Penta­cobalt(II) divanadium(III) tetrakis(diphosphate), Co₅V₂(P₂O₇)₄

Co₅V₂(P₂O₇)₄ was crystallized by chemical vapour transport using HCl as transport agent. Its crystal structure is isotypic to that of Fe^II₅Fe^III₂(P₂O₇)₄ and can be regarded as a member of the thortveitite structure family with corrugated layers of metal-oxygen polyhedra extending parallel to (010). Significant occupational disorder between cobalt(II) and vanadium(III) is observed. Four of the five cation sites are occupied by both cobalt and vanadium. The fifth cation site (Co1) is occupied by cobalt only. Sites Co1, M3 and M4 are located on twofold axes. Sites Co1, M2, M3 and M4 show o­cta­hedral coordination by oxygen; M5 has a square-pyramidal environment.

Key indicators

• Single-crystal X-ray study
• T = 293 K, P = 0.0 kPa
• Mean [sigma](Co-O) = 0.005 Å
• Disorder in main residue
• R factor = 0.046
• wR factor = 0.110
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  The absolute value of parameter shift to su ratio > 0.05
            Absolute value of the parameter shift to su ratio given   0.058
            Additional refinement cycles may be required.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.967
PLAT080_ALERT_2_C Maximum Shift/Error ............................       0.06
PLAT213_ALERT_2_C Atom Co1             has ADP max/min Ratio .....        3.1 prola
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              Co10 O56 P16 V4
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.085
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT975_ALERT_2_C Positive Residual Density at 0.59A from O11    .       0.76 eA-3

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          2
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................         13 Perc.
PLAT791_ALERT_4_G Note: The Model has Chirality at P1     (Verify)          R
PLAT791_ALERT_4_G Note: The Model has Chirality at P2     (Verify)          R
PLAT791_ALERT_4_G Note: The Model has Chirality at P3     (Verify)          S
PLAT791_ALERT_4_G Note: The Model has Chirality at P4     (Verify)          S
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         52
PLAT952_ALERT_5_G Reported and Calculated Lmax Values Differ by ..          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  14 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   4 ALERT type 5 Informative message, check

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S1. Comment

Equilibrium investigations in the ternary system CoO/V₂O₃/P₂O₅ revealed three new phosphates: Co^II₃V^III₄(PO₄)₆, Co^II₃V^III₂(P₂O₇)₃, and Co^II₅V^III₂(P₂O₇)₄ (Litterscheid, 2009).

Co^II₅V^III₂(P₂O₇)₄ crystallizes in the orthorhombic space group C222₁. The crystal structure is isotopic to that of Fe^II₅Fe^III₂(P₂O₇)₄ (Malaman et al., 1992). It consists of P₂O₇ groups and five independent polyhedra [MO_n] (n = 5 or 6; Fig. 1). Four of the five cation sites are occupied by both cobalt and vanadium, two lying on a two-fold axis. The fifth cation site (Co1) is occupied by cobalt only. Sites Co1, M3 and M4 are located on two-fold axes. Sites Co1, M2, M3 and M4 show octahedral coordination by oxygen. M5 has a square-pyramidal enviroment. The metal oxygen polyhedra form corrugated layers (stacked along the b-axis). These layers are separated by P₂O₇ groups (Fig. 3).

The pyrophosphate groups display bridging angles (P1,O5,P3)=134.8 ° and (P2,O9,P4)=135.2 °. The displacement parameters for O5 and O9 do not exhibit any anomalies. The pyrophosphate group (P1P3O₇) shows a staggered conformation while (P2P4O₇) has an almost eclipsed one (Fig.2).

Allowing for disorder in the crystal structure of Co₅V₂(P₂O₇)₄ led to significantly improved residuals. This refinement revealed disorder for four metal sites whereas the fifth site Co1 is fully occupied by cobalt (see table). The mean inter-atomic distances d(M-O) for the sites with mixed metal occupancy range from 2.01 Å to 2.17 Å. The average distance d(M-O) = 2.15 Å is found for [Co1O₆]. All distances d(M-O) are in agreement with those already known from other cobalt(II) (Krishnamachari and Calvo, 1972) and vanadium(III) (Palkina et al., 1985) phosphates.

