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1.
The reactions of the Zintl phase K2Cs2Sn9 with elemental tellurium and selenium in ethylenediamine have been investigated. From the reaction of K2Cs2Sn9 with elemental tellurium [K‐(2,2,2‐crypt)]4Te6Te4 ( 2 ) and [K‐(2,2,2‐crypt)]2Sn2Te3 ( 3 ) were obtained, whereas the reaction of K2Cs2Sn9 with elemental selenium led to the formation of [K‐(2,2,2‐crypt)]2Sn(Se4)3 ( 4 ) and [K‐(2,2,2‐crypt)]2Cs2Sn2Se6·2en ( 5 )1). Compounds 2 , 4 , 5 have been characterized by single crystal X‐ray structure determination.  相似文献   

2.
Reaction of A2CO3 (A = K, Rb) with Sn and Se in an H2O/CH3OH mixture at 115–130°C affords the isotypic selenidostannates(IV) A6Sn4Se11 _. xH2O (A = K, x = 8) 1 and 2 whose discrete [Sn4Se11]6– anions each contain two corner‐bridged ditetrahedral [Sn2Se6]4– species. Similar reaction conditions with A = Cs afford Cs2Sn2Se5 _. H2O ( 3a ) and Cs2Sn2Se5 ( 3b ) in which such [Sn2Se6]4– building blocks are connected through common Se atoms into infinite [Sn2Se52–] chains. The [Sn3Se72–] ribbons of (Et4N)2Sn3Se7 ( 4 ), formed by treating (Et4N)I with Sn and Se in methanol at 130°C, can be regarded as resulting from the condensation of [Sn2Se52–] chains with molecular [SnSe4]4– anions. The anions [Sn4Se11]6–, [Sn2Se52–], and [Sn3Se72–] represent the products of individual reaction steps on the potential condensation pathway of [Sn2Se6]4– to the lamellar selenidostannates(IV) [Sn4Se92–] or [Sn3Se72–].  相似文献   

3.
The title compound, tripotassium sodium tritin octaselenide, K3NaSn3Se8, has a molecular (zero‐dimensional) structure containing trimeric [Sn3Se8]4? units which consist of three edge‐sharing SnSe4 tetrahedra. The [Sn3Se8]4? anions and the tetrahedrally coordinated Na+ cations are arranged in an alternating fashion along the c axis to form SiS2‐like chains, which are then separated by eight‐coordinate K+ cations. The Sn—Se bond distances are normal, being in the range 2.477 (1)–2.612 (1) Å.  相似文献   

4.
Cs3AsGeSe5 and Cs4Ge2Se6 can be prepared by methanolothermal reaction of elemental As, Ge and Se with Cs2CO3 at 190 °C. The former quaternary phase contains zweier [{AsGeSe5}3?] chains consisting of corner‐bridged GeSe4 tetrahedra and AsSe3 pyramids and represents the first GeIV‐AsIII chalcogenidometalate. Cs4Ge2Se6 exhibits discrete [Ge2Se6]4? anions formed by two edge‐sharing GeSe4 tetrahedra.  相似文献   

5.
The perseleno‐selenoborates Rb2B2Se7 and Cs3B3Se10 were prepared from the metal selenides, amorphous boron and selenium, the thallium perseleno‐selenoborates Tl2B2Se7 and Tl3B3Se10 directly from the elements in evacuated carbon coated silica tubes by solid state reactions at temperatures between 920 K and 950 K. All structures were refined from single crystal X‐ray diffraction data. The isotypic perseleno‐selenoborates Rb2B2Se7 and Tl2B2Se7 crystallize in the monoclinic space group I 2/a (No. 15) with lattice parameters a = 12.414(3) Å, b = 7.314(2) Å, c = 14.092(3) Å, β = 107.30(3)°, and Z = 4 for Rb2B2Se7 and a = 11.878(2) Å, b = 7.091(2) Å, c = 13.998(3) Å, β = 108.37(3)° with Z = 4 for Tl2B2Se7. The isotypic perseleno‐selenoborates Cs3B3Se10 and Tl3B3Se10 crystallize in the triclinic space group P1 (Cs3B3Se10: a = 7.583(2) Å, b = 8.464(2) Å, c = 15.276(3) Å, α = 107.03(3)°, β = 89.29(3)°, γ = 101.19(3)°, Z = 2, (non‐conventional setting); Tl3B3Se10: a = 7.099(2) Å, b = 8.072(2) Å, c = 14.545(3) Å, α = 105.24(3)°, β = 95.82(3)°, γ = 92.79(3)°, and Z = 2). All crystal structures contain polymeric anionic chains of composition ([B2Se7]2–)n or ([B3Se10]3–)n formed by spirocyclically fused non‐planar five‐membered B2Se3 rings and six‐membered B2Se4 rings in a molar ratio of 1 : 1 or 2 : 1, respectively. All boron atoms have tetrahedral coordination with corner‐sharing BSe4 tetrahedra additionally connected via Se–Se bridges. The cations are situated between three polymeric anionic chains leading to a nine‐fold coordination of the rubidium and thallium cations by selenium in M2B2Se7 (M = Rb, Tl). Coordination numbers of Cs+ (Tl+) in Cs3B3Se10 (Tl3B3Se10) are 12(11) and 11(9).  相似文献   

