Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109045089/ku3013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109045089/ku3013Isup2.hkl |
CCDC reference: 763593
(Hmim)3[NaMo8O26(mim)2] was prepared from aqueous solutions containing water (5 ml), Na2MoO4 (200 mg, 0.97 mmol) and 1-methylimidazole (1.2 ml). This solution was stirred at room temperature with 30% H2O2 (1.0 ml) added dropwise at 263 K. The resulting dark-red–brown solution was stirred for an additional 2–4 h. During this period of time the red–brown solution turned to light yellow. Finally, the solution was concentrated by evacuation and left for crystallization at room temperature. After a few weeks, rectangular transparent and colorless crystals of the title compound were formed. A crystal suitable for crystal structure analysis was fixed onto a glass filament and coated in perfluorated oil (Kel-F).
H atoms were positioned geometrically [C—H = 0.93–0.96 Å, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C,N)]. During structure refinement, one of the methylimidazolium cations was found to be disordered (Fig. 1). This was dealt with using split atom positions. When refining the relevant site occupation factors, values near 50% were identified, and these site occupancies were subsequently fixed at 0.5.
Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2009).
(C4H7N2)3[NaMo8O26(C4H6N2)2] | F(000) = 1732 |
Mr = 1784.29 | Dx = 2.253 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6846 reflections |
a = 11.692 (2) Å | θ = 3.0–60.0° |
b = 10.298 (2) Å | µ = 1.95 mm−1 |
c = 22.190 (4) Å | T = 298 K |
β = 100.12 (3)° | Rectangular, colorless |
V = 2630.2 (9) Å3 | 0.4 × 0.2 × 0.2 mm |
Z = 2 |
Stoe IPDS II diffractometer | 7219 independent reflections |
Radiation source: fine-focus sealed tube | 5717 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
imaging plate diffraction system scans | θmax = 29.6°, θmin = 2.2° |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1999) | h = −16→16 |
Tmin = 0.393, Tmax = 0.528 | k = −14→14 |
22631 measured reflections | l = −30→25 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0602P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.002 |
7219 reflections | Δρmax = 1.11 e Å−3 |
378 parameters | Δρmin = −0.96 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0032 (2) |
(C4H7N2)3[NaMo8O26(C4H6N2)2] | V = 2630.2 (9) Å3 |
Mr = 1784.29 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.692 (2) Å | µ = 1.95 mm−1 |
b = 10.298 (2) Å | T = 298 K |
c = 22.190 (4) Å | 0.4 × 0.2 × 0.2 mm |
β = 100.12 (3)° |
Stoe IPDS II diffractometer | 7219 independent reflections |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1999) | 5717 reflections with I > 2σ(I) |
Tmin = 0.393, Tmax = 0.528 | Rint = 0.058 |
