The novel chain-like anion _∞¹[NaMo₈O₂₆(mim)₂]³⁻ in (Hmim)₃[NaMo₈O₂₆(mim)₂] (mim is 1-methyl­imidazole)

Tris(1-methyl­imidazolium) bis­(1-methyl­imidazole)hexa­cosa­oxidoocta­molybdatesodium, (C₄H₇N₂)₃[NaMo₈O₂₆(C₄H₆N₂)₂], prepared from an aqueous solution containing Na₂MoO₄ and 1-methyl­imidazole, contains the novel chain-like anion _∞¹[NaMo₈O₂₆(mim)₂]³⁻ (mim is 1-methyl­imidazole). The [Mo₈O₂₆(mim)₂]⁴⁻ building unit, which lies across a center of inversion, is comprised of eight edge-sharing MoO₆ and MoO₅(N_mim) octa­hedra. These molybdate units are inter­linked by sodium, itself exhibiting a sixfold coordination with O atoms.

S1. Comment

Polyoxometalates (POMs) are of particular interest because of their fascinating structures, properties and potential applications, such as catalysis, sorption and magnetism (Müller & Pope, 1991; Cheetham, 1994; Proust et al., 2008). The class of materials is characterized by complex building units and a diverse chemical reactivity (Heyns et al., 1991; Wang et al., 1992). Molybdate-based POMs in particular have attracted a lot of attention since some of the largest inorganic clusters have been identified here, for instance, Na₄₈[H_xMo₃₆₈O₁₀₃₂(H₂O)₂₄₀(SO₄)₄₈].xH₂O with x ≈ 1000 (Müller et al., 2002). The fundamental building unit is quite often related to the well known octamolybdate [Mo₈O₂₆]^4-. With this study, we report a novel chain-like _∞¹[NaMo₈O₂₆(mim)₂]^3- anion (mim = 1-methylimidazole) that is constituted of sodium-interlinked [Mo₈O₂₆(mim)₂]^4- building units. Although, alkali-metal-interlinked chains of octamolybdate units have already been identified (McCann et al., 1994; Jia et al., 1999; Chen et al., 2005; Liu et al., 2006; Yu et al., 2008; Kobayashi et al., 2009), the title compound, (I), when examined in detail shows some significant structural differences.

According to single-crystal structure analysis, (Hmim)₃[NaMo₈O₂₆(mim)₂] contains the chain-like anion _∞¹[NaMo₈O₂₆(mim)₂]^3-, which is oriented in parallel to the crystallographic b axis. The molybdate unit exhibits a center of inversion, resulting in only four crystallographically independent Mo sites. Between the chains, protonated methylimidazole is incorporated as the cation (Fig. 1). In detail, the _∞¹[NaMo₈O₂₆(mim)₂]^3- ion is constituted of eight edge-sharing octahedra. The resulting [Mo₈O₂₆(mim)₂]^4- units are interlinked by sodium cations to form infinite chains. Here, sodium possesses sixfold coordination to the terminal O atoms of two molybdate units (Fig. 2). _∞¹[NaMo₈O₂₆(mim)₂]^3- – or _∞¹[NaMo₈O₂₆(N_mim)₂]^3- when only considering the coordinating N atom – can be compared, firstly, to the well known _∞¹[NaMo₈O₂₆]^3- building unit (McCann et al., 1994; Chen et al., 2005; Liu et al., 2006; Kobayashi et al., 2009) and, secondly, to [Mo₈O₂₈]^8-. Both _∞¹[NaMo₈O₂₆(N_mim)₂]^3- and _∞¹[NaMo₈O₂₆]^3- exhibit a chain-like interlinking of octamolybdate units via Na atoms (Fig. 3). However, because of to the different stoichiometry, the (MoO₆) octahedra in _∞¹[NaMo₈O₂₆]^3- show a higher degree of condensation. Moreover, the coordination between the octamolybdate units and sodium is different. This holds for the coordination number (sixfold and eightfold) as well as for the relative orientation of the octamolybdate unit inside the _∞¹[NaMo₈O₂₆(N_mim)₂]^3- and _∞¹[NaMo₈O₂₆]^3- chains. [Mo₈O₂₈]^8-, which is also comparable to [Mo₈O₂₆(N_mim)₂]^4- in the title compound, has been identified both in layer-type structures with a direct Mo—O—Mo interlinking between the octamolybdate units (Evain et al., 2006) and as an individual octamolybdate unit that is interlinked via hydrogen-bridge bonding only (Bharadwaj et al., 1986; You et al., 1989).

