Acta Cryst. (2008). E64, m41 [ doi:10.1107/S1600536807062897 ]
The title compound, (C8H8N5)2[Mo6O19], was prepared by reaction of Mo(CO)6 and dipyrimidylamine in refluxing toluene. The hexanuclear polyoxomolybdate anions lie on centres of inversion. Each 2-(pyrimidin-2-ylamino)pyrimidinium cation forms an intramolecular N-H
N hydrogen bond and the cations are linked through self-complementary pairs of N-HN hydrogen bonds into dimers across centres of inversion. The cations and anions are interlinked through C-HO contacts.
Mo(CO)6 (0.52 g, 2.00 mmol) was added to a solution of dipyrimidylamine (dipm) (0.34 g, 2.00 mmol) in 20 ml toluene. The mixture was refluxed for 18 h to yield an orange solution. The solvent was reduced and n-hexanes added to induce precipitation. The precipitate was filtered and washed by ether (3 × 10 ml) and then dried under reduced pressure to give an orange powder. The green plate crystals were obtained by slow diffusion of ether into a CH2Cl2 solution of the orange powder. The crystals were filtered and washed by ether (3 × 10 ml) and then dried under reduced pressure. Overall crystal yield: 0.207 g (8.43%, based on Mo). Elemental analysis calculated: C, 15.16%; H, 1.31%; N, 11.41%; found: C, 15.02%; H, 1.34%; N, 11.03%.
H atoms were placed geometrically with C—H = 0.93 Å and N—H = 0.86 Å, and refined as riding with Uiso(H) = Ueq(C/N).
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997.
![[Figure 1]](./bi2259fig1thm.gif)
| Fig. 1. The molecular structure of the title compound showing displacement ellipsoids at the 30% probability level for non-H atoms. |
![[Figure 2]](./bi2259fig2thm.gif)
| Fig. 2. Partial packing diagram showing N—H···N hydrogen bonding between Hdipm molecules and C—H···O contacts to the polyoxometalate. |
| (C8H8N5)2[Mo6O19] | F000 = 1172 |
| Mr = 1228.03 | Dx = 2.664 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 31 reflections |
| a = 10.4338 (19) Å | θ = 4.8–12.5º |
| b = 13.7437 (19) Å | µ = 2.48 mm−1 |
| c = 11.0792 (17) Å | T = 295 (2) K |
| β = 105.471 (13)º | Plate, green |
| V = 1531.2 (4) Å3 | 0.40 × 0.20 × 0.05 mm |
| Z = 2 |
| Bruker P4 diffractometer | Rint = 0.082 |
| Radiation source: fine-focus sealed tube | θmax = 25.0º |
| Monochromator: graphite | θmin = 2.4º |
| T = 295(2) K | h = −1→12 |
| ω scans | k = −1→16 |
| Absorption correction: ψ scan (North et al., 1968) | l = −13→12 |
| Tmin = 0.578, Tmax = 0.883 | 3 standard reflections |
| 3399 measured reflections | every 97 reflections |
| 2660 independent reflections | intensity decay: none |
| 1833 reflections with I > 2σ(I) |
