Home Physical Sciences The crystal structure of bis(trimethylsulfoxonium) catena-poly[µ2-hexabromido-indium(III)sodium(I)] C6H18O2S2NaInBr6
Article Open Access

The crystal structure of bis(trimethylsulfoxonium) catena-poly[µ2-hexabromido-indium(III)sodium(I)] C6H18O2S2NaInBr6

  • Shifeng Jin ORCID logo EMAIL logo and Jiali Lu ORCID logo
Published/Copyright: October 10, 2023

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.

CCDC no.: 2284914

Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

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]
Table 2:

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*
  1. 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 [58]. 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).


Corresponding author: Shifeng Jin, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China; and School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 101408, China, E-mail:

Funding source: National Key Research and Development Program of China

Award Identifier / Grant number: (Grant No. 2018YFE0202600)

  1. Research ethics: Not applicable.

  2. Author contributions: The authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Competing interests: The authors state no conflict of interest.

  4. Research funding: We gratefully acknowledge support by the National Key Research and Development Program of China (Grant No. 2018YFE0202600) for financial support.

  5. 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

Received: 2023-08-18
Accepted: 2023-09-27
Published Online: 2023-10-10
Published in Print: 2023-12-15

© 2023 the author(s), published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

Articles in the same Issue

  1. Frontmatter
  2. New Crystal Structures
  3. Crystal structure of bis(dimethylammonium) poly[(μ4-1,1′-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylato))-κ6O1, N2:O2:O3:O1′,N2′]nickel (II)], C22H26N6NiO8
  4. Hydrothermal synthesis and crystal structure of catena-poly[diaqua-bis(μ2-4-((pyridin-4-ylmethyl)amino)benzoato-κ2N:O)cobalt(II)] 4,4′-bipyridine – water (1/2/2)
  5. Crystal structure of (2S,3S,4S,5S, Z)-2,3,5,6-tetrakis(benzyloxy)-4-hydroxyhexanal oxime, C34H37NO6
  6. The crystal structure of hexakis(3-thiophenecarboxylato-κ2O,O″)-bis(1,10-phenanthroline-κ2N,N′) trimanganese(II), C54H34N4O12S6Mn3
  7. Crystal structure of catena-poly[(μ2-1,4-di(pyridin-4-yl)benzene-κ2N:N′)-(4-bromobenzoate-κ2O:O′)-(μ-2-bromobenzoate-κ2O,O′)nickel(II)] – water (2/1), C30H21Br2N2NiO4.5
  8. The crystal structure of poly[(μ3-1,3-phenylenedioxydiacetate-κ5O,O,O′,O″,O‴)-bis(4′-(4-(1H-imidazol-1-yl)phenyl)-4,2′:6′,4″-terpyridine-kN) cadmium(II)], C58H42CdN10O6
  9. The crystal structure of 5-chloro-6′-methyl-3-(4-(methylsulfonyl)phenyl)-[2,3′-bipyridin]-1′-ium 4-methylbenzenesulfonate
  10. Crystal structure of poly[(μ-benzoato)-(μ-cis-4–hydroxy-D-proline)lithium], C12H14LiNO5
  11. The crystal structure of catena-poly[aqua-(4-iodopyridine-2,6-dicarboxylato-κ3N,O,O)-copper(II)] monohydrate, C7H6NO6ICu
  12. The crystal structure of catena-[diaqua-(4-acetylphenoxyacetato-κ2O,O)-bis(4-acetylphenoxyacetato-κ3O,O:O)-dihydrate-lanthanum(III)]–4,4′-bipyridine (2/1), C35H35NO14La
  13. The crystal structure of catena-poly[(4-iodopyridine-2,6-dicarboxylato-κ4 O,N,O′,O′′)(4-imidazol-1-yl-pyridine-κN)copper(II)], C15H9N4O4ICu
