Structural Stability and Vibrational Analyses of Haloselenonyl Azides, XSeO2-NNN, where X is F, Cl, Br
Abstract
:Introduction
Ab initio calculations
Torsional potential scans
MP2 | |||
Parameter | X = F | X = Cl | X = Br |
bond lengths (Å) | |||
Se1 - X2 | 1.7747 | 2.1874 | 2.3572 |
Se1 - N3 | 1.8391 | 1.8599 | 1.8688 |
Se1 = O4 | 1.5941 | 1.5994 | 1.6018 |
Se1 = O5 | 1.5847 | 1.5903 | 1.5930 |
N3 = N6 | 1.2568 | 1.2542 | 1.2532 |
N6 = N7 | 1.1501 | 1.1518 | 1.1525 |
bond angles (degree) | |||
(N3Se1X2) | 96.65 | 99.08 | 99.70 |
(X2Se1O4) | 104.72 | 106.43 | 107.12 |
(X2Se1O5) | 106.33 | 107.83 | 108.54 |
(Se1N3N6) | 111.41 | 110.92 | 110.87 |
(N3N6N7) | 171.97 | 172.42 | 172.83 |
torsional angles (degree) | |||
(N3X2Se1O4) | 113.60 | 113.41 | 113.41 |
(N3X2Se1O5) | -108.84 | -108.71 | -108.67 |
(X2Se1N3N6) | 76.18 | 76.18 | 73.87 |
total energy (H) | |||
Et | -2813.4541988 | -3173.4367477 | -5286.2910420 |
total dipole moment (Debye) | |||
µt | 3.2588 | 3.2584 | 3.4999 |
rotational constants (GHz) | |||
A | 3.85980 | 2.30429 | 1.61847 |
B | 1.47242 | 1.42066 | 1.14392 |
C | 1.46064 | 1.14140 | 0.81268 |
DFT/B3LYP | |||
Parameter | X = F | X = Cl | X = Br |
bond lengths (Å) | |||
Se1 - X2 | 1.7869 | 2.2231 | 2.3866 |
Se1 - N3 | 1.8757 | 1.9001 | 1.9088 |
Se1 = O4 | 1.6082 | 1.6148 | 1.6176 |
Se1 = O5 | 1.5990 | 1.6057 | 1.6086 |
N3 = N6 | 1.2519 | 1.2480 | 1.2466 |
N6 = N7 | 1.1248 | 1.1267 | 1.1274 |
bond angles (degrees) | |||
(N3Se1X2) | 97.13 | 100.30 | 101.22 |
(X2Se1O4) | 105.03 | 106.97 | 107.70 |
(X2Se1O5) | 106.44 | 107.72 | 108.25 |
(Se1N3N6) | 112.34 | 112.15 | 112.16 |
(N3N6N7) | 172.45 | 173.36 | 173.50 |
torsional angles (degrees) | |||
(N3X2Se1O4) | 114.35 | 114.23 | 114.18 |
(N3X2Se1O5) | -108.91 | -109.12 | -109.18 |
(X2Se1N3N6) | 79.03 | 82.75 | 84.06 |
total energy (H) | |||
Et | -2816.0122882 | -3176.376035 | -5290.3039151 |
total dipole moment (Debye) | |||
µt | 2.2964 | 2.1935 | 2.3910 |
rotational constants (GHz) | |||
A | 3.77760 | 2. 28284 | 1.70586 |
B | 1.44238 | 1.35332 | 1.02641 |
C | 1.42986 | 1.09894 | 0.77273 |
Quantity | X = F | X = Cl | X = Br |
V0 | 2.0910 | 2.2961 | 2.2462 |
V1 | 0.4423 | 0.7409 x 10-1 | 0.1828 x 10-1 |
V2 | -1.9892 | -2.0817 | -2.0485 |
V3 | -0.4604 | -0.4314 | -0.3915 |
V4 | 0.2529 x 10-1 | -0.3348 x 10-1 | -0.4481 x 10-1 |
V5 | 0.7158 x 10-3 | -0.3756 x 10-1 | -0.3175 x 10-1 |
V6 | -0.5353 x 10-2 | -0.1161 x 10-2 | 0.5389 x 10-2 |
rms | 0.1368 x 10-1 | 0.3625 x 10-2 | 0.4879 x 10-2 |
E0 | -2816.012294 | -3176.376037 | -5290.303921 |
Vibrational modes and normal coordinate analyses
No. | Coordinate | Definition | |
1 | Se1-X2 | stretch | Q |
2 | Se1-N3 | stretch | T |
3 | Se1-O4 | stretch | X1 |
4 | Se1-O5 | stretch | X2 |
5 | N3-N6 | stretch | R1 |
6 | N6-N7 | stretch | R2 |
7 | N3Se1X2 | bend | θ |
8 | X2Se1O4 | bend | ε1 |
9 | X2Se1O5 | bend | ε2 |
10 | O4Se1O3 | bend | π1 |
11 | O5Se1O3 | bend | π2 |
12 | O4Se1O5 | bend | δ |
13 | Se1N3N6 | bend | γ |
14 | N3N6N7 | bend | σ1 |
15 | N7N6N3Se1 | wag | σ2 |
16 | N6N3Se1O4 + N6N3Se1O5 | torsion | τ |
Description | Symmetry coordinate |
X - Se stretch | S1 = Q |
Se - N stretch | S2 = T |
NNN symmetric stretch | S3 = R1 + R2 |
SeO2 symmetric stretch | S4 = X1 + X2 |
NNN antisymmetric stretch | S5 = R1 - R2 |
