Crystal structure and Hirshfeld surface analysis of 1-(2-chloro­acet­yl)-3-methyl-2,6-bis­(4-methylphen­yl)piperidin-4-one

Divyabharathi, S.; Rajeswari, K.; Vidhyasagar, T.; Selvanayagam, S.

doi:10.1107/S2056989026000083

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 82| Part 2| February 2026| Pages 152-155

https://doi.org/10.1107/S2056989026000083

Open

access

Crystal structure and Hirshfeld surface analysis of 1-(2-chloroacetyl)-3-methyl-2,6-bis(4-methylphenyl)piperidin-4-one

Sivagnanam Divyabharathi,^a Krishnan Rajeswari,^b,^c Thankakan Vidhyasagar ^b ^* and Sivashanmugam Selvanayagam ^d ‡

^aDepartment of Chemistry, Vel Tech Multi Tech Dr Rangarajan Dr Sakunthala Engineering College, Avadi, Chennai 600 062, India, ^bDepartment of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, India, ^cPG & Research Department of Chemistry, Government Arts College, Chidambaram 608 102, India, and ^dPG & Research Department of Physics, Government Arts College, Melur 625 106, India
^*Correspondence e-mail: [email protected]

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 24 November 2025; accepted 6 January 2026; online 8 January 2026)

In the crystal structure of the title compound, C₂₂H₂₄ClNO₂, the piperidine ring adopts a boat conformation. Intra- and intermolecular C—H⋯Cl hydrogen bonds are observed. The intermolecular interactions were quantified and analysed using Hirshfeld surface analysis, revealing that H⋯H interactions contribute most to the crystal packing (56.1%).

Keywords: piperidine derivative; intermolecular hydrogen bonds; Hirshfeld surface analysis; crystal structure.

CCDC reference: 2184416

1. Chemical context

Piperidin-4-one derivatives represent a significant class of heterocyclic compounds widely documented for their versatility in the field of medicinal chemistry. The piperidin-4-one scaffold serves as a valuable synthetic intermediate and as a promising pharmacophore showing diverse biological activities (Sahu et al., 2013 ). Among piperidin-4-one derivatives, 3-alkyl-2,6-diarylpiperidin-4-one derivatives have been extensively investigated, particularly with respect to their synthesis, stereochemistry, and diverse biological activities. 3-Alkyl-2,6-diarylpiperidone derivatives predominantly adopt a chair conformation with an equatorial orientation of the alkyl and phenyl substituents (Pandiarajan et al., 1991 ). The introduction of groups such as –NO, –CHO, –COCH₃, and N—COCH₂Cl onto the ring nitrogen atom of a 2,6-diarylpiperidin-4-one moiety significantly alter the ring conformation and the orientation of its substituents. Delocalization of the nitrogen lone pair into the –COR π-system imparts partial double-bond character to the —N—CO linkage, thereby restricting its rotation. The steric interaction between the N—CO group and the neighbouring equatorial substituent causes molecular strain, which is relieved by adopting a chair form with an axial orientation of the phenyl substituents or a boat form with one phenyl substituent in the flagpole position. The effects of such substitutions on the geometry of the piperidin-4-one nucleus have been extensively reported. Structural variations such as N-benzoyl (Krishnapillay et al., 2000 ), N-nitroso (Ravindran et al., 1991 ), N-formyl (Pandiarajan et al., 1997 ), N-chloroacetyl (Aridoss et al., 2007a ,b ; Divyabharathi et al., 2024 ) and N-thiocyanatoacetyl (Karthiga et al., 2024 , 2025 ) derivatives have all been studied. Furthermore, investigations into the DNA-binding properties of N-acetyl analogues (Mohanraj & Ponnuswamy, 2018 ) and their antibacterial activities (Aridoss et al., 2008 ) have also been reported. In the present work, crystal structure and Hirshfeld surface analysis of 1-(2-chloroacetyl)-3-methyl-2,6-bis(4-methylphenyl)piperidin-4-one, are reported.

