Crystal structure of hexa­glycinium dodeca­iodo­triplumbate

Tonoyan, G.S.; Giester, G.; Ghazaryan, V.V.; Chilingaryan, R.Y.; Margaryan, A.A.; Mkrtchyan, A.H.; Petrosyan, A.M.

doi:10.1107/S2056989024007606

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ISSN: 2056-9890

Volume 80| Part 9| September 2024| Pages 916-920

https://doi.org/10.1107/S2056989024007606

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Crystal structure of hexaglycinium dodecaiodotriplumbate

Gayane S. Tonoyan,^a ^* Gerald Giester,^b Vahram V. Ghazaryan,^a Ruben Yu. Chilingaryan,^a Arthur A. Margaryan,^a Artak H. Mkrtchyan ^a and Aram M. Petrosyan ^a

^aInstitute of Applied Problems of Physics, NAS of Armenia, 25 Nersessyan Str., 0014 Yerevan, Armenia, and ^bInstitute of Mineralogy and Crystallography, University of Vienna, Josef-Holaubek-Platz 2, A-1090 Vienna, Austria
^*Correspondence e-mail: itonoyan1@gmail.com

Edited by J. Reibenspies, Texas A & M University, USA (Received 31 May 2024; accepted 1 August 2024; online 6 August 2024)

The crystal structure of hexaglycinium tetra-μ-iodido-octaiodidotriplumbate, (C₂H₆NO₂)₆[Pb₃I₁₂] or (GlyH)₆[Pb₃I₁₂], is reported. The compound crystallizes in the triclinic space group P $[\overline{1}]$ . The [Pb₃I₁₂]⁶⁻ anion is discrete and located around a special position: the central Pb ion located on the inversion center is holodirected, while the other two are hemidirected. The supramolecular nature is mainly based on C—H⋯I, N—H⋯I, O—H⋯I and N—H⋯O hydrogen bonds. Dimeric cations of type (A⁺⋯A⁺) for the amino acid glycine are observed for the first time.

Keywords: metal–organic compound; iodoplumbate; crystal structure; tetrel bond; dimeric cation.

CCDC reference: 2368898

1. Chemical context

Various inorganic and organic–inorganic hybrid materials are used in third-generation photovoltaic devices as solar energy converters (Peng et al., 2015 ; Ahmed et al., 2015 ; Zhou et al., 2018 ).

Haloplumbates were also considered to be `solar' materials (Kojima et al., 2009 ; Nazarenko et al., 2018 ), but it turned out that plumbates have unfavorable properties, such as instability and toxicity. However, these compounds may have applications in other interesting areas: white–light emitting materials (Peng et al., 2018 ), luminescent sensing (Wang et al., 2019 ; Wang, 2020 ; Martínez Casado et al., 2012 ), ferroelectric materials (Gao et al., 2017 ), non-linear optical materials (Chen et al., 2020 ) and semiconductors (Terpstra et al., 1997 ).

Our research group has been studying various amino acid salts for a long time (Fleck & Petrosyan, 2014 ), and we assumed that amino acids could be used to synthesize organic–inorganic hybrid materials. After the successful synthesis of (GlyH)PbBr₃ (Tonoyan et al., 2024 ), efforts were focused on obtaining (GlyH)PbI₃.

These compounds are also interesting for lead chemistry. Pb²⁺ has an electronic configuration of [Xe]6s² 4f¹⁴ 5d¹⁰. The 6s² electrons determine the stereochemistry of Pb^II. Upon hybridization of the s and p orbitals, the stereochemically active 6s² electron pair occupies a position in the coordination sphere of the metal (hemidirected coordination). In this case, such hybridization does not occur, the 6s² electron pair has only s character and is stereochemically inactive (holodirected coordination) (Casas et al., 2006 ; Seth et al., 2018 ). As the lead ion has released its two 6p² electrons, σ-hole interactions are possible. These interactions are known among elements of group IV and usually include the tetrel bonding interaction. In other words, the hemidirectional nature of lead(II) centers is the basic reason for different tetrel bonding interactions such as Pb⋯O (S, N, Cl, Br, I), which lead to the formation of supramolecular assemblies.

Instead of (GlyH)PbI₃ crystals, those of (GlyH)₆(Pb₃I₁₂) were formed unexpectedly. The [Pb₃I₁₂]⁶⁻ anion is already known (Wang et al., 2015 , 2017 ; Lemmerer & Billing, 2012 ); it has three lead centers, which can be stereochemically different. In the [Pb₃I₁₂]⁶⁻ anion of {(tbp)₂[Pb₃I₁₂]}_n obtained by Wang et al. (2015), the lead centers are holodirected, coordinated by six iodine atoms, and have an octahedral geometry. In (GlyH)₆(Pb₃I₁₂), the Pb1 center has a holodirected coordination and is bound to six I atoms, while the Pb2 centers with hemidirected coordination are linked to five I atoms. The anion described by Lemmerer & Billing (2012), as well as that reported by Wang et al. (2017) both correspond to our case considering the long Pb1—I6 distance [3.482 (1) Å]; however, these authors misinterpreted the coordination as holodirected or six-coordinate.

