A one‐dimensional heterometallic coordination polymer with a three‐dimensional supramolecular framework: poly[μ2‐aqua‐diaqua(2,2′‐bipyridyl)(μ5‐2‐sulfonatobutanedioato)copper(II)sodium(I)]

The title compound, [CuNa(C₄H₃O₇S)(C₁₀H₈N₂)(H₂O)₃]_n, consists of one Cu^II cation, one Na^I cation, one 2‐sulfonatobutanedioate trianion (SSC³⁻), one 2,2′‐bipyridyl (bpy) ligand and three coordinated water molecules as the building unit. The coordination of the Cu^II cation is composed of two pyridyl N atoms, one water O atom and two carboxylate O atoms in a distorted square‐pyramidal coordination geometry with an axial elongation. The Na^I cation is six‐coordinated by three water molecules and three carboxylate O atoms from three SSC³⁻ ligands in a distorted octahedral geometry. Two SSC³⁻ ligands link two Cu^II cations to form a Cu₂(SSC)₂(bpy)₂ macrocyclic unit lying across an inversion centre, which is further linked by Na^I cations via Na—O bonds to give a one‐dimensional chain. Interchain hydrogen bonds link these chains to form a two‐dimensional layer, which is further extended into a three‐dimensional supramolecular framework through π–π stacking interactions. The thermal stability of the title compound has also been investigated.     

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H‐benzotriazole: poly[μ3‐benzotriazolato‐κ3N1:N2:N3‐copper(I)]

The title complex, [Cu(C₆H₄N₃)]_n, was synthesized by the reaction of cupric nitrate, 1H‐benzotriazole (BTAH) and aqueous ammonia under hydrothermal conditions. The asymmetric unit contains three crystallographically independent Cu^I cations and two 1H‐benzotriazolate ligands. Two of the Cu^I cations, one with a linear two‐coordinated geometry and one with a four‐coordinated tetrahedral geometry, are located on sites with crystallographically imposed twofold symmetry. The third Cu^I cation, with a planar three‐coordinated geometry, is on a general position. Two Cu^I cations are doubly bridged by two BTA⁻ ligands to afford a noncentrosymmetric planar [Cu₂(BTA)₂] subunit, and two [Cu₂(BTA)₂] subunits are arranged in an antiparallel manner to form a centrosymmetric [Cu₂(BTA)₂]₂ secondary building unit (SBU). The SBUs are connected in a crosswise manner via the sharing of four‐coordinated Cu^I cations, Cu—N bonding and bridging by two‐coordinate Cu^I cations, resulting in a one‐dimensional chain along the c axis. These one‐dimensional chains are further linked by C—H...π and weak van der Waals interactions to form a three‐dimensional supramolecular architecture.     

A mixed‐valence copper coordination polymer generated by a hydrothermal metal/ligand redox reaction process

The title coordination polymer, poly[(μ₄‐2‐oxidoisophthalato‐κ⁶O¹,O²:O²,O³:O^3′:O^3′)(μ₂‐quinoxaline‐κ²N:N′)copper(I)copper(II)], [Cu₂(C₈H₃O₅)(C₈H₆N₂)]_n, contains two crystallographically distinct Cu ions, one quinoxaline (QA) unit and one 2‐oxidoisophthalate trianion (L) derived from 2‐hydroxyisophthalic acid (H₃L). The Cu^II ion is strongly coordinated by four O atoms in a distorted square geometry, of which two belong to two phenoxide groups and the other two to carboxylate groups of two L ligands. In addition, the Cu^II cation interacts weakly with a symmetry‐related carboxylate O atom which belongs to the L ligand in an adjacent layer, giving a square‐pyramidal coordination geometry. The Cu^I ion is trigonally coordinated by two N atoms from two QA molecules and one O atom from an L carboxylate group. The Cu^I centres are bridged by QA ligands to give a chain along the c axis. Two Cu^II ions and two L ligands form a [Cu₂L₂]²⁻ `metallo‐ligand', which coordinates two Cu^I ions. Thus, the chains of Cu^I and QA are linked by the [Cu₂L₂]²⁻ metallo‐ligand to yield a two‐dimensional (6,3) sheet. These sheets are further linked by symmetry‐related carboxylate O atoms of neighbouring layers into a three‐dimensional framework. The in situ reaction from benzene‐1,2,3‐tricarboxylic acid (H₃L1) to L in the present system has rarely been observed before, although a few novel in situ reactions, such as ligand oxidative coupling, hydrolysis and substitution, have been observed during the hydrothermal process.     

