A new symmetric branched 4-nitrophenyl hydrazine compound has been prepared in one-step procedure by direct condensation of aromatic ketone with hydrazine in MeOH. The synthesized compound, red isomer, was characterized by IR, ¹H and ¹³C NMR spectroscopy, Elemental analyses, Mass spectrometry and X-ray crystallography. Refluxing in MeOH solution led to thermo-isomerism offering a white isomer product that was characterized by X-ray crystallography. The red isomer crystallizes in the orthorhombic system having space group Pbcn, with a = 12.7612(4), b = 11.5197(3), c = 20.1586(7) Å, V = 2963.42(16)ų, Z = 8 while the white isomer crystallizes in the triclinic system having space group P−1, with a = 7.8007(4), 8.5966(7), 12.224 (1) Å, 𝛼 = 71.133(7), 𝛽 = 81.281(5), 𝛾 = 74.895(5)°, V = 746.86(9)ų, Z = 2. Molecules of both compounds are twisted at N2–N3 bond with the C7-N2-N3-C9 torsion angle of 155.23(12) and −113.36(18)°, respectively. The crystal structures of both compounds are stabilized by weak intramolecular C—H. . .N contacts and intermolecular C—H. . .O hydrogen bonding interactions. In addition, 𝜋–𝜋 stacking interactions are observed between the same aromatic rings of molecules.