Bis(iminodiethylenedi­ammonium) di-μ₅-hydrogen­phosphato-penta­molybdate(VI) tetra­hydrate

The crystal structure of the title compound, (C₄H₁₅N₃)₂[Mo₅O₁₅(HPO₄)₂]·4H₂O, is made up of [Mo₅O₁₅(HPO₄)₂]⁴⁻ clusters, iminodiethylenediammonium cations and solvent water mol­ecules. The [Mo₅O₁₅(HPO₄)₂]⁴⁻ cluster, with approximate C₂ symmetry, can be considered as a ring formed by five distorted edge- and corner-sharing MoO₆ octa­hedra, capped on both poles by a hydro­phosphate tetra­hedron. There exist N—H...O, O—H...N and C—H...O hydrogen bonds between the organic ammonium groups and the clusters, with inter­atomic N...O distances ranging from 2.675 (3) to 2.999 (3) Å, and C...O distances ranging from 3.139 (5) to 3.460 (5) Å.

S1. Comment

Over the past few decades, polyoxometalates have been found to be extremely versatile inorganic building blocks for the construction of organic–inorganic hybrid materials, owing to the wide range of their topological properties and potential applications in catalysis, photochemistry, electrochromism and magnetism (Braun et al., 1999). An important class of metal oxide cluster based on molybdenum phosphate anions has been attracting much attention owing to their novel structures and unusual properties (Guo & Liu, 2003). Typical examples include (NH₄)₂[(CH₃)₄N]₂[Fe₂Mo₁₂O₃₀(H₂PO₄)₆(HPO₄)₂] (Meyer & Haushalter, 1993), (H₂en)₃[P₂Mo₅O₂₃]·6H₂O (en is ethylenediamine; Aranzabe et al., 1997), [H₂en]₂[{Cu(en)(H₂O)}Mo₅P₂O₂₃]·4H₂O (Lu et al., 1998), (H₂en)₁₀(H₃O)₃(H₅O₂)Na₂[MnMo₁₂O₂₄(OH)₆(PO₄)₄(HPO₄)₄][MnMo₁₂O₂₄(OH)₆(PO₄)₆(HPO₄)₂]·9H₂O (Xu et al. 1999), (C₄H₁₂N₂)_0.5[Co(en)₃][(Mo₅O₁₅)(HPO₄)₂] (He et al., 2004), [{Cu(bpy)₂}{Cu(bpy)(H₂O)}(Mo₅O₁₅){O₃P(CH₂)₄PO₃}] (bpy is 2,2'-bipyridine; Finn et al., 2001) and (H₂bpy)_0.5{[Ni(H₂O)₅][Ni(Hbpy)(H₂O)₄[Mo₅P₂O₂₃]} (Lu et al. 2005). Compared with ethylenediamine or pyridine templates, the hybrid materials containing diethylenetriamine (tren) or its ammonium analog remain largely unexplored (Lin et al., 2003). We report here the hydrothermal synthesis and crystal structure of the title novel organic–inorganic hybrid, viz. (H₂tren)₂[Mo₅O₁₅(HPO₄)₂]·4H₂O, (I).

The crystal structure of (I) is made up of [Mo₅O₁₅(HPO₄)₂]⁴⁻ anionic clusters, (H₂tren)²⁺ cations and solvent water molecules. As shown in Fig. 1, the [Mo₅O₁₅(HPO₄)₂]⁴⁻ cluster has approximate C₂ symmetry, with atoms Mo4 and O12 lying on the axis. The five MoO₆ octahedra in the cluster aggregate in a compact edge-sharing or corner-sharing arrangement to form a ring with two PO₄ tetrahedra coordinated above and below the ring. The Mo₅ ring is nearly planar, with a mean least-squares deviation of 0.2238 Å, and the interatomic distance between atoms P1 and P2 is 3.8024 (11) Å, the orientation of the P1···P2 vector to the ring being 84.5 (2)°. Each hydrophosphate subunit has one terminal OH group, and three bridging O atoms shared with the molybdenum ring, where one of these oxo-groups adopts the µ₂-bridging mode, linking one molybdenum and one phosphorus site, and the other two adopt the µ₃-bridging mode, linking two molybdenum sites and one phosphorus sit. The five MoO₆ octahedra can be classified into two groups, viz. (1) the corner-sharing octahedra around Mo1 and Mo2, each of which has two terminal oxygen atoms (O_t), two O_b atoms shared by two molybdenum sites, one Oµ₂ atom and one Oµ₃ atom, and (2) the edge-sharing octahedra surrounding atoms Mo3, Mo4 and Mo5, each of which has two O_t, two O_b and two Oµ₃ atoms. Different types of O atoms have different Mo—O bond distances [Mo—O_t = 1.706 (2)–1.734 (2) Å, Mo—O_b = 1.914 (2)–1.960 (2) Å, Mo—Oµ₂ = 2.216 (2)–2.217 (2) Å and Mo—Oµ₃ = 2.183 (2)–2.440 (2) Å; Table 1]. These bond distances are in accordance with those observed in (C₆H₁₁NH₃)₅H(P₂Mo₅O₂₃)·4H₂O (Wang et al., 2004) and (H₂bpy)_0.5{[Ni(H₂O)₅][Ni(Hbpy)(H₂O)₄][Mo₅P₂O₂₃]} (Lu et al. 2005). The PO₄ tetrahedra exhibit distorted geometry, with P—O bond distances ranging from 1.514 (2) to 1.568 (2) Å and the O—P—O bond angles are between 106.32 (12) and 110.99 (12)°, which are in agreement with those previously reported (Aranzabe et al. 1997). Valence sum calculations (Brown & Altermatt, 1985) demonstrated that all Mo atoms in (I) have valence sums ranging from 5.835 to 5.987, with an average value of 5.925, very close to the ideal value of six for Mo^VI. Atoms O17 and O20 have valence sums of 1.208 and 1.225, respectively, which suggests that both of the terminal O atoms of PO₄ tetrahedra are protonated.

