A solution-phase parallel synthesis of alkylated guanidines from thioisocyanates and amines.

An efficient solution-phase parallel synthesis of alkylated guanidines from commercial thioisocyanates and amines is described. In the first step, a thioisocyanate reacts with one equivalent of ammonia or a primary or secondary amine to give a thiourea intermediate. The latter is S-alkylated with n-dodecyl bromide resulting in the corresponding thiouronium bromide. Finally, the reaction of the thiouronium salt with a second equivalent of ammonia or a primary amine yields an alkylated guanidine. All three synthetic steps are easily combined in a one-pot high-yielding procedure with a simple work-up. Ca. 250 guanidine derivatives with high structural and functional diversity were synthesized by the developed method. 35 representatives reported in this study were fully characterized.

Tris(2,2'-bipyridine-κ(2)N,N')cobalt(III) bis-[bis-(pyridine-2,6-dicarboxyl-ato-κ(3)O(2),N,O(6))cobaltate(III)] perchlorate dimethyl-formamide hemisolvate 1.3-hydrate.

In the title compound, [Co(C(10)H(8)N(2))(3)][Co(C(7)H(3)NO(4))(2)](2)(ClO(4))·0.5C(3)H(7)NO·1.3H(2)O, the Co(III) atom in the complex cation is pseudoocta-hedrally coordinated by six N atoms of three chelating bipyridine ligands. The Co(III) atom in the complex anion is coordinated by two pyridine N atoms and four carboxyl-ate O atoms of two doubly deprotonated pyridine-2,6-dicarboxyl-ate ligands in a distorted octa-hedral geometry. One dimethyl-formamide solvent mol-ecule and two water mol-ecules are half-occupied and one water mol-ecule is 0.3-occupied. O-H⋯O hydrogen bonds link the water mol-ecules, the perchlorate anions and the complex anions. π-π inter-actions between the pyridine rings of the complex anions are also observed [centroid-centroid distance = 3.804 (3) Å].

Collapsed Cu(II)-hydroxamate metallacrowns.

Degradation of a strained, thermodynamically destabilized pentanuclear copper(II) 12-metallacrown-4 complex based on a picoline hydroxamic acid resulted in the formation of the tetranuclear compounds which are the first examples of solely hydroxamate-based Cu(II) metallacrown complexes with a collapse of the metallamacrocyclic cavity.

Poly[di-µ(2)-aqua-µ(5)-(pyridine-2,6-dicarboxyl-ato)-µ(3)-(pyridine-2,6-dicarboxyl-ato)-cobalt(II)disodium].

In the title compound, [CoNa(2)(C(7)H(3)NO(4))(2)(H(2)O)(2)](n), the Co(II) atom is coordinated by two pyridine N atoms and four carboxyl-ate O atoms from two doubly deprotonated pyridine-2,6-dicarboxyl-ate ligands in a distorted octa-hedral geometry. One Na(+) cation is coordinated by three carboxyl-ate O atoms and two water mol-ecules and the other is coordinated by five carboxyl-ate O atoms and two water mol-ecules in an irregular geometry. The bis-(pyridine-2,6-dicarboxyl-ato)cobalt complex units are connected by Na(+) cations and bridging water mol-ecules into a three-dimensional coordination network. O-H⋯O hydrogen bonds are formed between the water mol-ecules and the carboxyl-ate O atoms.

Diaqua-bis-(pyridine-2-carboxyl-ato-κN,O)manganese(II) dimethyl-formamide hemisolvate.

There are two crystallographically independent complex mol-ecules with very similar geometries in the unit cell of the title compound, [Mn(C(6)H(4)NO(2))(2)(H(2)O)(2)]·0.5C(3)H(7)NO. The central ion is situated in a distorted octa-hedral environment of two N- and four O-donor atoms from two pyridine-2-carboxyl-ate ligands and two cis-disposed water mol-ecules. The carboxyl-ate ligands are coordinated in a chelate fashion with the formation of two five-membered rings. In the crystal, the complex mol-ecules are connected by O-H⋯O hydrogen bonds between the coordinated water mol-ecules and the uncoordinated carboxyl-ate O atoms, thus forming hydrogen-bonded walls disposed perpendicularly to the bc plane.

fac-Tris(pyridine-2-carboxyl-ato-κN,O)cobalt(III).

In the title compound, [Co(C(6)H(4)NO(2))(3)], the Co(III) ion lies on a threefold rotation axis and is in a distorted octa-hedral environment defined by three N and three O donor atoms from three fac-disposed pyridine-2-carboxyl-ate ligands. The ligands are coordinated in a chelate fashion, forming three five-membered rings. In the crystal, translationally related complex molecules are organized into columns along [001] via C-H⋯O hydrogen bonds.

2-Hydroxy-amino-2-oxoacetohydrazide.

In the title compound, C(2)H(5)N(3)O(3), the hydroxamic group adopts an anti orientation with respect to the hydrazide group. In the crystal, mol-ecules are connected by N-H⋯O and O-H⋯N hydrogen bonds into zigzag chains along the c axis.

µ-Oxalato-bis-[(2,2'-bipyridyl)-copper(II)] bis(perchlorate) dimethyl-formamide disolvate monohydrate.

The title compound, [Cu(2)(C(2)O(4))(C(10)H(8)N(2))(4)](ClO(4))(2)·2C(3)H(7)NO·H(2)O, contains doubly charged centrosymmetric dinuclear oxalato-bridged copper(II) complex cations, perchlorate anions, and DMF and water solvate mol-ecules. In the complex cation, the oxalate ligand is coordinated in a bis-bidentate bridging mode to the Cu atoms. Each Cu atom has a distorted tetra-gonal-bipyramidal environment, being coordinated by two N atoms of the two chelating bipy ligands and two O atoms of the doubly deprotonated oxalate anion. Pairs of perchlorate anions and water mol-ecules are linked into recta-ngles by O-H⋯O bonds in which the perchlorate O atoms act as acceptors and the water mol-ecules as donors. Methyl groups of the DMF solvent molecule are disordered over two sites with occupancies of 0.453 (7):0.547 (7), and the water molecule is half-occupied.