Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031352/wm2131sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031352/wm2131Isup2.hkl |
CoCl6.6H2O (0.90 g), MnCl2 (0.10 g), H3PO4 (0.5 ml, 75wt%) and H2O (7 ml) were mixed and transferred into a 23 ml Teflon-lined stainless steel autoclave and heated at 453 K for 3 d. Then the autoclave was cooled to room temperature at a rate of 10 K h-1. The crystalline material was separated by filtration, washed with distilled water and dried in air at room temperature. Two varieties of crystals were obtained, one with pink and one with purple colour. Single-crystal X-ray diffraction revealed that the pink crystals belong to the solid solution Mn5 - xCox(HPO4)2(PO4)2(H2O)4 (Larrea et al., 2007), whereas the purple crystals could be assigned to the title compound (I). Their composition is in good agreement with the results of the energy dispersive spectrometrical (EDS) analysis (weight percentage): Mn, 14.5%; Co, 26.9%; P, 19.2% and O, 39.4%.
The site occupation factors for all metal sites were refined with their sums constrained to unity. The metal positions M1 are occupied by 73% Co and 27% Mn, M2 by 42% Co and 58% Mn, M3 by 80% Co and 20% Mn, and M4 by 54% Co and 58% Mn. H atoms of the hydrogenphosphate anion were localized in Fourier maps and were refined isotropically, with an O—H distance restraint of 0.85 (1) Å. The highest peak and the deepest hole in the final Fourier map are located 0.36 and 0.38 Å, respectively, from O1.
A large variety of Co(II) and Mn(II) phosphates is known and many of the corresponding compounds crystallize isotypically, for instance Mn5(OH)5(PO4)2 and Co5(OH)5(PO4)2 (Ruszala et al., 1977), Mn(H2PO4)2.2H2O and Co(H2PO4)2.2H2O (Boudjada & Durif, 1979; Effenberger, 1992), Mn5(HPO4)2(PO4)2(H2O)4 and Co5(HPO4)2(PO4)2(H2O)4 (Han et al., 2006; Menchetti & Sabelli, 1973; Gerault et al., 1987), and Mn7(HPO4)4(PO4)2 and Co7(HPO4)4(PO4)2 (Riou et al., 1987; Lightfoot & Cheetham, 1988). Hydrothermal and solvothermal methods have been used to synthesize numerous novel transition metal phosphates with three-dimensional framework structures such as Fe (Zhou et al., 2002), Co (Lightfoot et al., 1988) and Mn (Riou et al., 1987) containing phosphates.
The title compound, (I), is a solid solution in the series Co7 - xMnx(HPO4)4(PO4)2 with x = 2.68, and crystallizes in the Fe7(PO4)6 structure type. It is isotypic with the end members M7(HPO4)4(PO4)2 (M = Mn, Co). The asymmetric unit of the structure is shown in Fig. 1. The crystal structure consists of a complex framework built up from edge-sharing MO6 and MO5 polyhedra that are linked via corner-sharing with PO4 tetrahedra into a three-dimensional framework (Fig. 2). The four metal positions are statistically occupied by Co and Mn. The metal position M2 is located on an inversion centre and has a slightly distorted octahedral coordination environment while the M1 and M3 sites exhibit more distorted octahedra. The metal position M4 is surrounded by five O atoms to give a coordination polyhedron which is best described as an irregular trigonal bipyramid (Fig. 2, Table 1).
The M—O distances range from 2.0604 (11) Å to 2.2430 (12) Å and agree with those found in the solid solution Mn5 - xCox(HPO4)2(PO4)2(H2O)4 (x = 1.25, 2, 2.5 and 3; Larrea et al., 2007). The fully deprotonized orthophosphate groups deviate slightly from the ideal tetrahedral geometry, with P—O bond lenghts ranging from 1.5298 (11) to 1.5512 (11) Å, which is in good agreement with those reported for other divalent-metal compounds with PO4 groups (Nord, 1986). The two HPO4 groups exhibit elongated P—O bonds of 1.5777 (11) Å (P1—O3) and 1.5799 (12) Å (P2—O7) which is characteristic for P—OH distances of acidic phosphates and confirms the location of the H atoms (Table 1). Strong O—H···.O hydrogen bonds help to consolidate the crystal structure (Table 2).
