Synthesis and structure of [Zn8(HPO4)8(H2PO4)8]•[(C2H8N)8]•4H2O

A chain-like zincophosphate [Zn₈(HPO₄)₈(H₂PO₄)₈]•[(C₂H₈N)₈]•4H₂O was obtained at room temperature from a ZnO/P₂O₅/dimethylamine/H₂O mixture. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is monoclinic a=1.26450(7)nm, b=1.08477(5)nm, c=1.46311(4)nm, β=98.793(5)°, space group Cc. The structure consists of chains of zinc-corner-sharing Zn₂P₂O₄ four rings. The negative charge of the chains is compensated by the protonated dimethylamine. The characterization by ³¹P solid state nmr spectroscopy is also reported.     

Studies on organolanthanide complexes: XLII. Synthesis of the unsolvated monomeric complexes (MeOCH2CH2C5H4)3Ln (Ln  La,Pr) and X-ray structure of (MeOCH2CH2C5H4)3Pr

(MeOCH₂CH₂C₅H₄)₃Ln (Ln  La, Pr) complexes have been synthesized by reaction of LnCl₃ with MeOCH₂CH₂C₅H₄Na in THF at room temperature. A single-crystal X-ray diffraction study shows that the complex (MeOCH₂CH₂C₅H₄)₃Pr is monomeric in structure, and that the coordination number of the central Pr atom is 11. This is the first example of unsolvated monomeric La and Pr metallocene complexes with the largest possible coordination number of the metal.     

Synthesis and properties of bis(indenyl) derivatives of ytterbium and lutetium. Molecular structures of the complexes (C9H7)2Ln(μ-Cl)2Li(Et2O)2 (Ln = Yb, Lu) and [(C9H7)2YbCl2][Li(DME)3]

The heterobimetallic bis(indenyl) chloride complexes of ytterbium and lutetium (C₉H₇)₂Ln(μ-Cl)₂Li(Et₂O)₂ (Ln = Yb or Lu) were synthesized by the metathesis reaction of LnCl₃ with two equivalents of indenyllithium in diethyl ether. In the case of ytterbium, the analogous reaction in 1,2-dimethoxyethane afforded the ionic complex [(C₉H₇)₂YbCl₂]⁻[Li(DME)₃]⁺. The reaction of YbCl₃ with indenylpotassium in a molar ratio of 1: 2 in THF is accompanied by reduction of the metal atom to give the bis(indenyl) derivative of Yb^II, (C₉H₇)₂Yb(THF)₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 39–44, January, 2008.     

Structure of [Dy(Phen)(C4H8NCS2)3]·3CH2Cl2 solvate. Magnetic properties and photoluminiscence of [Ln(Phen)(C4H8NCS2)3] (Ln = Sm,Eu, Tb,Dy, Tm) complexes

It is found that diffraction patterns of complexes I–V of the composition [Ln(Phen)(C₄H₈NCS₂)₃] (Ln = Sm, Eu, Tb, Dy, and Tm respectively) are similar. Single crystals of [Dy(Phen)(C₄H₈NCS₂)₃]·3CH₂Cl₂ (VI) obtained are. According to the X-ray crystallographic data, in the structure of VI the unit cell contains two crystallographically independent molecules of the [Dy(Phen)(C₄H₈NCS₂)₃] complex and six CH₂Cl₂ molecules. The N₂S₆ coordination polyhedron of the Dy atom is a distorted square antiprism. In the range of 2–300 K the magnetic properties of complexes I–V are studied. It is found that complex III passes to the magnetically ordered state; the spontaneous magnetization at 2 K is 24 600 G·cm³/mol. At 300 K compounds I–IV exhibit photoluminescence in the visible spectral range. It is found that the photoluminescence intensity of complex I is several times higher than the photoluminescence intensity of complexes II–IV.     

