supplementary materials
Tetraimidazolium bis(imidazole-![[kappa]](/logos/entities/kappa_rmgif.gif)
N)di-![[mu]](/logos/entities/mu_rmgif.gif)
4-oxido-tetra-3-oxido-hexa-2-oxido-tetradecaoxidooctamolybdate(VI) monohydrate
The anion of the title salt, (C3H5N2)4[Mo8O26(C3H4N2)2]·H2O, is a centrosymmetric Mo8O26 species in which two Mo atoms are each coordinated by an imidazole heterocycle. The anion is made up of two MoNO5 and six MoO6 edge-sharing octahedra. The cations interact with the tetraanion to give rise to a three-dimensional hydrogen-bonded network. The asymmetric unit features three cations, two of which lie on centers of inversion; the solvent water molecule is disordered with respect to one of these two cations.
Sodium molybdate dihydrate, Na2MoO4.2H2O (0.65 g, 2.7 mmol) and ammonium
acetate (0.15 g, 2 mmol) were dissolved in 30 ml water. Imidazole (0.10 g, 1.5 mmol) was added and the pH of the mixture adjusted to about 3.8 by the
addition of acetic acid. The solution was heated at 333 K for about 12 h. It
was then set aside for the growth of faint yellow crystals.
Two imidazolium cations are disordered about centers-of-inversion. For these two
five-membered rings, the 1,2-related distances were restrained to 1.35±0.01 Å and the 1,3-related ones to 2.18±0.01 Å. The rings were also restrained
to be almost planar. The rings are necessarily of half-occupancy only; one of
the rings is also disordered with respect to a water molecule. (The presence
of water in the compound was confirmed by an infrared spectrum.) The O1w atom
occupies the same position as the N5 atom of the ring; the temperature factors
of the two atoms were restrained to be identical. Additionally, the
anisotropic displacement parameters of all disordered atoms were restrained to
be nearly isotropic.
The carbon- and nitrogen-boud hydrogen atoms were placed at calculated
positions (C–H 0.95 and N–H 0.86 Å), and were included in the refinement
in the riding model approximation, with U(H) set to 1.2 times
Ueq(C,N). The hydrogen atoms of the half-occupancy water
molecule were placed in chemically sensible positions on the basis of hydrogen
bonds but were not refined; their temperature factors were set to 1.5 times
Ueq(O).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
Tetraimidazolium
bis(imidazole-
κN)di-µ
4-oxido-tetra-µ
3-oxido-hexa-µ
2-oxido-\
tetradecaoxido-octamolybdate(VI) monohydrate
top
Crystal data top
| (C3H5N2)4[Mo8O26(C3H4N2)2]·H2O | Z = 1 |
| Mr = 1614.06 | F(000) = 774 |
| Triclinic, P1 | Dx = 2.631 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.9723 (6) Å | Cell parameters from 6997 reflections |
| b = 10.9891 (7) Å | θ = 2.6–26.1° |
| c = 11.0273 (7) Å | µ = 2.49 mm−1 |
| α = 73.411 (1)° | T = 295 K |
