Macrocycle 1 crystalizes in the P 21/n space group with two molecules per unit cell. As shown in Figure , it is only slightly distorted from planarity, with the dihedral angle between the planes of fluorinated and non-fluorinated rings of 9.58 °, and the distance between two intraannular hydrogens of 2.42(3) Å. The extended packing diagram (Figure ) shows that the macrocycles organize into columnar stacks through slipped parallel stacking as shown in Figure . Closer inspection of the packing shows that the crystal structure is held together by the T-shaped fluoroarene-fluoroarene interactions between the macrocycles of 1 with 2.91(3) Å short contact between a fluorine and a carbon atom (Figure ). The interactions between the neighboring macrocycles within the stack are not the expected fluoroarene-arene interactions, but instead the apparent fluoroarene-alkyne [π•••π] interactions highlighted in Figure . Two macrocycles arrange in a slipped stacking interaction in a way where two of the carbon atoms of the fluoroarene reside above the alkyne with a centroid-centroid distance of 3.29(3) Å, and two additional short arene-alkyne contacts of 3.37(3) Å; both are shorter than the sum of the van der Waals radii of two carbon atoms (3.40 Å). Macrocycle 2 (Figure ) crystalizes in the P 21/c space group with two molecules per unit cell. The dihedral angle between the planes of fluorinated and non-fluorinated rings is again very small (5.84 °) and the distance between the intraannular hydrogen atoms is 2.43(3) Å. As seen in macrocycle 1, macrocycle 2 also forms a continuous columnar stack (Figure ) with slipped stacking between the macrocycles (Figure ) and T-shaped interactions (Figure ). However, their closer inspection reveals an interaction different from that observed in 1: the molecules of 2 are not forming the stacking via the fluroarene-alkyne interaction but via fluroarenefluroarene and alkyne-alkyne interactions (Figure ). The two macrocycles are slipped in a way which results in the shortest contacts of 3.22(2) Å between the carbons of the fluoroarenes, and 3.32(2) Å between the carbons of alkynes. The third interaction between the two molecules of the macrocycle 2 is hydrogen bonding in the ester group with a short contact of 2.71(2) Å between the oxygen and hydrogen of the methyl group. This