Ethyl 3-bromo-1-(3-chloro-2-pyrid­yl)-4,5-dihydro-1H-pyrazole-5-carboxyl­ate

Chen, H.; Yang, H.; Yu, H.; Li, B.

doi:10.1107/S1600536809050673

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3267

doi:10.1107/S1600536809050673

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Ethyl 3-bromo-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylate

Hua Chen,^a Huibin Yang,^b Haibo Yu ^b and Bin Li ^b ^*

^aShenyang Institute of Chemical Technology, Shenyang 110142, People's Republic of China, and ^bAgrochemicals Division, Shenyang Research Institute of Chemical Industry, Shenyang 110021, People's Republic of China
^*Correspondence e-mail: libin1@sinochem.com

(Received 24 November 2009; accepted 25 November 2009; online 28 November 2009)

The title compound, C₁₁H₁₁BrClN₃O₂, contains two molecules in the asymmetric unit in which the dihedral angles between the pyrazole and pyridine rings are 30.0 (2) and 22.3 (2)°.

Related literature

For background to the use of anthranilamide compounds containing N-pyridyl pyrazole groups as potential insecticides, see: Lahm et al. (2003 ). For the synthesis, see: Lahm et al. (2005 ).

Experimental

Crystal data

C₁₁H₁₁BrClN₃O₂
M_r = 332.59
Monoclinic, P 2₁ /n
a = 11.9977 (18) Å
b = 10.8520 (17) Å
c = 20.762 (3) Å
β = 93.388 (3)°
V = 2698.4 (7) Å³
Z = 8
Mo Kα radiation
μ = 3.24 mm⁻¹
T = 296 K
0.38 × 0.32 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.356, T_max = 1.000
13418 measured reflections
4760 independent reflections
2823 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.126
S = 1.02
4760 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050673/hb5251sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050673/hb5251Isup2.hkl

checkCIF report

Related literature top

For background to the use of anthranilamide compounds containing N-pyridyl pyrazole groups as potential insecticides, see: Lahm et al. (2003). For the synthesis, see: Lahm et al. (2005).

Experimental top

According to the reported procedure of Lahm et al., (2005), the title compound was synthesized by ethyl 2-(3-chloro-2-Pyridinyl)-5-oxo-3-pyrazolidinecarboxylate with phosphorus oxybromide under basic condition in acetonitrile. The crude products were purified by silica-gel column chromatography and then grown from acetone to afford colorless single crystals suitable for X-ray diffraction.To a solution of ethyl 2-(3-chloro-2-Pyridinyl)-5-oxo-3-pyrazolidinecarboxylate (2.70 g, 10.0 mmol) in acetonitrile (30 ml) was added the solution of phosphorusoxybromide (2.01 g, 7.0 mmol) in acetonitrile (30 ml) at 333 K.The reaction mixturewas heated to reflux at 369 K over period of 1 h. Then neutralize concentrated reaction mixture with sodium bicarbonate until the PH=8.Then the mixture was extracted with ethyl acetate; the organic extracts were dried overmagnesium sulfate and concentrated. Afford the title product compound as a white solid (2.5 g, 75%). Anal. Calcd for C₁₁H₁₁N₃O₂: C, 39.72; H, 3.33; N, 12.63. Found: C, 39.91; H, 3.27; N, 12.50. ¹H NMR (DMSO): 1.15(t, 3H, CH₃), 3.29 (dd, 1H, pyrazole-H), 3.60 (dd, 1H, pyrazole-H),4.11(q,2H,CH₂),5.20 (dd, 1H, pyrazole-H), 6.99 (dd, 1H, pyridine-H), 7.84 (d, 1H, pyridine-H), 8.12 (d, 1H, pyridine-H).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (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 (I), with 30% probability displacement ellipsoids.

Ethyl 3-bromo-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylate top

Crystal data top

C₁₁H₁₁BrClN₃O₂	F(000) = 1328
M_r = 332.59	D_x = 1.637 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2849 reflections
a = 11.9977 (18) Å	θ = 2.5–23.4°
b = 10.8520 (17) Å	µ = 3.24 mm⁻¹
c = 20.762 (3) Å	T = 296 K
β = 93.388 (3)°	Block, colourless
V = 2698.4 (7) Å³	0.38 × 0.32 × 0.30 mm
Z = 8

Data collection top

Bruker SMART CCD diffractometer	4760 independent reflections
Radiation source: fine-focus sealed tube	2823 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
T_min = 0.356, T_max = 1.000	k = −12→8
13418 measured reflections	l = −20→24

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0609P)² + 0.7833P] where P = (F_o² + 2F_c²)/3
4760 reflections	(Δ/σ)_max = 0.001
327 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₁₁H₁₁BrClN₃O₂	V = 2698.4 (7) Å³
M_r = 332.59	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.9977 (18) Å	µ = 3.24 mm⁻¹
b = 10.8520 (17) Å	T = 296 K
c = 20.762 (3) Å	0.38 × 0.32 × 0.30 mm
β = 93.388 (3)°

Data collection top

Bruker SMART CCD diffractometer	4760 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2823 reflections with I > 2σ(I)
T_min = 0.356, T_max = 1.000	R_int = 0.029
13418 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.02	Δρ_max = 0.64 e Å⁻³
4760 reflections	Δρ_min = −0.49 e Å⁻³
327 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	0.61938 (4)	0.12589 (5)	0.11537 (3)	0.0919 (2)
Br2	0.12166 (4)	1.34462 (4)	0.11712 (3)	0.0871 (2)
Cl1	0.84050 (8)	0.53502 (11)	0.12056 (6)	0.0843 (4)
Cl2	0.33983 (8)	0.94532 (12)	0.10673 (7)	0.0940 (4)
O1	0.4918 (3)	0.6080 (3)	0.20858 (15)	0.0867 (10)
O2	0.3214 (2)	0.5466 (3)	0.17635 (13)	0.0802 (9)
O3	0.0011 (3)	0.8736 (3)	0.20050 (14)	0.0864 (10)
O4	−0.1747 (2)	0.9229 (3)	0.17066 (12)	0.0680 (8)
N1	0.5454 (2)	0.6660 (3)	0.05716 (14)	0.0553 (8)
N2	0.5862 (2)	0.4848 (3)	0.11040 (15)	0.0610 (9)
N3	0.6393 (3)	0.3738 (3)	0.10056 (16)	0.0601 (9)
N4	0.0445 (2)	0.8001 (3)	0.05316 (15)	0.0577 (8)
N5	0.0807 (2)	0.9898 (3)	0.09552 (19)	0.0750 (10)
N6	0.1371 (2)	1.0989 (3)	0.09295 (15)	0.0579 (8)
C1	0.5772 (3)	0.7712 (4)	0.03040 (18)	0.0640 (11)
H1	0.5218	0.8257	0.0153	0.077*
C2	0.6850 (3)	0.8036 (4)	0.02391 (19)	0.0700 (12)
H2	0.7031	0.8752	0.0023	0.084*
C3	0.7664 (3)	0.7272 (4)	0.05023 (19)	0.0619 (11)
H3	0.8413	0.7475	0.0475	0.074*
C4	0.7373 (3)	0.6211 (4)	0.08063 (18)	0.0548 (10)
C5	0.6239 (3)	0.5907 (3)	0.08114 (16)	0.0477 (9)
C6	0.5731 (3)	0.2893 (4)	0.11589 (18)	0.0595 (10)
C7	0.4634 (3)	0.3298 (4)	0.13789 (19)	0.0610 (10)
H7A	0.4583	0.3175	0.1839	0.073*
H7B	0.4019	0.2878	0.1147	0.073*
C8	0.4669 (3)	0.4674 (3)	0.12040 (17)	0.0528 (9)
H8	0.4219	0.4833	0.0803	0.063*
C9	0.4312 (3)	0.5498 (4)	0.17334 (18)	0.0592 (10)
C10	0.2759 (5)	0.6186 (6)	0.2280 (3)	0.119 (2)
H10A	0.3045	0.5872	0.2695	0.143*
H10B	0.2990	0.7039	0.2246	0.143*
C11	0.1599 (6)	0.6115 (7)	0.2238 (3)	0.159 (3)
H11A	0.1319	0.6407	0.1823	0.238*
H11B	0.1303	0.6614	0.2569	0.238*
H11C	0.1373	0.5274	0.2292	0.238*
C12	0.0767 (3)	0.6904 (4)	0.03225 (19)	0.0664 (11)
H12	0.0218	0.6335	0.0197	0.080*
C13	0.1851 (3)	0.6570 (4)	0.0282 (2)	0.0708 (12)
H13	0.2042	0.5807	0.0117	0.085*
C14	0.2656 (3)	0.7401 (4)	0.0494 (2)	0.0658 (11)
