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

inorganic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages i67-i68

doi:10.1107/S1600536808028377

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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

(Received 29 August 2008; accepted 4 September 2008; online 13 September 2008)

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 PO₄³⁻ 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—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_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 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[F² > 2σ(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
Δρ_max = 0.55 e Å⁻³
Δρ_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—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H5⋯O3^iv	0.894 (10)	2.25 (8)	2.764 (4)	116 (7)
O4—H5⋯O7^v	0.894 (10)	2.49 (8)	3.209 (3)	138 (9)
O4—H6⋯O3^vi	0.894 (10)	2.02 (7)	2.764 (4)	140 (10)
O5—H4⋯O3^vii	0.892 (10)	2.25 (2)	3.133 (5)	170 (8)
O5—H4⋯O3^viii	0.892 (10)	2.66 (8)	3.133 (5)	115 (6)
O6—H1⋯O1^vii	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) $[x, -y+{\script{1\over 2}}, z+1]$ ; (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 ).

Supporting information

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

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

checkCIF report

Comment top

The synthesis and investigation of open-framework transition-metal phosphates has been a growing area of research over recent times. This is not only because of the rich structural chemistry involved, but is also due to many potential applications such as for catalysis, as alternatives for zeolites in separation and storage applications and, in particular, as potential gas storage materials (Kuzicki et al., 2001; Chen et al., 2006; Jiang & Gao, 2007; Cheetham et al., 1999). For example, microporous nickel phosphates incorporating 24-membered rings such as VSB-5 (Versailles/Santa Barbara-5) have been demonstrated to exhibit hydrogen uptake at low temperatures (Forster et al., 2003). Over the past couple of decades, a considerable number of metal phosphates/phosphites with open molecular architectures have also been synthesized incorporating organic units (see, for example: Jiang et al., 2001) and ionic liquids (Cooper et al., 2004) as structure-directing agents, often under hydrothermal or solvothermal conditions. One of the best known families of this type consists of zinc phosphate structures; individual materials of this type can exist as one dimensional (chain and ladder), two dimensional (layer) and three dimensional framework arrangements (Choudhury et al., 2000).

We are currently investigating the synthesis of a variety of similar functional materials through templation effects under hydrothermal conditions. The title compound, Co₃(PO₄)₂.4H₂O, (I), and the related compound Co₃(PO₄)₂.H₂O (Lee et al., 2008) were synthesized and structurally characterized as a part of these studies.

The structure of (I) is isotypic with the mineral hopeite, Zn₃(PO₄)₂.4H₂O (Liebau, 1965) and contains two different Co²⁺ centres bridged by orthophosphate anions (Fig. 1). The coordination environment of Co1 is slightly distorted tetrahedral while that of Co2 is close to octahedral (Table 1). Co1 is bonded to the O atoms of four different phosphate ligands, while Co2 is bonded to the O atoms of two orthophosphate ligands in a cis-arrangement. The other coordination sites are occupied by O atoms of the water ligands. A mirror plane passes through Co2 and two of the water molecules (O4 and O5). This coordination geometry leads to the formation of a three-dimensional framework (Fig. 2). A number of hydrogen bonding interactions O—H···O are present and stabilize the structure (Table 2).

Related literature top

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 top

H₃PO₄ (85%_wt, 2.3 g, 20 mmol) was added to an aqueous solution (20 ml) of Co(NO₃)₂.6H₂O (2.6 g, 9 mmol) with stirring for 30 min and the ionic liquid, 1-butyl-3-methylimidazolium bromide (2.7 g, 9 mmol), was added dropwise under continuous stirring. The mixture was transferred to a teflon-coated autoclave, heated at 453 K for 3 d and then allowed to cool slowly. A mixture of plate-like and prismatic purple crystals had formed and was filtered off. The crystals were washed with water, dried under vacuum and were manually separated under a microscope. The yields were approximately 0.4 g of the plate-like crystals of the compound Co₃(PO₄)₂.H₂O (Lee et al., 2008) and and 0.2 g of the prismatic crystals of compound (I).

Computing details top

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).

Figures top

	Fig. 1. The asymmetric unit of compound (I), drawn with displacement parameters at the 50% probability level. H atoms are given as spheres of arbitrary radius.
	Fig. 2. A schematic representation of a section of the three-dimensional network in a projection along [001]. Hydrogen atoms are omitted for clarity.

