Two polyoxometallate-based supra­molecular compounds influenced by the ratio between the polyoxometallate anion and organic cation

Two polyoxometallate-based compounds, tris­[1,1'-(butane-1,4-di­yl)bis­(1H-imidazol-3-ium)] bis­[tetra­cosa-[mu]₂-oxido-do­deca­­oxido-[mu]₁₂-phosphato-dodeca­molybdenum(VI)], (C₁₀H₁₆N₄)₃[PMo₁₂O₄₀]₂, (I), and 1,1'-(butane-1,4-di­yl)bis­(1H-imid­azol-3-ium) 1-[4-(1H-imidazol-1-yl)but­yl]-1H-imidazol-3-ium tetra­cosa-[mu]₂-oxido-dodeca­oxido-[mu]₁₂-phosphato-dodeca­molyb­denum(VI) dihydrate, (C₁₀H₁₆N₄)(C₁₀H₁₅N₄)[PMo₁₂O₄₀]·2H₂O, (II), were synthesized by hydro­thermal techniques at different pH values. The stoichiometric ratio between the polyoxometallate (POM) anions and organic cations is 2:3 in (I), with one of the cations lying on an inversion centre. The doubly protonated 1,1'-(butane-1,4-di­yl)di­imidazole (BIM) cations are linked to the [PMo₁₂O₄₀]^3- anions by hydrogen bonds to form a three-dimensional supra­molecular network. The stoichiometric ratio of POM anions and organic cations is 1:2 in (II), and the anion is located about a centre of inversion. The partly protonated BIM cations and solvent water mol­ecules form hydrogen bonds with the [PMo₁₂O₄₀]^3- anions, yielding a two-dimensional supra­molecular layer. The different lattice architectures of (I) and (II) may be governed by the ratio between the POM anions and organic cations, which, in turn, is determined by the pH value.

S1. Comment

The development of new inorganic–organic hybrids has emerged as a major research area for the rational design of new materials, due to their intriguing topological structures and their widespead applications (Chae et al., 2004; Seo et al., 2000; Kahn & Martinez, 1998) as catalysts, nonlinear optical materials etc. Polyoxometalalte (POM) clusters can be viewed as transferable building blocks, offering interesting and exciting perspectives for the design of new materials. Thus, POMs are often employed as important inorganic units for constructing inorganic–organic supramolecular hybrids with various organic molecules (Ishii et al., 2004; Peng, 2004; Zhao et al., 2007; Zheng et al., 2008). Studies of supramolecular hybrids are mainly focused on the understanding of intermolecular interactions with respect to crystal packing, and the utilization of such knowledge in the design of new solids with desired physical and chemical properties (Lehn, 1990).

There are many reports on the intermolecular interactions in POM-based supramolecular hybrids. Some are focused on the recognition and development of novel supramolecular synthons (Wintijes et al., 2008; Han et al., 2009), while others explore novel lattice architectures resulting from the different nature of the organic molecules (Long et al., 2003; Yan et al., 2010; Ritchie et al., 2009; Chullikkattil et al., 2010). In our ongoing studies of POM-based supramolecules, we have found that the lattice architectures are affected not only by supramolecular synthons and the nature of the organic molecules, but also by the degree of protonation of the organic molecules. In this work, two POM-based hybrids, namely tris[1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium)] bis[tetracosa-µ₂-oxido-dodecaoxido-µ₁₂-phosphato-dodecamolybdenum(VI)], (I), and 1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium) 1-[4-(1H-imidazol-1-yl)butyl]-1H-imidazol-3-ium tetracosa-µ₂-oxido-dodecaoxido-µ₁₂-phosphato-dodecamolybdenum(VI) dihydrate, (II), were synthesized at different pH values. In these two compounds, the organic molecules are protonated to different degrees and combine with the POM anions in different stoichiometric ratios to form different lattice architectures.

X-ray single-crystal diffraction studies reveal that (I) crystallizes in the triclinic system (space group P1). The asymmetric unit of (I) (Fig. 1) consists of one [PMo₁₂O₄₀] cluster and one-and-a-half doubly protonated 1,1'-(butane-1,4-diyl)diimidazole (BIM) molecules. The [PMo₁₂O₄₀]^3- cluster shows a wellknown Keggin-type structure. It is formed by a central PO₄ tetrahedron surrounded by four Mo₃O₁₃ triplets, in which three MoO₆ octahedra share edges. One PO₄ tetrahedron and 12 MoO₆ octahedra from four Mo₃O₁₃ triplets share corners and make up the Keggin-type [PMo₁₂O₄₀] cluster. The P—O distances are in the range 1.526 (5)–1.544 (5) Å and the Mo—O distances can be grouped into three sets, viz. Mo—O_t = 1.670 (5)–1.687 (5) Å, Mo—O_b = 1.863 (5)–1.986 (5) Å and Mo—O_c = 2.409 (5)–2.456 (5) Å (c = central, b = bridging and t = terminal).

Bond-valence sum (BVS) analyses (Brown, 2002) using the parameters of Brese & O'Keeffe (1991) revealed minor deviations from the expected values of 6 valence units (v.u.) for all the Mo atoms of (I), 2 v.u. for all the O atoms and 5 v.u. for the P atom. Thus, the Keggin-type POM cluster adopts an oxidation state of -3. Because the ratio of POM to BIM is 2:3, the three imidazole rings from one and a half independent BIM molecules should all be protonated in order to maintain charge balance, i.e. the BIM molecules in (I) are doubly protonated.

It should be mentioned that the BIM cations in (I) exhibit two different conformations, one W-shaped (Fig. 2a) and the other Z-shaped (Fig. 2b). These two kinds of doubly protonated BIM cations link the POM cluster trianions to form a three-dimensional supramolecular network through N—H···O hydrogen bonds. As shown in Fig. 3(a), the protonated imidazole rings N1/N2 and N3/N4 from the W-shaped BIM cation form hydrogen bonds with two POM anions, with N1···O36ⁱ = 2.809 (10) Å and N3···O9 = 2.952 (10) Å [symmetry code: (i) x, y - 1, z + 1]. Each POM anion accepts hydrogen bonds from two W-shaped BIM cations using two bridging O atoms, to form a one-dimensional chain along the [011] direction. The N5/N6 imidazole ring from the the Z-shaped BIM cation forms trifurcated hydrogen bonds with two terminal O atoms (O2ⁱⁱ and O13) and one bridging O atom (O12ⁱⁱⁱ) from three POM anions, with N5···O2ⁱⁱ = 3.079 (9) Å, N5···O13 = 3.076 (9) Å and N5···O12ⁱⁱⁱ = 3.147 (9) Å [symmetry codes: (ii) -x + 1, -y + 1, -z + 1; (iii) x - 1, y, z]. Thus, each Z-shaped BIM cation links six POM anions through weak hydrogen bonds, and each POM anion is connected to three such BIM cations to form a two-dimensional layer parallel to the [101] plane (Fig. 3b). As shown in Fig. 3(c), the one-dimensional chain along the [011] direction and the two-dimensional layer parallel to the [101] plane cross each other, to form a three-dimensional network with POM cluster anions as the junctions. Briefly, the POM cluster anions in (I) are linked by hydrogen bonds to five doubly protonated BIM cations (two W-shaped and three Z-shaped) using their five O atoms, and the two types of BIM cations link the POM anions to form a three-dimensional supramolecular network.

Compound (II) also crystallizes in the triclinic system, space group P1. The asymmetric unit consists of half a Keggin-type [PMo₁₂O₄₀]^3- POM cluster anion, one BIM cation and one solvent water molecule (Fig. 4). In the POM anion, the central P atom is surrounded by a cube of eight half-occupied O atoms, which often appears in Keggin-type structures (Fender et al., 1998; Attanasio et al. 1990). The P—O [1.501 (13)–1.595 (14) Å] and Mo—O bond lengths [2.426 (14)–2.510 (13) Å for Mo—O_c, 1.853 (8)–1.963 (8) for Mo—O_b and 1.671 (7)–1.650 (7) Å for Mo—O_t] are similar to those of (I) and the reported Keggin-type POM (Han et al., 2009).

The BVS analysis of (II) reveals that the POM cluster also adopts an oxidation state of -3. The stoichiometric ratio between POM and BIM ions in (II) is 1:2, i.e. there are two BIM cations per anion. Thus, for charge balance, one BIM cation should be doubly protonated and the other should be singly protonated.

The BIM cations in (II) adopt an Ω conformation (Fig. 2c). As shown in Fig. 5(a), the protonated BIM cations form hydrogen bonds with the POM anions, yielding a one-dimensional supramolecular chain along the [110] direction. In the POM–BIM chain, the N2···O19ⁱ distance is 2.897 (12) Å and the N4···O9ⁱⁱ distance is 2.971 (10) Å [symmetry codes: (i) x + 1, y + 1, z; (ii) x - 1, y, z], and each POM anion accepts hydrogen bonds from four BIM cations using four bridging O atoms. The solvent water molecule also acts as a hydrogen-bond donor and is linked to two POM anions (Fig. 5b). Each POM anion, using two terminal and two bridging O atoms, is linked by hydrogen bonds to four solvent water molecules to form a one-dimensional POM–H₂O supramolecular chain along the [100] direction. The POM–H₂O and POM–BIM chains cross each other, to form a two-dimensional supramolecular layer with the POM clusters as the junctions. Briefly, for (II), POM cluster anions are linked by hydrogen bonds to four BIM cations using their eight O atoms, and to four solvent water molecules, to form a two-dimensional supramolecular layer (Fig. 5c).

In summary, two POM-based inorganic–organic hybride compounds, (I) and (II), have been synthesized. The three-dimensional supramolecular compound, (I), in which the BIM molecules are doubly protonated, was synthesized at a lower pH (pH = 1) and has a 2:3 stoichiometric ratio between POM and BIM. The two-dimensional supramolecular compound, (II), in which the BIM molecules are partially protonated, was obtained at a relatively high pH (pH = 5) and the ratio between POM and BIM is 1:2. It can thus be concluded that the degree of protonation of the organic molecules, affected by pH, defines the stoichiometric ratio between the POM anions and the BIM cations, which can further affect the lattice architecture.

