Synthesis, properties and X-ray crystal structure of a new heteropolyacid supermolecular charge-transfer complex [(VB₁)₂DMFHPMo₁₂O₄₀·5DMF]

The title complex [(VB₁)₂DMFHPMo₁₂O₄₀·5DMF, VB₁ = vitamin B₁ (thiamine chloride), DMF = N,N-dimethylformamide] has been synthesized and characterized by elemental analysis, IR, UV-Vis, electron spin resonance, X-ray photoelectron spectroscopy and cyclic voltammetry methods. The X-ray crystal structure revealed that there is one independent molecule in the unit cell of the title complex that contains one mixed-valence heteropolyanion, two VB₁⁺ cations and six DMF molecules. The title complex possesses a centrosymmetrical arrangement in the unit cell, with the P atom at the symmetry center of the heteropoly­anion and with eight O atoms surrounding the central P atom, such that two sets of PO₄ tetrahedra are formed. The PO₄ tetrahedra and MoO₆^6-(7-) octahedra are disordered in the heteropolyanion. The bond distances of P-O_a and Mo=O_d are in the ranges 1.57 (4)-1.70 (4) Å and 1.61 (2)-1.67 (2) Å, respectively.

Computing details

Program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993).

Figures

(I)

Crystal data

C42H76Mo12N14O52PS2	Z = 1
Mr = 2855.54	F(000) = 1393
Triclinic, P1	Dx = 2.323 Mg m^−3
a = 12.322 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.607 (3) Å	Cell parameters from 23 reflections
c = 14.160 (3) Å	θ = 4.9–9.7°
α = 103.900 (3)°	µ = 1.96 mm^−1
β = 98.87 (3)°	T = 293 K
γ = 112.85 (3)°	0.50 × 0.42 × 0.40 mm
V = 2040.9 (7) Å^3

Data collection

Radiation source: fine-focus sealed tube	Rint = 0.079
Graphite monochromator	θmax = 23.0°, θmin = 1.5°
6706 measured reflections	h = −1→13
5563 independent reflections	k = −13→13
4509 reflections with I > 2σ(I)	l = −15→15

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)] = 0.089	Calculated w = 1/[σ^2(Fo^2) + (0.1012P)^2 + 51.6101P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.268	(Δ/σ)max = 3.172
S = 1.12	Δρmax = 1.35 e Å^−3
5407 reflections	Δρmin = −1.63 e Å^−3
552 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0159 (11)
Primary atom site location: structure-invariant direct methods

