research communications
Crystal structures of (12E)-12-(4-benzylidene)-7,7,16-trimethyl-3-(4-methylphenyl)-1-oxa-16-azatetracyclo[11.2.1.02,11.04,9]hexadeca-2(11),4(9)-dien-5-one and (12E)-12-(4-bromobenzylidene)-73-(4-bromophenyl)-,7,16-trimethyl-10-oxa-16-azatetracyclo[11.2.1.02,11.04,9]hexadeca-2(11),4(9)-dien-5-one
aDepartment of Physics, The Madura College, Madurai 625 011, India, bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, cPG & Research Department of Physics, Government Arts College, Melur 625 106, India, and dDepartment of Physics, Bhairahawa M. Campus, Tribhuvan University, Nepal
*Correspondence e-mail: shalikaa.bh@gmail.com
The title compounds, C32H35NO2, (I), and C30H29Br2NO2, (II), differ by the presence of a bromine atom instead of a methyl atom in the para position of two benzene rings of compound (II). The two compounds have a structural overlap r.m.s. deviation of 0.27 Å. The pyran and seven-membered cycloheptene rings in both structures adopt boat and boat-sofa conformations, respectively. Intra- and intermolecular C—H⋯O hydrogen bonds are responsible for the consolidation of the crystal packing of both molecules. In addition to this, weak C—H⋯π interactions are also observed. The intermolecular interactions were quantified and analysed using Hirshfeld surface analysis.
1. Chemical context
The tropane skeleton is found widely in both natural and manufactured medications. It is the fundamental component of many beneficial et al., 2013; Afewerki et al., 2019; Dongbang et al., 2021). It is also a key component in the synthesis of newer types of drugs. Tropane derivatives are used to treat irritable bowel syndrome, peptic ulcers, colic, cystitis, and pancreatitis thanks to their anti-spasmodic properties. In view of the above importance, we have undertaken a single-crystal X-ray diffraction study for the title compounds, and the results are presented herein.
including atropine, scopolamine, and cocaine, whose derivatives are important in the treatment of neurological and psychiatric conditions such depression and panic disorder (Cheenpracha2. Structural commentary
The molecular structure of the title compounds (I) and (II) are illustrated in Figs. 1 and 2, respectively. Fig. 3 shows the superposition of the two compounds except for atom C21 using Qmol (Gans & Shalloway, 2001); the r.m.s. deviation is 0.27 Å. The methylphenyl rings in (I) are oriented at a dihedral angle of 57.7 (1)°. The methyl atoms C31 and C32 in (I) deviate by −0.036 (1) and 0.053 (1) Å, respectively, from the rings to which they are attached. The bromophenyl rings in (II) are oriented at a dihedral angle of 54.3 (1)°. Bromine atoms Br1 and Br2 deviate by 0.050 (1) and 0.037 (1) Å, respectively, from the rings to which they are attached.
The seven-membered ring (C1–C7) in both compounds has a boat-sofa conformation, with puckering parameters (Boessenkool & Boeyens, 1980) q2 = 1.021 (2) and q3 = 0.391 (2) Å in (I) and q2 = 1.053 (2) and q3 = 0.374 (2) Å in (II). The piperidine ring (N1/C4–C7/C1) has a half-boat conformation in both compounds, with atoms C4–C7/C1 in the plane and atom N1 deviating by −0.793 (1) [in (I)] or 0.785 (1) Å [in (II)] from this plane. The pyran ring (C6/O1/C15/C20/C21/C7) adopts boat conformation in both structures with puckering parameters (Cremer & Pople, 1975) q2 = QT = 0.185 (2) Å and φ = 43.9 (1)° [in (I)] and q2 = QT = 0.087 (1) Å and φ = 47.1 (1)° [in (II)]. The cyclohexene ring (C15–C20) has a distorted sofa conformation in both (I) and (II), with ΔCs(C17) asymmetry parameters (Nardelli, 1983) of 0.058 (1) and 0.004 (1), respectively.
Intramolecular C—H⋯O hydrogen bonds are observed (Tables 1 and 2)
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3. Supramolecular features
In the crystal of (I), molecules associate via C—H⋯O intermolecular interactions (C14—H14⋯O2i, Table 1), forming chains propagating along the [100] direction, see Fig. 4. In addition to this, inversion-related molecules are linked into chains by C—H⋯π interactions [C3—H3B⋯Cg, where Cg is the centroid of the C22–C27 benzene ring of the symmetry-related molecule at (− + x, − y, −z), see Fig. 4]. These two interactions form chains running in a helical manner along [101].
In the crystal of (II), molecules are also linked via C—H⋯O intermolecular interaction (C30—H30A⋯O2i, Table 2), here forming centrosymmetrical dimers with an R22(12) ring motif (Fig. 5). The dimers are further linked into chains by C—H⋯π interactions (C3—H3B⋯Cg, where Cg is the centroid of the C9–C14 benzene ring of the symmetry-related molecule at (2 − x, 2 − y, −z), see Fig. 4]. These two interactions form chains running diagonally along [110].
4. Hirshfeld surface analysis
To further characterize the intermolecular interactions in the title compound, we carried out a Hirshfeld surface (HS) analysis (Spackman & Jayatilaka, 2009) using Crystal Explorer 21 (Spackman et al., 2021) and generated the associated two dimensional fingerprint plots (McKinnon et al., 2007). The HS mapped over dnorm in the range −0.0701 to +1.6693 a.u. for compound (I) and −0.1162 to +1.5964 a.u. for compound (II) are illustrated in Figs. 6 and 7, using colours to indicate contacts that are shorter (red areas), equal to (white areas), or longer than (blue areas) the sum of the van der Waals radii (Ashfaq et al., 2021).
The two-dimensional fingerprint plots provide quantitative information about the non-covalent interactions and the crystal packing in terms of the percentage contribution of the interatomic contacts (Spackman & McKinnon, 2002; Ashfaq et al., 2021). The HS analysis reveals that H⋯H (74.2%) and H⋯C/C⋯H (16.2%) contacts are the main contributors to the crystal packing, followed by O⋯H/H⋯O (8.2%) and N⋯H/H⋯N (1.3%) contacts for compound (I) (Fig. 8). In compound (II), H⋯H (51.2%) and H⋯Br/Br⋯H (20.9%) contacts are the main contributors to the crystal packing, followed by C⋯H/H⋯C (14%) and O⋯H/H⋯O (8.5%) contacts (Fig. 9). The fragment patches on the HS provide an easy way to investigate the nearest neighbour coordination environment of a molecule (coordination number), which is 14 for compound (I) and 15 for compound (II).
5. Synthesis and crystallization
Compound (I) was synthesized from a mixture of 8-methyl-8-azabicyclo[3.2.1]octan-3-one and two equivalents of 4-methylbenzaldehyde and 5,5-dimethylcyclohexane-1,3-dione dissolved in ethanol/acetic acid and refluxed for 12 h. After completion of the reaction, as indicated by thin layer (TLC), the mixture was cooled to room temperature, poured into ice-cold water and neutralized with a of sodium bicarbonate. The compound was further recrystallized from ethanol to obtain crystals suitable for single crystal X-ray analysis.
Compound (II) was synthesized from a mixture of 8-methyl-8-azabicyclo[3.2.1]octan-3-one, two equivalents of 4-bromobenzaldehyde and 5,5-dimethylcyclohexane-1,3-dione dissolved in ethanol/acetic acid and refluxed for 12 h. After completion of the reaction, as indicated by thin layer (TLC), the mixture was cooled to room temperature, poured into ice-cold water and neutralized with a of sodium bicarbonate. The compound was further recrystallized from ethanol to obtain crystals suitable for single crystal X-ray analysis.
6. Refinement
Crystal data, data collection and structure . In both (I) and (II), H atoms were placed in idealized positions and allowed to ride on their parent atoms: C—H = 0.93–0.98 Å, with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S205698902300275X/zn2026sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300275X/zn2026Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S205698902300275X/zn2026IIsup3.hkl
For both structures, data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2020); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015b) and PLATON (Spek, 2020).C32H35NO2 | Dx = 1.175 Mg m−3 |
Mr = 465.61 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 118400 reflections |
a = 16.7576 (6) Å | θ = 3.1–27.8° |
b = 16.3223 (7) Å | µ = 0.07 mm−1 |
c = 19.2416 (8) Å | T = 293 K |
V = 5263.0 (4) Å3 | Block, colourless |
Z = 8 | 0.21 × 0.18 × 0.16 mm |
F(000) = 2000 |
Bruker SMART APEX CCD area-detector diffractometer | Rint = 0.097 |
Radiation source: fine-focus sealed tube | θmax = 30.5°, θmin = 2.9° |
ω and φ scans | h = −23→23 |
186331 measured reflections | k = −23→23 |
8013 independent reflections | l = −27→27 |
5206 reflections with I > 2σ(I) |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.059 | w = 1/[σ2(Fo2) + (0.1059P)2 + 1.8765P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.213 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.31 e Å−3 |
8013 reflections | Δρmin = −0.23 e Å−3 |
319 parameters | Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0063 (9) |
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 | ||
O1 | 0.21074 (7) | 0.58367 (7) | 0.03767 (7) | 0.0427 (3) | |
O2 | 0.34366 (9) | 0.72866 (9) | −0.13951 (8) | 0.0577 (4) | |
N1 | 0.16512 (8) | 0.78470 (9) | 0.16257 (8) | 0.0424 (3) | |
C1 | 0.18856 (10) | 0.80464 (10) | 0.09126 (10) | 0.0405 (4) | |
H1 | 0.228435 | 0.848551 | 0.090424 | 0.049* | |
C2 | 0.10849 (11) | 0.83394 (11) | 0.06103 (11) | 0.0463 (4) | |
H2A | 0.105807 | 0.823989 | 0.011381 | 0.056* | |
H2B | 0.100310 | 0.891866 | 0.069747 | 0.056* | |
C3 | 0.04652 (10) | 0.78136 (11) | 0.10060 (11) | 0.0459 (4) | |
H3A | 0.009062 | 0.815815 | 0.125555 | 0.055* | |
H3B | 0.017141 | 0.746445 | 0.068828 | 0.055* | |
C4 | 0.09680 (10) | 0.72978 (10) | 0.15142 (9) | 0.0400 (4) | |
H4 | 0.067771 | 0.720868 | 0.194982 | 0.048* | |
C5 | 0.12141 (9) | 0.64808 (10) | 0.11912 (9) | 0.0370 (3) | |
C6 | 0.18632 (9) | 0.65699 (9) | 0.06908 (9) | 0.0371 (3) | |
C7 | 0.21783 (9) | 0.72967 (10) | 0.05213 (9) | 0.0376 (3) | |
C8 | 0.08674 (10) | 0.57522 (10) | 0.13228 (9) | 0.0396 (4) | |
H8 | 0.109249 | 0.529878 | 0.110539 | 0.048* | |
C9 | 0.01749 (10) | 0.55924 (10) | 0.17700 (9) | 0.0382 (3) | |
C10 | 0.01149 (11) | 0.48435 (10) | 0.21179 (10) | 0.0435 (4) | |
H10 | 0.050998 | 0.445040 | 0.205445 | 0.052* | |
C11 | −0.05206 (12) | 0.46743 (11) | 0.25556 (10) | 0.0475 (4) | |
H11 | −0.053642 | 0.417504 | 0.278801 | 0.057* | |
C12 | −0.11325 (11) | 0.52321 (11) | 0.26546 (10) | 0.0452 (4) | |
C13 | −0.10909 (12) | 0.59637 (12) | 0.22870 (11) | 0.0511 (5) | |
H13 | −0.149884 | 0.634551 | 0.233678 | 0.061* | |
C14 | −0.04585 (11) | 0.61396 (11) | 0.18485 (11) | 0.0486 (4) | |
H14 | −0.045578 | 0.663009 | 0.160261 | 0.058* | |
C15 | 0.25631 (10) | 0.59020 (10) | −0.02083 (9) | 0.0377 (3) | |
C16 | 0.26745 (11) | 0.50897 (11) | −0.05506 (10) | 0.0447 (4) | |
H16A | 0.218260 | 0.493661 | −0.078242 | 0.054* | |
H16B | 0.278380 | 0.468083 | −0.019734 | 0.054* | |
C17 | 0.33577 (11) | 0.50880 (11) | −0.10836 (10) | 0.0459 (4) | |
C18 | 0.32508 (13) | 0.58496 (12) | −0.15407 (10) | 0.0511 (4) | |
H18A | 0.369117 | 0.587793 | −0.186698 | 0.061* | |
H18B | 0.276320 | 0.579014 | −0.180759 | 0.061* | |
C19 | 0.32134 (10) | 0.66405 (11) | −0.11423 (9) | 0.0420 (4) | |
C20 | 0.28567 (9) | 0.66154 (10) | −0.04453 (9) | 0.0368 (3) | |
C21 | 0.28068 (9) | 0.73973 (10) | −0.00295 (9) | 0.0386 (3) | |
H21 | 0.264501 | 0.784237 | −0.034095 | 0.046* | |
C22 | 0.36107 (10) | 0.76184 (11) | 0.02941 (10) | 0.0418 (4) | |
C23 | 0.39866 (12) | 0.83551 (12) | 0.01558 (13) | 0.0555 (5) | |
H23 | 0.375068 | 0.873040 | −0.014421 | 0.067* | |
C24 | 0.47229 (14) | 0.85379 (15) | 0.04666 (15) | 0.0689 (7) | |
H24 | 0.496623 | 0.903724 | 0.037033 | 0.083* | |
C25 | 0.50927 (12) | 0.79995 (16) | 0.09086 (13) | 0.0624 (6) | |
C26 | 0.47107 (13) | 0.72732 (17) | 0.10501 (14) | 0.0688 (6) | |
H26 | 0.494539 | 0.690036 | 0.135313 | 0.083* | |
C27 | 0.39826 (12) | 0.70872 (14) | 0.07493 (13) | 0.0596 (5) | |
