Synthesis,Spectroscopic and Structural Aspects of Mono‐ and Diorganothallium(III) Complexes of 2, 6‐Diacetylpyridine Bis(thiosemicarbazone) (H2DAPTSC) — A New Coordination Mode of the HDAPTSC— Anion

The reaction of 2, 6‐diacetylpyridine bis(thiosemicarbazone) (H₂DAPTSC) with dimethylthallium hydroxide yielded the complexes [(TlMe₂)₂(DAPTSC)] and [TlMe₂(HDAPTSC)]. The structure of [TlMe₂(HDAPTSC)], determined by X‐ray diffractometry, exhibits a hitherto unknown coordination mode of the HDAPTSC^— anion in which its deprotonated thiosemicarbazone chain coordinates one metal atom through its sulphur and hydrazinic N atoms while a second metal atom is weakly coordinated through the S atom of the undeprotonated thiosemicarbazone chain. Each thallium atom is coordinated in both ways, with the result that the [TlMe₂(HDAPTSC)] units are linked in infinite helical chains in the direction of the b axis. When reacting with diphenylthallium(III) hydroxide, H₂DAPTSC induced a dephenylation process which led to the monophenylthallium(III) complex [TlPh(DAPTSC)]. Recrystallization from acetone yielded crystals of [TlPh(DAPTSC)]·C₃H₆O in which X‐ray diffractometry showed DAPTSC^2— to be pentadentate, coordinating through its sulphur, azomethine N and pyridine N atoms. The ¹H, ¹³C and ²⁰⁵Tl NMR data of [TlPh(DAPTSC)] indicate that its solid state molecular structure persists in DMSO solution, while those of [TlMe₂(HDAPTSC)] indicate rapid alternation between coordination of the metal atom to one of the HDAPTSC^— thiosemicarbazone chains and its coordination to the other.     

Dimethylthallium(III) complexes with picolinic acid and its hydroxyl derivatives

The reaction of dimethylthallium(III) hydroxide with picolinic acid (Hpic), 3-hydroxypicolinic acid (H₂3hpic) and 6-hydroxypicolinic acid (H₂6hpic) in an aqueous/methanol mixture afforded the complexes [TlMe₂(pic)] (1), [TlMe₂(H3hpic)] (2) and [TlMe₂(H6hpic)] (3), respectively. Complex 3′, [NaTlMe₂(6hpic)₂]_n, was obtained as a minor product from a methanolic solution of 3. Compounds 1–3 were characterized by IR and Raman spectroscopy and, in the cases of 1, 2 and 3′, by single-crystal X-ray diffraction. Complex 3′ is the first example of an H6hpic⁻ heterobimetallic compound to be isolated. The ¹H and ¹³C NMR spectra of 1 and 2 are also discussed.     

New thallium(III) chloride complexes with pyridine carboxylic acids: from molecular compounds to supramolecular associations

Reactions of TlCl₃ with picolinic acid (Hpic), nicotinic acid (Hnic), isonicotinic acid (Hinic) and 3-hydroxy-picolinic acid (H3hpic) afford the isolation of new chlorothallium(III) complexes. The compounds are characterized by IR, Raman and multinuclear NMR (¹H,¹³C,²⁰⁵Tl). The molecular structures of [TlCl₂(pic)(Hpic)]·0.5H₂O (1), [TlCl₂(nic)(Hnic)] (2), [TlCl(inic)₂]·0.6C₂H₅OH (3) and [TlCl(3hpic)₂(h3hpic)] (4) are determined by single-crystal X-ray diffraction. A distorted octahedral TlCl₂N₂O₂ core containing the O,N-chelating ligands is achieved in the monomeric complex 1. The coordination polyhedron in compounds 2–4 is pentagonal bipyramidal, i.e. TlCl₂NO₄ in 2, and TlClN₂O₄ in 3 and 4, respectively. O,O′,N-Bridging ligands result in a polymer chain for 2 and a three-dimensional polymeric association in 3, while compound 4 is monomeric (O, N-and O,O-chelating ligands).     