| β = 68.510 (1)° | Block, yellow |
| γ = 66.702 (1)° | 0.32 × 0.20 × 0.18 mm |
| V = 1018.7 (1) Å3 | |
Data collection top
Bruker APEXII area-detector
diffractometer | 4001 independent reflections |
| Radiation source: fine-focus sealed tube | 3818 reflections with I > 2σ(I) |
| graphite | Rint = 0.019 |
| φ and ω scans | θmax = 26.1°, θmin = 2.6° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −12→12 |
| Tmin = 0.509, Tmax = 0.663 | k = −13→13 |
| 8712 measured reflections | l = −13→13 |
Refinement top
| 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)] = 0.019 | H-atom parameters constrained |
| wR(F2) = 0.050 | w = 1/[σ2(Fo2) + (0.0244P)2 + 1.3243P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max = 0.001 |
| 4001 reflections | Δρmax = 0.56 e Å−3 |
| 335 parameters | Δρmin = −0.53 e Å−3 |
| 84 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0115 (4) |
Crystal data top
| (C3H5N2)4[Mo8O26(C3H4N2)2]·H2O | γ = 66.702 (1)° |
| Mr = 1614.06 | V = 1018.7 (1) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 9.9723 (6) Å | Mo Kα radiation |
| b = 10.9891 (7) Å | µ = 2.49 mm−1 |
| c = 11.0273 (7) Å | T = 295 K |
| α = 73.411 (1)° | 0.32 × 0.20 × 0.18 mm |
| β = 68.510 (1)° | |
Data collection top
Bruker APEXII area-detector
diffractometer | 4001 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 3818 reflections with I > 2σ(I) |
| Tmin = 0.509, Tmax = 0.663 | Rint = 0.019 |
| 8712 measured reflections | θmax = 26.1° |
Refinement top
| R[F2 > 2σ(F2)] = 0.019 | H-atom parameters constrained |
| wR(F2) = 0.050 | Δρmax = 0.56 e Å−3 |
| S = 1.03 | Δρmin = −0.53 e Å−3 |
| 4001 reflections | Absolute structure: ? |
| 335 parameters | Flack parameter: ? |
| 84 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | Occ. (<1) |
| Mo1 | 0.66852 (3) | 0.39691 (3) | 0.78701 (2) | 0.02253 (8) | |
| Mo2 | 0.68776 (3) | 0.69805 (2) | 0.70065 (2) | 0.02160 (8) | |
| Mo3 | 0.90982 (3) | 0.78651 (2) | 0.41399 (2) | 0.02006 (7) | |
| Mo4 | 0.85357 (2) | 0.48189 (2) | 0.46941 (2) | 0.01675 (7) | |
| O1 | 0.7212 (3) | 0.2601 (2) | 0.9016 (2) | 0.0378 (5) | |
| O2 | 0.4752 (2) | 0.4615 (3) | 0.8447 (2) | 0.0391 (5) | |
| O3 | 0.7318 (2) | 0.5242 (2) | 0.81780 (19) | 0.0260 (4) | |
| O4 | 0.6743 (2) | 0.54871 (19) | 0.60330 (18) | 0.0202 (4) | |
| O5 | 0.4939 (2) | 0.7582 (2) | 0.7651 (2) | 0.0347 (5) | |
| O6 | 0.7564 (3) | 0.7744 (2) | 0.7672 (2) | 0.0344 (5) | |
| O7 | 0.7015 (2) | 0.80454 (19) | 0.52633 (19) | 0.0226 (4) | |
| O8 | 0.9465 (2) | 0.8797 (2) | 0.4910 (2) | 0.0306 (5) | |
| O9 | 0.8773 (3) | 0.8888 (2) | 0.2709 (2) | 0.0339 (5) | |
| O10 | 0.8527 (2) | 0.62994 (19) | 0.35338 (19) | 0.0229 (4) | |
| O11 | 1.1133 (2) | 0.66457 (19) | 0.35825 (18) | 0.0213 (4) | |