The arrangement of the [Mo₅O₁₅(HPO₄)₂]⁴⁻ clusters, the (H₂tren)²⁺ cations and the solvent water molecules in the crystal structure of (I) along the b axis is demonstrated in Fig. 2, which shows the extensive hydrogen bonding. As listed in Table 2, the N—H···O and O—H···N hydrogen bonds between the organic ammonium groups and the clusters have N···O interatomic distances ranging from 2.675 (3) to 2.999 (3) Å and hydrogen-bond angles from 124 to 173°. There also exist C—H···O hydrogen bonds between the CH groups of the organic cations and the O atoms from the clusters, with C···O distances between 3.139 (5) and 3.460 (5) Å and hydrogen-bond angles between 122 and 160°. These hydrogen bonds hold the [Mo₅O₁₅(HPO₄)₂]⁴⁻ clusters and the (H₂tren)²⁺ cations in (I) together into a three-dimensional supramolecular network, completed by the solvent water molecules, which form N —H···O and O—H···O hydrogen bonds with the geometric parameters 2.890 (4)–3.113 (5) Å and 118 (3)–175 (5)°.

S2. Experimental

Compound (I) was hydrothermally synthesized under autogenous pressure in a 17 ml Teflon-lined stainless steel autoclave with a fill factor of approximate 40%. A mixture of (NH₄)₆Mo₇O₂₄·4H₂O, Nd₂O₃, H₃PO₄, diethylenetriamine and water in the molar ratio of 1:1:2.8:1.15:333 was heated at 393 K for 6 d. After slow cooling to ambient temperature, colorless block-shaped crystals of (I) were obtained. The crystals were filtered off, washed with distilled water and dried in a desiccator at ambient temperature (yield ca 60% based on molybdenum). The pH value of the reactive system increased from 3.42 before heating to 3.68 at the end of the reaction. The strong band at 952 cm⁻¹ in the IR spectrum is assigned to the Mo—O_t stretching vibrations, and the bands at 892, 775 and 676 cm⁻¹ are related to the Mo—O—Mo vibrations, while the characteristic bands at 1091 and 1025 cm⁻¹ are attributed to the P—O vibrations. Bands ranging from 1330 to 1268 cm⁻¹ are characteristic of C—N and C—C bonds of the organic groups. Analysis calculated for C₈H₄₀Mo₅N₆O₂₇P₂: C 8.13, H 3.27, N 6.98, P 5.20, Mo 40.11%; found: C 8.05, H 3.36, N 7.12, P 5.08, Mo 40.03%.

S3. Refinement

While the H atoms attached to C, N and hydroxy O atoms were placed in calculated positions, those on water molecules were located in a difference Fourier map and then refined with the O—H distances restrained to 0.96 (s.u.?) Å and the H—O—H angles to 104 (s.u.?)°. All H atoms were included in the refinement with U_iso (H) values of 1.2U_eq(parent atom).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1987); cell refinement: TEXSAN (Molecular Structure Corporation, 1987); data reduction: TEXSAN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit in (I), showing the atom-labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. A packing view of (I) along the b axis, showing the arrangement of the [Mo5O15(HPO4)2]^4− clusters (polyhedron), the (H2tren)^2+ cations and the solvent water molecules in the crystal structure. The dashed lines denote the hydrogen-bonding interactions, and H atoms not involved in such interactions have been omitted for clarity.