The crystal structure of Co^II₅V^III₂(P₂O₇)₄ shows close similarity to the thortveitite structure family (Gossner & Mussgnug, 1929; Cruickshank et al., 1962; Zachariasen et al., 1930). This relation is visualized in Fig. 4 by comparison of the structures of Co^II₅V^III₂(P₂O₇)₄ and Mn₂P₂O₇ (Stefanidis et al., 1984). With respect to the composition of the latter pyrophosphate 5/8 of the Mn²⁺ sites are occupied by Co²⁺, 2/8 by V³⁺ and 1/8 remains empty for charge balance. In contrast to the honeycomb network of [MnO₆] octahedra (Fig. 4) in Mn₂P₂O₇ the polyhedra [MO_n] in Co^II₅V^III₂(P₂O₇)₄ show lower connectivity. This follows from the presence of octahedral voids and the reduced coordination number for polyhedron [M5O₅].

Related literature

For related structures, see: Cruickshank et al. (1962); Gossner & Mussgnug (1929); Krishnamachari & Calvo (1972); Litterscheid (2009); Malaman et al. (1992); Palkina et al. (1985); Stefanidis & Nord (1984); Zachariasen (1930). For the preparation, see: Binnewies et al. (2012); Litterscheid (2009).

S2. Experimental

For the synthesis of Co^II₅V^III₂(P₂O₇)₄ a pellet was prepared of thoroughly ground V₄(P₂O₇)₃ (82.97 mg) and Co₂P₂O₇ (166.99 mg). This pellet was transferred into a silica tube and sealed under vacuum. Heating at 1173 K for three days led to a single phase product. Pink single-crystals of Co₅V₂(P₂O₇)₄ were obtained by chemical vapour transport (Binnewies et al., 2012) in a temperature gradient 1273 → 1173 K for seven days using HCl as transport agent. HCl was obtained by in situ reaction of NH₄Cl (2.7 mg) and PtCl₂ (19.9 mg). In agreement with chemical vapour transport of other phosphates by HCl(g) as transport agent, we suggest the following transport reaction:

Co₅V₂(P₂O₇)₄(s) + 16 HCl(g) = 5 CoCl₂(g) + VCl₂(g) + VCl₄(g) + 2 P₄O₁₀(g) + 8 H₂O(g)

S3. Refinement

Cobalt/vanadium disorder has been refined assuming full occupancy of metal sites M1 to M5. To maintain charge balance the refinement was constrained to a total of 20 Co²⁺ and 8 V³⁺ in the unit cell. The refinement indicated no disorder for site M1, for which in the final refinement cycles full occupancy by cobalt was assumed. Displacement parameters for sites with mixed occupancy Co/V were constrained to be identical for Co²⁺ and V³⁺. No hint on racemic twinning was observed.

Even after several hundred refinement cycles the occupancy ratio Co:V for site M2 showed a rather large value of 0.01 for the ratio shift/esd. Since there are no other hints on hidden problems with the crystal structure we think that this indicator just reflects the problems generally encountered when refining occupancy factors for atoms of similar atomic number. Actually, it was quite unexpected that the refinement of the mixed occupancies Co/V proceeded without further problems.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures

	Fig. 1. ORTEP style representation of metal-oxygen coordination polyhedra in Co5V2(P2O7)4. M1: Co, M2: Co0.45V0.55, M3: Co0.86V0.14, M4: Co0.69V0.31, M5: Co0.77V0.23. Ellipsoids at 50% probability level.
	Fig. 2. ORTEP style representation of the pyrophosphate groups. Ellipsoids at 50% probability level.
	Fig. 3. Projection along the a axis of the crystal structure of Co5V2(P2O7)4 with schematic coordination polyhedra. M1: Co, M2: Co0.45V0.55, M3: Co0.86V0.14, M4: Co0.69V0.31, M5: Co0.77V0.23.
	Fig. 4. Comparison of the metal-oxygen co-ordination polyhedra and of their linkage in the crystal structures of Co5V2(P2O7)4 and Mn2P2O7. The same colour scheme as in Fig. 3 has been used.

