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Volume 69 
Part 4 
Pages o606-o607  
April 2013  

Received 8 March 2013
Accepted 18 March 2013
Online 28 March 2013

Key indicators
Single-crystal X-ray study
T = 90 K
Mean [sigma](C-C) = 0.002 Å
R = 0.033
wR = 0.098
Data-to-parameter ratio = 24.0
Details
Open access

Bis(1,2,3-benzotriazolium) sulfate dihydrate

aY-Not Chemical Consulting, 14400 Williams Road, Zachary, LA 70791, USA, and bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
Correspondence e-mail: ffroncz@lsu.edu

In the asymmetric unit of the title hydrated salt, 2C6H6N3+·SO42-·2H2O, there are two independent sulfate ions, one lying on a twofold axis, and the other in a general position. There are three independent benzotriazolium cations and three independent water molecules. The sulfate ion in a general position forms hydrogen-bonded chains of stoichiometry SO42-·3H2O in the b-axis direction. The sulfate on the twofold axis is unhydrated and accepts hydrogen bonds from four surrounding benzotriazoles. The benzotriazolium cations form two types of stacks along b. One stack contains only one type of independent cation, related by inversion centers. The other stack contains two alternating independent cations and no symmetry. The two types of stacks have orientations which are rotated by about 79° in the ac plane. 12 symmetrically distinct hydrogen bonds of type N-H...O(sulfate), N-H...O(water), O-H...O(sulfate) and O-H...O(water), with donor-acceptor distances in the range 2.5490 (13)-2.7871 (12) Å, form a three-dimensional array.

Related literature

For the structure of benzotriazole hydrogensulfate, see: Giordano (1980[Giordano, F. (1980). Acta Cryst. B36, 2458-2460.]); Meléndez et al. (1996[Meléndez, R., Robinson, F. & Zaworotko, M. J. (1996). Supramol. Chem. 7, 275-293.]); Ramos-Organillo & Contreras (2007[Ramos-Organillo, A. & Contreras, R. (2007). Acta Cryst. C63, o501-o503.]). For the structure of benzotriazolium dihydrogen phosphate, see: Emsley et al. (1985[Emsley, J., Reza, N. M., Dawes, H. M. & Hursthouse, M. B. (1985). J. Chem. Soc. Chem. Commun. pp. 1458-1460.]) and for the structure of benzotriazolium perchlorate monohydrate, see: Sieron (2007[Sieron, L. (2007). Acta Cryst. E63, o2089-o2090.]). For the preparation and purification of benzotriazole with discussion of impurities, see: Damschroder & Peterson (1955[Damschroder, R. E. & Peterson, W. D. (1955). Org. Synth. Coll. Vol. 3, pp. 106-107.]); Miller & Schlaudecker (1958[Miller, E. B. & Schlaudecker, G. F. (1958). US Patent No. 2861078.]); Howard & Popplewell (1967[Howard, D. K. & Popplewell, A. F. (1967). US Patent No. 3334054.]); Spatz & Evans (1973[Spatz, S. M. & Evans, F. E. (1973). US Patent No. 3732239.]). For a purification method for aryltriazoles as their sulfate salts, see: Belter (2013[Belter, R. K. (2013). US Patent Appl. In preparation.]).

[Scheme 1]

Experimental

Crystal data
  • 2C6H6N3+·SO42-·2H2O

  • Mr = 372.37

  • Monoclinic, C 2/c

  • a = 38.312 (3) Å

  • b = 6.7621 (10) Å

  • c = 20.987 (2) Å

  • [beta] = 113.410 (5)°

  • V = 4989.5 (10) Å3

  • Z = 12

  • Mo K[alpha] radiation

  • [mu] = 0.24 mm-1

  • T = 90 K

  • 0.28 × 0.22 × 0.18 mm

Data collection
  • Bruker Kappa APEXII DUO CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004[Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.]) Tmin = 0.936, Tmax = 0.958

  • 33853 measured reflections

  • 9017 independent reflections

  • 7722 reflections with I > 2[sigma](I)

  • Rint = 0.023

Refinement
  • R[F2 > 2[sigma](F2)] = 0.033

  • wR(F2) = 0.098

  • S = 1.03

  • 9017 reflections

  • 375 parameters

  • 30 restraints

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

  • [Delta][rho]max = 0.56 e Å-3

  • [Delta][rho]min = -0.46 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N1-H1N...O3 0.96 (1) 1.65 (1) 2.5981 (11) 173 (1)
N3-H3N...O2Wi 0.96 (1) 1.59 (1) 2.5492 (11) 176 (1)
N4-H4N...O4 0.96 (1) 1.63 (1) 2.5822 (10) 170 (1)
N6-H6N...O6ii 0.94 (1) 1.66 (1) 2.5834 (11) 170 (1)
N7-H7N...O3W 0.94 (1) 1.68 (1) 2.6119 (11) 172 (1)
N9-H9N...O5 0.96 (1) 1.62 (1) 2.5735 (11) 178 (1)
O1W-H11W...O2iii 0.85 (1) 1.98 (1) 2.7498 (10) 151 (2)
O1W-H12W...O2 0.84 (1) 1.96 (1) 2.7871 (11) 172 (2)
O2W-H21W...O1iv 0.84 (1) 1.90 (1) 2.7345 (11) 170 (2)
O2W-H22W...O1W 0.83 (1) 1.82 (1) 2.6507 (12) 178 (2)
O3W-H31W...O3 0.83 (1) 1.87 (1) 2.7034 (10) 176 (2)
O3W-H32W...O1iv 0.81 (1) 1.96 (1) 2.7594 (11) 169 (2)
Symmetry codes: (i) [-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]; (ii) -x+1, -y+1, -z+1; (iii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iv) x, y-1, z.

Data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2006[Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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.]); software used to prepare material for publication: SHELXL97.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2540 ).


Acknowledgements

Upgrade of the diffractometer was made possible by grant No. LEQSF(2011-12)-ENH-TR-01, administered by the Louisiana Board of Regents.

References

Belter, R. K. (2013). US Patent Appl. In preparation.
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Damschroder, R. E. & Peterson, W. D. (1955). Org. Synth. Coll. Vol. 3, pp. 106-107.
Emsley, J., Reza, N. M., Dawes, H. M. & Hursthouse, M. B. (1985). J. Chem. Soc. Chem. Commun. pp. 1458-1460.  [CrossRef]
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [ISI] [CrossRef] [ChemPort] [details]
Giordano, F. (1980). Acta Cryst. B36, 2458-2460.  [CrossRef] [details] [ISI]
Howard, D. K. & Popplewell, A. F. (1967). US Patent No. 3334054.
Meléndez, R., Robinson, F. & Zaworotko, M. J. (1996). Supramol. Chem. 7, 275-293.
Miller, E. B. & Schlaudecker, G. F. (1958). US Patent No. 2861078.
Ramos-Organillo, A. & Contreras, R. (2007). Acta Cryst. C63, o501-o503.  [CrossRef] [details]
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Sieron, L. (2007). Acta Cryst. E63, o2089-o2090.  [CrossRef] [details]
Spatz, S. M. & Evans, F. E. (1973). US Patent No. 3732239.


Acta Cryst (2013). E69, o606-o607   [ doi:10.1107/S1600536813007472 ]

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