Acta Cryst. (2008). E64, i20 [ doi:10.1107/S1600536808003851 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
O)sulfato(2O,O')molybdate(VI)The title compound, K4[MoVIO2(SO4)3], was precipitated from a melt of molybdenum(VI) oxide and potassium sulfate in potassium disulfate. The compound contains monomeric [MoVIO2(SO4)3]4- anions, with the MoVI atom, both oxide ligands, and the S atom and both ligating O atoms of the bidentate sulfate group lying on a crystallographic mirror plane. One of the potassium cations is nine-coordinate, while the other is eight-coordinate.
Crystals were grown from a melt of 28.0 mol% molybdenum(VI) oxide, 43.9 mol% potassium sulfate, and 28.1 mol% potassium disulfate, using a method described previously (Nørbygaard et al., 1998).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bi2277fig1thm.gif)
| Fig. 1. The [MoVIO2(SO4)3]4- anion and four K+ cations, showing displacement ellipsoids at 50% probability. |
![[Figure 2]](./bi2277fig2thm.gif)
| Fig. 2. The crystal packing, viewed along the a axis. |
| K4[MoO2(SO4)3] | F000 = 1112 |
| Mr = 572.52 | Dx = 2.781 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 9999 reflections |
| a = 7.5931 (5) Å | θ = 2.3–28.0º |
| b = 17.1276 (11) Å | µ = 2.71 mm−1 |
| c = 10.5132 (7) Å | T = 120 (2) K |
| V = 1367.26 (16) Å3 | Tabular, colorless |
| Z = 4 | 0.28 × 0.18 × 0.08 mm |
| Bruker SMART APEX CCD diffractometer | 1693 independent reflections |
| Radiation source: normal-focus sealed tube | 1681 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.019 |
| T = 120(2) K | θmax = 28.0º |
| ω scans | θmin = 2.3º |
| Absorption correction: gaussian (XPREP; Bruker, 2002) | h = −9→10 |
| Tmin = 0.512, Tmax = 0.684 | k = −22→22 |
| 16179 measured reflections | l = −13→13 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0174P)2 + 1.7854P] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.016 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.041 | Δρmax = 0.59 e Å−3 |
| S = 1.11 | Δρmin = −0.46 e Å−3 |
| 1693 reflections | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 110 parameters | Extinction coefficient: 0.00164 (15) |
| Primary atom site location: structure-invariant direct methods |
| K4[MoO2(SO4)3] | V = 1367.26 (16) Å3 |
| Mr = 572.52 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα |
| a = 7.5931 (5) Å | µ = 2.71 mm−1 |
| b = 17.1276 (11) Å | T = 120 (2) K |
| c = 10.5132 (7) Å | 0.28 × 0.18 × 0.08 mm |
| Bruker SMART APEX CCD diffractometer | 1693 independent reflections |
| Absorption correction: gaussian (XPREP; Bruker, 2002) | 1681 reflections with I > 2σ(I) |
| Tmin = 0.512, Tmax = 0.684 | Rint = 0.019 |
| 16179 measured reflections |
