CH⋯π and π⋯π interaction in benzene-acetylene clusters

► Structure of benzene-acetylene clusters investigated using the CCSD(T) method. ► T-shaped geometry most stable for the 1:1 benzene-acetylene complex. ► Ring-shaped geometry most stable for the 1:2 complex. ► ωB97X-D functional most suited for energetic studies of bz-ac clusters. ► Intermolecular interaction seems to be pair-wise additive for the hetero clusters.