H14	0.3407	0.7203	0.0474	0.079*
C15	0.2355 (3)	0.8510 (4)	0.07329 (19)	0.0556 (10)
C16	0.1219 (3)	0.8812 (3)	0.07301 (17)	0.0490 (9)
C17	0.0712 (3)	1.1825 (4)	0.10999 (18)	0.0561 (10)
C18	−0.0415 (3)	1.1433 (4)	0.1270 (2)	0.0679 (12)
H18A	−0.0997	1.1861	0.1013	0.081*
H18B	−0.0524	1.1557	0.1724	0.081*
C19	−0.0372 (3)	1.0054 (3)	0.10966 (17)	0.0534 (9)
H19	−0.0863	0.9873	0.0715	0.064*
C20	−0.0653 (3)	0.9256 (4)	0.16513 (18)	0.0551 (10)
C21	−0.2137 (5)	0.8554 (5)	0.2256 (2)	0.0970 (17)
H21A	−0.1850	0.7719	0.2256	0.116*
H21B	−0.1870	0.8950	0.2654	0.116*
C22	−0.3344 (5)	0.8532 (6)	0.2213 (3)	0.133 (3)
H22A	−0.3623	0.9361	0.2203	0.199*
H22B	−0.3606	0.8109	0.2581	0.199*
H22C	−0.3603	0.8111	0.1826	0.199*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0860 (4)	0.0580 (3)	0.1307 (5)	0.0064 (2)	−0.0007 (3)	0.0112 (3)
Br2	0.0843 (4)	0.0538 (3)	0.1226 (4)	−0.0033 (2)	0.0012 (3)	−0.0117 (3)
Cl1	0.0455 (6)	0.0807 (8)	0.1243 (10)	0.0010 (5)	−0.0147 (6)	0.0073 (7)
Cl2	0.0447 (6)	0.0696 (8)	0.1656 (12)	−0.0029 (5)	−0.0116 (7)	−0.0069 (8)
O1	0.086 (2)	0.093 (2)	0.080 (2)	−0.0312 (19)	0.0031 (17)	−0.0221 (18)
O2	0.0583 (18)	0.104 (3)	0.0802 (19)	−0.0035 (16)	0.0172 (14)	−0.0382 (18)
O3	0.086 (2)	0.096 (3)	0.077 (2)	0.0324 (18)	−0.0057 (17)	0.0147 (17)
O4	0.0564 (17)	0.084 (2)	0.0646 (17)	−0.0057 (14)	0.0118 (13)	0.0251 (15)
N1	0.0409 (17)	0.063 (2)	0.061 (2)	−0.0002 (16)	0.0015 (14)	0.0043 (17)
N2	0.0402 (17)	0.056 (2)	0.088 (2)	−0.0019 (15)	0.0116 (15)	0.0054 (18)
N3	0.0498 (19)	0.057 (2)	0.073 (2)	0.0037 (16)	−0.0023 (16)	0.0003 (17)
N4	0.0416 (17)	0.062 (2)	0.070 (2)	0.0016 (16)	0.0021 (15)	−0.0019 (17)
N5	0.0445 (19)	0.051 (2)	0.132 (3)	0.0018 (16)	0.0298 (19)	−0.002 (2)
N6	0.0467 (18)	0.050 (2)	0.077 (2)	−0.0038 (16)	0.0032 (15)	0.0022 (17)
C1	0.055 (2)	0.071 (3)	0.065 (3)	0.005 (2)	0.0026 (19)	0.010 (2)
C2	0.060 (3)	0.077 (3)	0.074 (3)	−0.010 (2)	0.016 (2)	0.015 (2)
C3	0.048 (2)	0.065 (3)	0.074 (3)	−0.009 (2)	0.0169 (19)	−0.007 (2)
C4	0.040 (2)	0.061 (3)	0.064 (2)	0.0042 (18)	0.0026 (17)	−0.007 (2)
C5	0.039 (2)	0.052 (2)	0.053 (2)	−0.0038 (17)	0.0079 (16)	−0.0054 (18)
C6	0.054 (2)	0.056 (3)	0.067 (3)	−0.003 (2)	−0.0088 (19)	0.002 (2)
C7	0.059 (2)	0.060 (3)	0.065 (3)	−0.012 (2)	0.0060 (19)	−0.009 (2)
C8	0.043 (2)	0.059 (3)	0.056 (2)	−0.0105 (17)	0.0055 (16)	−0.0042 (19)
C9	0.055 (2)	0.062 (3)	0.060 (2)	−0.016 (2)	0.004 (2)	−0.002 (2)
C10	0.086 (4)	0.155 (6)	0.120 (5)	0.000 (4)	0.034 (3)	−0.070 (4)
C11	0.172 (7)	0.171 (7)	0.137 (6)	0.073 (6)	0.047 (5)	−0.040 (5)
C12	0.055 (2)	0.071 (3)	0.073 (3)	−0.006 (2)	−0.001 (2)	−0.015 (2)
C13	0.060 (3)	0.067 (3)	0.087 (3)	0.009 (2)	0.018 (2)	−0.015 (2)
C14	0.046 (2)	0.064 (3)	0.089 (3)	0.009 (2)	0.021 (2)	0.000 (2)
C15	0.039 (2)	0.053 (2)	0.075 (3)	−0.0008 (17)	0.0065 (18)	0.007 (2)
C16	0.040 (2)	0.050 (2)	0.057 (2)	0.0047 (17)	0.0104 (17)	0.0067 (18)
C17	0.055 (2)	0.049 (2)	0.064 (3)	0.0074 (19)	0.0002 (18)	0.003 (2)
C18	0.060 (3)	0.057 (3)	0.089 (3)	0.013 (2)	0.021 (2)	0.014 (2)
C19	0.043 (2)	0.052 (2)	0.066 (2)	0.0070 (17)	0.0114 (17)	0.0065 (19)
C20	0.051 (2)	0.050 (2)	0.064 (3)	0.0070 (19)	0.001 (2)	−0.002 (2)
C21	0.111 (4)	0.106 (4)	0.077 (3)	−0.013 (3)	0.030 (3)	0.032 (3)
C22	0.138 (6)	0.166 (7)	0.100 (4)	−0.078 (5)	0.042 (4)	0.012 (4)

Geometric parameters (Å, º) top

Br1—C6	1.858 (4)	C7—C8	1.538 (5)
Br2—C17	1.863 (4)	C7—H7A	0.9700
Cl1—C4	1.724 (4)	C7—H7B	0.9700
Cl2—C15	1.731 (4)	C8—C9	1.499 (5)
O1—C9	1.184 (4)	C8—H8	0.9800
O2—C9	1.323 (4)	C10—C11	1.392 (9)
O2—C10	1.459 (5)	C10—H10A	0.9700
O3—C20	1.192 (4)	C10—H10B	0.9700
O4—C20	1.325 (4)	C11—H11A	0.9600
O4—C21	1.455 (5)	C11—H11B	0.9600
N1—C5	1.321 (4)	C11—H11C	0.9600
N1—C1	1.335 (5)	C12—C13	1.357 (5)
N2—N3	1.383 (4)	C12—H12	0.9300
N2—C5	1.388 (5)	C13—C14	1.374 (6)
N2—C8	1.471 (4)	C13—H13	0.9300
N3—C6	1.266 (5)	C14—C15	1.358 (5)
N4—C16	1.327 (5)	C14—H14	0.9300
N4—C12	1.332 (5)	C15—C16	1.401 (5)
N5—N6	1.366 (4)	C17—C18	1.480 (5)
N5—C16	1.371 (5)	C18—C19	1.541 (5)
N5—C19	1.470 (4)	C18—H18A	0.9700
N6—C17	1.267 (5)	C18—H18B	0.9700
C1—C2	1.355 (5)	C19—C20	1.495 (5)
C1—H1	0.9300	C19—H19	0.9800
C2—C3	1.370 (5)	C21—C22	1.445 (8)
C2—H2	0.9300	C21—H21A	0.9700
C3—C4	1.368 (5)	C21—H21B	0.9700
C3—H3	0.9300	C22—H22A	0.9600
C4—C5	1.401 (5)	C22—H22B	0.9600
C6—C7	1.486 (5)	C22—H22C	0.9600

