—O23ii | 99.44 (5) | H41—OW4—H42 | 65.24 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x, y, z−1; (vi) x−1, y, z−1; (vii) −x+1, −y+1, −z; (viii) x+1, y, z; (ix) x+1, y, z+1; (x) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H11···O22i | 0.7727 (9) | 1.9424 (11) | 2.7103 (15) | 172.49 (9) |
OW1—H12···O23ii | 0.8025 (9) | 1.9922 (11) | 2.7939 (15) | 176.88 (8) |
OW2—H21···O12iii | 0.8035 (11) | 1.9784 (13) | 2.7620 (17) | 164.87 (9) |
OW2—H21···OW1 | 0.8035 (11) | 2.6479 (12) | 2.7617 (16) | 89.60 (8) |
OW2—H22···OW3iii | 0.8430 (11) | 1.9628 (15) | 2.8015 (19) | 173.01 (8) |
OW3—H31···O1 | 0.8368 (15) | 1.9813 (12) | 2.803 (2) | 166.83 (12) |
OW3—H32···O13viii | 0.9536 (17) | 2.2200 (15) | 3.171 (2) | 174.98 (10) |
OW4—H41···O22 | 0.8936 (2) | 2.0483 (12) | 2.9263 (14) | 167.11 (3) |
OW4—H42···O24v | 0.8822 (2) | 2.1329 (13) | 2.9740 (13) | 159.17 (3) |
OW4—H42···O21v | 0.8822 (2) | 2.8064 (12) | 3.1926 (12) | 108.10 (3) |
N1—H53···O24i | 0.8362 (13) | 2.0534 (10) | 2.8536 (17) | 159.99 (9) |
N1—H51···O24vi | 0.7706 (13) | 2.1396 (12) | 2.8994 (18) | 168.82 (10) |
N1—H54···OW3ii | 0.8342 (14) | 2.5784 (17) | 2.902 (2) | 104.51 (10) |
N1—H52···O12 | 0.7942 (13) | 2.1621 (14) | 2.923 (2) | 160.61 (10) |
N1—H52···O2 | 0.7942 (13) | 2.5891 (13) | 3.0488 (19) | 118.48 (10) |
N1—H54···O23ii | 0.8342 (14) | 2.2724 (14) | 3.074 (2) | 161.35 (9) |
N1—H54···O22ii | 0.8342 (14) | 2.6245 (13) | 3.151 (2) | 122.40 (9) |
N2—H63···O23 | 0.7241 (14) | 2.1851 (11) | 2.8450 (18) | 152.03 (13) |
N2—H61···O14iv | 0.7869 (15) | 2.0752 (14) | 2.857 (2) | 172.46 (12) |
N2—H62···O12ix | 0.8260 (15) | 2.0435 (13) | 2.862 (2) | 170.62 (11) |
N2—H64···O13viii | 0.8674 (16) | 2.0791 (15) | 2.899 (2) | 157.46 (10) |
N2—H63···O1 | 0.7241 (14) | 2.5386 (12) | 3.006 (2) | 124.25 (12) |
N2—H63···OW3iii | 0.7241 (14) | 2.9058 (17) | 3.087 (2) | 97.63 (13) |
N2—H64···O11viii | 0.8674 (16) | 2.5675 (11) | 3.181 (2) | 128.49 (10) |
N3—H72···O14 | 0.8747 (16) | 2.0530 (14) | 2.805 (2) | 143.54 (11) |
N3—H74···OW2iv | 0.9709 (17) | 2.0948 (11) | 2.825 (2) | 130.69 (14) |
N3—H71···O13viii | 0.8939 (18) | 2.0982 (12) | 2.923 (2) | 153.10 (15) |
N3—H72···O1 | 0.8747 (16) | 2.4473 (11) | 3.062 (2) | 127.71 (12) |
N3—H74···O14vii | 0.9709 (17) | 2.5170 (19) | 3.101 (3) | 118.58 (13) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x, y, z−1; (vi) x−1, y, z−1; (vii) −x+1, −y+1, −z; (viii) x+1, y, z; (ix) x+1, y, z+1. |
Experimental details
Crystal data |
Chemical formula | (NH4)3·[VO2(SO4)2(OH2)2]·1.5H2O |
Mr | 392.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.748 (2), 14.164 (3), 6.268 (2) |
α, β, γ (°) | 91.54 (2), 95.30 (2), 88.25 (2) |
V (Å3) | 684.4 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.10 |
Crystal size (mm) | 0.60 × 0.50 × 0.20 |
|
Data collection |
Diffractometer | RIGAKU AFC-5R automated four-circle diffractometer |
Absorption correction | ψ scan TEXSAN (Molecular Structure Corporation, 1995) |
Tmin, Tmax | 0.576, 0.802 |
