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

Meenatchi, C.S.; Vishnupriya, R.; Suresh, J.; Rubina, S.R.; Selvanayagam, S.; Bhandari, S.R.

doi:10.1107/S205698902300275X

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 79| Part 4| April 2023| Pages 392-396

https://doi.org/10.1107/S205698902300275X

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Crystal structures of (12E)-12-(4-benzylidene)-7,7,16-trimethyl-3-(4-methylphenyl)-1-oxa-16-azatetracyclo[11.2.1.0^2,11.0^4,9]hexadeca-2(11),4(9)-dien-5-one and (12E)-12-(4-bromobenzylidene)-73-(4-bromophenyl)-,7,16-trimethyl-10-oxa-16-azatetracyclo[11.2.1.0^2,11.0^4,9]hexadeca-2(11),4(9)-dien-5-one

C. Selva Meenatchi,^a R. Vishnupriya,^a J. Suresh,^a S. Raja Rubina,^b S. Selvanayagam ^c ‡ and S. R. Bhandari ^d ^*

^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

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 20 February 2023; accepted 23 March 2023; online 28 March 2023)

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.

Keywords: crystal structure; azabicyclo derivatives; superposition; C—H⋯O intramolecular interactions; C—H⋯O intermolecular hydrogen bonds; Hirshfeld surface analysis.

CCDC references: 2251053; 2251052

1. Chemical context

The tropane skeleton is found widely in both natural and manufactured medications. It is the fundamental component of many beneficial alkaloids, including atropine, scopolamine, and cocaine, whose derivatives are important in the treatment of neurological and psychiatric conditions such depression and panic disorder (Cheenpracha 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.

2. 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.

Figure 1
A view of the molecular structure of compound (I)

, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
A view of the molecular structure of compound (II)

, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
Superposition of compound (I)

(violet) and compound (II)

(brown) except for atoms Br1, Br2 and C21.

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 = Q_T = 0.185 (2) Å and φ = 43.9 (1)° [in (I)] and q₂ = Q_T = 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 ΔC_s(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)

Table 1
Hydrogen-bond geometry (Å, °) for (I)

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) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Table 2
Hydrogen-bond geometry (Å, °) for (II)

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) ; (ii) .

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 (− $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, −z), see Fig. 4]. These two interactions form chains running in a helical manner along [101].

Figure 4
The crystal packing of the title compound (I)

viewed along b axis. The C—H⋯O and C—H⋯π intermolecular interactions are shown as dashed lines. For clarity, H atoms not involved in these interactions have been omitted.

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].

Figure 5
The centrosymmetrical dimer formed in compound (II)

via C—H⋯O hydrogen bonds (dashed lines). The dimers are linked by C—H⋯π interactions (dashed lines). For clarity H atoms, not involved in these interactions have been omitted.

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 d_norm 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 ).

Figure 6
A view of the Hirshfeld surface mapped over d_norm in the range −0.0701 to +1.6693 arbitrary units for compound (I)

Figure 7
A view of the Hirshfeld surface mapped over d_norm in the range −0.1162 to +1.5964 arbitrary units for compound (II)

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).

Figure 8
Two-dimensional fingerprint plots for compound (I)

, showing (a) all interactions, and delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) O⋯H/H⋯O and (e) N⋯H/H⋯N interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

Figure 9
Two-dimensional fingerprint plots for compound (II)

, showing (a) all interactions, and delineated into (b) H⋯H, (c) Br⋯H/H⋯Br, (d) C⋯H/H⋯C and (e) O⋯H/H⋯O interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

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 chromatography (TLC), the mixture was cooled to room temperature, poured into ice-cold water and neutralized with a saturated solution 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 chromatography (TLC), the mixture was cooled to room temperature, poured into ice-cold water and neutralized with a saturated solution 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 refinement details are summarized in Table 3. 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 U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms.

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₃₂H₃₅NO₂	C₃₀H₂₉Br₂NO₂
M_r	465.61	595.36
Crystal system, space group	Orthorhombic, Pbca	Monoclinic, P2₁/n
Temperature (K)	293	293
a, b, c (Å)	16.7576 (6), 16.3223 (7), 19.2416 (8)	16.051 (3), 9.7793 (17), 17.005 (3)
α, β, γ (°)	90, 90, 90	90, 96.312 (5), 90
V (Å³)	5263.0 (4)	2653.1 (8)
Z	8	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.07	3.08
Crystal size (mm)	0.21 × 0.18 × 0.16	0.20 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector	Bruker SMART APEX CCD area-detector
No. of measured, independent and observed [I > 2σ(I)] reflections	186331, 8013, 5206	133143, 6556, 4933
R_int	0.097	0.091
(sin θ/λ)_max (Å⁻¹)	0.714	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.213, 1.04	0.050, 0.141, 1.09
No. of reflections	8013	6556
No. of parameters	319	316
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23	0.54, −0.71
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC references: 2251053; 2251052

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S205698902300275X/zn2026sup1.cif

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

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2009); cell refinement: 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).

(12E)-12-(4-Benzylidene)-7,7,16-trimethyl-3-(4-methylphenyl)-1-oxa-16-azatetracyclo[11.2.1.0^2,11.0^4,9]hexadeca-2(11),4(9)-dien-5-one (I) top

Crystal data top

C₃₂H₃₅NO₂	D_x = 1.175 Mg m⁻³
M_r = 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

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	R_int = 0.097
Radiation source: fine-focus sealed tube	θ_max = 30.5°, θ_min = 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 top

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(F_o²) + (0.1059P)² + 1.8765P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.213	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.31 e Å⁻³
8013 reflections	Δρ_min = −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)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

(12E)-12-(4-Bromobenzylidene)-73-(4-bromophenyl)-,7,16-trimethyl-10-oxa-16-azatetracyclo[11.2.1.0^2,11.0^4,9]hexadeca-2(11),4(9)-dien-5-one (II) top

Crystal data top

C₃₀H₂₉Br₂NO₂	F(000) = 1208
M_r = 595.36	D_x = 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

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	R_int = 0.091
Radiation source: fine-focus sealed tube	θ_max = 28.3°, θ_min = 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 top

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(F_o²) + (0.0695P)² + 2.235P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.004
6556 reflections	Δρ_max = 0.54 e Å⁻³
316 parameters	Δρ_min = −0.71 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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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