22631 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 0.97 | Δρmax = 1.11 e Å−3 |
7219 reflections | Δρmin = −0.96 e Å−3 |
378 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 | Occ. (<1) | |
Mo1 | 0.36916 (3) | 0.72008 (3) | 0.579880 (16) | 0.01950 (9) | |
Mo2 | 0.52428 (3) | 0.93453 (3) | 0.373499 (16) | 0.02093 (9) | |
Mo3 | 0.59280 (3) | 0.87367 (3) | 0.533358 (15) | 0.01805 (9) | |
Mo4 | 0.34864 (3) | 0.75230 (3) | 0.432644 (16) | 0.02078 (9) | |
Na1 | 0.5000 | 0.5000 | 0.5000 | 0.0269 (5) | |
O1 | 0.2793 (3) | 0.7499 (3) | 0.63099 (15) | 0.0293 (6) | |
O2 | 0.3566 (3) | 0.5555 (3) | 0.56340 (14) | 0.0262 (6) | |
O3 | 0.5017 (2) | 0.7235 (3) | 0.51633 (13) | 0.0211 (5) | |
O4 | 0.4645 (2) | 0.8887 (3) | 0.59393 (13) | 0.0204 (5) | |
O5 | 0.2829 (2) | 0.7866 (3) | 0.50632 (13) | 0.0225 (6) | |
O6 | 0.6501 (3) | 0.9168 (3) | 0.34484 (17) | 0.0369 (8) | |
O7 | 0.4207 (3) | 0.9657 (3) | 0.31079 (15) | 0.0331 (7) | |
O8 | 0.5733 (2) | 1.0579 (3) | 0.54859 (13) | 0.0206 (5) | |
O9 | 0.4759 (3) | 0.7601 (3) | 0.38683 (14) | 0.0245 (6) | |
O10 | 0.6536 (2) | 0.8890 (3) | 0.46729 (14) | 0.0240 (6) | |
O11 | 0.7073 (2) | 0.8319 (3) | 0.58829 (15) | 0.0272 (6) | |
O12 | 0.2323 (3) | 0.8031 (3) | 0.38030 (15) | 0.0320 (7) | |
O13 | 0.3395 (3) | 0.5852 (3) | 0.43181 (14) | 0.0269 (6) | |
N1 | 0.5129 (3) | 0.6509 (3) | 0.65255 (16) | 0.0217 (6) | |
N2 | 0.6129 (3) | 0.5135 (4) | 0.71659 (17) | 0.0275 (7) | |
C1 | 0.5821 (3) | 0.7203 (4) | 0.6984 (2) | 0.0254 (8) | |
H1 | 0.5860 | 0.8103 | 0.7014 | 0.030* | |
C2 | 0.6436 (4) | 0.6349 (4) | 0.7383 (2) | 0.0299 (9) | |
H2 | 0.6962 | 0.6553 | 0.7736 | 0.036* | |
C3 | 0.5350 (4) | 0.5263 (4) | 0.6652 (2) | 0.0252 (8) | |
H3 | 0.5009 | 0.4574 | 0.6415 | 0.030* | |
C4 | 0.6617 (6) | 0.3927 (5) | 0.7433 (3) | 0.0483 (15) | |
H4A | 0.6180 | 0.3209 | 0.7235 | 0.072* | |
H4B | 0.6584 | 0.3916 | 0.7862 | 0.072* | |
H4C | 0.7412 | 0.3856 | 0.7379 | 0.072* | |
N3 | 0.0886 (3) | 0.3841 (4) | 0.4053 (2) | 0.0336 (8) | |
N4 | 0.0731 (4) | 0.3526 (5) | 0.4999 (2) | 0.0385 (9) | |
H4 | 0.0899 | 0.3486 | 0.5392 | 0.046* | |
C5 | 0.1431 (4) | 0.3914 (5) | 0.4637 (2) | 0.0360 (10) | |
H5 | 0.2190 | 0.4198 | 0.4764 | 0.043* | |
C6 | 0.1397 (5) | 0.4139 (6) | 0.3510 (3) | 0.0418 (12) | |
H6A | 0.1813 | 0.3394 | 0.3403 | 0.063* | |
H6B | 0.1923 | 0.4858 | 0.3598 | 0.063* | |
H6C | 0.0791 | 0.4359 | 0.3175 | 0.063* | |
C7 | −0.0208 (4) | 0.3403 (6) | 0.4051 (3) | 0.0429 (12) | |
H7A | −0.0779 | 0.3269 | 0.3709 | 0.051* | |
C8 | −0.0313 (4) | 0.3195 (6) | 0.4651 (3) | 0.0416 (12) | |
H8 | −0.0966 | 0.2888 | 0.4792 | 0.050* | |
N5 | 0.1214 (4) | 0.3454 (5) | 0.6223 (2) | 0.0450 (11) | |
C9 | 0.0598 (5) | 0.3210 (7) | 0.6683 (3) | 0.0516 (14) | |
H9A | −0.0195 | 0.3039 | 0.6621 | 0.062* | 0.50 |
