Dicobalt copper bis-[orthophosphate(V)] monohydrate, Co(2.39)Cu(0.61)(PO(4))(2)·H(2)O.

In an attempt to hydro-thermally synthesize a phase with composition Co(2)Cu(PO(4))(2)·H(2)O, we obtained the title compound, Co(2.39)Cu(0.61)(PO(4))(2)·H(2)O 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: CoO(6) octa-hedra, (Cu/Co)O(5) square pyramids and PO(4) tetra-hedra. The first layer is formed by pairs of edge-sharing (Cu/Co)O(5) square pyramids linked via a common edge of each end of the (Cu/Co)(2)O(8) dimer to PO(4) tetra-hedra. The second layer is undulating and is built up from edge-sharing CoO(6) octa-hedra. The linkage between the two layers is accomplished by PO(4) tetra-hedra. The presence of water mol-ecules in the CoO(4)(H(2)O)(2) octa-hedron 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 ▶); Gao & Gao (2005 ▶); Viter & Nagornyi (2009 ▶); Harrison et al. (1995 ▶). For compounds with the same structure, see: Anderson et al. (1976 ▶); Liao et al. (1995 ▶); Sørensen et al. (2004 ▶); Moore & Araki (1975 ▶).

Experimental

Crystal data

Co2.39Cu0.61(PO4)2·H2O

M = 387.57

Monoclinic,

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

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

Co2.39Cu0.61(PO4)2·H2O	F(000) = 745
Mr = 387.57	Dx = 3.942 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13678 reflections
a = 8.086 (2) Å	θ = 2.9–38.0°
b = 9.826 (3) Å	µ = 8.49 mm−1
c = 9.042 (3) Å	T = 296 K
β = 114.621 (1)°	Block, dark violet
V = 653.1 (3) Å3	0.24 × 0.12 × 0.06 mm
Z = 4

Bruker X8 APEX diffractometer	3531 independent reflections
Radiation source: fine-focus sealed tube	3278 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 38.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→14
Tmin = 0.306, Tmax = 0.601	k = −16→16
13678 measured reflections	l = −15→15

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

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)
Cu3	0.14535 (2)	0.125674 (19)	−0.43994 (2)	0.00920 (5)	0.613 (11)
Co3	0.14535 (2)	0.125674 (19)	−0.43994 (2)	0.00920 (5)	0.387 (11)
Co1	0.51531 (2)	0.129584 (19)	0.27594 (2)	0.00646 (4)
Co2	0.11526 (2)	0.133641 (19)	0.03006 (2)	0.00808 (4)
P1	0.38414 (4)	0.16385 (4)	−0.13938 (4)	0.00589 (6)
P2	0.20915 (4)	−0.08141 (3)	−0.67010 (4)	0.00519 (6)
O1	0.57091 (13)	0.22680 (11)	−0.09698 (12)	0.01030 (17)
O2	0.36035 (14)	0.13059 (11)	0.01540 (12)	0.00958 (16)
O3	0.35326 (13)	0.03970 (11)	−0.25406 (12)	0.00944 (16)
O4	0.22753 (13)	0.25872 (11)	−0.25036 (12)	0.00952 (16)
O5	0.08457 (14)	−0.02059 (11)	−0.59509 (12)	0.01044 (17)
O6	0.08992 (13)	−0.18315 (10)	−0.80105 (11)	0.00813 (15)
O7	0.37173 (13)	−0.15475 (11)	−0.53900 (12)	0.00950 (16)
O8	0.27312 (13)	0.03376 (10)	−0.74946 (12)	0.00871 (16)
O9	−0.10961 (14)	0.08498 (12)	0.07202 (12)	0.01199 (18)
H9A	−0.2021	0.1199	−0.0001	0.018*
H9B	−0.1031	0.0899	0.1749	0.018*

	U11	U22	U33	U12	U13	U23
Cu3	0.01172 (8)	0.00784 (8)	0.00548 (7)	0.00309 (5)	0.00105 (6)	−0.00054 (5)
Co3	0.01172 (8)	0.00784 (8)	0.00548 (7)	0.00309 (5)	0.00105 (6)	−0.00054 (5)
Co1	0.00605 (7)	0.00578 (8)	0.00694 (7)	0.00026 (5)	0.00208 (5)	−0.00043 (5)
Co2	0.00620 (7)	0.00832 (8)	0.00848 (7)	−0.00025 (5)	0.00182 (6)	0.00165 (6)
P1	0.00590 (11)	0.00584 (13)	0.00529 (12)	0.00016 (10)	0.00170 (9)	−0.00011 (10)
P2	0.00508 (11)	0.00526 (13)	0.00475 (11)	−0.00017 (9)	0.00156 (9)	0.00037 (9)
O1	0.0077 (4)	0.0124 (5)	0.0107 (4)	−0.0029 (3)	0.0037 (3)	−0.0035 (3)
O2	0.0093 (4)	0.0125 (4)	0.0068 (4)	−0.0004 (3)	0.0033 (3)	0.0012 (3)
O3	0.0091 (4)	0.0081 (4)	0.0081 (4)	0.0015 (3)	0.0006 (3)	−0.0024 (3)
O4	0.0093 (4)	0.0095 (4)	0.0086 (4)	0.0038 (3)	0.0026 (3)	0.0017 (3)
O5	0.0102 (4)	0.0120 (4)	0.0115 (4)	−0.0003 (3)	0.0069 (3)	−0.0029 (3)
O6	0.0088 (4)	0.0067 (4)	0.0067 (3)	−0.0016 (3)	0.0011 (3)	−0.0004 (3)
O7	0.0087 (4)	0.0090 (4)	0.0076 (4)	0.0012 (3)	0.0002 (3)	0.0017 (3)
O8	0.0082 (3)	0.0081 (4)	0.0092 (4)	−0.0017 (3)	0.0029 (3)	0.0024 (3)
O9	0.0104 (4)	0.0165 (5)	0.0094 (4)	0.0019 (3)	0.0045 (3)	0.0015 (3)

