Conversion of 2-methyl-4-styryl­quino­lines into 2,4-distyryl­quino­lines: synthesis, and spectroscopic and structural characterization of five examples

Four new 2,4-distyryl­quino­lines and one 2-styryl-4-[2-(thio­phen-2-yl)vin­yl]quinoline have been synthesized using indium trichloride condensation reactions between aromatic aldehydes and the corresponding 2-methyl­quino­lines, which were themselves prepared using Friedländer annulation reactions between mono- or diketones and (2-amino­phen­yl)chalcones: the products have all been fully characterized by spectroscopic and crystallographic methods. 2,4-Bis[(E)-styr­yl]quino­line, C₂₅H₁₉N, (IIa), and its di­chloro analogue, 2-[(E)-2,4-di­chloro­styr­yl]-4-[(E)-styr­yl]quino­line, C₂₅H₁₇Cl₂N, (IIb), exhibit different orientations of the 2-styryl unit relative to the quino­line nucleus. In each of the 3-benzoyl analogues {2-[(E)-4-bromo­styr­yl]-4-[(E)-styr­yl]quinolin-3-yl}(phen­yl)methanone, C₃₂H₂₂BrNO, (IIc), {2-[(E)-4-bromo­styr­yl]-4-[(E)-4-chloro­styr­yl]quinolin-3-yl}(phen­yl)methanone, C₃₂H₂₁BrClNO, (IId), and {2-[(E)-4-bromo­styr­yl]-4-[(E)-2-(thio­phen-2-yl)vin­yl]quinolin-3-yl}(phen­yl)methanone, C₃₀H₂₀BrNOS, (IIe), the orientation of the 2-styryl unit is similar to that in (IIa), but the orientation of the 4-aryl­vinyl units show considerable variation. The thio­phene unit in (IIe) is disordered over two sets of atomic sites having occupancies of 0.926 (3) and 0.074 (3). There are no hy­dro­gen bonds of any kind in the structure of (IIa), but in (IId), a single C—H⋯O hy­dro­gen bond links the mol­ecules into cyclic centrosymmetric R₂²(20) dimers. A combination of C—H⋯N and C—H⋯π hy­dro­gen bonds links the mol­ecules of (IIb) into a three-dimensional framework structure. A combination of three C—H⋯π hy­dro­gen bonds links the mol­ecules of (IIc) into sheets, and a combination of C—H⋯O and C—H⋯π hy­dro­gen bonds forms sheets in (IIe). Comparisons are made with the structures of some related compounds.

1. Introduction

The quino­line nucleus is considered to be one of the most privileged scaffolds and to be a crucial pharmacophore in drug discovery because of its occurrence in a wide variety of natural and synthetic biologically active mol­ecules (Solomon & Lee, 2011; Musiol et al., 2017; Matada et al., 2021). The outstanding therapeutic importance of quino­line derivatives is well known, particularly in the treatment of, for example, microbial (Lam et al., 2014; Zhang et al., 2018), malarial (Kaur et al., 2010; Hu et al., 2017; Okombo & Chibale, 2018; Orozco et al., 2020), fungal (Musiol et al., 2010; Kumar et al., 2011), inflammatory (Chen et al., 2006; Gilbert et al., 2008), viral (Ghosh et al., 2008; Matada et al., 2021), protozoal (Fakhfakh et al., 2003; Franck et al., 2004; Kumar et al., 2009), cardiovascular (Cai et al., 2007; Bernotas et al., 2009) and neoplastic diseases (Afzal et al., 2015; Musiol, 2017; Cortes et al., 2018; Lauria et al., 2021; Yadav & Kamal, 2021).

Among different classes of quino­line derivatives, styryl­quino­lines, especially 2-styryl­quino­lines and to a lesser extent 4-styryl­quino­lines, have been studied extensively, mainly because of their potential as inhibitors of HIV-1 integrase (Leonard & Roy, 2008; Mahajan et al., 2018; Mousnier et al., 2004) and as anti­microbial (Kamal et al., 2015), anti­fungal (Cieslik et al., 2012; Szczepaniak et al., 2017), anti-asthma (Matada et al., 2021) and anti­cancer agents (Chang et al., 2010; Mrozek-Wilczkiewicz et al., 2015, 2019). The pharmacological

relevance of these types of quino­line derivatives has prompted the development of different methodologies for the synthesis of drug-like compounds containing such styryl­quino­line scaffolds (Staderine et al., 2011; Yaragorla et al., 2015; Sharma et al., 2017; Musiol, 2020; Hazra et al., 2020; Zhang et al., 2020; Li et al., 2021; Omar & Hormi, 2009; Lee et al., 2009 Alacíd & Nájera, 2009; Jamal & Teo, 2014; Jamal et al., 2016; Satish et al., 2019; Meléndez et al., 2020).

Unlike 2-styryl- and 4-styryl­quino­lines, the closely-related 2,4-distyryl­quino­lines have been scarcely investigated, with very few publications related to their synthesis and biological evaluation, and this scarcity may be due, at least in part, to the lack of satisfactory methods for their synthesis. The few re­ported 2,4-distyryl­quino­lines have been prepared by methods such as one-pot successive Arbuzov/Horner–Wadsworth–Emmons reactions using ethyl 4-(bromo­meth­yl)-2-(chloro­meth­yl)quino­line-3-carboxyl­ate as the key precursor (Gao et al., 2018), and the Knoevenagel-type condensation of 2-methyl-4-styryl­quino­line with aromatic aldehydes, catalysed by sodium acetate (Satish et al., 2019).

We have recently described an efficient and straightforward synthetic pathway, based on Friedländer annulation and starting from readily available 1-(2-amino­phen­yl)-3-aryl­prop-2-en-1-ones, to obtain several new series of polysubstituted 2-methyl-4-styryl­quino­lines (Meléndez et al., 2020; Vera et al., 2022). In an expansion of the scope of this route, in respect of both utility and flexibility, we now describe the synthesis, spectroscopic characterization, and mol­ecular and supra­molecular structures of a matched set of five closely-related 2,4-distyryl­quino­lines, namely, 2,4-bis­[(E)-styr­yl]quino­line, (IIa), 2-[(E)-2,4-di­chloro­styr­yl]-4-[(E)-styr­yl]quino­line, (IIb), {2-[(E)-4-bromo­styr­yl]-4-[(E)-styr­yl]quinolin-3-yl}(phen­yl)methanone, (IIc), {2-[(E)-4-bromo­styr­yl]-4-[(E)-4-chloro­styr­yl]quinolin-3-yl}(phen­yl)methanone, (IId), and {2-[(E)-4-bromo­styr­yl]-4-[(E)-2-(thio­phen-2-yl)vin­yl]quinolin-3-yl}(phen­yl)methanone, (IIe) (see Scheme 1), which differ only in the nature of the substituents at position C3 of the quino­line ring and the substituents in the 4-(aryl­vin­yl) fragments. To the best of our knowledge, these 2,4-distyryl­quino­lines have not been reported previously.

The work reported here can be regarded as a continuation of an earlier crystallographic study which reported the structures of 4-styryl­quino­lines having different substituents at the C2 and C3 positions (Rodríguez et al., 2020; Vera et al., 2022; Ardila et al., 2022).

2. Experimental

2.1. Synthesis and crystallization

For the synthesis of compounds (IIa)–(IIe), a mixture of the appropriate 2-methyl-4-styryl­quino­line, (I) (see Scheme 1), prepared as described previously (Meléndez et al., 2020; Vera et al., 2022) (1.0 mmol), the appropriate aromatic aldehyde (4.0 mmol) and indium trichloride (10 mmol%) in dry toluene (1.2 ml) was stirred magnetically and heated at 393 K until the reactions were complete, shown by the complete consumption of (I), as monitored by thin-layer chromatography (TLC). The reaction times for completion were 18 h for (IIa), 16 h for (IIb), 17 h for (IIc) and 21 h for both (IId) and (IIe). Each reaction mixture was then allowed to cool to ambient tem­pe­ra­ture, washed with chloro­form and the resulting suspension was removed by filtration before the filtrate was con­cen­trated under reduced pressure. In each case, the resulting crude product was purified by silica-gel column chromatography using hepta­ne–ethyl acetate mixtures as eluent (compositions ranged from 10:1 to 2:1 v/v) to give the required solid products (IIa)–(IIe). Crystallization from ethyl acetate–heptane, at ambient tem­pe­ra­ture and in the presence of air, gave crystals suitable for single-crystal X-ray diffraction.

In the NMR data listed below, unprimed ring atoms form part of the quino­line units; ring atoms carrying a single prime form part of the styryl units attached at position C2 of the quino­line system; ring atoms carrying double primes form part of the styryl units attached at position C4 for compounds (IIa) and (IIb), or part of the benzoyl units attached at position C3 for compounds (IIc)–(IIe); and ring atoms carrying triple primes form part of the styryl units attached at position C4 for compounds (IIc)–(IIe).

2,4-Bis[(E)-styr­yl]quino­line, (IIa). Yellow solid, yield 0.11 g (71%), m.p. 393–394 K, R_F = 0.40 (21% ethyl acetate–hepta­ne). IR (ATR, cm⁻¹): 3019 [C(sp²)H], 1723 (C=N), 1633 (C=C_vin­yl), 1581 (C=C_arom), 1541 (C=C_arom), 961 (=C—H_trans). NMR (CDCl₃): δ(¹H) (400 MHz) 8.15 (d, J = 8.3 Hz, 1H, H5), 8.12 (d, J = 8.4 Hz, 1H, H8), 7.84 (d, J = 1.3 Hz, 1H, H3), 7.81 (d, J = 16.1 Hz, 1H, H_A′′C=), 7.76 (d, J = 16.0 Hz, 1H, =CH_B′), 7.72–7.68 (m, 1H, H7), 7.68–7.65 (m, 4H, H2′, H6′, H2′′, H6′′), 7.53 (ddt, J = 8.2, 6.9, 1.3 Hz, 1H, H6), 7.47–7.43 (m, 1H, H_A′C=), 7.46–7.41 (m, 4H, H3′, H5′, H3′′, H5′′), 7.40–7.32 (m, 2H, H4′, H4′′), 7.38–7.34 (m, 1H, =CH_B′′); δ(¹³C) (100 MHz) 155.7 (C2), 148.8 (C8a), 143.3 (C4), 136.7 (C1′′), 136.6 (C1′), 135.0 (=CH_B′′), 134.3 (=CH_B′), 129.9 (C8), 129.6 (C7), 128.9 (C3′′, C5′′), 128.8 (C3′, C5′, C4′′, H_A′C=), 128.6 (C4′), 127.3 (C2′′, C6′′), 127.2 (C2′, C6′), 126.2 (C6), 125.7 (C4a), 123.4 (C5, H_A′—C=), 115.6 (C3). HRMS (ESI⁺) m/z found for [M + H]⁺ 334.1590, C₂₅H₁₉N requires 333.1589.

2-[(E)-2,4-Di­chloro­styr­yl]-4-[(E)-styr­yl]quino­line, (IIb). Yellow solid, yield 0.19 g (77%), m.p. 449–450 K, R_F = 0.41 (21% ethyl acetate–hepta­ne). IR (ATR, cm⁻¹): 3055 [C(sp²)H], 1639 (C=N), 1580 (C=C_vin­yl), 1541 (C=C_arom), 1473 (C=C_arom), 960 (=C—H_trans). NMR (CDCl₃): δ(¹H) (400 MHz) 8.17 (dd, J = 8.4, 1.5 Hz, 1H, 5H), 8.11 (dd, J = 8.6, 1.3 Hz, 1H, 8H), 8.03 (d, J = 16.3 Hz, 1H, =CH_B′), 7.86 (s, 1H, 3H), 7.81 (d, J = 16.3 Hz, 1 H, H_A′′C=), 7.75 (d, J = 8.4 Hz, 1H, H6′), 7.73 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H, H7), 7.67–7.64 (m, 2H, H2′′, H6′′), 7.56 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H, H6), 7.47–7.42 (m, 3H, H3′, H3′′, H5′′), 7.39 (d, J = 16.3 Hz, 1H, =CH_B′′), 7.39–7.35 (m, 1H, H4′′), 7.38 (d, J = 16.3 Hz, 1H, H_A′C=), 7.29 (dd, J = 8.2, 2.0 Hz, 1H, H5′); δ(¹³C) (100 MHz) 155.1 (C2), 148.8 (C8a), 143.5 (C4), 136.6 (C1′′), 135.3 (=CH_B′′), 134.6 (C2′), 134.5 (C4′), 133.4 (C1′), 132.3 (H_A′C=), 130.1 (C8), 129.8 (C7, C3′), 129.0 (C3′′, C5′′), 128.9 (=CH_B′), 128.8 (C4′′), 127.7 (C6′), 127.5 (C5′), 127.2 (C2′′, C6′′), 126.5 (C6), 125.8 (C4a), 123.5 (C5), 123.2 (H_A′′C=), 115.4 (C3). HRMS (ESI⁺) m/z found for [M + H]⁺ 402.0812, C₂₅H₁₇³⁵Cl₂N requires 402.0811.

{2-[(E)-4-Bromo­styr­yl]-4-[(E)-styr­yl]quinolin-3-yl}(phen­yl)methanone, (IIc). Orange solid. yield 0.20 g (86%), m.p. 471–472 K, R_F = 0.38 (9.1% ethyl acetate–hepta­ne). IR (ATR, cm⁻¹): 3025 [C(sp²)H], 1666 (C=O), 1627 (C=N), 1595 (C=C_vin­yl), 1535 (C=C_arom), 1483 (C=C_arom), 957 (=C—H_trans). NMR (CDCl₃): δ(¹H) (400 MHz) 8.20 (dd, J = 8.5, 1.2 Hz, 1H, H8), 8.12 (dd, J = 8.4, 1.4 Hz, 1H, H5), 8.00 (d, J = 15.5 Hz, 1H, =CH_B′), 7.80 (ddd, J = 8.6, 6.9, 1.3 Hz 1H, H7), 7.78–7.76 (m, 2H, H2′′, H6′′), 7.57 (ddd, J = 8.3, 6.9, 1.2 Hz, 1H, H6), 7.56–7.52 (m, 1H, H4′′), 7.44–7.42 (m, 2H, H3′, H5′), 7.39 (t, J = 7.8 Hz, 2H, H3′′, H5′′), 7.35–7.32 (m, 2H, H2′, H6′), 7.30–7.26 (m, 5H, H2′′′, H6′′′, H3′′′, H5′′′, H4′′′), 7.23 (dd, J = 16.4, 0.8 Hz, 1H, H_A′′′C=), 7.09 (dd, J = 15.5, 0.8 Hz, 1H, H_a′C=), 6.87 (d, J = 16.4 Hz, 1H, =CH_B′′′); δ(¹³C) (100 MHz) 198.4 (C=O), 151.4 (C2), 148.1 (C8a), 142.4 (C4), 139.5 (=CH_B′′′), 137.9 (C1′′), 136.3 (C1′′′), 135.4 (C1′), 135.0 (=CH_B′), 134.0 (C4′′), 131.8 (C3′, C5′), 131.1 (C3), 130.6 (C7), 130.0 (C8), 129.5 (C2′′, C6′′), 129.0 (C2′, C6′), 128.9 (C3′′, C5′′), 128.8 (C4′′′), 128.7 (C3′′′, C5′′′), 126.9 (C6), 126.8 (C2′′′, C6′′′), 125.4 (C4a), 125.2 (C5), 125.0 (H_A′C=), 122.7 (C4′), 122.1 (H_A′′C=). HRMS (ESI⁺) m/z found for [M + H]⁺ 516.09656, C₃₂H₂₂⁷⁹BrNO requires 516.09575.

{2-[(E)-4-Bromo­styr­yl]-4-[(E)-4-chloro­styr­yl]quinolin-3-yl}(phen­yl)methanone, (IId). Orange solid, yield 0.19 g (80%), m.p. 476–477 K, R_F = 0.35 (9.1% ethyl acetate–hepta­ne). IR (ATR, cm⁻¹): 3046 [C(sp²)H], 1661 (C=O), 1630 (C=N), 1590, 1595 (C=C_vin­yl), 1540 (C=C_arom), 1487 (C=C_arom), 978 (=C—H_trans). NMR (CDCl₃): δ(¹H) 8.20 (400 MHz) (dd, J = 8.4, 1.4 Hz, 1H, H8), 8.08 (ddd, J = 8.4, 1.4, 0.7 Hz, 1H, H5), 8.00 (d, J = 15.5 Hz, 1H, =CH_B′), 7.80 (ddd, J = 8.4, 6.8, 1.3 Hz, 1H, H7), 7.76–7.74 (m, 2H, H2′′, H6′′), 7.57 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H, H6), 7.56–7.52 (m, 1H, H4′′), 7.44–7.42 (m, 2H, H3′, H5′), 7.39 (t, J = 7.8 Hz, 2H, H3′′, H5′′), 7.34–7.31 (m, 2H, H2′, H6′), 7.27–7.25 (m, 2H, H3′′′, H5′′′), 7.22–7.18 (m, 2H, H2′′′, H6′′′), 7.20 (d, J = 16.4 Hz, 1H, H_A′′′C=), 7.08 (d, J = 15.5 Hz, 1H, H_A′C=), 6.81 (d, J = 16.4 Hz, 1H, =CH_B′′′); δ(¹³C) (100 MHz) 198.4 (C=O), 151.4 (C2), 148.1 (C8a), 142.0 (C4), 138.1 (=CH_B′′′), 137.9 (C1′′), 135.4 (C1′), 135.1 (=CH_B′), 134.7 (C4′′′), 134.6 (C1′′′), 134.1 (C4′′), 131.8 (C3′, C5′), 131.1 (C3), 130.7 (C7), 130.0 (C8), 129.5 (C2′′, C6′′), 129.0 (C2′, C6′, C3′′′, C5′′′), 128.9 (C3′′, C5′′), 128.0 (C2′′′, C6′′′), 127.0 (C6), 125.2 (C4a), 125.1 (HH_A′C=), 124.9 (C5), 122.7 (C4′, H_A′′′C=). HRMS (ESI⁺) m/z found for [M + H]⁺ 550.05750, C₃₂H₂₁⁷⁹Br³⁵ClNO requires 550.05678.

{2-[(E)-4-Bromo­styr­yl]-4-[(E)-2-(thio­phen-2-yl)vin­yl]quino­lin-3-yl}(phen­yl)methanone, (IIe). Yellow solid, yield 0.24 g (93%), m.p. 472–473 K, R_F = 0.38 (9.1% ethyl acetate–hep­ta­ne). IR (ATR, cm⁻¹): 3026 [C(sp²)H], 1663 (C=O), 1627 (C=N), 1589 (C=C_vin­yl), 1537 (C=C_arom), 1483 (C=C_arom), 957 (=C—H_trans). NMR (CDCl₃): δ(¹H) (400 MHz) 8.18 (d, J = 8.3 Hz, 1H, H8), 8.11 (d, J = 8.3 Hz, 1H, H5), 7.99 (d, J = 15.5 Hz, 1H, =CH_B′), 7.82–7.78 (m, 1H, H7), 7.77–7.75 (m, 2H, H2′′, H6′′), 7.58 (ddd, J = 8.3, 6.8, 1.2 Hz, 1H, H6), 7.56–7.52 (m, 1H, H4′′), 7.43 (d, J = 8.4 Hz, 2H, H3′, H5′), 7.38 (t, J = 7.8 Hz, 2H, H3′′, H5′′), 7.33 (d, J = 8.4 Hz, 2H, H2′, H6′), 7.21 (d, J = 4.9 Hz, 1H, H3′′′), 7.08 (d, J = 15.5 Hz, 1H, H_A′C=), 7.08 (d, J = 16.2 Hz, 1H, H_a′′′C=), 6.99 (d, J = 16.2 Hz, 1H, =CH_B′′′), 6.98–6.95 (m, 2H, H4′′′, H5′′′); δ(¹³C) (100 MHz) 198.5 (C=O), 151.4 (C2), 148.1 (C8a), 141.7 (C4), 141.3 (C2′′′), 137.8 (C1′′), 135.4 (C1′), 135.0 (=CH_B′), 134.0 (C4′′), 132.3 (=CH_B′′′), 131.8 (C3′, C5′), 130.9 (C3), 130.6 (C7), 130.0 (C8), 129.5 (C2′′, C6′′), 129.0 (C2′, C6′), 128.9 (C3′′, C5′′), 128.0 (C5′′′), 127.7 (C4′′′), 127.0 (C6), 126.1 (C3′′′), 125.2 (C4a), 125.1 (H_A′C=), 124.9 (C5), 122.7 (C4′), 121.1 (H_A′′′C=). HRMS (ESI⁺) m/z found for [M + H]⁺ 522.05249, C₃₀H₂₀⁷⁹BrNOS = requires 522.05217.

2.2. Refinement

Crystal data, data collection and refinement details for compounds (IIa)–(IIe) are summarized in Table 1. For compound (IId), the reflection 100, which had been attenuated by the beam stop, was removed from the data set. In addition, a small number of bad outlier reflections [04 for (IIa) and 141, 231, 241, 033 and 03 for (IIc)] were also removed. Compound (IIc) was handled as a nonmerohedral twin, with twin matrix (−0.053, 0.000, 0.947/0.000, −1.000, 0.000/1.053, 0.000, 0.053) and with refined twin fractions of 0.865 (2) and 0.135 (2). In compound (IIe), the thienyl unit was disordered over two sets of atomic sites having unequal occupancies. For the minor-disorder component, the bonded distances and the 1,3 nonbonded distances were restrained to be the same as the corresponding distances in the major-disorder component, subject to s.u. values of 0.01 and 0.02 Å, respectively. In addition, the anisotropic displacement parameters for pairs of partial-occupancy atoms occupying essentially the same physical space were constrained to be identical. All H atoms, apart from those in the minor-disorder component of compound (IIe), were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C); the H atoms in the minor-disorder component of compound (IIe) were included in the refinement in exactly the same manner. Subject to these conditions, the refined occupancy values for the disorder components of (IIe) were 0.926 (3) and 0.074 (3). In the final difference map, the largest maximum of 1.65 e Å⁻³ was 0.86 Å from atom Br24, while the largest minimum of −1.18 e Å⁻³ was 0.66 Å from Br24. While these features might indicate some further minor disorder, the anisotropic displacement parameters provided no support for this possibility, which was therefore not pursued further.

Table 1
Experimental details

Experiments were carried out at 100 K with Mo Kα radiation using a Bruker D8 Venture diffractometer. Absorption was corrected for by multi-scan methods (SADABS; Bruker, 2016). H-atom parameters were constrained.

	(IIa)	(IIb)	(IIc)
Crystal data
Chemical formula	C25H19N	C25H17Cl2N	C32H22BrNO
Mr	333.41	402.29	516.41
Crystal system, space group	Monoclinic, P21/c	Monoclinic, C2/c	Monoclinic, P21/n
a, b, c (Å)	12.6112 (6), 8.6352 (4), 17.3080 (8)	28.4950 (7), 9.5384 (3), 16.0520 (5)	12.287 (2), 15.528 (3), 12.844 (3)
α, β, γ (°)	90, 105.925 (2), 90	90, 118.581 (1), 90	90, 99.877 (6), 90
V (Å^3)	1812.51 (15)	3831.2 (2)	2414.2 (8)
Z	4	8	4
μ (mm^−1)	0.07	0.35	1.73
Crystal size (mm)	0.19 × 0.14 × 0.08	0.21 × 0.10 × 0.09	0.15 × 0.12 × 0.08
Data collection
Tmin, Tmax	0.924, 0.994	0.901, 0.969	0.720, 0.871
No. of measured, independent and observed [I > 2σ(I)] reflections	38720, 4161, 3388	47555, 4414, 3914	5530, 5530, 4290
Rint	0.060	0.056	–
(sin θ/λ)max (Å^−1)	0.650	0.650	0.653
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.050, 0.118, 1.09	0.032, 0.078, 1.09	0.064, 0.196, 1.05
No. of reflections	4161	4414	5530
No. of parameters	235	253	317
No. of restraints	0	0	0
Δρmax, Δρmin (e Å^−3)	0.25, −0.24	0.35, −0.22	1.40, −0.70

	(IId)	(IIe)
Crystal data
Chemical formula	C32H21BrClNO	C30H20BrNOS
Mr	550.86	522.44
Crystal system, space group	Triclinic, P	Orthorhombic, Pbca
a, b, c (Å)	9.9051 (12), 11.3936 (16), 11.8192 (16)	15.5785 (8), 16.4215 (7), 18.3126 (9)
α, β, γ (°)	77.727 (5), 76.116 (5), 86.448 (5)	90, 90, 90
V (Å^3)	1265.2 (3)	4684.8 (4)
Z	2	8
μ (mm^−1)	1.76	1.87
Crystal size (mm)	0.19 × 0.12 × 0.10	0.20 × 0.12 × 0.08
Data collection
Tmin, Tmax	0.735, 0.836	0.768, 0.861
No. of measured, independent and observed [I > 2σ(I)] reflections	61838, 5807, 5014	63672, 5363, 4456
Rint	0.064	0.060
(sin θ/λ)max (Å^−1)	0.650	0.649
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.028, 0.065, 1.03	0.040, 0.101, 1.02
No. of reflections	5807	5363
No. of parameters	325	320
No. of restraints	0	10
Δρmax, Δρmin (e Å^−3)	0.33, −0.39	1.65, −1.18
Computer programs: APEX3 (Bruker, 2018), SAINT (Bruker, 2017), SHELXT2014 (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2020).

3. Results and discussion

The 2-methyl-4-styryl­quino­line precursors of type (I) (see Scheme 1) were prepared in high yields using Friedländer annulation reactions (Meléndez et al., 2020; Vera et al., 2022) between (2-amino­phen­yl)chalcones and either acetone, for compounds (Ia) and (Ib), or 1-phenyl­butane-l-1,3-dione, for compounds (Ic)–(Ie). These precursors of type (I) were then converted successfully into the target 2,4-distyryl­quino­lines (IIa)–(IIe) in yields of 71–93% by means of indium tri­chloride-catalyzed Knoevenagel-type condensation reactions with the appropriate aromatic aldehydes (see Scheme 1). Compounds (IIa)–(IIe) were all fully characterized by standard spectroscopic means (FT–IR, ¹H and ¹³C NMR spectroscopy, and high-resolution mass spectrometry) and full details of the spectroscopic characterization are provided in Section 2.1.

The formation of the second styryl fragment in products (IIa)–(IIe) was established by the disappearance from both the ¹H and ¹³C NMR spectra of the signals from the methyl group at position C2, and their replacement by new sets of signals corresponding to the newly-introduced C and H atoms; thus, eight new C atoms in each case and seven new H atoms in (IIa), five in (IIb) and six in each of (IIc)–(IIe). In each case, the Knoevenagel-type condensation proceeded in a highly stereoselective manner giving exclusively the E stereoisomers, as indicated by the ¹H NMR spectra. The E configuration of the newly-formed styryl fragment was deduced on the basis of the coupling constant values (³J_HA′,HB′ ca 16.0 Hz) between HA′ and HB′. The constitutions of compounds (IIa)–(IIe), which were deduced from the spectroscopic data, were then fully confirmed by the results of single-crystal X-ray diffraction, which additionally provided information on the mol­ecular conformations and the inter­molecular inter­actions in the solid state.

The versatility of this synthetic route to 2,4-distyryl­quino­lines and their analogues is underpinned by the possibility of incorporating a wide variety of substituents into the initial chalcone precursor, into the ketone employed in the annulation step and into the aldehyde used in the final condensation step.

In compound (IIe), the thio­phene unit is disordered over two sets of atomic sites having occupancies of 0.926 (3) and 0.074 (3), such that the two disorder forms are related by a rotation of approximately 180° around the exocyclic C—C bond; the dihedral angle between the mean planes of the two disorder components is only 4(2)°.

The mol­ecules of compounds (IIa)–(IIe) exhibit no inter­nal symmetry and hence these compounds are all conformationally chiral (Moss, 1996; Flack & Bernardinelli, 1999), but the centrosymmetric space groups (Table 1) confirm that equal numbers of the two conformational enanti­omers are present in each of (IIa)–(IIe).

For the 3-benzoyl products (IIc)–(IIe), the reference mol­ecules are all such that the torsion angle C2—C3—C31—C311 has a positive sign (Table 2), while the value of the torsion angle C3—C4—C41—C42 in (IIc) is markedly different from those in the other four compound reported here (Table 2 and Figs. 1–5). In each of (IIa)–(IIe), the 2-styryl unit is close to being coplanar with the quino­line unit, while the 4-substituent is twisted well out of the plane of the quino­line unit. These observations thus complement the general pattern in styryl­quino­lines that we have noted previously (Vera et al., 2022; Ardila et al., 2022). Amongst the styryl­quino­lines whose structures are recorded in the Cambridge Structural Database (Groom et al., 2016), 2-styryl- and 8-styryl­quino­lines all have mol­ecular skeletons which are effectively planar, while in 4-styryl­quino­lines, the styryl unit is always markedly twisted out of the plane of the quino­line unit by a rotation about the exocyclic bond corresponding to C4—C41 in the numbering system used here.

Table 2
Selected torsion angles (°) for compounds (IIa)–(IIe)

Parameter	(IIa)	(IIb)	(IIc)	(IId)	(IIe)
C3—C2—C21—C22	−178.77 (14)	−12.9 (2)	−171.8 (4)	179.16 (16)	178.5 (2)
C21—C22—C221—C222	−173.99 (15)	−161.58 (14)	171.4 (4)	−171.95 (17)	−174.5 (3)
C2—C3—C31—C311			87.2 (5)	109.43 (17)	85.9 (3)
C3—C31—C311—C312			−15.6 (6)	−12.3 (2)	−10.9 (3)
C3—C4—C41—C42	19.8 (2)	23.4 (2)	−131.9 (4)	−44.4 (2)	37.6 (4)
C41—C42—C421—C422	8.3 (2)	−6.1 (2)	−4.5 (6)	−21.4 (3)
C41—C42—C422—S421					0.8 (4)
C41—C42—C522—S521					−175.9 (7)

Figure 1 The mol­ecular structure of compound (IIa), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2 The mol­ecular structure of compound (IIb), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 3 The mol­ecular structure of compound (IIc), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 4 The mol­ecular structure of compound (IId), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 5 The mol­ecular structure of compound (IIe), showing the conformational disorder and the atom-labelling scheme. The major-disorder component is drawn with full lines and the minor-disorder component is drawn using broken lines. Displacement ellipsoids are drawn at the 50% probability level.

Despite this, there are some unexpected differences in the mol­ecular orientations of the two aryl­vinyl units (Figs. 1–5 and Table 2). Thus, the orientation of the 2-styryl substituent in (IIb) differs from that in each of (IIa) and (IIc)–(IIe) by a rotation about the C2—C21 bond of approximately 180°. In addition, the orientation of the 4-stryl unit in (IIc) differs markedly from that in each of the other examples, but the torsion angle C3—C4—C41—C42 shows quite a wide range of variation (Table 2). These differences in conformation cannot reasonably be explained in terms of the patterns of hy­dro­gen bonding discussed below (cf. Table 3).

Table 3
Hydrogen bonds and short inter­molecular contacts (Å, °) for compounds (IIb)–(IIe)

Cg1–Cg4 represent the centroids of rings C421–C426, C4A/C5–C8/C8A, C311–C316 and C221–C216, respectively.

Compound	D—H⋯A		D—H	H⋯A	D⋯A	D—H⋯A
(IIb)	C225—H225⋯N1^i		0.95	2.62	3.522 (2)	158
	C6—H6⋯Cg1^ii		0.95	2.65	3.4152 (16)	138
	C422—H422⋯Cg2^iii		0.95	2.88	3.5843 (17)	132
(IIc)	C8—H8⋯O31^iv		0.95	2.51	3.164 (6)	126
	C5—H5⋯Cg3^v		0.95	2.96	3.728 (4)	138
	C42—H42⋯Cg4^vi		0.95	2.88	3.766 (5)	155
	C223—H223⋯Cg2^vii		0.95	2.84	3.429 (3)	122
(IId)	C225—H225⋯O31^v		0.95	2.37	3.266 (2)	156
(IIe)	C8—H8⋯O31^viii		0.95	2.58	3.122 (3)	116
	C425—H425⋯O31^ix		0.95	2.45	3.361 (4)	161
	C5—H5⋯Cg3^v		0.95	2.90	3.647 (3)	136
	C423—H423⋯Cg3^v		0.95	2.76	3.449 (3)	130
Symmetry codes: (i) −x + , y − , −z + ; (ii) x, −y + 2, z + ; (iii) −x + 1, y, −z + ; (iv) x + , −y + , z + ; (v) −x + 1, −y + 1, −z + 1; (vi) x + , −y + , z − ; (vii) x − , −y + , z + ; (viii) −x + , y − , z; (ix) x, −y + 2, z − .

The patterns of supra­molecular assembly in compounds (IIa)–(IIe) show some wide variations. Despite the large numbers of aromatic rings and C—H bonds in the mol­ecules of (IIa), the crystal structure contains no significant direction-specific inter­molecular inter­actions of any sort. By contrast, in the di­chloro analogue (IIb), a combination of one C—H⋯N hy­dro­gen bond and two independent C—H⋯π(arene) hy­dro­gen bonds (Table 3) links the mol­ecules into a three-dimensional framework structure, whose formation is readily analysed in terms of three simple substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). The C—H⋯N hy­dro­gen bonds link mol­ecules of (IIb) which are related by the 2₁ screw axis along (, y, ) to form a C(8) (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 6). In the second substructure, the C—H⋯π(arene) hy­dro­gen bond having atom C6 as the donor links mol­ecules which are related by the c-glide plane at y = 1 to form a chain running parallel to the [001] direction (Fig. 7). The combination of the chains along [010] and [001] generates a sheet lying parallel to (100) in the domain 0 < x < . A second sheet, related to the first by inversion, lies in the domain < x < 1.0, and adjacent sheets are linked by the third substructure which takes the form of a cyclic centrosymmetric dimer built from C—H⋯π(arene) hy­dro­gen bonds having atom C422 as the donor (Fig. 8).

Figure 6 Part of the crystal structure of compound (IIb), showing the formation of a C(8) chain parallel to [010], built from C—H⋯N hy­dro­gen bonds, which are drawn as dashed lines. For the sake of clarity, H atoms which are not involved in the motif shown have been omitted.

Figure 7 Part of the crystal structure of compound (IIb), showing the formation of a chain parallel to [001], built from C—H⋯π(arene) hy­dro­gen bonds, which are drawn as dashed lines. For the sake of clarity, H atoms which are not involved in the motif shown have been omitted.

Figure 8 Part of the crystal structure of compound (IIb), showing the formation of a centrosymmetric dimer built from C—H⋯π(arene) hy­dro­gen bonds, which are drawn as dashed lines. For the sake of clarity, H atoms which are not involved in the motif shown have been omitted.

The short inter­molecular C—H⋯O contact in compound (IIc) has a very small C—H⋯O angle (Table 3), and so cannot be regarded as structurally significant (Wood et al., 2009). However, the co-operative action of two C—H⋯π(arene) hy­dro­gen bonds links mol­ecules which are related by the n-glide plane at y = into a chain of rings running parallel to the [10] direction (Fig. 9). The structure also contains a third C—H⋯π(arene) contact, involving atom C5, but here the H⋯A distance is quite long; if this were regarded as structurally significant, its action would be to link the chains of rings into a sheet parallel to (101).

Figure 9 Part of the crystal structure of compound (IIc), showing the formation of a chain of rings running parallel to the [10] direction and built from two independent C—H⋯π(arene) hy­dro­gen bonds, which are drawn as dashed lines. For the sake of clarity, H atoms which are not involved in the motif shown have been omitted.

A single C—H⋯O hy­dro­gen bond links inversion-related mol­ecules of compound (IId) into a cyclic centrosymmetric R₂²(20) dimer (Fig. 10), but there are no direction-specific inter­actions between adjacent dimers.

Figure 10 Part of the crystal structure of compound (IId), showing the formation of a cyclic R2^2(20) dimer built from C—H⋯O hy­dro­gen bonds, which are drawn as dashed lines. For the sake of clarity, H atoms which are not involved in the motif shown have been omitted.

In the crystal structure of compound (IIe), the C—H⋯O contact involving atom C8 is not structurally significant (Wood et al., 2009), but the combination of the C—H⋯O hy­dro­gen bond involving atom C425 with the two C—H⋯π(arene) hy­dro­gen bonds links the mol­ecules into a complex sheet lying parallel to (100) in the domain < x < (Fig. 11). A second sheet, related to the first by the action of the 2₁ screw axes, lies in the domain < x < 1.35, but there are no direction-specific inter­actions between adjacent sheets.

Figure 11 Part of the crystal structure of compound (IIe), showing the formation of a sheet lying parallel to {100} and built from a combination of C—H⋯O and C—H⋯π(arene) hy­dro­gen bonds, which are drawn as dashed lines. For the sake of clarity, the minor-disorder component and H atoms which are not involved in the motif shown have been omitted.

It is of inter­est briefly to compare the supra­molecular assembly in compounds (IIa)–(IIe) reported here with those of some simpler 2-methyl-4-styryl­quino­line analogues. Crystal structures have been reported (Vera et al., 2022) for compounds (IIIa)–(IIIc) (see Scheme 2), which have no sub­sti­tuent at position C3 of the quino­line unit, and are thus related to compounds (IIa) and (IIb) reported here. In the crystal structure of (IIIa), the mol­ecules are linked into sheets by a combination of C—H⋯N hy­dro­gen bonds and π–π stacking inter­actions, while a similar combination of inter­actions links the mol­ecules of (IIIb) into chains of rings. There are no hy­dro­gen bonds in the structure of (IIIc), but a π–π stacking inter­action links the mol­ecules into stacks.

Compounds of the type (IV) (see Scheme 2), carrying a 3-acetyl substituent, are thus analogous to compounds (IIc)–(IIe). Compounds (IVa)–(IVc) are isomorphous (Rod­ríguez et al., 2020); in each, the mol­ecules are linked into chains by a C—H⋯O hy­dro­gen bond, but only in (IVa) is this augmented by a C—H⋯π hy­dro­gen bonds to form a chain of rings. Thus, although (IVa)–(IVc) are isomorphous, they are not strictly isostructural.

4. Summary

We have developed an efficient and highly versatile route to 2,4-distyryl­quino­lines and to their 2-aryl­vin­yl analogues, using only simple and readily accessible building blocks such as simple aldehydes and ketone. We have characterized by spectroscopic means (IR, ¹H and ¹³C NMR spectroscopy, and HRMS) five representative examples and we have determined their mol­ecular and crystal structures, which fully confirm the mol­ecular constitutions deduced from the spectroscopic data, as well as providing further information on their mol­ecular conformations in the solid state, and on their supra­molecular assemblies.

Supporting information

Computing details

For all structures, data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2020).

2,4-Bis[(E)-2-phenylethenyl]quinoline (IIa)

Crystal data

C25H19N	F(000) = 704
Mr = 333.41	Dx = 1.222 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.6112 (6) Å	Cell parameters from 4167 reflections
b = 8.6352 (4) Å	θ = 2.5–27.5°
c = 17.3080 (8) Å	µ = 0.07 mm^−1
β = 105.925 (2)°	T = 100 K
V = 1812.51 (15) Å^3	Block, yellow
Z = 4	0.19 × 0.14 × 0.08 mm

Data collection

Bruker D8 Venture diffractometer	4161 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3388 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.060
φ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −16→16
Tmin = 0.924, Tmax = 0.994	k = −10→11
38720 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0378P)^2 + 0.9448P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
4161 reflections	Δρmax = 0.25 e Å^−3
235 parameters	Δρmin = −0.24 e Å^−3
0 restraints

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.30510 (10)	0.54242 (14)	0.21630 (7)	0.0228 (3)
C2	0.39111 (12)	0.48035 (16)	0.26929 (8)	0.0217 (3)
C3	0.49565 (12)	0.46407 (16)	0.25495 (9)	0.0224 (3)
H3	0.5541	0.4169	0.2946	0.027*
C4	0.51400 (11)	0.51553 (16)	0.18435 (9)	0.0212 (3)
C4A	0.42226 (11)	0.58233 (15)	0.12564 (8)	0.0203 (3)
C5	0.42744 (12)	0.63945 (16)	0.04991 (8)	0.0227 (3)
H5	0.4943	0.6307	0.0350	0.027*
C6	0.33789 (12)	0.70684 (17)	−0.00194 (9)	0.0251 (3)
H6	0.3435	0.7459	−0.0520	0.030*
C7	0.23722 (12)	0.71894 (17)	0.01804 (9)	0.0264 (3)
H7	0.1754	0.7664	−0.0184	0.032*
C8	0.22845 (12)	0.66260 (17)	0.08957 (9)	0.0257 (3)
H8	0.1600	0.6701	0.1023	0.031*
C8A	0.31991 (11)	0.59285 (16)	0.14540 (8)	0.0207 (3)
C21	0.37736 (12)	0.43385 (16)	0.34781 (9)	0.0241 (3)
H21	0.4403	0.3959	0.3870	0.029*
C22	0.28261 (12)	0.44134 (16)	0.36762 (9)	0.0240 (3)
H22	0.2198	0.4754	0.3271	0.029*
C221	0.26566 (13)	0.40205 (16)	0.44600 (9)	0.0248 (3)
C222	0.15863 (14)	0.40227 (18)	0.45468 (10)	0.0310 (3)
H222	0.0981	0.4265	0.4099	0.037*
C223	0.13992 (15)	0.3673 (2)	0.52835 (11)	0.0383 (4)
H223	0.0669	0.3684	0.5335	0.046*
C224	0.22673 (16)	0.3313 (2)	0.59377 (10)	0.0401 (4)
H224	0.2136	0.3083	0.6440	0.048*
C225	0.33301 (15)	0.32869 (19)	0.58609 (10)	0.0352 (4)
H225	0.3927	0.3017	0.6309	0.042*
C226	0.35281 (14)	0.36517 (18)	0.51339 (9)	0.0288 (3)
H226	0.4263	0.3652	0.5091	0.035*
C41	0.62282 (12)	0.50961 (17)	0.16929 (9)	0.0238 (3)
H41	0.6340	0.5758	0.1284	0.029*
C42	0.70752 (12)	0.42098 (17)	0.20709 (9)	0.0243 (3)
H42	0.6975	0.3542	0.2481	0.029*
C421	0.81585 (11)	0.41880 (17)	0.19004 (9)	0.0229 (3)
C422	0.84436 (12)	0.52532 (18)	0.13856 (10)	0.0273 (3)
H422	0.7932	0.6033	0.1138	0.033*
C423	0.94624 (12)	0.51886 (18)	0.12314 (10)	0.0297 (3)
H423	0.9643	0.5921	0.0878	0.036*
C424	1.02212 (12)	0.40646 (19)	0.15887 (10)	0.0318 (4)
H424	1.0925	0.4033	0.1489	0.038*
C425	0.99439 (13)	0.2989 (2)	0.20920 (11)	0.0365 (4)
H425	1.0457	0.2204	0.2333	0.044*
C426	0.89210 (13)	0.30456 (19)	0.22480 (10)	0.0304 (3)
H426	0.8740	0.2299	0.2595	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0218 (6)	0.0222 (6)	0.0253 (6)	−0.0004 (5)	0.0082 (5)	−0.0011 (5)
C2	0.0230 (7)	0.0179 (6)	0.0253 (7)	−0.0007 (5)	0.0086 (6)	−0.0015 (5)
C3	0.0213 (7)	0.0209 (7)	0.0241 (7)	0.0021 (5)	0.0050 (5)	0.0010 (6)
C4	0.0211 (7)	0.0161 (6)	0.0270 (7)	−0.0009 (5)	0.0076 (6)	−0.0023 (5)
C4A	0.0219 (7)	0.0155 (6)	0.0239 (7)	−0.0019 (5)	0.0072 (5)	−0.0034 (5)
C5	0.0232 (7)	0.0209 (7)	0.0263 (7)	−0.0009 (6)	0.0104 (6)	−0.0022 (6)
C6	0.0306 (8)	0.0228 (7)	0.0225 (7)	−0.0009 (6)	0.0080 (6)	0.0007 (6)
C7	0.0248 (7)	0.0244 (7)	0.0273 (7)	0.0027 (6)	0.0026 (6)	0.0019 (6)
C8	0.0210 (7)	0.0268 (7)	0.0299 (8)	0.0006 (6)	0.0080 (6)	−0.0009 (6)
C8A	0.0215 (7)	0.0172 (6)	0.0235 (7)	−0.0013 (5)	0.0064 (5)	−0.0032 (5)
C21	0.0269 (7)	0.0207 (7)	0.0250 (7)	0.0020 (6)	0.0077 (6)	0.0015 (6)
C22	0.0283 (7)	0.0206 (7)	0.0238 (7)	−0.0001 (6)	0.0080 (6)	−0.0014 (6)
C221	0.0334 (8)	0.0171 (7)	0.0267 (7)	−0.0015 (6)	0.0132 (6)	−0.0031 (6)
C222	0.0354 (8)	0.0275 (8)	0.0331 (8)	−0.0025 (7)	0.0143 (7)	−0.0034 (7)
C223	0.0458 (10)	0.0361 (9)	0.0418 (10)	−0.0111 (8)	0.0270 (8)	−0.0055 (8)
C224	0.0637 (12)	0.0323 (9)	0.0305 (9)	−0.0137 (8)	0.0233 (8)	−0.0029 (7)
C225	0.0529 (11)	0.0247 (8)	0.0275 (8)	−0.0045 (7)	0.0102 (7)	−0.0005 (6)
C226	0.0363 (8)	0.0232 (7)	0.0280 (8)	−0.0006 (6)	0.0105 (6)	−0.0031 (6)
C41	0.0228 (7)	0.0243 (7)	0.0262 (7)	0.0000 (6)	0.0097 (6)	0.0017 (6)
C42	0.0235 (7)	0.0235 (7)	0.0266 (7)	−0.0014 (6)	0.0083 (6)	0.0017 (6)
C421	0.0194 (7)	0.0231 (7)	0.0256 (7)	−0.0002 (5)	0.0050 (5)	−0.0029 (6)
C422	0.0206 (7)	0.0230 (7)	0.0372 (8)	0.0010 (6)	0.0063 (6)	0.0030 (6)
C423	0.0251 (7)	0.0265 (8)	0.0387 (9)	−0.0036 (6)	0.0109 (6)	0.0021 (7)
C424	0.0204 (7)	0.0335 (8)	0.0437 (9)	0.0009 (6)	0.0126 (6)	−0.0020 (7)
C425	0.0260 (8)	0.0373 (9)	0.0472 (10)	0.0109 (7)	0.0115 (7)	0.0118 (8)
C426	0.0264 (8)	0.0332 (8)	0.0325 (8)	0.0044 (6)	0.0097 (6)	0.0077 (7)

Geometric parameters (Å, º)

N1—C2	1.3263 (18)	C222—C223	1.392 (2)
N1—C8A	1.3624 (18)	C222—H222	0.9500
C2—C3	1.414 (2)	C223—C224	1.378 (3)
C2—C21	1.472 (2)	C223—H223	0.9500
C3—C4	1.378 (2)	C224—C225	1.383 (3)
C3—H3	0.9500	C224—H224	0.9500
C4—C4A	1.4348 (19)	C225—C226	1.385 (2)
C4—C41	1.4663 (19)	C225—H225	0.9500
C4A—C5	1.4185 (19)	C226—H226	0.9500
C4A—C8A	1.4261 (19)	C41—C42	1.331 (2)
C5—C6	1.365 (2)	C41—H41	0.9500
C5—H5	0.9500	C42—C421	1.475 (2)
C6—C7	1.408 (2)	C42—H42	0.9500
C6—H6	0.9500	C421—C426	1.394 (2)
C7—C8	1.363 (2)	C421—C422	1.395 (2)
C7—H7	0.9500	C422—C423	1.383 (2)
C8—C8A	1.4195 (19)	C422—H422	0.9500
C8—H8	0.9500	C423—C424	1.384 (2)
C21—C22	1.332 (2)	C423—H423	0.9500
C21—H21	0.9500	C424—C425	1.383 (2)
C22—C221	1.470 (2)	C424—H424	0.9500
C22—H22	0.9500	C425—C426	1.389 (2)
C221—C222	1.399 (2)	C425—H425	0.9500
C221—C226	1.402 (2)	C426—H426	0.9500
C2—N1—C8A	117.65 (12)	C223—C222—H222	119.7
N1—C2—C3	122.94 (13)	C221—C222—H222	119.7
N1—C2—C21	117.88 (13)	C224—C223—C222	120.38 (16)
C3—C2—C21	119.12 (13)	C224—C223—H223	119.8
C4—C3—C2	121.01 (13)	C222—C223—H223	119.8
C4—C3—H3	119.5	C223—C224—C225	119.83 (15)
C2—C3—H3	119.5	C223—C224—H224	120.1
C3—C4—C4A	117.29 (13)	C225—C224—H224	120.1
C3—C4—C41	122.64 (13)	C224—C225—C226	120.32 (16)
C4A—C4—C41	120.02 (13)	C224—C225—H225	119.8
C5—C4A—C8A	118.27 (13)	C226—C225—H225	119.8
C5—C4A—C4	124.16 (13)	C225—C226—C221	120.80 (16)
C8A—C4A—C4	117.57 (12)	C225—C226—H226	119.6
C6—C5—C4A	121.08 (13)	C221—C226—H226	119.6
C6—C5—H5	119.5	C42—C41—C4	126.64 (14)
C4A—C5—H5	119.5	C42—C41—H41	116.7
C5—C6—C7	120.60 (13)	C4—C41—H41	116.7
C5—C6—H6	119.7	C41—C42—C421	124.87 (14)
C7—C6—H6	119.7	C41—C42—H42	117.6
C8—C7—C6	120.00 (13)	C421—C42—H42	117.6
C8—C7—H7	120.0	C426—C421—C422	118.31 (13)
C6—C7—H7	120.0	C426—C421—C42	119.34 (14)
C7—C8—C8A	121.10 (13)	C422—C421—C42	122.33 (13)
C7—C8—H8	119.4	C423—C422—C421	120.84 (14)
C8A—C8—H8	119.5	C423—C422—H422	119.6
N1—C8A—C8	117.53 (12)	C421—C422—H422	119.6
N1—C8A—C4A	123.53 (13)	C422—C423—C424	120.47 (15)
C8—C8A—C4A	118.93 (13)	C422—C423—H423	119.8
C22—C21—C2	124.43 (14)	C424—C423—H423	119.8
C22—C21—H21	117.8	C425—C424—C423	119.30 (14)
C2—C21—H21	117.8	C425—C424—H424	120.3
C21—C22—C221	126.46 (14)	C423—C424—H424	120.3
C21—C22—H22	116.8	C424—C425—C426	120.49 (15)
C221—C22—H22	116.8	C424—C425—H425	119.8
C222—C221—C226	118.04 (14)	C426—C425—H425	119.8
C222—C221—C22	119.21 (14)	C425—C426—C421	120.57 (15)
C226—C221—C22	122.74 (14)	C425—C426—H426	119.7
C223—C222—C221	120.62 (16)	C421—C426—H426	119.7
C8A—N1—C2—C3	−0.4 (2)	C2—C21—C22—C221	−177.49 (14)
C8A—N1—C2—C21	176.56 (12)	C21—C22—C221—C222	−173.99 (15)
N1—C2—C3—C4	1.2 (2)	C21—C22—C221—C226	6.5 (2)
C21—C2—C3—C4	−175.69 (13)	C226—C221—C222—C223	0.2 (2)
C2—C3—C4—C4A	−1.5 (2)	C22—C221—C222—C223	−179.25 (15)
C2—C3—C4—C41	176.08 (13)	C221—C222—C223—C224	−0.3 (3)
C3—C4—C4A—C5	−179.49 (13)	C222—C223—C224—C225	−0.5 (3)
C41—C4—C4A—C5	2.8 (2)	C223—C224—C225—C226	1.3 (3)
C3—C4—C4A—C8A	1.10 (19)	C224—C225—C226—C221	−1.4 (2)
C41—C4—C4A—C8A	−176.57 (12)	C222—C221—C226—C225	0.6 (2)
C8A—C4A—C5—C6	1.8 (2)	C22—C221—C226—C225	−179.93 (14)
C4—C4A—C5—C6	−177.56 (13)	C3—C4—C41—C42	19.8 (2)
C4A—C5—C6—C7	−1.1 (2)	C4A—C4—C41—C42	−162.67 (14)
C5—C6—C7—C8	−0.2 (2)	C4—C41—C42—C421	−179.93 (14)
C6—C7—C8—C8A	0.7 (2)	C41—C42—C421—C426	−170.19 (15)
C2—N1—C8A—C8	−178.53 (13)	C41—C42—C421—C422	8.3 (2)
C2—N1—C8A—C4A	0.0 (2)	C426—C421—C422—C423	−0.7 (2)
C7—C8—C8A—N1	178.61 (14)	C42—C421—C422—C423	−179.23 (14)
C7—C8—C8A—C4A	0.0 (2)	C421—C422—C423—C424	−0.2 (2)
C5—C4A—C8A—N1	−179.79 (13)	C422—C423—C424—C425	1.1 (3)
C4—C4A—C8A—N1	−0.3 (2)	C423—C424—C425—C426	−0.9 (3)
C5—C4A—C8A—C8	−1.31 (19)	C424—C425—C426—C421	0.0 (3)
C4—C4A—C8A—C8	178.13 (12)	C422—C421—C426—C425	0.9 (2)
N1—C2—C21—C22	4.2 (2)	C42—C421—C426—C425	179.40 (15)
C3—C2—C21—C22	−178.77 (14)

2-[(E)-2-(2,4-Dichlorophenyl)ethenyl]-4-[(E)-2-phenylethenyl]quinoline (IIb)

Crystal data

C25H17Cl2N	F(000) = 1664
Mr = 402.29	Dx = 1.395 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 28.4950 (7) Å	Cell parameters from 4414 reflections
b = 9.5384 (3) Å	θ = 2.3–27.5°
c = 16.0520 (5) Å	µ = 0.35 mm^−1
β = 118.581 (1)°	T = 100 K
V = 3831.2 (2) Å^3	Needle, yellow
Z = 8	0.21 × 0.10 × 0.09 mm

Data collection

Bruker D8 Venture diffractometer	4414 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3914 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.056
φ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −36→36
Tmin = 0.901, Tmax = 0.969	k = −12→12
47555 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0269P)^2 + 5.0618P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
4414 reflections	Δρmax = 0.35 e Å^−3
253 parameters	Δρmin = −0.22 e Å^−3
0 restraints

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.34810 (5)	0.64678 (13)	0.74277 (9)	0.0163 (2)
C2	0.35420 (6)	0.55453 (15)	0.68669 (10)	0.0156 (3)
C3	0.38455 (6)	0.58355 (15)	0.63990 (10)	0.0154 (3)
H3	0.3877	0.5141	0.6005	0.018*
C4	0.40950 (5)	0.71125 (15)	0.65081 (10)	0.0137 (3)
C4A	0.40294 (5)	0.81360 (14)	0.71004 (10)	0.0129 (3)
C5	0.42460 (5)	0.95117 (15)	0.72584 (10)	0.0154 (3)
H5	0.4465	0.9781	0.6988	0.018*
C6	0.41446 (6)	1.04583 (15)	0.77956 (10)	0.0169 (3)
H6	0.4292	1.1375	0.7890	0.020*
C7	0.38231 (6)	1.00820 (16)	0.82102 (10)	0.0179 (3)
H7	0.3751	1.0748	0.8575	0.021*
C8	0.36151 (6)	0.87583 (16)	0.80862 (10)	0.0169 (3)
H8	0.3403	0.8507	0.8374	0.020*
C8A	0.37117 (5)	0.77557 (15)	0.75332 (10)	0.0141 (3)
C21	0.32776 (6)	0.41923 (16)	0.67809 (11)	0.0187 (3)
H21	0.3149	0.4024	0.7219	0.022*
C22	0.31970 (5)	0.31729 (15)	0.61607 (10)	0.0146 (3)
H22	0.3335	0.3292	0.5731	0.018*
C221	0.29064 (5)	0.18744 (14)	0.61034 (10)	0.0133 (3)
C222	0.29510 (5)	0.06659 (15)	0.56496 (10)	0.0132 (3)
Cl22	0.33362 (2)	0.06845 (4)	0.50727 (2)	0.01717 (9)
C223	0.26987 (5)	−0.05849 (15)	0.56351 (10)	0.0147 (3)
H223	0.2746	−0.1396	0.5340	0.018*
C224	0.23759 (5)	−0.06212 (15)	0.60632 (10)	0.0149 (3)
Cl24	0.20662 (2)	−0.21921 (4)	0.60666 (3)	0.01962 (9)
C225	0.22975 (6)	0.05596 (15)	0.64870 (10)	0.0158 (3)
H225	0.2066	0.0530	0.6760	0.019*
C226	0.25633 (5)	0.17802 (15)	0.65033 (10)	0.0150 (3)
H226	0.2512	0.2588	0.6797	0.018*
C41	0.44200 (6)	0.74136 (15)	0.60404 (10)	0.0154 (3)
H41	0.4686	0.8120	0.6306	0.018*
C42	0.43613 (6)	0.67480 (15)	0.52616 (10)	0.0153 (3)
H42	0.4082	0.6076	0.4993	0.018*
C421	0.46824 (5)	0.69448 (15)	0.47787 (10)	0.0145 (3)
C422	0.50747 (6)	0.79820 (16)	0.50348 (11)	0.0186 (3)
H422	0.5137	0.8613	0.5535	0.022*
C423	0.53739 (6)	0.80969 (18)	0.45648 (11)	0.0223 (3)
H423	0.5637	0.8811	0.4742	0.027*
C424	0.52924 (6)	0.71746 (17)	0.38357 (11)	0.0214 (3)
H424	0.5501	0.7251	0.3520	0.026*
C425	0.49045 (6)	0.61427 (16)	0.35741 (11)	0.0207 (3)
H425	0.4847	0.5509	0.3078	0.025*
C426	0.45998 (6)	0.60331 (15)	0.40360 (10)	0.0177 (3)
H426	0.4332	0.5331	0.3846	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0176 (6)	0.0181 (6)	0.0158 (6)	−0.0030 (5)	0.0101 (5)	−0.0026 (5)
C2	0.0170 (6)	0.0156 (7)	0.0154 (7)	−0.0022 (5)	0.0087 (6)	−0.0009 (5)
C3	0.0180 (6)	0.0152 (7)	0.0151 (7)	−0.0009 (5)	0.0096 (6)	−0.0016 (5)
C4	0.0137 (6)	0.0147 (6)	0.0137 (6)	0.0005 (5)	0.0073 (5)	0.0004 (5)
C4A	0.0114 (6)	0.0142 (6)	0.0122 (6)	0.0004 (5)	0.0048 (5)	0.0001 (5)
C5	0.0143 (6)	0.0163 (7)	0.0149 (7)	−0.0014 (5)	0.0065 (5)	0.0012 (5)
C6	0.0176 (7)	0.0137 (7)	0.0175 (7)	−0.0014 (5)	0.0069 (6)	−0.0011 (5)
C7	0.0191 (7)	0.0185 (7)	0.0162 (7)	0.0021 (6)	0.0085 (6)	−0.0032 (6)
C8	0.0162 (6)	0.0206 (7)	0.0160 (7)	−0.0005 (6)	0.0093 (6)	−0.0017 (6)
C8A	0.0135 (6)	0.0158 (7)	0.0129 (6)	−0.0005 (5)	0.0061 (5)	−0.0004 (5)
C21	0.0236 (7)	0.0186 (7)	0.0198 (7)	−0.0048 (6)	0.0150 (6)	−0.0011 (6)
C22	0.0143 (6)	0.0159 (7)	0.0152 (7)	−0.0007 (5)	0.0083 (5)	0.0017 (5)
C221	0.0132 (6)	0.0144 (6)	0.0120 (6)	−0.0004 (5)	0.0059 (5)	0.0007 (5)
C222	0.0123 (6)	0.0173 (7)	0.0123 (6)	0.0001 (5)	0.0077 (5)	0.0013 (5)
Cl22	0.01978 (17)	0.01936 (17)	0.01910 (17)	−0.00169 (13)	0.01472 (14)	−0.00115 (13)
C223	0.0163 (6)	0.0148 (6)	0.0142 (6)	−0.0003 (5)	0.0082 (5)	−0.0015 (5)
C224	0.0147 (6)	0.0146 (6)	0.0151 (6)	−0.0027 (5)	0.0070 (5)	0.0021 (5)
Cl24	0.02385 (18)	0.01647 (17)	0.02334 (18)	−0.00653 (13)	0.01515 (15)	−0.00166 (14)
C225	0.0157 (6)	0.0194 (7)	0.0156 (7)	0.0002 (5)	0.0100 (6)	0.0011 (6)
C226	0.0165 (6)	0.0154 (7)	0.0150 (7)	−0.0002 (5)	0.0090 (5)	−0.0016 (5)
C41	0.0157 (6)	0.0139 (6)	0.0187 (7)	−0.0020 (5)	0.0101 (6)	0.0000 (5)
C42	0.0149 (6)	0.0154 (6)	0.0168 (7)	−0.0008 (5)	0.0086 (5)	0.0010 (5)
C421	0.0143 (6)	0.0162 (7)	0.0135 (6)	0.0026 (5)	0.0070 (5)	0.0023 (5)
C422	0.0177 (7)	0.0239 (8)	0.0157 (7)	−0.0028 (6)	0.0092 (6)	−0.0024 (6)
C423	0.0169 (7)	0.0304 (8)	0.0210 (8)	−0.0037 (6)	0.0102 (6)	0.0000 (6)
C424	0.0204 (7)	0.0300 (8)	0.0198 (7)	0.0067 (6)	0.0145 (6)	0.0052 (6)
C425	0.0281 (8)	0.0203 (7)	0.0169 (7)	0.0059 (6)	0.0134 (6)	0.0014 (6)
C426	0.0220 (7)	0.0155 (7)	0.0161 (7)	0.0015 (6)	0.0096 (6)	0.0014 (5)

Geometric parameters (Å, º)

N1—C2	1.3285 (18)	C222—C223	1.3874 (19)
N1—C8A	1.3650 (18)	C222—Cl22	1.7421 (14)
C2—C3	1.4178 (19)	C223—C224	1.3872 (19)
C2—C21	1.4672 (19)	C223—H223	0.9500
C3—C4	1.3785 (19)	C224—C225	1.388 (2)
C3—H3	0.9500	C224—Cl24	1.7403 (14)
C4—C4A	1.4360 (19)	C225—C226	1.382 (2)
C4—C41	1.4728 (19)	C225—H225	0.9500
C4A—C5	1.4204 (19)	C226—H226	0.9500
C4A—C8A	1.4268 (19)	C41—C42	1.339 (2)
C5—C6	1.371 (2)	C41—H41	0.9500
C5—H5	0.9500	C42—C421	1.4671 (19)
C6—C7	1.412 (2)	C42—H42	0.9500
C6—H6	0.9500	C421—C422	1.399 (2)
C7—C8	1.368 (2)	C421—C426	1.401 (2)
C7—H7	0.9500	C422—C423	1.387 (2)
C8—C8A	1.418 (2)	C422—H422	0.9500
C8—H8	0.9500	C423—C424	1.392 (2)
C21—C22	1.331 (2)	C423—H423	0.9500
C21—H21	0.9500	C424—C425	1.387 (2)
C22—C221	1.4681 (19)	C424—H424	0.9500
C22—H22	0.9500	C425—C426	1.389 (2)
C221—C222	1.4015 (19)	C425—H425	0.9500
C221—C226	1.4061 (19)	C426—H426	0.9500
C2—N1—C8A	117.96 (12)	C223—C222—Cl22	116.95 (11)
N1—C2—C3	122.71 (13)	C221—C222—Cl22	120.32 (10)
N1—C2—C21	114.75 (13)	C224—C223—C222	118.32 (13)
C3—C2—C21	122.54 (13)	C224—C223—H223	120.8
C4—C3—C2	120.89 (13)	C222—C223—H223	120.8
C4—C3—H3	119.6	C223—C224—C225	121.52 (13)
C2—C3—H3	119.6	C223—C224—Cl24	118.71 (11)
C3—C4—C4A	117.53 (12)	C225—C224—Cl24	119.76 (11)
C3—C4—C41	121.29 (13)	C226—C225—C224	118.53 (13)
C4A—C4—C41	121.18 (12)	C226—C225—H225	120.7
C5—C4A—C8A	118.08 (12)	C224—C225—H225	120.7
C5—C4A—C4	124.28 (13)	C225—C226—C221	122.65 (13)
C8A—C4A—C4	117.61 (12)	C225—C226—H226	118.7
C6—C5—C4A	121.07 (13)	C221—C226—H226	118.7
C6—C5—H5	119.5	C42—C41—C4	123.72 (13)
C4A—C5—H5	119.5	C42—C41—H41	118.1
C5—C6—C7	120.56 (13)	C4—C41—H41	118.1
C5—C6—H6	119.7	C41—C42—C421	126.98 (13)
C7—C6—H6	119.7	C41—C42—H42	116.5
C8—C7—C6	119.97 (13)	C421—C42—H42	116.5
C8—C7—H7	120.0	C422—C421—C426	118.31 (13)
C6—C7—H7	120.0	C422—C421—C42	123.22 (13)
C7—C8—C8A	120.86 (13)	C426—C421—C42	118.46 (13)
C7—C8—H8	119.6	C423—C422—C421	120.57 (14)
C8A—C8—H8	119.6	C423—C422—H422	119.7
N1—C8A—C8	117.28 (12)	C421—C422—H422	119.7
N1—C8A—C4A	123.26 (13)	C422—C423—C424	120.58 (15)
C8—C8A—C4A	119.44 (13)	C422—C423—H423	119.7
C22—C21—C2	127.60 (13)	C424—C423—H423	119.7
C22—C21—H21	116.2	C425—C424—C423	119.43 (14)
C2—C21—H21	116.2	C425—C424—H424	120.3
C21—C22—C221	123.61 (13)	C423—C424—H424	120.3
C21—C22—H22	118.2	C424—C425—C426	120.19 (14)
C221—C22—H22	118.2	C424—C425—H425	119.9
C222—C221—C226	116.14 (12)	C426—C425—H425	119.9
C222—C221—C22	122.53 (12)	C425—C426—C421	120.91 (14)
C226—C221—C22	121.33 (13)	C425—C426—H426	119.5
C223—C222—C221	122.74 (12)	C421—C426—H426	119.5
C8A—N1—C2—C3	1.6 (2)	C21—C22—C221—C226	18.6 (2)
C8A—N1—C2—C21	−179.32 (12)	C226—C221—C222—C223	−3.6 (2)
N1—C2—C3—C4	0.0 (2)	C22—C221—C222—C223	176.63 (13)
C21—C2—C3—C4	−179.02 (13)	C226—C221—C222—Cl22	176.57 (10)
C2—C3—C4—C4A	−0.8 (2)	C22—C221—C222—Cl22	−3.22 (19)
C2—C3—C4—C41	178.76 (13)	C221—C222—C223—C224	2.1 (2)
C3—C4—C4A—C5	−177.89 (13)	Cl22—C222—C223—C224	−178.06 (11)
C41—C4—C4A—C5	2.5 (2)	C222—C223—C224—C225	0.9 (2)
C3—C4—C4A—C8A	0.08 (19)	C222—C223—C224—Cl24	−178.95 (10)
C41—C4—C4A—C8A	−179.49 (12)	C223—C224—C225—C226	−2.1 (2)
C8A—C4A—C5—C6	−1.3 (2)	Cl24—C224—C225—C226	177.75 (11)
C4—C4A—C5—C6	176.68 (14)	C224—C225—C226—C221	0.4 (2)
C4A—C5—C6—C7	0.3 (2)	C222—C221—C226—C225	2.3 (2)
C5—C6—C7—C8	0.8 (2)	C22—C221—C226—C225	−177.90 (13)
C6—C7—C8—C8A	−0.9 (2)	C3—C4—C41—C42	23.4 (2)
C2—N1—C8A—C8	176.15 (13)	C4A—C4—C41—C42	−157.03 (14)
C2—N1—C8A—C4A	−2.4 (2)	C4—C41—C42—C421	−177.25 (13)
C7—C8—C8A—N1	−178.68 (13)	C41—C42—C421—C422	−6.1 (2)
C7—C8—C8A—C4A	−0.1 (2)	C41—C42—C421—C426	172.66 (14)
C5—C4A—C8A—N1	179.65 (13)	C426—C421—C422—C423	−0.2 (2)
C4—C4A—C8A—N1	1.6 (2)	C42—C421—C422—C423	178.56 (14)
C5—C4A—C8A—C8	1.14 (19)	C421—C422—C423—C424	−0.6 (2)
C4—C4A—C8A—C8	−176.96 (13)	C422—C423—C424—C425	0.6 (2)
N1—C2—C21—C22	168.07 (15)	C423—C424—C425—C426	0.1 (2)
C3—C2—C21—C22	−12.9 (2)	C424—C425—C426—C421	−0.8 (2)
C2—C21—C22—C221	−177.26 (14)	C422—C421—C426—C425	0.9 (2)
C21—C22—C221—C222	−161.58 (14)	C42—C421—C426—C425	−177.92 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C225—H225···N1^i	0.95	2.62	3.522 (2)	158
C6—H6···Cg1^ii	0.95	2.65	3.4152 (16)	138
C422—H422···Cg2^iii	0.95	2.88	3.5843 (17)	132

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x, −y+2, z+1/2; (iii) −x+1, y, −z+3/2.

{2-[(E)-2-(4-Bromophenyl)ethenyl]-4-[(E)-2-phenylethenyl]quinolin-3-yl}(phenyl)methanone (IIc)

Crystal data

C32H22BrNO	F(000) = 1056
Mr = 516.41	Dx = 1.421 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.287 (2) Å	Cell parameters from 5610 reflections
b = 15.528 (3) Å	θ = 2.1–27.6°
c = 12.844 (3) Å	µ = 1.73 mm^−1
β = 99.877 (6)°	T = 100 K
V = 2414.2 (8) Å^3	Block, orange
Z = 4	0.15 × 0.12 × 0.08 mm

Data collection

Bruker D8 Venture diffractometer	5530 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	4290 reflections with I > 2σ(I)
Multilayer mirror monochromator	θmax = 27.7°, θmin = 2.1°
φ and ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −20→20
Tmin = 0.720, Tmax = 0.871	l = −13→16
5530 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.196	w = 1/[σ^2(Fo^2) + (0.1201P)^2 + 3.4939P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
5530 reflections	Δρmax = 1.40 e Å^−3
317 parameters	Δρmin = −0.70 e Å^−3
0 restraints

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.

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.4215 (3)	0.3390 (2)	0.8002 (3)	0.0148 (7)
C2	0.3349 (3)	0.3701 (2)	0.7353 (3)	0.0128 (8)
C3	0.3391 (3)	0.3892 (2)	0.6276 (3)	0.0141 (8)
C4	0.4366 (3)	0.3801 (2)	0.5881 (3)	0.0126 (7)
C4A	0.5332 (3)	0.3511 (3)	0.6594 (3)	0.0131 (7)
C5	0.6411 (3)	0.3442 (3)	0.6328 (3)	0.0157 (8)
H5	0.6538	0.3631	0.5656	0.019*
C6	0.7264 (3)	0.3106 (3)	0.7039 (3)	0.0190 (9)
H6	0.7977	0.3061	0.6852	0.023*
C7	0.7098 (3)	0.2828 (3)	0.8042 (3)	0.0184 (8)
H7	0.7688	0.2572	0.8515	0.022*
C8	0.6083 (3)	0.2925 (3)	0.8338 (3)	0.0182 (8)
H8	0.5981	0.2749	0.9023	0.022*
C8A	0.5189 (3)	0.3285 (3)	0.7637 (3)	0.0128 (8)
C21	0.2315 (3)	0.3833 (3)	0.7768 (3)	0.0154 (8)
H21	0.1662	0.3971	0.7286	0.018*
C22	0.2255 (3)	0.3765 (3)	0.8796 (3)	0.0157 (8)
H22	0.2930	0.3658	0.9261	0.019*
C221	0.1265 (3)	0.3837 (3)	0.9281 (3)	0.0164 (8)
C222	0.1348 (4)	0.3630 (3)	1.0353 (3)	0.0181 (8)
H222	0.2050	0.3487	1.0750	0.022*
C223	0.0431 (4)	0.3628 (3)	1.0853 (4)	0.0209 (9)
H223	0.0500	0.3477	1.1578	0.025*
C224	−0.0587 (4)	0.3850 (3)	1.0271 (4)	0.0195 (9)
Br24	−0.18670 (4)	0.38279 (3)	1.09166 (4)	0.02932 (18)
C225	−0.0702 (3)	0.4086 (3)	0.9209 (4)	0.0199 (9)
H225	−0.1403	0.4247	0.8824	0.024*
C226	0.0224 (3)	0.4081 (3)	0.8724 (3)	0.0178 (8)
H226	0.0154	0.4245	0.8003	0.021*
C31	0.2347 (3)	0.4121 (3)	0.5521 (3)	0.0138 (8)
O31	0.1835 (3)	0.3554 (2)	0.5000 (3)	0.0226 (7)
C311	0.1978 (3)	0.5040 (3)	0.5436 (3)	0.0145 (8)
C312	0.2408 (3)	0.5642 (3)	0.6201 (3)	0.0161 (8)
H312	0.2989	0.5484	0.6756	0.019*
C313	0.1985 (4)	0.6477 (3)	0.6148 (3)	0.0199 (9)
H313	0.2256	0.6884	0.6682	0.024*
C314	0.1159 (4)	0.6713 (3)	0.5308 (4)	0.0200 (9)
H314	0.0868	0.7280	0.5273	0.024*
C315	0.0762 (4)	0.6118 (3)	0.4521 (4)	0.0194 (9)
H315	0.0223	0.6287	0.3935	0.023*
C316	0.1154 (3)	0.5281 (3)	0.4594 (3)	0.0164 (8)
H316	0.0863	0.4870	0.4072	0.020*
C41	0.4372 (3)	0.3989 (3)	0.4752 (3)	0.0143 (8)
H41	0.4039	0.4513	0.4478	0.017*
C42	0.4805 (3)	0.3485 (3)	0.4088 (3)	0.0145 (8)
H42	0.5158	0.2972	0.4372	0.017*
C421	0.4788 (3)	0.3649 (3)	0.2956 (3)	0.0142 (8)
C422	0.4231 (3)	0.4349 (3)	0.2418 (3)	0.0195 (9)
H422	0.3809	0.4724	0.2777	0.023*
C423	0.4292 (4)	0.4499 (3)	0.1362 (3)	0.0236 (9)
H423	0.3914	0.4975	0.1003	0.028*
C424	0.4910 (4)	0.3950 (3)	0.0828 (3)	0.0222 (9)
H424	0.4960	0.4059	0.0110	0.027*
C425	0.5451 (3)	0.3243 (3)	0.1344 (3)	0.0186 (9)
H425	0.5867	0.2866	0.0981	0.022*
C426	0.5376 (3)	0.3094 (3)	0.2400 (3)	0.0162 (8)
H426	0.5732	0.2605	0.2748	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0167 (16)	0.0156 (17)	0.0127 (16)	−0.0016 (13)	0.0040 (13)	0.0026 (13)
C2	0.0146 (18)	0.0130 (18)	0.0117 (18)	−0.0005 (14)	0.0045 (14)	−0.0014 (14)
C3	0.0177 (18)	0.0105 (18)	0.0147 (19)	0.0015 (14)	0.0047 (15)	−0.0016 (15)
C4	0.0155 (18)	0.0125 (18)	0.0101 (18)	0.0005 (14)	0.0033 (14)	0.0004 (14)
C4A	0.0127 (17)	0.0166 (19)	0.0111 (18)	0.0009 (14)	0.0049 (14)	−0.0015 (15)
C5	0.0166 (19)	0.021 (2)	0.0105 (18)	−0.0027 (16)	0.0037 (15)	−0.0021 (16)
C6	0.0134 (18)	0.022 (2)	0.021 (2)	0.0005 (16)	0.0031 (16)	−0.0010 (17)
C7	0.0149 (18)	0.022 (2)	0.017 (2)	0.0010 (16)	−0.0009 (16)	0.0023 (17)
C8	0.020 (2)	0.022 (2)	0.0131 (19)	−0.0001 (16)	0.0031 (16)	0.0040 (16)
C8A	0.0143 (18)	0.0128 (18)	0.0113 (18)	−0.0001 (14)	0.0023 (14)	−0.0006 (14)
C21	0.0137 (18)	0.0181 (19)	0.0147 (19)	0.0006 (15)	0.0037 (15)	−0.0013 (15)
C22	0.0152 (19)	0.0143 (19)	0.018 (2)	−0.0016 (14)	0.0037 (16)	−0.0005 (15)
C221	0.020 (2)	0.0140 (19)	0.017 (2)	−0.0008 (15)	0.0080 (16)	−0.0010 (16)
C222	0.022 (2)	0.018 (2)	0.015 (2)	0.0004 (16)	0.0044 (17)	0.0004 (16)
C223	0.029 (2)	0.018 (2)	0.018 (2)	−0.0036 (17)	0.0112 (18)	−0.0006 (17)
C224	0.023 (2)	0.015 (2)	0.026 (2)	−0.0047 (16)	0.0182 (18)	−0.0063 (17)
Br24	0.0283 (3)	0.0292 (3)	0.0366 (3)	−0.00666 (19)	0.0230 (2)	−0.0062 (2)
C225	0.0143 (19)	0.021 (2)	0.025 (2)	−0.0026 (16)	0.0063 (17)	−0.0024 (18)
C226	0.021 (2)	0.018 (2)	0.016 (2)	−0.0017 (16)	0.0075 (16)	−0.0026 (16)
C31	0.0116 (17)	0.0198 (19)	0.0109 (18)	0.0023 (15)	0.0043 (14)	−0.0007 (15)
O31	0.0221 (15)	0.0184 (15)	0.0245 (17)	−0.0016 (12)	−0.0035 (13)	−0.0064 (13)
C311	0.0133 (18)	0.017 (2)	0.0148 (19)	−0.0010 (15)	0.0073 (15)	0.0015 (15)
C312	0.0149 (18)	0.019 (2)	0.0132 (19)	0.0003 (15)	−0.0004 (15)	0.0003 (15)
C313	0.023 (2)	0.017 (2)	0.019 (2)	0.0012 (16)	0.0021 (17)	−0.0027 (17)
C314	0.021 (2)	0.017 (2)	0.023 (2)	0.0033 (16)	0.0041 (17)	0.0006 (17)
C315	0.0156 (19)	0.022 (2)	0.019 (2)	0.0018 (16)	−0.0001 (16)	0.0054 (17)
C316	0.0140 (18)	0.021 (2)	0.015 (2)	−0.0023 (15)	0.0032 (15)	−0.0009 (16)
C41	0.0135 (18)	0.019 (2)	0.0105 (18)	−0.0016 (14)	0.0016 (14)	0.0023 (15)
C42	0.0180 (19)	0.0143 (18)	0.0108 (18)	−0.0010 (15)	0.0013 (15)	0.0009 (15)
C421	0.0151 (18)	0.016 (2)	0.0112 (19)	−0.0044 (14)	0.0016 (15)	0.0004 (15)
C422	0.020 (2)	0.021 (2)	0.017 (2)	0.0020 (16)	0.0006 (16)	−0.0005 (17)
C423	0.031 (2)	0.025 (2)	0.014 (2)	−0.0016 (19)	0.0002 (17)	0.0059 (17)
C424	0.024 (2)	0.033 (3)	0.0100 (19)	−0.0086 (18)	0.0036 (16)	−0.0005 (17)
C425	0.021 (2)	0.021 (2)	0.014 (2)	−0.0068 (16)	0.0069 (16)	−0.0052 (16)
C426	0.0155 (18)	0.017 (2)	0.0158 (19)	−0.0034 (15)	0.0022 (15)	−0.0011 (16)

Geometric parameters (Å, º)

N1—C2	1.325 (5)	C225—H225	0.9500
N1—C8A	1.368 (5)	C226—H226	0.9500
C2—C3	1.424 (6)	C31—O31	1.214 (5)
C2—C21	1.474 (5)	C31—C311	1.496 (6)
C3—C4	1.387 (6)	C311—C312	1.393 (6)
C3—C31	1.512 (5)	C311—C316	1.399 (6)
C4—C4A	1.441 (5)	C312—C313	1.395 (6)
C4—C41	1.480 (5)	C312—H312	0.9500
C4A—C8A	1.425 (5)	C313—C314	1.397 (6)
C4A—C5	1.429 (5)	C313—H313	0.9500
C5—C6	1.370 (6)	C314—C315	1.395 (6)
C5—H5	0.9500	C314—H314	0.9500
C6—C7	1.406 (6)	C315—C316	1.382 (6)
C6—H6	0.9500	C315—H315	0.9500
C7—C8	1.374 (6)	C316—H316	0.9500
C7—H7	0.9500	C41—C42	1.334 (6)
C8—C8A	1.410 (6)	C41—H41	0.9500
C8—H8	0.9500	C42—C421	1.474 (5)
C21—C22	1.338 (6)	C42—H42	0.9500
C21—H21	0.9500	C421—C426	1.397 (6)
C22—C221	1.463 (6)	C421—C422	1.401 (6)
C22—H22	0.9500	C422—C423	1.391 (6)
C221—C222	1.400 (6)	C422—H422	0.9500
C221—C226	1.406 (6)	C423—C424	1.396 (7)
C222—C223	1.388 (6)	C423—H423	0.9500
C222—H222	0.9500	C424—C425	1.391 (7)
C223—C224	1.387 (7)	C424—H424	0.9500
C223—H223	0.9500	C425—C426	1.394 (6)
C224—C225	1.396 (6)	C425—H425	0.9500
C224—Br24	1.899 (4)	C426—H426	0.9500
C225—C226	1.388 (6)
C2—N1—C8A	118.9 (3)	C225—C226—C221	121.1 (4)
N1—C2—C3	121.9 (4)	C225—C226—H226	119.4
N1—C2—C21	118.1 (4)	C221—C226—H226	119.4
C3—C2—C21	120.0 (4)	O31—C31—C311	122.0 (4)
C4—C3—C2	120.8 (4)	O31—C31—C3	119.0 (4)
C4—C3—C31	118.7 (4)	C311—C31—C3	119.0 (3)
C2—C3—C31	120.3 (4)	C312—C311—C316	120.1 (4)
C3—C4—C4A	117.9 (3)	C312—C311—C31	121.0 (4)
C3—C4—C41	119.2 (3)	C316—C311—C31	118.8 (4)
C4A—C4—C41	122.9 (3)	C311—C312—C313	119.8 (4)
C8A—C4A—C5	118.4 (4)	C311—C312—H312	120.1
C8A—C4A—C4	117.0 (3)	C313—C312—H312	120.1
C5—C4A—C4	124.6 (4)	C312—C313—C314	119.7 (4)
C6—C5—C4A	120.3 (4)	C312—C313—H313	120.1
C6—C5—H5	119.8	C314—C313—H313	120.1
C4A—C5—H5	119.8	C315—C314—C313	120.3 (4)
C5—C6—C7	120.9 (4)	C315—C314—H314	119.9
C5—C6—H6	119.6	C313—C314—H314	119.9
C7—C6—H6	119.6	C316—C315—C314	119.9 (4)
C8—C7—C6	120.1 (4)	C316—C315—H315	120.1
C8—C7—H7	120.0	C314—C315—H315	120.1
C6—C7—H7	120.0	C315—C316—C311	120.1 (4)
C7—C8—C8A	120.8 (4)	C315—C316—H316	120.0
C7—C8—H8	119.6	C311—C316—H316	120.0
C8A—C8—H8	119.6	C42—C41—C4	125.4 (4)
N1—C8A—C8	117.4 (4)	C42—C41—H41	117.3
N1—C8A—C4A	123.3 (3)	C4—C41—H41	117.3
C8—C8A—C4A	119.3 (4)	C41—C42—C421	126.1 (4)
C22—C21—C2	122.8 (4)	C41—C42—H42	116.9
C22—C21—H21	118.6	C421—C42—H42	116.9
C2—C21—H21	118.6	C426—C421—C422	118.6 (4)
C21—C22—C221	127.2 (4)	C426—C421—C42	118.4 (4)
C21—C22—H22	116.4	C422—C421—C42	123.0 (4)
C221—C22—H22	116.4	C423—C422—C421	120.4 (4)
C222—C221—C226	117.9 (4)	C423—C422—H422	119.8
C222—C221—C22	118.4 (4)	C421—C422—H422	119.8
C226—C221—C22	123.6 (4)	C422—C423—C424	120.1 (4)
C223—C222—C221	121.8 (4)	C422—C423—H423	120.0
C223—C222—H222	119.1	C424—C423—H423	120.0
C221—C222—H222	119.1	C425—C424—C423	120.3 (4)
C224—C223—C222	118.7 (4)	C425—C424—H424	119.9
C224—C223—H223	120.7	C423—C424—H424	119.9
C222—C223—H223	120.7	C424—C425—C426	119.2 (4)
C223—C224—C225	121.5 (4)	C424—C425—H425	120.4
C223—C224—Br24	119.9 (3)	C426—C425—H425	120.4
C225—C224—Br24	118.6 (3)	C425—C426—C421	121.4 (4)
C226—C225—C224	119.0 (4)	C425—C426—H426	119.3
C226—C225—H225	120.5	C421—C426—H426	119.3
C224—C225—H225	120.5
C8A—N1—C2—C3	2.9 (6)	C222—C223—C224—Br24	178.5 (3)
C8A—N1—C2—C21	−178.4 (4)	C223—C224—C225—C226	1.2 (7)
N1—C2—C3—C4	−3.6 (6)	Br24—C224—C225—C226	−178.2 (3)
C21—C2—C3—C4	177.7 (4)	C224—C225—C226—C221	0.5 (6)
N1—C2—C3—C31	171.0 (4)	C222—C221—C226—C225	−2.4 (6)
C21—C2—C3—C31	−7.7 (6)	C22—C221—C226—C225	175.9 (4)
C2—C3—C4—C4A	−0.1 (6)	C4—C3—C31—O31	81.8 (5)
C31—C3—C4—C4A	−174.8 (4)	C2—C3—C31—O31	−92.8 (5)
C2—C3—C4—C41	178.8 (3)	C4—C3—C31—C311	−98.1 (4)
C31—C3—C4—C41	4.2 (6)	C2—C3—C31—C311	87.2 (5)
C3—C4—C4A—C8A	4.0 (5)	O31—C31—C311—C312	164.5 (4)
C41—C4—C4A—C8A	−174.9 (4)	C3—C31—C311—C312	−15.6 (6)
C3—C4—C4A—C5	−175.5 (4)	O31—C31—C311—C316	−12.9 (6)
C41—C4—C4A—C5	5.6 (6)	C3—C31—C311—C316	167.0 (4)
C8A—C4A—C5—C6	4.8 (6)	C316—C311—C312—C313	2.6 (6)
C4—C4A—C5—C6	−175.7 (4)	C31—C311—C312—C313	−174.8 (4)
C4A—C5—C6—C7	−0.4 (6)	C311—C312—C313—C314	−2.4 (7)
C5—C6—C7—C8	−2.9 (7)	C312—C313—C314—C315	−0.2 (7)
C6—C7—C8—C8A	1.5 (7)	C313—C314—C315—C316	2.6 (7)
C2—N1—C8A—C8	−178.0 (4)	C314—C315—C316—C311	−2.4 (6)
C2—N1—C8A—C4A	1.4 (6)	C312—C311—C316—C315	−0.2 (6)
C7—C8—C8A—N1	−177.7 (4)	C31—C311—C316—C315	177.2 (4)
C7—C8—C8A—C4A	2.9 (6)	C3—C4—C41—C42	−131.9 (4)
C5—C4A—C8A—N1	174.7 (4)	C4A—C4—C41—C42	46.9 (6)
C4—C4A—C8A—N1	−4.9 (6)	C4—C41—C42—C421	178.0 (4)
C5—C4A—C8A—C8	−6.0 (6)	C41—C42—C421—C426	173.9 (4)
C4—C4A—C8A—C8	174.5 (4)	C41—C42—C421—C422	−4.5 (6)
N1—C2—C21—C22	9.4 (6)	C426—C421—C422—C423	−1.8 (6)
C3—C2—C21—C22	−171.8 (4)	C42—C421—C422—C423	176.5 (4)
C2—C21—C22—C221	−176.5 (4)	C421—C422—C423—C424	0.1 (7)
C21—C22—C221—C222	171.4 (4)	C422—C423—C424—C425	1.1 (7)
C21—C22—C221—C226	−6.8 (7)	C423—C424—C425—C426	−0.4 (6)
C226—C221—C222—C223	2.6 (6)	C424—C425—C426—C421	−1.4 (6)
C22—C221—C222—C223	−175.7 (4)	C422—C421—C426—C425	2.5 (6)
C221—C222—C223—C224	−1.0 (6)	C42—C421—C426—C425	−175.9 (4)
C222—C223—C224—C225	−1.0 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O31^i	0.95	2.51	3.164 (6)	126
C5—H5···Cg3^ii	0.95	2.96	3.728 (4)	138
C42—H42···Cg4^iii	0.95	2.88	3.766 (5)	155
C223—H223···Cg2^iv	0.95	2.84	3.429 (3)	122

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

{2-[(E)-2-(4-Bromophenyl)ethenyl]-4-[(E)-2-(4-chlorophenyl)ethenyl]quinolin-3-yl}(phenyl)methanone (IId)

Crystal data

C32H21BrClNO	Z = 2
Mr = 550.86	F(000) = 560
Triclinic, P1	Dx = 1.446 Mg m^−3
a = 9.9051 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.3936 (16) Å	Cell parameters from 5808 reflections
c = 11.8192 (16) Å	θ = 2.1–27.5°
α = 77.727 (5)°	µ = 1.76 mm^−1
β = 76.116 (5)°	T = 100 K
γ = 86.448 (5)°	Needle, orange
V = 1265.2 (3) Å^3	0.19 × 0.12 × 0.10 mm

Data collection

Bruker D8 Venture diffractometer	5807 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	5014 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.064
φ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −12→12
Tmin = 0.735, Tmax = 0.836	k = −14→14
61838 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0211P)^2 + 0.9058P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
5807 reflections	Δρmax = 0.33 e Å^−3
325 parameters	Δρmin = −0.39 e Å^−3
0 restraints

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.25739 (15)	0.14281 (12)	0.26486 (12)	0.0186 (3)
C2	0.27568 (17)	0.25070 (15)	0.28341 (14)	0.0177 (3)
C3	0.18801 (17)	0.35119 (15)	0.25316 (14)	0.0174 (3)
C4	0.07281 (17)	0.33605 (15)	0.21049 (14)	0.0178 (3)
C4A	0.04978 (18)	0.21906 (15)	0.19294 (14)	0.0186 (3)
C5	−0.06396 (19)	0.19160 (16)	0.15045 (16)	0.0229 (4)
H5	−0.1308	0.2522	0.1338	0.027*
C6	−0.0786 (2)	0.07815 (17)	0.13304 (17)	0.0259 (4)
H6	−0.1550	0.0612	0.1037	0.031*
C7	0.0187 (2)	−0.01340 (17)	0.15836 (16)	0.0268 (4)
H7	0.0077	−0.0915	0.1458	0.032*
C8	0.1287 (2)	0.00997 (16)	0.20101 (16)	0.0239 (4)
H8	0.1936	−0.0523	0.2182	0.029*
C8A	0.14692 (18)	0.12607 (15)	0.21983 (14)	0.0189 (3)
C21	0.39417 (17)	0.26536 (15)	0.33401 (15)	0.0189 (3)
H21	0.4107	0.3431	0.3446	0.023*
C22	0.47975 (17)	0.17587 (15)	0.36585 (14)	0.0187 (3)
H22	0.4604	0.0981	0.3572	0.022*
C221	0.60111 (17)	0.18767 (15)	0.41304 (14)	0.0184 (3)
C222	0.69215 (19)	0.09039 (16)	0.42888 (16)	0.0222 (4)
H222	0.6732	0.0169	0.4104	0.027*
C223	0.81012 (19)	0.09851 (17)	0.47115 (16)	0.0248 (4)
H223	0.8715	0.0317	0.4812	0.030*
C224	0.83589 (18)	0.20575 (17)	0.49815 (15)	0.0217 (4)
Br24	0.99791 (2)	0.22361 (2)	0.55228 (2)	0.02713 (6)
C225	0.74666 (19)	0.30359 (16)	0.48620 (16)	0.0231 (4)
H225	0.7650	0.3760	0.5071	0.028*
C226	0.63015 (18)	0.29440 (16)	0.44326 (16)	0.0218 (4)
H226	0.5689	0.3615	0.4341	0.026*
C31	0.22620 (17)	0.47358 (15)	0.26497 (15)	0.0179 (3)
O31	0.22130 (14)	0.49477 (11)	0.36281 (11)	0.0243 (3)
C311	0.27711 (17)	0.56428 (15)	0.15343 (15)	0.0177 (3)
C312	0.31444 (17)	0.53198 (15)	0.04237 (15)	0.0188 (3)
H312	0.3043	0.4512	0.0366	0.023*
C313	0.36616 (19)	0.61701 (16)	−0.05946 (16)	0.0228 (4)
H313	0.3914	0.5944	−0.1347	0.027*
C314	0.38126 (19)	0.73545 (16)	−0.05168 (16)	0.0243 (4)
H314	0.4170	0.7936	−0.1215	0.029*
C315	0.3439 (2)	0.76857 (16)	0.05844 (17)	0.0264 (4)
H315	0.3534	0.8496	0.0637	0.032*
C316	0.29282 (19)	0.68348 (16)	0.16068 (16)	0.0240 (4)
H316	0.2684	0.7062	0.2359	0.029*
C41	−0.02388 (17)	0.43635 (15)	0.18546 (15)	0.0188 (3)
H41	−0.0546	0.4478	0.1136	0.023*
C42	−0.07061 (17)	0.51205 (15)	0.25875 (15)	0.0191 (3)
H42	−0.0399	0.4977	0.3308	0.023*
C421	−0.16475 (17)	0.61522 (15)	0.23908 (15)	0.0176 (3)
C422	−0.18229 (19)	0.67061 (16)	0.12605 (16)	0.0236 (4)
H422	−0.1320	0.6407	0.0587	0.028*
C423	−0.2715 (2)	0.76825 (16)	0.11010 (16)	0.0252 (4)
H423	−0.2825	0.8052	0.0328	0.030*
C424	−0.34445 (18)	0.81098 (15)	0.20919 (16)	0.0214 (4)
Cl44	−0.45721 (5)	0.93371 (4)	0.19179 (5)	0.03007 (11)
C425	−0.32830 (18)	0.75949 (16)	0.32232 (16)	0.0215 (4)
H425	−0.3780	0.7905	0.3892	0.026*
C426	−0.23864 (18)	0.66202 (16)	0.33677 (15)	0.0206 (3)
H426	−0.2271	0.6264	0.4142	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0214 (7)	0.0165 (7)	0.0177 (7)	0.0009 (6)	−0.0040 (6)	−0.0039 (6)
C2	0.0202 (8)	0.0173 (8)	0.0143 (8)	0.0006 (6)	−0.0016 (6)	−0.0031 (6)
C3	0.0218 (8)	0.0157 (8)	0.0133 (7)	0.0001 (6)	−0.0017 (6)	−0.0029 (6)
C4	0.0208 (8)	0.0170 (8)	0.0140 (8)	0.0015 (6)	−0.0014 (6)	−0.0033 (6)
C4A	0.0227 (8)	0.0176 (8)	0.0145 (8)	−0.0008 (7)	−0.0022 (6)	−0.0032 (6)
C5	0.0240 (9)	0.0220 (9)	0.0228 (9)	0.0000 (7)	−0.0066 (7)	−0.0036 (7)
C6	0.0290 (9)	0.0249 (9)	0.0255 (9)	−0.0060 (8)	−0.0088 (8)	−0.0048 (7)
C7	0.0381 (11)	0.0198 (9)	0.0244 (9)	−0.0043 (8)	−0.0081 (8)	−0.0067 (7)
C8	0.0316 (10)	0.0178 (9)	0.0225 (9)	0.0001 (7)	−0.0058 (7)	−0.0052 (7)
C8A	0.0230 (8)	0.0178 (8)	0.0151 (8)	−0.0004 (7)	−0.0023 (6)	−0.0038 (6)
C21	0.0217 (8)	0.0178 (8)	0.0173 (8)	−0.0012 (6)	−0.0029 (6)	−0.0052 (6)
C22	0.0212 (8)	0.0183 (8)	0.0164 (8)	−0.0009 (6)	−0.0014 (6)	−0.0065 (6)
C221	0.0200 (8)	0.0201 (8)	0.0137 (8)	−0.0007 (6)	−0.0012 (6)	−0.0039 (6)
C222	0.0259 (9)	0.0179 (8)	0.0234 (9)	0.0003 (7)	−0.0055 (7)	−0.0060 (7)
C223	0.0251 (9)	0.0229 (9)	0.0260 (9)	0.0037 (7)	−0.0068 (7)	−0.0044 (7)
C224	0.0187 (8)	0.0288 (10)	0.0167 (8)	−0.0023 (7)	−0.0039 (6)	−0.0028 (7)
Br24	0.02189 (9)	0.03552 (11)	0.02435 (10)	−0.00343 (7)	−0.00719 (7)	−0.00397 (7)
C225	0.0263 (9)	0.0215 (9)	0.0229 (9)	−0.0026 (7)	−0.0046 (7)	−0.0082 (7)
C226	0.0226 (8)	0.0198 (9)	0.0243 (9)	0.0024 (7)	−0.0060 (7)	−0.0077 (7)
C31	0.0191 (8)	0.0168 (8)	0.0187 (8)	0.0039 (6)	−0.0060 (6)	−0.0052 (6)
O31	0.0362 (7)	0.0207 (6)	0.0183 (6)	0.0028 (5)	−0.0089 (5)	−0.0073 (5)
C311	0.0173 (8)	0.0180 (8)	0.0187 (8)	0.0016 (6)	−0.0054 (6)	−0.0049 (6)
C312	0.0198 (8)	0.0174 (8)	0.0203 (8)	0.0031 (6)	−0.0046 (7)	−0.0072 (7)
C313	0.0247 (9)	0.0238 (9)	0.0192 (8)	0.0017 (7)	−0.0021 (7)	−0.0065 (7)
C314	0.0247 (9)	0.0215 (9)	0.0227 (9)	−0.0005 (7)	−0.0009 (7)	−0.0005 (7)
C315	0.0333 (10)	0.0164 (9)	0.0288 (10)	−0.0027 (7)	−0.0048 (8)	−0.0051 (7)
C316	0.0300 (9)	0.0209 (9)	0.0223 (9)	0.0004 (7)	−0.0058 (7)	−0.0073 (7)
C41	0.0202 (8)	0.0187 (8)	0.0168 (8)	−0.0003 (6)	−0.0046 (6)	−0.0019 (6)
C42	0.0189 (8)	0.0211 (9)	0.0159 (8)	0.0004 (7)	−0.0029 (6)	−0.0021 (7)
C421	0.0183 (8)	0.0178 (8)	0.0171 (8)	−0.0009 (6)	−0.0029 (6)	−0.0055 (6)
C422	0.0298 (9)	0.0226 (9)	0.0180 (8)	0.0051 (7)	−0.0029 (7)	−0.0079 (7)
C423	0.0341 (10)	0.0220 (9)	0.0206 (9)	0.0048 (8)	−0.0093 (8)	−0.0046 (7)
C424	0.0200 (8)	0.0166 (8)	0.0296 (9)	0.0027 (7)	−0.0072 (7)	−0.0083 (7)
Cl44	0.0321 (2)	0.0214 (2)	0.0424 (3)	0.01031 (18)	−0.0158 (2)	−0.0138 (2)
C425	0.0217 (8)	0.0220 (9)	0.0220 (9)	0.0002 (7)	−0.0014 (7)	−0.0110 (7)
C426	0.0208 (8)	0.0231 (9)	0.0179 (8)	0.0002 (7)	−0.0033 (7)	−0.0059 (7)

Geometric parameters (Å, º)

N1—C2	1.324 (2)	C225—H225	0.9500
N1—C8A	1.366 (2)	C226—H226	0.9500
C2—C3	1.430 (2)	C31—O31	1.220 (2)
C2—C21	1.472 (2)	C31—C311	1.492 (2)
C3—C4	1.387 (2)	C311—C312	1.397 (2)
C3—C31	1.510 (2)	C311—C316	1.399 (2)
C4—C4A	1.432 (2)	C312—C313	1.385 (2)
C4—C41	1.472 (2)	C312—H312	0.9500
C4A—C5	1.415 (2)	C313—C314	1.391 (3)
C4A—C8A	1.424 (2)	C313—H313	0.9500
C5—C6	1.373 (3)	C314—C315	1.391 (3)
C5—H5	0.9500	C314—H314	0.9500
C6—C7	1.410 (3)	C315—C316	1.388 (3)
C6—H6	0.9500	C315—H315	0.9500
C7—C8	1.368 (3)	C316—H316	0.9500
C7—H7	0.9500	C41—C42	1.336 (2)
C8—C8A	1.416 (2)	C41—H41	0.9500
C8—H8	0.9500	C42—C421	1.469 (2)
C21—C22	1.335 (2)	C42—H42	0.9500
C21—H21	0.9500	C421—C422	1.397 (2)
C22—C221	1.465 (2)	C421—C426	1.400 (2)
C22—H22	0.9500	C422—C423	1.387 (2)
C221—C222	1.395 (2)	C422—H422	0.9500
C221—C226	1.402 (2)	C423—C424	1.387 (3)
C222—C223	1.392 (2)	C423—H423	0.9500
C222—H222	0.9500	C424—C425	1.384 (3)
C223—C224	1.380 (3)	C424—Cl44	1.7434 (17)
C223—H223	0.9500	C425—C426	1.386 (2)
C224—C225	1.384 (3)	C425—H425	0.9500
C224—Br24	1.9012 (17)	C426—H426	0.9500
C225—C226	1.385 (2)
C2—N1—C8A	118.52 (14)	C225—C226—C221	121.07 (16)
N1—C2—C3	122.50 (15)	C225—C226—H226	119.5
N1—C2—C21	117.24 (15)	C221—C226—H226	119.5
C3—C2—C21	120.24 (15)	O31—C31—C311	121.58 (15)
C4—C3—C2	120.13 (15)	O31—C31—C3	120.48 (15)
C4—C3—C31	121.16 (15)	C311—C31—C3	117.85 (14)
C2—C3—C31	118.69 (14)	C312—C311—C316	119.22 (16)
C3—C4—C4A	117.81 (15)	C312—C311—C31	121.46 (15)
C3—C4—C41	121.26 (15)	C316—C311—C31	119.27 (15)
C4A—C4—C41	120.93 (15)	C313—C312—C311	120.39 (16)
C5—C4A—C8A	118.69 (15)	C313—C312—H312	119.8
C5—C4A—C4	123.41 (16)	C311—C312—H312	119.8
C8A—C4A—C4	117.90 (15)	C312—C313—C314	120.10 (16)
C6—C5—C4A	120.61 (17)	C312—C313—H313	119.9
C6—C5—H5	119.7	C314—C313—H313	119.9
C4A—C5—H5	119.7	C315—C314—C313	119.93 (17)
C5—C6—C7	120.58 (17)	C315—C314—H314	120.0
C5—C6—H6	119.7	C313—C314—H314	120.0
C7—C6—H6	119.7	C316—C315—C314	120.11 (17)
C8—C7—C6	120.17 (17)	C316—C315—H315	119.9
C8—C7—H7	119.9	C314—C315—H315	119.9
C6—C7—H7	119.9	C315—C316—C311	120.24 (16)
C7—C8—C8A	120.65 (17)	C315—C316—H316	119.9
C7—C8—H8	119.7	C311—C316—H316	119.9
C8A—C8—H8	119.7	C42—C41—C4	123.27 (15)
N1—C8A—C8	117.71 (15)	C42—C41—H41	118.4
N1—C8A—C4A	122.99 (15)	C4—C41—H41	118.4
C8—C8A—C4A	119.29 (16)	C41—C42—C421	126.48 (16)
C22—C21—C2	123.88 (16)	C41—C42—H42	116.8
C22—C21—H21	118.1	C421—C42—H42	116.8
C2—C21—H21	118.1	C422—C421—C426	118.16 (16)
C21—C22—C221	125.45 (16)	C422—C421—C42	122.70 (15)
C21—C22—H22	117.3	C426—C421—C42	119.14 (15)
C221—C22—H22	117.3	C423—C422—C421	121.44 (16)
C222—C221—C226	118.02 (16)	C423—C422—H422	119.3
C222—C221—C22	119.70 (15)	C421—C422—H422	119.3
C226—C221—C22	122.27 (15)	C424—C423—C422	118.73 (16)
C223—C222—C221	121.57 (16)	C424—C423—H423	120.6
C223—C222—H222	119.2	C422—C423—H423	120.6
C221—C222—H222	119.2	C425—C424—C423	121.45 (16)
C224—C223—C222	118.52 (17)	C425—C424—Cl44	118.81 (14)
C224—C223—H223	120.7	C423—C424—Cl44	119.73 (14)
C222—C223—H223	120.7	C424—C425—C426	119.11 (16)
C223—C224—C225	121.76 (16)	C424—C425—H425	120.4
C223—C224—Br24	120.44 (14)	C426—C425—H425	120.4
C225—C224—Br24	117.80 (13)	C425—C426—C421	121.10 (16)
C224—C225—C226	119.04 (16)	C425—C426—H426	119.5
C224—C225—H225	120.5	C421—C426—H426	119.5
C226—C225—H225	120.5
C8A—N1—C2—C3	−2.9 (2)	C223—C224—C225—C226	−1.6 (3)
C8A—N1—C2—C21	178.93 (14)	Br24—C224—C225—C226	177.93 (13)
N1—C2—C3—C4	4.7 (2)	C224—C225—C226—C221	0.6 (3)
C21—C2—C3—C4	−177.11 (15)	C222—C221—C226—C225	0.8 (3)
N1—C2—C3—C31	−173.35 (15)	C22—C221—C226—C225	−179.12 (16)
C21—C2—C3—C31	4.8 (2)	C4—C3—C31—O31	114.68 (19)
C2—C3—C4—C4A	−2.9 (2)	C2—C3—C31—O31	−67.3 (2)
C31—C3—C4—C4A	175.12 (15)	C4—C3—C31—C311	−68.6 (2)
C2—C3—C4—C41	176.29 (15)	C2—C3—C31—C311	109.43 (17)
C31—C3—C4—C41	−5.7 (2)	O31—C31—C311—C312	164.36 (16)
C3—C4—C4A—C5	179.71 (16)	C3—C31—C311—C312	−12.3 (2)
C41—C4—C4A—C5	0.5 (3)	O31—C31—C311—C316	−13.2 (2)
C3—C4—C4A—C8A	−0.3 (2)	C3—C31—C311—C316	170.18 (15)
C41—C4—C4A—C8A	−179.52 (15)	C316—C311—C312—C313	−0.1 (2)
C8A—C4A—C5—C6	−1.4 (3)	C31—C311—C312—C313	−177.67 (15)
C4—C4A—C5—C6	178.57 (16)	C311—C312—C313—C314	0.0 (3)
C4A—C5—C6—C7	0.7 (3)	C312—C313—C314—C315	−0.2 (3)
C5—C6—C7—C8	0.2 (3)	C313—C314—C315—C316	0.6 (3)
C6—C7—C8—C8A	−0.3 (3)	C314—C315—C316—C311	−0.7 (3)
C2—N1—C8A—C8	−179.77 (15)	C312—C311—C316—C315	0.5 (3)
C2—N1—C8A—C4A	−0.6 (2)	C31—C311—C316—C315	178.07 (16)
C7—C8—C8A—N1	178.69 (16)	C3—C4—C41—C42	−44.4 (2)
C7—C8—C8A—C4A	−0.5 (3)	C4A—C4—C41—C42	134.79 (18)
C5—C4A—C8A—N1	−177.83 (16)	C4—C41—C42—C421	178.76 (16)
C4—C4A—C8A—N1	2.2 (2)	C41—C42—C421—C422	−21.4 (3)
C5—C4A—C8A—C8	1.3 (2)	C41—C42—C421—C426	159.74 (17)
C4—C4A—C8A—C8	−178.65 (15)	C426—C421—C422—C423	−0.9 (3)
N1—C2—C21—C22	−2.6 (2)	C42—C421—C422—C423	−179.73 (17)
C3—C2—C21—C22	179.16 (16)	C421—C422—C423—C424	−0.1 (3)
C2—C21—C22—C221	178.02 (15)	C422—C423—C424—C425	1.0 (3)
C21—C22—C221—C222	−171.95 (17)	C422—C423—C424—Cl44	179.93 (14)
C21—C22—C221—C226	7.9 (3)	C423—C424—C425—C426	−0.9 (3)
C226—C221—C222—C223	−1.2 (3)	Cl44—C424—C425—C426	−179.89 (13)
C22—C221—C222—C223	178.68 (16)	C424—C425—C426—C421	0.0 (3)
C221—C222—C223—C224	0.3 (3)	C422—C421—C426—C425	0.9 (3)
C222—C223—C224—C225	1.1 (3)	C42—C421—C426—C425	179.82 (16)
C222—C223—C224—Br24	−178.35 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C225—H225···O31^i	0.95	2.37	3.266 (2)	156

Symmetry code: (i) −x+1, −y+1, −z+1.

{2-[(E)-2-(4-Bromophenyl)ethenyl]-4-[(E)-2-(thiophen-2-yl)ethenyl]quinolin-3-yl}(phenyl)methanone (IIe)

Crystal data

C30H20BrNOS	Dx = 1.481 Mg m^−3
Mr = 522.44	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 5363 reflections
a = 15.5785 (8) Å	θ = 2.1–27.5°
b = 16.4215 (7) Å	µ = 1.87 mm^−1
c = 18.3126 (9) Å	T = 100 K
V = 4684.8 (4) Å^3	Needle, yellow
Z = 8	0.20 × 0.12 × 0.08 mm
F(000) = 2128

Data collection

Bruker D8 Venture diffractometer	5363 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	4456 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.060
φ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −20→19
Tmin = 0.768, Tmax = 0.861	k = −21→19
63672 measured reflections	l = −23→23

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 11.0155P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
5363 reflections	Δρmax = 1.65 e Å^−3
320 parameters	Δρmin = −1.17 e Å^−3
10 restraints

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.32950 (13)	0.39696 (13)	0.69963 (11)	0.0180 (4)
C2	0.36313 (14)	0.47051 (14)	0.70599 (13)	0.0158 (5)
C3	0.38281 (14)	0.52091 (14)	0.64445 (13)	0.0160 (5)
C4	0.36504 (15)	0.49389 (14)	0.57424 (13)	0.0163 (5)
C4A	0.33141 (15)	0.41306 (14)	0.56663 (13)	0.0170 (5)
C5	0.31541 (16)	0.37594 (16)	0.49792 (14)	0.0214 (5)
H5	0.3277	0.4050	0.4543	0.026*
C6	0.28259 (17)	0.29886 (16)	0.49372 (14)	0.0236 (5)
H6	0.2730	0.2746	0.4473	0.028*
C7	0.26283 (17)	0.25507 (16)	0.55779 (14)	0.0236 (5)
H7	0.2379	0.2024	0.5543	0.028*
C8	0.27928 (16)	0.28802 (15)	0.62478 (14)	0.0210 (5)
H8	0.2671	0.2575	0.6676	0.025*
C8A	0.31445 (15)	0.36752 (15)	0.63117 (13)	0.0171 (5)
C21	0.37733 (15)	0.50202 (15)	0.78042 (13)	0.0179 (5)
H21	0.4008	0.5552	0.7852	0.021*
C22	0.35954 (16)	0.46108 (15)	0.84131 (13)	0.0194 (5)
H22	0.3366	0.4079	0.8356	0.023*
C221	0.37195 (16)	0.49021 (16)	0.91640 (13)	0.0204 (5)
C222	0.35708 (19)	0.43739 (17)	0.97459 (15)	0.0274 (6)
H222	0.3391	0.3832	0.9650	0.033*
C223	0.36818 (19)	0.46261 (18)	1.04677 (15)	0.0299 (6)
H223	0.3579	0.4261	1.0860	0.036*
C224	0.39418 (16)	0.54118 (17)	1.06010 (14)	0.0234 (5)
Br24	0.40941 (2)	0.57825 (2)	1.15760 (2)	0.03048 (10)
C225	0.40920 (19)	0.59520 (18)	1.00377 (15)	0.0284 (6)
H225	0.4273	0.6493	1.0137	0.034*
C226	0.39754 (18)	0.56930 (17)	0.93253 (15)	0.0269 (6)
H226	0.4073	0.6065	0.8937	0.032*
C31	0.41532 (15)	0.60611 (14)	0.65844 (12)	0.0159 (4)
O31	0.36482 (12)	0.66263 (11)	0.66219 (10)	0.0226 (4)
C311	0.50923 (15)	0.61866 (14)	0.67052 (12)	0.0161 (5)
C312	0.56445 (16)	0.55250 (15)	0.68127 (14)	0.0186 (5)
H312	0.5431	0.4985	0.6773	0.022*
C313	0.65043 (17)	0.56566 (17)	0.69773 (15)	0.0245 (5)
H313	0.6877	0.5207	0.7054	0.029*
C314	0.68187 (17)	0.64456 (17)	0.70291 (15)	0.0266 (6)
H314	0.7405	0.6534	0.7147	0.032*
C315	0.62798 (18)	0.71048 (16)	0.69097 (15)	0.0257 (6)
H315	0.6500	0.7643	0.6941	0.031*
C316	0.54200 (17)	0.69794 (15)	0.67447 (14)	0.0213 (5)
H316	0.5054	0.7432	0.6659	0.026*
C41	0.37274 (17)	0.54578 (15)	0.50877 (14)	0.0220 (5)
H41	0.3302	0.5378	0.4723	0.026*
C42	0.43069 (17)	0.60160 (17)	0.49439 (14)	0.0234 (5)
H42	0.4758	0.6081	0.5288	0.028*
S421	0.35458 (5)	0.65236 (4)	0.36256 (4)	0.0220 (2)	0.926 (3)
C422	0.43224 (18)	0.65476 (17)	0.43028 (15)	0.0260 (6)	0.926 (3)
C423	0.4861 (3)	0.7044 (3)	0.4156 (3)	0.0241 (8)	0.926 (3)
H423	0.5325	0.7140	0.4481	0.029*	0.926 (3)
C424	0.4798 (2)	0.7505 (2)	0.3465 (2)	0.0254 (7)	0.926 (3)
H424	0.5194	0.7901	0.3294	0.031*	0.926 (3)
C425	0.4069 (2)	0.72597 (18)	0.31194 (17)	0.0252 (7)	0.926 (3)
H425	0.3875	0.7465	0.2663	0.030*	0.926 (3)
S521	0.5097 (9)	0.7195 (10)	0.4125 (10)	0.0241 (8)	0.074 (3)
C522	0.43224 (18)	0.65476 (17)	0.43028 (15)	0.0260 (6)	0.074 (3)
C523	0.3793 (18)	0.647 (2)	0.3830 (13)	0.0220 (2)	0.074 (3)
H523	0.3346	0.6079	0.3856	0.026*	0.074 (3)
C524	0.389 (2)	0.704 (2)	0.3200 (15)	0.0252 (7)	0.074 (3)
H524	0.3551	0.7046	0.2770	0.030*	0.074 (3)
C525	0.456 (2)	0.755 (3)	0.336 (2)	0.0254 (7)	0.074 (3)
H525	0.4707	0.8023	0.3087	0.031*	0.074 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0142 (9)	0.0210 (10)	0.0189 (10)	0.0000 (8)	0.0003 (8)	0.0015 (8)
C2	0.0106 (10)	0.0179 (11)	0.0189 (11)	0.0024 (8)	0.0007 (8)	0.0014 (9)
C3	0.0114 (10)	0.0162 (11)	0.0203 (11)	0.0018 (9)	0.0007 (9)	−0.0005 (9)
C4	0.0133 (11)	0.0166 (11)	0.0191 (11)	0.0030 (9)	0.0012 (9)	0.0029 (9)
C4A	0.0147 (11)	0.0185 (11)	0.0177 (11)	0.0005 (9)	−0.0006 (9)	0.0005 (9)
C5	0.0230 (12)	0.0235 (12)	0.0177 (12)	−0.0020 (10)	0.0007 (10)	0.0010 (10)
C6	0.0263 (13)	0.0243 (13)	0.0202 (12)	−0.0045 (11)	0.0012 (10)	−0.0044 (10)
C7	0.0239 (13)	0.0200 (12)	0.0271 (13)	−0.0064 (10)	0.0039 (10)	−0.0033 (10)
C8	0.0184 (12)	0.0207 (12)	0.0240 (13)	−0.0037 (10)	0.0040 (10)	0.0022 (10)
C8A	0.0136 (11)	0.0190 (11)	0.0187 (11)	−0.0004 (9)	0.0012 (9)	−0.0004 (9)
C21	0.0148 (11)	0.0185 (11)	0.0203 (12)	−0.0002 (9)	−0.0007 (9)	0.0005 (9)
C22	0.0192 (12)	0.0188 (11)	0.0202 (12)	−0.0002 (9)	0.0008 (9)	−0.0004 (9)
C221	0.0161 (11)	0.0269 (13)	0.0181 (12)	0.0009 (10)	0.0013 (9)	0.0025 (10)
C222	0.0331 (15)	0.0254 (13)	0.0237 (13)	−0.0021 (11)	0.0009 (11)	0.0039 (11)
C223	0.0342 (15)	0.0340 (15)	0.0214 (13)	0.0036 (12)	0.0008 (11)	0.0091 (11)
C224	0.0185 (12)	0.0344 (14)	0.0174 (12)	0.0052 (10)	−0.0011 (9)	0.0009 (10)
Br24	0.02658 (15)	0.04757 (19)	0.01730 (14)	0.00720 (12)	−0.00317 (10)	−0.00200 (11)
C225	0.0321 (15)	0.0297 (14)	0.0234 (13)	−0.0051 (12)	−0.0009 (11)	−0.0013 (11)
C226	0.0343 (15)	0.0280 (14)	0.0184 (12)	−0.0048 (11)	0.0020 (11)	0.0024 (10)
C31	0.0193 (11)	0.0155 (11)	0.0128 (10)	0.0016 (9)	0.0012 (9)	0.0018 (8)
O31	0.0252 (9)	0.0189 (9)	0.0236 (9)	0.0081 (7)	−0.0018 (7)	−0.0016 (7)
C311	0.0181 (11)	0.0170 (11)	0.0131 (11)	−0.0015 (9)	0.0019 (9)	0.0004 (9)
C312	0.0188 (11)	0.0153 (11)	0.0217 (12)	−0.0006 (9)	0.0013 (9)	0.0002 (9)
C313	0.0187 (12)	0.0285 (14)	0.0263 (13)	0.0007 (10)	−0.0022 (10)	−0.0001 (11)
C314	0.0207 (13)	0.0358 (15)	0.0233 (13)	−0.0094 (11)	−0.0002 (10)	−0.0038 (11)
C315	0.0313 (14)	0.0232 (13)	0.0227 (13)	−0.0119 (11)	0.0036 (11)	−0.0042 (10)
C316	0.0299 (13)	0.0149 (11)	0.0190 (12)	−0.0014 (10)	0.0042 (10)	−0.0024 (9)
C41	0.0274 (13)	0.0191 (12)	0.0195 (12)	0.0049 (10)	0.0005 (10)	−0.0006 (10)
C42	0.0255 (13)	0.0256 (13)	0.0191 (12)	0.0045 (10)	0.0004 (10)	−0.0006 (10)
S421	0.0248 (4)	0.0210 (3)	0.0200 (4)	0.0039 (3)	−0.0026 (3)	0.0021 (3)
C422	0.0310 (15)	0.0255 (13)	0.0214 (13)	0.0130 (12)	0.0010 (11)	−0.0028 (11)
C423	0.021 (2)	0.031 (2)	0.0194 (12)	0.0092 (17)	−0.0008 (18)	−0.0012 (14)
C424	0.0302 (18)	0.0221 (13)	0.0240 (16)	0.0075 (14)	0.0074 (13)	0.0057 (11)
C425	0.0382 (18)	0.0166 (16)	0.0209 (13)	0.0095 (13)	0.0112 (13)	0.0099 (11)
S521	0.021 (2)	0.031 (2)	0.0194 (12)	0.0092 (17)	−0.0008 (18)	−0.0012 (14)
C522	0.0310 (15)	0.0255 (13)	0.0214 (13)	0.0130 (12)	0.0010 (11)	−0.0028 (11)
C523	0.0248 (4)	0.0210 (3)	0.0200 (4)	0.0039 (3)	−0.0026 (3)	0.0021 (3)
C524	0.0382 (18)	0.0166 (16)	0.0209 (13)	0.0095 (13)	0.0112 (13)	0.0099 (11)
C525	0.0302 (18)	0.0221 (13)	0.0240 (16)	0.0075 (14)	0.0074 (13)	0.0057 (11)

Geometric parameters (Å, º)

N1—C2	1.322 (3)	C226—H226	0.9500
N1—C8A	1.364 (3)	C31—O31	1.219 (3)
C2—C3	1.431 (3)	C31—C311	1.494 (3)
C2—C21	1.475 (3)	C311—C312	1.400 (3)
C3—C4	1.388 (3)	C311—C316	1.400 (3)
C3—C31	1.510 (3)	C312—C313	1.390 (4)
C4—C4A	1.434 (3)	C312—H312	0.9500
C4—C41	1.476 (3)	C313—C314	1.388 (4)
C4A—C5	1.420 (3)	C313—H313	0.9500
C4A—C8A	1.423 (3)	C314—C315	1.387 (4)
C5—C6	1.367 (4)	C314—H314	0.9500
C5—H5	0.9500	C315—C316	1.388 (4)
C6—C7	1.410 (4)	C315—H315	0.9500
C6—H6	0.9500	C316—H316	0.9500
C7—C8	1.365 (4)	C41—C42	1.313 (4)
C7—H7	0.9500	C41—H41	0.9500
C8—C8A	1.421 (3)	C42—C422	1.463 (4)
C8—H8	0.9500	C42—H42	0.9500
C21—C22	1.331 (3)	S421—C425	1.728 (3)
C21—H21	0.9500	S421—C422	1.733 (3)
C22—C221	1.469 (3)	C422—C423	1.201 (5)
C22—H22	0.9500	C423—C424	1.476 (5)
C221—C226	1.390 (4)	C423—H423	0.9500
C221—C222	1.393 (4)	C424—C425	1.361 (5)
C222—C223	1.396 (4)	C424—H424	0.9500
C222—H222	0.9500	C425—H425	0.9500
C223—C224	1.374 (4)	S521—C525	1.738 (10)
C223—H223	0.9500	C523—C524	1.492 (11)
C224—C225	1.381 (4)	C523—H523	0.9500
C224—Br24	1.901 (3)	C524—C525	1.366 (11)
C225—C226	1.384 (4)	C524—H524	0.9500
C225—H225	0.9500	C525—H525	0.9500
C2—N1—C8A	118.2 (2)	C225—C226—H226	119.2
N1—C2—C3	122.9 (2)	C221—C226—H226	119.2
N1—C2—C21	117.5 (2)	O31—C31—C311	121.3 (2)
C3—C2—C21	119.5 (2)	O31—C31—C3	119.9 (2)
C4—C3—C2	120.1 (2)	C311—C31—C3	118.8 (2)
C4—C3—C31	121.4 (2)	C312—C311—C316	119.4 (2)
C2—C3—C31	118.3 (2)	C312—C311—C31	121.0 (2)
C3—C4—C4A	117.3 (2)	C316—C311—C31	119.5 (2)
C3—C4—C41	123.5 (2)	C313—C312—C311	120.1 (2)
C4A—C4—C41	119.0 (2)	C313—C312—H312	119.9
C5—C4A—C8A	118.5 (2)	C311—C312—H312	119.9
C5—C4A—C4	123.2 (2)	C314—C313—C312	120.0 (3)
C8A—C4A—C4	118.3 (2)	C314—C313—H313	120.0
C6—C5—C4A	120.9 (2)	C312—C313—H313	120.0
C6—C5—H5	119.6	C315—C314—C313	120.3 (2)
C4A—C5—H5	119.6	C315—C314—H314	119.9
C5—C6—C7	120.4 (2)	C313—C314—H314	119.9
C5—C6—H6	119.8	C314—C315—C316	120.2 (2)
C7—C6—H6	119.8	C314—C315—H315	119.9
C8—C7—C6	120.3 (2)	C316—C315—H315	119.9
C8—C7—H7	119.8	C315—C316—C311	120.1 (2)
C6—C7—H7	119.8	C315—C316—H316	120.0
C7—C8—C8A	120.7 (2)	C311—C316—H316	120.0
C7—C8—H8	119.6	C42—C41—C4	128.5 (2)
C8A—C8—H8	119.6	C42—C41—H41	115.8
N1—C8A—C8	117.9 (2)	C4—C41—H41	115.8
N1—C8A—C4A	123.0 (2)	C41—C42—C422	126.1 (3)
C8—C8A—C4A	119.1 (2)	C41—C42—H42	117.0
C22—C21—C2	124.5 (2)	C422—C42—H42	117.0
C22—C21—H21	117.8	C425—S421—C422	92.22 (15)
C2—C21—H21	117.8	C423—C422—C42	126.6 (3)
C21—C22—C221	126.3 (2)	C423—C422—S421	110.1 (3)
C21—C22—H22	116.8	C42—C422—S421	123.3 (2)
C221—C22—H22	116.8	C422—C423—C424	119.5 (4)
C226—C221—C222	117.8 (2)	C422—C423—H423	120.2
C226—C221—C22	122.7 (2)	C424—C423—H423	120.2
C222—C221—C22	119.4 (2)	C425—C424—C423	107.7 (3)
C221—C222—C223	121.3 (3)	C425—C424—H424	126.2
C221—C222—H222	119.4	C423—C424—H424	126.2
C223—C222—H222	119.4	C424—C425—S421	110.5 (2)
C224—C223—C222	118.9 (3)	C424—C425—H425	124.7
C224—C223—H223	120.6	S421—C425—H425	124.7
C222—C223—H223	120.6	C524—C523—H523	122.5
C223—C224—C225	121.4 (3)	C525—C524—C523	107.4 (11)
C223—C224—Br24	120.3 (2)	C525—C524—H524	126.3
C225—C224—Br24	118.3 (2)	C523—C524—H524	126.3
C224—C225—C226	119.0 (3)	C524—C525—S521	109.4 (10)
C224—C225—H225	120.5	C524—C525—H525	125.3
C226—C225—H225	120.5	S521—C525—H525	125.3
C225—C226—C221	121.7 (3)
C8A—N1—C2—C3	1.2 (3)	C222—C223—C224—Br24	179.6 (2)
C8A—N1—C2—C21	178.8 (2)	C223—C224—C225—C226	0.1 (4)
N1—C2—C3—C4	1.3 (3)	Br24—C224—C225—C226	−179.4 (2)
C21—C2—C3—C4	−176.2 (2)	C224—C225—C226—C221	−0.6 (4)
N1—C2—C3—C31	175.8 (2)	C222—C221—C226—C225	0.8 (4)
C21—C2—C3—C31	−1.7 (3)	C22—C221—C226—C225	−179.7 (3)
C2—C3—C4—C4A	−3.4 (3)	C4—C3—C31—O31	82.8 (3)
C31—C3—C4—C4A	−177.7 (2)	C2—C3—C31—O31	−91.6 (3)
C2—C3—C4—C41	171.8 (2)	C4—C3—C31—C311	−99.7 (3)
C31—C3—C4—C41	−2.5 (4)	C2—C3—C31—C311	85.9 (3)
C3—C4—C4A—C5	−176.0 (2)	O31—C31—C311—C312	166.6 (2)
C41—C4—C4A—C5	8.6 (4)	C3—C31—C311—C312	−10.9 (3)
C3—C4—C4A—C8A	3.1 (3)	O31—C31—C311—C316	−10.5 (3)
C41—C4—C4A—C8A	−172.3 (2)	C3—C31—C311—C316	172.1 (2)
C8A—C4A—C5—C6	1.5 (4)	C316—C311—C312—C313	1.8 (4)
C4—C4A—C5—C6	−179.5 (2)	C31—C311—C312—C313	−175.3 (2)
C4A—C5—C6—C7	0.9 (4)	C311—C312—C313—C314	−0.6 (4)
C5—C6—C7—C8	−2.5 (4)	C312—C313—C314—C315	−0.7 (4)
C6—C7—C8—C8A	1.6 (4)	C313—C314—C315—C316	0.6 (4)
C2—N1—C8A—C8	179.2 (2)	C314—C315—C316—C311	0.6 (4)
C2—N1—C8A—C4A	−1.5 (3)	C312—C311—C316—C315	−1.8 (4)
C7—C8—C8A—N1	−179.9 (2)	C31—C311—C316—C315	175.3 (2)
C7—C8—C8A—C4A	0.8 (4)	C3—C4—C41—C42	37.6 (4)
C5—C4A—C8A—N1	178.5 (2)	C4A—C4—C41—C42	−147.3 (3)
C4—C4A—C8A—N1	−0.7 (3)	C4—C41—C42—C422	−176.1 (2)
C5—C4A—C8A—C8	−2.3 (3)	C41—C42—C422—C423	−177.8 (4)
C4—C4A—C8A—C8	178.6 (2)	C41—C42—C422—S421	0.8 (4)
N1—C2—C21—C22	0.8 (4)	C425—S421—C422—C423	1.1 (3)
C3—C2—C21—C22	178.5 (2)	C425—S421—C422—C42	−177.7 (2)
C2—C21—C22—C221	−179.5 (2)	C42—C422—C423—C424	177.2 (3)
C21—C22—C221—C226	6.0 (4)	S421—C422—C423—C424	−1.6 (5)
C21—C22—C221—C222	−174.5 (3)	C422—C423—C424—C425	1.4 (6)
C226—C221—C222—C223	−0.5 (4)	C423—C424—C425—S421	−0.4 (4)
C22—C221—C222—C223	180.0 (3)	C422—S421—C425—C424	−0.3 (3)
C221—C222—C223—C224	0.1 (4)	C523—C524—C525—S521	10 (6)
C222—C223—C224—C225	0.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O31^i	0.95	2.58	3.122 (3)	116
C425—H425···O31^ii	0.95	2.45	3.361 (4)	161
C5—H5···Cg3^iii	0.95	2.90	3.647 (3)	136
C423—H423···Cg2^iv	0.95	2.76	3.449 (3)	130

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y+3/2, −z+3/2; (iv) −x+1, −y+1, −z+1.