Physicochemical properties of a new hybrid compound (C 7H 9N 2O) 3HSO 4SO 4 are synthesized in aqueous solution and characterized by various physicochemical studies. This compound crystallizes in the monoclinic space group P2 1/c and a unit cell with a = 10.3028(2)A°, b = 12.4995(2)A°, c = 20.6730(2)A°, V = 2600.61(7)A° 3, and Z = 8. The structure has been solved using direct method and refined to a reliability R factor of 4.6%. The atomic arrangement of this compound is built up by (HS 2O 8) 3- anionic pairs interconnected with two types (C 7H 9N 2O) 2 2+ cationic pairs via (N, O)-H...O hydrogen bonds. The characterization of these salts was carried out using X-ray diffraction, IR spectroscopy and thermal analysis.
The synthesis of new hybrid materials based sulfate, phosphate and arsenate may contain original physical properties, is one of several research studies in chemistry laboratories in the world, due to its importance in both biological processes; in various industrial applications and technological [
Crystals of the title compound, (C7H9N2O)3HSO4SO4, were prepared by slow evaporation at room temperature of an aqueous solution of sulfuric acid (98wt% from Fluka) and the organic molecule 2-Aminobenzamide (Sigma-Aldrich ) in a 2:3 molar ratio. The corresponding acid-base chemical reaction can be written as follows:
After agitation, the resulting solution was left to slowly evaporate at room temperature until single crystals suitable for X-ray structure analysis formulates and remain stable under normal conditions of temperature and humidity.
The title compound has been studied by various physico-chemical methods: X-ray diffraction, Infrared spectroscopy and Thermal analysis.
X-ray intensity data of the title compound were collected on a Nonius Kappa-CCD diffractometer using monochromated Mo Kα radiation. For the crystal, 90 frames were recorded, each being of 2˚ in
Crystal data and experimental parameters used for the intensity data collection are summarized in
Setaram TG-DTA92 star system Mettler Toledo thermoanalysers were used to perform thermal treatment on samples of (C7H9N2O)3HSO4SO4. The TG-DTA experiments were carried out with 19.8 mg sample in an open alumina crucible. In this technique, samples were heated in an air atmosphere with heating rates of 5˚C∙min−1.
IR spectrum of the compound was recorded at room temperature with a Biored FTS 6000 FTIR spectrometer over the wave number range of 4000 - 400 cm−1 with a resolution of about 4 cm−1. Thin transparent pellet was made by compacting an intimate mixture obtained by shaking 2 mg of the samples in 100 mg of KBr.
The atomic arrangement of the structure of the tris (2-amoniumbenzamide) sulfate (C7H9N2O)3HSO4SO4 was
Compound | (C7H9N2O)3HSO4SO4 |
---|---|
Color/shape | Colorless/prismatic |
Formula weight | 314.29 g/mol |
Crystal system | monoclinic |
Space group | P21/c |
Temperature, K | 293(2) |
Unit cell dimensions | |
a = 10.3028(2)Å | α = 90.00 |
b = 12.4995(2) | β = 102.355(2) |
c = 20.6730(2)Å | γ = 90.00 |
Cell volume, Å3 | 2600.61(7) |
Z | 8 |
Density (calculated), g/cm3 | 1.61 |
Absorption coefficient, mm−1 | 0.45 |
diffraction measurement device | Kappa CCD Nonius |
Radiation, graphite monochr. | MoKα (λ = 0.71073 Å) |
Max. crystal dimensions, mm | 0.36 × 0.29 × 0.21 |
scan mode | Φ (CCD diffract.) |
θ range | 2 - 25˚ |
Range of h, k, l | −12 ≤ h ≤ 11, 0 ≤ k ≤ 14, 0 ≤ l ≤ 24 |
Number of scanned reflections | 4571 |
Number of independent ref. | 4441 |
Number of observed reflections | 4441 |
Reflections observed criterion | I > 2σ(I) |
Data reductions programs | Denzo [ |
Computer programs | SHELX-97 [ |
Refined parameters | 473 |
Goodness of fit on F2 | 0.952 |
R | 0.046 |
Rw | 0.114 |
described by a three-dimensional network of structural units formed by a cluster (HS2O8)3− sulfate and three organic cations (C7H9N2O)+.
