Two Mercury Antimony Chalcogenides Cs2HgSb4S8

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Article Cite This: ACS Omega 2018, 3, 15168−15173

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Two Mercury Antimony Chalcogenides Cs2HgSb4S8 and Cs2Hg2Sb2Se6 with Cesium Cations as Counterions Cui-Xia Du,† Fei-Yan Qi,† Juan Chen, and Menghe Baiyin* College of Chemistry & Environmental Science, Inner Mongolia Normal University, Hohhot, Inner Mongolia 010022, P.R. China

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S Supporting Information *

ABSTRACT: Two novel layer structure compounds, Cs2HgSb4S8 and Cs2Hg2Sb2Se6, were synthesized in organic solvent under solvothermal conditions. The Cs2HgSb4S8 is formed of [HgSb4S8]2− ribbons and S atoms by corner sharing. The Cs2Hg2Sb2Se6 is made up of [SbHg2Se6]5− ribbon and disorder trigonal-pyramidal SbSe3 by sharing μ3-Se. These compounds are characterized by single-crystal X-ray diffraction, powder X-ray diffraction, solid-state optical absorption spectra, and so on.

1. INTRODUCTION Since Bedard et al.1 reported the solvothermally synthesized open-framework structure of tin(IV) sulfides in 1989, a significant method has been developed in the synthesis of chalcogenides. Meanwhile, chalcogenides also have been attracting extensive research interest due to their excellent performance in the fields of semiconductor, ion exchange, and nonlinear optics.2−9 Very recently, a number of antimony chalcogenides have been continuously prepared because the stereochemical effect of lone electron pairs and the various coordinations of stibium by chalcogen atoms can give rise to large structural and compositional diversities.10,11 In other words, the stibium atom is coordinated with chalcogen atoms to form pyramidal [SbIIIQ3]3− or tetrahedral [SbVQ4]4− (Q = S, Se) primary units. The pyramidal [SbQ3]3− unit has a powerful tendency of a variety of condensations to form polynuclear anions which can link by sharing corners or edges to come into being rings or chains structure. However, the tetrahedral [SbVQ4]4− mostly binds cations directly to form low-dimensional structure because building chalcogen atoms need to stay charge balanced.12−14 In recent years, researchers have focused on the incorporation of transition metal (TM) ions into antimony chalcogenides to form novel chalcogenide materials.15 The transition metal ions contain Co2+, Ni2+, Fe2+, and Mn2+, and they are coordinated with organic amine to form [TM(amine)n]2+ complex cations acting as counterions, resulting in low-dimensional structural antimony chalcogenides.16 A large number of A-Hg-Sb-Q (A= [TM(amine)n]2+) compounds are known in which the transition metal ions are integrated into organic amine frameworks as charge balancing ions, such as [Ni(en)3]0.5HgSbS3 (en = ethylenediamine),17 [Co(en)3]Hg2Sb2S6, [Ni(1,2-dap)3]2HgSb3S7Cl (1,2-dap = 1,2-diamino© 2018 American Chemical Society

