Energetic Salts of Low-Symmetry Methylated 5-Aminotetrazoles
4), –115.6 (1 N, N-1), –115.7 (1 N, N-2), –339.7 (1 N, NH2) ppm.
(20 mL) was added to a solution of 6 (2.37 g, 9.83 mmol) in meth-
Raman: ν (rel. int.) = 3213 (19), 3025 (21), 2960 (90), 1646 (18), anol (20 mL) and stirred under light exclusion for 1 h. The precipi-
˜
1544 (53), 1449 (26), 1375 (76), 1314 (17), 1200 (40), 1127 (17),
1084 (85), 1056 (30), 1016 (73), 805 (17), 649 (100), 473 (48), 319
tated silver iodide was then filtered and washed with methanol.
After removing the solvent, the colourless residue was dissolved in
a small amount of methanol and recrystallized overnight in an
ether chamber. After filtering the colourless solid, this was dried
(42), 159 (37) cm–1. IR (KBr): ν = 3385 (s), 3307 (s), 3217 (s), 3083
˜
(w), 2959 (w), 2758 (w), 1635 (s), 1553 (s), 1448 (m), 1420 (w), 1409
(m), 1376 (m), 1314 (m), 1204 (s), 1124 (w), 1084 (w), 1054 (w), on air (1.63 g, 78%). C3H8ClN5O4 (213.02): calcd. C 16.89, H 3.78,
1015 (m), 808 (m), 757 (m), 649 (s), 488 (m) cm–1.
N 32.86, Cl 16.41; found C 16.91, H 3.86, N 32.72, Cl 17.73. DSC
(5 °C min–1 °C, onset): 132.3 (m.p.), 285.1 (dec.). MS (FAB+, xe-
non, 6 keV, m-NBA matrix): m/z = 114.2 [cation]+. 1H NMR ([D6]-
DMSO, 499.78 MHz, TMS): δ = 8.23 (s, 2 H, NH2), 4.30 (s, 3 H,
3-CH3), 3.87 (s, 3 H, 2-CH3) ppm. 13C{1H} NMR ([D6]DMSO,
100.52 MHz, TMS): δ = 158.09 (1 C, C-ring), 42.54 (1 C, 3-CH3),
34.18 (1 C, 2-CH3) ppm. 35Cl NMR ([D6]DMSO, 39.21 MHz,
NaCl): δ = 1.01 (ClO4). 15N{1H} NMR ([D6]DMSO, 40.55 MHz,
MeNO2): δ = –31.43 (1 N, N-4), –108.71 (1 N, N-3), –110.76 (1
N,N-2),–180.26(1N,N-5),–327.01(1N,NH2) ppm.15NNMR([D6]-
DMSO, 40.51 MHz, MeNO2): δ = –32.04 (q, 2J = 2.79 Hz, 1 N,
N-4), –109.32 (q, 3J = 1.86 Hz, 1 N, N-3), –111.30 (q, 2J = 2.79 Hz,
1 N, N-2), –180.84 (q, 3J = 1.86 Hz, 1 N, N-5), –327.18 (t, 1J =
Synthesis of 2-Methyl-5-aminotetrazol-4-ium Perchlorate (7):
Tetrazole 5 (0.25 g, 2.52 mmol) was dissolved in the minimum
amount of 72% concentrated perchloric acid. The reaction mixture
was layered with diethyl ether and stored in a fridge overnight
yielding colourless plates of the product, which were filtered,
washed with diethyl ether and allowed to air-dry. No further purifi-
cation was necessary. Single crystals of the compound suitable for
X-ray analysis were obtained by ether diffusion into a concentrated
methanolic solution (0.39 g, 77%). C2H6ClN5O4 (199.01): calcd. C
12.02, H 3.05, N 35.12, Cl 17.57; found C 12.04, H 3.03, N 35.09,
Cl 17.98, DSC (5 °C min–1 °C, onset): 125 (m.p.), 196 (dec.). MS
(FAB+, xenon, 6 keV, m-NBA matrix): m/z = 100.0 [cation]+. 1H
NMR ([D6]DMSO, 400.18 MHz, TMS): δ = 8.67 (s, 2 H, NH2),
7.51 (s, 1 H, NH), 3.97 (s, 3 H, CH3) ppm. 13C{1H} NMR ([D6]-
DMSO, 100.63 MHz, TMS): δ = 166.8 (1 C, C-ring), 40.7 (1 C,
CH3) ppm. 15N NMR ([D6]DMSO, 40.55 MHz, MeNO2): δ = –8.8
(q, J = 1.33 Hz, 1 N, N-3), –90.0 (s, 1 N, N-4) –113.4 (s, 1 N, N-
89.51 Hz, 1 N, NH ) ppm. Raman: ν (rel. int.) = 3427 (1), 3238 (2),
˜
2
3053 (10), 3025 (11), 2966 (46), 2818 (2), 1666 (9), 1595 (4), 1500
(6), 1442 (13), 1416 (29), 1396 (9), 1294 (5), 1261 (15), 1118 (8),
1076 (12), 1015 (6), 936 (100), 854 (21), 820 (2), 680 (11), 634 (33),
529 (4), 464 (22), 318 (21), 290 (8), 238 (10), 194 (4), 84 (1) cm–1.