| 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)] = 0.057 | H-atom parameters constrained |
| wR(F2) = 0.146 | w = 1/[σ2(Fo2) + (0.0858P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 2660 reflections | Δρmax = 0.91 e Å−3 |
| 232 parameters | Δρmin = −1.78 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| (C8H8N5)2[Mo6O19] | V = 1531.2 (4) Å3 |
| Mr = 1228.03 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 10.4338 (19) Å | µ = 2.48 mm−1 |
| b = 13.7437 (19) Å | T = 295 (2) K |
| c = 11.0792 (17) Å | 0.40 × 0.20 × 0.05 mm |
| β = 105.471 (13)º |
| Bruker P4 diffractometer | 1833 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.082 |
| Tmin = 0.578, Tmax = 0.883 | 3 standard reflections |
| 3399 measured reflections | every 97 reflections |
| 2660 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.057 | 232 parameters |
| wR(F2) = 0.146 | H-atom parameters constrained |
| S = 1.02 | Δρmax = 0.91 e Å−3 |
| 2660 reflections | Δρmin = −1.78 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 | 0.06601 (9) | 0.95848 (7) | 0.32376 (8) | 0.0380 (3) | |
| Mo2 | −0.15184 (9) | 0.87281 (7) | 0.46013 (9) | 0.0418 (3) | |
| Mo3 | 0.16049 (9) | 0.89727 (7) | 0.61876 (9) | 0.0434 (3) | |
| N1 | 0.4384 (8) | 0.9695 (6) | 0.3239 (8) | 0.040 (2) | |
| H1N | 0.4607 | 1.0166 | 0.3764 | 0.048* | |
| N2 | 0.4053 (10) | 1.0908 (7) | 0.1792 (9) | 0.052 (2) | |
| N3 | 0.3659 (9) | 0.9281 (7) | 0.1128 (8) | 0.043 (2) | |
| H3N | 0.3676 | 0.8676 | 0.1331 | 0.052* | |
| N4 | 0.4025 (9) | 0.8036 (6) | 0.2961 (9) | 0.046 (2) | |
| N5 | 0.4845 (8) | 0.8709 (6) | 0.4968 (9) | 0.040 (2) | |
| O1 | 0.1142 (7) | 0.9318 (7) | 0.1952 (7) | 0.065 (2) | |
| O2 | −0.2622 (8) | 0.7811 (6) | 0.4336 (9) | 0.072 (3) | |
| O3 | 0.2743 (9) | 0.8222 (7) | 0.7019 (9) | 0.076 (3) | |
| O4 | 0.0000 | 1.0000 | 0.5000 | 0.0286 (19) | |
| O5 | −0.0732 (7) | 0.8658 (5) | 0.3211 (7) | 0.052 (2) | |
| O6 | 0.1775 (7) | 1.0683 (5) | 0.3902 (7) | 0.0414 (17) | |
| O7 | 0.1797 (7) | 0.8825 (5) | 0.4514 (7) | 0.0446 (18) | |
| O8 | 0.0033 (7) | 0.8138 (5) | 0.5623 (8) | 0.056 (2) | |
| O9 | −0.0736 (7) | 1.0520 (6) | 0.2626 (6) | 0.052 (2) | |
| O10 | −0.2525 (6) | 0.9816 (6) | 0.3719 (6) | 0.0465 (19) | |
| C1 | 0.4034 (10) | 0.9955 (8) | 0.1993 (9) | 0.041 (3) | |
| C2 | 0.3673 (12) | 1.1171 (10) | 0.0578 (12) | 0.060 (3) | |
| H2 | 0.3699 | 1.1827 | 0.0376 | 0.072* | |
| C3 | 0.3249 (13) | 1.0509 (11) | −0.0372 (12) | 0.064 (4) | |
| H3 | 0.2968 | 1.0711 | −0.1202 | 0.077* | |
| C4 | 0.3252 (12) | 0.9553 (10) | −0.0069 (11) | 0.055 (3) | |
| H4 | 0.2971 | 0.9089 | −0.0694 | 0.066* | |
