Synthesis, crystal structure and Hirshfeld surface analysis of 7-oxo-6-phenyl-6,7-di­hydro-5H-thieno[2,3-f]iso­indole-8-carb­oxy­lic acid

Shelukho, E.R.; Zaytsev, V.P.; Khrustalev, V.N.; Hökelek, T.; Hasanov, K.I.; Guliyeva, N.A.; Javadzade, T.A.; Al-Douh, M.H.

doi:10.1107/S2056989025008618

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ISSN: 2056-9890

Volume 81| Part 11| November 2025| Pages 1000-1003

https://doi.org/10.1107/S2056989025008618

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Synthesis, crystal structure and Hirshfeld surface analysis of 7-oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid

Evgeniya R. Shelukho,^a Vladimir P. Zaytsev,^a Victor N. Khrustalev,^a,^b Tuncer Hökelek,^c Khudayar I. Hasanov,^d Narmina A. Guliyeva,^e Tahir A. Javadzade ^f and Mohammed Hadi Al-Douh ^g ^*

^aRUDN University, 6 Miklukho-Maklaya Str., 117198 Moscow, Russian Federation, ^bZelinsky Institute of Organic Chemistry of RAS, Leninsky Prospect 47, 119991 Moscow, Russian Federation, ^cHacettepe University, Department of Physics, 06800 Beytepe-Ankara, Türkiye, ^dAzerbaijan Medical University, Scientific Research Centre (SRC), A. Kasumzade Str. 14, AZ1022, Baku, Azerbaijan, ^eBaku Engineering University, Khirdalan, Hasan Aliyev Str. 120, AZ0101 Absheron, Azerbaijan, ^fDepartment of Chemistry and Chemical Engineering, Khazar University, Mahsati Str. 41, AZ1096, Baku, Azerbaijan, and ^gChemistry Department, Faculty of Science, Hadhramout University, Mukalla, Hadhramout, Yemen
^*Correspondence e-mail: [email protected]

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 5 August 2025; accepted 30 September 2025; online 7 October 2025)

In the title compound, C₁₇H₁₁NO₃S, the thieno[2,3-f]isoindole ring system and the phenyl ring are oriented at a dihedral angle of 20.57 (13)°. The strong intramolecular O—H⋯O hydrogen bond partly ensures the coplanarity of the carboxyl group and the ring system. In crystal, the molecules are linked through C—H⋯O hydrogen bonds, enclosing R²₂(14) ring motifs, into a three-dimensional architecture. π–π interactions between parallel five-membered and phenyl rings [centroid-to-centroid distances of 3.564 (3) and 3.591 (3) Å] further contribute to the cohesion of the crystal structure. The Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯H (35.5%), H⋯O/O⋯H (21.3%), C⋯C (14.1%) and H⋯C/C⋯H (12.8%) interactions.

Keywords: intramolecular didehydro-Diels–Alder reaction; propargylamine; IMDDA reaction; thieno[2,3-f]isoindole; crystal structure.

CCDC reference: 2492514

1. Chemical context

It is widely recognized that in the field of [4 + 2]-cycloaddition chemistry, the terms diene and dienophile are not limited to compounds with only double bonds. In the Diels–Alder reaction, alkynes can also serve as dienophiles, and conjugated 1,3-diynes or 1,3-enynes can act as dienes. Such pericyclic reactions are referred in the literature as dehydro-Diels–Alder reactions (Wessig et al., 2008 ; Johnson, 2010 ; Ajaz et al., 2011 ; Li et al., 2016 ), and intramolecular dehydro-Diels–Alder (IMDDA) reactions are widely used in organic synthesis to construct polycyclic molecules (Hoye et al., 2012 ; Brummond et al., 2015 ; Wang et al., 2016 ; Rana et al., 2017 ; Krishna et al., 2022 ). A special case of this type of transformation is the intramolecular didehydro-Diels–Alder reaction, in which an alkene dienophile reacts with an enyne. There are only a few publications related to the intramolecular dehydro-Diels–Alder reaction of the thiophene series that demonstrate the fundamental possibility of IMDDA transformations (Klemm et al., 1965 , 1966 ; Lu et al., 2005 ; Bober et al., 2017 ; Huang et al., 2017 ).

