Di‐μ‐acesulfamato‐κ3N,O:O;κ3O:N,O‐bis[(acesulfamato‐κ2N,O)bis(3‐methylpyridine)cadmium(II)]

In the structure of the title compound, [Cd₂(C₄H₄NO₄S)₂(C₆H₇N)₂], the dinuclear Cd^II complex is located on a twofold axis with two Cd²⁺ ions bridged by two oxide O atoms. Each Cd²⁺ ion is additionally coordinated in an equatorial plane by two N and three O atoms of the acesulfamate ligands and axially by two N atoms of the 3‐methylpyridine ligands, resulting in a distorted pentagonal bipyramidal coordination. We present here an example of a supramolecular assembly based on hydrogen bonds in a mixed‐ligand metal complex; intermolecular C—H...O hydrogen bonds give rise to R₄⁴(40) rings, which lead to one‐dimensional chains.     

Bis(di‐2‐pyridyl sulfide‐κ2N,N′)(4‐methylpyrimidin‐2‐yl 2‐pyridylmethyl sulfide‐κ2N,S)ruthenium(II) bis(hexafluorophosphate) acetonitrile solvate

The crystal structure of the title compound, [Ru(C₁₀H₈N₂S)₂(C₁₁H₁₁N₃S)](PF₆)₂·C₂H₃N, is composed of a bivalent octa­hedral Ru^II complex, two PF₆⁻ anions and an acetonitrile solvent mol­ecule. Two PF₆⁻ units are found on a crystallographic binary axis, therefore contributing just one half each to the asymmetric unit cell. The structure displays a peculiar stereochemistry of the cation. Three bidentate ligands around the Ru centre, together with the coordination of the non‐symmetric S atom, mean that these two atoms are chiral. This would lead to four stereoisomers, but only an enantiomeric pair was found in the analyzed sample.     

cis‐Bis(acetato‐κO)bis(dimethyl sulfide‐κS)platinum(II)

The title compound, cis‐[Pt(CH₃COO)₂(C₂H₆S)₂], crystallizes in the P2₁/c space group with a pseudo‐square‐planar coordination geometry. The complex forms centrosymmetric dimeric packing units, with C—H...O—Pt interactions and a short Pt...Pt distance [3.5868 (2) Å]. The coordination mode of the acetate ligands is monodentate and they are oriented almost perpendicular to the coordination plane. Cambridge Structural Database [Allen (2002). Acta Cryst. B 58 , 380–388] data show a preferred staggered conformation with respect to the coordination plane for Me₂S in complexes with Pt^II.     

Bis(2‐chloro‐5‐methylpyridine‐κN)bis(nitrato‐κ2O,O′)copper(II)

In the molecule of the title compound, [Cu(NO₃)₂(C₆H₆ClN)₂], the Cu atom lies on an inversion centre and is six‐coordinated by two pyridine N atoms and four nitrate O atoms in trans positions. The nitrate acts as an unsymmetrical bidentate ligand. The coordination geometry is octahedral, with the Cu—N and the two Cu—O distances being 1.9939 (16), 2.0246 (16) and 2.4866 (19) Å, respectively. There are five types of C—H⋯O hydrogen bonds. Two of these generate two‐dimensional molecular networks in the direction of the a axis, and the others connect adjacent molecular networks.     

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‐Bis(isothiocyanato‐κN)bis(methanol‐κO)bis[2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine‐κN2]manganese(II)

The title compound, [Mn(NCS)₂(C₁₈H₁₂N₆)₂(CH₄O)₂], con­tains a centrosymmetric octahedral Mn^II centre and three pairs of trans‐coordinating ligands. It is the first example of a mononuclear metal complex with the 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine (tpt) ligand. Intermolecular π–π stacking of the planar tpt ligands, as well as hydrogen bonds between pyridyl N and methanol H atoms, results in the formation of a three‐dimensional network.     