C9—O2—C10	115.9 (3)	C10—C11—H11A	109.5
C20—O4—C21	116.4 (3)	C10—C11—H11B	109.5
C5—N1—C1	118.1 (3)	H11A—C11—H11B	109.5
N3—N2—C5	119.5 (3)	C10—C11—H11C	109.5
N3—N2—C8	111.7 (3)	H11A—C11—H11C	109.5
C5—N2—C8	120.8 (3)	H11B—C11—H11C	109.5
C6—N3—N2	107.0 (3)	N4—C12—C13	123.8 (4)
C16—N4—C12	118.8 (3)	N4—C12—H12	118.1
N6—N5—C16	122.8 (3)	C13—C12—H12	118.1
N6—N5—C19	113.2 (3)	C12—C13—C14	117.5 (4)
C16—N5—C19	122.5 (3)	C12—C13—H13	121.2
C17—N6—N5	106.9 (3)	C14—C13—H13	121.2
N1—C1—C2	124.1 (4)	C15—C14—C13	120.1 (4)
N1—C1—H1	118.0	C15—C14—H14	120.0
C2—C1—H1	118.0	C13—C14—H14	120.0
C1—C2—C3	117.8 (4)	C14—C15—C16	119.0 (4)
C1—C2—H2	121.1	C14—C15—Cl2	118.0 (3)
C3—C2—H2	121.1	C16—C15—Cl2	122.9 (3)
C4—C3—C2	119.8 (4)	N4—C16—N5	114.6 (3)
C4—C3—H3	120.1	N4—C16—C15	120.6 (3)
C2—C3—H3	120.1	N5—C16—C15	124.8 (3)
C3—C4—C5	118.5 (3)	N6—C17—C18	117.0 (4)
C3—C4—Cl1	118.8 (3)	N6—C17—Br2	119.6 (3)
C5—C4—Cl1	122.6 (3)	C18—C17—Br2	123.3 (3)
N1—C5—N2	115.7 (3)	C17—C18—C19	100.3 (3)
N1—C5—C4	121.4 (3)	C17—C18—H18A	111.7
N2—C5—C4	122.7 (3)	C19—C18—H18A	111.7
N3—C6—C7	116.3 (4)	C17—C18—H18B	111.7
N3—C6—Br1	119.9 (3)	C19—C18—H18B	111.7
C7—C6—Br1	123.7 (3)	H18A—C18—H18B	109.5
C6—C7—C8	100.2 (3)	N5—C19—C20	110.5 (3)
C6—C7—H7A	111.7	N5—C19—C18	101.8 (3)
C8—C7—H7A	111.7	C20—C19—C18	111.7 (3)
C6—C7—H7B	111.7	N5—C19—H19	110.8
C8—C7—H7B	111.7	C20—C19—H19	110.8
H7A—C7—H7B	109.5	C18—C19—H19	110.8
N2—C8—C9	110.5 (3)	O3—C20—O4	124.4 (4)
N2—C8—C7	101.4 (3)	O3—C20—C19	125.2 (4)
C9—C8—C7	113.2 (3)	O4—C20—C19	110.4 (3)
N2—C8—H8	110.5	C22—C21—O4	109.1 (4)
C9—C8—H8	110.5	C22—C21—H21A	109.9
C7—C8—H8	110.5	O4—C21—H21A	109.9
O1—C9—O2	124.2 (4)	C22—C21—H21B	109.9
O1—C9—C8	125.4 (4)	O4—C21—H21B	109.9
O2—C9—C8	110.3 (3)	H21A—C21—H21B	108.3
C11—C10—O2	109.9 (5)	C21—C22—H22A	109.5
C11—C10—H10A	109.7	C21—C22—H22B	109.5
O2—C10—H10A	109.7	H22A—C22—H22B	109.5
C11—C10—H10B	109.7	C21—C22—H22C	109.5
O2—C10—H10B	109.7	H22A—C22—H22C	109.5
H10A—C10—H10B	108.2	H22B—C22—H22C	109.5

C5—N2—N3—C6	−161.8 (3)	C7—C8—C9—O2	−75.6 (4)
C8—N2—N3—C6	−12.7 (4)	C9—O2—C10—C11	177.3 (5)
C16—N5—N6—C17	172.2 (4)	C16—N4—C12—C13	−1.9 (6)
C19—N5—N6—C17	6.1 (4)	N4—C12—C13—C14	2.6 (7)
C5—N1—C1—C2	2.8 (6)	C12—C13—C14—C15	0.0 (6)
N1—C1—C2—C3	−4.5 (6)	C13—C14—C15—C16	−3.0 (6)
C1—C2—C3—C4	1.3 (6)	C13—C14—C15—Cl2	173.6 (3)
C2—C3—C4—C5	3.0 (6)	C12—N4—C16—N5	−178.0 (4)
C2—C3—C4—Cl1	−173.3 (3)	C12—N4—C16—C15	−1.4 (5)
C1—N1—C5—N2	177.8 (3)	N6—N5—C16—N4	−152.2 (4)
C1—N1—C5—C4	2.0 (5)	C19—N5—C16—N4	12.6 (5)
N3—N2—C5—N1	139.1 (3)	N6—N5—C16—C15	31.3 (6)
C8—N2—C5—N1	−7.1 (5)	C19—N5—C16—C15	−163.9 (3)
N3—N2—C5—C4	−45.1 (5)	C14—C15—C16—N4	3.8 (6)
C8—N2—C5—C4	168.6 (3)	Cl2—C15—C16—N4	−172.6 (3)
C3—C4—C5—N1	−4.9 (5)	C14—C15—C16—N5	−179.9 (4)
Cl1—C4—C5—N1	171.4 (3)	Cl2—C15—C16—N5	3.7 (6)
C3—C4—C5—N2	179.7 (3)	N5—N6—C17—C18	0.0 (5)
Cl1—C4—C5—N2	−4.1 (5)	N5—N6—C17—Br2	176.5 (3)
N2—N3—C6—C7	0.8 (5)	N6—C17—C18—C19	−5.4 (5)
N2—N3—C6—Br1	−175.1 (2)	Br2—C17—C18—C19	178.2 (3)
N3—C6—C7—C8	10.3 (4)	N6—N5—C19—C20	−127.9 (4)
Br1—C6—C7—C8	−173.9 (3)	C16—N5—C19—C20	66.0 (5)
N3—N2—C8—C9	138.6 (3)	N6—N5—C19—C18	−9.0 (4)
C5—N2—C8—C9	−72.8 (4)	C16—N5—C19—C18	−175.2 (4)
N3—N2—C8—C7	18.3 (4)	C17—C18—C19—N5	7.8 (4)
C5—N2—C8—C7	166.9 (3)	C17—C18—C19—C20	125.8 (3)
C6—C7—C8—N2	−15.7 (3)	C21—O4—C20—O3	2.7 (6)
C6—C7—C8—C9	−134.1 (3)	C21—O4—C20—C19	−175.9 (4)
C10—O2—C9—O1	−1.4 (7)	N5—C19—C20—O3	12.4 (5)
C10—O2—C9—C8	177.2 (4)	C18—C19—C20—O3	−100.1 (5)
N2—C8—C9—O1	−9.9 (6)	N5—C19—C20—O4	−169.0 (3)
C7—C8—C9—O1	103.0 (5)	C18—C19—C20—O4	78.4 (4)
N2—C8—C9—O2	171.5 (3)	C20—O4—C21—C22	−175.3 (4)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁BrClN₃O₂
M_r	332.59
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	11.9977 (18), 10.8520 (17), 20.762 (3)
β (°)	93.388 (3)
V (Å³)	2698.4 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.24
Crystal size (mm)	0.38 × 0.32 × 0.30

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.356, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13418, 4760, 2823
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.126, 1.02
No. of reflections	4760
No. of parameters	327
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.49

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lahm, G. P., Selby, T. P. & Freudenberger, J. H. (2005). Bioorg. Med. Chem. Lett. 15, 4898–4906. Web of Science CrossRef PubMed CAS Google Scholar
Lahm, G. P., Selby, T. P. & Stevenson, T. M. (2003). World Patent No. WO 03/015519. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar