Transformation of a C-methylcalix[4]resorcinarene-based host-guest complex from a wave-like to a novel triangular brick-wall architecture

A novel 2D triangular brick-wall framework based on CMCR and bpe with included ruthenocene guest molecules is formed with time by conversion of a 1D wave-like polymer structure with an accompanying bowl-to-boat conformational change of the CMCR molecules.     

Supramolecular solids as a medium for single-crystal-to-single-crystal E/Z photoisomerization: kinetic study of the photoreactions of two Zn-coordinated tiglic acid molecules

[Zn(TA)2(H2O)2] (H-TA=tiglic acid) has been embedded in a framework composed of CECR (CECR=C-ethylcalix[4]resorcinarene) molecules to examine its E-->Z photoisomerization in a periodic framework. The photoisomerization of tiglic acid in CECR-[Zn(TA)2(H2O)2]4 H2O proceeds without the [2+2]-dimerization reaction that often occurs in crystals of uncomplexed analogues, and without breakdown of the crystal lattice that frequently occurs in neat crystals. The two Zn-coordinated TA molecules are located in different size cavities. The rate constants of the isomerization reaction are strongly affected by the size of the reaction cavity. Analysis of the temperature dependence of the reaction rates and the occupancies in the final photostationary state shows that the activation energies and the standard enthalpies of activation are dependent on the difference between the reaction cavities. This is the first quantitative diffraction study of solid-state E/Z isomerization of a metal-coordinated ligand in a periodic host environment.     

Interdigitation, interpenetration and intercalation in layered cuprous tricyanomethanide derivatives

Reaction of Cu(I), tricyanomethanide (tcm , C(CN)3-) and L = either hexamethylenetetramine (hmt), 4,4'-bipyridine (bipy) or 1,2-bis(4-pyridyl)ethene (bpe) gives crystals of [Cu(tcm)(hmt)] (1), [Cu(tcm)(bipy)] (2) and [Cu(tcm)(bpe)] x 0.25 bpe x 0.5 MeCN (3), respectively. Crystal structure analysis shows 1-3 all contain closely related puckered (4,4) sheets composed of tetrahedral Cu(I) ions bridged by 2-connecting tcm- and L. The crystal packing, however, varies markedly with L. In 1 the sheets interdigitate in pairs. In 2 the sheets participate in parallel interpenetration in pairs. In 3 guest bpe and MeCN molecules are intercalated in channels formed by the stacking of the sheets.     

Asymmetrical polar modification of a bivanadium-capped Keggin POM by multiple Cu-N coordination polymeric chains

An unprecedented asymmetrically modified bivanadium-capped Keggin polyoxometalate (POM), {AsMo12O40(VO)[VO(H2O)]}.[Cu(4,4'-bipy)]5.H2O (1) (bipy = bipyridine), has been hydrothermally synthesized and structurally characterized by a routine technique. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a unique (3,4,6)-connected 3D framework with a (6(2).8(1))2(8(3))2(6(4).8(2))2(6(1).8(14)) topology, constructed from {AsMo12O40(VO)[VO(H2O)]}5- polyoxoanions modified by six {Cu(bipy)}n coordination polymeric chains. The asymmetrical polar coordination mode has never been found in the POM chemistry hitherto. It is also the first example of the bivanadium-capped POM as an anionic template to construct a 3D framework with the highest connection number of bicapped POMs. Additionally, by just changing the length of the organic ligand, a new compound {[AsMo12O40(VO)2][Cu(bpe)]2}.[Cu(bpe)].[H2bpe].H2O (2) (bpe = bis(4-pyridyl)ethylene), has been obtained, in which the {AsMo12O40(VO)2} sections are modified by double monotrack {Cu(bpe)}n coordination polymeric chains to form a "rail-like" 1D structure.     

Various forms of linear dipyridyls in discrete rectangles, dinuclear rods, and one-dimensional networks containing (eta5-pentamethylcyclopentadienyl)rhodium(III)

