Benzotriazolium 4-methyl­benzene­sulfonate

Thirunavukkarasu, A.; Silambarasan, A.; Kumar, R.M.; Umarani, P.R.; Chakkaravarthi, G.

doi:10.1107/S1600536814003857

organic compounds

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Volume 70| Part 3| March 2014| Page o350

doi:10.1107/S1600536814003857

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Benzotriazolium 4-methylbenzenesulfonate

A. Thirunavukkarasu,^a A. Silambarasan,^a R. Mohan Kumar,^a P. R. Umarani ^b ^* and G. Chakkaravarthi ^c ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bKunthavai Naacchiyaar Govt. Arts College (W), Thanjavur 613 007, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: kan_uma6@yahoo.com, chakkaravarthi_2005@yahoo.com

(Received 18 February 2014; accepted 19 February 2014; online 22 February 2014)

In the title molecular salt, C₆H₆N₃⁺·C₇H₇O₃S⁻, the components are linked by N—H⋯O hydrogen bonds into zigzag chains along [100]. These chains are further connected by weak C—H⋯O, C—H⋯π and π–π (centroid-to-centroid distances = 3.510, 3.701 and 3.754 Å) interactions into a three-dimensional network.

CCDC reference: 987882

Related literature

For biological activities of benzotriazole derivates, see: Dubey et al. (2011 ); Gaikwad et al. (2012 ). For related structures, see: Sudhahar et al. (2013 ); Yang et al. (2010 ).

Experimental

Crystal data

C₆H₆N₃⁺·C₇H₇O₃S⁻
M_r = 291.32
Orthorhombic, P b c a
a = 12.2330 (5) Å
b = 13.4144 (6) Å
c = 16.3320 (9) Å
V = 2680.1 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 295 K
0.26 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.937, T_max = 0.951
45507 measured reflections
3889 independent reflections
2766 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.108
S = 1.08
3889 reflections
191 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.87 (1)	1.82 (1)	2.661 (2)	161 (2)
N3—H3A⋯O3ⁱⁱ	0.87 (1)	1.77 (1)	2.6326 (19)	176 (2)
C3—H3⋯O2ⁱⁱⁱ	0.93	2.48	3.359 (2)	158
C12—H12⋯Cg1^iv	0.93	2.66	3.500 (2)	150
Symmetry codes: (i) -x+2, -y, -z; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{3\over 2}}, y, -z-{\script{1\over 2}}]$ .

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.

Supporting information

CCDC reference: 987882

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814003857/bt6963sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814003857/bt6963Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814003857/bt6963Isup3.cml

checkCIF report

Comment top

Benzotriazole derivates exhibit antitubercular and antimicrobial (Dubey et al., 2011; Gaikwad et al., 2012) bio-activities. We herewith report the crystal structure of the title compound (Fig. 1). In the title compound, the geometric parameters are comparable with reported structures (Sudhahar et al., 2013; Yang et al., 2010).

The crystal structure exhibits intermolecular N-H···O, C-H···O, C-H···π (Table 1; Fig. 2) and π···π interactions [Cg1···Cg2ⁱ: 3.510Å; Cg2···Cg3ⁱⁱ: 3.754Å; Cg3···Cg3ⁱⁱ: 3.701Å; symmetry operators: (i) x,y,z; (ii) 1-x,-y,-z; Cg1, Cg2 and Cg3 are the centroids of the rings (C1-C6), (N1/N2/C8/C13/N3) and (C8-C13), respectively].

Related literature top

For biological activities of benzotriazole derivates, see: Dubey et al. (2011); Gaikwad et al. (2012). For reported structures, see: Sudhahar et al. (2013); Yang et al. (2010).

Experimental top

Benzotriazole (C₆H₅N₃, 1.1913 g) and p-toluenesulfonic acid (CH₃C₆H₄S0₃H, 1.90 g) were taken in an equimolar ratio and dissolved in methanol and water. The solution was allowed for slow evaporation at room temperature. The crystals were collected after a the period of 45 days.

