Synthesis,Spectrothermal and Structural Characterization of Saccharinatobis(tris‐hydroxymethylaminomethane)zinc(II)saccharinate Complex, [Zn(sac)(tham)2](sac)

A novel Zn^II complex of the saccharinate ligand (sac) with tris‐hydroxymethylaminomethane (tham) was synthesized and characterized by elemental analysis, FT‐IR spectroscopy, simultaneous TG and DTA techniques, and X‐ray diffraction. The complex, [Zn(sac)(tham)₂](sac), crystallizes in monoclinic system with space group P2₁/c [a = 7.55954(3) Å, b = 13.0532(6) Å, c = 27.7777(10) Å, β = 100.539(3)°, Z = 4]. The Zn^II ion has a distorted octahedral coordination. The tham ligand has chemically different functions in the structure, acting as both bidentate and tridentate ligands. There are also sac moieties to act as N‐bonded ligand and as a counter anion. The molecular packing of the complex is provided by moderate hydrogen bonds as well as π···π interactions between the sac moieties. The IR spectra and the thermal decomposition of the complex are also discussed.     

Earth Alkaline Tetrathiosquarates. II. – Syntheses and Crystal Structures of SrC4S4·4 H2O and Ba4K2(C4S4)5·16 H2O

Concentrated aqueous solutions of strontium chloride and barium chloride, respectively, allow on addition of the potassium salt of tetrathiosquarate, K₂C₄S₄·H₂O, the isolation of the earth alkaline salts SrC₄S₄·4 H₂O ( 1 ) and Ba₄K₂(C₄S₄)₅·16 H₂O ( 2 ), both as dark red crystals. The crystal structure determinations ( 1 : orthorhombic, Pnma, a = 8.149(1), b = 12.907(2), c = 10.790(2) Å, Z = 4; 2 : orthorhombic, Pbca, a = 15.875(3), b = 21.325(5), c = 16.119(1) Å, Z = 4) show the presence of C₄S₄²⁻ ions with only slightly distorted D_4h symmetry having average C–C and C–S bond lengths of 1.41Å and 1.681Å for 1 and 1.450Å and 1.657Å for 2 . The structure of 1 contains concatenated edge‐sharing Sr(H₂O)₆S₂ polyhedra. The Sr²⁺ ions are in eight‐fold coordination with Sr–O distances of 2.50–2.72Å and Sr–S distances of 3.21Å, (C₄S₄)²⁻ acts as a chelating ligand towards Sr²⁺. The structure is closely related to the previously reported Ca²⁺ containing analogue, which is of lower symmetry belonging to the monoclinic crystal system. A supergroup‐subgroup relation between the space groups of both structures is present. The structure of 2 is made up of Ba²⁺ and K⁺ ions in eight and nine‐fold coordination by H₂O molecules and (C₄S₄)²⁻ ions which act as chelating ligands towards one cation and bridging between two cations. The coordination polyhedra of the cations are connected by common edges and corners in two dimensions to layers which are connected by tetrathiosquarate ions to a three‐dimensional network. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds.     

Synthese und Kristallstruktur von K2Mn3S4

Synthesis and Crystal Structure of K₂Mn₃S₄ Single crystals of K₂Mn₃S₄ have been prepared by a fusion reaction of potassium carbonate with manganese in a stream of hydrogen sulfide at 900 °C. K₂Mn₃S₄ crystallizes in a new monoclinic layered structure type (P2/c, a = 7.244(2) Å, b = 5.822(1) Å, c = 11.018(5) Å, β = 112.33(3)°, Z = 2) which can be described as a stacking variant of the orthorhombic Cs₂Mn₃S₄ structure type. Measurements of the magnetic susceptibilities show antiferro‐magnetic interactions.     

