Conformational preferences and supramolecular aggregation in 2-nitrophenylthiolates: disulfides and thiosulfonates

2000 ◽  
Vol 56 (5) ◽  
pp. 893-905 ◽  
Author(s):  
Christopher Glidewell ◽  
John N. Low ◽  
James L. Wardell
Keyword(s):  
Hydrogen Bonds ◽  
Nitro Group ◽  
Molecular Conformation ◽  
Three Dimensional ◽  
Asymmetric Unit ◽  
Aryl Ring ◽  
Conformational Preferences ◽  
Independent Molecules ◽  
Centrosymmetric Dimers ◽  
Supramolecular Aggregation

In each of the asymmetrically substituted disulfides 2-nitro-4′-methyldiphenyl disulfide, C13H11NO2S2 (1), 2-nitro-4′-chlorodiphenyl disulfide, C12H8ClNO2S2 (2), 2,4-dinitro-4′-methyldiphenyl disulfide, C13H10N2O4S2 (3), and 2,4-dinitrophenyl-2′-methoxycarbonylmethyl disulfide, C9H8N2O6S2 (4), and in both of the symmetrically substituted disulfides bis(2-nitrophenyl) disulfide, C12H8N2O4S2 (5), and bis(2-nitro-4-trifluoromethylphenyl) disulfide, C14H6F6N2O4S2 (6), the 2-nitro groups are essentially coplanar with the adjacent aryl ring and the S atom remote from the nitrated aryl ring is also essentially coplanar and transoid to the nitro group. In S-(2-nitrophenyl) 2-nitrobenzene thiosulfonate, C12H8N2O6S2 (7), which contains three independent molecules in the asymmetric unit, all six of the independent nitro groups are twisted out of the plane of the adjacent aryl rings. The crystal structures of (1)–(3) contain isolated molecules, that of (4) contains centrosymmetric dimers held together by C—H...O hydrogen bonds, while in the structures of (5)—(7), respectively, the C—H...O hydrogen bonds generate one-, two- and three-dimensional arrays. The interplay between molecular conformation and supramolecular aggregation is discussed.

Interplay of hydrogen bonds, iodo...nitro interactions and aromatic π...π stacking interactions in iodo-nitroanilines

2002 ◽  
Vol 58 (4) ◽  
pp. 701-709 ◽  
Author(s):  
Simon J. Garden ◽  
Silvia P. Fontes ◽  
James L. Wardell ◽  
Janet M. S. Skakle ◽  
John N. Low ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Nitro Group ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Single Type ◽  
Stacking Interactions ◽  
Π Stacking ◽  
Independent Molecules ◽  
Related Compounds ◽  
Centrosymmetric Dimers

Molecules of 2-iodo-5-nitroaniline (I) are linked by N—H...O hydrogen bonds into centrosymmetric dimers and by asymmetric three-centre iodo...nitro interactions into chains, so forming chains of fused centrosymmetric rings: these chains are linked by aromatic π...π stacking interactions to form a three-dimensional structure. In the isomeric 4-iodo-2-nitroaniline (II), each of the two independent molecules forms hydrogen-bonded chains that are linked by two-centre iodo...nitro interactions into sheets of two types, each containing only a single type of molecule: π...π stacking interactions are absent. In 2,4-diiodo-3-nitroaniline (III), where the nitro group is almost orthogonal to the aryl ring, a combination of N—H...O hydrogen bonds and two distinct two-centre iodo...nitro interactions links the molecules into a three-dimensional framework that is reinforced by aromatic π...π stacking interactions. Bond lengths and conformations are discussed and comparisons are drawn with related compounds.

scholarly journals N-(4-Bromophenyl)methoxycarbothioamide

Molbank ◽  
10.3390/m1012 ◽  
2018 ◽  
Vol 2018 (3) ◽  
pp. M1012
Author(s):  
Chien Yeo ◽  
Edward Tiekink
Keyword(s):  
Molecular Structure ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Title Compound ◽  
Molecular Conformation ◽  
Three Dimensional ◽  
Halogen Bonding ◽  
Asymmetric Unit ◽  
Weak Intermolecular Interactions ◽  
Independent Molecules

The synthesis, spectroscopic and crystallographic characterisation of the title compound, O-methyl-N-4-bromophenyl thiocarbamate, MeOC(=S)N(H)PhBr-4 (1), are described. Spectroscopy confirmed the formation of the compound and the molecular structure was determined crystallographically. Two independent but chemically similar molecules comprise the asymmetric unit of 1. The C‒S and C‒N bond lengths confirm the presence of the thioamide tautomer. The thione-S and amide-N‒H atoms are syn, enabling the formation of amide-N‒H…S(thione) hydrogen bonds between the two independent molecules that generates a two-molecule aggregate via an eight-membered {…HNCS}2 synthon. The aggregates are connected into a three-dimensional architecture via weak intermolecular interactions, including Br…π(4-bromophenyl), S…π(4-bromophenyl), and weak Br…S halogen bonding contacts. The overall molecular conformation, thioamide tautomer, and the presence of amide-N‒H…S(thione) hydrogen bonding in the crystal conform with expectation for this class of compound.

Conformational preferences in 2-nitrophenylthiolates: interplay between intra- and intermolecular forces; structures of (E)-1-(4-methyl-2-nitrobenzenethiolato)-2-phenylethene, S-(2-nitrophenyl)benzenecarbothiolate and 1-(2-nitrophenylthio)-2,5-pyrrolidinedione

2000 ◽  
Vol 56 (1) ◽  
pp. 58-67 ◽  
Author(s):  
John N. Low ◽  
Emily J. Storey ◽  
Mary McCarron ◽  
James L. Wardell ◽  
George Ferguson ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Nitro Group ◽  
Intermolecular Forces ◽  
Aryl Ring ◽  
Local Energy Minimum ◽  
Conformational Preferences ◽  
A Chain ◽  
Related Compounds ◽  
Scf Calculations ◽  
Intramolecular Forces

In (E)-1-(4-methyl-2-nitrobenzenethiolato)-2-phenylethene, C15H13NO2S (1) (orthorhombic Pbca), the nitro group is almost coplanar with the adjacent aryl ring, but the dihedral angles between the nitro-aryl and styryl fragments is ∼121°. The molecules are linked by paired C—H...O hydrogen bonds in a chain of rings. In S-(2-nitrophenyl)benzenecarbothiolate, C13H9NO3S (2) (monoclinic P21/a), the nitro group is rotated by 33.0 (2)° out of the plane of the adjacent aryl ring and the thiobenzoate group is strongly twisted away from the plane of the disubstituted aryl ring. The molecules of (2) are linked into chains by C—H...O hydrogen bonds, and each chain is linked to two neighbouring chains by means of aromatic π...π stacking interactions. In 1-(2-nitrophenylthio)-2,5-pyrrolidinedione, C10H8N2O4S (3) (monoclinic P21/a), the nitro group is again almost coplanar with the adjacent aryl ring, but the pyrrolidinedione unit is almost orthogonal to the O2NC6H4SN plane. There are three types of C—H...O hydrogen bond in the structure, and these link the molecules into a two-dimensional net. The conformations of these molecules have been investigated by SCF calculations and two energy minima have been identified for each: the molecules of (1) and (3) adopt conformations in their crystals which are close to those at the overall energy minima calculated for isolated molecules, while molecules of (2) adopt a conformation in the crystal close to that calculated for the local energy minimum. Comparisons are made with the structures of some related compounds and it is concluded that, while the nature of the two conformational minima is determined by intramolecular forces, the choice between them is determined primarily by intermolecular forces.

scholarly journals 6,7-Dimethoxy-2,4-diphenylquinoline

2014 ◽  
Vol 70 (2) ◽  
pp. o165-o165
Author(s):  
M. Prabhuswamy ◽  
S. Madan Kumar ◽  
T. R. Swaroop ◽  
K. S. Rangappa ◽  
N. K. Lokanath
Keyword(s):  
Hydrogen Bonds ◽  
Dihedral Angle ◽  
Title Compound ◽  
Three Dimensional ◽  
Asymmetric Unit ◽  
Compound C ◽  
Centroid Distance ◽  
Phenyl Rings ◽  
Independent Molecules ◽  
Dimeric Aggregates

In the title structure of the title compound, C23H19NO2, two conformationally similar molecules (AandB) comprise the asymmetric unit. The dihedral angle between phenyl rings bridged by the quinoline moiety are 76.25 (8)° in moleculeAand 70.39 (9)° in moleculeB. In the crystal, the independent molecules are connected by C—H...O hydrogen bonds and the resulting dimeric aggregates are linked by π–π [inter-centroid distance = 3.7370 (8) Å] and C—H...π interactions, forming a three-dimensional architecture.

scholarly journals (3aR*,8bR*)-3a,8b-Dihydroxy-1-(4-methylphenyl)-2-methylsulfanyl-3-nitro-1,8b-dihydroindeno[1,2-b]pyrrol-4(3aH)-one

2014 ◽  
Vol 70 (3) ◽  
pp. o279-o280
Author(s):  
R. A. Nagalakshmi ◽  
J. Suresh ◽  
R. Ranjith Kumar ◽  
V. Jeyachandran ◽  
P. L. Nilantha Lakshman
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Title Compound ◽  
Three Dimensional ◽  
Dihedral Angles ◽  
Asymmetric Unit ◽  
Compound C ◽  
Dimensional Network ◽  
Independent Molecules ◽  
Hydroxy Groups

The asymmetric unit of the title compound, C19H16N2O5S, contains four independent molecules (A,B,CandD), with two molecules (BandD) displaying disorder in their methylsulfanyl groups [occupancy ratios of 0.797 (11):0.203 (11) and 0.85 (2):0.15 (2)]. The nitro groups are twisted slightly out of the planes of the 2-pyrroline rings to which they are bonded with dihedral angles of 10.17 (1), 8.01 (1), 9.44 (1) and 8.87 (1)° in moleculesA,B,CandD, respectively. The 2-pyrroline rings are almost orthogonal to the attached tolyl rings, forming dihedral angles of 73.44 (1), 81.21 (1), 88.18 (8) and 73.94 (1)° for moleculesA,B,CandD, respectively. A weak intramolecular O—H...O interaction is observed in moleculesBandC. The two hydroxy groups in each molecule are involved in intermolecular O—H...O hydrogen bonding. In the crystal, molecules are connectedviaO—H...O and C—H...O hydrogen bonds, forming a complex three-dimensional network.

scholarly journals Crystal structure ofN-(quinolin-6-yl)hydroxylamine

2014 ◽  
Vol 70 (11) ◽  
pp. 322-324 ◽  
Author(s):  
Anuruddha Rajapakse ◽  
Roman Hillebrand ◽  
Sarah M. Lewis ◽  
Zachary D. Parsons ◽  
Charles L. Barnes ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Title Compound ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Asymmetric Unit ◽  
Π Interactions ◽  
Compound C ◽  
Independent Molecules ◽  
A Minor

The title compound, C9H8N2O, crystallized with four independent molecules in the asymmetric unit. The four molecules are linkedviaone O—H...N and two N—H...N hydrogen bonds, forming a tetramer-like unit. In the crystal, molecules are further linked by O—H...N and N—H...O hydrogen bonds forming layers parallel to (001). These layers are linkedviaC—H...O hydrogen bonds and a number of weak C—H...π interactions, forming a three-dimensional structure. The crystal was refined as a non-merohedral twin with a minor twin component of 0.319.

scholarly journals 1-(6-Fluoro-1,3-benzothiazol-2-yl)-2-(1-phenylethylidene)hydrazine

2012 ◽  
Vol 68 (8) ◽  
pp. o2438-o2439 ◽  
Author(s):  
Hoong-Kun Fun ◽  
Ching Kheng Quah ◽  
D. Munirajasekhar ◽  
M. Himaja ◽  
B. K. Sarojini
Keyword(s):  
Hydrogen Bonds ◽  
Dihedral Angle ◽  
Phenyl Ring ◽  
Three Dimensional ◽  
Ring System ◽  
The Other ◽  
Asymmetric Unit ◽  
Compound C ◽  
Dimensional Network ◽  
Independent Molecules

The asymmetric unit of the title compound, C15H12FN3S, consists of two independent molecules with comparable geometries. In one molecule, the 1,3-benzothiazole ring system (r.m.s. deviation = 0.011 Å) forms a dihedral angle of 19.86 (6)° with the phenyl ring. The corresponding r.m.s. deviation and dihedral angle for the other molecule are 0.014 Å and 22.32 (6)°, respectively. In the crystal, molecules are linkedviaN—H...N, C—H...F and C—H...N hydrogen bonds into a three-dimensional network. The crystal studied was a non-merohedral twin with a refined BASF value of 0.301 (2).

scholarly journals 2,2′-Bis{8-[(benzylamino)methylidene]-1,6-dihydroxy-5-isopropyl-3-methylnaphthalen-7(8H)-one}

2013 ◽  
Vol 69 (11) ◽  
pp. o1626-o1627
Author(s):  
Shukhrat M. Hakberdiev ◽  
Samat A. Talipov ◽  
Davranbek N. Dalimov ◽  
Bakhtiyar T. Ibragimov
Keyword(s):  
Hydrogen Bonds ◽  
Title Compound ◽  
Three Dimensional ◽  
The Other ◽  
Supramolecular Architecture ◽  
Asymmetric Unit ◽  
Ring Systems ◽  
Compound C ◽  
Phenyl Rings ◽  
Independent Molecules

The asymmetric unit of the title compound, C44H44N2O6, contains two independent molecules with similar conformations. The dihydronaphthalene ring systems are approximately planar [maximum deviations = 0.036 (2), 0.128 (2), 0.0.24 (2) and 0.075 (2) Å]. The dihedral angle between two dihydronaphthalene ring systems is 83.37 (4)° in one molecule and 88.99 (4)° in the other. The carbonyl O atom is linked with the adjacent hydroxy and imino groupsviaintramolecular O—H...O and N—H...O hydrogen bonds. In the crystal, molecules are linked through O—H...O hydrogen bonds into layers parallel to (001), and adjacent layers are further stacked by π–π interactions between dihydronaphthalene and phenyl rings into a three-dimensional supramolecular architecture. In the crystal, one of the isopropyl groups is disordered over two positions with an occupancy ratio of 0.684 (8):0.316 (8).

scholarly journals Crystal structure of (E)-1,3-dimethyl-2-[3-(3-nitrophenyl)triaz-2-en-1-ylidene]-2,3-dihydro-1H-imidazole

2014 ◽  
Vol 70 (10) ◽  
pp. 224-227 ◽  
Author(s):  
Siddappa Patil ◽  
Alejandro Bugarin
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Benzene Ring ◽  
Three Dimensional ◽  
Imidazole Ring ◽  
Asymmetric Unit ◽  
Framework Structure ◽  
Compound C ◽  
Centroid Distance ◽  
Independent Molecules

The title compound, C11H12N6O2, a π-conjugated triazene, crystallized with two independent molecules (AandB) in the asymmetric unit. Both molecules have anEconformation about the –N=N– bond and have slightly twisted overall conformations. In moleculeA, the imidazole ring is inclined to the benzene ring by 8.12 (4)°, while in moleculeBthe two rings are inclined to one another by 7.73 (4)°. In the crystal, the independent molecules are linked to each other by C—H...O hydrogen bonds, forming –A–A–A– and –B–B–B–chains along [100]. The chains are linked by C—H...O and C—H...N hydrogen bonds, forming sheets lying parallel to (001). The sheets are linked by further C—H...N hydrogen bonds and π–π interactions [centroid–centroid distance = 3.5243 (5) Å; involving the imidazole ring of molecule A and the benzene ring of moleculeB], forming a three-dimensional framework structure.

scholarly journals Crystal structure of (S)-5-chloro-N-({2-oxo-3-[4-(3-oxomorpholin-4-yl)phenyl]oxazolidin-5-yl}methyl)thiophene-2-carboxamide

2018 ◽  
Vol 74 (1) ◽  
pp. 51-54 ◽  
Author(s):  
Jie Shen ◽  
Gu-Ping Tang ◽  
Xiu-Rong Hu
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Title Compound ◽  
Three Dimensional ◽  
Supramolecular Architecture ◽  
Asymmetric Unit ◽  
Torsion Angles ◽  
Independent Molecules

The asymmetric unit of the crystal of the title compound (common name rivaroxaban), C19H18ClN3O5, contains two rivaroxaban molecules with different conformations; the C—C—N—C torsion angles between the oxazolidine and thiophene rings are −171.1 (7) and −106.8 (9)° in the two independent molecules. In the crystal, classical N—H...O hydrogen bonds and weak C—H...O hydrogen bonds link the molecules into a three-dimensional supramolecular architecture.

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