Substituted Nitrogen-Rich Tetrazoles
(NCH2), 48.3 (CH2OH) ppm. MS (FAB+): m/z = 75 [CH7N4+].
solved in warm water (approx. 20 mL). The clear solution was
mixed with a solution of AgNO3 (2.55 g, 15 mmol) in water
(10 mL). The mixture was stirred for 5 min at room temperature in
the darkness. The white precipitate was separated by centrifugation,
washed twice with water until free of acid, and finally resuspended
in water (approx. 20 mL). This suspension of silver 1-(2-hydroxy-
ethyl)-5-nitriminotetrazolate was mixed with a solution of azidofor-
mamidinium chloride (1.82 g, 15 mmol) in warm water (approx.
15 mL). This mixture was stirred for 30 min at 30 °C in darkness.
The AgCl precipitate was removed by filtration. The clear solution
was evaporated to dryness under reduced pressure, and the product
was recrystallized from ethanol/water to yield 2.88 g (11.1 mmol,
74%) of 9 as very fine needles. Unfortunately no crystals suitable
for X-ray crystallography were obtained. DSC (5 °C min–1): 154 °C
MS (FAB–): m/z = 173.0 [C3H5N6O3 ]. C4H12N10O3 (248.22): calcd.
–
C 19.36, H 4.87, N 56.43; found C 19.30, H 4.89, N 56.55. Impact
sensitivity: 10 J. Friction sensitivity: 192 N. ESD: 0.15 J.
Diaminoguanidinium 1-(2-Hydroxyethyl)-5-nitriminotetrazolate (7):
1-(2-Hydroxyethyl)-5-nitriminotetrazole (2.62 g, 15 mmol) was dis-
solved in warm water (approx. 20 mL). The clear solution was
mixed with a solution of AgNO3 (2.55 g, 15 mmol) in water (ap-
prox. 10 mL). The resulting mixture was stirred for 5 min at room
temp. in the darkness. The white precipitate was separated by cen-
trifugation, washed twice with water until free of acid, and resus-
pended in water (approx. 20 mL). The suspension of silver-1-(2-
hydroxyethyl)-5-nitriminotetrazolate was mixed with a solution of
diaminoguanidinium iodide (3.26 g, 15 mmol) in warm water (ap-
prox. 15 mL). The mixture was stirred for 30 min at 30 °C in dark-
ness. The AgI precipitate was removed by filtration. The clear solu-
tion was evaporated to dryness under reduced pressure, and the
product was recrystallized from ethanol/water; yield 71% (2.80 g,
10.65 mmol). DSC (5 °C min–1): 110 °C (m.p.), 208 °C (dec.). IR
(dec.). IR (KBr): ν = 3551 (m), 3474 (s), 3413 (vs), 3236 (w), 2984
˜
(m), 2962 (m), 2643 (w), 2102 (w), 2023 (w), 1911 (w), 1637 (m),
1618 (m), 1578 (vs), 1491 (s), 1454 (m), 1426 (m), 1403 (m), 1364
(m), 1330 (s), 1266 (s), 1222 (m), 1153 (m), 1050 (s), 1033 (s), 991
(m), 949 (m), 887 (m), 871 (m), 862 (m), 777 (w), 724 (m), 684 (w),
668 (w), 583 (m), 523 (m), 485 (w) cm–1. Raman (1064 nm, 500 mW,
(KBr): ν = 3441 (s), 3339 (vs), 3289 (vs), 2981 (w), 2955 (w), 2352
˜
25 °C): ν = 3006 (21), 2988 (46), 2963 (76), 2956 (71), 2903 (16),
˜
(w), 1674 (vs), 1629 (vs), 1556 (w), 1508 (vs), 1455 (s), 1446 (s),
1421 (m), 1344 (vs), 1318 (vs), 1268 (s), 1231 (m), 1174 (m), 1112
(m), 1063 (m), 1049 (m), 1031 (m), 971 (m), 918 (w), 879 (w), 864
(w), 778 (w), 742 (w), 670 (w), 520 (w) cm–1. Raman (1064 nm,
1589 (100), 1465 (11), 1450 (9), 1429 (12), 1411 (33), 1404 (41),
1362 (13), 1307 (7), 1258 (8), 1225 (34), 1158 (3), 1043 (18), 995
(13), 952 (4), 874 (11), 863 (11), 778 (3), 762 (17), 724 (3), 670 (10),
524 (9), 488 (7), 449 (5), 327 (3), 278 (11) cm–1. 1H NMR ([D6]-
DMSO, 25 °C): δ = 9.36 [s, 5 H, {C–(NH2)2}, –OH], 4.23 (t, 2 H,
NCH2), 3.77 (t, 2 H, CH2OH) ppm. 13C NMR ([D6]DMSO, 25 °C):
δ = 156.8 (CN4), 150.7 [C(NH2)2], 58.1 (NCH2), 50.4 (CH2OH)
500 mW, 25 °C): ν = 3340 (3), 3262 (8), 3002 (3), 2984 (15), 2956
˜
(5), 2892 (3), 1505 (100), 1341 (18), 1274 (7), 1177 (3), 1111 (7),
1052 (4), 1033 (30), 992 (8), 936 (5), 865 (5), 748 (7), 671 (4), 489
1
(3) cm–1. H NMR ([D6]DMSO, 25 °C): δ = 8.55 [s, 2 H, C(–NH–
ppm. MS (FAB+): m/z = 86.1 [CH4N5+]. MS (FAB–): m/z = 173.0
NH2)2], 7.14 (s, 2 H, C=NH2), 4.93 (s, 1 H, OH), 4.59 [s, 4 H,
C(–NH–NH2)2], 4.07 (t, 2 H, N–CH2), 3.70 (t, 2 H, CH2–OH)
–
[C3H5N6O3 ]. C4H9N11O3 (259.19): calcd.
C 18.54, H 3.50,
N 59.45; found C 19.71, H 3.62, N 49.60. Impact sensitivity: 9 J.
Friction sensitivity: 120 N. ESD: 0.15 J.
ppm. 13C NMR ([D6]DMSO, 25 °C):
δ = 160.3 [C(NH–
NH2)2(NH2)+], 157.6 (CN4), 59.1 (NCH2), 48.8 (CH2OH) ppm.
MS (FAB+): m/z = 90.1 [CH8N5+]. MS (FAB–): m/z = 173.0
–
[C3H5N6O3 ]. C4H13N11O3 (263.22): calcd. C 18.25, H 4.98,
Diaminouronium 1-(2-Hydroxyethyl)-5-nitriminotetrazolate (10): 1-
(2-Hydroxyethyl)-5-nitriminotetrazole (1.74 g, 10 mmol) was dis-
solved in water (10 mL) and diaminourea (0.90 g, 10 mmol) was
added to the clear solution. The free base dissolved immediately,
the mixture was warmed to 50 °C for 5 min, and the solution was
evaporated to dryness. Recrystallization of the crude material from
ethanol/water affords 2.34 g (8.86 mmol, 86%) of 10 as a colorless
solid. Unfortunately, no crystals suitable for X-ray crystallography
by recrystallization either from water, dimethyl formamide or an
ethanol/water mixture were obtained. DSC (5 °C min–1): 136 °C
N 58.53; found C 18.17, H 4.87, N 58.07. Impact sensitivity: Ͼ 40
J. Friction sensitivity: 144 N. ESD: 0.20 J.
Triaminoguanidinium 1-(2-Hydroxyethyl)-5-nitriminotetrazolate (8):
1-(2-Hydroxyethyl)-5-nitriminotetrazole (1.74 g, 10 mmol) was dis-
solved in water (10 mL) and triaminoguanidine (1.04 g, 10 mmol)
was added under nitrogen. The free base dissolved immediately, the
mixture was warmed to 40 °C for 5 min., and the clear solution
was evaporated to dryness. Recrystallization of the crude material
from ethanol/water affords 2.20 g (7.91 mmol, 79%) of 8 as color-
less crystals. DSC (5 °C min–1): 142 °C (m.p.), 215 °C (dec.). IR
(m.p.), 191 °C (dec.). IR (KBr): ν = 3460 (m), 3377 (m), 3335 (m),
˜
3295 (m), 3230 (m), 3121 (m), 3024 (w), 2962 (w), 2946 (w), 2896
(w), 2796 (w), 2694 (w), 2379 (w), 2030 (w), 1691 (m), 1624 (m),
1504 (s), 1458 (m), 1430 (m), 1376 (s), 1337 (s), 1311 (vs), 1253 (m),
1234 (m), 1176 (m), 1158 (m), 1117 (m), 1059 (m), 1035 (m), 996
(w), 970 (m), 940 (w), 879 (w), 871 (w), 773 (w), 747 (w), 742 (w),
687 (w), 664 (m), 583 (m), 567 (m), 527 (w) cm–1. Raman (1064 nm,
(KBr): ν = 3552 (s), 3477 (s), 3414 (vs), 3348 (s), 3213 (s), 1685 (s),
˜
1637 (m), 1617 (s), 1508 (s), 1451 (s), 1423 (m), 1392 (s), 1360 (s),
1337 (s), 1267 (m), 1241 (m), 1227 (m), 1202 (m), 1160 (w), 1128
(m), 1111 (m), 1073 (m), 1054 (w), 1034 (w), 990 (m), 952 (m), 884
(w), 861 (w), 778 (w), 749 (w), 702 (w), 637 (m), 608 (m), 511 (w),
483 (m) cm–1. Raman (1064 nm, 500 mW, 25 °C): ν = 3345 (13),
˜
500 mW, 25 °C): ν = 3377 (1), 3333 (1), 3298 (2), 3025 (3), 2971
˜
3321 (13), 3267 (18), 3007 (7), 2966 (14), 2883 (6), 1687 (3), 1513
(100), 1459 (5), 1423 (7), 1341 (19), 1274 (9), 1110 (12), 1035 (49),
991 (8), 752 (10), 671 (5), 512 (3), 483 (5) cm–1. 1H NMR (D2O,
25 °C): δ = 4.67 [s, 10 H, C(-NH-NH2)3, -OH], 4.25 (t, 2 H, NCH2),
3.85 (t, 2 H, CH2OH) ppm. 13C NMR (D2O, 25 °C): δ = 159.6
[C(-NH-NH2)3], 156.2 (CN4), 59.2 (NCH2), 48.8 (CH2OH) ppm.
MS (FAB+): m/z = 105.1 [CH9N6+]. MS (FAB–): m/z = 173.0
(10), 2898 (2), 1690 (3), 1548 (3), 1502 (100), 1458 (2), 1418 (3),
1375 (7), 1336 (28), 1281 (3), 1231 (2), 1177 (6), 1118 (17), 1052
(7), 1035 (62), 999 (4), 972 (4), 939 (3), 881 (7), 749 (10), 666 (7),
586 (3), 490 (4), 444 (3), 385 (3), 308 (13), 274 (11) cm–1. 1H NMR
([D6]DMSO, 25 °C): δ = 7.75 (s, 8 H, –NH–NH2, NH–NH3,
–OH), 4.08 (t, 2 H, NCH2), 3.70 (t, 2 H, CH2OH) ppm. 13C NMR
([D6]DMSO, 25 °C): δ = 159.4 [C(–NH–NH2)(–NH–NH3)], 157.3
(CN4), 59.1 (NCH2), 48.9 (CH2OH) ppm. MS (FAB+): m/z = 91.0
–
[C3H5N6O3 ]. C4H14N12O3 (278.23): calcd. C 17.27, H 5.07,
N 60.41; found C 17.13, H 4.88, N 60.27. Impact sensitivity: 18 J.
Friction sensitivity: Ͼ 360 N. ESD: 0.80 J.
[CH7N4O+]. MS (FAB–): m/z = 173.0 [C3H5N6O3 ]. C4H14N10O4
–
(264.20): calcd. C 18.18, H 4.58, N 53.01; found C 18.29, H 4.52,
Azidoformamidinium 1-(2-Hydroxyethyl)-5-nitriminotetrazolate (9): N 52.18. Impact sensitivity: 40 J. Friction sensitivity: 288 N. ESD:
1-(2-Hydroxyethyl)-5-nitriminotetrazole (2.62 g, 15 mmol) was dis- 0.60 J.
Eur. J. Inorg. Chem. 2011, 4471–4480
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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