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New derivatives of thiosemicarbazone Schiff base with isatin moiety were synthesized L1-L6. The structures of these compounds were characterized based on the spectroscopic techniques. Compound L6 was further characterized by XRD single crystal. The interaction of these compounds with calf thymus (CT-DNA) exhibited high intrinsic binding constant (k(b)=5.03-33.00×10(5) M(-1)) for L1-L3 and L5 and (6.14-9.47×10(4) M(-1)) for L4 and L6 which reflect intercalative activity of these compounds toward CT-DNA. This result was also confirmed by the viscosity data. The electrophoresis studies reveal the higher cleavage activity of L1-L3 than L4-L6. The in vitro anti-proliferative activity of these compounds against human colon cancer cell line (HCT 116) revealed that the synthesized compounds (L3, L6 and L2) exhibited good anticancer potency., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In the title compound, C(11)H(11)FN(4)OS, an intra-molecular N-H⋯O hydrogen bond generates an S(6) ring. In the crystal, mol-ecules form chains through N-H⋯O hydrogen bonds, which are extended by N-H⋯S hydrogen bonds into an infinite three-dimensional network.

In the crystal structure of the title compound, C(7)H(14)N(4)OS, mol-ecules are linked through N-H⋯S and O-H⋯N hydrogen bonds and C-H⋯S interactions, forming chains propagating along [21-1].

The asymmetric unit of the title compound, [Ni(C(15)H(11)N(4)OS)(2)]·C(3)H(7)NO, contains one Ni(II) complex mol-ecule and one disordered dimethyl-formamide solvent mol-ecule. The Ni(II) ion is six-coordinated in a distorted octa-hedral geometry by two N, two O and two S atoms. An intra-molecular C-H⋯S hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are linked through inter-molecular N-H⋯S, N-H⋯O, C-H⋯N, C-H⋯O and C-H⋯S hydrogen bonds into infinite two-dimensional network parallel to the ab plane. The structure is further stablized by weak C-H⋯π inter-actions. The dimethylformamide solvent molecule is disordered over two sets of sites in a 0.514 (15):0.486 (15) ratio.

In the title compound, C(10)H(9)N(5)O(3)S, an intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are linked via N-H⋯S hydrogen bonds into a zigzag chain along the b axis. C-H⋯O inter-actions are observed between the chains.

In the title compound, C(11)H(12)N(4)OS, an intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, the mol-ecules form a helical chain along the a axis through an N-H⋯O hydrogen bond. These chains are extended by an N-H⋯S hydrogen bond and a C-H⋯π inter-action into a three-dimensional network.

In the title compound, C(10)H(9)ClN(4)OS, an intra-molecular N-H⋯O hydrogen-bonding inter-action and an N-H⋯N inter-action generate ring motifs [graph sets S(6) and S(5), respectively]. In the crystal, mol-ecules form a chain through N-H⋯O hydrogen bonds, and these are extended by N-H⋯S hydrogen-bonding inter-actions into an infinite three-dimensional network. The crystal structure also exhibits weak C-H⋯π inter-actions.

In the title compound, C(15)H(12)N(4)OS, the dihedral angle between the nine-membered indolin-2-one ring system and the phenyl ring is 2.72 (7)°. Intra-molecular cyclic N-H⋯O and C-H⋯S hydrogen-bonding inter-actions [graph set S(6)] are present, as are weak N-H⋯N inter-actions [graph set S(5)]. In the crystal, mol-ecules form centrosymmetric cyclic dimers through pairs of N-H⋯O hydrogen bonds [graph set R(2) (2)(8)] and these are extended by C-H⋯S inter-actions. The crystal structure also features weak C-H⋯π inter-actions.

In the title complex, [Ni(C(7)H(14)N(4)OS)(2)]Cl(2), the Ni(II) ion is six-coordinated in a distorted octa-hedral geometry by four N atoms from the two imine and two oxime groups, and two S atoms from the thione groups. Two chloride ions complete the asymmetric unit. In the crystal, mol-ecules are linked through N-H⋯Cl and O-H⋯Cl hydrogen bonds into an infinite chain propagating along [101].

