2,4-Bis(2-bromo­phen­yl)-7-tert-pentyl-3-aza­bicyclo­[3.3.1]nonan-9-one

Park, D.H.; Ramkumar, V.; Parthiban, P.

doi:10.1107/S1600536812039128

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2946

https://doi.org/10.1107/S1600536812039128

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2,4-Bis(2-bromophenyl)-7-tert-pentyl-3-azabicyclo[3.3.1]nonan-9-one

Dong Ho Park,^a V. Ramkumar ^b and P. Parthiban ^a ^*

^aDepartment of Biomedicinal Chemistry, Inje University, Gimhae, Gyeongnam 621 749, Republic of Korea, and ^bDepartment of Chemistry, IIT Madras, Chennai 600 036, TamilNadu, India
^*Correspondence e-mail: parthisivam@yahoo.co.in

(Received 9 September 2012; accepted 13 September 2012; online 19 September 2012)

The title compound, C₂₅H₂₉Br₂NO, is a tert-pentyl analog of 2,4-bis(2-bromophenyl)-3-azabicyclo[3.3.1]nonan-9-one [Parthiban et al. (2008 ). Acta Cryst. E64, o2385]. Similar to its analog, the title compound exists in a twin-chair conformation with an equatorial orientation of the 2-bromophenyl groups. The benzene rings are inclined to each other at a dihedral angle of 29.6 (3)°. The tert-pentyl group on the cyclohexanone ring also adopts an exocyclic equatorial disposition.

Related literature

For the synthesis, stereochemistry and biological activity of 3-azabicyclo[3.3.1]nonan-9-ones, see: Park et al. (2011 , 2012a ). For the crystal structure of closely related compound, see: Parthiban et al. (2008). For examples of azabicycles with different conformations, see: Parthiban et al. (2010 ); Park et al. (2012b ); Padegimas & Kovacic (1972 ).

Experimental

Crystal data

C₂₅H₂₉Br₂NO
M_r = 519.31
Triclinic, $[P \overline 1]$
a = 7.7342 (7) Å
b = 10.6409 (10) Å
c = 15.0924 (12) Å
α = 105.856 (4)°
β = 101.242 (4)°
γ = 97.112 (4)°
V = 1151.08 (18) Å³
Z = 2
Mo Kα radiation
μ = 3.54 mm⁻¹
T = 298 K
0.18 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.569, T_max = 0.719
16189 measured reflections
6006 independent reflections
3081 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.212
S = 1.02
6006 reflections
259 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −1.26 e Å⁻³

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812039128/cv5341sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S1600536812039128/cv5341Isup2.mol

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812039128/cv5341Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812039128/cv5341Isup4.cml

checkCIF report

Comment top

The bycyclic compounds posses three major conformations, viz., chair-chair (Parthiban et al., 2010), chair-boat (Park et al., 2012b) and boat-boat (Padegimas & Kovacic, 1972), depending upon the nature and position of the substituents on the bicycle. The aim of the present study was to explore the stereochemistry as well as the impact of tert-pentyl on the twin-chair conformation of the 2,4-bis(2-bromophenyl)-3-azabicyclo[3.3.1]nonan-9-one (Parthiban et al., 2008).

Examination of the asymmery parameters and torsion angles of the title compound (Fig. 1) reveals that the values are very similar to those in its analog. In detail, the torsion angles of the title compound C2—C8—C6—C7, C1—C2—C8—C6, C5—C6—C8—C2 and C3—C2—C8—C6 are -61.2 (5), 61.9 (5), 63.4 (5) and -63.8 (5)°, respectively. These clearly assign slightly distorted chair conformation to both six-membered rings, and the cyclohexanone ring is compratively flattened. Furthermore, the orientation of the bromophenyl groups on both sides of the secondary amino group is identified by their torsion angles. The torsion angle of C9—C1—C2—C8 and C8—C6—C7—C15 are 178.0 (4) and -178.6 (4)°, respectively. This clearly conform their euatorial orientations, and it is similar to its non-tert-pentyl analog [C9—C1—C2—C8 and C8—C6—C7—C15 are 177.8 (4) and -179.4 (6)°, respectively]. Also the orientation of tert-pentyl group on the cyclohexanone ring is identified by its torsion angles [C21—C4—C5—C6 and C2—C3—C4—C21 are 171.4 (4) and -172.2 (4)°, respectively]. In addition to the above similarities, the title compound and its analog's benzene rings orientations are very similar. In titile compound, the benzene rings are inclined to echh other with an angle of 29.6 (3)°; it is 29.1° for its analog. Hence, the title compound, C₂₅H₂₉Br₂NO, exists in a twin-chair conformation with an euatorial orientation of the ortho-bromophenyl groups as its non-tert-pentyl analog. The tert-pentyl group on the cyclohexnone also adopts an exocyclic equtorial disposition.

Related literature top

For the synthesis, stereochemistry and biological activity of 3-azabicyclo[3.3.1]nonan-9-ones, see: Park et al. (2011, 2012a). For the crystal structure of closely related compound, see: Parthiban et al. (2008). For examples of azabicycles with different conformations, see: Parthiban et al. (2010); Park et al. (2012b); Padegimas & Kovacic (1972).

Experimental top

The 2,4-bis(2-bromophenyl)-7-(tert-pentyl) -3-azabicyclo[3.3.1]nonan-9-one was synthesized by a modified and an optimized Mannich condensation in one-pot, using 2-bromobenzaldehyde (0.1 mol, 18.50 g/11.58 ml), 4-tert-pentylcyclohexanone (0.05 mol, 8.41 g/9.15 ml) and ammonium acetate (0.075 mol, 5.78 g) in a 50 ml of absolute ethanol (Park et al., 2011). The mixture was gently warmed on a hot plate at 303–308 K (30–35° C) with moderate stirring till the complete consumption of the starting materials, which was monitored by TLC. At the end, the crude azabicyclic ketone was separated by filtration and gently washed with 1:5 cold ethanol-ether mixture. X-ray diffraction quality crystals of the title compound were obtained by slow evaporation from ethanol.

Structure description top

For the synthesis, stereochemistry and biological activity of 3-azabicyclo[3.3.1]nonan-9-ones, see: Park et al. (2011, 2012a). For the crystal structure of closely related compound, see: Parthiban et al. (2008). For examples of azabicycles with different conformations, see: Parthiban et al. (2010); Park et al. (2012b); Padegimas & Kovacic (1972).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing the atomic numbering and displacement ellipsoids drawn at the 30% probability level.

2,4-Bis(2-bromophenyl)-7-tert-pentyl-3-azabicyclo[3.3.1]nonan-9-one top

Crystal data top

C₂₅H₂₉Br₂NO	Z = 2
M_r = 519.31	F(000) = 528
Triclinic, P1	D_x = 1.498 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7342 (7) Å	Cell parameters from 4160 reflections
b = 10.6409 (10) Å	θ = 2.7–22.8°
c = 15.0924 (12) Å	µ = 3.54 mm⁻¹
α = 105.856 (4)°	T = 298 K
β = 101.242 (4)°	Prism, colourless
γ = 97.112 (4)°	0.18 × 0.15 × 0.10 mm
V = 1151.08 (18) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	6006 independent reflections
Radiation source: fine-focus sealed tube	3081 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
phi and ω scans	θ_max = 29.5°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
T_min = 0.569, T_max = 0.719	k = −14→14
16189 measured reflections	l = −20→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.212	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.117P)²] where P = (F_o² + 2F_c²)/3
6006 reflections	(Δ/σ)_max = 0.001
259 parameters	Δρ_max = 1.24 e Å⁻³
1 restraint	Δρ_min = −1.26 e Å⁻³

