Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112026005/yp3013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112026005/yp3013Isup2.hkl |
CCDC reference: 893486
For related literature, see: Brown & Altermatt (1985); De Burgomaster, Liu, O'Connor & Zubieta (2010); Feng & Xu (2001); Ushak et al. (2006); Venegas-Yazigi, Brown, Vega, Calvo, Aliaga, Santana, Cardoso-Gil, Kniep, Schnelle & Spodine (2011); Yang et al. (2010); Yucesan et al. (2005).
Cupric oxide (CuO; 0.1934 g, 2.43 mmol), 1,10-phenanthroline (phen; 0.0849 g, 0.47 mmol), orthophosphoric acid (H3PO4; 0.41 g, 4.2 mmol), sodium vanadate (NaVO3; 0.0881 g, 1 mmol) and water (H2O; 10 ml, 555.56 mmol) in a 5.2:1:8.9:1.5:1182 molar ratio were mixed in a Teflon Parr reactor, and then heated at 473 K for 4 d. The pH of the reaction mixture was 1.1. After the reaction solution had cooled down to room temperature, the products were filtered off and dried at 313 K. Rhombohedral green crystals of (I) were separated manually under a microscope. These proved to be of good quality for single-crystal X-ray diffraction (yield 23.6%, based on V). IR (Medium?, ν, cm-1): bands 1076 (s) and 1000 (m) are assigned to the P—O stretch, the band at 889 (s) is due to the stretching vibrations of the terminal V═O group, 773 (s) is assigned to the V—O—V stretching vibrations, 731 (w), 511 (w) and 413 (w) correspond to the stretching vibrations of the V—O or V—O—P bonds, and 1610 (m), 1601 (m) and 1473 (s) correspond to the organic ligand 1,10-phenanthroline. Analysis, calculated for C12H11CuN2O10P2V: C 27.74, H 2.13, N 5.39%; found: C 26.5, H 2.2, N 5.9%.
The H-atom positions were calculated after each cycle of refinement using a riding model, with C—H = 0.93 Å, and with Uiso(H) = 1.2Ueq. Efforts to locate the phosphovanadate H atoms in the final Fourier difference map were unsuccessful; those reported for the formula are based on charge-balance analysis. During the last stages of refinement, some disorder was evident on the position of the atom O10, which bonds a vanadyl and a phosphate group. This is reasonable, since the terminal PO4 group has no other covalent bond. The disorder was modelled by introducing two positions for O10, A and B, and their occupancies were subsequently refined subject to the condition that they summed to 1. When it was clear that the occupancies had reached constant values, at 0.60 and 0.40 for A and B, respectively, the values were set constant for the final refinement stages.