Regarding their coordination, the O atoms in _∞¹[NaMo₈O₂₆(mim)₂]^3- can be divided into six categories. First of all, one group of atoms is exclusively coordinated to molybdenum: ten terminal O atoms with bond distances (Mo—O_µ1) ranging from 1.698 (1) to 1.722 (3) Å; six atoms with twofold coordination and distances (Mo—O_µ2) of 1.742 (7)–2.271 (5) Å; two three-coordinated atoms with Mo—O_µ3 = 1.945 (4) Å; and finally two four-coordinated atoms with Mo—O_µ4 = 2.236 (3) Å. In the second group, the O atoms are coordinated to sodium as well as to molybdenum. Here, the 〈Na—O〉 distances average 2.377 (2) Å and the 〈Mo—O_Na〉 distances 1.909 (3) Å. All these distances as well as the variation with increasing coordination number are in aggreement with literature data (Evain et al., 2006; Bharadwaj et al., 1986; You et al., 1989). Finally, two Mo atoms are coordinated by 1-methylimidazole, resulting in an Mo—N bond length of 2.229 (9) Å, which is also in accordance with the literature (2.2–2.5 Å; Cotton & Ilsey, 1972; Brisdon & Woolf, 1978; Schrauzer et al., 1982). On the basis of the composition of the compound as well as with regard to coordination and bond distances, all Mo atoms exhibit an oxidation state of +6.

Related literature

For related literature, see: Bharadwaj et al. (1986); Brisdon & Woolf (1978); Cheetham (1994); Chen et al. (2005); Evain et al. (2006); Heyns et al. (1991); Jia et al. (1999); Kobayashi et al. (2009); Liu et al. (2006); Müller & Pope (1991); Müller et al. (2002); McCann et al. (1994); You et al. (1989); Yu et al. (2008); Zhai et al. (1992).

S2. Experimental

(Hmim)₃[NaMo₈O₂₆(mim)₂] was prepared from aqueous solutions containing water (5 ml), Na₂MoO₄ (200 mg, 0.97 mmol) and 1-methylimidazole (1.2 ml). This solution was stirred at room temperature with 30% H₂O₂ (1.0 ml) added dropwise at 263 K. The resulting dark-red–brown solution was stirred for an additional 2–4 h. During this period of time the red–brown solution turned to light yellow. Finally, the solution was concentrated by evacuation and left for crystallization at room temperature. After a few weeks, rectangular transparent and colorless crystals of the title compound were formed. A crystal suitable for crystal structure analysis was fixed onto a glass filament and coated in perfluorated oil (Kel-F).

S3. Refinement

H atoms were positioned geometrically [C—H = 0.93–0.96 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C,N)]. During structure refinement, one of the methylimidazolium cations was found to be disordered (Fig. 1). This was dealt with using split atom positions. When refining the relevant site occupation factors, values near 50% were identified, and these site occupancies were subsequently fixed at 0.5.

Computing details

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures

	Fig. 1. Figure 1: The unit cell of (Hmim)3[NaMo8O26(mim)2] with polyhedra indicating the chain-like anion ∞^1[NaMo8O26(mim)2]^3^- [in the electronic version of the paper (MoO6) octahedra: green; (NaO6) octahedra: blue]. For clarity H atoms have been omitted; the disordered 1-methylimidazolium unit (indicated as *) is shown with one position only.
	Fig. 2. Figure 2: The chain-like anion ∞^1[NaMo8O26(mim)2]^3^-.
	Fig. 3. Figure 3: Scheme illustrating the different condensation, interlinking and Na^+ coordination in ∞^1[NaMo8O26(Nmim)2]^3^- (a) and ∞^1[NaMo8O26]^3^- (b).

Tris(1-methylimidazolium) bis(1-methylimidazole)hexacosaoxidooctamolybdatesodium

Crystal data

(C4H7N2)3[NaMo8O26(C4H6N2)2]	F(000) = 1732
Mr = 1784.29	Dx = 2.253 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6846 reflections
a = 11.692 (2) Å	θ = 3.0–60.0°
b = 10.298 (2) Å	µ = 1.95 mm^−1
c = 22.190 (4) Å	T = 298 K
β = 100.12 (3)°	Rectangular, colorless
V = 2630.2 (9) Å^3	0.4 × 0.2 × 0.2 mm
Z = 2

