Crystal structure of bis­(β-alaninium) tetra­bromidoplumbate

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

doi:10.1107/S2056989024007722

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 80| Part 9| September 2024| Pages 931-935

https://doi.org/10.1107/S2056989024007722

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Crystal structure of bis(β-alaninium) tetrabromidoplumbate

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 L. Suescun, Universidad de la República, Uruguay (Received 10 June 2024; accepted 5 August 2024; online 9 August 2024)

The title compound, poly[bis(β-alaninium) [[dibromidoplumbate]-di-μ-dibromido]] {(C₂H₈NO₂)₂[PbBr₄]}_n or (β-AlaH)₂PbBr₄, crystallizes in the monoclinic space group P2₁/n. The (PbBr₄)²⁻ anion is located on a general position and has a two-dimensional polymeric structure. The Pb center is holodirected. The supramolecular network is mainly based on O—H⋯Br, N—H⋯Br and N—H⋯O hydrogen bonds.

Keywords: organic–inorganic crystal; hybrid crystal; bromoplumbate; crystal structure.

CCDC reference: 2368897

1. Chemical context

As plumbiferous compounds are commonly toxic, they are unfavorable for photovoltaic devices. Nonetheless, they have other important applications such as 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 ). Lead-containing materials also are attractive from a stereochemical point of view. The Pb²⁺ ion has a 6s² electron pair, which is crucial for the stereochemistry of Pb^II. When the 6s² electron pair takes part in hybridization between the s and p orbitals, the lead atom is stereochemically active and has a hemidirected coordination, otherwise the lead atom exhibits a regular coordination sphere (Casas et al., 2006 ; Seth et al., 2018 ).

Our research group has been studying various amino acid salts for a long time (Fleck & Petrosyan, 2014 ), and we assumed that amino acids could also 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 and related phases. Later, it was attempted to synthesize salts of β-alanine in the same manner; however, instead of (β-AlaH)PbBr₃, crystals of (β-AlaH)₂PbBr₄ were formed.

In (β-AlaH)₂PbBr₄ the anion is slightly distorted and the Pb—Br bond lengths range from 2.8952 (3) to 3.2714 (2) Å. This indicates that the Pb^II center is not stereochemically active and the anion has holodirected stereochemistry. Recently a paper was published (Zu et al., 2023 ) in which the authors investigated the relationship between the structures and optoelectronic properties of [(HOOC_nH_2n−2NH₃)₂]PbBr₄ (n = 3–8) crystals, also including (β-AlaH)₂PbBr₄ (see also Cazals et al., 2024 ). In our work, we focused on characterizing the structure from a stereochemical point of view, discussing the Pb^II character in a structure solved using XRD data collected at 200 K.

2. Structural commentary

The title compound (β-AlaH)₂PbBr₄ crystallizes in the monoclinic space group P2₁/n. The asymmetric unit contains one formula unit. The molecular arrangement is shown in Fig. 1. As can be seen from the dihedral angles (Table 1), both β-alaninium cations have the most common gauche conformation (Fleck et al., 2012 ).

Table 1
Selected geometric parameters (Å, °)

Pb1—Br1	3.0589 (4)	Pb1—Br2ⁱ	3.2714 (2)
Pb1—Br3	2.9230 (4)	Pb1—Br4	2.9477 (3)
Pb1—Br2	2.8952 (3)	Pb1—Br4ⁱⁱ	3.0591 (3)

Br1—Pb1—Br2	88.107 (9)	Br2ⁱ—Pb1—Br4ⁱⁱ	81.63 (1)
Br1—Pb1—Br2ⁱ	80.90 (1)	Br3—Pb1—Br2	87.836 (9)
Br1—Pb1—Br4	87.683 (8)	Br3—Pb1—Br4	92.596 (8)
Br1—Pb1—Br4ⁱⁱ	89.760 (8)	Br3—Pb1—Br4ⁱⁱ	90.472 (8)
Br2—Pb1—Br4	90.568 (9)	Pb1—Br2—Pb1ⁱⁱⁱ	168.87 (1)
Br2—Pb1—Br4ⁱⁱ	96.645 (9)	Pb1—Br2ⁱ—Pb1ⁱ	168.87 (1)
Br2ⁱ—Pb1—Br4	90.75 (1)	Pb1—Br4—Pb1^iv	168.90 (1)