The hydrothermal preparation of transition metal phosphates has been described for M = Fe (Zhou et al., 2002), Co (Lightfoot & Cheetham, 1988) and Mn (Riou et al., 1987). For isotypic phosphates with M = Co or Mn, see: M5(OH)5(PO4)2 (Ruszala et al., 1977), M(H2PO4)2.2H2O (Boudjada & Durif, 1979; Effenberger, 1992), M5(HPO4)2(PO4)2(H2O)4 (Han et al., 2006; Menchetti & Sabelli, 1973; Gerault et al., 1987) and M7(HPO4)4(PO4)2 (Riou et al., 1987; Lightfoot et al., 1988). The solid solution series Mn5 - xCox(HPO4)2(PO4)2(H2O)4 (x = 1.25, 2, 2.5 and 3) was characterized by Larrea et al. (2007). The geometry of the PO4 tetrahedron has been reviewed by Nord (1986).
Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).
Co4.32Mn2.68(HPO4)4(PO4)2 | Z = 1 |
Mr = 974.07 | F(000) = 469.6 |
Triclinic, P1 | Dx = 3.739 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5119 (12) Å | Cell parameters from 9895 reflections |
b = 7.9623 (12) Å | θ = 2.4–40.1° |
c = 9.5799 (10) Å | µ = 6.65 mm−1 |
α = 104.428 (3)° | T = 293 K |
β = 109.180 (1)° | Prism, colourless |
γ = 101.389 (3)° | 0.10 × 0.10 × 0.10 mm |
V = 432.64 (11) Å3 |
Bruker APEXII CCD area-detector diffractometer | Rint = 0.022 |
Graphite monochromator | θmax = 40.4°, θmin = 2.4° |
φ and ω scans | h = −11→9 |
10685 measured reflections | k = −13→14 |
5484 independent reflections | l = −16→17 |
4111 reflections with I > 2σ(I) |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0676P)2 + 0.8077P] where P = (Fo2 + 2Fc2)/3 |
5484 reflections | (Δ/σ)max = 0.001 |
171 parameters | Δρmax = 1.06 e Å−3 |
0 restraints | Δρmin = −0.82 e Å−3 |
Co4.32Mn2.68(HPO4)4(PO4)2 | γ = 101.389 (3)° |
Mr = 974.07 | V = 432.64 (11) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.5119 (12) Å | Mo Kα radiation |
b = 7.9623 (12) Å | µ = 6.65 mm−1 |
c = 9.5799 (10) Å | T = 293 K |
α = 104.428 (3)° | 0.10 × 0.10 × 0.10 mm |
β = 109.180 (1)° |
Bruker APEXII CCD area-detector diffractometer | 4111 reflections with I > 2σ(I) |
10685 measured reflections | Rint = 0.022 |
5484 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 1.06 e Å−3 |
5484 reflections | Δρmin = −0.82 e Å−3 |
171 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) | |
Co3 | 0.38449 (3) | 0.45668 (3) | 0.10926 (2) | 0.00799 (5) | 0.796 (12) |
