2,3-Diamino-pyridinium 3-carb-oxy-4-hy-droxy-benzene-sulfonate monohydrate.

In the title hydrated mol-ecular salt, C(5)H(8)N(3) (+)·C(7)H(5)O(6)S(-)·H(2)O, the ion pairs and water mol-ecules are connected by N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds, thereby forming a three-dimensional network. There is an intra-molecular O-H⋯O hydrogen bond in the 3-carb-oxy-4-hy-droxy-benzene-sulfonate anion, which generates an S(6) ring motif.

Related literature

For background to 5-sulfosalicylic acid and related compounds, see: Marzotto et al. (2001 ▶); Onoda et al. (2001 ▶); Baskar Raj et al. (2003 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H8N3 +·C7H5O6S−·H2O

M = 345.33

Monoclinic,

a = 7.0407 (7) Å

b = 15.5775 (16) Å

c = 13.6244 (12) Å

β = 101.491 (2)°

V = 1464.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 100 K

0.36 × 0.31 × 0.08 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.910, T max = 0.981

6890 measured reflections

3880 independent reflections

3645 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.087

S = 1.03

3880 reflections

268 parameters

2 restraints

All H-atom parameters refined

Δρmax = 0.33 e Å−3

Δρmin = −0.19 e Å−3

Absolute structure: Flack (1983 ▶), 1770 Friedel pairs

Flack parameter: −0.02 (5)

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 datablock(s) global, I. DOI: 10.1107/S160053681104445X/hb6457sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104445X/hb6457Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681104445X/hb6457Isup3.cml

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

C5H8N3+·C7H5O6S−·H2O	F(000) = 720
Mr = 345.33	Dx = 1.566 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 3903 reflections
a = 7.0407 (7) Å	θ = 3.0–32.4°
b = 15.5775 (16) Å	µ = 0.26 mm−1
c = 13.6244 (12) Å	T = 100 K
β = 101.491 (2)°	Plate, brown
V = 1464.3 (2) Å3	0.36 × 0.31 × 0.08 mm
Z = 4

Bruker APEXII DUO CCD diffractometer	3880 independent reflections
Radiation source: fine-focus sealed tube	3645 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 30.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.910, Tmax = 0.981	k = −20→21
6890 measured reflections	l = −18→19

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)] = 0.033	All H-atom parameters refined
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0525P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3880 reflections	Δρmax = 0.33 e Å−3
268 parameters	Δρmin = −0.19 e Å−3
2 restraints	Absolute structure: Flack (1983), 1770 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.02 (5)

