Dichlorido(dipyrido[3,2-a:2′,3′-c]phenazine)manganese(II)

Mao-Liang Xu; Shu-Bo Sun; Xiu-Ying Li; Guang-Bo Che

doi:10.1107/S1600536808043468

. 2009 Jan 8;65(Pt 2):m136. doi: 10.1107/S1600536808043468

Dichlorido(dipyrido[3,2-a:2′,3′-c]phenazine)manganese(II)

Mao-Liang Xu ^a, Shu-Bo Sun ^b, Xiu-Ying Li ^c, Guang-Bo Che ^c,^*

PMCID: PMC2968193 PMID: 21581752

Abstract

The complete molecule of the title compound, [MnCl₂(C₁₈H₁₀N₄)₂], is generated by crystallographic twofold symmetry with the Mn atom lying on the rotation axis. The Mn coordination geometry is a distorted cis-MnCl₂N₄ octahedron, arising from two N,N′-bidentate dipyrido[3,2-a:2′,3′-c]phenazine (DPPZ) ligands and two chloride ions. In the crystal structure, neighbouring mononuclear units pack together through π–π contacts between the DPPZ rings [shortest centroid–centroid distance = 3.480 (2) Å], leading to a chain-like structure along [001]. C—H⋯Cl hydrogen bonds complete the structure.

Related literature

For background, see: Che et al. (2006 ▶, 2008 ▶); Xu et al. (2008 ▶).

Experimental

Crystal data

[MnCl₂(C₁₈H₁₀N₄)₂]
M _r = 690.44
Monoclinic,
a = 8.4017 (17) Å
b = 12.256 (3) Å
c = 28.226 (6) Å
β = 95.09 (3)°
V = 2895.0 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 292 (2) K
0.38 × 0.24 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.821, T _max = 0.864
11873 measured reflections
2866 independent reflections
1748 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.120
S = 1.00
2866 reflections
243 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043468/hb2884sup1.cif

e-65-0m136-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043468/hb2884Isup2.hkl

e-65-0m136-Isup2.hkl^{(137.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn—N1	2.283 (3)
Mn—N2	2.316 (3)
Mn—Cl	2.4644 (12)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Clⁱ	1.09 (3)	2.67 (3)	3.737 (4)	168 (2)
C15—H15⋯Clⁱⁱ	1.04 (3)	2.64 (3)	3.648 (4)	163 (3)

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

Acknowledgments

The authors thank the Doctoral Foundation of Jilin Normal University (grant Nos. 2006006 and 2007009) and the Subject and Base Construction Foundation of Jilin Normal University (grant No. 2006041).

supplementary crystallographic information

Comment

1,10-Phenanthroline (phen) and its derivatives, as chelating N-containing aromatic ligands, has been extensively studied in the chemistry of coordination polymers (Che et al., 2008). Here, we report the crystal structure of the title compound, [Mn(DPPZ)₂Cl₂] or [Mn(C₁₈H₁₀N₄)₂Cl₂] (I), based on the dipyrido[3,2 - a:2',3'-c]-phenazine (DPPZ) ligand (Xu et al., 2008).

In compound (I), the Mn atom (site symmetry 2) is coordinated in a distorted octahedral fashion (Fig. 1) by four N atoms from two DPPZ ligands and two Cl ions (Table 1). The DPPZ ring systems is almost planar and the dihedral angle between the two symmetry-related DPPZ planes is 70.66°.

π-π stacking interactions between the DPPZ ligands assemble mononuclear complex molecules into one-dimensional chains along (001) [centroid-centroid distances = 3.480 (2) Å] (Fig. 2). Finally, C—H···Cl hydrogen bonds involving the hydrogen of aromatic rings and the Cl ions further stabilize the crystal structure (Table 2).

Experimental

The DPPZ ligand was synthesized according to the literature method of Che et al. (2006). A mixture of DPPZ, MnCl₂ and water in a molar ratio of 2:1:5000 was sealed in a Teflon-lined autoclave and heated to 423 K for 3 d. Upon cooling and opening the bomb, yellow blocks of (I) were obtained (81% yield based on Mn).