Bis(4-amino-pyridinium) sulfate monohydrate.

The asymmetric unit of the title compound, 2C(5)H(7)N(2) (+)·SO(4) (2-)·H(2)O, contains two 4-amino-pyridinium cations (A and B), a sulfate dianion and a water mol-ecule. One of the 4-amino-pyridinium cations (B) is disordered over two orientations with refined site occupancies of 0.568 (4) and 0.432 (4). The non-H atoms of the 4-amino-pyridinium cations are essentially coplanar, with a maximum deviation of 0.055 (1) Å (in cation A), 0.022 (3) Å (for the major component in cation B) and 0.009 (3) Å (for the minor component in cation B). In the crystal, the sulfate O atoms link the 4-amino-pyridinium cations and water mol-ecules into a three-dimensional network via inter-molecular O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds. The crystal structure is further consolidated by N-H⋯O(water) and C-H⋯O(water) hydrogen bonds.

Related literature

For general background to and the applications of the title compound, see: Judge & Bever (2006 ▶); Schwid et al. (1997 ▶); Strupp et al. (2004 ▶); Onoda et al. (2001 ▶); Zhang et al. (2004 ▶); Pflugrath & Quiocho, (1985 ▶); Jacobson & Quiocho (1988 ▶). For related structures, see: Quah et al. (2008a ▶,b ▶, 2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

2C5H7N2 +·SO4 2−·H2O

M = 304.33

Triclinic,

a = 6.4434 (1) Å

b = 8.4153 (1) Å

c = 12.4488 (2) Å

α = 96.365 (1)°

β = 97.534 (1)°

γ = 95.387 (1)°

V = 661.02 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.27 mm−1

T = 100 K

0.33 × 0.25 × 0.07 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.916, T max = 0.981

10717 measured reflections

3839 independent reflections

3279 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.106

S = 1.06

3839 reflections

259 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.55 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/S1600536810030941/bt5310sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030941/bt5310Isup2.hkl

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

2C5H7N2+·SO42−·H2O	Z = 2
Mr = 304.33	F(000) = 320
Triclinic, P1	Dx = 1.529 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4434 (1) Å	Cell parameters from 3597 reflections
b = 8.4153 (1) Å	θ = 3.1–30.1°
c = 12.4488 (2) Å	µ = 0.27 mm−1
α = 96.365 (1)°	T = 100 K
β = 97.534 (1)°	Plate, colourless
γ = 95.387 (1)°	0.33 × 0.25 × 0.07 mm
V = 661.02 (2) Å3

Bruker SMART APEXII CCD area-detector diffractometer	3839 independent reflections
Radiation source: fine-focus sealed tube	3279 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 30.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.916, Tmax = 0.981	k = −11→11
10717 measured reflections	l = −17→17

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) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0441P)2 + 0.4122P] where P = (Fo2 + 2Fc2)/3
3839 reflections	(Δ/σ)max < 0.001
259 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.55 e Å−3

