Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113011554/yf3031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113011554/yf3031Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113011554/yf3031IIsup3.hkl |
CCDC references: 950422; 950423
For the snthesis of (I) and (II), mixtures of (NH4)6Mo7O24.4H2O (0.2 g), Cu(OAc)2.2H2O (0.10 g), BIM (0.10 g) and H2O (10 ml) were stirred at room temperature, and the pH was adjusted to 1 [for (I)] or 5 [for (II)] using H3PO4 solution. The mixtures were then heated in 15 ml Teflon-lined reaction vessels at 453 K for 5 d. After the mixtures had been cooled at room temperature, black block-shaped crystals of (I) and (II) were isolated and washed with water.
All H atoms were positioned geometrically and treated as riding on their parent atoms, with alkyl C—H = 0.97 Å, aryl C—H = 0.93 Å, N—H = 0.86 Å and O—H = 0.85 Å, and with Uiso(H) = 1.2Ueq(C,N, O). According to the BVS results for (II), the BIM ligands are partly protonated, and therefore the occupancy of atom H4 attached to atom N4 was fixed at 0.5. Because of the higher Ueq parameters of some atoms compared with their neighbours, the soft-restraint commands SIMU and DELU (SHELXL97; Sheldrick, 2008) were used intensively.
For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
(C10H16N4)3[PMo12O40]2 | Z = 1 |
Mr = 4221.30 | F(000) = 1990 |
Triclinic, P1 | Dx = 3.114 Mg m−3 |
a = 11.838 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.1071 (11) Å | Cell parameters from 7806 reflections |
c = 17.8029 (18) Å | θ = 1.8–25.0° |
α = 74.134 (2)° | µ = 3.38 mm−1 |
β = 71.044 (1)° | T = 298 K |
γ = 71.872 (1)° | Block, black |
V = 2250.9 (4) Å3 | 0.20 × 0.10 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 7806 independent reflections |
Radiation source: fine-focus sealed tube | 5770 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −13→14 |
Tmin = 0.552, Tmax = 0.729 | k = −12→14 |
11740 measured reflections | l = −12→21 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0358P)2 + 12.874P] where P = (Fo2 + 2Fc2)/3 |
7806 reflections | (Δ/σ)max = 0.001 |
667 parameters | Δρmax = 1.71 e Å−3 |
380 restraints | Δρmin = −1.38 e Å−3 |
(C10H16N4)3[PMo12O40]2 | γ = 71.872 (1)° |
Mr = 4221.30 | V = 2250.9 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.838 (1) Å | Mo Kα radiation |
b = 12.1071 (11) Å | µ = 3.38 mm−1 |
c = 17.8029 (18) Å | T = 298 K |
α = 74.134 (2)° | 0.20 × 0.10 × 0.10 mm |
β = 71.044 (1)° |
Bruker SMART CCD area-detector diffractometer | 7806 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 5770 reflections with I > 2σ(I) |
Tmin = 0.552, Tmax = 0.729 | Rint = 0.021 |
11740 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 380 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0358P)2 + 12.874P] where P = (Fo2 + 2Fc2)/3 |
7806 reflections | Δρmax = 1.71 e Å−3 |
667 parameters | Δρmin = −1.38 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement 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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
Mo1 | 0.99424 (7) | 0.42510 (6) | 0.34239 (4) | 0.03161 (18) | |
Mo2 | 0.74375 (6) | 0.64312 (7) | 0.45053 (4) | 0.03106 (18) | |
Mo3 | 1.05567 (7) | 0.69686 (6) | 0.35901 (4) | 0.03089 (18) | |
Mo4 | 0.56804 (6) | 0.65669 (6) | 0.32704 (4) | 0.02652 (17) | |
Mo5 | 0.62298 (6) | 0.90948 (6) | 0.34163 (5) | 0.03151 (18) | |
Mo6 | 0.93257 (7) | 0.96349 (6) | 0.25275 (5) | 0.03079 (18) | |
Mo7 | 1.16548 (6) | 0.76336 (7) | 0.15366 (4) | 0.03072 (18) | |
Mo8 | 1.10781 (7) | 0.48781 (6) | 0.13666 (4) | 0.03321 (19) | |
Mo9 | 0.82205 (6) | 0.43561 (6) | 0.21860 (5) | 0.03061 (18) | |
Mo10 | 0.74417 (8) | 0.98154 (6) | 0.11731 (5) | 0.0373 (2) | |
Mo11 | 0.68863 (6) | 0.72772 (6) | 0.10527 (4) | 0.02799 (17) | |
Mo12 | 0.97741 (7) | 0.77721 (7) | 0.02113 (4) | 0.03281 (18) | |
P1 | 0.86781 (16) | 0.70541 (15) | 0.23596 (10) | 0.0149 (4) | |
O1 | 1.0496 (6) | 0.3056 (5) | 0.4063 (3) | 0.0419 (15) | |
O2 | 0.7157 (5) | 0.5948 (5) | 0.5516 (3) | 0.0409 (15) | |
O3 | 1.1316 (5) | 0.6669 (5) | 0.4298 (3) | 0.0403 (15) | |
O4 | 0.8485 (5) | 0.5011 (4) | 0.4099 (3) | 0.0271 (12) | |
O5 | 0.8912 (5) | 0.6906 (4) | 0.4230 (3) | 0.0267 (12) | |
O6 | 1.0691 (5) | 0.5392 (4) | 0.3461 (3) | 0.0286 (12) | |
O7 | 1.1179 (4) | 0.3966 (4) | 0.2410 (3) | 0.0281 (12) | |
O8 | 0.8959 (5) | 0.3584 (4) | 0.3044 (3) | 0.0269 (12) | |
O9 | 0.6108 (5) | 0.6035 (5) | 0.4286 (3) | 0.0281 (12) | |
O10 | 0.6507 (5) | 0.8014 (4) | 0.4424 (3) | 0.0278 (12) | |
O11 | 1.0046 (5) | 0.8644 (5) | 0.3407 (3) | 0.0279 (12) | |
O12 | 1.1867 (5) | 0.7076 (5) | 0.2621 (3) | 0.0291 (12) | |
O13 | 0.4329 (5) | 0.6182 (5) | 0.3540 (3) | 0.0382 (14) | |
O14 | 0.5197 (5) | 1.0261 (5) | 0.3787 (4) | 0.0406 (15) | |
O15 | 0.9345 (5) | 1.0963 (5) | 0.2628 (4) | 0.0386 (14) | |
O16 | 1.3084 (5) | 0.7744 (5) | 0.1012 (3) | 0.0397 (15) | |
O17 | 1.2303 (5) | 0.4102 (5) | 0.0776 (4) | 0.0431 (16) | |
O18 | 0.7650 (5) | 0.3316 (5) | 0.2090 (4) | 0.0376 (14) | |
O19 | 0.5142 (5) | 0.8143 (4) | 0.3482 (3) | 0.0284 (12) | |
O20 | 0.7745 (5) | 0.9451 (4) | 0.3254 (3) | 0.0277 (12) | |
O21 | 1.0921 (5) | 0.9171 (4) | 0.1821 (3) | 0.0280 (12) | |
O22 | 1.1733 (4) | 0.6031 (4) | 0.1520 (3) | 0.0275 (12) | |
O23 | 0.9823 (5) | 0.4118 (4) | 0.1450 (3) | 0.0270 (12) | |
O24 | 0.6823 (5) | 0.5198 (4) | 0.2914 (3) | 0.0263 (12) | |
O25 | 0.7518 (4) | 0.7213 (4) | 0.3077 (3) | 0.0204 (11) | |
O26 | 0.9628 (4) | 0.7576 (4) | 0.2464 (3) | 0.0214 (11) | |
O27 | 0.9224 (4) | 0.5739 (4) | 0.2342 (3) | 0.0190 (11) | |
O28 | 0.8332 (4) | 0.7691 (4) | 0.1564 (3) | 0.0209 (11) | |
O29 | 0.5878 (5) | 0.7231 (4) | 0.2138 (3) | 0.0265 (12) | |
O30 | 0.6407 (5) | 0.9587 (4) | 0.2306 (3) | 0.0290 (12) | |
O31 | 0.8572 (5) | 0.9953 (4) | 0.1699 (3) | 0.0297 (12) | |
O32 | 1.0799 (5) | 0.8073 (4) | 0.0729 (3) | 0.0284 (12) | |
O33 | 1.0393 (5) | 0.6159 (5) | 0.0595 (3) | 0.0291 (12) | |
O34 | 0.7649 (4) | 0.5693 (4) | 0.1366 (3) | 0.0249 (12) | |
O35 | 0.6516 (5) | 0.9002 (5) | 0.0926 (3) | 0.0300 (12) | |
O36 | 0.8311 (5) | 0.7477 (4) | 0.0148 (3) | 0.0266 (12) | |
O37 | 0.8755 (5) | 0.9390 (4) | 0.0286 (3) | 0.0310 (13) | |
O38 | 0.6810 (6) | 1.1233 (5) | 0.0829 (4) | 0.0503 (17) | |
O39 | 0.5914 (5) | 0.7204 (5) | 0.0570 (3) | 0.0358 (14) | |
O40 | 1.0544 (6) | 0.7971 (5) | −0.0765 (3) | 0.0417 (15) | |
C1 | 0.7966 (11) | −0.1365 (10) | 0.8169 (7) | 0.0649 (8) | |
H1 | 0.8655 | −0.1987 | 0.8061 | 0.078* | |
C2 | 0.6440 (11) | −0.0096 (10) | 0.8797 (7) | 0.0652 (8) | |
H2 | 0.5923 | 0.0311 | 0.9205 | 0.078* | |
C3 | 0.6361 (11) | 0.0099 (10) | 0.8046 (7) | 0.0649 (8) | |
H3 | 0.5751 | 0.0655 | 0.7826 | 0.078* | |
