organic compounds
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 2H5N4+·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.
of the title molecular salt, 3CRelated 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
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Data collection: APEX2 (Bruker, 2011); cell 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).
Supporting information
10.1107/S1600536812044492/ru2044sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044492/ru2044Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812044492/ru2044Isup3.cml
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.
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
for amino and O-bound H atoms respectively.Data collection: APEX2 (Bruker, 2011); cell
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).Fig. 1. A view of the title compound, showing 40% probability displacement ellipsoids and arbitrary spheres for the H atoms. | |
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. | |
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. | |
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. |
3C2H5N4+·HO4P2−·H2O4P−·3H2O | F(000) = 524 |
Mr = 502.31 | Dx = 1.662 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yc | Cell parameters from 5573 reflections |
a = 10.4793 (13) Å | θ = 3.0–31.8° |
b = 8.7655 (11) Å | µ = 0.30 mm−1 |
c = 11.4536 (14) Å | T = 100 K |
β = 107.489 (2)° | Block, colourless |
V = 1003.5 (2) Å3 | 0.60 × 0.35 × 0.18 mm |
Z = 2 |
Bruker SMART APEX CCD diffractometer | 6229 independent reflections |
Radiation source: fine-focus sealed tube | 6132 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 32.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | h = −14→15 |
Tmin = 0.693, Tmax = 0.746 | k = −12→13 |
13833 measured reflections | l = −16→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.023 | H 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 reflections | Δρmax = 0.33 e Å−3 |
322 parameters | Δρmin = −0.19 e Å−3 |
32 restraints | Absolute structure: Flack (1983), 2950 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (4) |
3C2H5N4+·HO4P2−·H2O4P−·3H2O | V = 1003.5 (2) Å3 |
Mr = 502.31 | Z = 2 |
Monoclinic, Pc | Mo Kα radiation |
a = 10.4793 (13) Å | µ = 0.30 mm−1 |
b = 8.7655 (11) Å | T = 100 K |
c = 11.4536 (14) Å | 0.60 × 0.35 × 0.18 mm |
β = 107.489 (2)° |
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 = 0.746 | Rint = 0.016 |
13833 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.059 | Δρmax = 0.33 e Å−3 |
S = 1.04 | Δρmin = −0.19 e Å−3 |
6229 reflections | Absolute structure: Flack (1983), 2950 Friedel pairs |
322 parameters | Absolute structure parameter: −0.02 (4) |
32 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
N1A | 0.62032 (11) | 0.15272 (11) | 0.77449 (9) | 0.01772 (18) | |
H1A1 | 0.6049 (17) | 0.2392 (16) | 0.7386 (16) | 0.021* | |
