Syntheses and Crystal Structures of the Novel Ternary Thioborates Na3BS3, K3BS3, and Rb3BS3

The orthothioborates Na₃BS₃, K₃BS₃ and Rb₃BS₃ were prepared from the metal sulfides, amorphous boron and sulfur in solid state reactions at temperatures between 923 and 973 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction experiments. Na₃BS₃ crystallizes in the monoclinic space group C2/c (No. 15) with a = 11.853(14) Å, b = 6.664(10) Å, c = 8.406(10) Å, β = 118.18(2)° and Z = 4. K₃BS₃ and Rb₃BS₃ are monoclinic, space group P2₁/c (No. 14) with a = 10.061(3) Å, b = 6.210(2) Å, c = 12.538(3) Å, β = 112.97(2) and a = 10.215(3) Å, b = 6.407(1) Å, c = 13.069(6) Å, β = 103.64(5)°, Z = 4. The potassium and rubidium compounds are not isotypic. All three compounds contain isolated [BS₃]^3– anions with boron in a trigonal‐planar coordination. The sodium cations in Na₃BS₃ are located between layers of orthothioborate anions, in the case of K₃BS₃ and Rb₃BS₃ stacks of [BS₃]^3– entities are connected via the corresponding cations. X‐ray powder patterns were measured and compared to calculated ones obtained from single crystal X‐ray structure determinations.     

Novel Alkaline Earth Metal Chalcogenoborates: Syntheses and Crystal Structures of Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se

Systematic studies on quaternary thio‐ and selenoborates containing heavier alkaline earth metal cations led to the two new isotypic crystalline phases Sr_4.2Ba_2.8(BS₃)₄S and Ba₇(BSe₃)₄Se. Both compounds consist of trigonal‐planar BQ₃ (Q = S, Se) units, isolated Q^2– anions and the corresponding counter‐ions. The two new chalcogenoborates were prepared in solid state reactions from the metal sulfides (selenides), amorphous boron and sulfur (selenium). Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 870 K were applied. Sr_4.2Ba_2.8(BS₃)₄S and Ba₇(BSe₃)₄Se crystallize in the monoclinic space group C2/c (no. 15) with a = 9.902(3) Å, b = 23.504(9) Å, c = 9.884(3) Å, β = 90.01(3)° and Z = 4 in the case of the thioborate, while for the selenoborate the lattice parameters a = 10.513(2) Å, b = 25.021(5) Å, c = 10.513(2) Å, β = 90.10(3)° were determined. X‐ray powder patterns are compared to calculated diffraction data obtained from single crystal X‐ray structure determination.     

Sr3(BS3)2 und Sr3(B3S6)2: Zwei neue nicht‐oxidische Chalkogenoborate mit trigonal‐planar koordiniertem Bor

Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂: Two Novel Non‐oxidic Chalcogenoborates with Boron in a Trigonal‐Planar Coordination The thioborates Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂ were prepared from strontium sulfide, amorphous boron and sulfur in solid state reactions at a temperature of 1123 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction. Sr₃(BS₃)₂ crystallizes in the monoclinic spacegroup C2/c (No. 15) with a = 10.187(4) Å, b = 6.610(2) Å, c = 15.411(7) Å, β = 102.24(3)° and Z = 4. The crystal structure of Sr₃(B₃S₆)₂ is trigonal, spacegroup R3¯ (Nr. 148), with a = 8.605(1) Å, c = 21.542(4) Å and Z = 3. Sr₃(BS₃)₂ contains isolated [BS₃]^3— anions with boron in a trigonal‐planar coordination. The strontium cations are found between the layers of orthothioborate anions. Sr₃(B₃S₆)₂ consists of cyclic [B₃S₆]^3— anions and strontium cations, respectively.     