H9B | −0.0106 | 0.2769 | 0.6639 | 0.062* | 0.50 |
C10A | 0.2273 (10) | 0.3675 (14) | 0.6494 (6) | 0.039 (3)* | 0.50 |
H10A | 0.2902 | 0.3797 | 0.6296 | 0.047* | 0.50 |
N6A | 0.2325 (9) | 0.3701 (12) | 0.7103 (5) | 0.045 (2)* | 0.50 |
C11A | 0.1280 (12) | 0.3249 (16) | 0.7229 (7) | 0.048 (3)* | 0.50 |
H11A | 0.1097 | 0.3025 | 0.7606 | 0.058* | 0.50 |
C12A | 0.3307 (13) | 0.4082 (17) | 0.7585 (7) | 0.060 (3)* | 0.50 |
H12A | 0.3775 | 0.3333 | 0.7715 | 0.091* | 0.50 |
H12B | 0.3013 | 0.4437 | 0.7928 | 0.091* | 0.50 |
H12C | 0.3771 | 0.4722 | 0.7426 | 0.091* | 0.50 |
C10B | 0.2161 (11) | 0.4118 (15) | 0.6511 (6) | 0.044 (3)* | 0.50 |
H10B | 0.2721 | 0.4460 | 0.6306 | 0.052* | 0.50 |
N6B | 0.2211 (9) | 0.4233 (11) | 0.7108 (5) | 0.042 (2)* | 0.50 |
C11B | 0.1195 (11) | 0.3727 (14) | 0.7223 (6) | 0.043 (3)* | 0.50 |
H11B | 0.0945 | 0.3730 | 0.7598 | 0.051* | 0.50 |
C12B | 0.3162 (14) | 0.4805 (17) | 0.7551 (8) | 0.064 (4)* | 0.50 |
H12D | 0.3889 | 0.4446 | 0.7488 | 0.096* | 0.50 |
H12E | 0.3047 | 0.4613 | 0.7959 | 0.096* | 0.50 |
H12F | 0.3170 | 0.5729 | 0.7495 | 0.096* | 0.50 |
C16 | 1.0905 (18) | 1.022 (2) | 0.5716 (11) | 0.048 (4) | 0.50 |
H16A | 1.0483 | 1.0801 | 0.5935 | 0.073* | 0.50 |
H16B | 1.1641 | 1.0600 | 0.5682 | 0.073* | 0.50 |
H16C | 1.1031 | 0.9411 | 0.5933 | 0.073* | 0.50 |
N7 | 0.8762 (13) | 0.9657 (19) | 0.4385 (12) | 0.050 (4) | 0.50 |
H7 | 0.8065 | 0.9526 | 0.4194 | 0.060* | 0.50 |
C13 | 1.0651 (9) | 0.9887 (13) | 0.4576 (7) | 0.050 (3) | 0.50 |
H13 | 1.1425 | 0.9952 | 0.4531 | 0.060* | 0.50 |
C14 | 0.9741 (14) | 0.9677 (14) | 0.4136 (8) | 0.057 (3) | 0.50 |
H14 | 0.9771 | 0.9562 | 0.3724 | 0.068* | 0.50 |
N8 | 1.0232 (9) | 0.9987 (15) | 0.5100 (8) | 0.047 (3) | 0.50 |
C15 | 0.9084 (12) | 0.9879 (13) | 0.4981 (10) | 0.057 (4) | 0.50 |
H15 | 0.8590 | 0.9946 | 0.5265 | 0.069* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.01900 (14) | 0.02007 (15) | 0.01890 (17) | −0.00250 (11) | 0.00188 (11) | 0.00202 (11) |
Mo2 | 0.02534 (16) | 0.01955 (15) | 0.01828 (17) | −0.00030 (11) | 0.00487 (12) | −0.00039 (12) |
Mo3 | 0.01766 (14) | 0.01667 (14) | 0.01949 (17) | −0.00037 (10) | 0.00230 (11) | 0.00049 (11) |
Mo4 | 0.02299 (15) | 0.01944 (15) | 0.01832 (17) | −0.00298 (11) | −0.00077 (12) | 0.00073 (12) |
Na1 | 0.0291 (11) | 0.0209 (10) | 0.0288 (13) | 0.0026 (8) | 0.0003 (9) | −0.0004 (9) |
O1 | 0.0252 (13) | 0.0368 (17) | 0.0259 (16) | −0.0020 (12) | 0.0042 (12) | 0.0002 (13) |
O2 | 0.0279 (13) | 0.0261 (14) | 0.0223 (15) | −0.0058 (11) | −0.0019 (11) | 0.0046 (11) |
O3 | 0.0231 (12) | 0.0168 (12) | 0.0233 (14) | −0.0025 (9) | 0.0036 (10) | −0.0009 (10) |
O4 | 0.0222 (12) | 0.0180 (12) | 0.0213 (14) | −0.0038 (9) | 0.0047 (10) | −0.0010 (10) |
O5 | 0.0193 (11) | 0.0261 (13) | 0.0210 (14) | −0.0019 (10) | 0.0003 (10) | 0.0038 (11) |
