DFT and MP2 study of the geometry, IR and UV-Vis spectroscopy and first hyperpolarizability of 2-, 3- and 4-aminopyridines in the gas phase and in solvents

Nuha Ahmed Wazzan

King Abdulaziz University, Chemistry Department, Faculty of Science, Jeddah, KSA

E-Mail: ; Fax: + 966 2 695 2000/63170; Tel: + 966 12 561404754

Supplementary data

SD1: Optimized geometries

Table 1: Optimized geometry parameters of 3-APY calculated at B3LYP, and MP2 using different basis sets in the gas phase.

Coordinate / 6-31++G(d,p) / 6-31++G(2d,2p) / 6-311++G(d,p) / 6-311++G(2d,2p) / Crystal[1, 2]
B3LYP / MP2 / B3LYP / MP2 / B3LYP / MP2 / B3LYP / MP2
R(1,2) / 1.397 / 1.397 / 1.395 / 1.398 / 1.393 / 1.398 / 1.391 / 1.394 / 1.372
R(1,6) / 1.340 / 1.347 / 1.338 / 1.346 / 1.337 / 1.345 / 1.335 / 1.344 / 1.331
R(1,8) / 1.087 / 1.083 / 1.085 / 1.083 / 1.085 / 1.087 / 1.083 / 1.081 / 0.92
R(2,3) / 1.393 / 1.394 / 1.391 / 1.395 / 1.389 / 1.396 / 1.387 / 1.391 / 1.376
R(2,9) / 1.086 / 1.083 / 1.084 / 1.083 / 1.084 / 1.086 / 1.081 / 1.081 / 0.93
R(3,4) / 1.403 / 1.401 / 1.400 / 1.402 / 1.400 / 1.403 / 1.396 / 1.398 / 1.391
R(3,7) / 1.087 / 1.084 / 1.086 / 1.084 / 1.086 / 1.088 / 1.083 / 1.082 / 0.96
R(4,5) / 1.409 / 1.406 / 1.406 / 1.406 / 1.406 / 1.408 / 1.403 / 1.403 / 1.399
R(4,11) / 1.395 / 1.400 / 1.396 / 1.401 / 1.394 / 1.400 / 1.395 / 1.398 / 1.384
R(5,6) / 1.334 / 1.343 / 1.331 / 1.341 / 1.330 / 1.340 / 1.329 / 1.339 / 1.336
R(5,10) / 1.090 / 1.086 / 1.089 / 1.087 / 1.089 / 1.090 / 1.086 / 1.085 / 1.00
R(11,12) / 1.011 / 1.011 / 1.010 / 1.009 / 1.009 / 1.012 / 1.007 / 1.007 / 0.92
R(11,13) / 1.011 / 1.011 / 1.010 / 1.010 / 1.009 / 1.012 / 1.008 / 1.007 / 0.91
A(2,1,6) / 122.482 / 122.862 / 122.453 / 122.910 / 122.444 / 122.994 / 122.398 / 122.778 / 123.1
A(2,1,8) / 121.014 / 121.063 / 120.987 / 120.892 / 120.993 / 120.815 / 120.988 / 120.921 / 123
A(6,1,8) / 116.504 / 116.073 / 116.560 / 116.198 / 116.564 / 116.190 / 116.614 / 116.301 / 114
A(1,2,3) / 119.216 / 119.183 / 119.199 / 119.154 / 119.231 / 119.135 / 119.244 / 119.241 / 119.3
A(1,2,9) / 120.289 / 120.270 / 120.281 / 120.282 / 120.269 / 120.267 / 120.257 / 120.253 / 122
A(3,2,9) / 120.495 / 120.537 / 120.520 / 120.564 / 120.500 / 120.592 / 120.499 / 120.506 / 119
A(2,3,4) / 119.003 / 118.885 / 119.009 / 118.892 / 119.019 / 118.809 / 119.041 / 118.867 / 119.5
A(2,3,7) / 120.752 / 120.861 / 120.758 / 120.867 / 120.731 / 120.921 / 120.726 / 120.866 / 122
A(4,3,7) / 120.244 / 120.245 / 120.233 / 120.241 / 120.250 / 120.264 / 120.233 / 120.266 / 118
A(3,4,5) / 117.108 / 117.470 / 117.113 / 117.335 / 117.073 / 117.334 / 117.121 / 117.441 / 116.7
A(3,4,11) / 121.909 / 121.540 / 121.889 / 121.699 / 121.909 / 121.627 / 121.894 / 121.676 / 121.5
A(5,4,11) / 120.920 / 120.769 / 120.931 / 120.864 / 120.953 / 120.836 / 120.916 / 120.789 / 121.7
A(4,5,6) / 124.017 / 124.139 / 123.997 / 124.349 / 124.003 / 124.370 / 123.941 / 124.165 / 123.9
A(4,5,10) / 119.599 / 119.809 / 119.546 / 119.512 / 119.553 / 119.461 / 119.557 / 119.579 / 119
A(6,5,10) / 116.385 / 116.046 / 116.456 / 116.138 / 116.444 / 116.164 / 116.503 / 116.256 / 117
A(1,6,5) / 118.174 / 117.427 / 118.229 / 117.359 / 118.230 / 117.332 / 118.256 / 117.508 / 117.5
A(4,11,12) / 116.254 / 114.446 / 115.510 / 114.059 / 116.125 / 114.109 / 115.500 / 114.332 / 114
A(4,11,13) / 116.005 / 114.313 / 115.251 / 113.904 / 115.869 / 114.001 / 115.247 / 114.146 / 118
A(12,11,13) / 112.543 / 110.939 / 111.773 / 110.496 / 112.438 / 110.709 / 111.808 / 110.859 / 116
D(6,1,2,3) / 0.089 / 0.808 / 0.121 / 0.113 / 0.085 / 0.646 / 0.113 / 0.131 / -
D(6,1,2,9) / -179.926 / 179.680 / -179.867 / -179.959 / -179.947 / 179.754 / -179.886 / -179.908 / -
D(8,1,2,3) / 179.977 / -179.716 / -179.984 / -179.995 / 179.993 / -179.780 / -179.985 / -179.949 / -
D(8,1,2,9) / -0.038 / -0.844 / 0.028 / -0.067 / -0.038 / -0.672 / 0.016 / 0.013 / -
D(2,1,6,5) / -0.048 / -0.352 / -0.072 / -0.047 / -0.037 / -0.285 / -0.075 / -0.047 / -
D(8,1,6,5) / -179.941 / -179.852 / -179.972 / -179.943 / -179.949 / -179.877 / -179.980 / -179.971 / -
D(1,2,3,4) / -0.124 / -1.682 / -0.089 / -0.229 / -0.130 / -1.457 / -0.097 / -0.202 / -
D(1,2,3,7) / 179.623 / 179.428 / 179.687 / 179.578 / 179.603 / 179.491 / 179.656 / 179.560 / -
D(9,2,3,4) / 179.891 / 179.448 / 179.899 / 179.844 / 179.902 / 179.439 / 179.902 / 179.836 / -
D(9,2,3,7) / -0.362 / 0.558 / -0.326 / -0.350 / -0.365 / 0.387 / -0.345 / -0.402 / -
D(2,3,4,5) / 0.119 / 2.082 / 0.017 / 0.276 / 0.127 / 1.880 / 0.048 / 0.193 / -
D(2,3,4,11) / 177.248 / 176.717 / 177.056 / 176.633 / 177.222 / 176.734 / 177.040 / 176.685 / -
D(7,3,4,5) / -179.629 / -179.021 / -179.759 / -179.532 / -179.607 / -179.061 / -179.707 / -179.571 / -
D(7,3,4,11) / -2.501 / -4.386 / -2.721 / -3.175 / -2.512 / -4.207 / -2.714 / -3.079 / -
D(3,4,5,6) / -0.083 / -1.724 / 0.032 / -0.222 / -0.083 / -1.616 / -0.010 / -0.116 / -
D(3,4,5,10) / 179.816 / 179.114 / 179.930 / 179.732 / 179.789 / 179.156 / 179.883 / 179.781 / -
D(11,4,5,6) / -177.242 / -176.403 / -177.037 / -176.612 / -177.208 / -176.513 / -177.034 / -176.641 / -
D(11,4,5,10) / 2.657 / 4.436 / 2.861 / 3.343 / 2.664 / 4.259 / 2.859 / 3.256 / -
D(3,4,11,12) / 25.412 / 30.446 / 26.965 / 30.100 / 25.749 / 30.584 / 26.927 / 29.341 / -
D(3,4,11,13) / 161.158 / 159.952 / 159.768 / 158.219 / 161.006 / 159.144 / 159.769 / 158.462 / -
D(5,4,11,12) / -157.568 / -155.094 / -156.108 / -153.670 / -157.268 / -154.741 / -156.193 / -154.283 / -
D(5,4,11,13) / -21.822 / -25.589 / -23.305 / -25.551 / -22.010 / -26.181 / -23.351 / -25.163 / -
D(4,5,6,1) / 0.046 / 0.837 / -0.005 / 0.105 / 0.037 / 0.798 / 0.023 / 0.041 / -
D(10,5,6,1) / -179.855 / -179.973 / -179.906 / -179.851 / -179.839 / -179.951 / -179.873 / -179.859 / -

Table 2: Optimized geometry parameters of 4-APY calculated at B3LYP, and MP2 using different basis sets in the gas phase.

Coordinate / 6-31++G(d,p) / 6-31++G(2d,2p) / 6-311++G(d,p) / 6-311++G(2d,2p) / Crystal[3]
B3LYP / MP2 / B3LYP / MP2 / B3LYP / MP2 / B3LYP / MP2
R(1,2) / 1.392 / 1.394 / 1.390 / 1.394 / 1.389 / 1.395 / 1.386 / 1.391 / 1.374
R(4,5) / 1.392 / 1.394 / 1.390 / 1.394 / 1.389 / 1.395 / 1.386 / 1.391 / 1.370
R(1,6), / 1.342 / 1.347 / 1.339 / 1.346 / 1.338 / 1.345 / 1.336 / 1.343 / 1.338
R(5,6) / 1.342 / 1.347 / 1.339 / 1.346 / 1.338 / 1.345 / 1.336 / 1.343 / 1.352
R(1,7) / 1.088 / 1.084 / 1.087 / 1.084 / 1.087 / 1.088 / 1.084 / 1.082 / 0.98
R(4,10) / 1.088 / 1.084 / 1.087 / 1.084 / 1.087 / 1.088 / 1.084 / 1.082 / 0.98
R(5,9) / 1.088 / 1.084 / 1.087 / 1.084 / 1.087 / 1.088 / 1.084 / 1.082 / 0.99
R(2,3) / 1.407 / 1.402 / 1.404 / 1.402 / 1.403 / 1.403 / 1.400 / 1.398 / 1.401
R(3,4) / 1.407 / 1.402 / 1.404 / 1.402 / 1.403 / 1.403 / 1.400 / 1.398 / 1.406
R(2,8) / 1.087 / 1.084 / 1.085 / 1.084 / 1.085 / 1.087 / 1.082 / 1.082 / 0.95
R(3,11) / 1.384 / 1.395 / 1.385 / 1.395 / 1.383 / 1.394 / 1.384 / 1.392 / 1.363
R(11,12) / 1.009 / 1.010 / 1.009 / 1.009 / 1.008 / 1.011 / 1.006 / 1.006 / 0.94
R(11,13) / 1.009 / 1.010 / 1.009 / 1.009 / 1.008 / 1.011 / 1.006 / 1.006 / 0.91
A(2,1,6) / 124.546 / 124.388 / 124.471 / 124.439 / 124.491 / 124.505 / 124.409 / 124.282 / 125.1
A(4,5,6) / 124.546 / 124.388 / 124.471 / 124.439 / 124.491 / 124.505 / 124.409 / 124.282 / 124.7
A(2,1,7) / 119.475 / 119.770 / 119.471 / 119.605 / 119.479 / 119.557 / 119.487 / 119.631 / 121
A(4,5,9) / 119.475 / 119.770 / 119.471 / 119.605 / 119.479 / 119.557 / 119.487 / 119.631 / 122
A(6,1,7) / 115.979 / 115.842 / 116.058 / 115.956 / 116.030 / 115.938 / 116.104 / 116.088 / 115.0
A(6,5,9) / 115.979 / 115.842 / 116.058 / 115.956 / 116.030 / 115.938 / 116.104 / 116.088 / 114
A(1,2,3) / 118.988 / 119.129 / 119.005 / 119.261 / 119.016 / 119.160 / 119.051 / 119.283 / 119.4
A(3,4,5) / 118.988 / 119.129 / 119.005 / 119.261 / 119.016 / 119.160 / 119.051 / 119.283 / 119.4
A(1,2,8) / 120.232 / 120.096 / 120.248 / 120.009 / 120.223 / 120.078 / 120.219 / 120.020 / 122
A(5,4,10) / 120.232 / 120.096 / 120.248 / 120.009 / 120.223 / 120.078 / 120.219 / 120.020 / 121
A(3,2,8) / 120.779 / 120.769 / 120.748 / 120.731 / 120.760 / 120.758 / 120.730 / 120.698 / 119
A(3,4,10) / 120.779 / 120.769 / 120.748 / 120.731 / 120.760 / 120.758 / 120.730 / 120.698 / 119
A(2,3,4) / 116.972 / 117.171 / 116.975 / 116.925 / 116.936 / 116.948 / 116.970 / 116.991 / 116.4
A(2,3,11) / 121.493 / 121.322 / 121.486 / 121.489 / 121.510 / 121.437 / 121.488 / 121.448 / 122.6
A(4,3,11) / 121.493 / 121.322 / 121.486 / 121.489 / 121.510 / 121.437 / 121.488 / 121.448 / 121
A(1,6,5) / 115.961 / 115.771 / 116.074 / 115.675 / 116.050 / 115.701 / 116.110 / 115.880 / 115.0
A(3,11,12) / 117.556 / 115.045 / 116.752 / 114.773 / 117.410 / 114.749 / 116.674 / 114.983 / 120
A(3,11,13) / 117.556 / 115.045 / 116.752 / 114.773 / 117.410 / 114.749 / 116.674 / 114.983 / 119
A(12,11,13) / 114.182 / 111.741 / 113.384 / 111.491 / 114.097 / 111.601 / 113.364 / 111.820 / 116
D(6,1,2,3) / -0.004 / -0.971 / -0.026 / -0.194 / -0.025 / -0.898 / -0.004 / -0.131 / -
D(6,1,2,8) / 179.801 / 179.923 / 179.822 / 179.777 / 179.779 / 179.846 / 179.812 / 179.760 / -
D(7,1,2,3) / 179.886 / 179.330 / 179.872 / 179.762 / 179.895 / 179.354 / 179.862 / 179.778 / -
D(7,1,2,8) / -0.309 / 0.223 / -0.280 / -0.268 / -0.301 / 0.098 / -0.321 / -0.331 / -
D(2,1,6,5) / -0.080 / 0.085 / -0.064 / -0.041 / -0.061 / 0.056 / -0.083 / -0.038 / -
D(7,1,6,5) / -179.974 / 179.795 / -179.965 / -179.998 / -179.983 / 179.812 / -179.953 / -179.950 / -
D(1,2,3,4) / 0.090 / 1.774 / 0.108 / 0.409 / 0.110 / 1.658 / 0.109 / 0.296 / -
D(1,2,3,11) / 177.735 / 176.903 / 177.491 / 176.877 / 177.726 / 176.882 / 177.467 / 176.911 / -
D(8,2,3,4) / -179.714 / -179.125 / -179.739 / -179.561 / -179.693 / -179.091 / -179.706 / -179.594 / -
D(8,2,3,11) / -2.069 / -3.996 / -2.355 / -3.093 / -2.077 / -3.867 / -2.348 / -2.980 / -
D(2,3,4,5) / -0.090 / -1.774 / -0.103 / -0.406 / -0.110 / -1.657 / -0.127 / -0.304 / -
D(2,3,4,10) / 179.714 / 179.125 / 179.741 / 179.563 / 179.693 / 179.090 / 179.696 / 179.619 / -
D(11,3,4,5) / -177.736 / -176.903 / -177.486 / -176.874 / -177.727 / -176.881 / -177.485 / -176.917 / -
D(11,3,4,10) / 2.068 / 3.996 / 2.358 / 3.095 / 2.076 / 3.866 / 2.337 / 3.006 / -
D(2,3,11,12) / 19.976 / 26.521 / 21.992 / 26.304 / 20.293 / 26.894 / 22.128 / 25.777 / -
D(2,3,11,13) / 162.485 / 158.558 / 160.741 / 157.401 / 162.199 / 158.108 / 160.636 / 157.797 / -
D(4,3,11,12) / -162.485 / -158.552 / -160.743 / -157.389 / -162.199 / -158.096 / -160.633 / -157.761 / -
D(4,3,11,13) / -19.976 / -26.516 / -21.993 / -26.292 / -20.294 / -26.882 / -22.125 / -25.741 / -
D(3,4,5,6) / 0.005 / 0.970 / 0.015 / 0.187 / 0.026 / 0.896 / 0.042 / 0.146 / -
D(3,4,5,9) / -179.886 / -179.329 / -179.866 / -179.755 / -179.896 / -179.352 / -179.885 / -179.813 / -
D(10,4,5,6) / -179.801 / -179.923 / -179.831 / -179.782 / -179.778 / -179.846 / -179.781 / -179.777 / -
D(10,4,5,9) / 0.309 / -0.223 / 0.289 / 0.275 / 0.300 / -0.094 / 0.292 / 0.264 / -
D(4,5,6,1) / 0.080 / -0.084 / 0.069 / 0.045 / 0.060 / -0.055 / 0.063 / 0.031 / -
D(9,5,6,1) / 179.974 / -179.796 / 179.953 / -180.011 / 179.984 / -179.815 / 179.992 / 179.991 / -