Related literature

For related literature, see: Attanasio et al. (1990); Brese & O'Keeffe (1991); Brown (2002); Chae et al. (2004); Chullikkattil et al. (2010); Fender et al. (1998); Han et al. (2009); Ishii et al. (2004); Kahn & Martinez (1998); Lehn (1990); Long et al. (2003); Peng (2004); Ritchie et al. (2009); Seo et al. (2000); Sheldrick (2008); Wintijes et al. (2008); Yan et al. (2010); Zhao et al. (2007); Zheng et al. (2008).

S2. Experimental

For the snthesis of (I) and (II), mixtures of (NH₄)₆Mo₇O₂₄.4H₂O (0.2 g), Cu(OAc)₂.2H₂O (0.10 g), BIM (0.10 g) and H₂O (10 ml) were stirred at room temperature, and the pH was adjusted to 1 [for (I)] or 5 [for (II)] using H₃PO₄ solution. The mixtures were then heated in 15 ml Teflon-lined reaction vessels at 453 K for 5 d. After the mixtures had been cooled at room temperature, black block-shaped crystals of (I) and (II) were isolated and washed with water.

S3. Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms, with alkyl C—H = 0.97 Å, aryl C—H = 0.93 Å, N—H = 0.86 Å and O—H = 0.85 Å, and with U_iso(H) = 1.2U_eq(C,N, O). According to the BVS results for (II), the BIM ligands are partly protonated, and therefore the occupancy of atom H4 attached to atom N4 was fixed at 0.5. Because of the higher U_eq parameters of some atoms compared with their neighbours, the soft-restraint commands SIMU and DELU (SHELXL97; Sheldrick, 2008) were used intensively.

Computing details

For both compounds, 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 structure of the asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The conformations of the BIM cation in (I) and (II). (a) The W shape and (b) the Z shape in (I). (c) The Ω shape in (II). [Part (b) looks cropped - please send complete image]
	Fig. 3. For (I), the doubly protonated BIM ligands link the POM anions to form (a) a one-dimensional supramolecular chain along the [011] direction and (b) a two-dimensional layer parallel to the ac plane. (c) These layers and chains cross each other to form a three-dimensional supramolecular network. [Symmetry codes: (i) x, y - 1, z + 1; (ii) -x + 1, -y + 1, -z + 1; (iii) x - 1, y, z.] [There is also atom N5^iv - please provide symop]
	Fig. 4. The structure of the asymmetric unit of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 5. (a) For (II), the protonated BIM ligands link the POM anions to form a one-dimensional supramolecular chain along the [110] direction. (b) The solvent water molecules link the POM anions to form a one-dimensional supramolecular chain along the a direction. (c) These chains cross each other to form a two-dimensional supramolecular network. [Symmetry codes: (i) x - 1, y, z; (ii) x + 1, y + 1, z; (iii) -x + 1, -y + 1, -z + 1.]

(I) Tris[1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium)] bis[tetracosa-µ₂-oxido-dodecaoxido-µ₁₂-phosphato-dodecamolybdenum(VI)]

Crystal data

(C10H16N4)3[PMo12O40]2	Z = 1
Mr = 4221.30	F(000) = 1990
Triclinic, P1	Dx = 3.114 Mg m^−3
a = 11.838 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.1071 (11) Å	Cell parameters from 7806 reflections
c = 17.8029 (18) Å	θ = 1.8–25.0°
α = 74.134 (2)°	µ = 3.38 mm^−1
β = 71.044 (1)°	T = 298 K
γ = 71.872 (1)°	Block, black
V = 2250.9 (4) Å^3	0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	7806 independent reflections
Radiation source: fine-focus sealed tube	5770 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→14
Tmin = 0.552, Tmax = 0.729	k = −12→14
11740 measured reflections	l = −12→21

