The method of symmetry breaking potential and first order cluster expansion technique for the partition functions adopted for the theory of ordering in liquid crystals has been extended to symmetric and asymmetric molecules. The order parameter is calculated as a function of temperature and packing coefficient as a function of position of double bond in alkenyl chain length for homologous series of 4–alkenyl bicyclohexylnitrile Compounds. The theoretical calculations account fairly well for the gradient differences in the order parameters of symmetric and asymmetric molecules and packing coefficients.