This work is a continuation of studies on the tandem acylation/[4 + 2] cycloaddition reaction between 3-(thienyl)propargylamines and maleic anhydride as an example of the IMDDA approach (Shelukho et al., 2025 ). Thienylpropargylamine 1 readily reacts with maleic anhydride to provide a mixture of products, where the product 2 has been published previously (Shelukho et al., 2025), but the major acid 3 could not be isolated and characterized due to the formation of a mixture of products. In this work, we successfully isolated and characterized 7-oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid, 3. The detection of acid 3 directly confirms the assumption that type 2 dihydroacid is prone to easy oxidation under aerobic conditions. Herein, we report the synthesis and molecular and crystal structure, together with the Hirshfeld surface analysis of the title compound, 3.

2. Structural commentary

The asymmetric unit of the title compound, C₁₇H₁₁NO₃S, contains an essentially planar [r.m.s. deviation = 0.02 (4) Å] thieno[2,3-f]isoindole ring system (A; S1/C2/C3/C3A/C4/C4A/C5/N6/C7/C7A/C8/C8A), and a phenyl ring (B; C9–C14) oriented at a dihedral angle of 20.57 (13)°. The carboxyl group (C1/O2/O3/C8) is oriented at a dihedral angle of 0.22 (12)° with respect to the thieno[2,3-f]isoindole ring system. Thus, they are almost coplanar, partly as a result of the strong intramolecular O3—H3O⋯O1 hydrogen bond between the carboxyl hydrogen and isoindole oxygen atoms (Table 1, Fig. 1). On the other hand, the dihedral angle between the carboxylate group and ring B is 21.2 (4)°. Atom O1 is 0.037 (3) Å away from the best least-squares plane of the thieno[2,3-f]isoindole ring system. In the carboxylate group, the O2—C1 and O3—C1 bond lengths are 1.217 (6) and 1.303 (6) Å, respectively. Thus, the C—O bonds in the carboxylate group indicate mainly localized single and double bounds rather than a delocalized bonding arrangement. The O2—C1—O3 [120.9 (4)°] bond angle seems to be decreased compared to that present in a free acid (122.2°; Sim et al., 1955 ) and compares with corresponding values of 122.42 (14)° in C₁₇H₁₃NO₂ (Refcode UYATIZ; Mague et al., 2016 ), 122.55 (12)° in C₁₄H₁₁NO₃ (BIYJEC; El-Mrabet et al., 2023 ) and 122.70 (12)° in C₁₂H₁₀ClNO₃ (PEDKAO; Filali Baba et al., 2022 ). As indicated by the O2—C1—C8—C7A [179.9 (4)°] and O3—C1—C8—C8A [179.7 (4)°] torsion angles, the carboxyl group attached to the thieno[2,3-f]isoindole ring system is in a anti peripheral conformation.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1	0.74 (8)	1.76 (8)	2.496 (5)	175 (8)
C5—H5A⋯O2ⁱ	0.99	2.37	3.343 (6)	167
C5—H5B⋯O2ⁱⁱ	0.99	2.37	3.013 (6)	122
C11—H11⋯O1ⁱⁱⁱ	0.95	2.50	3.333 (6)	146
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) .

Figure 1
The asymmetric unit of the title compound with the atom-numbering scheme and 50% probability ellipsoids.

