Browsing by Author "Schleid, Thomas"

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Open Access
A-type Ce2NCl3
(2011) Schurz, Christian M.; Schleid, Thomas
The crystal structure of cerium nitride chloride (A-type) as well as the synthesis method is described in this paper.
Open Access
About lanthanoid fluoride selenide oxoselenotantalates with the composition Ln3F2Se2TaO4 (Ln = La - Nd)
(2020) Grossholz, Hagen; Buyer, Constantin; Lotter, Sebastian M. A.; Wolf, Sarah; Schleid, Thomas
After solid-state reactions of the light lanthanoid metals, their oxides and fluorides as well as selenium in sealed tantalum ampoules with sodium chloride as a fluxing agent at 850 °C for 8 days needle-shaped single crystals of Ln3F2Se2TaO4 (Ln = La - Nd) were obtained. They crystallize in the orthorhombic space group Pnma analogous to La3F2Se2NbO4 with a = 1133-1120 pm, b = 400-393 pm and c = 1812-1778 pm (Ln = La - Nd) for Z = 4 as the first known quinary lanthanoid(III) oxoselenotantalates(V) with fluoride and selenide anions. The three crystallographically different Ln3+ cations are all surrounded by nine anions (O2-, F- and Se2-) each. Tantalum resides in an octahedral chalcogen coordination by forming trans-vertex oxygen-connected [TaO5Se]7- polyhedra, which build up chains 1∞{[TaOV2/2Ot3/1Set1/1]5-} along [010]. The sites of the four crystallographically different oxygen atoms and the two distinct fluoride anions were established by bond-valence calculations. One fluorine and three oxygen atoms are surrounded tetrahedrally by cations, while another fluoride and oxide anion exhibit just triangular non-planar coordination spheres. The two independent Se2- anions have five or six cationic neighbors.
Open Access
Ba7C2Al2O9 : a barium oxide carbide oxoaluminate with the structured formula Ba7O[C2][AlO4]2
(2025) Reckeweg, Olaf; Lissner, Falk; Locke, Ralf J. C.; Schleid, Thomas
The mixed‐anionic barium compound Ba7O[C2][AlO4]2 is obtained by serendipity via a high‐temperature synthesis route designed to yield “Ba5[AlC2]2”. Its new crystal structure is determined from X‐ray diffraction data of selected single crystals exhibiting the orthorhombic space group Pnma with the lattice parameters a = 2264.21(16), b = 597.08(4), and c = 1114.67(8) pm for Z = 4. Isolated [AlO4]5- tetrahedra alongside O2- and [C2]2- anions provide appropriate coordination spheres for the seven crystallographically independent Ba2+ cations with C.N. = 7-9. These structural elements and their incremental volumes are compared to those of related compounds. Irregular [OBa5+1]10+ octahedra and ([C2]Ba5+2)12+ polyhedra complete the crystal structure of Ba7O[C2][AlO4]2, whose most covalent features (ortho‐oxoaluminate tetrahedra [AlO4]5- and acetylide dumbbells -[C≡C]-) can also be identified unambiguously by single‐crystal Raman spectroscopy.
Open Access
A challenge toward novel quaternary sulfides SrLnCuS3 (Ln = La, Nd, Tm) : unraveling synthetic pathways, structures and properties
(2022) Ruseikina, Anna V.; Grigoriev, Maxim V.; Solovyov, Leonid A.; Chernyshev, Vladimir A.; Aleksandrovsky, Aleksandr S.; Krylov, Alexander S.; Krylova, Svetlana N.; Shestakov, Nikolai P.; Velikanov, Dmitriy A.; Garmonov, Alexander A.; Matigorov, Alexey V.; Eberle, Marcel A.; Schleid, Thomas; Safin, Damir A.
We report on the novel heterometallic quaternary sulfides SrLnCuS3 (Ln = La, Nd, Tm), obtained as both single crystals and powdered samples. The structures of both the single crystal and powdered samples of SrLaCuS3 and SrNdCuS3 belong to the orthorhombic space group Pnma but are of different structural types, while both samples of SrTmCuS3 crystallize in the orthorhombic space group Cmcm with the structural type KZrCuS3. Three-dimensional crystal structures of SrLaCuS3 and SrNdCuS3 are formed from the (Sr/Ln)S7 capped trigonal prisms and CuS4 tetrahedra. In SrLaCuS3, alternating 2D layers are stacked, while the main backbone of the structure of SrNdCuS3 is a polymeric 3D framework [(Sr/Ln)S7]n, strengthened by 1D polymeric chains (CuS4)n with 1D channels, filled by the other Sr2+/Ln3+ cations, which, in turn, form 1D dimeric ribbons. A 3D crystal structure of SrTmCuS3 is constructed from the SrS6 trigonal prisms, TmS6 octahedra and CuS4 tetrahedra. The latter two polyhedra are packed together into 2D layers, which are separated by 1D chains (SrS6)n and 1D free channels. In both crystal structures of SrLaCuS3 obtained in this work, the crystallographic positions of strontium and lanthanum were partially mixed, while only in the structure of SrNdCuS3, solved from the powder X-ray diffraction data, were the crystallographic positions of strontium and neodymium partially mixed. Band gaps of SrLnCuS3 (Ln = La, Nd, Tm) were found to be 1.86, 1.94 and 2.57 eV, respectively. Both SrNdCuS3 and SrTmCuS3 were found to be paramagnetic at 20-300 K, with the experimental magnetic characteristics being in good agreement with the corresponding calculated parameters.
Open Access
Composition and crystal structure of SmSb2O4Cl revisited : and the analogy of Sm1.5Sb1.5O4Br
(2019) Goerigk, Felix C.; Schleid, Thomas
The quaternary halide‐containing samarium(III) oxidoantimonates(III) Sm1.3Sb1.7O4Cl and Sm1.5Sb1.5O4Br were synthesized through solid‐state reactions from the binary components (Sm2O3, Sb2O3 and SmX3, X = Cl and Br) at 750 °C in evacuated fused silica ampoules. They crystallize tetragonally in the space group P4/mmm, like the basically isotypic bismuthate(III) compounds SmBi2O4Cl and SmBi2O4Br, but show larger molar volumes and therefore contradict an ideal composition of “SmSb2O4X” (X = Cl and Br). Both single‐crystal X‐ray diffraction and quantitative electron‐beam microprobe analysis revealed the actual compositions of the investigated antimony(III) compounds, which can be understood as heavily Sm3+‐doped derivatives of “SmSb2O4X” hosts at the Sb3+ site. (Sm1)3+ is coordinated eightfold by oxygen atoms in the shape of a cube. The mixed‐occupied (Sb/Sm2)3+ cation has four oxygen atoms and four halide anions as neighbors forming a square antiprism. The oxygen atoms and anions establish alternating layers parallel to the ab‐plane, which alternate when stacked along [001].
Open Access
Crystal structure of digadolinium(III) oxide disulfide, Gd2OS2
(2003) Wontcheu, Joseph; Schleid, Thomas
Gd2OS2, monoclinic, P121/c1 (No. 14), a = 8.3365(6) Å, b = 6.9872(5) Å, c = 6.9231(5) Å, β = 99.463(6)°, V = 397.8Å3, Z = 4, Rgt(F) = 0.022, wRref(F2) = 0.047, T = 293 K.
Open Access
Crystal structure of hexapraseodymium(III) trinitride tetrasulfide chloride, Pr6N3S4Cl
(1999) Meyer, M.; Schleid, Thomas
ClN3Pr6S4, orthorhombic, Pnma (No. 62), a = 11.3987(8) Å, b = 4.0235(3) Å, c = 26.999(1) Å, V = 1238.3 Å3 ,Z = 4, Rgt{F) = 0.037, Rw(F2) = 0.079, T = 293 Κ.
Open Access
Crystal structure of tetracerium(III) trisulfide heptaoxodisilicate(IV), Ce4S3[Si2O7]
(2002) Hartenbach, Ingo; Schleid, Thomas
Ce4O7S3Si2, tetragonal, I41/amd (No. 141), a = 12.0543(8) Å, c = 14.2351(9) Å, V = 2068.4 Å3, Z = 8, Rgt(F) = 0.027, wRref(F2) = 0.060, T = 298 K.
Open Access
Crystal structure of trirubidium dodekaselenoheptadysprosate(III), Rb3Dy7Se12
(2000) Folchnandt, Matthias; Schleid, Thomas
Dy7Rb3Se12, orthorhombic, Pnnm (No. 58), a = 12.590(1) Å, b = 26.183(2) Å, с = 4.1271(4) Å, V= 1360.5 Å 3 , Z = 2, Rgt(F) = 0.054, wR(F2) = 0.119, Τ = 293 К.
Open Access
The crystal structures of two hydro-closo-borates with divalent tin in comparison : Sn(H2O)3[B10H10] · 3 H2O and Sn(H2O)3[B12H12] · 4 H2O
(2021) Kleeberg, Fabian M.; Zimmermann, Lucas W.; Schleid, Thomas
Single crystals of Sn(H2O)3[B10H10] · 3 H2O and Sn(H2O)3[B12H12] · 4 H2O are easily accessible by reactions of aqueous solutions of the acids (H3O)2[B10H10] and (H3O)2[B12H12] with an excess of tin metal powder after isothermal evaporation of the clear brines. Both compounds crystallize with similar structures in the triclinic system with space group P1¯ and Z = 2. The crystallographic main features are electroneutral 1∞{Sn(H2O)3/1[B10H10]3/3} and 1∞{ Sn(H2O)3/1[B12H12]3/3} double chains running along the a-axes. Each Sn2+ cation is coordinated by three water molecules of hydration (d(Sn-O) = 221-225 pm for the B10 and d(Sn-O) = 222-227 pm for the B12 compound) and additionally by hydridic hydrogen atoms of the three nearest boron clusters (d(Sn-H) = 281-322 pm for the B10 and d(Sn-H) = 278-291 pm for the B12 compound), which complete the coordination sphere. Between these tin(II)-bonded water and the three or four interstitial crystal water molecules, classical bridging hydrogen bonds are found, connecting the double chains to each other. Furthermore, there is also non-classical hydrogen bonding between the anionic [BnHn]2- (n = 10 and 12) clusters and the crystal water molecules pursuant to B-Hδ-⋯δ+H-O interactions often called dihydrogen bonds.
Open Access
Cs3Sm7Se12
(2012) Schneck, Christof; Elbe, Andreas; Schurz, Christian M.; Schleid, Thomas
The crystal structure of Cs3Sm7Se12 is described in the paper.
Open Access
Defect scheelite-type lanthanoid(III) ortho-oxomolybdates(VI) Ln0.667[MoO4] (Ln = Ce, Pr, Nd, and Sm) and their relationship to zircon and the NaTl-type structure
(2011) Schustereit, Tanja; Müller, Sabine L.; Schleid, Thomas; Hartenbach, Ingo
The rare-earth metal(III) ortho-oxomolybdates with the formula Ln0.667[MoO4] (Ln = Ce, Pr, Nd, and Sm) and defect scheelite-type structure crystallize in the tetragonal space group I41/a (a = 533–525, c = 1183–1158 pm) with four formula units per unit cell. The Ln3+ cations at Wyckoff position 4b exhibit a coordination sphere of eight oxygen atoms in the shape of a trigonal dodecahedron. The same site symmetry ( 4 ..) is observed for the tetrahedral oxomolybdate(VI) entities [MoO4]2–, since their central Mo6+ cation is situated at the 4a position. Due to this equal site multiplicity, the lanthanoid(III) cations have to be statistically under-occupied to maintain electroneutrality, thus a defect scheelite structure emerges. The partial structure of both the Ln3+ cations and the [MoO4]2– anions (if shrunk to their centers of gravity) can be best described as distorted diamond-like arrangements. Therefore, these two interpenetrating partial structures exhibit a similar setup as found in the zircon-type as well as in the NaTl-type structure.
Open Access
The defect scheelite-type lanthanum(III) ortho-oxidomolybdate(VI) La0.667[MoO4]
(2013) Schustereit, Tanja; Schleid, Thomas; Hartenbach, Ingo
The crystal structure of La0.667[MoO4] in the Scheelite-type is described in that paper.
Open Access
The first members of the monoclinic lanthanoid(III) fluoride oxoarsenate(III) series Ln2F2[As2O5] (Ln=La - Nd and Sm)
(2025) Locke, Ralf J. C.; Zimmer, Frank C.; Schleid, Thomas
In synthesis experiments for the preparation of Ln5F3[AsO3]4 representatives in evacuated glassy silica ampoules at temperatures of maximum 825 °C, surprisingly compounds with the composition Ln2F2[As2O5] could be obtained and subsequently also reproduced on target. The new Ln2F2[As2O5] representatives with Ln = La - Nd and Sm crystallize needle‐shaped in the monoclinic space group P21/c with lattice parameters ranging from a = 793.24(5) pm, b = 1346.39(9) pm, c = 1359.41(9) pm and β = 106.932(3)° for La2F2[As2O5] to a = 769.11(5) pm, b = 1307.50(9) pm, c = 1328.74(9) pm and β = 106.819(3)° for Sm2F2[As2O5] with Z = 8. Their crystal structure can be broken down into two parts consisting of infinite [Ln2F2]4+ and discrete [As2O5]4− units. Three distinct kinds of fluoride anions are trigonally planar surrounded by lanthanoid cations and another one carries even a fourth of them in their coordination sphere with a secondary contact resulting in a distorted tetrahedron. These [FLn3]8+ and [FLn3+1]11+ building blocks share common corners and edges creating strands {[F2Ln2]4+}, which propagate along [100]. The four different As3+ lone‐pair cations form ψ1‐tetrahedra [AsO3]3− with three oxygen atoms and are conversurally linked pairwisely creating dinuclear pyroanionic [As2O5]4− units. These [As2O5]4− groups arrange themselves alternatingly along [100] with their lone pairs pointing into central empty channels. The {[F2Ln2]4+} strands are linked to the [As2O5]4− units via four distinguishable Ln3+ cations providing them coordination numbers of eight and nine. Raman spectroscopy confirmed that no (OH)− groups resulting from the synthesis were present apt to replace part of the F− and the stoichiometry Ln2F2[As2O5] was verified using WDXS elemental analyses.
Open Access
Ho2[As4O9] : the first ternary catena‐oxotetraarsenate(III) of the lanthanoids
(2025) Locke, Ralf Jules Christian; Locke, Klaus; Schleid, Thomas
The pale yellow holmium(III) catena‐oxotetraarsenate(III) Ho2[As4O9] crystallizes needle‐shaped from a CsBr‐flux‐assisted metallothermic reaction between As2O3 and elemental holmium at 875 °C in the monoclinic space group P21/c with the lattice parameters a = 802.98(6) pm, b = 548.83(4) pm, c = 1101.62(9) pm and β = 107.519(3)° for Z = 2. The singular Ho3+ cation is surrounded by seven oxygen atoms in the shape of a capped distorted octahedron [HoO7]11-. These polyhedra link with each other twice via edge and twice via corner to form layers described by the Niggli formula , which spread out parallel to the (100) plane. Both distinct As3+ cations form ψ1‐tetrahedral [AsO3]3- units with three oxygen atoms, which are vertex‐condensed to a catena‐oxotetraarsenate(III) anion [As4O9]6-. All [As4O9]6- groups serve as linkers between the layers, while the stereochemically active free electron pairs at the As3+ cations arrange themselves to create lone‐pair channels along the [010] direction. Furthermore, Raman‐spectroscopic investigations, which frequently show Ho3+ luminescence, and effective coordination number calculations are carried out for the new crystal structure of Ho2[As4O9].
Open Access
Hydrothermal synthesis, crystal structure, and spectroscopic properties of pure and Eu3+-doped NaY[SO4]2 ∙ H2O and its anhydrate NaY[SO4]2
(2021) Buyer, Constantin; Enseling, David; Jüstel, Thomas; Schleid, Thomas
The water-soluble colorless compound NaY[SO4]2 ∙ H2O was synthesized with wet methods in a Teflon autoclave by adding a mixture of Na2[SO4] and Y2[SO4]3 ∙ 8 H2O to a small amount of water and heating it up to 190 °C. By slow cooling, single crystals could be obtained and the trigonal crystal structure of NaY[SO4]2 ∙ H2O was refined based on X-ray diffraction data in space group P3221 (a = 682.24(5) pm, c = 1270.65(9) pm, Z = 3). After its thermal decomposition starting at 180 °C, the anhydrate NaY[SO4]2 can be obtained with a monoclinic crystal structure refined from powder X-ray diffraction data in space group P21/m (a = 467.697(5) pm, b = 686.380(6) pm, c = 956.597(9) pm, β = 96.8079(5), Z = 2). Both compounds display unique Y3+-cation sites with eightfold oxygen coordination (d(Y-Os = 220-277 pm)) from tetrahedral [SO4]2− anions (d(S-O = 141-151 pm)) and a ninth oxygen ligand from an H2O molecule (d(Y-Ow = 238 pm) in the hydrate case. In both compounds, the Na+ cations are atoms (d(Na-Os = 224-290 pm) from six independent [SO4]2- tetrahedra each. Thermogravimetry and temperature-dependent PXRD experiments were performed as well as IR and Raman spectroscopic studies. Eu3+-doped samples were investigated for their photoluminescence properties in both cases. The quantum yield of the red luminescence for the anhydrate NaY[SO4]2:Eu3+ was found to be almost 20 times higher than the one of the hydrate NaY[SO4]2 ∙ H2O:Eu3+. The anhydrate NaY[SO4]2:Eu3+ exhibits a decay time of about τ1/e = 2.3 µm almost independent of the temperature between 100 and 500 K, while the CIE1931 color coordinates at x = 0.65 and y = 0.35 are very temperature-consistent too. Due to these findings, the anhydrate is suitable as a red emitter in lighting for emissive displays.
Open Access
La11Si11P21Te5 and La20.667Si18P46Te11.333 : two novel 3D‐polyanionic lanthanum compounds following the Zintl‐Klemm concept
(2024) Djendjur, Patrik; Anschütz, Zoë A.; Niewa, Rainer; Schleid, Thomas
During attempts to synthesize La3PTe3, after participation of the SiO2-container material, two so far unknown compounds could be isolated, which both follow the Zintl-Klemm concept. The novel quaternary lanthanum tellurides La11Si11P21Te5 and La20.667Si18P46Te11.333 crystallize hexagonally in the non-centrosymmetric space group Pmathematical equation c with the unit-cell parameters a=1204.97(6)-pm and c=1802.38(9)-pm (c/a=1.496) or a=1205.78(6)-pm and c=1802.16(9)-pm (c/a=1.495), respectively. Their very similar crystal structures can be divided into two interpenetrating three-dimensional sublattices, mathematical equation {[La11Te5]23+} (d(La3+-Te2-)=314-335-pm plus 352-pm) and mathematical equation {[Si11P21]23-} (d(Si-P)=221-225-pm, d(Si-Si)=230-231-pm, d(P-P)=220-221-pm) for La11Si11P21Te5 (Z=2), displaying unique structural features as compared to related compounds. The linkage of these two sublattices occurs through attractive La3+-Si- and La3+-P- interactions (d(La-Si)=333-pm, d(La-P)=298-318-pm). For La20.667Si18P46Te11.333 (Z=1), 4/3 out of 22 La3+cations in the doubled formula La22Si22P42Te10 have to be omitted, while the four Si- anions need to be replaced with phosphorus atoms. The La3+ vacancies are filled up with tellurium, partly forming [Te2]2- dumbbells (d(Te-Te)=274-pm). La11Si11P21Te5 can be obtained on target by reacting the elements (La, Si, P and Te) in their respective amounts with an excess of potassium chloride as fluxing agent in evacuated and torch-sealed glassy silica ampoules for four days at 900 °C as black pillars or thick plates with hexagonal cross-section.
Open Access
Li2Eu3Br2[BO3]2 : a new europium(II) halide oxoborate with yellow luminescence
(2020) Hoslauer, Jean‐Louis; Lissner, Falk; Blaschkowski, Björn; Schleid, Thomas
The europium(II) oxoborate Li2Eu3Br2[BO3]2 featuring lithium and bromide ions was synthesized by the reaction of Eu2O3 with Li[BH4] as lithium‐ and boron‐ as well as EuBr3 as bromide‐source at 750 °C for 24 h in silica‐jacketed sealed niobium capsules. The yellow, air‐stable and yellow fluorescent compound crystallizes in the trigonal space group R3m (a = 1049.06(7) pm, c = 2993.1(3) pm, c/a = 2.853, Z = 12). The two crystallographically distinguishable Eu2+ cations show either an eightfold coordination as bicapped trigonal prism ([EuO6Br2]12-) or a ninefold coordination as monocapped square antiprism ([EuO5Br4]12-). All oxygen atoms stem from isolated triangular [BO3]3- anions and the Li+ cations reside in octahedral voids provided by both oxygen atoms and Br- anions.
Open Access
Li4Ln[PS4]2Cl : chloride-containing lithium thiophosphates with lanthanoid participation (Ln = Pr, Nd and Sm)
(2023) Lange, Pia L.; Bette, Sebastian; Strobel, Sabine; Dinnebier, Robert E.; Schleid, Thomas
The synthesis and structural analysis of three new chloride-containing lithium thiophosphates(V) Li4Ln[PS4]2Cl with trivalent lanthanoids (Ln = Pr, Nd and Sm) are presented and discussed. Single crystals of Li4Sm[PS4]2Cl were obtained and used for crystal structure determination by applying X-ray diffraction. The other compounds were found to crystallize isotypically in the monoclinic space group C2/c. Thus, Li4Sm[PS4]2Cl (a = 2089.31(12) pm, b = 1579.69(9) pm, c = 1309.04(8) pm, β = 109.978(3)°, Z = 12) was used as a representative model to further describe the crystal structure in detail since Li4Pr[PS4]2Cl and Li4Nd[PS4]2Cl were confirmed to be isotypic using powder X-ray diffraction measurements (PXRD). In all cases, a trigonal structure in the space group R3̲ (e.g., a = 1579.67(9) pm, c = 2818.36(16) pm, c/a = 1.784, Z = 18, for Li4Sm[PS4]2Cl) displaying almost identical building units worked initially misleadingly. The structure refinement of Li4Sm[PS4]2Cl revealed bicapped trigonal prisms of sulfur atoms coordinating the two crystallographically distinct (Sm1)3+ and (Sm2)3+ cations, which are further coordinated by four anionic [PS4]3- tetrahedra. The compounds also contain chloride anions residing within channel-like pores made of [PS4]3- units. Eight different sites for Li+ cations were identified with various coordination environments (C.N. = 4-6) with respect to chlorine and sulfur. EDXS measurements supported the stoichiometric formula of Li4Ln[PS4]2Cl, and diffuse reflectance spectroscopy revealed optical band gaps of 2.69 eV, 3.52 eV, and 3.49 eV for Li4Sm[PS4]2Cl, Li4Nd[PS4]2Cl, and Li4Pr[PS4]2Cl, respectively. The activation energy for Li+-cation mobility in Li4Sm[PS4]2Cl was calculated as Ea(Li+) = 0.88 eV using BVEL, which indicates potential as a Li+-cation conductor.
Open Access
Luminescence properties of Y3F[Si3O10]:Ln3+ (Ln = Eu, Tb, Er) with thalenite-type host lattice and crystal structure of Tm3F[Si3O10]
(2023) Schäfer, Marion C.; Petter, Michael; Hartenbach, Ingo; Locke, Ralf J. C.; Zhang, Shuang; Wickleder, Claudia; Schleid, Thomas
With Tm3F[Si3O10], a new representative of the Ln3F[Si3O10] series could be synthesized by the reaction of Tm2O3, TmF3 and SiO2 (molar ratio: 1:1:3), applying an excess of CsBr as a fluxing agent in gas-tightly sealed platinum crucibles for eight days at 750 °C, and designed to yield Tm3F3[Si3O9] or Cs2TmF[Si4O10]. Single crystals of Tm3F[Si3O10] (monoclinic, P21/n; a = 725.04(6), b = 1102.43(9), c = 1032.57(8) pm, β = 97.185(7)°; Z = 4) appear as pale celadon, transparent, air- and water-resistant rhombic plates. According to its thalenite-type structure, Tm3F[Si3O10] contains catena-trisilicate anions [Si3O10]8− and triangular [FTm3]8+ cations. The three crystallographically different Tm3+ cations are coordinated by seven plus one (Tm1) or only seven anions (Tm2 and Tm3) exhibiting a single F- anion for each polyhedron, additional to the majority of O2- anions. Furthermore, the luminescence properties of the isotypic colorless compound Y3F[Si3O10] doped with Eu3+ (red emission), Tb3+ (green emission) and Er3+ (yellow and infrared emission), respectively, are reported in presenting their different excitation and emission spectra.