Crystal Structure and Stablility of the Fullerene – Chalcogene Co‐Crystal C60Se8CS2

C₆₀Se₈CS₂ was prepared, for the first time, by slow concentration of a solution of C₆₀ and Se₈ in carbondisulfide. The crystal structure (P2₁/c, a = 1330.05(17), b = 2900.6(4), c = 988.09(13) pm, b = 91.760(2)°; Z = 4; 8910 independent reflections; R₁ = 0.073; wR₂ = 0.186) contains fully ordered fullerene molecules. It may be derived from the NiAs‐structure‐type with Se₈‐rings and CS₂ filling the octahedral voids of the distorted hexagonal close packing of fullerene molecules. The results are completed by Raman‐spectroscopic and thermogravimetric investigations.     

Synthesis,Characterization, Crystal Structure,and hybrid DFT Computation of Antimony(III) Chloride Diazide,SbCl(N3)2

SbCl(N₃)₂ was synthesized by the reaction of two equivalents of sodium azide with SbCl₃ in CH₂Cl₂. The structure of the compound was determined by X‐ray structure determination. SbCl(N₃)₂ crystallizes in the monoclinic space group C2/c with a = 11.694(4), b = 7.751(4) and c = 12.241(5) Å, β = 100.45(1)°, with 8 formula units per unit cell. The SbCl(N₃)₂ molecules show interactions to form chains. The frequencies obtained by Raman and infrared spectroscopy were assigned to the normal modes of the SbCl(N₃)₂ molecules in comparison with computational results.     

Darstellung und Kristallstrukturen von Ln2Al3Si2 und Ln2AlSi2 (Ln: Y,Tb–Lu)

Synthesis and Crystal Structures of Ln ₂Al₃Si₂ and Ln ₂AlSi₂ ( Ln : Y, Tb–Lu) Eight new ternary aluminium silicides were prepared by heating mixtures of the elements and investigated by means of single‐crystal X‐ray methods. Tb₂Al₃Si₂ (a = 10.197(2), b = 4.045(1), c = 6.614(2) Å, β = 101.11(2)°) and Dy₂Al₃Si₂ (a = 10.144(6), b = 4.028(3), c = 6.580(6) Å, β = 101.04(6)°) crystallize in the Y₂Al₃Si₂ type structure, which contains wavy layers of Al and Si atoms linked together by additional Al atoms and linear Si–Al–Si bonds. Through this there are channels along [010], which are filled by Tb and Dy atoms respectively. The silicides Ln₂AlSi₂ with Ln = Y (a = 8.663(2), b = 5.748(1), c = 4.050(1) Å), Ho (a = 8.578(2), b = 5.732(1), c = 4.022(1) Å), Er (a = 8.529(2), b = 5.719(2), c = 4.011(1) Å), Tm (a = 8.454(5), b = 5.737(2), c = 3.984(2) Å) and Lu (a = 8.416(2), b = 5.662(2), c = 4.001(1) Å) crystallize in the W₂CoB₂ type structure (Immm; Z = 2), whereas the structure of Yb₂AlSi₂ (a = 6.765(2), c = 4.226(1) Å; P4/mbm; Z = 2) corresponds to a ternary variant of the U₃Si₂ type structure. In all compounds the Si atoms are coordinated by trigonal prisms of metal atoms, which are connected by common faces so that Si₂ pairs (d_Si–Si: 2.37–2.42 Å) are formed.     

Novel Lanthanide(III) Ternary Complexes with Naphthoyltrifluoroacetone: A Synthetic and Spectroscopic Study

A series of lanthanide complexes with general formula [Ln(NTA)₃X] were prapared [Ln = Y ( a ), Er ( b ), Eu ( c ), NTA = naphthoyltrifluoroacetone, X = H₂O ( 1 ), phen = phenanthroline ( 2 ), bpyO1 = 2, 2′‐bipyridine N‐oxide ( 3 ), and bpyO2 = 2, 2′‐bipyridine‐N,N′‐dioxide ( 4 )]. The crystal structures of [Eu(NTA)₃bpyO2] ( 4b ), [Er(NTA)₃bpyO1] ( 3c ), and [Er(NTA)₃phen] ( 2c ) were determined. X‐ray crystallographic analysis reveals that the complexes are of mononuclear structure with three NTA and one ancillary ligand. The photoluminescence spectra of 3c and 4b exhibit strong characteristic emissions arising from Eu³⁺ central ion due to the efficient sensitization of bpyO1 and bpyO2, respectively.     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalysen von (n-Bu4N)2[ReBr5(NCS)] und (n-Bu4N)2[ReBr5(NCSe)]

Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of ( n -Bu₄N)₂[ReBr₅(NCS)] and ( n -Bu₄N)₂[ReBr₅(NCSe)] The X-ray structure determinations on single crystals of (n-Bu₄N)₂[ReBr₅(NCS)] ( 1 ) (monoclinic, space group P2₁/n, a = 10.9860(9), b = 11.6860(7), c = 35.551(3) Å, β = 91.960(9)°, Z = 4) and (n-Bu₄N)₂[ReBr₅(NCSe)] ( 2 ) (monoclinic, space group P2₁/n, a = 11.0208(15), b = 11.7418(16), c = 35.621(12) Å, β = 92.003(18)°, Z = 4) reveal that the thiocyanate and the selenocyanate group are bonded with the Re–N–C angle of 168.5° ( 1 ) and 169.9° ( 2 ). Based on the molecular parameters of the X-ray determinations the IR and Raman spectra have been assigned by normal coordinate analysis. The valence force constants f_d(ReN) are 1.81 ( 1 ) and 1.75 mdyn/Å ( 2 ).     

Zur Kenntnis von Strontiumhydroxidchlorid und Strontiumhydroxidbromid – Darstellung,Kristallstrukturen, IR- und Raman-Spektren

Strontium Hydroxide Chloride and Strontium Hydroxide Bromide – Preparation, Crystal Structure, and IR and Raman Spectra The partly hitherto unknown compounds Sr(OH)Cl, Sr(OH)Br mC16 and Sr(OH)Br cP16 have been established by both dehydration of the hydrates (Sr(OH)Cl, Sr(OH)Br mC16) and melting together stoichiometric mixtures of Sr(OH)₂ and SrCl₂ or SrBr₂ (Sr(OH)Cl, Sr(OH)Br cP16). The monoclinic polymorph of the bromide is monotropically changed above 650 K (high-temperature X-ray and high-temperature Raman studies) into the cubic modification. Sr(OH)Cl crystallizes in the Cd(OH)Cl structure type (space group P6₃mc, Z = 2, a = 414.41(2), c = 995.16(10) pm), Sr(OH)Br mC16 and cP16 crystallizing in own structures (C2/m, Z = 4, a = 1100.66(7), b = 429.55(3), c = 726.25(5) pm, β = 106.285(4)°, P2₁3, Z = 4, a = 675.79(2) pm). The structures were refined from X-ray powder diffractograms (Sr(OH)Cl: R_I = 11.4%, 4668 observations, Sr(OH)Br mon.: R_I = 13%, 1082 observations), neutron powder diffractograms (Sr(OD)Br cub.: R_I = 3,8%, 793 observations), and X-ray single-crystal studies, respectively (Sr(OH)Br cub.: R1 = 5.02%, 585 independent reflections). The positions of the hydrogen atoms of Sr(OH)Cl and Sr(OH)Br mon. were determined by the method of minimum cohesive energy. Sr(OH)Cl and Sr(OH)Br mon. crystallize in layered structures with monocapped distorted octahedrally (3 OH^– and 4 X^–) coordinated strontium ions. Sr(OH)Br cub. crystallizes in a structure built up of three-dimensional nets, the coordination of Sr, however, corresponds to that of Sr(OH)Cl and Sr(OH)Br mon. IR and Raman spectra are presented and discussed together with the structure data with respect to the strength of the O–H…X hydrogen bonds (stretching modes of matrix isolated OD^– ions: 2641 cm^–1 (Sr(OH)Cl), 2662 cm^–1 (Sr(OH)Br mon.), and 2614 cm^–1 and 2572 cm^–1 (Sr(OH)Br cub.) (295 K)) and the dependence of the librations of the OH^– ions on the strength of the hydrogen bonds and the packing of the structure. The OH^– ions of Sr(OH)Br cub. display a temperature dependent disorder between a thermodynamically more stable position with trifurcated hydrogen bonds and one with stronger, almost linear bonds.     

Synthesis and X-ray crystal structure of oxamido-bridged heterobinuclear Ni(Ⅱ)-Cu(Ⅱ) complexes

The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment.     

