Modified polyoxometalate: a novel monocapped bi-supporting and reduced α-Keggin structure {PMo₁₂O₄₀[Cu(2,2′-bpy)]}[Cu(2,2′-bpy)(en)(H₂O)]₂

A novel modified polyoxometalate, {PMo₁₂O₄₀[Cu(2,2′-bpy)]}[Cu(2,2′-bpy)(en)(H₂O)]₂ [2,2′-bpy is 2,2′-bipyridyl (C₁₀H₈N₂) and en is ethyl­enedi­amine (C₂H₈N₂)], has been synthesized hydro­thermally and structurally characterized by elemental analysis, TG, IR, XPS and single-crystal X-ray diffraction. The structural analysis reveals that the com­pound contains the reduced Keggin polyanion [PMo₁₂O₄₀]⁶⁻ as the parent unit, which is monocapped by [Cu(2,2′-bpy)]²⁺ fragments via four bridging O atoms on an {Mo₄O₄} pit and bi-supported by two [Cu(2,2′-bpy)(en)(H₂O)]²⁺ coordination cations simultaneously. There exist strong intra­molecular π–π stacking between the capping and supporting units, which play a stabilizing role during the crystallization of the com­pound. Adjacent POM clusters are further aggregated to form a three-dimensional supra­molecular network through noncovalent forces, hydrogen bonding and π–π stacking inter­actions. In addition, the photocatalytic properties were investigated in detail, and the results indicated that the com­pound can be used as a photocatalyst towards the decom­position of the organic pollutant methyl­ene blue (MB).

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: pubCIF (Westrip, 2010).

(I)

Crystal data

{[PMo12O40]Cu(C10H8N2)}[Cu(C10H8N2)(C2H8N2)(H2O)]2	F(000) = 5040
Mr = 2637.69	Dx = 2.732 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2yc	Cell parameters from 9970 reflections
a = 18.9465 (8) Å	θ = 2.2–26.1°
b = 14.7806 (6) Å	µ = 3.36 mm^−1
c = 24.5444 (10) Å	T = 296 K
β = 111.093 (1)°	Prism, black
V = 6412.9 (5) Å^3	0.36 × 0.27 × 0.21 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	6363 independent reflections
Radiation source: fine-focus sealed tube	5864 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 26.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −22→23
Tmin = 0.377, Tmax = 0.539	k = −17→18
17366 measured reflections	l = −21→30

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0198P)^2 + 10.7248P] where P = (Fo^2 + 2Fc^2)/3
6363 reflections	(Δ/σ)max = 0.002
545 parameters	Δρmax = 0.55 e Å^−3
2 restraints	Δρmin = −0.48 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	0.5000	−0.11132 (6)	0.2500	0.00891 (18)
Mo1	0.336787 (13)	−0.118060 (14)	0.120477 (10)	0.01141 (6)
Mo2	0.474146 (13)	−0.279639 (14)	0.142142 (10)	0.01214 (6)
Mo3	0.358431 (13)	−0.282904 (15)	0.221090 (10)	0.01269 (6)
