Abstract
C6H18O2S2NaInBr6, orthorhombic, Pmn21 (no. 31), a = 10.5451(3) Å, b = 7.1169(2) Å, c = 13.7034(4) Å, V = 1028.42(5) Å3, Z = 2, Rgt(F) = 0.0354, wRref(F2) = 0.0923, T = 293 K.
Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colourless block |
| Size: | 0.1 × 0.1 × 0.1 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 13.0 mm−1 |
| Diffractometer, scan mode: | Bruker SMART APEX-II, φ and ω |
| θmax, completeness: | 28.3°, 97 % |
| N(hkl)measured, N(hkl)unique, Rint: | 11,509, 2123, 0.060 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2σ(Iobs), 2060 |
| N(param)refined: | 101 |
| Programs: | Bruker [1], SHELX [2, 3], Olex2 [4] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/Ueq |
|---|---|---|---|---|
| In1 | 1.000000 | 0.34184 (11) | 0.80861 (7) | 0.01694 (17) |
| Br1 | 0.82409 (8) | 0.12288 (13) | 0.72308 (7) | 0.0263 (2) |
| Br2 | 1.000000 | 0.10833 (18) | 0.96279 (9) | 0.0255 (3) |
| Br3 | 0.82369 (8) | 0.55848 (13) | 0.89490 (7) | 0.0263 (2) |
| Br4 | 1.000000 | 0.57592 (17) | 0.65460 (8) | 0.0260 (3) |
| S1 | 0.500000 | 0.4728 (4) | 0.7017 (2) | 0.0214 (5) |
| S2 | 1.000000 | 0.0245 (4) | 0.41421 (19) | 0.0208 (5) |
| Na1 | 1.000000 | 0.8419 (6) | 0.8077 (4) | 0.0138 (7) |
| O1 | 0.500000 | 0.4330 (14) | 0.8045 (8) | 0.034 (2) |
| O2 | 1.000000 | 0.0554 (14) | 0.3096 (8) | 0.033 (2) |
| C1 | 0.500000 | 0.2694 (19) | 0.6284 (10) | 0.030 (3) |
| H1Aa | 0.577438 | 0.201220 | 0.638438 | 0.045* |
| H1Ba | 0.493338 | 0.304824 | 0.560952 | 0.045* |
| H1Ca | 0.429223 | 0.191468 | 0.645730 | 0.045* |
| C2 | 0.6330 (10) | 0.6017 (15) | 0.6660 (8) | 0.033 (2) |
| H2A | 0.708395 | 0.538805 | 0.687799 | 0.050* |
| H2B | 0.629269 | 0.724859 | 0.694363 | 0.050* |
| H2C | 0.634459 | 0.612156 | 0.596152 | 0.050* |
| C3 | 1.000000 | 0.2354 (19) | 0.4800 (11) | 0.033 (3) |
| H3Aa | 0.935173 | 0.316903 | 0.454936 | 0.050* |
| H3Ba | 1.081130 | 0.295355 | 0.473561 | 0.050* |
| H3Ca | 0.983697 | 0.209671 | 0.547626 | 0.050* |
| C4 | 0.8673 (11) | −0.0982 (16) | 0.4541 (8) | 0.039 (3) |
| H4A | 0.877036 | −0.229105 | 0.438947 | 0.058* |
| H4B | 0.793097 | −0.050243 | 0.422028 | 0.058* |
| H4C | 0.858381 | −0.083075 | 0.523384 | 0.058* |
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aOccupancy: 0.5.
1 Source of material
All chemicals used were purchased commercially. An amount of 0.2 mol of trimethylsulfoxonium bromide, 0.1 mol of sodium bromide, and 0.1 mol of indium bromide were dissolved in deionized water. To prevent the hydrolysis of the indium cation, 2 mL of hydrobromic acid was added. Bulk, colorless crystals were obtained by slow evaporation of the saturated solution.
2 Experimental details
The Flack parameter (x) larger than 0 indicates that the structure may be centrosymmetric. Based on the available isomorphous structures, a potential space group could be Pnma (no. 62). However, subsequent nonlinear optical experiments shows that this material is second harmonic generation active, proving it is non-centrosymmetric. Detailed structure analysis reveals the ordering of In and Na atoms in two distinct sites, making the slip plane perpendicular to the c-axis in Pnma (no. 62) impossible (cf. right part of the figure). Finally, the correct space group is determined to be Pmn21 (no. 31), which is a subgroup of Pnma (no. 62). For all hydrogen atoms, their positions were assigned geometrically based on their corresponding parent carbon atoms. The hydrogen atoms bonded to C2 and C3 exhibit orientational disorder, with an occupancy of 0.5 each.
