A three-dimensional hybrid framework based on novel [Co₄Mo₄] bimetallic oxide clusters with 3,5-bis(3-pyridyl)-1,2,4-triazole ligands

In the title organic–inorganic hybrid complex, poly[[[μ-3,5-bis(3-pyridyl)-1,2,4-triazole]tri-μ₃-oxido-tetra-μ₂-oxido-oxidodicobalt(II)dimolybdenum(VI)] monohydrate], {[Co₂Mo₂O₈(C₁₂H₉N₅)]·H₂O}_n, the asymmetric unit is composed of two Co^II centers, two [Mo^VIO₄] tetra­hedral units, one neutral 3,5-bis(3-pyridyl)-1,2,4-triazole (BPT) ligand and one solvent water mol­ecule. The cobalt centers both exhibit octa­hedral [CoO₅N] coordination environments. Four Co^II and four Mo^VI centers are linked by μ₂-oxide and/or μ₃-oxide bridges to give an unprecedented bimetallic octa­nuclear [Co₄Mo₄O₂₂N₄] clus­ter, which can be regarded as the first example of a metal-substituted octa­molybdate and exhibits a structure differ­ent from those of the eight octa­molybdate isomers reported to date. The bimetallic oxide clusters are linked to each other through corner-sharing to give two-dimensional inorganic layers, which are further bridged by trans-BPT ligands to generate a three-dimensional organic–inorganic hybrid architecture with six-connected distorted α-Po topology.

S1. Comment

The vast compositional range, considerable structural diversity, extensive physical properties and significant applications of inorganic oxides have stimulated continuous interest in the rational design of new metal oxides (Pope & Müller, 1991). In recent years, one powerful tool for the design of novel oxide solids has been the incorporation of organic molecules to alter the inorganic microstructure or to transmit structural preferences inherent in the coordination preferences of the metal centers (Stupp & Braun, 1997). Such organic–inorganic hybrid materials combine the unique characteristics of the components to provide novel structural types, as well as new properties arising from the synergistic interplay of the two components (Sanchez et al., 2001, and references therein). Hagrman et al. (1999) successfully exploited this method in the development of the structural chemistries of the molybdenum oxides of the Mo/O/M'/ligand family (M' = Fe, Co, Ni, Cu, Zn etc.). Of this hybrid family, the most common example of a metal oxide is the octamolybdate anion [Mo₈O₂₆]^4–, for which eight isomeric forms have been reported, namely α, β, γ, δ, ε, ζ, η and θ. A comprehensive investigation of these isomers has been reported by Allis et al. (2004). However, to the best of our knowledge, no example of a transition metal-substituted octamolybdate has been obtained to date. Herein, we report the title complex, (I), in which an unprecedented bimetallic octanuclear cluster [Co₄Mo₄O₂₂N₄] is observed: this may be regarded as the first metal-substituted octamolybdate cluster and exhibits a structure different from any of the eight known isomers.

The title compound, (I), is composed of two-dimensional inorganic bimetallic layers based on unique [Mo₄Co₄] octanuclear clusters linked by 3,5-di-3-pyridyl-1,2,4-triazole (BPT) ligands to generate a three-dimensional organic–inorganic hybrid framework. As shown in Fig. 1, two independent [Mo^VIO₄] units, two Co^II cations, one neutral BPT ligand and one solvent water molecule occupy the asymmetric unit of (I). In the two [MoO₄] units, the Mo—O distances are in the range 1.699 (4)–1.818 (3) Å (Table 1). The coordination environments around Co1 and Co2 are both distorted octahedral, the six coordination sites being occupied by one N atom from a BPT ligand and five O atoms from five different [MoO₄] units. The Co—N distances are 2.129 (4) and 2.093(4 Å, and the Co–O distances range from 2.051 (3) to 2.215 (3)Å. The corresponding bond angles around metal centers are in the ranges 106.57 (18)–112.61 (15)° for O—Mo—O, 80.54 (13)–99.43 (14)° and 163.80 (14)–170.73 (13)° for O—Co—O, and 86.20 (14)–102.10 (15)° and 171.84 (16)–173.08 (15)° for N—Co—O. Moreover, the Mo—O—Co angles range from 116.56 (16) to 164.8 (2)°.

