Nine closely related tetrahydro-1,4-epoxy-1-benzazepines carrying pendant heterocyclic substituents: hydrogen-bonded supramolecular assembly in zero, one and two dimensions

2012 ◽  
Vol 68 (3) ◽  
pp. o131-o140 ◽  
Author(s):  
Maria C. Blanco ◽  
Alirio Palma ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Supramolecular Assembly ◽  
Two Dimensions ◽  
Specific Interactions ◽  
Space Groups ◽  
Racemic Mixtures ◽  
Sheet Structure ◽  
A Chain ◽  
Related Compounds

The structures are reported of nine closely related tetrahydro-1,4-epoxy-1-benzazepines carrying pendant heterocyclic substituents, namely: 2-exo-(5-nitrofuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C14H12N2O4, (I), 7-fluoro-2-exo-(1-methyl-1H-pyrrol-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H15FN2O, (II), 7-fluoro-2-exo-(5-methylfuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H14FNO2, (III), 7-fluoro-2-exo-(3-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H14FNOS, (IV), 7-fluoro-2-exo-(5-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H14FNOS, (V), 7-chloro-2-exo-(5-methylfuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H14ClNO2, (VI), 2-exo-(5-methylfuran-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C16H14F3NO3, (VII), 2-exo-(3-methylthiophen-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C16H14F3NO2S, (VIII), and 2-exo-(5-nitrofuran-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H11F3N2O5, (IX). All nine compounds crystallize in centrosymmetric space groups as racemic mixtures with configuration (2RS,4SR). There are no direction-specific interactions between the molecules in (V). The molecules in (III), (IV), (VI) and (VII) are linked into simple chains, by means of a single C—H...O hydrogen bond in each of (III), (VI) and (VII), and by means of a single C—H...π(arene) hydrogen bond in (IV), while the molecules in (VIII) are linked into a chain of rings. In each of (I) and (II), a combination of one C—H...O hydrogen bond and one C—H...π(arene) hydrogen bond links the molecules into sheets, albeit of completely different construction in the two compounds. In (IX), the sheet structure is built from a combination of four independent C—H...O hydrogen bonds and one C—H...π(arene) hydrogen bond. Comparisons are made with some related compounds.

2-Amino-6-methoxy-4-(4-methylanilino)-5-nitrosopyrimidine and ethylN-[4-(adamantan-1-ylamino)-2-amino-5-nitrosopyrimidin-6-yl]-3-aminopropionate: polarized electronic structures and hydrogen-bonded supramolecular assembly in one and two dimensions

2012 ◽  
Vol 68 (5) ◽  
pp. o199-o203 ◽  
Author(s):  
Andrés F. Yépes ◽  
Alirio Palma ◽  
Antonio Marchal ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Electronic Structures ◽  
Supramolecular Assembly ◽  
Two Dimensions ◽  
A Chain ◽  
Hydrogen Bonded

In both 2-amino-6-methoxy-4-(4-methylanilino)-5-nitrosopyrimidine, C12H13N5O2, (I), and ethylN-[4-(1-adamantylamino)-2-amino-5-nitrosopyrimidin-6-yl]-3-aminopropionate, C19H28N6O3, (II), the nitrosopyrimidine unit is planar and the bond distances provide evidence for significant polarization of the electronic structures. In (II), the ethoxycarbonyl fragment of the molecule is disordered over two sets of sites with occupancies of 0.910 (4) and 0.090 (4). In the molecules of both compounds, there is an intramolecular N—H...O hydrogen bond. The molecules of (I) are linked into a chain of rings by a combination of N—H...O and C—H...O hydrogen bonds, while the molecules of (II) are linked by a two-centre N—H...N hydrogen bond and a three-centre N—H...(N,O) hydrogen bond to form sheets containing four distinct types of ring.

scholarly journals Twelve 4-(4-methoxyphenyl)piperazin-1-ium salts containing organic anions: supramolecular assembly in one, two and three dimensions