(Hexafluorosilicato‐κ2F,F′)bis(1,10‐phenanthroline‐κ2N,N′)zinc(II) methanol monosolvate

The title compound, [Zn(SiF₆)(C₁₂H₈N₂)₂]·CH₃OH, contains a neutral heteroleptic tris‐chelate Zn^II complex, viz. [Zn(SiF₆)(phen)₂] (phen is 1,10‐phenanthroline), exhibiting approximate molecular C₂ point‐group symmetry. The Zn^II cation adopts a severely distorted octahedral coordination. As far as can be ascertained, the title complex represents the first structurally characterized example of a Zn^II complex bearing a bidentate‐bound hexafluorosilicate ligand. A density functional theory study of the isolated [Zn(SiF₆)(phen)₂] complex was undertaken to reveal the influence of crystal packing on the molecular structure of the complex. In the crystal structure, the methanol solvent molecule forms a hydrogen bond to one F atom of the hexafluorosilicate ligand. The hydrogen‐bonded assemblies so formed are tightly packed in the crystal, as indicated by a high packing coefficient (74.1%).     

Bis(μ‐4‐chloro­benzoato‐κ2O:O)bis[(2‐aminopyridine‐κN)silver(I)]

The title compound, [Ag₂(C₇H₄ClO₂)₂(C₅H₆N₂)₂], lies about an inversion centre and the Ag atom is three‐coordinated by two O atoms and one N atom from three different ligands. The 4‐chloro­benzoate anion acts as a monodonor ligand, bridging two inversion‐related Ag atoms of the compound into a dimer. There are weak intermolecular N—H⋯O hydrogen bonds in the structure.     

(Nitrato‐κO)bis(pyridine‐2‐carboxamide‐κ2N1,O)mercury(II) nitrate

In the title compound, [Hg(NO₃)(C₆H₆N₂O)₂]NO₃, the Hg^II atom is five‐coordinate. The distorted square‐pyramidal mercury(II) coordination environment is achieved by two N,O‐bidentate picolinamide ligands, with one O‐monodentate nitrate ion in the apical position. A seven‐coordinate extended coordination environment is completed by two additional weak Hg...O interactions, one from the coordinated nitrate ion and one from the other nitrate ion, to give seven‐coordination. The molecules are linked into a two‐dimensional network by N—H...O hydrogen bonds.     

Bis(acesulfamato‐κ2N3,O4)bis­(2‐amino­pyrimidine‐κN1)copper(II)

In the crystal structure of the title compound, bis­(2‐amino­pyrimidine‐κN¹)bis­[6‐meth­yl‐1,2,3‐oxathia­zin‐4(3H)‐one 2,2‐dioxide(1−)‐κ²N³,O⁴]copper(II), [Cu(C₄H₄NO₄S)₂(C₄H₅N₃)₂], the first mixed‐ligand complex of acesulfame, the Cu^II centre resides on a centre of symmetry and has an octa­hedral geometry that is distorted both by the presence of four‐membered chelate rings and by the Jahn–Teller effect. The equatorial plane is formed by the N atoms of two amino­pyrimidine (ampym) ligands and by the weakly basic carbonyl O atoms of the acesulfamate ligands, while the more basic deprotonated N atoms of these ligands are in the elongated axial positions with a strong misdirected valence. The crystal is stabilized by pyrimidine ring stacking and by inter­molecular hydrogen bonding involving the NH₂ moiety of the ampym ligand and the carbon­yl O atom of the acesulfamate moiety.     

(1,3‐Dimethylimidazolidine‐2‐selone‐κSe)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) bis(perchlorate) and bis(2,2′‐bipyridyl‐κ2N,N′)(imidazolidine‐2‐thione‐κS)copper(II) bis(perchlorate)

In the first title salt, [Cu(C₁₂H₈N₂)₂(C₅H₁₀N₂Se)](ClO₄)₂, the Cu^II centre occupies a distorted trigonal–bipyramidal environment defined by four N donors from two 1,10‐phenanthroline (phen) ligands and by the Se donor of a 1,3‐dimethylimidazolidine‐2‐selone ligand, with the equatorial plane defined by the Se and by two N donors from different phen ligands and the axial sites occupied by the two remaining N donors, one from each phen ligand. The Cu—N distances span the range 1.980 (10)–2.114 (11) Å and the Cu—Se distance is 2.491 (3) Å. Intermolecular π–π contacts between imidazolidine rings and the central rings of phen ligands generate chains of cations. In the second salt, [Cu(C₁₀H₈N₂)₂(C₃H₆N₂S)](ClO₄)₂, the Cu^II centre occupies a similar distorted trigonal–bipyramidal environment comprising four N donors from two 2,2′‐bipyridyl (bipy) ligands and an S donor from an imidazolidine‐2‐thione ligand. The equatorial plane is defined by the S donor and two N donors from different bipy ligands. The Cu—N distances span the range 1.984 (6)–2.069 (7) Å and the Cu—S distance is 2.366 (3) Å. Intermolecular π–π contacts between imidazolidine and pyridyl rings form chains of cations. A major difference between the two structures is due to the presence in the second complex of two N—H...O hydrogen bonds linking the imidazolidine N—H hydrogen‐bond donors to perchlorate O‐atom acceptors.     