SeO2 antisymmetric stretch | S6 = X1 - X2 |
XSeN bend | S7 = 5θ-ε1-ε2-π1-π2-δ |
SeNN bend | S8 = γ |
NNN in-plane bend | S9 = σ1 |
NNN out-of-plane bend | S10 = σ2 |
SeO2 deformation | S11 = 4δ- ε1-ε2-π1-π2 |
SeO2 rock | S12 = ε1-ε2+π1-π2 |
SeO2 twist | S13 = ε1-ε2-π1+π2 |
SeO2 wag | S14 = ε1+ε2-π1-π2 |
NNN torsion | S15 = τ |
ki | Ii | Si | ρi | PED |
Fluoroselenonyl azide (X = F) | ||||
2237 | 411.8 | 133.6 | 0.36 | 88% S5, 12% S3 |
1214 | 206.6 | 3.4 | 0.72 | 85% S3, 13% S5 |
996 | 99.7 | 12.7 | 0.64 | 98% S6 |
912 | 75.2 | 28.7 | 0.07 | 97% S4 |
675 | 7.1 | 9.1 | 0.20 | 49% S9, 31% S8, 17% S2 |
591 | 120.4 | 15.1 | 0.09 | 97% S1 |
554 | 3.1 | 0.9 | 0.67 | 96% S10 |
441 | 90.1 | 25.8 | 0.12 | 68% S2, 17% S9 |
329 | 40.2 | 5.0 | 0.44 | 30% S12, 22% S11, 18% S14, 13% S9 |
311 | 22.2 | 6.0 | 0.62 | 70% S14, 15% S12 |
308 | 21.7 | 6.7 | 0.53 | 47% S11, 35% S12 |
251 | 0.8 | 6.4 | 0.62 | 78% S13 |
231 | 0.7 | 1.6 | 0.74 | 78% S7, 17% S11 |
130 | 1.4 | 4.0 | 0.52 | 54% S8, 15% S12, 15% S13, 14% S9 |
52 | 0.0 | 3.3 | 0.75 | 95% S15 |
Chloroselenonyl azide (X = Cl) | ||||
2221 | 444.1 | 154.9 | 0.37 | 88% S5, 12% S3 |
1220 | 201.1 | 4.5 | 0.75 | 86% S3, 13% S5 |
977 | 92.6 | 15.9 | 0.64 | 97% S6 |
899 | 77.2 | 30.2 | 0.05 | 97% S4 |
669 | 4.8 | 9.5 | 0.19 | 51% S9, 32% S8, 14% S2 |
550 | 4.8 | 0.9 | 0.63 | 97% S10 |
420 | 86.6 | 29.7 | 0.15 | 72% S2, 16% S9 |
378 | 123.1 | 15.6 | 0.11 | 67% S1, 17% S14, 12% S11 |
311 | 29.6 | 6.1 | 0.36 | 42% S11, 24% S14, 11% S12 |
289 | 5.3 | 18.6 | 0.36 | 43% S14, 32% S1, 22% S11 |
281 | 4.8 | 10.6 | 0.53 | 47% S12, 11% S11 |
211 | 1.2 | 4.8 | 0.70 | 76% S13, 18% S12 |
188 | 1.4 | 2.8 | 0.75 | 83% S7 |
126 | 1.2 | 5.2 | 0.47 | 53% S8, 17% S12, 14% S9, 11% S13 |
38 | 0.1 | 6.6 | 0.74 | 95% S15 |
Bromoselenonyl azide (X = Br) | ||||
2215 | 458.4 | 167.5 | 0.37 | 88% S5, 12% S3 |
1223 | 199.7 | 5.3 | 0.75 | 86% S3, 13% S5 |
970 | 90.6 | 18.5 | 0.65 | 97% S6 |
893 | 78.5 | 31.9 | 0.05 | 97% S4 |
668 | 4.6 | 9.4 | 0.20 | 52% S9, 32% S8, 13% S2 |
550 | 4.4 | 1.0 | 0.56 | 97% S10 |
412 | 85.2 | 34.0 | 0.16 | 74% S2, 15% S9 |
341 | 109.8 | 2.5 | 0.21 | 40% S14, 32% S11, 20% S1 |
306 | 27.1 | 5.5 | 0.36 | 39% S11, 30 S14 |
275 | 3.3 | 1.7 | 0.49 | 42% S12, 13% S13, 11% S11 |
222 | 1.1 | 23.1 | 0.25 | 78% S1, 15% S14 |
188 | 1.0 | 2.9 | 0.71 | 70% S13, 21% S12 |
165 | 1.6 | 2.6 | 0.74 | 75% S7 |
123 | 1.2 | 5.5 | 0.43 | 50% S8, 16% S12, 14% S7, 13% S9 |
33 | 0.1 | 7.2 | 0.73 | 94% S15 |
Discussion
Acknowledgements
References
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Förner, W.; Badawi, H.M.; Seddigi, Z.S. Structural Stability and Vibrational Analyses of Haloselenonyl Azides, XSeO2-NNN, where X is F, Cl, Br. Int. J. Mol. Sci. 2005, 6, 230-244. https://doi.org/10.3390/i6090230
Förner W, Badawi HM, Seddigi ZS. Structural Stability and Vibrational Analyses of Haloselenonyl Azides, XSeO2-NNN, where X is F, Cl, Br. International Journal of Molecular Sciences. 2005; 6(9):230-244. https://doi.org/10.3390/i6090230
Chicago/Turabian StyleFörner, Wolfgang, Hassan M. Badawi, and Zaki S. Seddigi. 2005. "Structural Stability and Vibrational Analyses of Haloselenonyl Azides, XSeO2-NNN, where X is F, Cl, Br" International Journal of Molecular Sciences 6, no. 9: 230-244. https://doi.org/10.3390/i6090230