Co3(PO4)2·4H2O

Lee, Y.H.; Clegg, J.K.; Lindoy, L.F.; Lu, G.Q.M.; Park, Y.-C.; Kim, Y.

doi:10.1107/S1600536808028377

Volume 64
Part 10
Pages i67-i68
October 2008

Received 29 August 2008
Accepted 4 September 2008
Online 13 September 2008

Key indicators
Single-crystal X-ray study
T = 150 K
Mean (Co-O) = 0.003 Å
R = 0.035
wR = 0.103
Data-to-parameter ratio = 12.2
Details

Co₃(PO₄)₂·4H₂O

Young Hoon Lee,^a Jack K. Clegg,^b Leonard F. Lindoy,^b G. Q. Max Lu,^c Yu-Chul Park ^a and Yang Kim ^d ^*

^aDepartment of Chemistry, Kyungpook National University, Daegu 702-701, Republic of Korea,^bCentre for Heavy Metals Research, School of Chemistry, F11, University of Sydney, New South Wales 2006, Australia,^cARC Centre of Excellence for Functional Nanomaterials, AIBN, University of Queensland, Brisbane, Queensland 4072, Australia, and ^dDepartment of Chemistry and Advanced Materials, Kosin University, 149-1 Dongsam-dong, Yeongdo-gu, Busan 606-701, Republic of Korea
Correspondence e-mail: ykim@kosin.ac.kr

Single crystals of Co₃(PO₄)₂·4H₂O, tricobalt(II) bis[orthophosphate(V)] tetrahydrate, were obtained under hydrothermal conditions. The title compound is isotypic with its zinc analogue Zn₃(PO₄)₂·4H₂O (mineral name hopeite) and contains two independent Co²⁺ cations. One Co²⁺ cation exhibits a slightly distorted tetrahedral coordination, while the second, located on a mirror plane, has a distorted octahedral coordination environment. The tetrahedrally coordinated Co²⁺ is bonded to four O atoms of four PO₄^3- anions, whereas the six-coordinate Co²⁺ is cis-bonded to two phosphate groups and to four O atoms of four water molecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O-HO are present throughout the crystal structure.

Related literature

Besides crystals of the title compound, crystals of Co₃(PO₄)₂·H₂O (Lee et al., 2008) have also been obtained under hydrothermal conditions. For reviews, synthesis, structures and applications of open framework structures with different cations and/or structure directing molecules, see: Kuzicki et al. (2001); Chen et al. (2006); Jiang & Gao (2007); Cheetham et al. (1999); Forster et al. (2003); Jiang et al. (2001); Cooper et al. (2004); Choudhury et al. (2000). The structure of the isotypic mineral hopeite was first described by Liebau (1965).

Experimental

Crystal data

Co₃(PO₄)₃·4H₂O
M_r = 438.79
Orthorhombic, P n m a
a = 10.604 (3) Å
b = 18.288 (5) Å
c = 5.0070 (13) Å
V = 971.0 (5) Å³
Z = 4
Mo K radiation
= 5.46 mm^-1
T = 150 (2) K
0.52 × 0.39 × 0.38 mm

Data collection

Siemens SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) T_min = 0.068, T_max = 0.125
8780 measured reflections
1228 independent reflections
1166 reflections with I > 2(I)
R_int = 0.026

Refinement

R[F² > 2(F²)] = 0.035
wR(F²) = 0.102
S = 1.16
1228 reflections
101 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.55 e Å^-3
_min = -1.38 e Å^-3

Table 1
Selected bond lengths (Å)

Co1-O7ⁱ	1.901 (3)
Co1-O1	1.918 (3)
Co1-O2ⁱⁱ	1.983 (3)
Co1-O2ⁱⁱⁱ	1.986 (3)
Co2-O4	2.106 (4)
Co2-O5	2.118 (4)
Co2-O6	2.138 (3)
P1-O7	1.519 (3)
P1-O3	1.521 (3)
P1-O1	1.537 (3)
P1-O2	1.570 (3)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O4-H5O3^iv	0.894 (10)	2.25 (8)	2.764 (4)	116 (7)
O4-H5O7^v	0.894 (10)	2.49 (8)	3.209 (3)	138 (9)
O4-H6O3^vi	0.894 (10)	2.02 (7)	2.764 (4)	140 (10)
O5-H4O3^vii	0.892 (10)	2.25 (2)	3.133 (5)	170 (8)
O5-H4O3^viii	0.892 (10)	2.66 (8)	3.133 (5)	115 (6)
O6-H1O1^vii	0.90 (4)	1.94 (3)	2.690 (4)	140 (4)
O6-H2O7	0.90 (3)	2.35 (3)	3.008 (5)	130 (3)
Symmetry codes: (iv) $[x, -y+{\script{1\over 2}}, z+1]$ ; (v) $[x, -y+{\script{1\over 2}}, z]$ ; (vi) x, y, z+1; (vii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (viii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and XPREP (Siemens, 1995); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), WebLab ViewerPro (Molecular Simulations, 2000) and POV-RAY (Cason, 2002); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2193 ).

Acknowledgements

We gratefully acknowledge the Brain Korea 21 programme and the Australian Research Council for support.

References

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inorganic compounds