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Volume 68 
Part 12 
Pages o3257-o3258  
December 2012  

Received 7 October 2012
Accepted 26 October 2012
Online 3 November 2012

Key indicators
Single-crystal X-ray study
T = 100 K
Mean [sigma](N-C) = 0.002 Å
R = 0.023
wR = 0.059
Data-to-parameter ratio = 19.3
Details
Open access

Tris(5-amino-1H-1,2,4-triazol-4-ium) dihydrogenphosphate hydrogenphosphate trihydrate

aLaboratoire de Chimie des Matériaux, Faculté des sciences de Bizerte, 7021 Zarzouna, Tunisia, and bYoungstown State University, Department of Chemistry, One University Plaza, Youngstown, Ohio 44555-3663, USA
Correspondence e-mail: cherif_bennasr@yahoo.fr

In the crystal structure of the title molecular salt, 3C2H5N4+·HPO42-·H2PO4-·3H2O, the phosphate-based framework is built upon layers parallel to (010) made up from the H2PO4- and HPO42- anions and water molecules, which are interconnected through O-H...O hydrogen bonds. The organic cations are located between the phosphate-water layers and are connected to them via N-H...O hydrogen bonds. The bond-length features are consistent with an imino resonance form for the exocyclic amino group, as is commonly found for a C-N single bond involving sp2-hybridized C and N atoms.

Related literature

For applications of organic phosphate complexes, see: Bringley & Rajeswaran (2006[Bringley, J. F. & Rajeswaran, M. (2006). Acta Cryst. E62, m1304-m1305.]); Dai et al. (2002[Dai, J.-C., Wu, X.-T., Fu, Z.-Y., Cui, C.-P., Wu, S.-M., Du, W.-X., Wu, L.-M., Zhang, H.-H. & Sun, Q.-Q. (2002). Inorg. Chem. 41, 1391-1396.]); Masse et al. (1993[Masse, R., Bagieu-Beucher, M., Pecaut, J., Levy, J. P. & Zyss, J. (1993). J. Nonlinear Opt. 5, 413-423.]). For graph-set motifs and theory, see: Bernstein et al. (1995[Bernstein, J., Davids, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For reference structural data, see: Kaabi et al. (2004[Kaabi, K., Ben Nasr, C. & Lefebvre, F. (2004). Mater. Res. Bull. 39, 205-215.]); Shanmuga Sundara Raj et al. (2000[Shanmuga Sundara Raj, S., Fun, H.-K., Zhao, P.-S., Jian, F.-F., Lu, L.-D., Yang, X.-J. & Wang, X. (2000). Acta Cryst. C56, 742-743.]). For P-OH bond lengths, see: Chtioui & Jouini (2005[Chtioui, A. & Jouini, A. (2005). Mater. Res. Bull. 41, 569-575.]).

[Scheme 1]

Experimental

Crystal data
  • 3C2H5N4+·HO4P2-·H2O4P-·3H2O

  • Mr = 502.31

  • Monoclinic, P c

  • a = 10.4793 (13) Å

  • b = 8.7655 (11) Å

  • c = 11.4536 (14) Å

  • [beta] = 107.489 (2)°

  • V = 1003.5 (2) Å3

  • Z = 2

  • Mo K[alpha] radiation

  • [mu] = 0.30 mm-1

  • T = 100 K

  • 0.60 × 0.35 × 0.18 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2011[Bruker (2011). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wsiconsin, USA.]) Tmin = 0.693, Tmax = 0.746

  • 13833 measured reflections

  • 6229 independent reflections

  • 6132 reflections with I > 2[sigma](I)

  • Rint = 0.016

Refinement
  • R[F2 > 2[sigma](F2)] = 0.023

  • wR(F2) = 0.059

  • S = 1.04

  • 6229 reflections

  • 322 parameters

  • 32 restraints

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

  • [Delta][rho]max = 0.33 e Å-3

  • [Delta][rho]min = -0.19 e Å-3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 2950 Friedel pairs

