trans‐Bis(hexafluoroantimonato)(phthalocyaninato)copper(II)

The title compound, trans‐bis­(hexa­fluoro­antimonato‐F)(phthalocyaninato‐κ⁴N^29,30,31,32)copper(II), [Cu(SbF₆)₂(C₃₂­H₁₆N₈)] or Cu(pc)(SbF₆)₂ (pc is phthalocyaninate), comprises a six‐coordinate Cu atom, lying on an inversion center, bonded to four N atoms of a phthalocyanine ring and to F atoms of two trans SbF₆^? groups. The compound is presumed to consist of a Cu^II center and a doubly oxidized phthalocyanine ring, by analogy with Cu(pc)(ReO₄)₂.     

Structural properties of trans‐cyclohexane‐1,2‐diamine complexes of copper(II) and zinc(II) acesulfamates

The title compounds, trans‐bis(trans‐cyclohexane‐1,2‐diamine)bis(6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ido)copper(II), [Cu(C₄H₄NO₄S)₂(C₆H₁₄N₂)₂], (I), and trans‐diaquabis(cyclohexane‐1,2‐diamine)zinc(II) 6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ide dihydrate, [Zn(C₆H₁₄N₂)₂(H₂O)₂](C₄H₄NO₄S)₂·2H₂O, (II), are two‐dimensional hydrogen‐bonded supramolecular complexes. In (I), the Cu^II ion resides on a centre of symmetry in a neutral complex, in a tetragonally distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two N atoms of two acesulfamate ligands. Intermolecular N—H...O and C—H...O hydrogen bonds produce R₂²(12) motif rings which lead to two‐dimensional polymeric networks. In contrast, the Zn^II ion in (II) resides on a centre of symmetry in a complex dication with a less distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two O atoms from aqua ligands. In (II), an extensive two‐dimensional network of N—H...O, O—H...O and C—H...O hydrogen bonds includes R₂¹(6) and R₄⁴(16) motif rings.     

Synthesis of novel substituted pyridine derivatives from 3,5‐diacetyl‐2,6‐dimethylpyridine

A series of novel (1‐acetyl‐5‐aryl‐4,5‐dihydro)‐1H‐pyrazole substituted pyridine derivatives and poly substituted [2,3′‐bipyridine]‐5‐carbonitrile derivatives were synthesized from 3,5‐diacetyl‐2,6‐dimethylpyridine. The structures of two typical 3,5‐bis[1‐acetyl‐5‐(4‐chlorophenyl)‐4,5‐dihydro‐1H‐pyrazol‐3‐yl]‐2,6‐dimethylpyridines [ 3b(1) and 3b(2) ] were confirmed by X‐ray diffraction analysis. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:123–130, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20522     

(+ac,−ac)‐trans‐Bis(hinokitiolato)copper(II) and its chloroform disolvate

The complex trans‐bis(hinokitiolato)copper(II) [systematic name: trans‐bis(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trienolato)copper(II); abbreviated name: trans‐Cu(hino)₂], [Cu(C₁₀H₁₁O₂)₂], is a biologically active compound. Three polymorphs of this square‐planar monomer, all with (+sp,−sp) isopropyl substituents, have been reported previously. A fourth polymorph containing (+ac,−ac) isopropyl groups and its chloroform disolvate, [Cu(C₁₀H₁₁O₂)₂]·2CHCl₃, both exhibiting nonmerohedral twinning and with all Cu atoms on centers of crystallographic inversion symmetry, are reported here. One of the differences between all of these polymorphs is the relative conformation of the isopropyl groups with respect to the plane of the molecule. Stacking and Cu...olefin π distances ranging from 3.214 (4) to 3.311 (2) Å are observed, and the chloroform solvent molecules participate in bifurcated C—H...O hydrogen bonds [H...O = 2.26–2.40 Å, C...O = 3.123 (5)–3.214 (5) Å, C—H...O = 127–151° and O...H...O = 74°].     

trans‐Diaquabis(3‐hydroxybenzoato‐κO1)bis(nicotinamide‐κN1)copper(II)

The title compound, [Cu(C₇H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], is a two‐dimensional hydrogen‐bonded supramolecular complex. The Cu^II ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two pyridine N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₂²(4), R₂²(8) and R₂²(15) rings which lead to one‐dimensional polymeric chains. An extensive two‐dimensional network of N—H...O and O—H...O hydrogen bonds and C—H...π interactions are responsible for crystal stabilization.     