| O12 | 1.0724 (2) | 0.39639 (18) | 0.43058 (18) | 0.0195 (4) | |
| O13 | 0.8008 (2) | 0.3943 (2) | 0.4009 (2) | 0.0262 (4) | |
| O1w | 0.3555 (4) | 1.0254 (4) | 0.8580 (3) | 0.0679 (9) | 0.50 |
| H1w1 | 0.3986 | 0.9668 | 0.8068 | 0.102* | 0.50 |
| H1w2 | 0.2719 | 1.0777 | 0.8417 | 0.102* | 0.50 |
| N1 | 0.6259 (3) | 0.2831 (2) | 0.6778 (2) | 0.0260 (5) | |
| N2 | 0.5113 (3) | 0.2301 (3) | 0.5761 (3) | 0.0368 (6) | |
| H2n | 0.4468 | 0.2366 | 0.5392 | 0.044* | |
| N3 | 0.1740 (3) | 0.7977 (3) | 0.8697 (3) | 0.0374 (6) | |
| H3n | 0.2508 | 0.7723 | 0.8983 | 0.045* | |
| N4 | 0.0393 (3) | 0.8412 (3) | 0.7417 (3) | 0.0415 (7) | |
| H4n | 0.0137 | 0.8491 | 0.6736 | 0.050* | |
| C1 | 0.7039 (3) | 0.1532 (3) | 0.6544 (3) | 0.0318 (7) | |
| H1 | 0.7924 | 0.0974 | 0.6771 | 0.038* | |
| C2 | 0.6319 (4) | 0.1197 (3) | 0.5934 (3) | 0.0348 (7) | |
| H2 | 0.6593 | 0.0372 | 0.5682 | 0.042* | |
| C3 | 0.5111 (4) | 0.3266 (3) | 0.6266 (4) | 0.0359 (7) | |
| H3 | 0.4401 | 0.4126 | 0.6260 | 0.043* | |
| C4 | 0.0271 (4) | 0.8470 (4) | 0.9408 (3) | 0.0416 (8) | |
| H4 | −0.0082 | 0.8596 | 1.0284 | 0.050* | |
| C5 | −0.0579 (4) | 0.8742 (4) | 0.8598 (4) | 0.0424 (8) | |
| H5 | −0.1636 | 0.9091 | 0.8810 | 0.051* | |
| C6 | 0.1799 (4) | 0.7951 (4) | 0.7497 (4) | 0.0424 (8) | |
| H6 | 0.2679 | 0.7657 | 0.6821 | 0.051* | |
| N5 | 0.3555 (4) | 1.0254 (4) | 0.8580 (3) | 0.0679 (9) | 0.50 |
| H5n | 0.3196 | 0.9993 | 0.8148 | 0.081* | 0.50 |
| N6 | 0.4811 (8) | 1.0259 (7) | 0.9896 (8) | 0.041 (2) | 0.50 |
| H6n | 0.5364 | 0.9982 | 1.0414 | 0.049* | 0.50 |
| C7 | 0.3365 (6) | 1.1560 (6) | 0.8651 (5) | 0.0470 (18) | 0.50 |
| H7 | 0.2792 | 1.2331 | 0.8211 | 0.056* | 0.50 |
| C8 | 0.4124 (7) | 1.1557 (6) | 0.9444 (6) | 0.0411 (16) | 0.50 |
| H8 | 0.4167 | 1.2306 | 0.9642 | 0.049* | 0.50 |
| C9 | 0.4474 (7) | 0.9492 (6) | 0.9394 (6) | 0.0488 (18) | 0.50 |
| H9 | 0.4814 | 0.8558 | 0.9567 | 0.059* | 0.50 |
| N7 | 0.9672 (17) | 0.4876 (9) | 0.9137 (14) | 0.050 (3) | 0.50 |
| H7n | 0.9340 | 0.4812 | 0.8557 | 0.060* | 0.50 |
| N8 | 1.1196 (12) | 0.4892 (9) | 1.0082 (13) | 0.039 (2) | 0.50 |
| H8n | 1.2000 | 0.4842 | 1.0223 | 0.047* | 0.50 |
| C10 | 0.8828 (10) | 0.5156 (13) | 1.0355 (17) | 0.056 (4) | 0.50 |
| H10 | 0.7784 | 0.5313 | 1.0716 | 0.067* | 0.50 |
| C11 | 0.978 (2) | 0.5166 (13) | 1.0951 (8) | 0.056 (4) | 0.50 |
| H11 | 0.9520 | 0.5331 | 1.1804 | 0.067* | 0.50 |
| C12 | 1.1117 (12) | 0.4716 (7) | 0.8992 (9) | 0.053 (2) | 0.50 |
| H12 | 1.1931 | 0.4514 | 0.8240 | 0.064* | 0.50 |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Mo1 | 0.01925 (13) | 0.03160 (14) | 0.02000 (13) | −0.01112 (10) | −0.00580 (9) | −0.00471 (10) |
| Mo2 | 0.01642 (12) | 0.02691 (14) | 0.02408 (13) | −0.00400 (9) | −0.00577 (9) | −0.01252 (10) |
