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Single crystals of the solid solution cobalt manganese tetra­kis(hydrogen phosphate) bis­(phosphate), Co4.32Mn2.68(HPO4)4(PO4)2, have been prepared under hydro­thermal conditions. The compound crystallizes in the Fe7(PO4)6 structure type and is isotypic with the Co and Mn end members of the solid solution Co7-xMnx(HPO4)4(PO4)2. The structure is based on a three-dimensional framework of distorted edge-sharing MO6 and MO5 polyhedra (M = Co or Mn) which are inter­linked by corner-sharing with PO4 tetra­hedra. The four metal positions are statistically occupied by Co and Mn. Strong hydrogen bonds between the OH groups of the HPO4 tetra­hedra and the O atoms help to consolidate the crystal structure. Except for one metal site located on a position with \overline{1} symmetry, all atoms are on general positions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031352/wm2131sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031352/wm2131Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](P-O) = 0.001 Å
  • Disorder in main residue
  • R factor = 0.027
  • wR factor = 0.064
  • Data-to-parameter ratio = 32.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms .. ? PLAT301_ALERT_3_C Main Residue Disorder ......................... 14.00 Perc. PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 M1 O11 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 M1 O3 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 M1 O1 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 M1 O11 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 M1 O7 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 M1 O5 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M2 M2 O12 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M2 M2 O12 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M2 M2 O4 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M2 M2 O4 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M2 M2 O8 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M2 M2 O8 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 M3 O9 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 M3 O6 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 M3 O9 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 M3 O10 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 M3 O4 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 M3 O2 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 M3 M3 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M4 M4 O10 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M4 M4 O8 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M4 M4 O2 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M4 M4 O5 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M4 M4 O1 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M4 O2 M4 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 O2 M3 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 O6 M3 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 O7 M1 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M4 O5 M4 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 O5 M1 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 O3 M1 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M2 O8 M2 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 O9 M3 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M3 O9 M3 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 O11 M1 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M1 O1 M1 PLAT711_ALERT_1_C BOND Unknown or Inconsistent Label .......... M4 O1 M4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 O6 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 O9 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O6 M3 O9 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 O10 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O6 M3 O10 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 O10 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O6 M3 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O10 M3 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 O2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O6 M3 O2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 O2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O10 M3 O2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O4 M3 O2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O6 M3 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O9 M3 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O10 M3 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O4 M3 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 O2 M3 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O11 M1 O3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O11 M1 O1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O3 M1 O1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O11 M1 O11 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O3 M1 O11 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O1 M1 O11 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O11 M1 O7 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O3 M1 O7 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O1 M1 O7 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O11 M1 O7 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O11 M1 O5 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O3 M1 O5 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O1 M1 O5 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O11 M1 O5 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 O7 M1 O5 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O12 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O4 M2 O4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O4 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O4 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O12 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O4 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O4 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 O8 M2 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O10 M4 O8 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O10 M4 O2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O8 M4 O2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O10 M4 O5 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O8 M4 O5 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O2 M4 O5 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O10 M4 O1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O8 M4 O1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O2 M4 O1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 O5 M4 O1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 P1 O4 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 P1 O4 M2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 M3 O4 M2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 P1 O2 M4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 P1 O2 M4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 P1 O2 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 M4 O2 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 M4 O2 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 P1 O2 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 M4 O2 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 P2 O6 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 P2 O7 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 M1 O7 H2P PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 M1 O7 H2P PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 P2 O5 M4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 P2 O5 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 M4 O5 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 P2 O5 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 M4 O5 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 P1 O3 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 P1 O3 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 M1 O3 H1P PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 M1 O3 H1P PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 P2 O8 M4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 P2 O8 M2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 M4 O8 M2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 M4 O8 M2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 P3 O10 M4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 P3 O10 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 M4 O10 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 P3 O9 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 P3 O9 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 M3 O9 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 P3 O9 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M3 M3 O9 M3 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 P3 O11 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 P3 O11 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 M1 O11 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 M1 O11 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M2 P3 O12 M2 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 P1 O1 M1 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M4 P1 O1 M4 PLAT712_ALERT_1_C ANGLE Unknown or Inconsistent Label .......... M1 M1 O1 M4
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT793_ALERT_1_G Check the Absolute Configuration of P1 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of P2 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of P3 = ... S PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............ 4 Times
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 144 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 145 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

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).

