3-Hydroxy­anilinium hydrogensulfate

In the title compound, C₆H₈NO⁺·HSO₄^-, there is an intricate cation-cation, cation-anion and anion-anion three-dimensional hydrogen-bond network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.099
• Data-to-parameter ratio = 18.5

checkCIF/PLATON results

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Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           29.95
           From the CIF: _reflns_number_total               2420
           Count of symmetry unique reflns         1325
           Completeness (_total/calc)            182.64%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1095
           Fraction of Friedel pairs measured     0.826
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   0 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Crystal engineering of organic-inorganic hybrid compounds is currently of great interest and these matrials have received increasing attention during the past few decades (Mazeaud et al., 2000; Soghomonian et al., 1995) owing to their interesting structural topologies and potential application in materials science, such as ion-exchange, adsorption, molecular recognition, catalysis and magnetism (Aakeroy et al., 1999; Hagrman et al., 1999). The crystal structure of m-hydroxyanilinuim bisulfate, (I), was determined as part of our investigations on the structural characteristics of organic-inorganic layered compounds and an ongoing study on D—H···A hydrogen-bonding in systems of hybrid materials including anilinium derivatives such as 4-Carboxyanilinium hydrogensulfate (Benali-Cherif, Direm et al., 2007), 2-carboxyanilinium dihydrogenphosphate (Benali-Cherif, Allouche et al., 2007) and m-Carboxyphenylanilinium bisulfate (Cherouana, et al., 2003),

The asymmetric unit of (I) contains a monoprotonated p-hydroxyanilinium cation and bisulfate anion (Figure 1). Intra atomic bond distance and angles in the title compound shows the monprotonation of the organic entity and confirms the presence of the bisulfate (HSO₄^-) anion.

The crystal structure of the title compound is built up from intricate cation-cation, cation-anion and anion-anion hydrogen-bonds interaction in a three-dimensional network. Strong and moderate N—H···N, N—H···O, O—H···O hydrogen bonding ensure the cohesion of the crystal through the formation of three-dimensional hydrogen bond network and the strongest one are observed between cation and anion (O41—H···O4 2.695 (2) Å, (O1—H1···O41 2.642 (2) Å)). Principal hydrogen bonding values are listed in Table 1, and the interactions are illustrated in Fig. 2.

Related literature

For related literature, see: Aakeroy et al. (1999); Benali-Cherif, Allouche et al. (2007); Benali-Cherif, Direm et al. (2007); Cherouana et al. (2003); Hagrman et al. (1999); Mazeaud et al. (2000); Soghomonian et al. (1995).

S2. Experimental

Single crystals of the title compound are prepared by slow evaporation at room temperature of an aqueous solution of 4-hydroxyaniline acid C₆H₇NO and sulfate acid (H₂SO₄).

S3. Refinement

The OH and NH₃ H-atoms of the anion and cation entities were located in difference Fourier syntheses and refined as riding atoms with distances constraints of N—H = 0.89 Å and O—H = 0.82 Å [U_iso (H) = 1.5U_eq(N,O)]. Aromatic H atoms were located in difference Fourier syntheses and were allowed to ride on their parent C atoms with C—H = 0.93 Å and U_iso = 1.2U_eq(C).

Computing details

Data collection: KappaCCD Server Software (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. View of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H bond is shown as dashed line. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the three dimensionnal hydrogen-bonding network.

3-Hydroxyanilinium hydrogensulfate

Crystal data

C6H8NO^+·HSO4^−	F(000) = 216
Mr = 207.21	Dx = 1.641 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5862 reflections
a = 7.3142 (3) Å	θ = 2.1–30.0°
b = 5.8612 (2) Å	µ = 0.38 mm^−1
c = 9.8969 (2) Å	T = 293 K
β = 98.829 (2)°	Prism, colourless
V = 419.25 (2) Å^3	0.15 × 0.12 × 0.10 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	2150 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 30.0°, θmin = 2.1°
ω/θ scans	h = −8→10
5851 measured reflections	k = −7→8
2241 independent reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0598P)^2 + 0.051P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.001
2241 reflections	Δρmax = 0.32 e Å^−3
121 parameters	Δρmin = −0.45 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1095 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (8)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2336 (2)	0.1606 (4)	0.28583 (15)	0.0237 (3)
C2	0.3143 (3)	0.3498 (4)	0.35270 (18)	0.0280 (4)
H2	0.3587	0.4675	0.3037	0.034*
C3	0.3287 (3)	0.3631 (3)	0.49435 (19)	0.0281 (4)
H3	0.3824	0.4902	0.5408	0.034*
C4	0.2629 (2)	0.1865 (4)	0.56539 (15)	0.0249 (3)
C5	0.1808 (3)	−0.0052 (4)	0.4976 (2)	0.0310 (4)
H5	0.1367	−0.1234	0.5463	0.037*
C6	0.1661 (3)	−0.0165 (4)	0.35594 (19)	0.0297 (4)
H6	0.1112	−0.1424	0.3088	0.036*
N1	0.2226 (2)	0.1419 (3)	0.13659 (15)	0.0271 (3)
H1A	0.2343	0.2798	0.1012	0.041*
H1B	0.1137	0.0826	0.1011	0.041*
H1C	0.3130	0.0520	0.1171	0.041*
O41	0.2772 (3)	0.1876 (3)	0.70515 (13)	0.0385 (3)
H41	0.2966	0.3181	0.7336	0.058*
O2	0.8476 (2)	0.0097 (3)	0.04947 (17)	0.0373 (4)
O1	0.8468 (2)	0.3880 (3)	0.13117 (15)	0.0333 (3)
H1	0.8085	0.4545	0.1941	0.050*
O3	0.5869 (2)	0.2501 (3)	−0.03018 (17)	0.0474 (5)
O4	0.6326 (2)	0.1115 (3)	0.20212 (15)	0.0334 (3)
S1	0.71804 (5)	0.17750 (8)	0.08525 (3)	0.02299 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0227 (6)	0.0291 (9)	0.0187 (6)	0.0027 (8)	0.0019 (5)	−0.0021 (7)
C2	0.0348 (10)	0.0259 (9)	0.0246 (8)	−0.0047 (8)	0.0085 (7)	0.0005 (7)
C3	0.0340 (9)	0.0245 (9)	0.0260 (8)	−0.0040 (7)	0.0056 (7)	−0.0035 (7)
C4	0.0294 (7)	0.0255 (8)	0.0202 (6)	0.0047 (9)	0.0046 (5)	−0.0006 (8)
C5	0.0390 (10)	0.0290 (10)	0.0253 (8)	−0.0072 (8)	0.0061 (7)	0.0017 (7)
C6	0.0341 (10)	0.0280 (10)	0.0261 (8)	−0.0056 (8)	0.0015 (7)	−0.0035 (7)
N1	0.0283 (6)	0.0325 (10)	0.0202 (6)	0.0031 (7)	0.0029 (5)	−0.0008 (6)
O41	0.0659 (9)	0.0314 (7)	0.0192 (5)	−0.0074 (9)	0.0092 (5)	−0.0022 (6)
O2	0.0310 (7)	0.0397 (9)	0.0432 (8)	0.0016 (7)	0.0120 (6)	−0.0167 (7)
O1	0.0339 (7)	0.0315 (8)	0.0366 (7)	−0.0064 (6)	0.0115 (6)	−0.0055 (6)
O3	0.0462 (9)	0.0469 (9)	0.0423 (8)	−0.0053 (8)	−0.0144 (7)	0.0167 (7)
O4	0.0407 (7)	0.0331 (8)	0.0303 (6)	−0.0025 (6)	0.0176 (6)	0.0004 (5)
S1	0.02315 (18)	0.0258 (2)	0.02035 (18)	0.00081 (18)	0.00441 (12)	0.00186 (16)

Geometric parameters (Å, º)

C1—C2	1.377 (3)	C6—H6	0.9300
C1—C6	1.382 (3)	N1—H1A	0.8900
C1—N1	1.4709 (19)	N1—H1B	0.8900
C2—C3	1.392 (3)	N1—H1C	0.8900
C2—H2	0.9300	O41—H41	0.8200
C3—C4	1.379 (3)	O2—S1	1.4467 (16)
C3—H3	0.9300	O1—S1	1.5759 (15)
C4—O41	1.3710 (18)	O1—H1	0.8200
C4—C5	1.396 (3)	O3—S1	1.4389 (15)
C5—C6	1.391 (3)	O4—S1	1.4491 (14)
C5—H5	0.9300
C2—C1—C6	121.59 (15)	C1—C6—H6	120.3
C2—C1—N1	119.74 (18)	C5—C6—H6	120.3
C6—C1—N1	118.66 (18)	C1—N1—H1A	109.5
C1—C2—C3	119.31 (17)	C1—N1—H1B	109.5
C1—C2—H2	120.3	H1A—N1—H1B	109.5
C3—C2—H2	120.3	C1—N1—H1C	109.5
C4—C3—C2	119.56 (17)	H1A—N1—H1C	109.5
C4—C3—H3	120.2	H1B—N1—H1C	109.5
C2—C3—H3	120.2	C4—O41—H41	109.5
O41—C4—C3	122.2 (2)	S1—O1—H1	109.5
O41—C4—C5	116.7 (2)	O3—S1—O2	112.88 (11)
C3—C4—C5	121.13 (16)	O3—S1—O4	113.33 (10)
C6—C5—C4	118.94 (19)	O2—S1—O4	113.12 (10)
C6—C5—H5	120.5	O3—S1—O1	107.06 (10)
C4—C5—H5	120.5	O2—S1—O1	102.60 (9)
C1—C6—C5	119.47 (18)	O4—S1—O1	106.89 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.89	2.03	2.830 (2)	149
N1—H1B···O2^ii	0.89	1.98	2.853 (2)	166
N1—H1C···O3^iii	0.89	2.14	2.962 (2)	152
N1—H1C···O4	0.89	2.39	2.975 (2)	124
O41—H41···O4^iv	0.82	1.88	2.695 (2)	174
O1—H1···O41^iv	0.82	1.86	2.642 (2)	160

Symmetry codes: (i) −x+1, y+1/2, −z; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z; (iv) −x+1, y+1/2, −z+1.