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

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	Occ. (<1)
S1	0.41695 (5)	0.12500 (4)	0.29301 (3)	0.01520 (10)
O4	0.28974 (17)	0.13054 (13)	0.38487 (9)	0.0210 (2)
O3	0.52927 (17)	0.28476 (13)	0.29263 (10)	0.0217 (2)
O2	0.56565 (18)	0.00390 (14)	0.30613 (10)	0.0256 (3)
O1	0.27120 (18)	0.08095 (15)	0.18901 (10)	0.0277 (3)
N2	−0.0310 (2)	0.34101 (15)	0.35023 (11)	0.0172 (2)
C5	0.2971 (2)	0.72142 (18)	0.42897 (12)	0.0182 (3)
H5A	0.4373	0.7607	0.4527	0.022*
N1	0.1519 (2)	0.82613 (16)	0.41396 (11)	0.0192 (3)
C3	0.0277 (2)	0.49838 (17)	0.37303 (11)	0.0144 (3)
C2	−0.1204 (2)	0.61239 (18)	0.36079 (12)	0.0168 (3)
H2A	−0.2625	0.5775	0.3392	0.020*
O1W	0.8386 (2)	0.96841 (16)	0.15025 (14)	0.0355 (3)
C4	0.2413 (2)	0.55943 (17)	0.40997 (11)	0.0160 (3)
H4A	0.3428	0.4891	0.4212	0.019*
C1	−0.0540 (2)	0.77280 (18)	0.38069 (12)	0.0189 (3)
H1A	−0.1514	0.8467	0.3713	0.023*
C2A	0.7722 (12)	0.4735 (7)	1.0588 (7)	0.0238 (7)	0.568 (4)
H2AA	0.8019	0.5311	1.1282	0.029*	0.568 (4)
C1A	0.7613 (4)	0.3094 (4)	1.0482 (3)	0.0238 (7)	0.568 (4)
H1AA	0.7854	0.2567	1.1097	0.029*	0.568 (4)
C5A	0.6790 (11)	0.2982 (7)	0.8591 (6)	0.0237 (11)	0.568 (4)
H5AA	0.6461	0.2370	0.7910	0.028*	0.568 (4)
C4A	0.6891 (9)	0.4594 (7)	0.8661 (5)	0.0175 (10)	0.568 (4)
H4AA	0.6624	0.5082	0.8030	0.021*	0.568 (4)
N2A	0.7527 (4)	0.7162 (3)	0.9771 (2)	0.0185 (6)	0.568 (4)
H2NA	0.7286	0.7515	0.9160	0.028*	0.568 (4)
H1NA	0.7770	0.7672	1.0350	0.028*	0.568 (4)
C3A	0.7401 (4)	0.5559 (4)	0.9691 (2)	0.0134 (6)	0.568 (4)
N1A	0.7155 (4)	0.2243 (4)	0.9482 (3)	0.0263 (7)	0.568 (4)
H1AB	0.7039	0.1217	0.9350	0.032*	0.568 (4)
N2B	0.7174 (5)	0.1525 (5)	0.9860 (3)	0.0219 (8)	0.432 (4)
H1NB	0.7542	0.1178	1.0500	0.033*	0.432 (4)
H2NB	0.7106	0.0855	0.9312	0.033*	0.432 (4)
C1B	0.7723 (6)	0.5882 (5)	1.0409 (4)	0.0270 (10)	0.432 (4)
H1BB	0.7821	0.6760	1.0868	0.040*	0.432 (4)
N1B	0.7377 (5)	0.6283 (6)	0.9395 (4)	0.0257 (9)	0.432 (4)
H1BA	0.7421	0.7279	0.9294	0.038*	0.432 (4)
C3B	0.7256 (5)	0.3062 (6)	0.9719 (3)	0.0173 (8)	0.432 (4)
C4B	0.6880 (12)	0.3543 (9)	0.8640 (6)	0.0168 (13)	0.432 (4)
H4BA	0.6584	0.2771	0.8030	0.020*	0.432 (4)
C5B	0.6959 (13)	0.5103 (9)	0.8524 (7)	0.0208 (13)	0.432 (4)
H5BA	0.6721	0.5400	0.7824	0.025*	0.432 (4)
C2B	0.7688 (12)	0.4344 (6)	1.0631 (6)	0.0153 (12)	0.432 (4)
