4-Amino-pyridinium 4-amino-benzene-sulfonate 4-ammonio-benzene-sulfonate monohydrate.

The asymmetric unit of the title compound, C(5)H(7)N(2) (+)·C(6)H(6)NO(3)S(-)·C(6)H(7)NO(3)S·H(2)O, contains one 4-ammonio-benzene-sulfonate zwitterion ((+)H(3)NC(6)H(4)SO(3) (-)), one 4-amino-benzene-sulfonate anion (H(2)NC(6)H(4)SO(3) (-)), one 4-amino-pyridinium cation and two half-mol-ecules of water, each lying on a twofold rotation axis. The various ions and molecules in the structure are linked through N-H⋯O, N-H⋯N and N-H⋯S hydrogen bonds and C-H-π inter-actions into a three-dimensional framework.

Related literature

For related literature, see: Anderson et al. (2005 ▶); Banu & Golzar Hossain (2006 ▶); Chao & Schempp (1977 ▶); Judge & Bever (2006 ▶); Rae & Maslen (1962 ▶); Schwid et al. (1997 ▶); Strupp et al. (2004 ▶).

Experimental

Crystal data

C5H7N2 +·C6H6NO3S−·C6H7NO3S·H2O

M = 458.53

Monoclinic,

a = 24.9902 (2) Å

b = 5.7475 (1) Å

c = 15.1930 (1) Å

β = 115.415 (1)°

V = 1971.00 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 100.0 (1) K

0.35 × 0.18 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.895, T max = 0.972

30055 measured reflections

9157 independent reflections

7528 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.114

S = 1.06

9157 reflections

272 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.66 e Å−3

Absolute structure: Flack (1983 ▶), 4029 Friedel pairs

Flack parameter: −0.01 (4)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808006259/ci2568sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006259/ci2568Isup2.hkl

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

C5H7N2+·C6H6NO3S–·C6H7NO3S·H2O	F000 = 960
Mr = 458.53	Dx = 1.545 Mg m−3
Monoclinic, C2	Mo Kα radiation λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 6986 reflections
a = 24.9902 (2) Å	θ = 2.7–35.1º
b = 5.7475 (1) Å	µ = 0.32 mm−1
c = 15.1930 (1) Å	T = 100.0 (1) K
β = 115.415 (1)º	Plate, yellow
V = 1971.00 (4) Å3	0.35 × 0.18 × 0.08 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	Rint = 0.051
φ and ω scans	θmax = 36.2º
Absorption correction: multi-scan(SADABS; Bruker, 2005)	θmin = 1.5º
Tmin = 0.895, Tmax = 0.972	h = −41→41
30055 measured reflections	k = −9→9
9157 independent reflections	l = −25→25
7528 reflections with I > 2σ(I)

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0544P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.048	(Δ/σ)max = 0.001
wR(F2) = 0.114	Δρmax = 0.43 e Å−3
S = 1.06	Δρmin = −0.66 e Å−3
9157 reflections	Extinction correction: none
272 parameters	Absolute structure: Flack (1983), 4029 Friedel pairs
6 restraints	Flack parameter: −0.01 (4)

Geometry. Experimental. The low-temperature data was collected with the Oxford Crysosystem Cobra low-temperature attachement.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.

