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and Hirshfeld surface analysis of 1-[6-bromo-2-(3-bromophenyl)-1,2,3,4-tetrahydroquinolin-4-yl]pyrrolidin-2-one
aRUDN University, 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation, bFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskiy prospect 31-4, Moscow 119071, Russian Federation, cWestern Caspian University, Istiqlaliyyat Street 31, AZ1001, Baku, Azerbaijan, dAzerbaijan Medical University, Scientific Research Centre (SRC), A. Kasumzade St. 14. AZ 1022, Baku, Azerbaijan, eDepartment of Chemistry, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan, fDepartment of Chemistry and Chemical Engineering, Khazar University, Mahsati St. 41, AZ 1096, Baku, Azerbaijan, gDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, and hDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np
This study presents the synthesis, characterization and Hirshfeld surface analysis of 1-[6-bromo-2-(3-bromophenyl)-1,2,3,4-tetrahydroquinolin-4-yl]pyrrolidin-2-one, C19H18Br2N2O. In the title compound, the pyrrolidine ring adopts a distorted envelope configuration. In the crystal, molecules are linked by intermolecular N—H⋯O, C—H⋯O and C—H⋯Br hydrogen bonds, forming a three-dimensional network. In addition, pairs of molecules along the c axis are connected by C—H⋯π interactions. According to a Hirshfeld surface study, H⋯H (36.9%), Br⋯H/H⋯Br (28.2%) and C⋯H/H⋯C (24.3%) interactions are the most significant contributors to the crystal packing.
Keywords: crystal structure; hydrogen bonds; the Povarov method; tetrahydroquinoline; Hirshfeld surface analysis.
CCDC reference: 2378018
1. Chemical context
Currently, a large number of derivatives of known tetrahydroquinolines are promising candidates for testing against various types of biological activity. This class of N-heterocyclic compounds has attracted attention of biochemists for the past 50 years, as derivatives of the tetrahydroquinoline frame possess antibacterial, antitumor, and antiallergic properties. Some are already used as medicinal agents (Ghashghaei et al., 2018).
In this regard, the synthesis and modification of the tetrahydroquinoline system to search for new drugs is an important task in organic chemistry. Over the years, several synthetic routes have been developed to obtain variously substituted tetrahydroquinolines (Sridharan et al., 2011). However, the advantage remains with the Povarov reaction, due to the flexibility of this method, allowing the one-step synthesis of variously substituted 1,2,3,4-tetrahydroquinolines (Zubkov et al., 2007
, 2010
; Kouznetsov, 2009
; Varma et al., 2010
; Zaytsev et al., 2013
). Furthermore, the Povarov reaction is characterized by good yields and mild reaction conditions. Usually the reaction proceeds in two stages. The first stage is an aza-Diels–Alder reaction between N-arylimine and an electron-rich olefin in the presence of catalytic amounts of which leads to the formation of a cycloadduct. The second stage involves a 1,3-H shift in the cycloadduct and results in the formation of the tetrahydroquinoline moiety.
In this work, the synthesis of the corresponding azomethine 3 was carried out using a condensation reaction between 4-bromoaniline (1) and 3-bromobenzaldehyde (2) to form product 3, which was then introduced into the Povarov reaction. N-Vinylpyrrolidin-2-one was used as the alkene, and boron trifluoride etherate served as the (Fig. 1).
![]() | Figure 1 Synthesis of 1-[6-bromo-2-(3-bromophenyl)-1,2,3,4-tetrahydroquinolin-4-yl]pyrrolidin-2-one (4). |
Thus, the Povarov method provides a convenient approach for the one-pot synthesis of substituted, partially hydrogenated quinolines and medicinal preparations based on the tetrahydroquinoline frame. Some stereochemical features of the resulting adduct 4 are discussed in this work. This work also discusses some stereochemical features of the resulting adduct 4.