Four [MoO₄] tetrahedra and four [CoNO₅] octahedra link to each other via corner- and edge-sharing to give an octanuclear [Co₄Mo₄O₂₂N₄] motif as depicted in Fig. 2 (left). The structure can be described as a zigzag Co₄ cluster constructed from two pairs of [CoNO₅] octahedra linked through edge-sharing and capped on both faces by two [MoO₄] tetrahedra. Except for the four coordination sites occupied by the BPT N donors, two Co1 octahedra and four capping [MoO₄] tetrahedra all exhibit two terminal oxide groups. Thus, there exist 12 µ_t-O, (where µ_t–O denotes a terminal O atom), six µ₂-O and four µ₃-O atoms in this octanuclear cluster. This novel octanuclear motif can therefore be regarded as the first metal-substituted octamolybdate cluster, although it is not a discrete structure. Comparison of the basic structural characteristics (Allis et al., 2004) of the eight octamolybdate isomers reported to date indicates that the structure of [Mo₄Co₄O₂₂N₄] is unprecedented. It should be noted that although the δ-octamolybdate also consists of four octahedra and four tetrahedra, 14 µ_t-O, ten µ₂-O and two µ₃-O atoms are observed. The empirical bond valence calculation for (I) led to S values of 5.856, 5.873, 2.121 and 2.173 for Mo1, Mo2, Co1 and Co2, respectively (Brown & Altermatt, 1985). The average values for the calculated oxidation states of molybdenum and cobalt are 5.865 and 2.147, which accord well with the charge neutrality of compound (I).

As depicted in Fig. 2 (right), ten terminal oxide groups from each octanuclear cluster act as µ₂ or µ₃ bridges linking four adjacent octanuclear motifs to generate a two-dimensional inorganic layer in the ab plane. Furthermore, all the BPT organic ligands adopt the transoid configuration (Dong et al., 2005; Zhang et al., 2005; Du et al., 2008) and serve as µ₂ bridges linking adjacent two-dimensional inorganic layers into a three-dimensional organic–inorganic hybrid framework (Fig. 3). For the purpose of classifying this three-dimensional hybrid structure, we define the [Mo₄Co₄] octanuclear cluster as a single point. Thus, the two-dimensional inorganic layer can be regarded as a four-connected 4⁴-net, and each octanuclear cluster links two adjacent [Mo₄Co₄] clusters from adjacent inorganic layers through four trans-BPT ligands. Each [Mo₄Co₄] motif can therefore be considered as a six-connected node with BPT molecules as linkers. The overall topology of this three-dimensional framework can be described as a distorted α-Po net because parallel inorganic (4,4)-nets are cross-linked by zigzag chains. The internode distances are 7.001 (1) and 9.332 (4) Å in the same inorganic (4,4)-net, and 14.646 (2) Å between two neighboring nets. It should be noted that of the currently known networks of α-Po topology, the majority are twofold or threefold interpenetrated frameworks (Wang et al., 2006). However, (I) exhibits a non-interpenetrated structure owing to the existence of two-dimensional Mo—O—Co inorganic layers, in which, the metal centers are only bridged by small O atoms [what do you mean by "small O atoms"?]. This linking mode generates an extraordinarily rigid two-dimensional net, which presents insufficient space for the interpenetration despite the linkage of BPT organic ligands affording voids between adjacent inorganic layers.

Related literature

For related literature, see: Allis et al. (2004); Du et al. (2008); Hagrman et al. (1999); Pope & Müller (1991); Sanchez et al. (2001); Stupp & Braun (1997); Wang et al. (2006).