3. Supramolecular features

In the crystal, the molecules are linked through C—H⋯O hydrogen bonds, enclosing R₂²(14) ring motifs, into a three-dimensional architecture (Fig. 2). There are π–π interactions between the parallel five-membered (S1/C2/C3/C3A/C8A and N6/C5/C4A/C7A/C7) rings and the phenyl (C3A/C4/C4A/C7A/C8/C8A) ring with centroid-to-centroid distances of 3.564 (3) Å (α = 0.92° and slippage = 1.031 Å) and 3.591 (3) Å (α = 0.70° and slippage = 1.041 Å), respectively.

Figure 2
A partial packing diagram of the title compound viewed down the a-axis direction. Intramolecular O—H⋯O and intermolecular C—H⋯O hydrogen bonds are shown as dashed lines. H atoms not involved in these interactions have been omitted for clarity.

4. Hirshfeld surface analysis

To visualize the intermolecular interactions, a Hirshfeld surface (HS) analysis was carried out using Crystal Explorer 17.5 (Spackman et al., 2021 ). In the HS plotted over d_norm (Fig. 3), the contact distances equal, shorter and longer with respect to the sum of van der Waals radii are shown in white, red and blue, respectively. According to the two-dimensional fingerprint plots, H⋯H, H⋯O/O⋯H, C⋯C and H⋯C/C⋯H contacts make the most important contributions to the HS (Fig. 4).

Figure 3
View of the three-dimensional Hirshfeld surface plotted over d_norm.

Figure 4
The full two-dimensional fingerprint plots showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) C⋯C, (e) H⋯C/C⋯H, (f) H⋯S/S⋯H, (g) C⋯O/O⋯C, (h) C⋯S/S⋯C, (i) C⋯N/N⋯C, (j) O⋯S/S⋯O, (k) O⋯O, (l) H⋯N/N⋯H, (m) S ⋯ S and (n) N⋯N interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

5. Synthesis and crystallization

Maleic anhydride (61.0 mg, 0.62 mmol) was added to N-(3-(thiophen-3-yl)prop-2-ynyl)aniline (1) (132.3 mg, 0.62 mmol) diluted in PhCH₃ (3 mL) at a 5 mL round-bottom flask. The resulting mixture was heated under reflux for 5 h, and then cooled to room temperature. The resulting precipitate was filtered, washed with PhMe (3 mL), Et₂O (2 × 3 mL), and air dried to give acid 2 (20.0 mg, 10%) as a colourless solid (for full characteristics see Shelukho et al., 2025). After cooling mother liquor at 278 K, the precipitate was filtered, washed with mother liquor (3 mL), Et₂O (2 × 3 mL), and air dried to give the title compound 3 as yellow plates (yield 49%, 96.4 mg, m.p. > 523 K). IR (KBr), ν (cm⁻¹): 1704 (CO₂), 1591 (N—C=O). ¹H NMR (700.2 MHz, DMSO-d₆): δ (J, Hz) 16.45 (br.s., 1H, CO₂H), 8.45 (s, 1H, H-Ar), 8.18 (d, J = 5.5 Hz, 1H, H-2 Thien), 7.91 (d, J = 7.6 Hz, 2H, H-Ar), 7.70 (d, J = 5.5 Hz, 1H, H-Thien), 7.56 (t, J = 7.6 Hz, 2H, H-Ar), 7.37 (t, J = 7.6 Hz, 1H, H-Ar), 5.33 (s, 2H, NCH₂) ppm. ¹³C {¹H} NMR (176.1 MHz, DMSO-d₆): δ 169.1, 165.9, 1447, 142.3, 138.6, 138.1, 136.7, 129.7 (2C), 126.9, 126.8, 123.6, 123.4, 122.6, 122.2 (2C), 52.3 ppm. MS (ESI) m/z: [M + H]⁺ 310. Elemental analysis calculated (%) for C₁₇H₁₁NO₃S: C 66.01, H 3.58, N 4.53, S 10.36; found: C 65.84, H 3.49, N 4.69, S 10.17.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydroxy hydrogen atom was located in a difference Fourier map and refined isotropically. The C-bound hydrogen-atom positions were calculated geometrically at distances of 0.95 Å (for aromatic CH) and 0.99 Å (for CH₂) and refined using a riding model by applying the constraint U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₁NO₃S
M_r	309.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	3.89128 (10), 15.8505 (5), 21.6531 (7)
β (°)	93.596 (3)
V (Å³)	1332.91 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.28
Crystal size (mm)	0.13 × 0.07 × 0.02

