High-pressure high-temperature synthesis and crystal structure of the isotypic rare earth (RE)-thioborate-sulfides RE9[BS3]2[BS4]3S3, (RE=Dy-Lu)

Application of high-pressure high-temperature conditions (3.5 GPa at 1673 K for 5 h) to mixtures of the elements (RE:B:S=1:3:6) yielded crystalline samples of the isotypic rare earth-thioborate-sulfides RE₉[BS₃]₂[BS₄]₃S₃, (RE=Dy-Lu), which crystallize in space group P6₃ (Z=2/3) and adopt the Ce₆Al_3.33S₁₄ structure type. The crystal structures were refined from X-ray powder diffraction data by applying the Rietveld method. Dy: a=9.4044(2) Å, c=5.8855(3) Å; Ho: a=9.3703(1) Å, c=5.8826(1) Å; Er: a=9.3279(12) Å, c=5.8793(8) Å; Tm: a=9.2869(3) Å, c=5.8781(3) Å; Yb: a=9.2514(5) Å, c=5.8805(6) Å; Lu: a=9.2162(3) Å, c=5.8911(3) Å. The crystal structure is characterized by the presence of two isolated complex ions [BS₃]^3- and [BS₄]^5- as well as [□(S^2-)₃] units.     

Structural characterization and catalytic properties of bis(1,1,3,3-tetramethylguanidinium) dichromate

The structure of bis(1,1,3,3-tetramethylguanidinium) dichromate was determined from powder X-ray diffraction data. The compound crystallizes in the monoclinic system (space group P2₁/n) with a = 10.79714 (15) Å, b = 11.75844 (16) Å, c = 8.15097 (11) Å, β = 109.5248 (6)°. The structure consists of dichromate anions (Cr₂O₇²⁻) stabilized by tetramethylguanidinium cations ([H₂NC(N(CH₃)₂)₂]⁺ or [TMGH]⁺). Phase transitions of [TMGH]₂Cr₂O₇ were determined by differential scanning calorimetry, thermal gravimetric analysis and in situ Raman spectroscopy, where the decomposition of the matrix into CrO_x was found at 171-172 °C. Further heat treatment to above 400 °C resulted in formation of the thermodynamically stable Cr₂O₃, most likely with the [TMGH]⁺ cation as reductant. The catalytic activity of [TMGH]₂Cr₂O₇ supported on TiO₂ anatase in the selective catalytic reduction (SCR) of nitrogen oxide was also investigated, however only moderate activity was observed in the temperature range 100-400 °C compared to the activity of e.g., vanadia supported on titania.     

Unusual one-dimensional branched-chain structures assembled by a novel imidazole-containing tripodal ligand with cadmium(II) salts and their fluorescent property

Three novel coordination polymers [Cd₃(L)₂(μ-Br)(μ-Cl)Br₃Cl] (1), [Cd₃(L)₂(μ-Cl)₂Cl₄] (2) and [Cd(L)Cl]₂[CdCl₄]·H₂O (3) were obtained by reactions of an imidazole-containing tripodal ligand N¹-(2-aminoethyl)-N¹-(2-imidazolethyl)-ethane-1,2-diamine (L) with Cd(II) salts. Their structures were determined by X-ray crystallography. Crystal data for 1, monoclinic system, P2₁/c, a=7.752(4) Å, b=31.70(2) Å, c=14.012(7) Å, β=109.439(7)°, V=3247(3) Å³, Z=4. 2, monoclinic system, P2₁/c, a=7.6564(15) Å, b=31.433(6) Å, c=13.925(3) Å, β=109.89(3)°, V=3151.1(11) Å³, Z=4. 3, orthorhombic system, Pbcn, a=22.950(2) Å, b=8.435(7) Å, c=17.360(2) Å, V=3360.3(51) Å³, Z=4. Complexes 1 and 2 have similar one-dimensional (1D) branched-chain structure while complex 3 features a 1D zigzag cationic chain with [CdCl₄]²⁻ serving as counter anion. The photoluminescent measurements reveal that all the complexes exhibit blue fluorescence at room temperature in the solid state.     