Bis(μ‐N,N‐dimethyldithiocarbamato‐κ3S,S′:S′)bis[(dimethoxyphenylphosphane‐κP)(N,N‐dimethyldithiocarbamato‐κ2S,S′)cobalt(III)] bis(hexafluorophosphate)

Purple prismatic crystals of the title compound, [Co₂(C₃H₆NS₂)₄(C₈H₁₁O₂P)₂](PF₆)₂, were obtained by repeated recrystallization of trans‐[Co(C₃H₆NS₂)₂‐(C₈H₁₁O₂P)₂]PF₆ from CH₃CN/Et₂O and then from MeOH/CH₂Cl₂; during recrystallization one of the P(OMe)₂Ph ligands was dissociated from the Co^III center and the resulting Co^III complex fragment underwent dimerization. The complex cation has a dinuclear structure bridged by one S atom of each of two of the N,N‐di­methyl­di­thio­carbamate ligands, and has crystallographically imposed C₂ symmetry. Two P(OMe)₂Ph ligands are coordinated at the transoid positions of the Co₂(μ‐C₃H₆NS₂)₂(C₃H₆NS₂)₂ moiety, with Co—P bond lengths of 2.1921 (11) Å.     

A novel dinuclear bismuth(III) coordination compound: bis(μ‐pyridine‐2,6‐dicarboxylato)‐κ4O2,N,O6:O6′;κ4O2:O2′,N,O6‐bis[(azido‐κN)(1,10‐phenanthroline‐κ2N,N′)bismuth(III)] tetrahydrate

A novel dinuclear bismuth(III) coordination compound, [Bi₂(C₇H₃NO₄)₂(N₃)₂(C₁₂H₈N₂)₂]·4H₂O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy‐dispersive X‐ray spectroscopy, IR, X‐ray photoelectron spectroscopy and single‐crystal X‐ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi^III centre is seven‐coordinated by three O atoms and four N atoms. The coordination geometry of each Bi^III atom is distorted pentagonal–bipyramidal (BiO₃N₄), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O—H...O hydrogen bonds, resulting in the formation of a three‐dimensional supramolecular structure. Two types of π–π stacking interactions are found, with centroid‐to‐centroid distances of 3.461 (4) and 3.641 (4) Å.     

Dichlorido{2‐[(2,6‐diethylphenyl)iminomethyl]quinoline‐κ2N,N′}palladium(II) acetonitrile monosolvate

The title complex, [PdCl₂(C₂₀H₂₀N₂)]·CH₃CN, was synthesized by the reaction of 2‐[(2,6‐diethylphenyl)iminomethyl]quinoline with dichlorido(cycloocta‐1,5‐diene)palladium(II) in dry CH₂Cl₂. The Pd^II ion is coordinated by two N atoms of the bidentate quinoline ligand and by two chloride anions, generating a distorted square‐planar coordination geometry around the metal centre. There is a detectable trans influence for the chloride ligands. The crystal packing is characterized by π–π stacking between the quinoline rings. The use of acetonitrile as the crystallization solvent was essential for obtaining good‐quality crystals.     

A new polymorphic form of bis(acetato‐κO)bis[2‐(pyridin‐2‐yl)ethanol‐κ2N,O]nickel(II)

A new polymorph of a mononuclear nickel(II) acetate complex with 2‐(pyridin‐2‐yl)ethanol ligands, [Ni(CH₃COO)₂(C₇H₉NO)₂], has been prepared and structurally characterized. Its molecular structure resembles the structures of two previously reported polymorphs in that the Ni^II atom is located on an inversion centre and is coordinated by pairs of acetate and 2‐(pyridin‐2‐yl)ethanol ligands. The acetate anions are coordinated in a monodentate manner, while the 2‐(pyridin‐2‐yl)ethanol ligands are coordinated in a bidentate chelating mode involving the endocyclic N atom and the hydroxy O atom of the ligand side chain. A strong bifurcated intramolecular hydrogen‐bond interaction was observed involving the hydroxy O atom as donor and both acetate O atoms as acceptors. No classical intermolecular hydrogen‐bond contacts were observed. However, the crystal packing is effected through π–π and C—H...π interactions, giving rise to a different packing arrangement. A brief comparison of the three polymorphic forms is presented.     

Bis(di‐2‐pyridylamine‐κ2N2,N2′)(nitrato‐κ2O,O′)nickel(II) nitrate

<!?tpct=26.8pt>In the ionic title compound, [Ni(NO₃)(C₁₀H₉N₃)₂]NO₃, the central Ni^II atom exhibits cis‐NiN₄O₂ octahedral coordination with three chelating ligands, viz. one nitrate anion and two di‐2‐pyridylamine (dpya) molecules. A second nitrate group acts as a counter‐ion. The complex cations and the nitrate anions are also linked by N—H...O hydrogen bonds. The compound was prepared in two different reproducible ways: direct synthesis from Ni(NO₃)₂ and dpya yielded systematically twinned crystals (the twinning law is discussed), while single crystals were obtained unexpectedly from the Ni(NO₃)₂/dpya/maleic acid/NaOH system.     

Ethylenediammonium bis{bis[N‐(2‐aminoethyl)glycinato‐κ3N,N′,O]chromium(III)} tetrachloride dihydrate at 293 and 100 K

The crystal structure of the title compound, (C₂H₁₀N₂)[Cr(C₄H₉N₂O₂)₂]₂Cl₄·2H₂O, has been determined by single‐crystal X‐ray diffraction studies at 293 and 100 K. The analyses demonstrated that the crystal consists of ethyl­enedi­ammonium dications (which lie about inversion centres), bis­[N‐(2‐amino­ethyl)­glycin­ato]­chromium(III) monocations, Cl^? anions and hydrate water mol­ecules, in a molecular ratio of 1:2:4:2. The complex cation unit has a slightly distorted octahedrally coordinated Cr atom, with two Cr—O and four Cr—N bonds in the ranges 1.951 (1)–1.953 (1) and 2.054 (1)–2.089 (2) Å, respectively, at 293 K. The geometry of the bis­[N‐(2‐amino­ethyl)­glycinato]­chromium(III) moiety was found to be trans,cis,cis with respect to the carboxyl­ate O atom and the primary and secondary amine N atoms. The two analyses, at 293 and 100 K, exhibited no remarkable structural differences, although the colour of the crystals did differ, being red at 293 K and orange at 100 K.     

Bis(1,10‐phenanthroline‐κ2N,N′)(squarato‐κO)copper(II) trihydrate

The title mononuclear [Cu(sq)(phen)₂]·3H₂O complex [sq is squarate (C₄O₄) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)] has been synthesized and the structure consists of a neutral mononuclear [Cu(sq)(phen)₂] unit and three solvate water mol­ecules. The Cu^II ion has distorted square‐pyramidal coordination geometry, comprised of one carboxyl­ate O atom from a monodentate squarate ligand and four N atoms from two chelating phen ligands. An extensive three‐dimensional network of OW—H⋯O/OW hydrogen bonds, face‐to‐face π–­π interactions between the 1,10‐phenanthroline aromatic rings and a weak π–ring interaction are responsible for crystal stabilization.     

Weak antiferromagnetic inter­actions in hydro­nium diaqua‐1κO,2κO‐trichloro‐1κCl,2κ2Cl‐μ‐dimethyl­glycinato‐1κO:2κ2O′,N‐dimethyl­glycinato‐1κ2N,O‐dicuprate(II)

The crystal structure of the title compound, (H₃O)[Cu₂(C₄H₈NO₂)₂Cl₃(H₂O)₂], contains two Cu^II ions bridged by the carboxyl­ate group of a dimethyl­glycinate ion in an anti–anti configuration. The Cu^II atoms both have an approximately square‐pyramidal conformation geometry and are 5.977 (2) Å apart. The two dimethyl­glycinate ligands have similar conformations, although they play different roles in the structure. A weak antiferromagnetic inter­action between the two copper ions could be inferred from the magnetic susceptibility measurements.