research communications
0.21(H2O)yWS2
and electrical resistance property of RbaState Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, People's Republic of China, and bSchool of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, People's Republic of China
*Correspondence e-mail: huangfq@mail.sic.ac.cn
Rb0.21(H2O)yWS2, rubidium hydrate dithiotungstate, is a new quasi two-dimensional sulfide. Its consists of ordered WS2 layers, separated by disordered Rb+ ions and water molecules. All atomic sites are located on mirror planes. The WS2 layers are composed of edge-sharing [WS6] octahedra and extend parallel to (001). The presence of structural water was revealed by thermogravimetry, but the position and exact amount could not be determined in the present study. The temperature dependence of the electrical resistance indicates that Rb0.21(H2O)yWS2 is semiconducting between 80–300 K.
CCDC reference: 1920386
1. Chemical context
Typical two-dimensional structures of MS2 compounds (M = transition metals of group IVB–VIB) facilitate the intercalation of various atoms, ions or organic molecules (Whittingham et al., 1978). For example, AxMS2 (A = alkali metal; M = Nb, Ta, Ti, V) compounds can be prepared in high-temperature solid-state reactions (800–1000 K). These compounds can react with water molecules to form ionic hydrates A+x(H2O)y[MS2]x− (Omloo & Jellinek, 1970; Lerf & Schöllhorn, 1977; Lobert et al., 1992) that exhibit ion-exchange and solvent-exchange capacities. Some of the A+x(H2O)y[MS2]x− compounds show unusual superconducting properties (Schöllhorn & Weiss, 1974; Sernetz et al., 1974). Recently, by removing alkali ions from intercalated A+x(H2O)y[MS2]x− (A = alkali metal) compounds, several metastable MS2 (M = Mo, W) phases with new crystal structures and novel physical properties were reported (Fang et al., 2018, 2019). In order to identify the formation mechanism of metastable MS2 from A+x(H2O)y[MS2]x−, it is necessary to uncover the role of alkali ions intercalated into the interlayers of MS2.
In this communication, we report the preparation of Rb0.21(H2O)yWS2, its determination by single crystal X-ray diffraction, its thermal behaviour and its electrical resistance property.
2. Structural commentary
Rb0.21(H2O)yWS2 crystallizes in the monoclinic P21/m (No. 11) The structure consists of one independent W site, two independent S sites and two independent Rb sites, all of them located on a mirror plane (Wyckoff position 2e). The features ordered WS2 layers separated by disordered Rb+ ions, and of water molecules. The latter could not be localized in the current study, hence y in Rb0.21(H2O)yWS2 remains undetermined (see Experimental, and discussion below). Compared with [WS6]8– trigonal prisms in 2H-WS2 (Schutte et al., 1987), the WS2 layer in Rb0.21(H2O)yWS2 is composed of edge-sharing [WS6]8.21– octahedra. The W—S bond lengths range from 2.403 (4) Å to 2.550 (5) Å, and thus the average W—S distance is larger than that in 2H-WS2 [2.405 (5) Å; Schutte et al., 1987]. The WS2 layers extend parallel to (001) (Fig. 1). The shortest W—W bond length of 2.7678 (15) Å is between pairs of W atoms aligned in the [10] direction, much shorter than the W⋯W distance of 3.2524 (18) Å along [010]. Similar metal–metal separations also exist in some metastable MS2 phases prepared by de-intercalating alkali ions from Ax(H2O)yMS2 compounds (Yu et al., 2018; Shang et al., 2018). The Rb+ cations show a one-sided coordination to the S atoms of the adjacent layer. The Rb—S bonds range from 3.47 (7) Å to 3.64 (5) Å, comparable to the Rb—S bonds [3.344 (7)–3.561 (1) Å] in RbCr5S8 (Huster, 1978).
Similar to Kx(H2O)yTaS2 and Kx(H2O)yNbS2 (Graf et al., 1977), it was impossible to determine the light O atoms of water molecules in the title compound from X-ray diffraction data at room temperature, as a result of diffuse electron density in the interlayer space. However, we could localize the positions of disordered Rb+ ions with large displacement parameters. Stacking disorder of the layers is common for layered dichalcogenides, which may contribute to the diffuse electron density. Large displacement parameters of exchangeable cations and water molecules were also reported for Ax(H2O)yTaS2 and Ax(H2O)yNbS2 (A = alkali metal) compounds (Röder et al., 1979; Wein et al. 1986; Lobert et al., 1992).