The title compound, C(15)H(11)FN(4)OS, crystallizes with three independent mol-ecules (A, B and C) in the asymmetric unit. The dihedral angles between the nine-membered 5-fluoro-indolin-2-one ring system and the benzene ring are 22.14 (11), 12.56 (11) and 3.70 (11)° in mol-ecules A, B and C, respectively. In all three mol-ecules, intra-molecular cyclic N-H⋯O and C-H⋯S hydrogen-bonding inter-actions [graph set S(6)] are present in the N-N-C-N chain between the ring systems. In the crystal, the A mol-ecules form centrosymmetric cyclic dimers through inter-molecular N-H⋯O hydrogen bonds, which are linked into a supramolecular chain along [100] via C-H⋯F interactions; each type of hydrogen bond has graph set graph set R(2) (2)(8). A similar chain stabilised by similar interactions and also along [100] but, comprising alternating molecules of B and C is found. The latter chains are connected via C-H⋯S interactions, forming a layer with a zigzag topology parallel to (001).

The title compound, C(7)H(6)N(2)O(4), is approximately planar (r.m.s. deviation = 0.026 Å for the 13 non-H atoms). The mol-ecular structure is stabilized by intra-molecular N-H⋯O hydrogen bonds, which generate S(6) ring motifs. In the crystal, mol-ecules are linked via inter-molecular N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds into a three-dimensional network.

The asymmetric unit of the title compound, [Ni(C(6)H(12)N(4)OS)(2)]Cl(2), contains two independent Ni(II) complex cations and four chloride anions. Each Ni(II) ion is six-coordinated in a distorted octa-hedral geometry by four N atoms from the two imine and two oxime groups and two S atoms from the thione group. In the crystal, the cations and anions are linked through N-H⋯Cl and O-H⋯Cl hydrogen bonds into infinite chains propagating along [10[Formula: see text]]. Weak inter-molecular C-H⋯O and C-H⋯Cl hydrogen bonds are also observed.

In the title compound, C(6)H(12)N(4)OS, an intra-molecular N-H⋯N hydrogen-bond is present giving rise to an S(5) ring motif. In the crystal, double-stranded chains propagating along [10[Formula: see text]] are formed via pairs of O-H⋯S and N-H⋯S hydrogen bonds. The chains are further stabilized by C-H⋯S interactions.

Lycopene extraction was carried out via the ultrasonic assisted extraction (UAE) with response surface methodology (RSM). Sonication enhanced the efficiency of relative lycopene yield (enhancement of 26% extraction yield of lycopene in 6 replications at 40.0 min, 40.0 °C and 70.0% v/w in the presence of ultrasound), lowered the extraction temperature and shortened the total extraction time. The extraction was applied with the addition of oxygen-free nitrogen flow and change of water route during water bath sonication. The highest relative yield of lycopene obtained was 100% at 45.0 °C with total extraction time of 50.0 min (30:10:10) and ratio of solvent to freeze-dried tomato sample (v/w) of 80.0:1. Optimisation of the lycopene extraction had been performed, giving the average relative lycopene yield of 99% at 45.6 min, 47.6 °C and ratio of solvent to freeze-dried tomato sample (v/w) of 74.4:1. From the optimised model, the average yield of all-trans lycopene obtained was 5.11±0.27 mg/g dry weight. The all-trans lycopene obtained from the high-performance liquid chromatography (HPLC) chromatograms was 96.81±0.81% with 3.19±0.81% of cis-lycopenes. The purity of total-lycopene obtained was 98.27±0.52% with β-carotene constituted 1.73±0.52% of the extract. The current improved, UAE of lycopene from tomatoes with the aid of RSM also enhanced the extraction yield of trans-lycopene by 75.93% compared to optimised conventional method of extraction. Hence, the current, improved UAE of lycopene promotes the extraction yield of lycopene and at the same time, minimises the degradation and isomerisation of lycopene., (Copyright © 2011 Elsevier B.V. All rights reserved.)

