Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112043648/sf3184sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112043648/sf3184Isup2.hkl |
CCDC reference: 915087
A mixture of (NH4)6Mo7O24.4H2O (0.2 g), Cu(OAc)2.2H2O (0.10 g), DPPP (0.10 g) and H2O (10 ml) was stirred at room temperature and the pH adjusted to 3 using a H3PO4 solution. The mixture was the heated in a 15 ml Teflon-lined reaction vessel at 453 K for 5 d. After the mixture had been cooled at room temperature, green block-shaped crystals were isolated and washed with water.
All H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)].
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).
[CuMo4O13(C21H15N3)2] | Z = 1 |
Mr = 1274.02 | F(000) = 625 |
Triclinic, P1 | Dx = 2.103 Mg m−3 |
a = 8.1756 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.3263 (4) Å | Cell parameters from 3268 reflections |
c = 13.8965 (8) Å | θ = 2.6–28.6° |
α = 78.369 (1)° | µ = 1.81 mm−1 |
β = 83.065 (2)° | T = 293 K |
γ = 76.501 (1)° | Block, green |
V = 1006.13 (9) Å3 | 0.45 × 0.13 × 0.10 mm |
Bruker SMART diffractometer | 3545 independent reflections |
Radiation source: fine-focus sealed tube | 3099 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
phi and ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −9→9 |
Tmin = 0.496, Tmax = 0.840 | k = −10→11 |
6181 measured reflections | l = −13→16 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0209P)2 + 1.7942P] where P = (Fo2 + 2Fc2)/3 |
3545 reflections | (Δ/σ)max = 0.001 |
301 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[CuMo4O13(C21H15N3)2] | γ = 76.501 (1)° |
Mr = 1274.02 | V = 1006.13 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.1756 (4) Å | Mo Kα radiation |
b = 9.3263 (4) Å | µ = 1.81 mm−1 |
c = 13.8965 (8) Å | T = 293 K |
α = 78.369 (1)° | 0.45 × 0.13 × 0.10 mm |
β = 83.065 (2)° |
Bruker SMART diffractometer | 3545 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 3099 reflections with I > 2σ(I) |
Tmin = 0.496, Tmax = 0.840 | Rint = 0.022 |
6181 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.50 e Å−3 |
3545 reflections | Δρmin = −0.56 e Å−3 |
301 parameters |
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 | ||
Mo2 | 0.20305 (4) | 0.38472 (4) | −0.04893 (2) | 0.01664 (10) | |
Mo1 | 0.33602 (4) | 0.67904 (4) | 0.07478 (2) | 0.01823 (10) | |
Cu1 | 0.0000 | 1.0000 | 0.0000 | 0.02298 (17) | |
O1 | 0.1353 (3) | 0.2255 (3) | −0.0509 (2) | 0.0282 (6) | |
O2 | 0.0000 | 0.5000 | 0.0000 | 0.0304 (10) | |
O3 | 0.2044 (4) | 0.4709 (3) | −0.1681 (2) | 0.0356 (7) | |
O4 | 0.3040 (3) | 0.5490 (3) | 0.0063 (2) | 0.0257 (6) | |
