(31 E,32 Z,71 E,72 Z)-4,8-Bis(3,5-dichlorophenyl)-14,33,53,73-tetrapropyl-11 H,32 H,51 H,72 H-1,5(2,5),3,7(5,2)-tetrapyrrola-2,6(2,5)-dithiophenacyclooctaphane

In the title compound, [24]dithiaamethyrin(1.0.0.1.0.0); C50H44Cl4N4S2, the macrocycle can be described as a highly planar structure with a mean-plane deviation (MPD) value of 0.0416 Å. The molecular conformation is stabilized by two intramolecular N—H⋯N interactions. In the crystal, molecules are also linked via C—H⋯π interactions forming a three-dimensional network.

Purple crystals of the title compound, C 50 H 44 Cl 4 N 4 S 2 were obtained from the reaction of 2,5-bis(4-propyl-1H-pyrrol-2-yl)thiophene and 3,5-dichlorobenzaldehyde in the presence of trifluoroacetic acid for 3 h and subsequent addition of p-chloranil.The macrocycle in the title compound can be described as a highly planar structure wthe the average deviation of the 32 macrocyclic atoms from the least-squares plane being 0.0416 A ˚. Its molecular conformation is stabilized by two intramolecular N-H� � �N bonds and a three-dimensional network is formed by C-H� � �� interactions.

Structure description
The molecular structures and electronic properties of hexapyrrolic expanded porphyrins with different numbers of �-electrons and meso-like positions have been studied extensively (Sessler et al., 1995;Saito & Osuka et al., 2011;Setsune et al., 2015).Furthermore, the crucial influence of a heteroatom on the macrocycle conformation of core-modified hexaphyrins has been demonstrated (Narayanan et al., 1998(Narayanan et al., , 1999)).
[24]Amethyrin is a hexapyrrolic expanded porphyrin that has recently been a focus of theoretical studies, and exploring the molecular structures and electronic properties of its derivatives is highly desirable.Dithiaamethyrin is a core-modified amethyline with Group-16 heterocycles and meso-dichlorophenyl groups (Alka et al., 2019).In a continuation of our research on the synthesis and characterization of expanded porphyrin derivatives (Ishimaru et al., 2015(Ishimaru et al., , 2022)), we synthesized the title compound, [24]dithiaamethyrin(1.0.0.1.0.0), and elucidated its crystal structure.It has a highly planar macrocyclic core and its 1 H NMR chemical shifts indicate strong antiaromaticity.Its molecular structure is shown in Fig. 1.Its planarity is reinforced by two intramolecular N1-H1� � �N2 hydrogen bonds (Table 1) in the dipyrromethene moiety, as shown in Fig. 1.All the bond lengths are consistent with those reported in a previous study on other dithiaamethyrins (Ishimaru et al., 2015).The mean plane deviation (MPD) value of the 32 macrocyclic atoms is 0.0416 A ˚, and the meso-phenyl ring is twisted by 92.51 � from the mean plane of

Synthesis and crystallization
The title compound was prepared by a modified previously reported method by Ishimaru et al. (2015).2,5-Bis(4-propyl-2pyrrolyl)thiophene (200 mg) was dissolved in CH 2 Cl 2 (ca 300 mL) under an Ar atmosphere, to which 3,5-dichlorobenzaldehyde (68.4 mL) and trifluoroacetic acid (160 mL) were added.The reaction mixture was stirred for 3 h, p-chloranil (544 mg) was added to it, and the mixture was stirred overnight at ambient temperature.Then, the mixture was neutralized with an aqueous NaHCO 3 solution, and the crude products were passed through an alumina column.Finally, the products were purified by chromatography on a silica gel column using chloroform as elute.The third blue (2%) fraction afforded the title compound.The compound was recrystallized from a mixture of hexane and chloroform.Purple plates of suitable quality for diffraction were obtained by slow-diffusing hexane into chloroform. 1 H NMR (400 MHz, CDCl 3 ): � (ppm) 24.0 (br, 2H, pyrrole NH), 7. 6H,o,  The molecular structure of the title compound showing the atom labelling.Displacement ellipsoids are drawn at the 50% probability level.Non-labeled atoms are generated by symmetry operation À x + 1, À y + 1, À z + 1.

Figure 2
Figure 2 View of the molecular arrangement of the title compound in the crystal.Dashed lines indicate the C-H� � �� interactions (ring centroids are shown as coloured spheres).

Table 2
Experimental details.