Bis[tris­(phenanthroline-κ2N,N′)cobalt(II)] undeca­tungsto(VI)vanado(V)phosphate dihydrate

Hajsalem, A.; Aoun, S.; Planchat, A.; Rzaigui, M.; Toumi, S.A.

doi:10.1107/S160053681400484X

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 4| April 2014| Pages m125-m126

doi:10.1107/S160053681400484X

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Bis[tris(phenanthroline-κ²N,N′)cobalt(II)] undecatungsto(VI)vanado(V)phosphate dihydrate

Assia Hajsalem,^a Sameh Aoun,^b Aurelien Planchat,^b Mohamed Rzaigui ^a and Samah Akriche Toumi ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bLaboratoire CEISAM, UMR CNRS 6230, UFR des Sciences et des Techniques, 2 rue de la Houssinière, BP 92208, 44322 Nantes Cedex 03, France
^*Correspondence e-mail: samah.akriche@fsb.rnu.tn

(Received 26 February 2014; accepted 3 March 2014; online 8 March 2014)

In the title hydrated salt, [Co(C₁₂H₈N₂)₃]₂[PVW₁₁O₄₀]·2H₂O, the complete Kegggin ion is generated by crystallographic inversion symmetry, which imposes statistical disorder on the O atoms of its central PO₄ group. The V atom is statistically disordered over all the metal sites of the anion. In the cation, the Co²⁺ ion is coordinated by three bidentate 1,10-phenanthroline (phen) ligands, generating a distorted CoN₆ octahedron. Possible very weak intramolecular C—H⋯π interactions occur in the cation. In the crystal, the components are linked by O—H⋯O and C—H⋯O interactions, building a three-dimensional network featuring one-dimensional voids along the c-axis direction.

CCDC reference: 989480

Related literature

For related vanadium-substituted Keggin-ion structures, see: Glinskaya et al. (1989 ); Klevtsova et al. (1990 , 1991 ); Li et al. (2008 ); Radkov & Beer (1995 ). For IR spectroscopy investigations of Keggin ions, see: Lee & Misono (1997 ); Deltcheff et al. (1983 ); Watras & Teplyakov (2005 ). For bond-valence calculations, see: Brown & Altermatt (1985 ). For background to polyoxidometalate chemistry, see: Pope & Müller (1991 , 1994 ).

Experimental

Crystal data

[Co(C₁₂H₈N₂)₃][PVW₁₁O₄₀]·2H₂O
M_r = 3979.38
Monoclinic, C 2/c
a = 19.487 (2) Å
b = 18.049 (3) Å
c = 25.216 (2) Å
β = 100.22 (3)°
V = 8728.4 (18) Å³
Z = 4
Mo Kα radiation
μ = 15.02 mm⁻¹
T = 295 K
0.13 × 0.08 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.202, T_max = 0.421
62427 measured reflections
11235 independent reflections
8172 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.095
S = 1.16
11235 reflections
688 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.39 e Å⁻³
Δρ_min = −1.51 e Å⁻³

Table 1
Selected bond lengths (Å)

Co—N3	2.053 (9)
Co—N6	2.060 (8)
Co—N1	2.066 (10)
Co—N4	2.066 (11)
Co—N2	2.078 (10)
Co—N5	2.085 (8)

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N1/C1–C4/C12 and N3/C13–C16/C24 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1E	0.85 (1)	2.17 (11)	2.928 (14)	149 (20)
O1W—H2W1⋯O3Eⁱ	0.85 (1)	1.99 (3)	2.836 (13)	173 (17)
C9—H9⋯O5Eⁱⁱ	0.93	2.55	3.208 (15)	128
C26—H26⋯O12ⁱⁱⁱ	0.93	2.46	2.973 (15)	114
C33—H33⋯O5^iv	0.93	2.53	3.345 (13)	147
C34—H34⋯O8	0.93	2.43	3.114 (13)	130
C34—H34⋯Cg1	0.93	3.04	3.811 (12)	142
C25—H25⋯Cg2	0.93	2.99	3.777 (13)	143
Symmetry codes: (i) -x+2, -y, -z+1; (ii) $[x, -y, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000 ); data reduction: EVALCCD (Duisenberg et al., 2003 ); 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, 2012 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 989480

Crystal structure: contains datablock I. DOI: 10.1107/S160053681400484X/hb7203sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681400484X/hb7203Isup2.hkl

checkCIF report

Comment top

A bibliographic survey shows only a few examples of substituted vanadium keggin-type [XV₁W₁₁O₄₀]^p^- clusters associated to organometallic or organic moieties: such as (C₂N₂H₁₀)₂[VV₁W₁₁O₄₀]·6H₂O (Glinskaya et al., 1989), [N(CH₃)₄]₄[VV₁W₁₁O₄₀]·4.5H₂O (Klevtsova et al., 1991),[(CH₃)₂NCHO]₄H₄[VV₁W₁₁O₄₀].2[(CH₃)₂NCHO]·2H₂O (Klevtsova et al., 1990), [Cu(phen)₂]₂[PVW₁₁O₄₀] (phen = phenanthroline)(Li et al., 2008),(n-Bu₄N)₄[PMW₁₁O₄₀] (n-Bu = n-Butyl and M = V, Nb, Ta) (Radkov & Beer, 1995). Here, we report a new monosubstituted vanadium tungstophosphate Keggin-type cluster decorated by mononuclear metal-organic complex [Co(phen)₃]₂[PVW₁₁O₄₀]·2H₂O (phen = phenanthroline) (I).

The asymmetric unit of of I consists of a mononuclear complex [Co(phen)₃]²⁺ cation and a half of Keggin-type [PVW₁₁O₄₀]^4- anion and one water molecule. As P atom is located on centre of inversion symmetry, the whole [PVW₁₁O₄₀]^4- polyoxidoanion is generated by this element and so is composed of a disordered PO₄ tetrahedron surrounded by four vertex-sharing M₃O₁₃ (with M = W/V) subunits which result from the association of three edge-sharing MO₆ octahedra enwrapping a PO₈ cube with oxygen atom site occupancy of 0.5. In the MO₆ (with M = W/V) octahedra, the position of metal atom is crystallographically disordered and constrained as 11/12 W and 1/12 V, with occupancies of 0.083 and 0.917 for W and V respectively.

The contents of W and V revealed by X-ray analysis are consistent with the results from elemental analyses and scanning electronic microscopy (Fig. 2) as well as the IR spectroscopy wich shows that the streching vibration of (P—O) splits into two absoption bands at 1095 cm^-1 and 1068 cm^-1 because of the lower symmetry so as well confirm the presence of monosubstituted vanadium keggin-type clusters in I (Lee et al., 1997; Deltcheff et al., 1983; Watras et al., 2005).

The assignment of oxidation states for the tungsten and vanadium atoms is confirmed by bond valence sum calculations (Brown & Altermatt, 1985)) which show that vanadium atom has +V oxidation state (average 4.98 valence units) while tungsten atoms have +VI oxidation state (average 6.23 valence units). These oxidation states are identical with the charge balance considerations and so consistent with the expected [PV^+VW^+VI₁₁O₄₀]^4- subunits.

The P—O bond distances range 1.481 (11)—1.582 (11) Å and O—P—O bond angles interval 105.5 (6)—112.6 (6) °. Commonly, the M—O bond distances are grouped into three sets: M—Ot, M—Ob and M—Oc (with Ot: terminal oxygen atoms, Oc: central oxygen atoms, Ob: bridging oxygen atoms) which are respectively ranged between 1.667 (8)—1.677 (7) Å, 2.396 (11)—2.526 (12) Å and 1.750 (18)—2.085 (14) Å. With regard to the mononuclear complex,the Co²⁺ metal is also coordinated by six nitrogen atoms from three chelating 1,10-phenanthroline ligands to form a slightly distorted MN₆ octahedron with bond lenghts around Co, are 2.053 (9)—2.085 (8) Å (Co—N) and 80.0 (4)—173.9 (4)° (N—Co—N) (Table 1).