3. Electrical resistance property
The electrical resistance of Rb0.21(H2O)yWS2 increases with the decrease of temperature (80–300 K) (Fig. 2), which is characteristic of a semiconductor.
4. Synthesis and crystallization
A rubidium dithiotungstate RbxWS2 was synthesized in a solid-state reaction. The starting Rb2S2 powder was prepared in a reaction of stoichiometric amounts of Rb pieces and S powder in liquid NH3. The obtained Rb2S2 powder, W powder and S powder were mixed in the molar ratio of 1:1:1 in a filled with Ar. The mixture was ground carefully and loaded in a carbon-coated fused-silica tube. The tube was sealed under a 10−4 Torr atmosphere and slowly heated to 1123 K at 5 K min−1. After three days, the furnace was cooled down naturally to room temperature. Subsequent removal of the extra by washing with distilled water led to the isolation of crystals of Rb0.21(H2O)yWS2. The morphology and element composition were investigated by using an EDXS-equipped Hitachi S-4800 scanning electronic microscope. In addition, the Rb/W ratio in the Rbx(H2O)yWS2 crystals was determined by ICP-OES. The SEM image and EDX spectrum of Rb0.21(H2O)yWS2 crystals are shown in Fig. 3. The ratio of Rb/W from the EDXS analysis is close to 0.21, which is consistent with the the diffraction data and results from ICP–OES measurements (Table 1). The experimental powder X-ray diffraction (PXRD) pattern matches well with the simulated one (Fig. 4) by using the method (Rodríguez-Carvajal, 1993; Rp = 9.9%, Rwp = 12.6% and χ2 = 1.3). In the TG–DTA analyses (Fig. 5), one obvious endothermic effect and concomitant mass loss were observed at 343 K, which is associated with water evaporation. In order to judge whether water molecules are surface-adsorbed water or structural water, the Rb0.21(H2O)yWS2 crystals were heated up to 373 K for further PXRD measurement. The sample was prepared in an Ar-protected and sealed with vacuum tape. The (002) reflection clearly moved to higher diffraction angles, indicating the shrinkage of the due to loss of intercalated water (Fig. 6). However, it was impossible to accurately determine the water content by mass loss alone because of the interference of possible surface-adsorbed water.
|
5. details
Crystal data, data collection and structure . The localization of ordered W and S sites of the WS2 layers was unproblematic. The highest interlayer difference electron density peak was then treated as a single but partially occupied Rb site. No evidence of reflections in was found for the ordering of the Rb site. Then, the W, S sites and the underoccupied Rb site were refined with anisotropic displacement parameters. Because of very large anisotropic displacement parameters (U11 = 0.59 Å2) of the Rb site, splitting of this site was considered, resulting in a residual R1 = 0.051. Modelling the O sites as being part of this disorder, or of remaining electron density peaks in the vicinity of the Rb sites was not successful, and therefore we did not include the apparently disordered water molecules in the final structure model. The remaining maximum and minimum electron densities are located 0.87 and 1.14 Å, respectively, from the W1 site.
