4-Methyl­anilinium 3-carb­oxy-4-hy­droxy­benzene­sulfonate

Kalaiyarasi, S.; Suresh, S.; Akilan, R.; Kumar, R.M.; Chakkaravarthi, G.

doi:10.1107/S2414314617002541

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170254

https://doi.org/10.1107/S2414314617002541

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4-Methylanilinium 3-carboxy-4-hydroxybenzenesulfonate

S. Kalaiyarasi,^a S. Suresh,^a R. Akilan,^b R. Mohan Kumar ^a ^* and G. Chakkaravarthi ^c ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of physics, Aksheyaa College of Engineering, Kancheepuram 603 314, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: mohan66@hotmail.com, chakkaravarthi_2005@yahoo.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 13 February 2017; accepted 14 February 2017; online 24 February 2017)

In the title molecular salt, C₇H₁₀N⁺·C₇H₅O₆S⁻, the anion is deprotonated at the hydroxy O atom of the sulfonate group. In the anion, an intra-ionic O—H⋯O hydrogen bond generates an S(6) graph-set motif. In the crystal, the inter-ionic N—H⋯O and O—H⋯O hydrogen bonds generate an R₂⁴(12) ring-set motif, linking the anions and cations into an infinite three-dimensional framework. The crystal structure also features C—H⋯π and π–π [centroid-to-centroid distance = 3.5946 (11) Å] interactions.

Keywords: crystal structure; molecular salt; hydrogen bonding.

CCDC reference: 1532573

Structure description

Amino derivatives of benzoic acid are of considerable importance because of their use as anti-inflammatory and anti-cancer agents (Congiu et al., 2005 ). We herein report the synthesis and the crystal structure of the title molecular salt (Fig. 1). The asymmetric unit contains a 4-methylanilinium cation and a 3-carboxy-4-hydroxybenzenesulfonate anion. The geometric parameters are comparable with those of reported similar structures for 4-methylanilinium (Benali-Cherif et al., 2009 ) and 3-carboxy-4-hydroxybenzenesulfonate (Hemamalini & Fun, 2010 ). The cation is protonated at the amine atom N1 and the anion is deprotonated at the hydroxy atom O5. The O1—H1⋯O3 hydrogen bond generates an S(6) graph-set motif (Fig. 1) in the anion.

Figure 1
The molecular structure of the title molecular salt, with the atom labelling and 30% probability displacement ellipsoids.

A pair of inter-ionic N1—H1A⋯O6ⁱ and N1—H1B⋯O4ⁱⁱ hydrogen bonds (for symmetry codes, see Table 1) generate an R₂⁴(12) ring-set motif (Fig. 2). In the crystal structure, the inter-ionic N—H⋯O and O—H⋯O hydrogen bonds (Table 1 and Fig. 3) link the adjacent anions and cations into an infinite three-dimensional framework. The crystal structure is also influenced by weak C—H⋯π (Table 1) and π–π [Cg1⋯Cg1(1 − x,1 − y,1 − z) = 3.5946 (11) Å; Cg1 is the centroid of the C8–C13 ring] interactions.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3	0.83 (1)	1.83 (2)	2.587 (2)	150 (3)
N1—H1A⋯O6ⁱ	0.89	1.95	2.837 (3)	172
N1—H1B⋯O4ⁱⁱ	0.89	1.94	2.821 (2)	169
O2—H2A⋯O5ⁱⁱ	0.82 (1)	1.79 (1)	2.6159 (19)	176 (3)
N1—H1C⋯O3ⁱⁱⁱ	0.89	2.30	2.7548 (19)	112
N1—H1C⋯O5^iv	0.89	2.59	3.461 (3)	166
C10—H10⋯Cg2^v	0.93	2.66	3.549 (2)	160
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+2, -z+1; (v) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
A partial view of the crystal packing showing the ring-set motif.

Figure 3
The crystal packing of the title molecular salt viewed along the a axis. The hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.

Synthesis and crystallization

The title compound was synthesized from p-methyl aniline and 2-hydroxy-5-sulfobenzoic acid in a stoichiometric ratio and dissolved in a mixed solvent of water and acetone at ambient temperature. The solution was filtered and allowed to evaporate and yielded crystals suitable for X-ray diffraction after two weeks.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·C₇H₅O₆S⁻
M_r	325.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	9.5114 (8), 12.3080 (11), 12.5537 (11)
β (°)	98.962 (3)
V (Å³)	1451.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.25
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD Diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.609, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	26625, 4730, 3474
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.738

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.142, 1.10
No. of reflections	4730
No. of parameters	208
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.76
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1532573

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617002541/bt4043sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002541/bt4043Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617002541/bt4043Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).