A hybrid material based on [Mo6Br14] inorganic cluster units and [BEDO-TTF] organic monocationic radicals: Synthesis, structure and properties of (BEDO-TTF)2Mo6Br14(PhCN)4

The first charge transfer salt based on non- dimerized [BEDO-TTF]⁺ monocationic radical (BEDO-TTF=bis(ethylenedioxy)tetrathiafulvalene) associated with [Mo₆Br₁₄]²⁻ cluster anions has been synthesized by conventional electro-oxidation and characterized by single crystal X-ray diffraction, UV-VIS-NIR absorption and magnetic susceptibility measurements. (BEDO-TTF)₂Mo₆Br₁₄(PhCN)₄ crystallizes in the monoclinic system, space group P2₁/n, a=10.414(4) Å, b=21.711(7) Å, c=15.958(5) Å, β=93.65(3)°, V=3601(2) Å³, Z=2, R₁=0.0578, wR₂=0.0731. The structure of this hybrid compound is built up from a [BEDO-TTF]⁺ and PhCN (benzonitrile) organic framework in which are hosted the [Mo₆Br₁₄]²⁻ inorganic cluster units. It results in non- dimerized [BEDO-TTF]⁺ cations that exhibit a paramagnetic behavior characteristic of one unpaired electron.     

Syntheses and crystal structures of binuclear ruthenium complexes bearing 1,8′-bis(diphenylphosphinomethyl)naphthalene

Treatment of [RuCl₂(η⁶-C₆H₆)]_x with bidentate phosphine ligand BDNA [1,8-bis(diphenylphosphinomethyl)naphthalene] in methanol at room temperature gave η⁶-benzene-ruthenium complexes Ru₂Cl₄(η⁶-C₆H₆)₂(μ-BDNA) (1). Complex 1 further reacted with AgBF₄ to form complex [Ru₂Cl₂(μ-Cl)(η⁶-C₆H₆)₂(μ-BDNA)](BF₄) (2). [RuCl₂(η⁶-C₆H₆)]_x reacted with BDNA in refluxing methanol and then the reaction solution was treated with AgBF₄ to generate complex [Ru₂Cl₂(η⁶-C₆H₆)₂(μ-BDNA)₂](BF₄)₂ (3). Their compositions and structures had been determined by elemental analyses, NMR spectra and single crystal X-ray diffractions. X-ray diffraction showed that complex 1 belonged to monoclinic crystal system, P2₁/c space group with Z = 4, a = 12.810 Å, b = 21.507 Å, c = 18.471 Å, β = 107.95°; complex 2 belonged monoclinic crystal system, P2₁/n space group with Z = 4, a = 14.498 Å, b = 15.644 Å, c = 20.788 Å, β = 103.404°, and complex 3 belonged to monoclinic crystal system, P2₁/n space group with Z = 2, a = 13.732 Å, b = 14.351 Å, c = 19.733 Å, β = 94.82°.     

Structure determination of Na3DySi6O15 and crystal chemistry of zektzerite related compounds

The crystal structure of Na₃DySi₆O₁₅ has been solved and refined to an R₁=2.97% (wR₂=8.25%) for 1311 independent reflections. The compound was found to crystallize within the orthorhombic system with the space group Cmca (Z=8) and the lattice parameters: a=14.590(7) Å, b=17.813(4) Å, c=10.519(2) Å, V=2734.0 Å³, D_cal=3.11 g/cm³. The structure of Na₃DySi₆O₁₅ is a filled variant of the zektzerite with S like corrugated double chains of [SiO₄] tetrahedral, connected via Na⁺ and Dy³⁺ cations and running parallel to c-axis. The three-dimensional network results from the packing of these chains along [100] by skewering them in rods represented by the tunnels delimited by the S shape of the silicate chains. One of the main peculiar features of the Na₃DySi₆O₁₅ structure is the location of Na⁺ in tetrahedral sites with rather short Na-O bond lengths (2×2.243 and 2×2.262 Å).     

