Copper(I) halide complexes with 2,2′-bis(diphenylphosphano)-1,1′-binaphthyl (rac-binap) and heterocyclic thiones. Racemic compounds in chiral and achiral crystal space groups

Reactions of copper(I) halides with racemic 2,2′-bis(diphenylphosphano)-1,1′-binaphthyl (rac-binap) in 1:1 molar ratio afforded mononuclear complexes of the type [CuX(rac-binap)] (X = Cl, Br, I) which, on further treatment with 1 equiv. of pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH) or 4,6-dimethyl-pyrimidine-2-thione (dmpymtH) gave rise to the formation of mixed-ligand complexes of the formula [CuX(rac-binap)(thione)]. The molecular structures of [CuBr(rac-binap)(py2SH)] · 2CH₂Cl₂, [CuBr(rac-binap)(py2SH)] · CH₂Cl₂ and [CuBr(rac-binap)(dmpymtH)] · CH₂Cl₂ have been established by single-crystal X-ray diffraction. Each of the complexes features a distorted tetrahedral copper(I) center with the phosphane acting in a chelating fashion. The complexes are strongly luminescent in the solid state at ambient temperature. Unusually, the [CuBr(rac-binap)(py2SH)] · 2CH₂Cl₂ molecules crystallise in a chiral space group with independent S- and R-enantiomers in the asymmetric unit.     

Zur Reaktion der Alkin-Kupfer(I)-Komplexe [CuX(S-Alkin)] (X = Cl,Br, I; S-Alkin = 3,3,6,6-Tetramethyl-1-thia-4-cycloheptin) mit dem Chelat-Liganden N,N,N′,N′-Tetramethylethylendiamin (tmeda)

Organometallic Compounds of Copper. XVII. On the Reaction of the Alkyne-Copper(I) Complexes [CuX(S-Alkyne)] (X = Cl, Br, I; S-Alkyne = 3,3,6,6-Tetramethyl-1-thiacyclohept-4-yne) with the Chelate Ligand N,N,N′,N′-Tetramethylethylendiamine (tmeda) The alkyne copper(I) chloride complex [CuCl(S-Alkyne)]_n ( 2 a ) (S-Alkyne = 3,3,6,6–tetramethyl-1-thiacyclohept-4-yne) adds tetramethylethylene diamine (tmeda) to form the mononuclear compound [CuCl(S-Alkyne)(tmeda)] ( 4 ). The alkyne copper halide complexes [CuBr(S-Alkyne)]_n ( 2 b ) and [CuI(S-Alkyne)]_n ( 2 c ) react with tmeda to yield the complex salts [Cu(S-Alkyne)(tmeda)]⁺ [CuX₂(S-Alkyne)]^– (X = Br ( 5 a ), X = I ( 5 b )). X-ray diffraction studies on all new compounds 4 and 5 reveal distorted tetrahedral coordination of the copper atom in complex 4 and trigonal-planar coordinated copper atoms in the cations and anions of the ionic compounds 5 .     

Synthesis and Characterization of Copper(I) Complexes Containing Tri(2‐Pyridylmethyl)Amine Ligand

Reaction of copper halides CuX (X=Cl, Br, I) with tri(2‐pyridylmethyl)amine) (TPMA) in THF under N₂ affords a series of monomeric copper(I) complexes CuX(TPMA) (X=Cl ( 1 ), Br ( 2 ) and I ( 3 )). Treatment of [CuCl(TPMA)] ( 1 ) with 0.5 equivalent of 1,4‐diisocyanobenzene following by equimolar amount of NaBF₄ affords a novel binuclear complex [(TPMA)Cu(μ‐1,4‐CNC₆H₄NC)Cu(TPMA)](BF₄)₂ ( 4 ). The copper(I) halide TPMA complexes show interesting fluxional behaviors in temperature dependence in the ¹H NMR spectrum that can be explained by the dissociation and reassociation of the pyridyl group and alkylamine nitrogen of TPMA ligand. The crystal structures of 1 , 3 and 4 are determined by an X‐ray diffractometer. Complexes 1 and 3 are distorted tetrahedral coordinates with strong bonding between three pyridyl N atoms and the corresponding halide donor. Crystallographic results of 4 clearly indicates two Cu(I) ions are bridged by 1,4‐diisocyanobenzene, forming a centro‐symmetrical homobinuclear complex with a “dangling” uncoordinated pyridyl group.     