2. Structural commentary
In the title compound (Fig. 2), the 1,2,3,4-tetrahydropyridine ring (N1/C2–C4/C4A/C8A) of the 1,2,3,4-tetrahydroquinoline ring system (N1/C2–C4/C4A/C5–C8/C8A) adopts an [the puckering parameters (Cremer & Pople, 1975
) are QT = 0.523 (2) Å, θ = 131.7 (2)°, φ = 300.9 (3)°], while the benzene ring (C4A/C5–C8/C8A) is essentially planar (r.m.s. deviation = 0.002 Å). The plane (r.m.s deviation = 0.002 Å) of the 1,2,3,4-tetrahydroquinoline ring system forms angles of 56.85 (9) and 83.05 (10)°, respectively, with the bromobenzene ring (C21–C26) and the pyrrolidine ring (N11/ C12–C15; r.m.s deviation = 0.002 Å), which has a distorted [the puckering parameters are Q(2) = 0.225 (2) Å, φ(2) = 117.2 (6)°]. The angle between the pyrrolidine and bromobenzene rings is 84.92 (12)°. The geometric parameters in the molecule are normal and in good agreement with those in the compounds discussed in the Database survey (section 4).
![]() | Figure 2 View of the title molecule. Displacement ellipsoids are drawn at the 50% probability level. |
3. Supramolecular features and Hirshfeld surface analysis
In the crystal, molecules are linked by intermolecular N—H⋯O, C—H⋯O and C—H⋯Br hydrogen bonds, forming a three-dimensional network (Table 1; Figs. 3
, 4
and 5
). In addition, pairs of molecules along the c axis are connected by C—H⋯π interactions (Table 1
; Figs. 6
, 7
and 8
). To quantify the intermolecular interactions in the crystal, the Hirshfeld surfaces of the title molecule and the two-dimensional fingerprints were generated with CrystalExplorer17.5 (Spackman et al., 2021
). On the dnorm surfaces, bright-red spots show the locations of the N—H⋯O, C—H⋯O and C—H⋯Br interactions (Table 1
; Fig. 9
a,b). The overall two-dimensional fingerprint plot for the title compound and those delineated into H⋯H (Fig. 10
b; 36.9%), Br⋯H/H⋯Br (Fig. 10
c; 28.2%) and C⋯H/H⋯C (Fig. 10
d; 24.3%) contacts are shown in Fig. 10
. O⋯H/H⋯O (7.1%), Br⋯O/O⋯Br (1.8%), Br⋯C/C⋯Br (0.9%), N⋯H/H⋯N (0.4%) and Br⋯N/N⋯Br (0.3%) contacts have little directional influence on the molecular packing.
|
![]() | Figure 3 A view of the molecular packing along the a axis of the title compound, showing the N—H⋯O, C—H⋯O and C—H⋯Br hydrogen bonds as dashed lines. |
![]() | Figure 4 A view of the molecular packing along the b axis of the title compound. |
![]() | Figure 5 A view of the molecular packing along the c axis of the title compound. |
![]() | Figure 6 A view of the molecular packing along the a axis of the title compound, showing the C—H⋯π interactions. |
![]() | Figure 7 A view of the molecular packing along the b axis of the title compound. |
![]() | Figure 8 A view of the molecular packing along the c axis of the title compound. |
![]() | Figure 9 (a) Front and (b) back views of the three-dimensional Hirshfeld surface for the title compound. Some N—H⋯O, C—H⋯O and C—H⋯Br interactions are shown as dashed lines. |
![]() | Figure 10 The two-dimensional fingerprint plots for the title compound showing (a) all interactions, and delineated into (b) H⋯H, (c) Br⋯H/H⋯Br and (d) C⋯H/H⋯C interactions. The di and de values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface. |
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016) for similar structures with the 1,2,3,4-tetrahydroquinoline unit showed that the seven most closely related to the title compound are refcodes POSWAZ (Pronina et al., 2024
), EZOMIR (Çelik et al., 2016
), SUFDEE (Jeyaseelan, et al., 2015c
), NOVGAI (Jeyaseelan et al., 2015a
), WUFBEG (Jeyaseelan et al., 2015b
), WACWOO (Çelik et al., 2010a
) and CEDNUW (Çelik et al., 2010b
).
In the crystal of POSWAZ, molecules are linked by intermolecular N—H⋯O, C—H⋯O, C—H⋯F and C—H⋯Br hydrogen bonds, forming a three-dimensional network. In addition, C—H⋯π interactions connect molecules into ribbons along the b-axis direction, consolidating the molecular packing. In the crystal of EZOMIR, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R22(12) loops. In the crystal of SUFDEE, molecules are linked by weak C—H⋯O hydrogen bonds, generating C(8) and C(4) chains propagating along [100] and [010], respectively, which together generate (001) sheets. In the crystal of NOVGAI, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R22(8) loops. In the crystal of WUFBEG, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R22(10) loops. Additional intermolecular C—H⋯O hydrogen bonds generate C(7) chains along [100]. The of WACWOO is stabilized by weak aromatic π–π interactions [centroid–centroid distance = 3.802 (4) Å] between the pyridine and benzene rings of the quinoline ring systems of adjacent molecules. In the crystal of CEDNUW, π–π stacking interactions are present between the pyridine and benzene rings of adjacent molecules [centroid–centroid distances = 3.634 (4) Å], and short Br⋯Br contacts [3.4443 (13) Å] occur.
5. Synthesis and crystallization
N-[(E)-(3-Bromophenyl)methylidene]-4-bromoaniline (3): A mixture of 4-bromoaniline (1) (2.00 g, 0.012 mol), 3-bromobenzaldehyde (2) (2.22 g, 0.012 mol) and anhydrous MgSO4 (2.89 g, 0.024 mol) was stirred in CH2Cl2 (40 mL) for 24 h at room temperature. Then, the reaction mixture was passed through a silica gel layer (2 × 3 cm) (eluent CH2Cl2) and the solvent was evaporated under reduced pressure. Compound 3 was isolated as a yellow powder in 87% yield (3.54 g).
1-(6-Bromo-2-(3-bromophenyl)-1,2,3,4-tetrahydroquinolin-4-yl)pyrrolidin-2-one (4): Boron trifluoride ether (0.25 mL, 0.002 mol) and N-vinylpyrrolidin-2-one (1.18 mL, 0.011 mol) were added sequentially to a solution of the azomethine (3) (3.5 g, 0.010 mol) in freshly distilled CH2Cl2 (30 mL), under cooling (275–277 K) and constant stirring. The reaction was monitored by TLC (EtOAc/hexane, 1:2). After the reaction was complete (∼24 h), the reaction mixture was treated with a small amount of water (0.2–0.3 mL) to decompose the catalyst. Then the resulting mixture was passed through a layer of silica gel (2 × 3 cm) and washed with dry CH2Cl2 (2 × 25 mL). The solvent was evaporated under reduced pressure. The obtained precipitate was recrystallized from a mixture of hexane/EtOAc. The desired product, 4, was isolated as a white microcrystalline precipitate in 39% yield (1.76 g), m.p. 470.3–471.8 K. IR (KBr), ν (cm−1): 3344 (NH), 2951 (Ph), 2889 (Ph), 1667 (N—C=O). 1H NMR (700.2 MHz, CDCl3, 298 K) (J, Hz): δ 2.01–2.10 (m, 4H, H-3 + H-4-pyrrole), 2.43–2.48 (m, 1H, H-3-pyrrole-A), 2.52–2.57 (m, 1H, H-3-pyrrole-B), 3.19–3.26 (m, 2H, H-5-pyrrole), 4.07 (s, 1H, NH), 4.54 (dd, J = 11.2, J = 2.9, 1H, H-2), 5.66 (dd, J = 11.7, J = 6.0 Hz, 1H, H-4), 6.49 (d, J = 8.6, 1H, H-8), 6.95 (s, 1H, H-5), 7.15 (dd, J = 8.6, J = 2.2, 1H, H-7), 7.24 (t, J = 7.9, 1H, H-5-C6H4-Br), 7.31 (d, J = 7.6, 1H, H-6-C6H4-Br), 7.45 (d, J = 7.9, 1H, H-4-C6H4-Br), 7.61 (s, 1H, H-2-C6H4-Br) ppm. 13C{1H} NMR (176 MHz, CDCl3, 298 K): δ 18.00, 31.00, 34.58, 42.03, 47.79, 55.60, 109.93, 116.48, 120.73, 122.71, 125.08, 128.93, 129.17, 130.20, 130.95, 131.00, 144.33, 144.69, 175.66 ppm.
Elemental analysis calculated (%) for C19H18Br2N2O: C, 50.69; H, 4.03; N, 6.22; found: C, 50.61; H, 3.94; N, 6.42.
Single crystals (splices of prisms) of compound 4 were grown from a mixture of hexane and ethyl acetate (∼3:1).
6. Refinement
Crystal data, data collection and structure . The C-bound H atoms were placed in calculated positions (0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The N-bound H atom was located in a difference map and freely refined.
|
Supporting information
CCDC reference: 2378018
https://doi.org/10.1107/S2056989024008144/nx2012sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024008144/nx2012Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989024008144/nx2012Isup3.cml
C19H18Br2N2O | F(000) = 896 |
Mr = 450.17 | Dx = 1.694 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8691 (8) Å | Cell parameters from 5029 reflections |
b = 9.4578 (7) Å | θ = 2.9–26.4° |
c = 17.7217 (14) Å | µ = 4.60 mm−1 |
β = 104.364 (3)° | T = 100 K |
V = 1764.8 (2) Å3 | Bulk, colourless |
Z = 4 | 0.36 × 0.32 × 0.26 mm |
Bruker Kappa APEXII area-detector diffractometer | 3231 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.054 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | θmax = 27.5°, θmin = 4.2° |
Tmin = 0.714, Tmax = 1.000 | h = −13→14 |
25906 measured reflections | k = −11→12 |
4041 independent reflections | l = −23→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.0176P)2 + 1.5651P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
4041 reflections | Δρmax = 0.47 e Å−3 |
220 parameters | Δρmin = −0.47 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C2 | 0.3972 (2) | 0.7031 (2) | 0.42197 (14) | 0.0095 (5) | |
H2 | 0.417106 | 0.695439 | 0.480026 | 0.011* | |
C3 | 0.5184 (2) | 0.7407 (2) | 0.39791 (14) | 0.0103 (5) | |
H3A | 0.551079 | 0.833284 | 0.420260 | 0.012* | |
H3B | 0.500982 | 0.746994 | 0.340468 | 0.012* | |
C4 | 0.6161 (2) | 0.6251 (2) | 0.42821 (14) | 0.0090 (5) | |
H4A | 0.623691 | 0.617392 | 0.485461 | 0.011* | |
C4A | 0.5649 (2) | 0.4840 (2) | 0.39280 (14) | 0.0103 (5) | |
C5 | 0.6438 (2) | 0.3756 (2) | 0.37979 (14) | 0.0116 (5) | |
H5A | 0.732382 | 0.391768 | 0.387756 | 0.014* | |
C6 | 0.5933 (2) | 0.2444 (2) | 0.35526 (14) | 0.0141 (5) | |
C7 | 0.4649 (2) | 0.2184 (2) | 0.34323 (14) | 0.0153 (5) | |
H7A | 0.431556 | 0.127113 | 0.327685 | 0.018* | |
C8 | 0.3852 (2) | 0.3264 (2) | 0.35403 (14) | 0.0141 (5) | |
H8A | 0.296550 | 0.309470 | 0.344583 | 0.017* | |
C8A | 0.4337 (2) | 0.4609 (2) | 0.37876 (14) | 0.0099 (5) | |
C12 | 0.8464 (2) | 0.6433 (2) | 0.47857 (15) | 0.0108 (5) | |
C13 | 0.9605 (2) | 0.6920 (2) | 0.45130 (16) | 0.0164 (6) | |
H13A | 1.014249 | 0.610573 | 0.444761 | 0.020* | |
H13B | 1.012448 | 0.759132 | 0.488933 | 0.020* | |
C14 | 0.9045 (2) | 0.7642 (2) | 0.37321 (16) | 0.0183 (6) | |
H14A | 0.954217 | 0.740510 | 0.335083 | 0.022* | |
H14B | 0.903707 | 0.868151 | 0.379516 | 0.022* | |
C15 | 0.7689 (2) | 0.7064 (2) | 0.34649 (15) | 0.0140 (5) | |
H15A | 0.708860 | 0.781053 | 0.321194 | 0.017* | |
H15B | 0.764491 | 0.626563 | 0.309794 | 0.017* | |
C21 | 0.2979 (2) | 0.8177 (2) | 0.39562 (14) | 0.0098 (5) | |
C22 | 0.2170 (2) | 0.8162 (2) | 0.32186 (14) | 0.0108 (5) | |
H22 | 0.219100 | 0.739884 | 0.287317 | 0.013* | |
C23 | 0.1327 (2) | 0.9274 (2) | 0.29887 (14) | 0.0113 (5) | |
C24 | 0.1280 (2) | 1.0400 (2) | 0.34733 (16) | 0.0176 (6) | |
H24 | 0.070147 | 1.115604 | 0.330570 | 0.021* | |
C25 | 0.2095 (3) | 1.0404 (3) | 0.42109 (17) | 0.0207 (6) | |
H25 | 0.207518 | 1.117252 | 0.455296 | 0.025* | |
C26 | 0.2935 (2) | 0.9304 (2) | 0.44550 (15) | 0.0157 (5) | |
H26 | 0.348384 | 0.931566 | 0.496389 | 0.019* | |
N1 | 0.35049 (19) | 0.5666 (2) | 0.38807 (12) | 0.0121 (4) | |
H1 | 0.283 (3) | 0.538 (3) | 0.3999 (15) | 0.014* | |
N11 | 0.74188 (18) | 0.65967 (19) | 0.41920 (12) | 0.0105 (4) | |
O1 | 0.84580 (15) | 0.59639 (17) | 0.54316 (10) | 0.0153 (4) | |
Br1 | 0.70318 (3) | 0.09579 (2) | 0.34029 (2) | 0.02171 (8) | |
Br2 | 0.01897 (2) | 0.91972 (2) | 0.19816 (2) | 0.01641 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C2 | 0.0097 (12) | 0.0106 (11) | 0.0073 (13) | 0.0004 (9) | 0.0003 (9) | 0.0003 (9) |
C3 | 0.0121 (12) | 0.0083 (10) | 0.0106 (13) | 0.0009 (9) | 0.0031 (10) | 0.0009 (9) |
C4 | 0.0072 (11) | 0.0102 (10) | 0.0097 (13) | 0.0008 (8) | 0.0025 (9) | 0.0018 (9) |
C4A | 0.0143 (13) | 0.0078 (10) | 0.0088 (13) | 0.0014 (9) | 0.0031 (10) | 0.0028 (9) |
C5 | 0.0144 (13) | 0.0126 (11) | 0.0092 (13) | 0.0020 (9) | 0.0052 (10) | 0.0031 (9) |
C6 | 0.0222 (14) | 0.0103 (11) | 0.0114 (13) | 0.0063 (10) | 0.0073 (11) | 0.0023 (10) |
C7 | 0.0257 (15) | 0.0089 (11) | 0.0098 (14) | −0.0016 (10) | 0.0016 (11) | −0.0014 (9) |
C8 | 0.0156 (13) | 0.0135 (11) | 0.0120 (14) | −0.0024 (10) | 0.0011 (10) | 0.0017 (10) |
C8A | 0.0132 (13) | 0.0106 (10) | 0.0059 (12) | 0.0003 (9) | 0.0021 (10) | 0.0031 (9) |
C12 | 0.0106 (12) | 0.0065 (10) | 0.0149 (14) | 0.0024 (9) | 0.0023 (10) | −0.0036 (9) |
C13 | 0.0094 (13) | 0.0146 (12) | 0.0248 (16) | 0.0010 (9) | 0.0034 (11) | −0.0036 (10) |
C14 | 0.0140 (13) | 0.0136 (12) | 0.0302 (17) | 0.0008 (10) | 0.0111 (12) | 0.0043 (11) |
C15 | 0.0152 (13) | 0.0117 (11) | 0.0170 (14) | 0.0037 (9) | 0.0074 (11) | 0.0025 (10) |
C21 | 0.0079 (12) | 0.0109 (11) | 0.0117 (13) | −0.0005 (9) | 0.0047 (10) | 0.0021 (9) |
C22 | 0.0110 (12) | 0.0115 (11) | 0.0107 (13) | −0.0001 (9) | 0.0044 (10) | −0.0009 (9) |
C23 | 0.0081 (11) | 0.0128 (11) | 0.0117 (13) | −0.0021 (9) | 0.0003 (9) | 0.0032 (10) |
C24 | 0.0131 (13) | 0.0112 (11) | 0.0283 (17) | 0.0045 (9) | 0.0047 (11) | 0.0039 (10) |
C25 | 0.0245 (15) | 0.0128 (12) | 0.0253 (16) | 0.0015 (10) | 0.0074 (12) | −0.0068 (11) |
C26 | 0.0163 (13) | 0.0188 (12) | 0.0098 (13) | −0.0004 (10) | −0.0009 (10) | −0.0013 (10) |
N1 | 0.0070 (10) | 0.0101 (9) | 0.0194 (12) | −0.0008 (8) | 0.0036 (9) | −0.0001 (8) |
N11 | 0.0100 (10) | 0.0113 (9) | 0.0106 (11) | 0.0010 (8) | 0.0030 (8) | 0.0012 (8) |
O1 | 0.0141 (9) | 0.0190 (9) | 0.0112 (9) | 0.0034 (7) | 0.0001 (7) | −0.0003 (7) |
Br1 | 0.03536 (17) | 0.01082 (12) | 0.02535 (16) | 0.00804 (11) | 0.01967 (13) | 0.00283 (11) |
Br2 | 0.01226 (13) | 0.01562 (12) | 0.01764 (15) | −0.00140 (10) | −0.00331 (10) | 0.00727 (10) |
C2—N1 | 1.460 (3) | C12—C13 | 1.511 (3) |
C2—C21 | 1.519 (3) | C13—C14 | 1.528 (4) |
C2—C3 | 1.524 (3) | C13—H13A | 0.9900 |
C2—H2 | 1.0000 | C13—H13B | 0.9900 |
C3—C4 | 1.526 (3) | C14—C15 | 1.532 (3) |
C3—H3A | 0.9900 | C14—H14A | 0.9900 |
C3—H3B | 0.9900 | C14—H14B | 0.9900 |
C4—N11 | 1.453 (3) | C15—N11 | 1.459 (3) |
C4—C4A | 1.520 (3) | C15—H15A | 0.9900 |
C4—H4A | 1.0000 | C15—H15B | 0.9900 |
C4A—C5 | 1.392 (3) | C21—C22 | 1.383 (3) |
C4A—C8A | 1.402 (3) | C21—C26 | 1.393 (3) |
C5—C6 | 1.383 (3) | C22—C23 | 1.389 (3) |
C5—H5A | 0.9500 | C22—H22 | 0.9500 |
C6—C7 | 1.380 (4) | C23—C24 | 1.376 (3) |
C6—Br1 | 1.905 (2) | C23—Br2 | 1.903 (2) |
C7—C8 | 1.383 (3) | C24—C25 | 1.385 (4) |
C7—H7A | 0.9500 | C24—H24 | 0.9500 |
C8—C8A | 1.404 (3) | C25—C26 | 1.381 (3) |
C8—H8A | 0.9500 | C25—H25 | 0.9500 |
C8A—N1 | 1.386 (3) | C26—H26 | 0.9500 |
C12—O1 | 1.229 (3) | N1—H1 | 0.86 (3) |
C12—N11 | 1.352 (3) | ||
N1—C2—C21 | 110.84 (19) | C14—C13—H13A | 110.8 |
N1—C2—C3 | 109.13 (19) | C12—C13—H13B | 110.8 |
C21—C2—C3 | 110.18 (18) | C14—C13—H13B | 110.8 |
N1—C2—H2 | 108.9 | H13A—C13—H13B | 108.9 |
C21—C2—H2 | 108.9 | C13—C14—C15 | 104.92 (19) |
C3—C2—H2 | 108.9 | C13—C14—H14A | 110.8 |
C2—C3—C4 | 107.97 (18) | C15—C14—H14A | 110.8 |
C2—C3—H3A | 110.1 | C13—C14—H14B | 110.8 |
C4—C3—H3A | 110.1 | C15—C14—H14B | 110.8 |
C2—C3—H3B | 110.1 | H14A—C14—H14B | 108.8 |
C4—C3—H3B | 110.1 | N11—C15—C14 | 102.9 (2) |
H3A—C3—H3B | 108.4 | N11—C15—H15A | 111.2 |
N11—C4—C4A | 114.22 (19) | C14—C15—H15A | 111.2 |
N11—C4—C3 | 113.07 (18) | N11—C15—H15B | 111.2 |
C4A—C4—C3 | 109.42 (19) | C14—C15—H15B | 111.2 |
N11—C4—H4A | 106.5 | H15A—C15—H15B | 109.1 |
C4A—C4—H4A | 106.5 | C22—C21—C26 | 119.6 (2) |
C3—C4—H4A | 106.5 | C22—C21—C2 | 121.3 (2) |
C5—C4A—C8A | 119.8 (2) | C26—C21—C2 | 119.0 (2) |
C5—C4A—C4 | 122.5 (2) | C21—C22—C23 | 119.2 (2) |
C8A—C4A—C4 | 117.5 (2) | C21—C22—H22 | 120.4 |
C6—C5—C4A | 120.0 (2) | C23—C22—H22 | 120.4 |
C6—C5—H5A | 120.0 | C24—C23—C22 | 121.8 (2) |
C4A—C5—H5A | 120.0 | C24—C23—Br2 | 119.92 (18) |
C7—C6—C5 | 121.1 (2) | C22—C23—Br2 | 118.28 (18) |
C7—C6—Br1 | 119.47 (17) | C23—C24—C25 | 118.5 (2) |
C5—C6—Br1 | 119.45 (19) | C23—C24—H24 | 120.7 |
C6—C7—C8 | 119.4 (2) | C25—C24—H24 | 120.7 |
C6—C7—H7A | 120.3 | C26—C25—C24 | 120.8 (2) |
C8—C7—H7A | 120.3 | C26—C25—H25 | 119.6 |
C7—C8—C8A | 120.9 (2) | C24—C25—H25 | 119.6 |
C7—C8—H8A | 119.6 | C25—C26—C21 | 120.1 (2) |
C8A—C8—H8A | 119.6 | C25—C26—H26 | 119.9 |
N1—C8A—C4A | 122.1 (2) | C21—C26—H26 | 119.9 |
N1—C8A—C8 | 119.0 (2) | C8A—N1—C2 | 121.08 (19) |
C4A—C8A—C8 | 118.9 (2) | C8A—N1—H1 | 115.4 (17) |
O1—C12—N11 | 124.7 (2) | C2—N1—H1 | 114.1 (17) |
O1—C12—C13 | 127.0 (2) | C12—N11—C4 | 121.4 (2) |
N11—C12—C13 | 108.3 (2) | C12—N11—C15 | 114.0 (2) |
C12—C13—C14 | 104.5 (2) | C4—N11—C15 | 124.49 (19) |
C12—C13—H13A | 110.8 | ||
N1—C2—C3—C4 | −60.0 (2) | N1—C2—C21—C26 | 149.1 (2) |
C21—C2—C3—C4 | 178.05 (19) | C3—C2—C21—C26 | −90.0 (3) |
C2—C3—C4—N11 | −171.22 (19) | C26—C21—C22—C23 | 0.0 (3) |
C2—C3—C4—C4A | 60.2 (2) | C2—C21—C22—C23 | −176.4 (2) |
N11—C4—C4A—C5 | 22.9 (3) | C21—C22—C23—C24 | 0.5 (4) |
C3—C4—C4A—C5 | 150.8 (2) | C21—C22—C23—Br2 | −178.16 (17) |
N11—C4—C4A—C8A | −162.0 (2) | C22—C23—C24—C25 | −0.5 (4) |
C3—C4—C4A—C8A | −34.1 (3) | Br2—C23—C24—C25 | 178.1 (2) |
C8A—C4A—C5—C6 | −1.9 (4) | C23—C24—C25—C26 | 0.0 (4) |
C4—C4A—C5—C6 | 173.1 (2) | C24—C25—C26—C21 | 0.5 (4) |
C4A—C5—C6—C7 | 0.0 (4) | C22—C21—C26—C25 | −0.5 (4) |
C4A—C5—C6—Br1 | −178.40 (18) | C2—C21—C26—C25 | 176.0 (2) |
C5—C6—C7—C8 | 1.6 (4) | C4A—C8A—N1—C2 | −7.4 (4) |
Br1—C6—C7—C8 | −179.91 (18) | C8—C8A—N1—C2 | 173.0 (2) |
C6—C7—C8—C8A | −1.5 (4) | C21—C2—N1—C8A | 155.7 (2) |
C5—C4A—C8A—N1 | −177.6 (2) | C3—C2—N1—C8A | 34.2 (3) |
C4—C4A—C8A—N1 | 7.2 (3) | O1—C12—N11—C4 | 1.7 (3) |
C5—C4A—C8A—C8 | 2.0 (3) | C13—C12—N11—C4 | −178.46 (19) |
C4—C4A—C8A—C8 | −173.2 (2) | O1—C12—N11—C15 | −175.2 (2) |
C7—C8—C8A—N1 | 179.3 (2) | C13—C12—N11—C15 | 4.7 (3) |
C7—C8—C8A—C4A | −0.3 (4) | C4A—C4—N11—C12 | −101.7 (2) |
O1—C12—C13—C14 | −169.8 (2) | C3—C4—N11—C12 | 132.3 (2) |
N11—C12—C13—C14 | 10.3 (2) | C4A—C4—N11—C15 | 74.8 (3) |
C12—C13—C14—C15 | −20.3 (2) | C3—C4—N11—C15 | −51.2 (3) |
C13—C14—C15—N11 | 22.5 (2) | C14—C15—N11—C12 | −17.5 (2) |
N1—C2—C21—C22 | −34.5 (3) | C14—C15—N11—C4 | 165.80 (19) |
C3—C2—C21—C22 | 86.4 (3) |
Cg3 is the centroid of the C4A/C5–C8/C8A benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13A···O1i | 0.99 | 2.46 | 3.431 (3) | 169 |
C13—H13A···Br2ii | 0.99 | 3.06 | 3.740 (3) | 127 |
C14—H14A···Br2ii | 0.99 | 3.12 | 3.664 (3) | 116 |
C14—H14B···Br1iii | 0.99 | 3.02 | 3.786 (2) | 135 |
C15—H15A···Br1iii | 0.99 | 3.00 | 3.748 (2) | 133 |
C15—H15B···Br2ii | 0.99 | 3.09 | 3.768 (2) | 127 |
C22—H22···Br1iv | 0.95 | 2.94 | 3.820 (2) | 155 |
C24—H24···Br2v | 0.95 | 3.04 | 3.932 (2) | 158 |
N1—H1···O1vi | 0.86 (3) | 2.30 (3) | 3.115 (3) | 159 (2) |
C2—H2···Cg3vi | 1.00 | 2.66 | 3.655 (3) | 173 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) x, y+1, z; (iv) −x+1, y+1/2, −z+1/2; (v) −x, y+1/2, −z+1/2; (vi) −x+1, −y+1, −z+1. |
Acknowledgements
The authors' contributions are as follows. Conceptualization, MA and AB; synthesis, AAP and AGK; X-ray analysis, MSG, KIH and NDS; writing (review and editing of the manuscript) AAP, KIH and NDS; funding acquisition, AB and MA; supervision, MA and AB.
Funding information
This work was supported by the Western Caspian University (Azerbaijan), Azerbaijan Medical University and Baku State University. This publication has been also supported by the RUDN University Scientific Projects Grant System, project No. 021408–2-000. EDY and ERS thank the Common Use Center "Physical and Chemical Research of New Materials, Substances and Catalytic Systems".
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