  14. Crystal structure of polybis(μ 4-3,5-dicarboxylatopyrazol-1-yl)-bis(N,N-dimethylformamide)tri-copper(II)–acetonitrile (1/2), C20H22Cu3N8O10
  15. Crystal structure of poly[(μ2-5-hydroxy-isophthalato-κ4O,O′:O″,O‴)-(μ2-1,5-bis(imidazol-2-methyl)pentane-κ2N:N′)cadmium(II)], C21H24CdN4O5
  16. The crystal structure of poly[bis(μ2-1,4-bi(1-imidazolyl)benzene-κ2N:N′)bis(μ2-4,4′-methylenebis(3-hydroxy-2-naphthoate)-κ2O:O′)cobalt(II)], C35H24CoN4O6
  17. The crystal structure of a cobalt-vanadium-oxido hydrate
  18. The crystal structure of catena-poly[(μ 2-2H-1,2,3-triazole-4,5-dicarboxylato-κ 2 O, O′)-(μ 2-1,3-bis((1H-imidazol-1-yl)methyl)benzene-κ 2 N,N′) zinc(II)], C18H15N7O4Zn
  19. Crystal structure of poly[diaqua-(bis(m2-1,4-bis(imidazol-1-ylmethyl)benzene)-κ2N,N′-manganese] dichloride, C28H32MnN8O2Cl2
  20. The crystal structure of 9,10-dimethoxy-5,6-dihydro-[1,3]dioxolo[4,5-g]isoquinolino [3,2-a]isoquinolin-7-ium (E)-3-(4-nitrophenyl)acrylate pentahydrate, C29H34N2O13
  21. Crystal structure of poly[(μ6-ammoniotris(methylene))tris(hydrogen phosphonato)cadmium(II)], C3H10CdNO9P3
  22. Crystal structure of Zn2[(1,1′-(hexane-1,6-diyl)bis(3-(pyridin-3-yl)urea))·(H2O)2·(DMF)2·(SO4)2], C24H50N8O18S2Zn2
  23. The crystal structure of 2-anilino-1,4-naphthoquinone, C10H11NO2
  24. Crystal structure of (E)-2-(2-(4-(diethylamino)styryl)-1-ethyl-1,4-dihydroquinolin-4-yl) malononitrile, C26H26N4
  25. Crystal structure of ethyl 2-((2,6-dichloro-4-(cyanomethyl)phenyl) amino)benzoate, C17H14Cl2N2O2
  26. Synthesis and crystal structure of 2-(3-oxo-3-phenylpropyl)isoindoline-1,3-dione, C17H13NO3
  27. The crystal structure of bis(acetonitrile-κ1N)tetrakis(μ2-2,6-difluorobenzoato-κ2O:O′)rhodium(II) (Rh–Rh), C32H18F8O8N2Rh2
  28. The crystal structure of a new polymorph of 6-hydroxy-2-naphthoic acid, C11H8O3
  29. The crystal structure of [(8-carboxymethoxy-quinoline-2-carboxylate-κ4N,O,O,O)-2,2′-bipyridine-κ2N-copper(II)] tetrahydrate, C22H23N3O9Cu
  30. The crystal structure of ethyl 4-hydroxy-2-(4-methoxyphenyl)-5-oxo-1-(2-oxo-2H-chromen-6-yl)-2,5-dihydro-1H-pyrrole-3-carboxylate, C23H19NO7
  31. Crystal structure of 7-hydroxy-3,4-dihydronaphthalen-1(2H)-one, C10H10O2
  32. Crystal structure of bis(tetrapropylammonium) dodecacarbonyltetratelluridotetraferrate(2-), (Pr4N)2[Fe4Te4(CO)12]
  33. The crystal structure of poly[bis(μ2−3−aminopyridine−4−carboxylatoκ2N:O)Zinc(II)], [Zn(C6H5N2O2)2] n
  34. The crystal structure of methyl 5-nitro-2-(tosyloxy)benzoate, C15H13NO7S
  35. The crystal structure of 18-crown-6 ― tetraaqua-dichlorido-di-μ2-chloridodicopper(II) (2/1), C12H32O10Cu2Cl4
  36. Crystal structure of 6,6a,7,8,9,10-hexahydro-5H-pyrazino [2,3-e]pyrido[1,2-a]pyrazine, C10H14N4
  37. Crystal structure of catena-poly-{diaqua-bis[μ-(((4-chlorophenyl)sulfonyl)glycinato-κO)](μ2-4, 4′-bipyridine-κ2N:N′)cobalt(II)} dihydrate, C26H30Cl2CoN4O12S2
  38. Crystal structure of bis{N′-[1,3-diphenylprop-2-en-1-ylidene]-N-phenylcarbamohydrazonothioato}zinc(II), C44H36N6S2Zn
  39. Crystal structure of tetraaqua-bis(((4-chlorophenyl)sulfonyl)glycinato-κO)cobalt(II) dihydrate, C16H26Cl2CoN2O14S2
  40. Crystal structure of 2-(5-phenyl-1-(quinolin-2-yl)-4,5-dihydro-1H-pyrazol-3-yl)phenol, C24H19N3O
