Computational study of NTO (5-Nitro-2,4-dihydro-3H-1,2,4-triazol-3-one) tautomeric properties in aqueous solution
Anastasiia Golius,1 Leonid Gorb,2 Andrea Michalkova Scott,3 Frances C. Hill,3 and Jerzy Leszczynski1*
1Department of Chemistry and Biochemistry, Jackson State University, Jackson, Mississippi, USA, 1400 JR Lynch Street, Jackson, MS 39217-0510, USA
2Badger Technical Services LLC, Vicksburg, Mississippi, USA
3U.S. Army Engineer Research and Development Center, Vicksburg, Mississippi, USA
*Jerzy Leszczynski
Email:
Geometrical parameters for NTO and its tautomers
M062x / CPCMN1N2 / N2C3 / C3N4 / N4C5 / C5N1 / C3O6 / C5N7 / N7O8 / N7O9
1 / 1.34942 / 1.38405 / 1.3892 / 1.35931 / 1.28785 / 1.21629 / 1.44439 / 1.21288 / 1.21953
2 / 1.34443 / 1.34862 / 1.31766 / 1.34788 / 1.3088 / 1.32038 / 1.45626 / 1.21679 / 1.21613
3 / 1.34219 / 1.32729 / 1.3528 / 1.31187 / 1.33046 / 1.33078 / 1.44837 / 1.21969 / 1.21182
4 / 1.36226 / 1.31996 / 1.35024 / 1.35983 / 1.29775 / 1.29775 / 1.43782 / 1.21426 / 1.22163
5 / 1.3686 / 1.39165 / 1.40537 / 1.29032 / 1.33126 / 1.21796 / 1.4704 / 1.21658 / 1.20793
6 / 1.33717 / 1.37131 / 1.41909 / 1.33296 / 1.3095 / 1.2251 / 1.4314 / 1.21784 / 1.21614
7 / 1.26405 / 1.45574 / 1.37566 / 1.36769 / 1.38118 / 1.20761 / 1.31446 / 1.22999 / 1.36229
8 / 1.28822 / 1.39867 / 1.30434 / 1.36049 / 1.37052 / 1.32331 / 1.34539 / 1.21147 / 1.34365
9 / 1.2967 / 1.44603 / 1.35078 / 1.34187 / 1.34264 / 1.22743 / 1.37546 / 1.20165 / 1.32999
Table S1-S6 Bond lengths (Å) for NTO tautomers (1-9) for all considered methods
Table S1
Table S2
M062x / PCMN1N2 / N2C3 / C3N4 / N4C5 / C5N1 / C3O6 / C5N7 / N7O8 / N7O9
1 / 1.34942 / 1.38405 / 1.3892 / 1.35931 / 1.28785 / 1.21629 / 1.44439 / 1.21288 / 1.21953
2 / 1.34445 / 1.34863 / 1.31764 / 1.3479 / 1.3088 / 1.3204 / 1.45631 / 1.21678 / 1.21612
3 / 1.3422 / 1.32728 / 1.35284 / 1.31185 / 1.3305 / 1.33076 / 1.44838 / 1.21972 / 1.21179
4 / 1.36226 / 1.31993 / 1.35026 / 1.35988 / 1.29774 / 1.31928 / 1.43785 / 1.21422 / 1.22168
5 / 1.36875 / 1.39176 / 1.4055 / 1.2902 / 1.33143 / 1.21784 / 1.47047 / 1.21662 / 1.20788
6 / 1.33713 / 1.37139 / 1.41921 / 1.33298 / 1.30954 / 1.225 / 1.43135 / 1.21785 / 1.21615
7 / 1.26403 / 1.45579 / 1.37574 / 1.36771 / 1.38124 / 1.20757 / 1.31444 / 1.22995 / 1.36241
8 / 1.28818 / 1.39875 / 1.3043 / 1.3605 / 1.3706 / 1.32332 / 1.34535 / 1.21149 / 1.34371
