Syntheses and characterizations of a series of silver-carboxylate polymers

Self-assembly reaction of H3btc (1,3,5-benzenetricarboxylic acid), H2ta (1,4-benzenedicarboxylic acid) or 1,2,4,5-benzenetetracarboxylic dianhydride with Ag(NO3) in mixed H2O/MeOH solution at room temperature gave rise to four novel 3D polymeric silver(I) complexes, [{Ag(H2btc)}{Ag2(Hbtc)}]n (1), [Ag(ta)1/2]n (2), [Ag2(btec)1/2]n (3) and [{Ag3(btec)3/4}{Ag(H2O)2(btec)1/4}]n (4) (H4btec=1,2,4,5-benzenetetracarboxylic acid). Complex 1 crystallizes in orthorhombic space group Fddd, with a=14.877(5), b=25.926(1), c=36.377(7) Å, Z=32. Complex 2 crystallizes in monoclinic space group P21/c, with a=7.257(6), b=8.949(8), c=6.346(5) Å, β=111.654(3)°, Z=4. Complex 3 crystallizes in orthorhombic space group P21/c, with a=8.333(8), b=6.335(5), c=10.964(9) Å, Z=4, whereas complex 4 crystallizes in triclinic space group , with a=7.509(1), b=9.351(1), c=10.307(7) Å, α=69.514(2), β=84.521(2), γ=83.638(2)°, Z=2. All compounds possess 3D framework and short Ag–Ag contacts are present in 1–4. In 1, the ligand unsupported Ag–Ag interactions play an important role in the formation of the complex, which is constructed by silver chains formed by Ag–Ag interactions and carboxylate spacers.