H1A2 | 0.6042 (17) | 0.1391 (19) | 0.8421 (13) | 0.021* | |
N2A | 0.60906 (10) | 0.04376 (11) | 0.58172 (9) | 0.01488 (17) | |
H2A | 0.6141 | 0.1293 | 0.5432 | 0.018* | |
N3A | 0.59896 (10) | −0.09961 (11) | 0.52940 (9) | 0.01524 (17) | |
N4A | 0.60216 (9) | −0.11435 (11) | 0.72352 (9) | 0.01336 (16) | |
H4A | 0.6017 | −0.1543 | 0.7939 | 0.016* | |
C1A | 0.61011 (10) | 0.03524 (12) | 0.69840 (10) | 0.01299 (18) | |
C2A | 0.59494 (11) | −0.19168 (13) | 0.61746 (10) | 0.01451 (18) | |
H2AA | 0.5879 | −0.2995 | 0.6093 | 0.017* | |
N1B | 0.95278 (11) | 0.16763 (12) | 0.67577 (9) | 0.01933 (19) | |
H1B1 | 0.9835 (17) | 0.2502 (16) | 0.7144 (15) | 0.023* | |
H1B2 | 0.9369 (18) | 0.0936 (17) | 0.7129 (16) | 0.023* | |
N2B | 0.92010 (10) | 0.02876 (11) | 0.48939 (9) | 0.01598 (17) | |
H2B1 | 0.8958 | −0.0591 | 0.5132 | 0.019* | |
N3B | 0.93026 (11) | 0.05748 (11) | 0.37327 (10) | 0.01706 (18) | |
N4B | 0.98316 (9) | 0.26338 (10) | 0.49075 (8) | 0.01343 (16) | |
H4B | 1.0082 | 0.3574 | 0.5133 | 0.016* | |
C1B | 0.95240 (10) | 0.15303 (12) | 0.56033 (10) | 0.01362 (18) | |
C2B | 0.96750 (11) | 0.19962 (13) | 0.37803 (10) | 0.01543 (19) | |
H2B2 | 0.9821 | 0.2531 | 0.3110 | 0.019* | |
N1C | 0.28072 (10) | 0.15370 (11) | 0.42295 (9) | 0.01621 (17) | |
H1C1 | 0.2900 (16) | 0.137 (2) | 0.4966 (12) | 0.019* | |
H1C2 | 0.2796 (17) | 0.2424 (15) | 0.3916 (15) | 0.019* | |
N2C | 0.28411 (10) | 0.04801 (11) | 0.23314 (8) | 0.01377 (16) | |
H2C | 0.2843 | 0.1345 | 0.1942 | 0.017* | |
N3C | 0.28565 (10) | −0.09510 (11) | 0.18257 (9) | 0.01465 (17) | |
N4C | 0.28158 (9) | −0.11349 (11) | 0.37482 (8) | 0.01238 (16) | |
H4C | 0.2795 | −0.1547 | 0.4443 | 0.015* | |
C1C | 0.28234 (10) | 0.03715 (12) | 0.34900 (9) | 0.01169 (17) | |
C2C | 0.28461 (10) | −0.18892 (12) | 0.27069 (10) | 0.01394 (18) | |
H2CA | 0.2858 | −0.2969 | 0.2636 | 0.017* | |
P1A | 0.23842 (2) | 0.41894 (3) | 0.11253 (2) | 0.00876 (5) | |
O1A | 0.09137 (7) | 0.45148 (9) | 0.04480 (7) | 0.01176 (13) | |
O2A | 0.31520 (8) | 0.55501 (9) | 0.07195 (7) | 0.01273 (14) | |
H2AB | 0.3902 (19) | 0.5380 (10) | 0.0918 (15) | 0.019* | |
O3A | 0.26391 (8) | 0.42577 (8) | 0.25172 (7) | 0.01225 (14) | |
O4A | 0.28676 (8) | 0.26682 (9) | 0.07706 (7) | 0.01314 (14) | |
P1B | 0.59788 (2) | 0.42266 (3) | 0.46934 (2) | 0.00962 (5) | |
O1B | 0.49521 (8) | 0.52280 (9) | 0.37270 (7) | 0.01584 (15) | |
H1B | 0.4300 (18) | 0.4769 (15) | 0.3450 (15) | 0.024* | |
O2B | 0.73507 (8) | 0.50517 (10) | 0.48323 (7) | 0.01466 (14) | |
H2BA | 0.7526 (10) | 0.5008 (18) | 0.4177 (17) | 0.022* | |
O3B | 0.57479 (8) | 0.43008 (9) | 0.59371 (7) | 0.01269 (14) | |
O4B | 0.59985 (9) | 0.26114 (9) | 0.42328 (7) | 0.01614 (15) | |
O1 | 0.78679 (8) | 0.52112 (11) | 0.77991 (8) | 0.01834 (16) | |
H1D | 0.8624 (15) | 0.502 (2) | 0.7733 (18) | 0.028* | |
H1E | 0.7308 (17) | 0.484 (2) | 0.7240 (15) | 0.028* | |
