New sodium-rich mixed Mn/In chalcogenido metallates Na12MnIn2Q10 (Q = S, Se)

2020 ◽  
Vol 75 (9-10) ◽  
pp. 825-832
Author(s):  
Michael Langenmaier ◽  
Julian Brantl ◽  
Caroline Röhr
Keyword(s):  
Structure Type ◽  
Close Packing ◽  
Monoclinic Space Group ◽  
Crystallographic Site ◽  
Slow Cooling ◽  
Sodium Cations ◽  
Structure Relation ◽  
Pure Phase ◽  
Maximum Temperatures ◽  
Tetrahedral Voids

AbstractThe sodium-rich sulfido and selenido metallates Na12MnIn2Q10 (Q = S/Se) were synthesized in pure phase from melts composed of stoichiometric quantities of the manganese monochalcogenides MnQ, elemental indium and the chalcogens together with either Na2S (Q = S) or elemental sodium (Q = Se) as starting material. The samples were heated up to maximum temperatures of 1000/900 °C under an argon atmosphere; crystallization was achieved by slow cooling rates of 10 K h−1. The two isotypic compounds (monoclinic, space group P21/m, a = 678.26(2)/698.85(10), b = 2202.77(7)/2298.7(3), c = 766.39(3)/800.59(13) pm, β = 90.232(2)/90.147(5)°, Z = 2, R1 = 0.0516/0.0575) crystallize in a new structure type. According to the division of the formula as Na12[InQ4][MnInQ6] the salts contain ortho indate anions [InIIIQ4]5− besides hetero-bimetallic dimers [MnIIInIIIQ6]7−, which consist of two edge-sharing [MQ4] tetrahedra. The seven crystallographically different sodium cations exhibit an either tetrahedral or octahedral coordination by the chalcogen atoms. Thus, the overall structure of the salt is best described by a hexagonal close packing of the sulfide/selenide anions, in which the octahedral voids of every second interlayer section are fully occupied by the (overall 5/f.u.) Na+ positions with CN = 6. In the other half of the interlayer sheets, all tetrahedral voids (overall 10/f.u.) are occupied by the seven CN = 4 Na+ cations, one In3+ of the ortho anion and the two Mn2+/In3+ cations (which statistically occupy one crystallographic site). This structure relation is also verified by a Bärnighausen group-subgroup tree connecting the h.c.p. (Mg type) aristotype (with its tetrahedral and octahedral voids) by an overall index of 60 with the structure of the two title compounds.

Alkali chalcogenido ortho manganates(II) A6MnQ4 (A=Rb, Cs; Q=S, Se, Te)

2018 ◽  
Vol 73 (11) ◽  
pp. 837-848 ◽  
Author(s):  
Michael Langenmaier ◽  
Tobias Rackl ◽  
Dirk Johrendt ◽  
Caroline Röhr
Keyword(s):  
Magnetic Measurements ◽  
Magnetic Moments ◽  
Electronic Band ◽  
Chiral Structures ◽  
Pure Phase ◽  
Maximum Temperatures ◽  
Alkali Elements ◽  
Electronic Band Structures ◽  
Bonding Characteristics ◽  
Tetrahedral Voids

