2-Amino-5-bromo-pyridinium 3-amino-benzoate.

In the title salt, C(5)H(6)BrN(2) (+)·C(7)H(6)NO(2) (-), the pyridine N atom of the 2-amino-5-bromo-pyridine mol-ecule is protonated. In the crystal, the protonated N atom and the 2-amino group are hydrogen-bonded to the carboxyl-ate O atoms via a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. Two inversion-related 3-amino-benzoate anions are linked through N-H⋯O hydrogen-bonds, forming an R(2) (2)(14) ring motif. The crystal structure is further stabilized by π⋯π inter-actions involving the benzene and pyridinium rings with a centroid-centroid distance of 3.7743 (15) Å.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). Balasubramani & Fun (2009 ▶). For related structures, see: Goubitz et al. (2001 ▶); Vaday & Foxman (1999 ▶). For details of 3-amino­benzoic acid, see: Windholz (1976 ▶); Voogd et al. (1980 ▶). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C5H6BrN2 +·C7H6NO2 −

M = 309.15

Monoclinic,

a = 10.1650 (7) Å

b = 11.0431 (7) Å

c = 11.9550 (9) Å

β = 113.710 (2)°

V = 1228.71 (15) Å3

Z = 4

Mo Kα radiation

μ = 3.34 mm−1

T = 296 K

0.42 × 0.39 × 0.11 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.332, T max = 0.708

15251 measured reflections

3565 independent reflections

2650 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.137

S = 1.06

3565 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.51 e Å−3

Δρmin = −0.54 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810006288/tk2628sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810006288/tk2628Isup2.hkl

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

C5H6BrN2+·C7H6NO2−	F(000) = 620
Mr = 309.15	Dx = 1.671 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4215 reflections
a = 10.1650 (7) Å	θ = 2.6–26.8°
b = 11.0431 (7) Å	µ = 3.34 mm−1
c = 11.9550 (9) Å	T = 296 K
β = 113.710 (2)°	Blcok, brown
V = 1228.71 (15) Å3	0.42 × 0.39 × 0.11 mm
Z = 4

Bruker APEX DUO CCD area-detector diffractometer	3565 independent reflections
Radiation source: fine-focus sealed tube	2650 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
Tmin = 0.332, Tmax = 0.708	k = −15→14
15251 measured reflections	l = −16→16

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0846P)2 + 0.125P] where P = (Fo2 + 2Fc2)/3
3565 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.54 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	0.82844 (3)	0.52926 (3)	0.04268 (3)	0.05749 (15)
N1	0.5198 (2)	0.30649 (19)	0.06832 (17)	0.0383 (4)
N2	0.4208 (3)	0.2756 (2)	0.2082 (2)	0.0499 (5)
H2A	0.3715	0.2168	0.1638	0.060*
H2B	0.4125	0.2940	0.2749	0.060*
C1	0.5087 (2)	0.3373 (2)	0.1739 (2)	0.0378 (5)
C2	0.5959 (3)	0.4328 (3)	0.2429 (2)	0.0442 (5)
H2	0.5897	0.4569	0.3151	0.053*
C3	0.6892 (3)	0.4899 (2)	0.2043 (3)	0.0448 (5)
H3	0.7469	0.5525	0.2502	0.054*
C4	0.6971 (2)	0.4537 (2)	0.0954 (2)	0.0387 (5)
C5	0.6125 (2)	0.3619 (2)	0.0294 (2)	0.0387 (5)
H5	0.6183	0.3370	−0.0428	0.046*
O1	0.3733 (2)	1.13481 (18)	0.91776 (17)	0.0528 (5)
O2	0.2423 (2)	1.11501 (19)	1.02651 (17)	0.0549 (5)
N3	−0.0679 (3)	0.7483 (2)	0.8606 (3)	0.0677 (7)
H3A	−0.1118	0.6865	0.8182	0.081*
H3B	−0.0901	0.7746	0.9185	0.081*
C6	0.2439 (3)	0.9284 (2)	0.7774 (2)	0.0426 (5)
H6	0.3115	0.9693	0.7576	0.051*
C7	0.1775 (3)	0.8250 (3)	0.7134 (2)	0.0477 (6)
H7	0.2012	0.7963	0.6508	0.057*
C8	0.0755 (3)	0.7644 (2)	0.7426 (2)	0.0461 (6)
H8	0.0315	0.6954	0.6992	0.055*
C9	0.0388 (3)	0.8058 (2)	0.8355 (2)	0.0445 (5)
C10	0.1058 (3)	0.9094 (2)	0.9004 (2)	0.0412 (5)
H10	0.0820	0.9380	0.9630	0.049*
C11	0.2085 (3)	0.9701 (2)	0.8712 (2)	0.0375 (5)
C12	0.2807 (3)	1.0815 (2)	0.9441 (2)	0.0399 (5)
H1	0.4617	0.2439	0.0129	0.048*