S2. Experimental

A mixture of Co(NO₃)₂.6H₂O (0.29 g, 1.0 mmol), Na₂MoO₄.2H₂O (0.12 g, 0.5 mmol), MoO₃ (0.07 g, 1.0 mmol) and 3,5-di-3-pyridyl-1,2,4-triazole (BPT) (0.22 g, 1.0 mmol) in water (10 ml) was introduced into a Parr Teflon-lined stainless steel vellel (25 ml), after which the vessel was sealed and heated at 453 K for 5 d under autogenous pressure. After the reaction had been cooled to room temperature over a period of 72 h, red crystals of (I) were produced (yield 51% based on Mo). Analysis calculated for C₁₂H₁₁Co₂Mo₂N₅O₉: C 21.23, H 1.63, N 10.31%; found: C 21.35, H 1.58, N 10.33%. IR (KBr, cm^-1): 3438 (w), 1614 (w), 1411 (w), 921 (m), 869 (m), 786 (m), 647 (s), 549 (w).

S3. Refinement

The H atoms were positioned geometrically and included in the refinement using a riding model [C—H = 0.93Å, N—H = 0.86Å and O—H = 0.85Å, and U_iso(H) = 1.2U_eq(parent atom)]. The directions of the O—H vectors were aligned with peaks initially located from difference maps. The maximum residual electron density of 1.35 e Å^-3 is located 1.22Å from atom O9W and the minimum density of -1.03 e Å^-3 lies 0.82Å from atom Mo2.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 200); software used to prepare material for publication: SHELXTL (Sheldrick, 200) and publCIF (Westrip, 2009).

Figures

	Fig. 1. The asymmetric unit in (I), shown with 30% probability displacement ellipsoids. All H atoms have been omitted for clarity. [Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y+1, z+1; (iii) x+1, y, z; (iv) -x+1, -y+2, -z+1.]
	Fig. 2. The unprecedented [Mo4Co4] octanuclear cluster (left) and a polyhedral representation of the two-dimensional inorganic layer (right) in (I).
	Fig. 3. The three-dimensional organic–inorganic hybrid framework of (I) viewed along the a-axis direction. All H atoms have been omitted for clarity.

poly[[(µ-3,5-di-3-pyridyl-1,2,4-triazole)tri-µ₃-oxido-tetra-µ₂-oxido- oxidodicobalt(II)dimolybdenum(VI)] monohydrate]

Crystal data

[Co2Mo2O8(C12N5H9)]·H2O	Z = 2
Mr = 679.00	F(000) = 656
Triclinic, P1	Dx = 2.516 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9999 (3) Å	Cell parameters from 2154 reflections
b = 9.3318 (4) Å	θ = 3.0–27.5°
c = 14.2802 (12) Å	µ = 3.25 mm^−1
α = 85.341 (11)°	T = 293 K
β = 84.805 (11)°	Block, red
γ = 75.127 (9)°	0.12 × 0.10 × 0.08 mm
V = 896.22 (9) Å^3

