catena-Poly[[[aqua­manganese(III)]-μ-(E)-5-bromo-N-[2-(5-bromo-2-oxidobenzyl­idene­amino)-4-nitro­phen­yl]-2-oxidobenzamidato] N,N-dimethyl­fomamide monosolvate]

Abeer Mohamed Farag; Teoh Siang Guan; Hasnah Osman; Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S1600536812008501

. 2012 Mar 3;68(Pt 4):m365–m366. doi: 10.1107/S1600536812008501

catena-Poly[[[aquamanganese(III)]-μ-(E)-5-bromo-N-[2-(5-bromo-2-oxidobenzylideneamino)-4-nitrophenyl]-2-oxidobenzamidato] N,N-dimethylfomamide monosolvate]

Abeer Mohamed Farag ^a, Teoh Siang Guan ^a, Hasnah Osman ^a, Madhukar Hemamalini ^b, Hoong-Kun Fun ^b,^*,^‡

PMCID: PMC3343787 PMID: 22589761

Abstract

The asymmetric unit of the title complex, {[Mn(C₂₀H₁₀Br₂N₃O₅)(H₂O)]·(CH₃)₂NCHO}_n, consists of one Mn^III ion, one (E)-5-bromo-N-[2-(5-bromo-2-oxidobenzylideneamino)-4-nitrophenyl]-2-oxidobenzamidate ligand (Schiff base), one water molecule and an N,N-dimethylformamide molecule. The coordination geometry around the Mn^III ion is a distorted octahedron, being surrounded by two O and two N atoms from the Schiff base, which are positioned in the equatorial plane. The water molecule and the O atom of the carbonyl group from the adjacent Mn^III complex are situated at the axial positions, leading to a polymeric chain along the c axis. In the crystal, the complex and N,N-dimethylformamide molecules are connected via O—H⋯O, C—H⋯O and C—H⋯Br hydrogen bonds, forming a three-dimensional network.

Related literature

For details of the coordination chemistry and biological importance of manganese, see: Maneiro et al. (2003 ▶); Chandra et al. (2009 ▶); Chrisianson & Cox (1999 ▶); Ni et al. (2009 ▶); Zhang et al. (2005 ▶); Huh & Lee (2008 ▶); Pastoriza-Santos & Liz-Marzań (2009 ▶). For related structures, see: Su & Xu (2005 ▶); Ma et al. (2004 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Mn(C₂₀H₁₀Br₂N₃O₅)(H₂O)]·C₃H₇NO
M _r = 678.18
Monoclinic,
a = 11.0746 (6) Å
b = 24.9781 (13) Å
c = 9.5563 (5) Å
β = 114.658 (1)°
V = 2402.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.93 mm⁻¹
T = 100 K
0.52 × 0.17 × 0.11 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.234, T _max = 0.672
27005 measured reflections
8188 independent reflections
6617 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.085
S = 1.02
8188 reflections
344 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.85 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I, an. DOI: 10.1107/S1600536812008501/is5080sup1.cif

e-68-0m365-sup1.cif^{(33.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008501/is5080Isup2.hkl

e-68-0m365-Isup2.hkl^{(392.5KB, 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—H1W2⋯O5ⁱ	0.73 (4)	2.03 (4)	2.736 (2)	163 (4)
O1W—H2W2⋯O1ⁱⁱ	0.77 (3)	2.55 (3)	3.178 (2)	140 (3)
O1W—H2W2⋯O2ⁱⁱ	0.77 (3)	2.19 (3)	2.890 (2)	153 (3)
C2—H2⋯O5ⁱⁱⁱ	0.93	2.42	3.351 (2)	175
C5—H5⋯O4^iv	0.93	2.49	3.395 (3)	166
C7—H7⋯O3^iv	0.93	2.60	3.509 (2)	167
C18—H18⋯Br2^v	0.93	2.83	3.449 (2)	125
C23—H23A⋯O5^vi	0.96	2.40	3.350 (3)	170

