Crystal structure of 7'-(4-chloro-phen-yl)-2''-(4-meth-oxy-phen-yl)-7',7a',7'',8''-tetra-hydro-1'H,3'H,5''H-di-spiro-[indoline-3,5'-pyrrolo-[1,2-c]thia-zole-6',6''-quinoline]-2,5''-dione and an unknown solvent.

The asymmetric unit of the title compound, C34H28ClN3O3S, contains two independent mol-ecules (A and B). They differ essentially in the orientation of the 4-meth-oxy-phenyl ring with respect to the pyridine ring of the quinoline moiety; this dihedral angle is 37.01 (18)° in mol-ecule A but only 7.06 (17)° in mol-ecule B. In both mol-ecules, the cyclo-hexa-none ring of the iso-quinoline unit has a half-chair conformation. In the pyrrolo-thia-zole ring system, the pyrrolo ring in mol-ecule A has a twisted conformation on the N-C fused bond and an envelope conformation in mol-ecule B with the N atom as the flap. The thia-zole rings of both mol-ecules have twisted conformations on the N-C fused bond. In the crystal, the A mol-ecules are linked by pairs of N-H⋯O hydrogen bonds, forming inversion dimers with an R 2 2(8) ring motif. These dimers are linked to the B mol-ecules by an N-H⋯N hydrogen bond and a series of C-H⋯O hydrogen bonds, forming layers lying parallel to the (101) plane. The layers are linked by C-H⋯π inter-actions and offset π-π inter-actions [inter-centroid distance = 3.427 (1) Å], forming a supra-molecular framework. The contribution to the scattering from a region of highly disordered solvent mol-ecules was removed with the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18]. The solvent formula mass and unit-cell characteristics were not taken into account during refinement.

Crystal structure and Hirshfeld surface analysis of 4'-(2-chloro-phen-yl)-1'-methyl-3''-phenyl-7'',8''-di-hydro-5''H-di-spiro-[indoline-3,2'-pyrrolidine-3',6''-iso-quinoline]-2,5''-dione.

In the title di-spiro compound, C32H26ClN3O2, the cyclo-hexa-none ring of the iso-quinoline unit has a distorted envelope conformation, with the methyl-ene C atom adjacent to the spiro C atom as the flap. The central 1-methyl-pyrrolidine ring has an envelope conformation with the N atom as the flap. The mean planes of the indolin-2-one ring system, the chloro-benzene ring and the iso-quinoline ring system are inclined to the mean plane of the central 1-methyl-pyrrolidine ring by 87.95 (11), 71.01 (12) and 88.81 (10)°, respectively. There are two short C-H⋯O intra-molecular contacts present. In the crystal, mol-ecules are linked via C-H⋯ O hydrogen bonds, forming chains along the a-axis direction. The NH H atom is involved in a weak N-H⋯O hydrogen bond with the same carbonyl O atom. There are no further significant inter-molecular contacts present. The largest contribution to the overall Hirshfeld surface of 52.3% is due to H-H contacts.

Crystal structure of 2-benzyl-amino-4-p-tolyl-6,7-di-hydro-5H-cyclo-penta-[b]pyridine-3-carbo-nitrile.

The title compound, C23H21N3, comprises a 2-amino-3-cyano-pyridine ring fused with a cyclo-pentane ring. The later adopts an envelope conformation with the central methyl-ene C atom as the flap. The benzyl and and p-tolyl rings are inclined to one another by 56.18 (15)°, and to the pyridine ring by 81.87 (14) and 47.60 (11)°, respectively. In the crystal, mol-ecules are linked by pairs of N-H⋯Nnitrile hydrogen bonds, forming inversion dimers with an R 2 (2)(12) ring motif. The dimers are linked by C-H⋯π and π-π inter-actions [centroid-centroid distance = 3.7211 (12) Å], forming a three-dimensional framework.

Crystal structure of 1',1''-dimethyl-4'-(4-cholorophen-yl)di-spiro-[11H-indeno[1,2-b]quinoxaline-11,2'-pyrrolidine-3',3''-piperidin]-4''-one.