Pentacobalt(II) divanadium(III) tetrakis(diphosphate)

Crystal data

Co5V2(P2O7)4	F(000) = 2100
Mr = 1092.29	Dx = 3.75 Mg m^−3
Orthorhombic, C2221	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 4330 reflections
a = 8.3551 (4) Å	θ = 1.0–29.1°
b = 9.7067 (5) Å	µ = 5.92 mm^−1
c = 23.8555 (11) Å	T = 293 K
V = 1934.69 (16) Å^3	Isometric, pink
Z = 4	0.08 × 0.08 × 0.08 mm

Data collection

Stoe IPDS 2T 2-circle goniometer diffractometer	3800 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2832 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
profile data from θ/2θ scans	θmax = 34.1°, θmin = 3.6°
Absorption correction: multi-scan (Blessing, 1995)	h = −12→12
Tmin = 0.495, Tmax = 0.647	k = −13→15
9445 measured reflections	l = −28→35

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0575P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.046	(Δ/σ)max = 0.058
wR(F^2) = 0.110	Δρmax = 1.02 e Å^−3
S = 0.92	Δρmin = −1.17 e Å^−3
3800 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008)
201 parameters	Extinction coefficient: 0.00114 (15)
1 restraint	Absolute structure: Flack (1983), 2275 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

