A second polymorph with composition Co(3)(PO(4))(2)·H(2)O.

Single crystals of Co(3)(PO(4))(2)·H(2)O, tricobalt(II) bis-[ortho-phosphate(V)] monohydrate, were obtained under hydro-thermal conditions. The compound is the second polymorph of this composition and is isotypic with its zinc analogue, Zn(3)(PO(4))(2)·H(2)O. Three independent Co(2+) cations are bridged by two independent orthophosphate anions. Two of the metal cations exhibit a distorted tetra-hedral coordination while the third exhibits a considerably distorted [5 + 1] octa-hedral 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 mol-ecule, leading to a framework structure. Additional hydrogen bonds of the type O-H⋯O 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 = 384.75

Monoclinic,

a = 8.7038 (15) Å

b = 4.8667 (9) Å

c = 16.705 (3) Å

β = 95.670 (3)°

V = 704.1 (2) Å3

Z = 4

Mo Kα radiation

μ = 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 > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.095

S = 1.07

1697 reflections

133 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.73 e Å−3

Δρmin = −1.39 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/S1600536808028365/wm2194sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028365/wm2194Isup2.hkl

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

Co3(PO4)2·H2O	F(000) = 740
Mr = 384.75	Dx = 3.629 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4684 reflections
a = 8.7038 (15) Å	θ = 2.5–28.4°
b = 4.8667 (9) Å	µ = 7.47 mm−1
c = 16.705 (3) Å	T = 150 K
β = 95.670 (3)°	Plate, purple
V = 704.1 (2) Å3	0.46 × 0.14 × 0.08 mm
Z = 4

Siemens SMART 1000 CCD diffractometer	1697 independent reflections
Radiation source: sealed tube	1603 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω scans	θmax = 28.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	h = −11→11
Tmin = 0.247, Tmax = 0.554	k = −6→6
6569 measured reflections	l = −21→21

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)] = 0.033	Hydrogen site location: difference Fourier map
wR(F2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0597P)2 + 3.2629P] where P = (Fo2 + 2Fc2)/3
1697 reflections	(Δ/σ)max < 0.001
133 parameters	Δρmax = 0.74 e Å−3
2 restraints	Δρmin = −1.39 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.

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
Co1	0.32855 (5)	0.20270 (9)	0.94291 (3)	0.00253 (14)
Co2	0.56640 (5)	−0.20252 (9)	0.84576 (3)	0.00303 (15)
Co3	0.92910 (6)	0.49852 (10)	0.82254 (3)	0.00814 (16)
P1	0.68190 (11)	0.29320 (19)	0.94510 (6)	0.0086 (2)
P2	0.23599 (11)	−0.51187 (19)	0.78087 (6)	0.0087 (2)
O1	0.5357 (3)	0.1481 (6)	0.90286 (17)	0.0114 (5)
O2	0.3621 (3)	0.3976 (6)	1.04804 (16)	0.0106 (5)
O3	0.1907 (3)	0.3427 (6)	0.85760 (17)	0.0119 (5)
O4	0.2836 (3)	−0.1747 (6)	0.96996 (17)	0.0121 (6)
O5	0.7445 (3)	−0.2368 (6)	0.78428 (17)	0.0116 (5)
O6	0.8153 (3)	0.2545 (6)	0.89463 (17)	0.0120 (5)
O7	0.9749 (4)	0.7679 (6)	0.91711 (18)	0.0137 (6)
O8	0.9060 (3)	0.1703 (6)	0.74391 (17)	0.0108 (5)
O9	0.3852 (3)	−0.3512 (6)	0.79103 (18)	0.0148 (6)
H1	1.0769 (18)	0.797 (12)	0.929 (3)	0.022*
H2	0.933 (6)	0.936 (5)	0.909 (3)	0.022*

