4-Methyl­anilinium 4-hy­droxy­benzene­sulfonate

Jovita, J.V.; Sathya, S.; Usha, G.; Vasanthi, R.; Sagayaraj, P.

doi:10.1107/S1600536813009410

organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o725

https://doi.org/10.1107/S1600536813009410

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4-Methylanilinium 4-hydroxybenzenesulfonate

J. V. Jovita,^a S. Sathya,^a G. Usha,^a ^* R. Vasanthi ^a and P. Sagayaraj ^b

^aPG and Research Department of Physics, Queen Mary's College, Chennai-4, Tamilnadu, India, and ^bDepartment of Physics, Loyola college, Chennai-34, Tamilnadu, India
^*Correspondence e-mail: guqmc@yahoo.com

(Received 8 March 2013; accepted 7 April 2013; online 13 April 2013)

In the crystal of the title molecular salt, C₇H₁₀N⁺·C₆H₅O₄S⁻, the benzenesulfonate units are linked through phenol–sulfonate O—H⋯O hydrogen bonds, forming chains along the c-axis direction. These chains are linked via N—H⋯O hydrogen bonds involving two of the three H atoms of the ammonium group of the 4-methylanilium cation, giving rise to two-dimensional networks parallel to the bc plane which are further connected through an additional N—H⋯O interaction in which the third ammonium H atom is involved, generating a three-dimensional network.

Related literature

For the biological activity of related compounds, see: Fukami et al. (2000 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₁₀N⁺·C₆H₅O₄S⁻
M_r = 281.32
Monoclinic, P 2₁ /c
a = 11.6450 (2) Å
b = 7.1670 (1) Å
c = 16.3080 (3) Å
β = 107.654 (1)°
V = 1296.96 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.926, T_max = 0.950
11047 measured reflections
2285 independent reflections
2045 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.091
S = 1.06
2285 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1ⁱ	0.89	1.96	2.8367 (19)	169
N1—H1B⋯O4ⁱⁱ	0.89	1.96	2.839 (2)	170
N1—H1A⋯O2ⁱⁱⁱ	0.89	1.94	2.8091 (19)	166
O4—H4⋯O3ⁱⁱⁱ	0.82	1.82	2.6343 (17)	173
Symmetry codes: (i) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813009410/lr2102sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813009410/lr2102Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813009410/lr2102Isup3.cml

checkCIF report

Comment top

The stucture of the title compound, (I), is shown in Figure 1. Bond lengh and angles are within the standard values (Allen et al., 1987). In the crystal the phenolsulfonate units are joined together through O4-H4···O3 hydrogen bonds, forming chains along the c crystallographic axis. These chains are subsequently linked together through N-H···O interactions involving the 4-methylanilium units. First, giving rise to a two-dimensional network parallel to bc plane, through interactions involving two of the three hydrogens of the ammonium moiety: N1-H1A···O2 and N1-H1C···O1 and finally generating a three-dimensional network through the use of the third hydrogen atom bonded to the nitrogen: N1-H1B···O4 (Table 1 and Figure 2).

Related literature top

For the biological activity of related compounds, see: Fukami et al. (2000). For standard bond lengths, see: Allen et al. (1987).

Experimental top

The 4-MAPS compound was synthesized by the reaction of equimolar mixture of 4-methyl aniline and phenolsulfonic acid. To a saturated solution of 4-methyl aniline in acetone, phenolsulfonic acid was slowly added at room temperature. The solution was stirred for six hours to get an homogeneous solution, filtered and kept for slow evaporation at room temperature. After that a saturated solution of 4-MAPS was prepared by using methanol at room temperature. The prepared solution was kept to constant temperature in water bath at 30° C to avoid the effect of fluctuation in room temperature. An slow evaporation process was allowed for a period of 15 days. The grown crystals of an approximate size of 12 x 9 x 2 mm3 were harvested and re-crystallized to grow pure crystals for further studies.

Structure description top

For the biological activity of related compounds, see: Fukami et al. (2000). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the the packing of the the title compound. Dashed lines indicate hydrogen bonds.