	U11	U22	U33	U12	U13	U23
Br1	0.0532 (2)	0.0605 (2)	0.0637 (2)	−0.01495 (12)	0.02867 (15)	−0.00314 (12)
N1	0.0453 (10)	0.0357 (10)	0.0354 (9)	−0.0041 (8)	0.0179 (8)	−0.0056 (8)
N2	0.0630 (14)	0.0513 (13)	0.0451 (11)	−0.0075 (10)	0.0320 (10)	−0.0064 (10)
C1	0.0432 (11)	0.0364 (12)	0.0346 (10)	0.0035 (9)	0.0165 (8)	−0.0018 (9)
C2	0.0519 (13)	0.0432 (13)	0.0391 (12)	0.0008 (11)	0.0200 (10)	−0.0102 (10)
C3	0.0454 (13)	0.0388 (12)	0.0480 (13)	−0.0018 (10)	0.0167 (10)	−0.0113 (10)
C4	0.0357 (11)	0.0374 (12)	0.0438 (12)	−0.0006 (8)	0.0168 (9)	−0.0014 (9)
C5	0.0427 (11)	0.0401 (13)	0.0356 (11)	−0.0004 (9)	0.0183 (9)	−0.0031 (9)
O1	0.0679 (12)	0.0533 (12)	0.0469 (10)	−0.0214 (9)	0.0332 (9)	−0.0119 (8)
O2	0.0784 (13)	0.0500 (11)	0.0479 (10)	−0.0120 (9)	0.0376 (10)	−0.0104 (8)
N3	0.0686 (16)	0.0571 (16)	0.094 (2)	−0.0195 (13)	0.0496 (15)	−0.0166 (15)
C6	0.0455 (12)	0.0433 (13)	0.0412 (12)	−0.0013 (10)	0.0196 (9)	−0.0006 (10)
C7	0.0490 (13)	0.0480 (15)	0.0467 (13)	0.0038 (11)	0.0198 (10)	−0.0063 (11)
C8	0.0443 (13)	0.0380 (13)	0.0508 (14)	0.0026 (10)	0.0137 (10)	−0.0052 (11)
C9	0.0384 (11)	0.0407 (13)	0.0546 (14)	0.0005 (9)	0.0191 (10)	0.0024 (11)
C10	0.0430 (12)	0.0389 (13)	0.0457 (12)	0.0005 (9)	0.0221 (10)	0.0008 (10)
C11	0.0422 (11)	0.0334 (12)	0.0353 (11)	0.0024 (8)	0.0139 (9)	0.0034 (9)
C12	0.0493 (13)	0.0365 (12)	0.0336 (10)	−0.0017 (9)	0.0163 (9)	0.0021 (9)