[Cp*Rh(eta1-NO3)(eta2-NO3)] (1) reacted with pyrazine (pyz) to give a dinuclear complex [Cp*Rh(eta1-NO3)(mu-pyz)(0.5)]2.CH2Cl2(3.CH2Cl2). Tetranuclear rectangles of the type [Cp*Rh(eta1,mu-X)(mu-L)(0.5)]4(OTf)4(4a: X = N3, L = bpy; 4b: X = N3, L = bpe; 4c: X = NCO, L = bpy) were prepared from [Cp*Rh(H2O)3](OTf)2 (2), a pseudo-halide (Me3SiN3 or Me3SiNCO), and a linear dipyridyl [4,4'-bipyridine (bpy) or trans-1,2-bis(4-pyridyl)ethylene (bpe)] by self-assembly through one-pot synthesis at room temperature. Treating complex with NH4SCN and dipyridyl led to the formation of dinuclear rods, [Cp*Rh(eta1-SCN)3]2(LH2) (5a: L = bpy; 5b: L = bpe), in which two Cp*Rh(eta1-SCN)3 units are connected by the diprotonated dipyridyl (LH2(2+)) through N(+)-H...N hydrogen bonds. Reactions of complex 2 with 1-(trimethylsilyl)imidazole (TMSIm) and dipyridyl (bpy or bpe) also produced another family of dinuclear rods [Cp*Rh(ImH)3]2.L (6a: L = bpy; 6b: L = bpe). Treating 1 and 2 with TMSIm and NH4SCN (in the absence of dipyridyl) generated a 1-D chain [Cp*Rh(ImH)3](NO3)2 (7) and a 1-D helix [Cp*Rh(eta1-SCN)2(eta1-SHCN)].H2O (8.H2O), respectively. The structures of complexes 3.CH2Cl2, 4a.H2O, 4c.2H2O, 5b, 6a, 7 and 8.H2O were determined by X-ray diffraction.     

Homochiral frameworks derived from magnesium, zinc and copper salts of l-tartaric acid

Five metal-organic frameworks derived from l-tartarate (l-tart=C₄H₄O₆) and the divalent metal ions magnesium, zinc or copper have been prepared and structurally characterized. The frameworks were prepared from the reaction of potassium l-tartrate [KC₄H₅O₆] with the appropriate metal salt in water solutions. The magnesium compound [Mg(l-tart)(H₂O)⊃1.5H₂O], 1, crystallizes as a two-dimensional 6³ sheet structure. The addition of the divergent linker molecules 4,4′-bipyridine (bipy) or trans-1,2-bispyridylethylene (bpe) to systems involving Zn²⁺ and Cu²⁺ results in the formation of the homochiral three-dimensional structures [Zn₂(l-tart)2(biyp)(H₂O)⊃5.25H₂O], 2, [Cu(l-tart)(bipy)⊃2.33H₂O], 3, and [Cu(l-tart)(bpe)⊃8H₂O], 5. Removal of solvent water molecules from 3 resulted in [Cu(l-tart)(bipy)⊃0.2H₂O], 4. Similar experiments on 2 and 5 resulted in breakdown of the frameworks, illustrating the dependence of the stability of these structures on the guest water molecules. This study reports the structures of two new topological types of binodal nets.     

Synthesis and guest exchange reactions of inclusion compounds of cucurbit[8]uril with nickel(II) and copper(II) complexes

Inclusion compounds of the macrocyclic cavitand cucurbit[8]uril (CB[8]) with the nickel(II) complex, {trans-[Ni(en)₂(H₂O)₂]@CB[8]}Cl₂ · 23.5H₂O, the copper(II) complex, {2[Cu(dien)(bipy)(H₂O)]@CB[8]}(ClO₄)₄ · 11H₂O, and the organic molecules, 2(pyCN)@CB[8]} · 16H₂O and {2(bpe)@CB[8]} · 17H₂O, where bipy is 4,4′-bipyridyl, pyCN is 4-cyanopyridine, and bpe is trans-1,2-bis(4-pyridyl)ethylene, were synthesized. The inclusion compounds with organic molecules were synthesized starting from inclusion compounds of cucurbit[8]uril with cyclam and ethylenediamine complexes of copper(II) and nickel(II) by the guest exchange method, which is based on the replacement of one guest with another in the cavity of the cavitand The resulting compounds were characterized by X-ray diffraction, ESR, ¹H NMR, IR, and electronic absorption spectroscopy, and electrospray mass spectrometry. Photochemically induced [2+2]-cycloaddition of two 1,2-bis(4-pyridyl)ethylene molecules included in cucurbit[8]uril was studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 25–34, January, 2006.     

Syntheses, structures, photoluminescence and theoretical studies of xanthone in crystalline resorcinarene-based inclusion complexes

Two new crystalline resorcinarene-based xanthone inclusion complexes, CECRxanthoneMeOH (1), and HECR2 xanthone6 MeOH (2) (CECR = C-ethylcalix[4]resorcinarene, HECR = hexaethylresorcin[6]arene) have been prepared to study the relation between photophysical properties and solid-state structure. Compared with the neat crystals, the xanthone phosphorescence is severely quenched in both solids, but the lifetime is an order of magnitude larger in 2, in which xanthone occurs as a dimer, than in 1, in which it occurs as a monomer. The electronic transitions involved in the photoluminescent process, and the relation between the energy levels of host and guest and emission quenching of the guest in the supramolecular solid have been investigated by means of time-dependent density functional theory (TDDFT) calculations.     

Single-crystal-to-single-crystal E-->Z and Z-->E isomerizations of 3-chloroacrylic acid within the nanocavities of a supramolecular framework

Single-crystal-to-single-crystal E-->Z and Z-->E photo-isomerizations of 3-chloroacrylic acid (HClA) take place with full retention of the crystal lattice in the framework cavities of the supramolecular crystals CECR.HClA.2MeOH.1.5H(2)O (CECR = C-ethylcalix[4] resorcinarene); their progress has been monitored as the reaction proceeds.     

Layer and Cavity Structures of Manganese(II) Diphenate Coordination Polymers

Two novel metal‐organic coordination polymers, [Mn₂(dpa)₂(4,4′‐bipy)₂(H₂O)₂]_n ( 1 ) and [Mn(Hdpa)₂(bpe)(H₂O)₂]_n ( 2 ) (H₂dpa = diphenic acid, 4,4′‐bipy = 4,4′‐dipyridine, bpe = 1,2‐bis(4‐pyridyl)ethene), have been hydrothermally synthesized. Single crystal X‐ray diffraction analyses reveal the two‐dimensional and three‐dimensional structures for complexes 1 and 2 , respectively. In 1 , the dpa ligands link metal ions with different modes into one‐dimensional chains, and the 4,4′‐bipy terminally coordinate to the metal ions extending the chains into a layer. Whereas in 2 , the flexible bpe ligands link the structure motifs into chains, and the hydrogen bonding interactions between the chains lead to the formation of cavity structure.     

Two- and three-fold interpenetrated metal-organic frameworks from one-pot crystallization

Two different three-dimensional interpenetrating metal-organic frameworks, {[Co(bpe)(muco)](DMF)(H 2O)} n ( 1) and {[Co(bpe)(muco)(H 2O) 2].4(H 2O)} n ( 2) [bpe = 4,4'-bipyridyl ethylene, H 2-muco = trans,trans-muconic acid, DMF = dimethyl formamide] have been co-crystallized in one-pot reaction. This work offers some insights into the intricacy of designing coordination polymers with variable interpenetration, showing new modes of entanglements. Single crystal X-ray diffraction analyses reveal that the compound 1 has a highly distorted cubic (alpha-Po) net with 2-fold interpenetrated structures while compound 2 displays a 3-fold interpenetrating net-work with an unprecedented 6 (6) topology which is different from other well-known 4-connected nets such as diamond or hexagonal diamond. Despite varied interpenetrations, both compounds retain open channels, filled with aggregated guest solvent molecules. As far as the ratios of Co/muco/bpe are concerned, these two complexes can be considered as supramolecular isomers. Formation of a particular isomer in major quantity can be obtained by varying the countercation of the muconate salt in different solvents, by layering, and by changing the order of the components.     

Structural Characterization of l-proline and Morpholine Appended Chiral Calix[4]resorcinarene Molecules

Calix[4]resorcinarenes serve as host molecules for small guest molecules. Recently calixarenes have been appended to chiral molecules in an attempt to promote chiral recognition. To take advantage of both cavity host and chiral substituent properties the position of the chiral moiety is important. We report the synthesis and structural characterization of two calix[4]resorcinarene based molecules that have helical chirality in the solid state. The calix[4]resorcinarene 1 has chiral l-proline ethyl ester substituents positioned perpendicular to the cavity whereas the calix[4]resorcinarene 2 has morpholines positioned parallel to the cavity which extend the depth of the cavity. Compound 1 is one of the first compounds to show the position of chiral centers with respect to the calixarene cavity. 1H and 13C NMR spectroscopy indicate that the helical chirality of 2 is retained at low temperature in nonpolar solvents.     

Transformation from a 2D stacked layer to 3D interpenetrated framework by changing the spacer functionality: synthesis, structure, adsorption, and magnetic properties

Two novel coordination polymers of Cu(II), viz. [Cu(bipy)(1,4-napdc)(H2O)2]n and {[Cu(bpe)1.5(1,4-napdc)](H2O)}n (bipy=4,4'-bipyridine; bpe=1,2-bis(4-pyridyl)ethane; 1,4-napdc2-=1,4-naphthalenedicarboxylate), have been synthesized and structurally characterized by changing only the pillar motifs. Both the compounds crystallize by slow evaporation from the ammoniacal solution of the as-synthesized solid. Framework 1 crystallizes in monoclinic crystal system, space group P2/n (No. 13), with a=11.028(19) A, b=11.16(3) A, c=7.678(13) A, beta=103.30(5) degrees, and Z=2. Framework 2 crystallizes in triclinic system, space group, P (No. 2), a=10.613(4) A, b=10.828(10) A, c=13.333(9) A, alpha=85.25(9) degrees, beta=82.59(6) degrees, gamma=60.37(5) degrees, and Z=2. The structure determination reveals that has a 2D network based on rectangular grids, where each Cu(II) is in 4+2 coordination mode. The 2D networks stacked in a staggered manner through the pi-pi interaction to form a 3D supramolecular network. In the case of, a {Cu(bpe)1.5}n ladder connected by 1,4-napdc2- results a 2D cuboidal bilayer network and each bilayer network is interlocked by two adjacent identical network (upper and lower) forming 3-fold interpenetrated 3D framework with small channel along the c-axis, which accommodates two water molecules. The TGA and XRPD measurements reveal that both the frameworks are stable after dehydration. Adsorption measurements (N2, CO2, and different solvents, like H2O, MeOH, etc.) were carried out for both frameworks. Framework shows type-II sorption profile with N2 in contrast to H2O and MeOH, which are chemisorbed in the framework. In case of, only H2O molecules can diffuse into the micropore, whereas N2, CO2, and MeOH cannot be adsorbed, as corroborated by the smaller channel aperture. The low-temperature (300-2 K) magnetic measurement of and reveals that both are weakly antiferromagnetically coupled (J=-1.85 cm-1, g=2.02; J=-0.153 cm-1, g=2.07), which is correlated by the magnetic pathway to the corresponding structure.     

Structural analyses and magnetic properties of 3D coordination polymeric networks of nickel(II) maleate and manganese(II) adipate with the flexible 1,2-bis(4-pyridyl)ethane ligand

Two novel inorganic-organic hybrid 3D extended networks of Ni(II) and Mn(II) having molecular formulas [(maleate)(2)Ni(3)(bpe)(4)(H(2)O)(4)](NO(3))(2).H(2)O (1) and [(adipate)Mn(bpe)] (2) (bpe = 1, 2-bis(4-pyridyl)ethane), respectively, have been synthesized and characterized by single-crystal X-ray diffraction studies and low-temperature (300-2 K) magnetic measurements. Compound 1 crystallizes in the monoclinic system, space group C2/c (No. 15), with chemical formula C(56)H(62)N(10)Ni(3)O(19), a = 30.955(4) A, b = 12.705(3) A, c = 17.058(5) A, beta = 117.26(2) degrees, and Z = 4. Compound 2 crystallizes in the triclinic system, space group Ponemacr; (No. 2), with chemical formula C(18)H(20)MnN(2)O(4), a = 8.492(2) A, b = 9.444(2) A, c = 11.533(3) A, alpha = 97.19(1) degrees, beta = 94.64(1) degrees, gamma = 105.02(1) degrees, and Z = 2. The structure determination reveals for both a 3D network. Compound 1 contains two crystallographically independent Ni(II) ions in different octahedral environments. Ni(1) lies on an inversion center, and its coordination environment comprises two chelating maleate anions and two bpe nitrogen donors, while the Ni(2) ion is surrounded by meridionally disposed three bpe N atoms, two water molecules, and one oxygen donor from the dicarboxylate anion. Of the three crystallographic independent bpe ligand, one presents an anti and the others a gauche conformation. The corresponding N-to-N distances are 9.344, 6.543, and 6.187 A. Variable-temperature magnetic susceptibility measurement of the complex reveals the existence of a dominant ferromagnetic interaction within the molecule. Compound 2 is composed of Mn(2) dimer units linked by adipate anions to form corrugated 2D sheets which, on interconnection through bpe (anti conformation, N-to-N distance of 9.391 A), produces an interpenetrated 3D alpha-polonium-related type net. Complex 2 reveals to be antiferromagnetic fitting data using a dimeric Mn(II) model that considers negligible magnetic transmission through the carbon skeleton of adipate and the bpe pathway.     

Tetraphosphinite resorcinarene complexes: silver(I) capsule complexes

Resorcinarene tetraphosphinite ligands, P4, react with silver(I) trifluoroacetate or silver(I) triflate, AgX, to give the corresponding [Ag4X4(P4)] complexes. The resorcinarene skeleton in these complexes adopts a boat conformation with the silver(I) phosphinite units on the horizontal, rather than the upright, arene units of the resorcinarene. The [Ag4X4(P4)] complexes react with free P4 ligand to yield the [Ag2X2(P4)] or [AgX(P4)] complexes, which are characterized in solution by NMR spectroscopy to have a conformation opposite to that of the [Ag4X4(P4)] complexes; the silver(I) phosphinite groups are on the upright arene rings of the resorcinarene "boat" instead of the horizontal arene units. There is an easy equilibrium between these complexes. When X = triflate, the [Ag4X4(P4)] complexes disproportionate and add aqua ligands during slow crystallization to give "capsule complexes", which are characterized crystallographically as [Ag10(O3SCF3)10(OH2)6(P4)2], [Ag10(O3SCF3)6(OH2)8(P4)2][O3SCF3]4, or [Ag13(O3SCF3)13(OH2)7(P4)2] depending on the resorcinarene tetraphosphinite ligand P4 used. These unusual capsule complexes are formed by the tail-to-tail self-assembly of pairs of [Ag4(P4)]4+ units linked by additional silver ions that bind to the phenyl substituents of one resorcinarene through {Ag(eta2-C6H5)}+ binding and to the bridging triflate ligands, aqua ligands, or both of the other resorcinarene unit.     

Novel hexagonal {V=O}6-containing sandwich-type cluster accompanied by in situ carbon-carbon bond formation of organic cations

Two novel sandwich-type polyanions containing hexagonal {V=O}(6) group (H(2)tpy)(Hbpe)(3)H[(VO)(6)(SbW(9)O(33))(2)]·2H(2)O (1) and (H(2)tcy)(6)(Hbpp)(6)H(4)[VW(12)O(40)][(VO)(6)(SbW(9)O(33))(2)](3)·30H(2)O (2) (tpy = 4-(2,3,4-tri(pyridin-4-yl)butyl)pyridine, bpe = 1,2-(4-pyridyl)ethene, tcy = 1,2,4,5-tetra(pyridin-4-yl)cyclohexanol, bpp = 1,3-bis-(4-pyridyl)propane), were reported. Both compounds are built upon the complex hydrogen bonding networks of C-H···O and N-H···O occurred among inorganic anions and organic cations. Unusual in situ organic reactions involving C-C coupling are also observed in 1 and 2 regardless of the rigid bpe or flexible bpp. Compound 2 represents a rare case in which nano-sized α-Keggin [VW(12)O(40)](4-) and sandwich-type [(VO)(6)(SbW(9)O(33))(2)](6-) anionic clusters are present in a common crystal framework.     

大环多胺配体BDBPH的设计合成及其晶体结构

用Pb(SN)₂作模板,2,6-二甲酰基对甲苯酚与二亚乙基三胺通过[2+2]缩合反应,经NaBH₄还原、脱Pb²⁺、酸化等操作,得晶体BDBPH·6HBr·4H₂O.晶体属单斜晶系,P2_1/c空间群,晶体学参数:a=1.4441(5)nm,b=1.1482(4)nm,c=1.2090(6)nm,α=90°,β=96.92°,γ=90°,V=1.9900nm³大环分子采取椅式构型,6个Br-和4个H₂O分子对称分布于大环两侧.该大环配体结构新颖,可用于多种金属配合物的研究,对进一步了解金属酶活性中心的结构及其催化作用机理具有重要价值.     

具有纳米孔结构的配位聚合物[Co2(HO-BDC)2(bpe)2(H2O)2]n·n(py)·nH2O的合成、晶体结构与热稳定性

在水-吡啶混合体系中, 以5-羟基-1,3-苯二甲酸(简作HO-H2BDC )、1,2-二(4-吡啶)乙烷(简作bpe)为配体与Co(NO3)2·6H2O反应, 培养出[Co2(HO-BDC)2(bpe)2(H2O)2]n·n(py)·nH2O(py=pyridine)的紫色单晶, 该晶体属三斜晶系, P1空间群, 晶胞参数a=1.0245(3) nm, b=1.1467(3) nm, c=1.2430(4) nm, α=68.915(5)°, β=67.163(4)°, γ=71.373(4)°, V=1.2279(6) nm3, Z=1, Mr=979.70, Dc=1.325 Mg/m3, F(000)=506, μ=0.740 mm-1, R1=0.0515, wR2=0.1058. 该配位聚合物中在ac平面上具有规则平行四边形纳米尺寸的孔, 其孔径大小约为1.025 nm×1.354 nm, 而且通过氢键相互作用连成具有双层结构的2D网络结构. TGA曲线表明, 配位聚合物的失重发生在110~150 ℃之间, 总失重约为80.1%, 最终产物为Co2O3.     

Influence of anionic sulfonate-containing co-ligands on the solid structures of silver complexes supported by 4,4'-bipyridine bridges

In this paper, ten new silver compounds, namely [Ag(bipy)](L1).H2O (1), [Ag(bipy)](L2).2H2O (2), [Ag2(bipy)2(H2O)2](L3).H2O (3), [Ag(L4)(bipy)].H2O (4), [Ag(L5)(bipy)] (5), [Ag(L6)(bipy)].0.5CH3CN (6), [Ag3(L7)2(bipy)2].2(H2O) (7), [Ag2(L8)(bipy)1.5(H2O)].H2O (8), [Ag2(L9)(bipy)2(H2O)2] (9) and [Ag3(L10)(bipy)2][(bipy)(H2O)2].(H2O)3.5 (10) (where bipy = 4,4'-bipyridine, L1 = 6-amino-1-naphthalenesulfonate anion, L2 = 2-naphthalenesulfonate anion, L3 = sulfosalicylate anion, L4 = p-aminobenzenesulfonate anion, L5 = 4-dimethyaminoazobenzenen-4'-sulfonate anion, L6 = 2,5-dichloro-4-amino-benzenesulfonate anion, L7 = 8-hydroxyquinoline-5-sulfonate anion, L8 = 2-nitroso-1-naphthol-4-sulfonate anion, L9 = 2,6-naphthalenedisulfonate anion and L10 = 1,3,5-naphthalenetrisulfonate anion), have been synthesized and characterized by elemental analyses, IR spectroscopy and X-ray crystallography. In compounds 1-6, Ag(I) centers are linked by bipy ligands to form 1D Ag-bipy chain structures, in which the sulfonate anions of compounds 1-3 act as counter ions. The sulfonate anions of compounds 4 and 5 connect Ag-bipy chains to form 1D double chain structures, respectively. The sulfonate anions of compound 6 connect Ag-bipy chains to form a 2D layer structure. Unexpectedly, compound 7 shows a hinged chain structure, and these chains interlace with each other through hydrogen bonds and pi-pi interactions to generate a 3D structure with channels along the c axis. Compounds 8 and 9 show 1D ladder-like structures. In compound 10, the Ag-bipy chains are connected by sulfonate anions to generate a 3D poly-threaded network, in which an isolated Ag-bipy chain is inserted. The results indicate that the anionic sulfonate-containing co-ligands play an important role in the final structures of the Ag(I) complexes. Additionally, the luminescent properties of these compounds were also studied.     

Direct Electrochemical Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ) Complex: [(bipy)2Cu(PhCOO)]ClO4·(benzil) (benzil = 1,2-Diphenyl-ethane-1,2-dione)

A new mononuclear copper(Ⅱ) complex [(bipy)2Cu(PhCOO)]ClO4·(benzil) (bipy=2,2'-bipyridine, benzil=1,2-diphenyl-ethane-1,2-dione) was synthesized by direct electrochemical oxidation of Cu electrode in an acetonitrile solution with benzoic acid, 2,2'-bipyridine and benzoin. As soon as the current flowed in the cell, benzoin was oxidized to benzil quickly. The crystal structure was determined by X-ray diffraction. It belongs to monoclinic system, space group P21/c with a=14.860(2), b=20.784(3), c=11.9150(17) (A), β=101.401(3)°, V=3607.3(9) (A)3, Z=4, Mr=806.69, Dc=1.485 g/cm3, F(000)=1660, μ=0.742 mm-1, R=0.0788 and wR=0.1519 for 6254 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). The complex contains a mononuclear [(bipy)2Cu(PhCOO)] cation, a solvate benzil molecule and a ClO4- anion which locates around the cation outside acting as the counter ion. The Cu(Ⅱ) ion is coordinated by two 2,2'-bipyridines and one benzoato ligand to form a distorted square-pyramid.