Crystal structure and Hirshfeld surface analysis of phenyl­alanine hydro­bromide

Kucheriv, O.I.; Bargan, A.; Potaskalov, V.; Brusylovets, O.; Prysiazhna, O.

doi:10.1107/S2056989026010406

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 82| Part 11| November 2026| Pages 1304-1308

https://doi.org/10.1107/S2056989026010406

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Crystal structure and Hirshfeld surface analysis of phenylalanine hydrobromide

Olesia I. Kucheriv,^a ^* Alexandra Bargan,^b Vadim Potaskalov,^c Oleksii Brusylovets ^a and Olena Prysiazhna ^d,^e

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska St. 64, Kyiv 01601, Ukraine, ^bDepartment of Inorganic Polymers, Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41-A, Iasi 700487, Romania, ^cDepartment of General and Inorganic Chemistry, National Technical University of Ukraine Igor Sikorsky Kyiv Polytechnic Institute, Beresteiskyi Pr. 37, Kyiv 03056, Ukraine, ^dBakul Institute for Superhard Materials, National Academy of Sciences of Ukraine, Avtozavodska St. 2, Kyiv 04074, Ukraine, and ^eInstitute of Innovative Education of Kyiv National University of Construction and Architecture, 4 Osvity Street, Kyiv 03037, Ukraine
^*Correspondence e-mail: [email protected]

Edited by X. Hao, Institute of Chemistry, Chinese Academy of Sciences (Received 1 October 2026; accepted 8 October 2026; online 20 October 2026)

Amino acid salts represent a diverse class of molecular solids in which ionic interactions and hydrogen bonding between protonated amino acid species and counter-ions govern the formation of supramolecular architectures. Phenylalanine hydrobromide (systematic name: 1-carboxy-2-phenylethan-1-aminium bromide, C₉H₁₂NO₂⁺·Br⁻) crystallizes in the chiral orthorhombic space group P2₁2₁2₁. Its structure is built from protonated phenylalaninium cations, which interact with bromide anions through a network of N—H⋯Br and O—H⋯Br hydrogen bonds, forming bilayers propagating parallel to the ab plane, with the polar groups oriented toward the interior of the bilayers. The crystal structure is additionally consolidated by three types of weak T-shaped C(sp²)—H⋯π interactions.

Keywords: crystal structure; amino acid salt; phenylalanine; bromide.

CCDC reference: 2593846

1. Chemical context

Amino acids are fundamental building blocks of living systems and play a central role in biological processes, while their diverse chemical functionality also makes them important molecular components in supramolecular and materials chemistry (Wang et al., 2024 ). In the solid state, amino acids commonly exist as zwitterions and form extended networks through hydrogen bonding and electrostatic interactions (Görbitz, 2015 ; Moggach et al., 2015 ). Consequently, knowledge of their crystal structures is essential for understanding the relationship between molecular structure, intermolecular interactions and the resulting properties of the solid phase. Amino acids have therefore long attracted attention in crystallographic studies, providing important model systems for investigating hydrogen-bonding patterns, molecular packing, polymorphism and structure–property relationships (Yamada et al., 2008 ; de Moraes et al., 2018 ). Modification of the ionic environment through protonation of the amino group and incorporation of inorganic counter-ions offers an additional means of controlling crystal packing and generating new structural motifs (Fleck & Petrosyan, 2014 ). In particular, halide salts of amino acids provide useful model systems in which the hydrogen-bonding functionality of the organic component is combined with different inorganic counter-ions. Their crystal structures offer insight into how the nature of the halide and the presence of solvent molecules influence intermolecular interactions, crystal packing and the resulting supramolecular organization (Petrosyan et al., 2020 ).

Amino acid halide salts have also emerged as useful precursors and building blocks for hybrid organic–inorganic perovskites. Hybrid halide perovskites have attracted considerable attention due to their compositional and structural tunability, which gives rise to a broad range of optical, electronic and other functional properties (Kucheriv et al., 2023 ; Kucheriv et al., 2025 ). The incorporation of amino-acid-derived cations into metal–halide frameworks enables the introduction of chirality and additional hydrogen-bonding interactions, while retaining the characteristic structural flexibility of hybrid halide materials. Sirenko and co-workers demonstrated that α-alanine can serve as an organic component of chiral lead–halide hybrid perovskites, yielding (AlaH)PbX₃ compounds with distinct low-dimensional inorganic architectures and semiconducting optical properties (Sirenko et al., 2021 ). Similar structural principles were subsequently extended to L-histidine, affording two-dimensional hybrid perovskites in which the amino acid cations separate the inorganic layers and induce noncentrosymmetric structures (Sirenko et al., 2022 ). More recently, proline-based lead bromide perovskites further demonstrated the substantial structural diversity accessible through the use of amino-acid-derived organic cations (Sirenko et al., 2023 ). These examples highlight the importance of understanding the crystal structures and intermolecular interactions of amino acid halide salts themselves, as such structural information is relevant to their role as molecular building blocks for the rational development of functional hybrid materials.

