Abstract: Protonated N,N,N',N'-tetrabenzyl-ethylenediamine(L) can form second-sphere complexes with [MCl₄]^2-(M=Mn, Co, Cu). In these crystals, thick 1D ribbons and 2D layer frameworks are constructed through N—H…Cl interactions. The orientations of benzyl groups of compound L in the ribbon or layer are horizontal and perpendicular, respectively, through C—H…Cl interactions, so that the ribbon and layer with alternately convex-concave site arrangement are formed. The caves between layers are formed by C—H…H—C interaction of convex-concave sites on the layers, thus constructing a 3D hydrophobic channel framework, and alcohol molecules are accommodated in the channel. However, due to the absence of C—H…Br interactions between benzyls and [CuBr₄]^2- in L·2H⁺·[CuBr₄]^2-, the orientation of benzyls of compound L adopts the same direction as a molecular long axis , thus, the 2D layer framework formed by compound L with [CuBr₄]^2- is planar, and the 3D hydrophobic channel framework and the inclusion of alcohol molecules are not observed.

Key words: N,N,N’,N’-Tetrabenzyl-ethylenediamine, Crystal engineering, Second-sphere coordination, [MnCl₄/CoCl₄/CuCl₄]^2-, [CuBr₄]^2-