Tricobalt(II) bis[orthophosphate(V)] tetrahydrate top

Crystal data top

Co₃(PO₄)₃·4H₂O	F(000) = 860
M_r = 438.79	D_x = 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

Data collection top

Siemens SMART 1000 CCD diffractometer	1228 independent reflections
Radiation source: sealed tube	1166 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	h = −13→13
T_min = 0.068, T_max = 0.125	k = −24→24
8780 measured reflections	l = −6→6

Refinement top

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(F_o²) + (0.059P)² + 3.8213P] where P = (F_o² + 2F_c²)/3
1228 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.55 e Å⁻³
10 restraints	Δρ_min = −1.38 e Å⁻³

Crystal data top

Co₃(PO₄)₃·4H₂O	V = 971.0 (5) Å³
M_r = 438.79	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 10.604 (3) Å	µ = 5.46 mm⁻¹
b = 18.288 (5) Å	T = 150 K
c = 5.0070 (13) Å	0.52 × 0.39 × 0.38 mm

Data collection top

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

Refinement top

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

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—O3^iv	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—O6^iv	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)
O3^iv—Co2—O3	86.26 (16)	P1—O1—Co1	130.42 (18)
O3^iv—Co2—O4	93.09 (12)	P1—O2—Co1^v	128.01 (16)
O3—Co2—O4	93.09 (12)	P1—O2—Co1ⁱⁱⁱ	115.24 (15)
O3^iv—Co2—O5	91.00 (12)	Co1^v—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)
O3^iv—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)
O3^iv—Co2—O6^iv	93.16 (12)	H3—O5—H4	134 (3)
O3—Co2—O6^iv	178.01 (12)	Co2—O6—H1	100 (4)
O4—Co2—O6^iv	85.03 (11)	Co2—O6—H2	110.7 (10)
O5—Co2—O6^iv	90.91 (12)	H1—O6—H2	132 (2)
O6—Co2—O6^iv	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)	O3^iv—Co2—O3—P1	153.57 (18)
O2ⁱⁱⁱ—Co1—O1—P1	132.9 (2)	O4—Co2—O3—P1	60.7 (3)
O7—P1—O2—Co1^v	34.1 (3)	O5—Co2—O3—P1	−115.5 (3)
O3—P1—O2—Co1^v	−88.5 (2)	O6—Co2—O3—P1	−24.5 (3)
O1—P1—O2—Co1^v	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)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, y, −z+1/2; (iii) −x+1, −y, −z; (iv) x, −y+1/2, z; (v) x−1/2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H5···O3^vi	0.89 (1)	2.25 (8)	2.764 (4)	116 (7)
O4—H5···O7^iv	0.89 (1)	2.49 (8)	3.209 (3)	138 (9)
O4—H6···O3^vii	0.89 (1)	2.02 (7)	2.764 (4)	140 (10)
O5—H4···O3^v	0.89 (1)	2.25 (2)	3.133 (5)	170 (8)
O5—H4···O3^viii	0.89 (1)	2.66 (8)	3.133 (5)	115 (6)
O6—H1···O1^v	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) x, −y+1/2, z; (v) x−1/2, y, −z+1/2; (vi) x, −y+1/2, z+1; (vii) x, y, z+1; (viii) x−1/2, −y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	Co₃(PO₄)₃·4H₂O
M_r	438.79
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	150
a, b, c (Å)	10.604 (3), 18.288 (5), 5.0070 (13)
V (Å³)	971.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.46
Crystal size (mm)	0.52 × 0.39 × 0.38

Data collection
Diffractometer	Siemens SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1999)
T_min, T_max	0.068, 0.125
No. of measured, independent and observed [I > 2σ(I)] reflections	8780, 1228, 1166
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.102, 1.16
No. of reflections	1228
No. of parameters	101
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −1.38

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and XPREP (Siemens, 1995), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WebLab ViewerPro (Molecular Simulations, 2000) and POV-RAY (Cason, 2002), enCIFer (Allen et al., 2004).

Selected bond lengths (Å) top

Co1—O7ⁱ	1.901 (3)	Co2—O6	2.138 (3)
Co1—O1	1.918 (3)	P1—O7	1.519 (3)
Co1—O2ⁱⁱ	1.983 (3)	P1—O3	1.521 (3)
Co1—O2ⁱⁱⁱ	1.986 (3)	P1—O1	1.537 (3)
Co2—O4	2.106 (4)	P1—O2	1.570 (3)
Co2—O5	2.118 (4)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, y, −z+1/2; (iii) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H5···O3^iv	0.894 (10)	2.25 (8)	2.764 (4)	116 (7)
O4—H5···O7^v	0.894 (10)	2.49 (8)	3.209 (3)	138 (9)
O4—H6···O3^vi	0.894 (10)	2.02 (7)	2.764 (4)	140 (10)
O5—H4···O3^vii	0.892 (10)	2.25 (2)	3.133 (5)	170 (8)
O5—H4···O3^viii	0.892 (10)	2.66 (8)	3.133 (5)	115 (6)
O6—H1···O1^vii	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) x, −y+1/2, z+1; (v) x, −y+1/2, z; (vi) x, y, z+1; (vii) x−1/2, y, −z+1/2; (viii) x−1/2, −y+1/2, −z+1/2.

Acknowledgements

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

References

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