Bromo-benzene Rings Research Articles

5-Bromo-1-(4-bromophenyl)isatin

In the title compound [systematic name: 5-bromo-1-(4-bromophenyl)-2,3-dihydro-1H-indole-2,3-dione], C14H7Br2NO2, all of the atoms except the C—H groups in the bromobenzene ring lie on a (010) crystallographic mirror plane, with the benzene ring completed by reflection. The dihedral angle between the ring systems is constrained to be 90° by symmetry. In the crystal, molecules are linked by weak C—H...Br interactions in the [001] direction and paired very weak C—H...O interactions to the same acceptor in the [100] direction, generating (010) sheets. Possible extremely weak π–π stacking occurs between the layers.

Crystal structure and Hirshfeld surface analysis of 1-(4-bromo-phen-yl)-2-{[5-(pyridin-3-yl)-1,3,4-oxa-diazol-2-yl]sulfan-yl}ethan-1-one.

In the title compound, C15H10BrN3O2S, the dihedral angles between the 1,3,4-oxa-diazole ring and the 3-pyridinyl and bromo-benzene rings are 12.17 (15) and 18.74 (15)°, respectively. In the crystal, the mol-ecules are linked into [100] chains by way of C-H⋯O, C-H⋯N, C-H⋯S hydrogen bonds. The Hirshfeld surface analysis indicates that the most important contributions to the packing are H⋯H (19.5%), N⋯H (17.3%), C⋯H (15.5%), Br⋯H (11.7%), and O⋯H (11.0%) inter-actions.

Crystal structure of N-(p-methylbenzylidene)-p-bromoaniline

The asymmetric unit of the title compound C14H12BrN (systematic name (E)-N-(4-bromophenyl)-1-(p-tolyl)methanimine) contains one half-molecule: a crystallographic center of inversion is located at the midpoint of the bridging N=C bond. The central HC=N unit makes dihedral angles of 15.7(3)° and 15.2(4)° with bromobenzene and methylbenzene ring systems, respectively. The C and N atoms of the HC=N central unit are disordered over two sites in a 50:50 ratio. The Br atom of the 4-bromoaniline ring and the methyl atom of the 4-methylbenzilidene ring systems are also 50% disordered. In the crystal, molecules are linked by C–H⋯π interactions forming slabs parallel to the bc plane. The atomic coordinates are not available for the previously reported crystal structure of the title compound: CSD refcode MBZCLE. The reported R factor of 0.103 for the analysis in the space group P21/a is much higher than in the present analysis, which gives 0.033 in the space group P21/c.

2-(5-Bromo-1H-indol-3-yl)-4-(4-bromophenyl)-5-(4-chlorobenzoyl)-1H-pyrrole-3-carbonitrile dimethyl sulfoxide monosolvate

In the title solvated compound, C26H14Br2ClN3O·C2H6OS, the indole ring is inclined to the central pyrrole ring by 25.7 (2)°. The chlorobenzene ring and the bromobenzene rings subtend dihedral angles of 56.5 (2) and 53.4 (2)°, respectively, with the central pyrrole ring. In the crystal, molecules are bridged by N—H...O hydrogen bonds, involving the dimethyl sulfoxide solvent molecule, forming chains along [010]. There are no other significant intermolecular interactions present.

N′-[(1E)-4-Bromobenzylidene]-5-phenyl-1H-pyrazole-3-carbohydrazide

In the title compound, C17H13BrN4O, the dihedral angles between the pyrazole ring and the pedant phenyl and bromobenzene rings are 21.61 (11) and 28.09 (11)°, respectively. In the crystal, N—H...O hydrogen bonds link the molecules into [010] chains, which are reinforced by C—H...O interactions.

Crystal structure of 4-bromo-phenyl-2-oxo-2H-chromene-3-carboxyl-ate.

In the title compound, C16H9BrO4, the coumarin ring system is approximately planar, with an r.m.s deviation of the ten fitted non-H atoms of 0.031 Å, and forms a dihedral angle of 25.85 (10)° with the bromo­benzene ring. The carbonyl atoms are syn. In the crystal, mol­ecules are connected along [001] via C—H⋯O inter­actions, forming C(6) chains. Neighbouring C(6) chains are connected via several π–π inter­actions [range of centroid–centroid distances = 3.7254 (15)–3.7716 (16) Å], leading to sheets propagating in the bc plane.

Crystal structure of 2-benzyl-amino-4-(4-bromo-phen-yl)-6,7-di-hydro-5H-cyclo-penta-[b]pyridine-3-carbo-nitrile.

In the title compound C22H18BrN3, the cyclo-pentane ring adopts an envelope conformation with the central methyl-ene C atom as the flap. The dihedral angles between the central pyridine ring and the pendant benzyl and and bromo-benzene rings are 82.65 (1) and 47.23 (1)°, respectively. In the crystal, inversion dimers linked by pairs of N-H⋯Nn (n = nitrile) hydrogen bonds generate R 2 (2)(12) loops. These dimers are linked by weak π-π inter-actions [centroid-centroid distance = 3.7713 (14) Å] into a layered structure.