Data collection

Bruker SMART CCD diffractometer	4027 independent reflections
Radiation source: sealed tube	3434 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 14.6306 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
profile fitting scans	h = −7→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→11
Tmin = 0.697, Tmax = 0.781	l = −18→18
6929 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0456P)^2 + 3.1203P] where P = (Fo^2 + 2Fc^2)/3
4027 reflections	(Δ/σ)max = 0.001
271 parameters	Δρmax = 1.35 e Å^−3
0 restraints	Δρmin = −1.05 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(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
Mo1	0.33538 (6)	0.54735 (4)	0.61500 (3)	0.01356 (11)
Mo2	0.79610 (6)	0.81367 (4)	0.48598 (3)	0.01245 (11)
Co1	0.31603 (10)	0.80272 (7)	0.42622 (4)	0.01342 (15)
Co2	0.86114 (10)	0.47543 (7)	0.59389 (4)	0.01348 (15)
O1	0.2773 (6)	0.5535 (4)	0.7330 (3)	0.0270 (9)
O2	0.5847 (5)	0.4294 (4)	0.5963 (2)	0.0177 (7)
O3	0.3270 (5)	0.7300 (4)	0.5719 (2)	0.0193 (7)
O4	0.1535 (5)	0.4816 (4)	0.5605 (2)	0.0164 (7)
O5	0.7736 (5)	0.7030 (4)	0.5898 (2)	0.0169 (7)
O6	0.6030 (5)	0.8224 (4)	0.4121 (2)	0.0187 (7)
O7	0.2220 (6)	1.0088 (4)	0.4807 (3)	0.0212 (8)
O8	0.0383 (5)	0.7520 (3)	0.4253 (2)	0.0137 (7)
O9W	0.6090 (8)	0.0907 (5)	0.2937 (3)	0.0378 (11)
H1	0.6079	0.1456	0.3385	0.045*
H2	0.5831	0.0125	0.3205	0.045*
N1	0.4487 (8)	0.8027 (6)	−0.1134 (3)	0.0346 (12)
N2	0.3361 (8)	0.8969 (6)	−0.0506 (3)	0.0354 (12)
N3	0.2671 (6)	0.8975 (5)	0.2871 (3)	0.0186 (9)
N4	0.5482 (8)	0.7085 (6)	0.0243 (3)	0.0292 (11)
H4B	0.6094	0.6524	0.0687	0.035*
N5	0.8647 (7)	0.4627 (5)	−0.2593 (3)	0.0209 (9)
C1	0.4010 (9)	0.8355 (7)	0.0312 (4)	0.0265 (12)
C2	0.3077 (9)	0.9050 (6)	0.1187 (4)	0.0259 (12)
C3	0.1600 (10)	1.0338 (7)	0.1144 (4)	0.0335 (14)
H3A	0.1246	1.0804	0.0562	0.040*
C4	0.0640 (10)	1.0945 (7)	0.1955 (4)	0.0319 (14)
H4A	−0.0364	1.1818	0.1932	0.038*
C5	0.1210 (8)	1.0221 (6)	0.2809 (4)	0.0244 (11)
H5A	0.0552	1.0615	0.3362	0.029*
C6	0.3609 (8)	0.8391 (6)	0.2070 (4)	0.0216 (11)
H6A	0.4633	0.7531	0.2107	0.026*
C7	0.5741 (9)	0.6923 (7)	−0.0677 (4)	0.0283 (13)
C8	0.7180 (9)	0.5700 (6)	−0.1144 (4)	0.0258 (12)
C9	0.8370 (10)	0.4517 (7)	−0.0643 (4)	0.0328 (14)
H9A	0.8254	0.4457	0.0012	0.039*
C10	0.9712 (10)	0.3444 (7)	−0.1124 (4)	0.0349 (14)
H10A	1.0559	0.2669	−0.0799	0.042*