| Mo3 | 0.01810 (12) | 0.01817 (13) | 0.02476 (13) | −0.00365 (9) | −0.00905 (9) | −0.00422 (9) |
| Mo4 | 0.01450 (12) | 0.01969 (12) | 0.01785 (12) | −0.00303 (9) | −0.00688 (9) | −0.00644 (9) |
| O1 | 0.0425 (13) | 0.0477 (14) | 0.0291 (11) | −0.0227 (11) | −0.0158 (10) | 0.0037 (10) |
| O2 | 0.0244 (11) | 0.0538 (15) | 0.0419 (13) | −0.0139 (10) | −0.0021 (10) | −0.0201 (11) |
| O3 | 0.0255 (10) | 0.0355 (11) | 0.0226 (10) | −0.0108 (9) | −0.0097 (8) | −0.0082 (8) |
| O4 | 0.0154 (9) | 0.0242 (10) | 0.0222 (9) | −0.0034 (7) | −0.0066 (7) | −0.0083 (8) |
| O5 | 0.0207 (10) | 0.0409 (13) | 0.0418 (13) | −0.0046 (9) | −0.0047 (9) | −0.0190 (10) |
| O6 | 0.0366 (12) | 0.0411 (13) | 0.0371 (12) | −0.0132 (10) | −0.0143 (10) | −0.0175 (10) |
| O7 | 0.0172 (9) | 0.0214 (10) | 0.0291 (10) | −0.0010 (7) | −0.0102 (8) | −0.0069 (8) |
| O8 | 0.0271 (11) | 0.0294 (11) | 0.0406 (12) | −0.0084 (9) | −0.0106 (9) | −0.0133 (9) |
| O9 | 0.0367 (12) | 0.0287 (11) | 0.0356 (12) | −0.0091 (9) | −0.0180 (10) | 0.0035 (9) |
| O10 | 0.0234 (10) | 0.0236 (10) | 0.0233 (10) | −0.0050 (8) | −0.0100 (8) | −0.0055 (8) |
| O11 | 0.0181 (9) | 0.0243 (10) | 0.0214 (9) | −0.0056 (8) | −0.0069 (7) | −0.0038 (8) |
| O12 | 0.0157 (9) | 0.0218 (9) | 0.0208 (9) | −0.0029 (7) | −0.0061 (7) | −0.0070 (7) |
| O13 | 0.0267 (10) | 0.0281 (11) | 0.0299 (11) | −0.0073 (8) | −0.0120 (8) | −0.0110 (8) |
| O1w | 0.0488 (19) | 0.081 (3) | 0.068 (2) | −0.0181 (17) | −0.0152 (16) | −0.0111 (19) |
| N1 | 0.0218 (12) | 0.0279 (13) | 0.0307 (13) | −0.0075 (10) | −0.0113 (10) | −0.0047 (10) |
| N2 | 0.0321 (14) | 0.0407 (16) | 0.0495 (17) | −0.0065 (12) | −0.0253 (13) | −0.0146 (13) |
| N3 | 0.0322 (14) | 0.0409 (16) | 0.0471 (17) | −0.0132 (12) | −0.0201 (13) | −0.0052 (13) |
| N4 | 0.0448 (17) | 0.0482 (17) | 0.0431 (17) | −0.0137 (14) | −0.0205 (14) | −0.0161 (14) |
| C1 | 0.0243 (15) | 0.0256 (15) | 0.0468 (19) | −0.0036 (12) | −0.0169 (14) | −0.0055 (13) |
| C2 | 0.0321 (16) | 0.0300 (16) | 0.0441 (19) | −0.0080 (13) | −0.0101 (14) | −0.0132 (14) |
| C3 | 0.0298 (16) | 0.0322 (17) | 0.052 (2) | −0.0018 (13) | −0.0240 (15) | −0.0125 (15) |
| C4 | 0.045 (2) | 0.053 (2) | 0.0300 (17) | −0.0220 (17) | −0.0085 (15) | −0.0072 (15) |
| C5 | 0.0315 (17) | 0.050 (2) | 0.050 (2) | −0.0112 (15) | −0.0137 (15) | −0.0144 (17) |
| C6 | 0.0357 (18) | 0.048 (2) | 0.048 (2) | −0.0140 (16) | −0.0065 (16) | −0.0211 (17) |
| N5 | 0.0488 (19) | 0.081 (3) | 0.068 (2) | −0.0181 (17) | −0.0152 (16) | −0.0111 (19) |
| N6 | 0.031 (4) | 0.061 (6) | 0.031 (3) | −0.016 (4) | −0.014 (3) | 0.000 (4) |
| C7 | 0.034 (3) | 0.058 (4) | 0.036 (4) | −0.013 (3) | −0.004 (3) | 0.001 (3) |
| C8 | 0.042 (4) | 0.043 (4) | 0.037 (3) | −0.020 (3) | 0.000 (3) | −0.009 (3) |
| C9 | 0.050 (4) | 0.043 (4) | 0.049 (4) | −0.023 (3) | 0.005 (3) | −0.017 (3) |
| N7 | 0.044 (5) | 0.071 (5) | 0.055 (6) | −0.024 (5) | −0.033 (5) | −0.006 (4) |
| N8 | 0.046 (5) | 0.050 (4) | 0.037 (5) | −0.021 (3) | −0.025 (4) | −0.006 (4) |
| C10 | 0.047 (5) | 0.073 (6) | 0.050 (8) | −0.030 (5) | 0.004 (5) | −0.021 (6) |
| C11 | 0.051 (8) | 0.092 (7) | 0.030 (4) | −0.025 (6) | −0.010 (5) | −0.016 (4) |
| C12 | 0.045 (5) | 0.087 (6) | 0.034 (5) | −0.025 (4) | −0.014 (4) | −0.012 (4) |
Geometric parameters (Å, °) top
| Mo1—O1 | 1.706 (2) | N3—C4 | 1.352 (5) |
| Mo1—O2 | 1.704 (2) | N3—H3n | 0.8500 |
| Mo1—O3 | 1.896 (2) | N4—C6 | 1.317 (5) |
| Mo1—O4 | 2.225 (2) | N4—C5 | 1.355 (5) |
| Mo1—O11i | 2.158 (2) | N4—H4n | 0.8500 |
| Mo1—N1 | 2.203 (2) | C1—C2 | 1.344 (4) |
| Mo2—O3 | 1.964 (2) | C1—H1 | 0.9300 |
| Mo2—O4 | 2.269 (2) | C2—H2 | 0.9300 |
| Mo2—O5 | 1.711 (2) | C3—H3 | 0.9300 |
| Mo2—O6 | 1.699 (2) | C4—C5 | 1.344 (5) |
| Mo2—O7 | 1.932 (2) | C4—H4 | 0.9300 |
| Mo2—O12i | 2.292 (2) | C5—H5 | 0.9300 |
| Mo3—O7 | 1.954 (2) | C6—H6 | 0.9300 |
| Mo3—O8 | 1.710 (2) | N6—C9 | 1.326 (8) |
| Mo3—O9 | 1.713 (2) | N6—C8 | 1.350 (7) |
| Mo3—O10 | 2.333 (2) | N6—H6n | 0.8500 |
| Mo3—O11 | 1.923 (2) | C7—C8 | 1.348 (7) |
| Mo3—O12i | 2.232 (2) | C7—H1w2 | 1.383 (7) |
| Mo4—O4 | 1.887 (2) | C7—H7 | 0.9300 |
| Mo4—O10 | 1.759 (2) | C8—H8 | 0.9300 |
| Mo4—O13 | 1.697 (2) | C9—H9 | 0.9300 |
| Mo4—O11i | 2.146 (2) | N7—C12 | 1.334 (8) |
| Mo4—O12 | 1.937 (2) | N7—C10 | 1.346 (8) |
| Mo4—O12i | 2.402 (2) | N7—H7n | 0.8500 |
| O1w—H1w1 | 0.85 | N8—C12 | 1.304 (10) |
| O1w—H1w2 | 0.85 | N8—C11 | 1.355 (7) |
| N1—C3 | 1.320 (4) | N8—H8n | 0.8500 |
| N1—C1 | 1.377 (4) | C10—C11 | 1.345 (8) |
| N2—C3 | 1.331 (4) | C10—H10 | 0.9300 |
| N2—C2 | 1.355 (4) | C11—H11 | 0.9300 |
| N2—H2n | 0.8500 | C12—H12 | 0.9300 |
| N3—C6 | 1.311 (4) | | |
| | | |
| O2—Mo1—O1 | 105.35 (12) | Mo3—O11—Mo4i | 105.25 (8) |
| O2—Mo1—O3 | 101.92 (10) | Mo3—O11—Mo1i | 151.90 (10) |
| O1—Mo1—O3 | 102.68 (10) | Mo4i—O11—Mo1i | 102.74 (8) |
| O2—Mo1—O11i | 156.67 (10) | Mo4—O12—Mo3i | 101.61 (8) |
| O1—Mo1—O11i | 92.44 (10) | Mo4—O12—Mo2i | 154.72 (10) |
| O3—Mo1—O11i | 88.40 (8) | Mo3i—O12—Mo2i | 92.40 (7) |
| O2—Mo1—N1 | 85.71 (10) | Mo4—O12—Mo4i | 103.28 (8) |
| O1—Mo1—N1 | 93.59 (10) | Mo3i—O12—Mo4i | 96.46 (7) |
| O3—Mo1—N1 | 159.31 (9) | Mo2i—O12—Mo4i | 95.84 (6) |
| O11i—Mo1—N1 | 78.10 (8) | H1w1—O1w—H1w2 | 108.5 |
| O2—Mo1—O4 | 92.04 (10) | C3—N1—C1 | 105.7 (3) |
| O1—Mo1—O4 | 162.36 (9) | C3—N1—Mo1 | 125.4 (2) |
| O3—Mo1—O4 | 75.99 (8) | C1—N1—Mo1 | 128.82 (19) |
| O11i—Mo1—O4 | 69.99 (7) | C3—N2—C2 | 108.3 (3) |
| N1—Mo1—O4 | 84.62 (8) | C3—N2—H2n | 125.8 |
| O6—Mo2—O5 | 104.82 (11) | C2—N2—H2n | 125.8 |
| O6—Mo2—O7 | 101.14 (10) | C6—N3—C4 | 109.6 (3) |
| O5—Mo2—O7 | 97.72 (10) | C6—N3—H3n | 125.2 |
| O6—Mo2—O3 | 96.44 (10) | C4—N3—H3n | 125.2 |
| O5—Mo2—O3 | 99.64 (10) | C6—N4—C5 | 108.7 (3) |
| O7—Mo2—O3 | 151.18 (8) | C6—N4—H4n | 125.6 |
| O6—Mo2—O4 | 161.32 (9) | C5—N4—H4n | 125.6 |
| O5—Mo2—O4 | 92.62 (9) | C2—C1—N1 | 109.3 (3) |
| O7—Mo2—O4 | 82.71 (7) | C2—C1—H1 | 125.4 |
| O3—Mo2—O4 | 73.70 (7) | N1—C1—H1 | 125.4 |
| O6—Mo2—O12i | 90.97 (9) | C1—C2—N2 | 106.2 (3) |
| O5—Mo2—O12i | 163.23 (9) | C1—C2—H2 | 126.9 |
| O7—Mo2—O12i | 73.26 (7) | N2—C2—H2 | 126.9 |
| O3—Mo2—O12i | 83.85 (8) | N1—C3—N2 | 110.4 (3) |
| O4—Mo2—O12i | 72.49 (6) | N1—C3—H3 | 124.8 |
| O8—Mo3—O9 | 105.42 (11) | N2—C3—H3 | 124.8 |
| O8—Mo3—O11 | 98.40 (9) | C5—C4—N3 | 106.4 (3) |
| O9—Mo3—O11 | 104.31 (10) | C5—C4—H4 | 126.8 |
| O8—Mo3—O7 | 96.66 (9) | N3—C4—H4 | 126.8 |
| O9—Mo3—O7 | 101.11 (10) | C4—C5—N4 | 107.2 (3) |
| O11—Mo3—O7 | 145.67 (8) | C4—C5—H5 | 126.4 |
| O8—Mo3—O12i | 96.90 (9) | N4—C5—H5 | 126.4 |
| O9—Mo3—O12i | 157.63 (9) | N3—C6—N4 | 108.0 (3) |
| O11—Mo3—O12i | 73.43 (7) | N3—C6—H6 | 126.0 |
| O7—Mo3—O12i | 74.25 (7) | N4—C6—H6 | 126.0 |
| O8—Mo3—O10 | 167.65 (9) | C9—N6—C8 | 108.3 (5) |
| O9—Mo3—O10 | 86.49 (9) | C9—N6—H6n | 125.8 |
| O11—Mo3—O10 | 81.41 (7) | C8—N6—H6n | 125.8 |
| O7—Mo3—O10 | 77.49 (7) | C8—C7—H1w2 | 141.5 (5) |
| O12i—Mo3—O10 | 71.14 (7) | C8—C7—H7 | 124.6 |
| O13—Mo4—O10 | 103.16 (9) | H1w2—C7—H7 | 91.4 |
| O13—Mo4—O4 | 102.77 (9) | C7—C8—N6 | 107.0 (5) |
| O10—Mo4—O4 | 100.08 (9) | C7—C8—H8 | 126.5 |
| O13—Mo4—O12 | 103.31 (9) | N6—C8—H8 | 126.5 |
| O10—Mo4—O12 | 97.93 (8) | N6—C9—H9 | 124.3 |
| O4—Mo4—O12 | 143.81 (8) | C12—N7—C10 | 108.6 (6) |
| O13—Mo4—O11i | 97.64 (9) | C12—N7—H7n | 125.7 |
| O10—Mo4—O11i | 159.11 (8) | C10—N7—H7n | 125.7 |
| O4—Mo4—O11i | 76.84 (8) | C12—N8—C11 | 108.6 (5) |
| O12—Mo4—O11i | 75.20 (8) | C12—N8—H8n | 125.7 |
| O13—Mo4—O12i | 179.16 (8) | C11—N8—H8n | 125.7 |
| O10—Mo4—O12i | 77.66 (7) | C11—C10—N7 | 106.9 (5) |
| O4—Mo4—O12i | 76.85 (7) | C11—C10—H10 | 126.6 |
| O12—Mo4—O12i | 76.72 (8) | N7—C10—H10 | 126.6 |
| O11i—Mo4—O12i | 81.54 (7) | C10—C11—N8 | 107.5 (5) |
| Mo1—O3—Mo2 | 113.87 (9) | C10—C11—H11 | 126.3 |
| Mo4—O4—Mo1 | 109.41 (8) | N8—C11—H11 | 126.3 |
| Mo4—O4—Mo2 | 113.61 (8) | N8—C12—N7 | 108.5 (6) |
| Mo1—O4—Mo2 | 92.07 (7) | N8—C12—H12 | 125.8 |
| Mo2—O7—Mo3 | 114.32 (9) | N7—C12—H12 | 125.8 |
| Mo4—O10—Mo3 | 114.67 (9) | | |
| | | |
| O2—Mo1—O3—Mo2 | −70.97 (13) | O11—Mo3—O10—Mo4 | 77.92 (10) |
| O1—Mo1—O3—Mo2 | −179.92 (11) | O7—Mo3—O10—Mo4 | −74.82 (10) |
| O11i—Mo1—O3—Mo2 | 87.93 (10) | O12i—Mo3—O10—Mo4 | 2.59 (9) |
| N1—Mo1—O3—Mo2 | 39.0 (3) | O8—Mo3—O11—Mo4i | 79.29 (10) |
| O4—Mo1—O3—Mo2 | 18.16 (9) | O9—Mo3—O11—Mo4i | −172.35 (9) |
| O6—Mo2—O3—Mo1 | 178.21 (11) | O7—Mo3—O11—Mo4i | −35.79 (17) |
| O5—Mo2—O3—Mo1 | 71.93 (12) | O12i—Mo3—O11—Mo4i | −15.45 (7) |
| O7—Mo2—O3—Mo1 | −54.3 (2) | O10—Mo3—O11—Mo4i | −88.22 (8) |
| O4—Mo2—O3—Mo1 | −18.00 (9) | O8—Mo3—O11—Mo1i | −95.6 (2) |
| O12i—Mo2—O3—Mo1 | −91.51 (10) | O9—Mo3—O11—Mo1i | 12.7 (2) |
| O13—Mo4—O4—Mo1 | 87.02 (10) | O7—Mo3—O11—Mo1i | 149.31 (18) |
| O10—Mo4—O4—Mo1 | −166.87 (8) | O12i—Mo3—O11—Mo1i | 169.6 (2) |
| O12—Mo4—O4—Mo1 | −48.16 (17) | O10—Mo3—O11—Mo1i | 96.9 (2) |
| O11i—Mo4—O4—Mo1 | −7.97 (7) | O13—Mo4—O12—Mo3i | −79.55 (10) |
| O12i—Mo4—O4—Mo1 | −92.20 (8) | O10—Mo4—O12—Mo3i | 174.83 (8) |
| O13—Mo4—O4—Mo2 | −171.69 (9) | O4—Mo4—O12—Mo3i | 55.51 (16) |
| O10—Mo4—O4—Mo2 | −65.58 (10) | O11i—Mo4—O12—Mo3i | 14.97 (7) |
| O12—Mo4—O4—Mo2 | 53.13 (17) | O12i—Mo4—O12—Mo3i | 99.58 (9) |
| O11i—Mo4—O4—Mo2 | 93.32 (9) | O13—Mo4—O12—Mo2i | 42.8 (2) |
| O12i—Mo4—O4—Mo2 | 9.08 (8) | O10—Mo4—O12—Mo2i | −62.8 (2) |
| O2—Mo1—O4—Mo4 | −156.55 (11) | O4—Mo4—O12—Mo2i | 177.84 (17) |
| O1—Mo1—O4—Mo4 | 13.9 (3) | O11i—Mo4—O12—Mo2i | 137.3 (2) |
| O3—Mo1—O4—Mo4 | 101.67 (10) | O12i—Mo4—O12—Mo2i | −138.1 (3) |
| O11i—Mo1—O4—Mo4 | 8.21 (8) | O13—Mo4—O12—Mo4i | −179.13 (9) |
| N1—Mo1—O4—Mo4 | −71.06 (10) | O10—Mo4—O12—Mo4i | 75.25 (9) |
| O2—Mo1—O4—Mo2 | 87.49 (9) | O4—Mo4—O12—Mo4i | −44.07 (16) |
| O1—Mo1—O4—Mo2 | −102.1 (3) | O11i—Mo4—O12—Mo4i | −84.61 (8) |
| O3—Mo1—O4—Mo2 | −14.29 (7) | O12i—Mo4—O12—Mo4i | 0.0 |
| O11i—Mo1—O4—Mo2 | −107.74 (8) | O2—Mo1—N1—C3 | 34.4 (3) |
| N1—Mo1—O4—Mo2 | 172.98 (8) | O1—Mo1—N1—C3 | 139.6 (3) |
| O6—Mo2—O4—Mo4 | −38.3 (3) | O3—Mo1—N1—C3 | −78.3 (4) |
| O5—Mo2—O4—Mo4 | 162.41 (11) | O11i—Mo1—N1—C3 | −128.7 (3) |
| O7—Mo2—O4—Mo4 | 64.96 (10) | O4—Mo1—N1—C3 | −58.0 (3) |
| O3—Mo2—O4—Mo4 | −98.31 (10) | O2—Mo1—N1—C1 | −141.6 (3) |
| O12i—Mo2—O4—Mo4 | −9.73 (8) | O1—Mo1—N1—C1 | −36.5 (3) |
| O6—Mo2—O4—Mo1 | 73.9 (3) | O3—Mo1—N1—C1 | 105.6 (3) |
| O5—Mo2—O4—Mo1 | −85.34 (9) | O11i—Mo1—N1—C1 | 55.3 (3) |
| O7—Mo2—O4—Mo1 | 177.21 (7) | O4—Mo1—N1—C1 | 125.9 (3) |
| O3—Mo2—O4—Mo1 | 13.94 (7) | C3—N1—C1—C2 | −1.9 (4) |
| O12i—Mo2—O4—Mo1 | 102.52 (7) | Mo1—N1—C1—C2 | 174.7 (2) |
| O6—Mo2—O7—Mo3 | 67.07 (12) | N1—C1—C2—N2 | 1.5 (4) |
| O5—Mo2—O7—Mo3 | 173.91 (11) | C3—N2—C2—C1 | −0.5 (4) |
| O3—Mo2—O7—Mo3 | −59.4 (2) | C1—N1—C3—N2 | 1.6 (4) |
| O4—Mo2—O7—Mo3 | −94.41 (10) | Mo1—N1—C3—N2 | −175.2 (2) |
| O12i—Mo2—O7—Mo3 | −20.57 (9) | C2—N2—C3—N1 | −0.7 (4) |
| O8—Mo3—O7—Mo2 | −74.29 (12) | C6—N3—C4—C5 | 0.3 (4) |
| O9—Mo3—O7—Mo2 | 178.51 (11) | N3—C4—C5—N4 | −0.2 (4) |
| O11—Mo3—O7—Mo2 | 41.28 (19) | C6—N4—C5—C4 | 0.1 (4) |
| O12i—Mo3—O7—Mo2 | 21.03 (9) | C4—N3—C6—N4 | −0.3 (4) |
| O10—Mo3—O7—Mo2 | 94.68 (10) | C5—N4—C6—N3 | 0.1 (4) |
| O13—Mo4—O10—Mo3 | 177.47 (9) | C9—N6—C8—C7 | −0.2 (5) |
