Crystal structure and Hirshfeld surface analysis of (3aR,4S,7S,7aS)-4,5,6,7,8,8-hexa­chloro-2-{6-[(3aR,4R,7R,7aS)-4,5,6,7,8,8-hexa­chloro-1,3-dioxo-1,3,3a,4,7,7a-hexa­hydro-2H-4,7-methano­isoindol-2-yl]hex­yl}-3a,4,7,7a-tetra­hydro-1H-4,7-methano­iso­indole-1,3(2H)-dione

Alikhanova, A.I.; Atioğlu, Z.; Akkurt, M.; Mlowe, S.

doi:10.1107/S2056989021006952

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 77| Part 8| August 2021| Pages 775-779

https://doi.org/10.1107/S2056989021006952

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Crystal structure and Hirshfeld surface analysis of (3aR,4S,7S,7aS)-4,5,6,7,8,8-hexachloro-2-{6-[(3aR,4R,7R,7aS)-4,5,6,7,8,8-hexachloro-1,3-dioxo-1,3,3a,4,7,7a-hexahydro-2H-4,7-methanoisoindol-2-yl]hexyl}-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione

Aygun I. Alikhanova,^a Zeliha Atioğlu,^b Mehmet Akkurt ^c and Sixberth Mlowe ^d ^*

^aInstitute of Polymer Materials, National Academy of Sciences of Azerbaijan, Sumgayit, 5004, Azerbaijan, ^bDepartment of Aircraft Electrics and Electronics, School of Applied Sciences, Cappadocia University, Mustafapaşa, 50420 Ürgüp, Nevşehir, Turkey, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^dUniversity of Dar es Salaam, Dar es Salaam University College of Education, Department of Chemistry, PO Box 2329, Dar es Salaam, Tanzania
^*Correspondence e-mail: sixberth.mlowe@duce.ac.tz

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 29 June 2021; accepted 6 July 2021; online 9 July 2021)

The molecule of the title compound, C₂₄H₁₆Cl₁₂N₂O₄, is generated by a crystallographic inversion centre at the midpoint of the central C—C bond. A kink in the molecule is defined by a torsion angle of −169.86 (15)° about this central bond of the alkyl bridge. The pyrrolidine ring is essentially planar [max. deviation = 0.014 (1) Å]. The cyclohexane ring has a boat conformation, while both cyclopentane rings adopt an envelope conformation. In the crystal structure, molecules are linked by intermolecular C—H⋯O, C—H⋯Cl and C—Cl⋯π interactions, and short intermolecular Cl⋯O and Cl⋯Cl contacts, forming a three-dimensional network.

Keywords: crystal structure; pyrrolidine ring; cyclopentane ring; cyclohexane ring; Hirshfeld surface analysis.

CCDC reference: 2094787

1. Chemical context

N-heterocyclic compounds are of interest in the fields of synthetic organic chemistry, coordination chemistry and medicinal chemistry because of their important biological properties (Mahmoudi et al., 2016 , 2017a ,b ,c , 2018a ,b ; 2019 ; Viswanathan et al., 2019 ). For this reason, many approaches have been developed for their efficient and versatile synthesis (Gurbanov et al., 2017 , 2018a ,b ; Ma et al., 2017a ,b ). On the other hand, N-heterocycles or N-ligands can also be used as precursors in the synthesis of coordination compounds (Ma et al., 2020 , 2021 ; Mahmudov et al., 2013 ), and as building blocks in the construction of supramolecular structures as they have both hydrogen-bond donor and acceptor capabilities (Gurbanov et al., 2020a ; Kopylovich et al., 2011a ,b ; Asgarova et al., 2019 ). In fact, attachment of suitable functional groups to N-ligands can improve their solubility and the catalytic activity of the corresponding coordination compounds (Mizar et al., 2012 ; Gurbanov et al., 2020b ; Khalilov et al., 2011 , 2018a ,b ; Maharramov et al., 2019 ; Shikhaliyev et al., 2019 ; Shixaliyev et al., 2014 ). Intermolecular halogen bonds and other types of non-covalent interactions in halogenated N-heterocyclic compounds can improve their solubility and other functional properties. In order to continue our work in this perspective, we have synthesized a new halogenated N-heterocyclic compound, (3aR,4S,7S,7aS)-4,5,6,7,8,8-hexachloro-2-{6-[(3aR,4R,7R,7aS)-4,5,6,7,8,8-hexachloro-1,3-dioxo-1,3,3a,4,7,7a-hexahydro-2H-4,7-methanoisoindol-2-yl]hexyl}-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione, which provides multiple inermolecular non-covalent interactions.