O6 | 0.0423 (18) | 0.0338 (17) | 0.037 (2) | 0.0039 (14) | 0.0148 (15) | 0.0045 (14) |
O7 | 0.0464 (18) | 0.0230 (15) | 0.0268 (17) | −0.0024 (13) | −0.0018 (14) | −0.0014 (12) |
O8 | 0.0224 (12) | 0.0163 (12) | 0.0232 (14) | −0.0009 (9) | 0.0042 (10) | 0.0006 (10) |
O9 | 0.0314 (14) | 0.0193 (13) | 0.0232 (15) | 0.0003 (10) | 0.0059 (11) | −0.0004 (11) |
O10 | 0.0241 (12) | 0.0234 (13) | 0.0250 (15) | 0.0011 (10) | 0.0057 (11) | 0.0003 (11) |
O11 | 0.0251 (13) | 0.0259 (14) | 0.0290 (16) | 0.0005 (11) | 0.0004 (12) | 0.0015 (12) |
O12 | 0.0324 (15) | 0.0378 (17) | 0.0222 (16) | −0.0035 (13) | −0.0046 (12) | 0.0009 (13) |
O13 | 0.0331 (14) | 0.0230 (14) | 0.0233 (15) | −0.0034 (11) | 0.0013 (12) | −0.0027 (11) |
N1 | 0.0259 (15) | 0.0204 (15) | 0.0187 (16) | 0.0006 (12) | 0.0034 (12) | 0.0017 (12) |
N2 | 0.0322 (17) | 0.0240 (17) | 0.0235 (18) | 0.0026 (13) | −0.0030 (14) | 0.0044 (13) |
C1 | 0.0273 (18) | 0.0227 (18) | 0.024 (2) | 0.0007 (14) | 0.0001 (15) | −0.0008 (15) |
C2 | 0.032 (2) | 0.028 (2) | 0.027 (2) | −0.0038 (16) | −0.0027 (17) | 0.0027 (17) |
C3 | 0.0286 (18) | 0.0233 (18) | 0.023 (2) | −0.0026 (14) | 0.0024 (15) | 0.0011 (15) |
C4 | 0.062 (3) | 0.030 (2) | 0.043 (3) | 0.010 (2) | −0.019 (3) | 0.008 (2) |
N3 | 0.0287 (18) | 0.036 (2) | 0.036 (2) | −0.0029 (15) | 0.0038 (15) | −0.0026 (17) |
N4 | 0.037 (2) | 0.042 (2) | 0.037 (2) | −0.0041 (17) | 0.0066 (17) | −0.0017 (18) |
C5 | 0.0265 (19) | 0.046 (3) | 0.035 (3) | −0.0056 (18) | 0.0043 (18) | −0.004 (2) |
C6 | 0.044 (3) | 0.049 (3) | 0.033 (3) | −0.001 (2) | 0.009 (2) | −0.001 (2) |
C7 | 0.027 (2) | 0.046 (3) | 0.052 (3) | −0.0052 (19) | −0.001 (2) | 0.003 (2) |
C8 | 0.029 (2) | 0.044 (3) | 0.052 (3) | −0.0078 (19) | 0.008 (2) | 0.005 (2) |
N5 | 0.050 (2) | 0.047 (3) | 0.040 (3) | −0.009 (2) | 0.014 (2) | 0.004 (2) |
C9 | 0.040 (3) | 0.066 (4) | 0.053 (4) | −0.002 (3) | 0.018 (2) | 0.002 (3) |
C16 | 0.037 (13) | 0.042 (7) | 0.067 (12) | −0.011 (9) | 0.011 (10) | 0.006 (6) |
N7 | 0.012 (6) | 0.046 (7) | 0.093 (13) | −0.005 (5) | 0.015 (6) | 0.010 (7) |
C13 | 0.025 (5) | 0.056 (7) | 0.068 (9) | −0.002 (4) | 0.006 (5) | 0.002 (7) |
C14 | 0.046 (7) | 0.053 (8) | 0.072 (10) | −0.001 (6) | 0.012 (7) | 0.009 (7) |
N8 | 0.035 (11) | 0.036 (4) | 0.072 (13) | 0.010 (7) | 0.012 (7) | 0.015 (6) |
C15 | 0.035 (7) | 0.042 (6) | 0.098 (14) | 0.004 (5) | 0.018 (9) | 0.004 (7) |
Mo1—O1 | 1.704 (3) | N3—C5 | 1.342 (6) |
Mo1—O2 | 1.734 (3) | N3—C7 | 1.355 (6) |
Mo1—O5 | 1.890 (3) | N3—C6 | 1.469 (7) |
Mo1—O4 | 2.058 (3) | N4—C5 | 1.306 (7) |
Mo1—N1 | 2.232 (3) | N4—C8 | 1.369 (6) |
Mo1—O3 | 2.271 (3) | N4—H4 | 0.8600 |
Mo1—Na1 | 3.4017 (7) | C5—H5 | 0.9300 |
Mo2—O7 | 1.707 (3) | C6—H6A | 0.9600 |
Mo2—O6 | 1.712 (4) | C6—H6B | 0.9600 |