C4 | 0.7471 (11) | −0.0891 (10) | 0.6875 (6) | 0.0650 (8) | |
H4A | 0.8090 | −0.1625 | 0.6801 | 0.078* | |
H4B | 0.6699 | −0.0995 | 0.6861 | 0.078* | |
C5 | 0.7814 (11) | 0.0014 (10) | 0.6233 (6) | 0.0647 (8) | |
H5A | 0.8554 | 0.0156 | 0.6272 | 0.078* | |
H5B | 0.7167 | 0.0736 | 0.6289 | 0.078* | |
C6 | 0.8064 (11) | −0.0268 (10) | 0.5353 (6) | 0.0642 (8) | |
H6A | 0.8679 | −0.1010 | 0.5301 | 0.077* | |
H6B | 0.7311 | −0.0350 | 0.5292 | 0.077* | |
C7 | 0.8503 (10) | 0.0701 (9) | 0.4704 (7) | 0.0640 (8) | |
H7A | 0.9092 | 0.0946 | 0.4856 | 0.077* | |
H7B | 0.8920 | 0.0405 | 0.4205 | 0.077* | |
C8 | 0.7293 (11) | 0.2737 (10) | 0.4762 (7) | 0.0634 (8) | |
H8 | 0.7738 | 0.2909 | 0.5042 | 0.076* | |
N3 | 0.6394 (8) | 0.3464 (8) | 0.4511 (5) | 0.0633 (8) | |
H9 | 0.6120 | 0.4191 | 0.4569 | 0.076* | |
C10 | 0.6643 (10) | 0.1830 (10) | 0.4169 (7) | 0.0634 (8) | |
H10 | 0.6568 | 0.1244 | 0.3955 | 0.076* | |
C11 | 0.4566 (8) | 0.5044 (8) | 0.1934 (5) | 0.0408 (8) | |
H11 | 0.4643 | 0.5821 | 0.1753 | 0.049* | |
C12 | 0.3953 (8) | 0.3489 (8) | 0.2687 (5) | 0.0411 (8) | |
H12 | 0.3528 | 0.3002 | 0.3110 | 0.049* | |
C13 | 0.4806 (8) | 0.3160 (8) | 0.2017 (5) | 0.0410 (8) | |
H13 | 0.5093 | 0.2403 | 0.1898 | 0.049* | |
C14 | 0.6056 (8) | 0.4231 (8) | 0.0738 (5) | 0.0408 (8) | |
H14A | 0.6711 | 0.3511 | 0.0732 | 0.049* | |
H14B | 0.6422 | 0.4888 | 0.0642 | 0.049* | |
C15 | 0.5464 (8) | 0.4399 (8) | 0.0063 (5) | 0.0403 (8) | |
H15A | 0.5046 | 0.3773 | 0.0183 | 0.048* | |
H15B | 0.6106 | 0.4322 | −0.0437 | 0.048* | |
N1 | 0.7436 (8) | −0.1015 (8) | 0.8841 (6) | 0.0652 (8) | |
H1A | 0.7684 | −0.1329 | 0.9273 | 0.078* | |
N2 | 0.7331 (9) | −0.0660 (8) | 0.7660 (6) | 0.0649 (8) | |
C9 | 0.5931 (11) | 0.2943 (10) | 0.4142 (7) | 0.0634 (8) | |
H3A | 0.5264 | 0.3278 | 0.3918 | 0.076* | |
N4 | 0.7497 (9) | 0.1715 (8) | 0.4570 (5) | 0.0634 (8) | |
N5 | 0.3835 (7) | 0.4630 (6) | 0.2631 (4) | 0.0410 (8) | |
H5 | 0.3358 | 0.5041 | 0.2990 | 0.049* | |
N6 | 0.5164 (7) | 0.4159 (6) | 0.1545 (4) | 0.0405 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.0437 (4) | 0.0206 (4) | 0.0280 (4) | 0.0012 (3) | −0.0149 (3) | −0.0046 (3) |
Mo2 | 0.0264 (4) | 0.0439 (4) | 0.0179 (4) | −0.0038 (3) | −0.0045 (3) | −0.0053 (3) |
Mo3 | 0.0341 (4) | 0.0364 (4) | 0.0290 (4) | −0.0130 (3) | −0.0163 (3) | −0.0021 (3) |
Mo4 | 0.0233 (4) | 0.0320 (4) | 0.0263 (4) | −0.0106 (3) | −0.0008 (3) | −0.0114 (3) |
Mo5 | 0.0286 (4) | 0.0239 (4) | 0.0392 (4) | −0.0023 (3) | −0.0013 (3) | −0.0155 (3) |
Mo6 | 0.0337 (4) | 0.0215 (4) | 0.0431 (4) | −0.0074 (3) | −0.0125 (3) | −0.0118 (3) |
Mo7 | 0.0237 (4) | 0.0417 (4) | 0.0315 (4) | −0.0134 (3) | −0.0009 (3) | −0.0159 (3) |
Mo8 | 0.0324 (4) | 0.0239 (4) | 0.0336 (4) | −0.0061 (3) | 0.0094 (3) | −0.0126 (3) |
Mo9 | 0.0289 (4) | 0.0218 (4) | 0.0463 (5) | −0.0047 (3) | −0.0115 (3) | −0.0144 (3) |
Mo10 | 0.0632 (5) | 0.0181 (4) | 0.0352 (4) | −0.0017 (3) | −0.0270 (4) | −0.0048 (3) |
Mo11 | 0.0322 (4) | 0.0337 (4) | 0.0238 (4) | −0.0144 (3) | −0.0123 (3) | −0.0013 (3) |
Mo12 | 0.0307 (4) | 0.0466 (5) | 0.0194 (4) | −0.0145 (3) | −0.0043 (3) | −0.0006 (3) |
P1 | 0.0168 (9) | 0.0129 (9) | 0.0147 (9) | −0.0028 (7) | −0.0040 (7) | −0.0034 (7) |
O1 | 0.059 (4) | 0.025 (3) | 0.035 (3) | 0.008 (3) | −0.022 (3) | −0.005 (3) |
O2 | 0.040 (4) | 0.055 (4) | 0.023 (3) | −0.008 (3) | −0.008 (3) | −0.004 (3) |
O3 | 0.040 (3) | 0.053 (4) | 0.037 (3) | −0.012 (3) | −0.024 (3) | −0.006 (3) |
O4 | 0.035 (3) | 0.025 (3) | 0.022 (3) | −0.006 (2) | −0.007 (2) | −0.006 (2) |
O5 | 0.033 (3) | 0.028 (3) | 0.021 (3) | −0.006 (2) | −0.008 (2) | −0.008 (2) |
O6 | 0.031 (3) | 0.024 (3) | 0.031 (3) | −0.002 (2) | −0.013 (2) | −0.005 (2) |
O7 | 0.021 (3) | 0.026 (3) | 0.035 (3) | 0.002 (2) | −0.007 (2) | −0.012 (2) |
O8 | 0.036 (3) | 0.018 (3) | 0.026 (3) | −0.007 (2) | −0.006 (2) | −0.004 (2) |
O9 | 0.031 (3) | 0.031 (3) | 0.019 (3) | −0.009 (2) | −0.002 (2) | −0.005 (2) |
O10 | 0.028 (3) | 0.029 (3) | 0.025 (3) | −0.001 (2) | −0.005 (2) | −0.012 (2) |
O11 | 0.030 (3) | 0.035 (3) | 0.025 (3) | −0.011 (2) | −0.008 (2) | −0.011 (2) |
O12 | 0.026 (3) | 0.033 (3) | 0.031 (3) | −0.005 (2) | −0.011 (2) | −0.009 (3) |
O13 | 0.030 (3) | 0.052 (4) | 0.040 (3) | −0.017 (3) | 0.000 (3) | −0.022 (3) |
O14 | 0.037 (3) | 0.032 (3) | 0.052 (4) | −0.002 (3) | −0.007 (3) | −0.021 (3) |
O15 | 0.040 (3) | 0.026 (3) | 0.058 (4) | −0.009 (3) | −0.013 (3) | −0.018 (3) |
O16 | 0.029 (3) | 0.056 (4) | 0.040 (3) | −0.019 (3) | 0.001 (3) | −0.019 (3) |
O17 | 0.036 (3) | 0.037 (3) | 0.047 (4) | −0.011 (3) | 0.015 (3) | −0.023 (3) |
O18 | 0.040 (3) | 0.028 (3) | 0.048 (4) | −0.013 (3) | −0.008 (3) | −0.011 (3) |
O19 | 0.025 (3) | 0.029 (3) | 0.033 (3) | −0.004 (2) | −0.005 (2) | −0.014 (3) |
O20 | 0.029 (3) | 0.027 (3) | 0.030 (3) | −0.006 (2) | −0.005 (2) | −0.015 (2) |
O21 | 0.033 (3) | 0.028 (3) | 0.025 (3) | −0.012 (2) | −0.002 (2) | −0.010 (2) |
O22 | 0.024 (3) | 0.027 (3) | 0.033 (3) | −0.007 (2) | −0.003 (2) | −0.012 (2) |
O23 | 0.029 (3) | 0.024 (3) | 0.028 (3) | −0.005 (2) | −0.001 (2) | −0.013 (2) |
O24 | 0.030 (3) | 0.025 (3) | 0.024 (3) | −0.009 (2) | −0.001 (2) | −0.009 (2) |
O25 | 0.023 (3) | 0.022 (3) | 0.016 (3) | −0.003 (2) | −0.005 (2) | −0.006 (2) |
O26 | 0.022 (3) | 0.017 (3) | 0.026 (3) | −0.004 (2) | −0.007 (2) | −0.006 (2) |
O27 | 0.021 (3) | 0.017 (2) | 0.020 (3) | −0.007 (2) | −0.004 (2) | −0.003 (2) |
O28 | 0.027 (3) | 0.018 (3) | 0.019 (3) | −0.005 (2) | −0.008 (2) | −0.004 (2) |
O29 | 0.028 (3) | 0.031 (3) | 0.024 (3) | −0.005 (2) | −0.009 (2) | −0.010 (2) |
O30 | 0.030 (3) | 0.028 (3) | 0.032 (3) | −0.004 (2) | −0.012 (2) | −0.009 (2) |
O31 | 0.039 (3) | 0.027 (3) | 0.024 (3) | −0.009 (2) | −0.008 (2) | −0.004 (2) |
O32 | 0.032 (3) | 0.028 (3) | 0.026 (3) | −0.011 (2) | −0.003 (2) | −0.008 (2) |
O33 | 0.032 (3) | 0.031 (3) | 0.026 (3) | −0.010 (2) | −0.005 (2) | −0.011 (2) |
O34 | 0.028 (3) | 0.029 (3) | 0.021 (3) | −0.009 (2) | −0.003 (2) | −0.009 (2) |
O35 | 0.035 (3) | 0.028 (3) | 0.031 (3) | −0.003 (2) | −0.020 (3) | −0.003 (2) |
O36 | 0.035 (3) | 0.032 (3) | 0.017 (3) | −0.012 (2) | −0.007 (2) | −0.006 (2) |
O37 | 0.043 (3) | 0.022 (3) | 0.028 (3) | −0.009 (2) | −0.011 (3) | 0.000 (2) |
O38 | 0.081 (5) | 0.025 (3) | 0.045 (4) | −0.001 (3) | −0.033 (4) | −0.002 (3) |
O39 | 0.037 (3) | 0.047 (4) | 0.030 (3) | −0.016 (3) | −0.014 (3) | −0.007 (3) |
O40 | 0.048 (4) | 0.050 (4) | 0.025 (3) | −0.023 (3) | −0.001 (3) | −0.001 (3) |
C1 | 0.0721 (19) | 0.0580 (17) | 0.0616 (17) | −0.0053 (14) | −0.0288 (15) | −0.0052 (15) |
C2 | 0.0722 (19) | 0.0583 (17) | 0.0617 (17) | −0.0053 (14) | −0.0286 (15) | −0.0050 (15) |
C3 | 0.0721 (19) | 0.0581 (17) | 0.0615 (17) | −0.0053 (14) | −0.0288 (15) | −0.0053 (15) |