4-Methylanilinium 3-carboxy-4-hydroxybenzenesulfonate top

Crystal data top

C₇H₁₀N⁺·C₇H₅O₆S⁻	F(000) = 680
M_r = 325.33	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.5114 (8) Å	Cell parameters from 8665 reflections
b = 12.3080 (11) Å	θ = 2.3–31.5°
c = 12.5537 (11) Å	µ = 0.25 mm⁻¹
β = 98.962 (3)°	T = 295 K
V = 1451.7 (2) Å³	Block, colourless
Z = 4	0.24 × 0.20 × 0.18 mm

Data collection top

Bruker Kappa APEXII CCD Diffractometer	3474 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.040
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 31.6°, θ_min = 2.3°
T_min = 0.609, T_max = 0.746	h = −14→13
26625 measured reflections	k = −17→17
4730 independent reflections	l = −18→18

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.051	w = 1/[σ²(F_o²) + (0.0514P)² + 0.973P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.142	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 0.40 e Å⁻³
4730 reflections	Δρ_min = −0.76 e Å⁻³
208 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2016), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.030 (2)

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
C1	0.41299 (18)	1.08104 (15)	0.28078 (14)	0.0309 (4)
C2	0.3200 (2)	1.16342 (16)	0.29414 (16)	0.0352 (4)
H2	0.311647	1.223576	0.248763	0.042*
C3	0.2388 (2)	1.15537 (17)	0.37648 (16)	0.0387 (4)
H3	0.175095	1.210620	0.385736	0.046*
C4	0.2507 (2)	1.06667 (18)	0.44518 (15)	0.0385 (4)
C5	0.3410 (2)	0.98278 (19)	0.42574 (17)	0.0438 (5)
H5	0.346720	0.920894	0.468705	0.053*
C6	0.4227 (2)	0.98922 (18)	0.34377 (17)	0.0403 (4)
H6	0.482924	0.932553	0.331607	0.048*
C7	0.1721 (3)	1.0633 (2)	0.54056 (19)	0.0593 (7)
H7A	0.230980	1.093739	0.602444	0.089*
H7B	0.149500	0.989370	0.555340	0.089*
H7C	0.085869	1.104711	0.524619	0.089*
C8	0.36092 (18)	0.65002 (14)	0.58334 (13)	0.0283 (3)
C9	0.4344 (2)	0.59570 (16)	0.67204 (14)	0.0344 (4)
H9	0.389513	0.581016	0.731168	0.041*
C10	0.5734 (2)	0.56345 (16)	0.67298 (14)	0.0357 (4)
H10	0.621603	0.526240	0.732126	0.043*
C11	0.64165 (18)	0.58672 (15)	0.58512 (14)	0.0298 (3)
C12	0.56786 (17)	0.64118 (13)	0.49562 (12)	0.0250 (3)
C13	0.42673 (17)	0.67244 (14)	0.49550 (13)	0.0264 (3)
H13	0.377117	0.708411	0.436115	0.032*
C14	0.63914 (18)	0.66439 (15)	0.40202 (14)	0.0290 (3)
