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

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028978/dn2197sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028978/dn2197Isup2.hkl
Contains datablock I

CCDC reference: 654990

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

No syntax errors found



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

Comment top

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 top

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).

Experimental top

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).

Refinement top

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 [Uiso (H) = 1.5Ueq(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 Uiso = 1.2Ueq(C).

Structure description top

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.

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).

Computing details top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. Partial packing view showing the three dimensionnal hydrogen-bonding network.
3-Hydroxyanilinium hydrogensulfate top
Crystal data top
C6H8NO+·HSO4F(000) = 216
Mr = 207.21Dx = 1.641 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 5862 reflections
a = 7.3142 (3) Åθ = 2.1–30.0°
b = 5.8612 (2) ŵ = 0.38 mm1
c = 9.8969 (2) ÅT = 293 K
β = 98.829 (2)°Prism, colourless
V = 419.25 (2) Å30.15 × 0.12 × 0.10 mm
Z = 2
Data collection top
Nonius KappaCCD area-detector
diffractometer
2150 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.043
Graphite monochromatorθmax = 30.0°, θmin = 2.1°
ω/θ scansh = 810
5851 measured reflectionsk = 78
2241 independent reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0598P)2 + 0.051P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.001
2241 reflectionsΔρmax = 0.32 e Å3
121 parametersΔρmin = 0.45 e Å3
1 restraintAbsolute structure: Flack (1983), with 1095 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (8)
Crystal data top
C6H8NO+·HSO4V = 419.25 (2) Å3
Mr = 207.21Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.3142 (3) ŵ = 0.38 mm1
b = 5.8612 (2) ÅT = 293 K
c = 9.8969 (2) Å0.15 × 0.12 × 0.10 mm
β = 98.829 (2)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
2150 reflections with I > 2σ(I)
5851 measured reflectionsRint = 0.043
2241 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.099Δρmax = 0.32 e Å3
S = 1.14Δρmin = 0.45 e Å3
2241 reflectionsAbsolute structure: Flack (1983), with 1095 Friedel pairs
121 parametersAbsolute structure parameter: 0.02 (8)
1 restraint
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.2336 (2)0.1606 (4)0.28583 (15)0.0237 (3)
C20.3143 (3)0.3498 (4)0.35270 (18)0.0280 (4)
H20.35870.46750.30370.034*
C30.3287 (3)0.3631 (3)0.49435 (19)0.0281 (4)
H30.38240.49020.54080.034*
C40.2629 (2)0.1865 (4)0.56539 (15)0.0249 (3)
C50.1808 (3)0.0052 (4)0.4976 (2)0.0310 (4)
H50.13670.12340.54630.037*
C60.1661 (3)0.0165 (4)0.35594 (19)0.0297 (4)
H60.11120.14240.30880.036*
N10.2226 (2)0.1419 (3)0.13659 (15)0.0271 (3)
H1A0.23430.27980.10120.041*
H1B0.11370.08260.10110.041*
H1C0.31300.05200.11710.041*
O410.2772 (3)0.1876 (3)0.70515 (13)0.0385 (3)
H410.29660.31810.73360.058*
O20.8476 (2)0.0097 (3)0.04947 (17)0.0373 (4)
O10.8468 (2)0.3880 (3)0.13117 (15)0.0333 (3)
H10.80850.45450.19410.050*
O30.5869 (2)0.2501 (3)0.03018 (17)0.0474 (5)
