Bromo-phenyl Rings Research Articles

Crystal structure and Hirshfeld surface analysis of 2-(4-bromo-phen-yl)-4-methyl-6-oxo-1-phenyl-1,6-di-hydro-pyridine-3-carbo-nitrile.

In the title compound, C19H13BrN2O, the pyridine ring is essentially planar [maximum deviation = 0.024 (4) Å for the N atom] and makes dihedral angles of 74.6 (2) and 65.8 (2)°, respectively, with the phenyl and bromo-phenyl rings, which subtend a dihedral angle of 63.1 (2)°. In the crystal, mol-ecules are connected along the c-axis direction via C-Br⋯π inter-actions, generating zigzag chains parallel to the (010) plane. C-H⋯N and C-H⋯O hydrogen-bonding inter-actions further connect the mol-ecules, forming a three-dimensional network and reinforcing the mol-ecular packing. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (36.2%), C⋯H/H⋯C (21.6%), N⋯H/H⋯N (12.2%), and Br⋯H/H⋯Br (10.8%) inter-actions.

Synthesis, crystal structure and Hirshfeld surface analysis of dimethyl 3-(3-bromo-phen-yl)-6-methyl-7-oxo-3,5,6,7-tetra-hydro-pyrazolo-[1,2-a]pyrazole-1,2-di-carboxyl-ate.

The title compound, C17H17BrN2O5, resulted from the 1,3-dipolar cyclo-addition reaction between dimethyl acetyl-enedi-carboxyl-ate and (3-bromo-benzyl-idene)-4-methyl-5-oxopyrazolidin-2-ium-1-ide in CHCl3. The dihedral angle between the pyrazole rings (all atoms) is 32.91 (10)°; the oxo-pyrazole ring displays an envelope conformation whereas the other pyrazole ring adopts a twisted conformation. The bromo-phenyl ring subtends a dihedral angle of 88.95 (9)° with the mean plane of its attached pyrazole ring. In the crystal, the mol-ecules are linked by C-H⋯O hydrogen bonds and aromatic π-π inter-actions with an inter-centroid distance of 3.8369 (10) Å. The Hirshfeld surface analysis and fingerprint plots reveal that the mol-ecular packing is governed by H⋯H (37.1%), O⋯H/H⋯O (31.3%), Br⋯H/H⋯Br (13.5%) and C⋯H/H⋯C (10.6%) contacts. The energy framework indicates that dispersion energy is the major contributor to the mol-ecular packing.

4‐(4‐Bromophenyl)thiazol‐2‐amine: Crystal structure determination, DFT calculations, visualizing intermolecular interactions using Hirshfeld surface analysis, and DNA binding studies

Abstract2‐Aminothiazole is a valuable synthon in organic synthesis and an important structural unit of pharmaceutically active drugs. It is accessible via several synthetic routes. In the current account, compound 4 {4‐(4‐bromophenyl) thiazol‐2‐amine} was synthesized by employing a recently reported procedure of Gabriel synthesis using Lawesson reagent. The title compound was characterized through spectro‐elemental analytical data, and its crystal structure was determined by single‐crystal X‐ray diffraction. The torsion angles, bond lengths, and bond strengths between the planes of the thiazole and phenyl rings were optimized by theoretical calculations by applying the B3LYP/6‐311++G(d,p) level for the purpose of investigating the conformational effects on the stabilization of the crystal packing. HOMO‐LUMO analysis, vibrational analysis, and thermodynamic parameters were also investigated. A detailed analysis of the intermolecular interactions of thiazole moiety bearing the amino and bromophenyl ring has been performed based on the Hirshfeld surfaces and their associated two‐dimensional fingerprint plots. The relative contributions of the main intermolecular contacts as well as the enrichment ratios derived from the Hirshfeld surface analysis establish the 2‐aminothiazole synthon to be a molecule of great interest. DNA binding studies pointed towards anticancer potency of the synthesized compound via reversible binding.

4-(4-Bromophenyl)-2-(3-(4-bromophenyl)-5-{3-[5-methyl-1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl]-1-phenyl-1H-pyrazol-4-yl}-4,5-dihydro-1H-pyrazol-1-yl)-1,3-thiazole

In the title compound, C37H28Br2N8S, the dihedral angles between the planes of tolyl–triazolyl–pyrazolyl–phenyl rings are 47.5 (1), 11.4 (2) and 22.4 (2)°, respectively, and the angles between the bromophenyl–thiazolyl–dihydropyrazolyl–bromophenyl rings are 16.0 (2), 5.1 (2) and 0.8 (2)°, respectively. The dihedral angle between the planes of the pyrazolyl and dihydropyrazolyl rings is 67.7 (1)°. In the crystal, weak C—H...Br interactions form chains of molecules propagating in the [010] direction.

