Citation: Ji-Long LI, Wen MA, Jian-Ce JIN, Mei-Ling FENG, Xiao-Ying HUANG. Syntheses, Crystal Structures and Optoelectronic Properties of Two New Inorganic Thioantimonates[J]. Chinese Journal of Structural Chemistry, ;2021, 40(4): 443-452. doi: 10.14102/j.cnki.0254-5861.2011-3075 shu

Syntheses, Crystal Structures and Optoelectronic Properties of Two New Inorganic Thioantimonates

Ji-Long LI ^{a, b} ,
Wen MA ^b ,
Jian-Ce JIN ^b ,
Mei-Ling FENG ^b,, ,
Xiao-Ying HUANG ^b

a.
College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China
b.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Corresponding author: Mei-Ling FENG, fml@fjirsm.ac.cn
Received Date: 21 December 2020
Accepted Date: 21 January 2021

Fund Project: the National Science Foundations of China 22076185the National Science Foundations of China 21771183the Natural Science Foundation of Fujian Province 2020J06033FJIRSM & IUE Joint Research Fund RHZX-2018-005

Figures(5)

Two new thioantimonates, (NH₄)₂Sb₁₀S₁₆ (1) and K_1.4(NH₄)_0.6Sb₁₀S₁₆ (2), have been synthesized by solvothermal method with the yields of 80% and 85%, respectively. Single-crystal X-ray diffraction (SCXRD) study reveals that 1 crystallizes in the monoclinic space group of Pn with a = 8.1284(4), b = 19.4587(9), c = 9.1030(4) Å, β = 91.736(5)°, V = 1439.14(12) Å³, Z = 2, D_c = 4.077 g·cm^-3, F(000) = 1576, μ = 10.389 mm^-1, R = 0.0343 and wR = 0.0624 (I > 2σ(I)); 2 also crystallizes in the monoclinic space group of Pn with a = 8.0989(6), b = 19.3730(17), c = 9.0411(6) Å, β = 91.879(6)°, V = 1417.79(19) Å³, Z = 2, D_c = 4.207 g·cm^-3, F(000) = 1598, μ = 10.748 mm^-1, R = 0.0323 and wR = 0.0664 (I > 2σ(I)). The anionic frameworks of two compounds both feature two-dimensional (2D) [Sb₁₀S₁₆]_n^2n- layers. The stabilities and optoelectronic properties of 1 and 2 have been characterized. In particular, they are stable under acidic or alkaline conditions (pH = 0 or 12.5), showing excellent acid-based resistance.
- solvothermal synthesis,
- crystal structure,
- thioantimonates,
- optoelectronic property
1. [1]
  Zheng, N.; Bu, X. H.; Vu, H.; Feng, P. Y. Open-framework chalcogenides as visible-light photocatalysts for hydrogen generation from water. Angew. Chem. Int. Ed. 2005, 44, 5299−5303. doi: 10.1002/anie.200500346
2. [2]
  Yu, J. M.; Cai, T.; Ma, Z. J.; Wang, F.; Wang, H.; Yu, J. P.; Xiao, L. L.; Cheng, F. F.; Xiong, W. W. Using thiol-amine solvent mixture to prepare main group heterometallic chalcogenides. Inorg. Chim. Acta 2020, 509, 119698−7. doi: 10.1016/j.ica.2020.119698
3. [3]
  Feng, M. L.; Kong, D. N.; Xie, Z. L.; Huang, X. Y. Three-dimensional chiral microporous germanium antimonysulfide with ion-exchange properties. Angew. Chem. Int. Ed. 2008, 47, 8623−8626. doi: 10.1002/anie.200803406
4. [4]
  Ding, N.; Kanatzidis, M. G. Selective incarceration of caesium ions by Venus flytrap action of a flexible framework sulfide. Nat. Chem. 2010, 2, 187−191. doi: 10.1038/nchem.519
5. [5]
  Chung, I.; Kanatzidis, M. G. Metal chalcogenides: a rich source of nonlinear optical materials. Chem. Mater. 2014, 26, 849−869. doi: 10.1021/cm401737s
6. [6]
  Bag, S.; Trikalitis, P. N.; Chupas, P. J.; Armatas, G. S.; Kanatzidis, M. G. Porous semiconducting gels and aerogels from chalcogenide clusters. Science 2007, 317, 490−493. doi: 10.1126/science.1142535
7. [7]
  Zheng, N. F.; Bu, X. G.; Wang, B.; Feng, P. Y. Microporous and photoluminescent chalcogenide zeolite analogs. Science 2002, 298, 2366−2369. doi: 10.1126/science.1078663
8. [8]
  Xiong, W. W.; Miao, J. W.; Ye, K. Q.; Wang, Y.; Liu, B.; Zhang, Q. C. Threading chalcogenide layers with polymer chains. Angew. Chem. Int. Ed. 2015, 54, 546−550.