O5 | 0.5501 (3) | 0.7066 (3) | 0.0583 (2) | 0.0275 (6) | |
O6 | 0.2857 (4) | 0.6190 (4) | 0.1958 (2) | 0.0413 (8) | |
O7 | 0.2045 (3) | 0.8534 (3) | 0.0382 (2) | 0.0256 (6) | |
N1 | 0.2561 (4) | 0.2517 (4) | 0.1187 (2) | 0.0230 (7) | |
N2 | 0.9111 (5) | −0.6487 (4) | 0.4850 (3) | 0.0406 (10) | |
N3 | 0.0659 (4) | −0.0251 (4) | 0.8585 (2) | 0.0230 (7) | |
C1 | 0.3405 (6) | 0.1089 (5) | 0.1263 (3) | 0.0370 (11) | |
H1 | 0.3808 | 0.0722 | 0.0686 | 0.044* | |
C2 | 0.3708 (6) | 0.0139 (5) | 0.2143 (3) | 0.0397 (12) | |
H2 | 0.4297 | −0.0845 | 0.2151 | 0.048* | |
C3 | 0.3135 (5) | 0.0647 (4) | 0.3022 (3) | 0.0228 (8) | |
C4 | 0.2259 (5) | 0.2123 (5) | 0.2942 (3) | 0.0272 (9) | |
H4 | 0.1840 | 0.2521 | 0.3507 | 0.033* | |
C5 | 0.2007 (5) | 0.3005 (5) | 0.2027 (3) | 0.0257 (9) | |
H5 | 0.1419 | 0.3993 | 0.1996 | 0.031* | |
C6 | 0.3465 (5) | −0.0361 (4) | 0.3987 (3) | 0.0217 (8) | |
C7 | 0.4711 (4) | −0.1617 (4) | 0.3996 (3) | 0.0149 (7) | |
H7 | 0.5305 | −0.1834 | 0.3411 | 0.018* | |
C8 | 0.5085 (5) | −0.2554 (4) | 0.4863 (3) | 0.0213 (8) | |
C9 | 0.4240 (4) | −0.2248 (4) | 0.5728 (2) | 0.0152 (7) | |
H9 | 0.4523 | −0.2892 | 0.6316 | 0.018* | |
C10 | 0.2978 (5) | −0.0998 (4) | 0.5736 (3) | 0.0221 (8) | |
C11 | 0.2569 (5) | −0.0043 (4) | 0.4860 (3) | 0.0219 (8) | |
H11 | 0.1701 | 0.0804 | 0.4855 | 0.026* | |
C12 | 0.8237 (5) | −0.6137 (5) | 0.5673 (4) | 0.0377 (11) | |
H12 | 0.8520 | −0.6778 | 0.6263 | 0.045* | |
C13 | 0.6940 (5) | −0.4892 (5) | 0.5719 (3) | 0.0303 (10) | |
H13 | 0.6392 | −0.4711 | 0.6323 | 0.036* | |
C14 | 0.6467 (5) | −0.3923 (4) | 0.4860 (3) | 0.0213 (8) | |
C15 | 0.7340 (5) | −0.4288 (5) | 0.3990 (3) | 0.0305 (10) | |
H15 | 0.7060 | −0.3688 | 0.3386 | 0.037* | |
C16 | 0.8623 (5) | −0.5547 (5) | 0.4032 (4) | 0.0383 (11) | |
H16 | 0.9196 | −0.5757 | 0.3439 | 0.046* | |
C17 | 0.0649 (5) | 0.0889 (5) | 0.7828 (3) | 0.0294 (10) | |
H17 | 0.0155 | 0.1853 | 0.7936 | 0.035* | |
C18 | 0.1339 (5) | 0.0702 (5) | 0.6892 (3) | 0.0266 (9) | |
H18 | 0.1291 | 0.1529 | 0.6386 | 0.032* | |
C19 | 0.2104 (5) | −0.0720 (4) | 0.6707 (3) | 0.0222 (8) | |
C20 | 0.2047 (6) | −0.1905 (5) | 0.7489 (3) | 0.0302 (10) | |
H20 | 0.2509 | −0.2884 | 0.7398 | 0.036* | |
C21 | 0.1308 (5) | −0.1634 (5) | 0.8397 (3) | 0.0280 (9) | |
H21 | 0.1257 | −0.2447 | 0.8903 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo2 | 0.01457 (16) | 0.01654 (19) | 0.01885 (18) | −0.00316 (13) | −0.00176 (13) | −0.00324 (13) |
Mo1 | 0.01609 (17) | 0.01690 (19) | 0.02142 (19) | −0.00337 (13) | −0.00098 (13) | −0.00330 (14) |
Cu1 | 0.0197 (3) | 0.0264 (4) | 0.0183 (3) | 0.0029 (3) | −0.0006 (3) | −0.0032 (3) |
