Bis[2-meth­oxy-6-(phenyl­iminiomethyl)phenolate-κ2 O,O′]bis­(thio­cyanato-κN)manganese(II)

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

doi:10.1107/S1600536811009330

. 2011 Mar 19;67(Pt 4):m463. doi: 10.1107/S1600536811009330

Bis[2-methoxy-6-(phenyliminiomethyl)phenolate-κ² O,O′]bis(thiocyanato-κN)manganese(II)

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

PMCID: PMC3099895 PMID: 21753979

Abstract

The Mn^II atom in the title complex, [Mn(NCS)₂(C₁₄H₁₃NO₂)₂], lies on a center of inversion in a MnO₄N₂ octahedral geometry. The Schiff base is present in its zwitterionic form and is O,O′-chelated to the metal atom. The imino N atom is protonated and is involved in an intramolecular hydrogen bond with the phenolate O atom.

Related literature

For Schiff base ligands derived from o-vanillin and aniline and their rare earth complexes, see: Li et al. (2008 ▶); Liu et al. (2009 ▶); Xian et al. (2008 ▶); Zhao et al. (2005 ▶, 2007 ▶).

Experimental

Crystal data

[Mn(NCS)₂(C₁₄H₁₃NO₂)₂]
M _r = 625.61
Triclinic,
a = 9.0204 (2) Å
b = 9.3070 (2) Å
c = 9.4087 (2) Å
α = 87.417 (1)°
β = 82.010 (1)°
γ = 65.693 (1)°
V = 712.81 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 296 K
0.29 × 0.17 × 0.05 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.877, T _max = 0.970
9483 measured reflections
2509 independent reflections
2233 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.077
S = 1.06
2509 reflections
188 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.24 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 I, global. DOI: 10.1107/S1600536811009330/ng5130sup1.cif

e-67-0m463-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009330/ng5130Isup2.hkl

e-67-0m463-Isup2.hkl^{(123.2KB, 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
N1—H1A⋯O1	0.86	1.97	2.6501 (16)	135

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supplementary crystallographic information

Comment

For many years, there has been considerable interest in the study of Schiff base compounds due to their biological activity (Zhao et al., 2005). Interested in this field, we have been synthesized several analogous Schiff bases derived from o-vanillin and prepared their transitional and rare metal complexes further. In a few of articles we have reported our partial research results (Zhao et al., 2007; Xian et al. 2008; Li et al. 2008; Liu et al. 2009). Herein, we describe a new Mn(II) complex.

The structure of complex (1) was shown in Fig. 1 and the coordination environment of Mn(II) was shown in Fig. 2. In this complex the Mn(II) is six- coordinated by two N atoms from thiocyanate ions and four O atoms from the Schiff bases (HL), which can be described as a distorted octahedral geometry. There thiocyanate anions coordinate to Mn(II) ion with N atoms occupying the apices and two HL ligands chelate the Mn(II) ion with four O atoms from deprotonated phenol groups and methoxyl groups occupying the equatorial positions. The Mn—O and Mn—N bond distances were listed in Table 1, The distances between Mn(II) and methoxyl O atoms are obvious longer than Mn—O(phenolic) bond distances, which are similar to the analogous complexes (Zhao et al., 2007; Li et al., 2008, Liu et al., 2009).

The hydrogen bonds and π–π weak non-covalent interactions lend stability to the structure. The stacking plot of this compound was shown in Fig. 3. In HL ligand, two protons of phenolic hydroxyl groups considered to have transferred to imine N atoms involve in forming intramolecular hydrogen bonds. The π–π interactions exist both intra and extra molecules between the approximate paralleled participating benzene rings, which may be the primary forces keep the complex molecules packing together.

Experimental

Reagents and solvents used were of commercially available quality and without purified before using. The Schiff base ligand 2-(phenyliminomethyl)-6-methoxyphenol was synthesized from condensation of o-vanillin and aniline. The title compound was synthesized by traditional method. 1 mmol HL ligand was dissolved in ethanol, then 0.5 mmol Mn(NO₃)₂.6H₂O (in ethanol) was added to the upper solution. The mixture solution was stirred for 2 h at room temperature. Furthermore, 1 mmol NH₄SCN (dissolved in ethanol) was added. The mixture was stirred again for 8 h at room temperature. At last, deposit was filtered out and the reddish-brown solution was kept in the open air. The red crystal was obtained after several days.