Bis(benzoyl­acetonato)bis­(1,3-di-4-pyridyl­propane)manganese(II)

Yan Zhou; Wen-Na Zhao; Lei Han

doi:10.1107/S1600536809009891

. 2009 Mar 25;65(Pt 4):m423–m424. doi: 10.1107/S1600536809009891

Bis(benzoylacetonato)bis(1,3-di-4-pyridylpropane)manganese(II)

Yan Zhou ^a, Wen-Na Zhao ^b, Lei Han ^a,^*

PMCID: PMC2969015 PMID: 21582365

Abstract

In the title compound, [Mn(C₁₀H₉O₂)₂(C₁₃H₁₄N₂)₂], the Mn^II ion lies on a crystallographic inversion center and has a slightly distorted octahedral coordination environment. Weak π–π stacking interactions, with centroid–centroid distances of 3.862 (2) and 3.887 (5) Å, and significant C—H⋯π interactions help to stabilize the crystal structure. The atoms of the unique terminal 4-pyridinepropane group are disordered over two sites, the ratio of refined occpancies being 0.712 (7):0.288 (7).

Related literature

For the β-diketone group, see: Yoshida et al. (1999 ▶). For factors influencing structures and applications, see: Ghosh et al. (2004 ▶). For the 1-benzoylacetone ligand, see: Han & Zhou (2008 ▶); Bučar & Meštrović (2003 ▶); Meštrović et al. (2004 ▶). For 1,3-bis(4-pyridyl)propane, see: Carlucci et al. (2002 ▶); Han et al. (2007 ▶).

Experimental

Crystal data

[Mn(C₁₀H₉O₂)₂(C₁₃H₁₄N₂)₂]
M _r = 773.81
Triclinic,
a = 9.771 (2) Å
b = 10.269 (2) Å
c = 10.485 (2) Å
α = 79.84 (3)°
β = 77.68 (3)°
γ = 89.45 (3)°
V = 1011.3 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 298 K
0.43 × 0.27 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.886, T _max = 0.949
9996 measured reflections
4583 independent reflections
2625 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.131
S = 1.11
4583 reflections
279 parameters
22 restraints
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009891/lh2780sup1.cif

e-65-0m423-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009891/lh2780Isup2.hkl

e-65-0m423-Isup2.hkl^{(224.5KB, hkl)}

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

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

Mn1—O2	2.124 (2)
Mn1—O1	2.157 (2)
Mn1—N1	2.330 (3)

Open in a new tab

O2—Mn1—O2ⁱ	180
O2—Mn1—O1ⁱ	97.35 (8)
O2—Mn1—O1	82.65 (8)
O1ⁱ—Mn1—O1	180
O2—Mn1—N1	90.12 (9)
O1—Mn1—N1	91.32 (9)
O2—Mn1—N1ⁱ	89.88 (9)
O1—Mn1—N1ⁱ	88.68 (9)
N1—Mn1—N1ⁱ	180

Open in a new tab

Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯Cg1	0.93	2.56	3.159 (4)	122
C14—H14A⋯Cg2ⁱⁱ	0.93	2.91	3.738 (5)	149
C14—H14A⋯Cg3ⁱⁱ	0.93	2.63	3.440 (9)	147
C15—H15A⋯Cg1	0.93	2.60	3.206 (3)	123
C20—H20A⋯Cg4ⁱⁱⁱ	0.93	2.65	3.529 (7)	158

Open in a new tab

Symmetry codes: (ii) Inline graphic ; (iii) .Cg1, Cg2, Cg3 and Cg4 are the centroids of the Mn1/O1/C1–C3/O2, N2/C19–C23, N2A/C19A–C23A and C4–C9 rings, respectively.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (20701022), the Natural Science Foundation of Zhejiang Province (Y4080435), the Natural Science Foundation of Ningbo Municipality (2007A610024) and the K.C. Wong Magna Fund of Ningbo University.

supplementary crystallographic information

Comment

Great attention has been given to the β-diketone group, as it can chelate divalent 3d-electron metal elements with a heterocyclic base as an electron donor and a number of complexes have been reported in the literature (Yoshida et al., 1999). Many factors, such as guests with different shapes and sizes, the shape of counterions, metal ions and nonconcovalent inter- or intramolecular forces (e.g. hydrogen bonding, π···π stacking and C—H···π interactions) play important roles in determining their structures and applications (Ghosh et al., 2004). 1-Benzoylacetone (Hbzac) is an excellent choice of ligand, not only due to its chelating coordinating effect to the metal center, but also to its ability to act as an anionic ligand to balance the charge and form a neutral framework (Han & Zhou, 2008; Bučar et al., 2003; Meštrović et al., 2004). Another organic ligand, 1,3-bis(4-pyridyl)propane) (bpp), is a long and flexible multi-functional linker, which can adopt different conformations with respect to the relative orientations of the CH₂ groups (Han et al., 2007; Carlucci et al., 2002). Recently, we synthesized a neutral monomer, [Mn(bzac)₂(bpp)₂] through the ambient evaporation of a mixed solution, of which weak π···π stacking and significant C—H···πinteractions are observed in the crystal structure.

There title compound, [Mn(bzac)₂(bpp)₂] (1), is centrosymmetric with the Mn^II ion adopting a slightly distorted octahedral coordination geometry. As shown in Fig. 1, the asymmetric unit consists of one-half of the molecule. The Mn^II ion is coordinated by four O atoms from two symmetry realted bzac anionic ligands in the equatorial plane and two N atoms from two symmetry realted bpp ligands in the axial sites. The chelate ring (Mn/O1/C1/C2/C3/O2) is essentially planar and forms a dihedral angle of 84.96 (8)° with the N1/C11-C15 ring and an angle of 12.49 (9)° with the C4-C9 ring. In the crystal structure there are weak π···π interactions between symmetry related (N1/C11-C15) pyridine rings (symmetry code: 2-x,1-y,1-z) with a centroid-to-centroid distance of 3.862 (2) Å and a perpendicular distance of 3.536 (2)Å and between symmetry related N2/C19-C23 rings (symmetry code: 2-x,2-y,2-z) with a centroid-to-centroid distance of 3.887 (5)Å and a perpendicular distance of 3.280 (3)Å (see Fig .2). In addition, significant C—H···π interactions (Spek, 2009) (Table 2) help stabilize the crystal structure.

Experimental

A mixture of 1-benzoylacetone (0.0358 g, 0.2 mmol) and 1,3-bis(4-pyridyl)propane (0.0830 g, 0.4 mmol) in mixed solution of CH₃CN (10ml) and H₂O (10ml) was stirred for 30 min. Then MnCl₂.4H₂O (0.1547g, 0.8 mmol) was added to the solution and stirred for 1 h. The mixed solution was allowed to stand at room temperature for 15 days. A quantity of yellow block-shaped crystals were obtained and collected by filtration with 20% yield based on MnCl₂.4H₂O.