Poly[bis­{μ₂-4-[3,5-bis­(pyridin-4-yl)phen­yl]pyridine}­nona-μ₂-oxido-tetra­oxidocopper(II)tetra­molybdenum(VI)]

The title compound, [CuMo₄O₁₃(C₂₁H₁₅N₃)₂]_n, was synthesized by the reaction of ammonium molybdate, copper acetate and 4-[3,5-bis­(pyridin-4-yl)phen­yl]pyridine (DPPP) in an aqueous medium under hydro­thermal conditions. The two unique molybdenum centers and the copper center adopt MoO₄ tetra­hedral, MoO₅N octa­hedral and CuO₄N₂ octa­hedral geometries, respectively. These polyhedra are connected to each other through corner-sharing to form a two-dimensional Cu–Mo–O layer, which is further linked by the DPPP ligands to form the three-dimensional inorganic–organic hybrid framework.

S1. Comment

The exploration of metal oxide-based inorganic–organic hybrid compounds is of great interest in the fields of solid-state chemistry, not only because of various structures but also their fascinating properties and potential applications in many fields, such as catalysis, sorption, electrical conductivity, magnetism and optical materials (Cheetham, 1994; Pope et al., 1991; Li et al., 1999). Currently, molybdenum polyoxoanions have recieved much attention due to their versatile stoichiometry, different structure and high reactivity (Kong et al., 2004). By exploiting the strategy of synergistic interaction of inorganic components and organic amines, many examples of molybdenum oxide-based solid materials with one-dimensional chains, two-dimensional layers and three-dimensional framework structures have been successfully synthesized under hydrothermal conditions (Hagrman et al., 1999; Lu et al., 2002; Wu et al., 2002; Yu et al., 2009; Wang et al., 2010; Tripathi et al., 2003; Hagrman et al., 1999; Thomas et al., 2008). Among which, most examples are discrete molybdenum oxides clusters, which are modified by transition metals and organic ligands. Molybdenum oxide chains have been less reported (Chen et al., 2005, 2006; Yang, Chen et al., 2011; Yang, Lin et al., 2011).

It is well known that the Mo atom usually adopts octahedral coordination geometry in the reported molybdenum oxides clusters and chains. Comparing with the MoO₆ octahedron, the MoO₅N octahedron, which often exists in organoimido or pyridine substituted isopolymolybdate clusters, is relatively less reported (Wei et al., 2001; Peng 2004; Wu et al., 2010; Zhang et al., 2010; Meng et al., 2009). In this work, a novel molybdenum oxides compound modified by transition metal Cu and organic ligands [Cu(Mo₄O₁₃)(C₂₁N₃H₁₅)₂]_n has been synthesized. In the title compound, the MoO₄ tetrahedra and MoO₅N octahedra connect each other via sharing corners to form [Mo₃O₁₃N₂]_n chain, which are further connected by Cu^II and 4-(3,5-di(pyridin-4-yl)phenyl)pyridine (DPPP) ligand to form three-dimensional framework.

The asymmetric unit of the title compound consists of two Mo^VI atoms, six and a half O atoms, half of a Cu^II atom and one DPPP ligand (shown in Fig. 1). As shown in Fig. 2, the Mo1 atom adopts tetrahedral coordination geometry and is coordinated by one terminal O atom (O6) and three µ₂-bridging O atoms (O4, O5 and O7). The Mo2 center adopts an octahedral geometry and is coordinated by one terminal O atom (O3), four µ₂-bridging O atoms (O1, O2, O4 and O5A) and one N atom (N1) from the DPPP ligand. The average Mo—O_terminal and Mo—O_bridging bond lengths are 1.691 and 1.873 Å, respectively, which are similar to the reported values of molybdenum oxide clusters (1.685–1.702 and 1.726–1.996 Å, respectively; Han et al., 2009; Fielden et al., 2009) The Mo—N bond length of 2.447 Å is slightly shorter than similar reported values (2.426 and 2.248 Å; Wang et al., 2011; Zapf et al., 1998). Atoms Mo1 and Mo2 and symmetry-related Mo1A and Mo2A are bridged alternatively by four µ₂-bridging O atoms (O4, O5, O4A and O5A) to form an [Mo₄O₁₃N₂] tetramolybdate unit. Atom O2, which is located on an inversion center with an occupancy of 1/2, is also µ₂-bridging and coordinates with Mo2 and its symmetry-related counterpart from the other [Mo₄O₁₃N₂] tetramer unit. So, each [Mo₄O₁₃N₂] tetrameric unit links two adjacent units to form an [Mo₄O₁₃N₂]_n chain along the a axis through corner-sharing of MoO₅N octahedra.

