Preparation and characterization of 3,5-dinitro-1H-1,2,4-triazole. Supplementary Information

Transcription

1 Electronic Supplementary Material (ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2015 Preparation and characterization of 3,5-dinitro-1H-1,2,4-triazole Supplementary Information R. Haiges, G. Bélanger-Chabot, S. M. Kaplan and K. O. Christe Loker Hydrocarbon Research Institute, University of Southern California, Los Angeles, CA , USA. Tel: Table of Contents Experimental Details...2 Materials and apparatus...2 X-ray Crystal Structure Determination...2 Synthesis of potassium 3,5-dinitro-1,2,4-triazolate (method Synthesis of potassium 3,5-dinitro-1,2,4-triazolate (method Synthesis of 3,5-dinitro-1H-1,2,4-triazole (HDNT...4 Synthesis of PPN + 3,5-dinitro-1,2,4-triazolate [PPN][DNT]...5 Crystallographic Information...6 Crystal Structure Report for the monoclinic modification HDNT Crystal Structure Report for the triclinic modification HDNT Crystal Structure Report for (HDNT 3 4 H 2 O...25 Crystal Structure Report for 5-ethoxy-1-methyl-3-nitro-1H-1,2,4-triazole Crystal Structure Report for 1-acetyl-3,5-diamino-1H-1,2,4-triazole Crystal Structure Report for 1-(i-propyl-3,5-dinitro-1H-1,2,4-triazole Crystal Structure Report for the co-crystal of 1-(i-propyl-3,5-dinitro-1H-1,2,4-triazole and 3-nitro- 1H-1,2,4-triazole Crystal Structure Report for sodium 3-nitro-1,2,4-triazol-5-olate monohydrate 5 H 2 O...70 Crystal Structure Report for the co-crystal of 5-azido-3-nitro-1,2,4-triazole and PPN + 5-azido-3-nitro- 1,2,4-triazolate Crystal Structure Report for 5-azido-3-nitro-1,2,4-triazolate containing PPN + 3,5-dinitro-1H-1,2,4- triazolate...91 References

2 Experimental Details Caution! The compounds of this work are energetic materials that might explode under certain conditions (e.g., elevated temperature, impact, friction or electric discharge. Appropriate safety precautions, such as the use of shields or barricades in a fume hood and personal protection equipment (safety glasses, face shields, ear plugs, as well as gloves and suits made from leather and/or Kevlar 1 should be taken at all the time when handling these materials. Pure HDNT decomposes explosively when heated above 160 C, and certain impurities might further lower the decomposition temperature. The sublimation of HDNT should be carried-out behind a blast shield and only on a small scale. Ignoring safety precautions may lead to serious injuries! Materials and apparatus All chemicals and solvents were obtained from Sigma-Aldrich or Alfa-Aesar and were used as supplied. NMR spectra were recorded at 298 K on Bruker AMX500 or Varian VNMRS-600s spectrometers using (CD 3 2 CO or D 2 O solutions in standard 5 mm o.d. glass tubes. Chemical shifts are given relative to neat tetramethylsilane ( 1 H, 13 C or neat CH 3 NO 2 ( 14 N, 15 N. Raman spectra were recorded at ambient temperatures in Pyrex glass tubes in the range of cm -1 on a Bruker Equinox 55 FT-RA spectrometer using a Nd-YAG laser at 1064 nm or a Cary 83 spectrometer using an Ar laser at 488 nm. Infrared spectra were recorded in the range cm -1 on a Midac, M Series spectrometer using KBr pellets or on a Bruker Optics Alpha FT-IR ATR spectrometer. KBr pellets were prepared very carefully using an Econo mini-press (Barnes Engineering Co.. Differential thermal analysis (DTA curves were recorded with a purge of dry nitrogen gas and a heating rate of 5 C/min on an OZM Research DTA552-Ex instrument with the Meavy software. The sample sizes were 3-15 mg. The impact and friction sensitivity data were determined with an OZM Research BAM Fall Hammer BFH-10 and an OZM Research BAM Friction apparatus FSKM-10, respectively, through five individual measurements that were averaged. Both instruments were calibrated using RDX. The samples were finely powdered materials that were not sifted. X-ray Crystal Structure Determination The single crystal X-ray diffraction data for HDNT-1, HDNT-2, 3, 3 4 (co-crystals, and 5 H 2 O were collected on a Bruker SMART diffractometer, equipped with an APEX CCD detector, using Mo K radiation (graphite monochromator from a fine-focus tube. The single crystal X- ray diffraction data for the remaining structures were collected on a Bruker SMART APEX DUO diffractometer, equipped with an APEX II CCD detector, using Mo K radiation (TRIUMPH curved-crystal monochromator from a fine-focus tube or Cu K from an I S micro-source. The frames were integrated using the SAINT algorithm to give the hkl files corrected for Lp/decay. 2 The absorption correction was performed using the SADABS program. 3 The structures were 2

3 solved and refined on F 2 using the Bruker SHELXTL Software Package. 4-7 Non-hydrogen atoms were refined anisotropically. Structure drawings were prepared using the ORTEP-III for Windows V2.02 and Mercury programs. 8, 9 Further crystallographic details can be obtained from the Cambridge Crystallographic Data Centre (CCDC, 12 Union Road, Cambridge CB21EZ, UK (Fax: ( ; deposit@ccdc.cam.ac.uk on quoting the deposition no. CCDC , and , and from the Fachinformationszentrum Karlsruhe, Eggenstein-Leopoldshafen, Germany (Fax: ( , crysdata@fiz-karlsruhe.de, on quoting the deposition numbers CSD Synthesis of potassium 3,5-dinitro-1,2,4-triazolate (method 1 In a 2000 ml three-necked round-bottom flask, equipped with a reflux condenser, an addition funnel and a mechanical stirrer, a mixture of sodium nitrite (220 g, 3.28 mol in water (350 ml was heated to 50 C using a water bath until all sodium nitrite had dissolved. A solution of 3,5- diamino-1,2,4-triazole (40.0 g, mol in water (500 ml and concentrated sulfuric acid (36 ml was added slowly and carefully through the addition funnel while the reaction mixture was stirred vigorously. Immediately, the reaction mixture turned red, foamed and formed some dark red precipitate. In addition, brown-orange fumes of nitric oxide were produced. After about one to two hours, the addition was completed and 80% sulfuric acid (220 ml was added carefully while the reaction mixture was stirred vigorously in order to avoid excessive foam formation. The reaction mixture was then refluxed for about 60 minutes and then allowed to cool to C. Activated decolorizing charcoal (10 g was added and the mixture stirred at ambient temperature for eight hours. The reaction mixture was then filtered over Celite 545 and the filtrate extracted six times with ethyl acetate (150 ml each. The combined organic phases were dried over magnesium sulphate and the solvent removed immediately using a rotary evaporator without (! heating of the sample. The obtained yellow to orange oil or paste was dissolved immediately in acetone (200 ml and the yellow solution poured onto potassium carbonate (60 g. Immediately, a gas was evolved and the mixture was stirred at ambient temperature. After about two hours, the mixture was filtered and the orange solid residue was washed extensively with acetone. The combined yellow filtrates were taken to dryness on a rotary evaporator leaving behind a yellow solid. Recrystallization from water resulted in the isolation of yellow crystals of KDNT 2H 2 O that were dried in vacuo at 50 C for eight hours, resulting in colourless to pale yellow KDNT (yield: 52.5 g, 65.9 %. DTA: 265 C decomposition; NMR (CD 3 CN δ(ppm: 13 C ( MHz (C-NO 2 ; 14 N (36.14 MHz (s, 1/2 = 65Hz, 2N, C-NO 2, -52 (s, 1/2 = 500 Hz, DNT -. Raman (200 mw ῦ/cm -1 : 1545 (0.3, 1500 (0.2, 1425 (0.2, 1403 (10.0, 1388 (0.4, 1359 (1.6, 1310 (0.3, 1107 (0.3, 1100 (6.1, 1067 (0.1, 1028 (0.3, 834 (0.8, 769 (0.4, 515 (0.2. IR (ATR ῦ/cm -1 : 3604 (m, 3414 (m, 3327 (w, 3233 (w, 2749 (w, 2694 (w, 2663 (w, 2459 (w, 2144 (w, 1672 (w, 1643 (m, 1552 (w, 1536 (s, 1493 (s, 1440 (w, 1415 (w, 1388 (s,

