2-Amino-5-bromo-pyridinium 5-chloro-2-hy-droxy-benzoate.

In the 5-chloro-salicylate anion of the title salt, C5H6BrN2 (+)·C7H4ClO3 (-), an intra-molecular O-H⋯O hydrogen bond with an S(6) graph-set motif is formed, so that the anion is essentially planar with a dihedral angle of 1.3 (5)° between the benzene ring and the carboxyl-ate group. In the crystal, the protonated N atom and the 2-amino group of the cation 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. The crystal structure also features N-H⋯O and weak C-H⋯O inter-actions, resulting in a layer parallel to the (10-1) plane.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For related structures, see: Goubitz et al. (2001 ▶); Quah et al. (2010 ▶); Thanigaimani et al. (2013 ▶); Raza et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H6BrN2 +·C7H4ClO3 −

M = 345.58

Monoclinic,

a = 8.9769 (17) Å

b = 5.6601 (12) Å

c = 12.753 (2) Å

β = 90.662 (5)°

V = 647.9 (2) Å3

Z = 2

Mo Kα radiation

μ = 3.38 mm−1

T = 100 K

0.31 × 0.04 × 0.03 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.417, T max = 0.894

8030 measured reflections

4233 independent reflections

3014 reflections with I > 2σ(I)

R int = 0.087

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.091

S = 0.91

4233 reflections

188 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.84 e Å−3

Δρmin = −0.98 e Å−3

Absolute structure: Flack (1983 ▶), 1558 Friedel pairs

Flack parameter: 0.037 (11)

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681300665X/is5251sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300665X/is5251Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681300665X/is5251Isup3.cml

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

C5H6BrN2+·C7H4ClO3−	F(000) = 344
Mr = 345.58	Dx = 1.771 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1541 reflections
a = 8.9769 (17) Å	θ = 3.9–25.8°
b = 5.6601 (12) Å	µ = 3.38 mm−1
c = 12.753 (2) Å	T = 100 K
β = 90.662 (5)°	Needle, colourless
V = 647.9 (2) Å3	0.31 × 0.04 × 0.03 mm
Z = 2

Bruker SMART APEXII DUO CCD area-detector diffractometer	4233 independent reflections
Radiation source: fine-focus sealed tube	3014 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
φ and ω scans	θmax = 32.7°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→13
Tmin = 0.417, Tmax = 0.894	k = −7→8
8030 measured reflections	l = −19→19

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3
S = 0.91	(Δ/σ)max < 0.001
4233 reflections	Δρmax = 0.84 e Å−3
188 parameters	Δρmin = −0.98 e Å−3
1 restraint	Absolute structure: Flack (1983), 1558 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.037 (11)

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
Br1	0.79689 (4)	0.54521 (9)	0.42592 (3)	0.02463 (10)
Cl1	0.50091 (11)	0.29983 (19)	0.90762 (8)	0.0253 (2)
O1	0.8634 (3)	1.0293 (8)	0.87224 (17)	0.0248 (6)
O2	0.8465 (3)	1.1615 (5)	0.7080 (2)	0.0205 (6)
O3	0.6812 (3)	0.9496 (7)	0.5736 (2)	0.0239 (7)
N1	0.9596 (4)	0.0044 (6)	0.2466 (2)	0.0190 (8)
N2	0.9338 (4)	−0.1193 (7)	0.0762 (3)	0.0209 (8)
C1	0.8982 (4)	0.0324 (11)	0.1506 (2)	0.0177 (7)
C2	0.8005 (4)	0.2245 (7)	0.1337 (3)	0.0196 (8)
H2A	0.7561	0.2495	0.0666	0.024*
C3	0.7703 (4)	0.3746 (7)	0.2152 (3)	0.0196 (8)
H3A	0.7039	0.5034	0.2050	0.024*
C4	0.8375 (4)	0.3379 (7)	0.3134 (3)	0.0188 (8)
C5	0.9301 (4)	0.1523 (7)	0.3275 (3)	0.0207 (8)
H5A	0.9748	0.1252	0.3943	0.025*
C6	0.7012 (4)	0.8297 (7)	0.7544 (3)	0.0162 (7)
C7	0.6406 (4)	0.8057 (8)	0.6536 (3)	0.0177 (7)
C8	0.5392 (4)	0.6258 (7)	0.6314 (3)	0.0223 (9)
H8A	0.4986	0.6110	0.5626	0.027*
C9	0.4971 (4)	0.4687 (7)	0.7085 (3)	0.0210 (8)
H9A	0.4290	0.3447	0.6932	0.025*
C10	0.5563 (4)	0.4956 (7)	0.8089 (3)	0.0187 (9)
C11	0.6566 (4)	0.6721 (7)	0.8323 (3)	0.0169 (8)
H11A	0.6957	0.6868	0.9016	0.020*
C12	0.8105 (4)	1.0173 (9)	0.7811 (3)	0.0188 (8)
H1O3	0.721 (5)	1.068 (16)	0.582 (4)	0.025 (16)*
H1N1	1.027 (5)	−0.101 (9)	0.256 (4)	0.023 (12)*
H1N2	1.000 (6)	−0.248 (12)	0.092 (4)	0.039 (15)*
H2N2	0.898 (4)	−0.093 (8)	0.013 (4)	0.021 (11)*

