A new photoluminescence supramolecular compound [Cu(HIm)(PPh3)2I] was synthesized and characterized by single crystal X-ray diffraction, elemental analysis, as well as IR, UV-Vis absorption and luminescence spectrometry. It crystallizes in monoclinic system, space group P21/n with a=1.333 5(14) nm, b=1.310 3(9) nm, c=2.154 4(16) nm, α=90.00°, β=101.130(10)°, γ=90.00°, V=3.694(5) nm3, Z=4, Dc=1.408 Mg·m-3. The single crystal structure indicates that the 2D supramolecular network structure is established by intermolecular weak N-H...I and C-H...I hydrogen-bonding interactions. The N-H...I is responsible for the conformation of one-dimensional zigzag chains and the C-H...I connects these chains to form two-dimensional supramolecular hydrogen-bonding network. At room temperature in the solid state, the complex is photoluminescent with an emission peak maximum at 460 nm, upon excitation at 330 nm. The emission is assigned to the metal-perturbed intraligand (PPh3) in nature. CCDC: 228743.
