Trans‐bis(saccharinato)cadmium(II) Complexes with 2‐Aminomethylpyridine and 2‐Aminoethylpyridine — Synthesis,Crystal Structures,Spectral and Thermal Characterization of trans‐[Cd(sac)2(ampy)2] and trans‐[Cd(sac)2(aepy)2]

Two trans‐bis(saccharinato) (sac) complexes of cadmium(II ) with 2‐aminomethylpyridine (ampy) and 2‐aminoethylpyridine (aepy) were synthesized and characterized by means of elemental analysis, FT‐IR spectroscopy and thermal analysis. In addition, their solid‐state structures were determined by single crystal X‐ray diffraction studies. The [Cd(sac)₂(ampy)₂] ( 1 ) and [Cd(sac)₂(aepy)] ( 2 ) complexes consist of neutral monomeric units and crystallize in the orthorhombic (Pbca) and monoclinic (P2₁/c) crystal systems, respectively. The cadmium(II ) ions in 1 and 2 sit on inversion centres andexhibit distorted octahedral coordination by two sac anions and two aminopyridine ligands. The sac ligands in both complexes are N‐coordinated and located in trans positions, while the ampy and aepy ligands act as a bidentate ligand forming two symmetrically chelate rings around cadmium(II ). IR spectra and thermal decompositions of the complexes are also discussed.     

A One‐dimensional Lead(II) Coordination Polymer with Bridging Saccharinate and 2‐Aminomethylpyridine Ligands: Synthesis,IR Spectra,and Crystal Structure of [Pb(ampy)(μ‐sac)2]n

A complex with eight‐coordinate lead(II ) atom and saccharinate (sac) and 2‐aminomethylpyridine ligands was characterized by IR, elemental analysis and X‐ray crystallography. The lead(II ) complex crystallizes in the monoclinic crystal system with space group P2₁/c. The single crystal X‐ray analysis shows that the complex is a coordination polymer, [Pb(ampy)(μ‐sac)₂]_n, in which the lead(II ) ions have a highly distorted bicapped trigonal antiprism coordination. Lead(II ) ions are bridged by carboxyl groups of sac forming one‐dimensional linear chains, running parallel to the a axis. The intrachain Pb···Pb distances are 4.4490(3) and 4.4679(3)Å. The individual chains are connected by N—H···O_sulfonyl and C_ampy—H···O_sulfonyl type hydrogen bonds, resulting in a three‐dimensional network. The sac ligand acts as bidentate and bridging ligand, while ampy behaves as an N, N′ donor. The IR spectra of the lead(II ) complex are discussed in detail.     

Bis(saccharinato)copper(II) complexes with 2-aminomethylpyridine and 2-aminoethylpyridine: Syntheses,crystal structures,spectral and thermal characterizations of trans-[Cu(sac)2(ampy)2] and [Cu(sac)2(aepy)(H2O)] (ampy = 2-aminomethylpyridine and aepy = 2-aminoethylpyridine)

Two bis(saccharinato)copper(II) complexes with 2-aminomethylpyridine (ampy) and 2-aminoethylpyridine (aepy) have been prepared and characterized by elemental analyses, IR and electronic spectroscopy, magnetic measurements and single-crystal X-ray diffraction. The copper(II) ion in trans-[Cu(sac)₂(ampy)₂] has ?1 site symmetry and is octahedrally coordinated by two neutral ampy and two anionic sac ligands, whereas the copper(II) ion in [Cu(sac)₂(aepy)(H₂O)] is five-coordinate with a distorted square-pyramidal coordination geometry. Both ampy and aepy behave as bidentate (N,N′) chelating ligands, while the saccharinate anion (sac) in the title complexes is N-coordinated. IR spectra of both complexes display typical absorption bands of bidentate aminopyridines and N-bonded sac ligands. Thermal decomposition behavior of the complexes is described in detail.     

