Yong-Hong Liu

Synthesis and structure of a Schiff base and its bivalent transition metal complexes

A Schiff base (HCSmz) was synthesized via (E)-cinnamaldehyde with S-methyl dithiocarbazate and six bivalent transition metal complexes [M(CSmz)2] (M=Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Hg2+) were prepared. The complexes were characterized by elemental analyses, IR, 1H NMR, and UV-Vis spectra, and the Ni(II) and Zn(II) complexes were also characterized by single crystal X-ray diffraction. After tautomerism of thiotone to thioenol and deprotonization of the thioenol, two ligands chelate the metal by two nitrogens of azomethine and two sulfurs of thioenol. Ni(CSmz)2 crystallizes in the centrosymmetric space group P21 /n with a perfectly square planar trans-configuration with Ni located at the center of the square; crystal packing is stabilized by intra- and intermolecular C–H···S hydrogen bonds. Zn(CSmz)2 is in the mirror-symmetric space group I41 /a in a distorted tetrahedral geometry with two equivalent Zn–N and Zn–S bonds; crystal packing is stabilized by intermolecular C–H···π hydrogen bonds.

(E)-1-Ferrocenyl-3-phenyl­prop-2-en-1-one

The title compound, [Fe(C5H5)(C14H11O)], exists as the E isomer, and the substituent is fully conjugated with the attached five-membered ring. In the ferrocene unit, the substituted cyclopentadienyl ring (Cps) plane and unsubstituted cyclopentadienyl ring (Cp) plane are almost parallel, and the C atoms in Cp and Cps are in an eclipsed conformation. In the crystal structure, molecules are linked into C(5) chains via intermolecular C—H⋯O hydrogen bonds, and neighbouring chains are assembled into sheets by intermolecular C—H⋯π(arene) hydrogen bonds along the c axis.

Benzyl 5-ferrocenyl-3-(4-methyl-phen-yl)-2-pyrazoline-1-dithio-carboxyl-ate.

In the title compound, [Fe(C5H5)(C23H21N2S2)], the cyclopentadienyl rings of the ferrocenyl unit deviate slightly from the eclipsed form. In the pyrazoline ring, the N atom bonded to S-benzyl dithiocarbazate exhibits unconventional sp 2-hybrid character in order to form an extended conjugated system. The pyrazoline ring displays an envelope conformation. The molecules are linked into chains along the b axis via C—H⋯S intermolecular hydrogen bonds.

(E)-1-Ferrocenyl-3-(3-nitro-phen-yl)prop-2-en-1-one.

In the title compound, [Fe(C5H5)(C14H10NO3)], one cyclopentadiene ring is substituted and one is unsubstituted. The two rings are almost parallel and are eclipsed and ordered. The conjugated substituent is slightly twisted with respect to the cyclopentadiene ring. The crystal structure contains four intermolecular C—H⋯O hydrogen-bonds in the range 3.324 (3)–3.539 (3) Å and one π(aryl ring)–π (Cp ring) stacking interaction with a ring–centroid distance of 3.894 (2) Å.

(3Z)-3-[(Z)-2-(2-Oxoindolin-3-yl­idene)hydrazin-1-yl­idene]indolin-2-one 0.17-hydrate

In the title compound, C16H10N4O2·0.17H2O, prepared by the one-step condensation reaction of isatin with hydrazine hydrate under microwave irradiation, the complete organic molecule is generated by crystallographic inversion symmetry and therefore exists in an S-trans conformation. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, generating a three-dimensional framework with [001] channels, which are occupied by the disordered water molecules.

(E)-1-Ferrocenyl-3-(2-fur­yl)prop-2-en-1-one

The title compound, [Fe(C5H5)(C12H9O2)], exhibits an E configuration. In the ferrocene unit, the two cyclopentadienyl rings are almost parallel [dihedral angle = 0.76 (12)°] and the C atoms are in an eclipsed conformation. An intramolecular C—H⋯O hydrogen bond generates an S(5) ring. In the crystal, the molecules are linking into zigzag chains via two C—H⋯O hydrogen-bonding interactions along the c axis and neighbouring chains are stabilized by electrostatic interaction forces.

1,3-Dithian-2-one azine.

In an asymmetric unit of the title compound, C8H12N2S4, there are two crystallographically independent half molecules lying on inversion centers. One of the molecules is disordered over two positions with relative occupancies of 82.0 (2) and 18.0 (2) for the major and minor components. In the crystal structure, molecules are linked into a three-dimensional framework via intermolecular C—H⋯N hydrogen-bonding interactions.

Methyl 3-methyl-5-oxo-4-(phenyl-hydrazono)-4,5-dihydro-1H-pyrazole-1-carbodithio-ate.

The title compound, C12H11N4OS2, has been synthesized by the condensation reaction of 3-oxo-2-(phenylhydrazono)butanate and S-methyldithiocarbazate. The hydrazine unit and the pyrazole ring are coplanar [dihedral angle 3.8 (4)°] due to extensive conjugation and the N—H⋯O=C intramolecular hydrogen bond. Two adjacent molecules form dimers due to short C—H⋯O=C [R 2 2 (18)] and C—H⋯S=C [R 2 2 (22)] intermolecular interactions. C—H⋯S—C [R 2 2 (14)] interactions link these dimers into ribbons in the [011] direction.

N-[(E,Z)-1,3-Diphenyl-prop-2-enyl-idene]-N'-(1,3-dithio-lan-2-yl-idene)hydrazine.

Molecules of the title compound, C18H16N2S2, exist as the (2E, 1′Z)-isomer. The 1,3-dithiolane ring has an envelope conformation; the atoms of the C—C bond are disordered over two positions with occupancies of 0.47 (7) and 0.53 (7). The structure exhibits intermolecular C—H⋯S and C—H⋯π(arene) hydrogen bonds.

(E)-1-Ferrocenyl-3-(4-methoxy­phen­yl)­prop-2-en-1-one

In the title compound, [Fe(C5H5)(C15H13O2)], a conjugated substituent group bridges a five-membered η5-C5H4 ring and a benzene ring. In the ferrocene unit, the substituted (Cps) and unsubstituted (Cp) cyclopentadienyl rings are eclipsed and almost parallel [Cps—Fe—Cps angle = 176.1 (2)°]. The molecule is linked into an S(5) motif via intramolecular C—H⋯O hydrogen bonds. The molecules are arranged into a three-dimensional framework by five intermolecular C—H⋯O hydrogen bonds and one intermolecular C—H⋯π(Cps) interaction.