2-Amino-5-bromo­pyridinium 2-carb­oxy­benzoate

Quah, C.K.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536810030977

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Pages o2269-o2270

https://doi.org/10.1107/S1600536810030977

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2-Amino-5-bromopyridinium 2-carboxybenzoate

Ching Kheng Quah,^a ‡ Madhukar Hemamalini ^a and Hoong-Kun Fun ^a ^*§

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 26 July 2010; accepted 3 August 2010; online 11 August 2010)

The asymmetric unit of the title compound, C₅H₆BrN₂⁺·C₈H₅O₄⁻, consists of two crystallographically independent 2-amino-5-bromopyridinium cations (A and B) and two 2-carboxybenzoate anions (A and B). Each 2-amino-5-bromopyridinium cation is approximately planar, with a maximum deviation of 0.047 (1) Å in cation A and 0.027 (1) Å in cation B. The 2-amino-5-bromopyridinium unit in cation A is inclined at dihedral angles of 4.9 (3) and 2.2 (3)° with the phenyl rings of the A and B 2-carboxybenzoate anions, respectively. The corresponding angles for cation B are 3.0 (3) and 5.6 (3)°. The molecular structure is stabilized by an intramolecular O—H⋯O hydrogen bond,which generates an S(7) ring motif. The cations and anions are linked via intermolecular N—H⋯O and C—H⋯O hydrogen bonds, generating R₂²(8) ring motifs. In the crystal packing, molecules are linked into wave-like chains along [001] via adjacent ring motifs. Short intermolecular distances between the phenyl and pyridine rings [3.613 (4) and 3.641 (4) Å] indicate the existence of π–π interactions. The crystal structure is a non-merohedral twin with a contribution of 0.271 (3) of the minor component.

Related literature

For applications of phthalic acid, see: Dale et al. (2004 ); Ballabh et al. (2005 ). For related structures, see: Schuckmann et al. (1978 ); Küppers (1978 ); Jessen & Küppers (1991 ); Quah et al. (2008 , 2010a ,b ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ). For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₅H₆BrN₂⁺·C₈H₅O₄⁻
M_r = 339.15
Triclinic, $[P \overline 1]$
a = 9.0192 (4) Å
b = 10.2689 (5) Å
c = 14.4092 (6) Å
α = 82.269 (2)°
β = 83.969 (2)°
γ = 87.845 (2)°
V = 1314.72 (10) Å³
Z = 4
Mo Kα radiation
μ = 3.14 mm⁻¹
T = 100 K
0.24 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.526, T_max = 0.740
7631 measured reflections
7631 independent reflections
5583 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.194
S = 1.09
7631 reflections
364 parameters
H-atom parameters constrained
Δρ_max = 1.14 e Å⁻³
Δρ_min = −1.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1N1⋯O4A	0.86	1.80	2.664 (7)	176
N2A—H2NA⋯O4Bⁱ	0.94	1.97	2.910 (8)	175
N2A—H3NA⋯O3A	0.98	1.97	2.930 (7)	167
O3B—H2O3⋯O2B	0.75	1.68	2.391 (6)	159
N1B—H2N1⋯O1B	0.92	1.82	2.647 (7)	147
N2B—H3N2⋯O1Aⁱⁱ	1.00	1.91	2.903 (8)	176
N2B—H4N2⋯O2B	0.81	2.20	2.971 (7)	160
C4A—H4AA⋯O3Bⁱ	0.93	2.44	3.219 (9)	141
C4B—H4BA⋯O2Aⁱⁱ	0.93	2.42	3.175 (9)	139
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z-1.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810030977/bt5311sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030977/bt5311Isup2.hkl

checkCIF report

Comment top

Phthalic acid forms hydrogen phthalate salts with various organic and other compounds. The crystal structures of hydrogen phthalates include calcium phthalate monohydrate (Schuckmann et al., 1978), lithium hydrogen phthalate monohydrate (Küppers, 1978) and tetramethylammonium hydrogen phthalate (Jessen & Küppers, 1991) have been reported in the literature. Hydrogen phthalates also form supramolecular assemblies, such as extended chains, ribbons and three-dimensional networks (Dale et al., 2004; Ballabh et al., 2005). In this paper, the hydrogen-bonding patterns of 2-amino-5-bromopyridinium hydrogenphthalate, (I), are discussed.

