Co(3)(PO(4))(2)·4H(2)O.

Single crystals of Co(3)(PO(4))(2)·4H(2)O, tricobalt(II) bis-[ortho-phosphate(V)] tetra-hydrate, were obtained under hydro-thermal conditions. The title compound is isotypic with its zinc analogue Zn(3)(PO(4))(2)·4H(2)O (mineral name hopeite) and contains two independent Co(2+) cations. One Co(2+) cation exhibits a slightly distorted tetra-hedral coordination, while the second, located on a mirror plane, has a distorted octa-hedral coordination environment. The tetra-hedrally coordinated Co(2+) is bonded to four O atoms of four PO(4) (3-) anions, whereas the six-coordinate Co(2+) is cis-bonded to two phosphate groups and to four O atoms of four water mol-ecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O-H⋯O 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 = 438.79

Orthorhombic,

a = 10.604 (3) Å

b = 18.288 (5) Å

c = 5.0070 (13) Å

V = 971.0 (5) Å3

Z = 4

Mo Kα radiation

μ = 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 > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.102

S = 1.16

1228 reflections

101 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −1.38 e Å−3

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028377/wm2193sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028377/wm2193Isup2.hkl

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

Co3(PO4)3·4H2O	F(000) = 860
Mr = 438.79	Dx = 3.002 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 5943 reflections
a = 10.604 (3) Å	θ = 2.9–28.3°
b = 18.288 (5) Å	µ = 5.46 mm−1
c = 5.0070 (13) Å	T = 150 K
V = 971.0 (5) Å3	Prism, purple
Z = 4	0.52 × 0.39 × 0.38 mm

Siemens SMART 1000 CCD diffractometer	1228 independent reflections
Radiation source: sealed tube	1166 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	h = −13→13
Tmin = 0.068, Tmax = 0.125	k = −24→24
8780 measured reflections	l = −6→6

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)] = 0.035	Hydrogen site location: difference Fourier map
wR(F2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ2(Fo2) + (0.059P)2 + 3.8213P] where P = (Fo2 + 2Fc2)/3
1228 reflections	(Δ/σ)max < 0.001
101 parameters	Δρmax = 0.55 e Å−3
10 restraints	Δρmin = −1.38 e Å−3

Experimental. The crystal was coated in Exxon Paratone N hydrocarbon oil and mounted on a thin mohair fibre attached to a copper pin. Upon mounting on the diffractometer, the crystal was quenched to 150(K) under a cold nitrogen gas stream supplied by an Oxford Cryosystems Cryostream and data were collected at this temperature.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.64313 (4)	0.00064 (2)	0.20676 (8)	0.00402 (17)
Co2	0.26113 (6)	0.2500	0.42866 (12)	0.00838 (19)
P1	0.39745 (9)	0.09462 (5)	0.27639 (18)	0.0123 (2)
O1	0.5259 (3)	0.07872 (14)	0.1463 (7)	0.0202 (6)
O2	0.3026 (2)	0.03968 (15)	0.1432 (5)	0.0148 (5)
O3	0.3601 (3)	0.17305 (16)	0.2139 (6)	0.0201 (7)
O4	0.3927 (4)	0.2500	0.7439 (7)	0.0155 (8)
O5	0.1149 (4)	0.2500	0.1406 (9)	0.0192 (8)
O6	0.1642 (3)	0.16927 (15)	0.6593 (6)	0.0197 (6)
O7	0.4000 (4)	0.08075 (16)	0.5755 (6)	0.0311 (8)
H1	0.098 (4)	0.161 (3)	0.553 (10)	0.047*
H2	0.2194 (15)	0.1390 (19)	0.739 (9)	0.047*
H3	0.132 (8)	0.280 (5)	0.005 (15)	0.047*	0.50
H4	0.044 (5)	0.231 (5)	0.204 (18)	0.047*	0.50
H5	0.403 (13)	0.296 (3)	0.80 (3)	0.047*	0.50
H6	0.366 (13)	0.210 (4)	0.83 (3)	0.047*	0.50

	U11	U22	U33	U12	U13	U23
Co1	0.0038 (3)	0.0055 (3)	0.0027 (3)	0.00152 (13)	0.00023 (14)	0.00025 (13)
Co2	0.0081 (3)	0.0088 (3)	0.0082 (3)	0.000	0.0006 (2)	0.000
P1	0.0179 (5)	0.0077 (4)	0.0114 (4)	0.0004 (3)	−0.0004 (3)	0.0003 (3)
O1	0.0128 (13)	0.0123 (12)	0.0357 (16)	−0.0008 (10)	−0.0008 (12)	0.0038 (12)
O2	0.0135 (12)	0.0177 (12)	0.0134 (11)	−0.0024 (10)	0.0020 (10)	−0.0028 (10)
O3	0.0331 (17)	0.0099 (13)	0.0174 (14)	0.0061 (11)	0.0094 (11)	0.0022 (10)
O4	0.017 (2)	0.0169 (19)	0.0130 (16)	0.000	−0.0012 (15)	0.000
O5	0.0136 (18)	0.026 (2)	0.0183 (18)	0.000	−0.0003 (16)	0.000
O6	0.0175 (14)	0.0149 (13)	0.0267 (14)	−0.0024 (11)	0.0027 (12)	0.0026 (12)
O7	0.066 (2)	0.0131 (13)	0.0142 (13)	−0.0105 (14)	−0.0095 (15)	0.0020 (10)