Data collection

Stoe IPDS II diffractometer	7219 independent reflections
Radiation source: fine-focus sealed tube	5717 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
imaging plate diffraction system scans	θmax = 29.6°, θmin = 2.2°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1999)	h = −16→16
Tmin = 0.393, Tmax = 0.528	k = −14→14
22631 measured reflections	l = −30→25

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0602P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.002
7219 reflections	Δρmax = 1.11 e Å^−3
378 parameters	Δρmin = −0.96 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0032 (2)

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	Occ. (<1)
Mo1	0.36916 (3)	0.72008 (3)	0.579880 (16)	0.01950 (9)
Mo2	0.52428 (3)	0.93453 (3)	0.373499 (16)	0.02093 (9)
Mo3	0.59280 (3)	0.87367 (3)	0.533358 (15)	0.01805 (9)
Mo4	0.34864 (3)	0.75230 (3)	0.432644 (16)	0.02078 (9)
Na1	0.5000	0.5000	0.5000	0.0269 (5)
O1	0.2793 (3)	0.7499 (3)	0.63099 (15)	0.0293 (6)
O2	0.3566 (3)	0.5555 (3)	0.56340 (14)	0.0262 (6)
O3	0.5017 (2)	0.7235 (3)	0.51633 (13)	0.0211 (5)
O4	0.4645 (2)	0.8887 (3)	0.59393 (13)	0.0204 (5)
O5	0.2829 (2)	0.7866 (3)	0.50632 (13)	0.0225 (6)
O6	0.6501 (3)	0.9168 (3)	0.34484 (17)	0.0369 (8)
O7	0.4207 (3)	0.9657 (3)	0.31079 (15)	0.0331 (7)
O8	0.5733 (2)	1.0579 (3)	0.54859 (13)	0.0206 (5)
O9	0.4759 (3)	0.7601 (3)	0.38683 (14)	0.0245 (6)
O10	0.6536 (2)	0.8890 (3)	0.46729 (14)	0.0240 (6)
O11	0.7073 (2)	0.8319 (3)	0.58829 (15)	0.0272 (6)
O12	0.2323 (3)	0.8031 (3)	0.38030 (15)	0.0320 (7)
O13	0.3395 (3)	0.5852 (3)	0.43181 (14)	0.0269 (6)
N1	0.5129 (3)	0.6509 (3)	0.65255 (16)	0.0217 (6)
N2	0.6129 (3)	0.5135 (4)	0.71659 (17)	0.0275 (7)
C1	0.5821 (3)	0.7203 (4)	0.6984 (2)	0.0254 (8)
H1	0.5860	0.8103	0.7014	0.030*
C2	0.6436 (4)	0.6349 (4)	0.7383 (2)	0.0299 (9)
H2	0.6962	0.6553	0.7736	0.036*
C3	0.5350 (4)	0.5263 (4)	0.6652 (2)	0.0252 (8)
H3	0.5009	0.4574	0.6415	0.030*
C4	0.6617 (6)	0.3927 (5)	0.7433 (3)	0.0483 (15)
H4A	0.6180	0.3209	0.7235	0.072*
H4B	0.6584	0.3916	0.7862	0.072*
H4C	0.7412	0.3856	0.7379	0.072*
N3	0.0886 (3)	0.3841 (4)	0.4053 (2)	0.0336 (8)
N4	0.0731 (4)	0.3526 (5)	0.4999 (2)	0.0385 (9)
H4	0.0899	0.3486	0.5392	0.046*
C5	0.1431 (4)	0.3914 (5)	0.4637 (2)	0.0360 (10)
H5	0.2190	0.4198	0.4764	0.043*
C6	0.1397 (5)	0.4139 (6)	0.3510 (3)	0.0418 (12)
