A novel, tunable manganese coordination system based on a flexible "spacer" unit: noncovalent templation effects.

The reaction of bis(hexafluoroacetylacetonato)manganese(II) trihydrate (2), an approximately 90 degrees corner unit, with flexible linking unit 4,4'-trimethylenedipyridine (1) allows for the potential formation of three different types of solid-state coordination species: infinite helical polymers, closed dimeric systems, and infinite one-dimensional polymers. While the un-templated starting material is known to give a coordination helix, the other two possible species can be realized through the selective use of a variety of simple, organic guests: toluene (3), diphenylmethane (4), cis-stilbene (5), 1,3-diphenylpropane (6), benzyl alcohol (7), nitrobenzene (8), and cyanobenzene (9). When solutions of 1 and 2 are crystallized in the presence of all of these clathrates, the dimeric macrocycles result in all cases, except for that of 6, in which a syndiotactic, wedge-shaped polymer forms. Employing a linker that is less rigid than is typically used in crystal engineering, such as 1, enables the nucleophilic donor subunit to be more than just a simple "spacer", instead making it an essential, tunable component in the overall crystal lattice. In so doing, a great deal of molecular "information" is lost, but this is compensated for by an in-depth investigation into the weaker host-guest and/or guest-guest interactions, such as nonclassical hydrogen bonding and an assortment of hydrophobic interactions, present in the various systems.

A chloro(2-pyridinecarboxaldehyde)(2,2':6',2"-terpyridine)ruthenium(II) complex.

The aldehyde moiety in the title complex, chloro(2-pyridinecarboxaldehyde-N,O)(2,2':6',2"-terpyridine-kappa(3)N)ruthenium(II)-chloro(2-pyridinecarboxylic acid-N,O)(2,2':6',2"-terpyridine-kappa(3)N)ruthenium(II)-perchlorate-chloroform-water (1.8/0.2/2/1/1), [RuCl(C6H5NO)(C15H11N3)](1.8)[RuCl(C6H5NO2)(C15H11N3)](0.2)(ClO4)2-CHCl3-H2O, is a structural model of substrate coordination to a transfer hydrogenation catalyst. The title complex features two independent Ru(II) complex cations that display very similar distorted octahedral coordination provided by the three N atoms of the 2,2':6',2"-terpyridine ligand, the N and O atoms of the 2-pyridinecarboxaldehyde (pyCHO) ligand and a chloride ligand. One of the cation sites is disordered such that the aldehyde group is replaced by a 20 (1)% contribution from a carboxylic acid group (aldehyde H replaced by carboxyl O-H). Notable dimensions in the non-disordered complex cation are Ru-N 2.034 (2) A and Ru-O 2.079 (2) A to the pyCHO ligand and O-C 1.239 (4) A for the pyCHO carbonyl group.

Carbonates, thiocarbonates, and the corresponding monoalkyl derivatives. 2. X-ray crystal structure of potassium methyltrithiocarbonate (KS(2)CSCH(3)).

This study presents the first crystal structure determination of a potassium S-alkylthiocarbonate, the title compound potassium methyltrithiocarbonate (KS(2)CSCH(3)) Single crystals of KS(2)CSCH(3) were obtained by the slow introduction of methylene chloride into a saturated solution of KS(2)CSCH(3) in a 1:1 mixture of methylene chloride and tetrahydrofuran at 0 degrees C in a dry N(2) atmosphere. The compound crystallizes in the monoclinic space group P2(1)/c containing Z = 4 K(+) cations and S(2)CSCH(3-) anions per unit cell. The unit cell dimensions are a = 7.6639(3) A, b = 6.5804(2) A, c = 12.8426(5) A, and beta = 91.565(2) degrees. The isomorphism to the structurally closely related compounds KO(2)COCH(3), KOSCOCH(3), and KS(2)COCH(3) is examined.

Solvent dependence of the structure and magnetic ordering of ferrimagnetic manganese(III) meso-tetraphenylporphyrin tetracyanoethenide, [MnTPP]+[TCNE]*-.

