Optimized geometrical parameters for ethylenediammonium chloride thiocyanate computed at HF/6-311++G (d. p), B3LYP/6-31++G (d. p) and B3LYP/6-311++G(d. p) basis sets.
The C2H10N2 Cl NCS (EDCT) compound is characterized by using infrared spectroscopy. The infrared spectrum of the title compound was recorded (400–4000 cm−1) at room temperature and discussed, essentially in terms of vibrational modes of [C2H10N2]2+ cations and [SCN]− and [Cl]− anions. Ethylenediammonium thiocyanate chloride crystallizes, at room temperature, in the triclinic system, space group P1 (Ci). The entities [C2H10N2]2+, [SCN]− and [Cl]− occupy sites of symmetry (C1). Several ground state thermodynamic parameters were calculated using the ab initio Hartree-Fock (HF) and DFT (B3LYP) methods with 6-31++G (d, p) and 6-311++G (d, p) basic sets such as vibration frequencies, rotation constants, and optimized molecular geometry. The comparison between the theoretical and experimental infrared spectrum showed good agreement.
- ethylenediammonium chloride thiocyanate
- vibrational spectra
- DFT calculations
This chapter is devoted to the characterization of C2H10N2 Cl NCS by infrared vibrational spectroscopy. These studies make it possible to highlight the structural analogies and to possibly provide some additional information to those obtained by X-ray diffraction. In this chapter, we used group theory; indeed, this valuable tool allows both to count the normal vibration modes of vibration of a crystal and to describe these vibrations in symmetrical coordinate terms. In addition, an attempt is made to assign the various modes of vibration to all the bands that have appeared. It is based on predictions theories and previous work carried out on similar compounds. Infrared is a research tool can also provide exquisite structural insights into the molecule and characterizes the vibrational modes of the molecules and has enfolded within it much information on chemical structure . The combined use of FT-IR spectroscopy extracts most of the obtainable information and these are the popular tools in the chemist and physicist. Amine, amino acid and Schiff bases [2, 3, 4, 5, 6] have recently been the focus of coordination chemists due to their preparative accessibilities, structural varieties, and varied denticities. With those purposes, first, the EDCT was synthesized  and then characterized it by Infrared Spectroscopy. Simultaneously, to obtain the ground state optimized geometries and the vibrational wavenumbers of the different normal modes, we carried out the ab initio HF and DFT calculations. Here, the hybrid B3LYP method was used together with the 6-31++G (d, p) and 6-311++G (d, p) basis sets .
2. Experimental details
The title compound has been obtained by mixing, in stoichiometric proportions, a solution of ethylenediamine, a freshly prepared solution of thiocyanic acid HSCN and a solution of potassium halide. KX (X = Cl) .
2.2 IR spectroscopy
Infrared absorption spectrum was recorded at room temperature in the 400–4000 cm−1 frequency range on a Perkin-Elmer spectrometer equipped with a Universal ATR Accessory (UATR).
2.3 Computational details
Numerous studies [9, 10, 11, 12] have shown that the method DFT-B3LYP in combination with the bases 6-31++G (d, p) and 6-311++G (d, p) allowed to determine with precision energies, molecular structures and infrared vibratory frequencies. In the ground state the molecular structure of the C2H10N2Cl NCS (EDCT) phase calculated was optimized by the use of the DFT/B3LYP methods with the methods 6-31++G (d, p) and 6-311++G (d, p) base set, and the calculated optimized structure was used in vibrational frequency calculations. The calculated harmonic vibratory frequencies and the minimal energy of the geometric structure were scaled by (B3LYP) with the base set 6-31++G (d, p) and 6-311++G (d, p). HF/DFT calculations for EDCT are performed using GAUSSIAN 03W program [13, 14]. On the other hand, the energies of the frontier orbital’s were used to calculate the gap energy values and some interesting descriptors in order to predict their reactivities an behaviors at the same level of theory [14, 15, 16, 17].