C11	0.9803 (9)	0.3520 (7)	−0.2098 (4)	0.0288 (12)
H11A	1.0700	0.2773	−0.2419	0.035*
C12	0.7374 (8)	0.5714 (6)	−0.2117 (4)	0.0235 (11)
H12A	0.6595	0.6506	−0.2459	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0117 (2)	0.0134 (2)	0.0158 (2)	−0.00336 (15)	−0.00141 (15)	−0.00084 (15)
Mo2	0.0115 (2)	0.0111 (2)	0.0147 (2)	−0.00289 (15)	−0.00072 (15)	−0.00083 (15)
Co1	0.0122 (3)	0.0124 (3)	0.0162 (3)	−0.0038 (2)	−0.0014 (2)	−0.0010 (2)
Co2	0.0127 (3)	0.0126 (3)	0.0157 (3)	−0.0043 (2)	−0.0005 (2)	−0.0008 (2)
O1	0.027 (2)	0.034 (2)	0.0200 (19)	−0.0086 (17)	−0.0015 (16)	0.0017 (16)
O2	0.0119 (17)	0.0136 (16)	0.0281 (19)	−0.0036 (13)	−0.0002 (14)	−0.0046 (14)
O3	0.0216 (19)	0.0182 (18)	0.0197 (17)	−0.0069 (15)	−0.0056 (15)	−0.0004 (14)
O4	0.0127 (17)	0.0175 (17)	0.0199 (17)	−0.0056 (14)	−0.0031 (13)	0.0019 (13)
O5	0.0228 (19)	0.0110 (16)	0.0163 (16)	−0.0040 (14)	0.0019 (14)	−0.0017 (13)
O6	0.0138 (17)	0.0200 (18)	0.0230 (18)	−0.0060 (14)	−0.0045 (14)	0.0041 (14)
O7	0.026 (2)	0.0125 (17)	0.0266 (19)	−0.0068 (15)	−0.0032 (16)	−0.0004 (14)
O8	0.0130 (17)	0.0102 (15)	0.0173 (16)	−0.0009 (12)	−0.0021 (13)	−0.0032 (12)
O9W	0.072 (3)	0.026 (2)	0.0185 (19)	−0.018 (2)	−0.006 (2)	−0.0007 (16)
N1	0.041 (3)	0.043 (3)	0.017 (2)	−0.003 (2)	−0.002 (2)	−0.006 (2)
N2	0.037 (3)	0.049 (3)	0.017 (2)	−0.004 (3)	0.000 (2)	−0.009 (2)
N3	0.019 (2)	0.023 (2)	0.016 (2)	−0.0081 (18)	−0.0037 (17)	−0.0016 (16)
N4	0.032 (3)	0.043 (3)	0.014 (2)	−0.012 (2)	−0.0030 (19)	0.000 (2)
N5	0.025 (2)	0.024 (2)	0.015 (2)	−0.0097 (19)	−0.0042 (17)	0.0028 (17)
C1	0.030 (3)	0.033 (3)	0.017 (2)	−0.010 (3)	−0.001 (2)	−0.001 (2)
C2	0.027 (3)	0.031 (3)	0.021 (3)	−0.009 (2)	0.000 (2)	−0.003 (2)
C3	0.045 (4)	0.036 (3)	0.018 (3)	−0.008 (3)	−0.007 (3)	0.007 (2)
C4	0.037 (4)	0.032 (3)	0.020 (3)	0.002 (3)	−0.007 (2)	0.004 (2)
C5	0.022 (3)	0.030 (3)	0.019 (2)	−0.003 (2)	−0.004 (2)	−0.002 (2)
C6	0.019 (3)	0.024 (3)	0.022 (3)	−0.006 (2)	−0.001 (2)	−0.002 (2)
C7	0.033 (3)	0.037 (3)	0.016 (2)	−0.014 (3)	0.001 (2)	−0.001 (2)
C8	0.028 (3)	0.034 (3)	0.021 (3)	−0.018 (2)	0.000 (2)	−0.002 (2)
C9	0.040 (4)	0.042 (4)	0.019 (3)	−0.016 (3)	−0.008 (3)	0.004 (2)
C10	0.038 (4)	0.035 (3)	0.029 (3)	−0.005 (3)	−0.009 (3)	0.009 (3)
C11	0.027 (3)	0.030 (3)	0.030 (3)	−0.006 (2)	−0.007 (2)	−0.001 (2)
C12	0.024 (3)	0.026 (3)	0.018 (2)	−0.004 (2)	0.003 (2)	−0.001 (2)