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).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of the title compound, viewed down a axis. Intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

Benzotriazolium 4-methylbenzenesulfonate top

Crystal data top

C₆H₆N₃⁺·C₇H₇O₃S⁻	F(000) = 1216
M_r = 291.32	D_x = 1.444 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9880 reflections
a = 12.2330 (5) Å	θ = 2.5–29.4°
b = 13.4144 (6) Å	µ = 0.25 mm⁻¹
c = 16.3320 (9) Å	T = 295 K
V = 2680.1 (2) Å³	Block, colourless
Z = 8	0.26 × 0.24 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3889 independent reflections
Radiation source: fine-focus sealed tube	2766 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω and φ scan	θ_max = 30.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
T_min = 0.937, T_max = 0.951	k = −18→18
45507 measured reflections	l = −22→23

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0359P)² + 1.3937P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3889 reflections	Δρ_max = 0.26 e Å⁻³
191 parameters	Δρ_min = −0.35 e Å⁻³
2 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: 0.0071 (5)

Crystal data top

C₆H₆N₃⁺·C₇H₇O₃S⁻	V = 2680.1 (2) Å³
M_r = 291.32	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.2330 (5) Å	µ = 0.25 mm⁻¹
b = 13.4144 (6) Å	T = 295 K
c = 16.3320 (9) Å	0.26 × 0.24 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3889 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2766 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.951	R_int = 0.037
45507 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	2 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.26 e Å⁻³
3889 reflections	Δρ_min = −0.35 e Å⁻³
191 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	0.90878 (12)	0.03041 (12)	0.16244 (9)	0.0333 (3)
C2	0.81836 (14)	0.05952 (13)	0.20733 (11)	0.0418 (4)
H2	0.7961	0.1258	0.2066	0.050*
C3	0.76102 (15)	−0.00918 (15)	0.25324 (11)	0.0460 (4)
H3	0.6998	0.0114	0.2824	0.055*
C4	0.79293 (15)	−0.10826 (14)	0.25669 (11)	0.0432 (4)
C5	0.88410 (16)	−0.13637 (13)	0.21152 (12)	0.0475 (4)
H5	0.9074	−0.2023	0.2132	0.057*
C6	0.94106 (15)	−0.06856 (13)	0.16406 (11)	0.0429 (4)
H6	1.0009	−0.0894	0.1333	0.051*
C7	0.73032 (19)	−0.18330 (17)	0.30695 (13)	0.0633 (6)
H7A	0.6711	−0.2097	0.2750	0.095*
H7B	0.7017	−0.1515	0.3550	0.095*
H7C	0.7783	−0.2366	0.3228	0.095*