	x	y	z	Uiso*/Ueq
S1	0.367717 (17)	0.30668 (6)	−0.07087 (3)	0.01197 (7)
S2	0.349420 (17)	1.00691 (6)	0.42455 (3)	0.01122 (7)
O1	0.41498 (6)	0.4675 (2)	−0.06022 (10)	0.0217 (3)
O2	0.31451 (5)	0.3430 (2)	−0.16138 (8)	0.0158 (2)
O3	0.38660 (5)	0.0621 (2)	−0.06024 (9)	0.0157 (2)
O4	0.39347 (5)	0.8372 (2)	0.42552 (8)	0.0146 (2)
O5	0.29296 (5)	0.9811 (2)	0.33955 (8)	0.0147 (2)
O6	0.37175 (5)	1.2447 (2)	0.43941 (8)	0.0148 (2)
N1	0.30210 (6)	0.5120 (3)	0.25477 (10)	0.0144 (2)
H1N1	0.33	0.456	0.3111	0.017*
H2N1	0.2963	0.6634	0.263	0.017*
N2	0.30594 (6)	0.8065 (3)	0.77520 (9)	0.0129 (2)
H1N2	0.3084	0.6527	0.7875	0.016*
H2N2	0.2691	0.8528	0.7635	0.016*
H3N2	0.3364	0.8664	0.8275	0.016*
N3	0.50936 (7)	0.5548 (3)	0.15575 (11)	0.0228 (3)
H1N3	0.5201	0.5786	0.1072	0.027*
N4	0.46259 (7)	0.4675 (3)	0.38104 (11)	0.0205 (3)
H4A	0.4406	0.5691	0.3911	0.025*
H4B	0.4742	0.3462	0.4175	0.025*
C1	0.34758 (7)	0.3645 (3)	0.02502 (11)	0.0106 (3)
C2	0.35850 (7)	0.2020 (3)	0.09866 (11)	0.0142 (3)
H2A	0.3759	0.0601	0.0969	0.017*
C3	0.34344 (8)	0.2509 (3)	0.17467 (12)	0.0145 (3)
H3A	0.3507	0.1414	0.2236	0.017*
C4	0.31746 (7)	0.4633 (3)	0.17813 (11)	0.0120 (3)
C5	0.30432 (7)	0.6223 (3)	0.10179 (12)	0.0142 (3)
H5A	0.2852	0.7612	0.1017	0.017*
C6	0.31977 (7)	0.5733 (3)	0.02616 (12)	0.0145 (3)
H6A	0.3115	0.6805	−0.0239	0.017*
C7	0.33669 (7)	0.9400 (3)	0.52796 (11)	0.0110 (3)
C8	0.35436 (7)	0.7288 (3)	0.57586 (12)	0.0143 (3)
H8A	0.373	0.6182	0.554	0.017*
C9	0.34381 (8)	0.6843 (3)	0.65743 (12)	0.0144 (3)
H9A	0.3555	0.5438	0.6906	0.017*
C10	0.31584 (7)	0.8516 (3)	0.68843 (11)	0.0112 (3)
C11	0.29681 (7)	1.0617 (3)	0.63989 (12)	0.0132 (3)
H11A	0.2774	1.1707	0.661	0.016*
C12	0.30754 (7)	1.1049 (3)	0.55864 (11)	0.0133 (3)
H12A	0.2952	1.2443	0.5248	0.016*
C13	0.47866 (7)	0.4979 (3)	0.30921 (12)	0.0164 (3)
C14	0.51422 (8)	0.3311 (3)	0.28971 (14)	0.0211 (3)
H14A	0.5278	0.1998	0.3288	0.025*
C15	0.52825 (8)	0.3652 (4)	0.21303 (14)	0.0218 (4)
H15A	0.5513	0.2554	0.2002	0.026*
C16	0.47601 (9)	0.7162 (4)	0.17268 (14)	0.0244 (4)
H16A	0.4632	0.8455	0.1322	0.029*
C17	0.46057 (8)	0.6940 (4)	0.24815 (13)	0.0213 (4)
H17A	0.438	0.8089	0.2592	0.026*
O1W	0.5	1.0580 (4)	0.5	0.0317 (5)
H1W1	0.5296	0.9626	0.5253	0.048*
O2W	0.5	−0.1247 (3)	0	0.0196 (4)
H1W2	0.4689	−0.035	−0.0196	0.029*