Two new polymorphs of trans‐bis(hinokitiolato)copper(II)

The title complex [systematic name: trans‐bis(3‐iso­propyl‐7‐oxo­cyclo­hepta‐1,3,5‐trienolato)copper(II)], [Cu(C₁₀H₁₁O₂)₂],is a substance possessing antimicrobial activity. The compound crystallizes in a number of polymorphic forms, the structures for two of which are reported here. Stacks of square‐planar mol­ecules exhibiting weak intermolecular copper–olefin π interactions (not observed in earlier reports on this substance) are described. The mol­ecules have crystallographically imposed inversion symmetry, with stacking and copper–olefin π distances ranging from 3.226 (2) to 3.336 (1) Å.     

trans‐Di­aqua­tetrakis(3,5‐di­methyl­pyrazole‐N2)­nickel(II) dichloride

The X‐ray structure analysis of [Ni(C₅H₈N₂)₄(H₂O)₂]Cl₂ was undertaken to elucidate the geometry around the Ni²⁺ ion. The molecule lies on a twofold axis which runs through the O—Ni—O atoms. The geometry around the Ni²⁺ ion is best described as slightly distorted tetragonal bipyramidal.     

Tetraaquabis(3,5‐dicarboxybenzoato‐O)cobalt(II)

The hydro­thermal reaction of cobalt(II) chloride with trimesate (3,5‐di­carboxy­benzoate) ions in aqueous solution gives the novel title complex, [Co(C₉H₅O₆)₂(H₂O)₄]. The Co^II ion lies on an inversion centre and is octahedrally coordinated to two trimesate anions and four water mol­ecules. Hydro­gen bonds ensure the three‐dimensional architecture of the structure.     

trans‐Di­aqua­bis(6‐hydroxy­picolinato‐κ2N,O2)copper(II)

In the title compound, [Cu(C₆H₄NO₃)₂(H₂O)₂], the Cu^II ion lies on an inversion centre and has an elongated octahedral environment, equatorially trans‐coordinated by two N,O‐bidentate picolinate ligands and axially coordinated by two water O atoms. The complex mol­ecules form layers, which are linked by O—H⋯O hydrogen bonds between the aqua ligands and neighbouring carboxyl­ate groups. An intramolecular hydrogen bond between the coordinated carboxyl­ate O atom and the hydroxy H atom is also observed.     

trans‐Bis(3‐acetyl­pyridine‐κN)diiodoplatinum(II)

In the square‐planar title complex, [PtI₂(C₇H₇NO)₂], the Pt atom lies on a crystallographic inversion center, coinciding with an anti arrangement of the 3‐acetyl­pyridine ligands. The dihedral angles between the pyridine rings and the Pt coordination plane are 67.5 (2)°, while those between the pyridine rings and the acetyl planes are 20.8 (5)°. The ¹⁹⁵Pt NMR resonance of the title complex (CD₂Cl₂) was observed at −3224 p.p.m. The major structural parameters are compared with those from previously reported related structures.     

catena‐Poly[copper(II)‐di‐μ‐acetylacetonato‐copper(II)‐bis(μ‐4‐hydroxy‐3‐methoxybenzaldehyde picoloylhydrazonato)] and (acetylacetonato)(4‐methoxybenzaldehyde picoloylhydrazonato)copper(II)

In the two title copper(II) complexes, [CuL(C₅H₇O₂)]_n, (I), and [CuL′(C₅H₇O₂)], (II), respectively, where HL is 4‐hydroxy‐3‐methoxybenzaldehyde picoloylhydrazone, C₁₄H₁₂N₃O₃, and HL′ is 4‐methoxybenzaldehyde picoloylhydrazone, C₁₄H₁₂N₃O₂, the Cu^II ions display a highly Jahn–Teller‐distorted octahedral and a square‐planar coordination geometry, respectively. In complex (I), two neighbouring Cu^II atoms are bridged by L⁻ and acetylacetonate, alternately, giving rise to a one‐dimensional chain of CuN₂O₄ octahedra interconnected by these two ligands along the a axis. In addition, the hydroxy H atom of the vanillin group connects to the carboxyl O atom of the adjacent chain via an O—H...O hydrogen bond, giving rise to a three‐dimensional supramolecular assembly. Complex (II) displays a discrete structure.     

trans‐Bis(hinokitiolato)copper(II) trans‐bis(hinokitiolato)palladium(II) cocrystals with (5/1) and (3/2) formulations

trans‐Bis(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)copper(II) trans‐bis(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)palladium(II) as the (5/1) and (3/2) composites [Cu(C₁₀H₁₁O₂)₂]·0.2[Pd(C₁₀H₁₁O₂)₂] and [Cu(C₁₀H₁₁O₂)₂]·0.67[Pd(C₁₀H₁₁O₂)₂], respectively, where 3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olate is the systematic name for the hinokitiolate anion (hino), are the first mixed‐metal cocrystalline products isolated from the M_x(hino)_y family of complexes. These cocrystals contain square‐planar trans‐Cu(hino)₂ and trans‐Pd(hino)₂ molecules possessing crystallographic inversion symmetry. The bulk formulation for these cocrystalline compounds is Cu_1−xPd_x(hino)₂, where x is 0.166 (4) for the (5/1) product and 0.399 (4) for the (3/2) product. This bulk formulation is simply a convenient average expression of the whole‐molecule substitutional disorder present in these compounds. The M—O bonds are in the range 1.9210 (11)–1.9453 (10) Å, the O—M—O bite angles are in the range 82.94 (4)–83.36 (4)°, and all of the hinokitiolate O atoms are involved in C—H...O hydrogen‐bonding interactions.     

trans‐Bis[3,5‐bis­(trifluoro­meth­yl)‐1H‐pyrazole‐κN2]dichloro­palladium(II) monohydrate

The palladium(II) center in the title compound, trans‐[PdCl₂(C₅H₂F₆N₂)₂]·H₂O, possesses a distorted square‐planar geometry. The NH groups are positioned on the same side of the PdN₂Cl₂ coordination plane. Four symmetry‐independent strong hydrogen bonds of three types (N—H⋯Cl, N—H⋯Cl and O—H⋯Cl) hold the structure together.     

Diamminebis(2,4,6‐tribromophenolato‐O)copper(II)

The title compound, [Cu(C₆H₂Br₃O)₂(NH₃)₂], a monomeric centrosymmetric Cu^II complex, crystallizes in the monoclinic system. The CuO₂N₂ coordination sphere is trans planar, [Cu—O 1.943 (5) Å and Cu—N 1.977 (6) Å], with the fifth and sixth coordination sites occupied by Br atoms from the phenoxide ions [Cu—Br 3.129 (1) Å], resulting in an elongated distorted octahedral structure for the CuO₂N₂Br₂ coordination. Each of the NH₃ groups forms two hydrogen bonds with the Br and O atoms of the CuO₂N₂Br₂ moiety of a neighbouring mol­ecule. This arrangement constitutes a one‐dimensional chain along the x axis of the unit cell.     

(−)‐Sparteine copper(II) diacetate

The chiral nitrogen‐chelating alkaloid (?)‐sparteine acts as a bidentate ligand, reacting with copper(II) acetate in ethanol to form the title complex, [Cu(CH₃COO)₂(C₁₅H₂₆N₂)], with the two acetate groups occupying the remaining coordination sites in a monodentate fashion to produce a distorted four‐coordinate tetrahedral structure. The dihedral angle between the N—Cu—N and O—Cu—O planes is 45.8 (3)°.     

trans‐Bis(3,5‐di­aza‐1‐azonia‐7‐phosphaadamantane‐κP)­bis­(thiocyanato‐κS)­palladium(II) bis­(thio­cyanate)

The crystal structure of the title compound, trans‐[Pd(NCS)₂(C₆H₁₃N₃P)₂](NCS)₂, is one of the few pal­ladium(II) complexes containing two protonated water‐soluble 1,3,5‐tri­aza‐7‐phos­pha­adamantane (PTA) ligands re­ported to date. The compound displays a distorted square‐planar geometry, with the Pd atom on an inversion centre and with the S atoms of the thio­cyanate counter‐ions occupying the axial positions above and below the equatorial plane described by the phosphine and thio­cyanate ligands. Geometric parameters for the formal coordination polyhedron include a Pd—P distance of 2.2940 (8) Å, a Pd—S distance of 2.3509 (8) Å and a P—Pd—S angle of 89.45 (3)°. The effective cone angle for the PTA ligands was calculated as 114.5°.     

trans‐Bis(dimethyl sulfoxide‐κO)bis(3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylato‐κ2N1,O2)copper(II)

The title compound, [Cu(C₉H₅N₂O₃)₂(C₂H₆OS)₂], consists of octahedrally coordinated Cu^II ions, with the 3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylate ligands acting in a bidentate manner [Cu—O = 1.9116 (14) Å and Cu—N = 2.1191 (16) Å] and a dimethyl sulfoxide (DMSO) molecule coordinated axially via the O atom [Cu—O = 2.336 (5) and 2.418 (7) Å for the major and minor disorder components, respectively]. The whole DMSO molecule exhibits positional disorder [0.62 (1):0.38 (1)]. The octahedron around the Cu^II atom, which lies on an inversion centre, is elongated in the axial direction, exhibiting a Jahn–Teller effect. The ligand exhibits tautomerization by H‐atom transfer from the hydroxyl group at position 3 to the N atom at position 4 of the quinoxaline ring of the ligand. The complex molecules are linked through an intermolecular N—H...O hydrogen bond [N...O = 2.838 (2) Å] formed between the quinoxaline NH group and a carboxylate O atom, and by a weak intermolecular C—H...O hydrogen bond [3.392 (11) Å] formed between a carboxylate O atom and a methyl C atom of the DMSO ligand. There is a weak intramolecular C—H...O hydrogen bond [3.065 (3) Å] formed between a benzene CH group and a carboxylate O atom.     

trans‐Diaquabis(nicotinamide‐κN)bis(salicylato‐κO)cobalt(II)

The title compound, [Co(C₇H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], forms a three‐dimensional hydrogen‐bonded supramolecular structure. The Co^II ion is in an octahedral coordination environment comprising two pyridyl N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₂²(8), R₂²(12) and R₂²(14) rings, which lead to two‐dimensional chains. An extensive three‐dimensional supramolecular network of C—H...O, N—H...O and O—H...O hydrogen bonds and C—H...π interactions is responsible for crystal structure stabilization. This study is an example of the construction of a supramolecular assembly based on hydrogen bonds in mixed‐ligand metal complexes.     

(S)‐trans‐Cyclohexane‐1,2‐dicarboximide

The molecule of the title compound, C₈H₁₁NO₂, contains a strained bicyclic system with a significantly twisted imide chromophore. The five‐membered ring fragment containing the imide function is strongly puckered and adopts a half‐chair conformation. The six‐membered ring has a slightly distorted chair conformation. The mol­ecules are joined by strong N—H?O and weak C—H?O hydrogen bonds into infinite chains.