Synthesis and Crystal Structures of Copper Zinc Phenylthiolate and the First Copper Zinc Selenolate and Tellurolate Complexes

Five copper zinc phenylchalcogenolate complexes [(iPr₃PCu)₃(ZnMe₂)₂(SPh)₃] ( 1 ), [(iPr₃PCu)₂(ZnPh)₄(SPh)₆] ( 2 ), [(iPr₃PCu)₂(ZnEt)₄(SPh)₆] ( 3 ), [(iPr₃PCu)₃(ZnEt)(SePh)₄] ( 4 ), and [(iPr₃PCu)₃Cu(iPr₃PZn)(TePh)₆] ( 5 ) were synthesized by the reaction of phosphine stabilized copper phenylchalcogenolate complexes with ZnR₂ (R = Me, Et, Ph) with and without additional chalcogenol. The novel mixed metal compounds were characterized by single‐crystal X‐ray structure analysis and NMR spectroscopy. 4 and 5 are the first examples of compounds with a Zn–Se–Cu or a Zn–Te–Cu linkage, respectively.     

First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

Three new complexes with phosphanylphosphido ligands, [Cu₄{μ₂‐P(SiMe₃)‐PtBu}₄] ( 1 ), [Ag₄{μ₂‐P(SiMe₃)‐PtBu₂}₄] ( 2 ) and [Cu{η¹‐P(SiMe₃)‐PiPr₂}₂]^–[Li(Diglyme)₂]⁺ ( 3 ) were synthesized and structurally characterized by X‐ray diffraction, NMR spectroscopy, and elemental analysis. Complexes 1 and 2 were obtained in the reactions of lithium derivative of diphosphane tBu₂P‐P(SiMe₃)Li · 2.7THF with CuCl and [iBu₃PAgCl]₄, respectively. The X‐ray diffraction analysis revealed that the complexes 1 and 2 present macrocyclic, tetrameric form with Cu₄P₄ and Ag₄P₄ core. Complex 3 was prepared in the reaction of CuCl with a different derivative of lithiated diphosphane iPr₂P‐P(SiMe₃)Li · 2(Diglyme). Surprisingly, the X‐ray analysis of 3 revealed that in this reaction instead of the tetramer the monomeric form, ionic complex [Cu{η¹‐P(SiMe₃)‐PiPr₂}₂]^–[Li(Diglyme)₂]⁺ was formed.     

Complexes of 2, 6‐Bis(hydroxymethyl)pyridine with Different Copper(II) Salts Involving the Anions Chloride,Perchlorate, Nitrate and Acetate. Synthesis and Crystal Structures of the Complexes

Complexes of 2, 6‐bis(hydroxymethyl)pyridine (dhmp) with different Cu^II salts [CuCl₂·6H₂O, Cu(ClO₄)₂·6H₂O, Cu(NO₃)₂·3H₂O, Cu(CH₃COO)₂·H₂O] are prepared ( 1 — 5 , respectively), studied by IR, and their crystal structures reported. Dependent on the anion kind, influences on the distortion of the co‐ordination polyhedron, the distribution of donor sites, the formation of a mono‐ or binuclear complex, and the resultant packing structure of the complex are observed, although in no case the counterions of the used Cu^II salts or water of hydration were found in the co‐ordination sphere. Crystal structures of 1 — 5 indicate hexaco‐ordination of the Cu^II ions with N₂O₄‐environment and show that 1 — 4 are mononuclear 2:1 (L:M) complexes, but 5 is a binuclear 4:2 complex. Crystallization of Cu(ClO₄)₂·6H₂O with dhmp yielded two different complexes ( 2 / 3 ). In 3 , one of the dhmp components is mono‐deprotonated and acts as an anionic ligand. The same behavior is found in 5 . Whereas in the neutral ligand complexes 1 , 2 and 4 the basal planes are occupied by O donors, and N atoms are in the axial positions of the octahedrons, in 3 and 5 the bases are formed by two O and two N donor atoms, and O atoms are in the axes. Moreover, complex 3 shows the N atoms in trans position, but 5 in cis position. The packing of the cationic complex units is typical of strong and weak H bond interactions involving the counterions and hydroxylic or aromatic hydrogen atoms to yield complex network structures.     