4-Methylanilinium 4-hydroxybenzenesulfonate top

Crystal data top

C₇H₁₀N⁺·C₆H₅O₄S⁻	F(000) = 592
M_r = 281.32	D_x = 1.441 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5614 reflections
a = 11.6450 (2) Å	θ = 2.8–29.4°
b = 7.1670 (1) Å	µ = 0.26 mm⁻¹
c = 16.3080 (3) Å	T = 293 K
β = 107.654 (1)°	Block, colourless
V = 1296.96 (4) Å³	0.30 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2285 independent reflections
Radiation source: fine-focus sealed tube	2045 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and φ scan	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→13
T_min = 0.926, T_max = 0.950	k = −8→8
11047 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0467P)² + 0.4532P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2285 reflections	Δρ_max = 0.24 e Å⁻³
175 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0070 (12)

Crystal data top

C₇H₁₀N⁺·C₆H₅O₄S⁻	V = 1296.96 (4) Å³
M_r = 281.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.6450 (2) Å	µ = 0.26 mm⁻¹
b = 7.1670 (1) Å	T = 293 K
c = 16.3080 (3) Å	0.30 × 0.30 × 0.20 mm
β = 107.654 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2285 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2045 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.950	R_int = 0.029
11047 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
2285 reflections	Δρ_min = −0.29 e Å⁻³
175 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.65813 (14)	0.2000 (2)	0.30612 (10)	0.0311 (4)
C2	0.54731 (14)	0.1192 (2)	0.26762 (10)	0.0375 (4)
H2	0.5057	0.0616	0.3011	0.045*
C3	0.49842 (14)	0.1242 (2)	0.17924 (10)	0.0391 (4)
H3	0.4240	0.0688	0.1532	0.047*
C4	0.55951 (14)	0.2109 (2)	0.12920 (10)	0.0328 (4)
C5	0.67033 (15)	0.2933 (2)	0.16791 (11)	0.0365 (4)
H5	0.7116	0.3521	0.1345	0.044*
C6	0.71913 (14)	0.2878 (2)	0.25594 (10)	0.0355 (4)
H6	0.7935	0.3432	0.2820	0.043*
C7	0.91246 (16)	−0.3025 (2)	0.27651 (11)	0.0420 (4)
C8	0.79646 (16)	−0.2324 (3)	0.24420 (12)	0.0455 (4)
H8	0.7542	−0.2001	0.2822	0.055*
C9	0.74260 (15)	−0.2096 (2)	0.15731 (12)	0.0423 (4)
H9	0.6646	−0.1628	0.1367	0.051*
C10	0.80527 (14)	−0.2568 (2)	0.10108 (11)	0.0353 (4)