O1A—C1A—C2A—C3a	−164.4 (2)	O1B—C1B—C2B—C3B	171.4 (2)
C1A—C2A—C3A—N1A	−62.9 (3)	C1B—C2B—C3B—N1B	59.7 (3)
Symmetry codes: (i) ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
Molecular structure of (β-AlaH)₂PbBr₄. Displacement ellipsoids are shown at the 50% probability level. Symmetry codes: (i) x − 1, y, z; (ii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) x + 1, y, z; (iv) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .

The Pb²⁺ centers of the anion exhibit a holodirected six-coordination with an octahedral geometry. Therefore, for neighboring bromine atoms, the Br—Pb—Br angles are close to right angles, varying from 80.90 (1) to 103.14 (1)° (Table 1). The lead atom forms three partial covalent bonds Pb1—Br2, Pb1—Br3, and Pb1—Br4, and also three coordination bonds with partial covalent character Pb1—Br1, Pb1—Br2ⁱ and Pb1—Br4ⁱⁱ (Table 1). Despite the range of Pb1—Br distances, the average value of 3.0259 Å is close to the average value of 3.0310 Å in PbBr₆ octahedra, regardless of the anion, for 284 structures in the Cambridge Structural Database (CSD2023.2.0, version 5.45, November update; Groom et al., 2016 ). The PbBr₆ octahedra form a 2D structure with four shared vertices: Br2, Br2ⁱ, Br4, and Br4ⁱⁱ (Fig. 2). The octahedra share only vertices, not edges nor faces. The two terminal opposite atoms Br1 and Br3 are located on the surfaces of the layer and the octahedra are arranged in such a way that the angles of the Pb—Br—Pb bridges are close to linear (Table 1), which leads to square-shaped voids between the octahedra.

Figure 2
2D structure of the PbBr₄ anion viewed along the c axis. Part of the anion is shown in an octahedral style. Symmetry codes: (i) x − 1, y, z; (ii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) x + 1, y, z; (iv) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .

3. Supramolecular features

The packing in the crystal together with the hydrogen-bond network is shown in Fig. 3. The anionic layers are parallel to the (001) plane, with an interlayer distance of 11.026 (1) Å. The β-alaninium cations are positioned between the anionic layers with the amino and carboxyl groups oriented towards those layers. The β-alaninium cations cross-link neighboring layers of anions through hydrogen bonds between terminal bromine atoms and NH₃⁺, and OH groups (Table 2). Each carboxyl group forms one O—H⋯Br hydrogen bond, while the ammonium groups form two and three N—H⋯Br hydrogen bonds. Intramolecular N1A—H11A⋯O2A and N1B—H12B⋯O2B hydrogen bonds are present in the β-alaninium moieties (Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1A⋯Br3ⁱⁱ	0.90 (2)	2.35 (3)	3.241 (2)	171 (4)
N1A—H11A⋯O2A	0.91	2.18	2.853 (3)	130
N1A—H12A⋯Br1^v	0.91	2.73	3.619 (2)	166
N1A—H13A⋯Br1^vi	0.91	2.58	3.445 (2)	159
O1B—H1B⋯Br1^v	0.88 (2)	2.32 (3)	3.188 (2)	167 (4)
N1B—H11B⋯Br3^vii	0.91	2.49	3.343 (2)	157
N1B—H12B⋯Br1ⁱⁱⁱ	0.91	2.76	3.484 (2)	137
N1B—H12B⋯O2B	0.91	2.17	2.839 (3)	129
N1B—H13B⋯Br4^vii	0.91	2.56	3.407 (2)	155
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) ; (v) ; (vi) ; (vii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
Packing diagram of the structure of (β-AlaH)₂PbBr₄ viewed along the a axis. Hydrogen bonds are shown as dotted lines.