Special details

Experimental. To reach the desired data resolution with the given experimental setup the image plate had been tilted by 15 degrees. This is also the explanation for the asymmetrie in the upper and lower limits of observed hkl values.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	−0.08177 (13)	0	−0.5	0.0231 (3)
Co2	−0.06997 (9)	−0.35558 (9)	−0.38065 (4)	0.01028 (16)	0.3452 (5)
V2	−0.06997 (9)	−0.35558 (9)	−0.38065 (4)	0.01028 (16)	0.6548 (5)
Co3	0.29241 (13)	0	−0.5	0.0162 (3)	0.934 (19)
V3	0.29241 (13)	0	−0.5	0.0162 (3)	0.066 (19)
Co4	0	−0.71981 (12)	−0.25	0.0106 (3)	0.72 (2)
V4	0	−0.71981 (12)	−0.25	0.0106 (3)	0.28 (2)
Co5	0.31161 (9)	−0.36011 (9)	−0.35848 (4)	0.0146 (2)	0.827 (12)
V5	0.31161 (9)	−0.36011 (9)	−0.35848 (4)	0.0146 (2)	0.173 (12)
P1	0.09658 (15)	−0.29386 (13)	−0.49912 (6)	0.0084 (2)
P2	0.11867 (16)	−0.05623 (14)	−0.37555 (6)	0.0088 (3)
P3	0.10814 (15)	−0.64697 (13)	−0.37996 (6)	0.0075 (2)
P4	0.23708 (16)	−0.46167 (13)	−0.23058 (6)	0.0088 (2)
O1	0.1176 (4)	−0.4895 (4)	−0.37362 (15)	0.0091 (7)
O2	0.1166 (5)	−0.2135 (4)	−0.37347 (17)	0.0128 (7)
O3	0.1028 (4)	−0.1378 (4)	−0.49593 (17)	0.0119 (7)
O4	0.1778 (5)	−0.5885 (4)	−0.25902 (18)	0.0148 (8)
O5	0.0296 (5)	−0.3310 (4)	−0.55996 (17)	0.0161 (8)
O6	−0.2299 (4)	−0.5048 (4)	−0.40502 (16)	0.0119 (7)
O7	−0.1713 (4)	−0.8684 (4)	−0.27171 (17)	0.0121 (7)
O8	−0.0110 (5)	−0.7125 (4)	−0.33991 (17)	0.0144 (8)
O9	0.1241 (4)	−0.0051 (4)	−0.31260 (17)	0.0138 (7)
O10	−0.0396 (4)	−0.3561 (4)	−0.46426 (16)	0.0116 (7)
O11	−0.2444 (5)	0.1430 (5)	−0.48668 (19)	0.0174 (8)
O12	0.4680 (4)	−0.4907 (5)	−0.39934 (16)	0.0132 (7)
O13	−0.2302 (5)	−0.2113 (4)	−0.38130 (18)	0.0131 (7)
O14	0.1101 (5)	−0.3849 (4)	−0.19772 (17)	0.0132 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0073 (4)	0.0060 (4)	0.0559 (9)	0	0	−0.0023 (5)
Co2	0.0092 (3)	0.0085 (3)	0.0131 (4)	0.0004 (3)	−0.0003 (3)	0.0004 (3)
V2	0.0092 (3)	0.0085 (3)	0.0131 (4)	0.0004 (3)	−0.0003 (3)	0.0004 (3)
Co3	0.0109 (5)	0.0116 (5)	0.0260 (7)	0	0	−0.0022 (5)
V3	0.0109 (5)	0.0116 (5)	0.0260 (7)	0	0	−0.0022 (5)
Co4	0.0102 (5)	0.0075 (5)	0.0140 (6)	0	0.0005 (4)	0
V4	0.0102 (5)	0.0075 (5)	0.0140 (6)	0	0.0005 (4)	0
Co5	0.0118 (3)	0.0124 (4)	0.0197 (4)	−0.0005 (3)	0.0000 (3)	−0.0020 (3)
V5	0.0118 (3)	0.0124 (4)	0.0197 (4)	−0.0005 (3)	0.0000 (3)	−0.0020 (3)
P1	0.0081 (5)	0.0056 (5)	0.0114 (6)	0.0001 (4)	0.0015 (5)	0.0001 (5)
P2	0.0078 (5)	0.0064 (5)	0.0123 (7)	−0.0010 (4)	−0.0001 (5)	−0.0002 (5)
P3	0.0081 (5)	0.0043 (5)	0.0100 (5)	0.0012 (5)	−0.0004 (5)	0.0004 (5)
P4	0.0086 (6)	0.0070 (5)	0.0107 (6)	−0.0016 (4)	0.0009 (5)	0.0008 (4)
O1	0.0080 (14)	0.0060 (15)	0.0132 (18)	0.0023 (14)	0.0035 (14)	0.0015 (14)
O2	0.0141 (16)	0.0110 (17)	0.0133 (19)	−0.0008 (15)	0.0011 (16)	0.0030 (15)
O3	0.0112 (16)	0.0081 (15)	0.0162 (18)	0.0030 (14)	−0.0014 (16)	0.0017 (16)
O4	0.0163 (18)	0.0109 (17)	0.017 (2)	−0.0048 (15)	0.0022 (16)	−0.0004 (15)
O5	0.0145 (18)	0.019 (2)	0.0147 (19)	−0.0017 (15)	0.0007 (16)	−0.0063 (16)
O6	0.0106 (15)	0.0094 (16)	0.0157 (18)	−0.0007 (15)	0.0007 (14)	−0.0009 (14)
O7	0.0112 (15)	0.0103 (17)	0.0148 (18)	−0.0009 (14)	−0.0018 (14)	0.0043 (15)
O8	0.0179 (19)	0.0112 (18)	0.0142 (18)	−0.0027 (15)	−0.0001 (16)	−0.0004 (15)
O9	0.0102 (15)	0.0141 (17)	0.0171 (19)	−0.0014 (15)	0.0002 (14)	−0.0024 (16)
O10	0.0116 (16)	0.0128 (17)	0.0104 (17)	0.0014 (15)	0.0032 (14)	0.0001 (15)
O11	0.0107 (16)	0.0112 (17)	0.030 (2)	0.0046 (15)	0.0018 (16)	0.0011 (17)
O12	0.0080 (15)	0.0157 (18)	0.0158 (19)	−0.0022 (14)	0.0008 (14)	0.0036 (16)
O13	0.0114 (16)	0.0065 (16)	0.021 (2)	0.0020 (13)	−0.0019 (16)	−0.0014 (15)
O14	0.0122 (16)	0.0170 (19)	0.0102 (17)	0.0015 (15)	0.0014 (15)	−0.0011 (14)

