NEW THREE DIMENSIONAL [Cd(CN)2]n FRAMEWORK FORMED WITH CADMIUM CYANIDE AND Cd(CN)2·(18-CROWN-6): CRYSTAL STRUCTURE OF [Cd(CN)2]·1/2[Cd(CN)2 (18-CROWN-6)]·3/2EtOH+

Abstract

The cadmium complex Cd(CN)₂·(18-crown-6) (1) was synthesized and its structure was determined by X-ray crystallography. The cadmium ion in 1 has a hexagonal bipyramidal geometry containing six equatorial oxygen atoms from the crown ether and two axial CN ligands. The NC-Cd-CN ‘rod’ is perfectly linear with an end-to-end distance of 6.509 (12) Å. When 1 was allowed to diffuse into a cadmium cyanide solution, the infinite coordination complex [Cd(CN)₂]·1/2[(Cd(CN)₂·(18-crown-6)]·3/2EtOH (2) was obtained in which the cadmium macrocycle 1 was trapped in a 10-faced-cage formed by the [Cd(CN)₂]n framework. The terminal nitrogen atoms of 1 bind two Cd centers across the cage. The trapped Cd(CN)₂·(18-crown-6) has a significantly bent NC-Cd-CN unit and the crown ether ligand disordered over two orientations. The [Cd(CN)₂]_n framework viewed down the c axis shows two types of channels, one octagonal and one tetragonal, which are filled with Cd(CN)₂·(18-crown-6) and ethanol molecules, respectively. Crystallographic data of 1: trigonal, space group R·3 (hexagonal axis), a = 11.757 (1), c = 12.105 (1) Å, V = 1449.1 (2) ų, Z = 3, R = 0.0566, R_w = 0.0674 for 827 unique reflections (I>3σ(I)). Crystallographic data of 2: orthorhombic, Pbcn, a = 16.632 (1), b = 17.391 (3), c = 15.685 (2) Å, V = 4536.8 (9) ų, Z = 8. R = 0.0486, R_w = 0.0492 for 929 unique reflections (I>3σ(I)).     

COPPER(I) COMPLEXES WITH N-(P-NITROPHENYL)-N′-ALKOXYCARBONYLTHIOUREA: SYNTHESES AND CRYSTAL STRUCTURES OF [Cu(H2net)2CI] · CH2CI2 AND [Cu(H2nmt)2CI]2·(CHCI3)2

Abstract

Two copper(I) complexes, [Cu(H₂net)₂Cl] · CH₂Cl₂ (1) and [Cu(H₂nmt)₂Cl]₂ · (CHCl₃)₂ (2), were synthesized by the reaction of CuCl₂ · 2H₂O with N-(p-nitrophenyl)-N′-(ethoxycarbonyl)-thiourea (H₂net) and N-(p-nitrophenyl)-N′-(methoxycarbonyl)-thiourea(H₂nmt), respectively. Both complexes crystallize in the monoclinic space group C2/c. For complex 1, a = 29.52(2), b=13.920(6), c = 14.873(3)Å; β= 101.75(2)°, V = 5984(4) ų, Z = 8 and R = 0.053; for complex 2, a = 30.68(1), b = 13.369(4), c = 14.226(7) Å, β = 99.52(4)°. V = 5754(4) ų, Z = 4 and R = 0.063. In complex 1, two H₂net molecules are bonded to Cu(I) atom through two S atoms forming a mononuclear complex with trigonal geometry for the Cu(I) ion [Cl(1)-Cu-S(1)=118.54(7), Cl(1)-Cu-S(2)=119.70(7), S(1)-Cu-S(2)=112.17(8)°, Cu-S(1) = 2.251(2), Cu-S(2) = 2.255(2), Cu-Cl(1) = 2.263(2) Å]. Complex 2 is a dimer formed by long Cu-S interactions [Cu-S* = 2.607(3) Å] from adjacent twc H₂nmt molecules; the Cu(I) ion has distorted tetrahedral coordination [Cl(1)-Cu-S(1) = 119.8(1), Cl(1)-Cu-S(2)=120.0(1), S(1)-Cu-S(2)=108.85(9)°] with unequal Cu-S [2.268(2), 2.247(2)Å] and Cu-Cl(1) [2.255(2)Å] bonds.     