Tetraphenylporphinatomanganate(III) tetracyanoethenide, [MnTPP][TCNE], is the prototype of a growing family of linear chain (1-D) coordination polymers that magnetically order as ferrimagnets. [MnTPP][TCNE].xS [S = PhMe (x = 2), 1,2-C(6)H(4)Me(2) (x = 1), 1,2-C(6)H(4)Cl(2) (x = 3), 1,2,4-C(6)H(3)Cl(3) (x = 2), and 1,3-C(6)H(4)Cl(2) (x = 2)] have been prepared and structurally and magnetically characterized. All form 1-D chain structures with intrachain Mn.Mn separations ranging from 9.202 to 10.218 A. The 173 K crystal structure of [MnTPP][TCNE].2PhMe has been rerefined, revealing that the [TCNE](*)(-) is 2-fold-disordered and coordinated to Mn(III) by a pair of trans cyano nitrogen atoms to form parallel one-dimensional chains. The two orientations of [TCNE](*)(-) are related by a 180 degrees rotation about the diagonal axis joining the trans nitrogen atoms bound to Mn(III). The major form has an occupancy of 83.3(4)% with a Mn-N(TCNE) distance of 2.328(3) A and a MnNC angle of 146.8(8) degrees. The minor form, with 16.7(4)% occupancy, has a Mn-N(TCNE) distance of 2.176(15) A and a MnNC angle of 152.3(39) degrees. Lattice packing and molecular bonding imply static as opposed to dynamic disorder. The magnetic properties depend on the type and quantity of the solvent present in the structure. Desolvation via heating in n-octane (127 degrees C), n-dodecane (216 degrees C), and/or vacuum thermolysis (175 degrees C) leads to numerous different desolvated materials with differing magnetic properties. At higher temperatures the magnetic susceptibility can be fit by the Curie-Weiss expression, chi varies with (T - theta)(-1), with theta = 44, 52, 72, 55, and 77 K for the toluene, 1,2-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,2,4-trichlorobenzene solvates, respectively. The T(c)'s were taken as the maximum in 10 Hz chi'(T) and are 7.8, 9.2, 11.3, 10.8, and 8.2 K for the PhMe, 1,2-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,2,4-trichlorobenzene solvates, respectively. Upon desolvation the T(c)'s increase for the PhMe, 1,2-xylene, 1,2,4-trichlorobenzene solvates and decrease for the 1,2- and 1,3-dichlorobenezene solvates. The compounds show one-dimensional ferrimagnetic exchange behavior at high temperatures with intrachain exchange of J/k(b) = -63, -99, -234, -100, and -200 K for toluene, 1,2-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,2,4-trichlorobenzene solvates, respectively, as determined from fits to the Seiden expression, which models isolated 1-D interactions among alternating S = 2 classical and S = (1)/(2) quantum spins. For variation in the temperature at which the peak occurs per decade of frequency, phi, (DeltaT(f)/T(f))/Delta(log omega) is 0.167, 0.168, 0.066, 0.171, and 0.024 for toluene, 1,2-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,2,4-trichlorobenzene, respectively, typical of spin glass behavior. Since [TCNE](*)(-) is only disordered for the PhMe solvate and all five solvates exhibit spin glass behavior, the spin glass behavior cannot be attributed to this disorder.

Coordination-driven assembly of molecular rectangles via an organometallic "clip".

The combination of linear dipyridyl ligands with a new type of modular building unit, based upon a 1,8-platinum-functionalized anthracene, leads to the self-organization of rectangular frameworks. X-ray crystallography confirms the cyclic structure of the supramolecular cationic complexes. Spectral assignments were provided by 2D NOESY (1)H NMR experiments.

A norbornenyl derivative with through-space ketone pi-interaction.

The title compound, endo,exo-12-oxotetracyclo[6.2.1.1(3,6).0(2, 7)]dodeca-9-en-anti-11-yl p-bromobenzoate, C(19)H(17)BrO(3), consists of norbornene with an anti-p-bromobenzoate substituent at the methano bridge and an exo-fused norbornanone unit bonded to the ethano bridge. The spatially proximate ketone and alkene interact through space and the ketone C atom is substantially pyramidalized. Through-space ketone pi-interaction is probably responsible for the low solvolysis rate of the anti-11-chloride derivative.

Hypertension.

The current JNC-VI criteria for diagnosis and classification of hypertension are discussed. The laboratory evaluation of both essential and secondary hypertension is examined, and recommendations are made in this regard. Finally, the complications and treatment of essential hypertension and the causes and management of resistant hypertension are discussed.

Copper(II) benzoate nitroxide dimers and chains: structure and magnetic studies.

Copper(II) benzoate dimers and linear chains have been synthesized and exhibit very different magnetic behaviors. The benzoate dimers, 1a, show typical dimeric singlet-triplet transitions and strong antiferromagnetic coupling (JST = -206 K (-143 cm-1); H = -2JSTSa.Sb). The bromobenzoate dimer can be converted into linear chains of hydrogen-bonded monomers, showing 1-D ferromagnetic coupling (6a, theta = +9 K). Copper(II) sites can also be bridged by nitroxide-substituted benzoates, 1b and 1c, that is, 2-(4'-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (NNBA, 3a), with JST = -216 K (-150 cm-1), with comparable interactions between the nitroxide and triplet Cu(II) spins, theta T = -157 K. A 1-D chain similar to the bromobenzoate monomers can also be produced with NNBA, also exhibiting ferromagnetic coupling (6b, theta = +0.67 K), albeit much weaker. Other nitroxides have been introduced into the Cu(II) dimer system by capping copper(II) acetate with the polydentate 2-(4'-pyridyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (PYNN, 3b), which exhibits almost no coupling to the copper centers when both ends of the dimer are capped (1d, theta = -5.8 K). In contrast, strong coupling is observed when only one PYNN is used (2, theta = -300 K), which is the result of direct coordination of the nitroxide to the copper centers, producing a chain of the dimer units.

Molecular structure and biological and pharmacological properties of 3-hydroxy-2-methyl-1-(beta-D-ribofuranosyl or pyranosyl)-4-pyridinone: potential iron overload drugs for oral administration.

Replacing alkyl groups by sugar moieties at N-1 position of 3-hydroxy-2-methyl-4-pyridinone did not affect the geometry of the iron chelating sites but increased the hydrophilic nature. The formation of a polymer cluster through the intermolecular hydrogen bonds was also revealed by X-ray crystal structure analysis for the first time in all known 3-hydroxy-4-pyridinone crystal structures. Iron removal from ferritin by the title compounds was more efficient than with DFO.