2. Structural commentary

The title salt (GlyH)₆(Pb₃I₁₂) crystallizes in the triclinic space group P $[\overline{1}]$ with the asymmetric unit containing half of the formula unit. Selected bond lengths are given in Table 1 and the molecular structure is shown in Fig. 1. In (GlyH)₆(Pb₃I₁₂) the [Pb₃I₁₂]⁶⁻ anion is discrete. The Pb1 center has a holodirected coordination with six I atoms, thus forming an octahedron. The two Pb2 centers have hemidirected coordinations with five I atoms, forming distorted tetragonal pyramids. These hemidirected lead ions have stereochemically active lone pairs. Despite this, any donor–acceptor, covalent or tetrel bonds are missing. The lead centers are connected with each other via Pb—I—Pb covalent bonds (Fig. 2). The anions are located parallel to each other, and the glycinium cations cross-link the entire structure through C—H⋯I, N—H⋯I and O—H⋯I hydrogen bonds (Fig. 3).

Table 1
Selected bond lengths (Å)

C1A—O1A	1.304 (4)	C1B—O1B	1.302 (4)	C1C—O1C	1.322 (4)
C1A—O2A	1.209 (4)	C1B—O2B	1.210 (4)	C1C—O2C	1.196 (4)
C1A—C2A	1.502 (4)	C1B—C2B	1.499 (4)	C1C—C2C	1.507 (5)
C2A—N1A	1.474 (4)	C2B—N1B	1.476 (4)	C2C—N1C	1.477 (4)

Pb1—I1	3.1575 (3) 2×	Pb2—I1	3.4049 (3)	Pb2—I4	3.0213 (3)
Pb1—I2	3.1988 (2) 2×	Pb2—I2	3.4063 (3)	Pb2—I5	3.0926 (3)
Pb1—I3	3.2432 (3) 2×			Pb2—I6	3.0663 (3)

Figure 1
Molecular structure of (GlyH)₆(Pb₃I₁₂). Symmetry code: (i) −x + 1, −y + 1, −z + 1.

Figure 2
The packing of (GlyH)₆(Pb₃I₁₂).

Figure 3
Parallel anions in the packing of (GlyH)₆(Pb₃I₁₂) viewed along the a axis.

3. Supramolecular features

The crystal structure is consolidated via O—H⋯O, O—H⋯I, N—H⋯O, N—H⋯I and C—H⋯I hydrogen bonds (Table 2). The carboxyl group of the glycinium cation A forms a hydrogen bond [O1A—H1A⋯O2A, 2.637 (3) Å] with a symmetry-related glycinium A cation; the same is the case for the cation B: O1B—H1B⋯O2B [2.667 (3) Å]. However, the carboxyl group of the glycinium cation C establishes a hydrogen bond O1C—H1C⋯I5 [3.445 (3) Å] with the anion. Thus, the A and B glycinium cations form centrosymmetric (A⁺⋯A⁺) type dimeric cations, which so far have not been reported for glycine (Fleck & Petrosyan, 2014).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1A⋯O2Aⁱ	0.79 (5)	1.85 (3)	2.638 (3)	171 (4)
C2A—H21A⋯I1ⁱⁱ	0.99	3.10	3.669 (3)	118
C2A—H22A⋯I2	0.99	3.33	4.271 (4)	160
N1A—H11A⋯I4ⁱⁱⁱ	0.91	3.05	3.549 (3)	116
N1A—H11A⋯I5ⁱⁱ	0.91	3.27	3.983 (3)	137
N1A—H11A⋯I6	0.91	3.04	3.655 (3)	126
N1A—H12A⋯I5ⁱⁱⁱ	0.91	2.69	3.588 (3)	170
N1A—H13A⋯I4	0.91	2.75	3.605 (3)	156
O1B—H1B⋯O2B^iv	0.82 (4)	1.85 (4)	2.667 (3)	176 (4)
C2B—H21B⋯I2	0.99	3.03	3.976 (3)	161
C2B—H22B⋯I6^v	0.99	3.18	3.775 (3)	120
N1B—H11B⋯I3^vi	0.91	2.82	3.648 (3)	151
N1B—H12B⋯I1	0.91	3.11	3.647 (3)	119
N1B—H12B⋯O1A^vii	0.91	2.49	3.320 (4)	151
N1B—H13B⋯I6^v	0.91	2.79	3.528 (3)	139
O1C—H1C⋯I5^viii	0.90 (5)	2.57 (3)	3.445 (3)	164 (4)
N1C—H11C⋯I1ⁱⁱ	0.91	3.09	3.711 (3)	127
N1C—H11C⋯I2	0.91	3.13	3.640 (3)	117
N1C—H11C⋯I6	0.91	3.31	3.868 (3)	122
N1C—H12C⋯I2^ix	0.91	3.00	3.779 (3)	145
N1C—H13C⋯I3	0.91	2.73	3.628 (3)	170
C2C—H21C⋯I3ⁱⁱ	0.99	3.14	4.068 (3)	156
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .

The NH₃⁺ groups form rather strong: N1A—H11A⋯I4 [3.549 (3) Å], N1A—H12A⋯I5 [3.588 (3) Å], N1B—H11B⋯I3 [3.648 (3) Å], N1B—H12B⋯I1 [3.647 (3) Å], N1C—H13C⋯I3 [3.628 (3) Å] and weak: N1A—H11A⋯I6 [3.655 (3) Å], N1A—H13A⋯I4 [3.605 (3) Å], N1B—H12B⋯I1 [3.647 (3) Å], N1C—H11C⋯I1 [3.711 (3) Å], N1C—H11C⋯I2 [3.640 (3) Å], N1C—H12C⋯I2 [3.779 (3) Å] hydrogen bonds with the anions. There are also C—H⋯I-type contacts: C2A—H21A⋯I1 [3.669 (3) Å], C2B—H21B⋯I2 [3.976 (3) Å], and C2C—H21C⋯I3 [4.068 (3) Å], which can be considered as very weak hydrogen bonds. Thus, these glycinium cations cross-link the entire structure and consolidate it.

4. Database survey

A survey of the Cambridge Structural Database (CSD2023.2.0, version 5.45, November update; Groom et al., 2016 ) revealed several similar structures. Currently, the Cambridge Structural Database contains 23 entries for the [Pb₃I₁₂]⁶⁻ anion, which can exist in both discrete and polymeric forms that also have different subtypes. In particular, the discrete type has three subtypes: when the middle lead atom of the trinuclear [Pb₃I₁₂]⁶⁻ anion has one (Leng et al., 2023 ), two, or three (Wang et al., 2015; Yue et al., 2019 ; Zhang et al., 2022 ) bridging iodine atoms. When there are one or two bridging iodine atoms, the central lead center has a holodirected coordination and the outer lead atoms have a hemidirected coordination. The anions presented in these works (Lemmerer & Billing, 2012; Wang et al., 2017; Cheng et al., 2023 ) correspond to our case, where the central lead atom has two bridging iodine atoms and the lead centers have different stereochemistry: holodirected (six-coordinate) and hemidirected (five-coordinate). The polymeric [Pb₃I₁₂]⁶⁻ anion can be linear (Liang et al., 2023 ) or cross-linked (Michael & Harald, 2018 ; Nazarenko et al., 2018; Passarelli et al., 2020 ). In summary, 15 [Pb₃I₁₂]⁶⁻ anions from the 23 entries in the CSD are discrete, 7 are polymeric and one case is remarkable (Yao et al., 2022 ) with both a polymer and a discrete [Pb₃I₁₂]⁶⁻ anion being present in the crystal structure.

5. Synthesis and crystallization

As initial reagents we used amino acid glycine (99%) and hydriodic acid (57% w/w, distilled, stabilized with <1.5% hypophosphorous acid, 99.95%). Initially, lead and hydriodic acid were taken in a 1:3 stoichiometric ratio. When the amount of acid in the solution decreases, the reaction between metal and acid slows and eventually almost stops (when no H₂ gas is released). At this point, the amount of obtained lead(II) iodide (PbI₂) and remaining acid (HI) was calculated (1:6 stoichiometric ratio). Next, the appropriate amount of glycine was added and mixed. The final stoichiometric ratio of Gly, PbI₂ and HI was 1:1:6. Instead of the desired compound (GlyH)PbI₃, only (GlyH)₆(Pb₃I₁₂) was obtained. Light-red, needle-shaped crystals were obtained by solvent evaporation in a closed container, using silica gel as an absorber. (GlyH)₆(Pb₃I₁₂) is very hygroscopic: in the IR spectrum the absorption band at 3524 cm⁻¹ corresponds to the ν(OH) stretching modes of the hygroscopic water molecules. The band with a peak at 3036 cm⁻¹ is caused by ν(NH) of the NH₃⁺ groups of glycinium cations. The peaks at 2916 cm⁻¹ and 2854 cm⁻¹ are assigned to ν(CH) of the CH₂ groups, and the strong band at 1716 cm⁻¹ to ν(C=O) of the carboxyl groups.

An attenuated total reflection Fourier-transform infrared spectrum (ATR-FTIR) was recorded on an Agilent Cary 630 spectrometer using a germanium (Ge) ATR sampling module (Ge crystal, Happ–Genzel apodization, ATR distortion corrected, 64 scans, 4 cm⁻¹ resolution). The IR spectrum is shown in Fig. 4.

Figure 4
FTIR spectrum of the title compound.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms were treated as riding on their parent atoms [C—H = 0.99 Å, N—H = 0.91 Å; U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(N)] except those of the carboxyl group, which were refined with the restraint U_iso(H) = 1.5U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	(C₂H₆NO₂)₆[Pb₃I₁₂]
M_r	2600.84
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	200
a, b, c (Å)	8.5437 (5), 11.2672 (7), 14.8534 (9)
α, β, γ (°)	105.900 (2), 92.647 (2), 111.477 (2)
V (Å³)	1262.40 (13)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	17.36
Crystal size (mm)	0.1 × 0.08 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.548, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	54402, 9640, 8389
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.771

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.039, 1.03
No. of reflections	9640
No. of parameters	215
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.29, −2.49
Computer programs: APEX5 Bruker (2024 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and ShelXle (Hübschle et al., 2011 ).

Supporting information

CCDC reference: 2368898

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024007606/jy2048sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024007606/jy2048Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024007606/jy2048Isup4.mol

Supporting information file. DOI: https://doi.org/10.1107/S2056989024007606/jy2048sup5.docx

