Crystal structures of hybrid completely reduced phospho­molybdates and catalytic performance applied as mol­ecular catalysts for the reduction of chromium(VI)

Tian, X.; Xin, X.; Gao, Y.; Dai, D.; Huang, J.; Han, Z.

doi:10.1107/S2053229618013025

Crystal structures of hybrid completely reduced phosphomolybdates and catalytic performance applied as molecular catalysts for the reduction of chromium(VI)

X. Tian, X. Xin, Y. Gao, D. Dai, J. Huang and Z. Han

The exploration of highly efficient and low-cost catalysts for the treatment of hexavalent chromium Cr^VI in environmental remediation is currently one of the most challenging topics. Here, three phosphomolybdate hybrid compounds have been successfully isolated by the hydrothermal method and been applied as supramolecular catalysts for the reduction of Cr^VI. Single-crystal X-ray diffraction revealed their formulae as (H₂bpp)₂[Fe(H₂O)][Sr(H₂O)₄]₂{Fe[Mo₆O₁₂(OH)₃(H₂PO₄)(HPO₄)(PO₄)₂]₂}·5H₂O (1), (H₂bpp)₂[Na(H₂O)(OC₂H₅)][Fe(H₂O)₂][Ca(H₂O)₂]₂{Fe[Mo₆O₁₂(OH)₃(H₂PO₄)(HPO₄)(PO₄)₂]₂}·4H₂O (2) and (H₂bpe)₃{Fe[Mo₆O₁₂(OH)₃(HPO₄)₃(H₂PO₄)]₂}·8H₂O (3) [bpp is 1,3-bis(pyridin-4-yl)propane (C₁₃H₁₄N₂) and bpe is trans-1,2-bis(pyridin-4-yl)ethylene (C₁₂H₁₀N₂)]. The three hybrids consist of supramolecular networks built up by noncovalent interactions between {Fe[P₄Mo₆^VO₃₁]₂}²²⁻ polyanions and protonated organic cations. This kind of hybrid polyoxometalate could be applied as heterogeneous molecular catalysts for the reduction of Cr^VI. It was found that the organic moiety plays a vital role in influencing the catalytic activity of the polyanions. Organic bpp-containing hybrids 1 and 2 are highly active in the catalytic reduction of heavy metal Cr^VI ions using HCOOH as reductant, while bpe-containing hybrid 3 is inactive to this reaction. This work is significant for the design of new catalysts, as well as the exploration of reaction mechanisms at a molecular level.

Keywords: polyoxometalates; crystal structure; catalytic performance; hexavalent chromium.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618013025/jr3018sup1.cif Contains datablocks 1, 2, 3, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618013025/jr30181sup2.hkl Contains datablock 1
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618013025/jr30182sup3.hkl Contains datablock 2
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618013025/jr30183sup4.hkl Contains datablock 3

CCDC references: 1842298; 1842297; 1842296

Computing details top

For all structures, data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(1) top

Crystal data top

(C₁₃H₁₆N₂)₂[Fe(H₂O)][Sr(H₂O)₄]₂ {Fe[Mo₆O₁₂(OH)₃(H₂PO₄)(HPO₄)(PO₄)₂]₂}·5H₂O	Z = 1
M_r = 3338.82	F(000) = 1612
Triclinic, P1	D_x = 2.460 Mg m⁻³
a = 11.385 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.121 (3) Å	Cell parameters from 6029 reflections
c = 15.126 (4) Å	θ = 2.4–28.3°
α = 69.259 (3)°	µ = 3.35 mm⁻¹
β = 82.422 (4)°	T = 296 K
γ = 88.086 (4)°	Block, brown
V = 2254.0 (9) Å³	0.17 × 0.15 × 0.13 mm

Data collection top

Bruker SMART CCD area detector diffractometer	5705 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.033
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 25.0°, θ_min = 2.2°
T_min = 0.571, T_max = 0.647	h = −13→10
10357 measured reflections	k = −16→16
7715 independent reflections	l = −17→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.0682P)² + 32.5759P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
7715 reflections	Δρ_max = 2.59 e Å⁻³
616 parameters	Δρ_min = −1.40 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.57784 (9)	0.13710 (6)	0.16185 (6)	0.0200 (2)
Mo2	0.74318 (8)	0.20453 (6)	−0.06481 (6)	0.0198 (2)
Mo3	0.78967 (8)	−0.14855 (6)	0.01976 (6)	0.0194 (2)
Mo4	0.66655 (9)	−0.19228 (6)	0.18635 (6)	0.0205 (2)
Mo5	0.64028 (9)	0.22227 (7)	−0.21242 (6)	0.0227 (2)
Mo6	0.34944 (9)	0.11409 (7)	0.18114 (6)	0.0204 (2)
Sr1	0.77683 (11)	0.56098 (8)	0.09982 (9)	0.0339 (3)
Fe1	0.5000	0.0000	0.0000	0.0185 (5)
Fe2	0.5000	0.5000	0.0000	0.0211 (5)
P1	0.5384 (2)	0.71460 (19)	0.04041 (18)	0.0174 (6)
P2	0.7434 (2)	0.34275 (19)	0.0705 (2)	0.0201 (6)
P3	0.1238 (3)	0.2705 (2)	0.1310 (2)	0.0243 (6)
P4	0.5250 (3)	−0.3822 (2)	0.3651 (2)	0.0285 (7)
O1	0.6345 (6)	0.1121 (5)	−0.0875 (5)	0.0171 (15)
O2	0.6509 (6)	−0.0831 (5)	0.0641 (5)	0.0211 (16)
O3	0.4805 (6)	0.0532 (5)	0.1189 (5)	0.0206 (16)
O4	0.5719 (6)	0.2448 (5)	0.0079 (5)	0.0193 (15)
O5	0.5016 (6)	−0.1465 (5)	0.2334 (5)	0.0225 (16)
O6	0.7649 (6)	−0.0528 (5)	−0.1177 (5)	0.0210 (16)
O7	0.5576 (7)	0.6035 (5)	0.0559 (5)	0.0231 (16)
O8	0.7217 (6)	0.1034 (5)	0.0775 (5)	0.0204 (16)
O9	0.9025 (7)	−0.0820 (6)	0.0299 (6)	0.0324 (19)
O10	0.7738 (6)	−0.2722 (5)	0.1303 (5)	0.0229 (16)
O11	0.4486 (7)	0.2185 (5)	0.1901 (5)	0.0240 (16)
O12	0.6863 (7)	0.2525 (5)	0.1548 (5)	0.0255 (17)
O13	0.6476 (6)	−0.2233 (5)	−0.0251 (5)	0.0192 (15)
O14	0.8773 (7)	0.1639 (6)	−0.0958 (6)	0.0332 (19)
O15	0.1768 (8)	0.3823 (6)	0.0850 (6)	0.037 (2)
O16	0.6076 (7)	0.0573 (6)	0.2677 (5)	0.0306 (18)
O17	0.8002 (7)	0.3080 (5)	−0.0102 (5)	0.0236 (16)
O18	0.5277 (6)	0.7343 (5)	0.1357 (5)	0.0212 (16)
O19	0.6330 (7)	−0.3228 (6)	0.3013 (5)	0.0313 (19)
O20	0.1132 (7)	0.2385 (6)	0.0460 (5)	0.0278 (18)
O21	0.7126 (7)	0.3202 (5)	−0.1729 (5)	0.0270 (17)
O22	0.8461 (7)	0.3845 (5)	0.1067 (6)	0.0289 (18)
O23	0.6614 (7)	0.4316 (5)	0.0392 (6)	0.0294 (18)
O24	0.2097 (7)	0.2058 (6)	0.1964 (5)	0.0276 (17)
O25	0.7476 (8)	0.1840 (6)	−0.2791 (6)	0.036 (2)
O26	0.0044 (7)	0.2743 (6)	0.1863 (6)	0.0327 (19)
O27	0.7487 (8)	−0.1362 (6)	0.2373 (5)	0.034 (2)
O28	0.3255 (8)	0.0279 (6)	0.2908 (5)	0.034 (2)
O29	0.4114 (8)	−0.3429 (6)	0.3230 (6)	0.037 (2)
O30	0.5208 (9)	−0.3648 (6)	0.4611 (6)	0.048 (3)
H30	0.4636	−0.3954	0.4978	0.071*
O31	0.5377 (9)	−0.4943 (6)	0.3817 (6)	0.041 (2)
C1	0.9973 (15)	0.8774 (18)	0.2727 (16)	0.077 (6)
H1	1.0307	0.8189	0.2662	0.092*
C2	0.9599 (17)	0.8808 (17)	0.3610 (13)	0.078 (6)
H2	0.9713	0.8249	0.4147	0.094*
C3	0.9053 (17)	0.9652 (16)	0.3726 (14)	0.073 (5)
C4	0.8930 (16)	1.0440 (14)	0.2890 (14)	0.069 (5)
H4	0.8543	1.1018	0.2926	0.082*
C5	0.9350 (15)	1.0415 (14)	0.2009 (12)	0.064 (5)
H5	0.9279	1.0967	0.1457	0.077*
C6	0.8547 (19)	0.9660 (17)	0.4675 (14)	0.085 (6)
H6A	0.8726	1.0307	0.4719	0.103*
H6B	0.8920	0.9137	0.5160	0.103*
C7	0.717 (2)	0.9477 (16)	0.4880 (13)	0.089 (7)
H7A	0.6891	0.9522	0.5498	0.107*
H7B	0.6800	1.0015	0.4406	0.107*
C8	0.677 (2)	0.8479 (16)	0.4874 (16)	0.095 (7)
H8A	0.6973	0.8459	0.4238	0.114*
H8B	0.7190	0.7941	0.5304	0.114*
C9	0.385 (3)	0.7544 (14)	0.6339 (13)	0.091 (8)
H9	0.3545	0.7203	0.6972	0.109*
C10	0.506 (2)	0.7815 (16)	0.6066 (13)	0.085 (6)
H10	0.5576	0.7661	0.6528	0.102*
C11	0.5478 (19)	0.8285 (13)	0.5158 (11)	0.065 (5)
C12	0.4692 (19)	0.8551 (12)	0.4482 (11)	0.066 (5)
H12	0.4966	0.8919	0.3848	0.079*
C13	0.355 (2)	0.8283 (12)	0.4732 (12)	0.077 (6)
H13	0.3036	0.8433	0.4270	0.092*
N1	0.9860 (11)	0.9569 (13)	0.1979 (10)	0.062 (4)
H1A	1.0133	0.9545	0.1430	0.075*
N2	0.3145 (16)	0.7804 (11)	0.5638 (10)	0.080 (5)
H2A	0.2403	0.7651	0.5789	0.095*
O1W	0.4017 (9)	0.4128 (6)	0.1351 (6)	0.041 (2)
O2W	0.9998 (9)	0.5614 (9)	0.1097 (9)	0.070 (3)
O3W	0.7289 (17)	0.4716 (14)	0.2704 (12)	0.039 (4)	0.5
O4W	0.3427 (15)	0.4794 (11)	0.2759 (11)	0.105 (5)
O5W	0.9230 (19)	0.268 (2)	0.3702 (13)	0.169 (10)
O6W	0.833 (2)	0.622 (2)	0.420 (2)	0.105 (10)	0.5
O7W	0.199 (4)	0.599 (3)	0.473 (3)	0.165 (18)	0.5
O8W	0.886 (5)	0.615 (3)	0.596 (3)	0.174 (18)	0.5
O9W	0.821 (4)	0.513 (4)	0.282 (2)	0.17 (2)	0.5
O3W'	0.614 (2)	0.4526 (18)	0.2350 (16)	0.079 (8)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.0321 (5)	0.0110 (4)	0.0181 (5)	0.0005 (4)	−0.0053 (4)	−0.0060 (4)
Mo2	0.0266 (5)	0.0113 (4)	0.0226 (5)	−0.0001 (4)	−0.0026 (4)	−0.0075 (4)
Mo3	0.0269 (5)	0.0117 (4)	0.0205 (5)	0.0000 (4)	−0.0043 (4)	−0.0062 (4)
Mo4	0.0340 (6)	0.0106 (4)	0.0168 (5)	−0.0007 (4)	−0.0049 (4)	−0.0040 (4)
Mo5	0.0329 (6)	0.0151 (5)	0.0182 (5)	−0.0029 (4)	−0.0015 (4)	−0.0039 (4)
Mo6	0.0312 (5)	0.0129 (4)	0.0178 (5)	0.0003 (4)	−0.0025 (4)	−0.0064 (4)
Sr1	0.0405 (7)	0.0183 (6)	0.0494 (7)	0.0048 (5)	−0.0110 (6)	−0.0183 (5)
Fe1	0.0292 (12)	0.0109 (10)	0.0163 (10)	0.0003 (8)	−0.0041 (9)	−0.0056 (8)
Fe2	0.0290 (12)	0.0103 (10)	0.0269 (12)	0.0016 (9)	−0.0086 (9)	−0.0083 (9)
P1	0.0259 (15)	0.0096 (12)	0.0169 (13)	0.0004 (10)	−0.0036 (11)	−0.0047 (10)
P2	0.0268 (15)	0.0105 (13)	0.0261 (15)	0.0010 (11)	−0.0064 (12)	−0.0095 (11)
P3	0.0281 (16)	0.0192 (14)	0.0278 (16)	0.0034 (12)	−0.0021 (12)	−0.0117 (12)
P4	0.052 (2)	0.0132 (14)	0.0174 (14)	−0.0007 (13)	−0.0052 (13)	−0.0010 (11)
O1	0.028 (4)	0.009 (3)	0.016 (4)	−0.002 (3)	−0.007 (3)	−0.004 (3)
O2	0.032 (4)	0.015 (4)	0.017 (4)	−0.001 (3)	0.001 (3)	−0.008 (3)
O3	0.025 (4)	0.012 (3)	0.027 (4)	0.003 (3)	−0.001 (3)	−0.010 (3)
O4	0.025 (4)	0.013 (4)	0.021 (4)	0.002 (3)	−0.004 (3)	−0.007 (3)
O5	0.028 (4)	0.018 (4)	0.023 (4)	0.001 (3)	−0.001 (3)	−0.011 (3)
O6	0.031 (4)	0.009 (3)	0.020 (4)	−0.001 (3)	−0.007 (3)	−0.001 (3)
O7	0.032 (4)	0.010 (4)	0.030 (4)	−0.002 (3)	−0.004 (3)	−0.011 (3)
O8	0.034 (4)	0.009 (3)	0.021 (4)	0.009 (3)	−0.011 (3)	−0.007 (3)
O9	0.034 (5)	0.027 (4)	0.038 (5)	−0.006 (4)	−0.009 (4)	−0.011 (4)
O10	0.027 (4)	0.017 (4)	0.027 (4)	−0.001 (3)	−0.009 (3)	−0.008 (3)
O11	0.039 (5)	0.016 (4)	0.021 (4)	0.004 (3)	−0.007 (3)	−0.011 (3)
O12	0.040 (5)	0.019 (4)	0.024 (4)	−0.003 (3)	−0.005 (3)	−0.014 (3)
O13	0.020 (4)	0.018 (4)	0.019 (4)	−0.001 (3)	−0.003 (3)	−0.007 (3)
O14	0.032 (5)	0.035 (5)	0.037 (5)	0.012 (4)	−0.010 (4)	−0.018 (4)
O15	0.050 (6)	0.025 (4)	0.035 (5)	−0.007 (4)	0.000 (4)	−0.010 (4)
O16	0.047 (5)	0.019 (4)	0.026 (4)	0.008 (4)	−0.009 (4)	−0.007 (3)
O17	0.031 (4)	0.016 (4)	0.027 (4)	−0.002 (3)	−0.005 (3)	−0.012 (3)
O18	0.035 (4)	0.009 (3)	0.019 (4)	−0.003 (3)	−0.002 (3)	−0.006 (3)
O19	0.042 (5)	0.021 (4)	0.020 (4)	−0.005 (4)	−0.003 (4)	0.006 (3)
O20	0.026 (4)	0.033 (4)	0.029 (4)	0.008 (3)	−0.007 (3)	−0.016 (4)
O21	0.045 (5)	0.013 (4)	0.020 (4)	−0.003 (3)	−0.006 (3)	−0.002 (3)
O22	0.035 (5)	0.018 (4)	0.042 (5)	0.007 (3)	−0.013 (4)	−0.019 (4)
O23	0.042 (5)	0.013 (4)	0.039 (5)	0.004 (3)	−0.006 (4)	−0.015 (3)
O24	0.036 (5)	0.026 (4)	0.021 (4)	0.005 (3)	0.000 (3)	−0.010 (3)
O25	0.048 (5)	0.032 (5)	0.031 (5)	−0.001 (4)	−0.004 (4)	−0.016 (4)
O26	0.031 (5)	0.034 (5)	0.035 (5)	0.008 (4)	−0.003 (4)	−0.017 (4)
O27	0.055 (6)	0.025 (4)	0.025 (4)	0.000 (4)	−0.011 (4)	−0.008 (4)
O28	0.052 (5)	0.027 (4)	0.020 (4)	−0.004 (4)	−0.001 (4)	−0.006 (4)
O29	0.043 (5)	0.029 (5)	0.025 (4)	−0.006 (4)	−0.003 (4)	0.006 (4)
O30	0.091 (8)	0.025 (5)	0.025 (5)	−0.013 (5)	0.000 (5)	−0.008 (4)
O31	0.071 (7)	0.014 (4)	0.031 (5)	−0.001 (4)	0.005 (4)	−0.004 (4)
C1	0.043 (10)	0.111 (17)	0.096 (15)	0.012 (10)	−0.022 (10)	−0.058 (14)
C2	0.081 (13)	0.108 (16)	0.050 (10)	0.033 (12)	−0.029 (9)	−0.028 (11)
C3	0.081 (13)	0.092 (15)	0.068 (12)	0.001 (11)	−0.010 (10)	−0.054 (12)
C4	0.066 (11)	0.069 (12)	0.082 (13)	−0.019 (9)	0.011 (10)	−0.047 (11)
C5	0.066 (11)	0.070 (12)	0.062 (11)	−0.032 (9)	0.021 (9)	−0.036 (9)
C6	0.090 (16)	0.099 (16)	0.079 (14)	−0.013 (12)	−0.013 (11)	−0.042 (12)
C7	0.14 (2)	0.089 (15)	0.048 (10)	0.021 (14)	−0.004 (11)	−0.045 (11)
C8	0.13 (2)	0.077 (14)	0.092 (15)	0.020 (13)	0.000 (14)	−0.053 (13)
C9	0.19 (3)	0.048 (11)	0.033 (10)	0.014 (14)	−0.019 (13)	−0.014 (8)
C10	0.14 (2)	0.091 (15)	0.039 (11)	0.008 (14)	−0.013 (11)	−0.038 (10)
C11	0.108 (15)	0.055 (10)	0.034 (9)	0.006 (10)	−0.006 (9)	−0.021 (8)
C12	0.121 (17)	0.043 (9)	0.026 (8)	0.001 (10)	−0.001 (9)	−0.007 (7)
C13	0.14 (2)	0.045 (10)	0.036 (10)	−0.005 (11)	0.007 (11)	−0.011 (8)
N1	0.048 (8)	0.096 (12)	0.055 (9)	−0.016 (8)	0.002 (7)	−0.041 (9)
N2	0.120 (14)	0.057 (9)	0.056 (10)	−0.011 (9)	0.002 (9)	−0.018 (8)
O1W	0.070 (7)	0.015 (4)	0.034 (5)	0.004 (4)	−0.004 (4)	−0.004 (4)
O2W	0.047 (7)	0.061 (7)	0.085 (8)	−0.019 (5)	−0.005 (6)	−0.003 (6)
O3W	0.044 (12)	0.042 (11)	0.029 (10)	0.008 (9)	−0.010 (9)	−0.009 (8)
O4W	0.151 (15)	0.077 (10)	0.099 (11)	−0.010 (9)	−0.019 (10)	−0.044 (9)
O5W	0.169 (19)	0.26 (3)	0.100 (13)	−0.095 (18)	0.037 (12)	−0.100 (16)
O6W	0.066 (18)	0.10 (2)	0.15 (3)	0.015 (15)	−0.051 (18)	−0.03 (2)
O7W	0.15 (3)	0.10 (3)	0.17 (4)	−0.04 (2)	0.06 (3)	0.02 (3)
O8W	0.26 (6)	0.12 (3)	0.15 (4)	0.00 (3)	−0.03 (4)	−0.05 (3)
O9W	0.18 (4)	0.25 (5)	0.047 (18)	0.12 (4)	−0.04 (2)	−0.04 (2)
O3W'	0.12 (2)	0.072 (16)	0.062 (15)	0.047 (15)	−0.029 (14)	−0.039 (13)