AbstractThe six isotypic alkali ortho chalcogenido manganates A6[MnIIQ4] (A=Rb, Cs; Q=S, Se, Te) were synthesized – in most cases in pure phase – from stoichiometric mixtures of the manganese monochalcogenides MnQ, the elemental chalcogens and Rb2S/Cs2S2 (sulfido salts) or the pure alkali elements (selenido and tellurido salts) as alkali sources at maximum temperatures between 650 and 800°C. Their hexagonal crystal structures were refined by means of X-ray single crystal data (space group P63mc, Na6ZnO4-type structure, Z=2; A/Q: Rb/S: a=1019.34(2), c=792.560(10) pm, R1=0.0166; Rb/Se: a=1055.74(2), c=821.14(2) pm, R1=0.0275; Rb/Te: a=1126.68(2), c=860.54(2) pm, R1=0.0152; Cs/S: a=1056.68(2), c=831.22(2) pm, R1=0.0168; Cs/Se: a=1096.04(3), c=858.13(2) pm, R1=0.0194; and Cs/Te: a=1167.72(3), c=896.95(2) pm, R1=0.0140). The chiral structures contain isolated C3 symmetric, but very close to ideal tetrahedral, ortho manganate(II) anions [MnIIQ4]6− with Mn–Q distances of 248.7–250.7 (Q=S), 260.7–263.0 (Q=Se) and 280.0–282.4 pm (Q=Te). The chalcogenide ions form a hexagonal closed packing with slightly puckered 36 nets, in which the A(2) cations occupy 3/4 of the octahedral interstices, whereas Mn takes 1/8 and A(1) 3/8 of the tetrahedral voids. Magnetic measurements on the three Cs compounds showed Curie-Weiss behavior down to a temperature of 1.9 K, with magnetic moments significantly reduced with respect to the expected spin-only value of a d5 ion. The electronic band structures of the four salts (Na/Rb)6Mn(S/Te)4, which were calculated within the GGA+U approach, allow a comparison of the chemical bonding characteristics and the magnetic properties within the alkali cation and the chalcogenido ligand series.

Neue Sulfido-Antimonate der schweren Alkalimetalle: Synthese, Kristallstruktur und chemische Bindung von (K=Rb=Cs)3SbS3 und Cs3SbS4 · H2O / New Sulfido Antimonates of the Heavy Alkali Metals: Synthesis, Crystal Structure and Chemical Bonding of (K=Rb=Cs)3SbS3 and Cs3SbS4 · H2O

2013 ◽  
Vol 68 (12) ◽  
pp. 1295-1309 ◽  
Author(s):  
Lisa V. Schindler ◽  
Michael Schwarz ◽  
Caroline Röhr
Keyword(s):  
Chemical Bonding ◽  
Alkali Metals ◽  
Lone Electron Pair ◽  
Electron Pair ◽  
Structure Type ◽  
Uniform Structure ◽  
Monoclinic Space Group ◽  
Space Group ◽  
Bond Lengths ◽  
Structure Relation

The new sulfido antimonates(III) (Rb=Cs)3SbS3 were prepared from the alkali metal sulfides Rb2S=Cs2S2 and elemental antimony and sulfur or Sb2S3 at reaction temperatures of about 700 °C. The known isotypic potassium compound was similarily synthesized from the elements. The structures of the light-yellow crystals were refined using single-crystal X-ray data. Both compounds are isotypic to the respective Na salt forming the Na3AsS3 structure type (cubic, space group P213, K/Rb/Cs: a = 947:21(7)=982:28(5)=1025:92(5) pm, Z = 4, R1 = 0:0159=0:0560=0:0582). The Ψ - tetrahedral SbS3-3 anions with Sb-S bond lengths of 242 pm are arranged in a cubic face centered packing, in which the three crystallographically different A+ cations occupy the tetrahedral and octahedral voids, overall exhibiting a distorted octahedral sulfur coordination. The chemical bonding and the characteristics of the stereochemically active lone electron pair have been investigated by means of FP-LAPW band structure calculations. Needle-shaped crystals of the monohydrate of the antimony(V) salt Cs3SbS4 · H2O were obtained from a suspension of Sb2O3, CsOH and elemental sulfur. Cs3SbS4 · H2O crystallizes in a new structure type (monoclinic, space group P21/c, a = 987:17(10), b = 994:83(7), c = 1600:46(14) pm, β = 126:895(8)°, Z = 4, R1 = 0:0234). As expected, the Sb-S distances (233.1 - 234.7 pm) in the nearly ideally tetrahedral anion SbS3-4 are considerably shorter than in the antimonates(III) but match the bond lengths in the anhydrous sulfido antimonate(V) Cs3SbS4. Due to their similar fcc-like anion packing and the stereochemically active lone electron pair of Sb in the antimonates(III), the whole series of compounds A3SbIII,VS3/4 shows a uniform structure relation, which is elucidated using crystallographic group-subgroup relations