Bis(aminodiethylammonium) di-µ₅-hydrogenphosphato-pentamolybdate(VI) tetrahydrate

Crystal data

(C4H15N3)2[Mo5O15(HPO4)2]·4H2O	Z = 2
Mr = 1194.10	F(000) = 1172
Triclinic, P1	Dx = 2.415 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 10.3497 (14) Å	Cell parameters from 100 reflections
b = 10.9934 (15) Å	θ = 10–15°
c = 15.751 (2) Å	µ = 2.06 mm^−1
α = 95.650 (6)°	T = 294 K
β = 95.734 (6)°	Block, colorless
γ = 111.408 (5)°	0.16 × 0.12 × 0.08 mm
V = 1642.4 (4) Å^3

Data collection

Rigaku AFC-5R diffractometer	6371 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 26.5°, θmin = 1.3°
ω–2θ scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = −13→13
Tmin = 0.734, Tmax = 0.852	l = −19→19
25131 measured reflections	3 standard reflections every 150 reflections
6733 independent reflections	intensity decay: 0.2%

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0569P)^2 + 0.165P] where P = (Fo^2 + 2Fc^2)/3
6733 reflections	(Δ/σ)max = 0.009
462 parameters	Δρmax = 0.92 e Å^−3
12 restraints	Δρmin = −0.93 e Å^−3

