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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): i44.
Published online 2010 April 30. doi:  10.1107/S1600536810015382
PMCID: PMC2979060

Dicobalt copper bis­[orthophosphate(V)] monohydrate, Co2.39Cu0.61(PO4)2·H2O

Abstract

In an attempt to hydro­thermally synthesize a phase with composition Co2Cu(PO4)2·H2O, we obtained the title compound, Co2.39Cu0.61(PO4)2·H2O instead. Chemical analysis confirmed the presence of copper in the crystal. The crystal structure of the title compound can be described as a three- dimensional network constructed from the stacking of two types of layers extending parallel to (010). These layers are made up from more or less deformed polyhedra: CoO6 octa­hedra, (Cu/Co)O5 square pyramids and PO4 tetra­hedra. The first layer is formed by pairs of edge-sharing (Cu/Co)O5 square pyramids linked via a common edge of each end of the (Cu/Co)2O8 dimer to PO4 tetra­hedra. The second layer is undulating and is built up from edge-sharing CoO6 octa­hedra. The linkage between the two layers is accomplished by PO4 tetra­hedra. The presence of water mol­ecules in the CoO4(H2O)2 octa­hedron also contributes to the cohesion of the layers through O—H(...)O hydrogen bonding.

Related literature

For the properties of and background to metal phosphates, see: Clearfield (1988 [triangle]); Gao & Gao (2005 [triangle]); Viter & Nagornyi (2009 [triangle]); Harrison et al. (1995 [triangle]). For compounds with the same structure, see: Anderson et al. (1976 [triangle]); Liao et al. (1995 [triangle]); Sørensen et al. (2004 [triangle]); Moore & Araki (1975 [triangle]).

Experimental

Crystal data

  • Co2.39Cu0.61(PO4)2·H2O
  • M r = 387.57
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00i44-efi1.jpg
  • a = 8.086 (2) Å
  • b = 9.826 (3) Å
  • c = 9.042 (3) Å
  • β = 114.621 (1)°
  • V = 653.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 8.49 mm−1
  • T = 296 K
  • 0.24 × 0.12 × 0.06 mm

Data collection

  • Bruker X8 APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.306, T max = 0.601
  • 13678 measured reflections
  • 3531 independent reflections
  • 3278 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.051
  • S = 1.10
  • 3531 reflections
  • 129 parameters
  • H-atom parameters constrained
  • Δρmax = 1.01 e Å−3
  • Δρmin = −0.79 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810015382/wm2323sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015382/wm2323Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

supplementary crystallographic information

Comment

Metal-phosphates have received great attention owing to their applications such as catalysts (Viter & Nagornyi, 2009; Gao & Gao, 2005) and as ion-exchangers (Clearfield, 1988)). Mainly, the flexibility of the metal coordination and the possibility to generate anionic frameworks MIIPO4-, analogous to AlSiO4- in the well known aluminosilicate zeolites, offer a rich structural diversity of this family of compounds.

Our interest is particularly focused on the hydrothermally synthesized orthophosphates with formula MM'2(PO4)2.H2O (M and M'= bivalent cations). In this work, a new dicobalt copper bis[orthophosphate] monohydrate, Co2.39Cu0.61(PO4)2.H2O was synthesized and structurally characterized.

A three-dimensional view of the crystal structure of the title compound is given in Fig. 1. It shows that the metal cations are located in three crystallographically different sites, two octahedra entirely occupied by cobalt and one square-pyramid statistically filled with Co/Cu. Refinement of the occupancy of this metal site has led to the following composition, Co2.39Cu0.61(PO4)2.H2O. The cationic distributions indicate that Cu prefers the site with a lower coordination number, whereas Co prefers coordination number of 6. This may be attributed to a gain in crystal field stabilisation energy for Co2+ in the octahedral sites and to the small difference between the sizes of the two cations Co2+ and Cu2+.

The network is built up from three different types of polyhedra more or less distorted: CoO6 octahedra , (Cu/Co)O5 square-pyramids and PO4 tetrahedra. One octahedron (Co1), slightly distorted, has a coordination sphere composed of O atoms from PO4 groups, while that of the other (Co2) is made up of four O atoms from PO4 groups and by two water molecules (O9). This fact explains its more pronounced distortion, with Co—O bond lengths in the range 2.0407 (11)-2.3310 (13) Å.