Darstellung und Kristallstruktur von TI3AgTe2 / Preparation and Crystal Structure of TI3AgTe2

1986 ◽  
Vol 41 (8) ◽  
pp. 941-945 ◽  
Author(s):  
Kurt O. Klepp
Keyword(s):  
Crystal Structure ◽  
Structure Type ◽  
Monoclinic Space Group ◽  
Stacking Sequence ◽  
Slow Cooling ◽  
Space Group ◽  
Tetrahedral Sites

Abstract The new compound Tl3AgTe2 was prepared by the reaction of Tl5Te3, Ag and Te at 550 °C, followed by slow cooling of the melt. It forms black crystals of metallic lustre which decompose by the influence of humidity. Tl3AgTe2 is monoclinic, space group P21/c, with a = 11.020(5), b = 7.427(2), c = 9.888(3) Å , β = 116.62(4)°, Z = 4. The crystal structure was determined from four-circle diffractometer data and refined to a conventional R of 0.083 for 1015 observed reflections. Tl3AgTe2 crystallizes with a new structure type, characterized by infinite layers, 2∞[AgTe2], running along (100), which are separated from each other by thallium atoms. The layers are built up by pairs of edge sharing AgTe4-tetrahedra linked together by common Te atoms according to 2∞[Ag (Te)Te3/3]. The crystal structure is based on an arrangement of distorted c.p. tellurium layers, stacked along [010] (stacking sequence h2). All octahedral voids are occupied by Tl-atoms, Ag-and Tl-atoms are regularly distributed over the tetrahedral sites.

Gemischte Alkalimetall-Oxidosulfidomolybdate A2[MoOxS4– x] (x = 1, 2, 3; A = K, Rb, Cs, NH4). Synthesen, Kristallstrukturen und Eigenschaften / Mixed Alkali Oxidosulfidomolybdates A2[MoOxS4−x] (x = 1, 2, 3; A = K, Rb, Cs, NH4).Synthesis, Crystal Structure and Properties

2012 ◽  
Vol 67 (2) ◽  
pp. 127-22
Author(s):  
Anna J. Lehner ◽  
Korina Kraut ◽  
Caroline Röhr
Keyword(s):  
Bathochromic Shift ◽  
Structure Type ◽  
Structure Theory ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
Coordination Numbers ◽  
Preparation Conditions ◽  
Vis Spectroscopy ◽  
Type Orthorhombic

Mixed sulfido/oxidomolybdate anions [MoOxS4−x]2− (x = 1, 2, 3) have been prepared by passing H2S gas through a solution of oxidomolybdates. The alkali salts of K+, Rb+, Cs+, and NH+4 precipitate as crystalline salts from these solutions depending on the pH, the polarity of the solvent, the educt concentrations and the temperature. Their structures have been determined by means of X-ray single-crystal diffraction data. All trisulfidomolybdates A2[MoOS3] (A = NH4/K/Rb/Cs) are isotypic with the tetrasulfido salts, exhibiting the β -K2[SO4] type (orthorhombic, space group Pnma, Z = 4; for A = Rb: a = 940.62(4), b = 713.32(4), c = 1164.56(5) pm, R1 = 0.0281). In contrast, the disulfidomolybdates exhibit a rich crystal chemistry, forming three different structure types depending on the preparation conditions and the size of the A cation: All four cations form salts crystallizing with the (NH4)2[WO2S2] structure type (monoclinic, space group C2/c, Z = 4, for A = Rb: a = 1144.32(11), b = 732.60(4), c = 978.99(10) pm, β = 120.324(7)°, R1 = 0.0274). For the three alkali metal cations a second polymorph with a new structure type (monoclinic, space group P21/c, Z = 4) is observed in addition (for A = Rb: a = 674.83(2), b = 852.98(3), c = 1383.10(9) pm, β = 115.19(1)°, R1 = 0.0216). The cesium salt also crystallizes with a third modification of another new structure type (orthorhombic, space group Pbcn, Z = 4, a = 915.30(6), b = 777.27(7), c = 1120.02(7) pm, R1 = 0.0350). Only for K, an anhydrous monosulfidomolybdate could be obtained (K2[MoO4] structure type, monoclinic, space group C2/m, Z = 4, a = 1288.7(3), b = 615.7(2), c = 762.2(1) pm, β = 109.59(1)°, R1 = 0.0736). The intramolecular chemical bonding in the molybdate anions is discussed and compared with the respective vanadates. Hereby aspects like bond lengths, bond strengths and force constants derived from Raman spectroscopy, are taken into account. Especially for the polymorphic disulfido salts, in-depth analyses of the local coordination numbers and the packing of the ions are presented. The gradual bathochromic shift of the crystal color with increasing S content and increasing size of the counter cations A and molar volumes (for the polymorphic forms), respectively, is in accordance with the increase of the experimental (UV/Vis spectroscopy) and calculated (FP-LAPW band structure theory) band gaps.

