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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 12| December 2012| Pages o3257-o3258

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

(Received 7 October 2012; accepted 26 October 2012; online 3 November 2012)

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

  • β = 107.489 (2)°

  • V = 1003.5 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 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 > 2σ(I)

  • Rint = 0.016

Refinement
  • R[F2 > 2σ(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

  • Δρmax = 0.33 e Å−3

  • Δρmin = −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 DA 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.]).

Supporting information


Comment top

Inorganic–organic hybrid compounds provide a class of materials with interesting technological applications (Bringley & Rajeswaran, 2006; Dai et al., 2002). Among these materials, compounds with noncentrosymmetric crystallographic structures are interesting for their applications in quadratic non-linear optical materials research (Masse et al., 1993). Their abilities to combine the rigidity and high cohesion of inorganic host matrices with the enhanced polarizability of organic guest chromophores within one molecular scale assists in better performance of optical signal-processing devices. The use of organic-inorganic polar crystalline materials for quadratic nonlinear optical applications is supported by two observations:

(i) the organic molecules, especially if they contain a delocalized π-system with asymmetric substitution by electron donor-acceptor groups, are highly polarizable entities idealy suited for NLO applications. Being organic materials, the nature of the substituents can be tailored so as to not affect optical transparency;

(ii) the ionic inorganic host matrices are able to increase the packing cohesion, can induce noncentrosymmetry, and also shift the transparency of crystal towards blue wavelengths.

Within a systematic investigation of new materials resulting from the association of organic chromophores with inorganic species, we report here the synthesis and the characterization of a new hybrid phosphate-amine material, (C2H5N4)3(HPO4)(H2PO4).3H2O, which includes the 3-amino-1H-1,2,4-triazolium cations, a chromophore which could be efficient in the blue-U.V. wavelength region. The title compound could exhibit a richness of interesting physical properties such as ferroelectricity and nonlinear optic phenomena like second harmonic generation. It crystallizes in a non-centrosymmetric setting in the space group Pc. The structure of this organic-inorganic hybrid material consists of one dihydrogenmonophosphate anion, one monohydrogenmonophosphate dianion, three crystallographically independent 3-amino-1H-1,2,4-triazolium cations and three water molecules (Fig. 1). The atomic arrangement is a typical layered organization as it is very often encountered in this kind of inorganic-organic hybrid compounds (Kaabi et al., 2004). The H2PO4- anions are hydrogen bonded with the HPO42- groups and one of the water molecules (that of O3) to form corrugated chains running parallel to the a-axis at (0, 0, 0) and (0, 0, 1/2). These chains are interconnected, via O(water)—H···O and O—H···O(water) hydrogen bonds, with the two remaining water molecules H2O(1) and H2O(2), associated through O1—H···O2 hydrogen bonds, on one hand, and with the HPO42- anions of the adjacent chain, trough O—H···O hydrogen bonds, on the other hand. These hydrogen bonds link the different inorganic units into infinite planar layers parallel to the (0 1 0) plane (Fig. 2) crossing the unit cell at y = (2n +1)/2 (Fig. 3). Within the layers, various graph-set motifs (Bernstein et al., 1995) are apparent, including R55(10) and R44(12) loops. The 3-amino-1H-1,2,4-triazolium cations are interconnected via weak N—H···N hydrogen bonds, with D—H···A distances between 3.003 (1) and 3.064 (1) Å, to form organic chains spreading along the c-axis at x ~ (n + 1)/3 (Fig. 4). The chains are build from the three crystallographically independent organic cations, labelled A, B and C, in such a way that each N—H···N connected chain incorporates only one type of cation: Molecules of type A are located at x ~1/3, chains at x ~ 0 consist of molecules of type B, and the chains at x~2/3 are made up of molecules C. Alternating molecules in each of these chains are created by the c-glide plane. In two of the chains, that of molecules A and C, alternating molecules are roughly coplanar. In the third, molecules are twisted against each other by an angle of 34.37°. The chains are roughly parallel to each other and weakly π-stacked, with interplanar distances between the mean planes of chains between 3.21 Å (between A and C), and up to 3.52 Å (for A and B). Despite of the quite close interplanar distances, π-π stacking interactions are limited due to molecule offsets in parallel layers, and the non-coplanarity of neighboring molecules in the chains of molecules B. The organic chains are anchored to the inorganic layers through N—H···O hydrogen bonds whose geometrical characteristics are given in Table 2. The projection of the whole arrangement along the a-axis (Fig. 4) shows how the organic chains alternate as to fill the space separating parallel inorganic layers. In this structure, three 3-amino-1H-1,2,4-triazolium cationic groups compensate the negative charges of the dihydrogenmonophosphate and the monohydrogenmonophosphate anions, leading to charge neutrality for the structure as a whole.

The sum of the angles around the N1A, N1B and N1C nitrogen atoms are 360° and the C—N bond distances of the NH2 groups are 1.332 (1) Å for N1A—C1A, 1.327 (1) Å for N1B—C1B and 1.330 (1) Å for N1C—C1C, which are short for C—N single bonds, but still not quite as contracted as one would expect for a fully established C=N double bond. These bond length features are consistent with an imino resonance form as it is commonly found for a C—N single bond involving sp2 hybridized C and N atoms (Shanmuga Sundara Raj et al., 2000). In agreement with this, the amino groups are not pyramidal but the electron densities of the hydrogen atoms of the amino groups were found to be in plane with the 3-amino-1H-1,2,4-triazolium skeleton. The detailed geometry of the HP(1 A)O42- and H2P(1B)O4- anions shows two kinds of P—O distances. The shortest ones, 1.5243 (8), 1.5294 (8) and 1.5364 Å for the first anion (labelled A) and 1.5132 (8) and 1.5163 (8) Å for the second one (labelled B), correspond to the phosphorous atom doubly bonded to the oxygen atom, while the largest ones 1.5845 (8) Å and (1.5612 (8), 1.5741 (8) Å, respectively, can be attributed to the P—OH bond length. This is in agreement with the literature data (Chtioui & Jouini, 2005). Refining the structure in the asymmetric space group gives a value of -0.02 (4) for the Flack parameter (Flack, 1983), confirming the absolute structure and absence of twinning.

Related literature top

For common 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 top

Crystals of the title compound were prepared at room temperature by slow addition of a solution of orthophosphoric acid (8 mmol in 30 ml of water) to an alcoholic solution of 3-amino-1H-1,2,4-triazole (12 mmol in 30 ml of ethanol). The acid was added until the alcoholic solution became turbid. After filtration, the solution was allowed to slowly evaporate at room temperature over several days leading to formation of transparent prismatic crystals with suitable dimensions for single-crystal structural analysis (1.2 mg, 2.4 mmol, yield 60%). The crystals are stable for months under normal conditions of temperature and humidity.

Refinement top

H atoms were placed in calculated positions with the exception of water and NH2 H atoms, which were located in difference density maps and were refined. C—H distances were set to 0.95 Å, Nring—H distances to 0.88 Å. H atoms of P-bound hydroxy groups were placed geometrically with fixed P—O—H angles, but with variable torional angles and O—H distances to best fit the experimental electron density (AFIX 148 in SHELXTL, Sheldrick 2008). All H2O O—H distances were restrained to be similar within a standard deviation of 0.02 Å. All amino N—H distances were also restrained to be similar within the same standard deviation. Uiso values of H atoms were set to 1.2 or 1.5 times Ueq of their respective carrier atom for amino and O-bound H atoms respectively.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); 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 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A view of the title compound, showing 40% probability displacement ellipsoids and arbitrary spheres for the H atoms.
[Figure 2] Fig. 2. Projection along the b-axis of the inorganic layers in the structure of the title compound. PO4 is given in the tetrahedral representation. Hydrogen bonds are shown as broken lines.
[Figure 3] Fig. 3. The packing diagram of the compound viewed down the a-axis. PO4 is given in the tetrahedral representation. Hydrogen bonds are shown as broken lines.
[Figure 4] Fig. 4. Projection along the b axis of the organic chains in the structure of the title compound. Hydrogen bonds are shown as broken lines. Numbers are interplanar spacings between layers of organic molecules of type A, B and C.
Tris(5-amino-1H-1,2,4-triazol-4-ium) dihydrogenphosphate hydrogenphosphate trihydrate top
Crystal data top
3C2H5N4+·HO4P2·H2O4P·3H2OF(000) = 524
Mr = 502.31Dx = 1.662 Mg m3
Monoclinic, PcMo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2ycCell parameters from 5573 reflections
a = 10.4793 (13) Åθ = 3.0–31.8°
b = 8.7655 (11) ŵ = 0.30 mm1
c = 11.4536 (14) ÅT = 100 K
β = 107.489 (2)°Block, colourless
V = 1003.5 (2) Å30.60 × 0.35 × 0.18 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer
6229 independent reflections
Radiation source: fine-focus sealed tube6132 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω scansθmax = 32.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2011)
h = 1415
Tmin = 0.693, Tmax = 0.746k = 1213
13833 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059 w = 1/[σ2(Fo2) + (0.0385P)2 + 0.0562P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
6229 reflectionsΔρmax = 0.33 e Å3
322 parametersΔρmin = 0.19 e Å3
32 restraintsAbsolute structure: Flack (1983), 2950 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (4)
Crystal data top
3C2H5N4+·HO4P2·H2O4P·3H2OV = 1003.5 (2) Å3
Mr = 502.31Z = 2
Monoclinic, PcMo Kα radiation
a = 10.4793 (13) ŵ = 0.30 mm1
b = 8.7655 (11) ÅT = 100 K
c = 11.4536 (14) Å0.60 × 0.35 × 0.18 mm
β = 107.489 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer
6229 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2011)
6132 reflections with I > 2σ(I)
Tmin = 0.693, Tmax = 0.746Rint = 0.016
13833 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059Δρmax = 0.33 e Å3
S = 1.04Δρmin = 0.19 e Å3
6229 reflectionsAbsolute structure: Flack (1983), 2950 Friedel pairs
322 parametersAbsolute structure parameter: 0.02 (4)
32 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.62032 (11)0.15272 (11)0.77449 (9)0.01772 (18)
H1A10.6049 (17)0.2392 (16)0.7386 (16)0.021*
H1A20.6042 (17)0.1391 (19)0.8421 (13)0.021*
N2A0.60906 (10)0.04376 (11)0.58172 (9)0.01488 (17)
H2A0.61410.12930.54320.018*
N3A0.59896 (10)0.09961 (11)0.52940 (9)0.01524 (17)
N4A0.60216 (9)0.11435 (11)0.72352 (9)0.01336 (16)
H4A0.60170.15430.79390.016*
C1A0.61011 (10)0.03524 (12)0.69840 (10)0.01299 (18)
C2A0.59494 (11)0.19168 (13)0.61746 (10)0.01451 (18)
H2AA0.58790.29950.60930.017*
N1B0.95278 (11)0.16763 (12)0.67577 (9)0.01933 (19)
H1B10.9835 (17)0.2502 (16)0.7144 (15)0.023*
H1B20.9369 (18)0.0936 (17)0.7129 (16)0.023*
N2B0.92010 (10)0.02876 (11)0.48939 (9)0.01598 (17)
H2B10.89580.05910.51320.019*
N3B0.93026 (11)0.05748 (11)0.37327 (10)0.01706 (18)
N4B0.98316 (9)0.26338 (10)0.49075 (8)0.01343 (16)
H4B1.00820.35740.51330.016*
C1B0.95240 (10)0.15303 (12)0.56033 (10)0.01362 (18)
C2B0.96750 (11)0.19962 (13)0.37803 (10)0.01543 (19)
H2B20.98210.25310.31100.019*
N1C0.28072 (10)0.15370 (11)0.42295 (9)0.01621 (17)
H1C10.2900 (16)0.137 (2)0.4966 (12)0.019*
H1C20.2796 (17)0.2424 (15)0.3916 (15)0.019*
N2C0.28411 (10)0.04801 (11)0.23314 (8)0.01377 (16)
H2C0.28430.13450.19420.017*
N3C0.28565 (10)0.09510 (11)0.18257 (9)0.01465 (17)
N4C0.28158 (9)0.11349 (11)0.37482 (8)0.01238 (16)
H4C0.27950.15470.44430.015*
C1C0.28234 (10)0.03715 (12)0.34900 (9)0.01169 (17)
C2C0.28461 (10)0.18892 (12)0.27069 (10)0.01394 (18)
H2CA0.28580.29690.26360.017*
P1A0.23842 (2)0.41894 (3)0.11253 (2)0.00876 (5)
O1A0.09137 (7)0.45148 (9)0.04480 (7)0.01176 (13)
O2A0.31520 (8)0.55501 (9)0.07195 (7)0.01273 (14)
H2AB0.3902 (19)0.5380 (10)0.0918 (15)0.019*
O3A0.26391 (8)0.42577 (8)0.25172 (7)0.01225 (14)
O4A0.28676 (8)0.26682 (9)0.07706 (7)0.01314 (14)
P1B0.59788 (2)0.42266 (3)0.46934 (2)0.00962 (5)
O1B0.49521 (8)0.52280 (9)0.37270 (7)0.01584 (15)
H1B0.4300 (18)0.4769 (15)0.3450 (15)0.024*
O2B0.73507 (8)0.50517 (10)0.48323 (7)0.01466 (14)
H2BA0.7526 (10)0.5008 (18)0.4177 (17)0.022*
O3B0.57479 (8)0.43008 (9)0.59371 (7)0.01269 (14)
O4B0.59985 (9)0.26114 (9)0.42328 (7)0.01614 (15)
O10.78679 (8)0.52112 (11)0.77991 (8)0.01834 (16)
H1D0.8624 (15)0.502 (2)0.7733 (18)0.028*
H1E0.7308 (17)0.484 (2)0.7240 (15)0.028*
O21.04601 (8)0.44288 (10)0.79982 (7)0.01506 (15)
H2D1.0714 (18)0.4441 (19)0.8747 (12)0.023*
H2E1.1091 (15)0.481 (2)0.7840 (17)0.023*
O30.91292 (8)0.75025 (9)0.58426 (8)0.01633 (15)
H3D0.8480 (15)0.699 (2)0.5712 (17)0.025*
H3E0.9680 (16)0.6944 (19)0.5732 (17)0.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0286 (5)0.0117 (4)0.0144 (4)0.0010 (4)0.0086 (4)0.0005 (3)