2019 ◽  
Vol 75 (10) ◽  
pp. 1494-1506 ◽  
Author(s):  
Haruvegowda Kiran Kumar ◽  
Hemmige S. Yathirajan ◽  
Sabine Foro ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Supramolecular Assembly ◽  
Organic Anions ◽  
Three Dimensions ◽  
Space Group ◽  
Dimensional Array ◽  
A Chain ◽  
Related Compounds

Twelve 4-(4-methoxyphenyl)piperazin-1-ium salts containing organic anions have been prepared and structurally characterized. The monohydrated benzoate, 4-fluorobenzoate, 4-chlorobenzoate and 4-bromobenzoate salts, C11H17N2O+·C7H5O2 −·H2O (I), C11H17N2O+·C7H4FO2 −·H2O (II), C11H17N2O+·C7H4ClO2 −·H2O (III), and C11H17N2O+·C7H4BrO2 −·H2O (IV), respectively, are isomorphous and all exhibit disorder in the 4-methoxyphenyl unit: the components are linked by N—H...O and O—H...O hydrogen bond to form chains of rings. The unsolvated 2-hydroxybenzoate, pyridine-3-carboxylate and 2-hydroxy-3,5-dinitrobenzoate salts, C11H17N2O+·C7H5O3 − (V), C11H17N2O+·C6H4NO2 − (VI) and C11H17N2O+·C7H3N2O7 − (VII), respectively, are all fully ordered: the components of (V) are linked by multiple N—H...O hydrogen bonds to form a chain of rings; those of (VI) are linked into a three-dimensional framework by a combination of N—H...O, C—H...O and C—H...N hydrogen bonds and those of (VII), where the anion has a structure reminiscent of the picrate anion, are linked into a three-dimensional array by N—H...O and C—H...O hydrogen bonds. The hydrogensuccinate and hydrogenfumarate salts, C11H17N2O+·C4H5O4 − (VIII) and C11H17N2O+·C4H3O3 − (IX), respectively, are isomorphous, and both exhibit disorder in the anionic component: N—H...O and O—H...O hydrogen bonds link the ions into sheets, which are further linked by C—H...π(arene) interactions. The anion of the hydrogenmaleate salt, C11H17N2O+·C4H3O3 − (X), contains a very short and nearly symmetrical O...H...O hydrogen bond, and N—H...O hydrogen bonds link the anions into chains of rings. The ions in the trichloroacetate salt, C11H17N2O+·C2Cl3O2 − (XI), are linked into simple chains by N—H...O hydrogen bonds. In the hydrated chloranilate salt, 2C11H17N2O+·C6Cl2O4 2−·2H2O (XII), which crystallizes as a non-merohedral twin, the anion lies across a centre of inversion in space group P21/n, and a combination of N—H...O and O—H...O hydrogen bonds generates complex sheets. Comparisons are made with the structures of some related compounds.

Hydrogen-bonded assembly in six closely related pyrazolo[3,4-b]pyridine derivatives; a simple chain, three types of chains of rings and a complex sheet structure

2011 ◽  
Vol 68 (1) ◽  
pp. o12-o18 ◽  
Author(s):  
Jairo Quiroga ◽  
Yurina Díaz ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Pyridine Derivatives ◽  
Space Group ◽  
Space Groups ◽  
Sheet Structure ◽  
Unit Cells ◽  
Simple Chain ◽  
A Chain ◽  
Hydrogen Bonded

Six closely related pyrazolo[3,4-b]pyridine derivatives, namely 6-chloro-3-methyl-1,4-diphenylpyrazolo[3,4-b]pyridine-5-carbaldehyde, C20H14ClN3O, (I), 6-chloro-3-methyl-4-(4-methylphenyl)-1-phenylpyrazolo[3,4-b]pyridine-5-carbaldehyde, C21H16ClN3O, (II), 6-chloro-4-(4-chlorophenyl)-3-methyl-1-phenylpyrazolo[3,4-b]pyridine-5-carbaldehyde, C20H13Cl2N3O, (III), 4-(4-bromophenyl)-6-chloro-3-methyl-1-phenylpyrazolo[3,4-b]pyridine-5-carbaldehyde, C20H13BrClN3O, (IV), 6-chloro-4-(4-methoxyphenyl)-3-methyl-1-phenylpyrazolo[3,4-b]pyridine-5-carbaldehyde, C21H16ClN3O2, (V), and 6-chloro-3-methyl-4-(4-nitrophenyl)-1-phenylpyrazolo[3,4-b]pyridine-5-carbaldehyde, C20H13ClN4O3, (VI), which differ only in the identity of a single small substituent on one of the aryl rings, crystallize in four different space groups spanning three crystal systems. The molecules of (I) are linked into a chain of rings by a combination of C—H...N and C—H...π(arene) hydrogen bonds; those of (II), (IV) and (V), which all crystallize in the space groupP\overline{1}, are each linked by two independent C—H...O hydrogen bonds to form chains of edge-fused rings running in different directions through the three unit cells; the molecules of (III) are linked into complex sheets by a combination of two C—H...O hydrogen bonds and one C—H...π(arene) hydrogen bond; finally, the molecules of (VI) are linked by a single C—H...O hydrogen bond to form a simple chain.

Synthesis and structures of six closely related N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]arylamides, together with an isolated reaction intermediate: order versus disorder, molecular conformations and hydrogen bonding in zero, one and two dimensions

2018 ◽  
Vol 74 (2) ◽  
pp. 203-211
Author(s):  
Belakavadi K. Sagar ◽  
Hemmige S. Yathirajan ◽  
Ravindranath S. Rathore ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Two Dimensions ◽  
The Other ◽  
Molecular Conformations ◽  
Reaction Intermediate ◽  
Different Types ◽  
Intermediate Order ◽  
Independent Molecules ◽  
Related Compounds

Six closely related N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]arylamides have been synthesized and structurally characterized, together with a representative reaction intermediate. In each of N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]benzamide, C20H16ClNO2S, (I), N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]-4-phenylbenzamide, C26H20ClNO2S, (II), and 2-bromo-N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]benzamide, C20H15BrClNO2S, (III), the molecules are disordered over two sets of atomic sites, with occupancies of 0.894 (8) and 0.106 (8) in (I), 0.832 (5) and 0.168 (5) in (II), and 0.7006 (12) and 0.2994 (12) in (III). In each of N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]-2-iodobenzamide, C20H15ClINO2S, (IV), and N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]-2-methoxybenzamide, C21H18ClNO3S, (V), the molecules are fully ordered, but in N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]-2,6-difluorobenzamide, C20H14ClF2NO2S, (VI), which crystallizes with Z′ = 2 in the space group C2/c, one of the two independent molecules is fully ordered, while the other is disordered over two sets of atomic sites having occupancies of 0.916 (3) and 0.084 (3). All of the molecules in compounds (I)–(VI) exhibit an intramolecular N—H...O hydrogen bond. The molecules of (I) and (VI) are linked by C—H...O hydrogen bonds to form finite zero-dimensional dimers, which are cyclic in (I) and acyclic in (VI), those of (III) are linked by C—H...π(arene) hydrogen bonds to form simple chains, and those of (IV) and (V) are linked into different types of chains of rings, built in each case from a combination of C—H...O and C—H...π(arene) hydrogen bonds. Two C—H...O hydrogen bonds link the molecules of (II) into sheets containing three types of ring. In benzotriazol-1-yl 3,4-dimethoxybenzoate, C15H13N3O4, (VII), the benzoate component is planar and makes a dihedral angle of 84.51 (6)° with the benzotriazole unit. Comparisons are made with related compounds.

scholarly journals Crystal structures of morpholinium hydrogen bromanilate at 130, 145 and 180 K

2015 ◽  
Vol 71 (10) ◽  
pp. 1226-1229
Author(s):  
Kazuma Gotoh ◽  
Yuki Tahara ◽  
Hiroyuki Ishida
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Title Compound ◽  
Site Occupancy ◽  
Molecular Geometry ◽  
Asymmetric Unit ◽  
Significant Difference ◽  
Sheet Structure ◽  
A Chain