Experimental top

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%.

Refinement top

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.

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) with atom labels (M = Co, Mn), drawn with displacement ellipsoids at the 50% probability level for all non-H atoms. H atoms are given as spheres of arbitrary radius.
[Figure 2] Fig. 2. Polyhedral representation of (I) showing the framework structure as viewed along the b axis. MO5 polyhedra are displayed in blue and MO6 polyhedra in green.
cobalt manganese tetrakis(hydrogen phosphate) bis(phosphate) top
Crystal data top
Co4.32Mn2.68(HPO4)4(PO4)2Z = 1
Mr = 974.07F(000) = 469.6
Triclinic, P1Dx = 3.739 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.5119 (12) ÅCell parameters from 9895 reflections
b = 7.9623 (12) Åθ = 2.4–40.1°
c = 9.5799 (10) ŵ = 6.65 mm1
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
Data collection top
Bruker APEXII CCD area-detector
diffractometer
Rint = 0.022
Graphite monochromatorθmax = 40.4°, θmin = 2.4°
φ and ω scansh = 119
10685 measured reflectionsk = 1314
5484 independent reflectionsl = 1617
4111 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H 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 parametersΔρmax = 1.06 e Å3
0 restraintsΔρmin = 0.82 e Å3
Crystal data top
Co4.32Mn2.68(HPO4)4(PO4)2γ = 101.389 (3)°
Mr = 974.07V = 432.64 (11) Å3
Triclinic, P1Z = 1
a = 6.5119 (12) ÅMo Kα radiation
b = 7.9623 (12) ŵ = 6.65 mm1
c = 9.5799 (10) ÅT = 293 K
α = 104.428 (3)°0.10 × 0.10 × 0.10 mm
β = 109.180 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
4111 reflections with I > 2σ(I)
10685 measured reflectionsRint = 0.022
5484 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 1.06 e Å3
5484 reflectionsΔρmin = 0.82 e Å3
171 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co30.38449 (3)0.45668 (3)0.10926 (2)0.00799 (5)0.796 (12)
Mn30.38449 (3)0.45668 (3)0.10926 (2)0.00799 (5)0.204 (12)
Co10.05082 (4)0.71421 (3)0.51524 (2)0.00797 (5)0.729 (12)
Mn10.05082 (4)0.71421 (3)0.51524 (2)0.00797 (5)0.271 (12)
Co20.00000.00000.00000.00878 (7)0.418 (16)
Mn20.00000.00000.00000.00878 (7)0.582 (16)
Co40.28343 (4)0.81332 (3)0.28480 (3)0.00936 (6)0.424 (12)
Mn40.28343 (4)0.81332 (3)0.28480 (3)0.00936 (6)0.576 (12)
P10.22577 (6)0.14388 (5)0.22339 (4)0.00662 (7)
P30.08771 (6)0.42078 (5)0.17407 (4)0.00616 (7)
P20.41114 (6)1.23356 (5)0.37360 (5)0.00817 (7)
O40.22221 (19)0.18779 (14)0.05752 (13)0.00969 (18)
