KHCoP₂O₇·2H₂O: a novel acidic pyrophosphate

Potassium cobalt hydrogenpyrophosphate dihydrate, KHCoP₂O₇·2H₂O, crystallizes in the orthorhombic space group Pnma. This salt is isotypic with KHMP₂O₇·2H₂O (M = Mn and Zn). The structure consists of alternating layers, built from HP₂O₇^3- acidic pyrophosphate groups and CoO₆ octahedra, joined by potassium ions and bridging hydrogen bonds. The Co, K and water O atoms lie on mirror planes. The pyrophosphate group consists of two symmetry-related PO₄ groups, with the bridging O atom on a mirror plane.

S1. Comment

Hydrated or anhydrous pyrophosphates containing acidic anionic [H₃P₂O₇]⁻,[H₂P₂O₇]²⁻ or [HP₂O₇]³⁻ entities are topics of wide-spread interest in the crystallographic literature (Corbridge, 1957; Dumas et al., 1973; Mathew & Schroeder, 1977; Durif & Averbuch-Pouchot, 1982; Haromy-Tuli et al., 1984; Effenberger, 1987; Haromy-Tuli et al., 1990; Simonova et al., 1991; Byrappa & Umesh Dutt, 1994; Hsu & Wang, 1999; Chehimi et al., 2001; Blum et al., 2002; Ivashkevich et al., 2002; Chehimi et al., 2002). The present paper is an extension of our earlier work on the acidic pyrophosphates that we have recently realised and analyzed, viz. KHMP₂O₇·2H₂O (M = Mn, Zn) (Assaaoudi et al., 2002) and Na₄Mg₂(H₂P₂O₇)₄·8H₂O (Harcharras et al., accepted). We report here the crystal structure of the new pyrophosphate, KHCoP₂O₇·2H₂O.

The pyrophosphate group consists of two symmetry-related PO₄ groups, with the bridging atom (O1) in a special position. The Co-atom octahedron and pyrophosphate groups are depicted in Figs. 1a and 1 b. The three-dimensional structure is built from acidic pyrophosphate–Co^II layers stacked along the c axis (Fig. 2), alternating with layers of K⁺ ions. The Co²⁺ ions are octahedrally surrounded by four O atoms from three different pyrophosphate anions and by two water molecules (Table 1).

It is possible to distinguish three types of P—O distances, viz. P—O1 bonds [1.618 (2) Å, which is the longest bond] corresponding to the bridging O atoms, P—O2 bonds [1.541 (2) Å] involving hydroxyl groups, and P—O(3,4) bonds corresponding to the external O atoms [mean 1.502 (2) Å, which are the shortest bonds). The HP₂O₇³⁻ anions show an eclipsed conformation, with a P—O—P bridging angle of 130.5 (2)°; the average O—P—O angle is 109.4°. The hydrogen-bond bridging is depicted in Table 2.

S2. Experimental

An aqueous solution of cobalt dichloride hexahydrate CoCl₂·6H₂O (0.1M) was added dropwise to a solution of K₄P₂O₇ (0.1M). Anhydrous tetrapotassium pyrophosphate, K₄P₂O₇, was prepared by dehydration of K₂HPO₄ at 873 K for 6 h. The pH of the mixture of these two solutions was controlled with concentrated hydrochloric acid. The solution was left at room temperature and crystals appeared in the solution after 4 d. They were identified as KHCoP₂O₇·2H₂O.

S3. Refinement

H atoms were located from difference Fourier maps and were restrained to lie 0.96 Šfrom their carrier atoms, with fixed displacement parameters of 0.035 Ų. H2 was split into two half-occupied positions around a centre of inversion.

Computing details

Data collection: KappaCCD; cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1996); program(s) used to refine structure: Xtal3.7 (Hall et al., 2000) CRYLSQ; molecular graphics: PLATON (Spek, 2003), ORTEP (Johnson, 1970), PLUTON (Spek, 1991); software used to prepare material for publication: Xtal BONDLA CIFIO PLATON.

Figures

	Fig. 1. Views of the CoO4(H2O)^2+ coordination polyhedron (a) and the pyrophosphate group (b). Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Projections of the crystal structure along the c axis, showing the network of pyrophosphate and CoO4(H2O) groups.

