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Volume 70 
Part 5 
Pages o600-o601  
May 2014  

Received 10 April 2014
Accepted 15 April 2014
Online 26 April 2014

Key indicators
Single-crystal X-ray study
T = 293 K
Mean [sigma](C-C) = 0.003 Å
R = 0.040
wR = 0.119
Data-to-parameter ratio = 16.8
Details
Open access

2-Amino-6-methyl­pyridinium 4-methyl­benzene­sulfonate

aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, Tamil Nadu, India, and bDepartment of Physics, The New College (Autonomous), Chennai 600 014, Tamil Nadu, India
Correspondence e-mail: mnizam_new@yahoo.in, professormohan@yahoo.co.in

In the asymmetric unit of the title salt, C6H9N2+·C7H7O3S-, there are two independent 2-amino-6-methyl­pyridinium cations and two independent 4-methyl­benzene­sulfonate anions. Both cations are protonated at their pyridine N atoms and their geometries reveal amine-imine tautomerism. In the 4-methyl­benzene­sulfonate anions, the carboxyl­ate groups are twisted out of the benzene ring planes by 88.4 (1) and 86.2 (2)°. In the crystal, the sulfonate O atoms of an anion inter­act with the protonated N atoms and the 2-amino groups of a cation via a pair of N-H...O hydrogen bonds, forming an R22(8) ring motif. These motifs are connected via N-H...O hydrogen bonds, forming chains running along the a-axis direction. Within the chains there are weak C-H...O hydrogen bonds present. In addition, aromatic [pi]-[pi] stacking inter­actions [centroid-centroid distances = 3.771 (2), 3.599 (2), 3.599 (2) and 3.497 (2) Å] involving neighbouring chains are also observed.

Related literature

For crystal structures of related pyridine derivatives and their applications, see: Babu et al. (2014[Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014). Acta Cryst. E70, o391-o392.]); Rajkumar et al. (2014[Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473-o474.]); Jin et al. (2005[Jin, Z.-M., Shun, N., Lü, Y.-P., Hu, M.-L. & Shen, L. (2005). Acta Cryst. C61, m43-m45.]). For unprotonated amino­pyridine derivatives, see: Anderson et al. (2005[Anderson, F. P., Gallagher, J. F., Kenny, P. T. M. & Lough, A. J. (2005). Acta Cryst. E61, o1350-o1353.]). For the structure of amino-methyl­pyridinium, see: Nahringbauer & Kvick (1977[Nahringbauer, I. & Kvick, Å. (1977). Acta Cryst. B33, 2902-2905.]). For details of sulfonates, see: Onoda et al. (2001[Onoda, A., Yamada, Y., Doi, M., Okamura, T. & Ueyama, N. (2001). Inorg. Chem. 40, 516-521.]); Baskar Raj et al. (2003[Baskar Raj, S., Sethuraman, V., Francis, S., Hemamalini, M., Muthiah, P. T., Bocelli, G., Cantoni, A., Rychlewska, U. & Warzajtis, B. (2003). CrystEngComm, 5, 70-76.]). For applications of benzene­sulfonic acid, see: Wang & Wei (2007[Wang, Z.-L. & Wei, L.-H. (2007). Acta Cryst. E63, o1448-o1449.]). For simple organic-inorganic salts containing strong inter­molecular hydrogen bonds, see: Sethuram et al. (2013a[Sethuram, M., Bhargavi, G., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013a). Acta Cryst. E69, o1301-o1302.],b[Sethuram, M., Rajasekharan, M. V., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013b). Acta Cryst. E69, o957-o958.]); Shihabuddeen Syed et al. (2013[Shihabuddeen Syed, A., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, i33.]); Showrilu et al. (2013[Showrilu, K., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, m469-m470.]); Huq et al. (2013[Huq, C. A. M. A., Fouzia, S. & NizamMohideen, M. (2013). Acta Cryst. E69, o1766-o1767.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). For studies on the tautomeric forms of 2-amino­pyridine systems, see: Ishikawa et al. (2002[Ishikawa, H., Iwata, K. & Hamaguchi, H. (2002). J. Phys. Chem. A, 106, 2305-2312.]). For graph-set analysis, see: Etter (1990[Etter, M. C. (1990). Acc. Chem. Res. 23, 120-126.]); Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C6H9N2+·C7H7O3S-

  • Mr = 280.35

  • Triclinic, [P \overline 1]

  • a = 7.5343 (2) Å

  • b = 13.6212 (5) Å

  • c = 13.9887 (5) Å

  • [alpha] = 106.307 (2)°

  • [beta] = 97.946 (1)°

  • [gamma] = 92.103 (2)°

  • V = 1360.31 (8) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.24 mm-1

  • T = 293 K

  • 0.35 × 0.25 × 0.20 mm

Data collection
  • Bruker Kappa APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004[Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.]) Tmin = 0.920, Tmax = 0.953

  • 32534 measured reflections

  • 6237 independent reflections

  • 4709 reflections with I > 2[sigma](I)

  • Rint = 0.026

Refinement
  • R[F2 > 2[sigma](F2)] = 0.040

  • wR(F2) = 0.119

  • S = 1.06

  • 6237 reflections

  • 372 parameters

  • 6 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • [Delta][rho]max = 0.33 e Å-3

  • [Delta][rho]min = -0.37 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N1-H1A...O2 0.90 (1) 1.88 (1) 2.772 (2) 171 (2)
N2-H2A...O3i 0.87 (1) 2.01 (1) 2.880 (2) 174 (2)
N2-H2B...O1 0.88 (1) 2.07 (1) 2.919 (2) 162 (2)
N3-H3A...O5 0.89 (1) 1.90 (1) 2.789 (2) 174 (2)
N4-H4A...O4ii 0.88 (1) 2.02 (1) 2.882 (2) 167 (2)
N4-H4B...O6 0.88 (1) 2.04 (1) 2.883 (2) 162 (2)
C22-H22...O5ii 0.93 2.58 3.455 (2) 157
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2 and SAINT (Bruker, 2004[Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT and XPREP (Bruker, 2004[Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).


Supporting information for this paper is available from the IUCr electronic archives (Reference: SU2726 ).


Acknowledgements

The authors are thankful to the SAIF, IIT Madras, for the data collection.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.  [CrossRef]
Anderson, F. P., Gallagher, J. F., Kenny, P. T. M. & Lough, A. J. (2005). Acta Cryst. E61, o1350-o1353.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014). Acta Cryst. E70, o391-o392.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
Baskar Raj, S., Sethuraman, V., Francis, S., Hemamalini, M., Muthiah, P. T., Bocelli, G., Cantoni, A., Rychlewska, U. & Warzajtis, B. (2003). CrystEngComm, 5, 70-76.  [Web of Science] [CSD] [CrossRef] [ChemPort]
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.  [CrossRef] [ChemPort] [Web of Science]
Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.
Etter, M. C. (1990). Acc. Chem. Res. 23, 120-126.  [CrossRef] [ChemPort] [Web of Science]
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Huq, C. A. M. A., Fouzia, S. & NizamMohideen, M. (2013). Acta Cryst. E69, o1766-o1767.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
Ishikawa, H., Iwata, K. & Hamaguchi, H. (2002). J. Phys. Chem. A, 106, 2305-2312.  [Web of Science] [CrossRef] [ChemPort]
Jin, Z.-M., Shun, N., Lü, Y.-P., Hu, M.-L. & Shen, L. (2005). Acta Cryst. C61, m43-m45.  [CSD] [CrossRef] [IUCr Journals]
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Nahringbauer, I. & Kvick, Å. (1977). Acta Cryst. B33, 2902-2905.  [CSD] [CrossRef] [IUCr Journals] [Web of Science]
Onoda, A., Yamada, Y., Doi, M., Okamura, T. & Ueyama, N. (2001). Inorg. Chem. 40, 516-521.  [Web of Science] [CSD] [CrossRef] [PubMed] [ChemPort]
Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473-o474.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
Sethuram, M., Bhargavi, G., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013a). Acta Cryst. E69, o1301-o1302.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
Sethuram, M., Rajasekharan, M. V., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013b). Acta Cryst. E69, o957-o958.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Shihabuddeen Syed, A., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, i33.  [CrossRef] [IUCr Journals]
Showrilu, K., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, m469-m470.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Wang, Z.-L. & Wei, L.-H. (2007). Acta Cryst. E63, o1448-o1449.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]


Acta Cryst (2014). E70, o600-o601   [ doi:10.1107/S1600536814008587 ]

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