Bis(3-carb­oxy-5-nitro­benzoato)bis­[2-(pyridin-4-yl)-1H-imidazo[4,5-f][1,10]phenanthroline]manganese(II)

Hong-Bin Xu; Shuai Ma; Yu He

doi:10.1107/S1600536811004569

. 2011 Feb 12;67(Pt 3):m326. doi: 10.1107/S1600536811004569

Bis(3-carboxy-5-nitrobenzoato)bis[2-(pyridin-4-yl)-1H-imidazo[4,5-f][1,10]phenanthroline]manganese(II)

Hong-Bin Xu ^a,^*, Shuai Ma ^b, Yu He ^b

PMCID: PMC3052015 PMID: 21522257

Abstract

In the title compound, [Mn(C₈H₄NO₆)₂(C₁₈H₁₁N₅)₂], the Mn^II atom is six-coordinated by two N,N′-bidentate 6-(pyridin-4-yl)-5H-cyclopenta[f][1,10]phenanthroline (pcp) ligands and two carboxylate O atoms from two monodentate 3-carboxy-5-nitrobenzoate anions in a distorted cis-MnO₂N₄ octahedral arrangement. Within the pcp ligands, the dihedral angles between the polycyclic skeletons and pendant pyridine rings are 6.2 (2) and 8.3 (2)°. In the crystal, molecules are linked by O—H⋯N and N—H⋯O hydrogen bonds. Several aromatic π–π stacking interactions [shortest centroid–centroid separation = 3.516 (3) Å] are also observed.

Related literature

For background to ligands based on 1,10-phenanthroline, see: Wang et al. (2010 ▶).

Experimental

Crystal data

[Mn(C₈H₄NO₆)₂(C₁₈H₁₁N₅)₂]
M _r = 1069.82
Monoclinic,
a = 21.791 (3) Å
b = 8.2215 (12) Å
c = 27.270 (4) Å
β = 111.767 (3)°
V = 4537.2 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.16 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.45, T _max = 0.69
22806 measured reflections
8037 independent reflections
3602 reflections with I > 2σ(I)
R _int = 0.105

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.126
S = 0.95
8037 reflections
694 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004569/hb5800sup1.cif

e-67-0m326-sup1.cif^{(30.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004569/hb5800Isup2.hkl

e-67-0m326-Isup2.hkl^{(385.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Mn1—O1	2.142 (3)
Mn1—O6	2.142 (3)
Mn1—N1	2.339 (4)
Mn1—N2	2.220 (3)
Mn1—N6	2.221 (4)
Mn1—N7	2.309 (4)

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N6—Mn1—N7	72.19 (14)
N2—Mn1—N1	72.42 (13)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H9A⋯N10ⁱ	0.82	1.81	2.629 (5)	176
O4—H4⋯N5ⁱⁱ	0.82	1.82	2.636 (5)	173
N9—H7A⋯O2ⁱⁱⁱ	0.86	1.94	2.789 (5)	171
N4—H4A⋯O5^iv	0.86	1.89	2.745 (5)	171

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

Acknowledgments

The authors thank Jilin Normal University for supporting this work.

supplementary crystallographic information

Comment

The coordination complexes based on 1,10-phenanthroline-like ligands have received intense interests of chemists (Wang et al., 2010). The (6-(pyridin-4-yl)-5H-cyclopenta[f][1,10]phenanthroline ligand (L), as a good candidate for N-donor ligand, has excellent coordinating ability. In this work, we selected 1,3-Hbdc ligand (1,3-Hbdc = 5-nitro-benzene-1-carboxylate-3-carboxylic acid) as a secondary ligand and L as a N-donor chelating ligand, generating a new molecular Mn^II complex, [Mn(L)₂(1,3-Hbdc)₂].

The central Mn^II atom is six-coordinated by four N atoms from two different L ligands, and two carboxylate O atoms from two different 1,3-Hbdc ligands in a distorted octahedral sphere. The O—H···N and N—H···O H-bonding interactions further stabilize the structure of (I).

Experimental

A mixture of MnCl₂^.4H₂O (0.5 mmol), 1,3-H₂bdc (0.5 mmol) and L (0.5 mmol) in 1 ml distilled water was heated at 460 K in a Teflon-lined stainless steel autoclave for seven days. The reaction system was then slowly cooled to room temperature. Pale yellow blocks of (I) were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature. Yield: 31% based on Mn(II).