propane), [Ni(1,2-dap)3]HgSb2S5, [Mn(dien)2]HgSb2S5 (dien = diethylenetriamine), [TM(tren)]HgSb2S5 (TM = Mn, Fe, Co, tren = tris(2-aminoethyl)amine), [TM(dien)2]Hg3Sb4S10 (TM = Mn, Co, Ni),18 [Co(dien)2]HgSb2S5, [Ni(dien)2]HgSb2S5,19 [Mn(phen)]2HgSb2S6 (phen = 1,10-phenanthroline), [TM(tren)]HgSb2Se5 (TM = Mn, Fe, Co),20 [Ni(1,2pda)]HgSb2Se5, [Mn(dien)2]HgSb2Se5, [Ni(en)3]Hg2Sb2Se6, [Ni(en)(teta)]Hg2Sb2Se6,21 and [TM(1,2-dap)3]HgSb2Se5 (TM = Co, Fe).22 On the contrary, only a few compounds of antimony chalcogenides with alkali metal ions or alkaline earth metal ions as counterions are known. Meanwhile, transition metal ions Ag+, Cu2+, and Hg2+ compared with Co2+, Ni2+, Fe2+, and Mn2+ are easily formed frameworks of group 15 elements. For example, CsAgSb4S7,23 KCu2SbS3,24 K2MSbS3 (SH) (M = Zn, Cd),25 K3Ag9Sb4S12, Rb3Ag9Sb4S12, Cs3Ag9Sb4S12,26 BaAgSbS3, BaAgSbS3·H2O,27 Rb2Cu2Sb2S5, Cs2Cu2Sb2S5,10 BaCuSbS3, and BaCuSbSe328 were synthesized by the high-temperature solid-state approach, reactive flux methods, and hydro(solvo)thermal methods. However, A-HgSb-Q (A= alkali metal cations) antimony chalcogenides were synthesized relatively little. As far as we know, there are only a few compounds of KHgSbS3,29 RbHgSbTe3,30 MHgSbSe3 (M = K, Rb, Cs),31 and [tetaH2]0.25Rb0.5HgSbSe3.17 Although most of the mercury(II)−antimony chalcogenides were synthesized by using organic amines or transition metal complexes as counterions, alkali metal ions or alkaline earth metal ions as counterions are still uncommon. In this article, we obtained two new mercury(II)−antimony chalcogenides Cs2HgSb4S8 (1) and Cs2Hg2Sb2Se6 (2). Received: August 16, 2018 Accepted: October 23, 2018 Published: November 9, 2018 15168

DOI: 10.1021/acsomega.8b02059 ACS Omega 2018, 3, 15168−15173

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2. RESULTS AND DISCUSSION We have investigated solvent factor in the synthesis of these compounds. For compound 1, we used 1,4-diaminobutane as reaction solvent. Other conditions remained unchanged, and a large number of small crystals were obtained. When we used 1,2-diaminopropane instead of 1,4-diaminobutane as the solvent to synthesize compound 2, a very small amount of the crystals was obtained. Their structures were determined by single-crystal X-ray diffraction. 2.1. Structural Descriptions. Cs2HgSb4S8 (1). Compound 1 has a novel layered structure, in which the two-dimensional (2D) layered [HgSb4S8]2n− network is separated by countern ions Cs + cations and stack along the a axis (Figure 1). The

tetrahedron of [Ni(en) 3 ]0.5 HgSbS 3 (Hg−S: 2.456(2)− 2.6756(18) Å) (Table S1).17 In compound 1 appears Sb3S3 six-membered rings, which are composed of three SbS3 units by corner sharing (Figure 2b), and it is similar to some thioantimonates.32,33 The [SbHgS5]n chain and Sb3S3 sixmembered rings form the [HgSb4S8]2− ribbon by sharing S(1) and S(5) self-assembly (Figure 2c). The Sb(3)−S(5) and Sb(2)−S(1) bond lengths are 0.2399(6) Å and 0.2471(6) Å, respectively. Such [HgSb4S8]2− ribbon further fused via sharing the μ2-S(4) atoms to form a 2-D anionic layer along the ab plane (Figure 2d). It is worth mentioning that the compound 1 possesses a new type of Hg−Sb−S structure. Up to now, this structure has been not reported. In addition, Mn2Sb4S8(N2H4)234 and compound 1 have similar Sb4S8 units, but we found that their structures are very different. The Mn2Sb4S8(N2H4)2 consists of hydrazine-bridged neighboring 2-D Mn2Sb4S8 layers to form 3-D networks.34 Although the Mn2Sb4S8(N2H4)2 and compound 1 are all composed of six-membered Sb3S3 rings, the formation of the two types of rings is completely different. There are two different Sb coordination geometries for S bS 4 and S bS 5 in Mn2Sb4S8(N2H4)2, while compound 1 only contains trigonal pyramidal SbS3. Cs2Hg2Sb2Se6 (2). The compound 2 has a layered structure. It consists of the 2-D [Hg2Sb2Se6]2− anion layer, and Cs+ cations stack along the c axis (Figure 3). The Hg atom is

Figure 1. 2-D layer anions [HgSb4S8]2n− are separated by the cations n Cs+ and stack along the a axis.

