Crystal structure of 4-bromo­anilinium 4-methyl­benzene­sulfonate

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.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.083
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

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Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O1     ..  O1      ..       2.84 Ang.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.979 Note
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...     Please Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         53 Report

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         13 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Structural commentary

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].

S2. Synthesis and crystallization

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.

S3. Refinement

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

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

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

	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

Crystal data

C6H7BrN^+·C7H7O3S^−	Z = 2
Mr = 344.22	F(000) = 3048
Triclinic, P1	Dx = 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) Å^3

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0406P)^2 + 0.3371P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3001 reflections	Δρmax = 0.45 e Å^−3
175 parameters	Δρmin = −0.56 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O1^i	0.89	2.46	2.971 (2)	117
N1—H1A···O2^i	0.89	2.46	3.096 (2)	129
N1—H1B···O3^ii	0.89	1.91	2.794 (2)	172
N1—H1C···O1^iii	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.