cis-Bis(2,2′-bipyridine-κ2 N,N′)dichlorido­iron(III) perchlorate

Zhi-Fang Zhang

doi:10.1107/S1600536811016035

. 2011 May 7;67(Pt 6):m677. doi: 10.1107/S1600536811016035

cis-Bis(2,2′-bipyridine-κ² N,N′)dichloridoiron(III) perchlorate

Zhi-Fang Zhang ^a,^*

PMCID: PMC3120418 PMID: 21754585

Abstract

In the crystal structure of the title compound, [FeCl₂(C₁₀H₈N₂)₂]ClO₄, the coordination around the Fe^III atom is approximately octahedral. The equatorial positions are occupied by two N atoms from two 2,2′-bipyridyl ligands [Fe—N = 2.121 (5) and 2.147 (5) Å] and two Cl atoms [Fe—Cl = 2.220 (2) and 2.2074 (18) Å]. Weak intermolecular C—H⋯O and C—H⋯Cl hydrogen bonds and C—H⋯π interactions consolidate the crystal packing.

Related literature

For the use of bipyridine and analogous ligands in the formation of transition metal complexes, see: Constable (1989 ▶). For applications of related compounds, see: Constable & Steel (1989 ▶); Steel et al. (1990 ▶). For related structures, see: Amani et al. (2007 ▶); Figgis et al. (1983 ▶).

Experimental

Crystal data

[FeCl₂(C₁₀H₈N₂)₂]ClO₄
M _r = 538.57
Orthorhombic,
a = 10.891 (2) Å
b = 11.522 (2) Å
c = 16.990 (3) Å
V = 2132.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 295 K
0.34 × 0.29 × 0.24 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.702, T _max = 0.775
5914 measured reflections
3534 independent reflections
2810 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.125
S = 1.08
3534 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.42 e Å⁻³
Absolute structure: Flack (1983 ▶), 1419 Friedel pairs
Flack parameter: 0.05 (3)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016035/zq2098sup1.cif

e-67-0m677-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016035/zq2098Isup2.hkl

e-67-0m677-Isup2.hkl^{(173.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg4 is the centroid of the N2,C6–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2	0.93	2.52	3.140 (11)	124
C7—H7⋯O3ⁱ	0.93	2.55	3.239 (9)	131
C8—H8⋯O2ⁱⁱ	0.93	2.30	3.152 (9)	152
C13—H13⋯O2ⁱⁱⁱ	0.93	2.54	3.423 (10)	158
C18—H18⋯O4^iv	0.93	2.51	3.387 (10)	158
C10—H10⋯Cl3	0.93	2.71	3.308 (7)	122
C20—H20⋯Cl2	0.93	2.79	3.382 (7)	123
C11—H11⋯Cg4	0.93	2.90	3.705 (8)	146

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

Acknowledgments

The author gratefully acknowledges financial support from the Natural Science Foundation of the Education Department of Shaanxi Provincial Government (09 J K844) and is grateful for support provided by the key industry problem plan of Yulin (gygg200807) and the special research projects of Yulin University (08YK17).

supplementary crystallographic information

Comment

Bipyridine and analogous ligands such as phenanthroline are commonly used in the formation of different complexes with a general variety of transition metals (Constable, 1989). Studies of these transition metal complexes are important in understanding electron transfer processes, mixed valence complexes, magnetic coupling and magnetic transitions (Constable et al., 1989; Steel et al., 1990). Although bipyridine coordination to iron has been widely investigated, most complexes are iron(II) complexes, little attention has been paid to bipyridine iron(III) complexes. In order to expand this field, the title compound has been synthesized, and its crystal structure is reported herein.

The molecular structure of the title compound (I) is shown in Fig. 1. The crystal is composed of cis-[Fe^III(bipy)₂C1₂]⁺ cations and [C1O₄]^- anions. The Fe^III atom is coordinated by two Cl anions and four N atoms from two 2,2'-bipyridyl ligands within a distorted octahedral geometry. The six-coordinate molecule is the cis-cis isomer considering the positions of the chlorine and pyridyl nitrogen atoms. The four Fe—N bond lengths [2.087 (4)–2.147 (5) Å] were similar and consistent with those reported earlier (Amani et al., 2007; Figgis et al., 1983). The distortion from a perfect octahedral geometry was primarily a consequence of the small bite-angle of the chelating ligands, which led to acute N1—Fe—N2 and N3—Fe—N4 angles of 75.96 (19)° and 75.4 (2)°, respectively.

Intermolecular C—H···O, C—H···Cl hydrogen bonds and C—H···π interactions stabilize the crystal structure (Table 1).

Experimental

All reagents were obtained from commercial sources and used without further purification. 2,2'-Bipyridine (0.312 g, 2.0 mmol) and NaClO₄ (0.122 g,1.0 mmol) were added to a solution of FeCl₃.6H₂O (0.270 g, 1.0 mmol) in methanol (30 ml), and the solution was stirred at 60–65 ^oC for 3 h. A red-brown precipitate was obtained. After filtration, the red-brown filtrate was allowed to stand at room temperature for two weeks to give red-brown block-shaped crystals suitable for X-ray analysis. Elemental analysis for C₂₀H₁₆Cl₃FeN₄O₄: C 44.60, H 2.99, N 10.40 %; found: C 44.52, H 3.03, N 10.39 %.