C11	0.92034 (15)	−0.3268 (2)	0.13049 (12)	0.0432 (4)
H11	0.9623	−0.3581	0.0922	0.052*
C12	0.97244 (15)	−0.3499 (3)	0.21799 (12)	0.0450 (4)
H12	1.0500	−0.3986	0.2382	0.054*
C13	0.9715 (2)	−0.3262 (3)	0.37143 (13)	0.0614 (6)
H13A	0.9581	−0.2166	0.4011	0.092*
H13B	1.0565	−0.3446	0.3825	0.092*
H13C	0.9377	−0.4327	0.3914	0.092*
N1	0.74899 (13)	−0.2321 (2)	0.00829 (9)	0.0424 (4)
H1A	0.7692	−0.1211	−0.0076	0.064*
H1B	0.6692	−0.2387	−0.0039	0.064*
H1C	0.7743	−0.3214	−0.0200	0.064*
O1	0.82148 (11)	0.05029 (17)	0.43307 (7)	0.0458 (3)
O2	0.77002 (13)	0.37156 (18)	0.44678 (8)	0.0559 (4)
O3	0.63246 (11)	0.1221 (2)	0.45415 (8)	0.0526 (4)
O4	0.50641 (11)	0.21139 (18)	0.04252 (7)	0.0450 (3)
H4	0.5499	0.2661	0.0192	0.068*
S1	0.72587 (4)	0.18720 (6)	0.41863 (2)	0.03519 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0357 (8)	0.0251 (8)	0.0341 (8)	0.0030 (6)	0.0128 (7)	−0.0003 (6)
C2	0.0401 (9)	0.0344 (9)	0.0402 (9)	−0.0053 (7)	0.0156 (7)	0.0051 (7)
C3	0.0354 (8)	0.0381 (9)	0.0416 (9)	−0.0091 (7)	0.0084 (7)	0.0018 (7)
C4	0.0377 (8)	0.0283 (8)	0.0332 (8)	0.0027 (6)	0.0119 (7)	−0.0009 (6)
C5	0.0384 (9)	0.0356 (9)	0.0404 (9)	−0.0032 (7)	0.0193 (7)	0.0013 (7)
C6	0.0329 (8)	0.0336 (9)	0.0405 (9)	−0.0048 (7)	0.0119 (7)	−0.0026 (7)
C7	0.0459 (9)	0.0283 (9)	0.0484 (10)	−0.0016 (7)	0.0093 (8)	−0.0028 (7)
C8	0.0492 (10)	0.0398 (10)	0.0502 (10)	0.0040 (8)	0.0192 (8)	−0.0065 (8)
C9	0.0358 (9)	0.0345 (9)	0.0548 (11)	0.0065 (7)	0.0108 (8)	−0.0039 (8)
C10	0.0376 (8)	0.0243 (8)	0.0429 (9)	−0.0023 (7)	0.0105 (7)	−0.0014 (7)
C11	0.0404 (9)	0.0381 (9)	0.0542 (11)	0.0022 (7)	0.0191 (8)	−0.0033 (8)
C12	0.0349 (9)	0.0372 (9)	0.0589 (11)	0.0045 (7)	0.0079 (8)	0.0003 (8)
C13	0.0728 (14)	0.0525 (12)	0.0495 (12)	0.0006 (10)	0.0045 (10)	−0.0017 (9)
N1	0.0475 (8)	0.0328 (8)	0.0455 (8)	−0.0036 (6)	0.0119 (7)	0.0014 (6)
O1	0.0507 (7)	0.0420 (7)	0.0437 (7)	0.0128 (6)	0.0126 (5)	0.0063 (5)
O2	0.0760 (9)	0.0356 (7)	0.0452 (7)	−0.0002 (7)	0.0020 (6)	−0.0077 (6)
O3	0.0587 (8)	0.0666 (9)	0.0394 (7)	0.0015 (7)	0.0252 (6)	0.0000 (6)
O4	0.0464 (7)	0.0555 (8)	0.0325 (6)	−0.0069 (6)	0.0110 (5)	−0.0001 (5)
S1	0.0436 (3)	0.0304 (2)	0.0315 (2)	0.00412 (16)	0.01122 (17)	−0.00084 (15)