O20.44797 (18)0.24541 (14)0.22778 (13)0.00928 (18)
O60.4801 (2)1.38550 (15)0.31163 (14)0.0130 (2)
O70.27261 (19)1.29718 (16)0.47367 (14)0.0125 (2)
O50.61929 (19)1.20780 (16)0.48908 (14)0.0124 (2)
O30.2064 (2)0.06486 (14)0.27465 (13)0.01030 (19)
O80.26319 (19)1.05504 (14)0.24010 (13)0.0118 (2)
O100.12308 (18)0.53885 (14)0.16495 (13)0.00955 (18)
O90.30343 (17)0.46328 (14)0.08719 (13)0.00871 (18)
O110.05564 (19)0.45695 (14)0.34663 (12)0.00933 (18)
O120.1130 (2)0.21731 (14)0.09879 (14)0.0118 (2)
O10.01773 (19)0.16985 (14)0.33822 (13)0.00999 (18)*
H1P0.184 (5)0.105 (4)0.205 (3)0.050*
H2P0.341 (5)1.401 (2)0.545 (3)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co30.00736 (9)0.00902 (9)0.00765 (9)0.00258 (6)0.00323 (7)0.00255 (7)
Mn30.00736 (9)0.00902 (9)0.00765 (9)0.00258 (6)0.00323 (7)0.00255 (7)
Co10.00849 (9)0.00820 (9)0.00707 (9)0.00228 (6)0.00329 (7)0.00231 (7)
Mn10.00849 (9)0.00820 (9)0.00707 (9)0.00228 (6)0.00329 (7)0.00231 (7)
Co20.00994 (14)0.00837 (12)0.00859 (13)0.00261 (10)0.00466 (11)0.00262 (10)
Mn20.00994 (14)0.00837 (12)0.00859 (13)0.00261 (10)0.00466 (11)0.00262 (10)
Co40.00927 (10)0.00836 (9)0.01135 (10)0.00333 (7)0.00496 (8)0.00313 (7)
Mn40.00927 (10)0.00836 (9)0.01135 (10)0.00333 (7)0.00496 (8)0.00313 (7)
P10.00609 (15)0.00688 (14)0.00704 (15)0.00198 (11)0.00281 (12)0.00232 (11)
P30.00582 (14)0.00670 (13)0.00642 (15)0.00232 (11)0.00254 (12)0.00254 (11)
P20.00638 (15)0.00853 (14)0.00817 (16)0.00225 (11)0.00178 (12)0.00199 (12)
O40.0116 (5)0.0090 (4)0.0076 (4)0.0015 (3)0.0045 (4)0.0017 (3)
O20.0076 (4)0.0090 (4)0.0111 (5)0.0009 (3)0.0049 (4)0.0027 (3)
O60.0136 (5)0.0119 (4)0.0119 (5)0.0006 (4)0.0037 (4)0.0057 (4)
O70.0089 (5)0.0161 (5)0.0107 (5)0.0037 (4)0.0044 (4)0.0010 (4)
O50.0090 (5)0.0195 (5)0.0099 (5)0.0072 (4)0.0031 (4)0.0056 (4)
O30.0146 (5)0.0071 (4)0.0104 (5)0.0032 (4)0.0069 (4)0.0024 (3)
O80.0111 (5)0.0104 (4)0.0097 (5)0.0009 (4)0.0022 (4)0.0010 (4)
O100.0072 (4)0.0103 (4)0.0113 (5)0.0017 (3)0.0047 (4)0.0033 (4)
O90.0063 (4)0.0119 (4)0.0083 (4)0.0038 (3)0.0021 (4)0.0043 (4)
O110.0122 (5)0.0097 (4)0.0058 (4)0.0036 (3)0.0030 (4)0.0028 (3)
O120.0161 (5)0.0078 (4)0.0136 (5)0.0050 (4)0.0081 (4)0.0029 (4)
Geometric parameters (Å, º) top
M1—O112.0833 (11)P1—O41.5486 (11)
M1—O3i2.0890 (11)P1—O31.5777 (11)
M1—O1ii2.0911 (11)P2—O81.5257 (12)
M1—O11iii2.1208 (11)P2—O61.5285 (12)
M1—O7iv2.1288 (12)P2—O51.5300 (12)
M1—O5v2.1322 (12)P2—O71.5799 (12)
M2—O122.1390 (11)P3—O91.5298 (11)
M2—O12vi2.1390 (11)P3—O111.5400 (11)