The Cu atom is also located on the inversion center with an occupancy of 0.5 and is coordinated by two N atoms (N3B and N3E) from two DPPP ligands and four µ₂-O atoms from four [Mo₄O₁₃N₂] units, which belong to two adjacent Mo—O chains. The Cu—O1, Cu—O7 and Cu—N3 bond lengths are 2.538 (3), 1.950 (3) and 2.021 (3) Å, respectively, which suggest that the Cu center is located at the center of an elongated octahedron with atoms O1B and O1C occupying the elongated axis sites. Thus, O1 and O7 adopt µ₂-coordination modes and bridge Mo2 and Cu1, and Mo1 and Cu1, respectively. Cu1 centers act as `glue' connecting the Mo—O chains to form a two-dimensional Cu—Mo—O layer parallel to the ab plane with the [CuMo₄O₁₃N₂] unit. As shown in Fig. 3, the DPPP ligands link the two-dimensional Cu—Mo—O layers to form three-dimensional inorganic–organic hybrid network using its two N atoms.

In the [CuMo₄O₁₃N₂] unit, the four Mo centers adopt tetrahedral and octahedral geometries and are coordinated by nine µ₂-O atoms and four terminal O atoms. As far as we know, in the most reported tetramolybdate clusters and molybdenum oxide chains, Mo atoms usually adopt an octahedral or a trigonal bipyramidal geometry and are bridged by µ₃-O or µ₄-O atoms (LaDuca et al., 2000; Lu et al., 2003; Burkholder et al., 2003; Quintal et al., 2001; Chen et al., 2005, 2006; Yang, Chen et al., 2011; Yang, Lin et al., 2011). Only several tetramolybdate clusters containing MoO₄ tetrahedra have been reported, in which the Mo centers are linked by five or six µ₂-O atoms (Attanasio et al., 1986; Harada et al., 2004). Several Mo—O chains containing MoO₄ tetrahedra and MoO₆ octahedra have also been reported (Jones et al., 2010; McKee et al., 1984). So, the [Mo₄O₁₃N₂]_n chain in the title compound is a novel example containing MoO₄ tetrahedra and MoO₅N octahedra.

Bond-valence sum (BVS) analysis (Brown, 2002) using the parameters of Brese & O'Keeffe (1991) revealed slight deviations from the expected values of 6 valence units (v.u.) for the Mo atoms and 2 v.u. for the Cu and O atoms. The deviations reflect the distortions in the polyhedra: Mo1 (coordination number = 4; BVS = 6.10 v.u.), Mo2 (6; 6.13), Cu1 (6; 2.28), O1 (2; 1.71), O2 (2; 2.11), O3 (1, 1.80), O4 (2; 1.92), O5 (2; 2.09), O6 (1; 1.77) and O7 (2; 2.52).

In summary, a novel three-dimensional molybdenum oxide-based inorganic–organic hybrid compound, (I), has been synthesized. In the compound, MoO₄ tetrahedra, MoO₅N octahedra and CuO₄N₂ octahedra are connected to each other via corner-sharing to form a [CuMo₃O₁₃N₂]_n layer, which are further connected by DPPP ligands to form the three-dimensional framework.

Related literature

For related literature, see: Attanasio et al. (1986); Brese & O'Keeffe (1991); Brown (2002); Burkholder et al. (2003); Cheetham (1994); Chen et al. (2005, 2006); Fielden et al. (2009); Hagrman et al. (1999); Han et al. (2009); Harada et al. (2004); Jones et al. (2010); Kong et al. (2004); LaDuca, Desciak, Laskoski, Rarig & Zubieta (2000); Li et al. (1999); Lu et al. (2002, 2003); McKee & Wilkins (1984); Meng et al. (2009); Peng (2004); Pope & Muller (1991); Quintal et al. (2001); Thomas & Ramanan (2008); Tripathi et al. (2003); Wang et al. (2010, 2011); Wei et al. (2001); Wu et al. (2002, 2010); Yang, Chen, Lin, Chen & Huang (2011); Yang, Lin, Chen, Zhang & Huang (2011); Yu et al. (2009); Zapf et al. (1998); Zhang (2010).