6.
Na6Sn4Se11 · 22 H2O can be crystallised at –8 °C as yellow‐orange needles from the 1 : 2 H2O/CH3OH mother liquor of a superheated reaction mixture of NaOH(s), Sn and Se. The bicyclic [Sn4Se11]6– anion exhibits crystallographic C2 symmetry and is composed of corner‐bridged SnSe4 tetrahedra. Two opposite tin atoms of an Sn4Se4 8‐membered ring are linked by a common Se atom, thereby affording two 6‐membered boat‐shaped Sn3Se3 rings with a shared Sn–Se–Sn bridging unit. [Sn4Se11]6– thus represents the immediate precursor of the well‐known adamantane‐like [Sn4Se10]4– anion.  相似文献   

7.
The reaction of diphenyltin dichloride with the binary Zintl phase K4Sn9 in the presence of excess lithium and 18‐crown‐6 in liquid ammonia led to the ammoniate [K(18‐crown‐6)(NH3)2]2Sn2Ph4 ( 1 ). The analogous reaction with K4Ge9 and potassium in the absence of further alkali metal ligands resulted in the compound [K2(NH3)12]Sn6Ph12 ? 4 NH3 ( 3 ). Cs6[Sn4Ph4](NH2)2 ? 8 NH3 ( 2 ) was prepared by reacting diphenyltin dichloride with a surplus of caesium in liquid ammonia. The low‐temperature single‐crystal structure determinations show all compounds to contain phenyl‐substituted polyanions of tin. Compound 1 is built from Sn2Ph anions consisting of Sn dumbbells with two Ph substituents at each Sn‐atom. Compound 2 contains cyclo‐Sn4Ph anions formed by a four‐membered tin ring in butterfly conformation with one Ph substituent at each Sn‐atom in an (all‐trans)‐configuration. Sn6Ph in 3 is a zig‐zag Sn6 chain with two substituents at each of the Sn‐atoms. Both 1 and 3 have molecular counter cations, in the latter case the unprecedented dinuclear potassiumammine complex [K2(NH3)12]2+ is observed. Compound 2 shows a complicated three‐dimensional network of Cs? Sn interactions.  相似文献   

8.
A new phase in europium‐tin‐chalcogenide chemistry has been prepared using the reactive flux method: Eu8(Sn4Se14)(Se3)2. The compound crystallizes in the orthorhombic space group P21212 with cell parameters a = 11.990(2) Å, b = 16.425(4) Å, c = 8.543(1) Å, and Z = 2. Eu8(Sn4Se14)(Se3)2 is a three dimensional structure with EuII cations linked together with an unusual (Sn4Se14)12– anionic unit and (Se3)2– chains. UV‐VIS‐NIR band‐gap analysis shows that these black metallic crystals are likely semiconductors with an optical band‐gap of 1.07 eV.  相似文献   

9.
Preparation and Crystal Structure of Rb2Sn3S7 · 2 H2O and Rb4Sn2Se6 Rb2Sn3S7 · 2 H2O has been prepared by hydrothermal reaction of SnS2 and Rb2CO3 in an with H2S saturated aqueous solution at 190°C. The crystal lattice contains chain anions [Sn3S72?] which display both SnS4 tetrahedra and SnS6 octahedra. Methanolothermal reaction of SnCl2 with Se and Rb2CO3 at 145°C leads to the formation of Rb4Sn2Se6 which contains edge-bridged bitetrahedral [Sn2Se6]4? anions.  相似文献   