Mixed-ligand complexes of copper(I) with heterocyclic thiones

Summary Novel mixed-ligand copper(I) complexes of general formula [TPP–Cu–(L)Cl] or [TPPhos–Cu–(L)Cl], where TPP=triphenylphosphine, TPPhos=triphenylphosphate and L=imidazolidine-2-thione [Imt],N-propylimidazolidice-2-thione [PrImt],N-i-propylimidazolidine-2-thione [iPrImt], and 1,3-diazinine-2-thione [Diaz] and bis coniplexes of formula [(L)₂CuCl] where L=[PrImt] and [iPrImt] have been prepared and characterized by electronic, vibrational and n.m.r. spectroscopy. The spectral data are consistent with S-donation of thiones. The magnitude of upfield shift in¹³Cn.m.r. of the thionreide carbon on complexation has been interpreted in terms of coordination geometry around the metal stoms. X-ray structure analysis agrees with the conclusions from the spectroscopic measurements. The structure of [(PrImt)₂CuCl] revealed three-coordinated copper(I) with crystal data:a=14.106(4),b=14.380(2),c=19.024(3) A, =108.8(2)°,z=8 and space group P2/c.     

Synthesis,crystal structure and characterization of 3-thiophene aldehyde thiosemicarbazone and its complexes with cobalt(II), nickel(II) and copper(II)

The reaction of cobalt(II), nickel(II), copper(II) chlorides and bromides with 3-thiophene aldehyde thiosemicarbazone (3TTSCH) leads to the formation of a series of new complexes: [Co(3TTSC)₂], [Ni(3TTSC)₂], [CuCl(3TTSC)]₂, [CuBr(3TTSC)]₂ and [CuBr₂(3TTSCH)]. The crystal structures of the free ligand and of the compound [Ni(3TTSC)₂] have been determined by X-ray diffraction methods. For all these complexes, the central ion is coordinated through the sulfur and the azomethine nitrogen atom of the thiosemicarbazone. [Co(3TTSC)₂], [Ni(3TTSC)₂] and [CuBr₂(3TTSCH)] are mononuclear species, while [CuCl(3TTSC)]₂ and [CuBr(3TTSC)]₂ are binuclear complexes.     

Solvent Effect on the Ligand Exchange between Bis(diethyldithiocarbamato)copper(II) and Bis(diethyldiselenocarbamato)copper(II)

EPR and spectrophotometric study on the products of ligand‐exchange taking place on mixing bis(diethyldiselenocarbamato)copper(II), [Cu(Et₂dsc)₂], and bis(diethyldithiocarbamato)copper(II), [Cu(Et₂dtc)₂], solutions is reported. EPR spectra monitored at room temperature for one month period reveal a stable equilibrium among the parents (chromophores CuS₄ and CuSe₄) and the obtained mixed‐chelate [Cu(Et₂dtc)(Et₂dsc)] complex (chromophore CuS₂Se₂) in heptane, hexane, benzene, toluene, acetone, DMFA, DMSO and dichloromethane. In CCl₄ and CHCl₃ two new additional EPR spectra appear attributed to the mixed‐chelate complexes with the chromophores CuSSe₃ and CuS₃Se which are not observed with electronic spectroscopy. The intensities of all five EPR spectra decrease with the time. It is assumed that the new mixed‐chelates observed in CCl₄ and CHCl₃ are obtained in a reaction of [Cu(Et₂dtc)(Et₂dsc)] or [Cu(Et₂dtc)₂] with the ester of diselenocarbamic acid which is formed in a parallel reaction of [Cu(dsc)₂]with CCl₄ or CHCl₃.     