The asymmetric unit of the title compound consists of two crystallographically independent 2-amino-5-bromopyridinium cations (A and B) and two 2-carboxybenzoate anions (A and B). The bond lengths (Allen et al., 1987) and angles in the title compound (Fig. 1) are within normal ranges and comparable with the related structures (Quah et al., 2008, 2010a, b). Each 2-amino-5-bromopyridinium cation is approximately planar, with a maximum deviation of 0.047 (1) Å for atom Br1A in cation A and 0.027 (1) Å for atom Br1B in cation B. The 2-amino-5-bromopyridinium in cation A is inclined at dihedral angles of 4.9 (3) and 2.2 (3)° with the C6A—C11A and C6B—C11B phenyl rings, respectively. The correspondence angles for cation B are 3.0 (3) and 5.6 (3)°. The molecular structure is stabilized by an intramolecular O3B—H2O3···O2B hydrogen bond which generates an S(7) ring motif (Bernstein et al., 1995).

The cations and anions are linked via intermolecular N–H···O and C–H···O hydrogen bonds (Table 1), generating R₂²(8) ring motifs. In the crystal packing (Fig. 2), the molecules are linked into one-dimensional wave-like chains along [001] via adjacent ring motifs. The crystal packing is further consolidated by π-π stacking interactions between the centroids of C6A—C11A (Cg1), N1B/C1B—C5B (Cg2) rings and C6B—C11B (Cg3), N1A/C1A—C5A (Cg4) rings, with Cg1···Cg2ⁱⁱⁱ and Cg3···Cg4 distances of 3.613 (4) and 3.641 (4) Å, respectively [symmetry code: (iii) x, y, 1 + z]

Related literature top

For applications of phthalic acid, see: Dale et al. (2004); Ballabh et al. (2005). For related structures, see: Schuckmann et al. (1978); Küppers (1978); Jessen & Küppers (1991); Quah et al. (2008, 2010a,b). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A hot methanol solution (20 ml) of 2-amino-5-bromopyridine (86 mg, Aldrich) and phthalic acid (83 mg, Merck) was mixed and warmed over a magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound appeared after a few days.

Structure description top

For applications of phthalic acid, see: Dale et al. (2004); Ballabh et al. (2005). For related structures, see: Schuckmann et al. (1978); Küppers (1978); Jessen & Küppers (1991); Quah et al. (2008, 2010a,b). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. Intramolecular interactions are shown in dashed lines.
	Fig. 2. The crystal structure of the title compound viewed along the b axis. H atoms not involved in intermolecular interactions (dashed lines) have been omitted for clarity.

2-Amino-5-bromopyridinium 2-carboxybenzoate top

Crystal data top

C₅H₆BrN₂⁺·C₈H₅O₄⁻	Z = 4
M_r = 339.15	F(000) = 680
Triclinic, P1	D_x = 1.713 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0192 (4) Å	Cell parameters from 9951 reflections
b = 10.2689 (5) Å	θ = 2.3–27.7°
c = 14.4092 (6) Å	µ = 3.14 mm⁻¹
α = 82.269 (2)°	T = 100 K
β = 83.969 (2)°	Block, colourless
γ = 87.845 (2)°	0.24 × 0.20 × 0.10 mm
V = 1314.72 (10) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7631 independent reflections
Radiation source: fine-focus sealed tube	5583 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
φ and ω scans	θ_max = 30.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
T_min = 0.526, T_max = 0.740	k = −14→14
7631 measured reflections	l = −6→20

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.194	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0079P)² + 15.1445P] where P = (F_o² + 2F_c²)/3
7631 reflections	(Δ/σ)_max < 0.001
364 parameters	Δρ_max = 1.14 e Å⁻³
0 restraints	Δρ_min = −1.25 e Å⁻³