Synthesis and Structure of a Molecular Zinc Phosphate [(C12H8N2Zn)2(HPO4)(H2PO4)2]

A hydrothermal reaction of a mixture of ZnCO₃, phosphoric acid, 1, 10‐phenanthroline in H₂O gave rise to large plates of a new zinc phosphate, [(C₁₂H₈N₂Zn)₂(HPO₄)(H₂PO₄)₂], I . The structure consists of ZnO₃N₂ distorted trigonal‐bipyramidal and PO₄ tetrahedral units linked through their vertices to give rise to a zero‐dimensional molecular solid (monomer). The structure of the monomer appears to be similar to the secondary building unit (SBU) 4 = 1, commonly found in many fibrous zeolites. To our knowledge, this is the first time this building unit has been isolated. The structure, with a unique composition, is stabilized by hydrogen bond interactions between the terminal —OH groups forms a one‐dimensional molecular wire and also by strong π…π interactions between the 1, 10‐phenanthroline units. Photoluminescence studies show that there is a ligand‐to‐metal charge transfer (LMCT). Crystal data: orthorhombic, space group = Fdd2 (no. 43), a = 40.4669(1), b = 7.4733(2), c = 17.4425(5)Å, V = 5274.9(2)ų, Z = 8.     

Synthesis and Structure of Copper(II) Nitrate Complexes with 2, 6‐Bis(pyrazolyl)pyridine

Three mononuclear copper(II) complexes of copper nitrate with 2, 6‐bis(pyrazol‐1‐yl)pyridine ( bPzPy ) and 2, 6‐bis(3′,5′‐dimethylpyrazol‐1‐yl)pyridine ( bdmPzPy ), [Cu(bPzPy)(NO₃)₂] ( 1 ), [Cu(bPzPy)(H₂O)(NO₃)₂] ( 2 ) and [Cu(bdmPzPy)(NO₃)₂] ( 3 ) were synthesized by the reaction of copper nitrate with the ligand in ethanol solution. The complexes have been characterized through analytical, spectroscopic and EPR measurements. Single crystal X‐ray structure analysis of complexes 1 and 2 revealed a five‐coordinate copper atom in 1 , whereas 2 contains a six‐coordinate (4+2) Cu^II ion with molecular units acting as supramolecular nodes. These neutral nodes are connected through O–H ··· O(nitrate) hydrogen bonds to give couples of parallel linear strips assembled in 1D‐chains in a zipper‐like motif.     

3‐(Arylhydrazono)pentane‐2, 4‐diones and their Complexes with Copper(II) and Nickel(II) — Synthesis and Crystal Structures

A series of new 3‐(arylhydrazono)pentane‐2, 4‐diones ( 1 ‐ 6 ) synthesized from pentane‐2, 4‐dione and diazonium salts of respective anilines using the procedure of Japp‐Klingemann are described. Complexes with Cu^II and Ni^II salts are prepared ( 7 ‐ 10 , respectively). Spectroscopic properties of these compounds have been studied and X‐ray crystal structures of selected hydrazones ( 3 , 4 , 6 ) and of the hydrazone complexes ( 7 ‐ 10 ) are reported. The structures of the uncomplexed hydrazones feature an intramolecular N‐H···O interaction to yield a six‐membered H‐bond ring reflecting preference of the hydrazone tautomeric structure. All the complexes are mononuclear 2:1 (L:M) structures of six‐membered chelate type involving N₂O₂ binding sites that are quadratic arranged but differ in the entire coordination environment dependent on the metal and the ligand substitution including distorted octahedral and quadratic pyramidal coordination geometries in the Cu^II complexes 7 and 8 or nearly regular square planar coordination geometry in the Ni^II complexes 9 and 10 , respectively. In the crystal packings, strong and weak H‐bond interactions cause supramolecular network structures.     

Synthesis and Molecular Structure of Two Zinc Complexes of 1,2‐Bis[(trimethylsilyl)imino]acenaphthene

The reaction of 1,2‐bis[(trimethylsilyl)imino]acenaphthene ( 1 , tms‐BIAN) with ZnCl₂ and ZnI₂ in THF and Et₂O afford (tms‐BIAN)ZnCl₂ ( 2 ) and (tms‐BIAN)ZnI₂ ( 3 ), respectively. The compounds 2 and 3 were characterized by IR‐ and NMR spectroscopy as well as by single crystal X‐ray analysis.     