Mo4	0.486698 (13)	0.054521 (14)	0.142939 (9)	0.01100 (6)
Mo5	0.623739 (13)	−0.106362 (15)	0.169174 (10)	0.01289 (6)
Mo6	0.642343 (13)	0.058302 (14)	0.269812 (10)	0.01166 (6)
Cu1	0.5000	0.18894 (3)	0.2500	0.01527 (10)
Cu2	0.570050 (19)	0.20825 (2)	0.060638 (14)	0.01556 (8)
O1	0.26363 (11)	−0.09360 (12)	0.05829 (8)	0.0162 (4)
O2	0.47990 (11)	−0.35763 (12)	0.09361 (8)	0.0166 (4)
O3	0.29622 (11)	−0.36381 (12)	0.22123 (8)	0.0170 (4)
O4	0.45804 (11)	0.13263 (12)	0.08892 (8)	0.0181 (4)
O5	0.67732 (11)	−0.12651 (12)	0.12867 (8)	0.0192 (4)
O6	0.70752 (11)	0.13955 (12)	0.29626 (8)	0.0171 (4)
O7	0.39043 (10)	−0.21110 (12)	0.09244 (8)	0.0140 (4)
O8	0.29887 (10)	−0.21498 (11)	0.15387 (8)	0.0134 (4)
O9	0.32482 (10)	−0.03216 (12)	0.17340 (8)	0.0135 (4)
O10	0.41312 (10)	−0.03319 (11)	0.11632 (7)	0.0129 (4)
O11	0.40624 (10)	−0.33943 (11)	0.17236 (8)	0.0140 (4)
O12	0.55398 (10)	−0.31369 (12)	0.21251 (8)	0.0152 (4)
O13	0.53959 (10)	−0.18767 (12)	0.13468 (8)	0.0149 (4)
O14	0.55650 (10)	−0.01209 (11)	0.12071 (8)	0.0142 (4)
O15	0.57115 (11)	0.11712 (11)	0.19952 (8)	0.0141 (4)
O16	0.43503 (10)	0.09580 (11)	0.19692 (8)	0.0136 (4)
O17	0.67675 (10)	−0.00923 (11)	0.21756 (8)	0.0139 (4)
O18	0.65857 (10)	−0.19045 (12)	0.23001 (8)	0.0148 (4)
O19	0.44260 (10)	−0.17127 (11)	0.20388 (7)	0.0116 (4)
O20	0.54325 (10)	−0.05232 (11)	0.22112 (7)	0.0114 (4)
O1W	0.64402 (15)	0.28826 (19)	0.01833 (11)	0.0365 (6)
N1	0.44137 (14)	0.29168 (15)	0.20129 (11)	0.0206 (5)
N2	0.48147 (13)	0.28857 (15)	0.01977 (10)	0.0170 (5)
N3	0.58804 (13)	0.30346 (15)	0.12243 (10)	0.0174 (5)
N4	0.66253 (15)	0.13739 (18)	0.10498 (11)	0.0192 (5)
N5	0.55660 (16)	0.11531 (16)	−0.00292 (11)	0.0180 (5)
C1	0.38204 (18)	0.2855 (2)	0.15137 (14)	0.0240 (7)
C2	0.3461 (2)	0.3610 (2)	0.12065 (17)	0.0338 (8)
C3	0.3731 (2)	0.4453 (2)	0.14171 (17)	0.0386 (9)
H3	0.3501	0.4969	0.1213	0.046*
C4	0.4336 (2)	0.4530 (2)	0.19247 (17)	0.0335 (8)
C5	0.46789 (17)	0.37479 (18)	0.22252 (14)	0.0233 (7)
C6	0.42231 (17)	0.2719 (2)	−0.02902 (13)	0.0209 (6)
C7	0.36729 (18)	0.3347 (2)	−0.05551 (13)	0.0268 (7)
C8	0.37382 (19)	0.4197 (2)	−0.03069 (14)	0.0292 (7)
C9	0.43438 (19)	0.4383 (2)	0.01986 (14)	0.0268 (7)
C10	0.48744 (17)	0.37155 (18)	0.04455 (12)	0.0192 (6)
C11	0.55105 (17)	0.38108 (18)	0.10072 (13)	0.0191 (6)
C12	0.5718 (2)	0.4614 (2)	0.13141 (15)	0.0284 (7)
C13	0.62931 (19)	0.4621 (2)	0.18492 (15)	0.0302 (7)
C14	0.66387 (18)	0.3817 (2)	0.20864 (14)	0.0255 (7)
C15	0.64171 (17)	0.3036 (2)	0.17582 (13)	0.0199 (6)
C16	0.68363 (18)	0.0805 (2)	0.06350 (13)	0.0217 (6)
C17	0.61254 (17)	0.04111 (19)	0.01998 (12)	0.0188 (6)
