Crystal structures of the homologous series of bis(pyridylcarboxamido)alkane derivatives having an odd number of carbon atoms in the alkyl spacer were analyzed and found to exhibit interesting structural and physical properties which differ significantly from those of their even analogues. The even members of this series have shown a remarkable preference to form one- or two-dimensional structures via N−H···N or N−H···O hydrogen bonds, while the odd ones have preferably exhibited 4-fold interpenetrated 3D networks such as diamondoid or quartz topologies via N−H···N hydrogen bonds. The odd members of the series have been found to adopt twisted conformations, in contrast to the linear conformation of the even ones. The melting points of the odd analogues are found to be lower than those of corresponding even members when the attached group (R) is a phenyl. However, such a trend in MP values has not been observed when the R group is a 4-pyridyl or 3-pyridyl group. The densities of these materials are found to decrease systematically with an increase in chain length and did not exhibit any dependence on the odd and even number of the -CH2- groups in the spacers.