Geometric parameters (Å, º)

Co1—O11	1.968 (4)	Co5—O12	2.065 (4)
Co1—O11^i	1.968 (4)	Co5—O7^iv	2.076 (4)
Co1—O3^i	2.044 (4)	Co5—O1	2.082 (4)
Co1—O3	2.044 (4)	Co5—O8^iv	2.109 (4)
Co2—O14^ii	1.921 (4)	Co5—O2	2.192 (4)
Co2—O13	1.937 (4)	P1—O11^v	1.493 (4)
Co2—O10	2.010 (4)	P1—O3	1.518 (4)
Co2—O1	2.043 (3)	P1—O10	1.533 (4)
Co2—O6	2.055 (4)	P1—O5	1.597 (4)
Co2—O2	2.089 (4)	P2—O12^vi	1.520 (4)
Co3—O3^i	2.075 (4)	P2—O2	1.527 (4)
Co3—O3	2.075 (4)	P2—O6^iv	1.531 (4)
Co3—O10^iii	2.156 (4)	P2—O9	1.582 (4)
Co3—O10^iv	2.156 (4)	P3—O13^v	1.489 (4)
Co3—O6^iii	2.274 (4)	P3—O8	1.519 (4)
Co3—O6^iv	2.274 (4)	P3—O1	1.538 (4)
Co4—O4^ii	1.969 (4)	P3—O5^vii	1.591 (4)
Co4—O4	1.969 (4)	P4—O4	1.490 (4)
Co4—O7	2.097 (4)	P4—O14	1.515 (4)
Co4—O7^ii	2.097 (4)	P4—O7^iv	1.539 (4)
Co4—O8	2.148 (4)	P4—O9^viii	1.608 (4)
Co4—O8^ii	2.148 (4)
O11—Co1—O11^i	92.7 (3)	O11^v—P1—O3	111.7 (2)
O11—Co1—O3^i	93.86 (16)	O11^v—P1—O10	113.0 (2)
O11^i—Co1—O3^i	167.12 (17)	O3—P1—O10	113.1 (2)
O11—Co1—O3	167.12 (17)	O11^v—P1—O5	113.6 (2)
O11^i—Co1—O3	93.86 (16)	O3—P1—O5	106.4 (2)
O3^i—Co1—O3	82.0 (2)	O10—P1—O5	98.3 (2)
O14^ii—Co2—O13	89.68 (18)	O12^vi—P2—O2	114.9 (3)
O14^ii—Co2—O10	170.85 (19)	O12^vi—P2—O6^iv	112.1 (2)
O13—Co2—O10	94.66 (17)	O2—P2—O6^iv	110.5 (2)
O14^ii—Co2—O1	87.68 (16)	O12^vi—P2—O9	104.3 (2)
O13—Co2—O1	172.15 (17)	O2—P2—O9	106.4 (2)
O10—Co2—O1	89.03 (15)	O6^iv—P2—O9	108.1 (2)
O14^ii—Co2—O6	93.29 (17)	O13^v—P3—O8	115.6 (2)
O13—Co2—O6	93.32 (16)	O13^v—P3—O1	111.9 (2)
O10—Co2—O6	78.44 (16)	O8—P3—O1	112.8 (2)
O1—Co2—O6	94.22 (15)	O13^v—P3—O5^vii	107.4 (2)
O14^ii—Co2—O2	98.53 (17)	O8—P3—O5^vii	103.9 (2)
O13—Co2—O2	92.24 (16)	O1—P3—O5^vii	104.1 (2)
O10—Co2—O2	89.36 (16)	O4—P4—O14	114.2 (2)
O1—Co2—O2	80.85 (15)	O4—P4—O7^iv	111.2 (2)
O6—Co2—O2	166.96 (16)	O14—P4—O7^iv	112.9 (2)
O3^i—Co3—O3	80.5 (2)	O4—P4—O9^viii	108.3 (2)
O3^i—Co3—O10^iii	153.63 (15)	O14—P4—O9^viii	107.6 (2)