In this article, we report the crystal structure of phenylalaninium bromide and discuss its structural features and intermolecular interactions.

2. Structural commentary

The title salt crystallizes in the space group P2₁2₁2₁. The asymmetric unit contains three protonated phenylalaninium cations and three bromide anions (Fig. 1). All bond lengths and angles are within the expected range. The phenylalaninium cation containing the C1–C6 aromatic ring is denoted as A, C10–C15 as B and C19–C24 as C. The C1—C7—C8—N1 and C10—C16—C17—N2 torsion angles in A and B are 56.6 (3) and 57.4 (3)°, respectively, indicating that these cations adopt anticlinal conformation. The C19—C25—C26—N3 torsion angle in C is 168.8 (2)°, which is close to an antiperiplanar conformation. Due to such conformations, the A and B cations feature intermolecular C2—H2⋯O1 and C15—H15⋯O3 hydrogen bonds, while such an interaction is geometrically impossible in C. The detailed geometric parameters of the hydrogen bonds which are formed in this crystal structure are given in Table 1. The carboxylic acid group exhibits the expected asymmetric C—O bond lengths in all three types of phenylalaninium cations, with the C=O and C—OH bonds measuring ca 1.20 and 1.35 Å, respectively, in all three cases. This pronounced differentiation is consistent with the presence of a localized carbonyl and hydroxyl functionality rather than a delocalized carboxylate group.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Br1	0.75	2.43	3.175 (2)	175
O3—H3A⋯Br2	0.76	2.41	3.165 (2)	173
O5—H5A⋯Br3	0.85	2.34	3.183 (2)	173
N1—H1A⋯Br2ⁱ	0.89	2.56	3.408 (2)	160
N1—H1B⋯Br3ⁱ	0.89	2.48	3.293 (2)	154
N1—H1B⋯O6ⁱ	0.89	2.67	3.140 (3)	114
N1—H1C⋯Br2ⁱⁱ	0.89	2.45	3.332 (2)	171
N2—H2A⋯Br1	0.87	2.65	3.428 (2)	149
N2—H2A⋯O2	0.87	2.52	3.038 (3)	119
N2—H2B⋯Br3ⁱⁱⁱ	0.87	2.44	3.301 (2)	170
N2—H2C⋯Br3ⁱ	0.87	2.54	3.391 (2)	164
N3—H3B⋯Br1	0.87	2.55	3.406 (2)	168
N3—H3C⋯Br2	0.87	2.47	3.309 (2)	162
N3—H3C⋯O4	0.87	2.59	2.913 (3)	103
N3—H3D⋯Br1^iv	0.87	2.48	3.324 (2)	163
C2—H2⋯O1	0.95	2.81	3.487 (4)	129
C8—H8⋯O2^iv	1.00	2.58	3.406 (3)	140
C12—H12⋯O5ⁱ	0.95	2.96	3.347 (4)	106
C15—H15⋯O3	0.95	2.77	3.449 (4)	129
C17—H17⋯O4^v	1.00	2.60	3.460 (3)	144
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) ; (v) .

Figure 1
The asymmetric unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

Phenylalaninium cations form an extensive network of N—H⋯Br and O—H⋯Br hydrogen bonds with bromide counter-ions (Table 1). Phenylalaninium cations are arranged in double layers propagating along the ab plane. Additional connection inside the layer is ensured by weak C8—H8⋯O2^iv and C17—H17⋯O4^v (Table 1) contacts. The carboxyl groups and ammonium cations face inside the double layers (Fig. 2). These double layers interact with each other by weak T-shaped C(sp²)—H⋯π interactions. In total, three types of C(sp²)—H⋯π interactions are formed: C24—H24⋯π(C) of 2.2898 (12) Å, C3—H3⋯π(B) of 2.6528 (12) Å and C14—H14⋯π(A) of 2.7747 (11) Å (Fig. 3).

Figure 2
Fragment of the title compound, showing propagation of the supramolecular bilayers in the ab plane.

Figure 3
Fragment of the title compound showing C(sp²)—H⋯π interactions.