Co1—O7i	1.901 (3)	P1—O7	1.519 (3)
Co1—O1	1.918 (3)	P1—O3	1.521 (3)
Co1—O2ii	1.983 (3)	P1—O1	1.537 (3)
Co1—O2iii	1.986 (3)	P1—O2	1.570 (3)
Co2—O3iv	2.058 (3)	O4—H5	0.893 (10)
Co2—O3	2.058 (3)	O4—H6	0.893 (10)
Co2—O4	2.106 (4)	O5—H3	0.892 (10)
Co2—O5	2.118 (4)	O5—H4	0.891 (10)
Co2—O6	2.138 (3)	O6—H1	0.89 (4)
Co2—O6iv	2.138 (3)	O6—H2	0.90 (3)
O7i—Co1—O1	121.18 (15)	O7—P1—O3	111.40 (17)
O7i—Co1—O2ii	105.64 (13)	O7—P1—O1	111.8 (2)
O1—Co1—O2ii	110.16 (12)	O3—P1—O1	108.79 (16)
O7i—Co1—O2iii	106.57 (12)	O7—P1—O2	108.84 (17)
O1—Co1—O2iii	108.97 (13)	O3—P1—O2	110.43 (17)
O2ii—Co1—O2iii	102.75 (8)	O1—P1—O2	105.46 (16)
O3iv—Co2—O3	86.26 (16)	P1—O1—Co1	130.42 (18)
O3iv—Co2—O4	93.09 (12)	P1—O2—Co1v	128.01 (16)
O3—Co2—O4	93.09 (12)	P1—O2—Co1iii	115.24 (15)
O3iv—Co2—O5	91.00 (12)	Co1v—O2—Co1iii	116.58 (13)
O3—Co2—O5	91.00 (12)	P1—O3—Co2	132.08 (17)
O4—Co2—O5	174.38 (15)	Co2—O4—H5	108 (10)
O3iv—Co2—O6	178.01 (12)	Co2—O4—H6	98 (10)
O3—Co2—O6	93.16 (12)	H5—O4—H6	133 (3)
O4—Co2—O6	85.03 (11)	Co2—O5—H3	112 (6)
O5—Co2—O6	90.91 (12)	Co2—O5—H4	112 (6)
O3iv—Co2—O6iv	93.16 (12)	H3—O5—H4	134 (3)
O3—Co2—O6iv	178.01 (12)	Co2—O6—H1	100 (4)
O4—Co2—O6iv	85.03 (11)	Co2—O6—H2	110.7 (10)
O5—Co2—O6iv	90.91 (12)	H1—O6—H2	132 (2)
O6—Co2—O6iv	87.36 (16)	P1—O7—Co1i	133.79 (19)
O7—P1—O1—Co1	41.2 (3)	O1—P1—O2—Co1iii	−20.9 (2)
O3—P1—O1—Co1	164.7 (2)	O7—P1—O3—Co2	−22.9 (3)
O2—P1—O1—Co1	−76.9 (3)	O1—P1—O3—Co2	−146.5 (2)
O7i—Co1—O1—P1	8.8 (3)	O2—P1—O3—Co2	98.2 (3)
O2ii—Co1—O1—P1	−115.1 (2)	O3iv—Co2—O3—P1	153.57 (18)
O2iii—Co1—O1—P1	132.9 (2)	O4—Co2—O3—P1	60.7 (3)
O7—P1—O2—Co1v	34.1 (3)	O5—Co2—O3—P1	−115.5 (3)
O3—P1—O2—Co1v	−88.5 (2)	O6—Co2—O3—P1	−24.5 (3)
O1—P1—O2—Co1v	154.17 (19)	O3—P1—O7—Co1i	143.7 (3)
O7—P1—O2—Co1iii	−140.96 (19)	O1—P1—O7—Co1i	−94.4 (4)
O3—P1—O2—Co1iii	96.45 (18)	O2—P1—O7—Co1i	21.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H5···O3vi	0.89 (1)	2.25 (8)	2.764 (4)	116 (7)
O4—H5···O7iv	0.89 (1)	2.49 (8)	3.209 (3)	138 (9)
O4—H6···O3vii	0.89 (1)	2.02 (7)	2.764 (4)	140 (10)
O5—H4···O3v	0.89 (1)	2.25 (2)	3.133 (5)	170 (8)
O5—H4···O3viii	0.89 (1)	2.66 (8)	3.133 (5)	115 (6)
O6—H1···O1v	0.90 (4)	1.94 (3)	2.690 (4)	140 (4)
O6—H2···O7	0.90 (3)	2.35 (3)	3.008 (5)	130 (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) ; (ii) ; (iii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H5⋯O3iv	0.894 (10)	2.25 (8)	2.764 (4)	116 (7)
O4—H5⋯O7v	0.894 (10)	2.49 (8)	3.209 (3)	138 (9)
O4—H6⋯O3vi	0.894 (10)	2.02 (7)	2.764 (4)	140 (10)
O5—H4⋯O3vii	0.892 (10)	2.25 (2)	3.133 (5)	170 (8)
O5—H4⋯O3viii	0.892 (10)	2.66 (8)	3.133 (5)	115 (6)
O6—H1⋯O1vii	0.90 (4)	1.94 (3)	2.690 (4)	140 (4)
O6—H2⋯O7	0.90 (3)	2.35 (3)	3.008 (5)	130 (3)

Symmetry codes: (iv) ; (v) ; (vi) ; (vii) ; (viii) .