Crystal structure and photophysical properties of a novel polyoxomolybdate porphyrin

A novel polyoxomolybdate with a diprotonated porphyrin as counter-cation, namely, 5,10,15,20-tetra­kis­(4-carb­oxy­phen­yl)-21H,22H,23H,24H-porphine(2+) hexa­molybdate(VI) penta­hydrate, (C₄₈H₃₂N₄O₈)[Mo₆O₁₉]·5H₂O or (H₂TCPP)[Mo₆O₁₉]·5H₂O, I, was prepared via the hydro­thermal reaction of MoCl₅, 5,10,15,20-tetra­kis(4-carb­oxy­phen­yl)-21H,23H-porphine (TCPP) and distilled water. The crystal structure of hydrated polyoxometalate (POM) salt I was characterized by single-crystal X-ray diffraction. The compound is characterized by an isolated (zero-dimensional, 0D) structure, because it cannot extend via covalent bonds. The structure contains one [Mo₆O₁₉]²⁻ anion, one (H₂TCPP)²⁺ cation and five lattice water mol­ecules. Each of the Mo⁶⁺ ions is six-coordinated and displays a distorted octa­hedral motif. The (H₂TCPP)²⁺ cation displays a distorted saddle motif. A three-dimensional (3D) supra­molecular framework is formed via hydrogen-bonding inter­actions. The compound shows a red photo­luminescence emission.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

5,10,15,20-Tetrakis(4-carboxyphenyl)-21H,22H,23H, \24H-porphine(2+) hexamolybdate(VI) pentahydrate

Crystal data

(C48H32N4O8)[Mo6O19]·5H2O	Dx = 2.053 Mg m^−3
Mr = 1762.49	Melting point: not measured K
Orthorhombic, Pnnm	Mo Kα radiation, λ = 0.71073 Å
a = 19.3159 (8) Å	Cell parameters from 3496 reflections
b = 15.0183 (5) Å	θ = 3.6–26.2°
c = 19.6537 (10) Å	µ = 1.38 mm^−1
V = 5701.4 (4) Å^3	T = 293 K
Z = 4	Needle-like, blue
F(000) = 3464	0.25 × 0.04 × 0.03 mm

Data collection

Rigaku SuperNova (Mo) X-ray Source diffractometer	5129 independent reflections
Radiation source: micro-focus sealed X-ray tube	2187 reflections with I > 2σ(I)
Detector resolution: 16.1787 pixels mm^-1	Rint = 0.090
ω scans	θmax = 25.0°, θmin = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −22→15
Tmin = 0.936, Tmax = 0.959	k = −17→12
15930 measured reflections	l = −21→23

Refinement

Refinement on F^2	57 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.092	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.175	w = 1/[σ^2(Fo^2) + (0.0397P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