The First Rare Earth Metal Thioborate: Synthesis and Crystal Structure of EuB2S4

Systematic studies on thio‐ and selenoborates containing heavier metal cations led to the new crystalline phase EuB₂S₄. The crystal structure of the europium metathioborate reveals polymeric [(B₂S₄)^2—]_n anions and divalent Eu‐cations which are connected via ionic interactions. The building blocks of the anions consist of BS₄‐tetrahedra. Condensation of these BS₄‐tetrahedra leads to corner‐ and edge‐sharing 2D‐networks running parallel to (1 0 0). Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 990 K were applied. EuB₂S₄ crystallizes in the monoclinic space group P2₁/c (no. 14) with a = 6.4331(6)Å, b = 14.099(1)Å, c = 6.0731(6)Å, β = 110.55(8)° and Z = 4.     

ChemInform Abstract: Novel Alkaline Earth Metal Chalcogenoborates: Syntheses and Crystal Structures of Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

BaB2S4: Das erste nicht‐oxidische Chalkogenoborat mit trigonal‐planar und tetraedrisch koordiniertem Bor

BaB₂S₄: The first non‐oxidic Chalcogenoborate with Boron in a trigonal‐planar and tetrahedral Coordination Hitherto we know boron in a trigonal‐planar and a tetrahedral coordination within one crystal structure from boron oxides in various compounds. With the novel bariummetathioborate BaB₂S₄ we now report a crystal structure containing BS₃ and BS₄ units in the ratio 1 : 1 forming infinite chains along [001]. BaB₂S₄ was synthesized in a solid state reaction at a temperature of 800 °C from barium sulfide, amorphous boron and sulfur and crystallizes in the monoclinic space group Cc (no. 9) with the following lattice parameters: a = 6.6465(5) Å, b = 15.699(1) Å, c = 6.0306(5) Å, β = 110.96(1)°, Z = 4.     

Three Nickel(II) and Zinc(II) Complexes with Two Novel Nitronyl Nitroxide Ligands: Syntheses,Crystal Structures,and Luminescent Properties

To explore the coordination abilities of nitronyl nitroxide ligands, two ligands substituted with quinoxaline ( L¹ ) and 2‐phenyl‐1, 2, 3‐triazole ( L² ) and their Ni^II and Zn^II complexes: Ni( L¹ )(hfac)₂ ( 1 ), Ni( L² )(hfac)₂ ( 2 ), and Zn( L² )(hfac)₂ ( 3 ) (hfac = hexafluoroacetylacetonate), were synthesized and characterized. X‐ray single‐crystal diffraction analysis shows that compound 1 has a mononuclear structure, which is further linked into a three‐dimensional (3D) supramolecular network by C–H ··· F hydrogen‐bonding, C–H ··· π, and π ··· π stacking interactions. Complexes 2 and 3 have similar mononuclear structures, which are further linked into one‐dimensional (1D) supramolecular chains by various intermolecular weak interactions, such as C–H ··· F hydrogen‐bonding, and π ··· π stacking interactions. The results indicate that the steric bulk of L¹ and L² and the existence of hexafluoroacetylacetonate (hfac) play important roles in controlling the formation of the final frameworks of complexes 1 – 3 . Moreover, the luminescent properties of the ligands and their complexes were investigated in detail.     

Syntheses,Crystal Structures and Photophysical Properties of a Series of Cadmium(II) Coordination Polymers

Three cadmium(II) coordination polymers [Cd(NA)₂(H₂O)₂]_n ( 1 ), {[Cd(NA)(phen)(NO₃)]·(H₂O)_1/2}_n ( 2 ), {[Cd(NA)(CH₃C₆H₄COO)(H₂O)₂]·(CH₃C₆H₄COOH)}_n ( 3 ) (HNA = nicotinic acid, phen = 1, 10‐phenanthroline) have been synthesized by hydrothermal method. Their single‐crystal structures were determined by X‐ray diffractometry. The absorption, excitation and emission spectra were investigated and all the complexes emit strong fluorescence: λ^em_max = 544 nm (λ^ex = 492 nm), 1 ; λ^em_max = 466 nm (λ^ex = 393 nm), 2 ; λ^em_max = 430 nm (λ^ex = 313 nm), 3 . At room temperature in the solid state the fluorescence lifetimes of the complexes were investigated and the relationships between the spectra were discussed as well as the connections of luminescence and crystal structures.     

