The Crystal Structures of Thallium(I) Fluoride

The effects of temperature and pressure on the crystal structures of thallium(I) fluoride have been investigated using powder neutron diffraction, with the aim of resolving the uncertainties present in the literature. Under ambient conditions, TlF adopts an orthorhombic structure in space group Pbcm with Z=4 and cell parameters a=6.09556(8) Å, b=5.48860(7) Å, and c=5.18300(7) Å. This structure can be derived from an idealized rocksalt-type arrangement, though with extensive distortions of the anion sublattice due to the presence of the 6s² inert pair of the Tl⁺ Above 355 K TlF becomes tetragonal with Z=2, a=3.78283(2) Å, c=6.12312(5) Å, and space group P4/nmm. The behavior of the compound is also studied under hydrostatic pressure but, contrary to previous reports, no structural transition was observed and TlF remains orthorhombic up to at least 3.5 GPa. The compressibility is greatest along the a and b axes. The relationship between the ambient- and high-temperature structures of TlF is described and the influence of the inert pair discussed in relation to the massicot structured polymorph of PbO.     

Crystal Structures and Magnetic Properties of Charge-Transfer Salts: Cobaltocenium Bis(cis 1,2-diphenylethene-1,2-dithiolato)metalates (Metal = Ni,Pd, Pt)

Charge-transfer salts [Co(C₅H₅)₂][M(dpt)₂] (M = Ni and Pt; dpt = cis-1,2-diphenylethene-1,2-dithiolate) were synthesized and crystallographically characterized. [Co(C₅H₅)₂][Ni(dpt)2] crystallizes in the monoclinic space group C2/c with a = 25, 607(3) Å, b = 9.4151(11) Å, c = 14.407(4) Å, β = 101.373(22)°, V = 3405.3(10) Å₃ and Z = 4. [Co(C₅H₅)₂][Pt(dpt)₂] belongs to the triclinic space group $ {\rm P}\bar 1 $ with a = 9.4666(11) Å, b = 13.9869(12) Å, c = 14.2652(9) Å, α = 99.983(6)°, β = 90.034(7)°, γ = 109.751(7)°, V = 1747.2(3) ų and Z = 2. Both structures consist of ··· D⁺A^?D⁺A^?D⁺A^? ··· linear chains with the local C₅ axis of the eclipsed [Co(C₅H₅)₂]⁺ cation parallel to the best MS₄ plane of the [M(dpt)₂]^? anion. Magnetic susceptibility measurements show that χ_M T values of the complexes [Co(C₅H₅)₂][M(dpt)₂] (M = Ni, Pd, and Pt) remain nearly constant in the temperature range 15–300 K, but decrease rapidly with further decreasing of temperature, indicating weak antiferromagnetic interactions at low temperatures.     

镍(II)的两种配位聚合物的合成、晶体结构和性质

分别用水热法和溶液法合成了镍的两种配位聚合物[2{Ni(HO-BDC)(bpe)H₂O}]_n·n(py)·nH₂O (1) (HO-H₂BDC=5-羟基-1,3-苯二甲酸，bpe=1,2-二(4-吡啶)乙烷，py=吡啶)和[Ni(HO-BDC)(bipy)]_n·nH₂O (2) (bipy=2,2’-联吡啶)，并对它们进行了元素分析、红外光谱等表征，并用X-射线单晶衍射测定了配合物的单晶结构。配位聚合物1晶体属三斜晶系,P1空间群,晶体学数据为：a= 1.019 2(2) nm, b=1.145 5(3) nm, c=1.246 0(3) nm, α=68.377(5)°, β=67.275(12)°, γ=71.821(7)°,V=1.222 7(5) nm³, Z=1, M_r=979.26, D_c=1.330 g·cm^-3, F(000)=508, μ=0.835, R₁=0.049 4, wR₂=0.112 1；配位聚合物2晶体属单斜晶系, P2/c空间群,晶体学数据为：a= 0.861 1(2) nm, b=1.106 8(3) nm, c=1.839 4(4) nm, β=104.267(9), V=1.699 0(7) nm³, Z=4, M_r=413.00, D_c=1.615 g·cm^-3, F(000)=848, μ=1.182, R₁=0.063 5, wR₂=0.196 9。配合物1中形成了具有纳米孔的2D结构，而配合物2则是一个1D链状结构，它们分别通过氢键和π-π堆积效应形成3D结构。     