3. Results and discussion
3.1 Molecular geometry
The structure of the EDCT belongs to Ci point group symmetry and its molecular structure is obtained from GAUSSAN 03W and GAUSSVIEW programs are shown in Figure 1. The molecule contains one diprotonated ethylenediammonium cation, one Cl− and one SCN− anions. The comparative optimized structural parameters such as bond lengths and bond angles are presented in Table 1. The comparative graphs of bond lengths and bond angles of ethylenediammonium chloride thiocyanate for two sets are presented in Figures 2 and 3 respectively. Most of the optimized bond lengths are slightly higher than the experimental values, depending on the theoretical values, because the theoretical calculations belong to isolated molecules in the gas phase and the experimental results to solid state molecules. The angles and binding lengths of B3LYP are compared with those of HF, the formers are generally larger than later and the values calculated by B3LYP are well correlated with the experimental data. The parameters (the vibration frequencies and the thermodynamic properties) represent a good approximation. The data presented in Table 1 show that the theoretical HF and DFT levels (B3LYP/6-311++G (d, p)) generally estimate the same values for some link lengths and angles. The calculated C▬N bond lengths are found same at two positions (C2▬N2 and C3▬N3) is 1.4847 and 1.5066 Å (HF and DFT), 0.0049 and 0.0012 Å, respectively, differed from the experimental value 1.4798(14) and 1.5054(15) Å [15, 16, 17]. The [C2H10N2]2+ dication shows an eclipsed conformation. The calculated N▬C▬C▬N torsion angle is 74.53° (HF and DFT), 2.44° differed from the experimental value 72.09(12)° . The thiocyanate ion, present as a monodentate ligand, is almost linear. The calculated angle is 173.60° but the experimental value 178.48 (11)° and an average calculated and experimental C▬S and C▬N bond lengths are 1.6314 and 1.1651, 1.6358 (12) and 1.1573 (16) Å , respectively.
|HF/6-311++G (d. p)||B3LYP/6-31++G (d. p)||B3LYP/6-311++G (d. p)||Experimental value |
|Bond length (Å)|
|Bond angle (°)|
3.2 Vibrational analysis
3.2.1 Contribution of IR spectrometry to the vibrational study of C2H10N2 Cl NCS
18.104.22.168 Theoretical analysis of C2H10N2 Cl NCS vibrations
The factor group method of classifying fundamental vibrational modes of crystals, as developed by Bhagavantam and Venkatarayudu , is certainly the most powerful method of treating C2H10N2 Cl NCS crystal structure. The unit cell of C2H10N2 Cl NCS contains 18 atoms which correspond to 54 degrees of vibrational freedom. To simplify the discussion of the IR data, the vibrational modes will be considered in two groups: the internal modes of SCN− anions and (C2H10N2)2+ cations. Ethylenediammonium thiocyanate chloride crystallizes, at room temperature, in the triclinic system, space group P1 (Ci). The entities [C2H10N2]2+, [SCN]− and [Cl]− occupy sites of symmetry (C1).
22.214.171.124 Counting by the factor group method
The number of normal modes of vibration of the group SCN− isolated of ideal symmetry C∞v is given by the representation:
While that of an isolated group [C2H10N2]2+ of symmetry C2v is given by the irreducible representation:
The correlation diagram is given in Table 2. The counting of the main vibrations of this compound by the factor group method leads to the following results:
Overall vibration representation: Г(ni) = 54Ag + 54Au
Translation modes: Г(T’) = 9Ag + 9Au
Rotation mode: Г(R’) = 5Ag + 5Au
The representation of the internal vibrations is: Г(n’i) = 40Ag + 40Au
The analysis in terms of internal vibrations, rotation R‘ and translation T’, is given in Table 3 with their activities in IR.
|EDA (C2v)||SCN− (C∞v)||Cl− (C1)||EDA (C2v)||SCN− (C∞v)||Cl− (C1)||EDA (C2v)||SCN− (C∞v)||Cl− (C1)||IR||R|
126.96.36.199 Enumeration by the site group method
This method was used in order to have a detailed description of the symmetry and the nature of the internal vibrations (deformation in the plane or out of the plane, symmetrical or asymmetrical elongation, torsion, etc.).
188.8.131.52.1 Vibrations of [C2H10N2]2+ in group (C1)
To describe the vibrations of the organic cation, we considered separately the vibrations of the groups (-NH3) and (-CH2-) and the skeleton (C2N2)2+.
a. Description of the normal modes of vibration of the grouping (▬NH3)
The group (▬NH3) supposed free, has the symmetry 3 m (C3v), it presents nine internal vibrations schematized in Figure 4.
Each group (▬NH3) occupies a site (C1) in the cation. The use of correlation tables allows us to describe the symmetry of these vibrations in the molecular group of the cation (Table 4). The result is:
b. Description of the normal modes of vibration of the grouping (▬CH2▬)
The group (▬CH2▬) supposed free, has the symmetry mm2 (C2v), it has six internal vibrations schematized in Figure 5.