The coordination chemistry of two symmetric double‐armed oxadiazole‐bridged organic ligands with copper salts

Two new symmetric double‐armed oxadiazole‐bridged ligands, 4‐methyl‐{5‐[5‐methyl‐2‐(pyridin‐3‐ylcarbonyloxy)phenyl]‐1,3,4‐oxadiazol‐2‐yl}phenyl pyridine‐3‐carboxylate (L1) and 4‐methyl‐{5‐[5‐methyl‐2‐(pyridin‐4‐ylcarbonyloxy)phenyl]‐1,3,4‐oxadiazol‐2‐yl}phenyl pyridine‐4‐carboxylate (L2), were prepared by the reaction of 2,5‐bis(2‐hydroxy‐5‐methylphenyl)‐1,3,4‐oxadiazole with nicotinoyl chloride and isonicotinoyl chloride, respectively. Ligand L1 can be used as an organic clip to bind Cu^II cations and generate a molecular complex, bis(4‐methyl‐{5‐[5‐methyl‐2‐(pyridin‐3‐ylcarbonyloxy)phenyl]‐1,3,4‐oxadiazol‐2‐yl}phenyl pyridine‐3‐carboxylate)bis(perchlorato)copper(II), [Cu(ClO₄)₂(C₂₈H₂₀N₄O₅)₂], (I). In compound (I), the Cu^II cation is located on an inversion centre and is hexacoordinated in a distorted octahedral geometry, with the pyridine N atoms of two L1 ligands in the equatorial positions and two weakly coordinating perchlorate counter‐ions in the axial positions. The two arms of the L1 ligands bend inward and converge at the Cu^II coordination point to give rise to a spirometallocycle. Ligand L2 binds Cu^I cations to generate a supramolecule, diacetonitriledi‐μ₃‐iodido‐di‐μ₂‐iodido‐bis(4‐methyl‐{5‐[5‐methyl‐2‐(pyridin‐4‐ylcarbonyloxy)phenyl]‐1,3,4‐oxadiazol‐2‐yl}phenyl pyridine‐4‐carboxylate)tetracopper(I), [Cu₄I₄(CH₃CN)₂(C₂₈H₂₀N₄O₅)₂], (II). The asymmetric unit of (II) indicates that it contains two Cu^I atoms, one L2 ligand, one acetonitrile ligand and two iodide ligands. Both of the Cu^I atoms are four‐coordinated in an approximately tetrahedral environment. The molecule is centrosymmetric and the four I atoms and four Cu^I atoms form a rope‐ladder‐type [Cu₄I₄] unit. Discrete units are linked into one‐dimensional chains through π–π interactions.     

Sterically Demanding AgI and CuI N-Heterocyclic Carbene Complexes: Synthesis,Structures, Steric Parameters,and Catalytic Activity

The synthesis and full characterization of new air-stable Ag^I and Cu^I complexes bearing structurally bulky expanded-ring N-heterocyclic carbene (erNHC) ligands is presented. The condensation of protonated NHC salts with Ag₂O afforded a collection of Ag^I complexes, and their first use as ligand transfer reagents led to novel isostructural Cu^I or Au^I complexes. In situ deprotonation of the NHC salts in the presence of a copper(I) source, provides a library of new Cu^I complexes. The solid-state structures feature large N-C_NHC-N angles (118–128°) and almost identical angles between the aryl groups on the nitrogen atoms and the plane of the N-C-N unit of the carbene (i.e. torsion angles close to 0°). Among the steric parameters, the percent buried volume (%V_bur) values span easily in the 50–57 % range, and that one of (9-Dipp)CuBr complex (%V_bur=57.5) overcomes to other known erNHC–metal complexes reported to date. Preliminary catalytic experiments in the copper-catalyzed coupling between N-tosylhydrazone and phenylacetylene, afforded 76–93 % product at the 0.5–2.5 mol % catalyst loading, proving the stability of Cu^I erNHC complexes at elevated temperatures (100 °C).     