| O4—Mo4—O10—Mo3 | 71.68 (10) | C12—N7—C10—C11 | 0.1 (3) |
| O12—Mo4—O10—Mo3 | −76.79 (10) | N7—C10—C11—N8 | 0.0 (3) |
| O11i—Mo4—O10—Mo3 | −7.8 (3) | C12—N8—C11—C10 | −0.1 (5) |
| O12i—Mo4—O10—Mo3 | −2.33 (8) | C11—N8—C12—N7 | 0.2 (6) |
| O8—Mo3—O10—Mo4 | −12.1 (4) | C10—N7—C12—N8 | −0.2 (5) |
| O9—Mo3—O10—Mo4 | −177.03 (12) | | |
| Symmetry codes: (i) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2n···O7ii | 0.85 | 2.10 | 2.926 (3) | 164 |
| N3—H3n···O1iii | 0.85 | 2.24 | 2.889 (4) | 134 |
| N4—H4n···O8iv | 0.85 | 2.25 | 3.094 (4) | 178 |
| N5—H5n···O9v | 0.85 | 2.25 | 2.866 (4) | 130 |
| N6—H6n···O1wvi | 0.85 | 1.72 | 2.556 (7) | 169 |
| N7—H7n···O3 | 0.85 | 2.05 | 2.760 (9) | 140 |
| N8—H8n···O3vii | 0.85 | 2.08 | 2.766 (9) | 138 |
| O1w—H1w1···O5 | 0.85 | 2.22 | 3.010 (4) | 154 |
| O1w—H1w2···O9v | 0.85 | 2.13 | 2.866 (4) | 144 |
| Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) x−1, y, z; (v) −x+1, −y+2, −z+1; (vi) −x+1, −y+2, −z+2; (vii) −x+2, −y+1, −z+2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2n···O7i | 0.85 | 2.10 | 2.926 (3) | 164 |
| N3—H3n···O1ii | 0.85 | 2.24 | 2.889 (4) | 134 |
| N4—H4n···O8iii | 0.85 | 2.25 | 3.094 (4) | 178 |
| N5—H5n···O9iv | 0.85 | 2.25 | 2.866 (4) | 130 |
| N6—H6n···O1wv | 0.85 | 1.72 | 2.556 (7) | 169 |
| N7—H7n···O3 | 0.85 | 2.05 | 2.760 (9) | 140 |
| N8—H8n···O3vi | 0.85 | 2.08 | 2.766 (9) | 138 |
| O1w—H1w1···O5 | 0.85 | 2.22 | 3.010 (4) | 154 |
| O1w—H1w2···O9iv | 0.85 | 2.13 | 2.866 (4) | 144 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) x−1, y, z; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+2, −z+2; (vi) −x+2, −y+1, −z+2. |
The authors thank Jilin Normal University and the University of Malaya for
supporting this study.
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Bruker (2005). APEX2 (Version 1.22A) and SAINT (Version 7.12A). Bruker AXS Inc., Madison, Winconsin, USA.
Martían-Zarza, P., Arrieta, J. M., Muñoz-Roca, M. C. & Gili, P. (1993). J. Chem. Soc. Dalton Trans. pp. 1551–1557.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Westrip, S. P. (2007). publCIF. In preparation.
![[Figure 1]](./bt2468fig1thm.gif)
The tetraanion of the title salt, tetrakis(imidazolium) bis(imidazole)-octamolybdate monohydrate, was previously identified as tetrakis(dimethylammonium) bis(imidazole)-octamolybdate trihydrate (Martían-Zarza et al., 1993). The anion is made up of two MoNO5 and six MoO6 edge-sharing octahedra as two of the molybdenum atoms are coordinated by the neutral N-heterocycles. In the present salt, two of the three cations of the asymmetric unit are disordered over different centers-of-inversion. The cations and tetraanion interact through hydrogen bonds to give rise to a three-dimensional network.