  41. Crystal structure of 2-((2-fluoro-4-(trifluoromethyl)phenyl)(hydroxy)methyl)-7-methoxy-3,4-dihydronaphthalen-1((2H))-one, C19H16F4O3
  42. Crystal structure of 2-amino-4-(2-fluoro-3-(trifluoromethyl)phenyl)-9-methoxy-1,4,5,6-tetrahydrobenzo[h]quinazolin-3-ium chloride, C20H18ClF4N3O
  43. Crystal structure of (2-phenylimino methylquinoline-κ 2 N,N′)-bis(1–phenylpyrazole-κ 2 C,N)-iridium(III) hexafluorophosphate, C34H26F6IrN6P
  44. Crystal structure of (3-hydroxy-4-methoxyphenyl)(pyrrolidin-1-yl)methanone, C12H15NO3
  45. The crystal structure of bis(trimethylsulfoxonium) catena-poly[µ2-hexabromido-indium(III)sodium(I)] C6H18O2S2NaInBr6
  46. Crystal structure of N-cyclopropyl-3-hydroxy-4-methoxybenzamide, C11H13NO3
  47. The crystal structure of (bis(benzimidazol-2-yl-methyl)amine-κ3N,N,N )-(dihydrogen L-malate-κ2O,O )copper(II) perchlorate dihydrate, CuC20H24ClN5O12
  48. Crystal structure of (1E,1′E)-4,4′-(9,9-diethyl-9H-fluorene-2,7-diyl)dibenzaldehyde dioxime, C31H28N2O2
  49. Crystal structure of diethyl 1,9-bis(4-fluorophenyl)-4,6-diphenylhexahydro-3H-2,7,3,5-(epimethanetriyliminomethanetriyl)cyclopenta [b]pyridine-3,7(2H)-dicarboxylate, C40H36F2N2O4
  50. Crystal structure of bis(benzene-1 carboxylato-O 3,5-carboxyl-κ1O)-[(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N′′,N′′′)nickel(II) ─ benzene-1,3,5-tricarboxylic acid ─ water (1/2/4), C52H66N4NiO28
  51. Crystal structure of 1,4-dibromo-2,5-bis(2-methoxyethoxy)benzene-1,4-diol, C12H16Br2O4
  52. Crystal structure of dicarbonyl[N,N′-(1,2-dimethyl-1,2-ethanediylidene)bis[2,6-bis(1-methylethyl)benzenamine]-N,N′]nickel(0), C30H40N2NiO2
  53. Crystal structure of 1,4-dibromo-2,5-bis(prop-2-yn-1-yloxy)benzene, C12H8Br2O2
  54. Crystal structure of O-(3-(benzo[d]thiazol-2-yl)naphthalen-2-yl) O-phenyl carbonothioate, C24H15NO2S2
  55. The crystal structure of (E)-4-fluoro-N′-(1-(4-hydroxyphenyl)propylidene)benzohydrazide, C16H15FN2O2
  56. Crystal structure of (E)-1-(benzo[d]thiazol-2-yl)-N-(4,5-dihydropyren-2-yl)methanimine, C24H16N2S
  57. Crystal structure of 3-((4-bromophenyl)thio)-1H-indole, C14H10BrNS
  58. Synthesis and crystal structure of 1-((7-hydroxy-3-(4-hydroxy-3-nitrophenyl)-4-oxo-4H-chromen-8-yl)methyl)piperidin-1-ium-4-carboxylate monohydrate, C22H22N2O9
  59. Synthesis and crystal structure of (3E,5S,10S,13S,14S,17Z)-17-ethylidene-10,13-dimethylhexadecahydro-3H-cyclopenta[α]phenanthren-3-one O-(methacryloyl) oxime, C50H74N2O4
  60. Crystal structure of the hydrogen storage active phase La12Mg46LiMn
  61. The crystal structure of the salt: 4-((1,3-dioxoisoindolin-2-yl)carbamoyl)pyridine-1-ium 2-carboxybenzoate, C14H10N3O3·C8H5O4
  62. Crystal structure of (2-(2-pyridine)-benzimidazole-κ2 N,N′)-bis(1-phenylpyrazole-κ2 C,N)iridium(III) hexafluorophosphate, C30H22F6IrN7P
  63. Crystal structure of dichlorido-bis[2-(2,4-difluorophenyl)pyridine-κ1N]platinum(II), C22H14Cl2F4N2Pt
  64. Crystal structure of (5R,8R,9R,10R,12R,13R,14R, 17S,17Z)-2-((3-fluoropyridin-4-yl)methylene)-12-hydroxy-4,4,8,10,14-pentamethyl-17-((R)-2,6,6-trimethyltetrahydro-2H-pyran-2-yl)hexadecahydro-3H-cyclopenta[a]phenanthren-3-one, C36H52FNO3
Downloaded on 4.2.2026 from https://www.degruyterbrill.com/document/doi/10.1515/ncrs-2023-0377/html
Scroll to top button