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The syntheses and characterization (NMR and XRD) of two substituted [2.2.2]bi­cyclo­octene ring systems are described here. The cyclo­hexene rings of these systems adopt a nearly perfect boat conformation according to analysis using Cremer–Pople parameters. Both structures contain a nearly planar imide ring that is oriented endo relative to a bridgehead cyclo­propyl ring. 4-(2-Phenyl­eth­yl)-4-aza­tetra­cyclo­[5.3.2.02,6.08,10]dodec-11-ene-3,5-dione, C19H19NO2, is substituted with a phenylethyl group that hosts C—H⋯π inter­actions in the crystal. 4-[2-(4-Hy­droxy­phen­yl)eth­yl]-4-aza­tetra­cyclo­[5.3.2.02,6.08,10]dodec-11-ene-3,5-dione, C19H19NO3, bears a 4-hy­droxy­phenylethyl group on the imide ring and contains O—H⋯O and C—H⋯O hydrogen bonds. [ABSTRACT FROM AUTHOR]

The reaction of ethane-1,2-di-amine (en, C 2 H 8 N 2 ), the sodium salt of naphthalene-1,5-di-sulfonic acid (H 2 NDS, C 10 H 8 O 6 S 2 ), and nickel sulfate in an aqueous solution resulted in the formation of the title salt, [Ni(C 2 H 8 N 2 )(H 2 O) 4 ](C 10 H 6 O 6 S 2 )·2H 2 O or [Ni(en)(H 2 O) 4 ](NDS)·2H 2 O. In the asymmetric unit, one half of an [Ni(en)(H 2 O) 4 ] 2+ cation and one half of an NDS 2- anion, and one water mol-ecule of crystallization are present. The Ni 2+ cation in the complex is positioned on a twofold rotation axis and exhibits a slight tetra-gonal distortion of the cis -NiO 4 N 2 octa-hedron, with an Ni-N bond length of 2.0782 (16) Å, and Ni-O bond lengths of 2.1170 (13) Å and 2.0648 (14) Å. The anion is completed by inversion symmetry. In the extended structure, the cations, anions, and non-coordinating water mol-ecules are connected by inter-molecular N-H⋯O and O-H⋯O hydrogen bonding, as well as C-H⋯π inter-actions, forming a three-dimensional network., (© Suyunov et al. 2023.)

The title compound, C26H20N2, was obtained during a search for new π-extended ligands with the potential to generate efficient phosphors with iridium(III) for organic light-emitting devices (OLEDs). The benzoquinoxaline ring system is almost planar (r.m.s. deviation = 0.076 Å). A pseudo-twofold rotation axis runs through the midpoints of the C2—C3 and C9—C10 bonds. The two phenyl rings are twisted relative to the benzoquinoxaline ring system, making dihedral angles of 53.91 (4) and 36.86 (6)°. In the crystal, C—H⋯π (arene) inter­actions link the mol­ecules, but no π–π inter­actions between aromatic rings are observed. [ABSTRACT FROM AUTHOR]

The crystal structures of ( Z )-(ethene-1,2-di-yl)bis-(di-phenyl-phosphine sulfide), C 26 H 22 P 2 S 2 ( I ), along with its complex with Pt II dichloride, di-chlorido[( Z )-(ethene-1,2-di-yl)bis-(di-phenyl-phosphine sulfide)-κ 2 S , S ']platinum(II), [PtCl 2 (C 26 H 22 P 2 S 2 )] ( II ), are described here. Compound I features P=S bond lengths of 1.9571 (15) and 1.9529 (15) Å, with a torsion angle of 166.24 (7)° between the two phosphine sulfide groups. The crystal of compound I features both intra-molecular C-H⋯S hydrogen bonds and π-π inter-actions. Mol-ecules of compound I are held together with inter-molecular π-π and C-H⋯π inter-actions to form chains that run parallel to the z -axis. The inter-molecular C-H⋯π inter-action has a H⋯ Cg distance of 2.63 Å, a D ⋯ Cg distance of 3.573 (5) Å and a D -H⋯ Cg angle of 171° (where Cg refers to the centroid of one of the phenyl rings). These chains are linked by relatively long C-H⋯S hydrogen bonds with D ⋯ A distances of 3.367 (4) and 3.394 (4) Å with D -H⋯ A angles of 113 and 115°. Compound II features Pt-Cl and Pt-S bond lengths of 2.3226 (19) and 2.2712 (19) Å, with a P=S bond length of 2.012 (3) Å. The Pt II center adopts a square-planar geometry, with Cl-Pt-Cl and S-Pt-S bond angles of 90.34 (10) and 97.19 (10)°, respectively. Mol-ecules of compound II are linked in the crystal by inter-molecular C-H⋯Cl and C-H⋯S hydrogen bonds., (© Rawls et al. 2023.)