scholarly journals Darstellung und Kristallstruktur von K2Sn2S5 und K2Sn2Se5 / Preparation and Crystal Structure of K2Sn2S5 and K2Sn2Se5

1992 ◽  
Vol 47 (2) ◽  
pp. 197-200 ◽  
Author(s):  
Kurt O. Klepp
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Structure Type ◽  
Slow Cooling ◽  
Bond Lengths ◽  
Trigonal Bipyramidal ◽  
Equatorial Bond ◽  
Binary Compounds ◽  
R Factors ◽  
Distorted Trigonal Bipyramidal

K2Sn2S5 and K2Sn2Se5 were prepared by reacting stoichiometric powdered mixtures of the binary compounds K2S or K2Se with Sn and the corresponding chalcogen at 1070 K, followed by slow cooling of the melt. The two compounds are isostructural and crystallize with the Tl2Sn2S5 structure type, s.g. C 2/c, Z = 4 with a = 11.072(5) Å, b = 7.806(3)Å, c = 11.517(5)Å, β = 108.43(2)° for K2Sn2S5 and a = 11.613(5)Å, b = 8.189(3) Å, c = 11,897(6) Å, β = 108.28(2)° for K2Sn2Se5. The crystal structures were refined to conventional R-factors of 0.032 and 0.031, respectively. Sn-atoms are in a distorted trigonal-bipyramidal chalcogen coordination. The average equatorial bond lengths are Sn -S: 2.427 Å and Sn -Se: 2.552 Å , the axial ones are Sn -S: 2.600 Å and Sn -Se: 2.774 Å.

Fluoride und Fluorosäuren, VIII [1]. Über eine fehlgeordnete feste Phase des SF4 sowie die Kristallstrukturen von Produkten seiner unbeabsichtigten Hydrolyse in Glasapparaturen, SiF4 (Neubestimmung) und SOF2 / Fluorides and Fluoro Acids, VIII [1]. On a Disordered Solid Phase of SF4 and the Crystal Structures of Products of its Unintentional Hydrolysis in Glass Apparatus, SiF4 (Redetermination) and SOF2

1984 ◽  
Vol 39 (10) ◽  
pp. 1295-1299 ◽  
Author(s):  
Dietrich Mootz ◽  
Lutz Korte
Keyword(s):  
Solid Phase ◽  
Zone Melting ◽  
Close Packing ◽  
Monoclinic Space Group ◽  
Space Group ◽  
Pyramidal Geometry ◽  
Vacuum Line ◽  
Melting Separation ◽  
Hydrolysis Of ◽  
Isolated Molecules

A structural investigation on single crystals of SF4 yielded the cubic space group Fm3m with a = 676.1(5) pm and Z = 4 and from this cubic close packing and at least sixfold disorder of isolated molecules. In one of the experiments of manipulating SF4 unintentional hydrolysis of the compound in a Duran-glass vacuum line occurred. The products SiF4 and SOF2 could be characterized by structure analysis after a miniature zone-melting separation and crystal growth in one and the same thin-walled capillary. The results for SiF4 [14̄3m, a = 547.6(1) pm, Z = 2 at -117 °C] confirm earlier work with a higher numerical accuracy. SOF2 crystallizes in the monoclinic space group P21/c with a = 524.7(1), b = 704.9(2), c = 1449.3(4) pm, β = 97.20(2)° at - 137 °C and Z = 8. Isolated molecules of pyramidal geometry are arranged in strongly folded layers with intermolecular S···O contacts.