| R[F2 > 2σ(F2)] = 0.016 | 110 parameters |
| wR(F2) = 0.041 | Δρmax = 0.59 e Å−3 |
| S = 1.11 | Δρmin = −0.46 e Å−3 |
| 1693 reflections |
Experimental. Five series of frames were filtered for statistical outliers then corrected for absorption using XPREP in SHELXTL (Sheldrick, 2008) before using SAINT & SADABS (Bruker, 2002) to sort, merge, and scale the combined data. A series of identical frames was collected twice during the experiment to monitor decay, and none was observed. |
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 | ||
| K1 | 0.43682 (4) | 0.08865 (2) | −0.24076 (3) | 0.01208 (8) | |
| K2 | 0.25655 (5) | 0.10844 (2) | 0.39352 (3) | 0.01644 (9) | |
| Mo1 | 0.32312 (3) | 0.2500 | 0.065899 (18) | 0.00961 (7) | |
| S1 | 0.62301 (7) | 0.2500 | −0.09790 (5) | 0.00926 (11) | |
| S2 | 0.23382 (5) | 0.06574 (2) | 0.06161 (3) | 0.00949 (9) | |
| O1 | 0.3105 (3) | 0.2500 | 0.22628 (17) | 0.0209 (4) | |
| O2 | 0.1129 (2) | 0.2500 | 0.0135 (2) | 0.0219 (4) | |
| O3 | 0.4316 (2) | 0.2500 | −0.13493 (15) | 0.0124 (3) | |
| O4 | 0.6095 (2) | 0.2500 | 0.04687 (15) | 0.0102 (3) | |
| O5 | 0.70888 (16) | 0.17874 (7) | −0.13903 (11) | 0.0135 (2) | |
| O6 | 0.36968 (15) | 0.13324 (7) | 0.05145 (11) | 0.0134 (2) | |
| O7 | 0.16034 (17) | 0.05557 (8) | −0.06586 (11) | 0.0161 (3) | |
| O8 | 0.10253 (17) | 0.08813 (8) | 0.15593 (12) | 0.0184 (3) | |
| O9 | 0.33322 (16) | −0.00276 (7) | 0.10186 (13) | 0.0176 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| K1 | 0.01082 (17) | 0.01361 (16) | 0.01182 (16) | 0.00149 (12) | −0.00089 (12) | 0.00023 (12) |
| K2 | 0.02176 (19) | 0.01335 (17) | 0.01422 (17) | 0.00508 (14) | 0.00204 (14) | −0.00023 (13) |
| Mo1 | 0.00891 (10) | 0.00789 (10) | 0.01203 (11) | 0.000 | 0.00220 (7) | 0.000 |
| S1 | 0.0105 (2) | 0.0077 (2) | 0.0096 (2) | 0.000 | 0.0013 (2) | 0.000 |
| S2 | 0.01081 (18) | 0.00829 (17) | 0.00938 (18) | −0.00132 (14) | 0.00002 (13) | 0.00071 (13) |
| O1 | 0.0304 (11) | 0.0172 (9) | 0.0150 (9) | 0.000 | 0.0080 (8) | 0.000 |
| O2 | 0.0117 (8) | 0.0178 (9) | 0.0364 (11) | 0.000 | −0.0020 (8) | 0.000 |
| O3 | 0.0119 (8) | 0.0139 (8) | 0.0115 (7) | 0.000 | −0.0019 (6) | 0.000 |
| O4 | 0.0115 (8) | 0.0102 (7) | 0.0089 (7) | 0.000 | 0.0001 (6) | 0.000 |
| O5 | 0.0158 (6) | 0.0095 (5) | 0.0153 (6) | 0.0017 (4) | 0.0044 (5) | −0.0012 (4) |
| O6 | 0.0116 (5) | 0.0088 (5) | 0.0197 (6) | −0.0019 (4) | 0.0022 (5) | −0.0001 (4) |
| O7 | 0.0187 (6) | 0.0186 (6) | 0.0111 (6) | −0.0037 (5) | −0.0034 (4) | 0.0017 (4) |
| O8 | 0.0163 (6) | 0.0201 (6) | 0.0187 (6) | −0.0045 (5) | 0.0072 (5) | −0.0055 (5) |
| O9 | 0.0181 (6) | 0.0116 (6) | 0.0232 (6) | −0.0002 (5) | −0.0046 (5) | 0.0058 (5) |