The crystal packing of I shows that the discrete polyoxidoanion subunits are interconnected through water molecules via O—H···O hydrogen bonding interactions with O···O separation ranging from 2.836 (13) to 2.928 (14) Å (Table 2), to perform alternating [PVW₁₁O₄₀(H₂O)₂]^4n- ribbons extending along [110] and [110] crystallographic directions. The so-obtained one-dimensional-subnetworks stack together by the metal-organic moieties thanks to weak C–H···O (mean C···O = 3.144 Å) (Table 1) and electrostatic interactions so as to build three-dimensional-supramolecular network generating vacant one-dimensional-channels along c axis as can be seen in Fig. 3. Very weak intramolecular C—H···π interactions of phen rings (Fig. 4) with mean distances of 3 Å (Table 2) are also observed.

Related literature top

For related vanadium-substituted Keggin-ion structures, see: Glinskaya et al. (1989); Klevtsova et al. (1990, 1991); Li et al. (2008); Radkov & Beer (1995). For IR spectroscopy investigations of Keggin ions, see: Lee & Misono (1997); Deltcheff et al. (1983); Watras & Teplyakov (2005). For bond-valence calculations, see: Brown & Altermatt (1985). For [please specify], see: Pope & Müller (1991, 1994).

Experimental top

A reaction mixture of Na₂WO₄·2H₂O (2 g, 6.064 mmol), NaH₂PO₄·2H₂O (0.1034 g, 0.6628 mmol), CoCl₂·6H₂O (0.1951 g, 0.8196 mmol), V₂O₅ (0,0455 g; 0.25 mmol) and phen·H₂O (0.3196 g, 1.7758 mmol) were added to water (10 ml). The mixture was adjusted to pH = 5.5 by the addition of 4M HCl aqueous solution then stirred for 30 min in air. The mixture solution was transferred into a 23 ml Teflon-lined autoclave and crystallized at 180°C for 4 days. Then the autoclave was cooled at 10°C.h^-1 to room temperature. The resulting dark yellow block crystals of I were filtered off, washed with water, and dried at ambient temperature to give yields of 68% based on W. Anal. Calc. For C₇₂H₅₂N₁₂Co₂O₄₂PVW₁₁ (%): C 21.79, H 1.27, N 4.20, W 50.92, V 1.28, P 0.78, Co 2.96; Found C 21.71, H 1.31, N 4.25, W 50.80, V 1.31, P 3/4, Co 2.98; IR (KBr, cm^-1): 966 ν(M=Ot), 887 ν(M—Ob—M), 799 ν(M—Oc—M) with M=W/V and 1095 and 1068 ν(P—O).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); 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, 2012) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. An ORTEP view of (I) with displacement ellipsoids drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are represented as dashed lines. [Symmetry code: (i) 1 - x, 1 - y, 1 - z]
	Fig. 2. EDAX pattern of I
	Fig. 3. Packing diagram of I viewed along c axis showing a three-dimensional-supramolecular structure featuring the voids represented as large yellow ball. The H-atoms not included in H-bond scheme are omitted.
	Fig. 4. View of intramolecular C—H···π interaction in (I). The H-atoms not included in H-bond scheme are omitted.

Bis[tris(phenanthroline-κ²N,N')cobalt(II)] undecatungsto(VI)vanado(V)phosphate dihydrate top

Crystal data top

[Co(C₁₂H₈N₂)₃][PVW₁₁O₄₀]·2H₂O	F(000) = 7240
M_r = 3979.38	D_x = 3.028 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.487 (2) Å	Cell parameters from 25 reflections
b = 18.049 (3) Å	θ = 9–11°
c = 25.216 (2) Å	µ = 15.02 mm⁻¹
β = 100.22 (3)°	T = 295 K
V = 8728.4 (18) Å³	PRISM, yellow
Z = 4	0.13 × 0.08 × 0.04 mm

Data collection top

Nonius KappaCCD diffractometer	11235 independent reflections
Radiation source: fine-focus sealed tube	8172 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0.070
Detector resolution: 9 pixels mm^-1	θ_max = 28.8°, θ_min = 6.4°
CCD rotation images, thick slices scans	h = −26→25
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −24→24
T_min = 0.202, T_max = 0.421	l = −34→32
62427 measured reflections

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + 250.0304P] where P = (F_o² + 2F_c²)/3
11235 reflections	(Δ/σ)_max = 0.002
688 parameters	Δρ_max = 1.39 e Å⁻³
3 restraints	Δρ_min = −1.51 e Å⁻³

Crystal data top

[Co(C₁₂H₈N₂)₃][PVW₁₁O₄₀]·2H₂O	V = 8728.4 (18) Å³
M_r = 3979.38	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.487 (2) Å	µ = 15.02 mm⁻¹
b = 18.049 (3) Å	T = 295 K
c = 25.216 (2) Å	0.13 × 0.08 × 0.04 mm
β = 100.22 (3)°

