The crystal structure of the title compound contains infinite inorganic two-dimensional layers formed by [GeI6]4− octahedra. These layers are interleaved with the organic 2-iodoethylammonium cations.
Keywords: crystal structure, hybrid perovskite, germanium(II), organic cation
Abstract
The title compound is a germanium-based hybrid metal halide that represents a less-toxic alternative to more popular lead-based analogues in optoelectronic applications. {(2-IC2H4NH3)2[GeI4]}n is composed of infinite inorganic layers that are formed by [GeI6]4− octahedra connected in a corner-sharing manner with four equatorial I atoms. The organic (2-IC2H4NH3)+ cations interleave the inorganic layers. There are two types of 2-iodoethylammonium cations, with synclinal and antiperiplanar conformations. The organic cations interact with the inorganic layers through hydrogen bonds and I⋯I contacts. The crystal under investigation was twinned by a 180° rotation around [100].
1. Chemical context
The number of functional materials with exceptional physical properties has been significantly expanded by numerous hybrid organic–inorganic halide perovskites in recent decades. These materials frequently display semiconducting properties that allow their application in various photovoltaic and optoelectronic devices (Zhao & Zhu, 2016 ▸). Hybrid perovskites have been shown to form effective active layers in solar cells (Huang et al., 2023 ▸), light-emitting diodes (Ngai et al., 2023 ▸), photodetectors (Moeini et al., 2022 ▸) and thermolectronic cells (Ngai et al., 2023 ▸).
Hybrid halide perovskites are compounds of the ABX3 type (where A is an organic cation, B is a metal cation and X is a halide anion), which contain fundamental BX6 octahedra that are organized in all-corner-sharing 3D network (Akkerman & Manna, 2020 ▸; Breternitz & Schorr, 2018 ▸). Upon development of the field, numerous analogues containing BX6 octahedra, which are connected in various manners (corner-sharing, edge-sharing and even face-sharing), and organic cations have been developed. Such hybrid metal–halide compounds can form structures in which the inorganic octahedra are connected in very different manners, forming infinite layers (frequently called layered perovskites in the case of corner-to-corner connection; McNulty & Lightfoot, 2021 ▸), polymeric chains, discrete moieties and more complicated structures that include double-chains and double-layers. Hybrid metal halides of different structural motifs tend to display distinctive physical properties. For example, 3D perovskites are known to have the narrowest bandgaps and therefore are the most promising for photovoltaic and optoelectronic applications (Younis et al., 2021 ▸). Layered metal halides have bandgaps which are usually ca. 1 eV higher than for 3D perovskites with corresponding halogens, but they display enhanced stability (Wong & Yang, 2021 ▸). Hybrid metal halides that form inorganic polymeric chains are the most efficient white-light emitters (Yuan et al., 2017 ▸), while hybrid metal halides containing discrete inorganic moieties are known to be very efficient emitters with high quantum yields (Zhang et al., 2021 ▸).
Importantly, the most applied and studied for today are hybrid perovskites and other metal halides that are formed with lead. However, the significant toxicity of this metal induces efforts towards research into lead-free analogues. Most frequently, lead is substituted with tin or germanium due to the chemical similarity of these elements, which allows retention of the physical properties of the target materials while reducing their toxicity.
Herein we describe the crystal structure of a new layered hybrid metal halide – (2-IC2H4NH3)2[GeI4]. The introduction of a 2-iodoethylammonium cation, which is able to create I⋯I contacts, ensures additional structural stability of the framework.
2. Structural commentary
The title compound (2-IC2H4NH3)2[GeI4] crystallizes in the centrosymmetric monoclinic P21/n space group. In its crystal structure, the Ge2+ cation has a significantly distorted octahedral coordination environment provided by six iodide anions (Fig. 1 ▸). The Ge—I bond lengths range from 2.7732 (12) to 3.3646 (11) Å, resulting in an octahedral distortion, which can be quantified by the quadratic elongation parameter: <λoct> = Σ(li/l0)2/6 = 1.0065, where li is the individual Ge—I bond length and l is average Ge—I bond length (Robinson et al., 1971 ▸). The cis-I—Ge—I angles are in the range of 75.23 (3)–95.46 (4)°, leading to a significant bond angle variance: σθ2 = Σ(θi − 90°)2/11 =34.047, where θi are the twelve individual cis-I—Ge—I angles in the coordination octahedron (Robinson et al., 1971 ▸). Such large distortion parameters are quite common for germanium halides. For example, in a series of layered (ClMBA)2GeI4 (ClMBA = 4-chloro-methylbenzylamine) with either enantiopure or racemic cations, bond-angle variances were in the 34.52–55.16° range, while the quadratic elongation parameter was almost the same for these materials (1.029; Coccia et al., 2024 ▸). In comparison with lead, germanium has a more active lone pair, which results in significantly larger distortions.