A stair‐like two‐dimensional silver(I) coordination polymer of N′‐(3‐cyanobenzylidene)nicotinohydrazide

The structure of the title compound, poly[[[μ₃‐N′‐(3‐cyanobenzylidene)nicotinohydrazide]silver(I)] hexafluoroarsenate], {[Ag(C₁₄H₁₀N₄O)](AsF₆)}_n, at 173 K exhibits a novel stair‐like two‐dimensional layer and a three‐dimensional supramolecular framework through C—H...Ag hydrogen bonds. The Ag^I cation is coordinated by three N atoms and one O atom from N′‐(3‐cyanobenzylidene)nicotinohydrazide (L) ligands, resulting in a distorted tetrahedral coordination geometry. The organic ligand acts as a μ₃‐bridging ligand through the pyridyl and carbonitrile N atoms and deviates from planarity in order to adapt to the coordination geometry. Two ligands bridge two Ag^I cations to construct a small 2+2 Ag₂L₂ ring. Four ligands bridge one Ag^I cation from each of four of these small rings to form a large grid. An interesting stair‐like two‐dimensional (3,6)‐net is formed through Ag^I metal centres acting as three‐connection nodes and through L molecules as tri‐linkage spacers.     

A two‐dimensional mixed‐valence CuII/CuI coordination polymer constructed from 2‐(pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylate

Coordination polymers are a thriving class of functional solid‐state materials and there have been noticeable efforts and progress toward designing periodic functional structures with desired geometrical attributes and chemical properties for targeted applications. Self‐assembly of metal ions and organic ligands is one of the most efficient and widely utilized methods for the construction of CPs under hydro(solvo)thermal conditions. 2‐(Pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylate (HPIDC²⁻) has been proven to be an excellent multidentate ligand due to its multiple deprotonation and coordination modes. Crystals of poly[aquabis[μ₃‐5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ⁵N¹,O⁵:N³,O⁴:N²]copper(II)dicopper(I)], [Cu^IICu^I₂(C₁₀H₅N₃O₄)₂(H₂O)]_n, (I), were obtained from 2‐(pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃PIDC) and copper(II) chloride under hydrothermal conditions. The asymmetric unit consists of one independent Cu^II ion, two Cu^I ions, two HPIDC²⁻ ligands and one coordinated water molecule. The Cu^II centre displays a square‐pyramidal geometry (CuN₂O₃), with two N,O‐chelating HPIDC²⁻ ligands occupying the basal plane in a trans geometry and one O atom from a coordinated water molecule in the axial position. The Cu^I atoms adopt three‐coordinated Y‐shaped coordinations. In each [CuN₂O] unit, deprotonated HPIDC²⁻ acts as an N,O‐chelating ligand, and a symmetry‐equivalent HPIDC²⁻ ligand acts as an N‐atom donor via the pyridine group. The HPIDC²⁻ ligands in the polymer serve as T‐shaped 3‐connectors and adopt a μ₃‐κ²N,O:κ²N′,O′:κN′′‐coordination mode, linking one Cu^II and two Cu^I cations. The Cu cations are arranged in one‐dimensional –Cu1–Cu2–Cu3– chains along the [001] direction. Further crosslinking of these chains by HPIDC²⁻ ligands along the b axis in a –Cu2–HPIDC²⁻–Cu3–HPIDC²⁻–Cu1– sequence results in a two‐dimensional polymer in the (100) plane. The resulting (2,3)‐connected net has a (12³)₂(12)₃ topology. Powder X‐ray diffraction confirmed the phase purity for (I), and susceptibilty measurements indicated a very weak ferromagnetic behaviour. A thermogravimetric analysis shows the loss of the apical aqua ligand before decomposition of the title compound.     

