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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m41.
Published online 2007 December 6. doi:  10.1107/S1600536807062897
PMCID: PMC2914927

Bis[2-(pyrimidin-2-ylamino)pyrimidin­ium] hexa­molybdate

Abstract

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—H(...)N hydrogen bonds into dimers across centres of inversion. The cations and anions are inter­linked through C—H(...)O contacts.

Related literature

For related literature, see: Shivaiah (2006 [triangle]); Bridgeman & Cavigliasso (2002 [triangle]); Shi et al. (2006 [triangle]); Wang et al. (2004 [triangle]); Guo et al. (2004 [triangle]); Burkholder & Zubieta (2004 [triangle]); Hagrman et al. (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00m41-scheme1.jpg

Experimental

Crystal data

  • (C8H8N5)2[Mo6O19]
  • M r = 1228.03
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m41-efi1.jpg
  • a = 10.4338 (19) Å
  • b = 13.7437 (19) Å
  • c = 11.0792 (17) Å
  • β = 105.471 (13)°
  • V = 1531.2 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.48 mm−1
  • T = 295 (2) K
  • 0.40 × 0.20 × 0.05 mm

Data collection

  • Bruker P4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.578, T max = 0.883
  • 3399 measured reflections
  • 2660 independent reflections
  • 1833 reflections with I > 2σ(I)
  • R int = 0.082
  • 3 standard reflections every 97 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.057
  • wR(F 2) = 0.146
  • S = 1.02
  • 2660 reflections
  • 232 parameters
  • H-atom parameters constrained
  • Δρmax = 0.91 e Å−3
  • Δρmin = −1.78 e Å−3

Data collection: XSCANS (Siemens, 1996 [triangle]); cell refinement: XSCANS; data reduction: XSCANS program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062897/bi2259sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062897/bi2259Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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).

Experimental

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%.

Refinement

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).

Figures

Fig. 1.
The molecular structure of the title compound showing displacement ellipsoids at the 30% probability level for non-H atoms.
Fig. 2.
Partial packing diagram showing N—H···N hydrogen bonding between Hdipm molecules and C—H···O contacts to the polyoxometalate.

Crystal data

(C8H8N5)2[Mo6O19]F000 = 1172
Mr = 1228.03Dx = 2.664 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 31 reflections
a = 10.4338 (19) Åθ = 4.8–12.5º
b = 13.7437 (19) ŵ = 2.48 mm1
c = 11.0792 (17) ÅT = 295 (2) K
β = 105.471 (13)ºPlate, green
V = 1531.2 (4) Å30.40 × 0.20 × 0.05 mm
Z = 2

