Five closely related 4-chloro-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepines: similar molecular structures but different supramolecular assemblies

2015 ◽  
Vol 71 (12) ◽  
pp. 1062-1068 ◽  
Author(s):  
Lina M. Acosta ◽  
Jorge Jurado ◽  
Alirio Palma ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Ring System ◽  
Supramolecular Assemblies ◽  
Molecular Structures ◽  
Synthetic Approach ◽  
Molecular Conformations ◽  
Π Stacking ◽  
Racemic Mixtures ◽  
Phenyl Rings ◽  
Π Stacking Interaction ◽  
Methoxy Substituent

Dibenz[b,f]azepine (DBA) is a privileged 6-7-6 tricyclic ring system of importance in both organic and medicinal chemistry. Benzo[b]pyrimido[5,4-f]azepines (BPAs), which also contain a privileged 6-7-6 ring system, are less well investigated, probably because of a lack of straightforward and versatile methods for their synthesis. A simple and versatile synthetic approach to BPAs based on intramolecular Friedel–Crafts alkylation has been developed. A group of closely-related benzo[b]pyrimido[5,4-f]azepine derivatives, namely (6RS)-4-chloro-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, C14H14ClN3, (I), (6RS)-4-chloro-8-hydroxy-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, C14H14ClN3O, (II), (6RS)-4-<!?tlsb=-0.14pt>chloro-8-methoxy-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, C15H16ClN3O, (III), and (6RS)-4-chloro-8-methoxy-6,11-dimethyl-2-phenyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, C21H20ClN3O, (IV), has been prepared and their structures compared with the recently published structure [Acosta-Quinteroet al.(2015).Eur. J. Org. Chem.pp. 5360–5369] of (6RS)-4-chloro-2,6,8,11-tetramethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, (V). All five compounds crystallize as racemic mixtures and they have very similar molecular conformations, with the azepine ring adopting a boat-type conformation in each case, although the orientation of the methoxy substituent in each of (III) and (IV) is different. The supramolecular assemblies in (II) and (IV) depend upon hydrogen bonds of the O—H...N and C—H...π(arene) types, respectively, those in (I) and (V) depend upon π–π stacking interactions involving pairs of pyrimidine rings, and that in (III) depends upon a π–π stacking interaction involving pairs of phenyl rings. Short C—Cl...π(pyrimidine) contacts are present in (I), (II) and (IV) but not in (III) or (V).

scholarly journals Crystal structure and computational studies of (3Z)-4-benzoyl-3-[(2,4-dinitrophenyl)hydrazinylidene]-5-phenylfuran-2(3H)-one

2016 ◽  
Vol 72 (12) ◽  
pp. 1852-1855
Author(s):  
Yavuz Köysal ◽  
Hakan Bülbül ◽  
İlhan Özer İlhan ◽  
Nazenin Akın ◽  
Necmi Dege
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Crystal Packing ◽  
Theoretical Calculations ◽  
Ring System ◽  
Computational Studies ◽  
System A ◽  
Compound C ◽  
Phenyl Rings ◽  
Π Stacking Interaction

In the molecular structure of the title compound, C23H14N4O7, the furan, dinitrophenyl and phenyl rings are almost in the same plane (r.m.s. deviation = 0.127 Å), with the benzoyl ring inclined by a dihedral angle of 56.4 (1)° to the three-ring system. A bifurcated intramolecular N—H...(O,O) hydrogen bond is present. In the crystal, adjacent molecules are linked by C—H...O hydrogen bonds into chains parallel to [001]. A π–π stacking interaction between the benzoyl and dinitrophenyl moieties contributes to the crystal packing. Theoretical calculations using DFT(B3YLP) methods were used to confirm the molecular structure.

scholarly journals Two polymorphs of 2,5-dichloro-3,6-bis(dibenzylamino)-p-hydroquinone with flexible dibenzylamino groups

