[Co^II₄Mo^V₁₂O₂₈(OH)₁₂(H₂O)₁₂]·12H₂O: facilitating single-crystal growth by deuteration

The structure of the neutral heterometal oxide cluster dodeca­aqua-di-μ₃-hydroxido-deca-μ₂-hydroxido-octa­cosaoxidotetra­cobalt(II)dodeca­molybdenum(V) dodeca­hydrate, [Mo₁₂O₂₈(μ₂-OH)₁₀(μ₃-OH)₂{Co(H₂O)₃}₄], is virtually identical to the previously reported Ni^II analogue [Mo₁₂O₂₈(μ₂-OH)₁₀(μ₃-OH)₂{Ni^II(H₂O)₃}₄] [Müller, Beugholt, Kögerler, Bögge, Budko & Luban (2000). Inorg. Chem. 39, 5176–5177], the first mol­ecular magnet to exhibit signs of magnetostriction. The formation kinetics of the neutral cluster species, which is insoluble in water, can be significantly slowed by the use of deuterated reactants in order to grow single crystals of sufficient size for single-crystal X-ray diffraction studies using standard diffractometers. One half of the main cluster and six solvent water mol­ecules constitute the asymmetric unit. The main cluster is located on a mirror plane.

S1. Comment

Magnetically functionalized polyoxomolybdates present a structurally very diverse source of molecular spin polytopes featuring a wide range of magnetic phenomena. In these species, the redox-active, otherwise diamagnetic, molybdate structures serve as scaffolds into which (currently up to 30) magnetic transition metal cations can be integrated, resulting in magnetic characteristics ranging from molecular spin frustration and spin-glass transitions (Kögerler et al., 2010) to magnetic metastability (Ritchie et al., 2008) and charge-dependent exchange coupling (Botar et al., 2009). The neutral polyoxomolybdate(V)-based cluster [Mo₁₂O₂₈(µ₂-OH)₁₀(µ₃-OH)₂{Ni^II(H₂O)₃}₄] (= {Ni₄Mo₁₂}), isolated as {Ni₄Mo₁₂}.14H₂O (Müller et al., 2000) represents the first molecular magnet featuring aspects of magnetostriction that were attributed to the `non-innocent' ε-Keggin polyanion serving as a superexchange pathway between the Ni^II centres defining a nearly regular tetrahedron (Schnack et al., 2006). In particular, both the exchange energies for the intramolecular antiferromagnetic coupling and the absorption intensities in the UV–Vis spectroscopic range depend on the external magnetic field. In order to explore these effects in more detail, isostructural derivatives with other spin centres were targeted, though their characterization was hampered by the fact that the charge-neutral {M^II₄Mo₁₂} clusters (where M is Co or Fe) are barely soluble in the aqueous reaction media, resulting in their immediate precipitation as microcrystalline products.

We herein report that this problem in obtaining single crystals of the {Co^IIMo₁₂} derivative suitable for X-ray diffraction studies can be prevented by utilizing deuterated reagents (D₂O, deuterated ammonium molybdate and deuterated hydrazine sulfate in our case). Apparently, the multiple condensation steps leading to the highly nucleophilic ε-Keggin polyanion [H_xMo^V₁₂O₄₀]^(20-x)- are slowed down significantly, so that the formation of this proposed intermediate becomes the rate-determining step for the overall reaction and thus the growth of crystals. Under otherwise identical reaction conditions, this results in crystals with dimensions that are approximately one order of magnitude larger (Fig. 1).

The {Co₄Mo₁₂} cluster was isolated as the dodecahydrate, [Mo^V₁₂O₃₀(µ₂-OH)₁₀H₂{Co^II(H₂O)₃}₄].12H₂O = {Co₄Mo₁₂}.12H₂O. The cluster (Fig. 2) is virtually isostructural with the {Ni₄Mo₁₂} species and is of crystallographic C_s symmetry (atoms Co1, Co2, Mo4 and Mo5 define the mirror plane). {Co₄Mo₁₂} features a tenfold protonated ε-Keggin core anion, [Mo^V₁₂O₃₈(µ₃-OH)₂]^18-, built up from four edge-sharing {Mo₃} groups (each consisting of three edge-sharing MoO₆ octahedra). Note that the T_d-symmetric ε-Keggin structure can be formally derived from the common α-Keggin isomer by rotating all four {Mo₃} groups by 60°. The ε-Keggin core comprises a central tetrahedral cavity defined by four µ₃-O sites (atom O11 and its symmetry equivalents, and atoms O18 and O22), and two H atoms bind to the four µ₃-O sites. This double protonation is common to all known ε-Keggin structures lacking a central heteroanion template. Within the ε-Keggin framework, the Mo positions form six Mo^V₂ groups with short Mo—Mo single bonds, with an average Mo···Mo separation of 2.586 (5) Å, but one longer distance for Mo4···Mo5 of 2.9284 (15) Å. The Mo—Mo single bonds result in spin pairing; the analogous {Mo^VI₄Mo^V₁₂}-type tetracapped ε-Keggin cluster, in which four Mo^VIO₃ groups assume the positions of the M^II(H₂O)₃ groups in the {M^IIMo₁₂} family, is diamagnetic (Müller et al., 2000). Mo—Mo single bonds with Mo···Mo distances ranging from 2.6 to 3.4 Å are also found in face-sharing Mo^VO₆ dimers present e.g. in {Mo₅₇M₆}- or {Mo₁₃₂}-type polyoxomolybdates, where these {Mo^V₂} dimers are diamagnetic as well (Müller et al., 1999; Müller et al., 2001). The assignment of the oxidation state +V to all 12 Mo positions is based on both charge neutrality arguments and the observed absence of a magnetic moment of the ε-Keggin core, although the bond-valence sum for atom Mo5 of 5.816 is closer to +VI than +V. Note that the diamagnetism of the ε-Keggin core, which rules out a paramagnetic {Mo^V₁₁Mo^VI₁} configuration, in both the title compound and the {Ni^II₄Mo^V₁₂} analogue is evident from their high-temperature susceptibility once the contributions of the four M^II spin centres are subtracted.