10.
About Selenidostannates. I Synthesis, Structure, and Properties of [Sn2Se6]4–, [Sn4Se10]4–, and [Sn3Se7]2– The selenidostannates [(C4H9)2NH2]4Sn2Se6 · H2O ( I ), [(C4H9)2NH2]4Sn4Se10 · 2 H2O ( II ) und [(C3H7)3NH]2Sn3Se7 ( III ) were prepared by hydrothermal syntheses from the elements and the amines. I crystallizes in the monoclinic spacegroup P21/n (a = 1262.9(3) pm, b = 1851.3(4) pm, c = 2305.2(4) pm, β = 104.13(3)° and Z = 4). The [Sn2Se6]4– anion consists of two edge‐sharing tetrahedra. II crystallizes in the orthorhombic spacegroup Pna21 (a = 2080.3(4) pm, b = 1308.2(3) pm, c = 2263.5(5) pm and Z = 4). The anion is formed from four SnSe4 tetrahedra which are joined by common corners to the adamantane cage [Sn4Se10]4–. III crystallizes in the orthorhombic spacegroup Pbcn (a = 1371.1(3) pm, b = 2285.4(5) pm, c = 2194.7(4) pm and Z = 8). The anion is a chain, built from edge‐sharing [Sn3Se5Se4/2]2– units, in which two corner sharing tetrahedra are connected to a trigonal bipyramid by an edge of one and a corner of the other tetrahedron. The results of the TG/DSC measurements and of temperature dependent X‐ray diffractograms reveal that I and II decompose at first by release of minor quantities of triethylammonium to compounds with layer structure and larger cell dimensions. At still higher temperature the rest of triethylammonium and H2Se is evolved, leaving SnSe2 and Se in the bulk. The former decomposes partially at the highest temperature to SnSe. In the measurements of III the complex intermediate compound was not observed. III decomposes directly to SnSe2.  相似文献   

11.
The compound [K([2.2.2]crypt)]Cs7[Sn9]2(en)3 ( 1 ) was synthesized from an alloy of formal composition KCs2Sn9 by dissolving in ethylenediamine (en) followed by the addition of [2.2.2]crypt and toluene. 1 crystallizes in the orthorhombic space group Pcca with a = 45.38(2), b = 9.092(4), c = 18.459(8) Å, and Z = 4. The structure consists of Cs7[Sn9]2 layers which contain [Sn9]4– anions and Cs+ cations. The layers are separated by [K([2.2.2]crypt)]+ units. In the intermetallic slab (Cs7[Sn9]2) compares the arrangement of pairs of symmetry‐related [Sn9]4– anions with the dimer ([Ge9]–[Ge9])6– in [K([2.2.2]crypt)]2Cs4([Ge9]–[Ge9]), in which the clusters are linked by a cluster‐exo bond. The shortest distance between atoms of such two clusters in 1 is 4.762 Å, e. g. there are no exo Sn‐Sn bonds. The [Sn9]4– anion has almost perfect C4v‐symmetry.  相似文献   

12.
Preparation and Crystal Structure of Na2Sn2Se5 A Novel Chalcogenostannate(IV) with Layered Complex Anions Na2Sn2Se5 was obtained from a stoichiometric mixture of Na2Se, Sn, and Se powders through a solid state reaction at 450 °C. It crystallizes orthorhombic, space group Pbca with a = 13.952(6) Å, b = 12.602(2) Å, c = 11.524(2) Å; Z = 8 and undergoes peritectic decomposition at 471(2) °C. The crystal structure was determined at ambient temperature from diffractometer data (MoKα‐radiation) and refined to a conventional R of 0.040 (1490 Fo's, 83 variables). Na2Sn2Se5 is characterized by layered complex anions running parallel to (100) which are built up by SnSe4 tetrahedra sharing common corners. The mean Sn–Se bond length calculates as 2.252(2) Å. The Na+ cations are coordinated to 6 or 7 Se in irregular configurations. The crystal structure can be described as a stacking of distorted c. p. 36 chalcogen layers and mixed square 44 alkali‐chalcogen layers.  相似文献   

