Synthesis and Crystal Structure of a Peroxo-Bridged Binuclear Rhodium (III) Complex and its Superoxo-Bridged Analogue

The reaction of the ammonia diol [(NH₃)₄Rh(OH)₂Rh(NH₃)₄]⁴⁺with H₂O₂ Yields among other products a peroxo-bridged dimeric species [(NH₃)₄Rh(O₂)(OH)Rh(NH₃)₃(H₂O)](CIO₄)₃. Its structure was determined by single-crystal X-ray diffraction. The crystals are monoclinic with space group P2₁/n and lattice constants a=12.269 (5) Å, b=10.769(4) Å, c=15.964(4) Å, β=107.17(3)°. The dihedral angle of the RhOORh group in the bimetallic ring deviates by 62δ from planarity. The peroxo-bridged complex was found to disproportionate in 1_M HCIO₄ and a red superoxo-bridged complex. [(NH₃)₄Rh(O₂)(OH)Rh(NH₃)₃(H₂O)](NO₃)₄, was isolated. Its structure was solved by single-crystal X-ray diffraction. The crystals are orthorhombic with space group Pna 2, and lattice constants a=14.997(5) Å, b=11.952(4) Å, C=10.489(4) Å. The dihedral angle off the RhOORh group deviates by 7δ from planarity.     

X‐ray crystal of diprotonated tetra‐(2‐pyridyl)pyrazine (H2TPPZ), aqua Fe3+‐phen crystal and new lanthanide complexes of TPPZ and their biochemical studies

New complexes derived from M³⁺ salts with polyazine as monometallic such as [Fe (TPPZ)Cl₃].½H₂O (1) , [Cr (TPPZ)₂Cl₂]Cl.2EtOH (2) , [La (TPPZ)(NO₃)₂(H₂O)₂]NO₃.H₂O (3) in addition to [Fe (Phen)₃]3Cl.7H₂O (4) were isolated. Three bimetallic, [H₂TPPZ][(AuCl₄)₂]. H₂O (5) , [Ce₂(TPPZ)EtOH (NO₃)₃]3NO₃ (6) and [Nd₂TPPZCl₂(H₂O)₄]4Cl.CHCl₃. 4H₂O (7) and mixed ligand complexes, [Fe (TPPZ)(Phen)₂]Cl₃ (8) , [Fe (TPPZ) (Phen)₂][TPPZCl₃] (9) , [La₂(TPPZ)(Phen)₂(EtOH)₂]6Cl.CHCl₃.EtOH.H₂O (10) and [Nd₂(TPPZ)(Phen)Cl₄]2Cl.3H₂O (11) were synthesized and characterized. Crystal data of (4) is tetragonal, I4₁/a, a = b 35.951 (3) Å, c = 11.9055 (8) Å, α = 80.201 (2)° β = 78.846 (2)°, γ = 89.687 (2)° V = 741.06 (5)ų, Z = 1 while triclinic, P1, a = 7.3913 (3) Å, b = 9.7344 (4) Å, c = 10.6577 (4) Å, α = β = γ = 90°, V = 741.06 (5)ų and Z = 170 for (5) . Analyses, spectral and cyclic voltammetry studies indicate the bonding and the redox properties. Anticancer studies promised to be effective in lanthanides and some complexes were screened against antibacterial or antifungal.     

一种新颖的二维4f-3d-5d多金属-异烟酸配合物的合成、晶体结构和磁性研究

通过水热方法合成了一种新颖的异金属金属-异烟酸无机-有机杂化体[Zn0.5(H2O)]{(Hg2Cl5)[Er(C6NO2H4)3(H2O)2]}(HgCl2)·0.5CH3OH·0.5H2O (1)并对其进行了单晶X-射线衍射结构表征。该化合物是首例4f-3d-5d多金属-异烟酸配合物。化合物1属于单斜晶系C2/c空间群,每个单胞中有8个分子,晶体学参数为：a = 34.165(4) Å,b = 9.4692(8) Å,c = 24.575(3) Å,β = 115.090(5)°,V = 7200(1) Å3,C18.50H21Cl7ErHg3N3O10Zn0.50,Mr = 1495.25,Dc = 2.759 g/cm3,T = 293(2) K,μ(MoKα) = 15.954 mm-1,F(000) = 5400, R1/wR2 = 0.0561/0.0909,共有6468个独立衍射点,其中[I > 2σ(I)]的有3157个。该化合物具有新颖的二维{(Hg2Cl5)[Er(C6NO2H4)3(H2O)2]}层状结构,由Hg2Cl5–连接[Er(C6NO2H4)3(H2O)2]链形成。该二维层和氯化汞及结晶水之间通过氢键形成三维结构,甲醇分子和水合锌离子位于该三维结构的空隙中。对化合物1的磁性测试显示该化合物具有反铁磁作用。     

