Home Physical Sciences Crystal structure of dirubidium trimercury(II) tetraselenide, Rb2Hg3Se4
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Crystal structure of dirubidium trimercury(II) tetraselenide, Rb2Hg3Se4

  • Kang-Woo Kim EMAIL logo
Published/Copyright: February 9, 2016

Abstract

Rb2Hg3Se4, orthorhombic, Ibam (no. 72), a = 6.4183(9) Å, b = 11.626(2) Å, c = 14.454(2) Å, V = 1078.5(3) Å3, Z = 4, Rgt(F) = 0.038, wRref(F2) = 0.142, T = 173 K.

CCDC no.:: 430729

The crystal structure is shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Orange red, plate, size 0.036×0.135×0.299 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:649.92 cm−1
Diffractometer, scan mode:Bruker APEX-II CCD, φ and ω scans
2θmax:56.65°
N(hkl)measured, N(hkl)unique:2562, 687
N(param)refined:25
Programs:SHELX [8], WinGX [9], Diamond [10]
Table 2

Atomic displacement parameters (Å2).

AtomSitexyzU11U22U33U12U13U23
Hg(1)4b00.50.250.0183(7)0.0187(5)0.0242(6)000
Hg(2)8g00.16487(4)0.250.0166(6)0.0309(6)0.0232(6)00.0022(2)0
Se(1)16k0.2235(2)0.36902(7)0.36504(7)0.0170(6)0.0132(6)0.0218(6)0.0019(4)0.0013(4)0.0012(4)
Rb(1)8j−0.2695(2)0.6202(1)00.0275(9)0.0134(7)0.0257(8)0.0012(5)00

Source of materials

HgCl2 (0.050 g, 0.18 mmol) and Rb2Se (0.092 g, 0.37 mmol) were charged to a Pyrex tube with a diameter of 9 mm under an argon atmosphere, and about 0.5 mL ethylenediamine was added as a solvent. While the solvent was being frozen, the Pyrex tube was evacuated under vacuum and sealed with the use of a flame. The sealed tube was heated at 160 °C for 24 h, then cooled to room temperature. Orange red crystals were isolated and washed with DMF and diethyl ether. Rectangular plates of Rb2Hg3Se4 were obtained in 25% yield, based on Hg.

Discussion

Low-dimensional ternary mercury chalcogenides, A2Hg3Q4 (A = alkali metal; Q = S, Se, Te) could be considered as dimensional reduction materials from 3D binary mercury chalcogenide, HgQ [1]. The known A2Hg3Q4 compounds, Na2Hg3S4 and Rb2Hg3Te4 possess 2D layered structure, whereas K2Hg3Q4 (Q = S, Se) and Cs2Hg3Se4 are in possession of 1D chain structures [1–3]. The title compound, Rb2Hg3Se4 is a new additon to the family of A2Hg3Q4. It is noteworthy to mention, that the Tl analog of A2Hg3Q4, Tl2Hg3Se4 was recently prepared and reported to be promising for high-density, wide-band-gap semiconductors [4].

In addition to A2Hg3Q4, known compounds in the system of A/Hg/Q (A = alkali metal; Q = S, Se, Te) are as follows: A2HgSe2 (A = Na, K), A6HgQ4 (A = K, Rb; Q = S, Se), Rb4Hg5Te13, and A2Hg6Q7 (A = K, Rb, Cs; Q = S, Se) [1, 5–7]. All the A/Hg/Q ternary compounds except Rb2Hg3Te4 and Rb4Hg5Te13 have been prepared by the direct method or the molten-salt flux method. Rb2Hg3Te4 and Rb4Hg5Te13 have been prepared by the ethylenediamine solvothermal method. The title compound, Rb2Hg3Se4 is another A/Hg/Q compound prepared by the ethylenediamine solvothermal method.

Rb2Hg3Se4 is composed of one-dimensional anionic (Hg3Se4)n2n- chains and charge-balancing Rb+ cations (see the Figure), representing the same structure as those of K2Hg3Q4 (Q = S, Se) and Cs2Hg3Se4 [1]. While K2Hg3Q4 (Q = S, Se) and Cs2Hg3Se4 crystallize in the space group Pbcn (no. 60), Rb2Hg3Se4 crystallizes in the space group Ibam (no. 72). The (Hg3Se4)n2n- chain of Rb2Hg3Se4 runs parallel to the crystallolgraphic a-axis and can be viewed as a spiro-polymer of eight-membered Hg4Se4 rings (see the Figure). There are two crystallographically independent Hg atoms in the asymmetric unit of Rb2Hg3Se4. The Hg1 atom, sitting on special position of 222 site symmetry, has tetrahedral geometry with the Se—Hg—Se angles of 103.05(4)°, 110.52(4)°, and 115.07(4)°. The Se—Hg—Se angle around the almost linear Hg2 atom is 161.59(4)°, which is comparable to those angles of 164.2(2)° and 158.8(2)° found in K2Hg3Se4 and Cs2Hg3Se4, respectively. A short Hg2—Se interchain contact, 3.234(1) Å might cause distortion from linear geometry toward trigonal geometry around Hg2 centers. The Hg—Se bond distance is 2.672(1) Å for the tetrahedral Hg1 atom and 2.464(1) Å for the “linear” Hg2 atom. For Rb2Hg3Se4, distance between two “linear” Hg2 atoms in the Hg4Se4 rings of (Hg3Se4)n2n- chain is 3.838(1) Å. This distance is larger than 3.508(1) Å for K2Hg3Se4 and smaller than 4.082(1) Å for Cs2Hg3Se4. As the alkali metal counter-cation becomes larger in the series of A2Hg3Se4 (A = K, Rb, Cs), the (Hg3Se4)n2n- chain becomes thicker.


Corresponding author: Kang-Woo Kim, Department of Chemistry, Incheon National University, Incheon 406-772, Korea, e-mail:

Acknowledgements:

This work was supported by the Incheon National University Research Grant in 2014. The authors thank Dr. Ji-Eun Lee at Central Instrument Facility, Gyeongsang National University for the X-ray measurements.

References

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Received: 2015-7-3
Accepted: 2016-1-18
Published Online: 2016-2-9
Published in Print: 2016-3-1

©2016 Kang-Woo Kim published by De Gruyter.

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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  96. Crystal structure of (Z)-1-(((3-acetyl-2-hydroxyphenyl)amino)methylene)naphthalen-2(1H)-one, C19H15NO3
  97. Crystal structure of (Z)-5-(4-chlorobenzylidene)-2-thioxothiazolidin-4-one —dimethylsulfoxide (1:1), C12H12ClNO2S3
  98. Crystal structure of 5,5′-((4-(trifluoromethyl)phenyl)methylene)bis(1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione) – diethylamine – dichloromethane (1/1/1) C25H32Cl2F3N5O6
  99. Crystal structure of 2-(dimethylsulfanylidene)-N-(4-methoxyphenyl)-3-oxo-3-phenylpropanamide
  100. Crystal structure of (1,10-phenanthroline-κ2N,N′)bis(thiocyanato-κN)platinum(II), C14H8N4PtS2
  101. Crystal structure of di(μ2-chlorido)bis[2-(2-pyridyl)phenyl-κ2N,C1]dipalladium(II), C22H16Cl2N2Pd2
  102. Crystal structure of trans-dibromidodi(pyridine-κN)palladium(II), PdBr2(C5H5N)2
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