Figure 1.
Expanded asymmetric unit of the title compound showing the atom-labeling scheme. Hydrogen bonds between organic and inorganic parts are shown as dotted lines. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 
− x, 
+ y, − z; (ii) 
− x, + y, − z.]
The negative charge of the inorganic coordination octahedra in this structure is compensated for by the 2-iodoethylammonium cations. There are two types of crystallographically independent cations in the structure: one of them adopts a synclinal conformation, while the other one is antiperiplanar. Torsion angles in these cations are −65.4 (11)° and 176.7 (7)°, respectively. The I—C, C—C and C—N bond lengths in the organic cations fall within the expected ranges (Allen et al., 1987 ▸).
The inorganic [GeI6]4− octahedra connect with each other in the corner-sharing mode, creating infinite 2D layers that propagate in the ab plane (Fig. 2 ▸). In this type of architecture, the four equatorial iodide anions are bridging (Ib) while two axial iodide anions are terminal (It). The coordination octahedra undergo out-of-plane tilting with respect to the ab plane with the I—Ge—I angles being 161.15 (3)°, thus the layers are slightly corrugated. The organic cations are located between the inorganic layers.
Figure 2.
Fragment of the title compound showing the propagation of infinite two-dimensional inorganic layers along the ab plane. I⋯I contacts between the organic cations and the inorganic layers are shown as pink dashed lines.
3. Supramolecular features
There is an extensive network of hydrogen bonds in the title structure. The 2-iodoethylammonium cation in a synclinal conformation forms three hydrogen bonds of the N—H⋯I type with inorganic layers: two of these hydrogen bonds involve bridging iodine atoms, while the remaining one is with a terminal iodine (Fig. 3 ▸). Detailed information about the hydrogen-bonding geometry is given in Table 1 ▸. The organic cations with an antiperiplanar conformation make four hydrogen bonds with the inorganic layers: three of them are also of the N—H⋯I type (one with a bridging iodine atom and two with terminal ones) while the fourth is of the C—H⋯I type (Fig. 2 ▸, Table 1 ▸). The cations with synclinal and antiperiplanar conformations are arranged in an alternating manner (Fig. 4 ▸). In addition, the iodine atoms of the antiperiplanar cations make I⋯I contacts with the terminal iodine atoms of neighboring inorganic layers, thus creating an infinite 3D supramolecular framework (Fig. 2 ▸). The presence of such I⋯I contacts has previously been shown to have a significant impact on the physical properties of hybrid metal halides. For example, the presence of a very similar organic cation, 4-iodobuthylammonium, in the layered metal halide [I-(CH2)4-NH3]2PbI4 was found to suppress phase transitions in this material in contrast to the very similar [H-(CH2)4-NH3]2PbI4. Phase-transition suppression is associated with the occurrence of I⋯I interactions between organic cations and the inorganic layers, which restrict the movement of organic cations in space (Chakraborty et al., 2022 ▸).
Figure 3.
Detail of the hydrogen bonds created between the 2-iodoethylammonium cations and the inorganic layer.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N1—H1A⋯I4i | 0.91 | 2.74 | 3.544 (11) | 147 |
| N1—H1B⋯I2ii | 0.91 | 3.11 | 3.782 (11) | 133 |
| N1—H1C⋯I3 | 0.91 | 2.86 | 3.735 (10) | 162 |
| N2—H2A⋯I4iii | 0.91 | 2.70 | 3.588 (9) | 166 |
| N2—H2B⋯I3i | 0.91 | 2.87 | 3.744 (9) | 160 |
| N2—H2C⋯I1 | 0.91 | 2.65 | 3.496 (9) | 154 |
| C4—H4A⋯I1iv | 0.99 | 3.13 | 3.790 (10) | 125 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
.
