4′-(4-Biphenylyl)-4,2′:6′,4′′-terpyridine (1) reacts with ZnCl 2 or ZnBr 2 to produce discrete metallohexacycles instead of the expected one-dimensional coordination polymers. Structural determination of [{ZnCl 2 (1)} 6 ] and [{ZnBr 2 (1)} 6 ] reveals that the metallomacrocycles adopt a conformation in which the biphenyl domains are in an alternating up/down arrangement (conformer I). The hexamers pack into tubes; within each tube, biphenyl domains of every second hexamer are interdigitated, and these assemblies then interlock to produce a rigid architecture supported by pyridine-phenyl face-to-face contacts. π-Stacking between 4,2′:6′,4′′-tpy domains operates between adjacent tubes. Reaction of ZnCl 2 or ZnBr 2 with 4′-(2′,3′,4′,5′,6′-pentafluorobiphenyl-4-yl)-4,2′:6′,4′′-terpyridine (2) leads to [{ZnCl 2 (2)} 6 ] and [{ZnBr 2 (2)} 6 ], each crystallizing in two conformations; the centrosymmetric chair-conformer (II) is dominant with respect to the tub-like conformer I. Both conformers pack into tube assemblies, but that consisting of conformer II is less rigid than that of I. Reaction of 4′-(4-(naphthalen-1-yl)phenyl)-4,2′:6′,4′′-terpyridine (3) with ZnCl 2 or ZnBr 2 leads to [{ZnX 2 (2)} 6 ] (X = Cl, Br) in conformer I; disordering of the naphthyl substituents is problematic.Assembly of the metallohexacycle in the presence of C 60 results in the formation of the host-guest complex [2{ZnCl 2 (3)} 6 ·C 60 ]·6MeOH·16H 2 O. The [{ZnCl 2 (3)} 6 ] units assemble into a tube-like array that mimics that observed in the parent host. In the host-guest complex, each crystallographically-ordered C 60 is trapped between six ordered naphthyl units, three from one hexamer and three from its interdigitated partner, and the C 60 -six-naphthyl unit sits centrally within a second [{ZnCl 2 (3)} 6 ] macrocycle. In contrast to previously described tube-like host-guest assemblies featuring fullerene entrapment, [2{ZnCl 2 (3)} 6 ·C 60 ] is unusual in having an ordered array of C 60 molecules present in every other available cavity, despite the fact that sterically, the 'empty' cavity could, in principle, host a C 60 guest. † Electronic supplementary information (ESI) available: Fig. S1-S6 ORTEP plots with atom labelling for the contents of the asymmetric units in the structures described in the paper. Crystallographic data for [{ZnCl 2 (1/2)} 6 ]·2CHCl 3 ·3MeOH·9H 2 O. CCDC 956344-956349. For ESI and crystallographic data in CIF or other electronic format see Scheme 1 (a) General structure of one-dimensional coordination polymers formed with 4′-substituted 4,2′:6′,4′′-terpyridines and ZnX 2 (X = Cl, Br, I; R = various). (b) Structure of the metallohexacycle formed with ZnCl 2 and 4′-(4-ethynylphenyl)-4,2′:6′,4′′-terpyridine (R = HCCC 6 H 4 ); the ring has a chair conformation in the solid state. Scheme 2 Structures of ligands 1-3.CrystEngComm Paper CrystEngComm, 2014, 16, 328-338 | 329 This journal is Scheme 3 Structure of the bis(nickellaporphyrin) complex 5 reported by Tani and coworkers. 41,42 CrystEngComm Paper CrystEngComm, 201...