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With alkyl carbazates as the green ester source, a novel palladium‐catalyzed oxidative free radical carbonylative transformation of the C–H bond on aromatic rings to produce esters has been developed. Good yields of the corresponding products have been obtained with wide functional group tolerance and excellent regioselectivity. A variety of alkyl carbazates are found to be suitable reactants for the ortho‐alkoxycarbonylation on the aromatic ring. [ABSTRACT FROM AUTHOR]

In the title compound, C14H15N3O4S, the tetra­hydro­pyrimidine ring adopts a half-boat form. There are inter­molecular N—H⋯O hydrogen bonds and π–π stacking inter­actions. [ABSTRACT FROM AUTHOR]

The title compound, C12H22ClNO, adopts the square conform­ation [3333] observed in other known saturated twelve-membered rings. Disorder is observed, resulting from exchange of the chloro and nitroso substituents. [ABSTRACT FROM AUTHOR]

The title compound, C21H24O6, is the reduced form of curcumin, and exhibits important cosmoceutical properties. The molecule is non-planar and the benzene rings positioned at the ends of the heptane chain are orthogonally placed, with a dihedral angle of 84.09 (7)° between them. The molecular geometry and H-atom locations reveal that the 'heptane-3,5dione' moiety exists in the keto-enol form, with the hydroxy H atom disordered over two adjacent sites. The packing of the molecules in the lattice is directed by strong O-H···O intermolecular hydrogen bonds, which generate two-dimensional sheets. These sheets are linked by C-H···O hydrogen bonds and weak C-H···π interactions to develop a threedimensional network. [ABSTRACT FROM AUTHOR]

In the title compound, C22H16N2S2, the benzothiazole and tolyl ring systems are inclined at an angle of 31.23 (8)°, and the dihedral angle between the phenyl and benzothiazole rings is 7.567 (2)°. In the crystal structure, intermolecular C—H...N hydrogen bonds link the molecules into a two-dimensional sheet and π–π stacking interactions [perpendicular distance 3.6170 (4) Å] reinforce the crystal cohesion. [ABSTRACT FROM AUTHOR]

The crystal structure of the title compound, C17H20N2O5, is stabilized by C—H...O and N—H...O hydrogen bonds. [ABSTRACT FROM AUTHOR]

In the title compound, C14H13N3O2S, the imidazothia­diazole ring system and the methoxy­phenyl ring are not coplanar, having an angle of 31.60 (7)° between their mean planes. In the crystal structure, inter­molecular C—H⋯O hydrogen-bond inter­actions link the mol­ecules into dimers and π–π stacking inter­actions reinforce the crystal cohesion. [ABSTRACT FROM AUTHOR]

In the title compound, C14H10O4S2·0.5CH3OH, the molecule adopts a gauche conformation around the central C—C bond. Intermolecular O—H...O hydrogen bonds between carboxyl groups link the molecules into zigzag chains. Between chains, the thiophene rings form π–π stacking interactions with a centroid–centroid distance of 3.98 Å. The methanol solvent molecule forms an O—H...O hydrogen bond to one carboxyl group and is disordered about a crystallographic centre of inversion. [ABSTRACT FROM AUTHOR]

In the title mol-ecule, C23H18F2N2O3S, the 4-fluoro-substituted and 2-fluoro-substituted benzene rings form dihedral angles of 88.16 (8) and 23.1 (1)°, respectively, with the thia-zole ring. The pyrimidine ring adopts a flattened sofa conformation with the sp (3)-hydridized C atom forming the flap. In the crystal, pairs of weak C-H⋯O hydrogen bonds link mol-ecules related by twofold rotation axes, forming R (2) 2(10) rings, which are in turn linked by weak C-H⋯N inter-actions to form chains of rings along [010]. In addition, weak C-H⋯π(arene) inter-actions link the chains into layers parallel to (001) and π-π inter-actions with a centroid-centroid distance of 3.836 (10) Å connect these layers into a three-dimensional network.

