2-Amino­anilinium 4-methyl­benzene­sulfonate

Narvekar, K.U.; Srinivasan, B.R.

doi:10.1107/S2414314620002308

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 2| February 2020| x200230

https://doi.org/10.1107/S2414314620002308

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2-Aminoanilinium 4-methylbenzenesulfonate

Kedar U. Narvekar ^a and Bikshandarkoil R. Srinivasan ^a ^*

^aSchool of Chemical Sciences, Goa University PO, Goa 403206, India
^*Correspondence e-mail: srini@unigoa.ac.in

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 February 2020; accepted 19 February 2020; online 21 February 2020)

In the extended structure of the title molecular salt, C₆H₉N₂⁺·C₇H₇O₃S⁻, the cations and anions are linked by N—H⋯O hydrogen bonds to generate [010] chains.

Keywords: crystal structure; benzene-1,2-diamine; N—H⋯O hydrogen bonds.

CCDC reference: 1985013

Structure description

As part of an ongoing research programme, we are investigating the structural chemistry of the molecular salts of benzene-1,2-diamine. In a recent data report we described the crystal structure of benzene-1,2-diaminium bis(4-methylbenzene-1-sulfonate), 2 (Narvekar & Srinivasan, 2020 ). The structure of another molecular salt of 4-methylbenzene-1-sulfonic acid containing both mono and diprotonated cations of benzene-1,2-diamine, namely 2-aminoanilinium benzene-1,2-diaminium tris(4-methylbenzene-1-sulfonate), 3, was reported earlier (Amirthakumar et al., 2018 ). The Cambridge Structural Database (CSD; Groom et al., 2016 ) lists several structurally characterized salts of benzene-1,2-diamine containing the monoprotonated 2-aminoanilinium cation or the diprotonated benzene-1,2-diaminium dication.

In this report, we describe the crystal structure of the title salt, 1, which is the third anhydrous compound that can be isolated from the benzene-1,2-diamine/4-methylbenzene-1-sulfonic acid/water system. The title salt was obtained by an aqueous reaction of the aromatic diamine with 4-methylbenzene-1-sulfonic acid in a 2:1 molar ratio, unlike 2, which was crystallized from a 1:2 reaction.

The asymmetric unit of 1 consists of one 2-aminoanilinium cation and one 4-methylbenzene-1-sulfonate anion (Fig. 1) with all atoms located in general positions. The geometric parameters of the cation and the anion are in their normal ranges and are in agreement with previously reported data (Mishra & Pallepogu, 2018 ; Narvekar & Srinivasan, 2020).

Figure 1
The molecular structure of 1 with displacement ellipsoids drawn at 50% probability level. Hydrogen bonds are shown as blue dashed lines.

All the oxygen atoms attached to the sulfur atom of the sulfonate moiety of the anion function as hydrogen-bond acceptors (Fig. 2), while four of the five H atoms attached to the N atoms of the 2-aminoanilinium cation function as hydrogen-bond donors, resulting in a total of four N—H⋯O hydrogen bonds (with two occurring within the arbitrarily chosen asymmetric unit; Table 1). Thus, the cations and the anions are linked only via N—H⋯O hydrogen bonds, as observed earlier for 2. The extended structure of 1 features [010] hydrogen-bonded chains, with adjacent cations and anions related by the 2₁ screw axis (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O11	0.89	1.89	2.7767 (17)	174
N1—H1B⋯O13ⁱ	0.89	1.93	2.8111 (17)	171
N1—H1C⋯O12ⁱⁱ	0.89	1.92	2.7914 (17)	165
N2—H2A⋯O12	0.90 (2)	2.22 (2)	3.097 (3)	165 (2)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1.

Figure 2
The hydrogen-bonding scheme around the 4-methylbenzene-1-sulfonate anion. Symmetry codes: (i) -x + 1, −y, −z + 1; (ii) −x + 1, −y + 1, −z + 1.

Figure 3
A view down [010] of the packing in 1 with N—H⋯O hydrogen bonds shown as dashed lines.