The (▬CH2▬) groups occupy E(C1) sites in the cation, the correlation method allows us to determine their vibrational symmetry in the C1 molecular group of the cation (Table 5). The result is:
c. Description of the vibration modes of the skeleton (NC2N)
To describe the vibrations of the skeleton (NC2N), the corresponding symmetrical coordinates as a function of the internal coordinates have been calculated as follows:
Increased C▬N bonds: Δri (i = 1, 2)
Increased C▬C bonds: Δr3
Increase of the CCN bond angles: Δφi (i = 1, 2)
Torsion of DC links: τCC
The number of coordinates is 6 = 3 N-6 (N: number of atoms in the backbone, here N = 4). Using the transforms of each coordinate under the symmetry operations of the point group Cs corresponding to the cation, six symmetrized coordinates were calculated (Table 6). At each coordinate a vibration mode has been assigned. These vibrations are shown schematically in Figure 6. The description of the normal modes of the NC2N backbone and their activities in IR are shown in Table 7. The irreducible representation of the internal vibration modes of the skeleton in Ci is:
d. Description of the vibration modes of SCN−
|Class||Symmetric coordinate||Vibration modes|
|A1||S1A1 = (∆r1 + ∆r2)|
S2A1 = ∆r3
S3A1 = (∆φ1 + ∆φ 2)
|Symmetrical elongation C-N: νs (C-N)|
Symmetrical elongation C-C: νs (C-C)
Symmetrical deformation in the plane CCN: δs (CCN)
|B1||S6B2 = τcc||Twist out of the plane CCN: τcc|
|B2||S4B1 = (∆r1 − ∆r2)|
S5B1 = (∆φ1 − ∆φ2)
|Asymmetrical elongation C-N: νas (C-N)|
Asymmetrical deformation in the plane CCN: δas(CCN)
|Description of mnv||C2v||C1 (site group)||Ci (factor group)|
|νs(CN)||A1(IR, R)||A(IR, R)||Ag(R) + Au(IR)|
|νas(CN)||B1(IR, R)||A(IR, R)||Ag(R) + Au(IR)|
|νs (CC)||A1(IR, R)||A(IR, R)||Ag(R) + Au(IR)|
|δs (CCN)||A1(IR, R)||A(IR, R)||Ag(R) + Au(IR)|
|δas (CCN)||B1(IR, R)||A(IR, R)||Ag(R) + Au(IR)|
|τCC||B2(IR, R)||A(IR, R)||Ag(R) + Au(IR)|
The internal vibrations of the SCN− anion have already been studied , they are described in terms of symmetrized coordinates as a function of the internal coordinates. These modes are divided in the group C∞v as follows:
These vibrations are shown schematically in Figure 7. The vibrational analysis in terms of internal vibrations is given in Table 8. The distribution of normal SCN group modes and their IR activity are shown in Table 9. The irreducible representation of the internal vibration modes of SCN− in Ci is:
|Description of mnv||C∞v||G.S (C1)||C.G (G.F)|
|ν1(CS)||A1(IR, R)||A(IR, R)||2Ag(R) + 2Au(IR)|
|ν2(CN)||A1(IR, R)||A(IR, R)||2Ag(R) + 2Au(IR)|
|δ(SCN)||E1||A(IR, R)||2Ag(R) + 2Au(IR)|
3.3 Group theory analysis
The comparisons of the experimental infrared spectra for EDCT, by using HF/6-311++G (d, p), (B3LYP) 311++G (d, p) and (B3LYP)/6-31++G (d, p) theory level, with the corresponding average predicted demonstrate good correlations as observed in Figure 8. Using the split triple valence base as well as the diffuse and polarization functions for computed harmonic vibratory frequencies of EDCT, 6-31++G (d, p) and 6-311++G (d, p), the frequencies FT-IR observed for various vibration modes were presented in Table 10. The comparative values of IR intensities activities are presented in Table 11 and their corresponding graph given in Figure 9. The comparative graph of vibratory frequencies calculated by the HF and DFT methods to HF/6-311++G (d, p), B3LYP/6-31++G (d, p) and B3LYP/6-311++G (d, p). The basic sets for the EDCT are shown in Figure 10. It appears from the figure that the frequencies calculated by B3LYP with 6-31++G (d, p) of basis sets are closer to the experimental frequencies as HF method with 6-311++G (d, p) base set.
|Calculated with HF/6-311++G (d. p)||Calculated with B3LYP/6-31++G (d. p)||Calculated with B3LYP/6-311++G (d. p)|
|Mode nos.||IR intensity||Mode nos.||IR intensity||IR intensity||IR intensity||IR intensity||IR intensity|
3.4 Bands assignments
3.4.1 NH3 modes
The asymmetric stretching νas(NH3) of symmetries (Ag + Au) are observed in IR at 3325 and 3326 cm−1. The symmetric stretching νs(NH3) of symmetries (Ag + Au) are observed in IR at 3210 cm−1. The asymmetric deformation δas(NH3) of symmetry (Ag + Au) observed IR at 1500 and 1570 cm−1. The symmetric deformation δs(NH3) of symmetries (Ag + Au) are observed in IR at 1467 cm−1. The Rocking δρ(NH3) of symmetries (Au) are observed only in IR at 493 and 498 cm−1. The torsion δτ(NH3) of symmetries (Au) observed in IR at 483 cm−1. The rocking and twisting modes are assigned as predicted by the calculations and in accordance with the expected regions for similar compounds [7, 8, 19, 20], as observed in Table 10.
