2-Amino-anilinium 6-carb-oxy-picolinate monohydrate.

In the title compound, C(6)H(9)N(2) (+)·C(7)H(4)NO(4) (-)·H(2)O, one amino group of diamino-benzene is protonated while one carb-oxy group of pyridine-2,6-dicarb-oxy-lic acid is deprotonated. In the anion, the CO(2) and CO(2)H groups make dihedral angles of 4.0 (5) and 8.7 (4)° with the pyridine ring. In the crystal, extensive N-H⋯O, N-H⋯N and O-H⋯O hydrogen bonds occur between anions, cations and water mol-ecules.

Related literature

For related compounds, see: Andre et al. (2011 ▶); Blagden et al. (2008 ▶); Smith et al. (2000 ▶); Kapildev et al. (2011 ▶).

Experimental

Crystal data

C6H9N2 +·C7H4NO4 −·H2O

M = 293.28

Monoclinic,

a = 12.408 (3) Å

b = 13.932 (3) Å

c = 8.0951 (16) Å

β = 102.41 (3)°

V = 1366.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 298 K

0.30 × 0.25 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.910, T max = 1.000

7343 measured reflections

1555 independent reflections

1393 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.117

S = 1.12

1555 reflections

191 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear data reduction: CrystalClear; 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811025050/xu5250sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811025050/xu5250Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811025050/xu5250Isup3.cml

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

C6H9N2+·C7H4NO4−·H2O	F(000) = 616
Mr = 293.28	Dx = 1.425 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1555 reflections
a = 12.408 (3) Å	θ = 2.2–27.4°
b = 13.932 (3) Å	µ = 0.11 mm−1
c = 8.0951 (16) Å	T = 298 K
β = 102.41 (3)°	Block, colorless
V = 1366.6 (5) Å3	0.30 × 0.25 × 0.15 mm
Z = 4

Rigaku Mercury2 diffractometer	1555 independent reflections
Radiation source: fine-focus sealed tube	1393 reflections with I > 2σ(I)
graphite	Rint = 0.041
Detector resolution: 13.6612 pixels mm-1	θmax = 27.4°, θmin = 2.2°
CCD profile fitting scans	h = −16→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
Tmin = 0.910, Tmax = 1.000	l = −10→10
7343 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.0734P)2] where P = (Fo2 + 2Fc2)/3
1555 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 0.19 e Å−3
2 restraints	Δρmin = −0.22 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1W	0.9144 (2)	0.11509 (17)	0.8457 (3)	0.0468 (6)
H1WA	0.9052	0.0737	0.9133	0.070*
H1WB	0.8972	0.0905	0.7516	0.070*
O1	0.75215 (19)	0.17288 (15)	0.4341 (3)	0.0456 (6)
O2	0.80493 (18)	0.02830 (16)	0.5392 (3)	0.0412 (5)
N3	0.56474 (19)	0.10218 (18)	0.2422 (3)	0.0286 (5)
O3	0.30560 (19)	0.10298 (17)	−0.0480 (3)	0.0436 (6)
O4	0.41055 (17)	0.22264 (15)	0.0827 (3)	0.0397 (5)
H4	0.3599	0.2569	0.0337	0.060*
N1	0.61623 (19)	0.31257 (19)	0.2363 (3)	0.0296 (5)
H1A	0.5582	0.3434	0.2587	0.044*
H1B	0.6772	0.3318	0.3080	0.044*
H1C	0.6076	0.2497	0.2476	0.044*
C8	0.6256 (2)	0.33386 (19)	0.0621 (3)	0.0290 (6)
N2	0.7964 (2)	0.2434 (2)	0.1010 (4)	0.0452 (7)
H2A	0.8342	0.2069	0.0413	0.054*
H2B	0.7933	0.2178	0.2020	0.054*
C1	0.7403 (2)	0.0831 (2)	0.4445 (4)	0.0304 (6)
C6	0.4728 (2)	0.0640 (2)	0.1448 (4)	0.0293 (6)
C7	0.3880 (2)	0.1321 (2)	0.0494 (3)	0.0296 (6)
C3	0.6225 (3)	−0.0586 (2)	0.3262 (4)	0.0371 (7)
H3A	0.6748	−0.0990	0.3909	0.044*
C9	0.7137 (2)	0.2968 (2)	0.0015 (4)	0.0336 (6)
C5	0.4515 (3)	−0.0335 (2)	0.1314 (4)	0.0392 (7)
H5A	0.3870	−0.0566	0.0623	0.047*
C13	0.5445 (3)	0.3890 (2)	−0.0392 (4)	0.0378 (7)
H13A	0.4864	0.4131	0.0041	0.045*
C4	0.5287 (3)	−0.0961 (2)	0.2238 (5)	0.0427 (8)
H4A	0.5173	−0.1621	0.2167	0.051*
C10	0.7174 (3)	0.3179 (3)	−0.1655 (5)	0.0471 (8)
H10A	0.7756	0.2946	−0.2097	0.057*
C2	0.6380 (2)	0.0403 (2)	0.3314 (4)	0.0289 (6)
C12	0.5500 (3)	0.4080 (3)	−0.2044 (5)	0.0503 (9)
H12A	0.4953	0.4444	−0.2731	0.060*
C11	0.6366 (4)	0.3728 (3)	−0.2669 (5)	0.0549 (10)
H11A	0.6409	0.3859	−0.3779	0.066*