Crystal data top

C₅H₆BrN₂⁺·C₈H₅O₄⁻	γ = 87.845 (2)°
M_r = 339.15	V = 1314.72 (10) Å³
Triclinic, P1	Z = 4
a = 9.0192 (4) Å	Mo Kα radiation
b = 10.2689 (5) Å	µ = 3.14 mm⁻¹
c = 14.4092 (6) Å	T = 100 K
α = 82.269 (2)°	0.24 × 0.20 × 0.10 mm
β = 83.969 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7631 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5583 reflections with I > 2σ(I)
T_min = 0.526, T_max = 0.740	R_int = 0.000
7631 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.194	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0079P)² + 15.1445P] where P = (F_o² + 2F_c²)/3
7631 reflections	Δρ_max = 1.14 e Å⁻³
364 parameters	Δρ_min = −1.25 e Å⁻³

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1A	0.79304 (8)	0.52547 (8)	0.47978 (5)	0.03121 (19)
N1A	0.6074 (6)	0.6549 (5)	0.7230 (4)	0.0196 (10)
H1N1	0.6339	0.6324	0.7790	0.023*
N2A	0.3893 (6)	0.7645 (6)	0.7726 (4)	0.0236 (11)
H2NA	0.2872	0.7862	0.7731	0.02 (2)*
H3NA	0.4231	0.7281	0.8335	0.03 (2)*
C1A	0.7009 (7)	0.6012 (7)	0.6581 (4)	0.0223 (13)
H1AA	0.7894	0.5596	0.6749	0.027*
C2A	0.6649 (7)	0.6083 (7)	0.5678 (4)	0.0223 (13)
C3A	0.5324 (7)	0.6715 (7)	0.5428 (4)	0.0243 (13)
H3AA	0.5077	0.6766	0.4813	0.029*
C4A	0.4383 (8)	0.7262 (7)	0.6095 (4)	0.0244 (13)
H4AA	0.3505	0.7696	0.5932	0.029*
C5A	0.4765 (7)	0.7158 (6)	0.7033 (4)	0.0206 (12)
H2O3	1.0538	0.7571	0.5815	0.031*
Br1B	0.69848 (8)	0.98559 (8)	0.01879 (5)	0.03200 (19)
N1B	0.8885 (6)	0.8524 (6)	0.2596 (4)	0.0221 (11)
H2N1	0.8515	0.8432	0.3223	0.027*
N2B	1.0992 (7)	0.7300 (6)	0.2998 (4)	0.0261 (12)
H3N2	1.2048	0.7046	0.2816	0.031*
H4N2	1.0882	0.7577	0.3502	0.031*
C1B	0.7963 (7)	0.9101 (7)	0.1972 (4)	0.0222 (13)
H1BA	0.7119	0.9571	0.2180	0.027*
C2B	0.8265 (7)	0.8995 (7)	0.1045 (4)	0.0229 (13)
C3B	0.9539 (8)	0.8290 (7)	0.0737 (5)	0.0257 (14)
H3BA	0.9755	0.8216	0.0101	0.031*
C4B	1.0461 (8)	0.7713 (7)	0.1368 (4)	0.0245 (13)
H4BA	1.1305	0.7237	0.1168	0.029*
C5B	1.0122 (7)	0.7843 (7)	0.2339 (4)	0.0222 (13)
O1B	0.7873 (6)	0.9253 (6)	0.4244 (3)	0.0348 (13)
O2B	0.9788 (5)	0.8164 (5)	0.4822 (3)	0.0255 (10)
O3B	1.0802 (6)	0.7552 (5)	0.6291 (3)	0.0301 (11)
O4B	1.0764 (6)	0.8386 (5)	0.7617 (3)	0.0291 (11)
C10B	0.8034 (7)	0.9257 (6)	0.5868 (4)	0.0195 (12)
C6B	0.7961 (8)	0.9415 (7)	0.7535 (4)	0.0232 (13)
H6BA	0.8386	0.9233	0.8101	0.028*
C7B	0.6601 (8)	1.0105 (7)	0.7525 (5)	0.0252 (13)
H7BA	0.6122	1.0362	0.8077	0.030*
C8B	0.5967 (8)	1.0405 (7)	0.6684 (5)	0.0253 (13)
H8BA	0.5074	1.0884	0.6663	0.030*
C9B	0.6676 (7)	0.9984 (7)	0.5881 (4)	0.0216 (12)
H9BA	0.6239	1.0188	0.5321	0.026*
C11B	0.8708 (7)	0.8986 (6)	0.6729 (4)	0.0202 (12)
C12B	0.8597 (7)	0.8867 (6)	0.4919 (4)	0.0200 (12)
C13B	1.0179 (7)	0.8290 (7)	0.6895 (5)	0.0233 (13)
O1A	0.4113 (6)	0.6654 (5)	1.2511 (3)	0.0313 (11)
O2A	0.3986 (6)	0.7420 (5)	1.1025 (3)	0.0284 (11)
H1OA	0.4630	0.7831	1.0627	0.043*
O3A	0.5145 (5)	0.6946 (5)	0.9528 (3)	0.0271 (10)
O4A	0.7025 (6)	0.5820 (6)	0.8916 (3)	0.0344 (13)
C6A	0.8161 (7)	0.5016 (7)	1.0550 (4)	0.0222 (13)
H6AB	0.8572	0.4762	0.9981	0.027*
C7A	0.8877 (7)	0.4632 (7)	1.1348 (5)	0.0247 (13)
H7AB	0.9766	0.4145	1.1309	0.030*
