Reduced 3,4'-bi-pyrazoles carrying thio-phene and thia-zole substituents: structures of two intermediates and two products.

Cyclo-addition reactions between 3-(5-ar-yloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-(thio-phen-2-yl)prop-2-en-1-ones and thio-semicarbazide leads to the formation of reduced 3,4'-bi-pyrazole-2-carbo-thio-amides. Further cyclo-addition of these inter-mediates with either diethyl acetyl-enedi-carboxyl-ate or 4-bromo-phenacyl bromide leads to reduced 3,4'-bi-pyrazoles carrying oxo-thia-zole or thia-zole substituents, respectively. The structures of two representative inter-mediates and two representative products established unambiguously the regiochemistry of the cyclo-addition reactions. The mol-ecules of 3'-methyl-5'-(2-methyl-phen-oxy)-1'-phenyl-5-(thio-phen-2-yl)-3,4-di-hydro-1'H,2H-3,4'-bi-pyra-zole-2-carbo-thio-amide, C25H23N5OS2 (Ia), are linked by N-H⋯N hydrogen bonds to form simple C(8) chains. The analogous compound 5'-(2,4-di-chloro-phen-oxy)-3'-methyl-1'-phenyl-5-(thio-phen-2-yl)-3,4-di-hydro-1'H,2H-3,4'-bi-pyra-zole-2-carbo-thio-amide hemihydrate crystallizes as a hemihydrate, C24H19Cl2N5OS2·0.5H2O (Ib), and the independent components are linked into a chain of spiro-fused R 4 4(20) rings by a combination of O-H⋯N and N-H⋯O hydrogen bonds. In the structure of ethyl (Z)-2-{2-[3'-methyl-1'-phenyl-5-(thio-phen-2-yl)-5'-(2-methyl-phen-oxy)-3,4-di-hydro-1'H,2H-3,4'-bi-pyrazole-2-yl]-4-oxo-4,5-di-hydro-thia-zol-5-yl-idene}acetate, C31H27N5O4S2 (II), inversion-related pairs of mol-ecules are linked by paired C-H⋯π(arene) hydrogen bonds to form cyclic centrosymmetric dimers, but there are no direction-specific inter-molecular inter-actions in 4-(4-bromo-phen-yl)-2-[5'-(2,4-di-chloro-phen-oxy)-3'-methyl-1'-phenyl-5-(thio-phen-2-yl)-3,4-di-hydro-1'H,2H-3,4'-bi-pyrazole-2-yl]-4-thia-zole, C32H22BrCl2N5OS2 (III). Comparisons are made with the structures of some related compounds.

The crystal structures of three disordered 2-substituted benzimidazole esters.

The crystal structures of three benzimidazole esters containing aryl or heterocyclic substituents at position 2 are reported, and all three exhibit disorder of mol-ecular entities. In ethyl 1-methyl-2-[4-(prop-2-yn-oxy)phen-yl]-1H-benzimidazole-5-carboxyl-ate, C20H18N2O3, (I), the prop-2-yn-1-oxyphenyl unit is disordered over two sets of atomic sites having effectively equal occupancies, 0.506 (5) and 0.494 (5). The propyl substituent in ethyl 1-propyl-2-(pyren-1-yl)-1H-benzimidazole-5-carboxyl-ate, C29H24N2O2, (II), is disordered over two sets of atomic sites having occupancies 0.601 (8) and 0.399 (8), and the ester unit in ethyl 1-methyl-2-(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1H-benzimidazole-5-carboxyl-ate, C21H19ClN4O2 (III), is disordered over two sets of atomic sites having occupancies 0.645 (7) and 0.355 (7). In each of the C-H⋯π(arene) hydrogen bonds in (I), the donor and acceptor form parts of different disorder components, so that no continuous aggregation is possible. The mol-ecules of (II) are linked by a single C-H⋯O hydrogen bond into C(10) chains, which are linked into sheets by a π-π stacking inter-action, whereas those of (III) are just linked into C(13) chains, again by a single C-H⋯O hydrogen bond. Comparisons are made with the structures of some related compounds.

Functionalized 3-(5-ar-yloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-(4-substituted-phen-yl)prop-2-en-1-ones: synthetic pathway, and the structures of six examples.

Five examples each of 3-(5-ar-yloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-[4-(prop-2-yn-1-yl-oxy)phen-yl]prop-2-en-1-ones and the corresponding 1-(4-azido-phen-yl)-3-(5-ar-yloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)prop-2-en-1-ones have been synthesized in a highly efficient manner, starting from a common source precursor, and structures have been determined for three examples of each type. In each of 3-[5-(2-chloro-phen-oxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl]-1-[4-(prop-2-yn-1-yl-oxy)phen-yl]prop-2-en-1-one, C28H21ClN2O3, (Ib), the isomeric 3-[5-(2-chloro-phen-oxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl]-1-[4-(prop-2-yn-1-yl-oxy)phen-yl]prop-2-en-1-one, (Ic), and 3-[3-methyl-5-(naphthalen-2-yl-oxy)-1-phenyl-1H-pyrazol-4-yl]-1-[4-(prop-2-yn-yloxy)phen-yl]prop-2-en-1-one, C32H24N2O3, (Ie), the mol-ecules are linked into chains of rings, formed by two independent C-H⋯O hydrogen bonds in (Ib) and by a combination of C-H⋯O and C-H⋯π(arene) hydrogen bonds in each of (Ic) and (Ie). There are no direction-specific inter-molecular inter-actions in the structure of 1-(4-azido-phen-yl)-3-[3-methyl-5-(2-methyl-phen-oxy)-1-phenyl-1H-pyrazol-4-yl]prop-2-en-1-one, C26H21N5O2, (IIa). In 1-(4-azido-phen-yl)-3-[5-(2,4-di-chloro-phen-oxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl]prop-2-en-1-one, C25H17Cl2N5O2, (IId), the di-chloro-phenyl group is disordered over two sets of atomic sites having occupancies 0.55 (4) and 0.45 (4), and the mol-ecules are linked by a single C-H⋯O hydrogen bond to form cyclic, centrosymmetric R 2 2(20) dimers. Similar dimers are formed in 1-(4-azido-phen-yl)-3-[3-methyl-5-(naphthalen-2-yl-oxy)-1-phenyl-1H-pyrazol-4-yl]prop-2-en-1-one, C29H21N5O2, (IIe), but here the dimers are linked into a chain of rings by two independent C-H..π(arene) hydrogen bonds. Comparisons are made between the mol-ecular conformations within both series of compounds.

Conversion of di-aryl-chalcones into 4,5-di-hydro-pyrazole-1-carbo-thio-amides: mol-ecular and supra-molecular structures of two precursors and three products.

Chalcones of type 4-XC6H4C(O)CH=CHC6H4(OCH2CCH)-4, where X = Cl, Br or MeO, have been converted to the corresponding 4,5-di-hydro-pyrazole-1-carbo-thio-amides using a cyclo-condensation reaction with thio-semicarbazide. The chalcones 1-(4-chloro-phen-yl)-3-[4-(prop-2-yn-yloxy)phen-yl]prop-2-en-1-one, C18H13ClO2, (I), and 1-(4-bromo-phen-yl)-3-[4-(prop-2-yn-yloxy)phen-yl]prop-2-en-1-one, C18H13BrO2, (II), are isomorphous, and their mol-ecules are linked into sheets by two independent C-H⋯π(arene) inter-actions, both involving the same aryl ring with one C-H donor approaching each face. In each of the products (RS)-3-(4-chloro-phen-yl)-5-[4-(prop-2-yn-yloxy)phen-yl]-4,5-di-hydro-pyrazole-1-carbo-thio-amide, C19H16ClN3OS, (IV), (RS)-3-(4-bromo-phen-yl)-5-[4-(prop-2-yn-yloxy)phen-yl]-4,5-di-hydro-pyrazole-1-carbo-thio-amide, C19H16BrN3OS, (V), and (RS)-3-(4-meth-oxy-phen-yl)-5-[4-(prop-2-yn-yloxy)phen-yl]-4,5-di-hydro-pyrazole-1-carbo-thio-amide, C20H19N3O2S, (VI), the reduced pyrazole ring adopts an envelope conformation with the C atom bearing the 4-prop-2-yn-yloxy)phenyl substituent, which occupies the axial site, displaced from the plane of the four ring atoms. Compounds (IV) and (V) are isomorphous and their mol-ecules are linked into chains of edge-fused rings by a combination of N-H⋯S and C-H⋯S hydrogen bonds. The mol-ecules of (VI) are linked into sheets by a combination of N-H⋯S, N-H⋯N and C-H⋯π(arene) hydrogen bonds. Comparisons are made with the structures of some related compounds.