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 on F² for ALL reflections except for 156 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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	0.57249 (13)	1.71194 (13)	0.38258 (12)	0.0342 (5)
Mo2	0.45421 (13)	1.22660 (12)	0.36716 (11)	0.0291 (5)
Mo3	0.71913 (14)	1.40458 (14)	0.57288 (12)	0.0355 (5)
Mo4	0.52727 (13)	1.43677 (12)	0.24877 (10)	0.0285 (5)
Mo5	0.79054 (13)	1.61636 (14)	0.45610 (12)	0.0349 (5)
Mo6	0.23461 (12)	1.32187 (12)	0.29269 (10)	0.0285 (5)
P	0.5000	1.5000	0.5000	0.047 (2)
S	0.9179 (8)	1.3688 (7)	0.3553 (7)	0.095 (2)
O1	0.4387 (19)	1.1019 (15)	0.3095 (17)	0.098 (7)
O2	0.602 (2)	1.8080 (17)	0.3291 (15)	0.112 (8)
O3	0.1125 (17)	1.2397 (18)	0.1939 (14)	0.102 (7)
O4	0.5297 (16)	1.5766 (17)	0.2694 (15)	0.092 (6)
O5	0.816 (2)	1.3514 (18)	0.6041 (15)	0.096 (6)
O6	0.544 (2)	1.408 (2)	0.1335 (13)	0.111 (8)
O7	0.3530 (17)	1.3724 (19)	0.2233 (18)	0.103 (7)
O8	0.9261 (16)	1.6657 (18)	0.4327 (16)	0.092 (6)
O9	0.5183 (15)	1.3053 (16)	0.2739 (17)	0.093 (6)
O10	0.4056 (17)	1.663 (2)	0.3668 (16)	0.130 (10)
O11	0.6155 (18)	1.287 (3)	0.4470 (18)	0.139 (11)
O12	0.6021 (19)	1.799 (2)	0.5151 (15)	0.125 (9)
O13	0.7287 (17)	1.7141 (16)	0.4304 (18)	0.109 (8)
O14	0.2991 (16)	1.2217 (16)	0.3044 (18)	0.094 (7)
O15	0.779 (2)	1.5437 (17)	0.6847 (14)	0.102 (7)
O16	0.6929 (18)	1.5102 (18)	0.321 (2)	0.126 (10)
O17	0.803 (3)	1.500 (2)	0.4950 (16)	0.136 (11)
O18	0.162 (3)	1.294 (2)	0.4007 (18)	0.147 (10)
O19	0.571 (3)	1.547 (3)	0.414 (3)	0.207 (19)
O20	0.356 (3)	1.469 (3)	0.452 (2)	0.189 (16)
O21	0.453 (3)	1.402 (4)	0.3928 (17)	0.201 (18)
O22	0.511 (3)	1.390 (3)	0.504 (3)	0.171 (12)
O23	0.857 (4)	1.266 (3)	0.048 (3)	0.245 (15)
H23	0.904 (4)	1.267 (3)	0.012 (3)	0.080*
O24	0.655 (2)	1.149 (2)	−0.238 (2)	0.128 (9)
H24	0.689 (2)	1.131 (2)	−0.281 (2)	0.080*
O25	1.193 (3)	1.029 (2)	0.824 (2)	0.126 (8)
H25	1.152 (3)	0.989 (2)	0.766 (2)	0.080*
O26	0.991 (4)	0.704 (3)	0.086 (3)	0.276 (14)
H26	1.039 (4)	0.714 (3)	0.051 (3)	0.080*
N1	0.8840 (18)	1.0316 (16)	0.5504 (14)	0.062 (5)
N2	0.900 (3)	1.018 (2)	0.389 (2)	0.099 (8)
N3	0.7370 (17)	1.0795 (15)	0.6088 (14)	0.073 (5)
N4	0.7606 (15)	1.1758 (17)	0.3259 (13)	0.059 (5)
N5	0.666 (3)	1.313 (3)	−0.141 (2)	0.108 (9)