In the title compound, C(16)H(14)N(4)OS, the dihedral angle between the nine-membered 5-methyl-indolin-2-one ring system and the benzene ring is 10.21 (7)°. Intra-molecular cyclic N-H⋯O and C-H⋯S hydrogen-bonding inter-actions [graph set S(6)] are present within the N-N-C-N chain between the ring systems. In the crystal, mol-ecules form centrosymmetric cyclic dimers through pairs of N-H⋯O hydrogen bonds [graph set R(2) (2)(8)].

In the title compound, C(15)H(11)ClN(4)OS, the dihedral angle between the nine-membered 5-chloro-indolin-2-one ring system and the benzene ring is 10.00 (6)°. Intra-molecular cyclic N-H⋯O and C-H⋯S hydrogen-bonding inter-actions [graph set S(6)] are present in the N-N-C-N chain between the ring systems. In the crystal, mol-ecules form centrosymmetric cyclic dimers through inter-molecular N-H⋯O hydrogen bonds [graph-set R(2) (2)(8)] and are extended by C-H⋯Cl inter-actions into infinite chains which propagate along [100].

In the title mononuclear complex, [Zn(C(21)H(16)N(3)O)Cl], the Zn(II) ion is coordinated in a distorted tetra-hedral geometry by two benzimidazole N atoms and one phenolate O atom from the tridentate Schiff base ligand and a chloride ligand. The benzimidazole ring system forms dihedral angles of 26.68 (9) and 56.16 (9)° with the adjacent benzene ring and the methyl-phenolate group benzene ring, respectively. In the crystal, mol-ecules are linked by N-H⋯Cl hydrogen bonds into chains along [100]. Furthermore, weak C-H⋯O and C-H⋯π inter-actions, in addition to π-π inter-actions with centroid-centroid distances in the range 3.5826 (13)-3.9681 (13) Å, are also observed.

In the zwitterionic title compound, C(18)H(16)N(2)O(4), the dihedral angle between the planes of the benzene and indole rings is 26.38 (10)°. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are linked through N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds into infinite chains propagating in [010].

The asymmetric unit of the title compound, C(20)H(15)N(3)O, contains two independent mol-ecules, each of which is disordered over two sets of sites corresponding to a rotation of approximately 180° of the dihydro-benzimidazoquinazoline moiety, with refined site occupancies of 0.7479 (13) and 0.2521 (12) for both mol-ecules. The pyrimidine rings are in sofa conformations. In one mol-ecule, the hy-droxy-substituted benzene ring forms dihedral angles of 83.9 (3) and 82.4 (4)° for the major and minor components, respectively, with the mean plane of the benzimidazole ring system. The corres-ponding dihedral angles in the other mol-ecule are 88.31 (14) and 85.8 (6)°. In the crystal, mol-ecules are linked via inter-molecular O-H⋯N and N-H.·O hydrogen bonds into chains along [100].

In the title compound, [Sn(C(6)H(5))(3)(C(7)H(3)ClNO(4))], the four-coordinate Sn(IV) atom exists in a distorted tetra-hedral geometry, formed by a monodentate carboxyl-ate group and three phenyl rings. The conformation is stabilized by an intra-molecular C-H⋯O hydrogen bond, which generates an S(5) ring. The aromatic ring of the 4-chloro-3-nitro-benzoate ligand makes dihedral angles of 75.64 (12), 64.37 (12) and 2.97 (12)° with the three phenyl ligands. The O atoms of the nitro group are disordered over two sets of sites in a 0.817 (5):0.183 (5) ratio. In the crystal, mol-ecules are linked via inter-molecular C-H⋯O hydrogen bonds into chains running parallel to [010].

The title compound, [Sn(C(6)H(5))(3)(C(7)H(5)N(2)O(4))](n), forms polymeric chains along [010]. The Sn(IV) ion is five-coordinated in a distorted trigonal-bipyramidal geometry by two monodentate carboxyl-ate groups and three phenyl rings. The axial sites are occupied by the O atoms of two symmetry-related carboxyl-ate groups [O-Sn-O = 170.88 (3)°]. The benzene ring of the 5-amino-2-nitro-benzoate ligand forms dihedral angles of 82.92 (6), 81.10 (6) and 83.54 (6)° with respect to the three phenyl rings. In the crystal, the chains are linked by inter-molecular N-H⋯O and weak C-H⋯O inter-actions into a three-dimensional network. The crystal structure is further stabilized by weak inter-molecular C-H⋯π inter-actions.