4-(4-Bromophenyl)-2-(3-(4-chlorophenyl)-5-{3-[5-methyl-1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl]-1-phenyl-1H-pyrazol-4-yl}-4,5-dihydro-1H-pyrazol-1-yl)thiazole

In the title compound, C37H28BrClN8O, the linked chlorophenyl, pyrazolyl and thiazolyl ringss are almost coplanar, with dihedral angles of 0.6 (3)° between the chlorophenyl and pyrazolyl rings and 5.4 (3)° between the pyrazolyl and thiazolyl rings. The dihedral angle between the thiazolyl and bromophenyl rings is 17.5 (2)°. The central pyrazolyl rings subtend a dihedral angle of 67.7 (1)°. In the crystal, π–π and C—H...Br interactions link the molecules to form columns parallel to [010]. The π–π interactions involve partially overlapping nonparallel bromophenyl and tolyl groups.

Synthesis, single crystal structure and spectroscopic aspects of chalcone 2(2E)-1-(4′-bromobiphenyl-4-yl)-3-(2, 3-dimethoxybenzaldhyde) prop-2-ene-1-one

Abstract The title compound, (2E)-1-(4′-bromobiphenyl-4-yl)-3-(3,4-dichlorophenyl)-3-hydroxypropan-1-one (BDCP) was synthesized, spectrally characterized (IR, UV, FT-IR, 1H NMR, and FT-Raman), and its three- dimensional structure was confirmed by single crystal diffraction studies. In addition, Second Harmonic Generation (SHG) efficiency of the crystal, thermogravimetric analysis (TGA), and powder XRD were performed. The bromo phenyl ring makes a dihedral angle of 50.8 (2)0 and 34.5 (2)° with the methoxy phenyl ring and central phenyl moiety. The dihedral angle between the methoxy phenyl ring and the central phenyl moiety is 17.1(2)0. The short contacts C9—O1…Cg1 and C3—H3…Cg3 are involved in crystal structure stabilization. The SHG conversion of the BDCP is found to be 1.33 times that of Urea.

(E)-1-(3-Bromophenyl)-3-(3-fluorophenyl)prop-2-en-1-one

In the title compound, C15H10BrFO, the olefinic double bond adopts an E conformation. The molecule is non-planar as seen by the dihedral angle of 48.92 (11)° between the bromophenyl and fluorophenyl rings. The carbonyl group is twisted from the plane of the bromophenyl ring and the olefinic double bond. The trans conformation of the C=C double bond in the central enone group is confirmed by the C—C=C—C torsion angle of −165.7 (2)°.

Crystal structure of (2E)-1-(1-benzo-furan-2-yl)-3-(2-bromo-phen-yl)prop-2-en-1-one monohydrate.

The title compound, C17H11BrO2·H2O, crystallizes as a monohydrate in the chiral ortho­rhom­bic space group P212121, and has non-linear optical (NLO) properties. The mol­ecule has an E conformation about the C=C bond and is relatively planar with the benzo­furan and bromo­phenyl rings being inclined to one another by 10.60 (14)°. In the crystal, the water mol­ecule is linked to the organic mol­ecule by O—H⋯O hydrogen bonds, forming an R 2 2(7) ring motif while C—H⋯O hydrogen bonds lead to the formation of helices along the b-axis direction.

The effect of bromine scanning around the phenyl group of 4-phenylquinolone derivatives.

Three quinolone compounds were synthesized and crystallized in an effort to study the structure-activity relationship of these calcium-channel antagonists. In all three quinolones, viz. ethyl 4-(4-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, (I), ethyl 4-(3-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, (II), and ethyl 4-(2-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, (III), all C21H24BrNO3, common structural features such as a flat boat conformation of the 1,4-dihydropyridine (1,4-DHP) ring, an envelope conformation of the fused cyclohexanone ring and a bromophenyl ring at the pseudo-axial position and orthogonal to the 1,4-DHP ring are retained. However, due to the different packing interactions in each compound, halogen bonds are observed in (I) and (III). Compound (III) crystallizes with two molecules in the asymmetric unit. All of the prepared derivatives satisfy the basic structural requirements to possess moderate activity as calcium-channel antagonists.