No. of measured, independent and observed [F2 > 2.0σ(F2)] reflections | 7201, 7201, 6049 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.857 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.100, 1.05 |
No. of reflections | 7201 |
No. of parameters | 179 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.90, −0.81 |
Selected geometric parameters (Å, º) topV1—O2 | 1.6206 (11) | S1—O13 | 1.4608 (11) |
V1—O1 | 1.6352 (10) | S1—O12 | 1.4725 (14) |
V1—O21 | 2.0026 (10) | S1—O11 | 1.5107 (11) |
V1—O11 | 2.0103 (10) | S2—O22 | 1.4622 (11) |
V1—OW1 | 2.2296 (11) | S2—O24 | 1.4665 (11) |
V1—OW2 | 2.2551 (12) | S2—O23 | 1.4672 (10) |
S1—O14 | 1.4591 (13) | S2—O21 | 1.5045 (9) |
| | | |
O2—V1—O1 | 103.80 (6) | O21—V1—OW1 | 78.73 (4) |
O2—V1—O21 | 97.41 (5) | O11—V1—OW1 | 79.56 (4) |
O1—V1—O21 | 97.72 (5) | O2—V1—OW2 | 170.71 (5) |
O2—V1—O11 | 97.06 (5) | O1—V1—OW2 | 85.45 (5) |
O1—V1—O11 | 98.77 (5) | O21—V1—OW2 | 81.85 (5) |
O21—V1—O11 | 154.76 (4) | O11—V1—OW2 | 80.55 (5) |
O2—V1—OW1 | 94.74 (6) | OW1—V1—OW2 | 76.02 (4) |
O1—V1—OW1 | 161.43 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H11···O22i | 0.7727 (9) | 1.9424 (11) | 2.7103 (15) | 172.49 (9) |
OW1—H12···O23ii | 0.8025 (9) | 1.9922 (11) | 2.7939 (15) | 176.88 (8) |
OW2—H21···O12iii | 0.8035 (11) | 1.9784 (13) | 2.7620 (17) | 164.87 (9) |
OW2—H21···OW1 | 0.8035 (11) | 2.6479 (12) | 2.7617 (16) | 89.60 (8) |
OW2—H22···OW3iii | 0.8430 (11) | 1.9628 (15) | 2.8015 (19) | 173.01 (8) |
OW3—H31···O1 | 0.8368 (15) | 1.9813 (12) | 2.803 (2) | 166.83 (12) |
OW3—H32···O13iv | 0.9536 (17) | 2.2200 (15) | 3.171 (2) | 174.98 (10) |
OW4—H41···O22 | 0.8936 (2) | 2.0483 (12) | 2.9263 (14) | 167.11 (3) |
OW4—H42···O24v | 0.8822 (2) | 2.1329 (13) | 2.9740 (13) | 159.17 (3) |
OW4—H42···O21v | 0.8822 (2) | 2.8064 (12) | 3.1926 (12) | 108.10 (3) |
N1—H53···O24i | 0.8362 (13) | 2.0534 (10) | 2.8536 (17) | 159.99 (9) |
N1—H51···O24vi | 0.7706 (13) | 2.1396 (12) | 2.8994 (18) | 168.82 (10) |
N1—H54···OW3ii | 0.8342 (14) | 2.5784 (17) | 2.902 (2) | 104.51 (10) |
N1—H52···O12 | 0.7942 (13) | 2.1621 (14) | 2.923 (2) | 160.61 (10) |
N1—H52···O2 | 0.7942 (13) | 2.5891 (13) | 3.0488 (19) | 118.48 (10) |
N1—H54···O23ii | 0.8342 (14) | 2.2724 (14) | 3.074 (2) | 161.35 (9) |
N1—H54···O22ii | 0.8342 (14) | 2.6245 (13) | 3.151 (2) | 122.40 (9) |
N2—H63···O23 | 0.7241 (14) | 2.1851 (11) | 2.8450 (18) | 152.03 (13) |
N2—H61···O14vii | 0.7869 (15) | 2.0752 (14) | 2.857 (2) | 172.46 (12) |
N2—H62···O12viii | 0.8260 (15) | 2.0435 (13) | 2.862 (2) | 170.62 (11) |
N2—H64···O13iv | 0.8674 (16) | 2.0791 (15) | 2.899 (2) | 157.46 (10) |
N2—H63···O1 | 0.7241 (14) | 2.5386 (12) | 3.006 (2) | 124.25 (12) |
N2—H63···OW3iii | 0.7241 (14) | 2.9058 (17) | 3.087 (2) | 97.63 (13) |
N2—H64···O11iv | 0.8674 (16) | 2.5675 (11) | 3.181 (2) | 128.49 (10) |
N3—H72···O14 | 0.8747 (16) | 2.0530 (14) | 2.805 (2) | 143.54 (11) |
N3—H74···OW2vii | 0.9709 (17) | 2.0948 (11) | 2.825 (2) | 130.69 (14) |
N3—H71···O13iv | 0.8939 (18) | 2.0982 (12) | 2.923 (2) | 153.10 (15) |
