Crystal structure of 4-bromo-anilinium 4-methyl-benzene-sulfonate.

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

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 ▸).

Experimental

Crystal data

C6H7BrN+·C7H7O3S−

M = 344.22

Triclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.083

S = 1.03

3001 reflections

175 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.56 e Å−3

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 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015002686/su5079sup1.cif

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

Click here for additional data file.

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

Click here for additional data file.

. DOI: 10.1107/S2056989015002686/su5079fig1.tif

The mol­ecular structure of the title mol­ecular salt, with atom labelling. Displacement ellipsoids ae drawn at the 30% probability level.

Click here for additional data file.

a . DOI: 10.1107/S2056989015002686/su5079fig2.tif

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).

CCDC reference: 1048164

Additional supporting information: crystallographic information; 3D view; checkCIF report

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) Å3

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 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(Fo2) + (0.0406P)2 + 0.3371P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (2)

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.

	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)

	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)

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)

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

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1AO2	0.89	2.07	2.879(2)	151
N1H1CO1i	0.89	2.46	2.971(2)	117
N1H1AO2i	0.89	2.46	3.096(2)	129
N1H1BO3ii	0.89	1.91	2.794(2)	172
N1H1CO1iii	0.89	2.04	2.904(2)	165

Symmetry codes: (i) ; (ii) ; (iii) .