H2BA	0.7932	0.4112	1.1347	0.018*	0.432 (4)
H1W1	0.750 (5)	0.985 (4)	0.201 (3)	0.067 (9)*
H2W1	0.963 (5)	1.006 (3)	0.172 (2)	0.054 (8)*
H1N1	0.193 (3)	0.929 (3)	0.4163 (18)	0.033 (6)*
H1N2	0.061 (4)	0.275 (3)	0.3623 (17)	0.031 (6)*
H2N2	−0.163 (3)	0.309 (2)	0.3310 (16)	0.023 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.01105 (16)	0.01034 (16)	0.02362 (18)	0.00082 (11)	0.00082 (12)	0.00180 (12)
O4	0.0194 (5)	0.0152 (5)	0.0305 (6)	0.0027 (4)	0.0077 (4)	0.0058 (4)
O3	0.0194 (5)	0.0141 (5)	0.0311 (6)	−0.0032 (4)	0.0040 (4)	0.0044 (4)
O2	0.0208 (6)	0.0197 (5)	0.0401 (7)	0.0100 (4)	0.0077 (5)	0.0098 (5)
O1	0.0191 (5)	0.0286 (6)	0.0303 (6)	0.0024 (5)	−0.0056 (5)	−0.0071 (5)
N2	0.0142 (6)	0.0140 (6)	0.0232 (6)	0.0016 (5)	0.0031 (5)	0.0004 (5)
C5	0.0158 (6)	0.0202 (7)	0.0181 (6)	−0.0016 (5)	0.0036 (5)	0.0021 (5)
N1	0.0226 (6)	0.0137 (6)	0.0217 (6)	−0.0008 (5)	0.0062 (5)	0.0027 (5)
C3	0.0158 (6)	0.0156 (6)	0.0123 (6)	0.0011 (5)	0.0036 (5)	0.0026 (5)
C2	0.0152 (6)	0.0182 (7)	0.0176 (6)	0.0024 (5)	0.0028 (5)	0.0032 (5)
O1W	0.0192 (6)	0.0249 (6)	0.0622 (10)	0.0008 (5)	0.0094 (6)	0.0017 (6)
C4	0.0145 (6)	0.0175 (7)	0.0163 (6)	0.0025 (5)	0.0024 (5)	0.0029 (5)
C1	0.0206 (7)	0.0169 (7)	0.0210 (7)	0.0049 (5)	0.0052 (5)	0.0048 (5)
C2A	0.0165 (11)	0.0299 (17)	0.0289 (14)	0.0066 (10)	0.0065 (9)	0.0130 (11)
C1A	0.0165 (11)	0.0299 (17)	0.0289 (14)	0.0066 (10)	0.0065 (9)	0.0130 (11)
C5A	0.0209 (17)	0.016 (3)	0.0340 (19)	0.003 (2)	0.0088 (13)	−0.005 (2)
C4A	0.0193 (15)	0.015 (3)	0.0171 (19)	0.001 (2)	0.0023 (12)	−0.0004 (19)
N2A	0.0209 (11)	0.0122 (13)	0.0214 (11)	0.0026 (8)	0.0036 (8)	−0.0034 (9)
C3A	0.0089 (11)	0.0152 (14)	0.0161 (15)	0.0024 (9)	0.0029 (9)	0.0000 (11)
N1A	0.0228 (13)	0.0104 (15)	0.0475 (19)	0.0020 (11)	0.0117 (12)	0.0029 (15)
N2B	0.0266 (17)	0.0202 (18)	0.0188 (15)	0.0024 (13)	0.0015 (12)	0.0037 (13)
C1B	0.0173 (18)	0.025 (2)	0.036 (3)	−0.0006 (14)	0.0071 (16)	−0.0072 (18)
N1B	0.0165 (16)	0.015 (2)	0.047 (2)	0.0037 (13)	0.0092 (14)	0.004 (2)
C3B	0.0114 (15)	0.020 (2)	0.020 (2)	0.0028 (14)	0.0025 (12)	0.0010 (16)
C4B	0.019 (2)	0.018 (4)	0.016 (2)	0.005 (3)	0.0026 (15)	0.007 (3)
C5B	0.018 (2)	0.017 (4)	0.030 (3)	0.007 (3)	0.0061 (17)	0.008 (2)
C2B	0.0112 (16)	0.029 (3)	0.0062 (16)	0.004 (2)	0.0031 (12)	0.002 (2)