oxygen O(2) of the anion
S(1) | O(1) | O(2) | O(3) | O(4) |
---|---|---|---|---|
O(1) | 1.456(3) | 107.1(2) | 110.3(20) | 109.3(2) |
O(2) | 2.381(1) | 1.506(4) | 108.96(18) | 108.7(2) |
O(3) | 2.397(1) | 2.419(1) | 1.466(3) | 112.38(17) |
O(4) | 2.362(1) | 2.391(2) | 2.413(0) | 1.438(3) |
S(2) | O(5) | O(6) | O(7) | O(8) |
O(5) | 1.466(3) | 109.4(2) | 105.25(19) | 112.2(2) |
O(6) | 2.404(1) | 1.479(3) | 107.33(19) | 113.7(2) |
O(7) | 2.354(1) | 2.397(2) | 1.497(3) | 108.4(2) |
O(8) | 2.421(0) | 2.455(0) | 2.392(1) | 1.452(3) |
Cation A | |||
---|---|---|---|
N(2)―C(7) | 1.333(6) | C(6)―C(1)―C(2) | 118.2(4) |
C(1)―C(6) | 1.387(6) | C(6)―C(1)―C(7) | 121.1(3) |
C(1)―C(7) | 1.521(6) | C(2)―C(1)―C(7) | 120.6(3) |
C(2)―N(3) | 1.458(6) | C(1)―C(2)―N(3) | 121.2(3) |
C(2)―C(1) | 1.411(6) | C(3)―C(2)―N(3) | 118.6(4) |
C(2)―C(3) | 1.380(6) | C(3)―C(2)―C(1) | 120.2(4) |
C(3)―C(4) | 1.382(7) | C(2)―C(3)―C(4) | 120.5(4) |
C(4)―C(5) | 1.376(7) | C(5)―C(4)―C(3) | 120.0(4) |
C(6)―C(5) | 1.389(7) | C(4)―C(5)―C(6) | 119.9(4) |
C(7)―O(11) | 1.225(5) | C(1)―C(6)―C(5) | 121.1(4) |
O(11)―C(7)―N(4) | 120.9(4) | ||
O(11)―C(7)―C(1) | 121.5(3) | ||
N(4)―C(7)―C(1) | 117.5(4) | ||
C(6)―C(1)―C(2) | 118.2(4) | ||
Cation B | |||
N(3)―C(8) | 1.446(6) | C(9)―C(8)―C(13) | 120.7(4) |
N(4)―C(14) | 1.331(6) | C(9)―C(8)―N(1) | 117.5(4) |
C(8)―C(9) | 1.383(6) | C(13)―C(8)―N(1) | 121.8(4) |
C(8)―C(13) | 1.398(6) | C(10)―C(9)―C(8) | 121.1(4) |
C(10)―C(9) | 1.374(7) | C(9)―C(10)―C(11) | 119,2(4) |
C(10)―C(11) | 1.383(7) | C(10)―C(11)―C(12) | 119.7(4) |
C(12)―C(11) | 1.387(6) | C(11)―C(12)―C(13) | 121.9(4) |
C(13)―C(12) | 1.389(6) | C(12)―C(13)―C(8) | 117.3(3) |
C(14)―C(13) | 1.504(6) | C(12)―C(13)―C(14) | 121.9(3) |
C(14)―O(9) | 1.241(5) | C(8)―C(13)―C(14) | 120.7(3) |
O(9)―C(14)―N2 | 120.1(4) | ||
O(9)―C(14)―C(13) | 121.5(3) | ||
N(2)―C(14)―C(13) | 118.4(3) | ||
C(9)―C(8)―C(13) | 120.7(4) | ||
Cation C | |||
N(5)―C(15) | 1.460(6) | C(16)―C(15)―N(5) | 117.8(4) |
N(6)―C(21) | 1.327(6) | C(20)―C(15)―N(5) | 121.6(3) |
C(15)―C(16) | 1.389(7) | C(16)―C(15)―C(20) | 120.6(4) |
C(16)―C(17) | 1.375(8) | C(17)―C(16)―C(15) | 120.5(4) |
C(18)―C(17) | 1.382(8) | C(16)―C(17)―C18 | 119.3(4) |
C(19)―C(18) | 1.369(7) | C(19)―C(18)―C(17) | 120.8(4) |
C(19)―C(20) | 1.400(6) | C(18)―C(19)―C(20) | 121.2(4) |
C(20)―C(21) | 1.505(6) | C(15)― C(20)―C(19) | 117.5(3) |
C(21)―O(10) | 1.244(5) | C(15)―C(20)―C(21) | 120.8(3) |
C(19)―C(20)―C(21) | 121.6(3) | ||
O(10)―C(21)―N(6) | 120.4(4) | ||
O(10)―C(21)―C(20) | 121.0(3) | ||
N(6)―C(21)―C(20) | 118.7(3) |
and N(5)-H(2N5)∙∙∙O(11) to form a first type of dimmer located in planes z = (2n + 1)/4. A second type of dimmer formed by two B cations that associate through hydrogen bond N(3)-H(2N3)・・・O(9) is situated around the center of inversion (0, 0, 0) (
The work demonstrating the important role of hydrogen bonds, the stability of the structure reveals two types of connections: O-H∙∙∙O and N-H∙∙∙O, the structure studied in this work, contains a single hydrogen bond of first type and the second type seventeen. The only link O(2)-H(O2)∙∙∙O(7) considered high [O(2)-H(O2)∙∙∙O(7) = 2.485(3)Å] [
The characteristics of the different hydrogen bonds are given in
The thermal study was conducted using a thermoanalyzer type Setaram TG-ATD92. The thermogram (TG- DTA) of
The TG curve shows no mass loss in the area, room temperature 200˚C. However it shows a significant loss from 200˚C up. The DTA curve shows two endothermic peaks less intense at 98˚C and 110˚C which is attributed to two transitions likely stage since at this temperature was noticed no mass loss. Note that the observed thermal phenomena in differential thermal analysis are many and varied. The majority of these peaks are endothermic such as melting, evaporation, sublimation, dehydration. The remaining peaks are exothermic such as adsorption, crystallization and decomposition; however, the last two phenomena can also be endothermic. The DTA curve shows a succession of exothermic and endothermic peaks between 200˚C and 400˚C can be explained by the decomposition of the molecule. The endothermic peak observed at 199˚C is attributed to the melting of the anhydrous compound.
N(O)-H(Å) | H・・・O(Å) | N(O)・・・O(Å) | N(O)-H・・・O(˚) | |
---|---|---|---|---|
N1-H1N∙∙∙O10(i) | 0.97 (5) | 2.2298 (4) | 2.7814 (4) | 115.41 (3) |
N1-H1N1∙∙∙O11 | 0.97 (5) | 1.8046 (5) | 2.6553 (5) | 145.81 (4) |
N1-H2N1∙∙∙O6 | 0.81 (5) | 1.7589 (6) | 2.7956 (5) | 173.54 (5) |
N1-H3N1∙∙∙O3 | 0.80 (5) | 2.0505 (5) | 2.8452 (5) | 177.63 (4) |
N2-H2N2∙∙∙O8(vii) | 0.87 (7) | 2.1151 (6) | 2.9045 (5) | 149.32 (5) |
N3-H1N3∙∙∙O5(iii) | 1.00 (6) | 1.7850 (5) | 2.7562 (5) | 163.01 (5) |
N3-H2N3∙∙∙O9 | 0.73 (5) | 2.0095 (4) | 2.6275 (5) | 142.71 (4) |
N3-H2N3 ∙∙O9(v) | 0.73 (5) | 2.4115 (4) | 2.9392 (5) | 130.62 (4) |
N3-H3N3∙∙∙O1 | 1.00 (8) | 1.7438 (8) | 2.7449 (5) | 166.81 (6) |
N4-H1N4∙∙∙O4(iv) | 0.81 (5) | 2.1193 (4) | 2.8967 (5) | 161.11 (4) |
N4-H2N4∙∙∙O3(v) | 0.81 (6) | 2.2504 (5) | 3.0311 (5) | 162.22 (4) |
N5-H1N5∙∙∙O1 | 0.89 (6) | 1.9790 (5) | 2.8361 (5) | 161.91 (4) |
N5-H2N5∙∙∙O10 | 0.89 (6) | 1.9040 (5) | 2.6208 (4) | 135.30 (4) |
N5-H2N5∙∙∙O11(ii) | 0.90 (5) | 2.1974 (5) | 2.8039 (4) | 124.25 (4) |
N5-H3N5∙∙∙O6(iii) | 0.90(5) | 1.5978 (9) | 2.7287 (4) | 156.46 (7) |
N6-H1N6∙∙∙O7(ii) | 0.91 (5) | 2.0838 (4) | 2.9929 (5) | 169.47 (4) |
N6-H2N6∙∙∙O5(vi) | 0.91 (5) | 2.2571 (4) | 3.0961 (5) | 153.70 (3) |
O2-HO2∙∙∙ O7 | 0.840 (4) | 1.838 (2) | 2.485 (3) | 132.60 (4) |
aSymmetry operators: i) −x, y − 1/2, −z + 1/2; ii) −x, y + 1/2, −z + 1/2; iii) x − 1, y, z; iv) x, −y + 3/2, z + 1/2; v) −x, −y + 1, −z + 1; vi) x − 1, −y + 3/2, z − 1/2; vii) −x + 1, y − 1/2, −z + 1/2.
The literature study, conducted over several sulfates [
An attempt to assign frequencies to different stretching vibrations and deformation of the organic cation is performed based on previous work [
Crystallographic data for the structural analysis have been deposited at the Cambridge Crystallographic Data Centre, CCDC No 1000722. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 IEZ, UK (fax: +44-1226-336033; e-mail: deposit@ccdc.cam).
The authors gratefully acknowledge financial support from the Ministry of Higher Education, Scientific Research and Technology of Tunisia.
SalouaBelghith,SondesChmengui,Latifa BenHamada, (2015) Crystal Structure and Physicochemical Properties of a New Tris (2-Amoniumbenzamide) Sulfate (C7H9N2O)3HSO4SO4. Open Journal of Inorganic Chemistry,05,112-121. doi: 10.4236/ojic.2015.54012