Second sphere coordination in fluoroanion binding: Synthesis, spectroscopic and X-ray structural study of [Co(phen)2CO3](Pfbz)·6H2O

To explore the anion receptor potential of [Co(phen)₂(CO)₃]⁺ for the pentafluorobenzoate ion, [Co(phen)₂(CO)₃](Pfbz)·6H₂O (where phen = 1,10-phenanthroline and Pfbz = pentafluorobenzoate) was synthesized by reacting appropriate salts in aqueous medium. A detailed packing analysis has been undertaken to delineate the role of second sphere C-H?F interactions amid other heteroatom interactions. The complex salt has been characterized by elemental analyses, spectroscopic studies (IR, UV/Vis, multinuclear NMR) and solubility product measurement. The complex salt crystallizes in the monoclinic crystal system with space group P2₁/n having the cell dimensions a = 13.377(3) Å, b = 17.204(3) Å, c = 15.408(3) Å, β = 108.11(3)°, V = 3370.1(12) Å³ and Z = 4. Single crystal X-ray structure determination revealed ionic structure consisting of complex cation, [Co(phen)₂(CO)₃]⁺, Pfbz anion and six lattice water molecules. In the crystal lattice, discrete ions [Co(phen)₂CO₃]⁺ are forming rectangular voids in which the Pfbz anions are entrapped. Crystal lattice is stabilized by electrostatic forces of attraction and hydrogen bonding interactions, i.e. O-H?O, C-H?O, and C-H?F, involving second sphere coordination besides π?π interactions.     

A new family of pyrazolyl-based anionic bidentate ligands and crystal structure of bis(N-phenyl-2-pyrazolyl-1-carboximidothioato)copper(II)

Three new N,S-donor bidentate pyrazolyl-based ligands abbreviated as [PhNCSPz]⁻, 1, [PhNCSPz^Me2]⁻, 2, and [PhNCSPz^Ph2]⁻, 3, have been synthesized in THF by direct mixing of phenylisothiocyanide with suspension of appropriate sodium-pyrazolate salts and characterized by the common spectroscopic and analytical methods. The Cu(II) complexes of these anionic chelate ligands have been characterized and the crystal structure of Cu(PhNCSPz)₂, 4, has been determined. The space group of complex is P2₁c, with a = 5.9313(3), b = 21.206(1) Å, c = 8.0667(4) Å, β = 103.822(1)°.     

Synthesis, characterization, and near-infrared luminescent properties of the ternary thulium complex covalently bonded to mesoporous MCM-41

The crystal structure of a ternary Tm(DBM)₃phen complex (DBM=dibenzoylmethane; phen=1, 10-phenanthroline) and the synthesis of hybrid mesoporous material in which the complex covalently bonded to mesoporous MCM-41 are reported. Crystal data: Tm(DBM)₃phen C₅₉H₄₇N₂O₇Tm, monoclinic, P21/c, a=19.3216(12) Å, b=10.6691(7) Å, c=23.0165(15) Å, α=90°, β=91.6330(10)°, γ=90°, V=4742.8(5) Å³, Z=4. The properties of the Tm(DBM)₃phen complex and the corresponding hybrid mesoporous material [Tm(DBM)₃phen-MCM-41] have been studied. The results reveal that the Tm(DBM)₃phen complex is successfully covalently bonded to MCM-41. Both Tm(DBM)₃phen complex and Tm(DBM)₃phen-MCM-41 display typical near-infrared (NIR) luminescence upon excitation at the maximum absorption of the ligands, which contributes to the efficient energy transfer from the ligands to the Tm³⁺ ion, an antenna effect. The full width at half maximum (FWHM) centered at 1474 nm in the emission spectrum of Tm(DBM)₃phen-MCM-41 is 110 nm, which is the potential candidate of broadening amplification band from C band (1530-1560 nm) to S⁺ band (1450-1480 nm) in optical area.     

