The title polymer compound with chlorobenzene as crystal solvents [Rh2II(4-Me-pf )2(O2CCMe3)2(1,4-dib)]n·n(chlorobenzene) (4-Me-pf− = N,N′-di-p-tolylformamidinate; 1,4-dib = 1,4-diisocyanobenzene) was isolated and the crystal structure was determined by the single-crystal X-ray diffraction method at 150 K. It crystallizes in the triclinc space group P1 with a = 10.6491(8)Å, b = 12.5796(11)Å, c = 19.3388(15)Å, α = 85.901(5)°, β = 77.146(5)°, γ = 85.792(5)°, V = 2514.9(4) Å3, Dx = 1.446 g/cm3, and Z = 2. The R1 [I > 2σ(I)] and wR2 (all data) values are 0.0555 and 0.1563, respectively, for all 8757 independent reflections. Two RhII atoms are bridged by two 4-Me-pf− and two pivalato ligands in the cis-(2:2) fashion. The axial sites of the dinuclear core are occupied by 1,4-dib ligands with distances of Rh–Cax = 2.129(6) and 2.129(7)Å to form a chain structure with alternated arrangement of cis-[Rh2II(4-Me-pf )2(O2CCMe3)2] and 1,4-dib. The Rh–Rh distance is 2.4845(6)Å, which is longer than the observed range for those of the lantern-type dirhodium(II) complexes with formamidinato and pivalato bridges and axially coordinating nitorgen atoms, reflecting the strong donor properies of the 1,4-dib carbon atoms. The diffuse reflectance spectra and adsorption properties for N2 were also examined.
