Crystal structure of 4,5,6,7,8,8-hexa­chloro-2-(3,4-di­meth­oxy­pheneth­yl)-3a,4,7,7a-tetra­hydro-1H-4,7-methano­iso­indole-1,3(2H)-dione [+solvent]

Manohar, R.; Harikrishna, M.; Etti, S.H.; Ramanathan, C.; Gunasekaran, K.

doi:10.1107/S2056989019004109

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 562-564

https://doi.org/10.1107/S2056989019004109

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Crystal structure of 4,5,6,7,8,8-hexachloro-2-(3,4-dimethoxyphenethyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione [+solvent]

R. Manohar,^a ‡ M. Harikrishna,^b S. Harikrishna Etti,^c C. Ramanathan ^b and K. Gunasekaran ^a ^*

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, ^bDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India, and ^cDepartment of Medical Physics, Bharathiar University, Coimbatore, India
^*Correspondence e-mail: gunaunom@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 21 February 2019; accepted 26 March 2019; online 2 April 2019)

In the title compound, C₁₉H₁₅Cl₆NO₄ [+solvent], 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, the structure features C—H⋯O intermolecular hydrogen bonds, an offset π–π interaction [intercentroid distance = 3.564 (1) Å] and a C—Cl⋯π interaction. The contribution of some disordered solvent to the scattering was removed using the SQUEEZE routine [Spek (2015 ). Acta Cryst. C71, 9–18] of PLATON. The solvent contribution was not included in the reported molecular weight and density.

Keywords: crystal structure; norbornene; hexachloro; isoindolene; hydrogen bonding; offset π–π interaction; C—Cl⋯π interaction.

CCDC reference: 1905872

1. Chemical context

One of the fundamental objectives of organic and medicinal chemistry is the design and synthesis of molecules having value as human therapeutic agents (Patil & Rajput, 2014 ). Succinimide derivatives are significant compounds found in various natural products, and have outstanding biological and pharmaceutical activity (Ahire & Mhaske, 2017 ). Cyclic imides and their derivatives contain an imide ring and the general structure –CO–-N(R)—CO–, and can cross biological membranes in vivo (Hargreaves et al., 1970 ). The variety of biological activities and pharmaceutical uses of compounds containing a succinimide moiety is considerable. They include activities such as antifungal (Hazra et al., 2004 ), anti-tubercular (Isaka et al., 2006 ), CNS depressant (Aeberli et al., 1976 ), antispasmodic (Nunes et al., 1995 ), cytostatic (Crider et al., 1980 ), analgesic (Correa et al., 1997 ), antibacterial (Zentz et al., 2002 ), anticancer (Hall et al., 1995 ), anorectic (Rich & Gardner, 1983 ), hypotensive (Coram & Brezenoff, 1983 ), nerve conduction blocking (Kaczorowski et al., 2008 ), bacteriostatic (Piper et al., 1971 ), anti-convulsant (Kornet et al., 1977 ) and muscle relaxant (Musso et al., 2003 ).

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The six-membered ring of the norbornene moiety (C2/C3/C5/C7–C9) adopts a boat conformation [puckering parameters: amplitude Q = 0.939 (2) Å, θ = 90.00 (12)°, φ = 299.27 (14)°]. The two five-membered rings, A (C2/C3/C5–C7) and B (C5–C9), have envelope conformations with atom C6 as the flap: puckering parameters and the smallest displacement asymmetric parameters are Q₂ = 0.619 (2) Å, φ₂ = 108.6 (2)° and Δs = 1.09° for ring A, and Q₂ = 0.582 (2) Å, φ₂ = 215.5 (2)° and Δs = 0.74° for ring B. Atom C6 is displaced from the mean plane through the other four atoms by 0.908 (2) Å in ring A and 0.875 (2) Å in ring B. The dihedral angle between the pyrrolidine ring (N1/C1–C4) and the benzene ring (C12–C17) is 14.83 (12)°, with the torsion angle N1—C10—C11—C12 being 175.8 (3)°. The lengths of the C—Cl bonds involving the chlorine atoms attached to the C8=C9 double bond are 1.692 (2) Å for C8—Cl2 and 1.692 (2) Å for C9—Cl3. The lengths of the bonds to chlorine atoms attached to the single C—C bonds vary from 1.744 (2) to 1.768 (2) Å. These value are close to those found in similar compounds; see §4 Database survey.

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at 30% probability level.

3. Supramolecular features

In the crystal, weak C19—H19A⋯O2ⁱ hydrogen bonds link the molecules to form a cyclic R₄⁴(48) ring motif (Table 1 and Fig. 2). The molecules are stacked in layers held together by offset π–π interactions (Fig. 2), with an intercentroid distance Cg1⋯Cg5ⁱⁱⁱ of 3.564 (1) Å [Cg1 and Cg5 are the centroids of the pyrrolidine (N1/C1–C4) and benzene (C12–C17) rings, respectively, α = 9.80 (12)°, interplanar distances are 3.448 (1) and 3.547 (1) Å, offset = 0.353 Å; symmetry code: (iii) −y + $[{3\over 4}]$ , x − $[{1\over 4}]$ , −z + $[{3\over 4}]$ ]. There is also an intermolecular C—Cl⋯π interaction present, involving atom Cl6 and the centroid of the benzene ring (C12–C17); see Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

Cg5 is the centroid of the C12–C17 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19A⋯O2ⁱ	0.96	2.57	3.408 (4)	146
C6—Cl6⋯Cg5ⁱⁱ	1.77 (1)	3.41 (1)	4.894 (2)	140 (1)
Symmetry codes: (i) $[y+{\script{1\over 4}}, -x+{\script{3\over 4}}, -z+{\script{7\over 4}}]$ ; (ii) $[-y+{\script{3\over 4}}, x-{\script{1\over 4}}, -z+{\script{3\over 4}}]$ .

Figure 2
A view along the c axis of the crystal packing of the title compound. The C—H⋯O hydrogen bonds (thin black lines; Table 1

) generate an R₄⁴(48) ring motif. The offset π–π interaction is shown as a thin red line. For clarity, H atoms not involved in hydrogen bonding have been omitted.

4. Database survey

A search of the Cambridge Structural Database (CSD, V 5.40, update February 2019; Groom et al., 2016 ) for the 4,5,6,7,8,8-hexachloro-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione skeleton yielded 17 hits (see supporting information). The majority of these compounds have thiophene substituents. One compound, 1,7,8,9,10,10-hexachloro-4-(2-phenylethyl)-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione (CSD refcode EVEDIT; Manohar et al., 2011 ), closely resembles the title compound but has a 2-phenethyl substituent rather than the 2-(3,4-dimethylphenethyl) group in the title compound. Here, the aryl ring is inclined to the pyrrolidine ring by 7.43 (16)° compared to 14.83 (12)° in the title compound, and the N—C—C—C_ar torsion angle is −169.3 (3)° compared to 175.8 (3)° in the title compound.

In all 17 structures, the five-membered ring has envelope conformations and the six-membered ring a boat conformation. The bond lengths and bond angles are very similar to those reported here for the title compound. For example, the Csp²—Cl bond lengths are shorter than the Csp³—Cl bond lengths; the former vary from ca 1.681 to 1.717 Å, while the latter vary from ca 1.725 to 1.798 Å. In the title compound these bond lengths are 1.691 (2)–1.692 (2) Å and 1.744 (2)–1.768 (2) Å, respectively.

5. Synthesis and crystallization

2-(3,4-Dimethoxyphenyl) ethanamine (1 equiv.) and 1,4,5,6,7,7-hexachloro-5- norbornene −2,3-dicarboxylic anhydride (1 equiv.) were stirred at room temperature in dry ethyl acetate for 30 min. The ethyl acetate was removed under reduced pressure and the resulting residue was dissolved in toluene. To this reaction mixture was added acetyl chloride (5 equiv.) and refluxed for 1 h. The reaction mixture was brought to room temperature and washed with aqueous Na₂CO₃ and dried over anhydrous Na₂SO₄. It was then filtered and the filtrate was concentrated under reduced pressure followed by silica gel column purification to afford the title compound in 82% yield. Colourless block-shaped crystals were obtained by slow evaporation of a solution in ethanol.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen atoms were placed in calculated positions and refined using a riding model: C—H = 0.93–0.98 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms. The contribution of the disordered solvent to the scattering was removed using the SQUEEZE routine of PLATON (Spek, 2015). The solvent contribution was not included in the reported molecular weight and density. Further details are given in the archived CIF.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₅Cl₆NO₄[+solvent]
M_r	534.02
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	293
a, c (Å)	29.6250 (9), 10.2427 (4)
V (Å³)	8989.4 (6)
Z	16
Radiation type	Mo Kα
μ (mm⁻¹)	0.79
Crystal size (mm)	0.26 × 0.21 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.752, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	10728, 5181, 3330
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.101, 1.04
No. of reflections	5181
No. of parameters	273
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.21
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ), SHELXL2018 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1905872

Crystal structure: contains datablocks Global, I. DOI: https://doi.org/10.1107/S2056989019004109/su5485sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004109/su5485Isup3.hkl

CSD search S1. DOI: https://doi.org/10.1107/S2056989019004109/su5485sup4.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2056989019004109/su5485Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015) and PLATON (Spek, 2009).

4,5,6,7,8,8-Hexachloro-2-(3,4-dimethoxyphenethyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione top

Crystal data top

C₁₉H₁₅Cl₆NO₄[+solvent]	D_x = 1.578 Mg m⁻³
M_r = 534.02	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 5181 reflections
a = 29.6250 (9) Å	θ = 2.8–29.2°
c = 10.2427 (4) Å	µ = 0.79 mm⁻¹
V = 8989.4 (6) Å³	T = 293 K
Z = 16	Block, colourless
F(000) = 4320	0.26 × 0.21 × 0.15 mm

Data collection top

Bruker SMART APEXII area-detector diffractometer	3330 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.021
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 29.2°, θ_min = 2.8°
T_min = 0.752, T_max = 0.863	h = −32→24
10728 measured reflections	k = −40→24
5181 independent reflections	l = −12→12

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.046P)² + 2.6033P] where P = (F_o² + 2F_c²)/3
5181 reflections	(Δ/σ)_max = 0.001
273 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.21 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	0.64197 (3)	0.18131 (2)	0.50159 (7)	0.0609 (2)
Cl2	0.53878 (2)	0.16505 (2)	0.39238 (6)	0.05182 (19)
Cl3	0.51735 (2)	0.05095 (2)	0.39790 (6)	0.04926 (18)
Cl4	0.60427 (3)	−0.00099 (2)	0.52552 (7)	0.0560 (2)
Cl5	0.68772 (2)	0.07881 (3)	0.59849 (7)	0.0604 (2)
Cl6	0.65299 (2)	0.08158 (2)	0.33757 (6)	0.05024 (19)
O1	0.55317 (7)	0.18699 (7)	0.73520 (19)	0.0638 (6)
O2	0.51935 (7)	0.03730 (7)	0.74848 (17)	0.0583 (5)
O3	0.29789 (7)	0.07109 (6)	0.78565 (19)	0.0606 (5)
O4	0.26332 (6)	0.14834 (6)	0.75279 (18)	0.0512 (5)
N1	0.52660 (7)	0.11436 (8)	0.74800 (18)	0.0436 (5)
C1	0.55897 (9)	0.14695 (10)	0.7253 (2)	0.0452 (6)
C2	0.60172 (8)	0.12358 (8)	0.6826 (2)	0.0374 (6)
H2	0.627206	0.131273	0.739349	0.045*
C3	0.59071 (7)	0.07269 (8)	0.6881 (2)	0.0345 (5)
H3	0.610647	0.056594	0.748616	0.041*
C4	0.54179 (9)	0.07055 (10)	0.7313 (2)	0.0419 (6)
C5	0.59788 (8)	0.05717 (7)	0.5446 (2)	0.0321 (5)
C6	0.63858 (7)	0.08698 (9)	0.5043 (2)	0.0359 (6)
C7	0.61330 (8)	0.13120 (8)	0.5366 (2)	0.0353 (5)
C8	0.57030 (7)	0.12315 (8)	0.45795 (19)	0.0304 (5)
C9	0.56157 (7)	0.07940 (8)	0.46217 (19)	0.0291 (5)
C10	0.47983 (9)	0.12501 (11)	0.7835 (2)	0.0561 (8)
H10A	0.478774	0.154042	0.827179	0.067*
H10B	0.468475	0.102335	0.843401	0.067*
C11	0.45025 (10)	0.12635 (15)	0.6621 (3)	0.0885 (13)
H11A	0.460751	0.150372	0.605383	0.106*
H11B	0.453546	0.098090	0.615245	0.106*
C12	0.40091 (10)	0.13382 (14)	0.6918 (3)	0.0630 (9)
C13	0.37364 (10)	0.09809 (11)	0.7279 (2)	0.0580 (8)
H13	0.386380	0.069607	0.737894	0.070*
C14	0.32777 (9)	0.10361 (9)	0.7495 (2)	0.0439 (6)
C15	0.30858 (8)	0.14660 (9)	0.7326 (2)	0.0396 (6)
C16	0.33546 (9)	0.18220 (10)	0.6993 (2)	0.0519 (7)
H16	0.322956	0.210806	0.689646	0.062*
C17	0.38163 (10)	0.17583 (13)	0.6796 (3)	0.0641 (9)
H17	0.399661	0.200407	0.657959	0.077*
C18	0.31333 (14)	0.02580 (11)	0.7890 (4)	0.0954 (13)
H18A	0.323689	0.017167	0.703745	0.143*
H18B	0.289057	0.006337	0.815147	0.143*
H18C	0.337711	0.023232	0.850281	0.143*
C19	0.24021 (10)	0.18878 (10)	0.7231 (3)	0.0670 (9)
H19A	0.249922	0.212192	0.781535	0.101*
H19B	0.208313	0.184150	0.732920	0.101*
H19C	0.246680	0.197481	0.634816	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0617 (5)	0.0460 (4)	0.0751 (5)	−0.0269 (4)	0.0008 (4)	0.0089 (3)
Cl2	0.0569 (4)	0.0473 (4)	0.0512 (4)	0.0131 (3)	−0.0095 (3)	0.0098 (3)
Cl3	0.0436 (4)	0.0551 (4)	0.0491 (4)	−0.0167 (3)	−0.0143 (3)	−0.0023 (3)
Cl4	0.0691 (5)	0.0336 (3)	0.0652 (4)	0.0060 (3)	0.0037 (4)	0.0058 (3)
Cl5	0.0315 (3)	0.0879 (6)	0.0618 (4)	0.0052 (4)	−0.0120 (3)	0.0078 (4)
Cl6	0.0448 (4)	0.0656 (5)	0.0404 (3)	−0.0024 (3)	0.0122 (3)	0.0030 (3)
O1	0.0729 (15)	0.0533 (13)	0.0651 (13)	0.0064 (11)	−0.0032 (11)	−0.0172 (10)
O2	0.0576 (12)	0.0645 (13)	0.0527 (11)	−0.0226 (11)	0.0096 (9)	0.0062 (10)
O3	0.0659 (13)	0.0456 (11)	0.0703 (13)	0.0102 (11)	−0.0031 (11)	0.0087 (10)
O4	0.0419 (11)	0.0452 (10)	0.0664 (12)	0.0106 (9)	−0.0006 (9)	0.0052 (9)
N1	0.0363 (12)	0.0636 (15)	0.0310 (10)	−0.0031 (11)	0.0025 (9)	−0.0060 (10)
C1	0.0504 (17)	0.0571 (17)	0.0282 (12)	−0.0019 (15)	−0.0080 (11)	−0.0082 (12)
C2	0.0345 (13)	0.0465 (15)	0.0312 (12)	−0.0078 (11)	−0.0062 (10)	−0.0023 (11)
C3	0.0310 (12)	0.0449 (14)	0.0275 (11)	−0.0035 (11)	−0.0047 (10)	0.0076 (10)
C4	0.0439 (15)	0.0561 (17)	0.0258 (12)	−0.0064 (14)	−0.0029 (11)	0.0023 (12)
C5	0.0362 (13)	0.0293 (12)	0.0309 (11)	−0.0027 (10)	−0.0018 (10)	0.0053 (10)
C6	0.0280 (12)	0.0471 (15)	0.0326 (12)	−0.0034 (11)	−0.0031 (10)	0.0063 (11)
C7	0.0341 (13)	0.0352 (13)	0.0366 (12)	−0.0143 (11)	−0.0020 (10)	0.0025 (11)
C8	0.0272 (12)	0.0397 (13)	0.0245 (10)	−0.0003 (10)	−0.0018 (9)	0.0029 (10)
C9	0.0261 (11)	0.0379 (13)	0.0234 (10)	−0.0044 (10)	−0.0026 (9)	−0.0002 (10)
C10	0.0403 (15)	0.089 (2)	0.0392 (14)	0.0055 (15)	0.0103 (12)	−0.0088 (14)
C11	0.0425 (17)	0.181 (4)	0.0419 (17)	0.017 (2)	0.0052 (14)	−0.009 (2)
C12	0.0434 (17)	0.115 (3)	0.0300 (14)	0.006 (2)	0.0000 (12)	−0.0106 (16)
C13	0.0549 (18)	0.086 (2)	0.0331 (14)	0.0287 (18)	−0.0063 (13)	−0.0089 (14)
C14	0.0463 (16)	0.0576 (17)	0.0278 (12)	0.0119 (14)	−0.0041 (11)	−0.0027 (12)
C15	0.0411 (15)	0.0490 (15)	0.0288 (12)	0.0042 (13)	−0.0035 (11)	−0.0023 (11)
C16	0.0534 (18)	0.0598 (18)	0.0426 (14)	−0.0016 (15)	0.0002 (13)	−0.0013 (14)
C17	0.0541 (19)	0.094 (3)	0.0438 (16)	−0.0127 (19)	0.0066 (14)	−0.0035 (17)
C18	0.114 (3)	0.056 (2)	0.116 (3)	0.029 (2)	−0.003 (3)	0.021 (2)
C19	0.0515 (18)	0.0576 (19)	0.092 (2)	0.0157 (16)	−0.0160 (17)	0.0047 (17)

Geometric parameters (Å, º) top

Cl1—C7	1.748 (2)	C6—C7	1.545 (3)
Cl2—C8	1.692 (2)	C7—C8	1.526 (3)
Cl3—C9	1.691 (2)	C8—C9	1.322 (3)
Cl4—C5	1.744 (2)	C10—C11	1.522 (4)
Cl5—C6	1.763 (2)	C10—H10A	0.9700
Cl6—C6	1.768 (2)	C10—H10B	0.9700
O1—C1	1.203 (3)	C11—C12	1.509 (4)
O2—C4	1.201 (3)	C11—H11A	0.9700
O3—C14	1.360 (3)	C11—H11B	0.9700
O3—C18	1.418 (3)	C12—C17	1.375 (4)
O4—C15	1.358 (3)	C12—C13	1.382 (4)
O4—C19	1.413 (3)	C13—C14	1.386 (4)
N1—C1	1.380 (3)	C13—H13	0.9300
N1—C4	1.384 (3)	C14—C15	1.405 (4)
N1—C10	1.467 (3)	C15—C16	1.365 (4)
C1—C2	1.508 (3)	C16—C17	1.395 (4)
C2—C3	1.543 (3)	C16—H16	0.9300
C2—C7	1.550 (3)	C17—H17	0.9300
C2—H2	0.9800	C18—H18A	0.9600
C3—C4	1.516 (3)	C18—H18B	0.9600
C3—C5	1.554 (3)	C18—H18C	0.9600
C3—H3	0.9800	C19—H19A	0.9600
C5—C9	1.518 (3)	C19—H19B	0.9600
C5—C6	1.551 (3)	C19—H19C	0.9600

C14—O3—C18	117.8 (2)	C8—C9—Cl3	128.85 (18)
C15—O4—C19	118.6 (2)	C5—C9—Cl3	123.33 (17)
C1—N1—C4	114.1 (2)	N1—C10—C11	110.3 (2)
C1—N1—C10	123.2 (2)	N1—C10—H10A	109.6
C4—N1—C10	122.6 (2)	C11—C10—H10A	109.6
O1—C1—N1	125.2 (3)	N1—C10—H10B	109.6
O1—C1—C2	126.7 (3)	C11—C10—H10B	109.6
N1—C1—C2	108.1 (2)	H10A—C10—H10B	108.1
C1—C2—C3	105.1 (2)	C12—C11—C10	113.4 (2)
C1—C2—C7	113.51 (19)	C12—C11—H11A	108.9
C3—C2—C7	102.98 (18)	C10—C11—H11A	108.9
C1—C2—H2	111.6	C12—C11—H11B	108.9
C3—C2—H2	111.6	C10—C11—H11B	108.9
C7—C2—H2	111.6	H11A—C11—H11B	107.7
C4—C3—C2	104.7 (2)	C17—C12—C13	118.3 (3)
C4—C3—C5	113.19 (18)	C17—C12—C11	121.1 (4)
C2—C3—C5	103.01 (17)	C13—C12—C11	120.5 (3)
C4—C3—H3	111.8	C12—C13—C14	121.7 (3)
C2—C3—H3	111.8	C12—C13—H13	119.2
C5—C3—H3	111.8	C14—C13—H13	119.2
O2—C4—N1	124.8 (2)	O3—C14—C13	126.7 (3)
O2—C4—C3	127.3 (3)	O3—C14—C15	114.3 (2)
N1—C4—C3	107.9 (2)	C13—C14—C15	118.9 (3)
C9—C5—C6	98.95 (17)	O4—C15—C16	125.8 (2)
C9—C5—C3	107.51 (18)	O4—C15—C14	114.5 (2)
C6—C5—C3	100.94 (17)	C16—C15—C14	119.7 (3)
C9—C5—Cl4	116.28 (16)	C15—C16—C17	120.2 (3)
C6—C5—Cl4	116.64 (17)	C15—C16—H16	119.9
C3—C5—Cl4	114.41 (15)	C17—C16—H16	119.9
C7—C6—C5	92.81 (17)	C12—C17—C16	121.1 (3)
C7—C6—Cl5	113.55 (16)	C12—C17—H17	119.4
C5—C6—Cl5	114.70 (15)	C16—C17—H17	119.4
C7—C6—Cl6	113.64 (16)	O3—C18—H18A	109.5
C5—C6—Cl6	113.18 (16)	O3—C18—H18B	109.5
Cl5—C6—Cl6	108.47 (12)	H18A—C18—H18B	109.5
C8—C7—C6	99.14 (18)	O3—C18—H18C	109.5
C8—C7—C2	107.55 (17)	H18A—C18—H18C	109.5
C6—C7—C2	100.98 (18)	H18B—C18—H18C	109.5
C8—C7—Cl1	115.47 (16)	O4—C19—H19A	109.5
C6—C7—Cl1	116.16 (16)	O4—C19—H19B	109.5
C2—C7—Cl1	115.42 (16)	H19A—C19—H19B	109.5
C9—C8—C7	107.41 (19)	O4—C19—H19C	109.5
C9—C8—Cl2	128.61 (18)	H19A—C19—H19C	109.5
C7—C8—Cl2	123.74 (17)	H19B—C19—H19C	109.5
C8—C9—C5	107.74 (19)

C4—N1—C1—O1	−179.4 (2)	C1—C2—C7—C8	−47.0 (3)
C10—N1—C1—O1	2.1 (4)	C3—C2—C7—C8	66.0 (2)
C4—N1—C1—C2	2.3 (3)	C1—C2—C7—C6	−150.4 (2)
C10—N1—C1—C2	−176.2 (2)	C3—C2—C7—C6	−37.3 (2)
O1—C1—C2—C3	179.7 (2)	C1—C2—C7—Cl1	83.5 (2)
N1—C1—C2—C3	−2.1 (2)	C3—C2—C7—Cl1	−163.44 (16)
O1—C1—C2—C7	−68.6 (3)	C6—C7—C8—C9	34.4 (2)
N1—C1—C2—C7	109.7 (2)	C2—C7—C8—C9	−70.2 (2)
C1—C2—C3—C4	1.1 (2)	Cl1—C7—C8—C9	159.29 (17)
C7—C2—C3—C4	−117.95 (19)	C6—C7—C8—Cl2	−150.73 (16)
C1—C2—C3—C5	119.72 (18)	C2—C7—C8—Cl2	104.6 (2)
C7—C2—C3—C5	0.6 (2)	Cl1—C7—C8—Cl2	−25.9 (3)
C1—N1—C4—O2	178.5 (2)	C7—C8—C9—C5	0.7 (2)
C10—N1—C4—O2	−3.0 (4)	Cl2—C8—C9—C5	−173.78 (16)
C1—N1—C4—C3	−1.6 (3)	C7—C8—C9—Cl3	177.45 (17)
C10—N1—C4—C3	176.95 (19)	Cl2—C8—C9—Cl3	3.0 (3)
C2—C3—C4—O2	−180.0 (2)	C6—C5—C9—C8	−35.4 (2)
C5—C3—C4—O2	68.6 (3)	C3—C5—C9—C8	69.1 (2)
C2—C3—C4—N1	0.1 (2)	Cl4—C5—C9—C8	−161.17 (16)
C5—C3—C4—N1	−111.3 (2)	C6—C5—C9—Cl3	147.60 (17)
C4—C3—C5—C9	45.4 (3)	C3—C5—C9—Cl3	−107.85 (19)
C2—C3—C5—C9	−67.1 (2)	Cl4—C5—C9—Cl3	21.9 (2)
C4—C3—C5—C6	148.5 (2)	C1—N1—C10—C11	94.0 (3)
C2—C3—C5—C6	36.1 (2)	C4—N1—C10—C11	−84.4 (3)
C4—C3—C5—Cl4	−85.4 (2)	N1—C10—C11—C12	175.8 (3)
C2—C3—C5—Cl4	162.17 (16)	C10—C11—C12—C17	99.6 (4)
C9—C5—C6—C7	52.57 (18)	C10—C11—C12—C13	−82.5 (4)
C3—C5—C6—C7	−57.35 (18)	C17—C12—C13—C14	1.1 (4)
Cl4—C5—C6—C7	178.05 (15)	C11—C12—C13—C14	−176.8 (2)
C9—C5—C6—Cl5	170.14 (16)	C18—O3—C14—C13	−7.2 (4)
C3—C5—C6—Cl5	60.2 (2)	C18—O3—C14—C15	172.3 (3)
Cl4—C5—C6—Cl5	−64.4 (2)	C12—C13—C14—O3	−179.7 (2)
C9—C5—C6—Cl6	−64.7 (2)	C12—C13—C14—C15	0.8 (4)
C3—C5—C6—Cl6	−174.59 (15)	C19—O4—C15—C16	7.7 (4)
Cl4—C5—C6—Cl6	60.8 (2)	C19—O4—C15—C14	−172.6 (2)
C5—C6—C7—C8	−52.15 (18)	O3—C14—C15—O4	−1.2 (3)
Cl5—C6—C7—C8	−170.68 (14)	C13—C14—C15—O4	178.4 (2)
Cl6—C6—C7—C8	64.71 (19)	O3—C14—C15—C16	178.5 (2)
C5—C6—C7—C2	57.87 (18)	C13—C14—C15—C16	−1.9 (3)
Cl5—C6—C7—C2	−60.66 (19)	O4—C15—C16—C17	−179.2 (2)
Cl6—C6—C7—C2	174.73 (15)	C14—C15—C16—C17	1.2 (4)
C5—C6—C7—Cl1	−176.50 (15)	C13—C12—C17—C16	−1.9 (4)
Cl5—C6—C7—Cl1	65.0 (2)	C11—C12—C17—C16	176.0 (2)
Cl6—C6—C7—Cl1	−59.6 (2)	C15—C16—C17—C12	0.8 (4)

Hydrogen-bond geometry (Å, º) top

Cg5 is the centroid of the C12–C17 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19A···O2ⁱ	0.96	2.57	3.408 (4)	146
C6—Cl6···Cg5ⁱⁱ	1.77 (1)	3.41 (1)	4.894 (2)	140 (1)

Symmetry codes: (i) y+1/4, −x+3/4, −z+7/4; (ii) −y+3/4, x−1/4, −z+3/4.

Footnotes

‡Current address: Center for Cellular Biology and Pharmacology Herbert Werthiem College of Medicine, Florida International University, ZIP-33199, FL, USA.

Funding information

RM thanks the UGC, Government of India for an SRF fellowship.

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