
%0 Journal Article
%A Curtis, Neil F. 
%A Gladkikh, Olga P. 
%A Weatherburn, David C. 
%A De Courcey, John S. 
%A Waters, T. Neil M. 
%T Compounds of Copper(II) and Nickel(II) with 6,8,8,13,13,15-Hexamethyl-1,2,4,5,9,12- hexaazacyclopentadeca-5,15(1)-diene and Some 3-Substituted Homologues
%J Australian Journal of Chemistry
%D 1998/07/13
%V 51
%N 7
%P 611-630
%K 
%R https://doi.org/10.1071/C97024
%U https://www.publish.csiro.au/paper/C97024 
%X Copper(II) and nickel(II) compounds, &#91;M(L)&#93;2+, of the macrocyclic ligand 6,8,8,13,13,15-hexamethyl-1,2,4,5,9,12-hexaazacyclopentadeca-5,15(1)-diene are formed by reaction of compounds of 4,4,9,9-tetramethyl-5,8-diazadodecane-2,11-dione dihydrazone with methanal. Analogous reactions with aldehydes RHCO, or ketones RR&#8242;CO, form compounds of 3-R or 3-RR&#8242; substituted ligands, &#91;M(r- L)&#93;2+ or &#91;M(rr&#8242;-L)&#93;2+, respectively. The nickel(II) cations form singlet ground state salts, e.g. &#91;Ni(L)&#93;X2, X = &#91;ClO4&#93;- or &#189;&#91;ZnCl4&#93;2-, and also triplet ground state compounds, e.g. &#91;Ni(L) (NCS)2&#93; and &#91;Ni(L)(X)&#93; (ClO4) (X = NO2-, C2O42-, N3-, etc.). The structures of &#91;Cu(L)&#93; (ClO4)2, &#91;Ni(L)&#93; (ClO4)2, the 3-propyl compound formed from butanal, &#91;Cu(pr-L)&#93; (ClO4)2.H2O, and the compounds of 9,11,11,16,16,18-hexamethyl-7,8,12,15,19,20-hexaazaspiro&#91;5.14&#93;eicosa-8,18(1)-diene (chex-L), formed from cyclohexanone, namely &#91;Cu(chex-L)&#93; (ClO4)2.MeOH, &#91;Ni(chex-L)&#93; (ClO4)2, and &#91;Ni(chex-L)&#93; (ClO4)2.MeOH, were determined. All have the metal ions in tetrahedrally twisted square-planar coordination, by N1, N5, N9 and N12 , with N9N12-rac, for the (L) and (pr-L) compounds, or by the structurally equivalent N3, N7, N10 and N14, with N7N10-rac, for the (chex-L) compounds. The &#91;Cu(L)&#93;2+ and &#91;Cu(pr-L)&#93;2+cations have saddle-like macrocycle conformations, with approximate mirror symmetry, while the other compounds have &#8242;twisted&#8242; macrocycle conformations with approximate twofold symmetry &#123;&#91;Cu(L)&#93; (ClO4)2, C15H32Cl2CuN6O8, orthorhombic,P 212121, a 8&#183;562(7), b 13&#183;096(8), c 20&#183;257(6) &#197;, Z 4, R 0&#183;041 for 1540 reflections; &#91;Ni(L)&#93; (ClO4)2, C15H32Cl2N6NiO8, orthorhombic, P21/n, a 13&#183;500(3), b 9&#183;207(2), c 19&#183;478(5) &#197;, &#946; 103&#183;94(2)&#176;, Z 4, R1 0&#183;055 for 2650 reflections; &#91;Cu(Pr-L)&#93; (ClO4)2.H2O, C18H40Cl2CuN6O9, monoclinic, C 2, a 24&#183;229(5), b 13&#183;780(3), c 8&#183;877(2) &#197;, &#946; 108&#183;79(3)&#176;, Z 4, R1 0&#183;067 for 1765 reflections; &#91;Cu(chex-L)&#93; (ClO4)2.MeOH, C21H44Cl2CuN6O9, monoclinic, C 2/c, a 17&#183;086(5), b 24&#183;539(2), c 14&#183;496(1) &#197;, &#946; 89&#183;94(2), Z 8, R1 0&#183;072 for 2521 reflections; &#91;Ni(chex-L)&#93; (ClO4)2, C20H40Cl2N6NiO8, monoclinic, P 21/c, a 14&#183;820(2), b 18&#183;599(4), c 10&#183;282(1) &#197;, &#946; 106&#183;26(1)&#176;, Z 4, R1 0&#183;067 for 2552 reflections; &#91;Ni(chex-L)&#93; (ClO4)2.MeOH, C21H44Cl2CuN6O9, monoclinic, C 2/c, a 14&#183;451(2), b 24&#183;11(2), c 16&#183;740(3) &#197;, &#946; 90&#183;14(1)&#176;, Z 8, R1 0&#183;064 for 2598 reflections&#125;. 