SD2: Mulliken atomic charges

Table 3: Mulliken atomic charges on selected atoms and TNC of 2-APY calculated at B3LYP and MP2 with different basis sets in the gas phase.

Method / Basis set / C1 / C2 / C3 / C4 / C5 / N6 / N11 / TNC
B3LYP / 6-31++G(d,p) / -0.191 / 0.133 / -0.574 / 0.487 / -0.256 / -0.277 / -0.467 / -1.765
6-31++G(2d,2p) / -0.323 / 0.137 / -0.420 / 0.449 / -0.216 / -0.164 / -0.291 / -1.414
6-311++G(d,p) / -0.313 / 0.079 / -0.534 / 0.564 / -0.547 / -0.139 / -0.270 / -1.803
6-311++G(2d,2p) / -0.047 / -0.119 / -0.251 / 0.206 / 0.038 / -0.399 / -0.274 / -1.090
MP2 / 6-31++G(d,p) / -0.044 / -0.065 / -0.399 / 0.227 / -0.078 / -0.349 / -0.538 / -1.473
6-31++G(2d,2p) / 0.120 / -0.263 / 0.011 / -0.165 / 0.366 / -0.442 / -0.432 / -1.302
6-311++G(d,p) / -0.177 / -0.189 / -0.407 / 0.375 / -0.344 / -0.243 / -0.373 / -1.733
6-311++G(2d,2p) / 0.044 / -0.150 / -0.156 / 0.210 / 0.191 / -0.550 / -0.329 / -1.185

Table 4: Mulliken atomic charges on selected atoms and TNC of 3-APY calculated at B3LYP and MP2 with different basis sets in the gas phase.

Method / Basis set / C1 / C2 / C3 / C4 / C5 / N6 / N11 / TNC
B3LYP / 6-31++G(d,p) / -0.281 / -0.022 / 0.078 / -0.103 / -0.090 / -0.178 / -0.531 / -1.205
6-31++G(2d,2p) / -0.278 / 0.005 / 0.171 / -0.051 / -0.250 / -0.079 / -0.320 / -0.978
6-311++G(d,p) / -0.398 / -0.048 / 0.146 / -0.133 / -0.290 / -0.074 / -0.314 / -1.257
6-311++G(2d,2p) / -0.116 / -0.122 / 0.077 / -0.102 / 0.012 / -0.276 / -0.291 / -0.907
MP2 / 6-31++G(d,p) / -0.149 / -0.111 / 0.108 / -0.318 / 0.043 / -0.235 / -0.545 / -1.358
6-31++G(2d,2p) / 0.096 / -0.221 / 0.156 / -0.219 / 0.189 / -0.336 / -0.454 / -1.230
6-311++G(d,p) / -0.404 / -0.165 / 0.150 / -0.140 / -0.218 / -0.130 / -0.400 / -1.457
6-311++G(2d,2p) / -0.003 / -0.178 / 0.231 / -0.054 / 0.037 / -0.411 / -0.326 / -0.972

Table 5: Mulliken atomic charges on selected atoms and TNC of 4-APY calculated at B3LYP and MP2 with different basis sets in the gas phase.

Method / Basis set / C1 / C2 / C3 / C4 / C5 / N6 / N11 / TNC
B3LYP / 6-31++G(d,p) / -0.448 / 0.672 / -0.909 / 0.672 / -0.448 / -0.181 / -0.497 / -2.483
6-31++G(2d,2p) / -0.386 / 0.500 / -0.666 / 0.500 / -0.386 / -0.096 / -0.274 / -1.808
6-311++G(d,p) / -0.506 / 0.433 / -0.580 / 0.433 / -0.506 / -0.093 / -0.294 / -1.979
6-311++G(2d,2p) / -0.154 / 0.199 / -0.330 / 0.199 / -0.154 / -0.302 / -0.270 / -1.210
MP2 / 6-31++G(d,p) / -0.210 / 0.442 / -0.878 / 0.442 / -0.210 / -0.281 / -0.524 / -2.103
6-31++G(2d,2p) / 0.092 / 0.032 / -0.236 / 0.032 / 0.092 / -0.371 / -0.433 / -1.040
6-311++G(d,p) / -0.461 / 0.350 / -0.505 / 0.350 / -0.461 / -0.201 / -0.379 / -2.007
6-311++G(2d,2p) / -0.020 / 0.078 / -0.037 / 0.078 / -0.020 / -0.463 / -0.304 / -0.844

SD3: IR frequencies