1D Coordination Polymers from Zinc(II) and Cadmium(II) Halides and 2,2′‐Dithiobis(pyridine N‐oxide): Isostructurality and Structural Diversity

Group 12 halides and 2,2′‐dithiobis(pyridine N‐oxide) (dtpo) form the crystalline the 1D coordination polymers [ZnX₂(μ‐dtpo‐κ²O:O′)]_n [X = Cl ( 1 ), Br ( 2 ), I ( 3 )], [Cd₃(μ‐Cl)₄Cl₂(μ‐dtpo‐κ²O:O′)₂(CH₃OH)₂]_n ( 4 ), [(CdBr₂)₂(μ₃‐dtpo‐κ³O,O:O′)₂(H₂O)₂]_n ( 5 ), and [(CdI₂)₂(μ‐dtpo‐κ²O:O′)₃]_n ( 6 ) in methanol. The compounds were structurally characterized by single‐crystal X‐ray analysis. Compounds 1 – 3 represent an isomorphous series of single‐stranded coordination polymers, whereas the Cd^II derivatives are structurally diverse. The metal nodes in 4 and 5 are trinuclear and dinuclear cadmium clusters, respectively. In 4 and 5 , the metal nodes are linked into double‐stranded 1D coordination polymers by two dtpo bridging ligands. Compound 6 contains mononuclear CdI₂ units as nodes and can be viewed as an alternating copolymer of CdI₂(μ‐dtpo‐κ²O:O′)₂ and CdI₂(μ‐dtpo‐κ²O:O′) entities. Owing to the disulfide moiety, the dtpo bridging ligand inevitably exhibits an axially chiral angular structure. The dtpo ligand adopts various coordination modes through the pyridine N‐oxide oxygen atoms.     

Polymeric Copper(II) Paddlewheel Carboxylate: Structural Description,Electrochemistry, and DNA‐binding Studies

A polymeric complex of copper(II) was isolated and purified from the self‐assembly of CuSO₄ and 2‐phenyl acetate in aqueous medium. It was characterized through FT‐IR, UV/Vis, electron spin resonance, electrochemical solution studies, and powder and single crystal XRD techniques. The structure was revealed to consist of directly interconnected dimeric paddlewheel building units without any intervening ligand. This type of polymeric paddlewheel structures are found very rarely. Each copper is lying in a CuO₅ square pyramid coordinated by four oxygen atoms in the square base while the axial oxygen belongs to the neighboring paddlewheel. Purity and uniform crystalline nature of the complex was assessed from matching theoretical and experimental powder XRD spectra. ESR spectrum consisted of a broad signal with g value = 2.2427, whereas electrochemical studies revealed diffusion controlled electron transfer processes with diffusion co‐efficient = 1.628 × 10^–7 cm² · s^–1. The results of spectroscopic techniques support each other. The complex afforded mixed binding mode with DNA yielding DNA‐binding constant values of 1.384 × 10⁴ m ^–1 and 8.845 × 10⁴ m ^–1 using absorption spectroscopy and cyclic voltammetry, respectively. The complex also exhibited significant activity against anti‐fungal strain Helminthosporium solani by inhibiting its 75 % ± 2.5 growth. The preliminary studies heralded excellent biological potential of the synthesized complex.     

Synthesis and Characterization of New M‐Triazole Complexes (M = Co,Cu, Zn)

Three new complexes with the ligand 3,5‐diamino‐1,2,4‐triazole (Hdatrz), [Co₃(μ₂‐Hdatrz)₆(H₂O)₆]·(NO₃)₈·4H₂O ( 1 ), [Cu₃(μ₂‐Hdatrz)₄(μ₂‐Cl)₂(H₂O)₂Cl₂]·Cl₂·4H₂O·2C₂H₅OH ( 2 ) and {[Zn₂(μ₂‐SO₄) (μ₃‐datrz)₂]·2H₂O}_n ( 3 ) have been synthesized and structurally characterized. Complex 1 has a linear trinuclear mixed‐valence cobalt structure with six neutral triazole ligands in the N(1), N(2)‐bridging mode. The central cobalt atom, Co(1), is coordinated to six nitrogen atoms (octahedral) whereas the terminal cobalt atom, Co(2), is coordinated to an N₃O₃ moiety (octahedral). In complex 1 , the uudd cyclic water clusters, nitrate anions and the trimeric cations are linked to a supramolecular structure. Complex 2 features a linear trinuclear copper(II) core, with four N(1), N(2)‐bridging triazole ligands and two chlorido bridges. The central copper atom is coordinated to an N₄Cl₂ moiety (octahedral) whereas the terminal copper is coordinated to an N₂Cl₂O moiety (square‐pyramidal). In complex 2 , tetrahedral hydrogen bonding interactions play an important role to form a supramolecular network. Complex 3 exhibits a polymeric structure, with N(1), N(2), N(4)‐bridging triazolate ligands and sulfate bridges, in which zinc is coordinated to an N₃O moiety (tetrahedral). In complex 3 , water molecules and sulfate anions construct the sulfate‐water supramolecular chain with hydrogen bonding interactions. In addition, the complexes were investigated by elemental analyses, IR spectroscopic, and thermogravimetric measurements.     

