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; Vladimir P Zaytsev; Victor N Khrustalev; Tuncer Hökelek; Khudayar I Hasanov; Narmina A Guliyeva; Tahir A Javadzade; Mohammed Hadi Al-Douh

doi:10.1107/S2056989025008618

. 2025 Oct 7;81(Pt 11):1000–1003. doi: 10.1107/S2056989025008618

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, Mohammed Hadi Al-Douh ^g,^*

Editor: J Ellena^h

PMCID: PMC12589846 PMID: 41209647

The molecule of the title compound contains a planar thieno[2,3-f]isoindole ring system and a phenyl ring. 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 further consolidate the crystal structure.

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

Abstract

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.

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

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

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 Inline graphic (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.

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 ▸).

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

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

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Computer programs: CrysAlis PRO (Rigaku OD, 2021 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸) and SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989025008618/ex2095sup1.cif

e-81-01000-sup1.cif^{(379.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989025008618/ex2095Isup2.hkl

e-81-01000-Isup2.hkl^{(222KB, hkl)}

e-81-01000-Isup3.cml^{(5.5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989025008618/ex2095Isup3.cml

CCDC reference: 2492514

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

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

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

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

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

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

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

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

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.

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7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

	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*

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7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Atomic displacement parameters (Å²)

	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)

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7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Geometric parameters (Å, º)

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)

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7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Hydrogen-bond geometry (Å, º)

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

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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.

Funding Statement

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. [DOI] [PubMed]
Bober, A. E., Proto, J. T. & Brummond, K. M. (2017). Org. Lett.19, 1500–1503. [DOI] [PubMed]
Brummond, K. M. & Kocsis, L. S. (2015). Acc. Chem. Res.48, 2320–2329. [DOI] [PubMed]
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. [DOI] [PMC free article] [PubMed]
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. [DOI] [PMC free article] [PubMed]
Hoye, T. R., Baire, B., Niu, D., Willoughby, P. H. & Woods, B. P. (2012). Nature490, 208–212. [DOI] [PMC free article] [PubMed]
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.
Johnson, R. P. (2010). J. Phys. Org. Chem.23, 283–292.
Kiemm, L. H. & Gopinath, K. W. (1965). J. Heterocycl. Chem.2, 225–227.
Klemm, L. H., Gopinath, K. W., Hsu Lee, D., Kelly, F. W., Trod, E. & McGuire, T. M. (1966). Tetrahedron22, 1797–1808.
Krishna, G., Grudinin, D. G., Nikitina, E. V. & Zubkov, F. I. (2022). Synthesis54, 797–863.
Li, W., Zhou, L. & Zhang, J. (2016). Chem. A Eur. J.22, 1558–1571.
Lu, K., Luo, T., Xiang, Z., You, Z., Fathi, R., Chen, J. & Yang, Z. (2005). J. Comb. Chem.7, 958–967. [DOI] [PubMed]
Mague, J. T., Akkurt, M., Mohamed, S. K., Al-badrany, K. A. & Ahmed, E. A. (2016). IUCrData1, x161500.
Rana, A., Paul, I. & Schmittel, M. (2017). J. Phys. Org. Chem.30, e3732.
Rigaku OD (2021). CryAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
Shelukho, E. R., Yakovleva, E. D., Logvinenko, N. A., Khrustalev, V. N., Novikov, R. A., Zubkov, F. I. & Zaytsev, V. P. (2025). Synlett36, 1358–1362.
Sim, G. A., Robertson, J. M. & Goodwin, T. H. (1955). Acta Cryst.8, 157–164.
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. [DOI] [PMC free article] [PubMed]
Wang, T., Niu, D. & Hoye, T. R. (2016). J. Am. Chem. Soc.138, 7832–7835. [DOI] [PMC free article] [PubMed]
Wessig, P. & Müller, G. (2008). Chem. Rev.108, 2051–2063. [DOI] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989025008618/ex2095sup1.cif

e-81-01000-sup1.cif^{(379.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989025008618/ex2095Isup2.hkl

e-81-01000-Isup2.hkl^{(222KB, hkl)}

e-81-01000-Isup3.cml^{(5.5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989025008618/ex2095Isup3.cml

CCDC reference: 2492514

Additional supporting information: crystallographic information; 3D view; checkCIF report

[bb1] 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. [DOI] [PubMed]

[bb2] Bober, A. E., Proto, J. T. & Brummond, K. M. (2017). Org. Lett.19, 1500–1503. [DOI] [PubMed]

[bb3] Brummond, K. M. & Kocsis, L. S. (2015). Acc. Chem. Res.48, 2320–2329. [DOI] [PubMed]

[bb4] 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. [DOI] [PMC free article] [PubMed]

[bb5] 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. [DOI] [PMC free article] [PubMed]

[bb6] Hoye, T. R., Baire, B., Niu, D., Willoughby, P. H. & Woods, B. P. (2012). Nature490, 208–212. [DOI] [PMC free article] [PubMed]

[bb7] 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.

[bb8] Johnson, R. P. (2010). J. Phys. Org. Chem.23, 283–292.

[bb9] Kiemm, L. H. & Gopinath, K. W. (1965). J. Heterocycl. Chem.2, 225–227.

[bb10] Klemm, L. H., Gopinath, K. W., Hsu Lee, D., Kelly, F. W., Trod, E. & McGuire, T. M. (1966). Tetrahedron22, 1797–1808.

[bb11] Krishna, G., Grudinin, D. G., Nikitina, E. V. & Zubkov, F. I. (2022). Synthesis54, 797–863.

[bb12] Li, W., Zhou, L. & Zhang, J. (2016). Chem. A Eur. J.22, 1558–1571.

[bb13] Lu, K., Luo, T., Xiang, Z., You, Z., Fathi, R., Chen, J. & Yang, Z. (2005). J. Comb. Chem.7, 958–967. [DOI] [PubMed]

[bb14] Mague, J. T., Akkurt, M., Mohamed, S. K., Al-badrany, K. A. & Ahmed, E. A. (2016). IUCrData1, x161500.

[bb15] Rana, A., Paul, I. & Schmittel, M. (2017). J. Phys. Org. Chem.30, e3732.

[bb16] Rigaku OD (2021). CryAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.

[bb17] Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

[bb18] Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.

[bb19] Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.

[bb20] Shelukho, E. R., Yakovleva, E. D., Logvinenko, N. A., Khrustalev, V. N., Novikov, R. A., Zubkov, F. I. & Zaytsev, V. P. (2025). Synlett36, 1358–1362.

[bb21] Sim, G. A., Robertson, J. M. & Goodwin, T. H. (1955). Acta Cryst.8, 157–164.

[bb22] 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. [DOI] [PMC free article] [PubMed]

[bb23] Wang, T., Niu, D. & Hoye, T. R. (2016). J. Am. Chem. Soc.138, 7832–7835. [DOI] [PMC free article] [PubMed]

[bb24] Wessig, P. & Müller, G. (2008). Chem. Rev.108, 2051–2063. [DOI] [PubMed]

PERMALINK

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

Vladimir P Zaytsev

Victor N Khrustalev

Tuncer Hökelek

Khudayar I Hasanov

Narmina A Guliyeva

Tahir A Javadzade

Mohammed Hadi Al-Douh

Roles

Abstract

1. Chemical context

2. Structural commentary

Table 1. Hydrogen-bond geometry (Å, °).

Figure 1.

3. Supra­molecular features

Figure 2.

4. Hirshfeld surface analysis

Figure 3.

Figure 4.

5. Synthesis and crystallization

6. Refinement

Table 2. Experimental details.

Supplementary Material

Acknowledgments

supplementary crystallographic information

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

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

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

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

7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Atomic displacement parameters (Å2)

7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Geometric parameters (Å, º)

7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Hydrogen-bond geometry (Å, º)

Funding Statement

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

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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

3. Supramolecular features

7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

7-Oxo-6-phenyl-6,7-dihydro-5H-thieno[2,3-f]isoindole-8-carboxylic acid . Atomic displacement parameters (Å²)