H6A	0.1813	0.3394	0.3403	0.063*
H6B	0.1923	0.4858	0.3598	0.063*
H6C	0.0791	0.4359	0.3175	0.063*
C7	−0.0208 (4)	0.3403 (6)	0.4051 (3)	0.0429 (12)
H7A	−0.0779	0.3269	0.3709	0.051*
C8	−0.0313 (4)	0.3195 (6)	0.4651 (3)	0.0416 (12)
H8	−0.0966	0.2888	0.4792	0.050*
N5	0.1214 (4)	0.3454 (5)	0.6223 (2)	0.0450 (11)
C9	0.0598 (5)	0.3210 (7)	0.6683 (3)	0.0516 (14)
H9A	−0.0195	0.3039	0.6621	0.062*	0.50
H9B	−0.0106	0.2769	0.6639	0.062*	0.50
C10A	0.2273 (10)	0.3675 (14)	0.6494 (6)	0.039 (3)*	0.50
H10A	0.2902	0.3797	0.6296	0.047*	0.50
N6A	0.2325 (9)	0.3701 (12)	0.7103 (5)	0.045 (2)*	0.50
C11A	0.1280 (12)	0.3249 (16)	0.7229 (7)	0.048 (3)*	0.50
H11A	0.1097	0.3025	0.7606	0.058*	0.50
C12A	0.3307 (13)	0.4082 (17)	0.7585 (7)	0.060 (3)*	0.50
H12A	0.3775	0.3333	0.7715	0.091*	0.50
H12B	0.3013	0.4437	0.7928	0.091*	0.50
H12C	0.3771	0.4722	0.7426	0.091*	0.50
C10B	0.2161 (11)	0.4118 (15)	0.6511 (6)	0.044 (3)*	0.50
H10B	0.2721	0.4460	0.6306	0.052*	0.50
N6B	0.2211 (9)	0.4233 (11)	0.7108 (5)	0.042 (2)*	0.50
C11B	0.1195 (11)	0.3727 (14)	0.7223 (6)	0.043 (3)*	0.50
H11B	0.0945	0.3730	0.7598	0.051*	0.50
C12B	0.3162 (14)	0.4805 (17)	0.7551 (8)	0.064 (4)*	0.50
H12D	0.3889	0.4446	0.7488	0.096*	0.50
H12E	0.3047	0.4613	0.7959	0.096*	0.50
H12F	0.3170	0.5729	0.7495	0.096*	0.50
C16	1.0905 (18)	1.022 (2)	0.5716 (11)	0.048 (4)	0.50
H16A	1.0483	1.0801	0.5935	0.073*	0.50
H16B	1.1641	1.0600	0.5682	0.073*	0.50
H16C	1.1031	0.9411	0.5933	0.073*	0.50
N7	0.8762 (13)	0.9657 (19)	0.4385 (12)	0.050 (4)	0.50
H7	0.8065	0.9526	0.4194	0.060*	0.50
C13	1.0651 (9)	0.9887 (13)	0.4576 (7)	0.050 (3)	0.50
H13	1.1425	0.9952	0.4531	0.060*	0.50
C14	0.9741 (14)	0.9677 (14)	0.4136 (8)	0.057 (3)	0.50
H14	0.9771	0.9562	0.3724	0.068*	0.50
N8	1.0232 (9)	0.9987 (15)	0.5100 (8)	0.047 (3)	0.50
C15	0.9084 (12)	0.9879 (13)	0.4981 (10)	0.057 (4)	0.50
H15	0.8590	0.9946	0.5265	0.069*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01900 (14)	0.02007 (15)	0.01890 (17)	−0.00250 (11)	0.00188 (11)	0.00202 (11)
Mo2	0.02534 (16)	0.01955 (15)	0.01828 (17)	−0.00030 (11)	0.00487 (12)	−0.00039 (12)
Mo3	0.01766 (14)	0.01667 (14)	0.01949 (17)	−0.00037 (10)	0.00230 (11)	0.00049 (11)
Mo4	0.02299 (15)	0.01944 (15)	0.01832 (17)	−0.00298 (11)	−0.00077 (12)	0.00073 (12)
Na1	0.0291 (11)	0.0209 (10)	0.0288 (13)	0.0026 (8)	0.0003 (9)	−0.0004 (9)
O1	0.0252 (13)	0.0368 (17)	0.0259 (16)	−0.0020 (12)	0.0042 (12)	0.0002 (13)
O2	0.0279 (13)	0.0261 (14)	0.0223 (15)	−0.0058 (11)	−0.0019 (11)	0.0046 (11)
O3	0.0231 (12)	0.0168 (12)	0.0233 (14)	−0.0025 (9)	0.0036 (10)	−0.0009 (10)
O4	0.0222 (12)	0.0180 (12)	0.0213 (14)	−0.0038 (9)	0.0047 (10)	−0.0010 (10)
O5	0.0193 (11)	0.0261 (13)	0.0210 (14)	−0.0019 (10)	0.0003 (10)	0.0038 (11)
O6	0.0423 (18)	0.0338 (17)	0.037 (2)	0.0039 (14)	0.0148 (15)	0.0045 (14)
O7	0.0464 (18)	0.0230 (15)	0.0268 (17)	−0.0024 (13)	−0.0018 (14)	−0.0014 (12)
O8	0.0224 (12)	0.0163 (12)	0.0232 (14)	−0.0009 (9)	0.0042 (10)	0.0006 (10)
O9	0.0314 (14)	0.0193 (13)	0.0232 (15)	0.0003 (10)	0.0059 (11)	−0.0004 (11)
O10	0.0241 (12)	0.0234 (13)	0.0250 (15)	0.0011 (10)	0.0057 (11)	0.0003 (11)
O11	0.0251 (13)	0.0259 (14)	0.0290 (16)	0.0005 (11)	0.0004 (12)	0.0015 (12)
O12	0.0324 (15)	0.0378 (17)	0.0222 (16)	−0.0035 (13)	−0.0046 (12)	0.0009 (13)
O13	0.0331 (14)	0.0230 (14)	0.0233 (15)	−0.0034 (11)	0.0013 (12)	−0.0027 (11)
N1	0.0259 (15)	0.0204 (15)	0.0187 (16)	0.0006 (12)	0.0034 (12)	0.0017 (12)
N2	0.0322 (17)	0.0240 (17)	0.0235 (18)	0.0026 (13)	−0.0030 (14)	0.0044 (13)
C1	0.0273 (18)	0.0227 (18)	0.024 (2)	0.0007 (14)	0.0001 (15)	−0.0008 (15)
C2	0.032 (2)	0.028 (2)	0.027 (2)	−0.0038 (16)	−0.0027 (17)	0.0027 (17)
C3	0.0286 (18)	0.0233 (18)	0.023 (2)	−0.0026 (14)	0.0024 (15)	0.0011 (15)
C4	0.062 (3)	0.030 (2)	0.043 (3)	0.010 (2)	−0.019 (3)	0.008 (2)
N3	0.0287 (18)	0.036 (2)	0.036 (2)	−0.0029 (15)	0.0038 (15)	−0.0026 (17)
N4	0.037 (2)	0.042 (2)	0.037 (2)	−0.0041 (17)	0.0066 (17)	−0.0017 (18)
C5	0.0265 (19)	0.046 (3)	0.035 (3)	−0.0056 (18)	0.0043 (18)	−0.004 (2)
C6	0.044 (3)	0.049 (3)	0.033 (3)	−0.001 (2)	0.009 (2)	−0.001 (2)
C7	0.027 (2)	0.046 (3)	0.052 (3)	−0.0052 (19)	−0.001 (2)	0.003 (2)
C8	0.029 (2)	0.044 (3)	0.052 (3)	−0.0078 (19)	0.008 (2)	0.005 (2)
N5	0.050 (2)	0.047 (3)	0.040 (3)	−0.009 (2)	0.014 (2)	0.004 (2)
C9	0.040 (3)	0.066 (4)	0.053 (4)	−0.002 (3)	0.018 (2)	0.002 (3)
C16	0.037 (13)	0.042 (7)	0.067 (12)	−0.011 (9)	0.011 (10)	0.006 (6)
N7	0.012 (6)	0.046 (7)	0.093 (13)	−0.005 (5)	0.015 (6)	0.010 (7)
C13	0.025 (5)	0.056 (7)	0.068 (9)	−0.002 (4)	0.006 (5)	0.002 (7)
C14	0.046 (7)	0.053 (8)	0.072 (10)	−0.001 (6)	0.012 (7)	0.009 (7)
N8	0.035 (11)	0.036 (4)	0.072 (13)	0.010 (7)	0.012 (7)	0.015 (6)
C15	0.035 (7)	0.042 (6)	0.098 (14)	0.004 (5)	0.018 (9)	0.004 (7)

