An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Herein we present the synthesis, structure and NMR and mass spectroscopic analyses of the antioxidant 2-(3,5-dimethoxyphenyl)-2,3-dihydroquinolin-4(1H)-one (1), a member of the 2-aryl-2,3-dihydroquinolin-4(1H)-one family of molecules that have been shown to display a range of potent biological properties. The title molecule, prepared by an alternative methodology to that recently reported, crystallizes in the centrosymmetric space group P21/c with unit cell dimensions a = 11.775(17) Å, b = 5.3592(8) Å, c = 22.462(3) Å and β = 96.576(11)°. Close analysis of the solid state structure reveals an array of weak N–H∙∙∙O hydrogen bonding as well as C–H∙∙∙O, and C–H∙∙∙π interactions between the neighboring molecules. The presence of 1 was also confirmed via NMR and mass spectroscopic analyses. Herein we present the solid state structure and results of mass spectroscopic and nuclear magnetic resonance analyses of the powerful antitumor compound 2-(3,5-dimethoxyphenyl)-2,3-dihydroquinolin-4(1H)-one prepared by an alternative synthetic avenue.

N-Substituted pyridinium salts constitute one of the most valuable reagent classes in organic synthesis, due to their versatility and ease of use. Herein we report a preliminary synthesis and detailed structural analysis of several N-(1-ethoxyvinyl)pyridinium triflates, an unusual class of pyridinium salts with potentially broad use as a reagent in organic synthesis. Treatment of pyridines with trifluoromethane sulfonic acid and ethoxyacetylene generates stable, isolable adducts which have been extensively characterized, due to their novelty. Three-dimensional structural stability is perpetuated by an array of C–H•••O hydrogen bonds involving oxygen atoms from the –SO3 groups of the triflate anion, and hydrogen atoms from the aromatic ring and vinyl group of the pyridinium cation. Predictions from density functional theory calculations of the energy landscape for rotation about the exocyclic C–N bond of 2-chloro-1-(1-ethoxyvinyl)pyridine-1-ium trifluoromethanesulfonate (7) and 1-(1-ethoxyvinyl)pyridine-1-ium trifluoromethanesulfonate (16) are also reported. Notably, the predicted global energy minimum of 7 was nearly identical to that found within the crystal structure.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Cancer cells often arise progressively from “normal” to “pre-cancer” to “transformed” to “local metastasis” to “metastatic disease” to “aggressive metastatic disease”. Recent whole genome sequencing (WGS) and spectral karyotyping (SKY) of cancer cells and tumorigenic models have shown this progression involves three major types of genome rearrangements: ordered small step-wise changes, more dramatic “punctuated evolution” (chromoplexy), and large catastrophic steps (chromothripsis) which all occur in random combinations to generate near infinite numbers of stochastically rearranged metastatic cancer cell genomes. This paper describes a series of mouse cell lines developed sequentially to mimic this type of progression. This starts with the new GhrasT-NIH/Swiss cell line that was produced from the NIH/3T3 cell line that had been transformed by transfection with HRAS oncogene DNA from the T24 human bladder carcinoma. These GhrasT-NIH/Swiss cells were injected s.c. into NIH/Swiss mice to produce primary tumors from which one was used to establish the T1-A cell line. T1-A cells injected i.v. into the tail vein of a NIH/Swiss mouse produced a local metastatic tumor near the base of the tail from which the T2-A cell line was established. T2-A cells injected i.v. into the tail vein of a nude NIH/Swiss mouse produced metastases in the liver and one lung from which the T3-HA (H=hepatic) and T3-PA (P=pulmonary) cell lines were developed, respectively. T3-HA cells injected i.v. into a nude mouse produced a metastasis in the lung from which the T4-PA cell line was established. PCR analysis indicated the human T24 HRAS oncogene was carried along with each in vitro/in vivo transfer step and found in the T2-A and T4-PA cell lines. Light photomicrographs indicate that all transformed cells are morphologically similar. GhrasT-NIH/Swiss cells injected s.c. produced tumors in 4% of NIH/Swiss mice in 6–10 weeks; T1-A cells injected s.c. produced tumors in 100% of NIH/Swiss mice in 7–10 days. T1-A, T-2A, T3-HA and T4-PA cells when injected i.v. into the tail produced local metastasis in non-nude or nude NIH/Swiss mice. T4-PA cells were more widely metastatic than T3-HA cells when injected i.v. into nude mice. Evaluation of the injected mice indicated a general increase in metastatic potential of each cell line in the progression as compared to the GhrasT-NIH/3T3 transformed cells. A new photomicrographic technique to follow growth rates within six preselected 2×2mm2 grids per plate is described. Average doubling times of the transformed cells GhrasT-NIH/3T3 (17h), T1A (17.5h), T2A (15.5h), T3-HA (17.5h) and T4-PA (18.5h) (average 17.2h) were significantly faster (P=0.006) than NIH Swiss primary embryonic cells and NIH/3T3 cells (22 h each). This cell series is currently used in this lab for studies of cancer cell inhibitors, mitochondrial biogenesis and gene expression and is available for further study by other investigators for intra- and inter-laboratory comparisons of WGS, transcriptome sequencing, SKY and other analyses. The genome rearrangements in these cells together with their phenotypic properties may help provide more insights into how one tumorigenic progression occurred to produce the various cell lines that led to the highly metastatic T4-PA cell line.