Br1—C4	1.885 (2)	O2—C12	1.252 (3)
N1—C5	1.353 (3)	N3—C9	1.390 (3)
N1—C1	1.355 (3)	N3—H3A	0.8600
N1—H1	0.9745	N3—H3B	0.8600
N2—C1	1.313 (3)	C6—C11	1.387 (3)
N2—H2A	0.8600	C6—C7	1.389 (4)
N2—H2B	0.8600	C6—H6	0.9300
C1—C2	1.410 (4)	C7—C8	1.391 (4)
C2—C3	1.365 (4)	C7—H7	0.9300
C2—H2	0.9300	C8—C9	1.384 (4)
C3—C4	1.395 (4)	C8—H8	0.9300
C3—H3	0.9300	C9—C10	1.396 (4)
C4—C5	1.358 (3)	C10—C11	1.398 (3)
C5—H5	0.9300	C10—H10	0.9300
O1—C12	1.254 (3)	C11—C12	1.515 (3)
C5—N1—C1	122.5 (2)	H3A—N3—H3B	120.0
C5—N1—H1	113.7	C11—C6—C7	119.5 (2)
C1—N1—H1	123.8	C11—C6—H6	120.3
C1—N2—H2A	120.0	C7—C6—H6	120.3
C1—N2—H2B	120.0	C6—C7—C8	120.2 (2)
H2A—N2—H2B	120.0	C6—C7—H7	119.9
N2—C1—N1	118.8 (2)	C8—C7—H7	119.9
N2—C1—C2	123.5 (2)	C9—C8—C7	120.8 (2)
N1—C1—C2	117.7 (2)	C9—C8—H8	119.6
C3—C2—C1	120.4 (2)	C7—C8—H8	119.6
C3—C2—H2	119.8	C8—C9—N3	120.6 (2)
C1—C2—H2	119.8	C8—C9—C10	119.2 (2)
C2—C3—C4	119.5 (2)	N3—C9—C10	120.2 (2)
C2—C3—H3	120.3	C9—C10—C11	120.1 (2)
C4—C3—H3	120.3	C9—C10—H10	120.0
C5—C4—C3	119.7 (2)	C11—C10—H10	120.0
C5—C4—Br1	120.33 (18)	C6—C11—C10	120.3 (2)
C3—C4—Br1	119.97 (19)	C6—C11—C12	120.8 (2)
N1—C5—C4	120.3 (2)	C10—C11—C12	118.9 (2)
N1—C5—H5	119.9	O2—C12—O1	124.2 (2)
C4—C5—H5	119.9	O2—C12—C11	117.4 (2)
C9—N3—H3A	120.0	O1—C12—C11	118.4 (2)
C9—N3—H3B	120.0
C5—N1—C1—N2	−177.0 (2)	C7—C8—C9—N3	176.9 (3)
C5—N1—C1—C2	1.5 (3)	C7—C8—C9—C10	−0.2 (4)
N2—C1—C2—C3	177.4 (3)	C8—C9—C10—C11	0.0 (4)
N1—C1—C2—C3	−1.0 (4)	N3—C9—C10—C11	−177.1 (3)
C1—C2—C3—C4	0.4 (4)	C7—C6—C11—C10	−0.7 (4)
C2—C3—C4—C5	−0.2 (4)	C7—C6—C11—C12	179.1 (2)
C2—C3—C4—Br1	−178.6 (2)	C9—C10—C11—C6	0.4 (4)
C1—N1—C5—C4	−1.3 (4)	C9—C10—C11—C12	−179.3 (2)
C3—C4—C5—N1	0.7 (4)	C6—C11—C12—O2	179.1 (2)
Br1—C4—C5—N1	178.99 (18)	C10—C11—C12—O2	−1.2 (3)
C11—C6—C7—C8	0.5 (4)	C6—C11—C12—O1	−0.2 (4)
C6—C7—C8—C9	−0.1 (4)	C10—C11—C12—O1	179.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.98	1.65	2.626 (3)	176
N2—H2A···O2i	0.86	1.99	2.826 (3)	165
N2—H2B···O1ii	0.86	2.06	2.909 (3)	170
N3—H3B···O2iii	0.86	2.26	3.028 (4)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.98	1.65	2.626 (3)	176
N2—H2A⋯O2i	0.86	1.99	2.826 (3)	165
N2—H2B⋯O1ii	0.86	2.06	2.909 (3)	170
N3—H3B⋯O2iii	0.86	2.26	3.028 (4)	148

Symmetry codes: (i) ; (ii) ; (iii) .