Geometric parameters (Å, º) top

C1—C2	1.380 (2)	C9—C10	1.376 (2)
C1—C6	1.386 (2)	C9—H9	0.9300
C1—S1	1.7662 (16)	C10—C11	1.374 (2)
C2—C3	1.380 (2)	C10—N1	1.466 (2)
C2—H2	0.9300	C11—C12	1.381 (3)
C3—C4	1.382 (2)	C11—H11	0.9300
C3—H3	0.9300	C12—H12	0.9300
C4—O4	1.3603 (19)	C13—H13A	0.9600
C4—C5	1.385 (2)	C13—H13B	0.9600
C5—C6	1.375 (2)	C13—H13C	0.9600
C5—H5	0.9300	N1—H1A	0.8900
C6—H6	0.9300	N1—H1B	0.8900
C7—C12	1.385 (3)	N1—H1C	0.8900
C7—C8	1.387 (2)	O1—S1	1.4487 (12)
C7—C13	1.501 (3)	O2—S1	1.4414 (13)
C8—C9	1.374 (3)	O3—S1	1.4556 (13)
C8—H8	0.9300	O4—H4	0.8200

C2—C1—C6	119.85 (15)	C11—C10—N1	119.19 (15)
C2—C1—S1	120.82 (12)	C9—C10—N1	119.79 (15)
C6—C1—S1	119.30 (12)	C10—C11—C12	118.74 (16)
C1—C2—C3	119.81 (15)	C10—C11—H11	120.6
C1—C2—H2	120.1	C12—C11—H11	120.6
C3—C2—H2	120.1	C11—C12—C7	121.83 (16)
C2—C3—C4	120.32 (15)	C11—C12—H12	119.1
C2—C3—H3	119.8	C7—C12—H12	119.1
C4—C3—H3	119.8	C7—C13—H13A	109.5
O4—C4—C3	117.48 (14)	C7—C13—H13B	109.5
O4—C4—C5	122.66 (14)	H13A—C13—H13B	109.5
C3—C4—C5	119.85 (15)	C7—C13—H13C	109.5
C6—C5—C4	119.78 (15)	H13A—C13—H13C	109.5
C6—C5—H5	120.1	H13B—C13—H13C	109.5
C4—C5—H5	120.1	C10—N1—H1A	109.5
C5—C6—C1	120.38 (14)	C10—N1—H1B	109.5
C5—C6—H6	119.8	H1A—N1—H1B	109.5
C1—C6—H6	119.8	C10—N1—H1C	109.5
C12—C7—C8	117.63 (17)	H1A—N1—H1C	109.5
C12—C7—C13	120.91 (17)	H1B—N1—H1C	109.5
C8—C7—C13	121.46 (17)	C4—O4—H4	109.5
C9—C8—C7	121.47 (17)	O2—S1—O1	112.76 (8)
C9—C8—H8	119.3	O2—S1—O3	113.86 (8)
C7—C8—H8	119.3	O1—S1—O3	110.38 (8)
C8—C9—C10	119.31 (16)	O2—S1—C1	106.67 (7)
C8—C9—H9	120.3	O1—S1—C1	106.46 (7)
C10—C9—H9	120.3	O3—S1—C1	106.13 (7)
C11—C10—C9	121.02 (16)

C6—C1—C2—C3	0.8 (2)	C8—C9—C10—C11	0.3 (3)
S1—C1—C2—C3	−177.26 (13)	C8—C9—C10—N1	−179.65 (15)
C1—C2—C3—C4	−0.5 (2)	C9—C10—C11—C12	0.2 (3)
C2—C3—C4—O4	−179.85 (15)	N1—C10—C11—C12	−179.88 (15)
C2—C3—C4—C5	0.0 (2)	C10—C11—C12—C7	−0.7 (3)
O4—C4—C5—C6	−179.95 (14)	C8—C7—C12—C11	0.8 (3)
C3—C4—C5—C6	0.2 (2)	C13—C7—C12—C11	−179.14 (17)
C4—C5—C6—C1	0.1 (2)	C2—C1—S1—O2	−134.51 (14)
C2—C1—C6—C5	−0.6 (2)	C6—C1—S1—O2	47.42 (14)
S1—C1—C6—C5	177.49 (12)	C2—C1—S1—O1	104.85 (14)
C12—C7—C8—C9	−0.3 (3)	C6—C1—S1—O1	−73.21 (14)
C13—C7—C8—C9	179.63 (17)	C2—C1—S1—O3	−12.76 (15)
C7—C8—C9—C10	−0.2 (3)	C6—C1—S1—O3	169.17 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1ⁱ	0.89	1.96	2.8367 (19)	169
N1—H1B···O4ⁱⁱ	0.89	1.96	2.839 (2)	170
N1—H1A···O2ⁱⁱⁱ	0.89	1.94	2.8091 (19)	166
O4—H4···O3ⁱⁱⁱ	0.82	1.82	2.6343 (17)	173

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·C₆H₅O₄S⁻
M_r	281.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.6450 (2), 7.1670 (1), 16.3080 (3)
β (°)	107.654 (1)
V (Å³)	1296.96 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.926, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	11047, 2285, 2045
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.091, 1.06
No. of reflections	2285
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.29

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1ⁱ	0.89	1.96	2.8367 (19)	169.0
N1—H1B···O4ⁱⁱ	0.89	1.96	2.839 (2)	169.5
N1—H1A···O2ⁱⁱⁱ	0.89	1.94	2.8091 (19)	165.7
O4—H4···O3ⁱⁱⁱ	0.82	1.82	2.6343 (17)	172.5

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

Acknowledgements

The authors thank Professor D. Velmurugan, Centre for Advanced Study in Crystallography and Biophysics, University of Madras, for providing data collection and computer facilities.

References

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