2-Amino-5-bromo-pyridinium 6-oxo-1,6-dihydro-pyridine-2-carboxyl-ate monohydrate.

In the crystal structure of the title salt, C(5)H(6)BrN(2) (+)·C(6)H(4)NO(3) (-)·H(2)O, the protonated 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, N-H⋯Br and C-H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane. The water mol-ecules self-assemble through O-H⋯O hydrogen bonds, forming one-dimensional supra-molecular chains along the a axis, with graph-set notation C(2) (2)(4).

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For details of 6-hy­droxy­picolinic acid, see: Sun et al. (2004 ▶); Soares-Santos et al. (2003 ▶). For a related structure, see: Sawada & Ohashi (1998 ▶). For details of n class="Chemical">hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C5H6BrN2 +·n class="Chemical">C6H4NO3 −·H2O

M = 330.15

Orthorhombic,

a = 3.8616 (1) Å

b = 15.8227 (2) Å

c = 20.8961 (3) Å

V = 1276.77 (4) Å3

Z = 4

Mo Kα radiation

μ = 3.23 mm−1

T = 296 K

0.35 × 0.18 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.400, T max = 0.694

8884 measured reflections

3718 independent reflections

3105 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.097

S = 1.09

3718 reflections

172 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.32 e Å−3

Absolute structure: Flack (1983 ▶), 1482 Friedel pairs

Flack parameter: 0.011 (12)

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/S1600536810030916/is2585sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030916/is2585Isup2.hkl

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

C5H6BrN2+·C6H4NO3−·H2O	F(000) = 664
Mr = 330.15	Dx = 1.718 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4297 reflections
a = 3.8616 (1) Å	θ = 2.6–27.5°
b = 15.8227 (2) Å	µ = 3.23 mm−1
c = 20.8961 (3) Å	T = 296 K
V = 1276.77 (4) Å3	Block, colourless
Z = 4	0.35 × 0.18 × 0.12 mm

Bruker SMART APEXII CCD area-detector diffractometer	3718 independent reflections
Radiation source: fine-focus sealed tube	3105 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 30.1°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
Tmin = 0.400, Tmax = 0.694	k = −22→19
8884 measured reflections	l = −20→29

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)] = 0.031	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.036P)2 + 0.5546P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
3718 reflections	Δρmax = 0.37 e Å−3
172 parameters	Δρmin = −0.32 e Å−3
3 restraints	Absolute structure: Flack (1983), 1482 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.011 (12)

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	0.68523 (9)	0.02155 (2)	0.832419 (15)	0.04315 (11)
N1	0.9529 (7)	0.01356 (17)	1.02199 (12)	0.0358 (5)
H1B	1.0573	−0.0221	1.0463	0.043*
N2	0.8795 (10)	0.09857 (18)	1.10959 (13)	0.0490 (8)
H2A	0.9800	0.0609	1.1327	0.059*
H2B	0.8067	0.1446	1.1268	0.059*
C1	0.9123 (9)	−0.00566 (19)	0.95935 (15)	0.0357 (7)
H1A	0.9939	−0.0570	0.9437	0.043*
C2	0.7526 (7)	0.04972 (19)	0.91899 (14)	0.0347 (7)
C3	0.6342 (9)	0.1270 (2)	0.94344 (16)	0.0408 (7)
H3A	0.5271	0.1657	0.9164	0.049*
C4	0.6750 (10)	0.14591 (18)	1.00655 (15)	0.0384 (7)
H4A	0.5981	0.1974	1.0227	0.046*
C5	0.8371 (10)	0.08579 (19)	1.04763 (14)	0.0363 (6)
O1	0.1449 (9)	0.24380 (15)	0.84486 (11)	0.0517 (7)
O2	0.1646 (8)	0.08864 (15)	0.59255 (11)	0.0525 (6)
O3	0.3456 (8)	0.03807 (15)	0.68650 (11)	0.0529 (7)
N3	0.1458 (8)	0.17784 (15)	0.74829 (11)	0.0337 (5)
H3B	0.2465	0.1354	0.7660	0.040*
C6	0.0674 (9)	0.24462 (19)	0.78634 (16)	0.0374 (7)
C7	−0.0997 (9)	0.3135 (2)	0.75378 (17)	0.0427 (8)
H7A	−0.1583	0.3621	0.7764	0.051*
C8	−0.1722 (11)	0.3084 (2)	0.69074 (17)	0.0438 (7)
H8A	−0.2841	0.3532	0.6708	0.053*
C9	−0.0818 (10)	0.2363 (2)	0.65430 (15)	0.0398 (7)
H9A	−0.1321	0.2333	0.6108	0.048*
C10	0.0787 (9)	0.1721 (2)	0.68434 (14)	0.0351 (7)
C11	0.2065 (10)	0.09186 (19)	0.65253 (14)	0.0378 (7)
O1W	0.5862 (19)	0.3110 (3)	0.51273 (19)	0.133 (2)
H1W	0.4451	0.3496	0.4906	0.159*
H2W	0.7111	0.2778	0.4832	0.159*

