302 Klapo¨tke and Miro´ Sabate´
(1C, C1/C2), 154.49 (1C, C2/C1); 14N NMR (DMSO-
d6, 28.92 MHz, 25◦C, CH3NO2) δ (ppm): −4.95 (1N,
NO3−); C2H7N5O4 (165.05 g mol−1, calcd/found): C
14.54/14.54, H 4.27/4.05, N 42.42/42.33; m/z (FAB+,
xenon, 6 keV, m-NBA matrix): 103.2 [GU]+; DSC
(5◦C min−1): 203◦C (mp + dec); Sensitivity data:
friction >360 N; shock >30 J; electrostatic discharge
insensitive.
NMR spectra were recorded on a JEOL Eclipse 400
instrument in DMSO-d6 at or near 25◦C. The chemi-
cal shifts are given relative to tetramethylsilane (1H
and 13C), CH3NO2 (14N), and NaCl (35Cl) as exter-
nal standards. Infrared (IR) spectra were recorded
on a Perkin-Elmer spectrum one FT-IR instrument
[9] as KBr pellets at 20◦C. Transmittance values are
qualitatively described as “very strong” (vs), “strong”
(s), “medium” (m), and “weak” (w). Raman spectra
were recorded on a Perkin-Elmer spectrum 2000R
NIR FT-Raman instrument equipped with a Nd:YAG
laser (1064 nm). The intensities are reported as per-
centages of the most intense peak and are given
in parentheses. Elemental analyses were performed
with a Netsch simultaneous thermal analyzer STA
429. Melting points were determined by differen-
tial scanning calorimetry (Linseis DSC PT-10 instru-
ment [10], calibrated with standard pure indium and
zinc). Measurements were performed at a heating
rate of 5◦C min−1 in closed aluminum sample pans
with a 1-µm hole in the top for gas release under a ni-
trogen flow of 20 mL min−1 with an empty identical
aluminum sample pan as a reference. For the calori-
metric measurements, a Parr 1356 bomb calorime-
ter (static jacket) equipped with a Parr 207A oxygen
bomb for the combustion of highly energetic mate-
rials was used [11].
Preparation of GUP
Cyanoguanidine (5.001 g, 59.47 mmol) was dissolved
in 20 mL water, and 70% concentrated perchloric
acid (17.001 g, 119.02 mmol) was added slowly. The
reaction mixture was brought to reflux and stirred
for 15 min. Crystals (suitable for X-ray diffraction)
of the title compound formed upon slow cooling
overnight and were washed with ethanol and ether
(9.919 g, 82%). No further purification was required.
Analytical Data of GUP
IR v˜ (cm−1; KBr, rel. int.): 3459(s), 3378(s), 3256(s),
3187(s), 1736(s), 1679(s), 1654(m), 1583(s), 1527(m),
1465(m), 1345(m), 1108(s), 1089(s), 931(w), 764(w),
713(w), 680(w), 625(m), 559(m), 463(w); Raman
v˜ (cm−1) (rel. int.): 3277(3), 3072(4), 2986(100),
2187(3), 1725(15), 1618(12), 1576(9), 1532(9),
1466(16), 1335(4), 1124(18), 1081(17), 932(99),
817(4), 782(5), 707(14), 631(21), 551(7), 461(38),
436(33), 338(6), 273(139); 1H NMR (DMSO-d6,
400.18 MHz, 25◦C, TMS) δ (ppm): 9.57 (1H, s,
NH), 8.00 (4H, s, H2N C NH+2 ), 7.08 (2H, s,
Preparation of GUN
Sixty-five percent concentrated nitric acid (11.351 g,
119.02 mmol) was added dropwise to a solution of
cyanoguanidine (5.001 g, 59.47 mmol) in 40 mL wa-
ter by means of a dropping funnel. The solution was
stirred for 15 min at room temperature and shortly
boiled. Slow cooling to room temperature resulted
first in cloudiness and finally in the formation of an
insoluble powder that was filtered, washed with ace-
tone, and dried under high vacuum (9.113 g, 93%).
No further purification was required.
1
NH2); 13C{ H} NMR (DMSO-d6, 100.63 MHz,
25◦C, TMS) δ (ppm): 155.5 (1C, C1/C2), 154.4 (1C,
C2/C1); 35Cl NMR (DMSO-d6, 400.18 MHz, 25◦C,
NaCl) δ (ppm): +1000 (ClO−4 ); C2H7N4O5Cl (202.01
g mol−1, calcd/found): C 11.88/11.79, H 3.49/3.35,
N 27.73/27.45; m/z (FAB+, xenon, 6 keV, m-NBA
matrix): 103.2 [GU]+; DSC (5◦C min−1): 204◦C
(dec), 241◦C (mp), 313◦C (bp); Sensitivity data:
friction >360 N; shock >30 J; electrostatic discharge
insensitive.
Analytical Data of GUN
IR v˜ (cm−1; KBr, rel. int.): 3456(s), 3384(s), 3295(s),
3208(s), 3032(m), 2427(w), 2199(w), 2034(w),
1733(s), 1688(s), 1635(s), 1590(s), 1533(m), 1456(s),
1385(s), 1347(s), 1148(m), 1053(s), 929(m), 817(m),
753(m), 705(m), 624(s), 559(m), 501(m); Raman
v˜ (cm−1) (rel. int.): 3236(2), 2986(43), 1744(4),
1693(3), 1635(3), 1583(6), 1451(5), 1388(4), 1142(7),
1054(100), 930(8), 718(8), 560(3), 448(20), 287(5),
139(6); 1H NMR (DMSO-d6, 400.18 MHz, 25◦C,
TMS) δ (ppm): 9.47 (1H, s, NH), 8.08 (4H, s,
X-Ray Structure Determination of GUP
Crystal
Data. Guanylurea
perchlorate,
C2H7N4O5Cl, M = 202.01 g mol−1, a = 8.0115(2),
◦
˚
b= 9.7328(2), c= 9.5770(2) A, and β = 105.895(2) ;
−3
˚
U = 718.21(3) A , space group P21/c, Z = 4, Dc =
1.873 g cm−3. Crystal dimensions 0.20 × 0.10 ×
H2N C NH+2 ), 7.10 (2H, s, NH2); 13C{ H} NMR
0.10 mm. µ(Mo − Kα) = 0.21 mm , λ = 0.71073 A,
F(000) = 416.
1
−1
˚
(DMSO-d6, 100.63 MHz, 25◦C, TMS) δ (ppm): 155.56
Heteroatom Chemistry DOI 10.1002/hc