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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).
Supporting information
CCDC reference: 1910111
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).
Crystal data top
{[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) Å3 | 0.36 × 0.27 × 0.21 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0198P)2 + 10.7248P] where P = (Fo2 + 2Fc2)/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 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. |
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
P1—O20 | 1.5337 (17) | Cu2—N4 | 1.995 (3) |
P1—O20i | 1.5337 (17) | Cu2—N2 | 2.005 (2) |
P1—O19 | 1.5373 (17) | Cu2—N3 | 2.006 (2) |
P1—O19i | 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—Mo6i | 1.8692 (18) |
Mo1—O10 | 1.9447 (17) | O12—Mo3i | 1.9158 (18) |
Mo1—O7 | 1.9751 (18) | O16—Mo6i | 1.9962 (18) |
Mo1—O19 | 2.4237 (17) | O18—Mo3i | 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—O12i | 1.9158 (18) | N5—C17 | 1.488 (4) |
Mo3—O18i | 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—C5i | 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—O9i | 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—O16i | 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—O16i | 1.9883 (18) | C15—H15 | 0.91 (3) |
Cu1—N1i | 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—O15i | 2.3835 (18) | C17—H17B | 0.99 (3) |
Cu1—Mo6i | 3.2085 (4) | C17—H17A | 1.00 (3) |
Cu1—Mo4i | 3.2310 (4) | | |
| | | |
O20—P1—O20i | 110.70 (13) | O20—Mo6—Mo5 | 46.08 (4) |
O20—P1—O19 | 109.96 (9) | Cu1—Mo6—Mo5 | 117.369 (9) |
O20i—P1—O19 | 108.31 (9) | O6—Mo6—Mo4 | 129.44 (7) |
O20—P1—O19i | 108.31 (9) | O9i—Mo6—Mo4 | 127.70 (5) |
O20i—P1—O19i | 109.96 (9) | O17—Mo6—Mo4 | 76.84 (5) |
O19—P1—O19i | 109.60 (14) | O15—Mo6—Mo4 | 28.17 (5) |
O1—Mo1—O9 | 102.41 (8) | O16i—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—O16i | 92.36 (10) |
O8—Mo1—O10 | 154.96 (8) | O16—Cu1—N1i | 174.51 (9) |
O1—Mo1—O7 | 101.06 (8) | O16i—Cu1—N1i | 93.11 (9) |
O9—Mo1—O7 | 155.84 (8) | O16—Cu1—N1 | 93.11 (9) |
O8—Mo1—O7 | 87.00 (7) | O16i—Cu1—N1 | 174.51 (9) |
O10—Mo1—O7 | 86.86 (7) | N1i—Cu1—N1 | 81.42 (14) |
O1—Mo1—O19 | 172.75 (7) | O16—Cu1—O15 | 71.55 (7) |
O9—Mo1—O19 | 84.54 (7) | O16i—Cu1—O15 | 72.52 (7) |
O8—Mo1—O19 | 73.70 (7) | N1i—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—O15i | 72.52 (7) |
O1—Mo1—Mo3 | 131.05 (6) | O16i—Cu1—O15i | 71.55 (7) |
O9—Mo1—Mo3 | 89.72 (5) | N1i—Cu1—O15i | 108.86 (8) |
O8—Mo1—Mo3 | 27.77 (5) | N1—Cu1—O15i | 110.61 (8) |
O10—Mo1—Mo3 | 127.23 (5) | O15—Cu1—O15i | 127.10 (8) |
O7—Mo1—Mo3 | 79.09 (5) | O16—Cu1—Mo6i | 36.45 (5) |
O19—Mo1—Mo3 | 45.94 (4) | O16i—Cu1—Mo6i | 88.34 (5) |
O1—Mo1—Mo2 | 128.21 (6) | N1i—Cu1—Mo6i | 143.32 (7) |
O9—Mo1—Mo2 | 129.35 (6) | N1—Cu1—Mo6i | 96.34 (7) |
O8—Mo1—Mo2 | 78.07 (5) | O15—Cu1—Mo6i | 104.77 (4) |
O10—Mo1—Mo2 | 85.42 (5) | O15i—Cu1—Mo6i | 37.72 (4) |
O7—Mo1—Mo2 | 27.41 (5) | O16—Cu1—Mo6 | 88.34 (5) |
O19—Mo1—Mo2 | 44.95 (4) | O16i—Cu1—Mo6 | 36.45 (5) |
Mo3—Mo1—Mo2 | 60.006 (7) | N1i—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) | O15i—Cu1—Mo6 | 104.77 (4) |
O2—Mo2—O12 | 103.12 (8) | Mo6i—Cu1—Mo6 | 105.998 (15) |
O13—Mo2—O12 | 86.76 (8) | O16—Cu1—Mo4 | 36.16 (5) |