Special details

Experimental. crystal coated in epoxy glue

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 > 2σ(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	0.39089 (3)	0.60436 (2)	0.187695 (16)	0.01835 (8)
Mo2	0.39619 (3)	0.93892 (2)	0.170885 (16)	0.01941 (9)
Mo3	0.08717 (3)	0.92692 (3)	0.233543 (17)	0.02224 (9)
Mo4	−0.02956 (3)	0.67519 (3)	0.346595 (16)	0.01979 (9)
Mo5	0.16309 (3)	0.48620 (2)	0.326644 (16)	0.01805 (8)
P1	0.08070 (7)	0.62918 (7)	0.14843 (4)	0.01494 (15)
P2	0.32796 (7)	0.81964 (7)	0.35333 (4)	0.01582 (15)
O1	0.4171 (2)	0.5272 (2)	0.09538 (15)	0.0292 (5)
O2	0.5434 (2)	0.6303 (3)	0.25490 (16)	0.0328 (5)
O3	0.5588 (2)	1.0639 (2)	0.18883 (15)	0.0333 (6)
O4	0.3428 (3)	0.9340 (2)	0.06257 (15)	0.0304 (5)
O5	−0.0010 (3)	0.9455 (3)	0.14158 (18)	0.0392 (6)
O6	0.0765 (3)	1.0418 (3)	0.31249 (19)	0.0409 (6)
O7	−0.0382 (3)	0.7693 (3)	0.43927 (15)	0.0369 (6)
O8	−0.1921 (2)	0.5460 (2)	0.32637 (16)	0.0300 (5)
O9	0.2713 (2)	0.4698 (2)	0.41132 (15)	0.0296 (5)
O10	0.0234 (2)	0.3365 (2)	0.30439 (16)	0.0304 (5)
O11	0.2604 (2)	0.45430 (19)	0.23219 (13)	0.0203 (4)
O12	0.4357 (2)	0.7804 (2)	0.16154 (14)	0.0220 (4)
O13	0.2812 (2)	1.0261 (2)	0.21756 (15)	0.0276 (5)
O14	−0.0617 (2)	0.7712 (2)	0.25721 (14)	0.0218 (4)
O15	0.0864 (2)	0.5900 (2)	0.39737 (12)	0.0211 (4)
O16	0.1854 (2)	0.5772 (2)	0.11471 (13)	0.0191 (4)
O17	−0.0519 (2)	0.5879 (2)	0.08146 (13)	0.0232 (4)
H17	−0.0640	0.5175	0.0524	0.028*
O18	0.1560 (2)	0.7830 (2)	0.16668 (13)	0.0197 (4)
O19	0.0402 (2)	0.5724 (2)	0.23316 (13)	0.0195 (4)
O20	0.3823 (2)	0.8342 (2)	0.44894 (13)	0.0236 (4)
H20	0.3821	0.9032	0.4739	0.028*
O21	0.3106 (2)	0.6805 (2)	0.30710 (13)	0.0189 (4)
O22	0.4326 (2)	0.9231 (2)	0.30974 (13)	0.0209 (4)
O23	0.1838 (2)	0.8348 (2)	0.34041 (14)	0.0197 (4)
N1	0.7558 (3)	−0.2197 (3)	0.53723 (19)	0.0330 (6)
H1C	0.8010	−0.1882	0.5906	0.040*
H1D	0.8160	−0.2270	0.5024	0.040*
H1E	0.6890	−0.2987	0.5368	0.040*
N2	0.6906 (3)	0.0415 (3)	0.42076 (18)	0.0249 (6)
H2C	0.6182	−0.0048	0.3790	0.030*
N3	0.7133 (4)	0.3401 (3)	0.43811 (19)	0.0370 (7)
H3C	0.6741	0.3953	0.4212	0.044*
H3D	0.8006	0.3862	0.4642	0.044*
H3E	0.6636	0.2925	0.4747	0.044*
N4	0.6934 (3)	0.5308 (3)	0.1352 (2)	0.0351 (7)
H4C	0.6897	0.5764	0.1842	0.042*
H4D	0.6404	0.5444	0.0920	0.042*
H4E	0.7818	0.5573	0.1248	0.042*
N5	0.7826 (3)	0.3060 (3)	0.04549 (17)	0.0259 (6)
H5C	0.7751	0.2598	−0.0065	0.031*
N6	1.0854 (3)	0.2982 (3)	0.06579 (18)	0.0274 (6)
H6C	1.0781	0.3112	0.0109	0.033*
H6D	1.1547	0.2697	0.0771	0.033*
H6E	1.1037	0.3737	0.0999	0.033*
