Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015735/br1277sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015735/br1277Isup2.hkl |
Small, lime green crystals of Ba3V2(HPO4)6 were prepared from a mixture of BaCO3 (1.365 g, 6.92 mmol), VCl3 (1.106 g, 7.03 mmol), H3PO4 (3.562 g of an 85% soln, 42.76 mmol), guanidinium carbonate (1.245 g, 6.91 mmol), and water (10.0 ml, 555 mmol), corresponding to a 1:1:6 Ba:V:P starting ratio. These components were heated to 453 K in a sealed teflon-lined hydrothermal bomb for 24 h and the solid products were recovered by vacuum filtration. Reactions omitting guanidine carbonate or starting from the stoichiometric 3:2:6 Ba:V:P atomic ratio led to other, as yet unidentified phases.
The highest difference peak is 0.85 Å from Ba1; the deepest difference hole is 0.82 Å from Ba1. The H atoms were assumed to be rifing on O3.
Data collection: SMART (Bruker, 1997b); cell refinement: SMART; data reduction: SMART; program(s) used to refine structure: CRYSTALS (Watkin et al., 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CRYSTALS.
Ba3V2(HPO4)6 | Melting point: decomposes before melting K |
Mr = 1089.75 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3c | Cell parameters from 3121 reflections |
a = 9.423 (1) Å | θ = 4–25° |
c = 36.945 (8) Å | µ = 7.69 mm−1 |
V = 2840.8 Å3 | T = 298 K |
Z = 6 | Block, yellow-green |
F(000) = 3008.66 | 0.04 × 0.04 × 0.04 mm |
Dx = 3.82 Mg m−3 |
Bruker SMART area detector diffractometer | 753 reflections with I > 1.00σ(I) |
Peak integration from area detector frames with the program SAINT (Bruker, 1997) scans | Rint = 0.064 |
Absorption correction: multi-scan (SADABS; Bruker, 1997a) | θmax = 29.0°, θmin = 2.0° |
Tmin = 0.52, Tmax = 0.70 | h = −10→10 |
11318 measured reflections | k = −12→12 |
830 independent reflections | l = −48→48 |
Refinement on F | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | Only H-atom displacement parameters refined |
wR(F2) = 0.049 | Chebychev polynomial (Carruthers & Watkin, 1979) with 3 parameters 0.560 0.493 0.317 |
S = 1.06 | (Δ/σ)max = 0.0002 |
753 reflections | Δρmax = 1.71 e Å−3 |
57 parameters | Δρmin = −1.20 e Å−3 |
Primary atom site location: structure-invariant direct methods |
Ba3V2(HPO4)6 | Z = 6 |
Mr = 1089.75 | Mo Kα radiation |
Trigonal, R3c | µ = 7.69 mm−1 |
a = 9.423 (1) Å | T = 298 K |
c = 36.945 (8) Å | 0.04 × 0.04 × 0.04 mm |
V = 2840.8 Å3 |
Bruker SMART area detector diffractometer | 830 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997a) | 753 reflections with I > 1.00σ(I) |
Tmin = 0.52, Tmax = 0.70 | Rint = 0.064 |
11318 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 57 parameters |
wR(F2) = 0.049 | Only H-atom displacement parameters refined |
S = 1.06 | Δρmax = 1.71 e Å−3 |
753 reflections | Δρmin = −1.20 e Å−3 |
Experimental. Crystal decay was monitored by collecting duplicate frames at the end of the experiment, and was found to be negligible. |
x | y | z | Uiso*/Ueq | ||
Ba1 | 0.40831 (4) | 0.0000 | 0.2500 | 0.0203 | |
