N-(4-Bromo-phen-yl)pyrazine-2-carbox-amide.

The mol-ecule of the title compound, C(11)H(8)BrN(3)O, is close to planar (r.m.s. deviation of all 16 non-H atoms = 0.103 Å), a conformation stabilized by an intra-molecular N-H⋯N hydrogen bond, which generates an S(5) ring. In the crystal structure, supra-molecular chains mediated by C-H⋯O contacts (along a) are linked into a double layer via N⋯Br halogen bonds [3.207 (5) Å] and C-Br⋯π inter-actions [Br⋯ring centroid(pyrazine) = 3.446 (3) Å]. The layers stack along the b axis via weak π-π inter-actions [ring centroid(pyrazine)⋯ring centroid(benzene) distance = 3.803 (4) Å].

Related literature

For the anti­mycobacterial activity of pyrazinamide, see: Chaisson et al. (2002 ▶); Gordin et al. (2000 ▶); de Souza (2006 ▶). For structural studies of pyrazinamide derivatives; see: Baddeley et al. (2009 ▶); Howie et al. (2010a ▶,b ▶,c ▶,d ▶). For the synthesis, see: Wardell et al. (2008 ▶); Vontor et al. (1989 ▶). For background to halogen bonding, see: Metrangolo et al. (2008 ▶); Pennington et al. (2008 ▶). For graph-set nomenclature of hydrogen bonds, see: Bernstein et al. (1995 ▶). For details of software used to analyse the shape of the mol­ecule, see: Spek (2009 ▶).

Experimental

Crystal data

C11H8BrN3O

M = 278.11

Triclinic,

a = 5.8396 (4) Å

b = 7.3317 (7) Å

c = 13.3362 (12) Å

α = 101.670 (4)°

β = 96.728 (5)°

γ = 110.524 (5)°

V = 512.55 (8) Å3

Z = 2

Mo Kα radiation

μ = 3.99 mm−1

T = 120 K

0.18 × 0.10 × 0.02 mm

Data collection

Enraf–Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.764, T max = 1.000

8923 measured reflections

2110 independent reflections

1792 reflections with I > 2σ(I)

R int = 0.078

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.163

S = 1.18

2110 reflections

148 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.52 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810039036/hb5661sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039036/hb5661Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H8BrN3O	Z = 2
Mr = 278.11	F(000) = 276
Triclinic, P1	Dx = 1.802 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8396 (4) Å	Cell parameters from 22175 reflections
b = 7.3317 (7) Å	θ = 2.9–27.5°
c = 13.3362 (12) Å	µ = 3.99 mm−1
α = 101.670 (4)°	T = 120 K
β = 96.728 (5)°	Plate, colourless
γ = 110.524 (5)°	0.18 × 0.10 × 0.02 mm
V = 512.55 (8) Å3

Enraf–Nonius KappaCCD diffractometer	2110 independent reflections
Radiation source: Enraf–Nonius FR591 rotating anode	1792 reflections with I > 2σ(I)
10 cm confocal mirrors	Rint = 0.078
Detector resolution: 9.091 pixels mm-1	θmax = 26.5°, θmin = 3.1°
φ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −9→9
Tmin = 0.764, Tmax = 1.000	l = −16→16
8923 measured reflections

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
2110 reflections	(Δ/σ)max = 0.001
148 parameters	Δρmax = 0.55 e Å−3
1 restraint	Δρmin = −0.52 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 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.