(I)

Crystal data

KHCoP2O7·2H2O	F(000) = 612
Mr = 309.01	Dx = 2.623 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ac 2n	Cell parameters from 955 reflections
a = 15.4724 (15) Å	θ = 2.6–27.5°
b = 7.7881 (8) Å	µ = 3.16 mm^−1
c = 6.4942 (6) Å	T = 250 K
V = 782.56 (14) Å^3	Plate, colourless
Z = 4	0.2 × 0.2 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer	955 reflections with F^2 > .00 sig(F^2)
Radiation source: fine-focus sealed tube	Rint = 0.041
ϕ–scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements) MULABS; Blessing, 1995	h = −15→20
Tmin = 0.569, Tmax = 0.669	k = −10→8
4664 measured reflections	l = −7→8
955 independent reflections

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.034	1/[900. + 0.01*(σ(Fo^2)^2) + 0.01/(σ(Fo^2))]
wR(F^2) = 0.039	(Δ/σ)max = 0.042
S = 1.38	Δρmax = 0.62 e Å^−3
955 reflections	Δρmin = −0.97 e Å^−3
80 parameters	Extinction correction: Zachariasen (1967), Eq22 p292 Cryst. Comp. Munksgaard 1970
3 restraints	Extinction coefficient: 1630 (119)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	0.30492 (4)	0.75000	0.56152 (11)	0.0108 (3)
K	0.53494 (7)	0.75000	0.61789 (19)	0.0189 (5)
P	0.13604 (5)	0.56130 (10)	0.36122 (14)	0.0106 (4)
O1	0.1125 (2)	0.75000	0.2732 (6)	0.0137 (16)
O2	0.07528 (13)	0.5311 (3)	0.5457 (4)	0.0149 (11)
H2	0.018 (3)	0.516 (14)	0.494 (18)	0.03500*	.50000
O3	0.11494 (12)	0.4429 (3)	0.1864 (4)	0.0136 (10)
O4	0.22892 (13)	0.5616 (3)	0.4301 (4)	0.0141 (10)
O5w	0.3944 (2)	0.75000	0.3090 (6)	0.0176 (17)
H5w	0.404 (3)	0.656 (3)	0.218 (5)	0.03500*
O6w	0.2153 (2)	0.75000	0.8164 (6)	0.0160 (17)
H6w	0.233 (3)	0.663 (4)	0.912 (5)	0.03500*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0105 (3)	0.0087 (3)	0.0133 (3)	0.00000	−0.0012 (3)	0.00000
K	0.0156 (5)	0.0219 (5)	0.0191 (6)	0.00000	0.0001 (5)	0.00000
P	0.0102 (3)	0.0075 (3)	0.0140 (4)	−0.0005 (3)	0.0003 (4)	−0.0009 (4)
O1	0.0180 (16)	0.0101 (12)	0.0132 (19)	0.00000	−0.0035 (15)	0.00000
O2	0.0129 (10)	0.0168 (10)	0.0149 (13)	−0.0013 (8)	0.0005 (10)	0.0004 (11)
O3	0.0136 (10)	0.0113 (8)	0.0157 (13)	−0.0019 (9)	−0.0019 (9)	−0.0041 (10)
O4	0.0131 (10)	0.0082 (9)	0.0211 (12)	0.0002 (8)	−0.0034 (10)	−0.0027 (11)
O5w	0.0247 (18)	0.0140 (14)	0.0141 (19)	0.00000	0.0044 (16)	0.00000
O6w	0.0172 (17)	0.0115 (14)	0.0193 (19)	0.00000	−0.0001 (15)	0.00000

Geometric parameters (Å, º)

