Synthesis, crystal structure and characterization of [C9H11N4] H2PO4

Journal of Molecular Structure 1063 (2014) 153–159

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Journal of Molecular Structure journal homepage: www.elsevier.com/locate/molstruc

Synthesis, crystal structure and characterization of [C9H11N4] H2PO4 A. Chtourou a, M. Boujelbene a,⇑, F. Allouch b, T. Mhiri a a b

Laboratory of the Physico-Chemistry of Solid States, LR11 ES51 of Sfax, Road of Soukra km 4, Sfax 3071, Tunisia Laboratoire de Chimie Applique´e: He´te´rocycles, Corps gras et Polyme‘res, Faculte´des Sciences de Sfax, BP 802, 3018 Sfax, Tunisia

h i g h l i g h t s  X-ray diffraction and description of the new compound [C9H11N4] H2PO4.  TGA/DTA thermograms were explained.  The characterization by

31

P and

13

C solid-state NMR spectroscopy is also reported and discussed.

 The observed frequencies in the infrared and Raman spectra were explained and discussed.

a r t i c l e

i n f o

Article history: Received 22 October 2013 Received in revised form 17 January 2014 Accepted 17 January 2014 Available online 28 January 2014 Keywords: Hybrid X-ray diffraction Crystal structure Nuclear magnetic resonance (NMR) Infrared spectroscopy

a b s t r a c t Chemical preparation crystal structure and spectroscopic investigations are given for a new organic-catin the ion dihydrogenomonophosphate (C9H11N4) H2PO4 in the solid state. This compound crystallizes 0 0 Å. b = 4.582 (5) A Å. monoclinic space group P 21 with the following unit cell parameters: a = 9.640 (5) A 0 3 c = 14.094 (5) A Å, b = 106.979 (5)°, Z = 2, V = 595.4 (7) Å . Crystal structure was solved with a final R = 0.054 for 2077 independent reflections. The atomic arrangement can be described as inorganic layers 13 C and 31P MAS-NMR specof H2 PO 4 anions between which are located the organic groups. Solid-state troscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of the phosphorous and carbon signals to the independent crystallographic sites and to the various atoms of the organic groups. Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction Among the various categories of monophosphates are the most numerous not only because they were the first to be investigated, but also because they are the most stable and therefore the only phosphates to be found in nature. The acidic monophosphate anions like [HPO4]2 and [H2PO4] exhibit a characteristic geometry to build infinite network via hydrogen bonds with various geometries: chains [1,2], ribbons [3], two-dimensional networks [4,5] and three-dimensional networks [6]. These entities can be associated to organic molecules to produce compounds having a particular interest in some application areas. As a contribution to the study of this monophosphate family. This compound was synthesized within a systematic search on new materials resulting from the association of organic and inorganic entities, which could be of particular interest in non-linear optics [7]. This compound has a great interest due to their biological and pharmacological activity as anti-tumor and inhibition of the activity of cholesterol. In addition, it has many ⇑ Corresponding author. Tel.: +216 22677645. E-mail address: [email protected] (M. Boujelbene). http://dx.doi.org/10.1016/j.molstruc.2014.01.049 0022-2860/Ó 2014 Elsevier B.V. All rights reserved.

applications in the field of agriculture [8]. We report in this work the chemical preparation and the structural investigation of a new 5-Amino-3-metyl-phenyl-1H-1,2,4-trizole dihydrogenmonophosphate [C9H11N4] [H2PO4] the characterization by 31P and 13C solid-state NMR spectroscopy is also reported.

2. Experimental 2.1. Chemical preparation Crystals of the title compound has been prepared according to the following chemical H2 O

C9 H10 N4 þ H3 PO4 ! ½C9 H11 N4 þ þ H2 PO4 By mixing equimolar portions (1:1) of two reagents amine and orthophosphoric acid in a solution of water. The obtained solution after reaction is slowly evaporated at room temperature for several days until the formation of good quality colorless and parallelipedic crystals. The compound chemical formula was determined by resolving its crystal structure by X-ray diffraction.