A linear cyclic oximate-bridged ­tetracopper(II) complex

The crystal structure of the title complex, tetrakis­[μ-6-amino-3-methyl-4-aza­hex-3-en-2-one oximato(1–)-κ⁴N,N′,N′′:O]tetracopper(II) tetraperchlorate 0.6-hydrate, [Cu₄(C₆H₁₂N₃O)₄](ClO₄)₄·0.6H₂O, shows the cation to be an oximate-bridged tetramer composed of four 6-amino-3-methyl-4-aza­hex-3-en-2-one oxime ligands and four copper(II) ions and to have crystallographically imposed symmetry. Each Cu^II atom is four-coordinated by the three N atoms of one oxime ligand and by the O atom of another oxime ligand in a distorted square-planar geometry.     

catena-Poly[[(acetonitrile-N)dichlorocopper(II)]-μ-2,5-dimethylpyrazine-κ2N:N′]

In the structure of the title compound, [CuCl₂­(C₂H₃N)(C₆H₈N₂)], each Cu²⁺ cation is surrounded by two 2,5-di­methyl­pyrazine ligands, one aceto­nitrile ligand and two Cl⁻ anions within a distorted tetragonal pyramid. The aceto­nitrile ligand, which forms the apex of the pyramid, the Cu²⁺ cation and the Cl⁻ anions are all located in general positions, whereas each of the 2,5-di­methyl­pyrazine ligands is located about a centre of inversion. The 2,5-di­methyl­pyrazine ligands connect the Cu²⁺ cations viaμ-N:N′ coordination to form chains.     

Bis[N,N′‐(2‐chlorobenzylidene)ethylenediamine‐κ2N,N′]copper(I) dichloridocuprate(I) acetonitrile solvate

The 1:1 adduct of N,N′‐bis(2‐chlorobenzylidene)ethylenediamine (cb₂en) with copper(I) chloride proves to be an ionic compound with Cu^I‐centred cations and anions, [Cu(C₁₆H₁₄Cl₂N₂)₂][CuCl₂]·CH₃CN. In the cation, the Cu^I atom has a flattened tetrahedral coordination geometry, with a small bite angle for the chelating ligands, which form a double‐helical arrangement around the metal centre. The anion is almost linear, as expected. The packing of the cations involves intermolecular π–π interactions, which lead to columns of translationally related cations along the shortest unit‐cell axis, with anions and solvent molecules in channels between them.     

A novel luminescent ionic trinuclear Cu3I2 cluster cuprous complex supported by a P^N ligand: synthesis,structure characterization,properties and TD–DFT calculations

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title ionic trinuclear Cu₃I₂ complex, tris[μ₂‐diphenyl(pyridin‐2‐yl)phosphane‐κ²P:N]di‐μ₃‐iodido‐tricopper(I)(3 Cu—Cu) hexafluoridophosphate, [Cu₃I₂(C₃₉H₃₂NP)₃]PF₆, conventionally abbreviated as [Cu₃I₂(Ph₂PPy)₃]PF₆, is described. Each Cu^I atom is coordinated by two μ₃‐iodide ligands and by a P and an N atom from two Ph₂PPy ligands, giving rise to a CuI₂PN tetrahedral coordination geometry about each Cu^I centre. The electronic absorption and photoluminescence properties of this trinuclear cluster have been studied on as‐synthesized samples, which had been examined previously by powder X‐ray diffraction. A detailed time‐dependent density functional theory (TD–DFT) study was carried out and showed a green emission derived from a halide‐to‐ligand charge transfer and metal‐to‐ligand charge transfer ³(X+M)LCT excited state.     

Reversible Transformation between Cubane and Stairstep Cu4I4 Clusters Using Heat or Solvent Vapor

The controlled self‐assembly of CuI and an asymmetric ligand with mixed N/S donors, 2‐(tert‐butylthio)‐N‐(pyridin‐3‐yl)acetamide ( L ), afforded three Cu^I coordination polymers (CPs), [Cu₄I₄ L ₂(MeCN)₂]_n ( 1 ), [Cu₄I₄ L ₂]_n ( 2 ), and {[Cu₄I₄ L ₂] ? MeOH}_n ( 3 ). X‐ray analyses showed that CPs 1 – 3 are supramolecular isomers with 1, 2, and 3D structures, respectively. CP 1 adopts a stairstep Cu₄I₄ cluster, whereas CPs 2 and 3 are composed of cubane‐like Cu₄I₄ clusters. Crystal‐to‐crystal transformations of 1 to 2 and 3 showed reversible transformations between different Cu₄I₄ clusters using heat or solvent (acetonitrile or methanol) vapor. CP 2 was reversibly transformed to 3 by the addition of methanol and heat. Therefore, the transformations between supramolecular isomers 1 , 2 , and 3 are completely reversible.     

catena‐Poly[[bis(nicotinamide‐κN1)copper(I)]‐μ‐thiocyanato‐κ2N:S]

The Cu^I cations in the title compound, [Cu(NCS)(C₆H₆N₂O)₂]_n, are coordinated by N atoms from each of two mirror‐related nicotin­amide ligands, as well as by one N atom of one thio­cyanate ligand and one S atom of a symmetry‐related thio­cyanate ligand, within a slightly distorted tetrahedron. The Cu^I cations and the thio­cyanate anions are located on a crystallographic mirror plane and the nicotin­amide ligands occupy general positions. The Cu^I cations are connected by the thio­cyanate anions to form chains in the direction of the crystallographic a axis. These chains are connected by hydrogen bonds between the amide H atoms and the O atoms of adjacent nicotin­amide ligands, to give a three‐dimensional structure.     

A Stable Crystalline Copper(I)–N2O Complex Stabilized as the Salt of a Weakly Coordinating Anion

Nitrous oxide is considered a poor ligand, and therefore only a handful of well‐defined metal–N₂O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag₂I₂][ An ]₂ ([ An ]^?=[Al(OC(CF₃)₃)₄]^?) in perfluorinated hexane leads to Cu^I[ An ], the first auxiliary ligand‐free Cu^I salt of the perfluorinated alkoxyaluminate anion. The compound is capable of forming a stable and crystalline complex with nitrous oxide, Cu(N₂O)[ An ], where the Cu?N₂O bond is by far the strongest among all other molecular metal–N₂O complexes known. Thorough characterization of the compounds together with the crystal structure of Cu(N₂O)[ An ] complex supported with DFT calculations are presented. These give insight into the bonding in the Cu⁺–N₂O system and confirm N‐end coordination of the ligand.     

Diamondoid framework solid with Sn(OCH3)2–tetrapyridylporphyrin linkers,CuI nodes and [CuICl2]− counter‐ions

We report on the synthesis of a new metal–organic framework (MOF) composed of Sn(OCH₃)₂–tetrakis(pyridin‐4‐yl)porphyrin linkers, Cu⁺ connecting nodes and [CuCl₂]⁻ counter‐ions, namely poly[[bis(methanolato‐κO)[μ₅‐5,10,15,20‐tetrakis(pyridin‐4‐yl)porphyrin‐κ⁸1κN⁵:1′κN¹⁰:1′′κN¹⁵:1′′′κN²⁰:2κ⁴N²¹,N²²,N²³,N²⁴]copper(I)tin(II)] dichloridocuprate(I)], [CuSn(C₄₀H₂₄N₈)(CH₃O)₂][CuCl₂]. Its crystal structure consists of a single‐framework coordination polymer of the organic ligand and the Cu^I ions. The latter are characterized by a tetrahedral coordination geometry [with CN (coordination number) = 4], linking to the pyridyl N‐atom sites of four different ligands and imparting to the positively charged polymeric assembly a diamondoid PtS‐type topology. Correspondingly, every porphyrin unit is coordinated to four different Cu^I connectors. The [CuCl₂]⁻ anions occupy the intra‐lattice voids, along with disordered molecules of the water crystallization solvent. The asymmetric unit of this structure consists of two halves of the porphyrin scaffold, located on centres of crystallographic inversion, and the Cu⁺ and [CuCl₂]⁻ ions. This report provides unique structural evidence for the formation of tetrapyridylporphyrin‐based three‐dimensional MOFs with a diamondoid architecture that have been observed earlier only on rare occasions.     

A three‐dimensional mixed‐valence CuII/CuI coordination polymer constructed from biphenyl‐3,4′,5‐tricarboxylate and 1,4‐bis(1H‐imidazol‐1‐yl)benzene ligands

Coordination polymers (CPs) built by coordination bonds between metal ions/clusters and multidentate organic ligands exhibit fascinating structural topologies and potential applications as functional solid materials. The title coordination polymer, poly[diaquabis(μ₄‐biphenyl‐3,4′,5‐tricarboxylato‐κ⁴O³:O^3′:O^4′:O⁵)tris[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)benzene‐κ²N³:N^3′]dicopper(II)dicopper(I)], [Cu^II₂Cu^I₂(C₁₅H₇O₆)₂(C₁₂H₁₀N₄)₃(H₂O)₂]_n, was crystallized from a mixture of biphenyl‐3,4′,5‐tricarboxylic acid (H₃bpt), 1,4‐bis(1H‐imidazol‐1‐yl)benzene (1,4‐bib) and copper(II) chloride in a water–CH₃CN mixture under solvothermal reaction conditions. The asymmetric unit consists of two crystallographically independent Cu atoms, one of which is Cu^II, while the other has been reduced to the Cu^I ion. The Cu^II centre is pentacoordinated by three O atoms from three bpt³⁻ ligands, one N atom from a 1,4‐bib ligand and one O atom from a coordinated water molecule, and the coordination geometry can be described as distorted trigonal bipyramidal. The Cu^I atom exhibits a T‐shaped geometry (CuN₂O) coordinated by one O atom from a bpt³⁻ ligand and two N atoms from two 1,4‐bib ligands. The Cu^II atoms are extended by bpt³⁻ and 1,4‐bib linkers to generate a two‐dimensional network, while the Cu^I atoms are linked by 1,4‐bib ligands, forming one‐dimensional chains along the [20] direction. In addition, the completely deprotonated μ₄‐η¹:η¹:η¹:η¹ bpt³⁻ ligands bridge one Cu^I and three Cu^II cations along the a (or [100]) direction to form a three‐dimensional framework with a (10³)₂(10)₂(4².6.10².12)₂(4².6.8².10)₂(8) topology via a 2,2,3,4,4‐connected net. An investigation of the magnetic properties indicated a very weak ferromagnetic behaviour.     

Reactions of 1,1′‐Diphosphaferrocene with CuCl and CuBr Resulting in Cu4P4X4Fe2 (X = Cl,Br) Complexes with Adamantane‐like Topologies

Cu₄P₄X₄Fe₂ (X = Cl, Br) cages are formed upon reactions of octaethyl‐1,1′‐diphosphaferrocene (odpf) with the respective Cu^I halide in CH₂Cl₂/CH₃CN solvent mixtures. These cages have adamantoid Cu₄X₄P₂ cores with two planar anelated CuP₂Fe rings as the flaps. Both complexes 1 and 2 feature tri‐ and tetracoordinate Cu^I ions and an additional acetonitrile solvent molecule in the crystal. In 1 , the solvent molecule is coordinated to one copper ion whereas it remains uncoordinated in 2 . The tricoordinate Cu^I ions show a slight pyramidalization at the metal atom and somewhat short contacts to the other tricoordinate Cu^I ion in 2 or the Cu₃‐triangle in 1 . NMR spectroscopy revealed easy decoordination of the acetonitrile ligand from 1 and a dynamic “windshield‐wiper”‐type process that interconverts the differently coordinated phospholide rings of each odpf ligand and the tri‐ and tetracoordinate Cu^I ions.     

