Tris(5,6-dimethyl-1,10-phenanthroline-κ2N,N′)iron(II) bis­(tricyano­methanide)

Váhovská, L.; Potočňák, I.

doi:10.1107/S1600536812046880

Volume 68
Part 12
Pages m1524-m1525
December 2012

Received 29 October 2012
Accepted 14 November 2012
Online 24 November 2012

Key indicators
Single-crystal X-ray study
T = 183 K
Mean (C-C) = 0.004 Å
R = 0.050
wR = 0.125
Data-to-parameter ratio = 14.2
Details

Tris(5,6-dimethyl-1,10-phenanthroline-²N,N')iron(II) bis(tricyanomethanide)

Lucia Váhovská ^a ^* and Ivan Potocnák ^a

^aInstitute of Chemistry, Faculty of Science, P.J. Safárik University, Moyzesova 11, SK-041 54 Kosice, Slovakia
Correspondence e-mail: lucia.vahovska@student.upjs.sk

The title compound, [Fe(C₁₄H₁₂N₂)₃](C₄N₃)₂, consists of one [Fe(dimephen)₃]²⁺ complex cation (dimephen = 5,6-dimethyl-1,10-phenanthroline) and two uncoordinating tcm anions (tcm = tricyanomethanide). In the complex cation, the Fe^II atom is coordinated by six N atoms from three chelating dimephen ligands at an average Fe-N distance of 1.963 (4) Å giving a distorted octahedral geometry. The crystal structure is stabilized by weak C-HN hydrogen bonds and C [triple bond] N [pi] interactions between planar [maximum deviations of 0.024 (3) and 0.015 (3) Å] tcm anions and pyridine rings of dimephen [N2centroid = 3.531 (3) and 3.726 (3) Å; CNcentroid = 96.4 (2) and 97.1 (2)°].

Related literature

[Fe(phen)₂(NCS)₂] (phen = 1,10-phenathroline) and [Fe(bpy)₂(NCS)₂] (bpy = 2,2-bipyridine) are the first known and most extensively studied compounds of iron(II) exhibiting a high spin [leftwards arrow] [rightwards arrow] low spin transition, see: König & Watson (1970); Müller et al. (1982). For [Fe(phen)₃]²⁺complexes, see: Aparici Plaza et al. (2007); Odoko & Okabe (2004); Koh et al. (1994); Uçar et al. (2005); Li et al. (2008). For bond lengths and angles in dimephen, see: Toledano-Magaña et al. (2012) and in tcm ligands, see: Potocnák et al. (2002); Luo et al. (2009). For the structure, properties and bonding modes of the tcm anion, see: Golub et al. (1986); Kohout et al. (2000). For the crystal and molecular structure of phen, see: Nishigaki et al. (1978). For similar Fe^II complexes, see: Váhovská & Potocnák (2012).

Experimental

Crystal data

[Fe(C₁₄H₁₂N₂)₃](C₄N₃)₂
M_r = 860.76
Triclinic, $[P \overline 1]$
a = 9.3676 (3) Å
b = 12.7079 (9) Å
c = 18.1998 (9) Å
= 75.458 (5)°
= 89.623 (3)°
= 82.323 (4)°
V = 2077.52 (19) Å³
Z = 2
Mo K radiation
= 0.42 mm^-1
T = 183 K
0.66 × 0.25 × 0.03 mm

Data collection

Agilent Xcalibur (Sapphire2) diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)] T_min = 0.874, T_max = 0.986
15408 measured reflections
8167 independent reflections
6309 reflections with I > 2(I)
R_int = 0.025

Refinement

R[F² > 2(F²)] = 0.050
wR(F²) = 0.125
S = 1.07
8167 reflections
574 parameters
H-atom parameters constrained
_max = 0.92 e Å^-3
_min = -0.40 e Å^-3

Table 1
Selected bond lengths (Å)

Fe1-N20	1.957 (2)
Fe1-N10	1.959 (2)
Fe1-N60	1.963 (2)
Fe1-N30	1.965 (2)
Fe1-N50	1.967 (2)
Fe1-N40	1.968 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
C52-H52N30	0.95	2.59	3.070 (3)	112
C22-H22N40	0.95	2.59	3.089 (4)	113
C32-H32N8	0.95	2.43	3.266 (4)	146
C42-H42N60	0.95	2.57	3.056 (3)	112
C22-H22N6ⁱ	0.95	2.54	3.271 (4)	134
C12-H12N2ⁱⁱ	0.95	2.55	3.352 (4)	142
C62-H62N3ⁱⁱⁱ	0.95	2.51	3.266 (4)	137
C44-H44N7^iv	0.95	2.59	3.312 (4)	133
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y, z; (iii) -x, -y+1, -z; (iv) x-1, y-1, z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2428 ).

Acknowledgements

This work was supported by the Slovak Research and Development Agency under contract No. APVV-0014-11 and by the internal P. J. Safárik University grant system (VVGS-PF-2012-24 and VVGS 1/12-13).

References

Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.
Aparici Plaza, L., Baranowska, K. & Becker, B. (2007). Acta Cryst. E63, m1537-m1539.
Brandenburg, K. (2001). DIAMOND. Crystal Impact, Bonn, Germany.
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897.
Golub, A. M., Köhler, H. & Skopenko, V. V. (1986). Chemistry of Pseudohalides, pp. 313-318. Amsterdam: Elsevier.
Koh, L. L., Xu, Y., Hsieh, A. K., Song, B., Wu, F. & Ji, L. (1994). Acta Cryst. C50, 884-886.
Kohout, J., Jäger, L., Hvastijová, M. & Kozísek, J. (2000). J. Coord. Chem. 51, 172-182.
König, E. & Watson, K. J. (1970). Chem. Phys. Lett. 6, 457-459.
Li, Z.-X., Yu, M.-M., Zhang, Y.-N. & Wei, L.-H. (2008). Acta Cryst. E64, m1514.
Luo, J., Zhang, X.-R., Qiu, L.-J., Liu, B.-S. & Zhang, Z.-Y. (2009). Acta Cryst. E65, m455-m456.
Müller, E. W., Spiering, H. & Gütlich, P. (1982). Chem. Phys. Lett. 93, 567-571.
Nishigaki, S., Yoshioka, H. & Nakatsu, K. (1978). Acta Cryst. B34, 875-879.
Odoko, M. & Okabe, N. (2004). Acta Cryst. E60, m1822-m1824.
Potocnák, I., Pohlová, M., Wagner, C. & Jäger, L. (2002). Acta Cryst. E58, m595-m596.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Toledano-Magaña, Y., García-Ramos, J.-C., García-Manrique, C., Flores-Alamo, M. & Ruiz-Azuara, L. (2012). Acta Cryst. E68, m987-m988.
Uçar, I., Pasaoglu, H., Büyükgüngör, O. & Bulut, A. (2005). Acta Cryst. E61, m1405-m1407.
Váhovská, L. & Potocnák, I. (2012). J. Chem. Crystallogr. Submitted.

metal-organic compounds

Tris(5,6-dimethyl-1,10-phenanthroline-2N,N')iron(II) bis(tricyanomethanide)