The tetrafluoroborate salt of bis{8-(diphenylphosphino)quinoline}copper(I), [Cu(Ph(2)Pqn)(2)]BF4, afforded orange prismatic (2O) or yellow columnar (2Y) crystals, dependent on the solvent and concentration of the recrystallization solution used. X-ray analysis revealed that crystals of 2O and 2Y had the same composition and exhibited different crystal systems: 2O was triclinic, with space group P (1) over bar and Z = 2, and 2Y was monoclinic with space group P2(1)/c and Z = 4. In these crystals, the tetrahedral copper(I) complex exhibited a strong "rocking distortion" toward a trigonal pyramidal coordination geometry (by a slide translation of one of the unsymmetrical bidentate chelating ligands along the tetrahedral edge). In addition, both the 2O and 2Y complexes showed a "flattening distortion", meaning that the dihedral angle between the two chelate planes were off-perpendicular and oriented toward opposite directions, which resulted in a pair of distortion isomers: syn clinal (sc: 2O) and anti clinal (ac: 2Y). P-31 CP-MAS NMR spectroscopy indicated that 2O and 2Y could be distinguished. Both isomers exhibited inequivalent P atoms, but a larger difference in chemical shift was observed in 2Y. TD-DFT calculations reproduced the difference in spectra between the orange- and yellow-colored complexes, which originated from metal-to-ligand charge-transfer transitions.