Co—O3	2.110 (2)	K—O2	2.840 (3)
Co—O3^i	2.110 (2)	K—O5w	2.958 (4)
Co—O4	2.065 (2)	P—O1	1.618 (2)
Co—O4	2.065 (2)	P—O2	1.541 (2)
Co—O5w	2.146 (4)	P—O3	1.499 (2)
Co—O6w	2.159 (4)	P—O4	1.505 (2)
Co—K	3.5778 (12)	O2—H2	0.96 (6)
K—O3^i	2.798 (2)	H2—H2^i	0.61 (9)
K—O3	2.798 (2)	O5w—H5w	0.96 (3)
K—O1	2.809 (4)	O5w—H5w	0.96 (3)
K—O6w	2.823 (3)	O6w—H6w	0.96 (3)
K—O2	2.840 (3)	O6w—H6w	0.96 (3)
H6w···H6w	1.35 (4)	P···O5w	3.815 (3)
H5w···H5w	1.47 (4)	O1···O2	3.824 (3)
O2···H2^i	1.51 (6)	O1···O2	3.824 (3)
O4···H6w	1.85 (3)	O5w···H6w	3.84 (3)
O2···H5w	1.86 (3)	O5w···H6w	3.84 (3)
P···H2	2.05 (7)	P···H2^ii	3.86 (10)
H2···H5w	2.31 (10)	O1···O6w	3.870 (5)
O2···O2^i	2.453 (3)	H2···O4^i	3.90 (5)
O1···O3^ii	2.458 (2)	K···P^i	3.9209 (12)
O1···O3	2.458 (2)	K···P	3.9209 (12)
H2···H5w	2.49 (9)	P···H6w	3.92 (3)
O2···O4	2.504 (3)	K···O2^i	3.927 (2)
O2···O3	2.509 (3)	K···O2	3.927 (2)
O1···O2	2.524 (4)	Co···O2	3.942 (2)
O1···O2^ii	2.524 (4)	Co···O2	3.942 (2)
O1···O4^ii	2.537 (3)	O4···O5w	3.948 (4)
O1···O4	2.537 (3)	P···H6w	3.96 (3)
O3···O4	2.544 (3)	P···H5w	3.97 (3)
H2···O3	2.56 (10)	H5w···O6w	3.98 (4)
Co···H6w	2.62 (3)	O2···H5w	3.99 (3)
Co···H6w	2.62 (3)	O4···H6w	3.99 (3)
P···H2	2.63 (6)	O2···O4	3.991 (3)
O4···O6w	2.679 (3)	O3···H6w	3.99 (3)
P···H6w	2.69 (4)	O2···O5w	4.005 (4)
O1···H2	2.74 (10)	K···P	4.0062 (14)
O1···H2^ii	2.74 (10)	K···P	4.0062 (14)
Co···H5w	2.81 (4)	P···O6w	4.023 (4)
Co···H5w	2.81 (4)	O2···O4	4.034 (3)
O2···O5w	2.818 (3)	P···O3^ii	4.038 (2)
O3···O5w	2.878 (4)	K···O5w	4.0722 (11)
O3···H6w	2.89 (4)	K···O5w	4.0722 (11)
O4···O6w	2.914 (4)	P···O3	4.100 (2)
P···H5w	2.93 (3)	O1···O4	4.107 (4)
O3···O4	2.934 (3)	O1···O4	4.107 (4)
O4···O4	2.935 (3)	K···O1	4.132 (4)
H2···O3^i	2.94 (9)	P···O5w	4.166 (3)
P···P^ii	2.9393 (11)	O3···O5w	4.167 (3)
O3···O3^i	3.004 (3)	O3···O4	4.174 (3)
O4···O5w	3.054 (4)	O2···O6w	4.184 (3)
O1···H6w	3.08 (3)	Co···O6w	4.2185 (15)
O1···H6w	3.08 (3)	Co···O6w	4.2185 (15)
O3···H6w	3.08 (3)	O5w···O6w	4.232 (5)
K···H2	3.12 (11)	P···H5w	4.24 (4)
K···H2	3.12 (11)	O5w···O6w	4.2485 (19)
O4···H5w	3.13 (4)	O5w···O6w	4.2485 (19)
