Synthesis,Crystal Structures and Luminescent Properties of Terbium,Neodymium and Yttrium Complexes with a New Amide Type Ligand

Solid complexes of terbium, neodymium and yttrium nitrates with an amide type ligand, N‐benzyl‐2‐(benzyloxy)benzamide ( L ) have been prepared in ethyl acetate and characterized by elemental analysis and IR spectroscopy. The crystal and molecular structures of the complexes Tb L ₃(NO₃)₃, Nd L ₃(NO₃)₃ and Y L ₃(NO₃)₃ have been determined by single crystal X‐ray diffraction. The crystal structures of the complexes are similar. The structures show that the crystal consists of two similar but independent molecules in the asymmetric unit and the metal ion is coordinated toward nine donor atoms, three of which belong to the oxygen atoms of three monodentate ligands and six oxygen atoms from three bidentate nitrates. Furthermore, the RE L ₃(NO)₃ complex units are linked by the intermolecular hydrogen bonds to form a three‐dimensional net. At the same time, the luminescent properties of the ligand and the complex Tb L ₃(NO₃)₃ were studied as well.     

Synthesis and structures of tris(pentafluorophenyl)silylamines

Tris(pentafluorophenyl)silylamines were synthesized by silylation of amines and imines with (C₆F₅)₃SiCl or (C₆F₅)₃SiOTf in the presence of triethylamine. The crystal structures of the (C₆F₅)₃SiN(H)CH₂Ph and (C₆F₅)₃SiN(CH=CMe₂)CH₂Ph compounds were studied by X-ray diffraction. The crystal packings were analyzed by quantum chemical calculations in terms of the density functional theory (PBE exchange-correlation functional). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1345–1352, July, 2007.     

Synthesis, crystal, molecular, and electronic structures of hydride carbonyl ruthenium(II) complexes with pseudohalide ligands

Two pseudohalide hydride carbonyl ruthenium(II) complexes with formulae: [RuH(N₃)(CO)(PPh₃)₃] (1) and [RuH(NCO)(CO)(PPh₃)₃] (2) have been synthesized by the reactions of [RuHCl(CO)(PPh₃)₃] with sodium azide or sodium cyanate, respectively, and are compared with the previously described thiocyanate analog [RuH(NCS)(CO)(PPh₃)₃]. The molecular structures of the new compounds were determined by X-ray crystallography and their spectroscopic properties have been studied. Based on the crystal structures, computational investigations have been carried out in order to determine the electronic structures of the complexes. The electronic spectra were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes.     

Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2

Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ were prepared by the reaction of Ni(NH₃)₂X₂ with NiX₂ at 350 °C in a steel autoclave. The crystal structures were determined by X‐ray powder diffraction using synchrotron radiation and refined by Rietveld methods. Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ are isotypic and crystallize in the space group I2/m with Z = 8 and for Ni(NH₃)Cl₂: a = 14.8976(3) Å, b = 3.56251(6) Å, c = 13.9229(3) Å, β = 106.301(1)°; Ni(NH₃)Br₂: a = 15.5764(1) Å, b = 3.74346(3) Å, c = 14.4224(1) Å, β = 105.894(1)°. The crystal structures are built up by two crystallographically distinct but chemically mostly equivalent polymeric octahedra double chains [NiX_3/3X_2/2(NH₃)] (X = Cl, Br) running along the short b‐axis. The octahedra NiX₅NH₃ share common edges therein. The crystal structures of the ammines Ni(NH₃)_mX₂ with m = 1, 2, 6 can be derived from that of the halides NiX₂ (X = Cl, Br) by successive fragmentation of its CdCl₂ like layers by NH₃.     