The asymmetric unit of the title compound, C15H21N3OSi, contains two mol-ecules with similar conformations (r.m.s. overlay fit for the 20 non-H atoms = 0.163 Å). The dihedral angles between the planes of the 1,2,3-triazole and 2,4-di-methyl-benzene rings are 27.0 (3) and 19.5 (3)°. In the crystal, mol-ecules are linked by very weak C-H⋯O and C-H⋯N hydrogen bonds to generate [100] chains. The chains are cross-linked by C-H⋯π inter-actions.

In the title mol-ecule, C20H22N2O4S, the pyrimidine ring is in a flattened half-chair conformation and the 3-meth-oxyphenyl substituent is in an axial arrangement. The thia-zole ring forms a dihedral angle of 81.3 (1)° with the benzene ring. In the crystal, weak C-H⋯S inter-actions link mol-ecules into chains along [001]. In addition, there are π-π inter-actions between inversion-related thia-zole rings with a centroid-centroid distance of 3.529 (2) Å. The ethyl group was refined as disordered over two sets of sites with an occupancy ratio of 0.52 (3):0.48 (2).

In the title mol-ecule, C23H18F2N2O3S, the pyrimidine ring is in a half-chair conformation and the 3-fluoro-phenyl group is in the axial position. The thia-zole ring (r.m.s. deviation = 0.0252 Å) forms dihedral angles of 84.8 (7) and 9.6 (7)° with the 3-fluoro-substituted and 4-fluoro-substituted benzene rings, respectively. In the crystal, weak C-H⋯F and C-H⋯O hydrogen bonds connect mol-ecules, forming zigzag chains along the b axis. In addition π-π stacking inter-actions with a centroid-centroid distance of 3.7633 (9) Å connect these chains into ladders via inversion-related 4-fluoro-phenyl groups.

In the title compound, C14H9F3N2, the mean planes of the benzimidazole ring system and the tri-fluoro-methyl-substituted benzene ring form a dihedral angle of 30.1 (1)°. In the crystal, mol-ecules are linked by N-H⋯N hydrogen bonds into chains along [010]. Weak C-H⋯F hydrogen bonds and a weak C-H⋯π inter-action connect the chains into a two-dimensional network parallel to (001).

In the title mol-ecule, C13H14N2O3S, the di-hydro-pyrimidine ring is in a flattened sofa conformation, with the methine C atom forming the flap. The dihedral angle between the mean plane of the five essentially planar atoms of the di-hydro-pyrimidine ring [maximum deviation = 0.056 (4) Å] and the benzene ring is 89.4 (2)°. The O atom of the carbonyl group is in a trans conformation with respect to the C=C bond of the di-hydro-pyrimidine ring. In the crystal, N-H⋯O and O-H⋯S hydrogen bonds connect mol-ecules, forming a two-dimensional network parallel to (001).

In the title mol-ecule, C13H8F2N2, the dihedral angle between the benzimidazole ring system and the di-fluoro-substituted benzene ring is 30.0 (1)°. In the crystal, mol-ecules are linked by N-H⋯N hydrogen bonds, forming chains along [010]. In addition, weak C-H⋯F hydrogen bonds connect chains into a two-dimensional network parallel to (001). A weak C-H⋯π inter-action is observed between an H atom of the benzimidazole ring sytem and the π system of the di-fluoro-substituted benzene ring.

The asymmetric unit of the title compound, C12H12ClNOS, contains three independent mol-ecules, with the thio-chroman ring adopting a sofa conformation in each one. The crystal structure features C-H⋯O inter-actions; one of the O atoms accepts three such bonds. Together, the hydrogen bonds give rise to a molecular tape propagating in [010].

In the title mol-ecule, C24H19BrN2O5S, the pyrimidine ring is in a flattened half-chair conformation and the 4-acet-oxy-phenyl group is substituted axially to this ring. The thia-zole ring is essentially planar [with a maximum deviation of 0.012 (2) Å for the N atom] and forms dihedral angles of 17.65 (13) and 88.95 (11)° with the bromo- and acet-oxy-substituted benzene rings, respectively. The dihedral angle between the benzene rings is 81.84 (13) Å. In the crystal, pairs of weak C-H⋯O hydrogen bonds lead to the formation of inversion dimers. A weak C-H⋯π inter-action and π-π stacking inter-actions with centroid-centroid distances of 3.5903 (14) Å are observed.