In the title compound, {Co₄Mo₁₂}, four [Co^II(H₂O)₃]²⁺ groups are each coordinated to three (non-protonated) µ₂-oxide centres that interlink the Mo positions of the {Mo^V₂} groups. This results in an octahedral O₃Co^II(H₂O)₃ coordination environment with all oxide and water ligands in trans orientations. The resulting Co—O bond lengths span very similar intervals: Co-(µ₂-O) = 2.015 (7)–2.072 (5) Å and Co—OH₂ = 2.027 (9)–2.118 (6) Å. This capping of the ε-Keggin core produces a near-regular Co₄ tetrahedron, in which the Co centres are coupled via –O—Mo—O– superexchange pathways. The Co···Co distances range from 6.520 (2) to 6.707 (2) Å, compared with 6.606 (5)–6.700 (5) Å in {Ni₄Mo₁₂}.

In the solid-state structure of {Co₄Mo₁₂}.12H₂O, the neutral cluster molecules are spaced apart by solvent water molecules (Fig. 3). The closest intermolecular Co···Co distance in the solid state is 7.162 (2) Å [Co1 to Co3(x - 1, y, z) of a neighbouring {Co₄Mo₁₂} molecule], rendering intermolecular (dipole–dipole) magnetic coupling insignificant. Preliminary magnetic studies show that the octahedrally coordinated Co^II centres (⁴T₁, S = 3/2) in {Co₄Mo₁₂} display pronounced single-ion ligand field and spin-orbit coupling effects (Speldrich et al., 2011) and are antiferromagnetically coupled. From preliminary field-dependent magnetization studies, the first-level crossing fields (i.e. steps in the magnetization versus field curve at 0.5 K) occur at 1.5 and 7.1 T. This pronounced deviation from equidistant crossing fields, also observed in {Ni₄Mo₁₂}, is an initial indication that {Co₄Mo₁₂} displays similar behaviour that could be caused by molecular magnetostriction.

Finally, we note that while the {Ni₄Mo₁₂}.14H₂O compound originally reported (Müller et al., 2000) crystallizes in the space group C2/m, we found that lowering the synthesis reaction temperature to 303 K (as required for the synthesis of the title compound, {Co₄Mo₁₂}.12H₂O) produces a derivative, {Ni₄Mo₁₂}.12H₂O, which also crystallizes in the space group P2₁/m [a = 12.145 (2) Å, b = 18.188 (3) Å, c = 12.174 (2) Å and β = 93.030 (3)°] and otherwise exhibits a lattice construction identical to that of {Co₄Mo₁₂}.12H₂O.

Related literature

For related literature, see: Botar et al. (2009); Kögerler et al. (2010); Müller et al. (1999, 2000, 2001); Ritchie et al. (2008); Schnack et al. (2006); Speldrich et al. (2011).

S2. Experimental

Ammonium molybdate, (NH₄)₆[Mo₇O₂₄].4H₂O (3.1 g, 2.5 mmol), and cobalt(II) acetate, Co(CH₃COO)₂.4H₂O (11.2 g, 45 mmol) were dissolved in H₂O (250 ml) and acetic acid (50%; 40 ml) in a 500 ml Erlenmeyer flask. After the formation of a clear solution, hydrazinium sulfate (650 mg, 5.0 mmol) was added in small portions under vigorous stirring (pH ca 3.5). The flask was covered with Parafilm and kept in an oil bath at 303 K for 3 d. The precipitated {Co₄Mo₁₂}.12H₂O was separated from the reaction solution by decanting and washed several times with distilled water (yield 1.8 g; 69% based on Mo). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3200 (s/br), 953 (s), 790 (m), 755 (m), 664 (w), 520 (m). Isolation of single crystals (brown plates) of sufficient size for single-crystal X-ray structure analysis required the use of D₂O, deuterated acetic acid, deuterated ammonium molybdate and deuterated hydrazine sulfate. As both H₂O and D₂O were present in the reaction mixture, it was not possible to determine the D:H ratio in the product (note that the formation of polyoxometalates in deuterated media generally results in products with H:D ratios that significantly deviate from the stochiometric H:D ratios of the reaction solutions). For simplicity, all H/D positions were therefore designated as H.

S3. Refinement

During the structure solution and refinement, none of expected H atoms were observed in a difference Fourier map and, therefore, they were not included in the refinement. The Mo centres are assumed to be Mo^V (see Comment) and each of the four Co centres binds to three terminal water ligands. In the very centre of the ε-Keggin cluster, a small cavity is defined by a tetrahedron of four µ₃-O atoms. As with all known ε-Keggin structures, two of them are expected to be protonated. To satisfy charge neutrality, the remaining ten H atoms are distributed over bridging O atoms on the cluster surface. The resulting formula and derived quantities were adjusted according to the analytical and physical properties of the compound. For this reason, the resulting formula is not in full accord with the atom list.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Microscope image, comparing size distributions between crystalline material obtained using deuterated (left) and non-deuterated (right) educts in the synthesis of {Co4Mo12}.12H2O.
	Fig. 2. The structure of the {Co4Mo12} cluster, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [In the electronic version of the journal, Co atoms are green, Mo blue, µ3-O atoms defining the central O4 tetrahedron are yellow, O (water ligands) are brown and the remaining O atoms are red]. Short Mo···Mo contacts are highlighted by dashed lines. H atoms have been omitted for clarity. [Symmetry code: (i) x, 1/2 - y, z.] [Please supply a revised plot with all labels having the same size and not overlapping bonds and atoms]
	Fig. 3. A packing diagram for {Co4Mo12}.12H2O, viewed approximately along a, with the cell edge of one unit cell outlined. The neutral {Co4Mo12} clusters are shown in a polyhedral representation and the oxygen atoms of the solvent water solvate are drawn as small spheres. H atoms have been omitted for clarity.

dodecaaquadi-µ₃-hydroxido-deca-µ₂-hydroxido- octacosaoxidotetracobalt(II)dodecamolybdenum(V) dodecahydrate

Crystal data

[Co4Mo12O28(OH)12(H2O)12]·12H2O	F(000) = 2368
Mr = 2471.48	Dx = 3.097 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 956 reflections
a = 12.061 (3) Å	θ = 3.6–27.7°
b = 18.151 (5) Å	µ = 4.09 mm^−1
c = 12.129 (3) Å	T = 193 K
β = 93.403 (5)°	Plate, brown
V = 2650.4 (12) Å^3	0.20 × 0.15 × 0.06 mm
Z = 2

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	6337 independent reflections
Radiation source: fine-focus sealed tube	5163 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ϕ and ω scans	θmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
Tmin = 0.62, Tmax = 0.76	k = −23→23
23238 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters not defined
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0436P)^2 + 27.542P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
6337 reflections	Δρmax = 1.80 e Å^−3
385 parameters	Δρmin = −1.58 e Å^−3
0 restraints

Special details

Experimental. An X-ray quality crystal was selected under ambient conditions and covered with Paratone oil. The crystal was mounted and centred in the X-ray beam using a video camera.The crystal evaluation and data collection were performed on a Bruker SMART1000 CCD diffractometer with a detector-to-crystal distance of 5 cm. The initial cell parameters were obtained from three series of ω scans at different starting angles. Each series consisted of 30 frames collected at intervals of 0.3 in a 10 range about ω with the exposure time of 10 s per frame. The obtained reflections were successfully indexed by an automated indexing routine built to SMART (Bruker, 2003).

The data were collected using the full sphere routine by collecting four sets of frames with 0.3 scans in ω with an exposure time 30 sec per frame. This data set was corrected for Lorentz and polarization effects. The absorption correction was based on a fit of a spherical harmonic function to the empirical transmission surface as sampled by multiple equivalent measurements using SADABS (Sheldrick, 1996).

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. The splitting model was tried for all oxygen atoms of the coordinated and solvent water molecules. This approach did not lead to an improvement of the refinement, therefore the original model was used for final outputs.

The systematic absences in the diffraction data were consistent for the stated space group. The position of almost all atoms were found by direct methods. The remaining atoms were located in an alternating series of least-squares cycles on difference Fourier maps. All non-hydrogen atoms were refined in full-matrix anisotropic approximation.

