Crystal structure of 4-bromo­anilinium 4-methyl­benzene­sulfonate

Sivakumar, P.K.; Kumar, M.K.; Kumar, R.M.; Chakkaravarthi, G.; Kanagadurai, R.

doi:10.1107/S2056989015002686

organic compounds

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Volume 71| Part 3| March 2015| Pages o163-o164

doi:10.1107/S2056989015002686

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Crystal structure of 4-bromoanilinium 4-methylbenzenesulfonate

P. K. Sivakumar,^a M. Krishna Kumar,^b R. Mohan Kumar,^b G. Chakkaravarthi ^c ^* and R. Kanagadurai ^b ^*

^aDepartment of Physics, M. N. M. Jain Engineering College, Chennai 600 097, India, ^bDepartment of Physics, Presidency College, Chennai 600 005, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, srkanagadurai@yahoo.co.in

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 5 February 2015; accepted 8 February 2015; online 13 February 2015)

In the crystal of the title molecular salt, C₆H₇BrN⁺·C₇H₇O₃S⁻, the anions and cations are linked via N—H⋯O hydrogen bonds forming layers, enclosing R₂²(4) ring motifs, lying parallel to (001). Within the layers there are short O⋯O contacts of 2.843 (2) Å.

Keywords: crystal structure; anilinium; 4-methylbenzenesulfonate; hydrogen bonding.

CCDC reference: 1048164

1. Related literature

For the crystal structure of 4-chloroanilinium 4-methylbenzenesulfonate, isostructural with the title salt, see: Jasinski et al. (2011 ). For the crystal structure of other 4-methylbenzenesulfonate salts, see, for example: Krishnakumar et al. (2012 ); Sudhahar et al. (2013 ).

2. Experimental

2.1. Crystal data

C₆H₇BrN⁺·C₇H₇O₃S⁻
M_r = 344.22
Triclinic, $[P \overline 1]$
a = 5.7908 (3) Å
b = 7.6004 (4) Å
c = 15.9073 (7) Å
α = 94.716 (2)°
β = 96.520 (3)°
γ = 92.732 (2)°
V = 692.09 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.12 mm⁻¹
T = 295 K
0.24 × 0.20 × 0.18 mm

2.2. Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.521, T_max = 0.603
11503 measured reflections
3001 independent reflections
2526 reflections with I > 2σ(I)
R_int = 0.030

2.3. Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.083
S = 1.03
3001 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.89	2.07	2.879 (2)	151
N1—H1C⋯O1ⁱ	0.89	2.46	2.971 (2)	117
N1—H1A⋯O2ⁱ	0.89	2.46	3.096 (2)	129
N1—H1B⋯O3ⁱⁱ	0.89	1.91	2.794 (2)	172
N1—H1C⋯O1ⁱⁱⁱ	0.89	2.04	2.904 (2)	165
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x, y-1, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supporting information

CCDC reference: 1048164

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015002686/su5079sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015002686/su5079Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015002686/su5079Isup3.cml

checkCIF report

Structural commentary top

The molecular structure of the title salt is illustrated in Fig. 1. The bond lengths and angles are similar to those reported for the 4-chloroanilinium analogue (Jasinski et al., 2011), and for other similar 4-methylbenzenesulfonate salts (Krishnakumar et al., 2012; Sudhahar et al., 2013).

In the crystal, the benzene rings (C1—C6) and (C8—C13) make a dihedral angle of 50.89 (11) °. The cations and anions are linked via N—H···O hydrogen bonds which generates R₂²(4) ring motifs, and form layers parallel to (001); see Table 1 and Fig. 2. Within the layers there are short O1···O1ⁱ contacts of 2.843 (2) Å [symmetry code: (i) -x+2, -y+2, -z+1].

Synthesis and crystallization top

The title compound was synthesized in ethanol by mixing 4-bromoaniline (2.37 g) and p-toluenesulfonicacid (2.62 g) in an equimolar ratio. The saturated solution was allowed to evaporating slowly at room temperature. After a period of three weeks colourless block-like crystals appeared.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically and refined using a riding model: N—H = 0.89 Å, C—H = 0.93 - 96 Å with U_iso(H) = 1.5U_eq(N,C) for the ammonium and methyl H atoms and = 1.2U_eq(C) for other H atoms.

