2-Amino-4-methyl-pyridinium 3-carb-oxy-4-hy-droxy-benzene-sulfonate monohydrate.

In the crystal structure of the title salt, C(6)H(9)N(2) (+)·C(7)H(5)O(6)S(-)·H(2)O, the water mol-ecule acts as an acceptor of bifurcated N-H⋯O hydrogen bonds from the pyridinium H atom and one H atom of the 2-amino group, forming an R(2) (1)(6) ring. The 3-carb-oxy-4-hy-droxy-benzene-sulfonate anions self-assemble via O-H⋯O hydrogen bonds, leading to supra-molecular chains along the a axis. These chains and R(2) (1)(6) motifs are linked via O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, forming a layer parallel to the ac plane. There is also an intra-molecular O-H⋯O hydrogen bond in the 3-carb-oxy-4-hy-droxy-benzene-sulfonate anion, generating an S(6) ring motif.

Related literature

For details of sulfonates, see: Onoda et al. (2001 ▶); Baskar Raj et al. (2003 ▶); Ma 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

C6H9N2 +·C7H5O6S−·H2O

M = 344.34

Monoclinic,

a = 8.3280 (9) Å

b = 24.122 (3) Å

c = 7.9355 (8) Å

β = 112.800 (3)°

V = 1469.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 100 K

0.22 × 0.13 × 0.04 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.945, T max = 0.989

19925 measured reflections

5266 independent reflections

3749 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.120

S = 1.03

5266 reflections

272 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.46 e Å−3

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/S1600536810028539/is2579sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028539/is2579Isup2.hkl

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

C6H9N2+·C7H5O6S−·H2O	F(000) = 720
Mr = 344.34	Dx = 1.556 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3564 reflections
a = 8.3280 (9) Å	θ = 2.9–31.3°
b = 24.122 (3) Å	µ = 0.26 mm−1
c = 7.9355 (8) Å	T = 100 K
β = 112.800 (3)°	Plate, colourless
V = 1469.6 (3) Å3	0.22 × 0.13 × 0.04 mm
Z = 4

Bruker APEXII DUO CCD area-detector diffractometer	5266 independent reflections
Radiation source: fine-focus sealed tube	3749 reflections with I > 2σ(I)
graphite	Rint = 0.054
φ and ω scans	θmax = 32.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→11
Tmin = 0.945, Tmax = 0.989	k = −34→36
19925 measured reflections	l = −11→12

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.056P)2 + 0.3252P] where P = (Fo2 + 2Fc2)/3
5266 reflections	(Δ/σ)max = 0.001
272 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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	0.72197 (18)	0.06878 (6)	0.66805 (18)	0.0152 (3)
N2	0.5709 (2)	0.13358 (6)	0.4490 (2)	0.0198 (3)
C1	0.7310 (2)	0.02604 (7)	0.7835 (2)	0.0178 (3)
C2	0.5828 (2)	0.00495 (7)	0.7925 (2)	0.0175 (3)
C3	0.4197 (2)	0.02782 (6)	0.6816 (2)	0.0150 (3)
C4	0.4152 (2)	0.07114 (7)	0.5679 (2)	0.0151 (3)
C5	0.5695 (2)	0.09223 (6)	0.5591 (2)	0.0143 (3)
C6	0.2550 (2)	0.00524 (8)	0.6887 (2)	0.0210 (3)
S1	1.05075 (5)	0.122233 (15)	1.12957 (5)	0.01150 (9)
O1	0.45088 (16)	0.26192 (5)	0.70255 (16)	0.0191 (2)
O2	0.25121 (14)	0.18998 (5)	0.77919 (15)	0.0163 (2)
O3	0.38003 (15)	0.11993 (5)	0.96906 (15)	0.0149 (2)
O4	0.99761 (15)	0.08555 (5)	1.24394 (14)	0.0162 (2)
O5	1.19053 (14)	0.15990 (5)	1.23096 (15)	0.0169 (2)
O6	1.08974 (14)	0.09095 (4)	0.99033 (14)	0.0143 (2)
C7	0.5829 (2)	0.22831 (6)	0.8014 (2)	0.0133 (3)
C8	0.7498 (2)	0.24303 (7)	0.8160 (2)	0.0160 (3)
C9	0.8917 (2)	0.21104 (6)	0.9167 (2)	0.0146 (3)
C10	0.86880 (19)	0.16349 (6)	1.00593 (19)	0.0117 (3)
C11	0.70415 (19)	0.14816 (6)	0.99271 (19)	0.0118 (3)
C12	0.55938 (19)	0.18022 (6)	0.88935 (19)	0.0115 (3)
C13	0.3834 (2)	0.16422 (6)	0.87474 (19)	0.0123 (3)
O1W	−0.05262 (17)	0.12872 (5)	0.54890 (17)	0.0207 (3)
H1A	0.850 (3)	0.0128 (9)	0.855 (3)	0.031 (6)*
H2A	0.592 (3)	−0.0256 (8)	0.870 (3)	0.020 (5)*
H4A	0.309 (3)	0.0871 (8)	0.485 (3)	0.018 (5)*
H6A	0.161 (3)	0.0148 (10)	0.581 (3)	0.044 (7)*
H6B	0.239 (4)	0.0168 (10)	0.796 (4)	0.051 (7)*
H6C	0.259 (4)	−0.0352 (11)	0.695 (4)	0.054 (8)*
H9A	1.007 (3)	0.2204 (8)	0.925 (3)	0.019 (5)*
H8A	0.766 (3)	0.2767 (9)	0.752 (3)	0.027 (5)*
H11A	0.683 (3)	0.1137 (8)	1.054 (3)	0.017 (5)*
H1W1	−0.027 (3)	0.1193 (9)	0.457 (3)	0.030 (6)*
H2W1	0.034 (3)	0.1488 (10)	0.614 (3)	0.035 (6)*
H1O1	0.353 (3)	0.2485 (10)	0.708 (3)	0.038 (6)*
H1O3	0.280 (3)	0.1160 (10)	0.969 (3)	0.040 (7)*
H1N1	0.822 (3)	0.0824 (9)	0.661 (3)	0.039 (7)*
H1N2	0.671 (3)	0.1437 (9)	0.450 (3)	0.031 (6)*
H2N2	0.471 (4)	0.1469 (11)	0.379 (3)	0.047 (7)*