In the title compound, C30H27ClN4O, the central pyrrolidine ring adopts an envelope conformation with the methyl-ene C atom being the flap. The quinoxaline and indane rings are each essentially planar, with r.m.s. deviations of 0.027 (1) and 0.0417 (1) Å, respectively. The pyrrolidine ring forms dihedral angles of 88.25 (1) and 83.76 (1)° with the quinoxaline and indane rings, respectively. A weak intra-molecular C-H⋯N inter-action is observed. In the crystal, C-H⋯π inter-actions lead to supra-molecular chains along [101] that assemble in the ac plane. Connections along the b axis are of the type Cl⋯Cl [3.6538 (16) Å].

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 structures of 2-benzyl-amino-4-(4-bromo-phen-yl)-6,7,8,9-tetra-hydro-5H-cyclo-hepta-[b]pyridine-3-carbo-nitrile and 2-benzyl-amino-4-(4-chloro-phen-yl)-6,7,8,9-tetra-hydro-5H-cyclo-hepta[b]pyridine-3-carbo-nitrile.

In the title compounds, C24H22BrN3, (I), and C24H22ClN3, (II), the 2-amino-pyridine ring is fused with a cyclo-heptane ring, which adopts a half-chair conformation. The planes of the phenyl and benzene rings are inclined to that of the central pyridine ring [r.m.s. deviations = 0.0083 (1) and 0.0093 (1) Šfor (I) and (II), respectively] by 62.47 (17) and 72.51 (14)°, respectively, in (I), and by 71.44 (9) and 54.90 (8)°, respectively, in (II). The planes of the aromatic rings are inclined to one another by 53.82 (17)° in (I) and by 58.04 (9)° in (II). In the crystals of both (I) and (II), pairs of N-H⋯Nnitrile hydrogen bonds link the mol-ecules, forming inversion dimers with R 2 (2)(12) ring motifs. In (I), the resulting dimers are connected through C-H⋯Br hydrogen bonds, forming sheets parallel to (10-1), and π-π inter-actions [inter-centroid distance = 3.7821 (16) Å] involving inversion-related pyridine rings, forming a three-dimensional network. In (II), the resulting dimers are connected through π-π inter-actions [inter-centroid distance = 3.771 (2) Å] involving inversion-related pyridine rings, forming a two-dimensional network lying parallel to (001).

Crystal structure of 1-benzyl-4-(4-chloro-phen-yl)-2-imino-1,2,5,6,7,8,9,10-octa-hydro-cyclo-octa-[b]pyridine-3-carbo-nitrile.

The title compound, C25H24ClN3, comprises a 2-imino-pyridine ring fused with a cyclo-octane ring, which adopts a twist boat-chair conformation. In the crystal, C-H⋯N inter-actions form R 2 (2)(14) ring motifs and mol-ecules are further connected by weak C-H⋯π inter-actions. The resulting supra-molecular structure is a two-dimensional framework parallel to the ab plane.

Crystal structure of 4-(1H-indol-3-yl)-2-(4-meth-oxy-phen-yl)-6-phenyl-pyridine-3-carbo-nitrile.

In the title compound, C27H19N3O, the dihedral angles between the plane of the pyridine ring and those of the indole (r.m.s. deviation = 0.018 Å), phenyl and meth-oxy-benzene substituents are 33.60 (6), 25.28 (7) and 49.31 (7)°, respectively. The N atom of the carbo-nitrile group is significantly displaced [0.288 (2) Å] from the plane of the pyridine ring, perhaps due to steric crowding. In the crystal, inversion dimers linked by pairs of N-H⋯Nn (n = nitrile) hydrogen bonds generate R 2 (2)(16) loops. Aromatic π-π stacking [centroid-centroid separation = 3.6906 (7) Å] and very weak C-H⋯π inter-actions are also observed".

