Azido{4,4′-dibromo-2,2′-[ethane-1,2-diyl­bis(nitrilo­methanylylidene)]diphenol­ato-κ4 O,N,N′,O′}manganese(III)

Yingxia Liu

doi:10.1107/S1600536811004594

. 2011 Feb 12;67(Pt 3):m322. doi: 10.1107/S1600536811004594

Azido{4,4′-dibromo-2,2′-[ethane-1,2-diylbis(nitrilomethanylylidene)]diphenolato-κ⁴ O,N,N′,O′}manganese(III)

Yingxia Liu ^a,^*

PMCID: PMC3052106 PMID: 21522254

Abstract

In the title compound, [Mn(C₁₆H₁₂Br₂N₂O₂)(N₃)], the Mn^III ion is chelated by a tetradentate Schiff base ligand and coordinated by the N atom of an azide ligand in a distorted square-pyramidal arrangement. It forms phenolate-bridged out-of-plane dimers with Mn⋯O_phenolate distances of 2.667 (2) Å between pairs of inversion-related molecules. In the crystal, there are offset inter-complex face-to-face π–π interactions [centroid–centroid distances = 3.598 (2) Å] involving one of the benzene rings of the ligands.

Related literature

For related structures, see: Mikuriya et al. (1992 ▶); Li et al. (1997 ▶); Lu et al. (2006 ▶); Wang et al. (2008 ▶).

Experimental

Crystal data

[Mn(C₁₆H₁₂Br₂N₂O₂)(N₃)]
M _r = 1042.13
Monoclinic,
a = 8.7068 (17) Å
b = 15.269 (3) Å
c = 13.684 (3) Å
β = 107.47 (3)°
V = 1735.4 (6) Å³
Z = 2
Mo Kα radiation
μ = 5.39 mm⁻¹
T = 153 K
0.20 × 0.17 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.352, T _max = 0.583
7747 measured reflections
3961 independent reflections
3093 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.074
S = 1.04
3961 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and maXus (Mackay et al., 1998 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811004594/pk2299sup1.cif

e-67-0m322-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004594/pk2299Isup2.hkl

e-67-0m322-Isup2.hkl^{(194.2KB, hkl)}

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

supplementary crystallographic information

Comment

In the past decade there has been much interest in the magneto-chemistry of manganese because of its special magnetic properties. As is well known, manganese (III) Schiff base complexes display interesting structural, magnetic properties and electronic effects which rank it among the most appealing candidates as a building paramagnetic motif for multidimensional expanded structures. The variation of in-plane chelating and axial sites often leads to a change in the spin state of the metal ions: high-spin, low-spin or spin-crossover state. The nature and the tuning of magnetic interactions between metal centers are crucial points in the conception of molecular-based magnetic materials.

The molecular structure of the title compound is shown in Figure 1. The Mn^III ion is involved in a distorted square-pyramidal arrangement by a N3O2 unit, in which the four basal sites are occupied by two N atoms and two O atoms from the Schiff base ligand, and the apical position is occupied by the N atom of an azido ligand. The bond distances are comparable to those found in related structures (Lu, et al., 2006; Mikuriya, et al., 1992; Li, et al., 1997; Wang, et al., 2008). The Mn^III ion lies above the basal plane formed by N2O2 unit by 0.228 (1) Å. The short intermolecular distance of Mn···O_phenolate 2.667 (2) Å indicates that there exists weak interaction between the two complexes related by inversion centers in the crystal (Figure 2). The phenyl groups of the Schiff base are involved in an offset face-to-face π-π inter-complexes stacking interaction (ring centroid separation Cg···Cgⁱ, 3.598 (2) Å) [symmetry code: 2 - x,1 - y,1 - z].

Experimental

This compound was synthesized by mixing a solution of Schiff base (2,2'-((1E,1'E)-(ethane-1,2-diylbis(azanylylidene)) bis(methanylylidene))bis(4-bromophenol)) (0.5 mmol) in methanol (5 ml) with a solution of MnCl₂.4H₂O (0.5 mmol) in methanol (5 ml), followed by the dropwise addition of an aqueous solution NaN₃(0.6 mmol, 2 mL) without stirring. The black mixture was allowed to stand for several days until good quality black block crystals of the compound were obtained in a yield of 68.3%.