Bis(2-amino-3-carb-oxy-pyridinium) sulfate trihydrate.

In the title compound, 2C(6)H(7)N(2)O(2) (+)·SO(4) (2-)·3H(2)O, there are two independent cations which are connected into N-H⋯O hydrogen-bonded dimers. In the crystal, O-H⋯O hydrogen-bonded sulfate-water sheets run parallel to (001) and are linked into a three-dimensional network via inter-molecular N-H⋯O and O-H⋯O hydrogen bonds through the 2-amino-nicotinium dimers. Further stabilization is provided by weak inter-molecular C-H⋯O hydrogen bonds. R(4) (3)(10) and R(2) (2)(8) graph-set rings are observed. The crystal studied was an inversion twin with refined components of 0.45 (6) and 0.55 (6).

Related literature

For related compounds, see: Athimoolam & Rajaram (2005 ▶); Berrah et al. (2005, ▶ 2011a ▶,b ▶); Dobson & Gerkin (1997 ▶); Giantsidis & Turnbull (2000 ▶); Pawlukojc et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter et al. (1990 ▶). For background to hydrogen bonding, see: Desiraju (2003 ▶).

Experimental

Crystal data

2C6H7N2O2 +·SO4 2−·3H2O

M = 428.39

Orthorhombic,

a = 6.5372 (5) Å

b = 12.3141 (10) Å

c = 23.0274 (19) Å

V = 1853.7 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 150 K

0.58 × 0.13 × 0.04 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T min = 0.845, T max = 0.970

23588 measured reflections

4229 independent reflections

3669 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.079

S = 1.06

4229 reflections

274 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.28 e Å−3

Absolute structure: Flack (1983 ▶), 1790 Friedel pairs

Flack parameter: 0.45 (6)

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010191/lh5219sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010191/lh5219Isup2.hkl

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

2C6H7N2O2+·SO42−·3H2O	Dx = 1.535 Mg m−3
Mr = 428.39	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 8735 reflections
a = 6.5372 (5) Å	θ = 2.4–27.2°
b = 12.3141 (10) Å	µ = 0.24 mm−1
c = 23.0274 (19) Å	T = 150 K
V = 1853.7 (3) Å3	Needle, colourless
Z = 4	0.58 × 0.13 × 0.04 mm
F(000) = 896

Bruker APEXII diffractometer	3669 reflections with I > 2σ(I)
graphite	Rint = 0.042
CCD rotation images, thin slices scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→5
Tmin = 0.845, Tmax = 0.970	k = −15→15
23588 measured reflections	l = −29→29
4229 independent reflections

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 atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079	w = 1/[σ2(Fo2) + (0.0369P)2 + 0.4264P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
4229 reflections	Δρmax = 0.27 e Å−3
274 parameters	Δρmin = −0.28 e Å−3
0 restraints	Absolute structure: Flack (1983), 1790 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.45 (6)

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.