Isotypic crystal structures of 1-benzyl-4-(4-bromo-phen-yl)-2-imino-1,2,5,6,7,8,9,10-octa-hydro-cyclo-octa-[b]pyridine-3-carbo-nitrile and 1-benzyl-4-(4-fluoro-phen-yl)-2-imino-1,2,5,6,7,8,9,10-octa-hydro-cyclo-octa-[b]pyridine-3-carbo-nitrile.

The mol-ecules of the two isotypic title compounds, C25H24BrN3, (I), and C25H24FN3, (II), comprise a 2-imino-pyridine ring fused with a cyclo-octane ring. In (I), the cyclo-octane ring adopts a twisted chair-chair conformation, while in (II), this ring adopts a twisted boat-chair conformation. The dihedral angles between the planes of the pyridine ring and the bromo-benzene and phenyl rings are 80.14 (12) and 71.72 (13)°, respectively, in (I). The equivalent angles in (II) are 75.25 (8) and 68.34 (9)°, respectively. In both crystals, inversion dimers linked by pairs of C-H⋯N inter-actions generate R 2 (2)(14) loops, which are further connected by weak C-H⋯π inter-actions, generating (110) sheets.

Crystal structure of 1-benzyl-4-(2,4-di-chloro-phenyl)-2-imino-1,2,5,6,7,8,9,10-octa-hydro-cyclo-octa-[b]pyridine-3-carbo-nitrile.

In the title compound, C25H23Cl2N3, the cyclo-octene ring adopts a twist chair-chair conformation. The dihedral angles between the central pyridine ring (r.m.s. deviation = 0.013 Å) and the pendant chloro-benzene and benzyl rings are 78.07 (11) and 87.47 (12)°, respectively. No directional inter-actions could be identified in the crystal and the packing is governed by van der Waals inter-actions.

Crystal structure of 2-(2-bromo-phen-yl)-4-(1H-indol-3-yl)-6-(thio-phen-2-yl)pyridine-3-carbo-nitrile.

In the title compound, C24H14BrN3S, the dihedral angles between the planes of the pyridine ring and the pendant thio-phene ring, the indole ring system (r.m.s. deviation = 0.022 Å) and the bromo-benzene ring are 9.37 (17), 21.90 (12) and 69.01 (15)°, respectively. The approximate coplanarity of the central ring and the indole ring system is supported by two intra-molecular C-H⋯N inter-actions. In the crystal, inversion dimers linked by pairs of N-H⋯N hydrogen bonds generate R 2 (2)(16) loops and the dimers are linked by C-H⋯π and aromatic π-π stacking [shortest centroid-centroid separation = 3.729 (3) Å] into a three-dimensional network.

Crystal structure of 5-amino-5'-chloro-6-(4-chloro-benzo-yl)-8-nitro-2,3-di-hydro-1H-spiro-[imidazo[1,2-a]pyridine-7,3'-indolin]-2'-one including an unknown solvent mol-ecule.

The asymmetric unit of the title compound, C21H15Cl2N5O4, contains two independent mol-ecules (A and B) having similar conformations. The amine (NH2) group forms an intra-molecular hydrogen bond with the benzoyl group, giving an S(6) ring motif in both mol-ecules. The central six-membered rings adopt sofa conformations and the imidazole rings are planar (r.m.s deviations = 0.0150 and 0.0166 Å). The pyridine and imidazole rings are inclined to one another by 3.54 (1) and 3.03 (1)° in mol-ecules A and B, respectively. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds, forming chains along the a axis which enclose R 2 (2)(16) ring motifs. The rings are linked by weak N-H⋯O and C-H⋯O hydrogen bonds and C-H⋯π inter-actions forming sheets lying parallel to (001). A region of disordered electron density, most probably disordered solvent mol-ecules, occupying voids of ca 753 Å(3) for an electron count of 260, was treated using the SQUEEZE routine in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155]. Their formula mass and unit-cell characteristics were not taken into account during refinement.

Crystal structure of 2-(4-chloro-phen-yl)-4-(1H-indol-3-yl)-6-phenyl-pyridine-3-carbo-nitrile.

In the title compound, C26H16ClN3, the dihedral angles between the central pyridine ring and the pendant phenyl, chloro-benzene and indole rings are 18.52 (12), 48.97 (11) and 21.20 (10)°, respectively. An intra-molecular C-H⋯Nc (c = cyanide) hydrogen bond occurs. In the crystal, inversion dimers linked by pairs of N-H⋯Nc hydrogen bonds generate R 2 (2)(16) loops.

4-(2-Fluoro-phen-yl)-2-meth-oxy-5,6,7,8,9,10-hexa-hydro-cyclo-octa-[b]pyridine-3-carbo-nitrile.

In the title compound, C19H19FN2O, the cyclo-octene ring adopts a twisted boat-chair conformation. The dihedral angle between the plane of the fluorophenyl substituent and that of the pyridine ring is 76.39 (8)°. The F and ortho-H atoms of the fluoro-benzene ring are disordered, with occupancy factors of 0.226 (5) and 0.774 (5). In the crystal, no significant inter-actions are observed between the mol-ecules beyond van der Waals contacts.

5-Amino-5'-bromo-6-(4-methyl-benzo-yl)-8-nitro-2,3-di-hydro-1H-spiro-[imidazo[1,2-a]pyridine-7,3'-indolin]-2'-one including an unknown solvate.

In the title compound, C22H18BrN5O4, the central six-membered ring, derived from 1,4-di-hydro-pyridine, adopts a distorted boat conformation with a puckering amplitude of 0.197 (3) Å, the imidazole ring adopts a twisted conformation with a puckering amplitude of 0.113 (3) Å, and the oxindole moiety is planar with an r.m.s. deviation of 0.0125 Å. Two intra-molecular N-H⋯O hydrogen bonds are formed, each closing an S(6) loop. In the crystal, strong N-H⋯O hydrogen bonds lead to the formation of zigzag chains along the c axis. These are consolidated in the three-dimensional crystal packing by weak N-H⋯O hydrogen bonding, as well as by C-H⋯O, C-H⋯Br and C-H⋯π inter-actions. A small region of electron density well removed from the main mol-ecule was removed with the SQUEEZE procedure in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155] following unsuccessful attempts to model it as a plausible solvent mol-ecule. The unit-cell characteristics do not take into account this feature of the structure.

2-Meth-oxy-4-(2-meth-oxy-phen-yl)-5,6,7,8,9,10-hexa-hydro-cyclo-octa-[b]pyridine-3-carbo-nitrile.

In the title compound, C20H22N2O2, the central pyridine ring forms a dihedral angle of 76.32 (8)° with the pseudo-axial benzene ring. The cyclo-octane ring adopts a twisted boat chair conformation. In the crystal, weak inter-molecular C-H⋯π inter-actions between inversion-related mol-ecules result in the formation of linear double chains along the b-axis direction.

5-Amino-6-benzoyl-8-nitro-2,3-di-hydro-1H-spiro-[imidazo[1,2-a]pyridine-7,3'-indolin]-2'-one dimethyl sulfoxide monosolvate.

In the title compound C21H17N5O4·C2H6OS, the central six-membered ring derived from 1,4-di-hydro-pyridine adopts a distorted boat conformation with a small puckering amplitude of 0.127 (3) Å. The sums of bond angles around the pyridine N atom [358.7 (2)°] and the other imidazolidine N atom [60 (2)°] indicate that these atoms are in sp(2) hybridization, leading to an essentially planar imidazolidine ring. The last heterocycle, an oxindole moiety, is also nearly planar with an r.m.s. deviation of 0.0185 (1) Å. The amine NH2 group forms an intra-molecular hydrogen bond with the benzoyl group, giving a S(6) motif. In the crystal, N-H⋯O hydrogen bonds lead to the formation of chains along the c-axis direction. Within the chains there are further N-H⋯O and C-H⋯O hydrogen bonds enclosing R (2) 2(14) ring motifs. The chains are linked via N-H⋯O and C-H⋯O hydrogen bonds involving the dimethyl sulfoxide solvent mol-ecule which acts as both an acceptor and a donor..

