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Safe 5-nitrotetrazolate anion transfer reagents

Thomas M. Klapotke* and Carles Miro Sabate

Published on 27 January 2009. Downloaded by RMIT Uni on 24/08/2014 12:59:01.

Received 24th October 2008, Accepted 19th December 2008

First published as an Advance Article on the web 27th January 2009
DOI: 10.1039/b818900p
Silver 5-nitrotetrazolate (1) and copper(II) 5-nitrotetrazolate 5-nitrotetrazole dihydrate (2) are useful
reagents for the synthesis of 5-nitrotetrazole (NT) salts. Both compounds were synthesized and
characterized by vibrational spectroscopy (IR and Raman) and differential scanning calorimetry
(DSC). In addition, their sensitivity towards friction, shock and electrostatic discharge was tested by
standard BAM methods. The extremely high sensitivity of both materials makes the transfer of the NTanion using 1 and 2 hazardous and not suitable for up-scaling. In order to diminish the hazards
involved with the transfer of the energetic anion and to render the synthesis of NT salts suitable for an
industrial scale the two compounds were stabilized by coordination with a chelating ligand and
silver(ethylendiamine) 5-nitrotetrazolate (3) and bis(ethylendiamine)copper(II) 5-nitrotetrazolate (4)
were synthesized in high yields. Both the stabilized NT- anion transfer reagents were characterized by
analytical and spectroscopic methods. In addition, the crystal structure of the ethylendiamine copper
;
complex (4) was determined: orthorombic, Pbca; a = 7.5200(1), b = 14.0124(2), c = 14.7740(2) A
3 . Furthermore, we synthesized triaminocopper(II) 5-nitrotetrazolate (5), which has
V = 1556.78(4) A
potential as a more environmentally-friendly primary explosive. Lastly, the synthetic potential of the
ethylediamine adducts 3 and 4 to form energetic salts of NT was investigated.

Introduction
The synthesis of highly energetic materials has been a long-term
goal in our research group.14 Azide, nitrate and perchlorate and
more recently dinitramide (- N(NO2 )2 ) or azotetrazolate ([C2 N10 ]2- )
have classically been used as counter-anions for the synthesis
of explosives.5 Recently, the use of 5-nitrotetrazolate (NT- ) as
an organic anion for the synthesis of energetic salts has gained
interest.68 The NT- anion has a low carbon content, which is
balanced out by a good oxygen balance at the same time it has
a high nitrogen content (~61% in 5-nitrotetrazole, NT).9 In 1963
Harris et. al. reported the synthesis of iron(II) 5-nitrotetrazolate
(Fe(NT)2 )10 by the reaction of sodium 5-nitrotetrazolate (NaNT)
with a solution of FeCl2 in diluted HCl and characterized the
compound only by IR and elemental analysis. Around a decade
later, Raymond et al.11 patented the synthesis of the Hg+ , Hg2+
and Ag+ salts from the reaction of a copper(II) 5-nitrotetrazolate
complex with ethylenediamine (4) with a suitable metal nitrate
and the thermal decomposition of these salts was studied later
on.12 The rst structural report of a salt containing the NTanion was that of a nickel(II) complex.13 It was not until the
beginning of this century that Zhilin et al.14 synthesized the
interesting tetrammine-cis-bis(nitro-2H-tetrazolato-N2 )cobalt(III)
perchlorate (BNCP) and Hiskey et al. patented salts of the
formula [Cat]z+ M2+ (NT)x (where Cat = NH4 , Na, K, Rb, Cs and
M = Fe, Co, Ni, Cu, Zn, Cr, Mn)15 and published their iron(II)
nitrotetrazolate salts hierarchy ([FeII NT3 ]- , [FeII NT4 ]2- , [FeII NT5 ]3and [FeII NT6 ]4- ).16 Some of these materials have found practical
applications. For example, NaNT has been used as a stand-alone
Butenandtstr. 513 (D), 81377 Munich, Germany. E-mail: tmk@cup.unimuenchen.de; Fax: +49 89 2180 77492; Tel: +49 89 2180 77491
CCDC reference number 704807. For crystallographic data in CIF or
other electronic format see DOI: 10.1039/b818900p

