R、S-三[N-(邻-氧α-萘亚甲基)-α-苯乙胺]合钴的合成、晶体结构及分子绝对构型

合成了R,S一三[N-(邻-氧α-萘亚甲基)-α-苯乙胺]合钴。x射线单晶衍射衍射测定了晶体结构及分子的绝对构型。晶体属正交晶系,D_2~4-P2_12_12_1空间群,晶胞参数:α=12.587(3),b=14.166(3),c=25.652(14)(?),v=4574.2(?)~3,z=4。用重原子法及差值Fourier合成解出结构,最后的R值为0.074。利用Co~( )对CuKa反常散射测定了分子的绝对构型。Co~( )为六配位,d~2sp~3杂化近正八面体构型。     

THE CRYSTAL AND MOLECULAR STRUCTURE OF PRASEODYMIUM(III) 2-FURANCARBOXYLATE DIHYDRATE

Abstract

Praseodymium(III) 2-furanocarboxylate dihydrate is monoclinic, space group P2₁/c. The lattice parameters area a = 10.349(2). b = 16.727(3), c = 9.458(1) Å, β = 92.61(1)°. The crystal structure was solved and refined by a full-matrix least-squares method to R = 0.034 and R_w = 0.039 from 2333 reflections. Carboxylic ions bond in the complex as bidentates and as bi- and terdentate-bridging ligands. The water molecules bond to the metal. The coordination number of the praseodymium atom is nine. The coordination polyhedron is intermediate between a distorted tricapped trigonal prism and a distorted monocapped square antiprism.     

SYNTHESIS AND CRYSTAL STRUCTURE OF OXAMIDATO-BRIDGED BINUCLEAR COPPER(II) COMPLEXES

Abstract

The compounds [Cu(oxpn)] (1), [(bpy)(H₂O)Cu(μ-cis-oxpn)Cu(H₂O)] · 2NO₃ · 2H₂O (2) and [(Him)(NO₃)Cu(μ-trans-oxpn)Cu(Him)(NO₃)] (3), where oxpn is the dianion of N,N′-bis(3-aminopropyl)oxamide, bpy is bipyridine and Him is imidazole, were prepared and characterized by elemental analysis and IR spectra. Complex (2) was also studied by thermochemical analysis and its structure determined by X-ray crystallography. The structure of complex (2) consists of binuclear copper(II) molecules in which the copper(II) atoms are bridged by an oxamidato group in the cis conformation resulting a copper-copper distance of 5.21 Å. Both copper(II) ions are in square-pyramidal surroundings with almost coplanar basal planes and a water molecule occupying the apical positions. The N atoms of the oxamidato moiety are trigonal. Two lattice water molecules together with the two coordinated ones hydrogen bond with nitrate ions.     

吡啶—2,6二甲酸铕配合物的晶体结构研究

合成了吡啶—2,6二甲酸铕配合物Na_3[Eu(DPC)_3]·14H_2O(DPC为吡啶—2,6二甲酸根)晶体,对该配合物的红外光谱、荧光光谱、热谱及电导等性质进行了研究.单晶结构分析表明,Na_3[Eu(DPC)_3]·14H_2O属三斜晶系,空间点群P(?).晶胞参数:a=1.1000(10),b=1.7268(22),c=1.0314(14)nm;α=102.53(11)°,β=107.05(8)°,γ=74.53(9)°;V=1.7845nm~3;Z=2;D_c=1.80g/cm~3;μ=18.9cm~(-1).吡啶—2,6二甲酸以三齿配位,铕的配位数为9,其配位多面体为畸变的三帽三角棱柱体.     

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.     

SYNTHESIS AND CHARACTERIZATION OF THE FORMAL Ni(III) AND Cu(III) COORDINATION COMPLEXES OF THE NEW 1,2-DITHIOLENE, 1,4-BUTANEDIYLDITHIOETHYLENE-1,2-DITHIOLATE

Abstract

The new 1,2-dithiolene, 1,4-butanediyldithioethylene-1,2-dithiolate, has been isolated. In addition, new monoanionic bis-complexes with nickel and copper have been prepared and isolated. The formal Ni(III) complex crystallizes in the orthorombic space group, P_bca, with a = 9.762(9), b = 12.53(2), and c = 23.166(3) Å, with 4 molecules in the unit cell. The structure was refined to an R = 9.01% (R_w = 8.95%). The formal Cu(III) complex crystallizes in the monoclinic space group, C_2/c, with a = 25.567(6), b = 8.011(3), c = 14.504(3) Å, and β = 106.17(2)° with 4 molecules in the unit cell. The structure refined to R = 4.2% with R _w = 4.3%. Comparisons to similar 1,2-dithiolenes suggest this ligand produces only modest structural and electronic differences when compared to the 1,3-propanediyldithioethylene-1,2-dithiolate complexes. The oxidation (to a neutral complex) and reduction (to a dianion) for the Ni(III) and Cu(III) complexes show large differences from those of maleonitriledithiolate. Other physical data are presented as well.     

STEREOCHEMISTRY OF COMPLEXES WITH N-ALKYLATED AMINO ACIDS. VIII. CRYSTAL STRUCTURE AND CONFORMATIONAL ANALYSIS OF AQUABIS(L-N,N-DIMETHYLTHREONINATO)COPPER(II) DIHYDRATE

Abstract

The structure of blue, monoclinic (space group P2₁) crystals of aquabis(L-N,N-dimethylthreoninato)copper(II) dihydrate was determined by X-ray diffraction and refined to R = 0.030. The coordination around the copper(II) atom is distorted square-pyramidal with threonine N and O atoms in trans orientations (Cu-O 1.930(3) and 1.926(3)Å, Cu-N 2.042(3) and 2.055(3)Å, O-Cu-O 163.9, N-Cu-N 164.0°) and apical water (Cu-O(W) 2.206 Å). The shape of the coordination polyhedron was reasonably well reproduced with molecular mechanics calculations, yielding root-mean-square deviations of ten valence angles around copper to 4.5°. The calculated strain energy of the crystal conformation is about 21 kJ mol^? higher than the energy of the most stable conformer. This was tentatively attributed to the additional stabilization of molecular conformation by intermolecular hydrogen bonds in the solid state.     

CRYSTAL STRUCTURE AND MAGNETIC MEASUREMENTS OF CIS-DICYANO-BIS (1,10-PHENANTHROLINE)IRON(III) SULFATE

Abstract

The structure of the solvatochromic complex cis-dicyano-bis(1,10-phenanthroline)iron(III) sulfate dihydrate was determined by X-ray diffraction. The complex crystallized in a compressed octahedral conformation with the cyanide ligands cis-bonded. The unit cell contains enantiomeric pairs of the compound with a network of sulfate ions and water molecules stabilized by hydrogen bonding. The magnetic moments of the perchlorate salt dissolved in both water and nonaqueous solvents were probed and found to be in accord with a solvated, low spin [Fe(III)(phen)₂(CN)₂]⁺ ion, (μ_exp = 2.0–2.6 BM, 298K), showing no dependence on the empirical solvent parameters AN, DN, E_T(30) and π?.     

SYNTHESIS,CHARACTERIZATION, AND REPRESENTATIVE CRYSTAL STRUCTURE OF LIPOPHILIC PLATINUMII (HOMOPIPERAZINE)CARBOXYLATE COMPLEXES

Abstract

A series of new lipophilic platinum(II) complexes of the type [Pt(HPIP)L₂] and [Pt(HPIP)L] (where HPIP = homopiperazine; L = acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, laureate, tridecanoate, myristate, pentadecanoate, palmitate, or heptadecanoate; and LL = oxalate, or tartronate) were synthesized and characterized by elemental analysis, IR, ¹³CNMR, and ¹⁹⁵Pt NMR. In addition, the crystal structure of a representative complex [Pt^II(HPIP)(pentadecanoate)₂], was determined by X-ray diffraction. The crystals were monoclinic, space group P2₁/c, with a = 28.212(6)Å, b = 3.661(3)Å, c = 10.218(2)Å, and Z = 4. A total of 3940 reflections were collected, and the structure refined to R1 = 0.0522 and wR2 = 0.1333. The slightly distorted square plane of the platinum included the amino groups of the HPIP molecule in cis positions and oxygens from two monodentate pentadecanoates. The HPIP molecule was in a boat conformation and formed five- and six-member chelating rings with platinum. Together, these molecules formed an intricate network of intermolecular hydrogen bonds that held the crystal lattices together.     

SOLVATION OF ALUMINIUM(III) AND IRON(III) COMPLEXES OF HYDROXAMATE LIGANDS IN ALCOHOL-WATER MIXTURES

Abstract

Solubilities and derived transfer chemical potential trends are reported for several tris(hydroxamato)-aluminium(III) and iron(III) complexes in methanol-water and in t-butylalcohol-water solvent mixtures. These trends are discussed in terms of hydrophilic and hydrophobic characteristics of the peripheries of these complexes.     

SYNTHESES,CRYSTAL STRUCTURES AND ELECTRONIC SPECTRA OF MIXED-LIGAND ZINC(II) COMPLEXES WITH DIIMINES AND DITHIOLATES

Abstract

Three zinc(II) complexes, [Zn(bipy)(dmit)]₂ (1), [Zn(phen)(dmit)]₂ (2) and Zn(py)(mnt) (3), where bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline, py = pyridine, H₂dmit = 4,5-dimer-capto-1,3-dithiol-2-thione, mnt = maleonitriledithiolate, have been synthesized and their crystal structures determined. Complex 1 is monoclinic, space group P2₁/c, with a = 11.570(3), b = 9.137(3), c = 15.051(6)Å, β = 109.56(2)°, Z = 2 and was refined to R ₁ = 0.039. Complex 2 is monoclinic, space group P2₁/n, with a = 9.363(2), b = 13.732(3), c = 12.767(3), β = 94.06(3)°, Z = 2 and was refined to R ₁ = 0.038. Complex 3 is orthorhombic, space group P2₁2₁2₁, with a = 8.621(3), b = 10.546(4), c = 16.848(2), Z = 4 and was refined to R ₁ = 0.040. IR and electronic absorption spectra were investigated.     

CRYSTAL STRUCTURE,SPECTRAL AND MAGNETIC BEHAVIOR OF COPPER(II)(5-CHLOROSALICYLATO)2 (AQUA)2

Abstract

The synthesis and characterization of Cu(5-Clsal)₂(H₂O)₂ (5-Clsal = 5-chlorosalicylate) are reported. Characterization of the compound was based on elemental analysis, electronic and EPR spectra, and magnetic susceptibility measurement over a temperature range 93–239 K.

An X-ray analysis of Cu(5-Clsal)₂(H₂O)₂ was carried out, showing a polymeric chain of copper(II) atoms bridged by pairs of water molecules with Cu-O(bridge) bond lengths of 1.970(2) and 2.718(2)Å. The coordination sphere about each copper(II) atom is completed (on the X-axis) by a trans-pair of unidentate 5-chlorosalicylate anions. The bridging oxygen atoms arrange a planar Cu₂O₂ rhombus. The relationship between degree of distortion and g-values from EPR spectra is also discussed.     

STRUCTURES AND PROPERTIES OF COPPER(II) COMPLEXES WITH IMINODIACETATO AND IMIDAZOLE OR RELATED LIGANDS. I. CRYSTAL STRUCTURE OF AQUA(IMIDAZOLE) (IMINODIACETATO)COPPER(II) MONOHYDRATE AND (IMIDAZOLE)(N-CARBOXYMETHYL-D,L-THREONINATO)COPPER(II)

Abstract

The crystal structures of two mixed-ligand copper(II) complexes having iminodiacetate(2-) (IDA) or N-carboxymethyl-D,L-threoninato(2-) ion (CMT) as terdentate ligands and imidazole (ImH) as an N-heterocyclic ligand are reported. Both compounds crystallize in the orthorhombic system, space group Pbca with Z = 8. Aqua(imidazole)(iminodiacetato)copper(II) monohydrate (I,R = 0.065, R _w = 0.075) consists of H₂O molecules and [Cu(IDA)(ImH)(H₂O)] complex units in a hydrogen bonding network. The structure of imidazole(N-carboxymethyl)-D,L-threoninatocopper(II) (IV, R = 0.066, Rω 0.078) is built up of hydrogen bonded polynuclear chains. In both compounds the Cu(II) ion exhibits a flattened and distorted square-based pyramidal coordination, with a terdentate aminoacidate ion, IDA or CMT, and one ImH ligand at the base and H₂O (in I) or the oxygen atom of the OH side chain from one adjacent CMT ion (in IV) as the fifth apical ligand. The nearly coplanar conformation of the two five-membered chelate rings in I and IV is discussed in connection with the known structure of corresponding aquacomplexes (with H₂O instead of ImH) and the ability of terdentate aminoacids to give ternary Cu(II) complexes having two N-heterocyclic donors (2 ImH or one 2,2′-bipy) per Cu(II) atom.     

NUCLEOPHILIC ADDITION OF WATER AND ETHANOL TO COORDINATED DI-(2-PYRIDYL)KETONE IN RHENIUM(V) AND TECHNETIUM(V) COMPLEXES. THE CRYSTAL STRUCTURE OF DICHLORO(HYDROXY-DI-(2-PYRIDYL)METHOXIDE)OXORHENIUM(V)

Abstract

Complexes of general formula MOCl₂[(C₅H₄N)₂C(O)(OR)] (M = Re, Tc; R = H, Et) were prepared by the reaction of trans-ReOCl₃(PPh₃)₂ and (n-Bu₄N)[TcOCl₄] with di-(2-pyridyl)ketone (DPK) in ethanol (R = Et) under nitrogen and in benzene, containing trace amounts of water, in air (R = H). The compounds were characterized by elemental analysis, vibrational, optical and proton nuclear magnetic resonance spectroscopy. The evidence suggests that the coordinated DPK ligand has undergone addition of water and ethanol at the carbonylic carbon atom, and that the (C₅H₄N)₂C(o)(OR) moiety acts as a uninegative, terdentate N,O,N-donor ligand. The X-ray crystal structure of the complex ReOCl₂[(C₅H₄N)₂C(O)(OH)] is also reported. Crystal data: C₁₁H₉N₂O₃Cl₂Re, orthorhombic, space group Pcca; a = 14.935(5), b = 11.896(8), c = 14.937(11)Å, and U = 2653.8 (2.7)ų to give Z = 8 for D _calc = 2.37 g cm_?3. The structure was solved by Patterson and Fourier methods and refined by least-squares methods to R = 0.076. The complex has an Re = O bond distance of 1.67(2)Å, and a deprotonated diolate oxygen of the ligand is coordinated in the position trans to the oxo group.     

[La(CH_2ClCOO)_2(NO_3)(phen)(H_2O)]_n的合成和晶体结构

合成了混合阴离子配合物［Ｌａ（ＣＨ２ＣｌＣＯＯ）２（ＮＯ３）（ｐｈｅｎ）（Ｈ２Ｏ）］ｎ。配合物经元素分析、ＩＲ、ＤＴＡＴＧ和ＵＶ等表征。用Ｘ射线单晶结构分析解析了标题配合物的晶体结构，三斜，空间群Ｐ１，晶胞参数为ａ＝１０５３３（２），ｂ＝１３１３６（３），ｃ＝７７７６（１），α＝９６５９（１）°，β＝９５７６（１）°，γ＝１０８４２（２）°，Ｖ＝１００３３（３）３，Ｚ＝２，Ｄｃ＝１９４０ｇ／ｃｍ３，Ｆ（０００）＝５７２，μ（ＭｏＫα）＝２４３６ｃｍ－１。     

DIRECT SYNTHESIS AND CRYSTAL STRUCTURE OF DIIODOETHYLENDIAMINELEAD(II) DIMETHYLSULFOXIDE

Abstract

A direct method of obtaining PbEnI₂.DMSO is reported. The crystal structure of the compound was determined by X-ray techniques. PbEnI₂.DMSO is triclinic, space group P 1, C₄H₁₄I₂N₂PbS, a=10.225(3), b=10.132(3), c=6.900(2) Å; α=90.83(2), β=88.30(2), γ=106.35(4)°; V=685.6(4) ų; z=2, calculated density 2.92 gcm^?3. Neutral PbEnI₂ complexes are associated with DMSO molecules via H-bonds. The lead(II) ion is covalently linked with a chelated En molecule (Pb-N 2.46–2.48 Å) and I^? anions (Pb-I 3.087–3.343 Å). Covalently bonded atoms form an umbrella-like coordination Pb(II) polyhedron. The side containing the lone electron pair of the lead(II) ion has coordination completed by two I^? anions of neighbouring molecules with the Pb-I 3.621–3.627 Å.     

STUDIES OF THE STRUCTURE OF VANADIUM(III) COMPLEXES WITH NITROGEN CONTAINING LIGANDS IN ALCOHOLIC SOLUTIONS. I. COMPLEXES OF V(III) WITH AZOLES

Abstract

Anhydrous vanadium trichloride reacts with azoles in low concentrated ethyl alcohol solution of V(III) to produce 1:1 electrolytic complexes of the type [V (azole)₄Cl₂]⁺. Studies of the visible spectra of all the above complexes demonstrate that the vanadium(III) is octahedrally co-ordinated. The room temperature magnetic moments of the complexes (～ 2.8 B.M.) are consistant with the presence of two unpaired electrons per vanadium atom. At higher concn. of V(III) the polynuclear violet-red complexes probably are formed.     

SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF BIS (2-AMINOMETHYLAZIRIDINE)NICKEL(II) PERCHLORATE

Abstract

The structure of the big (2-aminomethylaziridine = azida)nickel(II) complex was determined by X-ray diffraction methods. The compound, [Ni(azida)₂](C1O₄)2, crystallizes in the triclinic space group P1, Z=l, with a = 7.3545(4), b = 8.5235(5), c = 6.2156(4)Å, α= 101.871(6). β = 103.217(6), γ= 111.283(4)°, and V= 335.07(5) ų. The crystal shows discrete centrosymmetncal [Ni(azida)]²⁺ units in which azida acts as bidentate chelating ligand through N aziridine and N amino atoms. Thus, Ni has a four-coordinate square-planar geometry with four nitrogens of azida. The aziridine ring is almost perpendicular to the coordination plane. The dihedral angle between the aziridine plane and the coordination plane is 75.28°.     

以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

基于铁和锰的双核配合物在生物氧化还原过程中的重要作用及在化学的氧化还原过程中可能做为催化剂的应用前景,本文合成了两个新的以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)双核和Mn(Ⅱ)双核配合物:[Fe_2(phen)_4(μ-CA)](ClO_4)_4·2H_2O(1)和[Mn_2(phen)_4(μ-CA)](ClO_4)_2·3H_2O(2)(phen=1,10菲咯啉;CA=氯醌酸二价阴离子)。经元素分析、IR、电子光谱及磁性等测定,对两配合物进行了表征。     

STUDIES ON THE CRYSTAL STRUCTURE OF Al-(D-TRYPTOPHAN) INSULIN

We have determined the crystal structure of Al-(D-Trp) insulin and discovered that it belongs to the trigonal system with space group R3. The parameters of the unit cell are a=b=78.6, c=50.0. A set of data for half a sphere reciprocal space to a spacing of 2.2 were collected. The model was adjusted and refined by using a step-by-step approach and a stereochemically-restrained least squares program, assisted by manual revision based on the difference Fourier maps, to a final R-factor of 0.218. The main and side chains of both Al-D-Trp residues in the asymmetric unit are well ordered. The packing of Al-(D-Trp) insulin in the unit cell, the conformational differences with other insulin structures and its structure and function relationship bave also been discussed.