	U11	U22	U33	U12	U13	U23
N1	0.0115 (6)	0.0191 (6)	0.0148 (6)	0.0004 (5)	0.0047 (5)	−0.0003 (5)
N2	0.0177 (8)	0.0222 (7)	0.0193 (7)	−0.0003 (6)	0.0070 (6)	0.0056 (5)
C1	0.0166 (8)	0.0182 (7)	0.0160 (7)	0.0020 (6)	0.0035 (6)	−0.0001 (6)
C2	0.0201 (8)	0.0166 (7)	0.0150 (7)	0.0018 (6)	0.0060 (6)	0.0015 (5)
C3	0.0159 (8)	0.0173 (7)	0.0120 (6)	−0.0027 (6)	0.0057 (6)	−0.0030 (5)
C4	0.0129 (7)	0.0191 (7)	0.0127 (7)	0.0005 (6)	0.0044 (6)	0.0004 (5)
C5	0.0148 (7)	0.0169 (7)	0.0115 (6)	0.0004 (6)	0.0053 (5)	−0.0006 (5)
C6	0.0204 (9)	0.0242 (9)	0.0205 (8)	−0.0073 (7)	0.0100 (7)	−0.0015 (6)
S1	0.00831 (17)	0.01437 (17)	0.01216 (16)	0.00001 (13)	0.00434 (12)	0.00150 (12)
O1	0.0124 (6)	0.0204 (6)	0.0239 (6)	0.0034 (4)	0.0062 (5)	0.0083 (4)
O2	0.0093 (5)	0.0196 (5)	0.0186 (5)	0.0009 (4)	0.0038 (4)	0.0017 (4)
O3	0.0100 (5)	0.0166 (5)	0.0204 (5)	−0.0003 (4)	0.0085 (4)	0.0033 (4)
O4	0.0124 (5)	0.0206 (6)	0.0162 (5)	0.0007 (4)	0.0062 (4)	0.0057 (4)
O5	0.0108 (5)	0.0196 (5)	0.0175 (5)	−0.0035 (4)	0.0023 (4)	−0.0011 (4)
O6	0.0118 (5)	0.0169 (5)	0.0166 (5)	0.0012 (4)	0.0079 (4)	0.0000 (4)
C7	0.0114 (7)	0.0147 (7)	0.0134 (6)	0.0018 (5)	0.0044 (5)	0.0023 (5)
C8	0.0132 (7)	0.0172 (7)	0.0188 (7)	−0.0005 (6)	0.0075 (6)	0.0044 (6)
C9	0.0110 (7)	0.0168 (7)	0.0169 (7)	−0.0012 (5)	0.0066 (6)	0.0017 (5)
C10	0.0109 (7)	0.0142 (6)	0.0105 (6)	0.0000 (5)	0.0046 (5)	−0.0012 (5)
C11	0.0119 (7)	0.0130 (6)	0.0119 (6)	−0.0002 (5)	0.0063 (5)	−0.0010 (5)
C12	0.0099 (7)	0.0137 (6)	0.0116 (6)	0.0004 (5)	0.0050 (5)	0.0001 (5)
C13	0.0119 (7)	0.0139 (6)	0.0121 (6)	−0.0002 (5)	0.0059 (5)	−0.0016 (5)
O1W	0.0168 (6)	0.0282 (7)	0.0184 (6)	−0.0051 (5)	0.0083 (5)	−0.0024 (5)

