Bis(2-chloro- N , N -di-methyl-ethan-1-aminium) tetra-chlorido-cobaltate(II) and tetra-chlorido-zincate(II)

The few examples of structures containing the 2-chloro- , -di-methyl-ethan-1-aminium or 3-chloro- , -di-methyl-propan-1-aminium cations show a compet-ition between and conformations for the chloro-alkyl chain. To explore further the conformational landscape of these cations, and their possible use as mol-ecular switches, the title salts, (C H ClN) [CoCl ] and (C H ClN) [ZnCl ], were prepared and structurally characterized. Details of both structures are in close agreement. The inorganic complex exhibits a slightly flattened tetra-hedral geometry that likely arises from bifurcated N-H hydrogen bonds from the organic cations. The alkyl chain of the cation is disordered between and conformations with the conformation occupancy refined to 0.707 (2) for the cobaltate. The conformation places the terminal Cl atom at a tetra-hedral face of the inorganic complex with a contact distance of 3.7576 (9) Å to the Co center. The conformation places the terminal Cl atom at a contact distance to a neighboring conformation terminal Cl atom that is ∼1 Å less than the sum of the van der Waals radii. Thus, if the conformation is present at a site, then the nearest neighbor must be DFT geometry optimizations indicate the conformation is more stable by 0.226 eV, which reduces to 0.0584 eV when calculated in a uniform dielectric. DFT geometry optimizations for the unprotonated mol-ecule indicate the conformation is stabilized by 0.0428 eV , with no strongly preferred conformation in uniform dielectric, to provide support to the notion that this cation could function as a mol-ecular switch deprotonation.