Geometric parameters (Å, º) top

Mo1—O16	1.669 (7)	P1—O7	1.515 (7)
Mo1—O11	1.933 (7)	P1—O4ⁱⁱⁱ	1.528 (7)
Mo1—O3	1.969 (7)	P1—O18	1.551 (7)
Mo1—O12	2.041 (7)	P1—O13^iv	1.559 (7)
Mo1—O8	2.088 (7)	P2—O23	1.513 (8)
Mo1—O4	2.294 (7)	P2—O17	1.531 (7)
Mo1—Mo6	2.5965 (15)	P2—O12	1.536 (8)
Mo2—O14	1.680 (8)	P2—O22	1.566 (8)
Mo2—O21	1.919 (7)	P3—O26	1.509 (8)
Mo2—O1	1.972 (6)	P3—O24	1.526 (8)
Mo2—O17	2.073 (7)	P3—O20	1.526 (8)
Mo2—O8	2.107 (7)	P3—O15	1.586 (8)
Mo2—O4	2.267 (7)	P3—Sr1ⁱⁱⁱ	3.519 (3)
Mo2—Mo5	2.5874 (14)	P4—O29	1.517 (9)
Mo3—O9	1.671 (8)	P4—O31	1.517 (8)
Mo3—O10	1.937 (7)	P4—O19	1.526 (8)
Mo3—O2	1.965 (7)	P4—O30	1.551 (8)
Mo3—O20ⁱ	2.083 (7)	O4—P1ⁱⁱⁱ	1.528 (7)
Mo3—O6	2.090 (7)	O5—Mo5ⁱ	2.085 (7)
Mo3—O13	2.259 (7)	O6—Mo6ⁱ	2.088 (7)
Mo3—Mo4	2.5922 (13)	O10—Sr1ⁱⁱ	2.555 (7)
Mo3—Sr1ⁱⁱ	3.8453 (16)	O13—P1ⁱⁱ	1.559 (7)
Mo4—O27	1.663 (8)	O13—Mo6ⁱ	2.314 (7)
Mo4—O10	1.948 (7)	O15—Sr1ⁱⁱⁱ	2.605 (8)
Mo4—O2	1.970 (7)	O18—Mo4^iv	2.270 (7)
Mo4—O19	2.042 (7)	O18—Mo5ⁱⁱⁱ	2.285 (7)
Mo4—O5	2.084 (7)	O20—Mo3ⁱ	2.083 (7)
Mo4—O18ⁱⁱ	2.270 (7)	O20—Sr1ⁱⁱⁱ	3.087 (8)
Mo5—O25	1.679 (8)	O29—Mo5ⁱ	2.055 (8)
Mo5—O21	1.933 (7)	O30—H30	0.8200
Mo5—O1	1.972 (6)	C1—N1	1.30 (2)
Mo5—O29ⁱ	2.055 (8)	C1—C2	1.36 (2)
Mo5—O5ⁱ	2.085 (7)	C1—H1	0.9300
Mo5—O18ⁱⁱⁱ	2.285 (7)	C2—C3	1.38 (3)
Mo6—O28	1.667 (8)	C2—H2	0.9300
Mo6—O11	1.940 (7)	C3—C4	1.38 (3)
Mo6—O3	1.992 (7)	C3—C6	1.48 (2)
Mo6—O24	2.059 (7)	C4—C5	1.37 (2)
Mo6—O6ⁱ	2.088 (7)	C4—H4	0.9300
Mo6—O13ⁱ	2.314 (7)	C5—N1	1.32 (2)
Sr1—O3W	2.433 (18)	C5—H5	0.9300
Sr1—O10^iv	2.555 (7)	C6—C7	1.57 (3)
Sr1—O22	2.559 (7)	C6—H6A	0.9700
Sr1—O2W	2.563 (11)	C6—H6B	0.9700
Sr1—O15ⁱⁱⁱ	2.605 (8)	C7—C8	1.50 (3)
Sr1—O3W'	2.64 (3)	C7—H7A	0.9700
Sr1—O7	2.662 (8)	C7—H7B	0.9700
Sr1—O9W	2.70 (3)	C8—C11	1.48 (3)
Sr1—O23	2.751 (7)	C8—H8A	0.9700
Sr1—O20ⁱⁱⁱ	3.087 (8)	C8—H8B	0.9700
Sr1—P2	3.306 (3)	C9—N2	1.35 (2)
Sr1—P1	3.428 (3)	C9—C10	1.42 (3)
Fe1—O3	2.165 (7)	C9—H9	0.9300
Fe1—O3ⁱ	2.165 (7)	C10—C11	1.32 (2)
Fe1—O1ⁱ	2.178 (7)	C10—H10	0.9300
Fe1—O1	2.178 (7)	C11—C12	1.39 (2)
Fe1—O2ⁱ	2.183 (7)	C12—C13	1.34 (3)
Fe1—O2	2.183 (7)	C12—H12	0.9300
Fe2—O7ⁱⁱⁱ	2.089 (6)	C13—N2	1.32 (2)
Fe2—O7	2.089 (7)	C13—H13	0.9300
Fe2—O23	2.104 (8)	N1—H1A	0.8600
Fe2—O23ⁱⁱⁱ	2.104 (8)	N2—H2A	0.8600
Fe2—O1W	2.157 (8)	O3W—O9W	1.28 (5)
Fe2—O1Wⁱⁱⁱ	2.157 (8)	O3W—O3W'	1.55 (3)

