A correlated and relativistic calculations of the interaction energy, IR and NMR spectroscopic parameters for the HXeF monomer and the HXeF center dot center dot center dot HF complexes have been performed. The SAPT approach has beer, applied to analyze the physical contributions to the total interaction energy. The induction and dispersion terms proved to be crucial in establishing the preference for the bending over the colinear HXeF center dot center dot center dot HF structure. The insertion of the Xe atom into the HF molecule and the (HF)(2) dimer causes large decrease of the (129)Xe shielding constant on correlated CCSD and Dirac-Hartee-Fock level. When HF molecule is attached to the HXeF, the Xe-H bond becomes stronger and the Xe nucleus is deshielded in comparison to the HXeF monomer. (C) 2011 Elsevier B.V. All rights reserved.