Tris[tris­(1,10-phenanthroline-κ2N,N′)iron(II)] dodeca­tungstoferrate dihydrate

Ma, F.-X.; Chen, Y.-G.; Shi, D.-M.

doi:10.1107/S1600536808009896

Volume 64
Part 5
Page m672
May 2008

Received 24 March 2008
Accepted 10 April 2008
Online 16 April 2008

Key indicators
Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.027 Å
H completeness 95%
Disorder in solvent or counterion
R = 0.036
wR = 0.094
Data-to-parameter ratio = 11.0
Details

Tris[tris(1,10-phenanthroline-²N,N')iron(II)] dodecatungstoferrate dihydrate

Feng-Xia Ma,^a,^b Ya-Guang Chen ^a ^* and Dong-Mei Shi ^a

^aDepartment of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China, and ^bBasic Science Department, Jilin Agricultural Science and Technology College, Jilin 132101, People's Republic of China
Correspondence e-mail: chenyg146@nenu.edu.cn

The title compound, [Fe(C₁₂H₈N₂)₃]₃[FeW₁₂O₄₀]·2H₂O, was prepared under hydrothermal conditions. The discrete Keggin-type [FeW₁₂O₄₀]^6- heteropolyoxoanion has threefold symmetry, with the Fe^II atom located on the threefold rotation axis. The central FeO₄ tetrahedron in the anion shares its O atoms with four W₃O₁₃ trinuclear units, each of which is made up of three edge-shared WO₆ octahedral units. The Fe^II atom in the complex cation, viz [Fe(phen)₃]²⁺ (phen is 1,10-phenanthroline), shows a slightly distorted octahedral geometry defined by six N atoms from three phen ligands. The polyoxoanions pack together with the cations, with the disordered water molecules located in voids; the site occupancy factor for each water O atom is 0.33.

Related literature

For related literature, see: Brown (2002); Misono (1987); Pope (1983).

Experimental

Crystal data

[Fe(C₁₂H₈N₂)₃]₃[FeW₁₂O₄₀]·2H₂O
M_r = 4727.47
Trigonal, R 3
a = 25.088 (5) Å
c = 17.231 (5) Å
V = 9392 (4) Å³
Z = 3
Mo K radiation
= 11.51 mm^-1
T = 293 (2) K
0.24 × 0.21 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.075, T_max = 0.104
16084 measured reflections
6154 independent reflections
5557 reflections with I > 2(I)
R_int = 0.034

Refinement

R[F² > 2(F²)] = 0.035
wR(F²) = 0.093
S = 1.03
6154 reflections
560 parameters
1 restraint
H-atom parameters constrained
_max = 1.62 e Å^-3
_min = -1.55 e Å^-3
Absolute structure: Flack (1983), 3713 Friedel pairs
Flack parameter: -0.006 (6)

Table 1
Selected bond lengths (Å)

Fe1-O13	1.826 (8)
Fe1-O1	1.833 (18)
Fe2-N6	1.969 (11)
Fe2-N3	1.971 (12)
Fe2-N1	1.972 (10)
Fe2-N5	1.979 (12)
Fe2-N2	1.986 (11)
Fe2-N4	2.001 (11)
W1-O3	1.692 (9)
W1-O4	1.898 (9)
W1-O7	1.943 (8)
W1-O12	1.950 (8)
W1-O1	2.230 (9)
W2-O5	1.702 (10)
W2-O7	1.858 (9)
W2-O9	1.940 (9)
W2-O14ⁱ	1.954 (9)
W2-O11ⁱ	1.963 (10)
W2-O13ⁱ	2.211 (8)
W3-O6	1.742 (11)
W3-O2ⁱ	1.903 (9)
W3-O2	1.911 (9)
W3-O11	1.951 (10)
W3-O10	1.961 (10)
W3-O13	2.229 (10)
W4-O8	1.678 (9)
W4-O9	1.896 (8)
W4-O4	1.904 (9)
W4-O10	1.944 (11)
W4-O14	2.001 (9)
W4-O13	2.221 (8)
Symmetry code: (i) -x+y+1, -x+1, z.

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2126 ).

Acknowledgements

This work was supported by the Analysis and Testing Foundation of Northeast Normal University, Changchun, China.

References

Brown, I. D. (2002). The Chemical Bond in Inorganic Chemistry: the Bond Valence Model. Oxford University Press.
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Flack, H. D. (1983). Acta Cryst. A39, 876-881.
Misono, M. (1987). Cat. Rev. Sci. Eng. 29, 269-321.
Pope, M. T. (1983). Heteropoly and Isopoly Oxometalates. Berlin: Springer.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.

metal-organic compounds

Tris[tris(1,10-phenanthroline-2N,N')iron(II)] dodecatungstoferrate dihydrate