Ethyl 8-amino-6-bromoimidazo[1,2-a]pyridine-2-carb­oxy­late

Dahmani, S.; Kandri Rodi, Y.; Luis, S.V.; Essassi, E.M.; El Ammari, L.

doi:10.1107/S1600536811017077

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1390

doi:10.1107/S1600536811017077

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Ethyl 8-amino-6-bromoimidazo[1,2-a]pyridine-2-carboxylate

Siham Dahmani,^a ^* Youssef Kandri Rodi,^a Santiago V. Luis,^b El Mokhtar Essassi ^c and Lahcen El Ammari ^d

^aLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202 Fès, Morocco, ^bDepartamento de Quimica Inorganica & Organica, ESTCE, Universitat Jaume I, E-12080 Castellon, Spain, ^cLaboratoire de Chimie Organique Hétérocyclique URAC21, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco, and ^dLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: s_dahmani12@yahoo.fr

(Received 30 April 2011; accepted 5 May 2011; online 11 May 2011)

There are two independent molecules in the asymmetric unit of the title compound, C₁₀H₁₀BrN₃O₂, which are linked by N—H⋯O and C—H⋯O hydrogen bonds. The fused ring systems in both molecules are nearly planar with maximum deviations of 0.001 (3) and 0.029 (3) Å. All non-H atoms of the first molecule are approximately co-planar whereas in the second molecule, the ethyl group is almost perpendicular to the imidazo[1,2-a]pyridine system, the C—O—C—C torsion angles in the carboxylic acid ethyl group being −179.8 (4) and 112.1 (5)°, respectively.

Related literature

For the biological activity of imidazo[1,2-a]pyridine derivatives, see: Anderson et al. (2003 ); Trapani et al. (2003 ); Gueiffier et al. (1998 ); Mavel et al. (2002 ). For their pharmacological activity, see: Rival et al. (1992 ); Rupert et al. (2003 ); Katritzky et al. (2003 ).

Experimental

Crystal data

C₁₀H₁₀BrN₃O₂
M_r = 284.12
Monoclinic, P 2₁ /c
a = 8.366 (2) Å
b = 11.842 (3) Å
c = 22.743 (5) Å
β = 98.328 (6)°
V = 2229.3 (8) Å³
Z = 8
Mo Kα radiation
μ = 3.68 mm⁻¹
T = 292 K
0.44 × 0.19 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.437, T_max = 0.535
13222 measured reflections
4555 independent reflections
3156 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.116
S = 1.03
4555 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N5ⁱ	0.86	2.47	3.300 (4)	161
N3—H3B⋯O3ⁱⁱ	0.86	2.38	3.055 (5)	135
N6—H6B⋯O2	0.85	2.34	3.096 (4)	147
N6—H6A⋯O1ⁱⁱⁱ	0.86	2.58	3.183 (4)	129
N6—H6A⋯N2ⁱⁱⁱ	0.86	2.60	3.388 (4)	154
C5—H5⋯O4	0.93	2.26	3.074 (4)	146
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017077/dn2683sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811017077/dn2683Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811017077/dn2683Isup3.cml

checkCIF report

Comment top

Imidazo[1,2-a]pyridine derivatives are important intermediates in organic synthesis, especially in the synthesis of biologically active and medicinally useful agents. For instance, they are widely used in the synthesis of cyclin- dependent kinases (CDK) inhibitors (Anderson et al., 2003), anticonvulsant agents, (Trapani et al., 2003) and antiviral agents (Gueiffier et al.,1998; Mavel et al.,2002).

Derivatives containing the imidazo[1,2-a]- pyridine ring system have been shown to possess a broad range of useful pharmacological activities, including antibacterial, (Rival et al., 1992) and anti-inflammatory properties (Rupert et al., 2003). Drug formulations containing imidazo[1,2-a]pyridines currently available on the market include alpidem (anxiolytic), zolpidem (hypnotic), and zolimidine (antiulcer) (Katritzky et al.,2003).