4. Hirshfeld surface analysis

Hirshfeld surface analysis was performed separately for each crystallographically independent phenylalaninium cation. The Hirshfeld surfaces mapped over d_norm were generated at the standard resolution to visualize and characterize the intermolecular contacts in the crystal structure [Figs. 4(a)–(f)]. A fixed colour scale was used, with white regions corresponding to contacts close to the sum of the van der Waals radii, whereas shorter and longer contacts are indicated by red and blue regions, respectively. In all three cases, the most pronounced red regions correspond to the shortest N—H⋯Br and N—H⋯O contacts. The associated two-dimensional fingerprint plots provide a quantitative representation of the intermolecular contacts and their contributions to the crystal packing.

Figure 4
Hirshfeld surface and fingerprint plots of the (a)/(b) A, (c)/(d) B and (e)/(f) C phenylalaninium cations.

For all three cations, the most significant weak intermolecular contacts are O⋯H/H⋯O, C⋯H/H⋯C and Br⋯H/H⋯Br, each contributing approximately 15–20% to the Hirshfeld surface. The exact contributions vary slightly among the three crystallographically independent cations and are given in Figs. 4(b)–(d). The O⋯H/H⋯O contacts arise from both C—H⋯O and N—H⋯O interactions, whereas the Br⋯H/H⋯Br contacts are primarily associated with hydrogen bonding between the protonated ammonium or hydroxyl groups and bromide anions. The C⋯H/H⋯C contacts are associated with C—H⋯π interactions present in the crystal structure.

The remaining contribution to the fingerprint plots arises predominantly from H⋯H contacts. Although these contacts contribute appreciably to the overall Hirshfeld surface, they do not correspond to specific directional intermolecular interactions and mainly originate from H atoms at the terminal positions of the molecular fragments.

5. Database survey

A survey of the Cambridge Structural Database (CSD, Version 6.01, update of Fabruary 2026; Groom et al., 2016 ) revealed one chemically related structure of L-phenylalanine L-phenylalaninium bromide (CADLOK01), which contained cocrystallized L-phenylalanine and L-phenylalaninium bromide in a 1:1 ratio (Surekha et al., 2014 ).

6. Synthesis and crystallization

100 mg of phenylalanine were dissolved in 100 µl of concentrated (48%) HBr under heating and left to cool to room temperature. Within 1 h, colourless crystals suitable for X-ray analysis formed. The obtained crystals were stired in the mother liquor prior to measurement.

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 U_iso(H) = 1.2U_eq(C), 1.2U_eq(N) or 1.5U_eq(O). Ternary CH, secondary CH₂ and aromatic H were refined with riding coordinates. Idealized NH₃ and idealized tetrahedral OH were refined as rotating groups with stretchable bonds.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₂NO₂⁺·Br⁻
M_r	246.11
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	5.5716 (1), 21.6685 (4), 25.9870 (5)
V (Å³)	3137.36 (10)
Z	12
Radiation type	Mo Kα
μ (mm⁻¹)	3.90
Crystal size (mm)	0.25 × 0.09 × 0.04

Data collection
Diffractometer	Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2024 )
T_min, T_max	0.605, 0.880
No. of measured, independent and observed [I > 2σ(I)] reflections	20376, 7687, 6897
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.709

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.046, 1.02
No. of reflections	7687
No. of parameters	364
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.28
Absolute structure	Flack x determined using 2670 quotients [(I⁺)−(I⁻)]/[(I⁺)+ (I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.008 (4)
Computer programs: CrysAlis PRO (Rigaku OD, 2024), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2593846

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026010406/nx2040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026010406/nx2040Isup2.hkl

checkCIF report

Computing details top

1-Carboxy-2-phenylethan-1-aminium bromide top

Crystal data top

C₉H₁₂NO₂⁺·Br⁻	D_x = 1.563 Mg m⁻³
M_r = 246.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 11408 reflections
a = 5.5716 (1) Å	θ = 2.5–29.5°
b = 21.6685 (4) Å	µ = 3.90 mm⁻¹
c = 25.9870 (5) Å	T = 100 K
V = 3137.36 (10) Å³	Block, colourless
Z = 12	0.25 × 0.09 × 0.04 mm
F(000) = 1488

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	7687 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	6897 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.0000 pixels mm^-1	θ_max = 30.2°, θ_min = 2.5°
ω scans	h = −6→7
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2024)	k = −24→29
T_min = 0.605, T_max = 0.880	l = −32→29
20376 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0197P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.046	(Δ/σ)_max = 0.002
S = 1.02	Δρ_max = 0.39 e Å⁻³
7687 reflections	Δρ_min = −0.28 e Å⁻³
364 parameters	Absolute structure: Flack x determined using 2670 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.008 (4)

