Solvothermal Syntheses and Crystal Structures of Two Novel Borates: [(CH3)3NH][B5O6(OH)4] and Na2[H2TMED][B7O9(OH)5]2

Two novel borates [(CH₃)₃NH][B₅O₆(OH)₄] (I) and Na₂[H₂TMED][B₇O₉(OH)₅]₂ (II) have been synthesized under solvothermal conditions, and characterized by elemental analyses, FT-IR spectroscopy, and single crystal X-ray diffraction. Crystal data for I: monoclinic, P2₁/c, a = 9.3693(11) Å, b = 14.0375(17) Å, c = 10.0495(9) Å, β = 91.815(9)°, Z = 4. Crystal data for II: monoclinic, P2₁/c, a = 11.6329(2) Å, b = 11.9246(3) Å, c = 10.2528(2) Å, β = 100.178(2)°, Z = 4. Their crystal structures both have 3D supramolecular framework with large channels constructed by O–H···O hydrogen-bonding among the polyanions of [B₅O₆(OH)₄]^? or [B₇O₉(OH)₅]^2? clusters. The templating organic amines cations in I and II are both located in the channels of 3D supramolecular frameworks, respectively, and interact with the polyborate frameworks both electrostatically and via hydrogen bonds of N–H···O. Na₂[H₂TMED][B₇O₉(OH)₅]₂ is the first example of heptaborate co-templated by alkali metal and organic base, which is also rare in borates. The photoluminescence property of the synthetic sample of Na₂[H₂TMED][B₇O₉(OH)₅]₂ in the solid state at room temperature was also investigated by fluorescence spectrophotometer.     

Crystal structure, magnetic property and thermal analysis of a novel manganese complex with phenyldicarboxylate and benzidine ligands

A new complex [Mn₂(C₁₂H₁₂N₂)₃(C₁₄H₈O₄)₂ (C₂H₅OH)₂] _n (where C₁₄H₈O₄ is 2,2′-bi-phenyldicarboxy- late, bpda; C₁₂H₁₂N₂ is benzidine), has been solvothermally synthesized at 443 K and characterized by the elemental analyses, IR, and the single crystal X-ray diffraction analysis. The title complex crystallizes in the triclinic system, space group P-1, with a=9.472 (4) Å, b=12.638(5) Å, c=13.434(5) Å, and Z=1. The compound consists of one-dimensional S-shaped subchains which interlinked by μ₃-2,2′-bpda into a 2-D sheet. The lattice alcohol molecules are located between the layers of the sheet. The magnetic susceptibility has been measured and indicates possible antiferromagnetic coupling between adjacent Mn(II). Based on the TGA curve, the thermal decomposition mechanism of the compound has also been discussed.     

Crystal structure and thermal behavior of a chromium-piperazinium phosphate

(C₄N₂H₁₂)CrO(H_1.5PO₄)₂·H₂O has been synthesized hydrothermally using piperazine as organic template. Its crystal structure was solved ab initio using synchrotron powder X-ray diffraction data [monoclinic, a = 16.9649(4) Å, b = 9.8609(2) Å, c = 7.14375(14) Å, and β = 94.896(3)°, space group P2₁/a, Z = 4]. 1D structure is composed by isolated infinite anionic chains [CrO(H_1.5PO₄)₂]_n (vertex-sharing {CrO₆} octahedra joined by phosphate moieties). Their 2D plate-like morphology is propitiated by a very strong inter-chain interaction (P–O···H···O–P symmetric hydrogen bonds). KAS isoconversional method was applied to determine the activation energy for both thermal and thermo-oxidative decomposition of (C₄N₂H₁₂)CrO(H_1.5PO₄)₂·H₂O.     

Synthesis and structural characterization of a novel tricobalt cluster with 4,4′-dichloro-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol

A novel chelating bisoxime ligand, 4,4′-dichloro-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol (H₂L), and its corresponding trinuclear Co(II) cluster {[CoL(C₂H₅OH)]₂(OAc)₂Co} · 2C₂H₅OH (1) have been synthesized and characterized by elemental analyses, IR, ¹H NMR, TG-DTA and X-ray diffraction methods. The Co(II) cluster crystallizes in the triclinic system, space group P ? 1 with cell dimensions a = 9.412(2) Å, b = 11.868(2) Å, c = 14.280(2) Å, α = 108.131(3)°, β = 108.924(3)°, γ = 97.909(2)°, V = 1382.6(4) Å³, Z = 1, R ₁ = 0.0790, wR ₂ = 0.1869. In the Co(II) cluster, there are two ligand moieties (which provide N₂O₂ donors), two acetate ions and two ethanol molecules, which result in the formation of three slightly distorted octahedral geometries around the Co(II) ions.     

Synthesis,spectroscopic, structural and thermal characterizations of [(C7H6NO4)2TeBr6·4H2O]

Tellurium (IV) complexes with pyridine-2,6-dicarboxylate ligand were synthesized by slow evaporation from aqueous solutions yielding a new compound: [(C₇H₆NO₄)₂TeBr₆·4H₂O]. The structure of this compound was solved and refined by single-crystal X-ray diffraction. The compound is centrosymmetric P2₁/c (N°: 14) with the parameters a = 8.875(5) Å, b = 15.174(5) Å, c = 10.199(5) Å, β = 94.271° (5) and Z = 2. The structure consists of isolated H₂O, isolated [TeBr₆]^2? octahedral anions and (pyridine-2,6-dicarboxylate) [C₇H₆NO₄]⁺ cations. The stability of the structure was ensured by ionic and hydrogen bonding contacts (N–H?Br and O–H?Br) and Van-Der Walls interaction. The thermal decomposition of the compound was studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The FTIR and Raman spectroscopy at different temperatures confirm the existence of vibrational modes that correspond to the organic, inorganic and water molecular groups. Additionally, the UV–Vis diffuse reflectance spectrum was recorded in order to investigate the band gap nature. The measurements show that this compound exhibits a semiconducting behavior with an optical band gap of 2.66 eV.     

Synthesis,characterization, crystal and molecular structure analysis of a novel 1-benzhydryl piperazine derivative: 1-benzhydryl-4-(2-nitro-benzenesulfonyl)-piperazine

A novel 1-benzhydryl piperazine derivative 1-benzhydryl-4-(2-nitro-benzenesulfonyl)-piperazine was synthesized by the nucleophilic substitution of 1-benzhydryl piperazine with 2-nitro-benzenesulfonyl chloride. The product obtained was characterized spectroscopically and finally confirmed by X-ray diffraction study. The title compound, C₂₃H₂₃N₃O₄S crystallizes in the monoclinic space group C2/c with cell parameters a = 13.1120(9) Å, b = 21.4990(9) Å, c = 16.655(1) Å, β = 111.352(2)°, Z = 8, and V = 4372.7(4) Å. The structure reveals that the piperazine ring is in a chair conformation. The geometry around the S atom is distorted tetrahedral. There is a large discrepancy in the bond angles around the piperazine N atoms. The structure is stablized by C–H···O type intermolecular hydrogen bonding interactions.     

Synthesis and Solid-State Structure of Cyclobutyltellurium(IV)-Containing Dimeric Tungstoarsenates(III)

