Citation: He-Lin WANG, Zhi-Liang GUO, Bo-Zhi LIU, Zhuang-Ze WU, Li-Xu LEI. Less solvent solid-state consecutive coordination reaction of copper chloride[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(8): 1536-1544. doi: 10.11862/CJIC.2023.093 shu

Less solvent solid-state consecutive coordination reaction of copper chloride

School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China

Corresponding author: Li-Xu LEI, lixu.lei@seu.edu.cn
Received Date: 16 January 2023
Revised Date: 23 April 2023

Figures(6)

The less solvent solid-state reaction (LSR) between CuCl₂·2H₂O and NH₄Cl in a little water produced only (NH₄)₂[CuCl₄(H₂O)₂] since NH₄[CuCl₃] was not stable in water; however, in a little absolute ethanol at 60 ℃, the LSR produced NH₄[CuCl₃], or (NH₄)₂[CuCl₄] according to the mixed stoichiometric ratio. The LSR of CuCl₂ and NH₄Cl in a 1∶2 molar ratio proceeds in two steps: the formation of NH₄[CuCl₃] at an early stage and a further reaction between NH₄[CuCl₃] and remaining NH₄Cl to form the final product (NH₄)₂[CuCl₄]. In contrast, the LSR of CuCl₂·2H₂O and 2, 2′-bipyridine (bipy) in 1∶1 molar ratio in a little water produced solely [Cu(bipy)Cl₂], but the 1∶2 product, [Cu(bipy)₂Cl₂]·2H₂O did appear in its early stage. The reason may be that the structure of the solid CuCl₂·2H₂O, which is polymerized planer trans-[CuCl₂(H₂O)₂], converts to molecular trans-[CuCl₂(H₂O)₄] in water, and the latter makes the activation energy of successive substitution of two H₂O molecules by bipy closer. Thus, bipy rapidly and successively replaces four water molecules in trans-[CuCl₂(H₂O)₄] to form a 1∶2 product. This surprising result indicates that the LSR of [Cu(bipy)₂Cl₂]·2H₂O and CuCl₂·2H₂O is also spontaneous, and according to thermodynamics, it is possible if the Δ_rG^⊖ of the second reaction is bigger than that of the first one of the consecutive reactions. Therefore, the LSR could also proceed stepwise, which is hard to find in solution reactions.
- less solvent solid-state reaction,
- consecutive reaction,
- stepwise reaction,
- X-ray diffraction,
- reaction of 100% yield
1. [1]
  XIN X Q, ZHENG L M. Solid state reaction at room temperature and low-heating temperature[J]. University Chemistry, 1994,9(6):1-7.
2. [2]
  LEI L X, ZHOU Y M. Solvent-free or less-solvent solid state reactions[J]. Prog. Chem, 2020,32(8):1158-1171.
3. [3]
  Anastas P, Eghbali N. Green chemistry: Principles and practice[J]. Chem. Soc. Rev., 2010,39(1):301-312. doi: 10.1039/B918763B
4. [4]
  Ardila-Fierro K J, Hernandez J G. Sustainability assessment of mechanochemistry by using the twelve principles of green chemistry[J]. ChemSusChem, 2021,14(10):2145-2162. doi: 10.1002/cssc.202100478
5. [5]
  Cuccu F, De Luca L, Delogu F, Colacino E, Solin N, Mocci R, Porcheddu A. Mechanochemistry: New tools to navigate the uncharted territory of "impossible" reactions[J]. ChemSusChem, 2022,15(17)e202200362.
6. [6]
  HAN W K, TIAN L, XU Z L, ZHU W, LI Z H, LI T, GU Z G, LI Z J. Self-sorting of binuclear Schiff-base complexes under solvent-free grinding conditions[J]. Chinese J. Inorg. Chem, 2017,33(4):550-559.
7. [7]
  TAN J, LI Z F, YANG X F, LI J, ZHANG T T. Effect of dry and wet environment of ball milling on visible light catalytic performance of sulfur-doped carbon nitride[J]. Chinese J. Inorg. Chem, 2020,36(3):475-484.
8. [8]
  WU W J, LI Y T, FENG Q, DING W X. Perovskite dual-function passivator: Room temperature ionic liquid obtained from mechanochemical preparation[J]. Acta Chim. Sin, 2022,80(11):1469-1475.
9. [9]
  JIANG H L, LIU C, LEI L X. Ammonium carnallite prepared from a less-solvent solid state reaction[J]. University Chemistry, 2021,36(12)2102008.
10. [10]
  Kamyshny A. Solubility of cyclooctasulfur in pure water and sea water at different temperatures[J]. Geochim. Cosmochim. Acta, 2009,73(20):6022-6028. doi: 10.1016/j.gca.2009.07.003