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

	x	y	z	Uiso*/Ueq
Mo1	−0.06085 (5)	0.32114 (3)	0.47739 (5)	0.01059 (14)
Mo2	0.35913 (5)	0.34625 (3)	0.41800 (5)	0.00958 (13)
Mo3	−0.03327 (5)	0.41679 (3)	0.24242 (5)	0.01033 (14)
Mo4	0.21968 (8)	0.2500	0.01241 (8)	0.0158 (2)
Mo5	0.39867 (8)	0.2500	0.18646 (8)	0.01441 (19)
Mo6	0.17395 (5)	0.41428 (3)	0.44272 (5)	0.00948 (13)
Mo7	−0.01087 (5)	0.34683 (3)	0.05879 (5)	0.01041 (13)
Co1	−0.21395 (11)	0.2500	0.22494 (11)	0.0105 (3)
Co2	0.19486 (11)	0.2500	0.62470 (11)	0.0086 (3)
Co3	0.25794 (8)	0.42960 (5)	0.15337 (8)	0.0100 (2)
O1	0.2171 (5)	0.5380 (3)	0.2013 (5)	0.0211 (12)
O2	0.2505 (5)	0.4660 (3)	−0.0089 (5)	0.0252 (13)
O3	0.4523 (4)	0.3264 (3)	0.2855 (4)	0.0133 (10)
O4	0.2674 (4)	0.4076 (3)	0.3172 (4)	0.0120 (10)
O5	0.4213 (5)	0.4591 (4)	0.1542 (6)	0.0301 (14)
O6	0.2249 (5)	0.4881 (3)	0.5160 (4)	0.0178 (11)
O7	0.0696 (4)	0.4869 (3)	0.3451 (4)	0.0130 (10)
O8	0.2409 (4)	0.3299 (3)	0.5184 (4)	0.0118 (10)
O9	0.0420 (6)	0.2500	0.5481 (6)	0.0124 (14)
O10	0.0453 (4)	0.4041 (3)	0.5539 (4)	0.0136 (10)
O11	0.0549 (4)	0.3470 (3)	0.3612 (4)	0.0112 (10)
O12	−0.1399 (4)	0.4016 (3)	0.3723 (4)	0.0138 (10)
O13	−0.1356 (6)	0.2500	0.3777 (6)	0.0129 (14)
O14	−0.1083 (4)	0.3301 (3)	0.1787 (4)	0.0144 (10)
O15	0.0919 (4)	0.4083 (3)	0.1476 (4)	0.0132 (10)
O16	−0.0829 (4)	0.4020 (3)	−0.0315 (4)	0.0185 (12)
O17	−0.0831 (6)	0.2500	−0.0113 (6)	0.0136 (15)
O18	0.0772 (6)	0.2500	0.1336 (6)	0.0122 (14)
O19	0.1199 (4)	0.3270 (3)	−0.0374 (4)	0.0146 (11)
O20	0.3054 (7)	0.2500	−0.0931 (6)	0.0178 (16)
O21	0.2925 (4)	0.3208 (3)	0.1169 (4)	0.0142 (10)
O22	0.2817 (6)	0.2500	0.3298 (6)	0.0103 (14)
O23	0.4315 (6)	0.2500	0.4884 (6)	0.0139 (15)
O24	0.1484 (5)	0.3340 (3)	0.7295 (4)	0.0213 (12)
O25	0.3529 (7)	0.2500	0.6917 (7)	0.0268 (19)
O26	−0.1531 (5)	0.3389 (3)	0.5743 (5)	0.0194 (12)
O27	−0.3206 (5)	0.3331 (3)	0.2677 (6)	0.0307 (15)
O28	−0.2822 (7)	0.2500	0.0665 (8)	0.042 (3)
O29	−0.1070 (5)	0.4907 (3)	0.1948 (5)	0.0210 (12)
O30	0.5006 (6)	0.2500	0.0981 (7)	0.0192 (17)
O31	0.4517 (5)	0.4019 (3)	0.4855 (5)	0.0199 (12)
O32	0.102 (2)	0.7500	0.2278 (11)	0.136 (9)
O33	0.6466 (9)	0.2500	0.5135 (14)	0.076 (4)
O34	0.6129 (8)	0.4095 (5)	0.0460 (9)	0.068 (3)
O35	0.3731 (8)	0.6185 (6)	0.3288 (8)	0.064 (3)
O36	0.3382 (8)	0.4047 (5)	0.8120 (8)	0.062 (2)
O37	0.5721 (11)	0.4928 (7)	0.3216 (8)	0.105 (5)
O38	0.5343 (9)	0.3274 (6)	0.8615 (9)	0.077 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0154 (3)	0.0072 (3)	0.0093 (3)	0.0005 (2)	0.0022 (2)	−0.0007 (2)
Mo2	0.0135 (3)	0.0071 (3)	0.0081 (3)	−0.0001 (2)	0.0001 (2)	−0.0001 (2)
Mo3	0.0140 (3)	0.0078 (3)	0.0091 (3)	0.0017 (2)	0.0004 (2)	0.0004 (2)
Mo4	0.0241 (5)	0.0110 (4)	0.0133 (5)	0.000	0.0100 (4)	0.000
Mo5	0.0188 (5)	0.0097 (4)	0.0158 (5)	0.000	0.0090 (4)	0.000