| C5 | 0.4425 (9) | 0.8789 (7) | 0.3750 (10) | 0.037 (2) | |
| C6 | 0.4060 (12) | 0.7135 (9) | 0.3495 (12) | 0.054 (3) | |
| H6 | 0.3774 | 0.6596 | 0.2987 | 0.064* | |
| C7 | 0.4491 (11) | 0.7019 (8) | 0.4714 (11) | 0.048 (3) | |
| H7 | 0.4537 | 0.6402 | 0.5068 | 0.057* | |
| C8 | 0.4876 (10) | 0.7831 (8) | 0.5462 (10) | 0.046 (3) | |
| H8 | 0.5161 | 0.7758 | 0.6327 | 0.055* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mo1 | 0.0374 (5) | 0.0496 (6) | 0.0324 (5) | −0.0021 (4) | 0.0188 (4) | −0.0061 (4) |
| Mo2 | 0.0393 (5) | 0.0414 (5) | 0.0508 (6) | −0.0114 (4) | 0.0228 (4) | −0.0095 (4) |
| Mo3 | 0.0400 (5) | 0.0502 (6) | 0.0424 (6) | 0.0122 (4) | 0.0151 (4) | 0.0098 (5) |
| N1 | 0.043 (5) | 0.041 (5) | 0.035 (5) | −0.002 (4) | 0.009 (4) | −0.005 (4) |
| N2 | 0.059 (6) | 0.049 (6) | 0.048 (6) | −0.006 (5) | 0.016 (5) | 0.000 (5) |
| N3 | 0.053 (5) | 0.046 (5) | 0.034 (5) | 0.004 (4) | 0.016 (4) | −0.005 (4) |
| N4 | 0.047 (5) | 0.042 (5) | 0.051 (6) | 0.003 (4) | 0.018 (4) | −0.007 (5) |
| N5 | 0.036 (5) | 0.045 (5) | 0.038 (5) | 0.004 (4) | 0.009 (4) | 0.001 (4) |
| O1 | 0.046 (4) | 0.120 (7) | 0.036 (4) | −0.014 (5) | 0.023 (4) | −0.025 (5) |
| O2 | 0.069 (6) | 0.067 (6) | 0.100 (7) | −0.029 (5) | 0.054 (5) | −0.034 (5) |
| O3 | 0.067 (6) | 0.088 (7) | 0.075 (6) | 0.035 (5) | 0.026 (5) | 0.038 (5) |
| O4 | 0.024 (4) | 0.037 (5) | 0.029 (5) | −0.002 (4) | 0.014 (4) | −0.009 (4) |
| O5 | 0.047 (4) | 0.055 (5) | 0.061 (5) | −0.024 (4) | 0.029 (4) | −0.029 (4) |
| O6 | 0.040 (4) | 0.042 (4) | 0.049 (4) | 0.004 (3) | 0.025 (3) | 0.003 (3) |
| O7 | 0.042 (4) | 0.042 (4) | 0.058 (5) | 0.012 (3) | 0.028 (4) | 0.003 (4) |
| O8 | 0.062 (5) | 0.032 (4) | 0.085 (6) | 0.012 (4) | 0.037 (5) | 0.014 (4) |
| O9 | 0.042 (4) | 0.083 (6) | 0.034 (4) | 0.013 (4) | 0.017 (3) | 0.016 (4) |
| O10 | 0.028 (3) | 0.077 (5) | 0.035 (4) | −0.003 (4) | 0.009 (3) | −0.002 (4) |
| C1 | 0.046 (6) | 0.047 (7) | 0.034 (6) | −0.002 (5) | 0.018 (5) | 0.004 (5) |
| C2 | 0.063 (8) | 0.066 (8) | 0.053 (8) | 0.001 (7) | 0.021 (7) | 0.007 (7) |
| C3 | 0.067 (8) | 0.085 (10) | 0.039 (7) | −0.007 (7) | 0.011 (6) | 0.010 (7) |
| C4 | 0.055 (7) | 0.066 (8) | 0.046 (8) | 0.004 (6) | 0.017 (6) | −0.005 (6) |
| C5 | 0.025 (5) | 0.047 (6) | 0.038 (6) | −0.001 (4) | 0.008 (4) | −0.012 (5) |
| C6 | 0.061 (7) | 0.044 (7) | 0.060 (9) | 0.002 (6) | 0.023 (6) | −0.012 (6) |
| C7 | 0.058 (7) | 0.035 (6) | 0.048 (8) | 0.000 (5) | 0.011 (6) | −0.002 (5) |
| C8 | 0.051 (7) | 0.052 (7) | 0.041 (7) | 0.007 (5) | 0.023 (5) | 0.008 (6) |
| Mo1—O1 | 1.673 (7) | N3—C1 | 1.315 (13) |
| Mo1—O7 | 1.897 (7) | N3—C4 | 1.333 (14) |
| Mo1—O9 | 1.926 (7) | N3—H3N | 0.860 |