The Reduction of AuF3 in Super Acidic Solution

AuF₃ is reduced in superacidic HF/SbF₅ solutions giving three products. 1. Orange [Au₃F₈·2SbF₅]. It has a layered structure built up by square planar Au^IIF₄ and Au^IIIF₄ units: Crystal structure: space group P2₁/c, a = 9.049(2), b = 8.424(1), c = 9.645(1)Å, β = 115.08(1)°. 2. Black [Au₃F₇·3SbF₅] has a ribbon structure, similarly built up by square planar Au^IIF₄ and Au^IIIF₄ units: Crystal structure: space group Pc, a = 9.991(1), b = 10.728(1), c = 15.222(1)Å, β = 95.304(2)°. 3. Yellow green [(Au(HF)₂] (SbF₆)₂·2HF with square planar Au^IIF₄ units that are formed by two fluorine atoms of the anions and two HF molecules as complex ligands. Crystal structure: Space group P¯, a = 5.482(1), b = 5.848(1), c = 9.309(2)Å, α = 89.522(4), β = 85.635(4), γ = 87.509(4)°.     

Dipotassium Sodium Diantimonidoindate,K2Na[InSb2], a compound with the polyanion [In2Sb2Sb4/2]6−

The novel compound K₂Na[InSb₂] was synthesized from the elements at 900 K in sealed niobium ampoules. The compound forms plate-like crystals with silver metallic luster, which are very unstable in air and moisture. The crystal structure of K₂NaInSb₂ has been determined using single-crystal X-ray diffraction methods (space group Cmca (No. 64); a = 14.032(2), b = 16.399(3), c = 7.009(1) Å; Z = 8; Pearson symbol oC48). The structure contains pairs of edge-sharing InSb₄ tetrahedra which are linked to four other pairs via common vertices and form a two-dimensional [In₂Sb₂Sb_4/2]^6? anionic partial structure. The resulting pairs of tetrahedral holes are filled by Na⁺ cations. These [In₂Sb₂Sb_4/2]^6? layers are stacked along the b-axis and are interconnected by K⁺ cations. The whole structure can be considered as an ordered derivative of the KMnP structure (PbFCl type).     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen der Tetrahalogeno‐bis‐Pyridin‐Osmium(III)‐Komplexe cis‐(n‐Bu4N)[OsCl4Py2] und trans‐(n‐Bu4N)[OsX4Py2], X = Cl,Br

Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Tetrahalogeno‐bis‐Pyridine‐Osmium(III) Complexes cis ‐( n ‐Bu₄N)[OsCl₄Py₂] and trans ‐( n ‐Bu₄N)[OsX₄Py₂], X = Cl, Br By reaction of (n‐Bu₄N)₂[OsX₆], X = Cl, Br, with pyridine and (n‐Bu₄N)[BH₄] tetrahalogeno‐bis‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of cis‐(n‐Bu₄N)[OsCl₄Py₂] ( 1 ) (triclinic, space group P1, a = 9.4047(9), b = 10.8424(18), c = 17.007(2) Å, α = 71.833(2), β = 81.249(10), γ = 67.209(12)°, Z = 2), trans‐(n‐Bu₄N)[OsCl₄Py₂] ( 2 ) (orthorhombic, space group P2₁2₁2₁, a = 8.7709(12), b = 20.551(4), c = 17.174(4) Å, Z = 4) and trans‐(n‐Bu₄N)[OsBr₄Py₂] ( 3 ) (triclinic, space group P1, a = 9.132(3), b = 12.053(3), c = 15.398(2) Å, α = 95.551(18), β = 94.12(2), γ = 106.529(19)°, Z = 2). Based on the molecular parameters of the X‐ray structure determinations and assuming C₂ point symmetry for the anion of 1 and D_2h point symmetry for the anions of 2 and 3 the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants of 1 are in the Cl–Os–Cl axis f_d(OsCl) = 1.58, in the asymmetrically coordinated N′–Os–Cl ^· axes f_d(OsCl ^· ) = 1.45, f_d(OsN′) = 2.48, of 2 f_d(OsCl) = 1.62, f_d(OsN) = 2.42 and of 3 f_d(OsBr) = 1.39 and f_d(OsN) = 2.34 mdyn/Å.     

