A second polymorph with composition Co3(PO4)2·H2O

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

doi:10.1107/S1600536808028365

Volume 64
Part 10
Pages i69-i70
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 (P-O) = 0.003 Å
R = 0.033
wR = 0.095
Data-to-parameter ratio = 12.8
Details

A second polymorph with composition Co₃(PO₄)₂·H₂O

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·H₂O, tricobalt(II) bis[orthophosphate(V)] monohydrate, were obtained under hydrothermal conditions. The compound is the second polymorph of this composition and is isotypic with its zinc analogue, Zn₃(PO₄)₂·H₂O. Three independent Co²⁺ cations are bridged by two independent orthophosphate anions. Two of the metal cations exhibit a distorted tetrahedral coordination while the third exhibits a considerably distorted [5 + 1] octahedral coordination environment with one very long Co-O distance of 2.416 (3) Å. The former cations are bonded to four different phosphate anions, and the latter cation is bonded to four anions (one of which is bidentate) and one water molecule, leading to a framework structure. Additional hydrogen bonds of the type O-HO stabilize this arrangement.

Related literature

Besides crystals of the title compound, crystals of the related phase Co₃(PO₄)₂·4H₂O (Lee et al., 2008) were also obtained under hydrothermal conditions. For a review of metal complexes of organophosphate esters and open-framework metal phosphates, see: Murugavel et al. (2008). For different cobalt(II) phosphates, see: Mellor (1935). The first polymorph of composition Co₃(PO₄)₂·H₂O was reported by Anderson et al. (1976), and the crystal structure of the isotypic Zn analogue Zn₃(PO₄)₂·H₂O was described by Riou et al. (1986).

Experimental

Crystal data

Co₃(PO₄)₂·H₂O
M_r = 384.75
Monoclinic, P 2₁ /c
a = 8.7038 (15) Å
b = 4.8667 (9) Å
c = 16.705 (3) Å
= 95.670 (3)°
V = 704.1 (2) Å³
Z = 4
Mo K radiation
= 7.47 mm^-1
T = 150 (2) K
0.46 × 0.14 × 0.08 mm

Data collection

Siemens SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) T_min = 0.247, T_max = 0.554
6569 measured reflections
1697 independent reflections
1603 reflections with I > 2(I)
R_int = 0.026

Refinement

R[F² > 2(F²)] = 0.033
wR(F²) = 0.095
S = 1.07
1697 reflections
133 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.73 e Å^-3
_min = -1.39 e Å^-3

Table 1
Selected bond lengths (Å)

Co1-O3	1.897 (3)
Co1-O4	1.941 (3)
Co1-O2	1.992 (3)
Co1-O1	2.002 (3)
Co2-O9	1.887 (3)
Co2-O5	1.949 (3)
Co2-O1	1.986 (3)
Co2-O2ⁱ	2.054 (3)
Co3-O6	2.019 (3)
Co3-O7	2.061 (3)
Co3-O8	2.065 (3)
Co3-O8ⁱⁱ	2.075 (3)
Co3-O5ⁱⁱⁱ	2.108 (3)
Co3-O3^iv	2.416 (3)
P1-O6	1.513 (3)
P1-O4ⁱ	1.534 (3)
P1-O2^v	1.560 (3)
P1-O1	1.561 (3)
P2-O9	1.511 (3)
P2-O8^vi	1.544 (3)
P2-O3^vii	1.549 (3)
P2-O5^vi	1.565 (3)
Symmetry codes: (i) -x+1, -y, -z+2; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y+1, z; (iv) x+1, y, z; (v) -x+1, -y+1, -z+2; (vi) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) x, y-1, z.

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O7-H2O6ⁱⁱⁱ	0.90 (3)	1.86 (4)	2.753 (4)	170 (5)
O7-H1O4^viii	0.903 (10)	1.864 (15)	2.758 (4)	171 (5)
Symmetry codes: (iii) x, y+1, z; (viii) x+1, y+1, z.

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: WM2194 ).

Acknowledgements

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

References

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inorganic compounds