This journal is The Royal Society of Chemistry 2009

energetic material and as an additive in explosive and propellants

mixtures,17 whereas BNCP has found application in detonators
that are integral to the re suppression systems for military and
commercial aircrafts.14
We recently reported the synthesis of nitrogen-rich7,8 and
alkali metal18 salts with the NT- anion, which have interesting
properties as high-explosives and/or propellants and as initiators,
respectively. However, the preparation of such materials often
involves handling highly sensitive species with associated hazards. Silver 5-nitrotetrazolate (1) and copper(II) 5-nitrotetrazolate
5-nitrotetrazole dihydrate (2) are two of these highly sensitive
compounds. We envisioned 1 as a useful NT- anion transfer
reagent due to the high insolubility of silver halogenides in most
common solvents and also the readily precipitation of copper(II)
oxide should render 2 a useful starting material for the synthesis
of NT- salts. Unfortunately, the above mentioned high sensitivity
of the compounds would render up-scaling reactions pointing at
the synthesis of salts of NT unsafe, when using 1 or 2. In this
context we would like to present our results on the synthesis and
characterization of two ethylendiamine adducts, which are useful
and non-hazardous transfer reagents of the energetic NT- anion
as exemplied by the hereby reported alternative synthesis of the
5-aminotetrazolium and 1,3-dimethyl-5-aminotetrazolium salts.

Results and discussion

Synthesis
Silver 5-nitrotetrazolate (1) was prepared by precipitation
from the sodium salt (NaNT)18 and silver nitrate in water as a white, highly sensitive powder. Copper(II) 5nitrotetrazolate 5-nitrotetrazole dihydrate (2) was prepared as
a turquoise highly insoluble and highly sensitive powder from
Dalton Trans., 2009, 18351841 | 1835

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(1)

5-amino-1H-tetrazole (5-At) according to a known literature

procedure.19 Silver(ethylendiamine) 5-nitrotetrazolate (3) and
bis(ethylendiamine)copper(II) 5-nitrotetrazolate (4) were synthesized from NaNT by addition of an excess of ethylendiamine (en)
in hot ethanol and subsequent reux with an equivalent amount
of silver nitrate or copper(II) chloride, respectively. Slightly yellow
crystals of 3 precipitated upon cooling whereas 4, insoluble in hot
ethanol, separated from the hot reaction mixture as a lilac powder
(eqn (1)).
In addition, the reaction between NaNT and copper(II) sulfate
in ammonia led to the formation of a blue compound, which
separated as a powder upon cooling the reaction mixture. Elemental analysis of this solid pointed, somewhat unexpectedly,
at the formation of a copper complex containing three amino
ligands instead of the expected four and obeying to the formula
triaminocopper(II) 5-nitrotetrazolate (5, eqn (2)). Compound 5
might have either a square planar conguration completed by coordination to three ammonia ligands and one m1 -5-nitrotetrazolate
ligand or a distorted octahedron geometry with the ammonia
ligands and one chelate and one m1 -5-nitrotetrazolate ligands.

(2)
The ethylendiamine complexes 3 and 4 are readily soluble in
polar solvents such as DMSO, DMF and hot water (3 also in hot
ethanol) and in coordinating solvents (e.g., ammonia, pyridine,
ethylendiamine etc.) and insoluble in most other common solvents.
In contrast, compounds 1, 2 and 5 do not appreciably dissolve
neither in polar nor in less polar or apolar solvents (only 1 dissolves
slightly in acetonitrile).
As mentioned above both the silver and the copper ethylendiamine complexes (3 and 4, respectively) show promise because they
offer an alternative safer synthesis of previously reported com-

pounds such as tetrazolium 5-nitrotetrazolate salts 610 (eqn (3)).