Cu3—O5	1.9236 (11)	P1—O4	1.5558 (11)
Cu3—O1i	1.9411 (11)	P2—O7	1.5343 (11)
Cu3—O3	2.0026 (11)	P2—O8	1.5402 (11)
Cu3—O4	2.0347 (12)	P2—O6	1.5427 (11)
Cu3—O5ii	2.2614 (11)	P2—O5	1.5496 (10)
Co1—O3iii	2.0274 (11)	O1—Co3vi	1.9411 (11)
Co1—O6iv	2.0791 (11)	O1—Cu3vi	1.9411 (11)
Co1—O8v	2.0976 (11)	O3—Co1iii	2.0274 (11)
Co1—O4vi	2.1321 (11)	O4—Co1i	2.1320 (11)
Co1—O2	2.1588 (12)	O5—Co3ii	2.2613 (11)
Co1—O7iii	2.1779 (12)	O5—Cu3ii	2.2613 (11)
Co2—O2	2.0407 (11)	O6—Co1viii	2.0790 (11)
Co2—O9	2.0625 (11)	O6—Co2ii	2.1010 (11)
Co2—O7iv	2.0818 (13)	O7—Co2viii	2.0818 (12)
Co2—O6ii	2.1010 (11)	O7—Co1iii	2.1779 (12)
Co2—O8v	2.1088 (11)	O8—Co1ix	2.0976 (10)
Co2—O9vii	2.3310 (13)	O8—Co2ix	2.1087 (11)
P1—O2	1.5254 (11)	O9—Co2vii	2.3310 (13)
P1—O1	1.5257 (11)	O9—H9A	0.8342
P1—O3	1.5525 (11)	O9—H9B	0.9111
O5—Cu3—O1i	96.74 (5)	O9—Co2—O7iv	104.98 (4)
O5—Cu3—O3	99.61 (5)	O2—Co2—O6ii	109.20 (4)
O1i—Cu3—O3	145.59 (4)	O9—Co2—O6ii	80.81 (4)
O5—Cu3—O4	171.47 (4)	O7iv—Co2—O6ii	79.25 (4)
O1i—Cu3—O4	91.68 (5)	O2—Co2—O8v	80.38 (4)
O3—Cu3—O4	72.46 (4)	O9—Co2—O8v	87.19 (4)
O5—Cu3—O5ii	77.63 (4)	O7iv—Co2—O8v	115.29 (4)
O1i—Cu3—O5ii	114.90 (4)	O6ii—Co2—O8v	163.32 (4)
O3—Cu3—O5ii	98.14 (5)	O2—Co2—O9vii	79.64 (4)
O4—Cu3—O5ii	100.04 (4)	O9—Co2—O9vii	89.19 (4)
O3iii—Co1—O6iv	172.66 (4)	O7iv—Co2—O9vii	158.15 (4)
O3iii—Co1—O8v	97.15 (5)	O6ii—Co2—O9vii	86.90 (4)
O6iv—Co1—O8v	90.19 (4)	O8v—Co2—O9vii	81.36 (4)
O3iii—Co1—O4vi	86.13 (5)	O2—P1—O1	110.26 (6)
O6iv—Co1—O4vi	86.65 (4)	O2—P1—O3	113.44 (6)
O8v—Co1—O4vi	167.68 (4)	O1—P1—O3	110.69 (6)
O3iii—Co1—O2	89.25 (4)	O2—P1—O4	109.89 (6)
O6iv—Co1—O2	92.14 (4)	O1—P1—O4	111.95 (6)
O8v—Co1—O2	77.97 (4)	O3—P1—O4	100.30 (6)
O4vi—Co1—O2	90.24 (4)	O7—P2—O8	111.04 (6)
O3iii—Co1—O7iii	101.61 (4)	O7—P2—O6	110.42 (6)
O6iv—Co1—O7iii	77.57 (4)	O8—P2—O6	110.02 (6)
O8v—Co1—O7iii	96.78 (4)	O7—P2—O5	110.30 (6)
O4vi—Co1—O7iii	94.16 (4)	O8—P2—O5	109.04 (6)
O2—Co1—O7iii	168.52 (4)	O6—P2—O5	105.87 (6)
O2—Co2—O9	164.36 (4)	H9A—O9—H9B	115.3
O2—Co2—O7iv	89.00 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O1i	0.83	1.97	2.768 (2)	159
O9—H9B···O5v	0.92	2.27	2.942 (2)	130
O9—H9B···O4x	0.92	2.30	2.905 (2)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O1	0.83	1.97	2.768 (2)	159
O9—H9B⋯O5i	0.92	2.27	2.942 (2)	130
O9—H9B⋯O4ii	0.92	2.30	2.905 (2)	123

Symmetry codes: (i) ; (ii) .