The crystal structures and Hirshfeld surface analyses of four 3,5-diacetyl-2-methyl-2,3-di-hydro-1,3,4-thia-diazol-2-yl derivatives.

The title compounds, 4-(5-acetamido-3-acetyl-2-methyl-2,3-di-hydro-1,3,4-thia-diazol-2-yl)phenyl benzoate, C20H19N3O4S (I), 4-(5-acetamido-3-acetyl-2-methyl-2,3-di-hydro-1,3,4-thia-diazol-2-yl)phenyl isobutyrate 0.25-hydrate, C17H21N3O4S·0.25H2O (II), 4-(5-acetamido-3-acetyl-2-methyl-2,3-di-hydro-1,3,4-thia-diazol-2-yl)phenyl propionate, C16H19N3O4S (III) and 4-(5-acetamido-3-acetyl-2-methyl-2,3-di-hydro-1,3,4-thia-diazol-2-yl)phenyl cinnamate chloro-form hemisolvate, C22H21N3O4S·0.5CHCl3 (IV), all crystallize with two independent mol-ecules (A and B) in the asymmetric unit in the triclinic P space group. Compound II crystallizes as a quaterhydrate, while compound IV crystallizes as a chloro-form hemisolvate. In compounds I, II, III (mol-ecules A and B) and IV (mol-ecule A) the five-membered thia-diazole ring adopts an envelope conformation, with the tetra-substituted C atom as the flap. In mol-ecule B of IV this ring is flat (r.m.s. deviation 0.044 Å). The central benzene ring is in general almost normal to the mean plane of the thia-diazole ring in each mol-ecule, with dihedral angles ranging from 75.8 (1) to 85.5 (2)°. In the crystals of all four compounds, the A and B mol-ecules are linked via strong N-H⋯O hydrogen bonds and generate centrosymmetric four-membered R 4 4(28) ring motifs. There are C-H⋯O hydrogen bonds present in the crystals of all four compounds, and in I and II there are also C-H⋯π inter-actions present. The inter-molecular contacts in the crystals of all four compounds were analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.

Crystal structures of two new isocoumarin derivatives: 8-amino-6-methyl-3,4-diphenyl-1H-isochromen-1-one and 8-amino-3,4-diethyl-6-methyl-1H-isochromen-1-one.

The title compounds, 8-amino-6-methyl-3,4-diphenyl-1H-isochromen-1-one, C22H17NO2, (I), and 8-amino-3,4-diethyl-6-methyl-1H-isochromen-1-one, C14H17NO2, (II), are new isocoumarin derivatives in which the isochromene ring systems are planar. Compound II crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. In I, the two phenyl rings are inclined to each other by 56.41 (7)° and to the mean plane of the 1H-isochromene ring system by 67.64 (6) and 44.92 (6)°. In both compounds, there is an intra-molecular N-H⋯O hydrogen bond present forming an S(6) ring motif. In the crystal of I, mol-ecules are linked by N-H⋯π inter-actions, forming chains along the b-axis direction. A C-H⋯π inter-action links the chains to form layers parallel to (100). The layers are then linked by a second C-H⋯π inter-action, forming a three-dimensional structure. In the crystal of II, the two independent mol-ecules (A and B) are linked by N-H⋯O hydrogen bonds, forming -A-B-A-B- chains along the [101] direction. The chains are linked into ribbons by C-H⋯π inter-actions involving inversion-related A mol-ecules. The latter are linked by offset π-π inter-actions [inter-centroid distances vary from 3.506 (1) to 3.870 (2) Å], forming a three-dimensional structure.

Crystal structure and Hirshfeld surface analysis of 2-[(2-oxo-2H-chromen-4-yl)-oxy]acetic acid dimethyl sulfoxide monosolvate.