Data collection
Diffractometer	Rigaku XtaLAB Synergy-S, HyPix-6000HE area-detector
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2021 ).
T_min, T_max	0.857, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11945, 2775, 2269
R_int	0.119

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.097, 0.238, 1.03
No. of reflections	2775
No. of parameters	203
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.48
Computer programs: CrysAlis PRO (Rigaku OD, 2021), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2492514

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025008618/ex2095sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025008618/ex2095Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025008618/ex2095Isup3.cml

checkCIF report

Computing details top

7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid top

Crystal data top

C₁₇H₁₁NO₃S	F(000) = 640
M_r = 309.33	D_x = 1.541 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 3.89128 (10) Å	Cell parameters from 3873 reflections
b = 15.8505 (5) Å	θ = 3.5–78.8°
c = 21.6531 (7) Å	µ = 2.28 mm⁻¹
β = 93.596 (3)°	T = 100 K
V = 1332.91 (7) Å³	Plate, yellow
Z = 4	0.13 × 0.07 × 0.02 mm

Data collection top

Rigaku XtaLAB Synergy-S, HyPix-6000HE area-detector diffractometer	2269 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.119
φ and ω scans	θ_max = 79.8°, θ_min = 3.5°
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2021).	h = −3→4
T_min = 0.857, T_max = 1.000	k = −19→19
11945 measured reflections	l = −27→27
2775 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.097	Hydrogen site location: mixed
wR(F²) = 0.238	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.088P)² + 6.9P] where P = (F_o² + 2F_c²)/3
2775 reflections	(Δ/σ)_max < 0.001
203 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

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	0.1382 (3)	0.55415 (8)	0.87334 (5)	0.0250 (3)
O1	0.7474 (9)	0.5121 (2)	0.63096 (15)	0.0265 (8)
O2	0.4093 (9)	0.6550 (2)	0.79077 (16)	0.0276 (8)
O3	0.6243 (11)	0.6318 (2)	0.70111 (19)	0.0332 (9)
H3O	0.671 (19)	0.596 (5)	0.681 (4)	0.05 (2)*
C1	0.4827 (12)	0.6057 (3)	0.7506 (2)	0.0239 (10)
C2	−0.0144 (12)	0.4688 (3)	0.9129 (2)	0.0278 (10)
H2	−0.1150	0.4741	0.9516	0.033*
C3	0.0211 (12)	0.3938 (3)	0.8842 (2)	0.0249 (10)
H3	−0.0494	0.3413	0.9004	0.030*
C3A	0.1779 (11)	0.4030 (3)	0.8264 (2)	0.0216 (9)
C4	0.2556 (11)	0.3396 (3)	0.7848 (2)	0.0213 (9)
H4	0.2094	0.2821	0.7932	0.026*
C4A	0.4011 (11)	0.3632 (3)	0.7312 (2)	0.0181 (9)
C5	0.5110 (12)	0.3077 (3)	0.6796 (2)	0.0219 (9)
H5A	0.6944	0.2680	0.6945	0.026*
H5B	0.3141	0.2753	0.6607	0.026*
N6	0.6397 (9)	0.3689 (2)	0.63574 (17)	0.0204 (8)
C7	0.6339 (12)	0.4491 (3)	0.6577 (2)	0.0218 (9)
C7A	0.4790 (11)	0.4474 (3)	0.7184 (2)	0.0205 (9)
C8	0.4125 (11)	0.5128 (3)	0.7595 (2)	0.0209 (9)
C8A	0.2606 (11)	0.4884 (3)	0.8140 (2)	0.0219 (9)
C9	0.7463 (11)	0.3427 (3)	0.5766 (2)	0.0213 (9)
C10	0.7616 (12)	0.3990 (3)	0.5276 (2)	0.0272 (10)
H10	0.7054	0.4567	0.5330	0.033*
C11	0.8587 (13)	0.3705 (3)	0.4710 (2)	0.0292 (11)
H11	0.8698	0.4092	0.4377	0.035*
C12	0.9398 (12)	0.2871 (4)	0.4619 (2)	0.0297 (11)
H12	1.0073	0.2684	0.4228	0.036*
C13	0.9218 (13)	0.2306 (3)	0.5106 (2)	0.0299 (11)
H13	0.9781	0.1730	0.5046	0.036*
C14	0.8225 (12)	0.2572 (3)	0.5679 (2)	0.0249 (10)
H14	0.8065	0.2180	0.6008	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0238 (6)	0.0237 (6)	0.0280 (6)	0.0030 (4)	0.0046 (4)	−0.0064 (4)
O1	0.0360 (19)	0.0144 (16)	0.0301 (17)	−0.0061 (13)	0.0105 (14)	0.0027 (13)
O2	0.0290 (18)	0.0184 (16)	0.0359 (18)	0.0002 (13)	0.0047 (14)	−0.0047 (14)
O3	0.050 (2)	0.0135 (17)	0.038 (2)	−0.0018 (15)	0.0152 (17)	−0.0018 (15)
C1	0.019 (2)	0.019 (2)	0.034 (2)	0.0045 (17)	0.0034 (18)	−0.0033 (18)
C2	0.025 (2)	0.034 (3)	0.025 (2)	0.002 (2)	0.0050 (18)	0.000 (2)
C3	0.021 (2)	0.028 (3)	0.025 (2)	−0.0034 (19)	0.0008 (17)	0.0016 (19)
C3A	0.016 (2)	0.023 (2)	0.026 (2)	0.0028 (17)	0.0013 (16)	−0.0021 (18)
C4	0.024 (2)	0.016 (2)	0.024 (2)	−0.0030 (17)	0.0043 (17)	0.0020 (17)
C4A	0.016 (2)	0.015 (2)	0.024 (2)	−0.0001 (16)	0.0024 (15)	−0.0014 (16)
C5	0.027 (2)	0.015 (2)	0.024 (2)	−0.0025 (17)	0.0071 (17)	0.0010 (17)
N6	0.0211 (19)	0.0150 (18)	0.0255 (19)	−0.0024 (14)	0.0048 (14)	0.0036 (15)
C7	0.023 (2)	0.014 (2)	0.029 (2)	0.0023 (17)	0.0051 (17)	0.0021 (18)
C7A	0.020 (2)	0.017 (2)	0.024 (2)	0.0016 (17)	0.0041 (16)	0.0001 (17)
C8	0.018 (2)	0.020 (2)	0.025 (2)	0.0016 (17)	0.0037 (16)	−0.0037 (17)
C8A	0.014 (2)	0.023 (2)	0.028 (2)	0.0016 (17)	0.0018 (16)	−0.0050 (18)
C9	0.017 (2)	0.023 (2)	0.025 (2)	−0.0015 (17)	0.0050 (16)	−0.0021 (18)
C10	0.028 (3)	0.023 (2)	0.031 (2)	−0.0008 (19)	0.0091 (19)	0.003 (2)
C11	0.023 (2)	0.035 (3)	0.030 (2)	−0.003 (2)	0.0088 (18)	0.002 (2)
C12	0.023 (2)	0.041 (3)	0.026 (2)	−0.005 (2)	0.0077 (18)	−0.003 (2)
C13	0.032 (3)	0.027 (3)	0.031 (3)	0.002 (2)	0.004 (2)	−0.007 (2)
C14	0.023 (2)	0.028 (3)	0.025 (2)	−0.0024 (19)	0.0054 (18)	0.0005 (19)

Geometric parameters (Å, º) top

S1—C2	1.726 (5)	C5—H5A	0.9900
S1—C8A	1.745 (5)	C5—H5B	0.9900
O1—C7	1.249 (6)	N6—C7	1.358 (6)
O2—C1	1.217 (6)	N6—C9	1.431 (6)
O3—C1	1.303 (6)	C7—C7A	1.479 (6)
O3—H3O	0.74 (8)	C7A—C8	1.402 (6)
C1—C8	1.512 (7)	C8—C8A	1.406 (6)
C2—C3	1.353 (7)	C9—C10	1.392 (7)
C2—H2	0.9500	C9—C14	1.402 (7)
C3—C3A	1.434 (6)	C10—C11	1.380 (7)
C3—H3	0.9500	C10—H10	0.9500
C3A—C4	1.396 (6)	C11—C12	1.376 (8)
C3A—C8A	1.420 (7)	C11—H11	0.9500
C4—C4A	1.373 (6)	C12—C13	1.387 (8)
C4—H4	0.9500	C12—H12	0.9500
C4A—C7A	1.400 (6)	C13—C14	1.388 (7)
C4A—C5	1.505 (6)	C13—H13	0.9500
C5—N6	1.467 (6)	C14—H14	0.9500

C2—S1—C8A	90.9 (2)	O1—C7—C7A	127.0 (4)
C1—O3—H3O	112 (6)	N6—C7—C7A	108.1 (4)
O2—C1—O3	120.9 (4)	C4A—C7A—C8	121.8 (4)
O2—C1—C8	118.8 (4)	C4A—C7A—C7	107.4 (4)
O3—C1—C8	120.3 (4)	C8—C7A—C7	130.7 (4)
C3—C2—S1	114.4 (4)	C7A—C8—C8A	115.7 (4)
C3—C2—H2	122.8	C7A—C8—C1	126.7 (4)
S1—C2—H2	122.8	C8A—C8—C1	117.7 (4)
C2—C3—C3A	111.9 (4)	C8—C8A—C3A	122.3 (4)
C2—C3—H3	124.1	C8—C8A—S1	127.0 (4)
C3A—C3—H3	124.1	C3A—C8A—S1	110.7 (3)
C4—C3A—C8A	120.1 (4)	C10—C9—C14	119.8 (4)
C4—C3A—C3	127.7 (4)	C10—C9—N6	121.7 (4)
C8A—C3A—C3	112.2 (4)	C14—C9—N6	118.4 (4)
C4A—C4—C3A	117.9 (4)	C11—C10—C9	119.7 (5)
C4A—C4—H4	121.1	C11—C10—H10	120.2
C3A—C4—H4	121.1	C9—C10—H10	120.2
C4—C4A—C7A	122.2 (4)	C12—C11—C10	121.3 (5)
C4—C4A—C5	128.3 (4)	C12—C11—H11	119.4
C7A—C4A—C5	109.5 (4)	C10—C11—H11	119.4
N6—C5—C4A	102.7 (4)	C11—C12—C13	119.2 (5)
N6—C5—H5A	111.2	C11—C12—H12	120.4
C4A—C5—H5A	111.2	C13—C12—H12	120.4
N6—C5—H5B	111.2	C12—C13—C14	120.9 (5)
C4A—C5—H5B	111.2	C12—C13—H13	119.5
H5A—C5—H5B	109.1	C14—C13—H13	119.5
C7—N6—C9	126.7 (4)	C13—C14—C9	119.1 (5)
C7—N6—C5	112.2 (4)	C13—C14—H14	120.4
C9—N6—C5	121.1 (4)	C9—C14—H14	120.4
O1—C7—N6	124.9 (4)

C8A—S1—C2—C3	0.0 (4)	C7—C7A—C8—C1	1.0 (8)
S1—C2—C3—C3A	−0.4 (5)	O2—C1—C8—C7A	179.9 (4)
C2—C3—C3A—C4	179.7 (5)	O3—C1—C8—C7A	−1.2 (7)
C2—C3—C3A—C8A	0.7 (6)	O2—C1—C8—C8A	0.8 (6)
C8A—C3A—C4—C4A	−2.3 (6)	O3—C1—C8—C8A	179.7 (4)
C3—C3A—C4—C4A	178.8 (4)	C7A—C8—C8A—C3A	−0.3 (6)
C3A—C4—C4A—C7A	1.5 (7)	C1—C8—C8A—C3A	178.8 (4)
C3A—C4—C4A—C5	179.4 (4)	C7A—C8—C8A—S1	−178.6 (3)
C4—C4A—C5—N6	179.1 (4)	C1—C8—C8A—S1	0.5 (6)
C7A—C4A—C5—N6	−2.8 (5)	C4—C3A—C8A—C8	1.8 (7)
C4A—C5—N6—C7	3.5 (5)	C3—C3A—C8A—C8	−179.2 (4)
C4A—C5—N6—C9	−174.9 (4)	C4—C3A—C8A—S1	−179.7 (3)
C9—N6—C7—O1	−5.8 (8)	C3—C3A—C8A—S1	−0.6 (5)
C5—N6—C7—O1	175.8 (4)	C2—S1—C8A—C8	178.8 (4)
C9—N6—C7—C7A	175.4 (4)	C2—S1—C8A—C3A	0.3 (3)
C5—N6—C7—C7A	−3.0 (5)	C7—N6—C9—C10	−19.4 (7)
C4—C4A—C7A—C8	−0.1 (7)	C5—N6—C9—C10	158.8 (4)
C5—C4A—C7A—C8	−178.4 (4)	C7—N6—C9—C14	163.3 (4)
C4—C4A—C7A—C7	179.5 (4)	C5—N6—C9—C14	−18.5 (6)
C5—C4A—C7A—C7	1.2 (5)	C14—C9—C10—C11	−1.3 (7)
O1—C7—C7A—C4A	−177.7 (5)	N6—C9—C10—C11	−178.6 (4)
N6—C7—C7A—C4A	1.0 (5)	C9—C10—C11—C12	0.3 (8)
O1—C7—C7A—C8	1.8 (8)	C10—C11—C12—C13	0.3 (8)
N6—C7—C7A—C8	−179.5 (5)	C11—C12—C13—C14	0.2 (8)
C4A—C7A—C8—C8A	−0.5 (6)	C12—C13—C14—C9	−1.2 (7)
C7—C7A—C8—C8A	−179.9 (4)	C10—C9—C14—C13	1.8 (7)
C4A—C7A—C8—C1	−179.6 (4)	N6—C9—C14—C13	179.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1	0.74 (8)	1.76 (8)	2.496 (5)	175 (8)
C5—H5A···O2ⁱ	0.99	2.37	3.343 (6)	167
C5—H5B···O2ⁱⁱ	0.99	2.37	3.013 (6)	122
C11—H11···O1ⁱⁱⁱ	0.95	2.50	3.333 (6)	146

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

Acknowledgements

The authors' contributions are as follows. Conceptualization, TH and MHAD; synthesis, ERS and VPZ; X-ray analysis, VNK and NAG; Hirshfeld surface analysis, TH; writing (review and editing of the manuscript), TH, KIH and TAJ; supervision, TH and MHAD.

Funding information

This publication has been supported by the Russian Science Foundation (project number: 24–23-00212), see https://rscf.ru/project/24–23-00212/. KIH, NAG and TAJ thank the Azerbaijan Medical University, Baku Engineering University and Khazar University, respectively. TH is also grateful to Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

References

Ajaz, A., Bradley, A. Z., Burrell, R. C., Li, W. H. H., Daoust, K. J., Bovee, L. B., DiRico, K. J. & Johnson, R. P. (2011). J. Org. Chem. 76, 9320–9328. Web of Science CrossRef CAS PubMed Google Scholar
Bober, A. E., Proto, J. T. & Brummond, K. M. (2017). Org. Lett. 19, 1500–1503. Web of Science CrossRef CAS PubMed Google Scholar
Brummond, K. M. & Kocsis, L. S. (2015). Acc. Chem. Res. 48, 2320–2329. Web of Science CrossRef CAS PubMed Google Scholar
El-Mrabet, A., Haoudi, A., Dalbouha, S., Skalli, M. K., Hökelek, T., Capet, F., Kandri Rodi, Y., Mazzah, A. & Sebbar, N. K. (2023). Acta Cryst. E79, 883–889. Web of Science CSD CrossRef IUCr Journals Google Scholar
Filali Baba, Y., Hayani, S., Dalbouha, S., Hökelek, T., Ouazzani Chahdi, F., Mague, J. T., Kandri Rodi, Y., Sebbar, N. K. & Essassi, E. M. (2022). Acta Cryst. E78, 425–432. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hoye, T. R., Baire, B., Niu, D., Willoughby, P. H. & Woods, B. P. (2012). Nature 490, 208–212. Web of Science CrossRef CAS PubMed Google Scholar
Huang, J., Du, X., Van Hecke, K., Van der Eycken, E. V., Pereshivko, O. P. & Peshkov, V. A. (2017). Eur. J. Org. Chem. pp. 4379–4388. Web of Science CSD CrossRef Google Scholar
Johnson, R. P. (2010). J. Phys. Org. Chem. 23, 283–292. Web of Science CrossRef CAS Google Scholar
Kiemm, L. H. & Gopinath, K. W. (1965). J. Heterocycl. Chem. 2, 225–227. CrossRef Google Scholar
Klemm, L. H., Gopinath, K. W., Hsu Lee, D., Kelly, F. W., Trod, E. & McGuire, T. M. (1966). Tetrahedron 22, 1797–1808. CrossRef CAS Web of Science Google Scholar
Krishna, G., Grudinin, D. G., Nikitina, E. V. & Zubkov, F. I. (2022). Synthesis 54, 797–863. CAS Google Scholar
Li, W., Zhou, L. & Zhang, J. (2016). Chem. A Eur. J. 22, 1558–1571. Web of Science CrossRef CAS Google Scholar
Lu, K., Luo, T., Xiang, Z., You, Z., Fathi, R., Chen, J. & Yang, Z. (2005). J. Comb. Chem. 7, 958–967. Web of Science CrossRef PubMed CAS Google Scholar
Mague, J. T., Akkurt, M., Mohamed, S. K., Al-badrany, K. A. & Ahmed, E. A. (2016). IUCrData 1, x161500. Google Scholar
Rana, A., Paul, I. & Schmittel, M. (2017). J. Phys. Org. Chem. 30, e3732. Web of Science CrossRef Google Scholar
Rigaku OD (2021). CryAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals 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
Shelukho, E. R., Yakovleva, E. D., Logvinenko, N. A., Khrustalev, V. N., Novikov, R. A., Zubkov, F. I. & Zaytsev, V. P. (2025). Synlett 36, 1358–1362. CAS Google Scholar
Sim, G. A., Robertson, J. M. & Goodwin, T. H. (1955). Acta Cryst. 8, 157–164. CSD CrossRef IUCr Journals Web of Science 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
Wang, T., Niu, D. & Hoye, T. R. (2016). J. Am. Chem. Soc. 138, 7832–7835. Web of Science CrossRef CAS PubMed Google Scholar
Wessig, P. & Müller, G. (2008). Chem. Rev. 108, 2051–2063. Web of Science CrossRef PubMed CAS Google Scholar

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