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2.2. Investigation techniques 2.2.1. X-ray diffraction The intensity data collection was performed using a Brüker APEXII CCD the strategy used for the structure determination and its final results are gathered in Table 1. The structure was solved with a direct method from the SHELXS-97 programs. Which permitted the location of the PO4 groups. The remaining non-hydrogen atoms were located by the successive difference Fourier maps using the SHELXL-97 programs [9]. The final atomic coordinates are given in Table 2. The main geometrical features bond distances and angles are reported in Table 3. 2.2.2. NMR spectroscopy All NMR spectra were recorded on a Bruker DSX-300 spectrometer operating at 300 MHz for 1H. 75.49 MHz for 13C and 121.51 MHz for 31P with a classical 4 mm probehead allowing spinning rates up to 10 KHz. 1H and 13C NMR. Chemical shifts are given relative to tetramethylsiline and 31P ones relative to 85% H3PO4 (external references precision 0.5 ppm). Phosphorous and proton spectra were recorded under classical MAS conditions while the carbons were recorded by use of cross-polarization from protons (contact time 5 ms). To determine the NMR chemical shifts of the atoms. Ab initio calculations were made with the Gaussian 98 software. 2.2.3. Infrared spectroscopy Spectrum was recorded in the range of 4000–400 cm1 with a ‘‘Perkin–Elmer FTIR’’ spectrophotometer 1000 using a sample dispersed in spectroscopically pure KBr pellet. 2.2.4. Raman measurements Furthermore, Raman spectra were measured with a LABRAMHR 800 triple monochromator under a 50 LF objective microscope. A He–Ne ion laser operating at about 20 mW was used (on the sample) as an excitation source (514.5 nm), with a spectral steps of 3 cm1.

Table 1 Crystal structure data for [C9H11N4] [H2PO4]. Crystal data Formula/formula weight Crystal system Space group/Z Lattice parameters

Volume Å3 Density (calculated) (g/cm3) Absorption coefficient m (mm1) F(0 0 0) Size (mm)/color Wavelength. Mo Temperature Theta range h. k. l range No. of independent reflections Structure determination Unique reflections included: (I > 2sI) Programs used SHELX-97 No. of refined parameters R (anisotropic) Rw (anisotropic) Extinction coefficient Drmin./Drmax. (e/Å3)

(C9H11N4)(H2PO4)/272 g mol1 Monolinic P 21/2 a = 9.640 (5) Å; b = 4.582 (5) Å; c = 14.094 (5) Å 595.4 (7) Å 1.518 0.25 284 0.53 mm_0.15 mm_0.08 mm/colorless K a = 0.71073 Å 293 1.5/25 11/11. 5/5. 16/16 4451

Table 2 The final atomic coordinates and equivalent temperature factors for (C9H11N4) (H2PO4).

P O(3) O(2) O(4) O(1) N(1) N(3) N(4) H(04A) H(04B) H(04C) N(2) C(1) C(2) H(2) C(7) C(6) H(6) C(9) H(09A) H(09B) H(09C) C(4) H(4) C(8) C(5) H(5) C(3) H(3) H(1)

x

y

z

Uiso/Ueq

1.34092 (12) 1.2298 (4) 1.3378 (4) 1.3150 (4) 1.4951 (4) 0.9765 (4) 0.8092 (4) 0.9787 (5) 1.0643 0.9172 0.9893 0.8857 (5) 1.1048 (6) 1.2301 (6) 1.2304 0.9275 (5) 1.1064 (7) 1.0241 0.6652 (7) 0.5759 0.6767 0.6632 1.3562 (6) 1.4404 0.7883 (5) 1.2324 (7) 1.2342 1.3533 (6) 1.4360 1.538 (7)

0.1491 (3) 0.0864 (7) 0.2435 (8) 0.4063 (8) 0.0441 (9) 0.1195 (12) 0.3883 (11) 0.2003 (13) 0.2891 0.2792 0.0113 0.1986 (11) 0.0421 (12) 0.0038 (13) 0.1399 0.2319 (11) 0.2344 (14) 0.2602 0.5003 (16) 0.4469 0.7084 0.4369 0.3465 (17) 0.4507 0.3591 (13) 0.3878 (15) 0.5195 0.1518 (15) 0.1243 0.085 (17)

0.55928 (9) 0.5587 (3) 0.4556 (3) 0.6240 (3) 0.6197 (3) 0.7802 (3) 0.6868 (3) 0.6128 (3) 0.6255 0.5592 0.6022 0.8382 (3) 0.8249 (4) 0.7972 (4) 0.7482 0.6891 (4) 0.9010 (4) 0.9218 0.8041 (5) 0.7558 0.8041 0.8686 0.9160 (4) 0.9460 0.7789 (4) 0.9459 (4) 0.9965 0.8420 (4) 0.8218 0.575 (5)