Data collection top

Nonius KappaCCD diffractometer	11235 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	8172 reflections with I > 2σ(I)
T_min = 0.202, T_max = 0.421	R_int = 0.070
62427 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	3 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + 250.0304P] where P = (F_o² + 2F_c²)/3
11235 reflections	Δρ_max = 1.39 e Å⁻³
688 parameters	Δρ_min = −1.51 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
W1	0.90431 (2)	0.16939 (2)	0.468951 (18)	0.03506 (10)	0.91
V1	0.90431 (2)	0.16939 (2)	0.468951 (18)	0.03506 (10)	0.09
W2	0.91248 (2)	0.27877 (3)	0.587700 (17)	0.03574 (11)	0.91
V2	0.91248 (2)	0.27877 (3)	0.587700 (17)	0.03574 (11)	0.09
W3	0.83223 (2)	0.10207 (3)	0.579002 (19)	0.04092 (12)	0.92
V3	0.83223 (2)	0.10207 (3)	0.579002 (19)	0.04092 (12)	0.08
W4	0.82438 (2)	0.32068 (3)	0.391898 (18)	0.04283 (12)	0.92
V4	0.82438 (2)	0.32068 (3)	0.391898 (18)	0.04283 (12)	0.08
W5	0.67180 (3)	0.07254 (3)	0.48920 (2)	0.04756 (13)	0.92
V5	0.67180 (3)	0.07254 (3)	0.48920 (2)	0.04756 (13)	0.08
W6	0.74373 (3)	0.14331 (3)	0.380723 (19)	0.04799 (13)	0.92
V6	0.74373 (3)	0.14331 (3)	0.380723 (19)	0.04799 (13)	0.08
O1E	0.9773 (4)	0.1310 (5)	0.4547 (4)	0.072 (3)
O2E	0.9883 (4)	0.2925 (5)	0.6293 (3)	0.064 (2)
O3E	0.8718 (5)	0.0319 (5)	0.6152 (3)	0.066 (2)
O4E	0.8576 (4)	0.3557 (5)	0.3403 (3)	0.057 (2)
O5E	0.6360 (4)	−0.0117 (4)	0.4862 (3)	0.052 (2)
O6E	0.7424 (5)	0.0939 (5)	0.3244 (3)	0.069 (3)
O1	0.9412 (4)	0.2330 (4)	0.5277 (3)	0.051 (2)
O2	0.8823 (4)	0.1027 (4)	0.5215 (3)	0.053 (2)
O3	0.8945 (5)	0.2558 (5)	0.4245 (3)	0.073 (3)
O4	0.8351 (5)	0.1247 (5)	0.4175 (4)	0.079 (3)
O5	0.8869 (4)	0.1821 (4)	0.6090 (3)	0.053 (2)
O6A	0.8877 (8)	0.3591 (10)	0.5382 (7)	0.038 (4)	0.50
O6B	0.9132 (8)	0.3772 (9)	0.5575 (6)	0.030 (3)	0.50
O7	0.8556 (4)	0.3900 (6)	0.4469 (4)	0.081 (3)
O8	0.7761 (5)	0.2355 (5)	0.3599 (3)	0.072 (3)
O9A	0.8604 (7)	0.3245 (9)	0.6394 (6)	0.032 (3)	0.50
O9B	0.8340 (7)	0.3084 (10)	0.6198 (6)	0.035 (4)	0.50
O10	0.7634 (4)	0.1309 (7)	0.6194 (4)	0.086 (4)
O11A	0.7035 (10)	0.0633 (11)	0.4178 (7)	0.041 (4)	0.50
O11B	0.7226 (10)	0.0845 (10)	0.4384 (7)	0.038 (4)	0.50
O12	0.7599 (4)	0.0525 (6)	0.5323 (4)	0.081 (3)
P	0.7500	0.2500	0.5000	0.0229 (6)
O1C	0.7595 (6)	0.3206 (7)	0.4667 (4)	0.028 (3)	0.50
O3C	0.7921 (6)	0.2294 (7)	0.4564 (5)	0.028 (3)	0.50
O4C	0.8176 (6)	0.2148 (7)	0.5224 (4)	0.027 (3)	0.50
O2C	0.7968 (6)	0.3041 (7)	0.5406 (4)	0.028 (3)	0.50
O1W	1.0714 (7)	0.1131 (6)	0.3771 (6)	0.098 (4)
H1W1	1.033 (6)	0.115 (9)	0.388 (8)	0.147*
H2W1	1.092 (8)	0.071 (5)	0.380 (9)	0.147*
Co	0.80233 (7)	0.31178 (8)	0.15603 (5)	0.0367 (3)
N1	0.8600 (5)	0.2468 (6)	0.2151 (4)	0.051 (2)
N2	0.7596 (5)	0.2088 (5)	0.1326 (4)	0.047 (2)
N3	0.8759 (5)	0.3135 (5)	0.1070 (3)	0.041 (2)
N4	0.8545 (6)	0.4082 (6)	0.1827 (4)	0.054 (3)
N5	0.7316 (4)	0.3680 (5)	0.0981 (3)	0.0375 (19)
N6	0.7208 (4)	0.3243 (5)	0.1973 (3)	0.0365 (19)
C1	0.9090 (6)	0.2668 (9)	0.2556 (5)	0.064 (4)
H1	0.9240	0.3158	0.2573	0.077*
C2	0.9398 (8)	0.2178 (13)	0.2961 (6)	0.083 (5)
H2	0.9743	0.2340	0.3239	0.099*
C3	0.9184 (9)	0.1468 (12)	0.2937 (6)	0.085 (5)
H3	0.9379	0.1135	0.3203	0.102*
C4	0.8660 (7)	0.1226 (8)	0.2505 (5)	0.061 (3)
C5	0.8418 (9)	0.0467 (8)	0.2431 (6)	0.075 (4)
H5	0.8620	0.0104	0.2671	0.089*
C6	0.7912 (9)	0.0282 (8)	0.2025 (6)	0.073 (4)
H6	0.7755	−0.0205	0.1995	0.088*
C7	0.7601 (7)	0.0823 (7)	0.1630 (5)	0.060 (3)
C8	0.7059 (8)	0.0667 (8)	0.1192 (6)	0.070 (4)
H8	0.6881	0.0190	0.1136	0.084*
C9	0.6808 (8)	0.1224 (9)	0.0859 (6)	0.072 (4)
H9	0.6444	0.1135	0.0574	0.086*
C10	0.7080 (7)	0.1908 (8)	0.0936 (5)	0.060 (3)
H10	0.6891	0.2279	0.0698	0.072*
C11	0.7863 (6)	0.1554 (6)	0.1681 (4)	0.046 (3)
C12	0.8393 (6)	0.1741 (8)	0.2123 (5)	0.054 (3)
C13	0.8843 (6)	0.2656 (7)	0.0680 (5)	0.052 (3)
H13	0.8576	0.2226	0.0639	0.062*
C14	0.9317 (6)	0.2776 (8)	0.0331 (5)	0.059 (3)
H14	0.9351	0.2440	0.0057	0.071*
C15	0.9731 (6)	0.3399 (7)	0.0398 (5)	0.058 (3)
H15	1.0055	0.3478	0.0174	0.069*
C16	0.9669 (6)	0.3917 (7)	0.0805 (5)	0.051 (3)
C17	1.0060 (6)	0.4588 (7)	0.0903 (6)	0.060 (3)
H17	1.0397	0.4700	0.0696	0.072*
C18	0.9948 (6)	0.5058 (7)	0.1291 (6)	0.064 (4)
H18	1.0210	0.5491	0.1347	0.077*
C19	0.9437 (6)	0.4915 (7)	0.1621 (5)	0.057 (3)
C20	0.9284 (8)	0.5398 (8)	0.2027 (6)	0.066 (4)
H20	0.9512	0.5851	0.2089	0.079*
C21	0.8798 (9)	0.5191 (8)	0.2324 (6)	0.073 (4)
H21	0.8715	0.5488	0.2607	0.087*
C22	0.8431 (8)	0.4549 (7)	0.2207 (5)	0.063 (4)
H22	0.8084	0.4435	0.2403	0.076*
C23	0.9041 (6)	0.4266 (6)	0.1535 (4)	0.046 (3)
C24	0.9158 (5)	0.3752 (6)	0.1129 (4)	0.043 (2)
C25	0.7358 (7)	0.3868 (7)	0.0480 (5)	0.057 (3)
H25	0.7775	0.3777	0.0361	0.068*
C26	0.6827 (7)	0.4185 (7)	0.0127 (5)	0.058 (3)
H26	0.6883	0.4298	−0.0222	0.069*
C27	0.6220 (7)	0.4333 (7)	0.0292 (5)	0.059 (3)
H27	0.5860	0.4561	0.0058	0.071*
C28	0.6129 (6)	0.4147 (6)	0.0813 (4)	0.044 (3)
C29	0.5491 (6)	0.4251 (8)	0.1015 (5)	0.063 (4)
H29	0.5109	0.4472	0.0800	0.076*
C30	0.5453 (6)	0.4023 (9)	0.1519 (6)	0.069 (4)
H30	0.5036	0.4096	0.1643	0.083*
C31	0.6020 (5)	0.3676 (8)	0.1873 (5)	0.054 (3)
C32	0.6007 (6)	0.3421 (9)	0.2395 (5)	0.067 (4)
H32	0.5605	0.3479	0.2541	0.080*
C33	0.6570 (6)	0.3094 (8)	0.2688 (5)	0.060 (3)
H33	0.6559	0.2934	0.3037	0.072*
C34	0.7170 (6)	0.2996 (7)	0.2464 (4)	0.049 (3)
H34	0.7552	0.2753	0.2662	0.058*
C35	0.6646 (5)	0.3573 (6)	0.1679 (4)	0.036 (2)
C36	0.6705 (5)	0.3812 (6)	0.1147 (4)	0.036 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.0286 (2)	0.0352 (2)	0.0414 (2)	0.00378 (18)	0.00621 (17)	−0.00271 (19)