2018 ◽  
Vol 74 (4) ◽  
pp. 437-441
Author(s):  
In-Sub Shin ◽  
Yuta Shimada ◽  
Emi Horiguchi-Babamoto ◽  
Shinya Matsumoto
Keyword(s):  
Crystal Structures ◽  
Intermolecular Interactions ◽  
Structural Difference ◽  
Molecular Structures ◽  
The Other ◽  
Molecular Conformations ◽  
Stacking Pattern ◽  
Structural Differences ◽  
Form Part ◽  
Phenyl Rings

We obtained two conformational polymorphs of 2,5-dichloro-3,6-bis(dibenzylamino)-p-hydroquinone, C34H30Cl2N2O2. Both polymorphs have an inversion centre at the centre of the hydroquinone ring (Z′ = 1 \over 2), and there are no significant differences between their bond lengths and angles. The most significant structural difference in the molecular conformations was found in the rotation of the phenyl rings of the two crystallographically independent benzyl groups. The crystal structures of the polymorphs were distinguishable with respect to the arrangement of the hydroquinone rings and the packing motif of the phenyl rings that form part of the benzyl groups. The phenyl groups of one polymorph are arranged in a face-to-edge motif between adjacent molecules, with intermolecular C—H...π interactions, whereas the phenyl rings in the other polymorph form a lamellar stacking pattern with no significant intermolecular interactions. We suggest that this partial conformational difference in the molecular structures leads to the significant structural differences observed in their molecular arrangements.

scholarly journals 2,3-Bis(benzylthio)-6-methylquinoxaline

IUCrData ◽  
2017 ◽  
Vol 2 (9) ◽  
Author(s):  
Ayman Zouitini ◽  
Youssef Kandri Rodi ◽  
Younes Ouzidan ◽  
Jerry P. Jasinski ◽  
Manpreet Kaur ◽  
...  
Keyword(s):  
Benzene Ring ◽  
Title Compound ◽  
Ring System ◽  
Stacking Interactions ◽  
Methyl Group ◽  
Compound C ◽  
Π Stacking ◽  
Phenyl Rings ◽  
The Mean ◽  
Quinoxaline Ring

In the title compound, C23H20N2S2, the mean planes of the phenyl rings are twisted with respect to the mean plane of the quinoxaline ring system by 73.8 (8) and 72.2 (8)°. A weak intramolecular C—H...N interactions is observed. The methyl group attached to the quinoxaline ring system is disordered over two sets of sites on the benzene ring having occupancies 0.531 (7) and 0.469 (7), respectively. One of the phenyl rings is disordered over two sets of sites having occupancies 0.649 (7) and 0.351 (10), respectively. In the crystal, π–π stacking interactions occur.

scholarly journals 1-Benzoylnaphthalene-2,7-diyl dibenzoate

2013 ◽  
Vol 69 (2) ◽  
pp. o210-o210 ◽  
Author(s):  
Rei Sakamoto ◽  
Kosuke Sasagawa ◽  
Daichi Hijikata ◽  
Akiko Okamoto ◽  
Noriyuki Yonezawa
Keyword(s):  
Hydrogen Bonds ◽  
Title Compound ◽  
Three Dimensional ◽  
Ring System ◽  
Naphthalene Ring ◽  
Π Interactions ◽  
Compound C ◽  
Π Stacking ◽  
Dimensional Network ◽  
Phenyl Rings

In the title compound, C31H20O5, the phenyl rings of the benzoyloxy and benzoyl groups are twisted away from the naphthalene ring system by 64.27 (6), 73.62 (5) and 80.41 (6)°. In the crystal, C—H...O hydrogen bonds and C—H...π interactions link the molecules, forming tubular chains parallel to thebaxis. The chains are further connected into a three-dimensional network by C—H...π interactions and π–π stacking contacts [centroid–centroid distances = 3.622 (10)–3.866 (12) Å].

