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1.
In the crystals of bis(pyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu2(C5H11O2Si)4(C5H5N)2], (I), the dinuclear CuII complexes have cage structures with Cu?Cu distances of 2.632 (1) and 2.635 (1) Å. In the crystals of bis(2‐­methylpyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu2(C5H11O2Si)4(C6H7N)2], (II), bis­(3‐methylpyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu2(C5H11O2Si)4(C6H7N)2], (III), and bis(quinoline‐N)­tetrakis(μ‐­trimethylsilylacetato‐O:O′)dicopper(II), [Cu2(C5H11O2Si)4(C9H7N)2], (IV), the centrosymmetric dinuclear CuII complexes have a cage structure with Cu?Cu distances of 2.664 (1), 2.638 (3) and 2.665 (1) Å, respectively. In the crystals of catena‐poly­[tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II)], [Cu2(C5H11O2Si)4]n, (V), the dinuclear CuII units of a cage structure are linked by the cyclic Cu—O bonds at the apical positions to form a linear chain by use of a glide translation.  相似文献   

2.
In the crystals of the five title compounds, tetrakis‐(μ‐3,3‐dimethylbutyrato‐O:O′)bis(ethanol‐O)dicopper(II)–ethanol (1/2), [Cu2(C6H11O2)4(C2H6O)2]·2C2H6O, (I), tetrakis(μ‐3,3‐dimethylbutyrato‐O:O′)bis(2‐methylpyridine‐N)di­copper(II), [Cu2(C6H11O2)4(C6H7N)2], (II), tetrakis‐(μ‐3,3‐dimethylbutyrato‐O:O′)bis(3‐methylpyridine‐N)di‐copper(II), [Cu2(C6H11O2)4(C6H7N)2], (III), tetrakis‐(μ‐3,3‐dimethylbutyrato‐O:O′)bis(4‐methylpyridine‐N)di‐copper(II), [Cu2(C6H11O2)4(C6H7N)2], (IV), and tetrakis‐(μ‐3,3‐dimethylbutyrato‐O:O′)bis(3,3‐dimethylbutyric acid‐O)dicopper(II), [Cu2(C6H11O2)4(C6H12O2)2], (V), the di­nuclear CuII complexes all have centrosymmetric cage structures and (IV) has two independent molecules. The Cu?Cu separations are: (I) 2.602 (3) Å, (II) 2.666 (3) Å, (III) 2.640 (2) Å, (IV) 2.638 (4) Å and (V) 2.599 (1) Å.  相似文献   

3.
The coordination polymers catena‐poly[[[(4,4′‐bi‐1,2,4‐triazole‐κN1)bis(thiocyanato‐κN)copper(II)]‐μ‐4,4′‐bi‐1,2,4‐triazole‐κ2N1:N1′] dihydrate], {[Cu(NCS)2(C4H4N6)2]·2H2O}n, (I), and poly[tetrakis(μ‐4,4′‐bi‐1,2,4‐triazole‐κ2N1:N1′)bis(μ‐thiocyanato‐κ2N:S)tetrakis(thiocyanato‐κN)tricadmium(II)], [Cd3(NCS)6(C4H4N6)4]n, (II), exhibit chain and two‐dimensional layer structures, respectively. The differentiation of the Lewis acidic nature of CuII and CdII has an influence on the coordination modes of the triazole and thiocyanate ligands, leading to topologically different polymeric motifs. In (I), copper ions are linked by bitriazole N:N′‐bridges into zigzag chains and the tetragonal–pyramidal CuN5 environment is composed of two thiocyanate N atoms and three triazole N atoms [basal Cu—N = 1.9530 (18)–2.0390 (14) Å and apical Cu—N = 2.2637 (15) Å]. The structure of (II) contains two types of crystallographically unique CdII atoms. One type lies on an inversion center in a distorted CdN6 octahedral environment, with bitriazole ligands in the equatorial plane and terminal isothiocyanate N atoms in the axial positions. The other type lies on a general position and forms centrosymmetric binuclear [Cd2(μ‐NCS‐κ2N:S)2(NCS)2] units (tetragonal–pyramidal CdN4S coordination). N:N′‐Bridging bitriazole ligands link the Cd centers into a flat (4,4)‐network.  相似文献   

4.
One μ‐alkoxo‐μ‐carboxylato bridged dinuclear copper(II) complex, [Cu2(L1)(μ‐C6H5CO2)] ( 1 )(H3L1 = 1,3‐bis(salicylideneamino)‐2‐propanol)), and two μ‐alkoxo‐μ‐dicarboxylato doubly‐bridged tetranuclear copper(II) complexes, [Cu4(L1)2(μ‐C8H10O4)(DMF)2]·H2O ( 2 ) and [Cu4(L2)2(μ‐C5H6O4]·2H2O·2CH3CN ( 3 ) (H3L2 = 1,3‐bis(5‐bromo‐salicylideneamino)‐2‐propanol)) have been prepared and characterized. The single crystal X‐ray analysis shows that the structure of complex 1 is dimeric with two adjacent copper(II) atoms bridged by μ‐alkoxo‐μ‐carboxylato ligands where the Cu···Cu distances and Cu‐O(alkoxo)‐Cu angles are 3.5 11 Å and 132.8°, respectively. Complexes 2 and 3 consist of a μ‐alkoxo‐μ‐dicarboxylato doubly‐bridged tetranuclear Cu(II) complex with mean Cu‐Cu distances and Cu‐O‐Cu angles of 3.092 Å and 104.2° for 2 and 3.486 Å and 129.9° for 3 , respectively. Magnetic measurements reveal that 1 is strong antiferromagnetically coupled with 2J =‐210 cm?1 while 2 and 3 exhibit ferromagnetic coupling with 2J = 126 cm?1 and 82 cm?1 (averaged), respectively. The 2J values of 1–3 are correlated to dihedral angles and the Cu‐O‐Cu angles. Dependence of the pH at 25 °C on the reaction rate of oxidation of 3,5‐di‐tert‐butylcatechol (3,5‐DTBC) to the corresponding quinone (3,5‐DTBQ) catalyzed by 1–3 was studied. Complexes 1–3 exhibit catecholase‐like active at above pH 8 and 25 °C for oxidation of 3,5‐di‐tert‐butylcatechol.  相似文献   

5.
(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)(CuCu), [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 CuI—CuI 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)(CuCu), [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 CuI—CuI distance is 2.6068 (11) Å.  相似文献   

6.
As an important class of heterocyclic compounds, 1,3,4‐thiadiazoles have a broad range of potential applications in medicine, agriculture and materials chemistry, and were found to be excellent precursors for the crystal engineering of organometallic materials. The coordinating behaviour of allyl derivatives of 1,3,4‐thiadiazoles with respect to transition metal ions has been little studied. Five new crystalline copper(I) π‐complexes have been obtained by means of an alternating current electrochemical technique and have been characterized by single‐crystal X‐ray diffraction and IR spectroscopy. The compounds are bis[μ‐5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine]bis[nitratocopper(I)], [Cu2(NO3)2(C6H9N3S)2], (1), bis[μ‐5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine]bis[(tetrafluoroborato)copper(I)], [Cu2(BF4)2(C6H9N3S)2], (2), μ‐aqua‐bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}bis[nitratocopper(I)], [Cu2(NO3)2(C5H7N3S2)2(H2O)], (3), μ‐aqua‐(hexafluorosilicato)bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}dicopper(I)–acetonitrile–water (2/1/4), [Cu2(SiF6)(C5H7N3S2)2(H2O)]·0.5CH3CN·2H2O, (4), and μ‐benzenesulfonato‐bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}dicopper(I) benzenesulfonate–methanol–water (1/1/1), [Cu2(C6H5O3S)(C5H7N3S2)2](C6H5O3S)·CH3OH·H2O, (5). The structure of the ligand 5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine (Mepeta ), C6H9N3S, was also structurally characterized. Both Mepeta and 5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine (Pesta ) (denoted L ) reveal a strong tendency to form dimeric {Cu2L 2}2+ fragments, being attached to the metal atom in a chelating–bridging mode via two thiadiazole N atoms and an allylic C=C bond. Flexibility of the {Cu2(Pesta )2}2+ unit allows the CuI atom site to be split into two positions with different metal‐coordination environments, thus enabling the competitive participation of different molecules in bonding to the metal centre. The Pesta ligand in (4) allows the CuI atom to vary between water O‐atom and hexafluorosilicate F‐atom coordination, resulting in the rare case of a direct CuI…FSiF52− interaction. Extensive three‐dimensional hydrogen‐bonding patterns are formed in the reported crystal structures. Complex (5) should be considered as the first known example of a CuI(C6H5SO3) coordination compound. To determine the hydrogen‐bond interactions in the structures of (1) and (2), a Hirshfeld surface analysis has been performed.  相似文献   

7.
Reaction of CuI with 1 or 2 equivalent(s) N,N′‐Bis(diphenylphosphino)‐2,6‐diaminopyridine (BDDP) gives two different complexes, [Cu(I)μ‐(BDDP‐κP,Npy)]2 ( 1 ) and [Cu(BDDP‐κP,Npy)2]I ( 2 ), in high yields. The determination of the molecular structure show that both CuI atoms are tetrahedrally coordinated, rather than a square‐planar geometry reported for Cr0, NiII‐BDDP complexes before, which contains a planar tridentate chelate ring system. The introduction of AuCl(tht) (tht = tetrahydrothiophene) into [Cu(BDDP‐κP,Npy)2]I leads unexpectedly to the formation of a digold complex 2,6‐[(ClAuPh2P)HN]2C5H3N and dimeric [Cu(I)μ‐(BDDP‐κP,Npy)]2.  相似文献   

8.
5‐[(Imidazol‐1‐yl)methyl]benzene‐1,3‐dicarboxylic acid (H2L) was synthesized and the dimethylformamide‐ and dimethylacetamide‐solvated structures of its adducts with CuII, namely catena‐poly[[copper(II)‐bis[μ‐3‐carboxy‐5‐[(imidazol‐1‐yl)methyl]benzoato]] dimethylformamide disolvate], {[Cu(C12H9N2O4)2]·2C3H7NO}n, (I), and catena‐poly[[copper(II)‐bis[μ‐3‐carboxy‐5‐[(imidazol‐1‐yl)methyl]benzoato]] dimethylacetamide disolvate], {[Cu(C12H9N2O4)2]·2C4H9NO}n, (II), the formation of which are associated with mono‐deprotonation of H2L. The two structures are isomorphous and isometric. They consist of one‐dimensional coordination polymers of the organic ligand with CuII in a 2:1 ratio, [Cu(μ‐HL)2]n, crystallizing as the dimethylformamide (DMF) or dimethylacetamide (DMA) disolvates. The CuII cations are characterized by a coordination number of six, being located on centres of crystallographic inversion. In the polymeric chains, each CuII cation is linked to four neighbouring HL ligands, and the organic ligand is coordinated via Cu—O and Cu—N bonds to two CuII cations. In the corresponding crystal structures of (I) and (II), the coordination chains, aligned parallel to the c axis, are further interlinked by strong hydrogen bonds between the noncoordinated carboxy groups in one array and the coordinated carboxylate groups of neighbouring chains. Molecules of DMF and DMA (disordered) are accommodated at the interface between adjacent polymeric assemblies. This report provides the first structural evidence for the formation of coordination polymers with H2Lvia multiple metal–ligand bonds through both carboxylate and imidazole groups.  相似文献   

9.
The title racemic complex, bis[μ‐N‐(2‐oxidobenzylidene)‐d ,l ‐glutamato(2−)]bis[(isoquinoline)copper(II)] ethanol disolvate, [Cu2(C12H11NO5)2(C9H7N)2]·2C2H6O, adopts a square‐pyramidal CuII coordination mode with a tridentate N‐salicylideneglutamato Schiff base dianion and an isoquinoline ligand bound in the basal plane. The apex of the pyramid is occupied by a phenolic O atom from the adjacent chelate molecule at an apical distance of 2.487 (3) Å, building a dimer located on the crystallographic inversion center. The Cu...Cu spacing within the dimers is 3.3264 (12) Å. The ethanol solvent molecules are hydrogen bonded to the dimeric complex molecules, forming infinite chains in the a direction. The biological activity of the title complex has been studied.  相似文献   

10.
The title compound, [Cu(C9H7N2O)2]·2CH3OH, contains a crystallographically centrosymmetric near‐regular square planar CuII centre with trans‐disposed chelating ligands. The complex mol­ecules associate into a one‐dimensional polymeric chain via hydrogen bonding to the solvent mol­ecules.  相似文献   

11.
In the title compound, [Cu(CN)(C4H5N3)]n or [Cu(μ‐CN)(μ‐PyzNH2)]n (PyzNH2 is 2‐aminopyrazine), the CuI center is tetrahedrally coordinated by two cyanide and two PyzNH2 ligands. The CuI–cyano links give rise to [Cu–CN] chains running along the c axis, which are bridged by bidentate PyzNH2 ligands. The three‐dimensional framework can be described as being formed by two interpenetrated three‐dimensional honeycomb‐like networks, both made of 26‐membered rings of composition [Cu6(μ‐CN)2(μ‐PyzNH2)4].  相似文献   

12.
The present structure determination of di‐μ‐hydroxo‐bis{[N,N′‐bis­(dipiperidino­methyl­ene)­propane‐1,3‐di­amine‐κ2N,N′]copper(II)} bis­(hexa­fluoro­phosphate), [Cu2(OH)2(C25H46N6)2](PF6)2, is the first to crystallographically characterize a Cu2(μ‐OH)2 complex with a bidentate guanidine ligand. The cation lies on a crystallographic inversion centre and shows planar fourfold coordination of the copper centres. The Cu2(μ‐OH)2 species can be distinguished from Cu2(μ‐O)2 by the Cu—O bond lengths. The packing is determined by strong intermolecular anion–cation hydrogen bonds.  相似文献   

13.
The title compound, [Cu(C7H3O6S)2(C10H9N3)2][CuI(C10H9N3)2]2·2H2O, consists of anionic CuII moieties, cationic CuI species and uncoordinated water mol­ecules. The anionic dimeric unit consists of one crystallographically independent fully deprotonated 5‐sulfosalicylate (2‐oxido‐5‐sulfonatobenzoate) anion, a di‐2‐pyridylamine group and a CuII atom. Each CuII atom is five‐coordinate within a square‐pyramidal geometry. The anion lies on a special position of site symmetry. In the cationic monomer, the CuI atom adopts tetra­hedral geometry. The cations and anions are connected by O—H·O and N—H·O hydrogen bonds.  相似文献   

14.
The title centrosymmetric CuII binuclear complex, bis(μ‐N,N‐diethyl‐1,1‐di­seleno­carbamato‐Se,Se′:Se)­bis­[(N,N‐diethyl‐1,1‐di­seleno­carbamato‐Se,Se′)copper(II)], [Cu(Se2CNEt2)2]2 or [Cu2(C5H10NSe2)4], is built from two symmetry‐related [Cu{Se2CN(Et)2}2] units by pairs of Cu—Se bonds. The coordination geometry at the unique Cu atom is distorted square pyramidal, with Cu—Se distances in the range 2.4091 (11)—2.9095 (10) Å.  相似文献   

15.
A new polymeric copper complex, viz.catena‐poly[[[μ‐N,N′‐bis(3‐amino­propyl)oxa­mid­ato‐κ6N,N′,O:N′′,N′′′,O′]­dicopper(II)]‐di‐μ‐dicyan­amido‐1:1′κ2N1:N5;2:2′κ2N1:N5], [Cu2(C8H16N4O2)(C2N3)2]n or [Cu(oxpn)0.5{N(CN)2}]n [where H2oxpn is N,N′‐bis(3‐amino­propyl)­ox­amide], has been ­synthesized by the reaction of Cu(oxpn), [Cu(ClO4)2]·6H2O and NaN3. In the crystal structure, the Cu atom is five‐coordinate and has a square‐pyrimidal (SP) configuration. In the polymer, dicyan­amide (dca) groups link CuII cations in a μ‐1,5‐bridging mode, generating novel ladders in which each step is composed of dimeric [Cu2(oxpn)]2+ cations. Abundant hydrogen bonds connect the polymer ladders into a two‐dimensional network structure.  相似文献   

16.
Multifunctional 2‐amino‐5‐sulfobenzoic acid (H2afsb) can exhibit a variety of roles during the construction of supramolecular coordination polymers. The pendant carboxylic acid, sulfonic acid and amino groups could not only play a role in directing bonding but could also have the potential to act as hydrogen‐bond donors and acceptors, resulting in extended high‐dimensional supramolecular networks. Two new CuII coordination compounds, namely catena‐poly[[[diaquacopper(II)]‐μ‐1,6‐bis(1H‐1,2,4‐triazol‐1‐yl)hexane‐κ2N4:N4′] bis(3‐amino‐4‐carboxybenzenesulfonate) dihydrate], {[Cu(C10H16N6)2(H2O)2](C7H6NO5S)2·2H2O}n or {[Cu(bth)2(H2O)2](Hafsb)2·2H2O}n, (1), and bis(μ‐2‐amino‐5‐sulfonatobenzoato‐κ2O1:O1′)bis{μ‐1,2‐bis[(1H‐imidazol‐1‐yl)methyl]benzene‐κ2N3:N3′}bis[aquacopper(II)] trihydrate, [Cu2(C7H5NO5S)2(C14H14N4)2(H2O)2]·3H2O or [Cu2(afsb)2(obix)2(H2O)2]·3H2O, (2), have been obtained through the assembly between H2afsb and the CuII ion in the presence of the flexible N‐donor ligands 1,6‐bis(1H‐1,2,4‐triazol‐1‐yl)hexane (bth) and 1,2‐bis[(1H‐1,2,4‐triazol‐1‐yl)methyl]benzene (obix), respectively. Compound (1) consists of a cationic coordination polymeric chain and 3‐amino‐4‐carboxybenzenesulfonate (Hafsb) anions. Compound (2) exhibits an asymmetric dinuclear structure. There are hydrogen‐bonded networks within the lattices of (1) and (2). Interestingly, both (1) and (2) exhibit reversible dehydration–rehydration behaviour.  相似文献   

17.
The title compound, catena‐poly­[[μ‐cyano‐1:2κ2C:N‐dicyano‐1κ2C‐bis(N,N‐di­methyl­ethyl­enedi­amine‐2κ2N,N′)­pallad­ium(II)­copper(II)]‐μ‐cyano‐1:2′κ2C:N], [CuPd(CN)4(C4H12N2)2]n, consists of infinite quasi‐linear chains with all metal positions on centers of symmetry. The paramagnetic [Cu(dmen)2]2+ cations are linked by diamagnetic [Pd(CN)4]2− anions via bridging cyano groups, which occupy trans positions in both cation and anion, giving rise to 2,2‐TT‐type chains. The coordination polyhedron of the paramagnetic Cu atom is an octahedron exhibiting typical elongation due to the Jahn–Teller effect, with two longer Cu—N([triple‐bond]C) bonds in the axial positions [2.5528 (13) Å] and four shorter Cu—Ndmen bonds (dmen is N,N‐dimethylethylenediamine) in the equatorial plane [1.9926 (11) and 2.1149 (12) Å]. The Cu—N[triple‐bond]C angle is 138.03 (12)°. Neighboring chains form weak N—H⋯NC hydrogen bonds.  相似文献   

18.
The title compound, [Cu2(OH)2(C14H17N3)2]Cl2·6H2O, is a crystallographically centrosymmetric dimer of square‐pyramidal CuII 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.  相似文献   

19.
In the crystal structure of the synthetically prepared title compound, [Cu(C14H12N2)2](C4HO4)·0.5H2O or [Cu(dmphen)2](HSq)·0.5H2O (dmphen is 2,9‐dimethyl‐1,10‐phenanthroline or neocuproine and HSq is hydrogen squarate), the CuI centre has distorted tetra­hedral coordination geometry comprised of four N atoms from two bidentate dmphen ligands. The squarate monoanions form a ten‐membered dimer, graph set R22(10), linked by two strong inter­molecular O—H⋯O hydrogen bonds. These squarate dimers are linked into chains that propagate along the [100] direction. An extensive three‐dimensional network of C—H⋯O hydrogen bonds and π–π inter­actions is responsible for stabilization of the crystal structure.  相似文献   

20.
In the title compound, [Cu2(C19H24N2O4)2(H2O)2]·2H2O, the asymmetric unit consists of one half of the bis{μ‐6,6′‐dimethoxy‐2,2′‐[propane‐1,2‐diylbis(iminomethylene)]diphenolato}bis[aquacopper(II)] complex and two water molecules. Two CuII centres are bridged through a pair of phenolate groups, resulting in a complex with a centrosymmetric structure, with the centre of inversion at the middle of the Cu2O2 plane. The Cu atoms are in a slightly distorted square‐pyramidal coordination environment (τ = 0.07). The average equatorial Cu—O bond length and the axial Cu—O bond length are 1.928 (3) and 2.486 (3) Å, respectively. The Cu—O(water) bond length is 2.865 (4) Å, so the compound could be described as having a weakly coordinating water molecule at each CuII ion and two solvent water molecules per dimetallic unit. The Cu...Cu distance and Cu—O—Cu angle are 3.0901 (10) Å and 87.56 (10)°, respectively. The molecules are linked into a sheet by O—H...O and C—H...O hydrogen bonds parallel to the [001] plane.  相似文献   

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