Crystal structure of 1,6-di-thia-cyclo-deca-cis-3,cis-8-diene (DTCDD).

The title compound, C8H12S2 (trivial name DTCDD), was obtained as a side product of the reaction between cis-1,4-di-chloro-but-2-ene and sodium sulfide. The asymmetric unit consists of one-quarter of the mol-ecule (S site symmetry 2) and the complete mol-ecule has 2/m (C 2h ) point symmetry with the C=C bond in an E conformation. The geometry of the title compound is compared to those of a chloro derivative and a mercury complex.

Two organophosphorus pesticides: methyl parathion and dicapthon.

Structural studies performed in this laboratory of organophosphorus pesticides continue with these related compounds. The -NO2 groups of methyl parathion (systematic name: dimethyl 4-nitrophenyl phosphorothioate, C8H10NO5PS) and dicapthon (systematic name: 2-chloro-4-nitrophenyl dimethyl phosphorothioate, C8H9ClNO5PS) make dihedral angles of 10.67 (8) and 5.8 (1)°, respectively, with the planes of their attached rings, which accompanies angular distortion at the ring C atoms to which the -NO2 groups are attached. Similar distortions are observed at the C atom to which the thiophosphate groups are attached. Significant differences in distances and angles around the phenolic O, versus the -OMe groups, explain why it is the site of hydrolysis for these compounds. A comparison of a torsion angle involving the thiophosphate group and phenolic O atom with similar pesticide structures is given and indicates steric influences on that angle.

Two molybdenum pentacarbonyl complexes with electroneutral phosphane ligands: [bis(morpholin-4-yl)(pentafluoroethyl)phosphane-κP]pentacarbonylmolybdenum(0) and pentacarbonyl[(pentafluoroethyl)bis(piperidin-1-yl)phosphane-κP]molybdenum(0).

The crystal structures of the title compounds, [Mo{(C4H8NO)2P(C2F5)}(CO)5], (1a), and [Mo{(C5H10N)2P(C2F5)}(CO)5], (2a), were determined as part of a larger project that focuses on the synthesis and coordination chemistry of phosphane ligands possessing moderate (electroneutral, i.e. neither electron-rich nor electron-deficient) electronic characteristics. Both complexes feature a slightly distorted octahedral geometry at the metal center, due to the electronic and steric repulsions between two of the four equatorial CO groups and the pentafluoroethyl group attached to the phosphane ligand. Bond length and angle data for (1a) and (2a) support the conclusion that the free phosphane ligands are electroneutral. For complex (1a), the Mo-P, Mo-Cax and Mo-Ceq(ave) bond lengths are 2.5063 (5), 2.018 (2) and 2.048 (2) Å, respectively, and for complex (2a) these values are 2.5274 (5), 2.009 (3) and 2.050 (3) Å, respectively. Geometric data for (1a) and (2a) are compared with similar data reported for analogous Mo(CO)5 complexes.

O,O-Dimethyl O-(4-sulfamoylphen-yl) phospho-rothio-ate (cythio-ate).

The title mol-ecule, C8H12NO5PS2, exhibits a crystallographic mirror plane that is perpendicular to the ring and bis-ects the sulfamoyl and thio-phosphate ester groups. In the crystal, mol-ecules are linked by N-H⋯O hydrogen-bonding inter-actions reminiscent of carb-oxy-lic acid hydrogen bonding pairs, forming chains parallel to the b-axis direction.

2-Amino-5-(3,4-dimethoxybenzylidene)-1-methylimidazol-4(5H)-one N,N-dimethylformamide monosolvate.

The crystal structure of the title compound, C(13)H(15)N(3)O(3) x C(3)H(7)NO, was determined as part of a larger project focusing on creatinine derivatives as potential pharmaceuticals. The molecule is essentially planar, in part because of intramolecular hydrogen bonding. Inversion-related pairs of molecules result from intermolecular hydrogen bonding. The pi systems of 2-amino-5-(3,4-dimethoxybenzylidene)-1-methylimidazol-4(5H)-one and an inversion-related molecule overlap slightly, indicating a small amount of pi-pi stacking. Bond lengths, angles and torsion angles are consistent with similar structures, except in the imidazolone ring near the doubly bonded C atom, where significant differences occur.

N-Ethyl-6-ethyl-amino-4-oxo-1,3,5-triazin-2-aminium chloride (Oxysimazine·HCl).

In the title molecular salt, C(7)H(14)N(5)O(+)·Cl(-) (the HCl salt of the oxo derivative of the triazine herbicide simazine), the cation and anion are linked by N-H⋯Cl hydrogen bonds. The chloride ion is also involved in a close electrostatic inter-action with an inversion-related triazine ring [Cl⋯centroid distance = 3.201 (1) Å]. A π-π inter-action having a centroid⋯centroid distance of 3.456 (2) Šexists between pairs of rings via another inversion relation. The triazine ring and adjacent non-H atoms are essentially planar (r.m.s. deviation = 0.042 Å), while both methyl groups are approximately perpendicular and on the same side of the plane [torsion angles = 79.3 (3) and -84.6 (3)°]. Upon exposure to X-rays for about two days, the color of the title compound changed from colorless to a pale yellow-orange with no apparent affect on the structure as evidenced by no significant change in the intensities of the standard reflections.

2-Methyl-4,4-dioxo-N-phenyl-5,6-di-hydro-1,4-oxathiine-3-carboxamide (Oxycarboxin).