details are summarized in Table 2Supporting information
CCDC reference: 1920386
https://doi.org/10.1107/S2056989019007941/wm5498sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019007941/wm5498Isup2.hkl
Data collection: APEX3 (Bruker, 2015); cell
SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: publCIF (Westrip, 2010).Rb0.21(H2O)yWS2 | F(000) = 237 |
Mr = 277.23 | Dx = 5.345 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 5.703 (3) Å | Cell parameters from 68 reflections |
b = 3.2524 (18) Å | θ = 3.9–23.0° |
c = 9.423 (5) Å | µ = 39.25 mm−1 |
β = 99.724 (16)° | T = 298 K |
V = 172.27 (16) Å3 | Plate, black |
Z = 2 | 0.05 × 0.03 × 0.01 mm |
Bruker APEXII CCD diffractometer | 327 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.030 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | θmax = 24.9°, θmin = 2.2° |
Tmin = 0.251, Tmax = 0.674 | h = −6→6 |
1167 measured reflections | k = −3→3 |
352 independent reflections | l = −11→10 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters not defined |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.1024P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.124 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 2.45 e Å−3 |
352 reflections | Δρmin = −1.66 e Å−3 |
33 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
W1 | 0.19782 (11) | 0.7500 | 1.00615 (8) | 0.0371 (5) | |
S2 | 0.3744 (9) | 0.2500 | 0.8600 (6) | 0.0376 (12) | |
S3 | 0.1409 (10) | 0.2500 | 1.1850 (6) | 0.0401 (12) | |
Rb4 | 0.21 (4) | −0.2500 | 0.534 (6) | 0.14 (6) | 0.14 (7) |
Rb5 | 0.38 (2) | −0.2500 | 0.525 (8) | 0.17 (2) | 0.20 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.0319 (7) | 0.0374 (7) | 0.0423 (7) | 0.000 | 0.0073 (4) | 0.000 |
S2 | 0.034 (2) | 0.038 (3) | 0.041 (3) | 0.000 | 0.007 (2) | 0.000 |
S3 | 0.041 (3) | 0.039 (3) | 0.041 (3) | 0.000 | 0.008 (2) | 0.000 |
Rb4 | 0.28 (14) | 0.12 (4) | 0.04 (2) | 0.000 | 0.06 (4) | 0.000 |
Rb5 | 0.18 (6) | 0.24 (6) | 0.08 (3) | 0.000 | 0.01 (3) | 0.000 |
W1—S3i | 2.403 (4) | Rb4—Rb5 | 0.99 (10) |
W1—S3 | 2.403 (4) | Rb4—Rb4x | 2.9 (3) |
W1—S3ii | 2.408 (5) | Rb4—Rb4xi | 2.9 (3) |
W1—S2 | 2.454 (4) | Rb4—Rb5xii | 3.0 (3) |
W1—S2i | 2.454 (4) | Rb4—Rb5xiii | 3.0 (3) |
W1—S2iii | 2.550 (5) | Rb4—Rb4i | 3.252 (2) |
W1—W1ii | 2.7678 (15) | Rb4—Rb4v | 3.2524 (19) |
W1—W1iv | 2.7678 (15) | Rb4—Rb5i | 3.40 (3) |
S2—W1v | 2.454 (4) | Rb4—Rb5v | 3.40 (3) |
S2—W1iii | 2.550 (5) | Rb4—S2v | 3.47 (7) |
S2—Rb4 | 3.47 (7) | Rb4—S3vii | 3.58 (11) |
S2—Rb4i | 3.47 (7) | Rb5—Rb5xii | 2.23 (19) |
S2—Rb5i | 3.56 (8) | Rb5—Rb5xiii | 2.23 (19) |
S2—Rb5 | 3.56 (8) | Rb5—Rb4xii | 3.0 (3) |
S3—W1v | 2.403 (4) | Rb5—Rb4xiii | 3.0 (3) |
S3—W1ii | 2.408 (5) | Rb5—Rb5i | 3.2524 (18) |
S3—Rb5vi | 3.53 (6) | Rb5—Rb5v | 3.2524 (18) |
S3—Rb4vii | 3.58 (11) | Rb5—Rb4v | 3.40 (3) |
S3—Rb4viii | 3.63 (4) | Rb5—Rb4i | 3.40 (3) |
S3—Rb4ix | 3.63 (4) | Rb5—S3vi | 3.53 (6) |
S3—Rb5viii | 3.64 (5) | Rb5—S2v | 3.56 (8) |
S3—Rb5ix | 3.64 (5) | ||
S3i—W1—S3 | 85.18 (18) | Rb5xii—Rb4—Rb5i | 40 (3) |
S3i—W1—S3ii | 109.76 (14) | Rb5xiii—Rb4—Rb5i | 106 (4) |
S3—W1—S3ii | 109.76 (14) | Rb4i—Rb4—Rb5i | 16.9 (16) |
S3i—W1—S2 | 163.5 (2) | Rb4v—Rb4—Rb5i | 163.1 (16) |
S3—W1—S2 | 93.55 (13) | Rb5—Rb4—Rb5v | 73.1 (16) |
S3ii—W1—S2 | 86.20 (17) | Rb4x—Rb4—Rb5v | 71 (3) |
S3i—W1—S2i | 93.55 (13) | Rb4xi—Rb4—Rb5v | 140 (7) |
S3—W1—S2i | 163.5 (2) | Rb5xii—Rb4—Rb5v | 106 (4) |
S3ii—W1—S2i | 86.20 (17) | Rb5xiii—Rb4—Rb5v | 40 (3) |
S2—W1—S2i | 82.99 (18) | Rb4i—Rb4—Rb5v | 163.1 (16) |
S3i—W1—S2iii | 83.36 (18) | Rb4v—Rb4—Rb5v | 16.9 (16) |
S3—W1—S2iii | 83.36 (18) | Rb5i—Rb4—Rb5v | 146 (3) |
S3ii—W1—S2iii | 161.7 (2) | Rb5—Rb4—S2v | 87 (10) |
S2—W1—S2iii | 80.13 (16) | Rb4x—Rb4—S2v | 91.3 (12) |
S2i—W1—S2iii | 80.13 (16) | Rb4xi—Rb4—S2v | 124 (4) |
S3i—W1—W1ii | 102.78 (13) | Rb5xii—Rb4—S2v | 108 (5) |
S3—W1—W1ii | 54.97 (13) | Rb5xiii—Rb4—S2v | 79 (2) |
S3ii—W1—W1ii | 54.79 (10) | Rb4i—Rb4—S2v | 118.0 (6) |
S2—W1—W1ii | 89.78 (11) | Rb4v—Rb4—S2v | 62.0 (6) |
S2i—W1—W1ii | 140.78 (13) | Rb5i—Rb4—S2v | 116 (4) |
S2iii—W1—W1ii | 136.53 (8) | Rb5v—Rb4—S2v | 62 (2) |
S3i—W1—W1iv | 54.97 (13) | Rb5—Rb4—S2 | 87 (10) |
S3—W1—W1iv | 102.78 (13) | Rb4x—Rb4—S2 | 124 (4) |
S3ii—W1—W1iv | 54.79 (10) | Rb4xi—Rb4—S2 | 91.3 (12) |
S2—W1—W1iv | 140.78 (13) | Rb5xii—Rb4—S2 | 79 (2) |
S2i—W1—W1iv | 89.78 (11) | Rb5xiii—Rb4—S2 | 108 (5) |
S2iii—W1—W1iv | 136.53 (8) | Rb4i—Rb4—S2 | 62.0 (6) |
W1ii—W1—W1iv | 71.96 (5) | Rb4v—Rb4—S2 | 118.0 (6) |
W1v—S2—W1 | 82.99 (18) | Rb5i—Rb4—S2 | 62 (2) |
W1v—S2—W1iii | 99.87 (16) | Rb5v—Rb4—S2 | 116 (4) |
W1—S2—W1iii | 99.87 (16) | S2v—Rb4—S2 | 56.0 (12) |
W1v—S2—Rb4 | 96.3 (15) | Rb5—Rb4—S3vii | 138 (10) |
W1—S2—Rb4 | 137 (3) | Rb4x—Rb4—S3vii | 68 (4) |
W1iii—S2—Rb4 | 122 (3) | Rb4xi—Rb4—S3vii | 68 (4) |
W1v—S2—Rb4i | 137 (3) | Rb5xii—Rb4—S3vii | 133.8 (12) |
W1—S2—Rb4i | 96.3 (15) | Rb5xiii—Rb4—S3vii | 133.8 (12) |
W1iii—S2—Rb4i | 122 (3) | Rb4i—Rb4—S3vii | 90.000 (2) |
Rb4—S2—Rb4i | 56.0 (12) | Rb4v—Rb4—S3vii | 90.000 (1) |
W1v—S2—Rb5i | 150.1 (12) | Rb5i—Rb4—S3vii | 102.5 (13) |
W1—S2—Rb5i | 105.1 (13) | Rb5v—Rb4—S3vii | 102.5 (12) |
W1iii—S2—Rb5i | 106.8 (18) | S2v—Rb4—S3vii | 56.3 (7) |
Rb4—S2—Rb5i | 57.9 (7) | S2—Rb4—S3vii | 56.3 (7) |
Rb4i—S2—Rb5i | 16.1 (18) | Rb4—Rb5—Rb5xii | 132 (4) |
W1v—S2—Rb5 | 105.1 (13) | Rb4—Rb5—Rb5xiii | 132 (4) |
W1—S2—Rb5 | 150.1 (12) | Rb5xii—Rb5—Rb5xiii | 94 (10) |
W1iii—S2—Rb5 | 106.8 (18) | Rb4—Rb5—Rb4xii | 146 (2) |
Rb4—S2—Rb5 | 16.1 (18) | Rb5xii—Rb5—Rb4xii | 14.3 (18) |
Rb4i—S2—Rb5 | 57.9 (7) | Rb5xiii—Rb5—Rb4xii | 80 (8) |
Rb5i—S2—Rb5 | 54.4 (14) | Rb4—Rb5—Rb4xiii | 146 (2) |
W1v—S3—W1 | 85.18 (18) | Rb5xii—Rb5—Rb4xiii | 80 (8) |
W1v—S3—W1ii | 70.24 (14) | Rb5xiii—Rb5—Rb4xiii | 14.3 (18) |
W1—S3—W1ii | 70.24 (14) | Rb4xii—Rb5—Rb4xiii | 66 (7) |
W1v—S3—Rb5vi | 111.4 (15) | Rb4—Rb5—Rb5i | 90.00 (5) |
W1—S3—Rb5vi | 111.4 (16) | Rb5xii—Rb5—Rb5i | 43 (5) |
W1ii—S3—Rb5vi | 178 (2) | Rb5xiii—Rb5—Rb5i | 137 (5) |
W1v—S3—Rb4vii | 132.7 (12) | Rb4xii—Rb5—Rb5i | 57 (3) |
W1—S3—Rb4vii | 132.7 (11) | Rb4xiii—Rb5—Rb5i | 123 (3) |
W1ii—S3—Rb4vii | 94 (3) | Rb4—Rb5—Rb5v | 90.00 (10) |
Rb5vi—S3—Rb4vii | 83.2 (13) | Rb5xii—Rb5—Rb5v | 137 (5) |
W1v—S3—Rb4viii | 159 (2) | Rb5xiii—Rb5—Rb5v | 43 (5) |
W1—S3—Rb4viii | 109.0 (6) | Rb4xii—Rb5—Rb5v | 123 (3) |
W1ii—S3—Rb4viii | 129 (3) | Rb4xiii—Rb5—Rb5v | 57 (3) |
Rb5vi—S3—Rb4viii | 49 (5) | Rb5i—Rb5—Rb5v | 180.00 (7) |
Rb4vii—S3—Rb4viii | 47 (5) | Rb4—Rb5—Rb4v | 73.1 (17) |
W1v—S3—Rb4ix | 109.0 (6) | Rb5xii—Rb5—Rb4v | 153 (5) |
W1—S3—Rb4ix | 159 (2) | Rb5xiii—Rb5—Rb4v | 60 (6) |
W1ii—S3—Rb4ix | 129 (3) | Rb4xii—Rb5—Rb4v | 140 (3) |
Rb5vi—S3—Rb4ix | 49 (5) | Rb4xiii—Rb5—Rb4v | 74 (4) |
Rb4vii—S3—Rb4ix | 47 (5) | Rb5i—Rb5—Rb4v | 163.1 (16) |
Rb4viii—S3—Rb4ix | 53.3 (7) | Rb5v—Rb5—Rb4v | 16.9 (16) |
W1v—S3—Rb5viii | 147.5 (16) | Rb4—Rb5—Rb4i | 73.1 (16) |
W1—S3—Rb5viii | 103.9 (12) | Rb5xii—Rb5—Rb4i | 60 (6) |
W1ii—S3—Rb5viii | 142.2 (16) | Rb5xiii—Rb5—Rb4i | 153 (5) |
Rb5vi—S3—Rb5viii | 36 (3) | Rb4xii—Rb5—Rb4i | 74 (4) |
Rb4vii—S3—Rb5viii | 61 (4) | Rb4xiii—Rb5—Rb4i | 140 (3) |
Rb4viii—S3—Rb5viii | 15.7 (16) | Rb5i—Rb5—Rb4i | 16.9 (16) |
Rb4ix—S3—Rb5viii | 55.8 (6) | Rb5v—Rb5—Rb4i | 163.1 (16) |
