cis-Dichloridobis­(5,5′-dimethyl-2,2′-bipyridine)­manganese(II) 2.5-hydrate

Lívia Batista Lopes; Charlane Cimini Corrêa; Renata Diniz

doi:10.1107/S1600536811021805

. 2011 Jun 11;67(Pt 7):m906–m907. doi: 10.1107/S1600536811021805

cis-Dichloridobis(5,5′-dimethyl-2,2′-bipyridine)manganese(II) 2.5-hydrate

Lívia Batista Lopes ^a, Charlane Cimini Corrêa ^a, Renata Diniz ^a,^*

PMCID: PMC3152002 PMID: 21836893

Abstract

The metal site in the title compound [MnCl₂(C₁₂H₁₂N₂)₂]·2.5H₂O has a distorted octahedral geometry, coordinated by four N atoms of two 5,5′-dimethyl-2,2′-dipyridine ligands and two Cl atoms. Two and a half water molecules of hydration per complex unit are observed in the crystal structure. The compounds extend along the c axis with O—H⋯Cl, O—H⋯O, C—H⋯Cl and C—H⋯O hydrogen bonds and π–π interactions [centroid-centroid distance = 3.70 (2) Å] contributing substantially to the crystal packing. The Mn and one of the water O atoms, the latter being half-occupied, are located on special positions, in this case a rotation axis of order 2.

Related literature

For the structures and applications of bipyridine and analogous ligands, see: Hazell (2004 ▶); Bakir et al. (1992 ▶); Cordes et al. (1982 ▶); Hung-Low et al. (2009 ▶). For the structure and applications of 5,5′-dimethyl-2,2′-dipyridine, see: Marandi et al. (2009 ▶); van Albada et al. (2005 ▶). For weak intermolecular interactions, see: Calhorda (2000 ▶); Desiraju (1996 ▶); Janiak (2000 ▶).

Experimental

Crystal data

[MnCl₂(C₁₂H₁₂N₂)₂]·2.5H₂O
M _r = 539.35
Monoclinic,
a = 18.6703 (9) Å
b = 14.0598 (4) Å
c = 12.0536 (7) Å
β = 122.430 (7)°
V = 2670.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 293 K
0.47 × 0.35 × 0.34 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2008 ▶) based on expressions derived by Clark & Reid (1995 ▶)] T _min = 0.470, T _max = 0.697
11860 measured reflections
3317 independent reflections
2499 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.150
S = 1.09
3317 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021805/im2285sup1.cif

e-67-0m906-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021805/im2285Isup2.hkl

e-67-0m906-Isup2.hkl^{(159.5KB, 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
O1—H1A⋯Cl1	0.84	2.42	3.243 (3)	168
O1—H1B⋯Cl1ⁱ	0.81	2.73	3.358 (4)	136
O2—H2A⋯O1	0.86	2.16	2.951 (6)	153
C3—H3⋯O1ⁱⁱ	0.93	2.49	3.257 (5)	140
C6—H6A⋯Cl1ⁱ	0.96	2.79	3.717 (4)	162

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

Acknowledgments

The authors thank CNPq, CAPES and FAPEMIG (Brazilian agencies) for financial support, and LabCri (Federal University of Minas Gerais) for measuring the X-ray diffraction data.

supplementary crystallographic information

Comment

Bipyridine and analogous ligands are commonly used in the formation of different complexes with a general variety of transition metals (Hazell, 2004; Bakir et al., 1992; Cordes et al.,1982; Hung-Low et al.,2009;). The ligand 5,5'-Dimethyl-2,2'-dipyridine (abbreviated as dmdpy) acts as a chelator and usually gives rise to monomeric compounds (Marandi et al., 2009). Only a limited number of X-ray crystal structures with the ligand dmdpy has been published (van Albada et al., 2005). In this study we used the ligand 5,5'-dimethyl-2,2'-dipyridine and manganese chloride tetrahydrate. This mixture resulted in the compound [Mn(C₁₂H₁₂N₂)₂Cl₂] × 2.5 H₂O (Scheme 1).

The molecular structure of the complex unit of the titlecompound [Mn(C₁₂H₁₂N₂)₂Cl₂] × 2.5 H₂O is shown in Figure 1. The metal site is coordinated by four nitrogen atoms N1, N2, N1ⁱ and N2ⁱ of the ligand dmdpy and two chlorides Cl1 and Cl1ⁱ adopting a distorted octahedral geometry as evidenced by the Mn—N1 distances (2.3111 (19) Å), Mn—N2 (2.245 (2) Å) and Mn—Cl1 (2.4702 (6) Å). The Mn atom is located in a special position, which in this case is a rotation axis of order 2.

The compound crystallizes in the monoclinic system and its unit cell is shown in Figure 2. The compound [Mn(C₁₂H₁₂N₂)₂Cl₂] × 2.5 H₂O is a complex that stretches along the crystallographic c axis with the molecular entities being interconnected by weak hydrogen bonds (Desiraju, 1996; Calhorda, 2000) shown in Figure 2. These hydrogen bonds are formed by the interaction between oxygen atoms of water molecules O1 and O2 and the chlorine atom Cl1 which is coordinated to the metal. The distances O1—O2 and O1—Cl1 charge 2.951 (6) Å and 3.243 (3) Å, respectively. π-π interactions between aromatic rings of the nitrogen ligand dmdpy are also shown in Figure 2. These interactions contribute substantially to the crystal packing (Janiak, 2000). In this compound the centroid-centroid distance is 3.70 (2) Å, and there was a substantial overlap between the aromatic rings of the ligand dmdpy, being centroid-plane distance of 3.45 (1)Å and the horizontal displacement of 1.37 (2) Å.

Experimental

All chemicals were obtained commercially and used without further purification. The complex was synthesized by mixing of 0.38 mmol of dmdpy dissolved in ethanol and 0.38 mmol of MnCl₂ × 4 H₂O dissolved in water. The mixture was placed under agitation for 40 h. After a few weeks, yellow single crystals suitable for the analysis of X-ray diffraction were obtained (yield: 39%).