Octa-kis[2,2',5,5'-tetra-thia-fulvalenium(0.5+)] bis-[hexa-molybdate(2-)] acetonitrile solvate.

The asymmetric unit of the title compound, (C(6)H(4)S(4))(8)[Mo(6)O(19)](2)·CH(3)CN, contains two halves of two centrosymmetric [Mo(6)O(19)](2-) hexa-molybdate anions, which are each built up from six distorted MoO(6) octa-hedra sharing common edges and one common vertex at the central O atom, six tetra-thia-fulvalene cations (three of which are located on mirror planes) to balance the charge and a half of an acetonitrile solvent mol-ecule, likewise located on a mirror plane. The two central hexa-molybdate O atoms occupy special positions 2a and 2d, respectively. The cations and anions are inter-linked through C-H⋯O contacts.

Related literature

For the chemical and physical properties of polyoxo­molybdates, see: Shi et al. (2006 ▶); Wang et al. (2004 ▶); Hagrman et al. (1999 ▶). For the structure of ammonium tris­(tetra­ethyl­ammonium) hexa­cosa­oxidoocta­molybdate, see: Zebiri et al. (2008 ▶). The title compound is isostructural with its tungsten analogue, see: Triki et al. (1993 ▶). The structure of the anions is the same as that in bis­[2-(pyrimidin-2-yl­amino)pyrimidinium] hexa­molybdate, see: Yeh et al. (2008 ▶). For Mo—O distances, see: Boyle et al. (1998 ▶); Deng et al. (2006 ▶); Maeda et al. (2006 ▶).

Experimental

Crystal data

(C6H4S4)8[Mo6O19]2·C2H3N

M = 3434.99

Monoclinic,

a = 14.3179 (8) Å

b = 20.2299 (10) Å

c = 16.7625 (10) Å

β = 101.266 (3)°

V = 4761.7 (5) Å3

Z = 2

Mo Kα radiation

μ = 2.31 mm−1

T = 100 K

0.25 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.597, T max = 0.802

45527 measured reflections

11170 independent reflections

8144 reflections with I > 2σ(I)

R int = 0.072

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.073

S = 1

11170 reflections

629 parameters

H-atom parameters constrained

Δρmax = 0.88 e Å−3

Δρmin = −0.70 e Å−3

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PARST (Nardelli, 1995 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031092/hg2545sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031092/hg2545Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C6H4S4)8[Mo6O19]2·C2H3N	F(000) = 3324
Mr = 3434.99	Dx = 2.396 Mg m−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2190 reflections
a = 14.3179 (8) Å	θ = 2.8–27.3°
b = 20.2299 (10) Å	µ = 2.31 mm−1
c = 16.7625 (10) Å	T = 100 K
β = 101.266 (3)°	Plates, colourless
V = 4761.7 (5) Å3	0.25 × 0.15 × 0.1 mm
Z = 2

Nonius KappaCCD diffractometer	11170 independent reflections
Radiation source: fine-focus sealed X-ray tube	8144 reflections with I > 2σ(I)
graphite	Rint = 0.072
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
Tmin = 0.597, Tmax = 0.802	k = −26→26
45527 measured reflections	l = −21→21