Investigation of mesitylene-solvated group 13 mixed-metal halides: syntheses and crystal structures of bis(1,3,5-trimethylbenzene)gallium(I) tetrachlorido- and tetrabromidoaluminate(III) and (1,3,5-trimethylbenzene)gallium(I) tetraiodidoaluminate(III). Variation of the gallium-π-arene bond strength

2019 ◽  
Vol 74 (10) ◽  
pp. 773-782
Author(s):  
Luca Küppers ◽  
Walter Frank
Keyword(s):  
Structure Type ◽  
Monoclinic Space Group ◽  
Metal Halides ◽  
Group 13 ◽  
Space Group ◽  
X Ray ◽  
Mixed Metal ◽  
Main Group Metal ◽  
Arene Complex ◽  
Polymeric Chains

AbstractBis(1,3,5-trimethylbenzene)gallium(I) tetra­chloridoaluminate(III), [(1,3,5-(CH3)3C6H3)2Ga][AlCl4] (1), bis(1,3,5-trimethylbenzene)gallium(I) tetrabromido­aluminate(III), [(1,3,5-(CH3)3C6H3)2Ga][AlBr4] (2) and (1,3,5-trimethylbenzene)gallium(I) tetraiodidoaluminate(III), [1,3,5-(CH3)3C6H3Ga][AlI4] (3) were synthesized from the corresponding subvalent GaI/AlIII mixed metal halides and characterized via C,H analysis, Raman spectroscopy, X-ray powder diffraction and X-ray single crystal diffraction. Compound 1 crystallizes in the noncentrosymmetric monoclinic space group Cc isotypic to [(1,3,5-(CH3)3C6H3)2Ga][GaCl4]. For 2 and 3 the monoclinic space group P21/n is found, however, they are neither isotypic nor homotypic. While 2 is isotypic to [(1,3,5-(CH3)3C6H3)2In][InBr4], 3 establishes a new structure type. In the solids of all three title compounds coordination polymeric chains are found, in 1 and 2 built up from bis(arene)-coordinated, in 3 from mono(arene)-coordinated Ga+ ions and the corresponding AlX4− anions in a 1κCl:2κCl′ (1), 1κCl,Cl′:2κCl″ (2) or 1κCl,Cl′:2κCl″:3κCl‴ (3) bridging mode. Taking into account the weaker coordinating character of the AlCl4− as compared to the AlBr4− anion, in line with expectations the number of gallium halogen contacts is increased and the strength of the π-arene bonding is reduced in the bromide 2 as compared to the chloride 1. Finally, with the even more strongly coordinating AlI4− anion the arene coordination is limited to one molecule. Considering mesitylene complexes of gallium, the formation of a mono(arene) complex is unprecedented and even considering group 13 elements in general, the formation of a mono(mesitylene) complex like 3 is unusual. Furthermore, compound 3 is the first structurally characterized arene solvate of a main group metal tetraiodidometallate.

Synthesis and Crystal Structure of Tetraphenylarsonium Pentachlorocarbonylosmate(IV), (Ph4As)[OsCl5(CO)]

1997 ◽  
Vol 52 (8) ◽  
pp. 978-980 ◽  
Author(s):  
M Höhling ◽  
W Preetz
Keyword(s):  
Crystal Structure ◽  
Complex Anion ◽  
Structure Type ◽  
Close Packing ◽  
Cation Sublattice ◽  
X Ray Diffraction ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Positional Disorder ◽  
Intermolecular Contacts