layer can be described as being composed of 12-membered rings and 16-membered rings. The [SbHgS5]n chain is composed of trigonal−pyramidal Sb(4)S3 units and tetrahedron HgS4 units by corner sharing (Figure 2a). In trigonal− pyramidal Sb(4)S3 units, the Sb(4) atom is coordinated by three S atoms, and the Sb−S distances range from 2.358(6) to 2.461(6) Å with S−Sb(4)−S angles ranging from 93.0(2) to 96.8(2)° (Table S1). In tetrahedron HgS4 units, the Hg atom is integrated into four atoms, and the Hg−S distances range from 2.415(6) to 2.659(6) Å with angles ranging from 95.0(2) to 133.1(2)°. The Hg−S bond lengths are similar to the HgS4

Figure 3. 2-D [Hg2Sb2Se6]2− anion layer and Cs+ cations stack along the c axis.

Figure 2. (a) [SbHgS5]n chain. (b) The Sb3S3 six-membered rings. (c) The [HgSb4S8]2− ribbon. (d) 2-D anionic layer stack along the ab plane. 15169


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Figure 4. (a) [Hg2Se6]n chain. (b) Sb(3)Se4 units. (c) [SbHg2Se6]5− ribbon. (d) The disorder trigonal pyramidal SbSe3 units. (e) 2-D anionic layer stack along the bc plane.

Figure 5. (a) Solid-state optical absorption spectra of Cs2HgSb4S8. (b) Solid-state optical absorption spectra of Cs2Hg2Sb2Se6.

Sb−Se distances range from 2.762(15) to 2.876(15) Å with Se−Sb−Se angles ranging from 95.2(5)−126(2)°. The CsHgSbSe331 and compound 2 have the same stoichiometry of Cs:Hg:Sb:S (1:1:1:3), while their structure makes a difference. The CsHgSbSe3 includes terminal Se atoms, while 2 has none. On the other hand, their structures all include [Hg2Se6]n chains, but the [Hg2Se6]n chains of CsHgSbSe3 are connected with trigonal pyramidal SbSe3 units to form twodimensional (2D) anionic layers of 2∞[HgSbSe3]−. The [Hg2Se6]n chains of 2 are connected with tetrahedron SbSe4 units and trigonal pyramidal SbSe3 units, forming 2D anionic layers of [Sb2Hg2Se6]2−. As far as we know, these compounds, which contain [enH2]0.5HgSbS3, [tetaH2]0.5HgSbS3, [1,2pdaH]HgSbS3, [tetaH2]0.25Rb0.5HgSbSe3, [Ni(en) 3 ] 0.5 HgSbS 3 , 17 [Co(en) 3 ]Hg 2 Sb 2 S 6 , 18 [Ni(en) 3 ]Hg 2 Sb 2 Se 6 , [Ni(en)(teta)]Hg 2 Sb 2 Se 6 , 2 1 KHgSbS 3 , 2 9 RbHgSbTe3,30 and MHgSbSe3 (M = K, Rb, Cs),31 and compound 2 have the same stoichiometry of Hg:Sb:Q (Q = S, Se, Te) (1:1:3). It is different that these compounds are all composed of ring structure. In contrast, compound 2 appears to have a ribbon structure, and the most interesting is SbSe4 in compound 2. We found that RbHgSbTe3, RbHgSbSe3,

similar to compound 1, coordinated with four Se atoms to form tetrahedron HgSe4 units. In tetrahedron HgSe4 units, Hg−Se distances range from 2.585(7) to 2.753(10) Å with Se−Hg−Se angles ranging from 106.7(3) to 120.6(2)°. The [Hg2Se6]n chain consists of tetrahedron HgSe4 units through sharing Se(1) and Se(4) (Figure 4a). The Sb(3) atom is coordinated by four Se atoms, forming distorted tetrahedron Sb(3)Se4 units (Figure 4b). Sb(3)−Se distances range from 2.902(12) to 3.007(12) Å with Se−Sb(3)−Se angles ranging from 91.2(3) to 174.3(4)° (Table S2). The ribbon structure is composed of a [Hg2Se6]n chain and tetrahedron SbSe4 units by corner sharing (Figure 4c). An anionic layer is made up of a ribbon and two distorted trigonal pyramidal [SbHg2Se6]5− n SbSe3 units by sharing μ3-Se atom self-assembly along the bc plane (Figure 4e). There are two different types of Sb atoms in the crystal structure. The main difference is attributable to the coordination environment of Se atoms. In Sb(3)Se4 units, the Sb(3)−Se bond lengths are longer than those of other selenioantimonates,35 which are similar to the distorted ψSbSe4 trigonal bipyramid of [Mn(dien)2]2Sb4Se9 (Sb2− Se6:2.8087(11) and 3.0002(11) Å).14 In disorded trigonal− pyramidal SbSe3 units (Figure 4d), Sb1 and Sb2 atoms are disordered; the Sb atom is coordinated by three Se atoms; and 15170


