METAL COMPLEXES OF POLYCYCLIC TERTIARY. AMINES. PART VIII. SYNTHESIS AND CRYSTAL STRUCTURE OF 1,4-DIAZABICYCLO[2.2.2]OCTANEPENTACARBONYLMOLYBDENUM(0), (CH_2)_6N_2·Mo(CO)_5

<正> C11H12N2MoO5, Mr = 348.17, orthorhombic, space group p212121,a= 7.048(1), b = 11.060(4), c = 18.039(7) A, V = 1406.2(8) A3, Z = 4, D x=1.645, Dm = 1.61 (flotation in aqueous KI) g cm-3 , graphite-monochromatizedMo-Kα,λ = 0.71069 A, μ = 9.25 cm-1, F(OOO) = 695.73, T = 295°K, final RF =0.035 and RwF2 = 0.051 for 1335 observed reflections with |F0| > 3σ(|F0|). The measured molecular dimensions.reflect the trans influence and steric bulk of the organic cage ligand.     

TRANSITION METAL COMPLEXES WITH HYDRAZIDES AND HYDRAZONES. PART 81. X-RAY CRYSTAL STRUCTURE OF A CATENA-POLYBROMO (ACETONE-1-NAPHTHOYLHYDRAZONE) COPPER(II)-COPPER(I) COMPLEX

Abstract

The title compound [Cu₃Br₄C₂₈H₂₈N₄O₂] is a type of polymeric three-centre octahedral-trigonal planar coordination complex. The copper(II) atom located at a centre of symmetry is six-coordinate with two bidentate (N3, O1) ligands of acetone-1-naphthoylhydrazone forming the equatorial plane and two bromine ions in axial positions (Cul-Brl = 2.946(1)Å). The ligands are in trans positions. The Cu(I) atoms are in trigonal planar coordination by two bridging Br^? ions (Cu2-Br2 = 2.412(1)Å, Cu2-Br2? = 2.407(2)Å) which connect two Cu(I) atoms and a third bromine ion shared with the octahedral Cu(II) ion (Cu2-Br1 = 2.304(1)Å). The arrangement forms an infinite chain along the b axis.     

THE CRYSTAL AND MOLECULAR STRUCTURE OF BENZYL (2-METHOXYPHENYL)-DIPHENYLPHOSPHONIUM BROMIDE

Abstract

The crystal structure of benzyl(2-methoxyphenyl)diphenylphosphonium bromide has been determined from three dimensional X-ray data collected on a three circle diffractometer using MoKα radiation. The salt crystallized in the orthorhombic space group Pbca with cell constants α=15.528 (7), b=16.892 (7), and c=17.921 (8) A. The observed and calculated densities for 8 molecules per unit cell are 1.308 (5) and 1.309 g · cm^?3 respectively. The structure was refined by full matrix least squares to final residuals of R=0.089 and R _w0.120 for the 1757 independent reflections in the range 2° > 2θ> 42° whose intensities were above background. The cation has near tetrahedral geometry with an average P-C bond distance of 1.819 (14) A and the configuration of the ion is such that the oxygen atom of the methoxy group is trans to the alkyl carbon atom of the benzyl group. The phosphorus-oxygen distance of 2.878 (12) Å suggests a weak bonding interaction and qualitative support for this view is obtained from energy minimization calculations in which the total steric energy made up primarily of bond stretching energies and van der Waals non-bonded interactions is treated. The results are in accord with nmr data previously reported and from which it was concluded that a weak bonding interaction between the methoxy oxygen and the phosphorus atoms causes an upfield shift of the methyl protons of the benzyl group. The molecular structure of the phosphonium cation depicted herein makes it highly improbable that the observed chemical shift is attributable to a magnetic anisotropic effect.     

TRANSITION METAL COMPLEXES OF OLIGOTHIOETHER QUINOLYLOXY TERMINATED PODANDS: PART 2. CRYSTAL AND MOLECULAR STRUCTURE OF (1,8-BIS(QUINOLYLOXY)-3,6-DITHIAOCTANE)-COPPER(II) DIPERCHLORATE TRIHYDRATE

Abstract

The synthesis of the new ligand 1,8-bis(quinolyloxy)-3,6-dithiaoctane (1) and the corresponding Cu(II), Cu(I) and Co(II) complexes is reported. The crystal and molecular structure of the copper(II) complex, [Cu(1)](ClO₄)₂.3H₂O, has been determined by X-ray diffraction methods. The complex crystallizes in the orthorhombic space group Fddd, with cell data Z = 16, a = 20.326(2), b = 20.879(3) and c = 28.308(4)Å. The structure consists of discrete [Cu(1)]^?2+ cations separated by (structurally disordered) perchlorate anions and three lattice water molecules per cation. The coordination geometry about the copper atom is pseudo-octahedral with the quinoline nitrogen and thioether sulfur atoms at the equatorial positions and the ether oxygen atoms at the axial positions. ¹H NMR line-broadening experiments indicate that electron-transfer self-exchange reactions between the copper(I) and copper(II) complexes of (1) is immeasurably slow on the NMR time-scale. The coordination chemistry of (1) is compared with its oxygen analogue, 1,8-bis(quinolyloxy)-3,6-dioxaoctane.     

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.     

PREPARATION AND CRYSTAL STRUCTURE OF CYCLOPENTADI-ENYL TETRAMETHYLETHENE-BRIDGED DICYCLOPENTA-DIENYLSAMARIUM(Ⅲ) TETRAHYDROFURANATE

<正> (CH3)4C2(C5H4)2Sm(C5H5)(OC4H8),Mr=499.4,orthorhom-bic,Cc2a,a=11.696(6),b=12.539(5),c=29.432(15)A,V=4316(4)A3,Z=8,Dc=1.54g/cm3,μ(MoKa)=27.8cm-1,F(000)=2024,R=0.077 for 1833 observed reflections.The samarium atom in the molecule is bonded to three cyclopen-tadienyl rings and one oxygen atom of tetrahydrofuran(THF)to form a tetrahedral configuration.The average Sm-C(η5-Cp)distances for the three cyclopentadienyl groups are 2.72(3),2.76(3)and 2.78(3)A,respectively,and the Sm-O bond is 2.53(1)A.     

N-PHOSPHORYL AMINO ACIDS AND PEPTIDES: PART I. THE CRYSTAL AND MOLECULAR STRUCTURE OF N-(O,O-DIISOPROPYL PHOSPHORYL)-TRANS-4-HYDROXY-D,L-PROLINE

Abstract

The crystal and molecular structure of N-(O,O-diisopropyl phosphoryl)-trans-4-hydroxy-D,L-proline has been determined by X-ray diffraction analysis and is compared with proline or hydroxyproline residue in a peptide chain described in the literature. The compound crystallized in orthorhombic system with space group P2₁2₁2₁, a=6.934(2), b=8.694(3), c=26.727(7) Å, V=1611.3(8) ų, Z=4, Dx=1.22 g/cm³. The structure was solved by direct method and refined by anisotropic least squares to a discrepancy index R=0.072. In the compound, the nitrogen atom is trigonal and its remaining 2p orbital is conjugated with the P?Oπ system; the conformation of the phosphorimidate function is favoured by the trans orientation of the P=O bond with respect to the N-C4 bond. In the pyrrolidine ring moeity, the C2-C1-N-C4 atoms are nearly copolnar and the C3 atom is out of the plane by about 0.47 Å.     

PREPARATION AND CRYSTAL STRUCTURE OF TETRAKIS(TETRAHYDROFURAN) MAGNESIUM DICHLORIDE[MgCl_2·4THF]

<正> INTRODUCTION. The magnesim, dichloride is widely used as a supporter of the highly efficient Ziegler-Natta catalyst with ether or ester as a donor. To study the interaction between the supporter and the donor would lead to a better understanding of the mechenisms of stereoregular polymerization. Here we wish to report the preparation and X-ray crystal structure of MgCl_2 4THF, which is the first example of the MgCl_2 complex uncontaining coordinated water or solvent water.     

CRYSTAL STRUCTURE OF BINUCLEAR Eu(Ⅲ) AND Tb(Ⅲ) COMPLEXES WITH 3,4-FURANDICARBOXYLIC ACID

<正> INTRODUCTION. Rare earth complexes with carboxylic acids have been investigated extensively, but little attention has been paid tothose with furan acid ligands. Here we describe the synthesis and structures of two     

PREPARATION AND CRYSTAL STRUCTURE OF THE TANTALUM BROMIDE CLUSTER COMPLEX [Li(diglyme)2]2[Ta6Br18]

Journal of Structural Chemistry - Extracting the reaction product of Ta, Br2, and LiBr (720&nbsp;°C, 48 h, mole ratio 1.5:1.75:1.0) with diglyme yields crystals of complex...     

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.     

SYNTHESIS OF MONOSUBSTITUTED PENTAKIS(2,6-DIETHYLPHENYLISO CYANIDE)- COBALT(I) COMPLEXES WITH BIDENTATE TERTIARY PHOSPHINE LIGANDS. I. MONOMETALLIC COMPLEXES

Abstract

Reaction of [Co(CNC₆H₃Et₂-2,6)5]BF₄ with bidentate phosphines leads to monosubstituted Co(I) complexes, [Co(CNC₆H₃Et₂-2,6)₄(L-L)]BF4, where L-L = Ph₂P(CH₂)n PPh₂, n = 1-4,6; Ph₂PCH₂-CH₂AsPh₂, Ph₂PC₆H₄PPh₂-p, Ph₂PCH[dbnd]CHPPh₂-trans. Reaction conditions are such that disubstitution would be possible, but bidentate bridging to form bimetallic complexes is not favoured. Comparison of v([sbnd]N°C) IR, electronic spectra, and molar conductivities with values for [Co(CNC₆H₃Et₂-2,6)4L]X, where X = ClO₄, BF₄; L = monodentate triarylphosphine; indicates that these new complexes must also be five-coordinate Co(I) complexes, in which the potentially bidentate phosphine ligands are coordinated through only one P atom. Structures are approximately trigonal bipyramidal in solution and the solid state, with the phosphine ligand occupying an axial position.     

STUDIES OF PHOSPHAZENES. PART VI.1 THE PREPARATION OF THE ISOMERIC TETRACHLOROBIS-ISOPROPYLAMINOCYCLOTRIPHOSPHAZATRIENES

Abstract

The three isomers of N₃P₃Cl₄(NHPr¹)₂ have been prepared and separated by gas-liquid chromatography. Their structures have been assigned on the basis of ¹H and ³¹P nmr data.     

SYNTHESIS OF MONOSUBSTITUTED PENTAKIS(2,6-DIETHYLPHENYLISO-CYANIDE)COBALT(I) COMPLEXES WITH BIDENTATE TERTIARY PHOSPHINE LIGANDS. II. BIMETALLIC COMPLEXES

Abstract

Reaction of bidentate tertiary phosphines with excess [Co(CNR)₅]BF₄, or reaction of [Co(CNR)₄L-L]BF₄ with excess [Co(CNR)₅]BF₄, leads to bimetallic complexes of the form, [(RNC)₄CoL-LCo(CNR)₄](BF₄)₂, R = 2,6-Et₂C₆H₃, L-L = p-Ph₂PC₆H₄PPh₂, Ph₂PC═CPPh₂, Me₂PCH₂CH₂PMe₂, Ph₂PCH₂CH₂PPh₂, Ph₂PCH₂CH₂CH₂PPh₂. Comparison of the v(? N═C) IR patterns, electronic spectra, and molar conductivity values of these bimetallic complexes with data for other Co(I)-organoisocyanide complexes indicates that the two -Co(CNR)₄ moieties are almost totally independent of each other. Recorded λ_max values are the same as for the [Co(CNR)₄L-L]BF₄ complexes, but the ε values, although very large, are less than double. Λ_M values in acetone, and probably also in CH₂Cl₂, are better interpreted as twice the normal conductivity for 1:1 electrolytes than conductivity for 2:1 electrolytes.     

SYNTHESIS,CRYSTAL STRUCTURE AND ANTIMICROBIAL ACTIVITY OF COBALT(III) COMPLEXES WITH SCHIFF BASE LIGANDS

Journal of Structural Chemistry - Three new mononuclear cobalt(III) complexes, [CoL1(4-Brsal)] (1), [CoL3(4-Brsal)] (2), and [Co(L2)2]NO3 (3), where L1, L2, L3 and 4-Brsal are the deprotonated form...     

Me_4Bzo_2[14]六烯(2-)N_4金属配合物的结构和反应性研究 Ⅰ.溴碘加成物的合成和振动光谱研究

本文合成了Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Cu(Ⅱ)大环配合物及其溴碘加成物,研究了远红外和Raman光谱,对MN_4局部进行了伸缩振动的简正坐标分析,求得了各化合物的键角和伸缩力常。通过Raman光谱初步确定了溴碘的存在形式。对溴碘加成物的叠层结构和各化合物的成键进行了讨论。     

Me4Bzo2[14]六烯(2-)N4金属配合物的结构和反应性研究 Ⅰ.溴碘加成物的合成和振动光谱研究

本文合成了Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Cu(Ⅱ)大环配合物及其溴碘加成物,研究了远红外和Raman光谱,对MN₄局部进行了伸缩振动的简正坐标分析,求得了各化合物的键角和伸缩力常.通过Raman光谱初步确定了溴碘的存在形式.对溴碘加成物的叠层结构和各化合物的成键进行了讨论.     

CRYSTAL STRUCTURES AND TRIBOLUMINESCENT ACTIVITIES OF SAMARIUM(III) COMPLEXES

Abstract

The triboluminescence spectra and crystal structures of 1,2-dimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (1) and 1,2,6-trimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (2) were determined. The triboluminescent maximums are similar to those of the photoluminescence. Complex 1 is centrosymmetric and the triboluminescent emission may correlate with the disorder of all S atoms, all CF₃ groups and the cation. The triboluminescent activity of complex 2 may correlate with its noncentrosymmetric space group. Complex 1 crystallizes in the monoclinic space group P2₁/a with cell parameters a = 19.874(2) Å, b = 22.922(2)Å, c = 21.188(1)Å, β = 108.126(6)°, V = 9173(1)ų; Z = 8; R = 0.0758 and R_w = 0.1315. Complex 2 crystallizes in the monoclinic space group Pn with cell parameters a = 11.2808(6)Å, b = 11.0199(5)Å c c = 18.4336(9)Å, β = 108.126(6)° V = 2285.28(19)ų; Z = 4; R = 0.0347 and R_w = 0.0900. All the structures were refined by full-matrix least squares methods.