助熔剂法合成钨氧氯化合物Li23CuW10O40Cl5

doi:10.15541/jim20190598

摘要/Abstract

摘要：

由于不同阴离子之间的电负性、离子半径、极化率和氧化态之间的差异, 混合阴离子化合物可以产生不同于单一类型阴离子的新特性。混合阴离子金属材料在电子、湿度探测器、气体传感器、太阳能电池电极等领域有着广泛的应用前景。助熔剂方法是一种广泛应用于混合离子晶体生长的方法, 它以适当的金属盐作为助熔剂, 在较温和的条件下进行复分解反应。助熔剂法在混合阴离子化合物的合成中具有重要意义。钨氧氯化合物Li₂₃CuW₁₀O₄₀Cl₅单晶以高质量的Li₄WO₅为前驱体, 以CuCl₂为助熔剂通过两步法合成。通过X射线单晶衍射确定其晶体结构。结果表明, Li₂₃CuW₁₀O₄₀Cl₅结晶属于P6₃/mcm空间群, 晶胞参数分别为a=1.02846(3) nm, c=1.98768(9) nm, V=1.82076(11) nm³, Z=2。单胞中分别包含五个晶体学独立的Li原子, 两个W原子, 一个Cu原子, 两个Cl原子以及五个O原子。结构中, W(1)原子和一个Cl原子及五个O原子相连接, 形成畸变八面体, 而W(2)原子与四个O原子相连接形成四面体, Cu原子与六个O原子相连形成八面体。因此, Li₂₃CuW₁₀O₄₀Cl₅的晶体结构主要由[CuO₆]和[W(1)O₅Cl]八面体以及[W(2)O₄]四面体构成。助熔剂法合成钨氧氯化合物Li₂₃CuW₁₀O₄₀Cl₅对今后探索新型的混合阴离子化合物具有重要意义。

关键词: 钨氧氯化合物, CuCl₂助熔剂, 晶体结构, X射线衍射

Abstract:

Mixed anion compounds can generate the emergence of novel properties that differ from those with mono-type anion due to the difference of electronegativities, ionic radii, polarizabilities, and oxidation states between unlike anions. Abundant research has been conducted on metallic mixed-anion materials with potential application in electronics, detectors of moisture, gas sensors, electrodes for solar batteries, etc. The flux method has been widely applied for mixed-anion crystal growth, which based on metathetical reaction with appropriate metal-salts ?ux under mild conditions. It is meaningful to synthesize the mixed anion compounds by the flux method. Single crystals of tungsten oxychloride Li₂₃CuW₁₀O₄₀Cl₅ were prepared via CuCl₂ flux-growth method by two steps, which using high quality and phase-pure polycrystalline Li₄WO₅ as precursor. The crystal structure was determined by single-crystal X-ray diffraction analysis, which indicates that Li₂₃CuW₁₀O₄₀Cl₅ crystallizes in P6₃/mcm space group (a= 1.02846(3) nm, c=1.98768(9) nm, V=1.82076(11) nm ³, and Z=2). There are crystallographically independent five Li, two W, one Cu, two Cl, and five O atoms in the unit cell, where W(1) atoms are coordinated with one Cl and five O atoms in a distorted octahedra geometry, while W(2) atoms are connected with four O atoms in a tetrahedral coordination. The Cu atoms are connected with six O atoms forming [CuO₆] octahedra. Thus, the crystal structure of the titled compound consists of [CuO₆] and [W(1)O₅Cl] octahedra, and [W(2)O₄] tetrahedra. The successful synthesis of tungsten oxychloride Li₂₃CuW₁₀O₄₀Cl₅ through flux-growth method is meaningful for explore new mixed anion compounds in future.

Key words: tungsten oxychloride, CuCl₂ flux, crystal structure, X-ray diffraction

中图分类号:

TQ174

李淑芳, 赵爽, 李满荣. 助熔剂法合成钨氧氯化合物Li₂₃CuW₁₀O₄₀Cl₅[J]. 无机材料学报, 2020, 35(7): 834-838.

LI Shufang, ZHAO Shuang, LI Manrong. Flux Growth of Tungsten Oxychloride Li₂₃CuW₁₀O₄₀Cl₅[J]. Journal of Inorganic Materials, 2020, 35(7): 834-838.

图/表 7

参考文献 28

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Chemical formula	Li₂₃CuW₁₀O₄₀Cl₅	Chemical formula	Li₂₃CuW₁₀O₄₀Cl₅
Formula weight	2878.91	μ/mm^-1	32.505
Crystal size/mm³	0.162×0.115×0.090	θ_range/(°)	3.07-25.49
Crystal system	Hexagonal	GOF on F²	1.171
Space group	P6₃/mcm	R₁^a [I >2s (I)]	0.0229
a/nm	1.02846(3)	wR₂^b [I >2s (I)]	0.0637
c/nm	1.98768(9)	R₁^a (all data)	0.0232
V/nm³	1.82076(11)	wR₂^b(all data)	0.0640
Z	2	Extinction coefficient	0.00171(14)
D_calcd/(g·cm^-3)	5.251

Chemical formula	Li₂₃CuW₁₀O₄₀Cl₅	Chemical formula	Li₂₃CuW₁₀O₄₀Cl₅
Formula weight	2878.91	μ/mm^-1	32.505
Crystal size/mm³	0.162×0.115×0.090	θ_range/(°)	3.07-25.49
Crystal system	Hexagonal	GOF on F²	1.171
Space group	P6₃/mcm	R₁^a [I >2s (I)]	0.0229
a/nm	1.02846(3)	wR₂^b [I >2s (I)]	0.0637
c/nm	1.98768(9)	R₁^a (all data)	0.0232
V/nm³	1.82076(11)	wR₂^b(all data)	0.0640
Z	2	Extinction coefficient	0.00171(14)
D_calcd/(g·cm^-3)	5.251