Syntheses and Crystal Structures of BaAgTbS3, BaCuGdTe3, BaCuTbTe3, BaAgTbTe3, and CsAgUTe3

Five new quaternary chalcogenides of the 1113 family, namely BaAgTbS₃, BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and CsAgUTe₃, were synthesized by the reactions of the elements at 1173–1273 K. For CsAgUTe₃ CsCl flux was used. Their crystal structures were determined by single‐crystal X‐ray diffraction studies. The sulfide BaAgTbS₃ crystallizes in the BaAgErS₃ structure type in the monoclinic space group C³,_2h‐C2/m, whereas the tellurides BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and CsAgUTe₃ crystallize in the KCuZrS₃ structure type in the orthorhombic space group D¹_,2⁷_,h‐Cmcm. The BaAgTbS₃ structure consists of edge‐sharing [TbS₆^9–] octahedra and [AgS₅^9–] trigonal pyramids. The connectivity of these polyhedra creates channels that are occupied by Ba atoms. The telluride structure features ²_∞[MLnTe₃^2–] layers for BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and ²_∞[AgUTe₃^1–] layers for CsAgUTe₃. These layers comprise [MTe₄] tetrahedra and [LnTe₆] or [UTe₆] octahedra. Ba or Cs atoms separate these layers. As there are no short Q ··· Q (Q = S or Te) interactions these compounds achieve charge balance as Ba²⁺M⁺Ln³⁺(Q^2–)₃ (Q = S and Te) and Cs⁺Ag⁺U⁴⁺(Te^2–)₃.     

Syntheses and Crystal Structures of Two Novel Linear Trinuclear Schiff Base Nickel(II) and Cadmium(II) Complexes

Two novel linear trinuclear Schiff base complexes, [Ni{Ni(C₁₇H₁₄Br₂N₂O₂)(NO₃)(H₂O)}₂] · 2MeOH · 2H₂O ( 1 ), and [Cd{Ni(C₂₅H₂₀N₂O₂)(CH₃COO)}₂] ( 2 ), were synthesized and characterized by elemental analyses, infrared spectroscopy, and X‐ray single crystal determinations. There are three bridges across the Ni‐M atom pairs (M is Ni for 1 , and Cd for 2 ) in each complex, involving two phenolate O atoms of a Schiff base ligand (N,N′‐bis(5‐bromosalicylidene)‐1,3‐propanediaminate (BSPD) for 1 and N,N′‐bis(2‐hydroxynaphthylmethenylimino)‐1,3‐propanediaminate (HNPD) for 2 ), and an O‐N‐O moiety of a μ‐nitrato group for 1 or an O‐C‐O moiety of a μ‐acetato group for 2 . In each of the complexes, the central M²⁺ is located on an inversion center and has an octahedral coordination involving four bridging O atoms from two Schiff base ligands in the equatorial plane and one O atom from each bridging nitrate or acetate group in the axial positions. The coordination around the terminal Ni²⁺ ions is also octahedral for 1 , but square pyramidal for 2 . The nitrate or acetate bridges linking the central and terminal metal ions are mutually trans. The Ni···M distances are 3.006(2) Å in 1 , and 3.175(2) Å in 2 .     

1-[1-(4-氯苯基)环丁基]-3-甲基丁胺席夫碱的合成、表征及晶体结构

采用减肥药盐酸西布曲明的中间体1-[1-(4-氯苯基)环丁基]-3-甲基丁胺分别与水杨醛、3,5-二氯水杨醛缩合,得到相应的席夫碱化合物2-[[1-[1-(4-氯苯基)环丁基]-3-甲基丁亚氨基]甲基]苯酚(1)和2,4-二氯-6-[[1-[1-(4-氯苯基)环丁基]-3-甲基丁亚氨基]甲基]苯酚(2).通过单晶X-射线衍射、红外光谱、核磁共振谱、元素分析等表征确定了两个席夫碱化合物的组成及结构.1是单斜晶体,空间群C2/c.2是三斜晶体,空间群P-1.化合物主要通过氢键或π-π相互作用形成超分子结构.两个席夫碱化合物具有相似的荧光性质,是潜在多功能蓝色荧光材料.     