2-{4-[Bis(4-bromo-phen-yl)amino]-benzyl-idene}malono-nitrile.

In the crystal structure of the title compound, C22H13Br2N3, the two bromo­phenyl rings are rotated out of the plane of the central benzyl­idene ring by 68.7 (1) and 69.3 (1)°. Both cyano substituents are located nearly in the plane of the benzylidene ring, with the mean plane of the methylmalononitrile group being inclined to this ring by 5.8 (1)°. In the crystal, the mol­ecules are linked by weak C—H⋯N hydrogen bonds into layers parallel to the bc plane.

Evaluation of BDE-47 hydroxylation metabolic pathways based on a strong electron-withdrawing pentafluorobenzoyl derivatization gas chromatography/electron capture negative ionization quadrupole mass spectrometry.

Understanding the metabolic pathways of polybrominated diphenyl ethers (PBDEs) is a key issue in the evaluation of their cytotoxicity after they enter the biota. In order to obtain more information concerning the metabolic pathways of PBDEs, we developed a strong electron-withdrawing pentafluorobenzoyl (PFBoyl) derivatization capillary gas chromatography/electron capture negative ionization quadrupole mass spectrometry (GC/ECNI-qMS). PFBoyl esterification greatly improves separation of the metabolites of PBDEs such as hydroxylated PBDEs (OH-PBDEs) and bromophenols (BPs) metabolites in rat liver microsomes (RLMs). On the other hand, the strong electron-withdrawing property of PFBoyl derivatized on OH-PBDEs and/or BPs makes cleavage of the ester bond on ECNI easier resulting in higher abundance of the structure-informative characteristic fragment ions at a high m/z region, which facilitate the identification of OH-PBDEs metabolites. Subsequent quantification can be performed by monitoring not only 79Br- (or 81Br-) but also their characteristic fragment ions, achieving more accurate isotope dilution quantification using GC/ECNI-qMS. These merits allow us to identify totally 12 metabolites of BDE-47, a typical example of PBDEs, in the RLMs in vitro incubation systems. In addition to the already known metabolites of BDE-47, one dihydroxylated 3,6-di-OH-BDE-47 and one dihydroxylated 3,5-di-OH-tetrabrominated dioxin were found. Moreover, the second hydroxylation took place on the same bromophenyl ring, where the first hydroxyl group was located, and was further confirmed via the identification of the dihydroxylated 2',6'-di-OH-BDE-28 of an asymmetric 2'-OH-BDE-28. This methodological development and its subsequent findings of the metabolic pathways of BDE-47 provided experimental evidence for understanding its dioxin-like behavior and endocrine disrupting risk.

4-Bromo-N-(pyridin-2-ylmethylidene)aniline-κ2N,N′]iodido(triphenylphosphane-κP)copper(I)

In the title compound, [CuI(C12H9BrN2)(C18H15P)], the CuI ion is bonded to one I atom, one triphenyl­phosphane P atom and two N atoms of the diimine ligand in a distorted tetra­hedral geometry. The Schiff base acts as a chelating ligand and coordinates to the CuI atom via two N atoms. In the diimine ligand, the dihedral angle between the pyridine and bromo­phenyl rings is 19.2 (2)°. In the crystal, mol­ecules are connected by π–π stacking inter­actions between inversion-related pyridine rings [centroid–centroid distance = 3.404 (3) Å].

Ethyl (3E)-3-[2-(4-bromophenylsulfonyl)hydrazin-1-ylidene]butanoate

The asymmetric unit of title compound, C12H15BrN2O4S, contains two mol­ecules (A and B), with slightly different conformations: the bromo­phenyl rings and the SO2 planes of the sulfonyl groups are oriented at dihedral angles of 50.2 (2) (mol­ecule A) and 58.24 (7)° (mol­ecule B), and the ethyl acetate groups make dihedral angles of 63.99 (19)° (A) and 65.35 (16)° (B) with their bromo­phenyl groups. In the crystal, both mol­ecules exist as inversion dimers linked by pairs of N—H⋯O hydrogen bonds, which generate R 2 2(14) loops. The dimers are linked by C—H⋯O inter­actions.