	x	y	z	Uiso*/Ueq
C1A	0.7166 (3)	0.27959 (15)	0.00318 (8)	0.0216 (4)
C1B	0.6471 (3)	0.70977 (15)	0.03679 (8)	0.0200 (4)
C2A	0.7181 (3)	0.23143 (14)	0.06245 (7)	0.0207 (4)
C2B	0.6478 (3)	0.75822 (15)	−0.02254 (7)	0.0190 (4)
C3A	0.7116 (3)	0.29935 (14)	0.11251 (7)	0.0201 (3)
C3B	0.6631 (3)	0.68958 (14)	−0.07242 (7)	0.0190 (4)
C4A	0.7238 (3)	0.14018 (15)	0.17195 (8)	0.0263 (4)
H4A	0.726	0.1102	0.21	0.032*
C4B	0.6481 (3)	0.84839 (16)	−0.13233 (8)	0.0262 (4)
H4B	0.6479	0.8782	−0.1704	0.031*
C5A	0.7264 (3)	0.07309 (16)	0.12519 (8)	0.0312 (5)
H5A	0.728	−0.0036	0.1297	0.037*
C5B	0.6322 (3)	0.91558 (16)	−0.08559 (8)	0.0282 (4)
H5B	0.6211	0.992	−0.0904	0.034*
C6A	0.7268 (3)	0.12083 (16)	0.07029 (9)	0.0279 (4)
H6A	0.7333	0.0752	0.0371	0.034*
C6B	0.6326 (3)	0.86880 (16)	−0.03039 (8)	0.0247 (4)
H6B	0.6222	0.9145	0.0027	0.03*
N1A	0.7020 (3)	0.40640 (12)	0.11129 (7)	0.0278 (3)
H11A	0.7	0.4434	0.144	0.033*
H12A	0.6976	0.4407	0.0778	0.033*
N1B	0.6788 (3)	0.58296 (12)	−0.07142 (7)	0.0270 (4)
H11B	0.6894	0.5465	−0.1041	0.032*
H12B	0.6785	0.5482	−0.038	0.032*
N2A	0.7181 (2)	0.24906 (12)	0.16507 (6)	0.0215 (3)
H2A	0.7187	0.2899	0.1964	0.026*
N2B	0.6642 (2)	0.73990 (13)	−0.12524 (6)	0.0225 (3)
H2B	0.6761	0.6992	−0.1565	0.027*
O1	0.7971 (2)	0.35697 (10)	0.26811 (5)	0.0259 (3)
O1A	0.7192 (2)	0.20503 (10)	−0.03781 (5)	0.0294 (3)
H1A	0.714	0.2352	−0.0705	0.044*
O1B	0.6533 (2)	0.78383 (10)	0.07796 (5)	0.0277 (3)
H1B	0.6398	0.7538	0.1105	0.042*
O2	0.7597 (2)	0.52317 (11)	0.32163 (5)	0.0311 (3)
O1W	0.6295 (3)	0.71875 (14)	0.18121 (6)	0.0467 (5)
H1W	0.652 (5)	0.765 (3)	0.2061 (14)	0.07*
H2W	0.653 (5)	0.664 (3)	0.1933 (14)	0.07*
O2A	0.7137 (2)	0.37665 (11)	−0.00595 (5)	0.0296 (3)
O2B	0.6414 (2)	0.61242 (10)	0.04572 (5)	0.0266 (3)
O3	0.9930 (2)	0.51502 (12)	0.24034 (6)	0.0301 (3)
O2W	0.3026 (2)	0.36878 (11)	0.23220 (6)	0.0270 (3)
H3W	0.201 (4)	0.405 (2)	0.2347 (11)	0.04*
H4W	0.405 (4)	0.417 (2)	0.2307 (11)	0.04*
O4	0.6310 (2)	0.50965 (11)	0.22342 (5)	0.0259 (3)
O3W	0.2063 (3)	0.23235 (12)	0.14171 (6)	0.0325 (3)
H5W	0.239 (4)	0.271 (2)	0.1664 (11)	0.049*
H6W	0.227 (4)	0.170 (2)	0.1557 (11)	0.049*
S1	0.79804 (7)	0.47766 (4)	0.263808 (18)	0.01992 (10)