O16—Mo1—O11	105.3 (3)	O7—Sr1—P2	87.04 (15)
O16—Mo1—O3	102.8 (3)	O9W—Sr1—P2	105.7 (11)
O11—Mo1—O3	95.6 (3)	O23—Sr1—P2	26.99 (16)
O16—Mo1—O12	96.7 (3)	O20ⁱⁱⁱ—Sr1—P2	128.75 (15)
O11—Mo1—O12	86.0 (3)	O3W—Sr1—P1	103.7 (5)
O3—Mo1—O12	159.3 (3)	O10^iv—Sr1—P1	62.70 (17)
O16—Mo1—O8	98.1 (3)	O22—Sr1—P1	138.91 (18)
O11—Mo1—O8	155.2 (3)	O2W—Sr1—P1	143.6 (3)
O3—Mo1—O8	86.9 (3)	O15ⁱⁱⁱ—Sr1—P1	81.5 (2)
O12—Mo1—O8	83.2 (3)	O3W'—Sr1—P1	80.9 (5)
O16—Mo1—O4	169.9 (3)	O7—Sr1—P1	24.99 (14)
O11—Mo1—O4	83.4 (3)	O9W—Sr1—P1	115.2 (8)
O3—Mo1—O4	81.0 (3)	O23—Sr1—P1	84.77 (17)
O12—Mo1—O4	78.7 (3)	O20ⁱⁱⁱ—Sr1—P1	75.76 (15)
O8—Mo1—O4	72.6 (2)	P2—Sr1—P1	111.53 (7)
O16—Mo1—Mo6	100.5 (3)	O3—Fe1—O3ⁱ	180.0
O11—Mo1—Mo6	48.0 (2)	O3—Fe1—O1ⁱ	84.6 (2)
O3—Mo1—Mo6	49.4 (2)	O3ⁱ—Fe1—O1ⁱ	95.4 (2)
O12—Mo1—Mo6	133.7 (2)	O3—Fe1—O1	95.4 (2)
O8—Mo1—Mo6	135.29 (19)	O3ⁱ—Fe1—O1	84.6 (2)
O4—Mo1—Mo6	89.11 (18)	O1ⁱ—Fe1—O1	180.0
O14—Mo2—O21	105.4 (4)	O3—Fe1—O2ⁱ	95.1 (3)
O14—Mo2—O1	102.7 (3)	O3ⁱ—Fe1—O2ⁱ	84.9 (3)
O21—Mo2—O1	95.3 (3)	O1ⁱ—Fe1—O2ⁱ	83.8 (3)
O14—Mo2—O17	97.5 (3)	O1—Fe1—O2ⁱ	96.2 (3)
O21—Mo2—O17	85.9 (3)	O3—Fe1—O2	84.9 (3)
O1—Mo2—O17	158.5 (3)	O3ⁱ—Fe1—O2	95.1 (3)
O14—Mo2—O8	96.2 (3)	O1ⁱ—Fe1—O2	96.2 (3)
O21—Mo2—O8	157.6 (3)	O1—Fe1—O2	83.8 (3)
O1—Mo2—O8	85.4 (3)	O2ⁱ—Fe1—O2	180.0
O17—Mo2—O8	85.5 (3)	O7ⁱⁱⁱ—Fe2—O7	180.0 (3)
O14—Mo2—O4	168.2 (3)	O7ⁱⁱⁱ—Fe2—O23	98.3 (3)
O21—Mo2—O4	85.1 (3)	O7—Fe2—O23	81.7 (3)
O1—Mo2—O4	81.2 (3)	O7ⁱⁱⁱ—Fe2—O23ⁱⁱⁱ	81.7 (3)
O17—Mo2—O4	77.6 (3)	O7—Fe2—O23ⁱⁱⁱ	98.3 (3)
O8—Mo2—O4	72.8 (3)	O23—Fe2—O23ⁱⁱⁱ	180.0
O14—Mo2—Mo5	100.8 (3)	O7ⁱⁱⁱ—Fe2—O1W	88.1 (3)
O21—Mo2—Mo5	48.0 (2)	O7—Fe2—O1W	91.9 (3)
O1—Mo2—Mo5	48.99 (19)	O23—Fe2—O1W	93.1 (3)
O17—Mo2—Mo5	133.5 (2)	O23ⁱⁱⁱ—Fe2—O1W	86.9 (3)
O8—Mo2—Mo5	133.7 (2)	O7ⁱⁱⁱ—Fe2—O1Wⁱⁱⁱ	91.9 (3)
O4—Mo2—Mo5	90.15 (18)	O7—Fe2—O1Wⁱⁱⁱ	88.1 (3)
O9—Mo3—O10	107.2 (3)	O23—Fe2—O1Wⁱⁱⁱ	86.9 (3)
O9—Mo3—O2	102.5 (3)	O23ⁱⁱⁱ—Fe2—O1Wⁱⁱⁱ	93.1 (3)
O10—Mo3—O2	95.3 (3)	O1W—Fe2—O1Wⁱⁱⁱ	180.0
O9—Mo3—O20ⁱ	98.1 (4)	O7—P1—O4ⁱⁱⁱ	112.4 (4)
O10—Mo3—O20ⁱ	83.9 (3)	O7—P1—O18	111.4 (4)
O2—Mo3—O20ⁱ	158.6 (3)	O4ⁱⁱⁱ—P1—O18	108.7 (4)
O9—Mo3—O6	95.5 (3)	O7—P1—O13^iv	108.8 (4)
O10—Mo3—O6	156.3 (3)	O4ⁱⁱⁱ—P1—O13^iv	107.9 (4)
O2—Mo3—O6	86.2 (3)	O18—P1—O13^iv	107.5 (4)
O20ⁱ—Mo3—O6	86.2 (3)	O7—P1—Sr1	47.9 (3)
O9—Mo3—O13	168.7 (3)	O4ⁱⁱⁱ—P1—Sr1	157.2 (3)
O10—Mo3—O13	82.7 (3)	O18—P1—Sr1	91.3 (3)
O2—Mo3—O13	81.5 (3)	O13^iv—P1—Sr1	74.7 (3)
O20ⁱ—Mo3—O13	77.1 (3)	O23—P2—O17	114.1 (4)
O6—Mo3—O13	74.1 (3)	O23—P2—O12	113.3 (5)
O9—Mo3—Mo4	101.5 (3)	O17—P2—O12	110.6 (4)
O10—Mo3—Mo4	48.3 (2)	O23—P2—O22	104.1 (4)
O2—Mo3—Mo4	48.9 (2)	O17—P2—O22	107.0 (4)
O20ⁱ—Mo3—Mo4	131.8 (2)	O12—P2—O22	107.1 (4)
O6—Mo3—Mo4	134.3 (2)	O23—P2—Sr1	55.6 (3)
O13—Mo3—Mo4	89.17 (17)	O17—P2—Sr1	128.9 (3)
O9—Mo3—Sr1ⁱⁱ	124.7 (3)	O12—P2—Sr1	119.2 (3)
O10—Mo3—Sr1ⁱⁱ	36.3 (2)	O22—P2—Sr1	48.7 (3)
O2—Mo3—Sr1ⁱⁱ	116.6 (2)	O26—P3—O24	111.1 (4)
O20ⁱ—Mo3—Sr1ⁱⁱ	53.2 (2)	O26—P3—O20	111.8 (5)
O6—Mo3—Sr1ⁱⁱ	123.18 (18)	O24—P3—O20	113.1 (4)
O13—Mo3—Sr1ⁱⁱ	60.64 (18)	O26—P3—O15	108.1 (5)
Mo4—Mo3—Sr1ⁱⁱ	79.68 (3)	O24—P3—O15	107.8 (5)
O27—Mo4—O10	106.7 (4)	O20—P3—O15	104.5 (5)
O27—Mo4—O2	101.8 (3)	O26—P3—Sr1ⁱⁱⁱ	125.0 (3)
O10—Mo4—O2	94.8 (3)	O24—P3—Sr1ⁱⁱⁱ	121.7 (3)
O27—Mo4—O19	96.5 (3)	O20—P3—Sr1ⁱⁱⁱ	61.2 (3)
O10—Mo4—O19	86.2 (3)	O15—P3—Sr1ⁱⁱⁱ	43.4 (3)
O2—Mo4—O19	160.5 (3)	O29—P4—O31	110.4 (5)
O27—Mo4—O5	97.5 (4)	O29—P4—O19	111.3 (4)
O10—Mo4—O5	155.1 (3)	O31—P4—O19	110.6 (5)
O2—Mo4—O5	85.5 (3)	O29—P4—O30	108.6 (5)
O19—Mo4—O5	85.5 (3)	O31—P4—O30	109.7 (5)
O27—Mo4—O18ⁱⁱ	169.9 (3)	O19—P4—O30	106.1 (5)
O10—Mo4—O18ⁱⁱ	82.5 (3)	Mo5—O1—Mo2	82.0 (2)
O2—Mo4—O18ⁱⁱ	81.1 (3)	Mo5—O1—Fe1	133.7 (3)
O19—Mo4—O18ⁱⁱ	79.7 (3)	Mo2—O1—Fe1	135.7 (3)
O5—Mo4—O18ⁱⁱ	72.9 (3)	Mo3—O2—Mo4	82.4 (3)
O27—Mo4—Mo3	100.6 (3)	Mo3—O2—Fe1	135.2 (3)
O10—Mo4—Mo3	48.0 (2)	Mo4—O2—Fe1	133.4 (4)
O2—Mo4—Mo3	48.7 (2)	Mo1—O3—Mo6	81.9 (2)
O19—Mo4—Mo3	134.0 (2)	Mo1—O3—Fe1	134.8 (4)
O5—Mo4—Mo3	133.2 (2)	Mo6—O3—Fe1	134.9 (4)
O18ⁱⁱ—Mo4—Mo3	88.69 (18)	P1ⁱⁱⁱ—O4—Mo2	125.1 (4)
O25—Mo5—O21	106.5 (4)	P1ⁱⁱⁱ—O4—Mo1	127.2 (4)
O25—Mo5—O1	102.2 (4)	Mo2—O4—Mo1	100.6 (3)
O21—Mo5—O1	94.9 (3)	Mo4—O5—Mo5ⁱ	113.5 (3)
O25—Mo5—O29ⁱ	95.9 (4)	Mo6ⁱ—O6—Mo3	113.1 (3)
O21—Mo5—O29ⁱ	87.1 (3)	P1—O7—Fe2	136.1 (5)
O1—Mo5—O29ⁱ	160.4 (3)	P1—O7—Sr1	107.1 (4)
O25—Mo5—O5ⁱ	97.9 (3)	Fe2—O7—Sr1	110.3 (3)
O21—Mo5—O5ⁱ	154.8 (3)	Mo1—O8—Mo2	113.5 (3)
O1—Mo5—O5ⁱ	85.6 (3)	Mo3—O10—Mo4	83.7 (3)
O29ⁱ—Mo5—O5ⁱ	84.5 (3)	Mo3—O10—Sr1ⁱⁱ	117.1 (3)
O25—Mo5—O18ⁱⁱⁱ	170.1 (3)	Mo4—O10—Sr1ⁱⁱ	139.9 (3)
O21—Mo5—O18ⁱⁱⁱ	82.6 (3)	Mo1—O11—Mo6	84.2 (3)
O1—Mo5—O18ⁱⁱⁱ	80.4 (3)	P2—O12—Mo1	132.1 (4)
O29ⁱ—Mo5—O18ⁱⁱⁱ	80.5 (3)	P1ⁱⁱ—O13—Mo3	126.5 (4)
O5ⁱ—Mo5—O18ⁱⁱⁱ	72.6 (3)	P1ⁱⁱ—O13—Mo6ⁱ	126.2 (4)
O25—Mo5—Mo2	101.3 (3)	Mo3—O13—Mo6ⁱ	99.3 (3)
O21—Mo5—Mo2	47.6 (2)	P3—O15—Sr1ⁱⁱⁱ	111.9 (4)
O1—Mo5—Mo2	49.01 (19)	P2—O17—Mo2	131.3 (4)
O29ⁱ—Mo5—Mo2	134.4 (2)	P1—O18—Mo4^iv	126.7 (4)
O5ⁱ—Mo5—Mo2	133.4 (2)	P1—O18—Mo5ⁱⁱⁱ	126.4 (4)
O18ⁱⁱⁱ—Mo5—Mo2	87.72 (18)	Mo4^iv—O18—Mo5ⁱⁱⁱ	99.9 (3)
O28—Mo6—O11	105.9 (3)	P4—O19—Mo4	137.6 (5)
O28—Mo6—O3	102.4 (4)	P3—O20—Mo3ⁱ	135.7 (5)
O11—Mo6—O3	94.7 (3)	P3—O20—Sr1ⁱⁱⁱ	93.2 (4)
O28—Mo6—O24	96.7 (4)	Mo3ⁱ—O20—Sr1ⁱⁱⁱ	94.1 (3)
O11—Mo6—O24	85.6 (3)	Mo2—O21—Mo5	84.4 (3)
O3—Mo6—O24	160.0 (3)	P2—O22—Sr1	103.9 (4)
O28—Mo6—O6ⁱ	97.7 (3)	P2—O23—Fe2	154.2 (5)
O11—Mo6—O6ⁱ	155.4 (3)	P2—O23—Sr1	97.4 (4)
O3—Mo6—O6ⁱ	86.5 (3)	Fe2—O23—Sr1	106.7 (3)
O24—Mo6—O6ⁱ	85.1 (3)	P3—O24—Mo6	134.9 (4)
O28—Mo6—O13ⁱ	170.1 (3)	P4—O29—Mo5ⁱ	137.7 (5)
O11—Mo6—O13ⁱ	83.0 (3)	P4—O30—H30	109.5
O3—Mo6—O13ⁱ	80.5 (3)	N1—C1—C2	119.3 (19)
O24—Mo6—O13ⁱ	79.6 (3)	N1—C1—H1	120.4
O6ⁱ—Mo6—O13ⁱ	72.9 (2)	C2—C1—H1	120.4
O28—Mo6—Mo1	100.7 (3)	C1—C2—C3	121.5 (19)
O11—Mo6—Mo1	47.8 (2)	C1—C2—H2	119.2
O3—Mo6—Mo1	48.6 (2)	C3—C2—H2	119.2
O24—Mo6—Mo1	133.1 (2)	C4—C3—C2	114.8 (16)
O6ⁱ—Mo6—Mo1	134.2 (2)	C4—C3—C6	123.2 (19)
O13ⁱ—Mo6—Mo1	88.38 (17)	C2—C3—C6	122 (2)
O3W—Sr1—O10^iv	89.1 (5)	C5—C4—C3	123.3 (18)
O3W—Sr1—O22	81.4 (5)	C5—C4—H4	118.4
O10^iv—Sr1—O22	157.9 (2)	C3—C4—H4	118.4
O3W—Sr1—O2W	93.0 (5)	N1—C5—C4	117.0 (18)
O10^iv—Sr1—O2W	85.9 (3)	N1—C5—H5	121.5
O22—Sr1—O2W	74.9 (3)	C4—C5—H5	121.5
O3W—Sr1—O15ⁱⁱⁱ	167.5 (5)	C3—C6—C7	112.8 (15)
O10^iv—Sr1—O15ⁱⁱⁱ	103.4 (2)	C3—C6—H6A	109.0
O22—Sr1—O15ⁱⁱⁱ	87.2 (3)	C7—C6—H6A	109.0
O2W—Sr1—O15ⁱⁱⁱ	89.1 (3)	C3—C6—H6B	109.0
O3W—Sr1—O3W'	35.3 (7)	C7—C6—H6B	109.0
O10^iv—Sr1—O3W'	102.1 (5)	H6A—C6—H6B	107.8
O22—Sr1—O3W'	81.4 (5)	C8—C7—C6	114.8 (17)
O2W—Sr1—O3W'	126.1 (6)	C8—C7—H7A	108.6
O15ⁱⁱⁱ—Sr1—O3W'	137.7 (6)	C6—C7—H7A	108.6
O3W—Sr1—O7	98.6 (5)	C8—C7—H7B	108.6
O10^iv—Sr1—O7	86.7 (2)	C6—C7—H7B	108.6
O22—Sr1—O7	114.3 (2)	H7A—C7—H7B	107.5
O2W—Sr1—O7	166.1 (3)	C11—C8—C7	113.7 (16)
O15ⁱⁱⁱ—Sr1—O7	81.3 (3)	C11—C8—H8A	108.8
O3W'—Sr1—O7	67.1 (5)	C7—C8—H8A	108.8
O3W—Sr1—O9W	28.2 (11)	C11—C8—H8B	108.8
O10^iv—Sr1—O9W	74.1 (11)	C7—C8—H8B	108.8
O22—Sr1—O9W	88.6 (10)	H8A—C8—H8B	107.7
O2W—Sr1—O9W	68.5 (10)	N2—C9—C10	117.1 (18)
O15ⁱⁱⁱ—Sr1—O9W	157.5 (10)	N2—C9—H9	121.5
O3W'—Sr1—O9W	63.1 (13)	C10—C9—H9	121.5
O7—Sr1—O9W	120.4 (9)	C11—C10—C9	120 (2)
O3W—Sr1—O23	97.7 (5)	C11—C10—H10	119.8
O10^iv—Sr1—O23	147.4 (2)	C9—C10—H10	119.8
O22—Sr1—O23	54.3 (2)	C10—C11—C12	119 (2)
O2W—Sr1—O23	125.2 (3)	C10—C11—C8	120 (2)
O15ⁱⁱⁱ—Sr1—O23	71.2 (2)	C12—C11—C8	121.1 (17)
O3W'—Sr1—O23	69.1 (5)	C13—C12—C11	120.8 (16)
O7—Sr1—O23	60.8 (2)	C13—C12—H12	119.6
O9W—Sr1—O23	122.9 (12)	C11—C12—H12	119.6
O3W—Sr1—O20ⁱⁱⁱ	141.7 (5)	N2—C13—C12	120 (2)
O10^iv—Sr1—O20ⁱⁱⁱ	56.0 (2)	N2—C13—H13	120.2
O22—Sr1—O20ⁱⁱⁱ	124.6 (2)	C12—C13—H13	120.2
O2W—Sr1—O20ⁱⁱⁱ	71.3 (3)	C1—N1—C5	124.1 (16)
O15ⁱⁱⁱ—Sr1—O20ⁱⁱⁱ	50.3 (2)	C1—N1—H1A	118.0
O3W'—Sr1—O20ⁱⁱⁱ	153.5 (5)	C5—N1—H1A	118.0
O7—Sr1—O20ⁱⁱⁱ	94.8 (2)	C13—N2—C9	123 (2)
O9W—Sr1—O20ⁱⁱⁱ	116.7 (13)	C13—N2—H2A	118.5
O23—Sr1—O20ⁱⁱⁱ	120.1 (2)	C9—N2—H2A	118.5
O3W—Sr1—P2	87.8 (4)	O9W—O3W—O3W'	163 (3)
O10^iv—Sr1—P2	172.53 (18)	O9W—O3W—Sr1	87.7 (17)
O22—Sr1—P2	27.39 (18)	O3W'—O3W—Sr1	79.5 (12)
O2W—Sr1—P2	101.1 (3)	O3W—O9W—Sr1	64.1 (15)
O15ⁱⁱⁱ—Sr1—P2	79.70 (18)	O3W—O3W'—Sr1	65.2 (12)
O3W'—Sr1—P2	71.6 (5)

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

(2) top

Crystal data top

(C₁₃H₁₆N₂)₂[Na(H₂O)(C₂H₅O)][Fe(H₂O)₂][Ca(H₂O)₂]2 {Fe[Mo₆O₁₂(OH)₃(H₂PO₄)(HPO₄)(PO₄)₂]₂}·4H₂O	F(000) = 6340
M_r = 3260.77	D_x = 2.410 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.317 (7) Å	Cell parameters from 9260 reflections
b = 18.533 (6) Å	θ = 2.4–27.9°
c = 22.838 (8) Å	µ = 2.31 mm⁻¹
β = 95.130 (5)°	T = 296 K
V = 8986 (5) Å³	Block, red
Z = 4	0.19 × 0.17 × 0.15 mm

Data collection top

Bruker SMART CCD area detector diffractometer	7629 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.022
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 25.0°, θ_min = 1.8°
T_min = 0.652, T_max = 0.708	h = −25→19
19982 measured reflections	k = −22→21
7781 independent reflections	l = −27→26