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
Br1	0.17873 (4)	0.65257 (2)	0.67621 (2)	0.01527 (7)
Br2	0.78091 (5)	0.82203 (2)	0.80185 (2)	0.01596 (7)
Br3	0.25455 (4)	0.99336 (2)	0.68558 (2)	0.01323 (7)
O1	0.5903 (4)	0.55574 (10)	0.65121 (9)	0.0224 (5)
H1	0.489 (6)	0.5774 (13)	0.6558 (11)	0.034*
O2	0.3724 (3)	0.49088 (9)	0.70016 (9)	0.0161 (5)
O3	0.3734 (4)	0.72749 (9)	0.83319 (9)	0.0201 (5)
H3A	0.479 (6)	0.7486 (12)	0.8276 (12)	0.030*
O4	0.5867 (3)	0.65787 (10)	0.78801 (8)	0.0148 (4)
O5	0.5947 (4)	0.88562 (10)	0.64538 (9)	0.0275 (6)
H5A	0.496 (6)	0.9136 (13)	0.6539 (12)	0.041*
O6	0.3590 (3)	0.82479 (10)	0.69374 (8)	0.0196 (5)
N1	0.7272 (4)	0.40849 (10)	0.70936 (9)	0.0134 (5)
H1A	0.592 (3)	0.3912 (6)	0.6987 (5)	0.016*
H1B	0.712 (3)	0.4195 (2)	0.7421 (6)	0.016*
H1C	0.847 (3)	0.3817 (6)	0.7063 (6)	0.016*
N2	0.2357 (4)	0.57364 (10)	0.78988 (9)	0.0125 (5)
H2A	0.250 (3)	0.58000 (18)	0.7569 (6)	0.015*
H2B	0.118 (2)	0.5481 (5)	0.7955 (6)	0.015*
H2C	0.369 (3)	0.5579 (5)	0.8018 (5)	0.015*
N3	0.6877 (4)	0.73528 (10)	0.69898 (9)	0.0140 (5)
H3B	0.546 (3)	0.7193 (6)	0.6942 (4)	0.017*
H3C	0.696 (3)	0.7508 (3)	0.7298 (5)	0.017*
H3D	0.796 (3)	0.7067 (6)	0.6954 (5)	0.017*
C1	0.7015 (5)	0.40577 (13)	0.59356 (10)	0.0124 (6)
C2	0.4939 (5)	0.42966 (14)	0.57039 (12)	0.0149 (6)
H2	0.459171	0.472434	0.573325	0.018*
C3	0.3396 (5)	0.39180 (16)	0.54340 (12)	0.0200 (7)
H3	0.198754	0.408471	0.528201	0.024*
C4	0.3900 (6)	0.32964 (16)	0.53849 (12)	0.0237 (8)
H4	0.284106	0.303673	0.519730	0.028*
C5	0.5940 (6)	0.30515 (15)	0.56078 (12)	0.0211 (7)
H5	0.628197	0.262391	0.557441	0.025*
C6	0.7497 (5)	0.34346 (14)	0.58824 (10)	0.0174 (6)
H6	0.890139	0.326542	0.603431	0.021*
C7	0.8698 (4)	0.44712 (14)	0.62374 (11)	0.0130 (6)
H7A	0.896221	0.485554	0.603939	0.016*
H7B	1.026675	0.426083	0.627167	0.016*
C8	0.7793 (4)	0.46417 (12)	0.67745 (11)	0.0124 (6)
H8	0.909917	0.487770	0.695034	0.015*
C9	0.5549 (5)	0.50447 (13)	0.67785 (12)	0.0129 (6)
C10	0.2838 (5)	0.58765 (13)	0.90514 (10)	0.0113 (6)
C11	0.2425 (5)	0.52576 (13)	0.91687 (11)	0.0140 (6)
H11	0.103093	0.505814	0.903990	0.017*
C12	0.4030 (5)	0.49308 (15)	0.94713 (12)	0.0181 (7)
H12	0.374020	0.450834	0.954657	0.022*
C13	0.6066 (5)	0.52212 (14)	0.96649 (12)	0.0156 (7)
H13	0.715685	0.499804	0.987537	0.019*
C14	0.6502 (5)	0.58351 (14)	0.95512 (11)	0.0139 (6)
H14	0.790007	0.603240	0.968066	0.017*
C15	0.4894 (4)	0.61617 (14)	0.92475 (11)	0.0127 (6)
H15	0.519442	0.658375	0.917216	0.015*
C16	0.1064 (4)	0.62332 (13)	0.87211 (11)	0.0109 (6)
H16A	0.078216	0.664093	0.888195	0.013*
H16B	−0.048354	0.600878	0.871971	0.013*
C17	0.1859 (4)	0.63338 (12)	0.81636 (11)	0.0113 (6)
H17	0.051278	0.654129	0.797699	0.014*
C18	0.4083 (5)	0.67351 (13)	0.81056 (11)	0.0120 (6)
C19	0.8038 (5)	0.79904 (12)	0.56348 (10)	0.0120 (6)
C20	1.0195 (5)	0.83066 (13)	0.56674 (12)	0.0178 (7)
H20	1.112471	0.828004	0.597308	0.021*
C21	1.1015 (5)	0.86625 (14)	0.52580 (13)	0.0218 (7)
H21	1.249390	0.887782	0.528716	0.026*
C22	0.9702 (6)	0.87050 (14)	0.48114 (13)	0.0219 (7)
H22	1.026983	0.894670	0.453172	0.026*
C23	0.7545 (5)	0.83918 (14)	0.47738 (11)	0.0213 (7)
H23	0.662621	0.841877	0.446675	0.026*
C24	0.6716 (5)	0.80379 (13)	0.51828 (11)	0.0143 (6)
H24	0.522950	0.782619	0.515326	0.017*
C25	0.7183 (5)	0.75706 (12)	0.60608 (10)	0.0131 (6)