M2—O4vi2.1710 (11)P3—O101.5445 (11)
M2—O42.1710 (11)P3—O121.5512 (11)
M2—O8vii2.2430 (12)O2—M4ix2.0976 (11)
M2—O8ii2.2430 (12)O2—M3ix2.2199 (11)
M3—O9ii2.0748 (11)O6—M3x2.0882 (12)
M3—O6vii2.0882 (12)O7—M1iv2.1288 (12)
M3—O9viii2.1032 (11)O7—H2P0.85 (3)
M3—O102.1149 (11)O5—M4v2.1081 (12)
M3—O42.1320 (11)O5—M1v2.1322 (12)
M3—O2ix2.2199 (11)O3—M1xi2.0890 (11)
M3—M3ix3.0824 (5)O3—H1P0.85 (3)
M4—O102.0604 (11)O8—M2x2.2430 (12)
M4—O82.0926 (12)O9—M3ii2.0748 (11)
M4—O2ix2.0976 (11)O9—M3xii2.1032 (11)
M4—O5v2.1081 (12)O11—M1iii2.1208 (11)
M4—O1ii2.2034 (12)O1—M1ii2.0911 (11)
P1—O11.5274 (12)O1—M4ii2.2034 (12)
P1—O21.5310 (11)
O9ii—M3—O6vii177.41 (4)O1—P1—O4110.72 (6)
O9ii—M3—O9viii84.92 (4)O2—P1—O4114.57 (6)
O6vii—M3—O9viii93.39 (4)O1—P1—O3108.54 (6)
O9ii—M3—O1091.88 (4)O2—P1—O3106.78 (6)
O6vii—M3—O1089.13 (5)O4—P1—O3104.08 (6)
O9viii—M3—O10161.97 (4)O9—P3—O11108.96 (6)
O9ii—M3—O484.43 (4)O9—P3—O10110.59 (6)
O6vii—M3—O497.60 (4)O11—P3—O10110.28 (6)
O9viii—M3—O491.92 (4)O9—P3—O12109.91 (6)
O10—M3—O4105.44 (4)O11—P3—O12108.53 (6)
O9ii—M3—O2ix81.10 (4)O10—P3—O12108.55 (6)
O6vii—M3—O2ix96.76 (4)O8—P2—O6111.66 (7)
O9viii—M3—O2ix83.03 (4)O8—P2—O5111.13 (7)
O10—M3—O2ix78.94 (4)O6—P2—O5111.70 (7)
O4—M3—O2ix165.03 (4)O8—P2—O7109.60 (6)
O9ii—M3—M3ix42.81 (3)O6—P2—O7107.40 (7)
O6vii—M3—M3ix135.46 (4)O5—P2—O7105.06 (7)
O9viii—M3—M3ix42.10 (3)P1—O4—M3120.45 (6)
O10—M3—M3ix132.14 (3)P1—O4—M2122.03 (6)
O4—M3—M3ix87.57 (3)M3—O4—M2116.38 (5)
O2ix—M3—M3ix79.23 (3)P1—O2—M4ix138.88 (6)
O11—M1—O3i163.60 (4)P1—O2—M4ix138.88 (6)
O11—M1—O1ii90.18 (4)P1—O2—M3ix123.34 (6)
O3i—M1—O1ii105.01 (4)M4ix—O2—M3ix96.67 (4)
O11—M1—O11iii78.20 (5)M4ix—O2—M3ix96.67 (4)
O3i—M1—O11iii87.39 (4)P1—O2—M3ix123.34 (6)
O1ii—M1—O11iii166.41 (4)M4ix—O2—M3ix96.67 (4)
O11—M1—O7iv96.03 (4)P2—O6—M3x141.22 (7)
O3i—M1—O7iv89.65 (4)P2—O7—M1iv148.04 (7)
O1ii—M1—O7iv92.17 (5)P2—O7—H2P114 (2)
O11iii—M1—O7iv82.20 (4)M1iv—O7—H2P94 (2)
O11—M1—O5v94.92 (4)M1iv—O7—H2P94 (2)
O3i—M1—O5v82.07 (5)P2—O5—M4v136.06 (7)
O1ii—M1—O5v79.53 (4)P2—O5—M1v121.90 (7)
O11iii—M1—O5v108.19 (4)M4v—O5—M1v98.92 (5)
O7iv—M1—O5v166.27 (5)P2—O5—M1v121.90 (7)
O12—M2—O12vi180.00 (6)M4v—O5—M1v98.92 (5)
O12—M2—O4vi90.32 (4)P1—O3—M1xi135.93 (7)
O12vi—M2—O4vi89.68 (4)P1—O3—M1xi135.93 (7)
O12—M2—O489.68 (4)P1—O3—H1P107.8 (19)
O12vi—M2—O490.32 (4)M1xi—O3—H1P106 (2)
O4vi—M2—O4180.00 (5)M1xi—O3—H1P106 (2)
O12—M2—O8vii89.04 (4)P2—O8—M4117.24 (7)
O12vi—M2—O8vii90.96 (4)P2—O8—M2x131.08 (7)
O4vi—M2—O8vii85.96 (4)M4—O8—M2x111.53 (5)
O4—M2—O8vii94.04 (4)M4—O8—M2x111.53 (5)
O12—M2—O8ii90.96 (4)P3—O10—M4126.48 (6)
O12vi—M2—O8ii89.04 (4)P3—O10—M3128.41 (6)
O4vi—M2—O8ii94.04 (4)M4—O10—M3101.20 (5)
O4—M2—O8ii85.96 (4)P3—O9—M3ii129.37 (6)
O8vii—M2—O8ii180.00 (6)P3—O9—M3xii135.51 (7)
O10—M4—O8136.28 (5)M3ii—O9—M3xii95.08 (4)
O10—M4—O2ix83.06 (4)P3—O9—M3xii135.51 (7)
O8—M4—O2ix105.04 (4)M3ii—O9—M3xii95.08 (4)
O10—M4—O5v95.67 (5)P3—O11—M1124.87 (6)
O8—M4—O5v123.79 (5)P3—O11—M1iii132.69 (6)
O2ix—M4—O5v100.18 (4)M1—O11—M1iii101.80 (5)
O10—M4—O1ii88.72 (4)M1—O11—M1iii101.80 (5)
O8—M4—O1ii83.01 (4)P3—O12—M2153.67 (7)
O2ix—M4—O1ii171.24 (4)P1—O1—M1ii137.39 (7)
O5v—M4—O1ii77.56 (4)P1—O1—M4ii121.67 (6)
O1—P1—O2111.62 (6)M1ii—O1—M4ii97.21 (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, y1, z; (viii) x+1, y, z; (ix) x+1, y+1, z; (x) x, y+1, z; (xi) x, y1, z1; (xii) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H1P···O12vi0.85 (3)1.63 (3)2.4663 (18)169 (3)
O7—H2P···O6xiii0.85 (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 formulaCo4.32Mn2.68(HPO4)4(PO4)2
Mr974.07
Crystal system, space groupTriclinic, 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)
V3)432.64 (11)
Z1
Radiation typeMo Kα
µ (mm1)6.65
Crystal size (mm)0.10 × 0.10 × 0.10
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10685, 5484, 4111
Rint0.022
(sin θ/λ)max1)0.911
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.064, 1.05
No. of reflections5484
No. of parameters171
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Selected bond lengths (Å) top
M1—O112.0833 (11)M4—O102.0604 (11)
M1—O3i2.0890 (11)M4—O82.0926 (12)
M1—O1ii2.0911 (11)M4—O2ix2.0976 (11)
M1—O11iii2.1208 (11)M4—O5v2.1081 (12)
M1—O7iv2.1288 (12)M4—O1ii2.2034 (12)
M1—O5v2.1322 (12)P1—O11.5274 (12)
M2—O122.1390 (11)P1—O21.5310 (11)
M2—O12vi2.1390 (11)P1—O41.5486 (11)
M2—O4vi2.1710 (11)P1—O31.5777 (11)
M2—O42.1710 (11)P2—O81.5257 (12)
M2—O8vii2.2430 (12)P2—O61.5285 (12)
M2—O8ii2.2430 (12)P2—O51.5300 (12)
M3—O9ii2.0748 (11)P2—O71.5799 (12)
M3—O6vii2.0882 (12)P3—O91.5298 (11)
M3—O9viii2.1032 (11)P3—O111.5400 (11)
M3—O102.1149 (11)P3—O101.5445 (11)
M3—O42.1320 (11)P3—O121.5512 (11)
M3—O2ix2.2199 (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, y1, z; (viii) x+1, y, z; (ix) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H1P···O12vi0.85 (3)1.63 (3)2.4663 (18)169 (3)
O7—H2P···O6x0.85 (2)1.77 (2)2.6143 (18)172 (3)
Symmetry codes: (vi) x, y, z; (x) x+1, y+3, z+1.
 

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