Novel Conformational Isomerism in a Six-Coordinate Silver(I) Complex of a Sexadentate Macrocycle With an N₃S₃ Donor Set

Abstract

The synthesis and structural characterization of the condensation product formed by a template reaction of 2,6-diacetylpyridine and 3,6,9-trithiaundecane-1,11-diamine about silver(I) (as perchlorate ) are described. Crystals are monoclinic, C2/c, a 27.114(10), b 7.546(5), c 22.137(10) Å, β 105.35(3)°, Z= 8×[AgL]⁺(ClO₄)^-(L = C₁₇H₂₅N₃S₃). R was 0.057 for 2372 'observed' reflections. The six-coordinate silver(I) atom lies in a novel environment comprised of a mer-triaza moiety derived from 2,6-diacetylpyridine [Ag-N, 2.422(8) (central), 2. 538(8), 2.546(9)Å (distal)] and a fac-trithia moiety straddling its plane [Ag-S, 2.603(6) (central), 2.815(4), 2.881(3) Å (distal)]. The complex cation is a different conformational isomer to that found in the previously studied tetraphenylborate salt. In the latter, Ag-N are 2.422(9) (central), 2.613(9), 2.399(7) Å (distal), with Ag-S 2.670(3) (central), 2.655(3), 2.949(4) Å (alstal).