The crystal structure of the title compound, [AuCl(C 16 H 13 PS)], is reported. The mol-ecular structure features a nearly linear arrangement of the chloride and phosphino ligands around the gold(I) center, with a P-Au-Cl bond angle of 179.42 (9)°. The Au-P and Au-Cl bond lengths are 2.226 (2) and 2.287 (2) Å, respectively. The geometry of the groups bonded to the phospho-rus atom of the ligand is a slightly distorted tetra-hedron. The phenyl and thienyl rings of the ligand are extensively disordered, with the thienyl refined over all three possible positions on the phospho-rus atom. The relative occupancy ratio between these positions was found to be 0.406 (3):0.406 (2):0.188 (2). One of the major thienyl ring positions with the relative occupancy of 0.406 was modeled as two rotational isomers around the C-P bond with a relative occupancy ratio of 0.278 (3):0.128 (3). Inter-molecular C-H⋯π inter-actions present in the crystal lattice link mol-ecules of the title compound together to form a complex three-dimensional network., (© Neils et al. 2022.)

In the title compound, C 23 H 19 NO 5 , the cyano group adopts an axial orientation and the ester group an equatorial orientation. The dihedral angle between the pendant phenyl group and the benzene ring of the fused-ring system is 25.97 (8)°. Intra-molecular O-H⋯O and C-H⋯O hydrogen bonds are observed and the packing is consolidated by C-H⋯O and C-H⋯π inter-actions., (© Surya Prakash Rao et al. 2022.)

In the title compound, C 12 H 10 O 6 , an intra-molecular O-H⋯O hydrogen bond forms an S (6) ring motif. The mol-ecule is essentially planar with an r.m.s. deviation of 0.051 Å for all non-H atoms. In the crystal mol-ecules are linked by C-H⋯O hydrogen bonds and a C-H⋯π inter-action, forming a supra-molecular framework., (© Tiouabi et al. 2020.)

The syntheses and crystal structures of the two title compounds, C 11 H 10 O 3 ( I ) and C 17 H 14 BrNO 2 ( II ), both containing the bi-cyclo-[2.2.2]octene ring system, are reported here [the structure of I has been reported previously: White & Goh (2014 ▸). Private Communication (refcode HOKRIK). CCDC, Cambridge, England]. The bond lengths and angles of the bi-cyclo-[2.2.2]octene ring system are similar for both structures. The imide functional group of II features carbonyl C=O bond lengths of 1.209 (2) and 1.210 (2) Å, with C-N bond lengths of 1.393 (2) and 1.397 (2) Å. The five-membered imide ring is nearly planar, and it is positioned exo relative to the alkene bridgehead carbon atoms of the bi-cyclo-[2.2.2]octene ring system. Non-covalent inter-actions present in the crystal structure of II include a number of C-H⋯O inter-actions. The extended structure of II also features C-H⋯O hydrogen bonds as well as C-H⋯π and lone pair-π inter-actions, which combine together to create supra-molecular sheets., (© Hulsman et al. 2020.)

The title compound, C 15 H 17 NO 2 S, was synthesized via a substitution reaction between 4-methyl-benzyl-amine and p -toluene-sulfonyl chloride. In the crystal, N-H⋯O hydrogen bonds link the mol-ecules, forming ribbons running along the b -axis direction. One of the aromatic rings hosts two inter-molecular C-H⋯π inter-actions that link these hydrogen-bonded ribbons into a three-dimensional network., (© Stenfors et al. 2020.)

