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Volume 69 
Part 11 
Pages m605-m606  
November 2013  

Received 18 July 2013
Accepted 18 September 2013
Online 16 October 2013

Key indicators
Single-crystal X-ray study
T = 293 K
Mean [sigma](C-C) = 0.019 Å
R = 0.040
wR = 0.075
Data-to-parameter ratio = 16.3
Details
Open access

Ethyl­enedi­ammonium sodium tetra­kis­[bis­(ethyl­enedi­amine-[kappa]2N,N')(oxalato-[kappa]2O1,O2)cobalt(III)] [penta­hydrogen di(phosphato­octa­deca­tungstate)] tetra­deca­hydrate

aDepartment of Material Engineering Invention Examination, Patent Examination Cooperation Center of the Patent Office, SIPO, Beijing, People's Republic of China
Correspondence e-mail: zhangshuzhuo_1@sipo.gov.cn

The title compound, Na(C2H10N2)[Co(C2O4)(C2H8N2)2]4[H5(P2W18O62)2]·14H2O, prepared under hydro­thermal conditions, consists of two Dawson-type [P2W18O62]6- anions, four isolated [Co(en)2(ox)]+ cations (en = ethyl­enedi­amine and ox = oxalate), one Na+ cation, one [H2en]2+ cation, and a number of ordered (14) and disordered solvent water mol­ecules. The [P2W18O62]6- polyoxidometalate anion has site symmetry 1 and contains two structurally distinct types of W atoms: viz. six W atoms on vertical pseudo-mirror planes grouped in two sets of three, and 12 equatorial W atoms that do not lie in the pseudo-mirror planes grouped in two sets of six. In each [Co(en)2(ox)]+ cation, the CoIII ion is coordinated by four N atoms from two en ligands and two O atoms from the ox ligands, completing a distorted octa­hedral structure. The sodium cation lies on an inversion centre and additionally links the complex cations and anions. In the crystal, the various units are linked by N-H...O and O-H...O hydrogen bonds, which together with C-H...O hydrogen bonds form a three-dimensional structure. The contribution of a region of disordered electron density, possibly highly disordered solvent water mol­ecules, to the scattering was removed with the SQUEEZE option of PLATON [Spek (2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]). Acta Cryst. D65, 148-155]. To equilibrate the charges five H+ ions have been added to the polyoxidometalate. These H+ ions and the disordered solvent contribution were not included in the reported mol­ecular weight and density.

Related literature

For general background to polyoxidometalate-based materials, see: Du et al. (2013[Du, D.-Y., Yan, L.-K., Su, Z.-M., Li, S.-L., Lan, Y.-Q. & Wang, E.-B. (2013). Coord. Chem. Rev. 257, 702-717.]); Dolbecq et al. (2010[Dolbecq, A., Dumas, E., Mayer, C. R. & Mialane, P. (2010). Chem. Rev. 110, 6009-6048.]); Zheng & Yang (2012[Zheng, S.-T. & Yang, G.-Y. (2012). Chem. Soc. Rev. 41, 7623-7646.]). For organic-inorganic hybrid materials constructed from components based on saturated polyoxidoanions and transition metal coordination complexes (TMCs), see: Liu et al. (2011[Liu, H.-Y., Wu, H., Yang, J., Liu, Y.-Y., Ma, J.-F. & Bai, H.-Y. (2011). Cryst. Growth Des. 11, 1786-1797.]); Wang et al. (2010[Wang, X.-L., Li, Y.-G., Lu, Y., Fu, H., Su, Z.-M. & Wang, E.-B. (2010). Cryst. Growth Des. 10, 4227-4230.]). For related organic-inorganic hybrid compounds based on saturated Wells-Dawson-type polyoxidoanions and TMCs, and the synthesis of the POM precursor, Na6[P2W18O62]·19H2O, see: Wang et al. (2010[Wang, X.-L., Li, Y.-G., Lu, Y., Fu, H., Su, Z.-M. & Wang, E.-B. (2010). Cryst. Growth Des. 10, 4227-4230.]); Contant (1990[Contant, R. (1990). Inorganic Syntheses, Vol. 27, pp. 108-110. New York: John Wiley & Sons.]).

[Scheme 1]

Experimental

Crystal data
  • Na(C2H10N2)[Co(C2O4)(C2H8N2)2]4[H5(P2W18O62)2]·14H2O

  • Mr = 10132.09

  • Triclinic, [P \overline 1]

  • a = 14.5999 (4) Å

  • b = 16.5714 (4) Å

  • c = 18.0165 (4) Å

  • [alpha] = 83.693 (2)°

  • [beta] = 84.586 (2)°

  • [gamma] = 87.992 (2)°

  • V = 4311.88 (18) Å3

  • Z = 1

  • Mo K[alpha] radiation

  • [mu] = 24.42 mm-1

  • T = 293 K

  • 0.12 × 0.06 × 0.05 mm

Data collection
  • Oxford Diffraction multiwire proportional diffractometer

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.158, Tmax = 0.375

  • 49498 measured reflections

  • 17862 independent reflections

  • 12523 reflections with I > 2[sigma](I)

  • Rint = 0.057

Refinement
  • R[F2 > 2[sigma](F2)] = 0.040

  • wR(F2) = 0.075

  • S = 0.96

  • 17862 reflections

  • 1096 parameters

  • 12 restraints

  • H-atom parameters constrained

  • [Delta][rho]max = 2.01 e Å-3

  • [Delta][rho]min = -1.98 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N2-H2A...O100i 0.90 2.59 3.314 (14) 138
N2-H2A...O103i 0.90 2.07 2.940 (14) 163
N2-H2B...O38 0.90 2.26 3.115 (13) 157
O2W-H2WA...O57ii 0.85 2.44 2.919 (17) 117
N3-H3C...O103i 0.90 2.48 2.994 (14) 117
O2W-H2WB...O6W 0.85 2.04 2.86 (3) 162
N4-H4D...O1W 0.90 2.06 2.939 (18) 167
O3W-H3WA...O102i 0.85 2.16 3.000 (18) 172
O4W-H4WA...O12iii 0.85 2.14 2.983 (18) 173
N7-H7D...O5W 0.90 2.11 3.010 (17) 176
O4W-H4WB...O42 0.85 2.05 2.891 (16) 173
N5-H8A...O102 0.89 1.86 2.740 (15) 170
N5-H8B...O45ii 0.89 2.23 3.076 (13) 158
N5-H8B...O57ii 0.89 2.54 3.166 (14) 128
N5-H8C...O2W 0.89 2.05 2.881 (17) 155
N8-H8E...O7W 0.90 2.23 3.07 (2) 154
N9-H9C...O63i 0.90 2.12 3.023 (13) 175
N9-H9D...O49ii 0.90 2.20 3.088 (13) 170
C3-H3A...O29 0.97 2.49 3.417 (17) 160
C4-H4B...O10 0.97 2.47 3.396 (18) 160
C11-H11A...O33ii 0.97 2.52 3.376 (17) 147
C12-H12A...O25ii 0.97 2.51 3.297 (16) 139
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]); 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2626 ).


References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Contant, R. (1990). Inorganic Syntheses, Vol. 27, pp. 108-110. New York: John Wiley & Sons.
Dolbecq, A., Dumas, E., Mayer, C. R. & Mialane, P. (2010). Chem. Rev. 110, 6009-6048.  [Web of Science] [CrossRef] [ChemPort] [PubMed]
Du, D.-Y., Yan, L.-K., Su, Z.-M., Li, S.-L., Lan, Y.-Q. & Wang, E.-B. (2013). Coord. Chem. Rev. 257, 702-717.  [Web of Science] [CrossRef] [ChemPort]
Liu, H.-Y., Wu, H., Yang, J., Liu, Y.-Y., Ma, J.-F. & Bai, H.-Y. (2011). Cryst. Growth Des. 11, 1786-1797.  [CSD] [CrossRef] [ChemPort]
Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Wang, X.-L., Li, Y.-G., Lu, Y., Fu, H., Su, Z.-M. & Wang, E.-B. (2010). Cryst. Growth Des. 10, 4227-4230.  [CSD] [CrossRef]
Zheng, S.-T. & Yang, G.-Y. (2012). Chem. Soc. Rev. 41, 7623-7646.  [Web of Science] [CrossRef] [ChemPort] [PubMed]


Acta Cryst (2013). E69, m605-m606   [ doi:10.1107/S160053681302583X ]

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