Formation of chain and large-ring polymeric metal complexes by the 'extended reach' sulfur donor ligands N,N '-ethylenebis(pyrrolidine-2-thione) and N,N '-p-phenylenedimethylenebis(pyrrolidine-2-thione)

摘要

The preparations are reported of the "extended-reach" sulfur donor ligands N,N'-ethylenebis(pyrrolidine-2-thione) (EBPT) and N,N'-p-phenylenedimethylenebis(pyrrolidine-XBPT) and of a range of complexes with Co-II, Ni-II Cu-II, Cu-I, Zn-II, Cd-II and Ag-I, seven of which have been structurally characterized by X-ray crystallography. [Co(NCS)(2)(EBPT)](n) crystallizes in the orthorhombic space group Pna2(1), with a = 10.339(4) Angstrom, b = 10.074(5) Angstrom, c = 16.832(7) Angstrom, and Z = 4. [ZnBr2(EBPT)](n) crystallizes in the monoclinic space group P2(1), with a = 9.979(4) Angstrom, b = 9.871(3) Angstrom, c = 16.057(6) Angstrom, beta = 99.95(2)degrees, and Z = 8. Both of these complexes contain tetrahedrally coordinated metal ions linked by EBPT bridges to form chains. [CoCl2(EBPT)](2) crystallizes in the tetragonal space group l4(1)/acd, with a = b = 14.400(1) Angstrom, c = 28.426(4) Angstrom, and Z = 16. This compound forms discrete 18-membered rings. [CuCl(EBPT)](n) crystallizes in the monoclinic space group C2/c, with a = 19.188(3) Angstrom, b = 9.987(2) Angstrom, c = 15.964(3) Angstrom, beta = 123.12(1)degrees, and Z = 8. In this compound each EBPT ligand employs one monodentate S atom and one mu 2-S atom and forms ribbons of alternating Cu-2(EBPT)(2) 18-membered rings and four-membered Cu-2(mu(2)-S)(2) rings. {[CuBr(EBPT)].MeNO2}(n) crystallizes in the monoclinic space group C2/c, with a = 18.117(3) Angstrom, b = 9.932(1) Angstrom, c = 18.113(3) Angstrom, beta = 90.70(1)degrees, and Z = 4. This compound also has a ribbon structure, but here 18-membered Cu-2(EBPT)(2) rings alternate with Br-bridged Cu2Br2 units. [Ni(NO3)(2)(p-XBPT)](n) crystallizes in the monoclinic space group C2/c, with a = 10.900(3) Angstrom, b = 14.474(4) Angstrom, c = 13.488(4) Angstrom, beta = 99.24(2)degrees, and Z = 4. The nickel atoms are bonded to two bidentate nitrates and two bridging p-XBPT ligands, forming chains. {[Co(p-XBPT)(2)](ClO4)(2).4MeNO(2)}(n) crystallizes in the monoclinic space group C2/c,. with a = 18.284(2) Angstrom, b = 17.897(3) Angstrom, c = 31.136(4) Angstrom, beta = 102.38(1)degrees, and Z = 8. Each Co is tetrahedrally coordinated to four sulfur atoms from four p-XBPT units which connect the metal centers into sheets of contiguous 52-membered rings. EBPT crystallizes in the monoclinic space group P2(1), with a = 5.479(2) Angstrom, b = 9.560(4) Angstrom, c = 11.171(7) Angstrom, beta = 95.79(2)degrees, and Z = 2; the thiolactam rings are coplanar and the sulfur atoms anti-disposed. The role of ligand conformation in determining structural types is discussed. [References: 35]