C4 | 0.0723 (18) | 0.0580 (17) | 0.0616 (17) | −0.0052 (14) | −0.0285 (15) | −0.0054 (14) |
C5 | 0.0721 (18) | 0.0577 (17) | 0.0613 (17) | −0.0053 (14) | −0.0284 (15) | −0.0057 (14) |
C6 | 0.0719 (18) | 0.0574 (17) | 0.0610 (17) | −0.0055 (14) | −0.0286 (15) | −0.0061 (14) |
C7 | 0.0718 (18) | 0.0573 (17) | 0.0608 (17) | −0.0055 (14) | −0.0286 (15) | −0.0063 (14) |
C8 | 0.0715 (18) | 0.0570 (17) | 0.0605 (17) | −0.0060 (14) | −0.0288 (15) | −0.0066 (14) |
N3 | 0.0716 (19) | 0.0567 (17) | 0.0604 (17) | −0.0059 (14) | −0.0286 (15) | −0.0068 (15) |
C10 | 0.0716 (19) | 0.0569 (17) | 0.0606 (17) | −0.0060 (14) | −0.0289 (15) | −0.0068 (15) |
C11 | 0.0417 (18) | 0.0452 (19) | 0.0365 (18) | −0.0119 (15) | −0.0041 (15) | −0.0157 (15) |
C12 | 0.0418 (19) | 0.0454 (19) | 0.0367 (18) | −0.0119 (15) | −0.0038 (15) | −0.0154 (16) |
C13 | 0.0418 (18) | 0.0453 (19) | 0.0367 (18) | −0.0119 (15) | −0.0038 (15) | −0.0155 (15) |
C14 | 0.0416 (18) | 0.0452 (19) | 0.0365 (18) | −0.0119 (15) | −0.0039 (15) | −0.0156 (16) |
C15 | 0.0414 (19) | 0.0451 (19) | 0.0363 (18) | −0.0122 (15) | −0.0042 (15) | −0.0159 (16) |
N1 | 0.0721 (19) | 0.0584 (17) | 0.0617 (17) | −0.0053 (14) | −0.0287 (15) | −0.0047 (15) |
N2 | 0.0722 (19) | 0.0580 (17) | 0.0614 (17) | −0.0053 (14) | −0.0289 (15) | −0.0054 (15) |
C9 | 0.0714 (19) | 0.0570 (17) | 0.0605 (17) | −0.0059 (14) | −0.0288 (15) | −0.0065 (15) |
N4 | 0.0715 (18) | 0.0569 (17) | 0.0605 (17) | −0.0058 (14) | −0.0288 (15) | −0.0066 (14) |
N5 | 0.0418 (18) | 0.0454 (19) | 0.0366 (18) | −0.0117 (15) | −0.0038 (15) | −0.0156 (16) |
N6 | 0.0414 (18) | 0.0451 (19) | 0.0364 (18) | −0.0120 (15) | −0.0042 (15) | −0.0157 (15) |
Mo1—O1 | 1.676 (5) | Mo11—O29 | 1.910 (5) |
Mo1—O4 | 1.881 (5) | Mo11—O36 | 1.942 (5) |
Mo1—O6 | 1.884 (5) | Mo11—O35 | 1.959 (5) |
Mo1—O7 | 1.957 (5) | Mo11—O28 | 2.409 (5) |
Mo1—O8 | 1.965 (5) | Mo12—O40 | 1.670 (5) |
Mo1—O27 | 2.427 (5) | Mo12—O33 | 1.877 (5) |
Mo2—O2 | 1.688 (5) | Mo12—O32 | 1.908 (5) |
Mo2—O5 | 1.880 (5) | Mo12—O36 | 1.917 (5) |
Mo2—O10 | 1.883 (5) | Mo12—O37 | 1.969 (5) |
Mo2—O4 | 1.947 (5) | Mo12—O28 | 2.455 (5) |
Mo2—O9 | 1.957 (5) | P1—O27 | 1.526 (5) |
Mo2—O25 | 2.441 (5) | P1—O28 | 1.534 (5) |
Mo3—O3 | 1.676 (5) | P1—O26 | 1.531 (5) |
Mo3—O11 | 1.895 (5) | P1—O25 | 1.544 (5) |
Mo3—O12 | 1.913 (5) | C1—N1 | 1.276 (13) |
Mo3—O5 | 1.923 (5) | C1—N2 | 1.317 (13) |
Mo3—O6 | 1.936 (5) | C1—H1 | 0.9300 |
Mo3—O26 | 2.426 (5) | C2—C3 | 1.320 (14) |
Mo4—O13 | 1.688 (5) | C2—N1 | 1.354 (13) |
Mo4—O24 | 1.898 (5) | C2—H2 | 0.9300 |
Mo4—O19 | 1.915 (5) | C3—N2 | 1.346 (13) |
Mo4—O29 | 1.920 (5) | C3—H3 | 0.9300 |
Mo4—O9 | 1.922 (5) | C4—C5 | 1.400 (14) |
Mo4—O25 | 2.426 (5) | C4—N2 | 1.447 (13) |
Mo5—O14 | 1.684 (5) | C4—H4A | 0.9700 |
Mo5—O30 | 1.863 (5) | C4—H4B | 0.9700 |
Mo5—O20 | 1.888 (5) | C5—C6 | 1.609 (14) |
Mo5—O19 | 1.938 (5) | C5—H5A | 0.9700 |
Mo5—O10 | 1.966 (5) | C5—H5B | 0.9700 |
Mo5—O25 | 2.423 (5) | C6—C7 | 1.493 (14) |
Mo6—O15 | 1.673 (5) | C6—H6A | 0.9700 |
Mo6—O31 | 1.857 (5) | C6—H6B | 0.9700 |
Mo6—O21 | 1.910 (5) | C7—N4 | 1.448 (13) |
Mo6—O20 | 1.938 (5) | C7—H7A | 0.9700 |
Mo6—O11 | 1.955 (5) | C7—H7B | 0.9700 |
Mo6—O26 | 2.434 (4) | C8—N3 | 1.272 (13) |
Mo7—O16 | 1.673 (5) | C8—N4 | 1.304 (13) |
Mo7—O32 | 1.890 (5) | C8—H8 | 0.9300 |
Mo7—O22 | 1.922 (5) | N3—C9 | 1.343 (13) |
Mo7—O21 | 1.923 (5) | N3—H9 | 0.8600 |
Mo7—O12 | 1.935 (5) | C10—C9 | 1.346 (14) |
Mo7—O26 | 2.440 (5) | C10—N4 | 1.369 (13) |
Mo8—O17 | 1.671 (5) | C10—H10 | 0.9300 |
Mo8—O7 | 1.905 (5) | C11—N6 | 1.320 (10) |
Mo8—O22 | 1.908 (5) | C11—N5 | 1.332 (10) |
Mo8—O23 | 1.926 (5) | C11—H11 | 0.9300 |
Mo8—O33 | 1.930 (5) | C12—N5 | 1.322 (11) |
Mo8—O27 | 2.452 (5) | C12—C13 | 1.352 (11) |
Mo9—O18 | 1.671 (5) | C12—H12 | 0.9300 |
Mo9—O8 | 1.884 (5) | C13—N6 | 1.371 (11) |
Mo9—O23 | 1.910 (5) | C13—H13 | 0.9300 |
Mo9—O24 | 1.933 (5) | C14—N6 | 1.479 (10) |
Mo9—O34 | 1.968 (5) | C14—C15 | 1.518 (12) |
Mo9—O27 | 2.449 (4) | C14—H14A | 0.9700 |
Mo10—O38 | 1.674 (6) | C14—H14B | 0.9700 |
Mo10—O37 | 1.878 (5) | C15—C15i | 1.537 (17) |
Mo10—O35 | 1.894 (5) | C15—H15A | 0.9700 |
Mo10—O31 | 1.932 (5) | C15—H15B | 0.9700 |
Mo10—O30 | 1.987 (5) | N1—H1A | 0.8600 |
Mo10—O28 | 2.453 (5) | C9—H3A | 0.9300 |
Mo11—O39 | 1.679 (5) | N5—H5 | 0.8600 |
Mo11—O34 | 1.863 (5) | ||
O1—Mo1—O4 | 102.9 (3) | O29—Mo11—O35 | 88.2 (2) |
O1—Mo1—O6 | 103.1 (3) | O36—Mo11—O35 | 84.5 (2) |
O4—Mo1—O6 | 88.2 (2) | O39—Mo11—O28 | 169.8 (2) |
O1—Mo1—O7 | 99.8 (3) | O34—Mo11—O28 | 85.04 (19) |
O4—Mo1—O7 | 157.2 (2) | O29—Mo11—O28 | 84.46 (19) |
O6—Mo1—O7 | 89.1 (2) | O36—Mo11—O28 | 72.91 (18) |
O1—Mo1—O8 | 99.8 (3) | O35—Mo11—O28 | 73.16 (18) |
O4—Mo1—O8 | 89.3 (2) | O40—Mo12—O33 | 103.4 (3) |
O6—Mo1—O8 | 156.9 (2) | O40—Mo12—O32 | 103.4 (3) |
O7—Mo1—O8 | 84.4 (2) | O33—Mo12—O32 | 86.6 (2) |
O1—Mo1—O27 | 169.9 (2) | O40—Mo12—O36 | 100.7 (3) |
O4—Mo1—O27 | 84.27 (19) | O33—Mo12—O36 | 91.5 (2) |
O6—Mo1—O27 | 84.09 (19) | O32—Mo12—O36 | 155.6 (2) |
O7—Mo1—O27 | 72.92 (18) | O40—Mo12—O37 | 100.4 (3) |
O8—Mo1—O27 | 72.85 (18) | O33—Mo12—O37 | 156.2 (2) |
O2—Mo2—O5 | 103.5 (3) | O32—Mo12—O37 | 87.3 (2) |
O2—Mo2—O10 | 102.3 (3) | O36—Mo12—O37 | 84.7 (2) |
O5—Mo2—O10 | 91.5 (2) | O40—Mo12—O28 | 170.1 (2) |
O2—Mo2—O4 | 102.0 (3) | O33—Mo12—O28 | 83.92 (19) |
O5—Mo2—O4 | 84.9 (2) | O32—Mo12—O28 | 83.44 (19) |
O10—Mo2—O4 | 155.6 (2) | O36—Mo12—O28 | 72.19 (18) |
O2—Mo2—O9 | 100.7 (2) | O37—Mo12—O28 | 72.52 (19) |
O5—Mo2—O9 | 155.3 (2) | O27—P1—O28 | 109.3 (3) |
O10—Mo2—O9 | 88.0 (2) | O27—P1—O26 | 109.4 (3) |
O4—Mo2—O9 | 85.4 (2) | O28—P1—O26 | 109.8 (3) |
O2—Mo2—O25 | 171.7 (2) | O27—P1—O25 | 109.6 (3) |
O5—Mo2—O25 | 83.68 (19) | O28—P1—O25 | 109.6 (3) |
O10—Mo2—O25 | 72.95 (18) | O26—P1—O25 | 109.1 (3) |
O4—Mo2—O25 | 82.65 (18) | Mo1—O4—Mo2 | 150.0 (3) |
O9—Mo2—O25 | 72.55 (18) | Mo2—O5—Mo3 | 153.9 (3) |
O3—Mo3—O11 | 102.1 (3) | Mo1—O6—Mo3 | 149.8 (3) |
O3—Mo3—O12 | 101.1 (3) | Mo8—O7—Mo1 | 124.8 (3) |
O11—Mo3—O12 | 89.2 (2) | Mo9—O8—Mo1 | 124.8 (3) |
O3—Mo3—O5 | 102.4 (3) | Mo4—O9—Mo2 | 124.1 (3) |
O11—Mo3—O5 | 89.1 (2) | Mo2—O10—Mo5 | 125.5 (3) |
O12—Mo3—O5 | 156.2 (2) | Mo3—O11—Mo6 | 124.9 (2) |
O3—Mo3—O6 | 101.4 (3) | Mo3—O12—Mo7 | 125.0 (3) |
O11—Mo3—O6 | 156.4 (2) | Mo4—O19—Mo5 | 124.6 (3) |
O12—Mo3—O6 | 87.4 (2) | Mo5—O20—Mo6 | 148.0 (3) |
O5—Mo3—O6 | 84.8 (2) | Mo6—O21—Mo7 | 125.4 (3) |
O3—Mo3—O26 | 172.5 (2) | Mo8—O22—Mo7 | 151.7 (3) |
O11—Mo3—O26 | 73.43 (18) | Mo9—O23—Mo8 | 125.1 (2) |
O12—Mo3—O26 | 73.14 (19) | Mo4—O24—Mo9 | 154.9 (3) |
O5—Mo3—O26 | 83.69 (19) | P1—O25—Mo5 | 125.3 (3) |
O6—Mo3—O26 | 83.29 (19) | P1—O25—Mo4 | 125.4 (3) |
O13—Mo4—O24 | 102.0 (2) | Mo5—O25—Mo4 | 89.42 (16) |