N6	1.194 (3)	1.029 (3)	0.981 (2)	0.121 (11)
N7	0.833 (4)	0.687 (4)	0.106 (4)	0.149 (15)*
C1	0.8418 (18)	1.038 (2)	0.4592 (17)	0.059 (6)
C2	0.833 (3)	1.053 (3)	0.621 (2)	0.081 (8)
C3	0.880 (3)	1.044 (3)	0.724 (2)	0.091 (9)
H3A	0.834 (3)	1.062 (3)	0.769 (2)	0.080*
H3B	0.965 (3)	1.096 (3)	0.753 (2)	0.080*
H3C	0.870 (3)	0.969 (3)	0.716 (2)	0.080*
C4	0.695 (3)	1.087 (2)	0.518 (2)	0.078 (8)
H4	0.633 (3)	1.110 (2)	0.510 (2)	0.080*
C5	0.738 (2)	1.062 (3)	0.4411 (18)	0.072 (7)
C6	0.687 (2)	1.071 (2)	0.3436 (17)	0.069 (7)
H6A	0.679 (2)	1.007 (2)	0.2892 (17)	0.080*
H6B	0.605 (2)	1.065 (2)	0.3407 (17)	0.080*
C7	0.858 (3)	1.266 (3)	0.396 (3)	0.089 (10)
C8	0.814 (3)	1.305 (3)	0.245 (2)	0.085 (8)
C9	0.729 (2)	1.200 (3)	0.2374 (17)	0.075 (7)
C10	0.623 (3)	1.118 (3)	0.153 (2)	0.100 (10)
H10A	0.581 (3)	1.053 (3)	0.171 (2)	0.080*
H10B	0.650 (3)	1.097 (3)	0.095 (2)	0.080*
H10C	0.569 (3)	1.151 (3)	0.138 (2)	0.080*
C11	0.816 (4)	1.377 (4)	0.176 (3)	0.146 (17)
H11A	0.736 (4)	1.341 (4)	0.127 (3)	0.080*
H11B	0.827 (4)	1.450 (4)	0.217 (3)	0.080*
C12	0.902 (4)	1.394 (6)	0.125 (4)	0.19 (3)
H12A	0.983 (4)	1.423 (6)	0.170 (4)	0.080*
H12B	0.902 (4)	1.445 (6)	0.088 (4)	0.080*
C13	0.563 (3)	1.246 (4)	−0.107 (3)	0.15 (2)
H13A	0.546 (3)	1.296 (4)	−0.058 (3)	0.080*
H13B	0.584 (3)	1.197 (4)	−0.077 (3)	0.080*
H13C	0.491 (3)	1.201 (4)	−0.164 (3)	0.080*
C14	0.716 (4)	1.427 (3)	−0.106 (3)	0.21 (3)
H14A	0.678 (4)	1.451 (3)	−0.057 (3)	0.080*
H14B	0.703 (4)	1.455 (3)	−0.162 (3)	0.080*
H14C	0.802 (4)	1.458 (3)	−0.075 (3)	0.080*
C15	0.695 (4)	1.251 (3)	−0.208 (3)	0.124 (13)
H15	0.754 (4)	1.291 (3)	−0.236 (3)	0.080*
C16	1.310 (4)	1.113 (4)	1.025 (4)	0.21 (3)
H16A	1.350 (4)	1.129 (4)	0.974 (4)	0.080*
H16B	1.355 (4)	1.089 (4)	1.068 (4)	0.080*
H16C	1.307 (4)	1.179 (4)	1.065 (4)	0.080*
C17	1.124 (4)	0.990 (4)	1.042 (4)	0.255 (17)
H17A	1.045 (4)	0.932 (4)	1.001 (4)	0.080*
H17B	1.116 (4)	1.051 (4)	1.085 (4)	0.080*
H17C	1.164 (4)	0.960 (4)	1.082 (4)	0.080*
C18	1.149 (3)	0.987 (3)	0.882 (2)	0.085 (8)
H18	1.077 (3)	0.920 (3)	0.855 (2)	0.080*
C19	0.700 (4)	0.658 (4)	0.072 (3)	0.221 (14)
H19A	0.662 (4)	0.643 (4)	0.125 (3)	0.080*
H19B	0.661 (4)	0.592 (4)	0.012 (3)	0.080*
H19C	0.692 (4)	0.720 (4)	0.057 (3)	0.080*
C20	0.873 (4)	0.684 (4)	0.205 (4)	0.236 (17)
H20A	0.806 (4)	0.665 (4)	0.235 (4)	0.080*
H20B	0.938 (4)	0.756 (4)	0.247 (4)	0.080*
H20C	0.903 (4)	0.628 (4)	0.201 (4)	0.080*
C21	0.865 (6)	0.701 (5)	0.028 (5)	0.21 (2)
H21	0.832 (6)	0.707 (5)	−0.033 (5)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0316 (9)	0.0379 (10)	0.0357 (9)	0.0147 (7)	0.0081 (7)	0.0185 (7)
Mo2	0.0293 (8)	0.0249 (8)	0.0281 (8)	0.0162 (7)	0.0043 (6)	−0.0046 (6)
Mo3	0.0361 (9)	0.0531 (11)	0.0359 (9)	0.0372 (8)	0.0117 (7)	0.0155 (8)
Mo4	0.0295 (8)	0.0361 (9)	0.0187 (8)	0.0172 (7)	0.0070 (6)	0.0023 (6)
Mo5	0.0242 (8)	0.0441 (10)	0.0464 (10)	0.0187 (7)	0.0202 (7)	0.0191 (8)
Mo6	0.0249 (8)	0.0285 (9)	0.0227 (8)	0.0111 (7)	−0.0028 (6)	−0.0004 (6)
P	0.054 (5)	0.052 (5)	0.037 (4)	0.027 (4)	0.011 (4)	0.012 (3)
S	0.095 (6)	0.095 (6)	0.100 (6)	0.041 (5)	0.037 (5)	0.035 (5)
O1	0.116 (15)	0.072 (12)	0.151 (19)	0.062 (11)	0.091 (15)	0.046 (12)
O2	0.130 (19)	0.084 (14)	0.075 (13)	0.025 (13)	−0.017 (12)	0.014 (11)
O3	0.064 (11)	0.117 (16)	0.068 (12)	0.002 (11)	−0.017 (9)	0.021 (11)
O4	0.071 (11)	0.097 (14)	0.088 (13)	0.042 (11)	−0.010 (10)	0.009 (11)
O5	0.142 (18)	0.125 (16)	0.097 (14)	0.112 (15)	0.053 (13)	0.063 (13)
O6	0.156 (19)	0.19 (2)	0.048 (10)	0.122 (18)	0.055 (12)	0.043 (12)
O7	0.073 (12)	0.126 (17)	0.16 (2)	0.061 (13)	0.063 (13)	0.094 (16)
O8	0.053 (10)	0.116 (16)	0.106 (15)	0.036 (11)	0.037 (10)	0.030 (12)
O9	0.054 (10)	0.090 (13)	0.135 (17)	0.027 (10)	0.009 (10)	0.056 (13)
O10	0.053 (11)	0.21 (3)	0.077 (14)	0.014 (14)	0.020 (10)	0.029 (15)
O11	0.059 (12)	0.20 (3)	0.101 (18)	0.035 (15)	0.020 (12)	−0.002 (18)
O12	0.078 (14)	0.19 (3)	0.067 (13)	0.041 (15)	0.001 (10)	0.014 (14)
O13	0.054 (11)	0.071 (13)	0.142 (19)	0.007 (10)	−0.016 (11)	−0.004 (13)
O14	0.052 (10)	0.076 (13)	0.16 (2)	0.022 (9)	0.023 (11)	0.053 (13)
O15	0.19 (2)	0.094 (14)	0.070 (12)	0.097 (16)	0.071 (14)	0.035 (11)
O16	0.067 (13)	0.080 (14)	0.19 (3)	0.035 (11)	−0.016 (14)	0.010 (15)
O17	0.26 (4)	0.116 (17)	0.073 (13)	0.11 (2)	0.056 (17)	0.049 (13)
O18	0.27 (3)	0.15 (2)	0.093 (17)	0.13 (2)	0.089 (19)	0.070 (16)
O19	0.10 (2)	0.25 (4)	0.16 (3)	0.05 (3)	0.01 (2)	−0.06 (3)
O20	0.11 (2)	0.17 (3)	0.13 (2)	−0.05 (2)	0.028 (18)	−0.01 (2)
O21	0.13 (2)	0.41 (6)	0.046 (12)	0.12 (3)	0.021 (13)	0.04 (2)
O22	0.22 (3)	0.18 (3)	0.14 (3)	0.11 (3)	0.06 (3)	0.08 (2)
O23	0.19 (4)	0.30 (3)	0.24 (4)	0.09 (3)	0.09 (3)	0.08 (3)
O24	0.17 (2)	0.11 (2)	0.13 (2)	0.086 (18)	0.051 (17)	0.023 (18)
O25	0.15 (2)	0.15 (2)	0.08 (2)	0.078 (17)	0.019 (18)	0.029 (18)
O26	0.24 (4)	0.23 (3)	0.25 (4)	0.04 (3)	0.08 (3)	0.00 (3)
N1	0.078 (13)	0.075 (13)	0.049 (11)	0.053 (11)	0.016 (10)	0.015 (10)
N2	0.11 (2)	0.12 (2)	0.102 (19)	0.081 (18)	0.045 (16)	0.033 (17)
N3	0.097 (13)	0.073 (11)	0.072 (11)	0.054 (10)	0.028 (10)	0.032 (9)
N4	0.039 (9)	0.085 (14)	0.040 (10)	0.022 (10)	0.004 (8)	0.012 (9)
N5	0.13 (2)	0.12 (2)	0.088 (18)	0.09 (2)	0.015 (16)	0.004 (17)
N6	0.15 (3)	0.14 (3)	0.079 (17)	0.04 (2)	0.059 (19)	0.058 (17)
C1	0.035 (11)	0.080 (16)	0.057 (14)	0.028 (11)	0.007 (10)	0.016 (12)
C2	0.13 (3)	0.10 (2)	0.070 (18)	0.09 (2)	0.044 (17)	0.046 (16)
C3	0.085 (19)	0.11 (2)	0.071 (17)	0.026 (18)	0.023 (15)	0.050 (17)
C4	0.089 (19)	0.10 (2)	0.08 (2)	0.066 (17)	0.025 (16)	0.043 (16)
C5	0.064 (15)	0.13 (2)	0.051 (14)	0.069 (16)	0.020 (12)	0.030 (14)
C6	0.075 (17)	0.077 (17)	0.052 (13)	0.038 (14)	0.003 (12)	0.018 (12)
C7	0.08 (2)	0.08 (2)	0.10 (2)	0.021 (17)	0.054 (19)	0.027 (18)
C8	0.064 (17)	0.10 (2)	0.078 (18)	0.033 (17)	0.023 (14)	0.020 (16)
C9	0.069 (16)	0.11 (2)	0.040 (13)	0.051 (16)	0.002 (12)	0.010 (14)
C10	0.067 (18)	0.14 (3)	0.08 (2)	0.057 (19)	−0.001 (15)	0.016 (19)
C11	0.20 (4)	0.21 (5)	0.17 (4)	0.15 (4)	0.11 (3)	0.15 (4)
C12	0.08 (3)	0.28 (9)	0.13 (5)	−0.02 (4)	0.01 (3)	0.13 (5)
C13	0.08 (2)	0.26 (6)	0.10 (3)	0.07 (3)	0.03 (2)	0.04 (3)
C14	0.19 (4)	0.15 (4)	0.20 (4)	0.13 (3)	−0.13 (4)	−0.09 (3)
C15	0.14 (3)	0.09 (2)	0.14 (3)	0.04 (2)	0.09 (3)	0.01 (2)
C16	0.11 (3)	0.16 (5)	0.27 (7)	0.06 (3)	−0.08 (4)	−0.02 (5)
C17	0.24 (4)	0.22 (4)	0.25 (4)	0.04 (3)	0.10 (4)	0.09 (4)
C18	0.10 (2)	0.13 (2)	0.04 (2)	0.035 (17)	0.039 (17)	0.042 (17)
C19	0.22 (3)	0.19 (3)	0.23 (3)	0.08 (3)	0.04 (3)	0.06 (3)
C20	0.24 (4)	0.16 (4)	0.24 (5)	0.04 (4)	0.07 (4)	0.05 (4)
C21	0.20 (6)	0.18 (6)	0.22 (6)	0.06 (5)	0.12 (5)	0.03 (5)

Geometric parameters (Å, º)

Mo1—O2	1.61 (2)	P—O21^i	1.61 (3)
Mo1—O12	1.86 (2)	P—O20^i	1.64 (4)
Mo1—O10	1.86 (2)	P—O20	1.64 (4)
Mo1—O13	1.93 (2)	P—O19	1.71 (4)
Mo1—O4	1.95 (2)	P—O19^i	1.71 (4)
Mo1—O19	2.39 (5)	S—C7	1.60 (3)
Mo1—O22^i	2.46 (4)	S—C8	1.65 (3)
Mo2—O1	1.62 (2)	O10—Mo3^i	1.90 (2)
Mo2—O11	1.87 (2)	O12—Mo2^i	1.96 (2)
Mo2—O14	1.95 (2)	O15—Mo6^i	1.86 (2)
Mo2—O12^i	1.96 (2)	O18—Mo5^i	1.96 (3)
Mo2—O9	1.96 (2)	O20—Mo3^i	2.32 (5)
Mo2—O21	2.33 (5)	O20—Mo5^i	2.48 (3)
Mo2—O22	2.34 (4)	O21—O22	1.70 (4)
Mo3—O5	1.67 (2)	O22—Mo1^i	2.46 (4)
Mo3—O10^i	1.90 (2)	O23—C12	1.64 (7)
Mo3—O11	1.93 (2)	O24—C15	1.22 (4)
Mo3—O15	1.94 (2)	O25—C18	1.19 (3)
Mo3—O17	1.99 (2)	O26—C21	1.62 (7)
Mo3—O20^i	2.32 (5)	N1—C2	1.29 (3)
Mo3—O22	2.51 (4)	N1—C1	1.35 (3)
Mo4—O6	1.65 (2)	N2—C1	1.35 (3)
Mo4—O4	1.84 (2)	N3—C4	1.35 (3)
Mo4—O16	1.87 (2)	N3—C2	1.37 (3)
Mo4—O9	1.87 (2)	N4—C7	1.35 (3)
Mo4—O7	1.91 (2)	N4—C9	1.41 (3)
Mo4—O19	2.31 (3)	N4—C6	1.47 (3)
Mo4—O21	2.44 (3)	N5—C15	1.29 (4)
Mo5—O8	1.66 (2)	N5—C14	1.36 (4)
Mo5—O13	1.85 (2)	N5—C13	1.48 (4)
Mo5—O17	1.85 (2)	N6—C16	1.36 (5)
Mo5—O16	1.95 (2)	N6—C17	1.36 (4)
Mo5—O18^i	1.96 (3)	N6—C18	1.31 (4)
Mo5—O19	2.41 (3)	N7—C21	1.26 (6)
Mo5—O20^i	2.48 (3)	N7—C20	1.43 (5)
Mo6—O3	1.66 (2)	N7—C19	1.50 (4)
Mo6—O14	1.85 (2)	C1—C5	1.45 (3)
Mo6—O15^i	1.86 (2)	C2—C3	1.54 (4)
Mo6—O7	1.89 (2)	C4—C5	1.30 (3)
Mo6—O18	1.93 (2)	C5—C6	1.48 (3)
Mo6—O20	2.41 (3)	C8—C9	1.37 (4)
Mo6—O21	2.49 (3)	C8—C11	1.53 (4)
P—O22^i	1.57 (4)	C9—C10	1.45 (3)
P—O22	1.57 (4)	C11—C12	1.35 (5)
P—O21	1.61 (3)
O2—Mo1—O12	100.2 (12)	O7—Mo6—O20	94.6 (10)
O2—Mo1—O10	101.7 (13)	O18—Mo6—O20	68.6 (11)
O12—Mo1—O10	89.1 (10)	O3—Mo6—O21	155.8 (11)
O2—Mo1—O13	104.3 (12)	O14—Mo6—O21	62.2 (12)
O12—Mo1—O13	84.9 (10)	O15^i—Mo6—O21	98.1 (14)
O10—Mo1—O13	154.0 (11)	O7—Mo6—O21	64.2 (9)
O2—Mo1—O4	102.1 (10)	O18—Mo6—O21	97.1 (11)
O12—Mo1—O4	157.7 (11)	O20—Mo6—O21	46.4 (12)
O10—Mo1—O4	87.1 (10)	O22^i—P—O22	180.00 (2)
O13—Mo1—O4	88.9 (8)	O22^i—P—O21	115.4 (19)
O2—Mo1—O19	156.3 (13)	O22—P—O21	64.6 (19)
O12—Mo1—O19	98.3 (12)	O22^i—P—O21^i	64.6 (19)
O10—Mo1—O19	93.3 (13)	O22—P—O21^i	115.4 (19)
O13—Mo1—O19	62.7 (10)	O21—P—O21^i	180.000 (13)
O4—Mo1—O19	60.1 (10)	O22^i—P—O20^i	109.8 (19)
O2—Mo1—O22^i	157.1 (13)	O22—P—O20^i	70.2 (19)
O12—Mo1—O22^i	63.4 (12)	O21—P—O20^i	107.0 (15)
O10—Mo1—O22^i	64.3 (12)	O21^i—P—O20^i	73.0 (15)
O13—Mo1—O22^i	90.6 (12)	O22^i—P—O20	70.2 (19)
O4—Mo1—O22^i	95.4 (11)	O22—P—O20	109.8 (19)
O19—Mo1—O22^i	46.6 (12)	O21—P—O20	73.0 (15)
O1—Mo2—O11	98.0 (12)	O21^i—P—O20	107.0 (15)
O1—Mo2—O14	102.9 (10)	O20^i—P—O20	180.000 (6)
O11—Mo2—O14	158.9 (11)	O22^i—P—O19	71.4 (18)
O1—Mo2—O12^i	99.9 (11)	O22—P—O19	108.6 (18)
O11—Mo2—O12^i	88.7 (10)	O21—P—O19	68.2 (17)
O14—Mo2—O12^i	90.9 (9)	O21^i—P—O19	111.8 (17)
O1—Mo2—O9	100.1 (9)	O20^i—P—O19	76.4 (16)
O11—Mo2—O9	88.2 (10)	O20—P—O19	103.6 (16)
O14—Mo2—O9	85.0 (8)	O22^i—P—O19^i	108.6 (18)
O12^i—Mo2—O9	159.9 (11)	O22—P—O19^i	71.4 (18)
O1—Mo2—O21	160.2 (10)	O21—P—O19^i	111.8 (17)
O11—Mo2—O21	94.3 (12)	O21^i—P—O19^i	68.2 (17)
O14—Mo2—O21	64.7 (9)	O20^i—P—O19^i	103.6 (16)
O12^i—Mo2—O21	95.7 (11)	O20—P—O19^i	76.4 (16)
O9—Mo2—O21	64.8 (9)	O19—P—O19^i	180.000 (15)
O1—Mo2—O22	157.0 (12)	C7—S—C8	93.3 (18)
O11—Mo2—O22	66.1 (12)	Mo4—O4—Mo1	138.3 (11)
O14—Mo2—O22	94.7 (11)	Mo6—O7—Mo4	138.6 (13)
O12^i—Mo2—O22	64.7 (12)	Mo4—O9—Mo2	135.1 (12)
O9—Mo2—O22	96.0 (11)	Mo1—O10—Mo3^i	141.4 (14)
O21—Mo2—O22	42.7 (10)	Mo2—O11—Mo3	137.9 (14)
O5—Mo3—O10^i	101.0 (11)	Mo1—O12—Mo2^i	136.2 (15)
O5—Mo3—O11	98.9 (12)	Mo5—O13—Mo1	139.0 (11)
O10^i—Mo3—O11	87.2 (10)	Mo6—O14—Mo2	138.4 (11)
O5—Mo3—O15	102.8 (10)	Mo6^i—O15—Mo3	136.4 (12)
O10^i—Mo3—O15	88.3 (10)	Mo4—O16—Mo5	136.5 (15)
O11—Mo3—O15	158.3 (11)	Mo5—O17—Mo3	134.8 (17)
O5—Mo3—O17	102.2 (11)	Mo6—O18—Mo5^i	131.6 (17)
O10^i—Mo3—O17	156.9 (13)	P—O19—Mo4	124 (2)
O11—Mo3—O17	89.1 (11)	P—O19—Mo1	119.7 (17)
O15—Mo3—O17	86.7 (9)	Mo4—O19—Mo1	98.1 (17)
O5—Mo3—O20^i	161.5 (10)	P—O19—Mo5	117 (2)
O10^i—Mo3—O20^i	91.8 (12)	Mo4—O19—Mo5	97.3 (12)
O11—Mo3—O20^i	95.0 (12)	Mo1—O19—Mo5	94.8 (15)
O15—Mo3—O20^i	63.9 (9)	P—O20—Mo3^i	126.1 (16)
O17—Mo3—O20^i	65.7 (11)	P—O20—Mo6	122 (2)
O5—Mo3—O22	153.6 (12)	Mo3^i—O20—Mo6	96.5 (14)
O10^i—Mo3—O22	62.7 (11)	P—O20—Mo5^i	116.5 (19)
O11—Mo3—O22	61.8 (11)	Mo3^i—O20—Mo5^i	95.4 (13)
O15—Mo3—O22	97.4 (11)	Mo6—O20—Mo5^i	93.1 (8)
O17—Mo3—O22	95.6 (12)	P—O21—O22	56.7 (14)
O20^i—Mo3—O22	44.9 (10)	P—O21—Mo2	125.7 (18)
O6—Mo4—O4	101.1 (11)	O22—O21—Mo2	69 (2)
O6—Mo4—O16	98.3 (13)	P—O21—Mo4	122 (2)
O4—Mo4—O16	88.2 (9)	O22—O21—Mo4	135 (2)
O6—Mo4—O9	99.1 (11)	Mo2—O21—Mo4	96.0 (11)
O4—Mo4—O9	159.8 (10)	P—O21—Mo6	118.7 (16)
O16—Mo4—O9	88.8 (9)	O22—O21—Mo6	130 (2)
O6—Mo4—O7	102.4 (11)	Mo2—O21—Mo6	94.7 (15)
O4—Mo4—O7	88.6 (9)	Mo4—O21—Mo6	92.1 (8)
O16—Mo4—O7	159.3 (12)	P—O22—O21	59 (2)
O9—Mo4—O7	87.1 (8)	P—O22—Mo2	127 (2)
O6—Mo4—O19	155.6 (15)	O21—O22—Mo2	68 (2)
O4—Mo4—O19	63.0 (14)	P—O22—Mo1^i	122.3 (19)
O16—Mo4—O19	64.6 (12)	O21—O22—Mo1^i	136 (2)
O9—Mo4—O19	97.7 (14)	Mo2—O22—Mo1^i	95.0 (12)
O7—Mo4—O19	95.8 (11)	P—O22—Mo3	118.8 (18)
O6—Mo4—O21	158.1 (14)	O21—O22—Mo3	129 (2)
O4—Mo4—O21	96.7 (13)	Mo2—O22—Mo3	93.9 (13)
O16—Mo4—O21	94.9 (12)	Mo1^i—O22—Mo3	91.2 (12)
O9—Mo4—O21	63.6 (13)	C2—N1—C1	119 (2)
O7—Mo4—O21	65.1 (9)	C4—N3—C2	117 (2)
O19—Mo4—O21	46.0 (14)	C7—N4—C9	111 (2)
O8—Mo5—O13	103.2 (10)	C7—N4—C6	125 (2)
O8—Mo5—O17	96.6 (13)	C9—N4—C6	123.6 (19)
O13—Mo5—O17	160.1 (12)	C15—N5—C14	127 (4)
O8—Mo5—O16	98.5 (10)	C15—N5—C13	113 (3)
O13—Mo5—O16	88.8 (9)	C14—N5—C13	120 (4)
O17—Mo5—O16	89.8 (10)	C16—N6—C17	118 (4)
O8—Mo5—O18^i	99.5 (12)	C16—N6—C18	122 (4)
O13—Mo5—O18^i	86.6 (10)	C17—N6—C18	120 (4)
O17—Mo5—O18^i	88.7 (10)	C21—N7—C20	145 (6)
O16—Mo5—O18^i	162.0 (12)	C21—N7—C19	100 (5)
O8—Mo5—O19	154.2 (13)	C20—N7—C19	115 (5)
O13—Mo5—O19	63.0 (13)	N2—C1—N1	116 (2)
O17—Mo5—O19	99.2 (16)	N2—C1—C5	124 (2)
O16—Mo5—O19	61.4 (10)	N1—C1—C5	120 (2)
O18^i—Mo5—O19	101.2 (13)	N1—C2—N3	124 (2)
O8—Mo5—O20^i	155.2 (12)	N1—C2—C3	119 (3)
O13—Mo5—O20^i	96.5 (13)	N3—C2—C3	117 (2)
O17—Mo5—O20^i	64.0 (14)	C5—C4—N3	123 (2)
O16—Mo5—O20^i	96.7 (10)	C4—C5—C1	117 (2)
O18^i—Mo5—O20^i	66.6 (11)	C4—C5—C6	120 (2)
O19—Mo5—O20^i	50.1 (14)	C1—C5—C6	123 (2)
O3—Mo6—O14	100.5 (11)	N4—C6—C5	115 (2)
O3—Mo6—O15^i	99.4 (11)	N4—C7—S	114 (3)
O14—Mo6—O15^i	160.0 (10)	C9—C8—C11	131 (3)
O3—Mo6—O7	99.2 (10)	C9—C8—S	112 (2)
O14—Mo6—O7	84.2 (9)	C11—C8—S	116 (3)
O15^i—Mo6—O7	90.2 (9)	C8—C9—N4	110 (2)
O3—Mo6—O18	99.5 (12)	C8—C9—C10	129 (3)
O14—Mo6—O18	89.4 (10)	N4—C9—C10	121 (3)
O15^i—Mo6—O18	89.8 (10)	C12—C11—C8	117 (4)
O7—Mo6—O18	161.0 (12)	C11—C12—O23	102 (4)
O3—Mo6—O20	157.6 (13)	O24—C15—N5	129 (4)
O14—Mo6—O20	98.4 (13)	O25—C18—N6	125 (3)
O15^i—Mo6—O20	62.9 (13)	N7—C21—O26	84 (5)

Symmetry code: (i) −x+1, −y+3, −z+1.