Mo6	0.0150 (3)	0.0058 (3)	0.0076 (3)	0.0015 (2)	0.0012 (2)	−0.0007 (2)
Mo7	0.0140 (3)	0.0093 (3)	0.0078 (3)	0.0011 (2)	−0.0002 (2)	0.0015 (2)
Co1	0.0086 (6)	0.0109 (6)	0.0119 (7)	0.000	−0.0004 (5)	0.000
Co2	0.0136 (7)	0.0067 (6)	0.0055 (6)	0.000	0.0012 (5)	0.000
Co3	0.0134 (5)	0.0103 (4)	0.0064 (4)	−0.0011 (4)	0.0002 (3)	0.0028 (3)
O1	0.029 (3)	0.013 (3)	0.021 (3)	−0.001 (2)	−0.001 (2)	0.002 (2)
O2	0.029 (3)	0.029 (3)	0.017 (3)	−0.002 (3)	0.000 (2)	0.009 (2)
O3	0.017 (3)	0.016 (2)	0.007 (2)	0.001 (2)	0.0022 (19)	0.000 (2)
O4	0.016 (3)	0.010 (2)	0.010 (2)	0.0030 (19)	0.002 (2)	0.0006 (19)
O5	0.021 (3)	0.032 (3)	0.038 (4)	−0.004 (3)	0.005 (3)	0.002 (3)
O6	0.024 (3)	0.010 (2)	0.018 (3)	0.000 (2)	−0.002 (2)	−0.006 (2)
O7	0.018 (3)	0.009 (2)	0.012 (3)	0.003 (2)	−0.002 (2)	0.000 (2)
O8	0.016 (3)	0.011 (2)	0.009 (2)	0.002 (2)	0.0020 (19)	−0.0004 (19)
O9	0.016 (4)	0.010 (3)	0.011 (4)	0.000	0.004 (3)	0.000
O10	0.019 (3)	0.009 (2)	0.013 (3)	0.002 (2)	0.005 (2)	−0.004 (2)
O11	0.017 (3)	0.010 (2)	0.007 (2)	−0.0004 (19)	0.0024 (19)	0.0007 (19)
O12	0.014 (3)	0.012 (2)	0.016 (3)	0.004 (2)	0.005 (2)	−0.002 (2)
O13	0.009 (3)	0.012 (3)	0.017 (4)	0.000	−0.003 (3)	0.000
O14	0.015 (3)	0.014 (2)	0.014 (3)	0.004 (2)	0.002 (2)	−0.004 (2)
O15	0.019 (3)	0.012 (2)	0.009 (2)	0.000 (2)	0.003 (2)	0.004 (2)
O16	0.019 (3)	0.020 (3)	0.016 (3)	0.006 (2)	−0.004 (2)	0.004 (2)
O17	0.020 (4)	0.015 (4)	0.006 (3)	0.000	0.002 (3)	0.000
O18	0.015 (4)	0.011 (3)	0.010 (3)	0.000	−0.001 (3)	0.000
O19	0.018 (3)	0.013 (2)	0.013 (3)	0.002 (2)	0.000 (2)	0.003 (2)
O20	0.024 (4)	0.014 (4)	0.016 (4)	0.000	0.009 (3)	0.000
O21	0.015 (3)	0.022 (3)	0.005 (2)	0.000 (2)	−0.0009 (19)	0.004 (2)
O22	0.018 (4)	0.006 (3)	0.007 (3)	0.000	0.002 (3)	0.000
O23	0.018 (4)	0.010 (3)	0.013 (4)	0.000	−0.001 (3)	0.000
O24	0.036 (3)	0.019 (3)	0.009 (3)	0.006 (2)	0.006 (2)	0.002 (2)
O25	0.025 (5)	0.043 (5)	0.012 (4)	0.000	0.000 (3)	0.000
O26	0.027 (3)	0.014 (3)	0.017 (3)	0.002 (2)	0.009 (2)	0.001 (2)
O27	0.017 (3)	0.024 (3)	0.051 (4)	0.005 (2)	−0.003 (3)	−0.011 (3)
O28	0.016 (4)	0.090 (9)	0.019 (5)	0.000	−0.002 (4)	0.000
O29	0.023 (3)	0.016 (3)	0.024 (3)	0.005 (2)	0.000 (2)	0.000 (2)
O30	0.020 (4)	0.017 (4)	0.021 (4)	0.000	0.011 (3)	0.000
O31	0.018 (3)	0.019 (3)	0.022 (3)	−0.003 (2)	−0.003 (2)	−0.001 (2)
O32	0.30 (3)	0.097 (13)	0.013 (6)	0.000	−0.003 (11)	0.000
O33	0.026 (6)	0.075 (9)	0.126 (13)	0.000	−0.009 (7)	0.000
O34	0.073 (6)	0.048 (5)	0.089 (7)	−0.001 (5)	0.035 (5)	0.007 (5)
O35	0.057 (6)	0.074 (6)	0.062 (6)	−0.012 (5)	−0.002 (5)	−0.004 (5)
O36	0.076 (6)	0.044 (5)	0.068 (6)	−0.018 (4)	0.011 (5)	−0.006 (4)
O37	0.146 (11)	0.126 (11)	0.041 (6)	−0.073 (9)	−0.015 (6)	0.003 (6)
O38	0.088 (7)	0.068 (6)	0.078 (7)	−0.016 (6)	0.033 (6)	−0.003 (5)