4-Bromobenzoic acid–6-(4-bromophenyl)-3-methyl-1,2,4-triazolo[3,4-b][1,3,4]thiadiazole (1/1)

In the title 1:1 co-crystal, C10H7BrN4S·C7H5BrO2, the triazolothia­diazole system is approximately planar [with a maximum deviation of 0.030 (4) Å] and forms a dihedral angle of 8.6 (1)° with the bromo­phenyl ring. In the carb­oxy­lic acid mol­ecule, the carboxyl group is rotated by 6.4 (3)° out of the benzene ring plane. The crystal structure features O—H⋯N and C—H⋯O hydrogen bonds, π–π stacking inter­actions [centroid–centroid distances = 3.713 (2), 3.670 (2) and 3.859 (3) Å] and short S⋯N [2.883 (4) Å] contacts.

Ethyl 2-(4-bromophenyl)-1-sec-butyl-1H-benzimidazole-5-carboxylate

In the title compound, C20H21BrN2O2, the bromo­phenyl ring is twisted by 40.13 (8)° from the benzimidazole mean plane and the Br atom deviates by 0.753 (1) Å from that plane. The sec-butyl group is disordered over two conformations in a 0.898 (5):0.102 (5) ratio. In the crystal, mol­ecules related by translation along [10] are linked into chains via weak C—H⋯Br hydrogen bonds.

(9R,10R,10aR)-9-(2-Bromophenyl)-10-nitro-6-phenyl-10,10a-dihydro-9H-benzo[c]chromene-8-carbaldehyde

The title compound, C26H18BrNO4, features a functionalized chromene. The cyclo­hexene ring adopts a sofa conformation and has the nitro group and the bromo­phenyl ring in an axial position. The ten atoms of the chromene moiety lie close to a common plane (r.m.s. deviation = 0.066 Å). The attached phenyl ring is twisted by 32.89 (10)° from the chromene plane. The crystal packing is stabilized by C—H⋯O inter­actions.

Ethyl 1-benzyl-3-(4-bromophenyl)-1H-pyrazole-5-carboxylate

In the title compound, C19H17BrN2O2, the pyrazole ring makes dihedral angles of 88.00 (16) and 5.78 (13)° with the phenyl and bromo­phenyl rings, respectively. In the crystal, mol­ecules are linked by weak inter­molecular C—H⋯O hydrogen bonds.

25,26,27,28-Tetrakis(3-bromobenzyloxy)calix[4]arene

In the title compound, C56H44Br4O4, the calix[4]arene unit displays the 1,2-alternate conformation with crystallograpically imposed inversion symmetry. The four phen­oxy rings of the calix[4]arene unit are twisted about the mean plane defined by the four methyl­ene C atoms bridging the benzene rings, with dihedral angles of 46.73 (6) and 66.11 (5)°. The dihedral angle between adjacent phen­oxy rings is 74.75 (7)°. The two pendant bromo­phenyl rings on the same side of the calix[4]arene unit are nearly perpendicular to each other, with a dihedral angle of 72.85 (10)° due to an intra­molecular C—H⋯π inter­action. In the crystal, a Br⋯Br contact of 3.6350 (5) Å, an inter­molecular C—H⋯Br hydrogen bond and an inter­molecular C—H⋯π inter­action are observed.

2,3-Dibromo-3-(2-bromophenyl)-1-(3-phenylsydnon-4-yl)propan-1-one

In the title compound [systematic name: 2,3-dibromo-3-(2-bromo­phen­yl)-1-(5-oxido-3-phenyl-1,2,3-oxadiazol-3-ium-4-yl)propan-1-one], C17H11Br3N2O3, the oxadiazole ring is essentially planar, with a maximum deviation of 0.003 (1) Å. The –CHBr–CHBr– chain and bromo­phenyl ring are disordered over two sets of sites with a refined occupany ratio of 0.756 (5):0.244 (5). The central oxadiazole ring makes dihedral angles of 54.07 (11) and 13.76 (18)° with the attached phenyl and the major component of the bromo-substituted benzene rings, respectively. The dihedral angle between the major and minor components of the bromo­phenyl rings is 13.4 (5)°. In the crystal structure, mol­ecules are connected by C—H⋯O hydrogen bonds, forming [010] ribbons.

Ethyl 7-(4-bromophenyl)-5-trifluoromethyl-4,7-dihydrotetrazolo[1,5-a]pyrimidine-6-carboxylate

In the title compound, C14H11BrF3N5O2, the pyrimidine ring adopts a flattened envelope conformation with sp 3-hybridized carbon as the flap [deviation = 0.177 (3) Å]. The dihedral angle between tetra­zole and bromo­phenyl rings is 84.3 (1)°. In the crystal, mol­ecules are linked into centrosymmetric dimers by pairs of N—H⋯N hydrogen bonds.