11. [11]
  Wang H L, Liu C, Jiang H L, Guo Z L, Zheng Y P, Qi Q, Lei L X. A laboratory experiment on preparation of 3PbO·PbSO₄·H₂O using less solvent solid state reaction for undergraduate students[J]. Educ. Chem. Eng., 2023,43:92-99.
12. [12]
  Li C X, Lei L X, Xin X Q. Synthesis of M(biN)_nCl₂ by solid-solid reactions[J]. Chin. Sci. Bull., 1994(4):349-350.
13. [13]
  Lei L X, Xin X Q. Stepwise reaction of CuCl₂·2H₂O with 2, 2'-bipyridyl in the solid state[J]. J. Solid State Chem., 1995,119(2):299-303.
14. [14]
  Lei L X, Xin X Q. Solid state synthesis of a new compound Cu(HQ)Cl₂ and its formation reaction[J]. Thermochim. Acta, 1996,273:61-67.
15. [15]
  Lei L X, Wang Z, Xin X Q. The solid state reaction of CuCl₂·2H₂O and 8-hydroxylquinoline[J]. Thermochim. Acta, 1997,297(1/2):193-197.
16. [16]
  Lei L X, Jing S, Walton R I, Xin X Q, O'Hare D. Investigation of the solid state reaction of FeSO₄·7H₂O with 1, 10-phenanthroline[J]. J. Chem. Soc.-Dalton Trans., 2002,18(18):3477-3481.
17. [17]
  Kinyon J S, Clark R, Dalal N S, Choi E S. Ferroelectricity in the gapless quantum antiferromagnet NH₄CuCl₃[J]. Phys. Rev. B, 2015,92(14)144103.
18. [18]
  Kinyon J S, Dalal N S, Clark R J, Zhou H D, Choi K Y. Closing the spin gap of (NH₄)_xK_1-xCuCl₃ through chemical substitution[J]. Phys. Rev. Mater., 2021,5(5)054413.
19. [19]
  Shiramura W, Takatsu K, Kurniawan B, Tanaka H, Uekusa H, Ohashi Y, Takizawa K, Mitamura H, Goto T. Magnetization plateaus in NH₄CuCl₃[J]. J. Phys. Soc. Jpn.,, 1998,67(5):1548-1551.
20. [20]
  Canhota F P, Salomã o G C, Carvalho N M F, Antunes O A C. Cyclohexane oxidation catalyzed by 2, 2'-bipyridyl Cu? complexes[J]. Catal. Commun., 2008,9(1):182-185.
21. [21]
  Sirdeshmukh D B, Deshpand V T. X-ray measurement of thermal expansion of ammonium chloride[J]. Acta Crystallogr. Sect. A, 1970,A26(2)295.
22. [22]
  Brownstein S, Han N F, Gabe E, Lepage Y. A redetermination of the crystal-structure of cupric chloride dihydrate[J]. Z. Kristall., 1989,189(1/2):13-15.
23. [23]
  Bhakaytamhane S N, Sequeira A, Chidambaram R. Disorder of ammonium ions in diammonium tetrachlorocuprate dihydrate, (NH₄)₂CuCl₄·2H₂O: A high-precision neutron diffraction study[J]. Acta Crystallogr. Sect. B, 1980,B36(12):2925-2929.
24. [24]
  Burns P C, Hawthorne F C. Tolbachite, CuCl₂, the first example of Cu²⁺ octahedrally coordinated by Cl^-[J]. Am. Miner., 1993,78(1/2):187-189.
25. [25]
  O'Bannon G, Willet R D. A redetermination of the crystal structure of NH₄CuCl₃ and a magnetic study of NH₄CuX₃ (X=Cl, Br)[J]. Inorg. Chim. Acta, 1981,53:L131-L132.
26. [26]
  Willett R D. Crystal structure of (NH₄)₂CuCl₄[J]. J. Chem. Phys., 1964,41(8):2243-2244.
27. [27]
  Louis B, Detoni C, Carvalho N M F, Duarte C D, Antunes O A C. Cu? bipyridine and phenanthroline complexes: Tailor-made catalysts for the selective oxidation of tetralin[J]. Appl. Catal. A-Gen., 2009,360(2):218-225.
28. [28]
  Engberg Å, Staffansson L I. An X-Ray Refinement of the Crystal Structure of Copper? chloride dihydrate[J]. Acta Chem. Scand., 1970,24(10):3510-3526.
29. [29]
  Medeiros F E O, Araujo B S, Ayala A P. Raman spectroscopy investigation of the thermal stability of the multiferroic CuCl₂ and its hydrated form[J]. Vib. Spectrosc., 2018,99:1-6.
30. [30]
  Fronczek F R, Collins S N, Chan J Y. Refinement of ferrous sulfate heptahydrate (melanterite) with low-temperature CCD data[J]. Acta Crystallogr. Sect. E., 2001,57(4):i26-i27.
31. [31]
  Speight J G. Lange's Handbook of Chemistry. New York: McGraw-Hill, 2005: 363-379
1. [1]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
2. [2]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
3. [3]