Crystal structures of the title compound (systematic name: morpholin-4-ium 2,5-dibromo-4-hydroxy-3,6-dioxocyclohexa-1,4-dien-1-olate), C4H10NO+·C6HBr2O4−, were determined at three temperatures,viz.130, 145 and 180 K. The asymmetric unit comprises one morpholinium cation and two halves of crystallographically independent bromanilate monoanions, which are located on inversion centres. The conformations of the two independent bromanilate anions are different from each other with respect to the O—H orientation. In the crystal, the two different anions are linked alternately into a chain along [211] through a short O—H...O hydrogen bond, in which the H atom is disordered over two positions. The refined site-occupancy ratios, which are almost constant in the temperature range studied, are 0.49 (3):0.51 (3), 0.52 (3):0.48 (3) and 0.50 (3):0.50 (3), respectively, at 130, 145 and 180 K, and no significant difference in the molecular geometry and the molecular packing is observed at the three temperatures. The morpholinium cation links adjacent chains of anionsviaN—H...O hydrogen bonds, forming a sheet structure parallel to (-111).

Conversion of substituted 5-aryloxypyrazolecarbaldehydes into reduced 3,4′-bipyrazoles: synthesis and characterization, and the structures of four precursors and two products, and their supramolecular assembly in zero, one and two dimensions

2019 ◽  
Vol 75 (6) ◽  
pp. 768-776 ◽  
Author(s):  
Haruvegowda Kiran Kumar ◽  
Hemmige S. Yathirajan ◽  
Nagaraj Manju ◽  
Balakrishna Kalluraya ◽  
Ravindranath S. Rathore ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Supramolecular Assembly ◽  
Two Dimensions ◽  
Subsequent Reaction ◽  
Orientational Disorder ◽  
New Compounds ◽  
Cyclocondensation Reactions ◽  
Related Compounds ◽  
Centrosymmetric Dimers ◽  
C Nmr

The reaction of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde with phenols under basic conditions yields the corresponding 5-aryloxy derivatives; the subsequent reaction of these carbaldehydes with substituted acetophenones yields the corresponding chalcones, which in turn undergo cyclocondensation reactions with hydrazine in the presence of acetic acid to form N-acetylated reduced bipyrazoles. Structures are reported for three 5-aryloxycarbaldehydes and the 5-piperidino analogue, and for two reduced bipyrazole products. 5-(2-Chlorophenoxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, C17H13ClN2O2, (II), which crystallizes with Z′ = 2 in the space group P\overline{1}, exhibits orientational disorder of the carbaldehyde group in each of the two independent molecules. Each of 3-methyl-5-(4-nitrophenoxy)-1-phenyl-1H-pyrazole-4-carbaldehyde, C17H13N3O4, (IV), 3-methyl-5-(naphthalen-2-yloxy)-1-phenyl-1H-pyrazole-4-carbaldehyde, C21H16N2O2, (V), and 3-methyl-1-phenyl-5-(piperidin-1-yl)-1H-pyrazole-4-carbaldehyde, C16H19N3O, (VI), (3RS)-2-acetyl-5-(4-azidophenyl)-5′-(2-chlorophenoxy)-3′-methyl-1′-phenyl-3,4-dihydro-1′H,2H-[3,4′-bipyrazole] C27H22ClN7O2, (IX) and (3RS)-2-acetyl-5-(4-azidophenyl)-3′-methyl-5′-(naphthalen-2-yloxy)-1′-phenyl-3,4-dihydro-1′H,2H-[3,4′-bipyrazole] C31H25N7O2, (X), has Z′ = 1, and each is fully ordered. The new compounds have all been fully characterized by analysis, namely IR spectroscopy, 1H and 13C NMR spectroscopy, and mass spectrometry. In each of (II), (V) and (IX), the molecules are linked into ribbons, generated respectively by combinations of C—H...N, C—H...π and C—Cl...π interactions in (II), C—H...O and C—H...π hydrogen bonds in (V), and C—H...N and C—H...O hydrogen bonds in (IX). The molecules of compounds (IV) and (IX) are both linked into sheets, by multiple C—H...O and C—H...π hydrogen bonds in (IV), and by two C—H...π hydrogen bonds in (IX). A single C—H...N hydrogen bond links the molecules of (X) into centrosymmetric dimers. Comparisons are made with the structures of some related compounds.

scholarly journals Three closely related 4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridines: synthesis, molecular conformations and hydrogen bonding in zero, one and two dimensions

2017 ◽  
Vol 73 (3) ◽  
pp. 298-304
Author(s):  
Belakavadi K. Sagar ◽  
Kachigere B. Harsha ◽  
Hemmige S. Yathirajan ◽  
Kanchugarakoppal S. Rangappa ◽  
Ravindranath S. Rathore ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Pyridine Ring ◽  
Chair Conformation ◽  
Two Dimensions ◽  
Relative Orientation ◽  
Molecular Conformations ◽  
Space Groups ◽  
Related Compounds ◽  
Trifluoromethyl Groups ◽  
Centrosymmetric Dimers

In each of 1-(4-fluorophenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C21H19F4N3O2S, (I), 1-(4-chlorophenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C21H19ClF3N3O2S, (II), and 1-(3-methylphenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C22H22F3N3O2S, (III), the reduced pyridine ring adopts a half-chair conformation with the methylsulfonyl substituent occupying an equatorial site. Although compounds (I) and (II) are not isostructural, having the space groups Pbca and P212121, respectively, their molecular conformations are very similar, but the conformation of compound (III) differs from those of (I) and (II) in the relative orientation of the N-benzyl and methylsulfonyl substituents. In compounds (II) and (III), but not in (I), the trifluoromethyl groups are disordered over two sets of atomic sites. Molecules of (I) are linked into centrosymmetric dimers by C—H...π(arene) hydrogen bonds, molecules of (II) are linked by two C—H...O hydrogen bonds to form ribbons of R 3 3(18) rings, which are themselves further linked by a C—Cl...π(arene) interaction, and a combination of C—H...O and C—H...π(arene) hydrogen bonds links the molecules of (III) into sheets. Comparisons are made with the structures of some related compounds.

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 Fifteen 4-(2-methoxyphenyl)piperazin-1-ium salts containing organic anions: supramolecular assembly in zero, one, two and three dimensions

2020 ◽  
Vol 76 (11) ◽  
pp. 1779-1793
Author(s):  
Chayanna Harish Chinthal ◽  
Channappa N. Kavitha ◽  
Hemmige S. Yathirajan ◽  
Sabine Foro ◽  
Ravindranath S. Rathore ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Supramolecular Assembly ◽  
Organic Anions ◽  
Three Dimensions ◽  
Ribbon Structure ◽  
Related Compounds ◽  
Fumarate Salt

Fifteen 4-(2-methoxyphenyl)piperazin-1-ium salts containing organic anions have been prepared and structurally characterized. In the isostructural 4-chlorobenzoate and 4-bromobenzoate salts, C11H17N2O+·C7H4ClO2 − (I) and C11H17N2O+·C7H4BrO2 − (II), and the 4-iodobenzoate salt C11H17N2O+·C7H4IO2 − (III), the ions are linked by N—H...O hydrogen bonds, forming centrosymmetric R 4 4(12) four-ion aggregates; a similar aggregate is formed in the 2-chlorobenzoate salt (V), isomeric with (I). In the 2-fluorobenzoate salt C11H17N2O+·C7H4FO2 − (IV), and the isomorphous pair of salts, the 2-bromobenzoate (VI), isomeric with (II) and 2-iodobenzoate (VII), isomeric with (III), N—H...O and C—H...π(arene) interactions link the components into three-dimensional arrays. Four-ion R 4 4(12) aggregates are also found in the 2-methylbenzoate, 4-aminobenzoate and 4-nitrobenzoate salts, C11H17N2O+·C8H7O2 − (VIII), C11H17N2O+·C7H6NO2 − (IX) and C11H17N2O+·C7H4NO4 − (X), but those in (IX) are linked into complex sheets by an additional N—H...O hydrogen bond. In the 3,5-dinitrobenzoate salt, C11H17N2O+·C7H3N2O6 −·2H2O (XI), N—H...O and O—H...O hydrogen bonds link the components into a complex ribbon structure. In the picrate salt, C11H17N2O+·C6H2N3O7 − (XII), the four-ion aggregates are linked into chains of rings by C—H...O hydrogen bonds. In the hydrogen maleate salt, C11H17N2O+·C4H3O4 − (XIII), two- and three-centre hydrogen bonds link the ions into a ribbon structure while both anions contain very short but asymmetric O—H...O hydrogen bonds, having O...O distances of 2.4447 (16) and 2.4707 (17) Å. O—H...O Hydrogen bonds link the anions in the hydrogen fumarate salt (XIV), isomeric with (XIII), into chains that are linked into sheets via N—H...O hydrogen bonds. In the hydrogen (2R,3R)-tartrate salt, C11H17N2O+·C4H5O6 −·1.698H2O (XV), the anions are linked into sheets by O—H...O hydrogen bonds. Comparisons are made with the structures of some related compounds.

A concise, efficient and versatile synthesis of amino-substituted benzo[b]pyrimido[5,4-f]azepines: synthesis and spectroscopic characterization, together with the molecular and supramolecular structures of three products and one intermediate

2018 ◽  
Vol 74 (3) ◽  
pp. 312-320 ◽  
Author(s):  
Lina M. Acosta Quintero ◽  
Isidro Burgos ◽  
Alirio Palma ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Mass Spectrometry ◽  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Spectroscopic Characterization ◽  
Supramolecular Structures ◽  
Boat Conformation ◽  
Reaction Intermediates ◽  
A Chain ◽  
Related Compounds ◽  
C Nmr

A concise, efficient and versatile synthesis of amino-substituted benzo[b]pyrimido[5,4-f]azepines is described: starting from a 5-allyl-4,6-dichloropyrimidine, the synthesis involves base-catalysed aminolysis followed by intramolecular Friedel–Crafts cyclization. Four new amino-substituted benzo[b]pyrimido[5,4-f]azepines are reported, and all the products and reaction intermediates have been fully characterized by IR,1H and13C NMR spectroscopy and mass spectrometry, and the molecular and supramolecular structures of three products and one intermediate have been determined. In each ofN,2,6,11-tetramethyl-N-phenyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepin-4-amine, C22H24N5, (III), 4-(1H-benzo[d]imidazol-1-yl)-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, which crystallizes as a 0.374-hydrate, C21H19N5·0.374H2O, (VIIIa), and 6,7,9,11-tetramethyl-4-(5-methyl-1H-benzo[d]imidazol-1-yl)-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, C24H25N5, (VIIIc), the azepine ring adopts a boat conformation, but with a different configuration at the stereogenic centre in (VIIIc), as compared with (III) and (VIIIa). In the intermediate 5-allyl-6-(1H-benzo[d]imidazol-1-yl)-N-methyl-N-(4-methylphenyl)pyrimidin-4-amine, C22N21N5, (VIIb), the immediate precursor of 4-(1H-benzo[d]imidazol-1-yl)-6,8,11-trimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, (VIIIb), the allyl group is disordered over two sets of atomic sites having occupancies of 0.688 (5) and 0.312 (5). The molecules of (III) are linked into chains by a C—H...π(pyrimidine) hydrogen bond, and those of (VIIb) are linked into complex sheets by three hydrogen bonds, one of the C—H...N type and two of C—H...π(arene) type. The molecules of the organic component in (VIIIa) are linked into a chain of rings by two C—H...π(arene) hydrogen bonds, and these chains are linked into sheets by the water components; a single weak C—H...N hydrogen bond links molecules of (VIIIc) into centrosymmetricR22(10) dimers. Comparisons are made with some related compounds.

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