O3···O6w	3.141 (3)	O4···O6w	4.252 (4)
O2···H5w	3.15 (3)	Co···O2	4.256 (2)
K···H6w	3.15 (4)	Co···O2^i	4.256 (2)
K···H6w	3.15 (4)	O2···O3	4.262 (3)
O3···H5w	3.15 (3)	P···O5w	4.273 (3)
O4···H6w	3.16 (3)	O5w···O6w	4.305 (5)
H2···O5w	3.21 (10)	P···H5w	4.31 (4)
O4···H6w	3.23 (3)	O3···O5w	4.316 (4)
Co···P	3.2404 (10)	K···K	4.3218 (8)
Co···P^i	3.2404 (10)	K···K	4.3218 (8)
O4···H5w	3.25 (4)	Co···O1	4.3226 (16)
O1···H2	3.26 (9)	Co···O1	4.3226 (16)
O1···H2	3.26 (9)	P···O4	4.351 (2)
Co···P	3.2679 (10)	P···O5w	4.354 (3)
Co···P	3.2679 (10)	O1···O5w	4.368 (5)
O2···O6w	3.270 (4)	P···H2	4.37 (10)
H2···O5w	3.29 (10)	O2···O2	4.379 (3)
O2···H5w	3.30 (4)	K···H2^ii	4.38 (11)
P···O4^ii	3.300 (2)	K···H2	4.38 (11)
H5w···H6w	3.30 (5)	P···O3	4.394 (2)
K···H2^i	3.31 (11)	K···O4	4.397 (2)
K···H2	3.31 (11)	K···O4	4.397 (2)
O1···H5w	3.31 (4)	Co···O2	4.410 (2)
O1···H5w	3.31 (4)	Co···O2	4.410 (2)
H2···O4	3.31 (5)	Co···H6w	4.41 (3)
K···O3^ii	3.341 (2)	Co···H6w	4.41 (3)
K···O3	3.341 (2)	K···O4	4.447 (2)
P···O6w	3.354 (2)	K···O4	4.447 (2)
O1···O6w	3.366 (5)	K···H5w	4.45 (3)
K···H5w	3.38 (4)	K···H5w	4.45 (3)
K···H5w	3.38 (4)	Co···O3	4.505 (2)
P···H6w	3.38 (3)	Co···O3	4.505 (2)
H2···H5w	3.38 (11)	K···H2	4.62 (11)
H2···H5w	3.40 (10)	K···H2	4.62 (11)
P···O2	3.402 (2)	K···O1	4.6246 (19)
O2···O2	3.409 (3)	K···O1	4.6246 (19)
Co···H6w	3.41 (3)	K···O2	4.638 (3)
Co···H6w	3.41 (3)	K···O2	4.638 (3)
O1···O5w	3.417 (5)	Co···K	4.6672 (13)
O2···O3^i	3.425 (3)	K···O2^ii	4.676 (3)
O2···H6w	3.44 (4)	K···O2	4.676 (3)
O4···O4	3.448 (3)	P···P	4.6779 (11)
O4···O4	3.448 (3)	Co···K	4.7603 (8)
Co···O4^i	3.448 (2)	Co···K	4.7603 (8)
Co···O4	3.448 (2)	Co···O4	4.793 (2)
O4···H6w	3.46 (3)	Co···O4	4.793 (2)
K···H5w	3.47 (3)	K···H5w	4.84 (3)
K···H5w	3.47 (3)	K···H5w	4.84 (3)
H5w···H6w	3.50 (5)	P···P	4.8488 (12)
Co···O1	3.517 (3)	K···O4^ii	4.881 (3)
P···O2^ii	3.521 (2)	K···O4	4.881 (3)
O3···H6w	3.52 (3)	P···P	4.8879 (12)
P···O6w	3.522 (3)	P···P	4.8879 (12)
O3···H5w	3.55 (3)	K···O5w	4.987 (4)
O2···H6w	3.56 (4)	K···H6w	5.09 (4)
H5w···H6w	3.59 (5)	K···H6w	5.09 (4)