9. [9]
  Wang, F.; Yang, D. D.; Liao, Y. Y.; Ma, Z. J.; Hu, B.; Wang, Y. Q.; Xiong, W. W.; Huang, X. Y. Synthesizing crystalline chalcogenidoarsenates in thiol-amine solvent mixtures. Inorg. Chem. 2020, 59, 2337−2347. doi: 10.1021/acs.inorgchem.9b03165
10. [10]
  Parise, J. B. An antimony sulfide with a two-dimensional, intersecting system of channels. Science 1991, 251, 293−294. doi: 10.1126/science.251.4991.293
11. [11]
  Berlepsch, P.; Miletich, R.; Armbruster, T. The crystal structures of synthetic KSb₅S₈ and (Tl_0.598, K_0.402)Sb₅S₈ and their relation to parapierrotite (TlSb₅S₈). Z. Kristallogr. 1999, 214, 57−63.
12. [12]
  Zhou, J.; Dai, J.; Bian, G. Q.; Li, C. Y. Solvothermal synthesis of group 13~15 chalcogenidometalates with chelating organic amines. Coord. Chem. Rev. 2009, 253, 1221−1247.
13. [13]
  Sheldrick, W. S.; Wachhold, M. Chalcogenidometalates of the heavier group 14 and 15 elements. Coord. Chem. Rev. 1998, 176, 211−322. doi: 10.1016/S0010-8545(98)00120-9
14. [14]
  Kiebach, R.; Nather, C.; Bensch, W. Solvothermal synthesis of (C₆H₁₇N₃)Sb₁₀S₁₆: a new thioantimonate(Ⅲ) with an in-situ formed organic amine cation. Z. Naturforsch., B: Chem. Sci. 2004, 59, 1314−1319. doi: 10.1515/znb-2004-11-1250
15. [15]
  Vaqueiro, P.; Darlow, D. P.; Powell, A. V.; Chippindale, A. M. Solvothermal synthesis of novel antimony sulphides containing [Sb₄S₇]^2- units. Solid State Ionics 2004, 172, 601−605. doi: 10.1016/j.ssi.2004.01.064
16. [16]
  Spetzler, V.; Nather, C.; Bensch, W. (C₆N₂H₁₈)Sb₄S₇ a thioantimonate(Ⅲ) with a layered [Sb₄S₇]^2- anion in the presence of a diprotonated amine as structure director. Z. Naturforsch., B: Chem. Sci. 2006, 61, 715−720.
17. [17]
  Ko, Y. H.; Tan, K. M.; Parise, J. B.; Darovsky, A. Synthesis of a novel two-dimensional antimony sulfide, [C₄H₁₀N]₂Sb₈S₁₃·0.15H₂O, and its structure solution using synchrotron imaging plate data. Chem. Mater. 1996, 8, 493−496. doi: 10.1021/cm950402j
18. [18]
  Wang, X. Q.; Liebau, F. Synthesis and structure of (CH₃NH₃)₂Sb₈S₁₃: a nanoporous thioantimonate(Ⅲ) with a 2-dimensional channel system. J. Solid State Chem. 1994, 111, 385−389. doi: 10.1006/jssc.1994.1243
19. [19]
  Spetzler, V.; Kiebach, R.; Nather, C.; Bensch, W. Two novel thioantimonates(Ⅲ) with the same stoichiometric Sb: S ratio but different crystal structures: solvothermal synthesis, crystal structures, thermal stability and spectroscopy of (C₆N₃H₁₇)Sb₆S₁₀ and (C₇N₂H₁₃)₃Sb₉S₁₅. Z. Anorg. Allg. Chem. 2004, 630, 2398−2404. doi: 10.1002/zaac.200400194
20. [20]
  Sheldrick, W. S.; Hausler, H. J. On the preparation and crystal-structure of Cs₃Sb₅S₉, Cs₃Sb₅Se₉. Z. Anorg. Allg. Chem. 1988, 561, 149−156.
