Synthesis, crystal structure, and Hirshfeld surface analysis of 1,3-di­hydro-2H-benzimidazol-2-iminium 3-carb­oxy-4-hy­droxy­benzene­sulfonate

Mukhammadiev, S.; Rajabov, S.; Tojiboev, A.; Ashurov, J.; Murodov, S.; Daminova, S.

doi:10.1107/S2056989024008557

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ISSN: 2056-9890

Volume 80| Part 10| October 2024| Pages 999-1002

https://doi.org/10.1107/S2056989024008557

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Synthesis, crystal structure, and Hirshfeld surface analysis of 1,3-dihydro-2H-benzimidazol-2-iminium 3-carboxy-4-hydroxybenzenesulfonate

Salmon Mukhammadiev,^a ^* Sarvar Rajabov,^b Akmaljon Tojiboev,^c Jamshid Ashurov,^d Sardor Murodov ^b and Shahlo Daminova ^a,^e

^aUzbekistan Japan Innovation Center of Youth, University str. 2B, Tashkent, 100095, Uzbekistan, ^bNational University of Uzbekistan named after Mirzo Ulugbek, University str. 4, Tashkent 100174, Uzbekistan, ^cUniversity of Geological Sciences, Olimlar str. 64, Tashkent 100125, Uzbekistan, ^dInstitute of Bioorganic Chemistry of Academy of Sciences of Uzbekistan, Mirzo, Ulug`bek st. 83, Tashkent 100125, Uzbekistan, and ^eNational University of Uzbekistan named after Mirzo Ulugbek, University str., 4, Tashkent 100174, Uzbekistan
^*Correspondence e-mail: salmonmuxammadiyev97@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 4 June 2024; accepted 29 August 2024; online 6 September 2024)

The asymmetric unit of the title salt, C₇H₈N₃⁺·C₇H₅O₆S⁻, comprises two 1,3-dihydro-2H-benzimidazol-2-iminium cations and two 2-hydroxy-5-sulfobenzoate anions (Z′ = 2). In the crystal, the molecules interact through N—H⋯O, O—H⋯O hydrogen bonds and C—O⋯π contacts. The hydrogen-bonding interactions lead to the formation of layers parallel to ( $[\overline{1}]$ 01). Hirshfeld surface analysis revealed that H⋯H contacts contribute to most of the crystal packing with 38.9%, followed by H⋯O contacts with 36.2%.

Keywords: benzimidazolium; sulfobenzoate; crystal structure; Hirshfeld surface analysis.

CCDC reference: 2380553

1. Chemical context

The increasing development of benzimidazoles and their derivatives in medicine is still the subject of intensive research due to their diverse biological activities (Suku & Ravindran, 2023 ). Benzimidazole derivatives have antihypertensive, antiallergic, antidiabetic, anti-inflammatory, mycobacterial, antioxidant, antiprotozoal, antiviral and antimicrobial effects (Dokla et al., 2020 ; Dvornikova et al., 2019 ; Aboul-Enein & El Rashedy, 2015 ). In addition, benzimidazole derivatives are an important class of chemicals with regard to their activity against several viruses such as HIV, herpes (HSV-1), influenza, Epstein-Barr and Burkitt's lymphoma (Ramla et al., 2007 ), and their use as anti-cancer agents (Ottanà et al., 2005 ).

5-Sulfosalicylic acid is a particularly strong organic acid, which is capable of protonating N-containing heterocycles and other Lewis bases (Muthiah et al., 2003 ) and thus can form structures with a variety of supramolecular arrangements.

The present work was undertaken as part of our research program aimed at further understanding hydrogen-bonding interactions involving 2-aminobenzimidazole and 5-sulfosalicylic acid. Here, we report the synthesis, crystal structure, and Hirshfeld surface analysis of the new organic salt 1,3-dihydro-2H-benzimidazol-2-iminium 2-hydroxy-5-sulfobenzoate, C₇H₈N₃⁺·C₇H₅O₆S⁻.

2. Structural commentary

The asymmetric unit of the title salt (Fig. 1) contains two 1,3-dihydro-2H-benzimidazol-2-iminium cations and two 2-hydroxy-5-sulfobenzoate anions (Z′ = 2). The N—C and S—O bond lengths range from 1.318 (2) to 1.394 (2) Å and from 1.4417 (12) to 1.4727 (12) Å, respectively. The O—S—O and N—C—N angles range from 110.60 (7) to 113.71 (8)° and from 109.10 (13) to 125.67 (15)°, respectively (Table 1). Overlays of the two cations and the two anions show that they are almost identical (Figs. S1 and S2 in the ESI), with somewhat greater deviations between the two anions. Analysis of bond lengths and angles shows that these data differ only slightly from those of other related compounds with similar structural units (Saiadali Fathima et al., 2019 ; Atria et al., 2012 ; Low et al., 2003 ; ESI Table S1).

Table 1
Selected geometric parameters (Å, °)

S1—O3	1.4727 (12)	N1—C6	1.3886 (19)
S1—O1	1.4479 (13)	N2—C7	1.3350 (19)
S1—O2	1.4417 (12)	N2—C5	1.394 (2)
S1—C13	1.7634 (15)	N4—C21	1.340 (2)
S2—O7	1.4615 (12)	N4—C20	1.391 (2)
S2—O8	1.4455 (12)	N5—C21	1.335 (2)
S2—O9	1.4516 (14)	N5—C19	1.391 (2)
S2—C22	1.7645 (16)	N3—C7	1.322 (2)
N1—C7	1.3390 (19)	N6—C21	1.318 (2)

O1—S1—O3	110.60 (7)	N2—C7—N1	109.10 (13)
O2—S1—O3	111.98 (8)	N3—C7—N1	125.51 (14)
O2—S1—O1	113.71 (8)	N3—C7—N2	125.39 (15)
O8—S2—O7	111.30 (8)	N5—C21—N4	108.91 (14)
O8—S2—O9	113.02 (9)	N6—C21—N4	125.42 (15)
O9—S2—O7	111.40 (8)	N6—C21—N5	125.67 (15)

Figure 1
The structures of the molecular entities in the title salt. Displacement ellipsoids are drawn at the 50% probability level.