In the title compound, C 24 H 22 N 4 O 4 , the four pyridine rings are tilted slightly with respect to each other. The dihedral angles between the inner and outer pyridine rings are 12.51 (8) and 9.67 (9)°, while that between inner pyridine rings is 20.10 (7)°. Within the mol-ecule, intra-molecular C-H⋯O and C-H⋯N contacts are observed. In the crystal, adjacent mol-ecules are linked by π-π stacking inter-actions between pyridine rings and weak C-H⋯π inter-actions between a methyl H atom and the centroid of a pyridine ring, forming a two-dimensional layer structure extending parallel to the ac plane. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (52.9%) and H⋯C/C⋯H (17.3%) contacts., (© Moon et al. 2019.)

In the title compound, C 27 H 29 BrN 2 , the carbazole ring system is essentially planar, with an r.m.s. deviation of 0.0781 (16) Å. An intra-molecular N-H⋯N hydrogen bond forms an S (6) ring motif. One of the tert -butyl substituents shows rotational disorder over two sites with occupancies of 0.592 (3) and 0.408 (3). In the crystal, two mol-ecules are associated into an inversion dimer through a pair of C-H⋯π inter-actions. The dimers are further linked by another pair of C-H⋯π inter-actions, forming a ribbon along the c -axis direction. A C-H⋯π inter-action involving the minor disordered component and the carbazole ring system links the ribbons, generating a network sheet parallel to (100)., (© Kubono et al. 2019.)

The sterically hindered silicon compound 2-methyl-1,1,2,3,3-penta-phenyl-2-sila-propane, C 33 H 30 Si ( I ), was prepared via the reaction of two equivalents of di-phenyl-methyl-lithium (benzhydryllithium) and di-chloro-methyl-phenyl-silane. This bis-benzhydryl-substituted silicon compound was then reacted with tri-fluoro-methane-sulfonic acid, followed by hydrolysis with water to give the silanol 2-methyl-1,1,3,3-tetra-phenyl-2-silapropan-2-ol, C 27 H 26 OSi ( II ). Key geometric features for I are the Si-C bond lengths that range from 1.867 (2) to 1.914 (2) Å and a τ 4 descriptor for fourfold coordination around the Si atom of 0.97 (indicating a nearly perfect tetra-hedron). Key geometric features for compound II include Si-C bond lengths that range from 1.835 (4) to 1.905 (3) Å, a Si-O bond length of 1.665 (3) Å, and a τ 4 descriptor for fourfold coordination around the Si atom of 0.96. In compound II , there is an intra-molecular C-H⋯O hydrogen bond present. In the crystal of I , mol-ecules are linked by two pairs of C-H⋯π inter-actions, forming dimers that are linked into ribbons propagating along the b -axis direction. In the crystal of II , mol-ecules are linked by C-H⋯π and O-H⋯π inter-actions that result in the formation of ribbons that run along the a -axis direction.

The title pyridazin-3(2 H )-one derivative, C 25 H 19 FN 2 O 2 , crystallizes with two independent mol-ecules ( A and B ) in the asymmetric unit. In mol-ecule A , the 4-fluoro-phenyl ring, the benzyl ring and the phenyl ring are inclined to the central pyridazine ring by 86.54 (11), 3.70 (9) and 84.857 (13)°, respectively. In mol-ecule B , the corresponding dihedral angles are 86.80 (9), 10.47 (8) and 82.01 (10)°, respectively. In the crystal, the A mol-ecules are linked by pairs of C-H⋯F hydrogen bonds, forming inversion dimers with an R 2 2 (28) ring motif. The dimers are linked by C-H⋯O hydrogen bonds and a C-H⋯π inter-action, forming columns stacking along the a -axis direction. The B mol-ecules are linked to each other in a similar manner and form columns separating the columns of A mol-ecules.

