Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011719/qd0027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011719/qd0027Isup2.hkl |
Initially, `H2SeO3' (dissolved SeO2; 8 ml 0.5 M), water (4 ml), VOSO4·H2O (0.532 g) and CsCl (0.673 g)(starting ratio of Cs:V:Se = 1:1:1) were heated to 423 K in a 23-ml-capacity teflon-lined hydrothermal bomb for two days, resulting in a green plug, which was discarded, and a blue solution. –The solution was evaporated to dryness to result in a blue-green glass (amorphous by X-rays) which was returned to the bomb with H2O (5 ml) and heated to 423 K for a further four days. Product recovery by vacuum filtration and washing with water and acetone led to a mass of well faceted, pleochroic (dark orange–brown along the hexagonal axis; yellow–green normal to the hexagonal axis) hexagonal prisms of the title compound. These prisms varied in shape from plate-like to rod-like.
The largest difference peak is 0.82 Å from Cs1. Friedel pairs were not merged during data reduction to enable determination of the absolute structure by refinement of the Flack parameter. The structure has pseudosymmetry comparable with space group P63mc. However, the systematic absences are not consistent with P63mc, and the merging R factor of 0.131 for Laue group 6/mmm is significantly larger than that for 6/m (0.048). Structurally, P63mc appears to involve the vanadium atom being placed at the centre of its octahedron, which is a very unlikely situation for a vanadium(V) system.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: starting coordinates from isostructural material; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Cs·(VO2)3·(SeO3)2 | Dx = 4.091 Mg m−3 |
Mr = 635.65 | Melting point: decomposes before melting K |
Hexagonal, P63 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 6c | Cell parameters from 1888 reflections |
a = 7.1613 (5) Å | θ = 3.3–29.4° |
c = 11.6184 (8) Å | µ = 13.25 mm−1 |
V = 516.01 (6) Å3 | T = 298 K |
Z = 2 | Hexagonal column, yellow–green |
F(000) = 576 | 0.27 × 0.08 × 0.08 mm |
Bruker SMART 1000 diffractometer | 966 independent reflections |
Radiation source: fine-focus sealed tube | 895 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 30°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −9→7 |
Tmin = 0.172, Tmax = 0.346 | k = −6→9 |
3428 measured reflections | l = −16→16 |
Refinement on F2 | Secondary atom site location: none |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0336P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.029 | (Δ/σ)max < 0.001 |
wR(F2) = 0.063 | Δρmax = 2.23 e Å−3 |
S = 1.01 | Δρmin = −0.80 e Å−3 |
966 reflections | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
