Acetato­aqua­{4,4′,6,6′-tetra-tert-butyl-2,2′-[(2-pyridyl­meth­yl)imino­dimethyl­ene]diphenolato}manganese(III) ethanol solvate

Elliott Chard; Louise N Dawe; Christopher M Kozak

doi:10.1107/S1600536810021288

. 2010 Jun 16;66(Pt 7):m771. doi: 10.1107/S1600536810021288

Acetatoaqua{4,4′,6,6′-tetra-tert-butyl-2,2′-[(2-pyridylmethyl)iminodimethylene]diphenolato}manganese(III) ethanol solvate

Elliott Chard ^a, Louise N Dawe ^b, Christopher M Kozak ^a,^*

PMCID: PMC3006980 PMID: 21587701

Abstract

In the title complex, [Mn(C₃₆H₅₀N₂O₂)(CH₃COO)(H₂O)]·CH₃CH₂OH, the Mn^III atom is in an octahedral environment and is coordinated by the tetradentate amine–bis(phenolate) ligand, a monodentate acetate anion and a water molecule. An ethanol solvent molecule is also found in the asymmetric unit. The structure displays O—H⋯O and C—H⋯O hydrogen bonding.

Related literature

For a related structure, see: van Gorkum et al. (2008 ▶). For the structure of the unmetallated ligand, see: Chmura et al. (2006 ▶). For synthetic procedures, see: Kerton et al. (2008 ▶); Shimazaki et al. (2000 ▶).

Experimental

Crystal data

[Mn(C₃₆H₅₀N₂O₂)(C₂H₃O₂)(H₂O)]·C₂H₆O
M _r = 720.87
Monoclinic,
a = 16.505 (3) Å
b = 10.8310 (16) Å
c = 26.512 (5) Å
β = 118.798 (3)°
V = 4153.2 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 153 K
0.40 × 0.30 × 0.24 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: numerical (ABSCOR; Higashi, 2000 ▶) T _min = 0.906, T _max = 0.948
44205 measured reflections
8589 independent reflections
8248 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.138
S = 1.10
8589 reflections
444 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku/MSC, 2005 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021288/pv2284sup1.cif

e-66-0m771-sup1.cif^{(29.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021288/pv2284Isup2.hkl

e-66-0m771-Isup2.hkl^{(420.1KB, 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
O5—H41A⋯O6ⁱ	0.92	1.91	2.799 (2)	160
O6—H42⋯O4ⁱⁱ	0.91	1.81	2.723 (3)	171
O5—H41B⋯O4	0.93	1.79	2.677 (2)	160
C4—H4B⋯O1	0.98	2.36	2.991 (4)	122
C5—H5C⋯O1	0.98	2.28	2.929 (3)	123
C15—H15B⋯O5	0.99	2.54	3.202 (3)	124
C34—H34C⋯O2	0.98	2.45	3.102 (3)	123
C35—H35A⋯O2	0.98	2.32	3.010 (3)	126

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

Acknowledgments

This work was supported by Memorial University of Newfoundland, the Natural Sciences and Engineering Research Council (NSERC) of Canada, the Canada Foundation for Innovation and the Provincial Government of Newfoundland and Labrador.

supplementary crystallographic information

Comment

In the complex acetato[2-pyridylamino-N,N-bis(2-methylene-4,6-tert-butylphenolato)]aquamanganese(III) (1), the manganese(III) ion resides in a distorted octahedral geometry. Its coordination sphere is occupied by two phenolate oxygen atoms, a tertiary amine and a pyridine nitrogen donor. The phenolate oxygens, O1 and O2, of the tetradentate ligand are trans orientated and exhibit Mn1—O1 and Mn1—O2 bond lengths of 1.8532 (14) and 1.8770 (14) Å, respectively. The O3 atom of the monodentate acetate group is trans to the amine nitrogen, N1, and the Mn1—O3 and Mn1—N1 bond distances are 1.9958 (15) and 2.1058 (16) Å, respectively. The water ligand, O5, is trans to the pyridine nitrogen donor, N2. The Mn ion is Jahn-Teller distorted along the Mn1—N2 and Mn1—O5 bonds, which are considerably elongated giving bond distances of 2.2543 (17) and 2.2434 (15) Å, respectively. This elongated axis is similar to that reported by Van Gorkum et al. (2008), except that the previously reported structure possesses a bidentate acetate and no water ligand. Bond angles of trans-orientated ligands around Mn are slightly bent and range between 170.77 (6)° for O3—Mn1—N1 and 177.70 (6)° for O1—Mn1—O2.

The complex exhibits both intra- and intermolecular hydrogen bonding. The water ligand acts as a hydrogen bond donor to the uncoordinated O4 of the acetate ligand. The O4···O5 interatomic distance is 2.677 (2) Å and within the typical range for hydrogen bonding between oxygen-containing hydrogen bond donor-acceptors. The uncoordinated O4 of the acetate group also displays intermolecular hydrogen bonding to an ethanol solvate molecule. The interatomic distance between O4 of the acetate and O6 [x, y-1, z] of the ethanol molecule is 2.723 (2) Å, which is within the sum of the van der Waals radii. The ethanol ligand is the hydrogen bond donor and the acetate O6 is the acceptor. Another intermolecular hydrogen bond exists between the coordinated water ligand and the ethanol oxygen atom of a second ethanol molecule (2.7989 (18) Å for O5···O6 [-x+1, y-1/2, -z+3/2]). In this interaction, the water ligand acts as hydrogen bond donor and the solvate ethanol O-atom is the acceptor. These multiple intermolecular hydrogen bonding interactions effectively result in chains where the six-coordinate Mn complexes are bridged by solvate ethanol molecules.

Experimental

The 2-pyridylamino-N,N-bis(2-methylene-4,6-tert-butylphenol) ligand (abbreviated H₂(O₂NN')) was prepared according to the published methods (Kerton et al., 2008; Shimazaki et al., 2000). Mn(OAc)₂.4H₂O (0.5033 g, 2.0 mmol) and H₂(O₂NN') (0.5619 g, 1.00 mmol) were dissolved in 95% ethanol (20 ml) and heated to reflux for one hour. The resulting dark purple solution was filtered through a glass frit while hot. Distilled H₂O (10 ml) was added to the dark purple filtrate. As the solution cooled to room temperature, dark purple crystals suitable for X-ray diffraction precipitated out of the ethanol/water medium (580 mg, 86% yield). MS (MALDI-TOF) m/z, intensity (ion): 656.3305, 20% ([M—H₂O]⁺); 596.3156, 42% ([M—H₂O-OAc]⁺).