	x	y	z	Uiso*/Ueq
Br1	0.20472 (10)	0.24870 (9)	−0.39064 (4)	0.0227 (2)
O1	0.8942 (7)	0.2880 (7)	0.0884 (3)	0.0259 (10)
N1	0.4828 (9)	0.2414 (8)	0.0622 (4)	0.0204 (10)
H1N	0.366 (9)	0.234 (10)	0.099 (5)	0.024*
N2	0.9106 (9)	0.2715 (8)	0.3965 (4)	0.0223 (11)
N3	0.4723 (9)	0.2202 (8)	0.2621 (4)	0.0212 (11)
C1	0.6982 (10)	0.2603 (8)	0.1192 (4)	0.0193 (12)
C2	0.4304 (10)	0.2444 (8)	−0.0435 (4)	0.0170 (11)
C3	0.1796 (10)	0.1859 (9)	−0.0902 (5)	0.0211 (12)
H3	0.0531	0.1461	−0.0512	0.025*
C4	0.1156 (10)	0.1861 (9)	−0.1937 (5)	0.0215 (12)
H4	−0.0549	0.1452	−0.2257	0.026*
C5	0.2979 (11)	0.2453 (8)	−0.2498 (5)	0.0192 (12)
C6	0.5492 (11)	0.3087 (9)	−0.2035 (5)	0.0210 (12)
H6	0.6745	0.3519	−0.2427	0.025*
C7	0.6156 (11)	0.3088 (9)	−0.1011 (5)	0.0205 (12)
H7	0.7868	0.3525	−0.0694	0.025*
C8	0.6915 (11)	0.2522 (9)	0.2304 (4)	0.0203 (12)
C9	0.9064 (11)	0.2777 (9)	0.2980 (5)	0.0198 (12)
H9	1.0565	0.3004	0.2724	0.024*
C10	0.6933 (11)	0.2377 (10)	0.4279 (5)	0.0229 (13)
H10	0.6870	0.2303	0.4979	0.028*
C11	0.4790 (11)	0.2134 (10)	0.3620 (5)	0.0243 (13)
H11	0.3300	0.1909	0.3883	0.029*

	U11	U22	U33	U12	U13	U23
Br1	0.0268 (4)	0.0286 (4)	0.0140 (3)	0.0123 (3)	0.0025 (2)	0.0066 (2)
O1	0.021 (2)	0.040 (3)	0.019 (2)	0.0123 (19)	0.0067 (17)	0.010 (2)
N1	0.018 (2)	0.031 (3)	0.013 (2)	0.011 (2)	0.0028 (18)	0.005 (2)
N2	0.022 (2)	0.030 (3)	0.020 (3)	0.013 (2)	0.003 (2)	0.012 (2)
N3	0.018 (2)	0.024 (3)	0.017 (3)	0.005 (2)	0.0011 (19)	0.004 (2)
C1	0.020 (3)	0.015 (3)	0.019 (3)	0.005 (2)	0.003 (2)	0.002 (2)
C2	0.025 (3)	0.017 (3)	0.008 (3)	0.006 (2)	0.003 (2)	0.005 (2)
C3	0.016 (3)	0.026 (3)	0.020 (3)	0.008 (2)	0.005 (2)	0.004 (2)
C4	0.019 (3)	0.027 (3)	0.019 (3)	0.011 (2)	0.002 (2)	0.004 (2)
C5	0.026 (3)	0.016 (3)	0.018 (3)	0.011 (2)	0.005 (2)	0.007 (2)
C6	0.023 (3)	0.026 (3)	0.017 (3)	0.011 (2)	0.009 (2)	0.008 (2)
C7	0.018 (3)	0.023 (3)	0.021 (3)	0.007 (2)	0.000 (2)	0.010 (2)
C8	0.026 (3)	0.022 (3)	0.015 (3)	0.011 (2)	0.004 (2)	0.004 (2)
C9	0.022 (3)	0.020 (3)	0.019 (3)	0.010 (2)	0.007 (2)	0.004 (2)
C10	0.029 (3)	0.034 (3)	0.013 (3)	0.014 (3)	0.012 (2)	0.013 (2)
C11	0.024 (3)	0.033 (3)	0.021 (3)	0.012 (3)	0.014 (3)	0.012 (3)

Br1—C5	1.901 (6)	C3—H3	0.9500
O1—C1	1.226 (6)	C4—C5	1.369 (8)
N1—C1	1.337 (7)	C4—H4	0.9500
N1—C2	1.413 (7)	C5—C6	1.394 (8)
N1—H1N	0.88 (6)	C6—C7	1.375 (8)
N2—C9	1.321 (8)	C6—H6	0.9500
N2—C10	1.339 (8)	C7—H7	0.9500
N3—C11	1.340 (8)	C8—C9	1.387 (8)
N3—C8	1.352 (8)	C9—H9	0.9500
C1—C8	1.501 (8)	C10—C11	1.376 (8)
C2—C3	1.398 (8)	C10—H10	0.9500
C2—C7	1.402 (8)	C11—H11	0.9500
C3—C4	1.387 (8)
C1—N1—C2	128.5 (5)	C6—C5—Br1	120.2 (4)
C1—N1—H1N	113 (5)	C7—C6—C5	120.0 (5)
C2—N1—H1N	119 (5)	C7—C6—H6	120.0
C9—N2—C10	116.0 (5)	C5—C6—H6	120.0
C11—N3—C8	115.2 (5)	C6—C7—C2	120.0 (5)
O1—C1—N1	125.4 (6)	C6—C7—H7	120.0
O1—C1—C8	119.5 (5)	C2—C7—H7	120.0
N1—C1—C8	115.1 (5)	N3—C8—C9	121.6 (5)
C3—C2—C7	119.4 (5)	N3—C8—C1	118.2 (5)
C3—C2—N1	117.1 (5)	C9—C8—C1	120.2 (5)
C7—C2—N1	123.5 (5)	N2—C9—C8	122.6 (5)
C4—C3—C2	120.0 (5)	N2—C9—H9	118.7
C4—C3—H3	120.0	C8—C9—H9	118.7
C2—C3—H3	120.0	N2—C10—C11	122.1 (5)
C5—C4—C3	120.1 (5)	N2—C10—H10	119.0
C5—C4—H4	120.0	C11—C10—H10	119.0
C3—C4—H4	120.0	N3—C11—C10	122.6 (5)
C4—C5—C6	120.6 (6)	N3—C11—H11	118.7
C4—C5—Br1	119.1 (4)	C10—C11—H11	118.7
C2—N1—C1—O1	1.4 (10)	N1—C2—C7—C6	−179.5 (6)
C2—N1—C1—C8	179.5 (5)	C11—N3—C8—C9	−0.6 (8)
C1—N1—C2—C3	169.0 (5)	C11—N3—C8—C1	179.6 (5)
C1—N1—C2—C7	−13.3 (9)	O1—C1—C8—N3	−179.6 (5)
C7—C2—C3—C4	2.0 (9)	N1—C1—C8—N3	2.2 (8)
N1—C2—C3—C4	179.8 (5)	O1—C1—C8—C9	0.6 (8)
C2—C3—C4—C5	−0.6 (9)	N1—C1—C8—C9	−177.6 (5)
C3—C4—C5—C6	−1.0 (9)	C10—N2—C9—C8	0.4 (9)
C3—C4—C5—Br1	−178.8 (4)	N3—C8—C9—N2	0.3 (9)
C4—C5—C6—C7	1.2 (9)	C1—C8—C9—N2	−179.9 (5)
Br1—C5—C6—C7	179.0 (4)	C9—N2—C10—C11	−0.8 (9)
C5—C6—C7—C2	0.2 (9)	C8—N3—C11—C10	0.2 (9)
C3—C2—C7—C6	−1.8 (9)	N2—C10—C11—N3	0.5 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3	0.88 (6)	2.22 (6)	2.708 (7)	115 (5)
C3—H3···O1i	0.95	2.39	3.177 (8)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N3	0.88 (6)	2.22 (6)	2.708 (7)	115 (5)
C3—H3⋯O1i	0.95	2.39	3.177 (8)	140

Symmetry code: (i) .