13.
Ruby‐red, bead‐shaped single crystals of C‐type La2Se3 (a = 905.21(6) pm), Pr2Se3 (a = 891.17(6) pm), and Gd2Se3 (a = 872.56(5) pm) are obtained by oxidation of the respective rare‐earth metal (M = La, Pr and Gd) with selenium (molar ratio 2 : 3) in evacuated silica tubes at 750 °C in the presence of fluxing CsCl within seven days. Their crystal structure belongs to a cation‐deficient Th3P4‐type variant (cubic, I 4 3d) according to M2.6670.333Se4 (Z = 4) or M2Se3 (Z = 5.333) offering coordination numbers of eight (Se2– arranged as trigonal dodecahedra) to the M3+ cations. In spite of the high Cs+ activity in molten CsCl, no cesium incorporation into the M5.3330.667Se8‐frame structure (e. g. as CsM5Se8 with Z = 2) could be achieved, judged from both results of electron beam X‐ray microanalyses and refined occupation factors of the metal position very close to x = 8/9 for M3xSe4.  相似文献   

14.
Synthesis, Structure, and Properties of Some Selenidostannates. II. [(C2H5)3NH]2Sn3Se7 · 0,25 H2O and [(C3H7)2NH2]4Sn4Se10 · 4 H2O The new selenidostannate hydrates [(C2H5)3NH]2Sn3Se7 · 0.25 H2O ( I ) and [(C3H7)2NH2]4Sn4Se10 · 4 H2O ( II ) were synthesized from an aqueous suspension of triethylammonium (tripropylammonium), tin, selenium I and in addition sulfur II at 130 °C. I crystallizes at ambient temperature in the monoclinic space group P21/n (a = 2069,3(4) pm, b = 1396,6(3) pm, c = 2342,8(5) pm, β = 114,68(3)°, Z = 8) and is characterized by two different anions, chains from edge‐sharing [Se3Se7]2– units and nets from trigonal SnSe5 bipyramids. II crystallizes at ambient temperature in the tetragonal space group I41/amd (a = 2150,0(3) pm, c = 1174,4(2) pm, Z = 4) and contains adamantane like [Sn4Se10]4–‐cages. The UV‐VIS spectra of the selenidostannates demonstrate that the absorption edges red shift as the dimensionality of the compounds is increased.  相似文献   

15.
Hexapotassium Hexaselenodistannate(III) K6Sn2Se6 – Synthesis, Structure, and Properties of a New Salt-like SnIII Compound Reaction of stoichiometric amounts of potassium, tin, and selenium in sealed silica tubes yield at 900 °C K6Sn2Se6 ( 1 ) as red-orange solid of which small particles are very suitable for X-ray structural analysis. Space group P21/c, lattice dimensions at 203 K: a = 905.6(2), b = 1277.4(3), c = 888.7(2) pm, β = 115.86(3)°, R1 = 0.0332. Besides Cs6Sn2Se6, 1 represents the second hexaselenostannate(III) to be known and structurally characterized. Thus, it contributes to the completion of the hexachalcogenostannate(III) family. Additionally, 1 is isostructural and in some cases even isotypic to homologue compounds of the elements silicon and germanium.  相似文献   

16.
Selenostannates from Aqueous Solution, Preparation and Structure of Na4Sn2Se6 · 13 H2O The dimeric anion Sn2Se64? is prepared by reaction of SnSe2 with alkali metal selenide in a 1:1 molar ratio. The orange-red hydrated sodium salt Na4Sn2Se6 · 13 H2O is characterized by a complete X-ray structure analysis and by its vibrational spectrum. The compound is triclinic (P1 ) with a = 7.106(2), b = 10.330(2), c = 19.009(4) Å, α = 78.60(2), β = 85.66(2), γ = 72.85(2)° (?130°C), Z = 2. It contains isolated Sn2Se64? anions consisting of two edge-sharing tetrahedra [Sn? Se 2.456(1)–2.589(1) Å] which are in contact to the hydrated Na+ ions within an extensive hydrogen bridge system. Raman-active vibrations are observed at 260, 202, 188, 116, 93, and 78 cm?1.  相似文献   