| Mo1—O1 | 1.6889 (18) | K2—O8vi | 2.7005 (14) |
| Mo1—O2 | 1.6883 (18) | K2—O4vii | 2.7419 (8) |
| Mo1—O3 | 2.2665 (17) | K2—O8 | 2.7799 (14) |
| Mo1—O4 | 2.1837 (16) | K2—O5vii | 2.8710 (13) |
| Mo1—O6 | 2.0365 (12) | K2—O7viii | 2.9106 (14) |
| Mo1—O6i | 2.0365 (12) | K2—O9viii | 2.9220 (14) |
| S1—O3 | 1.5044 (17) | K2—O1 | 3.0229 (11) |
| S1—O4 | 1.5254 (16) | K2—O6vii | 3.0239 (13) |
| S1—O5 | 1.4497 (12) | O1—K2i | 3.0229 (11) |
| S1—O5i | 1.4497 (12) | O3—K1i | 2.9794 (7) |
| S2—O6 | 1.5532 (12) | O4—K2ix | 2.7419 (8) |
| S2—O7 | 1.4621 (12) | O4—K2vi | 2.7419 (8) |
| S2—O8 | 1.4575 (13) | O5—K1iii | 2.6408 (12) |
| S2—O9 | 1.4577 (12) | O5—K2vi | 2.8710 (13) |
| K1—O5ii | 2.6408 (12) | O6—K2vi | 3.0239 (13) |
| K1—O7iii | 2.7083 (12) | O7—K1ii | 2.7083 (12) |
| K1—O9iv | 2.7102 (12) | O7—K2v | 2.9106 (14) |
| K1—O5 | 2.7915 (13) | O8—K2vii | 2.7005 (14) |
| K1—O7 | 2.8476 (13) | O8—K1viii | 3.2305 (14) |
| K1—O3 | 2.9794 (7) | O9—K1iv | 2.7102 (12) |
| K1—O9v | 3.0176 (13) | O9—K2v | 2.9220 (13) |
| K1—O6 | 3.2064 (12) | O9—K1viii | 3.0176 (13) |
| K1—O8v | 3.2305 (14) | ||
| O5ii—K1—O7iii | 100.00 (4) | O1—Mo1—O6i | 94.84 (4) |
| O5ii—K1—O9iv | 175.76 (4) | O6—Mo1—O6i | 158.22 (7) |
| O7iii—K1—O9iv | 83.52 (4) | O2—Mo1—O4 | 155.71 (8) |
| O5ii—K1—O5 | 110.20 (4) | O1—Mo1—O4 | 98.52 (8) |
| O7iii—K1—O5 | 86.53 (4) | O6—Mo1—O4 | 79.65 (3) |
| O9iv—K1—O5 | 67.47 (4) | O6i—Mo1—O4 | 79.65 (3) |
| O5ii—K1—O7 | 86.68 (4) | O2—Mo1—O3 | 92.29 (8) |
| O7iii—K1—O7 | 154.84 (5) | O1—Mo1—O3 | 161.94 (8) |
| O9iv—K1—O7 | 91.09 (4) | O6—Mo1—O3 | 82.38 (3) |
| O5—K1—O7 | 114.09 (4) | O6i—Mo1—O3 | 82.38 (3) |
| O5ii—K1—O3 | 68.16 (4) | O4—Mo1—O3 | 63.43 (6) |
| O7iii—K1—O3 | 118.86 (4) | O3—S1—O4 | 101.14 (9) |
| O9iv—K1—O3 | 108.11 (4) | O5—S1—O5i | 114.68 (10) |
| O5—K1—O3 | 49.76 (4) | O5—S1—O3 | 110.93 (6) |
| O7—K1—O3 | 86.20 (4) | O5i—S1—O3 | 110.93 (6) |
| O5ii—K1—O9v | 64.98 (4) | O5—S1—O4 | 109.14 (6) |
| O7iii—K1—O9v | 84.97 (4) | O5i—S1—O4 | 109.14 (6) |
| O9iv—K1—O9v | 117.94 (5) | O8—S2—O9 | 111.62 (8) |
| O5—K1—O9v | 169.23 (4) | O8—S2—O7 | 113.20 (8) |
| O7—K1—O9v | 75.89 (4) | O9—S2—O7 | 111.58 (8) |
| O3—K1—O9v | 130.39 (4) | O8—S2—O6 | 107.77 (7) |
| O5ii—K1—O6 | 102.42 (4) | O9—S2—O6 | 105.97 (7) |
| O7iii—K1—O6 | 150.31 (4) | O7—S2—O6 | 106.20 (7) |
| O9iv—K1—O6 | 73.47 (4) | Mo1—O1—K2i | 126.04 (3) |
| O5—K1—O6 | 67.60 (3) | Mo1—O1—K2 | 126.04 (3) |
| O7—K1—O6 | 46.49 (3) | K2i—O1—K2 | 106.66 (6) |
| O3—K1—O6 | 54.49 (4) | S1—O3—Mo1 | 96.32 (8) |
| O9v—K1—O6 | 122.24 (3) | S1—O3—K1 | 94.81 (4) |
| O5ii—K1—O8v | 109.03 (4) | Mo1—O3—K1 | 110.65 (3) |
| O7iii—K1—O8v | 67.02 (4) | S1—O3—K1i | 94.81 (4) |
| O9iv—K1—O8v | 74.46 (4) | Mo1—O3—K1i | 110.65 (3) |
| O5—K1—O8v | 135.67 (3) | K1—O3—K1i | 136.12 (6) |
| O7—K1—O8v | 87.85 (4) | S1—O4—Mo1 | 99.11 (8) |
| O3—K1—O8v | 173.55 (4) | S1—O4—K2ix | 101.58 (4) |
| O9v—K1—O8v | 45.24 (3) | Mo1—O4—K2ix | 112.62 (4) |
| O6—K1—O8v | 122.05 (3) | S1—O4—K2vi | 101.58 (4) |
| O8vi—K2—O4vii | 123.65 (4) | Mo1—O4—K2vi | 112.62 (4) |
| O8vi—K2—O8 | 102.72 (3) | K2ix—O4—K2vi | 124.32 (6) |
| O4vii—K2—O8 | 98.32 (4) | S1—O5—K1iii | 158.35 (7) |
| O8vi—K2—O5vii | 110.47 (4) | S1—O5—K1 | 104.29 (6) |
| O4vii—K2—O5vii | 51.12 (4) | K1iii—O5—K1 | 88.78 (4) |
| O8—K2—O5vii | 143.83 (4) | S1—O5—K2vi | 98.14 (6) |
| O8vi—K2—O7viii | 72.12 (4) | K1iii—O5—K2vi | 95.88 (4) |
| O4vii—K2—O7viii | 155.26 (4) | K1—O5—K2vi | 101.88 (4) |
| O8—K2—O7viii | 95.87 (4) | S2—O6—Mo1 | 127.63 (7) |
| O5vii—K2—O7viii | 107.47 (3) | S2—O6—K2vi | 121.83 (6) |
| O8vi—K2—O9viii | 106.95 (4) | Mo1—O6—K2vi | 107.00 (5) |
| O4vii—K2—O9viii | 106.35 (4) | S2—O6—K1 | 89.66 (5) |
| O8—K2—O9viii | 119.86 (4) | Mo1—O6—K1 | 109.45 (5) |
| O5vii—K2—O9viii | 63.67 (3) | K2vi—O6—K1 | 89.74 (3) |
| O7viii—K2—O9viii | 48.91 (3) | S2—O7—K1ii | 154.47 (8) |
| O8vi—K2—O1 | 81.93 (5) | S2—O7—K1 | 106.67 (6) |
| O4vii—K2—O1 | 58.59 (4) | K1ii—O7—K1 | 86.31 (3) |
| O8—K2—O1 | 68.58 (4) | S2—O7—K2v | 99.59 (6) |
| O5vii—K2—O1 | 101.75 (4) | K1ii—O7—K2v | 103.16 (4) |
| O7viii—K2—O1 | 146.11 (4) | K1—O7—K2v | 86.41 (4) |
| O9viii—K2—O1 | 164.67 (4) | S2—O8—K2vii | 124.63 (7) |
| O8vi—K2—O6vii | 179.32 (4) | S2—O8—K2 | 110.89 (7) |
| O4vii—K2—O6vii | 55.70 (4) | K2vii—O8—K2 | 124.48 (5) |
| O8—K2—O6vii | 77.34 (4) | S2—O8—K1viii | 92.60 (6) |
| O5vii—K2—O6vii | 69.31 (3) | K2vii—O8—K1viii | 95.48 (4) |
| O7viii—K2—O6vii | 108.55 (3) | K2—O8—K1viii | 81.61 (4) |
| O9viii—K2—O6vii | 73.56 (3) | S2—O9—K1iv | 157.94 (8) |
| O1—K2—O6vii | 97.48 (4) | S2—O9—K2v | 99.22 (6) |
| O2—Mo1—O1 | 105.77 (10) | K1iv—O9—K2v | 102.59 (4) |
| O2—Mo1—O6 | 98.04 (4) | S2—O9—K1viii | 101.52 (6) |
| O1—Mo1—O6 | 94.84 (4) | K1iv—O9—K1viii | 82.98 (3) |
| O2—Mo1—O6i | 98.04 (4) | K2v—O9—K1viii | 87.16 (3) |
| Symmetry codes: (i) x, −y+1/2, z; (ii) x−1/2, y, −z−1/2; (iii) x+1/2, y, −z−1/2; (iv) −x+1, −y, −z; (v) −x+1/2, −y, z−1/2; (vi) x+1/2, y, −z+1/2; (vii) x−1/2, y, −z+1/2; (viii) −x+1/2, −y, z+1/2; (ix) x+1/2, −y+1/2, −z+1/2. |
| Mo1—O1 | 1.6889 (18) | S2—O6 | 1.5532 (12) |
| Mo1—O2 | 1.6883 (18) | S2—O7 | 1.4621 (12) |
| Mo1—O3 | 2.2665 (17) | S2—O8 | 1.4575 (13) |
| Mo1—O4 | 2.1837 (16) | S2—O9 | 1.4577 (12) |
| Mo1—O6 | 2.0365 (12) | K1—O5i | 2.6408 (12) |
| S1—O3 | 1.5044 (17) | K1—O8ii | 3.2305 (14) |
| S1—O4 | 1.5254 (16) | K2—O8iii | 2.7005 (14) |
| S1—O5 | 1.4497 (12) | K2—O6iv | 3.0239 (13) |
