AbstractCrystals of the title compound are monoclinic, a= 18.9 93 (11), b = 8.757(5), c= 13.267(8) Å, β = 106.60(5)°, Z = 4 in space group Cc (Cs4 , No. 9). The structure was determined by Patterson and electron-density methods and refined by least squares techniques to R= 0.081, R′ = 0.085 for 1293 independent reflections classified as observed. The molecule is found to adopt an almost regular trigonal bipyramidal geometry in which the two biphenylylene units span apical-equatorial positions and the 2-thienyl group occupies the remaining equatorial site. The 2-thienyl group, which is disordered, does not lie in the equatorial plane, and there is no indication of C2pπ → P3dπ-t interactions between the heteroaryl group and phosphorus. The steric requirements of the 2-thienyl group appear to be comparable with those of methyl and phenyl groups in bis(2,2′-biphenylylene)spiro-phosphoranes.