Crystal structure of monosamarium trithioborate, Sm[BS3]

Abstract

BS 3 Sm, orthorhombic, Pna2 1 (no. 33), a =7.3657(5) Å, b =6.0272(2) Å, c =8.8004(6) Å, V =390.69 Å 3 , Z =4, R(F 2 ) =0.068, R(P) =0.013, T =295 K. Source of materialSm[BS 3]w as prepared by using ah igh-temperature highpressure route. Molar ratios of 1:3:6 of samarium (powder, ChemPur, 99.9 %), amorphous boron (ABCR, 99 %) and sulfur (Alfa Aesar, 99.9995 %, sublimed under vacuum to reduce contamination by oxygen below 1%)were used. Molar ratios corresponding to the chemical composition of the title compound did not yield sufficiently pure materials. The educts were ground and filled into the assembly of the octahedral high pressure setup, under argon atmosphere of ag love box. Hexagonal boron nitride was used as the crucible material. High pressure conditions were achieved by using ahydraulic uniaxial press [1]. Force redistribution was accomplished by aW alker-type module and MgO octahedra with an edge length of 18 mm [2]. Elevated temperatures were realized by resistive heating of graphite tubes enclosing the sample crucible. For the synthesis of Sm[BS 3], the assembly was heated to 1673 Kand compressed to 3GPa for 5h. After the pressure and heating cycle, the arrangement was instantaneously removed and transferred into ag love box where the sample was isolated from the crucible. No indications of areaction between the sample and the crucible material were observed. The air-and humidity-sensitive compound Sm[BS 3 ]w as obtained as ared-brown polycrystalline material.Experimental details X-ray powder diffraction data were collected on aSTOE StadiP-MP diffractometer in Debye-Scherrer geometry. The GSAS software package [3] was used for the Rietveld refinements. The unit cell parameters at room temperature were determined from X-ray powder diffraction data (Cu K a1 ), using LaB 6 (a =4.15692(1) Å) as internal standard, and refined by least squares refinements using the WinCSD program [4]. The position of the boron atom was restrained to be near the centre of gravity of the sulfur atoms of the [BS 3] 3-unit. The isotropic displacement parameters of the sulfur atoms were constrained to be equal and the corresponding parameter of the boron site was constrained to be equal to that of the attached sulfur atoms. DiscussionThe new RE thioborate Sm [BS 3 ], obtained as ap roduct of the high-pressure high-temperature experiments, is an isotype of the RE [BS 3 ]series (RE =Ce, Pr, Nd) [5,6]. The crystal structure was refined from X-ray powder diffraction data using the Rietveld refinement method [7]. The crystal structure of Sm [BS 3 ]ischaracterized by corrugated kagome nets formed by sulfur atoms, with the boron atoms occupying every second triangle, while Sm cations center the large hexagons. The corrugated nets are stacked along [100] according to the sequence ABAB. The coordination sphere of Sm is formed by nine sulfur species originating from six neighboring thioborate units. Three of the [BS 3] 3-units act as bidentate ligands, while the other three are in monodentate function. The Sm-Sbond distance...

Crystal structure of monoterbium trithioborate, Tb[BS3]

“…The new RE thioborate Tb [BS 3 ], obtained by ah igh-pressure high-temperature route, is an isotype of RE [BS 3 ]series (RE =Ce, Pr, Nd, Sm) [5][6][7]. The X-ray powder diffraction data were used for the refinement of the crystal structure by application of the Rietveld refinement method [8].…”

Rare-earth-based chalcogenides and their derivatives: an encouraging IR nonlinear optical material candidate

“…Among them, REBS 3 (RE = La, Ce, Pr, Nd, Sm, and Tb) were rst to be reported by Hunger et al in 2010, but they required rigorous experimental conditions of high temperature and pressure. [163][164][165][166] Moreover, the samples produced using this method were only polycrystalline powders. Therefore, researchers like Hans-Conrad zur Loye et al explored a new method using the boron-chalcogen mixture approach, with raw materials including RE 2 O 3 /CeO 2 , B, S, and K 2 S/NaI-CsI acting as a ux.…”

“…In order to better illustrate the advantages of RE-based chalcogenide compounds and address the challenges in this field, this paper provides detailed explanations for 85 representative examples out of over 400 NCS compounds. 68–187 These examples are categorized into four groups based on the various asymmetric building motifs: (1) RE-based chalcogenides containing tetrahedral motifs; (2) RE-based chalcogenides containing lone-pair-electron motifs; (3) RE-based chalcogenides containing [BS 3 ] and [P 2 Q 6 ] motifs; and (4) RE-based chalcohalides and oxychalcogenides. Finally, the conclusions and perspectives for RE-based chalcogenides and their derivatives are provided for further exploration.…”

LaBS3 revisited: a promising mid-infrared nonlinear optical material

“…Hitherto, rare-earth thioborates reported include REBS 3 (RE = La, Ce, Pr, Nd, Sm, and Tb; Pna2 1 ), RE 9 [BS 3 ] 2 [BS 4 ] 3 S 3 (RE = Dy-Lu; P6 3 ) and EuB 2 S 4 (P2 1 /c). [27][28][29][30][31] The first syntheses of lanthanide ortho-thioborates by Hunger et al utilized high temperatures (800-1050 1C) and high pressures (3 Gpa) and yielded only polycrystalline powders. 25 Structurally, REBS 3 consist of [BS 3 ] 3À groups linked by RE-S bonds, and RE 9 [BS 3 ] 2 [BS 4 ] 3 S 3 is formed by the stacking of [BS 4 ] 5À tetrahedra and [BS 3 ] 3À triangles propagating along the 6 3 axes and interconnected by RES 6+1 mono-capped trigonal prisms, while EuB 2 S 4 features a centrosymmetric structure composed of polymeric [(B 2 S 4 ) 2À ] n -anions and divalent Eu 2+ cations.…”