Complexes of N‐Thiophosphorylthiourea α‐NaphthylNHC(S)NHP(S)(OiPr)2 (HL) with Copper(I). Crystal Structures of HL and Cu(PPh3)2L

Reaction of the potassium salt of N‐thiophosphorylated thiourea α‐naphthylNHC(S)NHP(S)(OiPr)₂ ( HL ) with Cu(PPh₃)₃I in aqueous EtOH/CH₂Cl₂ leads to the mononuclear complex [Cu(PPh₃)₂L–S,S′]. By using copper(I) iodide instead ofCu(PPh₃)₃I, the polynuclear complex [Cu_n(L–S,S′)_n] was obtained. The structures of these compounds were investigated by elemental analysis, ¹H and ³¹P{¹H} NMR and IR spectroscopy. The crystal structures of HL and Cu(PPh₃)₂L were determined by single‐crystal X‐ray diffraction.     

Palladium site ordering and the occurrence of superconductivity in Bi2Pd3Se2−xSx

The crystallographic and electronic structures of compounds related to parkerite (Bi₂Ni₃S₂) are investigated with respect to the recently reported occurrence (Bi₂Pd₃Se₂) and absence (Bi₂Pd₃S₂) of superconductivity. Similarities and differences of the crystal structures are discussed within the series of solid solutions Bi₂Pd₃S_2−xSe_x from powder and single crystal diffraction data. From crystal structure refinements, the question of different structures and settings of parkerite is discussed. Similar and different 2D and 3D partial Pd-Ch (Ch=S, Se) structures are related to half antiperovskite ordering schemes. To investigate the relation of low dimensional structures and the occurrence of superconductivity, electronic structures are analyzed by scalar-relativistic DFT calculations, including site projected DOS, ECOV and Fermi surfaces.     

New Saccharinato/Ammonia Complexes of Nickel(II) and Zinc(II). A Structural and Spectroscopic Study

Two new saccharinate/NH₃ complexes of composition [Ni(sac)₂(NH₃)₄] and [Zn(sac)₂(NH₃)₂] were obtained and their crystal structures determined by single crystal X‐ray diffractometry. The elongated octahedral Ni^II complex crystallizes in the monoclinic P2₁/c space group with Z = 2 whereas the tetrahedral Zn^II complex is triclinic (space group and Z = 2). For [Ni(sac)₂(NH₃)₄] the magnetic moment and electron absorption spectrum were obtained and discussed. The infrared spectra of both complexes were also recorded and briefly commented.     

Cinnamamide pharmacophore for anticonvulsant activity: evidence from crystallographic studies

A number of cinnamamide derivatives possess anticonvulsant activity due to the presence of a number of important pharmacophore elements in their structures. In order to study the correlations between anticonvulsant activity and molecular structure, the crystal structures of three new cinnamamide derivatives with proven anticonvulsant activity were determined by X‐ray diffraction, namely (R,S)‐(2E)‐N‐(2‐hydroxybutyl)‐3‐phenylprop‐2‐enamide–water (3/1), C₁₃H₁₇NO₂·0.33H₂O, ( 1 ), (2E)‐N‐(1‐hydroxy‐2‐methylpropan‐2‐yl)‐3‐phenylprop‐2‐enamide, C₁₃H₁₇NO₂, ( 2 ), and (R,S)‐(2E)‐N‐(1‐hydroxy‐3‐methyl‐butan‐2‐yl)‐3‐phenylprop‐2‐enamide, C₁₄H₁₉NO₂, ( 3 ). Compound ( 1 ) crystallizes in the space group P with three molecules in the asymmetric unit, whereas compounds ( 2 ) and ( 3 ) crystallize in the space group P2₁/c with one and two molecules, respectively, in their asymmetric units. The carbonyl group of ( 2 ) is engaged in an intramolecular hydrogen bond with the hydroxy group. This type of interaction is observed for the first time in these kinds of derivatives. A disorder of the substituent at the N atom occurs in the crystal structures of ( 2 ) and ( 3 ). The crystal packing of all three structures is dominated by a network of O—H…O and N—H…O hydrogen bonds, and leads to the formation of chains and/or rings. Furthermore, the crystal structures are stabilized by numerous C—H…O contacts. We analyzed the molecular structures and intermolecular interactions in order to propose a pharmacophore model for cinnamamide derivatives.     