Figure 4.
Alternating organic cations in synclinal (blue) and antiperiplanar (green) conformations within a layer.
Interestingly, in contrast to the antiperiplanar conformation, the synclinal conformation of an organic cation does not permit the formation of a close I⋯I contact with the inorganic layers due to steric hindrance. Such an effect has previously been observed for a series of (ICH2CH2NH3)2(CH3NH3)n-1PbnI3n+1 layered perovskites in which the organic cations in different conformations were shown to impact the structural symmetry and electronic band structure of the layered metal halides (Xue et al., 2023 ▸).
4. Hirshfeld surface analysis
Hirshfeld surface analysis was performed in order to get a deeper insight into the weak interactions found in the structure (Hirshfeld, 1977 ▸). The Hirshfeld surface was plotted with a standard resolution of dnorm over a fixed color scale that uses white to depict contacts whose distances are close to the sum of the van der Waals radii, while shorter distances are shown in red and longer in blue. The obtained plot demonstrates the presence of several strong H⋯I contacts, shown in red in Fig. 5 ▸a. The above-mentioned I⋯I contacts between organic cations in an antiperiplanar conformation with the iodine atoms of the inorganic layers can be observed in pale red. The associated fingerprint plots have also been calculated (Fig. 5 ▸b–d). The plots demonstrate that H⋯I contacts are most common and constitute 71.9% of all interactions present in the structure (Fig. 5 ▸c). In addition, an important contribution is provided by I⋯I interactions (10.2%), as shown in Fig. 5 ▸d.
Figure 5.
(a) Hirshfeld surface of the title compound plotted over dnorm, showing the strongest H⋯I interactions in red; (b)–(d) the two-dimensional fingerprint plots for the title compound.
The prevalence of H⋯I interactions underscores the critical role of hydrogen bonding in stabilizing the structure, while the I⋯I contacts contribute to the three-dimensional supramolecular framework. The remaining H⋯H contacts are statistically frequently observed in the structure due to the terminal positions of the H atoms; they are, however, chemically irrelevant.
It should be mentioned that the color map of the Hirshfeld surface displays the strength of contacts (the strongest contacts are shown in red) while the fingerprint plots indicate how frequently the corresponding contacts are observed in the structure. The Hirshfeld surface analysis was undertaken and the fingerprint plots were generated using Crystal Explorer 21.45 software (Spackman et al., 2021 ▸).
5. Database survey
A survey of the the Cambridge Structural Database (CSD version 5.45, update of September 2024; Groom et al., 2016 ▸) showed that the title compound has never been published before. The search revealed 13 previously known structures of hybrid metal halides containing the 2-iodoethylammonium cation. Two of these structures are (2-IC2H4NH3)SnI4 (Song et al., 2022 ▸) and the mixed-cation [Br-(CH2)2-NH3]2-x[I-(CH2)2-NH3]xPbBrxI4-x (Sourisseau et al., 2007b ▸), which are isostructural to the title compound. There are four reported structures of (2-IC2H4NH3)PbI4, which also form inorganic layers; however in contrast to the title compound, in this lead-based analogue all of the organic cations exhibit an antiperiplanar conformation (Sourisseau et al., 2007a ▸,b ▸; Lemmerer & Billing, 2010 ▸; Skorokhod et al., 2023 ▸). Seven of the found structures contain a second organic cation, methylammonium (MA), and can be described by the general formula (2-IC2H4NH3)2(MA)n-1PbnI3n+1 (n = 2–4). In these compounds there are from two to four consecutive inorganic layers, which are connected into multilayered structures. The methylammonium cations occupy positions in cuboctahedral voids within the multilayers, while the 2-iodoethylammonium cations separate the multilayers. When the number of layers is odd (n = 3), the 2-iodoethylammonium cation adopts an antiperiplanar conformation, while in the case of an even number of layers (n = 2, 4) this cation is in a synclinal conformation (Xue et al., 2023 ▸; Skorokhod et al., 2023 ▸).