4 (s, 1341 (w, 1299 (s, 1109 (m, 1100 (w, 1067 (w, 1050 (m, 997 (w, 877 (w, 846 (s, 835 (w, 770 (w, 749 (w, 684 (w, 648 (s, 605 (w, 515 (m, 502 (w, 483 (w, 472 (w, 457 (w, 404 (w. IR (AgCl pellet ῦ/cm -1 : 2757 (w, 2754 (w, 2748 (w, 2691 (w, 2658 (w, 2457 (m, 2399 (w, 2186 (w, 2158 (w, 2139 (w, 1563 (w, 1556 (s, 1540 (w, 1504 (s, 1439 (w, 1414 (m, 1392 (s, 1359 (s, 1343 (w, 1320 (w, 1310 (m, 1301 (s, 1296 (m, 1107 (w, 1100 (s, 1066 (w, 1050 (m, 1044 (m, 1019 (w, 850 (s, 837 (s, 831 (m, 771 (m, 768 (w, 652 (s, 606 (m, 519 (w, 515 (w. Synthesis of potassium 3,5-dinitro-1,2,4-triazolate (method 2 In a 1000 ml three-necked round-bottom flask that was cooled by a water bath, concentrated nitric acid (80 ml was slowly added to hydrazine hydrate (20.0 g, 0.40 mol. Water (140 ml and 2-cynaoguanidine (dicyandiamide (33.6 g, 0.40 mol was added and the reaction mixture heated to 50 C for one hour. A solution of concentrated sulfuric acid (35 ml in water (300 ml was added, and the resulting DAT solution transferred into an addition funnel from which it was added carefully to a vigorously stirred solution of sodium nitrite (220 g, 3.28 mol in water (350 ml at 50 C. After about one to two hours, the addition was completed and 80% sulfuric acid (220 ml was added carefully while the reaction mixture was stirred vigorously in order to avoid excessive foam formation. The reaction mixture was then refluxed for about 60 minutes and then allowed to cool to C. Activated decolorizing charcoal (10 g was added and the mixture stirred at ambient temperature for eight hours. The reaction mixture was then filtered over Celite 545 and the filtrate extracted six times with ethyl acetate (150 ml each. The combined organic phases were dried over magnesium sulphate and the solvent removed immediately using a rotary evaporator without (! heating of the sample. The obtained yellow to orange oil or paste was dissolved immediately in acetone (200 ml and the yellow solution poured onto potassium carbonate (60 g. Immediately, a gas was evolved and the mixture was stirred at ambient temperature. After about two hours, the mixture was filtered and the orange solid residue was washed extensively with acetone. The combined yellow filtrates were taken to dryness on a rotary evaporator leaving behind in a yellow-orange solid. Recrystallization from water resulted in the isolation of yellow crystals that were dried in vacuo at 50 C for eight hours, resulting in yellow KDNT containing various impurities (yield: 54.3 g, 69% based on KDNT. IR (ATR ῦ/cm -1 : 2753 (vw, 2692 (vw, 2662 (vw, 2457 (vw, 2399 (vw, 2178 (vw, 2140 (m, 1553 (s, 1532 (s, 1494 (vs, 1413 (w, 1386 (vs, 1354 (vs, 1342 (s, 1296 (vs, 1099 (m, 1049 (m, 847 (vs, 835 (m, 787 (vw, 770 (w, 747 (vw, 730 (vw, 648 (s, 604 (m, 515 (w. Synthesis of 3,5-dinitro-1H-1,2,4-triazole (HDNT A solution of KDNT (5.937 g, mmol in water (20 ml was acidified with 20% sulfuric acid (50 ml and the resulting yellow solution extracted four times with ethyl acetate (50 ml each. The combined organic phases were washed with water (50 ml, dried over magnesium 4

5 sulphate and the solvent removed using a rotary evaporator. The resulting yellow oil was further dried in a high vacuum at C for eight hour, resulting in light-yellow, solid HDNT (yield: g, 93.0%. HDNT of high-purity was obtained as a white solid through careful sublimation of the crude compound at C in a vacuum of less than 0.1 mtorr. The temperature was carefully monitored in order to avoid a potentially explosive decomposition of the HDNT. DTA: 170 C (onset explosive decomposition; Friction sensitivity: 144 N; Impact sensitivity: 35 J; NMR (CD 3 CN δ(ppm: 1H ( MHz 13.6 ( 1/2 = 100 Hz; 13 C ( MHz (C- NO 2 ; 14 N (36.14 MHz (s, 1/2 = 20 Hz C-NO 2. Raman (50 mw ῦ/cm -1 : 2863 (0.2, 1581 (0.8, 1574 (1.0, 1528 (0.4, 1499 (0.7, 1487 (0.9, 1451 (2.6, 1436 (10.0, 1382 (3.4, 1366 (1.1, 1317 (0.8, 1280 (0.6, 1181 (1.2, 1163 (0.6, 1048 (1.0, 1043 (1.1, 1027 (0.3, 1012 (0.7, 1007 (0.8, 829 (0.9, 826 (1.3, 774 (0.4, 762 (0.8, 510 (0.6, 357 (1.1, 290 (1.0, 182 (0.7, 171 (0.7, 111 (2.5, 95 (2.4. IR (ATR, 20 C ῦ/cm -1 : 3039 (vw, 2992 (vw, 2934 (vw, 2883 (vw, 2839 (vw, 2802 (vw, 2748 (vw, 2639 (vw, 2557 (vw, 2162 (vw, 1698 (vw, 1563 (vs, 1530 (s sh, 1485 (s, 1430 (w, 1377 (s sh, 1363 (s sh, 1313 (vs, 1281 (m sh, 1174 (m, 1038 (m, 1023 (m sh, 1008 (m sh, 839 (vs, 825 (vs, 764 (vw, 730 (vw, 649 (m, 634 (m sh, 593 (m, 509 (m, 500 (m sh. Synthesis of PPN + 3,5-dinitro-1,2,4-triazolate [PPN][DNT] [PPN][DNT] was prepared as described previously 10 by adding an aqueous solution of HDNT to an aqueous solution of [PPN][Cl]. The resulting [PPN][DNT] precipitate was filtered, washed with water and recrystallized from acetone. In one occation, reddish crystals were obtained from the aqueous filtrate. These crystals were identified by X-ray diffraction as [PPN][H(AzNT 2 ] (AzNT = azidonitrotriazolate. The vibrational spectra of the isolated [PPN][DNT] exhibited vibrational bands due to azido compounds. An X-ray structural analysis of some of the crystals showed an substitutional disorder in which the about 25% of the DNT - anions were relaced by AzNT - anions. Contaminated [PPN][DNT]: IR (ATR, 20 C ῦ/cm -1 : 3055 (w, 2122 (m, 1587 (w, 1531 (s, 1509 (w, 1480 (s, 1436 (s, 1423 (w, 1397 (w, 1373 (s, 1339 (m, 1325 (m, 1296 (w, 1281 (m, 1239 (vs, 1181 (w, 1162 (w, 1111 (s, 1073 (m, 1038 (w, 1024 (w, 997 (m, 932 (w, 858 (w, 838 (s, 828 (w, 803 (m, 760 (vw, 746 (s, 722 (vs, 690 (vs, 666 (vw, 616 (w, 597 (w, 553 (vs, 531 (w, 526 (vs, 498 (vs, 487 (w, 462 (w, 450 (w, 437 (w, 419 (vw. [PPN][H(AzNT 2 ]: IR (ATR, 20 C ῦ/cm -1 : 3063 (w, 2130 (s, 2017 (w, 1991 (vw, 1976 (w, 1896 (w, 1831 (vw, 1587 (w, 1573 (vw, 1556 (w, 1526 (m, 1479 (m, 1436 (m, 1383 (m, 1341 (w, 1294 (s, 1221 (w, 1183 (w, 1161 (w, 1113 (vs, 1024 (w, 1014 (w, 996 (m, 931 (vw, 839 (m, 793 (vw, 756 (vw, 749 (m, 721 (s, 690 (vs, 655 (w, 617 (vw, 549 (w, 528 (vs, 496 (s, 444 (m, 414 (vw. 5

6 Crystallographic Information Crystal Structure Report for the monoclinic modification HDNT-1 Figure S1: Asymmetric unit in the monoclinic modification HDNT-1. Figure S3: Projection of the packing in the monoclinic modification HDNT-1 perpendicular to the 001 plane. 6

7 Figure S3: Projection of the packing in the monoclinic modification HDNT-1 perpendicular to the 010 plane. Figure S3: Projection of the packing in the monoclinic modification HDNT-1 perpendicular to the 100 plane. 7

8 Table S1: Sample and crystal data for the monoclinic modification HDNT-1. Identification code HDNT-1 Chemical formula C 2 HN 5 O 4 Formula weight Temperature Wavelength Crystal size Crystal habit Crystal system g/mol 140(2 K Å x x mm clear colourless prism monoclinic Space group P 1 21/c 1 Unit cell dimensions a = (14 Å α = 90 b = 9.083(2 Å β = (3 c = 9.858(2 Å γ = 90 Volume 550.2(2 Å 3 Z 4 Density (calculated g/cm 3 Absorption coefficient mm -1 F(

9 Table S2: Data collection and structure refinement for the monoclinic modification HDNT-1. Diffractometer Radiation source Bruker SMART APEX fine-focus tube, MoKα Theta range for data collection 3.05 to Index ranges -8<=h<=8, -12<=k<=12, -13<=l<=13 Reflections collected Independent reflections 1470 [R(int = ] Absorption correction multi-scan Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXTL XT 2014/4 (Bruker AXS, 2014 Refinement method Full-matrix least-squares on F 2 Refinement program SHELXTL XL 2014/7 (Bruker AXS, 2014 Function minimized Σ w(f 2 o - F c2 2 Data / restraints / parameters 1470 / 0 / 103 Goodness-of-fit on F Final R indices 1305 data; I>2σ(I R1 = , wr2 = all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 +(0.0459P P] where P=(F o2 +2F c2 /3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 9