O13—Mo4—O19 | 101.4 (2) | P1—O25—Mo2 | 126.2 (3) |
O24—Mo4—O19 | 156.6 (2) | Mo5—O25—Mo2 | 89.45 (15) |
O13—Mo4—O29 | 102.6 (3) | Mo4—O25—Mo2 | 89.54 (16) |
O24—Mo4—O29 | 85.0 (2) | P1—O26—Mo3 | 126.5 (3) |
O19—Mo4—O29 | 88.7 (2) | P1—O26—Mo6 | 125.5 (3) |
O13—Mo4—O9 | 100.1 (3) | Mo3—O26—Mo6 | 89.20 (15) |
O24—Mo4—O9 | 89.1 (2) | P1—O26—Mo7 | 125.9 (3) |
O19—Mo4—O9 | 88.1 (2) | Mo3—O26—Mo7 | 89.11 (16) |
O29—Mo4—O9 | 157.3 (2) | Mo6—O26—Mo7 | 88.68 (15) |
O13—Mo4—O25 | 171.4 (2) | P1—O27—Mo1 | 125.4 (3) |
O24—Mo4—O25 | 83.84 (19) | P1—O27—Mo9 | 127.0 (3) |
O19—Mo4—O25 | 73.11 (18) | Mo1—O27—Mo9 | 88.76 (15) |
O29—Mo4—O25 | 84.14 (19) | P1—O27—Mo8 | 126.3 (3) |
O9—Mo4—O25 | 73.43 (19) | Mo1—O27—Mo8 | 89.09 (15) |
O14—Mo5—O30 | 102.5 (3) | Mo9—O27—Mo8 | 88.01 (15) |
O14—Mo5—O20 | 102.4 (2) | P1—O28—Mo11 | 125.9 (3) |
O30—Mo5—O20 | 88.2 (2) | P1—O28—Mo10 | 126.8 (3) |
O14—Mo5—O19 | 100.4 (2) | Mo11—O28—Mo10 | 89.07 (16) |
O30—Mo5—O19 | 90.4 (2) | P1—O28—Mo12 | 125.2 (3) |
O20—Mo5—O19 | 156.9 (2) | Mo11—O28—Mo12 | 89.58 (15) |
O14—Mo5—O10 | 100.6 (3) | Mo10—O28—Mo12 | 88.20 (15) |
O30—Mo5—O10 | 156.9 (2) | Mo11—O29—Mo4 | 148.8 (3) |
O20—Mo5—O10 | 87.7 (2) | Mo5—O30—Mo10 | 151.5 (3) |
O19—Mo5—O10 | 84.6 (2) | Mo6—O31—Mo10 | 156.0 (3) |
O14—Mo5—O25 | 170.2 (2) | Mo7—O32—Mo12 | 151.0 (3) |
O30—Mo5—O25 | 84.88 (19) | Mo12—O33—Mo8 | 151.9 (3) |
O20—Mo5—O25 | 84.07 (19) | Mo11—O34—Mo9 | 151.1 (3) |
O19—Mo5—O25 | 72.83 (18) | Mo10—O35—Mo11 | 124.5 (3) |
O10—Mo5—O25 | 72.09 (18) | Mo12—O36—Mo11 | 125.3 (2) |
O15—Mo6—O31 | 104.9 (3) | Mo10—O37—Mo12 | 125.2 (3) |
O15—Mo6—O21 | 101.3 (2) | N1—C1—N2 | 105.5 (10) |
O31—Mo6—O21 | 91.8 (2) | N1—C1—H1 | 127.2 |
O15—Mo6—O20 | 101.5 (2) | N2—C1—H1 | 127.2 |
O31—Mo6—O20 | 85.8 (2) | C3—C2—N1 | 104.9 (11) |
O21—Mo6—O20 | 156.9 (2) | C3—C2—H2 | 127.5 |
O15—Mo6—O11 | 99.2 (3) | N1—C2—H2 | 127.5 |
O31—Mo6—O11 | 155.7 (2) | C2—C3—N2 | 107.0 (11) |
O21—Mo6—O11 | 86.2 (2) | C2—C3—H3 | 126.5 |
O20—Mo6—O11 | 86.6 (2) | N2—C3—H3 | 126.5 |
O15—Mo6—O26 | 169.8 (2) | C5—C4—N2 | 113.3 (10) |
O31—Mo6—O26 | 83.96 (19) | C5—C4—H4A | 108.9 |
O21—Mo6—O26 | 73.11 (18) | N2—C4—H4A | 108.9 |
O20—Mo6—O26 | 83.81 (18) | C5—C4—H4B | 108.9 |
O11—Mo6—O26 | 72.31 (18) | N2—C4—H4B | 108.9 |
O16—Mo7—O32 | 103.4 (3) | H4A—C4—H4B | 107.7 |
O16—Mo7—O22 | 101.5 (2) | C4—C5—C6 | 113.9 (10) |
O32—Mo7—O22 | 85.8 (2) | C4—C5—H5A | 108.8 |
O16—Mo7—O21 | 102.0 (2) | C6—C5—H5A | 108.8 |
O32—Mo7—O21 | 90.1 (2) | C4—C5—H5B | 108.8 |
O22—Mo7—O21 | 156.5 (2) | C6—C5—H5B | 108.8 |
O16—Mo7—O12 | 100.5 (3) | H5A—C5—H5B | 107.7 |
O32—Mo7—O12 | 156.1 (2) | C7—C6—C5 | 110.6 (9) |
O22—Mo7—O12 | 87.8 (2) | C7—C6—H6A | 109.5 |
O21—Mo7—O12 | 86.7 (2) | C5—C6—H6A | 109.5 |
O16—Mo7—O26 | 171.2 (2) | C7—C6—H6B | 109.5 |
O32—Mo7—O26 | 83.93 (19) | C5—C6—H6B | 109.5 |
O22—Mo7—O26 | 83.80 (18) | H6A—C6—H6B | 108.1 |
O21—Mo7—O26 | 72.76 (18) | N4—C7—C6 | 111.8 (10) |
O12—Mo7—O26 | 72.47 (19) | N4—C7—H7A | 109.2 |
O17—Mo8—O7 | 100.9 (3) | C6—C7—H7A | 109.2 |
O17—Mo8—O22 | 102.3 (2) | N4—C7—H7B | 109.2 |
O7—Mo8—O22 | 90.8 (2) | C6—C7—H7B | 109.2 |
O17—Mo8—O23 | 101.2 (2) | H7A—C7—H7B | 107.9 |
O7—Mo8—O23 | 87.1 (2) | N3—C8—N4 | 109.9 (11) |
O22—Mo8—O23 | 156.4 (2) | N3—C8—H8 | 125.0 |
O17—Mo8—O33 | 102.8 (3) | N4—C8—H8 | 125.0 |
O7—Mo8—O33 | 156.3 (2) | C8—N3—C9 | 110.8 (10) |
O22—Mo8—O33 | 84.5 (2) | C8—N3—H9 | 124.6 |
O23—Mo8—O33 | 88.1 (2) | C9—N3—H9 | 124.6 |
O17—Mo8—O27 | 171.7 (2) | C9—C10—N4 | 107.7 (11) |
O7—Mo8—O27 | 73.15 (18) | C9—C10—H10 | 126.2 |
O22—Mo8—O27 | 83.78 (18) | N4—C10—H10 | 126.2 |
O23—Mo8—O27 | 73.15 (17) | N6—C11—N5 | 108.1 (8) |
O33—Mo8—O27 | 83.28 (19) | N6—C11—H11 | 126.0 |
O18—Mo9—O8 | 102.6 (3) | N5—C11—H11 | 126.0 |
O18—Mo9—O23 | 103.2 (2) | N5—C12—C13 | 107.6 (8) |
O8—Mo9—O23 | 88.7 (2) | N5—C12—H12 | 126.2 |
O18—Mo9—O24 | 101.4 (2) | C13—C12—H12 | 126.2 |
O8—Mo9—O24 | 90.3 (2) | C12—C13—N6 | 106.7 (8) |
O23—Mo9—O24 | 154.9 (2) | C12—C13—H13 | 126.7 |
O18—Mo9—O34 | 100.9 (2) | N6—C13—H13 | 126.7 |
O8—Mo9—O34 | 156.4 (2) | N6—C14—C15 | 112.5 (7) |
O23—Mo9—O34 | 88.5 (2) | N6—C14—H14A | 109.1 |
O24—Mo9—O34 | 82.5 (2) | C15—C14—H14A | 109.1 |
O18—Mo9—O27 | 174.8 (2) | N6—C14—H14B | 109.1 |
O8—Mo9—O27 | 73.58 (18) | C15—C14—H14B | 109.1 |
O23—Mo9—O27 | 73.47 (18) | H14A—C14—H14B | 107.8 |
O24—Mo9—O27 | 82.24 (18) | C14—C15—C15i | 113.7 (9) |
O34—Mo9—O27 | 83.11 (18) | C14—C15—H15A | 108.8 |
O38—Mo10—O37 | 103.0 (3) | C15i—C15—H15A | 108.8 |
O38—Mo10—O35 | 102.2 (3) | C14—C15—H15B | 108.8 |
O37—Mo10—O35 | 89.6 (2) | C15i—C15—H15B | 108.8 |
O38—Mo10—O31 | 102.4 (3) | H15A—C15—H15B | 107.7 |
O37—Mo10—O31 | 90.6 (2) | C1—N1—C2 | 112.4 (10) |
O35—Mo10—O31 | 154.6 (2) | C1—N1—H1A | 123.8 |
O38—Mo10—O30 | 101.0 (3) | C2—N1—H1A | 123.8 |
O37—Mo10—O30 | 155.8 (2) | C1—N2—C3 | 110.1 (10) |
O35—Mo10—O30 | 87.8 (2) | C1—N2—C4 | 123.3 (10) |
O31—Mo10—O30 | 81.7 (2) | C3—N2—C4 | 124.6 (10) |
O38—Mo10—O28 | 174.3 (2) | N3—C9—C10 | 105.0 (10) |
O37—Mo10—O28 | 73.97 (19) | N3—C9—H3A | 127.5 |
O35—Mo10—O28 | 73.11 (19) | C10—C9—H3A | 127.5 |
O31—Mo10—O28 | 82.56 (19) | C8—N4—C10 | 106.7 (10) |
O30—Mo10—O28 | 82.27 (19) | C8—N4—C7 | 125.4 (10) |
O39—Mo11—O34 | 103.1 (2) | C10—N4—C7 | 127.7 (10) |
O39—Mo11—O29 | 101.7 (2) | C12—N5—C11 | 109.6 (7) |
O34—Mo11—O29 | 87.9 (2) | C12—N5—H5 | 125.2 |
O39—Mo11—O36 | 100.6 (2) | C11—N5—H5 | 125.2 |
O34—Mo11—O36 | 91.0 (2) | C11—N6—C13 | 108.0 (7) |
O29—Mo11—O36 | 157.3 (2) | C11—N6—C14 | 126.2 (8) |
O39—Mo11—O35 | 98.7 (2) | C13—N6—C14 | 125.8 (7) |
O34—Mo11—O35 | 158.1 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···O9 | 0.86 | 2.15 | 2.952 (10) | 156 |
N1—H1A···O36ii | 0.86 | 1.98 | 2.809 (10) | 161 |
N5—H5···O2iii | 0.86 | 2.56 | 3.079 (9) | 120 |
N5—H5···O13 | 0.86 | 2.58 | 3.075 (9) | 118 |
N5—H5···O12iv | 0.86 | 2.60 | 3.147 (9) | 122 |
Symmetry codes: (ii) x, y−1, z+1; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z. |
(C10H16N4)(C10H15N4)[PMo12O40]·2H2O | Z = 1 |
Mr = 2240.80 | F(000) = 1065 |
Triclinic, P1 | Dx = 2.818 Mg m−3 |
a = 11.2350 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.7211 (13) Å | Cell parameters from 4586 reflections |
c = 11.8459 (13) Å | θ = 1.8–25.0° |
α = 102.194 (1)° | µ = 2.89 mm−1 |
β = 98.184 (1)° | T = 293 K |
γ = 115.998 (2)° | Block, black |
V = 1320.5 (2) Å3 | 0.22 × 0.22 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 4586 independent reflections |
Radiation source: fine-focus sealed tube | 3425 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −9→13 |
Tmin = 0.569, Tmax = 0.596 | k = −13→9 |
6912 measured reflections | l = −13→14 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.035P)2 + 18.6135P] where P = (Fo2 + 2Fc2)/3 |