Synthesis,characterization, and structural determination of copper(II) complexes with alkyl derivatives of hydroxybenzophenones

Four mononuclear copper(II) complexes, [Cu(LFQM-115)₂] (1), [Cu(LFQM-116)₂] (2), [Cu(LFQM-117)₂] (3) and [Cu(octyloxy)₂] (4) [LFQM-115 = 2-hydroxy-4-O-methylbenzophenone (C₁₄H₁₁O₃), LFQM-116 = 2-hydroxy-4-O-butylbenzophenone (C₁₇H₁₈O₃), LFQM-117 = 2-hydroxy-4-O-(33-dimethylallyl)benzophenone (C₁₈H₁₈O₃) and octyloxy = 2-hydroxy-4-O-octylbenzophenone (C₂₁H₂₅O₃)], have been prepared and investigated by infrared spectroscopy, thermal analysis, and powder and single crystal X-ray diffraction. Even though the synthesis and infrared analysis of 1, 2, and 4 have been reported previously, their crystal structures were elucidated for the first time here. In addition, the crystal structures of LFQM-116 and LFQM-117 were also determined by single crystal X-ray diffraction. The pseudo-translational symmetry found in LFQM-116 and the isomorphism between LFQM-115 and LFQM-117 are discussed. The complexes were prepared from a reaction of copper(II) nitrate trihydrate and the respective ligand in a (1:2) molar ratio in methanol (for 1 and 2) or THF (for 3 and 4) with addition of NaOH. Furthermore, crystallographic studies show that each copper(II) exhibits a square planar geometry, coordinated by four oxygens of two ligands. The nature and crystal packing of the intermolecular interactions are discussed. Compounds 2 and 3 are isomorphic crystals and all structures have the same supramolecular synthon.     

Volatile fluorinated trimethylplatinum(IV) β-diketonates with pyridine: Synthesis,properties, and structure

Volatile fluorinated trimethylplatinum(IV) β-diketonates with pyridine (CH₃)₃Pt(CH₃-CO-CH-CO-CF₃)Py (I) and (CH₃)₃Pt(CF₃-CO-CH-CO-CF₃)Py (II) obtained from trifluoroacetylacetone and hexafluoroacetylacetone were studied. The synthesis, elemental analysis data, and IR spectra were described. X-Ray diffraction analysis was performed and the crystal structure was determined; the geometric characteristics of complexes I and II were obtained. Both structures are monomeric molecular structures. The molecules in the crystal are connected only by weak van der Waals forces. The coordination polyhedron of platinum in I and II is a slightly distorted octahedron. The shortest Pt…Pt distances are 6.639 Å (for I) and 6.254 Å (for II). The average P-O, Pt-N, and P-C distances are 2.157, 2.182, and 2.030 Å, respectively. The deviations of the bond angles at Pt atoms from ideal values of 90° do not exceed 4.8°.     

Floridcarbonate der Alkalimetalle

Alkali Metal Fluoride Carbonates Alkali metal fluoride carbonates A₃(CO₃)F and A₂A′(CO₃)F with A,A′ = K, Rb, Cs have been obtained by solid state reaction between the respective alkali metal fluorides and carbonates. They crystallize isotype to K₃(CO₃)F. The cell dimensions of K₂Rb(CO₃)F, KRb₂(CO₃)F, and CsRb₂(CO₃)F have been determined and refined by X-ray powder diffraction methods. Solid solutions are formed between K₃(CO₃)F and Rb₃(CO₃)F. The crystal structures of K₂Rb(CO₃)F and KRb₂(CO₃)F were refined based on single crystal diffraction data. A factor group analysis allowed for interpretation of IR and Raman spectra of K₃(CO₃)F.     

Molecular structure and electrochemistry of carbon-bridged diferrocenyl compounds

Four diferrocenyl compounds: FcC(CH₃)₂Fc (1), Fc(CH₃)C(C₂H₅)Fc (2), Fc(CH₃)C(C₃H₇)Fc (3), and Fc(CH₃)C(C₆H₅)Fc (4) were synthesized and characterized by NMR, FT-IR, MS, and elemental analysis. The molecular structures were determined by using X-ray single crystal diffraction. The electrochemical interactions between two ferrocenyl units in these compounds were investigated by cyclic voltammetry and theoretical calculation. The electron density of bridging carbon was a key factor for the separation of two ferrocenyl units.     

水合希土硝酸盐与本并及单环己基-12-冠-4配合物的合成、性质及晶体结构

在乙腈介质中合成了苯并－１２－冠－４（简称Ｂ－１２－Ｃ－４）和单环己基－１２－冠－４（简称Ｃｙ－１２－Ｃ－４）的六种希土配合物：ＲＥ（ＮＯ３）３·Ｂ－１２－Ｃ－４（ＲＥ＝Ｐｒ，Ｇｄ，Ｙｂ，Ｌｕ），ＲＥ（ＮＯ３）３·Ｃｙ－１２－Ｃ－４（ＲＥ＝Ｌａ，Ｌｕ）。研究了它们的ＩＲ及＾１ＨＮＭＲ性质，并测定了四种单晶的结构，用ＩＮＤＯ法计算了Ｌｕ（ＮＯ３）３·Ｂ－１２－Ｃ－４，Ｌｕ（ＮＯ３）３·Ｃｙ－１２－Ｃ     

Synthesis and Characterization of Diorganocobalt Chlorides by Aliphatic Vinylic C–Cl Bond Activation

Three diorganocobalt chlorides [CoClMe(PMe₃)₂–{(C₅H₆)–CH=O}] ( 4 ), [CoClMe(PMe₃)₂–{(C₆H₈)–CH=O}] ( 5 ), and [CoClMe(PMe₃)₂–{(C₆H₇Memeta)–CH=O}] ( 6 ) were synthesized through cyclometalation reactions with aldehyde as an anchoring group involving aliphatic vinylic C–Cl bond activation. Complexes 4 – 6 were characterized by IR and NMR spectroscopy. The crystal and molecular structures of complexes 4 and 5 were determined by single‐crystal X‐ray diffraction. Complexes 4 – 6 are stable in solution at room temperature, but they decompose at above 30 °C affording C,C‐couplings products with the formation of [Co(PMe₃)₃Cl]. The results of this work will be important for people to deepen the understanding of the C–Cl bond activation mechanism.     

The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

The binary zirconium and hafnium polyazides [PPh₄]₂[M(N₃)₆] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF₄ by fluoride–azide exchange reactions with Me₃SiN₃ in the presence of two equivalents of [PPh₄][N₃]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N₃)₄], [M(N₃)₅]^? and [M(N₃)₆]^2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.     

Solvothermal Synthesis and Structure of Two 2D Tin–Selenides with Long Alkyldiamine NH2(CH2) n NH2 (n = 8, 10)

Reactions of NH₂(CH₂) _n NH₂ (n = 8,10) with elemental Sn and Se in a H₂O/CH₃OH mixture at 150°C afford two compounds (NH₃(CH₂)₈NH₃)Sn₃Se₇ (1) and (NH₃(CH₂)₈NH₃)Sn₃Se₇ (2). The crystal structures were determined by single crystal X-ray diffraction at room temperature. Both compounds exhibit the same anionic structure—a 6³ netted plane composed of [Sn₃Se₇]^2– subunits. The distance between the centers of crystal 1 layers is 7.5 Å, somewhat shorter than the distance (8.5 Å) in crystal 2.     

Syntheses,crystal structures and magnetic properties of complexes based on [Ni(L-L)3]2+ complex cations with dimethylderivatives of 2,2′-bipyridine and TCNQ

From the aqueous-methanolic systems Ni(NO₃)₂ – LiTCNQ – 5,5′-dmbpy and Ni(NO₃)₂ – LiTCNQ – 4,4′-dmbpy three novel complexes [Ni(5,5′-dmbpy)₃](TCNQ)₂ (1), [Ni(4,4′-dmbpy)₃](TCNQ)₂ (2) and [Ni(4,4′-dmbpy)₃]₂(TCNQ-TCNQ)(TCNQ)₂∙0.60H₂O (3), were isolated in single crystal form. The new compounds were identified using chemical analyses and IR spectroscopy. Single crystal studies of all samples corroborated their compositions and have shown that their ionic structures contain the complex cations [Ni(5,5′-dmbpy)]²⁺ (1) or [Ni(4,4′-dmbpy)]²⁺ (2 and 3). The anionic parts of the respective crystal structures 1–3 are formed by TCNQ^⋅- anion-radicals and in 3 also by a σ-dimerized dianion (TCNQ-TCNQ)^2- with a C-C distance of 1.663(5) Å. The supramolecular structures are governed by weak hydrogen bonding interactions. The variable-temperature (2–300 K) magnetic studies of 1 and 3 confirmed the presence of magnetically active Ni(II) atoms with S = 1 and TCNQ^⋅- anion-radicals with S = 1/2 while the (TCNQ-TCNQ)^2- dianion is magnetically silent. The magnetic behavior was described by a complex magnetic model assuming strong antiferromagnetic interactions between some TCNQ^⋅- anion-radicals.     

Rebuttal of the Existence of Solid Rare Earth Bicarbonates and the Crystal Structure of Holmium Nitrate Pentahydrate

The synthesis routes of Gd(HCO₃)₃ · 5H₂O and Ho(HCO₃)₃ · 6H₂O, which are the only known bicarbonates of rare earth metals, were refuted and the published crystal structures were discussed. Because of the structural relationship of Ho(HCO₃)₃ · 6H₂O to rare earth nitrate hexahydrates, 1 the synthesis of holmium nitrate hydrate was considered and the crystal structure of Ho(NO₃)₃ · 5H₂O was solved by single crystal X‐ray diffraction measurements. Ho(NO₃)₃ · 5H₂O was determined to crystallize in the triclinic space group P1 (no. 2) with a = 6.5680(14) Å, b = 9.503(2) Å, c = 10.462(2) Å, α = 63.739(14)°, β = 94.042(2)° and γ = 76.000(16)°. The crystal structure consists of isolated [Ho(H₂O)₄(NO₃)₃] polyhedra and non‐coordinating water molecules. It is isotypic to other rare earth nitrate pentahydrates.     

The New Carbodiimide Li2Gd2Sr(CN2)5 Having a Crystal Structure Related to That of Gd2(CN2)3

The new carbodiimide compounds Li₂RE₂Sr(CN₂)₅ (RE = Sm, Gd, Eu, Tb) were prepared by a straight forward solid state metathesis reaction of REF₃, SrF₂, and Li₂(CN₂) at around 600 °C. The crystal structure of Li₂Gd₂Sr(CN₂)₅ was solved based on X‐ray single‐crystal diffraction data. Corresponding Li₂RE₂Sr(CN₂)₅ compounds were analyzed by isotypic indexing of their powder patterns. The crystal structure of Li₂Gd₂Sr(CN₂)₅ can be well related to that of Gd₂(CN₂)₃, because both structures are based on layered structures composed of close packed layers of [N=C=N]^2– sticks, alternating with layers of metal ions. The crystal structure of Li₂Gd₂Sr(CN₂)₅ can be considered to contain an ABC layer sequence of [N = C=N]^2– layers with the interlayer voids being occupied by (three) distinct types of cations.     

X-ray diffraction study of [M<Superscript>I</Superscript>(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl] [M<Superscript>II</Superscript>Br<Subscript>6</Subscript>] (M<Superscript>I</Superscript> = Rh,Ir; M<Superscript>II</Superscript> = Re,Ir) polycrystals

Based on the X-ray diffraction data for polycrystals, the crystal structures of double complex salts [Rh(NH₃)₅Cl][ReBr₆] and [Ir(NH₃)₅Cl][ReBr₆] are refined. The structure of [Rh(NH₃)₅Cl][IrBr₆] is determined. Initial models are constructed using the Monte Carlo method in the straight space. Further refinement is made by the Rietveld method. It is shown that such an approach is suitable for the refinement of crystal structures composed of isolated rigid polyhedra and can be used to determine the structure of salts without structural analogues