C1	0.6938 (5)	−0.1316 (5)	0.5082 (3)	0.0538 (11)
H1A	0.6942	−0.0722	0.5581	0.065*
H1B	0.5965	−0.1834	0.4848	0.065*
C2	0.7577 (5)	−0.0516 (5)	0.4438 (3)	0.0548 (13)
H2A	0.7525	−0.1098	0.3920	0.066*
H2B	0.8561	−0.0016	0.4655	0.066*
C3	0.7838 (4)	0.1552 (4)	0.3825 (2)	0.0322 (7)
H3A	0.8082	0.1217	0.3297	0.039*
H3B	0.8699	0.2012	0.4224	0.039*
C4	0.7159 (4)	0.2518 (3)	0.3628 (2)	0.0293 (7)
H4A	0.7657	0.3052	0.3221	0.035*
H4B	0.6203	0.2024	0.3350	0.035*
C5	0.6415 (4)	0.3897 (4)	0.1427 (2)	0.0337 (8)
H5A	0.5471	0.3626	0.1571	0.040*
H5B	0.7003	0.3755	0.1895	0.040*
C6	0.6403 (3)	0.3050 (4)	0.0609 (2)	0.0287 (7)
H6A	0.6014	0.3349	0.0123	0.034*
H6B	0.5785	0.2147	0.0627	0.034*
C7	0.8490 (4)	0.2511 (4)	0.1132 (2)	0.0363 (8)
H7A	0.8963	0.3201	0.1618	0.044*
H7B	0.7760	0.1808	0.1335	0.044*
C8	0.9521 (4)	0.1983 (3)	0.0814 (3)	0.0408 (9)
H8A	0.9737	0.1468	0.1233	0.049*
H8B	0.9078	0.1387	0.0281	0.049*
O24	0.5736 (3)	0.5450 (3)	0.42094 (18)	0.0452 (7)
H24A	0.486 (2)	0.556 (5)	0.423 (2)	0.054*
H24B	0.592 (4)	0.554 (4)	0.3631 (10)	0.054*
O25	0.6979 (4)	0.8112 (5)	0.0987 (3)	0.0886 (13)
H25A	0.6025 (17)	0.794 (6)	0.107 (4)	0.106*
H25B	0.752 (5)	0.862 (6)	0.152 (2)	0.106*
O26	0.3961 (4)	0.2774 (3)	0.3115 (2)	0.0548 (8)
H26A	0.358 (5)	0.334 (3)	0.284 (3)	0.066*
H26B	0.353 (4)	0.1935 (19)	0.275 (2)	0.066*
O27	0.2840 (4)	0.1898 (4)	0.0668 (4)	0.0885 (14)
H27A	0.290 (8)	0.162 (5)	0.0083 (14)	0.106*
H27B	0.268 (7)	0.113 (3)	0.094 (3)	0.106*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01619 (14)	0.02517 (15)	0.01985 (15)	0.01276 (11)	0.00666 (10)	0.00809 (11)
Mo2	0.02075 (15)	0.02089 (15)	0.01756 (14)	0.00743 (11)	0.00433 (10)	0.00754 (10)
Mo3	0.02221 (15)	0.02244 (15)	0.02690 (16)	0.01346 (11)	0.00258 (11)	0.00691 (11)
Mo4	0.01618 (14)	0.02705 (15)	0.02116 (15)	0.01186 (11)	0.00679 (10)	0.00791 (11)
Mo5	0.01914 (15)	0.02189 (15)	0.01862 (14)	0.01157 (11)	0.00579 (10)	0.01017 (10)
P1	0.0136 (3)	0.0188 (3)	0.0158 (3)	0.0085 (3)	0.0037 (3)	0.0069 (3)
P2	0.0145 (3)	0.0219 (4)	0.0149 (3)	0.0099 (3)	0.0040 (3)	0.0067 (3)
O1	0.0291 (12)	0.0420 (14)	0.0263 (12)	0.0207 (11)	0.0118 (10)	0.0134 (10)
O2	0.0286 (12)	0.0482 (15)	0.0355 (13)	0.0257 (11)	0.0124 (10)	0.0180 (11)
O3	0.0273 (12)	0.0321 (13)	0.0270 (12)	−0.0043 (10)	0.0029 (10)	0.0041 (10)
O4	0.0390 (13)	0.0316 (13)	0.0238 (12)	0.0151 (10)	0.0060 (10)	0.0102 (10)
O5	0.0367 (14)	0.0350 (14)	0.0463 (16)	0.0153 (11)	−0.0032 (12)	0.0107 (12)
O6	0.0417 (15)	0.0404 (15)	0.0494 (16)	0.0263 (12)	0.0108 (12)	−0.0004 (12)