The title compound, C11H8O5·(CH3)2SO, is a new coumarin derivative. The asymmetric unit contains two coumarin mol-ecules (A and B) and two di-methyl-sulfoxide solvent mol-ecules (A and B). The dihedral angle between the pyran and benzene rings in the chromene moiety is 3.56 (2)° for mol-ecule A and 1.83 (2)° for mol-ecule B. In mol-ecule A, the dimethyl sulfoxide sulfur atom is disordered over two positions with a refined occupancy ratio of 0.782 (5):0.218 (5). In the crystal, mol-ecules are linked by O-H⋯O hydrogen bonds, forming chains running along the c-axis direction. The chains are linked by C-H⋯O hydrogen bonds, forming layers parallel to the ac plane. In addition, there are also C-H⋯π and π-π inter-actions present within the layers. The inter-molecular contacts in the crystal have been analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots, which indicate that the most important contributions to the packing are from H⋯H (33.9%) and O⋯H/H⋯O (41.2%) contacts.

The crystal structures of two new coumarin derivatives: 2-(4-{2-[(2-oxo-2H-chromen-4-yl)-oxy]acet-yl}piperazin-1-yl)acetamide and N-(2,4-di-meth-oxy-benz-yl)-2-[(2-oxo-2H-chromen-4-yl)-oxy]acetamide.

The title compounds, 2-(4-{2-[(2-oxo-2H-chromen-4-yl)-oxy]acet-yl}piperazin-1-yl)acetamide, C17H19N3O5, (I), and N-(2,4-di-meth-oxy-benz-yl)-2-[(2-oxo-2H-chromen-4-yl)-oxy]acetamide, C20H19NO6, (II), are new coumarin derivatives. In compound (I), the six-membered piperazine adopts a chair conformation. The dihedral angles between the mean planes of the chromene ring and amide plane is 82.65 (7)° in (I) and 26.2 (4)° in (II). The dihedral angles between the mean planes of the chromene ring and the four planar C atoms of the piperazine ring in (I) and the benzene ring in (II) are 87.66 (6) and 65.0 (4)°, respectively. There are short intra-molecular contacts in both mol-ecules forming S(5) ring motifs, viz. N-H⋯N and C-H⋯O in (I), and N-H⋯O and C-H⋯N in (II). In the crystals of both compounds, mol-ecules are linked by N-H⋯O hydrogen bonds, forming chains along [10] in (I) and [010] in (II). The chains are linked by C-H⋯O hydrogen bonds, forming layers parallel to the ab plane in the crystals of both compounds. In the crystal of (I), there are also C-H⋯π and offset π-π inter-actions [inter-centroid distance = 3.691 (1) Å] present within the layers. In the crystal of (II), there are only weak offset π-π inter-actions [inter-centroid distance = 3.981 (6) Å] present within the layers. The inter-molecular contacts in the crystals of both compounds have been analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.

The crystal structures and Hirshfeld surface analysis of N',N'''-((1E,1'E)-{[methyl-enebis(-oxy)]bis-(6-bromo-3,1-phenyl-ene)}bis-(methan-ylyl-idene))bis-(isonicotinohydrazide) dihydrate and N',N'''-((1E,1'E)-{[butane-1,4-diylbis(-oxy)]bis-(2,1-phenyl-ene)}bis-(methan-ylyl-idene))bis-(isonicotino-hydrazide) [+ solvent].