Synthesis and crystallization

Freshly recrystallized benzene-1,2-diamine (216 mg, 1 mmol) was dissolved in aqueous ethanol (25–30 ml). Into this, an aqueous solution of 4-methylbenzene-1-sulfonic acid (190 mg, 1 mmol) was added. The clear reaction mixture thus obtained was left aside for crystallization. After a few days crystals of 1 in the form of colourless blocks slowly separated. The crystals were filtered and dried in air. Yield 45%.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₇H₇O₃S⁻
M_r	280.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.6392 (5), 5.7111 (2), 17.5295 (6)
β (°)	102.349 (1)
V (Å³)	1431.66 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.23
Crystal size (mm)	0.45 × 0.37 × 0.33

Data collection
Diffractometer	Bruker D8 Quest ECO
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.682, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	22028, 4362, 3253
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.127, 1.06
No. of reflections	4362
No. of parameters	182
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.31
Computer programs: APEX3 and SAINT (Bruker, 2019 ), SHELXT2014 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and shelXle (Hübschle et al., 2011 ).

Structural data

CCDC reference: 1985013

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314620002308/hb4337sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620002308/hb4337Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620002308/hb4337Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and shelXle (Hübschle et al., 2011); software used to prepare material for publication: shelXle (Hübschle et al., 2011).

2-Aminoanilinium 4-methylbenzenesulfonate top

Crystal data top

C₆H₉N₂⁺·C₇H₇O₃S⁻	F(000) = 592
M_r = 280.34	D_x = 1.301 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.6392 (5) Å	Cell parameters from 7623 reflections
b = 5.7111 (2) Å	θ = 2.9–30.2°
c = 17.5295 (6) Å	µ = 0.23 mm⁻¹
β = 102.349 (1)°	T = 293 K
V = 1431.66 (9) Å³	Block, colourless
Z = 4	0.45 × 0.37 × 0.33 mm

Data collection top

Bruker D8 Quest ECO diffractometer	3253 reflections with I > 2σ(I)
Radiation source: Sealed Tube	R_int = 0.027
φ and ω scans	θ_max = 30.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −20→20
T_min = 0.682, T_max = 0.746	k = −8→8
22028 measured reflections	l = −25→25
4362 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0529P)² + 0.3765P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.010
4362 reflections	Δρ_max = 0.21 e Å⁻³
182 parameters	Δρ_min = −0.31 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.

