organic compounds
Benzotriazolium 4-methylbenzenesulfonate
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
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
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Data collection: APEX2 (Bruker, 2004); cell 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
10.1107/S1600536814003857/bt6963sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814003857/bt6963Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814003857/bt6963Isup3.cml
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.
All H atoms were located in a difference Fourier map. N-bound H atoms were refined with an N-H distance restraint of 0.86 (1)Å. The C-bound H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 and Uiso(H) = 1.2Ueq(C) for CH and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for CH3.
Data collection: APEX2 (Bruker, 2004); cell
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).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. |
C6H6N3+·C7H7O3S− | F(000) = 1216 |
Mr = 291.32 | Dx = 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 |
Bruker Kappa APEXII CCD diffractometer | 3889 independent reflections |
Radiation source: fine-focus sealed tube | 2766 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω and φ scan | θmax = 30.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.937, Tmax = 0.951 | k = −18→18 |
45507 measured reflections | l = −22→23 |
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(Fo2) + (0.0359P)2 + 1.3937P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3889 reflections | Δρmax = 0.26 e Å−3 |
191 parameters | Δρmin = −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) |
C6H6N3+·C7H7O3S− | V = 2680.1 (2) Å3 |
Mr = 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 |
Bruker Kappa APEXII CCD diffractometer | 3889 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2766 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.951 | Rint = 0.037 |
45507 measured reflections |
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 | Δρmax = 0.26 e Å−3 |
3889 reflections | Δρmin = −0.35 e Å−3 |
191 parameters |
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 | 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)* |
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) |
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) |
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···Cg1iv | 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. |
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···Cg1iv | 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.
References
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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].