cis-Dichloridobis(di-2-pyridylamine-κ2 N,N′)manganese(II)

In the title complex, [MnCl2(C10H9N3)2], the MnII ion is six-coordinated in a considerably distorted cis-N4Cl2 octahedral environment defined by four N atoms of two chelating di-2-pyridylamine (dpa) ligands and two Cl− anions. In the crystal, the dpa ligands are not planar, the dihedral angles between the two pyridine rings being 29.3 (2) and 30.9 (2)°. The complex molecules are stacked in columns along the c axis and are connected by intermolecular N—H⋯Cl hydrogen bonds, forming a three-dimensional network. Weak inter- and intramolecular π–π interactions are present between the pyridine rings, the shortest centroid—centroid distance being 4.406 (3) Å.

In the title complex, [MnCl 2 (C 10 H 9 N 3 ) 2 ], the Mn II ion is sixcoordinated in a considerably distorted cis-N 4 Cl 2 octahedral environment defined by four N atoms of two chelating di-2pyridylamine (dpa) ligands and two Cl À anions. In the crystal, the dpa ligands are not planar, the dihedral angles between the two pyridine rings being 29.3 (2) and 30.9 (2) . The complex molecules are stacked in columns along the c axis and are connected by intermolecular N-HÁ Á ÁCl hydrogen bonds, forming a three-dimensional network. Weak inter-and intramolecularinteractions are present between the pyridine rings, the shortest centroid-centroid distance being 4.406 (3) Å .

Related literature
For the crystal structures of related Mn II complexes with dpa, see: Bose et al. (2005); Ha (2011a,b).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97. In the title complex, [MnCl 2 (dpa) 2 ], the Mn II ion is six-coordinated in a considerably distorted cis-N 4 Cl 2 octahedral environment defined by four N atoms of two chelating dpa ligands and two Clanions ( Fig. 1). The main contributions to the distortion are the tight N-Mn-N chelating angles (Table 1) (Table 1), the different trans effects of the Cl and N atoms cannot be observed reliably. In the crystal structure, the dpa ligands are not planar, the dihedral angles between the two pyridine rings being 29.3 (2)° and 30.9 (2)°. The complex molecules are stacked in columns along the c axis and connected by intermolecular N-H···Cl hydrogen bonds, forming a three-dimensional network (Fig. 2, Table 2). In the columns, numerous weak inter-and intramolecular π-π interactions are present between the pyridine rings, the shortest centroid-centroid distance being 4.406 (3) Å.

Experimental
To a solution of MnCl 2 .4H 2 O (0.1988 g, 1.005 mmol) in EtOH (20 ml) was added di-2-pyridylamine (0.3465 g, 2.024 mmol) and stirred for 3 h at room temperature. The formed precipitate was separated by filtration and washed with EtOH and acetone, and dried at 323 K, to give a white powder (0.2982 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH 3 CN solution.

Refinement
Carbon-bound H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C-H = 0.95 Å and U iso (H) = 1.2U eq (C)]. Nitrogen-bound H atoms were located from Fourier difference maps then allowed to ride on their parent atoms in the final cycles of refinement with N-H = 0.92 Å and U iso (H) = 1.5 U eq (N). The highest peak (0.51 e Å -3 ) and the deepest hole (-0.56 e Å -3 ) in the difference Fourier map are located 1.40 Å and 1.08 Å from the atoms H9 and N4, respectively.
supplementary materials sup-2 Figures Fig. 1. The molecular structure of the title complex, with displacement ellipsoids drawn at the 40% probability level for non-H atoms.