Cation-controled formation of N,N′-dialkylimidazolium cadmium-thiocyanate complexes: synthesis and structural characterization

Three new N,N′-dialkylimidazolium salts of cadmium-thiocyanate, [EtMeIm]₂[Cd₂(SCN)₆] (2), [C₆H₄(CH₂ImMe)₂][Cd(SCN)₄] (3), [C₆Me₃(CH₂ImMe)₃][CdBr₃(SCN)](NO₃) (4) have been prepared, and their crystal structures have been determined by X-ray diffraction. Crystal data: 2, monoclinic, C2/c, a=18.349(4) Å, b=7.8667(18) Å, c=21.399(5) Å, β=110.346(4)°, V=2896.1(11) Å³, Z=4, and R1=0.0561; 3, monoclinic, C2/c, a=20.347(7) Å, b=14.029(5) Å, c=9.380(3) Å, β=112.034(6)°, V=2482.1(15) Å³, Z=4, and R1=0.0397; 4, hexagonal, P6₃, a=b=10.7634(8) Å, c=16.0315(17) Å, V=1608.4(2) Å³, Z=2, and R1=0.0569. Compound 2 consists of triply bridged infinite one-dimensional cadmium-thiocyanate chains, and two independent cadmium atoms are octahedrally coordinated in 2N4S and 4N2S geometry, respectively. In 3, the cadmium atom is octahedrally coordinated with two cis N-bonded monodentate NCS⁻ ligands and four bridging SCN⁻ in a S trans to S, and N trans to N coordination fashion, and thus form doubly bridged infinite one-dimensional chains. Whereas 4 is mononuclear, consisting of a discrete [C₆Me₃(CH₂ImMe)₃]³⁺ cation, a nitrate, and [CdBr₃(SCN)]⁻ ion, and each cadmium(II) ion is coordinated to three bromide and one nitrogen atom of SCN⁻ ion. The structures of these compounds are dictated by the imidazolium cations.     

Synthesis and crystal structure of two tin fluoride materials: NaSnF3 (BING-12) and Sn3F3PO4

A new compound, sodium tin trifluoride (NaSnF₃, which we denote BING-12 for SUNY at Binghamton, Structure No. 12), was synthesized solvothermally from a pyridine-water solvent system. The new compound crystallized in the monoclinic space group C2/c (No. 15), with a=11.7429(12) Å, b=17.0104(18) Å, c=6.8528(7) Å, β=100.6969(2)°, V=1345.1(2) Å³ and Z=16. The layered structure consists of outer pyramidal SnF₃ units, where the fluorides surround a central layer of six- and seven-coordinate sodium atoms. The layers are stabilized by charged Na⁺ galleries that reside in the center of the layers. Tin trifluorophosphate (Sn₃F₃PO₄, Compound 2) was isolated from a related synthetic system, and crystallized in the rhombohedral space group R3 (No. 146), with a=11.8647(11) Å, c=4.6291(6) Å, V=564.34(10) Å³ and Z=3. The framework is made up of helical -Sn-F- chains, which are connected by phosphate groups. The materials were characterized by powder X-ray diffraction (PXRD), variable temperature PXRD (VT-PXRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM).     

Synthesis and structural investigation of the compounds containing HF2 anions: Ca(HF2)2, Ba4F4(HF2)(PF6)3 and Pb2F2(HF2)(PF6)

Three new compounds Ca(HF₂)₂, Ba₄F₄(HF₂)(PF₆)₃ and Pb₂F₂(HF₂)(PF₆) were obtained in the system metal(II) fluoride and anhydrous HF (aHF) acidified with excessive PF₅. The obtained polymeric solids are slightly soluble in aHF and they crystallize out of their aHF solutions. Ca(HF₂)₂ was prepared by simply dissolving CaF₂ in a neutral aHF. It represents the second known compound with homoleptic HF environment of the central atom besides Ba(H₃F₄)₂. The compounds Ba₄F₄(HF₂)(PF₆)₃ and Pb₂F₂(HF₂)(PF₆) represent two additional examples of the formation of a polymeric zigzag ladder or ribbon composed of metal cation and fluoride anion (MF⁺)_n besides PbF(AsF₆), the first isolated compound with such zigzag ladder. The obtained new compounds were characterized by X-ray single crystal diffraction method and partly by Raman spectroscopy. Ba₄F₄(HF₂)(PF₆)₃ crystallizes in a triclinic space group P1¯ with a=4.5870(2) Å, b=8.8327(3) Å, c=11.2489(3) Å, α=67.758(9)°, β=84.722(12), γ=78.283(12)°, V=413.00(3) Å³ at 200 K, Z=1 and R=0.0588. Pb₂F₂(HF₂)(PF₆) at 200 K: space group P1¯, a=4.5722(19) Å, b=4.763(2) Å, c=8.818(4) Å, α=86.967(10)°, β=76.774(10)°, γ=83.230(12)°, V=185.55(14) ų, Z=1 and R=0.0937. Pb₂F₂(HF₂)(PF₆) at 293 K: space group P1¯, a=4.586(2) Å, b=4.781(3) Å, c=8.831(5) Å, α=87.106(13)°, β=76.830(13)°, γ=83.531(11)°, V=187.27(18) Å³, Z=1 and R=0.072. Ca(HF₂)₂ crystallizes in an orthorhombic Fddd space group with a=5.5709(6) Å, b=10.1111(9) Å, c=10.5945(10) Å, V=596.77(10) Å³ at 200 K, Z=8 and R=0.028.     