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
N1	0.9025 (3)	0.36254 (11)	−0.04106 (15)	0.0419 (4)
N2	0.7986 (3)	0.24446 (13)	−0.14072 (14)	0.0438 (4)
N3	0.7871 (3)	0.14977 (13)	0.03470 (16)	0.0482 (4)
C1	0.8513 (2)	0.27950 (12)	−0.04911 (15)	0.0328 (3)
C2	0.8521 (2)	0.23206 (13)	0.04046 (14)	0.0349 (4)
C3	0.9159 (3)	0.27470 (17)	0.12994 (16)	0.0465 (4)
C4	0.9699 (3)	0.36114 (19)	0.1331 (2)	0.0551 (6)
C5	0.9615 (3)	0.40443 (15)	0.0472 (2)	0.0516 (5)
S1	0.36330 (5)	0.48126 (2)	−0.18842 (3)	0.02841 (9)
O1	0.4248 (2)	0.23706 (10)	0.14554 (10)	0.0430 (3)
O2	0.2649 (2)	0.55517 (9)	−0.15649 (10)	0.0430 (3)
O3	0.5610 (2)	0.50245 (9)	−0.19835 (11)	0.0408 (3)
O4	0.2514 (2)	0.44146 (9)	−0.27754 (10)	0.0402 (3)
O5	0.2302 (2)	0.15275 (9)	−0.14779 (11)	0.0444 (3)
O6	0.2779 (3)	0.11944 (10)	0.01427 (12)	0.0484 (4)
C6	0.4112 (2)	0.28932 (11)	0.06627 (12)	0.0305 (3)
C7	0.4712 (3)	0.37427 (12)	0.08458 (13)	0.0337 (3)
C8	0.4596 (2)	0.43146 (11)	0.00715 (13)	0.0312 (3)
C9	0.3843 (2)	0.40512 (10)	−0.09102 (11)	0.0253 (3)
C10	0.3256 (2)	0.32121 (10)	−0.11074 (12)	0.0258 (3)
C11	0.3407 (2)	0.26183 (10)	−0.03244 (12)	0.0264 (3)
C12	0.2809 (2)	0.17180 (11)	−0.05209 (13)	0.0306 (3)
O1W	0.3732 (3)	0.08650 (11)	0.25895 (15)	0.0533 (4)
H3	0.930 (4)	0.2373 (19)	0.1958 (19)	0.046 (7)*
H4	1.007 (5)	0.389 (2)	0.193 (3)	0.069 (9)*
H5	1.011 (5)	0.463 (2)	0.039 (2)	0.067 (9)*
H7	0.515 (4)	0.3983 (18)	0.149 (2)	0.041 (6)*
H8	0.510 (4)	0.4874 (19)	0.021 (2)	0.043 (7)*
H10	0.271 (3)	0.3039 (15)	−0.1722 (17)	0.025 (5)*
H1N1	0.899 (5)	0.393 (2)	−0.098 (2)	0.057 (8)*
H1N2	0.820 (4)	0.277 (2)	−0.192 (2)	0.053 (8)*
H2N2	0.793 (4)	0.1894 (19)	−0.146 (2)	0.042 (6)*
H1N3	0.763 (4)	0.1187 (19)	−0.021 (2)	0.047 (7)*
H2N3	0.794 (4)	0.1179 (18)	0.092 (2)	0.044 (6)*
H1O1	0.354 (4)	0.181 (2)	0.122 (2)	0.053 (7)*
H1O5	0.203 (5)	0.100 (2)	−0.149 (2)	0.057 (8)*
H1W1	0.265 (5)	0.055 (2)	0.250 (2)	0.053 (8)*
H2W1	0.490 (8)	0.071 (4)	0.234 (4)	0.110 (16)*

	U11	U22	U33	U12	U13	U23
N1	0.0392 (8)	0.0377 (9)	0.0515 (10)	0.0004 (6)	0.0154 (7)	0.0051 (7)
N2	0.0607 (10)	0.0399 (10)	0.0340 (8)	0.0010 (7)	0.0169 (7)	0.0017 (7)
N3	0.0721 (12)	0.0387 (9)	0.0373 (9)	−0.0017 (8)	0.0194 (8)	0.0054 (8)
C1	0.0297 (7)	0.0335 (8)	0.0366 (8)	0.0024 (6)	0.0103 (6)	0.0016 (7)
C2	0.0330 (8)	0.0385 (10)	0.0352 (9)	0.0044 (6)	0.0116 (7)	0.0007 (8)
C3	0.0452 (10)	0.0592 (13)	0.0343 (10)	0.0045 (9)	0.0058 (8)	0.0009 (9)
C4	0.0444 (11)	0.0639 (15)	0.0538 (14)	−0.0043 (9)	0.0017 (9)	−0.0239 (12)
C5	0.0415 (9)	0.0405 (11)	0.0723 (15)	−0.0054 (8)	0.0105 (10)	−0.0113 (10)
S1	0.03858 (18)	0.02089 (16)	0.02544 (16)	−0.00344 (14)	0.00561 (12)	−0.00076 (14)
O1	0.0647 (9)	0.0366 (7)	0.0267 (6)	−0.0019 (6)	0.0068 (6)	0.0070 (5)
O2	0.0621 (8)	0.0302 (7)	0.0362 (7)	0.0129 (6)	0.0085 (6)	0.0010 (5)
O3	0.0469 (7)	0.0314 (6)	0.0462 (8)	−0.0108 (5)	0.0141 (6)	0.0010 (5)
O4	0.0577 (8)	0.0349 (7)	0.0264 (6)	−0.0101 (6)	0.0043 (5)	−0.0034 (5)
O5	0.0663 (9)	0.0270 (6)	0.0374 (7)	−0.0146 (6)	0.0043 (6)	−0.0016 (5)
O6	0.0745 (11)	0.0289 (7)	0.0416 (8)	−0.0115 (7)	0.0114 (7)	0.0064 (6)
C6	0.0364 (8)	0.0281 (8)	0.0275 (7)	0.0003 (6)	0.0078 (6)	0.0019 (6)
C7	0.0417 (8)	0.0323 (9)	0.0256 (8)	0.0013 (6)	0.0031 (6)	−0.0057 (6)
C8	0.0349 (7)	0.0246 (7)	0.0323 (8)	−0.0024 (6)	0.0027 (6)	−0.0067 (6)
C9	0.0303 (7)	0.0209 (6)	0.0250 (7)	−0.0012 (5)	0.0060 (5)	0.0000 (5)
C10	0.0310 (7)	0.0208 (6)	0.0257 (7)	−0.0020 (5)	0.0063 (5)	−0.0019 (5)
C11	0.0298 (7)	0.0220 (7)	0.0285 (8)	−0.0008 (5)	0.0083 (6)	0.0001 (5)
C12	0.0337 (7)	0.0245 (7)	0.0342 (8)	−0.0029 (6)	0.0084 (6)	0.0010 (6)
O1W	0.0539 (9)	0.0464 (9)	0.0617 (10)	−0.0046 (7)	0.0169 (8)	−0.0035 (8)

