2-Hy­droxy­benzenaminium acetate

Moussa Slimane, N.; Benarous, N.; Bougueria, H.; Cherouana, A.

doi:10.1107/S2414314622001122

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 2| February 2022| x220112

https://doi.org/10.1107/S2414314622001122

Open

access

2-Hydroxybenzenaminium acetate

Nabila Moussa Slimane,^a Nesrine Benarous,^a ^* Hassiba Bougueria ^a,^b and Aouatef Cherouana ^a

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Département de Chimie, Université des Frères Mentouri, Constantine-1, 25017 Constantine, Algeria, and ^bCentre Universitaire Abd El Hafid Boussouf, Mila, 43000 Mila, Algeria
^*Correspondence e-mail: nesrine.benarous@umc.edu.dz

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 12 January 2022; accepted 31 January 2022; online 3 February 2022)

In the title molecular salt, C₆H₈NO⁺·C₂H₃O₂⁻, the cations and anions are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating a three-dimensional network.

Keywords: crystal structure; 2-hydroxybenzenaminium cation; acetate anion; hydrogen bond.

CCDC reference: 2149479

Structure description

In recent years, substituted anilines and their derivatives have been studied extensively for applications as antibacterials and in non-linear optical systems (Vivek & Murugakoothan, 2014 ). Aminophenols containing equal stoichiometries of –OH, and –NH₂ groups have been widely studied to understand the supramolecular synthons existing in their assemblies (Allen et al., 1997 ; Dey et al., 2004 ).

In spite of this interest, there has been very little structural characterization of ortho-hydroxyanilinium salts. The structures reported include 2-hydroxyanilinium squarate (Yeşilel, 2007 ), 2-hydroxyanilinium hydrogen phthalate (Jagan & Sivakumar, 2009 ), 2-hydroxyanilinium 3,5-dinitrosalicylate (Smith et al., 2011 ), 2-hydroxyanilinium 3,5-dinitrobenzoate (Zhao, 2012 ), and 2-hydroxyanilinium 2-hydroxy-5-nitrobenzoate and 2-hydroxyanilinium 3,5-dinitrobenzoate (Jin & Wang, 2013 ).

Here, we report the structure of 2-hydroxybenzenaminium acetate, C₆H₈NO⁺·C₂H₃O₂⁻, 1, obtained from the reaction of 2-hydroxyaniline and acetic acid. The molecular structure of the title compound is shown in Fig.1. The asymmetric unit contains one 2-hydroxybenzenaminium cation and one acetate anion. The cation is protonated at the amine N atom (N1) and linked to the anion by an N—H⋯O hydrogen bond (Fig. 1 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.894 (14)	1.709 (14)	2.6025 (9)	177.8 (16)
N1—H1A⋯O2	0.930 (13)	1.807 (13)	2.7251 (9)	168.7 (12)
N1—H1B⋯O2ⁱⁱ	0.923 (12)	1.891 (12)	2.8019 (9)	168.8 (11)
N1—H1C⋯O3ⁱⁱⁱ	0.935 (12)	1.834 (12)	2.7531 (8)	167.2 (12)
C6—H6⋯O3ⁱⁱⁱ	0.95	2.55	3.2493 (11)	131
Symmetry codes: (i) x, y+1, z; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
Diagram showing the C₆H₈NO⁺ cation and C₂H₃O₂⁻ anion linked by an N—H⋯O interaction (shown as a dashed line). Displacement ellipsoids are drawn at the 50% probability level.

The best planes through the 2-hydroxybenzenaminium cation and acetate anion are almost perpendicular to each other, subtending a dihedral angle of 79.23 (4)°. The C—OH bond length (C2—O1) of 1.3520 (9) Å is similar to that observed for structures containing 2-hydroxybenzenaminium as a cation [1.350 (3) Å; Jin & Wang, 2013]. All bond lengths and angles in the 2-hydroxybenzenaminium cation are within normal ranges (Zhao, 2012).

