Bis{4‐[N,N‐bis(2‐cyano­ethyl)­amino]­pyridine‐κN1}silver(I) perchlorate,with the perchlorate anion located in the cation cavity

The title complex, bis­[3,3′‐(pyridine‐4‐imino‐κN¹)­di­propane­nitrile]silver(I) perchlorate, [Ag(CEAP)₂]ClO₄ {CEAP is 4‐[N,N‐bis(2‐cyano­ethyl)­amino]­pyridine, C₁₁H₁₂N₄}, has been prepared and characterized. The unit cell consists of two crystallographically non‐equivalent mol­ecules. Cation cavities are constructed by [Ag(CEAP)₂]⁺ cations through hydrogen bonds, and the ClO₄⁻ anions are incorporated into the cavities in μ₄‐ and μ₂‐ClO₄⁻ bridging modes through C—H⃛O hydrogen bonds.     

Bis[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(perchlorato‐κO)copper(II) bis­[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(methanol‐κO)copper(II) bis­(perchlorate) methanol disolvate

The title compound, [Cu(ClO₄)₂(C₄H₉N₃O₂)₂][Cu(C₄H₉N₃O₂)₂(CH₄O)₂](ClO₄)₂·2CH₃OH, comprises two independent Cu^II species lying on different inversion sites. In the Cu complexes, a distorted octa­hedral geometry arises (from basic square‐planar N₄ coordination) from the weak coordination of two perchlorate ions (as Cu—O) in one species and two methanol mol­ecules in the other (also as Cu—O). Inter­actions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive inter­molecular hydrogen‐bonding network.     

trans‐(dl‐Isoleucinato‐N,O)[tris(2‐aminoethyl)amine‐κ4N]cobalt(III) diperchlorate

The racemic title compound, trans‐[N,N‐bis(2‐amino­ethyl)‐1,2‐ethanediamine‐κ⁴N]­(dl ‐isoleucinato‐N,O)­cobalt(III) di­per­chlor­ate, [Co(C₆H₁₈N₄)(C₆H₁₂NO₂)](ClO₄)₂, crystallizes in the enantiomorphous space group P2₁2₁2₁ with Z = 12 (Z′ = 3). Each of the three cations in the asymmetric unit represents a different chirality of the isoleucine ligand; two of them are R (or d ) and the third is the S (or l ) enantiomer. The mixture crystallizes in a so‐called unbalanced crystallization, in which the cations adopt a chiral array of composition RRS or SSR, depending on the crystal selected for data collection.     

A novel crystal structure of {tris[4‐(1H‐pyrazol‐3‐yl‐κN2)‐3‐azabut‐3‐enyl]amine‐κN}iron(II) bis(tetrafluoridoborate) methanol monosolvate featuring a low‐spin configuration

Mononuclear complexes are good model systems for evaluating the effects of different ligand systems on the magnetic properties of iron(II) centres. A novel crystal structure of the title compound, [Fe(C₁₈H₂₄N₁₀)](BF₄)₂·CH₃OH, with one molecule of methanol per formula unit exhibits a strictly sixfold coordination sphere associated with a low‐spin configuration at the metal centre. The incorporated methanol solvent molecule promotes extended hydrogen‐bonding networks between the tetrafluoridoborate anions and the cationic units. A less constrained crystal structure regarding close contacts between the tetrafluoridoborate anions and the cationic units allows a spin transition which is inhibited in the previously published hydrate of the title compound.     

Di‐μ‐hydroxo‐bis({bis­[2‐(2‐pyridyl)ethyl]amine‐κ3N}copper(II)) dichloride hexahydrate

The title compound, [Cu₂(OH)₂(C₁₄H₁₇N₃)₂]Cl₂·6H₂O, is a crystallographically centrosymmetric dimer of square‐pyramidal Cu^II centres, with a basal–basal [Cu₂(μ‐OH)₂]²⁺ bridging motif and apical pyridyl donors. The Cl⁻ anion is hydrogen bonded to one O—H and one N—H group, and to three different water mol­ecules. Because of disorder, the network of intramolecular hydrogen bonding in the hydrated lattice is only partly resolved.     

Bis[4‐(dimethylamino)pyridine‐κN1]silver(I) nitrate dihydrate

The title compound, [Ag(C₇H₁₀N₂)₂]NO₃·2H₂O or [Ag(dmap)₂]NO₃·2H₂O, where dmap is 4‐(dimethylamino)pyridine, has a distorted linear coordination geometry around the Ag^I ion. A novel pattern of water–nitrate hydrogen‐bonded anionic strands is formed in the c direction, with the cationic [Ag(dmap)₂]⁺ monomers trapped between them. The Ag^I ion and the nitrate group atoms, as well as the water molecules (including the H atoms), are on a crystallographic mirror plane (Wyckoff position 4a). The influence of bulky methyl substituents in position 4 of the 4‐(dimethylamino)pyridine ligand on packing is discussed. The absolute structure was determined unequivocally.     

cis‐Dichloridobis{dimethyl[3‐(9‐phosphabicyclo[3.3.1]non‐9‐yl)propyl]amine‐κP}platinum(II)