Geometric parameters (Å, º)

Mo1—O1	1.699 (4)	N1—N2	1.357 (7)
Mo1—O3	1.753 (3)	N2—C1	1.324 (7)
Mo1—O4	1.806 (3)	N3—C5	1.340 (7)
Mo1—O2	1.818 (3)	N3—C6	1.348 (7)
Mo2—O7^i	1.731 (3)	N4—C7	1.325 (7)
Mo2—O5	1.755 (3)	N4—C1	1.360 (8)
Mo2—O6	1.770 (3)	N4—H4B	0.8600
Mo2—O8^ii	1.808 (3)	N5—C11	1.333 (7)
Co1—O6	2.054 (4)	N5—C12	1.349 (7)
Co1—O7	2.058 (4)	N5—Co2^vi	2.093 (4)
Co1—O8	2.117 (3)	C1—C2	1.476 (8)
Co1—N3	2.129 (4)	C2—C3	1.371 (8)
Co1—O3	2.138 (3)	C2—C6	1.395 (7)
Co1—O2^iii	2.139 (3)	C3—C4	1.373 (8)
Co2—O5	2.051 (3)	C3—H3A	0.9300
Co2—O4^ii	2.073 (3)	C4—C5	1.386 (7)
Co2—O2	2.084 (3)	C4—H4A	0.9300
Co2—O8^iii	2.090 (3)	C5—H5A	0.9300
Co2—N5^iv	2.093 (4)	C6—H6A	0.9300
Co2—O4^iii	2.215 (3)	C7—C8	1.475 (8)
O2—Co1^iii	2.139 (3)	C8—C12	1.383 (7)
O4—Co2^v	2.073 (3)	C8—C9	1.390 (8)
O4—Co2^iii	2.215 (3)	C9—C10	1.367 (9)
O7—Mo2^i	1.731 (3)	C9—H9A	0.9300
O8—Mo2^v	1.808 (3)	C10—C11	1.384 (8)
O8—Co2^iii	2.090 (3)	C10—H10A	0.9300
O9W—H1	0.8501	C11—H11A	0.9300
O9W—H2	0.8500	C12—H12A	0.9300
N1—C7	1.336 (8)
O1—Mo1—O3	106.57 (18)	Mo2^v—O8—Co2^iii	116.56 (16)
O1—Mo1—O4	109.74 (17)	Mo2^v—O8—Co1	135.84 (17)
O3—Mo1—O4	109.23 (16)	Co2^iii—O8—Co1	98.76 (14)
O1—Mo1—O2	108.07 (18)	H1—O9W—H2	104.6
O3—Mo1—O2	110.44 (16)	C7—N1—N2	109.7 (5)
O4—Mo1—O2	112.61 (15)	C1—N2—N1	102.8 (5)
O7^i—Mo2—O5	106.87 (16)	C5—N3—C6	118.8 (4)
O7^i—Mo2—O6	108.22 (17)	C5—N3—Co1	115.1 (3)
O5—Mo2—O6	111.68 (16)	C6—N3—Co1	126.0 (4)
O7^i—Mo2—O8^ii	106.65 (16)	C7—N4—C1	102.9 (5)
O5—Mo2—O8^ii	111.04 (16)	C7—N4—H4B	128.5
O6—Mo2—O8^ii	112.07 (15)	C1—N4—H4B	128.5
O6—Co1—O7	90.42 (15)	C11—N5—C12	118.1 (5)
O6—Co1—O8	170.17 (13)	C11—N5—Co2^vi	124.1 (4)
O7—Co1—O8	99.09 (14)	C12—N5—Co2^vi	117.7 (4)
O6—Co1—N3	91.12 (15)	N2—C1—N4	114.3 (5)
O7—Co1—N3	91.28 (15)	N2—C1—C2	119.1 (5)
O8—Co1—N3	86.20 (15)	N4—C1—C2	126.6 (5)
O6—Co1—O3	94.13 (14)	C3—C2—C6	118.7 (5)
O7—Co1—O3	82.45 (14)	C3—C2—C1	119.9 (5)
O8—Co1—O3	89.63 (13)	C6—C2—C1	121.4 (5)
N3—Co1—O3	171.84 (16)	C2—C3—C4	120.4 (5)
O6—Co1—O2^iii	90.81 (14)	C2—C3—H3A	119.8