W1v—S3—Rb5ix | 103.9 (12) | Rb4v—Rb5—Rb4i | 146 (3) |
W1—S3—Rb5ix | 147.5 (16) | Rb4—Rb5—S3vi | 125 (9) |
W1ii—S3—Rb5ix | 142.2 (16) | Rb5xii—Rb5—S3vi | 75 (3) |
Rb5vi—S3—Rb5ix | 36 (3) | Rb5xiii—Rb5—S3vi | 75 (3) |
Rb4vii—S3—Rb5ix | 61 (4) | Rb4xii—Rb5—S3vi | 67 (4) |
Rb4viii—S3—Rb5ix | 55.8 (6) | Rb4xiii—Rb5—S3vi | 67 (4) |
Rb4ix—S3—Rb5ix | 15.7 (16) | Rb5i—Rb5—S3vi | 90.000 (5) |
Rb5viii—S3—Rb5ix | 53.0 (8) | Rb5v—Rb5—S3vi | 90.000 (2) |
Rb5—Rb4—Rb4x | 141 (2) | Rb4v—Rb5—S3vi | 100 (3) |
Rb5—Rb4—Rb4xi | 141 (2) | Rb4i—Rb5—S3vi | 100 (3) |
Rb4x—Rb4—Rb4xi | 69 (9) | Rb4—Rb5—S2v | 77 (8) |
Rb5—Rb4—Rb5xii | 34 (2) | Rb5xii—Rb5—S2v | 128 (3) |
Rb4x—Rb4—Rb5xii | 157 (2) | Rb5xiii—Rb5—S2v | 87 (3) |
Rb4xi—Rb4—Rb5xii | 107.5 (14) | Rb4xii—Rb5—S2v | 123 (3) |
Rb5—Rb4—Rb5xiii | 34 (2) | Rb4xiii—Rb5—S2v | 92.3 (10) |
Rb4x—Rb4—Rb5xiii | 107.5 (13) | Rb5i—Rb5—S2v | 117.2 (7) |
Rb4xi—Rb4—Rb5xiii | 157 (2) | Rb5v—Rb5—S2v | 62.8 (7) |
Rb5xii—Rb4—Rb5xiii | 66 (7) | Rb4v—Rb5—S2v | 59.7 (19) |
Rb5—Rb4—Rb4i | 90.00 (5) | Rb4i—Rb5—S2v | 112 (3) |
Rb4x—Rb4—Rb4i | 125 (5) | S3vi—Rb5—S2v | 55.4 (8) |
Rb4xi—Rb4—Rb4i | 55 (5) | Rb4—Rb5—S2 | 77 (8) |
Rb5xii—Rb4—Rb4i | 57 (3) | Rb5xii—Rb5—S2 | 87 (3) |
Rb5xiii—Rb4—Rb4i | 123 (3) | Rb5xiii—Rb5—S2 | 128 (3) |
Rb5—Rb4—Rb4v | 90.000 (19) | Rb4xii—Rb5—S2 | 92.3 (10) |
Rb4x—Rb4—Rb4v | 55 (5) | Rb4xiii—Rb5—S2 | 123 (3) |
Rb4xi—Rb4—Rb4v | 125 (5) | Rb5i—Rb5—S2 | 62.8 (7) |
Rb5xii—Rb4—Rb4v | 123 (3) | Rb5v—Rb5—S2 | 117.2 (7) |
Rb5xiii—Rb4—Rb4v | 57 (3) | Rb4v—Rb5—S2 | 112 (3) |
Rb4i—Rb4—Rb4v | 180.00 (10) | Rb4i—Rb5—S2 | 59.7 (19) |
Rb5—Rb4—Rb5i | 73.1 (16) | S3vi—Rb5—S2 | 55.4 (8) |
Rb4x—Rb4—Rb5i | 140 (7) | S2v—Rb5—S2 | 54.4 (14) |
Rb4xi—Rb4—Rb5i | 71 (3) |
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x, −y+2, −z+2; (v) x, y−1, z; (vi) −x+1, −y, −z+2; (vii) −x, −y, −z+2; (viii) x, y+1, z+1; (ix) x, y, z+1; (x) −x, −y−1, −z+1; (xi) −x, −y, −z+1; (xii) −x+1, −y, −z+1; (xiii) −x+1, −y−1, −z+1. |
Funding information
This work was supported financially by the National Key Research and Development Program (grant No. 2016YFB0901600), the National Science Foundation of China (grant No. 21871008), the Science and Technology Commission of Shanghai (grant Nos. 16ZR1440500 and 16JC1401700), the Key Research Program of the Chinese Academy of Sciences (grants Nos. QYZDJ-SSW-JSC013 and KGZD-EW-T06) and the CAS Center for Excellence in Superconducting Electronics.
References
Brandenburg, K. (2004). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2015). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fang, Y. Q., Hu, X. Z., Zhao, W., Pan, J., Wang, D., Bu, K. J., Mao, Y. L., Chu, S. F., Liu, P., Zhai, T. Y. & Huang, F. Q. (2019). J. Am. Chem. Soc. 141, 790–793. Web of Science CrossRef CAS PubMed Google Scholar
Fang, Y. Q., Pan, J., He, J. Q., Luo, R. C., Wang, D., Che, X. L., Bu, K. J., Zhao, W., Liu, P., Mu, G., Zhang, H., Lin, T. Q. & Huang, F. Q. (2018). Angew. Chem. Int. Ed. 130, 1246–1249. CrossRef Google Scholar
Graf, H. A., Lerf, A. & Schöllhorn, R. (1977). J. Less-Common Met. 55, 213–220. CrossRef ICSD CAS Web of Science Google Scholar
Huster, J. (1978). Z. Anorg. Allg. Chem. 447, 89–96. CrossRef ICSD CAS Web of Science Google Scholar
Lerf, A. & Schöllhorn, R. (1977). Inorg. Chem. 16, 2950–2956. CrossRef CAS Web of Science Google Scholar
Lobert, M., Müller-Warmuth, W., Katzke, H. & Schöllhorn, R. (1992). Ber. Bunsenges. Phys. Chem. 96, 1564–1568. CrossRef CAS Web of Science Google Scholar
Omloo, W. P. & Jellinek, F. (1970). J. Less-Common Met. 20, 121–129. CrossRef ICSD CAS Web of Science Google Scholar
Röder, U., Müller–Warmuth, W. & Schöllhorn, R. (1979). J. Chem. Phys. 70, 2864–2870. Google Scholar
Rodríguez-Carvajal, J. (1993). Physica B, 192, 55–69. CrossRef Web of Science Google Scholar
Schöllhorn, R. & Weiss, A. (1974). J. Less-Common Met. 36, 229–236. Google Scholar
Schutte, W. J., De Boer, J. L. & Jellinek, F. (1987). J. Solid State Chem. 70, 207–209. CrossRef ICSD CAS Web of Science Google Scholar
Sernetz, F., Lerf, A. & Schöllhorn, R. (1974). Mater. Res. Bull. 9, 1597–1602. CrossRef CAS Web of Science Google Scholar
Shang, C., Fang, Y. Q., Zhang, Q., Wang, N. Z., Wang, Y. F., Liu, Z., Lei, B., Meng, F. B., Ma, L. K., Wu, T., Wang, Z. F., Zeng, C. G., Huang, F. Q., Sun, Z. & Chen, X. H. (2018). Phys. Rev. B, 98, 184513–184523. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Wein, E., Müller-Warmuth, W. & Schoöllhorn, R. (1986). Ber. Bunsenges. Phys. Chem. 90, 158–162. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Whittingham, M. S. (1978). Prog. Solid State Chem. 12, 41–99. CrossRef CAS Web of Science Google Scholar
Yu, Y. F., Nam, G. H., He, Q. Y., Wu, X. J., Zhang, K., Yang, Z. Z., Chen, J. Z., Ma, Q. L., Zhao, M. T., Liu, Z. Q., Ran, F. R., Wang, X. Z., Li, H., Huang, X., Li, B., Xiong, Q. H., Zhang, Q., Liu, Z., Gu, L., Du, Y., Huang, W. & Zhang, H. (2018). Nat. Chem. 10, 638–643. Web of Science CrossRef CAS PubMed Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.