IR (KBr): ν = 3434 (m), 3308 (m), 3220 (m), 3217 (m), 3047 (s),
˜
1), –114.2 (s, 1 N, N-2), –340.1 (s, 1 N, NH ) ppm. Raman: ν (rel.
˜
2
2946 (m), 2840 (w), 2767 (w), 2704 (w), 2657 (w), 2501 (w), 2439
(vw), 2184 (w), 2122 (w), 2024 (w), 1923 (w), 1864 (w), 1666 (vs),
1593 (s), 1566 (w), 1497 (w), 1468 (m), 1430 (m), 1384 (w), 1363
(m), 1290 (m), 1251 (m), 1144 (s), 1120 (s), 1088 (s), 1013 (m), 940
(w), 852 (m), 726 (w), 674 (w), 626 (m), 568 (w) cm–1.
int.) = 3198 (5), 3046 (8), 2972 (22), 1686 (7), 1492 (7), 1442 (22),
1411 (13), 1385 (19), 1182 (9), 1091 (21), 1024 (27), 926 (100), 803
(14), 651 (25), 637 (21), 623 (16), 479 (19), 468 (20), 453 (22), 321
(19), 224 (9) cm–1. IR (KBr): ν = 3287 (s), 3254 (s), 3183 (s), 3097
˜
(s), 3025 (m), 2756 (m), 2480 (w), 2351 (w), 2319 (w), 2139 (w),
2030 (w), 1661 (vs), 1586 (m), 1575 (w), 1442 (w), 1408 (w), 1391
(w), 1333 (w), 1180 (m), 1145 (s), 1109 (vs), 1089 (vs), 1018 (m),
940 (w), 923 (w), 803 (w), 732 (w), 696 (m), 672 (w), 647 (m), 637
(m), 626 (s), 481 (w) cm–1.
Synthesis of 5-Amino-1,3-dimethyltetrazol-3-ium Nitrate (10): A
solution of silver nitrate (0.60 g, 3.53 mmol) in methanol (5 mL)
was added with stirring to a solution of 6 (0.85 g, 3.53 mmol) in
methanol (10 mL). Under exclusion of light the solution was stirred
at room temperature for 50 min and then filtered. After evaporating
the solvent the slightly brown residue was dissolved in the mini-
mum amount of methanol and crystallized overnight in an ether
chamber. The colourless precipitate was then filtered under vacuum
and dried in air (0.52 g, 79%). C3H8N6O3 (176.06): calcd. C 20.46,
H 4.58, N 47.71; found C 20.38, H 4.48, N 47.66. DSC (5 °Cmin–1
°C, onset): 150.1 (m.p.), 198.5 (dec.). MS (FAB+, xenon, 6 keV, m-
NBA matrix): m/z = 114.2 [cation]+. 1H NMR ([D6]DMSO,
399.78 MHz, TMS): δ = 8.27 (s, 2 H, NH2), 4.30 (s, 3 H, 3-CH3),
Synthesis of 5-Amino-2-methyltetrazol-4-ium Nitrate (8): Solid crys-
talline 5 (0.100 g, 1.0 mmol) was dissolved in a minimum of con-
centrated (65%) nitric acid. The clear, colourless reaction mixture
was stirred until all 5 had dissolved. The solution was then cooled
to 4 °C overnight to yield the formation of clear colourless crystals
suitable for X-ray analysis, which were filtered off cold and washed
until dry and acid-free with diethyl ether. No further purification
was necessary (0.073 g, 73%). C2H6N6O3 (162.05): calcd. C 14.81,
H 3.73, N 51.84; found C 14.70, H 3.68, N 51.26. DSC (5 °Cmin–1
°C, onset): 123.2 (m.p.), 161.4 (dec.). MS (FAB+, xenon, 6 keV, m-
NBA matrix): m/z = 100.0 [2MAT]+. 1H NMR ([D6]DMSO,
400.18 MHz, TMS): δ = 8.50 (s, 3 H, NH + NH2), 4.01 (s, 3 H,
CH3) ppm. 13C{1H} NMR ([D6]DMSO, 100.63 MHz, TMS): δ =
167.2 (1 C, C-ring), 38.9 (1 C, CH3) ppm. 14N{1H} NMR ([D6]-
3.87 (s,
3
H, 2-CH3) ppm. 13C{1H} NMR ([D6]DMSO,
100.52 MHz, TMS): δ = 158.60 (1 C, C-ring), 43.04 (1 C, 3-CH3),
34.64 (1 C, 2-CH3) ppm. 14N NMR ([D6]DMSO, 28.88 MHz,
MeNO2): δ = 3.82 (1 N, NO3 ) ppm. 15N NMR ([D6]DMSO,
–
40.51 MHz, MeNO2): δ = –4.54 (s, 1 N, NO3), –32.63 (q, 2J =
2.32 Hz, 1 N, N-4), –109.61 (q, 3J = 1.86 Hz, 1 N, N-3), –111.08
–
DMSO, 40.55 MHz, MeNO2): δ = –14 (1 N, NO3 ), –111 (2 N, N-
2
1
1/N-2) ppm. 15N NMR ([D6]DMSO, 40.55 MHz, MeNO2): δ =
(q, J = 2.79 Hz, 1 N, N-2), –181.18 (m, 1 N, N-5), –326.05 (s, J
= 89.5 Hz, 1 N, NH ) ppm. Raman: ν (rel. int.) = 3028 (7), 2994
–
˜
–6.9 (q, J = 1.30 Hz, 1 N, N-3), –15.1 (s, 1 N, NO3 ), –84.4 (s, 1
2
(5), 2965 (29), 1660 (5), 1593 (5), 1444 (10), 1415 (18), 1294 (5),
1257 (12), 1126 (5), 1077 (13), 1049 (100), 1014 (7), 852 (17), 714
(11), 678 (9), 632 (19), 534 (5), 363 (4), 328 (15), 300 (6) 236 (7),
N, N-4) –114.4 (s, 1 N, N-1), –114.9 (s, 1 N, N-2), –339.5 (s, 1 N,
NH ) ppm. Raman: ν (rel. int.) = 3192 (3), 3049 (11), 3039 (9),
˜
2
2968 (30), 1663 (9), 1437 (21), 1383 (27), 1297 (5), 1189 (11), 1086
(18), 1043 (100), 1010 (18), 789 (15), 728 (11), 713 (9), 649 (33),
207 (6), 105 (1), 85 (1) cm–1. IR (KBr): ν = 3307 (w), 3217 (m),
˜
480 (14), 321 (23), 212 (9), 141 (22) cm–1. IR (KBr): ν = 3383 (m),
3045 (m), 2767 (w), 2703 (w), 2657 (w), 2499 (w), 2426 (w), 2395
(w), 2184 (w), 2122 (w), 1659 (s), 1593 (m), 1384 (vs), 1289 (w),
1250 (m), 1116 (m), 1081 (w), 1014 (w), 851 (w), 825 (w), 725 (w),
674 (w), 627 (w), 569 (w), 365 (w), 332 (w) cm–1.
˜
3249 (m), 3184 (m), 3049 (w), 2925 (w), 2853 (w), 2637 (w), 2426
(w), 1677 (s), 1430 (m), 1384 (s), 1308 (m), 1187 (w), 1073 (m),
1041 (m), 1010 (m), 953 (w), 823 (m), 787 (m), 726 (m), 647 (m),
575 (m), 478 (w) cm–1.
Synthesis of 5-Amino-1,3-dimethyltetrazol-3-ium Azide (11): The
salt 6 (2.13 g, 8.85 mmol) was added to a suspension of freshly
prepared silver azide (1.50 g, 10.01 mmol) in methanol (50 mL).
Synthesis of 5-Amino-1,3-dimethyltetrazol-3-ium Perchlorate (9): A
solution of silver perchlorate (2.04 g, 9.84 mmol) in methanol
Eur. J. Inorg. Chem. 2009, 880–896
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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