5129 reflections	Δρmax = 0.81 e Å^−3
448 parameters	Δρmin = −0.73 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mo5	0.26588 (7)	1.20235 (8)	0.38203 (6)	0.0748 (4)
Mo4	0.35201 (8)	1.30858 (9)	0.500000	0.0692 (6)
Mo3	0.34855 (8)	1.09164 (8)	0.500000	0.0537 (5)
Mo2	0.18223 (8)	1.31143 (8)	0.500000	0.0550 (5)
Mo1	0.17981 (8)	1.09494 (8)	0.500000	0.0514 (5)
O18	0.2650 (5)	1.2016 (5)	0.500000	0.040 (2)
O17	0.2714 (6)	1.3786 (6)	0.500000	0.074 (4)
O16	0.1246 (6)	1.3939 (7)	0.500000	0.100 (5)
O15	0.2612 (5)	1.0234 (5)	0.500000	0.048 (3)
O14	0.1298 (5)	1.2080 (6)	0.500000	0.062 (3)
O13	0.2019 (4)	1.2950 (5)	0.4053 (4)	0.072 (2)
O12	0.4165 (8)	1.3829 (9)	0.500000	0.120 (5)
O11	0.3372 (5)	1.2865 (5)	0.4055 (5)	0.090 (3)
O10	0.1952 (4)	1.1194 (5)	0.4047 (4)	0.072 (3)
O9	0.1154 (6)	1.0229 (7)	0.500000	0.095 (5)
O8	0.4004 (6)	1.1960 (6)	0.500000	0.084 (4)
O7	0.4077 (6)	1.0102 (6)	0.500000	0.099 (5)
O6	0.3308 (4)	1.1100 (5)	0.4053 (4)	0.070 (2)
O5	0.2668 (7)	1.2044 (8)	0.2979 (5)	0.165 (6)
O4	−0.1500 (4)	0.9368 (5)	0.8105 (4)	0.073 (3)
H4A	−0.173889	0.949916	0.843455	0.110*
O3	−0.0730 (4)	0.9072 (5)	0.8914 (4)	0.069 (3)
O2	0.5551 (5)	0.8958 (6)	0.8886 (4)	0.085 (3)
O1	0.6303 (4)	0.9359 (6)	0.8075 (4)	0.077 (3)
H1A	0.654994	0.948135	0.840096	0.115*
O4W	0.2386 (4)	0.7006 (5)	0.500000	0.037 (2)
O3W	0.1298 (6)	1.5818 (7)	0.500000	0.040 (3)
O2W	0.3437 (5)	1.5707 (7)	0.500000	0.043 (3)
O1W	0.2384 (4)	1.5074 (5)	0.3789 (4)	0.066 (2)
N3	0.1310 (5)	0.8379 (6)	0.500000	0.023 (3)
H3A	0.172412	0.859121	0.500000	0.028*
N2	0.2394 (4)	0.8366 (5)	0.6073 (3)	0.0250 (18)
H2A	0.239099	0.804374	0.571138	0.030*
N1	0.3480 (5)	0.8386 (6)	0.500000	0.025 (3)
H1B	0.307644	0.862693	0.499999	0.030*
C24	0.0226 (5)	0.8585 (6)	0.7943 (5)	0.030 (2)
H24A	0.032888	0.850763	0.840088	0.036*
C23	0.0717 (5)	0.8379 (6)	0.7451 (5)	0.035 (3)
H23A	0.113475	0.812254	0.758074	0.042*
C22	0.0588 (5)	0.8555 (5)	0.6756 (5)	0.023 (2)
C21	−0.0061 (5)	0.8877 (6)	0.6585 (5)	0.029 (2)
H21A	−0.016739	0.898870	0.613135	0.035*
C20	−0.0544 (5)	0.9030 (5)	0.7077 (5)	0.032 (3)
H20A	−0.098211	0.922823	0.695080	0.038*
C19	−0.0399 (5)	0.8897 (6)	0.7757 (5)	0.025 (2)
C18	−0.0907 (5)	0.9121 (7)	0.8305 (6)	0.043 (3)
C17	0.5368 (5)	0.8986 (6)	0.7072 (5)	0.032 (3)
H17A	0.580583	0.918424	0.694653	0.039*
C16	0.4867 (5)	0.8839 (6)	0.6573 (5)	0.032 (3)
H16A	0.497155	0.895368	0.611933	0.038*
C15	0.4212 (5)	0.8523 (6)	0.6746 (5)	0.028 (2)
C14	0.4077 (6)	0.8341 (6)	0.7433 (5)	0.041 (3)
H14A	0.365236	0.810079	0.755942	0.049*
C13	0.4567 (6)	0.8515 (6)	0.7918 (5)	0.041 (3)
H13A	0.446413	0.841467	0.837424	0.049*
C12	0.5222 (6)	0.8843 (6)	0.7737 (5)	0.035 (3)
C11	0.5736 (6)	0.9047 (7)	0.8285 (6)	0.041 (3)
C10	0.0314 (5)	0.7781 (6)	0.5342 (4)	0.034 (3)
H10A	−0.003619	0.755112	0.561487	0.040*
C9	0.0923 (5)	0.8181 (5)	0.5582 (5)	0.022 (2)
C8	0.1128 (5)	0.8452 (5)	0.6230 (5)	0.023 (2)
C7	0.1809 (5)	0.8672 (6)	0.6412 (4)	0.027 (2)
C6	0.2059 (5)	0.9214 (6)	0.6947 (4)	0.031 (2)
H6A	0.178545	0.952226	0.725745	0.037*
C5	0.2758 (5)	0.9213 (6)	0.6937 (4)	0.028 (2)
H5A	0.304374	0.952661	0.723304	0.033*
C4	0.2981 (6)	0.8658 (6)	0.6404 (4)	0.030 (2)
C3	0.3670 (5)	0.8422 (5)	0.6230 (5)	0.028 (2)
C2	0.3851 (5)	0.8165 (6)	0.5577 (5)	0.032 (3)
C1	0.4456 (5)	0.7711 (5)	0.5345 (4)	0.030 (3)
H1C	0.479418	0.745810	0.562057	0.037*
H1WA	0.254 (5)	1.456 (3)	0.390 (5)	0.046*
H1WB	0.2390 (4)	1.5394 (13)	0.4151 (4)	0.046*
H2WA	0.3881 (7)	1.574 (8)	0.500000	0.046*
H2WB	0.306 (3)	1.540 (7)	0.500000	0.046*
H4WA	0.2828 (5)	0.7062 (9)	0.500000	0.046*
H3WA	0.112 (4)	1.577 (6)	0.460 (2)	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo5	0.0985 (11)	0.0840 (9)	0.0419 (7)	0.0115 (8)	0.0095 (7)	0.0090 (6)
Mo4	0.0343 (11)	0.0334 (8)	0.1400 (19)	−0.0065 (7)	0.000	0.000
Mo3	0.0387 (11)	0.0324 (7)	0.0902 (13)	0.0034 (7)	0.000	0.000
Mo2	0.0402 (11)	0.0311 (7)	0.0937 (14)	0.0068 (7)	0.000	0.000
Mo1	0.0341 (10)	0.0314 (7)	0.0887 (13)	−0.0056 (7)	0.000	0.000
O18	0.047 (7)	0.034 (5)	0.037 (6)	0.004 (5)	0.000	0.000
O17	0.065 (9)	0.033 (6)	0.124 (11)	−0.005 (6)	0.000	0.000
O16	0.063 (10)	0.053 (8)	0.183 (15)	0.029 (7)	0.000	0.000
O15	0.044 (7)	0.018 (4)	0.081 (8)	0.000 (5)	0.000	0.000
O14	0.015 (7)	0.056 (7)	0.114 (10)	0.009 (5)	0.000	0.000
O13	0.087 (7)	0.066 (5)	0.063 (6)	0.023 (5)	−0.019 (5)	0.020 (4)
O12	0.101 (9)	0.091 (8)	0.169 (9)	−0.017 (7)	0.000	0.000
O11	0.088 (8)	0.068 (6)	0.115 (8)	−0.017 (5)	0.020 (6)	0.019 (5)
O10	0.090 (7)	0.069 (5)	0.056 (6)	0.004 (5)	−0.042 (5)	−0.011 (4)
O9	0.047 (9)	0.045 (7)	0.192 (15)	−0.023 (6)	0.000	0.000
O8	0.032 (8)	0.041 (6)	0.180 (14)	−0.007 (6)	0.000	0.000
O7	0.068 (10)	0.034 (6)	0.194 (16)	0.018 (6)	0.000	0.000
O6	0.069 (7)	0.067 (5)	0.074 (6)	0.018 (5)	0.030 (5)	−0.004 (4)
O5	0.268 (17)	0.188 (12)	0.039 (7)	0.022 (11)	0.017 (7)	0.023 (7)
O4	0.058 (6)	0.122 (7)	0.038 (5)	0.029 (6)	0.029 (4)	0.014 (5)
O3	0.070 (7)	0.114 (7)	0.023 (5)	0.029 (5)	0.005 (4)	0.005 (5)
O2	0.122 (9)	0.101 (7)	0.031 (6)	−0.029 (6)	−0.024 (5)	0.018 (5)
O1	0.050 (6)	0.121 (8)	0.060 (6)	−0.018 (6)	−0.030 (5)	−0.010 (5)
O4W	0.023 (6)	0.037 (5)	0.050 (6)	0.002 (5)	0.000	0.000
O3W	0.056 (8)	0.053 (6)	0.010 (6)	−0.004 (5)	0.000	0.000
O2W	0.011 (6)	0.065 (7)	0.055 (7)	−0.014 (6)	0.000	0.000
O1W	0.061 (6)	0.080 (6)	0.056 (5)	0.009 (5)	−0.007 (4)	0.013 (5)
N3	0.007 (7)	0.047 (6)	0.017 (7)	0.004 (5)	0.000	0.000
N2	0.024 (5)	0.041 (4)	0.010 (4)	0.004 (4)	−0.001 (4)	−0.005 (3)
N1	0.017 (4)	0.032 (4)	0.025 (5)	0.002 (4)	0.000	0.000
C24	0.025 (7)	0.047 (6)	0.018 (6)	0.000 (5)	0.008 (5)	0.007 (4)
C23	0.026 (4)	0.042 (4)	0.036 (5)	0.005 (4)	−0.005 (4)	0.008 (4)
C22	0.016 (4)	0.034 (4)	0.020 (4)	0.002 (3)	0.003 (3)	−0.002 (3)
C21	0.026 (7)	0.040 (6)	0.022 (6)	0.004 (5)	0.006 (5)	−0.001 (4)
C20	0.032 (7)	0.035 (5)	0.030 (7)	0.008 (5)	−0.006 (5)	0.006 (5)
C19	0.012 (4)	0.032 (4)	0.030 (4)	0.002 (3)	0.005 (4)	−0.002 (3)
C18	0.014 (7)	0.057 (7)	0.058 (9)	0.013 (5)	−0.010 (6)	0.007 (6)
C17	0.018 (4)	0.042 (4)	0.036 (5)	−0.001 (4)	−0.005 (4)	−0.001 (4)
C16	0.023 (4)	0.039 (4)	0.033 (4)	−0.001 (4)	0.004 (4)	−0.001 (3)
C15	0.026 (7)	0.035 (5)	0.024 (6)	0.009 (5)	0.002 (5)	0.002 (4)
C14	0.053 (8)	0.052 (6)	0.018 (6)	0.000 (6)	0.004 (6)	0.014 (5)
C13	0.062 (9)	0.045 (6)	0.014 (7)	0.014 (6)	0.001 (6)	0.004 (5)
C12	0.044 (8)	0.035 (6)	0.026 (7)	0.003 (5)	0.000 (6)	0.002 (4)
C11	0.035 (8)	0.048 (6)	0.040 (8)	−0.005 (6)	−0.007 (7)	−0.006 (6)
C10	0.030 (7)	0.041 (6)	0.029 (6)	0.001 (5)	0.005 (4)	0.002 (4)
C9	0.015 (4)	0.026 (4)	0.025 (4)	0.001 (3)	−0.003 (4)	0.003 (3)
C8	0.009 (6)	0.036 (5)	0.025 (6)	0.006 (4)	0.000 (5)	0.007 (4)
C7	0.016 (6)	0.038 (5)	0.028 (6)	0.004 (5)	0.008 (5)	0.004 (4)
C6	0.043 (7)	0.037 (5)	0.012 (5)	0.002 (5)	0.004 (5)	−0.009 (4)
C5	0.006 (6)	0.045 (6)	0.031 (6)	−0.006 (4)	−0.004 (5)	−0.001 (5)
C4	0.047 (8)	0.028 (5)	0.013 (6)	0.003 (5)	−0.004 (5)	0.002 (4)
C3	0.023 (7)	0.029 (5)	0.032 (7)	0.000 (4)	0.001 (5)	0.000 (4)
C2	0.026 (7)	0.037 (5)	0.033 (7)	0.000 (5)	0.002 (5)	0.003 (5)
C1	0.031 (7)	0.035 (5)	0.026 (6)	0.003 (5)	0.001 (4)	−0.003 (4)

Geometric parameters (Å, º)

Mo5—O5	1.653 (9)	N2—C4	1.377 (11)
Mo5—O10	1.902 (8)	N2—C7	1.391 (11)
Mo5—O13	1.917 (8)	N2—H2A	0.8600
Mo5—O6	1.925 (8)	N1—C2^i	1.382 (11)
Mo5—O11	1.926 (9)	N1—C2	1.382 (11)
Mo5—O18	2.3187 (11)	N1—H1B	0.8600
Mo4—O12	1.672 (14)	C24—C19	1.345 (12)
Mo4—O17	1.879 (11)	C24—C23	1.389 (12)
Mo4—O11	1.907 (9)	C24—H24A	0.9300
Mo4—O11^i	1.907 (9)	C23—C22	1.413 (12)
Mo4—O8	1.932 (10)	C23—H23A	0.9300
Mo4—O18	2.325 (9)	C22—C21	1.385 (12)
Mo3—O7	1.674 (10)	C22—C8	1.477 (12)
Mo3—O8	1.860 (10)	C21—C20	1.364 (12)
Mo3—O6^i	1.912 (8)	C21—H21A	0.9300
Mo3—O6	1.912 (8)	C20—C19	1.380 (12)
Mo3—O15	1.974 (9)	C20—H20A	0.9300
Mo3—O18	2.309 (9)	C19—C18	1.496 (13)
Mo2—O16	1.666 (11)	C17—C12	1.354 (12)
Mo2—O14	1.854 (10)	C17—C16	1.395 (12)
Mo2—O13^i	1.915 (8)	C17—H17A	0.9300
Mo2—O13	1.915 (8)	C16—C15	1.394 (12)
Mo2—O17	1.996 (11)	C16—H16A	0.9300
Mo2—O18	2.297 (9)	C15—C14	1.401 (12)
Mo1—O9	1.649 (10)	C15—C3	1.465 (13)
Mo1—O15	1.904 (9)	C14—C13	1.368 (13)
Mo1—O10	1.931 (8)	C14—H14A	0.9300
Mo1—O10^i	1.931 (8)	C13—C12	1.405 (13)
Mo1—O14	1.954 (9)	C13—H13A	0.9300
Mo1—O18	2.297 (9)	C12—C11	1.496 (14)
O4—C18	1.267 (11)	C10—C10^i	1.345 (16)
O4—H4A	0.8200	C10—C9	1.401 (12)
O3—C18	1.247 (11)	C10—H10A	0.9300
O2—C11	1.242 (12)	C9—C8	1.394 (12)
O1—C11	1.260 (12)	C8—C7	1.403 (12)
O1—H1A	0.8200	C7—C6	1.416 (11)
O4W—H4WA	0.859 (5)	C6—C5	1.349 (12)
O3W—H3WA	0.859 (5)	C6—H6A	0.9300
O3W—H3WA^i	0.859 (5)	C5—C4	1.407 (11)
O2W—H2WA	0.860 (5)	C5—H5A	0.9300
O2W—H2WB	0.860 (5)	C4—C3	1.420 (12)
O1W—H1WA	0.860 (5)	C3—C2	1.386 (12)
O1W—H1WB	0.859 (5)	C2—C1	1.427 (12)
N3—C9^i	1.400 (10)	C1—C1^i	1.355 (16)
N3—C9	1.400 (10)	C1—H1C	0.9300
N3—H3A	0.8600
O5—Mo5—O10	104.7 (5)	Mo2—O14—Mo1	117.3 (5)
O5—Mo5—O13	103.4 (5)	Mo2—O13—Mo5	117.0 (3)
O10—Mo5—O13	87.5 (4)	Mo4—O11—Mo5	117.1 (4)
O5—Mo5—O6	104.1 (5)	Mo5—O10—Mo1	117.5 (3)
O10—Mo5—O6	86.5 (3)	Mo3—O8—Mo4	118.5 (6)
O13—Mo5—O6	152.4 (3)	Mo3—O6—Mo5	116.9 (3)
O5—Mo5—O11	102.7 (5)	C18—O4—H4A	109.5
O10—Mo5—O11	152.6 (3)	C11—O1—H1A	109.5
O13—Mo5—O11	85.9 (4)	H3WA—O3W—H3WA^i	131 (10)
O6—Mo5—O11	87.1 (4)	H2WA—O2W—H2WB	151 (10)
O5—Mo5—O18	179.2 (5)	H1WA—O1W—H1WB	107 (7)
O10—Mo5—O18	76.0 (3)	C9^i—N3—C9	109.7 (11)
O13—Mo5—O18	76.1 (3)	C9^i—N3—H3A	125.2
O6—Mo5—O18	76.3 (3)	C9—N3—H3A	125.2
O11—Mo5—O18	76.6 (3)	C4—N2—C7	109.7 (7)
O12—Mo4—O17	104.1 (6)	C4—N2—H2A	125.1
O12—Mo4—O11	103.2 (2)	C7—N2—H2A	125.1
O17—Mo4—O11	88.5 (3)	C2^i—N1—C2	110.3 (12)
O12—Mo4—O11^i	103.2 (2)	C2^i—N1—H1B	124.9
O17—Mo4—O11^i	88.5 (3)	C2—N1—H1B	124.9
O11—Mo4—O11^i	153.5 (5)	C19—C24—C23	120.1 (9)
O12—Mo4—O8	102.9 (6)	C19—C24—H24A	119.9
O17—Mo4—O8	152.9 (4)	C23—C24—H24A	119.9
O11—Mo4—O8	85.4 (3)	C24—C23—C22	120.7 (9)
O11^i—Mo4—O8	85.4 (3)	C24—C23—H23A	119.7
O12—Mo4—O18	178.1 (5)	C22—C23—H23A	119.7
O17—Mo4—O18	77.7 (4)	C21—C22—C23	117.3 (8)
O11—Mo4—O18	76.8 (2)	C21—C22—C8	120.3 (8)
O11^i—Mo4—O18	76.8 (2)	C23—C22—C8	122.2 (8)
O8—Mo4—O18	75.2 (4)	C20—C21—C22	120.4 (9)
O7—Mo3—O8	104.4 (5)	C20—C21—H21A	119.8
O7—Mo3—O6^i	103.2 (2)	C22—C21—H21A	119.8
O8—Mo3—O6^i	88.6 (2)	C21—C20—C19	121.5 (9)
O7—Mo3—O6	103.2 (2)	C21—C20—H20A	119.2
O8—Mo3—O6	88.6 (2)	C19—C20—H20A	119.2
O6^i—Mo3—O6	153.3 (4)	C24—C19—C20	119.7 (9)
O7—Mo3—O15	101.8 (5)	C24—C19—C18	118.1 (9)
O8—Mo3—O15	153.8 (4)	C20—C19—C18	122.1 (9)
O6^i—Mo3—O15	85.5 (2)	O3—C18—O4	124.3 (11)
O6—Mo3—O15	85.5 (2)	O3—C18—C19	119.9 (10)
O7—Mo3—O18	178.7 (5)	O4—C18—C19	115.8 (10)
O8—Mo3—O18	76.9 (4)	C12—C17—C16	120.6 (10)
O6^i—Mo3—O18	76.8 (2)	C12—C17—H17A	119.7
O6—Mo3—O18	76.8 (2)	C16—C17—H17A	119.7
O15—Mo3—O18	76.9 (3)	C15—C16—C17	120.7 (9)
O16—Mo2—O14	104.9 (5)	C15—C16—H16A	119.6
O16—Mo2—O13^i	103.2 (2)	C17—C16—H16A	119.6
O14—Mo2—O13^i	90.0 (3)	C16—C15—C14	118.1 (9)
O16—Mo2—O13	103.2 (2)	C16—C15—C3	120.9 (9)
O14—Mo2—O13	90.0 (3)	C14—C15—C3	120.9 (9)
O13^i—Mo2—O13	152.7 (5)	C13—C14—C15	120.3 (10)
O16—Mo2—O17	101.6 (5)	C13—C14—H14A	119.8
O14—Mo2—O17	153.5 (4)	C15—C14—H14A	119.8
O13^i—Mo2—O17	83.9 (3)	C14—C13—C12	120.9 (10)
O13—Mo2—O17	83.9 (3)	C14—C13—H13A	119.6
O16—Mo2—O18	177.9 (5)	C12—C13—H13A	119.6
O14—Mo2—O18	77.2 (4)	C17—C12—C13	119.2 (10)
O13^i—Mo2—O18	76.7 (2)	C17—C12—C11	121.7 (10)
O13—Mo2—O18	76.7 (2)	C13—C12—C11	119.1 (10)
O17—Mo2—O18	76.3 (4)	O2—C11—O1	127.0 (11)
O9—Mo1—O15	104.7 (5)	O2—C11—C12	118.2 (11)
O9—Mo1—O10	103.9 (2)	O1—C11—C12	114.6 (11)
O15—Mo1—O10	88.9 (2)	C10^i—C10—C9	109.7 (5)
O9—Mo1—O10^i	103.9 (2)	C10^i—C10—H10A	125.2
O15—Mo1—O10^i	88.9 (2)	C9—C10—H10A	125.2
O10—Mo1—O10^i	151.7 (5)	C8—C9—N3	122.1 (9)
O9—Mo1—O14	101.4 (5)	C8—C9—C10	132.1 (9)
O15—Mo1—O14	154.0 (4)	N3—C9—C10	105.4 (8)
O10—Mo1—O14	84.9 (2)	C9—C8—C7	124.7 (8)
O10^i—Mo1—O14	84.9 (2)	C9—C8—C22	118.0 (8)
O9—Mo1—O18	176.8 (5)	C7—C8—C22	117.3 (8)
O15—Mo1—O18	78.6 (3)	N2—C7—C8	124.2 (8)
O10—Mo1—O18	76.0 (2)	N2—C7—C6	105.6 (8)
O10^i—Mo1—O18	76.0 (2)	C8—C7—C6	130.2 (9)
O14—Mo1—O18	75.4 (3)	C5—C6—C7	109.2 (8)
Mo1—O18—Mo2	90.1 (3)	C5—C6—H6A	125.4
Mo1—O18—Mo3	90.1 (3)	C7—C6—H6A	125.4
Mo2—O18—Mo3	179.8 (4)	C6—C5—C4	108.5 (8)
Mo1—O18—Mo5^i	90.5 (2)	C6—C5—H5A	125.7
Mo2—O18—Mo5^i	90.1 (2)	C4—C5—H5A	125.7
Mo3—O18—Mo5^i	89.9 (2)	N2—C4—C5	106.8 (9)
Mo1—O18—Mo5	90.5 (2)	N2—C4—C3	125.4 (8)
Mo2—O18—Mo5	90.1 (2)	C5—C4—C3	127.9 (9)
Mo3—O18—Mo5	89.9 (2)	C2—C3—C4	121.9 (9)
Mo5^i—O18—Mo5	179.0 (5)	C2—C3—C15	119.4 (9)
Mo1—O18—Mo4	179.5 (4)	C4—C3—C15	118.6 (9)
Mo2—O18—Mo4	90.4 (3)	N1—C2—C3	124.2 (9)
Mo3—O18—Mo4	89.4 (3)	N1—C2—C1	106.1 (9)
Mo5^i—O18—Mo4	89.5 (2)	C3—C2—C1	129.5 (9)
Mo5—O18—Mo4	89.5 (2)	C1^i—C1—C2	108.7 (5)
Mo4—O17—Mo2	115.6 (5)	C1^i—C1—H1C	125.7
Mo1—O15—Mo3	114.4 (4)	C2—C1—H1C	125.7

Symmetry code: (i) x, y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O1W^ii	0.82	1.90	2.656 (11)	152
O2W—H2WA···O3^iii	0.86 (2)	2.28 (2)	2.694 (10)	110 (1)
O2W—H2WA···O3^iv	0.86 (2)	2.28 (2)	2.694 (10)	110 (1)
O4—H4A···O1W^v	0.82	1.94	2.675 (11)	149
O3W—H3WA···O2^vi	0.86 (5)	1.83 (7)	2.644 (11)	157 (8)
O4W—H4WA···O2W^vii	0.86 (1)	2.35 (2)	2.816 (13)	114 (1)
N2—H2A···O4W	0.86	2.09	2.936 (9)	166
O4W—H4WA···N1	0.86 (1)	2.35 (2)	2.960 (12)	118 (1)

Symmetry codes: (ii) x+1/2, −y+5/2, z+1/2; (iii) x+1/2, −y+5/2, −z+3/2; (iv) x+1/2, −y+5/2, z−1/2; (v) x−1/2, −y+5/2, z+1/2; (vi) x−1/2, −y+5/2, z−1/2; (vii) x, y−1, z.