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) = 0.103	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 12.874P] where P = (Fo^2 + 2Fc^2)/3
7806 reflections	(Δ/σ)max = 0.001
667 parameters	Δρmax = 1.71 e Å^−3
380 restraints	Δρmin = −1.38 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
Mo1	0.99424 (7)	0.42510 (6)	0.34239 (4)	0.03161 (18)
Mo2	0.74375 (6)	0.64312 (7)	0.45053 (4)	0.03106 (18)
Mo3	1.05567 (7)	0.69686 (6)	0.35901 (4)	0.03089 (18)
Mo4	0.56804 (6)	0.65669 (6)	0.32704 (4)	0.02652 (17)
Mo5	0.62298 (6)	0.90948 (6)	0.34163 (5)	0.03151 (18)
Mo6	0.93257 (7)	0.96349 (6)	0.25275 (5)	0.03079 (18)
Mo7	1.16548 (6)	0.76336 (7)	0.15366 (4)	0.03072 (18)
Mo8	1.10781 (7)	0.48781 (6)	0.13666 (4)	0.03321 (19)
Mo9	0.82205 (6)	0.43561 (6)	0.21860 (5)	0.03061 (18)
Mo10	0.74417 (8)	0.98154 (6)	0.11731 (5)	0.0373 (2)
Mo11	0.68863 (6)	0.72772 (6)	0.10527 (4)	0.02799 (17)
Mo12	0.97741 (7)	0.77721 (7)	0.02113 (4)	0.03281 (18)
P1	0.86781 (16)	0.70541 (15)	0.23596 (10)	0.0149 (4)
O1	1.0496 (6)	0.3056 (5)	0.4063 (3)	0.0419 (15)
O2	0.7157 (5)	0.5948 (5)	0.5516 (3)	0.0409 (15)
O3	1.1316 (5)	0.6669 (5)	0.4298 (3)	0.0403 (15)
O4	0.8485 (5)	0.5011 (4)	0.4099 (3)	0.0271 (12)
O5	0.8912 (5)	0.6906 (4)	0.4230 (3)	0.0267 (12)
O6	1.0691 (5)	0.5392 (4)	0.3461 (3)	0.0286 (12)
O7	1.1179 (4)	0.3966 (4)	0.2410 (3)	0.0281 (12)
O8	0.8959 (5)	0.3584 (4)	0.3044 (3)	0.0269 (12)
O9	0.6108 (5)	0.6035 (5)	0.4286 (3)	0.0281 (12)
O10	0.6507 (5)	0.8014 (4)	0.4424 (3)	0.0278 (12)
O11	1.0046 (5)	0.8644 (5)	0.3407 (3)	0.0279 (12)
O12	1.1867 (5)	0.7076 (5)	0.2621 (3)	0.0291 (12)
O13	0.4329 (5)	0.6182 (5)	0.3540 (3)	0.0382 (14)
O14	0.5197 (5)	1.0261 (5)	0.3787 (4)	0.0406 (15)
O15	0.9345 (5)	1.0963 (5)	0.2628 (4)	0.0386 (14)
O16	1.3084 (5)	0.7744 (5)	0.1012 (3)	0.0397 (15)
O17	1.2303 (5)	0.4102 (5)	0.0776 (4)	0.0431 (16)
O18	0.7650 (5)	0.3316 (5)	0.2090 (4)	0.0376 (14)
O19	0.5142 (5)	0.8143 (4)	0.3482 (3)	0.0284 (12)
O20	0.7745 (5)	0.9451 (4)	0.3254 (3)	0.0277 (12)
O21	1.0921 (5)	0.9171 (4)	0.1821 (3)	0.0280 (12)
O22	1.1733 (4)	0.6031 (4)	0.1520 (3)	0.0275 (12)
O23	0.9823 (5)	0.4118 (4)	0.1450 (3)	0.0270 (12)
O24	0.6823 (5)	0.5198 (4)	0.2914 (3)	0.0263 (12)
O25	0.7518 (4)	0.7213 (4)	0.3077 (3)	0.0204 (11)
O26	0.9628 (4)	0.7576 (4)	0.2464 (3)	0.0214 (11)
O27	0.9224 (4)	0.5739 (4)	0.2342 (3)	0.0190 (11)
O28	0.8332 (4)	0.7691 (4)	0.1564 (3)	0.0209 (11)
O29	0.5878 (5)	0.7231 (4)	0.2138 (3)	0.0265 (12)
O30	0.6407 (5)	0.9587 (4)	0.2306 (3)	0.0290 (12)
O31	0.8572 (5)	0.9953 (4)	0.1699 (3)	0.0297 (12)
O32	1.0799 (5)	0.8073 (4)	0.0729 (3)	0.0284 (12)
O33	1.0393 (5)	0.6159 (5)	0.0595 (3)	0.0291 (12)
O34	0.7649 (4)	0.5693 (4)	0.1366 (3)	0.0249 (12)
O35	0.6516 (5)	0.9002 (5)	0.0926 (3)	0.0300 (12)
O36	0.8311 (5)	0.7477 (4)	0.0148 (3)	0.0266 (12)
O37	0.8755 (5)	0.9390 (4)	0.0286 (3)	0.0310 (13)
O38	0.6810 (6)	1.1233 (5)	0.0829 (4)	0.0503 (17)
O39	0.5914 (5)	0.7204 (5)	0.0570 (3)	0.0358 (14)
O40	1.0544 (6)	0.7971 (5)	−0.0765 (3)	0.0417 (15)
C1	0.7966 (11)	−0.1365 (10)	0.8169 (7)	0.0649 (8)
H1	0.8655	−0.1987	0.8061	0.078*
C2	0.6440 (11)	−0.0096 (10)	0.8797 (7)	0.0652 (8)
H2	0.5923	0.0311	0.9205	0.078*
C3	0.6361 (11)	0.0099 (10)	0.8046 (7)	0.0649 (8)
H3	0.5751	0.0655	0.7826	0.078*
C4	0.7471 (11)	−0.0891 (10)	0.6875 (6)	0.0650 (8)
H4A	0.8090	−0.1625	0.6801	0.078*
H4B	0.6699	−0.0995	0.6861	0.078*
C5	0.7814 (11)	0.0014 (10)	0.6233 (6)	0.0647 (8)
H5A	0.8554	0.0156	0.6272	0.078*
H5B	0.7167	0.0736	0.6289	0.078*
C6	0.8064 (11)	−0.0268 (10)	0.5353 (6)	0.0642 (8)
H6A	0.8679	−0.1010	0.5301	0.077*
H6B	0.7311	−0.0350	0.5292	0.077*
C7	0.8503 (10)	0.0701 (9)	0.4704 (7)	0.0640 (8)
H7A	0.9092	0.0946	0.4856	0.077*
H7B	0.8920	0.0405	0.4205	0.077*
C8	0.7293 (11)	0.2737 (10)	0.4762 (7)	0.0634 (8)
H8	0.7738	0.2909	0.5042	0.076*
N3	0.6394 (8)	0.3464 (8)	0.4511 (5)	0.0633 (8)
H9	0.6120	0.4191	0.4569	0.076*
C10	0.6643 (10)	0.1830 (10)	0.4169 (7)	0.0634 (8)
H10	0.6568	0.1244	0.3955	0.076*
C11	0.4566 (8)	0.5044 (8)	0.1934 (5)	0.0408 (8)
H11	0.4643	0.5821	0.1753	0.049*
C12	0.3953 (8)	0.3489 (8)	0.2687 (5)	0.0411 (8)
H12	0.3528	0.3002	0.3110	0.049*
C13	0.4806 (8)	0.3160 (8)	0.2017 (5)	0.0410 (8)
H13	0.5093	0.2403	0.1898	0.049*
C14	0.6056 (8)	0.4231 (8)	0.0738 (5)	0.0408 (8)
H14A	0.6711	0.3511	0.0732	0.049*
H14B	0.6422	0.4888	0.0642	0.049*
C15	0.5464 (8)	0.4399 (8)	0.0063 (5)	0.0403 (8)
H15A	0.5046	0.3773	0.0183	0.048*
H15B	0.6106	0.4322	−0.0437	0.048*
N1	0.7436 (8)	−0.1015 (8)	0.8841 (6)	0.0652 (8)
H1A	0.7684	−0.1329	0.9273	0.078*
N2	0.7331 (9)	−0.0660 (8)	0.7660 (6)	0.0649 (8)
C9	0.5931 (11)	0.2943 (10)	0.4142 (7)	0.0634 (8)
H3A	0.5264	0.3278	0.3918	0.076*
N4	0.7497 (9)	0.1715 (8)	0.4570 (5)	0.0634 (8)
N5	0.3835 (7)	0.4630 (6)	0.2631 (4)	0.0410 (8)
H5	0.3358	0.5041	0.2990	0.049*
N6	0.5164 (7)	0.4159 (6)	0.1545 (4)	0.0405 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0437 (4)	0.0206 (4)	0.0280 (4)	0.0012 (3)	−0.0149 (3)	−0.0046 (3)
Mo2	0.0264 (4)	0.0439 (4)	0.0179 (4)	−0.0038 (3)	−0.0045 (3)	−0.0053 (3)
Mo3	0.0341 (4)	0.0364 (4)	0.0290 (4)	−0.0130 (3)	−0.0163 (3)	−0.0021 (3)
Mo4	0.0233 (4)	0.0320 (4)	0.0263 (4)	−0.0106 (3)	−0.0008 (3)	−0.0114 (3)
Mo5	0.0286 (4)	0.0239 (4)	0.0392 (4)	−0.0023 (3)	−0.0013 (3)	−0.0155 (3)
Mo6	0.0337 (4)	0.0215 (4)	0.0431 (4)	−0.0074 (3)	−0.0125 (3)	−0.0118 (3)
Mo7	0.0237 (4)	0.0417 (4)	0.0315 (4)	−0.0134 (3)	−0.0009 (3)	−0.0159 (3)
Mo8	0.0324 (4)	0.0239 (4)	0.0336 (4)	−0.0061 (3)	0.0094 (3)	−0.0126 (3)
Mo9	0.0289 (4)	0.0218 (4)	0.0463 (5)	−0.0047 (3)	−0.0115 (3)	−0.0144 (3)
Mo10	0.0632 (5)	0.0181 (4)	0.0352 (4)	−0.0017 (3)	−0.0270 (4)	−0.0048 (3)
Mo11	0.0322 (4)	0.0337 (4)	0.0238 (4)	−0.0144 (3)	−0.0123 (3)	−0.0013 (3)
Mo12	0.0307 (4)	0.0466 (5)	0.0194 (4)	−0.0145 (3)	−0.0043 (3)	−0.0006 (3)
P1	0.0168 (9)	0.0129 (9)	0.0147 (9)	−0.0028 (7)	−0.0040 (7)	−0.0034 (7)
O1	0.059 (4)	0.025 (3)	0.035 (3)	0.008 (3)	−0.022 (3)	−0.005 (3)
O2	0.040 (4)	0.055 (4)	0.023 (3)	−0.008 (3)	−0.008 (3)	−0.004 (3)
O3	0.040 (3)	0.053 (4)	0.037 (3)	−0.012 (3)	−0.024 (3)	−0.006 (3)
O4	0.035 (3)	0.025 (3)	0.022 (3)	−0.006 (2)	−0.007 (2)	−0.006 (2)
O5	0.033 (3)	0.028 (3)	0.021 (3)	−0.006 (2)	−0.008 (2)	−0.008 (2)
O6	0.031 (3)	0.024 (3)	0.031 (3)	−0.002 (2)	−0.013 (2)	−0.005 (2)
O7	0.021 (3)	0.026 (3)	0.035 (3)	0.002 (2)	−0.007 (2)	−0.012 (2)
O8	0.036 (3)	0.018 (3)	0.026 (3)	−0.007 (2)	−0.006 (2)	−0.004 (2)
O9	0.031 (3)	0.031 (3)	0.019 (3)	−0.009 (2)	−0.002 (2)	−0.005 (2)
O10	0.028 (3)	0.029 (3)	0.025 (3)	−0.001 (2)	−0.005 (2)	−0.012 (2)
O11	0.030 (3)	0.035 (3)	0.025 (3)	−0.011 (2)	−0.008 (2)	−0.011 (2)
O12	0.026 (3)	0.033 (3)	0.031 (3)	−0.005 (2)	−0.011 (2)	−0.009 (3)
O13	0.030 (3)	0.052 (4)	0.040 (3)	−0.017 (3)	0.000 (3)	−0.022 (3)
O14	0.037 (3)	0.032 (3)	0.052 (4)	−0.002 (3)	−0.007 (3)	−0.021 (3)
O15	0.040 (3)	0.026 (3)	0.058 (4)	−0.009 (3)	−0.013 (3)	−0.018 (3)
O16	0.029 (3)	0.056 (4)	0.040 (3)	−0.019 (3)	0.001 (3)	−0.019 (3)
O17	0.036 (3)	0.037 (3)	0.047 (4)	−0.011 (3)	0.015 (3)	−0.023 (3)
O18	0.040 (3)	0.028 (3)	0.048 (4)	−0.013 (3)	−0.008 (3)	−0.011 (3)
O19	0.025 (3)	0.029 (3)	0.033 (3)	−0.004 (2)	−0.005 (2)	−0.014 (3)
O20	0.029 (3)	0.027 (3)	0.030 (3)	−0.006 (2)	−0.005 (2)	−0.015 (2)
O21	0.033 (3)	0.028 (3)	0.025 (3)	−0.012 (2)	−0.002 (2)	−0.010 (2)
O22	0.024 (3)	0.027 (3)	0.033 (3)	−0.007 (2)	−0.003 (2)	−0.012 (2)
O23	0.029 (3)	0.024 (3)	0.028 (3)	−0.005 (2)	−0.001 (2)	−0.013 (2)
O24	0.030 (3)	0.025 (3)	0.024 (3)	−0.009 (2)	−0.001 (2)	−0.009 (2)
O25	0.023 (3)	0.022 (3)	0.016 (3)	−0.003 (2)	−0.005 (2)	−0.006 (2)
O26	0.022 (3)	0.017 (3)	0.026 (3)	−0.004 (2)	−0.007 (2)	−0.006 (2)
O27	0.021 (3)	0.017 (2)	0.020 (3)	−0.007 (2)	−0.004 (2)	−0.003 (2)
O28	0.027 (3)	0.018 (3)	0.019 (3)	−0.005 (2)	−0.008 (2)	−0.004 (2)
O29	0.028 (3)	0.031 (3)	0.024 (3)	−0.005 (2)	−0.009 (2)	−0.010 (2)
O30	0.030 (3)	0.028 (3)	0.032 (3)	−0.004 (2)	−0.012 (2)	−0.009 (2)
O31	0.039 (3)	0.027 (3)	0.024 (3)	−0.009 (2)	−0.008 (2)	−0.004 (2)
O32	0.032 (3)	0.028 (3)	0.026 (3)	−0.011 (2)	−0.003 (2)	−0.008 (2)
O33	0.032 (3)	0.031 (3)	0.026 (3)	−0.010 (2)	−0.005 (2)	−0.011 (2)
O34	0.028 (3)	0.029 (3)	0.021 (3)	−0.009 (2)	−0.003 (2)	−0.009 (2)
O35	0.035 (3)	0.028 (3)	0.031 (3)	−0.003 (2)	−0.020 (3)	−0.003 (2)
O36	0.035 (3)	0.032 (3)	0.017 (3)	−0.012 (2)	−0.007 (2)	−0.006 (2)
O37	0.043 (3)	0.022 (3)	0.028 (3)	−0.009 (2)	−0.011 (3)	0.000 (2)
O38	0.081 (5)	0.025 (3)	0.045 (4)	−0.001 (3)	−0.033 (4)	−0.002 (3)
O39	0.037 (3)	0.047 (4)	0.030 (3)	−0.016 (3)	−0.014 (3)	−0.007 (3)
O40	0.048 (4)	0.050 (4)	0.025 (3)	−0.023 (3)	−0.001 (3)	−0.001 (3)
C1	0.0721 (19)	0.0580 (17)	0.0616 (17)	−0.0053 (14)	−0.0288 (15)	−0.0052 (15)
C2	0.0722 (19)	0.0583 (17)	0.0617 (17)	−0.0053 (14)	−0.0286 (15)	−0.0050 (15)
C3	0.0721 (19)	0.0581 (17)	0.0615 (17)	−0.0053 (14)	−0.0288 (15)	−0.0053 (15)
C4	0.0723 (18)	0.0580 (17)	0.0616 (17)	−0.0052 (14)	−0.0285 (15)	−0.0054 (14)
C5	0.0721 (18)	0.0577 (17)	0.0613 (17)	−0.0053 (14)	−0.0284 (15)	−0.0057 (14)
C6	0.0719 (18)	0.0574 (17)	0.0610 (17)	−0.0055 (14)	−0.0286 (15)	−0.0061 (14)
C7	0.0718 (18)	0.0573 (17)	0.0608 (17)	−0.0055 (14)	−0.0286 (15)	−0.0063 (14)
C8	0.0715 (18)	0.0570 (17)	0.0605 (17)	−0.0060 (14)	−0.0288 (15)	−0.0066 (14)
N3	0.0716 (19)	0.0567 (17)	0.0604 (17)	−0.0059 (14)	−0.0286 (15)	−0.0068 (15)
C10	0.0716 (19)	0.0569 (17)	0.0606 (17)	−0.0060 (14)	−0.0289 (15)	−0.0068 (15)
C11	0.0417 (18)	0.0452 (19)	0.0365 (18)	−0.0119 (15)	−0.0041 (15)	−0.0157 (15)
C12	0.0418 (19)	0.0454 (19)	0.0367 (18)	−0.0119 (15)	−0.0038 (15)	−0.0154 (16)
C13	0.0418 (18)	0.0453 (19)	0.0367 (18)	−0.0119 (15)	−0.0038 (15)	−0.0155 (15)
C14	0.0416 (18)	0.0452 (19)	0.0365 (18)	−0.0119 (15)	−0.0039 (15)	−0.0156 (16)
C15	0.0414 (19)	0.0451 (19)	0.0363 (18)	−0.0122 (15)	−0.0042 (15)	−0.0159 (16)
N1	0.0721 (19)	0.0584 (17)	0.0617 (17)	−0.0053 (14)	−0.0287 (15)	−0.0047 (15)
N2	0.0722 (19)	0.0580 (17)	0.0614 (17)	−0.0053 (14)	−0.0289 (15)	−0.0054 (15)
C9	0.0714 (19)	0.0570 (17)	0.0605 (17)	−0.0059 (14)	−0.0288 (15)	−0.0065 (15)
N4	0.0715 (18)	0.0569 (17)	0.0605 (17)	−0.0058 (14)	−0.0288 (15)	−0.0066 (14)
N5	0.0418 (18)	0.0454 (19)	0.0366 (18)	−0.0117 (15)	−0.0038 (15)	−0.0156 (16)
N6	0.0414 (18)	0.0451 (19)	0.0364 (18)	−0.0120 (15)	−0.0042 (15)	−0.0157 (15)