3.4.2 CH2 modes
By comparison with previous works reported on similar compounds containing [C2H10N2]2+ , we have attributed the bands observed in IR at 3222 and 2427 cm−1 to asymmetric stretching νas(CH2) and symmetric νs(CH2) of symmetries (Ag + Au), respectively. The asymmetric deformation δas(CH2) and symmetric δs(CH2) is observed at 1452 and 1200 cm−1 in IR spectrum at 1341 and 1454 cm−1. The calculated frequencies of B3LYP/6-31++G (d, p) and B3LYP/6-311++G (d, p) methods for CH2 asymmetric and as asymmetric vibrations showed excellent agreement with recorded spectrum as well as literature data. The Rocking δρ (CH2) of symmetries (Ag + Au) are observed in IR at 1000 cm−1. The torsion δτ(CH2) of symmetry (Ag + Au) observed in IR at 1124 cm−1. The rocking and twisting modes are assigned as predicted by calculations, as indicated in Table 10.
3.4.3 Skeletal modes
The NCCN skeleton gives six normal modes of vibration that may be described as three skeleton stretching (2νCN + 1νCC), two NCCN deformation modes and one torsional mode around the C▬C bond. The symmetrical elongations of the symmetry skeleton νs (CC) of symmetries (Ag + Au) appear in IR at 750 cm−1. The asymmetric stretching νas(CN) of symmetries (Ag + Au) observed in IR at 544 cm−1. The symmetric stretching νs(CN) of symmetries (Au) observed in IR at 532 cm−1. The asymmetric deformation δas(CCN) of symmetry (Ag + Au), is observed in IR at 435 cm−1. The symmetric deformation δs(CCN) of symmetry (Au) observed only in IR at 430 cm−1.
3.4.4 Internal modes of the thiocyanate group (SCN−)
The thiocyanate group (SCN−) has four vibrations in the C∞v group: two of valence denoted [ν1(CS), ν2(CN)] of symmetry (Σ+) and a doubly degenerate deformation vibration denoted δ1 (SCN) of symmetry (π). From the bibliographic results [22, 23, 24, 25, 26, 27, 28] and the analysis by group theory, an attempt to attribute these vibrations observed in IR is illustrated in Table 10. The deformation δ1 (SCN) of symmetry (1Au) is observed in IR at 409 and 424 cm−1. The calculated frequencies of B3LYP/6-31++G (d, p) and B3LYP/6-311++G (d, p) methods for SCN deformation symmetric vibrations showed excellent agreement with recorded spectrum as well as literature data. We note a rise of degeneracy of the symmetry π of δ1 (SCN) with a burst of 33 cm−1. The symmetric stretching ν1 (C〓S) of symmetries (1Ag + 1Au) are observed in IR at 450 and 484 cm−1. The calculated frequencies of B3LYP/6-31++G (d, p) and B3LYP/6-311++G (d, p) methods for C〓S symmetric vibrations showed excellent agreement with recorded spectrum as well as literature data. The symmetric stretching ν2 (C〓N) of symmetries (1Ag + 1Au), predicted by the group theory, are observed in IR at 1616 cm−1.
3.5 Other molecular properties
Several calculated thermodynamic parameters are presented in Table 12. Scale factors have been recommended  for an accurate prediction in determining the zero-point vibration energies, and the entropy. It can be seen that the total energies decrease with the increase of the size of the basic set. Changes in the total entropy of EDCT at room temperature and in different basic sets are only marginal.
|Parameters||HF/6-311++ (d, p)||B3LYP/6-31++(d, p)||B3LYP/6-311++G (d. p)|
|Zero point vibration energy||105.84889||100.34649||98.57158|
|Molar capacity at constant volume|
The present document attempts to define the appropriate frequency assignments for the thiocyanate ethylenediammonium chloride compound from the FT-IR spectrum. Vibrational frequencies and infrared intensities are calculated and analyzed by the theoretical HF and DFT (B3LYP) levels, using the 6-31++G (d, p) and 6-311++G (d, p)base sets.. The comparison between the calculated vibrational frequencies and the experimental values indicates that both methods can predict the FT-IR spectra of the title compound. The results of DFT-B3LYP method indicate better fit to experimental ones than ab initio HF upon evaluation of vibrational frequencies. Several thermodynamic parameters of the title molecule are comparatively discussed. The observed and the calculated wavenumbers are found to be in good agreement with majority modes.