H17B	0.6255 (16)	0.0119 (19)	−0.0115 (13)	0.015 (7)*
H16B	0.7085 (18)	0.1196 (19)	0.0465 (13)	0.018 (8)*
H7	0.3280 (14)	0.322 (2)	−0.0884 (10)	0.026 (9)*
H17A	0.5901 (17)	−0.002 (2)	0.0407 (13)	0.020 (8)*
H12	0.548 (2)	0.511 (2)	0.1182 (15)	0.036 (10)*
H6	0.4182 (18)	0.214 (2)	−0.0444 (14)	0.027 (9)*
H9	0.4394 (19)	0.4929 (15)	0.0374 (14)	0.038 (10)*
H15	0.6651 (16)	0.251 (2)	0.1913 (12)	0.015 (7)*
H4A	0.6539 (19)	0.101 (2)	0.1319 (15)	0.028 (9)*
H14	0.7045 (18)	0.3757 (19)	0.2436 (14)	0.021 (8)*
H8	0.337 (2)	0.460 (2)	−0.0478 (15)	0.032 (9)*
H16A	0.7176 (17)	0.0341 (19)	0.0826 (12)	0.012 (7)*
H1	0.3666 (18)	0.226 (2)	0.1397 (14)	0.026 (9)*
H13	0.6432 (19)	0.515 (2)	0.2027 (14)	0.029 (9)*
H4	0.454 (2)	0.508 (3)	0.2084 (16)	0.046 (11)*
H4B	0.6956 (19)	0.170 (2)	0.1202 (14)	0.023 (10)*
H2	0.303 (2)	0.357 (2)	0.0877 (16)	0.036 (10)*
H2W	0.639 (3)	0.268 (3)	−0.019 (2)	0.080 (16)*
H1W	0.673 (3)	0.323 (3)	0.0301 (19)	0.053 (14)*
H5A	0.5611 (19)	0.138 (2)	−0.0330 (15)	0.028 (9)*
H5B	0.515 (2)	0.097 (2)	−0.0170 (14)	0.016 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0104 (5)	0.0076 (4)	0.0097 (4)	0.000	0.0048 (4)	0.000
Mo1	0.01247 (12)	0.01077 (11)	0.01030 (11)	−0.00017 (8)	0.00327 (9)	0.00066 (8)
Mo2	0.01642 (12)	0.00973 (11)	0.01031 (11)	0.00097 (9)	0.00486 (9)	−0.00107 (8)
Mo3	0.01332 (12)	0.01225 (11)	0.01191 (12)	−0.00303 (9)	0.00383 (9)	0.00129 (8)
Mo4	0.01399 (12)	0.00961 (11)	0.01051 (11)	−0.00084 (8)	0.00575 (9)	0.00102 (8)
Mo5	0.01486 (12)	0.01301 (11)	0.01261 (12)	0.00004 (9)	0.00713 (9)	−0.00125 (8)
Mo6	0.01353 (12)	0.01025 (11)	0.01242 (11)	−0.00187 (8)	0.00614 (9)	−0.00060 (8)
Cu1	0.0200 (3)	0.0089 (2)	0.0169 (2)	0.000	0.0066 (2)	0.000
Cu2	0.01852 (18)	0.01345 (16)	0.01318 (16)	−0.00004 (13)	0.00387 (13)	−0.00072 (13)
O1	0.0171 (10)	0.0143 (9)	0.0153 (10)	−0.0011 (8)	0.0036 (8)	0.0002 (7)
O2	0.0217 (11)	0.0130 (9)	0.0145 (10)	0.0015 (8)	0.0056 (8)	−0.0014 (7)
O3	0.0182 (10)	0.0177 (9)	0.0144 (10)	−0.0036 (8)	0.0052 (8)	0.0009 (8)
O4	0.0232 (11)	0.0155 (9)	0.0178 (10)	−0.0005 (8)	0.0102 (8)	0.0045 (8)
O5	0.0220 (11)	0.0202 (10)	0.0188 (10)	0.0000 (8)	0.0114 (9)	−0.0022 (8)
O6	0.0196 (10)	0.0154 (9)	0.0176 (10)	−0.0034 (8)	0.0083 (8)	−0.0027 (8)
O7	0.0165 (10)	0.0144 (9)	0.0101 (9)	0.0006 (7)	0.0036 (8)	−0.0002 (7)
O8	0.0145 (10)	0.0133 (9)	0.0128 (9)	0.0004 (7)	0.0054 (8)	0.0027 (7)
O9	0.0129 (10)	0.0136 (9)	0.0157 (9)	0.0003 (7)	0.0074 (8)	0.0010 (7)
O10	0.0171 (10)	0.0122 (8)	0.0114 (9)	0.0005 (7)	0.0078 (8)	0.0002 (7)
O11	0.0174 (10)	0.0105 (9)	0.0142 (9)	−0.0016 (7)	0.0060 (8)	−0.0004 (7)
O12	0.0164 (10)	0.0137 (9)	0.0134 (9)	0.0000 (7)	0.0028 (8)	−0.0015 (7)