C8A	0.8256 (8)	0.4979 (7)	1.2215 (4)	0.0245 (13)
H8AB	0.8736	0.4741	1.2755	0.029*
C9A	0.6919 (7)	0.5682 (6)	1.2255 (4)	0.0219 (12)
H9AB	0.6506	0.5902	1.2834	0.026*
C10A	0.6164 (7)	0.6075 (6)	1.1468 (4)	0.0197 (12)
C11A	0.6819 (7)	0.5788 (6)	1.0570 (4)	0.0190 (12)
C12A	0.4671 (8)	0.6747 (7)	1.1692 (5)	0.0240 (13)
C13A	0.6295 (7)	0.6207 (7)	0.9607 (4)	0.0215 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1A	0.0271 (4)	0.0455 (4)	0.0232 (3)	−0.0034 (3)	0.0011 (3)	−0.0148 (3)
N1A	0.022 (3)	0.024 (3)	0.013 (2)	−0.003 (2)	−0.0037 (19)	−0.0040 (19)
N2A	0.022 (3)	0.030 (3)	0.020 (3)	−0.001 (2)	−0.002 (2)	−0.006 (2)
C1A	0.020 (3)	0.026 (3)	0.021 (3)	−0.005 (2)	−0.002 (2)	−0.004 (2)
C2A	0.024 (3)	0.030 (3)	0.014 (3)	−0.008 (3)	0.003 (2)	−0.008 (2)
C3A	0.026 (3)	0.033 (4)	0.017 (3)	−0.007 (3)	−0.006 (2)	−0.008 (3)
C4A	0.023 (3)	0.030 (4)	0.020 (3)	−0.005 (3)	−0.007 (2)	0.000 (2)
C5A	0.022 (3)	0.022 (3)	0.019 (3)	−0.005 (2)	−0.003 (2)	−0.004 (2)
Br1B	0.0262 (4)	0.0485 (5)	0.0208 (3)	−0.0002 (3)	−0.0066 (3)	0.0002 (3)
N1B	0.023 (3)	0.028 (3)	0.016 (2)	0.000 (2)	0.001 (2)	−0.006 (2)
N2B	0.028 (3)	0.031 (3)	0.019 (3)	0.004 (2)	0.000 (2)	−0.004 (2)
C1B	0.021 (3)	0.024 (3)	0.022 (3)	−0.005 (2)	−0.002 (2)	−0.004 (2)
C2B	0.022 (3)	0.028 (3)	0.020 (3)	−0.005 (3)	−0.004 (2)	−0.004 (2)
C3B	0.028 (3)	0.030 (4)	0.019 (3)	−0.006 (3)	0.003 (2)	−0.009 (3)
C4B	0.026 (3)	0.029 (3)	0.018 (3)	0.000 (3)	0.003 (2)	−0.008 (2)
C5B	0.024 (3)	0.023 (3)	0.019 (3)	−0.005 (2)	0.001 (2)	−0.002 (2)
O1B	0.036 (3)	0.051 (3)	0.018 (2)	0.014 (3)	−0.007 (2)	−0.007 (2)
O2B	0.022 (2)	0.033 (3)	0.021 (2)	0.0008 (19)	0.0014 (18)	−0.0059 (19)
O3B	0.034 (3)	0.037 (3)	0.020 (2)	0.012 (2)	−0.008 (2)	−0.007 (2)
O4B	0.029 (3)	0.033 (3)	0.028 (2)	0.003 (2)	−0.014 (2)	−0.004 (2)
C10B	0.022 (3)	0.021 (3)	0.016 (3)	−0.003 (2)	−0.003 (2)	−0.001 (2)
C6B	0.033 (3)	0.024 (3)	0.014 (3)	0.000 (3)	−0.005 (2)	−0.004 (2)
C7B	0.030 (3)	0.027 (3)	0.019 (3)	−0.003 (3)	0.001 (3)	−0.008 (2)
C8B	0.023 (3)	0.030 (4)	0.024 (3)	0.004 (3)	−0.001 (2)	−0.007 (3)
C9B	0.023 (3)	0.027 (3)	0.015 (3)	−0.002 (2)	−0.001 (2)	−0.002 (2)
C11B	0.022 (3)	0.021 (3)	0.018 (3)	−0.002 (2)	−0.001 (2)	−0.004 (2)
C12B	0.020 (3)	0.023 (3)	0.016 (3)	−0.002 (2)	−0.001 (2)	0.000 (2)
C13B	0.020 (3)	0.024 (3)	0.026 (3)	0.004 (2)	−0.008 (2)	−0.004 (2)
O1A	0.035 (3)	0.033 (3)	0.021 (2)	0.008 (2)	0.008 (2)	0.002 (2)
O2A	0.030 (3)	0.035 (3)	0.018 (2)	0.009 (2)	0.0023 (18)	−0.0023 (19)
O3A	0.027 (2)	0.036 (3)	0.019 (2)	0.010 (2)	−0.0050 (18)	−0.0047 (19)
O4A	0.033 (3)	0.057 (4)	0.013 (2)	0.015 (3)	−0.0048 (19)	−0.005 (2)
C6A	0.021 (3)	0.029 (3)	0.016 (3)	0.000 (3)	0.003 (2)	−0.006 (2)
C7A	0.021 (3)	0.028 (3)	0.022 (3)	0.002 (3)	0.001 (2)	0.002 (3)
C8A	0.026 (3)	0.030 (3)	0.018 (3)	−0.003 (3)	−0.005 (2)	0.000 (2)
C9A	0.028 (3)	0.023 (3)	0.014 (3)	−0.002 (3)	0.001 (2)	−0.004 (2)
C10A	0.023 (3)	0.020 (3)	0.016 (3)	0.000 (2)	0.002 (2)	−0.005 (2)
C11A	0.021 (3)	0.022 (3)	0.014 (3)	−0.002 (2)	0.002 (2)	−0.004 (2)
C12A	0.028 (3)	0.020 (3)	0.024 (3)	0.002 (3)	0.001 (3)	−0.004 (2)
C13A	0.022 (3)	0.028 (3)	0.015 (3)	−0.004 (2)	−0.002 (2)	−0.002 (2)