Data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT (Bruker, 1999); program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-NT (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008) and ORTEPIII (Farrugia 1997); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008).
[CuV(HPO4)(H2PO4)O2(C12H8N2)] | Z = 2 |
Mr = 519.66 | F(000) = 512 |
Triclinic, P1 | Dx = 1.991 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2350 (14) Å | Cell parameters from 600 reflections |
b = 10.705 (2) Å | θ = 2.5–22.1° |
c = 11.624 (2) Å | µ = 2.02 mm−1 |
α = 75.25 (3)° | T = 293 K |
β = 82.58 (3)° | Polyhedron, green |
γ = 84.91 (3)° | 0.21 × 0.11 × 0.09 mm |
V = 861.9 (3) Å3 |
Siemens SMART CCD area-detector diffractometer | 3031 independent reflections |
Radiation source: fine-focus sealed tube | 2737 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→8 |
Tmin = 0.56, Tmax = 0.80 | k = −12→12 |
16352 measured reflections | l = −13→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0402P)2 + 1.0381P] where P = (Fo2 + 2Fc2)/3 |
3031 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
[CuV(HPO4)(H2PO4)O2(C12H8N2)] | γ = 84.91 (3)° |
Mr = 519.66 | V = 861.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2350 (14) Å | Mo Kα radiation |
b = 10.705 (2) Å | µ = 2.02 mm−1 |
c = 11.624 (2) Å | T = 293 K |
α = 75.25 (3)° | 0.21 × 0.11 × 0.09 mm |
β = 82.58 (3)° |
Siemens SMART CCD area-detector diffractometer | 3031 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2737 reflections with I > 2σ(I) |
Tmin = 0.56, Tmax = 0.80 | Rint = 0.022 |
16352 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.76 e Å−3 |
3031 reflections | Δρmin = −0.49 e Å−3 |
262 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 | Occ. (<1) | |
Cu1 | 1.12123 (4) | 0.63888 (3) | 0.79354 (3) | 0.02349 (11) | |
V1 | 0.64322 (6) | 0.62598 (4) | 0.83604 (4) | 0.02653 (13) | |
P1 | 0.92146 (9) | 0.38207 (6) | 0.92512 (6) | 0.02031 (15) | |
P2 | 0.57687 (10) | 0.80389 (6) | 1.03196 (7) | 0.02956 (18) | |
O1 | 0.7417 (3) | 0.46947 (19) | 0.91659 (19) | 0.0348 (5) | |
O2 | 1.0856 (2) | 0.45305 (17) | 0.85199 (17) | 0.0276 (4) | |
O3 | 0.9501 (3) | 0.32515 (19) | 1.05341 (16) | 0.0327 (4) | |
O4 | 0.9004 (3) | 0.2714 (2) | 0.86304 (19) | 0.0357 (5) | |
O5 | 0.7869 (3) | 0.6841 (2) | 0.7222 (2) | 0.0448 (5) | |
O6 | 0.4540 (3) | 0.6055 (2) | 0.7902 (2) | 0.0509 (6) | |
O7 | 0.3863 (3) | 0.86317 (18) | 1.0534 (2) | 0.0390 (5) | |
O8 | 0.6202 (3) | 0.7018 (2) | 1.1470 (2) | 0.0576 (7) | |
O9 | 0.7233 (3) | 0.9043 (2) | 1.0087 (3) | 0.0721 (10) | |
O10A | 0.5764 (11) | 0.7266 (9) | 0.9405 (9) | 0.0552 (19) | 0.60 |