N2A0.0231 (4)0.0110 (4)0.0115 (4)0.0008 (3)0.0067 (3)0.0012 (3)
N3A0.0212 (4)0.0128 (4)0.0127 (4)0.0002 (3)0.0067 (3)0.0007 (3)
N4A0.0176 (4)0.0118 (4)0.0114 (4)0.0000 (3)0.0054 (3)0.0021 (3)
C1A0.0142 (4)0.0125 (5)0.0123 (5)0.0003 (3)0.0041 (3)0.0017 (3)
C2A0.0177 (4)0.0134 (5)0.0134 (5)0.0004 (4)0.0061 (4)0.0002 (3)
N1B0.0291 (5)0.0157 (4)0.0145 (4)0.0063 (4)0.0085 (4)0.0010 (3)
N2B0.0207 (4)0.0123 (4)0.0155 (4)0.0025 (3)0.0063 (3)0.0011 (3)
N3B0.0207 (4)0.0154 (4)0.0154 (4)0.0004 (3)0.0058 (3)0.0014 (3)
N4B0.0169 (4)0.0105 (4)0.0129 (4)0.0015 (3)0.0045 (3)0.0001 (3)
C1B0.0139 (4)0.0119 (4)0.0146 (5)0.0004 (3)0.0037 (3)0.0000 (3)
C2B0.0172 (4)0.0154 (5)0.0139 (5)0.0002 (4)0.0048 (4)0.0006 (4)
N1C0.0248 (4)0.0124 (4)0.0129 (4)0.0016 (3)0.0079 (3)0.0013 (3)
N2C0.0222 (4)0.0099 (4)0.0106 (4)0.0010 (3)0.0070 (3)0.0005 (3)
N3C0.0225 (4)0.0101 (4)0.0123 (4)0.0017 (3)0.0066 (3)0.0002 (3)
N4C0.0167 (4)0.0104 (4)0.0109 (4)0.0008 (3)0.0054 (3)0.0008 (3)
C1C0.0135 (4)0.0112 (5)0.0107 (4)0.0004 (3)0.0040 (3)0.0008 (3)
C2C0.0186 (5)0.0113 (4)0.0126 (4)0.0005 (4)0.0056 (4)0.0006 (3)
P1A0.01123 (10)0.00815 (11)0.00727 (11)0.00019 (8)0.00335 (8)0.00021 (8)
O1A0.0118 (3)0.0126 (3)0.0107 (3)0.0004 (3)0.0031 (2)0.0007 (3)
O2A0.0126 (3)0.0103 (3)0.0161 (4)0.0001 (3)0.0057 (3)0.0030 (3)
O3A0.0152 (3)0.0137 (3)0.0078 (3)0.0001 (3)0.0034 (3)0.0008 (2)
O4A0.0200 (3)0.0094 (3)0.0113 (3)0.0015 (3)0.0067 (3)0.0003 (3)
P1B0.01187 (10)0.00900 (11)0.00812 (11)0.00035 (8)0.00319 (8)0.00054 (8)
O1B0.0154 (3)0.0138 (4)0.0150 (4)0.0008 (3)0.0006 (3)0.0036 (3)
O2B0.0131 (3)0.0193 (4)0.0127 (3)0.0036 (3)0.0057 (3)0.0023 (3)
O3B0.0136 (3)0.0160 (4)0.0095 (3)0.0003 (3)0.0051 (3)0.0022 (3)
O4B0.0291 (4)0.0099 (3)0.0115 (3)0.0003 (3)0.0093 (3)0.0011 (3)
O10.0131 (3)0.0292 (5)0.0127 (4)0.0018 (3)0.0039 (3)0.0045 (3)
O20.0152 (3)0.0208 (4)0.0099 (3)0.0028 (3)0.0047 (3)0.0007 (3)
O30.0162 (3)0.0120 (4)0.0225 (4)0.0001 (3)0.0083 (3)0.0010 (3)
Geometric parameters (Å, º) top
N1A—C1A1.3325 (14)N2C—C1C1.3361 (13)
N1A—H1A10.854 (13)N2C—N3C1.3838 (13)
N1A—H1A20.849 (13)N2C—H2C0.8800
N2A—C1A1.3353 (14)N3C—C2C1.3044 (14)
N2A—N3A1.3826 (13)N4C—C1C1.3537 (14)
N2A—H2A0.8800N4C—C2C1.3724 (14)
N3A—C2A1.3022 (14)N4C—H4C0.8800
N4A—C1A1.3504 (15)C2C—H2CA0.9500
N4A—C2A1.3732 (14)P1A—O4A1.5243 (8)
N4A—H4A0.8800P1A—O1A1.5294 (8)
C2A—H2AA0.9500P1A—O3A1.5364 (8)
N1B—C1B1.3272 (15)P1A—O2A1.5845 (8)
N1B—H1B10.859 (13)O2A—H2AB0.7639
N1B—H1B20.820 (13)P1B—O4B1.5132 (8)
N2B—C1B1.3401 (14)P1B—O3B1.5163 (8)
N2B—N3B1.3888 (14)P1B—O1B1.5612 (8)
N2B—H2B10.8800P1B—O2B1.5741 (8)
N3B—C2B1.3018 (15)O1B—H1B0.7742
N4B—C1B1.3524 (14)O2B—H2BA0.8262
N4B—C2B1.3706 (14)O1—H1D0.835 (14)
N4B—H4B0.8800O1—H1E0.796 (14)
C2B—H2B20.9500O2—H2D0.819 (13)
N1C—C1C1.3304 (14)O2—H2E0.808 (13)
N1C—H1C10.833 (13)O3—H3D0.790 (13)
N1C—H1C20.855 (13)O3—H3E0.795 (13)
C1A—N1A—H1A1113.9 (12)C1C—N1C—H1C2115.6 (11)
C1A—N1A—H1A2119.3 (12)H1C1—N1C—H1C2124.9 (16)
H1A1—N1A—H1A2120.2 (17)C1C—N2C—N3C110.88 (9)
C1A—N2A—N3A111.07 (9)C1C—N2C—H2C124.6
C1A—N2A—H2A124.5N3C—N2C—H2C124.6
N3A—N2A—H2A124.5C2C—N3C—N2C104.11 (9)
C2A—N3A—N2A104.11 (9)C1C—N4C—C2C106.08 (9)
C1A—N4A—C2A106.34 (9)C1C—N4C—H4C127.0
C1A—N4A—H4A126.8C2C—N4C—H4C127.0
C2A—N4A—H4A126.8N1C—C1C—N2C125.74 (10)
N1A—C1A—N2A125.90 (10)N1C—C1C—N4C127.44 (10)
N1A—C1A—N4A127.52 (10)N2C—C1C—N4C106.81 (9)
N2A—C1A—N4A106.56 (9)N3C—C2C—N4C112.11 (10)
N3A—C2A—N4A111.92 (10)N3C—C2C—H2CA123.9
N3A—C2A—H2AA124.0N4C—C2C—H2CA123.9
N4A—C2A—H2AA124.0O4A—P1A—O1A113.13 (4)
C1B—N1B—H1B1118.9 (12)O4A—P1A—O3A110.03 (4)
C1B—N1B—H1B2120.0 (13)O1A—P1A—O3A110.70 (4)
H1B1—N1B—H1B2120.2 (18)O4A—P1A—O2A109.97 (5)
C1B—N2B—N3B110.80 (9)O1A—P1A—O2A103.52 (4)
C1B—N2B—H2B1124.6O3A—P1A—O2A109.26 (4)
N3B—N2B—H2B1124.6P1A—O2A—H2AB109.5
C2B—N3B—N2B103.98 (9)O4B—P1B—O3B112.98 (5)
C1B—N4B—C2B106.33 (9)O4B—P1B—O1B110.95 (5)
C1B—N4B—H4B126.8O3B—P1B—O1B111.80 (5)
C2B—N4B—H4B126.8O4B—P1B—O2B110.94 (5)
N1B—C1B—N2B127.37 (10)O3B—P1B—O2B106.50 (4)
N1B—C1B—N4B126.03 (10)O1B—P1B—O2B103.13 (5)
N2B—C1B—N4B106.60 (10)P1B—O1B—H1B109.5
N3B—C2B—N4B112.29 (10)P1B—O2B—H2BA109.5
N3B—C2B—H2B2123.9H1D—O1—H1E109.7 (19)
N4B—C2B—H2B2123.9H2D—O2—H2E101.5 (17)
C1C—N1C—H1C1119.1 (12)H3D—O3—H3E104.3 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A1···O3B0.85 (1)2.31 (1)3.1356 (13)162 (2)
N1A—H1A2···N3Ai0.85 (1)2.19 (1)3.0305 (15)170 (2)
N2A—H2A···O4B0.881.772.6130 (13)161
N4A—H4A···O4Bi0.881.762.6314 (13)171
N1B—H1B1···O20.86 (1)1.96 (1)2.8214 (13)178 (2)
N1B—H1B2···N3Bi0.82 (1)2.28 (1)3.0639 (15)160 (2)
N2B—H2B1···O3ii0.881.842.6824 (13)159
N4B—H4B···O1Aiii0.881.872.7376 (12)167
N1C—H1C1···N3Ci0.83 (1)2.18 (1)3.0028 (14)172 (2)
N1C—H1C2···O3A0.86 (1)2.24 (1)3.0589 (13)160 (2)
N2C—H2C···O4A0.881.782.6278 (12)161
N4C—H4C···O4Ai0.881.792.6645 (12)170
O2A—H2AB···O3Biv0.761.952.6593 (11)155
O1B—H1B···O3A0.771.802.5495 (12)161
O2B—H2BA···O1iv0.831.732.5552 (12)176
O1—H1D···O20.84 (1)1.93 (1)2.7439 (12)166 (2)
O1—H1E···O3B0.80 (1)1.91 (1)2.6968 (12)168 (2)
O2—H2D···O1Av0.82 (1)1.90 (1)2.7024 (11)168 (2)
O2—H2E···O3Aiii0.81 (1)1.95 (1)2.7566 (12)178 (2)
O3—H3D···O2B0.79 (1)2.14 (2)2.8515 (12)149 (2)
O3—H3E···O1Aiii0.80 (1)1.92 (1)2.7085 (11)176 (2)
Symmetry codes: (i) x, y, z+1/2; (ii) x, y1, z; (iii) x+1, y+1, z+1/2; (iv) x, y+1, z1/2; (v) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula3C2H5N4+·HO4P2·H2O4P·3H2O
Mr502.31
Crystal system, space groupMonoclinic, Pc
Temperature (K)100
a, b, c (Å)10.4793 (13), 8.7655 (11), 11.4536 (14)
β (°) 107.489 (2)
V3)1003.5 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.60 × 0.35 × 0.18
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2011)
Tmin, Tmax0.693, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
13833, 6229, 6132
Rint0.016
(sin θ/λ)max1)0.746
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.059, 1.04
No. of reflections6229
No. of parameters322
No. of restraints32
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.33, 0.19
Absolute structureFlack (1983), 2950 Friedel pairs
Absolute structure parameter0.02 (4)

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SHELXLE (Hübschle et al., 2011), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A1···O3B0.854 (13)2.311 (14)3.1356 (13)162.4 (16)
N1A—H1A2···N3Ai0.849 (13)2.190 (13)3.0305 (15)170.4 (16)
N2A—H2A···O4B0.881.772.6130 (13)160.7
N4A—H4A···O4Bi0.881.762.6314 (13)171.3
N1B—H1B1···O20.859 (13)1.963 (13)2.8214 (13)177.5 (17)
N1B—H1B2···N3Bi0.820 (13)2.282 (14)3.0639 (15)159.5 (17)
N2B—H2B1···O3ii0.881.842.6824 (13)158.6
N4B—H4B···O1Aiii0.881.872.7376 (12)167.2
N1C—H1C1···N3Ci0.833 (13)2.175 (13)3.0028 (14)172.4 (15)
N1C—H1C2···O3A0.855 (13)2.241 (13)3.0589 (13)160.3 (15)
N2C—H2C···O4A0.881.782.6278 (12)161.1
N4C—H4C···O4Ai0.881.792.6645 (12)170.3
O2A—H2AB···O3Biv0.761.952.6593 (11)154.7
O1B—H1B···O3A0.771.802.5495 (12)161.3
O2B—H2BA···O1iv0.831.732.5552 (12)176.2
O1—H1D···O20.835 (14)1.927 (14)2.7439 (12)165.6 (19)
O1—H1E···O3B0.796 (14)1.913 (14)2.6968 (12)168 (2)
O2—H2D···O1Av0.819 (13)1.897 (14)2.7024 (11)167.9 (18)
O2—H2E···O3Aiii0.808 (13)1.949 (13)2.7566 (12)178.1 (19)
O3—H3D···O2B0.790 (13)2.143 (15)2.8515 (12)149.4 (18)
O3—H3E···O1Aiii0.795 (13)1.915 (13)2.7085 (11)175.9 (19)
Symmetry codes: (i) x, y, z+1/2; (ii) x, y1, z; (iii) x+1, y+1, z+1/2; (iv) x, y+1, z1/2; (v) x+1, y, z+1.
 

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

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Volume 68| Part 12| December 2012| Pages o3257-o3258
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