	U11	U22	U33	U12	U13	U23
S1	0.01387 (17)	0.01226 (16)	0.01171 (16)	−0.00155 (13)	0.00731 (14)	−0.00131 (13)
S2	0.01273 (17)	0.01111 (15)	0.01161 (16)	−0.00077 (13)	0.00692 (13)	−0.00047 (13)
O1	0.0231 (7)	0.0258 (7)	0.0228 (6)	−0.0136 (5)	0.0160 (5)	−0.0090 (5)
O2	0.0201 (6)	0.0144 (6)	0.0110 (5)	0.0003 (4)	0.0048 (4)	0.0008 (4)
O3	0.0170 (6)	0.0153 (5)	0.0146 (5)	0.0045 (4)	0.0067 (5)	−0.0004 (4)
O4	0.0150 (5)	0.0149 (6)	0.0170 (5)	0.0016 (4)	0.0097 (5)	−0.0016 (4)
O5	0.0145 (5)	0.0175 (6)	0.0109 (5)	−0.0005 (4)	0.0042 (4)	−0.0014 (4)
O6	0.0190 (6)	0.0116 (5)	0.0156 (5)	−0.0025 (4)	0.0091 (5)	−0.0001 (4)
N1	0.0188 (6)	0.0133 (6)	0.0140 (6)	0.0011 (5)	0.0097 (5)	−0.0005 (5)
N2	0.0156 (6)	0.0125 (5)	0.0113 (5)	−0.0002 (5)	0.0064 (5)	0.0001 (5)
N3	0.0204 (8)	0.0333 (9)	0.0189 (7)	−0.0037 (6)	0.0123 (6)	−0.0033 (6)
N4	0.0241 (8)	0.0220 (8)	0.0209 (7)	0.0005 (6)	0.0150 (6)	−0.0014 (5)
C1	0.0105 (6)	0.0109 (6)	0.0104 (6)	−0.0007 (5)	0.0045 (5)	−0.0002 (5)
C2	0.0176 (8)	0.0123 (6)	0.0144 (7)	0.0022 (5)	0.0085 (6)	0.0015 (5)
C3	0.0195 (8)	0.0118 (6)	0.0148 (7)	0.0020 (5)	0.0097 (6)	0.0029 (5)
C4	0.0118 (7)	0.0128 (7)	0.0125 (6)	−0.0011 (5)	0.0063 (6)	−0.0010 (5)
C5	0.0168 (8)	0.0116 (6)	0.0157 (7)	0.0009 (5)	0.0085 (6)	0.0004 (5)
C6	0.0182 (8)	0.0127 (6)	0.0135 (7)	0.0015 (6)	0.0074 (6)	0.0014 (5)
C7	0.0116 (7)	0.0112 (6)	0.0110 (6)	−0.0004 (5)	0.0057 (5)	−0.0003 (5)
C8	0.0176 (8)	0.0119 (6)	0.0149 (7)	0.0032 (6)	0.0087 (6)	0.0014 (5)
C9	0.0178 (8)	0.0120 (6)	0.0157 (7)	0.0024 (5)	0.0092 (6)	0.0018 (5)
C10	0.0123 (7)	0.0113 (6)	0.0104 (6)	−0.0009 (5)	0.0053 (5)	0.0000 (5)
C11	0.0158 (7)	0.0116 (6)	0.0141 (7)	0.0009 (5)	0.0082 (6)	−0.0004 (5)
C12	0.0168 (7)	0.0115 (6)	0.0124 (7)	0.0008 (5)	0.0071 (6)	0.0010 (5)
C13	0.0134 (7)	0.0201 (7)	0.0165 (7)	−0.0022 (6)	0.0073 (6)	−0.0046 (6)
C14	0.0219 (9)	0.0196 (8)	0.0250 (9)	−0.0014 (7)	0.0132 (7)	−0.0031 (7)
C15	0.0204 (9)	0.0253 (9)	0.0241 (9)	−0.0032 (7)	0.0136 (7)	−0.0067 (7)
C16	0.0215 (9)	0.0315 (10)	0.0232 (9)	0.0013 (8)	0.0123 (8)	0.0046 (8)
C17	0.0192 (9)	0.0255 (9)	0.0221 (9)	0.0040 (7)	0.0116 (7)	0.0017 (7)
O1W	0.0145 (9)	0.0162 (9)	0.0556 (14)	0	0.0067 (9)	0
O2W	0.0160 (8)	0.0161 (8)	0.0278 (10)	0	0.0104 (7)	0