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4.4. Single-Crystal X-ray Determination. Single crystals of 1 and 2 with dimensions of 0.29 × 0.25 × 0.20 mm and 0.26 × 0.21 × 0.18 mm were collected with intensity data on a Bruker APEX-II CCD diffractometer equipped with the graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) at 296 K. The structures of 1 and 2 were solved by direct methods and refined by full-matrix least-square methods on F2 by the SHELXL 97 package.37 Crystallographic data and structural refinement parameters for the two compounds are summarized in Table 1. Some relevant bond distances and bond angles are listed in the Supporting Information.

KHgSbSe3, and compound 2 have similar [Hg2Se6]n chains, whereas their counterions are also very different. 2.2. Optical Properties. The solid-state optical absorption spectra indicate that the optical band gaps of Cs2HgSb4S8 and Cs2Hg2Sb2Se6 are 2.13 and 1.77 eV, respectively (Figure 5). The band gaps of 1 show a red shift of the optical absorption edge compared with those of [enH2]0.5HgSbS3 (2.49 eV), [tetaH2]0.5HgSbS3 (teta = triethylenetetramine) (2.40 eV), [1,2-pdaH]HgSbS3 (2.55 eV), and [Ni(en)3]0.5HgSbS3 (2.68 eV).17 The band gaps of 2 show a blue shift of the optical absorption edge compared with those of CsHgSbSe3 (1.65 eV),31 RbHgSbSe3 (1.75 eV),30 and [tetaH2]0.25Rb0.5HgSbSe3 (1.42 eV).17 2.3. Thermogravimetric and Differential Scanning Calorimeter Analyses. The thermogravimetric (TG) curve of compounds 1 and 2 shows the weight loss of 30% and 24%, which corresponds to the collapse of the structure of the compound. Differeential scanning calorimeter (DSC) curves of compounds 1 and 2 display the endothermic peak at 343 and 354 °C, respectively (Figure S2).

Table 1. Crystal Data and Structure Refinement Parameters for 1 and 2 chemical formula formula weight temperature/K wavelength/nm crystal system space group a/Å b/Å c/Å α (deg) β (deg) γ (deg) V/Å3 Z Dc/(Mg·m−3) μ (mm−1) θ range (deg) GOF on F2 (I > 2σ(I))