N1	0.50396 (18)	1.09139 (15)	0.19685 (14)	0.0400 (4)
H1A	0.457317	1.127520	0.140822	0.060*
H1B	0.526763	1.025568	0.175674	0.060*
H1C	0.582911	1.127370	0.223231	0.060*
O1	0.77811 (15)	0.55499 (14)	0.58997 (12)	0.0447 (4)
O2	0.55929 (15)	0.71141 (14)	0.32111 (11)	0.0442 (4)
O3	0.76397 (14)	0.64117 (14)	0.40068 (12)	0.0438 (4)
O4	0.11033 (19)	0.60551 (15)	0.62629 (18)	0.0701 (6)
O5	0.1984 (2)	0.78754 (13)	0.65703 (13)	0.0531 (4)
O6	0.12809 (16)	0.72387 (15)	0.47508 (13)	0.0517 (4)
S1	0.18523 (5)	0.69380 (4)	0.58472 (4)	0.03677 (15)
H1	0.804 (3)	0.576 (2)	0.5332 (13)	0.055*
H2A	0.601 (3)	0.715 (2)	0.2685 (15)	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0271 (8)	0.0397 (9)	0.0268 (8)	−0.0058 (7)	0.0066 (6)	−0.0079 (7)
C2	0.0398 (10)	0.0326 (9)	0.0351 (9)	−0.0034 (7)	0.0115 (8)	−0.0064 (7)
C3	0.0365 (9)	0.0413 (10)	0.0403 (10)	−0.0034 (8)	0.0121 (8)	−0.0140 (8)
C4	0.0346 (9)	0.0506 (11)	0.0315 (9)	−0.0148 (8)	0.0090 (7)	−0.0103 (8)
C5	0.0491 (12)	0.0487 (12)	0.0340 (10)	−0.0033 (9)	0.0072 (9)	0.0055 (9)
C6	0.0375 (10)	0.0463 (11)	0.0371 (10)	0.0067 (8)	0.0059 (8)	−0.0023 (8)
C7	0.0565 (14)	0.0821 (18)	0.0453 (13)	−0.0183 (13)	0.0266 (11)	−0.0090 (12)
C8	0.0302 (8)	0.0322 (8)	0.0250 (8)	−0.0026 (7)	0.0121 (6)	−0.0036 (6)
C9	0.0424 (10)	0.0411 (10)	0.0222 (8)	−0.0052 (8)	0.0122 (7)	0.0010 (7)
C10	0.0405 (10)	0.0416 (10)	0.0243 (8)	−0.0006 (8)	0.0034 (7)	0.0076 (7)
C11	0.0285 (8)	0.0321 (8)	0.0286 (8)	−0.0014 (7)	0.0041 (6)	0.0030 (7)
C12	0.0260 (7)	0.0284 (8)	0.0218 (7)	−0.0017 (6)	0.0077 (6)	−0.0006 (6)
C13	0.0276 (7)	0.0312 (8)	0.0216 (7)	0.0006 (6)	0.0081 (6)	0.0013 (6)
C14	0.0271 (7)	0.0343 (8)	0.0277 (8)	−0.0008 (6)	0.0107 (6)	0.0018 (7)
N1	0.0364 (8)	0.0490 (10)	0.0380 (9)	−0.0026 (7)	0.0170 (7)	−0.0066 (7)
O1	0.0306 (7)	0.0602 (10)	0.0437 (8)	0.0088 (6)	0.0067 (6)	0.0175 (7)
O2	0.0345 (7)	0.0713 (10)	0.0301 (7)	0.0101 (7)	0.0157 (5)	0.0189 (7)
O3	0.0292 (6)	0.0624 (10)	0.0435 (8)	0.0085 (6)	0.0170 (6)	0.0121 (7)
O4	0.0482 (9)	0.0539 (10)	0.1196 (17)	−0.0002 (8)	0.0485 (10)	0.0197 (11)
O5	0.0716 (11)	0.0506 (9)	0.0456 (9)	0.0087 (8)	0.0357 (8)	−0.0088 (7)
O6	0.0382 (8)	0.0744 (11)	0.0441 (9)	0.0165 (8)	0.0111 (6)	−0.0048 (8)
S1	0.0362 (2)	0.0396 (3)	0.0400 (3)	0.00331 (19)	0.02343 (19)	−0.00040 (19)