Zur Reaktion der Alkin‐Kupfer(I)‐Komplexe [CuCl(S‐Alkin)] und [Cu2Br2(S‐Alkin)(dms)] (S‐Alkin = 3,3,6,6‐Tetramethyl‐1‐thia‐4‐cycloheptin,dms = Dimethylsulfid) mit den Lithiumorganylen Phenyllithium und Fluorenyllithium

Organometallic Compounds of Copper. XX On the Reaction of the Alkyne Copper(I) Complexes [CuCl(S‐Alkyne)] and [Cu₂Br₂(S‐Alkyne)(dms)] (S‐Alkyne = 3,3,6,6‐Tetramethyl‐1‐thiacyclohept‐4‐yne; dms = Dimethylsulfide) with the Lithiumorganyls Phenyllithium und Fluorenyllithium The alkyne copper(I) bromide complex [Cu₂Br₂(S‐Alkyne)(dms)] ( 3 b ) (S‐Alkyne = 3,3,6,6‐tetramethyl‐1‐thiacyclohept‐4‐yne; dms = dimethylsulfide) reacts with phenyllithium to form a tetranuclear copper(I) complex of the composition [Cu₄(C₆H₅)₂(S‐Alkenyl)₂] ( 7 ) in low yield (4%). The reaction of the alkyne copper(I) chloride complex [CuCl(S‐Alkyne)] ( 2 a ) with fluorenyllithium in tetrahydrofuran (thf) affords a lithium cuprate of the composition [Li(thf)₄]⁺ [Cu₂(fluorenyl)₃(S‐Alkyne)₂]^– ( 8 ) (yield 32%). The structures of both new complexes 7 and 8 were determined by X–ray diffraction.     

Luminescent silver nitrate complexes of bis[2-(diphenylphosphano)phenyl]ether (DPEphos): Crystal structure of [Ag(DPEphos)(py2SH)2]NO3

Heteroleptic silver(I) nitrate complexes containing the bis[2-(diphenylphosphano)phenyl]ether (DPEphos) ligand and the heterocyclic thioamides pyridine-2(1H)-thione (py2SH), pyrimidine-2(1H)-thione (pymtH), 4,6-dimethylpyrimidine-2(1H)-thione (dmpymtH), 1,4,5,6-tetrahydropyrimidine-2-thione (thpymtH) or 1,3-imidazolidine-2-thione (imtH₂) have been synthesized and characterized by IR and UV-Vis spectroscopy, elemental analyses and melting point determinations. The complexes can be obtained by the addition of the thioamide ligand to an AgNO₃-diphosphane adduct in dichloromethane/ethanol solution. The molecular structure of [Ag(DPEphos)(py2SH)₂]NO₃ complex has been established by single-crystal X-ray diffraction. The structure features a tetrahedral silver(I) center with two phosphorus atoms from the chelating diphos ligand, and the exocyclic sulfur atom of two heterocyclic thioamide units. Intense blue-green emission is observed in the region 470-483 nm for all the complexes in the solid state and in solution at ambient temperature.     

Ligating properties oftert-phosphine/arsine sulphides or selenides,Part IX. Preparation and spectroscopic studies of copper(I)/copper(II) complexes with bis(—phosphine chalcogenides)

Summary The analytical, molar conductance and spectroscopic studies of new complexes of copper(I) and copper(II) with bis(—phosphine chalcogenides), Ph₂P(E)(CH₂)_n-P(E)Ph₂(L-L) are reported. The complexes are of the types: (a) [CuX(L-L)](X, n, E: Cl, 2–4, Br, 2, S; Cl, Br, 1, Se); (b) [Cu₂X₂(L-L)] (X, n, E: Cl, Br, 2, 3, Se) and (c) [CuCl₂(L-L)] (n, E: 2, 3, S). Possible structures have been derived.     