Bismuth(III) Complexes with N,N‐Di(2‐hydroxylethyl)aminodithiocarboxylate: Synthesis and Crystal Structure of {Bi[S2CN(C2H4OH)2]2[1, 10‐Phen]2(NO3)}·3H2O and (Bi[S2CN(C2H4OH)2]3}2

Two novel one‐ and two‐dimensional network structure bismuth(III) complexes with N, N‐di(2‐hydroxylethyl)‐aminodithiocarboxylate, {Bi[S₂CN(C₂H₄OH)₂]₂[1, 10‐Phen]₂(NO₃)}·3H₂O (1) and (Bi[S₂CN(C₂H₄OH)₂]₃)₂ (2) were synthesized. Their crystal and molecular structures were determined by X‐ray single crystal diffraction analysis. The crystal 1 belongs to monoclinic system with space group C2/c, a=1.6431(7) nm, b=2.4323(10) nm, c= 1.2646(5) nm, β=126. 237(5), Z=4, V=4.076(3) nm³, D_c=1.757 Mg/m^3, μ=4.598 mm^?1, F(000)=2156, R= 0.0211, wR=0.0369. The structure shows a distorted square antiprism configuration with eight‐coordination for the central Bi atom. The one‐dimensional chain structure was formed by H‐bonding interaction between hydroxyl group of N, N‐di(2‐hydroxylethyl)aminodithiocarboxylate ligands and crystal water. The crystal 2 belongs to monoclinic system with space group p2(1)/c, a= 1.1149(4) nm, b=2.1274(8) nrn, c=2.2107(8) nm, β=98.325(8)°, 2=4, V=5. 188(3) nm³, Dc=1.920 Mg/m³, μ=7.315 mm^?1, F(000)=2944, R=0.0565, wR=0.0772. The structure shows a distorted square antiprism configuration with eight‐coordination for the central Bi atoms. The two‐dimensional network structure was formed by H‐bonding interaction between adjacent molecules.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen von trans-(PNP)[TcCl4(Py)2] und trans-(PNP)[TcBr4(Py)2]

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of trans-(PNP)[TcCl₄(Py)₂] and trans-(PNP)[TcBr₄(Py)₂] By reaction of (PNP)₂[TcX₆] with pyridine in the presence of [BH₄]^? (PNP)[TcX₄(Py)₂], X = Cl, Br, are formed. X-ray structure determinations on single crystals of these isotypic Tc^III complexes (monoclinic, space group P2₁/n, Z = 2, for X = Cl: a = 13.676(4), b = 9.102(3), c = 17.144(2) Å, β = 91.159(1)°; for X = Br: a = 13.972(2), b = 9.146(3), c = 17.285(4) Å, β = 90.789(2)°) result in the averaged bond distances Tc? Cl: 2.386, Tc? Br: 2.519, Tc? N: 2.132(3) (X = Cl) and 2.143(4) Å (X = Br). The two pyridine rings are coplanar and vertical to the X? Tc? X-axes, forming angles of 42.28° (X = Cl) and 43.11° (X = Br). Using the molecular parameters of the X-ray structure determination and assuming D_2h point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis based on a modified valence force field. Good agreement between observed and calculated frequencies is obtained with the valence force constants f_d(TcCl) = 1.45, f_d(TcBr) = 1.035, f_d(TcN) = 1.37 (X = Cl) and 1.45 mdyn/ Å (X = Br), respectively.     

Study on the Structure of a Mixed KCl and K2SO4 Aqueous Solution Using a Modified X-ray Scattering Device,Raman Spectroscopy,and Molecular Dynamics Simulation

The microstructure of a mixed KCl and K₂SO₄ aqueous solution was studied using X-ray scattering (XRS), Raman spectroscopy, and molecular dynamics simulation (MD). Reduced structure functions [F(Q)], reduced pair distribution functions [G(r)], Raman spectrum, and pair distribution functions (PDF) were obtained. The XRS results show that the main peak (r = 2.81 Å) of G(r) shifted to the right of the axis (r = 3.15 Å) with increased KCl and decreased K₂SO₄. The main peak was at r = 3.15 Å when the KCl concentration was 26.00% and the K₂SO₄ concentration was 0.00%. It is speculated that this phenomenon was caused by the main interaction changing, from K-O_W (r = 2.80 Å) and O_W-O_W (r = 2.80 Å), to Cl⁻-O_W (r = 3.14 Å) and K⁺-Cl⁻ (r = 3.15 Å). According to the trend of the hydrogen bond structure in the Raman spectrum, when the concentration of KCl was high and K₂SO₄ was low, the destruction of the tetrahedral hydrogen bond network in the solution was more serious. This shows that the destruction strength of the anion to the hydrogen bond network structure in solution was Cl⁻ > SO₄²⁻. In the MD simulations, the coordination number of O_W-O_W decreased with increasing KCl concentration, indicating that the tetrahedral hydrogen bond network was severely disrupted, which confirmed the results of the Raman spectroscopy. The hydration radius and coordination number of SO₄²⁻ in the mixed solution were larger than Cl⁻, thus revealing the reason why the solubility of KCl in water was greater than that of K₂SO₄ at room temperature.     