N1—C5	1.352 (2)	S1—O6	1.4744 (10)
N1—C1	1.362 (2)	S1—C10	1.7598 (15)
N1—H1N1	0.91 (3)	O1—C7	1.3464 (18)
N2—C5	1.329 (2)	O1—H1O1	0.89 (2)
N2—H1N2	0.87 (2)	O2—C13	1.2354 (18)
N2—H2N2	0.86 (3)	O3—C13	1.3108 (17)
C1—C2	1.362 (2)	O3—H1O3	0.84 (3)
C1—H1A	0.98 (2)	C7—C8	1.396 (2)
C2—C3	1.413 (2)	C7—C12	1.4059 (19)
C2—H2A	0.946 (19)	C8—C9	1.378 (2)
C3—C4	1.372 (2)	C8—H8A	0.99 (2)
C3—C6	1.496 (2)	C9—C10	1.399 (2)
C4—C5	1.408 (2)	C9—H9A	0.96 (2)
C4—H4A	0.95 (2)	C10—C11	1.384 (2)
C6—H6A	0.94 (3)	C11—C12	1.399 (2)
C6—H6B	0.96 (3)	C11—H11A	1.013 (19)
C6—H6C	0.98 (3)	C12—C13	1.476 (2)
S1—O5	1.4498 (12)	O1W—H1W1	0.87 (2)
S1—O4	1.4539 (10)	O1W—H2W1	0.86 (3)
C5—N1—C1	122.70 (14)	O4—S1—O6	111.41 (6)
C5—N1—H1N1	117.5 (15)	O5—S1—C10	106.72 (7)
C1—N1—H1N1	119.8 (15)	O4—S1—C10	106.72 (7)
C5—N2—H1N2	117.3 (15)	O6—S1—C10	105.29 (6)
C5—N2—H2N2	117.0 (17)	C7—O1—H1O1	107.9 (15)
H1N2—N2—H2N2	126 (2)	C13—O3—H1O3	109.5 (17)
N1—C1—C2	120.18 (15)	O1—C7—C8	117.20 (13)
N1—C1—H1A	114.5 (13)	O1—C7—C12	123.15 (13)
C2—C1—H1A	125.3 (13)	C8—C7—C12	119.64 (14)
C1—C2—C3	119.59 (15)	C9—C8—C7	120.56 (14)
C1—C2—H2A	118.8 (12)	C9—C8—H8A	119.9 (13)
C3—C2—H2A	121.5 (12)	C7—C8—H8A	119.5 (13)
C4—C3—C2	118.76 (15)	C8—C9—C10	119.87 (14)
C4—C3—C6	120.69 (15)	C8—C9—H9A	121.1 (12)
C2—C3—C6	120.55 (14)	C10—C9—H9A	119.0 (12)
C3—C4—C5	121.00 (15)	C11—C10—C9	120.40 (14)
C3—C4—H4A	122.9 (12)	C11—C10—S1	120.31 (11)
C5—C4—H4A	115.9 (12)	C9—C10—S1	119.26 (11)
N2—C5—N1	119.28 (15)	C10—C11—C12	120.00 (13)
N2—C5—C4	122.94 (15)	C10—C11—H11A	122.3 (11)
N1—C5—C4	117.77 (14)	C12—C11—H11A	117.7 (11)
C3—C6—H6A	109.5 (15)	C11—C12—C7	119.53 (13)
C3—C6—H6B	112.1 (16)	C11—C12—C13	120.35 (13)
H6A—C6—H6B	112 (2)	C7—C12—C13	120.11 (13)
C3—C6—H6C	110.6 (17)	O2—C13—O3	123.31 (13)
H6A—C6—H6C	107 (2)	O2—C13—C12	122.56 (13)
H6B—C6—H6C	105 (2)	O3—C13—C12	114.11 (13)
O5—S1—O4	114.09 (7)	H1W1—O1W—H2W1	103 (2)
O5—S1—O6	111.96 (6)
C5—N1—C1—C2	0.2 (2)	O6—S1—C10—C11	101.97 (12)