O7	0.0372 (14)	0.0613 (17)	0.0249 (12)	0.0298 (13)	0.0133 (11)	0.0121 (12)
O8	0.0190 (11)	0.0325 (13)	0.0327 (13)	0.0027 (9)	0.0047 (9)	0.0049 (10)
O9	0.0318 (12)	0.0357 (13)	0.0297 (12)	0.0204 (11)	0.0054 (10)	0.0126 (10)
O10	0.0319 (13)	0.0261 (12)	0.0335 (13)	0.0095 (10)	0.0076 (10)	0.0088 (10)
O11	0.0254 (11)	0.0164 (10)	0.0230 (11)	0.0104 (8)	0.0081 (8)	0.0075 (8)
O12	0.0200 (10)	0.0283 (11)	0.0235 (11)	0.0122 (9)	0.0100 (8)	0.0113 (9)
O13	0.0235 (11)	0.0295 (12)	0.0309 (12)	0.0106 (9)	0.0041 (9)	0.0080 (10)
O14	0.0183 (10)	0.0178 (10)	0.0334 (12)	0.0095 (8)	0.0045 (9)	0.0111 (9)
O15	0.0264 (11)	0.0341 (12)	0.0122 (9)	0.0197 (9)	0.0084 (8)	0.0084 (8)
O16	0.0176 (10)	0.0229 (10)	0.0213 (10)	0.0113 (8)	0.0061 (8)	0.0066 (8)
O17	0.0199 (10)	0.0350 (12)	0.0203 (10)	0.0156 (9)	0.0034 (8)	0.0085 (9)
O18	0.0197 (10)	0.0192 (10)	0.0199 (10)	0.0066 (8)	0.0037 (8)	0.0037 (8)
O19	0.0208 (10)	0.0277 (11)	0.0164 (10)	0.0139 (9)	0.0064 (8)	0.0097 (8)
O20	0.0271 (11)	0.0276 (11)	0.0177 (10)	0.0126 (9)	0.0010 (8)	0.0040 (8)
O21	0.0167 (10)	0.0250 (11)	0.0185 (10)	0.0097 (8)	0.0080 (8)	0.0075 (8)
O22	0.0203 (10)	0.0248 (11)	0.0191 (10)	0.0084 (9)	0.0045 (8)	0.0091 (8)
O23	0.0150 (10)	0.0206 (10)	0.0259 (11)	0.0089 (8)	0.0017 (8)	0.0076 (8)
N1	0.0421 (17)	0.0305 (15)	0.0306 (15)	0.0186 (13)	0.0057 (13)	0.0042 (12)
N2	0.0237 (13)	0.0240 (13)	0.0289 (14)	0.0105 (11)	0.0064 (11)	0.0038 (11)
N3	0.054 (2)	0.0380 (17)	0.0256 (15)	0.0221 (15)	0.0116 (14)	0.0098 (13)
N4	0.0229 (14)	0.0373 (16)	0.0481 (19)	0.0149 (12)	0.0104 (13)	0.0010 (14)
N5	0.0282 (14)	0.0372 (15)	0.0195 (13)	0.0184 (12)	0.0069 (11)	0.0100 (11)
N6	0.0250 (14)	0.0344 (15)	0.0244 (14)	0.0144 (12)	0.0005 (11)	0.0032 (11)
C1	0.061 (3)	0.062 (3)	0.058 (3)	0.041 (2)	0.015 (2)	0.023 (2)
C2	0.061 (3)	0.071 (3)	0.068 (3)	0.052 (3)	0.034 (2)	0.042 (3)
C3	0.0248 (16)	0.0376 (19)	0.0366 (19)	0.0111 (14)	0.0096 (14)	0.0138 (15)
C4	0.0412 (19)	0.0264 (16)	0.0214 (16)	0.0136 (14)	0.0048 (14)	0.0059 (13)
C5	0.0319 (18)	0.046 (2)	0.0322 (18)	0.0225 (16)	0.0128 (15)	0.0098 (16)
C6	0.0216 (15)	0.0381 (18)	0.0271 (16)	0.0121 (13)	0.0040 (13)	0.0048 (14)
C7	0.0354 (19)	0.046 (2)	0.036 (2)	0.0186 (16)	0.0105 (15)	0.0250 (17)
C8	0.0276 (18)	0.0221 (17)	0.071 (3)	0.0075 (14)	0.0035 (17)	0.0099 (17)
O24	0.0421 (15)	0.0584 (18)	0.0346 (15)	0.0171 (14)	0.0040 (12)	0.0147 (13)
O25	0.051 (2)	0.113 (4)	0.093 (3)	0.023 (2)	0.015 (2)	0.002 (3)
O26	0.068 (2)	0.0374 (16)	0.061 (2)	0.0224 (15)	0.0170 (17)	−0.0004 (14)
O27	0.057 (2)	0.072 (3)	0.158 (5)	0.039 (2)	0.027 (3)	0.051 (3)