2. Structural commentary

The molecular structure is presented in Fig. 1. The compound is chiral due to the presence of stereogenic centres. Although the molecular structure depicted in Fig. 1 shows the 2R,3S,6S enantiomer, the crystal contains a racemic mixture of enantiomers. The O1—C3 [1.207 (2) Å] and O2—C6 [1.221 (2) Å] bond lengths confirm the double-bond character. The sum of the angles around atom N1 (357.1°) indicates that nitrogen adopts an almost trigonal–planar geometry. Conjugation between the carbonyl group and the adjacent C—C bond, combined with steric hindrance from the chloromethyl substituent, restricts free rotation about the C6—C7 bond. This limited rotational freedom results in distinct preferred conformations, which is reflected in the observed torsion angles O2—C6—C7—Cl1 [100.5 (2)°] and N1—C6—C7—Cl1 [−80.4 (2)°]. The piperidine ring adopts a boat conformation; the puckering parameters (Cremer & Pople, 1975 ) are: q₂ = 0.677 (2) Å, q₃ = −0.060 (2) Å, Q_T = 0.680 (2) Å and φ = 107.4 (2)°. Atoms C2 and C5 in the piperidine ring (N1/C1–C5) deviate by −0.528 (2) and −0.604 (2) Å, respectively, from the least-squares plane through the remaining four atoms. The methylphenyl rings C8–C13 and C15–C21 are planar, with their attached methyl atoms C14 and C22 deviate by −0.024 (3) and 0.003 (3) Å, respectively, from their ring planes. These methylphenyl rings are oriented with a dihedral angle of 51.7 (1)° with respect to each other. A weak intramolecular contact (Table 1) between a methine H atom and the Cl atom attached to the 2-chloroacetaldehyde moiety (C6/O2/C7/Cl1) leads to the stabilization of the molecular conformation. This C5—H5⋯Cl1 interaction forms an S(6) ring motif (Bernstein et al., 1995 ), as shown in Fig. 1.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Cl1	0.98	2.61	3.342 (2)	132
C1—H1⋯Cl1ⁱ	0.98	2.79	3.674 (2)	151
C7—H7A⋯Cgⁱⁱ	0.97	2.85	3.575 (2)	133
Symmetry codes: (i) ; (ii) .

Figure 1
Molecular structure showing the atom-labelling scheme and the intramolecular hydrogen bond (dashed line). Ellipsoids are drawn at the 30% probability level.

3. Supramolecular features

In the crystal, molecules associate pairwise via C1—H1⋯Cl1ⁱ hydrogen bonds (Table 1) into inversion dimers with an R₂²(12) graph-set motif (Etter et al., 1990 ), as shown in Fig. 2. Moreover, molecules are further linked into an R₂²(14) graph-set motif by C—H⋯π interactions, C7—H7A⋯Cg, where Cg is the centroid of the symmetry-related C8–C13 benzene ring at (2 − x, 2 − y, 1 − z) (Table 1).

Figure 2
Centrosymmetric dimer through C—H⋯Cl hydrogen bonds [Symmetry code: (a) −x + 1, −y, −z + 1].

4. Hirshfeld surface analysis

The intermolecular interactions were quantified by a Hirshfeld surface (HS) analysis (Spackman & Jayatilaka, 2009 ) using CrystalExplorer (Spackman et al., 2021 ). The HS mapped over d_norm is illustrated in Fig. 3. where no red spot occurs. This represents the non-availability of potential hydrogen bonds in this crystal. The associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) provide quantitative information about the non-covalent interactions in the crystal packing in terms of the percentage contribution of the interatomic contacts (Spackman & McKinnon, 2002 ). The overall two-dimensional fingerprint plot is shown in Fig. 4a (top left). The HS analysis reveals that H⋯H and H⋯O/O⋯H contacts are the main contributors to the crystal packing followed by H⋯C/C⋯H, H⋯Cl/Cl⋯H, Cl⋯C/C⋯Cl, C⋯C and Cl⋯O/O⋯Cl contacts; see Fig. 4b–h.

Figure 3
Hirshfeld surface mapped over d_norm.

Figure 4
Two-dimensional fingerprint plots showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯C/C⋯H, (e)H⋯Cl/Cl⋯H, (f) Cl⋯C/C⋯Cl, (g) C⋯C and (h) Cl⋯O/O⋯Cl 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

The compound has been previously reported, and all characterization data are consistent with those described by Aridoss et al., 2007a,b. The compound was synthesized by mixing 3-methyl-2,6-di-p-tolylpiperidin-4-one (0.75 g, 2.5 mmol) and chloroacetyl chloride (1.0 mL, 10 mmol). The mixture was stirred in anhydrous benzene (50 mL) at room temperature. Then, triethylamine (1.4 mL, 10 mmol) was added as a base to initiate the reaction. The reaction mixture was maintained at room temperature for 6 h. Upon completion, the precipitated triethylammonium chloride salt was removed by filtration. The resulting organic layer was washed thoroughly with water then dried over anhydrous Na₂SO₄. The solvent was removed and the crude product was recrystallized from a mixture of petroleum ether and ethyl acetate (9:1, v/v) to afford the product as colourless crystals.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were placed in idealized positions and allowed to ride on their parent atoms: C—H = 0.93–0.98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and U_iso(H) = 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₂H₂₄ClNO₂
M_r	369.87
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	298
a, b, c (Å)	8.7654 (5), 11.3919 (6), 11.6090 (7)
α, β, γ (°)	110.594 (2), 102.709 (2), 107.595 (2)
V (Å³)	962.71 (10)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.21
Crystal size (mm)	0.35 × 0.23 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.711, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	24328, 5355, 3183
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.135, 1.03
No. of reflections	5355
No. of parameters	238
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.27
Computer programs: APEX3 and SAINT (Bruker, 2017 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2184416

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989026000083/tx2106sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026000083/tx2106Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989026000083/tx2106sup3.txt

checkCIF report

Computing details top

1-(2-Chloroacetyl)-3-methyl-2,6-bis(4-methylphenyl)piperidin-4-one top

Crystal data top

C₂₂H₂₄ClNO₂	Z = 2
M_r = 369.87	F(000) = 392
Triclinic, P1	D_x = 1.276 Mg m⁻³
a = 8.7654 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.3919 (6) Å	Cell parameters from 6744 reflections
c = 11.6090 (7) Å	θ = 2.6–28.8°
α = 110.594 (2)°	µ = 0.21 mm⁻¹
β = 102.709 (2)°	T = 298 K
γ = 107.595 (2)°	Block, colourless
V = 962.71 (10) Å³	0.35 × 0.23 × 0.19 mm

Data collection top

Bruker APEXII CCD diffractometer	3183 reflections with I > 2σ(I)
Radiation source: i-mu-s microfocus source	R_int = 0.043
φ and ω scans	θ_max = 30.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→12
T_min = 0.711, T_max = 0.746	k = −15→16
24328 measured reflections	l = −15→16
5355 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.0437P)² + 0.2977P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
5355 reflections	Δρ_max = 0.18 e Å⁻³
238 parameters	Δρ_min = −0.27 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	0.25775 (8)	−0.21845 (5)	0.47830 (6)	0.0760 (2)
O1	0.85771 (18)	0.29415 (17)	0.90454 (19)	0.0905 (6)
O2	0.20241 (19)	0.06629 (14)	0.46708 (13)	0.0676 (4)
N1	0.34459 (17)	0.11084 (13)	0.67584 (13)	0.0436 (3)
C1	0.4496 (2)	0.25412 (16)	0.70160 (16)	0.0430 (4)
H1	0.493746	0.246576	0.629971	0.052*
C2	0.6072 (2)	0.33108 (17)	0.83254 (17)	0.0467 (4)
H2	0.563298	0.350761	0.904614	0.056*
C3	0.7039 (2)	0.2449 (2)	0.84836 (19)	0.0544 (4)
C4	0.5966 (2)	0.09311 (18)	0.79297 (19)	0.0523 (4)
H4A	0.639400	0.060054	0.854009	0.063*
H4B	0.608122	0.044809	0.710194	0.063*
C5	0.4065 (2)	0.05969 (17)	0.76895 (16)	0.0459 (4)
H5	0.345337	−0.041045	0.722924	0.055*
C6	0.2292 (2)	0.02538 (18)	0.55034 (17)	0.0498 (4)
C7	0.1282 (2)	−0.12542 (18)	0.5127 (2)	0.0589 (5)
H7A	0.025083	−0.164551	0.435285	0.071*
H7B	0.093917	−0.133089	0.584595	0.071*
C8	0.3460 (2)	0.33884 (16)	0.69974 (16)	0.0436 (4)
C9	0.2647 (2)	0.36976 (18)	0.78849 (18)	0.0501 (4)
H9	0.266432	0.332410	0.848017	0.060*
C10	0.1809 (2)	0.45532 (19)	0.79026 (19)	0.0551 (5)
H10	0.125999	0.473644	0.850156	0.066*
C11	0.1777 (2)	0.51415 (19)	0.70398 (19)	0.0577 (5)
C12	0.2585 (3)	0.4826 (2)	0.6152 (2)	0.0632 (5)
H12	0.257599	0.520543	0.556190	0.076*
C13	0.3407 (3)	0.39610 (19)	0.61200 (17)	0.0552 (5)
H13	0.392961	0.375967	0.550488	0.066*
C14	0.0891 (3)	0.6093 (2)	0.7089 (3)	0.0801 (7)
H14A	0.090380	0.653225	0.796661	0.120*
H14B	−0.027693	0.557154	0.647625	0.120*
H14C	0.148117	0.678073	0.685548	0.120*
C15	0.7241 (3)	0.4697 (2)	0.8473 (2)	0.0629 (5)
H15A	0.665406	0.529360	0.857365	0.094*
H15B	0.753294	0.455989	0.769991	0.094*
H15C	0.827119	0.511073	0.923769	0.094*
C16	0.3612 (2)	0.10762 (17)	0.89173 (17)	0.0459 (4)
C17	0.4756 (3)	0.15250 (19)	1.01738 (18)	0.0566 (5)
H17	0.586631	0.158729	1.028921	0.068*
C18	0.4274 (3)	0.1882 (2)	1.12598 (19)	0.0623 (5)
H18	0.507013	0.218030	1.209176	0.075*
C19	0.2642 (3)	0.18084 (19)	1.1142 (2)	0.0605 (5)
C20	0.1502 (3)	0.1367 (2)	0.9891 (2)	0.0628 (5)
H20	0.039547	0.131290	0.977987	0.075*
C21	0.1972 (2)	0.1003 (2)	0.87960 (19)	0.0546 (5)
H21	0.117321	0.070404	0.796475	0.066*
C22	0.2150 (4)	0.2203 (3)	1.2342 (2)	0.0888 (8)
H22A	0.095320	0.202382	1.207207	0.133*
H22B	0.282704	0.316607	1.292575	0.133*
H22C	0.235683	0.167058	1.279197	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0787 (4)	0.0539 (3)	0.0795 (4)	0.0288 (3)	0.0323 (3)	0.0103 (3)
O1	0.0434 (8)	0.0746 (10)	0.1260 (15)	0.0156 (8)	0.0014 (9)	0.0413 (10)
O2	0.0794 (10)	0.0584 (8)	0.0419 (7)	0.0190 (7)	0.0066 (7)	0.0156 (6)
N1	0.0441 (8)	0.0359 (7)	0.0393 (7)	0.0099 (6)	0.0108 (6)	0.0130 (6)
C1	0.0439 (9)	0.0388 (8)	0.0402 (9)	0.0113 (7)	0.0144 (7)	0.0168 (7)
C2	0.0419 (9)	0.0395 (9)	0.0453 (9)	0.0094 (7)	0.0092 (7)	0.0154 (7)
C3	0.0427 (10)	0.0543 (11)	0.0571 (11)	0.0145 (9)	0.0129 (8)	0.0234 (9)
C4	0.0499 (10)	0.0485 (10)	0.0582 (11)	0.0215 (8)	0.0182 (9)	0.0237 (9)
C5	0.0464 (9)	0.0366 (8)	0.0468 (9)	0.0126 (7)	0.0129 (8)	0.0170 (7)
C6	0.0468 (10)	0.0432 (9)	0.0425 (10)	0.0138 (8)	0.0104 (8)	0.0092 (8)
C7	0.0478 (10)	0.0428 (10)	0.0591 (11)	0.0111 (8)	0.0088 (9)	0.0073 (9)
C8	0.0431 (9)	0.0375 (8)	0.0372 (8)	0.0094 (7)	0.0073 (7)	0.0138 (7)
C9	0.0524 (10)	0.0475 (10)	0.0484 (10)	0.0181 (8)	0.0160 (8)	0.0231 (8)
C10	0.0506 (10)	0.0515 (10)	0.0549 (11)	0.0194 (9)	0.0157 (9)	0.0189 (9)
C11	0.0486 (10)	0.0469 (10)	0.0573 (12)	0.0149 (9)	0.0006 (9)	0.0175 (9)
C12	0.0713 (13)	0.0591 (12)	0.0531 (11)	0.0229 (11)	0.0084 (10)	0.0308 (10)
C13	0.0650 (12)	0.0543 (11)	0.0415 (10)	0.0214 (10)	0.0146 (9)	0.0224 (8)
C14	0.0723 (15)	0.0693 (14)	0.0925 (17)	0.0371 (12)	0.0105 (13)	0.0352 (13)
C15	0.0533 (11)	0.0474 (10)	0.0654 (13)	0.0044 (9)	0.0095 (9)	0.0230 (10)
C16	0.0494 (10)	0.0372 (8)	0.0466 (10)	0.0124 (7)	0.0155 (8)	0.0199 (7)
C17	0.0559 (11)	0.0534 (11)	0.0502 (11)	0.0165 (9)	0.0132 (9)	0.0215 (9)
C18	0.0768 (14)	0.0496 (11)	0.0446 (10)	0.0157 (10)	0.0128 (10)	0.0187 (9)
C19	0.0852 (15)	0.0444 (10)	0.0581 (12)	0.0258 (10)	0.0336 (11)	0.0264 (9)
C20	0.0664 (13)	0.0701 (13)	0.0721 (14)	0.0326 (11)	0.0370 (11)	0.0427 (11)
C21	0.0539 (11)	0.0593 (11)	0.0542 (11)	0.0202 (9)	0.0202 (9)	0.0319 (9)
C22	0.133 (2)	0.0797 (16)	0.0738 (16)	0.0489 (17)	0.0600 (16)	0.0382 (13)

Geometric parameters (Å, º) top

Cl1—C7	1.789 (2)	C10—H10	0.9300
O1—C3	1.207 (2)	C11—C12	1.381 (3)
O2—C6	1.221 (2)	C11—C14	1.505 (3)
N1—C6	1.361 (2)	C12—C13	1.380 (3)
N1—C5	1.476 (2)	C12—H12	0.9300
N1—C1	1.493 (2)	C13—H13	0.9300
C1—C8	1.514 (2)	C14—H14A	0.9600
C1—C2	1.547 (2)	C14—H14B	0.9600
C1—H1	0.9800	C14—H14C	0.9600
C2—C3	1.509 (3)	C15—H15A	0.9600
C2—C15	1.526 (2)	C15—H15B	0.9600
C2—H2	0.9800	C15—H15C	0.9600
C3—C4	1.502 (3)	C16—C17	1.384 (2)
C4—C5	1.528 (2)	C16—C21	1.387 (3)
C4—H4A	0.9700	C17—C18	1.382 (3)
C4—H4B	0.9700	C17—H17	0.9300
C5—C16	1.523 (2)	C18—C19	1.380 (3)
C5—H5	0.9800	C18—H18	0.9300
C6—C7	1.519 (3)	C19—C20	1.381 (3)
C7—H7A	0.9700	C19—C22	1.506 (3)
C7—H7B	0.9700	C20—C21	1.385 (3)
C8—C9	1.383 (2)	C20—H20	0.9300
C8—C13	1.389 (2)	C21—H21	0.9300
C9—C10	1.384 (3)	C22—H22A	0.9600
C9—H9	0.9300	C22—H22B	0.9600
C10—C11	1.387 (3)	C22—H22C	0.9600

C6—N1—C5	122.82 (14)	C11—C10—H10	119.5
C6—N1—C1	115.84 (14)	C12—C11—C10	117.69 (18)
C5—N1—C1	118.41 (13)	C12—C11—C14	122.0 (2)
N1—C1—C8	113.14 (13)	C10—C11—C14	120.4 (2)
N1—C1—C2	112.07 (13)	C13—C12—C11	121.62 (18)
C8—C1—C2	110.05 (13)	C13—C12—H12	119.2
N1—C1—H1	107.1	C11—C12—H12	119.2
C8—C1—H1	107.1	C12—C13—C8	120.64 (18)
C2—C1—H1	107.1	C12—C13—H13	119.7
C3—C2—C15	112.14 (15)	C8—C13—H13	119.7
C3—C2—C1	112.78 (14)	C11—C14—H14A	109.5
C15—C2—C1	110.77 (14)	C11—C14—H14B	109.5
C3—C2—H2	106.9	H14A—C14—H14B	109.5
C15—C2—H2	106.9	C11—C14—H14C	109.5
C1—C2—H2	106.9	H14A—C14—H14C	109.5
O1—C3—C4	121.39 (18)	H14B—C14—H14C	109.5
O1—C3—C2	122.60 (18)	C2—C15—H15A	109.5
C4—C3—C2	115.99 (15)	C2—C15—H15B	109.5
C3—C4—C5	112.45 (15)	H15A—C15—H15B	109.5
C3—C4—H4A	109.1	C2—C15—H15C	109.5
C5—C4—H4A	109.1	H15A—C15—H15C	109.5
C3—C4—H4B	109.1	H15B—C15—H15C	109.5
C5—C4—H4B	109.1	C17—C16—C21	117.32 (17)
H4A—C4—H4B	107.8	C17—C16—C5	122.49 (16)
N1—C5—C16	112.38 (14)	C21—C16—C5	120.10 (15)
N1—C5—C4	108.01 (14)	C18—C17—C16	121.07 (19)
C16—C5—C4	116.21 (14)	C18—C17—H17	119.5
N1—C5—H5	106.5	C16—C17—H17	119.5
C16—C5—H5	106.5	C19—C18—C17	121.76 (19)
C4—C5—H5	106.5	C19—C18—H18	119.1
O2—C6—N1	122.11 (16)	C17—C18—H18	119.1
O2—C6—C7	118.71 (16)	C18—C19—C20	117.24 (18)
N1—C6—C7	119.17 (17)	C18—C19—C22	120.7 (2)
C6—C7—Cl1	109.87 (13)	C20—C19—C22	122.1 (2)
C6—C7—H7A	109.7	C19—C20—C21	121.4 (2)
Cl1—C7—H7A	109.7	C19—C20—H20	119.3
C6—C7—H7B	109.7	C21—C20—H20	119.3
Cl1—C7—H7B	109.7	C20—C21—C16	121.20 (18)
H7A—C7—H7B	108.2	C20—C21—H21	119.4
C9—C8—C13	117.95 (16)	C16—C21—H21	119.4
C9—C8—C1	122.47 (15)	C19—C22—H22A	109.5
C13—C8—C1	119.44 (16)	C19—C22—H22B	109.5
C8—C9—C10	121.14 (17)	H22A—C22—H22B	109.5
C8—C9—H9	119.4	C19—C22—H22C	109.5
C10—C9—H9	119.4	H22A—C22—H22C	109.5
C9—C10—C11	120.95 (19)	H22B—C22—H22C	109.5
C9—C10—H10	119.5

C6—N1—C1—C8	70.04 (18)	C2—C1—C8—C9	−63.9 (2)
C5—N1—C1—C8	−128.78 (15)	N1—C1—C8—C13	−122.15 (16)
C6—N1—C1—C2	−164.83 (15)	C2—C1—C8—C13	111.63 (17)
C5—N1—C1—C2	−3.6 (2)	C13—C8—C9—C10	−0.1 (3)
N1—C1—C2—C3	46.1 (2)	C1—C8—C9—C10	175.48 (16)
C8—C1—C2—C3	172.88 (14)	C8—C9—C10—C11	−0.8 (3)
N1—C1—C2—C15	172.67 (15)	C9—C10—C11—C12	1.0 (3)
C8—C1—C2—C15	−60.51 (19)	C9—C10—C11—C14	−178.77 (18)
C15—C2—C3—O1	21.0 (3)	C10—C11—C12—C13	−0.3 (3)
C1—C2—C3—O1	146.9 (2)	C14—C11—C12—C13	179.49 (19)
C15—C2—C3—C4	−160.61 (16)	C11—C12—C13—C8	−0.7 (3)
C1—C2—C3—C4	−34.7 (2)	C9—C8—C13—C12	0.9 (3)
O1—C3—C4—C5	160.7 (2)	C1—C8—C13—C12	−174.90 (17)
C2—C3—C4—C5	−17.7 (2)	N1—C5—C16—C17	−138.29 (17)
C6—N1—C5—C16	−118.60 (17)	C4—C5—C16—C17	−13.2 (2)
C1—N1—C5—C16	81.61 (17)	N1—C5—C16—C21	45.3 (2)
C6—N1—C5—C4	111.89 (17)	C4—C5—C16—C21	170.40 (16)
C1—N1—C5—C4	−47.90 (18)	C21—C16—C17—C18	0.1 (3)
C3—C4—C5—N1	58.85 (19)	C5—C16—C17—C18	−176.44 (16)
C3—C4—C5—C16	−68.5 (2)	C16—C17—C18—C19	0.0 (3)
C5—N1—C6—O2	−166.44 (17)	C17—C18—C19—C20	−0.3 (3)
C1—N1—C6—O2	−6.2 (3)	C17—C18—C19—C22	179.97 (19)
C5—N1—C6—C7	14.5 (2)	C18—C19—C20—C21	0.5 (3)
C1—N1—C6—C7	174.76 (15)	C22—C19—C20—C21	−179.78 (19)
O2—C6—C7—Cl1	100.48 (19)	C19—C20—C21—C16	−0.4 (3)
N1—C6—C7—Cl1	−80.42 (19)	C17—C16—C21—C20	0.1 (3)
N1—C1—C8—C9	62.3 (2)	C5—C16—C21—C20	176.72 (16)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C8–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cl1	0.98	2.61	3.342 (2)	132
C1—H1···Cl1ⁱ	0.98	2.79	3.674 (2)	151
C7—H7A···Cgⁱⁱ	0.97	2.85	3.575 (2)	133

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

Footnotes

‡Additional correspondence author, e-mail: [email protected].

Acknowledgements

The authors thank the Single Crystal XRD Facility at the Department of Chemistry, Annamalai University,Tamil Nadu, India, for providing the instrumentation and support necessary for this study.

References

Aridoss, G., Amirthaganesan, S., Ashok Kumar, N., Kim, J. T., Lim, K. T., Kabilan, S. & Jeong, Y. T. (2008). Bioorg. Med. Chem. Lett. 18, 6542–6548. Web of Science CSD CrossRef PubMed CAS Google Scholar
Aridoss, G., Balasubramanian, S., Parthiban, P. & Kabilan, S. (2007b). Spectrochim. Acta A Mol. Biomol. Spectrosc. 68, 1153–1163. Web of Science CrossRef PubMed CAS Google Scholar
Aridoss, G., Balasubramanian, S., Parthiban, P., Ramachandran, R. & Kabilan, S. (2007a). Med. Chem. Res. 16, 188–204. Web of Science CrossRef CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2017). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Divyabharathi, S., Karthiga, A. R., Shalo, R. R., Rajeswari, K., Vidhyasagar, T. & Selvanayagam, S. (2024). Acta Cryst. E80, 981–985. Web of Science CSD CrossRef IUCr Journals Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kant Sahu, S., Kumar Dubey, B., C. Tripathi, A., Koshy, M. & K. Saraf, S. (2013). Mini Rev. Med. Chem. 13, 565–583. Google Scholar
Karthiga, A. R., Divyabharathi, S., Shalo, R. R., Rajeswari, K. & Vidhyasagar, T. (2025). Chem. Data Collect. 56, 101183. Google Scholar
Karthiga, A. R., Divyabharathi, S., Shalo, R. R., Rajeswari, K., Vidhyasagar, T. & Selvanayagam, S. (2024). Acta Cryst. E80, 1014–1019. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Krishnapillay, M., Kumar, R. K., Nagarajan, A. & Jeyaraman, G. (2000). Indian J. Chem. Sect. B 39, 419–425. Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Mohanraj, V. & Ponnuswamy, S. (2018). J. Mol. Struct. 1171, 420–428. Web of Science CrossRef CAS Google Scholar
Pandiarajan, K., Manimekalai, A. & Kalaiselvi, N. (1997). Magn. Reson. Chem. 35, 372–378. CrossRef CAS Google Scholar
Pandiarajan, K., Sekar, R., Anantharaman, R., Ramalingam, V. & Marko, D. (1991). Indian J. Chem. Sect. B 30, 490–493. Google Scholar
Ravindran, R., Jeyaraman, R., Murray, R. W. & Singh, M. (1991). J. Org. Chem. 56, 4833–4840. CrossRef CAS Web of Science 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, M. A. & McKinnon, J. J. (2002). CrystEngComm 4, 378–392. 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
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.