In the title compound, C(12)H(13)NO(4)S, a systemic fungicide, the heterocycle adopts a lounge chair conformation and the dihedral angle between the ring planes is 25.8 (2)°. Inter-molecular C-H⋯O hydrogen bonds are noted in the crystal structure. Also observed is a short inter-action of a methyl-ene hydrogen atom with the π-electron system of a phenyl ring in an adjacent mol-ecule.

1-(4-Bromo-3-chloro-phen-yl)-3-meth-oxy-3-methyl-urea (chlorbromuron).

In the title urea-based herbicide, C(9)H(10)BrClN(2)O(2), there exist multiple inter- and intra-molecular inter-actions. Most notably, the intra-molecular hydrogen bond between the urea carbonyl O atom and an aromatic H atom affects the planarity and torsion angles of the mol-ecule by restricting rotations about the Ar-secondary amine N and the secondary amine N and the carbonyl C. The two N atoms in the urea fragment are in different environments. One is planar; the other, pseudo-C(3v). It is likely that the different nitro-gen-atom geometries and the restricted rotations within the mol-ecule impact the bioactivity of chlorbromuron.

N,N,N',N'-Tetra-methyl-ethylene-diammonium tetra-chloridocobaltate(II).

The asymmetric unit of the title compound, [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)][CoCl(4)], contains a tetra-chlorido-cobalt-ate(II) dianion and two halves of two centrosymmetric, crystallographically-independent, dications. One independent dication is disordered between two conformations in a 0.784 (13):0.216 (13) ratio. In the crystal, inter-molecular N-H⋯Cl hydrogen bonds link cations and anions into chains propagated in [01]. These hydrogen bonds contribute to the distorted tetra-hedral geometry at the Co(II) atom.

Chlorido(η-1,5-cyclo-octa-diene)[(penta-fluoro-eth-yl)diphenyl-phosphane]iridium(I).

The title structure,[IrCl(C(8)H(12))(C(14)H(10)F(5)P)], reveals that (C(2)F(5))PPh(2) (penta-fluoro-ethyl-diphenyl-phosphane or pfepp) disrupts the iridium dimer [(cod)IrCl](2) (cod = cyclo-octa-1,5-diene) by rupturing the bridging chloride ligands and binding in the open coordination site to form (cod)Ir(pfepp)Cl with the Ir(I) atom in a distorted square-planar coordination environment. The structure deviates very little from the Ir(I)-triphenyl-phosphine analog, although a significantly (∼20σ) shorter Ir-P bond is noted for the title compound.

New chiral benzothiazine ligand and its use in the synthesis of a chiral receptor.

The development of chiral ligands to direct the course and stereoselectivity of many catalytic asymmetric reactions is an important area of interest for many research groups. As part of a program examining the chemistry of 2,1-benzothiazines, we have prepared a new chiral benzothiazine ligand. This ligand can be made in as few as three steps from commercially available starting materials. Presented herein is the synthesis of the ligand along with the synthesis of a chiral molecular receptor that potentially presages a new class of chiral molecular tweezers.

2,4-Dinitrophenylhydrazones of 2,4-dihydroxybenzaldehyde, 2,4-dihydroxyacetophenone and 2,4-dihydroxybenzophenone.

In 2,4-dihydroxybenzaldehyde 2,4-dinitrophenylhydrazone N,N-dimethylformamide solvate [or 4-[(2,4-dinitrophenyl)hydrazonomethyl]benzene-1,3-diol N,N-dimethylformamide solvate], C(13)H(10)N(4)O(6).C(3)H(7)NO, (X), 2,4-dihydroxyacetophenone 2,4-dinitrophenylhydrazone N,N-dimethylformamide solvate (or 4-[1-[(2,4-dinitrophenyl)hydrazono]ethyl]benzene-1,3-diol N,N-dimethylformamide solvate), C(14)H(12)N(4)O(6).C(3)H(7)NO, (XI), and 2,4-dihydroxybenzophenone 2,4-dinitrophenylhydrazone N,N-dimethylacetamide solvate (or 4-[[(2,4-dinitrophenyl)hydrazono]phenylmethyl]benzene-1,3-diol N,N-dimethylacetamide solvate), C(19)H(14)N(4)O(6).C(4)H(9)NO, (XII), the molecules all lack a center of symmetry, crystallize in centrosymmetric space groups and have been observed to exhibit non-linear optical activity. In each case, the hydrazone skeleton is fairly planar, facilitated by the presence of two intramolecular hydrogen bonds and some partial N-N double-bond character. Each molecule is hydrogen bonded to one solvent molecule.

1,1'-Di(hydrazinocarbonylmethyl)-2,2'-biimidazole monohydrate and 1,1'-di[2-(hydrazinocarbonyl)ethyl]-2,2'-biimidazole.

The crystal structures of the title compounds, alternatively called 2,2'-(2,2'-biimidazole-1,1'-diyl)diacetohydrazide monohydrate, C(10)H(14)N(8)O(2).H(2)O, (I), and 3,3'-(2,2'-biimidazole-1,1'-diyl)dipropionohydrazide, C(12)H(18)N(8)O(2), (II), respectively, have been determined. The molecules consist of half-molecule asymmetric units related by a twofold rotation in (I) and by a center of inversion in (II). The imidazole rings of both molecules crystallize in a nearly coplanar fashion [dihedral angles of 5.91 (3) and 0.0 (1) degrees for (I) and (II), respectively]. Both planar hydrazinocarbonylalkyl substituents are essentially planar and assume the E orientation.