Geometric parameters (Å, º)

Mo1—O1	1.706 (2)	N2—C3	1.497 (4)
Mo1—O2	1.723 (2)	N2—H2C	0.9000
Mo1—O12	1.916 (2)	N3—C4	1.466 (4)
Mo1—O11	1.956 (2)	N3—H3C	0.8900
Mo1—O16	2.216 (2)	N3—H3D	0.8900
Mo1—O21	2.332 (2)	N3—H3E	0.8900
Mo2—O3	1.715 (2)	N4—C5	1.466 (5)
Mo2—O4	1.729 (2)	N4—H4C	0.8900
Mo2—O12	1.925 (2)	N4—H4D	0.8900
Mo2—O13	1.936 (2)	N4—H4E	0.8900
Mo2—O22	2.217 (2)	N5—C7	1.502 (4)
Mo2—O18	2.440 (2)	N5—C6	1.512 (4)
Mo3—O5	1.703 (3)	N5—H5C	0.8999
Mo3—O6	1.724 (3)	N6—C8	1.478 (4)
Mo3—O14	1.939 (2)	N6—H6C	0.8900
Mo3—O13	1.960 (2)	N6—H6D	0.8900
Mo3—O18	2.183 (2)	N6—H6E	0.8900
Mo3—O23	2.366 (2)	C1—C2	1.458 (6)
Mo4—O7	1.733 (3)	C1—H1A	0.9700
Mo4—O8	1.734 (2)	C1—H1B	0.9700
Mo4—O14	1.914 (2)	C2—H2A	0.9700
Mo4—O15	1.932 (2)	C2—H2B	0.9700
Mo4—O23	2.283 (2)	C3—C4	1.511 (5)
Mo4—O19	2.334 (2)	C3—H3A	0.9700
Mo5—O9	1.721 (2)	C3—H3B	0.9700
Mo5—O10	1.723 (2)	C4—H4A	0.9700
Mo5—O15	1.940 (2)	C4—H4B	0.9700
Mo5—O11	1.951 (2)	C5—C6	1.511 (5)
Mo5—O21	2.198 (2)	C5—H5A	0.9700
Mo5—O19	2.338 (2)	C5—H5B	0.9700
P1—O16	1.514 (2)	C6—H6A	0.9700
P1—O17	1.538 (2)	C6—H6B	0.9700
P1—O19	1.559 (2)	C7—C8	1.492 (5)
P1—O18	1.564 (2)	C7—H7A	0.9700
P2—O20	1.525 (2)	C7—H7B	0.9700
P2—O22	1.530 (2)	C8—H8A	0.9700
P2—O23	1.557 (2)	C8—H8B	0.9700
P2—O21	1.568 (2)	O24—H24A	0.96 (2)
O17—H17	0.8200	O24—H24B	0.96 (2)
O20—H20	0.8200	O25—H25A	0.96 (4)
N1—C1	1.429 (5)	O25—H25B	0.96 (4)
N1—H1C	0.8900	O26—H26A	0.96 (4)
N1—H1D	0.8900	O26—H26B	0.96 (2)
N1—H1E	0.8900	O27—H27A	0.94 (4)
N2—C2	1.484 (5)	O27—H27B	0.95 (4)
O1—Mo1—O2	101.04 (11)	P1—O18—Mo2	134.96 (12)
O1—Mo1—O12	101.36 (10)	Mo3—O18—Mo2	94.57 (7)
O2—Mo1—O12	98.53 (11)	P1—O19—Mo4	125.67 (12)
O1—Mo1—O11	100.93 (10)	P1—O19—Mo5	128.63 (11)
O2—Mo1—O11	99.97 (10)	Mo4—O19—Mo5	92.63 (7)
O12—Mo1—O11	147.57 (9)	P2—O20—H20	109.5
O1—Mo1—O16	85.40 (10)	P2—O21—Mo5	127.82 (11)
O2—Mo1—O16	173.41 (10)	P2—O21—Mo1	135.19 (11)
O12—Mo1—O16	81.40 (8)	Mo5—O21—Mo1	96.29 (8)
O11—Mo1—O16	77.23 (8)	P2—O22—Mo2	122.97 (12)
O1—Mo1—O21	168.93 (9)	P2—O23—Mo4	126.11 (12)
O2—Mo1—O21	87.52 (10)	P2—O23—Mo3	130.50 (12)
O12—Mo1—O21	84.10 (8)	Mo4—O23—Mo3	92.34 (7)
O11—Mo1—O21	70.39 (8)	C1—N1—H1C	109.5
O16—Mo1—O21	85.92 (7)	C1—N1—H1D	109.5
O3—Mo2—O4	102.49 (12)	H1C—N1—H1D	109.5
O3—Mo2—O12	104.02 (11)	C1—N1—H1E	109.5
O4—Mo2—O12	97.88 (10)	H1C—N1—H1E	109.5
O3—Mo2—O13	101.94 (12)	H1D—N1—H1E	109.5
O4—Mo2—O13	98.16 (11)	C2—N2—C3	113.4 (3)
O12—Mo2—O13	145.57 (9)	C2—N2—H2C	105.8
O3—Mo2—O22	86.04 (10)	C3—N2—H2C	106.1
O4—Mo2—O22	171.42 (10)	C4—N3—H3C	109.5
O12—Mo2—O22	80.70 (8)	C4—N3—H3D	109.5
O13—Mo2—O22	78.94 (9)	H3C—N3—H3D	109.5
O3—Mo2—O18	169.88 (10)	C4—N3—H3E	109.5
O4—Mo2—O18	83.62 (10)	H3C—N3—H3E	109.5
O12—Mo2—O18	82.86 (8)	H3D—N3—H3E	109.5
O13—Mo2—O18	68.95 (8)	C5—N4—H4C	109.5
O22—Mo2—O18	87.81 (7)	C5—N4—H4D	109.5
O5—Mo3—O6	105.04 (13)	H4C—N4—H4D	109.5
O5—Mo3—O14	96.60 (11)	C5—N4—H4E	109.5
O6—Mo3—O14	99.11 (12)	H4C—N4—H4E	109.5
O5—Mo3—O13	100.40 (11)	H4D—N4—H4E	109.5
O6—Mo3—O13	96.67 (12)	C7—N5—C6	113.7 (3)
O14—Mo3—O13	152.91 (9)	C7—N5—H5C	109.0
O5—Mo3—O18	93.45 (11)	C6—N5—H5C	109.7
O6—Mo3—O18	160.76 (11)	C8—N6—H6C	109.5
O14—Mo3—O18	83.69 (8)	C8—N6—H6D	109.5
O13—Mo3—O18	74.41 (9)	H6C—N6—H6D	109.5
O5—Mo3—O23	162.72 (10)	C8—N6—H6E	109.5
O6—Mo3—O23	89.85 (11)	H6C—N6—H6E	109.5
O14—Mo3—O23	71.98 (8)	H6D—N6—H6E	109.5
O13—Mo3—O23	86.24 (8)	N1—C1—C2	117.6 (4)
O18—Mo3—O23	72.82 (8)	N1—C1—H1A	107.9
O7—Mo4—O8	103.78 (12)	C2—C1—H1A	107.9
O7—Mo4—O14	103.00 (11)	N1—C1—H1B	107.9
O8—Mo4—O14	97.38 (10)	C2—C1—H1B	107.9