O7—Mo2—O12 | 157.60 (7) | O16i—Cu1—Mo4 | 87.47 (5) |
O2—Mo2—O11 | 100.43 (8) | N1i—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) | O15i—Cu1—Mo4 | 104.82 (4) |
O2—Mo2—O19 | 170.14 (8) | Mo6i—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—Mo4i | 87.47 (5) |
O12—Mo2—O19 | 84.37 (7) | O16i—Cu1—Mo4i | 36.16 (5) |
O11—Mo2—O19 | 73.25 (6) | N1i—Cu1—Mo4i | 96.69 (7) |
O2—Mo2—Mo3 | 127.53 (6) | N1—Cu1—Mo4i | 144.65 (7) |
O13—Mo2—Mo3 | 130.01 (5) | O15—Cu1—Mo4i | 104.82 (4) |
O7—Mo2—Mo3 | 79.29 (5) | O15i—Cu1—Mo4i | 36.54 (4) |
O12—Mo2—Mo3 | 86.81 (6) | Mo6i—Cu1—Mo4i | 64.435 (8) |
O11—Mo2—Mo3 | 27.73 (5) | Mo6—Cu1—Mo4i | 72.023 (9) |
O19—Mo2—Mo3 | 45.58 (4) | Mo4—Cu1—Mo4i | 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—O12i | 102.87 (8) | N3—Cu2—O1W | 90.86 (9) |
O8—Mo3—O12i | 156.83 (8) | N5—Cu2—O1W | 86.01 (11) |
O3—Mo3—O18i | 103.27 (8) | N4—Cu2—O4 | 105.05 (9) |
O8—Mo3—O18i | 89.20 (7) | N2—Cu2—O4 | 77.29 (8) |
O12i—Mo3—O18i | 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) |
O12i—Mo3—O11 | 88.19 (8) | Mo4—O4—Cu2 | 115.04 (9) |
O18i—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) | Mo6i—O9—Mo1 | 154.72 (10) |
O12i—Mo3—O19 | 83.55 (7) | Mo4—O10—Mo1 | 156.52 (10) |
O18i—Mo3—O19 | 83.91 (7) | Mo2—O11—Mo3 | 124.75 (9) |
O11—Mo3—O19 | 72.74 (6) | Mo2—O12—Mo3i | 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) |
O12i—Mo3—Mo1 | 129.16 (5) | Mo4—O15—Mo6 | 123.12 (9) |
O18i—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—Mo6i | 107.27 (8) |
O3—Mo3—Mo2 | 127.34 (6) | Cu1—O16—Mo4 | 108.02 (8) |
O8—Mo3—Mo2 | 78.63 (5) | Mo6i—O16—Mo4 | 142.27 (9) |
O12i—Mo3—Mo2 | 87.11 (5) | Mo5—O17—Mo6 | 125.50 (9) |
O18i—Mo3—Mo2 | 129.18 (5) | Mo5—O18—Mo3i | 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—C5i | 115.22 (17) |
O18—Mo5—O20 | 84.72 (7) | C4—C5—C5i | 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—O9i | 102.86 (9) | N3—C11—C10 | 114.9 (2) |
O6—Mo6—O17 | 104.58 (8) | C12—C11—C10 | 124.5 (3) |
O9i—Mo6—O17 | 91.40 (7) | C13—C12—C11 | 119.9 (3) |
O6—Mo6—O15 | 101.53 (8) | C13—C12—H12 | 119 (2) |
O9i—Mo6—O15 | 155.30 (7) | C11—C12—H12 | 121 (2) |
O17—Mo6—O15 | 86.23 (8) | C12—C13—C14 | 119.3 (3) |
O6—Mo6—O16i | 100.94 (8) | C12—C13—H13 | 118 (2) |
O9i—Mo6—O16i | 89.42 (7) | C14—C13—H13 | 123 (2) |
O17—Mo6—O16i | 153.60 (7) | C13—C14—C15 | 118.3 (3) |
O15—Mo6—O16i | 82.15 (7) | C13—C14—H14 | 125.6 (18) |
O6—Mo6—O20 | 173.92 (8) | C15—C14—H14 | 115.8 (19) |
O9i—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) |
O16i—Mo6—O20 | 80.69 (7) | N4—C16—C17 | 108.3 (2) |
O6—Mo6—Cu1 | 95.13 (6) | N4—C16—H16B | 105.1 (18) |
O9i—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) |
O16i—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) |
O9i—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) |
O16i—Mo6—Mo5 | 126.69 (5) | H17B—C17—H17A | 113 (2) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···O3ii | 0.77 (3) | 2.58 (3) | 3.059 (3) | 122 (3) |
N4—H4B···O8ii | 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···O7iii | 0.84 (3) | 2.26 (4) | 3.070 (3) | 162 (3) |
O1W—H1W···O1ii | 0.74 (4) | 2.02 (5) | 2.747 (3) | 171 (5) |
O1W—H2W···O7iii | 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. |
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