Related literature top

For the crystal structure of 4-chloroanilinium 4-methylbenzenesulfonate, isostructural with the title salt, see: Jasinski et al. (2011). For the crystal structure of other 4-methylbenzenesulfonate salts, see, for example: Krishnakumar et al. (2012); Sudhahar et al. (2013).

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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecular salt, with atom labelling. Displacement ellipsoids ae drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title molecular salt, viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

4-Bromoanilinium 4-methylbenzenesulfonate top

Crystal data top

C₆H₇BrN⁺·C₇H₇O₃S⁻	Z = 2
M_r = 344.22	F(000) = 3048
Triclinic, P1	D_x = 1.652 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7908 (3) Å	Cell parameters from 348 reflections
b = 7.6004 (4) Å	θ = 1.3–27.1°
c = 15.9073 (7) Å	µ = 3.12 mm⁻¹
α = 94.716 (2)°	T = 295 K
β = 96.520 (3)°	Block, colourless
γ = 92.732 (2)°	0.24 × 0.20 × 0.18 mm
V = 692.09 (6) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	3001 independent reflections
Radiation source: fine-focus sealed tube	2526 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and ϕ scan	θ_max = 27.1°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.521, T_max = 0.603	k = −9→9
11503 measured reflections	l = −20→20

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0406P)² + 0.3371P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3001 reflections	Δρ_max = 0.45 e Å⁻³
175 parameters	Δρ_min = −0.56 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: 0.034 (2)

Crystal data top

C₆H₇BrN⁺·C₇H₇O₃S⁻	γ = 92.732 (2)°
M_r = 344.22	V = 692.09 (6) Å³
Triclinic, P1	Z = 2
a = 5.7908 (3) Å	Mo Kα radiation
b = 7.6004 (4) Å	µ = 3.12 mm⁻¹
c = 15.9073 (7) Å	T = 295 K
α = 94.716 (2)°	0.24 × 0.20 × 0.18 mm
β = 96.520 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3001 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2526 reflections with I > 2σ(I)
T_min = 0.521, T_max = 0.603	R_int = 0.030
11503 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.03	Δρ_max = 0.45 e Å⁻³
3001 reflections	Δρ_min = −0.56 e Å⁻³
175 parameters

