Synthesis, Crystal Structure and QuantumChemical Study on 3-Phenylamino-4-Phenyl-1,2,4-Triazole-5-Thione
Abstract
:Introduction
Results and Discussion
Description of the crystal structure
Bond lengths (Å) | Exp. | B3LYP/6-311G** | PBE1PBE/6-311G** | Bond lengths (Å) | Exp. | B3LYP/6-311G** | PBE1PBE/6-311G** |
---|---|---|---|---|---|---|---|
S(1)-C(13) | 1.692(3) | 1.6684 | 1.659 | N(1)-C(14) | 1.339(4) | 1.3644 | 1.3581 |
N(1)-C(6) | 1.424(4) | 1.4073 | 1.3985 | N(2)-C(14) | 1.301(4) | 1.3034 | 1.2995 |
N(2)-N(4) | 1.383(4) | 1.3822 | 1.3683 | N(3)-C(13) | 1.365(4) | 1.3985 | 1.391 |
N(3)-C(14) | 1.388(4) | 1.3924 | 1.3844 | N(3)-C(12) | 1.433(4) | 1.431 | 1.4204 |
N(4)-C(13) | 1.313(4) | 1.3498 | 1.3439 | C(1)-C(2) | 1.374(5) | 1.3882 | 1.3846 |
C(3)-C(4) | 1.362(5) | 1.3916 | 1.388 | C(5)-C(6) | 1.374(5) | 1.3998 | 1.3959 |
C(7)-C(12) | 1.361(5) | 1.394 | 1.3904 | C(8)-C(9) | 1.378(6) | 1.3941 | 1.3907 |
C(9)-C(10) | 1.350(6) | 1.3931 | 1.3894 | C(11)-C(12) | 1.370(4) | 1.3947 | 1.3918 |
Bond angle (º) | Bond angle (º) | ||||||
C(13)-N(3)-C(14) | 107.6(3) | 107.7899 | 107.7477 | C(14)-N(2)-N(4) | 103.0(3) | 103.2568 | 103.2951 |
C(13)-N(4)-N(2) | 114.6(3) | 115.1305 | 115.2874 | C(13)-N(3)-C(12) | 127.4(3) | 125.9714 | 125.993 |
N(4)-C(13)-N(3) | 103.9(3) | 102.0667 | 102.0046 | C(7)-C(12)-N(3) | 119.2(3) | 119.6807 | 119.7079 |
C(5)-C(6)-N(1) | 123.6(3) | 123.3155 | 123.3114 | C(14)-N(1)-C(6) | 127.0(3) | 129.0576 | 128.8431 |
C(4)-C(3)-C(2) | 119.0(3) | 119.0961 | 119.0674 | C(2)-C(1)-C(6) | 120.6(3) | 120.3618 | 120.3537 |
C(10)-C(9)-C(8) | 120.5(4) | 120.146 | 120.1041 | C(6)-C(5)-C(4) | 119.0(3) | 119.3328 | 119.2883 |
C(12)-C(11)-C(10) | 119.1(4) | 119.4385 | 119.4273 | C(12)-C(7)-C(8) | 119.3(4) | 119.3845 | 119.2746 |
N(4)-C(13)-S(1) | 128.4(3) | 129.069 | 129.0636 | N(2)-C(14)-N(1) | 127.8(3) | 128.1275 | 128.2003 |
D-H•••A | Symmetry | D•••A (Å) | ∠D-H•••A (°) |
---|---|---|---|
N(1)-H(1A)•••S(1) | -1/2+x,1/2-y,-1/2+z | 3.6963 | 159.75 |
N(4)-H(4A)•••S(1) | x, 1-y, -1/2+z | 3.2696 | 139.09 |
C(5)-H(5A) ••• N(2) | 2.9298 | 122.23 | |
C(2)-H(2B)•••Cg(1) [triazolyl ring] | -1/2+x, 1/2-y, -1/2+z | 3.747 | 108.59 |
C(3)-H(3A)•••Cg(3)[C(7)-C(12)] | -1/2+x ,1/2-y, -3/2+ z | 3.685 | 164.73 |
C(5)-H(5A)•••Cg(1) [triazolyl ring] | x, 1-y, -1/2+ z | 3.944 | 134.62 |
C(8)-H(8A) •••Cg(2)[C(1)-C(6)] | 1/2+x, -1/2+y, 1+ z | 4.035 | 142.60 |
C(10)-H(10A)•••Cg(2)[C(1)-C(6)] | x , y, 1+ z | 3.562 | 148.46 |
Optimized geometry
Natural bond orbital (NBO) analysis
Bond | Occupancies(a.u) | Bond | Occupancies(a.u) | ||
---|---|---|---|---|---|
