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1 Supporting Information Prediction of the crystal packing of Di-tetrazine-tetroxide (DTTO) Energetic Material Jose L. Mendoza-Cortes 1,2,3,5, Qi An 1,5, William A. Goddard III 1 *, Caichao Ye 1,4, Sergey Zybin 1 1 Materials and Process Simulation Center, California Institute of Technology, 1200 E. California Blvd MC , Pasadena CA 91125, USA. 2 Present Address: Joint Center for Artificial Photosynthesis, Lawrence Berkeley National Laboratory, Materials Division, Berkeley, CA 94720, U.S.A. 3 Present Address: University of California, Berkeley, Department of Chemistry, Berkeley, CA 94720, USA. 4 School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing , P. R. China 5 These authors contributed equally wag@wag.caltech.edu Note: Originally we named the structure Tetrazino-tetrazine-tetraoxide (TTTO) but now it described as Di-tetrazine-tetroxide (DTTO). This is because most of the literature citations use DTTO.

2 S2 Contents Page Title S1 List of Contents S2 List of Figures S3 List of Tables S4 1 Structures from FF S5 2 Relative Energies from FF vs QM S6 3 Structures from QM S9 3.1 DTTO configuration 1 (c1) S9 3.2 DTTO configuration 2 (c2) S Coordinates for structures of DTTO configuration 1 (c1) S c1-dtto: space group C 2/c (15) S c1-dtto: space group P 1 (2) S c1-dtto: space group P 21/c (14) global minimum S c1-dtto: space group P 21/c (14) local minima S c1-dtto: space group P (19) S Coordinates for structures of DTTO configuration 2 (c2) S c1-dtto: space group C2 (5) S c1-dtto: space group C 2/c (15) S c1-dtto: space group C c (9) S c1-dtto: space group P n m a (62) S c1-dtto: space group P b c a (61) S16 4 PXRD S PXRD plot for c1-dtto S PXRD plot for c2-dtto S First peaks PXRD data for c1-dtto S First peaks PXRD data for c2-dtto S23 Bibliography S30

3 S3 List of Figures Page 1 Dreiding FF structures for the 10 most common space groups for the c1-isomer S5 2 Dreiding FF structures for the 10 most common space groups for the c2-isomer S5 3 FF relative energies vs QM relative energies S8 4 c1-dtto: space group C 2/c (15) S9 5 c1-dtto: space group P 1 (2) S9 6 c1-dtto: space group P 21/c (14) global minimum S10 7 c1-dtto: space group P 21/c (14) local minima S10 8 c1-dtto: space group P (19) S10 9 c2-dtto: space group C2 (5) S11 10 c2-dtto: space group C 2/c (15) S11 11 c2-dtto: space group C c (9) S12 12 c2-dtto: space group P n m a (62) S12 13 c2-dtto: space group P b c a (61) S12 14 PXRD for configuration 1 of DTTO with space group C 2/c (15), P 1 (2), P 21/c (14) and P (19) S18 15 PXRD for configuration 2 of DTTO with space group C2 (5), C 2/c (15), C c (9), P n m a (62) and P b c a (61) S19

4 S4 List of Tables Page 1 Dreiding packing for c S6 2 UFF packing for c S6 3 Dreiding packing for c S7 4 UFF packing for c S7 5 Table of reflexion parameters of the PXRD for c1-dtto with space group C 2/c (15) S20 6 Table of reflexion parameters of the PXRD for c1-dtto with space group P 1 (2) S20 7 Table of reflexion parameters of the PXRD for c1-dtto with space group P 21/c (14) S21 8 Table of reflexion parameters of the PXRD for c1-dtto with space group P 21/c (14) S21 9 Table of reflexion parameters of the PXRD for c1-dtto with space group P (19) S23 10 Table of reflexion parameters of the PXRD for c1-dtto with space group C2 (5) S23 11 Table of reflexion parameters of the PXRD for c1-dtto with space group C 2/c (15) S24 12 Table of reflexion parameters of the PXRD for c1-dtto with space group C c (9) S26 13 Table of reflexion parameters of the PXRD for c1-dtto with space group P n m a (62) S27 14 Table of reflexion parameters of the PXRD for c1-dtto with space group P b c a (61) S28