The complexes [(Cy2PCH2PCy2H)CoCl3] (1) and [(Cy2PCH2PCy2O)Co(NO3)(2)] (2), Cy = cyclohexyl (C6H11), have been prepared and characterized by EPR, UV-Vis, microanalysis and X-ray crystallography. The reaction CoCl2 (.) 6H(2)O and dcpm, dcpm = bis(dicyclohexylphosphino)methane, was found to form the monomeric, four coordinate, thermochromic and paramagnetic complex [(Cy2PCH2PCy2H)CoCl3] (1). Of particular interest is the formation of a zwitterion, or inner salt, in which the dangling phosphine adds a hydrogen atom, giving the phosphorus a +1 formal charge. The molecule adopts a pseudo-tetrahedral geometry around the central cobalt atom to which the cyclohexyl groups bind in an equatorial fashion to the phosphine. The reaction of Co(NO3)(2) (.) 6H(2)O and dcpm in a toluene/methanol/methylene chloride mixture yields the pseudo-octahedral complex [(Cy2PCH2PCy2O)Co(NO3)(2)] (2). The cobalt is in the +2 oxidation state with one of the phosphorus atoms again having a + 1 formal charge. The complex adopts a pseudo-octahedral geometry around the central cobalt atom with the cyclohexyl groups binding in an equatorial fashion to the phosphine similar to [(Cy2PCH2PCy2H)CoCl3]. (C) 2004 Elsevier B.V. All rights reserved.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The complexes [(dcpm)NiCl(2)] (1), [Ni(2)Cl(2)(mu-dcpm)(2)(mu-H)] (3), [Ni(2)(mu-PCy(2))(2)(PCy(2)Me)(2)] (4) and [Ni(dcpm)(2)](NO(3))(2). 2EtOH (2), dcpm = bis(dicyclohexylphosphino)methane, have been prepared and characterized by (31)p, (1)H NMR (or EPR) as well as X-ray crystallography. The salt NiCl(2). 6H(2)O was found to react with dcpm to form the monomeric, four-coordinate, diamagnetic complex [(dcpm)NiCl(2)] (1). Compound 1 was then reduced with (n)Bu(3)SnH (or LiH with heating) in toluene at room temperature to form the air sensitive 'A-frame' complex [Ni(2)Cl(2)(mu-dcpm)(2)(mu-H)] (3). The Ni-Ni bond distance for 3 was found to be 2.904(3) A showing a lack of any Ni-Ni metal bonding. [Ni(2)(mu-PCy(2))(2)(PCy(2)Me)(2)] (4) was then formed by the reaction of 1 and excess LiH, heating to 90 degrees C in an oil bath. [Ni(2)Cl(2)(mu-dcpm)(2)(mu-H)] (3) was shown to be an intermediate in the synthesis of the bridging phosphido nickel complex. The Ni-Ni bond distance in 4 is 2.3910(8) Angstrom corresponding to a single Ni-Ni metal bond. The reaction of Ni(NO(3))(2). 6H(2)O with dcpm in ethanol yields the square planar complex [Ni(dcpm)(2)](NO(3))(2). 2EtOH (2). (C) 2000 Elsevier Science S.A. All rights reserved.