21. [21]
  Zhu, A. M.; Jia, D. X.; Wang, P.; Zhang, Y. Solvothermal synthesis and crystal structure of a layered thioantimonate(Ⅲ) [C₄H₉NH₃]₂Sb₄S₇. Chin. J. Struc. Chem. 2007, 26, 1298−1302.
22. [22]
  Mertz, J. L.; Fard, Z. H.; Malliakas, C. D.; Manos, M. J.; Kanatzidis, M. G. Selective removal of Cs⁺, Sr²⁺, and Ni²⁺ by K_2xMg_xSn_3-xS₆ (x = 0.5~1) (KMS-2) relevant to nuclear waste remediation. Chem. Mater. 2013, 25, 2116−2127. doi: 10.1021/cm400699r
23. [23]
  Manos, M. J.; Kanatzidis, M. G. Highly efficient and rapid Cs⁺ uptake by the layered metal sulfide K_2xMn_xSn_3-xS₆ (KMS-1). J. Am. Chem. Soc. 2009, 131, 6599−6607. doi: 10.1021/ja900977p
24. [24]
  Zhang, X.; Yi, N.; Hoffmann, R.; Zheng, C.; Lin, J.; Huang, F. Semiconductive K₂MSbS₃(SH) (M = Zn, Cd) featuring one-dimensional _∞¹[ M₂Sb₂S₆(SH₂)]^4- chains. Inorg. Chem. 2016, 55, 9742−9747. doi: 10.1021/acs.inorgchem.6b01529
25. [25]
  Wang, K. Y.; Liu, H. W.; Zhang, S.; Ding, D.; Cheng, L.; Wang, C. Selenidostannates and a silver selenidostannate synthesized in deep eutectic solvents: crystal structures and thermochromic study. Inorg. Chem. 2019, 58, 2942−2953. doi: 10.1021/acs.inorgchem.8b02610
26. [26]
  Wang, K. Y.; Ding, D.; Zhang, S.; Wang, Y.; Liu, W.; Wang, S.; Wang, S. H.; Liu, D.; Wang, C. Preparation of thermochromic selenidostannates in deep eutectic solvents. Chem. Commun. 2018, 54, 4806−4809. doi: 10.1039/C8CC01614C
27. [27]
  Cai, T.; Zhu, J. N.; Cheng, F. F.; Li, P.; Li, W.; Zhao, M. Y.; Xiong, W. W. Growing crystalline selenidostannates in deep eutectic solvent. Inorg. Chim. Acta 2019, 484, 214−218. doi: 10.1016/j.ica.2018.09.046
28. [28]
  Ma, Z. M.; Weng, F.; Wang, Q. R.; Tang, Q.; Zhang, G. H.; Zheng, C.; Han, R. P. S.; Huang, F. Q. Low temperature synthesis and structures of alkaline earth metal chalcogenides Ba₃Cu₄SbS₆OH, BaCuSbS₃ and BaCu₂S₂. RSC Adv. 2014, 4, 28937−28940. doi: 10.1039/C3RA46878J
29. [29]
  Sheldrick, W. S.; Wachhold, M. Solventothermal synthesis of solid-state chalcogenidometalates. Angew. Chem. Int. Ed. 1997, 36, 207−224.
30. [30]
  Du, K. Z.; 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. doi: 10.1021/ic202246q
31. [31]
  Yang, D. D.; Li, W.; Xiong, W. W.; Li, J. R.; Huang, X. Y. Ionothermal synthesis of discrete supertetrahedral Tn (n = 4, 5) clusters with tunable components, band gaps, and fluorescence properties. Dalton Trans. 2018, 47, 5977−5984. doi: 10.1039/C8DT00524A
32. [32]
  Cordier, G.; Schwidetzky, C.; Schafer, H. New SbS₂ strings in the BaSb₂S₄ structure. J. Solid State Chem. 1984, 54, 84−88. doi: 10.1016/0022-4596(84)90134-8
33. [33]
  Cordier, G.; Schafer, H.; Schwidetzky, C. The crystal-structure of SrSb₄S₇·6H₂O. Z. Naturforsch., B: Chem. Sci. 1984, 39, 131−134. doi: 10.1515/znb-1984-0201
34. [34]
  Graf, H. A.; Schafer, H. Preparation and crystal-structure of K₂Sb₄S₇. Z. Naturforsch. B Chem. Sci. 1972, B27, 735−739.
35. [35]
  Kiebach, R.; Nather, C.; Sebastian, C. P.; Mosel, B. D.; Pottgen, R.; Bensch, W. [C₆H₂₁N₄][Sb₉S₁₄O]: solvothermal synthesis, crystal structure and characterization of the first non-centrosymmetric open Sb-S-O framework containing the new [SbS₂O] building unit. J. Solid State Chem. 2006, 179, 3082−3086.
36. [36]
  Powell, A. V.; Boissiere, S.; Chippindale, A. M. [(NH₃CH₂CH₂CH₂NH₂CH₂)₂]_0.5Sb₇S₁₁: a new two-dimensional antimony sulfide with antimony-antimony bonding. Chem. Mater. 2000, 12, 182−187. doi: 10.1021/cm990526m
37. [37]
  Dittmar, G.; Schafer, H. Preparation and crystal-structure of Cs₂Sb₄S₇. Z. Anorg. Allg. Chem. 1978, 441, 98−102. doi: 10.1002/zaac.19784410112
38. [38]
  Puls, A.; Nather, C.; Bensch, W. 2-Ammoniopropylammonium dodeca-mu-sulfido-tetrasulfidodecaantimony. Acta Crystallogr., Sect. E: Crystallogr. Commun. 2006, 62, M674−M676. doi: 10.1107/S0108270106041242
39. [39]
  Wang, X. Q. Synthesis and crystal-structure of a new microporous thioantimonate(Ⅲ) [H₃N(CH₂)₃NH₃]Sb₁₀S₁₆. Eur. J. Solid State Inorg. Chem. 1995, 32, 303−312.
40. [40]
  Zhang, M.; Sheng, T. L.; Huang, X. H.; Fu, R. B.; Wang, X.; Hu, S. M.; Xiang, S. C.; Wu, X. T. Solvothermal synthesis, crystal structure, and thermal stability of three-layered thioantimonate(Ⅲ) complexes: [Ni(C₃H₁₀N₂)₃]Sb₄S₇, [C₄H₁₄N₂]Sb₈S₁₃·H₂O, and [C₆H₁₈N₂]Sb₁₀S₁₆·H₂O. Eur. J. Inorg. Chem. 2007, 1606−1612.
41. [41]
  Dittmar, G.; Schafer, H. Preparation and crystal-structure of (NH₄)₂Sb₄S₇. Z. Anorg. Allg. Chem. 1977, 437, 183−187.
42. [42]
  Volk, K.; Bickert, P.; Kolmer, R.; Schafer, H. Preparation and crystal-structure of NH₄SbS₂. Z. Naturforsch., B: Chem. Sci. 1979, 34, 380−382. doi: 10.1515/znb-1979-0304
43. [43]
  Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2015, 71, 3−8. doi: 10.1107/S2053229614024218
44. [44]
  Luo, Q. P.; Yu, X. Y.; Lei, B. X.; Chen, H. Y.; Kuang, D. B.; Su, C. Y. Reduced graphene oxide-hierarchical ZnO hollow sphere composites with enhanced photocurrent and photocatalytic activity. J. Phys. Chem. C 2012, 116, 8111−8117. doi: 10.1021/jp2113329
45. [45]
  Li, G.; Miao, J. W.; Cao, J.; Zhu, J.; Liu, B.; Zhang, Q. C. Preparation and photoelectrochemical behavior of 1,4,6,8,11,13-hexazapentacene (HAP). Chem. Commun. 2014, 50, 7656−7658. doi: 10.1039/C4CC02908A
46. [46]
  Zhang, Q. C.; Liu, Y.; Bu, X. H.; Wu, T.; Feng, P. Y. A rare (3, 4)-connected chalcogenide superlattice and its photoelectric effect. Angew. Chem. Int. Ed. 2008, 47, 113−116. doi: 10.1002/anie.200703442
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