P···O4	3.622 (2)	K···O4	5.105 (2)
O5w···H6w	3.65 (4)	K···O4	5.105 (2)
O5w···H6w	3.65 (4)	K···O6w	5.110 (3)
O2···H2	3.65 (11)	K···O4^i	5.164 (2)
P···H5w	3.70 (4)	K···O4	5.164 (2)
O3···H5w	3.71 (4)	K···O3	5.260 (3)
H5w···O6w	3.71 (3)	K···O3	5.260 (3)
P···H6w	3.72 (3)	K···P	5.6401 (13)
O3···O6w	3.730 (4)	K···P	5.6401 (13)
O4···H5w	3.75 (4)	Co···K	6.0759 (14)
K···P^ii	3.7800 (14)	K···K	6.4003 (14)
K···P	3.7800 (14)	K···K	6.4003 (14)
O3···H5w	3.79 (3)	K···K	6.4942 (18)
O4···H6w	3.79 (3)	K···K	6.4942 (18)
O4—Co—O4	90.58 (9)	O6w—K—O2	70.52 (8)
O4—Co—O3	178.04 (9)	O6w—K—O2	70.52 (8)
O4—Co—O3^i	89.29 (8)	O6w—K—O5w	146.00 (11)
O4—Co—O5w	92.96 (9)	O6w—K—Co	177.18 (9)
O4—Co—O6w	87.21 (9)	O2—K—O2	73.75 (7)
O4—Co—K	127.49 (6)	O2—K—O5w	133.08 (6)
O4—Co—O3	89.29 (8)	O2—K—Co	107.30 (5)
O4—Co—O3^i	178.04 (9)	O2—K—O5w	133.08 (6)
O4—Co—O5w	92.96 (9)	O2—K—Co	107.30 (5)
O4—Co—O6w	87.21 (9)	O5w—K—Co	36.82 (7)
O4—Co—K	127.49 (6)	O1—P—O2	106.01 (15)
O3—Co—O3^i	90.77 (8)	O1—P—O3	104.03 (16)
O3—Co—O5w	85.09 (9)	O1—P—O4	108.56 (14)
O3—Co—O6w	94.74 (9)	O2—P—O3	111.23 (12)
O3—Co—K	51.39 (6)	O2—P—O4	110.59 (13)
O3^i—Co—O5w	85.09 (9)	O3—P—O4	115.72 (12)
O3^i—Co—O6w	94.74 (9)	P^ii—O1—P	130.5 (2)
O3^i—Co—K	51.39 (6)	P^ii—O1—K	114.54 (12)
O5w—Co—O6w	179.76 (14)	P—O1—K	114.54 (12)
O5w—Co—K	55.69 (10)	H2—O2—P	108 (6)
O6w—Co—K	124.07 (10)	H2—O2—K	98 (6)
O3^i—K—O3	64.92 (6)	P—O2—K	129.84 (11)
O3^i—K—O1	119.86 (8)	H2^i—H2—O2	148 (19)
O3^i—K—O6w	142.67 (6)	P—O3—Co	126.96 (12)
O3^i—K—O2	112.45 (8)	P—O3—K	129.15 (11)
O3^i—K—O2	74.80 (6)	Co—O3—K	92.51 (8)
O3^i—K—O5w	59.92 (7)	P—O4—Co	131.87 (13)
O3^i—K—Co	36.10 (5)	H5w—O5w—H5w	101 (3)
O3—K—O1	119.86 (8)	H5w—O5w—Co	125 (2)
O3—K—O6w	142.67 (6)	H5w—O5w—K	108 (2)
O3—K—O2	74.80 (6)	H5w—O5w—Co	125 (2)
O3—K—O2	112.45 (8)	H5w—O5w—K	108 (2)
O3—K—O5w	59.92 (7)	Co—O5w—K	87.49 (12)
O3—K—Co	36.10 (5)	H6w—O6w—H6w	90 (3)
O1—K—O6w	73.40 (11)	H6w—O6w—Co	108 (2)
O1—K—O2	126.98 (7)	H6w—O6w—K	101 (2)
O1—K—O2	126.98 (7)	H6w—O6w—Co	108 (2)
O1—K—O5w	72.60 (10)	H6w—O6w—K	101 (2)
O1—K—Co	109.42 (8)	Co—O6w—K	138.64 (16)