3. CONCLUSIONS In summary, we have prepared two-layer mercury antimony chalcogenides Cs2HgSb4S8 and Cs2Hg2Sb2Se6 by the solvothermal method. Two compouds have a similar ribbon structure, but the structure is different. Two compounds contain alkali metal ions (Cs+) as counterions, and transition metal ions (Hg 2+ ) were incorporated into antimony chalcogenides. The solid-state optical absorption spectra indicate that two compounds are semiconductors. 4. EXPERIMENTAL SECTION 4.1. Materials and Methods. All reagents and chemicals are analytical and without further purification. The powder Xray diffraction is done using a Rigaku XRD-6000 diffractometer using Cu−Kα radiation at 40 kV and 40 mA (Figure S1). The solid-state optical absorption spectra are on a Shimadzu UV2550 double monochromatic sepctrophotometer over the range of 220−800 nm at the room temperature with Ba2SO4 power as reflectance. The absorption spectrum data were calculated from the Kubelka−Munk function: α/S = (1 − R)2/ 2R, where α is the absorption coefficient, S the scattering coefficient, and R the reflectance.36 Thermogravimetric and differeential scanning calorimeter analyses were carried out with an STA 449 F5 Jupiter at 30 to 600 °C at 5 °C/min under a nitrogen atmosphere at 35 mL/min. 4.2. Syntheses of Cs2HgSb4S8 (1). Cs2CO3 (33 mg, 0.1 mmol), HgI2 (45 mg, 0.1 mmol), Sb2S3 (34 mg, 0.1 mmol), and S (13 mg, 0.4 mmol) were dispersed in 522 mg of 1,2diaminopropane (1,2-dap), and 127 mg of H2O was placed in a thick Pyrex tube (ca. 20 cm long). The sealed tube was heated at 140 °C for 7 days to obtain yellow block crystals of 1 (19% yield based mercury). The crystals were washed with ethanol and dried and stored under vacuum. 4.3. Syntheses of Cs2Hg2Sb2Se6 (2). Cs2CO3 (33 mg, 0.1 mmol), HgI2 (45 mg, 0.1 mmol), Sb2S3 (34 mg, 0.1 mmol), and Se (36 mg, 0.4 mmol) were dispersed in 500 mg of 1,4diaminobutane (1,4-dab), and 120 mg of H2O was placed in a thick Pyrex tube (ca. 20 cm long). The sealed tube was heated at 160 °C for 7 days to obtain red polyhedron crystals of 2 (25% yield based mercury). The crystals were washed with ethanol, dried, and stored under vacuum.

R indices (all data) a

Cs2HgSb4S8

Cs2Hg2Sb2Se6

1209.89 296(2) 0.071073 triclinic P-1 7.3196(19) 10.6224(6) 11.7739(14) 99.51(2) 92.06(2) 92.10(2) 901.4(3) 2 4.457 19.279 1.95−25.00 1.144 R1 = 0.0622 wR2 = 0.1435 R1 = 0.1345 wR2 = 0.1533

1384.26 296(2) 0.071073 triclinic P-1 8.029(5) 8.869(5) 12.091(7) 68.49(1) 84.22(1) 74.13(1) 770.5(7) 2 2.865 42.117 1.81−25.00 1.233 0.1042 0.2140 0.1928 0.2323

R1 = Σ∥Fo| − |Fc∥/Σ|Fo|, wR2 = Σ[(w(F2o − F2c )2)/Σ[w(F2o)2)]1/2.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsomega.8b02059. CIF file for Cs2 Hg S8 Sb4 (CIF) CIF file for 36 Cs2 Hg2 Sb2 Se6 (CIF) CIF file for 1-Cs2 Hg S8 Sb4 (CIF) CIF file for 2-Cs2 Hg2 Sb2 Se6 (CIF) Single-crystal X-ray determination, PXRD patterns, DSC curves, and tables (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Menghe Baiyin: 0000-0002-1025-5029 Author Contributions †

C.X.D. and F.Y.Q. contributed equally to this work.