O7—Co1—O2^iii	166.54 (14)	C4—C3—H3A	119.8
O8—Co1—O2^iii	80.54 (13)	C3—C4—C5	118.1 (6)
N3—Co1—O2^iii	102.10 (15)	C3—C4—H4A	120.9
O3—Co1—O2^iii	84.10 (13)	C5—C4—H4A	120.9
O5—Co2—O4^ii	90.87 (14)	N3—C5—C4	122.6 (5)
O5—Co2—O2	99.43 (14)	N3—C5—H5A	118.7
O4^ii—Co2—O2	163.80 (14)	C4—C5—H5A	118.7
O5—Co2—O8^iii	170.73 (13)	N3—C6—C2	121.4 (5)
O4^ii—Co2—O8^iii	85.44 (13)	N3—C6—H6A	119.3
O2—Co2—O8^iii	82.47 (13)	C2—C6—H6A	119.3
O5—Co2—N5^iv	91.50 (15)	N4—C7—N1	110.4 (5)
O4^ii—Co2—N5^iv	98.17 (16)	N4—C7—C8	125.6 (5)
O2—Co2—N5^iv	94.06 (16)	N1—C7—C8	124.0 (5)
O8^iii—Co2—N5^iv	97.44 (15)	C12—C8—C9	118.0 (6)
O5—Co2—O4^iii	81.57 (13)	C12—C8—C7	119.6 (5)
O4^ii—Co2—O4^iii	81.94 (14)	C9—C8—C7	122.5 (5)
O2—Co2—O4^iii	87.20 (13)	C10—C9—C8	119.3 (5)
O8^iii—Co2—O4^iii	89.48 (13)	C10—C9—H9A	120.4
N5^iv—Co2—O4^iii	173.08 (15)	C8—C9—H9A	120.4
Mo1—O2—Co2	131.28 (18)	C9—C10—C11	119.5 (6)
Mo1—O2—Co1^iii	130.48 (18)	C9—C10—H10A	120.3
Co2—O2—Co1^iii	98.22 (14)	C11—C10—H10A	120.3
Mo1—O3—Co1	123.92 (18)	N5—C11—C10	122.2 (6)
Mo1—O4—Co2^v	135.70 (19)	N5—C11—H11A	118.9
Mo1—O4—Co2^iii	117.24 (16)	C10—C11—H11A	118.9
Co2^v—O4—Co2^iii	98.06 (14)	N5—C12—C8	122.8 (5)
Mo2—O5—Co2	122.36 (18)	N5—C12—H12A	118.6
Mo2—O6—Co1	137.82 (19)	C8—C12—H12A	118.6
Mo2^i—O7—Co1	164.8 (2)
O1—Mo1—O2—Co2	−84.5 (3)	O3—Co1—O8—Mo2^v	61.0 (3)
O3—Mo1—O2—Co2	31.7 (3)	O2^iii—Co1—O8—Mo2^v	145.0 (3)
O4—Mo1—O2—Co2	154.1 (2)	O6—Co1—O8—Co2^iii	29.7 (8)
O1—Mo1—O2—Co1^iii	93.5 (3)	O7—Co1—O8—Co2^iii	−165.24 (13)
O3—Mo1—O2—Co1^iii	−150.3 (2)	N3—Co1—O8—Co2^iii	104.07 (16)
O4—Mo1—O2—Co1^iii	−27.9 (3)	O3—Co1—O8—Co2^iii	−82.95 (14)
O5—Co2—O2—Mo1	−11.8 (3)	O2^iii—Co1—O8—Co2^iii	1.13 (13)
O4^ii—Co2—O2—Mo1	−140.6 (4)	C7—N1—N2—C1	−0.5 (7)
O8^iii—Co2—O2—Mo1	177.3 (3)	O6—Co1—N3—C5	−120.6 (4)
N5^iv—Co2—O2—Mo1	80.4 (3)	O7—Co1—N3—C5	−30.1 (4)
O4^iii—Co2—O2—Mo1	−92.8 (2)	O8—Co1—N3—C5	68.9 (4)
O5—Co2—O2—Co1^iii	169.68 (13)	O3—Co1—N3—C5	9.4 (13)
O4^ii—Co2—O2—Co1^iii	40.9 (5)	O2^iii—Co1—N3—C5	148.4 (4)
O8^iii—Co2—O2—Co1^iii	−1.14 (13)	O6—Co1—N3—C6	63.4 (4)