V1	0.0286 (2)	0.0352 (2)	0.0414 (2)	0.00378 (18)	0.00621 (17)	−0.00271 (19)
W2	0.0295 (2)	0.0391 (2)	0.0366 (2)	0.00004 (18)	0.00030 (17)	0.00294 (18)
V2	0.0295 (2)	0.0391 (2)	0.0366 (2)	0.00004 (18)	0.00030 (17)	0.00294 (18)
W3	0.0345 (2)	0.0374 (3)	0.0478 (3)	0.00344 (19)	−0.00085 (19)	0.0026 (2)
V3	0.0345 (2)	0.0374 (3)	0.0478 (3)	0.00344 (19)	−0.00085 (19)	0.0026 (2)
W4	0.0409 (3)	0.0558 (3)	0.0327 (2)	−0.0115 (2)	0.00890 (19)	0.0005 (2)
V4	0.0409 (3)	0.0558 (3)	0.0327 (2)	−0.0115 (2)	0.00890 (19)	0.0005 (2)
W5	0.0452 (3)	0.0292 (2)	0.0711 (3)	−0.0081 (2)	0.0181 (2)	−0.0074 (2)
V5	0.0452 (3)	0.0292 (2)	0.0711 (3)	−0.0081 (2)	0.0181 (2)	−0.0074 (2)
W6	0.0643 (3)	0.0444 (3)	0.0366 (2)	−0.0025 (2)	0.0124 (2)	−0.0138 (2)
V6	0.0643 (3)	0.0444 (3)	0.0366 (2)	−0.0025 (2)	0.0124 (2)	−0.0138 (2)
O1E	0.042 (5)	0.056 (5)	0.129 (8)	0.000 (4)	0.046 (5)	−0.017 (5)
O2E	0.047 (5)	0.093 (7)	0.044 (4)	−0.032 (5)	−0.013 (4)	−0.003 (4)
O3E	0.094 (7)	0.044 (5)	0.062 (5)	0.022 (5)	0.021 (5)	0.014 (4)
O4E	0.046 (4)	0.082 (6)	0.042 (4)	−0.008 (4)	0.010 (4)	0.019 (4)
O5E	0.042 (4)	0.029 (4)	0.079 (6)	−0.007 (3)	−0.003 (4)	−0.001 (4)
O6E	0.071 (6)	0.080 (7)	0.055 (5)	−0.003 (5)	0.005 (4)	−0.041 (5)
O1	0.077 (5)	0.044 (4)	0.034 (4)	−0.018 (4)	0.017 (4)	−0.006 (3)
O2	0.079 (6)	0.042 (4)	0.041 (4)	−0.023 (4)	0.021 (4)	−0.011 (3)
O3	0.084 (6)	0.053 (5)	0.062 (5)	−0.022 (5)	−0.038 (5)	0.019 (4)
O4	0.097 (7)	0.047 (5)	0.072 (6)	−0.027 (5)	−0.045 (5)	0.011 (4)
O5	0.077 (6)	0.043 (4)	0.043 (4)	−0.024 (4)	0.021 (4)	−0.004 (3)
O6A	0.024 (9)	0.051 (11)	0.039 (10)	−0.005 (7)	0.003 (7)	0.003 (8)
O6B	0.028 (9)	0.032 (9)	0.028 (9)	0.005 (7)	−0.002 (6)	0.006 (6)
O7	0.029 (4)	0.124 (9)	0.091 (7)	−0.010 (5)	0.010 (4)	−0.070 (6)
O8	0.081 (6)	0.050 (5)	0.066 (5)	−0.024 (5)	−0.039 (5)	0.019 (4)
O9A	0.019 (8)	0.043 (9)	0.031 (8)	0.003 (7)	−0.006 (6)	0.003 (7)
O9B	0.009 (7)	0.063 (11)	0.028 (8)	−0.004 (7)	−0.007 (5)	−0.003 (7)
O10	0.027 (4)	0.137 (9)	0.092 (7)	−0.007 (5)	0.008 (4)	−0.070 (7)
O11A	0.041 (10)	0.039 (11)	0.044 (12)	0.000 (8)	0.009 (8)	−0.012 (8)
O11B	0.044 (11)	0.045 (11)	0.029 (9)	0.006 (8)	0.019 (8)	−0.010 (7)
O12	0.033 (4)	0.112 (8)	0.095 (7)	−0.008 (5)	0.004 (4)	−0.068 (6)
P	0.0258 (15)	0.0167 (14)	0.0257 (15)	−0.0004 (12)	0.0030 (12)	−0.0015 (12)
O1C	0.027 (6)	0.031 (7)	0.022 (6)	0.001 (5)	−0.003 (5)	0.005 (5)
O3C	0.026 (6)	0.030 (7)	0.030 (6)	0.005 (5)	0.010 (5)	−0.004 (5)
O4C	0.020 (6)	0.038 (7)	0.025 (6)	0.000 (5)	0.008 (5)	−0.001 (5)
O2C	0.025 (6)	0.031 (7)	0.022 (6)	−0.009 (5)	−0.010 (5)	−0.006 (5)
O1W	0.109 (10)	0.069 (7)	0.129 (10)	0.024 (7)	0.057 (8)	0.007 (7)
Co	0.0363 (7)	0.0382 (8)	0.0355 (7)	0.0024 (6)	0.0067 (6)	0.0015 (6)
N1	0.036 (5)	0.074 (7)	0.045 (5)	0.006 (5)	0.013 (4)	−0.004 (5)
N2	0.047 (5)	0.048 (6)	0.048 (5)	0.002 (4)	0.014 (4)	0.000 (4)
N3	0.047 (5)	0.034 (5)	0.041 (5)	0.007 (4)	0.002 (4)	0.000 (4)
N4	0.070 (7)	0.051 (6)	0.039 (5)	0.017 (5)	0.009 (5)	−0.001 (4)
N5	0.041 (5)	0.036 (5)	0.035 (4)	−0.004 (4)	0.005 (4)	0.006 (4)
N6	0.035 (4)	0.043 (5)	0.030 (4)	0.006 (4)	0.000 (3)	−0.005 (4)
C1	0.048 (7)	0.091 (11)	0.056 (8)	0.008 (7)	0.017 (6)	0.000 (7)
C2	0.051 (8)	0.139 (17)	0.058 (9)	0.012 (10)	0.007 (7)	−0.007 (10)
C3	0.076 (11)	0.114 (15)	0.067 (10)	0.040 (11)	0.020 (8)	0.025 (10)
C4	0.070 (9)	0.067 (9)	0.048 (7)	0.029 (7)	0.017 (6)	0.013 (6)
C5	0.103 (12)	0.060 (9)	0.069 (9)	0.040 (9)	0.040 (9)	0.019 (7)
C6	0.099 (12)	0.052 (8)	0.078 (10)	0.022 (8)	0.042 (9)	0.000 (7)
C7	0.077 (9)	0.049 (7)	0.064 (8)	0.008 (7)	0.038 (7)	−0.007 (6)
C8	0.082 (10)	0.057 (9)	0.079 (10)	−0.015 (8)	0.037 (8)	−0.028 (8)
C9	0.080 (10)	0.081 (11)	0.053 (8)	−0.001 (8)	0.006 (7)	−0.028 (8)
C10	0.060 (8)	0.069 (9)	0.050 (7)	−0.020 (7)	0.007 (6)	−0.018 (6)
C11	0.054 (7)	0.045 (7)	0.044 (6)	0.008 (5)	0.023 (5)	0.002 (5)
C12	0.049 (7)	0.068 (9)	0.049 (7)	0.010 (6)	0.020 (6)	0.007 (6)
C13	0.053 (7)	0.041 (7)	0.062 (7)	0.007 (5)	0.013 (6)	−0.005 (6)
C14	0.044 (7)	0.064 (8)	0.068 (8)	0.020 (6)	0.005 (6)	−0.017 (7)
C15	0.041 (6)	0.064 (8)	0.066 (8)	0.017 (6)	0.007 (6)	−0.010 (7)
C16	0.040 (6)	0.054 (7)	0.058 (7)	0.018 (6)	0.005 (5)	0.012 (6)
C17	0.038 (6)	0.048 (7)	0.093 (10)	0.011 (6)	0.009 (6)	0.003 (7)
C18	0.040 (7)	0.043 (7)	0.102 (11)	0.006 (6)	−0.006 (7)	0.015 (7)
C19	0.048 (7)	0.044 (7)	0.070 (8)	0.012 (6)	−0.014 (6)	0.004 (6)
C20	0.065 (9)	0.054 (8)	0.068 (9)	0.010 (7)	−0.022 (7)	0.000 (7)
C21	0.097 (12)	0.055 (9)	0.057 (8)	0.024 (8)	−0.012 (8)	−0.012 (7)
C22	0.085 (10)	0.049 (8)	0.055 (7)	0.017 (7)	0.009 (7)	−0.006 (6)
C23	0.044 (6)	0.045 (6)	0.043 (6)	0.011 (5)	−0.005 (5)	0.005 (5)
C24	0.032 (5)	0.040 (6)	0.053 (6)	0.007 (5)	−0.005 (5)	−0.006 (5)
C25	0.068 (8)	0.059 (8)	0.044 (6)	−0.004 (7)	0.014 (6)	0.007 (6)
C26	0.068 (8)	0.057 (8)	0.046 (7)	0.004 (6)	0.005 (6)	0.029 (6)
C27	0.058 (8)	0.049 (7)	0.060 (8)	−0.010 (6)	−0.014 (6)	0.024 (6)
C28	0.044 (6)	0.038 (6)	0.044 (6)	−0.010 (5)	−0.010 (5)	0.001 (5)
C29	0.032 (6)	0.083 (10)	0.068 (8)	0.004 (6)	−0.010 (6)	0.013 (7)
C30	0.030 (6)	0.104 (12)	0.069 (9)	0.016 (7)	−0.001 (6)	−0.006 (8)
C31	0.030 (5)	0.085 (9)	0.047 (6)	−0.006 (6)	0.010 (5)	−0.012 (6)
C32	0.037 (6)	0.116 (12)	0.050 (7)	0.001 (7)	0.015 (6)	−0.005 (7)
C33	0.052 (7)	0.093 (10)	0.036 (6)	−0.010 (7)	0.010 (5)	0.006 (6)
C34	0.044 (6)	0.069 (8)	0.031 (5)	0.001 (6)	0.005 (5)	0.001 (5)
C35	0.032 (5)	0.037 (5)	0.038 (5)	−0.002 (4)	0.002 (4)	0.002 (4)
C36	0.030 (5)	0.035 (5)	0.041 (5)	−0.010 (4)	−0.004 (4)	−0.002 (4)