V1 | 0.0000 | 0.0000 | 0.0000 | 0.0136 | |
V2 | 0.3333 | 0.6667 | −0.0833 | 0.0137 | |
P1 | 0.28500 (16) | 0.36482 (15) | −0.03241 (4) | 0.0178 | |
O1 | 0.1476 (4) | 0.1846 (4) | −0.0340 (1) | 0.0206 | |
O2 | 0.2246 (4) | 0.4662 (4) | −0.05233 (9) | 0.0184 | |
O3 | 0.3122 (4) | 0.4163 (5) | 0.00849 (11) | 0.0244 | |
O4 | 0.4439 (5) | 0.3845 (4) | −0.04806 (11) | 0.0218 | |
H1 | 0.4023 | 0.4898 | 0.02308 | 0.0200* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba1 | 0.0156 (2) | 0.0245 (3) | 0.0238 (3) | 0.01224 (13) | 0.00040 (7) | 0.00081 (14) |
V1 | 0.0095 (5) | 0.0095 (5) | 0.0220 (9) | 0.0047 (2) | 0.0000 | 0.0000 |
V2 | 0.0091 (5) | 0.0091 (5) | 0.0227 (9) | 0.0046 (2) | 0.0000 | 0.0000 |
P1 | 0.0125 (5) | 0.0122 (5) | 0.0279 (7) | 0.0056 (4) | −0.0027 (5) | 0.0021 (4) |
O1 | 0.0154 (15) | 0.0131 (15) | 0.0314 (19) | 0.0057 (13) | −0.0022 (13) | 0.0029 (13) |
O2 | 0.0164 (15) | 0.0145 (15) | 0.0276 (16) | 0.0102 (13) | 0.0001 (13) | 0.0036 (12) |
O3 | 0.0161 (16) | 0.0208 (18) | 0.031 (2) | 0.0052 (14) | −0.0035 (13) | −0.0020 (15) |
O4 | 0.0136 (15) | 0.0171 (16) | 0.034 (2) | 0.0071 (14) | 0.0012 (13) | −0.0001 (14) |
Ba1—O1i | 3.108 (3) | V1—O1xi | 2.030 (4) |
Ba1—O1ii | 3.043 (4) | V1—O1xii | 2.030 (4) |
Ba1—O1iii | 3.108 (3) | V1—O1xiii | 2.030 (4) |
Ba1—O1iv | 3.043 (4) | V2—O2 | 1.999 (3) |
Ba1—O2i | 2.755 (3) | V2—O2xiv | 1.999 (3) |
Ba1—O2iii | 2.755 (3) | V2—O2xv | 1.999 (3) |
Ba1—O3v | 2.849 (4) | V2—O2xvi | 1.999 (3) |
Ba1—O3vi | 2.849 (4) | V2—O2xvii | 1.999 (3) |
Ba1—O4vii | 3.030 (4) | V2—O2xviii | 1.999 (3) |
Ba1—O4ii | 2.872 (4) | P1—O1 | 1.537 (4) |
Ba1—O4viii | 3.030 (4) | P1—O2 | 1.524 (3) |
Ba1—O4iv | 2.872 (4) | P1—O3 | 1.569 (4) |
V1—O1 | 2.030 (4) | P1—O4 | 1.527 (4) |
V1—O1ix | 2.030 (4) | O3—H1 | 0.950 |
V1—O1x | 2.030 (4) | ||
O1i—Ba1—O1ii | 53.34 (13) | O3vi—Ba1—O4ii | 123.30 (11) |
O1i—Ba1—O1iii | 153.92 (13) | O4vii—Ba1—O4ii | 88.43 (16) |
O1ii—Ba1—O1iii | 151.66 (3) | O2iii—Ba1—O4viii | 66.7 (1) |
O1i—Ba1—O1iv | 151.66 (3) | O3v—Ba1—O4viii | 125.32 (11) |
O1ii—Ba1—O1iv | 102.32 (13) | O3vi—Ba1—O4viii | 51.8 (1) |
O1iii—Ba1—O1iv | 53.34 (13) | O4vii—Ba1—O4viii | 121.69 (15) |
O1i—Ba1—O2i | 49.38 (9) | O4ii—Ba1—O4viii | 147.15 (6) |
O1ii—Ba1—O2i | 99.20 (9) | O2iii—Ba1—O4iv | 128.35 (11) |
O1iii—Ba1—O2i | 105.03 (9) | O3v—Ba1—O4iv | 123.30 (11) |
O1iv—Ba1—O2i | 158.2 (1) | O3vi—Ba1—O4iv | 61.26 (11) |
O1i—Ba1—O2iii | 105.03 (9) | O4vii—Ba1—O4iv | 147.15 (6) |
O1ii—Ba1—O2iii | 158.2 (1) | O4ii—Ba1—O4iv | 66.98 (16) |
O1iii—Ba1—O2iii | 49.38 (9) | O4viii—Ba1—O4iv | 88.43 (16) |
O1iv—Ba1—O2iii | 99.20 (9) | O1—V1—O1ix | 180 |
O2i—Ba1—O2iii | 59.57 (13) | O1—V1—O1x | 85.72 (16) |
O1i—Ba1—O3v | 66.84 (11) | O1ix—V1—O1x | 94.28 (16) |
O1ii—Ba1—O3v | 64.1 (1) | O1—V1—O1xi | 94.28 (16) |
O1iii—Ba1—O3v | 112.0 (1) | O1ix—V1—O1xi | 85.72 (16) |
O1iv—Ba1—O3v | 119.2 (1) | O1x—V1—O1xi | 180 |
O2i—Ba1—O3v | 68.01 (11) | O1—V1—O1xii | 85.72 (16) |
O1i—Ba1—O3vi | 112.0 (1) | O1ix—V1—O1xii | 94.28 (16) |
O1ii—Ba1—O3vi | 119.2 (1) | O1x—V1—O1xii | 85.72 (16) |
O1iii—Ba1—O3vi | 66.84 (11) | O1xi—V1—O1xii | 94.28 (16) |
O1iv—Ba1—O3vi | 64.1 (1) | O1—V1—O1xiii | 94.28 (16) |
O2i—Ba1—O3vi | 107.7 (1) | O1ix—V1—O1xiii | 85.72 (16) |
O1i—Ba1—O4vii | 103.2 (1) | O1x—V1—O1xiii | 94.28 (16) |
O1ii—Ba1—O4vii | 115.2 (1) | O1xi—V1—O1xiii | 85.72 (16) |
O1iii—Ba1—O4vii | 63.3 (1) | O1xii—V1—O1xiii | 180 |
O1iv—Ba1—O4vii | 100.6 (1) | O2—V2—O2xiv | 90.41 (14) |
O2i—Ba1—O4vii | 66.7 (1) | O2—V2—O2xv | 90.41 (14) |
O1i—Ba1—O4ii | 99.6 (1) | O2xiv—V2—O2xv | 90.41 (14) |
O1ii—Ba1—O4ii | 50.3 (1) | O2—V2—O2xvi | 175.4 (2) |
O1iii—Ba1—O4ii | 102.1 (1) | O2xiv—V2—O2xvi | 92.9 (2) |
O1iv—Ba1—O4ii | 65.9 (1) | O2xv—V2—O2xvi | 86.4 (2) |
O2i—Ba1—O4ii | 128.35 (11) | O2—V2—O2xvii | 92.9 (2) |
O1i—Ba1—O4viii | 63.3 (1) | O2xiv—V2—O2xvii | 86.4 (2) |
O1ii—Ba1—O4viii | 100.6 (1) | O2xv—V2—O2xvii | 175.4 (2) |
O1iii—Ba1—O4viii | 103.2 (1) | O2xvi—V2—O2xvii | 90.41 (14) |
O1iv—Ba1—O4viii | 115.2 (1) | O2—V2—O2xviii | 86.4 (2) |
O2i—Ba1—O4viii | 63.22 (11) | O2xiv—V2—O2xviii | 175.4 (2) |
O1i—Ba1—O4iv | 102.1 (1) | O2xv—V2—O2xviii | 92.9 (2) |
O1ii—Ba1—O4iv | 65.9 (1) | O2xvi—V2—O2xviii | 90.41 (14) |
O1iii—Ba1—O4iv | 99.6 (1) | O2xvii—V2—O2xviii | 90.41 (14) |
O1iv—Ba1—O4iv | 50.3 (1) | O1—P1—O2 | 107.57 (19) |
O2i—Ba1—O4iv | 145.8 (1) | O1—P1—O3 | 107.2 (2) |
O2iii—Ba1—O3v | 107.7 (1) | O2—P1—O3 | 109.0 (2) |
O2iii—Ba1—O3vi | 68.01 (11) | O1—P1—O4 | 110.6 (2) |
O3v—Ba1—O3vi | 175.32 (15) | O2—P1—O4 | 113.1 (2) |
O2iii—Ba1—O4vii | 63.22 (11) | O3—P1—O4 | 109.2 (2) |
O3v—Ba1—O4vii | 51.8 (1) | V1—O1—P1 | 139.5 (2) |
O3vi—Ba1—O4vii | 125.32 (11) | V2—O2—P1 | 133.9 (2) |
O2iii—Ba1—O4ii | 145.8 (1) | P1—O3—H1 | 136.10 (14) |
O3v—Ba1—O4ii | 61.26 (11) |
Symmetry codes: (i) −y+2/3, x−y+1/3, z+1/3; (ii) −x+y+2/3, −x+1/3, z+1/3; (iii) −x+1/3, −x+y−1/3, −z+1/6; (iv) y+1/3, x−1/3, −z+1/6; (v) −x+2/3, −y+1/3, −z+1/3; (vi) −x+y+1/3, y−1/3, z+1/6; (vii) x−1/3, y−2/3, z+1/3; (viii) x−y+1/3, −y+2/3, −z+1/6; (ix) −x, −y, −z; (x) −y, x−y, z; (xi) y, −x+y, −z; (xii) −x+y, −x, z; (xiii) x−y, x, −z; (xiv) −y+1, x−y+1, z; (xv) −x+y, −x+1, z; (xvi) x−y+2/3, −y+4/3, −z−1/6; (xvii) −x+2/3, −x+y+1/3, −z−1/6; (xviii) y−1/3, x+1/3, −z−1/6. |
Experimental details
Crystal data | |
Chemical formula | Ba3V2(HPO4)6 |
Mr | 1089.75 |
Crystal system, space group | Trigonal, R3c |
Temperature (K) | 298 |
a, c (Å) | 9.423 (1), 36.945 (8) |
V (Å3) | 2840.8 |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 7.69 |
Crystal size (mm) | 0.04 × 0.04 × 0.04 |
Data collection | |
Diffractometer | Bruker SMART area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997a) |
Tmin, Tmax | 0.52, 0.70 |
No. of measured, independent and observed [I > 1.00σ(I)] reflections | 11318, 830, 753 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.049, 1.06 |
No. of reflections | 753 |
No. of parameters | 57 |
No. of restraints | ? |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 1.71, −1.20 |
Computer programs: SMART (Bruker, 1997b), SMART, CRYSTALS (Watkin et al., 1997), ORTEP-3 (Farrugia, 1997), CRYSTALS.
Ba1—O1i | 3.108 (3) | V1—O1 | 2.030 (4) |
Ba1—O1ii | 3.043 (4) | V2—O2 | 1.999 (3) |
Ba1—O2i | 2.755 (3) | P1—O1 | 1.537 (4) |
Ba1—O3iii | 2.849 (4) | P1—O2 | 1.524 (3) |
Ba1—O4iv | 3.030 (4) | P1—O3 | 1.569 (4) |
Ba1—O4ii | 2.872 (4) | P1—O4 | 1.527 (4) |
V1—O1—P1 | 139.5 (2) | V2—O2—P1 | 133.9 (2) |
Symmetry codes: (i) −y+2/3, x−y+1/3, z+1/3; (ii) −x+y+2/3, −x+1/3, z+1/3; (iii) −x+2/3, −y+1/3, −z+1/3; (iv) x−1/3, y−2/3, z+1/3. |
Barium vanadium phosphates (BaVPOs) show considerable structural variety with at least 15 well characterized BaVPO phases reported so far (Bircsak & Harrison, 1998). Here we report the hydrothermal synthesis of a new barium vanadium(III) hydrogen phosphate, Ba3V2(HPO4)6 (Figs. 1 and 2), which is built up from barium cations and a vertex-sharing network of VO6 octahedra and tetrahedral HPO4 units, fused together via V—O—P bonds.
The barium cation (site symmetry. 2) adopts 12-fold coordination, assuming a cut-off of 3.2 Å for the maximum Ba—O distance [dav(Ba—O) = 2.944 (4) Å]. The bond valence sum (BVS), calculated by the Brown formalism (1997), of 2.14 for Ba (expected value = 2.00) shows that its valence requirement is satisfied by this coordination.
The two distinct vanadium(III) cations in Ba3V2(HPO4)6 adopt typical, essentially regular octahedral geometries (Dvoncova et al., 1993), although the point symmetries of V1 (3) and V2 (32) are distinct. BVS values of 2.78 for V1 and 3.00 for V2 are unexceptional (expected: 3.00). The phosphorus atom shows its normal tetrahedral coordination [dav(P—O) = 1.537 (3) Å, BVS(P1) = 4.97, expected 5.00] and participates in P1—O1—V1, P1—O2—V2, and two terminal P—O bonds. The P1—O3 bond is assumed to be protonated, based on its length, whilst the P1—O4 bond is short, indicating some degree of multiple bond character. Based on geometrical placement of the H atom [d(O3—H) = 0.95 Å], an O3—H···O4 [d(H···O) = 1.62 Å, d(O···O) = 2.575 (6) Å] hydrogen bond is present.
The polyhedral connectivity in Ba3V2(HPO4)6 results in a three-dimensional network of VO6 and HPO4 polyhedra. The smallest identifiable polyhedral loop is a four ring (two VO6 and two HPO4 groups) with the proposed O—H···O hydrogen bond occurring across this loop. Every V1O6 octahedron bonds to six different V2O6 octahedra via six V1—O1—P1—O2—V2 links. The [V2(HPO4)6]6- framework encloses channels propagating along [100], [010], and [110], which are occupied by the barium cations.
Like the other vanadium(III)-containing BaVPOs (Bircsak & Harrison, 1998) this phase is three-dimensional in its V/P/O connectivity, and the VO6 moieties are close to being regular octahedra. Vanadium(IV) and vanadium(V)-containing BaVPOs have quite different, distorted vanadium coordinations (Wadewitz & Müller-Buschbaum, 1996; Kang et al., 1992) and tend to form structures with lower dimensionality. The A3B2(XO4)6 stoichiometry of Ba3V2(HPO4)6 appears to be a novel one for phosphates and no similar stoichiometries could be found in the Inorganic Crystal Structure Database (1999).