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

	x	y	z	U_iso*/U_eq
N1	0.36804 (8)	0.2361 (2)	0.46460 (7)	0.0440 (3)
H1A	0.414876	0.196763	0.442076	0.066*
H1B	0.350598	0.111606	0.488514	0.066*
H1C	0.386780	0.349023	0.499410	0.066*
N2	0.37965 (15)	0.6564 (3)	0.38220 (11)	0.0700 (5)
H2B	0.3826 (18)	0.763 (5)	0.3528 (16)	0.095 (9)*
H2A	0.4355 (16)	0.584 (4)	0.3963 (13)	0.076 (7)*
C1	0.28909 (9)	0.3195 (2)	0.40520 (8)	0.0394 (3)
C2	0.29793 (11)	0.5272 (3)	0.36608 (8)	0.0468 (3)
C3	0.21843 (15)	0.6058 (3)	0.31307 (10)	0.0657 (5)
H3	0.221090	0.744552	0.285849	0.079*
C4	0.13647 (15)	0.4805 (5)	0.30077 (12)	0.0804 (7)
H4	0.084179	0.536909	0.265797	0.096*
C5	0.13039 (14)	0.2741 (5)	0.33902 (13)	0.0774 (6)
H5	0.074746	0.189818	0.329632	0.093*
C6	0.20756 (11)	0.1926 (3)	0.39160 (10)	0.0552 (4)
H6	0.204453	0.052101	0.417768	0.066*
S11	0.59680 (3)	0.22022 (7)	0.39473 (2)	0.04691 (12)
O11	0.51524 (8)	0.0815 (2)	0.40070 (7)	0.0599 (3)
O12	0.58218 (10)	0.4676 (2)	0.40655 (7)	0.0702 (4)
O13	0.68108 (8)	0.1290 (2)	0.44434 (7)	0.0647 (3)
C11	0.6391 (2)	0.0983 (7)	0.06127 (15)	0.1203 (11)
H11A	0.607486	−0.041356	0.039393	0.180*
H11B	0.704391	0.086390	0.060695	0.180*
H11C	0.612753	0.231288	0.030895	0.180*
C12	0.62771 (14)	0.1275 (4)	0.14452 (12)	0.0720 (5)
C13	0.65754 (14)	−0.0419 (4)	0.19988 (13)	0.0732 (5)
H13	0.684183	−0.178430	0.185581	0.088*
C14	0.64892 (12)	−0.0142 (3)	0.27597 (11)	0.0609 (4)
H14	0.669112	−0.131566	0.312468	0.073*
C15	0.61010 (10)	0.1889 (3)	0.29789 (9)	0.0444 (3)
C16	0.58045 (14)	0.3615 (3)	0.24378 (11)	0.0619 (4)
H16	0.554920	0.499363	0.258252	0.074*
C17	0.58897 (16)	0.3279 (4)	0.16747 (12)	0.0764 (6)
H17	0.567940	0.443925	0.130691	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0443 (6)	0.0444 (6)	0.0411 (6)	−0.0028 (5)	0.0042 (5)	0.0072 (5)
N2	0.0852 (13)	0.0577 (10)	0.0664 (10)	−0.0219 (9)	0.0146 (9)	0.0133 (8)
C1	0.0403 (6)	0.0410 (7)	0.0348 (6)	−0.0001 (5)	0.0037 (5)	−0.0034 (5)
C2	0.0600 (9)	0.0424 (7)	0.0368 (7)	0.0031 (6)	0.0077 (6)	−0.0008 (6)
C3	0.0862 (13)	0.0619 (11)	0.0450 (8)	0.0282 (10)	0.0050 (8)	0.0040 (8)
C4	0.0615 (11)	0.1129 (19)	0.0574 (11)	0.0317 (12)	−0.0082 (8)	−0.0091 (12)
C5	0.0463 (9)	0.1129 (18)	0.0668 (12)	−0.0095 (10)	−0.0019 (8)	−0.0164 (12)
C6	0.0523 (9)	0.0601 (10)	0.0518 (8)	−0.0128 (7)	0.0083 (7)	−0.0102 (7)
S11	0.0464 (2)	0.0440 (2)	0.0472 (2)	−0.00369 (15)	0.00294 (14)	0.00788 (15)
O11	0.0509 (6)	0.0685 (8)	0.0641 (7)	−0.0118 (6)	0.0208 (5)	−0.0027 (6)
O12	0.1021 (10)	0.0465 (7)	0.0531 (7)	0.0017 (7)	−0.0033 (6)	−0.0028 (5)
O13	0.0512 (6)	0.0777 (8)	0.0597 (7)	−0.0014 (6)	−0.0007 (5)	0.0279 (6)
C11	0.117 (2)	0.184 (3)	0.0711 (15)	0.009 (2)	0.0443 (15)	−0.0057 (19)
C12	0.0600 (10)	0.0984 (16)	0.0623 (11)	−0.0045 (11)	0.0240 (9)	−0.0010 (11)
C13	0.0648 (11)	0.0780 (13)	0.0803 (13)	0.0103 (10)	0.0235 (10)	−0.0079 (11)
C14	0.0588 (10)	0.0544 (10)	0.0684 (11)	0.0089 (8)	0.0111 (8)	0.0072 (8)
C15	0.0361 (6)	0.0440 (7)	0.0513 (8)	−0.0042 (5)	0.0057 (5)	0.0086 (6)
C16	0.0720 (11)	0.0550 (9)	0.0590 (10)	0.0110 (8)	0.0146 (8)	0.0159 (8)
C17	0.0873 (14)	0.0843 (15)	0.0586 (11)	0.0096 (12)	0.0179 (10)	0.0261 (10)

Geometric parameters (Å, º) top

N1—C1	1.4601 (17)	S11—O12	1.4506 (13)
N1—H1A	0.8900	S11—O11	1.4554 (12)
N1—H1B	0.8900	S11—C15	1.7586 (16)
N1—H1C	0.8900	C11—C12	1.513 (3)
N2—C2	1.382 (2)	C11—H11A	0.9600
N2—H2B	0.81 (3)	C11—H11B	0.9600
N2—H2A	0.90 (2)	C11—H11C	0.9600
C1—C6	1.373 (2)	C12—C13	1.374 (3)
C1—C2	1.390 (2)	C12—C17	1.375 (3)
C2—C3	1.399 (2)	C13—C14	1.376 (3)
C3—C4	1.374 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.382 (2)
C4—C5	1.368 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.372 (2)
C5—C6	1.377 (3)	C16—C17	1.383 (3)
C5—H5	0.9300	C16—H16	0.9300
C6—H6	0.9300	C17—H17	0.9300
S11—O13	1.4462 (12)