O1 | 0.0264 (14) | 0.0240 (16) | 0.0374 (17) | −0.0079 (12) | −0.0064 (13) | −0.0081 (13) |
O2 | 0.0155 (19) | 0.033 (2) | 0.045 (3) | −0.0016 (17) | −0.0005 (18) | −0.017 (2) |
O3 | 0.0480 (18) | 0.0319 (18) | 0.0240 (16) | −0.0070 (14) | −0.0039 (14) | 0.0003 (13) |
O4 | 0.0232 (14) | 0.0186 (15) | 0.0383 (17) | −0.0049 (11) | −0.0053 (12) | −0.0099 (13) |
O5 | 0.0153 (13) | 0.0259 (16) | 0.0416 (18) | −0.0007 (11) | 0.0013 (12) | −0.0134 (13) |
O6 | 0.055 (2) | 0.040 (2) | 0.0263 (17) | −0.0125 (16) | 0.0023 (15) | 0.0013 (14) |
O7 | 0.0211 (13) | 0.0227 (16) | 0.0328 (16) | 0.0000 (11) | −0.0067 (12) | −0.0070 (12) |
N1 | 0.0269 (17) | 0.0201 (18) | 0.0214 (17) | −0.0061 (14) | −0.0024 (14) | −0.0008 (14) |
N2 | 0.032 (2) | 0.030 (2) | 0.060 (3) | 0.0033 (17) | −0.010 (2) | −0.016 (2) |
N3 | 0.0213 (16) | 0.025 (2) | 0.0209 (17) | −0.0015 (14) | −0.0018 (14) | −0.0037 (15) |
C1 | 0.058 (3) | 0.025 (3) | 0.024 (2) | 0.000 (2) | 0.004 (2) | −0.0083 (19) |
C2 | 0.066 (3) | 0.019 (2) | 0.027 (2) | 0.003 (2) | 0.000 (2) | −0.0047 (19) |
C3 | 0.025 (2) | 0.020 (2) | 0.023 (2) | −0.0069 (17) | 0.0006 (16) | −0.0043 (17) |
C4 | 0.030 (2) | 0.026 (2) | 0.021 (2) | 0.0016 (18) | 0.0026 (17) | −0.0057 (18) |
C5 | 0.027 (2) | 0.019 (2) | 0.028 (2) | 0.0003 (17) | −0.0008 (17) | −0.0035 (17) |
C6 | 0.026 (2) | 0.021 (2) | 0.019 (2) | −0.0086 (17) | −0.0025 (16) | −0.0032 (16) |
C7 | 0.0185 (18) | 0.0137 (19) | 0.0107 (17) | 0.0000 (15) | 0.0028 (14) | −0.0044 (14) |
C8 | 0.0221 (19) | 0.019 (2) | 0.023 (2) | −0.0048 (16) | −0.0020 (16) | −0.0043 (16) |
C9 | 0.0202 (18) | 0.0120 (19) | 0.0111 (17) | −0.0008 (15) | −0.0036 (14) | 0.0010 (14) |
C10 | 0.026 (2) | 0.020 (2) | 0.021 (2) | −0.0066 (17) | −0.0025 (16) | −0.0038 (16) |
C11 | 0.024 (2) | 0.018 (2) | 0.022 (2) | −0.0005 (16) | −0.0011 (16) | −0.0052 (16) |
C12 | 0.034 (2) | 0.032 (3) | 0.045 (3) | −0.002 (2) | −0.016 (2) | 0.001 (2) |
C13 | 0.030 (2) | 0.030 (3) | 0.029 (2) | −0.0018 (19) | −0.0059 (18) | −0.0038 (19) |
C14 | 0.0228 (19) | 0.020 (2) | 0.022 (2) | −0.0075 (16) | −0.0015 (16) | −0.0036 (16) |
C15 | 0.033 (2) | 0.029 (3) | 0.027 (2) | −0.0018 (19) | −0.0005 (19) | −0.0075 (19) |
C16 | 0.030 (2) | 0.041 (3) | 0.045 (3) | 0.001 (2) | 0.002 (2) | −0.025 (2) |
C17 | 0.029 (2) | 0.022 (2) | 0.029 (2) | 0.0078 (18) | −0.0001 (18) | −0.0027 (18) |
C18 | 0.033 (2) | 0.020 (2) | 0.020 (2) | 0.0010 (18) | 0.0014 (17) | 0.0021 (17) |
C19 | 0.025 (2) | 0.021 (2) | 0.021 (2) | −0.0040 (17) | −0.0033 (16) | −0.0042 (16) |
C20 | 0.050 (3) | 0.017 (2) | 0.023 (2) | −0.0040 (19) | −0.0029 (19) | −0.0047 (17) |
C21 | 0.042 (2) | 0.024 (2) | 0.019 (2) | −0.0113 (19) | −0.0033 (18) | 0.0020 (17) |
Mo2—O3 | 1.689 (3) | C4—C5 | 1.377 (5) |
Mo2—O1 | 1.708 (3) | C4—H4 | 0.9300 |
Mo2—O2 | 1.8876 (3) | C5—H5 | 0.9300 |
Mo2—O5i | 1.999 (2) | C6—C7 | 1.360 (5) |
Mo2—O4 | 2.199 (3) | C6—C11 | 1.387 (5) |
Mo2—N1 | 2.445 (3) | C7—C8 | 1.360 (5) |
Mo1—O6 | 1.695 (3) | C7—H7 | 0.9300 |
Mo1—O7 | 1.744 (3) | C8—C9 | 1.360 (5) |
Mo1—O4 | 1.766 (3) | C8—C14 | 1.494 (5) |
Mo1—O5 | 1.808 (3) | C9—C10 | 1.366 (5) |
Cu1—O7 | 1.950 (3) | C9—H9 | 0.9300 |
Cu1—O7ii | 1.950 (3) | C10—C11 | 1.381 (5) |
Cu1—N3iii | 2.021 (3) | C10—C19 | 1.490 (5) |
Cu1—N3iv | 2.021 (3) | C11—H11 | 0.9300 |
Cu1—O1v | 2.538 (3) | C12—C13 | 1.384 (6) |
O2—Mo2v | 1.8876 (3) | C12—H12 | 0.9300 |
O5—Mo2i | 1.999 (2) | C13—C14 | 1.381 (5) |
N1—C5 | 1.329 (5) | C13—H13 | 0.9300 |
N1—C1 | 1.338 (5) | C14—C15 | 1.389 (5) |
N2—C16 | 1.328 (6) | C15—C16 | 1.377 (6) |
N2—C12 | 1.331 (6) | C15—H15 | 0.9300 |
N3—C17 | 1.336 (5) | C16—H16 | 0.9300 |
N3—C21 | 1.340 (5) | C17—C18 | 1.382 (5) |
N3—Cu1vi | 2.021 (3) | C17—H17 | 0.9300 |
C1—C2 | 1.369 (6) | C18—C19 | 1.389 (5) |
C1—H1 | 0.9300 | C18—H18 | 0.9300 |
C2—C3 | 1.388 (5) | C19—C20 | 1.390 (5) |
C2—H2 | 0.9300 | C20—C21 | 1.377 (5) |
C3—C4 | 1.385 (5) | C20—H20 | 0.9300 |
C3—C6 | 1.489 (5) | C21—H21 | 0.9300 |
O3—Mo2—O1 | 103.23 (14) | C3—C4—H4 | 119.9 |
O3—Mo2—O2 | 99.11 (10) | N1—C5—C4 | 123.5 (4) |
O1—Mo2—O2 | 99.07 (9) | N1—C5—H5 | 118.3 |
O3—Mo2—O5i | 93.60 (13) | C4—C5—H5 | 118.3 |
O1—Mo2—O5i | 96.61 (12) | C7—C6—C11 | 120.1 (3) |
O2—Mo2—O5i | 156.94 (8) | C7—C6—C3 | 117.7 (3) |
O3—Mo2—O4 | 96.56 (13) | C11—C6—C3 | 122.3 (3) |
O1—Mo2—O4 | 160.02 (12) | C8—C7—C6 | 119.9 (3) |
O2—Mo2—O4 | 80.25 (7) | C8—C7—H7 | 120.1 |
O5i—Mo2—O4 | 79.24 (10) | C6—C7—H7 | 120.1 |
O3—Mo2—N1 | 169.75 (13) | C7—C8—C9 | 120.9 (3) |
O1—Mo2—N1 | 80.32 (12) | C7—C8—C14 | 119.1 (3) |
O2—Mo2—N1 | 89.72 (7) | C9—C8—C14 | 120.0 (3) |
O5i—Mo2—N1 | 76.36 (11) | C8—C9—C10 | 120.2 (3) |
O4—Mo2—N1 | 79.71 (10) | C8—C9—H9 | 119.9 |
O6—Mo1—O7 | 108.18 (14) | C10—C9—H9 | 119.9 |
O6—Mo1—O4 | 108.97 (14) | C9—C10—C11 | 119.6 (3) |
O7—Mo1—O4 | 109.97 (12) | C9—C10—C19 | 117.7 (3) |
O6—Mo1—O5 | 109.50 (14) | C11—C10—C19 | 122.7 (3) |
O7—Mo1—O5 | 107.06 (13) | C10—C11—C6 | 119.4 (4) |
O4—Mo1—O5 | 113.05 (12) | C10—C11—H11 | 120.3 |
O7—Cu1—O7ii | 180.000 (1) | C6—C11—H11 | 120.3 |
O7—Cu1—N3iii | 90.98 (12) | N2—C12—C13 | 125.0 (4) |
O7ii—Cu1—N3iii | 89.02 (12) | N2—C12—H12 | 117.5 |
O7—Cu1—N3iv | 89.02 (12) | C13—C12—H12 | 117.5 |
O7ii—Cu1—N3iv | 90.98 (12) | C14—C13—C12 | 119.3 (4) |
N3iii—Cu1—N3iv | 180.000 (1) | C14—C13—H13 | 120.3 |
O1v—Cu1—N3iii | 83.40 (12) | C12—C13—H13 | 120.3 |
O1v—Cu1—O7 | 83.20 (11) | C13—C14—C15 | 116.5 (4) |
O1v—Cu1—N3iv | 96.60 (11) | C13—C14—C8 | 121.8 (4) |
O1v—Cu1—O7ii | 96.80 (10) | C15—C14—C8 | 121.6 (4) |
Mo2v—O2—Mo2 | 180.000 (18) | C16—C15—C14 | 119.2 (4) |
Mo1—O4—Mo2 | 164.00 (15) | C16—C15—H15 | 120.4 |
Mo1—O5—Mo2i | 147.98 (16) | C14—C15—H15 | 120.4 |
Mo1—O7—Cu1 | 158.80 (16) | N2—C16—C15 | 125.4 (4) |
C5—N1—C1 | 116.4 (3) | N2—C16—H16 | 117.3 |
C5—N1—Mo2 | 127.8 (3) | C15—C16—H16 | 117.3 |
C1—N1—Mo2 | 115.6 (3) | N3—C17—C18 | 123.0 (4) |
C16—N2—C12 | 114.6 (4) | N3—C17—H17 | 118.5 |
C17—N3—C21 | 117.2 (3) | C18—C17—H17 | 118.5 |
C17—N3—Cu1vi | 124.0 (3) | C17—C18—C19 | 120.0 (4) |
C21—N3—Cu1vi | 118.5 (3) | C17—C18—H18 | 120.0 |
N1—C1—C2 | 123.8 (4) | C19—C18—H18 | 120.0 |
N1—C1—H1 | 118.1 | C18—C19—C20 | 116.5 (4) |
C2—C1—H1 | 118.1 | C18—C19—C10 | 123.1 (4) |
C1—C2—C3 | 119.9 (4) | C20—C19—C10 | 120.4 (3) |
C1—C2—H2 | 120.0 | C21—C20—C19 | 120.1 (4) |
C3—C2—H2 | 120.0 | C21—C20—H20 | 119.9 |
C4—C3—C2 | 116.3 (4) | C19—C20—H20 | 119.9 |
C4—C3—C6 | 122.8 (3) | N3—C21—C20 | 123.0 (4) |
C2—C3—C6 | 120.9 (4) | N3—C21—H21 | 118.5 |
C5—C4—C3 | 120.1 (4) | C20—C21—H21 | 118.5 |
C5—C4—H4 | 119.9 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z; (iii) −x, −y+1, −z+1; (iv) x, y+1, z−1; (v) −x, −y+1, −z; (vi) x, y−1, z+1. |
Experimental details
Crystal data | |
Chemical formula | [CuMo4O13(C21H15N3)2] |
Mr | 1274.02 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.1756 (4), 9.3263 (4), 13.8965 (8) |
α, β, γ (°) | 78.369 (1), 83.065 (2), 76.501 (1) |
V (Å3) | 1006.13 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.81 |
Crystal size (mm) | 0.45 × 0.13 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.496, 0.840 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6181, 3545, 3099 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.066, 1.04 |
No. of reflections | 3545 |
No. of parameters | 301 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.56 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Mo2—O3 | 1.689 (3) | Mo1—O7 | 1.744 (3) |
Mo2—O1 | 1.708 (3) | Mo1—O4 | 1.766 (3) |
Mo2—O2 | 1.8876 (3) | Mo1—O5 | 1.808 (3) |
Mo2—O5i | 1.999 (2) | Cu1—O7 | 1.950 (3) |
Mo2—O4 | 2.199 (3) | Cu1—N3ii | 2.021 (3) |
Mo2—N1 | 2.445 (3) | Cu1—O1iii | 2.538 (3) |
Mo1—O6 | 1.695 (3) | ||
O3—Mo2—O1 | 103.23 (14) | O6—Mo1—O7 | 108.18 (14) |
O3—Mo2—O2 | 99.11 (10) | O6—Mo1—O4 | 108.97 (14) |
O1—Mo2—O2 | 99.07 (9) | O7—Mo1—O4 | 109.97 (12) |
O3—Mo2—O5i | 93.60 (13) | O6—Mo1—O5 | 109.50 (14) |
O1—Mo2—O5i | 96.61 (12) | O7—Mo1—O5 | 107.06 (13) |
O2—Mo2—O5i | 156.94 (8) | O4—Mo1—O5 | 113.05 (12) |
