Synthesis and crystal structure of a new cesium thioantimonite Cs4Sb14S23

Kanishcheva, A. S.; Кузнецов, В. Г.; Mikhaǐlov, Yu. N.; Batog, V. N.; Скориков, В. М.

doi:10.1007/bf00746415

Cited by 8 publications

(6 citation statements)

References 6 publications

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“…The shortest Sb−S bond distances (2.418(6)−2.497(6) Å) are located in the equatorial plane of the trigonal bipyramids, and the longest Sb−S bond distances (2.830(6)−2.960(6) Å) are apical coordination sites, a general trend which has been observed previously. ,, Within the ψ-SbS 4 units, the axial S−Sb−S bond angles range from 169.8(2) to 177.8(2)°, the equatorial S−Sb−S bond angles vary from 89.9(2) to 99.4(2)°, and the bond angles between apical and equatorial sulfur atoms range from 84.0(2) to 95.3(2)°. The decrease in the equatorial bond angles from the ideal 120° indicates the presence of the lone pair occupying the fifth coordination site on Sb(III).…”

Section: Structural Descriptionsupporting

confidence: 77%

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Synthesis and Characterization of Cs₅Sb₈S₁₈(HCO₃): A New Layered Phase Containing Interstitial Cations and Anions

Schimek

Kolis

1997

Inorg. Chem.

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A new pseudoternary phase, Cs(5)Sb(8)S(18)(HCO(3)), was prepared from supercritical ammonia at 160 degrees C over 4 days using stoichiometric quantities of Cs(2)CO(3), Sb(2)S(3), and S(8). Red parallelepipeds of the title phase crystallize in the centrosymmetric monoclinic space group C2/c, with a = 27.064(3) Å, b = 11.634(4) Å, c = 12.642(3) Å, beta = 97.45(2) degrees, and Z = 4. The compound has a layered structure, with the layers formed from ribbons of condensed psi-SbS(4) trigonal bipyramids linked via S(3)(2)(-) chains, and both Cs(+) and HCO(3)(-) ions between the layers, giving rise to the formula Cs(5)Sb(8)S(12)(S(3))(2)(HCO(3)). Each layer is approximately 10 Å thick, with two layers per unit cell. The condensation of the group 15/16 building blocks into ribbons is the result of a combination of edge- and vertex-shared antimony(III) sulfide pseudo trigonal bipyramids. In this phase, the S(3) chains always link adjacent ribbons via apical coordination sites on the antimony atoms. The open cavities created by the linking trisulfide dianions between neighboring ribbons accommodate the antimony lone pairs and two unique cesium cations. A third cesium cation is located between layers. Unique to this compound, the anionic antimony sulfide layers are separated not only by cesium cations but also by bicarbonate anions. Results derived from infrared spectroscopy, diffuse reflectance, bond valence sums, and magnetic susceptibility measurements support the formulation of this compound as an electron-precise, wide-bandgap material. Thermal stability studies of Cs(5)Sb(8)S(18)(HCO(3)) are also discussed.

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Section: Structural Descriptionsupporting

confidence: 77%

“…In particular, the Cs−Sb−S system is structurally quite rich. The first compounds to be reported about 20 years ago were CsSbS 2 , Cs 2 Sb 4 S 7 , Cs 2 Sb 8 S 13 , and Cs 4 Sb 14 S 23 Cs 6 Sb 10 S 18 ·1.2H 2 O, and Cs 2 Sb 4 S 8 and CsSbS 6 …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Cs₅Sb₈S₁₈(HCO₃): A New Layered Phase Containing Interstitial Cations and Anions

Schimek

Kolis

1997

Inorg. Chem.

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“…Bond distances for the pyramidal antimony atoms range from 2.385(7) to 2.497 (6) Å and bond angles vary from 91.8(3) to 98.6(2)° (Tables and ). The previously reported compounds Cs 2 Ag 3 Sb 3 S 7 and ASbS 2 (A = Na,K,Cs) also contain [SbS 2 ] ∞ - chains with similar bond distances and angles. There are very few chalcogenide compounds which contain mixed oxidation state antimony atoms.…”

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confidence: 74%

Synthesis and Characterization of Novel One-Dimensional Phases from Supercritical Ammonia: Cs₃Ag₂Sb₃S₈, α- and β-Cs₂AgSbS₄, and Cs₂AgAsS₄