S1—O1	1.4531 (13)	C3—H3A	0.93
S1—O2	1.4604 (12)	C4—C5	1.400 (2)
S1—O3	1.4692 (13)	C5—C6	1.389 (2)
S1—C1	1.7651 (15)	C5—H5A	0.93
S2—O5	1.4548 (12)	C6—H6A	0.93
S2—O6	1.4570 (13)	C7—C8	1.386 (2)
S2—O4	1.4661 (12)	C7—C12	1.392 (2)
S2—C7	1.7737 (15)	C8—C9	1.397 (2)
N1—C4	1.4016 (19)	C8—H8A	0.93
N1—H1N1	0.90	C9—C10	1.385 (2)
N1—H2N1	0.90	C9—H9A	0.93
N2—C10	1.4650 (19)	C10—C11	1.388 (2)
N2—H1N2	0.90	C11—C12	1.393 (2)
N2—H2N2	0.90	C11—H11A	0.93
N2—H3N2	0.90	C12—H12A	0.93
N3—C16	1.343 (3)	C13—C17	1.405 (3)
N3—C15	1.347 (3)	C13—C14	1.422 (2)
N3—H1N3	0.90	C14—C15	1.367 (3)
N4—C13	1.326 (2)	C14—H14A	0.93
N4—H4A	0.86	C15—H15A	0.93
N4—H4B	0.86	C16—C17	1.364 (2)
C1—C6	1.391 (2)	C16—H16A	0.93
C1—C2	1.392 (2)	C17—H17A	0.93
C2—C3	1.388 (2)	O1W—H1W1	0.87
C2—H2A	0.93	O2W—H1W2	0.87
C3—C4	1.395 (2)
O1—S1—O2	112.46 (8)	C6—C5—C4	120.22 (15)
O1—S1—O3	112.88 (8)	C6—C5—H5A	119.9
O2—S1—O3	111.08 (7)	C4—C5—H5A	119.9
O1—S1—C1	107.12 (7)	C5—C6—C1	120.20 (14)
O2—S1—C1	106.46 (7)	C5—C6—H6A	119.9
O3—S1—C1	106.34 (7)	C1—C6—H6A	119.9
O5—S2—O6	113.23 (7)	C8—C7—C12	120.98 (14)
O5—S2—O4	112.27 (7)	C8—C7—S2	121.12 (12)
O6—S2—O4	112.74 (7)	C12—C7—S2	117.90 (12)
O5—S2—C7	106.85 (7)	C7—C8—C9	119.16 (15)
O6—S2—C7	105.57 (7)	C7—C8—H8A	120.4
O4—S2—C7	105.45 (7)	C9—C8—H8A	120.4
C4—N1—H1N1	109.9	C10—C9—C8	119.31 (15)
C4—N1—H2N1	115.3	C10—C9—H9A	120.3
H1N1—N1—H2N1	108.6	C8—C9—H9A	120.3
C10—N2—H1N2	109.7	C9—C10—C11	122.08 (14)
C10—N2—H2N2	108.9	C9—C10—N2	119.21 (14)
H1N2—N2—H2N2	107.7	C11—C10—N2	118.71 (14)
C10—N2—H3N2	108.7	C10—C11—C12	118.26 (15)
H1N2—N2—H3N2	103.7	C10—C11—H11A	120.9
H2N2—N2—H3N2	117.9	C12—C11—H11A	120.9
C16—N3—C15	120.58 (15)	C7—C12—C11	120.19 (15)
C16—N3—H1N3	118.7	C7—C12—H12A	119.9
C15—N3—H1N3	120.6	C11—C12—H12A	119.9
C13—N4—H4A	120	N4—C13—C17	121.57 (16)
C13—N4—H4B	120	N4—C13—C14	121.31 (17)
H4A—N4—H4B	120	C17—C13—C14	117.11 (16)
C6—C1—C2	119.74 (14)	C15—C14—C13	119.51 (18)
C6—C1—S1	119.59 (12)	C15—C14—H14A	120.2
C2—C1—S1	120.67 (12)	C13—C14—H14A	120.2
C3—C2—C1	120.20 (15)	N3—C15—C14	121.31 (17)
C3—C2—H2A	119.9	N3—C15—H15A	119.3
C1—C2—H2A	119.9	C14—C15—H15A	119.3
C2—C3—C4	120.37 (15)	N3—C16—C17	121.27 (19)
C2—C3—H3A	119.8	N3—C16—H16A	119.4
C4—C3—H3A	119.8	C17—C16—H16A	119.4
C3—C4—C5	119.18 (14)	C16—C17—C13	120.20 (18)