Mo2—O9 | 1.922 (3) | C6—H6C | 0.9600 |
Mo2—O4i | 1.954 (3) | C7—C8 | 1.374 (9) |
Mo2—O8i | 2.233 (3) | C7—H7A | 0.9300 |
Mo2—O10 | 2.394 (3) | C8—H8 | 0.9300 |
Mo3—O11 | 1.700 (3) | N5—C10A | 1.298 (13) |
Mo3—O10 | 1.746 (3) | N5—C10B | 1.362 (14) |
Mo3—O3 | 1.879 (3) | N5—C9 | 1.372 (8) |
Mo3—O8 | 1.948 (3) | C9—C11A | 1.328 (15) |
Mo3—O4 | 2.189 (3) | C9—C11B | 1.383 (15) |
Mo3—O8i | 2.516 (3) | C9—H9A | 0.9300 |
Mo4—O12 | 1.708 (3) | C9—H9B | 0.9300 |
Mo4—O13 | 1.724 (3) | C10A—N6A | 1.343 (17) |
Mo4—O9 | 1.946 (3) | C10A—H10A | 0.9300 |
Mo4—O5 | 1.957 (3) | N6A—C11A | 1.380 (18) |
Mo4—O8i | 2.166 (3) | N6A—C12A | 1.478 (18) |
Mo4—O3 | 2.360 (3) | C11A—H11A | 0.9300 |
Mo4—Na1 | 3.3447 (7) | C12A—H12A | 0.9600 |
Na1—O3 | 2.329 (3) | C12A—H12B | 0.9600 |
Na1—O3ii | 2.329 (3) | C12A—H12C | 0.9600 |
Na1—O13ii | 2.363 (3) | C10B—N6B | 1.321 (17) |
Na1—O13 | 2.363 (3) | C10B—H10B | 0.9300 |
Na1—O2 | 2.438 (3) | N6B—C11B | 1.362 (16) |
Na1—O2ii | 2.439 (3) | N6B—C12B | 1.471 (18) |
Na1—Mo4ii | 3.3447 (7) | C11B—H11B | 0.9300 |
Na1—Mo1ii | 3.4017 (7) | C12B—H12D | 0.9600 |
O4—Mo2i | 1.954 (3) | C12B—H12E | 0.9600 |
O8—Mo4i | 2.166 (3) | C12B—H12F | 0.9600 |
O8—Mo2i | 2.233 (3) | C16—N8 | 1.47 (3) |
O8—Mo3i | 2.516 (3) | C16—H16A | 0.9600 |
N1—C3 | 1.330 (5) | C16—H16B | 0.9600 |
N1—C1 | 1.381 (5) | C16—H16C | 0.9600 |
N2—C3 | 1.335 (5) | N7—C15 | 1.33 (3) |
N2—C2 | 1.365 (6) | N7—C14 | 1.356 (18) |
N2—C4 | 1.452 (6) | N7—H7 | 0.8600 |
C1—C2 | 1.362 (6) | C13—C14 | 1.33 (2) |
C1—H1 | 0.9300 | C13—N8 | 1.34 (3) |
C2—H2 | 0.9300 | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—H4A | 0.9600 | N8—C15 | 1.326 (18) |
C4—H4B | 0.9600 | C15—H15 | 0.9300 |
C4—H4C | 0.9600 | ||
O1—Mo1—O2 | 106.08 (15) | Mo4ii—Na1—Mo1 | 122.399 (15) |
O1—Mo1—O5 | 102.21 (14) | Mo4—Na1—Mo1 | 57.603 (15) |
O2—Mo1—O5 | 99.18 (13) | Mo1ii—Na1—Mo1 | 180.0 |
O1—Mo1—O4 | 97.37 (14) | Mo1—O2—Na1 | 108.03 (14) |
O2—Mo1—O4 | 151.66 (13) | Mo3—O3—Mo1 | 108.20 (13) |
O5—Mo1—O4 | 91.01 (12) | Mo3—O3—Na1 | 146.51 (14) |
O1—Mo1—N1 | 92.91 (14) | Mo1—O3—Na1 | 95.36 (10) |
O2—Mo1—N1 | 82.28 (13) | Mo3—O3—Mo4 | 112.29 (13) |
O5—Mo1—N1 | 163.66 (13) | Mo1—O3—Mo4 | 89.12 (10) |
O4—Mo1—N1 | 80.83 (12) | Na1—O3—Mo4 | 90.99 (9) |
O1—Mo1—O3 | 168.04 (13) | Mo2i—O4—Mo1 | 147.30 (15) |
O2—Mo1—O3 | 85.74 (13) | Mo2i—O4—Mo3 | 106.52 (12) |
O5—Mo1—O3 | 77.13 (11) | Mo1—O4—Mo3 | 105.00 (12) |
O4—Mo1—O3 | 70.77 (11) | Mo1—O5—Mo4 | 115.30 (14) |
N1—Mo1—O3 | 86.79 (12) | Mo3—O8—Mo4i | 148.63 (14) |
O1—Mo1—Na1 | 148.56 (11) | Mo3—O8—Mo2i | 105.05 (12) |
O2—Mo1—Na1 | 42.97 (11) | Mo4i—O8—Mo2i | 94.31 (11) |
O5—Mo1—Na1 | 90.70 (9) | Mo3—O8—Mo3i | 104.27 (11) |
O4—Mo1—Na1 | 111.10 (8) | Mo4i—O8—Mo3i | 97.58 (10) |
N1—Mo1—Na1 | 79.24 (9) | Mo2i—O8—Mo3i | 96.63 (10) |
