Supplemantary Materials

Transcription

1 Supplemantary Materials Mono and di(trinitromethyl)-substituted pyridines and their salts: syntheses, characterization and energetic properties Table of Contents 1. 1 H and 13 C NMR spectral data 2. TG and DSC data 3. X-ray crystallography 4. Heat of formation calculations

2 1 H and 13 C NMR spectra 2-trinitromethylpyridine 1 Figure S1. 1 H NMR spectrum of 1 in Chloroform-d Figure S2. 13 C NMR spectrum of 1 in Chloroform-d

3 2,6-ditrinitromethylpyridine 2 Figure S3. 1 H NMR spectrum of 2 in Chloroform-d Figure S4. 13 C NMR spectrum of 2 in Chloroform-d

4 2-cyano-6-trinitromethylpyridine 3 Figure S5. 1 H NMR spectrum of 3 in Chloroform-d Figure S6. 13 C NMR spectrum of 3 in Chloroform-d

5 Hydrazinium 2-dinitromethylpyridine 4 Figure S7. 1 H NMR spectrum of 4 in DMSO-d6 Figure S8. 13 C NMR spectrum of 4 in DMSO-d6

6 Dihydrazinium 2,6-di(dinitromethyl)pyridine 5 Figure S9. 1 H NMR spectrum of 5 in DMSO-d6 Figure S C NMR spectrum of 5 in DMSO-d6

7 TG and DSC data Figure S11. TG and DSC curves of 1 Figure S12. TG and DSC curves of 2

8 Figure S13. TG and DSC curves of 3 Figure S14. TG and DSC curves of 4

9 Figure S15. TG and DSC curves of 5

10 X-ray crystallography Table S1. Selected bond lengths [Å] and angles [ ] for compound 1 O1- N (2) O4 -N3 -C (17) O2 -N (2) O5 -N4 -O (18) O3 -N (2) O5 -N4 -C (17) O4 -N (2) O6 -N4 -C (16) O5 -N (2) N1 -C1 -H O6 -N (2) N1 -C1 -C (19) N1- C (2) C2 -C1 -H N1 -C (2) C1 -C2- H N2 -C (3) C3 -C2 -C (18) N3 -C (2) C3 -C2 -H N4 -C (2) C2 -C3 -H C1 -H C2 -C3 -C (18) C1 -C (3) C4 -C3 -H C2 -H C3 -C4 -H C2 -C (3) C5 -C4 -C (18) C3- H C5- C4 -H C3 -C (3) N1 -C5- C (17) C4 -H N1- C5 -C (15) C4 -C (3) C4 -C5 -C (16) C5 -C (2) N2 -C6 -N (14) C1- N1 -C (16) N4 -C6 -N (15) O1 -N2 -C (15) N4 -C6 -N (14) O2 -N2 -O (19) C5 -C6- N (14) O2 -N2 -C (17) C5 -C6 -N (15) O3 -N3 -O (18) C5 -C6 -N (14) O3 -N3 -C (16) Table S2. Torsion angles for 1 [ ] O1- N2 -C6 -N (15) O6- N4 -C6- N3-60.2(2) O1 -N2- C6 -N (19) O6 -N4 -C6 -C5 64.7(2) O1 -N2 -C6 -C5 60.3(2) N1 -C1 -C2 -C3-1.8(3) O2 -N2 -C6 -N3 4.3(2) N1 -C5 -C6 -N2 31.3(2) O2 -N2 -C6 -N (18) N1 -C5 -C6 -N (19) O2 -N2 -C6 -C (18) N1 -C5 -C6 -N (15) O3 -N3 -C6 -N (2) C1 -N1 -C5 -C4 0.9(3) O3 -N3 -C6 -N (2) C1 -N1 -C5 -C (16) O3 -N3 -C6 -C5 19.4(3) C1 -C2 -C3 -C4 1.4(3) O4 -N3 -C6 -N2 77.9(2) C2 -C3 -C4 -C5 0.1(3) O4 -N3 -C6 -N4-36.4(2) C3 -C4 -C5 -N1-1.3(3) O4- N3- C6 -C (19) C3 -C4 -C5- C (17) O5- N4 -C6 -N2 6.5(2) C4 -C5 -C6 -N (17)

11 O5- N4 -C6 -N (18) C4 -C5 -C6 -N3 92.0(2) O5- N4 -C6 -C (19) C4 -C5 -C6 -N4-27.8(2) O6 -N4 -C6 -N (15) C5 -N1- C1 -C2 0.7(3) Table S3. Selected bond lengths [Å] and angles [ ] for compound 2 O4 -N (4) O6 -N3 -C (3) O11- N (5) O8 -N5 -O (3) O12 -N (5) O8 -N5 -C (3) O10 -N (4) O7 -N5 -C (3) O9 -N (4) O1 -N1 -C (3) O8 -N (4) O2 -N1 -O (3) O3 -N (4) O2 -N1 -C (3) O7 -N (4) O4 -N2 -O (3) O5 -N (5) O4 -N2 -C (3) O6 -N (4) O3 -N2- C (3) O1 -N (4) N6 -C7 -N (3) O2 -N (4) N5 -C7 -N (3) N4 -C (5) N5 -C7 -N (3) N4 -C (5) C6 -C7 -N (3) N7 -C (5) C6 -C7 -N (3) N6 -C (5) C6 -C7 -N (3) N3 -C (5) N4 -C6- C (3) N5 -C (5) N4 -C6 -C (4) N1 -C (5) C5-C6- C (3) N2 -C (4) C6-C5 -H C7 -C (5) C4 C5 -C (4) C6 -C (5) C4-C5 -H C5 -H N4 -C2 -C (4) C5 -C (6) N4- C2 -C (3) C2 -C (5) C3 -C2 -C (3) C2 -C (5) C5 -C4 -H C4 -H C5 -C4 -C (4) C4 -C (5) C3 -C4 -H C3 -H C2 -C3 -H C6 -N4- C (3) C4 -C3 -C (4) O11- N7 -C (3) C4 -C3 -H O12 -N7 -O (3) N3 -C1- N (3) O12 -N7 -C (3) N3- C1 -N (3) O10 -N6- C (3) N2 -C1 -N (3) O9 -N6 -O (3) C2 -C1- N (3) O9 -N6- C (3) C2 -C1 -N (3) O5 -N3- O (4) C2- C1- N (3) O5 -N3 -C (3)

12 Table S4. Torsion angles for 2 [ ] O4-N2-C1-N3-83.6(4) O6-N3-C1-C (4) O4-N2-C1-N (3) O1-N1-C1-N (3) O4-N2-C1-C2 39.0(4) O1-N1-C1-N2-87.4(3) O11-N7-C7-N6-20.9(4) O1-N1-C1-C2 33.6(4) O11-N7-C7-N5 91.0(4) O2-N1-C1-N3-25.1(4) O11-N7-C7-C (3) O2-N1-C1-N2 90.3(4) O12-N7-C7-N (3) O2-N1-C1-C (3) O12-N7-C7-N5-89.1(4) N4-C6-C5-C4-2.8(6) O12-N7-C7-C6 33.2(5) N4-C2-C3-C4-1.4(6) O10-N6-C7-N7-92.8(3) N4-C2-C1-N3-15.7(4) O10-N6-C7-N (3) N4-C2-C1-N (4) O10-N6-C7-C6 30.8(4) N4-C2-C1-N (3) O9-N6-C7-N7 86.3(4) N7-C7-C6-N (3) O9-N6-C7-N5-26.4(4) N7-C7-C6-C5 54.7(5) O9-N6-C7-C (3) N6-C7-C6-N (3) O8-N5-C7-N (3) N6-C7-C6-C5-65.4(5) O8-N5-C7-N6-53.2(4) N5-C7-C6-N4-3.7(4) O8-N5-C7-C6 72.7(4) N5-C7-C6-C (4) O3-N2-C1-N3 95.6(3) C7-C6-C5-C (3) O3-N2-C1-N1-19.9(4) C6-N4-C2-C3-0.3(5) O3-N2-C1-C (3) C6-N4-C2-C (3) O7-N5-C7-N7 18.2(4) C6-C5-C4-C3 0.8(6) O7-N5-C7-N (3) C5-C4-C3-C2 1.1(6) O7-N5-C7-C (4) C2-N4-C6-C (3) O5-N3-C1-N1-47.2(4) C2-N4-C6-C5 2.4(5) O5-N3-C1-N (3) C3-C2-C1-N (3) O5-N3-C1-C2 77.1(4) C3-C2-C1-N1-73.8(4) O6-N3-C1-N (3) C3-C2-C1-N2 43.5(5) O6-N3-C1-N2 20.8(4) C1-C2-C3-C (3) Table S5. Selected bond lengths [Å] and angles [ ] for compound 3 N2- C (18) O3 -N4 -C (12) N2 -C (18) O6 -N5 -C (12) N3 -O (16) O5 -N5 -O (13) N3 -O (16) O5 -N5 -C (12) N3 -C (18) N2 -C6 -C (13) N4 -O (17) N2 -C6 -C (12) N4 -O (16) C5 -C6 -C (13) N4 -C (18) C4 -C3 -H N5 -O (16) C4 -C3 -C (13) N5 -O (17) C2 -C3 -H N5 -C (18) C6 -C5 -H C6 -C (2) C4 -C5 -C (14)

13 C6 -C (19) C4 -C5 -H C3 -H N1 -C1 -C (17) C3 -C (2) C3 -C4 -C (14) C3 -C (2) C3 -C4 -H C5 -H C5 -C4 -H C5 -C (2) N2 -C2 -C (14) C1 -N (2) N2 -C2 -C (13) C1 -C (2) C3 -C2 -C (13) C4 -H N3 -C7 -N (10) C6 -N2 -C (12) N5 -C7 -N (10) O2 -N3 -C (12) N5 -C7- N (11) O1 -N3 -O (13) C6 -C7 -N (11) O1 -N3 -C (11) C6 -C7 -N (11) O4 -N4 -O (13) C6 -C7 -N (11) O4 -N4- C (12) Table S6. Torsion angles for 3 [ ] N2 -C6 -C5 -C4 0.5(2) O4 -N4- C7 -C (16) N2 -C6 -C7 -N (13) O3 -N4 -C7 -N3-0.93(16) N2 -C6 -C7 -N (12) O3 -N4 -C7 -N (14) N2 -C6 -C7 -N5 3.01(17) O3 -N4 -C7 -C (13) O2 -N3- C7- N (14) C6 -N2 -C2 -C3 0.7(2) O2 -N3 -C7- N (15) C6 -N2 -C2- C (12) O2 -N3 -C7 -C (12) C6 -C5 -C4 -C3 0.1(2) O6 -N5 -C7 -N (14) C5 -C6 -C7 -N (16) O6 -N5 -C7 -N (12) C5 -C6 -C7 -N (17) O6 -N5 -C7 -C (14) C5 -C6 -C7 -N (12) O1 -N3 -C7 -N (13) C4 -C3 -C2 -N2-0.1(2) O1 -N3 -C7 -N (12) C4 -C3 -C2 -C (14) O1 -N3 -C7 -C (17) N1- C1- C2 -N2 118(23) O5 -N5 -C7 -N (13) N1 -C1 -C2 -C3-63(23) O5 -N5 -C7 -N (17) C2 -N2 -C6 -C5-0.9(2) O5 -N5 -C7 -C (14) C2 -N2 -C6 -C (12) O4 -N4 -C7 -N (12) C2 -C3 -C4 -C5-0.3(2) O4 -N4 -C7 -N (15) C7 -C6 -C5- C (13) Table S7. Selected bond lengths [Å] and angles [ ] for compound 4 O1 -N (16) C2 -N3- C (13) O2 -N (15) N1 -C1 -N (12) O3 -N (16) N1- C1 -C (12) O4 -N (17) N2- C1 -C (12) N1 -C (18) N3- C2 -C (12) N2 -C (18) N3- C2 -C (13) N3 -C (19) C3 -C2 -C (13)

14 N3 -C (19) C2 -C3 -H C1 -C (18) C4 -C3 -C (14) C2 -C (19) C4 -C3 -H C3 -H C3 -C4 -H C3 -C (2) C5 -C4 -C (14) C4 -H C5 -C4 -H C4 -C (2) C4 -C5 -H C5 -H C4 -C5 -C (14) C5 -C (2) C6 -C5 -H C6 -H N3 -C6 -C (14) N4 -H4A N3 -C6 -H N4 -H4B C5 -C6 -H N4 -H4C H4A -N4 -H4B N4 -N (16) H4A -N4 -H4C N5 -H5A 0.85 H4B -N4- H4C N5 -H5B 0.85 N5 -N4 -H4A O1 -N1 -C (11) N5 -N4 -H4B O2 -N1 -O (12) N5 -N4 -H4C O2 -N1 -C (12) N4 -N5 -H5A O3 -N2 -O (12) N4 -N5 -H5B O3 -N2 -C (12) H5A- N5- H5B O4 -N2- C (12) Table S8. Torsion angles for 4 [ ] O1 -N1- C1 -N (12) N2- C1 -C2- N (16) O1 -N1- C1 -C2 2.99(19) N2- C1 -C2 -C (17) O2 -N1- C1 -N2 3.7(2) N3 -C2 -C3 -C4 0.6(2) O2 -N1- C1 -C (13) C1 -C2 -C3 -C (13) O3 -N2 -C1 -N1-9.4(2) C2 -N3 -C6 -C5 0.7(2) O3 -N2 -C1 -C (13) C2 -C3 -C4 -C5 0.2(2) O4 -N2 -C1 -N (13) C3 -C4 -C5 -C6-0.6(2) O4 -N2 -C1- C2-7.80(19) C4 -C5 -C6 -N3 0.1(2) N1 -C1 -C2- N (17) C6 -N3 -C2 -C (13) N1 -C1 -C2- C (17) C6 -N3- C2 -C3-1.0(2) Table S9. Selected bond lengths [Å] and angles [ ] for compound 5 O3- N (3) O4 -N3- O (3) O1- N (4) O4- N3 -C (3) N1 -C (3) O1- N2 -C (3) N1 -C (3) O2 -N2 -O (3) N3 -O (4) O2 -N2 -C (3) N3 -C (4) C8 -C7 -H N2 -C (4) C9 -C7 -H N2 -O (4) C9 -C7 -C (3) C7 -H N1- C8 -C (3)

15 C7 -C (4) N1- C8 -C (3) C7 -C (4) C7 -C8 -C (3) C8 -C (4) C7 -C9 -C (4) C9 -C (4) C7 -C9 -H9 119 C9 -H C7 -C9 -H9 119 N4 -H4AB 0.86 N3 -C10 -N (3) N4 -H4AA 0.86 N3 -C10 -C (3) N4 -H4BC 0.86 N2 -C10 -C (3) N4 -H4BD 0.86 N5 -N4 -H4AB 108 N4 -H4CF 0.86 N5 -N4 -H4AA N4 -H4CE N6 -N4 -H4BC N4 -H4DG N6 -N4 -H4BD N4 -H4DH N8 -N4 -H4CF N4 -N (15) N8 -N4 -H4CE N4 -N (15) N9 -N4 -H4DG N4 -N (17) N9 -N4 -H4DH N4 -N (17) N4 -N5 -H5A N5 -H5A N4 -N5 -H5B N5 -H5B 0.89 N4 -N5 -H5C N5 -H5C 0.89 H5A- N5 -H N6 -H6A 0.89 H5A -N5 -H N6 -H6B H5B -N5- H N6 -H6C N4 -N6 -H6A N8 -H8A N4 -N6 -H6B N8 -H8B N4 -N6 -H6C N8 -H8C H6A- N6 -H N9 -H9A 0.89 H6A -N6 -H N9 -H9B H6B -N6- H N9 -H9C N4 -N8 -H8A C8 -N1- C (4) N4 -N8 -H8B O3 -N3 -C (2) N4 -N8- H8C 109 Table S10. Torsion angles for 5 [ ] O3- N3- C10- N (3) C7 -C8 -C10- N2-30.6(5) O3 -N3 -C10 -C8-8.4(4) C8 -N1 -C8 -C7 1.61(19) O1 -N2 -C10- N (3) C8 -N1- C8 -C (3 O1 -N2- C10- C8-16.9(4) C8- C7 -C9 -C7 1.6(2) N1 -C8 -C10 -N3-27.5(4) C9 -C7 -C8 -N1-3.2(4) N1 -C8 -C10 -N (3) C9 -C7 -C8 -C (2) O4 -N3 -C10 -N2-9.1(5) O2- N2 -C10- N3-20.8(5) O4 -N3 -C10 -C (3) O2 -N2- C10 -C (3) C7 -C8- C10 -N (3)

16 Heat of formation calculations The isodesmic reactions which are used to calculate the HOF of the target compounds are shown in Scheme S1. Scheme S1. Isodesmic reactions for 1, 2, 3, 4 anion and 5 anion. The change of enthalpy for the reactions at 298 K can be expressed as Equation (1). ΔH298 = ΣΔfH P ΣΔfH R (1) ΔfHR and ΔfHP are the HOF of the reactants and products at 298 K, respectively. ΔH298 can also be calculated as follows: ΔH298 = ΔE298 + Δ(PV) = ΔE0 + ΔZPE + ΔHT + ΔnRT (2) E0 is the total energy; ZPE is the zero-point energies (ZPE); HT is the thermal correction. On the right side of the Equation (2), it is the sum of the changes of corresponding parameters between the products and the reactants. For the isodesmic reactions, Δn = 0, so Δ(PV) = 0. Combining Equation (1) and (2), the HOF of target compounds can be obtained. Based on the Born-Haber energy cycle, the heats of formation of ionic salts can be simplified by Equation (3): H f o (ionic salts, 298 K) = H f o (cation, 298 K) + H f o (anion, 298 K) - H L (3) H L is the lattice energy of the ionic salts, which could be predicted by using the formula suggested by Jenkins et al. 1 H L = U POT + [p(n M /2-2) + q(n X /2-2)]RT (4)

17 n M and n X depend on the nature of the ions M p+ and X q-, respectively, and are equal to three for monoatomic ions, five for linear polyatomic ions, and six for nonlinear polyatomic ions. The equation for lattice potential energy U POT has the form Equation (5): U POT (kj mol -1 ) = γ(ρ m /M m ) 1/3 + δ (5) ρ m is the density (g cm -3 ) and M m is the chemical formula mass of the ionic material (g mol -1 ), and the coefficients γ (kj mol -1 cm) and δ (kj mol -1 ) are assigned literature values. Table S11. Calculated total energy (E0), zero-point energy (ZPE), thermal correction (HT), and heat of formation (HOF) of target compounds. Compd. E 0 /a.u. ZPE (kj/mol) H T (kj/mol) HOF (kj/mol) anion anion N 2 H References 1. H. D. B. Jenkins, D. Tudeal and L. Glasser, L. Inorg. Chem., 2002, 41, D. Fischer, T. M. Klapçtke, M. Reymann and J. Stierstorfer, Chem. Eur. J., 2014, 20,