0.0234 (3) 0.0302 (8) 0.0353 (9) 0.0376 (9) 0.0418 (10) 0.0341 (10) 0.0330 (10) 0.0450 (14) 0.067 0.067 0.067 0.0348 (11) 0.0321 (12) 0.0361 (13) 0.043 0.0311 (12) 0.0420 (14) 0.050 0.0477 (15) 0.072 0.072 0.072 0.0509 (15) 0.061 0.0349 (12) 0.0527 (17) 0.063 0.0472 (16) 0.057 0.058 (19)

Table 3 Main interatomic distances (Å) and bond angles (°) for (C9H11N4) (H2PO4). PO4 tetrahedron Distances (Å) PA(O2) PA(O3) PA(O4) PA(O1) O1A(H1)

1.515 (4) 1.519 (4) 1.555 (4) 1.558 (4) 1.04 (7)

C1AC6 C1AC2 C2AC3 C2AH2 C6AC5

1.384 (8) 1.391 (7) 1.371 (8) 0.9300 1.386 (9)

Angles (°) (O2)APA(O3) (O2)APA(O4) (O3)APA(O4) (O2)APA(O1) (O3)APA(O1) (O4)APA(O1) PAO1AH1

112.5 (2) 112.8 (2) 107.9 (2) 111.3 (2) 110.0 (2) 101.8 (2) 109 (3)

N4AC7AN1 N4AC7AN3 N1AC7AN3 C1AC6AC5 C1AC6AH6 C5AC6AH6 C8AC9AH09A

129.2 124.0 106.8 119.1 120.4 120.4 109.5

(5) (5) (4) (6)

2.2.5. Thermal analysis DTA/TGA investigations were performed using a multi-module 92 SETARAM analyzer operating from room temperature up to 400 °C at a constant rate of 5 °C min1 under flowing air.

3. Results and discussion 3.1. Structure description

2971 [7] 169 0.054 0.141 2 (15) (8) 0.35/0.60

The final atomic coordinates and thermal parameters are given in Table 2. Inter atomic distances and angles are listed in Table 3. A perspective view of the asymmetric unit of the structure drawing with 50% probability thermal ellipsoids is depicted in Fig. 1. A view of the structure projected along the direction Fig. 2 shows that the H2PO4 inorganic entities have a layered organization. The organic

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Fig. 1. Asymmetric unit of (C9H11N4)(H2PO4) at 50% probability.

Fig. 2. Projection along the b axis of the atomic arrangement in (C9H11N4)(H2PO4).

cations are trapped in the interlayer spacing and neutralize the negative charge of the inorganic layers. The asymmetric unit of the crystal structure consists of one phosphate anions and one organic cation. The present atomic arrangement exhibits two kinds of hydro0 gen bonds. The first type, OAH  O 2.573 Å A which ensure the cohesion of the tetrahedral groups them. The second one, NAH  O 0 between 2.829 and 3.336 Å A, in this type of structural arrangement, these hydrogen bonds established between the organic cation and the mineral structure. Examination of the H2PO4 geometrical features Table 3 shows two types of PAO distances. The longest ones (1.555 and 1.561 Å) Table 4 The calculated of the distortion indices. Compound

ID(PO)

ID(OO)

ID(OPO)

[C9H11N4] H2PO4

0.01251

0.01182

0.00041

Fig. 3. 31P MAS-NMR (C9H11N4)(H2PO4).

spectrum

of

the

dihydrogenomonophosphate

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Fig. 4.

13

C CP-MAS-NMR spectrum of crystalline dihydrogenomonophosphate (C9H11N4)(H2PO4).

Intensity (u.a)

25000 20000 15000 10000 5000 0 Fig. 5. Dihydrogenomonophosphate (C9H11N4)(H2PO4) (programme ChemDraw Ultra).

0

1000

2000

3000

4000

-1

wavenumber (cm ) Fig. 7. Raman spectrum of (C9H11N4)(H2PO4).

Fig. 6. IR-spectra of (C9H11N4)(H2PO4).

can be attributed to PAOH groups. The shortest ones corresponding to classical PAO bands as pointed out by Cruickshank [10]. The average values of the PAO distances and the OAPAO angles are 1.538(3) Å and 109.373°(17) respectively; they are in good

agreement with that generally observed in such anions in other phosphates. These values are similar to those observed in the structure [(4-C2H5C6H4NH3)H2PO4] [11]. The calculated average values of the distortion indices Table 4 corresponding to the different angles and distances in both PO4 tetrahedron DI(OPO) = 0.00041; DI(PO) = 0.01251 and DI(OO) = 0.01182 exhibit a pronounced distortion of the PO distances and OPO angles if compared to OO distances [12]. Dihydrogénomonphosphate the group can be described as a regular oxygen atom at the vertices of a tetrahedron and phosphorus atom moved the center of gravity of the tetrahedron PO4 tetrahedral arrangement.

3.2. NMR results The 31P MAS NMR spectrum of the crystalline monophosphate (C9H11N4) H2PO4 is shown in Fig. 3 and is in good agreement with

A. Chtourou et al. / Journal of Molecular Structure 1063 (2014) 153–159

the X-ray structure. Indeed it exhibits a single resonance peak corresponding to only one crystallographic site. The chemical shift value (0.103 ppm). The high resolution NMR spectroscopy is a powerful technique for the characterization of 13C. From the isotropic chemical shift values of NMR components structural aspects have been studied. The presence of a resonance peak number equal to five. The

157

simulated 13C NMR spectra of the title compound Fig. 4 proves the existence of one crystallographically organic cation in the asymmetric unit of the compound structure. The 13C NMR spectrum Fig. 5 has five signals for nine carbons, which proves that our molecule is partially symmetric. Five independent resonances in the unit. The first line located at 11.789 ppm is assigned to the C (9) carbon. The second line located

Table 5 Spectral data and band assignments.

(continued on next page)

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Note: vs, very strong; s, strong; m, medium; w, weak; V, stretching s, symmetric; as, asymmetric.

at 121.056 ppm is assigned to C (1) carbon. Carbons of C (2), C (6), C (4), C (3), and C (5) are equals to a core line located at 128.762 ppm. The fourth line located at 134.775 ppm is assigned to C (7). In the end the C (8) carbon located to 149.847 ppm. 4. IR spectroscopy investigations The IR and Raman spectra are shown in Figs. 6 and 7 respectively. The spectral data and proposed vibrational assignment is listed in Table 5. As shown in the Raman spectrum presented in

Fig. 7. One strong band at 914 cm1 is observed, which can be attributed to m1 (PO4). The peaks observed at 999, 1024 and 1052 cm1 and those recorded at 524, 532 and 569 cm1, can be accredited to the asymmetric stretching m3 and the asymmetric bending modes m4 of PO4 groups respectively. The peaks observed at 401, 420 and 442 cm1, they could be assigned to the symmetric bending m2 mode. With respect to the IR spectrum of the compound shown in Fig. 6, it is similar to that of the dihydrogenomonophosphate of generic formula (4C2H5C6H4NH3) H2PO4 [11]. With the bands corresponding to the asymmetric stretching m3

#Heat Flow/µV Exo

#TG/mg 0.0

3.2

-0.5 -1.0 -1.5

2.2

-2.0 -2.5 -3.0

1.2

-3.5 -4.0 -4.5

0.2

-5.0 -5.5 -6.0

-0.8

-6.5 -7.0 -7.5

50

100

150

200

250

300

Fig. 8. DTA and TGA curves of (C9H11N4)(H2PO4).

Température échantillon/°C

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(PO4) are located at 1000, 1012, 1029 cm1, the symmetric stretching m1 (PO4) mode is observed at 917 cm1. The peaks observed at 445, 430, 424 and 406 cm1, they could be assigned to the symmetric bending m2. Bending vibration bands between 528 and 565 cm1 corresponding to m4 (PO4). The high frequency peaks noted in the IR spectra at 2744, 2694, 2623 and 2339 cm1 most likely correspond to C, B and A m (POH) [13]. The broad band between 3050 and 3305 cm1 correspond at m (OH), mas (NAH) and ms (NAH) [14].

All the authors express their thanks to Prof. Hammadi Khemakhem for his help in the Raman study and Prof. Abdhamid Ben Salah for his help in the X-Ray diffraction.

5. Thermal behavior

References

The two curves corresponding to differential thermal analysis (DTA) and thermogravimetric analysis (TGA) in open air are given in Fig. 8. The DTA curve shows that this (C9H11N4) H2PO4 displays an endothermic melting peak at about 170 °C. Above this temperature the product undergoes a decomposition of the (C9H11N4) groups over a wide temperature range (170–400 °C). The TGA curve shows a continuous weight loss in all this temperature area.

single crystal X-ray analysis, showing that this compound crystallizes in a monoclinic space group P 21. The 31P NMR spectrum of the title compound confirms the existence of phosphorus atoms. Acknowledgements

[1] [2] [3] [4] [5] [6] [7] [8] [9]

6. Conclusion

[10] [11]

This paper presents the involving synthesis, structural determination of a new hybrid compound C9H11N4, and vibrational. Its structure (performed at room temperature) is determined by a

[12] [13] [14]

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