4. Database survey

A survey of the Cambridge Structural Database (CSD2023.2.0, version 5.45, November update; Groom et al., 2016) revealed 320 structures containing PbBr₄. There were 91 duplicate structures solved at different temperatures, and several inappropriate structures; thus, overall 224 structures were considered. Among them, the title compound was found with refcode YINFIO (Zu et al., 2023), determined at room temperature.

In the structures, the (PbBr₄)²⁻ anion can be in discrete 0D, polymeric 1D, and 2D forms. 0D anions are present in a pseudotrigonal–bipyramidal geometry (Fig. 4a: ARAJUB, Lin et al., 2019 ; BOKYAF, Han 2024 ; YIQPAP, Gröger et al., 2002 ) and in a trigonal–pyramidal geometry (Fig. 4b: UVELIT, Gong et al., 2021 ).

Figure 4
The (PbBr₄)²⁻ anion geometries. Note that one more 2D form is missing here as it is shown in Fig. 2

. The numbers of CCD structures for a given type of anion are indicated.

A 1D structure anion may consist of either PbBr₅ square-pyramids (3 structures) or PbBr₆ octahedra (16 structures). The square-pyramids are alternately connected by a shared bromine atom, with three bromine atoms remaining terminal. Chains can be linear (Fig. 4c: RUSBUF, Lv et al., 2020 ) or zigzag (Fig. 4d: SOHYAS, Li et al., 2019 ). Octahedral PbBr₆ monomers can attach two, three or four adjacent octahedra, have four or three shared bromine atoms, and two or three terminal atoms. Chains can be linear (Fig. 4e: COKYIO, Zhang et al., 2024 ), zigzag (Fig. 4f: CEKYIE, Fu et al., 2022 ), V-shaped (Fig. 4g: FERGER, Yuan et al., 2017 ), and double (Fig. 4h: HENLAR, Jin et al., 2022 ).

When each monomer has four adjacent monomers attached, and each pair of adjacent monomers shares one bromine atom, a 2D structure is formed (195 structures). Each lead atom has two terminal bromine atoms in the 2D structure of the anion. There are two main options, depending on the terminal atoms. When terminal atoms are trans positioned, a planar arrangement of octahedra is formed. In our case, the Pb—Br—Pb angles are close to linear (Table 1, Fig. 2). An ideal form of this is a rare centrosymmetric anion in the structure of COJKIZ01 (Long et al., 2024 ) with 180° Pb—Br—Pb angles, and square-shaped voids between the octahedra. There are 36 structures with square or near square voids, and this is the second most common geometry at 16%. In other cases, the Pb—Br—Pb angles differ from 180°, and values down to 139° can be encountered, causing rhombic voids (Fig. 4i: TAKZAK, Zhang, et al., 2020 ; OBAYAV, Zhang et al., 2021 ). This geometry is found in the prevailing number of structures, 141, almost 63%. However, in the case of cis positioning of terminal atoms, the anion has a zigzag arrangement of octahedra, forming stacked layers. Two-stacked layers can be formed having linear Pb—Br—Pb angles (Fig. 4g: SOHYAS01, Li et al., 2019) or obtuse angles in the range of 164–148° (Fig. 4k: RICBEO01, RICBEO02, Drozdowski et al., 2023 ; Fig. 4l: NIZQAP, Li et al., 2008 ). One structure has layers arranged in a zigzag manner that contain octahedra with both trans- and cis-positioned terminal bromine atoms (Fig. 4m: UBUFEG, Guo et al., 2021 ).