Mn3 | 0.38449 (3) | 0.45668 (3) | 0.10926 (2) | 0.00799 (5) | 0.204 (12) |
Co1 | 0.05082 (4) | 0.71421 (3) | 0.51524 (2) | 0.00797 (5) | 0.729 (12) |
Mn1 | 0.05082 (4) | 0.71421 (3) | 0.51524 (2) | 0.00797 (5) | 0.271 (12) |
Co2 | 0.0000 | 0.0000 | 0.0000 | 0.00878 (7) | 0.418 (16) |
Mn2 | 0.0000 | 0.0000 | 0.0000 | 0.00878 (7) | 0.582 (16) |
Co4 | 0.28343 (4) | 0.81332 (3) | 0.28480 (3) | 0.00936 (6) | 0.424 (12) |
Mn4 | 0.28343 (4) | 0.81332 (3) | 0.28480 (3) | 0.00936 (6) | 0.576 (12) |
P1 | 0.22577 (6) | 0.14388 (5) | −0.22339 (4) | 0.00662 (7) | |
P3 | −0.08771 (6) | 0.42078 (5) | 0.17407 (4) | 0.00616 (7) | |
P2 | 0.41114 (6) | 1.23356 (5) | 0.37360 (5) | 0.00817 (7) | |
O4 | 0.22221 (19) | 0.18779 (14) | −0.05752 (13) | 0.00969 (18) | |
O2 | 0.44797 (18) | 0.24541 (14) | −0.22778 (13) | 0.00928 (18) | |
O6 | 0.4801 (2) | 1.38550 (15) | 0.31163 (14) | 0.0130 (2) | |
O7 | 0.27261 (19) | 1.29718 (16) | 0.47367 (14) | 0.0125 (2) | |
O5 | 0.61929 (19) | 1.20780 (16) | 0.48908 (14) | 0.0124 (2) | |
O3 | 0.2064 (2) | −0.06486 (14) | −0.27465 (13) | 0.01030 (19) | |
O8 | 0.26319 (19) | 1.05504 (14) | 0.24010 (13) | 0.0118 (2) | |
O10 | 0.12308 (18) | 0.53885 (14) | 0.16495 (13) | 0.00955 (18) | |
O9 | −0.30343 (17) | 0.46328 (14) | 0.08719 (13) | 0.00871 (18) | |
O11 | −0.05564 (19) | 0.45695 (14) | 0.34663 (12) | 0.00933 (18) | |
O12 | −0.1130 (2) | 0.21731 (14) | 0.09879 (14) | 0.0118 (2) | |
O1 | 0.01773 (19) | 0.16985 (14) | −0.33822 (13) | 0.00999 (18)* | |
H1P | 0.184 (5) | −0.105 (4) | −0.205 (3) | 0.050* | |
H2P | 0.341 (5) | 1.401 (2) | 0.545 (3) | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co3 | 0.00736 (9) | 0.00902 (9) | 0.00765 (9) | 0.00258 (6) | 0.00323 (7) | 0.00255 (7) |
Mn3 | 0.00736 (9) | 0.00902 (9) | 0.00765 (9) | 0.00258 (6) | 0.00323 (7) | 0.00255 (7) |
Co1 | 0.00849 (9) | 0.00820 (9) | 0.00707 (9) | 0.00228 (6) | 0.00329 (7) | 0.00231 (7) |
Mn1 | 0.00849 (9) | 0.00820 (9) | 0.00707 (9) | 0.00228 (6) | 0.00329 (7) | 0.00231 (7) |
Co2 | 0.00994 (14) | 0.00837 (12) | 0.00859 (13) | 0.00261 (10) | 0.00466 (11) | 0.00262 (10) |
Mn2 | 0.00994 (14) | 0.00837 (12) | 0.00859 (13) | 0.00261 (10) | 0.00466 (11) | 0.00262 (10) |
Co4 | 0.00927 (10) | 0.00836 (9) | 0.01135 (10) | 0.00333 (7) | 0.00496 (8) | 0.00313 (7) |
Mn4 | 0.00927 (10) | 0.00836 (9) | 0.01135 (10) | 0.00333 (7) | 0.00496 (8) | 0.00313 (7) |
P1 | 0.00609 (15) | 0.00688 (14) | 0.00704 (15) | 0.00198 (11) | 0.00281 (12) | 0.00232 (11) |
P3 | 0.00582 (14) | 0.00670 (13) | 0.00642 (15) | 0.00232 (11) | 0.00254 (12) | 0.00254 (11) |
P2 | 0.00638 (15) | 0.00853 (14) | 0.00817 (16) | 0.00225 (11) | 0.00178 (12) | 0.00199 (12) |
O4 | 0.0116 (5) | 0.0090 (4) | 0.0076 (4) | 0.0015 (3) | 0.0045 (4) | 0.0017 (3) |
O2 | 0.0076 (4) | 0.0090 (4) | 0.0111 (5) | 0.0009 (3) | 0.0049 (4) | 0.0027 (3) |
O6 | 0.0136 (5) | 0.0119 (4) | 0.0119 (5) | 0.0006 (4) | 0.0037 (4) | 0.0057 (4) |
O7 | 0.0089 (5) | 0.0161 (5) | 0.0107 (5) | 0.0037 (4) | 0.0044 (4) | 0.0010 (4) |
O5 | 0.0090 (5) | 0.0195 (5) | 0.0099 (5) | 0.0072 (4) | 0.0031 (4) | 0.0056 (4) |
O3 | 0.0146 (5) | 0.0071 (4) | 0.0104 (5) | 0.0032 (4) | 0.0069 (4) | 0.0024 (3) |
O8 | 0.0111 (5) | 0.0104 (4) | 0.0097 (5) | 0.0009 (4) | 0.0022 (4) | 0.0010 (4) |
O10 | 0.0072 (4) | 0.0103 (4) | 0.0113 (5) | 0.0017 (3) | 0.0047 (4) | 0.0033 (4) |
O9 | 0.0063 (4) | 0.0119 (4) | 0.0083 (4) | 0.0038 (3) | 0.0021 (4) | 0.0043 (4) |
O11 | 0.0122 (5) | 0.0097 (4) | 0.0058 (4) | 0.0036 (3) | 0.0030 (4) | 0.0028 (3) |
O12 | 0.0161 (5) | 0.0078 (4) | 0.0136 (5) | 0.0050 (4) | 0.0081 (4) | 0.0029 (4) |
M1—O11 | 2.0833 (11) | P1—O4 | 1.5486 (11) |
M1—O3i | 2.0890 (11) | P1—O3 | 1.5777 (11) |
M1—O1ii | 2.0911 (11) | P2—O8 | 1.5257 (12) |
M1—O11iii | 2.1208 (11) | P2—O6 | 1.5285 (12) |
M1—O7iv | 2.1288 (12) | P2—O5 | 1.5300 (12) |
M1—O5v | 2.1322 (12) | P2—O7 | 1.5799 (12) |
M2—O12 | 2.1390 (11) | P3—O9 | 1.5298 (11) |
M2—O12vi | 2.1390 (11) | P3—O11 | 1.5400 (11) |
M2—O4vi | 2.1710 (11) | P3—O10 | 1.5445 (11) |
M2—O4 | 2.1710 (11) | P3—O12 | 1.5512 (11) |
M2—O8vii | 2.2430 (12) | O2—M4ix | 2.0976 (11) |
M2—O8ii | 2.2430 (12) | O2—M3ix | 2.2199 (11) |
M3—O9ii | 2.0748 (11) | O6—M3x | 2.0882 (12) |
M3—O6vii | 2.0882 (12) | O7—M1iv | 2.1288 (12) |
M3—O9viii | 2.1032 (11) | O7—H2P | 0.85 (3) |
M3—O10 | 2.1149 (11) | O5—M4v | 2.1081 (12) |
M3—O4 | 2.1320 (11) | O5—M1v | 2.1322 (12) |
M3—O2ix | 2.2199 (11) | O3—M1xi | 2.0890 (11) |
M3—M3ix | 3.0824 (5) | O3—H1P | 0.85 (3) |
M4—O10 | 2.0604 (11) | O8—M2x | 2.2430 (12) |
M4—O8 | 2.0926 (12) | O9—M3ii | 2.0748 (11) |
M4—O2ix | 2.0976 (11) | O9—M3xii | 2.1032 (11) |
M4—O5v | 2.1081 (12) | O11—M1iii | 2.1208 (11) |
M4—O1ii | 2.2034 (12) | O1—M1ii | 2.0911 (11) |
P1—O1 | 1.5274 (12) | O1—M4ii | 2.2034 (12) |
P1—O2 | 1.5310 (11) | ||
O9ii—M3—O6vii | 177.41 (4) | O1—P1—O4 | 110.72 (6) |
O9ii—M3—O9viii | 84.92 (4) | O2—P1—O4 | 114.57 (6) |
O6vii—M3—O9viii | 93.39 (4) | O1—P1—O3 | 108.54 (6) |
O9ii—M3—O10 | 91.88 (4) | O2—P1—O3 | 106.78 (6) |
O6vii—M3—O10 | 89.13 (5) | O4—P1—O3 | 104.08 (6) |
O9viii—M3—O10 | 161.97 (4) | O9—P3—O11 | 108.96 (6) |
O9ii—M3—O4 | 84.43 (4) | O9—P3—O10 | 110.59 (6) |
O6vii—M3—O4 | 97.60 (4) | O11—P3—O10 | 110.28 (6) |
O9viii—M3—O4 | 91.92 (4) | O9—P3—O12 | 109.91 (6) |
O10—M3—O4 | 105.44 (4) | O11—P3—O12 | 108.53 (6) |
O9ii—M3—O2ix | 81.10 (4) | O10—P3—O12 | 108.55 (6) |
O6vii—M3—O2ix | 96.76 (4) | O8—P2—O6 | 111.66 (7) |
O9viii—M3—O2ix | 83.03 (4) | O8—P2—O5 | 111.13 (7) |
O10—M3—O2ix | 78.94 (4) | O6—P2—O5 | 111.70 (7) |
O4—M3—O2ix | 165.03 (4) | O8—P2—O7 | 109.60 (6) |
O9ii—M3—M3ix | 42.81 (3) | O6—P2—O7 | 107.40 (7) |
O6vii—M3—M3ix | 135.46 (4) | O5—P2—O7 | 105.06 (7) |
O9viii—M3—M3ix | 42.10 (3) | P1—O4—M3 | 120.45 (6) |
O10—M3—M3ix | 132.14 (3) | P1—O4—M2 | 122.03 (6) |
O4—M3—M3ix | 87.57 (3) | M3—O4—M2 | 116.38 (5) |
O2ix—M3—M3ix | 79.23 (3) | P1—O2—M4ix | 138.88 (6) |
O11—M1—O3i | 163.60 (4) | P1—O2—M4ix | 138.88 (6) |
O11—M1—O1ii | 90.18 (4) | P1—O2—M3ix | 123.34 (6) |
O3i—M1—O1ii | 105.01 (4) | M4ix—O2—M3ix | 96.67 (4) |
O11—M1—O11iii | 78.20 (5) | M4ix—O2—M3ix | 96.67 (4) |
O3i—M1—O11iii | 87.39 (4) | P1—O2—M3ix | 123.34 (6) |
O1ii—M1—O11iii | 166.41 (4) | M4ix—O2—M3ix | 96.67 (4) |
O11—M1—O7iv | 96.03 (4) | P2—O6—M3x | 141.22 (7) |
O3i—M1—O7iv | 89.65 (4) | P2—O7—M1iv | 148.04 (7) |
O1ii—M1—O7iv | 92.17 (5) | P2—O7—H2P | 114 (2) |
O11iii—M1—O7iv | 82.20 (4) | M1iv—O7—H2P | 94 (2) |
O11—M1—O5v | 94.92 (4) | M1iv—O7—H2P | 94 (2) |
O3i—M1—O5v | 82.07 (5) | P2—O5—M4v | 136.06 (7) |
O1ii—M1—O5v | 79.53 (4) | P2—O5—M1v | 121.90 (7) |
O11iii—M1—O5v | 108.19 (4) | M4v—O5—M1v | 98.92 (5) |
O7iv—M1—O5v | 166.27 (5) | P2—O5—M1v | 121.90 (7) |
O12—M2—O12vi | 180.00 (6) | M4v—O5—M1v | 98.92 (5) |
O12—M2—O4vi | 90.32 (4) | P1—O3—M1xi | 135.93 (7) |
O12vi—M2—O4vi | 89.68 (4) | P1—O3—M1xi | 135.93 (7) |
O12—M2—O4 | 89.68 (4) | P1—O3—H1P | 107.8 (19) |
O12vi—M2—O4 | 90.32 (4) | M1xi—O3—H1P | 106 (2) |
O4vi—M2—O4 | 180.00 (5) | M1xi—O3—H1P | 106 (2) |
O12—M2—O8vii | 89.04 (4) | P2—O8—M4 | 117.24 (7) |
O12vi—M2—O8vii | 90.96 (4) | P2—O8—M2x | 131.08 (7) |
O4vi—M2—O8vii | 85.96 (4) | M4—O8—M2x | 111.53 (5) |
O4—M2—O8vii | 94.04 (4) | M4—O8—M2x | 111.53 (5) |
O12—M2—O8ii | 90.96 (4) | P3—O10—M4 | 126.48 (6) |
O12vi—M2—O8ii | 89.04 (4) | P3—O10—M3 | 128.41 (6) |
O4vi—M2—O8ii | 94.04 (4) | M4—O10—M3 | 101.20 (5) |
O4—M2—O8ii | 85.96 (4) | P3—O9—M3ii | 129.37 (6) |
O8vii—M2—O8ii | 180.00 (6) | P3—O9—M3xii | 135.51 (7) |
O10—M4—O8 | 136.28 (5) | M3ii—O9—M3xii | 95.08 (4) |
O10—M4—O2ix | 83.06 (4) | P3—O9—M3xii | 135.51 (7) |
O8—M4—O2ix | 105.04 (4) | M3ii—O9—M3xii | 95.08 (4) |
O10—M4—O5v | 95.67 (5) | P3—O11—M1 | 124.87 (6) |
O8—M4—O5v | 123.79 (5) | P3—O11—M1iii | 132.69 (6) |
O2ix—M4—O5v | 100.18 (4) | M1—O11—M1iii | 101.80 (5) |
O10—M4—O1ii | 88.72 (4) | M1—O11—M1iii | 101.80 (5) |
O8—M4—O1ii | 83.01 (4) | P3—O12—M2 | 153.67 (7) |
O2ix—M4—O1ii | 171.24 (4) | P1—O1—M1ii | 137.39 (7) |
O5v—M4—O1ii | 77.56 (4) | P1—O1—M4ii | 121.67 (6) |
O1—P1—O2 | 111.62 (6) | M1ii—O1—M4ii | 97.21 (4) |
Symmetry codes: (i) x, y+1, z+1; (ii) −x, −y+1, −z; (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1; (v) −x+1, −y+2, −z+1; (vi) −x, −y, −z; (vii) x, y−1, z; (viii) x+1, y, z; (ix) −x+1, −y+1, −z; (x) x, y+1, z; (xi) x, y−1, z−1; (xii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1P···O12vi | 0.85 (3) | 1.63 (3) | 2.4663 (18) | 169 (3) |
O7—H2P···O6xiii | 0.85 (2) | 1.77 (2) | 2.6143 (18) | 172 (3) |
Symmetry codes: (vi) −x, −y, −z; (xiii) −x+1, −y+3, −z+1. |
Experimental details
Crystal data | |
Chemical formula | Co4.32Mn2.68(HPO4)4(PO4)2 |
Mr | 974.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.5119 (12), 7.9623 (12), 9.5799 (10) |
α, β, γ (°) | 104.428 (3), 109.180 (1), 101.389 (3) |
V (Å3) | 432.64 (11) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 6.65 |
Crystal size (mm) | 0.10 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10685, 5484, 4111 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.911 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.064, 1.05 |
No. of reflections | 5484 |
No. of parameters | 171 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.06, −0.82 |
Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2001), WinGX (Farrugia, 1999).
M1—O11 | 2.0833 (11) | M4—O10 | 2.0604 (11) |
M1—O3i | 2.0890 (11) | M4—O8 | 2.0926 (12) |
M1—O1ii | 2.0911 (11) | M4—O2ix | 2.0976 (11) |
M1—O11iii | 2.1208 (11) | M4—O5v | 2.1081 (12) |
M1—O7iv | 2.1288 (12) | M4—O1ii | 2.2034 (12) |
M1—O5v | 2.1322 (12) | P1—O1 | 1.5274 (12) |
M2—O12 | 2.1390 (11) | P1—O2 | 1.5310 (11) |
M2—O12vi | 2.1390 (11) | P1—O4 | 1.5486 (11) |
M2—O4vi | 2.1710 (11) | P1—O3 | 1.5777 (11) |
M2—O4 | 2.1710 (11) | P2—O8 | 1.5257 (12) |
M2—O8vii | 2.2430 (12) | P2—O6 | 1.5285 (12) |
M2—O8ii | 2.2430 (12) | P2—O5 | 1.5300 (12) |
M3—O9ii | 2.0748 (11) | P2—O7 | 1.5799 (12) |
M3—O6vii | 2.0882 (12) | P3—O9 | 1.5298 (11) |
M3—O9viii | 2.1032 (11) | P3—O11 | 1.5400 (11) |
M3—O10 | 2.1149 (11) | P3—O10 | 1.5445 (11) |
M3—O4 | 2.1320 (11) | P3—O12 | 1.5512 (11) |
M3—O2ix | 2.2199 (11) |
Symmetry codes: (i) x, y+1, z+1; (ii) −x, −y+1, −z; (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1; (v) −x+1, −y+2, −z+1; (vi) −x, −y, −z; (vii) x, y−1, z; (viii) x+1, y, z; (ix) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1P···O12vi | 0.85 (3) | 1.63 (3) | 2.4663 (18) | 169 (3) |
O7—H2P···O6x | 0.85 (2) | 1.77 (2) | 2.6143 (18) | 172 (3) |
Symmetry codes: (vi) −x, −y, −z; (x) −x+1, −y+3, −z+1. |
A large variety of Co(II) and Mn(II) phosphates is known and many of the corresponding compounds crystallize isotypically, for instance Mn5(OH)5(PO4)2 and Co5(OH)5(PO4)2 (Ruszala et al., 1977), Mn(H2PO4)2.2H2O and Co(H2PO4)2.2H2O (Boudjada & Durif, 1979; Effenberger, 1992), Mn5(HPO4)2(PO4)2(H2O)4 and Co5(HPO4)2(PO4)2(H2O)4 (Han et al., 2006; Menchetti & Sabelli, 1973; Gerault et al., 1987), and Mn7(HPO4)4(PO4)2 and Co7(HPO4)4(PO4)2 (Riou et al., 1987; Lightfoot & Cheetham, 1988). Hydrothermal and solvothermal methods have been used to synthesize numerous novel transition metal phosphates with three-dimensional framework structures such as Fe (Zhou et al., 2002), Co (Lightfoot et al., 1988) and Mn (Riou et al., 1987) containing phosphates.
The title compound, (I), is a solid solution in the series Co7 - xMnx(HPO4)4(PO4)2 with x = 2.68, and crystallizes in the Fe7(PO4)6 structure type. It is isotypic with the end members M7(HPO4)4(PO4)2 (M = Mn, Co). The asymmetric unit of the structure is shown in Fig. 1. The crystal structure consists of a complex framework built up from edge-sharing MO6 and MO5 polyhedra that are linked via corner-sharing with PO4 tetrahedra into a three-dimensional framework (Fig. 2). The four metal positions are statistically occupied by Co and Mn. The metal position M2 is located on an inversion centre and has a slightly distorted octahedral coordination environment while the M1 and M3 sites exhibit more distorted octahedra. The metal position M4 is surrounded by five O atoms to give a coordination polyhedron which is best described as an irregular trigonal bipyramid (Fig. 2, Table 1).
The M—O distances range from 2.0604 (11) Å to 2.2430 (12) Å and agree with those found in the solid solution Mn5 - xCox(HPO4)2(PO4)2(H2O)4 (x = 1.25, 2, 2.5 and 3; Larrea et al., 2007). The fully deprotonized orthophosphate groups deviate slightly from the ideal tetrahedral geometry, with P—O bond lenghts ranging from 1.5298 (11) to 1.5512 (11) Å, which is in good agreement with those reported for other divalent-metal compounds with PO4 groups (Nord, 1986). The two HPO4 groups exhibit elongated P—O bonds of 1.5777 (11) Å (P1—O3) and 1.5799 (12) Å (P2—O7) which is characteristic for P—OH distances of acidic phosphates and confirms the location of the H atoms (Table 1). Strong O—H···.O hydrogen bonds help to consolidate the crystal structure (Table 2).