N1—C1	1.342 (3)	S1—C9	1.7640 (16)
N1—C5	1.358 (3)	O1—C6	1.341 (2)
N1—H1N1	0.91 (3)	O1—H1O1	1.02 (3)
N2—C1	1.345 (3)	O5—C12	1.315 (2)
N2—H1N2	0.90 (3)	O5—H1O5	0.84 (4)
N2—H2N2	0.86 (3)	O6—C12	1.221 (2)
N3—C2	1.358 (3)	C6—C7	1.396 (3)
N3—H1N3	0.88 (3)	C6—C11	1.404 (2)
N3—H2N3	0.92 (3)	C7—C8	1.371 (3)
C1—C2	1.426 (3)	C7—H7	0.95 (3)
C2—C3	1.382 (3)	C8—C9	1.398 (2)
C3—C4	1.397 (4)	C8—H8	0.95 (3)
C3—H3	1.06 (3)	C9—C10	1.381 (2)
C4—C5	1.342 (4)	C10—C11	1.400 (2)
C4—H4	0.91 (4)	C10—H10	0.89 (2)
C5—H5	0.99 (4)	C11—C12	1.473 (2)
S1—O4	1.4484 (14)	O1W—H1W1	0.90 (3)
S1—O2	1.4542 (14)	O1W—H2W1	0.98 (5)
S1—O3	1.4631 (14)
C1—N1—C5	124.4 (2)	O4—S1—C9	107.04 (8)
C1—N1—H1N1	118 (2)	O2—S1—C9	106.31 (8)
C5—N1—H1N1	117 (2)	O3—S1—C9	106.41 (8)
C1—N2—H1N2	115.9 (19)	C6—O1—H1O1	108.2 (16)
C1—N2—H2N2	118.6 (18)	C12—O5—H1O5	105 (2)
H1N2—N2—H2N2	120 (3)	O1—C6—C7	117.46 (16)
C2—N3—H1N3	124.8 (18)	O1—C6—C11	122.76 (16)
C2—N3—H2N3	120.1 (18)	C7—C6—C11	119.78 (15)
H1N3—N3—H2N3	113 (3)	C8—C7—C6	120.59 (15)
N1—C1—N2	119.15 (19)	C8—C7—H7	114.7 (16)
N1—C1—C2	118.33 (18)	C6—C7—H7	124.6 (16)
N2—C1—C2	122.50 (18)	C7—C8—C9	119.90 (15)
N3—C2—C3	123.45 (19)	C7—C8—H8	119.0 (17)
N3—C2—C1	119.73 (18)	C9—C8—H8	121.1 (17)
C3—C2—C1	116.80 (19)	C10—C9—C8	120.37 (15)
C2—C3—C4	121.9 (2)	C10—C9—S1	120.87 (12)
C2—C3—H3	116.2 (16)	C8—C9—S1	118.76 (12)
C4—C3—H3	121.7 (16)	C9—C10—C11	120.19 (14)
C5—C4—C3	119.5 (2)	C9—C10—H10	121.7 (15)
C5—C4—H4	120 (2)	C11—C10—H10	118.0 (15)
C3—C4—H4	120 (2)	C10—C11—C6	119.14 (14)
C4—C5—N1	118.9 (2)	C10—C11—C12	120.99 (15)
C4—C5—H5	127.2 (19)	C6—C11—C12	119.87 (14)
N1—C5—H5	113.4 (19)	O6—C12—O5	122.81 (16)
O4—S1—O2	112.20 (9)	O6—C12—C11	123.21 (16)
O4—S1—O3	112.80 (9)	O5—C12—C11	113.97 (15)
O2—S1—O3	111.58 (9)	H1W1—O1W—H2W1	124 (4)
C5—N1—C1—N2	−178.76 (19)	O2—S1—C9—C10	129.29 (13)
C5—N1—C1—C2	2.2 (3)	O3—S1—C9—C10	−111.65 (13)
N1—C1—C2—N3	175.05 (18)	O4—S1—C9—C8	−170.06 (13)
