2-Amino-5-bromo­pyridinium 5-chloro-2-hy­droxy­benzoate

Kaliyaperumal Thanigaimani; Nuridayanti Che Khalib; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S160053681300665X

. 2013 Mar 16;69(Pt 4):o537–o538. doi: 10.1107/S160053681300665X

2-Amino-5-bromopyridinium 5-chloro-2-hydroxybenzoate

Kaliyaperumal Thanigaimani ^a, Nuridayanti Che Khalib ^a, Suhana Arshad ^a, Ibrahim Abdul Razak ^a,^*,^‡

PMCID: PMC3629591 PMID: 23634078

Abstract

In the 5-chlorosalicylate anion of the title salt, C₅H₆BrN₂ ⁺·C₇H₄ClO₃ ⁻, an intramolecular 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 carboxylate group. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxylate 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 interactions, 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 ▶). graphic file with name e-69-0o537-scheme1.jpg

Experimental

Crystal data

C₅H₆BrN₂ ⁺·C₇H₄ClO₃ ⁻
M _r = 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
Δρ_max = 0.84 e Å⁻³
Δρ_min = −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 ▶).

Supplementary Material

Click here for additional data file.^{(22.1KB, cif)}

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

e-69-0o537-sup1.cif^{(22.1KB, cif)}

Click here for additional data file.^{(207.4KB, hkl)}

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

e-69-0o537-Isup2.hkl^{(207.4KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

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

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

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

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for research facilities and a USM Short Term Grant (No. 304/PFIZIK/6312078) to conduct this work. KT thanks the Academy of Sciences for the Developing World and USM for a TWAS-USM fellowship.

supplementary crystallographic information

Comment

Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). They are often involved in hydrogen-bonding interactions. Related crystal structures of 2-amino-5-bromopyridine (Goubitz et al., 2001), 2-amino-5-bromopyridinium 2-hydroxybenzoate (Quah et al., 2010) and 2-amino-5-methylpyridinium 2-hydroxy-5-chlorobenzoate (Thanigaimani et al., 2013) have been reported. In order to study potential hydrogen-bonding interactions, the crystal structure determination of the title compound (I) was carried out.

The asymmetric unit (Fig. 1) contains one 2-amino-5-bromopyridinium cation and one 5-chlorosalicylate anion. An intramolecular O3–H1O3···O2 hydrogen bond in the 5-chlorosalicylate anion generates an S(6) ring motif (Bernstein et al., 1995). This motif is also observed in the crystal structures of 5-chloro-2-hydroxybenzoic acid (Raza et al., 2010). In the 2-amino-5-bromopyridinium cation, a wide angle [122.5 (4)°] is subtended at the protonated N1 atom. The 2-amino-5-bromopyridinium cation and 5-chlorosalicylate anion are essentially planar, with a maximum deviation of 0.008 (4) Å for atom N2 and 0.026 (4) Å for atom O1, respectively. The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal packing (Fig. 2), the protonated N1 atom and a nitrogen atom of the 2-amino group (N2) are hydrogen-bonded to the carboxylate oxygen atoms (O1 and O2) via a pair of intermolecular N1—H1N1···O2ⁱ and N2—H1N2···O1ⁱ hydrogen bonds (symmetry code in Table 1), forming a ring motif R₂²(8) (Bernstein et al., 1995). The crystal structure is further stabilized by N2—H2N2···O1ⁱⁱ and C8—H8A···O3ⁱⁱⁱ (symmetry codes in Table 1) intermolecular interactions. These interactions have resulted in a molecular layer parallel to the (101) plane. This crystal structure is isomorphous to the crystal structure of 2-amino-5-methylpyridinium 2-hydroxy-5-chlorobenzoate (Thanigaimani et al., 2013).

Experimental

Hot methanol solutions (20 ml) of 2-amino-5-bromopyridine (43 mg, Aldrich) and 5-chlorosalicylic acid (43 mg, Aldrich) were mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound (I) appeared after a few days.