O2 | 1.04601 (8) | 0.44288 (10) | 0.79982 (7) | 0.01506 (15) | |
H2D | 1.0714 (18) | 0.4441 (19) | 0.8747 (12) | 0.023* | |
H2E | 1.1091 (15) | 0.481 (2) | 0.7840 (17) | 0.023* | |
O3 | 0.91292 (8) | 0.75025 (9) | 0.58426 (8) | 0.01633 (15) | |
H3D | 0.8480 (15) | 0.699 (2) | 0.5712 (17) | 0.025* | |
H3E | 0.9680 (16) | 0.6944 (19) | 0.5732 (17) | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0286 (5) | 0.0117 (4) | 0.0144 (4) | −0.0010 (4) | 0.0086 (4) | −0.0005 (3) |
N2A | 0.0231 (4) | 0.0110 (4) | 0.0115 (4) | −0.0008 (3) | 0.0067 (3) | 0.0012 (3) |
N3A | 0.0212 (4) | 0.0128 (4) | 0.0127 (4) | −0.0002 (3) | 0.0067 (3) | −0.0007 (3) |
N4A | 0.0176 (4) | 0.0118 (4) | 0.0114 (4) | 0.0000 (3) | 0.0054 (3) | 0.0021 (3) |
C1A | 0.0142 (4) | 0.0125 (5) | 0.0123 (5) | −0.0003 (3) | 0.0041 (3) | 0.0017 (3) |
C2A | 0.0177 (4) | 0.0134 (5) | 0.0134 (5) | −0.0004 (4) | 0.0061 (4) | 0.0002 (3) |
N1B | 0.0291 (5) | 0.0157 (4) | 0.0145 (4) | −0.0063 (4) | 0.0085 (4) | −0.0010 (3) |
N2B | 0.0207 (4) | 0.0123 (4) | 0.0155 (4) | −0.0025 (3) | 0.0063 (3) | −0.0011 (3) |
N3B | 0.0207 (4) | 0.0154 (4) | 0.0154 (4) | −0.0004 (3) | 0.0058 (3) | −0.0014 (3) |
N4B | 0.0169 (4) | 0.0105 (4) | 0.0129 (4) | −0.0015 (3) | 0.0045 (3) | −0.0001 (3) |
C1B | 0.0139 (4) | 0.0119 (4) | 0.0146 (5) | −0.0004 (3) | 0.0037 (3) | 0.0000 (3) |
C2B | 0.0172 (4) | 0.0154 (5) | 0.0139 (5) | −0.0002 (4) | 0.0048 (4) | −0.0006 (4) |
N1C | 0.0248 (4) | 0.0124 (4) | 0.0129 (4) | −0.0016 (3) | 0.0079 (3) | −0.0013 (3) |
N2C | 0.0222 (4) | 0.0099 (4) | 0.0106 (4) | 0.0010 (3) | 0.0070 (3) | 0.0005 (3) |
N3C | 0.0225 (4) | 0.0101 (4) | 0.0123 (4) | 0.0017 (3) | 0.0066 (3) | 0.0002 (3) |
N4C | 0.0167 (4) | 0.0104 (4) | 0.0109 (4) | −0.0008 (3) | 0.0054 (3) | 0.0008 (3) |
C1C | 0.0135 (4) | 0.0112 (5) | 0.0107 (4) | −0.0004 (3) | 0.0040 (3) | 0.0008 (3) |
C2C | 0.0186 (5) | 0.0113 (4) | 0.0126 (4) | 0.0005 (4) | 0.0056 (4) | 0.0006 (3) |
P1A | 0.01123 (10) | 0.00815 (11) | 0.00727 (11) | 0.00019 (8) | 0.00335 (8) | 0.00021 (8) |
O1A | 0.0118 (3) | 0.0126 (3) | 0.0107 (3) | 0.0004 (3) | 0.0031 (2) | 0.0007 (3) |
O2A | 0.0126 (3) | 0.0103 (3) | 0.0161 (4) | 0.0001 (3) | 0.0057 (3) | 0.0030 (3) |
O3A | 0.0152 (3) | 0.0137 (3) | 0.0078 (3) | 0.0001 (3) | 0.0034 (3) | −0.0008 (2) |
O4A | 0.0200 (3) | 0.0094 (3) | 0.0113 (3) | 0.0015 (3) | 0.0067 (3) | −0.0003 (3) |
P1B | 0.01187 (10) | 0.00900 (11) | 0.00812 (11) | −0.00035 (8) | 0.00319 (8) | −0.00054 (8) |
O1B | 0.0154 (3) | 0.0138 (4) | 0.0150 (4) | −0.0008 (3) | −0.0006 (3) | 0.0036 (3) |
O2B | 0.0131 (3) | 0.0193 (4) | 0.0127 (3) | −0.0036 (3) | 0.0057 (3) | −0.0023 (3) |
O3B | 0.0136 (3) | 0.0160 (4) | 0.0095 (3) | −0.0003 (3) | 0.0051 (3) | −0.0022 (3) |
O4B | 0.0291 (4) | 0.0099 (3) | 0.0115 (3) | −0.0003 (3) | 0.0093 (3) | −0.0011 (3) |
