MERCURY MACROCYCLIC COMPLEXES - SYNTHESIS AND CRYSTAL-STRUCTURES OF ([HGCL(MU-CL)(L1)][HG(MU-CL)2])N (L1 = 1,4,7,10-TETRAOXA-13-AZACYCLOPENTADECANE), [HG(L2)CL2] (L2 = 1,4,7,10,13-PENTAOXA-16-AZACYCLOOCTADECANE) AND [HG(L3)CL2] (L3 = 16-METHYL-1,4,7,10,13-PENTAOXA-16-AZACYCLOOCTADECANE)

The mercury(II) complexes of the fifteen- and eighteen-membered ring macrocycles 1,4,7,10,-tetraoxa-13-azacyclopentadecane (L1); 1,4,7,10,13-pentaoxa-16-azacyclooctadecane (L2) and 16-methyl-1,4,7,10,13-pentaoxa-16-azacyclooctadecane (L3) have been prepared. The complexes {[HgCl(mu-Cl)(L1)][Hg(mu-Cl)2]}n, [Hg((L2)Cl2] and [Hg(L3)Cl2] have been characterised by single crystal X-ray structural analysis. {[HgCl(mu-Cl)(L1)][Hg(mu-Cl)2]}n crystallises in the orthorhombic space group Pbca, with a=7.498(1), b=15.201(1), c=32.575(2) angstrom, U=3713(2) angstrom3, Z=8, D(c)=2.727 g cm-3, With R 0.039, R(w) 0.040. The structure consists of a polymeric chain of five-coordinate mercury atoms [Hg(mu-Cl)2] bearing [HgCl(mu-Cl)(L1)] substituents. One mercury atom is located above the plane of the macrocyclic ligand L1; bond lengths Hg-N 2.145(10), Hg-O 2.664(10)-2.806(9) angstrom. Two Cl ligands are located on the same side of the folded macrocyclic ring, Hg(1)-Cl(1) and Hg(1)-Cl(2) 2.291(4) and 3.129(4) angstrom, respectively, Cl(1)-Hg(1)-Cl(2) 102.37(13)-degrees. [Hg(L2)Cl2] crystallises in the monoclinic space group P2(1)/c, with a=7.648(1), b=7.858(1), c=15.366(3) angstrom, beta=92.462(8)-degrees, U=922.6(3) angstrom3, Z=2, D(c)=1.925 g cm-3 with R 0.029, R(w) 0.032. The mercury atom is eight-coordinate and is located at an inversion centre; bond lengths Hg-Cl 2.327(2), Hg-N/O(1) 2.748(8), av. Hg-O distance 2.856 angstrom; the Cl(1)-Hg-Cl(1a) angle was 180-degrees. [Hg(L3)Cl2] crystallises in the monoclinic space group C2/c, with a=11.751(4), b=10.504(3), c=31.38(2) angstrom, beta=91.92-degrees, U=3871(2) angstrom3, Z=8, D(c)=1.884 g cm-3 and R 0.027, R(w) 0.031. The metal ion is eight-coordinate (five oxygen, one tertiary amine and two chloride donors); there are two short (2.767(5), 2.753(6) angstrom), and three longer (2.961(6), 2.968(6), 2.922(6) angstrom) Hg-O bond lengths, with Hg-N 2.739(6) and Hg-Cl 2.327(2) angstrom. The Cl(1)-Hg(1)-Cl(2) angle was 174.07(8)-degrees.