Anionic Halide···Alcohol Clusters in the Solid State

The cationic (1,3,5-triazapentadiene)­PtII complexes [1]­(Cl)2, [2]­(Cl)2, [3]­(Br)2, and [4]­(Cl)2, were crystallized from ROH-containing systems (R = Me, Et) providing alcohol solvates studied by X-ray diffraction. In the crystal structures of [1–4]­[(Hal)2(ROH)2] (R = Me, Et), the Hal– ion interacts with two or three cations [1–4]2+ by means of two or three or four contacts thus uniting stacked arrays of complexes into the layers. The solvated MeOH or EtOH molecules occupy vacant space, giving contacts with [1–4]2+, and connects to the Hal– ion through a hydrogen bridge via the H­(1O)­O­(1S) H atom forming, by means of the Hal–···HOR (Hal = Cl, Br) contact, the halide–alcohol cluster. Properties of the Cl–···HO­(Me) H-bond in [1]­[(Cl)2(MeOH)2] were analyzed using theoretical DFT methods.