O10B | 0.6308 (15) | 0.7593 (12) | 0.9169 (12) | 0.041 (2) | 0.40 |
N1 | 1.1515 (3) | 0.8276 (2) | 0.7169 (2) | 0.0276 (5) | |
N2 | 1.1869 (3) | 0.6241 (2) | 0.62461 (19) | 0.0262 (5) | |
C1 | 1.2038 (4) | 0.5192 (3) | 0.5823 (3) | 0.0361 (7) | |
H1 | 1.1742 | 0.4401 | 0.6341 | 0.043* | |
C2 | 1.2648 (5) | 0.5238 (3) | 0.4622 (3) | 0.0456 (8) | |
H2 | 1.2780 | 0.4485 | 0.4353 | 0.055* | |
C3 | 1.3049 (5) | 0.6395 (4) | 0.3851 (3) | 0.0450 (8) | |
H3 | 1.3452 | 0.6432 | 0.3051 | 0.054* | |
C4 | 1.2855 (4) | 0.7532 (3) | 0.4258 (3) | 0.0376 (7) | |
C5 | 1.2264 (3) | 0.7394 (3) | 0.5481 (2) | 0.0272 (6) | |
C6 | 1.2054 (4) | 0.8496 (3) | 0.5976 (2) | 0.0287 (6) | |
C7 | 1.2380 (4) | 0.9737 (3) | 0.5238 (3) | 0.0396 (7) | |
C8 | 1.2105 (5) | 1.0770 (3) | 0.5791 (3) | 0.0508 (9) | |
H8 | 1.2286 | 1.1610 | 0.5340 | 0.061* | |
C9 | 1.1571 (5) | 1.0542 (3) | 0.6992 (4) | 0.0499 (9) | |
H9 | 1.1403 | 1.1224 | 0.7363 | 0.060* | |
C10 | 1.1278 (4) | 0.9276 (3) | 0.7663 (3) | 0.0379 (7) | |
H10 | 1.0906 | 0.9132 | 0.8480 | 0.046* | |
C11 | 1.2959 (5) | 0.9847 (4) | 0.3989 (3) | 0.0529 (9) | |
H11 | 1.3176 | 1.0659 | 0.3485 | 0.063* | |
C12 | 1.3195 (5) | 0.8801 (4) | 0.3532 (3) | 0.0514 (9) | |
H12 | 1.3590 | 0.8907 | 0.2721 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02796 (19) | 0.02098 (18) | 0.01874 (18) | −0.00315 (12) | 0.00142 (12) | −0.00118 (12) |
V1 | 0.0219 (2) | 0.0265 (2) | 0.0304 (3) | 0.00248 (18) | −0.00274 (18) | −0.00707 (19) |
P1 | 0.0212 (3) | 0.0189 (3) | 0.0196 (3) | −0.0020 (2) | −0.0003 (2) | −0.0031 (2) |
P2 | 0.0263 (4) | 0.0176 (3) | 0.0424 (4) | 0.0009 (3) | 0.0042 (3) | −0.0076 (3) |
O1 | 0.0237 (10) | 0.0339 (11) | 0.0401 (11) | 0.0035 (8) | −0.0014 (8) | 0.0003 (9) |
O2 | 0.0238 (9) | 0.0230 (9) | 0.0316 (10) | −0.0037 (7) | 0.0014 (8) | −0.0002 (8) |
O3 | 0.0413 (11) | 0.0310 (10) | 0.0207 (10) | 0.0069 (9) | −0.0003 (8) | −0.0018 (8) |
O4 | 0.0344 (11) | 0.0390 (11) | 0.0403 (12) | −0.0107 (9) | 0.0034 (9) | −0.0227 (10) |
O5 | 0.0400 (12) | 0.0388 (12) | 0.0461 (13) | −0.0007 (10) | 0.0074 (10) | 0.0002 (10) |
O6 | 0.0297 (11) | 0.0508 (14) | 0.0717 (17) | 0.0000 (10) | −0.0209 (11) | −0.0075 (12) |
O7 | 0.0251 (10) | 0.0214 (10) | 0.0672 (15) | −0.0005 (8) | 0.0039 (10) | −0.0096 (10) |
O8 | 0.0476 (14) | 0.0529 (15) | 0.0501 (15) | 0.0173 (12) | 0.0134 (11) | 0.0118 (12) |
O9 | 0.0264 (12) | 0.0267 (12) | 0.152 (3) | −0.0014 (9) | 0.0029 (15) | −0.0072 (15) |
O10A | 0.047 (5) | 0.063 (5) | 0.064 (5) | 0.001 (3) | 0.008 (3) | −0.041 (4) |