The conformations of two copper(I) complexes of 1H‐benzimidazole‐2(3H)‐thione and thiosaccharinate

(Acetonitrile‐1κN)[μ‐1H‐benzimidazole‐2(3H)‐thione‐1:2κ²S:S][1H‐benzimidazole‐2(3H)‐thione‐2κS]bis(μ‐1,1‐dioxo‐1λ⁶,2‐benzothiazole‐3‐thiolato)‐1:2κ²S³:N;1:2κ²S³:S³‐dicopper(I)(Cu—Cu), [Cu₂(C₇H₄NO₂S₂)₂(C₇H₆N₂S)₂(CH₃CN)] or [Cu₂(tsac)₂(Sbim)₂(CH₃CN)] [tsac is thiosaccharinate and Sbim is 1H‐benzimidazole‐2(3H)‐thione], (I), is a new copper(I) compound that consists of a triply bridged dinuclear Cu—Cu unit. In the complex molecule, two tsac anions and one neutral Sbim ligand bind the metals. One anion bridges via the endocyclic N and exocyclic S atoms (μ‐S:N). The other anion and one of the mercaptobenzimidazole molecules bridge the metals through their exocyclic S atoms (μ‐S:S). The second Sbim ligand coordinates in a monodentate fashion (κS) to one Cu atom, while an acetonitrile molecule coordinates to the other Cu atom. The Cu^I—Cu^I distance [2.6286 (6) Å] can be considered a strong `cuprophilic' interaction. In the case of [μ‐1H‐benzimidazole‐2(3H)‐thione‐1:2κ²S:S]bis[1H‐benzimidazole‐2(3H)‐thione]‐1κS;2κS‐bis(μ‐1,1‐dioxo‐1λ⁶,2‐benzothiazole‐3‐thiolato)‐1:2κ²S³:N;1:2κ²S³:S³‐dicopper(I)(Cu—Cu), [Cu₂(C₇H₄NO₂S₂)₂(C₇H₆N₂S)₃] or [Cu₂(tsac)₂(Sbim)₃], (II), the acetonitrile molecule is substituted by an additional Sbim ligand, which binds one Cu atom via the exocylic S atom. In this case, the Cu^I—Cu^I distance is 2.6068 (11) Å.     

catena‐Poly[copper(II)‐μ‐l‐tyrosyl‐l‐leucinato]

In the title compound, [Cu(C₁₅H₂₀N₂O₄)]_n, the copper(II) coordination is square planar. The anionic l ‐tyrosyl‐l ‐leucinate ligand binds in an N,N′,O‐tridentate mode to one Cu^II cation on one side and in an O‐monodentate mode to a second Cu^II cation on the other side, thus defining –Cu—O—C—O—Cu′– chains which run along the a axis. These chains are held together by a strong hydrogen bond involving the hydroxy H atom.     

Poly[(μ‐pentafluorobenzoato‐κ2O:O′)(pentafluorobenzoato‐κO)(μ‐pyrazine‐κ2N:N′)copper(II)]: a coordination polymer linked into a three‐dimensional network by intermolecular C—H...F—C interactions

In the title compound, [Cu(C₆F₅COO)₂(C₄H₄N₂)]_n, (I), the asymmetric unit contains one Cu^II cation, two anionic pentafluorobenzoate ligands and one pyrazine ligand. Each Cu^II centre is five‐coordinated by three O atoms from three independent pentafluorobenzoate anions, as well as by two N atoms from two pyrazine ligands, giving rise to an approximately square‐pyramidal coordination geometry. Adjacent Cu^II cations are bridged by a pyrazine ligand and two pentafluorobenzoate anions to give a two‐dimensional layer. The layers are stacked to generate a three‐dimensional supramolecular architecture via strong intermolecular C—H...F—C interactions, as indicated by the F...H distance of 2.38 Å.