N5^iv—Co2—O2—Co1^iii	−98.12 (17)	O7—Co1—N3—C6	153.9 (4)
O4^iii—Co2—O2—Co1^iii	88.70 (14)	O8—Co1—N3—C6	−107.1 (4)
O1—Mo1—O3—Co1	−164.3 (2)	O3—Co1—N3—C6	−166.6 (9)
O4—Mo1—O3—Co1	−45.9 (3)	O2^iii—Co1—N3—C6	−27.6 (4)
O2—Mo1—O3—Co1	78.5 (2)	N1—N2—C1—N4	0.2 (7)
O6—Co1—O3—Mo1	−107.6 (2)	N1—N2—C1—C2	−178.0 (5)
O7—Co1—O3—Mo1	162.5 (2)	C7—N4—C1—N2	0.1 (7)
O8—Co1—O3—Mo1	63.3 (2)	C7—N4—C1—C2	178.2 (6)
N3—Co1—O3—Mo1	122.5 (10)	N2—C1—C2—C3	−1.9 (9)
O2^iii—Co1—O3—Mo1	−17.3 (2)	N4—C1—C2—C3	−180.0 (6)
O1—Mo1—O4—Co2^v	23.4 (3)	N2—C1—C2—C6	175.4 (6)
O3—Mo1—O4—Co2^v	−93.1 (3)	N4—C1—C2—C6	−2.6 (9)
O2—Mo1—O4—Co2^v	143.8 (2)	C6—C2—C3—C4	−1.4 (9)
O1—Mo1—O4—Co2^iii	162.29 (19)	C1—C2—C3—C4	176.1 (6)
O3—Mo1—O4—Co2^iii	45.8 (2)	C2—C3—C4—C5	0.1 (10)
O2—Mo1—O4—Co2^iii	−77.3 (2)	C6—N3—C5—C4	−0.9 (8)
O7^i—Mo2—O5—Co2	−162.4 (2)	Co1—N3—C5—C4	−177.2 (5)
O6—Mo2—O5—Co2	79.5 (2)	C3—C4—C5—N3	1.1 (9)
O8^ii—Mo2—O5—Co2	−46.4 (3)	C5—N3—C6—C2	−0.5 (8)
O4^ii—Co2—O5—Mo2	64.3 (2)	Co1—N3—C6—C2	175.3 (4)
O2—Co2—O5—Mo2	−103.2 (2)	C3—C2—C6—N3	1.7 (8)
O8^iii—Co2—O5—Mo2	−2.1 (10)	C1—C2—C6—N3	−175.7 (5)
N5^iv—Co2—O5—Mo2	162.5 (2)	C1—N4—C7—N1	−0.4 (7)
O4^iii—Co2—O5—Mo2	−17.5 (2)	C1—N4—C7—C8	−179.7 (6)
O7^i—Mo2—O6—Co1	−91.2 (3)	N2—N1—C7—N4	0.6 (7)
O5—Mo2—O6—Co1	26.1 (3)	N2—N1—C7—C8	179.9 (5)
O8^ii—Mo2—O6—Co1	151.5 (3)	N4—C7—C8—C12	−176.3 (5)
O7—Co1—O6—Mo2	74.2 (3)	N1—C7—C8—C12	4.6 (9)
O8—Co1—O6—Mo2	−120.5 (7)	N4—C7—C8—C9	3.6 (9)
N3—Co1—O6—Mo2	165.5 (3)	N1—C7—C8—C9	−175.6 (6)
O3—Co1—O6—Mo2	−8.2 (3)	C12—C8—C9—C10	1.8 (9)
O2^iii—Co1—O6—Mo2	−92.4 (3)	C7—C8—C9—C10	−178.1 (6)
O6—Co1—O7—Mo2^i	15.6 (8)	C8—C9—C10—C11	−2.8 (10)
O8—Co1—O7—Mo2^i	−161.9 (8)	C12—N5—C11—C10	1.0 (8)
N3—Co1—O7—Mo2^i	−75.5 (8)	Co2^vi—N5—C11—C10	−176.9 (4)
O3—Co1—O7—Mo2^i	109.7 (8)	C9—C10—C11—N5	1.4 (10)
O2^iii—Co1—O7—Mo2^i	110.8 (9)	C11—N5—C12—C8	−2.1 (8)
O6—Co1—O8—Mo2^v	173.6 (6)	Co2^vi—N5—C12—C8	176.0 (4)
O7—Co1—O8—Mo2^v	−21.3 (3)	C9—C8—C12—N5	0.7 (9)
N3—Co1—O8—Mo2^v	−112.0 (3)	C7—C8—C12—N5	−179.4 (5)

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