All CoO6 octahedra are linked together by edge-sharing and sharing three corners of PO4 tetrahedra, in the way to built a layer parallel to (010) as shown in Fig. 2. Therefore, the presence of the water molecule involved in the formation of the CoO4(H2O)2 octahedron causes a corrugation in this layer through O—H···O hydrogen bonds. Furthermore, Fig. 3 shows that each pair of distorted square-pyramids share an edge and built up a dimer linked to two regular PO4 tetrahedra via a common edge. The sequence of (Cu/Co)O5 and PO4 polyhedra leads to the formation of another layer (Fig. 3). As a matter of fact, the network of this structure can be described by stacking these two types of layers as represented in Fig. 4.

Compounds isotypic with the title phase are relatively rare, however, there are four known compounds which adopt this structure, viz. Co3(PO4)2.H2O (Anderson et al., 1976), CuMn2(PO4)2.H2O (Liao et al., 1995), Co2.59Zn0.41(PO4)2.H2O (Sørensen et al., 2004) and Fe3(PO4)2.H2O (Moore & Araki, 1975).

Experimental

The crystals of the title compound were hydrothermally synthesized starting from a mixture of metallic copper (0.0381 g), basic cobalt(II) carbonate (0.0318 g), 85 %wt phosphoric acid (0.10 ml) and 10 ml distilled water. The hydrothermal synthesis was carried out in 23 ml Teflon-lined autoclave under autogeneous pressure at 468 K during 24 h. The product was filtered off, washed with deionized water and air dried. The reaction product consists of two types of crystals. The first one, dark violet crystals, corresponds to the title compound with the refined composition Co2.39Cu0.61(PO4)2.H2O. An elemental chemical analysis (EDS) confirms the presence of copper in the crystal. The second type of crystals is identified to be the known cobalt hydroxy phosphate Co2(OH)PO4 (Harrison et al., 1995).

Refinement

All H atoms were initially located in a difference map and refined with a O—H distance restraint of 0.84 (1) Å. Later they were refined in the riding model approximation with Uiso(H) set to 1.5 Ueq(O). Refinements of the site ocupancy factors of the metal sites revealed the octahedrally coordinated sites solely occupied by Co, whereas the 5-coordinated site shows a mixed occupancy of Co:Cu = 0.387 (11):0.613 (11).

Figures

Fig. 1.
A three-dimensional view of the crystal structure of the Co2.39Cu0.61(PO4)2.H2O compound drawn with displacement parameters at the 60% probability level. H atoms are given as small spheres of arbitrary radius. For symmetry operators, see geometric parameters ...
Fig. 2.
The undulated layer built up from edge sharing CoO6 octahedra and water molecules.
Fig. 3.
A copper phosphate layer formed by (Cu/Co)2P2O12 linked to PO4 tetrahedra.
Fig. 4.
Stacking of the two types of layers projected approximately along [101].

Crystal data

Co2.39Cu0.61(PO4)2·H2OF(000) = 745
Mr = 387.57Dx = 3.942 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 13678 reflections
a = 8.086 (2) Åθ = 2.9–38.0°
b = 9.826 (3) ŵ = 8.49 mm1
c = 9.042 (3) ÅT = 296 K
β = 114.621 (1)°Block, dark violet
V = 653.1 (3) Å30.24 × 0.12 × 0.06 mm
Z = 4

