Triaqua­bis­{2-meth­oxy-6-[(phenyl­iminium­yl)meth­yl]phenolate-κO 1}manganese(II) dinitrate

Guo-Di Ge; Jin-Bei Shen; Guo-Liang Zhao

doi:10.1107/S1600536811019593

. 2011 May 28;67(Pt 6):m813–m814. doi: 10.1107/S1600536811019593

Triaquabis{2-methoxy-6-[(phenyliminiumyl)methyl]phenolate-κO ¹}manganese(II) dinitrate

Guo-Di Ge ^a, Jin-Bei Shen ^a, Guo-Liang Zhao ^a,^b,^*

PMCID: PMC3120327 PMID: 21754686

Abstract

The crystal structure of the title compound, [Mn(C₁₄H₁₃NO₂)₂(H₂O)₃](NO₃)₂, is comprised of two Schiff base 2-methoxy-6-(N-phenylcarboximidoyl)phenol (HL) ligands and three coordinated water molecules. The Mn^II ion lies on a twofold axis that bisects one water O atom. The coordination sphere of the five-coordinate Mn atom is completed by the two monodentate HL ligands and three coordinated water molecules binding through their O atoms, affording a distorted tetragonal–pyramidal geometry. In the phenolate ligands, the hydroxy H atom transfers to the imine N atom. This H atom is also involved in an intramolecular N—H⋯O hydrogen bond that imposes a nearly planar conformation on each ligand, with dihedral angles of 2.78 (3) and 2.43 (5)° between the aromatic rings of each ligand. In the crystal, molecules are linked by intermolecular O—H⋯O hydrogen bonds.

Related literature

For Schiff base ligands derived from o-vanillin and aniline and their rare earth complexes, see: Garnovskii et al. (1993 ▶); Shen et al. (2011 ▶); Zhao et al. (2006 ▶). For the synthesis of related Schiff bases, see: Burrows & Bailar (1966 ▶).

Experimental

Crystal data

[Mn(C₁₄H₁₃NO₂)₂(H₂O)₃](NO₃)₂
M _r = 687.52
Orthorhombic,
a = 17.4364 (3) Å
b = 10.4199 (2) Å
c = 16.9014 (3) Å
V = 3070.74 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 296 K
0.26 × 0.14 × 0.06 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.918, T _max = 0.969
11534 measured reflections
2705 independent reflections
1864 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.118
S = 1.07
2705 reflections
210 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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 global. DOI: 10.1107/S1600536811019593/rn2084sup1.cif

e-67-0m813-sup1.cif^{(18.1KB, cif)}

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—H1WA⋯O5ⁱ	0.85	2.18	3.032 (3)	180
O1W—H1WB⋯O4ⁱⁱ	0.85	1.96	2.809 (3)	180
O2W—H2WA⋯O3ⁱⁱ	0.85	1.96	2.800 (3)	169
N1—H1A⋯O1	0.86	1.92	2.611 (2)	137

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

supplementary crystallographic information

Comment

It has well been documented that Schiff bases are important in diverse fields of chemistry and biochemistry owing to their biological activities (Garnovskii et al., 1993). The complexes prepared by ligands derived from o -vanillin have attracted considerable attention for a number of years due to the intriguing biological activities of o-vanillin and the convenience of the synthesis of related Schiff bases (Burrows & Bailar, 1966). For these reasons, we have been engaged in the syntheses of new Schiff bases derived from o-vanillin and their transition and rare earth metal complexes (Shen et al. 2011; Zhao et al. 2006). Herein, we describe a new Mn^II complex.

The structure of complex (1) is shown in Fig. 1, which contains two 2-methoxy-6-(N-phenylcarboximidoyl)phenol (HL) ligands, three coordinated water molecules and two independent nitrate ions. The coordination sphere of the five-coordinate Mn atom is completed by the two monodentate HL ligands and three coordinated water molecules binding through their O atoms, affording a distorted tetragonal pyramid geometry. The coordination geometry around Mn^II is better described as a distorted square pyramid with the basal positions occupied by the four O atoms; O1, O1A, O1W and O1WA. The apical position is occupied by O2W. The Mn^II ion lies on a twofold axis that bisects O2W. The five Mn—O bond distances are listed in Table 1.The Mn—O (phenolic) bonds are 2.118 (4) Å, which are shorter than the similar reported complexes (Shen et al. 2011).

The hydrogen bonds lend stability to the structure. The packing plot of this compound is shown in Fig. 2. In the phenolate ligands, the proton of the phenolic hydroxy group transfers to the imine N atom. This proton is also involved in an intramolecular N—H···O hydrogen bond that imposes a nearly planar conformation on each ligand, with dihedral angles of 2.78 (3) and 2.43 (5)° between the aromatic rings of each ligand. In the crystal structure, molecules are linked by intermolecular O—H···O hydrogen bonds.

Experimental

Reagents and solvents used were of commercially available quality. The Schiff base ligand 2-methoxy-6-(N-phenylcarboximidoyl)phenol was synthesized from condensation of o-vanillin and aniline. 1 mmol HLligand was dissolved in ethanol(20 ml), then 0.5 mmol Manganese nitrate solution (in ethanol). The mixture solution was stirred for 4 h at room temperature. The resulting solid was filtered out and the solution evaporated yielding red crystals of compound (1) after several days.