Atom	Site	x	y	z	U_eq./nm²
W(1)	12k	0.1904(1)	0	0.6257(1)	0.6(1)
W(2)	8h	2/3	1/3	0.5947(1)	0.6(1)
Cu(1)	2b	0	0	1/2	2.0(1)
Cl(1)	6g	0.4831(4)	0.4831(4)	3/4	1.6(1)
Cl(2)	4e	0	0	0.6693(6)	7.9(3)
O(1)	12k	0	0.8520(8)	0.5647(4)	1.3(2)
O(2)	12k	0.3077(8)	0	0.5594(4)	1.1(2)
O(3)	24l	0.3150(6)	0.1562(6)	0.6766(3)	1.1(1)
O(4)	24l	0.5092(7)	0.3447(6)	0.5644(3)	1.2(1)
O(5)	8h	2/3	1/3	0.6842(5)	1.2(2)
Li(1)	12j	0.2060(40)	0.2060(40)	3/4	1.4(2)
Li(2)	12k	1/2	1/2	1/2	2.2(6)
Li(3)	12i	0.3510(20)	z0.1755(12)	1/2	2.3(5)
Li(4)	6f	0.3520(30)	0.3520(30)	0.6319(1)	4.2(7)
Li(5)	6g	0.4800(30)	0.2210(30)	3/4	2.8(5)

Atom	Site	x	y	z	U_eq./nm²
W(1)	12k	0.1904(1)	0	0.6257(1)	0.6(1)
W(2)	8h	2/3	1/3	0.5947(1)	0.6(1)
Cu(1)	2b	0	0	1/2	2.0(1)
Cl(1)	6g	0.4831(4)	0.4831(4)	3/4	1.6(1)
Cl(2)	4e	0	0	0.6693(6)	7.9(3)
O(1)	12k	0	0.8520(8)	0.5647(4)	1.3(2)
O(2)	12k	0.3077(8)	0	0.5594(4)	1.1(2)
O(3)	24l	0.3150(6)	0.1562(6)	0.6766(3)	1.1(1)
O(4)	24l	0.5092(7)	0.3447(6)	0.5644(3)	1.2(1)
O(5)	8h	2/3	1/3	0.6842(5)	1.2(2)
Li(1)	12j	0.2060(40)	0.2060(40)	3/4	1.4(2)
Li(2)	12k	1/2	1/2	1/2	2.2(6)
Li(3)	12i	0.3510(20)	z0.1755(12)	1/2	2.3(5)
Li(4)	6f	0.3520(30)	0.3520(30)	0.6319(1)	4.2(7)
Li(5)	6g	0.4800(30)	0.2210(30)	3/4	2.8(5)

Bond	Bond length/nm	Bond	Bond length/nm	Bond	Bond length/nm
W(1)-O(3)	0.1786(6)	Li(1)-O(3)	0.2075(2)	Li(4)-O(4)	0.2086(5)
W(1)-O(3)	0.1786(6)	Li(1)-O(3)	0.2075(2)	Li(4)-O(4)	0.2086(5)
W(1)-O(2)	0.1787(7)	Li(1)-O(5)	0.213(2)	Li(4)-O(4)	0.2086(5)
W(1)-Cl(2)	0.2141(5)	Li(1)-O(5)	0.213(2)	Li(4)-O(4)	0.2086(5)
W(1)-O(1)	0.2154(5)	Li(1)-Cl(1)	0.248(3)	Li(4)-O(2)	0.2303(8)
W(1)-O(1)	0.2154(5)	Li(1)-Cl(1)	0.268(3)	Li(4)-O(2)	0.2303(8)
W(2)-O(5)	0.1778(9)	Li(2)-O(3)	0.2056(2)	(Li(4)-O)	0.2158(3)
W(2)-O(4)	0.1785(6)	Li(2)-O(3)	0.2056(2)	BVS	0.096
W(2)-O(4)	0.1785(6)	Li(2)-O(1)	0.2490(3)	Li(5)-O(3)	0.2054(8)
W(2)-O(4)	0.1785(6)	Li(2)-Cl(1)	0.2710(3)	Li(5)-O(3)	0.2054(8)
(W(2)-O)	0.1784(2)	Li(2)-O(4)	0.213(2)	Li(5)-O(3)	0.2054(8)
BVS	0.574	Li(2)-O(4)	0.213(2)	Li(5)-O(3)	0.2054(8)
Cu(1)-O(1)	0.1992(8)	Li(3)-O(2)	0.2012(6)	Li(5)-Cl(2)	0.266(3)
Cu(1)-O(1)	0.1992(8)	Li(3)-O(2)	0.2012(6)	Li(5)-Cl(2)	0.266(3)
Cu(1)-O(1)	0.1992(8)	Li(3)-O(1)	0.2346(2)	Li(5)-Cl(1)	0.285(4)
Cu(1)-O(1)	0.1992(8)	Li(3)-O(1)	0.2346(2)
Cu(1)-O(1)	0.1992(8)	Li(3)-O(4)	0.2117(2)
Cu(1)-O(1)	0.1992(8)	Li(3)-O(4)	0.2117(2)
(Cu(1)-O)	0.1992(8)	(Li(3)-O)	0.2158(3)
BVS	0.250	BVS	0.099

助熔剂法合成钨氧氯化合物Li₂₃CuW₁₀O₄₀Cl₅

Flux Growth of Tungsten Oxychloride Li₂₃CuW₁₀O₄₀Cl₅

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