MONO-ORGANOMERCURY AND DIORGANOTHALLIUM DERIVATIVES OF THIOHYDANTOIN AND 5-(BENZYLIDENE)-2-THIOHYDANTOIN: THE CRYSTAL STRUCTURE OF DIMETHYL-[5-(BENZYLIDENE)-2-THIOHYDANTOINATO]-THALLIUM(III)

Abstract

The complexes [TlR₂(Td)], [TlR₂(BTd)], [HgR(Td)] and [HgR(BTd)] (R = Me, Ph; HTd = thiohydantoin; HBTd = 5-(benzylidene)-2-thiohydantoin) were prepared by reacting the appropriate ligand with the appropriate diorganothallium hydroxide or mono-organomercury acetate. They have been studied in the solid state (by vibrational spectroscopy and mass spectrometry) and in solution (by using NMR). In addition, the crystal structure of [TlMe₂(BTd)] has been determined by X-ray diffraction. The crystals have a polymeric structure in which each thallium atom is coordinated to the two methyl C atoms, the S and N atoms of one BTd ligand. the S atom of another and the O atom of a third. The coordination modes of the two ligands in the other complexes are discussed on this basis in the light of spectroscopic data.     

金属离子导向自组装的磺酰化对氨基苯甲酸配合物的合成与表征

用普通溶液法合成了4个配合物：[Cu（Ts-p-aba）₂（phen）（H₂O）]_n（1）、[Zn（Ts-p-aba）₂（phen）（H₂O）]·H₂O（2）、[Pb（Ts-p-aba）₂（phen）]2（3）和{[Pb（Ts-p-aba）（phen）（NO₃）]（DMF）}_n（4）（Ts-p-aba=N-对甲苯磺酰对氨基苯甲酸,phen=菲咯啉,DMF=N,N-二甲基甲酰胺）。X-射线单晶衍射结果表明：配合物1和2均为三斜晶系,P1空间群。配合物1的中心铜离子处于变形的八面体配位环境,并通过配体N-对甲苯磺酰对氨基苯甲酸扩展为一维直线链结构;配合物2是个单核分子,锌离子的配位多面体为四角锥体。配合物3和4均为单斜晶系,P2₁/c空间群。配合物3由配体N-对甲苯磺酰对氨基苯甲酸桥联成二聚体,铅离子处于变形的八面体配位环境;配合物4是具有一维链状结构的配位聚合物,铅离子处于变形的一面心八面体配位环境。另外,对4个配合物的热稳定性、电化学性能和荧光性质也进行了研究。     

金属离子导向自组装的磺酰化对氨基苯甲酸配合物的合成与表征

用普通溶液法合成了4个配合物:[Cu(Ts-p-aba)2(phen)(H2O)]n(1)、[Zn(Ts-p-aba)2(phen)(H2O)]·H2O(2)、[Pb(Ts-p-aba)2(phen)]2(3)和{[Pb(Ts-p-aba)(phen)(NO3)](DMF)}n(4)(Ts-p-aba=N-对甲苯磺酰对氨基苯甲酸,phen=菲咯啉,DMF=N,N-二甲基甲酰胺)。X-射线单晶衍射结果表明:配合物1和2均为三斜晶系,P1空间群。配合物1的中心铜离子处于变形的八面体配位环境,并通过配体N-对甲苯磺酰对氨基苯甲酸扩展为一维直线链结构;配合物2是个单核分子,锌离子的配位多面体为四角锥体。配合物3和4均为单斜晶系,P21/c空间群。配合物3由配体N-对甲苯磺酰对氨基苯甲酸桥联成二聚体,铅离子处于变形的八面体配位环境;配合物4是具有一维链状结构的配位聚合物,铅离子处于变形的一面心八面体配位环境。另外,对4个配合物的热稳定性、电化学性能和荧光性质也进行了研究。     

{Bis­[2‐(2‐oxido‐1‐naphthylmethylidene­amino)­phenyl] disulfide}chloroiron(III)

The crystal structure of the title compound, {bis­[2‐(2‐oxido‐2‐naphthyl­idene­amino)­phenyl] di­sulfide‐κ⁵O,N,S,N′,O′}chloroiron(III), [FeCl(C₃₄H₂₂N₂O₂S₂)], has been determined. The structure consists of monomeric iron(III) complexes with distorted octahedral coordination. The di­sulfide functions as a pentadentate ligand and the Fe^III atom is coordinated through two N, two O and one S atom, and one chloride ion. The distance between the second S atom and the Fe^III atom is a non‐bonding 3.8473 (14) Å.     

Synthesis,spectral characterization of the zinc(II) mixed-ligand complexes of N(4)-allyl thiosemicarbazones and N,N,N′,N′-tetramethylethylenediamine,and crystal structure of the novel [ZnL2(tmen)] compound

Mixed-ligand zinc complexes with N,N,N′,N′-tetramethylethylenediamine (tmen) and R-salicylaldehyde N(4)-allyl thiosemicarbazones (R: 3-OCH₃ (L₁), 5-Br(L₂)), [ZnL_1,2(tmen)], were synthesized and the complexes were characterized by elemental analysis, atomic absorption spectrometer, magnetic susceptibility, molar conductivity, electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) mass spectra and IR, UV–Vis, ¹H NMR and ¹⁵N spectroscopies. Crystal of [ZnL₂(tmen)] have a slightly distorted square pyramid involving O, N, S atoms of thiosemicarbazone and one N atom of tmen in basal plane and the other N atom of tmen in apex of the pyramid. The non-coordinated allyl group is disordered.     

Coordination of water to organolead(IV) nitrates: The examples of [PbPh2(NO3)2(H2O)2] and [PbMe3(NO3)(H2O)]

The compound [PbPh₂(NO₃)₂(H₂O)₂] was synthesized and characterized by spectroscopic methods (IR; ¹H, ¹³C and ²⁰⁷Pb NMR) and mass spectrometry. An X-ray diffraction study showed that the crystal is a supramolecular tridimensional network of hydrogen-bonded PbPh₂(NO₃)₂(H₂O)₂ units in which the Pb atom is octacoordinated and adopts a distorted hexagonal bipyramidal geometry, with four O (bidentate nitrate) and two O (water) atoms in equatorial positions and two C-phenyl atoms in axial positions. The crystal of [PbMe₃(NO₃)(H₂O)], obtained as a byproduct in the synthesis of PbMe₂(NO₃)₂, contains chains of hydrogen-bonded PbMe₃(NO₃)(H₂O) units in which the Pb atom is pentacoordinated with a slightly distorted trigonal bipyramidal environment. In this arrangement the three C-methyl atoms are equatorial and the O atoms from the monodentate nitrate and the water molecule are axial.     

基于8-羟基喹啉与d10金属原位合成的双核配合物的合成、晶体结构及其光致发光性质

利用8-羟基喹啉原位反应,通过溶剂热方法制备出3种新颖的d~(10)配合物[M_2(HL)_3]NO_3·H_2O (M=Cd (1),Zn (2,3)),H_2L为1,1-(7,7′-二-(8-羟基喹啉))。单晶结构表明,3种配合物有着相同的带正电荷的结构单元[M_2(HL)_3]~+,但由于客体分子所处空间位置的不同表现为不同的空间结构,配合物1和3结晶于六方晶系(P6_3/m),配合物2结晶于三方晶系(R3)。中心金属离子以六配位的模式与来自HL-配体上的3个氧原子和3个氮原子形成一个轻微扭曲的八面体几何构型。存在于HL-配体与客体分子(NO_3~-,H_2O)间大量的弱作用力在结构空间堆积上起到了重要的作用。3种配合物均具有良好的热稳定性和绿色荧光发射性质。同时,通过从配合物1中提取出原位生成的配体H_2L,首次报道了其蓝色荧光发射性质。     

Crystal structure of Ir(acac-O,O)2(acac-C3)(pyridine)

Ir(acac-O,O)₂(acac-C³)(pyridine), 1 is synthesized, and its crystal structure is determined by single crystal X-ray diffraction. In the complex, the central Ir(III) atom displays a distorted octahedral geometry wherein the equatorial positions are occupied by four oxygen atoms of two acetylacetone ligands, and the apical positions are coordinated by a carbon atom of one acetylacetone ligand and a nitrogen atom of pyridine.     

Syntheses, structures and properties of two new neodymium complexes with N-P-acetamidobenzenesulfonyl-glycine acid

Two new neodymium complexes, [Nd₂(abglyH)₆(2,2′-bipy)₂(H₂O)₂] · 4H₂O 1 and {[Nd(abglyH)₃(H₂O)₂] · (4,4′-bipy) · 7H₂O}_n 2 (abglyH₂ = N-P-acetamidobenzenesulfonyl-glycine acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and their structures have been measured by X-ray crystallography. In 1, nine-coordinated Nd(III) ions are bridged by two syn–syn bidentate and two tridentate bridging carboxylate groups from four different abglyH⁻ anions to form dinuclear motifs, which are further connected into a 3-D supramolecular framework via hydrogen bonds between the binuclear motifs and the uncoordinated water molecules. In 2, eight-coordinated Nd(III) ions are linked by six carboxylate groups adopting a syn–syn bidentate bridging fashion to form a 1-D inorganic–organic alternating linear chain. These polymeric chains generate microchannels extending along the a direction, and these cavities are occupied by discrete tetradecameric water clusters, which interact with their surroundings and finally furnish the 3-D supramolecular network via hydrogen bonds. At the same time, π–π stacking interactions between benzene rings from abglyH⁻ anions also play an important role in stabilizing the network.     

(η2-Allyl­ammonium)­aqua­bis­(sulfam­ato-N)copper(I)

The Cu^I atom in the title complex, [Cu(NH₂SO₃)₂(C₃H₈N)(H₂O)], is coordinated by the C=C bond of the allyl­ammonium cation, two N atoms of the sulfamate anions and the O atom of the H₂O mol­ecule in the apical position. Thus, the central atom is in a distorted trigonal–pyramidal environment. Strong N—H⃛O and O—H⃛O contacts connect separate moieties of the complex into a three-dimensional framework. The title compound is representative of hitherto unknown copper(I)–sulfamate π-complexes.     

Binary and ternary complexes involving manganese(II), 2,2’-bipyridine and halide or thiocyanate ions inN,N-dimethylformamide

Ternary complexation involving the manganese(II) ion, 2,2’-bipyridine (bipy), and halide (chloride, bromide) or pseudohalide (thiocyanate) ions has been studied by precise titration calorimetry inN,N -dimethylformamide (DMF) at 298K. All the titration curves are explained well in terms of formation of mononuclear complexes of the type [MnX_m(bipy)_n](^2-m) + (X = CI, Br or SCN), and the formation of [MnCl(bipy)]⁺, [MnCl₂(bipy)], [MnCl(bipy)₂]⁺ and [MnCl₂(bipy)₂] has been established in the chloride system, [MnBr(bipy)]⁺, [MnBr₂(bipy)], [MnBr(bipy)₂]⁺ in the bromide system, and [Mn(NCS)(bipy)]⁺, [Mn(NCS)₂(bipy)], [Mn(NCS)₃(bipy)]^-, [Mn(NCS)(bipy)₂]⁺, and [Mn(NCS)₂(bipy)₂] in the thiocyanate system. The data were analyzed on the basis of the thermodynamic parameters for the binary Mn^lIbipy and Mn^II-X (X = Cl, Br and SCN) systems, the latter being determined in previous work. The formation constants, reaction enthalpies, and entropies of the ternary complexes were extracted. The thermodynamic parameters thus obtained are discussed in comparison with those of the corresponding systems of other transition metal(II) ions.     

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.     

(Dibenzyl sulfoxide‐κO)bis(1,3‐diphenylpropane‐1,3‐dionato‐κ2O,O′)dioxouranium(VI)

In the title compound, [UO₂(C₁₅H₁₁O₂)₂(C₁₄H₁₄OS)], the U^VI atom is coordinated by seven O atoms in a distorted pentagonal–bipyramidal geometry. Both di­phenyl­propane‐1,3‐dionate systems are nearly planar. The sulfoxide moiety is in a distorted tetrahedral geometry, while its two aromatic rings are nearly orthogonal to one another. The crystal packing is stabilized by two bifurcated hydrogen‐bonding interactions involving both uranyl O atoms.     

N-(1-亚氨基乙基)乙脒铂配合物合成、结构和性质

四氯合铂酸钾分别与邻、间、对磺基苯甲酸在乙腈和水中利用水热合成获得了3个铂的N-(1-亚氨基乙基)乙脒配合物:[Pt(NIA)₂]·(2-sb)·2H₂O(1),[Pt(NIA)₂]·(3-sb)·3H₂O(2)和[Pt(NIA)₂]·(1,4-dsb)·2H₂O(3)(NIA=N-(1-亚氨基乙基)乙脒,2-sb^2-=2-磺基苯甲酸二价阴离子、3-sb^2-=3-磺基苯甲酸二价阴离子、1,4-dsb^2-=1,4-二磺基苯二价阴离子)。合成过程中发生了乙氰三聚以及4-sb^2-转变为1,4-dsb^2-的反应。对配合物进行了元素分析、红外、紫外、荧光、热重和粉末X射线衍射表征,并利用单晶X射线衍射测定了配合物的晶体结构。3个配合物为阳离子-阴离子物种,阳离子为[Pt(NIA)₂]²⁺,中心金属离子四配位平面构型;阴离子与阳离子、水形成氢键,组成一个三维网络结构,但3个配合物的氢键模式不同。配合物在热稳定性、荧光性质上有一定差异。     

[CuCl3(H2O)]− complexes aggregated to form hydrate columns in methyl‐substituted pyridinium or piperidinium salts

1,2,3‐Trimethylpyridinium aquatrichloridocuprate(II), (C₈H₁₂N)[CuCl₃(H₂O)], (I), 3,4‐dimethylpyridinium aquatrichloridocuprate(II), (C₇H₁₀N)[CuCl₃(H₂O)], (II), and 2,3‐dimethylpyridinium aquatrichloridocuprate(II), (C₇H₁₀N)[CuCl₃(H₂O)], (III), exhibit the same fundamental structure, with (I) and (II) isomorphous and with the unit‐cell constants of (III) similar to the reduced unit‐cell constants of (I) and (II). The distorted square‐planar [CuCl₃(H₂O)]⁻ complex [mirror symmetric in (I) and (II)] forms two semicoordinate Cu...Cl bonds to a neighboring complex to produce a dimer with 2/m symmetry [only inversion symmetry in (III)]. The semicoordinate Cu...Cl bond length of the dimer shows significant elongation at 295 K compared with that at 100 K, while the coordinate Cu—Cl bond lengths are slightly contracted at 295 K compared with those at 100 K. The inorganic dimers are linked by eight hydrogen bonds to four neighboring dimers to establish a checkerboard network layer in the ab plane, with voids between the dimers that accommodate, on both sides, inversion‐related organic cation pairs. The organic cations are required by mirror‐plane symmetry to be disordered in (I) and (II). The organic cations and [CuCl₃(H₂O)]⁻ complexes are nearly coplanar and tilted out of the layer plane to establish a hybrid organic–inorganic layer structure parallel to (202) [(11) in (III)], with hydrate columns (defined by water molecules) and hydrophobic columns (defined by methyl groups) parallel to each other [and along the 2₁ axes in (I) and (II)]. In 1,1‐dimethylpiperidinium aquatrichloridocuprate(II), (C₇H₁₆N)[CuCl₃(H₂O)], (IV), the bulkier organic cation prevents semicoordinate bonding between complexes, which are hydrogen bonded side‐to‐side in zigzag chains that place water molecules in columns along half of the 2₁ axes.     

Coordinate Structures of PrIII, GdIII, TmIII, and YbIII Complexes with Nitrilotriacetic Acids

The crystal and molecular structures of the [Pr^III(nta)(H₂O)₂]·H₂O (nta = nitrilotriacetic acids), K₃[Gd^III(nta)₂(H₂O)]·6H₂O, and K₃[Yb^III(nta)₂]·5H₂O complexes have been determined by single-crystal X-ray structure analyses. In [Pr^III(nta)(H₂O)₂]·H₂O, the Pr^IIINO₈ part forms a nine-coordinate pseudo-monocapped square antiprismatic structure in which one N and three O atoms are from one nta ligand in the same molecule, three O atoms from another nta ligand in the neighboring molecule and two O atoms from two coordinate water molecules. In K₃[Gd^III(nta)₂(H₂O)]·6H₂O, the [Gd^III(nta)₂(H₂O)^3- complex anion has a nine-coordinate pseudo-monocapped square antiprismatic structure in which each nta acts as a tetradentate ligand with one N atom of the amino group and three O atoms of the carboxylic groups. In K₃[Yb^III(nta)₂]·5H₂O, each nta also acts as a tetradentate ligand with one N atom of amino group and three O atoms of the carboxylic groups, but the [Yb^III(nta)₂ ^3- complex anion has an eight-coordinate structure with a distorted square antiprismatic prism. All the results including those for [Tm^III(nta)(H₂O)₂]·2H₂O confirm the inferences on the coordinate structures and coordination numbers of rare earth metal complexes with the nta ligand.     

Two yttrium(III) coordination compounds containing a3-ptz or atza [a3-ptz = 5-[N-acetato(3-pyridyl)]tetrazole; atza = 5-aminotetrazole-1-acetato]

Two yttrium(III) coordination compounds, [Y(a3-ptz)₂(H₂O)₅]Cl?·?4H₂O (1) and [Y(atza)₂(H₂O)₂(CH₃OH)]Cl (2) [a3-ptz?=?5-[N-acetato(3-pyridyl)]tetrazole; atza?=?5-aminotetrazole-1-acetato], have been synthesized. Single-crystal X-ray diffraction analysis reveals that 1 has a distorted monocapped square-antiprism coordination geometry around Y^III. Complex 2 is a distorted pentagonal bipyramid with coordination from four atza ligands, two waters, and one methanol; the coordination of atza in 2 leads to its 1-D polymeric chain structure. 1 and 2 are self-assembled to form 3-D supramolecular structures through hydrogen bonds. The luminescence properties of 1 and Ka3-ptz were investigated at room temperature in the solid state.