Studies in intramolecular interactions of nitroamines studied by 1H, 13C, 15N and 17O NMR spectral and quantum chemical methods

Ryszard Gawinecki, Erkki Kolehmainen , Robert Dobosz, Hossein Loghmani-Khouzani and Subramanian Chandrasekaran

Optimized geometries of the studied systems / Page S2
Calculated 15N and 17O NMR chemical shifts (/ppm) for compounds 1-7 / Page S6

Optimized geometries of the studied systems [B3LYP/6-31G(2d,p)]

1

O -2.27428 0.26853 0.36737

N -2.20528 1.49704 0.4179

N -3.397 2.18518 0.59736

C -3.32673 3.58633 0.20079

C -4.57538 1.42389 0.2008

H -4.28966 4.03332 0.43619

H -2.54906 4.08613 0.768

H -3.12032 3.70301 -0.86705

H -5.4439 2.03431 0.43641

H -4.57337 1.18697 -0.86708

H -4.61935 0.50042 0.76786

O -1.17577 2.17092 0.36734

2

N -0.85515 3.16386 0.16705

C -0.89592 4.59912 0.38778

C 0.43057 2.50846 0.30972

H -1.89545 4.96776 0.1656

H -0.64752 4.86324 1.42055

H -0.18721 5.09339 -0.27704

H 0.4642 1.62623 -0.32987

H 1.21619 3.19326 -0.00347

H 0.62057 2.19914 1.34315

C -1.98483 2.43335 0.32637

C -2.05349 1.09333 0.51059

N -3.34031 0.46706 0.57693

O -3.34062 -0.75752 0.7684

O -4.36137 1.15593 0.45168

H -2.92038 2.97749 0.27087

H -1.23858 0.40059 0.62516

3

C -0.87569 0.79378 0.05804

C -0.87858 -0.59527 0.00036

C 0.33305 -1.27843 -0.02557

C 1.54454 -0.59504 0.00075

C 1.54137 0.79401 0.05841

C 0.33276 1.52719 0.10147

N 0.3332 -2.73736 -0.09104

O 1.42711 -3.30995 -0.11603

O -0.76058 -3.31015 -0.11699

H -1.82704 1.30509 0.06777

H -1.80509 -1.15106 -0.03112

H 2.47117 -1.15065 -0.03041

H 2.49262 1.3055 0.06843

N 0.33264 2.90733 0.20041

C -0.90696 3.61515 -0.07336

C 1.57221 3.61531 -0.0731

H -0.73046 4.683 0.03181

H -1.29263 3.42232 -1.08146

H -1.6756 3.33803 0.64856

H 1.39549 4.68315 0.0318

H 2.34066 3.33845 0.64911

H 1.95821 3.42236 -1.08104

4

C -0.28775 -0.89646 -0.40342

C -1.6614 -1.10074 -0.3128

C -2.47716 -0.02243 0.0225

C -1.95651 1.24616 0.26444

C -0.57845 1.42376 0.18206

C 0.29086 0.36119 -0.13555

N -3.92554 -0.22583 0.10758

O -4.62489 0.75107 0.39134

O -4.35759 -1.36197 -0.10827

H 0.34301 -1.7213 -0.71237

H -2.10843 -2.06322 -0.51748

H -2.62372 2.05908 0.51335

H -0.15947 2.40431 0.37941

C 1.72924 0.59889 -0.18038

C 2.65289 -0.38605 -0.03009

N 4.01607 -0.26687 -0.16015

C 4.83924 -1.15845 0.64077

C 4.55985 1.06027 -0.3664

H 2.04803 1.62756 -0.29637

H 2.3274 -1.39845 0.19101

H 5.82904 -1.24191 0.19171

H 4.95451 -0.81112 1.67447

H 4.38539 -2.14856 0.65891

H 5.62685 0.97883 -0.56793

H 4.07805 1.52131 -1.22843

H 4.41512 1.71336 0.50387

5

C -2.1519 0.12418 0.12925

C -2.23306 1.53347 0.08781

N -3.45042 2.18736 -0.0051

C -3.48863 3.60921 0.29479

C -4.65581 1.42628 0.27762

H -4.51307 3.96012 0.19366

H -3.13859 3.84037 1.30802

H -2.88031 4.16879 -0.41601

H -5.51677 2.08238 0.17223

H -4.77351 0.61412 -0.44005

H -4.66273 0.99934 1.28781

C -1.01335 2.25044 0.12645

C 0.20951 1.59576 0.17573

C -0.9218 -0.52142 0.1786

C 0.28744 0.19199 0.19917

C 1.53996 -0.5473 0.25073

C 2.77422 -0.02284 0.23512

N 3.94092 -0.88075 0.29325

O 5.0339 -0.29923 0.2728

O 3.78949 -2.1035 0.35764

H -3.0493 -0.47734 0.12519

H -1.01551 3.33092 0.12069

H 1.11336 2.19333 0.20667

H -0.89649 -1.60558 0.20751

H 1.48141 -1.63024 0.30343

H 3.04696 1.01908 0.17972

6

N 4.87385 -0.05869 -0.20569

C 5.56317 1.22052 -0.15328

C 5.56196 -1.17601 0.41973

H 5.31149 1.82847 -1.02215

H 5.32914 1.79589 0.7512

H 6.63567 1.04076 -0.18276

H 5.29202 -2.11258 -0.06787

H 6.63399 -1.04091 0.29326

H 5.34482 -1.2685 1.49143

C 3.48446 -0.03956 -0.13085

C 2.74615 -1.19825 0.1958

C 1.35449 -1.18479 0.21907

C 0.6269 -0.0188 -0.06321

C 1.35731 1.13897 -0.37111

C 2.74871 1.13492 -0.40247

C -0.846 -0.00936 -0.03035

C -1.55043 1.09811 0.47448

C -2.94328 1.11845 0.50691

C -3.63336 0.00658 0.03131

C -2.97781 -1.11296 -0.47412

C -1.58472 -1.10854 -0.50333

N -5.10111 0.01499 0.06395

O -5.68692 -0.98722 -0.35424

O -5.65624 1.0237 0.50758

H 3.25353 -2.11897 0.44534

H 0.82692 -2.08911 0.50192

H 0.83078 2.0546 -0.61698

H 3.25827 2.05452 -0.65197

H -0.99784 1.94221 0.86971

H -3.49424 1.96109 0.89978

H -3.55518 -1.94915 -0.84204

H -1.05948 -1.95865 -0.9223

7

C 2.03424 0.32611 0.02803

C 2.88261 1.37976 -0.3616

C 4.26765 1.23528 -0.38007

C 4.80858 0.0126 0.00722

C 4.01052 -1.05382 0.41734

C 2.62941 -0.88527 0.43241

N 6.26619 -0.15506 -0.00435

O 6.71742 -1.24964 0.34365

O 6.94864 0.80867 -0.36237

H 2.44417 2.32412 -0.6647

H 4.92369 2.03832 -0.68426

H 4.47565 -1.97851 0.72805

H 2.00578 -1.69826 0.7835

C 0.58698 0.52769 0.00613

C -0.34044 -0.45931 -0.00505

N -6.0154 0.1451 -0.2004

C -6.61221 1.29526 0.45856

C -6.81984 -1.0655 -0.21892

H -6.25368 2.22196 0.01086

H -7.68987 1.26009 0.31385

H -6.4047 1.32799 1.53554

H -6.59778 -1.65912 -1.10561

H -6.6662 -1.69528 0.66641

H -7.87016 -0.78652 -0.26868

C -4.63565 -0.00372 -0.11077

C -4.00455 -1.23324 -0.39958

C -2.62 -1.3573 -0.35332

C -1.78714 -0.27678 -0.01765

C -2.41766 0.93865 0.30311

C -3.79979 1.07472 0.26067

H -4.59055 -2.10264 -0.66068

H -2.17148 -2.31741 -0.5874

H -1.82398 1.78833 0.62068

H -4.22823 2.02857 0.53322

H 0.25624 1.56109 -0.04609

H -0.00035 -1.49159 -0.04435

Calculated 15N and 17O NMR chemical shifts (d/ppm) for compounds 1-7
Methoda / 1 / 2 / 3 / 4 / 5 / 6 / 7
N15
1 / -241.7 / -335.5 / -347.1 / -340.5 / -350.5 / -360.9 / -357.8
2 / -226.5 / -312.2 / -322.6 / -315.7 / -324.8 / -333.8 / -331.1
3 / -224.1 / -310.8 / -321 / -314.2 / -323.2 / -332.1 / -329.4
4 / -237.6 / -331.5 / -342.4 / -334.7 / -344.9 / -355.1 / -352.0
5 / -238.9 / -331.8 / -343.0 / -335.2 / -345.3 / -355.3 / -352.1
6 / -224.2 / -311.1 / -321.4 / -314.5 / -323.6 / -332.5 / -329.8
7 / -226.5 / -313.8 / -326.5 / -318.9 / -328.5 / -337.9 / -333.7
8 / -226.5 / -314.1 / -326.3 / -319.1 / -328.9 / -338.5 / -335.1
9 / -202.3 / -292.6 / -302.1 / -291.5 / -302.5 / -310.3 / -307.3
10 / -213.5 / -311.2 / -321.3 / -309.4 / -321.8 / -330.7 / -327.1
11 / -217.3 / -315.0 / -325.8 / -314.6 / -326.9 / -335.9 / -332.7
12 / -204.2 / -299.2 / -308.8 / -298.5 / -309.3 / -317.0 / -314.0
13 / -215.6 / -318.5 / -328.2 / -317.2 / -329.4 / -338.3 / -334.7
14 / -219.6 / -322.5 / -333.5 / -322.7 / -334.8 / -343.7 / -340.7
15 / -207.3 / -303.3 / -312.9 / -302.5 / -313.1 / -318.7 / -316.5
16 / -219.0 / -322.9 / -333.3 / -321.4 / -333.5 / -339.6 / -337.0
17 / -223.1 / -326.6 / -337.8 / -326.3 / -338.6 / -345.2 / -342.6
N18
1 / -36.0 / -10.7 / -17.2 / -17.0 / -8.9 / -14.8 / -15.9
2 / -33.3 / -8.5 / -12.1 / -12.4 / -6.6 / -10.8 / -11.7
3 / -30.0 / -7.0 / -11.3 / -10.7 / -5.2 / -9.4 / -10.2
4 / -32.9 / -7.9 / -14.1 / -13.8 / -6.5 / -12.2 / -13.1
5 / -32.1 / -7.6 / -13.0 / -12.6 / -6.6 / -11.2 / -12.1
6 / -29.9 / -7.1 / -11.5 / -10.8 / -5.3 / -9.5 / -10.4
7 / -34.1 / -10.8 / -15.5 / -15.1 / -8.9 / -12.6 / -13.7
8 / -34.1 / -10.7 / -15.3 / -15.1 / -9.2 / -12.8 / -14.1
9 / -23.0 / -4.2 / -5.9 / -5.5 / -2.1 / -5.0 / -5.5
10 / -25.5 / -4.9 / -8.3 / -8.2 / -3.1 / -7.5 / -8.3
11 / -27.4 / -7.0 / -10.7 / -10.7 / -4.9 / -9.5 / -10.8
12 / -21.9 / -4.9 / -6.7 / -6.2 / -2.5 / -5.6 / -6.1
13 / -24.0 / -5.6 / -9.0 / -8.9 / -3.5 / -8.0 / -8.9
14 / -26.1 / -8.0 / -12.3 / -11.8 / -5.6 / -10.4 / -11.7
15 / -21.4 / -8.8 / -9.7 / -8.9 / -6.3 / -8.1 / -8.9
16 / -23.4 / -10.0 / -12.6 / -12.0 / -7.8 / 10.9 / -11.8
17 / -25.4 / -12.3 / -15.2 / -14.7 / -9.8 / -13.2 / -14.2
O18
1 / 538.6 / 596.6 / 643.0 / 649.0 / 633.1 / 660.8 / 657.9
2 / 500.0 / 555.5 / 599.1 / 604.1 / 587.7 / 614.0 / 611.5
3 / 500.0 / 555.4 / 597.8 / 602.9 / 586.6 / 612.7 / 610.3
4 / 563.0 / 621.2 / 669.6 / 674.8 / 657.4 / 686.3 / 683.3
5 / 563.5 / 620.3 / 667.4 / 672.8 / 655.3 / 684.1 / 681.2
6 / 505.8 / 561.6 / 603.5 / 608.3 / 592.7 / 618.3 / 615.9
7 / 493.4 / 546.0 / 587.0 / 592.4 / 577.8 / 604.1 / 600.2
8 / 494.7 / 546.9 / 588.6 / 593.6 / 579.5 / 605.2 / 601.5
9 / 466.8 / 513.8 / 555.7 / 559.0 / 541.8 / 565.5 / 563.1
10 / 527.2 / 576.0 / 623.1 / 626.7 / 608.2 / 634.1 / 631.2
11 / 505.5 / 554.9 / 599.1 / 602.8 / 586.4 / 610.1 / 607.7
12 / 490.0 / 533.2 / 577.1 / 581.2 / 563.6 / 588.3 / 585.8
13 / 552.9 / 597.4 / 646.8 / 651.3 / 632.3 / 659.2 / 656.4
14 / 530.7 / 575.3 / 621.8 / 626.6 / 609.1 / 634.4 / 631.8
15 / 504.4 / 540.5 / 583.3 / 587.5 / 567.3 / 594.9 / 592.1
16 / 568.5 / 605.5 / 653.5 / 658.0 / 636.4 / 666.3 / 663.2
17 / 546.3 / 583.5 / 628.9 / 633.4 / 613.5 / 641.7 / 639.0
a 1: B3LYP/6-311++G(d,p)//HF/3-21G
2: B3LYP/6-31G(d,p)//HF/3-21G
3: B3LYP/6-31G(2d,p)//HF/3-21G
4: B3LYP/6-311G(d,p)//HF/3-21G
5: B3LYP/6-311G(2d,p)//HF/3-21G
6: B3LYP/6-31G(2d,2p)//HF/3-21G
7: B3LYP/6-31+G(2d,p)//HF/3-21G
8: B3LYP/6-31++G(2d,p)//HF/3-21G
9: B3LYP/6-31G(2d,p)//M05/6-31G(d,p)
10: B3LYP/6-311G(d,p)//M05/6-31G(d,p)
11: B3LYP/6-311++G(d,p)//M05/6-31G(d,p)
12: B3LYP/6-31G(2d,p)//B3LYP/6-31G(d,p)
13: B3LYP/6-311G(d,p)// B3LYP /6-31G(d,p)
14: B3LYP/6-311++G(d,p)// B3LYP /6-31G(d,p)
15: B3LYP/6-31G(2d,p)//MP2/6-31G(2d,p)
16: B3LYP/6-311G(d,p)//MP2/6-31G(2d,p)
17: B3LYP/6-311++G(d,p)//MP2/6-31G(2d,p)

10