Geometric parameters (Å, º)

Mo1—O1	1.676 (5)	Mo11—O29	1.910 (5)
Mo1—O4	1.881 (5)	Mo11—O36	1.942 (5)
Mo1—O6	1.884 (5)	Mo11—O35	1.959 (5)
Mo1—O7	1.957 (5)	Mo11—O28	2.409 (5)
Mo1—O8	1.965 (5)	Mo12—O40	1.670 (5)
Mo1—O27	2.427 (5)	Mo12—O33	1.877 (5)
Mo2—O2	1.688 (5)	Mo12—O32	1.908 (5)
Mo2—O5	1.880 (5)	Mo12—O36	1.917 (5)
Mo2—O10	1.883 (5)	Mo12—O37	1.969 (5)
Mo2—O4	1.947 (5)	Mo12—O28	2.455 (5)
Mo2—O9	1.957 (5)	P1—O27	1.526 (5)
Mo2—O25	2.441 (5)	P1—O28	1.534 (5)
Mo3—O3	1.676 (5)	P1—O26	1.531 (5)
Mo3—O11	1.895 (5)	P1—O25	1.544 (5)
Mo3—O12	1.913 (5)	C1—N1	1.276 (13)
Mo3—O5	1.923 (5)	C1—N2	1.317 (13)
Mo3—O6	1.936 (5)	C1—H1	0.9300
Mo3—O26	2.426 (5)	C2—C3	1.320 (14)
Mo4—O13	1.688 (5)	C2—N1	1.354 (13)
Mo4—O24	1.898 (5)	C2—H2	0.9300
Mo4—O19	1.915 (5)	C3—N2	1.346 (13)
Mo4—O29	1.920 (5)	C3—H3	0.9300
Mo4—O9	1.922 (5)	C4—C5	1.400 (14)
Mo4—O25	2.426 (5)	C4—N2	1.447 (13)
Mo5—O14	1.684 (5)	C4—H4A	0.9700
Mo5—O30	1.863 (5)	C4—H4B	0.9700
Mo5—O20	1.888 (5)	C5—C6	1.609 (14)
Mo5—O19	1.938 (5)	C5—H5A	0.9700
Mo5—O10	1.966 (5)	C5—H5B	0.9700
Mo5—O25	2.423 (5)	C6—C7	1.493 (14)
Mo6—O15	1.673 (5)	C6—H6A	0.9700
Mo6—O31	1.857 (5)	C6—H6B	0.9700
Mo6—O21	1.910 (5)	C7—N4	1.448 (13)
Mo6—O20	1.938 (5)	C7—H7A	0.9700
Mo6—O11	1.955 (5)	C7—H7B	0.9700
Mo6—O26	2.434 (4)	C8—N3	1.272 (13)
Mo7—O16	1.673 (5)	C8—N4	1.304 (13)
Mo7—O32	1.890 (5)	C8—H8	0.9300
Mo7—O22	1.922 (5)	N3—C9	1.343 (13)
Mo7—O21	1.923 (5)	N3—H9	0.8600
Mo7—O12	1.935 (5)	C10—C9	1.346 (14)
Mo7—O26	2.440 (5)	C10—N4	1.369 (13)
Mo8—O17	1.671 (5)	C10—H10	0.9300
Mo8—O7	1.905 (5)	C11—N6	1.320 (10)
Mo8—O22	1.908 (5)	C11—N5	1.332 (10)
Mo8—O23	1.926 (5)	C11—H11	0.9300
Mo8—O33	1.930 (5)	C12—N5	1.322 (11)
Mo8—O27	2.452 (5)	C12—C13	1.352 (11)
Mo9—O18	1.671 (5)	C12—H12	0.9300
Mo9—O8	1.884 (5)	C13—N6	1.371 (11)
Mo9—O23	1.910 (5)	C13—H13	0.9300
Mo9—O24	1.933 (5)	C14—N6	1.479 (10)
Mo9—O34	1.968 (5)	C14—C15	1.518 (12)
Mo9—O27	2.449 (4)	C14—H14A	0.9700
Mo10—O38	1.674 (6)	C14—H14B	0.9700
Mo10—O37	1.878 (5)	C15—C15^i	1.537 (17)
Mo10—O35	1.894 (5)	C15—H15A	0.9700
Mo10—O31	1.932 (5)	C15—H15B	0.9700
Mo10—O30	1.987 (5)	N1—H1A	0.8600
Mo10—O28	2.453 (5)	C9—H3A	0.9300
Mo11—O39	1.679 (5)	N5—H5	0.8600
Mo11—O34	1.863 (5)
O1—Mo1—O4	102.9 (3)	O29—Mo11—O35	88.2 (2)
O1—Mo1—O6	103.1 (3)	O36—Mo11—O35	84.5 (2)
O4—Mo1—O6	88.2 (2)	O39—Mo11—O28	169.8 (2)
O1—Mo1—O7	99.8 (3)	O34—Mo11—O28	85.04 (19)
O4—Mo1—O7	157.2 (2)	O29—Mo11—O28	84.46 (19)
O6—Mo1—O7	89.1 (2)	O36—Mo11—O28	72.91 (18)
O1—Mo1—O8	99.8 (3)	O35—Mo11—O28	73.16 (18)
O4—Mo1—O8	89.3 (2)	O40—Mo12—O33	103.4 (3)
O6—Mo1—O8	156.9 (2)	O40—Mo12—O32	103.4 (3)
O7—Mo1—O8	84.4 (2)	O33—Mo12—O32	86.6 (2)
O1—Mo1—O27	169.9 (2)	O40—Mo12—O36	100.7 (3)
O4—Mo1—O27	84.27 (19)	O33—Mo12—O36	91.5 (2)
O6—Mo1—O27	84.09 (19)	O32—Mo12—O36	155.6 (2)
O7—Mo1—O27	72.92 (18)	O40—Mo12—O37	100.4 (3)
O8—Mo1—O27	72.85 (18)	O33—Mo12—O37	156.2 (2)
O2—Mo2—O5	103.5 (3)	O32—Mo12—O37	87.3 (2)
O2—Mo2—O10	102.3 (3)	O36—Mo12—O37	84.7 (2)
O5—Mo2—O10	91.5 (2)	O40—Mo12—O28	170.1 (2)
O2—Mo2—O4	102.0 (3)	O33—Mo12—O28	83.92 (19)
O5—Mo2—O4	84.9 (2)	O32—Mo12—O28	83.44 (19)
O10—Mo2—O4	155.6 (2)	O36—Mo12—O28	72.19 (18)
O2—Mo2—O9	100.7 (2)	O37—Mo12—O28	72.52 (19)
O5—Mo2—O9	155.3 (2)	O27—P1—O28	109.3 (3)
O10—Mo2—O9	88.0 (2)	O27—P1—O26	109.4 (3)
O4—Mo2—O9	85.4 (2)	O28—P1—O26	109.8 (3)
O2—Mo2—O25	171.7 (2)	O27—P1—O25	109.6 (3)
O5—Mo2—O25	83.68 (19)	O28—P1—O25	109.6 (3)
O10—Mo2—O25	72.95 (18)	O26—P1—O25	109.1 (3)
O4—Mo2—O25	82.65 (18)	Mo1—O4—Mo2	150.0 (3)
O9—Mo2—O25	72.55 (18)	Mo2—O5—Mo3	153.9 (3)
O3—Mo3—O11	102.1 (3)	Mo1—O6—Mo3	149.8 (3)
O3—Mo3—O12	101.1 (3)	Mo8—O7—Mo1	124.8 (3)
O11—Mo3—O12	89.2 (2)	Mo9—O8—Mo1	124.8 (3)
O3—Mo3—O5	102.4 (3)	Mo4—O9—Mo2	124.1 (3)
O11—Mo3—O5	89.1 (2)	Mo2—O10—Mo5	125.5 (3)
O12—Mo3—O5	156.2 (2)	Mo3—O11—Mo6	124.9 (2)
O3—Mo3—O6	101.4 (3)	Mo3—O12—Mo7	125.0 (3)
O11—Mo3—O6	156.4 (2)	Mo4—O19—Mo5	124.6 (3)
O12—Mo3—O6	87.4 (2)	Mo5—O20—Mo6	148.0 (3)
O5—Mo3—O6	84.8 (2)	Mo6—O21—Mo7	125.4 (3)
O3—Mo3—O26	172.5 (2)	Mo8—O22—Mo7	151.7 (3)
O11—Mo3—O26	73.43 (18)	Mo9—O23—Mo8	125.1 (2)
O12—Mo3—O26	73.14 (19)	Mo4—O24—Mo9	154.9 (3)
O5—Mo3—O26	83.69 (19)	P1—O25—Mo5	125.3 (3)
O6—Mo3—O26	83.29 (19)	P1—O25—Mo4	125.4 (3)
O13—Mo4—O24	102.0 (2)	Mo5—O25—Mo4	89.42 (16)
O13—Mo4—O19	101.4 (2)	P1—O25—Mo2	126.2 (3)
O24—Mo4—O19	156.6 (2)	Mo5—O25—Mo2	89.45 (15)
O13—Mo4—O29	102.6 (3)	Mo4—O25—Mo2	89.54 (16)
O24—Mo4—O29	85.0 (2)	P1—O26—Mo3	126.5 (3)
O19—Mo4—O29	88.7 (2)	P1—O26—Mo6	125.5 (3)
O13—Mo4—O9	100.1 (3)	Mo3—O26—Mo6	89.20 (15)
O24—Mo4—O9	89.1 (2)	P1—O26—Mo7	125.9 (3)
O19—Mo4—O9	88.1 (2)	Mo3—O26—Mo7	89.11 (16)