In the crystal structure of the title compound, C14H15BrO2, weak C-H⋯O inter-actions link the mol-ecules into zigzag chains extending along the c-axis direction. These chains are further assembled into (100) layers via π-π stacking inter-actions between inversion-related chromenone fragments [inter-planar distance = 3.376 (2) Å].

In the title compound, C(14)H(9)F(3)N(2)O, the best planes of the benzimidazole group and benzene ring form a dihedral angle of 26.68 (3)°. In the crystal, N-H⋯N hydrogen bonds link the mol-ecules into infinite chains parallel to the c axis. Stacking inter-actions between the benzimidazole groups [centroid-centroid distance = 3.594 (5) Å] assemble the mol-ecules into layers parallel to (100). The trifluoro-methyl group is disordered over three sets of sites with site-occupancy factors of 0.787 (4), 0.107 (7) and 0.106 (7).

In the title compound, C(20)H(22)N(2)O(4)S, the central pyrimidine ring incorporating a chiral C atom is significantly puckered and adopts a slight boat conformation with C atom bearing the phenyl ring and the N atom opposite displaced by 0.367 (2) and 0.107 (2) Å, respectively, from the plane formed by the remaining ring atoms. The benzene ring is positioned axially to the pyrimidine ring, making a dihedral angle of 88.99 (5)°. The thia-zole ring is essentially planar (r.m.s. deviation = 0.0033 Å). In the crystal, pairs of C-H⋯O inter-actions result in centrosymmetric dimers with graph-set motifs R(1) (2)(7) and R(2) (2)(8). A weak C-H⋯π contact is also observed.

In the title compound, C(10)H(12)N(2)S, the thio-phene ring is essentially planar (r.m.s. deviation = 0.0290 Å). The two C atoms of the cyclo-hexene ring (at positions 6 and 7) are disordered over two sets of sites in a 0.810 (5):0.190 (5) ratio. The cyclo-hexene rings in both the major and minor occupancy conformers adopt a half-chair conformation. In the crystal, there are two types of N-H⋯N inter-action. One of these results in centrosymmetric head-to-head dimers corresponding to an R(2) (2)(12) graph-set motif and the other forms a 20-membered macrocyclic ring involving six mol-ecules.

In the title compound, C(12)H(16)N(4)S, the fused benzothio-phene and the pyrimidine rings are coplanar [dihedral angle = 1.61 (6)°]. Three C atoms of the cyclohexene ring (at positions 3, 6 and 7) are disordered over two sites with an occupancy ratio of 0.702 (8):0.298 (8). The cyclo-hexene ring in both the major and minor components adopts a half-chair conformation. The crystal structure is stabilized by N-H⋯N and C-H⋯N inter-actions, resulting in the formation of inversion dimers with R(2) (2)(10) and R(2) (2)(12) graph-set motifs.

In the title compound, C(7)H(7)ClN(4)O, the pyrazolo-pyrimidine ring is essentially planar, the r.m.s. deviation of the fitted atoms being 0.0071 Å. The crystal structure features strong N-H⋯O hydrogen bonds and further consolidated by weak C-H⋯O, C-H⋯N and C-H⋯Cl inter-actions.

In the title compound, C(17)H(20)N(2)O(4)S, the aryl ring is positioned perpendicular to the dihydro-pyrimidine ring, the dihedral angle between the ring planes being 77.48 (9)°. The carboxyl-ate and methyl groups are in a cis conformation with respect to the C=C bond. The dihydro-pyrimidine ring adopts a twist-boat conformation. The crystal structure is stabilized by N-H⋯O and C-H⋯O inter-actions, the former resulting in mol-ecular chains along the b axis and the latter forming inversion dimers.

In the title compound, C(22)H(17)BrN(2)O(4)S, the central dihydropyrimidine ring, with a chiral C atom, is significantly puckered and adopts a half-chair conformation with the chiral C atom displaced from the mean plane of the remaining ring atoms by 0.305 (6) Å. The hydroxy-phenyl ring is positioned axially to the pyrimidine ring and almost bisects it, the dihedral angle between the mean-planes of the two rings being 89.78 (12)°. The meth-oxy-carbonyl group is disordered over two sites with an occupancy ratio of 0.568 (5):0.432 (5), resulting in a major and a minor conformer. In the crystal, O-H⋯N and C-H⋯S inter-actions result in sheets along the c axis. The supra-molecular assembly is stabilized by π-π stacking inter-actions between the 2-bromo-benzyl-idene and thia-zolopyrimidine rings [centroid-centroid distance = 3.632 (1) Å]. In addition, C-H⋯π inter-actions are also observed in the crystal structure.

In the title compound, C(24)H(22)N(2)O(6)S, a pyrimidine ring substituted with 4-hy-droxy-3-meth-oxy-phenyl is fused with a thia-zole ring. The 4-hy-droxy-3-meth-oxy-phenyl group is positioned axially to the pyrimidine ring, making a dihedral angle 85.36 (7)°. The pyrimidine ring adopts a twist boat conformation. In the crystal, O-H⋯N inter-actions result in a chain running along the b axis. The carbonyl O atom bonded to the thia-zole ring is involved in two C-H⋯O hydrogen-bond inter-actions forming centrosymmetric dimers; the ten- and six-membered rings resulting from these inter-actions have R(2) (2)(10) and R(1) (2)(6) motifs, respectively.

In the title compound, C(11)H(13)N(3)S, two of the C atoms of the cyclo-hexene ring and the methyl group attached to it are disordered over two sets of sites in a 0.544 (2):0.456 (2) ratio. The benzothiene and pyrimidine rings are almost coplanar with an angular tilt of 2.371 (9)° between them. The thio-phene ring is essentially planar (r.m.s. deviation 0.05 Å), while the cyclo-hexene ring in both the major- and minor-occupancy conformers adopts a half-chair conformation. In the crystal structure, pairs of intermolecular N-H⋯N hydrogen bonds involving the amino groups result in centrosymmetric head-to-head dimers about inversion centres, corresponding to an R(2) (2)(8) graph-set motif. Further, N-H⋯N hydrogen bonding generates a two-dimensional hydrogen-bonded network perpendicular to the ac plane and running along the diagonal of the ac plane.

In the anion of the title compound, (C(14)H(13)N(2)S)(2)[CdBr(4)]·C(2)H(5)OH, the Cd(II) atom is in a distorted tetra-hedral environment and one of the Br atoms is disordered over three sites with site-occupancy factors of 0.828 (5), 0.106 (3) and 0.068 (4). In the crystal, inter-molecular N-H⋯O, C-H⋯O and N-H⋯Br inter-actions result in a two-dimensional polymeric network extending parallel to (010).

The asymmetric unit of the title compound, (C(14)H(13)N(2)S)(2)[CuBr(4)]·2H(2)O, contains two cations, one anion and two solvent water mol-ecules that are connected via O-H⋯Br, N-H⋯Br and N-H⋯O hydrogen bonds into a two-dimensional polymeric structure. The cations are arranged in a head-to-tail fashion and form stacks along [100]. The central Cu(II) atom of the anion is in a distorted tetra-hedral environment.

In the title compound, C(17)H(11)BrFN(3)S, the imidazothia-diazole and bromo-phenyl rings are individually almost planar, with maximum deviations of 0.0215 (4) and 0.0044 (4) Å, respectively, and are inclined at an angle of 27.34 (3)° with respect to each other. The dihedral angle between the mean planes of the fluoro-benzyl and imidazothia-diazole rings is 79.54 (3)°. The crystal structure is stabilized by inter-molecular C-H⋯N inter-actions resulting in chains of mol-ecules along the b axis.

In the title compound, C(17)H(14)N(4)S, the benzothieno moiety is fused at one end of the pyramidine ring while the triazole ring with a phenyl substituent is fused at the other side. The triazole ring is almost planar [maximum deviation = 0.0028 (3) Å] while the cyclo-hexane ring adopts a half-chair conformation. In the crystal, pairs of inter-molecular C-H⋯N hydrogen bonds form centrosymmetric head-to-head dimers, corresponding to an R(2) (2)(8) graph-set motif. Further C-H⋯N inter-actions generate a zigzag chain of mol-ecules along the c axis. The supra-molecular assembly is consolidated by π-π stacking inter-actions [centroid-centroid distance = 3.445 (4) Å].