The cage-like cyclobutyltellurium(IV)-containing tungstoarsenate(III) dimers [(C₄H₈Te-OH)₂(C₄H₈Te)₆{As₂W₁₇O₆₁(H₂O)}₂]^14? (1) and [{(C₄H₈Te)₂W₂O₅(H₂O)₂As₂W₁₉O₆₇(H₂O)}₂]^16? (2) were synthesized in moderately acidic aqueous medium by reaction of C₄H₈TeI₂ with the lacunary tungstoarsenates(III) [B-α-AsW₉O₃₃]^9? and [As₂W₁₉O₆₇(H₂O)]^14?, respectively. Polyanion 1 was isolated as a mixed cesium-guanidinium salt Cs_8.5(C(NH₂)₃)_5.5[(C₄H₈TeOH)₂(C₄H₈Te)₆{As₂W₁₇O₆₁(H₂O)}₂]·60H₂O (1a), whereas 2 crystallized as a mixed cesium-potassium salt Cs₉K₇[{(C₄H₈Te)₂W₂O₅(H₂O)₂As₂W₁₉O₆₇(H₂O)}₂]·90H₂O (2a). Single crystal X-ray analysis demonstrated that 1a and 2a crystallized in the triclinic space group \( P \bar{1} \), with a = 12.7738(8) Å, b = 18.7490(14) Å, c = 21.9831(14) Å, α = 111.155(4)^o, β = 93.312(3)^o, γ = 99.530(4) and Z = 1 for 1a and a = 19.309(6) Å, b = 24.674(8) Å, c = 26.071(8) Å, α = 63.218(17)°, β = 89.26(16)^°, γ = 79.948(17)^° and Z = 2 for 2a. The polyanion salts 1a and 2a were characterized by solid state NMR (¹H, ¹³C, ¹²⁵Te), FT-IR, TGA-DSC, and elemental analysis.     

Crystal structure,luminescent and thermochromic properties of bis(tetraethylammonium) hexachlorotellurate(IV)

The crystal structure of (C₂H₅)₄N)₂TeCl₆ was determined by X-ray diffraction (a = 14.130(2) Å, b = 14.547(2)Å, c = 13.296(2)Å, β= 90.356(3)°; space group C2/c, Z = 4, ρ_(calcd) = 1.387 g/cm³). The crystal structure is composed of the [TeCl₆]^2? anions and tetraethylammonium cations ((C₂H₅)₄N)⁺. The electronic and geometric aspects that determine the spectral luminescence and thermochromic properties of the complex are discussed.     

Crystal structure and thermal decomposition mechanism of a 5-aminotetrazole copper(II) complex

A novel 5-aminotetrazole mixed ligands complex of formula [Cu(PTS)₂(ATZ)₂(H₂O)₂] (C₁₆H₂₄CuN₁₀O₈S₂, PTS = p-toluenesulfonate, ATZ = 5-aminotetrazole) has been obtained by the reaction of 5-aminotetrazole with copper acetate and p-toluenesulfonic acid on heating in water. It was characterized by elemental analysis, FT-IR spectroscopy, and X-ray single crystal diffraction. The compound crystallizes in monoclinic system, space group P2₁/c, Z = 2, a = 14.079(4) Å, b = 6.088(3) Å, c = 14.632(4) Å, β = 105.268(4)°, V = 1209.8(5) Å³. The central copper(II) cation is coordinated by two N atoms and four O atoms from two ATZ ligands, two water molecules and two p-toluenesulfonate ions to form a six-coordinated and distorted octahedral structure. Neutral ATZ is coordinated in the monodentate mode by the N(4) atom. The sulfonate group of the PTS ligand remains weak-coordinated modes and forms a number of hydrogen bonds with water molecule ligands and ATZ ligands. A supramolecular framework is connected by electrostatic interaction, weak coordinated bonding, hydrogen-bonding, and π–π interaction. The thermal decomposition mechanism of the title compound was predicted based on DSC, TG-DTG, and FT-IR analyses. Thermolysis of ATZ and its several derivatives is compared.     

A New Organic-Paradodecatungstate Hybrid Compound: Synthesis, Characterization and Crystal Structure

An organic–inorganic hybrid compound Na₂(HAn)₈[H₂W₁₂O₄₂]·16H₂O (HAn: p-anisidinium, C₇H₁₀NO) has been synthesized under soft acidic conditions and characterized by infrared and UV–visible spectroscopies, thermogravimetric analysis, cyclic voltammetry and single crystal X-ray diffraction. The compound crystallizes in the monoclinic P2₁/n space group with a = 10.1920(4) Å, b = 34.2901(9) Å, c = 14.0745(5) Å, β = 95.830(3)°, V = 4,893.4(3) Å³ and Z = 4. The compound exhibits a 2D supramolecular structure formed by alternated [paradodecatungstate/Na] and p-anisidinium layers. The catalytic activity of the compound for oxidation of cyclooctene with H₂O₂ was proved and gives rise to good reaction yield.     

