Crystal structure of poly[(aceto-nitrile-κN)(µ3-7-{[bis-(pyridin-2-ylmeth-yl)amino]-meth-yl}-8-hy-droxy-quinoline-5-sulfonato-κ4N,O:O':O'')sodium].

In the title compound, [Na(C22H19N4O4S)(CH3CN)]n, the NaI atom adopts a distorted square-pyramidal coordination geometry, formed by one N and one O atom of the qunolinol moiety in the ligand, two O atoms of sulfonate moieties of two adjacent ligands and the N atom of the coordinated aceto-nitrile solvent. The NaI atom is located well above the mean basal plane of the square-based pyramid. The apical position is occupied by a sulfonate O atom of a neighboring ligand. Three N atoms of the bis-(pyridin-2-ylmeth-yl)amine moiety in the ligand are not coordinated by the sodium atom. The mol-ecule forms an intra-molecular bifurcated O-H⋯[N(tertiary amine),N(pyridine)] hydrogen bond, generating S(6) and S(5) rings. In the crystal, four mol-ecules are linked by four Na-O(sulfonato) bridged coordination bonds, forming a supra-molecular centrosymmetric tetra-mer unit comprising an eight-membered ring, and generating a two-dimensional network sheet. The mol-ecules of different sheets form inter-molecular C-H⋯O hydrogen bonds, and thereby a three-dimensional network structure.

Crystal structure of N-(1H-indol-2-yl-methyl-idene)-4-meth-oxy-aniline.

The mol-ecule of the title compound, C16H14N2O, contains an essentially planar indole ring system and a phenyl ring. In the crystal, the mol-ecules are linked by a weak inter-molecular C-H⋯O hydrogen bond and C-H⋯π inter-actions, forming a one-dimensional column structure along the b-axis direction. These columns are linked by other C-H⋯π inter-actions, forming a two-dimensional network structure.

Synthesis and crystal structure of anti-10-butyl-10,11,22,23-tetra-hydro-9H,21H-5,8:15,12-bis(metheno)[1,5,11]tri-aza-cyclo-hexa-decino[1,16-a:5,6-a']di-indole.

The title compound, C33H33N3, is a carbazolophane, which is a cyclo-phane composed of two carbazole fragments. It has a planar chirality but crystallizes as a racemate in the space group P . The mol-ecule adopts an anti-configuration, in which two carbazole fragments are partially overlapped. Both carbazole ring systems are slightly bent, with the C atoms at 3-positions showing the largest deviations from the mean planes. The dihedral angle between two carbazole fragments is 5.19 (3)°, allowing an intra-molecular slipped π-π inter-action [Cg⋯Cg = 3.2514 (8) Å]. In the crystal, the mol-ecules are linked via inter-molecular C-H⋯N hydrogen bonds and C-H⋯π inter-actions into a network sheet parallel to the ab plane. The mol-ecules of different sheets form other C-H⋯π inter-actions, thus forming a three-dimensional network.

Crystal structure of (7-{[bis-(pyridin-2-ylmeth-yl)amino-κ3 N,N',N'']meth-yl}-5-chloro-quinolin-8-ol)di-bromidozinc(II).

In the title compound, [ZnBr2(C22H19ClN4O)], the ZnII atom adopts a distorted square-pyramidal coordination geometry, formed by two bromido ligands and three N atoms of the bis-(pyridin-2-ylmeth-yl)amine moiety in the penta-dentate ligand containing quinolinol. The ZnII atom is located well above the mean basal plane of the square-based pyramid. The apical position is occupied by a Br atom. The O and N atoms of the quinolinol moiety in the ligand are not coordinated to the ZnII atom. An intra-molecular O-H⋯N hydrogen bond, generating an S(5) ring motif, stabilizes the mol-ecular structure. In the crystal, the mol-ecules are linked by inter-molecular C-H⋯Br hydrogen bonds, generating ribbon structures containing alternating R 2 2(22) and R 2 2(14) rings. These ribbons are linked through an inter-molecular C-H⋯Br hydrogen bond, forming a two-dimensional network sheet.

Crystal structure of tris-[4-(naphthalen-1-yl)phen-yl]amine.

In the title mol-ecule, C48H33N, the central N atom shows no pyramidalization, so that the N atom and the three C atoms bound to the N atom lie almost in the same plane. The three para-phenyl-ene rings bonded to the N atom are in a propeller form. All of the naphthalene ring systems are slightly bent. In the crystal, mol-ecules form an inversion dimer, through two pairs of C-H⋯π inter-actions, which further inter-acts with the adjacent dimer via another two pairs of C-H⋯π inter-actions, forming a column structure along the a axis. There are no significant inter-actions between these column structures.