O13	0.0171 (10)	0.0145 (9)	0.0133 (9)	−0.0006 (8)	0.0057 (8)	−0.0013 (7)
O14	0.0177 (10)	0.0137 (9)	0.0131 (9)	−0.0008 (7)	0.0078 (8)	0.0007 (7)
O15	0.0173 (10)	0.0121 (9)	0.0142 (9)	−0.0015 (7)	0.0072 (8)	0.0015 (7)
O16	0.0171 (10)	0.0105 (8)	0.0138 (9)	0.0003 (7)	0.0064 (8)	0.0010 (7)
O17	0.0142 (10)	0.0143 (9)	0.0146 (9)	−0.0019 (7)	0.0069 (8)	−0.0007 (7)
O18	0.0146 (10)	0.0146 (9)	0.0151 (9)	−0.0013 (7)	0.0053 (8)	−0.0027 (7)
O19	0.0138 (9)	0.0104 (8)	0.0106 (9)	−0.0008 (7)	0.0043 (7)	−0.0006 (7)
O20	0.0127 (9)	0.0102 (8)	0.0123 (9)	−0.0008 (7)	0.0058 (7)	−0.0001 (7)
O1W	0.0399 (15)	0.0494 (16)	0.0176 (12)	−0.0300 (13)	0.0074 (11)	−0.0031 (11)
N1	0.0249 (14)	0.0123 (11)	0.0285 (14)	0.0023 (10)	0.0143 (11)	0.0020 (10)
N2	0.0212 (13)	0.0166 (11)	0.0146 (12)	0.0005 (10)	0.0081 (10)	0.0022 (9)
N3	0.0194 (13)	0.0143 (11)	0.0187 (12)	−0.0002 (9)	0.0069 (10)	0.0000 (9)
N4	0.0196 (14)	0.0200 (12)	0.0159 (13)	−0.0012 (11)	0.0037 (11)	−0.0019 (11)
N5	0.0192 (14)	0.0190 (13)	0.0140 (13)	−0.0029 (11)	0.0040 (11)	−0.0011 (10)
C1	0.0265 (17)	0.0188 (15)	0.0282 (17)	0.0024 (13)	0.0117 (14)	0.0057 (13)
C2	0.0266 (19)	0.0324 (18)	0.042 (2)	0.0051 (15)	0.0113 (16)	0.0129 (16)
C3	0.036 (2)	0.0216 (17)	0.059 (2)	0.0106 (15)	0.0174 (18)	0.0165 (16)
C4	0.034 (2)	0.0128 (15)	0.056 (2)	0.0033 (14)	0.0200 (18)	0.0050 (15)
C5	0.0262 (17)	0.0133 (13)	0.0360 (18)	0.0019 (12)	0.0179 (14)	0.0016 (12)
C6	0.0237 (16)	0.0222 (15)	0.0172 (15)	−0.0007 (12)	0.0078 (12)	−0.0007 (12)
C7	0.0217 (17)	0.0377 (18)	0.0181 (15)	0.0008 (14)	0.0036 (13)	0.0013 (14)
C8	0.0274 (18)	0.0301 (17)	0.0286 (17)	0.0103 (15)	0.0080 (14)	0.0078 (14)
C9	0.0301 (18)	0.0187 (15)	0.0306 (18)	0.0044 (13)	0.0098 (14)	0.0001 (13)
C10	0.0225 (16)	0.0176 (13)	0.0190 (15)	−0.0013 (12)	0.0093 (12)	0.0014 (11)
C11	0.0228 (16)	0.0155 (13)	0.0208 (15)	0.0008 (11)	0.0101 (12)	0.0002 (11)
C12	0.0342 (19)	0.0159 (15)	0.0325 (18)	0.0023 (14)	0.0089 (15)	−0.0040 (13)
C13	0.0328 (19)	0.0215 (16)	0.0349 (19)	−0.0038 (14)	0.0103 (15)	−0.0129 (14)
C14	0.0201 (16)	0.0307 (17)	0.0232 (17)	−0.0013 (13)	0.0047 (13)	−0.0116 (13)
C15	0.0199 (15)	0.0190 (14)	0.0204 (15)	0.0004 (12)	0.0068 (12)	−0.0009 (12)
C16	0.0220 (16)	0.0230 (15)	0.0218 (15)	0.0038 (13)	0.0102 (13)	−0.0003 (13)
C17	0.0274 (17)	0.0169 (14)	0.0144 (14)	0.0007 (12)	0.0103 (13)	0.0003 (11)

Geometric parameters (Å, º)

P1—O20	1.5337 (17)	Cu2—N4	1.995 (3)
P1—O20^i	1.5337 (17)	Cu2—N2	2.005 (2)
P1—O19	1.5373 (17)	Cu2—N3	2.006 (2)
P1—O19^i	1.5373 (17)	Cu2—N5	2.025 (2)
Mo1—O1	1.6909 (19)	Cu2—O1W	2.343 (2)