Geometric parameters (Å, º)

Mo1—O26	1.697 (5)	Mo6—O8	1.937 (5)
Mo1—O13	1.953 (5)	Mo6—O4	1.951 (5)
Mo1—O9	1.953 (5)	Mo6—O11	2.088 (5)
Mo1—O11	2.095 (5)	Mo6—O10	2.123 (5)
Mo1—O12	2.126 (5)	Mo6—O7	2.132 (5)
Mo1—O10	2.152 (5)	Mo7—O16	1.687 (5)
Mo1—Mo1^i	2.5826 (14)	Mo7—O15	1.945 (5)
Mo2—O31	1.682 (5)	Mo7—O14	1.947 (5)
Mo2—O4	1.949 (5)	Mo7—O19	2.049 (5)
Mo2—O8	1.952 (5)	Mo7—O17	2.117 (4)
Mo2—O3	2.047 (5)	Mo7—O18	2.220 (4)
Mo2—O23	2.111 (4)	Co1—O13	2.029 (7)
Mo2—O22	2.225 (4)	Co1—O14^i	2.034 (5)
Mo2—Mo6	2.5849 (10)	Co1—O14	2.034 (5)
Mo3—O29	1.692 (5)	Co1—O28	2.045 (9)
Mo3—O14	1.951 (5)	Co1—O27^i	2.069 (6)
Mo3—O15	1.957 (5)	Co1—O27	2.069 (6)
Mo3—O12	2.110 (5)	Co2—O9	2.015 (7)
Mo3—O7	2.127 (5)	Co2—O25	2.027 (9)
Mo3—O11	2.152 (5)	Co2—O8^i	2.039 (5)
Mo3—Mo7	2.5917 (10)	Co2—O8	2.039 (5)
Mo4—O20	1.692 (7)	Co2—O24	2.082 (5)
Mo4—O19	1.918 (5)	Co2—O24^i	2.082 (5)
Mo4—O19^i	1.918 (5)	Co3—O4	2.023 (5)
Mo4—O21	1.973 (5)	Co3—O15	2.037 (5)
Mo4—O21^i	1.973 (5)	Co3—O5	2.042 (6)
Mo4—O18	2.326 (7)	Co3—O21	2.072 (5)
Mo4—Mo5	2.9284 (15)	Co3—O2	2.073 (6)
Mo5—O30	1.678 (7)	Co3—O1	2.118 (6)
Mo5—O3^i	1.921 (5)	O9—Mo1^i	1.953 (5)
Mo5—O3	1.921 (5)	O13—Mo1^i	1.953 (5)
Mo5—O21	1.969 (5)	O17—Mo7^i	2.117 (4)
Mo5—O21^i	1.969 (5)	O18—Mo7^i	2.220 (4)
Mo5—O22	2.303 (7)	O22—Mo2^i	2.225 (4)
Mo6—O6	1.703 (5)	O23—Mo2^i	2.111 (4)
O26—Mo1—O13	104.9 (3)	O6—Mo6—O7	89.2 (2)
O26—Mo1—O9	104.3 (3)	O8—Mo6—O7	165.4 (2)
O13—Mo1—O9	95.3 (2)	O4—Mo6—O7	87.4 (2)
O26—Mo1—O11	156.0 (2)	O11—Mo6—O7	74.44 (19)
O13—Mo1—O11	91.9 (3)	O10—Mo6—O7	88.7 (2)
O9—Mo1—O11	90.7 (2)	O6—Mo6—Mo2	98.58 (19)
O26—Mo1—O12	89.7 (2)	O8—Mo6—Mo2	48.59 (15)
O13—Mo1—O12	84.8 (2)	O4—Mo6—Mo2	48.44 (14)
O9—Mo1—O12	165.4 (2)	O11—Mo6—Mo2	103.91 (14)
O11—Mo1—O12	74.69 (19)	O10—Mo6—Mo2	134.52 (14)
O26—Mo1—O10	88.0 (2)	O7—Mo6—Mo2	135.76 (14)
O13—Mo1—O10	166.2 (3)	O16—Mo7—O15	107.8 (2)
O9—Mo1—O10	85.8 (2)	O16—Mo7—O14	105.5 (2)
O11—Mo1—O10	74.31 (19)	O15—Mo7—O14	93.9 (2)
O12—Mo1—O10	90.7 (2)	O16—Mo7—O19	96.8 (2)
O26—Mo1—Mo1^i	100.97 (18)	O15—Mo7—O19	86.0 (2)
O13—Mo1—Mo1^i	48.61 (14)	O14—Mo7—O19	156.5 (2)
O9—Mo1—Mo1^i	48.62 (14)	O16—Mo7—O17	92.8 (2)
O11—Mo1—Mo1^i	102.96 (13)	O15—Mo7—O17	158.7 (2)
O12—Mo1—Mo1^i	133.38 (14)	O14—Mo7—O17	85.3 (2)
O10—Mo1—Mo1^i	134.44 (14)	O19—Mo7—O17	86.4 (2)
O31—Mo2—O4	107.3 (2)	O16—Mo7—O18	162.1 (2)
O31—Mo2—O8	106.0 (2)	O15—Mo7—O18	87.3 (2)
O4—Mo2—O8	94.0 (2)	O14—Mo7—O18	82.4 (2)
O31—Mo2—O3	96.3 (2)	O19—Mo7—O18	74.2 (2)
O4—Mo2—O3	85.7 (2)	O17—Mo7—O18	71.5 (2)
O8—Mo2—O3	156.7 (2)	O16—Mo7—Mo3	101.01 (19)
O31—Mo2—O23	93.1 (3)	O15—Mo7—Mo3	48.57 (15)
O4—Mo2—O23	158.8 (2)	O14—Mo7—Mo3	48.40 (15)
O8—Mo2—O23	85.5 (2)	O19—Mo7—Mo3	134.30 (15)
O3—Mo2—O23	86.5 (2)	O17—Mo7—Mo3	133.66 (19)
O31—Mo2—O22	162.4 (3)	O18—Mo7—Mo3	96.22 (17)
O4—Mo2—O22	86.6 (2)	O13—Co1—O14^i	89.2 (2)
O8—Mo2—O22	83.0 (2)	O13—Co1—O14	89.2 (2)
O3—Mo2—O22	73.6 (2)	O14^i—Co1—O14	91.3 (3)
O23—Mo2—O22	72.3 (2)	O13—Co1—O28	176.0 (3)
O31—Mo2—Mo6	102.08 (19)	O14^i—Co1—O28	88.0 (2)
O4—Mo2—Mo6	48.53 (15)	O14—Co1—O28	88.0 (2)
O8—Mo2—Mo6	48.11 (14)	O13—Co1—O27^i	91.9 (2)
O3—Mo2—Mo6	133.92 (14)	O14^i—Co1—O27^i	87.5 (2)
O23—Mo2—Mo6	133.5 (2)	O14—Co1—O27^i	178.3 (3)
O22—Mo2—Mo6	95.15 (17)	O28—Co1—O27^i	90.8 (3)
O29—Mo3—O14	106.4 (2)	O13—Co1—O27	91.9 (2)
O29—Mo3—O15	105.7 (2)	O14^i—Co1—O27	178.3 (3)
O14—Mo3—O15	93.4 (2)	O14—Co1—O27	87.5 (2)
O29—Mo3—O12	91.6 (2)	O28—Co1—O27	90.8 (3)
O14—Mo3—O12	84.4 (2)	O27^i—Co1—O27	93.7 (4)
O15—Mo3—O12	162.5 (2)	O9—Co2—O25	176.2 (3)
O29—Mo3—O7	90.1 (2)	O9—Co2—O8^i	89.1 (2)
O14—Mo3—O7	162.7 (2)	O25—Co2—O8^i	88.2 (2)
O15—Mo3—O7	87.0 (2)	O9—Co2—O8	89.1 (2)
O12—Mo3—O7	90.1 (2)	O25—Co2—O8	88.2 (2)
O29—Mo3—O11	157.5 (2)	O8^i—Co2—O8	90.6 (3)
O14—Mo3—O11	89.5 (2)	O9—Co2—O24	90.5 (2)
O15—Mo3—O11	88.8 (2)	O25—Co2—O24	92.0 (2)
O12—Mo3—O11	73.86 (19)	O8^i—Co2—O24	178.2 (2)
O7—Mo3—O11	73.25 (19)	O8—Co2—O24	87.6 (2)
O29—Mo3—Mo7	100.1 (2)	O9—Co2—O24^i	90.5 (2)
O14—Mo3—Mo7	48.25 (15)	O25—Co2—O24^i	92.0 (2)
O15—Mo3—Mo7	48.17 (15)	O8^i—Co2—O24^i	87.6 (2)
O12—Mo3—Mo7	132.61 (14)	O8—Co2—O24^i	178.2 (2)
O7—Mo3—Mo7	135.17 (14)	O24—Co2—O24^i	94.1 (3)
O11—Mo3—Mo7	102.40 (13)	O4—Co3—O15	89.7 (2)
O20—Mo4—O19	99.3 (2)	O4—Co3—O5	92.8 (2)
O20—Mo4—O19^i	99.3 (2)	O15—Co3—O5	175.5 (2)
O19—Mo4—O19^i	93.5 (3)	O4—Co3—O21	91.23 (19)
O20—Mo4—O21	102.5 (3)	O15—Co3—O21	91.2 (2)
O19—Mo4—O21	88.5 (2)	O5—Co3—O21	92.6 (2)
O19^i—Mo4—O21	157.4 (2)	O4—Co3—O2	172.8 (2)
O20—Mo4—O21^i	102.5 (3)	O15—Co3—O2	92.4 (2)
O19—Mo4—O21^i	157.4 (2)	O5—Co3—O2	84.8 (3)
O19^i—Mo4—O21^i	88.5 (2)	O21—Co3—O2	95.7 (2)
O21—Mo4—O21^i	81.2 (3)	O4—Co3—O1	85.1 (2)
O20—Mo4—O18	170.1 (3)	O15—Co3—O1	86.7 (2)
O19—Mo4—O18	74.10 (19)	O5—Co3—O1	89.7 (2)
O19^i—Mo4—O18	74.10 (19)	O21—Co3—O1	175.7 (2)
O21—Mo4—O18	84.9 (2)	O2—Co3—O1	88.1 (2)
O21^i—Mo4—O18	84.9 (2)	Mo5—O3—Mo2	116.0 (3)
O20—Mo4—Mo5	95.0 (3)	Mo2—O4—Mo6	83.02 (19)
O19—Mo4—Mo5	130.45 (16)	Mo2—O4—Co3	136.5 (3)
O19^i—Mo4—Mo5	130.45 (16)	Mo6—O4—Co3	138.8 (3)
O21—Mo4—Mo5	41.96 (15)	Mo3—O7—Mo6	105.1 (2)
O21^i—Mo4—Mo5	41.96 (15)	Mo6—O8—Mo2	83.30 (19)
O18—Mo4—Mo5	94.87 (18)	Mo6—O8—Co2	137.8 (3)
O30—Mo5—O3^i	99.6 (2)	Mo2—O8—Co2	137.7 (3)
O30—Mo5—O3	99.6 (2)	Mo1—O9—Mo1^i	82.8 (3)
O3^i—Mo5—O3	92.3 (3)	Mo1—O9—Co2	137.93 (15)
O30—Mo5—O21	102.1 (3)	Mo1^i—O9—Co2	137.93 (15)
O3^i—Mo5—O21	157.7 (2)	Mo6—O10—Mo1	103.0 (2)
O3—Mo5—O21	89.1 (2)	Mo6—O11—Mo1	106.3 (2)
O30—Mo5—O21^i	102.1 (3)	Mo6—O11—Mo3	105.8 (2)
O3^i—Mo5—O21^i	89.1 (2)	Mo1—O11—Mo3	105.0 (2)
O3—Mo5—O21^i	157.7 (2)	Mo3—O12—Mo1	105.4 (2)
O21—Mo5—O21^i	81.5 (3)	Mo1^i—O13—Mo1	82.8 (3)
O30—Mo5—O22	170.7 (3)	Mo1^i—O13—Co1	137.58 (16)
O3^i—Mo5—O22	74.13 (19)	Mo1—O13—Co1	137.58 (16)
O3—Mo5—O22	74.13 (19)	Mo7—O14—Mo3	83.3 (2)
O21—Mo5—O22	84.9 (2)	Mo7—O14—Co1	137.1 (3)
O21^i—Mo5—O22	84.9 (2)	Mo3—O14—Co1	138.6 (3)
O30—Mo5—Mo4	94.4 (3)	Mo7—O15—Mo3	83.3 (2)
O3^i—Mo5—Mo4	131.09 (15)	Mo7—O15—Co3	136.1 (3)
O3—Mo5—Mo4	131.09 (15)	Mo3—O15—Co3	139.1 (3)
O21—Mo5—Mo4	42.09 (15)	Mo7^i—O17—Mo7	112.2 (3)
O21^i—Mo5—Mo4	42.09 (15)	Mo7^i—O18—Mo7	104.7 (3)
O22—Mo5—Mo4	94.90 (18)	Mo7^i—O18—Mo4	95.5 (2)
O6—Mo6—O8	104.3 (2)	Mo7—O18—Mo4	95.5 (2)
O6—Mo6—O4	104.4 (2)	Mo4—O19—Mo7	116.0 (2)
O8—Mo6—O4	94.4 (2)	Mo5—O21—Mo4	95.9 (2)
O6—Mo6—O11	157.5 (2)	Mo5—O21—Co3	131.6 (3)
O8—Mo6—O11	91.0 (2)	Mo4—O21—Co3	132.1 (3)
O4—Mo6—O11	90.4 (2)	Mo2^i—O22—Mo2	103.5 (3)
O6—Mo6—O10	89.5 (2)	Mo2^i—O22—Mo5	96.0 (2)
O8—Mo6—O10	86.0 (2)	Mo2—O22—Mo5	96.0 (2)
O4—Mo6—O10	165.5 (2)	Mo2^i—O23—Mo2	111.7 (3)
O11—Mo6—O10	75.06 (19)

Symmetry code: (i) x, −y+1/2, z.