Data collection

Bruker X8 APEX diffractometer3531 independent reflections
Radiation source: fine-focus sealed tube3278 reflections with I > 2σ(I)
graphiteRint = 0.023
[var phi] and ω scansθmax = 38.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −11→14
Tmin = 0.306, Tmax = 0.601k = −16→16
13678 measured reflectionsl = −15→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.051w = 1/[σ2(Fo2) + (0.0196P)2 + 0.5902P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
3531 reflectionsΔρmax = 1.01 e Å3
129 parametersΔρmin = −0.79 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0034 (3)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/UeqOcc. (<1)
Cu30.14535 (2)0.125674 (19)−0.43994 (2)0.00920 (5)0.613 (11)
Co30.14535 (2)0.125674 (19)−0.43994 (2)0.00920 (5)0.387 (11)
Co10.51531 (2)0.129584 (19)0.27594 (2)0.00646 (4)
Co20.11526 (2)0.133641 (19)0.03006 (2)0.00808 (4)
P10.38414 (4)0.16385 (4)−0.13938 (4)0.00589 (6)
P20.20915 (4)−0.08141 (3)−0.67010 (4)0.00519 (6)
O10.57091 (13)0.22680 (11)−0.09698 (12)0.01030 (17)
O20.36035 (14)0.13059 (11)0.01540 (12)0.00958 (16)
O30.35326 (13)0.03970 (11)−0.25406 (12)0.00944 (16)
O40.22753 (13)0.25872 (11)−0.25036 (12)0.00952 (16)
O50.08457 (14)−0.02059 (11)−0.59509 (12)0.01044 (17)
O60.08992 (13)−0.18315 (10)−0.80105 (11)0.00813 (15)
O70.37173 (13)−0.15475 (11)−0.53900 (12)0.00950 (16)
O80.27312 (13)0.03376 (10)−0.74946 (12)0.00871 (16)
O9−0.10961 (14)0.08498 (12)0.07202 (12)0.01199 (18)
H9A−0.20210.1199−0.00010.018*
H9B−0.10310.08990.17490.018*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu30.01172 (8)0.00784 (8)0.00548 (7)0.00309 (5)0.00105 (6)−0.00054 (5)
Co30.01172 (8)0.00784 (8)0.00548 (7)0.00309 (5)0.00105 (6)−0.00054 (5)
Co10.00605 (7)0.00578 (8)0.00694 (7)0.00026 (5)0.00208 (5)−0.00043 (5)
Co20.00620 (7)0.00832 (8)0.00848 (7)−0.00025 (5)0.00182 (6)0.00165 (6)
P10.00590 (11)0.00584 (13)0.00529 (12)0.00016 (10)0.00170 (9)−0.00011 (10)
P20.00508 (11)0.00526 (13)0.00475 (11)−0.00017 (9)0.00156 (9)0.00037 (9)
O10.0077 (4)0.0124 (5)0.0107 (4)−0.0029 (3)0.0037 (3)−0.0035 (3)
O20.0093 (4)0.0125 (4)0.0068 (4)−0.0004 (3)0.0033 (3)0.0012 (3)
O30.0091 (4)0.0081 (4)0.0081 (4)0.0015 (3)0.0006 (3)−0.0024 (3)
O40.0093 (4)0.0095 (4)0.0086 (4)0.0038 (3)0.0026 (3)0.0017 (3)
O50.0102 (4)0.0120 (4)0.0115 (4)−0.0003 (3)0.0069 (3)−0.0029 (3)
O60.0088 (4)0.0067 (4)0.0067 (3)−0.0016 (3)0.0011 (3)−0.0004 (3)
O70.0087 (4)0.0090 (4)0.0076 (4)0.0012 (3)0.0002 (3)0.0017 (3)
O80.0082 (3)0.0081 (4)0.0092 (4)−0.0017 (3)0.0029 (3)0.0024 (3)
O90.0104 (4)0.0165 (5)0.0094 (4)0.0019 (3)0.0045 (3)0.0015 (3)

Geometric parameters (Å, °)