Crystal data top

C₂₅H₂₉Br₂NO	γ = 97.112 (4)°
M_r = 519.31	V = 1151.08 (18) Å³
Triclinic, P1	Z = 2
a = 7.7342 (7) Å	Mo Kα radiation
b = 10.6409 (10) Å	µ = 3.54 mm⁻¹
c = 15.0924 (12) Å	T = 298 K
α = 105.856 (4)°	0.18 × 0.15 × 0.10 mm
β = 101.242 (4)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	6006 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3081 reflections with I > 2σ(I)
T_min = 0.569, T_max = 0.719	R_int = 0.047
16189 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	1 restraint
wR(F²) = 0.212	H-atom parameters constrained
S = 1.02	Δρ_max = 1.24 e Å⁻³
6006 reflections	Δρ_min = −1.26 e Å⁻³
259 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell e.s.d.'s are taken

into account individually in the estimation of e.s.d.'s in distances, angles

and torsion angles; correlations between e.s.d.'s in cell parameters are only

used when they are defined by crystal symmetry. An approximate (isotropic)

treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and

goodness of fit S are based on F², conventional R-factors R are based

on F, with F set to zero for negative F². The threshold expression of

F² > σ(F²) is used only for calculating R-factors(gt) etc. and is

not relevant to the choice of reflections for refinement. R-factors based

on F² are statistically about twice as large as those based on F, and R-

factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Br1	0.86819 (8)	0.90205 (5)	0.32088 (5)	0.0717 (3)
Br2	0.85323 (8)	0.28410 (7)	0.51276 (4)	0.0732 (3)
C1	0.6565 (6)	0.6164 (4)	0.3068 (3)	0.0411 (10)
H1	0.7614	0.6679	0.3573	0.049*
C2	0.7228 (6)	0.5383 (4)	0.2223 (3)	0.0440 (11)
H2	0.8022	0.6010	0.2042	0.053*
C3	0.5766 (7)	0.4547 (4)	0.1333 (3)	0.0486 (12)
H3A	0.4990	0.5124	0.1143	0.058*
H3B	0.6342	0.4219	0.0822	0.058*
C4	0.4601 (7)	0.3360 (4)	0.1455 (3)	0.0456 (11)
H4	0.3820	0.3730	0.1857	0.055*
C5	0.5749 (7)	0.2611 (4)	0.1995 (3)	0.0474 (12)
H5A	0.6321	0.2059	0.1558	0.057*
H5B	0.4959	0.2021	0.2195	0.057*
C6	0.7214 (6)	0.3469 (4)	0.2870 (3)	0.0441 (11)
H6	0.7977	0.2894	0.3093	0.053*
C7	0.6514 (6)	0.4244 (4)	0.3698 (3)	0.0408 (10)
H7	0.7552	0.4716	0.4223	0.049*
C8	0.8320 (7)	0.4438 (4)	0.2566 (3)	0.0462 (11)
C9	0.5400 (6)	0.7115 (4)	0.2822 (3)	0.0405 (10)
C10	0.6147 (7)	0.8408 (4)	0.2862 (3)	0.0461 (11)
C11	0.5088 (10)	0.9304 (5)	0.2667 (4)	0.0670 (16)
H11	0.5618	1.0158	0.2708	0.080*
C12	0.3248 (9)	0.8927 (6)	0.2414 (5)	0.0755 (18)
H12	0.2527	0.9530	0.2298	0.091*
C13	0.2472 (8)	0.7627 (6)	0.2332 (4)	0.0676 (16)
H13	0.1235	0.7341	0.2130	0.081*
C14	0.3574 (7)	0.6776 (5)	0.2555 (4)	0.0531 (13)
H14	0.3042	0.5925	0.2521	0.064*
C15	0.5335 (6)	0.3345 (4)	0.4043 (3)	0.0384 (10)
C16	0.3459 (6)	0.3148 (5)	0.3759 (3)	0.0483 (11)
H16	0.2941	0.3628	0.3382	0.058*
C17	0.2358 (8)	0.2263 (6)	0.4020 (4)	0.0596 (14)
H17	0.1119	0.2140	0.3809	0.072*
C18	0.3103 (8)	0.1554 (5)	0.4598 (4)	0.0586 (14)
H18	0.2364	0.0954	0.4773	0.070*
C19	0.4926 (8)	0.1744 (4)	0.4908 (3)	0.0509 (12)
H19	0.5431	0.1276	0.5298	0.061*
C20	0.6015 (6)	0.2631 (4)	0.4641 (3)	0.0415 (10)
N1	0.5541 (5)	0.5240 (3)	0.3436 (3)	0.0413 (9)
H1A	0.4463	0.5282	0.3493	0.050*
O1	0.9910 (5)	0.4487 (4)	0.2582 (3)	0.0695 (10)
C21	0.3326 (9)	0.2448 (5)	0.0486 (4)	0.0732 (18)
C24	0.2293 (15)	0.1222 (10)	0.0634 (7)	0.155 (4)
H24A	0.3131	0.0784	0.0950	0.186*
H24B	0.1656	0.0598	0.0023	0.186*
C22	0.1993 (13)	0.3238 (9)	0.0052 (6)	0.151 (5)
H22A	0.1380	0.2718	−0.0585	0.226*
H22B	0.2649	0.4062	0.0046	0.226*
H22C	0.1133	0.3417	0.0429	0.226*
C25	0.0936 (15)	0.1639 (10)	0.1242 (7)	0.155 (4)
H25A	0.1470	0.2459	0.1736	0.232*
H25B	0.0624	0.0959	0.1521	0.232*
H25C	−0.0126	0.1758	0.0847	0.232*
C23	0.4459 (12)	0.1841 (8)	−0.0222 (5)	0.113 (3)
H23A	0.5272	0.1372	0.0065	0.169*
H23B	0.5130	0.2542	−0.0373	0.169*
H23C	0.3671	0.1237	−0.0792	0.169*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0725 (4)	0.0449 (3)	0.0923 (5)	−0.0143 (3)	0.0195 (3)	0.0238 (3)
Br2	0.0604 (4)	0.0956 (5)	0.0726 (5)	0.0205 (3)	0.0054 (3)	0.0452 (4)
C1	0.045 (3)	0.026 (2)	0.051 (3)	−0.0006 (18)	0.012 (2)	0.0140 (18)
C2	0.047 (3)	0.035 (2)	0.056 (3)	0.0005 (19)	0.024 (2)	0.021 (2)
C3	0.067 (3)	0.035 (2)	0.049 (3)	0.005 (2)	0.021 (2)	0.019 (2)
C4	0.060 (3)	0.034 (2)	0.045 (3)	0.002 (2)	0.015 (2)	0.018 (2)
C5	0.070 (3)	0.028 (2)	0.050 (3)	0.007 (2)	0.021 (2)	0.0159 (19)
C6	0.049 (3)	0.039 (2)	0.054 (3)	0.013 (2)	0.017 (2)	0.023 (2)
C7	0.050 (3)	0.034 (2)	0.040 (3)	0.0032 (19)	0.011 (2)	0.0167 (19)
C8	0.047 (3)	0.041 (3)	0.053 (3)	0.009 (2)	0.020 (2)	0.014 (2)
C9	0.054 (3)	0.028 (2)	0.044 (3)	0.0075 (19)	0.020 (2)	0.0130 (18)
C10	0.068 (3)	0.031 (2)	0.045 (3)	0.008 (2)	0.024 (2)	0.0141 (19)
C11	0.111 (5)	0.039 (3)	0.066 (4)	0.019 (3)	0.037 (3)	0.027 (3)
C12	0.080 (4)	0.077 (4)	0.103 (5)	0.043 (4)	0.042 (4)	0.055 (4)
C13	0.061 (4)	0.079 (4)	0.080 (4)	0.027 (3)	0.028 (3)	0.040 (3)
C14	0.053 (3)	0.041 (3)	0.072 (4)	0.007 (2)	0.021 (3)	0.025 (2)
C15	0.045 (3)	0.031 (2)	0.040 (3)	0.0051 (18)	0.013 (2)	0.0095 (18)
C16	0.043 (3)	0.044 (3)	0.063 (3)	0.007 (2)	0.015 (2)	0.024 (2)
C17	0.050 (3)	0.064 (3)	0.064 (3)	−0.003 (3)	0.014 (3)	0.025 (3)
C18	0.075 (4)	0.046 (3)	0.055 (3)	−0.007 (3)	0.025 (3)	0.018 (2)
C19	0.076 (4)	0.039 (3)	0.043 (3)	0.008 (2)	0.018 (2)	0.019 (2)
C20	0.053 (3)	0.036 (2)	0.041 (3)	0.014 (2)	0.016 (2)	0.0135 (19)
N1	0.046 (2)	0.0310 (18)	0.057 (2)	0.0084 (16)	0.0239 (18)	0.0205 (17)
O1	0.050 (2)	0.078 (3)	0.096 (3)	0.019 (2)	0.033 (2)	0.039 (2)
C21	0.095 (5)	0.049 (3)	0.062 (4)	−0.017 (3)	0.001 (3)	0.021 (3)
C24	0.197 (9)	0.131 (6)	0.100 (5)	−0.054 (6)	0.005 (4)	0.034 (5)
C22	0.179 (9)	0.106 (6)	0.120 (7)	−0.064 (6)	−0.080 (6)	0.078 (5)
C25	0.197 (9)	0.131 (6)	0.100 (5)	−0.054 (6)	0.005 (4)	0.034 (5)
C23	0.160 (8)	0.107 (6)	0.041 (4)	−0.016 (5)	0.017 (4)	−0.004 (3)

Geometric parameters (Å, º) top

Br1—C10	1.908 (5)	C12—H12	0.9300
Br2—C20	1.904 (5)	C13—C14	1.380 (7)
C1—N1	1.476 (5)	C13—H13	0.9300
C1—C9	1.507 (6)	C14—H14	0.9300
C1—C2	1.537 (7)	C15—C20	1.400 (6)
C1—H1	0.9800	C15—C16	1.402 (6)
C2—C8	1.521 (6)	C16—C17	1.379 (7)
C2—C3	1.542 (7)	C16—H16	0.9300
C2—H2	0.9800	C17—C18	1.390 (8)
C3—C4	1.534 (6)	C17—H17	0.9300
C3—H3A	0.9700	C18—C19	1.367 (7)
C3—H3B	0.9700	C18—H18	0.9300
C4—C5	1.528 (6)	C19—C20	1.381 (6)
C4—C21	1.574 (7)	C19—H19	0.9300
C4—H4	0.9800	N1—H1A	0.8600
C5—C6	1.538 (6)	C21—C24	1.537 (10)
C5—H5A	0.9700	C21—C22	1.565 (11)
C5—H5B	0.9700	C21—C23	1.567 (10)
C6—C8	1.483 (6)	C24—C25	1.553 (12)
C6—C7	1.531 (6)	C24—H24A	0.9700
C6—H6	0.9800	C24—H24B	0.9700
C7—N1	1.468 (6)	C22—H22A	0.9600
C7—C15	1.503 (6)	C22—H22B	0.9600
C7—H7	0.9800	C22—H22C	0.9600
C8—O1	1.220 (6)	C25—H25A	0.9600
C9—C14	1.364 (7)	C25—H25B	0.9600
C9—C10	1.406 (6)	C25—H25C	0.9600
C10—C11	1.385 (7)	C23—H23A	0.9600
C11—C12	1.376 (8)	C23—H23B	0.9600
C11—H11	0.9300	C23—H23C	0.9600
C12—C13	1.401 (8)

N1—C1—C9	108.6 (4)	C14—C13—C12	119.0 (6)
N1—C1—C2	110.2 (3)	C14—C13—H13	120.5
C9—C1—C2	113.0 (4)	C12—C13—H13	120.5
N1—C1—H1	108.3	C9—C14—C13	123.5 (5)
C9—C1—H1	108.3	C9—C14—H14	118.2
C2—C1—H1	108.3	C13—C14—H14	118.2
C8—C2—C1	107.1 (4)	C20—C15—C16	115.7 (4)
C8—C2—C3	107.6 (4)	C20—C15—C7	123.0 (4)
C1—C2—C3	116.3 (4)	C16—C15—C7	121.3 (4)
C8—C2—H2	108.5	C17—C16—C15	122.0 (4)
C1—C2—H2	108.5	C17—C16—H16	119.0
C3—C2—H2	108.5	C15—C16—H16	119.0
C4—C3—C2	115.2 (4)	C16—C17—C18	120.0 (5)
C4—C3—H3A	108.5	C16—C17—H17	120.0
C2—C3—H3A	108.5	C18—C17—H17	120.0
C4—C3—H3B	108.5	C19—C18—C17	119.7 (5)
C2—C3—H3B	108.5	C19—C18—H18	120.1
H3A—C3—H3B	107.5	C17—C18—H18	120.1
C5—C4—C3	111.0 (4)	C18—C19—C20	119.8 (5)
C5—C4—C21	114.0 (4)	C18—C19—H19	120.1
C3—C4—C21	112.0 (4)	C20—C19—H19	120.1
C5—C4—H4	106.4	C19—C20—C15	122.7 (5)
C3—C4—H4	106.4	C19—C20—Br2	116.5 (3)
C21—C4—H4	106.4	C15—C20—Br2	120.8 (3)
C4—C5—C6	116.3 (4)	C7—N1—C1	114.5 (4)
C4—C5—H5A	108.2	C7—N1—H1A	122.7
C6—C5—H5A	108.2	C1—N1—H1A	122.7
C4—C5—H5B	108.2	C24—C21—C22	110.5 (7)
C6—C5—H5B	108.2	C24—C21—C23	103.6 (6)
H5A—C5—H5B	107.4	C22—C21—C23	111.4 (7)
C8—C6—C7	108.2 (4)	C24—C21—C4	109.9 (5)
C8—C6—C5	107.5 (4)	C22—C21—C4	110.9 (5)
C7—C6—C5	114.9 (4)	C23—C21—C4	110.3 (5)
C8—C6—H6	108.7	C21—C24—C25	110.3 (8)
C7—C6—H6	108.7	C21—C24—H24A	109.6
C5—C6—H6	108.7	C25—C24—H24A	109.6
N1—C7—C15	109.9 (4)	C21—C24—H24B	109.6
N1—C7—C6	111.0 (3)	C25—C24—H24B	109.6
C15—C7—C6	112.2 (3)	H24A—C24—H24B	108.1
N1—C7—H7	107.9	C21—C22—H22A	109.5
C15—C7—H7	107.9	C21—C22—H22B	109.5
C6—C7—H7	107.9	H22A—C22—H22B	109.5
O1—C8—C6	125.0 (4)	C21—C22—H22C	109.5
O1—C8—C2	123.3 (4)	H22A—C22—H22C	109.5
C6—C8—C2	111.7 (4)	H22B—C22—H22C	109.5
C14—C9—C10	116.3 (4)	C24—C25—H25A	109.5
C14—C9—C1	122.2 (4)	C24—C25—H25B	109.5
C10—C9—C1	121.5 (4)	H25A—C25—H25B	109.5
C11—C10—C9	122.0 (5)	C24—C25—H25C	109.5
C11—C10—Br1	116.8 (4)	H25A—C25—H25C	109.5
C9—C10—Br1	121.2 (4)	H25B—C25—H25C	109.5
C12—C11—C10	119.8 (5)	C21—C23—H23A	109.5
C12—C11—H11	120.1	C21—C23—H23B	109.5
C10—C11—H11	120.1	H23A—C23—H23B	109.5
C11—C12—C13	119.4 (5)	C21—C23—H23C	109.5
C11—C12—H12	120.3	H23A—C23—H23C	109.5
C13—C12—H12	120.3	H23B—C23—H23C	109.5

N1—C1—C2—C8	−56.2 (5)	C10—C11—C12—C13	−1.7 (9)
C9—C1—C2—C8	−178.0 (4)	C11—C12—C13—C14	3.2 (9)
N1—C1—C2—C3	64.1 (5)	C10—C9—C14—C13	−0.1 (8)
C9—C1—C2—C3	−57.7 (5)	C1—C9—C14—C13	179.5 (5)
C8—C2—C3—C4	52.9 (5)	C12—C13—C14—C9	−2.4 (9)
C1—C2—C3—C4	−67.2 (5)	N1—C7—C15—C20	−156.6 (4)
C2—C3—C4—C5	−43.5 (5)	C6—C7—C15—C20	79.4 (5)
C2—C3—C4—C21	−172.2 (4)	N1—C7—C15—C16	25.0 (6)
C3—C4—C5—C6	43.8 (5)	C6—C7—C15—C16	−99.0 (5)
C21—C4—C5—C6	171.4 (4)	C20—C15—C16—C17	−2.7 (7)
C4—C5—C6—C8	−53.5 (5)	C7—C15—C16—C17	175.8 (5)
C4—C5—C6—C7	67.0 (5)	C15—C16—C17—C18	1.3 (8)
C8—C6—C7—N1	55.2 (5)	C16—C17—C18—C19	0.3 (8)
C5—C6—C7—N1	−64.8 (5)	C17—C18—C19—C20	−0.4 (8)
C8—C6—C7—C15	178.6 (4)	C18—C19—C20—C15	−1.1 (7)
C5—C6—C7—C15	58.6 (5)	C18—C19—C20—Br2	179.1 (4)
C7—C6—C8—O1	118.8 (5)	C16—C15—C20—C19	2.6 (6)
C5—C6—C8—O1	−116.6 (5)	C7—C15—C20—C19	−175.9 (4)
C7—C6—C8—C2	−61.2 (5)	C16—C15—C20—Br2	−177.6 (3)
C5—C6—C8—C2	63.4 (5)	C7—C15—C20—Br2	3.9 (6)
C1—C2—C8—O1	−118.1 (5)	C15—C7—N1—C1	−178.9 (3)
C3—C2—C8—O1	116.2 (5)	C6—C7—N1—C1	−54.2 (5)
C1—C2—C8—C6	61.9 (5)	C9—C1—N1—C7	179.5 (3)
C3—C2—C8—C6	−63.8 (5)	C2—C1—N1—C7	55.1 (5)
N1—C1—C9—C14	−28.3 (6)	C5—C4—C21—C24	48.8 (8)
C2—C1—C9—C14	94.4 (5)	C3—C4—C21—C24	175.8 (6)
N1—C1—C9—C10	151.3 (4)	C5—C4—C21—C22	171.4 (6)
C2—C1—C9—C10	−86.0 (5)	C3—C4—C21—C22	−61.6 (7)
C14—C9—C10—C11	1.8 (7)	C5—C4—C21—C23	−64.8 (6)
C1—C9—C10—C11	−177.9 (4)	C3—C4—C21—C23	62.3 (6)
C14—C9—C10—Br1	−179.2 (4)	C22—C21—C24—C25	−54.6 (10)
C1—C9—C10—Br1	1.1 (6)	C23—C21—C24—C25	−174.0 (8)
C9—C10—C11—C12	−0.9 (8)	C4—C21—C24—C25	68.2 (10)
Br1—C10—C11—C12	−179.9 (5)

Experimental details

Crystal data
Chemical formula	C₂₅H₂₉Br₂NO
M_r	519.31
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.7342 (7), 10.6409 (10), 15.0924 (12)
α, β, γ (°)	105.856 (4), 101.242 (4), 97.112 (4)
V (Å³)	1151.08 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.54
Crystal size (mm)	0.18 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.569, 0.719
No. of measured, independent and observed [I > 2σ(I)] reflections	16189, 6006, 3081
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.693

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.212, 1.02
No. of reflections	6006
No. of parameters	259
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.24, −1.26

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Acknowledgements

This research was supported by the Brain Korea 21 (BK 21) Research Program (a human resource development program of the Korean government). The authors acknowledge the Department of Chemistry, IIT Madras, for the X-ray data collection.

References

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