The title compounds, C27H20Br2N6O4·2H2O, (I), and C30H28N6O4·[+ solvent], (II), both crystallize with one half-mol-ecule in the asymmetric unit. The whole mol-ecule of (I) is generated by twofold rotation symmetry, with the twofold rotation axis bis-ecting the C atom of the -O-CH2-O- bridge. This results in a folded or U-shaped conformation of the mol-ecule. The whole mol-ecule of (II) is generated by inversion symmetry, with the central CH2-CH2 bond of the -O-(CH2)4-O- bridge being located about a center of inversion. This results in a step-like conformation of the mol-ecule. The central C(=O)N-N=C regions of the isonicotinohydrazide moieties in both compounds are planar and the configuration about the imine C=N bonds is E. In compound (I), the benzene and pyridine rings are inclined to each other by 37.60 (6)°. The two symmetry-related pyridine rings are inclined to each other by 74.24 (6)°, and the two symmetry-related benzene rings by 7.69 (6)°. In compound (II), the benzene and pyridine rings are inclined to each other by 25.56 (11)°. The symmetry-related pyridine rings are parallel, as are the two symmetry-related benzene rings. In the crystal of (I), a pair of water mol-ecules link the organic mol-ecules via Owater-H⋯O and Owater-H⋯N hydrogen bonds, forming chains along [001], and enclosing an R 4 2(8) and two R 1 2(5) ring motifs. The chains are linked by N-H⋯Npyridine hydrogen bonds, forming a supra-molecular framework. There are also a number of C-H⋯O hydrogen bonds, and C-H⋯π and offset π-π inter-actions [inter-planar distance = 3.294 (1) Å] present reinforcing the framework. In the crystal of (II), mol-ecules are linked by N-H⋯Npyridine hydrogen bonds, forming a supra-molecular framework. Here too there are also a number of C-H⋯O hydrogen bonds present, and a C-H⋯π inter-action, reinforcing the framework. For compound (II), a region of disordered electron density was corrected for using the SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9-18] routine in PLATON. Their formula mass and unit-cell characteristics were not taken into account during refinement.

The crystal structures of 6'-(4-chloro-phen-yl)- and 6'-(4-meth-oxy-phen-yl)-6a'-nitro-6a',6b',7',9',10',12a'-hexa-hydro-2H,6'H,8'H-spiro-[ace-naphthyl-ene-1,12'-chromeno[3,4-a]indolizin]-2-one.

In the title compounds, C32H25ClN2O4 (I) and C33H28N2O5 (II), the six-membered pyran and piperidine rings adopt envelope and chair conformations, respectively. The five-membered pyrrolidine rings adopt twist conformations. Compound (II) crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. In all three mol-ecules there is a C-H⋯O intra-molecular hydrogen bond present enclosing an S(7) ring motif. In (I), both oxygen atoms of the nitro group are disordered, while in (II) the meth-oxy-benzene group is disordered in mol-ecule B. The geometries were regularized by soft restraints. In the crystal of (I), mol-ecules are linked by C-H⋯O hydrogen bonds, forming chains along [010]. The chains are linked by C-H⋯Cl hydrogen bonds, forming layers parallel to (10). Within the layer there are C-H⋯π inter-actions present. In the crystal of (II), the A and B mol-ecules are linked via C-H⋯O hydrogen bonds, forming a square four-membered A-B-A-B unit. These units are linked by a number of C-H⋯π inter-actions, forming a three-dimensional supra-molecular structure.

Crystal structure of 6-(4-chloro-phen-yl)-6a-nitro-6a,6b,8,9,10,12a-hexa-hydro-6H,7H-spiro[chromeno[3,4-a]indolizine-12,11'-indeno-[1,2-b]quinoxaline].

The title compound, C35H27ClN4O3, crystallized with two independent mol-ecules (A and B) in the asymmetric unit. In both mol-ecules, the pyran and pyridine rings adopt envelope and chair conformations, respectively. The conformation of the pyrrolidine and cyclo-pentene rings differ in the two mol-ecules; twisted and flat, respectively, in mol-ecule A, but envelope and twisted, respectively, in mol-ecule B. In both mol-ecules, there is a C-H⋯N intra-molecular hydrogen bond present. In both mol-ecules, the oxygen atoms of the nitro groups are disordered as is the chlorine atom in mol-ecule B. In the crystal, the B mol-ecules are linked by C-H⋯O hydrogen bonds, forming -B-B-B- chains along [010], and by C-H⋯π inter-actions. The A and B mol-ecules are also linked by a number of C-H⋯π inter-actions, resulting in the formation a supra-molecular three-dimensional structure. In mol-ecule A, the nitro group oxygen atoms are disordered over two positions with refined occupancy ratios of the nitro group oxygen atoms O3A and O4A in 0.59 (2):0.41 (2) while in molecule B one of the nitro O atoms is disordered over two positions with a refined occupancy ratio of 0.686 (13):0.314 (13) and the chlorine atoms is disordered over two positions with a refined occupancy ratio of 0.72 (3):0.28 (3).