6. Synthesis and crystallization
The title compound was obtained as a sub-product upon synthesis of (aziridinium)GeI3; the SXRD (single-crystal X-ray diffraction) experiment established the formation of (2-IC2H4NH3)GeI4 instead of the target perovskite. 63 mg of GeO2 were mixed with 0.9 ml of an aqueous HI solution (57% w/w) and 0.6 ml of H3PO2 (50% w/w). The obtained mixture was heated to 393 K in an oil bath and was kept at this temperature for 20 min upon constant mixing. The obtained transparent orange solution was allowed to cool to room temperature. 10 mg of aziridine were dissolved in 0.1 ml of water and added dropwise to 0.1 ml of the prior solution. The orange crystals that formed within 1 h were collected immediately and kept in Paratone© oil prior to measurements. SXRD measurements were performed at 100 K.
7. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms were placed at calculated positions and refined isotropically with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.2Ueq(N). H atoms of secondary CH2 groups were refined as riding, while H atoms of NH3+ groups were refined as rotating. The crystal under investigation was twinned by a 180° rotation around [100] and the intensity data processed into a HKLF5-type file; the twin components refined to a ratio of 0.8495:0.1504.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | (C2H7IN)2[GeI4] |
| M r | 924.16 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 100 |
| a, b, c (Å) | 8.1431 (2), 8.8362 (2), 25.1787 (7) |
| β (°) | 97.264 (2) |
| V (Å3) | 1797.16 (8) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 11.99 |
| Crystal size (mm) | 0.14 × 0.08 × 0.01 |
| Data collection | |
| Diffractometer | XtaLAB Synergy, Dualflex, HyPix |
| Absorption correction | Analytical (CrysAlis PRO; Rigaku OD, 2023 ▸) |
| Tmin, Tmax | 0.399, 0.852 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5413, 5413, 4967 |
| R int | 0.030 |
| (sin θ/λ)max (Å−1) | 0.708 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.092, 1.19 |
| No. of reflections | 5413 |
| No. of parameters | 121 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 1.21, −1.27 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989024011800/oo2009sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989024011800/oo2009Isup2.hkl
CCDC reference: 2407606
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Poly[bis(2-iodoethylammonium) [di-µ-iodido-diiodidogermanate(II)]]. Crystal data
| (C2H7IN)2[GeI4] | F(000) = 1608 |
| Mr = 924.16 | Dx = 3.416 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.1431 (2) Å | Cell parameters from 10013 reflections |
| b = 8.8362 (2) Å | θ = 3.3–30.5° |
| c = 25.1787 (7) Å | µ = 11.99 mm−1 |
| β = 97.264 (2)° | T = 100 K |
| V = 1797.16 (8) Å3 | Plate, clear intense orange |
| Z = 4 | 0.14 × 0.08 × 0.01 mm |
Poly[bis(2-iodoethylammonium) [di-µ-iodido-diiodidogermanate(II)]]. Data collection
| XtaLAB Synergy, Dualflex, HyPix diffractometer | 4967 reflections with I > 2σ(I) |
| Detector resolution: 10.0000 pixels mm-1 | Rint = 0.030 |