The reaction of 2′ 2′ 3′ 3′-tetrafluoropropyl-5-iodo-3-oxaoctafluoropentane sulfonate with dimethylsulfoxide and determination of the crystal structure of one of the products

The title reaction gave three known compounds (2, 3 and 4) and two new compounds, CH₃SCH₂(CF₂)₂H (5) and I(CF₂)₂O(CF₂)₂SO₃⁻S+(CH₃)₃ (6). The structure of 6 was confirmed by X-ray diffraction analysis. The crystals of 6 belong to monoclinic space group P2₁/C with a = 9.399, b = 15.651, c=10.934Å, β = 94.80° and z = 4. The structure was solved by heavy-atom method and refined by block-diagonal matrix least-squares procedure to a final R of 0.054 for 1999 independent observed reflexions. The S C bonds around the sulphur atom in trimethylsulphonium are pyramidal with the bond lengths of 1.814 Å, 1.800Å and 1.818 Å and the bond angles C-S-C of 101.06°, 101.52° and 102.53°. The distances of the sulphur atom in trimethylsulphonium to three oxygen atoms in the sulphonate radical are 3.79 Å, 3.64 Å and 3.34 Å respectively. These distances are out of the range of the normal S-O bond length. The structure consists of trimethylsulphonium cations and 5-iodo-3-oxaoctafluoropentane-sulphonate anions.     

Syntheses and crystal structures of cis - and trans -copper(II) complexes of L-arginine

Two copper(II) complexes of L-arginine, trans-[Cu(l-Arg)₂(NO₃)]NO₃ · 3H₂O (1) and {cis-[Cu(l-Arg)₂](NO₃)₂ · 3H₂O} _n (2) (Arg = arginine) were prepared by reaction of Cu(NO₃)₂ · 3H₂O and L-arginine in acetone and aqueous solution, respectively. X-ray analysis reveals 1 crystallizes in a monoclinic system, P2₁ with a = 10.3857(15), b = 16.885(3), c = 15.9586(19) Å, β = 15.9586(19)°, Z = 4, V = 2654.2(6) ų. The copper(II) centers lie in a distorted N₂O₃ square-pyramidal environment. While 1 adopts a mononuclear structure, and the axial position occupied by a nitrate with Cu1–O9 = 2.535 Å and Cu2–O20 = 2.581 Å, 2 features a 1-D infinite chain structure. In 1, adjacent monomeric units connect with each other to give a 2-D layer structure of (4, 4) nets through hydrogen bonds between the guanidinium and carboxylic groups of arginine, and 2-D layers further assemble to a 3-D supermolecular structure via a series of inter-layer hydrogen bonds.     

Molecular structures of 3‐[(2,2,3,3‐tetrafluoropropoxy)methyl]‐ and 3‐[(2,2,3,3,3‐pentafluoropropoxy)methyl]pyridinium saccharinates

The salts 3‐[(2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium saccharinate, C₉H₁₀F₄NO⁺·C₇H₄NO₃S⁻, (1), and 3‐[(2,2,3,3,3‐pentafluoropropoxy)methyl]pyridinium saccharinate, C₉H₉F₅NO⁺·C₇H₄NO₃S⁻, (2), i.e. saccharinate (or 1,1‐dioxo‐1λ⁶,2‐benzothiazol‐3‐olate) salts of pyridinium with –CH₂OCH₂CF₂CF₂H and –CH₂OCH₂CF₂CF₃meta substituents, respectively, were investigated crystallographically in order to compare their fluorine‐related weak interactions in the solid state. Both salts demonstrate a stable synthon formed by the pyridinium cation and the saccharinate anion, in which a seven‐membered ring reveals a double hydrogen‐bonding pattern. The twist between the pyridinium plane and the saccharinate plane in (2) is 21.26 (8)° and that in (1) is 8.03 (6)°. Both salts also show stacks of alternating cation–anion π‐interactions. The layer distances, calculated from the centroid of the saccharinate plane to the neighbouring pyridinium planes, above and below, are 3.406 (2) and 3.517 (2) Å in (1), and 3.409 (3) and 3.458 (3) Å in (2).     

Synthesis of Lanthanide–Alkylaluminium Bimetallic Complexes and Studies on Their Catalytic Activities for Polymerization of Some Polar Monomers

Three new lanthanide (Ln)–alkylaluminium (Al) bimetallic complexes with the formula [(μ-CF₃CO₂)₂Ln(μ-CF₃CHO₂)AlR₂ · 2THF]₂ (Ln=Nd, Y, R=i-C₄H₉ (i-Bu); Ln=Eu, R=C₂H₅(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF₃CO₂)₃ (Ln=Nd, Y) with HAl (i-Bu)₂ and of Eu(CF₃CO₂)₃ with AlEt₃, respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(μ-CF₃CO₂)₂Nd (μ-CF₃CHO₂)Al(i-Bu)₂ · 2THF]₂ (Nd–Al) and [(μ-CF₃CO₂)₂Y(μ-CF₃CHO₂)Al(i- Bu)₂ · 2THF]₂ (Y–Al) are isomorphous and crystallize in space group P 1 with a =12.441(3) Å [12.347(5) Å for Y–Al], b =12.832(3) Å [12.832(4) Å], c =11.334(3) Å [11.292(8) Å], α=104.93 (2)° [104.45(4)°], β=98.47(2)° [98.81(4)°], γ=64.60(2)° [64.30(3)°], R =0.519 [0.113], R _w=0.0532 [0.110], Z =1 and [(μ-CF₃CO₂)₂Eu(CF₃ CHO₂)AlEt₂ · 2THF]₂(Eu–Al) in space group P 2₁/ n with a =11.913(6) Å, b =14.051(9) Å, c =17.920(9) Å, α=101.88(11)°, β=γ=90°, R =0.0509, R _w=0.0471 and Z =2. The six CF₃CO     

Homo- und heterodinukleare α-Pyridonat-verbrückte Platin- und Palladium-komplexe mit Bis(N-methylimidazol-2-yl)keton (BMIK). Kristallstrukturen von [(BMIK)Pt(α-Pyridonat)2Pt(BMIK)](NO3)2 · 4H2O, [(BMIK)Pd(α-Pyridonat)2Pd(BMIK)](NO3)2 · 4H2O und [(BMIK)Pd(α-Pyridonat)2Pt/Pd(BMIK)](NO3)2 · 4H2O

Homo- and Heterodinuclear α-Pyridonate-bridged Platinum and Palladium Complexes with Bis(N-methylimidazol-2-yl)ketone (BMIK). Crystal Structures of [(BMIK)Pt(α-pyridonate)₂Pt(BMIK)](NO₃)₂ · 4H₂O, [(BMIK)Pd(α-pyridonate)₂Pd(BMIK)](NO₃)₂ · 4H₂O, and [(BMIK)Pd(α-pyridonate)₂Pt/Pd(BMIK)](NO₃)₂ · 4H₂O The isotypic dinuclear complexes [(BMIK)Pt(α-pyridonate)₂Pt(BMIK)](NO₃)₂ · 4H₂O ( 1 ) (P1 ; a = 12.197(5) Å, b = 12.505(5) Å, c = 12.866(5) Å, α = 88.17(3)°, β = 73.55(3)°, γ = 69.84(3)°; Z = 2) and [(BMIK)Pd(α-pyridonate)₂Pd(BMIK)](NO₃)₂ · 4H₂O ( 2 ) (a = 12.408(3) Å, b = 12.660(3) Å, c = 12.913(3) Å, α = 89.55(3)°, β = 74.59(2)°, γ = 68.68(2)°) were prepared by reaction of [Pt(BMIK)(H₂O)₂](NO₃)₂ or [Pd(BMIK)(H₂O)₂](NO₃)₂ with α-pyridone in aqueous solutions at 40°C and were isolated as red air-stable crystals (BMIK = bis(N-methylimidazol-2-yl)ketone). For the synthesis of mixed crystals of 2 with the heterometal complex [(BMIK)Pd(α-pyridonate)₂Pt(BMIK)](NO₃)₂ · 4H₂O ( 3 ) (a = 12.430(4) Å, b = 12.648(3) Å, c = 12.907(4) Å, α = 89.64(2)°, β = 74.57(2)°, γ = 68.65(2)°) α-pyridone was reacted with [Pd(BMIK)(H₂O)₂](NO₃)₂ in a molar ratio of 2 : 1 followed by addition of [Pt(BMIK)(H₂O)₂](NO₃)₂. The dinuclear cations consist of two M(BMIK) moieties (M = Pt, Pd) bridged by the N- and O-atoms of α-pyridonate, forcing the heterocyclic ring into head-head-orientation. Within the dinuclear cation, the two metal atoms are between 2.840 Å and 2.860 Å apart. The intermolecular distances are between 4.762 Å and 4.837 Å. The coordination geometry of both metal atoms is square-planar with the metal atoms being diplaced slightly from their respective coordination planes toward each other. ¹H and ¹⁹⁵Pt NMR spectra are reported for the complexes.     

Crystal structure of monoaquatetra(3,5-dimethylpyrazole)copper(II) nitrate [Cu(C5H8N2)4(H2O)](NO3)2

The crystal structure of monoaquatetra(3,5-dimethylpyrazole)copper(II) nitrate [Cu(C₅H₈N₂)₄(H₂O)]×(NO₃)₂ is determined (Syntex P2₁ automated diffractometer, θ/2θ scan mode within the 2θ range 3–55° at a variable rate, V_min=5 deg/min, λMoK_α graphite monochromator, 5170/2349 measured/observed I_hk1, absorption taken into account experimentally, R_aniso=0.069). The parameters of the monoclinic unit cell are as follows: a=23.569(4), b=8.177(2), c=17.250(6) Å, β=121.65(2)°, V=2830(2) ų, Z=4C₂₀H₃₄CuN₁₀O₇, d_calc=1.388 g/cm³. The space group P2₁ was chosen by the process of structure solution and refinement. The structure is of island type. The complex cations [CuL₄(H₂O)]²⁺ and the (NO₃)^? anions form mixed layers in the planes parallel to (010) at y?0.36 and 0.87. The central atoms of two crystallographically independent complex cations [CuL₄(H₂O)]²⁺ are surrounded with five atoms (O_{H 2 O}+4N) with average Cu?O_{H 2 O} and Cu?N distances of 2.23(2) and 2.04(4), respectively, which form distorted trigonal bipyramids. The average bond lengths in the pyrazole rings are the following: N?N=1.40, N?C=1.40, (C?C)_ring=1.42, and C_ring?C_Me=1.50 Å.     

Hydroxo Bridged Dinuclear Rare Earth Complexes: Syntheses and Crystal Structures of [Ln2(phen)4(H2O)4(OH)2](NO3)4(phen)2 with Ln = Er,Lu

Reactions of phenanthroline (phen) and Er(NO₃)₃ · 5 H₂O or Lu(NO₃)₃ · H₂O in CH₃OH/H₂O yield [Ln₂(phen)₄(H₂O)₄(OH)₂](NO₃)₄(phen)₂ with Ln = Er ( 1 ), Lu ( 2 ). Both isostructural complex compounds crystallize in the triclinic space group P 1 (no. 2) with the cell dimensions: a = 11.257(2) Å, b = 11.467(2) Å, c = 14.069(2) Å, α = 93.93(2)°, β = 98.18(1)°, γ = 108.14(1)°, V = 1696.0(6) ų, Z = 1 for ( 1 ) and a = 11.251(1) Å, b = 11.476(1) Å, c = 14.019(1) Å, α = 93.83(1)°, β = 98.27(1)°, γ = 108.27(1)°, V = 1689.0(3) ų, Z = 1 for ( 2 ). The crystal structures consist of the hydroxo bridged dinuclear [Ln₂(phen)₄(H₂O)₄(OH)₂]⁴⁺ complex cations, hydrogen bonded NO₃^– anions and π‐π stacking (phen)₂ dimers. The rare earth metal atoms are coordinated by four N atoms of two phen ligands and four O atoms of two H₂O molecules and two μ‐OH groups to complete tetragonal antiprisms. Via two common μ‐OH groups, two neighboring tetragonal antiprisms are condensed to a centrosymmetric dinuclear [Ln₂(phen)₄(H₂O)₄(OH)₂]⁴⁺ complex cation. Based on π‐π stacking interactions and hydrogen bonding, the complex cations and (phen)₂ dimers form 2 D layers parallel to (1 0 1), between which the hydrogen bonded NO₃^– anions are sandwiched. The structures can be simplified into a distorted CsCl structure when {[Ln₂(phen)₄(H₂O)₄(OH)₂](NO₃)₄} and (phen)₂ are viewed as building units.     