O7—Mo4—O15	98.69 (10)	H1A—C1—H1B	107.2
O8—Mo4—O15	101.04 (11)	C1—C2—N2	113.8 (3)
O14—Mo4—O15	147.18 (9)	C1—C2—H2A	108.8
O7—Mo4—O23	88.05 (11)	N2—C2—H2A	108.8
O8—Mo4—O23	166.99 (10)	C1—C2—H2B	108.8
O14—Mo4—O23	74.36 (8)	N2—C2—H2B	108.8
O15—Mo4—O23	82.15 (8)	H2A—C2—H2B	107.7
O7—Mo4—O19	166.14 (10)	N2—C3—C4	112.7 (3)
O8—Mo4—O19	88.90 (10)	N2—C3—H3A	109.0
O14—Mo4—O19	80.49 (8)	C4—C3—H3A	109.0
O15—Mo4—O19	73.00 (7)	N2—C3—H3B	109.0
O23—Mo4—O19	79.92 (8)	C4—C3—H3B	109.0
O9—Mo5—O10	105.04 (11)	H3A—C3—H3B	107.8
O9—Mo5—O15	94.76 (10)	N3—C4—C3	114.8 (3)
O10—Mo5—O15	101.10 (11)	N3—C4—H4A	108.6
O9—Mo5—O11	99.11 (10)	C3—C4—H4A	108.6
O10—Mo5—O11	96.31 (10)	N3—C4—H4B	108.6
O15—Mo5—O11	154.08 (9)	C3—C4—H4B	108.6
O9—Mo5—O21	94.75 (10)	H4A—C4—H4B	107.5
O10—Mo5—O21	159.07 (10)	N4—C5—C6	112.7 (3)
O15—Mo5—O21	83.66 (8)	N4—C5—H5A	109.1
O11—Mo5—O21	73.50 (8)	C6—C5—H5A	109.1
O9—Mo5—O19	162.97 (10)	N4—C5—H5B	109.1
O10—Mo5—O19	89.05 (10)	C6—C5—H5B	109.1
O15—Mo5—O19	72.78 (8)	H5A—C5—H5B	107.8
O11—Mo5—O19	88.58 (8)	C5—C6—N5	114.7 (3)
O21—Mo5—O19	72.77 (8)	C5—C6—H6A	108.6
O16—P1—O17	110.55 (12)	N5—C6—H6A	108.6
O16—P1—O19	109.07 (11)	C5—C6—H6B	108.6
O17—P1—O19	109.43 (12)	N5—C6—H6B	108.6
O16—P1—O18	106.32 (12)	H6A—C6—H6B	107.6
O17—P1—O18	110.79 (12)	C8—C7—N5	113.2 (3)
O19—P1—O18	110.63 (12)	C8—C7—H7A	108.9
O20—P2—O22	110.62 (12)	N5—C7—H7A	108.9
O20—P2—O23	110.99 (12)	C8—C7—H7B	108.9
O22—P2—O23	109.12 (12)	N5—C7—H7B	108.9
O20—P2—O21	109.86 (12)	H7A—C7—H7B	107.7
O22—P2—O21	107.23 (12)	N6—C8—C7	115.7 (3)
O23—P2—O21	108.94 (12)	N6—C8—H8A	108.3
Mo5—O11—Mo1	119.50 (10)	C7—C8—H8A	108.3
Mo1—O12—Mo2	148.20 (12)	N6—C8—H8B	108.3
Mo2—O13—Mo3	121.65 (12)	C7—C8—H8B	108.3
Mo4—O14—Mo3	121.06 (11)	H8A—C8—H8B	107.4
Mo4—O15—Mo5	121.52 (10)	H24A—O24—H24B	105 (3)
P1—O16—Mo1	124.87 (12)	H25A—O25—H25B	104 (3)
P1—O17—H17	109.5	H26A—O26—H26B	104 (3)
P1—O18—Mo3	128.59 (12)	H27A—O27—H27B	105 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O17—H17···N5^i	0.82	2.27	2.906 (4)	135
O20—H20···N2^ii	0.82	2.02	2.675 (3)	137
N1—H1C···O6^ii	0.89	2.04	2.868 (4)	154
N1—H1D···O7^iii	0.89	1.90	2.784 (4)	173
N1—H1E···O9^iv	0.89	2.27	2.867 (4)	124
N2—H2C···O22^v	0.90	1.95	2.822 (3)	162
N3—H3C···O24	0.89	2.25	3.107 (4)	163
N3—H3D···O15^ii	0.89	2.31	2.996 (4)	134
N3—H3E···O20^ii	0.89	1.89	2.731 (4)	157
N4—H4C···O2	0.89	2.18	2.930 (4)	142
N4—H4D···O1	0.89	2.26	2.851 (4)	124
N4—H4E···O17^vi	0.89	1.84	2.720 (4)	168
N5—H5C···O4^vii	0.90	2.08	2.778 (4)	134
N6—H6D···O27^vi	0.89	1.86	2.726 (5)	163
N6—H6E···O11^vi	0.89	2.38	2.999 (3)	127
N6—H6E···O16^vi	0.89	2.06	2.852 (4)	147
N6—H6C···O17^vii	0.89	1.97	2.792 (3)	153
C1—H1B···O20^v	0.97	2.31	3.139 (5)	142
C3—H3B···O7^ii	0.97	2.56	3.460 (5)	154
C4—H4B···O3^v	0.97	2.52	3.157 (4)	123
C4—H4A···O8^vi	0.97	2.51	3.150 (4)	123
C5—H5B···O8^vi	0.97	2.57	3.186 (4)	122
C6—H6A···O1^vii	0.97	2.42	3.349 (4)	160
C7—H7B···O3^v	0.97	2.44	3.371 (4)	160
C7—H7A···O10^vi	0.97	2.44	3.214 (5)	136
C8—H8A···O5^iii	0.97	2.36	3.205 (4)	145
O24—H24A···O9	0.96 (2)	2.06 (2)	2.914 (4)	148 (4)
O24—H24B···O2	0.96 (2)	2.07 (2)	2.890 (4)	143 (3)
O24—H24B···O8^vi	0.96 (2)	2.39 (3)	2.967 (4)	118 (3)
O25—H25A···O12	0.96 (4)	1.97 (4)	2.896 (5)	162 (5)
O26—H26A···O11	0.96 (4)	2.11 (5)	3.072 (4)	175 (5)
O26—H26B···O13^v	0.96 (2)	1.82 (2)	2.771 (4)	173 (3)
O27—H27A···O25^vii	0.94 (4)	1.75 (3)	2.632 (7)	151 (5)
O27—H27B···O13^v	0.95 (4)	2.26 (3)	3.113 (5)	148 (5)

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