	U11	U22	U33	U12	U13	U23
C1A	0.0196 (8)	0.0255 (10)	0.0197 (8)	−0.0003 (8)	−0.0009 (7)	−0.0008 (7)
C1B	0.0188 (9)	0.0236 (10)	0.0176 (8)	0.0009 (7)	−0.0004 (7)	−0.0013 (7)
C2A	0.0205 (9)	0.0210 (9)	0.0207 (8)	−0.0023 (7)	−0.0018 (7)	−0.0009 (7)
C2B	0.0192 (9)	0.0212 (9)	0.0165 (8)	−0.0012 (7)	−0.0016 (7)	−0.0003 (7)
C3A	0.0203 (8)	0.0203 (8)	0.0196 (8)	−0.0009 (8)	−0.0001 (8)	0.0007 (7)
C3B	0.0205 (9)	0.0199 (9)	0.0167 (8)	0.0008 (7)	−0.0006 (7)	0.0007 (7)
C4A	0.0318 (10)	0.0239 (9)	0.0232 (9)	0.0002 (8)	−0.0036 (8)	0.0062 (8)
C4B	0.0300 (11)	0.0261 (10)	0.0225 (9)	0.0020 (8)	−0.0008 (8)	0.0081 (8)
C5A	0.0451 (12)	0.0192 (9)	0.0293 (10)	−0.0003 (9)	−0.0034 (9)	0.0025 (8)
C5B	0.0336 (11)	0.0214 (10)	0.0294 (10)	0.0018 (8)	−0.0012 (8)	0.0047 (8)
C6A	0.0354 (11)	0.0218 (9)	0.0266 (10)	0.0000 (8)	−0.0017 (9)	−0.0036 (8)
C6B	0.0278 (10)	0.0221 (9)	0.0241 (9)	0.0003 (8)	−0.0007 (8)	−0.0021 (8)
N1A	0.0465 (9)	0.0181 (8)	0.0188 (7)	0.0007 (8)	−0.0003 (8)	−0.0004 (6)
N1B	0.0436 (10)	0.0204 (8)	0.0171 (7)	0.0013 (8)	−0.0001 (7)	−0.0006 (6)
N2A	0.0256 (8)	0.0214 (7)	0.0175 (7)	0.0004 (7)	−0.0014 (6)	0.0000 (6)
N2B	0.0270 (8)	0.0243 (8)	0.0162 (7)	0.0004 (6)	0.0004 (6)	−0.0011 (6)
O1	0.0404 (7)	0.0191 (6)	0.0181 (6)	−0.0016 (6)	−0.0021 (6)	0.0004 (5)
O1A	0.0454 (8)	0.0252 (7)	0.0176 (6)	0.0011 (7)	−0.0006 (6)	−0.0015 (5)
O1B	0.0414 (8)	0.0250 (7)	0.0166 (6)	0.0008 (6)	−0.0005 (6)	−0.0018 (5)
O2	0.0508 (9)	0.0240 (7)	0.0184 (6)	0.0046 (6)	0.0021 (6)	−0.0021 (6)
O1W	0.0970 (15)	0.0245 (8)	0.0185 (7)	0.0102 (9)	−0.0078 (8)	−0.0008 (6)
O2A	0.0453 (8)	0.0226 (7)	0.0208 (6)	0.0020 (6)	0.0017 (6)	0.0026 (5)
O2B	0.0363 (8)	0.0224 (7)	0.0212 (7)	0.0017 (6)	0.0004 (6)	0.0031 (6)
O3	0.0274 (7)	0.0295 (8)	0.0332 (8)	−0.0038 (6)	0.0025 (6)	0.0054 (7)
O2W	0.0264 (7)	0.0248 (7)	0.0297 (7)	−0.0016 (6)	0.0013 (7)	−0.0017 (6)
O4	0.0284 (7)	0.0260 (7)	0.0234 (7)	−0.0015 (6)	−0.0034 (5)	0.0041 (6)
O3W	0.0538 (9)	0.0244 (8)	0.0193 (7)	−0.0026 (7)	−0.0042 (7)	−0.0014 (6)
S1	0.0259 (2)	0.0184 (2)	0.01552 (19)	−0.00133 (19)	−0.00044 (18)	0.00021 (17)