An intramolecular O—H⋯O hydrogen bond between the hydroxy group and the non-protonated O atom of the carboxy group stabilizes the molecular conformation for each of the cations (O4—H4⋯O5; O10—H10⋯O11; Fig. 2, Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	2.08	2.8645 (16)	152
N2—H2⋯O9	0.86	2.07	2.8799 (19)	157
N3—H3A⋯O3ⁱ	0.86	2.37	3.0153 (19)	132
N3—H3B⋯O4ⁱⁱ	0.86	2.32	3.005 (2)	137
N4—H4B⋯O7	0.86	2.04	2.8760 (17)	163
N5—H5⋯O3	0.86	2.22	3.0331 (18)	158
N6—H6A⋯O2	0.86	2.17	2.877 (2)	140
N6—H6B⋯O8	0.86	2.06	2.845 (2)	152
O4—H4⋯O5	0.82	1.88	2.6007 (17)	147
O6—H6⋯O3ⁱⁱⁱ	0.82	1.89	2.6958 (16)	165
O10—H10⋯O11	0.82	1.90	2.619 (2)	146
O12—H12A⋯O7ⁱⁱⁱ	0.82	1.89	2.6746 (17)	159
Symmetry codes: (i) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) ; (iii) .

Figure 2
Crystal packing in a view along the b axis. Intermolecular N—H⋯O and O—H⋯O interactions are shown as light-blue dashed lines and intramolecular O—H⋯O interactions as dark-blue dashed lines.

3. Supramolecular features

In the crystal, the N atoms of the imidazolium cation form intermolecular N—H⋯O hydrogen bonds with oxygen atoms of the sulfate group of the two hydroxybenzoate anions. Moreover, O—H⋯O interactions between the carboxy group and one of the sulfonate O atoms are present (Fig. 2, Table 2). Additionally, π–π interactions between the aromatic rings with centroid-to-centroid distances between 3.5094 (9) and 3.9824 (10) Å (numerical details are given in ESI Table S2) as well as C14=O5⋯Cg4(x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z) interactions of 3.7089 (19) Å are present (Fig. 3). All of the above contacts contribute to the tri-periodic packing of the molecular entities in the crystal.

Figure 3
Interactions between aromatic rings in the title salt, leading to π–π stacking between the following ring centroids (Cg) shown as colored spheres: Cg1 (C8–C13, purple sphere); Cg2 (C22–C27, yellow sphere); Cg3 (N1/C5–C7/N2, green sphere); Cg4 (C1–C6, red sphere); Cg6 (N4/C19–C21/N5, black sphere); Cg7 (C15–C20, magenta sphere). The dashed red lines represent C14=O5⋯Cg4 contacts [3.7089 (19) Å].

4. Hirshfeld surface analysis

In order to quantify the intermolecular interactions in the title salt, the Hirshfeld surface (HS) (Spackman & Jayatilaka, 2009 ) was analysed and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) calculated with CrystalExplorer (Spackman et al., 2021 ). The HS mapped over d_norm is represented in Fig. 4. White surface areas indicate contacts with distances equal to the sum of van der Waals radii, whereas red and blue colors denote distances shorter or longer than the sum of the van der Waals radii. The red spots clearly visible in Fig. 4 emphasize the importance of classical hydrogen-bonding interactions in the title salt. The two-dimensional fingerprint plot for all contacts is depicted in Fig. 5a. H⋯H contacts are responsible for the largest contribution (38.9%) to the Hirshfeld surface (Fig. 5b). Besides these contacts, H⋯O/O⋯H (36.2%), C⋯C (10.2%), H⋯C/C⋯H (5.1%) and O⋯C/C⋯O (3.7%) interactions contribute significantly to the total Hirshfeld surface; their decomposed fingerprint plots are shown in Fig. 5c–f. The contributions of further contacts are only minor and amount to N⋯C/C⋯N (2.6%), O⋯O (2.1%) and N⋯H/H⋯N (1.1%).

Figure 4
HS plotted over d_norm (a) along the a axis, (b) along the b axis and (c) along the c axis.

Figure 5
Two-dimensional fingerprint plots for (a) all interactions and (b)–(i) individual interatomic contacts.

5. Database survey

A survey of the Cambridge Structural Database (CSD, version 5.43, update of November 2022; Groom et al., 2016 ) revealed 47 hits related to the 2-aminobenzimidazolium cation. Among them are those that form intermolecular hydrogen bonds like in the title salt: 2-aminobenzimidazolium hydrogen sulfate (DOKZEJ: You et al., 2009 ), 2-aminobenzimidazolium O-ethyl malonate (EMIHAJ: Low et al., 2003), 2-amino-1H-benzimidazol-3-ium 1,3-dioxo-1,3-dihydro-2H-isoindol-2-olate 2-hydroxy-1H-isoindole-1,3(2H)-dione (EPETOK: Mahendiran et al., 2016 ), 2-aminobenzimidazolium picrate (HUZSIE: El-Medani et al., 2003 ), 2-amino-1H-benzimidazol-3-ium 2-propanamidobenzoat (NUVZIQ: Amor et al., 2020 ) and 2-amino-1H-benzimidazol-3-ium pyridine-3-carboxylate (VARCOJ: Fathima et al., 2017 ). Eight hits containing sulfosalicylic acid in related organic salts were identified, among them 5-sulfosalicylic acid thiourea (ETABAC: Xiong et al., 2003 ), 2-hydroxy-5-sulfobenzoic acid aniline monohydrate (JUCJOG: Bakasova et al., 1991 ), tris(benzohydrazido)cobalt chloride hydroxide 2-hydroxy-5-sulfobenzoic acid monohydrate (MOWTAV: Antsyshkina et al., 2014 ). In all these structures intermolecular hydrogen bonds are the dominant motif in the crystal packing.