Geometric parameters (Å, º) top

Br1A—C2A	1.891 (6)	O3B—H2O3	0.7471
N1A—C1A	1.352 (8)	O4B—C13B	1.231 (8)
N1A—C5A	1.354 (8)	C10B—C9B	1.410 (9)
N1A—H1N1	0.8651	C10B—C11B	1.428 (8)
N2A—C5A	1.343 (8)	C10B—C12B	1.508 (9)
N2A—H2NA	0.9388	C6B—C7B	1.394 (10)
N2A—H3NA	0.9814	C6B—C11B	1.396 (9)
C1A—C2A	1.366 (9)	C6B—H6BA	0.9300
C1A—H1AA	0.9300	C7B—C8B	1.385 (9)
C2A—C3A	1.396 (10)	C7B—H7BA	0.9300
C3A—C4A	1.378 (9)	C8B—C9B	1.375 (9)
C3A—H3AA	0.9300	C8B—H8BA	0.9300
C4A—C5A	1.418 (9)	C9B—H9BA	0.9300
C4A—H4AA	0.9300	C11B—C13B	1.510 (9)
Br1B—C2B	1.889 (7)	O1A—C12A	1.226 (8)
N1B—C5B	1.340 (8)	O2A—C12A	1.302 (8)
N1B—C1B	1.352 (8)	O2A—H1OA	0.8532
N1B—H2N1	0.9235	O3A—C13A	1.267 (8)
N2B—C5B	1.345 (8)	O4A—C13A	1.239 (8)
N2B—H3N2	0.9952	C6A—C7A	1.381 (9)
N2B—H4N2	0.8108	C6A—C11A	1.421 (9)
C1B—C2B	1.353 (9)	C6A—H6AB	0.9300
C1B—H1BA	0.9300	C7A—C8A	1.399 (9)
C2B—C3B	1.400 (10)	C7A—H7AB	0.9300
C3B—C4B	1.359 (10)	C8A—C9A	1.382 (9)
C3B—H3BA	0.9300	C8A—H8AB	0.9300
C4B—C5B	1.423 (9)	C9A—C10A	1.389 (9)
C4B—H4BA	0.9300	C9A—H9AB	0.9300
O1B—C12B	1.241 (8)	C10A—C11A	1.428 (8)
O2B—C12B	1.277 (8)	C10A—C12A	1.514 (9)
O3B—C13B	1.300 (8)	C11A—C13A	1.515 (8)