Crystal structures of two (5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane)iron(III) complexes

Reported in this contribution are the synthesis and crystal structures of two new Fe^III complexes of 5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane (HMC), namely, dichlorido(5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane)iron(III) chloride, [FeCl₂(C₁₆H₃₆N₄)]Cl or cis‐[FeCl₂(rac‐HMC)]Cl ( 1 ), and dichlorido(5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane)iron(III) tetrachloridoferrate, [FeCl₂(C₁₆H₃₆N₄)][FeCl₄] or trans‐[FeCl₂(meso‐HMC)][FeCl₄] ( 2 ). Single‐crystal X‐ray diffraction studies revealed that both 1 and 2 adopt a pseudo‐octahedral geometry, where the macrocycles adopt folded and planar geometries, respectively. The chloride ligands in 1 are cis to each other, while those in 2 have a trans configuration. The relevant bond angles in 1 deviate substantially from an ideal octahedral coordination geometry, with the angles between the cis substituents varying from 81.55 (5) to 107.56 (4)°, and those between the trans‐ligating atoms varying from 157.76 (8) to 170.88 (3)°. In contrast, 2 adopts a less strained configuration, in which the N—Fe—N angles vary from 84.61 (8) to 95.39 (8)° and the N—Fe—Cl angles vary from 86.02 (5) to 93.98 (5)°.     

Synthesis,crystal structure of new linear trinuclear isovalence Co(II)([Co<Subscript>3</Subscript>(H–L)<Subscript>2</Subscript>(L)<Subscript>2</Subscript>]), and visualizing intermolecular interactions with Hirshfeld surface method

S-allyl-β-N-[(2-hydroxyphenyl)methylene]hyrazinecarbodithioate) (1, H₂L), the Schiff base of dithiocarbazate with unsaturated allyl substitution, can act as a new tridentate SNO ligand H₂–L and react with cobalt(II) nitrate hexahydrate to form the novel linear trinuclear isovalence Co(II) complex, [Co₃(H–L)₂(L)₂] 2C₂H₅OH (2). The compounds were characterized by elemental analysis, infrared, and ultraviolet spectroscopy. Compound 2 was also characterized by single-crystal X-ray analysis and crystallizes in the orthorhombic space group, Pbcn, with a = 30.643(1) Å, b = 9.118(4) Å, c = 19.017(7) Å, α = β = γ = 90°, V = 5312.95 Å³, Z = 4, and R ₁ = 0.0790, (wR ₂) = 0.1223. The six-coordinate central Co(II) atom is bonded to two deprotonated metal-containing ligands. The terminal Co(II) atoms are in a square planar SNON four-coordinate environment and connected to the central Co(II) by N-atoms from the ligand backbone. For quantifying the intermolecular interactions in crystal lattice, the new d _norm surface and the breakdown of fingerprint plots have been used for visualizing and exploring the compound 2.     

Molecular and crystal structure of 15-acetylsongorine and songoramine isolated from <Emphasis Type="Italic">Aconitum szechenyianum</Emphasis> Gay

Two napelline skeletal diterpenoid alkaloids 15-acetylsongorine, C₂₄H₃₃NO₄ I, and songoramine, C₂₂H₂₉NO₃ II, were first isolated from the roots of Aconitum Szechenyianum Gay. The crystal structures were determined by X-ray single-crystal diffraction analysis. The crystal I is the triclinic system with space group P1 having unit cell parameters of a = 9.360(8) Å, b = 11.593(9) Å, c = 11.830(16) Å, α = 113.223(15)°, β = 105.950(16)°, γ = 101.296(12)°, and Z = 2. Hydrogen bonds O–H···O and O–H···N joint the molecules into dimer. The crystal II belongs to the orthorhombic system with space group P2₁2₁2₁ having unit cell parameters of a = 8.950(2) Å, b = 13.272(3) Å, c = 15.454(4) Å and Z = 4. The O–H···O hydrogen bonding interaction links the molecule into linear chains. The distortion of rings of compound I and II were evaluated by calculation of the Cremer and Pople puckering parameters. The presence of the C–O–C bond in the compound II results in the changes of ring conformations compared with that of the compound I.     