Synthesis,Structure and Raman Data of the New Binuclear Zirconium Complex [Ph4P]2[(ZrCl4Py)2O], with a Zr‐O‐Zr Bridge

The new Zirconium(IV) coordination compound [Ph₄P]₂[(ZrCl₄Py)₂O] (Ph = phenyl, Py = pyridine) was synthesized by dissolving ZrCl₄, [Ph₄P]Cl and a stoichiometric amount of NaOH/Na mixture in pyridine or pyridine/organic solvent mixtures. The title phase was obtained as colourless crystals. The crystal structure of [Ph₄P]₂[(ZrCl₄Py)₂O] was determined. It crystallizes monoclinic, P2₁/c, Z = 4, a = 13.412(2), b = 13.461(2), c = 16.442(3) Å, β = 102.72(1)°. The structure consists of isolated tetraphenylphosphonium cations and [(ZrCl₄Py)₂O]^2? complex anions. The centrosymmetric complex anion contains a linear Zr–O–Zr bridge. Each Zr atom is coordinated by one oxygen dianion, the N atom of one pyridine ring and four chloro ligands in a distorted octahedral geometry. The Raman spectrum of [Ph₄P]₂[(ZrCl₄Py)₂O] is also reported. Most of the observed frequencies can be assigned to vibrations of the tetraphenylphosphonium cations and the pyridine rings.     

Synthesis,IR Spectra,Thermal Analysis and Crystal Structures of Bis(saccharinato)mercury(II) Complexes with 2–Aminomethylpyridine and 2–Aminoethylpyridine

Two bis(saccharinato) (sac) complexes of mercury(II) with 2–aminomethylpyridine (ampy) and 2–aminoethylpyridine (aepy) were synthesized and characterized by means of elemental analysis, FT–IR spectroscopy and thermal analysis and single crystal X–ray diffraction. trans–[Hg(sac)₂(ampy)₂] ( 1 ) crystallizes in the monoclinic space group P2₁/c [a = 10.8274(4), b = 16.4903(6), c = 7.7889(3) Å; β = 99.500(1)°] and [Hg(sac)₂(aepy)] ( 2 ) also crystallizes monoclinic in space group P2₁/n [a = 9.0423(4), b = 14.0594(6), c = 18.0146(8) Å; ß = 98.806(1)°]. Both 1 and 2 consist of neutral monomeric units. The mercury(II) ion in 1 lies on an inversion centre and exhibit distorted octahedral coordination by two sac anions and two ampy ligands, whereas the mercury(II) ion in 2 is tetrahedrally coordinated by an aepy and two sac ligands. The sac ligands in both complexes are N–coordinated, while the ampy and aepy ligands act as a bidentate ligand forming two symmetrically chelate rings around the mercury(II) ion.     

Strukturverfeinerung und magnetische Messungen an Mn2SnS4

Structure Redetermination and Magnetic Studies on Mn₂SnS₄ The crystal structure of Mn₂SnS₄ was redetermined by single crystal and powder X-ray studies. It has a deficient NaCl superstructure crystallizing in the orthorhombic space group Cmmm proposed by Wintenberger and Jumas in 1980 (Z = 2, a = 740.7(1), b = 1047.5(1) and c = 366.7(2) pm, R_f = 1.4% for 266 unique reflections with I > 0σ₁). Some additional reflections, which are not compatible with this cell, can be refined assuming formation of twinned trilling crystals. Mn₂SnS₄ undergoes antiferromagnetic ordering below 160 K. The effective magnetic moment μ_eff of Mn²⁺ is 5.92 B.M. The IR and Raman spectra display 5 and 3 bands in the range 150–320 cm^?1, respectively.     

Synthesis and Crystal Structure of β-Amino-α-Phenyl-α-Ferrocenylethanol

β-Amino-α-phenyl-α-ferrocenylethanol, FcC(OH)(Ph)CH₂NH₂ was prepared by the reduction of cyanohydrin trimethylsilyl ether of benzoylferrocene with lithium aluminum hydride. This new compound was characterized by elemental analysis, IR and ¹H NMR spectroscopy. The structure was also confirmed by a single crystal X-ray study. The compound crystallizes in monoclinic P2₁/c space group with unit cell dimensions: a = 12.5906(17), b = 5.9636(8), c = 19.8320(3) Å, β = 102.047(2)^∘, V = 1456.3(3) ų, Z = 4. The structure exhibits intra- and inter-molecular hydrogen bonding of the type N—H⋅ < eqid1 > ⋅O and O—H⋅ < eqid2 > ⋅N, respectively. The pattern of the inter-molecular hydrogen bonding interaction contains a 10-atom ring with two donors and two acceptors, showing a dimeric crystal packing.     

Synthesis,Characterization and Crystal Structures of new Coordination Polymers of Cerium(III) and Samarium(III) Containing 2,6‐Pyridinedicarboxylic Acid

The reaction of 2,6‐pyridinedicarboxylic acid ( 1 , LH₂) with CeCl₃·7H₂O and Sm(NO₃)₃·6H₂O in the presence of triethylamine led to the coordination polymer complexes [M(L)(LH)(H₂O)₂]·4H₂O [M = Ce ( 2 ) and Sm ( 3 )]. Both complexes were characterized by elemental analyses, IR spectroscopy and the crystal structures of 2 and 3 . Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1404.6(1), b = 1122.1(1), c = 1296.1(1) pm, β = 102.09(1)°, Z = 4, R₁ = 0.0217 and for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1395.1(1), b = 1120.1(1), c = 1282.8(1) pm, β = 102.71(1)°, Z = 4, R₁ = 0.019.     

Synthesis,Characterization and Crystal Structure of 4‐Amino‐1,2,4‐Δ2‐triazoline‐5‐thione and its Silver(I) Complex

The reaction of 4‐amino‐1,2,4‐Δ²‐triazoline‐5‐thione (ATT, 1 ) with AgNO₃ in methanol led to the complex [Ag(ATT)₂]NO₃ ( 2 ). 2 was characterized by elemental analyses, ¹H NMR, IR, and Raman spectroscopy as well as single‐crystal X‐ray diffraction. The molecular structure of 1 was also determined by single crystal X‐ray analysis. Crystal data for 1 at ?80 C: space group C2/c with a = 2107.4(2), b = 1425.1(1), c = 688.4(1) pm, β = 104.55(1)°, Z = 16, R₁ = 0.0514, crystal data for 2 at ?80 °C: space group P2₁/c with a = 675.7(1), b = 1321.1(1), c = 1311.2(1) pm, β = 90.03(1)°, Z = 4, R₁ = 0.0437.     

Strukturuntersuchungen an den Oxidnitriden SrTaO2N,CaTaO2N und LaTaON2 mittels Neutronen‐ und Röntgenbeugung

Structural Investigations on the Oxidenitrides SrTaO₂N, CaTaO₂N and LaTaON₂ by Neutron and X‐ray Powder Diffraction The crystal structures of the perovskite related oxidenitrides SrTaO₂N, LaTaON₂ and CaTaO₂N have been determined with special regard to the structures of the respective anionic partial structure. The structure refinements were performed by individual Rietveld analyses of both X‐ray and neutron powder diffractograms and in addition by joint refinements in order to confirm the results. Both refinement methods yield consistent structure solutions. At least the first two compounds have fully ordered anionic sublattices. The crystal structure of SrTaO₂N has been solved in the space group I4/mcm (a = 5.7049(3) Å, c = 8.0499(5) Å, R_p = 0.0706, R_wp = 0.0904, reflections: 70 (neutrons)/36 (X‐ray), R(F²)(n) = 0.147, R(F²)(X) = 0.0952), with an ordered anionic partial structure. LaTaON₂ crystallizes monoclinic (C2/m, a = 8.0922(3) Å, b = 8.0603(2) Å, c = 5.7118(2) Å, β = 134.815(1)°, R_p = 0.0592, R_wp = 0.0766, reflections: 235(n)/113(X), R(F²)(n) = 0.0944, R(F²)(X) = 0.165) and also shows a totally ordered distribution of the anions. In the case of CaTaO₂N (Pnma, a = 5.6239(3) Å, b = 7.8954(4) Å, c = 5.5473(3) Å, R_p = 0.0503, R_wp = 0.0656, reflections 206(n)/110(X), R(F²)(n) = 0.0985, R(F²)(X) = 0.0405) slightly unbalanced displacement parameters (neutron data, ordered O/N distribution model) hint at a partial exchange of oxygen and nitrogen.