Variation of structural parameters of dimethylammonium manganese formate [(CH3)2NH2]Mn[(HCOO)3] upon substitution by the transition elements Zn, Co, and Ni is studied by powder X-ray diffraction (PXRD) technique. These metal–organic framework (MOF) crystals were grown by solvothermal method. The PXRD patterns of all MOFs exhibited rhombohedral structure. PXRD patterns of MOFs were analyzed using Rietveld refinement method. While the parent Mn-MOF and Mn0.9Zn0.1MOF are found to have similar structural parameters, Co and Ni substituted Mn-MOFs have smaller structural parameters than that of parent Mn-MOF. The reason for this variation in the lattice parameters is explained based on the Shannon ionic radii.