Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010902397X/sq3194sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010902397X/sq3194Isup2.hkl |
The title crystal was synthesized by a hydrothermal reaction using NH4VO3 (0.2339 g), Co(OAc)2.2H2O (0.2490 g) and water (10 ml) in a molar ratio 2:1:555. The mixture was adjusted to pH 3 with H3PO4 (50%), placed in a 25 ml Teflon-lined autoclave and heated at 443 K for 7 d. After the sample was cooled to room temperature, washed with distilled water, filtered and dried in air, block-shaped green crystals of the title compound were obtained. The reduction of vanadium from +5 to +4 may be due to reaction with acetic acid, which may act as a reducing agent at low pH.
The unique H atom of the water molecule was located in a difference map and included in the refinement with the H—O bond length restrained to 0.82 (2) Å and with the Uiso(H) value fixed to 1.5Ueq(O1W).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Version 5.10; Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Version 5.10; Sheldrick, 2008).
Co0.50VOPO4·2H2O | Dx = 2.879 Mg m−3 |
Mr = 227.41 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4/m | Cell parameters from 58 reflections |
Hall symbol: -I 4 | θ = 2.4–24.6° |
a = 6.2570 (5) Å | µ = 3.69 mm−1 |
c = 13.400 (2) Å | T = 293 K |
V = 524.62 (10) Å3 | Block, green |
Z = 4 | 0.13 × 0.12 × 0.12 mm |
F(000) = 446 |
Bruker APEXII CCD diffractometer | 275 independent reflections |
Radiation source: fine-focus sealed tube | 274 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω scans | θmax = 25.8°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −6→7 |
Tmin = 0.645, Tmax = 0.666 | k = −7→7 |
1403 measured reflections | l = −16→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.017 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.040 | w = 1/[σ2(Fo2) + (0.P)2 + 1.2075P] where P = (Fo2 + 2Fc2)/3 |
S = 1.20 | (Δ/σ)max = 0.021 |
275 reflections | Δρmax = 0.27 e Å−3 |
30 parameters | Δρmin = −0.53 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0571 (12) |
Co0.50VOPO4·2H2O | Z = 4 |
Mr = 227.41 | Mo Kα radiation |
Tetragonal, I4/m | µ = 3.69 mm−1 |
a = 6.2570 (5) Å | T = 293 K |
c = 13.400 (2) Å | 0.13 × 0.12 × 0.12 mm |
V = 524.62 (10) Å3 |
Bruker APEXII CCD diffractometer | 275 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 274 reflections with I > 2σ(I) |
Tmin = 0.645, Tmax = 0.666 | Rint = 0.027 |
1403 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | 1 restraint |
wR(F2) = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | Δρmax = 0.27 e Å−3 |
275 reflections | Δρmin = −0.53 e Å−3 |
30 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 | ||
Co1 | 0.0000 | 0.0000 | 0.0000 | 0.01301 (11) | |
V1 | 0.0000 | 0.0000 | −0.27742 (3) | 0.00716 (9) | |
P1 | 0.5000 | 0.0000 | −0.2500 | 0.00769 (13) | |
O1 | 0.0000 | 0.0000 | −0.15812 (14) | 0.0146 (4) | |
O2 | 0.30301 (14) | −0.01887 (14) | −0.31812 (6) | 0.0108 (2) | |
O1W | 0.1814 (3) | −0.2717 (2) | 0.0000 | 0.0225 (3) | |
H1 | 0.176 (3) | −0.345 (3) | −0.0503 (10) | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01560 (15) | 0.01560 (15) | 0.0078 (2) | 0.000 | 0.000 | 0.000 |
V1 | 0.00733 (11) | 0.00733 (11) | 0.00681 (18) | 0.000 | 0.000 | 0.000 |
P1 | 0.00690 (16) | 0.00690 (16) | 0.0093 (3) | 0.000 | 0.000 | 0.000 |
O1 | 0.0164 (5) | 0.0164 (5) | 0.0109 (8) | 0.000 | 0.000 | 0.000 |
O2 | 0.0075 (4) | 0.0138 (4) | 0.0112 (4) | 0.0003 (3) | 0.0001 (3) | −0.0012 (3) |
O1W | 0.0334 (8) | 0.0225 (7) | 0.0118 (6) | 0.0063 (7) | 0.000 | 0.000 |
Co1—O1Wi | 2.0442 (15) | V1—O2v | 1.9764 (9) |
Co1—O1Wii | 2.0442 (15) | V1—O2 | 1.9764 (9) |
Co1—O1Wiii | 2.0442 (15) | V1—O2ii | 1.9764 (9) |
Co1—O1W | 2.0442 (15) | P1—O2 | 1.5383 (9) |
Co1—O1iii | 2.1189 (19) | P1—O2vi | 1.5383 (9) |
Co1—O1 | 2.1189 (19) | P1—O2vii | 1.5383 (9) |
V1—O1 | 1.5986 (19) | P1—O2viii | 1.5383 (9) |
V1—O2iv | 1.9764 (9) | O1W—H1 | 0.815 (13) |
O1Wi—Co1—O1Wii | 180.00 (9) | O2iv—V1—O2v | 85.632 (14) |
O1Wi—Co1—O1Wiii | 90.0 | O1—V1—O2 | 106.02 (3) |
O1Wii—Co1—O1Wiii | 90.0 | O2iv—V1—O2 | 85.632 (14) |
O1Wi—Co1—O1W | 90.0 | O2v—V1—O2 | 147.96 (5) |
O1Wii—Co1—O1W | 90.0 | O1—V1—O2ii | 106.02 (3) |
O1Wiii—Co1—O1W | 180.00 (8) | O2iv—V1—O2ii | 147.96 (5) |
O1Wi—Co1—O1iii | 90.0 | O2v—V1—O2ii | 85.632 (14) |
O1Wii—Co1—O1iii | 90.0 | O2—V1—O2ii | 85.632 (14) |
O1Wiii—Co1—O1iii | 90.0 | O2—P1—O2vi | 110.62 (3) |
O1W—Co1—O1iii | 90.0 | O2—P1—O2vii | 110.62 (3) |
O1Wi—Co1—O1 | 90.0 | O2vi—P1—O2vii | 107.20 (6) |
O1Wii—Co1—O1 | 90.0 | O2—P1—O2viii | 107.20 (6) |
O1Wiii—Co1—O1 | 90.0 | O2vi—P1—O2viii | 110.62 (3) |