checkCIF report

Computing details top

Hexaglycinium tetra-µ-iodido-octaiodidotriplumbate top

Crystal data top

(C₂H₆NO₂)₆[Pb₃I₁₂]	Z = 1
M_r = 2600.84	F(000) = 1128
Triclinic, P1	D_x = 3.421 Mg m⁻³
a = 8.5437 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2672 (7) Å	Cell parameters from 9918 reflections
c = 14.8534 (9) Å	θ = 2.6–32.9°
α = 105.900 (2)°	µ = 17.36 mm⁻¹
β = 92.647 (2)°	T = 200 K
γ = 111.477 (2)°	Block, yellow
V = 1262.40 (13) Å³	0.1 × 0.08 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	8389 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.029
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 33.2°, θ_min = 2.1°
T_min = 0.548, T_max = 0.746	h = −13→13
54402 measured reflections	k = −17→17
9640 independent reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.039	w = 1/[σ²(F_o²) + (0.0087P)² + 2.5693P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
9640 reflections	Δρ_max = 2.29 e Å⁻³
215 parameters	Δρ_min = −2.48 e Å⁻³
0 restraints	Extinction correction: SHELXL2019/2 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00049 (2)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pb1	0.500000	0.500000	0.500000	0.02041 (3)
Pb2	0.38342 (2)	0.18885 (2)	0.25654 (2)	0.02316 (3)
I1	0.19064 (2)	0.40522 (2)	0.33606 (2)	0.02537 (4)
I2	0.74935 (2)	0.46827 (2)	0.34936 (2)	0.02390 (4)
I3	0.41471 (2)	0.19237 (2)	0.49364 (2)	0.02463 (4)
I4	0.42551 (3)	0.22381 (2)	0.06337 (2)	0.03591 (5)
I5	0.03007 (3)	−0.03864 (2)	0.16590 (2)	0.03305 (5)
I6	0.59810 (3)	0.01929 (2)	0.23522 (2)	0.03749 (6)
O1A	1.0289 (4)	0.4863 (2)	0.11937 (18)	0.0392 (6)
H1A	1.044 (5)	0.540 (3)	0.0923 (19)	0.059*
O2A	0.8915 (4)	0.3408 (2)	−0.02294 (17)	0.0389 (6)
C1A	0.9400 (4)	0.3667 (3)	0.0605 (2)	0.0263 (6)
C2A	0.9034 (5)	0.2593 (3)	0.1076 (2)	0.0330 (7)
H21A	1.011081	0.252552	0.127759	0.040*
H22A	0.852011	0.282924	0.164719	0.040*
N1A	0.7854 (4)	0.1293 (3)	0.0409 (2)	0.0366 (7)
H11A	0.774867	0.062872	0.066806	0.055*
H12A	0.826984	0.112846	−0.014398	0.055*
H13A	0.681464	0.132077	0.029277	0.055*
O1B	0.6686 (3)	0.5891 (3)	0.10354 (18)	0.0352 (6)
H1B	0.6483 (17)	0.542 (5)	0.048 (3)	0.053*
O2B	0.3916 (3)	0.5535 (3)	0.07956 (16)	0.0347 (5)
C1B	0.5289 (4)	0.5982 (3)	0.1296 (2)	0.0270 (6)
C2B	0.5538 (5)	0.6726 (4)	0.2331 (2)	0.0316 (7)
H21B	0.578315	0.619973	0.271200	0.038*
H22B	0.652301	0.759908	0.248893	0.038*
N1B	0.3990 (4)	0.6954 (3)	0.2566 (2)	0.0316 (6)