In the zwitterionic title compound, C(18)H(16)N(2)O(4)·H(2)O, the dihedral angle between the planes of the benzene and indole rings is 39.20 (8)°. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, inter-molecular hy-droxy and water O-H⋯O(carboxyl-ate) and N(+)-H⋯O(carboxyl-ate) and indole N-H⋯O(water) hydrogen bonds give a three-dimensional structure.

In the title benzimidazole mononuclear complex, [ZnCl(2)(C(13)H(11)N(3))], the Zn(II) ion is four-coordinated in a distorted tetra-hedral geometry by an imidazole N, an amino N and two Cl atoms. The dihedral angle between the benzimidazole and benzene rings is 9.57 (1)°. In the crystal, mol-ecules are linked by weak N-H⋯Cl hydrogen bonds into layers parallel to the bc plane. π-π inter-actions with centroid-centroid distances in the range 3.4452 (8)-3.8074 (8) Å are also observed.

In the title complex, [Sn(4)(C(4)H(9))(8)(C(7)H(5)N(2)O(4))(4)O(2)], all four Sn(IV) atoms are five-coordinated with distorted trigonal-bipyramidal SnC(2)O(3) geometries. Two Sn(IV) atoms are coordin-ated by two butyl groups, one benzoate O atom and two bridging O atoms, whereas the other two Sn(IV) atoms are coordinated by two butyl groups, two benzoate O atoms and a bridging O atom. All the butyl groups are equatorial with respect to the SnO(3) trigonal plane. In the crystal, mol-ecules are linked into a two-dimensional layer parallel to the ab plane by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds and further stabilized by a π-π inter-action [centroid-centroid distance = 3.6489 (11) Å]. Intra-molecular N-H⋯O and C-H⋯O hydrogen bonds stabilize the mol-ecular structure. Two of the butyl groups are each disordered over two sets of sites with site-occupancy ratios of 0.510 (4):0.490 (4) and 0.860 (5):0.140 (5).

A series of Zn(II)-Schiff bases I, II and III complexes were synthesized by reaction of o-phenylenediamine with 3-methylsalicylaldehyde, 4-methylsalicylaldehyde and 5-methylsalicylaldehyde. These complexes were characterized using FT-IR, UV-Vis, Diffuse reflectance UV-Vis, elemental analysis and conductivity. Complex III was characterized by XRD single crystal, which crystallizes in the triclinic system, space group P-1, with lattice parameters a=9.5444(2) Å, b=11.9407(2) Å, c=21.1732(3) Å, V=2390.24(7) Å(3), D ( c )=1.408 Mg m(-3), Z=4, F(000)=1050, GOF=0.981, R1=0.0502, wR2=0.1205. Luminescence property of these complexes was investigated in DMF solution and in the solid state. Computational study of the electronic properties of complex III showed good agreement with the experimental data., (© Springer Science+Business Media, LLC 2011)

In the title solvated benzimidazole compound, C(20)H(15)N(3)O(2)·C(2)H(6)OS, both the benzimidazole fused-ring system and the complete dimethyl sulfoxide solvent mol-ecule are disordered over two sets of sites, in 0.750 (5):0.250 (5) and 0.882 (4):0.118 (4) ratios, respectively. The conformation of the pyrimidine ring is close to a half-chair for the major disorder component, whereas for the minor component it is close to a boat. The dihy-droxy-phenyl ring is almost perpendicular to the mean plane of the benzimidazole ring [dihedral angle = 87.3 (2)° for the major disorder component and 88.3 (5)° for the minor disorder component]. In the crystal, mol-ecules are linked into layers parallel to (110) by O-H⋯N and C-H⋯O hydrogen bonds. A bifurcated O-H⋯(O,S) bond links the benzimidazole and solvent mol-ecules.