Calixarene-Based Copper(I) Complexes as Models for Monocopper Sites in Enzymes

A cavity that acts as a molecular funnel is formed from calix[6]arene 1 and [Cu^I(NCCH₃)₄]PF₆ [Eq. (a)]. An exchange of the well-protected acetonitrile ligand for other nitriles RCN is only possible with small R groups. The protection of the copper ions precludes oxidative dimerization; thus, the complexes mimic the mononuclear site of copper enzymes.     

NMR Spectroscopic Structural Determination of Organozinc Reagents: Evidence for “Highly Coordinated” Zincates

The structures of ¹³ C-labeled methylzinc reagents have been studied by NMR spectroscopy. Analysis of the spectra gives information on the number of chemically equivalent methyl groups that are attached to the metal centers. Shown is the structure of trimethylzincate with the spin couplings that form the basis of the spin system used in the calculation.     

Nickel(II) Complexes of 1‐Alkyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.13,7]decane – Synthesis and Solid‐State Structures

Complexes [NiI₃(mpta)₂]I ( 1 ) and [NiI₃(ppta)₂]I ( 2 ) have been synthesized by reaction of nickel(II) halide salts with ‐1‐methyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.1^3,7]decane iodide (mpta⁺I^?) and 1‐(n‐propyl)‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.1^3,7]decane bromide (ppta⁺Br^?) respectively. The crystal structures of compounds 1 and 2 are described and are similar, with both compounds crystallizing in monoclinic space groups. The geometry about both nickel atoms is that of a trigonal bipyramid with the cationic phosphine ligands found in the axial positions and the iodide ligands arranged in the equatorial plane.     

Direct Synthesis and Characterization of New Copper(II) and Zinc(II) 5‐R‐Tetrazolato Complexes [R = Me,Ph, 4‐Py] with Ethylenediamine and DMSO as Coligands

Three novel 5‐R‐tetrazolato complexes (R = Me, Ph, 4‐Py), namely [Zn₂(MeCN₄)₄(DMSO)₂] ( 1 ), [Cu₂(PhCN₄)₄(en)₂] · 2DMSO ( 2 ), and [Cu(4‐PyCN₄)₂(DMSO)₂] · 4DMSO ( 3 ), were isolated as unexpected products under attempts to prepare heterometallic tetrazolates using a direct synthesis strategy in the Cu⁰‐ZnO‐en‐RCN₄H‐DMSO system (en = ethylenediamine). The prepared compounds were characterized by elemental, single‐crystal X‐ray, and thermal analyses, and IR spectroscopy. Variation of the 5‐substituent of the tetrazole ring causes different composition of complexes 1 – 3 and diverse coordination modes of 5‐R‐tetrazolato ligands. Complex 1 is a 3D coordination polymer due to N1, N4‐bridging of 5‐methyltetrazolato anions. Complex 2 , with en as a coligand, has a dinuclear structure with two copper atoms linked together by two 5‐phenyltetrazolato ligands by tetrazole N2, N3 bridges. Complex 3 represents a 2D coordination polymer, formed due to 5‐(4‐pyridyl)tetrazolato bridges between adjacent copper atoms (with the tetrazole and pyridine rings nitrogen atoms as coordination centers). DMSO molecules, included in all the compounds, are solvate and/or coordinated ones.     