O1 | 0.0131 (3) | 0.0292 (5) | 0.0127 (4) | −0.0018 (3) | 0.0039 (3) | −0.0045 (3) |
O2 | 0.0152 (3) | 0.0208 (4) | 0.0099 (3) | −0.0028 (3) | 0.0047 (3) | −0.0007 (3) |
O3 | 0.0162 (3) | 0.0120 (4) | 0.0225 (4) | −0.0001 (3) | 0.0083 (3) | −0.0010 (3) |
N1A—C1A | 1.3325 (14) | N2C—C1C | 1.3361 (13) |
N1A—H1A1 | 0.854 (13) | N2C—N3C | 1.3838 (13) |
N1A—H1A2 | 0.849 (13) | N2C—H2C | 0.8800 |
N2A—C1A | 1.3353 (14) | N3C—C2C | 1.3044 (14) |
N2A—N3A | 1.3826 (13) | N4C—C1C | 1.3537 (14) |
N2A—H2A | 0.8800 | N4C—C2C | 1.3724 (14) |
N3A—C2A | 1.3022 (14) | N4C—H4C | 0.8800 |
N4A—C1A | 1.3504 (15) | C2C—H2CA | 0.9500 |
N4A—C2A | 1.3732 (14) | P1A—O4A | 1.5243 (8) |
N4A—H4A | 0.8800 | P1A—O1A | 1.5294 (8) |
C2A—H2AA | 0.9500 | P1A—O3A | 1.5364 (8) |
N1B—C1B | 1.3272 (15) | P1A—O2A | 1.5845 (8) |
N1B—H1B1 | 0.859 (13) | O2A—H2AB | 0.7639 |
N1B—H1B2 | 0.820 (13) | P1B—O4B | 1.5132 (8) |
N2B—C1B | 1.3401 (14) | P1B—O3B | 1.5163 (8) |
N2B—N3B | 1.3888 (14) | P1B—O1B | 1.5612 (8) |
N2B—H2B1 | 0.8800 | P1B—O2B | 1.5741 (8) |
N3B—C2B | 1.3018 (15) | O1B—H1B | 0.7742 |
N4B—C1B | 1.3524 (14) | O2B—H2BA | 0.8262 |
N4B—C2B | 1.3706 (14) | O1—H1D | 0.835 (14) |
N4B—H4B | 0.8800 | O1—H1E | 0.796 (14) |
C2B—H2B2 | 0.9500 | O2—H2D | 0.819 (13) |
N1C—C1C | 1.3304 (14) | O2—H2E | 0.808 (13) |
N1C—H1C1 | 0.833 (13) | O3—H3D | 0.790 (13) |
N1C—H1C2 | 0.855 (13) | O3—H3E | 0.795 (13) |
C1A—N1A—H1A1 | 113.9 (12) | C1C—N1C—H1C2 | 115.6 (11) |
C1A—N1A—H1A2 | 119.3 (12) | H1C1—N1C—H1C2 | 124.9 (16) |
H1A1—N1A—H1A2 | 120.2 (17) | C1C—N2C—N3C | 110.88 (9) |
C1A—N2A—N3A | 111.07 (9) | C1C—N2C—H2C | 124.6 |
C1A—N2A—H2A | 124.5 | N3C—N2C—H2C | 124.6 |
N3A—N2A—H2A | 124.5 | C2C—N3C—N2C | 104.11 (9) |
C2A—N3A—N2A | 104.11 (9) | C1C—N4C—C2C | 106.08 (9) |
C1A—N4A—C2A | 106.34 (9) | C1C—N4C—H4C | 127.0 |
C1A—N4A—H4A | 126.8 | C2C—N4C—H4C | 127.0 |
C2A—N4A—H4A | 126.8 | N1C—C1C—N2C | 125.74 (10) |
N1A—C1A—N2A | 125.90 (10) | N1C—C1C—N4C | 127.44 (10) |
N1A—C1A—N4A | 127.52 (10) | N2C—C1C—N4C | 106.81 (9) |
N2A—C1A—N4A | 106.56 (9) | N3C—C2C—N4C | 112.11 (10) |
N3A—C2A—N4A | 111.92 (10) | N3C—C2C—H2CA | 123.9 |
N3A—C2A—H2AA | 124.0 | N4C—C2C—H2CA | 123.9 |
N4A—C2A—H2AA | 124.0 | O4A—P1A—O1A | 113.13 (4) |
C1B—N1B—H1B1 | 118.9 (12) | O4A—P1A—O3A | 110.03 (4) |
C1B—N1B—H1B2 | 120.0 (13) | O1A—P1A—O3A | 110.70 (4) |
H1B1—N1B—H1B2 | 120.2 (18) | O4A—P1A—O2A | 109.97 (5) |
C1B—N2B—N3B | 110.80 (9) | O1A—P1A—O2A | 103.52 (4) |
C1B—N2B—H2B1 | 124.6 | O3A—P1A—O2A | 109.26 (4) |
N3B—N2B—H2B1 | 124.6 | P1A—O2A—H2AB | 109.5 |
C2B—N3B—N2B | 103.98 (9) | O4B—P1B—O3B | 112.98 (5) |
C1B—N4B—C2B | 106.33 (9) | O4B—P1B—O1B | 110.95 (5) |
C1B—N4B—H4B | 126.8 | O3B—P1B—O1B | 111.80 (5) |
C2B—N4B—H4B | 126.8 | O4B—P1B—O2B | 110.94 (5) |
N1B—C1B—N2B | 127.37 (10) | O3B—P1B—O2B | 106.50 (4) |
N1B—C1B—N4B | 126.03 (10) | O1B—P1B—O2B | 103.13 (5) |
N2B—C1B—N4B | 106.60 (10) | P1B—O1B—H1B | 109.5 |
N3B—C2B—N4B | 112.29 (10) | P1B—O2B—H2BA | 109.5 |
N3B—C2B—H2B2 | 123.9 | H1D—O1—H1E | 109.7 (19) |
N4B—C2B—H2B2 | 123.9 | H2D—O2—H2E | 101.5 (17) |
C1C—N1C—H1C1 | 119.1 (12) | H3D—O3—H3E | 104.3 (18) |
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+1/2; (ii) x, y−1, z; (iii) x+1, −y+1, z+1/2; (iv) x, −y+1, z−1/2; (v) x+1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | 3C2H5N4+·HO4P2−·H2O4P−·3H2O |
Mr | 502.31 |
Crystal system, space group | Monoclinic, Pc |
Temperature (K) | 100 |
a, b, c (Å) | 10.4793 (13), 8.7655 (11), 11.4536 (14) |
β (°) | 107.489 (2) |
V (Å3) | 1003.5 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.60 × 0.35 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2011) |
Tmin, Tmax | 0.693, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13833, 6229, 6132 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.746 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.059, 1.04 |
No. of reflections | 6229 |
No. of parameters | 322 |
No. of restraints | 32 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.19 |
Absolute structure | Flack (1983), 2950 Friedel pairs |
Absolute structure parameter | −0.02 (4) |
Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SHELXLE (Hübschle et al., 2011), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A1···O3B | 0.854 (13) | 2.311 (14) | 3.1356 (13) | 162.4 (16) |
N1A—H1A2···N3Ai | 0.849 (13) | 2.190 (13) | 3.0305 (15) | 170.4 (16) |
N2A—H2A···O4B | 0.88 | 1.77 | 2.6130 (13) | 160.7 |
N4A—H4A···O4Bi | 0.88 | 1.76 | 2.6314 (13) | 171.3 |
N1B—H1B1···O2 | 0.859 (13) | 1.963 (13) | 2.8214 (13) | 177.5 (17) |
N1B—H1B2···N3Bi | 0.820 (13) | 2.282 (14) | 3.0639 (15) | 159.5 (17) |
N2B—H2B1···O3ii | 0.88 | 1.84 | 2.6824 (13) | 158.6 |
N4B—H4B···O1Aiii | 0.88 | 1.87 | 2.7376 (12) | 167.2 |
N1C—H1C1···N3Ci | 0.833 (13) | 2.175 (13) | 3.0028 (14) | 172.4 (15) |
N1C—H1C2···O3A | 0.855 (13) | 2.241 (13) | 3.0589 (13) | 160.3 (15) |
N2C—H2C···O4A | 0.88 | 1.78 | 2.6278 (12) | 161.1 |
N4C—H4C···O4Ai | 0.88 | 1.79 | 2.6645 (12) | 170.3 |
O2A—H2AB···O3Biv | 0.76 | 1.95 | 2.6593 (11) | 154.7 |
O1B—H1B···O3A | 0.77 | 1.80 | 2.5495 (12) | 161.3 |
O2B—H2BA···O1iv | 0.83 | 1.73 | 2.5552 (12) | 176.2 |
O1—H1D···O2 | 0.835 (14) | 1.927 (14) | 2.7439 (12) | 165.6 (19) |
O1—H1E···O3B | 0.796 (14) | 1.913 (14) | 2.6968 (12) | 168 (2) |
O2—H2D···O1Av | 0.819 (13) | 1.897 (14) | 2.7024 (11) | 167.9 (18) |
O2—H2E···O3Aiii | 0.808 (13) | 1.949 (13) | 2.7566 (12) | 178.1 (19) |
O3—H3D···O2B | 0.790 (13) | 2.143 (15) | 2.8515 (12) | 149.4 (18) |
O3—H3E···O1Aiii | 0.795 (13) | 1.915 (13) | 2.7085 (11) | 175.9 (19) |
Symmetry codes: (i) x, −y, z+1/2; (ii) x, y−1, z; (iii) x+1, −y+1, z+1/2; (iv) x, −y+1, z−1/2; (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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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.