The synthesis and characterization of two cobalt(II) complexes, Co(phen)(ma)Cl 1 and Co(ma)(2)(phen) 2, (phen=1,10-phenanthroline, ma(-)=maltolate or 2-methyl-4-oxo-4H-pyran-3-olate) are reported herein. The complexes have been characterized by FTIR, CHN analysis, fluorescence spectroscopy, UV-visible spectroscopy, conductivity measurement and X-ray crystallography. The number of chelated maltolate ligands seems to influence their DNA recognition, topoisomerase I inhibition and antiproliferative properties., (Copyright © 2010 Elsevier Inc. All rights reserved.)

In the title compound, [Cu(C(4)H(8)NO(3))Cl(C(10)H(8)N(2))]·H(2)O, the Cu(II) atom is in a slightly distorted square-pyramidal coordination geometry with the basal plane defined by the two N atoms of the bipyridine ligand and the N and O atoms from the threoninate ion and the apical site occupied by the Cl atom. In the crystal, inter-molecular O-H⋯O, N-H⋯O, O-H⋯Cl, C-H⋯O and C-H⋯Cl inter-actions link the mol-ecules into a three-dimensional network. A π-π inter-action with a centroid-centroid distance of 3.461 (1) Å is also present.

The title Schiff base compound, C(18)H(13)NO(2), is a zwitterion, with the naphthol hy-droxy group deprotonated and the imine N atom protonated. It adopts an E configuration about the central C=N double bond. The dihedral angle between the naphthyl ring system and the benzene ring is 1.73 (11)°. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, adjacent mol-ecules are connected by inter-molecular C-H⋯O hydrogen bonds, forming a supra-molecular ribbon along the b axis.

The title compound, C(7)H(6)ClNO(2), is almost planar, with an r.m.s. deviation of 0.040 Å. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are linked into centrosymmetric dimers by pairs of O-H⋯O hydrogen bonds. These dimers are stacked along [010].

In the title compound, C(13)H(8)ClN(3)O(3)·C(3)H(7)NO, the benzimidazole and benzene rings make a dihedral angle of 0.63 (11)°. An intra-molecular O-H⋯N hydrogen bond generates an S(6) ring motif. The solvent mol-ecule is hydrogen-bonded to the benzimidazole mol-ecule by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds, generating an R(1) (2)(7) ring motif. In the crystal, the mol-ecules are arranged into parallel layers perpendicular to the c axis and stabilized by weak π-π inter-actions [centroid-centroid distances in the range 3.4036 (18)-3.5878 (16) Å].

IN THE TITLE COMPOUND [SYSTEMATIC NAME: 3,3'-Dibutyl-1,1'-(5-methyl-m-phenyl-enedimethyl-ene)diimidazol-1-ium bis-(hexa-fluoridophosphate)], C(23)H(34)N(4) (2+)·2PF(6) (-), the imidazole rings are inclined at angles of 68.06 (7) and 75.05 (8)° with respect to the central benzene ring. In the crystal, mol-ecules are linked into one-dimensional columns along [010] via weak inter-molecular C-H⋯F hydrogen bonds. The crystal structure is further consolidated by weak C-H⋯π(arene) inter-actions. One of the n-butyl groups is disordered over two sites with refined occupancies of 0.694 (5) and 0.306 (5). In addition, four of the F atoms of one of the PF(6) (-) cations are disordered over two sites with occupancies of 0.64 (3) and 0.36 (3).

The tetranuclear molecules of the title compound, [Sn(4)(C(4)H(9))(8)(C(7)H(5)N(2)O(4))(4)O(2)], reside on a crystallographic inversion center. Both the two independent Sn atoms are five-coordinate, with distorted trigonal-bipyramidal geometries. One Sn atom is coordinated by two O atoms of the carboxyl-ate anions, one bridging O atom and two butyl groups and the other Sn atom is coordinated by an O atom of the carboxyl-ate anion, two bridging O atoms and two butyl groups. All the butyl groups are equatorial with respect to the SnO(3) trigonal plane. The mol-ecular structure is stabilized by intra-molecular N-H⋯O hydrogen bonds. In the crystal, pairs of inter-molecular bifurcated acceptor N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into chains along [10]. Weak inter-molecular C-H⋯π and π-π inter-actions [centroid-centroid distance = 3.713 (2) Å] are also observed.

The title Schiff base compound, C(13)H(11)N(3)O(5)S, exists in an E configuration with respect to the C=N double bond. The benzene rings are almost coplanar, making a dihedral angle of 2.82 (6). The sulfonamide group is twisted away from the attached phenyl ring with an N-S-C-C torsion angle of 64.84 (11)°. An intra-molecular O-H⋯N hydrogen bond stabilizes the mol-ecule, generating an S(6) ring motif. In the crystal, inter-molecular N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

The asymmetric unit of the title complex, [Ag(2)(C(22)H(30)N(4))(2)](PF(6))(2), consists of one Ag(I) ion, one 1,4-bis-[(3-butyl-imidazolium-1-yl)meth-yl]benzene ligand and one discrete hexa-fluoridophosphate anion. The formula unit is generated by an inversion center. The unique Ag(I) ion is coordinated by two C atoms of two heterocyclic carbene ligands in an essentially linear geometry. In the crystal structure, cations and anions are linked through weak C-H⋯F hydrogen bonds, forming a three-dimensional network.

The five-coordinate Sn atom in the title compound, [Sn(C(6)H(5))(3)(C(8)H(6)NO(4))(CH(3)OH)], exists in a trans-C(3)SnO(2) trigonal-bipyramidal coordination polyhedron of which the O atoms of the methanol mol-ecule and carboxyl-ate group occupy the apical sites. In the crystal, adjacent mol-ecules are linked by inter-molecular O-H⋯O inter-actions, generating a helical hydrogen-bonded chain running along the b axis.

The asymmetric unit of the title complex salt, [Ni(C(10)H(24)N(4))(H(2)O)(2)](C(4)H(2)O(4))·4H(2)O, comprises half of a nickel(II) complex dication, half of a fumarate dianion and two water mol-ecules. Both the Ni(II) cation and fumarate anion lie on a crystallographic inversion center. The Ni(II) ion in the cyclam complex is six-coordinated within a distorted N(4)O(2) octa-hedral geometry, with the four cyclam N atoms in the equatorial plane and the two water mol-ecules in apical positions. The six-membered metalla ring adopts a chair conformation, whereas the five-membered ring exists in a twisted form. In the crystal packing, inter-molecular O-H⋯O hydrogen bonds between the water molecules and the carboxyl groups of the fumarate anions lead to the formation of layers with R(4) (2)(8) ring motifs. Ni(II) complex cations are sandwiched between two such layers, being held in place by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, consolidating a three-dimensional network.

The title compound, C(13)H(11)NO(3), crystallizes in a zwitterionic form and has a trans configuration about the C=N bond. The mol-ecule is almost planar, the dihedral angle between the two benzene rings being 4.32 (8)°. The two hy-droxy substit-uents are coplanar with each of their attached benzene rings [r.m.s. deviations of 0.0053 (2) and 0.0052 (2) Å]. An intra-molecular N-H⋯O hydrogen bond formed between the iminium N and the phenolate O atom generates an S(6) ring motif. In the crystal, the mol-ecules are linked through O-H⋯O hydrogen bonds into chains along [110]. Two neighbouring chains are further connected through O-H⋯O hydrogen bonds in an anti-parallel manner. π-π inter-actions are also observed, with centroid-centroid distances of 3.7115 (19) and 3.743 (2) Å.