C1A—O2A	1.214 (2)	C5B—C6B	1.395 (3)
C1A—O1A	1.317 (2)	C5B—H5B	0.95
C1A—C2A	1.488 (2)	C6A—H6A	0.95
C1B—O2B	1.217 (2)	C6B—H6B	0.95
C1B—O1B	1.316 (2)	N1A—H11A	0.88
C1B—C2B	1.491 (2)	N1A—H12A	0.88
C2A—C6A	1.375 (3)	N1B—H11B	0.88
C2A—C3A	1.425 (2)	N1B—H12B	0.88
C2B—C6B	1.377 (3)	N2A—H2A	0.88
C2B—C3B	1.430 (2)	N2B—H2B	0.88
C3A—N1A	1.320 (2)	O1—S1	1.4895 (13)
C3A—N2A	1.360 (2)	O1A—H1A	0.84
C3B—N1B	1.317 (2)	O1B—H1B	0.84
C3B—N2B	1.365 (2)	O2—S1	1.4662 (13)
C4A—N2A	1.351 (2)	O1W—H1W	0.82 (3)
C4A—C5A	1.357 (3)	O1W—H2W	0.75 (3)
C4A—H4A	0.95	O3—S1	1.4591 (14)
C4B—N2B	1.350 (2)	O2W—H3W	0.80 (3)
C4B—C5B	1.362 (3)	O2W—H4W	0.89 (3)
C4B—H4B	0.95	O4—S1	1.4877 (13)
C5A—C6A	1.394 (3)	O3W—H5W	0.77 (3)
C5A—H5A	0.95	O3W—H6W	0.85 (3)
O2A—C1A—O1A	124.23 (16)	C2A—C6A—C5A	122.46 (18)
O2A—C1A—C2A	123.47 (16)	C2A—C6A—H6A	118.8
O1A—C1A—C2A	112.30 (15)	C5A—C6A—H6A	118.8
O2B—C1B—O1B	124.18 (16)	C2B—C6B—C5B	121.86 (18)
O2B—C1B—C2B	123.32 (16)	C2B—C6B—H6B	119.1
O1B—C1B—C2B	112.51 (15)	C5B—C6B—H6B	119.1
C6A—C2A—C3A	118.44 (16)	C3A—N1A—H11A	120
C6A—C2A—C1A	121.03 (16)	C3A—N1A—H12A	120
C3A—C2A—C1A	120.52 (15)	H11A—N1A—H12A	120
C6B—C2B—C3B	118.95 (16)	C3B—N1B—H11B	120
C6B—C2B—C1B	121.05 (16)	C3B—N1B—H12B	120
C3B—C2B—C1B	120.00 (15)	H11B—N1B—H12B	120
N1A—C3A—N2A	118.38 (15)	C4A—N2A—C3A	123.86 (15)
N1A—C3A—C2A	124.77 (15)	C4A—N2A—H2A	118.1
N2A—C3A—C2A	116.85 (15)	C3A—N2A—H2A	118.1
N1B—C3B—N2B	117.89 (16)	C4B—N2B—C3B	123.82 (16)
N1B—C3B—C2B	125.49 (15)	C4B—N2B—H2B	118.1
N2B—C3B—C2B	116.61 (15)	C3B—N2B—H2B	118.1
N2A—C4A—C5A	120.77 (17)	C1A—O1A—H1A	109.5
N2A—C4A—H4A	119.6	C1B—O1B—H1B	109.5
C5A—C4A—H4A	119.6	H1W—O1W—H2W	109 (3)
N2B—C4B—C5B	120.77 (17)	H3W—O2W—H4W	105 (2)
N2B—C4B—H4B	119.6	H5W—O3W—H6W	104 (3)
C5B—C4B—H4B	119.6	O3—S1—O2	111.42 (9)
C4A—C5A—C6A	117.56 (18)	O3—S1—O4	109.05 (8)
C4A—C5A—H5A	121.2	O2—S1—O4	109.93 (8)
C6A—C5A—H5A	121.2	O3—S1—O1	110.06 (9)
C4B—C5B—C6B	117.98 (18)	O2—S1—O1	108.68 (7)
C4B—C5B—H5B	121	O4—S1—O1	107.62 (8)
C6B—C5B—H5B	121
O2A—C1A—C2A—C6A	−178.3 (2)	C1B—C2B—C3B—N2B	−179.57 (16)
O1A—C1A—C2A—C6A	1.6 (3)	N2A—C4A—C5A—C6A	1.1 (3)
O2A—C1A—C2A—C3A	1.3 (3)	N2B—C4B—C5B—C6B	−0.1 (3)
O1A—C1A—C2A—C3A	−178.75 (18)	C3A—C2A—C6A—C5A	1.0 (3)
O2B—C1B—C2B—C6B	173.11 (18)	C1A—C2A—C6A—C5A	−179.38 (18)
O1B—C1B—C2B—C6B	−6.9 (2)	C4A—C5A—C6A—C2A	−2.1 (3)
O2B—C1B—C2B—C3B	−6.5 (3)	C3B—C2B—C6B—C5B	−0.1 (3)
O1B—C1B—C2B—C3B	173.45 (16)	C1B—C2B—C6B—C5B	−179.72 (17)
C6A—C2A—C3A—N1A	−179.65 (19)	C4B—C5B—C6B—C2B	−0.2 (3)
C1A—C2A—C3A—N1A	0.7 (3)	C5A—C4A—N2A—C3A	1.0 (3)
C6A—C2A—C3A—N2A	1.1 (3)	N1A—C3A—N2A—C4A	178.57 (18)
C1A—C2A—C3A—N2A	−178.53 (16)	C2A—C3A—N2A—C4A	−2.1 (3)
C6B—C2B—C3B—N1B	179.90 (18)	C5B—C4B—N2B—C3B	0.9 (3)
C1B—C2B—C3B—N1B	−0.5 (3)	N1B—C3B—N2B—C4B	179.60 (18)
C6B—C2B—C3B—N2B	0.8 (3)	C2B—C3B—N2B—C4B	−1.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···O3Wi	0.84	1.69	2.5152 (18)	167
O1B—H1B···O1W	0.84	1.69	2.5138 (18)	168
O1W—H1W···O2Wii	0.82 (4)	1.93 (3)	2.754 (2)	177 (4)
O3W—H5W···O2W	0.77 (3)	1.98 (3)	2.750 (2)	176 (3)
O1W—H2W···O4	0.75 (4)	2.03 (4)	2.752 (2)	164 (3)
O2W—H3W···O3iii	0.80 (3)	1.92 (3)	2.7151 (19)	169 (3)
O2W—H4W···O4	0.90 (3)	1.87 (3)	2.7675 (19)	175 (3)
O3W—H6W···O2iv	0.84 (2)	1.88 (2)	2.720 (2)	171 (3)
N2A—H2A···O1	0.88	1.92	2.7681 (18)	163
N2B—H2B···O1v	0.88	1.88	2.7419 (19)	167
N1A—H11A···O4	0.88	2.05	2.915 (2)	166
N1B—H11B···O2v	0.88	1.94	2.817 (2)	173
N1A—H12A···O2A	0.88	2.09	2.726 (2)	129
N1A—H12A···O2B	0.88	2.27	2.979 (2)	138
N1B—H12B···O2A	0.88	2.25	2.963 (2)	138
N1B—H12B···O2B	0.88	2.10	2.733 (2)	128
C4A—H4A···O3vi	0.95	2.46	3.143 (2)	129
C4B—H4B···O3vii	0.95	2.31	3.169 (2)	150
C6A—H6A···O1A	0.95	2.35	2.697 (2)	101
C6B—H6B···O1B	0.95	2.37	2.709 (2)	100