O3—Mo1—Na1 | 42.97 (7) | Mo2—O9—Mo4 | 113.08 (14) |
O7—Mo2—O6 | 104.47 (18) | Mo3—O10—Mo2 | 117.35 (14) |
O7—Mo2—O9 | 96.63 (14) | Mo4—O13—Na1 | 108.84 (13) |
O6—Mo2—O9 | 104.65 (15) | C3—N1—C1 | 106.1 (3) |
O7—Mo2—O4i | 96.79 (14) | C3—N1—Mo1 | 123.7 (3) |
O6—Mo2—O4i | 103.33 (15) | C1—N1—Mo1 | 129.5 (3) |
O9—Mo2—O4i | 144.70 (13) | C3—N2—C2 | 108.0 (3) |
O7—Mo2—O8i | 103.83 (15) | C3—N2—C4 | 126.4 (4) |
O6—Mo2—O8i | 151.67 (14) | C2—N2—C4 | 125.5 (4) |
O9—Mo2—O8i | 73.10 (11) | C2—C1—N1 | 108.6 (4) |
O4i—Mo2—O8i | 72.03 (11) | C2—C1—H1 | 125.7 |
O7—Mo2—O10 | 174.14 (15) | N1—C1—H1 | 125.7 |
O6—Mo2—O10 | 81.32 (14) | C1—C2—N2 | 106.6 (4) |
O9—Mo2—O10 | 80.88 (11) | C1—C2—H2 | 126.7 |
O4i—Mo2—O10 | 82.51 (11) | N2—C2—H2 | 126.7 |
O8i—Mo2—O10 | 70.40 (10) | N1—C3—N2 | 110.7 (4) |
O11—Mo3—O10 | 103.85 (15) | N1—C3—H3 | 124.6 |
O11—Mo3—O3 | 106.45 (14) | N2—C3—H3 | 124.6 |
O10—Mo3—O3 | 101.89 (13) | N2—C4—H4A | 109.5 |
O11—Mo3—O8 | 102.92 (13) | N2—C4—H4B | 109.5 |
O10—Mo3—O8 | 97.76 (13) | H4A—C4—H4B | 109.5 |
O3—Mo3—O8 | 139.24 (12) | N2—C4—H4C | 109.5 |
O11—Mo3—O4 | 96.66 (13) | H4A—C4—H4C | 109.5 |
O10—Mo3—O4 | 159.05 (12) | H4B—C4—H4C | 109.5 |
O3—Mo3—O4 | 75.89 (11) | C5—N3—C7 | 108.0 (5) |
O8—Mo3—O4 | 73.17 (11) | C5—N3—C6 | 126.0 (4) |
O11—Mo3—O8i | 178.15 (12) | C7—N3—C6 | 125.9 (5) |
O10—Mo3—O8i | 75.18 (11) | C5—N4—C8 | 108.8 (5) |
O3—Mo3—O8i | 75.34 (10) | C5—N4—H4 | 125.6 |
O8—Mo3—O8i | 75.73 (11) | C8—N4—H4 | 125.6 |
O4—Mo3—O8i | 84.19 (10) | N4—C5—N3 | 109.5 (4) |
O12—Mo4—O13 | 104.93 (15) | N4—C5—H5 | 125.2 |
O12—Mo4—O9 | 102.85 (15) | N3—C5—H5 | 125.2 |
O13—Mo4—O9 | 95.02 (14) | N3—C6—H6A | 109.5 |
O12—Mo4—O5 | 97.48 (15) | N3—C6—H6B | 109.5 |
O13—Mo4—O5 | 98.99 (14) | H6A—C6—H6B | 109.5 |
O9—Mo4—O5 | 151.38 (12) | N3—C6—H6C | 109.5 |
O12—Mo4—O8i | 96.48 (14) | H6A—C6—H6C | 109.5 |
O13—Mo4—O8i | 157.80 (12) | H6B—C6—H6C | 109.5 |
O9—Mo4—O8i | 74.21 (11) | N3—C7—C8 | 107.1 (5) |
O5—Mo4—O8i | 83.74 (12) | N3—C7—H7A | 126.5 |
O12—Mo4—O3 | 167.59 (14) | C8—C7—H7A | 126.5 |
O13—Mo4—O3 | 85.41 (12) | N4—C8—C7 | 106.6 (5) |
O9—Mo4—O3 | 82.68 (12) | N4—C8—H8 | 126.7 |
O5—Mo4—O3 | 73.77 (11) | C7—C8—H8 | 126.7 |
O8i—Mo4—O3 | 74.14 (10) | C10A—N5—C9 | 105.6 (7) |
O12—Mo4—Na1 | 146.86 (12) | C10B—N5—C9 | 103.4 (7) |
O13—Mo4—Na1 | 41.97 (10) | C11A—C9—N5 | 111.3 (8) |
O9—Mo4—Na1 | 82.67 (9) | N5—C9—C11B | 108.8 (7) |
O5—Mo4—Na1 | 91.24 (8) | C11A—C9—H9A | 124.4 |
O8i—Mo4—Na1 | 116.29 (7) | N5—C9—H9A | 124.4 |
O3—Mo4—Na1 | 44.13 (7) | C11B—C9—H9A | 122.7 |
O3—Na1—O3ii | 180.0 | C11A—C9—H9B | 119.3 |
O3—Na1—O13ii | 106.45 (10) | N5—C9—H9B | 125.6 |
O3ii—Na1—O13ii | 73.55 (10) | C11B—C9—H9B | 125.5 |
O3—Na1—O13 | 73.55 (10) | N5—C10A—N6A | 109.9 (10) |
O3ii—Na1—O13 | 106.45 (10) | N5—C10A—H10A | 125.0 |
O13ii—Na1—O13 | 180.00 (13) | N6A—C10A—H10A | 125.0 |