C1A—N1A—C5A	123.1 (5)	C7B—C6B—C11B	122.4 (6)
C1A—N1A—H1N1	111.1	C7B—C6B—H6BA	118.8
C5A—N1A—H1N1	124.9	C11B—C6B—H6BA	118.8
C5A—N2A—H2NA	126.7	C8B—C7B—C6B	119.4 (6)
C5A—N2A—H3NA	109.3	C8B—C7B—H7BA	120.3
H2NA—N2A—H3NA	115.7	C6B—C7B—H7BA	120.3
N1A—C1A—C2A	119.7 (6)	C9B—C8B—C7B	119.2 (6)
N1A—C1A—H1AA	120.2	C9B—C8B—H8BA	120.4
C2A—C1A—H1AA	120.2	C7B—C8B—H8BA	120.4
C1A—C2A—C3A	119.9 (6)	C8B—C9B—C10B	123.0 (6)
C1A—C2A—Br1A	118.9 (5)	C8B—C9B—H9BA	118.5
C3A—C2A—Br1A	121.1 (5)	C10B—C9B—H9BA	118.5
C4A—C3A—C2A	119.8 (6)	C6B—C11B—C10B	118.3 (6)
C4A—C3A—H3AA	120.1	C6B—C11B—C13B	113.6 (6)
C2A—C3A—H3AA	120.1	C10B—C11B—C13B	128.2 (6)
C3A—C4A—C5A	119.4 (6)	O1B—C12B—O2B	121.6 (6)
C3A—C4A—H4AA	120.3	O1B—C12B—C10B	118.0 (6)
C5A—C4A—H4AA	120.3	O2B—C12B—C10B	120.4 (6)
N2A—C5A—N1A	119.0 (6)	O4B—C13B—O3B	120.1 (6)
N2A—C5A—C4A	122.9 (6)	O4B—C13B—C11B	120.0 (6)
N1A—C5A—C4A	118.1 (6)	O3B—C13B—C11B	119.9 (6)
C5B—N1B—C1B	122.7 (6)	C12A—O2A—H1OA	108.9
C5B—N1B—H2N1	118.9	C7A—C6A—C11A	122.3 (6)
C1B—N1B—H2N1	116.7	C7A—C6A—H6AB	118.9
C5B—N2B—H3N2	120.3	C11A—C6A—H6AB	118.9
C5B—N2B—H4N2	117.1	C6A—C7A—C8A	119.7 (6)
H3N2—N2B—H4N2	112.4	C6A—C7A—H7AB	120.2
N1B—C1B—C2B	120.1 (6)	C8A—C7A—H7AB	120.2
N1B—C1B—H1BA	120.0	C9A—C8A—C7A	119.0 (6)
C2B—C1B—H1BA	120.0	C9A—C8A—H8AB	120.5
C1B—C2B—C3B	119.6 (6)	C7A—C8A—H8AB	120.5
C1B—C2B—Br1B	119.0 (5)	C8A—C9A—C10A	122.8 (6)
C3B—C2B—Br1B	121.4 (5)	C8A—C9A—H9AB	118.6
C4B—C3B—C2B	120.0 (6)	C10A—C9A—H9AB	118.6
C4B—C3B—H3BA	120.0	C9A—C10A—C11A	119.0 (6)
C2B—C3B—H3BA	120.0	C9A—C10A—C12A	113.5 (5)
C3B—C4B—C5B	119.3 (6)	C11A—C10A—C12A	127.5 (6)
C3B—C4B—H4BA	120.3	C6A—C11A—C10A	117.1 (6)
C5B—C4B—H4BA	120.3	C6A—C11A—C13A	113.9 (5)
N1B—C5B—N2B	119.5 (6)	C10A—C11A—C13A	129.0 (6)
N1B—C5B—C4B	118.2 (6)	O1A—C12A—O2A	120.2 (6)
N2B—C5B—C4B	122.2 (6)	O1A—C12A—C10A	119.2 (6)
C13B—O3B—H2O3	121.4	O2A—C12A—C10A	120.6 (6)
C9B—C10B—C11B	117.6 (6)	O4A—C13A—O3A	122.0 (6)
C9B—C10B—C12B	114.3 (5)	O4A—C13A—C11A	118.2 (6)
C11B—C10B—C12B	128.1 (6)	O3A—C13A—C11A	119.8 (5)