2. Structural commentary

The molecule of the title compound is generated by a crystallographic inversion centre at the midpoint of the central C—C bond. A kink in the molecule is defined by the C10—C11–C12—C12_a torsion angle of −169.86 (15)° about this central bond of the alkyl bridge (Fig. 1). The pyrrolidine ring (N1/C1/C2/C6/C7) is essentially planar [maximum deviation = −0.014 (1) Å for N1]. The cyclohexane ring (C2/C3/C5/C6/C8/C9) has a boat conformation [the puckering parameters (Cremer and Pople, 1975 ) are Q_T = 0.9300 (14) Å, θ = 89.99 (9)°, φ = 59.37 (9)°], while both the cyclopentane rings (C2–C6 and C3–C5/C8/C9) adopt an envelope conformation [Q(2) = 0.6308 (14) Å, φ(2) = 252.44 (13)° and Q(2) = 0.5835 (14) Å, φ(2) = 215.53 (14)°, respectively] with the C4 atom bearing the dichloromethane group as the flap.

Figure 1
The molecular structure of the title compound with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level. [Symmetry code: (a) 2 − x, 1 − y, −z].

3. Supramolecular features and Hirshfeld surface analysis

In the crystal structure, molecules are linked by intermolecular C—H⋯O, C—H⋯Cl and C—Cl⋯π interactions (Table 1), and short intermolecular contacts, listed in Table 2, forming a three-dimensional network (Figs. 2 and 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C1/C2/C6/C7 pyrrolidine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	1.00	2.43	3.3867 (16)	161
C10—H10A⋯O2ⁱⁱ	0.99	2.45	3.4402 (17)	178
C12—H12B⋯Cl2ⁱⁱⁱ	0.99	2.80	3.5299 (15)	131
C3—Cl1⋯Cg1ⁱⁱⁱ	1.75 (1)	3.89 (1)	4.9389 (14)	117 (1)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
Cl3⋯Cl2	3.4333 (5)	1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
O1⋯H6	2.43	2 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
Cl1⋯H11B	2.99	x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z
Cl3⋯H10B	2.96	−1 + x, y, z
O2⋯Cl4	3.4606 (11)	1 − x, −y, −z
H10A⋯O2	2.45	2 − x, −y, −z

Figure 2
Crystal packing of the title compound viewed along the a-axis direction. C—H⋯O, C—H⋯Cl hydrogen bonds and C—Cl⋯π interactions (Table 1

) are represented by dashed lines. H atoms not involved in hydrogen bonding are omitted for clarity.

Figure 3
Crystal packing viewed along the b axis, with intermolecular interactions shown as in Fig. 2

. H atoms not involved in hydrogen bonding are omitted for clarity.

In order to visualize the intermolecular interactions (Table 2) in the crystal of the title compound, a Hirshfeld surface analysis was carried out using Crystal Explorer 17.5 (Turner et al., 2017 ). Fig. 4 shows the Hirshfeld surface plotted over d_norm in the range −0.1922 to 1.7149 a.u. The red spots on the Hirshfeld surface represent C—H⋯O and C—H⋯Cl contacts. Fig. 5 shows the full two-dimensional fingerprint plot and those delineated into the major contacts: Cl⋯H/H⋯Cl (33.6%; Fig. 5b), Cl⋯Cl (29.3%; Fig. 5c), O⋯H/H⋯O (13.9%; Fig. 5d), Cl⋯O/O⋯Cl (11.4%; Fig. 5e) and H⋯H (7.0%; Fig. 5f) interactions. The remaining other weak interactions (contribution percentages) are Cl⋯C/C⋯Cl (3.2%), Cl⋯N/N⋯Cl (1.4%) and C⋯H/H⋯C (0.2%).

Figure 4
A view of the Hirshfeld surface for the title compound, plotted over d_norm in the range −0.1922 to 1.7149 a.u. together with interacting neighbouring molecules.