S2. Experimental

A mixture of (NH₄)₆Mo₇O₂₄.4H₂O (0.2 g), Cu(OAc)₂.2H₂O (0.10 g), DPPP (0.10 g) and H₂O (10 ml) was stirred at room temperature and the pH adjusted to 3 using a H₃PO₄ solution. The mixture was the heated in a 15 ml Teflon-lined reaction vessel at 453 K for 5 d. After the mixture had been cooled at room temperature, green block-shaped crystals were isolated and washed with water.

S3. Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetry unit of the title compound, showing the atom-labelling scheme and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The structure of the two-dimensional Cu—Mo—O layer. [Symmetry codes: (i) -x+1, -y+1, -z; (ii)-x, -y+1, -z+1; (iii) -x, -y+1, -z; (iv)-x, -y+2, -z; (v) x, y+1, z-1; (vi) x, y+1, z.]
	Fig. 3. The Cu—Mo—O layers linked by DPPP ligands to form the three-dimensional network.

Poly[bis{µ₂-4-[3,5-bis(pyridin-4-yl)phenyl]pyridine}nona-µ₂-oxido- tetraoxidocopper(II)tetramolybdenum(VI)]

Crystal data

[CuMo4O13(C21H15N3)2]	Z = 1
Mr = 1274.02	F(000) = 625
Triclinic, P1	Dx = 2.103 Mg m^−3
a = 8.1756 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3263 (4) Å	Cell parameters from 3268 reflections
c = 13.8965 (8) Å	θ = 2.6–28.6°
α = 78.369 (1)°	µ = 1.81 mm^−1
β = 83.065 (2)°	T = 293 K
γ = 76.501 (1)°	Block, green
V = 1006.13 (9) Å^3	0.45 × 0.13 × 0.10 mm

Data collection

Bruker SMART diffractometer	3545 independent reflections
Radiation source: fine-focus sealed tube	3099 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
phi and ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→9
Tmin = 0.496, Tmax = 0.840	k = −10→11
6181 measured reflections	l = −13→16

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0209P)^2 + 1.7942P] where P = (Fo^2 + 2Fc^2)/3
3545 reflections	(Δ/σ)max = 0.001
301 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