O29—Mo4—O9	157.3 (2)	Mo6—O26—Mo7	88.68 (15)
O13—Mo4—O25	171.4 (2)	P1—O27—Mo1	125.4 (3)
O24—Mo4—O25	83.84 (19)	P1—O27—Mo9	127.0 (3)
O19—Mo4—O25	73.11 (18)	Mo1—O27—Mo9	88.76 (15)
O29—Mo4—O25	84.14 (19)	P1—O27—Mo8	126.3 (3)
O9—Mo4—O25	73.43 (19)	Mo1—O27—Mo8	89.09 (15)
O14—Mo5—O30	102.5 (3)	Mo9—O27—Mo8	88.01 (15)
O14—Mo5—O20	102.4 (2)	P1—O28—Mo11	125.9 (3)
O30—Mo5—O20	88.2 (2)	P1—O28—Mo10	126.8 (3)
O14—Mo5—O19	100.4 (2)	Mo11—O28—Mo10	89.07 (16)
O30—Mo5—O19	90.4 (2)	P1—O28—Mo12	125.2 (3)
O20—Mo5—O19	156.9 (2)	Mo11—O28—Mo12	89.58 (15)
O14—Mo5—O10	100.6 (3)	Mo10—O28—Mo12	88.20 (15)
O30—Mo5—O10	156.9 (2)	Mo11—O29—Mo4	148.8 (3)
O20—Mo5—O10	87.7 (2)	Mo5—O30—Mo10	151.5 (3)
O19—Mo5—O10	84.6 (2)	Mo6—O31—Mo10	156.0 (3)
O14—Mo5—O25	170.2 (2)	Mo7—O32—Mo12	151.0 (3)
O30—Mo5—O25	84.88 (19)	Mo12—O33—Mo8	151.9 (3)
O20—Mo5—O25	84.07 (19)	Mo11—O34—Mo9	151.1 (3)
O19—Mo5—O25	72.83 (18)	Mo10—O35—Mo11	124.5 (3)
O10—Mo5—O25	72.09 (18)	Mo12—O36—Mo11	125.3 (2)
O15—Mo6—O31	104.9 (3)	Mo10—O37—Mo12	125.2 (3)
O15—Mo6—O21	101.3 (2)	N1—C1—N2	105.5 (10)
O31—Mo6—O21	91.8 (2)	N1—C1—H1	127.2
O15—Mo6—O20	101.5 (2)	N2—C1—H1	127.2
O31—Mo6—O20	85.8 (2)	C3—C2—N1	104.9 (11)
O21—Mo6—O20	156.9 (2)	C3—C2—H2	127.5
O15—Mo6—O11	99.2 (3)	N1—C2—H2	127.5
O31—Mo6—O11	155.7 (2)	C2—C3—N2	107.0 (11)
O21—Mo6—O11	86.2 (2)	C2—C3—H3	126.5
O20—Mo6—O11	86.6 (2)	N2—C3—H3	126.5
O15—Mo6—O26	169.8 (2)	C5—C4—N2	113.3 (10)
O31—Mo6—O26	83.96 (19)	C5—C4—H4A	108.9
O21—Mo6—O26	73.11 (18)	N2—C4—H4A	108.9
O20—Mo6—O26	83.81 (18)	C5—C4—H4B	108.9
O11—Mo6—O26	72.31 (18)	N2—C4—H4B	108.9
O16—Mo7—O32	103.4 (3)	H4A—C4—H4B	107.7
O16—Mo7—O22	101.5 (2)	C4—C5—C6	113.9 (10)
O32—Mo7—O22	85.8 (2)	C4—C5—H5A	108.8
O16—Mo7—O21	102.0 (2)	C6—C5—H5A	108.8
O32—Mo7—O21	90.1 (2)	C4—C5—H5B	108.8
O22—Mo7—O21	156.5 (2)	C6—C5—H5B	108.8
O16—Mo7—O12	100.5 (3)	H5A—C5—H5B	107.7
O32—Mo7—O12	156.1 (2)	C7—C6—C5	110.6 (9)
O22—Mo7—O12	87.8 (2)	C7—C6—H6A	109.5
O21—Mo7—O12	86.7 (2)	C5—C6—H6A	109.5
O16—Mo7—O26	171.2 (2)	C7—C6—H6B	109.5
O32—Mo7—O26	83.93 (19)	C5—C6—H6B	109.5
O22—Mo7—O26	83.80 (18)	H6A—C6—H6B	108.1
O21—Mo7—O26	72.76 (18)	N4—C7—C6	111.8 (10)
O12—Mo7—O26	72.47 (19)	N4—C7—H7A	109.2
O17—Mo8—O7	100.9 (3)	C6—C7—H7A	109.2
O17—Mo8—O22	102.3 (2)	N4—C7—H7B	109.2
O7—Mo8—O22	90.8 (2)	C6—C7—H7B	109.2
O17—Mo8—O23	101.2 (2)	H7A—C7—H7B	107.9
O7—Mo8—O23	87.1 (2)	N3—C8—N4	109.9 (11)
O22—Mo8—O23	156.4 (2)	N3—C8—H8	125.0
O17—Mo8—O33	102.8 (3)	N4—C8—H8	125.0
O7—Mo8—O33	156.3 (2)	C8—N3—C9	110.8 (10)
O22—Mo8—O33	84.5 (2)	C8—N3—H9	124.6
O23—Mo8—O33	88.1 (2)	C9—N3—H9	124.6
O17—Mo8—O27	171.7 (2)	C9—C10—N4	107.7 (11)
O7—Mo8—O27	73.15 (18)	C9—C10—H10	126.2
O22—Mo8—O27	83.78 (18)	N4—C10—H10	126.2
O23—Mo8—O27	73.15 (17)	N6—C11—N5	108.1 (8)
O33—Mo8—O27	83.28 (19)	N6—C11—H11	126.0
O18—Mo9—O8	102.6 (3)	N5—C11—H11	126.0
O18—Mo9—O23	103.2 (2)	N5—C12—C13	107.6 (8)
O8—Mo9—O23	88.7 (2)	N5—C12—H12	126.2
O18—Mo9—O24	101.4 (2)	C13—C12—H12	126.2
O8—Mo9—O24	90.3 (2)	C12—C13—N6	106.7 (8)
O23—Mo9—O24	154.9 (2)	C12—C13—H13	126.7
O18—Mo9—O34	100.9 (2)	N6—C13—H13	126.7
O8—Mo9—O34	156.4 (2)	N6—C14—C15	112.5 (7)
O23—Mo9—O34	88.5 (2)	N6—C14—H14A	109.1
O24—Mo9—O34	82.5 (2)	C15—C14—H14A	109.1
O18—Mo9—O27	174.8 (2)	N6—C14—H14B	109.1
O8—Mo9—O27	73.58 (18)	C15—C14—H14B	109.1
O23—Mo9—O27	73.47 (18)	H14A—C14—H14B	107.8
O24—Mo9—O27	82.24 (18)	C14—C15—C15^i	113.7 (9)
O34—Mo9—O27	83.11 (18)	C14—C15—H15A	108.8
O38—Mo10—O37	103.0 (3)	C15^i—C15—H15A	108.8
O38—Mo10—O35	102.2 (3)	C14—C15—H15B	108.8
O37—Mo10—O35	89.6 (2)	C15^i—C15—H15B	108.8
O38—Mo10—O31	102.4 (3)	H15A—C15—H15B	107.7
O37—Mo10—O31	90.6 (2)	C1—N1—C2	112.4 (10)
O35—Mo10—O31	154.6 (2)	C1—N1—H1A	123.8
O38—Mo10—O30	101.0 (3)	C2—N1—H1A	123.8
O37—Mo10—O30	155.8 (2)	C1—N2—C3	110.1 (10)
O35—Mo10—O30	87.8 (2)	C1—N2—C4	123.3 (10)
O31—Mo10—O30	81.7 (2)	C3—N2—C4	124.6 (10)
O38—Mo10—O28	174.3 (2)	N3—C9—C10	105.0 (10)
O37—Mo10—O28	73.97 (19)	N3—C9—H3A	127.5
O35—Mo10—O28	73.11 (19)	C10—C9—H3A	127.5
O31—Mo10—O28	82.56 (19)	C8—N4—C10	106.7 (10)
O30—Mo10—O28	82.27 (19)	C8—N4—C7	125.4 (10)
O39—Mo11—O34	103.1 (2)	C10—N4—C7	127.7 (10)
O39—Mo11—O29	101.7 (2)	C12—N5—C11	109.6 (7)
O34—Mo11—O29	87.9 (2)	C12—N5—H5	125.2
O39—Mo11—O36	100.6 (2)	C11—N5—H5	125.2
O34—Mo11—O36	91.0 (2)	C11—N6—C13	108.0 (7)
O29—Mo11—O36	157.3 (2)	C11—N6—C14	126.2 (8)
O39—Mo11—O35	98.7 (2)	C13—N6—C14	125.8 (7)
O34—Mo11—O35	158.1 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H9···O9	0.86	2.15	2.952 (10)	156
N1—H1A···O36^ii	0.86	1.98	2.809 (10)	161
N5—H5···O2^iii	0.86	2.56	3.079 (9)	120
N5—H5···O13	0.86	2.58	3.075 (9)	118
N5—H5···O12^iv	0.86	2.60	3.147 (9)	122