	U11	U22	U33	U12	U13	U23
Co1	0.0013 (2)	0.0038 (2)	0.0025 (2)	0.00007 (15)	−0.00013 (17)	0.00053 (15)
Co2	0.0006 (2)	0.0045 (3)	0.0040 (2)	−0.00041 (15)	0.00015 (17)	−0.00098 (15)
Co3	0.0077 (3)	0.0083 (3)	0.0088 (3)	−0.00123 (17)	0.00306 (19)	−0.00064 (17)
P1	0.0070 (5)	0.0090 (5)	0.0098 (5)	−0.0004 (3)	0.0014 (3)	−0.0002 (3)
P2	0.0067 (5)	0.0103 (4)	0.0091 (4)	0.0003 (3)	0.0008 (3)	0.0001 (3)
O1	0.0101 (13)	0.0112 (12)	0.0129 (13)	−0.0009 (10)	0.0004 (10)	−0.0005 (10)
O2	0.0114 (13)	0.0106 (13)	0.0099 (13)	0.0026 (10)	0.0011 (10)	−0.0003 (10)
O3	0.0121 (13)	0.0133 (13)	0.0102 (13)	−0.0003 (11)	0.0007 (11)	0.0014 (10)
O4	0.0135 (14)	0.0116 (13)	0.0110 (13)	−0.0005 (10)	−0.0004 (11)	0.0009 (10)
O5	0.0108 (14)	0.0131 (12)	0.0114 (13)	0.0007 (10)	0.0041 (10)	0.0008 (10)
O6	0.0106 (14)	0.0132 (12)	0.0127 (13)	−0.0009 (11)	0.0035 (11)	0.0007 (10)
O7	0.0110 (14)	0.0132 (13)	0.0164 (14)	0.0012 (11)	−0.0014 (11)	−0.0015 (11)
O8	0.0075 (13)	0.0122 (13)	0.0131 (13)	−0.0006 (10)	0.0026 (10)	−0.0022 (10)
O9	0.0109 (14)	0.0163 (13)	0.0171 (14)	−0.0033 (11)	0.0012 (11)	−0.0011 (11)