9 / 1.29665 / 1.44625 / 1.35076 / 1.34184 / 1.34273 / 1.22735 / 1.37541 / 1.20171 / 1.33004
Table S3
M062x / GasN1N2 / N2C3 / C3N4 / N4C5 / C5N1 / C3O6 / C5N7 / N7O8 / N7O9
1 / 1.35362 / 1.39084 / 1.39689 / 1.36277 / 1.28574 / 1.20705 / 1.44932 / 1.20823 / 1.22184
2 / 1.34918 / 1.34865 / 1.31085 / 1.35207 / 1.30812 / 1.32774 / 1.46385 / 1.21374 / 1.21353
3 / 1.34396 / 1.32526 / 1.35588 / 1.30889 / 1.33401 / 1.33147 / 1.45173 / 1.22287 / 1.20723
4 / 1.36587 / 1.31278 / 1.35191 / 1.36593 / 1.29496 / 1.32673 / 1.44355 / 1.20783 / 1.22543
5 / 1.39629 / 1.41752 / 1.42546 / 1.27337 / 1.35927 / 1.19895 / 1.4791 / 1.22029 / 1.20301
6 / 1.32939 / 1.38659 / 1.43774 / 1.33564 / 1.31407 / 1.2077 / 1.42362 / 1.22171 / 1.21752
7 / 1.2578 / 1.46605 / 1.38986 / 1.36788 / 1.39352 / 1.19744 / 1.30809 / 1.23061 / 1.38472
8 / 1.27909 / 1.40968 / 1.29828 / 1.36349 / 1.38307 / 1.32353 / 1.3357 / 1.21601 / 1.35911
9 / 1.28143 / 1.49529 / 1.34916 / 1.33529 / 1.36307 / 1.2082 / 1.35913 / 1.21455 / 1.348
Table S4
MP2 / PCMN1N2 / N2C3 / C3N4 / N4C5 / C5N1 / C3O6 / C5N7 / N7O8 / N7O9
1 / 1.35719 / 1.38652 / 1.39759 / 1.35506 / 1.31008 / 1.21933 / 1.44335 / 1.22836 / 1.23447
2 / 1.35059 / 1.35094 / 1.32783 / 1.35088 / 1.33197 / 1.32661 / 1.45285 / 1.23133 / 1.23176
3 / 1.34368 / 1.3443 / 1.35262 / 1.32773 / 1.34461 / 1.33612 / 1.44037 / 1.2352 / 1.23024
4 / 1.3775 / 1.32513 / 1.35742 / 1.35587 / 1.31824 / 1.32674 / 1.44191 / 1.22836 / 1.23449
5 / 1.37072 / 1.40076 / 1.40972 / 1.30307 / 1.34033 / 1.22092 / 1.46232 / 1.23276 / 1.22745
6 / 1.32988 / 1.39345 / 1.41591 / 1.34211 / 1.33613 / 1.22499 / 1.41524 / 1.23699 / 1.23719
7 / 1.32173 / 1.4331 / 1.38877 / 1.35807 / 1.34377 / 1.21971 / 1.36615 / 1.21213 / 1.37766
8 / 1.32805 / 1.38696 / 1.32723 / 1.35248 / 1.36931 / 1.32929 / 1.37062 / 1.21574 / 1.35981
9 / 1.31021 / 1.44778 / 1.373 / 1.33025 / 1.37354 / 1.22391 / 1.37652 / 1.22287 / 1.35106
Table S5
MP2 / CPCMN1N2 / N2C3 / C3N4 / N4C5 / C5N1 / C3O6 / C5N7 / N7O8 / N7O9
1 / 1.35717 / 1.38648 / 1.39753 / 1.35503 / 1.3101 / 1.21937 / 1.44331 / 1.22838 / 1.23445
2 / 1.35057 / 1.35093 / 1.32785 / 1.35087 / 1.33197 / 1.32658 / 1.4528 / 1.23133 / 1.23176
3 / 1.34366 / 1.3443 / 1.35258 / 1.32775 / 1.34458 / 1.33614 / 1.44034 / 1.23518 / 1.23026
4 / 1.37748 / 1.32516 / 1.35739 / 1.35582 / 1.31825 / 1.32671 / 1.44188 / 1.22839 / 1.23446
5 / 1.37045 / 1.40062 / 1.40955 / 1.30322 / 1.34015 / 1.22105 / 1.46221 / 1.23274 / 1.22748