O3—Co3—O10^iii	95.61 (15)	O7^iv—P4—O9^viii	101.8 (2)
O3^i—Co3—O10^iv	95.62 (15)	P3—O1—Co2	125.8 (2)
O3—Co3—O10^iv	153.62 (15)	P3—O1—Co5	131.1 (2)
O10^iii—Co3—O10^iv	98.8 (2)	Co2—O1—Co5	103.14 (16)
O3^i—Co3—O6^iii	82.97 (15)	P2—O2—Co2	131.7 (3)
O3—Co3—O6^iii	89.84 (15)	P2—O2—Co5	130.2 (2)
O10^iii—Co3—O6^iii	70.88 (14)	Co2—O2—Co5	98.01 (17)
O10^iv—Co3—O6^iii	115.74 (14)	P1—O3—Co1	128.7 (2)
O3^i—Co3—O6^iv	89.84 (15)	P1—O3—Co3	131.9 (2)
O3—Co3—O6^iv	82.97 (15)	Co1—O3—Co3	98.73 (16)
O10^iii—Co3—O6^iv	115.73 (14)	P4—O4—Co4	137.3 (3)
O10^iv—Co3—O6^iv	70.88 (14)	P3^vii—O5—P1	134.8 (3)
O6^iii—Co3—O6^iv	170.60 (19)	P2^ix—O6—Co2	129.6 (2)
O4^ii—Co4—O4	99.4 (3)	P2^ix—O6—Co3^ix	122.1 (2)
O4^ii—Co4—O7	87.52 (17)	Co2—O6—Co3^ix	102.37 (16)
O4—Co4—O7	158.93 (16)	P2^ix—O6—V3^ix	122.1 (2)
O4^ii—Co4—O7^ii	158.93 (16)	Co2—O6—V3^ix	102.37 (16)
O4—Co4—O7^ii	87.52 (17)	P4^ix—O7—V5^ix	128.6 (2)
O7—Co4—O7^ii	93.1 (2)	P4^ix—O7—Co5^ix	128.6 (2)
O4^ii—Co4—O8	93.18 (17)	P4^ix—O7—Co4	125.9 (2)
O4—Co4—O8	84.36 (17)	V5^ix—O7—Co4	105.46 (17)
O7—Co4—O8	75.35 (15)	Co5^ix—O7—Co4	105.46 (17)
O7^ii—Co4—O8	107.37 (16)	P3—O8—V5^ix	127.8 (2)
O4^ii—Co4—O8^ii	84.36 (17)	P3—O8—Co5^ix	127.8 (2)
O4—Co4—O8^ii	93.18 (17)	P3—O8—Co4	127.9 (2)
O7—Co4—O8^ii	107.37 (16)	V5^ix—O8—Co4	102.55 (18)
O7^ii—Co4—O8^ii	75.35 (15)	Co5^ix—O8—Co4	102.55 (18)
O8—Co4—O8^ii	176.2 (2)	P2—O9—P4^x	135.3 (3)
O12—Co5—O7^iv	113.79 (16)	P1—O10—Co2	129.1 (2)
O12—Co5—O1	92.30 (15)	P1—O10—V3^ix	121.6 (2)
O7^iv—Co5—O1	101.71 (15)	Co2—O10—V3^ix	108.17 (17)
O12—Co5—O8^iv	94.11 (16)	P1—O10—Co3^ix	121.6 (2)
O7^iv—Co5—O8^iv	76.62 (15)	Co2—O10—Co3^ix	108.17 (17)
O1—Co5—O8^iv	173.51 (15)	P1^vi—O11—Co1	150.7 (3)
O12—Co5—O2	142.34 (16)	P2^v—O12—Co5	127.2 (2)
O7^iv—Co5—O2	103.80 (15)	P3^vi—O13—Co2	158.5 (3)
O1—Co5—O2	77.59 (14)	P4—O14—V2^ii	134.3 (3)
O8^iv—Co5—O2	96.63 (16)	P4—O14—Co2^ii	134.3 (3)

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