10 Table S3: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for the monoclinic modification HDNT-1. U(eq is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq C ( ( ( (2 C ( ( ( (2 N ( ( ( (2 N ( ( ( (2 N ( ( ( (2 N ( ( ( (2 N ( ( ( (2 O ( ( ( (2 O ( ( ( (2 O ( ( ( (2 O ( ( ( (2 Table S1: Bond lengths (Å for the monoclinic modification HDNT-1. C1-N (14 C1-N (13 C1-N (14 C2-N (13 C2-N (13 C2-N (14 N1-N (13 N1-H (14 N4-O (13 N4-O (13 N5-O (13 N5-O (12 10

11 Table S1: Bond angles ( for the monoclinic modification HDNT-1. N2-C1-N (9 N2-C1-N (9 N3-C1-N (9 N3-C2-N (9 N3-C2-N (9 N1-C2-N (9 C2-N1-N (9 C2-N1-H (9 N2-N1-H (9 C1-N2-N (8 C2-N3-C (8 O1-N4-O (10 O1-N4-C (9 O2-N4-C (9 O4-N5-O (10 O4-N5-C (9 O3-N5-C (9 Table S1: Torsion angles ( for the monoclinic modification HDNT-1. N3-C2-N1-N2 0.31(12 N5-C2-N1-N (9 N3-C1-N2-N1-0.02(12 N4-C1-N2-N (9 C2-N1-N2-C1-0.16(11 N1-C2-N3-C1-0.28(11 N5-C2-N3-C (10 N2-C1-N3-C2 0.18(12 N4-C1-N3-C (9 N2-C1-N4-O (10 N3-C1-N4-O1-6.04(14 N2-C1-N4-O2-6.84(15 N3-C1-N4-O (9 N3-C2-N5-O (10 N1-C2-N5-O4-1.03(15 N3-C2-N5-O3 0.60(15 N1-C2-N5-O (9 11

12 Table S7: Anisotropic atomic displacement parameters (Å 2 for the monoclinic modification HDNT-1. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C ( ( ( ( ( (3 C ( ( ( ( ( (4 N ( ( ( ( ( (3 N ( ( ( ( ( (3 N ( ( ( ( ( (3 N ( ( ( ( ( (3 N ( ( ( ( ( (3 O ( ( ( ( ( (3 O ( ( ( ( ( (3 O ( ( ( ( ( (3 O ( ( ( ( ( (4 Table S8: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 for the monoclinic modification HDNT-1. x/a y/b z/c U(eq H ( ( (

13 Crystal Structure Report for the triclinic modification HDNT-2 Figure S3: Asymmetric unit in the triclinic modification HDNT-2. Figure S3: Projection of the packing in triclinic modification HDNT-2 perpendicular to the 001 plane. 13

14 Figure S3: Projection of the packing in triclinic modification HDNT-2 perpendicular to the 010 plane. 14

15 Figure S3: Projection of the packing in the triclinic modification HDNT-2 perpendicular to the 100 plane. 15

16 Table S1: Sample and crystal data for the triclinic modification HDNT-2. Identification code HDNT (2 Chemical formula C 2 HN 5 O 4 Formula weight Temperature Wavelength Crystal size Crystal habit Crystal system g/mol 140(2 K Å x x mm yellow prism triclinic Space group P -1 Unit cell dimensions a = (15 Å α = (2 b = (16 Å β = (3 c = (2 Å γ = (2 Volume 856.7(3 Å 3 Z 6 Density (calculated g/cm 3 Absorption coefficient mm -1 F(

17 Table S1: Data collection and structure refinement for the triclinic modification HDNT-2. Diffractometer Radiation source Bruker SMART APEX fine-focus tube, MoKα Theta range for data collection 1.86 to Index ranges -11<=h<=11, -11<=k<=11, -8<=l<=15 Reflections collected 5462 Independent reflections 3826 [R(int = ] Absorption correction multi-scan Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXTL XT 2014/4 (Bruker AXS, 2014 Refinement method Full-matrix least-squares on F 2 Refinement program SHELXTL XL 2014/7 (Bruker AXS, 2014 Function minimized Σ w(f 2 o - F c2 2 Data / restraints / parameters 3826 / 0 / 302 Goodness-of-fit on F Final R indices 2831 data; I>2σ(I R1 = , wr2 = all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 +(0.0601P P] where P=(F o2 +2F c2 /3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 17

18 Table S1: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for the triclinic modification HDNT-2. U(eq is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq C ( ( ( (5 C ( ( ( (5 C ( ( ( (5 C ( ( ( (5 C ( ( ( (5 C ( ( ( (5 N ( ( ( (4 N ( ( ( (4 N ( ( ( (4 N ( ( ( (5 N ( ( ( (5 N ( ( ( (5 N ( ( ( (5 N ( ( ( (4 N ( ( ( (5 N ( ( ( (5 N ( ( ( (4 N ( ( ( (4 N ( ( ( (4 N ( ( ( (5 N ( ( ( (5 O ( ( ( (5 18

19 x/a y/b z/c U(eq O ( ( ( (5 O ( ( ( (5 O ( ( ( (5 O ( ( ( (4 O ( ( ( (6 O ( ( ( (5 O ( ( ( (5 O ( ( ( (5 O ( ( ( (5 O ( ( ( (5 O ( ( ( (5 19

20 Table S1: Bond lengths (Å for the triclinic modification HDNT-2. C1-N (3 C1-N (3 C1-N (3 C2-N (3 C2-N (3 C2-N (3 C3-N (3 C3-N (3 C3-N (3 C4-N (3 C4-N (3 C4-N (3 C5-N (3 C5-N (3 C5-N (3 C6-N (3 C6-N (3 C6-N (3 N1-N (3 N1-H N2-H1A N4-O (3 N4-O (3 N5-O (3 N5-O (3 N6-N (3 N6-H2 0.91(3 N9-O (3 N9-O (3 N10-O (3 N10-O (3 N11-N (3 N11-H N12-H3A N14-O (3 N14-O (3 N15-O (3 N15-O (3 20

21 Table S1: Bond angles ( for the triclinic modification HDNT-2. N3-C1-N (2 N3-C1-N (2 N2-C1-N (2 N3-C2-N (2 N3-C2-N (2 N1-C2-N (2 N7-C3-N (2 N7-C3-N (2 N8-C3-N (2 N8-C4-N (2 N8-C4-N (2 N6-C4-N (2 N12-C5-N (2 N12-C5-N (2 N13-C5-N (2 N11-C6-N (2 N11-C6-N (2 N13-C6-N (2 C2-N1-N (19 C2-N1-H N2-N1-H C1-N2-N (18 C1-N2-H1A N1-N2-H1A C1-N3-C (19 O3-N4-O (2 O3-N4-C (2 O4-N4-C (2 O2-N5-O (2 O2-N5-C (2 O1-N5-C (2 C4-N6-N (2 C4-N6-H2 130.(2 N7-N6-H2 121.(2 C3-N7-N (19 C4-N8-C (19 O5-N9-O (2 O5-N9-C (2 O6-N9-C (2 O7-N10-O (2 O7-N10-C (2 O8-N10-C (2 C6-N11-N (19 C6-N11-H N12-N11-H C5-N12-N (18 C5-N12-H3A N11-N12-H3A C6-N13-C (19 O9-N14-O (2 21

22 O9-N14-C (2 O10-N14-C (2 O12-N15-O (2 O12-N15-C (2 O11-N15-C (2 Table S1: Anisotropic atomic displacement parameters (Å 2 for the triclinic modification HDNT-2. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C ( ( ( ( ( (9 C ( ( ( ( ( (9 C ( ( ( ( ( (9 C ( ( ( ( ( (9 C ( ( ( ( ( (9 C ( ( ( ( ( (9 N ( ( ( ( ( (8 N ( ( ( ( ( (8 N ( ( ( ( ( (8 N ( ( ( ( ( (9 N ( ( ( ( ( (9 N ( ( ( ( ( (9 N ( ( ( ( ( (9 N ( ( ( ( ( (8 N ( ( ( ( ( (9 N ( ( ( ( ( (9 N ( ( ( ( ( (8 N ( ( ( ( ( (8 22

23 U 11 U 22 U 33 U 23 U 13 U 12 N ( ( ( ( ( (8 N ( ( ( ( ( (9 N ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (8 O ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (10 O ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (9 23

24 Table S1: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 for the triclinic modification HDNT-2. x/a y/b z/c U(eq H H1A H ( ( ( (9 H H3A

25 Crystal Structure Report for (HDNT 3 4 H 2 O Figure S3: Asymmetric unit in the crystal structure of (HDNT 3 4H 2 O. 25

26 Figure S3: Projection of the packing in (HDNT 3 4H 2 O perpendicular to the 001 plane. 26

27 Figure S3: Projection of the packing in (HDNT 3 4H 2 O perpendicular to the 010 plane. Figure S3: Projection of the packing in (HDNT 3 4H 2 O perpendicular to the 100 plane. 27