Earth Alkaline Tetrathiosquarates: Syntheses and Crystal Structures of MgC4S4 · 6 H2O and CaC4S4 · 4 H2O

Concentrated aqueous solutions of magnesium chloride and calcium nitrate, respectively, allow on addition of the potassium salt of tetrathiosquarate, K₂C₄S₄ · H₂O, the isolation of the earth alkaline salts MgC₄S₄ · 6 H₂O ( 1 ) and CaC₄S₄ · 4 H₂O ( 2 ) as orange and red crystals. The crystal structure determinations ( 1 : monoclinic, C2/c, a = 17.2280(7), b = 5.9185(2), c = 13.1480(4) Å, β = 104.730(3)°, Z = 4; 2 : monoclinic, P2₁/m, a = 7.8515(3), b = 12.7705(5), c = 10.6010(4) Å, β = 93.228(2)°, Z = 4) show the presence of C₄S₄^2? ions with almost undistorted D_4h symmetry having average C–C and C–S bond lengths of 1.451Å and 1.659Å for 1 and 1.451Å and 1.655Å for 2 . The structure of 1 contains discrete, octahedral [Mg(H₂O)₆]²⁺ complexes. Several O–H····O and O–H····S bridges with H····O and H····S distances of less than 2.50Å connect cations and anions. The structure of 2 is built of concatenated, edge‐sharing Ca(H₂O)₆S₂ polyhedra. The Ca²⁺ ions have the coordination number eight, C₄S₄^2? act as a chelating ligands towards Ca²⁺ with Ca–S distances of 3.14Å. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds.     

SrPd4B and BaPd4B: New Type of Crystal Structure and Physical Properties

Two new intermetallic alkaline‐earth palladium borides, SrPd₄B and BaPd₄B were synthesised and their physical properties were investigated. The crystal structure of SrPd₄B was solved from powder X‐ray diffraction data: new structure type, space group Pnma, a = 6.0014(1) Å, b = 5.5041(1) Å, c = 11.8723(2) Å, R_I = 0.065, R_P = 0.093. BaPd₄B is isostructural with a = 6.0883(1) Å, b = 5.6066(1) Å, c = 12.0050(2) Å, R_I = 0.062, R_P = 0.097. The relationship of this structure type with the series of derivatives of the CaCu₅ type is discussed. Calculated electronic band structures for palladium, Pd₃B, SrPd₅, SrPd₄B and SrPd₃B are compared. The role of boron and strontium for the electronic properties is discussed in detail. SrPd₄B shows metallic behaviour with a DOS(E_F) ≈? 1.7 eV^–1 · f.u.^–1 at the Fermi level. Magnetic properties, electrical resistivity and specific heat capacity measurements reveal that the two compounds are diamagnetic metallic conductors with low electronic density of states, in agreement, with the electronic structure calculations.     

Synthesis,crystal structure,and magnetic properties of a salt containing [Cu2Cl7]3− and 4-nitrobenzyl-4′-dimethylaminopyridinium

A new salt, [NO₂BzDMAP]₃[Cu₂Cl₇]?·?H₂O (1), has been synthesized, where [NO₂BzDMAP]⁺ is 1-(4′-nitrobenzyl)-4-dimethylaminopyridinium. Herein, the synthesis, spectral and structural characterization, and magnetic behavior of 1 are reported. It is orthorhombic, with space group Pca2₁, and a?=?26.639(2)?Å, b?=?9.638(1)?Å, and c?=?20.011(2)?Å with V?=?5137.5(7)?ų for Z?=?4. The anion shows a chloride-bridged binuclear structure with Cu?···?Cu distance of 3.872?Å; the two Cu(II) ions have a tetrahedral geometry. The cations stack through p?···?π and π?···?π interactions, and a complicated hydrogen-bonding network structure is formed through C–H?···?Cl and C–H?···?O hydrogen bonds. The variable temperature magnetic susceptibility measurements reveal that 1 exhibits strong antiferromagnetic interaction with J?=??193.0?cm^?1.     

Synthesis and Crystal Structure of Rb6Ta4S22: The First Tantalum Polysulfide Composed of the Dimeric Complex Anion [Ta4S22]6–

The reaction of Rb₂S₃, Ta and S in a 1.3 : 1 : 5.6 molar ratio at 400 °C yields red‐orange crystals of the new ternary compound Rb₆Ta₄S₂₂ being the first tantalum polysulfide containing the dimeric complex anion [Ta₄S₂₂]^6–. The polysulfide anions are composed of two Ta₂S₁₁ subunits which are linked to Ta₄S₂₂ units via terminal sulfur ligands. The Ta⁵⁺ centers are coordinated by S₂^2– and S^2– ligands according to [(Ta₂(μ₂‐η²,η¹‐S₂)₃(η²‐S₂)(S)₂)₂(μ₂‐η¹,η¹‐S₂)]^6–. Every Ta⁵⁺ ion is surrounded by seven sulfur ions forming a strongly distorted pentagonal bipyramid. In the crystal structure the discrete [Ta₄S₂₂]^6– anions are stacked parallel to the crystallographic b‐axis. The Rb⁺ cations are located between these stacks. Rb₆Ta₄S₂₂ crystallizes in the monoclinic space group P2₁/c (No. 14) with a = 11.8253(9) Å, b = 7.9665(4) Å, c = 19.174(2) Å, β = 104.215(9)°, V = 1751.0(2) ų, Z = 2.     

The Upper Limit of Luminol's Amphiprotism: The Crystal Structure of 5-Ammonium-2-hydro-1,4-phthalzinediol Sulfate(IV)

Luminol is chemically sufficiently stable to be diprotonated at high proton concentrations as provided by concentrated sulfuric acid. The luminol dication (5-ammonium-2-hydro-1,4-phthalzinediol) sulfate was isolated as macroscopic single crystals and its structure was determined and refined from single-crystal X-ray data collected at 173 K [cell parameters: a = 8.3994(17) Å, b = 6.9985(14) Å, c = 17.486(4) Å, β = 90.85(3)°, V = 1027.8(4) ų, space group P2₁/c]. The structure is comprised of layers stacked along the b axis. Intralayer interactions are accomplished by strong hydrogen bonds of three luminol dications to one central [SO₄]^2– ion. Interlayer interactions are formed by weak hydrogen bonds of one luminol dication to two [SO₄]^2– ions in the adjacent layers, respectively, and alternating sandwich and parallel-displaced π-π-stacking of the 1-hydropyridazine-3,6-diol moieties of luminol dications in adjacent layers, respectively.     

Intermolecular interactions in the chiral and racemic forms of 3‐­hydroxy‐2‐(1‐oxoisoindolin‐2‐yl)­butanoic acid derived from threonine

The title compounds, C₁₂H₁₃NO₄, are derived from l ‐threonine and dl ‐threonine, respectively. Hydro­gen bonding in the chiral derivative, (2S/3R)‐3‐hydroxy‐2‐(1‐oxoisoindolin‐2‐yl)­butanoic acid, consists of O—H_acid?O_alkyl—H?O=C_indole chains [O?O 2.659 (3) and 2.718 (3) Å], Csp³—H?O and three C—H?π_arene interactions. In the (2R,3S/2S,3R) racemate, conventional carboxylic acid hydrogen bonding as cyclical (O—H?O=C)₂ [graph set R₂²(8)] is present, with O_alkyl—H?O=C_indole, Csp³—H?O and C—H?π_arene interactions. The COOH group geometry differs between the two forms, with C—O, C=O, C—C—O and C—C=O bond lengths and angles of 1.322 (3) and 1.193 (3) Å, and 109.7 (2) and 125.4 (3)°, respectively, in the chiral structure, and 1.2961 (17) and 1.2210 (18) Å, and 113.29 (12) and 122.63 (13)°, respectively, in the racemate structure. The O—C=O angles of 124.9 (3) and 124.05 (14)° are similar. The differences arise from the contrasting COOH hydrogen‐bonding environments in the two structures.     

Synthesis and Crystal Structure of α‐ThTe3

The binary thorium tritelluride, α‐ThTe₃, was synthesized by solid‐state methods at 1223 K. From a single‐crystal X‐ray diffraction study the material crystallizes in the TiS₃ structure type with two formula units in space group C²_2h–P2₁/m of the monoclinic system in a cell with lattice constants a = 6.1730 (4) Å, b = 4.3625(3) Å, c = 10.4161(6) Å, and β = 97.756(3)° (at 100 K). The asymmetric unit of this compound comprises one Th atom and three Te atoms each with site symmetry m. Each Th atom is coordinated to eight Te atoms in a bicapped trigonal‐pyramidal arrangement. Th–Te distances range from 3.1708(4) Å to 3.2496(6) Å. The structure features a Te–Te interaction 2.7631(8) Å in length, which is typical for a Te–Te single bond. Thus α‐ThTe₃ may be charge balanced and formulated as Th⁴⁺Te^2–Te₂^2–.     

Differing Coordination Modes of (O‐Alkyl)‐p‐Ethoxyphenyldithiophosphonato Ligands in Copper(I), Silver(I) and Gold(I) Triphenylphosphine Complexes

The three (O‐methyl)‐p‐ethoxyphenyldithiophosphonato triphenylphosphine complexes of copper, silver and gold, [(Ph₃P)_nM{S₂P(OMe)C₆H₄OEt‐p}] (M = Cu, n = 2; M = Ag, Au, n = 1) investigated structurally by X‐ray diffraction exhibit remarkable structural differences. The copper compound is a four‐coordinate chelate monomer with Cu–S 2.4417(6) and 2.5048(6) Å; P–Cu–S 104.24(2)–114.01(2)°; Cu–S–P 82.49(3)° and 80.85(2)°. The silver compound is a cyclic dimer with bridging dithiophosphonato ligands and three‐coordinate silver atoms [Ag–S 2.5371(5) and 2.6867(5) Å; P–Ag–S 122.88(2)° and 122.17(2)°; Ag–S–P 89.32(2)° and 103.56(2)°]. The gold compound is monomeric with linear dicoordinate gold [Au–S 2.3218(6) Å; P–Au–S 177.72(2)°, Au–S–P 100.97(3)°].     

Preparation and Crystal Structure of a New Uranyl Sulfate Templated by a Bis-isothiouronium Cation

Crystals of a new uranyl sulfate (C₂N₄H₈S₂)[UO₂(SO₄)₂] · 0.3H₂O ( 1 ) templated by a relatively rare bis-isothiouronium cation, were formed upon evaporation of aqueous solutions containing uranyl acetate, thiourea, and excess sulfuric acid. The new compound is orthorhombic, P2₁2₁2₁, a = 6.928(2) Å, b = 13.398(3) Å, c = 15.225(3) Å, Z = 2. Its crystal structure is comprised of [UO₂(SO₄)₂] moieties linked by hydrogen bonds formed between the template cations and terminal oxygen atoms of the sulfate tetrahedra. The C₂N₄H₈S₂²⁺ template is most likely formed in situ during a redox reaction between uranyl cation and thiourea in a strongly acidic medium, with UO₂²⁺ partially reduced to U⁴⁺.     

The sesquiterpenoid nootkatone and the absolute configuration of a di­bromo derivative

Nootkatone, or (4R,4aS,6R)‐4,4a,5,6,7,8‐hexa­hydro‐4,4a‐di­methyl‐6‐(1‐methyl­ethenyl)­naphthalen‐2(3H)‐one, C₁₅H₂₂O, a sesquiterpene with strong repellent properties against Formosan subterranean termites and other insects, has the valencene skeleton. The di­bromo derivative (1S,3R,4S,4aS,6R,8aR)‐1,3‐di­bromo‐6‐iso­propyl‐4,4a‐di­methyl‐1,2,3,4,5,6,7,8‐octa­hydro­naphthalen‐2‐one, C₁₅H₂₄Br₂O, has two independent mol­ecules in the asymmetric unit, which differ in the rotation of the iso­propyl group with respect to the main skeleton. The C—Br distances are in the range 1.950 (4)–1.960 (4) Å. Both independent molecules form zigzag chains, with very short intermolecular carbonyl–carbonyl interactions, having the perpendicular motif and O⋯C distances of 2.886 (6) and 2.898 (6) Å. These chains are flanked by intermolecular Br⋯Br interactions of distances in the range 4.067 (1)–4.218 (1) Å. The absolute configuration of the di­bromo derivative was determined, from which that of nootkatone was inferred.     

Vibrational Spectrum and Gas‐Phase Structure of Disulfur Dinitride (S2N2)

Gas‐phase FTIR spectra of the ν₆ (B‐type) and the ν₄ (C‐type) fundamental bands of S₂N₂ (D_2h) were recorded with a resolution of ≤0.004 cm^?1 and the vibrational spectrum of S₂N₂ (D_2h) in solid Ar has been revisited. All IR‐active fundamentals and four combination bands were assigned in excellent agreement with calculated values from anharmonic VPT2 and VCI theory based on (explicitly correlated) coupled‐cluster surfaces. Accurate experimental vibrational ground‐ and excited‐state rotational constants of ³²S₂¹⁴N₂ are obtained from a rovibrational analysis of the ν₆ and ν₄ fundamental bands, and precise zero‐point average r_z (R_z(SN)=1.647694(95) Å, α_z(NSN)=91.1125(33)°) and semi‐experimental equilibrium structures (R_e(SN)=1.64182(33) Å, α_e(NSN)=91.0716(93)°) of S₂N₂ have been established. These are compared to the solid‐state structure of S₂N₂ and structural properties of related sulfur nitrogen compounds and to results of ab initio structure calculations.     

The Crystal and Molecular Structure of γ‐P4S6

The crystal and molecular structure of γ‐P₄S₆ was determined from single‐crystal X‐ray diffraction. It crystallizes monoclinically in the space group P2₁/m (No. 11) with a = 6.627(3) Å, b = 10.504(7) Å, c = 6.878(3) Å, β = 90.18(4)°, V = 478.8(4) ų, and Z = 2. The structure consists of cage‐like P₄S₆ molecules with C_S symmetry arranged with the topology of a cubic close packing.     

Synthesis and characterization of N -(alky(aryl)carbamothioyl)cyclohexanecarboxamide derivatives and their Ni(II) and Cu(II) complexes

N-(R-carbamothioyl)cyclohexanecarboxamides (R: diethyl, di-n-propyl, di-n-butyl, diphenyl and morpholine-4) and their Ni(II) and Cu(II) complexes have been synthesized and characterized by elemental analyses, FT-IR and NMR methods. N-(diethylcarbamothioyl)cyclohexanecarboxamide, HL¹, C₁₂H₂₂N₂OS, crystallizes in the orthorhombic space group P2₁2₁2₁, with Z = 4, and unit cell parameters, a = 6.6925(13) Å, b = 9.0457(18) Å, c = 22.728(5) Å. The conformation of the HL¹ molecule with respect to the thiocarbonyl and carbonyl moieties is twisted, as reflected by the torsion angles O1–C6–N2–C5, C6–N2–C5–N1 and S1–C5–N2–C6 of 1.68°, ?67.47° and 115.50°, respectively. The structure of HL¹ also shows a delocalization of the π electrons of the thiocarbonyl group over the C–N bonds. The ring puckering analysis shows that the cyclohexane ring has a chair conformation. The bis(N-(morpholine-4-carbonothioyl)cyclohexane carboxamido)nickel(II) complex, Ni(L⁵)₂, C₂₄H₃₈N₄NiO₄S₂, crystallizes in the monoclinic space group P2₁/c, with Z = 4, and unit cell parameters, a = 16.919(3) Å, b = 8.3659(17) Å, c = 19.654(4) Å, β = 107.43(3)°. Ni(L⁵)₂ is a cis-complex with a slightly distorted square-planar coordination of the central nickel by two oxygen and two sulfur atoms.     

Tetrameric triphenylsilanol, (Ph3SiOH)4, and the adduct (Ph3SiOH)2–di­methyl sulfoxide,both at 120 K,and the adduct (Ph3SiOH)4–1,4‐dioxan at 150 K: interplay of O—H⋯O and C—H⋯π(arene) interactions

The structure of tetrameric tri­phenyl­silanol, C₁₈H₁₆OSi, (I), has been re‐investigated at 120 (2) K. The hydroxyl H atoms were readily located and one of the arene rings is disordered over two closely positioned sets of sites. The mol­ecules are linked into cyclic tetramers, having approximate (S₄) symmetry, via O—H?O hydrogen bonds [H?O 1.81–1.85 Å, O?O 2.634 (3)–2.693 (3) Å and O—H?O 156–166°]. At ambient temperature, there are indications of multiple disorder of the phenyl‐ring sites. In bis­(tri­phenyl­silanol) di­methyl sulfoxide solvate, 2C₁₈H₁₆OSi·C₂H₆OS, (II), the di­methyl sulfoxide component is disordered across a twofold rotation axis in C2/c, and the molecular components are linked by a single O—H?O hydrogen bond [H?O 1.85 Å, O?O 2.732 (2) Å and O—H?O 172°] into three‐mol­ecule aggregates, which are themselves linked into a single three‐dimensional framework by two C—H?π(arene) interactions. In tetrakis­(tri­phenyl­silanol) 1,4‐dioxan solvate, 4C₁₈H₁₆OSi·C₄H₈O₂, (III), the 1,4‐dioxan component lies across an inversion centre in space group P and centrosymmetric five‐mol­ecule aggregates are linked by paired C—H?π(arene) interactions to form molecular ladders.     

Synthesis,Crystal Structure,Spectral and Thermodynamic Properties of One Benzoindole Pentamethine Cyanine Dye

One benzoindole pentamethine cyanine dye was synthesized and characterized by ¹H NMR, IR, MS and UV‐Vis spectra. The UV‐Vis absorption and fluorescence spectra of the dye in chloroform, dimethyl sulfoxide, acetone, ethanol and methanol were investigated, and the λ_max of the dye was in the region 682.0–689.0 nm with large molar extinction coefficients (? > 10⁵ M^?1cm^?1) in different solvents. The structure of the dye was also characterized and analyzed by X‐ray diffraction. Crystallographic data revealed that the dye belonged to orthorhombic, with space group P2₁2₁2₁, a = 10.059(2) Å, b = 15.098(4) Å, c = 24.989(6) Å, V = 3794.8(15) ų, Z = 4. The C‐H···F intermolecular hydrogen bonds were displayed in the molecular system, which were effective in the molecular packing. The aggregation behavior and thermodynamic properties of the dye in aqueous methanol solution were also studied by means of UV‐Vis spectroscopy methods. The results indicated that the dye existed monomer‐dimer equilibrium in aqueous methanol solutions. The fundamental properties of the dye, such as the dimeric association constant K_D, the dimeric free energy ΔG_D, the dimeric entropy ΔS_D, and the dimeric enthalpy ΔH_D were determined. The ΔH_D of the dye was –46.0 kJ mol^?1.     

K13CoSn17–x (x = 0.1): A New Ternary Phase Containing ­Cobalt Centered [Sn9] Cluster Synthesized via High‐Temperature Reaction

A new ternary potassium cobalt stannide, K₁₃CoSn_17–x (x = 0.1), was obtained by reacting the mixture of the corresponding pure elements at high temperature, and structurally characterized by single‐crystal X‐ray diffraction study. K₁₃CoSn_17–x (x = 0.1) crystallizes in the orthorhombic space group Pbca (No. 61) with a = 26.2799(7) Å, b = 24.1541(6) Å, c = 29.8839(6) Å, V = 18969.3(8) ų, and Z = 16. Its structure contains isolated [CoSn₉] monocapped square antiprism and [Sn₄] tetrahedron in the ratio 1:2, forming a hierarchical variant of Laves phase MgZn₂. The structural relation between the title compound with MgZn₂ as well as other binary stannides is also discussed.