In the title compound, 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—Car bridge.
Keywords: crystal structure, norbornene, hexachloro, isoindolene, hydrogen bonding, offset π–π interaction, C—Cl⋯π interaction
Abstract
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—Car 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.
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 ▸).
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 Q 2 = 0.619 (2) Å, φ2 = 108.6 (2)° and Δs = 1.09° for ring A, and Q 2 = 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.
Supramolecular features
In the crystal, weak C19—H19A⋯O2i hydrogen bonds link the molecules to form a cyclic 
(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 + 
, x − 
, −z + ]. 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) 
; (ii) 
.
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 (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.
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[5.2.1.02,6]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—Car 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 Csp 2—Cl bond lengths are shorter than the Csp 3—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.
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.
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[F 2 > 2σ(F 2)], wR(F 2), S | 0.041, 0.101, 1.04 |
| No. of reflections | 5181 |
| No. of parameters | 273 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.33, −0.21 |
Supplementary Material
Crystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989019004109/su5485sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019004109/su5485Isup3.hkl
CSD search S1. DOI: 10.1107/S2056989019004109/su5485sup4.pdf
Supporting information file. DOI: 10.1107/S2056989019004109/su5485Isup4.cml
CCDC reference: 1905872
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| C19H15Cl6NO4[+solvent] | Dx = 1.578 Mg m−3 |
| Mr = 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
| Bruker SMART APEXII area-detector diffractometer | 3330 reflections with I > 2σ(I) |
| ω and φ scans | Rint = 0.021 |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | θmax = 29.2°, θmin = 2.8° |
| Tmin = 0.752, Tmax = 0.863 | h = −32→24 |
| 10728 measured reflections | k = −40→24 |
| 5181 independent reflections | l = −12→12 |
Refinement
| 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(Fo2) + (0.046P)2 + 2.6033P] where P = (Fo2 + 2Fc2)/3 |
| 5181 reflections | (Δ/σ)max = 0.001 |
| 273 parameters | Δρmax = 0.33 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| 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)
| 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)
| 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)
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.
Funding Statement
This work was funded by University Grants Commission grant SRF fellowship to R. Manohar.
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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) Global, I. DOI: 10.1107/S2056989019004109/su5485sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019004109/su5485Isup3.hkl
CSD search S1. DOI: 10.1107/S2056989019004109/su5485sup4.pdf
Supporting information file. DOI: 10.1107/S2056989019004109/su5485Isup4.cml
CCDC reference: 1905872
Additional supporting information: crystallographic information; 3D view; checkCIF report