catena‐Poly­[[tetrakis(2‐allyl­tetrazole‐κN4)‐tetra‐μ‐chloro‐tricopper(II)]‐di‐μ‐chloro]

In the crystal structure of the title compound, [Cu₃Cl₆(C₄H₆N₄)₄]_n, there are three Cu atoms, six Cl atoms and four 2‐allyl­tetrazole ligands in the asymmetric unit. The polyhedron of one Cu atom adopts a flattened octahedral geometry, with two 2‐allyl­tetrazole ligands in the axial positions [Cu—N4 = 1.990 (2) and 1.991 (2) Å] and four Cl atoms in the equatorial positions [Cu—Cl = 2.4331 (9)–2.5426 (9) Å]. The polyhedra of the other two Cu atoms have a square‐pyramidal geometry, with three basal sites occupied by Cl atoms [Cu—Cl = 2.2487 (9)–2.3163 (8) and 2.2569 (9)–2.3034 (9) Å] and one basal site occupied by a 2‐allyl­tetrazole ligand [Cu—N4 = 2.028 (2) and 2.013 (2) Å]. A Cl atom lies in the apical position of either pyramid [Cu—Cl = 2.8360 (10) and 2.8046 (9) Å]. The possibility of including the tetrazole N3 atoms in the coordination sphere of the two Cu atoms is discussed. Neighbouring copper polyhedra share their edges with Cl atoms to form one‐dimensional polymeric chains running along the a axis.     

Effects of Coordinating Solvents on the Supramolecular Assembling of Tectons arised from the Metallation of Sulfamethoxazole: Synthesis and Structural Characterization of Polymeric [Cd(sulfamethoxazolato)2(L)2]n {L = N,N‐dimethylformamide (DMF); Dimethyl Sulfoxide (DMSO)} and [Cd(sulfamethoxazolato)2(Py)2]n·n(Py)(Py =pyridine)

Cadmium acetate reacts with sulfamethoxazole (5‐methyl‐3‐isoxazolyl sulfanilamide) and with DMF / DMSO / pyridine to give the crystalline polymers [Cd(sulfamethoxazolato)₂(L₂)]_n {L = DMF ( 1 ), DMSO ( 2 )} and [Cd(sulfamethoxazolato)₂(Py)₂]_n·n(Py) ( 3 ). Complexes 1 , 2 and 3 confirm the tectonic character of the [Cd(sulfamethoxazolato)₂(L)₂] moieties and the remarkable ability of the {Cd(sulfamethoxazolato)₄} fragments to be non selectively stabilized by monodentate ligands. In the polymeric assemblies of the title complexes the cadmium(II) atoms are linked through sulfamethoxazolato anions which alternate in their coordination with the isoxazolic N‐atoms and the aromatic amino groups. The chains of vicinal rings build tunnels along the crystallographic c axis.     

Crystal structures of copper(II) complexes with methyliminodiacetate ions and 1,10-phenanthroline or imidazole [Cu(Phen)H<Subscript>2</Subscript>O][Cu(Mida)<Subscript>2</Subscript>]·2H<Subscript>2</Subscript>O and [Cu(Mida)Im]

Methyliminodiacetic acid (H₂Mida) and imidazole react with copper(II) to form crystals of the square pyramidal complex [Cu(Mida)Im]. One N and two O atoms of the Mida ligand (Cu-N 2.010(1) Å, Cu-O 1.955(1) Å, and 1.978(1) Å) and the imidazole N atom (1.950(1) Å) lie at the base of the pyramid. The carboxyl O atom of the neighboring complex lies at the apical position (2.411(1) Å); in this way the individual complexes are linked into infinite zigzag chains. Substitution of imidazole by 1,10-phenanthroline gave [Cu₂(Mida)₂(Phen)H₂O]·2H₂O crystals with two nonequivalent centrosymmetric octahedral anions [Cu(Mida)₂]^2? of face type (Cu-N 2.023 Å and 2.028(2) Å, Cu-O_ax 2.579 Å and 2.530(2) Å, Cu-O_bas 1.952 Å and 1.936(2) Å). The anions serve as bridges in chains between the [Cu(Phen)H₂O]²⁺ cation fragments to which they are bonded by their axial carboxyl groups. The Cu atom of the cation has a [4+1] environment (with the H₂O molecule lying on the axis of the pyramid, and with two N atoms of the ligand and two O atoms of the anions lying at the base).     

Syntheses,Crystal Structures,and Antibacterial Activities of Four Schiff Base Copper(II), Zinc(II), and Cadmium(II) Complexes Derived from 2‐[(2‐Dimethylaminoethylimino)methyl]phenol

Four Schiff base complexes, [Zn₂L₂(NCS)₂] ( 1 ), [Cd₂L₂(NCS)₂]_n ( 2 ), [Zn₄L₂(N₃)₂Cl₄(OH₂)(CH₃OH)] ( 3 ), and [Cu₄L₂(N₃)₂Cl₄(OH₂)(CH₃OH)] ( 4 ) (where L = 2‐[(2‐dimethylaminoethylimino)methyl]phenol), were synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X‐ray determinations. Both 1 and 2 are structurally similar polynuclear complexes. In 1 , each Zn atom has a slightly distorted square‐pyramidal coordination configuration. In the basal plane, the Zn atom is coordinated by one O and two N atoms of one L, and by one O atom of another L. The apical position is occupied by one terminal N atom of a coordinated thiocyanate anion. The Zn···Zn separation is 3.179(3) Å. While in 2 , the Cd1 atom is six‐coordinated in an octahedral coordination. In the equatorial plane, the Cd1 atom is coordinated by one O and two N atoms of one L, and by one O atom of another L. The axial positions are occupied by the terminal N and S atoms from two bridging thiocyanate anions. The coordination of Cd2 atom in 2 is similar to those of the zinc atoms in 1 . The Cd···Cd separation is 3.425(2) Å. Both 3 and 4 are novel tetra‐nuclear complexes. Each metal atom in the complexes has a slightly distorted square‐pyramidal coordination. The arrangements of the terminal metal atoms are similar, involving one O and two N atoms of one L ligand and one bridging Cl atom defining the basal plane, and one O atom of a coordinated water molecule or MeOH molecule occupying the apical position. The coordinations of the central metal atoms are also similar. The basal plane of each metal atom involves one O atom of one L ligand, one terminal Cl atom, and two terminal N atoms from two bridging azide groups. The apical position is occupied by a bridging Cl atom which also acts as a basal donor atom of the terminal metal atom. The Schiff base ligand and the four complexes showed high selectivity and antibacterial activities against most of the bacteria.     

Bis(methanol‐κO)dioxido[3,3′‐(1H‐1,2,4‐triazole‐3,5‐diyl)diphenolato‐κ3O,N4,O′]uranium(VI) methanol monosolvate

The structure of the title compound, [U(C₁₄H₉N₃O₂)O₂(CH₃OH)₂]·CH₃OH, is the first to be reported for an actinide complex including triazole ligands. The U^VI atom exhibits a pentagonal–bipyramidal NO₆ coordination environment, involving two axial oxide ligands [U=O = 1.766 (3) and 1.789 (3) Å], four equatorial O atoms [U—O = 2.269 (3)–2.448 (3) Å] from the ligand and the two coordinated methanol molecules, and one equatorial N atom [U—N = 2.513 (4) Å] from the ligand. In the crystal structure, the complex molecules are linked via intermolecular N—H...O and O—H...O hydrogen bonds to form a two‐dimensional structure.     

Tetra‐μ‐acetato‐κ2O:O′‐bis[(4‐phenylpyridine‐κN)copper(II)]

The title compound, [Cu₂(C₂H₃O₂)₄(C₁₁H₉N)₂] or [Cu₂(MeCO₂)₄(phpy)₂] (phpy is 4‐phenyl­pyridine), consists of centrosymmetric dimers in which the Cu^II atoms display a square‐pyramidal CuO₄N coordination, with four acetate O atoms in the basal plane [Cu—O 1.975 (3)–1.987 (3) Å] and the phpy N atom in the apical position [Cu—N 2.150 (3) Å]. The Cu atoms are 2.654 (1) Å apart and are bridged by four acetate groups. The discrete dimers are extended into a three‐dimensional supramolecular array through intermolecular π–π‐stacking interactions.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

Tetraaqua­bis[2‐(4‐pyridyl)ethanesul­fonato‐N]­zinc(II)

The title compound, [Zn(C₇H₈NO₃S)₂(H₂O)₄], has an octahedral coordination around the central Zn atom composed of two axial N atoms from the pyridine ligands and four equatorial O atoms of water mol­ecules, forming a monomeric centrosymmetric complex. The two Zn—N bond distances are 2.102 (3) Å, while the four Zn—O bond distances range from 2.114 (2) to 2.167 (2) Å. Packing is determined by hydrogen bonds formed by the water mol­ecules. The sulfonate group does not take part in coordination to the Zn atom.     

[1‐Allylpyridinium][Cu2Cl3]: Synthesis,X‐ray Structure and the Regularity of Crystal Architecture of 1‐Allyl/(amino)‐pyridinium Copper(I) Chloride π‐Complexes

By alternating‐current electrochemical technique crystals of copper(I) π‐complex with 1‐allylpyridinium chloride of [C₅H₅N(C₃H₅)][Cu₂Cl₃] ( 1 ) composition have been obtained and structurally investigated. Compound 1 crystallizes in monoclinic system, space group C2/c a = 24.035(1) Å, b = 11.4870(9) Å, c = 7.8170(5) Å, β = 95.010(5)°, V = 2150.0(2) ų (at 100 K), Z = 8, R = 0.028, for 4836 independent reflections. In the structure 1 trigonal‐pyramidal environment of π‐coordinated copper(I) atom is formed by a lengthened to 1.376(2) Å C=C bond of allyl group and by three chlorine atoms. Other two copper atoms are tetrahedrally surrounded by chlorine atoms only. The coordination polyhedra are combined into an original infinite (Cu₄Cl₆^2—)_n fragment. Structural comparison of 1 and the recently studied copper(I) chloride π‐complexes with 3‐amino‐, 2‐amino‐, 4‐amino‐1‐allylpyridinium chlorides of respective [LCu₂Cl₃] ( 2 ), [L₂Cu₂Cl₄] ( 3 ), and [LCuCl₂] ( 4 ) compositions allowed us to reveal the trend of the inorganic fragment complication which depends on pKa (base) value of the corresponding initial heterocycle.     

Synthese und Kristallstruktur von Ammin(μ3‐L‐glutamato)kupfer(II)

Synthesis and Crystal Structure of Ammine(μ₃‐L‐glutamato)copper(II) [Cu(L‐Glu)H₂O]·H₂O reacts with aqueous ammonia to give the ammine complex [Cu(L‐Glu)NH₃] ( 1 ). 1 forms orthorhombic crystals, space group P 2₁2₁2 with a = 1585,1(1) pm; b = 979,46(7) pm and c = 504,70(5) pm. In the crystal structure of 1 the copper atoms are linked by μ₃‐glutamate units to give a 2D layer structure. The copper atoms exhibit a square‐pyramidal coordination with two N atoms and two O atoms in the base plane and one O atom at the apex of the pyramid. The crystal structure is stabilized by a 3D network of N–H···O hydrogen bridges.     

Tetrakis(μ‐benzoato‐κ2O:O)bis{[4‐(dimethylamino)pyridine‐κN1]copper(II)}

The title compound, [Cu₂(C₇H₅O₂)₄(C₇H₁₀N₂)₂], is a crystallographically centrosymmetric binuclear complex, with Cu atoms [Cu...Cu = 2.6982 (4) Å] bridged by four benzoate ligands. Each of the Cu atoms in this bunuclear copper(II) acetate hydrate analogue is present in an approximately square‐pyramidal environment, with four O atoms in a plane and the pyridine N atom at the apical site. Selected geometric parameters are compared with values for related tetrabenzoate complexes of copper(II).     

Bis[1,1‐di­methyl­biguanide(1–)‐κ2N2,N5]copper(II) monohydrate

The crystal structure of the title compound, [Cu(C₄H₁₀N₅)₂]·H₂O, contains two independent copper N,N‐di­methyl­biguanide complex units, each with square‐planar coordination of the Cu atom by four N atoms. The two complexes have different symmetry, with one Cu atom lying on an inversion centre and the other on a twofold rotation axis. The Cu—N bond lengths are 1.923 (2) and 1.950 (2) Å in the centrosymmetric complex, and 1.928 (2) and 1.938 (2) Å in the non‐centrosymmetric complex. The crystal structure is stabilized by N—H⋯O, O—H⋯N and N—H⋯N hydrogen bonds; each water mol­ecule forms four hydrogen bonds involving three different Cu complexes.     

Syntheses,Crystal Structures,and Antibacterial Activities of Four Schiff Base Complexes of Copper and Zinc

Four Schiff base complexes, [Cu₂(L1)₂(μ‐NCS)₂] ( 1 ), [Cu₂(L2)₂(μ‐N₃)₂] ( 2 ), Cu[Cu(CH₃COO)(L3)]₂ ( 3 ), and [Zn{Zn(C₃H₄N₂)(L3)}₂(NO₃)](NO₃) ( 4 ) (where L1 = 2‐[(pyridin‐2‐ylmethylimino)methyl]phenol, L2 = 1‐[(pyridin‐2‐ylmethylimino)methyl]naphthalen‐2‐ol, and L3 = bis(salicylidene)‐1, 3‐propanediamine), were synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X‐ray determinations. Both 1 and 2 are structurally similar di‐nuclear complexes, which are located at crystallographic inversion centers (with the center of the central Cu₂N₂ ring). In 1 , each copper atom has a slightly distorted square pyramidal configuration, coordinated by two nitrogen atoms and one oxygen atom from L1 and another two terminal nitrogen atoms from two bridging thiocyanate anions. The Cu···Cu separation is 3.466(3) Å. The structure of 2 is similar to that of 1 , with Cu···Cu separation of 3.368(2) Å. Both 3 and 4 are linear tri‐nuclear complexes. In 3 , the central Cu²⁺ ion is located on an inversion centre and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands (L3) in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal Cu²⁺ ions is irregular‐square pyramidal, with two O and two N atoms of L3 in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal Cu²⁺ ions are mutually trans. The Cu···Cu separation is 3.009(3) Å. In 4 , the coordination configuration of the central and the terminal zinc atoms are similar to that of the 3 , with Zn···Zn separation of 3.153(4) Å. The three Schiff bases and the corresponding three copper complexes exhibit good antibacterial properties, while the zinc complex 4 has nearly no.     

Acetato(N‐phenylpyridine‐2‐carboxamidato‐κ2N,N)(N‐phenylpyridine‐2‐carboxamide‐κ2N1,O)copper(II)

The title complex, [Cu(C₁₂H₉N₂O)(C₂H₃O₂)(C₁₂H₁₀N₂O)], is a neutral Cu^II complex with a primary N₃O₂ coordination sphere. The Cu centre coordinates to both a deprotonated and a neutral molecule of N‐phenylpyridine‐2‐carboxamide and also to an acetate anion. The coordination around the metal centre is asymmetric, the deprotonated ligand providing two N donor atoms [Cu—N = 1.995 (2) and 2.013 (2) Å] and the neutral ligand providing one N and one O donor atom to the coordination environment [Cu—N = 2.042 (2) Å and Cu—O = 2.2557 (19) Å], the fifth donor being an O atom of the acetate ion [Cu—O = 1.9534 (19) Å]. The remaining O atom from the acetate ion can be considered as a weak donor atom [Cu—O = 2.789 (2) Å], conferring to the Cu complex an asymmetric octahedral geometry. The crystal structure is stabilized by intermolecular N—H...O, C—H...O and C—H...π interactions.     

catena‐Poly[[bis(cis‐1‐tert‐butyltetrazole‐κN4)copper(II)]‐di‐μ‐chloro]

The title polymeric compound, [CuCl₂(C₅H₁₀N₄)₂]_n, is the first structurally characterized complex with a bulky 1‐alkyl­tetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu—Cl distances of 2.2920 (8) and 2.2796 (9) Å, and by the two N‐4 atoms of the tetrazole ligands, with Cu—N distances of 2.023 (2) and 2.039 (2) Å. Two symmetry‐related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) Å from the Cu atom. The [CuCl₂(C₅H₁₀N₄)₂] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.     

Low‐dimensional compounds containing cyano groups. XVI. (Dicyanamido‐κN1)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) tetrafluoridoborate

The title compound, [Cu{N(CN)₂}(C₁₂H₈N₂)₂]BF₄, was prepared as part of our study of the shape of coordination polyhedra in five‐coordinated copper(II) complexes. Single‐crystal X‐ray analysis reveals that the structure consists of [Cu{N(CN)₂}(phen)₂]⁺ cations (phen is 1,10‐phenanthroline) and BF₄⁻ anions. The Cu centre is five‐coordinated in a distorted trigonal bipyramidal manner by four N atoms of two phen ligands and one N atom of a dicyanamide anion, which is coordinated in the equatorial plane at a distance of 1.996 (2) Å. The two axial Cu—N_phen distances have similar values [average 1.994 (6) Å] and are shorter than the two equatorial Cu—N_phen bonds [average 2.09 (6) Å]. This work demonstrates the effect of ligand rigidity on the shape of coordination polyhedra in five‐coordinated copper(II) complexes.     

(Acetonitrile){2,6‐bis[1‐(2,4,6‐trimethylphenylimino)ethyl]pyridine}dichloridoruthenium(II) dichloromethane solvate

In the title compound, [RuCl₂(C₂H₃N)(C₂₇H₃₁N₃)]·CH₂Cl₂, the Ru^II ion is six‐coordinated in a distorted octahedral arrangement, with the two Cl atoms located in the apical positions, and the pyridine (py) N atom, the two imino N atoms and the acetonitrile N atom located in the basal plane. The two equatorial Ru—N_imino distances are almost equal (mean 2.087 Å) and are substantially longer than the equatorial Ru—N_py bond [1.921 (4) Å]. It is observed that the N_imino—M—N_py angle for the five‐membered chelate rings of pyridine‐2,6‐diimine complexes is inversely related to the magnitude of the M—N_py bond. The title structure is stabilized by intra‐ and intermolecular C—H...Cl hydrogen bonds, as well as by van der Waals interactions.     

Die Reaktion von Ytterbium mit N‐Iod‐triphenylphosphanimin. Kristallstrukturen von [Yb2I(THF)2(NPPh3)4] · 2 THF, [YbI2(HNPPh3)(DME)2] und [{YbI2(DME)2}2(μ‐DME)]

The Reaction of Ytterbium with N‐iodo‐triphenylphosphaneimine. Crystal Structures of [Yb₂I(THF)₂(NPPh₃)₄] · 2 THF, [YbI₂(HNPPh₃)(DME)₂], and [{YbI₂(DME)₂}₂(μ‐DME)] When treated with ultrasound, the reaction of ytterbium powder with INPPh₃ in tetrahydrofuran leads to [YbI₂(THF)₄] and to the mixed‐valence phosphoraneiminato complex [Yb₂I(THF)₂(NPPh₃)₄] · 2 THF ( 1 ), which forms red single‐crystals. In the analogous reaction in 1,2‐dimethoxyethane (DME) only the ytterbium(II) iodide solvates [YbI₂(HNPPh₃)(DME)₂] ( 2 ) and [{YbI₂(DME)₂}₂ · (μ‐DME)] ( 3 ) can be isolated, which form yellow single crystals. All compounds were characterized by crystal structure analyses. 1 : Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1337.6(5), b = 1389.6(5), c = 2244.2(17) pm; α = 86.11(7)°, β = 88.06(7)°, γ = 88.63(4)°; R = 0.0759. In 1 the two ytterbium atoms are connected via the N atoms of two phosphoraneiminato groups (NPPh₃^–) to form a planar Yb₂N₂ four‐membered ring. The structure can also be described as an ion pair consisting of [YbI(THF)₂]⁺ and [Yb(NPPh₃)₄]^–. 2 : Space group P2₁, Z = 2, lattice dimensions at –80 °C: a = 811.9(1), b = 1114.0(1), c = 1741.3(1) pm; β = 95.458(5)°; R = 0.0246. 2 forms molecules in which the ytterbium atom is coordinated in a pentagonal‐bipyramidal fashion with the iodine atoms in the axial positions. The O atoms of the two DME‐chelates and the N atom of the phosphaneimine ligand HNPPh₃ are in the equatorial positions. 3 : Space group P1, Z = 2, lattice dimensions at –70 °C: a = 817.5(1), b = 1047.7(1), c = 1115.5(2) pm; α = 90.179(10)°, β = 97.543(15)°, γ = 91.087(12)°; R = 0.0317. 3 has a dimeric molecular structure, in which the two fragments {YbI₂(DME)₂} are connected centrosymmetrically via a μ‐DME bridge. As in 2 , the ytterbium atoms are coordinated in a pentagonal‐bipyramidal fashion with the iodine atoms in the axial positions, as well as with the two DME chelates and with one O atom each of the μ‐DME ligand in the equatorial positions.     

On the Search of Metallated Sulfonamides: Synthesis and X‐ray Characterization of the New Sulfathiazolato Nickel(II)‐Chelate Complex [Ni(STZ)2(Py)2]·2Py (STZ = Sulfathiazolato Anion; Sulfathiazole = N1‐2‐thiazolyl‐sulfanilamide; Py = Pyridine)

Sulfathiazole (HSTZ) reacts with triethylamine and Ni(CH₃COO)₂·4H₂O in methanol and further with pyridine to give the sulfathiazolato complex [Ni(STZ)₂(Py)₂]·2Py. In the new chelate complex the deprotonated sulfonamidic nitrogen atom does not take part in the coordination process, apparently retaining the negative charge. Two (STZ)^? moieties are symmetrically bonded to the Ni²⁺ ion through a thiazolyl nitrogen atom and an oxygen atom of the S(O)₂ group. Two pyridine molecules accomplish the fairly distorted octahedral coordination at the metal centre.     

{2‐[(3‐Amino­propyl)­amino­propyl­imino­methyl]­imidazol­ato‐N,N′,N′′,N′′′}­(methanol‐O)­copper(II) per­chlorate

In the title compound, [Cu(C₁₀H₁₈N₅)(CH₄O)]ClO₄, four N atoms from the deprotonated ligand derived from bis(3‐amino­propyl)­amine and 2‐imidazole­carbox­aldehyde are coordinated to the Cu atom. The four N atoms occupy equatorial positions with Cu—N bond distances ranging from 1.998 (2) to 2.046 (3) Å. The methanol O atom occupies one axial position with a Cu—O bond distance of 2.295 (2) Å.