H25A	0.816393	0.718980	0.605500	0.016*
H25B	0.550219	0.745061	0.598786	0.016*
C26	0.7294 (5)	0.78472 (12)	0.66055 (10)	0.0125 (6)
H26	0.891551	0.803235	0.666316	0.015*
C27	0.5384 (5)	0.83380 (13)	0.66893 (11)	0.0138 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01505 (13)	0.01604 (15)	0.01472 (16)	0.00555 (11)	−0.00005 (11)	0.00074 (13)
Br2	0.01382 (14)	0.01551 (14)	0.01854 (16)	−0.00551 (11)	−0.00003 (11)	−0.00128 (12)
Br3	0.01307 (12)	0.01245 (14)	0.01418 (15)	0.00420 (11)	0.00076 (12)	0.00126 (11)
O1	0.0219 (11)	0.0155 (12)	0.0299 (15)	0.0056 (9)	0.0108 (10)	0.0035 (11)
O2	0.0123 (9)	0.0187 (12)	0.0172 (12)	0.0027 (8)	0.0036 (8)	−0.0003 (9)
O3	0.0194 (11)	0.0140 (11)	0.0268 (14)	−0.0051 (9)	0.0091 (9)	−0.0021 (10)
O4	0.0126 (9)	0.0149 (11)	0.0171 (12)	−0.0021 (9)	0.0022 (8)	0.0014 (10)
O5	0.0383 (13)	0.0114 (12)	0.0329 (16)	0.0103 (10)	0.0213 (11)	0.0066 (11)
O6	0.0156 (10)	0.0192 (11)	0.0241 (13)	0.0053 (8)	0.0052 (9)	0.0011 (10)
N1	0.0112 (11)	0.0174 (13)	0.0115 (12)	0.0032 (10)	−0.0006 (10)	−0.0016 (10)
N2	0.0131 (11)	0.0131 (12)	0.0111 (12)	−0.0053 (10)	0.0013 (10)	−0.0013 (9)
N3	0.0136 (11)	0.0148 (13)	0.0135 (13)	0.0045 (9)	0.0016 (10)	0.0010 (10)
C1	0.0135 (13)	0.0168 (15)	0.0067 (15)	0.0003 (11)	0.0036 (11)	0.0008 (11)
C2	0.0150 (14)	0.0187 (17)	0.0112 (17)	0.0050 (12)	0.0022 (11)	−0.0007 (13)
C3	0.0140 (14)	0.036 (2)	0.0105 (16)	0.0016 (14)	−0.0001 (12)	0.0012 (14)
C4	0.0240 (17)	0.035 (2)	0.0118 (18)	−0.0132 (14)	0.0011 (13)	−0.0045 (15)
C5	0.0331 (18)	0.0180 (17)	0.0121 (18)	−0.0059 (14)	0.0038 (13)	0.0013 (14)
C6	0.0195 (14)	0.0214 (15)	0.0114 (15)	0.0040 (14)	0.0001 (12)	0.0012 (12)
C7	0.0094 (13)	0.0155 (16)	0.0139 (17)	0.0006 (11)	0.0028 (11)	0.0008 (13)
C8	0.0094 (12)	0.0134 (14)	0.0145 (15)	0.0008 (10)	−0.0012 (12)	−0.0021 (12)
C9	0.0157 (13)	0.0115 (16)	0.0114 (17)	0.0024 (11)	−0.0007 (12)	−0.0044 (14)
C10	0.0110 (13)	0.0166 (15)	0.0063 (14)	0.0013 (11)	0.0028 (11)	−0.0010 (11)
C11	0.0143 (13)	0.0156 (14)	0.0121 (14)	−0.0040 (12)	0.0031 (12)	−0.0019 (11)
C12	0.0211 (15)	0.0135 (16)	0.020 (2)	0.0023 (13)	0.0024 (12)	0.0005 (14)
C13	0.0166 (14)	0.0188 (17)	0.0114 (18)	0.0039 (12)	0.0007 (12)	0.0004 (13)
C14	0.0112 (13)	0.0201 (16)	0.0103 (16)	−0.0010 (12)	0.0012 (11)	−0.0025 (12)
C15	0.0137 (13)	0.0128 (15)	0.0115 (17)	−0.0017 (11)	0.0038 (11)	−0.0004 (13)
C16	0.0104 (12)	0.0117 (16)	0.0107 (16)	−0.0003 (11)	0.0024 (11)	−0.0019 (12)
C17	0.0114 (12)	0.0102 (14)	0.0122 (15)	0.0011 (10)	0.0005 (11)	0.0005 (11)
C18	0.0151 (13)	0.0120 (15)	0.0089 (16)	−0.0016 (11)	−0.0038 (11)	0.0032 (13)
C19	0.0154 (14)	0.0111 (13)	0.0096 (14)	0.0043 (11)	0.0025 (11)	−0.0031 (12)
C20	0.0147 (14)	0.0212 (19)	0.0176 (17)	0.0013 (11)	−0.0010 (12)	0.0000 (14)
C21	0.0187 (15)	0.0173 (17)	0.029 (2)	0.0002 (12)	0.0082 (13)	0.0023 (15)
C22	0.0316 (17)	0.0144 (18)	0.020 (2)	0.0043 (13)	0.0104 (14)	0.0030 (14)
C23	0.0325 (16)	0.0213 (17)	0.0100 (15)	0.0064 (15)	−0.0024 (13)	−0.0018 (12)
C24	0.0152 (14)	0.0143 (15)	0.0133 (16)	−0.0010 (11)	0.0000 (11)	−0.0039 (12)
C25	0.0152 (14)	0.0125 (14)	0.0116 (14)	0.0003 (12)	0.0003 (11)	−0.0012 (11)
C26	0.0137 (13)	0.0133 (14)	0.0106 (14)	−0.0002 (12)	0.0000 (11)	0.0013 (11)
C27	0.0174 (14)	0.0141 (18)	0.0100 (17)	−0.0002 (12)	−0.0038 (11)	−0.0022 (13)

Geometric parameters (Å, º) top

O1—H1	0.75 (4)	C8—H8	1.0000
O1—C9	1.324 (4)	C8—C9	1.525 (4)
O2—C9	1.207 (3)	C10—C11	1.394 (4)
O3—H3A	0.76 (4)	C10—C15	1.398 (4)
O3—C18	1.324 (3)	C10—C16	1.520 (4)
O4—C18	1.203 (3)	C11—H11	0.9500
O5—H5A	0.85 (4)	C11—C12	1.385 (4)
O5—C27	1.317 (3)	C12—H12	0.9500
O6—C27	1.205 (3)	C12—C13	1.391 (4)
N1—H1A	0.887 (15)	C13—H13	0.9500
N1—H1B	0.887 (15)	C13—C14	1.384 (4)
N1—H1C	0.887 (15)	C14—H14	0.9500
N1—C8	1.492 (3)	C14—C15	1.388 (4)
N2—H2A	0.872 (14)	C15—H15	0.9500
N2—H2B	0.872 (15)	C16—H16A	0.9900
N2—H2C	0.872 (15)	C16—H16B	0.9900
N2—C17	1.492 (3)	C16—C17	1.531 (4)
N3—H3B	0.871 (15)	C17—H17	1.0000
N3—H3C	0.871 (14)	C17—C18	1.521 (4)
N3—H3D	0.871 (14)	C19—C20	1.386 (4)
N3—C26	1.483 (3)	C19—C24	1.390 (4)
C1—C2	1.403 (4)	C19—C25	1.510 (4)
C1—C6	1.384 (4)	C20—H20	0.9500
C1—C7	1.516 (4)	C20—C21	1.391 (4)
C2—H2	0.9500	C21—H21	0.9500
C2—C3	1.380 (4)	C21—C22	1.375 (5)
C3—H3	0.9500	C22—H22	0.9500
C3—C4	1.382 (5)	C22—C23	1.384 (4)
C4—H4	0.9500	C23—H23	0.9500
C4—C5	1.381 (5)	C23—C24	1.390 (4)
C5—H5	0.9500	C24—H24	0.9500
C5—C6	1.397 (4)	C25—H25A	0.9900
C6—H6	0.9500	C25—H25B	0.9900
C7—H7A	0.9900	C25—C26	1.538 (4)
C7—H7B	0.9900	C26—H26	1.0000
C7—C8	1.529 (4)	C26—C27	1.520 (4)

C9—O1—H1	109.5	C11—C12—H12	120.0
C18—O3—H3A	109.5	C11—C12—C13	120.0 (3)
C27—O5—H5A	109.5	C13—C12—H12	120.0
H1A—N1—H1B	109.5	C12—C13—H13	120.0
H1A—N1—H1C	109.5	C14—C13—C12	120.0 (3)
H1B—N1—H1C	109.5	C14—C13—H13	120.0
C8—N1—H1A	109.5	C13—C14—H14	120.1
C8—N1—H1B	109.5	C13—C14—C15	119.9 (3)
C8—N1—H1C	109.5	C15—C14—H14	120.1
H2A—N2—H2B	109.5	C10—C15—H15	119.6
H2A—N2—H2C	109.5	C14—C15—C10	120.7 (3)
H2B—N2—H2C	109.5	C14—C15—H15	119.6
C17—N2—H2A	109.5	C10—C16—H16A	108.6
C17—N2—H2B	109.5	C10—C16—H16B	108.6
C17—N2—H2C	109.5	C10—C16—C17	114.8 (2)
H3B—N3—H3C	109.5	H16A—C16—H16B	107.6
H3B—N3—H3D	109.5	C17—C16—H16A	108.6
H3C—N3—H3D	109.5	C17—C16—H16B	108.6
C26—N3—H3B	109.5	N2—C17—C16	111.5 (2)
C26—N3—H3C	109.5	N2—C17—H17	107.8
C26—N3—H3D	109.5	N2—C17—C18	107.4 (2)
C2—C1—C7	120.9 (3)	C16—C17—H17	107.8
C6—C1—C2	118.5 (3)	C18—C17—C16	114.3 (2)
C6—C1—C7	120.6 (2)	C18—C17—H17	107.8
C1—C2—H2	119.6	O3—C18—C17	110.0 (2)
C3—C2—C1	120.8 (3)	O4—C18—O3	125.9 (3)
C3—C2—H2	119.6	O4—C18—C17	124.1 (3)
C2—C3—H3	120.0	C20—C19—C24	118.3 (3)
C2—C3—C4	120.0 (3)	C20—C19—C25	121.8 (3)
C4—C3—H3	120.0	C24—C19—C25	119.8 (2)
C3—C4—H4	119.9	C19—C20—H20	119.6
C5—C4—C3	120.2 (3)	C19—C20—C21	120.8 (3)
C5—C4—H4	119.9	C21—C20—H20	119.6
C4—C5—H5	120.1	C20—C21—H21	119.7
C4—C5—C6	119.8 (3)	C22—C21—C20	120.5 (3)
C6—C5—H5	120.1	C22—C21—H21	119.7
C1—C6—C5	120.7 (3)	C21—C22—H22	120.4
C1—C6—H6	119.7	C21—C22—C23	119.3 (3)
C5—C6—H6	119.7	C23—C22—H22	120.4
C1—C7—H7A	108.7	C22—C23—H23	119.8
C1—C7—H7B	108.7	C22—C23—C24	120.4 (3)
C1—C7—C8	114.3 (2)	C24—C23—H23	119.8
H7A—C7—H7B	107.6	C19—C24—H24	119.6
C8—C7—H7A	108.7	C23—C24—C19	120.7 (3)
C8—C7—H7B	108.7	C23—C24—H24	119.6
N1—C8—C7	112.1 (2)	C19—C25—H25A	108.5
N1—C8—H8	107.5	C19—C25—H25B	108.5
N1—C8—C9	107.4 (2)	C19—C25—C26	115.3 (2)
C7—C8—H8	107.5	H25A—C25—H25B	107.5
C9—C8—C7	114.5 (2)	C26—C25—H25A	108.5
C9—C8—H8	107.5	C26—C25—H25B	108.5
O1—C9—C8	110.8 (2)	N3—C26—C25	109.4 (2)
O2—C9—O1	125.6 (3)	N3—C26—H26	109.3
O2—C9—C8	123.7 (3)	N3—C26—C27	107.4 (2)
C11—C10—C15	118.7 (3)	C25—C26—H26	109.3
C11—C10—C16	120.4 (2)	C27—C26—C25	112.1 (2)
C15—C10—C16	120.9 (2)	C27—C26—H26	109.3
C10—C11—H11	119.7	O5—C27—C26	111.3 (2)
C12—C11—C10	120.6 (3)	O6—C27—O5	125.8 (3)
C12—C11—H11	119.7	O6—C27—C26	122.9 (3)

N1—C8—C9—O1	178.4 (2)	C11—C10—C16—C17	−103.3 (3)
N1—C8—C9—O2	−0.8 (4)	C11—C12—C13—C14	−0.7 (5)
N2—C17—C18—O3	179.6 (2)	C12—C13—C14—C15	0.6 (4)
N2—C17—C18—O4	0.5 (4)	C13—C14—C15—C10	−0.4 (4)
N3—C26—C27—O5	164.8 (2)	C15—C10—C11—C12	−0.4 (4)
N3—C26—C27—O6	−16.0 (4)	C15—C10—C16—C17	77.4 (3)
C1—C2—C3—C4	−0.7 (5)	C16—C10—C11—C12	−179.7 (3)
C1—C7—C8—N1	56.6 (3)	C16—C10—C15—C14	179.7 (3)
C1—C7—C8—C9	−66.1 (3)	C16—C17—C18—O3	−56.1 (3)
C2—C1—C6—C5	−0.5 (4)	C16—C17—C18—O4	124.7 (3)
C2—C1—C7—C8	76.6 (3)	C19—C20—C21—C22	−0.3 (5)
C2—C3—C4—C5	0.4 (5)	C19—C25—C26—N3	−168.8 (2)
C3—C4—C5—C6	−0.1 (5)	C19—C25—C26—C27	72.2 (3)
C4—C5—C6—C1	0.2 (4)	C20—C19—C24—C23	0.3 (4)
C6—C1—C2—C3	0.7 (4)	C20—C19—C25—C26	48.5 (4)
C6—C1—C7—C8	−103.4 (3)	C20—C21—C22—C23	0.3 (5)
C7—C1—C2—C3	−179.3 (3)	C21—C22—C23—C24	0.0 (4)
C7—C1—C6—C5	179.5 (3)	C22—C23—C24—C19	−0.3 (4)
C7—C8—C9—O1	−56.4 (3)	C24—C19—C20—C21	0.0 (4)
C7—C8—C9—O2	124.3 (3)	C24—C19—C25—C26	−135.3 (3)
C10—C11—C12—C13	0.5 (4)	C25—C19—C20—C21	176.2 (3)
C10—C16—C17—N2	57.4 (3)	C25—C19—C24—C23	−176.0 (2)
C10—C16—C17—C18	−64.6 (3)	C25—C26—C27—O5	−75.1 (3)
C11—C10—C15—C14	0.3 (4)	C25—C26—C27—O6	104.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br1	0.75	2.43	3.175 (2)	175
O3—H3A···Br2	0.76	2.41	3.165 (2)	173
O5—H5A···Br3	0.85	2.34	3.183 (2)	173
N1—H1A···Br2ⁱ	0.89	2.56	3.408 (2)	160
N1—H1B···Br3ⁱ	0.89	2.48	3.293 (2)	154
N1—H1B···O6ⁱ	0.89	2.67	3.140 (3)	114
N1—H1C···Br2ⁱⁱ	0.89	2.45	3.332 (2)	171
N2—H2A···Br1	0.87	2.65	3.428 (2)	149
N2—H2A···O2	0.87	2.52	3.038 (3)	119
N2—H2B···Br3ⁱⁱⁱ	0.87	2.44	3.301 (2)	170
N2—H2C···Br3ⁱ	0.87	2.54	3.391 (2)	164
N3—H3B···Br1	0.87	2.55	3.406 (2)	168
N3—H3C···Br2	0.87	2.47	3.309 (2)	162
N3—H3C···O4	0.87	2.59	2.913 (3)	103
N3—H3D···Br1^iv	0.87	2.48	3.324 (2)	163
C2—H2···O1	0.95	2.81	3.487 (4)	129
C8—H8···O2^iv	1.00	2.58	3.406 (3)	140
C12—H12···O5ⁱ	0.95	2.96	3.347 (4)	106
C15—H15···O3	0.95	2.77	3.449 (4)	129
C17—H17···O4^v	1.00	2.60	3.460 (3)	144

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

Acknowledgements

The authors are grateful to the FAIRE programme provided by the Cambridge Crystallographic Data Centre (CCDC) for the opportunity to use the Cambridge Structural Database (CSD) and associated software. AB is grateful for the support by a grant of the Ministry of Research, Innovation and Digitization, CCCDI–UEFISCDI (project No. PN-IV-P8-8.3-PM-RO-TR-2024-0046), within PNCDI IV [contract ctr.8 BMTR/2025 (SynTioPOSS)].

Funding information

Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant No. 24BF037-01M).

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