Special details

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
Mo2	0.20305 (4)	0.38472 (4)	−0.04893 (2)	0.01664 (10)
Mo1	0.33602 (4)	0.67904 (4)	0.07478 (2)	0.01823 (10)
Cu1	0.0000	1.0000	0.0000	0.02298 (17)
O1	0.1353 (3)	0.2255 (3)	−0.0509 (2)	0.0282 (6)
O2	0.0000	0.5000	0.0000	0.0304 (10)
O3	0.2044 (4)	0.4709 (3)	−0.1681 (2)	0.0356 (7)
O4	0.3040 (3)	0.5490 (3)	0.0063 (2)	0.0257 (6)
O5	0.5501 (3)	0.7066 (3)	0.0583 (2)	0.0275 (6)
O6	0.2857 (4)	0.6190 (4)	0.1958 (2)	0.0413 (8)
O7	0.2045 (3)	0.8534 (3)	0.0382 (2)	0.0256 (6)
N1	0.2561 (4)	0.2517 (4)	0.1187 (2)	0.0230 (7)
N2	0.9111 (5)	−0.6487 (4)	0.4850 (3)	0.0406 (10)
N3	0.0659 (4)	−0.0251 (4)	0.8585 (2)	0.0230 (7)
C1	0.3405 (6)	0.1089 (5)	0.1263 (3)	0.0370 (11)
H1	0.3808	0.0722	0.0686	0.044*
C2	0.3708 (6)	0.0139 (5)	0.2143 (3)	0.0397 (12)
H2	0.4297	−0.0845	0.2151	0.048*
C3	0.3135 (5)	0.0647 (4)	0.3022 (3)	0.0228 (8)
C4	0.2259 (5)	0.2123 (5)	0.2942 (3)	0.0272 (9)
H4	0.1840	0.2521	0.3507	0.033*
C5	0.2007 (5)	0.3005 (5)	0.2027 (3)	0.0257 (9)
H5	0.1419	0.3993	0.1996	0.031*
C6	0.3465 (5)	−0.0361 (4)	0.3987 (3)	0.0217 (8)
C7	0.4711 (4)	−0.1617 (4)	0.3996 (3)	0.0149 (7)
H7	0.5305	−0.1834	0.3411	0.018*
C8	0.5085 (5)	−0.2554 (4)	0.4863 (3)	0.0213 (8)
C9	0.4240 (4)	−0.2248 (4)	0.5728 (2)	0.0152 (7)
H9	0.4523	−0.2892	0.6316	0.018*
C10	0.2978 (5)	−0.0998 (4)	0.5736 (3)	0.0221 (8)
C11	0.2569 (5)	−0.0043 (4)	0.4860 (3)	0.0219 (8)
H11	0.1701	0.0804	0.4855	0.026*
C12	0.8237 (5)	−0.6137 (5)	0.5673 (4)	0.0377 (11)
H12	0.8520	−0.6778	0.6263	0.045*
C13	0.6940 (5)	−0.4892 (5)	0.5719 (3)	0.0303 (10)
H13	0.6392	−0.4711	0.6323	0.036*
C14	0.6467 (5)	−0.3923 (4)	0.4860 (3)	0.0213 (8)
C15	0.7340 (5)	−0.4288 (5)	0.3990 (3)	0.0305 (10)
H15	0.7060	−0.3688	0.3386	0.037*
C16	0.8623 (5)	−0.5547 (5)	0.4032 (4)	0.0383 (11)
H16	0.9196	−0.5757	0.3439	0.046*
C17	0.0649 (5)	0.0889 (5)	0.7828 (3)	0.0294 (10)
H17	0.0155	0.1853	0.7936	0.035*
C18	0.1339 (5)	0.0702 (5)	0.6892 (3)	0.0266 (9)
H18	0.1291	0.1529	0.6386	0.032*
C19	0.2104 (5)	−0.0720 (4)	0.6707 (3)	0.0222 (8)
C20	0.2047 (6)	−0.1905 (5)	0.7489 (3)	0.0302 (10)
H20	0.2509	−0.2884	0.7398	0.036*
C21	0.1308 (5)	−0.1634 (5)	0.8397 (3)	0.0280 (9)
H21	0.1257	−0.2447	0.8903	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo2	0.01457 (16)	0.01654 (19)	0.01885 (18)	−0.00316 (13)	−0.00176 (13)	−0.00324 (13)
Mo1	0.01609 (17)	0.01690 (19)	0.02142 (19)	−0.00337 (13)	−0.00098 (13)	−0.00330 (14)
