Three-dimensional organic–inorganic hybrid sodium halide perovskite: C₄H₁₂N₂·NaI₃ and a hydrogen-bonded supramolecular three-dimensional network in 3C₄H₁₂N₂·NaI₄·3I·H₂O

Abstract

Two new organic–inorganic hybrid sodium halides based on the piperazinediium dication have been synthesized, with C4H12N2·NaI3 presenting a three-dimensional perovskite structure and 3C4H12N2·NaI4·3I·H2O showing a three-dimensional hydrogen-bonded supra­molecular network.

Cs3Cu4In2Cl13 Nanocrystals: A Perovskite-Related Structure with Inorganic Clusters at A Sites

“…), 10 with rare examples of divalent organic cations, such as piperazine-1,4-diium (C4H12N4 2+ ) and a few others. [11][12][13][14] In our efforts to explore new metal halide materials, we have discovered a novel perovskite-related structure with a general formula Cs3Cu4In2Cl13, in the form of colloidal nanocrystals (NCs). The structure of these NCs was determined using three-dimensional electron diffraction (3D ED) on single NCs in combination with powder x-ray diffraction (XRD), as is discussed in detail below.…”

Syntheses and structures of piperazin-1-ium ABr2 (A = Cs or Rb): hybrid solids containing `curtain wall' layers of face- and edge-sharing ABr6 trigonal prisms

“…A search of the Cambridge Structural Database(CSD, version 5.40, last update 19 May 2019;Groom et al, 2016) for the mono-protonated C 4 H 11 N 2 + cation returned 55 crystal structures but none of them bear a close resemblance to the title compound. As noted in the chemical context section, the doubly protonated C 4 H 12 N 2 2+ species occurs in several hybrid RMX 3 perovskites including C 4 H 12 N 2 ÁACl 3 ÁH 2 O with A = K (CSD refcode GUYMIX), Rb (GUYMOD) and Cs (GUYMUJ)(Paton & Harrison, 2010) and C 4 H 12 N 2 ÁNaI 3 (MEXMAG;Chen et al, 2018).…”

“…; X = halide ion) octahedral networks have attracted intense interest because of their remarkable photophysical properties (Xu et al, 2019;Stylianakis et al, 2019;Zuo et al, 2019). A number of different organic cations occur in these hybrid structures, one of which is the doubly protonated C 4 H 12 N 2 2+ piperizinium (or piperazin-1,4-diium) ion as found in the C 4 H 12 N 2 ÁACl 3 ÁH 2 O (A = K, Rb, Cs) family (Paton & Harrison, 2010) and C 4 H 12 N 2 ÁNaI 3 (Chen et al, 2018).…”

Syntheses and crystal structures of a new family of hybrid perovskites: C5H14N2·ABr3·0.5H2O (A= K, Rb, Cs)

“…Notable features of these structures include the 'inverse' charges of the cations (R 2+ > M + ) compared to oxide perovskites, the inclusion of ISSN 2056-9890 water molecules of hydration in the C 4 H 12 N 2 ÁACl 3 ÁH 2 O (A = K, Rb, Cs) series and a novel chiral perovskite analogue (space group P3 2 21) for C 6 H 14 N 2 ÁRbCl 3 . This family has recently been extended by a number of phases (see Database survey) including C 6 H 14 N 2 ÁRbBr 3 and C 7 H 16 N 2 ÁRbI 3 (C 7 H 16 N 2 2+ = 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4diium) (Zhang et al, 2017), C 4 H 12 N 2 ÁRbBr 3 (C 4 H 12 N 2 2+ = 3ammoniopyrrolidinium) (Pan et al, 2017) and C 4 H 12 N 2 ÁNaI 3 (Chen et al, 2018), some of which have significant physical properties such as ferroelectricity.…”

“…Comparison of the structures of (a) MEXMAG (redrawn fromChen et al, 2018), (b) (I) and (c) GUYMIX (redrawn fromPaton and Harrison, 2010). In MEXMAG, (I) and GUYMIX, the two octahedral cages shown are stacked in the [001], [100] and [001] directions, respectively.…”