(Acetyl­acetonato-κ2 O,O′)aqua­[2-(2-nitro­phen­oxy)-N′-(2-oxidobenzyl­idene-κO)acetohydrazidato-κ2 O,N′]manganese(III)

Zi-Jing Xiao

doi:10.1107/S1600536809028177

. 2009 Jul 25;65(Pt 8):m986. doi: 10.1107/S1600536809028177

(Acetylacetonato-κ² O,O′)aqua[2-(2-nitrophenoxy)-N′-(2-oxidobenzylidene-κO)acetohydrazidato-κ² O,N′]manganese(III)

Zi-Jing Xiao ^a,^*

PMCID: PMC2977142 PMID: 21583428

Abstract

In the title complex, [Mn(C₁₅H₁₁N₃O₅)(C₅H₇O₂)(H₂O)], the Mn^III ion has a distorted octahedral coordination geometry. It is coordinated by a phenoxy O atom, a hydrazine N atom and a carbonyl O atom of the 2-(2-nitrophenoxy)-N′-(2-oxidobenzylidene-κO)acetohydrazidate dianion, by two O atoms of the acetylacetonate anion and by the O atom of a coordinated water molecule. In the crystal structure, complex molecules are linked into centrosymmetric dimeric units through four intermolecular O—H⋯O hydrogen bonds involving both H atoms of the coordinated water molecule.

Related literature

For the biological activity and chemical versatility of hydrazone complexes, see: Liu & Gao (1998 ▶); Iskander et al. (2001 ▶); Cariati et al. (2002 ▶); Sreekanth et al. (2004 ▶); Bai et al. (2006 ▶); Mondal et al. (2008 ▶). For phenoxyacetylhydrazone complexes, see: Chen & Liu (2004 ▶); Sun et al. (2005 ▶); Chen & Liu (2006 ▶).

Experimental

Crystal data

[Mn(C₁₅H₁₁N₃O₅)(C₅H₇O₂)(H₂O)]
M _r = 485.33
Monoclinic,
a = 8.5217 (6) Å
b = 13.9263 (10) Å
c = 17.6311 (10) Å
β = 92.725 (3)°
V = 2090.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 293 K
0.58 × 0.32 × 0.27 mm

Data collection

Rigaku R-AXIS RAPID Imaging Plate diffractometer
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999 ▶) T _min = 0.766, T _max = 0.832
4921 measured reflections
4735 independent reflections
3155 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.086
S = 0.88
4735 reflections
293 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: TEXRAY (Molecular Structure Corporation, 1999 ▶); cell refinement: TEXRAY; data reduction: TEXSAN (Molecular Structure Corporation, 1999 ▶); program(s) used to solve structure: SHELXS98 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL98 (Sheldrick, 2008 ▶); molecular graphics: ORTEX (McArdle, 1995 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028177/fj2221sup1.cif

e-65-0m986-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028177/fj2221Isup2.hkl

e-65-0m986-Isup2.hkl^{(232KB, 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—H01⋯O4ⁱ	0.88	2.16	2.955 (2)	150
O1W—H02⋯O2ⁱ	0.88	1.96	2.829 (2)	169

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful for financial support from the Natural Science Foundation of Fujian Province of China (No. E0640006).

supplementary crystallographic information

Comment

The design and construction of hydrazone complexes are of great interest due to their various structures and their biological activities and chemical versatility (Liu & Gao, 1998; Iskander et al., 2001; Cariati et al., 2002; Sreekanth et al., 2004; Bai et al., 2006; Mondal et al., 2008). Relatively speaking, only a few crystal structures of phenoxyacetylhydrazone complexes have been studied (Chen & Liu, 2004; Sun et al., 2005; Chen & Liu, 2006).

As shown in Fig. 1, the Mn^III ion in (I) is octahedrally coordinated by phenol atom O1, hydrazine atom N1 and carbonyl atom O2 from the phenoxyacetylhydrazone ligand L^2-, two oxygen atoms (O6 and O7) from an acac^- ligand, and O1W atom from coordinated water molecule. Atoms O1, N1, O2 and O7 form the equatorial plane, while the atoms O6 and O1W occupy the two axial positions. The bond distance of Mn1—O6(acac^-) (2.130 (2) Å) is much longer than the one of Mn1—O7(acac^-) (1.921 (1) Å) due to the Jahn-Teller effect of Mn(III) ion.

In most of phenoxyacetylhydrazone complexes, the phenoxy oxygen atom is not coordinated to metal atom. This structural phenomenon is found in the title complex (I) and was also found in several known complexes (Chen & Liu, 2004; Sun et al., 2005; Chen & Liu, 2006).

The complex Co(C₂H₃O₂)(C₄H₉NO)₂(C₁₅H₁₁N₃O₅) (II) (Sun et al., 2005) and the title complex Mn(C₁₅H₁₁N₃O₅)(C₅H₇O₂)(H₂O) (I) have the same N-salicylaldehyde-N'– (o-nitrophenoxyacyl) hydrazone ligand. The dihedral angles between the two benzene rings of the phenoxyacyl hydrazone ligand in complex (I) is 89.48 (8)°, while the corresponding one in (II) is 44.1 (1)°. This big difference of the two dihedral angles may come from the different sizes of the second ligands in the two complexes.

As shown in Fig. 2, two neighboring complex molecules are linked by four hydrogen bonds O—H(coordinated water molecule)···O(carbonyl O or oxygen in o-nitrate group) to form a centrosymmetrical dimer.

Experimental

The N-salicylaldehyde-N'- (o-nitrophenoxyacyl) hydrazone ligand, (H₂L) was prepared according the reference (Sun et al., 2005). H₂L (0.05 mmol) and Mn(acac)₃ (0.05 mmol) were dissolved in a mixed solution of 10 ml 95% EtOH and 1 ml DMF. The mixture was stirred for 3 h. After one week, Dark-brown crystals of (I) were obtained.