catena-Poly[[[{5,5′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}manganese(III)]-μ-acetato] methanol monosolvate]

Gervas E Assey; Anand M Butcher; Ray J Butcher; Yilma Gultneh

doi:10.1107/S160053681003984X

. 2010 Oct 9;66(Pt 11):m1384–m1385. doi: 10.1107/S160053681003984X

catena-Poly[[[{5,5′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}manganese(III)]-μ-acetato] methanol monosolvate]

Gervas E Assey ^a, Anand M Butcher ^a, Ray J Butcher ^a,^*, Yilma Gultneh ^a

PMCID: PMC3008984 PMID: 21588822

Abstract

The title Mn^III compound, {[Mn(C₁₈H₁₈N₂O₄)(CH₃COO)]·CH₃OH}_n, was synthesized by a reaction between manganese(II) acetate and ethylenebis(4-methoxysalicylaldimine). The structure is made up of bis(4-methoxysalicyldene)ethylenediaminatomanganese(III) units bridged by acetate groups, with Mn—N = 1.9786 (9), Mn—O = 1.8784 (10) and Mn—O_acetate = 2.056 (9) and 2.2571 (9) Å, forming a one dimensional polymer (–Mn–acetate–Mn–acetate–) along [100]. The Mn^III atom is in a Jahn–Teller-distorted octahedral environment with cis angles ranging from 81.87 (4) to 96.53 (4)° and trans angles ranging from 166.11 (3) to 173.93 (3)°. The methanol solvent molecule is hydrogen bonded to the phenolate O atom. In addition to this classical hydrogen bond, there are weak C—H⋯O interactions. The structure was determined from a crystal twinned by pseudo-merohedry.

Related literature

For the biological activity of manganese(III) complexes with tetradentate Schiff bases derived from salicylaldehyde, see: Watkinson et al. (1999 ▶); Mandal et al. (2009 ▶); Hulme et al. (1997 ▶); Suzuki et al. (1997 ▶); Thampidas et al. (2008 ▶). For the oxidation of organic compounds using transition metal catalysts, see: Jang & Jacobsen (1991 ▶); Kochi (1978 ▶).

Experimental

Crystal data

[Mn(C₁₈H₁₈N₂O₄)(C₂H₃O₂)]·CH₄O
M _r = 472.37
Monoclinic,
a = 6.6237 (2) Å
b = 21.5007 (6) Å
c = 14.5544 (4) Å
β = 97.539 (3)°
V = 2054.84 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 110 K
0.52 × 0.41 × 0.16 mm

Data collection

Oxford Diffraction Gemini diffractometer with Ruby detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.914, T _max = 1.000
27951 measured reflections
27951 independent reflections
23528 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.135
S = 1.03
27951 reflections
286 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681003984X/bt5366sup1.cif

e-66-m1384-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003984X/bt5366Isup2.hkl

e-66-m1384-Isup2.hkl^{(1.3MB, 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
O1S—H1S⋯O2	0.84	2.08	2.8484 (15)	153
C8—H8A⋯O11ⁱ	0.95	2.51	3.4152 (15)	158
C8—H8A⋯O12ⁱ	0.95	2.63	3.4802 (14)	150
C16—H16B⋯O3ⁱⁱ	0.98	2.52	3.0358 (17)	113

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

Acknowledgments

RJB wishes to acknowledge the NSF-MRI program (grant CHE-0619278) for funds to purchase the diffractometer.

supplementary crystallographic information

Comment

Manganese(III) complexes with tetradentate Schiff base derived from salicylaldehyde are of great importance due to their application in many biological activities (Watkinson et al., 1999). These biological activities involve the multinuclear cluster of manganese ions within the oxygen evolving complex (OEC) of photosystem(II). This cluster is involved in the photolytic oxidation of water to dioxygen within the OEC of the photosystem(II) (Hulme et al., 1997; Mandal et al., 2009). Other biological activities where the role of manganese has played part are in enzymes such as superoxide dismutase, catalase and orginase (Thampidas et al. 2008). The importance of molecular oxygen to all animals on earth including man is for metabolism and to provide energy for life (Suzuki et al., 1997).

Also organic compounds can be oxidized using transition metal catalysts (Kochi, 1978; Jang & Jacobsen, 1991).

In the title compound C₂₁H₂₅MnN₂O₇ the structure is made up of bis(4-methoxysalicyldene)ethylenediaminatomanganese(III) moieties bridged by acetate groups with Mn—N(1) = 1.9786 (9) Å and Mn—O(1) = 1.878 (10) Å and Mn—O_acetate = 2.056 (9) Å forming a one dimensional polymer (–Mn-acetate-Mn-acetate-). The Mn atom is in a distorted octahedral environment with cis angles ranging from 81.87 (4)° to 96.54 (4)°. Each manganese(III) ion is at the center of nearly square plane with bond lengths Mn—N(1) = 1.9786 (9) Å, Mn—N(2) = 1.9954 (11) Å, Mn—O(1) = 1.8784 (10) Å and Mn—O(2) = 1.9135 (7) Å. An axial elongation of Mn—O(acetate) i.e. Mn—O(II) = 2.2056 (9) Å is an indication of the Jahn Teller distortion which is expected for a high spin manganese(III) ion in six-coordinate environment. The methanol of solvation is hydrogen bonded to the phenolic oxygen. In addition there are weak C—H···O interactions.

The structure is made up of bis(4-methoxysalicyldene)ethylenediaminatomanganese(III) moieties bridged by acetate groups with Mn—N(1) = 1.9786 (9) Å and Mn—O(1) = 1.878 (10) Å and Mn—O\ãcetate\~ = 2.056 (9) Å forming a one dimensional polymer (–Mn-acetate-Mn-acetate-). The Mn atom is in a distorted octahedral environment with cis angles ranging from 81.87 (4)° to 96.54 (4)°. The methanol of solvation is hydrogen bonded to the phenolic oxygen. In addition there are weak C—H···O interactions.

Experimental

The synthesis of the ligand ethylenebis(4-methoxysalicylaldimine) was achieved by the reaction of a solution of (1 g, 16.6 mmol) ethylenediamine in 20 ml me thanol with a solution of (5.0 g, 33.3 mmol) 2-hydroxy-p-anisaldehyde in 40 ml e thanol. This was added dropwise using glass pipette into a round bottomed flask containing the ethylene diamine. The mixture was refluxed for 24 h. Yellow solids were obtained upon solvent removal by evaporation under reduced pressure and drying.

The synthesis of the complex C₂₁H₂₅MnN₂O₇ was achieved by adding a solution of (0.33 g, 1 mmol) ethylenebis(4-methoxysalicylaldimine) in 3 ml chloroform drop wise to a solution of Mn(CH₃COO)₂.4H₂O (0.25 g, 1 mmol) in 5 ml me thanol. The mixture was stirred for 1 h and then layered with diethyl ether for slow diffusion crystallization process. Crystals suitable for X-ray diffraction were obtained.