C1—N1—H1A	109.5	O12—S11—O11	111.82 (8)
C1—N1—H1B	109.5	O13—S11—C15	106.70 (7)
H1A—N1—H1B	109.5	O12—S11—C15	106.69 (7)
C1—N1—H1C	109.5	O11—S11—C15	106.01 (7)
H1A—N1—H1C	109.5	C12—C11—H11A	109.5
H1B—N1—H1C	109.5	C12—C11—H11B	109.5
C2—N2—H2B	115.8 (19)	H11A—C11—H11B	109.5
C2—N2—H2A	120.5 (15)	C12—C11—H11C	109.5
H2B—N2—H2A	111 (2)	H11A—C11—H11C	109.5
C6—C1—C2	122.28 (14)	H11B—C11—H11C	109.5
C6—C1—N1	118.54 (13)	C13—C12—C17	117.91 (18)
C2—C1—N1	119.16 (12)	C13—C12—C11	121.3 (2)
N2—C2—C1	121.50 (15)	C17—C12—C11	120.8 (2)
N2—C2—C3	121.66 (17)	C12—C13—C14	121.53 (19)
C1—C2—C3	116.73 (16)	C12—C13—H13	119.2
C4—C3—C2	120.76 (18)	C14—C13—H13	119.2
C4—C3—H3	119.6	C13—C14—C15	119.64 (17)
C2—C3—H3	119.6	C13—C14—H14	120.2
C5—C4—C3	121.20 (18)	C15—C14—H14	120.2
C5—C4—H4	119.4	C16—C15—C14	119.92 (16)
C3—C4—H4	119.4	C16—C15—S11	120.67 (13)
C4—C5—C6	119.28 (19)	C14—C15—S11	119.40 (12)
C4—C5—H5	120.4	C15—C16—C17	119.22 (18)
C6—C5—H5	120.4	C15—C16—H16	120.4
C1—C6—C5	119.73 (18)	C17—C16—H16	120.4
C1—C6—H6	120.1	C12—C17—C16	121.77 (18)
C5—C6—H6	120.1	C12—C17—H17	119.1
O13—S11—O12	113.46 (8)	C16—C17—H17	119.1
O13—S11—O11	111.59 (8)

C6—C1—C2—N2	178.01 (16)	C13—C14—C15—C16	0.0 (3)
N1—C1—C2—N2	−0.1 (2)	C13—C14—C15—S11	178.53 (14)
C6—C1—C2—C3	1.7 (2)	O13—S11—C15—C16	−139.99 (14)
N1—C1—C2—C3	−176.40 (13)	O12—S11—C15—C16	−18.38 (16)
N2—C2—C3—C4	−176.72 (18)	O11—S11—C15—C16	100.95 (15)
C1—C2—C3—C4	−0.4 (2)	O13—S11—C15—C14	41.48 (15)
C2—C3—C4—C5	−0.9 (3)	O12—S11—C15—C14	163.08 (13)
C3—C4—C5—C6	0.9 (3)	O11—S11—C15—C14	−77.59 (14)
C2—C1—C6—C5	−1.7 (2)	C14—C15—C16—C17	0.7 (3)
N1—C1—C6—C5	176.40 (16)	S11—C15—C16—C17	−177.78 (15)
C4—C5—C6—C1	0.4 (3)	C13—C12—C17—C16	0.5 (3)
C17—C12—C13—C14	0.3 (3)	C11—C12—C17—C16	−178.0 (2)
C11—C12—C13—C14	178.8 (2)	C15—C16—C17—C12	−1.0 (3)
C12—C13—C14—C15	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O11	0.89	1.89	2.7767 (17)	174
N1—H1B···O13ⁱ	0.89	1.93	2.8111 (17)	171
N1—H1C···O12ⁱⁱ	0.89	1.92	2.7914 (17)	165
N2—H2A···O12	0.90 (2)	2.22 (2)	3.097 (3)	165 (2)

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

Acknowledgements

BRS acknowledges the Department of Science & Technology (DST) New Delhi, for the sanction of a Bruker D8 Quest Eco single crystal X-ray diffractometer under the DST–FIST program.

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