6 / 1.32989 / 1.39336 / 1.41576 / 1.3421 / 1.33608 / 1.22509 / 1.41528 / 1.23697 / 1.23718
7 / 1.32178 / 1.43301 / 1.3887 / 1.35803 / 1.34372 / 1.21977 / 1.36619 / 1.21215 / 1.3775
8 / 1.32806 / 1.38689 / 1.32728 / 1.35243 / 1.36935 / 1.32919 / 1.37064 / 1.21574 / 1.35975
9 / 1.31019 / 1.44763 / 1.37298 / 1.3303 / 1.37348 / 1.22398 / 1.3765 / 1.22284 / 1.35101
Table S6
MP2 / GasN1N2 / N2C3 / C3N4 / N4C5 / C5N1 / C3O6 / C5N7 / N7O8 / N7O9
1 / 1.36114 / 1.393 / 1.4057 / 1.35899 / 1.30759 / 1.21133 / 1.44806 / 1.22632 / 1.23621
2 / 1.35516 / 1.35154 / 1.32171 / 1.3549 / 1.33045 / 1.33382 / 1.45822 / 1.23028 / 1.23081
3 / 1.34612 / 1.34316 / 1.35545 / 1.32498 / 1.34764 / 1.33636 / 1.4448 / 1.2372 / 1.22783
4 / 1.3805 / 1.31902 / 1.35937 / 1.36234 / 1.31492 / 1.33359 / 1.44722 / 1.22513 / 1.23716
5 / 1.40244 / 1.42596 / 1.42953 / 1.2877 / 1.36419 / 1.20424 / 1.47213 / 1.23468 / 1.22487
6 / 1.32738 / 1.40907 / 1.43549 / 1.34448 / 1.34239 / 1.20938 / 1.40933 / 1.24012 / 1.2395
7 / 1.30665 / 1.45136 / 1.4002 / 1.36382 / 1.36002 / 1.2087 / 1.35301 / 1.21288 / 1.41095
8 / 1.32154 / 1.3954 / 1.32283 / 1.35495 / 1.36711 / 1.3298 / 1.36711 / 1.21658 / 1.37942
9 / 1.31214 / 1.47273 / 1.38036 / 1.31917 / 1.38031 / 1.21003 / 1.38321 / 1.22557 / 1.36898
Tables S7-S12 Angles for NTO tautomers (1-9) for all considered methods
Table S7
MO62XCPCM
C5-N1-N2 / N1-N2-C3 / N2-C3-N4 / C3-N4-C5 / N4-C5-N1 / N4-C5-7N-O8
1 / 103.2627 / 114.0472 / 101.7421 / 106.9575 / 113.9905 / 180.00
2 / 100.955 / 109.9843 / 110.635 / 100.8141 / 117.6116 / 179.98
3 / 108.9914 / 102.1693 / 115.538 / 100.9349 / 112.3664 / 179.99
4 / 106.5872 / 107.0228 / 111.1996 / 102.8843 / 112.3061 / -180.00
5 / 103.9099 / 108.0943 / 106.8416 / 104.1316 / 116.5081 / -177.67
6 / 112.6499 / 105.6881 / 106.5197 / 107.1569 / 107.9854 / -179.96
7 / 108.6171 / 109.6455 / 105.4583 / 106.3013 / 109.9777 / 179.99
8 / 105.0116 / 106.22 / 114.5176 / 99.48488 / 114.766 / -179.94
9 / 100.9147 / 112.7326 / 105.1154 / 103.1698 / 118.0675 / -179.97
Table S8
MO62XPCM
C5-N1-N2 / N1-N2-C3 / N2-C3-N4 / C3-N4-C5 / N4-C5-N1 / N4-C5-7N-O8
1 / 103.2627 / 114.0472 / 101.7421 / 106.9575 / 113.9905 / 179.99874
2 / 100.9547 / 109.9839 / 110.6355 / 100.8146 / 117.6112 / 179.97726
3 / 108.9927 / 102.1681 / 115.5387 / 100.9356 / 112.365 / 179.99194
4 / 106.587 / 107.024 / 111.2008 / 102.882 / 112.3062 / -179.99896
5 / 103.8991 / 108.0929 / 106.84 / 104.1307 / 116.5184 / -177.61344
6 / 112.6559 / 105.6893 / 106.5138 / 107.159 / 107.982 / -179.96308
7 / 108.6173 / 109.6478 / 105.4561 / 106.3009 / 109.9779 / 179.98972
8 / 105.0087 / 106.2214 / 114.5186 / 99.48383 / 114.7675 / -179.936
9 / 100.9126 / 112.7339 / 105.1091 / 103.1744 / 118.0701 / -179.97191
Table S9
MO62XGas
C5-N1-N2 / N1-N2-C3 / N2-C3-N4 / C3-N4-C5 / N4-C5-N1 / N4-C5-7N-O8
1 / 103.1671 / 114.4558 / 101.023 / 107.271 / 114.083 / 179.99
2 / 100.917 / 109.7922 / 110.915 / 100.9126 / 117.4633 / 179.99
3 / 109.3063 / 101.8043 / 115.7958 / 101.0033 / 112.0904 / 179.98
4 / 106.508 / 107.0879 / 111.5411 / 102.5003 / 112.3627 / 179.93
5 / 102.4373 / 107.0542 / 107.0121 / 103.6823 / 118.2558 / -164.92
6 / 113.7845 / 105.682 / 105.6049 / 107.5474 / 107.3812 / -179.98
7 / 108.8649 / 109.9217 / 104.9732 / 106.4324 / 109.8078 / -179.92
8 / 104.8083 / 106.342 / 114.7495 / 99.32018 / 114.78 / -179.98
9 / 100.7484 / 112.9713 / 103.639 / 104.2884 / 118.3529 / -180.00
Table S10
MP2CPCM
C5-N1-N2 / N1-N2-C3 / N2-C3-N4 / C3-N4-C5 / N4-C5-N1 / N4-C5-7N-O8
1 / 102.3935 / 114.8961 / 101.1948 / 107.6553 / 113.8603 / -179.99
2 / 100.3077 / 110.5612 / 110.7179 / 100.7887 / 117.6244 / 176.74
3 / 109.6934 / 101.6215 / 116.0355 / 100.995 / 111.6546 / -179.94
4 / 105.8819 / 107.1065 / 111.2474 / 103.3155 / 112.4488 / 179.99
5 / 103.9097 / 108.0924 / 106.807 / 104.0632 / 116.164 / -173.57
6 / 113.3082 / 105.5991 / 106.1846 / 108.327 / 106.5811 / 180.00
7 / 107.136 / 109.2913 / 105.4861 / 105.894 / 112.187 / -176.88
8 / 103.586 / 106.0753 / 114.9707 / 98.73912 / 116.629 / -179.28
9 / 99.39106 / 113.8179 / 104.6821 / 103.229 / 118.88 / -179.94
Table S11
MP2PCM
C5-N1-N2 / N1-N2-C3 / N2-C3-N4 / C3-N4-C5 / N4-C5-N1 / N4-C5-7N-O8
1 / 102.3931 / 114.8987 / 101.1911 / 107.6558 / 113.8613 / -179.9902
2 / 100.3069 / 110.5611 / 110.7183 / 100.7888 / 117.6249 / 176.74297
3 / 109.6951 / 101.6192 / 116.0371 / 100.9952 / 111.6534 / -179.94788
4 / 105.881 / 107.1077 / 111.2486 / 103.3124 / 112.4502 / 179.98798
5 / 103.8932 / 108.0857 / 106.809 / 104.0579 / 116.1814 / -173.45697
6 / 113.3138 / 105.5993 / 106.1793 / 108.3291 / 106.5785 / 179.9962
7 / 107.1394 / 109.2914 / 105.4844 / 105.8935 / 112.1858 / -176.88503
8 / 103.5859 / 106.071 / 114.9771 / 98.73146 / 116.6346 / -178.90164
9 / 99.38625 / 113.8194 / 104.6771 / 103.2307 / 118.8866 / -179.93781
Table S12
MP2Gas
C5-N1-N2 / N1-N2-C3 / N2-C3-N4 / C3-N4-C5 / N4-C5-N1 / N4-C5-7N-O8