H11B	0.404495	0.721763	0.320722	0.047*
H12B	0.305401	0.618023	0.229916	0.047*
H13B	0.391713	0.760631	0.233660	0.047*
O1C	1.0019 (3)	0.1093 (3)	0.6226 (2)	0.0377 (6)
H1C	0.985 (5)	0.104 (4)	0.681 (3)	0.057*
O2C	0.8283 (3)	0.2202 (3)	0.64327 (18)	0.0373 (6)
N1C	0.8615 (4)	0.2696 (3)	0.4769 (2)	0.0352 (7)
H11C	0.867623	0.269306	0.415860	0.053*
H12C	0.923265	0.353762	0.517012	0.053*
H13C	0.750789	0.243678	0.485806	0.053*
C1C	0.9138 (4)	0.1728 (3)	0.5965 (2)	0.0268 (6)
C2C	0.9311 (4)	0.1753 (4)	0.4965 (2)	0.0304 (7)
H21C	1.052603	0.204456	0.488863	0.037*
H22C	0.867896	0.084242	0.451120	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.01827 (7)	0.02247 (7)	0.01990 (7)	0.00920 (6)	0.00231 (5)	0.00423 (6)
Pb2	0.02567 (6)	0.02343 (6)	0.02006 (5)	0.01115 (4)	0.00307 (4)	0.00437 (4)
I1	0.02081 (9)	0.02978 (10)	0.02544 (9)	0.01089 (8)	−0.00022 (7)	0.00788 (8)
I2	0.02197 (9)	0.02590 (10)	0.02631 (9)	0.01158 (7)	0.00746 (7)	0.00847 (7)
I3	0.02360 (9)	0.02525 (10)	0.02430 (9)	0.00811 (7)	0.00517 (7)	0.00853 (7)
I4	0.04911 (14)	0.02858 (11)	0.02416 (10)	0.00690 (10)	0.00171 (9)	0.01154 (8)
I5	0.02567 (10)	0.03563 (12)	0.03222 (11)	0.00594 (9)	0.00550 (8)	0.01039 (9)
I6	0.04793 (14)	0.03453 (12)	0.04935 (14)	0.02767 (11)	0.02635 (11)	0.02394 (11)
O1A	0.0489 (16)	0.0251 (12)	0.0306 (13)	0.0009 (11)	−0.0040 (11)	0.0096 (10)
O2A	0.0541 (16)	0.0256 (12)	0.0280 (12)	0.0052 (11)	−0.0012 (11)	0.0104 (10)
C1A	0.0240 (14)	0.0240 (15)	0.0280 (15)	0.0063 (12)	0.0050 (12)	0.0083 (12)
C2A	0.0415 (19)	0.0234 (16)	0.0288 (16)	0.0057 (14)	0.0033 (14)	0.0099 (13)
N1A	0.0476 (18)	0.0240 (14)	0.0322 (15)	0.0063 (13)	0.0139 (13)	0.0092 (12)
O1B	0.0322 (13)	0.0411 (15)	0.0307 (12)	0.0164 (11)	0.0089 (10)	0.0055 (11)
O2B	0.0351 (13)	0.0478 (15)	0.0253 (11)	0.0217 (12)	0.0083 (10)	0.0096 (11)
C1B	0.0346 (17)	0.0278 (16)	0.0269 (15)	0.0170 (14)	0.0112 (13)	0.0137 (13)
C2B	0.0414 (19)	0.0333 (18)	0.0260 (15)	0.0214 (15)	0.0051 (13)	0.0093 (13)
N1B	0.0427 (17)	0.0304 (15)	0.0267 (13)	0.0176 (13)	0.0148 (12)	0.0107 (12)
O1C	0.0382 (14)	0.0470 (16)	0.0442 (15)	0.0249 (12)	0.0123 (11)	0.0273 (13)
O2C	0.0384 (14)	0.0449 (15)	0.0391 (14)	0.0247 (12)	0.0158 (11)	0.0166 (12)
N1C	0.0302 (15)	0.0430 (17)	0.0437 (17)	0.0180 (13)	0.0108 (13)	0.0254 (14)
C1C	0.0216 (14)	0.0259 (15)	0.0329 (16)	0.0064 (12)	0.0034 (12)	0.0134 (13)
C2C	0.0298 (16)	0.0336 (18)	0.0345 (17)	0.0163 (14)	0.0081 (13)	0.0151 (14)