Figure 5
A view of the two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) Cl⋯H/H⋯Cl, (c) Cl⋯Cl and (d) O⋯H/H⋯O, (e) Cl⋯O/O⋯Cl and (f) H⋯H interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

4. Database survey

Four related compounds containing the methanoisoindole moiety were found in the Cambridge Structural Database (CSD, version 5.42, update of November 2020; Groom et al., 2016 ): 4,5,6,7,8,8-hexachloro-2-[2-(3,4-dimethoxyphenyl)ethyl]-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (refcode COHTUR: Manohar et al., 2019 ), 5-hydroxy-4-(4-methylphenyl)-4-azatricyclo[5.2.1.0^2,6]dec-8-en-3-one (QOVCAH: Aslantaş et al., 2015 ), (3aR,4S,7R,7aS)-2-(perfluoropyridin-4-yl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (MOJFUP: Peloquin et al., 2019 ) and (3aR,4S,7R,7aS)-2-[(perfluoropyridin-4-yl)oxy]-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (MOJGAW: Peloquin et al., 2019).

In COHTUR, the six-membered ring of the norbornene moiety adopts a boat conformation and the two five-membered rings have envelope conformations. The pyrrolidine ring makes a dihedral angle of 14.83 (12)° with the 3,4-dimethoxyphenyl ring, which are attached to each other by an extended N—CH₂—CH₂—C_ar bridge. In the crystal of COHTUR, weak C—H⋯O hydrogen bonds link the molecules, forming a cyclic R₄⁴(48) ring motif (Bernstein et al., 1995 ). The molecules are stacked in layers held together by offset π–π interactions, with a centroid–centroid distance of 3.564 (1) Å for the pyrrolidine and benzene rings. There is also an intermolecular C—Cl⋯π interaction present.

In the crystal of QOVCAH, the cyclohexene ring adopts a boat conformation, and the five-membered rings have envelope conformations with the bridging atom as the flap. Their mean planes are oriented at a dihedral angle of 86.51 (7)°. The molecular structure is stabilized by a short intramolecular C—H⋯O contact. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming chains propagating along [100]. The chains are linked by C—H⋯π interactions, forming slabs parallel to (001).

The compound MOJFUP crystallizes in the triclinic space group P $[\overline{1}]$ with two molecules, A and B, in the asymmetric unit, and MOJGAW in the monoclinic space group P2₁/n with one molecule per asymmetric unit. The synthesis of both compounds is conducted using endo starting materials, and the same configuration is observed in the resulting crystal structures. In MOJFUP, steric interactions between the ortho-fluorine atoms and the carbonyl oxygen atoms prevents free rotation about the nitrogen–ipso-carbon bond, which is evidenced by separate ¹⁹F NMR peaks in solution for the ortho-F atoms. In molecule A, the 2,3,5,6-tetrafluoropyridine plane is rotated by 58.05 (5)° relative to the pyrrolidine plane and the corresponding dihedral angle for molecule B is 61.65 (7)°. The addition of an oxygen atom between N and C in the bridge between the ring systems in MOJGAW alleviates this steric restriction and only one ¹⁹F NMR peak in solution is observed for the ortho-F atoms; even so, the dihedral angle between the 2,3,5,6-tetrafluoropyridine and pyrrolidine planes in the crystal of MOJGAW of 84.01 (5)° is larger than that found in MOJFUP.

The main directional interactions in the crystal structures of MOJFUP and MOJGAW are of the type C—H⋯O, C—H⋯F, C—O⋯π, and C—F⋯π. In both compounds, weak hydrogen-bonding interactions are observed for the hydrogen atom(s) α to the carbonyl groups (C—H⋯O and C— H⋯F in MOJFUP; C—H⋯O in MOJGAW) and the olefinic hydrogen atoms (C—H⋯F in MOJFUP; C—H⋯O in MOJGAW). A weak interaction is also observed for a bridge hydrogen atom in MOJGAW, C—H⋯F. The packing is further aided by π-interactions with the pyridine ring in MOJGAW.

5. Synthesis and crystallization

To 741 mg (2 mmol) of (3aR,4R,7R,7aS)-4,5,6,7,8,8-hexachloro-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione were added 0.12 mL (1 mmol) of hexane-1,6-diamine and 25 mL of dimethylformamide, and the mixture was stirred for 6 h at 373 K. Then, the reaction mixture was cooled to room temperature and poured into cold water. The obtained precipitate was filtered off, washed with water, recrystallized from chloroform and dried under vacuum. Yellow powder, yield 92%, m.p 404–405 K (decomp.). Analysis calculated for C₂₄H₁₆Cl₁₂N₂O₄ (M_r = 821.80): C 35.08, H 1.96, N 3.41%; found: C 35.03, H 2.00, N 3.35%. ESI–MS: m/z: 822.9 [M_r + H]^{+. 1}H NMR (300.130 MHz) in acetone-d₆, internal TMS, δ (ppm): 1.29–3.43 (12H, 6CH₂), 3.86 (4H, CH). ¹³C{¹H} NMR (75.468 MHz, acetone-d₆). δ: 25.8 (2CH₂), 27.2 (2CH₂), 39.3 (4C–H), 52.0 (2CH₂), 79.3 (4CCl), 104.4 (2CCl₂), 130.9 (2ClC=CCl) and 170.2 (4C=O). Off-white prismatic crystals suitable for X-ray analysis were obtained by slow evaporation of a chloroform–hexane (1/1, v/v) mixture.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.99 (methylene) and 1.00 Å (methine), with U_iso(H) = 1.2U_eq(C). Two reflections (100 and 002), affected by the incident beam-stop, and owing to poor agreement between observed and calculated intensities, two outliers (136 and 118) were omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₂₄H₁₆Cl₁₂N₂O₄
M_r	821.79
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	8.9549 (3), 10.5908 (4), 16.6043 (6)
β (°)	103.499 (1)
V (Å³)	1531.24 (10)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.12
Crystal size (mm)	0.34 × 0.32 × 0.28

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.684, 0.736
No. of measured, independent and observed [I > 2σ(I)] reflections	12567, 3403, 3141
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.053, 1.04
No. of reflections	3403
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.24
Computer programs: APEX2 and SAINT (Bruker, 2007 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2094787

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006952/vm2251sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006952/vm2251Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

(3aR,4S,7S,7aS)-4,5,6,7,8,8-Hexachloro-2-{6-[(3aR,4R,7R,7aS)-4,5,6,7,8,8-hexachloro-1,3-dioxo-1,3,3a,4,7,7a-hexahydro-2H-4,7-methanoisoindol-2-yl]hexyl}-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione top

Crystal data top

C₂₄H₁₆Cl₁₂N₂O₄	F(000) = 820
M_r = 821.79	D_x = 1.782 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.9549 (3) Å	Cell parameters from 7701 reflections
b = 10.5908 (4) Å	θ = 2.3–27.2°
c = 16.6043 (6) Å	µ = 1.12 mm⁻¹
β = 103.499 (1)°	T = 150 K
V = 1531.24 (10) Å³	Block, colourless
Z = 2	0.34 × 0.32 × 0.28 mm

Data collection top

Bruker APEXII CCD diffractometer	3141 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.023
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.2°, θ_min = 2.3°
T_min = 0.684, T_max = 0.736	h = −8→11
12567 measured reflections	k = −13→13
3403 independent reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0231P)² + 0.7545P] where P = (F_o² + 2F_c²)/3
3403 reflections	(Δ/σ)_max = 0.001
190 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.24 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
Cl1	0.81506 (4)	0.38645 (3)	0.33748 (2)	0.02092 (8)
Cl2	0.65657 (4)	0.08552 (3)	0.31569 (2)	0.02036 (8)
Cl3	0.45141 (4)	0.28198 (3)	0.24334 (2)	0.01993 (8)
Cl4	0.48797 (4)	0.05628 (3)	0.10287 (2)	0.02218 (8)
Cl5	0.75019 (4)	0.52267 (3)	0.15453 (2)	0.02455 (9)
Cl6	0.55737 (5)	0.31532 (4)	0.00843 (2)	0.02966 (9)
O1	1.10843 (11)	0.32935 (10)	0.22625 (6)	0.0224 (2)
O2	0.83761 (12)	0.05643 (10)	0.03360 (6)	0.0220 (2)
N1	0.99701 (12)	0.19567 (11)	0.11936 (7)	0.0156 (2)
C1	1.01234 (15)	0.25177 (13)	0.19624 (8)	0.0152 (3)
C2	0.88902 (15)	0.19800 (12)	0.23555 (8)	0.0139 (2)
H2	0.935586	0.153877	0.288724	0.017*
C3	0.76483 (15)	0.29560 (12)	0.24743 (8)	0.0142 (2)
C4	0.62421 (15)	0.20595 (12)	0.24022 (8)	0.0142 (2)
C5	0.63197 (15)	0.15971 (12)	0.15208 (8)	0.0140 (2)
C6	0.79769 (15)	0.10488 (12)	0.17088 (8)	0.0142 (2)
H6	0.801142	0.017191	0.193567	0.017*
C7	0.87382 (15)	0.11223 (12)	0.09843 (8)	0.0153 (3)
C8	0.71121 (15)	0.36779 (12)	0.16671 (8)	0.0153 (3)
C9	0.63396 (15)	0.28797 (13)	0.11034 (8)	0.0157 (3)
C10	1.09720 (16)	0.21915 (14)	0.06241 (8)	0.0200 (3)
H10A	1.112615	0.139247	0.034488	0.024*
H10B	1.198763	0.248383	0.094445	0.024*
C11	1.02959 (17)	0.31780 (14)	−0.00267 (8)	0.0213 (3)
H11A	1.081293	0.311153	−0.049094	0.026*
H11B	0.919312	0.299100	−0.024805	0.026*
C12	1.04563 (18)	0.45260 (13)	0.03013 (8)	0.0223 (3)
H12A	1.010849	0.455925	0.082477	0.027*
H12B	1.155427	0.476794	0.042781	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02260 (17)	0.01966 (17)	0.01950 (16)	0.00008 (13)	0.00287 (13)	−0.00824 (12)
Cl2	0.02766 (18)	0.01698 (16)	0.01742 (15)	0.00127 (13)	0.00727 (13)	0.00505 (12)
Cl3	0.01596 (15)	0.01944 (17)	0.02574 (17)	0.00286 (12)	0.00760 (13)	−0.00038 (12)
Cl4	0.01995 (16)	0.02252 (18)	0.02291 (16)	−0.00783 (13)	0.00266 (13)	−0.00581 (13)
Cl5	0.02410 (18)	0.01230 (16)	0.0374 (2)	−0.00025 (13)	0.00750 (15)	0.00650 (13)
Cl6	0.0340 (2)	0.0339 (2)	0.01635 (16)	0.00063 (16)	−0.00359 (14)	0.00900 (14)
O1	0.0162 (5)	0.0248 (5)	0.0257 (5)	−0.0038 (4)	0.0037 (4)	−0.0082 (4)
O2	0.0253 (5)	0.0215 (5)	0.0197 (5)	−0.0021 (4)	0.0061 (4)	−0.0076 (4)
N1	0.0153 (5)	0.0151 (6)	0.0165 (5)	0.0019 (4)	0.0043 (4)	−0.0011 (4)
C1	0.0124 (6)	0.0151 (6)	0.0168 (6)	0.0048 (5)	0.0008 (5)	−0.0006 (5)
C2	0.0146 (6)	0.0121 (6)	0.0139 (6)	0.0031 (5)	0.0008 (5)	−0.0012 (5)
C3	0.0147 (6)	0.0129 (6)	0.0145 (6)	0.0014 (5)	0.0021 (5)	−0.0018 (5)
C4	0.0153 (6)	0.0118 (6)	0.0154 (6)	0.0020 (5)	0.0037 (5)	0.0016 (5)
C5	0.0144 (6)	0.0128 (6)	0.0138 (6)	−0.0016 (5)	0.0015 (5)	−0.0002 (5)
C6	0.0163 (6)	0.0116 (6)	0.0142 (6)	0.0007 (5)	0.0023 (5)	0.0003 (5)
C7	0.0163 (6)	0.0117 (6)	0.0177 (6)	0.0035 (5)	0.0036 (5)	0.0000 (5)
C8	0.0135 (6)	0.0129 (6)	0.0200 (6)	0.0024 (5)	0.0049 (5)	0.0037 (5)
C9	0.0146 (6)	0.0173 (6)	0.0146 (6)	0.0036 (5)	0.0021 (5)	0.0049 (5)
C10	0.0189 (7)	0.0217 (7)	0.0220 (7)	−0.0003 (6)	0.0100 (5)	−0.0032 (5)
C11	0.0262 (7)	0.0211 (7)	0.0172 (6)	−0.0055 (6)	0.0067 (6)	−0.0023 (5)
C12	0.0274 (7)	0.0209 (7)	0.0178 (6)	−0.0054 (6)	0.0037 (6)	−0.0022 (5)

Geometric parameters (Å, º) top

Cl1—C3	1.7464 (13)	C3—C4	1.5592 (18)
Cl2—C4	1.7639 (13)	C4—C5	1.5599 (17)
Cl3—C4	1.7558 (13)	C5—C9	1.5269 (18)
Cl4—C5	1.7432 (13)	C5—C6	1.5559 (18)
Cl5—C8	1.6989 (14)	C6—C7	1.5168 (18)
Cl6—C9	1.6958 (13)	C6—H6	1.0000
O1—C1	1.2098 (17)	C8—C9	1.3293 (19)
O2—C7	1.2042 (16)	C10—C11	1.523 (2)
N1—C1	1.3855 (16)	C10—H10A	0.9900
N1—C7	1.3927 (17)	C10—H10B	0.9900
N1—C10	1.4686 (17)	C11—C12	1.5228 (19)
C1—C2	1.5186 (19)	C11—H11A	0.9900
C2—C6	1.5442 (17)	C11—H11B	0.9900
C2—C3	1.5642 (17)	C12—C12ⁱ	1.515 (3)
C2—H2	1.0000	C12—H12A	0.9900
C3—C8	1.5203 (17)	C12—H12B	0.9900

C1—N1—C7	113.85 (11)	C2—C6—C5	103.10 (10)
C1—N1—C10	125.21 (11)	C7—C6—H6	111.5
C7—N1—C10	120.94 (11)	C2—C6—H6	111.5
O1—C1—N1	125.37 (13)	C5—C6—H6	111.5
O1—C1—C2	126.60 (12)	O2—C7—N1	124.52 (13)
N1—C1—C2	108.03 (11)	O2—C7—C6	127.35 (12)
C1—C2—C6	105.12 (10)	N1—C7—C6	108.13 (11)
C1—C2—C3	114.59 (11)	C9—C8—C3	107.83 (11)
C6—C2—C3	103.47 (10)	C9—C8—Cl5	128.16 (11)
C1—C2—H2	111.1	C3—C8—Cl5	124.00 (10)
C6—C2—H2	111.1	C8—C9—C5	107.78 (11)
C3—C2—H2	111.1	C8—C9—Cl6	128.08 (11)
C8—C3—C4	98.94 (10)	C5—C9—Cl6	124.06 (10)
C8—C3—C2	107.98 (10)	N1—C10—C11	111.81 (11)
C4—C3—C2	99.97 (10)	N1—C10—H10A	109.3
C8—C3—Cl1	116.29 (9)	C11—C10—H10A	109.3
C4—C3—Cl1	116.31 (9)	N1—C10—H10B	109.3
C2—C3—Cl1	115.05 (9)	C11—C10—H10B	109.3
C3—C4—C5	92.94 (9)	H10A—C10—H10B	107.9
C3—C4—Cl3	114.83 (9)	C12—C11—C10	113.62 (11)
C5—C4—Cl3	113.84 (9)	C12—C11—H11A	108.8
C3—C4—Cl2	112.95 (9)	C10—C11—H11A	108.8
C5—C4—Cl2	113.80 (9)	C12—C11—H11B	108.8
Cl3—C4—Cl2	108.08 (7)	C10—C11—H11B	108.8
C9—C5—C6	108.14 (10)	H11A—C11—H11B	107.7
C9—C5—C4	98.88 (10)	C12ⁱ—C12—C11	113.19 (14)
C6—C5—C4	100.27 (9)	C12ⁱ—C12—H12A	108.9
C9—C5—Cl4	115.59 (9)	C11—C12—H12A	108.9
C6—C5—Cl4	115.22 (9)	C12ⁱ—C12—H12B	108.9
C4—C5—Cl4	116.55 (9)	C11—C12—H12B	108.9
C7—C6—C2	104.81 (10)	H12A—C12—H12B	107.8
C7—C6—C5	113.96 (10)

C7—N1—C1—O1	−178.12 (13)	C3—C2—C6—C5	0.55 (12)
C10—N1—C1—O1	1.4 (2)	C9—C5—C6—C7	−47.46 (14)
C7—N1—C1—C2	2.31 (14)	C4—C5—C6—C7	−150.44 (11)
C10—N1—C1—C2	−178.13 (11)	Cl4—C5—C6—C7	83.59 (12)
O1—C1—C2—C6	179.44 (13)	C9—C5—C6—C2	65.53 (12)
N1—C1—C2—C6	−1.01 (13)	C4—C5—C6—C2	−37.45 (12)
O1—C1—C2—C3	66.54 (17)	Cl4—C5—C6—C2	−163.42 (9)
N1—C1—C2—C3	−113.90 (12)	C1—N1—C7—O2	177.78 (13)
C1—C2—C3—C8	47.50 (14)	C10—N1—C7—O2	−1.8 (2)
C6—C2—C3—C8	−66.37 (12)	C1—N1—C7—C6	−2.63 (15)
C1—C2—C3—C4	150.38 (10)	C10—N1—C7—C6	177.79 (11)
C6—C2—C3—C4	36.51 (11)	C2—C6—C7—O2	−178.64 (13)
C1—C2—C3—Cl1	−84.24 (12)	C5—C6—C7—O2	−66.68 (18)
C6—C2—C3—Cl1	161.89 (9)	C2—C6—C7—N1	1.79 (13)
C8—C3—C4—C5	52.32 (10)	C5—C6—C7—N1	113.75 (12)
C2—C3—C4—C5	−57.86 (10)	C4—C3—C8—C9	−35.34 (13)
Cl1—C3—C4—C5	177.63 (9)	C2—C3—C8—C9	68.27 (13)
C8—C3—C4—Cl3	−65.69 (11)	Cl1—C3—C8—C9	−160.66 (10)
C2—C3—C4—Cl3	−175.87 (8)	C4—C3—C8—Cl5	145.71 (10)
Cl1—C3—C4—Cl3	59.62 (12)	C2—C3—C8—Cl5	−110.68 (11)
C8—C3—C4—Cl2	169.74 (9)	Cl1—C3—C8—Cl5	20.39 (15)
C2—C3—C4—Cl2	59.57 (11)	C3—C8—C9—C5	0.64 (14)
Cl1—C3—C4—Cl2	−64.95 (11)	Cl5—C8—C9—C5	179.54 (10)
C3—C4—C5—C9	−51.85 (10)	C3—C8—C9—Cl6	−176.19 (10)
Cl3—C4—C5—C9	66.99 (11)	Cl5—C8—C9—Cl6	2.7 (2)
Cl2—C4—C5—C9	−168.55 (9)	C6—C5—C9—C8	−69.69 (13)
C3—C4—C5—C6	58.55 (10)	C4—C5—C9—C8	34.26 (13)
Cl3—C4—C5—C6	177.40 (9)	Cl4—C5—C9—C8	159.47 (10)
Cl2—C4—C5—C6	−58.15 (11)	C6—C5—C9—Cl6	107.30 (11)
C3—C4—C5—Cl4	−176.38 (9)	C4—C5—C9—Cl6	−148.75 (10)
Cl3—C4—C5—Cl4	−57.54 (12)	Cl4—C5—C9—Cl6	−23.54 (15)
Cl2—C4—C5—Cl4	66.92 (11)	C1—N1—C10—C11	−96.26 (15)
C1—C2—C6—C7	−0.47 (13)	C7—N1—C10—C11	83.27 (15)
C3—C2—C6—C7	120.07 (11)	N1—C10—C11—C12	76.43 (15)
C1—C2—C6—C5	−119.99 (10)	C10—C11—C12—C12ⁱ	−169.86 (15)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/C1/C2/C6/C7 pyrrolidine ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱⁱ	1.00	2.43	3.3867 (16)	161
C10—H10A···O2ⁱⁱⁱ	0.99	2.45	3.4402 (17)	178
C12—H12B···Cl2^iv	0.99	2.80	3.5299 (15)	131
C3—Cl1···Cg1^iv	1.75 (1)	3.89 (1)	4.9389 (14)	117 (1)

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

Summary of short interatomic contacts (Å) in the title compound top

Contact	Distance	Symmetry operation
Cl3···Cl2	3.4333 (5)	1 - x, 1/2 + y, 1/2 - z
O1···H6	2.43	2 - x, 1/2 + y, 1/2 - z
Cl1···H11B	2.99	x, 1/2 - y, 1/2 + z
Cl3···H10B	2.96	-1 + x, y, z
O2···Cl4	3.4606 (11)	1 - x, -y, -z
H10A···O2	2.45	2 - x, -y, -z

Acknowledgements

The authors' contributions are as follows. Conceptualization, AIA and MA; methodology, AIA and ZA; investigation, AIA, ZA, and SM; writing (original draft), MA and SM; writing (review and editing of the manuscript), MA and SM; visualization, AIA and ZA; funding acquisition, AIA; resources, AIA, ZA and SHM; supervision, MA and SM.

Funding information

This work was supported by the Institute of Polymer Materials, National Academy of Sciences of Azerbaijan.

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