Cu1	0.0197 (3)	0.0264 (4)	0.0183 (3)	0.0029 (3)	−0.0006 (3)	−0.0032 (3)
O1	0.0264 (14)	0.0240 (16)	0.0374 (17)	−0.0079 (12)	−0.0064 (13)	−0.0081 (13)
O2	0.0155 (19)	0.033 (2)	0.045 (3)	−0.0016 (17)	−0.0005 (18)	−0.017 (2)
O3	0.0480 (18)	0.0319 (18)	0.0240 (16)	−0.0070 (14)	−0.0039 (14)	0.0003 (13)
O4	0.0232 (14)	0.0186 (15)	0.0383 (17)	−0.0049 (11)	−0.0053 (12)	−0.0099 (13)
O5	0.0153 (13)	0.0259 (16)	0.0416 (18)	−0.0007 (11)	0.0013 (12)	−0.0134 (13)
O6	0.055 (2)	0.040 (2)	0.0263 (17)	−0.0125 (16)	0.0023 (15)	0.0013 (14)
O7	0.0211 (13)	0.0227 (16)	0.0328 (16)	0.0000 (11)	−0.0067 (12)	−0.0070 (12)
N1	0.0269 (17)	0.0201 (18)	0.0214 (17)	−0.0061 (14)	−0.0024 (14)	−0.0008 (14)
N2	0.032 (2)	0.030 (2)	0.060 (3)	0.0033 (17)	−0.010 (2)	−0.016 (2)
N3	0.0213 (16)	0.025 (2)	0.0209 (17)	−0.0015 (14)	−0.0018 (14)	−0.0037 (15)
C1	0.058 (3)	0.025 (3)	0.024 (2)	0.000 (2)	0.004 (2)	−0.0083 (19)
C2	0.066 (3)	0.019 (2)	0.027 (2)	0.003 (2)	0.000 (2)	−0.0047 (19)
C3	0.025 (2)	0.020 (2)	0.023 (2)	−0.0069 (17)	0.0006 (16)	−0.0043 (17)
C4	0.030 (2)	0.026 (2)	0.021 (2)	0.0016 (18)	0.0026 (17)	−0.0057 (18)
C5	0.027 (2)	0.019 (2)	0.028 (2)	0.0003 (17)	−0.0008 (17)	−0.0035 (17)
C6	0.026 (2)	0.021 (2)	0.019 (2)	−0.0086 (17)	−0.0025 (16)	−0.0032 (16)
C7	0.0185 (18)	0.0137 (19)	0.0107 (17)	0.0000 (15)	0.0028 (14)	−0.0044 (14)
C8	0.0221 (19)	0.019 (2)	0.023 (2)	−0.0048 (16)	−0.0020 (16)	−0.0043 (16)
C9	0.0202 (18)	0.0120 (19)	0.0111 (17)	−0.0008 (15)	−0.0036 (14)	0.0010 (14)
C10	0.026 (2)	0.020 (2)	0.021 (2)	−0.0066 (17)	−0.0025 (16)	−0.0038 (16)
C11	0.024 (2)	0.018 (2)	0.022 (2)	−0.0005 (16)	−0.0011 (16)	−0.0052 (16)
C12	0.034 (2)	0.032 (3)	0.045 (3)	−0.002 (2)	−0.016 (2)	0.001 (2)
C13	0.030 (2)	0.030 (3)	0.029 (2)	−0.0018 (19)	−0.0059 (18)	−0.0038 (19)
C14	0.0228 (19)	0.020 (2)	0.022 (2)	−0.0075 (16)	−0.0015 (16)	−0.0036 (16)
C15	0.033 (2)	0.029 (3)	0.027 (2)	−0.0018 (19)	−0.0005 (19)	−0.0075 (19)
C16	0.030 (2)	0.041 (3)	0.045 (3)	0.001 (2)	0.002 (2)	−0.025 (2)
C17	0.029 (2)	0.022 (2)	0.029 (2)	0.0078 (18)	−0.0001 (18)	−0.0027 (18)
C18	0.033 (2)	0.020 (2)	0.020 (2)	0.0010 (18)	0.0014 (17)	0.0021 (17)
C19	0.025 (2)	0.021 (2)	0.021 (2)	−0.0040 (17)	−0.0033 (16)	−0.0042 (16)
C20	0.050 (3)	0.017 (2)	0.023 (2)	−0.0040 (19)	−0.0029 (19)	−0.0047 (17)
C21	0.042 (2)	0.024 (2)	0.019 (2)	−0.0113 (19)	−0.0033 (18)	0.0020 (17)