Data collection

Bruker P4 diffractometerRint = 0.082
Radiation source: fine-focus sealed tubeθmax = 25.0º
Monochromator: graphiteθmin = 2.4º
T = 295(2) Kh = −1→12
ω scansk = −1→16
Absorption correction: ψ scan(North et al., 1968)l = −13→12
Tmin = 0.578, Tmax = 0.8833 standard reflections
3399 measured reflections every 97 reflections
2660 independent reflections intensity decay: none
1833 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-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 reflectionsΔρmax = 0.91 e Å3
232 parametersΔρmin = −1.78 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Mo10.06601 (9)0.95848 (7)0.32376 (8)0.0380 (3)
Mo2−0.15184 (9)0.87281 (7)0.46013 (9)0.0418 (3)
Mo30.16049 (9)0.89727 (7)0.61876 (9)0.0434 (3)
N10.4384 (8)0.9695 (6)0.3239 (8)0.040 (2)
H1N0.46071.01660.37640.048*
N20.4053 (10)1.0908 (7)0.1792 (9)0.052 (2)
N30.3659 (9)0.9281 (7)0.1128 (8)0.043 (2)
H3N0.36760.86760.13310.052*
N40.4025 (9)0.8036 (6)0.2961 (9)0.046 (2)
N50.4845 (8)0.8709 (6)0.4968 (9)0.040 (2)
O10.1142 (7)0.9318 (7)0.1952 (7)0.065 (2)
O2−0.2622 (8)0.7811 (6)0.4336 (9)0.072 (3)
O30.2743 (9)0.8222 (7)0.7019 (9)0.076 (3)
O40.00001.00000.50000.0286 (19)
O5−0.0732 (7)0.8658 (5)0.3211 (7)0.052 (2)
O60.1775 (7)1.0683 (5)0.3902 (7)0.0414 (17)
O70.1797 (7)0.8825 (5)0.4514 (7)0.0446 (18)
O80.0033 (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)
C10.4034 (10)0.9955 (8)0.1993 (9)0.041 (3)
C20.3673 (12)1.1171 (10)0.0578 (12)0.060 (3)
H20.36991.18270.03760.072*
C30.3249 (13)1.0509 (11)−0.0372 (12)0.064 (4)
H30.29681.0711−0.12020.077*
C40.3252 (12)0.9553 (10)−0.0069 (11)0.055 (3)
H40.29710.9089−0.06940.066*
C50.4425 (9)0.8789 (7)0.3750 (10)0.037 (2)
C60.4060 (12)0.7135 (9)0.3495 (12)0.054 (3)
H60.37740.65960.29870.064*
C70.4491 (11)0.7019 (8)0.4714 (11)0.048 (3)
H70.45370.64020.50680.057*
C80.4876 (10)0.7831 (8)0.5462 (10)0.046 (3)
H80.51610.77580.63270.055*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mo10.0374 (5)0.0496 (6)0.0324 (5)−0.0021 (4)0.0188 (4)−0.0061 (4)
Mo20.0393 (5)0.0414 (5)0.0508 (6)−0.0114 (4)0.0228 (4)−0.0095 (4)
Mo30.0400 (5)0.0502 (6)0.0424 (6)0.0122 (4)0.0151 (4)0.0098 (5)
N10.043 (5)0.041 (5)0.035 (5)−0.002 (4)0.009 (4)−0.005 (4)
N20.059 (6)0.049 (6)0.048 (6)−0.006 (5)0.016 (5)0.000 (5)
N30.053 (5)0.046 (5)0.034 (5)0.004 (4)0.016 (4)−0.005 (4)
N40.047 (5)0.042 (5)0.051 (6)0.003 (4)0.018 (4)−0.007 (5)
N50.036 (5)0.045 (5)0.038 (5)0.004 (4)0.009 (4)0.001 (4)
O10.046 (4)0.120 (7)0.036 (4)−0.014 (5)0.023 (4)−0.025 (5)
O20.069 (6)0.067 (6)0.100 (7)−0.029 (5)0.054 (5)−0.034 (5)
O30.067 (6)0.088 (7)0.075 (6)0.035 (5)0.026 (5)0.038 (5)
O40.024 (4)0.037 (5)0.029 (5)−0.002 (4)0.014 (4)−0.009 (4)
O50.047 (4)0.055 (5)0.061 (5)−0.024 (4)0.029 (4)−0.029 (4)
O60.040 (4)0.042 (4)0.049 (4)0.004 (3)0.025 (3)0.003 (3)
O70.042 (4)0.042 (4)0.058 (5)0.012 (3)0.028 (4)0.003 (4)
O80.062 (5)0.032 (4)0.085 (6)0.012 (4)0.037 (5)0.014 (4)
O90.042 (4)0.083 (6)0.034 (4)0.013 (4)0.017 (3)0.016 (4)
O100.028 (3)0.077 (5)0.035 (4)−0.003 (4)0.009 (3)−0.002 (4)
C10.046 (6)0.047 (7)0.034 (6)−0.002 (5)0.018 (5)0.004 (5)
C20.063 (8)0.066 (8)0.053 (8)0.001 (7)0.021 (7)0.007 (7)
C30.067 (8)0.085 (10)0.039 (7)−0.007 (7)0.011 (6)0.010 (7)
C40.055 (7)0.066 (8)0.046 (8)0.004 (6)0.017 (6)−0.005 (6)
C50.025 (5)0.047 (6)0.038 (6)−0.001 (4)0.008 (4)−0.012 (5)
C60.061 (7)0.044 (7)0.060 (9)0.002 (6)0.023 (6)−0.012 (6)
C70.058 (7)0.035 (6)0.048 (8)0.000 (5)0.011 (6)−0.002 (5)
C80.051 (7)0.052 (7)0.041 (7)0.007 (5)0.023 (5)0.008 (6)

Geometric parameters (Å, °)

Mo1—O11.673 (7)N3—C11.315 (13)
Mo1—O71.897 (7)N3—C41.333 (14)
Mo1—O91.926 (7)N3—H3N0.860
Mo1—O51.926 (7)N4—C51.347 (13)
Mo1—O61.927 (7)N4—C61.369 (15)
Mo1—O42.3087 (9)N5—C51.308 (13)
Mo2—O21.680 (8)N5—C81.321 (13)
Mo2—O81.892 (8)O4—Mo1i2.3087 (9)
Mo2—O6i1.927 (7)O4—Mo3i2.3137 (9)
Mo2—O51.931 (8)O4—Mo2i2.3210 (9)
Mo2—O101.935 (7)O6—Mo2i1.927 (7)
Mo2—O42.3210 (9)O9—Mo3i1.916 (7)
Mo3—O31.655 (8)O10—Mo3i1.911 (8)
Mo3—O10i1.911 (8)C2—C31.372 (18)
Mo3—O9i1.916 (7)C2—H20.930
Mo3—O71.928 (8)C3—C41.356 (19)
Mo3—O81.963 (8)C3—H30.930
Mo3—O42.3137 (9)C4—H40.930
N1—C51.364 (13)C6—C71.314 (16)
N1—C11.378 (13)C6—H60.930
N1—H1N0.860C7—C81.384 (15)
N2—C11.329 (14)C7—H70.930
N2—C21.347 (15)C8—H80.930
O1—Mo1—O7104.1 (4)C1—N3—H3N120.6
O1—Mo1—O9102.6 (4)C4—N3—H3N120.6
O7—Mo1—O9153.3 (3)C5—N4—C6116.5 (10)
O1—Mo1—O5103.8 (4)C5—N5—C8117.9 (9)
O7—Mo1—O588.1 (3)Mo1i—O4—Mo1180.0
O9—Mo1—O586.5 (4)Mo1i—O4—Mo390.22 (4)
O1—Mo1—O6102.0 (4)Mo1—O4—Mo389.78 (4)
O7—Mo1—O687.3 (3)Mo1i—O4—Mo3i89.78 (4)
O9—Mo1—O686.2 (3)Mo1—O4—Mo3i90.22 (4)
O5—Mo1—O6154.1 (3)Mo3—O4—Mo3i180.0
O1—Mo1—O4178.3 (4)Mo1i—O4—Mo290.27 (3)
O7—Mo1—O476.9 (2)Mo1—O4—Mo289.73 (3)
O9—Mo1—O476.4 (2)Mo3—O4—Mo290.14 (4)
O5—Mo1—O477.4 (2)Mo3i—O4—Mo289.86 (4)
O6—Mo1—O476.7 (2)Mo1i—O4—Mo2i89.73 (3)
O2—Mo2—O8102.7 (4)Mo1—O4—Mo2i90.27 (3)
O2—Mo2—O6i102.7 (4)Mo3—O4—Mo2i89.86 (4)
O8—Mo2—O6i87.6 (3)Mo3i—O4—Mo2i90.14 (4)
O2—Mo2—O5103.9 (3)Mo2—O4—Mo2i180.0
O8—Mo2—O588.8 (4)Mo1—O5—Mo2115.7 (3)
O6i—Mo2—O5153.3 (3)Mo2i—O6—Mo1116.7 (3)
O2—Mo2—O10103.7 (4)Mo1—O7—Mo3117.0 (3)
O8—Mo2—O10153.6 (3)Mo2—O8—Mo3116.7 (3)
O6i—Mo2—O1085.9 (3)Mo3i—O9—Mo1116.9 (3)
O5—Mo2—O1085.6 (3)Mo3i—O10—Mo2116.6 (3)
O2—Mo2—O4179.1 (3)N3—C1—N2125.9 (10)
O8—Mo2—O477.2 (2)N3—C1—N1119.6 (10)
O6i—Mo2—O476.4 (2)N2—C1—N1114.3 (10)
O5—Mo2—O477.0 (2)N2—C2—C3122.4 (13)
O10—Mo2—O476.4 (2)N2—C2—H2118.8
O3—Mo3—O10i103.7 (4)C3—C2—H2118.8
O3—Mo3—O9i104.2 (4)C4—C3—C2118.3 (12)
O10i—Mo3—O9i88.2 (3)C4—C3—H3120.9
O3—Mo3—O7103.1 (4)C2—C3—H3120.9
O10i—Mo3—O788.0 (3)N3—C4—C3119.8 (12)
O9i—Mo3—O7152.6 (3)N3—C4—H4120.1
O3—Mo3—O8103.1 (4)C3—C4—H4120.1
O10i—Mo3—O8153.1 (3)N5—C5—N4124.5 (10)
O9i—Mo3—O885.6 (3)N5—C5—N1118.0 (9)
O7—Mo3—O885.7 (3)N4—C5—N1117.5 (9)
O3—Mo3—O4179.0 (4)C7—C6—N4121.1 (11)
O10i—Mo3—O477.1 (2)C7—C6—H6119.5
O9i—Mo3—O476.4 (2)N4—C6—H6119.5
O7—Mo3—O476.2 (2)C6—C7—C8118.8 (11)
O8—Mo3—O476.0 (2)C6—C7—H7120.6
C5—N1—C1128.6 (9)C8—C7—H7120.6
C5—N1—H1N115.7N5—C8—C7121.2 (10)
C1—N1—H1N115.7N5—C8—H8119.4
C1—N2—C2114.8 (10)C7—C8—H8119.4
C1—N3—C4118.7 (10)

Symmetry codes: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3N···N40.861.952.605 (12)132
N1—H1N···N5ii0.862.072.924 (13)180
C2—H2···O8iii0.932.653.444 (14)144
C4—H4···O2iv0.932.693.391 (14)133
C6—H6···O6v0.932.383.250 (15)157
C7—H7···O1vi0.932.513.196 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2259).

References

  • Bridgeman, A. J. & Cavigliasso, G. (2002). Inorg. Chem.41, 1761–1770. [PubMed]
  • Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Burkholder, E. & Zubieta, J. (2004). Inorg. Chim. Acta, 357, 279–284.
  • Guo, Y., Wang, X., Li, Y., Wang, E., Xu, L. & Hu, C. (2004). J. Coord. Chem.57, 445–451.
  • Hagrman, P. J., Hagrman, D. & Zubieta, Z. (1999). Angew. Chem. Int. Ed. Engl.38, 2638–2684. [PubMed]
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.
  • Shi, Y., Yang, W., Xue, G., Hu, H. & Wang, J. (2006). J. Mol. Struct.784, 244–248.
  • Shivaiah, V. (2006). Inorg. Chem. Commun.9, 1191–1194.
  • Siemens (1996). XSCANS Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Wang, X., Guo, Y., Wang, E., Duan, L., Xu, X. & Hu, C. (2004). J. Mol. Struct.691, 171–180.

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