5 Di-tetrazine-tetroxide (DTTO), aka Tetrazino-tetrazine-tetraoxide (TTTO) 1 Structures obtained from classical Force Fields Using classical Force Fields Dreiding and the Universal Force Field (UFF), we explore the structure of on the most stable isomers of DTTO we found: c1 and c2 would form stable packing structures. We explore their packing in the 10 most common space groups for molecular crystals: P21/c, P-1, P212121, P21, C2/c, PBCA, C2, PNA21, PBCN and CC. The space group symmetry was calculated within the atomistic simulation codes and also were corroborated at the beginning and at the end of the simulation with FINDSYM. [1] C2 C2-c CC P-1 P21 P21-C PBCA PBCN P PNA21 Figure S1: Dreiding FF structures for the 10 most common space groups for the c1-isomer P21 C2 C2-c CC P-1 PBCA P21-C P PBCN PNA21 Figure S2: Dreiding FF structures for the 10 most common space groups for the c2-isomer S5

6 2 Relative Energies from FF vs QM We show the relative energies ( E) with respect to the given force field and isomer in Table S1-S4. In general Dreiding and UFF give the same trends for this case. However the magnitude is different. Table S1: Dreiding packing for c1 Space group Formula Rank E (kcal/mol) DTTO alone C2N8O4 C2/c C16N64O C2 C8N32O CC C8N32O P-1 C4N16O P21/C C8N32O P21 C4N16O P C8N32O PBCA C16N64O PBCN C16N64O PNA21 C8N32O Table S2: UFF packing for c1 Space group Formula Rank E (kcal/mol) DTTO alone C2N8O4 C2/c C16N64O C2 C8N32O CC C8N32O P-1 C4N16O P21/C C8N32O P21 C4N16O P C8N32O PBCA C16N64O PBCN C16N64O PNA21 C8N32O S6

7 Table S3: Dreiding packing for c2 Space group Formula Rank E (kcal/mol) DTTO alone C2N8O4 C2/c C16N64O C2 C8N32O CC C8N32O P-1 C4N16O P21/C C8N32O P21 C4N16O P C8N32O PBCA C16N64O PBCN C16N64O PNA21 C8N32O Table S4: UFF packing for c2 Space group Formula Rank E (kcal/mol) DTTO alone C2N8O4 C2/c C16N64O C2 C8N32O CC C8N32O P-1 C4N16O P21/C C8N32O P21 C4N16O P C8N32O PBCA C16N64O PBCN C16N64O PNA21 C8N32O S7

8 A direct comparison shows that the top 5 structures predicted by UFF and Dreiding are the top 5 predicted by QM. In other words, the trend can be captured by a general purpose Force Field such as Dreiding or UFF. This can be seen more clearly in Figure S3. FF ranking vs QM ranking Dreiding Comp. DE P21/C P P C P c1 QM:PBE-ulg Comp. DE P P21 P21/C P21/C P C Dreiding Comp. DE C2/c 10.0 PBCA 20.1 CC 30.7 P C The trend can be captured by a general purpose Force Field such as Dreiding or UFF. c2 QM:PBE-ulg Comp. DE PBCA C2/c P PNMA CC C Energies: kcal/mol UFF Comp. DE P21/C P P C P c1 QM:PBE-ulg UFF c2 Comp. DE P21 P21/C P P21/C P C Comp. DE C C2/c PBCA CC P QM:PBE-ulg Comp. DE PBCA C2/c P PNMA CC C Figure S3: FF relative energies vs QM relative energies. S8

9 3 Structures obtained from periodic quantum mechanics (PBE-ulg) In the main text we discussed the top 5 structures obtained from the Force Field (FF) for configuration 1 and 2 of DTTO, which were further optimized with Quantum Mechanics at the DFT:PBE-ulg level. These structures are presented in the following section, first we present their representation followed by their coordinates. We present the space group with the Hermann-Mauguin alphanumeric code and in parenthesis we also show the space group sequential number(1-230). 3.1 DTTO configuration 1 (c1) In general we the space group obtained from FF is maintained after QM optimization. There is only one case where we found that the QM minimization found a minimum with a more symmetrical space group. This case is the structure for which the FF packing procedure found P 21 (4) and QM minimization found this structure transition to P 21/c (14). The FF procedure found this to be the 3rd most stable packing, however with the QM scheme this packing becomes the most stable packing for configuration 1 (c1) of DTTO. 4.1: view 1 4.2: view 2 Figure S4: c1-dtto: space group C 2/c (15) 5.1: view 1 5.2: view 2 Figure S5: c1-dtto: space group P 1 (2) S9