In this work, we report a novel and efficient method for the synthesis of 6-bromo-8-amino-imidazo[1,2-a]pyridine via the treatment of ethyl bromopyruvate with 5-bromo-2,3-diaminopyridine in the presence of NaHCO₃ in ethanol at reflux in 65% yield (scheme1).

The Plot of the two molecules building the asymmetric unit of the 8-Amino-6- bromo-imidazo[1,2-a]pyridin-2-carboxylic acid ethyl ester is shown in Fig.1. The two fused five and six-membered rings belonging to each molecule are nearly planar with the maximum deviation of -0.001 (3)Å from C7 and 0.029 (3)Å from C17. The dihedral angle between them is 26.06 (11)°. The ethyl group is almost perpendicular to the imidazo[1,2-a]pyridine system, in the second molecule, as indicated by the torsion angle C18–O3–C19–C20 of 112.1 (5)° (see Fig.2). The first molecule is approximately planar and the torsion angle C—O—C—C is in the range of -179.8 (4)°. In the crystal, the molecules are linked by intermolecular N—H···O and C—H···O hydrogen bonds building a three dimensionnal network (Table 1).

Related literature top

For the biological activity of imidazo[1,2-a]pyridine derivatives, see: Anderson et al. (2003); Trapani et al. (2003); Gueiffier et al. (1998); Mavel et al. (2002). For their pharmacological activity, see: Rival et al. (1992); Rupert et al. (2003); Katritzky et al. (2003).

Experimental top

A mixture of ethyl bromopyruvate (0.3 ml; 2.35 mmol), 5-bromo-2,3-diaminopyridine (0.5 g, 2.35 mmol) and NaHCO₃ (0.22 g, 2.35 mmol) in ethanol was stirred at reflux for the appropriate time. After completion of the reaction, as indicated by TLC, The solution was extracted with dichloromethane and the organic layer was dried over anhydrous Na₂SO₄. Evaporation of the solvent followed by recrystallization in hexane afforded yellow crystals of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. : Plot of of the two molecules building the asymmetric unit of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. View showing the fitting of the two molecules building the asymmetric unit of the title compound.

Ethyl 8-amino-6-bromoimidazo[1,2-a]pyridine-2-carboxylate top

Crystal data top

C₁₀H₁₀BrN₃O₂	F(000) = 1136
M_r = 284.12	D_x = 1.693 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 414(2) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.366 (2) Å	Cell parameters from 4555 reflections
b = 11.842 (3) Å	θ = 1.8–26.8°
c = 22.743 (5) Å	µ = 3.68 mm⁻¹
β = 98.328 (6)°	T = 292 K
V = 2229.3 (8) Å³	Fiber, yellow
Z = 8	0.44 × 0.19 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	4555 independent reflections
Radiation source: fine-focus sealed tube	3156 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 26.8°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
T_min = 0.437, T_max = 0.535	k = −11→14
13222 measured reflections	l = −24→28

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0571P)² + 1.0629P] where P = (F_o² + 2F_c²)/3
4555 reflections	(Δ/σ)_max = 0.001
291 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₁₀H₁₀BrN₃O₂	V = 2229.3 (8) Å³
M_r = 284.12	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.366 (2) Å	µ = 3.68 mm⁻¹
b = 11.842 (3) Å	T = 292 K
c = 22.743 (5) Å	0.44 × 0.19 × 0.17 mm
β = 98.328 (6)°

Data collection top

Bruker APEXII CCD diffractometer	4555 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3156 reflections with I > 2σ(I)
T_min = 0.437, T_max = 0.535	R_int = 0.032
13222 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.03	Δρ_max = 0.70 e Å⁻³
4555 reflections	Δρ_min = −0.51 e Å⁻³
291 parameters

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.

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 > 2σ(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
C1	0.6311 (4)	0.1790 (2)	0.24000 (15)	0.0364 (7)
C2	0.5137 (4)	0.1042 (3)	0.20858 (16)	0.0424 (8)
C3	0.3848 (4)	0.0737 (3)	0.23542 (17)	0.0463 (8)
H3	0.3073	0.0248	0.2162	0.056*
C4	0.3685 (4)	0.1156 (3)	0.29203 (17)	0.0457 (8)
C5	0.4772 (4)	0.1854 (3)	0.32284 (16)	0.0458 (8)
H5	0.4651	0.2114	0.3605	0.055*
C6	0.7346 (4)	0.2859 (3)	0.31519 (15)	0.0407 (7)
H6	0.7531	0.3244	0.3512	0.049*
C7	0.8290 (4)	0.2868 (3)	0.27069 (15)	0.0399 (7)
C8	0.9804 (4)	0.3528 (3)	0.27430 (17)	0.0442 (8)
C9	1.2055 (5)	0.4046 (4)	0.2303 (2)	0.0646 (11)
H9A	1.2805	0.3841	0.2653	0.078*
H9B	1.1815	0.4845	0.2327	0.078*
C10	1.2790 (6)	0.3820 (4)	0.1765 (2)	0.0738 (13)
H10A	1.3755	0.4263	0.1775	0.111*
H10B	1.2041	0.4018	0.1420	0.111*
H10C	1.3056	0.3033	0.1750	0.111*
N1	0.6074 (3)	0.2165 (2)	0.29548 (13)	0.0391 (6)
N2	0.7654 (3)	0.2206 (2)	0.22339 (12)	0.0387 (6)
N3	0.5421 (4)	0.0657 (3)	0.15447 (15)	0.0609 (9)
H3A	0.4634	0.0338	0.1320	0.073*
H3B	0.6048	0.1043	0.1351	0.073*
O1	1.0571 (3)	0.33902 (19)	0.22826 (11)	0.0493 (6)
O2	1.0266 (3)	0.4127 (2)	0.31636 (13)	0.0619 (7)
Br1	0.18490 (5)	0.07406 (4)	0.32785 (2)	0.06942 (17)
C11	0.8701 (4)	0.5979 (3)	0.45987 (15)	0.0382 (7)
C12	0.9608 (4)	0.6732 (3)	0.42770 (16)	0.0422 (8)
C13	1.0265 (4)	0.7670 (3)	0.45760 (17)	0.0472 (8)
H13	1.0798	0.8209	0.4379	0.057*
C14	1.0129 (4)	0.7813 (3)	0.51807 (17)	0.0450 (8)
C15	0.9362 (4)	0.7088 (3)	0.54986 (17)	0.0462 (8)
H15	0.9324	0.7195	0.5901	0.055*
C16	0.7710 (4)	0.5322 (3)	0.53803 (16)	0.0418 (8)
H16	0.7459	0.5214	0.5762	0.050*
C17	0.7243 (3)	0.4671 (3)	0.48894 (15)	0.0367 (7)
C18	0.6206 (4)	0.3662 (3)	0.48367 (16)	0.0432 (8)
C19	0.4773 (5)	0.2335 (4)	0.5359 (2)	0.0772 (14)
H19A	0.3926	0.2537	0.5590	0.093*
H19B	0.4272	0.2181	0.4956	0.093*
C20	0.5572 (7)	0.1346 (5)	0.5605 (4)	0.118 (2)
H20A	0.4790	0.0766	0.5638	0.177*
H20B	0.6147	0.1514	0.5991	0.177*
H20C	0.6320	0.1091	0.5351	0.177*
N4	0.8630 (3)	0.6170 (2)	0.51890 (13)	0.0399 (6)
N5	0.7852 (3)	0.5068 (2)	0.43990 (12)	0.0400 (6)
N6	0.9732 (4)	0.6470 (3)	0.37068 (14)	0.0565 (8)
H6A	1.0318	0.6877	0.3512	0.068*
H6B	0.9494	0.5790	0.3605	0.068*
O3	0.5891 (3)	0.3286 (2)	0.53566 (12)	0.0551 (6)
O4	0.5670 (3)	0.3250 (3)	0.43682 (13)	0.0718 (8)
Br2	1.11787 (5)	0.90661 (3)	0.55921 (2)	0.06673 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0447 (17)	0.0342 (16)	0.0290 (19)	0.0055 (13)	0.0002 (13)	−0.0018 (13)
C2	0.0483 (19)	0.0406 (18)	0.036 (2)	0.0027 (14)	−0.0025 (15)	−0.0035 (14)
C3	0.0489 (19)	0.0436 (19)	0.043 (2)	−0.0036 (14)	−0.0038 (15)	−0.0022 (15)
C4	0.0421 (18)	0.0477 (19)	0.048 (2)	−0.0002 (14)	0.0078 (15)	−0.0012 (16)
C5	0.0481 (19)	0.052 (2)	0.039 (2)	−0.0039 (15)	0.0119 (15)	−0.0082 (16)
C6	0.0470 (18)	0.0433 (18)	0.032 (2)	−0.0051 (14)	0.0057 (14)	−0.0103 (14)
C7	0.0445 (18)	0.0396 (17)	0.035 (2)	0.0010 (13)	0.0038 (14)	−0.0032 (14)
C8	0.050 (2)	0.0431 (19)	0.039 (2)	0.0005 (15)	0.0071 (15)	−0.0031 (15)
C9	0.050 (2)	0.071 (3)	0.075 (3)	−0.0188 (18)	0.015 (2)	−0.014 (2)
C10	0.073 (3)	0.076 (3)	0.076 (4)	−0.017 (2)	0.022 (2)	0.002 (2)
N1	0.0401 (14)	0.0400 (14)	0.0370 (18)	0.0004 (11)	0.0050 (11)	−0.0060 (12)
N2	0.0459 (15)	0.0400 (14)	0.0299 (16)	0.0022 (11)	0.0046 (11)	−0.0048 (11)
N3	0.071 (2)	0.074 (2)	0.036 (2)	−0.0150 (16)	0.0027 (15)	−0.0158 (15)
O1	0.0495 (13)	0.0516 (14)	0.0492 (17)	−0.0087 (10)	0.0148 (11)	−0.0136 (11)
O2	0.0700 (17)	0.0704 (18)	0.0464 (18)	−0.0226 (13)	0.0126 (13)	−0.0225 (14)
Br1	0.0567 (3)	0.0777 (3)	0.0779 (4)	−0.01732 (19)	0.0233 (2)	−0.0092 (2)
C11	0.0426 (17)	0.0423 (17)	0.0292 (19)	0.0124 (14)	0.0030 (13)	0.0034 (14)
C12	0.0444 (18)	0.0447 (19)	0.037 (2)	0.0086 (14)	0.0035 (14)	0.0056 (15)
C13	0.052 (2)	0.0419 (19)	0.048 (2)	0.0031 (15)	0.0075 (16)	0.0079 (16)
C14	0.0484 (19)	0.0375 (17)	0.047 (2)	0.0041 (14)	−0.0003 (15)	−0.0022 (15)
C15	0.056 (2)	0.0454 (19)	0.035 (2)	0.0031 (15)	0.0003 (15)	−0.0051 (15)
C16	0.0446 (18)	0.0478 (19)	0.033 (2)	0.0039 (14)	0.0062 (14)	0.0050 (15)
C17	0.0349 (15)	0.0437 (17)	0.032 (2)	0.0073 (13)	0.0047 (13)	−0.0007 (14)
C18	0.0396 (17)	0.0526 (19)	0.038 (2)	0.0056 (14)	0.0075 (15)	−0.0054 (16)
C19	0.067 (3)	0.074 (3)	0.089 (4)	−0.018 (2)	0.006 (2)	0.017 (3)
C20	0.096 (4)	0.076 (4)	0.183 (8)	−0.014 (3)	0.026 (4)	0.027 (4)
N4	0.0433 (15)	0.0402 (15)	0.0352 (18)	0.0041 (11)	0.0024 (12)	−0.0005 (11)
N5	0.0412 (14)	0.0463 (15)	0.0318 (17)	0.0057 (12)	0.0029 (11)	0.0002 (12)
N6	0.081 (2)	0.0522 (18)	0.039 (2)	−0.0051 (15)	0.0172 (15)	0.0063 (14)
O3	0.0587 (15)	0.0573 (15)	0.0489 (18)	−0.0115 (12)	0.0064 (12)	0.0049 (12)
O4	0.0805 (19)	0.088 (2)	0.049 (2)	−0.0289 (16)	0.0165 (14)	−0.0289 (15)
Br2	0.0787 (3)	0.0502 (2)	0.0698 (3)	−0.01168 (19)	0.0056 (2)	−0.01129 (19)

Geometric parameters (Å, º) top

C1—N2	1.331 (4)	C11—N5	1.335 (4)
C1—N1	1.379 (4)	C11—N4	1.371 (4)
C1—C2	1.434 (4)	C11—C12	1.437 (5)
C2—C3	1.363 (5)	C12—N6	1.352 (4)
C2—N3	1.365 (5)	C12—C13	1.376 (5)
C3—C4	1.405 (5)	C13—C14	1.407 (5)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.348 (5)	C14—C15	1.344 (5)
C4—Br1	1.904 (3)	C14—Br2	1.900 (3)
C5—N1	1.380 (4)	C15—N4	1.389 (4)
C5—H5	0.9300	C15—H15	0.9300
C6—N1	1.368 (4)	C16—C17	1.367 (5)
C6—C7	1.371 (5)	C16—N4	1.374 (4)
C6—H6	0.9300	C16—H16	0.9300
C7—N2	1.374 (4)	C17—N5	1.375 (4)
C7—C8	1.480 (5)	C17—C18	1.472 (5)
C8—O2	1.209 (4)	C18—O4	1.199 (4)
C8—O1	1.315 (4)	C18—O3	1.325 (4)
C9—O1	1.460 (4)	C19—C20	1.422 (7)
C9—C10	1.471 (6)	C19—O3	1.464 (5)
C9—H9A	0.9700	C19—H19A	0.9700
C9—H9B	0.9700	C19—H19B	0.9700
C10—H10A	0.9600	C20—H20A	0.9600
C10—H10B	0.9600	C20—H20B	0.9600
C10—H10C	0.9600	C20—H20C	0.9600
N3—H3A	0.8604	N6—H6A	0.8550
N3—H3B	0.8634	N6—H6B	0.8530

N2—C1—N1	112.3 (3)	N5—C11—N4	111.7 (3)
N2—C1—C2	129.3 (3)	N5—C11—C12	128.5 (3)
N1—C1—C2	118.4 (3)	N4—C11—C12	119.8 (3)
C3—C2—N3	124.6 (3)	N6—C12—C13	125.3 (3)
C3—C2—C1	118.0 (3)	N6—C12—C11	117.8 (3)
N3—C2—C1	117.3 (3)	C13—C12—C11	116.9 (3)
C2—C3—C4	120.3 (3)	C12—C13—C14	119.8 (3)
C2—C3—H3	119.8	C12—C13—H13	120.1
C4—C3—H3	119.8	C14—C13—H13	120.1
C5—C4—C3	123.1 (3)	C15—C14—C13	124.2 (3)
C5—C4—Br1	117.5 (3)	C15—C14—Br2	117.1 (3)
C3—C4—Br1	119.5 (3)	C13—C14—Br2	118.6 (3)
C4—C5—N1	116.5 (3)	C14—C15—N4	115.9 (3)
C4—C5—H5	121.7	C14—C15—H15	122.0
N1—C5—H5	121.7	N4—C15—H15	122.0
N1—C6—C7	105.5 (3)	C17—C16—N4	105.1 (3)
N1—C6—H6	127.3	C17—C16—H16	127.4
C7—C6—H6	127.3	N4—C16—H16	127.4
C6—C7—N2	112.0 (3)	C16—C17—N5	112.0 (3)
C6—C7—C8	122.9 (3)	C16—C17—C18	128.3 (3)
N2—C7—C8	125.1 (3)	N5—C17—C18	119.7 (3)
O2—C8—O1	124.4 (3)	O4—C18—O3	124.0 (3)
O2—C8—C7	121.8 (3)	O4—C18—C17	122.9 (3)
O1—C8—C7	113.8 (3)	O3—C18—C17	113.0 (3)
O1—C9—C10	109.4 (3)	C20—C19—O3	111.7 (4)
O1—C9—H9A	109.8	C20—C19—H19A	109.3
C10—C9—H9A	109.8	O3—C19—H19A	109.3
O1—C9—H9B	109.8	C20—C19—H19B	109.3
C10—C9—H9B	109.8	O3—C19—H19B	109.3
H9A—C9—H9B	108.2	H19A—C19—H19B	107.9
C9—C10—H10A	109.5	C19—C20—H20A	109.5
C9—C10—H10B	109.5	C19—C20—H20B	109.5
H10A—C10—H10B	109.5	H20A—C20—H20B	109.5
C9—C10—H10C	109.5	C19—C20—H20C	109.5
H10A—C10—H10C	109.5	H20A—C20—H20C	109.5
H10B—C10—H10C	109.5	H20B—C20—H20C	109.5
C6—N1—C1	106.6 (3)	C11—N4—C16	107.2 (3)
C6—N1—C5	129.8 (3)	C11—N4—C15	123.2 (3)
C1—N1—C5	123.7 (3)	C16—N4—C15	129.6 (3)
C1—N2—C7	103.7 (3)	C11—N5—C17	104.0 (3)
C2—N3—H3A	117.6	C12—N6—H6A	119.8
C2—N3—H3B	118.9	C12—N6—H6B	115.4
H3A—N3—H3B	113.5	H6A—N6—H6B	121.3
C8—O1—C9	114.8 (3)	C18—O3—C19	118.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N5ⁱ	0.86	2.47	3.300 (4)	161
N3—H3B···O3ⁱⁱ	0.86	2.38	3.055 (5)	135
N6—H6B···O2	0.85	2.34	3.096 (4)	147
N6—H6A···O1ⁱⁱⁱ	0.86	2.58	3.183 (4)	129
N6—H6A···N2ⁱⁱⁱ	0.86	2.60	3.388 (4)	154
C5—H5···O4	0.93	2.26	3.074 (4)	146
C19—H19B···O4	0.97	2.28	2.703 (6)	105

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀BrN₃O₂
M_r	284.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	8.366 (2), 11.842 (3), 22.743 (5)
β (°)	98.328 (6)
V (Å³)	2229.3 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.68
Crystal size (mm)	0.44 × 0.19 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.437, 0.535
No. of measured, independent and observed [I > 2σ(I)] reflections	13222, 4555, 3156
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.116, 1.03
No. of reflections	4555
No. of parameters	291
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.51

Computer programs: APEX2 (Bruker, 2009), SAINT-Plus (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N5ⁱ	0.86	2.47	3.300 (4)	161
N3—H3B···O3ⁱⁱ	0.86	2.38	3.055 (5)	135
N6—H6B···O2	0.85	2.34	3.096 (4)	147
N6—H6A···O1ⁱⁱⁱ	0.86	2.58	3.183 (4)	129
N6—H6A···N2ⁱⁱⁱ	0.86	2.60	3.388 (4)	154
C5—H5···O4	0.93	2.26	3.074 (4)	146
C19—H19B···O4	0.97	2.28	2.703 (6)	105

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+2, y+1/2, −z+1/2.

References

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Volume 67| Part 6| June 2011| Page o1390

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