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Volume 66 
Part 3 
Pages m263-m264  
March 2010  

Received 29 December 2009
Accepted 20 January 2010
Online 6 February 2010

Key indicators
Single-crystal X-ray study
T = 296 K
Mean [sigma](C-C) = 0.005 Å
Disorder in main residue
R = 0.020
wR = 0.053
Data-to-parameter ratio = 10.0
Details
Open access

Tris(piperazinediium) phosphatododecamolybo(V,VI)phosphate

aCollege of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao Shandong 266555, People's Republic of China,bCollege of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, People's Republic of China, and cCollege of Chemical Engineering, Northeast Dianli University, Jilin 132012, People's Republic of China
Correspondence e-mail: luyukun1983@sina.com

The title compound, (C4H12N2)3[PMo12O40] or (H2pip)3[PMo12O40] (pip is piperazine), was prepared under hydrothermal conditions. The asymmetric unit contains one-sixth of a mixed-valent Mo(V,VI) pseudo-Keggin-type [PMo12O40]6- anion and half a piperazinediium cation, (H2pip)2+. The discrete Keggin-type [PMo12O40]6- anion has [\overline{3}] site symmetry and the three (H2pip)2+ cations each have [\overline{1}] site symmetry at the centres of the molecules. The central P atom is on special position [\overline{3}], which is a roto-inversion position and generates the disorder of the PO4 tetrahedron. Furthermore, six doubly bridging oxide groups are also disordered with an occupancy factor of 0.5 for each O atom. The anions and cations are linked by an extensive network of intermolecular N-H...O and C-H...O hydrogen bonds.

Related literature

For polyoxometalate chemistry, see: Pope & Müller (1991[Pope, M. T. & Müller, A. (1991). Angew. Chem. Int. Ed. Engl. 30, 34-48.]); Hill (1998[Hill, C. L. (1998). Chem. Rev. 98, 1-2.]); Kurth et al. (2001[Kurth, D. G., Volkmer, D., Pope, M. T. & Müller, A. (2001). Polyoxometalate Chemistry, p. 301. Dordrecht: Kluwer.]). For related structures, see: Han et al. (2005[Han, Z. G., Zhao, Y. L., Peng, J., Tian, A. X., Liu, Q., Ma, J. F., Wang, E. B. & Hu, N. H. (2005). CrystEngComm, 7, 380-387.]); Li et al. (2007[Li, Y. G., Dai, L. M., Wang, Y. H., Wang, X. L., Wang, E. B., Su, Z. M. & Xu, L. (2007). Chem. Commun. pp. 2593-2595.]); Yuan et al. (2008[Yuan, J.-H., Wang, C., Yu, M.-J. & Li, J. (2008). Acta Cryst. E64, m831.]). For general background to bond-valence calculations, see: Brown & Altermatt (1985[Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.]).

[Scheme 1]

Experimental

Crystal data
  • (C4H12N2)3[PMo12O40]

  • Mr = 2086.72

  • Trigonal, [R \overline 3c ]

  • a = 17.890 (3) Å

  • c = 23.600 (6) Å

  • V = 6541 (2) Å3

  • Z = 6

  • Mo K[alpha] radiation

  • [mu] = 3.49 mm-1

  • T = 296 K

  • 0.20 × 0.16 × 0.11 mm

Data collection
  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.517, Tmax = 0.682

  • 11291 measured reflections

  • 1413 independent reflections

  • 1363 reflections with I > 2[sigma](I)

  • Rint = 0.056

Refinement
  • R[F2 > 2[sigma](F2)] = 0.020

  • wR(F2) = 0.053

  • S = 1.14

  • 1413 reflections

  • 142 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.66 e Å-3

  • [Delta][rho]min = -0.61 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N1-H1C...O6 0.90 2.22 2.812 (4) 123
N1-H1D...O50 0.90 2.43 2.926 (6) 115
N1-H1C...O4i 0.90 2.20 3.041 (7) 155
N1-H1C...O40i 0.90 2.16 3.047 (7) 168
N1-H1C...O30ii 0.90 2.52 3.091 (6) 122
N1-H1D...O5 0.90 2.19 2.852 (6) 130
N1-H1D...O1iii 0.90 2.14 2.900 (4) 142
C1-H1A...O6 0.97 2.58 3.101 (5) 114
C1-H1B...O4iv 0.97 2.58 3.347 (7) 137
C2-H2A...O2iv 0.97 2.43 3.291 (4) 148
C2-H2B...O3ii 0.97 2.43 3.156 (6) 132
C2-H2B...O2v 0.97 2.42 3.068 (4) 124
Symmetry codes: (i) -x+y, -x, z; (ii) y, -x+y, -z; (iii) [x+{\script{1\over 3}}, x-y+{\script{2\over 3}}, z+{\script{1\over 6}}]; (iv) [x-y+{\script{2\over 3}}, x+{\script{1\over 3}}, -z+{\script{1\over 3}}]; (v) [-y+{\script{2\over 3}}, -x+{\script{1\over 3}}, z-{\script{1\over 6}}].

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2235 ).


Acknowledgements

This work was supported by the National Natural Science Foundation of China (20571032 and 20333070).

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.  [CrossRef] [ISI] [details]
Han, Z. G., Zhao, Y. L., Peng, J., Tian, A. X., Liu, Q., Ma, J. F., Wang, E. B. & Hu, N. H. (2005). CrystEngComm, 7, 380-387.  [ISI] [CSD] [CrossRef] [ChemPort]
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Hill, C. L. (1998). Chem. Rev. 98, 1-2.  [CSD] [CrossRef] [PubMed] [ChemPort] [ISI]
Kurth, D. G., Volkmer, D., Pope, M. T. & Müller, A. (2001). Polyoxometalate Chemistry, p. 301. Dordrecht: Kluwer.
Li, Y. G., Dai, L. M., Wang, Y. H., Wang, X. L., Wang, E. B., Su, Z. M. & Xu, L. (2007). Chem. Commun. pp. 2593-2595.  [CSD] [CrossRef]
Pope, M. T. & Müller, A. (1991). Angew. Chem. Int. Ed. Engl. 30, 34-48.  [CrossRef] [ISI]
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Yuan, J.-H., Wang, C., Yu, M.-J. & Li, J. (2008). Acta Cryst. E64, m831.  [CSD] [CrossRef] [details]


Acta Cryst (2010). E66, m263-m264   [ doi:10.1107/S1600536810002473 ]

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