Hg(II), Tl(III), Cu(I), and Pd(II) Complexes with 2,2'-Diphenyl-4,4'-Bithiazole (DPBTZ), Syntheses and X-Ray Crystal Structure of [Hg(DPBTZ)(SCN)2]

Reaction of the ligand 2,2′-diphenyl-4,4′-bithiazole (DPBTZ) with Hg(SCN)₂, Tl(NO₃)₃, CuCl, and PdCl₂ gives complexes with stoichiometry [Hg(DPBTZ)(SCN)₂], [Tl(DPBTZ)(NO₃)₃], [Cu(DPBTZ)(H₂O)Cl]_, and [Pd(DPBTZ)Cl₂]. The new complexes were characterized by elemental analyses and infrared spectroscopy. The crystal structure of [Hg(DPBTZ)(SCN)₂] determined by X-ray crystallography. The Hg atom in the title monomeric complex, (2,2′-diphenyl-4,4′-bithiazole)mercury(II)bisthiocyanate, [Hg(C₁₈H₁₂N₂S₂)(SCN)₂], is four-coordinate having an irregular tetrahedral geometry composed of two S atoms of thiocyanate ions [Hg-S 2.4025(15) and 2.4073(15) Å] and two N atoms of 2,2′-diphenyl-4,4′-bithiazole ligand [Hg-N 2.411(4) and 2.459(4) Å]. The bond angle S(3)-Hg(1)-S(4) of 147.46(5)° has the greatest derivation from ideal tetrahedral geometry. Intermolecular interaction between Hg(1) and two S atoms of two neighboring molecules, 3.9318(15) and 3.9640(18) Å, make the Hg(1) distort from a tetrahedron to a disordered octahedron. The attempts for preparation complexes of Tl(I), Pb(II), Bi(III), Cd(II) ions with 2,2′-diphenyl-4,4′-bithiazole ligand were not successful and also the attempts for preparation complexes of 4,4′,5,5′-tetraphenyl-2,2′-bithizole ligand with Cu(II), Ni(II), Co(II), Co(III), Mn(II), Mn(III), Fe(II), Fe(III), Cr(III), Zn(II), Tl(III), Pb(II), Hg(II), Cu(I), Pd(II) were not successful. This point can be regarded as the initial electron withdrawing of phenyl rings and also their spatial steric effects.     

Silver(I) bromide complexes of the rigid diphosphanes 1,2-bis(diphenylphosphano)benzene (dppbz) and 4,5-bis(diphenylphosphano)-9,9-dimethyl-xanthene (xantphos): Crystal structures of [Ag(μ2-Br)(dppbz)]2, [AgBr(xantphos)] and [AgBr(xantphos)(py2SH)]

Reaction of silver(I) bromide with equimolar amounts of the rigid diphos ligands 1,2-bis(diphenylphosphano)benzene (dppbz) and 4,5-bis(diphenylphosphano)-9,9-dimethyl-xanthene (xantphos) in acetone and acetonitrile led to the corresponding chelates [Ag(μ₂-Br)(dppbz)]₂ (1) and [AgBr(xantphos)] (2). Treatment of 1 and 2 with pyridine-2-thione (py2SH) in ethanol gave the mixed-ligand complexes [AgBr(dppbz)(py2SH)] (3) and [AgBr(xantphos)(py2SH)] (4), respectively. Compounds 1, 2 and 4 have been characterized by X-ray diffraction, establishing distorted tetrahedral or trigonal planar coordination geometries of the silver atoms.     

Synthesis,structural characterization,antimicrobial, DNA-binding,and photo-induced DNA cleavage activity of some bio-sensitive Schiff base copper(II) complexes

Schiff base mixed-ligand copper complexes [CuL¹(phen)Cl₂], [CuL¹(bipy)Cl₂], [Cu(L¹)₂Cl₂], [Cu(L²)₂Cl₂], [CuL²(bipy)Cl₂], and [CuL²(phen)Cl₂] (where L^1?=?4-[3,4-dimethoxy-benzylidene]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazole-3-one; L^2?=?4-[3-hydroxy-4-nitro-benzylidene]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazole-3-one; phen?=?1,10-phenanthroline; and bipy?=?2,2′-bipyridine) have been synthesized and characterized. Their DNA-binding properties have been studied by electronic absorption spectra, viscosity, and electrochemical measurements. The absorption spectral and viscosity results suggest that the copper(II) complexes bind to DNA via partial intercalation. The addition of DNA resulting in the decrease of the peak current of the copper(II) complexes indicates their interaction. Interaction between the complexes and DNA has also been investigated by submarine gel electrophoresis. The copper complexes cleave supercoiled pUC19 DNA to nicked and linear forms through hydroxyl radical and singlet oxygen in the presence of 3-mercaptopropionic acid as the reducing agent. These copper complexes promote the photocleavage of pUC19 DNA under irradiation at 360?nm. Mechanistic study reveals that singlet oxygen is likely to be the reactive species responsible for the cleavage of plasmid DNA by the synthesized complexes. The in vitro antimicrobial study indicates that the metal chelates have higher activity against the bacterial and fungal strains than the free ligands.     

Zur Reaktion der Alkin‐Kupfer(I)‐Komplexe [CuX(S‐Alkin)] (X = Cl,Br, I; S‐Alkin = 3,3,6,6‐Tetramethyl‐1‐thia‐4‐cycloheptin) mit den Phosphanen PMe3 und Ph2PCH2CH2PPh2 (dppe)

Organometallic Compounds of Copper. XVIII. On the Reaction of the Alkyne Copper(I) Complexes [CuX(S‐Alkyne)] (X = Cl, Br, I; S‐Alkyne = 3,3,6,6‐Tetramethyl‐1‐thiacyclohept‐4‐yne) with the Phosphanes PMe₃ and Ph₂PCH₂CH₂PPh₂ (dppe) The alkyne copper(I) halide complexes [CuX(S‐Alkyne)]_n ( 2 ) ( 2 a : X = Cl, 2 b : X = Br, 2 c : X = I; S‐Alkyne = 3,3,6,6‐tetramethyl‐1‐thiacyclohept‐4‐yne; n = 2, ∞) add the phosphanes PMe₃ and Ph₂PCH₂CH₂PPh₂ (dppe) to form the mono‐ and dinuclear copper compounds [(S‐Alkyne)CuX(PMe₃)] ( 6 ) ( 6 a : X = Cl, 6 b : X = Br) and [(S‐Alkyne)CuX(μ‐dppe)CuX(S‐Alkyne)] ( 7 a : X = Cl, 7 b : X = Br, 7 c : X = I), respectively. By‐product in the reaction of 2 a with dppe is the tetranuclear complex [(S‐Alkyne)Cu(μ‐X)₂Cu(μ‐dppe)₂Cu(μ‐X)₂Cu(S‐Alkyne)] ( 8 ). In case of the compounds 7 prolonged reaction times yield the alkyne‐free dinuclear copper complexes [Cu₂X₂(dppe)₃] ( 9 ) ( 9 a : X = Cl, 9 b : X = Br, 9 c : X = I)). X‐ray diffraction studies were carried out with the new compounds 6 a , 6 b , 7 b , 8 , and 9 c .     

Synthesis and characterization of [Cu(Phca2en)(PPh3)X] (X=Cl, Br, I, NCS, N3) complexes: crystal structures of [Cu(Phca2en)(PPh3)Br] and [Cu(Phca2en)(PPh3)I]

New mixed-ligand copper(I) complexes, [Cu(Phca₂en)(PPh₃)X], [Phca₂en = N,N′-bis(β-phenylci-nnamaldehyde)-1,2-diiminoethane and X=Cl (1), Br (2), I (3), NCS (4), N₃ (5)] have been synthesized and characterized by various techniques. ¹H and ¹³C-NMR and IR spectral data of these copper(I) complexes are compared with the free ligand to elucidate some structural features. The structures of [Cu(Phca₂en)(PPh₃)Br] (2) and [Cu(Phca₂en)(PPh₃)I] (3) have been determined from single-crystal data showing that the coordination geometry around copper atom is a distorted tetrahedron. Furthermore, these Cu(I) complexes exhibit supramolecular motifs of the type multiple phenyl embraces resulting from attractive interactions between phenyl rings of PPh₃ moieties. The presence of the C–H…Cu weak intramolecular hydrogen bonds, due to the trapping of C–H bonds in the vicinity of the metal atoms, is also reported.     

Structural and electronic properties of luminescent copper(I) halide complexes of bis[2-(diphenylphosphano)phenyl] ether (DPEphos). Crystal structure of [CuCl(DPEphos)(dmpymtH

Heteroleptic copper(I) halide complexes containing the bis[2-(diphenylphosphano)phenyl]ether (DPEphos) ligand and the heterocyclic thioamides pyridine-2(1H)-thione (py2SH), pyrimidine-2(1H)-thione (pymtH) or 4,6-dimethylpyrimidine-2(1H)-thione (dmpymtH) have been synthesized and characterized by (1)H-NMR, IR spectroscopy, elemental analyses and melting point determinations. The complexes can be readily obtained by the addition of the thione ligand to a CuX-diphosphane adduct in dichloromethane-ethanol solution. The molecular structure of [CuCl(DPEphos)(dmpymtH)] complex has been established by single-crystal X-ray diffraction. The structure features a tetrahedral copper(I) center with two phosphorus atoms from the chelating diphos ligand, one halogen atom and the exocyclic sulfur atom of the heterocyclic thioamide unit. The complexes are strongly emissive in the solid state at ambient temperature. DFT and TD-DFT calculations were employed to study the structural, electronic and photophysical properties of the novel complexes. Electronic absorption spectra show two broad bands in the regions 275-290 and 380-398 nm of mixed MLCT/IL character. Intense blue-green emission is observed in the region 500-558 nm for complexes having py2SH or dmpymtH thione ligands. The emitting first triplet excited state, T(1) is mainly localized on the thione ligand.     

Copper(I) complexes with fluorinated hydrotris(pyrazolyl)borate: Influence of electronic effects on their structure,physicochemical properties,and reactivity

Copper(I) coordination complexes of the anionic fluorinated ligand, hydrotris(3-trifluoromethyl-5-methyl-1-pyrazolyl)borate (L0f⁻), i.e. the copper(I) carbonyl complex, [Cu^I(L0f)(CO)] (1), the copper(I) triphenylphosphine complex, [Cu^I(L0f)(PPh₃)] (2), the copper(I) acetonitrile complex, [Cu^I(L0f)(NCMe)] (3), and the corresponding copper(I) triphenylphosphine complex with hydrotris(3,5-diisopropyl-1-pyrazolyl)-borate anion (L1⁻), i.e. [Cu^I(L1)(PPh₃)] (4), were synthesized in order to investigate the influence of the electron-withdrawing groups on the pyrazolyl rings. The structures of complexes 1, 2, and 4 were determined by X-ray crystallography. While X-ray crystallography did not show definitive trends in terms of copper(I) atom geometry, the clear influence of the electronic structure of the pyrazolyl rings is observed by spectroscopic techniques, namely, IR and multinuclear NMR spectroscopy. Finally, the relative stability of the copper(I) complexes is discussed.     

Electronic structure and properties of camphorimine Cu(I) coordination polymers

The first Cu(I) coordination polymer with an aromatic‐substituted camphorimine ligand [(CuCl)(μ‐Cl) (Cu(H₂NC₆H₄NC₁₀H₁₄O)]_n was obtained from reaction of CuCl with 3‐(4‐aminophenylimino)‐1,7,7‐trimethylbicyclo[2.2.1]heptan‐2‐one (H₂NC₆H₄NC₁₀H₁₄O). The electronic and the surface properties (studied by X‐ray photoelectron spectroscopy) are consistent with two distinct coordination environments for the copper(I) atoms—tetrahedral and linear—for the polymer family [(CuCl)(μ‐Cl){Cu(YNC₁₀H₁₄O)}]_n. DFT band calculations reveal that the highest energy bands are more localized on the copper(I) tetrahedral sites than on the copper(I) linear sites. The redox properties of [(CuCl)(μ‐Cl){Cu(YNC₁₀H₁₄O)}]_n [Y = NMe₂ ( 2b ), NH₂, and H₂NC₆H₄NC₁₀H₁₄O ( 2a )] studied by cyclic voltammetry show that the oxidation potentials of the two copper centers are in fact indistinguishable. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Complex formation reactions between [Pd(piperazine)(H2O)2]2+ and biorelevant ligands: synthesis and equilibrium constants

[Pd(pip)Cl₂], [Pd(pip)(cbdca)] ? 2H₂O, and [Pd(pip)(malonate)] ? 2H₂O complexes were synthesized and characterized, where pip is piperazine and cbdca is cyclobutanedicarboxylate. The stoichiometry and stability of the complexes formed between [Pd(pip)(H₂O)₂]²⁺ and various biologically relevant ligands (amino acids, peptides, DNA constituents, and dicarboxylic acids) were investigated at 25°C and 0.1 M ionic strength. The stability constant of the complexes formed in solution was determined and the binding centers of the ligands were assigned. The concentration distribution diagrams of the complexes were evaluated.     

Mechanochemical synthesis in copper(II) halide/pyridine systems: single crystal X-ray diffraction and IR spectroscopic studies

Whereas complexes of divalent metal halides (X = Cl, Br, I) with/from pyridine commonly crystallise as trans-[M(py)(4)X(2)]·2py, M on a site of 222 symmetry in space group Ccca, true for CuCl(2) and CuBr(2) in particular, the copper(II) iodide adduct is of the form [Cu(py)(4)I]I·2py, Cu on a site of mm2 symmetry in space group Cmcm, and five-coordinate (square-pyramidal), the same cationic species also being found in 2[Cu(py)(4)I](I(3))·[(py)(2)Cu(μ-I)(2)Cu(py)(2)] (structurally defined). Bromide or N-thiocyanate may be substituted for the unbound iodide ion in the solvated salt, resulting in complexes which crystallize in space group Ccca, but with both anions and the metal atom disordered. In [Cu(py)(4)(I(3))(2)], a pair of long Cu···I contacts approach a square-planar Cu(py)(4) array. Assignments of the ν(CuN) and ν(CuX) (X = Br, I, SCN) bands in the far-IR spectra are made, the latter with the aid of analogous assignments for [Cu(py)(2)X(2)] (X = Cl, Br), which show a dependence of ν(CuX) on the Cu-X bond length that is very similar to that determined previously for copper(i) halide complexes. The structure of the adventitious complex [(trans-)(H(2)O)(py)(4)CuClCu(py)(4)](I(3))(3)·H(2)O is also recorded, with six- and five-coordinate copper atoms; rational synthesis provides [{Cu(py)(4)}(2)(μ-Cl)](I(3))(3)·H(2)O with one water molecule less. In [{Cu(py)(4)Cl}((∞|∞))](I(3))·3py, square pyramidal [Cu(py)(4)Cl](+) cations, assisted by Cl···Cu interactions, stack to give rise to infinite polymeric strings. Several of these compounds were prepared mechanochemically, illustrating the applicability of this method to syntheses involving redox reactions as well as to complex syntheses involving up to five components. The totality of results demonstrates that the [Cu(II)(py)(4)] entity can be stabilized in an unexpectedly diverse range of mononuclear and multinuclear complexes through the presence of lattice pyridine molecules, the bulky triiodide ion, or a combination of both.