| O2—Mo1—O1 | 105.77 (10) | O2—Mo1—O3 | 92.29 (8) |
| O2—Mo1—O6 | 98.04 (4) | O1—Mo1—O3 | 161.94 (8) |
| O1—Mo1—O6 | 94.84 (4) | O6—Mo1—O3 | 82.38 (3) |
| O6—Mo1—O6v | 158.22 (7) | O4—Mo1—O3 | 63.43 (6) |
| O2—Mo1—O4 | 155.71 (8) | O3—S1—O4 | 101.14 (9) |
| O1—Mo1—O4 | 98.52 (8) | O5—S1—O5v | 114.68 (10) |
| O6—Mo1—O4 | 79.65 (3) |
| Symmetry codes: (i) x−1/2, y, −z−1/2; (ii) −x+1/2, −y, z−1/2; (iii) x+1/2, y, −z+1/2; (iv) x−1/2, y, −z+1/2; (v) x, −y+1/2, z. |
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Efforts to improve the industrial vanadium-based sulfuric acid catalyst (Topsøe & Nielsen, 1947) have led to investigations of potassium disulfate's use as a suitable solvent for the production of new sulfate-containing catalysts. Many of the previously reported sulfato compounds precipitated from melts of potassium disulfate contain polymeric anions (Nørbygaard et al., 1998, Berg & Thorup, 2005), while some contain dimers (Nielsen et al., 1993, Rasmussen et al., 2003, Schäffer & Berg, 2005). Monomers such as that in the title compound (Fig. 1) are less common (Borup et al., 1990).
The coordination sphere of the MoVI atom contains two oxido ligands, two terminally bound sulfato ligands, and a bidentate sulfato ligand. Because of the bidentate ligand, the coordination sphere angles (see Table 1) in the mirror plane are grossly distorted from octahedral. The O3—Mo1—O4 angle is only 63.43 (6)°, while the O1—Mo1—O2 angle opposite to it is 105.77 (10)°. Deviations of 10° or less are found for the other angles between cis O atoms. The Mo=O bond distances are nearly equivalent (1.6883 (18)Å & 1.6889 (18) Å), which is expected since both bonds are trans to O atoms in the bidentate sulfato ligand. The Mo—O distance to the terminal sulfato [Mo1—O6] is slightly shorter than those to the bidentate sulfato ligand [Mo1—O3 and Mo1—O4]. The Mo—O distances compare well with previously reported values (Salles et al., 1996, Nørbygaard et al., 1998).
The S—O bond distances of 1.5044 (17)–1.5532 (17)Å involving O bound to Mo are longer than the terminal S—O bond lengths of 1.4497–1.4621 (12) Å, an effect typical for sulfato complexes of many different transition metal centers (Borup et al., 1990, Nielsen et al., 1993, Berg & Thorup, 2005). The sulfato ligands have approximately tetrahedral geometry. The angles vary from 101.14° for O3—S1—O4 to 114.68 (10)° for O5—S1—O5i [symmetry code (i): x, 1/2 - y, z]; both extremes involve the bidentate sulfato ligand. Five of the eight remaining independent O—S—O angles deviate by less than 2° from ideal. The potassium cation, K1, is nine-coordinate, while K2 is eight-coordinate. The K—O distances range from 2.6408 to 3.2305 (14) Å.