	U11	U22	U33	U12	U13	U23
Br1	0.02863 (18)	0.02674 (19)	0.01847 (16)	0.0061 (3)	−0.00223 (12)	−0.0056 (2)
Cl1	0.0287 (5)	0.0241 (5)	0.0232 (5)	−0.0076 (4)	−0.0007 (4)	0.0025 (4)
O1	0.0301 (12)	0.0291 (17)	0.0151 (11)	−0.0079 (18)	−0.0073 (9)	0.0053 (16)
O2	0.0256 (14)	0.0202 (14)	0.0158 (13)	−0.0045 (12)	−0.0028 (11)	0.0015 (11)
O3	0.0306 (18)	0.0268 (18)	0.0141 (14)	−0.0079 (15)	−0.0061 (12)	0.0035 (12)
N1	0.0225 (15)	0.020 (2)	0.0148 (13)	0.0051 (15)	−0.0014 (11)	−0.0013 (13)
N2	0.0232 (18)	0.027 (2)	0.0128 (16)	0.0059 (15)	−0.0048 (13)	−0.0038 (14)
C1	0.0196 (15)	0.0188 (19)	0.0147 (14)	0.001 (2)	0.0000 (11)	0.005 (2)
C2	0.023 (2)	0.021 (2)	0.0151 (17)	0.0002 (16)	−0.0060 (15)	0.0048 (15)
C3	0.0193 (19)	0.019 (2)	0.0204 (19)	0.0038 (16)	−0.0021 (15)	0.0031 (15)
C4	0.0206 (19)	0.022 (2)	0.0136 (17)	0.0026 (16)	0.0004 (14)	−0.0021 (15)
C5	0.027 (2)	0.022 (2)	0.0129 (17)	−0.0013 (17)	−0.0025 (15)	0.0010 (15)
C6	0.0192 (18)	0.0173 (19)	0.0119 (16)	0.0013 (15)	−0.0006 (13)	−0.0022 (14)
C7	0.0157 (17)	0.021 (2)	0.0158 (17)	−0.0011 (16)	−0.0032 (13)	−0.0027 (16)
C8	0.0209 (18)	0.027 (2)	0.0188 (18)	−0.0023 (16)	−0.0037 (15)	−0.0038 (15)
C9	0.0183 (18)	0.023 (2)	0.0218 (19)	−0.0046 (15)	−0.0005 (15)	−0.0051 (15)
C10	0.0198 (17)	0.016 (3)	0.0199 (17)	0.0029 (14)	0.0022 (14)	−0.0014 (14)
C11	0.0192 (18)	0.018 (2)	0.0130 (16)	−0.0001 (15)	−0.0019 (14)	−0.0011 (14)
C12	0.0198 (16)	0.019 (2)	0.0171 (15)	0.0002 (17)	−0.0022 (12)	0.0006 (17)