28 Table S1: Sample and crystal data for (HDNT 3 4H 2 O. Identification code HDNT_H2O Chemical formula C 6 H 11 N 15 O 16 Formula weight Temperature Wavelength Crystal size Crystal habit Crystal system g/mol 100(2 K Å x x mm yellow plate triclinic Space group P 1 Unit cell dimensions a = (2 Å α = (2 b = (3 Å β = (2 c = (3 Å γ = (3 Volume (3 Å 3 Z 1 Density (calculated g/cm 3 Absorption coefficient mm -1 F(

29 Table S1: Data collection and structure refinement for (HDNT 3 4H 2 O. Diffractometer Radiation source Bruker APEX DUO fine-focus tube, MoKα Theta range for data collection 2.29 to Index ranges -6<=h<=6, -10<=k<=10, -10<=l<=10 Reflections collected 5789 Independent reflections 2617 [R(int = ] Coverage of independent reflections 95.4% Absorption correction multi-scan Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXTL XT 2014/4 (Bruker AXS, 2014 Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014/6 (Sheldrick, 2014 Function minimized Σ w(f 2 o - F c2 2 Data / restraints / parameters 2617 / 3 / 343 Goodness-of-fit on F Δ/σ max Final R indices 2468 data; I>2σ(I R1 = , wr2 = all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 +(0.0347P 2 ] where P=(F o2 +2F c2 /3 Absolute structure parameter -0.2(8 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 Table S1: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for (HDNT 3 4H 2 O. 29

30 U(eq is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq C ( ( ( (9 C ( ( ( (9 C ( ( ( (9 C ( ( ( (9 C ( ( ( (9 C ( ( ( (9 N ( ( ( (8 N ( ( ( (7 N ( ( ( (7 N ( ( ( (8 N ( ( ( (8 N ( ( ( (8 N ( ( ( (8 N ( ( ( (7 N ( ( ( (8 N ( ( ( (8 N ( ( ( (8 N ( ( ( (8 N ( ( ( (8 N ( ( ( (8 N ( ( ( (9 O ( ( ( (7 O ( ( ( (7 O ( ( ( (7 30

31 x/a y/b z/c U(eq O ( ( ( (7 O ( ( ( (7 O ( ( ( (7 O ( ( ( (7 O ( ( ( (7 O ( ( ( (7 O ( ( ( (7 O ( ( ( (9 O ( ( ( (9 O ( ( ( (6 O ( ( ( (7 O ( ( ( (7 O ( ( ( (7 31

32 Table S1: Bond lengths (Å for (HDNT 3 4H 2 O. C1-N (5 C1-N (5 C1-N (5 C2-N (5 C2-N (5 C2-N (5 C3-N (5 C3-N (5 C3-N (5 C4-N (5 C4-N (5 C4-N (5 C5-N (5 C5-N (5 C5-N (5 C5-C (5 C6-N (5 C6-N (5 C6-N (5 N1-N (4 N2-H1 0.90(4 N4-O (4 N4-O (4 N5-O (4 N5-O (4 N6-N (4 N7-H2 0.84(4 N9-O (4 N9-O (4 N10-O (4 N10-O (4 N11-N (4 N12-H3 0.90(4 N14-O (4 N14-O (4 N15-O (4 N15-O (5 O13-H1W O13-H2W O14-H3W O14-H4W O15-H5W O15-H6W O16-H7W O16-H8W

33 Table S1: Bond angles ( for (HDNT 3 4H 2 O. N3-C1-N (3 N3-C1-N (3 N2-C1-N (3 N1-C2-N (3 N1-C2-N (3 N3-C2-N (3 N8-C3-N (3 N8-C3-N (3 N7-C3-N (3 N6-C4-N (3 N6-C4-N (3 N8-C4-N (3 N13-C5-N (3 N13-C5-N (3 N12-C5-N (3 N13-C5-C6 40.7(2 N12-C5-C6 72.1(2 N14-C5-C (3 N11-C6-N (3 N11-C6-N (4 N13-C6-N (4 N11-C6-C5 77.9(2 N13-C6-C5 39.6(2 N15-C6-C (3 C2-N1-N (3 C1-N2-N (3 C1-N2-H1 130.(2 N1-N2-H1 122.(2 C1-N3-C2 99.3(3 O1-N4-O (3 O1-N4-C (3 O2-N4-C (3 O4-N5-O (3 O4-N5-C (3 O3-N5-C (3 C4-N6-N (3 C3-N7-N (3 C3-N7-H2 132.(3 N6-N7-H2 119.(3 C3-N8-C4 99.0(3 O5-N9-O (3 O5-N9-C (3 O6-N9-C (3 O8-N10-O (3 O8-N10-C (3 O7-N10-C (3 C6-N11-N (3 C5-N12-N (3 C5-N12-H3 131.(3 N11-N12-H3 120.(3 33

34 C5-N13-C6 99.6(3 O9-N14-O (3 O9-N14-C (3 O10-N14-C (3 O11-N15-O (4 O11-N15-C (4 O12-N15-C (4 H1W-O13-H2W H3W-O14-H4W H5W-O15-H6W H7W-O16-H8W Table S1: Anisotropic atomic displacement parameters (Å 2 for (HDNT 3 4H 2 O. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C ( ( ( ( ( (17 C ( ( ( ( ( (17 C ( ( ( ( ( (18 C ( ( ( ( ( (18 C ( ( ( ( ( (18 C ( ( ( ( ( (2 N ( ( ( ( ( (15 N ( ( ( ( ( (14 N ( ( ( ( ( (15 N ( ( ( ( ( (15 N ( ( ( ( ( (16 N ( ( ( ( ( (15 N ( ( ( ( ( (16 N ( ( ( ( ( (15 N ( ( ( ( ( (17 N ( ( ( ( ( (16 34

35 U 11 U 22 U 33 U 23 U 13 U 12 N ( ( ( ( ( (16 N ( ( ( ( ( (16 N ( ( ( ( ( (15 N ( ( ( ( ( (17 N ( ( ( ( ( (2 O ( ( ( ( ( (13 O ( ( ( ( ( (13 O ( ( ( ( ( (13 O ( ( ( ( ( (13 O ( ( ( ( ( (13 O ( ( ( ( ( (13 O ( ( ( ( ( (14 O ( ( ( ( ( (13 O ( ( ( ( ( (15 O ( ( ( ( ( (15 O ( ( ( ( ( (17 O ( ( ( ( ( (17 O ( ( ( ( ( (11 O ( ( ( ( ( (12 O ( ( ( ( ( (12 O ( ( ( ( ( (12 Table S1: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 for (HDNT 3 4H 2 O. x/a y/b z/c U(eq 35

36 x/a y/b z/c U(eq H ( ( ( H ( ( ( H ( ( ( H1W H2W H3W H4W H5W H6W H7W H8W

37 Crystal Structure Report for 5-ethoxy-1-methyl-3-nitro-1H-1,2,4-triazole 1 Figure S3: Asymmetric unit in the crystal structure of 5-ethoxy-1-methyl-3-nitro-1H-1,2,4- triazole 1. Figure S1: Projection of the packing in 1 perpendicular to the 001 plane. 37

38 Figure S1: Projection of the packing in 1 perpendicular to the 010 plane. Figure S16: Projection of the packing in 1 perpendicular to the 100 plane. 38

39 Table S23: Data collection and structure refinement for 1. Identification code cu_usc01_0m Empirical formula C 5 H 8 N 4 O 3 Formula weight Temperature/K Crystal system triclinic Space group P-1 a/å (8 b/å (8 c/å (9 α/ (5 β/ (5 γ/ (6 Volume/Å (7 Z 2 ρ calc g/cm μ/mm F( Crystal size/mm Radiation CuKα (λ = Θ range for data collection/ to Index ranges -7 h 7, -9 k 9, -10 l 10 Reflections collected 8069 Independent reflections 1315 [R int = , R sigma = ] Data/restraints/parameters 1315/0/141 Goodness-of-fit on F Final R indexes [I>=2σ (I] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /

40 Table S1: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for 1. U eq is defined as 1/3 of of the trace of the orthogonalised U IJ tensor. Atom x y z U(eq N ( ( ( (3 N ( ( ( (3 N ( ( ( (3 N ( ( ( (3 O ( ( ( (2 O ( ( ( (3 O ( ( ( (3 C1 2746( ( ( (3 C2 2487( ( ( (3 C3 1138( ( ( (3 C4 859(3 9344( ( (3 C5 4190(3 2228( ( (3 40