Geometric parameters (Å, º) top

Pb1—I1ⁱ	3.1575 (3)	O1B—C1B	1.302 (4)
Pb1—I1	3.1575 (2)	O1B—H1B	0.82 (5)
Pb1—I2ⁱ	3.1988 (2)	O2B—C1B	1.210 (4)
Pb1—I2	3.1988 (2)	C1B—C2B	1.499 (4)
Pb1—I3	3.2432 (3)	C2B—N1B	1.476 (4)
Pb1—I3ⁱ	3.2432 (3)	C2B—H21B	0.9900
Pb2—I4	3.0213 (3)	C2B—H22B	0.9900
Pb2—I6	3.0663 (3)	N1B—H11B	0.9100
Pb2—I5	3.0926 (3)	N1B—H12B	0.9100
Pb2—I1	3.4049 (3)	N1B—H13B	0.9100
Pb2—I2	3.4063 (3)	O1C—C1C	1.322 (4)
O1A—C1A	1.304 (4)	O1C—H1C	0.90 (5)
O1A—H1A	0.79 (5)	O2C—C1C	1.196 (4)
O2A—C1A	1.209 (4)	N1C—C2C	1.477 (4)
C1A—C2A	1.502 (4)	N1C—H11C	0.9100
C2A—N1A	1.474 (4)	N1C—H12C	0.9100
C2A—H21A	0.9900	N1C—H13C	0.9100
C2A—H22A	0.9900	C1C—C2C	1.507 (5)
N1A—H11A	0.9100	C2C—H21C	0.9900
N1A—H12A	0.9100	C2C—H22C	0.9900
N1A—H13A	0.9100

I1ⁱ—Pb1—I1	180.0	C2A—N1A—H12A	109.5
I1ⁱ—Pb1—I2ⁱ	91.363 (7)	H11A—N1A—H12A	109.5
I1—Pb1—I2ⁱ	88.637 (8)	C2A—N1A—H13A	109.5
I1ⁱ—Pb1—I2	88.637 (7)	H11A—N1A—H13A	109.5
I1—Pb1—I2	91.363 (7)	H12A—N1A—H13A	109.5
I2ⁱ—Pb1—I2	180.0	C1B—O1B—H1B	109.5
I1ⁱ—Pb1—I3	88.797 (5)	O2B—C1B—O1B	126.6 (3)
I1—Pb1—I3	91.203 (5)	O2B—C1B—C2B	121.3 (3)
I2ⁱ—Pb1—I3	91.693 (5)	O1B—C1B—C2B	112.1 (3)
I2—Pb1—I3	88.307 (5)	N1B—C2B—C1B	110.1 (3)
I1ⁱ—Pb1—I3ⁱ	91.203 (5)	N1B—C2B—H21B	109.6
I1—Pb1—I3ⁱ	88.797 (6)	C1B—C2B—H21B	109.6
I2ⁱ—Pb1—I3ⁱ	88.307 (5)	N1B—C2B—H22B	109.6
I2—Pb1—I3ⁱ	91.693 (5)	C1B—C2B—H22B	109.6
I3—Pb1—I3ⁱ	180.0	H21B—C2B—H22B	108.2
I4—Pb2—I6	92.576 (7)	C2B—N1B—H11B	109.5
I4—Pb2—I5	88.198 (8)	C2B—N1B—H12B	109.5
I6—Pb2—I5	98.865 (9)	H11B—N1B—H12B	109.5
I4—Pb2—I1	98.685 (7)	C2B—N1B—H13B	109.5
I6—Pb2—I1	166.133 (7)	H11B—N1B—H13B	109.5
I5—Pb2—I1	89.602 (8)	H12B—N1B—H13B	109.5
I4—Pb2—I2	88.550 (7)	C1C—O1C—H1C	109.5
I6—Pb2—I2	88.468 (8)	C2C—N1C—H11C	109.5
I5—Pb2—I2	172.104 (7)	C2C—N1C—H12C	109.5
I1—Pb2—I2	83.779 (8)	H11C—N1C—H12C	109.5
Pb1—I1—Pb2	76.444 (6)	C2C—N1C—H13C	109.5
Pb1—I2—Pb2	75.892 (6)	H11C—N1C—H13C	109.5
C1A—O1A—H1A	109.5	H12C—N1C—H13C	109.5
O2A—C1A—O1A	125.6 (3)	O2C—C1C—O1C	126.1 (3)
O2A—C1A—C2A	122.0 (3)	O2C—C1C—C2C	123.3 (3)
O1A—C1A—C2A	112.4 (3)	O1C—C1C—C2C	110.6 (3)
N1A—C2A—C1A	109.8 (3)	N1C—C2C—C1C	108.8 (3)
N1A—C2A—H21A	109.7	N1C—C2C—H21C	109.9
C1A—C2A—H21A	109.7	C1C—C2C—H21C	109.9
N1A—C2A—H22A	109.7	N1C—C2C—H22C	109.9
C1A—C2A—H22A	109.7	C1C—C2C—H22C	109.9
H21A—C2A—H22A	108.2	H21C—C2C—H22C	108.3
C2A—N1A—H11A	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···O2Aⁱⁱ	0.79 (5)	1.85 (3)	2.638 (4)	171 (4)
C2A—H21A···I1ⁱⁱⁱ	0.99	3.10	3.669 (3)	118
C2A—H22A···I2	0.99	3.33	4.271 (4)	160
N1A—H11A···I4^iv	0.91	3.05	3.549 (3)	116
N1A—H11A···I5ⁱⁱⁱ	0.91	3.27	3.983 (3)	137
N1A—H11A···I6	0.91	3.04	3.655 (3)	126
N1A—H12A···I5^iv	0.91	2.69	3.588 (3)	170
N1A—H13A···I4	0.91	2.75	3.605 (3)	156
O1B—H1B···O2B^v	0.82 (4)	1.85 (4)	2.667 (3)	176 (4)
C2B—H21B···I2	0.99	3.03	3.976 (3)	161
C2B—H22B···I6^vi	0.99	3.18	3.775 (3)	120
N1B—H11B···I3ⁱ	0.91	2.82	3.648 (3)	151
N1B—H12B···I1	0.91	3.11	3.647 (3)	119
N1B—H12B···O1A^vii	0.91	2.49	3.320 (4)	151
N1B—H13B···I6^vi	0.91	2.79	3.528 (3)	139
O1C—H1C···I5^viii	0.90 (5)	2.57 (3)	3.445 (3)	164 (4)
N1C—H11C···I1ⁱⁱⁱ	0.91	3.09	3.711 (3)	127
N1C—H11C···I2	0.91	3.13	3.640 (3)	117
N1C—H11C···I6	0.91	3.31	3.868 (3)	122
N1C—H12C···I2^ix	0.91	3.00	3.779 (3)	145
N1C—H13C···I3	0.91	2.73	3.628 (3)	170
C2C—H21C···I3ⁱⁱⁱ	0.99	3.14	4.068 (3)	156

