Aqua­{6,6′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato-κ4 O,N,N′,O′}(formato-κO)manganese(III) dihydrate

See Mun Lee; Kong Mun Lo; Seik Weng Ng

doi:10.1107/S1600536811017648

. 2011 May 14;67(Pt 6):m746. doi: 10.1107/S1600536811017648

Aqua{6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato-κ⁴ O,N,N′,O′}(formato-κO)manganese(III) dihydrate

See Mun Lee ^a, Kong Mun Lo ^a, Seik Weng Ng ^a,^*

PMCID: PMC3120422 PMID: 21754637

Abstract

The Mn^III atom in the title complex, [Mn(C₁₈H₁₈N₂O₄)(CHO₂)(H₂O)]·2H₂O, is O,N,N′,O′-chelated by the deprotonated Schiff base; the four chelating atoms form an approximate square, with the O atoms of the water molecule and the formate ion in axial positions above and below the square plane. Two metal-bearing molecules are linked by an O—H_water⋯O hydrogen bond about a center of inversion, generating a hydrogen-bonded dinuclear species; adjacent dinuclear units are linked through the lattice water molecules, forming a three-dimensional network.

Related literature

For related Mn^III compounds with the same Schiff base, see: Bermejo et al. (2007 ▶); Li et al. (2009 ▶); Zhang et al. (1999 ▶, 2000 ▶).

Experimental

Crystal data

[Mn(C₁₈H₁₈N₂O₄)(CHO₂)(H₂O)]·2H₂O
M _r = 480.35
Monoclinic,
a = 11.5670 (2) Å
b = 19.9312 (3) Å
c = 8.7701 (1) Å
β = 96.859 (1)°
V = 2007.42 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 100 K
0.10 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.932, T _max = 0.932
18245 measured reflections
4600 independent reflections
3660 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.192
S = 1.12
4600 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 1.67 e Å⁻³
Δρ_min = −0.96 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017648/bt5546sup1.cif

e-67-0m746-sup1.cif^{(22KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017648/bt5546Isup2.hkl

e-67-0m746-Isup2.hkl^{(225.4KB, 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—H11⋯O3ⁱ	0.84	2.01	2.730 (4)	143
O1w—H12⋯O2ⁱ	0.84	2.09	2.813 (4)	145
O2w—H21⋯O6	0.84	2.04	2.793 (5)	148
O2w—H22⋯O3w	0.84	1.96	2.762 (7)	161
O3w—H31⋯O2wⁱⁱ	0.84	1.94	2.782 (7)	179

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

Acknowledgments

We thank the University of Malaya (grant No. RG020/09AFR) for supporting this study.

supplementary crystallographic information

Comment

The 6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenol Schiff base functions as a tetradentate dianionic ligand in a small number of manganese(III) derivatives (Bermejo et al., 2007; Li et al. 2009; Zhang et al., 1999, 2000). The counterion that balances the positive charge on the metal is involved in coordination. In the present study, the acetate portion of the manganese(III) acetate reactant undergoes carbon-carbon cleave to form a formate ion. The Mn^III atom in Mn(H₂O)(CHO₂)(C₁₈H₁₈N₂O₄)^.2H₂O (Scheme I) is O,N,N',O'-chelated by the deprotonated Schiff base; the four atoms involved in chelating form a square, above and below which are the O atoms of the water molecule and the formate ion (Fig. 1). Two molecules are linked by an O–H_water···O hydrogen bond dinuclear species; adjacent dinuclear units are linked through the lattice water molecules, forming a three-dimensional network (Table 1).

Experimental

N,N'-Ethylenebis(4-methoxysalicylindeneaminate) was prepared by reacting 0.2 ml (3.1 mmol) of ethylenediamine with 0.9 g (6 mmol) of 2-hydroxy-4-methoxybenzaldehyde in 50 ml of ethanol. An aqueous solution of 0.18 g (1 mmol) of manganese(II) nitrate was added to a hot methanol solution (100 ml) containing 0. 32 g (1 mmol) of the ligand and 0.28 g (2 mmol) of sodium acetate trihydrate. The immediate brown solution was refluxed for an hour, after which it was filtered. Slow evaporation of the filtrate gave brown crystals. Under the reaction conditions, the acetate ion used in the synthesis was converted to the formate ion in the product; the carbon-carbon bond cleavage was accompanied by oxidation of the Mn^II to Mn^III.