Addition of ethylene to solutions of the bis(cyclometallated) compounds [W(OC6H3PhC6H4)2(L)2] (1, LPMe2Ph; 2, LPMePh2; OC6H3PhC6H4 = cyclometallated 2,6-diphenylphenoxide) produces the η2-ethylene complexes [W(OC6H3PhC6H4)2(L)(η2-C2H4)] (3, LPMe2Ph; 4a, LPMePh2). Addition of α-olefins, RCHCH2 (RPh, SiMe3, CF3) to solutions of 2 produced an equilibrium mixture of 2, free PMePh2 and the corresponding η2-olefin complexes [W(OC6H3PhHC6H4)2(PMePh2)(η2-RCHCH2)] (4b, RPh; 4c, RSiMe3; 4d, RCF3). The solid state structure of the ethylene complex 3 shows a pseudo-octahedral environment about the tungsten metal centre, with mutually trans aryloxide oxygen atoms and mutually cis metallated phenyl rings. The olefin ligand is aligned co-planar with the WP bond, i.e. perpendicular to the OWO axis. The WC (olefin) distances of 2.275(8) and 2.229(8) Å are longer than the WC(phenyl) distances of 2.162(7) and 2.127(8) Å. This, combined with an olefin CC distance of 1.39(1) Å, shows a lack of strong π-backbonding from the tungsten metal centre. In solution, however, restricted rotation about the tungsten-ethylene bond in 3a is observed in the 1H NMR spectrum. The bonding of the olefin ligands in these complexes is discussed.

The diamagnetic bis-phosphine complex [W(OC(6)H(3)Ph-C6H4)(2)(PMePh(2))(2)] (1) (OC(6)H(3)Ph.C6H4 = cyclo-metallated 2,6-diphenylphenoxide) reacts rapidly in hydrocarbon solvent with nitrogen heterocyclic ligands to produce a new series of complexes [W(OC(6)H(3)Ph-C6H4)(2)(L)(2)] (2: L = substituted pyridine, 3: (L)(2) = substituted bipyridines; 4: (L)(2) = phenanthrolines). Complexes 2, 3, and 4 exhibit sharp, contact-shifted H-1 NMR spectra at 25 degrees C, the amount of contact shifting being strongly dependent on the nature of the nitrogen donor ligand. Assignment of the signals in the H-1 NMR spectra as well as their temperature dependence indicates that a thermal equilibrium exists between a singlet ground state for the d(2)-W(IV) metal center and a triplet excited state which undergoes through-bond coupling to the ligand protons. The temperature dependence of the chemical shifts of the four protons (H2, H3, H4, and H5) attached to the metalated arene rings has been used to calculate the hyperfine coupling constants and single-triplet energy gap (E) for the ligands (L) 4-tert-butylpyridine (E = 1138 cm(-1)), 4-pyrrolidinopyridine (714 cm(-1)), 4,4'-dimethyl-2,2'-bipyridine (528 cm(-1)), and 4,4'-diphenyl-2,2'-bipyridine (362 cm(-1)). The relative singlet-triplet energy gap for different ligands can also be estimated by measuring the amount of contact shifting of these aryl protons at 25 degrees C. It is found that substituents on pyridine that decrease the value of E in compounds 2 increase the value of E in complexes 3 and 4 when introduced onto the bipyridine or phenanthroline nucleus. It is argued that stronger pi-acid pyridine ligands stabilize the singlet ground state by interacting with the formally d(xy) (HOMO) orbital on the metal while stronger pi-acid bipyridine and phenanthroline ligands will stabilize the d(xz), d(yz) (LUMO) pair of orbitals. The fact that the cis-pyridine ligands in [W(OC(6)H(3)Ph-C6H3)(2)(py)(2)] (2a) lie along the O-W-O (Z) axis has been confirmed by a single-crystal X-ray diffraction analysis. Crystal data at 20 degrees C for WO2N2C46H34: a = 26.299(4) Angstrom,b = 14.802(3)Angstrom,c 10.1339(9) Angstrom,beta = 103.17(1)degrees, Z = 4 in space group C2,

The compound tris(diphenylmethylphosphine)oxo-[1.1':3',1''-terphenyl-2'-plato(2-)-(CO)-O-2]tungsten(IV) toluene solvate contains one cyclometallated 2',6-di-phenylphenoxide ligand. A speudo-octahedral geometry exists for the WO2CP3 core with the terminal oxo and aryloxide O atoms mutually trans. W-O(terminal oxo group) = 1.1717 (3), W-O(aryloxide) = 2.059 (3), W-C = 2.151 (5), W-P = 2.550 Angstrom (average).