In the title compound, C(10)H(12)N(2)S, one of the C atoms of the cyclo-hexene ring (at position 6) and the methyl group attached to it are disordered over two sets of sites in a 0.650 (3):0.350 (3) ratio. The cyclo-hexene ring in both the major and minor occupancy conformers adopts a half-chair conformation. The thio-phene ring is essentially planar (r.m.s. deviation = 0.05 Å). In the crystal, N-H⋯N hydrogen bonds involving the amino groups result in inversion dimers with R(2) (2)(12) graph-set motif. Further N-H⋯N hydrogen bonds involving the amino and carbonitrile groups generate zigzag chains along the a axis.

In the title compound, C(18)H(11)ClN(4)OS, the benzisoxazole and imidazothia-diazole rings are inclined at an angle of 23.81 (7)° with respect to each other. The imidazothia-diazole and chloro-phenyl rings make a dihedral angle of 27.34 (3)°. In the crystal, inter-molecular C-H⋯N inter-actions generate a chain along the c axis and C-H⋯O inter-actions form centrosymmetric dimers resulting in an R(2) (2)(26) graph-set motif. Moreover, the C-H⋯N and S⋯N [3.206 (4) Å] inter-actions links the mol-ecules into R(7) ring motifs. The packing is further stabilized by π-π stacking inter-actions between the thia-diazole rings with a shortest centroid-centroid distance of 3.497 (3) Å. In addition, C-H⋯π inter-actions are observed in the crystal structure.

In the cation of the title compound, C(14)H(13)N(2)S(+)·Br(-), the essentially planar benzimidazole system (r.m.s. deviation = 0.0082 Å) is substituted with a 4-methyl-sulfanylphenyl ring. The dihedral angle between the benzimidazole system and the 4-methyl-sulfanylphenyl ring is 2.133 (2)°. The crystal structure is characterized by strong and highly directional inter-molecular N-H⋯Br hydrogen bonds involving the bromide ion. Moreover, C-H⋯S inter-actions result in chains of mol-ecules along the c axis. The supra-molecular assembly is further stabilized by π-π stacking inter-actions between the benzimidazole system and 4-methyl-sulfanylphenyl rings [centroid-centroid distance = 3.477 (4) Å].

In the title compound, C(18)H(11)BrN(4)OS, the imidazothia-diazole and benzisoxazole rings are individually planar with maximum deviations of 0.025 (3) 0.015 (4) Å, respectively, and are inclined at an angle of 23.51 (7)° with respect to each other. The planes of the imidazothia-diazole and bromo-phenyl rings are inclined at an angle of 27.34 (3)°. In the crystal, inter-molecular C-H⋯N inter-actions result in chains of mol-ecules along the b and c axes. Moreover, C-H⋯O inter-actions result in centrosymmetric head-to-head dimers with R(2) (2)(24) graph-set motifs. The mol-ecular packing is further stabilized by π-π stacking inter-actions between the imidazole rings with a shortest centroid-centroid distance of 3.492 (3) Å. In addition, C-H⋯π inter-actions are observed in the crystal structure.

In the title compound, C(9)H(8)N(2)OS, the benzothio-phene ring is substituted with amino, oxo and carbonitrile groups. The thio-phene ring is essentially planar (r.m.s. deviation = 0.0003 Å), while the cyclo-hexene ring is in a half-chair conformation. In the crystal, N-H⋯O hydrogen bonds generate chains of mol-ecules in a zigzag pattern along the b axis. Pairs of N-H⋯N hydrogen bonds form centrosymmetric head-to-head dimers about inversion centres, corresponding to an R(2) (2)(12) graph-set motif. In addition, rather weak N-H⋯S inter-actions are also present in the structure and the supra-molecular assembly is further consolidated by π-π stacking inter-actions between the benzothio-phene rings, disposed at a distance of 3.742 (3) Å.

The crystal and molecular structure of the title compound, C(15)H(26)O(4)Si(2), reveals a self-assembly facilitated via the rare co-existence of dimeric and catemeric patterns, which is attributed to the influence of the trimethylsilyl groups. The structure is dicussed in the context of a database search and subsequent analysis of structures of cis-1,2-dicarboxylic acids.