The First Calcium(II) Complex with the Saccharinate Ligand: Synthesis,Crystal Structure,Spectral and Thermal Characterization of Trans—diaquabis[(2—hydroxyethyl)pyridinium]bis(saccharinato)calcium(II) Disaccharinate, [Ca(sac)2(H2O)2(Hpyet)2](sac)2

A new calcium(II) complex of the saccharinate ligand (sac) with 2—hydroxyethylpyridinium (Hpyet) was synthesized and characterized by elemental analysis, FT—IR spectroscopy, thermal analysis and single crystal X—ray diffractometry. The [Ca(sac)₂(H₂O)₂(Hpyet)₂](sac)₂ complex crystallizes in the triclinic space group (P1¯) with the cell dimensions a = 7.4360(7)Å, b = 12.5263(12)Å, c = 12.8329(13)Å, α = 82.534(8)°, β = 75.202(8)° and γ = 89.662(8)° (293 K). The title complex consists of a complex cation and two sac anions. In the complex cation, the calcium(II) ion is six—coordinate, bonding to two aqua ligands, two Hpyet ligands andtwo sac ligands located in the trans positions. Two of the sac ions are coordinated to the calcium(II) ion through the carbonyl O atom, while the other two remain outside the coordination sphere as the counter—ions. Thermal decomposition of the complex in air results in elimination of aqua, Hpyet, and sac ions, respectively.     

An Aqua‐Bridged Helical‐Chain Copper(II)‐Saccharinato Polymer Linked into a Two‐Dimensional Supramolecular Framework

A new assembly [Cu₂(sac)₂(μ‐dmea)₂(μ‐H₂O)]_n (sac = saccharinate and Hdmea = 2‐dimethylaminoethanol) has been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X‐ray diffraction. The complex crystallizes in the monoclinic space group C2/c and consists of dinuclear modules of [Cu₂(sac)₂(dmea)₂]. The sac ligand is N‐coordinated, while the dmea ligand is in the deprotanated form by losing the ethanol hydrogen atom and acts as a bidentate donor through the alkoxo group and N atom. The alkoxo group also serves as a bridge between two copper(II) ions, leading to an intra‐dimer Cu···Cu separation of 3.0229(7) Å. The dimeric units are bridged by aqua ligands to generate a one‐dimensional water‐bridged helical chain, in which the copper(II) ions exhibit a distorted square‐pyramidal CuN₂O₃ coordination. The Cu–Cu distance in the chain separated by the bridging aqua ligands is 5.297Å. The polymeric chains are further linked by π(sac)···π(sac) and C–H···π(sac) interactions into a two‐dimensional supramolecular network.     

A Mercury Iodide Adduct with 1,1‐Bis(diphenylphosphino)ferrocene – Synthesis,Crystal Structure,and Nonlinear Refractive Properties

A new mercury iodide complex of dppf, [HgI₂(dppf)] (adduct 1 , dppf = 1,1‐bis(diphenylphosphino)ferrocene) was prepared and characterized. Single crystal X‐ray diffraction analysis established that the compound crystallizes in the monoclinic system, space group C2c, with a = 34.992(3), b = 10.236(5), c = 18.765(4) Å, β = 99.410(2)°, Z = 8, V = 6631.2(9) ų. The coordination about the mercury atom is tetrahedral with two equivalent Hg–I and Hg–P bonds. Dppf functions as a chelating ligand. The nonlinear optical (NLO) properties were studied with an 8 ns‐pulsed laser at 532 nm. Its optical responses to the incident light exhibit weak optical absorptive and strong refractive effects, with n₂ = 6.86 × 10^–18 m² · W^–1 in a 2.48 × 10^–4 mol · dm^–3 DMF solution.     

Synthesis,Spectra, Thermal Analysis and Crystal Structure of Trans-Bis(2-Pyridinepropanol)Bis (Saccharinato)Cobalt(II)

The title complex, [Co(pypr)₂(sac)₂] (pypr = 2-pyridinepropanol and sac = saccharinate), has been prepared and characterized by elemental analysis, electronic and FTIR spectra, magnetic susceptibility measurements, thermal analysis and X-ray diffractometry. The complex crystallizes in triclinic space group PI with a = 8.1836(2), b = 10.0062(2), c = 10.4989(3) Å, α = 90.474(1), β = 107.989(1) and γ = 110.923(1)°. The cobalt(II) ion sits on a center of symmetry and is octahedrally coordinated by two pypr and two sac ligands. Both pypr and sac ligands occupy the trans positions of the coordination octahedron. The two pypr ligands are neutral and act as bidentate N- and O-donor ligands forming two symmetry-related seven-membered chelate rings around the cobalt(II) ion, while both sac ligands are O-coordinated through the carbonyl oxygen atoms. On heating the endothermic removal of two pypr ligands occurs in the first stages of decomposition and at higher temperatures the Co/sac intermediate decomposes to Co₃O₄ and finally to CoO.     

Synthesis,Spectrothermal and Structural Characterization of Saccharinatobis(tris‐hydroxymethylaminomethane)zinc(II)saccharinate Complex, [Zn(sac)(tham)2](sac)

A novel Zn^II complex of the saccharinate ligand (sac) with tris‐hydroxymethylaminomethane (tham) was synthesized and characterized by elemental analysis, FT‐IR spectroscopy, simultaneous TG and DTA techniques, and X‐ray diffraction. The complex, [Zn(sac)(tham)₂](sac), crystallizes in monoclinic system with space group P2₁/c [a = 7.55954(3) Å, b = 13.0532(6) Å, c = 27.7777(10) Å, β = 100.539(3)°, Z = 4]. The Zn^II ion has a distorted octahedral coordination. The tham ligand has chemically different functions in the structure, acting as both bidentate and tridentate ligands. There are also sac moieties to act as N‐bonded ligand and as a counter anion. The molecular packing of the complex is provided by moderate hydrogen bonds as well as π···π interactions between the sac moieties. The IR spectra and the thermal decomposition of the complex are also discussed.     

Bis(Saccharinato)Nickel(II) Complexes with 2-Aminomethyl and -Ethylpyridines. Syntheses,Crystal Structures,Spectral and Thermal Analyses of trans-[Ni(sac-N)2(ampy-N,N′)2] and trans-[Ni(sac-O)2(aepy-N,N′)2]

The trans-bis(saccharinato)nickel(II) complexes with 2-aminomethylpyridine (ampy) and 2-aminoethylpyridine (aepy) have been prepared and characterized by elemental analyses, i.r., u.v.–vis., magnetic measurements and single crystal X-ray diffraction. Both structures consist of discrete molecules of the title complexes, in which the nickel(II) ion lies on an inversion centre and is octahedrally coordinated by two bidentate (N,N) ampy or aepy ligands and two anionic sac ligands, occupying trans positions. The most interesting feature of the complexes is the coordination of sac. In [Ni(sac)₂(ampy)₂], sac is N-bonded, whereas it is O-coordinated in [Ni(sac)₂(aepy)₂]. The i.r. spectra and thermal behaviour of both complexes are discussed in detail.     

Three Ternary Rare Earth(III) Complexes Based on 3‐[(4,6‐Dimethyl‐2‐pyrimidinyl)thio]‐propanoic Acid and 1,10‐Phenanthroline: Synthesis,Crystal Structure and Antioxidant Activity

Three ternary rare earth [Nd^III ( 1 ), Sm^III ( 2 ) and Y^III ( 3 )] complexes based on 3‐[(4,6‐dimethyl‐2‐pyrimidinyl)thio]‐propanoic acid (HL) and 1,10‐phenanthroline (Phen) were synthesized and characterized by IR and UV/Vis spectroscopy, TGA, and single‐crystal X‐ray diffraction. The crystal structures showed that complexes 1 – 3 contain dinuclear rare earth units bridged by four propionate groups and are of general formula [REL₃(Phen)]₂ · nH₂O (for 1 and 2 : n = 2; for 3 : n = 0). All rare earth ions are nine‐coordinate with distorted mono‐capped square antiprismatic coordination polyhedra. Complex 1 crystallizes in the monoclinic system, space group P2₁/c with a = 16.241(7) Å, b = 16.095(7) Å, c = 19.169(6) Å, β = 121.48(2)°. Complex 2 crystallizes in the monoclinic system, space group P2₁/c with a = 16.187(5) Å, b = 16.045(4) Å, c = 19.001(4) Å, β = 120.956(18)°. Complex 3 crystallizes in the triclinic system, space group P1 with a = 11.390(6) Å, b = 13.636(6) Å, c = 15.958(7) Å, α = 72.310(17)°, β = 77.548(15)°, γ = 78.288(16)°. The antioxidant activity test shows that all complexes own higher antioxidant activity than free ligands.     

Different Coordination Modes of Saccharin in the Complexes of Lead(II) with 2‐Pyridylmethanol and Pyridine‐2, 6‐dimethanol — Synthesis,Spectral and Structural Characterization

New lead(II)‐saccharin complexes, [Pb(sac)₂(pym)] (1) and [Pb(sac)₂(pydm)] (2) (sac = saccharinate anion; pym = 2‐pyridylmethanol; pydm = pyridine‐2, 6‐dimethanol) were synthesized and characterized by IR spectroscopy and single crystal X‐ray diffractometry. Complex 1 crystallizes in the monoclinic P2₁/c space group with Z = 4, while the crystals of complex 2 are extremely X‐ray sensitive and decompose by the X‐ray beam within one day. Pym and pydm act as bi‐ and tridentate ligands, respectively. Most important feature of the complexes is non‐equivalent coordination of the sac ligands to the lead(II) atom. In the complex 1 , the sac ligands coordinate to the lead(II) ion in two distinct manners. One sac ligand behaves as a bridge between the lead(II) atoms through its N and carbonyl O atoms, whereas the other sac ligand acts as a bidentate chelating ligand through its N and carbonyl O atoms which is bicoordinating and also bridges the metal atoms to achieve the seven‐coordination. The structure is built up of three‐dimensional chains formed by the bridging of the PbN₃O₂ units and also held intermolecular hydrogen bonds. The IR spectra of the complexes were discussed in detail.     

Syntheses and Structures of two 1‐D Complexes, [Co(dmf)2(NCNCN)2] and [Cu(bipy)(NCNCN)]ClO4 with Bridging Dicyanamide Ligands

Two novel dicyanamide complexes [Co(dmf)₂(NCNCN)₂] ( 1 ) and [Cu(bipy)(NCNCN)]ClO₄ ( 2 ) have been synthesized and structurally characterized. 1 crystallizes in the monoclinic space group C2 with a = 13.568(6)Å, b = 7.403(3)Å, c = 8.118(3)Å and Z = 2, whereas 2 crystallizes in the monoclinic system, Cc group, a = 14.270(7)Å, b = 9.143(5)Å, c = 12.371(1) Å, β = 118.612(7)°, and Z = 4. According to X‐ray crystallographic studies, in complex 1 each Co^II ion is six‐coordinated with four nitrogen atoms from four μ_{1, 5}‐dca (dca = dicyanamide) ligands and two oxygen atoms from two dmf ligands to form distorted octahedra. 1 forms a 1‐D network bridged via μ_{1, 5}‐dca. 2 consists of a uniform Cu(NCNCN)Cu chain, each Cu^II ion is octahedrally coordinated with four nitrogen atoms from two μ_{1, 5}‐dca ligands and one bipy ligand and two oxygen atoms from two ClO₄^— ions. The octahedral Cu^II ion shows a significant Jahn‐Teller distortion, with two axial oxygen atoms considerably farther from the copper than the four equatorial nitrogens.     

Palladium(II) Complexes with the Mixed‐Donor Ligand CH3S‐(CH2)3‐PPh2 Crystal Structures of [PdCl2{CH3S‐(CH2)3‐PPh2}n](n = 1, 2)

The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by ¹H NMR and ¹³C NMR. Reactions of S‐P3 with [PdCl₂(PhCN)₂] afforded the complexes [PdCl₂(S‐P3)] ( I ) and [PdCl₂(S‐P3)₂] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P2₁/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)ų, Z = 4. Likewise, compound II crystallizes in monoclinic space group P2₁/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)ų, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom.     

Synthesis and Crystal Structure of Manganese(II) Bipyridine Carboxylato Complexes: [(bipy)2MnII(μ‐C2H5CO2)2MnII(bipy)2](ClO4)2 and [MnII(ClCH2CO2)(H2O)(bipy)2]ClO4 · H2O (bipy = 2,2′‐bipyridine)

Two manganese(II) bipyridine carboxylate complexes, [(bipy)₂Mn^II(μ‐C₂H₅CO₂)₂Mn^II(bipy)₂}₂](ClO₄)₂ ( 1 ), and [Mn^II(ClCH₂CO₂)(H₂O)(bipy)₂]ClO₄ · H₂O ( 2 ) were prepared. 1 crystallizes in the triclinic space group P 1 with a = 8.604(3), b = 12.062(3), c = 13.471(3) Å, α = 112.47(2), β = 93.86(2), γ = 92.87(3)°, V = 1211.1(6) ų and Z = 1. In the dimeric, cationic complex with a crystallographic center of symmetry two 2,2′‐bipyridine molecules chelate each manganese atom. These two metal fragments are then bridged by two propionato groups in a syn‐anti conformation. The Mn…Mn distance is 4.653 Å. 2 crystallizes in the monoclinic space group P2₁/c with a = 9.042(1), b = 13.891(1), c = 21.022(3) Å, β = 102.00(1)°, V = 2569.3(5) ų and Z = 4. 2  is a monomeric cationic complex in which two bipyridine ligands chelate the manganese atom in a cis fashion. A chloroacetato and an aqua ligand complete the six‐coordination. Only in 2 is the intermolecular packing controlled by weak π‐stacking besides C–H…π contacts between the bipyridine ligands.     

Synthesis,Spectroscopic, and X‐Ray Diffraction Studies of cis‐Dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl3 H‐pyrazol‐3‐onato) Tin(IV)

Reaction between an aqueous ethanol solution of tin(II) chloride and that of 4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐one in the presence of O₂ gave the compound cis‐dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐onato) tin(IV) [(C₂₆H₂₆N₄O₄)SnCl₂]. The compound has a six‐coordinated Sn^IV centre in a distorted octahedral configuration with two chloro ligands in cis position. The tin atom is also at a pseudo two‐fold axis of inversion for both the ligand anions and the two cis‐chloro ligands. The orange compound crystallizes in the triclinic space group P 1 with unit cell dimensions, a = 8.741(3) Å, b = 12.325(7) Å, c = 13.922(7) Å; α = 71.59(4), β = 79.39(3), γ = 75.18(4); Z = 2 and D_x = 1.575 g cm^–3. The important bond distances in the chelate ring are Sn–O [2.041 to 2.103 Å], Sn–Cl [2.347 to 2.351 Å], C–O [1.261 to 1.289 Å] and C–C [1.401 Å] the bond angles are O–Sn–O 82.6 to 87.7° and Cl–Sn–Cl 97.59°. The UV, IR, ¹H NMR and ¹¹⁹Sn Mössbauer spectral data of the compound are reported and discussed.     

Synthesis,Structural Characterization and Thermal Stability of [Mn(3‐bpd)2(NCS)2(H2O)2]·2H2O (1) and {[Mn(bpe)(NCS)2(H2O)2]·(3‐bpd)·(bpe)·H2O}n (2) from One‐Pot Crystallization

Two supramolecular architectures, [Mn(3‐bpd)₂(NCS)₂(H₂O)₂]·2H₂O ( 1 ) and {[Mn(bpe)(NCS)₂(H₂O)₂]·(3‐bpd)·(bpe)·H₂O}_n ( 2 ) [bpe = 1,2‐bis(4‐pyridyl)ethylene and 3‐bpd = 1,4‐bis(3‐pyridyl)‐2,3‐diaza‐1,3‐butadiene] have been synthesized and characterized by spectroscopic, elemental and single crystal X‐ray diffraction analyses. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, with chemical formula C₂₆H₂₈Mn N₁₀O₄S₂, a = 9.1360(6), b = 9.7490(6), c = 17.776(1) Å, β = 93.212(1)°, and Z = 2 while compound 2 crystallizes in the orthorhombic system, space group P2₁2₁2₁, with chemical formula C₃₈H₃₆Mn₁N₁₀O₃S₂, a = 14.1902(6), b = 15.4569(7), c = 18.2838(8) Å, α = β = γ = 90°, and Z = 4. Structural determination reveals that the coordination geometry at Mn(II) in compound 1 or 2 is a distorted octahedral which consists of two nitrogen donors of two NCS^?ligands, two oxygen donors of two water molecules, and two nitrogen donors of two 3‐bpd ligands for 1 and two dpe ligands for 2 , respectively. The two 3‐bpd ligands in 1 adopt a monodentate binding mode and the dpe in 2 adopts a bismonodentate bridging mode to connect the Mn(II) ions forming a 1D chain‐like coordination polymer. Both the π‐π stacking interactions between the coordinated and the free pyridyl‐based ligands and intermolecular hydrogen bonds among the coordinated and the crystallized water molecules and the free pyridyl‐based ligands play an important role in construction of these 3D supramolecular architectures.     

Three Crystal Structures,One Chemical Formula – Barium Dihydrogen‐hypodiphosphate(IV)‐dihydrate,BaH2P2O6·2H2O

Three polymorphs of barium dihydrogen‐hypodiphosphate(IV)‐dihydrate, BaH₂P₂O₆ · 2H₂O ( A , B and C ), were obtained and structurally characterized by single‐crystal X‐ray diffraction. A crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 7.459(1) Å, b = 8.066(1) Å, c = 12.460(2) Å, β = 91.27(1) ° and Z = 4. B crystallizes in the monoclinic space group C2/c (no. 15) with a = 11.049(8) Å, b = 6.486(3) Å, c = 10.956(6) Å, β = 106.89(5) ° and Z = 4. C crystallizes in the orthorhombic space group C222₁ (no. 20) with a = 9.193(3) Å, b = 6.199(2) Å, c = 12.888(4) Å and Z = 4. Discrete [H₂P₂O₆]^2– units, barium cations and water molecules, held together by intermolecular hydrogen bonds of the type O–H ··· O, build up the structures of the three polymorphs. The phase purity of A and C was verified by powder diffraction measurements.     

Caesiumchloropalladat(II)‐hydrate – zwei neue Verbindungen mit kondensierten [Pd2Cl6]‐Baugruppen

Caesiumchloropalladate(II)‐hydrates – Two New Compounds with Condensed [Pd₂Cl₆] Groups We were able to synthesize two caesiumchloropalladate(II)‐hydrates in the CsCl/PdCl₂/H₂O system by hydrothermal methods. Both compounds show combination of monomeric and dimeric Pd–Cl groups. We characterized the crystal structures by single‐crystal X‐ray diffraction. Cs₆Pd₅Cl₁₆ · 2 H₂O ( I ) crystallizes triclinic in space group type P1 (Nr. 2) with a = 8.972(1) Å, b = 11.359(1) Å, c = 18.168(1) Å, α = 83.61(1)°, β = 76.98(1)°, γ = 76.39(1)° and Z = 2, Cs₁₂Pd₉Cl₃₀ · 2 H₂O ( II ) monoclinic, space group type C2/m (No. 12) with a = 19.952(1) Å, b = 14.428(1) Å, c = 14.411(1) Å, β = 125.29(1)°, and Z = 2.     

Syntheses and Crystal Structures of Copper(II) and Copper(I) dpp Complexes, [Cu(dpp)Br2] and [Cu(dpp)2][CuBr2] (dpp = 2,9‐diphenyl‐1,10‐phenanthroline)

The complexes [Cu(dpp)Br₂] ( 1 ) and [Cu(dpp)₂][CuBr₂] ( 2 ) (dpp = 2,9‐diphenyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction methods. Reaction of copper(II) bromide with the dpp ligand in dichloromethane at room temperature afforded 1 , which is a rare example of non‐square planar four‐coordinate copper(II) complexes. Complex 1 crystallizes in the monoclinic space group C2/c with a = 15.352(3), b = 13.192(3), c = 11.358(2) Å, β = 120.61(3)°, V = 1979.6(7) ų, Z = 4, D_calc = 1.865 g cm^?3. The coordination geometry about the copper center is distorted about halfway between square planar and tetrahedral. The Cu‐N distance is 2.032(2) Å and the Cu‐Br distance 2.3521(5) Å. Heating a CH₂Cl₂ or acetone solution of 1 resulted in complex 2 , which consists of a slightly distorted tetrahedral [Cu(dpp)₂]⁺ cation and a linear two‐coordinate [CuBr₂]^? anion. 2 crystallizes in the triclinic space group with a = 10.445(2), b = 11.009(2), c = 18.458(4) Å, α = 104.72(3), β = 94.71(3), γ = 103.50(3)°, V = 1973.3(7) ų, Z = 2, D_calc = 1.602 g cm^?3. The four Cu(1)‐N distances are between 2.042(3) and 2.067(3) Å, the distance of Cu(2)‐Br(1) 2.2268(8) Å, and the disordered Cu(3)‐Br(2) distances are 2.139(7) and 2.237(4) Å, respectively. Complex 2 could also be prepared by directly reacting CuBr with dpp in CH₂Cl₂.     

Bis(phthalocyaninato(2–)rhenium(II)): Synthesis,Properties, and Crystal Structure

Blue, paramagnetic bis(phthalocyaninato(2–)rhenium(II)) (μ_eff = 0,88 μ_B, per Re, at 300 K) is prepared by thermal decomposition of trans-bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), in boiling triphenylphosphine. It crystallizes in the triclinic space group P 1 with cell parameters as follows: a = 7.799(3) Å, b = 12.563(7) Å, c = 12.69(1) Å, α = 89.97(5)°, β = 94.14(5)°, γ = 106.39(4)°; Z = 1. Two cofacial phthalocyaninates are bonded together by a Re–Re bond with a Re–Re distance of 2.285(2) Å. The Re atoms are located distinctly outside the centre of the (N_iso)₄ planes by 0.426(3) Å. The Re–N_iso distance varies from 1.99(1) to 2.04(1) Å (average 2.02 Å). The pc^2– ligands are in an eclipsed conformation and concavely distorted. In the UV-VIS-NIR spectrum the B region is split into two bands of comparable intensity due to strong excitonic coupling. The Re–Re stretching vibration at 240 cm^–1 is selectively enhanced in the resonance Raman spectrum (λ_exc = 488 nm).