B3LYP/6-311G** | PBE1PBE/6-311G** | B3LYP/6-311G** | PBE1PBE/6-311G** | ||
S(1)-C(13) | 1.99384 | 1.98157 | C(3)-C(4)π | 1.36614 | 1.67131 |
S(1)-C(13)π | 1.98170 | C(3)-C(4)π* | 0.33789 | 0.33783 | |
S(1)-C(13)π* | 0.56667 | C(4)-C(5) | 1.97530 | 1.97504 | |
N(3)-C(13) | 1.97620 | 1.97596 | C(5)-C(6) | 1.97189 | 1.97129 |
N(3)-C(14) | 1.97569 | 1.97544 | C(5)-C(6)π | 1.64608 | 1.64588 |
N(4)-C(13) | 1.98882 | 1.98854 | C(5)-C(6)π* | 0.39220 | 0.39257 |
N(2)-N(4) | 1.97738 | 1.97787 | C(7)-C(12) | 1.97212 | 1.97113 |
N(2)-C(14) | 1.98267 | 1.98223 | C(7)-C(8) | 1.97552 | 1.97532 |
N(2)-C(14)π | 1.92656 | 1.92444 | C(7)-C(8)π | 1.64506 | 1.64350 |
N(2)-C(14)π* | 0.39694 | 0.39702 | C(7)-C(8)π* | 0.30839 | 0.30585 |
N(1)-C(14) | 1.98381 | 1.98355 | C(8)-C(9) | 1.97949 | 1.97941 |
N(1)-C(6) | 1.98431 | 1.98387 | C(9)-C(10) | 1.97945 | 1.97930 |
N(3)-C(12) | 1.98196 | 1.98143 | C(9)-C(10)π | 1.65212 | 1.65422 |
C(1)-C(6) | 1.97048 | 1.96976 | C(9)-C(10)π* | 0.31849 | 0.31979 |
C(1)-C(2) | 1.97622 | 1.97617 | C(10)-C(11) | 1.97542 | 1.97514 |
C(1)-C(2)π | 1.70572 | 1.70603 | C(11)-C(12) | 1.97228 | 1.97152 |
C(1)-C(2)π* | 0.34018 | 0.33989 | C(11)-C(12)π | 1.68578 | 1.68803 |
C(2)-C(3) | 1.97847 | 1.97838 | C(11)-C(12)π* | 0.37620 | 0.38247 |
C(3)-C(4) | 1.97940 | 1.97909 |
Atomic charge distributions
Atom | Charges (e) | Atom | Charges (e) | Atom | Charges (e) | |||
---|---|---|---|---|---|---|---|---|
B3LYP | PBE1PBE | B3LYP | PBE1PBE | B3LYP | PBE1PBE | |||
S(1) | -0.25706 | -0.25839 | C(1) | -0.23800 | -0.24608 | C(7) | -0.17805 | -0.18447 |
N(2) | -0.37039 | -0.36728 | C(2) | -0.18199 | -0.18736 | C(8) | -0.18504 | -0.19000 |
N(3) | -0.46577 | -0.45806 | C(3) | -0.22327 | -0.23177 | C(9) | -0.18313 | -0.19100 |
N(4) | -0.37746 | -0.37514 | C(4) | -0.17350 | -0.17946 | C(10) | -0.18927 | -0.19689 |
C(13) | 0.23522 | 0.23106 | C(5) | -0.24558 | -0.25464 | C(11) | -0.19869 | -0.22115 |
C(14) | 0.59570 | 0.58960 | C(6) | 0.17109 | 0.16826 | C(12) | 0.12351 | 0.12458 |
N(1) | -0.59232 | -0.59554 |
Calculation of nonlinear optical properties
Thermodynamic propertes
The title compound | 3-Benzyl-4-phenyl-1,2,4-triazole-5-thione | ||||||||
---|---|---|---|---|---|---|---|---|---|
B3LYP/6-311G** | PBE1PBE/6-311G** | B3LYP/6-311G** | |||||||
T/K | C0p,m† | S0m† | H0m‡ | C0p,m† | S0m† | H0m‡ | C0p,m† | S0m† | H0m‡ |
100.0 | 110.75 | 368.74 | 7.61 | 109.37 | 361.77 | 7.43 | 110.23 | 369.32 | 7.68 |
200.0 | 187.75 | 468.16 | 22.39 | 185.89 | 460.10 | 22.06 | 184.54 | 467.31 | 22.24 |
298.1 | 272.63 | 558.90 | 44.98 | 270.04 | 549.96 | 44.42 | 270.94 | 556.94 | 44.56 |
