6-Bromo-1-butylindoline-2,3-dione

Ji, L.; Fang, Q.; Fan, J.

doi:10.1107/S1600536808042098

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o136

doi:10.1107/S1600536808042098

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6-Bromo-1-butylindoline-2,3-dione

Lei Ji,^a Qi Fang ^b ^* and Jian-dong Fan ^b

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, Shandong Province, People's Republic of China, and ^bState Key Laboratory of Crystalline Materials, Shandong University, Jinan 250100, Shandong Province, People's Republic of China
^*Correspondence e-mail: fangqi@sdu.edu.cn

(Received 12 October 2008; accepted 10 December 2008; online 17 December 2008)

There are two independent molecules in the asymmetric unit of the title compound, C₁₂H₁₂BrNO₂. The C—C bond lengths of the two carbonyl C atoms of the five-membered rings are distinctly longer than a normal Csp²—Csp² single bond. One of the molecules makes parallel self-coupled (inversion) dimers by π–π interactions with phenyl–phenyl interplanar distances of 3.403 (2) Å. The other molecule also forms self-dimers at longer phenyl–phenyl plane distances [3.649 (2) Å]. In the crystal, a C—H⋯O interaction is seen.

Related literature

For synthesis and applications, see: Kopka et al. (2006 ); Pirrung et al. (2005 ); Zhou et al. (2006 ). For related crystal structures, see: Goldschmidt & Llewellyn (1950 ); Palenik et al. (1990 ).

Experimental

Crystal data

C₁₂H₁₂BrNO₂
M_r = 282.14
Monoclinic, P 2₁ /c
a = 13.3097 (2) Å
b = 11.8793 (2) Å
c = 16.2238 (2) Å
β = 112.340 (1)°
V = 2372.62 (6) Å³
Z = 8
Mo Kα radiation
μ = 3.45 mm⁻¹
T = 296 (2) K
0.37 × 0.13 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.526, T_max = 0.744 (expected range = 0.487–0.689)
16713 measured reflections
5170 independent reflections
2424 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.070
S = 0.93
5170 reflections
364 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Selected bond lengths (Å)

N1—C1	1.375 (3)
N1—C8	1.411 (4)
N1—C9	1.425 (4)
C1—C2	1.545 (4)
N2—C21	1.373 (3)
N2—C28	1.401 (3)
N2—C29	1.467 (4)
C21—C22	1.558 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O3ⁱ	0.95 (3)	2.44 (3)	3.367 (5)	165 (2)
Symmetry code: (i) -x, -y, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042098/cs2100sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042098/cs2100Isup2.hkl

checkCIF report

Comment top

Isatin, 2,3-indolinedione is traditionally obtained from oxidation of oxindole and indigo blue. Its derivates have long been used as precursors of medicines and reductive dyes (Zhou et al., 2006; Pirrung et al., 2005; Kopka et al., 2006). The first crystal structure report on isatin was by Goldschmidt and Llewellyn, 1950. Here we report the crystal structure of N-butyl-6-bromoisatin. There are two independent molecules in the asymmetric unit with very similar bond parameters. Except for the fused aromatic bond of C3≐C8 in one molecule and C23≐C28 bond in the other molecule, four other bonds in the five-membered heterocyclic rings can be classified as single C—C bonds and π-conjugated C≐N bonds. The C1—C2 (1.545 (4) Å) and C21—C22 (1.558 (4) Å) bond lengths are longer than expected for a C(sp²)-C(sp²) single bond. This may be the result of the repulsion of the lone pair electrons of the two oxygen atoms in cis-diones (Palenik et al., 1990). Nitrogen atoms and their three bonded carbons are perfectly co-planar, showing that the sp² N atoms allocate two p_z electrons for π-bonding. The bond lengths of the π-conjugated N≐C bonds (c.f. Table 1) are much shorter than a single C—N bond length. Molecules are packed in dimers (Figure 2). One kind of the independent molecules are linked through a symmetry center to form dimer stack A while two other molecules form another dimer stack B. Mean planes of A and B dimers have a dihedral angle of 85.8 (1)°. The phenyl-phenyl spacing (3.40 (1) Å) in A dimers is considerably shorter than the spacing (3.65 (1) Å) in teh B dimers, indicating relatively stronger intermolecular π-π interactions between these A molecules. The intermolecular interactions in dimer A are further strengthened by C–Br short contacts. The C1···Br1[-x+1, -y+1, -z] and C2···Br1[-x+1, -y+1, -z] in dimer A are 3.476 (3) Å and 3.538 (3) Å, respectively. By comparison, the corresponding C···Br contacts in dimer B are much longer with the shortest distance being 3.672 (4) Å for C22···Br2[-x+1, -y+1, -z]. It may be the result of these different C···Br contacts that the C1—C2 bond length in dimer A is marginally shorter than the C21—C22 bond in dimer B. Amongst intermolecular C—H···O hydrogen bonds the strongest is the C7—H7···O3 one between dimers A and B (see Table 2).

Related literature top

For synthesis and applications, see: Kopka et al. (2006); Pirrung et al. (2005); Zhou et al. (2006). For related crystal structures, see: Goldschmidt & Llewellyn (1950); Palenik et al. (1990).

Experimental top

6-Bromoisatin (10.5 g) was dissolved in 100 ml DMSO in a three-necked flask. Then KI (3.50 g), cetyltrimethyl ammonium bromide (1.00 g), and KOH (30.0 g) in 20.0 g water were added. Then 40.0 ml of n-bromobutane was added drop-wise into the above mixture with stirring. The mixture was stirred at 343 K for 2 days under nitrogen protection. The reaction mixture was washed by water, extracted with CHCl₃, then the chloroform layer was dried by Na₂SO₄. After vaporizing the solvent, the crude product was purified by column chromatography, resulting in 9.5 g (yield 71%) N-butyl-6-bromoisatin product. The compound was dissolved in chloroform again. On most of the solvent evaporating at room temperature orange lump title crystals were formed.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Two N-butyl-6-bromoisatin molecules in the asymmetric unit with 30% probability displacement ellipsoids
	Fig. 2. The molecular packing of the crystal showing the dimer structure [symmetry code: (i)-x+1, -y+1, -z]

6-Bromo-1-butylindoline-2,3-dione top

Crystal data top

C₁₂H₁₂BrNO₂	F(000) = 1136
M_r = 282.14	D_x = 1.580 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3677 reflections
a = 13.3097 (2) Å	θ = 2.2–23.8°
b = 11.8793 (2) Å	µ = 3.45 mm⁻¹
c = 16.2238 (2) Å	T = 296 K
β = 112.340 (1)°	Plank, orange
V = 2372.62 (6) Å³	0.37 × 0.13 × 0.11 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	5170 independent reflections
Radiation source: fine-focus sealed tube	2424 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.0°, θ_min = 1.7°
phi and ω scans	h = −16→17
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −15→10
T_min = 0.526, T_max = 0.744	l = −20→20
16713 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0158P)²] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max = 0.001
5170 reflections	Δρ_max = 0.39 e Å⁻³
364 parameters	Δρ_min = −0.49 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00147 (12)

Crystal data top

C₁₂H₁₂BrNO₂	V = 2372.62 (6) Å³
M_r = 282.14	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.3097 (2) Å	µ = 3.45 mm⁻¹
b = 11.8793 (2) Å	T = 296 K
c = 16.2238 (2) Å	0.37 × 0.13 × 0.11 mm
β = 112.340 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5170 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2424 reflections with I > 2σ(I)
T_min = 0.526, T_max = 0.744	R_int = 0.076
16713 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.39 e Å⁻³
5170 reflections	Δρ_min = −0.49 e Å⁻³
364 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.25474 (2)	0.52247 (4)	0.03130 (3)	0.07546 (17)
O1	0.82928 (15)	0.3064 (2)	0.18511 (13)	0.0649 (7)
O2	0.82426 (16)	0.5497 (2)	0.22161 (15)	0.0682 (7)
N1	0.64300 (18)	0.3303 (3)	0.12570 (15)	0.0448 (7)
C1	0.7490 (2)	0.3648 (3)	0.1675 (2)	0.0477 (9)
C2	0.7445 (2)	0.4919 (3)	0.18633 (19)	0.0475 (9)
C3	0.6286 (2)	0.5203 (3)	0.15321 (19)	0.0431 (9)
C4	0.5754 (3)	0.6195 (4)	0.1517 (2)	0.0519 (10)
H4	0.616 (2)	0.688 (3)	0.1810 (18)	0.058 (10)*
C5	0.4628 (3)	0.6193 (4)	0.1150 (2)	0.0535 (10)
H5	0.4240 (19)	0.690 (3)	0.1167 (16)	0.047 (9)*
C6	0.4095 (2)	0.5211 (4)	0.0815 (2)	0.0476 (9)
C7	0.4595 (2)	0.4196 (4)	0.0807 (2)	0.0435 (9)
H7	0.4227 (18)	0.351 (2)	0.0576 (16)	0.036 (9)*
C8	0.5720 (2)	0.4213 (3)	0.11826 (18)	0.0382 (8)
C9	0.6102 (3)	0.2182 (3)	0.0965 (3)	0.0504 (10)
H9A	0.538 (2)	0.218 (3)	0.040 (2)	0.073 (10)*
H9B	0.659 (2)	0.185 (3)	0.081 (2)	0.078 (13)*
C10	0.5921 (3)	0.1458 (4)	0.1651 (3)	0.0640 (11)
H10B	0.537 (2)	0.185 (2)	0.1859 (17)	0.052 (9)*
H10A	0.658 (2)	0.147 (3)	0.221 (2)	0.070 (11)*
C11	0.5557 (4)	0.0275 (4)	0.1272 (3)	0.0831 (14)
H11A	0.613 (3)	−0.012 (3)	0.121 (2)	0.100*
H11B	0.477 (3)	0.032 (3)	0.085 (2)	0.100*
C12	0.5496 (3)	−0.0541 (4)	0.1927 (3)	0.1061 (15)
H12A	0.6201	−0.0628	0.2392	0.138 (10)*
H12B	0.5253	−0.1253	0.1641	0.138 (10)*
H12C	0.4993	−0.0276	0.2179	0.138 (10)*
Br2	0.25658 (2)	−0.10901 (4)	0.09621 (3)	0.07726 (17)
O3	−0.32733 (16)	−0.1957 (2)	0.03877 (14)	0.0728 (8)
O4	−0.30063 (18)	−0.2190 (2)	−0.13304 (15)	0.0795 (8)
N2	−0.14314 (18)	−0.1581 (2)	0.08915 (16)	0.0493 (7)
C21	−0.2438 (3)	−0.1837 (3)	0.0266 (2)	0.0550 (10)
C22	−0.2278 (3)	−0.1969 (3)	−0.0632 (2)	0.0538 (9)
C23	−0.1117 (2)	−0.1769 (3)	−0.0404 (2)	0.0446 (8)
C24	−0.0483 (3)	−0.1808 (3)	−0.0900 (3)	0.0552 (10)
H24	−0.084 (2)	−0.193 (3)	−0.1480 (19)	0.060 (11)*
C25	0.0612 (3)	−0.1618 (3)	−0.0495 (3)	0.0599 (10)
H25	0.1067 (18)	−0.164 (2)	−0.0805 (16)	0.035 (8)*
C26	0.1047 (2)	−0.1379 (3)	0.0399 (2)	0.0513 (9)
C27	0.0439 (2)	−0.1332 (3)	0.0925 (2)	0.0501 (10)
H27	0.0727 (17)	−0.120 (2)	0.1503 (16)	0.034 (9)*
C28	−0.0653 (2)	−0.1544 (3)	0.0505 (2)	0.0443 (8)
C29	−0.1191 (3)	−0.1497 (4)	0.1850 (2)	0.0545 (11)
H29A	−0.1731 (19)	−0.188 (2)	0.1991 (16)	0.045 (9)*
H29B	−0.056 (2)	−0.198 (3)	0.2144 (19)	0.068 (11)*
C30	−0.1031 (3)	−0.0315 (4)	0.2208 (3)	0.0592 (11)
H30B	−0.049 (2)	0.010 (3)	0.200 (2)	0.077 (11)*
H30A	−0.162 (2)	0.016 (3)	0.195 (2)	0.067 (12)*
C31	−0.0728 (4)	−0.0318 (4)	0.3219 (3)	0.0771 (13)
H31B	−0.002 (3)	−0.071 (3)	0.355 (2)	0.112 (17)*
H31A	−0.133 (3)	−0.073 (3)	0.333 (2)	0.103 (14)*
C32	−0.0463 (3)	0.0819 (4)	0.3617 (2)	0.0941 (14)
H32A	0.0122	0.1132	0.3483	0.129 (9)*
H32B	−0.0249	0.0766	0.4252	0.129 (9)*
H32C	−0.1090	0.1295	0.3376	0.129 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03753 (19)	0.1118 (4)	0.0741 (3)	0.0122 (2)	0.01790 (17)	0.0168 (3)
O1	0.0405 (12)	0.082 (2)	0.0631 (16)	0.0147 (13)	0.0090 (11)	−0.0007 (14)
O2	0.0450 (13)	0.081 (2)	0.0662 (16)	−0.0181 (13)	0.0076 (12)	−0.0127 (15)
N1	0.0369 (14)	0.046 (2)	0.0473 (17)	−0.0027 (15)	0.0110 (12)	−0.0079 (17)
C1	0.0397 (19)	0.060 (3)	0.039 (2)	−0.0006 (19)	0.0107 (16)	0.001 (2)
C2	0.0372 (17)	0.062 (3)	0.038 (2)	−0.0066 (19)	0.0086 (15)	0.003 (2)
C3	0.0376 (17)	0.049 (3)	0.038 (2)	−0.0040 (19)	0.0091 (15)	−0.005 (2)
C4	0.056 (2)	0.045 (3)	0.051 (2)	−0.007 (2)	0.0165 (18)	−0.006 (2)
C5	0.053 (2)	0.051 (3)	0.056 (2)	0.010 (2)	0.0202 (19)	0.002 (2)
C6	0.0317 (16)	0.069 (3)	0.039 (2)	0.006 (2)	0.0095 (15)	0.005 (2)
C7	0.0361 (18)	0.049 (3)	0.042 (2)	−0.008 (2)	0.0114 (16)	−0.003 (2)
C8	0.0375 (17)	0.044 (2)	0.0305 (18)	0.0009 (18)	0.0100 (14)	0.0031 (18)
C9	0.052 (2)	0.043 (3)	0.053 (3)	0.005 (2)	0.016 (2)	−0.007 (2)
C10	0.072 (3)	0.050 (3)	0.064 (3)	−0.009 (2)	0.019 (2)	−0.004 (3)
C11	0.087 (3)	0.075 (4)	0.077 (3)	−0.005 (3)	0.020 (3)	0.003 (3)
C12	0.121 (4)	0.080 (4)	0.107 (4)	−0.018 (3)	0.032 (3)	−0.006 (4)
Br2	0.0453 (2)	0.0909 (4)	0.0969 (3)	0.0008 (2)	0.0285 (2)	−0.0097 (3)
O3	0.0427 (12)	0.090 (2)	0.0790 (17)	−0.0143 (13)	0.0160 (12)	−0.0119 (15)
O4	0.0672 (15)	0.094 (2)	0.0514 (16)	−0.0202 (15)	−0.0066 (13)	−0.0106 (16)
N2	0.0385 (14)	0.070 (2)	0.0342 (16)	−0.0056 (14)	0.0078 (12)	−0.0067 (16)
C21	0.048 (2)	0.059 (3)	0.049 (2)	−0.008 (2)	0.0089 (18)	−0.010 (2)
C22	0.055 (2)	0.042 (3)	0.052 (2)	−0.0093 (19)	0.0065 (18)	−0.004 (2)
C23	0.0489 (19)	0.043 (2)	0.036 (2)	−0.0037 (17)	0.0100 (17)	−0.0023 (19)
C24	0.072 (3)	0.050 (3)	0.036 (2)	−0.003 (2)	0.012 (2)	−0.003 (2)
C25	0.069 (3)	0.063 (3)	0.059 (3)	0.007 (2)	0.036 (2)	0.003 (2)
C26	0.0444 (18)	0.050 (3)	0.057 (2)	0.0006 (17)	0.0175 (18)	−0.001 (2)
C27	0.0423 (19)	0.064 (3)	0.038 (2)	0.0006 (18)	0.0095 (18)	−0.006 (2)
C28	0.0395 (17)	0.050 (2)	0.038 (2)	−0.0023 (16)	0.0089 (16)	−0.0028 (19)
C29	0.048 (2)	0.070 (3)	0.048 (2)	−0.007 (2)	0.0202 (19)	−0.004 (2)
C30	0.057 (2)	0.064 (3)	0.058 (3)	−0.006 (2)	0.023 (2)	−0.008 (3)
C31	0.103 (4)	0.076 (4)	0.065 (3)	−0.021 (3)	0.046 (3)	−0.020 (3)
C32	0.116 (3)	0.101 (4)	0.076 (3)	−0.027 (3)	0.048 (2)	−0.029 (3)

Geometric parameters (Å, º) top

Br1—C6	1.906 (3)	Br2—C26	1.907 (3)
O1—C1	1.214 (3)	O3—C21	1.209 (3)
O2—C2	1.210 (3)	O4—C22	1.208 (3)
N1—C1	1.375 (3)	N2—C21	1.373 (3)
N1—C8	1.411 (4)	N2—C28	1.401 (3)
N1—C9	1.425 (4)	N2—C29	1.467 (4)
C1—C2	1.545 (4)	C21—C22	1.558 (4)
C2—C3	1.468 (4)	C22—C23	1.465 (4)
C3—C4	1.370 (4)	C23—C24	1.370 (4)
C3—C8	1.395 (4)	C23—C28	1.391 (4)
C4—C5	1.387 (4)	C24—C25	1.371 (4)
C4—H4	0.99 (3)	C24—H24	0.89 (3)
C5—C6	1.366 (4)	C25—C26	1.372 (4)
C5—H5	1.00 (3)	C25—H25	0.92 (2)
C6—C7	1.379 (4)	C26—C27	1.382 (4)
C7—C8	1.386 (4)	C27—C28	1.374 (4)
C7—H7	0.95 (3)	C27—H27	0.88 (2)
C9—C10	1.496 (5)	C29—C30	1.503 (5)
C9—H9A	1.05 (3)	C29—H29A	0.95 (3)
C9—H9B	0.87 (3)	C29—H29B	0.98 (3)
C10—C11	1.536 (6)	C30—C31	1.532 (5)
C10—H10B	1.03 (3)	C30—H30B	1.04 (3)
C10—H10A	0.99 (3)	C30—H30A	0.93 (3)
C11—C12	1.464 (6)	C31—C32	1.481 (5)
C11—H11A	0.94 (4)	C31—H31B	1.00 (4)
C11—H11B	1.01 (3)	C31—H31A	1.01 (4)
C12—H12A	0.9600	C32—H32A	0.9600
C12—H12B	0.9600	C32—H32B	0.9600
C12—H12C	0.9600	C32—H32C	0.9600

C1—N1—C8	110.0 (3)	C21—N2—C28	110.9 (2)
C1—N1—C9	124.8 (3)	C21—N2—C29	123.9 (3)
C8—N1—C9	125.3 (3)	C28—N2—C29	124.9 (2)
O1—C1—N1	126.3 (3)	O3—C21—N2	127.2 (3)
O1—C1—C2	127.4 (3)	O3—C21—C22	127.0 (3)
N1—C1—C2	106.3 (3)	N2—C21—C22	105.7 (3)
O2—C2—C3	130.8 (4)	O4—C22—C23	131.7 (3)
O2—C2—C1	123.8 (3)	O4—C22—C21	123.5 (3)
C3—C2—C1	105.5 (3)	C23—C22—C21	104.7 (3)
C4—C3—C8	121.5 (3)	C24—C23—C28	120.3 (3)
C4—C3—C2	132.0 (3)	C24—C23—C22	132.2 (3)
C8—C3—C2	106.5 (3)	C28—C23—C22	107.4 (3)
C3—C4—C5	118.2 (4)	C23—C24—C25	119.6 (3)
C3—C4—H4	120.7 (16)	C23—C24—H24	115.6 (18)
C5—C4—H4	120.8 (16)	C25—C24—H24	124.7 (19)
C6—C5—C4	119.1 (4)	C24—C25—C26	119.0 (3)
C6—C5—H5	122.6 (15)	C24—C25—H25	122.3 (15)
C4—C5—H5	118.3 (15)	C26—C25—H25	118.7 (15)
C5—C6—C7	124.8 (3)	C25—C26—C27	123.4 (3)
C5—C6—Br1	118.4 (3)	C25—C26—Br2	119.2 (3)
C7—C6—Br1	116.8 (3)	C27—C26—Br2	117.4 (3)
C6—C7—C8	115.3 (3)	C28—C27—C26	116.3 (3)
C6—C7—H7	125.2 (15)	C28—C27—H27	120.7 (16)
C8—C7—H7	119.5 (15)	C26—C27—H27	123.0 (16)
C7—C8—C3	121.1 (3)	C27—C28—C23	121.4 (3)
C7—C8—N1	127.1 (3)	C27—C28—N2	127.3 (3)
C3—C8—N1	111.8 (3)	C23—C28—N2	111.3 (2)
N1—C9—C10	113.9 (3)	N2—C29—C30	114.5 (3)
N1—C9—H9A	110.8 (17)	N2—C29—H29A	110.0 (15)
C10—C9—H9A	107.0 (17)	C30—C29—H29A	111.5 (17)
N1—C9—H9B	111 (2)	N2—C29—H29B	106.1 (17)
C10—C9—H9B	108 (2)	C30—C29—H29B	112.8 (18)
H9A—C9—H9B	106 (3)	H29A—C29—H29B	101 (2)
C9—C10—C11	110.1 (4)	C29—C30—C31	110.6 (4)
C9—C10—H10B	108.8 (16)	C29—C30—H30B	109.3 (18)
C11—C10—H10B	112.8 (16)	C31—C30—H30B	115.0 (17)
C9—C10—H10A	109.7 (18)	C29—C30—H30A	115 (2)
C11—C10—H10A	114.1 (19)	C31—C30—H30A	109 (2)
H10B—C10—H10A	101 (2)	H30B—C30—H30A	98 (3)
C12—C11—C10	114.3 (4)	C32—C31—C30	112.8 (4)
C12—C11—H11A	91 (3)	C32—C31—H31B	100 (2)
C10—C11—H11A	111 (2)	C30—C31—H31B	113 (2)
C12—C11—H11B	101 (2)	C32—C31—H31A	116 (2)
C10—C11—H11B	108 (2)	C30—C31—H31A	107 (2)
H11A—C11—H11B	129 (3)	H31B—C31—H31A	109 (3)
C11—C12—H12A	109.5	C31—C32—H32A	109.5
C11—C12—H12B	109.5	C31—C32—H32B	109.5
H12A—C12—H12B	109.5	H32A—C32—H32B	109.5
C11—C12—H12C	109.5	C31—C32—H32C	109.5
H12A—C12—H12C	109.5	H32A—C32—H32C	109.5
H12B—C12—H12C	109.5	H32B—C32—H32C	109.5

C8—N1—C1—O1	179.0 (3)	C28—N2—C21—O3	178.2 (4)
C9—N1—C1—O1	0.6 (5)	C29—N2—C21—O3	5.0 (6)
C8—N1—C1—C2	−1.6 (3)	C28—N2—C21—C22	−0.5 (4)
C9—N1—C1—C2	180.0 (3)	C29—N2—C21—C22	−173.6 (3)
O1—C1—C2—O2	0.6 (5)	O3—C21—C22—O4	1.8 (6)
N1—C1—C2—O2	−178.8 (3)	N2—C21—C22—O4	−179.6 (3)
O1—C1—C2—C3	−179.3 (3)	O3—C21—C22—C23	−178.2 (3)
N1—C1—C2—C3	1.3 (3)	N2—C21—C22—C23	0.4 (3)
O2—C2—C3—C4	0.2 (6)	O4—C22—C23—C24	−2.7 (7)
C1—C2—C3—C4	−180.0 (3)	C21—C22—C23—C24	177.3 (4)
O2—C2—C3—C8	179.6 (3)	O4—C22—C23—C28	179.8 (4)
C1—C2—C3—C8	−0.5 (3)	C21—C22—C23—C28	−0.2 (4)
C8—C3—C4—C5	0.7 (5)	C28—C23—C24—C25	−0.3 (5)
C2—C3—C4—C5	180.0 (3)	C22—C23—C24—C25	−177.6 (4)
C3—C4—C5—C6	−0.5 (5)	C23—C24—C25—C26	−0.8 (5)
C4—C5—C6—C7	−0.2 (5)	C24—C25—C26—C27	0.8 (6)
C4—C5—C6—Br1	−179.9 (2)	C24—C25—C26—Br2	−179.0 (3)
C5—C6—C7—C8	0.8 (5)	C25—C26—C27—C28	0.2 (5)
Br1—C6—C7—C8	−179.6 (2)	Br2—C26—C27—C28	−180.0 (2)
C6—C7—C8—C3	−0.6 (4)	C26—C27—C28—C23	−1.3 (5)
C6—C7—C8—N1	−179.6 (3)	C26—C27—C28—N2	177.9 (3)
C4—C3—C8—C7	−0.1 (5)	C24—C23—C28—C27	1.4 (5)
C2—C3—C8—C7	−179.6 (3)	C22—C23—C28—C27	179.3 (3)
C4—C3—C8—N1	179.1 (3)	C24—C23—C28—N2	−177.9 (3)
C2—C3—C8—N1	−0.4 (3)	C22—C23—C28—N2	0.0 (4)
C1—N1—C8—C7	−179.6 (3)	C21—N2—C28—C27	−179.0 (3)
C9—N1—C8—C7	−1.2 (5)	C29—N2—C28—C27	−5.9 (5)
C1—N1—C8—C3	1.3 (3)	C21—N2—C28—C23	0.3 (4)
C9—N1—C8—C3	179.7 (3)	C29—N2—C28—C23	173.4 (3)
C1—N1—C9—C10	89.8 (4)	C21—N2—C29—C30	−106.6 (4)
C8—N1—C9—C10	−88.3 (4)	C28—N2—C29—C30	81.2 (4)
N1—C9—C10—C11	179.3 (3)	N2—C29—C30—C31	−177.1 (3)
C9—C10—C11—C12	172.4 (4)	C29—C30—C31—C32	174.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱ	0.95 (3)	2.44 (3)	3.367 (5)	165 (2)

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂BrNO₂
M_r	282.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.3097 (2), 11.8793 (2), 16.2238 (2)
β (°)	112.340 (1)
V (Å³)	2372.62 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.45
Crystal size (mm)	0.37 × 0.13 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.526, 0.744
No. of measured, independent and observed [I > 2σ(I)] reflections	16713, 5170, 2424
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.070, 0.93
No. of reflections	5170
No. of parameters	364
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.49

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

N1—C1	1.375 (3)	N2—C21	1.373 (3)
N1—C8	1.411 (4)	N2—C28	1.401 (3)
N1—C9	1.425 (4)	N2—C29	1.467 (4)
C1—C2	1.545 (4)	C21—C22	1.558 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱ	0.95 (3)	2.44 (3)	3.367 (5)	165 (2)

Symmetry code: (i) −x, −y, −z.

Acknowledgements

This work are supported by the PhD Foundation of the Ministry of Education of China and by the National Natural Science Foundation of China (grant No. 50673054).

References

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