Br1—C4	1.893 (4)	C3—C4	1.399 (5)
Cl1—C10	1.754 (4)	C3—H3A	0.9500
O1—C12	1.252 (4)	C4—C5	1.350 (5)
O2—C12	1.284 (5)	C5—H5A	0.9500
O3—C7	1.359 (5)	C6—C7	1.396 (5)
O3—H1O3	0.77 (8)	C6—C11	1.398 (5)
N1—C1	1.346 (4)	C6—C12	1.483 (6)
N1—C5	1.357 (5)	C7—C8	1.393 (5)
N1—H1N1	0.86 (5)	C8—C9	1.382 (6)
N2—C1	1.321 (6)	C8—H8A	0.9500
N2—H1N2	0.96 (6)	C9—C10	1.389 (5)
N2—H2N2	0.88 (5)	C9—H9A	0.9500
C1—C2	1.412 (6)	C10—C11	1.375 (5)
C2—C3	1.372 (6)	C11—H11A	0.9500
C2—H2A	0.9500
C7—O3—H1O3	123 (4)	C7—C6—C11	118.7 (4)
C1—N1—C5	122.5 (4)	C7—C6—C12	122.1 (3)
C1—N1—H1N1	119 (3)	C11—C6—C12	119.2 (3)
C5—N1—H1N1	118 (3)	O3—C7—C8	117.7 (3)
C1—N2—H1N2	120 (3)	O3—C7—C6	121.9 (4)
C1—N2—H2N2	117 (3)	C8—C7—C6	120.3 (4)
H1N2—N2—H2N2	122 (4)	C9—C8—C7	120.6 (4)
N2—C1—N1	118.4 (4)	C9—C8—H8A	119.7
N2—C1—C2	123.1 (3)	C7—C8—H8A	119.7
N1—C1—C2	118.5 (4)	C8—C9—C10	118.7 (4)
C3—C2—C1	119.3 (4)	C8—C9—H9A	120.6
C3—C2—H2A	120.4	C10—C9—H9A	120.6
C1—C2—H2A	120.4	C11—C10—C9	121.5 (4)
C2—C3—C4	120.0 (4)	C11—C10—Cl1	119.6 (3)
C2—C3—H3A	120.0	C9—C10—Cl1	118.9 (3)
C4—C3—H3A	120.0	C10—C11—C6	120.1 (3)
C5—C4—C3	119.6 (4)	C10—C11—H11A	120.0
C5—C4—Br1	120.3 (3)	C6—C11—H11A	120.0
C3—C4—Br1	120.1 (3)	O1—C12—O2	122.9 (4)
C4—C5—N1	120.2 (4)	O1—C12—C6	119.7 (4)
C4—C5—H5A	119.9	O2—C12—C6	117.4 (3)
N1—C5—H5A	119.9
C5—N1—C1—N2	179.6 (4)	O3—C7—C8—C9	177.9 (4)
C5—N1—C1—C2	0.6 (6)	C6—C7—C8—C9	0.0 (6)
N2—C1—C2—C3	−179.6 (4)	C7—C8—C9—C10	0.9 (6)
N1—C1—C2—C3	−0.5 (6)	C8—C9—C10—C11	−0.9 (6)
C1—C2—C3—C4	0.7 (6)	C8—C9—C10—Cl1	178.9 (3)
C2—C3—C4—C5	−1.0 (6)	C9—C10—C11—C6	0.1 (5)
C2—C3—C4—Br1	179.8 (3)	Cl1—C10—C11—C6	−179.7 (3)
C3—C4—C5—N1	1.0 (6)	C7—C6—C11—C10	0.8 (5)
Br1—C4—C5—N1	−179.7 (3)	C12—C6—C11—C10	−179.4 (3)
C1—N1—C5—C4	−0.8 (6)	C7—C6—C12—O1	−178.9 (4)
C11—C6—C7—O3	−178.6 (3)	C11—C6—C12—O1	1.3 (6)
C12—C6—C7—O3	1.6 (6)	C7—C6—C12—O2	1.1 (5)
C11—C6—C7—C8	−0.8 (6)	C11—C6—C12—O2	−178.7 (3)
C12—C6—C7—C8	179.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O2	0.77 (8)	2.02 (5)	2.553 (4)	127 (6)
N1—H1N1···O2i	0.86 (5)	1.82 (5)	2.666 (4)	172 (4)
N2—H1N2···O1i	0.96 (6)	1.81 (6)	2.770 (5)	175 (4)
N2—H2N2···O1ii	0.88 (5)	1.95 (5)	2.799 (5)	164 (3)
C8—H8A···O3iii	0.95	2.53	3.410 (5)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1O3⋯O2	0.77 (8)	2.02 (5)	2.553 (4)	127 (6)
N1—H1N1⋯O2i	0.86 (5)	1.82 (5)	2.666 (4)	172 (4)
N2—H1N2⋯O1i	0.96 (6)	1.81 (6)	2.770 (5)	175 (4)
N2—H2N2⋯O1ii	0.88 (5)	1.95 (5)	2.799 (5)	164 (3)
C8—H8A⋯O3iii	0.95	2.53	3.410 (5)	154

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