3 Comment
Organic–inorganic metal halide hybrids are an emerging generation of functional materials with potential applications in ferroelectrics, piezoelectrics, pyroelectrics, barocalorics, and magnetics [5–8]. The title compound is a new one-dimensional organic–inorganic composite double perovskite compound. According to the single-crystal structure analysis, the compound consists of two parts: organic C3H9OS cations and one-dimensional chains formed by the coplanar and alternating NaBr6 and InBr6 octahedra, the chain is almost along the b-axis (cf. left part of the figure). Similar one-dimensional organic–inorganic metal halide hybrids were widely reported such as C3H9OSCdCl3, C3H9OSCdBr3, C3H9OSPbBr3 and C3H9OSPbl3 [9, 10] with the space group Pnma (no. 62). However, it is important to note that while the organic motifs remain the same, the inorganic framework in the title double perovskite compound differs from those previously reported. In the title structure, the central metal atoms within the octahedra are arranged alternately as In and Na, distinguishing it from the aforementioned centrosymmetric structures (cf. the figure). This arrangement disrupts the slip plane perpendicular to the c-axis along the one-dimensional chain, resulting in a reduction of the space group from Pnma (no. 62) to Pmn21 (no. 31).
Funding source: National Key Research and Development Program of China
Award Identifier / Grant number: (Grant No. 2018YFE0202600)
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Research ethics: Not applicable.
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Author contributions: The authors have accepted responsibility for the entire content of this manuscript and approved its submission.
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Competing interests: The authors state no conflict of interest.
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Research funding: We gratefully acknowledge support by the National Key Research and Development Program of China (Grant No. 2018YFE0202600) for financial support.
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Data availability: The raw data can be obtained on request from the corresponding author.
References
1. BRUKER. SAINT. Version 8.23B; Bruker AXS Inc.: Madison, Wisconsin, USA, 2013.Search in Google Scholar
2. Sheldrick, G. M. SHELXTL – integrated space-group and crystal-structure determination. Acta Crystallogr. 2015, A71, 3–8; https://doi.org/10.1107/s2053273314026370.Search in Google Scholar PubMed PubMed Central
3. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. 2015, C71, 3–8; https://doi.org/10.1107/s2053229614024218.Search in Google Scholar PubMed PubMed Central
4. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K., Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 2009, 42, 339–341; https://doi.org/10.1107/s0021889808042726.Search in Google Scholar
5. Wei, Z. H., Jiang, Z. T., Zhang, X. X., Li, M. L., Tang, Y. Y., Chen, X. G., Cai, H., Xiong, R. G. Rational design of ceramic-like molecular ferroelectric by quasi-spherical theory. J. Am. Chem. Soc. 2020, 142, 1995–2000; https://doi.org/10.1021/jacs.9b11665.Search in Google Scholar PubMed
6. Zhou, J., Jin, S., Chai, C., Hao, M., Zhong, X., Ying, T., Guo, J., Chen, X. Discovery of amantadine formate: toward achieving ultrahigh pyroelectric performances in organics. Innovation 2022, 3, 100204; https://doi.org/10.1016/j.xinn.2021.100204.Search in Google Scholar PubMed PubMed Central
7. Li, B., Kawakita, Y., Ohira-Kawamura, S., Sugahara, T., Wang, H., Wang, J., Chen, Y., Kawaguchi, S. I., Kawaguchi, S., Ohara, K., Li, K., Yu, D., Mole, R., Hattori, T., Kikuchi, T., Yano, S., Zhang, Z., Zhang, Z., Ren, W., Lin, S., Sakata, O., Nakajima, K., Zhang, Z. Colossal barocaloric effects in plastic crystals. Nature 2019, 567, 506–510; https://doi.org/10.1038/s41586-019-1042-5.Search in Google Scholar PubMed
8. Chai, C., Zhou, J., Hao, M., Li, Q., Lu, J., Jin, S., Chen, X. Nanostructuring of rare-earth-based single-molecule magnets as long-range ordered arrays in the framework of organic metal halide perovskites. Angew. Chem. Int. Ed. 2023, 62, e202300413; https://doi.org/10.1002/anie.202300413.Search in Google Scholar PubMed
9. Puget, R., Jannin, M., De Brauer, C., Perret, R. Structures of trimethyloxosulfonium Salts. V. The catena-tri-chloro-cadmate and the catena-tri-bromo-cadmate. Acta Crystallogr. 1991, C47, 1803–1805; https://doi.org/10.1107/s0108270190013701.Search in Google Scholar
10. Pipitone, C., Giannici, F., Martorana, A., García-Espejo, G., Carlotto, S., Casarin, M., Guagliardi, A., Masciocchi, N. Heterovalent Bi III/Pb II ionic substitution in one-dimensional trimethylsulfoxonium halide pseudo-perovskites (X = I, Br). J. Phys. Chem. C 2021, 125, 11728–11742; https://doi.org/10.1021/acs.jpcc.1c02571.Search in Google Scholar
© 2023 the author(s), published by De Gruyter, Berlin/Boston
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