5. Synthesis and crystallization

As initial reagents, we used amino acid β-alanine (99% NT) and hydrobromic acid (48%) purchased from Sigma-Aldrich and lead (reactive grade). Initially, an excess volume of hydrobromic acid was added to a preliminary weighted amount of lead. When the reaction between them was completed (when no H₂ gas is released), the unreacted lead was removed by filtration, dried and weighed. The quantities of lead(II) bromide (PbBr₂) obtained and unreacted acid (HBr) in the filtrate were calculated. The appropriate amount of β-alanine was added to it and mixed to achieve a final solution with a 1:1:6 molar ratio of β-Ala, PbBr₂ and HBr, respectively. Instead of the desired compound (β-AlaH)PbBr₃, (β-AlaH)₂PbBr₄ was obtained as yellow crystals (Fig. 5).

Figure 5
Yellow crystals of (β-AlaH)₂PbBr₄ under the microscope.

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 groups, which were refined with the restraint U_iso(H) = 1.5U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	(C₃H₈NO₂)₂[PbBr₄]
M_r	707.04
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	6.1377 (4), 11.9291 (8), 22.1508 (14)
β (°)	95.402 (2)
V (Å³)	1614.62 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	20.35
Crystal size (mm)	0.20 × 0.18 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.346, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	53070, 6172, 5328
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.770

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.044, 1.07
No. of reflections	6172
No. of parameters	163
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.51, −1.16
Computer programs: APEX5 Bruker (2024 ), SHELXT (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and ShelXle (Hübschle et al., 2011 ).

Supporting information

CCDC reference: 2368897

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024007722/oo2006sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024007722/oo2006Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024007722/oo2006Isup3.mol

checkCIF report

Computing details top

Poly[bis(β-alaninium) [[dibromidoplumbate]-di-µ-dibromido]] top

Crystal data top

(C₃H₈NO₂)₂[PbBr₄]	F(000) = 1280
M_r = 707.04	D_x = 2.909 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.1377 (4) Å	Cell parameters from 9846 reflections
b = 11.9291 (8) Å	θ = 3.4–32.8°
c = 22.1508 (14) Å	µ = 20.35 mm⁻¹
β = 95.402 (2)°	T = 200 K
V = 1614.62 (18) Å³	Plate, yellow
Z = 4	0.20 × 0.18 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	5328 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.046
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 33.2°, θ_min = 1.9°
T_min = 0.346, T_max = 0.747	h = −9→9
53070 measured reflections	k = −18→18
6172 independent reflections	l = −33→33

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.044	w = 1/[σ²(F_o²) + (0.0092P)² + 2.110P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.003
6172 reflections	Δρ_max = 1.51 e Å⁻³
163 parameters	Δρ_min = −1.16 e Å⁻³
2 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: 0.00134 (4)

Special details top

Experimental. A selected fragment of a crystal was mounted on a MiTeGen loop with silicone grease and examined by single crystal X-ray diffraction at 200 K on a Bruker APEX II diffractometer equipped with a CCD area detector, an Incoatec Microfocus Source IµS (30 W, multilayer mirror, Mo-K_α) and an Oxford Cryosystems Cryostream 800 Plus LT device. Several sets of phi- and omega-scans with 2° scanwidth were combined at a crystal-detector distances of 40 mm to achieve respective full sphere data up to 65° 2θ. Data handling with integration and absorption correction by evaluation of multi-scans was done with the Bruker Apex5 suite (Bruker, 2024). The structure was solved by direct methods (Sheldrick, 2015a); subsequent difference Fourier syntheses and least-squares refinements yielded the positions of the remaining atoms using the SHELX software (Sheldrick, 2015b) implemented in the ShelXle GUI tool (Hübschle et al. 2011). Non-hydrogen atoms were refined with independent anisotropic displacement parameters.