300.0 | 274.21 | 560.59 | 45.48 | 271.60 | 551.64 | 44.92 | 272.58 | 558.62 | 45.06 |
400.0 | 354.11 | 650.71 | 77.00 | 351.00 | 640.93 | 76.15 | 355.90 | 648.73 | 76.59 |
500.0 | 419.70 | 737.05 | 115.82 | 416.47 | 726.56 | 114.65 | 424.90 | 735.85 | 115.76 |
600.0 | 471.45 | 818.34 | 160.48 | 468.34 | 807.26 | 158.99 | 479.58 | 818.34 | 161.09 |
700.0 | 512.41 | 894.20 | 209.75 | 509.50 | 882.66 | 207.96 | 522.99 | 895.65 | 211.30 |
B3LYP/6-311G** | C0p,m = 4.722 + 1.042 T – 4.443*10 -4T 2 ( R2 = 0.9987 ) |
S0m = 266.297 + 1.047 T – 2.135*10 -4T 2 ( R2 = 0.9999) | |
H0m = -2.665 + 5.726*10-2 T + 3.542*10-4T 2( R2 = 0.9998 ) | |
PBE1PBE/6-311G** | C0p,m = 4.434 + 1.031 T – 4.342*10 -4T 2 ( R2 = 0.9988 ) |
S0m = 260.483 + 1.035 T –2.077*10 -4T 2 ( R2 = 0.9999) | |
H0m =-2.649 + 5.573*10-2 T + 3.527*10-4T 2( R2 = 0.9998 ) |
Biological activity
Experimental and Theoretical Methods
General
Synthesis
Crystallographic study
Empirical formula | C14H12N4S |
Formula weight | 268.34 |
Temperature | 293(2) K |
Wavelength | 0.71073 Å |
Crystal system, space group | Monoclinic, Cc |
Unit cell dimensions | a = 15.232(3) Å, b = 11.758(2) Å, c = 8.6025(17) Å, β = 121.66(3)° |
Volume | 1311.5(5) Å3 |
Z, Calculated density | 4, 1.359 Mg/m3 |
Absorption coefficient | 0.238 mm-1 |
F(000) | 560 |
θ range for data collection | 2.34 to 25.99° |
Limiting indices | -18≤ h ≤ 18, -9 ≤ k ≤ 14, -10≤ l ≤10 |
Reflections collected / unique | 2794 / 2221 [Rint = 0.0223 ] |
Refinement method | Full-matrix least-squares on F2 |
Data / restraints / parameters | 2221 / 2 / 172 |
Goodness-of-fit on F2 | 1.075 |
Final R indices [I>2σ (I)] | R1 = 0.0463, wR2 = 0.0980 |
R indices (all data) | R1 = 0.0492, wR2 = 0.1006 |
Largest diff. peak and hole | 0.203and -0.232e. Å-3 |
Computational methods
Acknowledgments
References and Notes
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Wang, H.-Y.; Zhao, P.-S.; Li, R.-Q.; Zhou, S.-M. Synthesis, Crystal Structure and QuantumChemical Study on 3-Phenylamino-4-Phenyl-1,2,4-Triazole-5-Thione. Molecules 2009, 14, 608-620. https://doi.org/10.3390/molecules14020608
Wang H-Y, Zhao P-S, Li R-Q, Zhou S-M. Synthesis, Crystal Structure and QuantumChemical Study on 3-Phenylamino-4-Phenyl-1,2,4-Triazole-5-Thione. Molecules. 2009; 14(2):608-620. https://doi.org/10.3390/molecules14020608
Chicago/Turabian StyleWang, Hong-Yan, Pu-Su Zhao, Rong-Qing Li, and Su-Min Zhou. 2009. "Synthesis, Crystal Structure and QuantumChemical Study on 3-Phenylamino-4-Phenyl-1,2,4-Triazole-5-Thione" Molecules 14, no. 2: 608-620. https://doi.org/10.3390/molecules14020608