On Verdigris,Part III: Crystal Structure,Magnetic and Spectral Properties of Anhydrous Copper(II) Acetate,a Paddle Wheel Chain

Pure anhydrous Cu(CH₃COO)₂ was obtained both, by thermal dehydration of Cu(CH₃COO)₂ · H₂O and by drying a commercially purchased mixture of Cu(CH₃COO)₂ · H₂O and Cu(CH₃COO)₂ in a nitrogen atmosphere using P₂O₅ as drying agent. The crystal structure was solved ab initio from synchrotron X‐ray powder diffraction (XRPD) data at 150 °C and from laboratory XRPD data at ambient conditions and found to be isotypic to anhydrous chromium(II), molybdenum(II) and rhodium(II) acetate. Cu(CH₃COO)₂ crystallizes in space group P1 (no. 2) with lattice parameters of a = 5.1486(3) Å, b = 7.5856(6) Å, c = 8.2832(6) Å, α = 77.984(4)°, β = 75.911(8)°, γ = 84.256(6)° at ambient conditions. Cu₂(CH₃COO)₄ paddle wheels with short (2.6 Å) Cu–Cu distances form chains in a direction, which is the main motif in the crystal structure. Due to their identical structural main motif Cu(CH₃COO)₂ · H₂O and Cu(CH₃COO)₂ exhibit a similar bluish‐green color, almost identical UV/Vis spectra and comparable magnetic properties. The temperature dependent magnetic susceptibility also indicates only weak inter‐dimer spin exchange between neighbouring Cu₂(CH₃COO)₄ paddle wheels.     

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.     

Copper(I) Complexes with a Proximal Aromatic Ring: Novel Copper–Indole Bonding

A unique bonding of indole to a metal ion has been established. Two new tridentate N ligands with a pendent indole ring gave Cu^I complexes 1 and 2 , the latter of which exhibits the new form of bonding between the Cu^I ion in a distorted tetrahedral geometry and the indole C(2)−C(3) moiety. The bond is dependent upon the length of the side chain and therefore the accessibility of the ring to the metal center.     

Assemblies of 1D and 2D Copper(II) Chiral Coordination Polymers by Salicylaldehyde Schiff Bases: Synthesis,Crystal Structures,and Magnetic Properties

Reaction of CuCl₂ · 2H₂O with chiral Schiff bases and sodium dicyanamide led to the formation of two chiral copper(II) coordination polymers, namely [Cu₄(L¹)₂(dca)₄]_n ( 1 ) and [Cu₂(L²)(μ‐Cl)(dca)(H₂O)]_n · nH₂O ( 2 ) {H₂L¹ = (1R, 3S)‐N′,N′′‐bis[salicylidene]‐1,3‐diamino‐ 1,2,2‐trimethylcyclopentane, H₂L² = (1R, 3S)‐N′,N′′‐bis[3‐ethoxysalicylidene]‐1,3‐diamino‐ 1,2,2‐trimethylcyclopentane, dca = dicyanamide}. Both complexes were structurally characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. Complex 1 exhibits a two‐dimensional polymeric structure formed by single dca bridging tetranuclear Cu₄ units. Complex 2 displays a left‐handed helical chain structure constructed from Cu₂ dimers with single dca bridges. The chirality of 1 and 2 was confirmed by circular dichroism (CD) measurements in solution. Both complexes exhibit strong antiferromagnetic couplings with J = –308(4) cm^–1 for 1 and J = –123(1) cm^–1 for 2 in 2–300 K.     

Preparation and X-ray characterization of two-coordinate Cu(I) complex of aliphatic thiolato ligand: Effect of steric bulk on coordination features

We have synthesized in a single-step procedure from available copper(I) precursor at RT two Cu(I) thiolato clusters of the formula [Cu₄(μ-SCH(CH₃)₂)₆]²⁻ and [Cu₅(μ-SC(CH₃)₃)₆]⁻ as revealed by X-ray crystallography, where increased steric bulk leads to a bigger cage with some two-coordinate metal centers. In addition, we identified a mononuclear two coordinate thiolato complex with the bulkier ligand, of the formula NEt₄[Cu(SC(CH₃)₃)₂]. This is only the second example of such a complex of an aliphatic ligand that is structurally characterized. The X-ray structure reveals an S–Cu–S angle of 176.7–179.5°, with Cu–S distances of 2.14 Å.     

Metal-Directed Formation of Tetra-, Hexa-, Octa-, and Nonanuclear Complexes of Magnesium,Calcium, Manganese,Copper, and Cadmium

Efficacious metal control of self-assembly of dialkylketipinate dianions leads to completely different supramolecular assemblies. The structures of grid 1 , double-decker 2 , triple-decker 3 , and metalla-spherand 4 were characterized by X-ray crystallographic analyses or by NMR spectroscopy.