41 Table S25: Anisotropic Displacement Parameters (Å for 1. The Anisotropic displacement factor exponent takes the form: -2π 2 [h 2 a* 2 U 11 +2hka*b*U 12 + ]. Atom U 11 U 22 U 33 U 23 U 13 U 12 N1 21.9(5 22.9(5 28.8(6-0.6(4-7.3(4-8.2(4 N2 23.2(5 20.6(5 28.2(6-0.1(4-8.3(4-7.7(4 N3 22.7(5 23.1(5 29.4(6 2.2(4-8.3(4-9.1(4 N4 26.3(5 26.9(6 28.9(6 1.1(4-6.3(4-11.1(4 O1 31.4(5 19.7(5 29.6(5 0.4(4-11.5(4-6.4(4 O2 46.3(6 32.6(5 30.3(5-4.1(4-7.6(4-16.6(4 O3 41.4(6 29.2(5 32.4(5 6.8(4-12.6(4-12.6(4 C1 20.0(6 23.4(6 27.7(7 0.4(5-6.6(5-8.8(5 C2 19.9(6 21.2(6 29.8(7 1.7(5-8.5(5-7.8(5 C3 26.3(6 19.0(6 35.1(7-0.7(5-10.8(6-6.6(5 C4 36.7(8 24.8(7 40.8(8 3.5(6-16.7(7-8.3(6 C5 34.8(7 23.7(7 31.2(7-2.8(5-7.7(6-9.4(6 Table S25: Bond Lengths for 1. Atom Atom Length/Å Atom Atom Length/Å N1 C (16 N4 O (15 N1 C (16 N4 O (15 N2 N (15 N4 C (17 N2 C (16 O1 C (16 N2 C (17 O1 C (15 N3 C (16 C3 C (19 41

42 Table S27: Bond Angles for 1. Atom Atom Atom Angle/ Atom Atom Atom Angle/ C2 N1 C (10 C2 O1 C (10 N3 N2 C (10 N1 C1 N (11 C2 N2 N (10 N3 C1 N (12 C2 N2 C (11 N3 C1 N (11 C1 N3 N (10 N1 C2 N (11 O2 N4 O (12 O1 C2 N (11 O2 N4 C (11 O1 C2 N (11 O3 N4 C (11 O1 C3 C (11 Table S27: Hydrogen Atom Coordinates (Å 10 4 and Isotropic Displacement Parameters (Å for 1. Atom x y z U(eq H3A 2160( ( (18 26(4 H3B -330( ( (18 25(4 H4A 2320( (20 970(20 43(5 H4B 130( ( (20 38(4 H4C -130( ( (20 44(5 H5A 5370( ( (30 64(6 H5B 2900( ( (30 61(6 H5C 4830(30 920( (20 45(5 42

43 Crystal Structure Report for 1-acetyl-3,5-diamino-1H-1,2,4-triazole 2 Figure S16: Projection of the packing in 2 perpendicular to the 001 plane. 43

44 Figure S16: Projection of the packing in 2 perpendicular to the 010 plane. 44

45 Figure S16: Projection of the packing in 2 perpendicular to the 100 plane. 45

46 Table S29: Sample and crystal data for 2. Identification code AcDNT Chemical formula C 4 H 7 N 5 O Formula weight Temperature 100(2 K Wavelength Å Crystal system triclinic Space group P -1 Unit cell dimensions a = (10 Å α = (10 b = (10 Å β = (10 c = (10 Å γ = (10 Volume (8 Å 3 Z 2 Density (calculated g/cm 3 Absorption coefficient mm -1 F(

47 Table S30: Data collection and structure refinement for 2. Diffractometer Bruker APEX DUO Radiation source fine-focus tube, MoKα Theta range for data collection 2.61 to Index ranges -8<=h<=8, -12<=k<=12, -14<=l<=14 Reflections collected Independent reflections 2865 [R(int = ] Absorption correction multi-scan Structure solution technique direct methods Structure solution program SHELXTL XS 2013/1 (Sheldrick, 2013 Refinement method Full-matrix least-squares on F 2 Refinement program SHELXTL XLMP 2014/1 (Bruker AXS, 2013 Function minimized Σ w(f 2 o - F c2 2 Data / restraints / parameters 2865 / 0 / 109 Goodness-of-fit on F Final R indices R1 = , wr2 = 2727 data; I>2σ(I all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 +(0.0463P P] where P=(F o2 +2F c2 /3 Extinction coefficient (110 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 47

48 Table S24: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for 2. U(eq is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq C ( ( ( (8 C ( ( ( (8 C ( ( ( (8 C ( ( ( (9 N ( ( ( (7 N ( ( ( (8 N ( ( ( (8 N ( ( ( (8 N ( ( ( (8 O ( ( ( (9 Table S25: Bond lengths (Å for 2. C1-N (6 C1-N (6 C1-N (6 C2-N (6 C2-N (6 C2-N (6 C3-O (6 C3-N (6 C3-C (7 C4-H4A 0.98 C4-H4B 0.98 C4-H4C 0.98 N1-N (6 N4-H (12 N4-H (12 N5-H (12 N5-H (11 48

49 Table S26: Bond angles ( for 2. N2-C1-N (4 N2-C1-N (4 N4-C1-N (4 N3-C2-N (4 N3-C2-N (4 N5-C2-N (4 O1-C3-N (4 O1-C3-C (4 N1-C3-C (4 C3-C4-H4A C3-C4-H4B H4A-C4-H4B C3-C4-H4C H4A-C4-H4C H4B-C4-H4C C2-N1-C (4 C2-N1-N (4 C3-N1-N (4 C1-N2-N (4 C2-N3-C (4 C1-N4-H (8 C1-N4-H (7 H1-N4-H (11 C2-N5-H (8 C2-N5-H (7 H3-N5-H (10 Table S27: Anisotropic atomic displacement parameters (Å 2 for 2. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C ( ( ( ( ( (12 C ( ( ( ( ( (12 C ( ( ( ( ( (13 C ( ( ( ( ( (14 N ( ( ( ( ( (11 N ( ( ( ( ( (11 N ( ( ( ( ( (11 N ( ( ( ( ( (12 N ( ( ( ( ( (12 O ( ( ( ( ( (13 49

50 Table S28: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 for 2. x/a y/b z/c U(eq H4A H4B H4C H ( ( ( (3 H ( ( ( (2 H ( ( ( (3 H ( ( ( (2 50

51 Crystal Structure Report for 1-(i-propyl-3,5-dinitro-1H-1,2,4-triazole 3 Figure S20: Asymmetric unit in the crystal structure of 3. Figure S21: Projection of the packing in 3 perpendicular to the 001 plane. 51

52 Figure S22: Projection of the packing in 3 perpendicular to the 010 plane. Figure S23: Projection of the packing in 3 perpendicular to the 100 plane. 52

53 Table S36: Sample and crystal data for 3. Identification code HDNTimpurity Chemical formula C 5 H 7 N 5 O 4 Formula weight Temperature 130(2 K Wavelength Å Crystal size x x mm Crystal habit clear pale yellow prism Crystal system orthorhombic Space group P b c a Unit cell dimensions a = (19 Å α = 90 b = (2 Å β = 90 c = (4 Å γ = 90 Volume (6 Å 3 Z 8 Density (calculated g/cm 3 Absorption coefficient mm -1 F(

54 Table S30: Data collection and structure refinement for 3. Diffractometer Bruker SMART APEX Radiation source fine-focus tube, MoKα Theta range for data collection 2.36 to Index ranges -12<=h<=12, -14<=k<=14, -23<=l<=22 Reflections collected Independent reflections 2124 [R(int = ] Coverage of independent reflections 95.9% Absorption correction multi-scan Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXTL XT 2013/6 (Sheldrick, 2013 Refinement method Full-matrix least-squares on F 2 Refinement program SHELXTL XLMP 2014/1 (Bruker AXS, 2013 Function minimized Σ w(f 2 o - F c2 2 Data / restraints / parameters 2124 / 0 / 129 Goodness-of-fit on F Final R indices R1 = , wr2 = 1538 data; I>2σ(I all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 +(0.0450P P] where P=(F o2 +2F c2 /3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 54

55 Table S31: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for 3. U(eq is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq C ( ( ( (3 C ( ( ( (3 C ( ( ( ( ( ( (5 C ( ( (5 C ( (2 N ( ( ( (3 N ( ( ( (3 N ( ( ( (3 N ( ( ( (3 N ( ( ( (3 O ( ( ( (4 O ( ( ( (4 O ( ( ( (4 O ( ( ( (3 Table S32: Bond lengths (Å for 3. C1-N (2 C1-N (2 C1-N (2 C2-N (2 C2-N (2 C2-N (2 C3-N (2 C3-C (3 C3-C (2 C3-H3 1.0 C4-H4A 0.98 C4-H4B 0.98 C4-H4C 0.98 C5-H5A 0.98 C5-H5B 0.98 C5-H5C 0.98 N1-N (18 N4-O (19 55

56 N4-O (18 N5-O (19 N5-O (18 56

57 Table S40: Bond angles ( for 3. N2-C1-N (14 N2-C1-N (14 N3-C1-N (14 N3-C2-N (14 N3-C2-N (14 N1-C2-N (14 N1-C3-C (14 N1-C3-C (14 C4-C3-C (15 N1-C3-H C4-C3-H C5-C3-H C3-C4-H4A C3-C4-H4B H4A-C4-H4B C3-C4-H4C H4A-C4-H4C H4B-C4-H4C C3-C5-H5A C3-C5-H5B H5A-C5-H5B C3-C5-H5C H5A-C5-H5C H5B-C5-H5C C2-N1-N (12 C2-N1-C (13 N2-N1-C (13 C1-N2-N (13 C2-N3-C (13 O2-N4-O (14 O2-N4-C (14 O1-N4-C (14 O3-N5-O (15 O3-N5-C (14 O4-N5-C (14 57

58 Table S34: Anisotropic atomic displacement parameters (Å 2 for 3. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C ( ( ( ( ( (6 C ( ( ( ( ( (6 C ( ( ( ( ( (7 C ( ( ( ( ( (9 C ( ( ( ( ( (9 N ( ( ( ( ( (5 N ( ( ( ( ( (6 N ( ( ( ( ( (5 N ( ( ( ( ( (6 N ( ( ( ( ( (6 O ( ( ( ( ( (6 O ( ( ( ( ( (7 O ( ( ( ( ( (8 O ( ( ( ( ( (5 58

59 TableS35: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 for 3. x/a y/b z/c U(eq H H4A H4B H4C H5A H5B H5C

60 Crystal Structure Report for the co-crystal of 1-(i-propyl-3,5-dinitro-1H-1,2,4-triazole and 3-nitro-1H-1,2,4-triazole 3 4. Figure S24: Asymmetric unit in the crystal structure of

61 Figure S20: Projection of the packing in 3 4 perpendicular to the 100 plane. 61

62 Figure S21: Projection of the packing in 3 4 perpendicular to the 010 plane. 62

63 Figure S27: Projection of the packing in 3 4 perpendicular to the 001 plane. Table S36: Sample and crystal data for 3 4. Identification code HDNTimpurity2 Chemical formula C 7 H 9 N 9 O 6 Formula weight Temperature 130(2 K Wavelength Å Crystal size x x mm Crystal habit clear pale yellow prism Crystal system orthorhombic Space group P b c a Unit cell dimensions a = 9.472(2 Å α = 90 b = (2 Å β = 90 c = (5 Å γ = 90 Volume (9 Å 3 Z 8 63

64 Density (calculated g/cm 3 Absorption coefficient mm -1 F(

65 Table S37: Data collection and structure refinement for 3 4. Diffractometer Bruker SMART APEX Radiation source fine-focus tube, MoKα Theta range for data collection 1.71 to Index ranges -12<=h<=12, -14<=k<=14, -30<=l<=14 Reflections collected Independent reflections 2921 [R(int = ] Coverage of independent reflections 94.9% Absorption correction multi-scan Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXTL XT 2013/6 (Sheldrick, 2013 Refinement method Full-matrix least-squares on F 2 Refinement program SHELXTL XLMP 2014/1 (Bruker AXS, 2013 Function minimized Σ w(f 2 o - F c2 2 Data / restraints / parameters 2921 / 0 / 201 Goodness-of-fit on F Final R indices R1 = , wr2 = 2252 data; I>2σ(I all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 +(0.0973P P] where P=(F o2 +2F c2 /3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 65

66 Table S38: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for 3 4 U(eq is defined as one third of the trace of the orthogonalized U ij tensor. C (2 C (2 x/a y/b z/c U(eq C ( (2 C ( (3 C ( (3 C (2 C (2 N (2 N (19 N (2 N (2 N (2 N (19 N (2 N (19 N (2 O ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (5 66

67 x/a y/b z/c U(eq O ( ( ( (7 O (2 O (19 O (2 O ( ( ( ( ( ( ( ( ( ( ( ( (6 67

68 Table S39: Bond lengths (Å for 3 4. C1-N (3 C1-N (3 C1-N (3 C2-N (3 C2-N (3 C2-N (3 C3-N (3 C3-C (3 C3-C (4 C3-H3 1.0 C4-H4A 0.98 C4-H4B 0.98 C4-H4C 0.98 C5-H5A 0.98 C5-H5B 0.98 C5-H5C 0.98 C6-N (3 C6-N (3 C6-H C7-N (3 C7-N (3 N2-N (3 N4-O (3 N4-O (3 N5-O (3 N5-O (3 N6-N (3 N7-H N9-O (3 N9-O (3 68

69 Table S40: Bond angles ( for 3 4. N1-C1-N (2 N1-C1-N (2 N2-C1-N (2 N3-C2-N (2 N3-C2-N (2 N1-C2-N (19 N2-C3-C (2 N2-C3-C (2 C5-C3-C (2 N2-C3-H C5-C3-H C4-C3-H C3-C4-H4A C3-C4-H4B H4A-C4-H4B C3-C4-H4C H4A-C4-H4C H4B-C4-H4C C3-C5-H5A C3-C5-H5B H5A-C5-H5B C3-C5-H5C H5A-C5-H5C H5B-C5-H5C N7-C6-N (19 N7-C6-H N8-C6-H N6-C7-N (2 C1-N1-C (18 C1-N2-N (18 C1-N2-C (19 N3-N2-C (18 C2-N3-N (18 O2-N4-O (2 O2-N4-C (2 O1-N4-C (2 O3-N5-O (2 O3-N5-C (19 O4-N5-C (2 N7-N6-C (18 C6-N7-N (19 C6-N7-H N6-N7-H O5-N9-O (2 O5-N9-C (2 O6-N9-C (2 69

70 Table S41: Anisotropic atomic displacement parameters (Å 2 for 3 4. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C ( ( ( ( ( (9 C ( ( ( ( ( (9 C ( ( ( ( ( (10 C ( ( ( ( ( (13 C ( ( ( ( ( (13 C ( ( ( ( ( (7 C ( ( ( ( ( (9 N ( ( ( ( ( (8 N ( ( ( ( ( (8 N ( ( ( ( ( (8 N ( ( ( ( ( (9 N ( ( ( ( ( (9 N ( ( ( ( ( (8 N ( ( ( ( ( (9 N ( ( ( ( ( (8 N ( ( ( ( ( (10 O ( ( ( ( ( (7 O ( ( ( ( ( (12 O ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (10 O ( ( ( ( ( (10 70

71 Table S42: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 for 3 4. x/a y/b z/c U(eq H H4A H4B H4C H5A H5B H5C H H

72 Crystal Structure Report for sodium 3-nitro-1,2,4-triazol-5-olate monohydrate 5 H 2 O Figure S31: Asymmetric unit in the crystal structure of 5 H 2 O. Figure S32: Projection of the packing in 5 H 2 O down the a-axis. 72

73 Figure S27: Projection of the packing in 5 H 2 O down the b-axis. 73

74 Figure S28: Projection of the packing in 5 H 2 O down the c-axis. Table S51: Sample and crystal data for 5 H 2 O. Identification code DNTimpurity Chemical formula C 2 H 3 N 4 NaO 4 Formula weight Temperature 140(2 K Wavelength Å Crystal size x x mm Crystal habit clear orange blade Crystal system monoclinic Space group P 1 21/c 1 Unit cell dimensions a = (18 Å α = 90 b = (14 Å β = (2 c = (11 Å γ = 90 Volume (17 Å 3 Z 4 Density (calculated g/cm 3 Absorption coefficient mm -1 F(

75 Table S52: Data collection and structure refinement for 5 H 2 O. Diffractometer Bruker SMART APEX Radiation source fine-focus tube, MoKα Theta range for data collection 1.92 to Index ranges -13<=h<=14, -11<=k<=11, -8<=l<=9 Reflections collected 6577 Independent reflections 1444 [R(int = ] Coverage of independent reflections 94.4% Absorption correction multi-scan Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXTL XT 2013/6 (Sheldrick, 2013 Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014 (Sheldrick, 2014 Function minimized Σ w(f 2 o - F c2 2 Data / restraints / parameters 1444 / 0 / 112 Goodness-of-fit on F Final R indices R1 = , wr2 = 1061 data; I>2σ(I all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 +(0.0529P P] where P=(F o2 +2F c2 /3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 75

76 Table S53: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for 5 H 2 O. U(eq is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq C ( ( ( (3 9 C ( ( ( (3 9 N ( ( ( (3 6 N ( ( ( (3 6 N ( ( ( (3 6 N ( ( ( (3 7 Na ( ( ( (3 0 2 O ( ( ( (2 4 9 O ( ( ( (3 4 9 O ( ( ( (2 3 8 O ( ( ( (3 7 Table S54: Bond lengths (Å for 5 H 2 O. C1-O (2 C1-N (3 C1-N (3 C2-N (3 C2-N (3 C2-N (3 N1-N (2 N2-H1 0.89(3 N3-Na (19 N4-O (2 N4-O (2 Na1-O (19 Na1-O (16 Na1-N (19 Na1-O (2 Na1-O (17 Na1-O (17 Na1-Na (8 Na1-Na (8 Na1-H2 2.60(4 O1-Na (17 O3-Na (17 O4-Na (2 O4-H2 0.78(4 O4-H3 0.75(3 76