The structure of tetraphenylarsonium pentachlorocarbonylosmate(IV), (Ph4As)[OsCl5(CO)], the first example of a halogenocarbonyl complex with osmium in the oxidation state +IV, has been determined at 208 K by single crystal X-ray diffraction: tetragonal, space group P4/n with a = 12.821 , c = 8.084 Å, Z = 2. There are short intermolecular contacts between neighbouring anions along the tetragonal axis c and unusually large displacement ellipsoids of the carbonyl group and the four equatorial Cl ligands arising from a positional disorder of the complex anion. By analogy with a variety of reported structures of the (Ph4As)[RuNCl4] structure type this is attributed to the close packing of the cation sublattice. Compared to other monocarbonylosmates the Os-C bond of 1.94(2) Å is extraordinaryly long while the bond between Os and the trans coordinated Cl ligand of 2.286(3) Å is rather short.

Synthese und Struktur von Nb0,89Fe0,93Te2 und Ta0,77Fe0,90Te2 / Synthesis and Structure of Nb0.89Fe0.93Te2 and Ta0.77Fe0.90Te2

1992 ◽  
Vol 47 (9) ◽  
pp. 1203-1212 ◽  
Author(s):  
Jörg Neuhausen ◽  
Karl-Ludwig Stork ◽  
Elisabeth Potthoff ◽  
Wolfgang Tremel
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Chemical Transport ◽  
Structure Type ◽  
Close Packing ◽  
Hexagonal Close Packing ◽  
X Ray ◽  
The Relationship

Nb0.89Fe0.93Te2 and Ta0.77Fe0.90Te2 were prepared by chemical transport reactions. The crystal structures of both compounds were determined using X-ray single crystal methods. The structures of the layer compounds Nb0.89Fe0.93Te2 (Pmna, Z = 2, a = 7.951(1) Å, b = 7.241(1) A, c = 6.233(1) Å) and Ta0.77Fe0.90Te2 (Pmna, Z = 2, a = 7.890(2) Å, b = 7.252(2) Å, c = 6.192(1) Å) are based on a hexagonal close packing of Te atoms. Approximately one-half of the octahedral holes in this packing are occupied by Nb (Ta) atoms, about one-quarter of the tetrahedral holes are occupied by Fe atoms. The relationship to the NiAs structure type is discussed.

Synthese und Kristallstruktur von (TeCl3+)(MoOCl4–) / Synthesis and Crystal Structure of (TeCl3+)(MoOCl4–)

1991 ◽  
Vol 46 (2) ◽  
pp. 183-186
Keyword(s):  
Crystal Structure ◽  
Close Packing ◽  
Monoclinic Space Group ◽  
Chlorine Atoms ◽  
Synthesis And Crystal Structure ◽  
Lattice Constants ◽  
Layer Sequence ◽  
Octahedral Environment ◽  
Moisture Sensitive ◽  
Centrosymmetric Dimers

(TeCl3)(MoOCl4) is obtained by the reaction of TeCl4 and MoOCl3 in a sealed ampoule at 180 °C. It forms yellow-green moisture sensitive crystals. The crystal structure determination (lattice constants a = 734.8(1), b = 1281.5(3), c = 1172.2(2) pm, β = 94.62(2)°, monoclinic space group P 21/c, 2808 unique reflections for 92 parameters, final R = 0.029) shows that (TeCl3)(MoOCl4) consists of square pyramidal (MoOCl4-) anions and (TeCl3+) cations. The (MoOCl4-) anions are linked by asymmetric chlorine bridges and form centrosymmetric dimers (MoOCl4-)22- with the oxygen atoms located in the trans positions of the chlorine bridges. The coordination sphere for the Mo atom is a deformed octahedron of one oxygen and five chlorine atoms. Each trigonal pyramidal (TeCl3+) cation is connected by chlorine bridges to two neighboured (MoOCl4)22- anions resulting in a strongly deformed octahedral environment of six chlorine atoms for the Te atom. The MoOCl5 and TeCl6 octahedra are linked by edges and corners and form layers parallel to the be plane. Alternatively the structure can be regarded as a close packing of Cl and O atoms with the layer sequence ABAC, A ··· and Mo and Te atoms located in one quater of the octahedral holes.

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