Eight bis(nitronyl nitroxide) and bis(iminyl nitroxide) diradicals having thiophene (2,4NT, 2,5NT, 2,4IT, and 2,5IT) and 2,2’-bithienyl units (4,4’NB, 3,3’NB, 4,5’IB, and 5,5’IB) as couplers were prepared. Both 2,5NT and 4,4’NB crystallized in monoclinic space group P2(1)/n with a = 12.430(2) Angstrom, b = 13.968(4) Angstrom, c = 12.470(2) Angstrom, beta = 107.26(1)degrees, and Z = 4 and with a = 10.766(7) Angstrom, b = 10.186(3) Angstrom, c = 11.625(4) Angstrom, beta = 1199(3)degrees, and Z = 2. The dihedral angles between the imidazoline and thiophene rings were only 6 and 10 degrees in 2,5NT and 21 degrees in 4,4’NB. The 2,2’-bithienyl chromophore assumed a planar anti-conformation A dimer structure with the oxygen atom in one molecule and the nearest nitrogen atom in the other at a distance of 3.9 Angstrom stacks linearly along the b axis in 2,5NT. Each nitronyl nitroxide group at both ends of the 4,4’NB molecule is in close contact with that of the neighboring molecule to make a one-dimensional chain.