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

(II) 1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium) 1-[4-(1H-imidazol-1-yl)butyl]-1H-imidazol-3-ium tetracosa-µ₂-oxido-dodecaoxido-µ₁₂-phosphato-dodecamolybdenum(VI) dihydrate

Crystal data

(C10H16N4)(C10H15N4)[PMo12O40]·2H2O	Z = 1
Mr = 2240.80	F(000) = 1065
Triclinic, P1	Dx = 2.818 Mg m^−3
a = 11.2350 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.7211 (13) Å	Cell parameters from 4586 reflections
c = 11.8459 (13) Å	θ = 1.8–25.0°
α = 102.194 (1)°	µ = 2.89 mm^−1
β = 98.184 (1)°	T = 293 K
γ = 115.998 (2)°	Block, black
V = 1320.5 (2) Å^3	0.22 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4586 independent reflections
Radiation source: fine-focus sealed tube	3425 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→13
Tmin = 0.569, Tmax = 0.596	k = −13→9
6912 measured reflections	l = −13→14

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.035P)^2 + 18.6135P] where P = (Fo^2 + 2Fc^2)/3
4586 reflections	(Δ/σ)max < 0.001
394 parameters	Δρmax = 1.63 e Å^−3
1285 restraints	Δρmin = −1.42 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	Occ. (<1)
Mo1	0.46552 (9)	0.07220 (10)	0.22452 (8)	0.0388 (2)
Mo2	0.71523 (9)	0.32873 (8)	0.48705 (8)	0.0356 (2)
Mo3	0.40031 (9)	0.14709 (9)	0.73899 (7)	0.0333 (2)
Mo4	0.14615 (8)	−0.11069 (8)	0.48237 (7)	0.0306 (2)
Mo5	0.35826 (9)	0.21212 (9)	0.45929 (8)	0.0368 (2)
Mo6	0.24643 (8)	−0.25290 (8)	0.23868 (7)	0.0318 (2)
P1	0.5000	0.0000	0.5000	0.0218 (6)
O1	0.4647 (13)	−0.0627 (13)	0.3634 (12)	0.0342 (19)	0.50
O2	0.5070 (14)	0.1126 (13)	0.4417 (12)	0.0374 (17)	0.50
O3	0.3932 (13)	0.0373 (13)	0.5303 (12)	0.0355 (18)	0.50
O4	0.3576 (13)	−0.1168 (13)	0.4540 (11)	0.033 (2)	0.50
O5	0.5665 (8)	−0.0198 (8)	0.2060 (7)	0.0555 (16)
O6	0.4464 (8)	0.1011 (7)	0.0939 (6)	0.0484 (18)
O7	0.6272 (8)	0.2259 (8)	0.3169 (7)	0.0597 (16)
O8	0.3626 (8)	0.1427 (8)	0.2992 (7)	0.0592 (16)
O9	0.8292 (8)	0.2463 (8)	0.4710 (7)	0.0505 (16)
O10	0.8160 (8)	0.4785 (7)	0.4787 (7)	0.0531 (18)
O11	0.7576 (8)	0.3532 (8)	0.6503 (7)	0.0502 (15)
O12	0.5499 (8)	0.3320 (8)	0.4903 (7)	0.0612 (16)
O13	0.5931 (8)	0.2613 (8)	0.7842 (8)	0.0566 (17)
O14	0.3834 (8)	0.2366 (7)	0.6249 (7)	0.0534 (16)
O15	0.3521 (8)	0.2140 (8)	0.8482 (7)	0.056 (2)
O16	0.2255 (8)	−0.0002 (7)	0.6413 (7)	0.0562 (17)
O17	−0.0207 (7)	−0.1652 (9)	0.4700 (7)	0.056 (2)
O18	0.1963 (8)	0.0447 (7)	0.4316 (7)	0.0531 (15)
O19	0.1346 (8)	−0.2004 (7)	0.3191 (6)	0.0436 (14)
O20	0.2916 (8)	0.3094 (7)	0.4391 (7)	0.0528 (18)
O21	0.1251 (7)	−0.3728 (7)	0.1181 (6)	0.051 (2)
O22	0.3046 (8)	−0.1015 (8)	0.1882 (7)	0.0540 (16)
O23	0.9842 (10)	0.9348 (11)	0.1883 (9)	0.090 (3)
H23A	0.9002	0.8984	0.1890	0.108*
H23B	1.0339	0.9615	0.2595	0.108*
C1	0.7503 (11)	0.5833 (12)	0.2638 (11)	0.052 (2)
H1	0.7573	0.6472	0.3300	0.063*
C2	0.8040 (12)	0.4744 (12)	0.1247 (10)	0.051 (2)
H2	0.8549	0.4509	0.0785	0.062*
C3	0.6686 (12)	0.4038 (12)	0.1119 (11)	0.055 (2)
H3	0.6078	0.3225	0.0540	0.066*
C4	0.4988 (12)	0.4339 (13)	0.2214 (11)	0.055 (2)
H4A	0.5079	0.4968	0.2944	0.066*
H4B	0.4626	0.3465	0.2326	0.066*
C5	0.3995 (12)	0.4301 (13)	0.1194 (11)	0.056 (2)
H5A	0.3882	0.3649	0.0472	0.068*
H5B	0.4380	0.5166	0.1062	0.068*
C6	0.2565 (13)	0.3947 (13)	0.1414 (12)	0.065 (3)
H6A	0.2684	0.4491	0.2206	0.077*
H6B	0.2056	0.4153	0.0831	0.077*
C7	0.1789 (12)	0.2564 (13)	0.1323 (12)	0.063 (2)
H7A	0.2256	0.2361	0.1941	0.076*
H7B	0.1702	0.2009	0.0548	0.076*
C8	−0.0801 (13)	0.1642 (14)	0.0572 (12)	0.066 (3)
H8	−0.0876	0.1364	−0.0242	0.079*
N4	−0.1276 (10)	0.2105 (11)	0.2266 (10)	0.063 (2)
H4	−0.1729	0.2167	0.2782	0.075*	0.75
C10	0.0063 (14)	0.2593 (14)	0.2506 (13)	0.068 (3)
H10	0.0680	0.3069	0.3261	0.082*
N1	0.6357 (9)	0.4733 (9)	0.1997 (8)	0.0440 (17)
N2	0.8530 (10)	0.5886 (10)	0.2195 (9)	0.054 (2)
H2A	0.9365	0.6524	0.2453	0.065*	0.75
N3	0.0391 (10)	0.2287 (11)	0.1470 (10)	0.062 (2)
C9	−0.1832 (13)	0.1480 (14)	0.1057 (12)	0.063 (3)
H9	−0.2761	0.1026	0.0653	0.076*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0353 (5)	0.0578 (6)	0.0267 (4)	0.0231 (4)	0.0091 (4)	0.0175 (4)
Mo2	0.0345 (5)	0.0276 (4)	0.0343 (5)	0.0078 (4)	0.0109 (4)	0.0050 (4)
Mo3	0.0370 (5)	0.0371 (5)	0.0310 (5)	0.0226 (4)	0.0156 (4)	0.0053 (4)
Mo4	0.0221 (4)	0.0343 (5)	0.0322 (4)	0.0139 (4)	0.0063 (3)	0.0038 (4)
Mo5	0.0384 (5)	0.0412 (5)	0.0383 (5)	0.0288 (4)	0.0075 (4)	0.0064 (4)
Mo6	0.0246 (4)	0.0309 (5)	0.0288 (4)	0.0100 (4)	0.0011 (3)	−0.0001 (3)
P1	0.0234 (13)	0.0274 (13)	0.0218 (13)	0.0172 (11)	0.0100 (11)	0.0079 (11)
O1	0.031 (3)	0.041 (3)	0.036 (3)	0.023 (3)	0.011 (3)	0.010 (3)
O2	0.037 (2)	0.042 (2)	0.037 (3)	0.024 (2)	0.011 (2)	0.010 (2)
O3	0.035 (3)	0.039 (3)	0.035 (3)	0.021 (2)	0.012 (2)	0.008 (3)
O4	0.033 (3)	0.035 (3)	0.032 (3)	0.019 (3)	0.009 (3)	0.007 (3)
O5	0.041 (3)	0.053 (3)	0.065 (3)	0.016 (2)	0.008 (3)	0.024 (3)
O6	0.048 (4)	0.052 (4)	0.038 (4)	0.018 (3)	0.010 (3)	0.018 (3)
O7	0.043 (2)	0.065 (2)	0.049 (2)	0.017 (2)	0.012 (2)	−0.004 (2)
O8	0.043 (2)	0.062 (2)	0.049 (2)	0.015 (2)	0.011 (2)	−0.004 (2)
O9	0.061 (3)	0.052 (3)	0.043 (3)	0.034 (2)	0.012 (3)	0.009 (3)
O10	0.057 (4)	0.039 (4)	0.062 (4)	0.018 (3)	0.025 (3)	0.017 (3)
O11	0.061 (3)	0.052 (3)	0.041 (3)	0.033 (2)	0.015 (2)	0.009 (2)
O12	0.044 (2)	0.066 (2)	0.048 (2)	0.016 (2)	0.013 (2)	−0.007 (2)
O13	0.042 (3)	0.054 (3)	0.068 (3)	0.018 (2)	0.009 (3)	0.023 (3)
O14	0.053 (3)	0.043 (2)	0.043 (2)	0.010 (2)	0.001 (2)	0.011 (2)
O15	0.054 (4)	0.047 (4)	0.049 (4)	0.015 (3)	0.026 (4)	−0.007 (3)
O16	0.058 (3)	0.042 (3)	0.043 (3)	0.007 (2)	−0.001 (2)	0.010 (2)
O17	0.028 (4)	0.083 (5)	0.050 (4)	0.022 (4)	0.011 (3)	0.018 (4)
O18	0.055 (2)	0.043 (2)	0.042 (2)	0.012 (2)	0.003 (2)	0.010 (2)
O19	0.050 (3)	0.044 (3)	0.038 (2)	0.027 (2)	0.013 (2)	0.006 (2)
O20	0.054 (4)	0.045 (4)	0.060 (4)	0.032 (3)	0.002 (3)	0.011 (3)
O21	0.038 (4)	0.051 (4)	0.040 (4)	0.018 (3)	−0.008 (3)	−0.012 (3)
O22	0.042 (3)	0.052 (3)	0.062 (3)	0.018 (2)	0.009 (2)	0.020 (2)
O23	0.066 (6)	0.113 (7)	0.076 (6)	0.041 (5)	0.004 (5)	0.016 (5)
C1	0.041 (4)	0.051 (4)	0.055 (4)	0.020 (3)	0.014 (3)	0.002 (3)
C2	0.043 (4)	0.053 (4)	0.050 (4)	0.020 (3)	0.017 (3)	0.003 (4)
C3	0.044 (3)	0.053 (4)	0.053 (4)	0.015 (3)	0.015 (3)	0.002 (3)
C4	0.042 (3)	0.057 (3)	0.053 (3)	0.017 (3)	0.017 (3)	0.006 (3)
C5	0.041 (3)	0.062 (4)	0.057 (4)	0.018 (3)	0.017 (3)	0.010 (3)
C6	0.046 (4)	0.069 (4)	0.064 (4)	0.019 (4)	0.017 (4)	0.011 (4)
C7	0.044 (3)	0.070 (4)	0.063 (4)	0.021 (3)	0.010 (3)	0.013 (3)
C8	0.044 (4)	0.080 (4)	0.059 (4)	0.019 (4)	0.013 (4)	0.016 (4)
N4	0.044 (4)	0.075 (4)	0.059 (4)	0.022 (4)	0.013 (3)	0.016 (4)
C10	0.048 (4)	0.076 (4)	0.061 (4)	0.018 (4)	0.009 (4)	0.015 (4)
N1	0.038 (3)	0.045 (3)	0.048 (3)	0.020 (3)	0.016 (3)	0.010 (3)
N2	0.041 (3)	0.058 (4)	0.054 (4)	0.023 (3)	0.011 (3)	0.002 (3)
N3	0.041 (3)	0.073 (4)	0.059 (4)	0.018 (3)	0.012 (3)	0.019 (3)
C9	0.040 (4)	0.078 (5)	0.057 (4)	0.017 (4)	0.011 (4)	0.022 (4)