The title compound, [PtCl₂(C₁₃H₂₆NP)₂], is a rare example of a sterically bulky ligand adopting a cis geometry in a square‐planar complex. It crystallizes on a twofold rotation axis which bisects the Pt centre and the P—Pt—P′ and Cl—Pt—Cl′ angles. The ligand exhibits a random packing disorder in the N,N‐dimethylpropylamine substituent, with the two orientations refining to occupancies of 0.404 (15) and 0.596 (15). Weak intermolecular interactions between a Cl and a H atom of the ligand of a neighbouring molecule result in extended chains along the a axis. The effective cone angle for the dimethyl[3‐(9‐phosphabicyclo[3.3.1]non‐9‐yl)propyl]amine (Phoban[3.3.1]‐C₃NMe₂) ligand was determined as being in the range 160–181°, depending on the choice of atoms used in the calculations.     

[Tris(2‐amino­ethyl)­amine‐κ4N]chloro­(dimethyl sulfoxide‐O)­cobalt(III) diper­chlorate

The title compound, [CoCl(tren)(dmso)](ClO₄)₂ [tren is tris‐(2‐amino­ethyl)­amine, C₆H₁₈N₄; dmso is di­methyl sulfoxide, C₂H₆OS], is the first crystal structure reported with dmso coordinated to Co^III. It crystallizes with two independent mol­ecules in the asymmetric unit. A localized non‐crystallographic inversion centre is observed between the two cations.     

Bis{2,6‐bis[3‐(2,4,6‐trimethylphenyl)pyrazol‐1‐yl‐κN2]pyridine‐κN}zinc(II) diperchlorate bis(nitromethane) solvate

The title compound, [Zn(C₂₉H₂₉N₅)₂](ClO₄)₂·2CH₃NO₂, contains a Zn^II ion showing only small deviations from local D_2d symmetry. The lower rhombicity exhibited by this complex compared with that of its Cu^II congener suggests that the highly rhombic stereochemistry exhibited by the latter is largely imposed by the stereoelectronic preferences of the Cu^II ion.     

Bis(2‐amino­pyridine‐κN1)(benzoato‐κO)silver(I)

In the title compound, [Ag(C₇H₅O₂)(C₅H₆N₂)₂], the Ag^I atom is tricoordinated by two independent pyridine N atoms and one benzoate O atom in a nearly planar geometry. An intramolecular N—H⃛O hydrogen bond forms an S(8) graph ring. The packing is built from molecular layers stabilized by two types of N—H⃛O hydrogen bond. Intermolecular Ag⃛N and intramolecular Ag⃛O contacts were also observed, together with three weak intermolecular C—H⃛π interactions.     

Bis­(dicyan­amido)(diethyl­enetri­amine‐κ3N)copper(II) and (dicyan­amido)(tri­ethyl­enetetr­amine‐κ4N)copper(II) dicyan­amide

Two new complexes, [Cu(C₂N₃)₂(dien)] (dien is diethyl­ene­tri­amine, C₄H₁₃N₃), (I), and [Cu(C₂N₃)(trien)](C₂N₃) (trien is triethyl­ene­tetr­amine, C₆H₁₈N₄), (II), have been characterized by single‐crystal X‐ray diffraction. Both complexes display a distorted tetragonal–pyramidal geometry. In (I), the Cu atom is coordinated in the basal plane by three diethyl­ene­tri­amine N atoms [Cu—N = 2.000 (2), 2.004 (2) and 2.025 (2) Å] and one terminal N atom [Cu—N = 1.974 (2) Å] from one monodentate dicyan­amide group, and in the apical position by one terminal N atom [Cu—N = 2.280 (2) Å] from the other monodentate dicyan­amide group. In (II), the Cu atom is surrounded by four triethyl­ene­tetr­amine N atoms [Cu—N = 2.012 (2), 2.014 (2), 2.019 (2) and 2.031 (2) Å in the basal plane] and a terminal N atom [Cu—N = 2.130 (2) Å in the apical site] from one monodentate dicyan­amide group. The other dicyan­amide anion is not directly coordinated to the metal atom. In both (I) and (II), hydro­gen‐bond interactions between the uncoordinated terminal N atoms of two dicyan­amide ions and the amine H atoms lead to the formation of three‐dimensional networks.     

trans‐Bis­[N‐(2‐hydroxy­ethyl)­ethyl­ene­di­amine‐κ2N,N′]­bis­(iso­thio­cyanato‐κN)­nickel(II)

The crystal structure of the title compound, [Ni(NCS)₂(C₄H₁₂N₂O)₂], has two crystallographically independent half‐mol­ecules in the asymmetric unit, with each Ni atom residing on a centre of symmetry. The two mol­ecules exhibit similar coordination geometry but display differences with regard to other structural features. Each Ni^II centre is octahedrally coordinated by two mutually trans chelating hydroxy­ethyl­ethyl­ene­di­amine ligands and two mutually trans iso­thio­cyanate ions. The two independent mol­ecules form chains through different types of non‐covalent interactions. In the case of one of the mol­ecules, only NCS and free OH groups participate in hydrogen bonding, while in the chain based on the second mol­ecule, the NCS, NH, NH₂ and free OH groups are involved in intermolecular hydrogen bonding. The two chains interact with one another through hydrogen bonding, forming planar sheets. The third packing direction is mediated only by van der Waals interactions.     

Tris­(ethyl­enedi­amine‐N,N′)cobalt(III) oxalate perchlorate dihydrate

The crystallization behavior of the title compound, [Co(C₂H₈N₂)₃](C₂O₄)(ClO₄)·2H₂O, has been studied in order to evaluate the effect of the counter‐anion on the crystalline structures of [Co(en)₃](C₂O₄)·X (en = ethyl­enedi­amine). Two‐dimensional intermolecular hydrogen‐bonding networks are formed between the amine protons of the [Co(en)₃]³⁺ cations and the O atoms of the oxalate anions. Perchlorate and water mol­ecules fill in the channels between the two‐dimensional networks and form hydrogen‐bonding interactions with the two‐dimensional layers, thus constructing a three‐dimensional hydrogen‐bonding network.     

Di‐μ‐methoxo‐bis({N,N′‐bis­[2‐(3,5‐di­methyl­pyrazol‐1‐yl)­ethyl]­amine‐κ3N}copper(II)) bis­(hexa­fluoro­phosphate)

The title compound, [Cu₂(C₁₄H₂₃N₅)₂(CH₃O)₂](PF₆)₂, has a doubly methoxo‐bridged centrosymmetric copper dimer cation involving two tridentate bis­(pyrazolyl)­amine ligands. The geometry of each Cu^II atom is a distorted square pyramid with two N atoms of the pyrazole in bis­[2‐(3,5‐di­methyl‐1‐pyrazolyl)­ethyl]­amine (bpea) and two μ₂‐bridging O atoms of the methoxo ligands forming the basal plane, and the amine N atom occupying the axial position. In the bridging plane, the Cu—O bond lengths are 1.940 (4) and 1.942 (4) Å, and the bond angles for O—Cu—O and Cu—O—Cu are 76.1 (2) and 103.9 (2)°, respectively. The Cu?Cu distance is 3.058 (1) Å. The central four‐membered ring lies on an inversion centre.     

(Acetonitrile‐κN){2‐[bis­(2‐pyridylethyl)­amino]ethanol‐κ4N,N′,N′′,O}zinc(II) bis­(perchlorate) monohydrate

In the title compound, [Zn(C₂H₃N)(C₁₆H₂₁N₃O)](ClO₄)₂·H₂O, the Zn^II ion is coordinated by two pyridyl N atoms, one amine N atom, and an ethanol O atom from the N,N′,N′′,O‐tetra­dentate 2‐[bis­(2‐pyridylethyl)amino]­ethanol donor ligand. The fifth coordination site is filled by an acetonitrile N atom, and there is one solvent water mol­ecule in the asymmetric unit. The 2+ charge of the cationic portion of the complex is balanced by two perchlorate counter‐anions.     

trans‐Bis(2,2‐diphenyl­ethyl­amine‐κN)bis­(5,5‐diphenyl­hydantoinato‐κN3)copper(II) and its chloro­form disolvate

The crystal structures of the title compounds, [Cu(C₁₅H₁₁N₂O₂)₂(C₁₄H₁₅N)₂] and [Cu(C₁₅H₁₁N₂O₂)₂(C₁₄H₁₅N)₂]·2CHCl₃, respectively, have been determined. The red disolvate complex affords a square‐planar CuN₄ coordination environment in which the Cu^II atom lies on a centre of symmetry. The blue solvent‐free complex affords a distorted square‐pyramidal CuN₄O coordination environment and adjacent mol­ecules form centrosymmetric dimers. A comparison of the different crystal structures focuses on the role of the solvent mol­ecules in supramolecular assemblies of the copper(II) complexes.     

Bis(1,3,5‐triazine‐2,4,6‐triamine‐κN1)silver(I) nitrate

The title compound, [Ag(C₃H₆N₆)₂]NO₃, has an alternating two‐dimensional bilayer structure supported by extensive hydrogen bonds. The [Ag(melamine)₂]⁺ cationic monomers (melamine is 1,3,5‐triazine‐2,4,6‐triamine) are connected via N—H...N hydrogen bonds to form two‐dimensional sheets. Nitrate groups are sandwiched between two sheets through N—H...O hydrogen bonds. An almost perfectly linear coordination geometry is found for the Ag^I ions. The triazine ligands are slightly distorted due to π–π interactions.     

Bis{2,6‐bis[3‐(2,4,6‐trimethylphenyl)pyrazol‐1‐yl‐κN2]pyridine‐κN}cobalt(II) dinitrate at 290 and 150 K

The title compound, [Co(C₂₉H₂₉N₅)₂](NO₃)₂, contains a six‐coordinate high‐spin Co^II ion with approximate local D_2d symmetry. The bond lengths and angles at cobalt undergo only small changes between the two temperatures, which confirms that the Co^II ion does not undergo a spin‐state transition over this temperature range.