Notes

The authors declare no competing financial interest. 15171


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(15) Wang, F.; Tang, C. Y.; Chen, R. H.; Zhang, Y.; Jia, D. X. Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien)2 (μ-1κ,2κ2-AsS4)]n (Ln= = Sm,Eu, Gd) and [Ln(dien)2(1κ2-AsS4)] (Ln= = Tb, Dy, Ho). J. Solid State Chem. 2013, 206, 170−175. (16) Zhou, J.; Yin, X. H.; Zhang, F. Two Novel ThioindateThioantimonate Compounds [Ni(dien) 2 ]2 In2Sb4 S11 and [Ni(dien)2]3(In3Sb2S9)2·2H2O with Transition Metal Complexes. Inorg. Chem. 2010, 49, 9671−9676. (17) Kong, D. N.; Xie, Z. L.; Feng, M. L.; Ye, D.; Du, K. Z.; Li, J. R.; Huang, X. Y. From One-Dimensional Ribbon to Three-Dimensional Microporous Framework:The Syntheses,Crystal Structures, and Properties of a Series of Mercury Antimony Chalcogenides. Cryst. Growth Des. 2010, 10, 1364−1372. (18) Yue, C. Y.; Lei, X. W.; Liu, R. Q.; Zhang, H. P.; Zhai, X. R.; Zhou, M.; Zhao, Z. F.; Ma, Y. X.; Yang, Y. D. Syntheses, Crystal Structures, and Photocatalytic Properties of a Series of Mercury Thioantimonates Directed by Transition Metal Complexes. Cryst. Growth Des. 2014, 14, 2411−2421. (19) Tang, W. W.; Tang, C. Y.; Wang, F.; Chen, R. H.; Zhang, Y.; Jia, D. X. Solvothermal syntheses, crystal structures, and properties of new mercury(II)-thioantimonates(III) and a mixed-valent thioantimonate(III,V). J. Solid State Chem. 2013, 199, 287−294. (20) Wang, K. Y.; Zhou, L. J.; Feng, M. L.; Huang, X. Y. Assembly of novel organic-decorated quaternary TM-Hg-Sb-Q compounds (TM = Mn, Fe, Co; Q = S, Se) by the combination of three types of metal coordination geometries. Dalton Trans. 2012, 41, 6689−6695. (21) Wang, K. Y.; Ye, D.; Zhou, L. J.; Feng, M. L.; Huang, X. Y. Novel mercury selenidoantimonates with structures ranging from onedimensional ribbon to three-dimensional open-framework. Dalton Trans. 2013, 42, 5454−5461. (22) Zhao, L. J.; ZhaoRi, G.; Han, W. J.; Baiyin, M. Solvothermal Synthesis and Characterization of [TM(1,2-dap)3]HgSb2Se5 (TM = Co, Fe) with a Chain Structure. Chin. J. Struct. Chem. 2016, 35, 1222−1230. (23) Huang, F. Q.; Ibers, J. A. Synthesis, structure, band gap, and electronic structure of CsAgSb4S7. J. Solid State Chem. 2005, 178, 212−217. (24) Wang, R. Q.; Zhang, X.; He, J. Q.; Zheng, C.; Lin, J. H.; Huang, F. Q. Synthesis, crystal structure, electronic structure, and photoelectric response properties of KCu2SbS3. Dalton Trans. 2016, 45, 3473−3479. (25) Zhang, X.; Yi, N.; Hoffmann, R.; Zheng, C.; Lin, J. H.; Huang, F. Q. Semiconductive K2MSbS3 (SH) (M = Zn, Cd) Featuring One1 [M2Sb2S6(SH2)]4‑ Chains. Inorg. Chem. 2016, 55, Dimensional∞ 9742−9747. (26) Yao, H. G.; Zhou, P.; Ji, S. H.; Zhang, R. C.; Ji, M.; An, Y. L.; Ning, G. L. Syntheses and Characterization of a Series of SilverThioantimonates(III) and Thioarsenates(III) Containing Two Types of Silver-Sulfur Chains. Inorg. Chem. 2010, 49, 1186−1190. (27) Liu, C.; Shen, Y. Y.; Hou, P. P.; Zhi, M. J.; Zhou, C. M.; Chai, W. X.; Cheng, J. W.; Liu, Y. Hydrazine-Hydrothermal Synthesis and Characterization of the Two New Quaternary Thioantimonates(III) BaAgSbS3 and BaAgSbS3·H2O. Inorg. Chem. 2015, 54, 8931−8936. (28) Liu, C.; Hou, P. P.; Chai, W. X.; Tian, J. W.; Zheng, X. Y.; Shen, Y. Y.; Zhi, M. J.; Zhou, C. M.; Liu, Y. Hydrazine-hydrothermal syntheses, characterizations and photoelectrochemical properties of two quaternary chalcogenidoantimonates(III) BaCuSbQ3 (Q = S, Se). J. Alloys Compd. 2016, 679, 420−425. (29) Imafuku, M.; Nakai, I.; Nagashima, K. THE CRYSTAL STRUCTURE OF A NEW SYNTHETIC SULFOSALT, KHgSbS3. Mater. Res. Bull. 1986, 21, 493−501. (30) Li, J.; Chen, Z.; Wang, X. X.; Proserpio, D. M. A novel twodimensional mercury antimony telluride:low temperature synthesis and characterization of RbHgSbTe3. J. Alloys Compd. 1997, 262−263, 28−33. (31) Chen, Z.; Wang, R. J. Crystal Structures and Semiconductor Properties of Alkline Metal Selenides MHgSbSe3 (M = K,Rb,Cs). Acta Chim. Sin. 2000, 58, 326−331.

ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (21461019).

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REFERENCES

(1) Bedard, R. L.; Wilson, S. T.; Vail, L. D.; Bennett, J. M.; Flanigen, E. M. In Zeolites: Facts, Figures, Future; Jacobs, P., van Santen, R. A., Eds.; Elsevier: Amsterdam, 1989; pp 375−378. (2) Zhao, J.; Islam, S. M.; Kontsevoi, O. Y.; Tan, G.; Stoumpos, C. C.; Chen, H.; Li, R. K.; Kanatzidis, M. G. The Two-Dimensional AxCdxBi4‑xQ6 (A = K, Rb, Cs; Q = S, Se): Direct Bandgap Semiconductors and Ion-Exchange Materials. J. Am. Chem. Soc. 2017, 139, 6978−6987. (3) He, Y. H.; Kontsevoi, O. Y.; Stoumpos, C. C.; Trimarchi, G. G.; Islam, S. M.; Liu, Z. F.; Kostina, S. S.; Das, S.; Kim, J.; Lin, W. W.; Wessels, B. W.; Kanatzidis, M. G. Defect Antiperovskite Compounds Hg3Q2I2 (Q = S, Se, and Te) for Room-Temperature Hard Radiation Detection. J. Am. Chem. Soc. 2017, 139, 7939−7951. (4) Biswas, K.; Zhang, Q.; Chung, I.; Song, J. H.; Androulakis, J.; Freeman, A. J.; Kanatzidis, M. G. Synthesis in Ionic Liquids: [Bi2Te2Br](AlCl4), a Direct Gap Semiconductor with a Cationic Framework. J. Am. Chem. Soc. 2010, 132, 14760−14762. (5) Feng, M. L.; Sarma, D.; Qi, X. H.; Du, K. Z.; Huang, X. Y.; Kanatzidis, M. G. Efficient Removal and Recovery of Uranium by a Layered Organic-Inorganic Hybrid Thiostannate. J. Am. Chem. Soc. 2016, 138, 12578−12585. (6) Qi, X. H.; Du, K. Z.; Feng, M. L.; Gao, Y. J.; Huang, X. Y.; Kanatzidis, M. G. Layered A2Sn3S7·1.25H2O (A = Organic Cation) as Efficient Ion-Exchanger for Rare Earth Element Recovery. J. Am. Chem. Soc. 2017, 139, 4314−4317. (7) Zhao, J.; Islam, S. M.; Hao, S.; Tan, G.; Stoumpos, C. C.; Wolverton, C.; Chen, H.; Luo, Z.; Li, R.; Kanatzidis, M. G. Homologous Series of 2D Chalcogenides Cs-Ag-Bi-Q (Q = S, Se) with Ion-Exchange Properties. J. Am. Chem. Soc. 2017, 139, 12601− 12609. (8) Liao, J. H.; Marking, G. M.; Hsu, K. F.; Matsushita, Y.; Ewbank, M. D.; Borwick, R.; Cunningham, P.; Rosker, M. J.; Kanatzidis, M. G. α - and β - A2Hg3M2S8 (A = K, Rb; M = Ge, Sn): Polar Quaternary Chalcogenides with Strong Nonlinear Optical Response. J. Am. Chem. Soc. 2003, 125, 9484−9493. (9) Li, S. F.; Jiang, X. M.; Liu, B. W.; Yan, D.; Zeng, H. Y.; Guo, G. C. Strong Infrared Nonlinear Optical Efficiency and High Laser Damage Threshold Realized in Quaternary Alkali Metal Sulfides Na2Ga2MS6 (M= Ge, Sn) Containing Mixed Nonlinear Optically Active Motifs. Inorg. Chem. 2018, 57, 6783−6786. (10) Zhang, C.; Ji, M.; Ji, S. H.; An, Y. L. Mild Solvothermal Syntheses and Characterization of Layered Copper Thioantimonates(III) and Thioarsenate(III). Inorg. Chem. 2014, 53, 4856−4860. (11) Schur, M.; Bensch, W. Synthesis and Crystal Structures of New Antimony Polysulfido Complexes: [P(C6H5)4]3Sb3S25 and [P(C6H5)4]2Sb2S15·2(C3N2H6). Z. Anorg. Allg. Chem. 1998, 624, 310− 314. (12) Seidlhofer, B.; Spetzler, V.; Gonzalez, E. Q.; Näther, C.; Bensch, W. New Thioantimonates(III) with Different Sb:S Ratios: Solvothermal Syntheses and Crystal Structures of [(C3H10NO)(C 3 H 10 N)][Sb 8 S 13 ], [(C 2 H 8 NO)(C 2 H 8 N)(CH 5 N)][Sb 8 S 13 ], [(C6H16N2)(C6H14N2)][Sb6S10], and [C8H22N2][Sb4S7]. Z. Anorg. Allg. Chem. 2011, 637, 1295−1303. (13) Yue, C. Y.; Lei, X. W.; Ma, Y. X.; Sheng, N.; Yang, Y. D.; Liu, G. D.; Zhai, X. R. [TM(en)3][SnSb4S9] (TM = Ni, Co): 3D Chiral Framework of Mixed Main-Group Metals and [Mn(dien)2]2Sb4S9: 1D Chains with Mixed-Valent Sb Centers. Cryst. Growth Des. 2014, 14, 101−109. (14) Jia, D. X.; Zhang, Y.; Zhao, Q. X.; Deng, J. Mixed-Valent Selenidoantimonates(III,V) with Transition-Metal Complexes as Counterions: Solvothermal Syntheses and Characterization of [M(dien)2]2Sb4Se9 (M = Mn, Fe), [Co(dien)2]2Sb2Se6, and [Ni(dien)2]2Sb2Se. Inorg. Chem. 2006, 45, 9812−9817. 15172