Structural and Physicochemical Characteristics of Tetrabutylammonium Tetrahalogenoferrates(III), [(C4H9)4N][FeBr4−nCln]

A series of tetrahalogenoferrates(III), [FeBr_4?nCl_n]^? (n=0‐4) stabilized with the tetrabutylammonium cation, of general formula [(C₄H₉)₄N][FeBr_4?nCl_n], has been synthesized. The crystal and molecular structure of [(C₄H₉)₄N][FeCl₄] was determined. The iron cation adopts slightly distorted tetrahedral coordination with two opposite angles smaller than tetrahedral one, two equal to tetrahedral and two larger than tetrahedral. The bond valences were computed. The total valence of iron atom is equal to 3.08. In the structure can be found only one hydrogen bond C(1)–H···Cl. Except mentioned there are no unusually intermolecular short contacts between ions existing in the structure. All [(C₄H₉)₄N][FeBr_4?nCl_n] (n=0‐4) compounds are isostructural in solid state. On the basis of conductometric measurements, relative stabilities of the anions have been estimated in methanol (MeOH), dimethyl sulfoxide (DMSO), acetone (AC), acetonitrile (AN) and dichloromethane (CH₂Cl₂) representing both polar (including amphiprotic and aprotic) as well as non‐polar solvents. Further, the dissociation constants of the compounds were calculated from the expanded Pitt's conductivity equation. The results of the conductometric measurements were supported by electronic spectra.     

Tetranuclear manganese (III) salicylaldoxime ensemble

Crystal structure of {[Mn(salicylaldoximeH)(salicylaldoxime)]₄} · 3CHCl₃ 1 formed by the interaction of MnCl₂ · 4H₂O and salicylaldoxime in a 1:1 ratio is described. The compound crystallizes in the orthorhombic space group Pbca (No 61) with the lattice parameters; a = 27.769 (3), b = 22.672 (2), c = 21.650 (2) Å, V = 13630 (2) Å³, Z = 8, R ₁ = 0.0776, wR ₂ = 0.2356, S = 1.164. The cluster with four Mn (III) centers formed by four terminal and four bridging salicylaldoxime ligands results in a central rotating wheel-like core with the Mn–Mn separation varying from 3.531 to 3.576 Å and with the diagonal distances being 4.156–4.165 Å. Four intramolecular H-bonds between a terminal oxime (NOH) group and the adjacent phenolate oxygen atom of another ligand stabilize the structure of the cluster. Spectral, magnetic, and cyclic voltammetry studies corroborate a stable Mn (III) tetramer.     

Dicopper(II) Assembly Containing the Tetrameric Cluster of Water Constructed from Terephthalate Dianion and Copper(II) Macrocyclic Fragment

To utilized a mononuclear fragment of [Cu(L)Cl]ClO₄ (1) and TPHA bridged-ligand as building block by self-assembly technology, a new dinuclear copper(II) compound [(CuL)₂(μ-TPHA)](ClO₄)₂ · 4H₂O (2), where L = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1^6,9]octadecane, TPHA = terephthalate dianion, has been constructed and structurally characterized by X-ray crystallography. Crystal analyses denotes that crystal water molecules interact with each other give rise to a tetrameric cluster of water, which by sharing dinuclear units result in a 1D chain structure. Complex 2 crystallizes in monoclinic, space group P2₁/c, with a = 11.1586(14), b = 13.2240(16), c = 16.241(2) Å and β = 105.636(2)°. Magnetic measurements confirm that 2 present an antiferromagnetic interaction between the paramagnetic ions.     

