Aqua­{6,6′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}(4-hydroxy­benzoato)manganese(III)

R Reshma; P V Soumya; S M Simi; V S Thampidas; Robert D Pike

doi:10.1107/S1600536809032553

. 2009 Aug 22;65(Pt 9):m1110–m1111. doi: 10.1107/S1600536809032553

Aqua{6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}(4-hydroxybenzoato)manganese(III)

R Reshma ^a, P V Soumya ^a, S M Simi ^a, V S Thampidas ^a,^*, Robert D Pike ^b

PMCID: PMC2969974 PMID: 21577455

Abstract

The title compound, [Mn(C₁₈H₁₈N₂O₄)(C₇H₅O₃)(H₂O)], was synthesized by a template reaction of ethane-1,2-diamine and 3-methoxysalicylaldehyde in presence of manganese(II) 4-hydroxybenzoate. The Jahn–Teller-distorted manganese(III) centre has an octahedral geometry. Extensive O—H⋯O hydrogen-bonding interactions generate a two-dimensional sheet structure parallel to (103).

Related literature

For background to the coordination chemistry of manganese, see: Christou (2005 ▶); Yocum & Pecoraro (1999 ▶); McEvoy & Brudvig (2006 ▶); Pecoraro (1992 ▶). For the structures of manganese complexes containing Schiff base and carboxylate ligands, see: Bermejo et al. (2006 ▶); Hulme et al. (1997 ▶); Zhang & Janiak (2001 ▶).

Experimental

Crystal data

[Mn(C₁₈H₁₈N₂O₄)(C₇H₅O₃)(H₂O)]
M _r = 536.41
Monoclinic,
a = 8.5988 (3) Å
b = 13.5524 (5) Å
c = 21.1335 (8) Å
β = 93.280 (2)°
V = 2458.75 (16) Å³
Z = 4
Cu Kα radiation
μ = 4.82 mm⁻¹
T = 100 K
0.43 × 0.38 × 0.24 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: numerical (SADABS; Sheldrick, 2004 ▶) T _min = 0.229, T _max = 0.388
26252 measured reflections
4259 independent reflections
3766 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.082
S = 1.04
4259 reflections
329 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032553/bt5032sup1.cif

e-65-m1110-sup1.cif^{(25.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032553/bt5032Isup2.hkl

e-65-m1110-Isup2.hkl^{(208.7KB, 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
O8—H8⋯O5ⁱ	0.84	1.79	2.599 (2)	161
O3—H2W⋯O7ⁱⁱ	0.84	2.32	3.0025 (19)	139
O3—H2W⋯O2ⁱⁱ	0.84	2.11	2.8711 (17)	150
O3—H1W⋯O6ⁱⁱ	0.84	2.29	3.000 (2)	142
O3—H1W⋯O1ⁱⁱ	0.84	2.21	2.9475 (18)	147

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

Acknowledgments

We acknowledge the generosity of the Principal of SN College, Varkala, Kerala, for providing the facilities of the college for this research. We also acknowledge the NSF (CHE-0443345) and the College of William and Mary for the purchase of the X-ray equipment.

supplementary crystallographic information

Comment

Recent advances in the coordination chemistry of manganese have been mainly associated with (i) manganese clusters and the phenomenon of single-molecule magnetism (Christou, 2005) and (ii) its biological importance (Pecoraro, 1992). With its accessible oxidation states ranging from (II) to (V), and a propensity for coordination with N and O donor atoms, manganese exhibits rich redox and structural chemistry in biological systems like the oxygen-evolvingcomplex (OEC) of photosystem II (McEvoy & Brudvig, 2006), superoxide dismutase, catalase, arginase etc. (Yocum & Pecoraro, 1999). We have been interested in inorganic modeling of the active sites of these manganese-containing systems using complexes containing Schiff base and carboxylate ligands. The structural diversity displayed in such complexes has been amply demonstrated in previous reports (Hulme et al., 1997; Zhang & Janiak, 2001; Bermejo et al., 2006). In this paper, we report the crystal structure of a new manganese(III) complex with the Schiff base, m-salen [H₂msalen = N,N'-bis(3-methoxysalicylidene)-ethane-1,2-diamine] and 4-hydroxyobenzoate as an ancillary ligand (Figure 1).

The N₂O₂ donor set of the m-salen ligand holds the manganese(III) ion at the centre of an approximate square plane [Mn(1)-O(1) = 1.8848 (12) Å and Mn(1)-O(2) = 1.8821 (11) Å ;Mn(1)-N(1) = 1.9774 (15) Å and Mn(1)-N(2) = 1.9930 (14) Å]. Jahn-Teller distortion elongate of the axial Mn–O_carb [Mn(1)-O(4) = 2.1164 (13) Å] and the Mn–O_aq [Mn(1)-O(3) = 2.3257 (12) Å]. H-bonding interactions between the non-coordinated O atom of the carboxylate and the para O-H group of the carboxylate of an adjacent molecule produce chains progressing along a screw (2₁) axis parallel to the b-axis. Axial H₂O ligands and the m-salen ligands of neighboring molecules are involved in multiple H-bond interactions resulting in chains. These two interactions together produce a 2-dimensional sheet structure parallel to the (1 0 3) plane (Figure 2).

Experimental

To a solution of [Mn(4-OHC₆H₄CO₂)(H₂O)₂].H₂O (1.00 g, 2.61 mmol), and 3-methoxysalicylaldehyde (0.76 g, 5.22 mmol) in methanol (40 ml), ethane-1,2-diamine (0.16 g, 2.61 mmol) was added. The solution was stirred for 20 minutes, filtered and left to evaporation in an open conical flask. Brown crystals were deposited in 2–3 days. These were collected by filtration, washed with methanol, and dried in air. Crystals were grown from a DMF solution.