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. 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 > 2sigma(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	1.0889 (4)	0.8014 (3)	0.89050 (15)	0.0401 (6)
C2	1.2329 (4)	0.8603 (4)	0.83410 (17)	0.0428 (6)
H2	1.3820	0.9068	0.8546	0.051*
C3	1.1611 (4)	0.8518 (3)	0.74779 (15)	0.0353 (5)
H3	1.2613	0.8909	0.7106	0.042*
C4	0.9385 (3)	0.7845 (3)	0.71760 (12)	0.0233 (4)
C5	0.7913 (4)	0.7260 (3)	0.77291 (15)	0.0351 (5)
H5	0.6416	0.6807	0.7525	0.042*
C6	0.8673 (4)	0.7348 (4)	0.85901 (15)	0.0439 (6)
H6	0.7674	0.6952	0.8962	0.053*
C7	1.1741 (6)	0.8053 (5)	0.98404 (18)	0.0686 (9)
H7A	1.2377	0.6944	0.9958	0.103*
H7B	1.0464	0.8251	1.0166	0.103*
H7C	1.2922	0.8991	0.9992	0.103*
C8	0.4302 (4)	0.3193 (3)	0.77075 (14)	0.0317 (5)
C9	0.6357 (4)	0.2352 (3)	0.77106 (15)	0.0342 (5)
H9	0.7066	0.1958	0.8209	0.041*
C10	0.7353 (4)	0.2102 (3)	0.69649 (14)	0.0296 (5)
H10	0.8749	0.1548	0.6958	0.036*
C11	0.6259 (3)	0.2681 (3)	0.62306 (13)	0.0253 (4)
C12	0.4203 (4)	0.3529 (3)	0.62302 (14)	0.0309 (5)
H12	0.3492	0.3920	0.5731	0.037*
C13	0.3209 (4)	0.3792 (3)	0.69759 (15)	0.0329 (5)
H13	0.1826	0.4363	0.6986	0.039*
N1	0.7352 (3)	0.2443 (2)	0.54491 (11)	0.0301 (4)
H1A	0.8264	0.3397	0.5401	0.045*
H1B	0.6256	0.2287	0.5006	0.045*
H1C	0.8204	0.1499	0.5464	0.045*
O1	0.9616 (3)	0.9187 (2)	0.57494 (10)	0.0387 (4)
O2	0.9290 (3)	0.6031 (2)	0.57251 (10)	0.0372 (4)
O3	0.5965 (3)	0.7733 (3)	0.59796 (10)	0.0460 (4)
Br1	0.29548 (5)	0.35751 (4)	0.873294 (18)	0.05714 (14)
S1	0.84823 (9)	0.76863 (7)	0.60718 (3)	0.02575 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0476 (14)	0.0480 (14)	0.0238 (12)	0.0154 (11)	−0.0024 (10)	−0.0011 (10)
C2	0.0341 (12)	0.0518 (15)	0.0382 (14)	0.0012 (11)	−0.0083 (10)	−0.0035 (11)
C3	0.0298 (11)	0.0428 (13)	0.0327 (12)	−0.0022 (9)	0.0030 (9)	0.0032 (10)
C4	0.0287 (10)	0.0214 (9)	0.0200 (10)	0.0048 (8)	0.0029 (7)	0.0010 (8)
C5	0.0315 (11)	0.0463 (14)	0.0273 (12)	−0.0034 (10)	0.0038 (9)	0.0050 (10)
C6	0.0460 (14)	0.0625 (17)	0.0261 (12)	0.0034 (12)	0.0111 (10)	0.0106 (11)
C7	0.077 (2)	0.098 (3)	0.0278 (14)	0.0243 (19)	−0.0093 (14)	−0.0014 (16)
C8	0.0353 (11)	0.0310 (11)	0.0287 (12)	0.0018 (9)	0.0061 (9)	−0.0007 (9)
C9	0.0399 (12)	0.0358 (12)	0.0267 (11)	0.0083 (10)	−0.0007 (9)	0.0055 (9)
C10	0.0289 (10)	0.0283 (11)	0.0315 (12)	0.0075 (8)	0.0003 (8)	0.0034 (9)
C11	0.0263 (10)	0.0220 (10)	0.0262 (11)	−0.0013 (8)	0.0009 (8)	−0.0012 (8)
C12	0.0300 (11)	0.0321 (11)	0.0299 (12)	0.0054 (9)	−0.0020 (9)	0.0046 (9)
C13	0.0273 (11)	0.0333 (12)	0.0379 (13)	0.0070 (9)	0.0020 (9)	0.0015 (10)
N1	0.0298 (9)	0.0316 (9)	0.0286 (10)	0.0032 (7)	0.0019 (7)	0.0029 (8)
O1	0.0566 (10)	0.0325 (8)	0.0315 (9)	0.0091 (7)	0.0160 (7)	0.0109 (7)
O2	0.0531 (10)	0.0281 (8)	0.0297 (9)	0.0057 (7)	0.0065 (7)	−0.0053 (7)
O3	0.0321 (9)	0.0787 (13)	0.0263 (9)	0.0106 (8)	−0.0017 (7)	0.0025 (8)
Br1	0.0649 (2)	0.0722 (2)	0.03948 (19)	0.02182 (15)	0.02132 (13)	0.00502 (14)
S1	0.0313 (3)	0.0287 (3)	0.0179 (3)	0.0066 (2)	0.00382 (19)	0.0019 (2)

Geometric parameters (Å, º) top

C1—C2	1.379 (4)	C8—Br1	1.894 (2)
C1—C6	1.380 (4)	C9—C10	1.380 (3)
C1—C7	1.511 (3)	C9—H9	0.9300
C2—C3	1.384 (3)	C10—C11	1.379 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.382 (3)	C11—C12	1.381 (3)
C3—H3	0.9300	C11—N1	1.460 (3)
C4—C5	1.377 (3)	C12—C13	1.380 (3)
C4—S1	1.767 (2)	C12—H12	0.9300
C5—C6	1.385 (3)	C13—H13	0.9300
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—S1	1.4480 (16)
C7—H7C	0.9600	O2—S1	1.4513 (16)
C8—C9	1.377 (3)	O3—S1	1.4509 (17)
C8—C13	1.382 (3)