The asymmetric unit of title compound, [Fe(C(5)H(5))(C(9)H(12)N(3)S)], contains two crystallographically independent mol-ecules, A and B. The two cyclo-penta-dienyl (Cp) rings are parallel to each other in both mol-ecules, forming dihedral angles of 2.3 (3) and 1.0 (3)°, respectively, and adopt an eclipsed conformation. The mean plane of the semicarbazone group is twisted slightly away from the attached Cp ring in both mol-ecules, the dihedral angles between the mean plane and the Cp ring being 15.3 (2) and 10.8 (2)°. The ethyl group in mol-ecule A is coplanar with the mean plane of the semicarbazone group [C-N-C-C torsion angle = -175.2 (4)°], whereas it is nearly perpendicular in mol-ecule B [C-N-C-C torsion angle = 84.8 (6)°]. In the crystal structure, inter-molecular N-H⋯S hydrogen bonds link the mol-ecules into dimers. These dimers are further linked into chains via inter-molecular C-H⋯S hydrogen bonds. The crystal studied was a non-merohedral twin with a refined ratio of the twin components of 0.265 (2):0.735 (2).

The asymmetric unit of the title polymeric complex, {[Sn(2)=(C(6)H(5))(6)(C(3)H(2)O(4))(H(2)O)]·C(3)H(6)O}(n), comprises of two Sn cations, one malonate anion and a non-coordinating acetone solvent mol-ecule. Both crystallographically independent Sn cations are five-coordinated by two O and three C atoms in a distorted trigonal-bipyrimidal geometry. One of the Sn cations is bridged by the malonate units, affording polymeric chains which run along [001]. Weak intra-molecular C-H⋯π inter-actions stabilize the mol-ecular structure. In the crystal structure, adjacent chains are inter-connected by inter-molecular O-H⋯O and C-H⋯O hydrogen bonds into a three-dimensional supra-molecular structure. A weak inter-molecular C-H⋯π inter-action is also observed.

The asymmetric unit of the title compound, [Fe(C(5)H(5))(C(7)H(8)N(3)S)], consists of two crystallographically independent mol-ecules, A and B. The cyclo-penta-dienyl (Cp) rings in both mol-ecules adopt an eclipsed conformation and are parallel to each other, forming dihedral angles of 2.5 (3) and 1.1 (3)°, respectively. The mean plane of the semicarbazone group is coplanar with the attached Cp ring in mol-ecule A, whereas it is twisted away in mol-ecule B. In the crystal structure, inter-molecular N-H⋯S hydrogen bonds link the mol-ecules into two-dimensional planes parallel to the ab plane. The structure is further consolidated by C-H⋯π inter-actions.

The asymmetric unit of the title complex, [Tb(2)(C(7)H(5)O(2))(6)(C(12)H(8)N(2))(2)]·2C(7)H(6)O(2), consists of one-half of the complex mol-ecule, which lies on a crystallographic inversion centre, and one benzoic acid solvent mol-ecule. The two Tb(III) ions are linked by four bridging benzoate ions, with a Tb⋯Tb distance of 3.9280 (6) Å. Additionally, each Tb(III) ion is coordinated by one phenanthroline heterocycle and a bidentate benzoate ion. The irregular nine-coordinated geometry of the Tb(III) ion is composed of seven O and two N atoms. The mol-ecular structure is stabilized by intra-molecular C-H⋯O hydrogen bonds. In the crystal structure, mol-ecules are linked into chains along the a axis by inter-molecular C-H⋯O hydrogen bonds. The crystal structure is further stabilized by inter-molecular C-H⋯O and C-H⋯π inter-actions. Weak π-π inter-actions are also observed [centroid-centroid distances = 3.6275 (14)-3.6604 (14) Å].

The title compound, C(13)H(10)BrNO(2), crystallizes in a zwitterionic form. The zwitterion exists in a trans configuration about the C=N bond and is almost planar, the dihedral angle between the two benzene rings being 2.29 (9)°. An intra-molecular N-H⋯O hydrogen bond formed between the iminium NH(+) and the phenolate O(-) atoms generates an S(6) ring motif. In the crystal, the zwitterions are linked through O-H⋯O hydrogen bonds into chains along [101] and these chains are further connected through C-H⋯Br inter-actions into a two-dimensional network perpendicular to (101). C⋯C [3.572 (3)-3.592 (3) Å] and C⋯Br [3.5633 (19)-3.7339 (18) Å] short contacts are observed. The crystal studied was a twin with twin law 00, 00, 001 with a domain ratio of 0.09919 (2):0.90081 (2).