Geometric parameters (Å, º)

Mo1—O1	1.704 (3)	N3—C5	1.342 (6)
Mo1—O2	1.734 (3)	N3—C7	1.355 (6)
Mo1—O5	1.890 (3)	N3—C6	1.469 (7)
Mo1—O4	2.058 (3)	N4—C5	1.306 (7)
Mo1—N1	2.232 (3)	N4—C8	1.369 (6)
Mo1—O3	2.271 (3)	N4—H4	0.8600
Mo1—Na1	3.4017 (7)	C5—H5	0.9300
Mo2—O7	1.707 (3)	C6—H6A	0.9600
Mo2—O6	1.712 (4)	C6—H6B	0.9600
Mo2—O9	1.922 (3)	C6—H6C	0.9600
Mo2—O4^i	1.954 (3)	C7—C8	1.374 (9)
Mo2—O8^i	2.233 (3)	C7—H7A	0.9300
Mo2—O10	2.394 (3)	C8—H8	0.9300
Mo3—O11	1.700 (3)	N5—C10A	1.298 (13)
Mo3—O10	1.746 (3)	N5—C10B	1.362 (14)
Mo3—O3	1.879 (3)	N5—C9	1.372 (8)
Mo3—O8	1.948 (3)	C9—C11A	1.328 (15)
Mo3—O4	2.189 (3)	C9—C11B	1.383 (15)
Mo3—O8^i	2.516 (3)	C9—H9A	0.9300
Mo4—O12	1.708 (3)	C9—H9B	0.9300
Mo4—O13	1.724 (3)	C10A—N6A	1.343 (17)
Mo4—O9	1.946 (3)	C10A—H10A	0.9300
Mo4—O5	1.957 (3)	N6A—C11A	1.380 (18)
Mo4—O8^i	2.166 (3)	N6A—C12A	1.478 (18)
Mo4—O3	2.360 (3)	C11A—H11A	0.9300
Mo4—Na1	3.3447 (7)	C12A—H12A	0.9600
Na1—O3	2.329 (3)	C12A—H12B	0.9600
Na1—O3^ii	2.329 (3)	C12A—H12C	0.9600
Na1—O13^ii	2.363 (3)	C10B—N6B	1.321 (17)
Na1—O13	2.363 (3)	C10B—H10B	0.9300
Na1—O2	2.438 (3)	N6B—C11B	1.362 (16)
Na1—O2^ii	2.439 (3)	N6B—C12B	1.471 (18)
Na1—Mo4^ii	3.3447 (7)	C11B—H11B	0.9300
Na1—Mo1^ii	3.4017 (7)	C12B—H12D	0.9600
O4—Mo2^i	1.954 (3)	C12B—H12E	0.9600
O8—Mo4^i	2.166 (3)	C12B—H12F	0.9600
O8—Mo2^i	2.233 (3)	C16—N8	1.47 (3)
O8—Mo3^i	2.516 (3)	C16—H16A	0.9600
N1—C3	1.330 (5)	C16—H16B	0.9600
N1—C1	1.381 (5)	C16—H16C	0.9600
N2—C3	1.335 (5)	N7—C15	1.33 (3)
N2—C2	1.365 (6)	N7—C14	1.356 (18)
N2—C4	1.452 (6)	N7—H7	0.8600
C1—C2	1.362 (6)	C13—C14	1.33 (2)
C1—H1	0.9300	C13—N8	1.34 (3)
C2—H2	0.9300	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—H4A	0.9600	N8—C15	1.326 (18)
C4—H4B	0.9600	C15—H15	0.9300
C4—H4C	0.9600
O1—Mo1—O2	106.08 (15)	Mo4^ii—Na1—Mo1	122.399 (15)
O1—Mo1—O5	102.21 (14)	Mo4—Na1—Mo1	57.603 (15)
O2—Mo1—O5	99.18 (13)	Mo1^ii—Na1—Mo1	180.0
O1—Mo1—O4	97.37 (14)	Mo1—O2—Na1	108.03 (14)
O2—Mo1—O4	151.66 (13)	Mo3—O3—Mo1	108.20 (13)
O5—Mo1—O4	91.01 (12)	Mo3—O3—Na1	146.51 (14)
O1—Mo1—N1	92.91 (14)	Mo1—O3—Na1	95.36 (10)
O2—Mo1—N1	82.28 (13)	Mo3—O3—Mo4	112.29 (13)
O5—Mo1—N1	163.66 (13)	Mo1—O3—Mo4	89.12 (10)
O4—Mo1—N1	80.83 (12)	Na1—O3—Mo4	90.99 (9)
O1—Mo1—O3	168.04 (13)	Mo2^i—O4—Mo1	147.30 (15)
O2—Mo1—O3	85.74 (13)	Mo2^i—O4—Mo3	106.52 (12)
O5—Mo1—O3	77.13 (11)	Mo1—O4—Mo3	105.00 (12)
O4—Mo1—O3	70.77 (11)	Mo1—O5—Mo4	115.30 (14)
N1—Mo1—O3	86.79 (12)	Mo3—O8—Mo4^i	148.63 (14)
O1—Mo1—Na1	148.56 (11)	Mo3—O8—Mo2^i	105.05 (12)
O2—Mo1—Na1	42.97 (11)	Mo4^i—O8—Mo2^i	94.31 (11)
O5—Mo1—Na1	90.70 (9)	Mo3—O8—Mo3^i	104.27 (11)
O4—Mo1—Na1	111.10 (8)	Mo4^i—O8—Mo3^i	97.58 (10)
N1—Mo1—Na1	79.24 (9)	Mo2^i—O8—Mo3^i	96.63 (10)
O3—Mo1—Na1	42.97 (7)	Mo2—O9—Mo4	113.08 (14)
O7—Mo2—O6	104.47 (18)	Mo3—O10—Mo2	117.35 (14)
O7—Mo2—O9	96.63 (14)	Mo4—O13—Na1	108.84 (13)
O6—Mo2—O9	104.65 (15)	C3—N1—C1	106.1 (3)
O7—Mo2—O4^i	96.79 (14)	C3—N1—Mo1	123.7 (3)
O6—Mo2—O4^i	103.33 (15)	C1—N1—Mo1	129.5 (3)
O9—Mo2—O4^i	144.70 (13)	C3—N2—C2	108.0 (3)
O7—Mo2—O8^i	103.83 (15)	C3—N2—C4	126.4 (4)
O6—Mo2—O8^i	151.67 (14)	C2—N2—C4	125.5 (4)
O9—Mo2—O8^i	73.10 (11)	C2—C1—N1	108.6 (4)
O4^i—Mo2—O8^i	72.03 (11)	C2—C1—H1	125.7
O7—Mo2—O10	174.14 (15)	N1—C1—H1	125.7
O6—Mo2—O10	81.32 (14)	C1—C2—N2	106.6 (4)
O9—Mo2—O10	80.88 (11)	C1—C2—H2	126.7
O4^i—Mo2—O10	82.51 (11)	N2—C2—H2	126.7
O8^i—Mo2—O10	70.40 (10)	N1—C3—N2	110.7 (4)
O11—Mo3—O10	103.85 (15)	N1—C3—H3	124.6
O11—Mo3—O3	106.45 (14)	N2—C3—H3	124.6
O10—Mo3—O3	101.89 (13)	N2—C4—H4A	109.5
O11—Mo3—O8	102.92 (13)	N2—C4—H4B	109.5
O10—Mo3—O8	97.76 (13)	H4A—C4—H4B	109.5
O3—Mo3—O8	139.24 (12)	N2—C4—H4C	109.5
O11—Mo3—O4	96.66 (13)	H4A—C4—H4C	109.5
O10—Mo3—O4	159.05 (12)	H4B—C4—H4C	109.5
O3—Mo3—O4	75.89 (11)	C5—N3—C7	108.0 (5)
O8—Mo3—O4	73.17 (11)	C5—N3—C6	126.0 (4)
O11—Mo3—O8^i	178.15 (12)	C7—N3—C6	125.9 (5)
O10—Mo3—O8^i	75.18 (11)	C5—N4—C8	108.8 (5)
O3—Mo3—O8^i	75.34 (10)	C5—N4—H4	125.6
O8—Mo3—O8^i	75.73 (11)	C8—N4—H4	125.6
O4—Mo3—O8^i	84.19 (10)	N4—C5—N3	109.5 (4)
O12—Mo4—O13	104.93 (15)	N4—C5—H5	125.2
O12—Mo4—O9	102.85 (15)	N3—C5—H5	125.2
O13—Mo4—O9	95.02 (14)	N3—C6—H6A	109.5
O12—Mo4—O5	97.48 (15)	N3—C6—H6B	109.5
O13—Mo4—O5	98.99 (14)	H6A—C6—H6B	109.5
O9—Mo4—O5	151.38 (12)	N3—C6—H6C	109.5
O12—Mo4—O8^i	96.48 (14)	H6A—C6—H6C	109.5
O13—Mo4—O8^i	157.80 (12)	H6B—C6—H6C	109.5
O9—Mo4—O8^i	74.21 (11)	N3—C7—C8	107.1 (5)
O5—Mo4—O8^i	83.74 (12)	N3—C7—H7A	126.5
O12—Mo4—O3	167.59 (14)	C8—C7—H7A	126.5
O13—Mo4—O3	85.41 (12)	N4—C8—C7	106.6 (5)
O9—Mo4—O3	82.68 (12)	N4—C8—H8	126.7
O5—Mo4—O3	73.77 (11)	C7—C8—H8	126.7
O8^i—Mo4—O3	74.14 (10)	C10A—N5—C9	105.6 (7)
O12—Mo4—Na1	146.86 (12)	C10B—N5—C9	103.4 (7)
O13—Mo4—Na1	41.97 (10)	C11A—C9—N5	111.3 (8)
O9—Mo4—Na1	82.67 (9)	N5—C9—C11B	108.8 (7)
O5—Mo4—Na1	91.24 (8)	C11A—C9—H9A	124.4
O8^i—Mo4—Na1	116.29 (7)	N5—C9—H9A	124.4
O3—Mo4—Na1	44.13 (7)	C11B—C9—H9A	122.7
O3—Na1—O3^ii	180.0	C11A—C9—H9B	119.3
O3—Na1—O13^ii	106.45 (10)	N5—C9—H9B	125.6
O3^ii—Na1—O13^ii	73.55 (10)	C11B—C9—H9B	125.5
O3—Na1—O13	73.55 (10)	N5—C10A—N6A	109.9 (10)
O3^ii—Na1—O13	106.45 (10)	N5—C10A—H10A	125.0
O13^ii—Na1—O13	180.00 (13)	N6A—C10A—H10A	125.0
O3—Na1—O2	70.51 (10)	C10A—N6A—C11A	108.1 (11)
O3^ii—Na1—O2	109.49 (10)	C10A—N6A—C12A	128.7 (11)
O13^ii—Na1—O2	105.48 (11)	C11A—N6A—C12A	123.1 (12)
O13—Na1—O2	74.52 (11)	C9—C11A—N6A	103.8 (12)
O3—Na1—O2^ii	109.49 (10)	C9—C11A—H11A	128.1
O3^ii—Na1—O2^ii	70.51 (10)	N6A—C11A—H11A	128.1
O13^ii—Na1—O2^ii	74.52 (11)	N6B—C10B—N5	113.9 (11)
O13—Na1—O2^ii	105.48 (11)	N6B—C10B—H10B	123.0
O2—Na1—O2^ii	180.00 (14)	N5—C10B—H10B	123.0
O3—Na1—Mo4^ii	135.12 (7)	C10B—N6B—C11B	105.4 (11)
O3^ii—Na1—Mo4^ii	44.88 (7)	C10B—N6B—C12B	127.0 (12)
O13^ii—Na1—Mo4^ii	29.19 (7)	C11B—N6B—C12B	127.6 (12)
O13—Na1—Mo4^ii	150.81 (7)	N6B—C11B—C9	108.1 (11)
O2—Na1—Mo4^ii	106.73 (7)	N6B—C11B—H11B	126.0
O2^ii—Na1—Mo4^ii	73.27 (7)	C9—C11B—H11B	126.0
O3—Na1—Mo4	44.88 (7)	N6B—C12B—H12D	109.5
O3^ii—Na1—Mo4	135.12 (7)	N6B—C12B—H12E	109.5
O13^ii—Na1—Mo4	150.81 (7)	H12D—C12B—H12E	109.5
O13—Na1—Mo4	29.19 (7)	N6B—C12B—H12F	109.5
O2—Na1—Mo4	73.27 (7)	H12D—C12B—H12F	109.5
O2^ii—Na1—Mo4	106.73 (7)	H12E—C12B—H12F	109.5
Mo4^ii—Na1—Mo4	180.0	C15—N7—C14	106.9 (17)
O3—Na1—Mo1^ii	138.33 (7)	C15—N7—H7	126.6
O3^ii—Na1—Mo1^ii	41.67 (7)	C14—N7—H7	126.6
O13^ii—Na1—Mo1^ii	72.95 (8)	C14—C13—N8	106.3 (12)
O13—Na1—Mo1^ii	107.05 (8)	C14—C13—H13	126.9
O2—Na1—Mo1^ii	151.01 (7)	N8—C13—H13	126.9
O2^ii—Na1—Mo1^ii	28.99 (7)	C13—C14—N7	109.1 (19)
Mo4^ii—Na1—Mo1^ii	57.601 (15)	C13—C14—H14	125.4
Mo4—Na1—Mo1^ii	122.397 (15)	N7—C14—H14	125.4
O3—Na1—Mo1	41.67 (7)	C15—N8—C13	109.5 (13)
O3^ii—Na1—Mo1	138.33 (7)	C15—N8—C16	123.7 (17)
O13^ii—Na1—Mo1	107.05 (8)	C13—N8—C16	126.8 (13)
O13—Na1—Mo1	72.95 (8)	N8—C15—N7	108.2 (15)
O2—Na1—Mo1	29.00 (7)	N8—C15—H15	125.9
O2^ii—Na1—Mo1	151.01 (7)	N7—C15—H15	125.9

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