Bis(1H-imidazole-κN 3){2,2′-[propane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato-κ4 O,N,N′,O′}iron(III) perchlorate

Yoshihiro Kojima; Kazuya Kato; Yuuki Yamamoto; Katsuya Inoue; Shinya Hayami

doi:10.1107/S1600536810004010

. 2010 Feb 17;66(Pt 3):m302–m303. doi: 10.1107/S1600536810004010

Bis(1H-imidazole-κN ³){2,2′-[propane-1,2-diylbis(nitrilomethylidyne)]diphenolato-κ⁴ O,N,N′,O′}iron(III) perchlorate

Yoshihiro Kojima ^a, Kazuya Kato ^b, Yuuki Yamamoto ^b, Katsuya Inoue ^a, Shinya Hayami ^b,^*

PMCID: PMC2983534 PMID: 21580245

Abstract

The title compound, [Fe(C₁₇H₁₆N₂O₂)(C₃H₄N₂)₂]ClO₄, consists of monomeric [Fe(salmen)(HIm)₂]⁺ cations {salmen is the 2,2′-[propane-1,2-diylbis(nitrilomethylidyne)]diphenolate dianion and HIm is 1H-imiazole} and perchlorate anions. In the cation, the Fe³⁺ ion is octahedrally coordinated by two N atoms and two O atoms from a tetradentate salmen anion and two N atoms from two Him molecules. These ligands are coordinated to the iron ion in a direction perpendicular to the [Fe(salmen)]⁺ coordination plane. The benzene ring planes in the salmen ligands are oriented nearly parallel to one another intermolecularly [dihedral angle = 6.36 (3)°]. The dihedral angle between the mean planes through the imidazole rings in the cation is 76.9 (2)°. In the crystal, N—H⋯O interactions link the molecules into a one-dimensional double chain running along [101] and C—H⋯O interactions link the double chains into a two-dimensional network, running parallel to the ac plane.

Related literature

For salen–metal complexes with spin crossover properties, see: Brendan et al. (1984 ▶, 1987 ▶); Hernández-Molina et al. (1998 ▶).

Experimental

Crystal data

[Fe(C₁₇H₁₆N₂O₂)(C₃H₄N₂)₂]ClO₄
M _r = 571.78
Monoclinic,
a = 10.4898 (8) Å
b = 16.4312 (9) Å
c = 14.7729 (8) Å
β = 105.5081 (17)°
V = 2453.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 113 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID Imaging Plate diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 2001 ▶) T _min = 0.860, T _max = 0.860
20794 measured reflections
5615 independent reflections
3529 reflections with I > 2σ(I)
R _int = 0.086

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.179
S = 0.99
5615 reflections
335 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalClear (Molecular Structure Corporation and Rigaku, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Yadokari-XG (Wakita, 2000 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004010/kj2139sup1.cif

e-66-0m302-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004010/kj2139Isup2.hkl

e-66-0m302-Isup2.hkl^{(274.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Fe1—O1	1.879 (2)
Fe1—O2	1.914 (3)
Fe1—N1	2.119 (3)
Fe1—N2	2.108 (3)
Fe1—N3	2.161 (3)
Fe1—N5	2.161 (3)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O6ⁱ	0.95	2.53	3.436 (6)	161
C16—H16⋯O5	0.95	2.53	3.325 (6)	142
N4—H4A⋯O2ⁱⁱ	0.88	2.48	3.063 (4)	125
N4—H4A⋯O6ⁱⁱ	0.88	2.36	3.031 (4)	133
N6—H6A⋯O4ⁱⁱⁱ	0.88	2.03	2.892 (4)	167

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This work was supported by ‘Development of Molecular Devices in Ferroelectric Metallomesogens’ in 2006 of the New Energy and Industrial Technology Development Organization (NEDO) of Japan, and by Grants-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology of the Japanese Government (No. 20350028).

supplementary crystallographic information

Comment

A number of spin-crossover compounds have been studied. The salen molecule (salen = N,N'-ethylenebis(salicylideneiminato) dianion) has often been used as ligand in spin-crossover complexes (Brendan et al., 1984, Hernández-Molina et al., 1998). Brendan et al. reported Fe(III)-salen complexes [Fe(salen)(L)₂](Y) (L = imidazole series, Y = counter anion) and showed that the spin state can be tuned by using different imidazole series and counter anions (Brendan et al., 1987). They also showed that [Fe(salen)(HIm)₂](ClO₄)₂ has spin-crossover properties. In this study, the crystal stucture of the derivative [Fe(salmen)(HIm)₂](ClO₄)₂ is reported.

The title compound consists of a cation whose iron ion is coordinated by a salmen anion and two imidazole ligands. The structure further contains a perchlorate anion. The molecular planes of the benzene rings of all salmen ligands in the crystal are oriented essentially parallel to one another. The two imidazoles coordinated to the Fe³⁺ ion aren't coplanar; the dihedral angle between their mean planes is 76.9 (2)°. Imidazole ligands are coordinated to iron ion in a direction perpendicular to [Fe(salmen)]⁺, with the angle around iron ion O1— Fe1— N3 = 88.40 (12)°, O2—Fe1—N3 = 90.95 (12)°, O1—Fe1—N5 = 93.19 (12)° and O2—Fe1—N5 = 87.99 (12)°. The two benzene rings in a salmen ligand are nearly coplanar, but the bridging carbon atoms are not located in this plane. C2 is displaced 0.1057 (2)Å from the C5–C12 benzene plane and C3 is displaced 0.1785 (2)Å from the C12–C17 benzene plane. The torsion angle N1—C2—C3—N2 is 41.1 (5)°.

In addition, many intermolecular interactions are observed in the crystal structure. Intermolecular C—H···O hydrogen bonds link the benzene hydrogens H7 and H16 with the anion oxygens O6 and O5, respectively. N—H···O hydrogen bonds link the imidazole hydrogen H6A to anionic oxygen O4 and link the imidazole H4A in a bifurcated bond to the ring oxygen O2 and the anion oxygen O6. The N—H···O interactions link the molecules into a one-dimensional double chain (step ladder) running in the [1 0 1] direction, with N4—H4A···O2 acting as the rungs in the ladder. The C—H···O interactions link the double chains into a two-dimensional network, running parallel to the ac plane.

Experimental

The salmen ligand was prepared by the reaction of 1, 2-diaminopropane (2 mmol) and salicylaldehyde (4 mmol) in ethanol. The title compound was synthesized in accordance with the procedure reported in the literature (Brendan et al., 1987).