57 parameters | Extinction coefficient: 0.0030 (6) |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: from isostructural material | Absolute structure parameter: 0.00 (2) |
Cs·(VO2)3·(SeO3)2 | Z = 2 |
Mr = 635.65 | Mo Kα radiation |
Hexagonal, P63 | µ = 13.25 mm−1 |
a = 7.1613 (5) Å | T = 298 K |
c = 11.6184 (8) Å | 0.27 × 0.08 × 0.08 mm |
V = 516.01 (6) Å3 |
Bruker SMART 1000 diffractometer | 966 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 895 reflections with I > 2σ(I) |
Tmin = 0.172, Tmax = 0.346 | Rint = 0.048 |
3428 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 1 restraint |
wR(F2) = 0.063 | Δρmax = 2.23 e Å−3 |
S = 1.01 | Δρmin = −0.80 e Å−3 |
966 reflections | Absolute structure: Flack (1983) |
57 parameters | Absolute structure parameter: 0.00 (2) |
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 | ||
Cs1 | 0.3333 | 0.6667 | 0.98245 (5) | 0.02018 (18) | |
V1 | 0.78873 (16) | 0.12114 (15) | 0.79392 (8) | 0.00958 (19) | |
Se1 | 0.6667 | 0.3333 | 1.01597 (7) | 0.0105 (2) | |
Se2 | 1.0000 | 0.0000 | 0.57510 (9) | 0.00937 (19) | |
O1 | 0.8021 (6) | 0.2192 (6) | 0.9539 (3) | 0.0129 (8) | |
O2 | 0.8868 (6) | 0.1348 (6) | 0.6387 (3) | 0.0124 (8) | |
O3 | 0.5441 (6) | 0.0792 (7) | 0.7650 (4) | 0.0152 (8) | |
O4 | 0.7461 (6) | −0.1225 (7) | 0.8265 (4) | 0.0130 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cs1 | 0.0165 (2) | 0.0165 (2) | 0.0275 (3) | 0.00825 (12) | 0.000 | 0.000 |
V1 | 0.0071 (5) | 0.0071 (5) | 0.0138 (4) | 0.0030 (4) | 0.0003 (3) | 0.0003 (3) |
Se1 | 0.0108 (3) | 0.0108 (3) | 0.0099 (4) | 0.00541 (16) | 0.000 | 0.000 |
Se2 | 0.0094 (3) | 0.0094 (3) | 0.0093 (3) | 0.00471 (13) | 0.000 | 0.000 |
O1 | 0.014 (2) | 0.016 (2) | 0.0121 (19) | 0.0107 (17) | −0.0007 (13) | −0.0006 (13) |
O2 | 0.012 (2) | 0.0105 (19) | 0.0156 (19) | 0.0061 (16) | 0.0016 (14) | 0.0001 (13) |
O3 | 0.0084 (18) | 0.0146 (19) | 0.024 (2) | 0.0067 (15) | −0.0013 (16) | −0.0013 (18) |
O4 | 0.0124 (19) | 0.0124 (19) | 0.0164 (17) | 0.0079 (16) | 0.0032 (17) | 0.0031 (15) |
Cs1—O4i | 3.137 (4) | V1—O3 | 1.657 (4) |
Cs1—O4ii | 3.137 (4) | V1—O4 | 1.658 (4) |
Cs1—O4iii | 3.137 (4) | V1—O2 | 1.920 (4) |
Cs1—O2iv | 3.169 (4) | V1—O1 | 1.972 (4) |
Cs1—O2v | 3.169 (4) | V1—O4x | 2.176 (4) |
Cs1—O2vi | 3.169 (4) | V1—O3ix | 2.178 (4) |
Cs1—O1vii | 3.558 (4) | Se1—O1 | 1.709 (4) |
Cs1—O1viii | 3.558 (4) | Se1—O1ii | 1.709 (4) |
Cs1—O1ix | 3.558 (4) | Se1—O1ix | 1.709 (4) |
Cs1—O3i | 3.596 (4) | Se2—O2x | 1.708 (4) |
Cs1—O3iii | 3.596 (4) | Se2—O2xi | 1.708 (4) |
Cs1—O3ii | 3.596 (4) | Se2—O2 | 1.708 (4) |
O4i—Cs1—O4ii | 89.96 (11) | O1ix—Cs1—O3iii | 91.69 (9) |
O4i—Cs1—O4iii | 89.96 (11) | O3i—Cs1—O3iii | 76.07 (12) |
O4ii—Cs1—O4iii | 89.96 (11) | O4i—Cs1—O3ii | 100.05 (12) |
O4i—Cs1—O2iv | 70.25 (10) | O4ii—Cs1—O3ii | 44.85 (9) |
O4ii—Cs1—O2iv | 130.95 (11) | O4iii—Cs1—O3ii | 46.88 (9) |
O4iii—Cs1—O2iv | 132.49 (11) | O2iv—Cs1—O3ii | 170.13 (10) |
O4i—Cs1—O2v | 130.95 (11) | O2v—Cs1—O3ii | 97.63 (10) |
O4ii—Cs1—O2v | 132.49 (11) | O2vi—Cs1—O3ii | 95.15 (10) |
O4iii—Cs1—O2v | 70.25 (10) | O1vii—Cs1—O3ii | 91.69 (9) |
O2iv—Cs1—O2v | 90.44 (10) | O1viii—Cs1—O3ii | 119.67 (9) |
O4i—Cs1—O2vi | 132.49 (11) | O1ix—Cs1—O3ii | 43.87 (9) |
O4ii—Cs1—O2vi | 70.25 (10) | O3i—Cs1—O3ii | 76.07 (12) |
O4iii—Cs1—O2vi | 130.95 (11) | O3iii—Cs1—O3ii | 76.07 (12) |
O2iv—Cs1—O2vi | 90.44 (10) | O1—Se1—O1ii | 103.47 (15) |
O2v—Cs1—O2vi | 90.44 (10) | O1—Se1—O1ix | 103.47 (15) |
O4i—Cs1—O1vii | 79.45 (10) | O1ii—Se1—O1ix | 103.47 (14) |
O4ii—Cs1—O1vii | 46.83 (9) | O2x—Se2—O2xi | 102.67 (16) |
O4iii—Cs1—O1vii | 134.87 (10) | O2x—Se2—O2 | 102.67 (16) |
O2iv—Cs1—O1vii | 84.82 (10) | O2xi—Se2—O2 | 102.67 (16) |
O2v—Cs1—O1vii | 145.18 (10) | O3—V1—O4 | 103.5 (2) |
O2vi—Cs1—O1vii | 55.22 (9) | O3—V1—O2 | 98.3 (2) |
O4i—Cs1—O1viii | 46.83 (9) | O4—V1—O2 | 97.95 (19) |
O4ii—Cs1—O1viii | 134.87 (10) | O3—V1—O1 | 96.6 (2) |
O4iii—Cs1—O1viii | 79.45 (9) | O4—V1—O1 | 96.3 (2) |
O2iv—Cs1—O1viii | 55.22 (9) | O2—V1—O1 | 156.29 (17) |
O2v—Cs1—O1viii | 84.82 (9) | O3—V1—O4x | 166.77 (19) |
O2vi—Cs1—O1viii | 145.18 (10) | O4—V1—O4x | 89.7 (2) |
O1vii—Cs1—O1viii | 119.141 (19) | O2—V1—O4x | 80.63 (17) |
O4i—Cs1—O1ix | 134.87 (10) | O1—V1—O4x | 80.63 (16) |
O4ii—Cs1—O1ix | 79.45 (9) | O3—V1—O3ix | 89.8 (3) |
O4iii—Cs1—O1ix | 46.83 (9) | O4—V1—O3ix | 166.6 (2) |
O2iv—Cs1—O1ix | 145.18 (10) | O2—V1—O3ix | 81.73 (17) |
O2v—Cs1—O1ix | 55.22 (9) | O1—V1—O3ix | 80.02 (17) |
O2vi—Cs1—O1ix | 84.82 (9) | O4x—V1—O3ix | 77.02 (16) |
O1vii—Cs1—O1ix | 119.141 (19) | Se1—O1—V1 | 129.0 (2) |
O1viii—Cs1—O1ix | 119.14 (2) | Se1—O1—Cs1xii | 97.87 (16) |
O4i—Cs1—O3i | 44.85 (9) | V1—O1—Cs1xii | 104.38 (14) |
O4ii—Cs1—O3i | 46.88 (9) | Se1—O1—Cs1xiii | 92.58 (14) |
O4iii—Cs1—O3i | 100.05 (12) | V1—O1—Cs1xiii | 81.22 (12) |
O2iv—Cs1—O3i | 95.15 (10) | Cs1xii—O1—Cs1xiii | 160.46 (12) |
O2v—Cs1—O3i | 170.13 (10) | V1—O3—V1ii | 142.4 (3) |
O2vi—Cs1—O3i | 97.63 (10) | V1—O3—Cs1xiii | 88.73 (16) |
O1vii—Cs1—O3i | 43.87 (9) | V1ii—O3—Cs1xiii | 98.67 (15) |
O1viii—Cs1—O3i | 91.69 (8) | V1—O3—Cs1xiv | 97.11 (18) |
O1ix—Cs1—O3i | 119.67 (9) | V1ii—O3—Cs1xiv | 88.18 (13) |
O4i—Cs1—O3iii | 46.88 (9) | Cs1xiii—O3—Cs1xiv | 160.27 (14) |
O4ii—Cs1—O3iii | 100.05 (12) | V1—O4—V1xi | 140.6 (2) |
O4iii—Cs1—O3iii | 44.85 (9) | V1—O4—Cs1xiii | 105.77 (17) |
O2iv—Cs1—O3iii | 97.63 (10) | V1xi—O4—Cs1xiii | 113.58 (16) |
O2v—Cs1—O3iii | 95.15 (10) | Se2—O2—V1 | 130.0 (2) |
O2vi—Cs1—O3iii | 170.13 (10) | Se2—O2—Cs1xiv | 119.26 (18) |
O1vii—Cs1—O3iii | 119.67 (9) | V1—O2—Cs1xiv | 108.04 (16) |
O1viii—Cs1—O3iii | 43.87 (9) |
Symmetry codes: (i) −y, x−y, z; (ii) −x+y+1, −x+1, z; (iii) x, y+1, z; (iv) −x+1, −y+1, z+1/2; (v) x−y, x, z+1/2; (vi) y, −x+y+1, z+1/2; (vii) x−1, y, z; (viii) −x+y+1, −x+2, z; (ix) −y+1, x−y, z; (x) −x+y+2, −x+1, z; (xi) −y+1, x−y−1, z; (xii) x+1, y, z; (xiii) x, y−1, z; (xiv) −x+1, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | Cs·(VO2)3·(SeO3)2 |
Mr | 635.65 |
Crystal system, space group | Hexagonal, P63 |
Temperature (K) | 298 |
a, c (Å) | 7.1613 (5), 11.6184 (8) |
V (Å3) | 516.01 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 13.25 |
Crystal size (mm) | 0.27 × 0.08 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.172, 0.346 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3428, 966, 895 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.063, 1.01 |
No. of reflections | 966 |
No. of parameters | 57 |
No. of restraints | 1 |
Δρmax, Δρmin (e Å−3) | 2.23, −0.80 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.00 (2) |
Computer programs: SMART (Bruker, 1999), SMART, starting coordinates from isostructural material, SHELXL97 (Sheldrick, 1997).
The title compound is another member of the family of layered phases (Harrison et al., 1996) structurally related to hexagonal tungsten oxide, hex-WO3 (Gérand et al., 1979). It is built up from vertex sharing VO6 octahedra and SeO3 pyramids, fused together via V—O—V (θav = 141.5°) and V—O—Se (θav = 129.5°) bonds. Interlayer Cs+ cations complete the packing in Cs(VO2)3(SeO3)2 which is isostructural with NH4(VO2)3(SeO3)2 (Vaughey et al., 1994), K(VO2)3(SeO3)2 (Harrison et al., 1995), and Cs(VO2)3(TeO3)2 (Harrison & Buttery, 2000).
The VO6 grouping shows a distinctive distortion mode with the vanadium atom displaced by 0.36 Å from the geometric best centre (Balic Zunic & Makovicky, 1996) of its octahedron, essentially towards an octahedral edge (Harrison et al., 1996). This situation results in two short (d < 1.67 Å) V–O vertices, each of which is trans to a long (d > 2.16 Å) V—O bond. The two remaining V—O bonds are of intermediate length. The short and long bonds are involved in V—O—V links and the intermediate length bonds participate in V—O—Se connections. A bond valence sum (BVS; Brown, 1996) of 5.05 results for vanadium (expected value = 5.00 for VV). The two Se atoms have threefold symmetry and their expected pyramidal geometry [BVS(Se1) = 3.95, BVS(Se2) = 3.96, expected = 4.00]. The 12-coordinate [dav = 3.365 (4) Å] caesium cation, with site symmetry 3, serves to link adjacent anionic sheets by way of O—Cs—O bonds.