	U11	U22	U33	U12	U13	U23
Br1	0.04628 (18)	0.04800 (18)	0.03519 (15)	−0.00207 (15)	−0.00408 (15)	−0.00074 (15)
N1	0.0457 (14)	0.0297 (12)	0.0319 (11)	0.0062 (12)	−0.0001 (11)	0.0035 (11)
N2	0.076 (2)	0.0353 (13)	0.0355 (13)	0.0094 (15)	−0.0032 (15)	0.0006 (12)
C1	0.0412 (16)	0.0307 (15)	0.0353 (14)	0.0010 (12)	0.0025 (13)	−0.0024 (12)
C2	0.0359 (19)	0.0369 (14)	0.0312 (13)	−0.0034 (12)	0.0007 (12)	−0.0003 (12)
C3	0.0340 (18)	0.0442 (17)	0.0443 (16)	0.0034 (14)	−0.0016 (15)	0.0061 (14)
C4	0.0444 (16)	0.0276 (13)	0.0432 (16)	0.0049 (14)	0.0015 (17)	0.0124 (12)
C5	0.0387 (16)	0.0338 (14)	0.0365 (14)	0.0010 (14)	0.0007 (15)	−0.0001 (12)
O1	0.0781 (19)	0.0436 (13)	0.0334 (11)	−0.0015 (14)	−0.0032 (13)	−0.0099 (10)
O2	0.0727 (17)	0.0530 (13)	0.0318 (10)	0.0202 (14)	−0.0018 (13)	−0.0070 (10)
O3	0.0790 (19)	0.0410 (13)	0.0388 (11)	0.0190 (13)	−0.0049 (13)	−0.0051 (10)
N3	0.0465 (15)	0.0257 (11)	0.0288 (11)	0.0039 (11)	−0.0007 (12)	0.0035 (9)
C6	0.0464 (18)	0.0300 (15)	0.0357 (15)	−0.0040 (13)	0.0034 (14)	−0.0069 (13)
C7	0.044 (2)	0.0346 (16)	0.0492 (18)	0.0092 (14)	0.0090 (16)	−0.0031 (14)
C8	0.0439 (18)	0.0401 (16)	0.0475 (17)	0.0097 (17)	0.0011 (17)	0.0005 (14)
C9	0.0464 (18)	0.0403 (17)	0.0327 (15)	0.0047 (14)	0.0000 (13)	0.0055 (13)
C10	0.0374 (16)	0.0370 (15)	0.0308 (14)	0.0004 (13)	0.0030 (12)	−0.0009 (12)
C11	0.0475 (18)	0.0330 (14)	0.0329 (14)	0.0045 (14)	0.0000 (14)	−0.0007 (11)
O1W	0.216 (7)	0.109 (3)	0.074 (2)	−0.002 (4)	−0.033 (4)	0.026 (2)

Br1—C2	1.881 (3)	O2—C11	1.265 (4)
N1—C5	1.339 (4)	O3—C11	1.231 (4)
N1—C1	1.353 (4)	N3—C6	1.356 (4)
N1—H1B	0.8600	N3—C10	1.364 (4)
N2—C5	1.321 (4)	N3—H3B	0.8600
N2—H2A	0.8600	C6—C7	1.438 (5)
N2—H2B	0.8600	C7—C8	1.349 (5)
C1—C2	1.364 (4)	C7—H7A	0.9300
C1—H1A	0.9300	C8—C9	1.415 (5)
C2—C3	1.402 (5)	C8—H8A	0.9300
C3—C4	1.361 (5)	C9—C10	1.345 (5)
C3—H3A	0.9300	C9—H9A	0.9300
C4—C5	1.426 (4)	C10—C11	1.516 (4)
C4—H4A	0.9300	O1W—H1W	0.9404
O1—C6	1.259 (4)	O1W—H2W	0.9428
C5—N1—C1	122.7 (3)	C6—N3—H3B	117.2
C5—N1—H1B	118.6	C10—N3—H3B	117.2
C1—N1—H1B	118.6	O1—C6—N3	120.5 (3)
C5—N2—H2A	120.0	O1—C6—C7	125.0 (3)
C5—N2—H2B	120.0	N3—C6—C7	114.4 (3)
H2A—N2—H2B	120.0	C8—C7—C6	120.6 (3)
N1—C1—C2	120.4 (3)	C8—C7—H7A	119.7
N1—C1—H1A	119.8	C6—C7—H7A	119.7
C2—C1—H1A	119.8	C7—C8—C9	121.5 (3)
C1—C2—C3	118.9 (3)	C7—C8—H8A	119.2
C1—C2—Br1	120.3 (2)	C9—C8—H8A	119.2
C3—C2—Br1	120.8 (2)	C10—C9—C8	118.1 (3)
C4—C3—C2	120.4 (3)	C10—C9—H9A	121.0
C4—C3—H3A	119.8	C8—C9—H9A	121.0
C2—C3—H3A	119.8	C9—C10—N3	119.7 (3)
C3—C4—C5	119.2 (3)	C9—C10—C11	125.3 (3)
C3—C4—H4A	120.4	N3—C10—C11	115.0 (3)
C5—C4—H4A	120.4	O3—C11—O2	126.8 (3)
N2—C5—N1	118.8 (3)	O3—C11—C10	117.9 (3)
N2—C5—C4	122.9 (3)	O2—C11—C10	115.3 (3)
N1—C5—C4	118.4 (3)	H1W—O1W—H2W	109.7
C6—N3—C10	125.7 (3)
C5—N1—C1—C2	0.9 (5)	O1—C6—C7—C8	180.0 (4)
N1—C1—C2—C3	0.6 (5)	N3—C6—C7—C8	1.1 (5)
N1—C1—C2—Br1	−178.3 (2)	C6—C7—C8—C9	−1.1 (6)
C1—C2—C3—C4	−0.7 (5)	C7—C8—C9—C10	0.2 (6)
Br1—C2—C3—C4	178.1 (3)	C8—C9—C10—N3	0.7 (5)
C2—C3—C4—C5	−0.5 (5)	C8—C9—C10—C11	−177.5 (3)
C1—N1—C5—N2	178.2 (3)	C6—N3—C10—C9	−0.8 (5)
C1—N1—C5—C4	−2.2 (5)	C6—N3—C10—C11	177.6 (3)
C3—C4—C5—N2	−178.5 (4)	C9—C10—C11—O3	−179.1 (4)
C3—C4—C5—N1	1.9 (5)	N3—C10—C11—O3	2.6 (5)
C10—N3—C6—O1	−179.1 (4)	C9—C10—C11—O2	2.6 (6)
C10—N3—C6—C7	−0.1 (5)	N3—C10—C11—O2	−175.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2i	0.86	1.79	2.640 (4)	171.
O1W—H1W···O2ii	0.94	2.17	2.730 (5)	117.
N2—H2A···O3i	0.86	2.04	2.896 (4)	172.
N2—H2B···O1iii	0.86	1.96	2.819 (4)	173.
O1W—H2W···O1Wii	0.94	2.02	2.782 (9)	137.
N3—H3B···Br1	0.86	2.84	3.681 (3)	168.
C3—H3A···O1	0.93	2.44	3.351 (4)	167.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2i	0.86	1.79	2.640 (4)	171
O1W—H1W⋯O2ii	0.94	2.17	2.730 (5)	117
N2—H2A⋯O3i	0.86	2.04	2.896 (4)	172
N2—H2B⋯O1iii	0.86	1.96	2.819 (4)	173
O1W—H2W⋯O1Wii	0.94	2.02	2.782 (9)	137
N3—H3B⋯Br1	0.86	2.84	3.681 (3)	168
C3—H3A⋯O1	0.93	2.44	3.351 (4)	167

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