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

AMF, TSG and HO thank the Malaysian Government and Universiti Sains Malaysia (USM) for the RU research grant (1001/PKIMIA/815002). AMF thanks Naser Taha and Hema for their help. HKF and MH thanks the Malaysian Government and USM for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks USM for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

In recent years, the coordination chemistry of manganese has been intensively studied due to its presence in the active sites of some enzymes that participate in the chemistry of reactive oxygen species, such as the participation of Mn(II) complexes in peroxidase activity (Maneiro et al., 2003), antipathogenic activity (Chandra et al., 2009) and as essential cofactors in metalloenzymes (Chrisianson & Cox, 1999). X-Ray crystallography has shown a quasi- two-coordinate strongly bent geometry with Mn, which has an almost linear geometry with a wide N—Mn—N angle of 176.1° (Ni et al., 2009). Octahedral coordination is completed by N₄O₂ ligands (Zhang et al., 2005). The reaction system (solvent composition and reaction temperature) may cause dramatic changes in the structures. The preparation of the polymer results in the introduction of guest molecules such as DMF into its empty channels by the use of mixed solvents DMF-EtOH-H₂O under hydro(solvo)thermal conditions (Huh & Lee, 2008). The mechanism of oxidation by DMF have been proposed by Pastoriza-Santos & Liz-Marzań (2009). Due to these interesting features, the title compound was synthesized and its crystal structure presented here.

The asymmetric unit of the title polymeric complex, consisting of one Mn (III) ion, one (E)-5-bromo-N-(2- (5-bromo-2-hydroxybenzylideneamino)-4-nitrophenyl)-2-hydroxybenzamide (Schiff base), one water molecule and a dimethylformamide solvate molecule is shown in Fig. 1. The coordination geometry around Mn (III) is a distorted octahedron, with the Mn (III) ion being surrounded by two O and two N atoms from the Schiff base which are positioned in the equatorial plane. The water molecule and an atom from a carbonyl group are situated in the axial positions. The carbonyl groups bridge the Mn (III) ions, leading to polymeric chains along the c-axis (Fig. 2). The bond lengths are Mn1—O2 = 1.8557 (13); Mn1—O1 = 1.8875 (13); Mn1—N2 = 1.9750 (15); Mn1—N1 = 1.9782 (15); Mn1—O1W =2.2431(15; Mn1—O6 = 2.3448 (14) Å. All bond lengths are in agreement with those in the related structures (Su & Xu, 2005; Ma et al., 2004). In the crystal, (Fig. 3), the complexes are connected with the solvent molecules via O—H···O, C—H···O and C—H···Br hydrogen bonds (Table 1) to form a three-dimensional network.

Experimental

To the solution of 4-nitrobenzene-1,2-diamine (0.306 g, 2 mmol) in ethanol (30 mL) was added 5-bromo-2-hydroxybenzaldehyde (0.804 g, 4 mmol), after which the colour of solution became orange. The mixture was refluxed with stirring for three hours. On adding manganese(II) chloride (0.395 g, 2 mmol), followed by triethylamine (500 mL, 3.6 mmol), a brown precipitate was formed. The mixture was stirred with reflux for three hours. The precipitate, obtained by filtration, was washed by ethanol (5 mL) and dried, affording the title compound (87.33 % yield). Brown block-shaped single crystals suitable for X-ray structure determination were obtained from DMF: ethanol mixture (2:8) with decomposition pt. >340 °C. IR spectroscopy (KBr): ν = 3370 (-OH), 1612 (C═N), 1335 (NO₂), 639 (M–N), 480 (M–O) cm^-1. Anal. Calcd (found) for [C₂₀H₁₅Br₂N₃O₆Mn].C₃H₇NO: C 39.50 (39.55), H 2.49 (2.11), N 6.91 (6.55), Mn 9.03 (8.66). MASS Calcd (found) m/z: [605.87 - 2H₂O]⁺ = 569.87 (571.9).