S1—O3	1.4666 (11)	C5A—N1A	1.335 (9)
S1—O2	1.4706 (11)	C5A—C4A	1.345 (5)
S1—O1	1.4849 (12)	C5A—H5AA	0.9300
S1—O4	1.4909 (12)	C4A—C3A	1.422 (6)
N2—C3	1.3311 (18)	C4A—H4AA	0.9300
N2—H1N2	0.86 (2)	N2A—C3A	1.335 (4)
N2—H2N2	0.86 (2)	N2A—H2NA	0.8477
C5—N1	1.354 (2)	N2A—H1NA	0.7856
C5—C4	1.363 (2)	N1A—H1AB	0.8555
C5—H5A	0.9300	N2B—C3B	1.321 (6)
N1—C1	1.355 (2)	N2B—H1NB	0.8900
N1—H1N1	0.88 (2)	N2B—H2NB	0.8295
C3—C4	1.4208 (19)	C1B—N1B	1.339 (6)
C3—C2	1.421 (2)	C1B—C2B	1.352 (6)
C2—C1	1.362 (2)	C1B—H1BB	0.8750
C2—H2A	0.9300	N1B—C5B	1.367 (11)
O1W—H1W1	0.91 (3)	N1B—H2NA	1.1125
O1W—H2W1	0.83 (3)	N1B—H1BA	0.8600
C4—H4A	0.9300	C3B—C4B	1.443 (8)
C1—H1A	0.9300	C3B—C2B	1.456 (8)
C2A—C1A	1.366 (6)	C4B—C5B	1.334 (7)
C2A—C3A	1.381 (8)	C4B—H4BA	0.9300
C2A—H2AA	0.9300	C5B—H5BA	0.9300
C1A—N1A	1.347 (5)	C2B—H2BA	0.9300
C1A—H1AA	0.9300
O3—S1—O2	110.89 (7)	H1NA—N2A—H1BB	46.1
O3—S1—O1	109.12 (7)	C3A—N2A—H1BA	102.2
O2—S1—O1	109.99 (7)	H1NA—N2A—H1BA	138.1
O3—S1—O4	109.09 (7)	H1BB—N2A—H1BA	175.5
O2—S1—O4	109.35 (7)	N2A—C3A—C2A	122.9 (4)
O1—S1—O4	108.35 (7)	N2A—C3A—C4A	121.2 (4)
C3—N2—H1N2	119.4 (15)	C2A—C3A—C4A	115.9 (4)
C3—N2—H2N2	118.3 (13)	C2A—C3A—H1BA	145.0
H1N2—N2—H2N2	121.9 (19)	C4A—C3A—H1BA	99.1
N1—C5—C4	121.14 (13)	C5A—N1A—C1A	120.9 (4)
N1—C5—H5A	119.4	C5A—N1A—H1AB	113.9
C4—C5—H5A	119.4	C1A—N1A—H1AB	125.2
C5—N1—C1	120.88 (13)	C5A—N1A—H2NB	114.7
C5—N1—H1N1	119.8 (15)	C1A—N1A—H2NB	124.4
C1—N1—H1N1	118.7 (14)	C3B—N2B—H1AB	98.6
N2—C3—C4	121.37 (13)	C3B—N2B—H1NB	123.7
N2—C3—C2	121.41 (13)	H1AB—N2B—H1NB	136.0
C4—C3—C2	117.21 (13)	C3B—N2B—H2NB	117.9
C1—C2—H2A	120.0	H1NB—N2B—H2NB	116.1
C3—C2—H2A	120.0	N1B—C1B—C2B	123.4 (5)
H1W1—O1W—H2W1	114 (3)	N1B—C1B—H1NA	65.4
C5—C4—C3	119.81 (13)	C2B—C1B—H1NA	171.1
C5—C4—H4A	120.1	N1B—C1B—H1BB	108.0
C3—C4—H4A	120.1	C2B—C1B—H1BB	128.3
N1—C1—C2	120.94 (14)	C1B—N1B—C5B	119.7 (5)
N1—C1—H1A	119.5	C1B—N1B—H2NA	126.9
C2—C1—H1A	119.5	C5B—N1B—H2NA	113.3
C1A—C2A—C3A	121.7 (7)	C1B—N1B—H1BA	120.0
C1A—C2A—H2AA	119.1	C5B—N1B—H1BA	120.3
C3A—C2A—H2AA	119.1	N2B—C3B—C4B	120.9 (5)
N1A—C1A—C2A	119.7 (5)	N2B—C3B—C2B	122.3 (4)
N1A—C1A—H1AA	120.1	C4B—C3B—C2B	116.8 (5)
C2A—C1A—H1AA	120.1	C4B—C3B—H1AB	96.6
N1A—C5A—C4A	121.2 (6)	C2B—C3B—H1AB	146.6
N1A—C5A—H5AA	119.4	C5B—C4B—C3B	119.5 (6)