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1A⋯O3Wi	0.84	1.69	2.5152 (18)	167
O1B—H1B⋯O1W	0.84	1.69	2.5138 (18)	168
O1W—H1W⋯O2Wii	0.82 (4)	1.93 (3)	2.754 (2)	177 (4)
O3W—H5W⋯O2W	0.77 (3)	1.98 (3)	2.750 (2)	176 (3)
O1W—H2W⋯O4	0.75 (4)	2.03 (4)	2.752 (2)	164 (3)
O2W—H3W⋯O3iii	0.80 (3)	1.92 (3)	2.7151 (19)	169 (3)
O2W—H4W⋯O4	0.90 (3)	1.87 (3)	2.7675 (19)	175 (3)
O3W—H6W⋯O2iv	0.84 (2)	1.88 (2)	2.720 (2)	171 (3)
N2A—H2A⋯O1	0.88	1.92	2.7681 (18)	163
N2B—H2B⋯O1v	0.88	1.88	2.7419 (19)	167
N1A—H11A⋯O4	0.88	2.05	2.915 (2)	166
N1B—H11B⋯O2v	0.88	1.94	2.817 (2)	173
N1A—H12A⋯O2A	0.88	2.09	2.726 (2)	129
N1A—H12A⋯O2B	0.88	2.27	2.979 (2)	138
N1B—H12B⋯O2A	0.88	2.25	2.963 (2)	138
N1B—H12B⋯O2B	0.88	2.10	2.733 (2)	128
C4A—H4A⋯O3vi	0.95	2.46	3.143 (2)	129
C4B—H4B⋯O3vii	0.95	2.31	3.169 (2)	150

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