Synthesis, crystal structure and Hirshfeld surface analysis of bromido­tetra­kis­[5-(prop-2-en-1-yl­sulf­an­yl)-1,3,4-thia­diazol-2-amine-κN3]copper(II) bromide

Atashov, A.; Azamova, M.; Ziyatov, D.; Uzakbergenova, Z.; Torambetov, B.; Holczbauer, T.; Ashurov, J.; Kadirova, S.

doi:10.1107/S2056989024002652

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ISSN: 2056-9890

Volume 80| Part 4| April 2024| Pages 408-412

https://doi.org/10.1107/S2056989024002652

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Synthesis, crystal structure and Hirshfeld surface analysis of bromidotetrakis[5-(prop-2-en-1-ylsulfanyl)-1,3,4-thiadiazol-2-amine-κN³]copper(II) bromide

Aziz Atashov,^a Mukhlisakhon Azamova,^a Daminbek Ziyatov,^a Zamira Uzakbergenova,^b Batirbay Torambetov,^a ^* Tamas Holczbauer,^c Jamshid Ashurov ^d and Shakhnoza Kadirova ^a

^aNational University of Uzbekistan named after Mirzo Ulugbek, 4 University St., Tashkent, 100174, Uzbekistan, ^bKarakalpak State University, 1 Ch. Abdirov St. Nukus, 230112, Uzbekistan, ^cInstitute of Organic Chemistry, Research Centre for Natural Sciences, 2 Magyar Tudosok Korutja, H-1117 Budapest, Hungary, and ^dInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, M. Ulugbek, St, 83, Tashkent, 100125, Uzbekistan
^*Correspondence e-mail: torambetov_b@mail.ru

Edited by N. Alvarez Failache, Universidad de la Repüblica, Uruguay (Received 4 March 2024; accepted 21 March 2024; online 26 March 2024)

A novel cationic complex, bromidotetrakis[5-(prop-2-en-1-ylsulfanyl)-1,3,4-thiadiazol-2-amine-κN³]copper(II) bromide, [CuBr](C₅H₇N₃S₂)₄Br, was synthesized. The complex crystallizes with fourfold molecular symmetry in the tetragonal space group P4/n. The Cu^II atom exhibits a square-pyramidal coordination geometry. The Cu atom is located centrally within the complex, being coordinated by four nitrogen atoms from four AAT molecules, while a bromine anion is located at the apex of the pyramid. The amino H atoms of AAT interact with bromine from the inner and outer spheres, forming a two-dimensional network in the [100] and [010] directions. Hirshfeld surface analysis reveals that 33.7% of the intermolecular interactions are from H⋯H contacts, 21.2% are from S⋯H/H⋯S contacts, 13.4% are from S⋯S contacts and 11.0% are from C⋯H/H⋯C, while other contributions are from Br⋯H/H⋯Br and N⋯H/H⋯N contacts.

Keywords: crystal structure; copper(II); 1,3,4-thiadiazole; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 2341909

1. Chemical context

Nitrogen-containing heterocycles are a promising class of ligands for the synthesis of transition-metal complexes that are strongly responsive to the changes in external conditions (Lavrenova et al., 2023 ). Derivatives of 1,3,4-thiadiazole represent a relatively new class of compounds that demonstrate a broad array of biological activities, making them of significant interest to various fields in medicinal chemistry and pharmacology worldwide (Gowramma et al., 2018 ; Kaviarasan et al., 2020 ; Upadhyay & Mishra, 2017 ; Yusuf et al., 2008 ). 1,3,4-Thiadiazole derivatives exhibit many biological properties, such as antimicrobial (Li et al., 2014 ; Chen et al., 2019 ), antituberculosis (Foroumadi et al., 2004 ; Kolavi et al., 2006 ), antioxidant (Jakovljević et al., 2017 ; Swapna et al., 2013 ), anticancer (Altıntop et al., 2018 ; Aliabadi, 2016 ), herbicidal (Wang et al., 2011 ) and antifungal (Chen et al., 2007 ; Karaburun et al., 2018 ) activities. In addition, a limited number of studies mention the utilization of diverse thiadiazoles as ligands in the synthesis of biologically active metal complexes (Huxel et al., 2015 ; Chandra et al., 2015 ; Hangan et al., 2015 ).

The strong complexing capability of thiadiazole derivatives is associated with the existence of numerous sulfur and nitrogen atoms and the distinctiveness of its structure, specifically, the presence of unshared electron pairs and donor characteristics. They generate complexes with elements whose ions possess partially vacant d-orbitals or occupied d-orbitals and a low positive charge, exhibiting various polyhedral structures. In this context, investigating the complex-forming properties of thiadiazole derivatives is pertinent in delineating the characteristics of the molecular and electronic structure of the original ligands and the stereochemistry of the coordination polyhedron (Hassan et al., 2018 ). This study focuses on the synthesis, examination of the structure, and characteristics of the [Cu(L)4Br]Br complex, where L is 2-amino-5-allylthio-1,3,4-thiadiazole (AAT), employing single-crystal X-ray diffraction (SC-XRD).

2. Structural commentary

The crystals of [Cu(AAT)₄Br]Br possess an ionic-molecular structure. The complex crystallizes in the fourfold tetragonal system, space group P4/n, and the asymmetric unit comprises one molecule of 2-amino-5-allylthio-1,3,4-thiadiazole (AAT), one Cu²⁺ ion with a multiplicity of 0.25, and Br⁻ ions in two positions with multiplicities of 0.25 each. The Br⁻ ions occupy special positions on fourfold axes, and this symmetry transformation generates the formula unit. In [Cu(AAT)₄Br]Br, the copper atom exhibits a square-pyramidal geometry and its coordination sphere includes four nitrogen atoms (N2) from the heterocyclic ligands and a bromine anion at the top of the pyramid. These nitrogen atoms lie in one plane. The planar AAT molecules are nearly perpendicular to this plane, exhibiting a slight twist of the Br1CuN2 planes. All the amino groups are in a syn arrangement. One of the Br⁻ ions is integrated into the inner coordination sphere, while the second Br- ion resides in the outer sphere (Fig. 1). As a result, the inner coordination sphere of the complex takes the shape of a tetragonal pyramid, where the basal positions are filled by nitrogen atoms from the 2-amino-5-allylthio-1,3,4-thiadiazole ligands, and the apical position is occupied by the Br⁻ ion.

Figure 1
Molecular structure of the complex [Cu(AAT)₄Br]Br. Displacement ellipsoids are shown with 20% probability level for clarity. Symmetry codes: (a) −x, y, z; (b) − $[{3\over 2}]$ − y, x, z; (c) − $[{3\over 2}]$ − x, $[{3\over 2}]$ − y, z; (d) −y, $[{3\over 2}]$ − x, z.

The Cu—Br bond length in the compound measures 2.7474 (7) Å, closely resembling the Cu—Br distance in the [CuL₄Br₂](H₂O)₂ molecule, which is 2.9383 Å (Berezin et al., 2018 ). Apparently, the binding of the Br⁻ ion into the inner coordination sphere induces a distortion of the CuN₄ plane. The effect of this distortion is to the reduce N—Cu—N coordination angles [88.446 (18) and 161.04 (11)°], in contrast to the angles of 90 and 180° expected in an ideal square-planar structure. The sum of bond angles at the Cu atom is 353.8°. The Cu atom deviates from the (N2)₄ plane toward Br⁻ by 0.333 Å. The length of the Cu—N coordination bonds is 2.0206 (17) Å, similar to those bonds in analogous complexes. For instance, in nitrato-tetrakis(2-amino-5-ethyl-1,3,4-thiadiazole)copper(II) nitrate, the average Cu—N bond length is 2.003 Å (Kadirova et al., 2008 ), aligning with the sum of the covalent radii of Cu and N.

Additionally, the Br1 atom participates in the formation of an intramolecular hydrogen bond with hydrogen atoms of four amino groups NH₂ simultaneously (Table 1). By comparing the structures of some complexes based on 2-amino-1,3,4-thiadiazole derivatives, we see that copper(II) bromide, in contrast to chlorides and acetates of cobalt(II) and zinc(II) (Camí et al., 2005 ; Song et al., 2012 ; Wang et al., 2009 ; Kadirova et al., 2008; Ishankhodzhaeva et al., 2000 , 2001 ), exhibits a distinct behavior when reacted with 2-amino-5-allylthio-1,3,4-thiadiazole under identical conditions. Instead of forming a tetrahedral molecular complex as might be anticipated from analytical data, copper(II) bromide forms the tetragonal–pyramidal cationic complex [Cu(AAT)₄Br]Br.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Br1	0.86	2.52	3.3265 (1)	157
N3—H3B⋯Br2	0.86	2.54	3.3685 (1)	162
C5A—H5AA⋯Br1ⁱ	0.93	3.03	3.95 (2)	175
Symmetry code: (i) .

3. Supramolecular features

In the crystal structure of [Cu(AAT)₄Br]Br, in addition to the aforementioned intramolecular hydrogen bonds, there exist intermolecular hydrogen bonds. The second bromide ion, positioned in the outer sphere, forms a hydrogen bond with the second (not participating in the intramolecular hydrogen bond) hydrogen atom of the amino group N3H2 (Table 1). The outer-sphere Br2 ion also resides on the fourfold axis, resulting in the generation of a layer in the crystal perpendicular to the fourfold axis due to this symmetry transformation. As a result, in the crystal packing, the cationic coordination complexes form columns along the [001] crystallographic axis (Fig. 2). The bromine anions of the outer sphere of the complex are located between the columns due to the formation of the N3—H3B⋯Br2 intermolecular hydrogen bonds with the amino groups of the ligand (Table 1).

Figure 2
Packing of [Cu(AAT)₄Br]Br complex molecules in the crystal structure in projections along the (a) b and (b) c crystallographic axis. Hydrogen bonds are indicated by blue dashed lines.

The interaction energies of the secondary interactions system within the structure were calculated using the HF method (HF/3-21G) in CrystalExplorer17 (Spackman et al., 2021 ). Although these calculations may not yield precise values for an ionic interaction, they effectively highlight the direction of strong interactions. The result shows the total energy (E_tot), which is the sum of the Coulombic (E_ele), polar (E_pol), dispersion (E_dis) and repulsive (E_rep) contributions. The four energy components were scaled in the total energy (E_tot = 1.019E_ele + 0651E_pol + 0901E_dis + 0.811E_rep). The interaction energies were investigated for a 3.8 Å cluster around the reference molecule. The calculation reveals two stronger interactions within the neighbouring molecules. The strongest interaction total energy (E_tot) is −112.5 kJ mol⁻¹ (∼-27 kcal mol⁻¹), with the polar (−30.1 kJ mol⁻¹), dispersion (−123.3 kJ mol⁻¹), Coulombic (−58.5 kJ mol⁻¹) and repulsive (96.0 kJ mol⁻¹) energies (with green colour) (Fig. 3).

Figure 3
Interaction energy calculations within the structure were performed using the HF method (HF/3–21 G) (CrystalExplorer17; Spackman et al., 2021

. The thickness of the tube represents the value of the energy. The distribution of the interactions according to type shows strong interactions along the crystallographic a-axis direction (the largest values are represented here). The total energy framework (in blue) and its two main components, dispersion (in green) and Coulombic energy (in red), are shown for a cluster around a reference molecule also exhibit stronger interactions along the crystallographic a-axis direction.

4. Hirshfeld surface analysis

To further investigate the intermolecular interactions present in the title compound, a Hirshfeld surface analysis was performed, and the two-dimensional (2D) fingerprint plots were generated with CrystalExplorer17 (Spackman et al., 2021). Fig. 4 shows the three-dimensional (3D) Hirshfeld surfaces of the complex with d_norm (normalized contact distance) plotted. The hydrogen-bond interactions given in Table 1 play a key role in the molecular packing of the complex. The overall 2D fingerprint plot and those delineated into H⋯H, S⋯H/H⋯S, S⋯S, C⋯H/H⋯C, Br⋯H/H⋯Br and N⋯H/H⋯N interactions are shown in Fig. 5. The percentage contributions to the Hirshfeld surfaces from the various interatomic contacts are as follows: H⋯H 33.7%, S⋯H/H⋯S 21.2%, S⋯S 13.4, C⋯H/H⋯C 11%, Br⋯H/H⋯Br 9.2% and N⋯H/H⋯N 7.8%. Other minor contributions to the Hirshfeld surface are: S⋯C/C⋯S 1.9% and Br⋯S/S⋯Br 1.6%.

Figure 4
Views of the three-dimensional Hirshfeld surface of the complex [Cu(AAT)₄Br]⁺ cation plotted over d_{norm in} views along the (a) [110] and (b) [001] directions.

Figure 5
Contributions of the various contacts to the two-dimensional fingerprint plots built using the Hirshfeld surfaces of the title complex.

5. Database survey

A survey of the Cambridge Structural Database (CSD, version 5.43, update of March 2022; Groom et al., 2016 ) revealed that nearly a hundred crystal structures had been reported for complexes of 2-amino-1,3,4-thiadiazole derivatives and a number of metal ions, including Mn, Fe, Co, Ni, Cu, Zn, Mo, Ag, Pd, Cd, Sn, Re, Pt, Au and Hg, twelve of which are for Cu complexes. Six structures exhibit tetragonal–pyramidal polyhedra (HONDOG, Torambetov et al., 2019 ; RUFQIT, Kadirova et al., 2008; SUZVOY, SUZVUE, Lynch & Ewington, 2001 ; XIGWIU, Camí et al., 2005; ZEKWOE, Gurbanov, et al., 2018 ). In seven structures, AAT is attached to metal ions, making p-complexes (ODAPOC, Slyvka et al., 2022 ; CEDSEM, Slyvka, 2017a ; ESIBUG, Slyvka et al., 2021 ; HAJLUC, Ardan et al., 2017 ; HAJMAJ, HAJMIR, Ardan et al., 2017; YEBNAX, Slyvka, 2017b ). However, no complexes of CuBr₂ based on 2-amino-1,3,4-thiadiazole derivatives have been documented in the CSD.

6. Synthesis and crystallization

The ligand 2-amino-5-allylthio-1,3,4-thiadiazole (AAT) was synthesized by the method of Toshmurodov et al. (2016 ), yield: 93%, m.p. = 388–390 K. CuBr₂·4H₂O (0.296g, 1 mmol) was added under continuous stirring to a solution of AAT (0.692 g, 4 mmol) dissolved in 10 ml of methanol. The resulting dark-green solution was stirred for 3 h and was then left to stand at room temperature. After one week, green crystals suitable for X-ray diffraction were obtained (yield 86%) by the slow evaporation of the solvent, m.p. = 458–460 K.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically (N—H = 0.86 Å, C—H = 0.83–0.97 Å) and refined as riding with U_iso(H) = 1.2U_eq(C, N).

Table 2
Experimental details

Crystal data
Chemical formula	[CuBr(C₅H₇N₃S₂)₄]Br
M_r	916.38
Crystal system, space group	Tetragonal, P4/n
Temperature (K)	293
a, c (Å)	12.69368 (9), 11.35879 (13)
V (Å³)	1830.24 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	7.95
Crystal size (mm)	0.12 × 0.08 × 0.03

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.626, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18450, 1746, 1597
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.065, 1.05
No. of reflections	1746
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.28
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2341909

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024002652/ny2003sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024002652/ny2003Isup2.hkl

checkCIF report

Computing details top

Bromidotetrakis[5-(prop-2-en-1-ylsulfanyl)-1,3,4-thiadiazol-2-amine-κN³]copper(II) bromide top

Crystal data top

[CuBr(C₅H₇N₃S₂)₄]Br	D_x = 1.663 Mg m⁻³
M_r = 916.38	Cu Kα radiation, λ = 1.54184 Å
Tetragonal, P4/n	Cell parameters from 9121 reflections
a = 12.69368 (9) Å	θ = 3.5–70.8°
c = 11.35879 (13) Å	µ = 7.95 mm⁻¹
V = 1830.24 (3) Å³	T = 293 K
Z = 2	Block, green
F(000) = 918	0.12 × 0.08 × 0.03 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	1597 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.036
ω scans	θ_max = 69.9°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −15→15
T_min = 0.626, T_max = 1.000	k = −11→15
18450 measured reflections	l = −13→13
1746 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0273P)² + 0.9257P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.26 e Å⁻³
1746 reflections	Δρ_min = −0.28 e Å⁻³
118 parameters	Extinction correction: SHELXL-2016/6 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00018 (7)

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	Occ. (<1)
Br1	0.750000	0.750000	1.01564 (4)	0.04943 (15)
Br2	0.250000	0.750000	1.000000	0.05616 (16)
Cu1	0.750000	0.750000	0.77377 (5)	0.03890 (16)
S1	0.39660 (5)	0.70986 (6)	0.72047 (6)	0.06176 (19)
S2	0.42895 (6)	0.65094 (8)	0.46657 (7)	0.0831 (3)
N2	0.59625 (14)	0.71817 (14)	0.74447 (16)	0.0470 (4)
N1	0.57992 (14)	0.68882 (16)	0.62785 (18)	0.0544 (5)
N3	0.50405 (16)	0.7637 (2)	0.9157 (2)	0.0739 (7)
H3A	0.560992	0.775718	0.954484	0.089*
H3B	0.443808	0.771729	0.949189	0.089*
C1	0.50915 (16)	0.73279 (18)	0.8039 (2)	0.0500 (5)
C2	0.48136 (19)	0.6828 (2)	0.6037 (2)	0.0574 (6)
C3	0.5494 (3)	0.6360 (3)	0.3816 (3)	0.0984 (11)
H3BC	0.580640	0.704195	0.365145	0.118*	0.5
H3BD	0.600153	0.593336	0.423967	0.118*	0.5
H3AA	0.600532	0.688177	0.406669	0.118*	0.5
H3AB	0.579095	0.566715	0.395347	0.118*	0.5
C5A	0.5337 (16)	0.5753 (12)	0.1730 (17)	0.143 (7)	0.5
H5AA	0.587593	0.612982	0.136912	0.171*	0.5
H5AB	0.492013	0.529830	0.128742	0.171*	0.5
C4	0.5259 (9)	0.6502 (7)	0.2475 (9)	0.104 (3)	0.5
H4	0.516751	0.720330	0.226229	0.125*	0.5
C4A	0.5181 (8)	0.5852 (11)	0.2749 (8)	0.112 (3)	0.5
H4A	0.461720	0.541488	0.293578	0.134*	0.5
C5	0.5187 (14)	0.6021 (18)	0.1813 (12)	0.154 (8)	0.5
H5A	0.526312	0.529967	0.192763	0.185*	0.5
H5B	0.504113	0.628295	0.106619	0.185*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.05153 (19)	0.05153 (19)	0.0452 (3)	0.000	0.000	0.000
Br2	0.04993 (19)	0.04993 (19)	0.0686 (3)	0.000	0.000	0.000
Cu1	0.0362 (2)	0.0362 (2)	0.0443 (3)	0.000	0.000	0.000
S1	0.0387 (3)	0.0791 (4)	0.0675 (4)	0.0015 (3)	−0.0065 (3)	0.0060 (3)
S2	0.0637 (4)	0.1138 (7)	0.0718 (5)	−0.0029 (4)	−0.0179 (4)	−0.0189 (4)
N2	0.0405 (9)	0.0489 (10)	0.0517 (10)	−0.0013 (8)	−0.0029 (8)	0.0008 (8)
N1	0.0450 (10)	0.0610 (12)	0.0573 (11)	−0.0041 (9)	−0.0020 (8)	−0.0070 (9)
N3	0.0430 (11)	0.121 (2)	0.0573 (13)	0.0096 (12)	0.0002 (9)	−0.0060 (13)
C1	0.0388 (11)	0.0538 (12)	0.0574 (13)	0.0016 (9)	−0.0018 (9)	0.0079 (10)
C2	0.0489 (13)	0.0608 (14)	0.0626 (15)	−0.0020 (11)	−0.0058 (11)	−0.0008 (11)
C3	0.084 (2)	0.131 (3)	0.080 (2)	−0.004 (2)	−0.0020 (18)	−0.023 (2)
C5A	0.168 (13)	0.095 (7)	0.165 (16)	−0.031 (7)	0.075 (10)	−0.020 (7)
C4	0.173 (9)	0.068 (5)	0.070 (6)	−0.034 (5)	0.017 (5)	0.007 (4)
C4A	0.117 (7)	0.141 (10)	0.077 (6)	0.013 (7)	0.024 (5)	−0.019 (6)
C5	0.121 (9)	0.30 (2)	0.038 (4)	0.016 (12)	−0.010 (5)	−0.005 (8)

Geometric parameters (Å, º) top

Br1—Cu1	2.7474 (7)	C3—H3BC	0.9700
Cu1—N2ⁱ	2.0206 (17)	C3—H3BD	0.9700
Cu1—N2	2.0206 (17)	C3—H3AA	0.9700
Cu1—N2ⁱⁱ	2.0206 (17)	C3—H3AB	0.9700
Cu1—N2ⁱⁱⁱ	2.0206 (17)	C3—C4	1.562 (11)
S1—C1	1.739 (2)	C3—C4A	1.429 (10)
S1—C2	1.742 (3)	C5A—H5AA	0.9300
S2—C2	1.741 (3)	C5A—H5AB	0.9300
S2—C3	1.818 (4)	C5A—C4A	1.181 (19)
N2—N1	1.392 (3)	C4—H4	0.9300
N2—C1	1.308 (3)	C4—C5	0.973 (18)
N1—C2	1.283 (3)	C4A—H4A	0.9300
N3—H3A	0.8600	C5—H5A	0.9300
N3—H3B	0.8600	C5—H5B	0.9300
N3—C1	1.331 (3)

N2ⁱ—Cu1—Br1	99.48 (5)	S2—C3—H3BC	110.7
N2ⁱⁱⁱ—Cu1—Br1	99.48 (5)	S2—C3—H3BD	110.7
N2ⁱⁱ—Cu1—Br1	99.48 (5)	S2—C3—H3AA	109.6
N2—Cu1—Br1	99.48 (5)	S2—C3—H3AB	109.6
N2ⁱⁱ—Cu1—N2ⁱⁱⁱ	88.446 (18)	H3BC—C3—H3BD	108.8
N2ⁱⁱ—Cu1—N2	88.446 (18)	H3AA—C3—H3AB	108.1
N2ⁱⁱⁱ—Cu1—N2ⁱ	88.446 (18)	C4—C3—S2	110.2 (5)
N2ⁱ—Cu1—N2	88.445 (18)	C4—C3—H3AA	109.6
N2ⁱⁱ—Cu1—N2ⁱ	161.04 (11)	C4—C3—H3AB	109.6
N2ⁱⁱⁱ—Cu1—N2	161.04 (11)	C4A—C3—S2	105.3 (5)
C1—S1—C2	86.58 (11)	C4A—C3—H3BC	110.7
C2—S2—C3	100.25 (14)	C4A—C3—H3BD	110.7
N1—N2—Cu1	110.74 (13)	H5AA—C5A—H5AB	120.0
C1—N2—Cu1	134.66 (16)	C4A—C5A—H5AA	120.0
C1—N2—N1	113.76 (18)	C4A—C5A—H5AB	120.0
C2—N1—N2	111.4 (2)	C3—C4—H4	112.8
H3A—N3—H3B	120.0	C5—C4—C3	134.4 (15)
C1—N3—H3A	120.0	C5—C4—H4	112.8
C1—N3—H3B	120.0	C3—C4A—H4A	106.8
N2—C1—S1	112.94 (18)	C5A—C4A—C3	146.4 (13)
N2—C1—N3	125.1 (2)	C5A—C4A—H4A	106.8
N3—C1—S1	121.96 (17)	C4—C5—H5A	120.0
S2—C2—S1	119.40 (14)	C4—C5—H5B	120.0
N1—C2—S1	115.33 (19)	H5A—C5—H5B	120.0
N1—C2—S2	125.3 (2)

Cu1—N2—N1—C2	−170.89 (17)	C1—S1—C2—S2	−178.55 (17)
Cu1—N2—C1—S1	168.95 (12)	C1—S1—C2—N1	1.2 (2)
Cu1—N2—C1—N3	−9.9 (4)	C1—N2—N1—C2	0.2 (3)
S2—C3—C4—C5	−103 (2)	C2—S1—C1—N2	−1.01 (18)
S2—C3—C4A—C5A	148 (2)	C2—S1—C1—N3	177.9 (2)
N2—N1—C2—S1	−1.0 (3)	C2—S2—C3—C4	−158.1 (4)
N2—N1—C2—S2	178.68 (17)	C2—S2—C3—C4A	166.4 (6)
N1—N2—C1—S1	0.7 (2)	C3—S2—C2—S1	178.11 (19)
N1—N2—C1—N3	−178.2 (2)	C3—S2—C2—N1	−1.6 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Br1	0.86	2.52	3.3265 (1)	157
N3—H3B···Br2	0.86	2.54	3.3685 (1)	162
C5A—H5AA···Br1^iv	0.93	3.03	3.95 (2)	175

Symmetry code: (iv) x, y, z−1.

Funding information

This work was supported by Uzbekistan Ministry of Higher Education, Science and Innovation.

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