Geometric parameters (Å, º)

Mo1—O6	1.657 (7)	P1—O2	1.592 (14)
Mo1—O7	1.864 (8)	O1—O4	1.728 (18)
Mo1—O5	1.882 (8)	O1—O3^i	1.754 (18)
Mo1—O8	1.903 (8)	O1—Mo3^i	2.467 (12)
Mo1—O22	1.944 (8)	O2—O4^i	1.794 (18)
Mo1—O2	2.452 (13)	O2—O3	1.816 (19)
Mo1—O1	2.510 (13)	O3—O4	1.677 (18)
Mo2—O10	1.654 (7)	O3—O1^i	1.754 (18)
Mo2—O11	1.853 (7)	O4—O2^i	1.794 (18)
Mo2—O12	1.880 (8)	O5—Mo3^i	1.902 (8)
Mo2—O9	1.920 (8)	O9—Mo4^i	1.903 (8)
Mo2—O7	1.963 (8)	O11—Mo6^i	1.933 (8)
Mo2—O2	2.460 (14)	O13—Mo6^i	1.902 (8)
Mo3—O15	1.651 (7)	O23—H23A	0.8500
Mo3—O13	1.896 (8)	O23—H23B	0.8500
Mo3—O5^i	1.902 (8)	C1—N2	1.318 (14)
Mo3—O14	1.914 (8)	C1—N1	1.323 (14)
Mo3—O16	1.927 (8)	C1—H1	0.9300
Mo3—O1^i	2.467 (12)	C2—C3	1.341 (16)
Mo3—O3	2.507 (13)	C2—N2	1.378 (14)
Mo4—O17	1.666 (7)	C2—H2	0.9300
Mo4—O16	1.870 (7)	C3—N1	1.378 (14)
Mo4—O9^i	1.903 (8)	C3—H3	0.9300
Mo4—O18	1.912 (8)	C4—N1	1.478 (14)
Mo4—O19	1.953 (7)	C4—C5	1.502 (17)
Mo4—O3	2.439 (13)	C4—H4A	0.9700
Mo4—O4	2.475 (13)	C4—H4B	0.9700
Mo5—O20	1.653 (7)	C5—C6	1.549 (16)
Mo5—O14	1.883 (8)	C5—H5A	0.9700
Mo5—O12	1.910 (8)	C5—H5B	0.9700
Mo5—O8	1.916 (8)	C6—C7	1.436 (18)
Mo5—O18	1.923 (8)	C6—H6A	0.9700
Mo5—O2	2.429 (13)	C6—H6B	0.9700
Mo6—O21	1.671 (6)	C7—N3	1.503 (15)
Mo6—O22	1.865 (8)	C7—H7A	0.9700
Mo6—O13^i	1.902 (8)	C7—H7B	0.9700
Mo6—O19	1.906 (7)	C8—C9	1.323 (17)
Mo6—O11^i	1.933 (8)	C8—N3	1.365 (15)
Mo6—O1	2.439 (13)	C8—H8	0.9300
Mo6—O4	2.498 (12)	N4—C10	1.313 (16)
P1—O4	1.499 (13)	N4—C9	1.370 (16)
P1—O4^i	1.499 (13)	N4—H4	0.8600
P1—O3^i	1.508 (13)	C10—N3	1.353 (16)
P1—O3	1.508 (13)	C10—H10	0.9300
P1—O1	1.541 (13)	N2—H2A	0.8600
P1—O1^i	1.541 (13)	C9—H9	0.9300
P1—O2^i	1.592 (14)
O6—Mo1—O7	101.8 (4)	O4—P1—O2	109.1 (7)
O6—Mo1—O5	101.7 (4)	O4^i—P1—O2	70.9 (7)
O7—Mo1—O5	89.2 (4)	O3^i—P1—O2	108.4 (7)
O6—Mo1—O8	101.2 (4)	O3—P1—O2	71.6 (7)
O7—Mo1—O8	89.4 (3)	O1—P1—O2	73.6 (7)
O5—Mo1—O8	156.9 (4)	O1^i—P1—O2	106.4 (7)
O6—Mo1—O22	100.8 (3)	O2^i—P1—O2	180.000 (3)
O7—Mo1—O22	157.4 (4)	P1—O1—O4	54.2 (6)
O5—Mo1—O22	86.6 (3)	P1—O1—O3^i	54.0 (6)
O8—Mo1—O22	85.9 (3)	O4—O1—O3^i	91.6 (9)
O6—Mo1—O2	159.0 (4)	P1—O1—Mo6	125.6 (7)
O7—Mo1—O2	64.8 (4)	O4—O1—Mo6	71.3 (6)
O5—Mo1—O2	94.4 (4)	O3^i—O1—Mo6	136.4 (8)
O8—Mo1—O2	64.2 (4)	P1—O1—Mo3^i	124.6 (7)
O22—Mo1—O2	93.4 (4)	O4—O1—Mo3^i	134.3 (8)
O6—Mo1—O1	156.5 (4)	O3^i—O1—Mo3^i	70.6 (6)
O7—Mo1—O1	95.9 (4)	Mo6—O1—Mo3^i	92.7 (4)
O5—Mo1—O1	62.9 (4)	P1—O1—Mo1	120.6 (7)
O8—Mo1—O1	94.3 (4)	O4—O1—Mo1	130.3 (8)
O22—Mo1—O1	62.5 (4)	O3^i—O1—Mo1	126.8 (8)
O2—Mo1—O1	44.4 (4)	Mo6—O1—Mo1	92.5 (4)
O10—Mo2—O11	102.7 (4)	Mo3^i—O1—Mo1	91.7 (4)
O10—Mo2—O12	102.6 (4)	P1—O2—O4^i	52.1 (6)
O11—Mo2—O12	91.3 (3)	P1—O2—O3	52.0 (6)
O10—Mo2—O9	101.5 (4)	O4^i—O2—O3	87.5 (8)
O11—Mo2—O9	88.9 (3)	P1—O2—Mo5	123.5 (7)
O12—Mo2—O9	155.3 (4)	O4^i—O2—Mo5	134.0 (8)
O10—Mo2—O7	101.4 (4)	O3—O2—Mo5	71.5 (6)
O11—Mo2—O7	155.7 (4)	P1—O2—Mo1	121.4 (7)
O12—Mo2—O7	86.1 (3)	O4^i—O2—Mo1	129.4 (8)
O9—Mo2—O7	83.6 (3)	O3—O2—Mo1	130.7 (8)
O10—Mo2—O2	158.5 (4)	Mo5—O2—Mo1	93.5 (5)
O11—Mo2—O2	93.9 (4)	P1—O2—Mo2	123.5 (7)
O12—Mo2—O2	63.0 (4)	O4^i—O2—Mo2	71.3 (6)
O9—Mo2—O2	92.3 (4)	O3—O2—Mo2	133.1 (8)
O7—Mo2—O2	63.5 (4)	Mo5—O2—Mo2	93.6 (5)
O15—Mo3—O13	102.3 (4)	Mo1—O2—Mo2	93.3 (5)
O15—Mo3—O5^i	103.4 (4)	P1—O3—O4	55.9 (6)
O13—Mo3—O5^i	88.2 (3)	P1—O3—O1^i	55.8 (6)
O15—Mo3—O14	101.7 (4)	O4—O3—O1^i	93.6 (9)
O13—Mo3—O14	88.8 (3)	P1—O3—O2	56.3 (6)
O5^i—Mo3—O14	154.8 (4)	O4—O3—O2	92.3 (8)
O15—Mo3—O16	100.6 (4)	O1^i—O3—O2	89.3 (8)
O13—Mo3—O16	157.1 (4)	P1—O3—Mo4	127.1 (7)
O5^i—Mo3—O16	86.9 (3)	O4—O3—Mo4	71.2 (6)
O14—Mo3—O16	86.3 (3)	O1^i—O3—Mo4	133.8 (8)
O15—Mo3—O1^i	159.9 (4)	O2—O3—Mo4	133.1 (8)
O13—Mo3—O1^i	63.7 (4)	P1—O3—Mo3	123.9 (7)
O5^i—Mo3—O1^i	63.7 (4)	O4—O3—Mo3	134.8 (8)
O14—Mo3—O1^i	92.7 (4)	O1^i—O3—Mo3	68.1 (6)
O16—Mo3—O1^i	94.2 (4)	O2—O3—Mo3	126.7 (8)
O15—Mo3—O3	158.8 (4)	Mo4—O3—Mo3	91.7 (4)
O13—Mo3—O3	94.1 (4)	P1—O4—O3	56.4 (6)
O5^i—Mo3—O3	90.3 (4)	P1—O4—O1	56.5 (6)
O14—Mo3—O3	64.9 (4)	O3—O4—O1	94.2 (9)
O16—Mo3—O3	63.6 (4)	P1—O4—O2^i	57.0 (6)
O1^i—Mo3—O3	41.3 (4)	O3—O4—O2^i	92.8 (9)
O17—Mo4—O16	102.0 (4)	O1—O4—O2^i	90.9 (8)
O17—Mo4—O9^i	101.5 (4)	P1—O4—Mo4	125.3 (7)
O16—Mo4—O9^i	89.5 (3)	O3—O4—Mo4	68.9 (6)
O17—Mo4—O18	101.8 (4)	O1—O4—Mo4	134.5 (8)
O16—Mo4—O18	89.0 (3)	O2^i—O4—Mo4	130.3 (8)
O9^i—Mo4—O18	156.4 (4)	P1—O4—Mo6	124.2 (7)
O17—Mo4—O19	99.1 (3)	O3—O4—Mo6	132.6 (8)
O16—Mo4—O19	158.9 (3)	O1—O4—Mo6	67.7 (6)
O9^i—Mo4—O19	87.5 (3)	O2^i—O4—Mo6	129.1 (7)
O18—Mo4—O19	85.5 (3)	Mo4—O4—Mo6	92.6 (4)
O17—Mo4—O3	161.4 (4)	Mo1—O5—Mo3^i	141.3 (5)
O16—Mo4—O3	65.7 (4)	Mo1—O7—Mo2	137.8 (5)
O9^i—Mo4—O3	92.5 (4)	Mo1—O8—Mo5	137.1 (5)
O18—Mo4—O3	65.5 (4)	Mo4^i—O9—Mo2	138.8 (4)
O19—Mo4—O3	93.5 (4)	Mo2—O11—Mo6^i	140.4 (4)
O17—Mo4—O4	158.6 (4)	Mo2—O12—Mo5	140.0 (5)
O16—Mo4—O4	95.0 (4)	Mo3—O13—Mo6^i	138.4 (5)
O9^i—Mo4—O4	65.3 (4)	Mo5—O14—Mo3	139.9 (5)
O18—Mo4—O4	91.4 (4)	Mo4—O16—Mo3	138.5 (5)
O19—Mo4—O4	64.9 (4)	Mo4—O18—Mo5	137.7 (4)
O3—Mo4—O4	39.9 (4)	Mo6—O19—Mo4	137.3 (4)
O20—Mo5—O14	101.8 (4)	Mo6—O22—Mo1	139.5 (4)
O20—Mo5—O12	101.3 (4)	H23A—O23—H23B	108.7
O14—Mo5—O12	88.9 (3)	N2—C1—N1	109.6 (10)
O20—Mo5—O8	100.7 (4)	N2—C1—H1	125.2
O14—Mo5—O8	157.4 (4)	N1—C1—H1	125.2
O12—Mo5—O8	86.8 (3)	C3—C2—N2	106.6 (10)
O20—Mo5—O18	101.8 (4)	C3—C2—H2	126.7
O14—Mo5—O18	88.3 (3)	N2—C2—H2	126.7
O12—Mo5—O18	156.8 (4)	C2—C3—N1	107.8 (10)
O8—Mo5—O18	87.0 (3)	C2—C3—H3	126.1
O20—Mo5—O2	158.1 (4)	N1—C3—H3	126.1
O14—Mo5—O2	93.8 (4)	N1—C4—C5	112.0 (10)
O12—Mo5—O2	63.3 (4)	N1—C4—H4A	109.2
O8—Mo5—O2	64.6 (4)	C5—C4—H4A	109.2
O18—Mo5—O2	93.9 (4)	N1—C4—H4B	109.2
O21—Mo6—O22	102.8 (4)	C5—C4—H4B	109.2
O21—Mo6—O13^i	102.3 (4)	H4A—C4—H4B	107.9
O22—Mo6—O13^i	89.0 (3)	C4—C5—C6	113.4 (10)
O21—Mo6—O19	99.4 (3)	C4—C5—H5A	108.9
O22—Mo6—O19	89.6 (3)	C6—C5—H5A	108.9
O13^i—Mo6—O19	158.0 (3)	C4—C5—H5B	108.9
O21—Mo6—O11^i	100.9 (4)	C6—C5—H5B	108.9
O22—Mo6—O11^i	156.2 (3)	H5A—C5—H5B	107.7
O13^i—Mo6—O11^i	86.5 (3)	C7—C6—C5	112.0 (12)
O19—Mo6—O11^i	86.0 (3)	C7—C6—H6A	109.2
O21—Mo6—O1	160.7 (4)	C5—C6—H6A	109.2
O22—Mo6—O1	64.9 (4)	C7—C6—H6B	109.2
O13^i—Mo6—O1	64.2 (4)	C5—C6—H6B	109.2
O19—Mo6—O1	95.5 (4)	H6A—C6—H6B	107.9
O11^i—Mo6—O1	92.2 (4)	C6—C7—N3	108.6 (11)
O21—Mo6—O4	158.3 (4)	C6—C7—H7A	110.0
O22—Mo6—O4	92.4 (4)	N3—C7—H7A	110.0
O13^i—Mo6—O4	93.2 (4)	C6—C7—H7B	110.0
O19—Mo6—O4	64.9 (4)	N3—C7—H7B	110.0
O11^i—Mo6—O4	64.6 (4)	H7A—C7—H7B	108.4
O1—Mo6—O4	41.0 (4)	C9—C8—N3	108.5 (12)
O4—P1—O4^i	180.000 (2)	C9—C8—H8	125.8
O4—P1—O3^i	112.2 (7)	N3—C8—H8	125.8
O4^i—P1—O3^i	67.8 (7)	C10—N4—C9	108.7 (11)
O4—P1—O3	67.8 (7)	C10—N4—H4	125.6
O4^i—P1—O3	112.2 (7)	C9—N4—H4	125.6
O3^i—P1—O3	180.0 (10)	N4—C10—N3	108.5 (12)
O4—P1—O1	69.3 (7)	N4—C10—H10	125.8
O4^i—P1—O1	110.7 (7)	N3—C10—H10	125.8
O3^i—P1—O1	70.2 (7)	C1—N1—C3	107.5 (9)
O3—P1—O1	109.8 (7)	C1—N1—C4	125.2 (9)
O4—P1—O1^i	110.7 (7)	C3—N1—C4	127.3 (9)
O4^i—P1—O1^i	69.3 (7)	C1—N2—C2	108.4 (10)
O3^i—P1—O1^i	109.8 (7)	C1—N2—H2A	125.8
O3—P1—O1^i	70.2 (7)	C2—N2—H2A	125.8
O1—P1—O1^i	180.000 (3)	C10—N3—C8	107.0 (11)
O4—P1—O2^i	70.9 (7)	C10—N3—C7	127.1 (11)
O4^i—P1—O2^i	109.1 (7)	C8—N3—C7	125.9 (11)
O3^i—P1—O2^i	71.6 (7)	C8—C9—N4	107.2 (11)
O3—P1—O2^i	108.4 (7)	C8—C9—H9	126.4
O1—P1—O2^i	106.4 (7)	N4—C9—H9	126.4
O1^i—P1—O2^i	73.6 (7)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O9^ii	0.86	2.23	2.976 (13)	145
N2—H2A···O19^iii	0.86	2.03	2.892 (12)	175
O23—H23A···O15^iv	0.85	2.47	3.308 (13)	170
O23—H23B···O18^iii	0.85	2.23	3.071 (12)	170

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