CRYSTAL STRUCTURE OF [Cu(bpy)3] [{Cu(bpy)}2Re4Se4(CN)12]·3.5H2O

Journal of Structural Chemistry - Chain coordination polymer [Cu(bpy)3][{Cu(bpy)}2Re4Se4(CN)12]·3.5H2O (1) is obtained by the reaction of K4[Re4Se4(CN)12]·6H2O with CuCN and...     

CRYSTAL STRUCTURE AND CALCULATION OF SECOND ORDER POLARIZABILITY OF [Cd(NH_2CSNHNH_2)Br_2]·H_2O

<正> [Cd(NH2CSNHNH2) Br2]· H2O is a new nonlinear optical organometallic complex, and the single crystal structural analysis has been carried out by X-ray diffraction method. According to the model of the second order polarizabili-ty vector, the second order polarizability of one dimensional doubling frequency group of the title compound was calculated using the structural data and the second harmonic relative intensity I2ω/I2ω,KDP.     

DUAL BEHAVIOR OF ACETONITRILE IN A NEW CADMIUM CYANIDE CLATHRATE: CRYSTAL STRUCTURE OF Cd(CH3CN)2Cd(CN)4·2CH3CN

Abstract

We report a new crystal structure of the title clathrate containing tetrahedral and octahedral Cd atoms in a ratio of 1:1. The preparation of the compound is similar to that of the cristobalite-like clathrate Cd(CN)₂·G, where all Cd atoms are tetrahedral. The new inclusion compound crystallizes in the monoclinic space group C2/c, a = 12.337(4), b = 11.964(3), c = 13.594(3) Å, β = 108.60(2)°, Z = 4, R = 0.034 for 1631 reflections. The three-dimensional host framework is built of alternate linkages between the tetrahedral Cd atom of the tetracyanocadmate and the octahedral Cd atom similar to that of the Hofmann-Td and the en-Td types. In the new clathrate dual behavior of acetonitrile, one as a unidentate ligand in the three-dimensional host framework and the other as the guest in the cage-like cavity, has been demonstrated.     

CRYSTAL STRUCTURES OF COPPER (Ⅱ) AND COBALT (Ⅲ) COM- PLEXES OF o-HYDROXYBENZYLGLYCINATE (HBG)

<正> The structures of two complexes C(CuOC6H4CH2NHCH2COO)2 (H2 O)]·H2P(1) and [Co(NH3)6[Co(OC6H4CH2NHCH2COO)2]2[C1]·10H2O (2) were determined by X-ray analyses. Compound (1) crystallizes in the orthorhombic space group P212121 with a=11. 357(1),b= 24. 304(2),c=7.317(4) A,Z= 4;While compound (2) in the monoclinic space group A2/a(C2/c) with a=23. 486(9) ,b=26. 605(6) ,c= 10. 542(1) A,γ= 128. 42(4)°,Z= 4. In compound (1),two Cu(Ⅱ) ions are bonded together by the phenolic oxygen atoms of two tridentate chelating ligands and each of them is separately coordinated by the carboxyl oxygen,amino nitrogen of each chelate ligand and by the fifth oxygen atom as well (from aqua or the carbonyl group in adjacent molecule). Thus the coordination of each Cu(Ⅱ) is a square pyramid with distances of 1. 93- 1. 97A to the four corner atoms and 2. 30 and 2. 32 A to the apex atoms. The whole molecule has an approximately planar configuratioir with the two pyramid apexes pointing towards one side. Compound (2) consists of     

CLUSTER CONVERSION OF [MoW2O2(O2CEt)9]− TO [MoW2O4(O2 CEt)8]4- BY CHROMIUM HEXACARBONYL CRYSTAL STRUCTURES OF Na[MoW2O2(O2CMe)9] · H2O, [MoW2O2(O2CEt)6(H2O)3] ZnCl4 · 2H2O AND Na2Cr2[MoW2O4(O2CEt)8]2

Abstract

Reactions of Mo(CO)₆ with Na₂WO₄ · 2H₂O in refluxing carboxylic anhydride produce the triangular bioxo-capped mixed-metal carboxylate clusters Na[MoW₂O₂(O₂CR)₉] (R = Me, 1; Et, 2), the propionate being hydrolyzed in 2M HCl containing ZnCl₂ to form [MoW₂O₂(O₂CEt)⁶(H₂O)₃]ZnCl₄·2H₂O (3). Cluster 2 is converted to the incomplete cuboidal tetraanion [MoW₂O₄(O₂CEt)₈]^4- upon reacting with Cr(CO)₆ in propionic anhydride at 120°, the latter species being trapped by Cr^3± and Na^± ions in the reaction mixture to afford the octanuclear heterometallic chain-like cluster Na₂Cr₂ [MoW₂O₄(O₂CEt)₈]₂ (4). Clusters 1, 3 and 4 have been characterized by X-ray crystallography with the following crystal data, for 1: monoclinic, space group P2₁/c, a = 16.666(8), b = 11.096(3), c = 16.541(7) Å, β = 94.60(4)°, V = 3048.9 ų, Z = 4, R, Rw = 0.070, 0.079; for 3, monoclinic, space group Cm, a = 10.259(3), b = 15.756(3), c = 10.870(3) Å, β = 96.18(3)°, V = 1746.8 ų, Z = 2, R, Rw = 0.028, 0.034; for 4, triclinic, space group P-1, a = 13.013(5), b = 14.005(4), c = 12.357(4) Å, α = 109.71(2), β = 117.77(3), γ = 90.41(3)°, V = 1838.9 ų, Z = 1, R, Rw = 0.037, 0.042.     

f-ELEMENT/CROWN ETHER COMPLEXES 15. SYNTHESIS AND CRYSTAL STRUCTURE OF ([Lu(OH2)8]Cl3·1.5(12[sbnd]CROWN[sbnd]4)·2H2O

Abstract

The title complex was crystallized at 5°C from a reaction mixture of hydrated LuCl₃ and 12-crown-4 in a solution of CH₃OH:CH₃CN (1:3) after layering in pentane. The crystal and molecular structure of [Lu(OH₂)₈]Cl₃·1.5(12-crown-4)·2H₂O has been determined by single crystal X-ray diffraction. It crystallizes in the monoclinic space group P2₁/c with a=8.816(3), b=23.387(4), c=13.544(2)Å, β=95.14(2)°, and D_calc =1.73 g cm^?3 for Z=4. Least-squares refinement using 3819 independent observed [F₀  5σ(F₀ )] reflections led to the final conventional R value of 0.041. The Lu(III) cation is coordinated to eight water molecules (Lu[sbnd]O average 2.33(3)Å) in an approximate bicapped trigonal prismatic geometry. The crown ether molecules, chloride ions, and uncoordinated water molecules participate in hydrogen bonds to the cation. The hydrogen bonding of the [Lu(OH₂)₈]³⁺ cations to the crown ether molecules results in zigzag chains along c. The chains are further connected by hydrogen bonding to the chloride ions and uncoordinated water molecules. One crown ether resides around a crystallographic centre of inversion and has a C_i , conformation. The second crown has the C₄ conformation normally observed in metal complexes with this ligand.     

Syntheses and structures of seven-coordinate K3[Cd(Dtpa)], K2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O, and Na2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O complexes

The title complexes, K₃[Cd(Dtpa)] (H₅Dtpa = diethylenetriamine-N,N,N,N′,N′-pentaacetic acid, (I)), K₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid, (II)), and Na₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (III), were prepared, and their compositions and structures were determined by elemental analyses, IR spectra, and single-crystal X-ray diffraction techniques, respectively. In complex I, the Cd is seven-coordinated by one Dtpa ligand yielding a pseudo-monocapped trigonal prism conformation, and the complex crystallizes in the triclinic crystal system with the Pi space group. The crystal data are as follows: a = 8.7300(17), b = 9.1200(18), c = 15.110(3) Å, α = 95.52(3)°, β = 96.59(3)°, γ = 99.63(3)°, V = 1170.0(4) ų, Z = 2, ρ = 1.754 g/cm³, μ = 1.519 mm^?1, F(000) = 616, R = 0.0644 and wR = 0.1712 for 3842 observed reflections with I ≥ 2σ(I). For complex II, in the [Cd(Edta)(H₂O)]^2? complex anion the Cd²⁺ ion is seven-coordinated by one Edta ligand and one water molecule, yielding a pseudo-pentagonal bipyramid conformation. In the [Cd(H₂O)₄]²⁺ cation, the bridged Cd is six-coordinated, yielding an almost standard octahedral conformation. The complex crystallizes in the monoclinic system with P2₁/n space group. The crystal data are as follows: a = 9.098(3), b = 16.442(6), c = 12.023(4) Å, β = 91.053(6)°, V = 1798.3(12) ų, Z = 2, ρ = 2.098 g/cm³, μ = 2.086 mm^?1, F(000) =1124, R = 0.0406 and wR = 0.1152 for 3680 observed reflections with I ≥ 2σ(I). In complex III, the conformations of Cd²⁺ ions are similar to those of the potassium salt complex, and the complex also crystallizes in the monoclinic crystal system with the P2₁/n space group. The crystal data are as follows: a = 9.134(7), b = 16.500(13), c = 12.075(10) Å, β = 91.054(12)°, V = 1820(2) ų, Z = 2, ρ = 2.015 g/cm³, μ = 1.856 mm^?1, F(000) = 1092, R = 0.0363 and wR = 0.0879 for 3707 observed reflections with I ≥ 2σ(I).     

CRYSTAL AND MOLECULAR STRUCTURE OF BIS(L-VALINATO)COPPER(II) MONOHYDRATE Cu[(CH_3)_2CHCH(NH_2)COO]_2·H_2O

<正> Mr=313.8, monocllnic, C2, a=21.255(4), b=9.567(4), c=7.399(1)A, β=108.8(1)°, V=1423.8A3, Z=4, Dx=1.464 g.cm-3, MoKα , μ=15.496cm-1 , F(OOO) = 660, T=295K, final R=0.089 for 1644 observed reflections. Two amino acid ligands chelate to copper forming a planar-square configuration. An oxygen atom of water occupying the apical position makes the coordinating polyhedron of copper a square pyramid.     

THE CRYSTAL AND MOLECULAR STRUCTURE OF CHLORO(BIS-2,2''''-DIPYRIDYL) COPPER7,7'''',8,8''''-TETRACYANOQUINODIMETHANE [Cu(bipy)_2Cl]·TCNQ_2

The crystals of title compound are prepared by the electrochemical method and its structure has been determined by X-ray diffractions method. The crystals are triclinic with space group P(?). a=7.920, b=13.140, c=19.126; a=100.77°, β=94.45° and γ=101.08° ; Z=2, Calculating of electronic structure of TCNQ and its packing mode are discussed.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A HETERODINUCLEAR COMPLEX OF PALLADIUM SILVER WITH BRIDGING BIS-( DIPHENYLPHOSPHINO ) METHANE [ 1 ]

<正> A heterodinuclear complex, trans- dicyano- palladium (Ⅱ)- bis [β- bis (diphenylphosphino)methane]-nitritosilver(Ⅰ),has been prepared by treatment of trans-(NC)2Pd(dppm)2 with AgNO2 and characterized by elementary analysis, ir, nmr, and X-ray crystal structure determination. AgPdC52H44N3O2P4,Mr= 1081. 12,monoclinic,space group P21/c,a=14. 745(7),b= 19. 208(7),c= 17. 486(6) A ,β=94. 99°(2) ,and Z = 4. The final R=0. 032 for 8673 unique reflections. In the molecule,the Pd -Ag distance is 3. 205 A. The palladium moiety has an approximately square planar geometry, and the silver moiety has a severely distorted tetrahedral geometry.     

CRYSTAL STEOCTURE OF [Cu(HCOO)_2(HCOOH)_2]n

<正> Mr=245.6, monoclinic, V2l/c, a=7.778(4), b=7.946(4), c=8.008(4) X, B=115.31(4)? V=447.483, Z=2, Dx=1.82 g/cm3, X(Mokct)=0.710698, y=25.5cm~1 F(000)=245.96, T=293 K. The final R=0.059 for 423 unique observed reflections. Cu2-' is coordinated by six oxygen atoms to form a distorted octahedron. Cu2^ ions are linked together by formate groups in an anti-anti bridging arrangement to form a two dimensional polymer. Two oxygen atoms in a formate group are equivalent with C(l)-0(l)=l.25(1) and C(l)-0(2) = l. 2.5(1)8.     

ELECTRONIC STRUCTURES AND BONDING PROPERTIES OF MIXED LIGAND COPPER(II) COMPLEXES OF 2-(2-PYRIDYLETHYL)PICOLYLAMINE AND DIPICOLYLAMINE. MOLECULAR STRUCTURES OF (2,2′-BIPYRIDINE)[2-(2-PYRIDYLETHYL)PICOLYLAMINE]COPPER(II) PERCHLORATE AND (DIPICOLYLAMINE)(1,10-PHENANTHROLINE)COPPER(II) PERCHLORATE

Abstract

Mixed ligand copper(II) complexes of 2-(2-pyridylethyl)picolylamine (pepica) of [Cu(pepica)(pi-colinato)](ClO₄)(H₂O) and the [Cu(pepica)(L)](ClO₄)₂ type, where L stands for 2,2′-bipyridine (bipy), 1,10-phenanthroline, neocuproine, and ethylenediamine, and dipicolylamine(dipica) of the [Cu(dipica)(L)](ClO₄)₂(H₂O) _n type, where L for 2,2′-bipyridine (n = 0), 1,10-phenanthroline (phen, n = 0), and neocuproine (n = 1), have been synthesized and characterized by elemental analyses, and IR, electronic and EPR spectroscopic measurements. The molecular structures of [Cu(pepica)(bipy)](ClO₄)₂ (1) and [Cu(dipica)(phen)](ClO₄)₂ (2) have been determined using three dimensional X-ray diffraction data. Complex 1 consists of discrete distorted square pyramidal [Cu(pepica)(bipy)] cations, with a meridional pepica ligand and one of the pyridine rings of the bipy ligand forming a basal plane. The other pyridine nucleus of the bipy is bound at the apex having an elongated bond distance of 2.255 Å and tilted off the normal z axis by ～15°. Complex 2 comprises discrete distorted trigonal bipyramidal [Cu(dipica)(phen)] cations, with the two pyridine nuclei of the dipica ligand and one of the pyridine rings of the phen forming an equatorial trigonal plane and the remaining pyridine ring of the phen and the amine nitrogen of the dipica on the axial sites. The trigonal bipyramidal cation, distorted toward a square pyramidal structure, has an enlarged equatorial N(py)–Cu–N(py) angle of 132.4° and an elongated equatorial Cu–N(phen) bond of 2.156 Å. All of the complexes exhibit axial type EPR spectra. Gaussian resolved d-d spectra for these complexes, except the dipica-bipy and dipicaphen ones, yield an orbital sequence of d_x ²- _y ² ≥ d_z ² > d_xy > d_yz ～d_xz . The bonding properties of the tridentate and the bidentate ligands are elucidated.     

CRYSTAL STRUCTURE OF Na[Nd(S_2CN(C_2H_5)_2)_4]·CH_3CN

<正> Triclinic, PI, a=10.204(3), b=ll.384(2), c=18.399(4) X, a=84.19 (2), 6=106.15(2), Y=116.71(2)? V=1833.1(6)S3, Z=2, y=18.76cm, A=0.71069&, F(OOO)=809.91, room temperature, .R=0.059. In, the title compound the neodym-ium ion is coordinated by eight sulphur atoms from S2CNEt2ligands with the average distances of 2.88A and 2.<.Et2N桟桟\(:S桸Et2-Nb-\\C 桸Et2     

SYNTHESIS AND CRYSTAL STRUCTURE OF A POLYMERIC 1,2,4,5-BENZENETETRACARBOXYLATO COMPLEX OF Cu(II) WITH IMIDAZOLE,Cu2(C10H2O8)(C3H4N2)6(H2O)4 · 4H2O

Abstract

The title complex, Cu₂(C₁₀H₂O₈)(C₃H₄O₂)₆(H₂O)₄ · 4H₂O, consists of polymeric copper(II) complex anions and discrete copper(II) complex cations. Benzenetetracarboxyl anions bridge copper(II) atoms coordinated to water and imidazole groups to form the anionic polymeric chains along the a axis, while discrete copper(II) complex cations involving four imidazole and two water ligands are packed between parallel polymeric anionic chains, an extensive H-bonding network linking complex cations and anions.     

A polyoxoniobate based on dimeric hexanionbate: [Cu(en)2]4{[Nb6O19H2]K(H2O)5}2 · (H2en) · 17H2O

A polyoxoniobate, [Cu(en)₂]₄{[Nb₆O₁₉H₂]K(H₂O)₅}₂ ? (H₂en) ? 17H₂O (en = ethylenediamine) (1), has been synthesized and characterized by elemental analysis, IR, XPS, TGA, and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a = 12.3533(16) Å, b = 12.7188(16) Å, c = 29.626(4) Å, α = 93.235(2)°, β = 96.094(1)°, γ = 106.098(2)°, V = 4429.0(10) ų, Z = 2. The polyoxoanion is composed of a Lindqvist-type [Nb₆O₁₉H₂]^6? dimer bi-bridged via two K⁺. K⁺ is 10-coordinate with 10 oxygens, three from one [Nb₆O₁₉H₂]^6?, one from a terminal oxygen of another [Nb₆O₁₉H₂]^6? moiety, and the other six from water molecule. Adjacent dimeric polyoxoanions are linked to form an infinite 1-D chain via O–H ··· O hydrogen-bonding interactions which exist between the two water trimers and the dimeric polyoxoanions.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF BIS [4,4,4-TRIFLUOR-1-(2-THIENYL) Butandion-1,3] COPPER (Ⅱ) WITH DIMETHYLFORMAMIDE, [Cu(TTA)_2(DMF)]

<正> [Cu(C8H4F3O2S)2(C3H7NO)], Mr = 579. 0, monoclinic, P21/c, a = 9. 4851(6), b = 26. 6574(6), c=9.2619(6) A ,β=96.08(3)°, V = 2328.7A3, Z=4, Dc=1. 65gcm-3, μ(MoKa) = 7. 2cm-1, F (000) = 1172, MoKa radiation, final R = 0. 074 and Rw = 0. 068 for 1841 reflections with I≥3σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by five oxygen atoms, one of which from DMF is in the axial position, to form a square pyramidal geometry. That the thenoyl groups in the ligands take the cis-form around the Cu(Ⅱ) atom is explained by the hydrogen bonding effect.