Co1—O3	1.897 (3)	Co3—O3iv	2.416 (3)
Co1—O4	1.941 (3)	Co3—P2v	2.8266 (12)
Co1—O2	1.992 (3)	P1—O6	1.513 (3)
Co1—O1	2.002 (3)	P1—O4i	1.534 (3)
Co2—O9	1.887 (3)	P1—O2vi	1.560 (3)
Co2—O5	1.949 (3)	P1—O1	1.561 (3)
Co2—O1	1.986 (3)	P2—O9	1.511 (3)
Co2—O2i	2.054 (3)	P2—O8vii	1.544 (3)
Co3—O6	2.019 (3)	P2—O3viii	1.549 (3)
Co3—O7	2.061 (3)	P2—O5vii	1.565 (3)
Co3—O8	2.065 (3)	P2—Co3ix	2.8266 (12)
Co3—O8ii	2.075 (3)	O7—H1	0.903 (10)
Co3—O5iii	2.108 (3)	O7—H2	0.90 (3)
O3—Co1—O4	112.81 (13)	O4i—P1—O2vi	108.77 (15)
O3—Co1—O2	121.22 (12)	O6—P1—O1	109.15 (16)
O4—Co1—O2	105.11 (12)	O4i—P1—O1	108.94 (16)
O3—Co1—O1	108.70 (12)	O2vi—P1—O1	105.94 (16)
O4—Co1—O1	99.28 (12)	O9—P2—O8vii	112.91 (17)
O2—Co1—O1	107.42 (12)	O9—P2—O3viii	115.46 (17)
O9—Co2—O5	112.44 (13)	O8vii—P2—O3viii	102.81 (16)
O9—Co2—O1	114.62 (13)	O9—P2—O5vii	106.80 (16)
O5—Co2—O1	118.58 (12)	O8vii—P2—O5vii	110.75 (16)
O9—Co2—O2i	114.12 (12)	O3viii—P2—O5vii	108.04 (16)
O5—Co2—O2i	103.10 (12)	O9—P2—Co3ix	141.79 (13)
O1—Co2—O2i	91.48 (11)	O8vii—P2—Co3ix	45.96 (10)
O6—Co3—O7	89.20 (12)	O3viii—P2—Co3ix	58.69 (11)
O6—Co3—O8	84.37 (11)	O5vii—P2—Co3ix	110.73 (12)
O7—Co3—O8	168.15 (12)	P1—O1—Co2	117.61 (16)
O6—Co3—O8ii	164.15 (12)	P1—O1—Co1	120.63 (16)
O7—Co3—O8ii	93.56 (12)	Co2—O1—Co1	116.29 (14)
O8—Co3—O8ii	90.02 (7)	P1vi—O2—Co1	120.56 (16)
O6—Co3—O5iii	97.82 (11)	P1vi—O2—Co2i	115.98 (15)
O7—Co3—O5iii	85.85 (12)	Co1—O2—Co2i	123.17 (15)
O8—Co3—O5iii	104.85 (11)	P2iii—O3—Co1	126.29 (18)
O8ii—Co3—O5iii	97.95 (11)	P1i—O4—Co1	123.07 (17)
O6—Co3—O3iv	100.18 (11)	P2x—O5—Co2	116.94 (17)
O7—Co3—O3iv	84.70 (11)	P2x—O5—Co3viii	120.43 (16)
O8—Co3—O3iv	86.65 (10)	Co2—O5—Co3viii	120.96 (14)
O8ii—Co3—O3iv	64.61 (10)	P1—O6—Co3	135.08 (18)
O5iii—Co3—O3iv	159.51 (11)	Co3—O7—H1	113 (4)
O6—Co3—P2v	131.88 (9)	Co3—O7—H2	115 (4)
O7—Co3—P2v	94.83 (9)	H1—O7—H2	105 (5)
O8—Co3—P2v	82.21 (8)	P2x—O8—Co3	129.77 (16)
O8ii—Co3—P2v	32.34 (8)	P2x—O8—Co3xi	101.70 (14)
O5iii—Co3—P2v	130.28 (8)	Co3—O8—Co3xi	128.53 (14)
O6—P1—O4i	112.20 (17)	P2—O9—Co2	157.0 (2)
O6—P1—O2vi	111.63 (16)
O6—P1—O1—Co2	36.4 (2)	O1—Co2—O5—P2x	−54.5 (2)
O4i—P1—O1—Co2	−86.41 (19)	O2i—Co2—O5—P2x	−153.51 (18)
O2vi—P1—O1—Co2	156.73 (16)	O9—Co2—O5—Co3viii	−111.58 (17)
O6—P1—O1—Co1	−170.63 (17)	O1—Co2—O5—Co3viii	110.83 (17)
O4i—P1—O1—Co1	66.5 (2)	O2i—Co2—O5—Co3viii	11.79 (18)
O2vi—P1—O1—Co1	−50.3 (2)	O4i—P1—O6—Co3	−132.6 (2)
O9—Co2—O1—P1	−176.28 (16)	O2vi—P1—O6—Co3	−10.2 (3)
O5—Co2—O1—P1	−39.6 (2)	O1—P1—O6—Co3	106.6 (3)
O2i—Co2—O1—P1	66.23 (18)	O7—Co3—O6—P1	55.9 (3)
O9—Co2—O1—Co1	29.6 (2)	O8—Co3—O6—P1	−134.0 (3)
O5—Co2—O1—Co1	166.29 (13)	O8ii—Co3—O6—P1	156.2 (3)
O2i—Co2—O1—Co1	−87.91 (15)	O5iii—Co3—O6—P1	−29.8 (3)
O3—Co1—O1—P1	122.72 (19)	P2v—Co3—O6—P1	151.72 (19)
O4—Co1—O1—P1	−119.25 (19)	O6—Co3—O8—P2x	44.9 (2)
O2—Co1—O1—P1	−10.1 (2)	O7—Co3—O8—P2x	102.3 (6)
O3—Co1—O1—Co2	−83.97 (17)	O8ii—Co3—O8—P2x	−150.0 (2)
O4—Co1—O1—Co2	34.06 (16)	O5iii—Co3—O8—P2x	−51.7 (2)
O2—Co1—O1—Co2	143.21 (14)	P2v—Co3—O8—P2x	178.6 (2)
O3—Co1—O2—P1vi	−18.9 (2)	O6—Co3—O8—Co3xi	−134.86 (19)
O4—Co1—O2—P1vi	−148.23 (18)	O7—Co3—O8—Co3xi	−77.4 (6)
O1—Co1—O2—P1vi	106.71 (19)	O8ii—Co3—O8—Co3xi	30.29 (16)
O3—Co1—O2—Co2i	154.62 (15)	O5iii—Co3—O8—Co3xi	128.52 (17)
O4—Co1—O2—Co2i	25.34 (19)	P2v—Co3—O8—Co3xi	−1.19 (16)
O1—Co1—O2—Co2i	−79.72 (18)	O8vii—P2—O9—Co2	116.3 (5)
O4—Co1—O3—P2iii	−129.2 (2)	O3viii—P2—O9—Co2	−1.5 (6)
O2—Co1—O3—P2iii	105.0 (2)	O5vii—P2—O9—Co2	−121.7 (5)
O1—Co1—O3—P2iii	−20.1 (2)	Co3ix—P2—O9—Co2	69.4 (6)
O3—Co1—O4—P1i	−150.21 (19)	O5—Co2—O9—P2	137.1 (5)
O2—Co1—O4—P1i	−16.1 (2)	O1—Co2—O9—P2	−83.5 (6)
O1—Co1—O4—P1i	94.9 (2)	O2i—Co2—O9—P2	20.1 (6)
O9—Co2—O5—P2x	83.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H2···O6iii	0.90 (3)	1.86 (4)	2.753 (4)	170 (5)
O7—H1···O4v	0.90 (1)	1.86 (2)	2.758 (4)	171 (5)

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—O3iv	2.416 (3)
P1—O6	1.513 (3)
P1—O4i	1.534 (3)
P1—O2v	1.560 (3)
P1—O1	1.561 (3)
P2—O9	1.511 (3)
P2—O8vi	1.544 (3)
P2—O3vii	1.549 (3)
P2—O5vi	1.565 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H2⋯O6iii	0.90 (3)	1.86 (4)	2.753 (4)	170 (5)
O7—H1⋯O4viii	0.903 (10)	1.864 (15)	2.758 (4)	171 (5)

Symmetry codes: (iii) ; (viii) .