1996

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Synthetic efforts utilizing Cs2CO3, Ag, M2S3 (M = As, Sb), and S8 in supercritical ammonia (160 °C) have yielded four novel, one-dimensional compounds in the Cs−Ag−M−S system. These members were characterized by single-crystal X-ray diffraction and diffuse reflectance measurements. Cs3Ag2Sb3S8 (I) crystallizes in the monoclinic space group P21/m with lattice parameters of a = 10.539(3) Å, b = 7.234 (3) Å, c = 12.777 (3) Å, β = 101.96 (2)°, V = 952.7(9) Å3, z = 2, and R = 0.0377 (wR = 0.0445). The columnar framework of this compound consists of [SbS2]∞ - chains and SbS4 3- tetrahedra that are stitched together by Ag(I) ions. When the Cs/Sb ratio is doubled, α- and β-Cs2AgSbS4 (II and III, respectively) are obtained. Both phases contain identical anionic chains which pack in different ways. Compound II crystallizes in the monoclinic space group P21/c with a = 6.848(3) Å, b = 11.413(3) Å, c = 13.187(3) Å, β = 102.45(3)°, V = 1006.5(6) Å3, z = 4, and R = 0.0414 (wR = 0.0498). Compound III was refined in the triclinic space group P1̄ with a = 6.917(2) Å, b = 7.341(2) Å, c = 10.998(2) Å, α = 73.83(2)°, β = 76.08(2)°, γ = 71.71(2)°, V = 502.0(2) Å3, z = 2, and R = 0.0343 (wR = 0.0423). Compound IV, the isostructural arsenic analog of III, Cs2AgAsS4, has also been prepared and structured: a = 6.783(2) Å, b = 7.191(2) Å, c = 11.088(2) Å, α = 73.61(3)°, β = 75.10(3)°, γ = 70.83(3)°, V = 481.9(2) Å3, z = 2, and R = 0.0397 (wR = 0.0601). The infinite, one-dimensional anionic chains in the Cs2AgMS4 phases are built from isolated MS4 3- tetrahedra (M = As, Sb) joined by Ag(I) ions. In all four materials the silver atoms are tetrahedrally coordinated by sulfur atoms, and cesium(I) cations are located in the surrounding voids. Bond valence sums support the electron precise counts predicted for all three members: Cs3 IAg2 ISb2 IIISbVS8 -II and Cs2 IAgIMVS4 -II. Optical bandgaps determined via diffuse reflectance measurements indicate that these are wide bandgap materials (2.1−2.7eV) and thus are in agreement with the expected electronic configurations.

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“…Chains of corner-sharing pyramids are also known for As 3+ (AAsSe 2 , A = K, Rb, Cs) and Bi 3+ ([Et 4 N]BiSe 2 36 ) as well as for the antimony selenide compound [Ba(en) 4 ]Sb 2 Se 4 − However, the formation of pyramidal SbS 3 units in compounds 1 and 2 might be caused by the cation-size effect: The connectivity/dimensionality of the anionic framework is generally reduced in the presence of large cations . For instance, the compound β-NaSbS 2 1a (small Na + ions) possesses a three-dimensional cubic structure of the NaCl type with octahedral SbS 6 units, while the larger Cs cation favors the formation of a two-dimensional Sb/S and one dimensional framework of [SbS 2 ] - …”

Section: Resultsmentioning

confidence: 99%

“…Ternary antimony(III) sulfide compounds are accessible primarily via three synthetic methods. The first is the direct combination of binary sulfides A 2 S/Sb 2 S 3 (A = Na, K, Rb, Cs) and (AE)S/Sb 2 S 3 (AE = Ca, Sr, Ba) at high temperature gives ASbS 2 (A = Na, K, Rb, Cs), Ca 2 Sb 2 S 5 , Ba 8 Sb 6 S 17 , and Sr 3 Sb 4 S 9 , while flux reactions of Sb in CsS x melts gives Cs 2 Sb 4 S 8 and CsSbS 6 . The third method involves hydro(solvo)thermal conditions and is well suited not only for strictly inorganic materials such as Cs 3 Sb 5 S 9 , a , b -Rb 2 Sb 4 S 7 , Cs 6 Sb 10 S 18 ·1.2H 2 O, K 2 Sb 4 S 7 ·H 2 O, K 2 Sb 4 S 7 , Tl 2 Sb 3 S 5 , Cs 3 Ag 2 Sb 3 S 8 , and α,β-Cs 2 AgSbS 4 12 but also for open Sb/S frameworks in which the void space is filled with organic cations.…”

