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Volume 68 
Part 12 
Pages m1559-m1560  
December 2012  

Received 13 November 2012
Accepted 22 November 2012
Online 30 November 2012

Key indicators
Single-crystal X-ray study
T = 150 K
Mean [sigma](C-C) = 0.004 Å
R = 0.027
wR = 0.057
Data-to-parameter ratio = 17.8
Details
Open access

Hexacarbonyl-2[kappa]3C,3[kappa]3C-di-[mu]3-sulfido-tetrakis(tetrahydrofuran-1[kappa]O)calciumdiiron(II)(Fe-Fe)

aNikolaev Institute of Inorganic Chemistry, SB Russian Academy of Sciences, Akad. Lavrentiev prospekt 3, Novosibirsk 90, 630090 Russian Federation, and bNovosibirsk State University, Pirogov st. 2, Novosibirsk 90, 630090 Russian Federation
Correspondence e-mail: k_cadet@mail.ru

Reaction between [Fe2([mu]-S2)(CO)6] and [Ca(thf)4(dpp-BIAN)] [dpp-BIAN = 1,2-bis-(2,6-diisopropylphenylimino)acenaphthene and thf = tetrahydrofuran] proceeds as a redox process via a two-electron reduction of [Fe2([mu]-S2)(CO)6] and a two-electron oxidation of (dpp-BIAN)2-, resulting in the formation of the title heterometallic trinuclear cluster, [CaFe2([mu]3-S)2(C4H8O)4(CO)6], and neutral dpp-BIAN. In the cluster, the CaII atom is connected to two S atoms of an Fe2S2 core [Ca-S = 2.7463 (8) and 2.7523 (8) Å]. No Fe-Ca bonds are formed [Fe...Ca = 3.6708 (6) and 3.5802 (6) Å]. There are five close C-H...O-C contacts in the crystal structure.

Related literature

For the synthesis and structure of [Fe2(CO)6([mu]-S2)], see: Hieber & Beck (1958[Hieber, W. & Beck, J. (1958). Z. Anorg. Allg. Chem. 296, 91-103.]); Seyferth et al. (1982[Seyferth, D., Henderson, R. S. & Song, L. (1982). Organometallics, 1, 125-133.]), and of [Ca(thf)4(dpp-BIAN)], see: Fedushkin et al. (2003[Fedushkin, I. L., Skatova, A. A., Chudakova, V. A., Fukin, G. K., Dechert, S. & Schumann, H. (2003). Eur. J. Inorg. Chem. pp. 3336-3346.]). For the synthesis and structures of related heterometallic clusters with an Fe2S2 core, see: Konchenko et al. (2010[Konchenko, S. N., Sanden, T., Pushkarevsky, N. A., Köppe, R. & Roesky, P. W. (2010). Chem. Eur. J. 16, 14278-14280.]); Cowie et al. (1989[Cowie, M., DeKock, R. L., Wagenmaker, T. R., Seyferth, D., Henderson, R. S. & Gallagher, M. K. (1989). Organometallics, 8, 119-132.]); Veith et al. (2005[Veith, M., Auvray, N., Huch, V. & Braunstein, P. (2005). C. R. Chim. 8, 57-64.]); Eremenko et al. (1994[Eremenko, I. L., Berke, H., van der Zeijden, A. A. H., Kolobkov, B. I. & Novotortsev, V. M. (1994). J. Organomet. Chem. 471, 123-132.]); Pasynskii et al. (1993[Pasynskii, A. A., Kolobkov, B. I., Nefedov, S. E., Eremenko, I. L., Koltun, E. S., Yanovsky, A. I. & Struchkov, Yu. T. (1993). J. Organomet. Chem. 454, 229-236.]). For FeS-clusters as model compounds for active sites of hydrogenases, see: Gloaguen & Rauchfuss (2009[Gloaguen, F. & Rauchfuss, T. B. (2009). Chem. Soc. Rev. 38, 100-108.]).