C3—C4—N1	120.25 (14)	C16—C17—H17A	119.9
C5—C4—N1	120.50 (14)	C13—C17—H17A	119.9
O1—S1—C1—C6	68.17 (14)	O6—S2—C7—C12	45.63 (14)
O2—S1—C1—C6	−52.35 (14)	O4—S2—C7—C12	165.19 (12)
O3—S1—C1—C6	−170.88 (13)	C12—C7—C8—C9	−1.5 (2)
O1—S1—C1—C2	−112.74 (14)	S2—C7—C8—C9	179.53 (13)
O2—S1—C1—C2	126.73 (13)	C7—C8—C9—C10	0.2 (2)
O3—S1—C1—C2	8.21 (15)	C8—C9—C10—C11	1.2 (2)
C6—C1—C2—C3	−2.1 (2)	C8—C9—C10—N2	−178.73 (15)
S1—C1—C2—C3	178.85 (13)	C9—C10—C11—C12	−1.3 (2)
C1—C2—C3—C4	−0.2 (2)	N2—C10—C11—C12	178.68 (14)
C2—C3—C4—C5	2.8 (2)	C8—C7—C12—C11	1.4 (2)
C2—C3—C4—N1	179.77 (15)	S2—C7—C12—C11	−179.55 (12)
C3—C4—C5—C6	−3.2 (2)	C10—C11—C12—C7	−0.1 (2)
N1—C4—C5—C6	179.86 (15)	N4—C13—C14—C15	177.91 (17)
C4—C5—C6—C1	1.0 (2)	C17—C13—C14—C15	−1.1 (3)
C2—C1—C6—C5	1.7 (2)	C16—N3—C15—C14	0.0 (3)
S1—C1—C6—C5	−179.22 (13)	C13—C14—C15—N3	0.4 (3)
O5—S2—C7—C8	103.83 (14)	C15—N3—C16—C17	0.3 (3)
O6—S2—C7—C8	−135.36 (14)	N3—C16—C17—C13	−1.1 (3)
O4—S2—C7—C8	−15.81 (15)	N4—C13—C17—C16	−177.60 (18)
O5—S2—C7—C12	−75.17 (14)	C14—C13—C17—C16	1.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O1Wi	0.86	2.01	2.869 (2)	179
N2—H3N2···O3ii	0.90	1.98	2.8542 (19)	164
N1—H1N1···O6i	0.90	2.15	3.0111 (19)	160
N2—H1N2···O2iii	0.90	1.92	2.8101 (19)	168
N2—H1N2···S1iii	0.90	2.84	3.6066 (15)	144
N3—H1N3···O1iv	0.90	2.13	2.879 (2)	140
N3—H1N3···O2Wv	0.90	2.26	2.928 (2)	131
N2—H2N2···N1vi	0.90	1.91	2.799 (2)	168
N4—H4A···O4	0.86	2.14	2.9929 (19)	175
N1—H2N1···O5	0.90	2.19	3.0386 (19)	158
O1W—H1W1···O4vii	0.87	1.88	2.7189 (15)	162
O2W—H1W2···O3	0.87	1.96	2.7921 (14)	160
C12—H12A···Cg1vi	0.93	2.96	3.614 (19)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯O1Wi	0.86	2.01	2.869 (2)	179
N2—H3N2⋯O3ii	0.90	1.98	2.8542 (19)	164
N1—H1N1⋯O6i	0.90	2.15	3.0111 (19)	160
N2—H1N2⋯O2iii	0.90	1.92	2.8101 (19)	168
N2—H1N2⋯S1iii	0.90	2.84	3.6066 (15)	144
N3—H1N3⋯O1iv	0.90	2.13	2.879 (2)	140
N3—H1N3⋯O2Wv	0.90	2.26	2.928 (2)	131
N2—H2N2⋯N1vi	0.90	1.91	2.799 (2)	168
N4—H4A⋯O4	0.86	2.14	2.9929 (19)	175
N1—H2N1⋯O5	0.90	2.19	3.0386 (19)	158
O1W—H1W1⋯O4vii	0.87	1.88	2.7189 (15)	162
O2W—H1W2⋯O3	0.87	1.96	2.7921 (14)	160
C12—H12A⋯Cg1vi	0.93	2.96	3.614 (19)	129

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) . Cg1 is the centroid of the C7–C12 benzene ring.