The diazotisation of 2,2Ј-diaminotolane with one equivalent of HNO 2 yields the macrocyclic bis(tolanetriazene) (tolaneN 3 H) 2 in moderate yield. As shown by the crystal structure determination, the molecule is essentially planar. After deprotonation, the central cavity is suitable for complexation of transition metal ions. In pyridine solution, the anion (tolaneN 3 ) 2 2-is formed, which reacts with the acetates of Co 2+and Ni 2+ to the dark red coloured complexes [M((tolaneN 3 ) 2 )-(py) 2 ]. The metal ions are located in the centre of the macrocycles, coordinated by four N atoms of the two triazenide

SummaryTwo macrocyclic bis(ureas) 1 and 2, both based on diphenylurea, have been synthesized. Compound 1 represents the smaller ring with two ethynylene groups as linkers and 2 the larger ring with two butadiynylene groups. On thermal treatment to 130 °C molecule 1 splits up into two dihydroindoloquinolinone (3) molecules. Both compounds 1 and 2 form adducts with polar molecules such as dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) and act as complexing agents towards a series of anions (Cl−, Br−, I−, NO3 −, HSO4 −). The crystal structures of 3, 2·2DMSO, 2·2DMF, and of the complex NEt4[Br·2] have been determined. Quantitative investigations of the complexation equilibria were performed via 1H NMR titrations. While 1 is a rather weak complexing agent, the large ring of 2 binds anions with association constants up to log K = 7.93 for chloride ions.

The reaction of 2-(1,2,3,4-tetra­hydro­napthalen-1-yl­idene)hydrazinecarbo­thio­amide (TTSC) with pyrazine-2,3,5,6-tetra­carbo­nitrile (tetra­cyano­pyrazine, TCNP) yields the title 2:1 charge-transfer adduct, 2C11H12N3S·C6N8. The complete TCNP mol­ecule is generated by a crystallographic inversion centre and the non-aromatic ring in the TTSC mol­ecule adopts an envelope conformation with a methyl­ene C atom as the flap. In the crystal, the thio­semicarbazone mol­ecules are connected through inversion-related pairs of N—H⋯S inter­actions, building a polymeric chain along the b-axis direction. The TCNP mol­ecules are embedded in the structure, forming TTSC–TCNP–TTSC stacks with the aromatic rings of TTSC and the mol­ecular plane of TCNP in a parallel arrangement [centroid–centroid distance = 3.5558 (14) Å]. Charge-transfer (CT) via π-stacking is indicated by a CT band around 550 cm−1 in the single-crystal absorption spectrum.