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	0.28160 (2)	0.48657 (2)	0.24772 (2)	0.01445 (3)
Br1	0.29433 (4)	0.47456 (2)	0.38595 (2)	0.02132 (6)
Br2	0.75530 (4)	0.48144 (3)	0.26094 (2)	0.02559 (6)
Br3	0.30325 (5)	0.49665 (2)	0.11657 (2)	0.02542 (6)
Br4	0.28669 (5)	0.73272 (2)	0.25942 (2)	0.02607 (7)
O1A	0.3047 (4)	0.05338 (17)	0.52622 (10)	0.0313 (5)
H1A	0.278 (6)	0.046 (3)	0.4858 (11)	0.047*
O2A	0.1232 (3)	0.21235 (17)	0.50427 (9)	0.0269 (4)
C1A	0.2260 (4)	0.1520 (2)	0.54084 (12)	0.0186 (5)
C2A	0.2849 (5)	0.1821 (2)	0.60573 (12)	0.0200 (5)
H21A	0.441345	0.203553	0.611180	0.024*
H22A	0.265866	0.115205	0.631189	0.024*
C3A	0.1492 (5)	0.2771 (2)	0.62751 (14)	0.0239 (6)
H31A	−0.007460	0.256173	0.621905	0.029*
H32A	0.189159	0.289100	0.671382	0.029*
N1A	0.1826 (4)	0.38366 (19)	0.59418 (12)	0.0258 (5)
H11A	0.166295	0.370391	0.553548	0.039*
H12A	0.319688	0.410268	0.604972	0.039*
H13A	0.082103	0.435237	0.603713	0.039*
O1B	0.6103 (4)	0.3217 (2)	0.52220 (10)	0.0340 (5)
H1B	0.658 (6)	0.378 (3)	0.5458 (16)	0.051*
O2B	0.8138 (3)	0.39905 (15)	0.45540 (9)	0.0235 (4)
C1B	0.6963 (4)	0.3238 (2)	0.46965 (13)	0.0204 (5)
C2B	0.6369 (5)	0.2227 (2)	0.43163 (13)	0.0221 (5)
H21B	0.476516	0.211567	0.429550	0.026*
H22B	0.707312	0.156012	0.451675	0.026*
C3B	0.7035 (5)	0.2303 (2)	0.36840 (14)	0.0263 (6)
H31B	0.657467	0.161277	0.345882	0.032*
H32B	0.627841	0.294589	0.347349	0.032*
N1B	0.9441 (4)	0.2447 (2)	0.36811 (12)	0.0269 (5)
H11B	1.013572	0.182729	0.384263	0.040*
H12B	0.987954	0.305927	0.390577	0.040*
H13B	0.977876	0.254316	0.329319	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.01638 (5)	0.01111 (4)	0.01587 (5)	−0.00006 (3)	0.00157 (3)	0.00083 (3)
Br1	0.02060 (13)	0.02395 (12)	0.01946 (14)	0.00223 (9)	0.00222 (10)	−0.00132 (10)
Br2	0.01714 (12)	0.03413 (15)	0.02531 (15)	0.00159 (10)	0.00106 (11)	−0.00382 (11)
Br3	0.03326 (16)	0.02572 (13)	0.01649 (13)	−0.00212 (11)	−0.00183 (11)	0.00417 (10)
Br4	0.03725 (16)	0.01262 (11)	0.02997 (16)	−0.00035 (10)	0.01171 (12)	−0.00028 (10)
O1A	0.0530 (15)	0.0219 (10)	0.0179 (11)	0.0140 (9)	−0.0025 (10)	−0.0030 (8)
O2A	0.0340 (12)	0.0245 (10)	0.0209 (11)	0.0097 (8)	−0.0045 (9)	0.0011 (8)
C1A	0.0201 (13)	0.0166 (11)	0.0192 (13)	0.0010 (9)	0.0026 (10)	0.0001 (9)
C2A	0.0255 (14)	0.0184 (11)	0.0157 (13)	0.0034 (10)	0.0002 (10)	0.0002 (9)
C3A	0.0269 (14)	0.0203 (12)	0.0255 (15)	0.0000 (10)	0.0086 (12)	−0.0038 (11)
N1A	0.0255 (12)	0.0179 (10)	0.0350 (15)	0.0002 (9)	0.0082 (11)	−0.0043 (10)
O1B	0.0397 (13)	0.0392 (13)	0.0254 (12)	−0.0156 (10)	0.0152 (10)	−0.0090 (9)
O2B	0.0255 (10)	0.0172 (9)	0.0287 (11)	−0.0041 (7)	0.0066 (9)	−0.0009 (8)
C1B	0.0184 (13)	0.0221 (12)	0.0206 (14)	−0.0014 (9)	0.0013 (10)	0.0012 (10)
C2B	0.0222 (13)	0.0199 (12)	0.0244 (15)	−0.0052 (10)	0.0037 (11)	−0.0004 (10)
C3B	0.0283 (15)	0.0244 (13)	0.0254 (15)	0.0026 (11)	−0.0013 (12)	−0.0033 (11)
N1B	0.0305 (13)	0.0235 (11)	0.0283 (14)	0.0017 (10)	0.0111 (11)	−0.0014 (10)

Geometric parameters (Å, º) top

Pb1—Br1	3.0589 (4)	N1A—H11A	0.9100
Pb1—Br3	2.9230 (4)	N1A—H12A	0.9100
Pb1—Br2	2.8952 (3)	N1A—H13A	0.9100
Pb1—Br2ⁱ	3.2714 (2)	O1B—C1B	1.323 (3)
Pb1—Br4	2.9477 (3)	O1B—H1B	0.88 (2)
Pb1—Br4ⁱⁱ	3.0591 (3)	O2B—C1B	1.212 (3)
O1A—C1A	1.323 (3)	C1B—C2B	1.497 (4)
O1A—H1A	0.90 (2)	C2B—C3B	1.498 (4)
O2A—C1A	1.215 (3)	C2B—H21B	0.9900
C1A—C2A	1.493 (4)	C2B—H22B	0.9900
C2A—C3A	1.512 (4)	C3B—N1B	1.487 (4)
C2A—H21A	0.9900	C3B—H31B	0.9900
C2A—H22A	0.9900	C3B—H32B	0.9900
C3A—N1A	1.494 (4)	N1B—H11B	0.9100
C3A—H31A	0.9900	N1B—H12B	0.9100
C3A—H32A	0.9900	N1B—H13B	0.9100

Br1—Pb1—Br2	88.107 (9)	C2A—C3A—H32A	109.2
Br1—Pb1—Br2ⁱ	80.90 (1)	H31A—C3A—H32A	107.9
Br1—Pb1—Br4	87.683 (8)	C3A—N1A—H11A	109.5
Br1—Pb1—Br4ⁱⁱ	89.760 (8)	C3A—N1A—H12A	109.5
Br2—Pb1—Br4	90.568 (9)	H11A—N1A—H12A	109.5
Br2—Pb1—Br4ⁱⁱ	96.645 (9)	C3A—N1A—H13A	109.5
Br2ⁱ—Pb1—Br4	90.75 (1)	H11A—N1A—H13A	109.5
Br2ⁱ—Pb1—Br4ⁱⁱ	81.63 (1)	H12A—N1A—H13A	109.5
Br3—Pb1—Br2	87.836 (9)	C1B—O1B—H1B	112 (3)
Br3—Pb1—Br4	92.596 (8)	O2B—C1B—O1B	122.7 (3)
Br3—Pb1—Br4ⁱⁱ	90.472 (8)	O2B—C1B—C2B	124.7 (3)
Pb1—Br2—Pb1ⁱⁱⁱ	168.87 (1)	O1B—C1B—C2B	112.5 (2)
Pb1—Br2ⁱ—Pb1ⁱ	168.87 (1)	C1B—C2B—C3B	113.8 (2)
Pb1—Br4—Pb1^iv	168.90 (1)	C1B—C2B—H21B	108.8
Br3—Pb1—Br1	175.936 (9)	C3B—C2B—H21B	108.8
Br4—Pb1—Br4ⁱⁱ	172.266 (4)	C1B—C2B—H22B	108.8
C1A—O1A—H1A	107 (3)	C3B—C2B—H22B	108.8
O2A—C1A—O1A	122.8 (3)	H21B—C2B—H22B	107.7
O2A—C1A—C2A	124.2 (2)	N1B—C3B—C2B	111.7 (2)
O1A—C1A—C2A	112.9 (2)	N1B—C3B—H31B	109.3
C1A—C2A—C3A	113.4 (2)	C2B—C3B—H31B	109.3
C1A—C2A—H21A	108.9	N1B—C3B—H32B	109.3
C3A—C2A—H21A	108.9	C2B—C3B—H32B	109.3
C1A—C2A—H22A	108.9	H31B—C3B—H32B	107.9
C3A—C2A—H22A	108.9	C3B—N1B—H11B	109.5
H21A—C2A—H22A	107.7	C3B—N1B—H12B	109.5
N1A—C3A—C2A	112.0 (2)	H11B—N1B—H12B	109.5
N1A—C3A—H31A	109.2	C3B—N1B—H13B	109.5
C2A—C3A—H31A	109.2	H11B—N1B—H13B	109.5
N1A—C3A—H32A	109.2	H12B—N1B—H13B	109.5