| ω scans | θmax = 30.2°, θmin = 2.4° |
| Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2023) | h = −10→11 |
| Tmin = 0.399, Tmax = 0.852 | k = −11→11 |
| 5413 measured reflections | l = −31→31 |
| 5413 independent reflections |
Poly[bis(2-iodoethylammonium) [di-µ-iodido-diiodidogermanate(II)]]. Refinement
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0215P)2 + 42.6836P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.19 | (Δ/σ)max = 0.001 |
| 5413 reflections | Δρmax = 1.21 e Å−3 |
| 121 parameters | Δρmin = −1.27 e Å−3 |
Poly[bis(2-iodoethylammonium) [di-µ-iodido-diiodidogermanate(II)]]. Special details
| 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. |
| Refinement. Refined as a 2-component twin. |
Poly[bis(2-iodoethylammonium) [di-µ-iodido-diiodidogermanate(II)]]. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| I2 | 1.22418 (8) | 0.35127 (7) | 0.76979 (3) | 0.01606 (14) | |
| I3 | 0.72110 (8) | 0.41154 (7) | 0.76396 (3) | 0.01657 (14) | |
| I1 | 0.95890 (8) | 0.55334 (7) | 0.63911 (3) | 0.01699 (14) | |
| I4 | 1.06654 (8) | 0.65550 (7) | 0.87689 (3) | 0.01740 (14) | |
| I6 | 0.77665 (9) | −0.09924 (8) | 0.51564 (3) | 0.02055 (15) | |
| I5 | 0.25037 (9) | 0.56475 (9) | 0.51448 (3) | 0.02426 (16) | |
| Ge1 | 0.99725 (12) | 0.58843 (11) | 0.75456 (4) | 0.0128 (2) | |
| N1 | 0.4449 (15) | 0.5521 (12) | 0.6444 (4) | 0.035 (3) | |
| H1A | 0.423703 | 0.465891 | 0.624939 | 0.042* | |
| H1B | 0.352259 | 0.580595 | 0.658589 | 0.042* | |
| H1C | 0.528452 | 0.534821 | 0.671279 | 0.042* | |
| C3 | 0.9157 (12) | 0.1243 (11) | 0.6000 (4) | 0.016 (2) | |
| H3A | 0.957632 | 0.183196 | 0.571113 | 0.019* | |
| H3B | 0.798169 | 0.151794 | 0.600885 | 0.019* | |
| N2 | 1.0135 (11) | 0.1621 (10) | 0.6523 (4) | 0.0201 (19) | |
| H2A | 1.123115 | 0.148652 | 0.649940 | 0.024* | |
| H2B | 0.982275 | 0.100583 | 0.678197 | 0.024* | |
| H2C | 0.994867 | 0.260296 | 0.660675 | 0.024* | |
| C2 | 0.3521 (13) | 0.7312 (12) | 0.5719 (5) | 0.022 (2) | |
| H2D | 0.388261 | 0.820189 | 0.552453 | 0.026* | |
| H2E | 0.264226 | 0.765182 | 0.592961 | 0.026* | |
| C4 | 0.9289 (15) | −0.0421 (12) | 0.5888 (5) | 0.024 (2) | |
| H4A | 0.893086 | −0.100939 | 0.618776 | 0.028* | |
| H4B | 1.045603 | −0.068378 | 0.585890 | 0.028* | |
| C1 | 0.4942 (13) | 0.6745 (12) | 0.6091 (5) | 0.024 (2) | |
| H1D | 0.543005 | 0.759248 | 0.631442 | 0.029* | |
| H1E | 0.580109 | 0.635510 | 0.588073 | 0.029* |
Poly[bis(2-iodoethylammonium) [di-µ-iodido-diiodidogermanate(II)]]. Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| I2 | 0.0138 (3) | 0.0141 (3) | 0.0197 (3) | 0.0044 (2) | 0.0000 (2) | −0.0016 (2) |
| I3 | 0.0131 (3) | 0.0153 (3) | 0.0213 (3) | −0.0038 (2) | 0.0023 (2) | 0.0007 (2) |
| I1 | 0.0233 (3) | 0.0132 (3) | 0.0140 (3) | 0.0010 (2) | 0.0006 (3) | 0.0001 (2) |
| I4 | 0.0192 (3) | 0.0172 (3) | 0.0155 (3) | −0.0001 (3) | 0.0012 (3) | −0.0008 (2) |
| I6 | 0.0244 (3) | 0.0201 (3) | 0.0170 (3) | −0.0036 (3) | 0.0019 (3) | −0.0022 (3) |
| I5 | 0.0223 (3) | 0.0297 (4) | 0.0197 (4) | −0.0009 (3) | −0.0015 (3) | −0.0035 (3) |
| Ge1 | 0.0112 (4) | 0.0101 (4) | 0.0172 (5) | 0.0000 (4) | 0.0016 (4) | 0.0002 (4) |
| N1 | 0.056 (7) | 0.029 (5) | 0.019 (5) | 0.011 (5) | −0.003 (5) | 0.000 (4) |
| C3 | 0.016 (4) | 0.017 (5) | 0.016 (5) | −0.001 (4) | 0.004 (4) | −0.008 (4) |
| N2 | 0.025 (5) | 0.015 (4) | 0.020 (5) | 0.002 (3) | 0.001 (4) | 0.002 (3) |
| C2 | 0.024 (5) | 0.017 (5) | 0.022 (6) | −0.002 (4) | −0.004 (4) | 0.000 (4) |
| C4 | 0.030 (6) | 0.015 (5) | 0.025 (6) | −0.001 (4) | 0.001 (5) | 0.002 (4) |
| C1 | 0.021 (5) | 0.014 (5) | 0.035 (7) | −0.001 (4) | −0.006 (5) | −0.008 (5) |
Poly[bis(2-iodoethylammonium) [di-µ-iodido-diiodidogermanate(II)]]. Geometric parameters (Å, º)
| I2—Ge1 | 2.7881 (11) | C3—N2 | 1.487 (13) |
| I3—Ge1 | 2.7732 (12) | C3—C4 | 1.503 (14) |
| I1—Ge1 | 2.9006 (12) | N2—H2A | 0.9100 |
| I4—Ge1 | 3.1172 (12) | N2—H2B | 0.9100 |
| I6—C4 | 2.147 (11) | N2—H2C | 0.9100 |
| I5—C2 | 2.153 (10) | C2—H2D | 0.9900 |
| N1—H1A | 0.9100 | C2—H2E | 0.9900 |
| N1—H1B | 0.9100 | C2—C1 | 1.481 (14) |
| N1—H1C | 0.9100 | C4—H4A | 0.9900 |
| N1—C1 | 1.488 (16) | C4—H4B | 0.9900 |
| C3—H3A | 0.9900 | C1—H1D | 0.9900 |
| C3—H3B | 0.9900 | C1—H1E | 0.9900 |
| I2—Ge1—I1 | 92.47 (4) | H2A—N2—H2B | 109.5 |
| I2—Ge1—I4 | 88.45 (3) | H2A—N2—H2C | 109.5 |
| I3—Ge1—I2 | 95.46 (4) | H2B—N2—H2C | 109.5 |
| I3—Ge1—I1 | 92.27 (3) | I5—C2—H2D | 108.9 |
| I3—Ge1—I4 | 94.03 (4) | I5—C2—H2E | 108.9 |
| I1—Ge1—I4 | 173.52 (4) | H2D—C2—H2E | 107.7 |
| H1A—N1—H1B | 109.5 | C1—C2—I5 | 113.4 (7) |
| H1A—N1—H1C | 109.5 | C1—C2—H2D | 108.9 |
| H1B—N1—H1C | 109.5 | C1—C2—H2E | 108.9 |
| C1—N1—H1A | 109.5 | I6—C4—H4A | 109.6 |
| C1—N1—H1B | 109.5 | I6—C4—H4B | 109.6 |
| C1—N1—H1C | 109.5 | C3—C4—I6 | 110.1 (7) |
| H3A—C3—H3B | 108.2 | C3—C4—H4A | 109.6 |
| N2—C3—H3A | 109.7 | C3—C4—H4B | 109.6 |
| N2—C3—H3B | 109.7 | H4A—C4—H4B | 108.2 |
| N2—C3—C4 | 110.0 (9) | N1—C1—H1D | 109.2 |
| C4—C3—H3A | 109.7 | N1—C1—H1E | 109.2 |
| C4—C3—H3B | 109.7 | C2—C1—N1 | 112.1 (9) |
| C3—N2—H2A | 109.5 | C2—C1—H1D | 109.2 |
| C3—N2—H2B | 109.5 | C2—C1—H1E | 109.2 |
| C3—N2—H2C | 109.5 | H1D—C1—H1E | 107.9 |
| I5—C2—C1—N1 | −65.4 (11) | N2—C3—C4—I6 | 176.7 (7) |
Poly[bis(2-iodoethylammonium) [di-µ-iodido-diiodidogermanate(II)]]. Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···I4i | 0.91 | 2.74 | 3.544 (11) | 147 |
| N1—H1B···I2ii | 0.91 | 3.11 | 3.782 (11) | 133 |
| N1—H1C···I3 | 0.91 | 2.86 | 3.735 (10) | 162 |
| N2—H2A···I4iii | 0.91 | 2.70 | 3.588 (9) | 166 |
| N2—H2B···I3i | 0.91 | 2.87 | 3.744 (9) | 160 |
| N2—H2C···I1 | 0.91 | 2.65 | 3.496 (9) | 154 |
| C4—H4A···I1iv | 0.99 | 3.13 | 3.790 (10) | 125 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+5/2, y−1/2, −z+3/2; (iv) x, y−1, z.
Funding Statement
Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant No. 24BF037-01M; grant No. 24BF037-02).
References
- Akkerman, Q. A. & Manna, L. (2020). ACS Energy Lett.5, 604–610. [DOI] [PMC free article] [PubMed]
- Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–18.
- Breternitz, J. & Schorr, S. (2018). Adv. Energy Mater.8, 1–2.
- Chakraborty, R., Sheikh, T. & Nag, A. (2022). Chem. Mater.34, 288–296.
- Coccia, C., Moroni, M., Treglia, A., Boiocchi, M., Yang, Y., Milanese, C., Morana, M., Capsoni, D., Porta, A., Petrozza, A., Stroppa, A. & Malavasi, L. (2024). J. Am. Chem. Soc.146, 24377–24388. [DOI] [PubMed]
- Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst.42, 339–341.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Hirshfeld, H. L. (1977). Theor. Chim. Acta, 44, 129–138.
- Huang, Z., Bai, Y., Huang, X., Li, J., Wu, Y., Chen, Y., Li, K., Niu, X., Li, N., Liu, G., Zhang, Y., Zai, H., Chen, Q., Lei, T., Wang, L. & Zhou, H. (2023). Nature, 623, 531–537. [DOI] [PubMed]
- Lemmerer, A. & Billing, D. G. (2010). CrystEngComm, 12, 1290–1301.
- McNulty, J. A. & Lightfoot, P. (2021). IUCrJ, 8, 485–513. [DOI] [PMC free article] [PubMed]
- Moeini, A., Martínez-Sarti, L., Zanoni, K. P. S., Sessolo, M., Tordera, D. & Bolink, H. J. (2022). J. Mater. Chem. C.10, 13878–13885.
- Ngai, K. H., Sun, X., Wang, Y., Lin, L., Chen, Z., Wei, Q., Li, M., Luan, C., Zhang, W., Xu, J. & Long, M. (2023). Adv. Funct. Mater.33, 2211830.
- Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.
- Robinson, K., Gibbs, G. V. & Ribbe, P. H. (1971). Science, 172, 567–570. [DOI] [PubMed]
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
- Skorokhod, A., Quarti, C., Abhervé, A., Allain, M., Even, J., Katan, C. & Mercier, N. (2023). Chem. Mater.35, 2873–2883.
- Song, Z., Yu, B., Wei, J., Li, C., Liu, G. & Dang, Y. (2022). Inorg. Chem.61, 6943–6952. [DOI] [PubMed]
- Sourisseau, S., Louvain, N., Bi, W., Mercier, N., Rondeau, D., Boucher, F., Buzaré, J.-Y. & Legein, C. (2007a). Chem. Mater.19, 600–607. [DOI] [PubMed]
- Sourisseau, S., Louvain, N., Bi, W., Mercier, N., Rondeau, D., Buzaré, J.-Y. & Legein, C. (2007b). Inorg. Chem.46, 6148–6154. [DOI] [PubMed]
- Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst.54, 1006–1011. [DOI] [PMC free article] [PubMed]
- Wong, J. & Yang, K. (2021). Sol. RRL, 5, 2000395.
- Xue, J., Huang, Y., Liu, Y., Chen, Z., Sung, H. H. Y., Williams, I. D., Zhu, Z., Mao, L., Chen, X. & Lu, H. (2023). Angew. Chem. Int. Ed.62, e202304486. [DOI] [PubMed]
- Younis, A., Lin, C., Guan, X., Shahrokhi, S., Huang, C., Wang, Y., He, T., Singh, S., Hu, L., Retamal, J. R. D., He, J. & Wu, T. (2021). Adv. Mater.33, 2005000. [DOI] [PubMed]
- Yuan, Z., Zhou, C., Tian, Y., Shu, Y., Messier, J., Wang, J. C., van de Burgt, L. J., Kountouriotis, K., Xin, Y., Holt, E., Schanze, K., Clark, R., Siegrist, T. & Ma, B. (2017). Nat. Commun.8, 14051. [DOI] [PMC free article] [PubMed]
- Zhang, G., Dang, P., Xiao, H., Lian, H., Liang, S., Yang, L., Cheng, Z., Li, G. & Lin, J. (2021). Adv. Opt. Mater.9, 2101637.
- Zhao, Y. & Zhu, K. (2016). Chem. Soc. Rev.45, 655–689.
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989024011800/oo2009sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989024011800/oo2009Isup2.hkl
CCDC reference: 2407606
Additional supporting information: crystallographic information; 3D view; checkCIF report