Chlorido{6,6′-dimethyl-2,2′-[1,2-phenyl­enebis(nitrilo­methyl­idyne)]diphenolato-κ4 O,N,N′,O′}manganese(III) mono­hydrate

Naser Eltaher Eltayeb; Siang Guan Teoh; Suchada Chantrapromma; Hoong-Kun Fun; Rohana Adnan

doi:10.1107/S160053680800620X

. 2008 Mar 12;64(Pt 4):m535–m536. doi: 10.1107/S160053680800620X

Chlorido{6,6′-dimethyl-2,2′-[1,2-phenylenebis(nitrilomethylidyne)]diphenolato-κ⁴ O,N,N′,O′}manganese(III) monohydrate

Naser Eltaher Eltayeb ^a,^‡, Siang Guan Teoh ^a, Suchada Chantrapromma ^b,^§, Hoong-Kun Fun ^c,^*, Rohana Adnan ^a

PMCID: PMC2960973 PMID: 21201996

Abstract

In the title complex, [Mn(C₂₂H₁₈N₂O₂)Cl]·H₂O, the Mn^III center is in a distorted square-pyramidal configuration, with the N₂O₂ dianionic tetradentate Schiff base ligand in the basal plane and the chloride ion in the apical position. The dihedral angle between the two outer phenolate rings of the tetradentate ligand is 8.25 (8)°. The central benzene ring makes dihedral angles of 4.31 (8) and 7.37 (8)° with the two outer phenolate rings. The water molecule links to the complex via an O—H⋯Cl hydrogen bond. In addition, in the crystal structure, weak C—H⋯O interactions link the molecules into infinite one-dimensional chains along [010]. The crystal is further stabilized by O—H⋯O and O—H⋯Cl hydrogen bonds, together with weak C—H⋯π interactions

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For details of ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see for example: Eltayeb et al. (2007 ▶); Habibi et al. (2007 ▶); Mitra et al. (2006 ▶); Naskar et al. (2004 ▶). For background to the application of manganese complexes, see for example: Dixit & Srinivasan (1988 ▶); Glatzel et al. (2004 ▶); Lu et al. (2006 ▶); Stallings et al. (1985 ▶).

Experimental

Crystal data

[Mn(C₂₂H₁₈N₂O₂)Cl]·H₂O
M _r = 450.79
Monoclinic,
a = 27.1836 (6) Å
b = 6.8033 (1) Å
c = 21.8896 (4) Å
β = 108.976 (1)°
V = 3828.22 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 100.0 (1) K
0.42 × 0.26 × 0.11 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.714, T _max = 0.915
24765 measured reflections
5586 independent reflections
4459 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.100
S = 1.10
5586 reflections
264 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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/S160053680800620X/sj2469sup1.cif

e-64-0m535-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800620X/sj2469Isup2.hkl

e-64-0m535-Isup2.hkl^{(273.6KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯Cl1	0.87	2.54	3.3544 (16)	157
O1W—H2W1⋯O1ⁱ	0.84	2.43	3.191 (2)	151
O1W—H2W1⋯O2ⁱ	0.84	2.53	3.2642 (19)	146
C16—H16A⋯O1Wⁱⁱ	0.93	2.48	3.364 (2)	160
C7—H7A⋯Cg1ⁱⁱⁱ	0.93	3.39	3.9811 (17)	123

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the C1–C6 benzene ring.

Acknowledgments

The authors thank the Malaysian Government, Ministry of Science, Technology and Innovation (MOSTI) and Universiti Sains Malaysia for the E-Science Fund research grant (PKIMIA/613308) and facilities. The International University of Africa (Sudan) is acknowledged for providing study leave to NEE. The authors also thank Universiti Sains Malaysia for the Fundamental Research Grant Scheme (FRGS) grant No. 203/PFIZIK/671064.

supplementary crystallographic information

Comment

Schiff base ligands containing strong donor sites such as oxygen and imine nitrogen atoms and their metal complexes have been the subject of extensive investigation. Manganese complexes with Schiff base ligands have attracted considerable interest in the past decades and recently, due to their variety of applications in chemistry, biology, physics and advanced materials. They have been used as models for the oxygen-evolving complex of photosystem II (Glatzel et al., 2004), in catalysis (Dixit and Srinivasan, 1988), as single-molecule magnets (Lu et al., 2006) and serve as models for the active sites of manganese-containing metal enzymes (Stallings et al., 1985). Recently, we reported the crystal structure of 4,4'-Dimethoxy-2,2'-[1,2-phenylenebis(nitrilomethylidyne)]diphenol, (Eltayeb et al., 2007). We report here the crystal structure of a Mn(III) complex of the closely related ligand 2,2'-{1,2-phenylenebis[nitrilomethylylidene]}bis(6-methylphenol).

In the title complex molecule (Fig. 1), the coordination sphere of the Mn^III ion is a slightly distorted square-pyramid consisting of the N₂O₂ coordination plane of the dianionic tetradentate Schiff base ligand (coordinating through N1, N2, O1 and O2) and the axially bound chloride ion. The Mn—O distances [Mn1—O1 = 1.8672 (11) Å and Mn1—O2 = 1.8587 (13) Å] and Mn—N distances [Mn1—N1 = 1.9887 (4) Å and Mn1—N2 = 1.9922 (13) Å are quite similar to those observed in other related Mn^III complexes of N₂O₂ Schiff base ligands (Habibi et al., 2007; Mitra et al., 2006). Other bond lengths and angles observed in the structure are also normal (Allen et al., 1987). Coordination of the the N₂O₂ chelate ligand to the Mn^III ion results in the formation of a planar five-membered ring (Mn1/N1/N2/C8/C13) and two six-membered rings; the Mn1/O2/N2/C14/C15/C20 ring is almost planar whereas the Mn1/O1/N1/C1/C6/C7 ring adopts an envelope conformation with atom O1 displaced from the Mn1/N1/C1/C6/C7 plane by 0.159 (1) Å and with Cremer & Pople (1975) puckering parameters Q = 0.274 (1) °, θ = 61.3 (4) ° and φ = 12.8 (4) °. The dihedral angle between the two outer phenolate rings [C1–C6 and C15–C20] of the Schiff base ligand is 8.25 (8) °. The central benzene ring (C8–C13) makes dihedral angles of 4.31 (8) ° and 7.37 (8) ° with the two outer phenolate rings, respectively. The water molecule forms an O—H···Cl hydrogen bond with the complex.

In the crystal packing (Fig. 2), a weak C—H···O interaction [C16—H16···O1W; symmetry code -x, 1 - y, -z (Table 1)] links the molecules into infinite one-dimensional chains along the [0 1 0] direction. The crystal is further stabilized by O—H···O and O—H···Cl hydrogen bonds, together with weak C—H···π interactions (Table 1); Cg₁ is the centroid of the C1–C6 benzene ring.

Experimental

The title compound was synthesized by adding 2-hydroxy-3-methylbenzaldehyde (0.5 ml, 4 mmol) to a solution of o-phenylenediamine (0.216 g, 2 mmol) in ethanol 95% (30 ml). The mixture was refluxed with stirring for half an hour. Manganese chloride tetrahydrate (0.394 g, 2 mmol) in ethanol (10 ml) was then added, followed by triethylamine (0.5 ml, 3.6 mmol). The mixture was refluxed at room temperature for three hours. A brown precipitate was obtained, washed with about 5 ml e thanol, dried, and then washed with copious quantities of diethylether. Brown single crystals of the title compound suitable for x-ray structure determination were recrystallized from methanol by slow evaporation of the solvent at room temperature over several days.