O3—Co—K—O1	114.36 (8)	O3^i—Co—O6w—H6w	−93 (2)
O3—Co—K—O2	−104.58 (10)	O3^i—Co—O6w—K	134.41 (6)
O3—Co—K—O3	0.00 (11)	O3^i—Co—O6w—H6w	2 (2)
O3—Co—K—O5w	114.36 (8)	O4—Co—O6w—H6w	177 (2)
O3—Co—K—O6w	−65.64 (9)	O4—Co—O6w—K	45.36 (6)
O3—Co—K—O2	−26.70 (9)	O4—Co—O6w—H6w	−87 (2)
O3—Co—K—O3^i	−131.29 (12)	K—Co—O3^i—K	0.00 (3)
O4—Co—K—O1	63.60 (9)	O3—Co—O3^i—K	35.96 (8)
O4—Co—K—O2	−155.34 (10)	O4—Co—O3^i—K	−56 (2)
O4—Co—K—O3	−50.76 (12)	O5w—Co—O3^i—K	−49.05 (9)
O4—Co—K—O5w	63.60 (9)	O6w—Co—O3^i—K	130.78 (8)
O4—Co—K—O6w	−116.40 (10)	O4—Co—O3^i—K	−142.08 (9)
O4—Co—K—O2	−77.46 (11)	Co—K—O1—P	93.30 (16)
O4—Co—K—O3^i	177.95 (12)	Co—K—O1—P^ii	−93.30 (16)
O5w—Co—K—O1	−0.0001	O2—K—O1—P	−38.0 (2)
O5w—Co—K—O2	141.06 (5)	O2—K—O1—P^ii	135.39 (14)
O5w—Co—K—O3	−114.36 (8)	O3—K—O1—P	131.53 (15)
O5w—Co—K—O5w	0.0001	O3—K—O1—P^ii	−55.1 (2)
O5w—Co—K—O6w	180.000 (5)	O5w—K—O1—P	93.30 (16)
O5w—Co—K—O2	−141.06 (5)	O5w—K—O1—P^ii	−93.30 (16)
O5w—Co—K—O3^i	114.36 (8)	O6w—K—O1—P	−86.70 (16)
O6w—Co—K—O1	180.0000	O6w—K—O1—P^ii	86.70 (16)
O6w—Co—K—O2	−38.94 (5)	O2—K—O1—P	−135.39 (14)
O6w—Co—K—O3	65.64 (8)	O2—K—O1—P^ii	38.0 (2)
O6w—Co—K—O5w	180.0000	O3^i—K—O1—P	55.1 (2)
O6w—Co—K—O6w	−0.000 (6)	O3^i—K—O1—P^ii	−131.53 (15)
O6w—Co—K—O2	38.94 (5)	Co—K—O2—H2	11 (7)
O6w—Co—K—O3^i	−65.64 (8)	Co—K—O2—P	132.57 (14)
O3^i—Co—K—O1	−114.36 (8)	O1—K—O2—H2	143 (7)
O3^i—Co—K—O2	26.70 (9)	O1—K—O2—P	−95.33 (16)
O3^i—Co—K—O3	131.29 (12)	O3—K—O2—H2	−27 (7)
O3^i—Co—K—O5w	−114.36 (8)	O3—K—O2—P	94.48 (15)
O3^i—Co—K—O6w	65.64 (9)	O5w—K—O2—H2	42 (7)
O3^i—Co—K—O2	104.58 (10)	O5w—K—O2—P	163.62 (14)
O3^i—Co—K—O3^i	−0.00 (11)	O6w—K—O2—H2	−168 (7)
O4—Co—K—O1	−63.60 (9)	O6w—K—O2—P	−45.55 (15)
O4—Co—K—O2	77.46 (11)	O2—K—O2—H2	−93 (7)
O4—Co—K—O3	−177.95 (12)	O2—K—O2—P	29.06 (15)
O4—Co—K—O5w	−63.60 (9)	O3^i—K—O2—H2	27 (7)
O4—Co—K—O6w	116.40 (10)	O3^i—K—O2—P	148.50 (16)
O4—Co—K—O2	155.34 (10)	Co—K—O3—Co	0.00 (3)
O4—Co—K—O3^i	50.76 (12)	Co—K—O3—P	−144.3 (2)
K—Co—O3—K	−0.00 (3)	O1—K—O3—Co	−82.15 (9)
K—Co—O3—P	145.5 (2)	O1—K—O3—P	133.57 (14)
O4—Co—O3—K	142.08 (9)	O2—K—O3—Co	88.82 (9)
O4—Co—O3—P	−72.45 (17)	O2—K—O3—P	−55.46 (17)