4586 reflections | (Δ/σ)max < 0.001 |
394 parameters | Δρmax = 1.63 e Å−3 |
1285 restraints | Δρmin = −1.42 e Å−3 |
(C10H16N4)(C10H15N4)[PMo12O40]·2H2O | γ = 115.998 (2)° |
Mr = 2240.80 | V = 1320.5 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.2350 (12) Å | Mo Kα radiation |
b = 11.7211 (13) Å | µ = 2.89 mm−1 |
c = 11.8459 (13) Å | T = 293 K |
α = 102.194 (1)° | 0.22 × 0.22 × 0.20 mm |
β = 98.184 (1)° |
Bruker SMART CCD area-detector diffractometer | 4586 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 3425 reflections with I > 2σ(I) |
Tmin = 0.569, Tmax = 0.596 | Rint = 0.018 |
6912 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 1285 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.035P)2 + 18.6135P] where P = (Fo2 + 2Fc2)/3 |
4586 reflections | Δρmax = 1.63 e Å−3 |
394 parameters | Δρmin = −1.42 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mo1 | 0.46552 (9) | 0.07220 (10) | 0.22452 (8) | 0.0388 (2) | |
Mo2 | 0.71523 (9) | 0.32873 (8) | 0.48705 (8) | 0.0356 (2) | |
Mo3 | 0.40031 (9) | 0.14709 (9) | 0.73899 (7) | 0.0333 (2) | |
Mo4 | 0.14615 (8) | −0.11069 (8) | 0.48237 (7) | 0.0306 (2) | |
Mo5 | 0.35826 (9) | 0.21212 (9) | 0.45929 (8) | 0.0368 (2) | |
Mo6 | 0.24643 (8) | −0.25290 (8) | 0.23868 (7) | 0.0318 (2) | |
P1 | 0.5000 | 0.0000 | 0.5000 | 0.0218 (6) | |
O1 | 0.4647 (13) | −0.0627 (13) | 0.3634 (12) | 0.0342 (19) | 0.50 |
O2 | 0.5070 (14) | 0.1126 (13) | 0.4417 (12) | 0.0374 (17) | 0.50 |
O3 | 0.3932 (13) | 0.0373 (13) | 0.5303 (12) | 0.0355 (18) | 0.50 |
O4 | 0.3576 (13) | −0.1168 (13) | 0.4540 (11) | 0.033 (2) | 0.50 |
O5 | 0.5665 (8) | −0.0198 (8) | 0.2060 (7) | 0.0555 (16) | |
O6 | 0.4464 (8) | 0.1011 (7) | 0.0939 (6) | 0.0484 (18) | |
O7 | 0.6272 (8) | 0.2259 (8) | 0.3169 (7) | 0.0597 (16) | |
O8 | 0.3626 (8) | 0.1427 (8) | 0.2992 (7) | 0.0592 (16) | |
O9 | 0.8292 (8) | 0.2463 (8) | 0.4710 (7) | 0.0505 (16) | |
O10 | 0.8160 (8) | 0.4785 (7) | 0.4787 (7) | 0.0531 (18) | |
O11 | 0.7576 (8) | 0.3532 (8) | 0.6503 (7) | 0.0502 (15) | |
O12 | 0.5499 (8) | 0.3320 (8) | 0.4903 (7) | 0.0612 (16) | |
O13 | 0.5931 (8) | 0.2613 (8) | 0.7842 (8) | 0.0566 (17) | |
O14 | 0.3834 (8) | 0.2366 (7) | 0.6249 (7) | 0.0534 (16) | |
O15 | 0.3521 (8) | 0.2140 (8) | 0.8482 (7) | 0.056 (2) | |
O16 | 0.2255 (8) | −0.0002 (7) | 0.6413 (7) | 0.0562 (17) | |
O17 | −0.0207 (7) | −0.1652 (9) | 0.4700 (7) | 0.056 (2) | |
O18 | 0.1963 (8) | 0.0447 (7) | 0.4316 (7) | 0.0531 (15) | |
O19 | 0.1346 (8) | −0.2004 (7) | 0.3191 (6) | 0.0436 (14) | |
O20 | 0.2916 (8) | 0.3094 (7) | 0.4391 (7) | 0.0528 (18) | |
O21 | 0.1251 (7) | −0.3728 (7) | 0.1181 (6) | 0.051 (2) | |
O22 | 0.3046 (8) | −0.1015 (8) | 0.1882 (7) | 0.0540 (16) | |
O23 | 0.9842 (10) | 0.9348 (11) | 0.1883 (9) | 0.090 (3) | |
H23A | 0.9002 | 0.8984 | 0.1890 | 0.108* | |
H23B | 1.0339 | 0.9615 | 0.2595 | 0.108* | |
C1 | 0.7503 (11) | 0.5833 (12) | 0.2638 (11) | 0.052 (2) | |
H1 | 0.7573 | 0.6472 | 0.3300 | 0.063* | |
C2 | 0.8040 (12) | 0.4744 (12) | 0.1247 (10) | 0.051 (2) | |
H2 | 0.8549 | 0.4509 | 0.0785 | 0.062* | |
C3 | 0.6686 (12) | 0.4038 (12) | 0.1119 (11) | 0.055 (2) | |
H3 | 0.6078 | 0.3225 | 0.0540 | 0.066* | |
C4 | 0.4988 (12) | 0.4339 (13) | 0.2214 (11) | 0.055 (2) | |
H4A | 0.5079 | 0.4968 | 0.2944 | 0.066* | |
H4B | 0.4626 | 0.3465 | 0.2326 | 0.066* | |
C5 | 0.3995 (12) | 0.4301 (13) | 0.1194 (11) | 0.056 (2) | |
H5A | 0.3882 | 0.3649 | 0.0472 | 0.068* | |
H5B | 0.4380 | 0.5166 | 0.1062 | 0.068* | |
C6 | 0.2565 (13) | 0.3947 (13) | 0.1414 (12) | 0.065 (3) | |
H6A | 0.2684 | 0.4491 | 0.2206 | 0.077* | |
H6B | 0.2056 | 0.4153 | 0.0831 | 0.077* | |
C7 | 0.1789 (12) | 0.2564 (13) | 0.1323 (12) | 0.063 (2) | |
H7A | 0.2256 | 0.2361 | 0.1941 | 0.076* | |
H7B | 0.1702 | 0.2009 | 0.0548 | 0.076* | |
C8 | −0.0801 (13) | 0.1642 (14) | 0.0572 (12) | 0.066 (3) | |
H8 | −0.0876 | 0.1364 | −0.0242 | 0.079* | |
N4 | −0.1276 (10) | 0.2105 (11) | 0.2266 (10) | 0.063 (2) | |
H4 | −0.1729 | 0.2167 | 0.2782 | 0.075* | 0.75 |
C10 | 0.0063 (14) | 0.2593 (14) | 0.2506 (13) | 0.068 (3) | |
H10 | 0.0680 | 0.3069 | 0.3261 | 0.082* | |
N1 | 0.6357 (9) | 0.4733 (9) | 0.1997 (8) | 0.0440 (17) | |
N2 | 0.8530 (10) | 0.5886 (10) | 0.2195 (9) | 0.054 (2) | |
H2A | 0.9365 | 0.6524 | 0.2453 | 0.065* | 0.75 |
N3 | 0.0391 (10) | 0.2287 (11) | 0.1470 (10) | 0.062 (2) | |
C9 | −0.1832 (13) | 0.1480 (14) | 0.1057 (12) | 0.063 (3) | |
H9 | −0.2761 | 0.1026 | 0.0653 | 0.076* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.0353 (5) | 0.0578 (6) | 0.0267 (4) | 0.0231 (4) | 0.0091 (4) | 0.0175 (4) |
Mo2 | 0.0345 (5) | 0.0276 (4) | 0.0343 (5) | 0.0078 (4) | 0.0109 (4) | 0.0050 (4) |
Mo3 | 0.0370 (5) | 0.0371 (5) | 0.0310 (5) | 0.0226 (4) | 0.0156 (4) | 0.0053 (4) |
Mo4 | 0.0221 (4) | 0.0343 (5) | 0.0322 (4) | 0.0139 (4) | 0.0063 (3) | 0.0038 (4) |
Mo5 | 0.0384 (5) | 0.0412 (5) | 0.0383 (5) | 0.0288 (4) | 0.0075 (4) | 0.0064 (4) |
Mo6 | 0.0246 (4) | 0.0309 (5) | 0.0288 (4) | 0.0100 (4) | 0.0011 (3) | −0.0001 (3) |
P1 | 0.0234 (13) | 0.0274 (13) | 0.0218 (13) | 0.0172 (11) | 0.0100 (11) | 0.0079 (11) |
O1 | 0.031 (3) | 0.041 (3) | 0.036 (3) | 0.023 (3) | 0.011 (3) | 0.010 (3) |
O2 | 0.037 (2) | 0.042 (2) | 0.037 (3) | 0.024 (2) | 0.011 (2) | 0.010 (2) |
O3 | 0.035 (3) | 0.039 (3) | 0.035 (3) | 0.021 (2) | 0.012 (2) | 0.008 (3) |
O4 | 0.033 (3) | 0.035 (3) | 0.032 (3) | 0.019 (3) | 0.009 (3) | 0.007 (3) |
O5 | 0.041 (3) | 0.053 (3) | 0.065 (3) | 0.016 (2) | 0.008 (3) | 0.024 (3) |
O6 | 0.048 (4) | 0.052 (4) | 0.038 (4) | 0.018 (3) | 0.010 (3) | 0.018 (3) |
O7 | 0.043 (2) | 0.065 (2) | 0.049 (2) | 0.017 (2) | 0.012 (2) | −0.004 (2) |
O8 | 0.043 (2) | 0.062 (2) | 0.049 (2) | 0.015 (2) | 0.011 (2) | −0.004 (2) |
O9 | 0.061 (3) | 0.052 (3) | 0.043 (3) | 0.034 (2) | 0.012 (3) | 0.009 (3) |
O10 | 0.057 (4) | 0.039 (4) | 0.062 (4) | 0.018 (3) | 0.025 (3) | 0.017 (3) |
O11 | 0.061 (3) | 0.052 (3) | 0.041 (3) | 0.033 (2) | 0.015 (2) | 0.009 (2) |
O12 | 0.044 (2) | 0.066 (2) | 0.048 (2) | 0.016 (2) | 0.013 (2) | −0.007 (2) |
O13 | 0.042 (3) | 0.054 (3) | 0.068 (3) | 0.018 (2) | 0.009 (3) | 0.023 (3) |
O14 | 0.053 (3) | 0.043 (2) | 0.043 (2) | 0.010 (2) | 0.001 (2) | 0.011 (2) |
O15 | 0.054 (4) | 0.047 (4) | 0.049 (4) | 0.015 (3) | 0.026 (4) | −0.007 (3) |
O16 | 0.058 (3) | 0.042 (3) | 0.043 (3) | 0.007 (2) | −0.001 (2) | 0.010 (2) |
O17 | 0.028 (4) | 0.083 (5) | 0.050 (4) | 0.022 (4) | 0.011 (3) | 0.018 (4) |
O18 | 0.055 (2) | 0.043 (2) | 0.042 (2) | 0.012 (2) | 0.003 (2) | 0.010 (2) |
O19 | 0.050 (3) | 0.044 (3) | 0.038 (2) | 0.027 (2) | 0.013 (2) | 0.006 (2) |
O20 | 0.054 (4) | 0.045 (4) | 0.060 (4) | 0.032 (3) | 0.002 (3) | 0.011 (3) |
O21 | 0.038 (4) | 0.051 (4) | 0.040 (4) | 0.018 (3) | −0.008 (3) | −0.012 (3) |