新型氮杂环卡宾银(I)配合物的合成及其晶体结构

以取代苄氯(1a~1c)为起始原料,与咪唑经氮烷基化反应制得苄基咪唑氯盐(2a~2c); 2a~2c与氧化银经原位去质子化反应合成了3种新型的氮杂环卡宾银配合物--(NHC)AgCl［NHC: 1,3-二(4-甲氧基苄基)咪唑-2-亚基(3a), 1,3-二(3-甲氧基苄基)咪唑-2-亚基(3b)］和［(NHC)AgCl]₂［NHC=1,3-二(4-氯苄基)咪唑-2-亚基(3c)］,其结构经¹H NMR, ¹³C NMR, IR,元素分析和X-射线单晶衍射表征。3a~3c单晶结构均属单斜晶系,3a为P2₁/n空间群,3b和3c为P2₁/c空间群,3a和3b为单核银配合物,3c为双核银配合物。     

Synthesis,Crystal Structures,and Antibacterial Activity of Manganese(III) Complexes with Schiff Bases

Russian Journal of Coordination Chemistry - Two new manganese(III) complexes, [MnL1(EtOH)(Acac)] (I) and [MnL2(DMF)(Esal)] · H2O (II), where L1 and L2 are the dianionic form of...     

新型离子型配合物的合成、晶体结构及性质

利用水热法合成了4-(N,N′-双(4-羧基苄基)氨基)苯磺酸（H₃L）的两个离子型配合物：[Mn(phen)₂(H₂O)₂]?(HL)?(H₂O)₄（1）和[Zn(phen)₂(H₂O)₂]?(HL)?(H₂O)₆（2, phen =邻菲罗啉）,其结构经FL、 IR、元素分析、X-射线单晶衍射、 X-射线粉末衍射和TG表征。结果表明：化合物1属于单斜晶体,P2₁/c空间群,晶胞参数a=11.997(1) Å, b=22.978(1) Å, c=18.093(1) Å, β=92.749(3)°, V=4981.8(3) ų, Z=4。化合物2属于单斜晶体,P2₁/c空间群,晶胞参数a=11.861(1) Å, b=22.816(1) Å, c=18.251(1) Å, β=92.832(5)°, V=4932.8(5) ų,Z=4。化合物2有较好的荧光性质;初始分解温度为80 ℃。      

Synthesis and Crystal Structures of Novel Copper(I) Complexes of a Phosphanylborane

The novel copper iodide clusters [Cu₃(μ‐I)(μ₃‐I)₂(PH₂BH₂·NMe₃)₃] ( 2 ) and [Cu₄(μ‐I)₂(μ₃‐I)₂(PH₂BH₂·NMe₃)₃] ( 3 ) were synthesized by treating CuI with the primary phosphine (H₂PBH₂·NMe₃). The novel features of both compounds, which have been characterized by X‐ray crystallography, are the unsymmetrical constitution of the copper iodide core due to the influence of the monodentate phosphorus ligand. This results in copper atoms with different coordination numbers within the compound. Complex 2 , the major product of the reaction, contains a distorted octahedral Cu₃I₃‐core, in which one vertex is missing. Complex 3 was isolated as a by‐product and is composed of a Cu₄I₄‐core in a distorted octahedral coordination.     

Synthesis,Crystal Structures,and Magnetic Properties of Two Copper(II) Radical Heterospin Complexes

Two heterospin complexes [Cu(NIT3Py)(cda)H₂O] · H₂O ( 1 ) and [Cu(NIT2Py)(cda)H₂O] · H₂O · CH₃OH ( 2 ) with Cu^II ions and pyridyl‐substituted nitronyl nitroxide radicals (NITxPy = 2‐(x′‐pyridyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide, x = 3, 2; H₂cda = 4‐hydroxy‐pyridine‐2,6‐dicarboxylic acid) were synthesized and characterized structurally and magnetically. The single crystal structures show that the two complexes are both two‐spin complexes, in which the different radicals make the two complexes have different hydrogen bonding interactions to form 2D and 1D supramolecular network for complexes 1 and 2 , respectively. The magnetic measurements indicate that complexes 1 and 2 both exhibit antiferromagnetic interactions between Cu^II and radicals.     

Silver(I) Complexes with Dithioether Ligands: Syntheses,Crystal Structures,and Fluorescence Properties

Two new dithioether ligands, 1,4‐bis[(phenylsulfanyl)methyl]naphthalene ( L¹ ), and 4,4′‐bis[(tert‐butylsulfanyl)methyl]biphenyl ( L² ) were synthesized and their silver(I) complexes were studied. Both Ag^I complexes, [Ag L¹ (NO₃)]_n ( 1 ) and [Ag L² (NO₃)]₂ ( 2 ), were synthesized at ambient temperature and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction analysis. Single‐crystal X‐ray analysis shows that complex 1 has a one‐dimensional helical chain structure with the neutral repeating unit [Ag(μ₂‐ L¹ )(NO₃)], whereas complex 2 has a centrosymmetrical neutral dinuclear structure. Moreover, complexes 1 and 2 are further extended into three‐dimensional supramolecular frameworks by hydrogen bonding and π–π stacking interactions, respectively. In addition, complexes 1 and 2 display strong blue emission in the solid state at room temperature.     

Synthesis,Crystal Structures,and Biological Activity of Manganese(III) Complexes Derived from BIS-Schiff Bases

Two new manganese(III) complexes, [Mn^IIIL¹(Dca)(MeOH)] (I) and [Mn^IIIL₂(N₃)₂] (II), where L¹ and L² are the dianionic form of N,N'-3,4-chlorophenylene-bis(5-methylsalicylaldimine) (H₂L¹) and N,N'-3,4-nitrophenylene-bis(5-methylsalicylaldimine) (H₂L₂), respectively, and Dca is dicyanoamide, have been synthesized and characterized. The complexes were characterized by elemental analyses, IR, UV-Vis spectra, molar conductivity, and single crystal X-ray diffraction (CIF files nos. 1054200 (I), 1054336 (II)). The Mn atoms in the structures are in octahedral coordination. In the crystal structure of complex I, molecules are linked through intermolecular O–H···N hydrogen bonds to form 1D chains running along the x axis. In both complexes, there exist π···π interactions among molecules. The complexes and the Schiff bases were assayed for antibacterial activities against three Gram-positive bacterial strains (B. subtilis, S. aureus, and St. faecalis) and three Gram-negative bacterial strains (E. coli, P. aeruginosa, and E. cloacae) by MTT method.     

两个双核铁（Ⅲ）和三足配体的配合物的合成和晶体结构

运用三足四齿配体三（2－甲基吡啶）胺（TPA）或三（2－甲基苯丙咪唑）胺（TBA）,得到两个双核铁(III)配合物，[Fe₂L₂(μ₂-O)(μ₂-p-NH₂-C₆H₄COO)]³⁺ (L = TPA, 1 和 L = TBA, 2)。两个配合物均为单斜晶系，空间群为P2(1)/c.晶胞参数 1: a = 1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º, V = 4.900(3) nm³, z = 4, F(000) = 2344, 分子量M_r = 1142.91, Dc = 1.549 g/cm³, R₁ = 0.0544, R₂ = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c = 2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm³, z = 4, F (000) = 3116, 分子量M_r = 1505.08, Dc = 1.444 g/cm³, R₁ = 0.0793, R₂ = 0.1623. 在两个双核铁(III)配合物中，中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。     

Synthesis,Properties and X-ray Crystal Structures of Nickel(II) Complexes of a Hexaazamacrotetracyclic Ligand

The complexes [N₂(L²)₂(H₂O)₄]Cl₄(1) and [Ni(L²)](ClO₄)₂ [sdot]2H₂O (2) (L = 1,3,10,12,16,19-hexaazatetracyclo [17,3,1,1 ^12.16,0^4.9]tetracosane) have been synthesized and structurally characterized by X-ray crystallography, spectroscopic and cyclic voltammetry. The crystal structure of 1 has a distorted octahedral geometry with two secondary and two tertiary amines of the macrocycle and two water molecules. In 2, the coordination geometry around the nickel atom is square-planar with four nitrogen atoms of the macrocycle. The equilibrium [Ni(L²)]²⁺ + 2H₂O &rlhar2; [Ni(L²)(H₂O)₂]²⁺ has been studied in aqueous solution over a temperature range, yielding Δ H° = -19.0 ± 0.2 kJ mol^-1 and Δ S° = - 56.0 ± 0.4 JK^-1 mol^-1. Cyclic voltammetry of the complexes give two one-electron waves corresponding to Ni(II)/Ni(III) and Ni(II)/Ni(I) processes. The electronic spectra and redox potentials of the complexes are influenced significantly by the geometry.     

Synthesis,Crystal Structures and Magnetic Properties of Copper(II) Complexes with Nitronyl Nitroxide Radicals

Two new copper(II) compounds with imino nitroxide radicals [Cu(IM‐MeImz)₂ · (SCN)] 0.5[Cu(SCN)₄] ( 1 ) and [Cu(IM‐MeImz)₂ · (SCN)]ClO₄ · H₂O ( 2 ) (IM‐meImz = 2‐(5‐methylimidazol‐4‐yl)‐4,4,5,5‐tetramethyl‐2‐imidazoline‐1‐oxyl) have been synthesized and characterized structurally and magnetically. X‐ray analysis demonstrates that complex 1 contains Cu^II ions in both square‐pyramidal and square planar coordination. There are complete charge separation into [Cu(IM‐MeImz)₂(SCN)]⁺ cations and 0.5[Cu(SCN)₄]^? anions, in a 2:1 ratio. The complex 1 was connected as a one‐dimensional polymer by intermolecular interactions. In complex 2 , the coordination around the copper atom is distorted square pyramidal and the apical position is occupied by one nitrogen atom of SCN^? anion. The 2‐D network structure was formed and arranged through intermolecular H‐bonds interactions. The complex 1 exhibits intramolecular weak ferromagnetic coupling between Cu^II ion and the radicals.     

Synthesis and Crystal Structures of Antimony(III) Complexes With a Bis(amino)silane Ligand

Bis(amino)silane bearing bulky substituents on nitrogen, LH₂ [L = Me₂Si(NDipp)₂, Dipp = 2, 6‐diisopropylphenyl] was reacted with nBuLi (ratio 1:1 and 1:2) in toluene. The Me₂Si(LiNDipp)₂ was treated with SbCl₃ in a 1:1 ratio to yield the four‐membered SiN₂Sb ring compound of composition [η²(N,N)‐Me₂Si(NDipp)₂SbCl] ( 1 ). The mono lithiated bis(amino)silane was used to synthesize the monodentate heterotetraatomic complex [(η¹‐Me₂SiNDipp)NHDippSbCl₂] ( 2 ) by the reaction with SbCl₃. The complexes were characterized by ¹H and ¹³C NMR, elemental analysis, IR, and single‐crystal X‐ray structural analysis.     

Metal Complexes of Dithiolate Ligands: 5,6-Dihydro-1,4-dithiin-2,3-dithiolato (dddt(2-)), 5,7-Dihydro-1,4,6-trithiin-2,3-dithiolato (dtdt(2-)), and 2-Thioxo-1,3-dithiole-4,5-dithiolato (dmit(2-)). Synthesis, Electrochemical Studies, Crystal and Electronic Structures, and Conducting Properties

New precursors to potentially conductive noninteger oxidation state (NIOS) compounds based on metal complexes [ML(2)](n)()(-) [M = Ni, Pd, Pt; L = 5,6-dihydro-1,4-dithiin-2,3-dithiolato (dddt(2)(-)), 5,7-dihydro-1,4,6-trithiin-2,3-dithiolato (dtdt(2)(-)), and 2-thioxo-1,3-dithiole-4,5-dithiolato (dmit(2)(-)); n = 2, 1, 0] have been investigated. Complexes of the series (NR(4))[ML(2)] (R = Me, Et, Bu; L = dddt(2)(-), dtdt(2)(-)) have been isolated and characterized, and the crystal structure of (NBu(4))[Pt(dtdt)(2)] (1) has been determined {1 = C(24)H(44)NPtS(10), a = 12.064(2) ?, b = 17.201(3) ?, c = 16.878(2) ?, beta = 102.22(2) degrees, V = 3423(1) ?(3), monoclinic, P2(1)/n, Z = 4}. Oxidation of these complexes affords the corresponding neutral species [ML(2)](0). Another series of general formula (cation)(n)()[M(dmit)(2)] [cation = PPN(+), BTP(+), and (SMe(y)()Et(3)(-)(y)())(+) with y = 0, 1, 2, and 3, n = 2, 1, M = Ni, Pd] has also been studied. All of these (cation)(n)()[M(dmit)(2)] complexes have been isolated and characterized [with the exception of (cation)[Pd(dmit)(2)] for cation = (SMe(y)()Et(3)(-)(y)())(+)]. The crystal structures of (PPN)[Ni(dmit)(2)].(CH(3))(2)CO (2) and (SMeEt(2))[Ni(dmit)(2)] (3) have been determined {2 = C(45)H(36)NNiS(10)P(2)O, a = 12.310(2) ?, b = 13.328(3) ?, c = 15.850(3) ?, alpha = 108.19(3) degrees, beta = 96.64(2) degrees, gamma = 99.67(2) degrees, V = 2373(1) ?(3), triclinic, P&onemacr;, Z = 2; 3 = C(11)H(13)NiS(11), a = 7.171(9) ?, b = 17.802(3) ?, c = 16.251(3) ?, beta = 94.39(4) degrees, V = 2068(2) ?(3), monoclinic, P2(1)/n, Z = 4} NIOS salts derived from the preceding precursors were obtained by electrochemical oxidation. Electrochemical studies of the [M(dddt)(2)] complexes show that they may be used for the preparation of NIOS radical cation salts and [M(dddt)(2)][M'(dmit)(2)](x)() compounds, but not for the preparation of (cation)[M(dddt)(2)](z)() NIOS radical anion salts. The electrochemical oxidation of the [M(dtdt)(2)](-) complexes always yields the neutral [M(dtdt)(2)](0) species. The crystal structure of [Pt(dddt)(2)][Ni(dmit)(2)](2) (4) has been determined and is consistent with the low compaction powder conductivity (5 x 10(-)(5) S cm(-)(1) at room temperature) {4 = C(20)H(8)Ni(2)PtS(28), a = 20.336(4) ?, b = 7.189(2) ?, c = 14.181(2) ?, beta = 97.16(2) degrees, V = 2057(1) ?(3), monoclinic, C2/m, Z = 2}. The crystal structures of the semiconducting NIOS compounds (BTP)[Ni(dmit)(2)](3) (5) and (SMe(3))[Ni(dmit)(2)](2) (6) have been determined {5 = C(43)H(22)PNi(3)S(30), a = 11.927(2) ?, b = 24.919(2) ?, c = 11.829(3) ?, alpha = 93.11(1) degrees, beta = 110.22(1) degrees, gamma = 83.94(1) degrees, V = 3284(1) ?(3), triclinic, P&onemacr;, Z = 2; 6 = C(15)H(9)Ni(2)S(21), a = 7.882(1) ?, b = 11.603(2) ?, c = 17.731(2) ?, alpha = 77.44(1) degrees, beta = 94.39(1) degrees, gamma = 81.27(1) degrees, V = 1563(1) ?(3), triclinic, P&onemacr;, Z = 2}. The parent compound (SEt(3))[Ni(dmit)(2)](z) (unknown stoichiometry) is also a semiconductor with a single-crystal conductivity at room temperature of 10 S cm(-)(1). By contrast, the single-crystal conductivity at room temperature of (SMeEt(2))[Pd(dmit)(2)](2) (7) is rather high (100 S cm(-)(1)). 7 behaves as a pseudometal down to 150 K and undergoes an irreversible metal-insulator transition below this temperature. The crystal structure of 7 has been determined {7 = C(17)H(13)NPd(2)S(21), a = 7.804(4) ?, b = 36.171(18) ?, c = 6.284(2) ?, alpha = 91.68(4) degrees, beta = 112.08(4) degrees, gamma = 88.79(5) degrees, V = 1643(1) ?(3), triclinic, P&onemacr;, Z = 2}. The electronic structure of (SMeEt(2))[Pd(dmit)(2)](2) (7) and the possible origin of the metal-insulator transition at 150 K are discussed on the basis of tight-binding band structure calculations.     

Synthesis,Structures and Photophysical Properties of Cationic Cyclometalated Iridium(III) Complexes Bearing N-Phenylcarbazole Group

Four cationic cyclometalated Ir^III complexes [(MeOPCz)₂Ir(bpy)]PF₆ ( 3 ), [(MeOPCz)₂Ir(dtb-bpy)]PF₆ ( 4 ), [(TFPCz)₂Ir(bpy)]PF₆ ( 5 ), and [(TFPCz)₂Ir(dtb-bpy)]PF₆ ( 6 ) were successfully synthesized using two new cyclometalated ligands 9-phenyl-3-(4-methoxypyridin-2-yl)-9H-carbazole (MeOPCz) 1 and 9-phenyl-3-(4-trifluoromethylpyridin-2-yl)-9H-carbazole (TFPCz) 2 in combination with 2,2'-bipyridine (bpy) and 4,4'-di-tert-butyl-2,2'-bipyridine (dtb-bpy) as ancillary ligands. These complexes adopt the distorted octahedral configuration, and the complexes 5 and 6 crystallize in the centrosymmetric space group C2/c. Emission wavelength of these complexes can be tuned from 583 nm to 628 nm by the substituents (methoxy, trifluoromethyl and tert-butyl groups) in ligands. All of these complexes show relatively high emission efficiencies (0.28–0.41) and short lifetimes (0.242–0.461 μs).     

正T基黄原酸根合镉(Ⅱ)的合成和晶体结构

黄原酸配合物以及它们与各种路易斯碱反应的产物得到广泛的研究[1-4].可溶性的黄原酸碱金属盐广泛用于汞、银、镉等金属的萃取分离[4-7],并且这类盐对于汞中毒具有解毒作用[8].     

半夹心结构含1，2-二硫碳硼烷的铑配合物的合成以及结构表征

室温下,18-电子体系的半夹心铑配合物Cp*Rh(L)S₂C₂(B₁₀H₁₀)(L=4-ClCH₂-C₆H₄N (2a),4-CH₃SCH₂-C₆H₄N (2b))可以通过16-电子体系的半夹心铑配合物[Cp*Rh[₂C₂(B₁₀H₁₀)]与吡啶衍生物合成。化合物通过IR、¹H NMR和元素分析进行了表征,并用X-射线单晶衍射测定了配合物2a和2b的单晶结构。