The presence of hydroxyl groups leads to the formation of intermolecular O1—H1⋯O3 hydrogen bonds. The O1—H1⋯O3 and N1—H1C⋯O3 cation–anion hydrogen bonds generate a succession of infinite chains [graph set C₂¹(7)] that propagate in a zigzag manner along the c-axis direction (Fig. 2 and Table 1). The N1—H1A⋯O2 hydrogen bonds (Table 1) link the chains into corrugated layers parallel to the bc plane, which are formed by a succession of R₆⁵(22) rings (Fig. 2). N1—H1B⋯O2 hydrogen bonds lead to the formation of a three-dimensional network (Fig. 3). No significant π–π stacking interactions were observed, despite the presence of an aromatic ring in the cation.

Figure 2
A portion of one corrugated layer viewed along the b-axis direction. O—H\⋯O and N—H⋯O hydrogen bonds are shown as dashed lines.

Figure 3
View of two layers viewed along the b- and c-axis directions.

Synthesis and crystallization

The title compound was prepared by heating of a mixture of 2-aminophenol (Alfa Aesar, purity 98%) and acetic acid. This mixture was obtained by dissolution and agitation under reflux for 3 h of 0.5 g of the 2-aminophenol and 0.27 g of acetic acid in a 1:1 stoichiometric ratio in a hot ethanolic solution (20 ml). After warming for a few minutes using a water bath, the solution was cooled and kept at room temperature. Within a few days, yellow needle-like crystals suitable for the X-ray analysis were obtained (yield 60%) by evaporation of the solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₈NO⁺·C₂H₃O₂⁻
M_r	169.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.9150 (2), 7.2523 (2), 11.9573 (3)
β (°)	98.558 (2)
V (Å³)	850.23 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire2 CCD
Absorption correction	Integration (ABSORB; DeTitta, 1985 )
T_min, T_max	0.966, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	52913, 3105, 2736
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.766

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 1.05
No. of reflections	3105
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.27
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2149479

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622001122/vm4050sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622001122/vm4050Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622001122/vm4050Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-Hydroxybenzenaminium acetate top

Crystal data top

C₆H₈NO⁺·C₂H₃O₂⁻	F(000) = 360
M_r = 169.18	D_x = 1.322 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.9150 (2) Å	Cell parameters from 52927 reflections
b = 7.2523 (2) Å	θ = 3.3–33.0°
c = 11.9573 (3) Å	µ = 0.10 mm⁻¹
β = 98.558 (2)°	T = 100 K
V = 850.23 (4) Å³	Prism, yellow
Z = 4	0.1 × 0.1 × 0.08 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire2 CCD diffractometer	2736 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.038
Absorption correction: integration (ABSORB; DeTitta, 1985)	θ_max = 33.0°, θ_min = 3.3°
T_min = 0.966, T_max = 0.991	h = −15→15
52913 measured reflections	k = −11→11
3105 independent reflections	l = −17→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0542P)² + 0.320P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3105 reflections	Δρ_max = 0.49 e Å⁻³
122 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The hydrogen atoms of the NH₃ and hydroxyl groups were localized in the difference-Fourier map and refined with U_iso(H) set to 1.5U_eq(O) or 1.2U_eq(N). All the other hydrogen atoms were placed in calculated positions with C—H = 0.95 Å for aromatic CH and C—H = 0.96 Å for CH₃ and refined using a riding model with fixed isotropic displacement parameters [U_iso(H) = 1.2U_eq(C-aromatic) and U_iso(H) = 1.5U_eq(C-methyl)].