O22 | 0.042 (3) | 0.052 (3) | 0.062 (3) | 0.018 (2) | 0.009 (2) | 0.020 (2) |
O23 | 0.066 (6) | 0.113 (7) | 0.076 (6) | 0.041 (5) | 0.004 (5) | 0.016 (5) |
C1 | 0.041 (4) | 0.051 (4) | 0.055 (4) | 0.020 (3) | 0.014 (3) | 0.002 (3) |
C2 | 0.043 (4) | 0.053 (4) | 0.050 (4) | 0.020 (3) | 0.017 (3) | 0.003 (4) |
C3 | 0.044 (3) | 0.053 (4) | 0.053 (4) | 0.015 (3) | 0.015 (3) | 0.002 (3) |
C4 | 0.042 (3) | 0.057 (3) | 0.053 (3) | 0.017 (3) | 0.017 (3) | 0.006 (3) |
C5 | 0.041 (3) | 0.062 (4) | 0.057 (4) | 0.018 (3) | 0.017 (3) | 0.010 (3) |
C6 | 0.046 (4) | 0.069 (4) | 0.064 (4) | 0.019 (4) | 0.017 (4) | 0.011 (4) |
C7 | 0.044 (3) | 0.070 (4) | 0.063 (4) | 0.021 (3) | 0.010 (3) | 0.013 (3) |
C8 | 0.044 (4) | 0.080 (4) | 0.059 (4) | 0.019 (4) | 0.013 (4) | 0.016 (4) |
N4 | 0.044 (4) | 0.075 (4) | 0.059 (4) | 0.022 (4) | 0.013 (3) | 0.016 (4) |
C10 | 0.048 (4) | 0.076 (4) | 0.061 (4) | 0.018 (4) | 0.009 (4) | 0.015 (4) |
N1 | 0.038 (3) | 0.045 (3) | 0.048 (3) | 0.020 (3) | 0.016 (3) | 0.010 (3) |
N2 | 0.041 (3) | 0.058 (4) | 0.054 (4) | 0.023 (3) | 0.011 (3) | 0.002 (3) |
N3 | 0.041 (3) | 0.073 (4) | 0.059 (4) | 0.018 (3) | 0.012 (3) | 0.019 (3) |
C9 | 0.040 (4) | 0.078 (5) | 0.057 (4) | 0.017 (4) | 0.011 (4) | 0.022 (4) |
Mo1—O6 | 1.657 (7) | P1—O2 | 1.592 (14) |
Mo1—O7 | 1.864 (8) | O1—O4 | 1.728 (18) |
Mo1—O5 | 1.882 (8) | O1—O3i | 1.754 (18) |
Mo1—O8 | 1.903 (8) | O1—Mo3i | 2.467 (12) |
Mo1—O22 | 1.944 (8) | O2—O4i | 1.794 (18) |
Mo1—O2 | 2.452 (13) | O2—O3 | 1.816 (19) |
Mo1—O1 | 2.510 (13) | O3—O4 | 1.677 (18) |
Mo2—O10 | 1.654 (7) | O3—O1i | 1.754 (18) |
Mo2—O11 | 1.853 (7) | O4—O2i | 1.794 (18) |
Mo2—O12 | 1.880 (8) | O5—Mo3i | 1.902 (8) |
Mo2—O9 | 1.920 (8) | O9—Mo4i | 1.903 (8) |
Mo2—O7 | 1.963 (8) | O11—Mo6i | 1.933 (8) |
Mo2—O2 | 2.460 (14) | O13—Mo6i | 1.902 (8) |
Mo3—O15 | 1.651 (7) | O23—H23A | 0.8500 |
Mo3—O13 | 1.896 (8) | O23—H23B | 0.8500 |
Mo3—O5i | 1.902 (8) | C1—N2 | 1.318 (14) |
Mo3—O14 | 1.914 (8) | C1—N1 | 1.323 (14) |
Mo3—O16 | 1.927 (8) | C1—H1 | 0.9300 |
Mo3—O1i | 2.467 (12) | C2—C3 | 1.341 (16) |
Mo3—O3 | 2.507 (13) | C2—N2 | 1.378 (14) |
Mo4—O17 | 1.666 (7) | C2—H2 | 0.9300 |
Mo4—O16 | 1.870 (7) | C3—N1 | 1.378 (14) |
Mo4—O9i | 1.903 (8) | C3—H3 | 0.9300 |
Mo4—O18 | 1.912 (8) | C4—N1 | 1.478 (14) |
Mo4—O19 | 1.953 (7) | C4—C5 | 1.502 (17) |
Mo4—O3 | 2.439 (13) | C4—H4A | 0.9700 |
Mo4—O4 | 2.475 (13) | C4—H4B | 0.9700 |
Mo5—O20 | 1.653 (7) | C5—C6 | 1.549 (16) |
Mo5—O14 | 1.883 (8) | C5—H5A | 0.9700 |
Mo5—O12 | 1.910 (8) | C5—H5B | 0.9700 |
Mo5—O8 | 1.916 (8) | C6—C7 | 1.436 (18) |
Mo5—O18 | 1.923 (8) | C6—H6A | 0.9700 |
Mo5—O2 | 2.429 (13) | C6—H6B | 0.9700 |
Mo6—O21 | 1.671 (6) | C7—N3 | 1.503 (15) |
Mo6—O22 | 1.865 (8) | C7—H7A | 0.9700 |
Mo6—O13i | 1.902 (8) | C7—H7B | 0.9700 |
Mo6—O19 | 1.906 (7) | C8—C9 | 1.323 (17) |
Mo6—O11i | 1.933 (8) | C8—N3 | 1.365 (15) |
Mo6—O1 | 2.439 (13) | C8—H8 | 0.9300 |
Mo6—O4 | 2.498 (12) | N4—C10 | 1.313 (16) |
P1—O4 | 1.499 (13) | N4—C9 | 1.370 (16) |
P1—O4i | 1.499 (13) | N4—H4 | 0.8600 |
P1—O3i | 1.508 (13) | C10—N3 | 1.353 (16) |
P1—O3 | 1.508 (13) | C10—H10 | 0.9300 |
P1—O1 | 1.541 (13) | N2—H2A | 0.8600 |
P1—O1i | 1.541 (13) | C9—H9 | 0.9300 |
P1—O2i | 1.592 (14) | ||
O6—Mo1—O7 | 101.8 (4) | O4—P1—O2 | 109.1 (7) |
O6—Mo1—O5 | 101.7 (4) | O4i—P1—O2 | 70.9 (7) |
O7—Mo1—O5 | 89.2 (4) | O3i—P1—O2 | 108.4 (7) |
O6—Mo1—O8 | 101.2 (4) | O3—P1—O2 | 71.6 (7) |
O7—Mo1—O8 | 89.4 (3) | O1—P1—O2 | 73.6 (7) |
O5—Mo1—O8 | 156.9 (4) | O1i—P1—O2 | 106.4 (7) |
O6—Mo1—O22 | 100.8 (3) | O2i—P1—O2 | 180.000 (3) |
O7—Mo1—O22 | 157.4 (4) | P1—O1—O4 | 54.2 (6) |
O5—Mo1—O22 | 86.6 (3) | P1—O1—O3i | 54.0 (6) |
O8—Mo1—O22 | 85.9 (3) | O4—O1—O3i | 91.6 (9) |
O6—Mo1—O2 | 159.0 (4) | P1—O1—Mo6 | 125.6 (7) |
O7—Mo1—O2 | 64.8 (4) | O4—O1—Mo6 | 71.3 (6) |
O5—Mo1—O2 | 94.4 (4) | O3i—O1—Mo6 | 136.4 (8) |
O8—Mo1—O2 | 64.2 (4) | P1—O1—Mo3i | 124.6 (7) |
O22—Mo1—O2 | 93.4 (4) | O4—O1—Mo3i | 134.3 (8) |
O6—Mo1—O1 | 156.5 (4) | O3i—O1—Mo3i | 70.6 (6) |
O7—Mo1—O1 | 95.9 (4) | Mo6—O1—Mo3i | 92.7 (4) |
O5—Mo1—O1 | 62.9 (4) | P1—O1—Mo1 | 120.6 (7) |
O8—Mo1—O1 | 94.3 (4) | O4—O1—Mo1 | 130.3 (8) |
O22—Mo1—O1 | 62.5 (4) | O3i—O1—Mo1 | 126.8 (8) |
O2—Mo1—O1 | 44.4 (4) | Mo6—O1—Mo1 | 92.5 (4) |
O10—Mo2—O11 | 102.7 (4) | Mo3i—O1—Mo1 | 91.7 (4) |
O10—Mo2—O12 | 102.6 (4) | P1—O2—O4i | 52.1 (6) |
O11—Mo2—O12 | 91.3 (3) | P1—O2—O3 | 52.0 (6) |
O10—Mo2—O9 | 101.5 (4) | O4i—O2—O3 | 87.5 (8) |
O11—Mo2—O9 | 88.9 (3) | P1—O2—Mo5 | 123.5 (7) |
O12—Mo2—O9 | 155.3 (4) | O4i—O2—Mo5 | 134.0 (8) |
O10—Mo2—O7 | 101.4 (4) | O3—O2—Mo5 | 71.5 (6) |
O11—Mo2—O7 | 155.7 (4) | P1—O2—Mo1 | 121.4 (7) |
O12—Mo2—O7 | 86.1 (3) | O4i—O2—Mo1 | 129.4 (8) |
O9—Mo2—O7 | 83.6 (3) | O3—O2—Mo1 | 130.7 (8) |
O10—Mo2—O2 | 158.5 (4) | Mo5—O2—Mo1 | 93.5 (5) |
O11—Mo2—O2 | 93.9 (4) | P1—O2—Mo2 | 123.5 (7) |
O12—Mo2—O2 | 63.0 (4) | O4i—O2—Mo2 | 71.3 (6) |
O9—Mo2—O2 | 92.3 (4) | O3—O2—Mo2 | 133.1 (8) |
O7—Mo2—O2 | 63.5 (4) | Mo5—O2—Mo2 | 93.6 (5) |
O15—Mo3—O13 | 102.3 (4) | Mo1—O2—Mo2 | 93.3 (5) |
O15—Mo3—O5i | 103.4 (4) | P1—O3—O4 | 55.9 (6) |
O13—Mo3—O5i | 88.2 (3) | P1—O3—O1i | 55.8 (6) |
O15—Mo3—O14 | 101.7 (4) | O4—O3—O1i | 93.6 (9) |
O13—Mo3—O14 | 88.8 (3) | P1—O3—O2 | 56.3 (6) |
O5i—Mo3—O14 | 154.8 (4) | O4—O3—O2 | 92.3 (8) |
O15—Mo3—O16 | 100.6 (4) | O1i—O3—O2 | 89.3 (8) |
O13—Mo3—O16 | 157.1 (4) | P1—O3—Mo4 | 127.1 (7) |
O5i—Mo3—O16 | 86.9 (3) | O4—O3—Mo4 | 71.2 (6) |
O14—Mo3—O16 | 86.3 (3) | O1i—O3—Mo4 | 133.8 (8) |
O15—Mo3—O1i | 159.9 (4) | O2—O3—Mo4 | 133.1 (8) |
O13—Mo3—O1i | 63.7 (4) | P1—O3—Mo3 | 123.9 (7) |
O5i—Mo3—O1i | 63.7 (4) | O4—O3—Mo3 | 134.8 (8) |
O14—Mo3—O1i | 92.7 (4) | O1i—O3—Mo3 | 68.1 (6) |
O16—Mo3—O1i | 94.2 (4) | O2—O3—Mo3 | 126.7 (8) |
O15—Mo3—O3 | 158.8 (4) | Mo4—O3—Mo3 | 91.7 (4) |
O13—Mo3—O3 | 94.1 (4) | P1—O4—O3 | 56.4 (6) |
O5i—Mo3—O3 | 90.3 (4) | P1—O4—O1 | 56.5 (6) |
O14—Mo3—O3 | 64.9 (4) | O3—O4—O1 | 94.2 (9) |
O16—Mo3—O3 | 63.6 (4) | P1—O4—O2i | 57.0 (6) |
O1i—Mo3—O3 | 41.3 (4) | O3—O4—O2i | 92.8 (9) |
O17—Mo4—O16 | 102.0 (4) | O1—O4—O2i | 90.9 (8) |
O17—Mo4—O9i | 101.5 (4) | P1—O4—Mo4 | 125.3 (7) |
O16—Mo4—O9i | 89.5 (3) | O3—O4—Mo4 | 68.9 (6) |
O17—Mo4—O18 | 101.8 (4) | O1—O4—Mo4 | 134.5 (8) |
O16—Mo4—O18 | 89.0 (3) | O2i—O4—Mo4 | 130.3 (8) |
O9i—Mo4—O18 | 156.4 (4) | P1—O4—Mo6 | 124.2 (7) |
O17—Mo4—O19 | 99.1 (3) | O3—O4—Mo6 | 132.6 (8) |
O16—Mo4—O19 | 158.9 (3) | O1—O4—Mo6 | 67.7 (6) |
O9i—Mo4—O19 | 87.5 (3) | O2i—O4—Mo6 | 129.1 (7) |
O18—Mo4—O19 | 85.5 (3) | Mo4—O4—Mo6 | 92.6 (4) |
O17—Mo4—O3 | 161.4 (4) | Mo1—O5—Mo3i | 141.3 (5) |
O16—Mo4—O3 | 65.7 (4) | Mo1—O7—Mo2 | 137.8 (5) |
O9i—Mo4—O3 | 92.5 (4) | Mo1—O8—Mo5 | 137.1 (5) |
O18—Mo4—O3 | 65.5 (4) | Mo4i—O9—Mo2 | 138.8 (4) |