Geometric parameters (Å, º) top

C1—C2	1.373 (3)	C9—H9	0.9300
C1—C6	1.374 (3)	C10—C11	1.394 (2)
C1—N1	1.469 (2)	C10—H10	0.9300
C2—C3	1.387 (3)	C11—O1	1.348 (2)
C2—H2	0.9300	C11—C12	1.400 (2)
C3—C4	1.385 (3)	C12—C13	1.396 (2)
C3—H3	0.9300	C12—C14	1.473 (2)
C4—C5	1.389 (3)	C13—H13	0.9300
C4—C7	1.508 (3)	C14—O3	1.224 (2)
C5—C6	1.385 (3)	C14—O2	1.305 (2)
C5—H5	0.9300	N1—H1A	0.8900
C6—H6	0.9300	N1—H1B	0.8900
C7—H7A	0.9600	N1—H1C	0.8900
C7—H7B	0.9600	O1—H1	0.829 (10)
C7—H7C	0.9600	O2—H2A	0.824 (10)
C8—C13	1.378 (2)	O4—S1	1.4411 (17)
C8—C9	1.390 (3)	O5—S1	1.4612 (16)
C8—S1	1.7585 (17)	O6—S1	1.4470 (17)
C9—C10	1.379 (3)

C2—C1—C6	121.61 (17)	C9—C10—C11	119.87 (17)
C2—C1—N1	119.08 (17)	C9—C10—H10	120.1
C6—C1—N1	119.32 (17)	C11—C10—H10	120.1
C1—C2—C3	118.85 (19)	O1—C11—C10	117.93 (16)
C1—C2—H2	120.6	O1—C11—C12	122.28 (15)
C3—C2—H2	120.6	C10—C11—C12	119.78 (16)
C4—C3—C2	121.28 (19)	C13—C12—C11	119.65 (14)
C4—C3—H3	119.4	C13—C12—C14	120.50 (15)
C2—C3—H3	119.4	C11—C12—C14	119.84 (15)
C3—C4—C5	118.01 (17)	C8—C13—C12	120.03 (16)
C3—C4—C7	120.9 (2)	C8—C13—H13	120.0
C5—C4—C7	121.1 (2)	C12—C13—H13	120.0
C6—C5—C4	121.5 (2)	O3—C14—O2	122.76 (15)
C6—C5—H5	119.3	O3—C14—C12	122.26 (16)
C4—C5—H5	119.3	O2—C14—C12	114.99 (14)
C1—C6—C5	118.64 (19)	C1—N1—H1A	109.5
C1—C6—H6	120.7	C1—N1—H1B	109.5
C5—C6—H6	120.7	H1A—N1—H1B	109.5
C4—C7—H7A	109.5	C1—N1—H1C	109.5
C4—C7—H7B	109.5	H1A—N1—H1C	109.5
H7A—C7—H7B	109.5	H1B—N1—H1C	109.5
C4—C7—H7C	109.5	C11—O1—H1	106.3 (19)
H7A—C7—H7C	109.5	C14—O2—H2A	110.5 (19)
H7B—C7—H7C	109.5	O4—S1—O6	113.81 (13)
C13—C8—C9	120.18 (16)	O4—S1—O5	111.70 (11)
C13—C8—S1	119.83 (14)	O6—S1—O5	111.85 (10)
C9—C8—S1	119.97 (12)	O4—S1—C8	107.26 (10)
C10—C9—C8	120.47 (15)	O6—S1—C8	106.60 (8)
C10—C9—H9	119.8	O5—S1—C8	104.98 (10)
C8—C9—H9	119.8

C6—C1—C2—C3	2.9 (3)	O1—C11—C12—C14	0.7 (3)
N1—C1—C2—C3	−177.26 (17)	C10—C11—C12—C14	−179.09 (17)
C1—C2—C3—C4	0.4 (3)	C9—C8—C13—C12	−0.4 (3)
C2—C3—C4—C5	−3.4 (3)	S1—C8—C13—C12	177.76 (13)
C2—C3—C4—C7	174.4 (2)	C11—C12—C13—C8	0.2 (3)
C3—C4—C5—C6	3.3 (3)	C14—C12—C13—C8	179.79 (16)
C7—C4—C5—C6	−174.5 (2)	C13—C12—C14—O3	177.70 (18)
C2—C1—C6—C5	−3.0 (3)	C11—C12—C14—O3	−2.7 (3)
N1—C1—C6—C5	177.11 (18)	C13—C12—C14—O2	−2.3 (3)
C4—C5—C6—C1	−0.1 (3)	C11—C12—C14—O2	177.28 (17)
C13—C8—C9—C10	−0.2 (3)	C13—C8—S1—O4	136.91 (17)
S1—C8—C9—C10	−178.34 (15)	C9—C8—S1—O4	−44.95 (19)
C8—C9—C10—C11	0.9 (3)	C13—C8—S1—O6	14.65 (18)
C9—C10—C11—O1	179.15 (18)	C9—C8—S1—O6	−167.20 (16)
C9—C10—C11—C12	−1.0 (3)	C13—C8—S1—O5	−104.14 (15)
O1—C11—C12—C13	−179.73 (17)	C9—C8—S1—O5	74.00 (17)
C10—C11—C12—C13	0.5 (3)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	0.83 (1)	1.83 (2)	2.587 (2)	150 (3)
N1—H1A···O6ⁱ	0.89	1.95	2.837 (3)	172
N1—H1B···O4ⁱⁱ	0.89	1.94	2.821 (2)	169
O2—H2A···O5ⁱⁱ	0.82 (1)	1.79 (1)	2.6159 (19)	176 (3)
N1—H1C···O3ⁱⁱⁱ	0.89	2.30	2.7548 (19)	112
N1—H1C···O5^iv	0.89	2.59	3.461 (3)	166
C10—H10···Cg2^v	0.93	2.66	3.549 (2)	160

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

Acknowledgements

The authors acknowledge the SAIF, IIT, Madras, for the data collection.

References

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