N3—H72···O1 | 0.8747 (16) | 2.4473 (11) | 3.062 (2) | 127.71 (12) |
N3—H74···O14ix | 0.9709 (17) | 2.5170 (19) | 3.101 (3) | 118.58 (13) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x, y, z+1; (iv) x+1, y, z; (v) x, y, z−1; (vi) x−1, y, z−1; (vii) −x+1, −y+1, −z+1; (viii) x+1, y, z+1; (ix) −x+1, −y+1, −z. |
Vanadate solutions in concentrated sulfuric acid (2 ~6 M) are commercially used as an electrolyte for redox-flow batteries (Kazacos et al., 1990; Kumamoto et al., 1999). However, the chemistry of vanadate in such concentrated and highly acidic solutions is still sketchy and the exact composition and structure of the species in solution is not yet known. During the study of such a solution we have isolated the title compound, (I). \sch
The present compound (Fig. 1) consists of a discrete disulfatodiaquadioxovanadate anion, ammonium cations and water of crystallization. The anion shows the trans arrangement of the sulfate ligand about the vanadium atom. A similar connection mode has been observed for V(O3SCF3)2(C5NH5)4 (Ghosh et al., 1995) and K[VO2(SO4)(OH2)2] (Richter & Mattes, 1991). Four additional oxygen atoms bind to the metal centre to complete a distorted octahedral coordination. Those four oxygen atoms lie in a plane that contains the vanadium atom [+0.0161 (7) to −0.0141 (6) Å]. The V1—O distances for two of these O atoms are relatively long [V1—OW1 2.232 (1), V1—OW2 2.259 (1) Å] and indicate that these two oxygen atoms are those of coordinated water molecules. The distances for the other two [V1—O1 1.634 (1), V1—O2 1.620 (1) Å] are normal for terminal oxo ligands. Both terminal oxo ligands and water molecules assume a cis arrangement. In other words, the coordination site trans to an oxo ligand is occupied by a water molecule. The coordination around the vanadium atom is highly distorted and all the O—V1—O angles deviate significantly from the ideal values of 90 and 180°. In addition, the vanadium atom is displaced from the center of the octahedron towards two terminal oxo ligands. This kind of cis dioxo octahedral unit is commonly found in polymolybdates and polytungstates (Pope, 1983). However, the current compound is the first such example for discrete inorganic vanadates to the best of our knowledge. The sulfate tetrahedra, on the other hand, are quite normal. The bond lengths of S—O(—V1) [1.512 (1) Å for S1—O11 and 1.506 (1) Å for S2—O21] are longer than those of other S—O [1.460 (2) to 1.468 (1) Å] due to the coordination to the V atom. The angle S1—V1—S2 is 162.60 (1)° and thus the feature of the anion is slightly bent. Hydrogen bonds formed in the crystal are listed in Table 2. The water of crystallization (OW3 and OW4) and ammonium cations (N1, N2 and N3) form a hydrogen-bond network through the crystal with each other and the disulfatovanado anion. The slightly longer distance of V1—O1 than V1—O2 is probably caused by the rather short contact of OW3 to O1 [2.803 (2) Å].