Crystal structure of 7,7'-[(pyridin-2-yl)methyl-ene]bis-(5-chloro-quinolin-8-ol).

In the title compound, C24H15Cl2N3O2, one quinoline ring system is essentially planar and the other is slightly bent. An intra-molecular O-H⋯N hydrogen bond involving the hy-droxy group and a pyridine N atom forms an S(5) ring motif. In the crystal, two mol-ecules are associated into an inversion dimer with two R 2 2(7) ring motifs through inter-molecular O-H⋯N and O-H⋯O hydrogen bonds. The dimers are further linked by an inter-molecular C-H⋯O hydrogen bond and four C-H⋯π inter-actions, forming a two-dimensional network parallel to (001).

Combined Experimental and Theoretical Studies on Planar Chirality of Partially Overlapped C2-Symmetric [3.3](3,9)Dicarbazolophanes.

Partially overlapped dicarbazolophanes exhibit a planar chirality. In this study, C2-symmetrical [3.3](3,9)dicarbazolophane derivatives (CZ1-CZ3) have been optically resolved by preparative chiral high-performance liquid chromatography for the first time. In their circular dichroism (CD) spectra, moderate Cotton effects (CEs) were observed for their 1Lb and 1La transitions (|Δε| = 10-12 and 51-57 M-1 cm-1, respectively), while intense CEs were notified in their 1B transitions (|Δε| = 156-216 M-1 cm-1), absorption dissymmetry (gabs) factors being in orders of 10-2. Circularly polarized luminescence spectrum was also obtained for cyanamide derivative CZ1, with a comparative luminescence dissymmetry (glum) factor of 0.013. A computational investigation was applied to address the factors for such remarkable chiroptical responses in these dicarbazolophanes of planar chirality. Absolute configurations were unambiguously determined by the comparison of experimental and theoretical CD spectra, which was affirmed by the X-ray crystal structural analysis of enantiomerically pure sulfonamide derivative CZ2.

Crystal structure of 4-bromo-N-[(3,6-di-tert-butyl-9H-carbazol-1-yl)methyl-idene]aniline.

In the title compound, C27H29BrN2, 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).

Crystal structure of catena-poly[[[bis-(3-oxo-1,3-di-phenyl-prop-1-enolato-κ2 O,O')zinc(II)]-µ2-tris-[4-(pyridin-3-yl)phen-yl]amine-κ2 N:N'] tetra-hydro-furan monosolvate].

The reaction of bis-(3-oxo-1,3-di-phenyl-prop-1-enolato-κ2 O,O')zinc(II), [Zn(dbm)2], with tris-[4-(pyridin-3-yl)phen-yl]amine (T3PyA) in tetra-hydro-furan (THF) afforded the title crystalline coordination polymer, {[Zn(C15H11O2)2(C33H24N4)]·C4H8O} n . The asymmetric unit contains two independent halves of Zn(dbm)2, one T3PyA and one THF. Each ZnII atom is located on an inversion centre and adopts an elongated octa-hedral coordination geometry, ligated by four O atoms of two dbm ligands in equatorial positions and by two N atoms of pyridine moieties from two different bridging T3PyA ligands in axial positions. The crystal packing shows a one-dimensional polymer chain in which the two pyridyl groups of the T3PyA ligand bridge two independent Zn atoms of Zn(dbm)2. In the crystal, the coordination polymer chains are linked via C-H⋯π inter-actions into a sheet structure parallel to (010). The sheets are cross-linked via further C-H⋯π inter-actions into a three-dimensional network. The solvate THF mol-ecule shows disorder over two sets of atomic sites having occupancies of 0.631 (7) and 0.369 (7).

Crystal Structure of (E)-2-(3,3,3-tri-fluoro-prop-1-en-1-yl)aniline.

The mol-ecule of the title compound, C9H8F3N, adopts an E configuration with respect to the C=C double bond. The dihedral angle between the benzene ring and the prop-1-enyl group is 25.4 (3)°. In the crystal, mol-ecules are linked via pairs of N-H⋯F hydrogen bonds into inversion dimers with an R 2 2(16) ring motif. The dimers are linked by C-H⋯N hydrogen bonds, forming a ribbon structure along the b-axis direction. The ribbons are linked by N-H⋯π and C-H⋯π inter-actions, generating a three-dimensional network.

Crystal structure of 7-hy-droxy-8-[(4-methyl-piperazin-1-yl)meth-yl]-2H-chromen-2-one.