O1A—C1A—C2A—C3a	−164.4 (2)	O1B—C1B—C2B—C3B	171.4 (2)
C1A—C2A—C3A—N1A	−62.9 (3)	C1B—C2B—C3B—N1B	59.7 (3)

Symmetry codes: (i) x−1, y, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) −x+1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···Br3ⁱⁱ	0.90 (2)	2.35 (3)	3.241 (2)	171 (4)
N1A—H11A···O2A	0.91	2.18	2.853 (3)	130
N1A—H12A···Br1^v	0.91	2.73	3.619 (2)	166
N1A—H13A···Br1^vi	0.91	2.58	3.445 (2)	159
O1B—H1B···Br1^v	0.88 (2)	2.32 (3)	3.188 (2)	167 (4)
N1B—H11B···Br3^vii	0.91	2.49	3.343 (2)	157
N1B—H12B···Br1ⁱⁱⁱ	0.91	2.76	3.484 (2)	137
N1B—H12B···O2B	0.91	2.17	2.839 (3)	129
N1B—H13B···Br4^vii	0.91	2.56	3.407 (2)	155

Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x, −y+1, −z+1; (vii) −x+3/2, y−1/2, −z+1/2.

Cation geometry (°) top

Torsion angle	Value
O1A-C1A-C2A-C3A	-164.4 (2)
C1A-C2A-C3A-N1A	-62.9 (3)

O1B-C1B-C2B-C3B	171.4 (2)
C1B-C2B-C3B-N1B	59.7 (3)

Anion geometry (Å, °) top

Pb1-Br1	3.0589 (3)	Pb1-Br2	2.8952 (3)	Pb1-Br4	2.9477 (3)
Pb1-Br3	2.9230 (4)	Pb1-Br2ⁱ	3.2714 (2)	Pb1-Br4ⁱⁱ	3.0591 (3)

Br1-Pb1-Br2	88.11 (1)	Br2-Pb1-Br4	90.57 (1)	Br3-Pb1-Br2	103.14 (1)
Br1-Pb1-Br2ⁱ	80.90 (1)	Br2-Pb1-Br4ⁱⁱ	96.64 (1)	Br3-Pb1-Br2ⁱ	87.83 (1)
Br1-Pb1-Br4	87.68 (1)	Br2ⁱ-Pb1-Br4	90.75 (1)	Br3-Pb1-Br4	92.60 (1)
Br1-Pb1-Br4ⁱⁱ	89.76 (1)	Br2ⁱ-Pb1-Br4ⁱⁱ	81.63 (1)	Br3-Pb1-Br4ⁱⁱ	90.47 (1)

Pb1-Br2-Pb1ⁱⁱⁱ	168.87 (1)	Pb1-Br4-Pb1^iv	168.90 (1)
Pb1-Br2ⁱ-Pb1ⁱ	168.87 (1)	Pb1-Br4ⁱ-Pb1ⁱⁱ	168.90 (1)

Symmetry codes: (i) x-1, y, z; (ii) -x+1/2, y-1/2, -z+1/2; (iii) x+1, y, z; (iv) -x+1/2, y+1/2, -z+1/2.

Funding information

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

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