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(32) Du, Z. K.; Feng, M. L.; Li, L. H.; Hu, B.; Ma, Z. J.; Wang, P.; Li, J. R.; Wang, Y. L.; Zou, G. D.; Huang, X. Y. [Ni(phen)3]2Sb18S29: A Novel Three-Dimensional Framework Thioantimonate(III) Templated by [Ni(phen)3] Complexes. Inorg. Chem. 2012, 51, 3926− 3928. (33) Seidlhofer, B.; Djamil, J.; Näther, C.; Bensch, W. From Zero-to Three-Dimensional Thioantimonates: [Ni(aepa)2]3Sb6S12 (aepa = C5H15N3 = N-(aminoethyl)-1,3-propandiamine), Containing the Unique [Sb6S12]6‑ Cyclic Anion, [Ni(aepa)2]6(Sb3S6)2(SO4)3·2H2O, with Isolated [Sb3S6]3‑ anions and [Ni(aepa)2]Sb4S7, Characterized by a Three-Dimensional Network Structure. Cryst. Growth Des. 2011, 11, 5554−5560. (34) Liu, Y.; Tian, Y. F.; Wei, F. X.; Ping, M. S. C.; Huang, C. W.; Boey, F.; Kloc, C.; Chen, L.; Wu, T.; Zhang, Q. C. A new hydrazinebridged thioantimonate Mn2Sb4S8(N2H4)2: Synthesis, structure, optical and magnetic properties. Inorg. Chem. Commun. 2011, 14, 884−888. (35) Jia, D. X.; Jin, Q. Y.; Chen, J. F.; Pan, Y. L.; Zhang, Y. The Coordination of the Tetraselenidoantimonate [SbSe4]3‑ Anion with Trivalent Lanthanide Ions Tuned by Ethylene Polyamines. Inorg. Chem. 2009, 48, 8286−8293. (36) Kortüm, G. Reflectance Spectroscopy; Springer: New York, 1969. (37) Sheldrick, G. M. SHELXS-97: program for X-ray crystal structure solution; University of Göttingen: Göttingen, Germany, 1997.

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