8-Bromo-3-(cyclo­propanylcarbon­yl)-5-methyl­indolizine-1-carbonitrile

Fan, D.; Tang, F.; Wang, W.

doi:10.1107/S1600536812023161

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1897

doi:10.1107/S1600536812023161

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8-Bromo-3-(cyclopropanylcarbonyl)-5-methylindolizine-1-carbonitrile

Dahe Fan,^a Fan Tang ^a and Wei Wang ^a ^*

^aKey Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province, School of Chemical and Biological Engineering, Yancheng Institute of Technology, No. 9, Yingbin Avenue, Yancheng 224051, People's Republic of China
^*Correspondence e-mail: wangw@ycit.edu.cn

(Received 17 May 2012; accepted 21 May 2012; online 26 May 2012)

The asymmetric unit of the title compound, C₁₄H₁₁BrN₂O, contains three independent molecules with very similar geometries. The dihedral angles between the side chain of the cyclopropyl plane and the five-membered ring to which it is attached are 55.0 (2), 58.1 (2) and 60.2 (3)° for the three molecules. Each molecule forms an intramolecular C—H⋯O hydrogen bond.

Related literature

For background to indolizines, see: Sippl (2002 ); Sriram et al. (2005 ); Shen et al. (2007 ); Wu et al. (2011 ). For related structures, see: Shen et al. (2010 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₁BrN₂O
M_r = 303.16
Triclinic, $[P \overline 1]$
a = 8.3443 (7) Å
b = 14.5827 (13) Å
c = 16.9132 (14) Å
α = 70.418 (4)°
β = 88.849 (4)°
γ = 76.833 (4)°
V = 1884.5 (3) Å³
Z = 6
Mo Kα radiation
μ = 3.26 mm⁻¹
T = 296 K
0.48 × 0.33 × 0.11 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.283, T_max = 0.701
22759 measured reflections
6586 independent reflections
5163 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.086
S = 1.05
6586 reflections
487 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯O1	0.96	2.09	2.857 (4)	136
C28—H28C⋯O2	0.96	2.04	2.823 (4)	138
C42—H42B⋯O3	0.96	2.04	2.814 (4)	136

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023161/fj2561sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023161/fj2561Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812023161/fj2561Isup3.cml

checkCIF report

Comment top

Indolizines have been drawing greatly research interest owing to their special electronic structures high fluorescence efficiency (Shen et al., 2007), wide range of biological activity (Sippl, 2002; Wu et al., 2011) and the fact that their partially hydrogenated frameworks have been found in several natural products (Sriram et al., 2005). Meanwhile, the cyclopropane is a noteworthy structural motif because of its own biological activity and its effect to modify the bioactivity of the parent compounds(Shen et al., 2010). We report here the synthesis and crystal structure of the title indolizine compound which is containing cyclopropylcarbonyl group.

The molecular structure of the title compound is shown in Fig. 1. In the title compound, The distance of C—Br bond for these three molecules is 1.883 (3), 1.879 (3), 1.887 (3) Å respectively, similar to the value of 1.882 (3) Å found in the previously reported structure [Wu et al. (2011)]. The values of the geometric parameters for the others in the structure are normal (Allen et al., 1987). the indolizine plane is slightly twisted, with maximum deviations of 5.979 (7), 7.111 (8), and 7.0657 Å from the mean plane. The dihedral angle between the side chain of the cyclpropyl plane and the five-membered ring to which it is attached is 54.98 (20)°, 58.10 (21)° and 60.18 (30)° for the three molecules in the asymmetric unit. Each molecule forms an intramolecular C–H.. O hydrogen bond.

Related literature top

For background to indolizines, see: Sippl (2002); Sriram et al. (2005); Shen et al. (2007); Wu et al. (2011). For related structures, see: Shen et al. (2010). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of the 5-bromo-1-(2-cyclopropyl-2-oxoethyl)-2-methylpyridinium bromide salt (10 mmol), acrylonitrile (40 mmol), triethylamine (2 ml) and TPCD (4 g) in DMF (40 ml) was heated at 90° C for 5 h. After cooling, the reaction mixture was poured into an aqueous hydrochloric acid solution (5%, 100 ml), the precipitated crude product was collected by filtration and further purified by silica gel column chromatography with petroleum ether (bp 60–90 °C)-ethyl acetate as eluents. Yellow crystal. m.p.133–135 °C, Yield 75%. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in petroleum ether -ethyl acetate(5 mL:1 mL), at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with 30% probability displacement ellipsoids. Dashed lines indicate hydrogen bonds.