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) x+1, y, z; (iv) −x+1, −y, −z; (v) −x+1, −y+1, −z; (vi) x, y+1, z; (vii) x−1, y, z; (viii) −x+1, −y, −z+1; (ix) −x+2, −y+1, −z+1.

Selected bond lengths (Å) top

C1A—O1A	1.304 (4)	C1B—O1B	1.302 (4)	C1C—O1C	1.322 (4)
C1A—O2A	1.209 (4)	C1B—O2B	1.210 (4)	C1C—O2C	1.196 (4)
C1A—C2A	1.502 (4)	C1B—C2B	1.499 (4)	C1C—C2C	1.507 (5)
C2A—N1A	1.474 (4)	C2B—N1B	1.476 (4)	C2C—N1C	1.477 (4)

Pb1—I1	3.1575 (3) 2×	Pb2—I1	3.4049 (3)	Pb2—I4	3.0213 (3)
Pb1—I2	3.1988 (2) 2×	Pb2—I2	3.4063 (3)	Pb2—I5	3.0926 (3)
Pb1—I3	3.2432 (3) 2×			Pb2—I6	3.0663 (3)

Funding information

The work was supported by the Science Committee of RA, in the frame of research project No. 21AG-1D015.

References

Ahmed, M. I., Habib, A. & Javaid, S. S. (2015). Int. J. Photoenergy, 92308. http://dx.doi.org/10.1155/2015/592308 Google Scholar
Bruker (2024). APEX5. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Casas, J. S., Sordo, J. & Vidarte, M. J. (2006). Lead(II) coordination chemistry in the solid state. In Lead: Chemistry, Analytical Aspects, Environmental Impact and Health Effects, 1st ed., edited by J. S. Casas & J. Sordo, pp. 41–72. Amsterdam: Elsevier. Google Scholar
Chen, X., Jo, H. & Ok, K. M. (2020). Angew. Chem. Int. Ed. 59, 7514–7520. Web of Science CrossRef ICSD Google Scholar
Cheng, X., Han, Y., Cheng, T., Xie, Y., Chang, X., Lin, Y., Lv, L., Li, J., Yin, J. & Cui, B.-B. (2023). Appl. Mater. Interfaces, 15, 32506–32514. Web of Science CSD CrossRef Google Scholar
Fleck, M. & Petrosyan, A. M. (2014). Salts of Amino Acids: Crystallization, Structure and Properties. Dordrecht, Springer. Google Scholar
Gao, R., Reyes-Lillo, S. E., Xu, R., Dasgupta, A., Dong, Y., Dedon, L. R., Kim, J., Saremi, S., Chen, Z., Serrao, C. R., Zhou, H., Neaton, J. B. & Martin, L. W. (2017). Chem. Mater. 29, 6544–6551. Web of Science CrossRef Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. (2009). J. Am. Chem. Soc. 131, 6050–6051. Web of Science CrossRef PubMed CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Lemmerer, A. & Billing, D. G. (2012). CrystEngComm, 14, 1954–1966. Web of Science CSD CrossRef CAS Google Scholar
Leng, F., Zhang, X. & Yu, J.-H. (2023). Dalton Trans. 52, 5127–5140. Web of Science CSD CrossRef PubMed Google Scholar
Liang, B.-D., Fan, C.-C., Liu, C.-D., Ju, T.-Y., Chai, C.-Y., Han, X.-B. & Zhang, W. (2023). Inorg. Chem. Front. 10, 5035–5043. Web of Science CSD CrossRef Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Martínez Casado, F. J., Cañadillas-Delgado, L., Cucinotta, F., Guerrero-Martínez, A., Ramos Riesco, M., Marchese, L. & Rodríguez Cheda, J. A. (2012). CrystEngComm, 14, 2660–2668. Google Scholar
Michael, D. & Harald, H. (2018). Z. Kristallogr. Cryst. Mater. 233, 555–564. Google Scholar
Nazarenko, O., Kotyrba, M. R., Yakunin, S., Aebli, M., Rainò, G., Benin, B. M., Wörle, M. & Kovalenko, M. V. (2018). J. Am. Chem. Soc. 140, 3850–3853. Web of Science CSD CrossRef PubMed Google Scholar
Passarelli, J. V., Mauck, C. M., Winslow, S. W., Perkinson, C. F., Bard, J. C., Sai, H., Williams, K. W., Narayanan, A., Fairfield, D. J., Hendricks, M. P., Tisdale, W. A. & Stupp, S. I. (2020). Nat. Chem. 12, 672–682. Web of Science CSD CrossRef CAS PubMed Google Scholar
Peng, Ch., Zhuang, Z., Yang, H., Zhang, G. & Fei, H. (2018). Chem. Sci. 9, 1627–1633. Web of Science CSD CrossRef PubMed Google Scholar
Peng, G., Xu, X. & Xu, G. (2015). J. Nanomater., 41853. Google Scholar
Seth, S. K., Bauzá, A., Mahmoudi, Gh., Stilinović, V., López-Torres, E., Zaragoza, G., Keramidas, A. D. & Frontera, A. (2018). CrystEngComm, 20, 5033–5044. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Terpstra, H. J., De Groot, R. A. & Haas, C. (1997). J. Phys. Chem. Solids, 58, 561–566. CrossRef CAS Web of Science Google Scholar
Tonoyan, G. S., Giester, G., Ghazaryan, V. V., Badalyan, A. Y., Chilingaryan, R. Yu., Margaryan, A. A., Mkrtchyan, A. H. & Petrosyan, A. M. (2024). III Intern. Scientific School-Conference on Acoustophysics named after Academician A. R. Mkrtchyan, Book of Abstracts, p. 23., Yerevan-Sevan, Armenia. https://school. iapp. am/wp-content/uploads/2024/06/Book-of-Abstract-Sevan-2024.pdf Google Scholar
Wang, C.-H., Du, H.-J., Li, Y., Niu, Y.-Y. & Hou, H.-W. (2015). New J. Chem. 39, 7372–7378. Web of Science CSD CrossRef Google Scholar
Wang, J., Gao, L., Zhang, J., Zhao, L., Wang, X., Niu, X., Fan, L. & Hu, T. (2019). Cryst. Growth Des. 19, 630–637. Web of Science CSD CrossRef CAS Google Scholar
Wang, L. (2020). J. Inorg. Organomet. Polym. 30, 291–298. Web of Science CSD CrossRef CAS Google Scholar
Wang, R.-Y., Zhang, X., Huo, Q.-S., Yu, J.-H. & Xu, J.-Q. (2017). RSC Adv. 7, 19073–19080. Web of Science CSD CrossRef CAS Google Scholar
Yao, G., Zhao, L., Zeng, T. & Yang, Z. (2022). Nanotechnology, 33, 355701. Web of Science CSD CrossRef Google Scholar
Yue, C.-Y., Sun, H.-X., Liu, Q.-X., Wang, X.-M., Yuan, Z.-S., Wang, J., Wu, J.-H., Hu, B. & Lei, X.-W. (2019). Inorg. Chem. Front. 6, 2709–2717. Web of Science CSD CrossRef CAS Google Scholar
Zhang, Sh., Xiao, T., Fadaei Tirani, F., Scopelliti, R., Nazeeruddin, M. K., Zhu, D., Dyson, P. J. & Fei, Z. (2022). Inorg. Chem. 61, 5010–5016. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zhou, D., Zhou, T., Tian, Y., Zhu, X. & Tu, Y. (2018). J. Nanomaterials, 8148072. Google Scholar