1 / 102.3083 / 115.3379 / 100.4599 / 107.9468 / 113.947 / 179.99
2 / 100.2247 / 110.3911 / 110.9691 / 100.814 / 117.6006 / 161.18
3 / 110.0479 / 101.1869 / 116.3142 / 101.0643 / 111.3868 / -179.97
4 / 105.8333 / 107.1405 / 111.6018 / 102.8627 / 112.5617 / 179.94
5 / 102.3549 / 106.9231 / 107.0424 / 103.4819 / 118.1127 / -160.51
6 / 114.3524 / 105.4614 / 105.374 / 108.7729 / 106.0177 / -177.98
7 / 107.8491 / 109.3957 / 105.0804 / 105.9439 / 111.6263 / -178.94
8 / 103.3396 / 106.1183 / 115.2247 / 98.32845 / 116.9888 / -177.24
9 / 98.63501 / 114.1232 / 103.6228 / 103.5729 / 120.0455 / -176.63
Table S13 Molecular volume of NTO and it's tautomers at M062X and MP2 theory levels
M062X / MP2tautomer / Vgas(Å3) / VCPCM(Å3) / VPCM(Å3) / Vgas-Vcpcm(Å3) / Vcpcm-Vpcm / Vgas(Å3) / VCPCM(Å3) / VPCM(Å3) / Vgas-Vcpcm(Å3) / Vcpcm-Vpcm
1 / 341.99 / 341.94 / 341.94 / 0.05 / 0 / 343.06 / 343.17 / 343.17 / -0.11 / 0
2 / 344.16 / 344.36 / 344.36 / -0.2 / 0 / 346.05 / 345.38 / 345.38 / 0.67 / 0
3 / 342.62 / 342.71 / 342.71 / -0.09 / 0 / 344.13 / 344.5 / 344.5 / -0.37 / 0
4 / 342.53 / 342.42 / 342.47 / 0.11 / -0.05 / 343.64 / 344 / 344 / -0.36 / 0
5 / 342.36 / 343.28 / 343.21 / -0.92 / 0.07 / 343.56 / 344.52 / 344.62 / -0.96 / -0.1
6 / 340.67 / 340.44 / 340.44 / 0.23 / 0 / 342.95 / 342.23 / 342.24 / 0.72 / -0.01
7 / 345.24 / 344.65 / 344.66 / 0.59 / -0.01 / 346.59 / 346.48 / 346.49 / 0.11 / -0.01
8 / 345.47 / 345.65 / 345.65 / -0.18 / 0 / 347.39 / 347.14 / 347.13 / 0.25 / 0.01
9 / 345.31 / 344.34 / 344.29 / 0.97 / 0.05 / 347.05 / 346.14 / 346.14 / 0.91 / 0
Table S14 Selected bond lengths and torsion angles of NTO and it's tautomers at M062X theory levels
Tautomer / Average C-N bond length (Å) / N4-C5-7N-O8 / N1-N2-C3-N4CPCMa / Gasa / CPCM / Gas / CPCM / Gas
1 / 1.373 ± 0.057 / 1.377 ± 0.060 / 180.00 / 179.99 / -0.02 / -0.01
2 / 1.356 ± 0.059 / 1.357 ± 0.063 / 179.98 / 179.99 / 0.00 / 0.00
3 / 1.354 ± 0.055 / 1.355 ± 0.057 / 179.99 / 179.98 / 0.00 / 0.00
4 / 1.353 ± 0.053 / 1.354 ± 0.058 / -180.00 / 179.93 / 0.00 / -0.23
5 / 1.378 ± 0.070 / 1.391 ± 0.078 / -177.67 / -164.92 / 6.55 / 11.35
6 / 1.373 ± 0.053 / 1.380 ± 0.054 / -179.96 / -179.98 / 0.00 / -0.02
7 / 1.379 ± 0.050 / 1.385 ± 0.057 / 179.99 / -179.92 / 0.02 / 0.05
8 / 1.356 ± 0.035 / 1.358 ± 0.043 / -179.94 / -179.98 / 0.00 / 0.01
9 / 1.371 ± 0.044 / 1.380 ± 0.065 / -179.97 / -180.00 / 0.00 / 0.01