Geometric parameters (Å, º)

Mo2—O3	1.689 (3)	C4—C5	1.377 (5)
Mo2—O1	1.708 (3)	C4—H4	0.9300
Mo2—O2	1.8876 (3)	C5—H5	0.9300
Mo2—O5^i	1.999 (2)	C6—C7	1.360 (5)
Mo2—O4	2.199 (3)	C6—C11	1.387 (5)
Mo2—N1	2.445 (3)	C7—C8	1.360 (5)
Mo1—O6	1.695 (3)	C7—H7	0.9300
Mo1—O7	1.744 (3)	C8—C9	1.360 (5)
Mo1—O4	1.766 (3)	C8—C14	1.494 (5)
Mo1—O5	1.808 (3)	C9—C10	1.366 (5)
Cu1—O7	1.950 (3)	C9—H9	0.9300
Cu1—O7^ii	1.950 (3)	C10—C11	1.381 (5)
Cu1—N3^iii	2.021 (3)	C10—C19	1.490 (5)
Cu1—N3^iv	2.021 (3)	C11—H11	0.9300
Cu1—O1^v	2.538 (3)	C12—C13	1.384 (6)
O2—Mo2^v	1.8876 (3)	C12—H12	0.9300
O5—Mo2^i	1.999 (2)	C13—C14	1.381 (5)
N1—C5	1.329 (5)	C13—H13	0.9300
N1—C1	1.338 (5)	C14—C15	1.389 (5)
N2—C16	1.328 (6)	C15—C16	1.377 (6)
N2—C12	1.331 (6)	C15—H15	0.9300
N3—C17	1.336 (5)	C16—H16	0.9300
N3—C21	1.340 (5)	C17—C18	1.382 (5)
N3—Cu1^vi	2.021 (3)	C17—H17	0.9300
C1—C2	1.369 (6)	C18—C19	1.389 (5)
C1—H1	0.9300	C18—H18	0.9300
C2—C3	1.388 (5)	C19—C20	1.390 (5)
C2—H2	0.9300	C20—C21	1.377 (5)
C3—C4	1.385 (5)	C20—H20	0.9300
C3—C6	1.489 (5)	C21—H21	0.9300
O3—Mo2—O1	103.23 (14)	C3—C4—H4	119.9
O3—Mo2—O2	99.11 (10)	N1—C5—C4	123.5 (4)
O1—Mo2—O2	99.07 (9)	N1—C5—H5	118.3
O3—Mo2—O5^i	93.60 (13)	C4—C5—H5	118.3
O1—Mo2—O5^i	96.61 (12)	C7—C6—C11	120.1 (3)
O2—Mo2—O5^i	156.94 (8)	C7—C6—C3	117.7 (3)
O3—Mo2—O4	96.56 (13)	C11—C6—C3	122.3 (3)
O1—Mo2—O4	160.02 (12)	C8—C7—C6	119.9 (3)
O2—Mo2—O4	80.25 (7)	C8—C7—H7	120.1
O5^i—Mo2—O4	79.24 (10)	C6—C7—H7	120.1
O3—Mo2—N1	169.75 (13)	C7—C8—C9	120.9 (3)
O1—Mo2—N1	80.32 (12)	C7—C8—C14	119.1 (3)
O2—Mo2—N1	89.72 (7)	C9—C8—C14	120.0 (3)
O5^i—Mo2—N1	76.36 (11)	C8—C9—C10	120.2 (3)
O4—Mo2—N1	79.71 (10)	C8—C9—H9	119.9
O6—Mo1—O7	108.18 (14)	C10—C9—H9	119.9
O6—Mo1—O4	108.97 (14)	C9—C10—C11	119.6 (3)
O7—Mo1—O4	109.97 (12)	C9—C10—C19	117.7 (3)
O6—Mo1—O5	109.50 (14)	C11—C10—C19	122.7 (3)
O7—Mo1—O5	107.06 (13)	C10—C11—C6	119.4 (4)
O4—Mo1—O5	113.05 (12)	C10—C11—H11	120.3
O7—Cu1—O7^ii	180.000 (1)	C6—C11—H11	120.3
O7—Cu1—N3^iii	90.98 (12)	N2—C12—C13	125.0 (4)
O7^ii—Cu1—N3^iii	89.02 (12)	N2—C12—H12	117.5
O7—Cu1—N3^iv	89.02 (12)	C13—C12—H12	117.5
O7^ii—Cu1—N3^iv	90.98 (12)	C14—C13—C12	119.3 (4)
N3^iii—Cu1—N3^iv	180.000 (1)	C14—C13—H13	120.3
O1^v—Cu1—N3^iii	83.40 (12)	C12—C13—H13	120.3
O1^v—Cu1—O7	83.20 (11)	C13—C14—C15	116.5 (4)
O1^v—Cu1—N3^iv	96.60 (11)	C13—C14—C8	121.8 (4)
O1^v—Cu1—O7^ii	96.80 (10)	C15—C14—C8	121.6 (4)
Mo2^v—O2—Mo2	180.000 (18)	C16—C15—C14	119.2 (4)
Mo1—O4—Mo2	164.00 (15)	C16—C15—H15	120.4
Mo1—O5—Mo2^i	147.98 (16)	C14—C15—H15	120.4
Mo1—O7—Cu1	158.80 (16)	N2—C16—C15	125.4 (4)
C5—N1—C1	116.4 (3)	N2—C16—H16	117.3
C5—N1—Mo2	127.8 (3)	C15—C16—H16	117.3
C1—N1—Mo2	115.6 (3)	N3—C17—C18	123.0 (4)
C16—N2—C12	114.6 (4)	N3—C17—H17	118.5
C17—N3—C21	117.2 (3)	C18—C17—H17	118.5
C17—N3—Cu1^vi	124.0 (3)	C17—C18—C19	120.0 (4)
C21—N3—Cu1^vi	118.5 (3)	C17—C18—H18	120.0
N1—C1—C2	123.8 (4)	C19—C18—H18	120.0
N1—C1—H1	118.1	C18—C19—C20	116.5 (4)
C2—C1—H1	118.1	C18—C19—C10	123.1 (4)
C1—C2—C3	119.9 (4)	C20—C19—C10	120.4 (3)
C1—C2—H2	120.0	C21—C20—C19	120.1 (4)
C3—C2—H2	120.0	C21—C20—H20	119.9
C4—C3—C2	116.3 (4)	C19—C20—H20	119.9
C4—C3—C6	122.8 (3)	N3—C21—C20	123.0 (4)
C2—C3—C6	120.9 (4)	N3—C21—H21	118.5
C5—C4—C3	120.1 (4)	C20—C21—H21	118.5
C5—C4—H4	119.9

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