	U11	U22	U33	U12	U13	U23
O1W	0.0461 (14)	0.0470 (14)	0.0444 (13)	−0.0005 (11)	0.0035 (10)	0.0032 (10)
O1	0.0368 (12)	0.0319 (12)	0.0563 (14)	−0.0070 (10)	−0.0164 (10)	0.0073 (11)
O2	0.0311 (11)	0.0399 (12)	0.0452 (12)	0.0016 (9)	−0.0085 (9)	0.0071 (10)
N3	0.0222 (10)	0.0302 (13)	0.0312 (11)	−0.0011 (9)	0.0014 (9)	0.0013 (10)
O3	0.0307 (12)	0.0408 (13)	0.0504 (14)	0.0011 (9)	−0.0108 (10)	−0.0029 (10)
O4	0.0296 (11)	0.0318 (10)	0.0500 (13)	0.0023 (8)	−0.0086 (9)	0.0000 (10)
N1	0.0244 (11)	0.0326 (12)	0.0292 (12)	0.0008 (9)	−0.0003 (9)	−0.0013 (10)
C8	0.0278 (14)	0.0293 (13)	0.0286 (14)	−0.0010 (11)	0.0035 (10)	−0.0011 (11)
N2	0.0343 (14)	0.0463 (16)	0.0553 (18)	0.0115 (12)	0.0103 (13)	−0.0012 (14)
C1	0.0246 (13)	0.0325 (14)	0.0321 (14)	−0.0003 (11)	0.0015 (10)	0.0035 (12)
C6	0.0217 (12)	0.0314 (14)	0.0331 (14)	−0.0010 (11)	0.0020 (10)	−0.0005 (12)
C7	0.0228 (13)	0.0366 (14)	0.0272 (13)	−0.0010 (11)	0.0008 (10)	−0.0015 (12)
C3	0.0298 (16)	0.0312 (15)	0.0480 (18)	0.0007 (12)	0.0033 (13)	0.0080 (13)
C9	0.0298 (14)	0.0314 (15)	0.0395 (16)	−0.0014 (12)	0.0072 (12)	−0.0035 (12)
C5	0.0291 (16)	0.0372 (15)	0.0461 (18)	−0.0059 (13)	−0.0032 (13)	−0.0018 (14)
C13	0.0357 (15)	0.0397 (16)	0.0369 (17)	0.0079 (13)	0.0054 (12)	0.0033 (13)
C4	0.0363 (16)	0.0275 (15)	0.060 (2)	−0.0048 (13)	0.0016 (15)	0.0003 (14)
C10	0.049 (2)	0.053 (2)	0.045 (2)	0.0026 (16)	0.0206 (16)	−0.0055 (16)
C2	0.0228 (13)	0.0303 (14)	0.0320 (13)	−0.0012 (11)	0.0026 (11)	0.0021 (12)
C12	0.057 (2)	0.053 (2)	0.0387 (18)	0.0148 (18)	0.0064 (15)	0.0112 (16)
C11	0.072 (3)	0.061 (2)	0.0357 (19)	0.008 (2)	0.0202 (17)	0.0082 (17)

O1W—H1WA	0.8201	C1—C2	1.518 (4)
O1W—H1WB	0.8201	C6—C5	1.384 (4)
O1—C1	1.264 (4)	C6—C7	1.502 (4)
O2—C1	1.245 (4)	C3—C4	1.378 (5)
N3—C2	1.345 (4)	C3—C2	1.391 (4)
N3—C6	1.349 (4)	C3—H3A	0.9300
O3—C7	1.219 (3)	C9—C10	1.394 (5)
O4—C7	1.307 (4)	C5—C4	1.390 (5)
O4—H4	0.8201	C5—H5A	0.9300
N1—C8	1.470 (4)	C13—C12	1.379 (5)
N1—H1A	0.8900	C13—H13A	0.9300
N1—H1B	0.8900	C4—H4A	0.9300
N1—H1C	0.8900	C10—C11	1.382 (6)
C8—C13	1.386 (4)	C10—H10A	0.9300
C8—C9	1.390 (4)	C12—C11	1.373 (6)
N2—C9	1.378 (4)	C12—H12A	0.9300
N2—H2A	0.9002	C11—H11A	0.9300
N2—H2B	0.8998
H1WA—O1W—H1WB	106.3	C2—C3—H3A	120.4
C2—N3—C6	116.7 (2)	N2—C9—C8	122.5 (3)
C7—O4—H4	110.7	N2—C9—C10	120.3 (3)
C8—N1—H1A	109.5	C8—C9—C10	117.1 (3)
C8—N1—H1B	109.5	C6—C5—C4	118.4 (3)
H1A—N1—H1B	109.5	C6—C5—H5A	120.8
C8—N1—H1C	109.5	C4—C5—H5A	120.8
H1A—N1—H1C	109.5	C12—C13—C8	119.9 (3)
H1B—N1—H1C	109.5	C12—C13—H13A	120.0
C13—C8—C9	121.6 (3)	C8—C13—H13A	120.0
C13—C8—N1	118.8 (3)	C3—C4—C5	118.8 (3)
C9—C8—N1	119.6 (2)	C3—C4—H4A	120.6
C9—N2—H2A	113.6	C5—C4—H4A	120.6
C9—N2—H2B	125.0	C11—C10—C9	121.4 (3)
H2A—N2—H2B	113.1	C11—C10—H10A	119.3
O2—C1—O1	125.4 (3)	C9—C10—H10A	119.3
O2—C1—C2	118.4 (3)	N3—C2—C3	123.1 (3)
O1—C1—C2	116.3 (2)	N3—C2—C1	116.9 (2)
N3—C6—C5	123.8 (3)	C3—C2—C1	120.0 (3)
N3—C6—C7	117.6 (2)	C11—C12—C13	119.6 (3)
C5—C6—C7	118.6 (3)	C11—C12—H12A	120.2
O3—C7—O4	124.6 (3)	C13—C12—H12A	120.2
O3—C7—C6	121.3 (3)	C12—C11—C10	120.3 (3)
O4—C7—C6	114.1 (2)	C12—C11—H11A	119.8
C4—C3—C2	119.1 (3)	C10—C11—H11A	119.8
C4—C3—H3A	120.4
C2—N3—C6—C5	−0.6 (4)	C6—C5—C4—C3	0.7 (5)
C2—N3—C6—C7	177.7 (3)	N2—C9—C10—C11	−178.8 (4)
N3—C6—C7—O3	176.1 (3)	C8—C9—C10—C11	−0.5 (5)
C5—C6—C7—O3	−5.4 (4)	C6—N3—C2—C3	0.1 (4)
N3—C6—C7—O4	−4.8 (4)	C6—N3—C2—C1	−178.6 (3)
C5—C6—C7—O4	173.7 (3)	C4—C3—C2—N3	0.8 (5)
C13—C8—C9—N2	178.7 (3)	C4—C3—C2—C1	179.4 (3)
N1—C8—C9—N2	−2.8 (4)	O2—C1—C2—N3	174.0 (3)
C13—C8—C9—C10	0.4 (4)	O1—C1—C2—N3	−5.8 (4)
N1—C8—C9—C10	178.9 (3)	O2—C1—C2—C3	−4.7 (4)
N3—C6—C5—C4	0.2 (5)	O1—C1—C2—C3	175.5 (3)
C7—C6—C5—C4	−178.1 (3)	C8—C13—C12—C11	−0.6 (6)
C9—C8—C13—C12	0.2 (5)	C13—C12—C11—C10	0.6 (6)
N1—C8—C13—C12	−178.4 (3)	C9—C10—C11—C12	0.0 (7)
C2—C3—C4—C5	−1.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1Wi	0.89	2.13	3.004 (4)	166
N1—H1B···O3ii	0.89	1.98	2.862 (3)	170
N1—H1C···N3	0.89	2.12	3.003 (4)	171
N2—H2A···O1Wiii	0.90	2.41	3.303 (4)	172
N2—H2B···O1	0.90	2.14	3.029 (4)	168
O1W—H1WA···O2iv	0.82	2.27	3.034 (3)	155
O1W—H1WB···O2	0.82	2.04	2.831 (3)	161
O4—H4···O1i	0.82	1.71	2.532 (3)	179

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1Wi	0.89	2.13	3.004 (4)	166
N1—H1B⋯O3ii	0.89	1.98	2.862 (3)	170
N1—H1C⋯N3	0.89	2.12	3.003 (4)	171
N2—H2A⋯O1Wiii	0.90	2.41	3.303 (4)	172
N2—H2B⋯O1	0.90	2.14	3.029 (4)	168
O1W—H1WA⋯O2iv	0.82	2.27	3.034 (3)	155
O1W—H1WB⋯O2	0.82	2.04	2.831 (3)	161
O4—H4⋯O1i	0.82	1.71	2.532 (3)	179

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