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.073	w = 1/[σ2(Fo2) + (0.021P)2] where P = (Fo2 + 2Fc2)/3
S = 1	(Δ/σ)max = 0.003
11170 reflections	Δρmax = 0.88 e Å−3
629 parameters	Δρmin = −0.70 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.08 (2)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mo1	0.56723 (3)	0.411518 (19)	0.58067 (2)	0.01535 (9)
Mo2	0.37343 (3)	0.500847 (18)	0.56738 (2)	0.01262 (8)
Mo5	0.41862 (3)	0.425991 (19)	0.40423 (2)	0.01562 (9)
Mo3	0.09471 (3)	0.007942 (18)	0.90255 (2)	0.01440 (9)
Mo4	0.12057 (3)	0.050345 (18)	1.09450 (2)	0.01550 (9)
Mo6	−0.06607 (3)	0.102673 (18)	0.96110 (2)	0.01461 (9)
S4	0.69926 (8)	0.32365 (5)	0.32774 (7)	0.0171 (2)
S1	0.83864 (9)	0.32314 (6)	0.19478 (7)	0.0194 (3)
S2	0.31973 (9)	0.32349 (5)	0.68472 (7)	0.0193 (3)
S3	1.13888 (8)	0.41650 (5)	0.47871 (7)	0.0141 (2)
S5	0.85700 (8)	0.41673 (5)	0.53863 (7)	0.0134 (2)
S6	0.94719 (8)	0.41562 (5)	0.37833 (7)	0.0148 (2)
S7	1.04691 (8)	0.41757 (5)	0.64209 (7)	0.0158 (2)
S8	0.19893 (11)	0.75	0.39380 (10)	0.0162 (3)
S9	0.38303 (8)	0.16665 (6)	0.03769 (7)	0.0186 (3)
S10	−0.09582 (11)	0.75	0.43604 (10)	0.0167 (3)
S11	0.01173 (12)	0.75	0.27956 (10)	0.0187 (4)
S12	0.09410 (11)	0.75	0.54638 (9)	0.0157 (3)
S13	0.57537 (8)	0.16549 (5)	0.13620 (7)	0.0169 (2)
S14	0.47171 (8)	0.16799 (6)	−0.12637 (7)	0.0174 (2)
S15	0.66417 (8)	0.16465 (6)	−0.02771 (7)	0.0204 (3)
S18	0.21028 (8)	0.32348 (5)	0.83822 (7)	0.0177 (2)
O1	0	0	1	0.0106 (9)
O2	0.5	0.5	0.5	0.0119 (9)
O5	0.4513 (2)	0.43340 (14)	0.62260 (17)	0.0153 (7)
O4	0.2801 (2)	0.50318 (14)	0.61450 (18)	0.0159 (7)
O3	0.6587 (2)	0.43007 (14)	0.51664 (18)	0.0169 (7)
O6	0.4587 (2)	0.56620 (14)	0.62598 (17)	0.0150 (7)
O12	0.4888 (2)	0.36829 (14)	0.49387 (18)	0.0161 (7)
O7	0.6179 (2)	0.49293 (14)	0.64424 (17)	0.0166 (7)
O8	−0.0228 (2)	−0.03840 (14)	0.84668 (18)	0.0195 (7)
O9	0.3326 (2)	0.44003 (14)	0.47865 (18)	0.0159 (7)
O10	0.0391 (2)	0.12578 (13)	1.03983 (18)	0.0166 (7)
O11	0.0124 (2)	0.08657 (13)	0.88356 (18)	0.0178 (7)
O13	0.1560 (2)	−0.03770 (14)	1.10491 (19)	0.0204 (7)
O14	0.1549 (2)	0.01313 (14)	0.82549 (19)	0.0215 (7)
O15	0.1685 (2)	0.05279 (13)	0.99087 (18)	0.0158 (7)
O16	0.3610 (2)	0.36980 (15)	0.33835 (19)	0.0234 (8)
O19	−0.1227 (2)	0.17476 (14)	0.93106 (19)	0.0221 (7)
O18	0.2048 (2)	0.09129 (14)	1.1612 (2)	0.0245 (8)
O17	0.6166 (2)	0.35055 (15)	0.64365 (19)	0.0245 (8)
O20	0.1308 (2)	−0.07465 (14)	0.95163 (19)	0.0200 (7)
C1	0.7991 (4)	0.25	0.2352 (4)	0.0127 (13)
C4	0.9789 (3)	0.4167 (2)	0.5449 (3)	0.0145 (9)
C3	0.1983 (5)	0.75	0.2897 (4)	0.0204 (15)
H3	0.2548	0.75	0.2703	0.025*
C2	0.7423 (4)	0.25	0.2902 (4)	0.0143 (13)
C7	0.1143 (5)	0.75	0.2388 (4)	0.0224 (15)
H7	0.1107	0.75	0.1828	0.027*
C8	0.0738 (5)	0.75	0.3820 (4)	0.0170 (14)
C6	0.8635 (3)	0.4170 (2)	0.6423 (3)	0.0166 (10)
H6	0.8088	0.4169	0.6643	0.02*
C5	0.9505 (3)	0.4174 (2)	0.6901 (3)	0.0178 (10)
H5	0.9585	0.4176	0.7465	0.021*
C11	0.2420 (4)	0.25	0.7930 (4)	0.0149 (13)
C10	0.2854 (4)	0.25	0.7292 (4)	0.0160 (14)
C15	0.5424 (3)	0.1666 (2)	−0.0301 (3)	0.0174 (10)
C16	0.5044 (3)	0.1662 (2)	0.0406 (3)	0.0172 (10)
C13	0.5655 (3)	0.1660 (2)	−0.1775 (3)	0.0216 (11)
H13	0.5553	0.166	−0.234	0.026*
C12	0.1572 (3)	0.2831 (2)	0.9098 (3)	0.0223 (11)
H12	0.1297	0.3068	0.9468	0.027*
C14	0.6539 (3)	0.1643 (2)	−0.1321 (3)	0.0210 (11)
H14	0.7074	0.163	−0.1559	0.025*
C9	0.3514 (3)	0.2832 (2)	0.6016 (3)	0.0231 (11)
H9	0.3676	0.307	0.5588	0.028*
C22	1.0177 (3)	0.41639 (19)	0.4749 (3)	0.0132 (9)
C17	0.4818 (3)	0.1637 (2)	0.1873 (3)	0.0180 (10)
H17	0.4923	0.1623	0.2438	0.022*
C18	0.3931 (3)	0.1643 (2)	0.1421 (3)	0.0185 (10)
H18	0.3396	0.1635	0.1659	0.022*
C21	0.0295 (4)	0.75	0.4457 (4)	0.0165 (14)
C20	0.6422 (3)	0.2833 (2)	0.3968 (3)	0.0211 (11)
H20	0.6127	0.307	0.4325	0.025*
C19	0.9255 (3)	0.2830 (2)	0.1533 (3)	0.0235 (11)
H19	0.9704	0.3067	0.1319	0.028*
C24	1.0417 (3)	0.4110 (2)	0.3287 (3)	0.0197 (10)
H24	1.0322	0.4084	0.2723	0.024*
C23	1.1297 (3)	0.4114 (2)	0.3748 (3)	0.0174 (10)
H23	1.1836	0.4089	0.3516	0.021*
C26	−0.0077 (4)	0.75	0.5908 (4)	0.0184 (14)
H26	−0.0027	0.75	0.6469	0.022*
C25	−0.0915 (5)	0.75	0.5408 (4)	0.0186 (14)
H25	−0.1474	0.75	0.5613	0.022*
S16	0.43075 (9)	0.99818 (6)	0.10594 (7)	0.0200 (3)
S27	0.63331 (9)	0.99422 (6)	0.09037 (7)	0.0203 (3)
C27	0.5135 (3)	0.9988 (2)	0.0403 (3)	0.0166 (10)
C29	0.5178 (4)	0.9954 (2)	0.1949 (3)	0.0245 (11)
H29	0.5008	0.9954	0.2457	0.029*
C28	0.6083 (4)	0.9931 (2)	0.1884 (3)	0.0247 (11)
H28	0.6568	0.991	0.2342	0.03*
N1	0.1799 (6)	0.25	0.1110 (5)	0.061 (2)
C30	0.1822 (6)	0.25	0.1791 (7)	0.049 (3)
C31	0.1876 (6)	0.25	0.2689 (6)	0.050 (2)
H31A	0.1353	0.2749	0.2815	0.076*	0.5
H31B	0.2466	0.2697	0.2953	0.076*	0.5
H31C	0.1845	0.2054	0.2876	0.076*	0.5

	U11	U22	U33	U12	U13	U23
Mo1	0.0150 (2)	0.0195 (2)	0.0125 (2)	0.00474 (16)	0.00522 (16)	0.00528 (16)
Mo2	0.01036 (18)	0.0189 (2)	0.00921 (18)	0.00057 (16)	0.00335 (15)	0.00047 (15)
Mo5	0.0138 (2)	0.0217 (2)	0.01209 (19)	−0.00355 (16)	0.00420 (16)	−0.00492 (16)
Mo3	0.0168 (2)	0.0162 (2)	0.01122 (19)	−0.00087 (16)	0.00517 (16)	0.00087 (15)
Mo4	0.0164 (2)	0.0170 (2)	0.01202 (19)	−0.00345 (16)	0.00029 (16)	−0.00233 (15)
Mo6	0.0185 (2)	0.0131 (2)	0.01240 (19)	0.00125 (16)	0.00348 (16)	0.00127 (15)
S4	0.0199 (6)	0.0162 (6)	0.0154 (6)	0.0025 (5)	0.0038 (5)	−0.0010 (5)
S1	0.0213 (6)	0.0191 (6)	0.0189 (6)	−0.0011 (5)	0.0062 (5)	0.0029 (5)
S2	0.0241 (7)	0.0177 (6)	0.0166 (6)	−0.0050 (5)	0.0055 (5)	0.0010 (5)
S3	0.0110 (5)	0.0164 (6)	0.0148 (6)	−0.0019 (4)	0.0023 (5)	−0.0003 (4)
S5	0.0114 (5)	0.0163 (6)	0.0122 (5)	0.0001 (4)	0.0018 (4)	0.0009 (4)
S6	0.0148 (6)	0.0171 (6)	0.0117 (5)	−0.0021 (4)	0.0006 (5)	0.0014 (4)
S7	0.0152 (6)	0.0186 (6)	0.0121 (5)	−0.0005 (5)	−0.0008 (5)	0.0000 (4)
S8	0.0155 (8)	0.0175 (8)	0.0151 (8)	0	0.0017 (7)	0
S9	0.0149 (6)	0.0223 (6)	0.0184 (6)	−0.0005 (5)	0.0028 (5)	−0.0022 (5)
S10	0.0151 (8)	0.0176 (8)	0.0161 (8)	0	−0.0006 (7)	0
S11	0.0227 (9)	0.0184 (8)	0.0124 (8)	0	−0.0027 (7)	0
S12	0.0155 (8)	0.0173 (8)	0.0126 (8)	0	−0.0016 (7)	0
S13	0.0163 (6)	0.0215 (6)	0.0127 (6)	0.0001 (5)	0.0021 (5)	−0.0004 (5)
S14	0.0188 (6)	0.0213 (6)	0.0118 (6)	0.0011 (5)	0.0019 (5)	−0.0001 (5)
S15	0.0158 (6)	0.0278 (7)	0.0182 (6)	0.0030 (5)	0.0046 (5)	0.0017 (5)
S18	0.0210 (6)	0.0147 (6)	0.0177 (6)	−0.0002 (5)	0.0046 (5)	−0.0021 (5)
O1	0.013 (2)	0.012 (2)	0.007 (2)	−0.0012 (17)	0.0024 (17)	−0.0010 (16)
O2	0.010 (2)	0.016 (2)	0.011 (2)	0.0002 (17)	0.0043 (18)	0.0001 (17)
O5	0.0175 (17)	0.0193 (16)	0.0103 (15)	0.0010 (13)	0.0054 (13)	0.0021 (12)
O4	0.0135 (16)	0.0218 (17)	0.0133 (16)	−0.0001 (13)	0.0047 (13)	−0.0004 (13)
O3	0.0134 (16)	0.0221 (16)	0.0164 (17)	0.0041 (13)	0.0052 (14)	0.0028 (13)
O6	0.0153 (16)	0.0199 (16)	0.0109 (15)	−0.0017 (13)	0.0053 (13)	−0.0024 (13)
O12	0.0207 (17)	0.0149 (16)	0.0149 (16)	−0.0004 (13)	0.0091 (14)	−0.0004 (12)
O7	0.0131 (16)	0.0259 (17)	0.0102 (16)	0.0016 (13)	0.0012 (13)	0.0014 (13)
O8	0.0240 (18)	0.0230 (17)	0.0114 (16)	−0.0007 (14)	0.0032 (14)	−0.0036 (13)
O9	0.0137 (16)	0.0207 (17)	0.0149 (16)	−0.0036 (13)	0.0068 (13)	−0.0031 (13)
O10	0.0193 (17)	0.0122 (15)	0.0188 (17)	−0.0036 (13)	0.0049 (14)	−0.0019 (13)
O11	0.0200 (17)	0.0164 (16)	0.0168 (17)	−0.0021 (13)	0.0026 (14)	0.0020 (13)
O13	0.0192 (17)	0.0219 (17)	0.0173 (17)	−0.0010 (14)	−0.0034 (14)	0.0015 (14)
O14	0.0254 (19)	0.0192 (17)	0.0229 (19)	−0.0013 (14)	0.0120 (16)	0.0011 (14)
O15	0.0126 (16)	0.0171 (16)	0.0183 (17)	−0.0035 (13)	0.0040 (13)	−0.0032 (13)
O16	0.0220 (18)	0.0321 (19)	0.0167 (18)	−0.0051 (15)	0.0054 (15)	−0.0125 (14)
O19	0.0264 (19)	0.0181 (17)	0.0227 (18)	0.0025 (14)	0.0066 (16)	0.0043 (14)
O18	0.0244 (18)	0.0251 (18)	0.0215 (18)	−0.0084 (14)	−0.0017 (15)	−0.0043 (14)
O17	0.028 (2)	0.0275 (18)	0.0197 (19)	0.0115 (15)	0.0097 (16)	0.0075 (14)
O20	0.0219 (18)	0.0160 (16)	0.0245 (19)	−0.0015 (13)	0.0102 (15)	−0.0005 (14)
C1	0.015 (3)	0.013 (3)	0.011 (3)	0	0.006 (3)	0
C4	0.011 (2)	0.012 (2)	0.019 (2)	0.0005 (17)	−0.0005 (19)	0.0019 (18)
C3	0.022 (4)	0.028 (4)	0.012 (3)	0	0.006 (3)	0
C2	0.018 (3)	0.014 (3)	0.009 (3)	0	−0.002 (3)	0
C7	0.036 (4)	0.021 (4)	0.012 (3)	0	0.010 (3)	0
C8	0.026 (4)	0.019 (3)	0.005 (3)	0	−0.001 (3)	0
C6	0.016 (2)	0.017 (2)	0.018 (2)	0.0003 (18)	0.006 (2)	0.0009 (19)
C5	0.026 (3)	0.017 (2)	0.011 (2)	−0.002 (2)	0.005 (2)	−0.0006 (18)
C11	0.014 (3)	0.015 (3)	0.014 (3)	0	−0.003 (3)	0
C10	0.016 (3)	0.015 (3)	0.015 (3)	0	0.000 (3)	0
C15	0.016 (2)	0.021 (2)	0.014 (2)	0.0026 (19)	0.001 (2)	−0.0020 (19)
C16	0.019 (2)	0.018 (2)	0.015 (2)	−0.0004 (19)	0.004 (2)	−0.0005 (19)
C13	0.032 (3)	0.021 (3)	0.014 (2)	0.005 (2)	0.010 (2)	0.0023 (19)
C12	0.019 (3)	0.028 (3)	0.021 (3)	0.005 (2)	0.009 (2)	−0.001 (2)
C14	0.020 (3)	0.028 (3)	0.017 (3)	0.006 (2)	0.010 (2)	0.001 (2)
C9	0.024 (3)	0.031 (3)	0.016 (3)	−0.003 (2)	0.008 (2)	0.002 (2)
C22	0.014 (2)	0.007 (2)	0.016 (2)	−0.0029 (17)	−0.0017 (19)	−0.0001 (17)
C17	0.023 (3)	0.019 (2)	0.013 (2)	0.001 (2)	0.007 (2)	−0.0021 (19)
C18	0.021 (3)	0.016 (2)	0.022 (3)	−0.0033 (19)	0.011 (2)	−0.0040 (19)
C21	0.014 (3)	0.018 (3)	0.013 (3)	0	−0.006 (3)	0
C20	0.024 (3)	0.030 (3)	0.010 (2)	0.006 (2)	0.007 (2)	−0.0007 (19)
C19	0.023 (3)	0.034 (3)	0.017 (3)	−0.003 (2)	0.011 (2)	0.001 (2)
C24	0.025 (3)	0.022 (3)	0.011 (2)	−0.005 (2)	0.002 (2)	0.0009 (19)
C23	0.021 (2)	0.020 (2)	0.012 (2)	−0.0021 (19)	0.005 (2)	0.0018 (18)
C26	0.021 (4)	0.015 (3)	0.020 (4)	0	0.005 (3)	0
C25	0.027 (4)	0.013 (3)	0.017 (3)	0	0.006 (3)	0
S16	0.0263 (7)	0.0219 (6)	0.0124 (6)	0.0039 (5)	0.0053 (5)	−0.0005 (5)
S27	0.0219 (6)	0.0245 (6)	0.0127 (6)	0.0035 (5)	−0.0012 (5)	−0.0004 (5)
C27	0.021 (2)	0.015 (2)	0.013 (2)	0.0028 (19)	0.003 (2)	−0.0002 (18)
C29	0.039 (3)	0.022 (3)	0.010 (2)	0.002 (2)	−0.001 (2)	−0.0004 (19)
C28	0.035 (3)	0.022 (3)	0.012 (2)	0.005 (2)	−0.007 (2)	−0.0015 (19)
N1	0.071 (6)	0.060 (5)	0.050 (5)	0	0.002 (5)	0
C30	0.038 (5)	0.026 (5)	0.084 (8)	0	0.014 (6)	0
C31	0.051 (6)	0.033 (5)	0.071 (7)	0	0.021 (5)	0

Mo1—O17	1.686 (3)	S15—C14	1.727 (5)
Mo1—O12	1.872 (3)	S15—C15	1.736 (5)
Mo1—O3	1.886 (3)	S18—C12	1.743 (5)
Mo1—O5	1.974 (3)	S18—C11	1.768 (4)
Mo1—O7	2.018 (3)	O1—Mo6ii	2.3222 (4)
Mo1—O2	2.3345 (4)	O1—Mo3ii	2.3234 (4)
Mo2—O4	1.680 (3)	O1—Mo4ii	2.3363 (4)
Mo2—O5	1.887 (3)	O2—Mo2i	2.3151 (4)
Mo2—O9	1.931 (3)	O2—Mo5i	2.3335 (4)
Mo2—O6	1.932 (3)	O2—Mo1i	2.3345 (4)
Mo2—O3i	1.974 (3)	O3—Mo2i	1.974 (3)
Mo2—O2	2.3151 (4)	O6—Mo5i	1.928 (3)
Mo5—O16	1.684 (3)	O7—Mo5i	1.860 (3)
Mo5—O7i	1.860 (3)	O8—Mo4ii	1.879 (3)
Mo5—O6i	1.928 (3)	O13—Mo6ii	2.013 (3)
Mo5—O9	1.937 (3)	O20—Mo6ii	1.962 (3)
Mo5—O12	2.010 (3)	C1—C2	1.343 (8)
Mo5—O2	2.3335 (4)	C1—S1iii	1.766 (3)
Mo3—O14	1.690 (3)	C4—C22	1.393 (6)
Mo3—O15	1.876 (3)	C3—C7	1.331 (9)
Mo3—O20	1.889 (3)	C3—H3	0.93
Mo3—O11	1.968 (3)	C2—S4iii	1.774 (4)
Mo3—O8	1.993 (3)	C7—H7	0.93
Mo3—O1	2.3234 (4)	C8—C21	1.345 (9)
Mo4—O18	1.692 (3)	C6—C5	1.343 (6)
Mo4—O13	1.851 (3)	C6—H6	0.93
Mo4—O8ii	1.879 (3)	C5—H5	0.93
Mo4—O15	1.989 (3)	C11—C10	1.339 (9)
Mo4—O10	2.028 (3)	C11—S18iii	1.768 (4)
Mo4—O1	2.3363 (4)	C10—S2iii	1.774 (4)
Mo6—O19	1.696 (3)	C15—C16	1.398 (6)
Mo6—O10	1.858 (3)	C13—C14	1.343 (6)
Mo6—O11	1.905 (3)	C13—H13	0.93
Mo6—O20ii	1.962 (3)	C12—C12iii	1.340 (9)
Mo6—O13ii	2.013 (3)	C12—H12	0.93
Mo6—O1	2.3222 (4)	C14—H14	0.93
S4—C20	1.746 (5)	C9—C9iii	1.343 (9)
S4—C2	1.774 (4)	C9—H9	0.93
S1—C19	1.739 (5)	C17—C18	1.347 (6)
S1—C1	1.766 (3)	C17—H17	0.93
S2—C9	1.749 (5)	C18—H18	0.93
S2—C10	1.774 (4)	C20—C20iii	1.347 (9)
S3—C23	1.723 (4)	C20—H20	0.93
S3—C22	1.724 (4)	C19—C19iii	1.335 (9)
S5—C6	1.721 (5)	C19—H19	0.93
S5—C4	1.727 (4)	C24—C23	1.344 (6)
S6—C24	1.724 (5)	C24—H24	0.93
S6—C22	1.732 (4)	C23—H23	0.93
S7—C4	1.728 (4)	C26—C25	1.323 (9)
S7—C5	1.728 (5)	C26—H26	0.93
S8—C3	1.743 (6)	C25—H25	0.93
S8—C8	1.764 (7)	S16—C29	1.748 (5)
S9—C18	1.728 (5)	S16—C27	1.767 (5)
S9—C16	1.728 (5)	S27—C28	1.749 (5)
S10—C25	1.746 (6)	S27—C27	1.759 (5)
S10—C21	1.769 (6)	C27—C27iv	1.330 (8)
S11—C7	1.737 (7)	C29—C28	1.322 (7)
S11—C8	1.772 (6)	C29—H29	0.93
S12—C21	1.759 (6)	C28—H28	0.93
S12—C26	1.761 (7)	N1—C30	1.136 (12)
S13—C16	1.722 (5)	C30—C31	1.492 (13)
S13—C17	1.725 (5)	C31—H31A	0.96
S14—C15	1.729 (4)	C31—H31B	0.96
S14—C13	1.729 (5)	C31—H31C	0.96
O17—Mo1—O12	105.04 (14)	Mo2—O2—Mo5i	89.589 (13)
O17—Mo1—O3	104.43 (14)	Mo2i—O2—Mo5i	90.411 (14)
O12—Mo1—O3	91.61 (13)	Mo2—O2—Mo5	90.411 (14)
O17—Mo1—O5	102.70 (14)	Mo2i—O2—Mo5	89.589 (13)
O12—Mo1—O5	87.90 (12)	Mo5i—O2—Mo5	180.000 (15)
O3—Mo1—O5	152.02 (12)	Mo2—O2—Mo1	89.800 (13)
O17—Mo1—O7	101.69 (14)	Mo2i—O2—Mo1	90.200 (13)
O12—Mo1—O7	152.99 (12)	Mo5i—O2—Mo1	89.969 (14)
O3—Mo1—O7	85.42 (12)	Mo5—O2—Mo1	90.031 (14)
O5—Mo1—O7	82.51 (12)	Mo2—O2—Mo1i	90.200 (13)
O17—Mo1—O2	176.68 (11)	Mo2i—O2—Mo1i	89.800 (13)
O12—Mo1—O2	77.94 (9)	Mo5i—O2—Mo1i	90.031 (14)
O3—Mo1—O2	76.77 (9)	Mo5—O2—Mo1i	89.969 (14)
O5—Mo1—O2	75.78 (8)	Mo1—O2—Mo1i	180
O7—Mo1—O2	75.24 (8)	Mo2—O5—Mo1	116.42 (14)
O4—Mo2—O5	103.76 (13)	Mo1—O3—Mo2i	117.16 (14)
O4—Mo2—O9	103.37 (13)	Mo5i—O6—Mo2	116.11 (14)
O5—Mo2—O9	88.74 (12)	Mo1—O12—Mo5	116.50 (14)
O4—Mo2—O6	102.89 (13)	Mo5i—O7—Mo1	116.59 (14)
O5—Mo2—O6	89.50 (12)	Mo4ii—O8—Mo3	117.46 (15)
O9—Mo2—O6	153.33 (12)	Mo2—O9—Mo5	117.05 (14)
O4—Mo2—O3i	102.71 (13)	Mo6—O10—Mo4	116.53 (14)
O5—Mo2—O3i	153.52 (12)	Mo6—O11—Mo3	116.24 (15)
O9—Mo2—O3i	84.73 (12)	Mo4—O13—Mo6ii	116.26 (15)
O6—Mo2—O3i	85.07 (12)	Mo3—O15—Mo4	116.10 (14)
O4—Mo2—O2	178.36 (10)	Mo3—O20—Mo6ii	116.81 (15)
O5—Mo2—O2	77.87 (9)	C2—C1—S1	123.08 (17)
O9—Mo2—O2	76.54 (9)	C2—C1—S1iii	123.08 (17)
O6—Mo2—O2	77.07 (9)	S1—C1—S1iii	113.8 (3)
O3i—Mo2—O2	75.66 (8)	C22—C4—S5	120.9 (3)
O16—Mo5—O7i	104.41 (14)	C22—C4—S7	123.4 (3)
O16—Mo5—O6i	103.77 (14)	S5—C4—S7	115.7 (3)
O7i—Mo5—O6i	90.34 (12)	C7—C3—S8	118.0 (5)
O16—Mo5—O9	103.27 (14)	C7—C3—H3	121
O7i—Mo5—O9	89.55 (12)	S8—C3—H3	121
O6i—Mo5—O9	152.09 (12)	C1—C2—S4iii	122.83 (18)
O16—Mo5—O12	101.98 (14)	C1—C2—S4	122.83 (18)
O7i—Mo5—O12	153.60 (12)	S4iii—C2—S4	114.3 (4)
O6i—Mo5—O12	84.01 (12)	C3—C7—S11	118.3 (5)
O9—Mo5—O12	83.78 (12)	C3—C7—H7	120.8
O16—Mo5—O2	177.36 (11)	S11—C7—H7	120.8
O7i—Mo5—O2	78.16 (9)	C21—C8—S8	122.5 (5)
O6i—Mo5—O2	76.70 (8)	C21—C8—S11	123.0 (5)
O9—Mo5—O2	75.98 (8)	S8—C8—S11	114.5 (4)
O12—Mo5—O2	75.45 (8)	C5—C6—S5	117.6 (4)
O14—Mo3—O15	106.28 (14)	C5—C6—H6	121.2
O14—Mo3—O20	104.51 (14)	S5—C6—H6	121.2
O15—Mo3—O20	91.14 (13)	C6—C5—S7	117.0 (4)
O14—Mo3—O11	101.82 (14)	C6—C5—H5	121.5
O15—Mo3—O11	87.94 (12)	S7—C5—H5	121.5
O20—Mo3—O11	152.81 (13)	C10—C11—S18iii	122.77 (18)
O14—Mo3—O8	100.35 (14)	C10—C11—S18	122.77 (18)
O15—Mo3—O8	153.12 (13)	S18iii—C11—S18	114.5 (4)
O20—Mo3—O8	85.58 (13)	C11—C10—S2	123.05 (18)
O11—Mo3—O8	83.12 (12)	C11—C10—S2iii	123.05 (18)
O14—Mo3—O1	175.05 (11)	S2—C10—S2iii	113.8 (4)
O15—Mo3—O1	78.15 (9)	C16—C15—S14	122.5 (3)
O20—Mo3—O1	77.32 (9)	C16—C15—S15	122.4 (3)
O11—Mo3—O1	75.90 (9)	S14—C15—S15	115.1 (3)
O8—Mo3—O1	75.10 (9)	C15—C16—S13	122.1 (4)
O18—Mo4—O13	105.18 (14)	C15—C16—S9	122.2 (4)
O18—Mo4—O8ii	102.97 (15)	S13—C16—S9	115.7 (3)
O13—Mo4—O8ii	92.59 (13)	C14—C13—S14	117.2 (4)
O18—Mo4—O15	103.98 (14)	C14—C13—H13	121.4
O13—Mo4—O15	88.36 (13)	S14—C13—H13	121.4
O8ii—Mo4—O15	151.77 (12)	C12iii—C12—S18	117.92 (15)
O18—Mo4—O10	101.72 (13)	C12iii—C12—H12	121
O13—Mo4—O10	152.84 (12)	S18—C12—H12	121
O8ii—Mo4—O10	84.97 (12)	C13—C14—S15	117.2 (4)
O15—Mo4—O10	81.52 (12)	C13—C14—H14	121.4
O18—Mo4—O1	176.53 (11)	S15—C14—H14	121.4
O13—Mo4—O1	78.29 (9)	C9iii—C9—S2	117.77 (15)
O8ii—Mo4—O1	76.83 (9)	C9iii—C9—H9	121.1
O15—Mo4—O1	75.75 (8)	S2—C9—H9	121.1
O10—Mo4—O1	74.81 (8)	C4—C22—S3	122.2 (3)
O19—Mo6—O10	105.57 (14)	C4—C22—S6	122.1 (3)
O19—Mo6—O11	104.81 (14)	S3—C22—S6	115.7 (3)
O10—Mo6—O11	91.35 (13)	C18—C17—S13	117.3 (4)
O19—Mo6—O20ii	101.65 (14)	C18—C17—H17	121.3
O10—Mo6—O20ii	88.78 (13)	S13—C17—H17	121.3
O11—Mo6—O20ii	152.48 (12)	C17—C18—S9	117.0 (4)
O19—Mo6—O13ii	100.43 (14)	C17—C18—H18	121.5
O10—Mo6—O13ii	153.81 (12)	S9—C18—H18	121.5
O11—Mo6—O13ii	84.97 (13)	C8—C21—S12	121.4 (5)
O20ii—Mo6—O13ii	82.91 (13)	C8—C21—S10	123.7 (5)
O19—Mo6—O1	175.58 (11)	S12—C21—S10	115.0 (4)
O10—Mo6—O1	78.25 (9)	C20iii—C20—S4	117.88 (15)
O11—Mo6—O1	77.08 (8)	C20iii—C20—H20	121.1
O20ii—Mo6—O1	76.01 (9)	S4—C20—H20	121.1
O13ii—Mo6—O1	75.65 (8)	C19iii—C19—S1	117.84 (15)
C20—S4—C2	94.7 (2)	C19iii—C19—H19	121.1
C19—S1—C1	94.0 (2)	S1—C19—H19	121.1
C9—S2—C10	94.6 (2)	C23—C24—S6	117.3 (4)
C23—S3—C22	94.9 (2)	C23—C24—H24	121.4
C6—S5—C4	94.8 (2)	S6—C24—H24	121.4
C24—S6—C22	94.7 (2)	C24—C23—S3	117.4 (4)
C4—S7—C5	94.9 (2)	C24—C23—H23	121.3
C3—S8—C8	94.6 (3)	S3—C23—H23	121.3
C18—S9—C16	95.0 (2)	C25—C26—S12	117.1 (5)
C25—S10—C21	94.1 (3)	C25—C26—H26	121.4
C7—S11—C8	94.5 (3)	S12—C26—H26	121.4
C21—S12—C26	94.7 (3)	C26—C25—S10	119.1 (5)
C16—S13—C17	95.0 (2)	C26—C25—H25	120.4
C15—S14—C13	95.3 (2)	S10—C25—H25	120.4
C14—S15—C15	95.2 (2)	C29—S16—C27	94.5 (2)
C12—S18—C11	94.8 (2)	C28—S27—C27	95.1 (2)
Mo6—O1—Mo6ii	180.000 (19)	C27iv—C27—S27	123.3 (5)
Mo6—O1—Mo3ii	89.861 (13)	C27iv—C27—S16	122.4 (5)
Mo6ii—O1—Mo3ii	90.139 (13)	S27—C27—S16	114.3 (2)
Mo6—O1—Mo3	90.139 (13)	C28—C29—S16	118.5 (4)
Mo6ii—O1—Mo3	89.861 (13)	C28—C29—H29	120.8
Mo3ii—O1—Mo3	180.0000 (10)	S16—C29—H29	120.8
Mo6—O1—Mo4	90.402 (14)	C29—C28—S27	117.5 (4)
Mo6ii—O1—Mo4	89.598 (13)	C29—C28—H28	121.3
Mo3ii—O1—Mo4	90.504 (14)	S27—C28—H28	121.3
Mo3—O1—Mo4	89.496 (14)	N1—C30—C31	178.7 (11)
Mo6—O1—Mo4ii	89.598 (13)	C30—C31—H31A	109.5
Mo6ii—O1—Mo4ii	90.402 (14)	C30—C31—H31B	109.5
Mo3ii—O1—Mo4ii	89.496 (14)	H31A—C31—H31B	109.5
Mo3—O1—Mo4ii	90.504 (14)	C30—C31—H31C	109.5
Mo4—O1—Mo4ii	180.0000 (10)	H31A—C31—H31C	109.5
Mo2—O2—Mo2i	180	H31B—C31—H31C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O11v	0.93	2.28	3.192 (6)	167
C7—H7···O19vi	0.93	2.47	3.251 (7)	141
C7—H7···O19vii	0.93	2.47	3.251 (7)	141
C9—H9···O12	0.93	2.54	3.388 (5)	151
C13—H13···O17viii	0.93	2.41	3.239 (6)	149
C14—H14···O19ix	0.93	2.59	3.175 (5)	121
C18—H18···O18x	0.93	2.41	3.145 (5)	136
C19—H19···O10xi	0.93	2.41	3.298 (5)	160
C20—H20···O12	0.93	2.54	3.437 (5)	162
C24—H24···O8xii	0.93	2.25	3.075 (6)	148
C28—H28···O4xii	0.93	2.53	3.384 (6)	152
C29—H29···O5xii	0.93	2.52	3.256 (6)	137
C29—H29···O6xii	0.93	2.55	3.284 (6)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O11i	0.93	2.28	3.192 (6)	167
C7—H7⋯O19ii	0.93	2.47	3.251 (7)	141
C7—H7⋯O19iii	0.93	2.47	3.251 (7)	141
C9—H9⋯O12	0.93	2.54	3.388 (5)	151
C13—H13⋯O17iv	0.93	2.41	3.239 (6)	149
C14—H14⋯O19v	0.93	2.59	3.175 (5)	121
C18—H18⋯O18vi	0.93	2.41	3.145 (5)	136
C19—H19⋯O10vii	0.93	2.41	3.298 (5)	160
C20—H20⋯O12	0.93	2.54	3.437 (5)	162
C24—H24⋯O8viii	0.93	2.25	3.075 (6)	148
C28—H28⋯O4viii	0.93	2.53	3.384 (6)	152
C29—H29⋯O5viii	0.93	2.52	3.256 (6)	137
C29—H29⋯O6viii	0.93	2.55	3.284 (6)	136

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .