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

Mrad, M.L.; Zeller, M.; Hernandez, K.J.; Rzaigui, M.; Ben Nasr, C.

doi:10.1107/S1600536812044492

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 (N-C) = 0.002 Å
R = 0.023
wR = 0.059
Data-to-parameter ratio = 19.3
Details

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

Mohamed Lahbib Mrad,^a Matthias Zeller,^b Kristen J. Hernandez,^b Mohamed Rzaigui ^a and Cherif Ben Nasr ^a ^*

^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⁺·HPO₄^2-·H₂PO₄^-·3H₂O, the phosphate-based framework is built upon layers parallel to (010) made up from the H₂PO₄^- and HPO₄^2- anions and water molecules, which are interconnected through O-HO hydrogen bonds. The organic cations are located between the phosphate-water layers and are connected to them via N-HO 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); Dai et al. (2002); Masse et al. (1993). For graph-set motifs and theory, see: Bernstein et al. (1995). For reference structural data, see: Kaabi et al. (2004); Shanmuga Sundara Raj et al. (2000). For P-OH bond lengths, see: Chtioui & Jouini (2005).

Experimental

Crystal data

3C₂H₅N₄⁺·HO₄P^2-·H₂O₄P^-·3H₂O
M_r = 502.31
Monoclinic, P c
a = 10.4793 (13) Å
b = 8.7655 (11) Å
c = 11.4536 (14) Å
= 107.489 (2)°
V = 1003.5 (2) Å³
Z = 2
Mo K radiation
= 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) T_min = 0.693, T_max = 0.746
13833 measured reflections
6229 independent reflections
6132 reflections with I > 2(I)
R_int = 0.016

Refinement

R[F² > 2(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
_max = 0.33 e Å^-3
_min = -0.19 e Å^-3
Absolute structure: Flack (1983), 2950 Friedel pairs
Flack parameter: -0.02 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N1A-H1A1O3B	0.85 (1)	2.31 (1)	3.1356 (13)	162 (2)
N1A-H1A2N3Aⁱ	0.85 (1)	2.19 (1)	3.0305 (15)	170 (2)
N2A-H2AO4B	0.88	1.77	2.6130 (13)	161
N4A-H4AO4Bⁱ	0.88	1.76	2.6314 (13)	171
N1B-H1B1O2	0.86 (1)	1.96 (1)	2.8214 (13)	178 (2)
N1B-H1B2N3Bⁱ	0.82 (1)	2.28 (1)	3.0639 (15)	160 (2)
N2B-H2B1O3ⁱⁱ	0.88	1.84	2.6824 (13)	159
N4B-H4BO1Aⁱⁱⁱ	0.88	1.87	2.7376 (12)	167
N1C-H1C1N3Cⁱ	0.83 (1)	2.18 (1)	3.0028 (14)	172 (2)
N1C-H1C2O3A	0.86 (1)	2.24 (1)	3.0589 (13)	160 (2)
N2C-H2CO4A	0.88	1.78	2.6278 (12)	161
N4C-H4CO4Aⁱ	0.88	1.79	2.6645 (12)	170
O2A-H2ABO3B^iv	0.76	1.95	2.6593 (11)	155
O1B-H1BO3A	0.77	1.80	2.5495 (12)	161
O2B-H2BAO1^iv	0.83	1.73	2.5552 (12)	176
O1-H1DO2	0.84 (1)	1.93 (1)	2.7439 (12)	166 (2)
O1-H1EO3B	0.80 (1)	1.91 (1)	2.6968 (12)	168 (2)
O2-H2DO1A^v	0.82 (1)	1.90 (1)	2.7024 (11)	168 (2)
O2-H2EO3Aⁱⁱⁱ	0.81 (1)	1.95 (1)	2.7566 (12)	178 (2)
O3-H3DO2B	0.79 (1)	2.14 (2)	2.8515 (12)	149 (2)
O3-H3EO1Aⁱⁱⁱ	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); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXLE (Hübschle et al., 2011); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010).

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.
Bringley, J. F. & Rajeswaran, M. (2006). Acta Cryst. E62, m1304-m1305.
Bruker (2011). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wsiconsin, USA.
Chtioui, A. & Jouini, A. (2005). Mater. Res. Bull. 41, 569-575.
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.
Flack, H. D. (1983). Acta Cryst. A39, 876-881.
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.
Kaabi, K., Ben Nasr, C. & Lefebvre, F. (2004). Mater. Res. Bull. 39, 205-215.
Masse, R., Bagieu-Beucher, M., Pecaut, J., Levy, J. P. & Zyss, J. (1993). J. Nonlinear Opt. 5, 413-423.
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.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.

organic compounds