In the title compound, C15H18N2O3, the coumarin ring is essentially planar, with an r.m.s. deviation of 0.012 Å. An intra-molecular O-H⋯N hydrogen bond forms an S(6) ring motif. The piperazine ring adopts a chair conformation. In the crystal, a C-H⋯O hydrogen bond generates a C(4) chain motif running along the c axis. The chain structure is stabilized by a C-H⋯π inter-action. The chains are linked by π-π inter-actions [centroid-centroid distance of 3.5745 (11) Å], forming a sheet structure parallel to the bc plane.

Crystal structure of 7-{[bis-(pyridin-2-ylmeth-yl)amino]-meth-yl}-5-chloro-quinolin-8-ol.

In the title compound, C22H19ClN4O, the quinolinol moiety is almost planar [r.m.s. deviation = 0.012 Å]. There is an intra-molecular O-H⋯N hydrogen bond involving the hy-droxy group and a pyridine N atom forming an S(9) ring motif. The dihedral angles between the planes of the quinolinol moiety and the pyridine rings are 44.15 (9) and 36.85 (9)°. In the crystal, mol-ecules are linked via C-H⋯O hydrogen bonds forming inversion dimers with an R 4 (4)(10) ring motif. The dimers are linked by C-H⋯N hydrogen bonds, forming ribbons along [01-1]. The ribbons are linked by C-H⋯π and π-π inter-actions [inter-centroid distance = 3.7109 (11) Å], forming layers parallel to (01-1).

Photoinduced color change and photomechanical effect of naphthalene diimides bearing alkylamine moieties in the solid state.

Photoinduced color change of naphthalene diimides (NDIs) bearing alkylamine moieties has been observed in the solid state. The color change is attributed to the generation of a NDI radical-anion species, which may be formed through a photoinduced electron-transfer process from the alkylamine moiety to the NDI. The photosensitivity of NDIs is highly dependent on the structures of the alkylamine moieties. Crystallographic analysis, kinetic analysis, UV/Vis/NIR spectroscopic measurements, and analysis of the photoproduct suggested that a radical anion was formed through an irreversible process initiated by proton abstraction between an amine radical cation and the neutral amine moiety. The radical anions formed stacks including mixed-valence stacks and radical-anion stacks, as shown by the broad absorption bands in near-IR spectra. These photosensitive NDIs also showed crystal bending upon photoirradiation, which may be associated with a change in the intermolecular distance of the NDI stacks by the formation of monomeric radical anions, mixed-valence stacks, and radical-anion stacks.

Dynamical excimer formation in rigid carbazolophane via charge transfer state.

Formation dynamics of intramolecular excimer in dioxa[3.3](3,6)carbazolophane (CzOCz) was studied by time-resolved spectroscopic methods and computational calculations. In the ground state, the most stable conformer in CzOCz is the anti-conformation where two carbazole rings are in antiparallel alignment. No other isomers were observed even after the solution was heated up to 150 °C, although three characteristic isomers were found by the molecular mechanics calculation: the first is the anti-conformer, the second is the syn-conformer where two carbazole rings are stacked in the same direction, and the third is the int-conformer where two carbazole rings are aligned in an edge-to-face geometry. Because of the anti-conformation, the interchromophoric interaction in CzOCz is negligible in the ground state. Nonetheless, the intramolecular excimer in CzOCz was dynamically formed in an acetonitrile (MeCN) solution, indicating strong interchromophoric interaction and the isomerization from the anti- to syn-conformation in the excited state. The excimer formation in CzOCz is more efficient in polar solvents than in less polar solvents, suggesting the contribution of the charge transfer (CT) state to the excimer formation. The stabilization in the excited state is discussed in terms of molecular orbital interaction between two carbazole rings. The solvent-polarity-induced excimer formation is discussed in terms of the CT character in the int-conformation.

Di-µ 2-acetato-1:2κ (2) O:O';2:3κ (2) O:O'-bis-{µ 2-4,4'-di-chloro-2,2'-[2,2-di-methyl-propane-1,3-diylbis(nitrilo-methanylyl-idene)]diphenolato}-1:2κ (6) O,N,N',O':O,O';2:3κ (6) O,O':O,N,N',O'-tri-cadmium.

In the title linear homo-trinuclear complex, [Cd3(C19H18Cl2N2O2)2(C2H3O2)2], the central Cd(II) atom is located on a centre of inversion and has a distorted octa-hedral coordination geometry formed by four O atoms from two bidentate/tetra-dentate Schiff base ligands and two O atoms from two bridging acetate ligands. The coordination geometry of the terminal Cd(II) atom is square-pyramidal with the tetra-dentate part of the ligand in the basal plane and one O atom from an acetate ligand occupying the apical site. The six-membered CdN2C3 ring adopts a chair conformation. The acetate-bridged Cd⋯Cd distance is 3.3071 (2) Å. The crystal structure is stabilized by C-H⋯O hydrogen bonds, which form C(7) chain motifs and give rise to a two-dimensional supra-molecular network structure lying parallel to the ab plane.