H27 | 0.373750 | 0.659182 | 0.085642 | 0.071* | |
C28 | 0.22827 (13) | 0.75329 (15) | 0.20727 (12) | 0.0588 (5) | |
H28A | 0.206981 | 0.742153 | 0.252617 | 0.088* | |
H28B | 0.249391 | 0.703701 | 0.187734 | 0.088* | |
H28C | 0.270044 | 0.793302 | 0.210916 | 0.088* | |
C29 | 0.33113 (16) | 0.43051 (14) | −0.15184 (14) | 0.0669 (6) | |
H29A | 0.337967 | 0.383735 | −0.122184 | 0.100* | |
H29B | 0.280025 | 0.427542 | −0.174248 | 0.100* | |
H29C | 0.372469 | 0.431112 | −0.186370 | 0.100* | |
C30 | 0.41730 (12) | 0.51242 (14) | −0.07213 (13) | 0.0590 (5) | |
H30A | 0.420629 | 0.561454 | −0.044726 | 0.088* | |
H30B | 0.423397 | 0.465485 | −0.042538 | 0.088* | |
H30C | 0.458865 | 0.512600 | −0.106463 | 0.088* | |
C31 | −0.18224 (15) | 0.50520 (14) | 0.31352 (13) | 0.0645 (6) | |
H31A | −0.198385 | 0.449151 | 0.307978 | 0.097* | |
H31B | −0.226148 | 0.540633 | 0.302414 | 0.097* | |
H31C | −0.166058 | 0.514370 | 0.360747 | 0.097* | |
C32 | 0.59000 (14) | 0.8188 (2) | 0.12213 (18) | 0.0941 (10) | |
H32A | 0.605958 | 0.873155 | 0.109106 | 0.141* | |
H32B | 0.628525 | 0.780055 | 0.105291 | 0.141* | |
H32C | 0.586766 | 0.815138 | 0.171847 | 0.141* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0463 (6) | 0.0325 (6) | 0.0492 (7) | −0.0009 (5) | 0.0145 (5) | 0.0013 (5) |
O2 | 0.0641 (9) | 0.0546 (8) | 0.0545 (8) | −0.0103 (6) | 0.0075 (7) | 0.0150 (6) |
N1 | 0.0379 (7) | 0.0422 (8) | 0.0471 (8) | 0.0005 (6) | −0.0033 (6) | −0.0055 (6) |
C1 | 0.0366 (7) | 0.0319 (7) | 0.0530 (10) | −0.0008 (6) | 0.0002 (7) | −0.0028 (7) |
C2 | 0.0473 (9) | 0.0391 (9) | 0.0525 (10) | 0.0060 (7) | −0.0018 (8) | 0.0024 (7) |
C3 | 0.0367 (8) | 0.0425 (9) | 0.0585 (11) | 0.0037 (7) | −0.0035 (7) | −0.0012 (8) |
C4 | 0.0364 (7) | 0.0396 (8) | 0.0442 (9) | 0.0021 (6) | 0.0024 (6) | −0.0032 (7) |
C5 | 0.0334 (7) | 0.0377 (8) | 0.0400 (8) | 0.0012 (6) | 0.0020 (6) | 0.0010 (6) |
C6 | 0.0361 (7) | 0.0327 (7) | 0.0424 (8) | 0.0013 (6) | 0.0035 (6) | 0.0000 (6) |
C7 | 0.0323 (7) | 0.0346 (8) | 0.0460 (9) | −0.0001 (6) | 0.0003 (6) | −0.0004 (6) |
C8 | 0.0377 (8) | 0.0374 (8) | 0.0437 (9) | 0.0020 (6) | 0.0041 (6) | 0.0028 (7) |
C9 | 0.0391 (8) | 0.0360 (8) | 0.0395 (8) | −0.0014 (6) | 0.0010 (6) | 0.0042 (6) |
C10 | 0.0477 (9) | 0.0359 (8) | 0.0468 (9) | 0.0039 (7) | 0.0027 (7) | 0.0051 (7) |
C11 | 0.0587 (11) | 0.0376 (8) | 0.0460 (10) | −0.0014 (8) | 0.0041 (8) | 0.0098 (7) |
C12 | 0.0485 (9) | 0.0413 (9) | 0.0459 (10) | −0.0049 (7) | 0.0073 (7) | 0.0027 (7) |
C13 | 0.0441 (9) | 0.0442 (10) | 0.0649 (12) | 0.0032 (7) | 0.0139 (8) | 0.0083 (8) |
C14 | 0.0420 (9) | 0.0422 (9) | 0.0617 (11) | 0.0027 (7) | 0.0073 (8) | 0.0168 (8) |
C15 | 0.0343 (7) | 0.0379 (8) | 0.0410 (8) | 0.0003 (6) | 0.0052 (6) | 0.0025 (6) |
C16 | 0.0452 (9) | 0.0362 (8) | 0.0526 (10) | −0.0033 (7) | 0.0095 (8) | −0.0028 (7) |
C17 | 0.0479 (9) | 0.0410 (9) | 0.0489 (10) | 0.0037 (7) | 0.0111 (8) | 0.0010 (7) |
C18 | 0.0616 (11) | 0.0527 (11) | 0.0390 (9) | 0.0050 (9) | 0.0069 (8) | 0.0044 (8) |
C19 | 0.0353 (7) | 0.0464 (9) | 0.0442 (9) | 0.0007 (7) | 0.0010 (6) | 0.0084 (7) |
C20 | 0.0337 (7) | 0.0359 (8) | 0.0409 (8) | 0.0003 (6) | 0.0019 (6) | 0.0038 (6) |
C21 | 0.0362 (7) | 0.0322 (7) | 0.0475 (9) | −0.0008 (6) | 0.0039 (6) | 0.0051 (6) |
C22 | 0.0360 (8) | 0.0395 (8) | 0.0499 (9) | −0.0043 (6) | 0.0069 (7) | −0.0033 (7) |
C23 | 0.0500 (10) | 0.0446 (10) | 0.0720 (14) | −0.0095 (8) | 0.0080 (9) | −0.0017 (9) |
C24 | 0.0543 (12) | 0.0584 (13) | 0.0940 (18) | −0.0226 (10) | 0.0181 (12) | −0.0237 (13) |
C25 | 0.0369 (9) | 0.0826 (15) | 0.0677 (13) | −0.0041 (10) | 0.0078 (9) | −0.0285 (12) |
C26 | 0.0439 (10) | 0.0877 (17) | 0.0748 (15) | 0.0026 (10) | −0.0091 (10) | 0.0013 (13) |
C27 | 0.0437 (10) | 0.0609 (12) | 0.0741 (14) | −0.0087 (9) | −0.0059 (9) | 0.0121 (11) |
C28 | 0.0528 (11) | 0.0680 (13) | 0.0557 (12) | 0.0042 (10) | −0.0169 (9) | −0.0056 (10) |
C29 | 0.0819 (16) | 0.0496 (11) | 0.0690 (14) | 0.0036 (11) | 0.0217 (12) | −0.0115 (10) |
C30 | 0.0459 (10) | 0.0580 (12) | 0.0730 (14) | 0.0081 (9) | 0.0069 (9) | 0.0132 (10) |
C31 | 0.0683 (13) | 0.0578 (12) | 0.0674 (14) | −0.0054 (10) | 0.0250 (11) | 0.0097 (10) |
C32 | 0.0405 (11) | 0.129 (3) | 0.112 (2) | −0.0109 (14) | 0.0027 (13) | −0.055 (2) |
O1—C15 | 1.364 (2) | C16—H16B | 0.9700 |
O1—C6 | 1.4018 (19) | C17—C29 | 1.529 (3) |
O2—C19 | 1.220 (2) | C17—C18 | 1.533 (3) |
N1—C28 | 1.457 (2) | C17—C30 | 1.535 (3) |
N1—C1 | 1.464 (2) | C18—C19 | 1.503 (3) |
N1—C4 | 1.470 (2) | C18—H18A | 0.9700 |
C1—C7 | 1.518 (2) | C18—H18B | 0.9700 |
C1—C2 | 1.539 (2) | C19—C20 | 1.469 (2) |
C1—H1 | 0.9800 | C20—C21 | 1.509 (2) |
C2—C3 | 1.547 (3) | C21—C22 | 1.527 (2) |
C2—H2A | 0.9700 | C21—H21 | 0.9800 |
C2—H2B | 0.9700 | C22—C27 | 1.381 (3) |
C3—C4 | 1.541 (2) | C22—C23 | 1.383 (2) |
C3—H3A | 0.9700 | C23—C24 | 1.403 (3) |
C3—H3B | 0.9700 | C23—H23 | 0.9300 |
C4—C5 | 1.528 (2) | C24—C25 | 1.371 (4) |
C4—H4 | 0.9800 | C24—H24 | 0.9300 |
C5—C8 | 1.348 (2) | C25—C26 | 1.375 (4) |
C5—C6 | 1.460 (2) | C25—C32 | 1.512 (3) |
C6—C7 | 1.339 (2) | C26—C27 | 1.384 (3) |
C7—C21 | 1.503 (2) | C26—H26 | 0.9300 |
C8—C9 | 1.468 (2) | C27—H27 | 0.9300 |
C8—H8 | 0.9300 | C28—H28A | 0.9600 |
C9—C14 | 1.395 (2) | C28—H28B | 0.9600 |
C9—C10 | 1.397 (2) | C28—H28C | 0.9600 |
C10—C11 | 1.385 (3) | C29—H29A | 0.9600 |
C10—H10 | 0.9300 | C29—H29B | 0.9600 |
C11—C12 | 1.384 (3) | C29—H29C | 0.9600 |
C11—H11 | 0.9300 | C30—H30A | 0.9600 |
C12—C13 | 1.390 (3) | C30—H30B | 0.9600 |
C12—C31 | 1.509 (3) | C30—H30C | 0.9600 |
C13—C14 | 1.385 (3) | C31—H31A | 0.9600 |
C13—H13 | 0.9300 | C31—H31B | 0.9600 |
C14—H14 | 0.9300 | C31—H31C | 0.9600 |
C15—C20 | 1.344 (2) | C32—H32A | 0.9600 |
C15—C16 | 1.492 (2) | C32—H32B | 0.9600 |
C16—C17 | 1.537 (2) | C32—H32C | 0.9600 |
C16—H16A | 0.9700 | ||
C15—O1—C6 | 116.89 (12) | C29—C17—C16 | 109.18 (16) |
C28—N1—C1 | 115.90 (15) | C18—C17—C16 | 107.11 (15) |
C28—N1—C4 | 115.93 (15) | C30—C17—C16 | 111.09 (17) |
C1—N1—C4 | 102.00 (13) | C19—C18—C17 | 114.13 (16) |
N1—C1—C7 | 111.86 (14) | C19—C18—H18A | 108.7 |
N1—C1—C2 | 100.92 (14) | C17—C18—H18A | 108.7 |
C7—C1—C2 | 110.16 (15) | C19—C18—H18B | 108.7 |
N1—C1—H1 | 111.2 | C17—C18—H18B | 108.7 |
C7—C1—H1 | 111.2 | H18A—C18—H18B | 107.6 |
C2—C1—H1 | 111.2 | O2—C19—C20 | 120.85 (17) |
C1—C2—C3 | 103.11 (14) | O2—C19—C18 | 121.77 (17) |
C1—C2—H2A | 111.1 | C20—C19—C18 | 117.30 (15) |
C3—C2—H2A | 111.1 | C15—C20—C19 | 118.89 (15) |
C1—C2—H2B | 111.1 | C15—C20—C21 | 122.19 (15) |
C3—C2—H2B | 111.1 | C19—C20—C21 | 118.89 (14) |
H2A—C2—H2B | 109.1 | C7—C21—C20 | 108.68 (13) |
C4—C3—C2 | 104.38 (14) | C7—C21—C22 | 110.88 (15) |
C4—C3—H3A | 110.9 | C20—C21—C22 | 111.55 (13) |
C2—C3—H3A | 110.9 | C7—C21—H21 | 108.6 |
C4—C3—H3B | 110.9 | C20—C21—H21 | 108.6 |
C2—C3—H3B | 110.9 | C22—C21—H21 | 108.6 |
H3A—C3—H3B | 108.9 | C27—C22—C23 | 117.53 (18) |
N1—C4—C5 | 112.42 (13) | C27—C22—C21 | 120.54 (16) |
N1—C4—C3 | 100.68 (13) | C23—C22—C21 | 121.92 (17) |
C5—C4—C3 | 111.48 (15) | C22—C23—C24 | 120.2 (2) |
N1—C4—H4 | 110.6 | C22—C23—H23 | 119.9 |
C5—C4—H4 | 110.6 | C24—C23—H23 | 119.9 |
C3—C4—H4 | 110.6 | C25—C24—C23 | 121.7 (2) |
C8—C5—C6 | 122.22 (15) | C25—C24—H24 | 119.1 |
C8—C5—C4 | 125.27 (15) | C23—C24—H24 | 119.1 |
C6—C5—C4 | 112.48 (13) | C24—C25—C26 | 117.7 (2) |
C7—C6—O1 | 122.44 (15) | C24—C25—C32 | 121.4 (2) |
C7—C6—C5 | 122.87 (15) | C26—C25—C32 | 120.9 (3) |
O1—C6—C5 | 114.63 (13) | C25—C26—C27 | 121.1 (2) |
C6—C7—C21 | 123.02 (15) | C25—C26—H26 | 119.4 |
C6—C7—C1 | 117.77 (15) | C27—C26—H26 | 119.4 |
C21—C7—C1 | 119.21 (14) | C22—C27—C26 | 121.7 (2) |
C5—C8—C9 | 127.43 (16) | C22—C27—H27 | 119.2 |
C5—C8—H8 | 116.3 | C26—C27—H27 | 119.2 |
C9—C8—H8 | 116.3 | N1—C28—H28A | 109.5 |
C14—C9—C10 | 116.96 (15) | N1—C28—H28B | 109.5 |
C14—C9—C8 | 123.43 (15) | H28A—C28—H28B | 109.5 |
C10—C9—C8 | 119.55 (15) | N1—C28—H28C | 109.5 |
C11—C10—C9 | 121.39 (16) | H28A—C28—H28C | 109.5 |
C11—C10—H10 | 119.3 | H28B—C28—H28C | 109.5 |
C9—C10—H10 | 119.3 | C17—C29—H29A | 109.5 |
C10—C11—C12 | 121.46 (16) | C17—C29—H29B | 109.5 |
C10—C11—H11 | 119.3 | H29A—C29—H29B | 109.5 |
C12—C11—H11 | 119.3 | C17—C29—H29C | 109.5 |
C11—C12—C13 | 117.25 (17) | H29A—C29—H29C | 109.5 |
C11—C12—C31 | 121.57 (17) | H29B—C29—H29C | 109.5 |
C13—C12—C31 | 121.17 (18) | C17—C30—H30A | 109.5 |
C14—C13—C12 | 121.78 (17) | C17—C30—H30B | 109.5 |
C14—C13—H13 | 119.1 | H30A—C30—H30B | 109.5 |
C12—C13—H13 | 119.1 | C17—C30—H30C | 109.5 |
C13—C14—C9 | 121.03 (16) | H30A—C30—H30C | 109.5 |
C13—C14—H14 | 119.5 | H30B—C30—H30C | 109.5 |
C9—C14—H14 | 119.5 | C12—C31—H31A | 109.5 |
C20—C15—O1 | 123.55 (15) | C12—C31—H31B | 109.5 |
C20—C15—C16 | 125.05 (15) | H31A—C31—H31B | 109.5 |
O1—C15—C16 | 111.39 (13) | C12—C31—H31C | 109.5 |
C15—C16—C17 | 112.91 (14) | H31A—C31—H31C | 109.5 |
C15—C16—H16A | 109.0 | H31B—C31—H31C | 109.5 |
C17—C16—H16A | 109.0 | C25—C32—H32A | 109.5 |
C15—C16—H16B | 109.0 | C25—C32—H32B | 109.5 |
C17—C16—H16B | 109.0 | H32A—C32—H32B | 109.5 |
H16A—C16—H16B | 107.8 | C25—C32—H32C | 109.5 |
C29—C17—C18 | 110.96 (18) | H32A—C32—H32C | 109.5 |
C29—C17—C30 | 109.03 (18) | H32B—C32—H32C | 109.5 |
C18—C17—C30 | 109.47 (16) | ||
C28—N1—C1—C7 | 62.30 (19) | C8—C9—C14—C13 | −178.88 (19) |
C4—N1—C1—C7 | −64.57 (16) | C6—O1—C15—C20 | 7.7 (2) |
C28—N1—C1—C2 | 179.41 (15) | C6—O1—C15—C16 | −171.12 (14) |
C4—N1—C1—C2 | 52.53 (15) | C20—C15—C16—C17 | 17.0 (3) |
N1—C1—C2—C3 | −32.38 (17) | O1—C15—C16—C17 | −164.20 (15) |
C7—C1—C2—C3 | 85.97 (17) | C15—C16—C17—C29 | −167.58 (18) |
C1—C2—C3—C4 | 2.13 (18) | C15—C16—C17—C18 | −47.4 (2) |
C28—N1—C4—C5 | −58.9 (2) | C15—C16—C17—C30 | 72.1 (2) |
C1—N1—C4—C5 | 67.99 (16) | C29—C17—C18—C19 | 174.65 (17) |
C28—N1—C4—C3 | −177.62 (16) | C30—C17—C18—C19 | −65.0 (2) |
C1—N1—C4—C3 | −50.76 (15) | C16—C17—C18—C19 | 55.6 (2) |
C2—C3—C4—N1 | 28.68 (17) | C17—C18—C19—O2 | 150.97 (18) |
C2—C3—C4—C5 | −90.75 (17) | C17—C18—C19—C20 | −32.2 (2) |
N1—C4—C5—C8 | 146.10 (17) | O1—C15—C20—C19 | −168.96 (15) |
C3—C4—C5—C8 | −101.7 (2) | C16—C15—C20—C19 | 9.7 (3) |
N1—C4—C5—C6 | −36.0 (2) | O1—C15—C20—C21 | 8.9 (3) |
C3—C4—C5—C6 | 76.16 (18) | C16—C15—C20—C21 | −172.43 (16) |
C15—O1—C6—C7 | −12.9 (2) | O2—C19—C20—C15 | 174.93 (17) |
C15—O1—C6—C5 | 164.29 (14) | C18—C19—C20—C15 | −1.9 (2) |
C8—C5—C6—C7 | 175.52 (17) | O2—C19—C20—C21 | −3.0 (2) |
C4—C5—C6—C7 | −2.4 (2) | C18—C19—C20—C21 | −179.88 (15) |
C8—C5—C6—O1 | −1.7 (2) | C6—C7—C21—C20 | 13.3 (2) |
C4—C5—C6—O1 | −179.63 (14) | C1—C7—C21—C20 | −167.26 (14) |
O1—C6—C7—C21 | 1.4 (3) | C6—C7—C21—C22 | −109.67 (18) |
C5—C6—C7—C21 | −175.61 (15) | C1—C7—C21—C22 | 69.79 (19) |
O1—C6—C7—C1 | −178.09 (15) | C15—C20—C21—C7 | −18.3 (2) |
C5—C6—C7—C1 | 4.9 (3) | C19—C20—C21—C7 | 159.56 (14) |
N1—C1—C7—C6 | 30.9 (2) | C15—C20—C21—C22 | 104.24 (18) |
C2—C1—C7—C6 | −80.5 (2) | C19—C20—C21—C22 | −77.90 (19) |
N1—C1—C7—C21 | −148.60 (15) | C7—C21—C22—C27 | 61.8 (2) |
C2—C1—C7—C21 | 100.01 (17) | C20—C21—C22—C27 | −59.5 (2) |
C6—C5—C8—C9 | −174.93 (16) | C7—C21—C22—C23 | −117.10 (19) |
C4—C5—C8—C9 | 2.7 (3) | C20—C21—C22—C23 | 121.62 (19) |
C5—C8—C9—C14 | 33.7 (3) | C27—C22—C23—C24 | 0.7 (3) |
C5—C8—C9—C10 | −149.18 (19) | C21—C22—C23—C24 | 179.61 (18) |
C14—C9—C10—C11 | −4.0 (3) | C22—C23—C24—C25 | 0.4 (3) |
C8—C9—C10—C11 | 178.71 (17) | C23—C24—C25—C26 | −1.2 (3) |
C9—C10—C11—C12 | 1.5 (3) | C23—C24—C25—C32 | 177.8 (2) |
C10—C11—C12—C13 | 1.1 (3) | C24—C25—C26—C27 | 0.8 (4) |
C10—C11—C12—C31 | −179.5 (2) | C32—C25—C26—C27 | −178.1 (2) |
C11—C12—C13—C14 | −1.2 (3) | C23—C22—C27—C26 | −1.0 (3) |
C31—C12—C13—C14 | 179.5 (2) | C21—C22—C27—C26 | −179.9 (2) |
C12—C13—C14—C9 | −1.4 (3) | C25—C26—C27—C22 | 0.2 (4) |
C10—C9—C14—C13 | 3.9 (3) |
Cg is the centroid of the C22–C27 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O1 | 0.93 | 2.37 | 2.766 (2) | 105 |
C14—H14···O2i | 0.93 | 2.59 | 3.285 (2) | 131 |
C3—H3B···Cgi | 0.97 | 2.88 | 3.795 (2) | 152 |
Symmetry code: (i) x−1/2, −y+3/2, −z. |
C30H29Br2NO2 | F(000) = 1208 |
Mr = 595.36 | Dx = 1.491 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 16.051 (3) Å | Cell parameters from 102112 reflections |
b = 9.7793 (17) Å | θ = 3.5–27.5° |
c = 17.005 (3) Å | µ = 3.08 mm−1 |
β = 96.312 (5)° | T = 293 K |
V = 2653.1 (8) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.17 × 0.15 mm |
Bruker SMART APEX CCD area-detector diffractometer | Rint = 0.091 |
Radiation source: fine-focus sealed tube | θmax = 28.3°, θmin = 3.3° |
ω and φ scans | h = −21→21 |
133143 measured reflections | k = −13→13 |
6556 independent reflections | l = −22→22 |
4933 reflections with I > 2σ(I) |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.141 | w = 1/[σ2(Fo2) + (0.0695P)2 + 2.235P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.004 |
6556 reflections | Δρmax = 0.54 e Å−3 |
316 parameters | Δρmin = −0.71 e Å−3 |
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 | ||
Br1 | 1.13657 (3) | 1.48892 (4) | −0.08618 (3) | 0.07424 (18) | |
Br2 | 0.33512 (2) | 0.92555 (5) | 0.21664 (2) | 0.05914 (15) | |
O1 | 0.74355 (12) | 0.8697 (2) | −0.04204 (11) | 0.0324 (4) | |
O2 | 0.60743 (18) | 0.5052 (3) | 0.07177 (15) | 0.0552 (7) | |
N1 | 0.77700 (15) | 1.1142 (3) | 0.15803 (14) | 0.0350 (5) | |
C1 | 0.75767 (19) | 0.9713 (3) | 0.17268 (16) | 0.0349 (6) | |
H1 | 0.715499 | 0.963908 | 0.209986 | 0.042* | |
C2 | 0.8429 (2) | 0.9194 (4) | 0.21006 (17) | 0.0429 (7) | |
H2A | 0.848064 | 0.821331 | 0.203353 | 0.052* | |
H2B | 0.851861 | 0.941265 | 0.265987 | 0.052* | |
C3 | 0.90510 (19) | 0.9981 (3) | 0.16300 (17) | 0.0367 (6) | |
H3A | 0.947246 | 1.044848 | 0.198476 | 0.044* | |
H3B | 0.932793 | 0.936504 | 0.129481 | 0.044* | |
C4 | 0.84906 (17) | 1.1019 (3) | 0.11262 (16) | 0.0299 (6) | |
H4 | 0.877685 | 1.190003 | 0.109710 | 0.036* | |
C5 | 0.82292 (16) | 1.0451 (3) | 0.03006 (16) | 0.0278 (5) | |
C6 | 0.76206 (16) | 0.9339 (3) | 0.03146 (15) | 0.0277 (5) | |
C7 | 0.73047 (16) | 0.8929 (3) | 0.09691 (15) | 0.0280 (5) | |
C8 | 0.85228 (18) | 1.0867 (3) | −0.03686 (16) | 0.0319 (6) | |
H8 | 0.827454 | 1.047826 | −0.083593 | 0.038* | |
C9 | 0.91934 (18) | 1.1868 (3) | −0.04467 (17) | 0.0327 (6) | |
C10 | 0.9139 (2) | 1.2727 (4) | −0.11047 (19) | 0.0451 (8) | |
H10 | 0.866585 | 1.268859 | −0.147241 | 0.054* | |
C11 | 0.9776 (2) | 1.3637 (4) | −0.1222 (2) | 0.0529 (9) | |
H11 | 0.972788 | 1.420918 | −0.166140 | 0.064* | |
C12 | 1.0477 (2) | 1.3684 (3) | −0.0684 (2) | 0.0443 (8) | |
C13 | 1.05595 (19) | 1.2852 (3) | −0.0033 (2) | 0.0445 (7) | |
H13 | 1.103820 | 1.289674 | 0.032729 | 0.053* | |
C14 | 0.99204 (18) | 1.1939 (3) | 0.00834 (18) | 0.0385 (7) | |
H14 | 0.997839 | 1.136580 | 0.052242 | 0.046* | |
C15 | 0.69997 (16) | 0.7497 (3) | −0.04300 (15) | 0.0280 (5) | |
C16 | 0.69721 (19) | 0.6819 (3) | −0.12194 (16) | 0.0370 (7) | |
H16A | 0.749908 | 0.634979 | −0.125406 | 0.044* | |
H16B | 0.691302 | 0.751430 | −0.162876 | 0.044* | |
C17 | 0.6257 (2) | 0.5797 (3) | −0.13722 (18) | 0.0415 (7) | |
C18 | 0.6246 (3) | 0.4881 (4) | −0.0646 (2) | 0.0509 (9) | |
H18A | 0.573307 | 0.434798 | −0.070523 | 0.061* | |
H18B | 0.671080 | 0.424447 | −0.063439 | 0.061* | |
C19 | 0.63029 (19) | 0.5615 (3) | 0.01397 (18) | 0.0367 (6) | |
C20 | 0.66752 (16) | 0.6980 (3) | 0.01977 (16) | 0.0283 (5) | |
C21 | 0.67489 (16) | 0.7691 (3) | 0.09920 (15) | 0.0274 (5) | |
H21 | 0.702592 | 0.705638 | 0.138323 | 0.033* | |
C22 | 0.59016 (16) | 0.8069 (3) | 0.12632 (15) | 0.0276 (5) | |
C23 | 0.57771 (17) | 0.7910 (3) | 0.20543 (16) | 0.0332 (6) | |
H23 | 0.620545 | 0.755204 | 0.240721 | 0.040* | |
C24 | 0.50238 (18) | 0.8278 (3) | 0.23264 (17) | 0.0363 (6) | |
H24 | 0.494637 | 0.817617 | 0.285727 | 0.044* | |
C25 | 0.43931 (17) | 0.8796 (3) | 0.17940 (18) | 0.0354 (6) | |
C26 | 0.44916 (19) | 0.8963 (4) | 0.10059 (18) | 0.0412 (7) | |
H26 | 0.405744 | 0.930913 | 0.065491 | 0.049* | |
C27 | 0.52543 (19) | 0.8603 (3) | 0.07442 (17) | 0.0382 (7) | |
H27 | 0.533120 | 0.872186 | 0.021438 | 0.046* | |
C28 | 0.7072 (2) | 1.1975 (4) | 0.1221 (2) | 0.0519 (9) | |
H28A | 0.726219 | 1.289261 | 0.114943 | 0.078* | |
H28B | 0.686260 | 1.159519 | 0.071727 | 0.078* | |
H28C | 0.663230 | 1.198414 | 0.156123 | 0.078* | |
C29 | 0.6372 (3) | 0.4933 (4) | −0.2101 (2) | 0.0601 (11) | |
H29A | 0.591792 | 0.429284 | −0.219197 | 0.090* | |
H29B | 0.637705 | 0.551816 | −0.255393 | 0.090* | |
H29C | 0.689284 | 0.444488 | −0.201590 | 0.090* | |
C30 | 0.5420 (2) | 0.6584 (5) | −0.1527 (2) | 0.0626 (11) | |
H30A | 0.496677 | 0.594438 | −0.162336 | 0.094* | |
H30B | 0.533914 | 0.713077 | −0.107253 | 0.094* | |
H30C | 0.543537 | 0.716471 | −0.197980 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0454 (2) | 0.0471 (2) | 0.1313 (4) | −0.01677 (16) | 0.0145 (2) | 0.0214 (2) |
Br2 | 0.03657 (19) | 0.0783 (3) | 0.0654 (3) | 0.01380 (17) | 0.01814 (16) | 0.00151 (19) |
O1 | 0.0402 (11) | 0.0323 (10) | 0.0253 (9) | −0.0166 (8) | 0.0059 (8) | −0.0024 (8) |
O2 | 0.0722 (17) | 0.0448 (14) | 0.0517 (14) | −0.0212 (12) | 0.0207 (13) | 0.0075 (11) |
N1 | 0.0362 (13) | 0.0354 (13) | 0.0337 (12) | −0.0015 (10) | 0.0056 (10) | −0.0114 (10) |
C1 | 0.0394 (15) | 0.0426 (16) | 0.0234 (13) | −0.0106 (13) | 0.0066 (11) | −0.0059 (12) |
C2 | 0.0471 (18) | 0.0498 (19) | 0.0301 (14) | −0.0089 (14) | −0.0039 (13) | 0.0040 (13) |
C3 | 0.0332 (14) | 0.0429 (17) | 0.0324 (14) | −0.0025 (12) | −0.0036 (11) | −0.0013 (12) |
C4 | 0.0300 (13) | 0.0301 (13) | 0.0294 (13) | −0.0059 (11) | 0.0018 (10) | −0.0052 (11) |
C5 | 0.0275 (12) | 0.0268 (13) | 0.0286 (13) | −0.0040 (10) | 0.0007 (10) | −0.0023 (10) |
C6 | 0.0287 (12) | 0.0276 (13) | 0.0260 (12) | −0.0067 (10) | 0.0002 (10) | −0.0020 (10) |
C7 | 0.0260 (12) | 0.0318 (13) | 0.0262 (12) | −0.0039 (10) | 0.0036 (10) | −0.0035 (11) |
C8 | 0.0342 (14) | 0.0321 (14) | 0.0289 (13) | −0.0085 (11) | 0.0014 (11) | −0.0017 (11) |
C9 | 0.0354 (14) | 0.0273 (13) | 0.0360 (14) | −0.0064 (11) | 0.0064 (11) | −0.0034 (11) |
C10 | 0.0436 (17) | 0.0460 (18) | 0.0444 (17) | −0.0138 (14) | −0.0003 (14) | 0.0095 (14) |
C11 | 0.055 (2) | 0.0427 (19) | 0.061 (2) | −0.0121 (16) | 0.0045 (17) | 0.0216 (16) |
C12 | 0.0358 (15) | 0.0281 (15) | 0.070 (2) | −0.0075 (12) | 0.0128 (15) | 0.0017 (15) |
C13 | 0.0317 (15) | 0.0413 (17) | 0.060 (2) | −0.0050 (13) | 0.0021 (14) | −0.0040 (15) |
C14 | 0.0361 (15) | 0.0357 (16) | 0.0439 (16) | −0.0044 (12) | 0.0054 (13) | 0.0050 (13) |
C15 | 0.0258 (12) | 0.0285 (13) | 0.0300 (13) | −0.0077 (10) | 0.0035 (10) | −0.0024 (11) |
C16 | 0.0402 (15) | 0.0423 (16) | 0.0303 (14) | −0.0176 (13) | 0.0123 (12) | −0.0092 (12) |
C17 | 0.0429 (16) | 0.0484 (18) | 0.0340 (15) | −0.0232 (14) | 0.0079 (13) | −0.0104 (13) |
C18 | 0.065 (2) | 0.0374 (18) | 0.0516 (19) | −0.0236 (16) | 0.0127 (17) | −0.0066 (15) |
C19 | 0.0369 (15) | 0.0321 (15) | 0.0422 (16) | −0.0084 (12) | 0.0095 (12) | 0.0013 (13) |
C20 | 0.0267 (12) | 0.0274 (13) | 0.0317 (13) | −0.0044 (10) | 0.0075 (10) | 0.0009 (11) |
C21 | 0.0264 (12) | 0.0304 (13) | 0.0256 (12) | −0.0019 (10) | 0.0036 (10) | 0.0043 (10) |
C22 | 0.0267 (12) | 0.0273 (13) | 0.0294 (13) | −0.0032 (10) | 0.0052 (10) | 0.0044 (10) |
C23 | 0.0315 (13) | 0.0398 (15) | 0.0288 (13) | 0.0026 (12) | 0.0048 (11) | 0.0076 (12) |
C24 | 0.0373 (15) | 0.0426 (16) | 0.0305 (14) | 0.0011 (13) | 0.0107 (12) | 0.0044 (12) |
C25 | 0.0285 (13) | 0.0360 (15) | 0.0430 (16) | 0.0017 (11) | 0.0093 (12) | 0.0006 (12) |
C26 | 0.0333 (15) | 0.0524 (19) | 0.0374 (15) | 0.0102 (13) | 0.0014 (12) | 0.0091 (14) |
C27 | 0.0381 (15) | 0.0481 (18) | 0.0287 (14) | 0.0040 (13) | 0.0052 (12) | 0.0097 (13) |
C28 | 0.0456 (18) | 0.049 (2) | 0.061 (2) | 0.0079 (16) | 0.0042 (16) | −0.0160 (17) |
C29 | 0.074 (3) | 0.059 (2) | 0.049 (2) | −0.037 (2) | 0.0153 (18) | −0.0224 (17) |
C30 | 0.0434 (19) | 0.088 (3) | 0.054 (2) | −0.014 (2) | −0.0024 (16) | −0.001 (2) |
Br1—C12 | 1.899 (3) | C15—C20 | 1.338 (4) |
Br2—C25 | 1.906 (3) | C15—C16 | 1.493 (4) |
O1—C15 | 1.365 (3) | C16—C17 | 1.524 (4) |
O1—C6 | 1.401 (3) | C16—H16A | 0.9700 |
O2—C19 | 1.218 (4) | C16—H16B | 0.9700 |
N1—C1 | 1.458 (4) | C17—C29 | 1.528 (5) |
N1—C4 | 1.464 (4) | C17—C18 | 1.528 (5) |
N1—C28 | 1.464 (4) | C17—C30 | 1.544 (5) |
C1—C7 | 1.522 (4) | C18—C19 | 1.510 (5) |
C1—C2 | 1.531 (4) | C18—H18A | 0.9700 |
C1—H1 | 0.9800 | C18—H18B | 0.9700 |
C2—C3 | 1.550 (4) | C19—C20 | 1.462 (4) |
C2—H2A | 0.9700 | C20—C21 | 1.512 (4) |
C2—H2B | 0.9700 | C21—C22 | 1.529 (4) |
C3—C4 | 1.551 (4) | C21—H21 | 0.9800 |
C3—H3A | 0.9700 | C22—C27 | 1.389 (4) |
C3—H3B | 0.9700 | C22—C23 | 1.390 (4) |
C4—C5 | 1.525 (4) | C23—C24 | 1.389 (4) |
C4—H4 | 0.9800 | C23—H23 | 0.9300 |
C5—C8 | 1.342 (4) | C24—C25 | 1.378 (4) |
C5—C6 | 1.464 (4) | C24—H24 | 0.9300 |
C6—C7 | 1.335 (4) | C25—C26 | 1.376 (4) |
C7—C21 | 1.507 (4) | C26—C27 | 1.393 (4) |
C8—C9 | 1.472 (4) | C26—H26 | 0.9300 |
C8—H8 | 0.9300 | C27—H27 | 0.9300 |
C9—C10 | 1.394 (4) | C28—H28A | 0.9600 |
C9—C14 | 1.396 (4) | C28—H28B | 0.9600 |
C10—C11 | 1.386 (4) | C28—H28C | 0.9600 |
C10—H10 | 0.9300 | C29—H29A | 0.9600 |
C11—C12 | 1.371 (5) | C29—H29B | 0.9600 |
C11—H11 | 0.9300 | C29—H29C | 0.9600 |
C12—C13 | 1.368 (5) | C30—H30A | 0.9600 |
C13—C14 | 1.391 (4) | C30—H30B | 0.9600 |
C13—H13 | 0.9300 | C30—H30C | 0.9600 |
C14—H14 | 0.9300 | ||
C15—O1—C6 | 117.0 (2) | C15—C16—H16B | 109.0 |
C1—N1—C4 | 101.9 (2) | C17—C16—H16B | 109.0 |
C1—N1—C28 | 115.9 (3) | H16A—C16—H16B | 107.8 |
C4—N1—C28 | 116.0 (3) | C16—C17—C29 | 110.2 (3) |
N1—C1—C7 | 112.6 (2) | C16—C17—C18 | 108.8 (3) |
N1—C1—C2 | 101.0 (2) | C29—C17—C18 | 110.2 (3) |
C7—C1—C2 | 110.1 (3) | C16—C17—C30 | 109.1 (3) |
N1—C1—H1 | 110.9 | C29—C17—C30 | 108.5 (3) |
C7—C1—H1 | 110.9 | C18—C17—C30 | 110.1 (3) |
C2—C1—H1 | 110.9 | C19—C18—C17 | 115.5 (3) |
C1—C2—C3 | 102.6 (2) | C19—C18—H18A | 108.4 |
C1—C2—H2A | 111.3 | C17—C18—H18A | 108.4 |
C3—C2—H2A | 111.3 | C19—C18—H18B | 108.4 |
C1—C2—H2B | 111.3 | C17—C18—H18B | 108.4 |
C3—C2—H2B | 111.3 | H18A—C18—H18B | 107.5 |
H2A—C2—H2B | 109.2 | O2—C19—C20 | 121.0 (3) |
C4—C3—C2 | 104.1 (2) | O2—C19—C18 | 120.3 (3) |
C4—C3—H3A | 110.9 | C20—C19—C18 | 118.6 (3) |
C2—C3—H3A | 110.9 | C15—C20—C19 | 118.9 (2) |
C4—C3—H3B | 110.9 | C15—C20—C21 | 122.7 (2) |
C2—C3—H3B | 110.9 | C19—C20—C21 | 118.1 (2) |
H3A—C3—H3B | 109.0 | C7—C21—C20 | 109.6 (2) |
N1—C4—C5 | 111.2 (2) | C7—C21—C22 | 111.3 (2) |
N1—C4—C3 | 101.9 (2) | C20—C21—C22 | 113.3 (2) |
C5—C4—C3 | 110.7 (2) | C7—C21—H21 | 107.5 |
N1—C4—H4 | 110.9 | C20—C21—H21 | 107.5 |
C5—C4—H4 | 110.9 | C22—C21—H21 | 107.5 |
C3—C4—H4 | 110.9 | C27—C22—C23 | 118.7 (3) |
C8—C5—C6 | 122.4 (2) | C27—C22—C21 | 121.8 (2) |
C8—C5—C4 | 125.7 (2) | C23—C22—C21 | 119.5 (2) |
C6—C5—C4 | 111.9 (2) | C24—C23—C22 | 121.1 (3) |
C7—C6—O1 | 123.1 (2) | C24—C23—H23 | 119.4 |
C7—C6—C5 | 123.5 (2) | C22—C23—H23 | 119.4 |
O1—C6—C5 | 113.2 (2) | C25—C24—C23 | 118.7 (3) |
C6—C7—C21 | 122.9 (2) | C25—C24—H24 | 120.7 |
C6—C7—C1 | 117.0 (2) | C23—C24—H24 | 120.7 |
C21—C7—C1 | 119.9 (2) | C26—C25—C24 | 121.9 (3) |
C5—C8—C9 | 127.3 (3) | C26—C25—Br2 | 119.6 (2) |
C5—C8—H8 | 116.3 | C24—C25—Br2 | 118.4 (2) |
C9—C8—H8 | 116.3 | C25—C26—C27 | 118.7 (3) |
C10—C9—C14 | 117.5 (3) | C25—C26—H26 | 120.7 |
C10—C9—C8 | 119.4 (3) | C27—C26—H26 | 120.7 |
C14—C9—C8 | 122.9 (3) | C22—C27—C26 | 121.0 (3) |
C11—C10—C9 | 121.4 (3) | C22—C27—H27 | 119.5 |
C11—C10—H10 | 119.3 | C26—C27—H27 | 119.5 |
C9—C10—H10 | 119.3 | N1—C28—H28A | 109.5 |
C12—C11—C10 | 119.4 (3) | N1—C28—H28B | 109.5 |
C12—C11—H11 | 120.3 | H28A—C28—H28B | 109.5 |
C10—C11—H11 | 120.3 | N1—C28—H28C | 109.5 |
C13—C12—C11 | 121.2 (3) | H28A—C28—H28C | 109.5 |
C13—C12—Br1 | 119.4 (2) | H28B—C28—H28C | 109.5 |
C11—C12—Br1 | 119.4 (3) | C17—C29—H29A | 109.5 |
C12—C13—C14 | 119.4 (3) | C17—C29—H29B | 109.5 |
C12—C13—H13 | 120.3 | H29A—C29—H29B | 109.5 |
C14—C13—H13 | 120.3 | C17—C29—H29C | 109.5 |
C13—C14—C9 | 121.1 (3) | H29A—C29—H29C | 109.5 |
C13—C14—H14 | 119.4 | H29B—C29—H29C | 109.5 |
C9—C14—H14 | 119.4 | C17—C30—H30A | 109.5 |
C20—C15—O1 | 124.0 (2) | C17—C30—H30B | 109.5 |
C20—C15—C16 | 125.0 (2) | H30A—C30—H30B | 109.5 |
O1—C15—C16 | 110.9 (2) | C17—C30—H30C | 109.5 |
C15—C16—C17 | 113.1 (2) | H30A—C30—H30C | 109.5 |
C15—C16—H16A | 109.0 | H30B—C30—H30C | 109.5 |
C17—C16—H16A | 109.0 | ||
C4—N1—C1—C7 | −63.9 (3) | C8—C9—C14—C13 | 176.6 (3) |
C28—N1—C1—C7 | 63.1 (3) | C6—O1—C15—C20 | 6.7 (4) |
C4—N1—C1—C2 | 53.6 (2) | C6—O1—C15—C16 | −170.6 (2) |
C28—N1—C1—C2 | −179.4 (3) | C20—C15—C16—C17 | 23.8 (4) |
N1—C1—C2—C3 | −36.9 (3) | O1—C15—C16—C17 | −158.9 (3) |
C7—C1—C2—C3 | 82.4 (3) | C15—C16—C17—C29 | −168.1 (3) |
C1—C2—C3—C4 | 8.1 (3) | C15—C16—C17—C18 | −47.3 (4) |
C1—N1—C4—C5 | 70.2 (3) | C15—C16—C17—C30 | 72.8 (3) |
C28—N1—C4—C5 | −56.7 (3) | C16—C17—C18—C19 | 47.9 (4) |
C1—N1—C4—C3 | −47.8 (2) | C29—C17—C18—C19 | 168.7 (3) |
C28—N1—C4—C3 | −174.7 (2) | C30—C17—C18—C19 | −71.6 (4) |
C2—C3—C4—N1 | 23.3 (3) | C17—C18—C19—O2 | 159.9 (3) |
C2—C3—C4—C5 | −95.1 (3) | C17—C18—C19—C20 | −23.2 (5) |
N1—C4—C5—C8 | 140.3 (3) | O1—C15—C20—C19 | −173.2 (3) |
C3—C4—C5—C8 | −107.1 (3) | C16—C15—C20—C19 | 3.7 (4) |
N1—C4—C5—C6 | −41.3 (3) | O1—C15—C20—C21 | 0.8 (4) |
C3—C4—C5—C6 | 71.2 (3) | C16—C15—C20—C21 | 177.8 (3) |
C15—O1—C6—C7 | −8.7 (4) | O2—C19—C20—C15 | 172.8 (3) |
C15—O1—C6—C5 | 168.1 (2) | C18—C19—C20—C15 | −4.1 (4) |
C8—C5—C6—C7 | −178.4 (3) | O2—C19—C20—C21 | −1.5 (4) |
C4—C5—C6—C7 | 3.2 (4) | C18—C19—C20—C21 | −178.5 (3) |
C8—C5—C6—O1 | 4.8 (4) | C6—C7—C21—C20 | 4.1 (4) |
C4—C5—C6—O1 | −173.6 (2) | C1—C7—C21—C20 | −171.7 (2) |
O1—C6—C7—C21 | 3.0 (4) | C6—C7—C21—C22 | −122.0 (3) |
C5—C6—C7—C21 | −173.5 (2) | C1—C7—C21—C22 | 62.2 (3) |
O1—C6—C7—C1 | 178.9 (2) | C15—C20—C21—C7 | −6.0 (4) |
C5—C6—C7—C1 | 2.4 (4) | C19—C20—C21—C7 | 168.1 (2) |
N1—C1—C7—C6 | 29.9 (4) | C15—C20—C21—C22 | 118.9 (3) |
C2—C1—C7—C6 | −82.1 (3) | C19—C20—C21—C22 | −67.0 (3) |
N1—C1—C7—C21 | −154.1 (2) | C7—C21—C22—C27 | 82.3 (3) |
C2—C1—C7—C21 | 93.9 (3) | C20—C21—C22—C27 | −41.7 (4) |
C6—C5—C8—C9 | −173.3 (3) | C7—C21—C22—C23 | −96.0 (3) |
C4—C5—C8—C9 | 4.9 (5) | C20—C21—C22—C23 | 140.0 (3) |
C5—C8—C9—C10 | −145.2 (3) | C27—C22—C23—C24 | −0.1 (4) |
C5—C8—C9—C14 | 39.5 (5) | C21—C22—C23—C24 | 178.2 (3) |
C14—C9—C10—C11 | −1.1 (5) | C22—C23—C24—C25 | 0.5 (5) |
C8—C9—C10—C11 | −176.7 (3) | C23—C24—C25—C26 | −0.3 (5) |
C9—C10—C11—C12 | 0.6 (6) | C23—C24—C25—Br2 | 178.4 (2) |
C10—C11—C12—C13 | −0.1 (6) | C24—C25—C26—C27 | −0.4 (5) |
C10—C11—C12—Br1 | 178.0 (3) | Br2—C25—C26—C27 | −179.1 (3) |
C11—C12—C13—C14 | 0.1 (5) | C23—C22—C27—C26 | −0.6 (5) |
Br1—C12—C13—C14 | −178.0 (2) | C21—C22—C27—C26 | −178.9 (3) |
C12—C13—C14—C9 | −0.7 (5) | C25—C26—C27—C22 | 0.8 (5) |
C10—C9—C14—C13 | 1.2 (5) |
Cg is the centroid of the C9–C14 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O1 | 0.93 | 2.36 | 2.742 (3) | 105 |
C30—H30A···O2i | 0.96 | 2.58 | 3.306 (5) | 132 |
C3—H3B···Cgii | 0.97 | 2.84 | 3.798 (3) | 169 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+2, −z. |
Footnotes
‡Additional correspondence author, e-mail: s_selvanayagam@rediffmail.com.
Acknowledgements
The authors wish to thank the Management of The Madura College for their support
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