[Scheme 1]

Experimental

Crystal data
  • [CaFe2S2(C4H8O)4(CO)6]

  • Mr = 672.38

  • Orthorhombic, P 21 21 21

  • a = 10.9189 (4) Å

  • b = 12.4167 (5) Å

  • c = 21.4545 (9) Å

  • V = 2908.7 (2) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 1.37 mm-1

  • T = 150 K

  • 0.25 × 0.11 × 0.08 mm

Data collection
  • Bruker-Nonius X8 APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.726, Tmax = 0.899

  • 21313 measured reflections

  • 5951 independent reflections

  • 5319 reflections with I > 2[sigma](I)

  • Rint = 0.033

Refinement
  • R[F2 > 2[sigma](F2)] = 0.027

  • wR(F2) = 0.057

  • S = 1.01

  • 5951 reflections

  • 334 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.36 e Å-3

  • [Delta][rho]min = -0.32 e Å-3

  • Absolute structure: Flack (1983)[Flack, H. D. (1983). Acta Cryst. A39, 876-881.], 2601 Friedel pairs

  • Flack parameter: 0.006 (11)

Table 1
Selected bond lengths (Å)

Fe1-Fe2 2.5152 (5)
Fe1-S1 2.2999 (7)
Fe1-S2 2.3185 (7)
Fe2-S1 2.3077 (7)
Fe2-S2 2.3110 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
C34-H34A...O1i 0.99 2.57 3.437 (5) 146
C34-H34B...O2ii 0.99 2.62 3.329 (4) 129
C42-H42A...O6iii 0.99 2.63 3.362 (4) 131
C45-H45B...O3iv 0.99 2.65 3.470 (3) 141
C15-H15A...O1v 0.99 2.67 3.561 (3) 150
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (ii) [-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]; (iii) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]; (iv) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (v) x-1, y, z.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2517 ).


Acknowledgements

The authors are grateful to the Russian Foundation for Basic Research (grant Nos. 10-03-00385, 12-03-31759 and 12- 03-31530) and the Federal target program Kadry (contract No. 8631) for financial support.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Cowie, M., DeKock, R. L., Wagenmaker, T. R., Seyferth, D., Henderson, R. S. & Gallagher, M. K. (1989). Organometallics, 8, 119-132.  [CrossRef] [ChemPort]
Eremenko, I. L., Berke, H., van der Zeijden, A. A. H., Kolobkov, B. I. & Novotortsev, V. M. (1994). J. Organomet. Chem. 471, 123-132.  [CrossRef] [ChemPort]
Fedushkin, I. L., Skatova, A. A., Chudakova, V. A., Fukin, G. K., Dechert, S. & Schumann, H. (2003). Eur. J. Inorg. Chem. pp. 3336-3346.  [CrossRef]
Flack, H. D. (1983). Acta Cryst. A39, 876-881.  [CrossRef] [details]
Gloaguen, F. & Rauchfuss, T. B. (2009). Chem. Soc. Rev. 38, 100-108.  [ISI] [CrossRef] [PubMed] [ChemPort]
Hieber, W. & Beck, J. (1958). Z. Anorg. Allg. Chem. 296, 91-103.  [CrossRef] [ChemPort]
Konchenko, S. N., Sanden, T., Pushkarevsky, N. A., Köppe, R. & Roesky, P. W. (2010). Chem. Eur. J. 16, 14278-14280.  [CrossRef] [ChemPort] [PubMed]
Pasynskii, A. A., Kolobkov, B. I., Nefedov, S. E., Eremenko, I. L., Koltun, E. S., Yanovsky, A. I. & Struchkov, Yu. T. (1993). J. Organomet. Chem. 454, 229-236.  [ChemPort]
Seyferth, D., Henderson, R. S. & Song, L. (1982). Organometallics, 1, 125-133.  [CrossRef] [ChemPort]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Veith, M., Auvray, N., Huch, V. & Braunstein, P. (2005). C. R. Chim. 8, 57-64.  [CrossRef] [ChemPort]


Acta Cryst (2012). E68, m1559-m1560   [ doi:10.1107/S1600536812048039 ]

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