Mo1—O9	1.8874 (17)	Cu2—O4	2.7008 (19)
Mo1—O8	1.9142 (17)	O9—Mo6^i	1.8692 (18)
Mo1—O10	1.9447 (17)	O12—Mo3^i	1.9158 (18)
Mo1—O7	1.9751 (18)	O16—Mo6^i	1.9962 (18)
Mo1—O19	2.4237 (17)	O18—Mo3^i	1.9209 (18)
Mo1—Mo3	3.3874 (3)	O1W—H2W	0.93 (5)
Mo1—Mo2	3.4298 (3)	O1W—H1W	0.74 (4)
Mo2—O2	1.6891 (18)	N1—C1	1.335 (4)
Mo2—O13	1.8927 (18)	N1—C5	1.358 (4)
Mo2—O7	1.9073 (18)	N2—C6	1.336 (4)
Mo2—O12	1.9089 (18)	N2—C10	1.356 (3)
Mo2—O11	1.9167 (17)	N3—C15	1.339 (4)
Mo2—O19	2.4229 (17)	N3—C11	1.350 (3)
Mo2—Mo3	3.4090 (3)	N4—C16	1.482 (4)
Mo3—O3	1.6800 (18)	N4—H4A	0.91 (3)
Mo3—O8	1.9140 (18)	N4—H4B	0.77 (3)
Mo3—O12^i	1.9158 (18)	N5—C17	1.488 (4)
Mo3—O18^i	1.9209 (18)	N5—H5A	0.84 (3)
Mo3—O11	1.9309 (17)	N5—H5B	0.79 (3)
Mo3—O19	2.4350 (17)	C1—C2	1.381 (4)
Mo4—O4	1.6934 (18)	C1—H1	0.93 (3)
Mo4—O10	1.8427 (18)	C2—C3	1.376 (5)
Mo4—O14	1.8803 (18)	C2—H2	0.92 (4)
Mo4—O15	1.9353 (18)	C3—C4	1.361 (5)
Mo4—O16	2.0049 (17)	C3—H3	0.9300
Mo4—O20	2.4175 (17)	C4—C5	1.399 (4)
Mo4—Cu1	3.2310 (4)	C4—H4	0.92 (4)
Mo4—Mo5	3.4070 (3)	C5—C5^i	1.456 (6)
Mo4—Mo6	3.4332 (3)	C6—C7	1.372 (4)
Mo5—O5	1.6833 (18)	C6—H6	0.92 (3)
Mo5—O18	1.8710 (18)	C7—C8	1.382 (5)
Mo5—O17	1.9031 (18)	C7—H7	0.898 (18)
Mo5—O13	1.9317 (18)	C8—C9	1.381 (5)
Mo5—O14	1.9720 (18)	C8—H8	0.91 (3)
Mo5—O20	2.4472 (17)	C9—C10	1.382 (4)
Mo5—Mo6	3.3945 (3)	C9—H9	0.904 (18)
Mo6—O6	1.6768 (18)	C10—C11	1.476 (4)
Mo6—O9^i	1.8692 (18)	C11—C12	1.385 (4)
Mo6—O17	1.9152 (17)	C12—C13	1.372 (5)
Mo6—O15	1.9690 (18)	C12—H12	0.86 (3)
Mo6—O16^i	1.9962 (18)	C13—C14	1.381 (5)
Mo6—O20	2.4519 (17)	C13—H13	0.89 (3)
Mo6—Cu1	3.2085 (4)	C14—C15	1.384 (4)
Cu1—O16	1.9883 (18)	C14—H14	0.93 (3)
Cu1—O16^i	1.9883 (18)	C15—H15	0.91 (3)
Cu1—N1^i	2.003 (2)	C16—C17	1.503 (4)
Cu1—N1	2.003 (2)	C16—H16B	0.93 (3)
Cu1—O15	2.3834 (18)	C16—H16A	0.94 (3)
Cu1—O15^i	2.3835 (18)	C17—H17B	0.99 (3)
Cu1—Mo6^i	3.2085 (4)	C17—H17A	1.00 (3)
Cu1—Mo4^i	3.2310 (4)
O20—P1—O20^i	110.70 (13)	O20—Mo6—Mo5	46.08 (4)
O20—P1—O19	109.96 (9)	Cu1—Mo6—Mo5	117.369 (9)
O20^i—P1—O19	108.31 (9)	O6—Mo6—Mo4	129.44 (7)
O20—P1—O19^i	108.31 (9)	O9^i—Mo6—Mo4	127.70 (5)
O20^i—P1—O19^i	109.96 (9)	O17—Mo6—Mo4	76.84 (5)
O19—P1—O19^i	109.60 (14)	O15—Mo6—Mo4	28.17 (5)
O1—Mo1—O9	102.41 (8)	O16^i—Mo6—Mo4	81.84 (5)
O1—Mo1—O8	103.56 (8)	O20—Mo6—Mo4	44.76 (4)
O9—Mo1—O8	92.99 (7)	Cu1—Mo6—Mo4	58.100 (6)
O1—Mo1—O10	101.43 (8)	Mo5—Mo6—Mo4	59.864 (7)
O9—Mo1—O10	83.00 (7)	O16—Cu1—O16^i	92.36 (10)
O8—Mo1—O10	154.96 (8)	O16—Cu1—N1^i	174.51 (9)
O1—Mo1—O7	101.06 (8)	O16^i—Cu1—N1^i	93.11 (9)
O9—Mo1—O7	155.84 (8)	O16—Cu1—N1	93.11 (9)
O8—Mo1—O7	87.00 (7)	O16^i—Cu1—N1	174.51 (9)
O10—Mo1—O7	86.86 (7)	N1^i—Cu1—N1	81.42 (14)
O1—Mo1—O19	172.75 (7)	O16—Cu1—O15	71.55 (7)
O9—Mo1—O19	84.54 (7)	O16^i—Cu1—O15	72.52 (7)
O8—Mo1—O19	73.70 (7)	N1^i—Cu1—O15	110.61 (8)
O10—Mo1—O19	81.31 (7)	N1—Cu1—O15	108.86 (8)
O7—Mo1—O19	72.26 (6)	O16—Cu1—O15^i	72.52 (7)
O1—Mo1—Mo3	131.05 (6)	O16^i—Cu1—O15^i	71.55 (7)
O9—Mo1—Mo3	89.72 (5)	N1^i—Cu1—O15^i	108.86 (8)
O8—Mo1—Mo3	27.77 (5)	N1—Cu1—O15^i	110.61 (8)
O10—Mo1—Mo3	127.23 (5)	O15—Cu1—O15^i	127.10 (8)
O7—Mo1—Mo3	79.09 (5)	O16—Cu1—Mo6^i	36.45 (5)
O19—Mo1—Mo3	45.94 (4)	O16^i—Cu1—Mo6^i	88.34 (5)
O1—Mo1—Mo2	128.21 (6)	N1^i—Cu1—Mo6^i	143.32 (7)
O9—Mo1—Mo2	129.35 (6)	N1—Cu1—Mo6^i	96.34 (7)
O8—Mo1—Mo2	78.07 (5)	O15—Cu1—Mo6^i	104.77 (4)
O10—Mo1—Mo2	85.42 (5)	O15^i—Cu1—Mo6^i	37.72 (4)
O7—Mo1—Mo2	27.41 (5)	O16—Cu1—Mo6	88.34 (5)
O19—Mo1—Mo2	44.95 (4)	O16^i—Cu1—Mo6	36.45 (5)
Mo3—Mo1—Mo2	60.006 (7)	N1^i—Cu1—Mo6	96.34 (7)
O2—Mo2—O13	102.19 (8)	N1—Cu1—Mo6	143.32 (7)
O2—Mo2—O7	99.28 (8)	O15—Cu1—Mo6	37.72 (4)
O13—Mo2—O7	88.83 (8)	O15^i—Cu1—Mo6	104.77 (4)
O2—Mo2—O12	103.12 (8)	Mo6^i—Cu1—Mo6	105.998 (15)
O13—Mo2—O12	86.76 (8)	O16—Cu1—Mo4	36.16 (5)
O7—Mo2—O12	157.60 (7)	O16^i—Cu1—Mo4	87.47 (5)
O2—Mo2—O11	100.43 (8)	N1^i—Cu1—Mo4	144.65 (7)
O13—Mo2—O11	157.37 (7)	N1—Cu1—Mo4	96.69 (7)
O7—Mo2—O11	88.45 (8)	O15—Cu1—Mo4	36.54 (4)
O12—Mo2—O11	87.25 (8)	O15^i—Cu1—Mo4	104.82 (4)
O2—Mo2—O19	170.14 (8)	Mo6^i—Cu1—Mo4	72.023 (9)
O13—Mo2—O19	84.45 (7)	Mo6—Cu1—Mo4	64.435 (8)
O7—Mo2—O19	73.34 (7)	O16—Cu1—Mo4^i	87.47 (5)
O12—Mo2—O19	84.37 (7)	O16^i—Cu1—Mo4^i	36.16 (5)
O11—Mo2—O19	73.25 (6)	N1^i—Cu1—Mo4^i	96.69 (7)
O2—Mo2—Mo3	127.53 (6)	N1—Cu1—Mo4^i	144.65 (7)
O13—Mo2—Mo3	130.01 (5)	O15—Cu1—Mo4^i	104.82 (4)
O7—Mo2—Mo3	79.29 (5)	O15^i—Cu1—Mo4^i	36.54 (4)
O12—Mo2—Mo3	86.81 (6)	Mo6^i—Cu1—Mo4^i	64.435 (8)
O11—Mo2—Mo3	27.73 (5)	Mo6—Cu1—Mo4^i	72.023 (9)
O19—Mo2—Mo3	45.58 (4)	Mo4—Cu1—Mo4^i	104.107 (15)
O2—Mo2—Mo1	127.14 (6)	N4—Cu2—N2	175.23 (10)
O13—Mo2—Mo1	88.39 (5)	N4—Cu2—N3	94.52 (10)
O7—Mo2—Mo1	28.48 (5)	N2—Cu2—N3	81.19 (9)
O12—Mo2—Mo1	129.33 (5)	N4—Cu2—N5	84.63 (10)
O11—Mo2—Mo1	78.67 (5)	N2—Cu2—N5	99.54 (10)
O19—Mo2—Mo1	44.97 (4)	N3—Cu2—N5	176.79 (11)
Mo3—Mo2—Mo1	59.380 (7)	N4—Cu2—O1W	87.64 (11)
O3—Mo3—O8	100.29 (8)	N2—Cu2—O1W	90.34 (9)
O3—Mo3—O12^i	102.87 (8)	N3—Cu2—O1W	90.86 (9)
O8—Mo3—O12^i	156.83 (8)	N5—Cu2—O1W	86.01 (11)
O3—Mo3—O18^i	103.27 (8)	N4—Cu2—O4	105.05 (9)
O8—Mo3—O18^i	89.20 (7)	N2—Cu2—O4	77.29 (8)
O12^i—Mo3—O18^i	85.76 (8)	N3—Cu2—O4	91.80 (8)
O3—Mo3—O11	100.32 (8)	N5—Cu2—O4	91.41 (9)
O8—Mo3—O11	87.45 (8)	O1W—Cu2—O4	166.78 (8)
O12^i—Mo3—O11	88.19 (8)	Mo4—O4—Cu2	115.04 (9)
O18^i—Mo3—O11	156.39 (7)	Mo2—O7—Mo1	124.11 (9)
O3—Mo3—O19	170.58 (7)	Mo3—O8—Mo1	124.47 (10)
O8—Mo3—O19	73.43 (7)	Mo6^i—O9—Mo1	154.72 (10)
O12^i—Mo3—O19	83.55 (7)	Mo4—O10—Mo1	156.52 (10)
O18^i—Mo3—O19	83.91 (7)	Mo2—O11—Mo3	124.75 (9)
O11—Mo3—O19	72.74 (6)	Mo2—O12—Mo3^i	150.32 (10)
O3—Mo3—Mo1	127.77 (6)	Mo2—O13—Mo5	150.52 (10)
O8—Mo3—Mo1	27.77 (5)	Mo4—O14—Mo5	124.34 (9)
O12^i—Mo3—Mo1	129.16 (5)	Mo4—O15—Mo6	123.12 (9)
O18^i—Mo3—Mo1	86.57 (5)	Mo4—O15—Cu1	96.30 (7)
O11—Mo3—Mo1	79.65 (5)	Mo6—O15—Cu1	94.50 (7)
O19—Mo3—Mo1	45.66 (4)	Cu1—O16—Mo6^i	107.27 (8)
O3—Mo3—Mo2	127.34 (6)	Cu1—O16—Mo4	108.02 (8)
O8—Mo3—Mo2	78.63 (5)	Mo6^i—O16—Mo4	142.27 (9)
O12^i—Mo3—Mo2	87.11 (5)	Mo5—O17—Mo6	125.50 (9)
O18^i—Mo3—Mo2	129.18 (5)	Mo5—O18—Mo3^i	151.76 (11)
O11—Mo3—Mo2	27.51 (5)	P1—O19—Mo2	124.98 (10)
O19—Mo3—Mo2	45.29 (4)	P1—O19—Mo1	125.86 (9)
Mo1—Mo3—Mo2	60.615 (6)	Mo2—O19—Mo1	90.09 (6)
O4—Mo4—O10	102.33 (9)	P1—O19—Mo3	126.64 (9)
O4—Mo4—O14	100.98 (8)	Mo2—O19—Mo3	89.14 (6)
O10—Mo4—O14	92.87 (8)	Mo1—O19—Mo3	88.40 (6)
O4—Mo4—O15	100.67 (8)	P1—O20—Mo4	125.48 (10)
O10—Mo4—O15	156.26 (7)	P1—O20—Mo5	126.30 (9)
O14—Mo4—O15	88.42 (8)	Mo4—O20—Mo5	88.91 (6)
O4—Mo4—O16	102.40 (8)	P1—O20—Mo6	126.63 (9)
O10—Mo4—O16	87.79 (7)	Mo4—O20—Mo6	89.66 (5)
O14—Mo4—O16	155.90 (8)	Mo5—O20—Mo6	87.72 (6)
O15—Mo4—O16	81.63 (8)	Cu2—O1W—H2W	114 (3)
O4—Mo4—O20	172.98 (8)	Cu2—O1W—H1W	132 (3)
O10—Mo4—O20	83.37 (7)	H2W—O1W—H1W	114 (4)
O14—Mo4—O20	74.41 (7)	C1—N1—C5	119.1 (2)
O15—Mo4—O20	74.15 (6)	C1—N1—Cu1	126.81 (19)
O16—Mo4—O20	81.75 (7)	C5—N1—Cu1	114.0 (2)
O4—Mo4—Cu1	97.28 (6)	C6—N2—C10	118.5 (2)
O10—Mo4—Cu1	123.28 (5)	C6—N2—Cu2	128.33 (19)
O14—Mo4—Cu1	134.49 (6)	C10—N2—Cu2	113.06 (19)
O15—Mo4—Cu1	47.16 (5)	C15—N3—C11	119.3 (2)
O16—Mo4—Cu1	35.82 (5)	C15—N3—Cu2	127.12 (19)
O20—Mo4—Cu1	82.74 (4)	C11—N3—Cu2	112.01 (18)
O4—Mo4—Mo5	129.17 (6)	C16—N4—Cu2	108.92 (18)
O10—Mo4—Mo5	90.22 (5)	C16—N4—H4A	109 (2)
O14—Mo4—Mo5	28.55 (5)	Cu2—N4—H4A	111 (2)
O15—Mo4—Mo5	79.69 (5)	C16—N4—H4B	108 (2)
O16—Mo4—Mo5	127.42 (5)	Cu2—N4—H4B	110 (2)
O20—Mo4—Mo5	45.90 (4)	H4A—N4—H4B	110 (3)
Cu1—Mo4—Mo5	116.385 (8)	C17—N5—Cu2	109.52 (18)
O4—Mo4—Mo6	128.89 (7)	C17—N5—H5A	110 (2)
O10—Mo4—Mo6	128.78 (5)	Cu2—N5—H5A	113 (2)
O14—Mo4—Mo6	78.90 (6)	C17—N5—H5B	112 (2)
O15—Mo4—Mo6	28.71 (5)	Cu2—N5—H5B	114 (2)
O16—Mo4—Mo6	81.95 (5)	H5A—N5—H5B	99 (3)
O20—Mo4—Mo6	45.58 (4)	N1—C1—C2	122.2 (3)
Cu1—Mo4—Mo6	57.464 (6)	N1—C1—H1	114 (2)
Mo5—Mo4—Mo6	59.504 (7)	C2—C1—H1	123 (2)
O5—Mo5—O18	103.85 (9)	C3—C2—C1	118.9 (3)
O5—Mo5—O17	101.94 (8)	C3—C2—H2	118 (2)
O18—Mo5—O17	92.74 (8)	C1—C2—H2	123 (2)
O5—Mo5—O13	102.07 (8)	C4—C3—C2	119.7 (3)
O18—Mo5—O13	86.27 (8)	C4—C3—H3	120.1
O17—Mo5—O13	155.48 (7)	C2—C3—H3	120.1
O5—Mo5—O14	99.48 (8)	C3—C4—C5	119.5 (3)
O18—Mo5—O14	156.42 (7)	C3—C4—H4	123 (2)
O17—Mo5—O14	85.68 (7)	C5—C4—H4	117 (2)
O13—Mo5—O14	85.59 (7)	N1—C5—C4	120.5 (3)
O5—Mo5—O20	170.65 (8)	N1—C5—C5^i	115.22 (17)
O18—Mo5—O20	84.72 (7)	C4—C5—C5^i	124.3 (2)
O17—Mo5—O20	73.53 (7)	N2—C6—C7	123.3 (3)
O13—Mo5—O20	81.99 (7)	N2—C6—H6	117 (2)
O14—Mo5—O20	72.26 (6)	C7—C6—H6	120 (2)
O5—Mo5—Mo6	129.03 (7)	C6—C7—C8	118.3 (3)
O18—Mo5—Mo6	88.91 (5)	C6—C7—H7	122 (2)
O17—Mo5—Mo6	27.35 (5)	C8—C7—H7	120 (2)
O13—Mo5—Mo6	128.18 (5)	C9—C8—C7	119.4 (3)
O14—Mo5—Mo6	78.91 (5)	C9—C8—H8	123 (2)
O20—Mo5—Mo6	46.20 (4)	C7—C8—H8	118 (2)
O5—Mo5—Mo4	126.32 (7)	C8—C9—C10	119.3 (3)
O18—Mo5—Mo4	129.82 (5)	C8—C9—H9	121 (2)
O17—Mo5—Mo4	77.67 (5)	C10—C9—H9	120 (2)
O13—Mo5—Mo4	84.19 (5)	N2—C10—C9	121.2 (3)
O14—Mo5—Mo4	27.11 (5)	N2—C10—C11	114.4 (2)
O20—Mo5—Mo4	45.19 (4)	C9—C10—C11	124.2 (3)
Mo6—Mo5—Mo4	60.632 (7)	N3—C11—C12	120.6 (3)
O6—Mo6—O9^i	102.86 (9)	N3—C11—C10	114.9 (2)
O6—Mo6—O17	104.58 (8)	C12—C11—C10	124.5 (3)
O9^i—Mo6—O17	91.40 (7)	C13—C12—C11	119.9 (3)
O6—Mo6—O15	101.53 (8)	C13—C12—H12	119 (2)
O9^i—Mo6—O15	155.30 (7)	C11—C12—H12	121 (2)
O17—Mo6—O15	86.23 (8)	C12—C13—C14	119.3 (3)
O6—Mo6—O16^i	100.94 (8)	C12—C13—H13	118 (2)
O9^i—Mo6—O16^i	89.42 (7)	C14—C13—H13	123 (2)
O17—Mo6—O16^i	153.60 (7)	C13—C14—C15	118.3 (3)
O15—Mo6—O16^i	82.15 (7)	C13—C14—H14	125.6 (18)
O6—Mo6—O20	173.92 (8)	C15—C14—H14	115.8 (19)
O9^i—Mo6—O20	82.96 (7)	N3—C15—C14	122.4 (3)
O17—Mo6—O20	73.23 (7)	N3—C15—H15	119.4 (18)
O15—Mo6—O20	72.81 (6)	C14—C15—H15	118.2 (18)
O16^i—Mo6—O20	80.69 (7)	N4—C16—C17	108.3 (2)
O6—Mo6—Cu1	95.13 (6)	N4—C16—H16B	105.1 (18)
O9^i—Mo6—Cu1	125.42 (5)	C17—C16—H16B	112.9 (19)
O17—Mo6—Cu1	133.02 (5)	N4—C16—H16A	112.1 (17)
O15—Mo6—Cu1	47.78 (5)	C17—C16—H16A	110.4 (17)
O16^i—Mo6—Cu1	36.28 (5)	H16B—C16—H16A	108 (3)
O20—Mo6—Cu1	82.71 (4)	N5—C17—C16	108.5 (2)
O6—Mo6—Mo5	131.63 (6)	N5—C17—H17B	111.7 (17)
O9^i—Mo6—Mo5	87.09 (5)	C16—C17—H17B	108.3 (17)
O17—Mo6—Mo5	27.16 (5)	N5—C17—H17A	106.6 (17)
O15—Mo6—Mo5	79.63 (5)	C16—C17—H17A	108.8 (17)
O16^i—Mo6—Mo5	126.69 (5)	H17B—C17—H17A	113 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O3^ii	0.77 (3)	2.58 (3)	3.059 (3)	122 (3)
N4—H4B···O8^ii	0.77 (3)	2.50 (4)	3.262 (3)	171 (3)
N4—H4A···O14	0.91 (3)	2.43 (3)	3.102 (3)	131 (3)
N4—H4A···O17	0.91 (3)	2.57 (4)	3.445 (3)	161 (3)
N5—H5A···O7^iii	0.84 (3)	2.26 (4)	3.070 (3)	162 (3)
O1W—H1W···O1^ii	0.74 (4)	2.02 (5)	2.747 (3)	171 (5)
O1W—H2W···O7^iii	0.93 (5)	1.89 (5)	2.800 (3)	166 (4)

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