O3—Mo2—O4 | 96.56 (13) | O7—Cu1—N3ii | 90.98 (12) |
O1—Mo2—O4 | 160.02 (12) | O7iv—Cu1—N3ii | 89.02 (12) |
O2—Mo2—O4 | 80.25 (7) | O7—Cu1—N3v | 89.02 (12) |
O5i—Mo2—O4 | 79.24 (10) | O7iv—Cu1—N3v | 90.98 (12) |
O3—Mo2—N1 | 169.75 (13) | O1iii—Cu1—N3ii | 83.40 (12) |
O1—Mo2—N1 | 80.32 (12) | O1iii—Cu1—O7 | 83.20 (11) |
O2—Mo2—N1 | 89.72 (7) | O1iii—Cu1—N3v | 96.60 (11) |
O5i—Mo2—N1 | 76.36 (11) | O1iii—Cu1—O7iv | 96.80 (10) |
O4—Mo2—N1 | 79.71 (10) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) −x, −y+2, −z; (v) x, y+1, z−1. |
The exploration of metal oxide-based inorganic–organic hybrid compounds is of great interest in the fields of solid-state chemistry, not only because of various structures but also their fascinating properties and potential applications in many fields, such as catalysis, sorption, electrical conductivity, magnetism and optical materials (Cheetham, 1994; Pope et al., 1991; Li et al., 1999). Currently, molybdenum polyoxoanions have recieved much attention due to their versatile stoichiometry, different structure and high reactivity (Kong et al., 2004). By exploiting the strategy of synergistic interaction of inorganic components and organic amines, many examples of molybdenum oxide-based solid materials with one-dimensional chains, two-dimensional layers and three-dimensional framework structures have been successfully synthesized under hydrothermal conditions (Hagrman et al., 1999; Lu et al., 2002; Wu et al., 2002; Yu et al., 2009; Wang et al., 2010; Tripathi et al., 2003; Hagrman et al., 1999; Thomas et al., 2008). Among which, most examples are discrete molybdenum oxides clusters, which are modified by transition metals and organic ligands. Molybdenum oxide chains have been less reported (Chen et al., 2005, 2006; Yang, Chen et al., 2011; Yang, Lin et al., 2011).
It is well known that the Mo atom usually adopts octahedral coordination geometry in the reported molybdenum oxides clusters and chains. Comparing with the MoO6 octahedron, the MoO5N octahedron, which often exists in organoimido or pyridine substituted isopolymolybdate clusters, is relatively less reported (Wei et al., 2001; Peng 2004; Wu et al., 2010; Zhang et al., 2010; Meng et al., 2009). In this work, a novel molybdenum oxides compound modified by transition metal Cu and organic ligands [Cu(Mo4O13)(C21N3H15)2]n has been synthesized. In the title compound, the MoO4 tetrahedra and MoO5N octahedra connect each other via sharing corners to form [Mo3O13N2]n chain, which are further connected by CuII and 4-(3,5-di(pyridin-4-yl)phenyl)pyridine (DPPP) ligand to form three-dimensional framework.
The asymmetric unit of the title compound consists of two MoVI atoms, six and a half O atoms, half of a CuII atom and one DPPP ligand (shown in Fig. 1). As shown in Fig. 2, the Mo1 atom adopts tetrahedral coordination geometry and is coordinated by one terminal O atom (O6) and three µ2-bridging O atoms (O4, O5 and O7). The Mo2 center adopts an octahedral geometry and is coordinated by one terminal O atom (O3), four µ2-bridging O atoms (O1, O2, O4 and O5A) and one N atom (N1) from the DPPP ligand. The average Mo—Oterminal and Mo—Obridging bond lengths are 1.691 and 1.873 Å, respectively, which are similar to the reported values of molybdenum oxide clusters (1.685–1.702 and 1.726–1.996 Å, respectively; Han et al., 2009; Fielden et al., 2009) The Mo—N bond length of 2.447 Å is slightly shorter than similar reported values (2.426 and 2.248 Å; Wang et al., 2011; Zapf et al., 1998). Atoms Mo1 and Mo2 and symmetry-related Mo1A and Mo2A are bridged alternatively by four µ2-bridging O atoms (O4, O5, O4A and O5A) to form an [Mo4O13N2] tetramolybdate unit. Atom O2, which is located on an inversion center with an occupancy of 1/2, is also µ2-bridging and coordinates with Mo2 and its symmetry-related counterpart from the other [Mo4O13N2] tetramer unit. So, each [Mo4O13N2] tetrameric unit links two adjacent units to form an [Mo4O13N2]n chain along the a axis through corner-sharing of MoO5N octahedra.
The Cu atom is also located on the inversion center with an occupancy of 0.5 and is coordinated by two N atoms (N3B and N3E) from two DPPP ligands and four µ2-O atoms from four [Mo4O13N2] units, which belong to two adjacent Mo—O chains. The Cu—O1, Cu—O7 and Cu—N3 bond lengths are 2.538 (3), 1.950 (3) and 2.021 (3) Å, respectively, which suggest that the Cu center is located at the center of an elongated octahedron with atoms O1B and O1C occupying the elongated axis sites. Thus, O1 and O7 adopt µ2-coordination modes and bridge Mo2 and Cu1, and Mo1 and Cu1, respectively. Cu1 centers act as `glue' connecting the Mo—O chains to form a two-dimensional Cu—Mo—O layer parallel to the ab plane with the [CuMo4O13N2] unit. As shown in Fig. 3, the DPPP ligands link the two-dimensional Cu—Mo—O layers to form three-dimensional inorganic–organic hybrid network using its two N atoms.
In the [CuMo4O13N2] unit, the four Mo centers adopt tetrahedral and octahedral geometries and are coordinated by nine µ2-O atoms and four terminal O atoms. As far as we know, in the most reported tetramolybdate clusters and molybdenum oxide chains, Mo atoms usually adopt an octahedral or a trigonal bipyramidal geometry and are bridged by µ3-O or µ4-O atoms (LaDuca et al., 2000; Lu et al., 2003; Burkholder et al., 2003; Quintal et al., 2001; Chen et al., 2005, 2006; Yang, Chen et al., 2011; Yang, Lin et al., 2011). Only several tetramolybdate clusters containing MoO4 tetrahedra have been reported, in which the Mo centers are linked by five or six µ2-O atoms (Attanasio et al., 1986; Harada et al., 2004). Several Mo—O chains containing MoO4 tetrahedra and MoO6 octahedra have also been reported (Jones et al., 2010; McKee et al., 1984). So, the [Mo4O13N2]n chain in the title compound is a novel example containing MoO4 tetrahedra and MoO5N octahedra.
Bond-valence sum (BVS) analysis (Brown, 2002) using the parameters of Brese & O'Keeffe (1991) revealed slight deviations from the expected values of 6 valence units (v.u.) for the Mo atoms and 2 v.u. for the Cu and O atoms. The deviations reflect the distortions in the polyhedra: Mo1 (coordination number = 4; BVS = 6.10 v.u.), Mo2 (6; 6.13), Cu1 (6; 2.28), O1 (2; 1.71), O2 (2; 2.11), O3 (1, 1.80), O4 (2; 1.92), O5 (2; 2.09), O6 (1; 1.77) and O7 (2; 2.52).
In summary, a novel three-dimensional molybdenum oxide-based inorganic–organic hybrid compound, (I), has been synthesized. In the compound, MoO4 tetrahedra, MoO5N octahedra and CuO4N2 octahedra are connected to each other via corner-sharing to form a [CuMo3O13N2]n layer, which are further connected by DPPP ligands to form the three-dimensional framework.