Bis[μ-2-(2-benzoyl­hydrazinylidenemeth­yl)-6-methoxy­phenolato][2-(2-benzoyl­hydrazinylidenemeth­yl)-6-methoxy­phenolato]dimanganese(II) perchlorate methanol solvate

Gui-Miao Yu; Yun-Hui Li; Li-Fei Zou; Jian-Wei Zhu; Xiao-Qiu Liu

doi:10.1107/S1600536810018040

. 2010 May 22;66(Pt 6):m693–m694. doi: 10.1107/S1600536810018040

Bis[μ-2-(2-benzoylhydrazinylidenemethyl)-6-methoxyphenolato][2-(2-benzoylhydrazinylidenemethyl)-6-methoxyphenolato]dimanganese(II) perchlorate methanol solvate

Gui-Miao Yu ^a, Yun-Hui Li ^a, Li-Fei Zou ^a, Jian-Wei Zhu ^b,^*, Xiao-Qiu Liu ^b

PMCID: PMC2979386 PMID: 21579331

Abstract

In the title complex, [Mn₂(C₁₅H₁₃N₂O₃)₃]ClO₄·CH₃OH, the two Mn^II ions are bridged by two phenolate O atoms from two ligands, forming an Mn₂O₂ quadrangle. Each Mn^II ion has a distorted octahedral coordination geometry. One Mn^II ion is coordinated by two N atoms and four O atoms from two ligands, and the other is coordinated by one N atom and five O atoms from three ligands. A dimer is formed by intermolecular N—H⋯O hydrogen bonds. The dimers, perchlorate anions and methanol solvent molecules are further connected into a chain along [ Inline graphic 01] through N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For general background to the study of Schiff base compounds, see: Ando et al. (2004 ▶); Costes et al. (1995 ▶); Duda et al. (2003 ▶); Siddall et al. (1983 ▶). For related structures, see: Li et al. (2010 ▶); Huang & Li (2007 ▶); Mikuriya et al. (1992 ▶); Yin (2008 ▶); Yu et al. (2006 ▶). For the ligand synthesis, see: Pouralimardan et al. (2007 ▶); Sacconi (1954 ▶).

Experimental

Crystal data

[Mn₂(C₁₅H₁₃N₂O₃)₃]ClO₄·CH₄O
M _r = 1049.19
Triclinic,
a = 12.7184 (6) Å
b = 13.8723 (7) Å
c = 15.0885 (12) Å
α = 100.268 (1)°
β = 94.030 (1)°
γ = 115.826 (1)°
V = 2324.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 173 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.906, T _max = 0.936
11959 measured reflections
8138 independent reflections
6183 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.123
S = 1.05
8138 reflections
627 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810018040/hy2307sup1.cif

e-66-0m693-sup1.cif^{(30.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018040/hy2307Isup2.hkl

e-66-0m693-Isup2.hkl^{(398.1KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—O2	2.099 (2)
Mn1—O3	2.148 (2)
Mn1—O8	2.105 (2)
Mn1—O9	2.196 (2)
Mn1—N1	2.263 (2)
Mn1—N5	2.253 (3)
Mn2—O1	2.427 (2)
Mn2—O2	2.083 (2)
Mn2—O5	2.061 (2)
Mn2—O6	2.192 (2)
Mn2—O8	2.215 (2)
Mn2—N3	2.200 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O5ⁱ	0.88	2.04	2.907 (3)	168
N4—H4A⋯O13ⁱⁱ	0.88	2.08	2.910 (4)	156
N6—H6A⋯O14	0.88	1.98	2.810 (4)	156
O14—H14A⋯O10ⁱⁱⁱ	0.84	2.05	2.865 (4)	165

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

Acknowledgments

The authors thank Changchun University of Science and Technology for a research grant and Fujian Normal University for a technology grant.

supplementary crystallographic information

Comment

Studies of Schiff base compounds are of great interest in various aspects of chemistry, such as homogeneous catalysts in industry, antitumor activities, photoelectric materials, catalytic materials, etc. (Ando et al., 2004; Costes et al., 1995; Duda et al., 2003; Siddall et al., 1983). The crystal structures of metal complexes with salicylaldehyde benzoylhydrazide have been attracted tremendous interest (Huang & Li, 2007; Yin, 2008; Yu et al., 2006). As a continuation of our effort in this system, we investigated a novel Schiff base, 3-methoxysalicylaldehyde benzoylhydrazide (H₂L). This multidentate ligand has several O and N donors with suitable relative positions, which can coordinate to two or more metal centers. In addition, the vanillin group displays a variety of bonding geometries, such as monodentate, chelating, bidentate bridging, monodentate bridging, and chelating bridging (Li et al., 2010). We report here the synthesis and crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. There are two crystallographically independent Mn^II centers with different coordination environments in the asymmetric unit. The two Mn^II ions, Mnl and Mn2, are bridged by two phenolate O atoms (O2, O8) from two Schiff base ligands (Table 1). The Mn1···Mn2 separation is 3.284 (1) Å, and the Mn1—O2—Mn2 and Mn1—O8—Mn2 angles are 103.50 (9) and 98.92 (8)°, respectively. The coordination geometry of each Mn^II ion is distorted octahedral. The Mn1 atom is coordinated by two N atoms and four O atoms from two ligands. The square plane around the Mn1 atom is formed by O₂N₂ donor atoms (N1, N5, O8 and O9) and the axial positions are occupied by phenolate O2 and carbonyl O3. However, the Mn2 atom is coordinated by one N atom and five O atoms from three ligands. The distorted octahedral coordination is achieved by the equatorial plane donor atoms, methoxy O1, carbonyl O2, phenolate O8 and hydrazine N3, and the coordination of phenolate O5 and carbonyl O6 at the axial positions. In addition, the methoxy O1 is weakly bonded to Mn2 with a Mn2—O1 distance of 2.427 (2) Å, which is comparable to those reported for other binuclear Mn^II complexes (Mikuriya et al., 1992). In the crystal structure, two adjacent molecules participate in complementary N(hydrazine)—H···O(phenolate) hydrogen bonds, forming a dimeric structure (Fig. 2 and Table 2). The dimers, perchlorate anions and methanol solvent molecules are further connected into a chain structure through N—H···O and O—H···O hydrogen bonds (Fig. 3).

Experimental

The Schiff base ligand (H₂L) was prepared in a similar manner to the reported procedures (Pouralimardan et al., 2007; Sacconi, 1954). The title compound was synthesized by adding Mn(ClO₄)₂.6H₂O (36.6 mg, 0.1 mmol) and imidazole(6.8 mg, 0.1 mmol) to a solution of H₂L (27.3 mg, 0.1 mmol) in methanol (15 ml). The resulting mixture was stirred for 5 h at room temperature to afford a yellow solution, which was left unperturbed to allow slow evaporation of the solvent. Yellow single crystals suitable for X-ray diffraction analysis were formed after about two weeks.