17.
A new phase has been prepared by methanolothermal reaction of Cs2CO3, BiCl3 and Li3AsSe3 at 130 °C for 36 hours. Cs4BiAs3Se7 ( I ) reveals the first Bi‐selenoarsenate polyanionic chain [Bi(As2Se4)(AsSe3)]4–, consisting of Bi3+ ions in a distorted octahedral environment of [AsSe3]3– and trans‐[As2Se4]4– units. The latter anion consists of a central “As24+” dumb‐bell whereby two Se atoms are attached to each of the As atoms. Structural Data: Space Group P21/n, a = 13.404(4) Å, b = 23.745(8) Å, c = 13.880(4) Å, β = 99.324(6)°, Z = 8.  相似文献   

18.
On Sesquiselenides of the Lanthanoids: Single Crystals of C‐type Ce2Se3, U‐type Gd2Se3, and Z‐type Lu2Se3 Single crystals of lanthanoid sesquiselenides (M2Se3; here: M = Ce, Gd, Lu) are accessible through conversion of the elements (lanthanoid and selenium) in molar ratios of 2:3 within seven days at 850 °C from evacuated silica ampoules if equimolar amounts of NaCl serve as a flux. In the case of Ce2Se3 (a = 897.74(6) pm) und Gd2Se3 (a = 872.56(5) pm) the cubic C‐type (I4¯3d, Z = 5.333) forms as dark red beads, whereas the orthorhombic Z‐type (Fddd, Z = 16) emerges for Lu2Se3 (a = 1125.1(1), b = 798.06(8), c = 2387.7(2) pm) as orange‐yellow bricks. Upon oxidation of monochloride hydrides (MClHx or AyMClHx; M = Ce, Gd, Lu; x = 1; A = Li, Na; y = 0.5) with selenium in arc‐welded tantalum ampoules the same main products appear with C‐Ce2Se3 and Z‐Lu2Se3, even with a surplus of NaCl or LiCl as fluxing agent. In the case of Gd2Se3, however, black‐red needles of the orthorhombic U‐type (Pnma, Z = 4; a = 1118.2(1), b = 403.48(4); c = 1097.1(1) pm) are yielded instead of C‐Gd2Se3. C‐Ce2Se3 crystallizes in a cation‐deficient Th3P4‐type structure (Ce2S3 type) according to Ce2.6670.333Se4 (Z = 4) or with Z = 5.333 for the empirical formula Ce2Se3. Here, Ce3+ is coordinated by eight Se2— anions trigon‐dodecahedrally. In U‐Gd2Se3 (U2S3 type) two crystallographically independent Gd3+ cations with coordination numbers of 7 (Gd1) and 7+1 (Gd2), respectively, are present, exhibiting mono‐ or bicapped trigonal prisms as coordination polyhedra. The crystal structure of Z‐Lu2Se3 (Sc2S3 type) shows two different Lu3+ cations as well, which now both reside in octahedral coordination of six Se2— anions each.  相似文献   

19.
Systematic investigations of ternary barium selenoborates led to the new compounds BaB2Se6 and Ba2B4Se13 which represent the first alkaline earth perselenoborates. Appropriate amounts of barium selenide, boron and selenium were filled into carbon coated silica tubes which were sealed under vacuum. The high temperature reactions and subsequent annealing processes were performed in horizontal one‐zone furnaces. By means of single crystal X‐ray diffraction the structure of BaB2Se6 was determined to be orthorhombic, space group Cmca (no. 64) with a = 11.326(2)Å, b = 7.659(2)Å and c = 10.315(2)Å, while for Ba2B4Se13 the monoclinic space group P21/c (no. 14) was found with a = 12.790(3)Å, b = 11.560(2)Å, c = 12.862(3)Å and β = 103.22(3)°. BaB2Se6 exhibits infinite layers of [B2Se62—]‐anions oriented parallel to the a‐b‐plane. Each layer consists of B2Se2four‐membered rings, which are connected via four diselenide bridges. Thus, B6Se12‐rings are formed in which the barium cations are located. Likewise, in Ba2B4Se13 polymeric [B4Se134—]‐anions are running parallel to the a‐c‐plane resulting in a new layered structure type built of alternating B2Se4‐ and B2Se3‐rings which are connected by perseleno contacts.  相似文献   

20.
The title compound was synthesized by a reactive salt reaction at 773 K over a period of 5 d. It has a one-dimensional chain structure consisting of K+ cations and one-dimensional [Ag2Sn2Se6]2− anions. The chain is constructed by edge-sharing bitetrahedral [Sn2Se6] units connected in a 1:2 ratio via linear Ag+ ions.  相似文献   

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