Di-µ(2)-acetato-1:2κ(2)O:O';2:3κ(2)O:O'-bis-{µ(2)-4,4'-dichloro-2,2'-[2,2-dimethyl-propane-1,3-diylbis(nitrilo-methanylyl-idene)]diphenolato}-1:2κ(6)O,N,N',O':O,O';2:3κ(6)O,O':O,N,N',O'-tricopper(II).

The title compound, [Cu(3)(C(19)H(18)Cl(2)N(2)O(2))(2)(CH(3)CO(2))(2)], is a linear homo-trinuclear Cu(II) complex. The central Cu(II) atom is located on a centre of inversion and has a distorted octa-hedral coordination environment formed by six O atoms from two tetra-dentate Schiff base ligands and two bridging acetate ligands. The coordination geometry of the terminal Cu(II) atom is square-pyramidal with a tetra-dentate ligand in the basal plane. The apical site is occupied by one O atom from an acetate ligand. The acetate-bridged Cu⋯Cu distance is 3.0910 (5) Å. An intra-molecular C-H⋯O hydrogen bond forms an S(6) ring motif. The crystal of the trinuclear complex is stabilized by C-H⋯O hydrogen bonds.

1,2-Bis[5-(9-ethyl-9H-carbazol-3-yl)-2-methyl-thio-phen-3-yl]-3,3,4,4,5,5-hexa-fluoro-cyclo-pentene.

The title compound, C(43)H(32)F(6)N(2)S(2), is a new symmetrical photochromic diaryl-ethene derivative with 9-ethyl-carbazol-3-yl substituents. The mol-ecule adopts a photoactive anti-parallel conformation [Irie (2000). Chem. Rev.100, 1685-1716; Kobatake et al. (2002). Chem. Commun. pp. 2804-2805], with a dihedral angle between the mean planes of the two thio-phene rings of 56.23 (6)°. The distance between the two reactive C atoms is 3.497 (3) Å. In the crystal, two mol-ecules are associated through a pair of C-H⋯F inter-molecular hydrogen bonds, forming a centrosymmetric dimer. Dimers are linked by weak π-π inter-actions [centroid-centroid distance = 3.8872 (13) Å], forming chains along the c axis.

Aqua-{4,4',6,6'-tetra-fluoro-2,2'-[(piperazine-1,4-di-yl)dimethyl-ene]diphenolato}copper(II).

In the title compound, [Cu(C(18)H(16)F(4)N(2)O(2))(H(2)O)], the Cu(II) atom shows a distorted square-pyramidal coordination geometry with the N,N',O,O'-tetra-dentate piperazine-diphenolate ligand forming the basal plane. The apical site is occupied by the O atom of a coordinated water mol-ecule. Neighbouring complexes are associated through inter-molecular O-H⋯O and O-H⋯F hydrogen bonds between the water mol-ecule and a phenolate O atom or an F atom from an adjacent ligand, respectively, forming a centrosymmetric dimer. Dimers are linked by additional inter-molecular C-H⋯O and C-H⋯F hydrogen bonds, giving infinite chains propagating along the a axis.

Bis[µ-4,4',6,6'-tetra-chloro-2,2'-(piperazine-1,4-diyldimethyl-ene)diphenolato]dicopper(II).

In the centrosymmetric dinuclear Cu(II) title complex, [Cu(2)(C(18)H(16)Cl(4)N(2)O(2))(2)], the Cu(II) atom adopts a square-pyramidal geometry with a tetra-dentate ligand in the basal plane. The apical site is occupied by a phenolate O atom from an adjacent ligand, forming a dimer. The mol-ecular structure is stabilized by intra-molecular C-H⋯O and C-H⋯Cl hydrogen bonds.

4,4'-Dichloro-2,2'-(piperazine-1,4-diyldimethyl-ene)diphenol.

In the titile compound, C(18)H(20)Cl(2)N(2)O(2), the piperazine ring adopts a chair conformation. The mol-ecule has a non-crystallographic inversion centre in the middle of the piperazine ring at approximate position (3/4, 1/8, 3/8). There are intra-molecular O-H⋯N hydrogen bonds forming S(6) ring motifs. Inter-molecular C-H⋯O hydrogen bonds generate anti-parallel C(5) chain motifs propagating along the b axis, forming sheets parallel to the bc plane with a first-level graph-set S(6)C(5)R(6) (6)(26).