N2—C1—C2—N3	−3.9 (3)	O2—S1—C9—C8	−49.97 (14)
N1—C1—C2—C3	−3.3 (2)	O3—S1—C9—C8	69.09 (14)
N2—C1—C2—C3	177.74 (19)	C8—C9—C10—C11	0.1 (2)
N3—C2—C3—C4	−175.7 (2)	S1—C9—C10—C11	−179.10 (11)
C1—C2—C3—C4	2.5 (3)	C9—C10—C11—C6	1.7 (2)
C2—C3—C4—C5	−0.6 (4)	C9—C10—C11—C12	−179.31 (14)
C3—C4—C5—N1	−0.7 (4)	O1—C6—C11—C10	178.04 (16)
C1—N1—C5—C4	−0.2 (3)	C7—C6—C11—C10	−2.2 (2)
O1—C6—C7—C8	−179.37 (17)	O1—C6—C11—C12	−1.0 (2)
C11—C6—C7—C8	0.8 (3)	C7—C6—C11—C12	178.81 (15)
C6—C7—C8—C9	1.0 (3)	C10—C11—C12—O6	−174.36 (18)
C7—C8—C9—C10	−1.5 (2)	C6—C11—C12—O6	4.6 (3)
C7—C8—C9—S1	177.74 (14)	C10—C11—C12—O5	5.4 (2)
O4—S1—C9—C10	9.19 (15)	C6—C11—C12—O5	−175.63 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1Wi	0.91 (3)	1.95 (3)	2.806 (3)	158 (3)
N2—H1N2···O1i	0.90 (3)	2.48 (3)	3.222 (2)	140 (2)
N2—H1N2···O1Wi	0.90 (3)	2.28 (3)	3.060 (3)	145 (2)
N2—H2N2···O2ii	0.86 (3)	2.10 (3)	2.963 (2)	177 (3)
N3—H1N3···O2ii	0.89 (3)	2.10 (3)	2.970 (3)	168 (3)
N3—H2N3···O4iii	0.92 (3)	2.08 (3)	2.980 (3)	167 (3)
O1—H1O1···O6	1.03 (3)	1.75 (3)	2.625 (2)	141 (2)
O5—H1O5···O3iv	0.84 (3)	1.87 (3)	2.655 (2)	155 (3)
O1W—H1W1···O3v	0.89 (3)	1.94 (3)	2.757 (3)	151 (2)
O1W—H2W1···O4iii	0.98 (6)	1.89 (6)	2.838 (3)	162 (4)
C7—H7···O3vi	0.95 (3)	2.56 (3)	3.477 (2)	163 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1Wi	0.91 (3)	1.95 (3)	2.806 (3)	158 (3)
N2—H1N2⋯O1i	0.90 (3)	2.48 (3)	3.222 (2)	140 (2)
N2—H1N2⋯O1Wi	0.90 (3)	2.28 (3)	3.060 (3)	145 (2)
N2—H2N2⋯O2ii	0.86 (3)	2.10 (3)	2.963 (2)	177 (3)
N3—H1N3⋯O2ii	0.89 (3)	2.10 (3)	2.970 (3)	168 (3)
N3—H2N3⋯O4iii	0.92 (3)	2.08 (3)	2.980 (3)	167 (3)
O1—H1O1⋯O6	1.03 (3)	1.75 (3)	2.625 (2)	141 (2)
O5—H1O5⋯O3iv	0.84 (3)	1.87 (3)	2.655 (2)	155 (3)
O1W—H1W1⋯O3v	0.89 (3)	1.94 (3)	2.757 (3)	151 (2)
O1W—H2W1⋯O4iii	0.98 (6)	1.89 (6)	2.838 (3)	162 (4)
C7—H7⋯O3vi	0.95 (3)	2.56 (3)	3.477 (2)	163 (2)

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