Geometric parameters (Å, º) top

W1—O1E	1.677 (7)	N2—C11	1.355 (14)
W1—O4	1.880 (8)	N3—C13	1.342 (13)
W1—O2	1.895 (7)	N3—C24	1.350 (13)
W1—O3	1.909 (8)	N4—C22	1.325 (14)
W1—O1	1.912 (7)	N4—C23	1.357 (15)
W1—O4C	2.481 (11)	N5—C25	1.323 (13)
W2—O2E	1.672 (7)	N5—C36	1.352 (12)
W2—O1	1.893 (7)	N6—C34	1.328 (13)
W2—O5	1.917 (7)	N6—C35	1.348 (12)
W2—O6A	1.917 (18)	C1—C2	1.40 (2)
W2—O9A	1.971 (15)	C1—H1	0.9300
W2—O4C	2.526 (12)	C2—C3	1.35 (2)
W3—O3E	1.667 (8)	C2—H2	0.9300
W3—O5	1.873 (7)	C3—C4	1.42 (2)
W3—O2	1.886 (7)	C3—H3	0.9300
W3—O12	1.893 (8)	C4—C12	1.373 (17)
W3—O10	1.896 (8)	C4—C5	1.45 (2)
W3—O1Cⁱ	2.396 (11)	C5—C6	1.33 (2)
W3—O4C	2.473 (12)	C5—H5	0.9300
W4—O4E	1.676 (7)	C6—C7	1.45 (2)
W4—O3	1.875 (9)	C6—H6	0.9300
W4—O7	1.887 (8)	C7—C11	1.412 (17)
W4—O10ⁱ	1.897 (9)	C7—C8	1.41 (2)
W4—O8	1.905 (8)	C8—C9	1.35 (2)
W4—O1C	2.451 (12)	C8—H8	0.9300
W5—O5E	1.669 (7)	C9—C10	1.344 (19)
W5—O6Aⁱ	1.750 (18)	C9—H9	0.9300
W5—O12	1.897 (9)	C10—H10	0.9300
W5—O7ⁱ	1.908 (8)	C11—C12	1.421 (17)
W5—O11A	2.012 (19)	C13—C14	1.401 (17)
W5—O1Cⁱ	2.494 (12)	C13—H13	0.9300
W6—O6E	1.673 (7)	C14—C15	1.376 (18)
W6—O4	1.885 (9)	C14—H14	0.9300
W6—O8	1.887 (8)	C15—C16	1.410 (17)
W6—O11A	1.96 (2)	C15—H15	0.9300
W6—O9Aⁱ	2.085 (14)	C16—C24	1.426 (16)
O6A—W5ⁱ	1.750 (18)	C16—C17	1.429 (17)
O6B—V5ⁱ	2.064 (15)	C17—C18	1.342 (18)
O7—V5ⁱ	1.908 (8)	C17—H17	0.9300
O7—W5ⁱ	1.908 (8)	C18—C19	1.429 (19)
O9A—W6ⁱ	2.085 (14)	C18—H18	0.9300
O9B—V6ⁱ	1.746 (15)	C19—C23	1.397 (17)
O10—V4ⁱ	1.897 (9)	C19—C20	1.417 (19)
O10—W4ⁱ	1.897 (9)	C20—C21	1.36 (2)
P—O4C	1.481 (11)	C20—H20	0.9300
P—O4Cⁱ	1.481 (11)	C21—C22	1.37 (2)
P—O3C	1.530 (11)	C21—H21	0.9300
P—O3Cⁱ	1.530 (11)	C22—H22	0.9300
P—O1Cⁱ	1.554 (12)	C23—C24	1.430 (15)
P—O1C	1.554 (12)	C25—C26	1.366 (16)
P—O2C	1.582 (11)	C25—H25	0.9300
P—O2Cⁱ	1.582 (11)	C26—C27	1.347 (18)
O1C—O4Cⁱ	1.698 (16)	C26—H26	0.9300
O1C—W3ⁱ	2.396 (11)	C27—C28	1.399 (16)
O1C—W5ⁱ	2.494 (12)	C27—H27	0.9300
O4C—O1Cⁱ	1.698 (16)	C28—C36	1.413 (14)
O2C—V6ⁱ	2.453 (12)	C28—C29	1.436 (17)
O2C—V5ⁱ	2.462 (12)	C29—C30	1.351 (18)
O1W—H1W1	0.851 (10)	C29—H29	0.9300
O1W—H2W1	0.851 (10)	C30—C31	1.436 (17)
Co—N3	2.053 (9)	C30—H30	0.9300
Co—N6	2.060 (8)	C31—C32	1.398 (17)
Co—N1	2.066 (10)	C31—C35	1.406 (14)
Co—N4	2.066 (11)	C32—C33	1.346 (17)
Co—N2	2.078 (10)	C32—H32	0.9300
Co—N5	2.085 (8)	C33—C34	1.398 (16)
N1—C1	1.318 (16)	C33—H33	0.9300
N1—C12	1.369 (16)	C34—H34	0.9300
N2—C10	1.318 (14)	C35—C36	1.432 (14)