(3aR*,8bR*)-3a,8b-Dihy-droxy-1-(4-methyl-phen-yl)-2-methyl-sulfanyl-3-nitro-1,8b-di-hydro-indeno-[1,2-b]pyrrol-4(3aH)-one.

The asymmetric unit of the title compound, C19H16N2O5S, contains four independent mol-ecules (A, B, C and D), with two mol-ecules (B and D) displaying disorder in their methyl-sulfanyl groups [occupancy ratios of 0.797 (11):0.203 (11) and 0.85 (2):0.15 (2)]. The nitro groups are twisted slightly out of the planes of the 2-pyrroline rings to which they are bonded with dihedral angles of 10.17 (1), 8.01 (1), 9.44 (1) and 8.87 (1)° in mol-ecules A, B, C and D, respectively. The 2-pyrroline rings are almost orthogonal to the attached tolyl rings, forming dihedral angles of 73.44 (1), 81.21 (1), 88.18 (8) and 73.94 (1)° for mol-ecules A, B, C and D, respectively. A weak intra-molecular O-H⋯O inter-action is observed in mol-ecules B and C. The two hy-droxy groups in each mol-ecule are involved in inter-molecular O-H⋯O hydrogen bonding. In the crystal, mol-ecules are connected via O-H⋯O and C-H⋯O hydrogen bonds, forming a complex three-dimensional network.

10-(4-Chloro-phen-yl)-14a-hy-droxy-12-methyl-8,9,9a,10,12,13,14,14a-octa-hydro-5H-10a,14-methano-indeno-[2',1':4,5]azepino[3,4-b]pyrrolizine-5,15(7H,11H)-dione.

The asymmetric unit of the title compound, C26H25ClN2O3, contains two independent mol-ecules (A and B). The conformation of the two mol-ecules differs essentially in the dihedral angle involving the two benzene rings. They are inclined to one another by 52.47 (10) in A and by 31.75 (11)° in B. In both mol-ecules, the six-membered piperidin-3-one rings have chair conformations. In mol-ecule A, all four five-membered rings have twist conformations. In mol-ecule B, only three of the four five-membered rings have twist conformations. The fourth, of the inden-1-one moiety, has an envelope conformation with the spiro C atom, bonded to the N atom of the pyrrolidine ring, as the flap. A weak intra-molecular O-H⋯N hydrogen bond occurs in each independent mol-ecule while a C-H⋯O inter-action is also observed in mol-ecule A. In the crystal, pairs of O-H⋯O hydrogen bonds link the mol-ecules, forming inversion dimers with graph-set motif R 2 (2)(12). These dimers are further inter-connected by C-H⋯O and C-H⋯π inter-actions, forming a three-dimensional network.

Crystal structure of 2-benzyl-amino-4-(4-meth-oxy-phen-yl)-6,7,8,9-tetra-hydro-5H-cyclo-hepta-[b]pyridine-3-carbo-nitrile.

The title compound, C25H25N3O, comprises a 2-amino-pyridine ring fused with a cyclo-heptane ring, which adopts a chair conformation. The central pyridine ring (r.m.s. deviation = 0.013 Å) carries three substituents, viz. a benzyl-amino group, a meth-oxy-phenyl ring and a carbo-nitrile group. The N atom of the carbo-nitrile group is significantly displaced [by 0.2247 (1) Å] from the plane of the pyridine ring, probably due to steric crowding involving the adjacent substituents. The phenyl and benzene rings are inclined to one another by 58.91 (7)° and to the pyridine ring by 76.68 (7) and 49.80 (6)°, respectively. In the crystal, inversion dimers linked by pairs of N-H⋯Nnitrile hydrogen bonds generate R 2 (2)(14) loops. The dimers are linked by C-H⋯π and slipped parallel π-π inter-actions [centroid-centroid distance = 3.6532 (3) Å] into a three-dimensional structure.