O1W—Co1—O1 | 90.0 | O2vii—P1—O2viii | 110.62 (3) |
O1iii—Co1—O1 | 180.0 | V1—O1—Co1 | 180.0 |
O1—V1—O2iv | 106.02 (3) | P1—O2—V1 | 126.89 (5) |
O1—V1—O2v | 106.02 (3) | Co1—O1W—H1 | 116.3 (13) |
Symmetry codes: (i) y, −x, −z; (ii) −y, x, z; (iii) −x, −y, −z; (iv) y, −x, z; (v) −x, −y, z; (vi) y+1/2, −x+1/2, −z−1/2; (vii) −y+1/2, x−1/2, −z−1/2; (viii) −x+1, −y, z. |
Experimental details
Crystal data | |
Chemical formula | Co0.50VOPO4·2H2O |
Mr | 227.41 |
Crystal system, space group | Tetragonal, I4/m |
Temperature (K) | 293 |
a, c (Å) | 6.2570 (5), 13.400 (2) |
V (Å3) | 524.62 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.69 |
Crystal size (mm) | 0.13 × 0.12 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.645, 0.666 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1403, 275, 274 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.613 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.040, 1.20 |
No. of reflections | 275 |
No. of parameters | 30 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.53 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Version 5.10; Sheldrick, 2008).
Co1—O1W | 2.0442 (15) | V1—O2 | 1.9764 (9) |
Co1—O1 | 2.1189 (19) | P1—O2 | 1.5383 (9) |
V1—O1 | 1.5986 (19) | O1W—H1 | 0.815 (13) |
Over the past few decades, the synthesis of solid-state inorganic materials with new topological structures built up of oxygen polyhedra has received much attention because of the functional applications of these materials in ion-exchange, adsorption, catalysis and radioactive waste remediation. As the tetrahedral building elements of polyhedral frameworks, not only Si and Ge, but also P have been chosen to synthesize inorganic materials (Li et al., 1998; Xu et al., 2004; Xu et al., 2006). In the past few years, an important advance in layered materials has been the study of vanadophosphates (Soghomonian et al., 1993; Huang et al., 2001; Cui et al., 2004). Our research concentrates on connecting V—P—O layers by transition metals to make new three-dimensional inorganic materials. As part of this work, we designed and synthesized the title compound, which features a three-dimensional framework constructed from V—P—O layers and [Co(H2O)4]2+ cations.
The asymmetric unit of Co0.50VOPO4.2H2O contains nine crystallographically independent non-H atoms (Fig. 1). The octahedrally coordinated Co1 atom is located on the origin with 4/m symmetry. The four coordinated water molecules (O1W) are located in the equatorial (mirror) plane. Atom V1 is coordinated by five O atoms in a typical square pyramid. Both the V atom and the apical O atom are on the fourfold rotation axis. The basal O atoms, which are shared with the P atoms, make O—V—O angles of 85.56 (2) and 147.67 (8)° [or 85.632 (14) and 147.96 (5)°?]. The short apical V—O distance (Table 1) indicates a vanadyl-type interaction (V═O). The V atom carries a formal oxidation state of +4, which is confirmed by bond-valence sum calculations (Brown & Altermatt, 1985), S = (R/R0)-N = 4.0024. Atom P1 of the tetrahedral phosphate group is located on a special position of 4 symmetry. Each V atom makes four V—O—P linkages, and the polyhedra thus connect to produce a very flat VOPO4 layer (Fig. 2), which is similar to that found in the previously reported compounds (NH4)VOPO4.1.5H2O (Do et al., 2000a), Na0.5VOPO4.2H2O and K0.5VOPO4.1.5H2O (Wang et al., 1991), and (C4H12N2)[VO(VO2)PO4]2 (Do et al., 2000b). In contrast to these phases, the interlayer ammonium or alkali metal cations are replaced by [Co(H2O)4]2+ cations that coordinate to the vanadyl O atoms and thus link adjacent layers to generate a three-dimensional framework (Fig. 3). To the best of our knowledge, this is the first example in which a transition metal (Co2+) connects flat V—O—P layers. The layers, which are 7.44 (2) Å apart, contain channels running along the b direction. These secondary building units are constructed from four VO5 square pyramids, two PO4 tetrahedra and two CoO6 octahedra (Fig. 4). In the reported three-dimensional vanadophosphates with larger 10-polyhedron ring channels (Zhang et al., 1995; Chen et al., 2006), templating organic amines are located in the channels.
Thermal analysis of Co0.50VOPO4.2H2O in an N2 atmosphere shows a one-step mass loss of 15.85% between 573 and 623 K, with no further loss up to 1073 K. The total weight loss is in excellent agreement with the calculated weight loss for desorption of coordinated water. Powder X-ray diffraction indicates that the inorganic framework collapses completely after the removal of water.