Critical temperatures,pressures, and densities for the mixtures CO2–C3H8, CO2–nC4H10, C2H6–C3H8, and C3H8–nC4H10

A simple method is developed to estimate mixture critical temperatures (T_c), pressures (P_c), and densities (ρ_c) as a function of overall composition (X) from near critical region experimental coexistence data. This three-step method is applied to four mixtures, CO₂–C₃H₈, CO₂–nC₄H₁₀, C₂H₆–C₃H₈, and C₃H₈–nC₄H₁₀. Isothermal liquid–vapor coexistence data, which includes temperature, vapor pressure, coexisting densities (ρ^ℓ and ρ^v), and coexisting compositions for the more volatile component (x₁^v and x₁^ℓ) are used. In the first step, the difference of the saturated liquid and vapor densities (ρ^ℓ−ρ^v) is fitted to an empirical function in ((P_c−P)/P_c) to obtain P_c. Then P/P_c and ((ρ^ℓ+ρ^v)/2ρ_c) are simultaneously fitted to functions of a polynomial in (X₁−(x₁^v+x₁^ℓ)/2) yielding estimates of ρ_c and X₁. Finally, the discrete estimated critical data points are fitted with an equation to provide a continuous representation of the critical lines. The method is successfully tested for the mixtures, CO₂–C₃H₈ and CO₂–nC₄H₁₀, for which there is a reasonable amount of isothermal data. The procedure is then applied to the mixtures, C₂H₆–C₃H₈ and C₃H₈–nC₄H₁₀, for which there are sparse data. For all four mixtures, the critical temperature line, T_c vs. X₁, matches literature values within ±0.5%. The critical pressure line, P_c vs. X₁, and critical density line, ρ_c vs. X₁, match literature values, in general, within ±2%.     

Synthesis,crystal structure of Gd(H2O)(C2O4)2 · NH4 and of La(C2O4)2 · NH4. Characterization of the Ln(H2O)(C2O4)2 · NH4 with Ln=Eu…Yb

Single crystals of two lanthanide complexes, presenting similar formula Ln(H₂O)_x(C₂O₄)₂ · NH₄ with Ln=La, x=0 and Ln=Gd, x=1, have been prepared, in closed system at 200 °C. The gadolinium complex is bi-dimensional. A layer is built by the packing of the basic unit, [Gd(C₂O₄)]₄. The gadolinium atoms are related only by bischelating oxalate ligands, the ammonium ion and the water molecule (bound to the gadolinium atom) are localized into the interlayer space. The lanthanum complex is tri-dimensional. The basic building unit remains approximately the same and the packing of these units form a layer. However, within these units, the lanthanum atoms are related by either an oxalate ligand or an edge. Moreover, an oxalate ligand assumes the connection between the layers. The ammonium ion is localized into two sets of intersecting channels. Pure phase of the gadolinium complex has been prepared at 100 °C and extended to some lanthanide elements, Eu…Yb. As the size of the lanthanide ionic radius is decreasing, it is noticeable that the a unit–cell constant follows an expansion pattern while the others two follow an usual contraction one. The thermal behavior of this family shows that the anhydrous compounds are obtained and that some water molecule is sorbed during the cooling. Thus, the anhydrous compounds present a relatively open-framework with some small micropores.     

An infrared and Raman spectroscopic study of Td-type 4,4′-bipyridylcadmium(II) tetracyanometallate (II) benzene (1/2) clathrates: Cd(C10H8N2)Cd(CN)4 · 2C6H6 and Cd(C10H8N2)Hg(CN)4 · 2C6H6

Two new benzene clathrates of the form Cd(4,4-bipyridyl)M(CN)₄ · 2C₆H₆, (M=Cd or Hg) have been prepared in powder form. Their spectral data were compared with those of the corresponding host complexes and found to be consistent with the host structure found in Td-type clathrates.     

Molar heat capacity and thermodynamic properties of Lu(C5H9NO4)(C3H4N2)6(ClO4)3·5HClO4·10H2O

A complex of Lutetium perchloric acid coordinated with l-glutaminic acid (C₅H₉NO₄) and imidazole (C₃H₄N₂), Lu(C₅H₉NO₄)(C₃H₄N₂)₆(ClO₄)₃·5HClO₄·10H₂O was synthesized and characterized. Thermodynamic properties of the complex were studied with an adiabatic calorimeter (AC) from 80 to 390 K and differential scanning calorimetry (DSC) from 100 to 300 K. Two thermal abnormalities were discovered at 220.34 and 248.47 K, which were deduced to be phase transitions. One was interpreted as a freezing-in phenomenon of the reorientational motion of ClO₄ ^? ions and the other was attributed to the orientational order/disorder process of ClO₄ ^? ions. The low-temperature molar heat capacities were measured by AC and the thermodynamic functions [H _T  ? H _298.15] and [S _T  ? S _298.15] were derived in the temperature range from 80 to 390 K with temperature interval of 5 K. Thermal decomposition behavior of the complex was studied by thermogravimetric analysis and DSC.     

Synthesis,Spectroscopic Properties and Crystal Structure of (C4N2H12)2Zr(C2O4)4·H2O

The title compound (C4N2H12)2Zr(C2O4)4·H2O 1 was synthesized by the reaction of ZrOCl2·8H2O, H2C2O4·2H2O and piperazinium in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C16H26N4O17Zr, Mr = 637.63) crystallizes in the monoclinic system, space group P21/c with a = 9.0425(3), b = 13.3844(3), c = 19.1191(5)A, β = 98.365(1)o, V = 2289.34(11) A3, Z = 4, Dc = 1.850 g/cm3, F(000) = 1304, μ = 0.577 mm-1, the final R = 0.0240 and wR = 0.0628 for 4386 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Zr(C2O4)4]4- anion and two protonated piperazinium cations. The anions are linked through hydrogen bonds of piperazinium. FT-IR and Raman spectra clearly show the existence of oxalate groups in the crystal lattice.     

Low-temperature thermodynamics of Ln(Me2dtc)3(C12H8N2) (Me2dtc = dimethyldithiocarbamate, Ln = La, Pr, Nd, Sm)

The heat capacities of Ln(Me₂dtc)₃(C₁₂H₈N₂) (Ln = La, Pr, Nd, Sm, Me₂dtc = dimethyldithiocarbamate) have been measured by the adiabatic method within the temperature range 78–404 K. The temperature dependencies of the heat capacities, C _p,m [La(Me₂dtc)₃(C₁₂H₈N₂)] = 542.097 + 229.576 X ? 27.169 X ² + 14.596 X ³ ? 7.135 X ⁴ (J K^?1 mol^?1), C _p,m [Pr(Me₂dtc)₃(C₁₂H₈N₂)] = 500.252 + 314.114 X ? 17.596 X ² ? 0.131 X ³ + 16.627 X ⁴ (J K^?1 mol^?1), C _p,m [Nd(Me₂dtc)₃(C₁₂H₈N₂)] = 543.586 + 213.876 X ? 68.040 X ² + 1.173 X ³ + 2.563 X ⁴ (J K^?1 mol^?1) and C _p,m [Sm(Me₂dtc)₃(C₁₂H₈N₂)] = 528.650 + 216.408 X ? 16.492 X ² + 12.076 X ³ + 4.912 X ⁴ (J K^?1 mol^?1), were derived by the least-squares method from the experimental data. The heat capacities of Ce(Me₂dtc)₃(C₁₂H₈N₂) and Pm(Me₂dtc)₃(C₁₂H₈N₂) at 298.15 K were evaluated to be 617.99 and 610.09 J K^?1 mol^?1, respectively. Furthermore, the thermodynamic functions (entropy, enthalpy and Gibbs free energy) have been calculated using the obtained experimental heat capacity data.     

Thermal decomposition of Ln(C2H5CO2)3·H2O (Ln?=?Ho, Er, Tm and Yb)

The thermal decomposition of Ho(III), Er(III), Tm(III) and Yb(III) propionate monohydrates in argon was studied by means of thermogravimetry (TG), differential thermal analysis (DTA), IR-spectroscopy and X-ray diffraction (XRD). Dehydration takes place around 90?°C. It is followed by the decomposition of the anhydrous propionates to Ln₂O₂CO₃ (Ln?=?Ho, Er, Tm or Yb) with the evolution of CO₂ and 3-pentanone (C₂H₅COC₂H₅) between 300 and 400?°C. The further decomposition of Ln₂O₂CO₃ to the respective sesquioxides Ln₂O₃ is characterized by an intermediate plateau extending from approximately 500?C700?°C in the TG traces. This stage corresponds to an overall composition of Ln₂O_2.5(CO₃)_0.5 but is more probably a mixture of Ln₂O₂CO₃ and Ln₂O₃. The stability of this intermediate state decreases for the lighter rare-earth (RE) compounds studied. Full conversion to Ln₂O₃ is achieved at about 1,100?°C. The overall thermal decomposition behaviour of the title compounds is similar to that previously reported for Lu(C₂H₅CO₂)₃·H₂O.     

The magnetochemistry of novel cyano-bridged complexes Ln(DMF)4(H2O)2Mn(CN)6 · H2O (Ln = Tb,Dy, Er)

Using K₃Mn(CN)₆, DMF and Ln(NO₃)₃ · 6H₂O (Ln = Tb, Dy or Er), novel cyano-bridged complexes Ln(DMF)₄(H₂O)₂Mn(CN)₆ · H₂O (TbMn, DyMn and ErMn, respectively) were prepared and their magnetochemical properties were studied in detail. A weak antiferromagnetic interaction was found to exist between the rare earth ions and the manganese ion. Er(DMF)₄(H₂O)₂Mn(CN)₆ · H₂O, in particular, exhibits long-range magnetic ordering, a higher critical temperature (T _c = 17.5 K) and a stronger coercive force (H _c = 980 Oe).     

Synthesis and characterisation of MIL-43 and MIL-44, two new layered templated tetravalent phosphates: Zr(PO4)2·N2C2H10 and Ti2(PO4)2(HPO4)2·N2C2H10

Zr(PO₄)₂·N₂C₂H₁₀ or MIL-43 and Ti₂(PO₄)₂(HPO₄)₂·N₂C₂H₁₀ or MIL-44 were prepared hydrothermally (20 or 4 days, 473 or 453 K, respectively, autogenous pressure) in the presence of ethylenediamine. Their structures have been determined by single-crystal X-ray diffraction. MIL-43 crystallises in the monoclinic space group P2₁ (No. 4) with a=11.0722(1), b=10.6631(1), c=16.4642(2) Å, β=95.991(1)° and V=1933.21(3) Å³ (final agreement factors R₁(F)=0.0466, wR₂(F²)=0.1096). Due to the very poor quality of the crystal, only an approached structure of MIL-44 is given; it crystallises in the triclinic space group P1 (No. 1) with a=5.0845(4), b=6.3097(5), c=12.6111(9) Å, α=77.454(1), β=78.926(2), γ=89.986(1)° and V=387.21(5) Å³. Both solids are two-dimensional and are the ion-exchanged equivalents of the layered solids αZrP and γTiP. Inorganic sheets of MIL-43 are built up from pseudo-hexagonal arrays of ZrO₆ octahedra surrounded by PO₄ tetrahedra pointing their terminal oxygen alternatively up and down at the interlayer space. Layers of MIL-44 are made of double (TiOP) chains built from TiO₆ octahedra and PO₄ tetrahedra on which HPO₄ groups are grafted pointing towards the interlayer space. In both cases, diprotonated organic templates, located between the layers, interact with terminal phosphate groups and ensure via hydrogen bonds the stability of the structures.     

新型三维开放骨架稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4(Ln=Gd,Eu)的合成、结构及荧光性质

以哌嗪为模板剂,在水-乙醇混合溶剂体系中溶剂热合成了两个具有三维开放骨架结构的稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4（Ln = Gd,化合物1和Eu,化合物2）,并对其进行了结构表征、热重以及荧光光谱分析. 单晶结构解析表明,化合物1和2属于同构异质,均结晶于单斜晶系,P21/c空间群,化合物1,a = 19.691(3) ?,b = 19.249(3) ?,c = 13.186(2) ?,β = 92.33(0)o,V = 4993.5(1) ?3, Z =4. 化合物2,a = 19.7233(8) ?,b = 19.2791(8) ?,c = 13.2095(5) ?,β = 92.329(1)o,V = 5018.7(3) ?3, Z =4. 两个化合物在ab平面上由SO4,GdO8和GdO9多面体共边或共角交错连接形成含有八元环和十六元环的二维层状结构,该二维层沿c方向平行排列,相邻层通过SO4四面体相连形成具有孔道的三维开放骨架结构,其孔道之中包含平衡骨架负电荷的质子化哌嗪分子. 化合物2的固体荧光光谱分析显示其在397nm激发波长下,表现出典型的Eu3+发光性质.       

Investigation of Copper Halide:Hydrothermal Syntheses and Characterization of CuBr2(C12H8N2) and Cu3Br3(C12H8N2)2

The reaction of CuBr₂ with 1,10‐phen‐H₂O (1,10‐phen = 1,10‐phenanthroline) gave two compounds: CuBr₂(C₁₂H₈N₂) and Cu₃Br₃(C₁₂H₈N₂)₂. Their structures have been characterized by single‐crystal X‐ray diffraction analysis, elemental analyses, thermogravimetric analyses (TGA) and measurement of variable temperature magnetic susceptibility. Crystal data for CuBr₂(C₁₂‐H₈N₂): monoclinic, space group P2₁/n, a = 0.9977(3) nm, b = 0.65138(14) nm, c = 1.8207(4) nm, β = 91.624(18)°, V = 1.1828(5) nm³, Z = 2. Crystal data for Cu₃Br₃(C₁₂H₈N₂)₂: monoclinic, space group C2/c, a = 1.00167(11) nm, b = 1.4523(4) nm, c = 1.6295(3) nm, β = 94.386(14)°, V = 2.3635(8) nm³, Z = 3.     

Synthesis and structure of the organoantimony peroxide solvates [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·1.5C4H8O2 and [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·6C4H8O2

The organoantimony peroxide (Ar₂SbO)₄(O₂)₂ (Ar = C₆H₃OMe-2, Br-5) was synthesized by the oxidation of Ar3Sb with hydrogen peroxide in the presence or acetoxime or acetophenone oxime in dioxane. The product crystallizes with various content of the solvent molecules in the crystal unit cell [1.5 (I) and 6 (II), respectively]. An X-ray diffraction analysis of the solvates was performed. Four antimony atoms in the peroxide are in the octahedral coordination, and are linked through bridging oxygen atoms and two peroxide groups. The distances Sb-C, Sb-O_bridge, Sb-O_peroxide, O-O and Sb...Sb are 2.117–2.122, 1.960–1.972, 2.193–2.235, 1.461, 1.465 and 3.223–3.237 Å in I, and 2.112, 2.119, 1.957, 1,966, 2.204, 2,246, 1,467, and 3.2439 Å in II.     

Reduction of 2,5-di-tert-butylcyclopentadienone and pyridine with thulium diiodide. Structures of the complexes TmI2(THF)2[η5-But2C5H2O]TmI2(THF)3 and [TmI2(C5H5N)4]2(μ2-N2C10H10)

Reduction of 2,5-di-tert-butylcyclopentadienone with two equivalents of thulium diiodide in tetrahydrofuran afforded the binuclear thulium(iii) complex with the cyclopentadienyl oxide ligand, viz., TmI₂(THF)₂[⁵-Bu^t ₂C₅H₂O]TmI₂(THF)₃ (1). Shielding of the carbonyl carbon atom with two tert-butyl substituents prevents pinacolization of the ketyl radical anions that formed upon one-electron reduction of cyclopentadienone. The reaction of thulium diiodide with an excess of pyridine in tetrahydrofuran gave a product of reductive coupling of two pyridine radical anions, viz., [TmI₂(C₅H₅N)₄]₂(₂-N₂C₁₀H₁₀) (2). The structures of complexes 1 and 2 were established by single-crystal X-ray diffraction analysis.     

Quantum chemical calculations and the structure of Ni n (C2H2) complexes (n = 1–4)

Complexes of nickel atoms and small clusters with acetylene molecules are studied within the density functional theory. A trend toward the predominant formation of structures with bridge hydrogen atoms is observed in reactions between Ni _n and acetylene with rising n.     

Two binuclear complexes containing the enrofloxacinate anion: Cd2(C19H21N3O3F)4(H2O)2 · 4H2O and Pb2(C19H21N3O3F)4 · 4H2O

The syntheses and crystal structures of the closely related but non-isostructural Cd₂(C₁₉H₂₁N₃O₃F)₄(H₂O)₂?·?4H₂O (1) and Pb₂(C₁₉H₂₁N₃O₃F)₄?·?4H₂O (2) are described, where C₁₉H₂₁N₃O₃F^? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M₂O₂ (M?=?Cd, Pb) structural unit. The Cd²⁺ coordination polyhedron in 1 is a CdO₆ trigonal prism, including one coordinated water. The Pb²⁺ coordination polyhedron in 2 can be described as a very distorted square-based PbO₅ pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C₇₆H₉₆Cd₂F₄N₁₂O₁₈, M _r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?ų, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F ²)?=?0.079. 2: C₇₆H₈₈F₄N₁₂O₁₆Pb₂, M _r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?ų, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F ²)?=?0.049.     

Architecture of framework copper(I) halide π-complexes with N-allyl-N,N,N′,N′-tetramethyl-ethylenediaminium and N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium: Synthesis and crystal structure of [{C2H4N2(H+)×(CH3)4(C3H5)} Cu4Cl6] and [{C2H4N2(CH3)4(C3H5)2}0.5Cu2Cl1.67Br1.33]

N,N,N??,N??-tetramethylethylenediamine is obtained by the reaction of ethylenediamine with formaldehyde and formic acid (the Eschweiler-Clarke reaction) and then alkylated with allyl chloride (or bromide) in a ratio of 1:1 or 1:2 to obtain N-allyl-N,N,N??,N??-tetramethylethylenediaminium and N,N??-diallyl-N,N,N??,N??-tetramethylethylenediaminium bromide respectively. [{C₂H₄N₂(H⁺)(CH₃)₄(C₃H₅)}Cu₄Cl₆] (1) and [{C₂H₄N₂(CH₃)₄(C₃H₅)2}_0.5Cu₂Cl_1.67Br_1.33] (2) ??-complexes are obtained from alcohol solutions containing an ethylenediamine derivative and copper(II) chloride by ac-electrochemical synthesis on copper wire electrodes. An XRD study of the complexes is carried out. The crystals are monoclinic; 1: P2₁/n space group, a = 9.0081(6) ?, b = 12.5608(7) ?, c = 16.8610(10) ?, ?? = 102.061(3)°, V = 1865.7(2) ?³, Z = 4; 2: C2/c space group, a = 14.462(2) ?, b = 12.519(1) ?, c = 12.762(2) ?, ?? = 107.861(5)°, V = 2199.1(4) ?³, Z = 8. The structure of 1 consists of infinite copper halide networks with four crystallographically independent copper atoms, one of which coordinates the double bond of the allyl group of the ligand. The [C₂H₄N₂(H)(CH₃)₄(C₃H₅)]²⁺ cations are attached above and below the plane of the network. The individual fragments are bonded via an extensive system of (N)H??Cl and (C)H??Cl hydrogen bonds. The structure of 2 contains a three-dimensional copper halide framework whose cavities contain the [C₂H₄N₂(CH₃)₄(C₃H₅)₂]²⁺ cations that are ??-coordinated with copper(I) atoms. In both structures, the Cu(I) atom that coordinates the C=C bond has a trigonal-pyramidal coordination environment consisting of the double C=C bond of the corresponding ligand and three halogen atoms. The other Cu(I) atoms have a tetrahedral environment consisting solely of halogen atoms. The Cu-(C=C) distance is 1.958(1) ?, (1) and 1.974(1) ? (2).