Cu3—O51.9236 (11)P1—O41.5558 (11)
Cu3—O1i1.9411 (11)P2—O71.5343 (11)
Cu3—O32.0026 (11)P2—O81.5402 (11)
Cu3—O42.0347 (12)P2—O61.5427 (11)
Cu3—O5ii2.2614 (11)P2—O51.5496 (10)
Co1—O3iii2.0274 (11)O1—Co3vi1.9411 (11)
Co1—O6iv2.0791 (11)O1—Cu3vi1.9411 (11)
Co1—O8v2.0976 (11)O3—Co1iii2.0274 (11)
Co1—O4vi2.1321 (11)O4—Co1i2.1320 (11)
Co1—O22.1588 (12)O5—Co3ii2.2613 (11)
Co1—O7iii2.1779 (12)O5—Cu3ii2.2613 (11)
Co2—O22.0407 (11)O6—Co1viii2.0790 (11)
Co2—O92.0625 (11)O6—Co2ii2.1010 (11)
Co2—O7iv2.0818 (13)O7—Co2viii2.0818 (12)
Co2—O6ii2.1010 (11)O7—Co1iii2.1779 (12)
Co2—O8v2.1088 (11)O8—Co1ix2.0976 (10)
Co2—O9vii2.3310 (13)O8—Co2ix2.1087 (11)
P1—O21.5254 (11)O9—Co2vii2.3310 (13)
P1—O11.5257 (11)O9—H9A0.8342
P1—O31.5525 (11)O9—H9B0.9111
O5—Cu3—O1i96.74 (5)O9—Co2—O7iv104.98 (4)
O5—Cu3—O399.61 (5)O2—Co2—O6ii109.20 (4)
O1i—Cu3—O3145.59 (4)O9—Co2—O6ii80.81 (4)
O5—Cu3—O4171.47 (4)O7iv—Co2—O6ii79.25 (4)
O1i—Cu3—O491.68 (5)O2—Co2—O8v80.38 (4)
O3—Cu3—O472.46 (4)O9—Co2—O8v87.19 (4)
O5—Cu3—O5ii77.63 (4)O7iv—Co2—O8v115.29 (4)
O1i—Cu3—O5ii114.90 (4)O6ii—Co2—O8v163.32 (4)
O3—Cu3—O5ii98.14 (5)O2—Co2—O9vii79.64 (4)
O4—Cu3—O5ii100.04 (4)O9—Co2—O9vii89.19 (4)
O3iii—Co1—O6iv172.66 (4)O7iv—Co2—O9vii158.15 (4)
O3iii—Co1—O8v97.15 (5)O6ii—Co2—O9vii86.90 (4)
O6iv—Co1—O8v90.19 (4)O8v—Co2—O9vii81.36 (4)
O3iii—Co1—O4vi86.13 (5)O2—P1—O1110.26 (6)
O6iv—Co1—O4vi86.65 (4)O2—P1—O3113.44 (6)
O8v—Co1—O4vi167.68 (4)O1—P1—O3110.69 (6)
O3iii—Co1—O289.25 (4)O2—P1—O4109.89 (6)
O6iv—Co1—O292.14 (4)O1—P1—O4111.95 (6)
O8v—Co1—O277.97 (4)O3—P1—O4100.30 (6)
O4vi—Co1—O290.24 (4)O7—P2—O8111.04 (6)
O3iii—Co1—O7iii101.61 (4)O7—P2—O6110.42 (6)
O6iv—Co1—O7iii77.57 (4)O8—P2—O6110.02 (6)
O8v—Co1—O7iii96.78 (4)O7—P2—O5110.30 (6)
O4vi—Co1—O7iii94.16 (4)O8—P2—O5109.04 (6)
O2—Co1—O7iii168.52 (4)O6—P2—O5105.87 (6)
O2—Co2—O9164.36 (4)H9A—O9—H9B115.3
O2—Co2—O7iv89.00 (4)

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x, −y, −z−1; (iii) −x+1, −y, −z; (iv) −x+1/2, y+1/2, −z−1/2; (v) x, y, z+1; (vi) x+1/2, −y+1/2, z+1/2; (vii) −x, −y, −z; (viii) −x+1/2, y−1/2, −z−1/2; (ix) x, y, z−1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O9—H9A···O1i0.831.972.768 (2)159
O9—H9B···O5v0.922.272.942 (2)130
O9—H9B···O4x0.922.302.905 (2)123

Symmetry codes: i; (v) x, y, z+1; (x) x−1/2, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2323).

References

  • Anderson, J., Kostiner, E. & Ruszala, F. A. (1976). Inorg. Chem.15 2744–2748.
  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Clearfield, A. (1988). Chem. Rev.88, 125–148,
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Gao, D. & Gao, Q. (2005). Micropor. Mesopor. Mater.85 365–373.
  • Harrison, W. T. A., Vaughey, J. T., Dussack, L. L., Jacobson, A. J., Martin, T. E. & Stucky, G. D. (1995). J. Solid State Chem.114, 151–158.
  • Liao, J. H., Leroux, F., Guyomard, D., Piffard, Y. & Tournoux, M. (1995). Eur. J. Solid State Inorg. Chem.32, 403–414.
  • Moore, P. B. & Araki, T. (1975). Am. Mineral.60, 454–459.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sørensen, M. B., Hazell, R. G., Bentien, A., Bond, A. D. & Jensen, T. R. (2004). Dalton Trans. pp. 598–606. [PubMed]
  • Viter, V. N. & Nagornyi, P. G. (2009). Russ. J. Appl. Chem.82, 935–939.

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