Synthesis and crystal structure of a three-dimensional 3d-4f heterometallic supramolecular complex {Eu(DMF)4(H2O)2Cr(CN)6·;H2O} n

A lanthanide-transition heterometallic supramolecular complex {Eu(DMF)₄(H₂O)₂Cr(CN)₆·H₂O} _n (1) has been synthesized based on the reaction of K₃[Cr(CN)₆], N,N-dimethylformamide (DMF) and Eu(NO₃)₃·6H₂O. 1 crystallizes in the monoclinic space group P2(1)/c with a=13.130(6)Å, b=12.923(7)Å, c=19.184(9)Å and Z=4. In 1 each Eu(III) is eight-coordinate with six oxygen atoms from four DMF molecules and two H₂O molecules and two nitrogen atoms from two cis-bridging CN ligands to form a distorted dodecahedron. 1 has a three-dimensional network created by the incorporation of coordinative linkage, three inter-molecular and an intrachain hydrogen bond.     

Synthesis,characterization and thermal behaviour of Fe4(OH)11NO3·2H2O

A new iron basic salt, Fe₄(OH)₁₁NO₃·2H₂O, has been prepared by partially hydrolyzing a solution of Fe(NO₃)₃·9H₂O with urea. The X-ray powder diffraction pattern has been indexed within a monoclinic cella=9.99(3) ?,b=9.48(2) ?,c=3.074(3) ? andβ=90.57(1)°. Thermal decomposition reactions in still air and nitrogen flow have been studied by DTA and TG analysis, and the intermediate and final products have been characterized by X-ray diffraction and IR spectroscopy. When this material is thermally decomposed in an X-ray high temperature diffraction chamber, pure iron is formed at 900 °C together with Fe(III) and Fe(II) oxides.

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Zusammenfassung Mittels Hydrolyse einer L?sung von Fe(NO)₃)₃·9H₂O mit Karbamid wurde das neue basische Eisensalz Fe₄(OH)₁₁NO₃·2H₂O dargestellt. Aus einem R?ntgenpulververfahren resultierena=9,55(3) ?,b=9,48(2) ?,c=3,074(3) ? undβ=90,57(1)° für eine monozyklische Zelle. Mittels DTA- und TG-Untersuchungen wurden die thermischen Zersetzungsreaktionen an Luft und im Stickstoffflu? untersucht und die Zwischen- und Endprodukte mit r?ntgendiffraktionsverfahren und IR-Spectroskopie charakterisiert. Bei einer thermischen Zersetzung dieses Stoffes in einer Hochtemperatur-r?ntgendiffraktionskammer wird bei 900 °C elementares Eisen zusammen mit Fe(II)- und Fe(III)-oxiden gebildet.

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Резюме Частичным гидролизо м раствора соли Fe(NO₃)₃ · 9H₂O с мочевиной получен а новая основная соль Fe₄(OH)₁₁NO₃ · 2Н₂О, для которой методо м порошкового рентген оструктурного анализа была установ лена моноклинная стр уктура с параметрами ячейкиа=9,55(3) А,b=9,48(2) ?,c=3,074(3) ? иβ=90,57(1)°. Термиче ское разложение соли изучено методом ДТА и ТГ в динамическо й атмосфере воздуха и азота, а образующиеся промеж уточные и конечные продукты ре акции были охарактер изованы рентгенофазовым ана лизом и ИК спектроскопией. ˉПри термическом разложе нии соли в высокотемпературно й рентгено-диффракци онной камере при 900° образует ся чистое железо вмес те с оксидами двух- и трехвалентного желе за.

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The authors are greateful to Dr. R. M. Rojas for his helpful suggestions.     

THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION. PART 50. THE CRYSTALLIZATION BEHAVIOR OF [trans-Co(en)2(NO2)2]ClO4 (I), MESO-[Co-trans-Me-(N-Me-ETHYLENEDIAMINE)2-trans-(NO2)2]ClO4 (II), K[trans-Co(β-ALANINATO)2(NO2)2] (III) AND THE ISOLATION AND PARTIAL STRUCTURAL DESCRIPTION OF (H5O2)[trans-Co(β-ALANINATO)2(NO2)2] (IV)

Abstract

[trans-Co(en)₂(NO₂)₂]ClO₄ (I) crystallizes, at 22°C, from a deionized water solution, as a racemate, in space group P$1 (No. 2), with lattice constants: a = 6.581(2)Å, b = 8.274(1) Å, c = 12.660(3)Å, α = 77.28(2)Å, β = 76.58(2)°, γ = 75.20(2)° V = 638.71;ų and d(calc; MW = 370.59,z = 2) = 1.927gcm^?3. A total of 2233 data were collected over the range of 4° ≤ 2θ ≤ 50° of these, 1961 (independent and with I ≤ 3σ(I)) were used in the structural analysis. Data were corrected for absorption (μ = 15.989 cm^?1) and the relative transmission coefficients ranged from 0.6792 to 0.9874. The final R(F) and R≤(F) residuals were, respectively, 0.0738 and 0.0763. Two half cations are located at inversion centers; the anions are in general positions.

meso-[Co-trans-Me-(N-Me-ethylenediamine)₂-trans(NO₂)₂]ClO₄ (II) [(N-Meen) = N-methyl-ethylenediamine] crystallizes at 22°C, from a deionized water solution in space group Pbca (No. 61) with lattice constants: a = 16.882(5) Å, b = 11.990(3) Å, c = 15.017(5) Å; V = 3039.72 ų and d (calc;MW = 398.64, z = 8) = 1.742g cm^?3. A total of 5281 data were collected over the range of 4° ≤ 2θ ≤ 50° of these, 1779 (independent and with I ≤ 2.5σ(I) were used in the structural analysis. Data were corrected for absorption (μ = 13.501 cm^?1 and the transmission coefficients ranged from 0.7956 to 0.9947. The final refinement of the structure (anisotropic thermal parameters for the heavy atoms; idealized hydrogens for the cation) are R(F) = 0.045 and R_w (F) = 0.052). The -NO₂ ligands are trans to one another in the axial direction while the N-methyl groups are trans to one another across the basal plane. The cations are located in general positions and the torsional angles of the en rings are δ(N1-C1-C2-N2 = 52.0°) and δ(N3-C3-C4-C4 = 51.0°), in contrast with those of (I) which are of opposite helical chirality. This compound is one of two trans-Co(III)X₂ cations of which we are aware that, while sitting at a general position of the space group, has two ethytenediamine rings of the same helical chirality.

K[trans-Co(β-alaninato)₂(NO₂)₂] (III) obtained after several batches of crystals of (TV) had separated from the mother liquor (see Syntheses). (III) crystallizes at 22°C, in space group Cc (No. 9) with lattice constants: a = 12.385(6)Å, b=13.109(5)Å, c = 8.290(5)Å, β=115.19° V = 1217.97 ų and d(calc; MW = 366.22, z = 4) = 1.997 g cm^?3. A total of 1238 data were collected over the range of 4° ≤ 2θ 50° of these, 1016 (independent and with I ≤ 2.5σ(I) were used in the structural analysis. Data were corrected for absorption (μ 17.90cm^?1) and the transmission coefficients ranged from 0.5322 to 0.6627. The final R(F) and R_w (F) residuals were, respectively 0.020 and 0.022. Solution of the structure, using the first batch of crystals, proved that the compound isolated was the (H₅O₂)⁺ derivative (see below and Discussion). A later batch of crystals contained (III). We have previously observed the precipitation of hydronium salts, trapped by amine carboxylato salts of cobalt (see Discussion). The anions consist of two six-membered rings formed by the metal and two (O,N)-bound β-alaninato ligands; and, both have chair conformations.

(H₅O₂) [trans-Co(β-alaninato)₂(NO₂)₂] (IV) is the substance that first crystalized from an aqueous solution of (III) (see Experimental). It crystallizes, at 22°C, in space group Cc (No. 9) or C2/c (No. 15) with lattice constants: a=12.389(39)Å, b=13.120(11)Å, c=8.299(9) Å, β=115.09(19)° V=1221.72 ų and d(calc; MW=364.15, z=4) = 1.980 g cm^?3. An incomplete data set of 1592 reflections was collected over the range 4° ≤ 2θ ≤ 50° because the crystal decomposes in air due to rapid loss of water of crystallization, as shown by differential scanning calorimetry. 956 data were independent with I ≤ 2.5°(I) and were used in the structural analysis. Data were not corrected for absorption because of decomposition of the crystal. The final R(F) and R_w (F) residuals were, respectively, 0.14 and 0.16. To the precision of such a data set, the anions are identical with those found in (III); however the cation, which sits at an inversion center, consists of a proton sandwiched between the oxygens of two waters thus forming (H₅O₂)⁺ cations similar to those we have described in the past (see Refs. [15–18]).     

Kristallstruktur von CF3TeTeCF3 – Synthese,Charakterisierung und Eigenschaften von CF3TeI

Crystal Structure of CF₃TeTeCF₃. Synthesis, Characterization, and Properties of CF₃TeI Te₂(CF₃)₂ crystallizes in the monoclinic space group P2₁/a with four formular units in the unit cell. The lattice constants are a = 10.13(1) Å, b = 11.489(7) Å, c = 6.822(8) Å and β = 101.20(8)°. CF₃TeI is prepared by a quantitative reaction of Te₂(CF₃)₂ with equimolar amounts of iodine. This compound is very instable, no isolation is possible. NMR spectra have been registrated. From metathesis reactions CF₃TeX (X = C?CC₆H₅, t-C₄H₉, SCN, SC₆F₅) are prepared.     

X-RAY STRUCTURES OF BIS[(2-AMINOPHENYL)DIPHENYLPHOSPHINE]BIS-(ETHANOL)SILVER(I) NITRATE AND TRIS[(2-AMINOPHENYL)DIPHENYLPHOSPHINE] SILVER(I) NITRATE MONOHYDRATE

Abstract

The crystal structures of two Ag(I) salts, [Ag(LH)₂(EtOH)₂](NO₃) (1) and [Ag(LH)₃](NO₃).H₂O (2) where LH is (2-aminophenyl)diphenylphosphine, have been determined at room temperature. In 1 the Ag atom is coordinated by two P atoms derived from the phosphine ligands (Ag-P(1) 2.433(3) and Ag-P(2) 2.439(3) Å and P(1)-Ag-P(2) 160.1(1)°) and two O atoms derived from two weakly coordinating ethanol molecules (Ag-O(1a) 2.49(1) and Ag-O(2a) 2.75(1) Å). In 2 the three phosphine ligands coordinate via the P atoms (Ag-P 2.455(2), 2.462(2) and 2.484(2) Å) which define a trigonal planar geometry about the Ag atom. In neither case was any evidence found for a bonding interaction between the amino-N atom and the Ag atom. Crystals of 1 are monoclinic, space group P2₁/n with unit cell dimensions: a=10.272(4), b=16.358(2), c=23.709(3) Å, β=101.01(2)° and Z=4 and crystals of 2 are triclinic, space group P 1 with a=11.857(2), b=21.285(2), c=11.190(4) Å, α=91.77(1), β=104.50(2), γ=97.93(1)° and Z=2. The structures were each refined by a full-matrix least-squares procedure to final R=0.058 using 2433 reflections for 1 and to R=0.069 using 4428 reflections for 2.     

Cadmium(II) complex with 2-methyl-1H-4,5-imidazoledicarboxylic acid ligand: synthesis,characterization, and biological activity

A coordination polymer, [Cd(L)₂(H₂O)₂]_n (HL = 2-methyl-1H-4,5-imidazoledicarboxylic acid), was prepared from reactions of Cd(NO₃)₂ with L at room temperature. It was characterized by IR spectra and elemental analysis. The complex was structurally characterized by X-ray single-crystal diffraction revealing that the complex crystallizes in monoclinic with P2(1)/c space group, a = 12.203(10)?Å, b = 9.332(8)?Å, c = 7.554(7)?Å, β = 100.894(2)?Å, V = 844.7(13)?ų, Z = 2. Fluorescence and UV absorption spectroscopy indicated that the complex can bind to fish sperm DNA. Gel electrophoresis assay demonstrated the ability to cleave the HL-60 plasmid DNA. Apoptotic study showed that the complex exhibited significant cancer cell (JEKO and KB) inhibitory rate.     

A study of the structure and properties of mixed-ligand Cu(II) complexes with hexafluoroacetylacetone and methyl-, phenyl-ketoimines

The synthesis and X-ray single crystal study of two mixed-ligand Cu(II) complexes are performed: (CH₃C(NCH₃)CHC(O)CH₃)(CF₃C(O)CHC(O)CF₃)Cu (1) (space group P2₁/c, a = 7.0848(12) Å, b = 17.854(3) Å, c = 11.837(2) Å, β = 100.495(6)°, V = 1472.4(4) ų, Z = 4), (CH₃C(NC₆H₅)CHC(O)CH₃)· (CF₃C(O)CHC(O)CF₃)Cu (2) (space group P-1, a = 9.1119(4) Å, b = 9.6954(4) Å, c = 11.1447(6) Å, α = 113.784(2)°, β = 92.383(2)°, γ = 95.402(2)°, V = 893.52(7) ų, Z = 2). The structures are molecular, formed from neutral mixed-ligand copper complexes. The central copper atom has the (3O+N) coordination environment with average Cu-O distances of 1.948 Å and Cu-N of 1.932 Å; the chelate O-Cu-N angle (average) is 94.0°. In the structures, the complexes are linked into dimeric associates with Cu…Cu distances of 3.197 Å (for 1) and 3.246 Å (for 2). The volatility of mixed-ligand complexes 1 and 2 is in between of that of the starting homo-ligand complexes.     

Coordination of the new weakly coordinating anions Al(OCH(CF3)2)4−, Al(OC(CH3)(CF3)2)4−, and Al(OC(Ph)(CF3)2)4− to the monovalent metal ions Li+ and Tl+

The structures of Li⁺ or Tl⁺ salts of three new fluoroalkoxide-containing aluminate anions were determined by X-ray crystallography. For LiAl(OC(Ph)(CF₃)₂)₄, monoclinic, C2/c, a=42.297(6), b=10.641(1), c=19.132(2) Å, β=114.808(9)°, Z=8, T=−100°C, R=0.052; for TlAl(OC(CH₃)(CF₃)₂)₄, monoclinic, P2₁/c, a=12.650(3), b=9.970(2), c=21.237(4) Å, β=94.00(3)°, Z=4, T=−100°C, R=0.073; for TlAl(OCH(CF₃)₂)₄, monoclinic, P2₁/n, a=14.261(1), b=9.8024(9), c=16.911(2) Å, β=93.467(8), Z=4, T=−130°C, R=0.053. The monatomic, monovalent cations interact with their respective anions by means of M–O and M–F bonds. The Tl⁺ cations in TlAl(OCH(CF₃)₂)₄ and TlAl(OC(CH₃)(CF₃)₂)₄ interact with three different aluminate anions. The Li⁺ cation in LiAl(OC(Ph)(CF₃)₂)₄ interacts with only one aluminate anion, forming a rare trigonal–prismatic LiO₂F₄ coordination unit.     

A blue luminescent binuclear cadmium-orotate coordination polymer: synthesis,crystal structure,and thermogravimetric analysis

Assembly of orotic acid (H₃Or, 1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimidinecarboxylic) and Cd(NO₃)·6H₂O yielded a coordination polymer, [(Cd(Hor)·2.5H₂O)₂]_n (1), which has been characterized by X-ray single-crystal diffraction, TGA, and ?uorescence spectra. Single-crystal X-ray structural analyses reveal that 1 is a hydrogen-bonded binuclear Cd-orotate coordination polymer in which both Cd²⁺ ions have different coordination environments with identical distorted octahedral geometry. Crystal data for 1: monoclinic, space group P2₁/n, a = 7.0209(10) Å, b = 13.974(2) Å, c = 17.541(3) Å, β = 98.842(2)°, V = 1700.5(4) Å, Z = 4, R1 = 0.0269, wR2 = 0.0612, θ_max = 25.960. The emission spectrum of the Cd-complex recorded with 265 nm excitation wavelength reveals the complex has strong blue luminescence with the peak maximum 420 nm (2.95 eV) as a result of the n–π* and π–π* transitions on the H₃Or ligand.     

Bidentate coordination of a diketo phosphorus ylide: synthesis and structure of [(C6H5)3PC(COCH3)(COC6H5)-κO,O′]UO2(NO3)2

A 1?:?1 chelate complex [(C₆H₅)₃PC(COCH₃)(COC₆H₅)-κO,O′]UO₂(NO₃)₂ has been synthesized by reaction of (C₆H₅)₃PC(COCH₃)(COC₆H₅) with UO₂(NO₃)₂?·?6H₂O in methanol at room temperature and characterized by elemental analysis, spectroscopy as well as by single-crystal X-ray diffraction. The complex crystallizes in P2₁/n space group with a?=?10.007(2)?Å, b?=?15.285(7)?Å, c?=?19.20(1)?Å, β?=?91.22(3)°, V?=?2936(2)?ų, Z?=?4, D _c?=?1.847?g?cm^?3. In the solid state structure, the dihedral angle [88.1(4)°] between the planes defined by the two quartets of atoms O1 O8 O2 O4 and O6 O5 O3 O7 is close to 90°, as expected for a triangulated dodecahedral geometry around uranium.