C2—C1—C6	118.3 (2)	C8—C9—C10	119.2 (2)
C2—C1—C7	120.7 (3)	C8—C9—H9	120.4
C6—C1—C7	120.9 (3)	C10—C9—H9	120.4
C1—C2—C3	121.6 (2)	C11—C10—C9	119.39 (19)
C1—C2—H2	119.2	C11—C10—H10	120.3
C3—C2—H2	119.2	C9—C10—H10	120.3
C4—C3—C2	119.1 (2)	C10—C11—C12	121.2 (2)
C4—C3—H3	120.5	C10—C11—N1	118.94 (18)
C2—C3—H3	120.5	C12—C11—N1	119.80 (18)
C5—C4—C3	120.20 (19)	C13—C12—C11	119.56 (19)
C5—C4—S1	120.52 (16)	C13—C12—H12	120.2
C3—C4—S1	119.26 (16)	C11—C12—H12	120.2
C4—C5—C6	119.7 (2)	C12—C13—C8	118.9 (2)
C4—C5—H5	120.1	C12—C13—H13	120.5
C6—C5—H5	120.1	C8—C13—H13	120.5
C1—C6—C5	121.0 (2)	C11—N1—H1A	109.5
C1—C6—H6	119.5	C11—N1—H1B	109.5
C5—C6—H6	119.5	H1A—N1—H1B	109.5
C1—C7—H7A	109.5	C11—N1—H1C	109.5
C1—C7—H7B	109.5	H1A—N1—H1C	109.5
H7A—C7—H7B	109.5	H1B—N1—H1C	109.5
C1—C7—H7C	109.5	O1—S1—O3	113.04 (11)
H7A—C7—H7C	109.5	O1—S1—O2	111.33 (10)
H7B—C7—H7C	109.5	O3—S1—O2	113.23 (11)
C9—C8—C13	121.7 (2)	O1—S1—C4	106.17 (10)
C9—C8—Br1	119.41 (16)	O3—S1—C4	106.11 (10)
C13—C8—Br1	118.93 (17)	O2—S1—C4	106.31 (9)

C6—C1—C2—C3	−0.8 (4)	C9—C10—C11—C12	0.9 (3)
C7—C1—C2—C3	177.6 (3)	C9—C10—C11—N1	178.73 (19)
C1—C2—C3—C4	0.7 (4)	C10—C11—C12—C13	−0.5 (3)
C2—C3—C4—C5	−0.3 (3)	N1—C11—C12—C13	−178.31 (19)
C2—C3—C4—S1	−178.54 (19)	C11—C12—C13—C8	−0.1 (3)
C3—C4—C5—C6	0.0 (3)	C9—C8—C13—C12	0.4 (3)
S1—C4—C5—C6	178.18 (19)	Br1—C8—C13—C12	179.35 (16)
C2—C1—C6—C5	0.4 (4)	C5—C4—S1—O1	147.56 (18)
C7—C1—C6—C5	−178.0 (3)	C3—C4—S1—O1	−34.23 (19)
C4—C5—C6—C1	0.0 (4)	C5—C4—S1—O3	27.0 (2)
C13—C8—C9—C10	0.0 (3)	C3—C4—S1—O3	−154.76 (18)
Br1—C8—C9—C10	−178.95 (17)	C5—C4—S1—O2	−93.79 (19)
C8—C9—C10—C11	−0.7 (3)	C3—C4—S1—O2	84.42 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.89	2.07	2.879 (2)	151
N1—H1C···O1ⁱ	0.89	2.46	2.971 (2)	117
N1—H1A···O2ⁱ	0.89	2.46	3.096 (2)	129
N1—H1B···O3ⁱⁱ	0.89	1.91	2.794 (2)	172
N1—H1C···O1ⁱⁱⁱ	0.89	2.04	2.904 (2)	165

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.89	2.07	2.879 (2)	151
N1—H1C···O1ⁱ	0.89	2.46	2.971 (2)	117
N1—H1A···O2ⁱ	0.89	2.46	3.096 (2)	129
N1—H1B···O3ⁱⁱ	0.89	1.91	2.794 (2)	172
N1—H1C···O1ⁱⁱⁱ	0.89	2.04	2.904 (2)	165

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

Acknowledgements

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

References

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doi:10.1107/S2056989015002686

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