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0626P)² + 126.1618P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
7781 reflections	Δρ_max = 1.89 e Å⁻³
616 parameters	Δρ_min = −0.73 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.19573 (2)	0.39849 (2)	−0.11379 (2)	0.01551 (12)
Mo2	0.27126 (2)	0.40320 (2)	0.11744 (2)	0.01539 (12)
Mo3	0.42188 (2)	0.26408 (2)	−0.03694 (2)	0.01558 (12)
Mo4	0.29055 (2)	0.45615 (2)	0.01341 (2)	0.01544 (12)
Mo5	0.34973 (2)	0.22651 (3)	−0.13064 (2)	0.01646 (13)
Mo6	0.10529 (2)	0.30434 (2)	−0.10468 (2)	0.01554 (12)
P1	0.53381 (7)	0.17840 (8)	0.04940 (7)	0.0195 (3)
P2	0.31143 (8)	0.10455 (8)	−0.23305 (7)	0.0210 (3)
P3	0.21097 (7)	0.57394 (8)	−0.07794 (7)	0.0199 (3)
P4	0.13500 (7)	0.40689 (7)	0.02340 (6)	0.0139 (3)
Fe1	0.2500	0.2500	0.0000	0.0159 (2)
Ca1	0.15813 (7)	0.58587 (7)	0.05502 (6)	0.0315 (3)
Fe2	0.5000	0.0000	0.0000	0.0200 (3)
Na1	0.0495 (4)	0.4277 (5)	0.1438 (4)	0.080 (3)	0.5
O1	0.32807 (18)	0.2655 (2)	−0.05262 (17)	0.0166 (8)
O2	0.16924 (18)	0.3796 (2)	0.08254 (16)	0.0167 (8)
O3	0.28649 (18)	0.3540 (2)	0.04133 (17)	0.0180 (8)
O4	0.40033 (18)	0.15799 (19)	0.00802 (16)	0.0152 (8)
O5	0.25154 (19)	0.4983 (2)	0.08050 (17)	0.0192 (8)
O6	0.19656 (18)	0.3004 (2)	−0.07602 (17)	0.0170 (8)
O7	0.24688 (18)	0.3000 (2)	0.14807 (17)	0.0185 (8)
H7	0.2723	0.2715	0.1308	0.08 (3)*
O8	0.3684 (2)	0.4748 (2)	0.02342 (19)	0.0261 (9)
O9	0.5332 (2)	0.0995 (2)	0.0293 (2)	0.0294 (10)
O10	0.28819 (18)	0.4119 (2)	−0.07210 (17)	0.0195 (8)
H10A	0.3094	0.3638	−0.0698	0.05 (3)*
O11	0.3616 (2)	0.1532 (2)	−0.19819 (18)	0.0267 (9)
O12	0.1036 (2)	0.2613 (2)	−0.17037 (19)	0.0263 (9)
O13	0.18622 (18)	0.4329 (2)	−0.01728 (17)	0.0175 (8)
O14	0.2680 (2)	0.1448 (3)	−0.27817 (19)	0.0324 (11)
O15	0.09462 (19)	0.2099 (2)	−0.05261 (17)	0.0188 (8)
H15	0.1323	0.1823	−0.0539	0.04 (2)*
O16	0.51120 (19)	0.2321 (2)	−0.00166 (19)	0.0216 (9)
O17	0.2755 (2)	0.0595 (2)	−0.18823 (18)	0.0230 (9)
O18	0.10380 (19)	0.4076 (2)	−0.12222 (18)	0.0194 (8)
O19	0.49130 (18)	0.1899 (2)	0.10094 (18)	0.0212 (9)
O20	0.43748 (19)	0.2043 (2)	−0.10470 (18)	0.0216 (9)
O21	0.1524 (2)	0.5974 (2)	−0.0495 (2)	0.0306 (10)
O22	0.1966 (2)	0.5119 (2)	−0.12379 (18)	0.0217 (9)
O23	0.2157 (2)	0.3800 (2)	−0.18266 (19)	0.0273 (10)
O24	0.4429 (2)	0.3496 (2)	−0.0541 (2)	0.0273 (10)
O25	0.2632 (2)	0.5515 (2)	−0.02999 (19)	0.0247 (9)
O26	0.09176 (19)	0.4695 (2)	0.03649 (18)	0.0213 (9)
O27	0.6021 (2)	0.1967 (2)	0.0708 (2)	0.0307 (10)
O28	0.3512 (2)	0.3035 (2)	−0.17078 (19)	0.0297 (10)
O29	0.2387 (2)	0.6384 (2)	−0.1122 (2)	0.0351 (11)
H29	0.2482	0.6715	−0.0893	0.053*
O30	0.3454 (2)	0.4097 (2)	0.1503 (2)	0.0281 (10)
O31	0.3528 (2)	0.0478 (3)	−0.2656 (2)	0.0314 (10)
H31	0.3294	0.0189	−0.2839	0.047*
O32	0.0345 (15)	0.5075 (16)	0.2160 (14)	0.30 (2)	0.5
C1	0.0997 (6)	0.7473 (6)	0.8591 (6)	0.088 (4)
H1	0.0931	0.6981	0.8535	0.105*
C2	0.1292 (6)	0.7873 (5)	0.8177 (5)	0.068 (3)
H2	0.1434	0.7651	0.7849	0.082*
C3	0.1368 (4)	0.8611 (4)	0.8265 (3)	0.0391 (17)
C4	0.1143 (5)	0.8925 (6)	0.8757 (4)	0.059 (2)
H4	0.1183	0.9420	0.8816	0.070*
C5	0.0864 (5)	0.8513 (8)	0.9156 (5)	0.071 (3)
H5	0.0712	0.8725	0.9484	0.086*
C6	0.1672 (4)	0.9087 (4)	0.7830 (3)	0.0351 (16)
H6A	0.1912	0.8787	0.7582	0.042*
H6B	0.1963	0.9416	0.8043	0.042*
C7	0.1181 (4)	0.9525 (4)	0.7440 (3)	0.0413 (18)
H7A	0.0879	0.9195	0.7242	0.050*
H7B	0.0955	0.9838	0.7688	0.050*
C8	0.1476 (4)	0.9984 (4)	0.6978 (4)	0.046 (2)
H8A	0.1811	1.0278	0.7169	0.055*
H8B	0.1658	0.9671	0.6698	0.055*
C9	0.0381 (9)	1.1565 (7)	0.6595 (6)	0.131 (7)
H9	0.0287	1.2015	0.6745	0.158*
C10	0.0864 (8)	1.1140 (6)	0.6870 (6)	0.106 (6)
H10	0.1103	1.1316	0.7201	0.127*
C11	0.0991 (4)	1.0466 (4)	0.6657 (4)	0.0402 (18)
C12	0.0640 (5)	1.0244 (5)	0.6146 (5)	0.068 (3)
H12	0.0717	0.9797	0.5981	0.082*
C13	0.0179 (5)	1.0687 (6)	0.5885 (5)	0.075 (3)
H13	−0.0050	1.0539	0.5539	0.090*
C14	0.0582 (17)	0.657 (2)	0.2133 (11)	0.135 (16)	0.5
H14A	0.0331	0.6787	0.2414	0.202*	0.5
H14B	0.0549	0.6850	0.1779	0.202*	0.5
H14C	0.1014	0.6551	0.2293	0.202*	0.5
C15	0.0345 (12)	0.581 (2)	0.1997 (15)	0.117 (14)	0.5
H15A	−0.0105	0.5895	0.1950	0.141*	0.5
H15B	0.0461	0.5758	0.1597	0.141*	0.5
N1	0.0810 (4)	0.7798 (6)	0.9069 (4)	0.077 (3)
H1A	0.0649	0.7540	0.9330	0.092*
N2	0.0057 (4)	1.1307 (5)	0.6111 (4)	0.074 (3)
H2A	−0.0245	1.1563	0.5944	0.089*
O1W	0.4586 (2)	−0.0251 (3)	0.0820 (2)	0.0318 (10)
H1WA	0.4407	0.0201	0.0964	0.23 (10)*
H1WB	0.4226	−0.0522	0.0693	0.21 (9)*
O2W	0.1567 (5)	0.5737 (5)	0.1587 (3)	0.105 (4)
O3W	0.2425 (3)	0.6755 (4)	0.0632 (5)	0.091 (3)
O4W	0.8391 (6)	0.8120 (6)	0.4735 (5)	0.136 (5)
O6W	0.8065 (7)	0.2744 (6)	0.7882 (6)	0.147 (5)
O7W	−0.0088 (13)	0.3830 (17)	0.2048 (14)	0.30 (2)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.0199 (2)	0.0132 (2)	0.0129 (2)	0.00124 (18)	−0.00156 (18)	0.00079 (17)
Mo2	0.0193 (2)	0.0137 (2)	0.0125 (2)	0.00214 (18)	−0.00284 (18)	−0.00088 (17)
Mo3	0.0181 (2)	0.0118 (2)	0.0164 (3)	0.00086 (18)	−0.00142 (18)	0.00031 (17)
Mo4	0.0185 (2)	0.0127 (2)	0.0145 (3)	0.00104 (18)	−0.00167 (18)	0.00037 (17)
Mo5	0.0218 (3)	0.0142 (2)	0.0130 (3)	0.00137 (18)	−0.00041 (18)	0.00031 (18)
Mo6	0.0179 (2)	0.0131 (2)	0.0149 (3)	0.00159 (18)	−0.00281 (18)	−0.00085 (17)
P1	0.0181 (7)	0.0160 (7)	0.0238 (8)	0.0023 (6)	−0.0020 (6)	0.0014 (6)
P2	0.0282 (8)	0.0217 (8)	0.0126 (7)	0.0024 (6)	0.0000 (6)	−0.0036 (6)
P3	0.0270 (8)	0.0130 (7)	0.0191 (8)	−0.0007 (6)	−0.0007 (6)	0.0038 (6)
P4	0.0180 (7)	0.0101 (6)	0.0128 (7)	0.0019 (5)	−0.0023 (5)	−0.0005 (5)
Fe1	0.0182 (5)	0.0144 (5)	0.0147 (6)	0.0025 (4)	−0.0014 (4)	0.0008 (4)
Ca1	0.0365 (7)	0.0246 (7)	0.0319 (8)	0.0064 (6)	−0.0057 (6)	−0.0026 (5)
Fe2	0.0178 (6)	0.0155 (6)	0.0258 (6)	0.0026 (4)	−0.0025 (5)	−0.0010 (5)
Na1	0.070 (5)	0.076 (6)	0.087 (6)	0.035 (5)	−0.036 (5)	−0.011 (5)
O1	0.020 (2)	0.0144 (19)	0.015 (2)	0.0029 (15)	−0.0018 (15)	−0.0012 (15)
O2	0.022 (2)	0.0153 (19)	0.012 (2)	0.0016 (16)	−0.0019 (15)	0.0003 (15)
O3	0.022 (2)	0.017 (2)	0.014 (2)	0.0024 (16)	−0.0018 (15)	−0.0001 (15)
O4	0.0205 (19)	0.0099 (17)	0.0146 (19)	−0.0018 (15)	−0.0025 (15)	−0.0021 (14)
O5	0.024 (2)	0.0153 (19)	0.017 (2)	0.0029 (16)	−0.0019 (16)	−0.0028 (15)
O6	0.020 (2)	0.0147 (19)	0.015 (2)	0.0032 (15)	−0.0011 (15)	−0.0009 (15)
O7	0.020 (2)	0.017 (2)	0.019 (2)	0.0030 (16)	−0.0006 (16)	0.0014 (16)
O8	0.025 (2)	0.026 (2)	0.027 (2)	−0.0002 (18)	−0.0005 (18)	0.0031 (18)
O9	0.033 (2)	0.018 (2)	0.037 (3)	0.0074 (18)	0.002 (2)	−0.0014 (18)
O10	0.021 (2)	0.019 (2)	0.018 (2)	0.0019 (16)	0.0019 (16)	0.0013 (16)
O11	0.035 (2)	0.028 (2)	0.017 (2)	−0.0029 (19)	0.0048 (18)	−0.0097 (18)
O12	0.030 (2)	0.030 (2)	0.018 (2)	0.0002 (19)	−0.0030 (17)	−0.0081 (18)
O13	0.021 (2)	0.0149 (19)	0.016 (2)	−0.0005 (16)	−0.0011 (15)	0.0011 (15)
O14	0.045 (3)	0.034 (3)	0.017 (2)	0.011 (2)	−0.0021 (19)	−0.0012 (19)
O15	0.024 (2)	0.0135 (19)	0.019 (2)	0.0014 (16)	0.0008 (16)	−0.0012 (15)
O16	0.020 (2)	0.020 (2)	0.025 (2)	−0.0015 (16)	−0.0008 (17)	0.0048 (17)
O17	0.030 (2)	0.021 (2)	0.016 (2)	0.0008 (17)	−0.0039 (17)	−0.0066 (16)
O18	0.021 (2)	0.0159 (19)	0.020 (2)	0.0013 (16)	−0.0045 (16)	0.0023 (16)
O19	0.0165 (19)	0.024 (2)	0.022 (2)	0.0009 (16)	−0.0039 (16)	0.0018 (17)
O20	0.022 (2)	0.024 (2)	0.019 (2)	0.0009 (17)	0.0013 (16)	−0.0025 (17)
O21	0.032 (2)	0.028 (2)	0.031 (3)	0.0083 (19)	0.004 (2)	−0.0011 (19)
O22	0.031 (2)	0.015 (2)	0.018 (2)	−0.0043 (17)	−0.0046 (17)	0.0038 (16)
O23	0.035 (2)	0.027 (2)	0.019 (2)	−0.0029 (19)	−0.0002 (18)	−0.0015 (18)
O24	0.032 (2)	0.018 (2)	0.031 (2)	−0.0024 (18)	−0.0021 (19)	0.0013 (18)
O25	0.033 (2)	0.015 (2)	0.025 (2)	−0.0012 (17)	−0.0054 (18)	0.0034 (17)
O26	0.024 (2)	0.017 (2)	0.022 (2)	0.0062 (17)	−0.0027 (17)	−0.0014 (16)
O27	0.021 (2)	0.032 (2)	0.038 (3)	0.0011 (19)	−0.0059 (19)	0.004 (2)
O28	0.044 (3)	0.022 (2)	0.022 (2)	0.002 (2)	−0.0010 (19)	0.0079 (18)
O29	0.056 (3)	0.022 (2)	0.026 (3)	−0.014 (2)	−0.004 (2)	0.0035 (19)
O30	0.027 (2)	0.030 (2)	0.026 (2)	0.0020 (19)	−0.0077 (18)	−0.0012 (18)
O31	0.035 (3)	0.033 (3)	0.026 (2)	0.007 (2)	0.0016 (19)	−0.013 (2)
O32	0.18 (2)	0.28 (3)	0.40 (5)	0.15 (2)	−0.11 (3)	−0.16 (3)
C1	0.116 (10)	0.044 (6)	0.110 (10)	0.000 (6)	0.050 (8)	0.024 (6)
C2	0.103 (8)	0.039 (5)	0.068 (7)	−0.003 (5)	0.031 (6)	0.004 (4)
C3	0.040 (4)	0.044 (4)	0.033 (4)	0.009 (3)	0.002 (3)	0.003 (3)
C4	0.064 (6)	0.069 (6)	0.046 (5)	0.000 (5)	0.019 (4)	−0.007 (4)
C5	0.051 (6)	0.117 (10)	0.046 (6)	0.012 (6)	0.012 (4)	0.000 (6)
C6	0.040 (4)	0.029 (4)	0.036 (4)	−0.003 (3)	−0.002 (3)	0.001 (3)
C7	0.047 (4)	0.037 (4)	0.038 (4)	0.008 (3)	−0.006 (3)	−0.005 (3)
C8	0.039 (4)	0.041 (4)	0.057 (5)	0.009 (3)	−0.006 (4)	0.017 (4)
C9	0.23 (2)	0.075 (9)	0.078 (9)	0.093 (11)	−0.048 (11)	−0.011 (7)
C10	0.173 (15)	0.060 (7)	0.072 (8)	0.049 (8)	−0.055 (9)	−0.017 (6)
C11	0.041 (4)	0.036 (4)	0.042 (4)	0.006 (3)	−0.005 (3)	0.012 (3)
C12	0.083 (7)	0.047 (5)	0.069 (7)	0.023 (5)	−0.025 (5)	−0.012 (5)
C13	0.079 (7)	0.065 (7)	0.074 (7)	0.004 (6)	−0.031 (6)	0.010 (6)
C14	0.18 (3)	0.17 (3)	0.046 (15)	0.09 (3)	−0.056 (18)	−0.045 (18)
C15	0.058 (14)	0.18 (3)	0.12 (2)	0.046 (19)	0.022 (15)	0.09 (3)
N1	0.059 (5)	0.111 (8)	0.066 (6)	0.029 (5)	0.029 (4)	0.050 (6)
N2	0.083 (6)	0.069 (6)	0.067 (6)	0.046 (5)	−0.010 (5)	0.026 (5)
O1W	0.032 (2)	0.028 (2)	0.034 (3)	0.002 (2)	−0.004 (2)	−0.004 (2)
O2W	0.146 (8)	0.128 (7)	0.041 (4)	0.098 (7)	0.015 (4)	0.026 (4)
O3W	0.048 (4)	0.057 (4)	0.162 (9)	0.005 (3)	−0.023 (5)	−0.026 (5)
O4W	0.156 (10)	0.120 (8)	0.122 (8)	0.094 (8)	−0.050 (7)	−0.033 (7)
O6W	0.220 (14)	0.075 (7)	0.142 (10)	−0.042 (8)	−0.012 (9)	0.001 (7)
O7W	0.18 (2)	0.28 (3)	0.40 (5)	0.15 (2)	−0.11 (3)	−0.16 (3)