O40.6326 (2)0.1115 (3)0.20212 (15)0.0334 (3)
S10.71804 (5)0.17750 (8)0.08525 (3)0.02299 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0227 (6)0.0291 (9)0.0187 (6)0.0027 (8)0.0019 (5)0.0021 (7)
C20.0348 (10)0.0259 (9)0.0246 (8)0.0047 (8)0.0085 (7)0.0005 (7)
C30.0340 (9)0.0245 (9)0.0260 (8)0.0040 (7)0.0056 (7)0.0035 (7)
C40.0294 (7)0.0255 (8)0.0202 (6)0.0047 (9)0.0046 (5)0.0006 (8)
C50.0390 (10)0.0290 (10)0.0253 (8)0.0072 (8)0.0061 (7)0.0017 (7)
C60.0341 (10)0.0280 (10)0.0261 (8)0.0056 (8)0.0015 (7)0.0035 (7)
N10.0283 (6)0.0325 (10)0.0202 (6)0.0031 (7)0.0029 (5)0.0008 (6)
O410.0659 (9)0.0314 (7)0.0192 (5)0.0074 (9)0.0092 (5)0.0022 (6)
O20.0310 (7)0.0397 (9)0.0432 (8)0.0016 (7)0.0120 (6)0.0167 (7)
O10.0339 (7)0.0315 (8)0.0366 (7)0.0064 (6)0.0115 (6)0.0055 (6)
O30.0462 (9)0.0469 (9)0.0423 (8)0.0053 (8)0.0144 (7)0.0167 (7)
O40.0407 (7)0.0331 (8)0.0303 (6)0.0025 (6)0.0176 (6)0.0004 (5)
S10.02315 (18)0.0258 (2)0.02035 (18)0.00081 (18)0.00441 (12)0.00186 (16)
Geometric parameters (Å, º) top
C1—C21.377 (3)C6—H60.9300
C1—C61.382 (3)N1—H1A0.8900
C1—N11.4709 (19)N1—H1B0.8900
C2—C31.392 (3)N1—H1C0.8900
C2—H20.9300O41—H410.8200
C3—C41.379 (3)O2—S11.4467 (16)
C3—H30.9300O1—S11.5759 (15)
C4—O411.3710 (18)O1—H10.8200
C4—C51.396 (3)O3—S11.4389 (15)
C5—C61.391 (3)O4—S11.4491 (14)
C5—H50.9300
C2—C1—C6121.59 (15)C1—C6—H6120.3
C2—C1—N1119.74 (18)C5—C6—H6120.3
C6—C1—N1118.66 (18)C1—N1—H1A109.5
C1—C2—C3119.31 (17)C1—N1—H1B109.5
C1—C2—H2120.3H1A—N1—H1B109.5
C3—C2—H2120.3C1—N1—H1C109.5
C4—C3—C2119.56 (17)H1A—N1—H1C109.5
C4—C3—H3120.2H1B—N1—H1C109.5
C2—C3—H3120.2C4—O41—H41109.5
O41—C4—C3122.2 (2)S1—O1—H1109.5
O41—C4—C5116.7 (2)O3—S1—O2112.88 (11)
C3—C4—C5121.13 (16)O3—S1—O4113.33 (10)
C6—C5—C4118.94 (19)O2—S1—O4113.12 (10)
C6—C5—H5120.5O3—S1—O1107.06 (10)
C4—C5—H5120.5O2—S1—O1102.60 (9)
C1—C6—C5119.47 (18)O4—S1—O1106.89 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.892.032.830 (2)149
N1—H1B···O2ii0.891.982.853 (2)166
N1—H1C···O3iii0.892.142.962 (2)152
N1—H1C···O40.892.392.975 (2)124
O41—H41···O4iv0.821.882.695 (2)174
O1—H1···O41iv0.821.862.642 (2)160
Symmetry codes: (i) x+1, y+1/2, z; (ii) x1, y, z; (iii) x+1, y1/2, z; (iv) x+1, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC6H8NO+·HSO4
Mr207.21
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)7.3142 (3), 5.8612 (2), 9.8969 (2)
β (°) 98.829 (2)
V3)419.25 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.15 × 0.12 × 0.10
Data collection
DiffractometerNonius KappaCCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5851, 2241, 2150
Rint0.043
(sin θ/λ)max1)0.702
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.099, 1.14
No. of reflections2241
No. of parameters121
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.45
Absolute structureFlack (1983), with 1095 Friedel pairs
Absolute structure parameter0.02 (8)

Computer programs: KappaCCD Server Software (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.892.032.830 (2)148.9
N1—H1B···O2ii0.891.982.853 (2)165.9
N1—H1C···O3iii0.892.142.962 (2)152.4
N1—H1C···O40.892.392.975 (2)123.9
O41—H41···O4iv0.821.882.695 (2)174.0
O1—H1···O41iv0.821.862.642 (2)160.2
Symmetry codes: (i) x+1, y+1/2, z; (ii) x1, y, z; (iii) x+1, y1/2, z; (iv) x+1, y+1/2, z+1.
 

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