Synthesis of Some Octahedral Nickel(II) Complexes of One Isomer of Isomeric Me8[14]anes: X-ray Structure of Diisothiocyanato(3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane, LC)nickel(II), [NiLC(NCS)2]

One isomer, L_C of the isomeric Me₈[14]anes, L_A, L_B and L_C; on reaction with Ni(NCS)₂ produces a six coordinate octahedral diisothiocyanato complex, [NiL_C(NCS)₂]. This complex undergoes axial substitution reactions with the small ligands to yield corresponding monosubstituted derivatives having general formula [NiL_C(NCS)X] whereas X = Cl, Br, I, NO₂ or NO₃. The complexes have been characterized on the basis of analytical, spectroscopic, magnetic and conductance data. The structure of [NiL_C(NCS)₂] (triclinic, space group P?1, α = 8.0421(17) Å, β = 8.9085(18) Å, χ = 9.687(2) Å, α = 67.561(3) Å, β = 82,896(4) Å, ζ = 598.7(2) Å³, Z = 2, Dc = 1.352 mg/m³, μ(Mo Kα) = 1.003 mm^?1) was confirmed by X-ray crystallography.     

Synthesis, characterization, crystal and molecular structure analysis of N-(2,4-dimethylphenyl)-6-methyl-4-(3-nitrophenyl)-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxamide

A novel dihydropyrimidine (DHPM) derivative bearing a carbamoyl moiety was synthesized by an efficient three-component Biginelli reaction and was characterized spectroscopically and finally confirmed by X-ray diffraction studies. The title compound C₂₀H₂₀N₄O₄ crystallizes in the monoclinic space group P2₁/c with cell parameters a=12.8970(12) Å, b=13.6210(11) Å, c=11.8420(13) Å, β=115.860(3)°, Z=4 and V=1872.0(3) Å³. The conformation of the dihydropyrimidine ring is unusual; it is planar instead of the usual boat-like conformation. The 3-nitrophenyl ring is orthogonal to the 3,4-DHPM ring. The carbonyl group is in an anti-clinal conformation.     

Solvothermal synthesis and structural characterization of a novel erbium(III)-carboxylate polymeric complex

A novel erbium(III)-carboxylate polymeric complex [{Er(H₂btec)_2/4(btec)_3/6(H₂O)}·2H₂O] _n , simplified as ECPC, (H₄btec=1,2,4,5-benzenetetracarboxylic acid) was synthesized under solvothermal conditions (H₂O/acetic acid). ECPC obtained was characterized by differential thermal analysis/thermogravimetry (DTA/TG), single-crystal X-ray diffraction, elemental analysis and FT-IR analysis techniques. The result of single-crystal X-ray diffraction analysis shows that the ECPC crystallizes in monoclinic symmetry, and the space group P2(1)/n, a=10.6933(15) Å, b=7.1243(10) Å, c=17.092(2) Å, α=γ=90°, β=97.109(2)°, V=1292.1(3) Å³, Z=4, R ₁=0.0286, wR ₂=0.0686. ECPC demonstrates a 3-D supramolecular framework containing nine-coordinate erbium centers and channels. The uncoordinated water molecules occupy the channels in ECPC. The results of TG/DTA, IR and elemental analysis performed also give positive information of the proposed crystal structure.     

(R)‐1‐Phenyl­ethyl­ammonium 6‐amino‐5‐nitro­pyrimidine‐2,4(1H,3H)‐dionate (R)‐1‐phenyl­ethyl­amine hemisolvate: hydrogen‐bonded sheets of ions with pendent solvent mol­ecules

In the title compound, 2C₈H₁₂N⁺·2C₄H₃N₄O₄⁻·C₈H₁₁N, the anions are linked by paired N—H⋯N hydrogen bonds [H⋯N = 2.07 and 2.11 Å, N⋯N = 2.942 (3) and 2.978 (3) Å and N—H⋯N = 173 and 170°] and by paired N—H⋯O hydrogen bonds [H⋯O = 1.98 and 2.05 Å, N⋯O = 2.855 (3) and 2.917 (3) Å, and N—H⋯O = 173 and 167°] into chains of rings. These chains are linked into sheets by further N—H⋯O hydrogen bonds in which all of the donors are provided by the cations [H⋯O = 1.83–2.17 Å, N⋯O = 2.747 (3)–2.965 (3) Å and N—H⋯O = 141–168°]. The neutral amine molecule is pendent from the sheet and is linked to it by a single N—H⋯N hydrogen bond [H⋯N = 2.00 Å, N⋯N = 2.901 (3) Å and N—H⋯N = 175°].