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.12872 (6)	0.83288 (9)	0.65994 (5)	0.01629 (13)
H1	0.1381 (14)	0.928 (2)	0.6142 (12)	0.024*
O2	0.09592 (7)	0.29888 (8)	0.65411 (5)	0.01686 (13)
O3	0.15033 (7)	0.10731 (8)	0.52349 (5)	0.01664 (13)
N1	0.12133 (7)	0.56570 (9)	0.81635 (5)	0.01242 (13)
H1A	0.1133 (12)	0.4870 (19)	0.7543 (10)	0.015*
H1B	0.0461 (12)	0.6407 (18)	0.8160 (10)	0.015*
H1C	0.1280 (12)	0.4909 (18)	0.8806 (10)	0.015*
C3	0.35594 (9)	0.93249 (12)	0.74235 (7)	0.01774 (16)
H3	0.358215	1.025256	0.686567	0.021*
C5	0.46510 (9)	0.77468 (13)	0.90970 (8)	0.01994 (17)
H5	0.540747	0.760726	0.967953	0.024*
C4	0.46648 (9)	0.91021 (13)	0.82754 (8)	0.02042 (17)
H4	0.543738	0.988327	0.829677	0.025*
C2	0.24139 (8)	0.81883 (11)	0.73847 (6)	0.01328 (14)
C6	0.35205 (8)	0.65957 (12)	0.90596 (7)	0.01606 (15)
H6	0.350402	0.566114	0.961414	0.019*
C1	0.24197 (8)	0.68208 (10)	0.82091 (6)	0.01217 (14)
C8	0.13683 (8)	0.26870 (11)	0.56096 (6)	0.01288 (14)
C7	0.16938 (9)	0.42886 (12)	0.48900 (8)	0.01940 (16)
H7A	0.096016	0.443787	0.425025	0.029*
H7B	0.255531	0.405118	0.460661	0.029*
H7C	0.177717	0.541719	0.534587	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0172 (3)	0.0157 (3)	0.0153 (3)	−0.0014 (2)	0.0001 (2)	0.0046 (2)
O2	0.0220 (3)	0.0142 (3)	0.0157 (3)	−0.0024 (2)	0.0073 (2)	−0.0030 (2)
O3	0.0255 (3)	0.0124 (3)	0.0124 (2)	0.0019 (2)	0.0041 (2)	−0.00051 (19)
N1	0.0147 (3)	0.0109 (3)	0.0120 (3)	−0.0006 (2)	0.0030 (2)	0.0005 (2)
C3	0.0180 (3)	0.0161 (3)	0.0198 (4)	−0.0030 (3)	0.0053 (3)	0.0024 (3)
C5	0.0150 (3)	0.0222 (4)	0.0217 (4)	−0.0007 (3)	−0.0003 (3)	0.0001 (3)
C4	0.0154 (3)	0.0212 (4)	0.0248 (4)	−0.0040 (3)	0.0036 (3)	0.0000 (3)
C2	0.0149 (3)	0.0121 (3)	0.0131 (3)	0.0002 (2)	0.0032 (2)	0.0005 (2)
C6	0.0162 (3)	0.0160 (3)	0.0157 (3)	0.0013 (3)	0.0015 (3)	0.0011 (3)
C1	0.0133 (3)	0.0110 (3)	0.0126 (3)	−0.0001 (2)	0.0033 (2)	0.0000 (2)
C8	0.0128 (3)	0.0123 (3)	0.0135 (3)	0.0001 (2)	0.0019 (2)	0.0007 (2)
C7	0.0213 (4)	0.0154 (3)	0.0229 (4)	0.0008 (3)	0.0078 (3)	0.0063 (3)

Geometric parameters (Å, º) top

O1—H1	0.892 (14)	C5—H5	0.9500
O1—C2	1.3520 (9)	C5—C4	1.3912 (13)
O2—C8	1.2600 (9)	C5—C6	1.3930 (12)
O3—C8	1.2675 (9)	C4—H4	0.9500
N1—H1A	0.930 (13)	C2—C1	1.3978 (11)
N1—H1B	0.922 (13)	C6—H6	0.9500
N1—H1C	0.935 (12)	C6—C1	1.3863 (11)
N1—C1	1.4583 (10)	C8—C7	1.5087 (11)
C3—H3	0.9500	C7—H7A	0.9800
C3—C4	1.3903 (12)	C7—H7B	0.9800
C3—C2	1.3985 (11)	C7—H7C	0.9800

C2—O1—H1	109.4 (9)	O1—C2—C1	117.36 (7)
H1A—N1—H1B	112.7 (11)	C1—C2—C3	118.48 (7)
H1A—N1—H1C	106.7 (11)	C5—C6—H6	120.2
H1B—N1—H1C	107.7 (10)	C1—C6—C5	119.66 (8)
C1—N1—H1A	110.9 (8)	C1—C6—H6	120.2
C1—N1—H1B	108.5 (8)	C2—C1—N1	117.84 (7)
C1—N1—H1C	110.3 (7)	C6—C1—N1	120.74 (7)
C4—C3—H3	119.9	C6—C1—C2	121.40 (7)
C4—C3—C2	120.24 (8)	O2—C8—O3	122.53 (7)
C2—C3—H3	119.9	O2—C8—C7	119.65 (7)
C4—C5—H5	120.2	O3—C8—C7	117.81 (7)
C4—C5—C6	119.55 (8)	C8—C7—H7A	109.5
C6—C5—H5	120.2	C8—C7—H7B	109.5
C3—C4—C5	120.66 (8)	C8—C7—H7C	109.5
C3—C4—H4	119.7	H7A—C7—H7B	109.5
C5—C4—H4	119.7	H7A—C7—H7C	109.5
O1—C2—C3	124.17 (7)	H7B—C7—H7C	109.5

O1—C2—C1—N1	−0.22 (10)	C4—C3—C2—O1	178.84 (8)
O1—C2—C1—C6	−178.85 (7)	C4—C3—C2—C1	−0.83 (12)
C3—C2—C1—N1	179.48 (7)	C4—C5—C6—C1	−0.39 (13)
C3—C2—C1—C6	0.85 (12)	C2—C3—C4—C5	0.22 (13)
C5—C6—C1—N1	−178.83 (7)	C6—C5—C4—C3	0.40 (14)
C5—C6—C1—C2	−0.24 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.894 (14)	1.709 (14)	2.6025 (9)	177.8 (16)
N1—H1A···O2	0.930 (13)	1.807 (13)	2.7251 (9)	168.7 (12)
N1—H1B···O2ⁱⁱ	0.923 (12)	1.891 (12)	2.8019 (9)	168.8 (11)
N1—H1C···O3ⁱⁱⁱ	0.935 (12)	1.834 (12)	2.7531 (8)	167.2 (12)
C6—H6···O3ⁱⁱⁱ	0.95	2.55	3.2493 (11)	131

Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z+3/2; (iii) x, −y+1/2, z+1/2.

Acknowledgements

The authors acknowledge CRM2, Institut Jean Barriol (UMR 7036 CNRS, University de Lorraine, France), for providing access to the experimental crystallographic facilities.

References

Allen, F. H., Hoy, V. J., Howard, J. A. K., Thalladi, V. R., Desiraju, G. R., Wilson, C. C. & McIntyre, G. J. (1997). J. Am. Chem. Soc. 119, 3477–3480. CSD CrossRef CAS Web of Science Google Scholar
DeTitta, G. T. (1985). J. Appl. Cryst. 18, 75–79. CrossRef CAS Web of Science IUCr Journals Google Scholar
Dey, A., Desiraju, G. R., Mondal, R. & Howard, J. A. K. (2004). Chem. Commun. pp. 2528–2529. Web of Science CSD CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Jagan, R. & Sivakumar, K. (2009). Acta Cryst. C65, o414–o418. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Jin, S. & Wang, D. (2013). J. Mol. Struct. 1037, 242–255. Web of Science CSD CrossRef CAS Google Scholar
Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2011). J. Chem. Crystallogr. 41, 1649–1662. Web of Science CSD CrossRef CAS Google Scholar
Vivek, P. & Murugakoothan, P. (2014). Appl. Phys. A, 115, 1139–1146. Web of Science CrossRef CAS Google Scholar
Yeşilel, O. Z., Paşaoğlub, H., Yılan, O. O. & Büyükgüngör, O. (2007). Z. Naturforsch. Teil B, 62, 823–828. Google Scholar
Zhao, Q. (2012). Acta Cryst. E68, o1535. CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.