cis-Aquabis(di-2-pyridylamine-κ2 N,N′)iodidomanganese(II) iodide

The asymmetric unit of the title compound, [MnI(C10H9N3)2(H2O)]I, contains a cationic MnII complex and an I− anion. In the complex, the MnII ion is six-coordinated in a considerably distorted cis-N4IO octahedral environment defined by four N atoms of the two chelating di-2-pyridylamine (dpa) ligands, one I− anion and one O atom of a water ligand. As a result of the different trans effects of the I, N and O atoms, the Mn—N bond trans to the I atom is slightly longer than the Mn—N bond trans to the N or O atoms. The dpa ligands are not planar, with dihedral angles between the two pyridine rings of 26.2 (4) and 26.5 (4)°. The complex cations are stacked in columns along the a axis and are linked to the anions by intermolecular O—H⋯I and N—H⋯I hydrogen bonds.

The asymmetric unit of the title compound, [MnI(dpa) 2 (H 2 O)]I, consists of a cationic Mn II complex and an Ianion ( Fig.   1). In the complex, the Mn II ion is six-coordinated in a considerably distorted cis-N 4 IO octahedral environment defined by four N atoms of the two chelating dpa ligands, one Ianion and one O atom of a water ligand. The main contribution to the distortion is the tight N-Mn-N chelating angles (Table 1) (Table 1).
As a result of the different trans effects of the I, N and O atoms, the Mn1-N1 bond trans to the I atom is slightly longer than the Mn-N bond trans to the N or O atoms. In the crystal structure, the dpa ligands are not planar. The dihedral angles between the two pyridyl rings of dpa are 26.2 (4)° and 26.5 (4)°.
The complexes are stacked in columns along the a axis, and the component cations and anions are linked by intermolecular O-H···I and N-H···I hydrogen bonds (Fig. 2, Table 2). In the column, numerous inter-and intramolecular π-π interactions between the pyridyl rings are present, the shortest centroid-centroid distance being 3.728 (5) Å.

Experimental
To a solution of di-2-pyridylamine (0.3432 g, 2.005 mmol) in acetone (50 ml) was added MnI 2 (0.3108 g, 1.007 mmol) and refluxed for 7 h. The formed precipitate was separated by filtration and washed with acetone, and dried at 323 K, to give a white powder (0.1571 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from an MeOH 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-and oxygen-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, O-H = 0.84 Å and U iso (H) = 1.5 U eq (N, O). The highest peak (1.01 e Å -3 ) and the deepest hole (-1.13 e Å -3 ) in the difference Fourier map are located 1.01 Å and 0.79 Å from the atoms C8 and I1, respectively.
supplementary materials sup-2 Figures Fig. 1. The molecular structure the title compound, with displacement ellipsoids drawn at the 40% probability level for non-H atoms.  supplementary materials sup-9