C5A—N1A—C1A—C2A	0.5 (10)	C9B—C10B—C11B—C13B	−177.0 (6)
N1A—C1A—C2A—C3A	0.3 (10)	C12B—C10B—C11B—C13B	2.7 (11)
N1A—C1A—C2A—Br1A	−177.1 (5)	C9B—C10B—C12B—O1B	2.9 (9)
C1A—C2A—C3A—C4A	−0.1 (10)	C11B—C10B—C12B—O1B	−176.8 (6)
Br1A—C2A—C3A—C4A	177.3 (5)	C9B—C10B—C12B—O2B	−177.4 (6)
C2A—C3A—C4A—C5A	−0.9 (10)	C11B—C10B—C12B—O2B	2.9 (10)
C1A—N1A—C5A—N2A	178.9 (6)	C6B—C11B—C13B—O4B	−15.4 (9)
C1A—N1A—C5A—C4A	−1.6 (9)	C10B—C11B—C13B—O4B	163.8 (7)
C3A—C4A—C5A—N2A	−178.8 (6)	C6B—C11B—C13B—O3B	162.2 (6)
C3A—C4A—C5A—N1A	1.7 (10)	C10B—C11B—C13B—O3B	−18.6 (10)
C5B—N1B—C1B—C2B	0.5 (10)	C11A—C6A—C7A—C8A	1.5 (10)
N1B—C1B—C2B—C3B	−0.2 (10)	C6A—C7A—C8A—C9A	1.2 (10)
N1B—C1B—C2B—Br1B	−178.2 (5)	C7A—C8A—C9A—C10A	−0.7 (10)
C1B—C2B—C3B—C4B	0.2 (10)	C8A—C9A—C10A—C11A	−2.5 (10)
Br1B—C2B—C3B—C4B	178.1 (5)	C8A—C9A—C10A—C12A	175.9 (6)
C2B—C3B—C4B—C5B	−0.5 (10)	C7A—C6A—C11A—C10A	−4.6 (10)
C1B—N1B—C5B—N2B	179.7 (6)	C7A—C6A—C11A—C13A	174.7 (6)
C1B—N1B—C5B—C4B	−0.7 (10)	C9A—C10A—C11A—C6A	5.0 (9)
C3B—C4B—C5B—N1B	0.7 (10)	C12A—C10A—C11A—C6A	−173.1 (6)
C3B—C4B—C5B—N2B	−179.7 (7)	C9A—C10A—C11A—C13A	−174.2 (6)
C11B—C6B—C7B—C8B	−1.2 (11)	C12A—C10A—C11A—C13A	7.7 (11)
C6B—C7B—C8B—C9B	1.7 (10)	C9A—C10A—C12A—O1A	−14.9 (9)
C7B—C8B—C9B—C10B	−0.2 (11)	C11A—C10A—C12A—O1A	163.3 (7)
C11B—C10B—C9B—C8B	−1.7 (10)	C9A—C10A—C12A—O2A	164.9 (6)
C12B—C10B—C9B—C8B	178.5 (6)	C11A—C10A—C12A—O2A	−16.9 (10)
C7B—C6B—C11B—C10B	−0.7 (10)	C6A—C11A—C13A—O4A	2.3 (9)
C7B—C6B—C11B—C13B	178.5 (6)	C10A—C11A—C13A—O4A	−178.5 (7)
C9B—C10B—C11B—C6B	2.1 (9)	C6A—C11A—C13A—O3A	−177.0 (6)
C12B—C10B—C11B—C6B	−178.2 (6)	C10A—C11A—C13A—O3A	2.2 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1N1···O4A	0.86	1.80	2.664 (7)	176
N2A—H2NA···O4Bⁱ	0.94	1.97	2.910 (8)	175
N2A—H3NA···O3A	0.98	1.97	2.930 (7)	167
O3B—H2O3···O2B	0.75	1.68	2.391 (6)	159
N1B—H2N1···O1B	0.92	1.82	2.647 (7)	147
N2B—H3N2···O1Aⁱⁱ	1.00	1.91	2.903 (8)	176
N2B—H4N2···O2B	0.81	2.20	2.971 (7)	160
C4A—H4AA···O3Bⁱ	0.93	2.44	3.219 (9)	141
C4B—H4BA···O2Aⁱⁱ	0.93	2.42	3.175 (9)	139