| Mo1—O5 | 1.926 (7) | N4—C5 | 1.347 (13) |
| Mo1—O6 | 1.927 (7) | N4—C6 | 1.369 (15) |
| Mo1—O4 | 2.3087 (9) | N5—C5 | 1.308 (13) |
| Mo2—O2 | 1.680 (8) | N5—C8 | 1.321 (13) |
| Mo2—O8 | 1.892 (8) | O4—Mo1i | 2.3087 (9) |
| Mo2—O6i | 1.927 (7) | O4—Mo3i | 2.3137 (9) |
| Mo2—O5 | 1.931 (8) | O4—Mo2i | 2.3210 (9) |
| Mo2—O10 | 1.935 (7) | O6—Mo2i | 1.927 (7) |
| Mo2—O4 | 2.3210 (9) | O9—Mo3i | 1.916 (7) |
| Mo3—O3 | 1.655 (8) | O10—Mo3i | 1.911 (8) |
| Mo3—O10i | 1.911 (8) | C2—C3 | 1.372 (18) |
| Mo3—O9i | 1.916 (7) | C2—H2 | 0.930 |
| Mo3—O7 | 1.928 (8) | C3—C4 | 1.356 (19) |
| Mo3—O8 | 1.963 (8) | C3—H3 | 0.930 |
| Mo3—O4 | 2.3137 (9) | C4—H4 | 0.930 |
| N1—C5 | 1.364 (13) | C6—C7 | 1.314 (16) |
| N1—C1 | 1.378 (13) | C6—H6 | 0.930 |
| N1—H1N | 0.860 | C7—C8 | 1.384 (15) |
| N2—C1 | 1.329 (14) | C7—H7 | 0.930 |
| N2—C2 | 1.347 (15) | C8—H8 | 0.930 |
| O1—Mo1—O7 | 104.1 (4) | C1—N3—H3N | 120.6 |
| O1—Mo1—O9 | 102.6 (4) | C4—N3—H3N | 120.6 |
| O7—Mo1—O9 | 153.3 (3) | C5—N4—C6 | 116.5 (10) |
| O1—Mo1—O5 | 103.8 (4) | C5—N5—C8 | 117.9 (9) |
| O7—Mo1—O5 | 88.1 (3) | Mo1i—O4—Mo1 | 180.0 |
| O9—Mo1—O5 | 86.5 (4) | Mo1i—O4—Mo3 | 90.22 (4) |
| O1—Mo1—O6 | 102.0 (4) | Mo1—O4—Mo3 | 89.78 (4) |
| O7—Mo1—O6 | 87.3 (3) | Mo1i—O4—Mo3i | 89.78 (4) |
| O9—Mo1—O6 | 86.2 (3) | Mo1—O4—Mo3i | 90.22 (4) |
| O5—Mo1—O6 | 154.1 (3) | Mo3—O4—Mo3i | 180.0 |
| O1—Mo1—O4 | 178.3 (4) | Mo1i—O4—Mo2 | 90.27 (3) |
| O7—Mo1—O4 | 76.9 (2) | Mo1—O4—Mo2 | 89.73 (3) |
| O9—Mo1—O4 | 76.4 (2) | Mo3—O4—Mo2 | 90.14 (4) |
| O5—Mo1—O4 | 77.4 (2) | Mo3i—O4—Mo2 | 89.86 (4) |
| O6—Mo1—O4 | 76.7 (2) | Mo1i—O4—Mo2i | 89.73 (3) |
| O2—Mo2—O8 | 102.7 (4) | Mo1—O4—Mo2i | 90.27 (3) |
| O2—Mo2—O6i | 102.7 (4) | Mo3—O4—Mo2i | 89.86 (4) |
| O8—Mo2—O6i | 87.6 (3) | Mo3i—O4—Mo2i | 90.14 (4) |
| O2—Mo2—O5 | 103.9 (3) | Mo2—O4—Mo2i | 180.0 |
| O8—Mo2—O5 | 88.8 (4) | Mo1—O5—Mo2 | 115.7 (3) |
| O6i—Mo2—O5 | 153.3 (3) | Mo2i—O6—Mo1 | 116.7 (3) |
| O2—Mo2—O10 | 103.7 (4) | Mo1—O7—Mo3 | 117.0 (3) |
| O8—Mo2—O10 | 153.6 (3) | Mo2—O8—Mo3 | 116.7 (3) |
| O6i—Mo2—O10 | 85.9 (3) | Mo3i—O9—Mo1 | 116.9 (3) |
| O5—Mo2—O10 | 85.6 (3) | Mo3i—O10—Mo2 | 116.6 (3) |
| O2—Mo2—O4 | 179.1 (3) | N3—C1—N2 | 125.9 (10) |
| O8—Mo2—O4 | 77.2 (2) | N3—C1—N1 | 119.6 (10) |
| O6i—Mo2—O4 | 76.4 (2) | N2—C1—N1 | 114.3 (10) |
| O5—Mo2—O4 | 77.0 (2) | N2—C2—C3 | 122.4 (13) |
| O10—Mo2—O4 | 76.4 (2) | N2—C2—H2 | 118.8 |
| O3—Mo3—O10i | 103.7 (4) | C3—C2—H2 | 118.8 |
| O3—Mo3—O9i | 104.2 (4) | C4—C3—C2 | 118.3 (12) |
| O10i—Mo3—O9i | 88.2 (3) | C4—C3—H3 | 120.9 |
| O3—Mo3—O7 | 103.1 (4) | C2—C3—H3 | 120.9 |
| O10i—Mo3—O7 | 88.0 (3) | N3—C4—C3 | 119.8 (12) |