Compounds 3 and 4 can be normally used like 1 and 2, respectively,
and the ethylendiamine ligand can be conveniently removed after
the reaction by applying a vacuum.
Spectroscopic discussion
Due to the broad NMR signals expected for copper(II) complexes
and the low solubility of the silver salt 1 in every solvent tried, we
only measured the NMR spectra for compound 3, which shows
proton resonances for the ligand (i.e., ethylendiamine) at d = 2.7
(CH2 ) and 3.4 (NH2 ) ppm. In the 13 C NMR, the resonance for
the ring carbon atom is found at d = 168.4 ppm, to low eld
in respect to that of metal salts of 5-amino-1H-tetrazole20 and
to high eld compared to that of metal salts containing the 5,5azotetrazolate anion,21 in keeping with nitrogen-rich salts with the
same anion.8 Additionally, the methylene carbon atom resonance
in 3 is observed at d = 43.3 ppm. The high symmetry in the anion
allows to distinguish the three expected nitrogen atom resonances
in the 14 N NMR spectrum. They are observed at d = +19 (N2/N3),
-21 (NO2 ) and -62 (N1/N4) ppm and are broad (n 1/2 ~420, 60 and
400 Hz, respectively).
The most signicant IR and Raman frequencies can be assigned
by comparison with the calculated values.8 The Raman spectra
of the complexes 3, 4 and 5 are dominated by three bands at
~1410, 1050 and 1030 cm-1 corresponding to the coupled (in
phase) NO2 and N1CN4 stretching, N1CN4 deformation and
NO2 stretching and to the asymmetric ring deformation modes,
respectively, observed as one strong and two weak/medium bands
at ~1420, 1050 and 1030 cm-1 in the IR spectra. On the other
hand, the spectra of the pure NT salts 1 and 2 are characterized
by an strong signal at ~1430 cm-1 (Raman), which has medium
intensity in the IR spectra (~1425 cm-1 ) and also correspond to a
coupled NO2 and N1CN4 stretching vibration. In addition, the
IR spectra are dominated by the nitro-group asymmetric stretching (~1540 cm-1 , 1565 cm-1 for compound 2), nitro-group and
N1CN4 (out of phase) symmetric stretching (~1320 cm-1 ) and

(3)

1836 | Dalton Trans., 2009, 18351841

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) and angles ( ) in 4
Table 1 Selected bond distances (A

Table 2 Geometry for the coordination around the copper cations in 4

Bond distances/A

Bond distances/A

C1N1
C1N4
C1N5
N1N2
N3N2
N4N3

1.327(2)
1.326(2)
1.441(2)
1.340(2)
1.335(2)
1.341(2)

O2N5
O1N5
N6C2
C3C2
N7C3

1.226(2)
1.236(2)
1.480(2)
1.517(2)
1.482(2)

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Bond angles/
C1N1N2
N3N2N1
N2N3N4
C1N4N3
N4C1N1
N4C1N5

103.0(1)
109.4(1)
109.9(1)
102.7(1)
115.0(1)
122.3(1)

N1C1N5
O2N5C1
O1N5C1
O1N5O2
N6C2C3
N7C3C2

122.6(1)
118.2(1)
117.7(1)
124.1(1)
107.5(1)
107.4(1)

CuN1
CuN6
CuN7

2.578(1)
2.018(1)
2.022(1)

CuN1i
CuN6i
CuN7i

2.578(1)
2.018(1)
2.022(1)

N1CuN6i
N7CuN1i
N6CuN7i
N1CuN1i
N7CuN7i
N6CuN6i

90.7(1)
88.8(1)
95.4(1)
180.0(1)
180.0(1)
180.0(1)

Bond angles/
N1CuN7
N1CuN6
N6CuN7
C2N6Cu
C3N7Cu
N1CuN7i
N7CuN6i

91.2(1)
89.3(1)
84.6(1)
109.0(1)
108.2(1)
88.8(1)
95.4(1)

Symmetry code: (i) 1 - x, -y, 1 - z.

the nitro-group and N1CN4 (in phase) deformation (~840 cm-1 )

modes.5c,22

Table 3 Selected hydrogen bonds for 4 (see Fig. 1 for labelling scheme)
DH A

DH/A

H A/A

D A/A

DH A/

Crystal structure of 4

N6H6B O1
N7H7A N3ii
N7H7B N3iii
N7H7B N4iii
N6H6A N4iv
N6H6A O2iv

0.88(2)
0.85(1)
0.87(1)
0.87(1)
0.84(2)
0.84(1)

2.29(1)
2.40(1)
2.42(1)
2.57(1)
2.41(1)
2.59(1)

3.083(2)
3.128(1)
3.282(1)
3.371(1)
3.199(2)
3.226(1)

149(2)
144(1)
168(1)
153(1)
158(2)
134(2)

The structure of compound 4 was determined by X-ray analysis

using an Oxford Xcalibur3 diffractometer with a Spellman generator (voltage 50 kV, current 40 mA) and a KappaCCD detector.
Suitable crystals were grown as described in the Experimental. The
data collection was performed using the CrysAlis CCD software,23
and the data reduction was performed with the CrysAlis RED
software.24 The structure was solved by direct methods using the
standard software implemented in the WinGX package2528 and
nally checked with PLATON.29 All non-hydrogen atoms were
rened anisotropically. All hydrogen atoms were located from
difference Fourier electron density maps and rened isotropically.
The absorptions were corrected with the SCALE3 ABSPACK
multi-scan method.30 Selected bond lengths and angles are reported in Table 1 and coordination around the copper atoms in
Table 2. In addition, hydrogen bonding geometries and graph-sets
are tabulated in Tables 3 and 4, respectively.

