2-Amino-5-bromo-pyridinium 4-carb-oxy-butano-ate.

In the title salt, C(5)H(6)BrN(2) (+)·C(5)H(7)O(4) (-), the 2-amino-5-bromo-pyridinium cation is essentially planar, with a maximum deviation of 0.005 (3) Å. In the crystal structure, the proton-ated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The ion pairs are further connected via O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane. In the network, the hydrogen glutarate (4-carb-oxy-butano-ate) anions self-assemble through O-H⋯O hydrogen bonds, forming a supra-molecular chain along the c axis.

Related literature

For applications of weak intermolecular inter­actions, see: Moghimi et al. (2002 ▶); Aghabozorg et al. (2005 ▶); Lehn (1992 ▶). For the conformation of glutaric acid, see: Saraswathi et al. (2001 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C5H6BrN2 +·C5H7O4 −

M = 305.13

Orthorhombic,

a = 5.1499 (12) Å

b = 14.858 (4) Å

c = 16.022 (4) Å

V = 1226.0 (5) Å3

Z = 4

Mo Kα radiation

μ = 3.36 mm−1

T = 296 K

0.72 × 0.31 × 0.15 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.195, T max = 0.628

8937 measured reflections

4149 independent reflections

2911 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.116

S = 1.02

4149 reflections

170 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.42 e Å−3

Absolute structure: Flack (1983 ▶), 1734 Friedel pairs

Flack parameter: 0.024 (9)

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/S1600536810026280/is2573sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026280/is2573Isup2.hkl

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

C5H6BrN2+·C5H7O4−	F(000) = 616
Mr = 305.13	Dx = 1.653 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2942 reflections
a = 5.1499 (12) Å	θ = 2.7–26.8°
b = 14.858 (4) Å	µ = 3.36 mm−1
c = 16.022 (4) Å	T = 296 K
V = 1226.0 (5) Å3	Block, colourless
Z = 4	0.72 × 0.31 × 0.15 mm

Bruker APEXII DUO CCD area-detector diffractometer	4149 independent reflections
Radiation source: fine-focus sealed tube	2911 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 31.8°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
Tmin = 0.195, Tmax = 0.628	k = −22→21
8937 measured reflections	l = −21→23

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)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116	w = 1/[σ2(Fo2) + (0.0414P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
4149 reflections	Δρmax = 0.59 e Å−3
170 parameters	Δρmin = −0.42 e Å−3
0 restraints	Absolute structure: Flack (1983), 1734 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.024 (9)

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	0.34848 (8)	0.78522 (2)	0.59104 (2)	0.06364 (14)
N1	−0.1456 (5)	0.72632 (14)	0.78238 (14)	0.0388 (5)
N2	−0.2377 (6)	0.7831 (2)	0.91338 (17)	0.0548 (6)
C6	−0.0182 (6)	0.72501 (17)	0.70949 (16)	0.0400 (6)
H6A	−0.0563	0.6812	0.6699	0.048*
C5	0.1666 (6)	0.78770 (17)	0.69349 (17)	0.0424 (5)
C4	0.2211 (6)	0.8540 (2)	0.7532 (2)	0.0508 (7)
H4A	0.3458	0.8977	0.7425	0.061*
C3	0.0906 (6)	0.8540 (2)	0.8269 (2)	0.0506 (7)
H3A	0.1271	0.8977	0.8668	0.061*
C2	−0.1011 (6)	0.78778 (19)	0.84360 (16)	0.0412 (6)
O1	0.3976 (5)	0.64368 (15)	0.92821 (11)	0.0543 (6)
O2	0.5093 (4)	0.59455 (14)	0.80384 (11)	0.0464 (5)
O3	−0.1981 (4)	0.44309 (18)	1.10571 (14)	0.0577 (6)
O4	0.1873 (5)	0.46064 (19)	1.16336 (14)	0.0582 (6)
C7	0.3666 (5)	0.59209 (17)	0.86815 (13)	0.0345 (5)
C8	0.1501 (6)	0.52312 (18)	0.86922 (15)	0.0402 (5)
H8A	0.2232	0.4648	0.8554	0.048*
H8B	0.0267	0.5384	0.8257	0.048*
C9	0.0036 (6)	0.5146 (2)	0.95136 (17)	0.0405 (6)
H9A	−0.0472	0.5740	0.9706	0.049*
H9B	−0.1529	0.4795	0.9427	0.049*
C10	0.1701 (6)	0.46966 (19)	1.01720 (16)	0.0426 (6)
H10A	0.2264	0.4115	0.9965	0.051*
H10B	0.3239	0.5060	1.0266	0.051*
C11	0.0308 (5)	0.45656 (16)	1.09925 (16)	0.0369 (5)
H1N1	−0.270 (6)	0.681 (2)	0.7886 (19)	0.037 (7)*
H1N2	−0.335 (8)	0.740 (3)	0.923 (2)	0.045 (9)*
H2N2	−0.188 (8)	0.813 (2)	0.954 (2)	0.054 (10)*
H1O4	0.132 (11)	0.454 (3)	1.202 (3)	0.077 (15)*

	U11	U22	U33	U12	U13	U23
Br1	0.0722 (2)	0.05631 (18)	0.0624 (2)	−0.00719 (18)	0.02248 (18)	0.00228 (16)
N1	0.0394 (12)	0.0371 (10)	0.0400 (11)	−0.0100 (11)	−0.0015 (9)	−0.0063 (8)
N2	0.0634 (16)	0.0631 (15)	0.0380 (12)	−0.0189 (14)	−0.0009 (11)	−0.0141 (14)
C6	0.0444 (15)	0.0366 (12)	0.0390 (12)	−0.0025 (12)	−0.0050 (11)	−0.0050 (10)
C5	0.0438 (14)	0.0356 (11)	0.0479 (13)	−0.0004 (14)	0.0004 (12)	0.0015 (11)
C4	0.0439 (16)	0.0413 (14)	0.067 (2)	−0.0096 (13)	0.0036 (14)	−0.0033 (13)
C3	0.0520 (18)	0.0437 (13)	0.0562 (17)	−0.0128 (14)	−0.0056 (14)	−0.0111 (13)
C2	0.0463 (15)	0.0392 (12)	0.0380 (12)	−0.0033 (12)	−0.0070 (11)	−0.0055 (11)
O1	0.0721 (16)	0.0581 (11)	0.0327 (9)	−0.0205 (12)	0.0154 (9)	−0.0153 (8)
O2	0.0526 (12)	0.0619 (11)	0.0247 (8)	−0.0177 (11)	0.0048 (8)	−0.0074 (8)
O3	0.0367 (11)	0.0894 (16)	0.0470 (12)	−0.0027 (11)	0.0051 (9)	0.0139 (11)
O4	0.0492 (13)	0.0935 (18)	0.0320 (10)	−0.0119 (13)	0.0026 (10)	0.0173 (11)
C7	0.0397 (13)	0.0409 (12)	0.0229 (10)	−0.0022 (12)	−0.0023 (10)	0.0006 (8)
C8	0.0458 (14)	0.0450 (13)	0.0299 (11)	−0.0065 (13)	−0.0016 (11)	0.0015 (10)
C9	0.0369 (14)	0.0496 (13)	0.0349 (12)	−0.0016 (12)	0.0020 (11)	0.0095 (11)
C10	0.0399 (14)	0.0534 (14)	0.0344 (12)	0.0064 (14)	0.0079 (11)	0.0096 (10)
C11	0.0432 (14)	0.0351 (11)	0.0324 (12)	0.0038 (10)	0.0077 (11)	0.0064 (10)

Br1—C5	1.890 (3)	O2—C7	1.266 (3)
N1—C6	1.340 (4)	O3—C11	1.201 (4)
N1—C2	1.360 (3)	O4—C11	1.307 (4)
N1—H1N1	0.94 (3)	O4—H1O4	0.69 (5)
N2—C2	1.323 (4)	C7—C8	1.514 (4)
N2—H1N2	0.83 (4)	C8—C9	1.522 (4)
N2—H2N2	0.83 (4)	C8—H8A	0.9700
C6—C5	1.356 (4)	C8—H8B	0.9700
C6—H6A	0.9300	C9—C10	1.515 (4)
C5—C4	1.402 (4)	C9—H9A	0.9700
C4—C3	1.359 (5)	C9—H9B	0.9700
C4—H4A	0.9300	C10—C11	1.510 (4)
C3—C2	1.419 (4)	C10—H10A	0.9700
C3—H3A	0.9300	C10—H10B	0.9700
O1—C7	1.241 (3)
C6—N1—C2	123.8 (2)	O1—C7—C8	120.3 (2)
C6—N1—H1N1	114.6 (19)	O2—C7—C8	117.1 (2)
C2—N1—H1N1	121.7 (19)	C7—C8—C9	115.5 (2)
C2—N2—H1N2	122 (2)	C7—C8—H8A	108.4
C2—N2—H2N2	119 (3)	C9—C8—H8A	108.4
H1N2—N2—H2N2	116 (4)	C7—C8—H8B	108.4
N1—C6—C5	119.9 (2)	C9—C8—H8B	108.4
N1—C6—H6A	120.0	H8A—C8—H8B	107.5
C5—C6—H6A	120.0	C10—C9—C8	111.0 (2)
C6—C5—C4	119.6 (3)	C10—C9—H9A	109.4
C6—C5—Br1	119.9 (2)	C8—C9—H9A	109.4
C4—C5—Br1	120.5 (2)	C10—C9—H9B	109.4
C3—C4—C5	119.6 (3)	C8—C9—H9B	109.4
C3—C4—H4A	120.2	H9A—C9—H9B	108.0
C5—C4—H4A	120.2	C11—C10—C9	113.2 (2)
C4—C3—C2	120.5 (3)	C11—C10—H10A	108.9
C4—C3—H3A	119.7	C9—C10—H10A	108.9
C2—C3—H3A	119.7	C11—C10—H10B	108.9
N2—C2—N1	119.0 (3)	C9—C10—H10B	108.9
N2—C2—C3	124.4 (3)	H10A—C10—H10B	107.7
N1—C2—C3	116.6 (3)	O3—C11—O4	123.1 (3)
C11—O4—H1O4	117 (5)	O3—C11—C10	124.3 (3)
O1—C7—O2	122.6 (3)	O4—C11—C10	112.7 (2)
C2—N1—C6—C5	−0.2 (4)	C4—C3—C2—N2	−179.7 (3)
N1—C6—C5—C4	−0.6 (4)	C4—C3—C2—N1	−0.4 (4)
N1—C6—C5—Br1	179.5 (2)	O1—C7—C8—C9	−7.5 (4)
C6—C5—C4—C3	0.8 (5)	O2—C7—C8—C9	173.0 (2)
Br1—C5—C4—C3	−179.2 (3)	C7—C8—C9—C10	−71.7 (3)
C5—C4—C3—C2	−0.3 (5)	C8—C9—C10—C11	−178.0 (2)
C6—N1—C2—N2	−179.9 (3)	C9—C10—C11—O3	32.0 (4)
C6—N1—C2—C3	0.7 (4)	C9—C10—C11—O4	−148.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2i	0.94 (3)	1.73 (3)	2.666 (3)	177 (2)
N2—H1N2···O1i	0.83 (4)	1.99 (4)	2.806 (4)	170 (4)
N2—H2N2···O1ii	0.83 (3)	2.04 (3)	2.848 (3)	164 (3)
O4—H1O4···O2iii	0.69 (5)	1.93 (5)	2.601 (3)	166 (5)
C3—H3A···O3iv	0.93	2.57	3.382 (4)	146
C6—H6A···O3v	0.93	2.46	3.337 (4)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2i	0.94 (3)	1.73 (3)	2.666 (3)	177 (2)
N2—H1N2⋯O1i	0.83 (4)	1.99 (4)	2.806 (4)	170 (4)
N2—H2N2⋯O1ii	0.83 (3)	2.04 (3)	2.848 (3)	164 (3)
O4—H1O4⋯O2iii	0.69 (5)	1.93 (5)	2.601 (3)	166 (5)
C3—H3A⋯O3iv	0.93	2.57	3.382 (4)	146
C6—H6A⋯O3v	0.93	2.46	3.337 (4)	157

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