O3—Na1—O2 | 70.51 (10) | C10A—N6A—C11A | 108.1 (11) |
O3ii—Na1—O2 | 109.49 (10) | C10A—N6A—C12A | 128.7 (11) |
O13ii—Na1—O2 | 105.48 (11) | C11A—N6A—C12A | 123.1 (12) |
O13—Na1—O2 | 74.52 (11) | C9—C11A—N6A | 103.8 (12) |
O3—Na1—O2ii | 109.49 (10) | C9—C11A—H11A | 128.1 |
O3ii—Na1—O2ii | 70.51 (10) | N6A—C11A—H11A | 128.1 |
O13ii—Na1—O2ii | 74.52 (11) | N6B—C10B—N5 | 113.9 (11) |
O13—Na1—O2ii | 105.48 (11) | N6B—C10B—H10B | 123.0 |
O2—Na1—O2ii | 180.00 (14) | N5—C10B—H10B | 123.0 |
O3—Na1—Mo4ii | 135.12 (7) | C10B—N6B—C11B | 105.4 (11) |
O3ii—Na1—Mo4ii | 44.88 (7) | C10B—N6B—C12B | 127.0 (12) |
O13ii—Na1—Mo4ii | 29.19 (7) | C11B—N6B—C12B | 127.6 (12) |
O13—Na1—Mo4ii | 150.81 (7) | N6B—C11B—C9 | 108.1 (11) |
O2—Na1—Mo4ii | 106.73 (7) | N6B—C11B—H11B | 126.0 |
O2ii—Na1—Mo4ii | 73.27 (7) | C9—C11B—H11B | 126.0 |
O3—Na1—Mo4 | 44.88 (7) | N6B—C12B—H12D | 109.5 |
O3ii—Na1—Mo4 | 135.12 (7) | N6B—C12B—H12E | 109.5 |
O13ii—Na1—Mo4 | 150.81 (7) | H12D—C12B—H12E | 109.5 |
O13—Na1—Mo4 | 29.19 (7) | N6B—C12B—H12F | 109.5 |
O2—Na1—Mo4 | 73.27 (7) | H12D—C12B—H12F | 109.5 |
O2ii—Na1—Mo4 | 106.73 (7) | H12E—C12B—H12F | 109.5 |
Mo4ii—Na1—Mo4 | 180.0 | C15—N7—C14 | 106.9 (17) |
O3—Na1—Mo1ii | 138.33 (7) | C15—N7—H7 | 126.6 |
O3ii—Na1—Mo1ii | 41.67 (7) | C14—N7—H7 | 126.6 |
O13ii—Na1—Mo1ii | 72.95 (8) | C14—C13—N8 | 106.3 (12) |
O13—Na1—Mo1ii | 107.05 (8) | C14—C13—H13 | 126.9 |
O2—Na1—Mo1ii | 151.01 (7) | N8—C13—H13 | 126.9 |
O2ii—Na1—Mo1ii | 28.99 (7) | C13—C14—N7 | 109.1 (19) |
Mo4ii—Na1—Mo1ii | 57.601 (15) | C13—C14—H14 | 125.4 |
Mo4—Na1—Mo1ii | 122.397 (15) | N7—C14—H14 | 125.4 |
O3—Na1—Mo1 | 41.67 (7) | C15—N8—C13 | 109.5 (13) |
O3ii—Na1—Mo1 | 138.33 (7) | C15—N8—C16 | 123.7 (17) |
O13ii—Na1—Mo1 | 107.05 (8) | C13—N8—C16 | 126.8 (13) |
O13—Na1—Mo1 | 72.95 (8) | N8—C15—N7 | 108.2 (15) |
O2—Na1—Mo1 | 29.00 (7) | N8—C15—H15 | 125.9 |
O2ii—Na1—Mo1 | 151.01 (7) | N7—C15—H15 | 125.9 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C4H7N2)3[NaMo8O26(C4H6N2)2] |
Mr | 1784.29 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 11.692 (2), 10.298 (2), 22.190 (4) |
β (°) | 100.12 (3) |
V (Å3) | 2630.2 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.95 |
Crystal size (mm) | 0.4 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Stoe IPDS II diffractometer |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 1999) |
Tmin, Tmax | 0.393, 0.528 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22631, 7219, 5717 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.694 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.095, 0.97 |
No. of reflections | 7219 |
No. of parameters | 378 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.11, −0.96 |
Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2009).
Polyoxometalates (POMs) are of particular interest because of their fascinating structures, properties and potential applications, such as catalysis, sorption and magnetism (Müller & Pope, 1991; Cheetham, 1994; Proust et al., 2008). The class of materials is characterized by complex building units and a diverse chemical reactivity (Heyns et al., 1991; Wang et al., 1992). Molybdate-based POMs in particular have attracted a lot of attention since some of the largest inorganic clusters have been identified here, for instance, Na48[HxMo368O1032(H2O)240(SO4)48].xH2O with x ≈ 1000 (Müller et al., 2002). The fundamental building unit is quite often related to the well known octamolybdate [Mo8O26]4-. With this study, we report a novel chain-like ∞1[NaMo8O26(mim)2]3- anion (mim = 1-methylimidazole) that is constituted of sodium-interlinked [Mo8O26(mim)2]4- building units. Although, alkali-metal-interlinked chains of octamolybdate units have already been identified (McCann et al., 1994; Jia et al., 1999; Chen et al., 2005; Liu et al., 2006; Yu et al., 2008; Kobayashi et al., 2009), the title compound, (I), when examined in detail shows some significant structural differences.
According to single-crystal structure analysis, (Hmim)3[NaMo8O26(mim)2] contains the chain-like anion ∞1[NaMo8O26(mim)2]3-, which is oriented in parallel to the crystallographic b axis. The molybdate unit exhibits a center of inversion, resulting in only four crystallographically independent Mo sites. Between the chains, protonated methylimidazole is incorporated as the cation (Fig. 1). In detail, the ∞1[NaMo8O26(mim)2]3- ion is constituted of eight edge-sharing octahedra. The resulting [Mo8O26(mim)2]4- units are interlinked by sodium cations to form infinite chains. Here, sodium possesses sixfold coordination to the terminal O atoms of two molybdate units (Fig. 2). ∞1[NaMo8O26(mim)2]3- – or ∞1[NaMo8O26(Nmim)2]3- when only considering the coordinating N atom – can be compared, firstly, to the well known ∞1[NaMo8O26]3- building unit (McCann et al., 1994; Chen et al., 2005; Liu et al., 2006; Kobayashi et al., 2009) and, secondly, to [Mo8O28]8-. Both ∞1[NaMo8O26(Nmim)2]3- and ∞1[NaMo8O26]3- exhibit a chain-like interlinking of octamolybdate units via Na atoms (Fig. 3). However, because of to the different stoichiometry, the (MoO6) octahedra in ∞1[NaMo8O26]3- show a higher degree of condensation. Moreover, the coordination between the octamolybdate units and sodium is different. This holds for the coordination number (sixfold and eightfold) as well as for the relative orientation of the octamolybdate unit inside the ∞1[NaMo8O26(Nmim)2]3- and ∞1[NaMo8O26]3- chains. [Mo8O28]8-, which is also comparable to [Mo8O26(Nmim)2]4- in the title compound, has been identified both in layer-type structures with a direct Mo—O—Mo interlinking between the octamolybdate units (Evain et al., 2006) and as an individual octamolybdate unit that is interlinked via hydrogen-bridge bonding only (Bharadwaj et al., 1986; You et al., 1989).
Regarding their coordination, the O atoms in ∞1[NaMo8O26(mim)2]3- can be divided into six categories. First of all, one group of atoms is exclusively coordinated to molybdenum: ten terminal O atoms with bond distances (Mo—Oµ1) ranging from 1.698 (1) to 1.722 (3) Å; six atoms with twofold coordination and distances (Mo—Oµ2) of 1.742 (7)–2.271 (5) Å; two three-coordinated atoms with Mo—Oµ3 = 1.945 (4) Å; and finally two four-coordinated atoms with Mo—Oµ4 = 2.236 (3) Å. In the second group, the O atoms are coordinated to sodium as well as to molybdenum. Here, the 〈Na—O〉 distances average 2.377 (2) Å and the 〈Mo—ONa〉 distances 1.909 (3) Å. All these distances as well as the variation with increasing coordination number are in aggreement with literature data (Evain et al., 2006; Bharadwaj et al., 1986; You et al., 1989). Finally, two Mo atoms are coordinated by 1-methylimidazole, resulting in an Mo—N bond length of 2.229 (9) Å, which is also in accordance with the literature (2.2–2.5 Å; Cotton & Ilsey, 1972; Brisdon & Woolf, 1978; Schrauzer et al., 1982). On the basis of the composition of the compound as well as with regard to coordination and bond distances, all Mo atoms exhibit an oxidation state of +6.