  Jiaqi AN , Yunle LIU , Jianxuan SHANG , Yan GUO , Ce LIU , Fanlong ZENG , Anyang LI , Wenyuan WANG . Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1511-1518. doi: 10.11862/CJIC.20240072
4. [4]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
5. [5]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
6. [6]
  Jun Jiang , Tong Guo , Wuxin Bai , Mingliang Liu , Shujun Liu , Zhijie Qi , Jingwen Sun , Shugang Pan , Aleksandr L. Vasiliev , Zhiyuan Ma , Xin Wang , Junwu Zhu , Yongsheng Fu . Modularized sulfur storage achieved by 100% space utilization host for high performance lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(4): 108565-. doi: 10.1016/j.cclet.2023.108565
7. [7]
  Keke Han , Wenjun Rao , Xiuli You , Haina Zhang , Xing Ye , Zhenhong Wei , Hu Cai . Two new high-temperature molecular ferroelectrics [1,5-3.2.2-Hdabcni]X (X = ClO₄⁻, ReO₄⁻). Chinese Chemical Letters, 2024, 35(6): 108809-. doi: 10.1016/j.cclet.2023.108809
8. [8]
  Mianying Huang , Zhiguang Xu , Xiaoming Lin . Mechanistic analysis of Co2VO4/X (X = Ni, C) heterostructures as anode materials of lithium-ion batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100309-100309. doi: 10.1016/j.cjsc.2023.100309
9. [9]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
10. [10]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
11. [11]
  Jingqi Ma , Huangjie Lu , Junpu Yang , Liangwei Yang , Jian-Qiang Wang , Xianlong Du , Jian Lin . Rational design and synthesis of a uranyl-organic hybrid for X-ray scintillation. Chinese Journal of Structural Chemistry, 2024, 43(5): 100275-100275. doi: 10.1016/j.cjsc.2024.100275
12. [12]
  Xin Dong , Jing Liang , Zhijin Xu , Huajie Wu , Lei Wang , Shihai You , Junhua Luo , Lina Li . Exploring centimeter-sized crystals of bismuth-iodide perovskite toward highly sensitive X-ray detection. Chinese Chemical Letters, 2024, 35(6): 108708-. doi: 10.1016/j.cclet.2023.108708
13. [13]
  Xiuwen Xu , Quan Zhou , Yacong Wang , Yunjie He , Qiang Wang , Yuan Wang , Bing Chen . Expanding the toolbox of metal-free organic halide perovskite for X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109272-. doi: 10.1016/j.cclet.2023.109272
14. [14]
  Yujia LI , Tianyu WANG , Fuxue WANG , Chongchen WANG . Direct Z-scheme MIL-100(Fe)/BiOBr heterojunctions: Construction and photo-Fenton degradation for sulfamethoxazole. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 481-495. doi: 10.11862/CJIC.20230314
15. [15]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
16. [16]
  Cheng PENG , Jianwei WEI , Yating CHEN , Nan HU , Hui ZENG . First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi₂X₉ (X=Cl, Br, I). Chinese Journal of Inorganic Chemistry, 2024, 40(3): 555-560. doi: 10.11862/CJIC.20230282
17. [17]
  Hong-Jin Liao , Zhu Zhuo , Qing Li , Yoshihito Shiota , Jonathan P. Hill , Katsuhiko Ariga , Zi-Xiu Lu , Lu-Yao Liu , Zi-Ang Nan , Wei Wang , You-Gui Huang . A new class of crystalline X-ray induced photochromic materials assembled from anion-directed folding of a flexible cation. Chinese Chemical Letters, 2024, 35(8): 109052-. doi: 10.1016/j.cclet.2023.109052
18. [18]
  Xuying Yu , Jiarong Mi , Yulan Han , Cai Sun , Mingsheng Wang , Guocong Guo . A stable radiochromic semiconductive viologen-based metal–organic framework for dual-mode direct X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109233-. doi: 10.1016/j.cclet.2023.109233
19. [19]
  Xin Dong , Tianqi Chen , Jing Liang , Lei Wang , Huajie Wu , Zhijin Xu , Junhua Luo , Li-Na Li . Structure design of lead-free chiral-polar perovskites for sensitive self-powered X-ray detection. Chinese Journal of Structural Chemistry, 2024, 43(6): 100256-100256. doi: 10.1016/j.cjsc.2024.100256
20. [20]
  Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO₃₋_x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(705)
HTML views(36)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142