Control of Intramolecular π–π Stacking Interaction in Cationic Iridium Complexes via Fluorination of Pendant Phenyl Rings

2012 ◽  
Vol 51 (8) ◽  
pp. 4502-4510 ◽  
Author(s):  
Lei He ◽  
Dongxin Ma ◽  
Lian Duan ◽  
Yongge Wei ◽  
Juan Qiao ◽  
...  
Keyword(s):  
Iridium Complexes ◽  
Stacking Interaction ◽  
Π Stacking ◽  
Phenyl Rings ◽  
Π Stacking Interaction

scholarly journals 4-(Diphenylamino)benzaldehyde 4-phenylthiosemicarbazone

2012 ◽  
Vol 68 (8) ◽  
pp. o2402-o2403 ◽  
Author(s):  
Rafael Mendoza-Meroño ◽  
Laura Menéndez-Taboada ◽  
Santiago García-Granda
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Phenyl Ring ◽  
Crystal Packing ◽  
Stacking Interactions ◽  
Π Stacking ◽  
Phenyl Rings ◽  
Π Stacking Interaction ◽  
Title Molecule ◽  
Ring Motif

The title molecule, C26H22N4S, is composed of three main parts,viz.a triphenylamine group is connected to a phenyl ring by a thiosemicarbazone moiety. The C= N double bond has anEconformation. The crystal packing is dominated by strong hydrogen bonds through the thiosemicarbazone moiety, with pairs of N—H...S hydrogen bonds linking the molecules to form inversion dimers with anR22(8) ring motif. An intramolecular N—H...N hydrogen bond is also present, generating anS(5) ring motif. Although the structure contains four phenyl rings, π–π stacking interactions are not formed between them, probably due to the conformation adopted by the triphenylamine group. However, a weak π–π stacking interaction is observed between the phenyl ring and the delocalized thiosemicarbazone moiety.

scholarly journals Six 1-aroyl-4-(4-methoxyphenyl)piperazines: similar molecular structures but different patterns of supramolecular assembly

2019 ◽  
Vol 75 (8) ◽  
pp. 1253-1260 ◽  
Author(s):  
Haruvegowda Kiran Kumar ◽  
Hemmige S. Yathirajan ◽  
Belakavadi K. Sagar ◽  
Sabine Foro ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Supramolecular Assembly ◽  
Molecular Structures ◽  
Benzoic Acids ◽  
Coupling Reactions ◽  
Stacking Interaction ◽  
Π Stacking ◽  
Π Stacking Interaction ◽  
Related Compounds

Six new 1-aroyl-4-(4-methoxyphenyl)piperazines have been prepared, using coupling reactions between benzoic acids and N-(4-methoxyphenyl)piperazine. There are no significant hydrogen bonds in the structure of 1-benzoyl-4-(4-methoxyphenyl)piperazine, C18H20N2O2, (I). The molecules of 1-(2-fluorobenzoyl)-4-(4-methoxyphenyl)piperazine, C18H19FN2O2, (II), are linked by two C—H...O hydrogen bonds to form chains of rings, which are linked into sheets by an aromatic π–π stacking interaction. 1-(2-Chlorobenzoyl)-4-(4-methoxyphenyl)piperazine, C18H19ClN2O2, (III), 1-(2-bromobenzoyl)-4-(4-methoxyphenyl)piperazine, C18H19BrN2O2, (IV), and 1-(2-iodobenzoyl)-4-(4-methoxyphenyl)piperazine, C18H19IN2O2, (V), are isomorphous, but in (III) the aroyl ring is disordered over two sets of atomic sites having occupancies of 0.942 (2) and 0.058 (2). In each of (III)–(V), a combination of two C—H...π(arene) hydrogen bonds links the molecules into sheets. A single O—H...O hydrogen bond links the molecules of 1-(2-hydroxybenzoyl)-4-(4-methoxyphenyl)piperazine, C18H20N2O3, (VI), into simple chains. Comparisons are made with the structures of some related compounds.

scholarly journals Crystal structures of two new carbazole derivatives: 12-(4-nitrophenyl)-7-phenylsulfonyl-7H-benzofuro[2,3-b]carbazole and 2-methyl-4-(4-nitrophenyl)-9-phenylsulfonyl-9H-thieno[2,3-b]carbazole

2016 ◽  
Vol 72 (12) ◽  
pp. 1739-1743
Author(s):  
K. Swaminathan ◽  
P. Narayanan ◽  
K. Sethusankar ◽  
Velu Saravanan ◽  
Arasambattu K. Mohanakrishnan
Keyword(s):  
Hydrogen Bonds ◽  
Dihedral Angle ◽  
Ring System ◽  
Molecular Structures ◽  
Dihedral Angles ◽  
Compound I ◽  
Carbazole Derivatives ◽  
Phenyl Rings ◽  
The Mean ◽  
Compound Ii

The title compounds, C30H18N2O5S, (I), and C27H18N2O4S2, (II), are carbazole derivatives with a phenylsulfonyl group and a nitrophenyl group attached to the carbazole moiety in identical positions in both molecules. A benzofuran ring system in (I) and a methylthiophene ring in (II) are fused with the respective carbazole moieties on the same sides. The mean plane of the carbazole ring system makes a dihedral angle of 3.17 (7)° with the benzofuran ring system in (I) and a dihedral angle of 3.39 (11)° with the methylthiophene ring in (II), implying that both fused units are essentially planar. The mean planes of the carbazole ring systems in both the compounds are almost orthogonal to the respective nitro-substituted phenyl rings, making dihedral angles of 75.64 (10) and 77.63 (12)° in compounds (I) and (II), respectively. In (I), the phenylsulfonyl ring system is positionally disordered with a refined occupancy ratio of 0.63 (2):0.37 (2). In both compounds, the molecular structures are stabilized by intramolecular C—H...O hydrogen bonds, generatingS(6) ring motifs with the sulfone group O atoms. In the crystal of compound (I), molecules are linked by pairs of C—H...O hydrogen bonds, which generateR22(18) inversion dimers, and interconnected byC(14) chains running along thec-axis direction, whereas in compound (II), the C—H...O hydrogen bonds generateR43(37) ring motifs. In the crystals of both compounds, C—H...O hydrogen-bonded sheets are formed lying parallel to (10-1). In addition, C—H...π and offset π–π interactions [intercentroid distance = 3.7158 (14) Å in (I) and 3.9040 (15) Å in (II)] are also present in the crystals of both compounds.

scholarly journals Crystal structure of 10-[(3-oxo-3H-benzo[f]chromen-1-yl)methyl]-2-trifluoromethyl-9a,10-dihydrobenz[4,5]imidazo[1,2-a]pyrimidin-4(5aH)-one

2015 ◽  
Vol 71 (9) ◽  
pp. o672-o673
Author(s):  
Chandra ◽  
Shamantha Kumar. ◽  
K. B. Puttaraju ◽  
K. Shivashankar ◽  
M. Mahendra
Keyword(s):  
Crystal Structure ◽  
Dihedral Angle ◽  
Title Compound ◽  
Ring System ◽  
Stacking Interaction ◽  
Compound C ◽  
Π Stacking ◽  
Π Stacking Interaction

In the title compound, C25H14F3N3O3, the dihedral angle between the planes of the benz[4,5]imidazo[1,2-a]pyrimidine unit (r.m.s. deviation = 0.035 Å) and the benzochromene ring system (r.m.s. deviation = 0.106 Å) is 72.82 (5)°. In the crystal, molecules are linked by C—H...O interactions, generating [010]C(9) chains. A weak aromatic π–π stacking interaction [centroid–centroid separation = 3.5376 (15) Å] is also observed.

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