Crystal chemistry in the Ag2O-Nb2O5 system: AgNb3O8 structure determination

The investigation of the AgNbO₃-Nb₂O₅ system is carried out using solid-state routes. This investigation allows to confirm the existence of four compounds with structure related to the Na-based homologous. A new form of AgNb₃O₈ is evidenced and its structure is determined on the basis of single-crystal X-ray diffraction investigations. This compound crystallizes in the orthorhombic system (SG Pbam) with cell parameters a=12.453(4) Å; b=12.416(1) Å; c=3.9700(4) Å. It presents a TTB type host network in which triangular tunnels remain empty, square ones are fully filled with Ag⁺ and pentagonal ones show mixed occupancy with Ag⁺ and [NbO]³⁺ entities. Crystal-chemistry investigations show that despite a complex and more or less disordered structure, no evidence for solid solution domain is observed.     

Syntheses, crystal structures and optical spectroscopy of Ln2(SO4)3·8H2O (Ln=Ho, Tm) and Pr2(SO4)3·4H2O

The lanthanide sulphate octahydrates Ln₂(SO₄)₃·8H₂O (Ln=Ho, Tm) and the respective tetrahydrate Pr₂(SO₄)₃·4H₂O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln₂(SO₄)₃·8H₂O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a_Ho=13.4421(4) Å, b_Ho=6.6745(2) Å, c_Ho=18.1642(5) Å, β_Ho=102.006(1) Å³ and a_Tm=13.4118(14) Å, b_Tm=6.6402(6) Å, c_Tm=18.1040(16) Å, β_Tm=101.980(8) Å³), Pr₂(SO₄)₃·4H₂O adopts space group P2₁/n (a=13.051(3) Å, b=7.2047(14) Å, c=13.316(3) Å, β=92.55(3) Å³). The vibrational and optical spectra of Ho₂(SO₄)₃·8H₂O and Pr₂(SO₄)₃·4H₂O are also reported.     

Synthesis, structure of [H3dien]·(MF6)·H2O (M=Cr, Fe) and Fe Mössbauer study of [H3dien]·(FeF6)·H2O

Single crystals of [H₃dien]·(FeF₆)·H₂O (I) and [H₃dien]·(CrF₆)·H₂O (II) are obtained by solvothermal synthesis under microwave heating. I is orthorhombic (Pna2₁) with a=11.530(2) Å, b=6.6446(8) Å, c=13.787(3) Å, V=1056.3(2) Å³ and Z=4. II is monoclinic (P2₁/c) with a=13.706(1) Å, b=6.7606(6) Å, c=11.3181(9) Å, β=99.38(1)°, V=1034.7(1) Å³ and Z=4. The structure determinations, performed from single crystal X-ray diffraction data, lead to the R₁/wR₂ reliability factors 0.028/0.066 for I and 0.035/0.102 for II. The structures of I and II are built up from isolated FeF₆ or CrF₆ octahedra, water molecules and triprotonated amines. In both structures, each octahedron is connected by hydrogen bonds to six organic cations and two water molecules. The iron-based compound is also characterized by ⁵⁷Fe Mössbauer spectrometry: the hyperfine structure confirms the presence of Fe³⁺ in octahedral coordination and reveals the existence of paramagnetic spin fluctuations.     

La(Li1/3Ti2/3)O3: a new 1:2 ordered perovskite

A new 1:2 ordered perovskite La(Li_1/3Ti_2/3)O₃ has been synthesized via solid-state techniques. At temperature >1185°C, Li and Ti are randomly distributed on the B-sites and the X-ray powder patterns can be indexed in a tilted (b⁻b⁻c⁺) Pbnm orthorhombic cell (a=a_c√2=5.545 Å, b=a_c√2=5.561 Å, c=2a_c=7.835 Å). However, for T?1175°C, a 1:2 layered ordering of Li and Ti along 〈111〉_c yields a structure with a P2₁/c monoclinic cell with a=a_c√6=9.604 Å, b=a_c√2=5.552 Å, c=a_c3√2=16.661 Å, β=125.12°. While this type of order is well known in the A²⁺(B²⁺_1/3B⁵⁺_2/3)O₃ family of niobates and tantalates, La(Li_1/3Ti_2/3)O₃ is the first example of a titanate perovskite with a 1:2 ordering of cations on the B-sites.     

Synthesis, crystal structure and NLO property of a nonmetal pentaborate [C6H13N2][B5O6(OH)4]

A nonmetal pentaborate [C₆H₁₃N₂][B₅O₆(OH)₄] (1) has been synthesized by 1,4-diazabicyclo[2.2.2] octane (DABCO) and boric acid, and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system with space group Cc (no. 9), a=10.205(2) Å, b=14.143(3) Å, c=11.003(2) Å, β=113.97(3)°, V=1451.1(5) Å³, Z=4. The anionic units, [B₅O₆(OH)₄]⁻, are interlinked via hydrogen bonding to form a three-dimensional (3D) supramolecular network containing large channels, in which the protonated [C₆H₁₃N₂]⁺ cations are located. Second-harmonic generation (SHG) measurements on the powder samples reveal that 1 exhibits SHG efficiency approximately 0.9 times that of potassium dihydrogen phosphate (KDP).     

Syntheses, structures and magnetic properties of two new one-dimensional cobalt (II) phosphites with organic amines acting as ligands

Two new one-dimensional (1D) inorganic-organic hybrid cobalt (II) phosphites Co(HPO₃) (py) (1) and [Co(OH)(py)₃][Co(py)₂][HPO₂(OH)]₃ (2) have been prepared under solvothermal conditions in the presence of pyridine (py). Compound 1 crystallizes in the monoclinic system, space group p2(1)/c, a=5.3577(7) Å, b=7.7503(10) Å, c=17.816(2) Å, β=94.327(2)°, V=737.67(16) Å³, Z=4. Compound 2 is orthorhombic, Cmcm, a=16.3252(18) Å, b=15.7005(16) Å, c=13.0440(13) Å, β=90.00° V=3343.4(6) Å³ and Z=4. Compound 1 possesses a 1D ladder-like framework constructed from CoO₃N tetrahedral, HPO₃ pseudo-pyramids and pyridine ligands. While compound 2 is an unusual inorganic-organic hybrid 1D chain, which consists of corner-shared six-membered rings made of CoO₃N₃/CoO₄N₂ octahedra and HPO₃ pseudo-pyramids through sharing vertices.     

Syntheses, structures and Raman spectra of Cd(BF4)(AF6) (A = Ta, Bi) compounds

The compounds, Cd(BF₄)(TaF₆) and Cd(BF₄)(BiF₆), have been synthesized and characterized by single-crystal X-ray diffraction and Raman spectroscopy. Both isostructural compounds crystallize in the monoclinic P2₁/c space group with a = 8.2700(6) Å, b = 9.3691(6) Å, c = 8.8896(7) Å, β = 94.196(3)°, V = 686.94(9) Å³ for Cd(BF₄)(TaF₆) and a = 8.3412(8) Å, b = 9.4062(8) Å, c = 8.9570(7) Å, β = 93.320(5)°, V = 701.58(11) Å³ for Cd(BF₄)(BiF₆). Eight fluorine atoms (4 BF₄⁻ + 4 AF₆⁻) form a surrounding around the cadmium atom in the shape of distorted square antiprism. These compounds are not isostructural with mixed-anion analogues of Ca, Sr, Ba and Pb studied earlier.