6. Synthesis and crystallization

All reagents for synthesis and analysis were commercially available and purchased from Sigma Aldrich and used as received without further purification.

Sulfosalicylic acid and 2-aminobenzimidazole were reacted in a molar ratio of 1:1, using a solution of 0.133 g of 2-aminobenzimidazole in 5 ml of ethanol that was added dropwise to 0.228 g of the acid dissolved in 5 ml of ethanol. The mixture was stirred on a magnetic stirrer for 4 h. During the reaction time, the color of the solution changed from transparent to light brown. The solution was left for 2 weeks at room temperature for crystal growth. The formed crystals were filtered off and washed several times with ethanol to remove impurities.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were geometrically placed with C—H = 0.93 Å, O—H = 0.82 Å, N—H = 0.86 Å and with U_iso(H) = 1.2U_eq(C) and U_iso(H) = 1.5U_e_q(O,N).

Table 3
Experimental details

Crystal data
Chemical formula	C₇H₈N₃⁺·C₇H₅O₆S⁻
M_r	351.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	21.03214 (18), 8.61349 (6), 16.69445 (13)
β (°)	102.5549 (8)
V (Å³)	2952.05 (4)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	2.33
Crystal size (mm)	0.48 × 0.16 × 0.08

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.871, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	29960, 5715, 5051
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.099, 1.06
No. of reflections	5715
No. of parameters	438
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.36
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2380553

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024008557/wm5724sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024008557/wm5724Isup3.hkl

Table S1. DOI: https://doi.org/10.1107/S2056989024008557/wm5724sup4.docx

Table S2. DOI: https://doi.org/10.1107/S2056989024008557/wm5724sup5.docx

Fig. S1. DOI: https://doi.org/10.1107/S2056989024008557/wm5724sup6.tif

Fig. S2. DOI: https://doi.org/10.1107/S2056989024008557/wm5724sup7.tif

Supporting information file. DOI: https://doi.org/10.1107/S2056989024008557/wm5724Isup7.cml

checkCIF report

Computing details top

1,3-Dihydro-2H-benzimidazol-2-iminium 3-carboxy-4-hydroxybenzenesulfonate top

Crystal data top

C₇H₈N₃⁺·C₇H₅O₆S⁻	F(000) = 1456
M_r = 351.33	D_x = 1.581 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 21.03214 (18) Å	Cell parameters from 16513 reflections
b = 8.61349 (6) Å	θ = 2.7–71.3°
c = 16.69445 (13) Å	µ = 2.33 mm⁻¹
β = 102.5549 (8)°	T = 293 K
V = 2952.05 (4) Å³	Block, light brown
Z = 8	0.48 × 0.16 × 0.08 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	5715 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	5051 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 10.0000 pixels mm^-1	θ_max = 71.5°, θ_min = 4.3°
ω scans	h = −25→25
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2020)	k = −10→10
T_min = 0.871, T_max = 1.000	l = −20→20
29960 measured 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)] = 0.034	w = 1/[σ²(F_o²) + (0.0567P)² + 0.6854P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.099	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.27 e Å⁻³
5715 reflections	Δρ_min = −0.36 e Å⁻³
438 parameters	Extinction correction: SHELXL2016/6 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00055 (7)
Primary atom site location: dual

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
S1	0.11934 (2)	0.24229 (4)	0.55062 (2)	0.03300 (11)
S2	0.34651 (2)	0.27387 (4)	0.95601 (2)	0.03508 (12)
O3	0.15655 (6)	0.14053 (13)	0.50668 (7)	0.0400 (3)
O4	−0.01170 (6)	0.66757 (14)	0.29142 (7)	0.0440 (3)
H4	0.003130	0.755665	0.299245	0.066*
O1	0.07143 (6)	0.15365 (15)	0.58177 (7)	0.0470 (3)
O7	0.38626 (6)	0.15583 (13)	0.92733 (7)	0.0437 (3)
O5	0.06294 (6)	0.88704 (14)	0.36682 (7)	0.0471 (3)
O6	0.12027 (7)	0.83981 (13)	0.49325 (8)	0.0538 (4)
H6	0.124383	0.934506	0.494093	0.081*
O2	0.16137 (7)	0.33480 (14)	0.61221 (7)	0.0533 (4)
O8	0.31346 (7)	0.37100 (14)	0.88921 (8)	0.0548 (4)
O12	0.41101 (8)	0.86010 (14)	0.97231 (8)	0.0570 (4)
H12A	0.411808	0.954869	0.967980	0.085*
O11	0.47871 (7)	0.91026 (15)	1.09195 (9)	0.0538 (3)
O9	0.30261 (6)	0.20503 (17)	1.00215 (8)	0.0545 (3)
O10	0.52275 (7)	0.67731 (17)	1.18904 (8)	0.0574 (4)
H10	0.519921	0.768036	1.173804	0.086*
N1	0.13245 (6)	0.09746 (15)	0.75004 (7)	0.0341 (3)
H1	0.103915	0.126568	0.707628	0.041*
N2	0.19964 (6)	0.10264 (16)	0.86938 (8)	0.0356 (3)
H2	0.221336	0.135381	0.916026	0.043*
N4	0.33971 (7)	0.05422 (16)	0.76079 (8)	0.0377 (3)
H4B	0.361431	0.081968	0.808392	0.045*
N5	0.27558 (7)	0.06439 (16)	0.63948 (8)	0.0399 (3)
H5	0.249491	0.099795	0.596411	0.048*
N3	0.14323 (8)	0.33421 (16)	0.82363 (9)	0.0463 (4)
H3A	0.161926	0.384146	0.866979	0.056*
H3B	0.115343	0.380427	0.785840	0.056*
N6	0.28709 (8)	0.29260 (18)	0.71966 (10)	0.0509 (4)
H6A	0.261023	0.344077	0.682173	0.061*
H6B	0.304792	0.336881	0.765226	0.061*
C8	0.09424 (7)	0.52774 (17)	0.48123 (9)	0.0314 (3)
H8	0.125957	0.563268	0.525213	0.038*
C9	0.06462 (7)	0.63126 (17)	0.42016 (9)	0.0303 (3)
C7	0.15735 (8)	0.18636 (18)	0.81509 (9)	0.0327 (3)
C6	0.16017 (7)	−0.04933 (18)	0.76213 (9)	0.0327 (3)
C10	0.01692 (7)	0.57477 (18)	0.35440 (9)	0.0319 (3)
C5	0.20288 (7)	−0.04648 (18)	0.83812 (9)	0.0341 (3)
C13	0.07684 (7)	0.37327 (17)	0.47686 (9)	0.0308 (3)
C22	0.40035 (7)	0.39564 (18)	1.02406 (9)	0.0338 (3)
C12	0.02746 (8)	0.31920 (18)	0.41300 (9)	0.0352 (3)
H12	0.014833	0.215563	0.411341	0.042*
C14	0.08204 (8)	0.79738 (18)	0.42341 (10)	0.0360 (3)
C21	0.29989 (8)	0.14585 (19)	0.70729 (9)	0.0362 (3)
C11	−0.00241 (8)	0.42021 (18)	0.35255 (9)	0.0351 (3)
H11	−0.035660	0.384926	0.310287	0.042*
C19	0.29916 (8)	−0.0868 (2)	0.64961 (10)	0.0366 (3)
C25	0.48227 (8)	0.5887 (2)	1.13349 (10)	0.0390 (4)
C23	0.40528 (8)	0.55034 (18)	1.00533 (9)	0.0348 (3)
H23	0.381287	0.589129	0.955959	0.042*
C27	0.43664 (8)	0.33542 (19)	1.09781 (10)	0.0400 (4)
H27	0.433598	0.230805	1.110242	0.048*
C20	0.34016 (8)	−0.09308 (19)	0.72674 (10)	0.0361 (3)
C26	0.47681 (8)	0.4322 (2)	1.15167 (11)	0.0442 (4)
H26	0.500674	0.392696	1.200933	0.053*
C24	0.44597 (8)	0.64935 (18)	1.05978 (10)	0.0348 (3)
C1	0.15138 (9)	−0.1813 (2)	0.71355 (11)	0.0458 (4)
H1A	0.123446	−0.182244	0.662054	0.055*
C28	0.44777 (8)	0.81802 (19)	1.04362 (11)	0.0409 (4)
C15	0.37191 (9)	−0.2290 (2)	0.75666 (12)	0.0452 (4)
H15	0.399729	−0.233354	0.808185	0.054*
C4	0.23850 (9)	−0.1770 (2)	0.86892 (12)	0.0500 (5)
H4A	0.267711	−0.175518	0.919486	0.060*
C18	0.28712 (9)	−0.2161 (2)	0.59962 (11)	0.0462 (4)
H18	0.259158	−0.211927	0.548186	0.055*
C16	0.36023 (9)	−0.3572 (2)	0.70630 (13)	0.0514 (5)
H16	0.380914	−0.450282	0.724237	0.062*
C17	0.31836 (10)	−0.3514 (2)	0.62939 (12)	0.0517 (5)
H17	0.311335	−0.440819	0.597426	0.062*
C2	0.18617 (11)	−0.3113 (2)	0.74543 (14)	0.0577 (5)
H2A	0.180926	−0.402913	0.715202	0.069*
C3	0.22868 (10)	−0.3085 (2)	0.82137 (15)	0.0599 (6)
H3	0.251307	−0.398462	0.840797	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0425 (2)	0.02530 (18)	0.02788 (19)	0.00298 (14)	0.00036 (15)	0.00239 (13)
S2	0.0397 (2)	0.02640 (19)	0.0354 (2)	0.00288 (15)	−0.00023 (16)	−0.00232 (14)
O3	0.0455 (6)	0.0324 (6)	0.0411 (6)	0.0087 (5)	0.0071 (5)	0.0030 (5)
O4	0.0517 (7)	0.0398 (6)	0.0348 (6)	0.0040 (5)	−0.0032 (5)	0.0100 (5)
O1	0.0532 (7)	0.0468 (7)	0.0415 (6)	0.0019 (6)	0.0117 (5)	0.0151 (5)
O7	0.0562 (7)	0.0301 (6)	0.0429 (6)	0.0088 (5)	0.0067 (5)	−0.0024 (5)
O5	0.0556 (7)	0.0336 (6)	0.0481 (7)	−0.0027 (5)	0.0025 (6)	0.0135 (5)
O6	0.0771 (9)	0.0260 (6)	0.0485 (7)	−0.0054 (6)	−0.0076 (6)	0.0012 (5)
O2	0.0699 (8)	0.0341 (6)	0.0420 (7)	0.0021 (6)	−0.0182 (6)	−0.0023 (5)
O8	0.0699 (9)	0.0343 (6)	0.0467 (7)	0.0102 (6)	−0.0168 (6)	−0.0016 (5)
O12	0.0818 (10)	0.0277 (6)	0.0537 (8)	−0.0024 (6)	−0.0021 (7)	0.0057 (6)
O11	0.0555 (8)	0.0354 (6)	0.0666 (8)	−0.0102 (6)	0.0047 (6)	−0.0057 (6)
O9	0.0484 (7)	0.0638 (8)	0.0509 (7)	−0.0183 (6)	0.0099 (6)	−0.0115 (7)
O10	0.0562 (8)	0.0524 (8)	0.0528 (8)	−0.0137 (7)	−0.0117 (6)	−0.0037 (6)
N1	0.0405 (7)	0.0321 (7)	0.0262 (6)	0.0022 (5)	0.0000 (5)	0.0030 (5)
N2	0.0375 (7)	0.0386 (7)	0.0274 (6)	−0.0016 (6)	0.0001 (5)	0.0018 (5)
N4	0.0409 (7)	0.0364 (7)	0.0328 (7)	0.0032 (6)	0.0011 (5)	−0.0011 (5)
N5	0.0474 (8)	0.0405 (7)	0.0293 (7)	0.0064 (6)	0.0026 (6)	0.0017 (6)
N3	0.0593 (9)	0.0318 (7)	0.0452 (8)	0.0039 (7)	0.0056 (7)	−0.0024 (6)
N6	0.0648 (10)	0.0365 (8)	0.0449 (8)	0.0093 (7)	−0.0024 (7)	−0.0017 (6)
C8	0.0353 (8)	0.0284 (7)	0.0289 (7)	0.0021 (6)	0.0031 (6)	−0.0002 (6)
C9	0.0335 (7)	0.0274 (7)	0.0300 (7)	0.0025 (6)	0.0070 (6)	0.0021 (6)
C7	0.0365 (8)	0.0321 (8)	0.0300 (7)	−0.0017 (6)	0.0078 (6)	0.0024 (6)
C6	0.0350 (8)	0.0301 (7)	0.0342 (8)	0.0000 (6)	0.0101 (6)	0.0037 (6)
C10	0.0336 (8)	0.0348 (8)	0.0272 (7)	0.0063 (6)	0.0064 (6)	0.0031 (6)
C5	0.0330 (8)	0.0339 (8)	0.0361 (8)	0.0001 (6)	0.0090 (6)	0.0070 (6)
C13	0.0364 (8)	0.0280 (7)	0.0270 (7)	0.0039 (6)	0.0047 (6)	0.0007 (6)
C22	0.0351 (8)	0.0285 (7)	0.0362 (8)	0.0029 (6)	0.0041 (6)	−0.0002 (6)
C12	0.0406 (8)	0.0285 (7)	0.0343 (8)	−0.0007 (6)	0.0032 (6)	−0.0009 (6)
C14	0.0386 (8)	0.0305 (8)	0.0378 (8)	0.0005 (7)	0.0056 (6)	0.0038 (7)
C21	0.0395 (8)	0.0364 (8)	0.0323 (8)	0.0013 (7)	0.0069 (6)	0.0030 (6)
C11	0.0362 (8)	0.0358 (8)	0.0302 (7)	0.0002 (6)	0.0007 (6)	−0.0032 (6)
C19	0.0375 (8)	0.0387 (8)	0.0348 (8)	0.0023 (7)	0.0106 (6)	0.0008 (7)
C25	0.0349 (8)	0.0397 (9)	0.0398 (8)	−0.0035 (7)	0.0025 (7)	−0.0023 (7)
C23	0.0388 (8)	0.0299 (8)	0.0337 (8)	0.0039 (6)	0.0033 (6)	0.0017 (6)
C27	0.0429 (9)	0.0320 (8)	0.0415 (9)	0.0024 (7)	0.0012 (7)	0.0064 (7)
C20	0.0371 (8)	0.0365 (8)	0.0350 (8)	0.0017 (7)	0.0088 (6)	0.0013 (7)
C26	0.0431 (9)	0.0443 (9)	0.0390 (9)	0.0021 (8)	−0.0045 (7)	0.0071 (7)
C24	0.0353 (8)	0.0293 (8)	0.0394 (8)	0.0002 (6)	0.0070 (6)	0.0000 (6)
C1	0.0544 (10)	0.0393 (9)	0.0467 (10)	−0.0075 (8)	0.0176 (8)	−0.0069 (8)
C28	0.0420 (9)	0.0319 (8)	0.0492 (10)	−0.0023 (7)	0.0111 (7)	−0.0017 (7)
C15	0.0460 (10)	0.0425 (9)	0.0457 (10)	0.0068 (8)	0.0068 (8)	0.0054 (8)
C4	0.0416 (9)	0.0505 (11)	0.0578 (11)	0.0088 (8)	0.0105 (8)	0.0227 (9)
C18	0.0479 (10)	0.0491 (10)	0.0413 (9)	−0.0004 (8)	0.0089 (8)	−0.0094 (8)
C16	0.0510 (11)	0.0386 (9)	0.0665 (12)	0.0063 (8)	0.0167 (9)	0.0042 (9)
C17	0.0553 (11)	0.0408 (10)	0.0621 (12)	−0.0027 (8)	0.0196 (9)	−0.0131 (9)
C2	0.0669 (13)	0.0334 (9)	0.0813 (15)	−0.0004 (9)	0.0345 (11)	−0.0049 (9)
C3	0.0591 (12)	0.0354 (10)	0.0924 (16)	0.0144 (9)	0.0324 (12)	0.0181 (10)

Geometric parameters (Å, º) top

S1—O3	1.4727 (12)	C8—C13	1.378 (2)
S1—O1	1.4479 (13)	C9—C10	1.403 (2)
S1—O2	1.4417 (12)	C9—C14	1.475 (2)
S1—C13	1.7634 (15)	C6—C5	1.386 (2)
S2—O7	1.4615 (12)	C6—C1	1.385 (2)
S2—O8	1.4455 (12)	C10—C11	1.390 (2)
S2—O9	1.4516 (14)	C5—C4	1.386 (2)
S2—C22	1.7645 (16)	C13—C12	1.397 (2)
O4—H4	0.8200	C22—C23	1.378 (2)
O4—C10	1.3533 (17)	C22—C27	1.400 (2)
O5—C14	1.2188 (19)	C12—H12	0.9300
O6—H6	0.8200	C12—C11	1.376 (2)
O6—C14	1.3160 (19)	C11—H11	0.9300
O12—H12A	0.8200	C19—C20	1.386 (2)
O12—C28	1.321 (2)	C19—C18	1.382 (2)
O11—C28	1.216 (2)	C25—C26	1.391 (2)
O10—H10	0.8200	C25—C24	1.401 (2)
O10—C25	1.3507 (19)	C23—H23	0.9300
N1—H1	0.8600	C23—C24	1.396 (2)
N1—C7	1.3390 (19)	C27—H27	0.9300
N1—C6	1.3886 (19)	C27—C26	1.374 (2)
N2—H2	0.8600	C20—C15	1.386 (2)
N2—C7	1.3350 (19)	C26—H26	0.9300
N2—C5	1.394 (2)	C24—C28	1.480 (2)
N4—H4B	0.8600	C1—H1A	0.9300
N4—C21	1.340 (2)	C1—C2	1.380 (3)
N4—C20	1.391 (2)	C15—H15	0.9300
N5—H5	0.8600	C15—C16	1.378 (3)
N5—C21	1.335 (2)	C4—H4A	0.9300
N5—C19	1.391 (2)	C4—C3	1.373 (3)
N3—H3A	0.8600	C18—H18	0.9300
N3—H3B	0.8600	C18—C17	1.377 (3)
N3—C7	1.322 (2)	C16—H16	0.9300
N6—H6A	0.8600	C16—C17	1.391 (3)
N6—H6B	0.8600	C17—H17	0.9300
N6—C21	1.318 (2)	C2—H2A	0.9300
C8—H8	0.9300	C2—C3	1.384 (3)
C8—C9	1.395 (2)	C3—H3	0.9300

O3—S1—C13	106.05 (7)	C11—C12—C13	119.60 (14)
O1—S1—O3	110.60 (7)	C11—C12—H12	120.2
O1—S1—C13	107.55 (7)	O5—C14—O6	123.07 (15)
O2—S1—O3	111.98 (8)	O5—C14—C9	123.28 (14)
O2—S1—O1	113.71 (8)	O6—C14—C9	113.65 (13)
O2—S1—C13	106.47 (7)	N5—C21—N4	108.91 (14)
O7—S2—C22	106.97 (7)	N6—C21—N4	125.42 (15)
O8—S2—O7	111.30 (8)	N6—C21—N5	125.67 (15)
O8—S2—O9	113.02 (9)	C10—C11—H11	119.9
O8—S2—C22	106.64 (7)	C12—C11—C10	120.29 (14)
O9—S2—O7	111.40 (8)	C12—C11—H11	119.9
O9—S2—C22	107.12 (8)	C20—C19—N5	106.42 (14)
C10—O4—H4	109.5	C18—C19—N5	131.89 (15)
C14—O6—H6	109.5	C18—C19—C20	121.67 (16)
C28—O12—H12A	109.5	O10—C25—C26	117.85 (15)
C25—O10—H10	109.5	O10—C25—C24	122.28 (15)
C7—N1—H1	125.5	C26—C25—C24	119.86 (15)
C7—N1—C6	108.96 (12)	C22—C23—H23	119.7
C6—N1—H1	125.5	C22—C23—C24	120.60 (14)
C7—N2—H2	125.6	C24—C23—H23	119.7
C7—N2—C5	108.86 (13)	C22—C27—H27	120.3
C5—N2—H2	125.6	C26—C27—C22	119.40 (15)
C21—N4—H4B	125.6	C26—C27—H27	120.3
C21—N4—C20	108.88 (13)	C19—C20—N4	106.61 (14)
C20—N4—H4B	125.6	C15—C20—N4	131.96 (15)
C21—N5—H5	125.4	C15—C20—C19	121.42 (16)
C21—N5—C19	109.16 (13)	C25—C26—H26	119.6
C19—N5—H5	125.4	C27—C26—C25	120.88 (15)
H3A—N3—H3B	120.0	C27—C26—H26	119.6
C7—N3—H3A	120.0	C25—C24—C28	119.73 (14)
C7—N3—H3B	120.0	C23—C24—C25	118.95 (14)
H6A—N6—H6B	120.0	C23—C24—C28	121.17 (14)
C21—N6—H6A	120.0	C6—C1—H1A	121.7
C21—N6—H6B	120.0	C2—C1—C6	116.63 (18)
C9—C8—H8	119.8	C2—C1—H1A	121.7
C13—C8—H8	119.8	O12—C28—C24	113.61 (14)
C13—C8—C9	120.48 (13)	O11—C28—O12	122.87 (16)
C8—C9—C10	118.67 (14)	O11—C28—C24	123.50 (16)
C8—C9—C14	121.67 (13)	C20—C15—H15	121.6
C10—C9—C14	119.66 (13)	C16—C15—C20	116.70 (17)
N2—C7—N1	109.10 (13)	C16—C15—H15	121.6
N3—C7—N1	125.51 (14)	C5—C4—H4A	121.5
N3—C7—N2	125.39 (15)	C3—C4—C5	116.97 (18)
C5—C6—N1	106.56 (13)	C3—C4—H4A	121.5
C1—C6—N1	131.59 (15)	C19—C18—H18	121.5
C1—C6—C5	121.85 (15)	C17—C18—C19	117.00 (17)
O4—C10—C9	121.64 (14)	C17—C18—H18	121.5
O4—C10—C11	118.02 (13)	C15—C16—H16	119.1
C11—C10—C9	120.34 (13)	C15—C16—C17	121.86 (18)
C6—C5—N2	106.52 (13)	C17—C16—H16	119.1
C6—C5—C4	121.03 (16)	C18—C17—C16	121.34 (17)
C4—C5—N2	132.45 (16)	C18—C17—H17	119.3
C8—C13—S1	119.50 (11)	C16—C17—H17	119.3
C8—C13—C12	120.49 (14)	C1—C2—H2A	119.3
C12—C13—S1	119.97 (12)	C1—C2—C3	121.47 (19)
C23—C22—S2	119.88 (12)	C3—C2—H2A	119.3
C23—C22—C27	120.30 (15)	C4—C3—C2	122.02 (18)
C27—C22—S2	119.80 (12)	C4—C3—H3	119.0
C13—C12—H12	120.2	C2—C3—H3	119.0

S1—C13—C12—C11	−175.55 (12)	C6—C1—C2—C3	−1.3 (3)
S2—C22—C23—C24	177.81 (12)	C10—C9—C14—O5	−9.1 (2)
S2—C22—C27—C26	−177.85 (14)	C10—C9—C14—O6	170.92 (15)
O3—S1—C13—C8	−111.11 (13)	C5—N2—C7—N1	0.55 (18)
O3—S1—C13—C12	66.71 (14)	C5—N2—C7—N3	−178.33 (15)
O4—C10—C11—C12	176.78 (14)	C5—C6—C1—C2	1.5 (3)
O1—S1—C13—C8	130.53 (13)	C5—C4—C3—C2	1.1 (3)
O1—S1—C13—C12	−51.65 (15)	C13—C8—C9—C10	0.0 (2)
O7—S2—C22—C23	117.00 (14)	C13—C8—C9—C14	179.72 (15)
O7—S2—C22—C27	−64.59 (15)	C13—C12—C11—C10	0.8 (2)
O2—S1—C13—C8	8.31 (15)	C22—C23—C24—C25	0.6 (2)
O2—S1—C13—C12	−173.88 (13)	C22—C23—C24—C28	−175.03 (16)
O8—S2—C22—C23	−2.19 (16)	C22—C27—C26—C25	−0.6 (3)
O8—S2—C22—C27	176.22 (14)	C14—C9—C10—O4	3.1 (2)
O9—S2—C22—C23	−123.46 (14)	C14—C9—C10—C11	−176.73 (14)
O9—S2—C22—C27	54.95 (15)	C21—N4—C20—C19	0.50 (18)
O10—C25—C26—C27	−179.84 (17)	C21—N4—C20—C15	−178.85 (18)
O10—C25—C24—C23	179.85 (16)	C21—N5—C19—C20	−1.00 (18)
O10—C25—C24—C28	−4.4 (2)	C21—N5—C19—C18	177.32 (18)
N1—C6—C5—N2	−0.16 (17)	C19—N5—C21—N4	1.34 (19)
N1—C6—C5—C4	179.65 (15)	C19—N5—C21—N6	−178.87 (17)
N1—C6—C1—C2	−178.53 (17)	C19—C20—C15—C16	−0.6 (3)
N2—C5—C4—C3	178.81 (17)	C19—C18—C17—C16	−0.1 (3)
N4—C20—C15—C16	178.71 (18)	C25—C24—C28—O12	−179.47 (16)
N5—C19—C20—N4	0.30 (18)	C25—C24—C28—O11	−1.2 (3)
N5—C19—C20—C15	179.73 (15)	C23—C22—C27—C26	0.6 (3)
N5—C19—C18—C17	−178.94 (18)	C23—C24—C28—O12	−3.8 (2)
C8—C9—C10—O4	−177.17 (14)	C23—C24—C28—O11	174.42 (17)
C8—C9—C10—C11	3.0 (2)	C27—C22—C23—C24	−0.6 (2)
C8—C9—C14—O5	171.10 (16)	C20—N4—C21—N5	−1.14 (19)
C8—C9—C14—O6	−8.8 (2)	C20—N4—C21—N6	179.06 (17)
C8—C13—C12—C11	2.2 (2)	C20—C19—C18—C17	−0.8 (3)
C9—C8—C13—S1	175.20 (11)	C20—C15—C16—C17	−0.4 (3)
C9—C8—C13—C12	−2.6 (2)	C26—C25—C24—C23	−0.7 (2)
C9—C10—C11—C12	−3.4 (2)	C26—C25—C24—C28	175.07 (17)
C7—N1—C6—C5	0.49 (17)	C24—C25—C26—C27	0.6 (3)
C7—N1—C6—C1	−179.48 (17)	C1—C6—C5—N2	179.82 (15)
C7—N2—C5—C6	−0.24 (17)	C1—C6—C5—C4	−0.4 (2)
C7—N2—C5—C4	179.98 (17)	C1—C2—C3—C4	0.0 (3)
C6—N1—C7—N2	−0.65 (17)	C15—C16—C17—C18	0.7 (3)
C6—N1—C7—N3	178.23 (16)	C18—C19—C20—N4	−178.23 (16)
C6—C5—C4—C3	−0.9 (3)	C18—C19—C20—C15	1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.08	2.8645 (16)	152
N2—H2···O9	0.86	2.07	2.8799 (19)	157
N3—H3A···O3ⁱ	0.86	2.37	3.0153 (19)	132
N3—H3B···O4ⁱⁱ	0.86	2.32	3.005 (2)	137
N4—H4B···O7	0.86	2.04	2.8760 (17)	163
N5—H5···O3	0.86	2.22	3.0331 (18)	158
N6—H6A···O2	0.86	2.17	2.877 (2)	140
N6—H6B···O8	0.86	2.06	2.845 (2)	152
O4—H4···O5	0.82	1.88	2.6007 (17)	147
O6—H6···O3ⁱⁱⁱ	0.82	1.89	2.6958 (16)	165
O10—H10···O11	0.82	1.90	2.619 (2)	146
O12—H12A···O7ⁱⁱⁱ	0.82	1.89	2.6746 (17)	159
C3—H3···O8^iv	0.93	2.42	3.347 (2)	178
C8—H8···O2	0.93	2.46	2.8626 (19)	106
C23—H23···O8	0.93	2.47	2.872 (2)	106
C23—H23···O12	0.93	2.42	2.732 (2)	100

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

Acknowledgements

The authors acknowledge technical equipment support provided by the Institute of Bioorganic Chemistry of Academy of Sciences of Uzbekistan, Tashkent, Uzbekistan.

References

Aboul-Enein, H. Y. & El Rashedy, A. A. (2015). Med. Chem. 5, 318–325. Google Scholar
Amor, A. B. H., Akriche, S., Arfaoui, Y. & Abderrahim, R. (2020). J. Mol. Struct. 1222, 128921–128930. Web of Science CSD CrossRef CAS Google Scholar
Antsyshkina, A. S., Koksharova, T. V., Sergienko, V. S., Mandzii, T. V. & Sadikov, G. G. (2014). Russ. J. Inorg. Chem. 59, 1417–1423. Web of Science CrossRef CAS Google Scholar
Atria, A. M., Garland, M. T. & Baggio, R. (2012). Acta Cryst. C68, m185–m188. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bakasova, Z. B., Abdybaliev, D. A., Sharipov, Kh. T., Akbaev, A. A., Ibragimov, R. T., Talipov, S. A. & Ismankulov, A. I. (1991). Uzb. Khim. Zh. pp. 22–25. Google Scholar
Dokla, E. M. E., Abutaleb, N. S., Milik, S. N., Li, D., El-Baz, K., Shalaby, M., Al-Karaki, R., Nasr, M., Klein, C. D., Abouzid, K. A. M. & Seleem, M. N. (2020). Eur. J. Med. Chem. 186, 111850–111858. Web of Science CrossRef CAS PubMed Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Dvornikova, I. A., Buravlev, E. V., Fedorova, I. V., Shevchenko, O. G., Chukicheva, I. Y. & Kutchin, A. V. (2019). Russ. Chem. Bull. 68, 1000–1005. Web of Science CrossRef CAS Google Scholar
El-Medani, S. M., Youssef, T. A. & Ramadan, R. M. (2003). J. Mol. Struct. 644, 77–87. CAS Google Scholar
Fathima, K. S., Kavitha, P. & Anitha, K. (2017). J. Mol. Struct. 1143, 444–451. Web of Science CSD CrossRef CAS 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
Low, J. N., Cobo, J., Abonia, R., Insuasty, B. & Glidewell, C. (2003). Acta Cryst. C59, o669–o671. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mahendiran, D., Vinitha, G., Shobana, S., Viswanathan, V., Velmurugan, D. & Rahiman, A. K. (2016). RSC Adv. 6, 60336–60348. Web of Science CSD CrossRef CAS Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Muthiah, P. T., Francis, S., Bocelli, G. & Cantoni, A. (2003). Acta Cryst. E59, m1164–m1167. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ottanà, R., Carotti, S., Maccari, R., Landini, I., Chiricosta, G., Caciagli, B., Vigorita, G. M. & Mini, E. (2005). Bioorg. Med. Chem. Lett. 15, 3930–3933. Web of Science PubMed Google Scholar
Ramla, M. M., Omar, A. M., Tokuda, H. & El-Diwani, H. I. (2007). Bioorg. Med. Chem. 15, 6489–6496. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Saiadali Fathima, K., Sathiyendran, M. & Anitha, K. (2019). J. Mol. Struct. 1177, 457–468. Web of Science CSD CrossRef CAS 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
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Suku, S. & Ravindran, R. (2023). J. Mol. Struct. 1283, 135217–135228. Web of Science CSD CrossRef CAS Google Scholar
Xiong, J., Hu, M.-L., Shi, Q. & Xiao, H.-P. (2003). Z. Kristallogr. 218, 565–566. CAS Google Scholar
You, W., Fan, Y., Qian, H.-F., Yao, C. & Huang, W. (2009). Acta Cryst. E65, o115. Web of Science CSD CrossRef IUCr Journals Google Scholar

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