fac-[N,N′-Bis(3-chloro-2-fluoro­benzyl­idene)ethyl­enediamine]bromido­tri­carbonyl­rhenium(I)

Reza Kia; Hoong-Kun Fun

doi:10.1107/S1600536809001044

. 2009 Jan 14;65(Pt 2):m192–m193. doi: 10.1107/S1600536809001044

fac-[N,N′-Bis(3-chloro-2-fluorobenzylidene)ethylenediamine]bromidotricarbonylrhenium(I)

Reza Kia ^a, Hoong-Kun Fun ^a,^*

PMCID: PMC2968185 PMID: 21581793

Abstract

In the title compound, [ReBr(C₁₆H₁₂Cl₂F₂N₂)(CO)₃], the Re atom is in a slightly distorted octahedral coordination environment with the three carbonyl ligands having a fac configuration. The diimine ligand is equatorial and is bonded to the Re centre in an N,N′-bidentate chelating fashion, with a bite angle of 77.7 (2)°. The dihedral angle between the two benzene rings is 88.7 (6)°. In the crystal structure, there are F⋯O [2.856 (9) Å], Cl⋯C [3.150 (8) Å] and O⋯C [2.984 (10) Å] contacts which are shorter than the sum of the van der Waals radii for these atoms. In addition, symmetry-related molecules are linked via intermolecular C—H⋯O, C—H⋯Br and the F⋯O interactions into one-dimensional chains extending along the a axis. The crystal structure is further stabilized by intermolecular π–π interactions [centroid–centroid distance = 3.571 (5) Å].

Related literature

For values of standard bond lengths, see Allen et al. (1987 ▶). For related structures, see, for example: Kia et al. (2007 ▶). For backgroud to the applications of rhenium tricarbonyl diimine complexes, see, for example: Lee (1987 ▶); Farrell & Vlcek (2000 ▶); Collin & Sauvage (1989 ▶); Balzani et al. (1996 ▶).

Experimental

Crystal data

[ReBr(C₁₆H₁₂Cl₂F₂N₂)(CO)₃]
M _r = 691.32
Triclinic,
a = 7.3238 (3) Å
b = 12.3077 (4) Å
c = 13.1984 (5) Å
α = 116.504 (2)°
β = 99.707 (2)°
γ = 90.404 (2)°
V = 1044.84 (7) Å³
Z = 2
Mo Kα radiation
μ = 8.03 mm⁻¹
T = 100.0 (1) K
0.32 × 0.12 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.170, T _max = 0.569
33300 measured reflections
9014 independent reflections
7668 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.154
S = 1.08
9014 reflections
265 parameters
H-atom parameters constrained
Δρ_max = 4.36 e Å⁻³
Δρ_min = −2.86 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001044/lh2753sup1.cif

e-65-0m192-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001044/lh2753Isup2.hkl

e-65-0m192-Isup2.hkl^{(440.9KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Re1—C1	1.898 (7)
Re1—C3	1.911 (8)
Re1—C2	1.918 (7)
Re1—N2	2.190 (6)
Re1—N1	2.211 (6)
Re1—Br1	2.6564 (7)

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N2—Re1—N1

77.7 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯Br1	0.93	2.80	3.691 (7)	161
C10—H10A⋯Br1ⁱ	0.93	2.93	3.845 (7)	170
C11—H11B⋯O3ⁱ	0.97	2.48	3.264 (10)	137

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Symmetry code: (i) Inline graphic .

Acknowledgments

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Rhenium tricarbonyl diimine complexes have been the subject of much attention, mainly because of their photophysical and photochemical properties (Lee 1987; Farrell & Vlcek 2000; Balzani et al. 1996) and their use in the photoreducetion and electroreduction of CO₂ to CO (Collin & Sauvage 1989), a process of interest in the conversion and storage of solar energy. We report here the results of an X-ray structure determination of the title complex, (I).

In the title compound (I, Fig. 1), the Re atom is in a slightly distorted octahedral coordination environment. The bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to related structures (Kia et al., 2007). The three carbonyl ligands bonded to the Re atom are arranged in a fac configuration. The cis-equatorial bite angle [N1–Re1–N2] is 77.7 (2)°. The deviation of the Re atom from the mean plane defined by N1/N2/C2/C3 is 0.04 (4) Å. Due to the π-donor character of the bromine ligand, the length of the axial Re–C bond is slightly shorter than the values of the equatorial Re–C bonds (Table 1). In spite of the sp² hybrizidation of the donor nitrogen atoms of the diimine ligand, the ReN₂C₂ five-membered chelate ring is significantly puckered which is reflected in the deviation from 120° for the Re1–N1–C10 and Re1–N2–C13 angles being 135.2 (5)° and 131.4 (6)°, respectively. Some interesting features of the crystal structure are the F1···O2 [2.860 (12) Å; symmetry code: -1 + x, y, z], O2···C18 [2.981 (14); symmetry code: 1 - x, 1 - y, -z] and Cl2···C13 [3.143 (12) Å; symmetry code: 1 + x, y, z] contacts which are shorter than the sum of the van der Waals radii of these atoms. In addition, symmetry-related molecules are linked via intermolecular C—H···O, C—H···Br and C—F···O interactions into 1-D extended chains along the a-axis (Table 2, Fig. 2). The crystal structure is further stabilized by intramolecular C—H···Br and intermolecular π-π interactions [Cg1···Cg1 = 3.571 (5) Å; symmetry code: -x, -y, -z; Cg1 is the centroid of the C4–C9 benzene ring].

Experimental

The synthetic method has been described earlier (Kia et al., 2007), except that N,N'-bis(3-chloro-2-fluoro-benzylidene) ethylenediamine ligand and [Re(CO)₅Br] were used as starting materials. Single crystals suitable for X-ray diffraction were obtained by evaporation of an dichloromethane/toluene (4/1 ratio) solution at room temperature.