Geometric parameters (Å, º) top

Mo1—O23	1.700 (4)	Fe2—O9	2.065 (4)
Mo1—O18	1.959 (4)	Fe2—O9^iv	2.065 (4)
Mo1—O6	2.011 (4)	Fe2—O26ⁱ	2.133 (4)
Mo1—O22	2.114 (4)	Fe2—O26ⁱⁱ	2.133 (4)
Mo1—O10	2.125 (4)	Fe2—O1W	2.189 (5)
Mo1—O13	2.321 (4)	Fe2—O1W^iv	2.189 (5)
Mo1—Mo6	2.6222 (9)	Na1—O7W	2.12 (2)
Mo2—O30	1.691 (4)	Na1—O32	2.260 (18)
Mo2—O5	1.983 (4)	Na1—O1Wⁱⁱⁱ	2.454 (8)
Mo2—O3	2.014 (4)	Na1—O20ⁱ	2.628 (10)
Mo2—O17ⁱ	2.092 (4)	Na1—O11ⁱ	2.639 (9)
Mo2—O7	2.117 (4)	Na1—O26	2.794 (12)
Mo2—O2	2.290 (4)	Na1—Mo5ⁱ	3.604 (8)
Mo2—Mo4	2.6363 (10)	O2—Mo5ⁱ	2.306 (4)
Mo3—O24	1.703 (4)	O4—P4ⁱ	1.559 (4)
Mo3—O20	1.956 (4)	O4—Mo6ⁱ	2.329 (4)
Mo3—O1	2.000 (4)	O7—Mo5ⁱ	2.120 (4)
Mo3—O16	2.086 (4)	O7—H7	0.8753
Mo3—O15ⁱ	2.160 (4)	O9—Ca1ⁱⁱ	2.688 (5)
Mo3—O4	2.284 (4)	O10—H10A	0.9987
Mo3—Mo5	2.6155 (9)	O11—Na1ⁱ	2.639 (9)
Mo4—O8	1.690 (4)	O15—Mo3ⁱ	2.160 (4)
Mo4—O5	1.969 (4)	O15—H15	0.9561
Mo4—O3	2.001 (4)	O17—Mo2ⁱ	2.092 (4)
Mo4—O25	2.084 (4)	O19—Mo6ⁱ	2.071 (4)
Mo4—O10	2.115 (4)	O20—Na1ⁱ	2.628 (10)
Mo4—O13	2.312 (4)	O26—Fe2ⁱⁱⁱ	2.133 (4)
Mo5—O28	1.698 (4)	O27—Ca1ⁱⁱ	2.420 (5)
Mo5—O20	1.955 (4)	O29—H29	0.8200
Mo5—O1	2.014 (4)	O31—H31	0.8200
Mo5—O11	2.088 (4)	O32—C15	1.404 (19)
Mo5—O7ⁱ	2.120 (4)	C1—N1	1.339 (16)
Mo5—O2ⁱ	2.306 (4)	C1—C2	1.393 (14)
Mo5—Na1ⁱ	3.604 (8)	C1—H1	0.9300
Mo6—O12	1.697 (4)	C2—C3	1.390 (12)
Mo6—O18	1.954 (4)	C2—H2	0.9300
Mo6—O6	1.998 (4)	C3—C4	1.389 (11)
Mo6—O19ⁱ	2.071 (4)	C3—C6	1.516 (10)
Mo6—O15	2.139 (4)	C4—C5	1.365 (15)
Mo6—O4ⁱ	2.329 (4)	C4—H4	0.9300
P1—O9	1.532 (4)	C5—N1	1.343 (15)
P1—O27	1.531 (4)	C5—H5	0.9300
P1—O19	1.563 (4)	C6—C7	1.543 (10)
P1—O16	1.575 (4)	C6—H6A	0.9700
P1—Ca1ⁱⁱ	3.149 (2)	C6—H6B	0.9700
P2—O14	1.517 (5)	C7—C8	1.533 (11)
P2—O11	1.561 (4)	C7—H7A	0.9700
P2—O17	1.572 (5)	C7—H7B	0.9700
P2—O31	1.597 (4)	C8—C11	1.506 (10)
P3—O21	1.521 (5)	C8—H8A	0.9700
P3—O25	1.547 (4)	C8—H8B	0.9700
P3—O22	1.567 (4)	C9—N2	1.339 (17)
P3—O29	1.572 (5)	C9—C10	1.399 (16)
P3—Ca1	3.339 (2)	C9—H9	0.9300
P4—O26	1.528 (4)	C10—C11	1.377 (14)
P4—O4ⁱ	1.559 (4)	C10—H10	0.9300
P4—O2	1.561 (4)	C11—C12	1.391 (12)
P4—O13	1.572 (4)	C12—C13	1.375 (13)
P4—Ca1	3.421 (2)	C12—H12	0.9300
Fe1—O1	2.157 (4)	C13—N2	1.296 (14)
Fe1—O1ⁱ	2.157 (4)	C13—H13	0.9300
Fe1—O6	2.198 (4)	C14—C15	1.53 (4)
Fe1—O6ⁱ	2.198 (4)	C14—H14A	0.9600
Fe1—O3ⁱ	2.254 (4)	C14—H14B	0.9600
Fe1—O3	2.254 (4)	C14—H14C	0.9600
Ca1—O2W	2.381 (7)	C15—H15A	0.9700
Ca1—O21	2.388 (5)	C15—H15B	0.9700
Ca1—O27ⁱⁱⁱ	2.420 (5)	N1—H1A	0.8600
Ca1—O3W	2.443 (7)	N2—H2A	0.8600
Ca1—O26	2.593 (4)	O1W—Na1ⁱⁱ	2.454 (9)
Ca1—O5	2.594 (4)	O1W—H1WA	0.9884
Ca1—O9ⁱⁱⁱ	2.688 (5)	O1W—H1WB	0.9428
Ca1—P1ⁱⁱⁱ	3.149 (2)

O23—Mo1—O18	104.88 (19)	O3W—Ca1—O5	82.1 (2)
O23—Mo1—O6	102.81 (19)	O26—Ca1—O5	85.01 (13)
O18—Mo1—O6	95.18 (16)	O2W—Ca1—O9ⁱⁱⁱ	97.3 (3)
O23—Mo1—O22	95.43 (19)	O21—Ca1—O9ⁱⁱⁱ	79.17 (16)
O18—Mo1—O22	85.54 (16)	O27ⁱⁱⁱ—Ca1—O9ⁱⁱⁱ	57.29 (14)
O6—Mo1—O22	160.87 (16)	O3W—Ca1—O9ⁱⁱⁱ	131.4 (2)
O23—Mo1—O10	98.02 (19)	O26—Ca1—O9ⁱⁱⁱ	61.77 (13)
O18—Mo1—O10	155.98 (16)	O5—Ca1—O9ⁱⁱⁱ	146.49 (14)
O6—Mo1—O10	86.62 (15)	O2W—Ca1—P1ⁱⁱⁱ	90.39 (18)
O22—Mo1—O10	85.17 (15)	O21—Ca1—P1ⁱⁱⁱ	86.74 (12)
O23—Mo1—O13	169.78 (18)	O27ⁱⁱⁱ—Ca1—P1ⁱⁱⁱ	28.22 (11)
O18—Mo1—O13	84.16 (15)	O3W—Ca1—P1ⁱⁱⁱ	104.13 (17)
O6—Mo1—O13	80.76 (14)	O26—Ca1—P1ⁱⁱⁱ	90.08 (10)
O22—Mo1—O13	80.30 (15)	O5—Ca1—P1ⁱⁱⁱ	167.41 (11)
O10—Mo1—O13	72.47 (14)	O9ⁱⁱⁱ—Ca1—P1ⁱⁱⁱ	29.08 (9)
O23—Mo1—Mo6	100.70 (15)	O2W—Ca1—P3	158.9 (2)
O18—Mo1—Mo6	47.85 (11)	O21—Ca1—P3	24.27 (11)
O6—Mo1—Mo6	48.93 (11)	O27ⁱⁱⁱ—Ca1—P3	113.76 (13)
O22—Mo1—Mo6	133.13 (12)	O3W—Ca1—P3	79.0 (2)
O10—Mo1—Mo6	134.51 (11)	O26—Ca1—P3	91.15 (10)
O13—Mo1—Mo6	88.88 (10)	O5—Ca1—P3	81.26 (10)
O30—Mo2—O5	106.22 (19)	O9ⁱⁱⁱ—Ca1—P3	102.45 (12)
O30—Mo2—O3	101.47 (19)	P1ⁱⁱⁱ—Ca1—P3	110.49 (6)
O5—Mo2—O3	94.56 (16)	O2W—Ca1—P4	96.0 (3)
O30—Mo2—O17ⁱ	97.14 (19)	O21—Ca1—P4	83.24 (12)
O5—Mo2—O17ⁱ	86.41 (16)	O27ⁱⁱⁱ—Ca1—P4	142.26 (12)
O3—Mo2—O17ⁱ	160.27 (16)	O3W—Ca1—P4	140.04 (18)
O30—Mo2—O7	99.50 (19)	O26—Ca1—P4	24.90 (9)
O5—Mo2—O7	153.47 (16)	O5—Ca1—P4	62.23 (9)
O3—Mo2—O7	86.54 (16)	O9ⁱⁱⁱ—Ca1—P4	85.63 (10)
O17ⁱ—Mo2—O7	83.98 (16)	P1ⁱⁱⁱ—Ca1—P4	114.48 (6)
O30—Mo2—O2	171.12 (18)	P3—Ca1—P4	78.33 (5)
O5—Mo2—O2	82.14 (15)	O9—Fe2—O9^iv	180.0
O3—Mo2—O2	80.49 (15)	O9—Fe2—O26ⁱ	99.53 (16)
O17ⁱ—Mo2—O2	80.13 (15)	O9^iv—Fe2—O26ⁱ	80.47 (16)
O7—Mo2—O2	71.88 (14)	O9—Fe2—O26ⁱⁱ	80.47 (16)
O30—Mo2—Mo4	99.12 (16)	O9^iv—Fe2—O26ⁱⁱ	99.53 (16)
O5—Mo2—Mo4	47.93 (11)	O26ⁱ—Fe2—O26ⁱⁱ	180.0 (3)
O3—Mo2—Mo4	48.76 (11)	O9—Fe2—O1W	93.73 (18)
O17ⁱ—Mo2—Mo4	134.19 (12)	O9^iv—Fe2—O1W	86.27 (18)
O7—Mo2—Mo4	134.16 (11)	O26ⁱ—Fe2—O1W	87.98 (17)
O2—Mo2—Mo4	88.70 (10)	O26ⁱⁱ—Fe2—O1W	92.02 (17)
O24—Mo3—O20	106.2 (2)	O9—Fe2—O1W^iv	86.27 (18)
O24—Mo3—O1	103.04 (18)	O9^iv—Fe2—O1W^iv	93.73 (18)
O20—Mo3—O1	95.96 (16)	O26ⁱ—Fe2—O1W^iv	92.02 (17)
O24—Mo3—O16	95.98 (18)	O26ⁱⁱ—Fe2—O1W^iv	87.98 (17)
O20—Mo3—O16	86.01 (17)	O1W—Fe2—O1W^iv	180.00 (11)
O1—Mo3—O16	159.45 (15)	O7W—Na1—O32	69.3 (14)
O24—Mo3—O15ⁱ	94.49 (19)	O7W—Na1—O1Wⁱⁱⁱ	92.2 (9)
O20—Mo3—O15ⁱ	158.28 (16)	O32—Na1—O1Wⁱⁱⁱ	91.8 (9)
O1—Mo3—O15ⁱ	85.52 (15)	O7W—Na1—O20ⁱ	86.8 (10)
O16—Mo3—O15ⁱ	85.30 (16)	O32—Na1—O20ⁱ	152.1 (11)
O24—Mo3—O4	166.58 (18)	O1Wⁱⁱⁱ—Na1—O20ⁱ	103.8 (3)
O20—Mo3—O4	85.60 (16)	O7W—Na1—O11ⁱ	84.7 (8)
O1—Mo3—O4	81.60 (14)	O32—Na1—O11ⁱ	99.8 (9)
O16—Mo3—O4	78.16 (14)	O1Wⁱⁱⁱ—Na1—O11ⁱ	166.0 (4)
O15ⁱ—Mo3—O4	73.15 (14)	O20ⁱ—Na1—O11ⁱ	62.5 (2)
O24—Mo3—Mo5	101.96 (15)	O7W—Na1—O26	160.0 (10)
O20—Mo3—Mo5	48.01 (12)	O32—Na1—O26	122.5 (11)
O1—Mo3—Mo5	49.58 (11)	O1Wⁱⁱⁱ—Na1—O26	72.3 (3)
O16—Mo3—Mo5	133.61 (12)	O20ⁱ—Na1—O26	84.7 (3)
O15ⁱ—Mo3—Mo5	134.46 (11)	O11ⁱ—Na1—O26	107.2 (4)
O4—Mo3—Mo5	90.66 (9)	O7W—Na1—Mo5ⁱ	97.7 (9)
O8—Mo4—O5	106.93 (19)	O32—Na1—Mo5ⁱ	134.8 (9)
O8—Mo4—O3	102.73 (18)	O1Wⁱⁱⁱ—Na1—Mo5ⁱ	132.9 (3)
O5—Mo4—O3	95.41 (16)	O20ⁱ—Na1—Mo5ⁱ	31.94 (13)
O8—Mo4—O25	96.93 (19)	O11ⁱ—Na1—Mo5ⁱ	34.94 (13)
O5—Mo4—O25	85.05 (17)	O26—Na1—Mo5ⁱ	84.6 (2)
O3—Mo4—O25	159.25 (16)	Mo3—O1—Mo5	81.32 (14)
O8—Mo4—O10	98.41 (19)	Mo3—O1—Fe1	135.01 (19)
O5—Mo4—O10	153.60 (16)	Mo5—O1—Fe1	133.96 (19)
O3—Mo4—O10	85.93 (16)	P4—O2—Mo2	126.5 (2)
O25—Mo4—O10	84.67 (16)	P4—O2—Mo5ⁱ	126.9 (2)
O8—Mo4—O13	170.14 (18)	Mo2—O2—Mo5ⁱ	101.46 (14)
O5—Mo4—O13	81.26 (15)	Mo4—O3—Mo2	82.06 (15)
O3—Mo4—O13	81.54 (14)	Mo4—O3—Fe1	134.30 (19)
O25—Mo4—O13	78.02 (15)	Mo2—O3—Fe1	132.22 (19)
O10—Mo4—O13	72.84 (14)	P4ⁱ—O4—Mo3	124.4 (2)
O8—Mo4—Mo2	100.64 (15)	P4ⁱ—O4—Mo6ⁱ	127.1 (2)
O5—Mo4—Mo2	48.38 (12)	Mo3—O4—Mo6ⁱ	101.39 (14)
O3—Mo4—Mo2	49.18 (11)	Mo4—O5—Mo2	83.68 (15)
O25—Mo4—Mo2	133.21 (12)	Mo4—O5—Ca1	116.29 (17)
O10—Mo4—Mo2	134.03 (11)	Mo2—O5—Ca1	141.3 (2)
O13—Mo4—Mo2	88.89 (10)	Mo6—O6—Mo1	81.71 (14)
O28—Mo5—O20	106.1 (2)	Mo6—O6—Fe1	134.0 (2)
O28—Mo5—O1	101.12 (19)	Mo1—O6—Fe1	135.01 (19)
O20—Mo5—O1	95.53 (16)	Mo2—O7—Mo5ⁱ	114.23 (17)
O28—Mo5—O11	98.0 (2)	Mo2—O7—H7	102.4
O20—Mo5—O11	84.92 (17)	Mo5ⁱ—O7—H7	114.0
O1—Mo5—O11	159.96 (17)	P1—O9—Fe2	160.5 (3)
O28—Mo5—O7ⁱ	99.11 (19)	P1—O9—Ca1ⁱⁱ	92.4 (2)
O20—Mo5—O7ⁱ	153.54 (16)	Fe2—O9—Ca1ⁱⁱ	106.91 (17)
O1—Mo5—O7ⁱ	87.33 (16)	Mo4—O10—Mo1	113.79 (18)
O11—Mo5—O7ⁱ	83.68 (16)	Mo4—O10—H10A	108.9
O28—Mo5—O2ⁱ	170.58 (19)	Mo1—O10—H10A	108.4
O20—Mo5—O2ⁱ	83.10 (16)	P2—O11—Mo5	129.1 (3)
O1—Mo5—O2ⁱ	79.68 (14)	P2—O11—Na1ⁱ	110.0 (3)
O11—Mo5—O2ⁱ	80.49 (16)	Mo5—O11—Na1ⁱ	98.7 (3)
O7ⁱ—Mo5—O2ⁱ	71.51 (14)	P4—O13—Mo4	125.3 (2)
O28—Mo5—Mo3	100.37 (16)	P4—O13—Mo1	127.0 (2)
O20—Mo5—Mo3	48.04 (12)	Mo4—O13—Mo1	100.13 (15)
O1—Mo5—Mo3	49.10 (11)	Mo6—O15—Mo3ⁱ	112.22 (17)
O11—Mo5—Mo3	132.59 (13)	Mo6—O15—H15	106.9
O7ⁱ—Mo5—Mo3	134.87 (11)	Mo3ⁱ—O15—H15	110.9
O2ⁱ—Mo5—Mo3	87.29 (10)	P1—O16—Mo3	132.4 (2)
O28—Mo5—Na1ⁱ	125.6 (2)	P2—O17—Mo2ⁱ	128.4 (2)
O20—Mo5—Na1ⁱ	45.33 (18)	Mo6—O18—Mo1	84.15 (15)
O1—Mo5—Na1ⁱ	122.93 (19)	P1—O19—Mo6ⁱ	133.1 (2)
O11—Mo5—Na1ⁱ	46.38 (19)	Mo3—O20—Mo5	83.95 (16)
O7ⁱ—Mo5—Na1ⁱ	112.13 (19)	Mo3—O20—Na1ⁱ	145.8 (3)
O2ⁱ—Mo5—Na1ⁱ	59.6 (2)	Mo5—O20—Na1ⁱ	102.7 (2)
Mo3—Mo5—Na1ⁱ	88.17 (13)	P3—O21—Ca1	115.5 (3)
O12—Mo6—O18	106.3 (2)	P3—O22—Mo1	131.3 (2)
O12—Mo6—O6	102.46 (18)	P3—O25—Mo4	135.9 (3)
O18—Mo6—O6	95.74 (16)	P4—O26—Fe2ⁱⁱⁱ	132.3 (2)
O12—Mo6—O19ⁱ	96.78 (19)	P4—O26—Ca1	109.5 (2)
O18—Mo6—O19ⁱ	87.72 (16)	Fe2ⁱⁱⁱ—O26—Ca1	108.14 (16)
O6—Mo6—O19ⁱ	158.58 (16)	P4—O26—Na1	102.0 (3)
O12—Mo6—O15	96.41 (19)	Fe2ⁱⁱⁱ—O26—Na1	93.4 (2)
O18—Mo6—O15	156.08 (16)	Ca1—O26—Na1	107.5 (2)
O6—Mo6—O15	86.39 (15)	P1—O27—Ca1ⁱⁱ	103.4 (2)
O19ⁱ—Mo6—O15	82.16 (16)	P3—O29—H29	109.5
O12—Mo6—O4ⁱ	168.62 (18)	P2—O31—H31	109.5
O18—Mo6—O4ⁱ	84.23 (15)	C15—O32—Na1	116 (3)
O6—Mo6—O4ⁱ	80.29 (14)	N1—C1—C2	119.9 (10)
O19ⁱ—Mo6—O4ⁱ	79.04 (15)	N1—C1—H1	120.0
O15—Mo6—O4ⁱ	72.62 (14)	C2—C1—H1	120.0
O12—Mo6—Mo1	101.58 (15)	C1—C2—C3	118.7 (10)
O18—Mo6—Mo1	48.00 (12)	C1—C2—H2	120.7
O6—Mo6—Mo1	49.36 (11)	C3—C2—H2	120.7
O19ⁱ—Mo6—Mo1	135.21 (12)	C4—C3—C2	119.0 (8)
O15—Mo6—Mo1	134.74 (11)	C4—C3—C6	119.1 (8)
O4ⁱ—Mo6—Mo1	88.63 (9)	C2—C3—C6	121.9 (7)
O9—P1—O27	106.9 (3)	C5—C4—C3	120.6 (10)
O9—P1—O19	111.5 (3)	C5—C4—H4	119.7
O27—P1—O19	109.1 (3)	C3—C4—H4	119.7
O9—P1—O16	112.7 (3)	N1—C5—C4	119.3 (10)
O27—P1—O16	108.4 (2)	N1—C5—H5	120.3
O19—P1—O16	108.2 (2)	C4—C5—H5	120.3
O9—P1—Ca1ⁱⁱ	58.50 (18)	C3—C6—C7	112.1 (6)
O27—P1—Ca1ⁱⁱ	48.36 (18)	C3—C6—H6A	109.2
O19—P1—Ca1ⁱⁱ	125.87 (16)	C7—C6—H6A	109.2
O16—P1—Ca1ⁱⁱ	125.09 (17)	C3—C6—H6B	109.2
O14—P2—O11	114.3 (3)	C7—C6—H6B	109.2
O14—P2—O17	113.6 (3)	H6A—C6—H6B	107.9
O11—P2—O17	109.0 (2)	C8—C7—C6	113.0 (6)
O14—P2—O31	109.6 (3)	C8—C7—H7A	109.0
O11—P2—O31	103.7 (3)	C6—C7—H7A	109.0
O17—P2—O31	105.9 (2)	C8—C7—H7B	109.0
O21—P3—O25	109.9 (3)	C6—C7—H7B	109.0
O21—P3—O22	112.1 (3)	H7A—C7—H7B	107.8
O25—P3—O22	111.2 (2)	C11—C8—C7	111.1 (7)
O21—P3—O29	110.8 (3)	C11—C8—H8A	109.4
O25—P3—O29	106.2 (3)	C7—C8—H8A	109.4
O22—P3—O29	106.6 (2)	C11—C8—H8B	109.4
O21—P3—Ca1	40.20 (18)	C7—C8—H8B	109.4
O25—P3—Ca1	69.74 (18)	H8A—C8—H8B	108.0
O22—P3—Ca1	126.48 (17)	N2—C9—C10	118.4 (11)
O29—P3—Ca1	125.06 (19)	N2—C9—H9	120.8
O26—P4—O4ⁱ	113.6 (2)	C10—C9—H9	120.8
O26—P4—O2	108.7 (2)	C11—C10—C9	120.7 (11)
O4ⁱ—P4—O2	108.5 (2)	C11—C10—H10	119.7
O26—P4—O13	110.2 (2)	C9—C10—H10	119.7
O4ⁱ—P4—O13	107.3 (2)	C10—C11—C12	117.2 (8)
O2—P4—O13	108.4 (2)	C10—C11—C8	120.9 (8)
O26—P4—Ca1	45.61 (16)	C12—C11—C8	121.9 (8)
O4ⁱ—P4—Ca1	154.08 (16)	C13—C12—C11	119.8 (9)
O2—P4—Ca1	94.81 (15)	C13—C12—H12	120.1
O13—P4—Ca1	74.47 (15)	C11—C12—H12	120.1
O1—Fe1—O1ⁱ	180.00 (11)	N2—C13—C12	121.1 (10)
O1—Fe1—O6	82.79 (14)	N2—C13—H13	119.4
O1ⁱ—Fe1—O6	97.21 (14)	C12—C13—H13	119.4
O1—Fe1—O6ⁱ	97.21 (14)	C15—C14—H14A	109.5
O1ⁱ—Fe1—O6ⁱ	82.79 (14)	C15—C14—H14B	109.5
O6—Fe1—O6ⁱ	180.0	H14A—C14—H14B	109.5
O1—Fe1—O3ⁱ	97.77 (14)	C15—C14—H14C	109.5
O1ⁱ—Fe1—O3ⁱ	82.23 (14)	H14A—C14—H14C	109.5
O6—Fe1—O3ⁱ	84.14 (14)	H14B—C14—H14C	109.5
O6ⁱ—Fe1—O3ⁱ	95.86 (14)	O32—C15—C14	148 (3)
O1—Fe1—O3	82.23 (14)	O32—C15—H15A	99.8
O1ⁱ—Fe1—O3	97.77 (14)	C14—C15—H15A	99.8
O6—Fe1—O3	95.86 (14)	O32—C15—H15B	99.8
O6ⁱ—Fe1—O3	84.14 (14)	C14—C15—H15B	99.8
O3ⁱ—Fe1—O3	180.0	H15A—C15—H15B	104.1
O2W—Ca1—O21	176.4 (3)	C1—N1—C5	122.4 (9)
O2W—Ca1—O27ⁱⁱⁱ	83.2 (2)	C1—N1—H1A	118.8
O21—Ca1—O27ⁱⁱⁱ	95.23 (16)	C5—N1—H1A	118.8
O2W—Ca1—O3W	93.6 (4)	C13—N2—C9	122.6 (9)
O21—Ca1—O3W	89.3 (3)	C13—N2—H2A	118.7
O27ⁱⁱⁱ—Ca1—O3W	77.4 (2)	C9—N2—H2A	118.7
O2W—Ca1—O26	91.6 (3)	Fe2—O1W—Na1ⁱⁱ	102.1 (3)
O21—Ca1—O26	86.16 (15)	Fe2—O1W—H1WA	107.7
O27ⁱⁱⁱ—Ca1—O26	117.44 (15)	Na1ⁱⁱ—O1W—H1WA	114.8
O3W—Ca1—O26	164.8 (2)	Fe2—O1W—H1WB	103.3
O2W—Ca1—O5	78.2 (2)	Na1ⁱⁱ—O1W—H1WB	124.5
O21—Ca1—O5	104.45 (15)	H1WA—O1W—H1WB	103.0
O27ⁱⁱⁱ—Ca1—O5	151.29 (15)

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

(3) top

Crystal data top

(C₁₂H₁₄N₂)₃{Fe[Mo₆O₁₂(OH)₃(HPO₄)₃(H₂PO₄)]₂}·8H₂O	F(000) = 3072
M_r = 3159.85	D_x = 2.479 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.8121 (9) Å	Cell parameters from 9201 reflections
b = 22.6484 (16) Å	θ = 2.2–28.3°
c = 16.0089 (12) Å	µ = 2.15 mm⁻¹
β = 98.701 (1)°	T = 296 K
V = 4233.5 (5) Å³	Block, brown
Z = 2	0.19 × 0.15 × 0.13 mm

Data collection top

Bruker SMART CCD area detector diffractometer	7075 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.018
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 25.0°, θ_min = 2.0°
T_min = 0.685, T_max = 0.756	h = −14→11
20768 measured reflections	k = −22→26
7432 independent reflections	l = −19→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.050	w = 1/[σ²(F_o²) + (0.0214P)² + 6.4728P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
7432 reflections	Δρ_max = 0.72 e Å⁻³
628 parameters	Δρ_min = −0.59 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.29173 (2)	0.10155 (2)	−0.13897 (2)	0.01548 (6)
Mo2	0.58422 (2)	0.13730 (2)	−0.11323 (2)	0.01578 (6)
Mo3	0.70667 (2)	0.12867 (2)	0.03583 (2)	0.01592 (6)
Mo4	0.36395 (2)	0.05522 (2)	0.18837 (2)	0.01419 (6)
Mo5	0.57919 (2)	0.08259 (2)	0.20924 (2)	0.01492 (6)
Mo6	0.19815 (2)	0.06670 (2)	−0.01213 (2)	0.01551 (6)
Fe1	0.5000	0.0000	0.0000	0.01291 (11)
P1	0.42471 (6)	0.15907 (3)	0.04509 (4)	0.01395 (14)
P2	0.76911 (6)	0.18718 (3)	0.22285 (5)	0.01953 (15)
P3	0.10178 (6)	0.10738 (3)	0.16149 (5)	0.02016 (15)
P4	0.38953 (7)	0.22009 (3)	−0.22689 (5)	0.02158 (16)
O1	0.60533 (17)	0.07110 (8)	−0.03128 (11)	0.0166 (4)
O2	0.44798 (16)	0.12122 (8)	0.24506 (11)	0.0176 (4)
O3	0.65325 (17)	0.19655 (8)	−0.03302 (12)	0.0200 (4)
O4	0.18549 (17)	0.13936 (8)	−0.07578 (12)	0.0197 (4)
O5	0.45048 (17)	0.08830 (8)	−0.18085 (12)	0.0182 (4)
H5A	0.4662	0.0513	−0.1770	0.038 (10)*
O6	0.54235 (16)	0.14502 (8)	0.09499 (11)	0.0168 (4)
O7	0.36566 (18)	0.00329 (9)	0.26305 (12)	0.0249 (4)
O8	0.25157 (16)	0.01367 (8)	0.09375 (11)	0.0176 (4)
H8A	0.2830	−0.0170	0.0786	0.068 (15)*
O9	0.33550 (16)	0.11885 (8)	0.07558 (11)	0.0161 (4)
O10	0.71037 (17)	0.07104 (8)	0.13729 (12)	0.0183 (4)
H10A	0.7109	0.0339	0.1179	0.045 (11)*
O11	0.33592 (16)	0.03812 (8)	−0.05589 (11)	0.0161 (4)
O12	0.48878 (16)	0.02874 (8)	0.12813 (11)	0.0158 (4)
O13	0.22022 (17)	0.09800 (9)	0.21252 (12)	0.0218 (4)
O14	0.42692 (16)	0.14955 (8)	−0.04916 (11)	0.0157 (4)
O15	0.21073 (18)	0.06543 (9)	−0.21747 (13)	0.0254 (5)
O16	0.68317 (18)	0.12247 (9)	−0.17452 (13)	0.0263 (5)
O17	0.75679 (18)	0.19221 (9)	0.12701 (12)	0.0233 (4)
O18	0.09570 (18)	0.02219 (9)	−0.06138 (13)	0.0265 (5)
O19	0.29620 (18)	0.18141 (8)	−0.19907 (13)	0.0246 (4)
O20	0.50802 (18)	0.20688 (9)	−0.17904 (13)	0.0259 (5)
O21	0.83426 (18)	0.11294 (9)	0.00918 (14)	0.0283 (5)
O22	0.10384 (17)	0.10971 (9)	0.06682 (12)	0.0241 (4)
O23	0.39470 (19)	0.22459 (8)	0.05370 (12)	0.0234 (4)
H23A	0.4022	0.2399	0.1041	0.079 (16)*
O24	0.62769 (18)	0.03663 (9)	0.28820 (13)	0.0254 (5)
O25	0.66925 (17)	0.15631 (8)	0.25386 (12)	0.0221 (4)
O26	0.8794 (2)	0.15572 (11)	0.26037 (14)	0.0359 (6)
H26A	0.9508	0.1581	0.2328	0.080 (16)*
O27	0.04978 (19)	0.16256 (9)	0.19178 (14)	0.0308 (5)
O28	0.0280 (2)	0.05302 (11)	0.18183 (17)	0.0348 (6)
H28A	−0.003 (5)	0.039 (2)	0.148 (3)	0.08 (2)*
O29	0.3885 (2)	0.21579 (10)	−0.32086 (13)	0.0373 (6)
O30	0.7742 (2)	0.25196 (9)	0.25497 (15)	0.0336 (5)
H30A	0.7986	0.2535	0.3096	0.066 (14)*
O31	0.3561 (2)	0.28356 (9)	−0.20143 (15)	0.0329 (5)
H31A	0.3975	0.3168	−0.2193	0.072 (15)*
C1	1.0091 (4)	0.1796 (2)	0.6889 (3)	0.0648 (13)
H1	1.0439	0.2131	0.6709	0.078*
C2	0.9653 (5)	0.1387 (2)	0.6319 (3)	0.0672 (13)
H2	0.9691	0.1443	0.5748	0.081*
C3	0.9147 (4)	0.08854 (19)	0.6581 (3)	0.0539 (11)
C4	0.9078 (4)	0.08310 (17)	0.7443 (3)	0.0528 (11)
H4	0.8724	0.0503	0.7640	0.063*
C5	0.9535 (3)	0.12643 (17)	0.7999 (3)	0.0483 (10)
H5	0.9494	0.1232	0.8573	0.058*
C6	0.8704 (4)	0.0440 (2)	0.5939 (3)	0.0588 (12)
H6	0.8670	0.0545	0.5374	0.071*
C7	0.8362 (4)	−0.00794 (18)	0.6101 (3)	0.0528 (10)
H7	0.8374	−0.0184	0.6664	0.063*
C8	0.7371 (5)	−0.0840 (2)	0.4031 (3)	0.0615 (13)
H8	0.7255	−0.0762	0.3454	0.074*
C9	0.7789 (5)	−0.04090 (19)	0.4583 (3)	0.0610 (12)
H9	0.7967	−0.0040	0.4384	0.073*
C10	0.7949 (3)	−0.05206 (17)	0.5448 (2)	0.0440 (9)
C11	0.7658 (4)	−0.10720 (17)	0.5711 (2)	0.0507 (11)
H11	0.7737	−0.1158	0.6285	0.061*
C12	0.7254 (4)	−0.14922 (18)	0.5132 (2)	0.0500 (10)
H12	0.7067	−0.1865	0.5314	0.060*
C13	0.3812 (4)	0.83311 (15)	0.3958 (3)	0.0448 (9)
H13	0.3577	0.8131	0.3454	0.054*
C14	0.4127 (3)	0.89124 (14)	0.3946 (2)	0.0395 (9)
H14	0.4109	0.9107	0.3433	0.047*
C15	0.4473 (3)	0.92112 (13)	0.4698 (2)	0.0302 (7)
C16	0.4495 (4)	0.89016 (16)	0.5444 (2)	0.0426 (9)
H16	0.4731	0.9088	0.5958	0.051*
C17	0.4170 (4)	0.83217 (16)	0.5429 (3)	0.0472 (10)
H17	0.4178	0.8114	0.5932	0.057*
C18	0.4830 (3)	0.98314 (14)	0.4669 (2)	0.0336 (8)
H18	0.4814	1.0001	0.4139	0.040*
N1	1.0032 (3)	0.17258 (14)	0.7703 (2)	0.0496 (9)
H1A	1.0333	0.2052	0.8034	0.058 (13)*
N2	0.7125 (3)	−0.13723 (14)	0.43059 (19)	0.0454 (8)
H2A	0.6661	−0.1654	0.3885	0.092 (17)*
N3	0.3842 (3)	0.80562 (12)	0.4690 (2)	0.0413 (8)
H3A	0.3691	0.7656	0.4755	0.076 (15)*
O1W	0.1208 (3)	0.23304 (12)	0.34121 (19)	0.0513 (7)
H1WA	0.1011	0.2006	0.3049	0.12 (2)*
H1WB	0.1996	0.2395	0.3271	0.17 (3)*
O2W	0.8433 (3)	0.25122 (15)	0.91727 (18)	0.0652 (9)
H2WA	0.9111	0.2461	0.9452	0.071 (16)*
H2WB	0.7915	0.2301	0.9423	0.11 (2)*
O3W	0.0547 (3)	0.23455 (15)	0.0109 (2)	0.0785 (10)
H3WA	0.0755	0.2027	0.0352	0.118*
H3WB	0.0716	0.2493	−0.0345	0.118*
O4W	0.8772 (12)	0.1106 (5)	0.4230 (6)	0.145 (5)	0.5
H4WA	0.8205	0.1294	0.4446	0.217*
H4WB	0.9402	0.1311	0.4414	0.217*
O5W	0.9039 (10)	0.0537 (8)	0.3586 (12)	0.226 (10)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.02102 (13)	0.01320 (11)	0.01198 (11)	0.00036 (9)	0.00167 (9)	0.00130 (8)
Mo2	0.02169 (13)	0.01310 (11)	0.01328 (12)	−0.00064 (9)	0.00506 (9)	0.00043 (9)
Mo3	0.01905 (13)	0.01403 (11)	0.01505 (12)	−0.00090 (9)	0.00379 (9)	−0.00111 (9)
Mo4	0.01798 (13)	0.01363 (11)	0.01139 (11)	0.00042 (9)	0.00361 (9)	−0.00018 (8)
Mo5	0.01785 (13)	0.01473 (11)	0.01218 (11)	0.00060 (9)	0.00223 (9)	−0.00128 (9)
Mo6	0.01761 (13)	0.01603 (12)	0.01291 (12)	0.00089 (9)	0.00237 (9)	0.00018 (9)
Fe1	0.0174 (3)	0.0111 (2)	0.0106 (2)	0.0005 (2)	0.0033 (2)	−0.00001 (19)
P1	0.0192 (4)	0.0112 (3)	0.0117 (3)	0.0014 (3)	0.0029 (3)	−0.0001 (2)
P2	0.0197 (4)	0.0199 (4)	0.0188 (4)	−0.0018 (3)	0.0024 (3)	−0.0046 (3)
P3	0.0185 (4)	0.0232 (4)	0.0199 (4)	0.0017 (3)	0.0064 (3)	−0.0024 (3)
P4	0.0333 (4)	0.0149 (3)	0.0162 (4)	0.0000 (3)	0.0024 (3)	0.0055 (3)
O1	0.0222 (10)	0.0122 (9)	0.0156 (9)	−0.0001 (7)	0.0037 (8)	−0.0006 (7)
O2	0.0206 (10)	0.0174 (9)	0.0152 (9)	0.0003 (8)	0.0038 (8)	−0.0036 (7)
O3	0.0278 (11)	0.0134 (9)	0.0191 (10)	−0.0017 (8)	0.0045 (8)	−0.0002 (7)
O4	0.0215 (11)	0.0184 (9)	0.0186 (10)	0.0038 (8)	0.0012 (8)	0.0006 (8)
O5	0.0260 (11)	0.0118 (9)	0.0174 (10)	0.0003 (8)	0.0049 (8)	−0.0014 (7)
O6	0.0194 (10)	0.0171 (9)	0.0140 (9)	−0.0001 (8)	0.0029 (8)	0.0002 (7)
O7	0.0319 (12)	0.0251 (11)	0.0185 (10)	−0.0016 (9)	0.0068 (9)	0.0049 (8)
O8	0.0231 (10)	0.0145 (9)	0.0153 (9)	−0.0003 (8)	0.0033 (8)	−0.0008 (7)
O9	0.0178 (10)	0.0175 (9)	0.0129 (9)	0.0003 (7)	0.0024 (7)	0.0008 (7)
O10	0.0226 (11)	0.0151 (9)	0.0177 (10)	0.0021 (8)	0.0047 (8)	−0.0012 (7)
O11	0.0232 (10)	0.0124 (9)	0.0138 (9)	0.0031 (7)	0.0065 (8)	0.0024 (7)
O12	0.0191 (10)	0.0137 (9)	0.0152 (9)	0.0005 (7)	0.0040 (8)	−0.0021 (7)
O13	0.0220 (11)	0.0275 (11)	0.0166 (10)	0.0033 (8)	0.0051 (8)	−0.0034 (8)
O14	0.0208 (10)	0.0141 (9)	0.0129 (9)	0.0003 (7)	0.0044 (8)	−0.0010 (7)
O15	0.0305 (12)	0.0262 (11)	0.0186 (10)	−0.0041 (9)	0.0003 (9)	−0.0016 (8)
O16	0.0293 (12)	0.0288 (11)	0.0228 (11)	−0.0019 (9)	0.0102 (9)	−0.0026 (9)
O17	0.0265 (11)	0.0223 (10)	0.0212 (10)	−0.0065 (8)	0.0038 (9)	−0.0039 (8)
O18	0.0265 (12)	0.0286 (11)	0.0234 (11)	−0.0067 (9)	0.0011 (9)	−0.0002 (9)
O19	0.0295 (12)	0.0187 (10)	0.0242 (11)	−0.0007 (8)	−0.0004 (9)	0.0092 (8)
O20	0.0318 (12)	0.0194 (10)	0.0265 (11)	−0.0004 (9)	0.0051 (9)	0.0097 (8)
O21	0.0251 (12)	0.0306 (11)	0.0300 (12)	0.0017 (9)	0.0071 (9)	−0.0006 (9)
O22	0.0195 (11)	0.0338 (11)	0.0193 (10)	0.0070 (9)	0.0038 (8)	−0.0006 (9)
O23	0.0393 (13)	0.0140 (9)	0.0168 (10)	0.0048 (8)	0.0041 (9)	−0.0022 (8)
O24	0.0290 (12)	0.0263 (11)	0.0199 (10)	0.0043 (9)	0.0009 (9)	0.0032 (8)
O25	0.0250 (11)	0.0230 (10)	0.0190 (10)	−0.0051 (8)	0.0052 (8)	−0.0068 (8)
O26	0.0261 (12)	0.0574 (15)	0.0251 (12)	0.0118 (11)	0.0065 (10)	0.0041 (11)
O27	0.0276 (12)	0.0284 (11)	0.0384 (13)	0.0053 (9)	0.0115 (10)	−0.0062 (10)
O28	0.0385 (15)	0.0349 (13)	0.0314 (14)	−0.0138 (11)	0.0067 (11)	−0.0033 (11)
O29	0.0647 (17)	0.0294 (12)	0.0172 (11)	−0.0113 (11)	0.0042 (11)	0.0056 (9)
O30	0.0465 (15)	0.0233 (11)	0.0307 (13)	−0.0089 (10)	0.0053 (11)	−0.0100 (9)
O31	0.0420 (14)	0.0143 (10)	0.0446 (14)	0.0017 (9)	0.0139 (11)	0.0045 (9)
C1	0.069 (3)	0.050 (3)	0.074 (3)	−0.013 (2)	0.006 (3)	−0.007 (2)
C2	0.078 (4)	0.058 (3)	0.065 (3)	−0.014 (3)	0.013 (3)	−0.011 (2)
C3	0.050 (3)	0.050 (2)	0.060 (3)	0.004 (2)	0.003 (2)	−0.019 (2)
C4	0.044 (2)	0.035 (2)	0.077 (3)	−0.0023 (17)	0.004 (2)	−0.007 (2)
C5	0.040 (2)	0.043 (2)	0.058 (3)	0.0072 (18)	−0.0033 (19)	−0.0094 (19)
C6	0.073 (3)	0.055 (3)	0.049 (3)	−0.008 (2)	0.012 (2)	−0.002 (2)
C7	0.064 (3)	0.042 (2)	0.053 (3)	−0.002 (2)	0.011 (2)	−0.0044 (19)
C8	0.098 (4)	0.061 (3)	0.029 (2)	−0.014 (3)	0.020 (2)	−0.0005 (19)
C9	0.089 (4)	0.044 (2)	0.054 (3)	−0.020 (2)	0.022 (2)	−0.001 (2)
C10	0.046 (2)	0.043 (2)	0.041 (2)	−0.0013 (17)	0.0016 (17)	−0.0095 (17)
C11	0.078 (3)	0.041 (2)	0.0291 (19)	−0.004 (2)	−0.0071 (19)	−0.0022 (16)
C12	0.071 (3)	0.038 (2)	0.039 (2)	−0.0051 (19)	−0.002 (2)	−0.0015 (17)
C13	0.057 (3)	0.0270 (18)	0.047 (2)	−0.0051 (17)	−0.0004 (19)	−0.0091 (16)
C14	0.061 (3)	0.0245 (17)	0.0298 (18)	−0.0071 (16)	−0.0030 (17)	0.0021 (14)
C15	0.041 (2)	0.0199 (15)	0.0293 (17)	−0.0024 (13)	0.0035 (14)	0.0014 (13)
C16	0.066 (3)	0.0323 (18)	0.0298 (19)	−0.0067 (17)	0.0091 (18)	0.0024 (15)
C17	0.066 (3)	0.0314 (19)	0.046 (2)	−0.0029 (18)	0.015 (2)	0.0145 (17)
C18	0.056 (2)	0.0211 (15)	0.0235 (16)	−0.0055 (14)	0.0041 (15)	0.0044 (12)
N1	0.0411 (19)	0.0370 (18)	0.067 (2)	0.0014 (14)	−0.0045 (17)	−0.0176 (16)
N2	0.058 (2)	0.0446 (18)	0.0326 (17)	−0.0088 (15)	0.0037 (15)	−0.0132 (14)
N3	0.0449 (19)	0.0163 (13)	0.064 (2)	−0.0032 (12)	0.0124 (16)	0.0043 (14)
O1W	0.0472 (17)	0.0421 (15)	0.0632 (18)	−0.0007 (12)	0.0034 (14)	0.0031 (14)
O2W	0.060 (2)	0.088 (2)	0.0466 (17)	−0.0260 (17)	0.0040 (16)	0.0269 (16)
O3W	0.088 (3)	0.072 (2)	0.078 (2)	0.0247 (19)	0.020 (2)	0.0180 (19)
O4W	0.236 (14)	0.121 (8)	0.070 (6)	0.002 (9)	0.002 (7)	0.063 (6)
O5W	0.108 (9)	0.268 (17)	0.32 (2)	0.059 (10)	0.078 (11)	0.246 (17)

Geometric parameters (Å, º) top

Mo1—O15	1.673 (2)	P4—O31	1.561 (2)
Mo1—O4	1.9276 (19)	O5—H5A	0.8591
Mo1—O11	1.9736 (17)	O8—H8A	0.8411
Mo1—O19	2.0532 (19)	O10—H10A	0.8960
Mo1—O5	2.1062 (19)	O23—H23A	0.8711
Mo1—O14	2.2592 (18)	O26—H26A	1.0107
Mo1—Mo6	2.5782 (3)	O28—H28A	0.68 (5)
Mo2—O16	1.670 (2)	O30—H30A	0.8792
Mo2—O3	1.9487 (19)	O31—H31A	0.9642
Mo2—O1	1.9830 (18)	C1—N1	1.325 (6)
Mo2—O20	2.0290 (19)	C1—C2	1.348 (6)
Mo2—O5	2.0933 (19)	C1—H1	0.9300
Mo2—O14	2.2711 (18)	C2—C3	1.378 (6)
Mo2—Mo3	2.6039 (4)	C2—H2	0.9300
Mo3—O21	1.666 (2)	C3—C4	1.400 (6)
Mo3—O3	1.9408 (19)	C3—C6	1.478 (6)
Mo3—O1	1.9743 (18)	C4—C5	1.379 (6)
Mo3—O17	2.0715 (19)	C4—H4	0.9300
Mo3—O10	2.0789 (19)	C5—N1	1.321 (5)
Mo3—O6	2.3146 (19)	C5—H5	0.9300
Mo4—O7	1.6751 (19)	C6—C7	1.284 (6)
Mo4—O2	1.9419 (18)	C6—H6	0.9300
Mo4—O12	1.9733 (18)	C7—C10	1.474 (5)
Mo4—O13	2.042 (2)	C7—H7	0.9300
Mo4—O8	2.0819 (18)	C8—N2	1.331 (5)
Mo4—O9	2.2948 (18)	C8—C9	1.358 (6)
Mo4—Mo5	2.5890 (4)	C8—H8	0.9300
Mo5—O24	1.670 (2)	C9—C10	1.391 (6)
Mo5—O2	1.9404 (19)	C9—H9	0.9300
Mo5—O12	1.9734 (18)	C10—C11	1.379 (5)
Mo5—O25	2.0494 (19)	C11—C12	1.363 (5)
Mo5—O10	2.0823 (19)	C11—H11	0.9300
Mo5—O6	2.3006 (18)	C12—N2	1.337 (5)
Mo6—O18	1.677 (2)	C12—H12	0.9300
Mo6—O4	1.9295 (19)	C13—N3	1.323 (5)
Mo6—O11	1.9757 (18)	C13—C14	1.369 (5)
Mo6—O22	2.0527 (19)	C13—H13	0.9300
Mo6—O8	2.0953 (18)	C14—C15	1.387 (5)
Mo6—O9	2.3043 (18)	C14—H14	0.9300
Fe1—O1	2.1401 (18)	C15—C16	1.382 (5)
Fe1—O1ⁱ	2.1401 (18)	C15—C18	1.469 (4)
Fe1—O12	2.1751 (18)	C16—C17	1.368 (5)
Fe1—O12ⁱ	2.1751 (18)	C16—H16	0.9300
Fe1—O11ⁱ	2.1857 (18)	C17—N3	1.332 (5)
Fe1—O11	2.1858 (18)	C17—H17	0.9300
P1—O9	1.5277 (19)	C18—C18ⁱⁱ	1.318 (6)
P1—O6	1.528 (2)	C18—H18	0.9300
P1—O14	1.5283 (18)	N1—H1A	0.9462
P1—O23	1.5368 (19)	N2—H2A	1.0241
P2—O25	1.518 (2)	N3—H3A	0.9327
P2—O17	1.523 (2)	O1W—H1WA	0.9441
P2—O26	1.526 (2)	O1W—H1WB	1.0004
P2—O30	1.553 (2)	O2W—H2WA	0.8635
P3—O27	1.505 (2)	O2W—H2WB	0.9157
P3—O22	1.520 (2)	O3W—H3WA	0.8382
P3—O13	1.524 (2)	O3W—H3WB	0.8507
P3—O28	1.570 (2)	O4W—O5W	1.71 (2)
P4—O29	1.506 (2)	O4W—H4WA	0.9049
P4—O20	1.520 (2)	O4W—H4WB	0.8894
P4—O19	1.526 (2)

O15—Mo1—O4	105.52 (10)	O12—Fe1—O11	95.23 (7)
O15—Mo1—O11	102.31 (9)	O12ⁱ—Fe1—O11	84.77 (7)
O4—Mo1—O11	95.54 (8)	O11ⁱ—Fe1—O11	180.00 (8)
O15—Mo1—O19	97.53 (9)	O9—P1—O6	108.99 (10)
O4—Mo1—O19	85.38 (8)	O9—P1—O14	110.30 (10)
O11—Mo1—O19	159.09 (8)	O6—P1—O14	109.69 (11)
O15—Mo1—O5	97.28 (9)	O9—P1—O23	111.56 (11)
O4—Mo1—O5	155.78 (8)	O6—P1—O23	110.98 (11)
O11—Mo1—O5	87.33 (7)	O14—P1—O23	105.27 (10)
O19—Mo1—O5	83.63 (8)	O25—P2—O17	113.79 (11)
O15—Mo1—O14	169.09 (9)	O25—P2—O26	108.40 (13)
O4—Mo1—O14	84.60 (7)	O17—P2—O26	112.16 (12)
O11—Mo1—O14	80.33 (7)	O25—P2—O30	108.66 (12)
O19—Mo1—O14	78.96 (7)	O17—P2—O30	104.83 (12)
O5—Mo1—O14	72.15 (7)	O26—P2—O30	108.83 (14)
O15—Mo1—Mo6	100.21 (7)	O27—P3—O22	111.18 (12)
O4—Mo1—Mo6	48.09 (6)	O27—P3—O13	109.22 (12)
O11—Mo1—Mo6	49.28 (5)	O22—P3—O13	112.79 (11)
O19—Mo1—Mo6	133.10 (6)	O27—P3—O28	108.55 (14)
O5—Mo1—Mo6	135.69 (5)	O22—P3—O28	109.08 (13)
O14—Mo1—Mo6	89.55 (5)	O13—P3—O28	105.81 (13)
O16—Mo2—O3	105.39 (9)	O29—P4—O20	111.02 (14)
O16—Mo2—O1	101.99 (9)	O29—P4—O19	110.93 (13)
O3—Mo2—O1	94.97 (8)	O20—P4—O19	112.99 (11)
O16—Mo2—O20	98.39 (9)	O29—P4—O31	110.87 (13)
O3—Mo2—O20	85.17 (8)	O20—P4—O31	107.43 (13)
O1—Mo2—O20	158.79 (8)	O19—P4—O31	103.30 (12)
O16—Mo2—O5	97.47 (9)	Mo3—O1—Mo2	82.29 (7)
O3—Mo2—O5	156.01 (8)	Mo3—O1—Fe1	134.08 (9)
O1—Mo2—O5	87.18 (7)	Mo2—O1—Fe1	134.77 (10)
O20—Mo2—O5	84.40 (8)	Mo5—O2—Mo4	83.65 (7)
O16—Mo2—O14	169.44 (9)	Mo3—O3—Mo2	84.05 (7)
O3—Mo2—O14	84.70 (7)	Mo1—O4—Mo6	83.89 (7)
O1—Mo2—O14	79.81 (7)	Mo2—O5—Mo1	113.48 (8)
O20—Mo2—O14	79.08 (8)	Mo2—O5—H5A	110.0
O5—Mo2—O14	72.14 (7)	Mo1—O5—H5A	108.1
O16—Mo2—Mo3	100.51 (7)	P1—O6—Mo5	126.25 (11)
O3—Mo2—Mo3	47.84 (5)	P1—O6—Mo3	124.88 (10)
O1—Mo2—Mo3	48.71 (5)	Mo5—O6—Mo3	99.06 (7)
O20—Mo2—Mo3	132.49 (6)	Mo4—O8—Mo6	114.22 (8)
O5—Mo2—Mo3	134.85 (5)	Mo4—O8—H8A	108.8
O14—Mo2—Mo3	88.53 (5)	Mo6—O8—H8A	109.4
O21—Mo3—O3	104.65 (9)	P1—O9—Mo4	126.86 (11)
O21—Mo3—O1	102.53 (9)	P1—O9—Mo6	124.54 (10)
O3—Mo3—O1	95.50 (8)	Mo4—O9—Mo6	99.40 (7)
O21—Mo3—O17	98.97 (9)	Mo3—O10—Mo5	115.08 (9)
O3—Mo3—O17	83.31 (8)	Mo3—O10—H10A	108.6
O1—Mo3—O17	158.03 (8)	Mo5—O10—H10A	110.8
O21—Mo3—O10	98.80 (9)	Mo1—O11—Mo6	81.51 (7)
O3—Mo3—O10	155.19 (8)	Mo1—O11—Fe1	133.72 (9)
O1—Mo3—O10	87.13 (7)	Mo6—O11—Fe1	135.33 (9)
O17—Mo3—O10	85.16 (8)	Mo4—O12—Mo5	81.99 (7)
O21—Mo3—O6	170.46 (9)	Mo4—O12—Fe1	135.11 (9)
O3—Mo3—O6	83.39 (7)	Mo5—O12—Fe1	134.54 (9)
O1—Mo3—O6	81.45 (7)	P3—O13—Mo4	133.36 (12)
O17—Mo3—O6	76.62 (7)	P1—O14—Mo1	125.46 (11)
O10—Mo3—O6	72.58 (7)	P1—O14—Mo2	126.90 (11)
O21—Mo3—Mo2	100.37 (8)	Mo1—O14—Mo2	101.63 (7)
O3—Mo3—Mo2	48.11 (6)	P2—O17—Mo3	129.14 (12)
O1—Mo3—Mo2	49.00 (5)	P4—O19—Mo1	135.50 (13)
O17—Mo3—Mo2	130.81 (6)	P4—O20—Mo2	135.79 (12)
O10—Mo3—Mo2	134.93 (5)	P3—O22—Mo6	133.58 (12)
O6—Mo3—Mo2	88.80 (5)	P1—O23—H23A	118.4
O7—Mo4—O2	104.88 (9)	P2—O25—Mo5	130.49 (12)
O7—Mo4—O12	101.90 (9)	P2—O26—H26A	121.5
O2—Mo4—O12	95.48 (8)	P3—O28—H28A	116 (5)
O7—Mo4—O13	96.81 (9)	P2—O30—H30A	111.0
O2—Mo4—O13	85.82 (8)	P4—O31—H31A	118.8
O12—Mo4—O13	160.21 (8)	N1—C1—C2	120.8 (5)
O7—Mo4—O8	98.01 (9)	N1—C1—H1	119.6
O2—Mo4—O8	155.88 (7)	C2—C1—H1	119.6
O12—Mo4—O8	87.04 (7)	C1—C2—C3	120.0 (5)
O13—Mo4—O8	84.00 (8)	C1—C2—H2	120.0
O7—Mo4—O9	170.76 (9)	C3—C2—H2	120.0
O2—Mo4—O9	83.57 (7)	C2—C3—C4	117.8 (4)
O12—Mo4—O9	80.65 (7)	C2—C3—C6	118.3 (4)
O13—Mo4—O9	79.87 (7)	C4—C3—C6	123.9 (4)
O8—Mo4—O9	73.15 (7)	C5—C4—C3	119.9 (4)
O7—Mo4—Mo5	99.81 (7)	C5—C4—H4	120.1
O2—Mo4—Mo5	48.15 (6)	C3—C4—H4	120.1
O12—Mo4—Mo5	49.01 (5)	N1—C5—C4	118.9 (4)
O13—Mo4—Mo5	133.66 (6)	N1—C5—H5	120.5
O8—Mo4—Mo5	135.05 (5)	C4—C5—H5	120.5
O9—Mo4—Mo5	88.58 (5)	C7—C6—C3	125.1 (4)
O24—Mo5—O2	104.78 (9)	C7—C6—H6	117.5
O24—Mo5—O12	101.68 (9)	C3—C6—H6	117.5
O2—Mo5—O12	95.52 (8)	C6—C7—C10	124.0 (4)
O24—Mo5—O25	98.24 (9)	C6—C7—H7	118.0
O2—Mo5—O25	85.71 (8)	C10—C7—H7	118.0
O12—Mo5—O25	158.99 (8)	N2—C8—C9	120.8 (4)
O24—Mo5—O10	98.14 (9)	N2—C8—H8	119.6
O2—Mo5—O10	156.14 (8)	C9—C8—H8	119.6
O12—Mo5—O10	86.12 (7)	C8—C9—C10	119.9 (4)
O25—Mo5—O10	84.53 (8)	C8—C9—H9	120.1
O24—Mo5—O6	170.58 (9)	C10—C9—H9	120.1
O2—Mo5—O6	83.94 (7)	C11—C10—C9	117.8 (4)
O12—Mo5—O6	80.69 (7)	C11—C10—C7	117.9 (4)
O25—Mo5—O6	78.59 (7)	C9—C10—C7	124.2 (4)
O10—Mo5—O6	72.81 (7)	C12—C11—C10	120.2 (4)
O24—Mo5—Mo4	99.57 (7)	C12—C11—H11	119.9
O2—Mo5—Mo4	48.20 (5)	C10—C11—H11	119.9
O12—Mo5—Mo4	49.00 (5)	N2—C12—C11	120.5 (4)
O25—Mo5—Mo4	133.46 (6)	N2—C12—H12	119.8
O10—Mo5—Mo4	134.18 (5)	C11—C12—H12	119.8
O6—Mo5—Mo4	88.89 (5)	N3—C13—C14	119.6 (3)
O18—Mo6—O4	105.76 (9)	N3—C13—H13	120.2
O18—Mo6—O11	102.17 (9)	C14—C13—H13	120.2
O4—Mo6—O11	95.42 (8)	C13—C14—C15	120.1 (3)
O18—Mo6—O22	98.89 (9)	C13—C14—H14	119.9
O4—Mo6—O22	85.10 (8)	C15—C14—H14	119.9
O11—Mo6—O22	157.93 (8)	C16—C15—C14	117.8 (3)
O18—Mo6—O8	98.23 (9)	C16—C15—C18	122.9 (3)
O4—Mo6—O8	154.95 (8)	C14—C15—C18	119.2 (3)
O11—Mo6—O8	86.31 (7)	C17—C16—C15	120.2 (4)
O22—Mo6—O8	84.20 (8)	C17—C16—H16	119.9
O18—Mo6—O9	170.35 (8)	C15—C16—H16	119.9
O4—Mo6—O9	82.86 (7)	N3—C17—C16	119.5 (3)
O11—Mo6—O9	80.92 (7)	N3—C17—H17	120.3
O22—Mo6—O9	77.25 (7)	C16—C17—H17	120.3
O8—Mo6—O9	72.71 (7)	C18ⁱⁱ—C18—C15	125.7 (4)
O18—Mo6—Mo1	100.29 (7)	C18ⁱⁱ—C18—H18	117.2
O4—Mo6—Mo1	48.02 (6)	C15—C18—H18	117.2
O11—Mo6—Mo1	49.21 (5)	C5—N1—C1	122.7 (4)
O22—Mo6—Mo1	132.61 (6)	C5—N1—H1A	124.5
O8—Mo6—Mo1	134.43 (5)	C1—N1—H1A	112.7
O9—Mo6—Mo1	88.67 (5)	C8—N2—C12	120.9 (3)
O1—Fe1—O1ⁱ	180.0	C8—N2—H2A	118.0
O1—Fe1—O12	96.66 (7)	C12—N2—H2A	119.6
O1ⁱ—Fe1—O12	83.34 (7)	C13—N3—C17	122.7 (3)
O1—Fe1—O12ⁱ	83.34 (7)	C13—N3—H3A	125.2
O1ⁱ—Fe1—O12ⁱ	96.66 (7)	C17—N3—H3A	112.0
O12—Fe1—O12ⁱ	180.0	H1WA—O1W—H1WB	97.3
O1—Fe1—O11ⁱ	83.23 (7)	H2WA—O2W—H2WB	109.4
O1ⁱ—Fe1—O11ⁱ	96.77 (7)	H3WA—O3W—H3WB	130.1
O12—Fe1—O11ⁱ	84.77 (7)	O5W—O4W—H4WA	143.1
O12ⁱ—Fe1—O11ⁱ	95.23 (7)	O5W—O4W—H4WB	111.8
O1—Fe1—O11	96.77 (7)	H4WA—O4W—H4WB	105.0
O1ⁱ—Fe1—O11	83.23 (7)

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

Peak potential data (mV) for each peak of hybrids 1–3 at a sweep speed of 140 mV s^-1 top

Scan rate 140 mV s^-1	Ea/Ec (I)/mV E_1/2, ΔE	Ea/Ec (II)/mV E_1/2, ΔE	Ea/Ec (III)/mV E_1/2, ΔE	Ea/Ec (IV)/mV
Hybrid 1	11/-26 -8, 37	271/240 256, 31	424/380 402, 44	-122
Hybrid 2	30/-21 5, 51	277/234 256, 43	439/386 413, 53	-121
Hybrid 3	26/-4 11, 30	253/220 237, 33	412/348 380, 64	-122

Catalytic performance of catalysts 1–3 for the reduction of Cr^VI to Cr^III at 75 °C within 180 min. top

Hybrid	n(K₂Cr₂O₇) (10 ^-5 mol)	n(catalyst) (10 ^-6 mol)	Conversion (%)	TON^a	TOF^b (10 ^-4 s^-1)
1	2.2	5.98	94.68	6.97	6.45
2	2.2	6.13	97.38	6.99	6.47
3	2.2	6.33	41.01	2.85	2.64

Notes: (a) TON = 2 × moles of K₂Cr₂O₇ × conversion/moles of catalyst; (b) TOF = 2 × moles of K₂Cr₂O₇ × conversion/[moles of catalyst × time (180 × 60 s)].

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Crystal structures of hybrid completely reduced phospho­molybdates and catalytic performance applied as mol­ecular catalysts for the reduction of chromium(VI)

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Crystal structures of hybrid completely reduced phosphomolybdates and catalytic performance applied as molecular catalysts for the reduction of chromium(VI)