8-Bromo-3-(cyclopropanylcarbonyl)-5-methylindolizine-1-carbonitrile top

Crystal data top

C₁₄H₁₁BrN₂O	Z = 6
M_r = 303.16	F(000) = 912
Triclinic, P1	D_x = 1.603 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3443 (7) Å	Cell parameters from 9236 reflections
b = 14.5827 (13) Å	θ = 1.5–25.0°
c = 16.9132 (14) Å	µ = 3.26 mm⁻¹
α = 70.418 (4)°	T = 296 K
β = 88.849 (4)°	Block, brown
γ = 76.833 (4)°	0.48 × 0.33 × 0.11 mm
V = 1884.5 (3) Å³

Data collection top

Bruker APEXII diffractometer	6586 independent reflections
Radiation source: fine-focus sealed tube	5163 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −9→9
T_min = 0.283, T_max = 0.701	k = −17→15
22759 measured reflections	l = −20→20

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0481P)² + 0.4575P] where P = (F_o² + 2F_c²)/3
6586 reflections	(Δ/σ)_max = 0.001
487 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₁₄H₁₁BrN₂O	γ = 76.833 (4)°
M_r = 303.16	V = 1884.5 (3) Å³
Triclinic, P1	Z = 6
a = 8.3443 (7) Å	Mo Kα radiation
b = 14.5827 (13) Å	µ = 3.26 mm⁻¹
c = 16.9132 (14) Å	T = 296 K
α = 70.418 (4)°	0.48 × 0.33 × 0.11 mm
β = 88.849 (4)°

Data collection top

Bruker APEXII diffractometer	6586 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	5163 reflections with I > 2σ(I)
T_min = 0.283, T_max = 0.701	R_int = 0.021
22759 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.05	Δρ_max = 0.70 e Å⁻³
6586 reflections	Δρ_min = −0.57 e Å⁻³
487 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	0.19909 (4)	0.54881 (2)	0.167549 (17)	0.05758 (11)
Br2	0.46179 (4)	0.08329 (2)	0.081708 (18)	0.06287 (11)
Br3	−0.27413 (4)	1.16393 (2)	0.23629 (2)	0.06781 (12)
O1	0.3515 (2)	0.55570 (16)	−0.23976 (11)	0.0581 (5)
O2	0.7806 (2)	−0.26508 (16)	0.47575 (11)	0.0566 (5)
O3	0.1415 (2)	0.68795 (15)	0.26399 (12)	0.0577 (5)
N1	0.2480 (2)	0.50577 (15)	−0.06225 (12)	0.0356 (5)
N2	−0.0973 (4)	0.7573 (2)	0.02687 (16)	0.0707 (8)
N3	0.6118 (2)	−0.15356 (15)	0.30490 (12)	0.0353 (5)
N4	0.2182 (4)	0.1597 (2)	0.23731 (19)	0.0856 (10)
N5	0.0605 (3)	0.90135 (17)	0.24767 (13)	0.0424 (5)
N6	−0.2081 (4)	1.0176 (3)	0.46003 (18)	0.0832 (9)
C1	0.1094 (4)	0.7134 (3)	−0.36610 (17)	0.0610 (8)
H1A	0.0176	0.7695	−0.3929	0.073*
H1B	0.2148	0.7308	−0.3658	0.073*
C2	0.1090 (4)	0.6175 (3)	−0.37514 (18)	0.0628 (8)
H2A	0.2142	0.5755	−0.3803	0.075*
H2B	0.0169	0.6142	−0.4074	0.075*
C3	0.0760 (3)	0.6309 (2)	−0.29139 (16)	0.0497 (7)
H3A	−0.0378	0.6372	−0.2744	0.060*
C4	0.2085 (3)	0.5798 (2)	−0.22413 (16)	0.0434 (6)
C5	0.1577 (3)	0.5688 (2)	−0.13826 (15)	0.0384 (6)
C6	0.0458 (3)	0.6420 (2)	−0.12020 (16)	0.0439 (6)
H6A	−0.0318	0.6928	−0.1586	0.053*
C7	0.0660 (3)	0.6288 (2)	−0.03475 (15)	0.0411 (6)
C8	−0.0227 (4)	0.6977 (2)	0.00283 (17)	0.0491 (7)
C9	0.1922 (3)	0.54384 (18)	0.00154 (15)	0.0362 (6)
C10	0.2650 (3)	0.4931 (2)	0.08306 (16)	0.0438 (6)
C11	0.3832 (4)	0.4075 (2)	0.10048 (18)	0.0573 (8)
H11A	0.4347	0.3754	0.1541	0.069*
C12	0.4265 (4)	0.3683 (2)	0.03594 (19)	0.0568 (8)
H12A	0.5051	0.3081	0.0485	0.068*
C13	0.3596 (3)	0.4136 (2)	−0.04408 (17)	0.0438 (6)
C14	0.3917 (4)	0.3656 (2)	−0.10947 (19)	0.0585 (8)
H14A	0.4715	0.3030	−0.0872	0.088*
H14B	0.4334	0.4089	−0.1574	0.088*
H14C	0.2910	0.3540	−0.1261	0.088*
C15	0.5985 (4)	−0.3051 (3)	0.62270 (17)	0.0666 (9)
H15A	0.5205	−0.3340	0.6607	0.080*
H15B	0.7051	−0.3503	0.6255	0.080*
C16	0.5944 (5)	−0.1992 (3)	0.6058 (2)	0.0767 (11)
H16A	0.6984	−0.1792	0.5984	0.092*
H16B	0.5139	−0.1629	0.6335	0.092*
C17	0.5321 (3)	−0.2299 (2)	0.53902 (16)	0.0514 (7)
H17A	0.4123	−0.2129	0.5276	0.062*
C18	0.6347 (3)	−0.2247 (2)	0.46623 (15)	0.0420 (6)
C19	0.5511 (3)	−0.15996 (19)	0.38451 (15)	0.0383 (6)
C20	0.4309 (3)	−0.0747 (2)	0.37356 (16)	0.0436 (6)
H20A	0.3686	−0.0599	0.4159	0.052*
C21	0.4158 (3)	−0.01316 (19)	0.28948 (15)	0.0412 (6)
C22	0.3082 (4)	0.0835 (2)	0.25739 (18)	0.0535 (7)
C23	0.5298 (3)	−0.06160 (19)	0.24619 (15)	0.0361 (6)
C24	0.5740 (3)	−0.0387 (2)	0.16214 (15)	0.0423 (6)
C25	0.6904 (3)	−0.1037 (2)	0.13926 (16)	0.0472 (7)
H25A	0.7250	−0.0863	0.0847	0.057*
C26	0.7591 (3)	−0.1979 (2)	0.19828 (16)	0.0457 (7)
H26A	0.8365	−0.2433	0.1813	0.055*
C27	0.7170 (3)	−0.22544 (19)	0.27943 (16)	0.0403 (6)
C28	0.7673 (4)	−0.3313 (2)	0.33769 (19)	0.0589 (8)
H28A	0.8405	−0.3708	0.3105	0.088*
H28B	0.6712	−0.3577	0.3523	0.088*
H28C	0.8226	−0.3334	0.3877	0.088*
C29	0.3862 (4)	0.5520 (3)	0.3895 (2)	0.0724 (10)
H29A	0.3983	0.5487	0.3332	0.087*
H29B	0.4868	0.5249	0.4256	0.087*
C30	0.2311 (4)	0.5385 (3)	0.4284 (2)	0.0750 (10)
H30A	0.2362	0.5032	0.4885	0.090*
H30B	0.1476	0.5270	0.3962	0.090*
C31	0.2666 (4)	0.6409 (2)	0.39932 (19)	0.0583 (8)
H31A	0.2951	0.6665	0.4425	0.070*
C32	0.1748 (3)	0.7145 (2)	0.32149 (17)	0.0474 (7)
C33	0.1166 (3)	0.8167 (2)	0.31987 (16)	0.0437 (6)
C34	0.0518 (3)	0.8423 (2)	0.38694 (17)	0.0473 (7)
H34A	0.0720	0.8011	0.4429	0.057*
C35	−0.0480 (3)	0.9381 (2)	0.35932 (17)	0.0463 (7)
C36	−0.1394 (4)	0.9854 (2)	0.41319 (18)	0.0569 (8)
C37	−0.0449 (3)	0.9762 (2)	0.27152 (16)	0.0434 (6)
C38	−0.1185 (3)	1.0661 (2)	0.20829 (17)	0.0493 (7)
C39	−0.0805 (4)	1.0834 (2)	0.12739 (19)	0.0594 (8)
H39A	−0.1322	1.1424	0.0854	0.071*
C40	0.0386 (4)	1.0104 (3)	0.10818 (18)	0.0615 (9)
H40A	0.0698	1.0244	0.0531	0.074*
C41	0.1104 (4)	0.9210 (2)	0.16544 (17)	0.0510 (7)
C42	0.2461 (4)	0.8478 (3)	0.1459 (2)	0.0676 (9)
H42A	0.2645	0.8719	0.0870	0.101*
H42B	0.2167	0.7845	0.1598	0.101*
H42C	0.3450	0.8396	0.1781	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0736 (2)	0.0676 (2)	0.03688 (16)	−0.02012 (16)	0.00100 (13)	−0.02217 (15)
Br2	0.0887 (2)	0.0501 (2)	0.03824 (17)	−0.01080 (16)	−0.01259 (14)	−0.00278 (14)
Br3	0.0797 (2)	0.0513 (2)	0.0705 (2)	−0.01124 (16)	0.00471 (17)	−0.02090 (17)
O1	0.0445 (11)	0.0798 (15)	0.0409 (11)	−0.0090 (10)	0.0077 (8)	−0.0129 (10)
O2	0.0390 (11)	0.0724 (14)	0.0430 (11)	−0.0031 (10)	0.0027 (8)	−0.0065 (10)
O3	0.0696 (13)	0.0582 (13)	0.0530 (12)	−0.0119 (10)	−0.0043 (10)	−0.0303 (11)
N1	0.0396 (11)	0.0337 (12)	0.0327 (11)	−0.0100 (9)	0.0020 (8)	−0.0095 (9)
N2	0.092 (2)	0.0556 (17)	0.0534 (16)	−0.0006 (15)	0.0230 (14)	−0.0161 (14)
N3	0.0376 (11)	0.0353 (12)	0.0320 (11)	−0.0089 (9)	0.0011 (8)	−0.0097 (9)
N4	0.094 (2)	0.064 (2)	0.079 (2)	0.0265 (18)	−0.0247 (17)	−0.0258 (17)
N5	0.0517 (13)	0.0485 (14)	0.0366 (12)	−0.0235 (11)	0.0095 (10)	−0.0194 (11)
N6	0.090 (2)	0.097 (2)	0.0611 (18)	0.0017 (18)	0.0166 (16)	−0.0417 (18)
C1	0.0641 (19)	0.066 (2)	0.0413 (16)	−0.0130 (16)	−0.0015 (14)	−0.0040 (15)
C2	0.071 (2)	0.077 (2)	0.0420 (16)	−0.0137 (17)	−0.0046 (14)	−0.0242 (16)
C3	0.0417 (15)	0.069 (2)	0.0341 (14)	−0.0135 (14)	0.0028 (11)	−0.0119 (14)
C4	0.0454 (16)	0.0485 (17)	0.0349 (14)	−0.0147 (13)	0.0044 (11)	−0.0102 (12)
C5	0.0404 (14)	0.0432 (15)	0.0310 (13)	−0.0121 (12)	0.0019 (10)	−0.0101 (12)
C6	0.0428 (14)	0.0448 (16)	0.0357 (14)	−0.0060 (12)	0.0020 (11)	−0.0056 (12)
C7	0.0440 (14)	0.0415 (16)	0.0372 (14)	−0.0119 (12)	0.0103 (11)	−0.0117 (12)
C8	0.0580 (17)	0.0463 (18)	0.0387 (15)	−0.0134 (14)	0.0130 (13)	−0.0086 (14)
C9	0.0438 (14)	0.0336 (14)	0.0330 (13)	−0.0150 (11)	0.0060 (11)	−0.0099 (11)
C10	0.0559 (16)	0.0429 (16)	0.0349 (14)	−0.0179 (13)	−0.0001 (12)	−0.0118 (12)
C11	0.070 (2)	0.0491 (19)	0.0443 (16)	−0.0070 (16)	−0.0140 (14)	−0.0085 (14)
C12	0.0640 (19)	0.0373 (17)	0.0594 (19)	−0.0004 (14)	−0.0101 (15)	−0.0109 (15)
C13	0.0476 (15)	0.0355 (15)	0.0471 (15)	−0.0081 (12)	0.0037 (12)	−0.0136 (13)
C14	0.073 (2)	0.0442 (18)	0.0598 (19)	−0.0086 (15)	0.0099 (15)	−0.0230 (15)
C15	0.064 (2)	0.079 (3)	0.0362 (16)	−0.0077 (17)	0.0092 (14)	0.0007 (16)
C16	0.075 (2)	0.109 (3)	0.057 (2)	−0.019 (2)	0.0127 (17)	−0.044 (2)
C17	0.0418 (15)	0.066 (2)	0.0373 (15)	−0.0086 (13)	0.0050 (11)	−0.0093 (14)
C18	0.0421 (16)	0.0455 (16)	0.0354 (14)	−0.0127 (13)	0.0024 (11)	−0.0084 (12)
C19	0.0380 (13)	0.0415 (15)	0.0339 (13)	−0.0099 (11)	0.0035 (10)	−0.0105 (11)
C20	0.0413 (14)	0.0484 (17)	0.0392 (14)	−0.0051 (12)	0.0008 (11)	−0.0161 (13)
C21	0.0415 (14)	0.0402 (16)	0.0396 (14)	−0.0041 (12)	−0.0051 (11)	−0.0138 (12)
C22	0.0583 (18)	0.0524 (19)	0.0452 (16)	0.0007 (15)	−0.0118 (13)	−0.0189 (14)
C23	0.0410 (14)	0.0345 (14)	0.0343 (13)	−0.0121 (11)	−0.0044 (10)	−0.0109 (11)
C24	0.0536 (16)	0.0417 (16)	0.0317 (13)	−0.0163 (13)	−0.0067 (11)	−0.0088 (12)
C25	0.0541 (16)	0.0606 (19)	0.0333 (14)	−0.0217 (14)	0.0055 (12)	−0.0189 (14)
C26	0.0467 (15)	0.0482 (17)	0.0463 (16)	−0.0106 (13)	0.0052 (12)	−0.0219 (14)
C27	0.0415 (14)	0.0380 (15)	0.0428 (14)	−0.0098 (12)	0.0037 (11)	−0.0153 (12)
C28	0.072 (2)	0.0379 (17)	0.0585 (18)	−0.0051 (15)	0.0139 (15)	−0.0119 (14)
C29	0.067 (2)	0.075 (2)	0.064 (2)	0.0030 (18)	−0.0076 (17)	−0.0227 (19)
C30	0.080 (2)	0.061 (2)	0.071 (2)	−0.0128 (18)	0.0024 (18)	−0.0066 (18)
C31	0.0689 (19)	0.057 (2)	0.0499 (17)	−0.0105 (16)	−0.0032 (14)	−0.0215 (15)
C32	0.0485 (16)	0.0537 (18)	0.0457 (16)	−0.0161 (13)	0.0050 (12)	−0.0217 (14)
C33	0.0505 (15)	0.0497 (17)	0.0372 (14)	−0.0220 (13)	0.0075 (12)	−0.0166 (13)
C34	0.0550 (16)	0.0552 (19)	0.0366 (14)	−0.0209 (14)	0.0038 (12)	−0.0168 (13)
C35	0.0503 (16)	0.0552 (18)	0.0422 (15)	−0.0200 (14)	0.0099 (12)	−0.0235 (14)
C36	0.0617 (19)	0.063 (2)	0.0474 (17)	−0.0136 (16)	0.0080 (14)	−0.0223 (16)
C37	0.0486 (15)	0.0489 (17)	0.0413 (15)	−0.0217 (13)	0.0074 (12)	−0.0201 (13)
C38	0.0589 (17)	0.0450 (17)	0.0500 (17)	−0.0239 (14)	0.0070 (13)	−0.0164 (14)
C39	0.076 (2)	0.054 (2)	0.0504 (18)	−0.0285 (17)	0.0078 (15)	−0.0124 (15)
C40	0.081 (2)	0.078 (2)	0.0362 (16)	−0.0414 (19)	0.0160 (15)	−0.0181 (17)
C41	0.0628 (18)	0.064 (2)	0.0403 (15)	−0.0345 (16)	0.0160 (13)	−0.0244 (16)
C42	0.079 (2)	0.082 (3)	0.060 (2)	−0.0350 (19)	0.0335 (17)	−0.0380 (19)

Geometric parameters (Å, º) top

Br1—C10	1.883 (3)	C16—C17	1.489 (4)
Br2—C24	1.887 (3)	C16—H16A	0.9700
Br3—C38	1.879 (3)	C16—H16B	0.9700
O1—C4	1.215 (3)	C17—C18	1.476 (4)
O2—C18	1.213 (3)	C17—H17A	0.9800
O3—C32	1.219 (3)	C18—C19	1.467 (3)
N1—C13	1.389 (3)	C19—C20	1.368 (4)
N1—C9	1.398 (3)	C20—C21	1.394 (4)
N1—C5	1.413 (3)	C20—H20A	0.9300
N2—C8	1.135 (3)	C21—C23	1.397 (3)
N3—C27	1.387 (3)	C21—C22	1.420 (4)
N3—C23	1.403 (3)	C23—C24	1.409 (3)
N3—C19	1.410 (3)	C24—C25	1.343 (4)
N4—C22	1.136 (4)	C25—C26	1.398 (4)
N5—C41	1.398 (3)	C25—H25A	0.9300
N5—C37	1.405 (3)	C26—C27	1.358 (4)
N5—C33	1.408 (3)	C26—H26A	0.9300
N6—C36	1.134 (4)	C27—C28	1.494 (4)
C1—C2	1.458 (5)	C28—H28A	0.9600
C1—C3	1.497 (4)	C28—H28B	0.9600
C1—H1A	0.9700	C28—H28C	0.9600
C1—H1B	0.9700	C29—C30	1.464 (5)
C2—C3	1.505 (4)	C29—C31	1.501 (4)
C2—H2A	0.9700	C29—H29A	0.9700
C2—H2B	0.9700	C29—H29B	0.9700
C3—C4	1.476 (4)	C30—C31	1.504 (5)
C3—H3A	0.9800	C30—H30A	0.9700
C4—C5	1.471 (3)	C30—H30B	0.9700
C5—C6	1.363 (4)	C31—C32	1.480 (4)
C6—C7	1.401 (3)	C31—H31A	0.9800
C6—H6A	0.9300	C32—C33	1.450 (4)
C7—C9	1.394 (3)	C33—C34	1.373 (4)
C7—C8	1.425 (4)	C34—C35	1.382 (4)
C9—C10	1.401 (3)	C34—H34A	0.9300
C10—C11	1.350 (4)	C35—C37	1.402 (4)
C11—C12	1.399 (4)	C35—C36	1.429 (4)
C11—H11A	0.9300	C37—C38	1.400 (4)
C12—C13	1.358 (4)	C38—C39	1.351 (4)
C12—H12A	0.9300	C39—C40	1.401 (5)
C13—C14	1.486 (4)	C39—H39A	0.9300
C14—H14A	0.9600	C40—C41	1.349 (4)
C14—H14B	0.9600	C40—H40A	0.9300
C14—H14C	0.9600	C41—C42	1.484 (4)
C15—C16	1.466 (5)	C42—H42A	0.9600
C15—C17	1.492 (4)	C42—H42B	0.9600
C15—H15A	0.9700	C42—H42C	0.9600
C15—H15B	0.9700

C13—N1—C9	121.0 (2)	C20—C19—C18	123.7 (2)
C13—N1—C5	130.0 (2)	N3—C19—C18	126.3 (2)
C9—N1—C5	108.59 (19)	C19—C20—C21	109.8 (2)
C27—N3—C23	121.0 (2)	C19—C20—H20A	125.1
C27—N3—C19	130.0 (2)	C21—C20—H20A	125.1
C23—N3—C19	108.50 (19)	C20—C21—C23	107.7 (2)
C41—N5—C37	121.0 (2)	C20—C21—C22	124.3 (2)
C41—N5—C33	129.6 (2)	C23—C21—C22	127.8 (2)
C37—N5—C33	108.9 (2)	N4—C22—C21	175.1 (3)
C2—C1—C3	61.2 (2)	C21—C23—N3	107.0 (2)
C2—C1—H1A	117.6	C21—C23—C24	134.9 (2)
C3—C1—H1A	117.6	N3—C23—C24	118.1 (2)
C2—C1—H1B	117.6	C25—C24—C23	120.6 (2)
C3—C1—H1B	117.6	C25—C24—Br2	120.6 (2)
H1A—C1—H1B	114.8	C23—C24—Br2	118.7 (2)
C1—C2—C3	60.7 (2)	C24—C25—C26	119.4 (2)
C1—C2—H2A	117.7	C24—C25—H25A	120.3
C3—C2—H2A	117.7	C26—C25—H25A	120.3
C1—C2—H2B	117.7	C27—C26—C25	122.5 (2)
C3—C2—H2B	117.7	C27—C26—H26A	118.7
H2A—C2—H2B	114.8	C25—C26—H26A	118.7
C4—C3—C1	117.4 (2)	C26—C27—N3	117.6 (2)
C4—C3—C2	116.9 (3)	C26—C27—C28	121.9 (2)
C1—C3—C2	58.1 (2)	N3—C27—C28	120.2 (2)
C4—C3—H3A	117.1	C27—C28—H28A	109.5
C1—C3—H3A	117.1	C27—C28—H28B	109.5
C2—C3—H3A	117.1	H28A—C28—H28B	109.5
O1—C4—C5	122.6 (2)	C27—C28—H28C	109.5
O1—C4—C3	121.7 (2)	H28A—C28—H28C	109.5
C5—C4—C3	115.5 (2)	H28B—C28—H28C	109.5
C6—C5—N1	107.1 (2)	C30—C29—C31	60.9 (2)
C6—C5—C4	122.3 (2)	C30—C29—H29A	117.7
N1—C5—C4	127.0 (2)	C31—C29—H29A	117.7
C5—C6—C7	109.3 (2)	C30—C29—H29B	117.7
C5—C6—H6A	125.3	C31—C29—H29B	117.7
C7—C6—H6A	125.3	H29A—C29—H29B	114.8
C9—C7—C6	108.0 (2)	C29—C30—C31	60.8 (2)
C9—C7—C8	128.5 (2)	C29—C30—H30A	117.7
C6—C7—C8	123.4 (2)	C31—C30—H30A	117.7
N2—C8—C7	174.9 (3)	C29—C30—H30B	117.7
C7—C9—N1	107.0 (2)	C31—C30—H30B	117.7
C7—C9—C10	134.4 (2)	H30A—C30—H30B	114.8
N1—C9—C10	118.6 (2)	C32—C31—C29	116.1 (3)
C11—C10—C9	120.9 (2)	C32—C31—C30	116.7 (3)
C11—C10—Br1	120.5 (2)	C29—C31—C30	58.3 (2)
C9—C10—Br1	118.6 (2)	C32—C31—H31A	117.5
C10—C11—C12	118.4 (3)	C29—C31—H31A	117.5
C10—C11—H11A	120.8	C30—C31—H31A	117.5
C12—C11—H11A	120.8	O3—C32—C33	122.1 (3)
C13—C12—C11	123.4 (3)	O3—C32—C31	120.6 (3)
C13—C12—H12A	118.3	C33—C32—C31	117.0 (2)
C11—C12—H12A	118.3	C34—C33—N5	106.4 (2)
C12—C13—N1	117.3 (2)	C34—C33—C32	124.1 (3)
C12—C13—C14	122.8 (3)	N5—C33—C32	125.8 (2)
N1—C13—C14	119.8 (2)	C33—C34—C35	110.3 (2)
C13—C14—H14A	109.5	C33—C34—H34A	124.9
C13—C14—H14B	109.5	C35—C34—H34A	124.9
H14A—C14—H14B	109.5	C34—C35—C37	107.9 (2)
C13—C14—H14C	109.5	C34—C35—C36	124.2 (3)
H14A—C14—H14C	109.5	C37—C35—C36	127.9 (3)
H14B—C14—H14C	109.5	N6—C36—C35	175.7 (4)
C16—C15—C17	60.4 (2)	C38—C37—C35	135.4 (3)
C16—C15—H15A	117.7	C38—C37—N5	118.1 (2)
C17—C15—H15A	117.7	C35—C37—N5	106.6 (2)
C16—C15—H15B	117.7	C39—C38—C37	121.1 (3)
C17—C15—H15B	117.7	C39—C38—Br3	119.4 (2)
H15A—C15—H15B	114.9	C37—C38—Br3	119.4 (2)
C15—C16—C17	60.7 (2)	C38—C39—C40	118.5 (3)
C15—C16—H16A	117.7	C38—C39—H39A	120.8
C17—C16—H16A	117.7	C40—C39—H39A	120.8
C15—C16—H16B	117.7	C41—C40—C39	123.4 (3)
C17—C16—H16B	117.7	C41—C40—H40A	118.3
H16A—C16—H16B	114.8	C39—C40—H40A	118.3
C18—C17—C16	116.1 (3)	C40—C41—N5	117.2 (3)
C18—C17—C15	118.6 (2)	C40—C41—C42	122.8 (3)
C16—C17—C15	58.9 (2)	N5—C41—C42	119.8 (3)
C18—C17—H17A	116.9	C41—C42—H42A	109.5
C16—C17—H17A	116.9	C41—C42—H42B	109.5
C15—C17—H17A	116.9	H42A—C42—H42B	109.5
O2—C18—C19	123.6 (2)	C41—C42—H42C	109.5
O2—C18—C17	121.1 (2)	H42A—C42—H42C	109.5
C19—C18—C17	115.0 (2)	H42B—C42—H42C	109.5
C20—C19—N3	106.9 (2)

C2—C1—C3—C4	106.1 (3)	C20—C21—C23—C24	−179.8 (3)
C1—C2—C3—C4	−107.0 (3)	C22—C21—C23—C24	−3.0 (5)
C1—C3—C4—O1	−43.4 (4)	C27—N3—C23—C21	171.1 (2)
C2—C3—C4—O1	22.7 (4)	C19—N3—C23—C21	−1.6 (3)
C1—C3—C4—C5	131.3 (3)	C27—N3—C23—C24	−8.4 (3)
C2—C3—C4—C5	−162.6 (3)	C19—N3—C23—C24	178.9 (2)
C13—N1—C5—C6	170.1 (2)	C21—C23—C24—C25	−178.8 (3)
C9—N1—C5—C6	−1.7 (3)	N3—C23—C24—C25	0.5 (4)
C13—N1—C5—C4	−31.1 (4)	C21—C23—C24—Br2	−0.7 (4)
C9—N1—C5—C4	157.1 (3)	N3—C23—C24—Br2	178.63 (16)
O1—C4—C5—C6	135.9 (3)	C23—C24—C25—C26	4.8 (4)
C3—C4—C5—C6	−38.7 (4)	Br2—C24—C25—C26	−173.3 (2)
O1—C4—C5—N1	−20.0 (4)	C24—C25—C26—C27	−2.4 (4)
C3—C4—C5—N1	165.4 (3)	C25—C26—C27—N3	−5.3 (4)
N1—C5—C6—C7	1.7 (3)	C25—C26—C27—C28	168.8 (3)
C4—C5—C6—C7	−158.3 (2)	C23—N3—C27—C26	10.7 (3)
C5—C6—C7—C9	−1.1 (3)	C19—N3—C27—C26	−178.4 (2)
C5—C6—C7—C8	174.6 (2)	C23—N3—C27—C28	−163.5 (2)
C6—C7—C9—N1	0.0 (3)	C19—N3—C27—C28	7.5 (4)
C8—C7—C9—N1	−175.4 (3)	C30—C29—C31—C32	−106.6 (3)
C6—C7—C9—C10	−178.9 (3)	C29—C30—C31—C32	105.6 (3)
C8—C7—C9—C10	5.8 (5)	C29—C31—C32—O3	30.5 (4)
C13—N1—C9—C7	−171.7 (2)	C30—C31—C32—O3	−35.4 (4)
C5—N1—C9—C7	1.1 (3)	C29—C31—C32—C33	−154.0 (3)
C13—N1—C9—C10	7.4 (3)	C30—C31—C32—C33	140.1 (3)
C5—N1—C9—C10	−179.9 (2)	C41—N5—C33—C34	168.7 (3)
C7—C9—C10—C11	176.7 (3)	C37—N5—C33—C34	−2.8 (3)
N1—C9—C10—C11	−2.0 (4)	C41—N5—C33—C32	−32.5 (4)
C7—C9—C10—Br1	−5.0 (4)	C37—N5—C33—C32	156.0 (2)
N1—C9—C10—Br1	176.22 (17)	O3—C32—C33—C34	135.6 (3)
C9—C10—C11—C12	−2.6 (4)	C31—C32—C33—C34	−39.8 (4)
Br1—C10—C11—C12	179.1 (2)	O3—C32—C33—N5	−19.6 (4)
C10—C11—C12—C13	2.2 (5)	C31—C32—C33—N5	165.0 (3)
C11—C12—C13—N1	2.9 (4)	N5—C33—C34—C35	2.4 (3)
C11—C12—C13—C14	−172.6 (3)	C32—C33—C34—C35	−156.9 (3)
C9—N1—C13—C12	−7.7 (4)	C33—C34—C35—C37	−1.1 (3)
C5—N1—C13—C12	−178.7 (3)	C33—C34—C35—C36	177.2 (3)
C9—N1—C13—C14	167.9 (2)	C34—C35—C37—C38	179.6 (3)
C5—N1—C13—C14	−3.1 (4)	C36—C35—C37—C38	1.4 (5)
C15—C16—C17—C18	−109.1 (3)	C34—C35—C37—N5	−0.7 (3)
C16—C15—C17—C18	104.8 (3)	C36—C35—C37—N5	−178.9 (3)
C16—C17—C18—O2	52.5 (4)	C41—N5—C37—C38	9.5 (4)
C15—C17—C18—O2	−14.7 (4)	C33—N5—C37—C38	−178.1 (2)
C16—C17—C18—C19	−121.7 (3)	C41—N5—C37—C35	−170.2 (2)
C15—C17—C18—C19	171.1 (3)	C33—N5—C37—C35	2.2 (3)
C27—N3—C19—C20	−170.0 (2)	C35—C37—C38—C39	175.0 (3)
C23—N3—C19—C20	1.8 (3)	N5—C37—C38—C39	−4.7 (4)
C27—N3—C19—C18	29.4 (4)	C35—C37—C38—Br3	−5.5 (4)
C23—N3—C19—C18	−158.8 (2)	N5—C37—C38—Br3	174.84 (18)
O2—C18—C19—C20	−141.3 (3)	C37—C38—C39—C40	−1.9 (4)
C17—C18—C19—C20	32.7 (4)	Br3—C38—C39—C40	178.6 (2)
O2—C18—C19—N3	16.2 (4)	C38—C39—C40—C41	4.2 (5)
C17—C18—C19—N3	−169.8 (3)	C39—C40—C41—N5	0.5 (5)
N3—C19—C20—C21	−1.2 (3)	C39—C40—C41—C42	−174.8 (3)
C18—C19—C20—C21	160.0 (2)	C37—N5—C41—C40	−7.4 (4)
C19—C20—C21—C23	0.2 (3)	C33—N5—C41—C40	−178.1 (3)
C19—C20—C21—C22	−176.7 (3)	C37—N5—C41—C42	168.1 (3)
C20—C21—C23—N3	0.9 (3)	C33—N5—C41—C42	−2.6 (4)
C22—C21—C23—N3	177.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O1	0.96	2.09	2.857 (4)	136
C28—H28C···O2	0.96	2.04	2.823 (4)	138
C42—H42B···O3	0.96	2.04	2.814 (4)	136

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁BrN₂O
M_r	303.16
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.3443 (7), 14.5827 (13), 16.9132 (14)
α, β, γ (°)	70.418 (4), 88.849 (4), 76.833 (4)
V (Å³)	1884.5 (3)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	3.26
Crystal size (mm)	0.48 × 0.33 × 0.11

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.283, 0.701
No. of measured, independent and observed [I > 2σ(I)] reflections	22759, 6586, 5163
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.05
No. of reflections	6586
No. of parameters	487
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.57

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O1	0.96	2.09	2.857 (4)	136
C28—H28C···O2	0.96	2.04	2.823 (4)	138
C42—H42B···O3	0.96	2.04	2.814 (4)	136

Acknowledgements

We greatly appreciate the financial support of the Foundation of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province (AE201017) and the Scientific Project of Yancheng Institute of Technology (XKY2011003).

References

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