A new quinoline-based hydrazone, C 16 H 12 ClN 3 , was synthesized by a condensation reaction of 2-chloro-3-formyl-quinoline with phenyl-hydrazine. The quinoline ring system is essentially planar (r.m.s. deviation = 0.012 Å), and forms a dihedral angle of 8.46 (10)° with the phenyl ring. The mol-ecule adopts an E configuration with respect to the central C=N bond. In the crystal, mol-ecules are linked by a C-H⋯π-phenyl inter-action, forming zigzag chains propagating along the [10] direction. The N-H hydrogen atom does not participate in hydrogen bonding but is directed towards the phenyl ring of an adjacent mol-ecule, so linking the chains via weak N-H⋯π inter-actions to form of a three-dimensional structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (35.5%), C⋯H/H⋯C (33.7%), Cl⋯H/H⋯Cl (12.3%), N⋯H/H⋯N (9.5%) contacts.

The asymmetric unit of the title compound, C 14 H 14 O 6 , a monomeric compound of poly(butyl-ene 2,5-furandi-carboxyl-ate), consists of one half-mol-ecule, the whole all- trans mol-ecule being generated by an inversion centre. In the crystal, the mol-ecules are inter-connected via C-H⋯O inter-actions, forming a mol-ecular sheet parallel to (10). The mol-ecular sheets are further linked by C-H⋯π inter-actions.

In the title hydrated azo dye, C 10 H 10 N 4 OS·H 2 O, the benzene and thia-zole, are nearly coplanar, with a dihedral angle between their mean planes of 4.69 (17)°. The aromatic rings on the -N=N- moiety exhibit a trans configuration. The crystal structure features many types of inter-molecular inter-actions involving all the functional groups - strong hydrogen bonds (N⋯H and O⋯H), weak hydrogen bonds (C-H⋯O and C-H⋯N), C-H⋯π and π-π inter-actions - resulting in the formation of a three-dimensional framework.

The title complex, [Fe(C 44 H 28 N 4 )(C 5 H 8 N 2 ) 2 ]·C 4 H 8 O, possesses inversion symmetry with the iron(II) atom located on a center of symmetry. The metal atom is coordinated in a symmetric octa-hedral geometry by four pyrrole N atoms of the porphyrin ligand in the equatorial plane and two N atoms of 1-ethyl-imidazole ligands in the axial sites; the complex crystallizes with a tetra-hydro-furan solvent mol-ecule. The average Fe-N p (N p is a porphyrin N atom) bond length is 1.995 (3) Å and the axial Fe-N Im (N Im is an imidazole N atom) bond length is 1.994 (2) Å. The two 1-ethyl-imidazole ligands are mutually parallel. The dihedral angle between the 1-ethyl-imidazole plane and the plane of the closest Fe-N p vector is 24.5°. In the crystal, the only significant inter-molecular inter-actions present are C-H⋯π inter-actions.

The crystal structure of the title compound, C 9 H 6 OS 2 , represents a new polymorph. The crystal structure was solved in the ortho-rhom-bic space group Pbcn with one half of the mol-ecule in the asymmetric unit. The thio-phene rings are perfectly planar and twisted with respect to each other, showing the mol-ecule to be in an S,O- trans /S,O- trans conformation. In the crystal, C-H⋯O hydrogen bonds connect the mol-ecules into layers extending parallel to the ab plane. The crystal structure also features π-π inter-actions.

The title compounds, C 16 H 14 O 2 S 2 and C 16 H 14 O 3 S, which are monomeric models (models D and E ) for a polythio-noester and a poly(ester- co -thio-noester), respectively, crystallize in the space group P 2 1 / c and are isostructural with each other. The mol-ecule in each crystal is located on an inversion centre and has an all- trans structure. The asymmetric unit comprises one half-mol-ecule. In the crystal, there are inter-molecular C⋯S contacts [3.391 (3) and 3.308 (3) Å for models D and E , respectively] and C-H⋯π inter-actions, which form a layer structure parallel to the bc plane. The carbonyl and thio-carbonyl groups of the model E compound are each disordered over two equivalent sites about the inversion centre with equal occupancies.

In the title compound, C30H20O2S2, the dihedral angles between the central azulene ring system (r.m.s. deviation = 0.039 Å) and the pendant benzene rings are 28.96 (7) and 55.15 (7)°. The dihedral angles between the benzene rings and their attached acetyl-sulfanyl groups are 59.60 (10) and 84.79 (10)°. The expected π-π stacking inter-actions are not observed in the crystal structure; instead, the packing features C-H⋯O hydrogen bonds, which link the mol-ecules into C(12) [010] chains, which are supported by weak C-H⋯π contacts.

The asymmetric unit of the title compound, C13H10N2O4, contains two independent mol-ecules (A and B). The dihedral angle between the aromatic rings is 48.18 (14)° in mol-ecule A and 45.81 (14)° in mol-ecule B. The mean plane of the carbamate N-C(=O)-O group is twisted slightly from the attached benzene and phenyl rings, making respective dihedral angles of 12.97 (13) and 60.93 (14)° in A, and 23.11 (14) and 59.10 (14)° in B. In the crystal, A and B mol-ecules are arranged alternately through N-H⋯O hydrogen bonds and C-H⋯π inter-actions, forming chains along the a axis. The chains are further linked by C-H⋯O hydrogen bonds into a double-chain structure.

In the title compound, C16H23N3O3S, the dihedral angles between the thio-phene ring and the almost planar di-methyl-amino-methyl-ene-amino (r.m.s. deviation = 0.005 Å) and di-methyl-amino-acryloyl (r.m.s. deviation = 0.033 Å) substituents are 6.99 (8) and 6.69 (7)°, respectively. The ester CO2 group subtends a dihedral angle of 44.92 (18)° with the thio-phene ring. An intra-molecular C-H⋯O hydrogen bond generates an S(6) ring. In the crystal, inversion dimers linked by pairs of C-H⋯O hydrogen bonds generate R (2) 2(14) loops. In addition, a weak C-H⋯π inter-action is observed.

In the title compound, C20H18N2O2, the central pyrazoline ring has an envelope conformation with the atom substituted by the naphthalene ring as the flap. It bridges a benzene ring and a naphthalene ring system which are almost normal to one another, making a dihedral angle of 82.03 (6) °. There is an intra-molecular O-H⋯N hydrogen bond forming an S(6) ring motif. In the crystal, mol-ecules are linked by pairs of N-H⋯π inter-actions, forming inversion dimers. There are also C-H⋯π inter-actions present and the dimers are linked via C-H⋯O hydrogen bonds, forming ribbons propagating along the a-axis direction.

The title compound, C20H19IS, features a 1,3-disubstituted azulene involving an ethynylene elongated 4-(tert-butyl-sulfanyl)-phenyl sidearm and an iodine atom as the substituents. The azulene ring system is almost planar (r.m.s. deviation = 0.012 Å) and subtends a dihedral angle of 35.7 (1)° with the benzene ring. As a result of the inherent dipole character of the azulene core, a supra-molecular π-π dimer [separation between the centroids of the five- and seven-membered rings = 3.7632 (10) Å] with anti-parallel orientated mol-ecules can be observed in the crystal. The packing is consolidated by an unusual I⋯π(acetyl-ene) contact [I⋯Cg = 3.34 Å, C-I⋯Cg = 173.3°], and a very weak C-H⋯π inter-action is also found in the structure, with the azulene five-membered ring as the acceptor.

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].

The title compound, C24H27NO2, crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. The two mol-ecules have very similar conformations and each exhibits an intra-molecular C-H⋯π inter-action. The central piperidine rings adopt boat conformations and the p-tolyl rings are inclined to the mean plane of the piperidine ring by 71.21 (11) and 89.86 (12)° in mol-ecule A and by 68.01 (12) and 89.33 (12)° in mol-ecule B. The cyclopropanecarbonyl group is oriented at an angle of 68.5 (2)° with respect to the mean plane of the piperidine ring in mol-ecule A and 66.2 (2)° in mol-ecule B. In the crystal, the A and B mol-ecules are linked by C-H⋯O hydrogen bonds, enclosing R 2 (1)(6) ring motifs, forming ribbons running along the a-axis direction.