O10B | 0.033 (5) | 0.039 (5) | 0.055 (6) | −0.006 (3) | 0.005 (4) | −0.020 (4) |
N1 | 0.0263 (11) | 0.0259 (12) | 0.0279 (12) | −0.0022 (9) | −0.0025 (9) | −0.0018 (9) |
N2 | 0.0254 (11) | 0.0294 (12) | 0.0223 (11) | −0.0026 (9) | −0.0025 (9) | −0.0032 (9) |
C1 | 0.0405 (16) | 0.0372 (16) | 0.0316 (15) | −0.0020 (13) | −0.0049 (13) | −0.0101 (13) |
C2 | 0.055 (2) | 0.052 (2) | 0.0350 (17) | 0.0009 (16) | −0.0058 (15) | −0.0207 (15) |
C3 | 0.0439 (18) | 0.067 (2) | 0.0239 (15) | −0.0012 (16) | −0.0018 (13) | −0.0135 (15) |
C4 | 0.0314 (15) | 0.054 (2) | 0.0227 (14) | −0.0041 (14) | −0.0023 (12) | −0.0013 (13) |
C5 | 0.0208 (12) | 0.0351 (15) | 0.0216 (13) | −0.0035 (11) | −0.0028 (10) | 0.0011 (11) |
C6 | 0.0241 (13) | 0.0290 (14) | 0.0282 (14) | −0.0035 (11) | −0.0029 (11) | 0.0025 (11) |
C7 | 0.0374 (16) | 0.0325 (16) | 0.0402 (17) | −0.0076 (13) | −0.0043 (13) | 0.0086 (13) |
C8 | 0.056 (2) | 0.0270 (16) | 0.061 (2) | −0.0113 (15) | −0.0022 (17) | 0.0060 (15) |
C9 | 0.059 (2) | 0.0256 (16) | 0.066 (2) | −0.0033 (15) | −0.0066 (18) | −0.0119 (16) |
C10 | 0.0437 (17) | 0.0298 (15) | 0.0397 (17) | −0.0032 (13) | −0.0017 (14) | −0.0085 (13) |
C11 | 0.057 (2) | 0.049 (2) | 0.0390 (19) | −0.0140 (17) | 0.0007 (16) | 0.0161 (16) |
C12 | 0.054 (2) | 0.064 (2) | 0.0254 (16) | −0.0106 (18) | 0.0035 (14) | 0.0085 (16) |
Cu1—N1 | 2.009 (2) | N1—C10 | 1.327 (4) |
Cu1—N2 | 2.003 (2) | N1—C6 | 1.357 (4) |
Cu1—O2 | 1.9603 (19) | O6—Cu1iii | 2.399 (2) |
Cu1—O3i | 1.9122 (19) | C6—C7 | 1.407 (4) |
Cu1—O5 | 2.632 (2) | C6—C5 | 1.428 (4) |
Cu1—O6ii | 2.399 (2) | C1—C2 | 1.398 (4) |
V1—O6 | 1.584 (2) | C1—H1 | 0.9300 |
V1—O5 | 1.600 (2) | C5—C4 | 1.405 (4) |
V1—O10A | 1.814 (9) | C7—C8 | 1.402 (5) |
V1—O1 | 1.831 (2) | C7—C11 | 1.436 (5) |
V1—O10B | 1.888 (14) | C4—C3 | 1.404 (5) |
P1—O3 | 1.494 (2) | C4—C12 | 1.428 (5) |
P1—O2 | 1.5103 (19) | C2—C3 | 1.361 (5) |
P1—O1 | 1.532 (2) | C2—H2 | 0.9300 |
P1—O4 | 1.563 (2) | C10—C9 | 1.400 (4) |
P2—O7 | 1.484 (2) | C10—H10 | 0.9300 |
P2—O10A | 1.505 (9) | C9—C8 | 1.364 (5) |
P2—O10B | 1.526 (14) | C9—H9 | 0.9300 |
P2—O9 | 1.527 (2) | C3—H3 | 0.9300 |
P2—O8 | 1.544 (2) | C8—H8 | 0.9300 |
O3—Cu1i | 1.9122 (19) | C12—C11 | 1.345 (6) |
N2—C1 | 1.326 (4) | C12—H12 | 0.9300 |
N2—C5 | 1.354 (3) | C11—H11 | 0.9300 |
O3i—Cu1—O2 | 94.30 (9) | C10—N1—Cu1 | 129.4 (2) |
O3i—Cu1—N2 | 172.94 (9) | C6—N1—Cu1 | 111.98 (18) |
O2—Cu1—N2 | 92.16 (9) | V1—O6—Cu1iii | 150.57 (16) |
O3i—Cu1—N1 | 91.00 (9) | P2—O10A—V1 | 164.2 (6) |
O2—Cu1—N1 | 173.99 (9) | P2—O10B—V1 | 148.6 (6) |
N2—Cu1—N1 | 82.42 (10) | N1—C6—C7 | 123.0 (3) |
O3i—Cu1—O6ii | 102.09 (10) | N1—C6—C5 | 116.6 (2) |
O2—Cu1—O6ii | 92.22 (9) | C7—C6—C5 | 120.4 (3) |
N2—Cu1—O6ii | 80.48 (10) | N2—C1—C2 | 122.1 (3) |
N1—Cu1—O6ii | 89.43 (9) | N2—C1—H1 | 119.0 |
O6—V1—O5 | 108.35 (14) | C2—C1—H1 | 119.0 |
O6—V1—O10A | 104.9 (3) | N2—C5—C4 | 123.1 (3) |
O5—V1—O10A | 116.4 (2) | N2—C5—C6 | 116.7 (2) |
O6—V1—O1 | 109.28 (12) | C4—C5—C6 | 120.3 (3) |
O5—V1—O1 | 108.71 (11) | C8—C7—C6 | 116.7 (3) |
O10A—V1—O1 | 109.0 (3) | C8—C7—C11 | 125.4 (3) |
O6—V1—O10B | 115.1 (4) | C6—C7—C11 | 117.9 (3) |
O5—V1—O10B | 99.8 (3) | C3—C4—C5 | 116.5 (3) |
O1—V1—O10B | 114.9 (4) | C3—C4—C12 | 125.4 (3) |
O3—P1—O2 | 113.73 (12) | C5—C4—C12 | 118.1 (3) |
O3—P1—O1 | 109.99 (12) | C3—C2—C1 | 119.4 (3) |
O2—P1—O1 | 111.08 (11) | C3—C2—H2 | 120.3 |
O3—P1—O4 | 109.67 (12) | C1—C2—H2 | 120.3 |
O2—P1—O4 | 104.23 (11) | N1—C10—C9 | 122.0 (3) |
O1—P1—O4 | 107.83 (12) | N1—C10—H10 | 119.0 |
O7—P2—O10A | 108.8 (4) | C9—C10—H10 | 119.0 |
O7—P2—O10B | 118.8 (5) | C8—C9—C10 | 119.7 (3) |
O10A—P2—O10B | 20.8 (3) | C8—C9—H9 | 120.2 |
O7—P2—O9 | 110.99 (12) | C10—C9—H9 | 120.2 |
O10A—P2—O9 | 117.6 (3) | C2—C3—C4 | 120.3 (3) |
O10B—P2—O9 | 96.8 (3) | C2—C3—H3 | 119.9 |
O7—P2—O8 | 108.39 (13) | C4—C3—H3 | 119.9 |
O10A—P2—O8 | 104.2 (4) | C9—C8—C7 | 120.0 (3) |
O10B—P2—O8 | 114.4 (5) | C9—C8—H8 | 120.0 |
O9—P2—O8 | 106.33 (18) | C7—C8—H8 | 120.0 |
P1—O2—Cu1 | 130.63 (12) | C11—C12—C4 | 121.8 (3) |
P1—O1—V1 | 142.85 (13) | C11—C12—H12 | 119.1 |
P1—O3—Cu1i | 139.25 (13) | C4—C12—H12 | 119.1 |
C1—N2—C5 | 118.6 (2) | C12—C11—C7 | 121.5 (3) |
C1—N2—Cu1 | 129.1 (2) | C12—C11—H11 | 119.3 |
C5—N2—Cu1 | 112.23 (18) | C7—C11—H11 | 119.3 |
C10—N1—C6 | 118.6 (2) |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x+1, y, z; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [CuV(HPO4)(H2PO4)O2(C12H8N2)] |
Mr | 519.66 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.2350 (14), 10.705 (2), 11.624 (2) |
α, β, γ (°) | 75.25 (3), 82.58 (3), 84.91 (3) |
V (Å3) | 861.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.02 |
Crystal size (mm) | 0.21 × 0.11 × 0.09 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.56, 0.80 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16352, 3031, 2737 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.076, 1.06 |
No. of reflections | 3031 |
No. of parameters | 262 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −0.49 |
Computer programs: SMART-NT (Bruker, 2001), SAINT-NT (Bruker, 1999), SHELXTL-NT (Sheldrick, 2008) and ORTEPIII (Farrugia 1997).
Cu1—N1 | 2.009 (2) | Cu1—O3i | 1.9122 (19) |
Cu1—N2 | 2.003 (2) | Cu1—O5 | 2.632 (2) |
Cu1—O2 | 1.9603 (19) | Cu1—O6ii | 2.399 (2) |
O3i—Cu1—O2 | 94.30 (9) | N2—Cu1—N1 | 82.42 (10) |
O3i—Cu1—N2 | 172.94 (9) | O3i—Cu1—O6ii | 102.09 (10) |
O2—Cu1—N2 | 92.16 (9) | O2—Cu1—O6ii | 92.22 (9) |
O3i—Cu1—N1 | 91.00 (9) | N2—Cu1—O6ii | 80.48 (10) |
O2—Cu1—N1 | 173.99 (9) | N1—Cu1—O6ii | 89.43 (9) |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x+1, y, z. |
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New materials based on hybrid organic–inorganic compounds are of interest due to their low density compared with pure inorganic materials (Yucesan et al., 2005; Feng & Xu, 2001). Functionalized phosphovanadates have been studied extensively due to their catalytic and magnetic properties. From a catalytic point of view, they are interesting due to the interplay of the different possible oxidation states, and to their high insolubility, which together make them good candidates for heterogeneous catalysis reactions. From a magnetic point of view, they are interesting due to the possibility of being functionalized by secondary paramagnetic complexes.
Vanadium oxides can possess several coordination geometries and therefore present a rich variety of structures by condensation through phosphates Yang et al., 2010; De Burgomaster et al., 2010). The presence of organic ligands can drastically modify these structures. The use of copper(II) as a secondary metal also increases the range of possible structures, due to the structural plasticity of this metal ion (Ushak et al., 2006; Venegas-Yazigi et al., 2011).
The structure of the title compound, (I), is constructed from centrosymmetric (crystallographic) bimetallic [(phen)Cu-µ-(κ2O:O-VP2O10H3)2-Cu(phen)] units (phen is 1,10-phenanthroline), shown in Fig. 1. Within this unit, the CuII environment is defined by two N atoms of the phenanthroline ligand [Cu1—N1 = 2.004 (19) and Cu1—N2 = 2.009 (2) Å], two phosphate O atoms [Cu1—O2 = 1.960 (16) and Cu1—O3i = 1.912 (17) Å; symmetry code: (i) 2 - x, 1 - y, 2 - z] and two vanadyl O atoms [Cu1—O5 = 2.622 (19) and Cu1—O6ii = 2.398 (19) Å; symmetry code: (ii) 1 + x, y, z]. Therefore, the coordination geometry can be described as a slightly distorted octahedron.
The bond-valence sum for the V atom is 5.3, assuming tetrahedral geometry (Brown & Altermatt, 1985). This fits well with the oxidation state of VV computed from the observed crystal structure. This fact, combined with charge-balance analysis, leads us to establish the phosphovanadate fragments as [VP2O10H3]2-. Both the VV and PV atoms within this anion have tetrahedral environments.
The bimetallic unit contains two [Cu(phen)]2+ fragments which are bonded through two O—P—O bridges from [VP2O10H3]2- groups. Consequently, the intermetallic distance within the unit is Cu1—Cu1i = 5.142 (2) Å.
As described above, the coordination environment of each CuII centre of the bimetallic [(phen)Cu-µ-(κ2O:O-VP2O10H3)2-Cu(phen)] unit is completed with vanadyl O atoms from neighbouring units. This leads to the formation of a covalent one-dimensional structure growing along the [100] direction. In this way, the chain is formed from two vertex-sharing VO4 tetrahedra from [VP2O10H3]2- anions connecting consecutive [(phen)Cu-µ-(κ2O:O-VP2O10H3)2-Cu(phen)] units. The phen molecules are oriented perpendicular to the chain direction. The minimum distance between two phen molecules of neighbouring units is the same as the intermetallic Cu1···Cu1ii distance of 7.235 (2) Å.
No covalent bonds exist between neighbouring chains of (I). However, the crystal structure is stabilized by π–π interactions between two adjacent phen molecules of two neighbouring chains, as shown in Fig. 2.