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

Experimental details

Crystal data
Chemical formula	C₅H₆BrN₂⁺·C₈H₅O₄⁻
M_r	339.15
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.0192 (4), 10.2689 (5), 14.4092 (6)
α, β, γ (°)	82.269 (2), 83.969 (2), 87.845 (2)
V (Å³)	1314.72 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.14
Crystal size (mm)	0.24 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.526, 0.740
No. of measured, independent and observed [I > 2σ(I)] reflections	7631, 7631, 5583
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.194, 1.09
No. of reflections	7631
No. of parameters	364
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0079P)² + 15.1445P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.14, −1.25

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1N1···O4A	0.86	1.80	2.664 (7)	176
N2A—H2NA···O4Bⁱ	0.94	1.97	2.910 (8)	175
N2A—H3NA···O3A	0.98	1.97	2.930 (7)	167
O3B—H2O3···O2B	0.75	1.68	2.391 (6)	159
N1B—H2N1···O1B	0.92	1.82	2.647 (7)	147
N2B—H3N2···O1Aⁱⁱ	1.00	1.91	2.903 (8)	176
N2B—H4N2···O2B	0.81	2.20	2.971 (7)	160
C4A—H4AA···O3Bⁱ	0.93	2.44	3.219 (9)	141
C4B—H4BA···O2Aⁱⁱ	0.93	2.42	3.175 (9)	139

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

Footnotes

‡Thomson Reuters ResearcherID: A-5525-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). CKQ also thanks USM for the award of a USM fellowship and HM also thanks USM for the award of a postdoctoral fellowship.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Ballabh, A., Trivedi, D. R. & Dastidar, P. (2005). Cryst. Growth Des. 5, 1548–1553. Web of Science CSD CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Dale, S. H., Elsegood, M. R. J., Hemmings, M. & Wilkinson, A. L. (2004). CrystEngComm, 6, 207–214. Web of Science CSD CrossRef CAS Google Scholar
Jessen, S. M. & Küppers, H. (1991). J. Mol. Struct. 263, 247–265. CSD CrossRef CAS Web of Science Google Scholar
Küppers, H. (1978). Acta Cryst. B34, 3763–3765. CSD CrossRef IUCr Journals Web of Science Google Scholar
Quah, C. K., Hemamalini, M. & Fun, H.-K. (2010a). Acta Cryst. E66, o1932. Web of Science CSD CrossRef IUCr Journals Google Scholar
Quah, C. K., Hemamalini, M. & Fun, H.-K. (2010b). Acta Cryst. E66, o1935–o1936. Web of Science CSD CrossRef IUCr Journals Google Scholar
Quah, C. K., Jebas, S. R. & Fun, H.-K. (2008). Acta Cryst. E64, o1878–o1879. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Schuckmann, W., Fuess, H. & Bats, J. W. (1978). Acta Cryst. B34, 3754–3756. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar