Solid State Self‐Assembly of an Extended Curved‐Arm Nickel(II) Macrocycle with Fullerene C₆₀

Three new co-crystalline structures are reported that contain fullerene C₆₀ with the under-represented Ni(II)-dibenzotetraaza[14]annulene derivative, (5,14-dihydro-6,8,15,17-tetrabenzyl-2,3,11,12-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclo-tetradecine)nickel(II), [Ni(Bz₄TMTAA)]. The single-crystal X-ray analysis shows that the three studied compounds crystallize in the monoclinic C2/c, Pnma orthorhombic and triclinic P <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:mrow><mml:mn>1</mml:mn> <mml:mo>,</mml:mo> <mml:mi>c</mml:mi> <mml:mi>h</mml:mi> <mml:mi>a</mml:mi> <mml:mi>r</mml:mi> <mml:mo>/</mml:mo> <mml:mn>0</mml:mn> <mml:mi>x</mml:mi> <mml:mn>00</mml:mn> <mml:mi>A</mml:mi> <mml:mi>F</mml:mi> <mml:mi>n</mml:mi> <mml:mi>o</mml:mi> <mml:mi>t</mml:mi> <mml:mi>i</mml:mi> <mml:mi>m</mml:mi> <mml:mi>p</mml:mi> <mml:mi>l</mml:mi> <mml:mi>e</mml:mi> <mml:mi>m</mml:mi> <mml:mi>e</mml:mi> <mml:mi>n</mml:mi> <mml:mi>t</mml:mi> <mml:mi>e</mml:mi> <mml:mi>d</mml:mi></mml:mrow> <mml:annotation>${1,char/0x00AF not implemented}$</mml:annotation> </mml:semantics> </mml:math> space groups, with the two former compounds being polymorphs that are isostructural but differ in their symmetries. From the crystallographic results, a common packing arrangement is established, with C₆₀ and [Ni(Bz4TMTAA)] molecules organised around one-dimensional hollow channels, associated 1 : 1 and 1 : 2 complexation of the macrocycle and the fullerene molecules, the latter being organised into hexagonal arrays. Interestingly, one of the structures showed a skewed hexagonal channel arrangement with the introduction of water molecules. Hirshfeld surface analyses have been used to investigate non-covalent interactions and cumulative π…π, C-H…π, H…H, and N…C₆₀ interactions between fullerene C₆₀ and [Ni(Bz₄TMTAA)] host molecule which are deemed the stabilizing factors for forming the sophisticated arrangements in the solid-state. differences.