O1E—W1—O4	102.0 (5)	W3—O4C—W1	91.2 (4)
O1E—W1—O2	101.1 (4)	P—O4C—W2	123.5 (7)
O4—W1—O2	89.3 (4)	O1Cⁱ—O4C—W2	129.3 (7)
O1E—W1—O3	102.3 (5)	W3—O4C—W2	90.2 (4)
O4—W1—O3	87.7 (3)	W1—O4C—W2	90.8 (4)
O2—W1—O3	156.6 (4)	P—O2C—V6ⁱ	122.1 (6)
O1E—W1—O1	101.4 (4)	P—O2C—V5ⁱ	120.4 (6)
O4—W1—O1	156.7 (4)	V6ⁱ—O2C—V5ⁱ	91.7 (4)
O2—W1—O1	86.5 (3)	H1W1—O1W—H2W1	116 (2)
O3—W1—O1	87.1 (3)	N3—Co—N6	170.4 (3)
O1E—W1—O4C	159.7 (5)	N3—Co—N1	95.4 (3)
O4—W1—O4C	92.4 (5)	N6—Co—N1	93.8 (3)
O2—W1—O4C	64.5 (4)	N3—Co—N4	80.0 (4)
O3—W1—O4C	92.4 (4)	N6—Co—N4	97.0 (4)
O1—W1—O4C	65.1 (4)	N1—Co—N4	94.0 (4)
O2E—W2—O1	102.2 (4)	N3—Co—N2	97.5 (3)
O2E—W2—O5	101.8 (4)	N6—Co—N2	86.3 (3)
O1—W2—O5	87.4 (3)	N1—Co—N2	80.6 (4)
O2E—W2—O6A	112.9 (6)	N4—Co—N2	173.9 (4)
O1—W2—O6A	83.5 (6)	N3—Co—N5	90.9 (3)
O5—W2—O6A	145.3 (6)	N6—Co—N5	80.1 (3)
O2E—W2—O9A	91.4 (5)	N1—Co—N5	171.6 (4)
O1—W2—O9A	166.4 (5)	N4—Co—N5	92.5 (4)
O5—W2—O9A	90.3 (5)	N2—Co—N5	93.1 (4)
O6A—W2—O9A	90.8 (7)	C1—N1—C12	117.9 (12)
O2E—W2—O4C	160.0 (4)	C1—N1—Co	129.0 (10)
O1—W2—O4C	64.3 (3)	C12—N1—Co	112.9 (8)
O5—W2—O4C	64.5 (4)	C10—N2—C11	118.0 (11)
O6A—W2—O4C	81.4 (6)	C10—N2—Co	130.3 (9)
O9A—W2—O4C	102.7 (5)	C11—N2—Co	111.2 (8)
O3E—W3—O5	100.9 (4)	C13—N3—C24	118.0 (10)
O3E—W3—O2	100.0 (4)	C13—N3—Co	128.4 (8)
O5—W3—O2	88.3 (3)	C24—N3—Co	113.4 (7)
O3E—W3—O12	101.7 (5)	C22—N4—C23	117.6 (12)
O5—W3—O12	157.3 (4)	C22—N4—Co	129.5 (10)
O2—W3—O12	87.4 (4)	C23—N4—Co	112.8 (7)
O3E—W3—O10	102.5 (5)	C25—N5—C36	117.2 (9)
O5—W3—O10	88.7 (4)	C25—N5—Co	130.4 (8)
O2—W3—O10	157.5 (5)	C36—N5—Co	112.2 (6)
O12—W3—O10	86.8 (4)	C34—N6—C35	119.1 (9)
O3E—W3—O1Cⁱ	159.8 (4)	C34—N6—Co	127.5 (7)
O5—W3—O1Cⁱ	93.8 (4)	C35—N6—Co	113.2 (6)
O2—W3—O1Cⁱ	94.0 (4)	N1—C1—C2	123.2 (15)
O12—W3—O1Cⁱ	64.3 (4)	N1—C1—H1	118.4
O10—W3—O1Cⁱ	63.9 (5)	C2—C1—H1	118.4
O3E—W3—O4C	159.3 (4)	C3—C2—C1	118.6 (15)
O5—W3—O4C	66.2 (4)	C3—C2—H2	120.7
O2—W3—O4C	64.8 (4)	C1—C2—H2	120.7
O12—W3—O4C	91.9 (5)	C2—C3—C4	120.0 (15)
O10—W3—O4C	93.7 (5)	C2—C3—H3	120.0
O1Cⁱ—W3—O4C	40.8 (4)	C4—C3—H3	120.0
O4E—W4—O3	103.0 (4)	C12—C4—C3	117.4 (14)
O4E—W4—O7	101.6 (5)	C12—C4—C5	118.4 (13)
O3—W4—O7	88.7 (4)	C3—C4—C5	124.1 (14)
O4E—W4—O10ⁱ	99.9 (5)	C6—C5—C4	121.0 (13)
O3—W4—O10ⁱ	157.1 (5)	C6—C5—H5	119.5
O7—W4—O10ⁱ	88.2 (4)	C4—C5—H5	119.5
O4E—W4—O8	101.9 (4)	C5—C6—C7	121.5 (15)
O3—W4—O8	87.0 (4)	C5—C6—H6	119.3
O7—W4—O8	156.5 (4)	C7—C6—H6	119.3
O10ⁱ—W4—O8	86.8 (4)	C11—C7—C8	117.7 (13)
O4E—W4—O1C	157.0 (4)	C11—C7—C6	117.8 (14)
O3—W4—O1C	95.6 (4)	C8—C7—C6	124.5 (14)
O7—W4—O1C	65.0 (4)	C9—C8—C7	118.6 (13)
O10ⁱ—W4—O1C	62.7 (4)	C9—C8—H8	120.7
O8—W4—O1C	92.4 (4)	C7—C8—H8	120.7
O5E—W5—O6Aⁱ	112.5 (6)	C10—C9—C8	120.3 (14)
O5E—W5—O12	100.4 (4)	C10—C9—H9	119.9
O6Aⁱ—W5—O12	146.1 (6)	C8—C9—H9	119.9
O5E—W5—O7ⁱ	100.6 (4)	N2—C10—C9	124.4 (14)
O6Aⁱ—W5—O7ⁱ	79.6 (7)	N2—C10—H10	117.8
O12—W5—O7ⁱ	86.8 (4)	C9—C10—H10	117.8
O5E—W5—O11A	94.4 (6)	N2—C11—C7	121.0 (11)
O6Aⁱ—W5—O11A	89.5 (8)	N2—C11—C12	119.3 (11)
O12—W5—O11A	96.1 (6)	C7—C11—C12	119.7 (12)
O7ⁱ—W5—O11A	164.0 (7)	N1—C12—C4	122.8 (12)
O5E—W5—O1Cⁱ	155.8 (4)	N1—C12—C11	115.7 (11)
O6Aⁱ—W5—O1Cⁱ	84.0 (6)	C4—C12—C11	121.4 (13)
O12—W5—O1Cⁱ	62.1 (4)	N3—C13—C14	122.7 (11)
O7ⁱ—W5—O1Cⁱ	63.8 (4)	N3—C13—H13	118.6
O11A—W5—O1Cⁱ	103.7 (6)	C14—C13—H13	118.6
O6E—W6—O4	101.1 (5)	C15—C14—C13	119.1 (12)
O6E—W6—O8	100.9 (5)	C15—C14—H14	120.4
O4—W6—O8	87.8 (4)	C13—C14—H14	120.4
O6E—W6—O11A	93.7 (6)	C14—C15—C16	120.5 (12)
O4—W6—O11A	93.3 (6)	C14—C15—H15	119.8
O8—W6—O11A	164.8 (6)	C16—C15—H15	119.8
O6E—W6—O9Aⁱ	94.2 (5)	C15—C16—C24	115.9 (11)
O4—W6—O9Aⁱ	164.3 (5)	C15—C16—C17	125.1 (12)
O8—W6—O9Aⁱ	92.6 (5)	C24—C16—C17	119.0 (11)
O11A—W6—O9Aⁱ	82.3 (7)	C18—C17—C16	120.7 (12)
W2—O1—W1	139.3 (4)	C18—C17—H17	119.7
W3—O2—W1	138.9 (5)	C16—C17—H17	119.7
W4—O3—W1	139.2 (6)	C17—C18—C19	122.0 (13)
W1—O4—W6	139.7 (6)	C17—C18—H18	119.0
W3—O5—W2	138.3 (4)	C19—C18—H18	119.0
W5ⁱ—O6A—W2	149.7 (10)	C23—C19—C20	116.5 (13)
W4—O7—V5ⁱ	138.9 (5)	C23—C19—C18	118.9 (12)
W4—O7—W5ⁱ	138.9 (5)	C20—C19—C18	124.5 (13)
V5ⁱ—O7—W5ⁱ	0.00 (3)	C21—C20—C19	119.0 (14)
W6—O8—W4	139.3 (5)	C21—C20—H20	120.5
W2—O9A—W6ⁱ	123.3 (7)	C19—C20—H20	120.5
W3—O10—V4ⁱ	138.7 (6)	C20—C21—C22	120.2 (14)
W3—O10—W4ⁱ	138.7 (6)	C20—C21—H21	119.9
V4ⁱ—O10—W4ⁱ	0.00 (3)	C22—C21—H21	119.9
W6—O11A—W5	125.4 (9)	N4—C22—C21	123.2 (14)
W3—O12—W5	139.9 (6)	N4—C22—H22	118.4
O4C—P—O4Cⁱ	180.0 (8)	C21—C22—H22	118.4
O4C—P—O3C	67.4 (6)	N4—C23—C19	123.3 (11)
O4Cⁱ—P—O3C	112.6 (6)	N4—C23—C24	116.6 (11)
O4C—P—O3Cⁱ	112.6 (6)	C19—C23—C24	120.1 (11)
O4Cⁱ—P—O3Cⁱ	67.4 (6)	N3—C24—C16	123.8 (10)
O3C—P—O3Cⁱ	180.000 (3)	N3—C24—C23	116.9 (10)
O4C—P—O1Cⁱ	68.0 (6)	C16—C24—C23	119.3 (11)
O4Cⁱ—P—O1Cⁱ	112.0 (6)	N5—C25—C26	124.1 (12)
O3C—P—O1Cⁱ	108.6 (6)	N5—C25—H25	117.9
O3Cⁱ—P—O1Cⁱ	71.4 (6)	C26—C25—H25	117.9
O4C—P—O1C	112.0 (6)	C27—C26—C25	119.2 (11)
O4Cⁱ—P—O1C	68.0 (6)	C27—C26—H26	120.4
O3C—P—O1C	71.4 (6)	C25—C26—H26	120.4
O3Cⁱ—P—O1C	108.6 (6)	C26—C27—C28	120.5 (11)
O1Cⁱ—P—O1C	180.0 (7)	C26—C27—H27	119.8
O4C—P—O2C	69.2 (6)	C28—C27—H27	119.8
O4Cⁱ—P—O2C	110.8 (6)	C27—C28—C36	116.3 (11)
O3C—P—O2C	107.1 (6)	C27—C28—C29	124.3 (11)
O3Cⁱ—P—O2C	72.9 (6)	C36—C28—C29	119.4 (10)
O1Cⁱ—P—O2C	105.5 (6)	C30—C29—C28	119.3 (11)
O1C—P—O2C	74.5 (6)	C30—C29—H29	120.4
O4C—P—O2Cⁱ	110.8 (6)	C28—C29—H29	120.4
O4Cⁱ—P—O2Cⁱ	69.2 (6)	C29—C30—C31	123.6 (11)
O3C—P—O2Cⁱ	72.9 (6)	C29—C30—H30	118.2
O3Cⁱ—P—O2Cⁱ	107.1 (6)	C31—C30—H30	118.2
O1Cⁱ—P—O2Cⁱ	74.5 (6)	C32—C31—C35	116.5 (11)
O1C—P—O2Cⁱ	105.5 (6)	C32—C31—C30	126.1 (11)
O2C—P—O2Cⁱ	180.0 (7)	C35—C31—C30	117.4 (11)
P—O1C—O4Cⁱ	54.0 (6)	C33—C32—C31	120.8 (11)
P—O1C—W3ⁱ	126.0 (6)	C33—C32—H32	119.6
O4Cⁱ—O1C—W3ⁱ	72.0 (6)	C31—C32—H32	119.6
P—O1C—W4	122.9 (7)	C32—C33—C34	119.5 (11)
O4Cⁱ—O1C—W4	135.7 (7)	C32—C33—H33	120.2
W3ⁱ—O1C—W4	94.1 (4)	C34—C33—H33	120.2
P—O1C—W5ⁱ	120.0 (6)	N6—C34—C33	121.5 (11)
O4Cⁱ—O1C—W5ⁱ	129.8 (7)	N6—C34—H34	119.2
W3ⁱ—O1C—W5ⁱ	93.4 (4)	C33—C34—H34	119.2
W4—O1C—W5ⁱ	91.9 (4)	N6—C35—C31	122.5 (9)
P—O4C—O1Cⁱ	58.0 (5)	N6—C35—C36	117.2 (9)
P—O4C—W3	125.2 (6)	C31—C35—C36	120.3 (9)
O1Cⁱ—O4C—W3	67.2 (5)	N5—C36—C28	122.7 (9)
P—O4C—W1	125.4 (6)	N5—C36—C35	117.3 (9)
O1Cⁱ—O4C—W1	132.1 (7)	C28—C36—C35	119.9 (9)

N3—Co—N1—C1	83.6 (10)	Co—N1—C12—C4	−173.8 (9)
N6—Co—N1—C1	−94.0 (10)	C1—N1—C12—C11	179.9 (10)
N4—Co—N1—C1	3.3 (10)	Co—N1—C12—C11	4.1 (12)
N2—Co—N1—C1	−179.7 (10)	C3—C4—C12—N1	−1.5 (18)
N5—Co—N1—C1	−138 (2)	C5—C4—C12—N1	−178.5 (11)
N3—Co—N1—C12	−101.2 (7)	C3—C4—C12—C11	−179.3 (11)
N6—Co—N1—C12	81.2 (7)	C5—C4—C12—C11	3.8 (17)
N4—Co—N1—C12	178.5 (7)	N2—C11—C12—N1	−0.5 (15)
N2—Co—N1—C12	−4.5 (7)	C7—C11—C12—N1	−177.9 (10)
N5—Co—N1—C12	37 (3)	N2—C11—C12—C4	177.4 (10)
N3—Co—N2—C10	−89.4 (10)	C7—C11—C12—C4	0.0 (16)
N6—Co—N2—C10	81.8 (10)	C24—N3—C13—C14	−1.0 (16)
N1—Co—N2—C10	176.3 (10)	Co—N3—C13—C14	172.4 (9)
N4—Co—N2—C10	−155 (3)	N3—C13—C14—C15	2.1 (18)
N5—Co—N2—C10	1.9 (10)	C13—C14—C15—C16	−1.4 (18)
N3—Co—N2—C11	98.4 (7)	C14—C15—C16—C24	−0.2 (16)
N6—Co—N2—C11	−90.4 (7)	C14—C15—C16—C17	−178.5 (11)
N1—Co—N2—C11	4.1 (7)	C15—C16—C17—C18	177.9 (11)
N4—Co—N2—C11	33 (4)	C24—C16—C17—C18	−0.3 (17)
N5—Co—N2—C11	−170.3 (7)	C16—C17—C18—C19	−0.1 (19)
N6—Co—N3—C13	−105 (2)	C17—C18—C19—C23	−0.3 (18)
N1—Co—N3—C13	88.7 (10)	C17—C18—C19—C20	−178.3 (12)
N4—Co—N3—C13	−178.2 (10)	C23—C19—C20—C21	3.5 (17)
N2—Co—N3—C13	7.5 (10)	C18—C19—C20—C21	−178.4 (12)
N5—Co—N3—C13	−85.8 (9)	C19—C20—C21—C22	−4.4 (19)
N6—Co—N3—C24	68 (2)	C23—N4—C22—C21	−1.6 (18)
N1—Co—N3—C24	−97.7 (7)	Co—N4—C22—C21	−176.6 (10)
N4—Co—N3—C24	−4.5 (7)	C20—C21—C22—N4	4 (2)
N2—Co—N3—C24	−178.8 (7)	C22—N4—C23—C19	0.8 (16)
N5—Co—N3—C24	87.9 (7)	Co—N4—C23—C19	176.6 (8)
N3—Co—N4—C22	−180.0 (11)	C22—N4—C23—C24	179.7 (10)
N6—Co—N4—C22	9.2 (11)	Co—N4—C23—C24	−4.5 (12)
N1—Co—N4—C22	−85.2 (10)	C20—C19—C23—N4	−1.8 (16)
N2—Co—N4—C22	−113 (3)	C18—C19—C23—N4	−179.9 (10)
N5—Co—N4—C22	89.5 (10)	C20—C19—C23—C24	179.3 (10)
N3—Co—N4—C23	4.8 (7)	C18—C19—C23—C24	1.1 (16)
N6—Co—N4—C23	−166.0 (7)	C13—N3—C24—C16	−0.8 (15)
N1—Co—N4—C23	99.7 (8)	Co—N3—C24—C16	−175.2 (8)
N2—Co—N4—C23	71 (4)	C13—N3—C24—C23	177.9 (9)
N5—Co—N4—C23	−85.6 (8)	Co—N3—C24—C23	3.5 (11)
N3—Co—N5—C25	6.6 (10)	C15—C16—C24—N3	1.4 (16)
N6—Co—N5—C25	−176.6 (10)	C17—C16—C24—N3	179.8 (10)
N1—Co—N5—C25	−132 (2)	C15—C16—C24—C23	−177.3 (10)
N4—Co—N5—C25	86.7 (10)	C17—C16—C24—C23	1.1 (15)
N2—Co—N5—C25	−90.9 (10)	N4—C23—C24—N3	0.7 (14)
N3—Co—N5—C36	−179.0 (7)	C19—C23—C24—N3	179.7 (9)
N6—Co—N5—C36	−2.3 (7)	N4—C23—C24—C16	179.5 (9)
N1—Co—N5—C36	42 (3)	C19—C23—C24—C16	−1.5 (15)
N4—Co—N5—C36	−98.9 (7)	C36—N5—C25—C26	0.2 (17)
N2—Co—N5—C36	83.5 (7)	Co—N5—C25—C26	174.4 (9)
N3—Co—N6—C34	−162.2 (18)	N5—C25—C26—C27	1 (2)
N1—Co—N6—C34	3.7 (10)	C25—C26—C27—C28	−1.6 (19)
N4—Co—N6—C34	−90.8 (9)	C26—C27—C28—C36	0.9 (17)
N2—Co—N6—C34	84.0 (10)	C26—C27—C28—C29	−176.9 (13)
N5—Co—N6—C34	177.8 (10)	C27—C28—C29—C30	177.4 (13)
N3—Co—N6—C35	23 (2)	C36—C28—C29—C30	−0.4 (19)
N1—Co—N6—C35	−171.4 (7)	C28—C29—C30—C31	0 (2)
N4—Co—N6—C35	94.0 (7)	C29—C30—C31—C32	−179.1 (15)
N2—Co—N6—C35	−91.2 (7)	C29—C30—C31—C35	0 (2)
N5—Co—N6—C35	2.7 (7)	C35—C31—C32—C33	0 (2)
C12—N1—C1—C2	−1.2 (17)	C30—C31—C32—C33	179.1 (14)
Co—N1—C1—C2	173.8 (9)	C31—C32—C33—C34	−1 (2)
N1—C1—C2—C3	0 (2)	C35—N6—C34—C33	−2.3 (17)
C1—C2—C3—C4	0 (2)	Co—N6—C34—C33	−177.2 (9)
C2—C3—C4—C12	0 (2)	C32—C33—C34—N6	2 (2)
C2—C3—C4—C5	177.0 (14)	C34—N6—C35—C31	0.8 (16)
C12—C4—C5—C6	−5.0 (19)	Co—N6—C35—C31	176.4 (9)
C3—C4—C5—C6	178.3 (13)	C34—N6—C35—C36	−178.3 (9)
C4—C5—C6—C7	2 (2)	Co—N6—C35—C36	−2.7 (11)
C5—C6—C7—C11	1.5 (18)	C32—C31—C35—N6	0.5 (17)
C5—C6—C7—C8	−179.5 (13)	C30—C31—C35—N6	−178.9 (11)
C11—C7—C8—C9	−2.1 (18)	C32—C31—C35—C36	179.6 (11)
C6—C7—C8—C9	178.9 (12)	C30—C31—C35—C36	0.1 (17)
C7—C8—C9—C10	2 (2)	C25—N5—C36—C28	−1.0 (15)
C11—N2—C10—C9	−1.5 (18)	Co—N5—C36—C28	−176.1 (8)
Co—N2—C10—C9	−173.2 (10)	C25—N5—C36—C35	176.7 (10)
C8—C9—C10—N2	0 (2)	Co—N5—C36—C35	1.5 (11)
C10—N2—C11—C7	0.8 (15)	C27—C28—C36—N5	0.4 (15)
Co—N2—C11—C7	174.1 (8)	C29—C28—C36—N5	178.4 (10)
C10—N2—C11—C12	−176.5 (10)	C27—C28—C36—C35	−177.2 (10)
Co—N2—C11—C12	−3.3 (12)	C29—C28—C36—C35	0.7 (15)
C8—C7—C11—N2	0.9 (16)	N6—C35—C36—N5	0.8 (13)
C6—C7—C11—N2	180.0 (10)	C31—C35—C36—N5	−178.4 (10)
C8—C7—C11—C12	178.3 (10)	N6—C35—C36—C28	178.5 (9)
C6—C7—C11—C12	−2.7 (16)	C31—C35—C36—C28	−0.6 (15)
C1—N1—C12—C4	2.0 (16)