O5w—Co—O3—K	49.05 (8)	O5w—K—O3—Co	−39.12 (7)
O5w—Co—O3—P	−165.48 (17)	O5w—K—O3—P	176.61 (18)
O6w—Co—O3—K	−130.78 (8)	O6w—K—O3—Co	175.76 (13)
O6w—Co—O3—P	14.69 (17)	O6w—K—O3—P	31.5 (2)
O3^i—Co—O3—K	−35.96 (8)	O2—K—O3—Co	153.60 (9)
O3^i—Co—O3—P	109.51 (17)	O2—K—O3—P	9.33 (15)
O4—Co—O3—K	56 (2)	O3^i—K—O3—Co	29.26 (7)
O4—Co—O3—P	−159 (2)	O3^i—K—O3—P	−115.01 (17)
K—Co—O4—P	−166.27 (14)	Co—K—O5w—Co	0.0001
O3—Co—O4—P	156.5 (2)	Co—K—O5w—H5w	−126 (2)
O5w—Co—O4—P	−118.5 (2)	Co—K—O5w—H5w	126 (2)
O6w—Co—O4—P	61.7 (2)	O1—K—O5w—Co	−180.0000
O3^i—Co—O4—P	−112 (2)	O1—K—O5w—H5w	54 (2)
O4—Co—O4—P	−25.5 (2)	O1—K—O5w—H5w	−54 (2)
K—Co—O5w—K	−0.0001	O2—K—O5w—Co	−55.25 (9)
K—Co—O5w—H5w	110 (3)	O2—K—O5w—H5w	179 (2)
K—Co—O5w—H5w	−110 (3)	O2—K—O5w—H5w	71 (2)
O3—Co—O5w—K	−45.60 (6)	O3—K—O5w—Co	38.33 (6)
O3—Co—O5w—H5w	65 (3)	O3—K—O5w—H5w	−88 (2)
O3—Co—O5w—H5w	−156 (3)	O3—K—O5w—H5w	164 (2)
O4—Co—O5w—K	−134.64 (6)	O6w—K—O5w—Co	−180.0000
O4—Co—O5w—H5w	−24 (3)	O6w—K—O5w—H5w	54 (2)
O4—Co—O5w—H5w	115 (3)	O6w—K—O5w—H5w	−54 (2)
O6w—Co—O5w—K	−0.003 (3)	O2—K—O5w—Co	55.25 (9)
O6w—Co—O5w—H5w	110 (3)	O2—K—O5w—H5w	−71 (2)
O6w—Co—O5w—H5w	−110 (3)	O2—K—O5w—H5w	−179 (2)
O3^i—Co—O5w—K	45.60 (6)	O3^i—K—O5w—Co	−38.33 (6)
O3^i—Co—O5w—H5w	156 (3)	O3^i—K—O5w—H5w	−164 (2)
O3^i—Co—O5w—H5w	−65 (3)	O3^i—K—O5w—H5w	88 (2)
O4—Co—O5w—K	134.64 (6)	Co—K—O3^i—Co	−0.00 (3)
O4—Co—O5w—H5w	−115 (3)	O1—K—O3^i—Co	82.15 (9)
O4—Co—O5w—H5w	24 (3)	O2—K—O3^i—Co	−153.60 (9)
K—Co—O6w—H6w	−48 (2)	O3—K—O3^i—Co	−29.26 (7)
K—Co—O6w—K	180.0000 (15)	O5w—K—O3^i—Co	39.12 (7)
K—Co—O6w—H6w	48 (2)	O6w—K—O3^i—Co	−175.76 (13)
O3—Co—O6w—H6w	−2 (2)	O2—K—O3^i—Co	−88.82 (9)
O3—Co—O6w—K	−134.41 (6)	O2—P—O1—K	−112.01 (16)
O3—Co—O6w—H6w	93 (2)	O2—P—O1—P^ii	75.9 (3)
O4—Co—O6w—H6w	87 (2)	O4—P—O1—K	129.15 (15)
O4—Co—O6w—K	−45.36 (6)	O4—P—O1—P^ii	−42.9 (3)
O4—Co—O6w—H6w	−177 (2)	O3—P—O1—K	5.38 (18)
O5w—Co—O6w—H6w	−48 (2)	O3—P—O1—P^ii	−166.7 (2)
O5w—Co—O6w—K	−179.997 (3)	K—O2—H2—H2^i	−71 (35)
O5w—Co—O6w—H6w	48 (2)	P—O2—H2—H2^i	152 (33)

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