N1—C1—C2—C3	−0.2 (2)	O5—S1—C10—C9	43.01 (13)
C1—C2—C3—C4	−0.3 (2)	O4—S1—C10—C9	165.36 (11)
C1—C2—C3—C6	179.81 (15)	O6—S1—C10—C9	−76.13 (12)
C2—C3—C4—C5	0.8 (2)	C9—C10—C11—C12	0.1 (2)
C6—C3—C4—C5	−179.32 (14)	S1—C10—C11—C12	−177.97 (10)
C1—N1—C5—N2	−179.53 (14)	C10—C11—C12—C7	−0.8 (2)
C1—N1—C5—C4	0.2 (2)	C10—C11—C12—C13	−179.91 (13)
C3—C4—C5—N2	179.01 (14)	O1—C7—C12—C11	−178.68 (13)
C3—C4—C5—N1	−0.8 (2)	C8—C7—C12—C11	1.0 (2)
O1—C7—C8—C9	179.25 (14)	O1—C7—C12—C13	0.4 (2)
C12—C7—C8—C9	−0.4 (2)	C8—C7—C12—C13	−179.93 (13)
C7—C8—C9—C10	−0.3 (2)	C11—C12—C13—O2	−177.02 (13)
C8—C9—C10—C11	0.4 (2)	C7—C12—C13—O2	3.9 (2)
C8—C9—C10—S1	178.55 (12)	C11—C12—C13—O3	1.81 (19)
O5—S1—C10—C11	−138.89 (12)	C7—C12—C13—O3	−177.26 (12)
O4—S1—C10—C11	−16.54 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O4i	0.87 (2)	1.96 (2)	2.8108 (18)	168 (2)
O1W—H2W1···O2	0.86 (2)	2.04 (2)	2.8882 (18)	175 (2)
O1—H1O1···O2	0.89 (3)	1.84 (2)	2.6325 (18)	146 (2)
O3—H1O3···O6ii	0.84 (3)	1.76 (3)	2.5842 (18)	166 (2)
N1—H1N1···O1Wiii	0.92 (3)	1.96 (2)	2.808 (2)	153 (2)
N2—H1N2···O1Wiii	0.87 (3)	2.16 (3)	2.923 (2)	147.7 (19)
N2—H2N2···O5i	0.86 (3)	2.19 (3)	3.030 (2)	163 (3)
C2—H2A···O3iv	0.94 (2)	2.58 (2)	3.507 (2)	169.1 (17)
C4—H4A···O4i	0.96 (2)	2.56 (2)	3.449 (2)	155.4 (16)
C4—H4A···O5i	0.96 (2)	2.57 (2)	3.370 (2)	142 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O4i	0.87 (2)	1.96 (2)	2.8108 (18)	168 (2)
O1W—H2W1⋯O2	0.86 (2)	2.04 (2)	2.8882 (18)	175 (2)
O1—H1O1⋯O2	0.89 (3)	1.84 (2)	2.6325 (18)	146 (2)
O3—H1O3⋯O6ii	0.84 (3)	1.76 (3)	2.5842 (18)	166 (2)
N1—H1N1⋯O1Wiii	0.92 (3)	1.96 (2)	2.808 (2)	153 (2)
N2—H1N2⋯O1Wiii	0.87 (3)	2.16 (3)	2.923 (2)	147.7 (19)
N2—H2N2⋯O5i	0.86 (3)	2.19 (3)	3.030 (2)	163 (3)
C2—H2A⋯O3iv	0.94 (2)	2.58 (2)	3.507 (2)	169.1 (17)
C4—H4A⋯O4i	0.96 (2)	2.56 (2)	3.449 (2)	155.4 (16)
C4—H4A⋯O5i	0.96 (2)	2.57 (2)	3.370 (2)	142 (2)

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