Symmetry code: (i) −x+3/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/C1–C4/C12 and N3/C13–C16/C24 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1E	0.85 (1)	2.17 (11)	2.928 (14)	149 (20)
O1W—H2W1···O3Eⁱⁱ	0.85 (1)	1.99 (3)	2.836 (13)	173 (17)
C9—H9···O5Eⁱⁱⁱ	0.93	2.55	3.208 (15)	128
C26—H26···O12^iv	0.93	2.46	2.973 (15)	114
C33—H33···O5ⁱ	0.93	2.53	3.345 (13)	147
C34—H34···O8	0.93	2.43	3.114 (13)	130
C34—H34···Cg1	0.93	3.04	3.811 (12)	142
C25—H25···Cg2	0.93	2.99	3.777 (13)	143

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+2, −y, −z+1; (iii) x, −y, z−1/2; (iv) −x+3/2, y+1/2, −z+1/2.

Selected bond lengths (Å) top

Co—N3	2.053 (9)	Co—N4	2.066 (11)
Co—N6	2.060 (8)	Co—N2	2.078 (10)
Co—N1	2.066 (10)	Co—N5	2.085 (8)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/C1–C4/C12 and N3/C13–C16/C24 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1E	0.851 (10)	2.17 (11)	2.928 (14)	149 (20)
O1W—H2W1···O3Eⁱ	0.851 (10)	1.99 (3)	2.836 (13)	173 (17)
C9—H9···O5Eⁱⁱ	0.93	2.55	3.208 (15)	128
C26—H26···O12ⁱⁱⁱ	0.93	2.46	2.973 (15)	114
C33—H33···O5^iv	0.93	2.53	3.345 (13)	147
C34—H34···O8	0.93	2.43	3.114 (13)	130
C34—H34···Cg1	0.93	3.04	3.811 (12)	142
C25—H25···Cg2	0.93	2.99	3.777 (13)	143

Symmetry codes: (i) −x+2, −y, −z+1; (ii) x, −y, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+3/2, −y+1/2, −z+1.

Acknowledgements

The authors express their appreciation to the CNRS 6230 UFR Sciences and Techniques of Nantes in France for supporting this work.

References

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Volume 70| Part 4| April 2014| Pages m125-m126

doi:10.1107/S160053681400484X

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