Section: Introductionmentioning

confidence: 99%

Low-Dimensional Sulfoantimonates with Metal Complexes as Counterions. Hydrothermal Synthesis and Properties of [M(en)₃]Sb₂S₄ (M = Co, Ni) and [M(en)₃]Sb₄S₇ (M = Fe, Ni)

1997

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[M(en)(3)]Sb(2)S(4) (M = Co, Ni) and [M(en)(3)]Sb(4)S(7) (M = Fe, Ni) were prepared from the MX(2)/Na(3)SbS(3)/en system (X = Cl, Br; en = ethylenediamine) under hydrothermal conditions. Orange-yellow [Ni(en)(3)]Sb(2)S(4) (1) crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 10.538(2) Å, b = 14.460(4) Å, c = 12.434(5) Å, beta = 99.93(2) degrees, and Z = 4. Green-yellow [Co(en)(3)]Sb(2)S(4) (2) crystallizes as a superstructure of 1 with a = 21.131(4) Å, b = 14.619(2) Å, c = 12.540(2) Å, beta = 100.50(1) degrees, and Z = 8. The antimony sulfide frameworks in 1 and 2 consist of SbS(3) pyramids sharing two corners to form 1/infinity[SbS(2)](-) chains. Orange-yellow [Ni(en)(3)]Sb(4)S(7) (3) crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 9.930(1) Å, b = 14.212(2) Å, c = 17.242(2) Å, beta = 102.55(1) degrees, and Z = 4. The 1/infinity[Sb(4)S(7)](2)(-) chains are formed by corner-sharing SbS(3) units. Three of these pyramids are arranged to cyclic Sb(3)S(6) trimers which share two of the three exocyclic S-atoms with the fourth SbS(3) units to form infinite chains. [Fe(en)(3)]Sb(4)S(7) (4) is isostructural to 3. In all four compounds the tris(ethylenediamine)metal(II) complexes act as counterions. The thermal, magnetic and optical properties of compounds 1-4 are reported.

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Synthesis and crystal structure of a new cesium thioantimonite Cs4Sb14S23

Cited by 8 publications

References 6 publications

Synthesis and Characterization of Cs₅Sb₈S₁₈(HCO₃): A New Layered Phase Containing Interstitial Cations and Anions

Synthesis and Characterization of Cs₅Sb₈S₁₈(HCO₃): A New Layered Phase Containing Interstitial Cations and Anions

Synthesis and Characterization of Novel One-Dimensional Phases from Supercritical Ammonia: Cs₃Ag₂Sb₃S₈, α- and β-Cs₂AgSbS₄, and Cs₂AgAsS₄

Low-Dimensional Sulfoantimonates with Metal Complexes as Counterions. Hydrothermal Synthesis and Properties of [M(en)₃]Sb₂S₄ (M = Co, Ni) and [M(en)₃]Sb₄S₇ (M = Fe, Ni)

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Synthesis and crystal structure of a new cesium thioantimonite Cs4Sb14S23

Cited by 8 publications

References 6 publications

Synthesis and Characterization of Cs5Sb8S18(HCO3): A New Layered Phase Containing Interstitial Cations and Anions

Synthesis and Characterization of Cs5Sb8S18(HCO3): A New Layered Phase Containing Interstitial Cations and Anions

Synthesis and Characterization of Novel One-Dimensional Phases from Supercritical Ammonia: Cs3Ag2Sb3S8, α- and β-Cs2AgSbS4, and Cs2AgAsS4

Low-Dimensional Sulfoantimonates with Metal Complexes as Counterions. Hydrothermal Synthesis and Properties of [M(en)3]Sb2S4 (M = Co, Ni) and [M(en)3]Sb4S7 (M = Fe, Ni)

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Synthesis and Characterization of Cs₅Sb₈S₁₈(HCO₃): A New Layered Phase Containing Interstitial Cations and Anions

Synthesis and Characterization of Cs₅Sb₈S₁₈(HCO₃): A New Layered Phase Containing Interstitial Cations and Anions

Synthesis and Characterization of Novel One-Dimensional Phases from Supercritical Ammonia: Cs₃Ag₂Sb₃S₈, α- and β-Cs₂AgSbS₄, and Cs₂AgAsS₄

Low-Dimensional Sulfoantimonates with Metal Complexes as Counterions. Hydrothermal Synthesis and Properties of [M(en)₃]Sb₂S₄ (M = Co, Ni) and [M(en)₃]Sb₄S₇ (M = Fe, Ni)