O19—Mo4—O3 | 93.5 (4) | Mo2—O11—Mo6i | 140.4 (4) |
O17—Mo4—O4 | 158.6 (4) | Mo2—O12—Mo5 | 140.0 (5) |
O16—Mo4—O4 | 95.0 (4) | Mo3—O13—Mo6i | 138.4 (5) |
O9i—Mo4—O4 | 65.3 (4) | Mo5—O14—Mo3 | 139.9 (5) |
O18—Mo4—O4 | 91.4 (4) | Mo4—O16—Mo3 | 138.5 (5) |
O19—Mo4—O4 | 64.9 (4) | Mo4—O18—Mo5 | 137.7 (4) |
O3—Mo4—O4 | 39.9 (4) | Mo6—O19—Mo4 | 137.3 (4) |
O20—Mo5—O14 | 101.8 (4) | Mo6—O22—Mo1 | 139.5 (4) |
O20—Mo5—O12 | 101.3 (4) | H23A—O23—H23B | 108.7 |
O14—Mo5—O12 | 88.9 (3) | N2—C1—N1 | 109.6 (10) |
O20—Mo5—O8 | 100.7 (4) | N2—C1—H1 | 125.2 |
O14—Mo5—O8 | 157.4 (4) | N1—C1—H1 | 125.2 |
O12—Mo5—O8 | 86.8 (3) | C3—C2—N2 | 106.6 (10) |
O20—Mo5—O18 | 101.8 (4) | C3—C2—H2 | 126.7 |
O14—Mo5—O18 | 88.3 (3) | N2—C2—H2 | 126.7 |
O12—Mo5—O18 | 156.8 (4) | C2—C3—N1 | 107.8 (10) |
O8—Mo5—O18 | 87.0 (3) | C2—C3—H3 | 126.1 |
O20—Mo5—O2 | 158.1 (4) | N1—C3—H3 | 126.1 |
O14—Mo5—O2 | 93.8 (4) | N1—C4—C5 | 112.0 (10) |
O12—Mo5—O2 | 63.3 (4) | N1—C4—H4A | 109.2 |
O8—Mo5—O2 | 64.6 (4) | C5—C4—H4A | 109.2 |
O18—Mo5—O2 | 93.9 (4) | N1—C4—H4B | 109.2 |
O21—Mo6—O22 | 102.8 (4) | C5—C4—H4B | 109.2 |
O21—Mo6—O13i | 102.3 (4) | H4A—C4—H4B | 107.9 |
O22—Mo6—O13i | 89.0 (3) | C4—C5—C6 | 113.4 (10) |
O21—Mo6—O19 | 99.4 (3) | C4—C5—H5A | 108.9 |
O22—Mo6—O19 | 89.6 (3) | C6—C5—H5A | 108.9 |
O13i—Mo6—O19 | 158.0 (3) | C4—C5—H5B | 108.9 |
O21—Mo6—O11i | 100.9 (4) | C6—C5—H5B | 108.9 |
O22—Mo6—O11i | 156.2 (3) | H5A—C5—H5B | 107.7 |
O13i—Mo6—O11i | 86.5 (3) | C7—C6—C5 | 112.0 (12) |
O19—Mo6—O11i | 86.0 (3) | C7—C6—H6A | 109.2 |
O21—Mo6—O1 | 160.7 (4) | C5—C6—H6A | 109.2 |
O22—Mo6—O1 | 64.9 (4) | C7—C6—H6B | 109.2 |
O13i—Mo6—O1 | 64.2 (4) | C5—C6—H6B | 109.2 |
O19—Mo6—O1 | 95.5 (4) | H6A—C6—H6B | 107.9 |
O11i—Mo6—O1 | 92.2 (4) | C6—C7—N3 | 108.6 (11) |
O21—Mo6—O4 | 158.3 (4) | C6—C7—H7A | 110.0 |
O22—Mo6—O4 | 92.4 (4) | N3—C7—H7A | 110.0 |
O13i—Mo6—O4 | 93.2 (4) | C6—C7—H7B | 110.0 |
O19—Mo6—O4 | 64.9 (4) | N3—C7—H7B | 110.0 |
O11i—Mo6—O4 | 64.6 (4) | H7A—C7—H7B | 108.4 |
O1—Mo6—O4 | 41.0 (4) | C9—C8—N3 | 108.5 (12) |
O4—P1—O4i | 180.000 (2) | C9—C8—H8 | 125.8 |
O4—P1—O3i | 112.2 (7) | N3—C8—H8 | 125.8 |
O4i—P1—O3i | 67.8 (7) | C10—N4—C9 | 108.7 (11) |
O4—P1—O3 | 67.8 (7) | C10—N4—H4 | 125.6 |
O4i—P1—O3 | 112.2 (7) | C9—N4—H4 | 125.6 |
O3i—P1—O3 | 180.0 (10) | N4—C10—N3 | 108.5 (12) |
O4—P1—O1 | 69.3 (7) | N4—C10—H10 | 125.8 |
O4i—P1—O1 | 110.7 (7) | N3—C10—H10 | 125.8 |
O3i—P1—O1 | 70.2 (7) | C1—N1—C3 | 107.5 (9) |
O3—P1—O1 | 109.8 (7) | C1—N1—C4 | 125.2 (9) |
O4—P1—O1i | 110.7 (7) | C3—N1—C4 | 127.3 (9) |
O4i—P1—O1i | 69.3 (7) | C1—N2—C2 | 108.4 (10) |
O3i—P1—O1i | 109.8 (7) | C1—N2—H2A | 125.8 |
O3—P1—O1i | 70.2 (7) | C2—N2—H2A | 125.8 |
O1—P1—O1i | 180.000 (3) | C10—N3—C8 | 107.0 (11) |
O4—P1—O2i | 70.9 (7) | C10—N3—C7 | 127.1 (11) |
O4i—P1—O2i | 109.1 (7) | C8—N3—C7 | 125.9 (11) |
O3i—P1—O2i | 71.6 (7) | C8—C9—N4 | 107.2 (11) |
O3—P1—O2i | 108.4 (7) | C8—C9—H9 | 126.4 |
O1—P1—O2i | 106.4 (7) | N4—C9—H9 | 126.4 |
O1i—P1—O2i | 73.6 (7) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O9ii | 0.86 | 2.23 | 2.976 (13) | 145 |
N2—H2A···O19iii | 0.86 | 2.03 | 2.892 (12) | 175 |
O23—H23A···O15iv | 0.85 | 2.47 | 3.308 (13) | 170 |
O23—H23B···O18iii | 0.85 | 2.23 | 3.071 (12) | 170 |
Symmetry codes: (ii) x−1, y, z; (iii) x+1, y+1, z; (iv) −x+1, −y+1, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C10H16N4)3[PMo12O40]2 | (C10H16N4)(C10H15N4)[PMo12O40]·2H2O |
Mr | 4221.30 | 2240.80 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 298 | 293 |
a, b, c (Å) | 11.838 (1), 12.1071 (11), 17.8029 (18) | 11.2350 (12), 11.7211 (13), 11.8459 (13) |
α, β, γ (°) | 74.134 (2), 71.044 (1), 71.872 (1) | 102.194 (1), 98.184 (1), 115.998 (2) |
V (Å3) | 2250.9 (4) | 1320.5 (2) |
Z | 1 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 3.38 | 2.89 |
Crystal size (mm) | 0.20 × 0.10 × 0.10 | 0.22 × 0.22 × 0.20 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.552, 0.729 | 0.569, 0.596 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11740, 7806, 5770 | 6912, 4586, 3425 |
Rint | 0.021 | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.103, 1.06 | 0.050, 0.123, 1.04 |
No. of reflections | 7806 | 4586 |
No. of parameters | 667 | 394 |
No. of restraints | 380 | 1285 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0358P)2 + 12.874P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.035P)2 + 18.6135P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.71, −1.38 | 1.63, −1.42 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···O9 | 0.86 | 2.15 | 2.952 (10) | 155.6 |
N1—H1A···O36i | 0.86 | 1.98 | 2.809 (10) | 161.3 |
N5—H5···O2ii | 0.86 | 2.56 | 3.079 (9) | 120.1 |
N5—H5···O13 | 0.86 | 2.58 | 3.075 (9) | 117.8 |
N5—H5···O12iii | 0.86 | 2.60 | 3.147 (9) | 122.1 |
Symmetry codes: (i) x, y−1, z+1; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O9i | 0.86 | 2.23 | 2.976 (13) | 144.8 |
N2—H2A···O19ii | 0.86 | 2.03 | 2.892 (12) | 175.3 |
O23—H23A···O15iii | 0.85 | 2.47 | 3.308 (13) | 169.7 |
O23—H23B···O18ii | 0.85 | 2.23 | 3.071 (12) | 169.6 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y+1, z; (iii) −x+1, −y+1, −z+1. |
The development of new inorganic–organic hybrids has emerged as a major research area for the rational design of new materials, due to their intriguing topological structures and their widespead applications (Chae et al., 2004; Seo et al., 2000; Kahn & Martinez, 1998) as catalysts, nonlinear optical materials etc. Polyoxometalalte (POM) clusters can be viewed as transferable building blocks, offering interesting and exciting perspectives for the design of new materials. Thus, POMs are often employed as important inorganic units for constructing inorganic–organic supramolecular hybrids with various organic molecules (Ishii et al., 2004; Peng, 2004; Zhao et al., 2007; Zheng et al., 2008). Studies of supramolecular hybrids are mainly focused on the understanding of intermolecular interactions with respect to crystal packing, and the utilization of such knowledge in the design of new solids with desired physical and chemical properties (Lehn, 1990).
There are many reports on the intermolecular interactions in POM-based supramolecular hybrids. Some are focused on the recognition and development of novel supramolecular synthons (Wintijes et al., 2008; Han et al., 2009), while others explore novel lattice architectures resulting from the different nature of the organic molecules (Long et al., 2003; Yan et al., 2010; Ritchie et al., 2009; Chullikkattil et al., 2010). In our ongoing studies of POM-based supramolecules, we have found that the lattice architectures are affected not only by supramolecular synthons and the nature of the organic molecules, but also by the degree of protonation of the organic molecules. In this work, two POM-based hybrids, namely tris[1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium)] bis[tetracosa-µ2-oxido-dodecaoxido-µ12-phosphato-dodecamolybdenum(VI)], (I), and 1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium) 1-[4-(1H-imidazol-1-yl)butyl]-1H-imidazol-3-ium tetracosa-µ2-oxido-dodecaoxido-µ12-phosphato-dodecamolybdenum(VI) dihydrate, (II), were synthesized at different pH values. In these two compounds, the organic molecules are protonated to different degrees and combine with the POM anions in different stoichiometric ratios to form different lattice architectures.
X-ray single-crystal diffraction studies reveal that (I) crystallizes in the triclinic system (space group P1). The asymmetric unit of (I) (Fig. 1) consists of one [PMo12O40] cluster and one-and-a-half doubly protonated 1,1'-(butane-1,4-diyl)diimidazole (BIM) molecules. The [PMo12O40]3- cluster shows a wellknown Keggin-type structure. It is formed by a central PO4 tetrahedron surrounded by four Mo3O13 triplets, in which three MoO6 octahedra share edges. One PO4 tetrahedron and 12 MoO6 octahedra from four Mo3O13 triplets share corners and make up the Keggin-type [PMo12O40] cluster. The P—O distances are in the range 1.526 (5)–1.544 (5) Å and the Mo—O distances can be grouped into three sets, viz. Mo—Ot = 1.670 (5)–1.687 (5) Å, Mo—Ob = 1.863 (5)–1.986 (5) Å and Mo—Oc = 2.409 (5)–2.456 (5) Å (c = central, b = bridging and t = terminal).
Bond-valence sum (BVS) analyses (Brown, 2002) using the parameters of Brese & O'Keeffe (1991) revealed minor deviations from the expected values of 6 valence units (v.u.) for all the Mo atoms of (I), 2 v.u. for all the O atoms and 5 v.u. for the P atom. Thus, the Keggin-type POM cluster adopts an oxidation state of -3. Because the ratio of POM to BIM is 2:3, the three imidazole rings from one and a half independent BIM molecules should all be protonated in order to maintain charge balance, i.e. the BIM molecules in (I) are doubly protonated.
It should be mentioned that the BIM cations in (I) exhibit two different conformations, one W-shaped (Fig. 2a) and the other Z-shaped (Fig. 2b). These two kinds of doubly protonated BIM cations link the POM cluster trianions to form a three-dimensional supramolecular network through N—H···O hydrogen bonds. As shown in Fig. 3(a), the protonated imidazole rings N1/N2 and N3/N4 from the W-shaped BIM cation form hydrogen bonds with two POM anions, with N1···O36i = 2.809 (10) Å and N3···O9 = 2.952 (10) Å [symmetry code: (i) x, y - 1, z + 1]. Each POM anion accepts hydrogen bonds from two W-shaped BIM cations using two bridging O atoms, to form a one-dimensional chain along the [011] direction. The N5/N6 imidazole ring from the the Z-shaped BIM cation forms trifurcated hydrogen bonds with two terminal O atoms (O2ii and O13) and one bridging O atom (O12iii) from three POM anions, with N5···O2ii = 3.079 (9) Å, N5···O13 = 3.076 (9) Å and N5···O12iii = 3.147 (9) Å [symmetry codes: (ii) -x + 1, -y + 1, -z + 1; (iii) x - 1, y, z]. Thus, each Z-shaped BIM cation links six POM anions through weak hydrogen bonds, and each POM anion is connected to three such BIM cations to form a two-dimensional layer parallel to the [101] plane (Fig. 3b). As shown in Fig. 3(c), the one-dimensional chain along the [011] direction and the two-dimensional layer parallel to the [101] plane cross each other, to form a three-dimensional network with POM cluster anions as the junctions. Briefly, the POM cluster anions in (I) are linked by hydrogen bonds to five doubly protonated BIM cations (two W-shaped and three Z-shaped) using their five O atoms, and the two types of BIM cations link the POM anions to form a three-dimensional supramolecular network.
Compound (II) also crystallizes in the triclinic system, space group P1. The asymmetric unit consists of half a Keggin-type [PMo12O40]3- POM cluster anion, one BIM cation and one solvent water molecule (Fig. 4). In the POM anion, the central P atom is surrounded by a cube of eight half-occupied O atoms, which often appears in Keggin-type structures (Fender et al., 1998; Attanasio et al. 1990). The P—O [1.501 (13)–1.595 (14) Å] and Mo—O bond lengths [2.426 (14)–2.510 (13) Å for Mo—Oc, 1.853 (8)–1.963 (8) for Mo—Ob and 1.671 (7)–1.650 (7) Å for Mo—Ot] are similar to those of (I) and the reported Keggin-type POM (Han et al., 2009).
The BVS analysis of (II) reveals that the POM cluster also adopts an oxidation state of -3. The stoichiometric ratio between POM and BIM ions in (II) is 1:2, i.e. there are two BIM cations per anion. Thus, for charge balance, one BIM cation should be doubly protonated and the other should be singly protonated.
The BIM cations in (II) adopt an Ω conformation (Fig. 2c). As shown in Fig. 5(a), the protonated BIM cations form hydrogen bonds with the POM anions, yielding a one-dimensional supramolecular chain along the [110] direction. In the POM–BIM chain, the N2···O19i distance is 2.897 (12) Å and the N4···O9ii distance is 2.971 (10) Å [symmetry codes: (i) x + 1, y + 1, z; (ii) x - 1, y, z], and each POM anion accepts hydrogen bonds from four BIM cations using four bridging O atoms. The solvent water molecule also acts as a hydrogen-bond donor and is linked to two POM anions (Fig. 5b). Each POM anion, using two terminal and two bridging O atoms, is linked by hydrogen bonds to four solvent water molecules to form a one-dimensional POM–H2O supramolecular chain along the [100] direction. The POM–H2O and POM–BIM chains cross each other, to form a two-dimensional supramolecular layer with the POM clusters as the junctions. Briefly, for (II), POM cluster anions are linked by hydrogen bonds to four BIM cations using their eight O atoms, and to four solvent water molecules, to form a two-dimensional supramolecular layer (Fig. 5c).
In summary, two POM-based inorganic–organic hybride compounds, (I) and (II), have been synthesized. The three-dimensional supramolecular compound, (I), in which the BIM molecules are doubly protonated, was synthesized at a lower pH (pH = 1) and has a 2:3 stoichiometric ratio between POM and BIM. The two-dimensional supramolecular compound, (II), in which the BIM molecules are partially protonated, was obtained at a relatively high pH (pH = 5) and the ratio between POM and BIM is 1:2. It can thus be concluded that the degree of protonation of the organic molecules, affected by pH, defines the stoichiometric ratio between the POM anions and the BIM cations, which can further affect the lattice architecture.