10 Di-tetrazine-tetroxide (DTTO), aka Tetrazino-tetrazine-tetraoxide (TTTO) 6.1: view 1 6.2: view 2 Figure S6: c1-dtto: space group P 21/c (14) global minimum 7.1: view 1 7.2: view 2 Figure S7: c1-dtto: space group P 21/c (14) local minima 8.1: view 1 8.2: view 2 Figure S8: c1-dtto: space group P (19) S10

3.2 DTTO configuration 2 (c2) In a similar fashion as for c1, we found that for the configuration 2 (c2) of DTTO the symmetry from the structures

The structure obtained from the FF packing scheme with P 2 1 2 1 2 1 (19) space group transition to P n m a (62) space group after QM minimization.

periodic DFT:PBE-ulg the structure becomes the 3rd most stable structure besides transition to a more symmetrical space group, P n m a (62).

changes, i.e. FF: C 2/c (15) changes from 1st to QM: 2nd; FF:C c (9) changes from 3rd to QM: 4th; and FF:P b c a (61) changes from 2nd to QM: 1st.

11 3.2 DTTO configuration 2 (c2) In a similar fashion as for c1, we found that for the configuration 2 (c2) of DTTO the symmetry from the structures obtained from FF is maintained after QM optimization. There is only one exception for the cases studied. The structure obtained from the FF packing scheme with P (19) space group transition to P n m a (62) space group after QM minimization. In the FF scheme (packing + minimization) the structure with P (19) space group ranks as the 4th, however after minimization with periodic DFT:PBE-ulg the structure becomes the 3rd most stable structure besides transition to a more symmetrical space group, P n m a (62). As it was discussed in the main text the other structures maintain their symmetry through the QM minimization procedure, however their ranks changes, i.e. FF: C 2/c (15) changes from 1st to QM: 2nd; FF:C c (9) changes from 3rd to QM: 4th; and FF:P b c a (61) changes from 2nd to QM: 1st. [FF: C2 (5) does not change and remains in 5th also after QM.] 9.1: view 1 9.2: view 2 Figure S9: c2-dtto: space group C2 (5) 10.1: view : view 2 Figure S10: c2-dtto: space group C 2/c (15) S11

12 Di-tetrazine-tetroxide (DTTO), aka Tetrazino-tetrazine-tetraoxide (TTTO) 11.1: view : view 2 Figure S11: c2-dtto: space group C c (9) 12.1: view : view 2 Figure S12: c2-dtto: space group P n m a (62) 13.1: view : view 2 Figure S13: c2-dtto: space group P b c a (61) S12

13 3.3 Coordinates for structures of DTTO configuration 1 (c1) c1-dtto: space group C 2/c (15) _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume _symmetry_int_tables_number 15 _symmetry_space_group_name_h-m C 1 2/c 1 O O N N N N C c1-dtto: space group P 1 (2) _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume _symmetry_int_tables_number 2 _symmetry_space_group_name_h-m P -1 O O N N N N C c1-dtto: space group P 21/c (14) global minimum _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume _symmetry_int_tables_number 14 _symmetry_space_group_name_h-m P 1 21/c 1 O O N S13

14 N N N C c1-dtto: space group P 21/c (14) local minima _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume _symmetry_int_tables_number 14 _symmetry_space_group_name_h-m P 1 21/c 1 O O O O N N N N N N N N C C c1-dtto: space group P (19) _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _symmetry_space_group_name_h-m P _symmetry_int_tables_number 19 O O O O N N N N N N N N C S14

15 C Coordinates for structures of DTTO configuration 2 (c2) c1-dtto: space group C2 (5) _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume _symmetry_int_tables_number 5 _symmetry_space_group_name_h-m C N N N N N N N N C C O O O O c1-dtto: space group C 2/c (15) _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume _symmetry_int_tables_number 15 _symmetry_space_group_name_h-m C 1 2/c 1 N N N N N N N N C C O O O S15

16 O c1-dtto: space group C c (9) _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume _symmetry_int_tables_number 9 _symmetry_space_group_name_h-m C 1 c 1 N N N N N N N N C C O O O O c1-dtto: space group P n m a (62) _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume _symmetry_int_tables_number 62 _symmetry_space_group_name_h-m P n m a N N N N O O C C c1-dtto: space group P b c a (61) _cell_length_a _cell_length_b _cell_length_c _cell_angle_alpha 90 S16

17 _cell_angle_beta 90 _cell_angle_gamma 90 _symmetry_space_group_name_h-m P b c a _symmetry_int_tables_number 61 N N N N N N N N C C O O O O Simulation of the Powder X-ray of the most stable structures Based on the structures obtained from periodic DFT:PBE-ulg we have simulated the PXRD in order to facilitate its identification when their synthesis is attained. The parameters used for the simulation of the PXRD are X-ray (laboratory) with wavelength of Åand we assumed a conventional laboratory X-ray diffractometers thus both Lorentz and polarization correction were applied. We report the first peaks for every PXRD in order to quickly identified the crystal packing using crystalline powder, instead of waiting to growth a single crystal. If further refinement is needed, the coordinates for the structures reported above should be used. 4.1 PXRD plot for c1-dtto S17

18 Diffraction diagram: C2.cssr > Created by Cerius2 Page 1 of 1Diffraction diagram: P_1.cssr > Created by Cerius2 Page 1 of 1 Int. Int Theta 14.1: C 2/c (15) Diffraction diagram: P21.cssr > Created by Cerius Theta 14.2: P 1 (2) Page 1 of 1Diffraction diagram: P21c.cssr > Created by Cerius2 Page 1 of 1 Int. Int Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany. 0 Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany Theta 14.3: P 21/c (14) global minimum Diffraction diagram: P cssr > Created by Cerius Theta 14.4: P 21/c Page 1 (14) of 1 local minima Int Created with Diamond version 3.2i, Crystal 0 Impact GbR, Bonn, Germany. Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany Theta 14.5: P (19) Figure S14: PXRD for configuration 1 of DTTO with space group C 2/c (15), P 1 (2), P 21/c (14) and P (19) S18 Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany.

19 4.2 PXRD plot for c2-dtto Diffraction diagram: C2.cssr > Created by Cerius2 Page 1 of 1 Diffraction diagram: C2-C.cssr > Created by Cerius2 Page 1 of 1 Int. Int Theta 15.1: C2 (5) Diffraction diagram: CC.cssr > Created by Cerius Theta 15.2: C 2/c (15) Page 1 of 1Diffraction diagram: P212121_PNMA.cssr > Created by Cerius2 Page 1 of 1 Int. Int Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany. 0 Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany Theta 15.3: C c (9) Diffraction diagram: PBCA.cssr > Created by Cerius Theta 15.4: Page 1 Pof n1 m a (62) Int Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany. Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany Theta 15.5: P b c a (61) Figure S15: PXRD for configuration 2 of DTTO with space group C2 (5), C 2/c (15), C c (9), P n m a (62) and P b c a (61) S19 Created with Diamond version 3.2i, Crystal Impact GbR, Bonn, Germany.

20 4.3 First peaks PXRD data for c1-dtto Table S5: Table of reflexion parameters of the PXRD for c1-dtto with space group C 2/c (15) Table S6: Table of reflexion parameters of the PXRD for c1-dtto with space group P 1 (2) Continued on next page S20

21 Table S6 Continued from previous page Table S7: Table of reflexion parameters of the PXRD for c1-dtto with space group P 21/c (14) global minimum Table S8: Table of reflexion parameters of the PXRD for c1-dtto with space group P 21/c (14) local minima Continued on next page S21

22 Table S8 Continued from previous page S22

23 Table S9: Table of reflexion parameters of the PXRD for c1-dtto with space group P (19) First peaks PXRD data for c2-dtto Table S10: Table of reflexion parameters of the PXRD for c1-dtto with space group C2 (5) Continued on next page S23

24 Table S10 Continued from previous page Table S11: Table of reflexion parameters of the PXRD for c1-dtto with space group C 2/c (15) Continued on next page S24

25 Table S11 Continued from previous page Continued on next page S25

26 Table S11 Continued from previous page Table S12: Table of reflexion parameters of the PXRD for c1-dtto with space group C c (9) Continued on next page S26

27 Table S12 Continued from previous page Table S13: Table of reflexion parameters of the PXRD for c1-dtto with space group P n m a (62) S27

28 Table S14: Table of reflexion parameters of the PXRD for c1-dtto with space group P b c a (61) Continued on next page S28

29 Table S14 Continued from previous page S29

30 Bibliography [1] H. Stokes and D. M. Hatch, Findsym: Program for identifying the space group symmetry of a crystal, Journal of Applied Crystallography, vol. 38, pp , S30

Prediction of the Crystal Packing of Di-Tetrazine-Tetroxide (DTTO) Energetic Material

Prediction of the Crystal Packing of Di-Tetrazine-Tetroxide (DTTO) Energetic Material Jose L. Mendoza-Cortes, [a], Qi An, [a] William A. Goddard III,* [a] Caichao Ye, [a,b] and Sergey Zybin [a] Previous