| O9i—Mo3—O7 | 152.6 (3) | N3—C4—H4 | 120.1 |
| O3—Mo3—O8 | 103.1 (4) | C3—C4—H4 | 120.1 |
| O10i—Mo3—O8 | 153.1 (3) | N5—C5—N4 | 124.5 (10) |
| O9i—Mo3—O8 | 85.6 (3) | N5—C5—N1 | 118.0 (9) |
| O7—Mo3—O8 | 85.7 (3) | N4—C5—N1 | 117.5 (9) |
| O3—Mo3—O4 | 179.0 (4) | C7—C6—N4 | 121.1 (11) |
| O10i—Mo3—O4 | 77.1 (2) | C7—C6—H6 | 119.5 |
| O9i—Mo3—O4 | 76.4 (2) | N4—C6—H6 | 119.5 |
| O7—Mo3—O4 | 76.2 (2) | C6—C7—C8 | 118.8 (11) |
| O8—Mo3—O4 | 76.0 (2) | C6—C7—H7 | 120.6 |
| C5—N1—C1 | 128.6 (9) | C8—C7—H7 | 120.6 |
| C5—N1—H1N | 115.7 | N5—C8—C7 | 121.2 (10) |
| C1—N1—H1N | 115.7 | N5—C8—H8 | 119.4 |
| C1—N2—C2 | 114.8 (10) | C7—C8—H8 | 119.4 |
| C1—N3—C4 | 118.7 (10) |
| Symmetry codes: (i) −x, −y+2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···N4 | 0.86 | 1.95 | 2.605 (12) | 132 |
| N1—H1N···N5ii | 0.86 | 2.07 | 2.924 (13) | 180 |
| C2—H2···O8iii | 0.93 | 2.65 | 3.444 (14) | 144 |
| C4—H4···O2iv | 0.93 | 2.69 | 3.391 (14) | 133 |
| C6—H6···O6v | 0.93 | 2.38 | 3.250 (15) | 157 |
| C7—H7···O1vi | 0.93 | 2.51 | 3.196 (14) | 131 |
| Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x+1/2, −y+3/2, z−1/2; (v) −x+1/2, y−1/2, −z+1/2; (vi) x+1/2, −y+3/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···N4 | 0.86 | 1.95 | 2.605 (12) | 132 |
| N1—H1N···N5i | 0.86 | 2.07 | 2.924 (13) | 180 |
| C2—H2···O8ii | 0.93 | 2.65 | 3.444 (14) | 144 |
| C4—H4···O2iii | 0.93 | 2.69 | 3.391 (14) | 133 |
| C6—H6···O6iv | 0.93 | 2.38 | 3.250 (15) | 157 |
| C7—H7···O1v | 0.93 | 2.51 | 3.196 (14) | 131 |
| Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, z−1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) x+1/2, −y+3/2, z+1/2. |
We are grateful to the National Science Council of the Republic of China for support. This research was also supported by the project of the specific research fields in Chung Yuan Christian University, Taiwan, under grant CYCU-95-CR—CH.
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Polyoxomolybdates are an important class of metal-oxygen cluster compounds (Shivaiah, 2006; Bridgeman & Cavigliasso, 2002) which show interesting chemical and physical properties (Shi, et al., 2006; Wang, et al., 2004; Guo, et al., 2004; Burkholder & Zubieta, 2004; Hagrman, et al., 1999). Since the anions contain many oxygen atoms which are good hydrogen-bond acceptors, cocrystallization with organic cations should result in interesting supramolecular chemistry. In the title complex (Fig. 1), the protonated dipyrimidylamine molecules (Hdipm) are linked into dimers by N—H···N hydrogen bonds. The cations and anions are interlinked through C—H···O contacts (Fig. 2).