C8	0.67586 (12)	0.01515 (12)	0.03229 (10)	0.0344 (3)
C9	0.67158 (15)	0.11875 (12)	0.02304 (11)	0.0414 (4)
H9	0.7228	0.1535	−0.0079	0.050*
C10	0.58772 (16)	0.16563 (14)	0.06224 (12)	0.0486 (4)
H10	0.5809	0.2344	0.0569	0.058*
C11	0.51133 (16)	0.11404 (15)	0.11036 (12)	0.0504 (5)
H11	0.4563	0.1499	0.1363	0.061*
C12	0.51505 (15)	0.01289 (14)	0.12041 (11)	0.0448 (4)
H12	0.4647	−0.0211	0.1526	0.054*
C13	0.59940 (13)	−0.03593 (12)	0.07916 (10)	0.0349 (3)
N1	0.71524 (13)	−0.14630 (11)	0.02730 (11)	0.0486 (4)
N2	0.74412 (12)	−0.05667 (11)	0.00306 (10)	0.0430 (3)
N3	0.62856 (13)	−0.13358 (11)	0.07344 (10)	0.0425 (3)
O1	0.93251 (11)	0.11850 (10)	0.02148 (8)	0.0524 (3)
O2	1.09402 (10)	0.08554 (10)	0.10320 (9)	0.0507 (3)
O3	0.96735 (11)	0.21352 (9)	0.14451 (8)	0.0507 (3)
S1	0.98089 (3)	0.11794 (3)	0.10202 (3)	0.03644 (12)
H2A	0.8027 (13)	−0.0538 (18)	−0.0271 (13)	0.075 (8)*
H3A	0.5961 (17)	−0.1848 (12)	0.0946 (13)	0.068 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0331 (8)	0.0359 (8)	0.0310 (8)	0.0049 (6)	−0.0028 (6)	−0.0038 (6)
C2	0.0387 (8)	0.0433 (9)	0.0434 (9)	0.0115 (7)	−0.0001 (7)	−0.0048 (7)
C3	0.0345 (8)	0.0616 (11)	0.0419 (9)	0.0035 (8)	0.0046 (7)	−0.0070 (9)
C4	0.0439 (9)	0.0508 (10)	0.0349 (9)	−0.0100 (8)	−0.0045 (7)	−0.0063 (7)
C5	0.0605 (12)	0.0349 (8)	0.0471 (10)	0.0004 (8)	0.0034 (9)	−0.0053 (7)
C6	0.0455 (9)	0.0392 (9)	0.0440 (9)	0.0079 (7)	0.0083 (8)	−0.0063 (7)
C7	0.0662 (14)	0.0698 (14)	0.0539 (12)	−0.0192 (11)	0.0060 (10)	0.0002 (11)
C8	0.0292 (7)	0.0383 (8)	0.0356 (8)	−0.0036 (6)	−0.0033 (6)	0.0015 (6)
C9	0.0429 (9)	0.0369 (8)	0.0443 (9)	−0.0090 (7)	0.0000 (7)	0.0052 (7)
C10	0.0580 (11)	0.0344 (8)	0.0534 (11)	−0.0022 (8)	−0.0013 (9)	−0.0022 (8)
C11	0.0490 (10)	0.0524 (11)	0.0499 (11)	0.0039 (9)	0.0062 (9)	−0.0123 (9)
C12	0.0415 (9)	0.0531 (10)	0.0399 (9)	−0.0085 (8)	0.0070 (7)	−0.0001 (8)
C13	0.0349 (8)	0.0343 (8)	0.0356 (8)	−0.0063 (6)	−0.0049 (6)	0.0023 (6)
N1	0.0438 (8)	0.0392 (8)	0.0628 (10)	0.0038 (7)	−0.0060 (8)	0.0024 (7)
N2	0.0329 (7)	0.0426 (8)	0.0536 (9)	0.0011 (6)	0.0020 (7)	0.0027 (7)
N3	0.0429 (8)	0.0352 (7)	0.0496 (9)	−0.0059 (6)	−0.0045 (7)	0.0072 (6)
O1	0.0532 (8)	0.0656 (9)	0.0383 (7)	0.0041 (7)	−0.0027 (6)	0.0063 (6)
O2	0.0346 (6)	0.0543 (7)	0.0631 (9)	0.0069 (6)	0.0037 (6)	0.0067 (6)
O3	0.0629 (8)	0.0335 (6)	0.0558 (8)	0.0072 (6)	−0.0009 (7)	0.0004 (5)
S1	0.0347 (2)	0.0360 (2)	0.0387 (2)	0.00720 (16)	−0.00031 (16)	0.00142 (16)

Geometric parameters (Å, º) top

C1—C2	1.383 (2)	C8—C9	1.399 (2)
C1—C6	1.385 (2)	C9—C10	1.363 (3)
C1—S1	1.7694 (17)	C9—H9	0.9300
C2—C3	1.380 (3)	C10—C11	1.404 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.386 (3)	C11—C12	1.368 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.389 (3)	C12—C13	1.395 (2)
C4—C7	1.508 (3)	C12—H12	0.9300
C5—C6	1.383 (3)	C13—N3	1.361 (2)
C5—H5	0.9300	N1—N3	1.312 (2)
C6—H6	0.9300	N1—N2	1.314 (2)
C7—H7A	0.9600	N2—H2A	0.871 (9)
C7—H7B	0.9600	N3—H3A	0.866 (9)
C7—H7C	0.9600	O1—S1	1.4423 (14)
C8—N2	1.361 (2)	O2—S1	1.4507 (13)
C8—C13	1.389 (2)	O3—S1	1.4673 (13)

C2—C1—C6	119.24 (16)	C10—C9—H9	122.1
C2—C1—S1	120.46 (13)	C8—C9—H9	122.1
C6—C1—S1	120.29 (13)	C9—C10—C11	122.46 (17)
C3—C2—C1	120.40 (16)	C9—C10—H10	118.8
C3—C2—H2	119.8	C11—C10—H10	118.8
C1—C2—H2	119.8	C12—C11—C10	122.29 (18)
C2—C3—C4	121.28 (16)	C12—C11—H11	118.9
C2—C3—H3	119.4	C10—C11—H11	118.9
C4—C3—H3	119.4	C11—C12—C13	115.62 (16)
C3—C4—C5	117.69 (17)	C11—C12—H12	122.2
C3—C4—C7	121.27 (18)	C13—C12—H12	122.2
C5—C4—C7	121.04 (18)	N3—C13—C8	105.09 (15)
C6—C5—C4	121.57 (17)	N3—C13—C12	132.75 (16)
C6—C5—H5	119.2	C8—C13—C12	122.16 (15)
C4—C5—H5	119.2	N3—N1—N2	105.75 (14)
C5—C6—C1	119.81 (16)	N1—N2—C8	112.14 (15)
C5—C6—H6	120.1	N1—N2—H2A	115.6 (16)
C1—C6—H6	120.1	C8—N2—H2A	132.3 (16)
C4—C7—H7A	109.5	N1—N3—C13	112.12 (14)
C4—C7—H7B	109.5	N1—N3—H3A	119.8 (16)
H7A—C7—H7B	109.5	C13—N3—H3A	128.1 (16)
C4—C7—H7C	109.5	O1—S1—O2	113.90 (8)
H7A—C7—H7C	109.5	O1—S1—O3	112.36 (8)
H7B—C7—H7C	109.5	O2—S1—O3	111.30 (8)
N2—C8—C13	104.90 (14)	O1—S1—C1	107.91 (8)
N2—C8—C9	133.48 (16)	O2—S1—C1	105.62 (7)
C13—C8—C9	121.62 (15)	O3—S1—C1	105.06 (8)
C10—C9—C8	115.83 (16)

C6—C1—C2—C3	0.1 (3)	N2—C8—C13—C12	179.46 (15)
S1—C1—C2—C3	178.81 (13)	C9—C8—C13—C12	−0.8 (3)
C1—C2—C3—C4	0.9 (3)	C11—C12—C13—N3	−179.15 (18)
C2—C3—C4—C5	−0.7 (3)	C11—C12—C13—C8	1.2 (3)
C2—C3—C4—C7	179.93 (18)	N3—N1—N2—C8	−0.8 (2)
C3—C4—C5—C6	−0.5 (3)	C13—C8—N2—N1	0.63 (19)
C7—C4—C5—C6	178.86 (18)	C9—C8—N2—N1	−179.05 (18)
C4—C5—C6—C1	1.5 (3)	N2—N1—N3—C13	0.6 (2)
C2—C1—C6—C5	−1.2 (3)	C8—C13—N3—N1	−0.21 (19)
S1—C1—C6—C5	180.00 (14)	C12—C13—N3—N1	−179.87 (18)
N2—C8—C9—C10	179.18 (18)	C2—C1—S1—O1	−89.85 (15)
C13—C8—C9—C10	−0.4 (3)	C6—C1—S1—O1	88.90 (15)
C8—C9—C10—C11	1.2 (3)	C2—C1—S1—O2	147.97 (14)
C9—C10—C11—C12	−0.8 (3)	C6—C1—S1—O2	−33.28 (16)
C10—C11—C12—C13	−0.5 (3)	C2—C1—S1—O3	30.22 (15)
N2—C8—C13—N3	−0.24 (17)	C6—C1—S1—O3	−151.04 (14)
C9—C8—C13—N3	179.48 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.87 (1)	1.82 (1)	2.661 (2)	161 (2)
N3—H3A···O3ⁱⁱ	0.87 (1)	1.77 (1)	2.6326 (19)	176 (2)
C3—H3···O2ⁱⁱⁱ	0.93	2.48	3.359 (2)	158
C12—H12···Cg1^iv	0.93	2.66	3.500 (2)	150

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.871 (9)	1.822 (12)	2.661 (2)	161 (2)
N3—H3A···O3ⁱⁱ	0.866 (9)	1.768 (10)	2.6326 (19)	176 (2)
C3—H3···O2ⁱⁱⁱ	0.93	2.48	3.359 (2)	158
C12—H12···Cg1^iv	0.93	2.66	3.500 (2)	150

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

Acknowledgements

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

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