  • Flack parameter: -0.02 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N1A-H1A1...O3B 0.85 (1) 2.31 (1) 3.1356 (13) 162 (2)
N1A-H1A2...N3Ai 0.85 (1) 2.19 (1) 3.0305 (15) 170 (2)
N2A-H2A...O4B 0.88 1.77 2.6130 (13) 161
N4A-H4A...O4Bi 0.88 1.76 2.6314 (13) 171
N1B-H1B1...O2 0.86 (1) 1.96 (1) 2.8214 (13) 178 (2)
N1B-H1B2...N3Bi 0.82 (1) 2.28 (1) 3.0639 (15) 160 (2)
N2B-H2B1...O3ii 0.88 1.84 2.6824 (13) 159
N4B-H4B...O1Aiii 0.88 1.87 2.7376 (12) 167
N1C-H1C1...N3Ci 0.83 (1) 2.18 (1) 3.0028 (14) 172 (2)
N1C-H1C2...O3A 0.86 (1) 2.24 (1) 3.0589 (13) 160 (2)
N2C-H2C...O4A 0.88 1.78 2.6278 (12) 161
N4C-H4C...O4Ai 0.88 1.79 2.6645 (12) 170
O2A-H2AB...O3Biv 0.76 1.95 2.6593 (11) 155
O1B-H1B...O3A 0.77 1.80 2.5495 (12) 161
O2B-H2BA...O1iv 0.83 1.73 2.5552 (12) 176
O1-H1D...O2 0.84 (1) 1.93 (1) 2.7439 (12) 166 (2)
O1-H1E...O3B 0.80 (1) 1.91 (1) 2.6968 (12) 168 (2)
O2-H2D...O1Av 0.82 (1) 1.90 (1) 2.7024 (11) 168 (2)
O2-H2E...O3Aiii 0.81 (1) 1.95 (1) 2.7566 (12) 178 (2)
O3-H3D...O2B 0.79 (1) 2.14 (2) 2.8515 (12) 149 (2)
O3-H3E...O1Aiii 0.80 (1) 1.92 (1) 2.7085 (11) 176 (2)
Symmetry codes: (i) [x, -y, z+{\script{1\over 2}}]; (ii) x, y-1, z; (iii) [x+1, -y+1, z+{\script{1\over 2}}]; (iv) [x, -y+1, z-{\script{1\over 2}}]; (v) x+1, y, z+1.

Data collection: APEX2 (Bruker, 2011[Bruker (2011). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wsiconsin, USA.]); cell refinement: SAINT (Bruker, 2011[Bruker (2011). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wsiconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXLE (Hübschle et al., 2011[Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RU2044 ).


Acknowledgements

We would like to acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia. The diffractometer was funded by NSF grant 0087210, by Ohio Board of Regents grant CAP-491, and by YSU.

References

Bernstein, J., Davids, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.  [CrossRef] [ChemPort] [ISI]
Bringley, J. F. & Rajeswaran, M. (2006). Acta Cryst. E62, m1304-m1305.  [CSD] [CrossRef] [details]
Bruker (2011). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wsiconsin, USA.
Chtioui, A. & Jouini, A. (2005). Mater. Res. Bull. 41, 569-575.  [ISI] [CSD] [CrossRef]
Dai, J.-C., Wu, X.-T., Fu, Z.-Y., Cui, C.-P., Wu, S.-M., Du, W.-X., Wu, L.-M., Zhang, H.-H. & Sun, Q.-Q. (2002). Inorg. Chem. 41, 1391-1396.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Flack, H. D. (1983). Acta Cryst. A39, 876-881.  [CrossRef] [details]
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.  [ISI] [CrossRef] [details]
Kaabi, K., Ben Nasr, C. & Lefebvre, F. (2004). Mater. Res. Bull. 39, 205-215.  [ISI] [CSD] [CrossRef] [ChemPort]
Masse, R., Bagieu-Beucher, M., Pecaut, J., Levy, J. P. & Zyss, J. (1993). J. Nonlinear Opt. 5, 413-423.  [ChemPort]
Shanmuga Sundara Raj, S., Fun, H.-K., Zhao, P.-S., Jian, F.-F., Lu, L.-D., Yang, X.-J. & Wang, X. (2000). Acta Cryst. C56, 742-743.  [CSD] [CrossRef] [details]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [ISI] [CrossRef] [ChemPort] [details]


Acta Cryst (2012). E68, o3257-o3258   [ doi:10.1107/S1600536812044492 ]

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