Crystal structure of 2-(3-bromo-phen-yl)-1,3-di-thiane.

In the title compound, C10H11BrS2, the 1,3-di­thiane ring has a chair conformation with the 1,4-disposed C atoms being above and below the remaining four atoms. The bromo­benzene ring occupies an equatorial position and forms a dihedral angle of 86.38 (12)° with the least-squares plane through the 1,3-di­thiane ring. Thus, to a first approximation the mol­ecule has mirror symmetry with the mirror containing the bromo­benzene ring and the 1,4-disposed C atoms of the 1,3-di­thiane ring. In the crystal, mol­ecules associate via weak methyl­ene–bromo­benzene C—H⋯π and π–π [Cg⋯Cg = 3.7770 (14) Å for centrosymmetrically related bromo­benzene rings] inter­actions, forming supra­molecular layers parallel to [10-1]; these stack with no specific inter­molecular inter­actions between them.

Crystal structure of 4,6-bis-[(E)-4-bromo-styr-yl]-2-(butyl-sulfan-yl)pyrimidine.

In the title compound, C24H22Br2N2S, the dihedral angles between the central pyrimidine ring and the pendant bromo­benzene rings are 11.02 (11) and 13.20 (12)°. The butyl side chain adopts a gauche conformation [C—C—C—C = −67.4 (4)°]. In the crystal, weak aromatic π–π stacking is observed between the pyrimidine ring and one of the benzene rings [centroid–centroid separation = 3.6718 (17) Å].

Crystal structure of ethyl 2-[(4-bromo-phen-yl)amino]-3,4-di-methyl-pent-3-enoate.

In the title compound, C15H20BrNO2, there are two independent mol­ecules (A and B) comprising the asymmetric unit and these adopt very similar conformations. In A, the dihedral angle between the CO2 and MeC=CMe2 groups is 80.7 (3)°, and these make dihedral angles of 3.5 (3) and 84.09 (16)°, respectively, with the bromo­benzene ring. The equivalent dihedral angles for mol­ecule B are 78.4 (3), 2.1 (3) and 78.37 (12)°, respectively. The most prominent inter­actions in the crystal packing are amine-N—H⋯O(carbon­yl) hydrogen bonds between the two independent mol­ecules, resulting in non-centrosymmetric ten-membered {⋯OC2NH}2 synthons. Statistical disorder is noted for each of the terminal methyl groups of the ethyl residues.

4-{5-[(2-Bromobenzyl)sulfanyl]-1H-tetrazol-1-yl}benzoic acid

In the title compound, C15H11BrN4O2S, the tetra­zole ring makes dihedral angles of 45.97 (10) and 75.41 (1)°, respectively, with the benzoyl and bromo­benzene rings while the dihedral angle between the benzene rings is 73.77 (1)°. In the crystal, mol­ecules are linked through O—H⋯ N and C—H⋯ O hydrogen bonds, giving infinite chains in both the [110] and [1-10] directions. These chains are further connected by C—Br⋯π and C—O⋯π inter­actions and also by π–π stacking between tetra­zole rings [centroid–centroid distance = 3.312 (1) Å], generating a three-dimensional network.

2-(4-Bromoanilino)-6-(4-chlorophenyl)-5-methoxycarbonyl-4-methyl-3,6-dihydropyrimidin-1-ium chloride

In the title molecular salt, C19H18BrClN3O2 +·Cl−, the dihedral angles between the pyrimidine ring and the chlorobenzene and bromobenzene rings are 72.4 (2) and 45.5 (2)°, respectively. The dihedral angle between the chlorobenzene and bromobenzene rings is 27.5 (2)°. The conformation of the mol­ecule is stabilized by an intra­molecular C—H⋯O inter­action. In the crystal, the anion and cation are linked by an N—H⋯Cl hydrogen bond. Pairs of weak C—H⋯O and C—H⋯Cl hydrogen bonds form inversion dimers. Further N—H⋯Cl hydrogen bonds form R 2 1(6) motifs and link the dimers into chains along [101]. Br⋯Cl short contacts [3.482 (2) Å] inter­link the hydrogen-bonded chains along the b-axis direction.

Ethyl 2-amino-4-(4-bromophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate

In the title compound, C23H20BrNO4, the pyran ring has a flattened boat conformation with the O and methine C atoms lying to one side of the plane [0.160 (5) and 0.256 (6) Å, respectively] defined by the remaining atoms. Nevertheless, the 4H-benzo[h]chromene ring system approximates a plane (r.m.s. deviation = 0.116 Å) with the bromo­benzene ring almost perpendicular [dihedral angle = 83.27 (16)°] and the ester group coplanar [C—C—C—O = 3.4 (5)°]; the meth­oxy substituent is also coplanar [C—O—C—C = 174.5 (3)°]. In addition to an intra­molecular N—H⋯O(ester carbon­yl) hydrogen bond, the ester carbonyl O atom also forms an inter­molecular N—H⋯O hydrogen bond with the second amine H atom, generating a zigzag supra­molecular chain along the c axis in the crystal packing. The chains are linked into layers in the bc plane by N—H⋯Br hydrogen bonds, and these layers are consolidated into a three-dimensional architecture by C—H⋯π inter­actions.

6-Bromo-4-[2-(4-fluorobenzylidene)hydrazin-1-ylidene]-1-methyl-3,4-dihydro-1H-2λ6,1-benzothiazine-2,2-dione

In the title compound, C16H13BrFN3O2S, the dihedral angle between the aromatic rings is 2.55 (19)° and the C=N—N=C torsion angle is 178.9 (3)°. The conformation of the thia­zine ring is an envelope, with the S atom displaced by −0.811 (3) Å from the mean plane of the other five atoms (r.m.s. deviation = 0.042 Å). In the crystal, C—H⋯O inter­actions link the mol­ecules and weak aromatic π–π stacking between the fluoro­benzene and bromo­benzene rings [centroid–centroid separation = 3.720 (2) Å and inter­planar angle = 2.6 (2)°] is also observed.

(4E)-N-[(2-Bromophenyl)methoxy]-1,3-dimethyl-2,6-diphenylpiperidin-4-imine

In the title compound, C26H27BrN2O, the piperidine ring has a chair conformation and all ring substituents occupy equatorial positions, apart from the double-bonded N atom, which occupies a bis­ectional position. The dihedral angle formed between the phenyl rings is 61.18 (19)°, and the phenyl rings form dihedral angles of 49.78 (19) and 69.2 (18)° with the bromo­benzene ring. The latter is coplanar with the meth­oxy(methyl­idene)amine fragment [N—O—C—C torsion angle = −171.7 (2)°]. Linear supra­molecular chains, approximately along [112], sustained by C—H⋯π inter­actions, feature in the crystal packing.

2-[2-(2-Bromophenyl)-2-oxoethyl]-1λ6,2-benzothiazole-1,1,3-trione

The asymmetric unit of the title compound, C15H10BrNO4S, contains two different conformers in which the benzisothia­zole rings are essentially planar, with r.m.s. deviations of 0.012 and 0.017 Å. The mean planes of the benzene rings form dihedral angles 70.49 (13) and 72.79 (11)° with the benzisothia­zole rings. The orientation of the Br atoms in the two conformers exhibit the most pronounced difference, with opposing orientations in the two mol­ecules. The crystal structure is stabilized by π–π inter­actions between the benzene rings of the benzisothia­zole moieties of one mol­ecule and bromo­benzene rings of the other mol­ecule, with distances between the ring centroids of 3.599 (3) and 3.620 (3) Å, respectively. The crystal packing is further consolidated by pairs of weak inter­molecular C—H⋯O hydrogen bonds, which form inversion dimers.

6-(4-Bromophenyl)-3-methyl-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine

In the title compound, C11H9BrN4S, the 1,2,4-triazole ring is essentially planar (r.m.s. deviation = 0.020 Å) and makes a dihedral angle of 29.1 (5)° with the bromo­benzene ring. The 3,6-dihydro-1,3,4-thia­diazine ring adopts a twist-boat conformation. In the crystal, mol­ecules are linked by C—H⋯N inter­actions into sheets lying parallel to the (010) plane. The same N atom accepts two such hydrogen bonds.

4-Bromo-N-(4-hydroxybenzylidene)aniline

In the title compound, C13H10BrNO, the benzene ring planes are inclined at an angle of 48.85 (17)°, resulting in a nonplanar mol­ecule. A characteristic of aromatic Schiff bases with N-aryl substituents is that the terminal phenyl rings are twisted relative to the HC=N plane. In this case, the HC=N unit makes dihedral angles of 11.1 (4) and 38.5 (3)° with the hy­droxy­benzene and bromo­benzene rings, respectively. In the crystal, the molecules are linked by O—H⋯N hydrogen bonds to form infinite (C8) chains along the b axis.

3-(3-Bromobenzyl)-1H-isochromen-1-one

In the title compound, C16H11BrO2, the isocoumarin ring system is planar (r.m.s. deviation = 0.015 Å) and subtends a dihedral angle of 88.90 (2)° with the bromo­benzene ring. In the crystal, mol­ecules are linked, forming a three-dimensional packing pattern involving C—H⋯O inter­actions, Br⋯O contacts [3.4734 (10) Å] and π–π stacking inter­actions with centroid–centroid distances ranging from 3.667 (2) to 3.765 (2) Å.

(E)-4-[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)iminomethyl]phenyl 4-bromobenzenesulfonate

In the title compound, C24H20BrN3O4S, the central benzene ring makes dihedral angles of 17.13 (13), 39.83 (13) and 58.37 (13)°, respectively, with the pyrazolone ring, the bromo­benzene ring and the terminal phenyl ring. In the crystal structure, the packing is stabilized by a weak non-classical inter­molecular C—H⋯O hydrogen bond which links the mol­ecules into a chain propagating in [100].