C4A—C5A—H5AA	119.4	C5B—C4B—H4BA	120.2
C5A—C4A—C3A	120.6 (5)	C3B—C4B—H4BA	120.2
C5A—C4A—H4AA	119.7	C4B—C5B—N1B	122.4 (7)
C3A—C4A—H4AA	119.7	C4B—C5B—H5BA	118.8
C3A—N2A—H2NA	113.5	N1B—C5B—H5BA	118.8
C3A—N2A—H1NA	119.5	C1B—C2B—C3B	118.2 (5)
H2NA—N2A—H1NA	127.0	C1B—C2B—H2BA	120.9
C3A—N2A—H1BB	73.5	C3B—C2B—H2BA	120.9
H2NA—N2A—H1BB	172.0
C4—C5—N1—C1	0.7 (2)	C5A—C4A—C3A—N2A	179.3 (4)
N2—C3—C2—C1	−177.42 (14)	C5A—C4A—C3A—C2A	−1.6 (7)
C4—C3—C2—C1	2.2 (2)	C4A—C5A—N1A—C1A	0.7 (7)
N1—C5—C4—C3	0.4 (2)	C2A—C1A—N1A—C5A	−0.5 (7)
N2—C3—C4—C5	177.75 (13)	C2B—C1B—N1B—C5B	0.1 (8)
C2—C3—C4—C5	−1.9 (2)	N2B—C3B—C4B—C5B	179.5 (5)
C5—N1—C1—C2	−0.4 (2)	C2B—C3B—C4B—C5B	0.6 (8)
C3—C2—C1—N1	−1.1 (2)	C3B—C4B—C5B—N1B	−0.3 (10)
C3A—C2A—C1A—N1A	−0.9 (8)	C1B—N1B—C5B—C4B	0.0 (9)
N1A—C5A—C4A—C3A	0.3 (8)	N1B—C1B—C2B—C3B	0.2 (8)
C1A—C2A—C3A—N2A	−179.1 (4)	N2B—C3B—C2B—C1B	−179.4 (5)
C1A—C2A—C3A—C4A	1.8 (8)	C4B—C3B—C2B—C1B	−0.5 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2NA···O1i	0.85	2.03	2.822 (3)	156.
N2A—H1NA···O1Wii	0.79	2.07	2.812 (3)	159.
N1A—H1AB···O1iii	0.86	2.20	2.938 (4)	144.
O1W—H1W1···O2iv	0.91 (3)	1.88 (3)	2.7952 (19)	176 (3)
O1W—H2W1···O1v	0.83 (3)	2.00 (3)	2.8195 (18)	167 (2)
N1—H1N1···O4iv	0.88 (3)	1.85 (2)	2.7102 (17)	165 (2)
N2—H1N2···O4	0.86 (3)	2.01 (3)	2.8665 (17)	176 (2)
N2—H2N2···O3vi	0.862 (19)	1.96 (2)	2.8118 (17)	167.9 (16)
C1—H1A···O2vii	0.93	2.46	3.3688 (18)	167.
C1A—H1AA···O1Wviii	0.93	2.58	3.318 (4)	137.
C5A—H5AA···O2iii	0.93	2.44	3.228 (7)	143.
C4A—H4AA···O3i	0.93	2.54	3.362 (6)	147.
C5—H5A···O4i	0.93	2.52	3.3360 (18)	146.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2NA⋯O1i	0.85	2.03	2.822 (3)	156
N2A—H1NA⋯O1Wii	0.79	2.07	2.812 (3)	159
N1A—H1AB⋯O1iii	0.86	2.20	2.938 (4)	144
O1W—H1W1⋯O2iv	0.91 (3)	1.88 (3)	2.7952 (19)	176 (3)
O1W—H2W1⋯O1v	0.83 (3)	2.00 (3)	2.8195 (18)	167 (2)
N1—H1N1⋯O4iv	0.88 (3)	1.85 (2)	2.7102 (17)	165 (2)
N2—H1N2⋯O4	0.86 (3)	2.01 (3)	2.8665 (17)	176 (2)
N2—H2N2⋯O3vi	0.862 (19)	1.96 (2)	2.8118 (17)	167.9 (16)
C1—H1A⋯O2vii	0.93	2.46	3.3688 (18)	167
C1A—H1AA⋯O1Wviii	0.93	2.58	3.318 (4)	137
C5A—H5AA⋯O2iii	0.93	2.44	3.228 (7)	143
C4A—H4AA⋯O3i	0.93	2.54	3.362 (6)	147
C5—H5A⋯O4i	0.93	2.52	3.3360 (18)	146

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