TY - JOUR
T1 - Different packing motifs mediated by weak interactions and polymorphism in the crystal structures of five 2-(benzylidene)benzosuberone derivatives
AU - Seaman, Lewis J.
AU - da Costa, Cristiane F.
AU - de Souza, Marcus V. N.
AU - Wardell, Solange M. S. V.
AU - Wardell, James L
AU - Harrison, William T A
PY - 2019/11
Y1 - 2019/11
N2 - The syntheses and crystal structures of five 2-benzylidene-1-benzosuberone [1-benzosuberone is 6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one] derivatives, viz. 2-(4-methoxybenzylidene)-1-benzosuberone, C19H18O2, (I), 2-(4-ethoxybenzylidene)-1-benzosuberone, C20H20O2, (II), 2-(4-benzylbenzylidene)-1-benzosuberone, C25H22O2, (III), 2-(4-chlorobenzylidene)-1-benzosuberone, C18H15ClO, (IV) and 2-(4-cyanobenzylidene)-1-benzosuberone, C19H15NO, (V), are described. The conformations of the benzosuberone fused six- plus seven-membered ring fragments are very similar in each case, but the dihedral angles between the fused benzene ring and the pendant benzene ring differ somewhat, with values of 23.79 (3) for (I), 24.60 (4) for (II), 33.72 (4) for (III), 29.93 (8) for (IV) and 21.81 (7)° for (V). Key features of the packing include pairwise C—H⋯O hydrogen bonds for (II) and (IV), and pairwise C—H⋯N hydrogen bonds for (V), which generate inversion dimers in each case. The packing for (I) and (III) feature C—H⋯O hydrogen bonds, which lead to [010] and [100] chains, respectively. Weak C—H⋯π interactions consolidate the structures and weak aromatic π–π stacking is seen in (II) [centroid–centroid separation = 3.8414 (7) Å] and (III) [3.9475 (7) Å]. A polymorph of (I) crystallized from a different solvent has been reported previously [Dimmock et al. (1999[Dimmock, J. R., Kandepu, N. M., Nazarali, A. J., Kowalchuk, T. P., Motaganahalli, N., Quail, J. W., Mykytiuk, P., Audette, G. F., Prasad, L., Perjési, P., Allen, T. M., Santos, C. L., Szydlowski, J., De Clercq, E. & Balzarini, J. (1999). J. Med. Chem. 42, 1358-1366.]) J. Med. Chem. 42, 1358–1366] in the same space group but with a packing motif based on inversion dimers resembling that seen in (IV) in the present study. The Hirshfeld surfaces and fingerprint plots for (I) and its polymorph are compared and structural features of the 2-benzylidene-1-benzosuberone family of phases are surveyed.
AB - The syntheses and crystal structures of five 2-benzylidene-1-benzosuberone [1-benzosuberone is 6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one] derivatives, viz. 2-(4-methoxybenzylidene)-1-benzosuberone, C19H18O2, (I), 2-(4-ethoxybenzylidene)-1-benzosuberone, C20H20O2, (II), 2-(4-benzylbenzylidene)-1-benzosuberone, C25H22O2, (III), 2-(4-chlorobenzylidene)-1-benzosuberone, C18H15ClO, (IV) and 2-(4-cyanobenzylidene)-1-benzosuberone, C19H15NO, (V), are described. The conformations of the benzosuberone fused six- plus seven-membered ring fragments are very similar in each case, but the dihedral angles between the fused benzene ring and the pendant benzene ring differ somewhat, with values of 23.79 (3) for (I), 24.60 (4) for (II), 33.72 (4) for (III), 29.93 (8) for (IV) and 21.81 (7)° for (V). Key features of the packing include pairwise C—H⋯O hydrogen bonds for (II) and (IV), and pairwise C—H⋯N hydrogen bonds for (V), which generate inversion dimers in each case. The packing for (I) and (III) feature C—H⋯O hydrogen bonds, which lead to [010] and [100] chains, respectively. Weak C—H⋯π interactions consolidate the structures and weak aromatic π–π stacking is seen in (II) [centroid–centroid separation = 3.8414 (7) Å] and (III) [3.9475 (7) Å]. A polymorph of (I) crystallized from a different solvent has been reported previously [Dimmock et al. (1999[Dimmock, J. R., Kandepu, N. M., Nazarali, A. J., Kowalchuk, T. P., Motaganahalli, N., Quail, J. W., Mykytiuk, P., Audette, G. F., Prasad, L., Perjési, P., Allen, T. M., Santos, C. L., Szydlowski, J., De Clercq, E. & Balzarini, J. (1999). J. Med. Chem. 42, 1358-1366.]) J. Med. Chem. 42, 1358–1366] in the same space group but with a packing motif based on inversion dimers resembling that seen in (IV) in the present study. The Hirshfeld surfaces and fingerprint plots for (I) and its polymorph are compared and structural features of the 2-benzylidene-1-benzosuberone family of phases are surveyed.
KW - crystal structure
KW - suberone
KW - polymorphism
KW - Suberone
KW - Crystal structure
KW - Polymorphism
UR - http://www.scopus.com/inward/record.url?scp=85074781505&partnerID=8YFLogxK
U2 - 10.1107/S2056989019014245
DO - 10.1107/S2056989019014245
M3 - Article
SN - 2056-9890
VL - 75
SP - 1741
EP - 1747
JO - Acta Crystallographica Section E: Crystallographic Communications
JF - Acta Crystallographica Section E: Crystallographic Communications
IS - 11
ER -