77 77

78 Table S55: Bond angles ( for 5 H 2 O. O3-C1-N (19 O3-C1-N (19 N3-C1-N (17 N1-C2-N (19 N1-C2-N (19 N3-C2-N (19 C2-N1-N (17 N1-N2-C (17 N1-N2-H (16 C1-N2-H (17 C2-N3-C (17 C2-N3-Na (14 C1-N3-Na (14 O1-N4-O (18 O1-N4-C (18 O2-N4-C (18 O4-Na1-O (7 O4-Na1-N (7 O3-Na1-N (6 O4-Na1-O (7 O3-Na1-O (6 N3-Na1-O (7 O4-Na1-O (6 O3-Na1-O (7 N3-Na1-O (6 O4-Na1-O (6 O4-Na1-O (6 O3-Na1-O (5 N3-Na1-O (6 O4-Na1-O (6 O1-Na1-O (6 O4-Na1-Na (5 O3-Na1-Na (5 N3-Na1-Na (5 O4-Na1-Na (5 O1-Na1-Na (4 O3-Na1-Na (4 O4-Na1-Na (6 O3-Na1-Na (4 N3-Na1-Na (5 O4-Na1-Na (4 O1-Na1-Na (4 O3-Na1-Na (4 Na1-Na1-Na (5 O4-Na1-H2 17.0(8 O3-Na1-H2 92.0(8 N3-Na1-H (8 O4-Na1-H2 94.8(8 O1-Na1-H2 93.1(8 O3-Na1-H2 87.8(8 Na1-Na1-H2 52.5(8 Na1-Na1-H2 88.7(8 N4-O1-Na (13 C1-O3-Na (13 C1-O3-Na (12 Na1-O3-Na (6 Na1-O4-Na (7 Na1-O4-H2 101.(3 Na1-O4-H2 120.(3 Na1-O4-H3 122.(2 Na1-O4-H3 110.(2 H2-O4-H3 106.(3 78

79 Table S56: Anisotropic atomic displacement parameters (Å 2 for 5 H 2 O. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C ( ( ( ( ( (8 C ( ( ( ( ( (8 N ( ( ( ( ( (7 N ( ( ( ( ( (7 N ( ( ( ( ( (7 N ( ( ( ( ( (7 Na ( ( ( ( ( (3 O ( ( ( ( ( (7 O ( ( ( ( ( (7 O ( ( ( ( ( (6 O ( ( ( ( ( (7 Table S57: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 5 H 2 O. x/a y/b z/c U(eq H ( ( ( (7 H ( ( ( (12 H ( ( ( (10 79

80 Crystal Structure Report for the co-crystal of 5-azido-3-nitro-1,2,4-triazole and PPN + 5- azido-3-nitro-1,2,4-triazolate 6 Figure S32: Projection of the packing in 6 perpendicular to the 001 plane. Hydrogen atoms have been omitted for clarity. Figure S24: Projection of the packing in 6 perpendicular to the 010 plane. Hydrogen atoms have been omitted for clarity. 80

81 Figure S34: Projection of the packing in 6 perpendicular to the 100 plane. Hydrogen atoms have been omitted for clarity. Table S43: Sample and crystal data for 6. Identification code XGCMK4_02 Chemical formula C 40 H 31 N 15 O 4 P 2 Formula weight Temperature 100(2 K Wavelength Å Crystal size x x mm Crystal habit orange blade/prism Crystal system triclinic Space group P -1 Unit cell dimensions a = (11 Å α = (2 b = (12 Å β = (2 c = (16 Å γ = (2 Volume (3 Å 3 Z 2 Density (calculated g/cm 3 Absorption coefficient mm -1 F(

82 Table S58: Data collection and structure refinement for 6. Diffractometer Bruker APEX DUO Radiation source fine-focus tube, MoKα Theta range for data collection 1.40 to Index ranges -15<=h<=15, -17<=k<=17, -22<=l<=22 Reflections collected Independent reflections [R(int = ] Absorption correction multi-scan Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXTL XS 2013/1 (Sheldrick, 2013 Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2013 (Sheldrick, 2013 Function minimized Σ w(f 2 o - F c2 2 Data / restraints / parameters / 0 / 550 Goodness-of-fit on F Δ/σ max Final R indices R1 = , wr2 = 7692 data; I>2σ(I all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 +(0.0651P P] where P=(F o2 +2F c2 /3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 82

83 Table S45: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 for 6. U(eq is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq P ( ( ( (12 P ( ( ( (12 N ( ( ( (4 C ( ( ( (4 C ( ( ( (5 C ( ( ( (6 C ( ( ( (6 C ( ( ( (5 C ( ( ( (5 C ( ( ( (5 C ( ( ( (7 C ( ( ( (6 C ( ( ( (5 C ( ( ( (5 C ( ( ( (4 C ( ( ( (6 C ( ( ( (6 C ( ( ( (8 C ( ( ( (12 C ( ( ( (8 C ( ( ( (4 C ( ( ( (4 C ( ( ( (5 C ( ( ( (6 C ( ( ( (6 C ( ( ( (6 C ( ( ( (5 C ( ( ( (4 C ( ( ( (5 C ( ( ( (5 C ( ( ( (5 C ( ( ( (5 C ( ( ( (4 C ( ( ( (4 C ( ( ( (6 C ( ( ( (6 C ( ( ( (5 83

84 x/a y/b z/c U(eq C ( ( ( (6 C ( ( ( (5 O ( ( ( (6 O ( ( ( (7 N ( ( ( (5 N ( ( ( (5 N ( ( ( (5 N ( ( ( (5 N ( ( ( (5 N ( ( ( (6 N ( ( ( (4 C ( ( ( (5 C ( ( ( (5 O ( ( ( (6 O ( ( ( (6 N ( ( ( (5 N ( ( ( (5 N ( ( ( (5 N ( ( ( (5 N ( ( ( (5 N ( ( ( (6 N ( ( ( (4 C ( ( ( (5 C ( ( ( (5 84

85 Table S46: Bond lengths (Å for 6. P1-N (19 P1-C (2 P1-C (2 P1-C (2 P2-N (19 P2-C (2 P2-C (2 P2-C (2 C5-C (3 C5-C (3 C6-C (3 C6-H C7-C (4 C7-H C8-C (4 C8-H C9-C (3 C9-H C10-H C11-C (3 C11-C (3 C11-H C12-C (4 C12-H C13-C (4 C13-H C14-C (3 C14-H C15-C (3 C15-H C17-C (3 C17-C (3 C17-H C18-C (4 C18-H C19-C (5 C19-H C20-C (4 C20-H C21-C (3 C21-H C23-C (3 C23-C (3 C24-C (3 C24-H C25-C (4 C25-H C26-C (4 C26-H C27-C (3 C27-H C28-H C29-C (3 C29-C (3 C29-H C30-C (3 C30-H C31-C (3 C31-H C32-C (3 C32-H C33-C (3 C33-H C35-C (3 C35-C (3 C36-C (4 C36-C (3 C36-H C37-C (4 C37-H C38-H C39-C (3 C39-H C40-H O1-N (3 O2-N (3 N1-C (3 N2-C (3 N2-N (3 N3-C (3 85

86 N3-H N4-N (3 N4-C (3 N5-N (3 N7-C (3 N7-C (3 O3-N (3 O4-N (3 N8-C (3 N9-C (3 N9-N (3 N10-C (3 N10-H N11-N (3 N11-C (3 N12-N (3 N14-C (3 N14-C (3 86

87 Table S47: Bond angles ( for 6. N15-P1-C (11 N15-P1-C (10 C5-P1-C (10 N15-P1-C (10 C5-P1-C (10 C16-P1-C (10 N15-P2-C (10 N15-P2-C (10 C23-P2-C (10 N15-P2-C (11 C23-P2-C (10 C35-P2-C (10 P2-N15-P (15 C6-C5-C (2 C6-C5-P (17 C10-C5-P (17 C7-C6-C (2 C7-C6-H C5-C6-H C8-C7-C (2 C8-C7-H C6-C7-H C9-C8-C (2 C9-C8-H C7-C8-H C8-C9-C (2 C8-C9-H C10-C9-H C9-C10-C (2 C9-C10-H C5-C10-H C16-C11-C (2 C16-C11-H C12-C11-H C13-C12-C (2 C13-C12-H C11-C12-H C14-C13-C (2 C14-C13-H C12-C13-H C13-C14-C (2 C13-C14-H C15-C14-H C14-C15-C (2 C14-C15-H C16-C15-H C11-C16-C (2 C11-C16-P (16 C15-C16-P (17 C22-C17-C (3 C22-C17-H C18-C17-H C19-C18-C (3 C19-C18-H C17-C18-H C18-C19-C (2 C18-C19-H C20-C19-H C19-C20-C (3 C19-C20-H C21-C20-H C22-C21-C (3 C22-C21-H C20-C21-H C21-C22-C (2 C21-C22-P (18 C17-C22-P (18 C28-C23-C (2 C28-C23-P (17 C24-C23-P (17 C25-C24-C (2 C25-C24-H C23-C24-H C26-C25-C (2 C26-C25-H C24-C25-H C27-C26-C (2 C27-C26-H C25-C26-H C26-C27-C (2 87

88 C26-C27-H C28-C27-H C23-C28-C (2 C23-C28-H C27-C28-H C34-C29-C (2 C34-C29-H C30-C29-H C31-C30-C (2 C31-C30-H C29-C30-H C30-C31-C (2 C30-C31-H C32-C31-H C31-C32-C (2 C31-C32-H C33-C32-H C32-C33-C (2 C32-C33-H C34-C33-H C29-C34-C (2 C29-C34-P (17 C33-C34-P (17 C38-C35-C (2 C38-C35-P (16 C40-C35-P (17 C37-C36-C (2 C37-C36-H C38-C36-H C39-C37-C (2 C39-C37-H C36-C37-H C35-C38-C (2 C35-C38-H C36-C38-H C37-C39-C (2 C37-C39-H C40-C39-H C39-C40-C (2 C39-C40-H C35-C40-H O2-N1-O (2 O2-N1-C (2 O1-N1-C (2 C1-N2-N (2 C2-N3-N (19 C2-N3-H N2-N3-H N5-N4-C (2 N6-N5-N (3 C2-N7-C1 98.9(2 N2-C1-N (2 N2-C1-N (2 N7-C1-N (2 N7-C2-N (2 N7-C2-N (2 N3-C2-N (2 O4-N8-O (2 O4-N8-C (2 O3-N8-C (2 C3-N9-N (2 C4-N10-N (19 C4-N10-H N9-N10-H N12-N11-C (2 N13-N12-N (3 C4-N14-C3 98.7(2 N9-C3-N (2 N9-C3-N (2 N14-C3-N (2 N14-C4-N (2 N14-C4-N (2 N10-C4-N (2 Table S62: Torsion angles ( for 6. C23-P2-N15-P (7 C35-P2-N15-P1 17.4(8 88

89 C34-P2-N15-P (7 C5-P1-N15-P2 41.3(7 C16-P1-N15-P (7 C22-P1-N15-P2-80.0(7 N15-P1-C5-C (18 C16-P1-C5-C6 36.0(2 C22-P1-C5-C6-79.5(2 N15-P1-C5-C (2 C16-P1-C5-C (17 C22-P1-C5-C (19 C10-C5-C6-C7-1.9(4 P1-C5-C6-C (19 C5-C6-C7-C8 1.8(4 C6-C7-C8-C9 0.0(4 C7-C8-C9-C10-1.6(4 C8-C9-C10-C5 1.4(3 C6-C5-C10-C9 0.3(3 P1-C5-C10-C (17 C16-C11-C12-C13-0.2(4 C11-C12-C13-C14-0.3(5 C12-C13-C14-C15 0.4(4 C13-C14-C15-C16 0.1(4 C12-C11-C16-C15 0.7(4 C12-C11-C16-P (2 C14-C15-C16-C11-0.6(3 C14-C15-C16-P (18 N15-P1-C16-C (2 C5-P1-C16-C (2 C22-P1-C16-C11 8.2(2 N15-P1-C16-C (2 C5-P1-C16-C (19 C22-P1-C16-C (17 C22-C17-C18-C19 0.1(4 C17-C18-C19-C20-1.2(5 C18-C19-C20-C21 1.6(5 C19-C20-C21-C22-0.8(6 C20-C21-C22-C17-0.3(5 C20-C21-C22-P (3 C18-C17-C22-C21 0.7(4 C18-C17-C22-P (2 N15-P1-C22-C (2 C5-P1-C22-C (2 C16-P1-C22-C (2 N15-P1-C22-C (2 C5-P1-C22-C (2 C16-P1-C22-C (2 N15-P2-C23-C (2 C35-P2-C23-C (19 C34-P2-C23-C (18 N15-P2-C23-C (18 C35-P2-C23-C (19 C34-P2-C23-C (2 C28-C23-C24-C25-1.1(3 P2-C23-C24-C (17 C23-C24-C25-C26-0.7(3 C24-C25-C26-C27 2.4(4 C25-C26-C27-C28-2.3(4 C24-C23-C28-C27 1.2(4 P2-C23-C28-C (19 C26-C27-C28-C23 0.5(4 C34-C29-C30-C31-0.4(3 C29-C30-C31-C32 1.7(4 C30-C31-C32-C33-1.3(4 C31-C32-C33-C34-0.5(4 C30-C29-C34-C33-1.4(3 C30-C29-C34-P (16 C32-C33-C34-C29 1.8(3 C32-C33-C34-P (19 N15-P2-C34-C (2 C23-P2-C34-C (18 C35-P2-C34-C (17 N15-P2-C34-C (18 C23-P2-C34-C (19 C35-P2-C34-C (2 N15-P2-C35-C (19 C23-P2-C35-C38-6.0(2 C34-P2-C35-C (19 N15-P2-C35-C (2 C23-P2-C35-C (17 C34-P2-C35-C (19 C38-C36-C37-C39-0.9(4 C40-C35-C38-C36 0.7(3 P2-C35-C38-C (18 C37-C36-C38-C35 0.2(4 89

90 C36-C37-C39-C40 0.7(4 C37-C39-C40-C35 0.3(3 C38-C35-C40-C39-1.0(3 P2-C35-C40-C (18 C1-N2-N3-C2 0.7(2 N3-N2-C1-N7-0.7(3 N3-N2-C1-N (2 C2-N7-C1-N2 0.3(3 C2-N7-C1-N (2 O2-N1-C1-N2-0.8(4 O1-N1-C1-N (2 O2-N1-C1-N (2 O1-N1-C1-N7 2.2(4 C1-N7-C2-N3 0.2(3 C1-N7-C2-N (2 N2-N3-C2-N7-0.7(3 N2-N3-C2-N (2 N5-N4-C2-N7 5.2(4 N5-N4-C2-N (2 C3-N9-N10-C4-0.4(3 N10-N9-C3-N14 0.5(3 N10-N9-C3-N (2 C4-N14-C3-N9-0.4(3 C4-N14-C3-N (2 O4-N8-C3-N9 3.3(4 O3-N8-C3-N (2 O4-N8-C3-N (2 O3-N8-C3-N14 0.8(4 C3-N14-C4-N10 0.1(3 C3-N14-C4-N (2 N9-N10-C4-N14 0.2(3 N9-N10-C4-N (2 N12-N11-C4-N14-6.3(4 N12-N11-C4-N (2 90

91 Table S49: Anisotropic atomic displacement parameters (Å2 for 6.The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 P ( ( ( ( ( (18 P ( ( ( ( ( (19 N ( ( ( ( ( (8 C ( ( ( ( ( (8 C ( ( ( ( ( (10 C ( ( ( ( ( (12 C ( ( ( ( ( (10 C ( ( ( ( ( (9 C ( ( ( ( ( (8 C ( ( ( ( ( (9 C ( ( ( ( ( (10 C ( ( ( ( ( (11 C ( ( ( ( ( (10 C ( ( ( ( ( (9 C ( ( ( ( ( (8 C ( ( ( ( ( (9 C ( ( ( ( ( (10 C ( ( ( ( ( (12 C ( ( ( ( ( (2 C ( ( ( ( ( (16 C ( ( ( ( ( (8 C ( ( ( ( ( (8 C ( ( ( ( ( (8 C ( ( ( ( ( (9 C ( ( ( ( ( (9 C ( ( ( ( ( (10 C ( ( ( ( ( (9 C ( ( ( ( ( (8 C ( ( ( ( ( (8 C ( ( ( ( ( (10 C ( ( ( ( ( (10 C ( ( ( ( ( (9 C ( ( ( ( ( (8 C ( ( ( ( ( (8 C ( ( ( ( ( (11 C ( ( ( ( ( (11 C ( ( ( ( ( (9 C ( ( ( ( ( (10 91

92 U 11 U 22 U 33 U 23 U 13 U 12 C ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (11 N ( ( ( ( ( (10 N ( ( ( ( ( (9 N ( ( ( ( ( (8 N ( ( ( ( ( (8 N ( ( ( ( ( (9 N ( ( ( ( ( (11 N ( ( ( ( ( (8 C ( ( ( ( ( (10 C ( ( ( ( ( (9 O ( ( ( ( ( (9 O ( ( ( ( ( (10 N ( ( ( ( ( (10 N ( ( ( ( ( (9 N ( ( ( ( ( (8 N ( ( ( ( ( (8 N ( ( ( ( ( (9 N ( ( ( ( ( (10 N ( ( ( ( ( (8 C ( ( ( ( ( (10 C ( ( ( ( ( (9 92

93 Table S50: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 for 6. x/a y/b z/c U(eq H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H

94 Crystal Structure Report for 5-azido-3-nitro-1,2,4-triazolate containing PPN + 3,5-dinitro- 1H-1,2,4-triazolate Figure S35: Disordered anion in the crystal structure of 5-azido-3-nitro-1,2,4-triazolate containing PPN + 3,5-dinitro-1H-1,2,4-triazolate. 94

95 Figure S35: Projection of the packing for 5-azido-3-nitro-1,2,4-triazolate containing PPN + 3,5- dinitro-1h-1,2,4-triazolate perpendicular to the 001 plane. Hydrogens have been omitted for clarity. Figure S37: Projection of the packing for 5-azido-3-nitro-1,2,4-triazolate containing PPN + 3,5- dinitro-1h-1,2,4-triazolate e perpendicular to the 010 plane. Hydrogens have been omitted for clarity. 95