Highly Kinked Uranyl Chromate Nitrate Layers in the Crystal Structures of A[(UO2)(CrO4)(NO3)] (A = K,Rb)

Two first uranyl chromate nitrates, K[(UO₂)(CrO₄)(NO₃)] ( 1 ) and Rb[(UO₂)(CrO₄)(NO₃)] ( 2 ), were prepared by solid‐state reactions and characterized by electron microprobe analysis and single‐crystal X‐ray diffraction. The compounds are isotypic [ 1 : monoclinic, P2₁/c, a = 9.881(5), b = 7.215(4), c = 14.226(6) Å, β = 124.85(3)°, V = 832.3(7) ų; 2 : monoclinic, P2₁/c, a = 9.804(1), b = 7.359(1), c = 14.269(1) Å, β = 122.048(4), V = 872.6(1) ų]. The structures of 1 and 2 are based upon the complex [(UO₂)(CrO₄)(NO₃)]^– layers with unprecedented structural topology, which consist of the UrO₃NO₃ units linked through CrO₄ tetrahedra. The resulted kinked layer can be divided into chains arranged in the ladder fashion. The layers are parallel to (100) and are linked by A⁺ (A = K, Rb) cations located between the layers.     

Dimorphism of K4Ta2S11: Syntheses,Crystal Structures,and Properties of two Alkali Metal Tantalum Sulfides

The new ternary potassium tantalum polysulfide K₄Ta₂S₁₁ crystallizing in the triclinic space group P1 with a = 7.465(2), b = 11.441(3), c = 11.534(3) Å, α = 68.66(2), β = 86.59(2) and γ = 83.09(2)° represents a second modification of the already known orthorhombic form, space group Pca2₁ with a = 13.166(2), b = 7.449(2) and c = 18.000(2) Å. The interatomic distances and angles within the Ta₂S₁₁^4– anions of both forms are very similar, but significant differences are observed for the S…S distances between neighboured anions. Temperature dependent single crystal X‐ray experiments yield thermal expansion coefficients of 9.88(30) and 9.44(4) 10^–5 K^–1 for the triclinic and orthorhombic compound, respectively. The higher density for the orthorhombic form indicates that this modification is the thermodynamical more stable form at low temperatures. This assumption is supported by calculations of the electrostatic contributions to the lattice energies using MAPLE (Madelung part of lattice energy). The lattice energy of the orthorhombic form is about 46 kJ mol^–1 larger than that of the triclinic modification. Small differences are observed in the MIR (Medium Infrared Range) spectra of the two dimorphs which correlate well with the slightly different Ta = S bond lengths within the Ta₂S₁₁^4– anions. The compounds were also characterized using UV/Vis reflectance spectroscopy.     

Isopropylammonium Layered Uranyl Chromates: Syntheses and Crystal Structures of [(CH3)2CHNH3]3[(UO2)3(CrO4)2O(OH)3] and[(CH3)2CHNH3]2[(UO2)2(CrO4)3(H2O)]

Two novel isopropylamine‐templated uranyl chromates, [(CH₃)₂CHNH₃]₃[(UO₂)₃(CrO₄)₂O(OH)₃] ( 1 ) and [(CH₃)₂CHNH₃]₂[(UO₂)₂(CrO₄)₃(H₂O)] ( 2 ) were prepared by hydrothermal method at 100 °C. The compounds were characterized by electron microprobe analysis and X‐ray diffraction crystal structure analysis [ 1 : trigonal, P31m, a = 9.646(4), c = 8.469(4) Å, V = 682.4(5) ų; 2 : monoclinic, P2₁/c, a = 11.309(3), b = 11.465(3), c = 17.055(5) Å, β = 99.150(6)°, V = 2183.2(11) ų]. The structure of 1 is based upon trimers of uranyl bipyramids interlinked by CrO₄ tetrahedra to form [(UO₂)₃(CrO₄)₂O(OH)₃]^3– layers, whereas, in the structure of 2 , UO₇ and UO₆(H₂O) pentagonal bipyramids are linked through CrO₄ tetrahedra into the [(UO₂)₂(CrO₄)₃(H₂O)]^2– layers. The structures show many similarities to related uranyl selenate compounds, thus providing additional data on similarities and differences between uranyl sulfates, chromates, selenates, and molybdates.     

On the Flexibility of Thioantimonate Networks: Solvothermal Syntheses and Crystal Structures of Six New Thioantimonates(III) with the [Sb4S7]2− Anion

Six new thioantimonates(III) with the [Sb₄S₇]²⁻ anion were obtained under solvothermal conditions with in‐situ formed transition metal complexes as structure directors. In the two isostructural compounds [Fe(dien)₂]Sb₄S₇·H₂O ( 1 ) and [Co(dien)₂]Sb₄S₇·0.5 H₂O ( 2 ) (dien = diethylenetriamine; space group: P2₁/c) the layered [Sb₄S₇]²⁻ anion is characterized by Sb₈S₈ rings with a diameter of about 9.6·7.6Å. The cation complexes are located above and below the pores of the rings. Despite the larger size of the cation complex the network topology of the third thioantimonate [Ni(dien)(tren)]Sb₄S₇ ( 3 ) (tren = tris(2‐aminoethyl)amine; space group: P2₁/n) is similar to that of the first two compounds. In the isostructural thioantimonates [M(trien)]Sb₄S₇ (M = Zn ( 4 ); M = Mn ( 5 ); trien = triethylenetetramine; space group: ) the M²⁺ ions are fivefold coordinated by four N atoms of the amine molecule and by one S atom of the thioantimonate anion forming a MN₄S trigonal bipyramid. Sb₈S₁₆ building blocks are the central structural motifs of the anion. Two of the terminal S atoms at the periphery of the Sb₈S₁₆ units are bound to M²⁺ ions and the four remaining terminal S atoms connect adjacent Sb₈S₁₆ groups into the final [Sb₄S₇]²⁻ chain. [Ni(tren)]Sb₄S₇ ( 6 ) (space group: ) contains a one‐dimensional anionic chain. The Ni²⁺ ion has two bonds to the [Sb₄S₇]²⁻ anion which is a unique feature in the thioantimonate(III) chemistry. The NiN₄S₂ octahedron is severly distorted with one very long Ni‐S bond of 2.782(2) Å. In all compounds several short S···H distances indicate hydrogen bonding interactions.     

Das Zintl-Konzept als Syntheseprinzip: Darstellung und Kristallstrukturen von K2Ba3Sb4 und KBa4Sb3O

Starting from the Zintl-Concept: Syntheses and Crystal Structures of K₂Ba₃Sb₄ and KBa₄Sb₃O The black, metallic lustrous, air sensitive compounds K₂Ba₃Sb₄ and KBa₄Sb₃O were prepared from melts of mixtures of the elements, in case of KBa₄Sb₃O with a stoichiometric amount of Sb₂O₃. K₂Ba₃Sb₄ crystallizes in the orthorhombic system, space group Pnma (a = 870.5(1) pm, b = 1770.2(2) pm, c = 923.6(1) pm, Z = 4) and is the first Sb compound with only [Sb₂]^4– dumbbells in the anionic partial structure. The compound KBa₄Sb₃O crystallizes in the tetragonal system, space group I4/mcm (a = 882.4(1) pm, c = 1659.4(2) pm, Z = 4). In this structure antimony forms [Sb₂]^4–-dumbbells and isolated ions Sb^3–. Each antimony ion of the dumbbells – in K₂Ba₃Sb₄ as well as in KBa₄Sb₃O – is coordinated in form of a bicapped skew trigonal prism. The isolated Sb^3– ions in KBa₄Sb₃O center bicapped tetragonal antiprisms, the O^2– ions occupy tetrahedral voids.     

Syntheses,Structures, and Magnetic Properties of Two Novel Cobalt(II) Coordination Polymers Constructed from Pyridine‐2,6‐dicarboxylic Acid N‐oxide (PDCO)

Two new cobalt(II) coordination polymers, [Co(PDCO)(H₂O)₂]_n ( 1 ) and [Co(PDCO)(bix)(2H₂O)₂·H₂O]_n ( 2 ) ( PDCO= pyridine‐2,6‐dicarboxylic acid N‐oxide, bix = 1,4‐bis(imidazol‐1‐ylmethyl)‐benzene) have been synthesized under hydrothermal conditions. Single‐crystal X‐ray analyses show that compound 1 is a 1D helical chainlike structure with 4₁ screw axes parallel to the crystallographic c‐axis and interchain hydrogen‐bonding interactions further result in a 3D framework; for compound 2 , each bix ligand connects two Co1 atoms (or two Co2 atoms) to give a zigzag chain structure and these 1D chains are connected by offset face‐to‐face π···π and hydrogen bond interactions to generate a 3D architecture. The thermogravimetric analyses were investigated for 1 and 2 . The determination of variable temperature magnetic susceptibilities indicates an antiferromagnetic interaction between the metal atoms for 1 and 2 .     

Syntheses and X‐Ray Crystal Structures of New Copper(I) and Silver(I) Complexes containing Thione Ligands

The reaction of [(Ph₃P)₂CuCl]₂ with 4‐amino‐6‐methyl‐1,2,4‐triazine‐thione‐5‐one (AMTTO, 1 ) in methanol and further recrystallization from methanol/acetone solution gives [(C₄H₄N₃SON(=CMe₂)Cu(PPh₃)₂Cl] ( 2 ) as a neutral complex. [(C₄H₄N₃SON(=CMe₂)Ag(PPh₃)₂]NO₃ ( 4 ) can be obtained in excellent yield by the reaction of [(AMTTO)₂Ag]NO₃ ( 3 ) with triphenylphosphane in methanol/acetone. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at –80 °C: space group P1 with a = 1233.8(1), b = 1389.7(1), c = 1417.1(1) pm, α = 89.36(1)°; β = 65.10(1)°, γ = 65.95(1)°, Z = 2, R₁ = 0.0582 and for 4 at –80 °C: space group P1, with a = 1193.3(1), b = 1308.5(1), c = 1385.3(1) pm, α = 94.69(1)°, β = 109.14(1)°, γ = 93.42(1)°, Z = 2, R₁ = 0.0716.     

Novel Barium Beryllates Ba[Be2N2] and Ba3[Be5O8]: Syntheses,Crystal Structures and Bonding Properties

Ba[Be₂N₂] was prepared as a yellow‐green microcrystalline powder by reaction of Ba₂N with Be₃N₂ under nitrogen atmosphere. The crystal structure Rietfeld refinements (space group I4/mcm, a = 566.46(5) pm, c = 839.42(9) pm, R_int = 4.73 %, R_prof = 9.16 %) reveal the compound to crystallize as an isotype of the nitridoberyllates A[Be₂N₂] (A = Ca, Sr) consisting of planar 4.8² nets of mutually trigonal planar coordinated Be and N species. Averaged magnetic susceptibility values for the anion [(Be₂N₂)^2?] determined from measurements on A[Be₂N₂] with A = Mg, Ca, Ba allow to derive a diamagnetic increment for N^3? χ_dia = (?13±1stat.) · 10^?6emu mol^?1. Colorless Ba₃[Be₅O₈] was first obtained as an oxidation product of Ba[Be₂N₂] in air. The crystal structure was solved and refined from single crystal X‐ray diffaction data (space group Pnma, a = 942.9(1) pm, b = 1163.47(7) pm, c = 742.1(1) pm, R1 = 2.99 %, wR2 = 7.15 %) and contains infinite rods of Be in trigonal planar, tetrahedral and 3 + 1 coordination by O. The crystal structure is discussed in context with other known oxoberyllates. Electronic structure calculations and electron localization function diagrams for both compounds support the classification as nitrido‐ and oxoberyllate, respectively.