Structure renement of solution for compound 4: chemical formula:

C6 H16 N14 O4 Cu, M r = 411.87 g mol-1 , crystal system: orthorhombic, space
, b = 14.0124(2) A
, c = 14.7740(2) A
,a =b=
group: Pbca, a = 7.5200(1) A
3 , Z = 4, rcalcd = 1.757 g cm-3 , m = 1.455 mm-1 ,
g = 90 , V = 1556.78(4) A
F(000) = 844, q range: 3.8730.11 , T = 100(2) K, index range: -10
h 10, -19 k 19, -20 l 20, reections collected: 18 690, unique
reections: 2290, Rint = 0.0292, data/restraints/parameters: 2290/0/147,
GOF = 1.184, R1 [I > 4s(I)] = 0.0302, wR2 [I > 4s(I)] = 0.0606, R1 (all
data): 0.0448 and wR2 (all data): 0.0710.

Symmetry codes: (ii) -x + 3/2, y - 1/2, z; (iii) x + 1/2, -y + 1/2, -z + 1;

(iv) -x + 1/2, y - 1/2, z.

Compound 4 forms violet crystals, which arrange in an

orthorhombic cell in the space group Pbca and contain four
molecules in the unit cell. Half of the molecule can be generated
by symmetry (Fig. 1a, symmetry code: (i) 1 - x, -y, 1 - z) and the
copper atoms are surrounded by two ethylendiamine (en) moieties
and two anions with a total coordination number of six. The
en ligands are disposed in an envelope-type conformation with
the central copper atom with C3 and C2 pointing upwards and
downwards, respectively. The two ligands sit on the equatorial
to the metal, whereas the two anions
plane with distances ~2.02 A
to the central atom occupy the axial
with a distance of 2.578(1) A
positions (Fig. 1b). The geometry around the copper atom is that
of a slightly distorted octahedron with little JahnTeller effect
due to the high symmetry of the molecule (N1CuN1i =
N6CuN6i = N7CuN7i ~180 ). The geometry of the coordination around the metal centre is summarized in Table 2. The
maximum variations in the angles are found in the equatorial
plane where the angles are between 84.6(1) and 95.4(1) , whereas

Table 4 Graph-set table for 4 showing the unitary (diagonal) and secondary (off-diagonal) hydrogen bonding networks (see Fig. 1 for labelling scheme)

N6H6B O1 (A)
N7H7A N3ii (B)
N7H7B N3iii (C)
N7H7B N4iii (D)
N6H6A N4iv (E)
N6H6A O2iv (F)

D1,1(2)
C2,2(11)
R4,4(22)
R4,4(20)
R2,1(5)
C2,2(6)

D1,1(2)
R2,4(8)
R4,4(10)
C2,2(8)
C2,2(11)

D1,1(2)
R2,1(3)
R4,4(16)
C2,2(11)

D1,1(2)
R2,4(14)
C2,2(10)

D1,1(2)
C2,2(7)

D1,1(2)

Symmetry codes: (ii) -x + 3/2, y - 1/2, z; (iii) x + 1/2, -y + 1/2, -z + 1; (iv) -x + 1/2, y - 1/2, z.

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Dalton Trans., 2009, 18351841 | 1837

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Fig. 1 (a) Asymmetric unit showing the coordination around the copper atoms and (b) simplied coordination around the copper atoms in the crystal
structure of 4 (symmetry code: (i) 1 - x, -y, 1 - z).

the axial nitrogen atom (N1) forms angles between 88.8 and 91.2
with this plane. The distances for the coordination of the en
ligands to the copper atoms are comparable to those found
in copper salts of N,N,-bis-(1H-tetrazol-5-yl)-amine with amine
ligands,31 whereas those for the 5-nitrotetrazolate ring are between
common single and double bonds32 indicating delocalization of the
negative charge, in keeping with other crystallographic studies on
comparable compounds.7
Fig. 2 shows a view of the unit cell in 4. One host copper atom
is found at each corner and in each face (Z = 1/88 + 1/26 = 4)
forming a face centered cubic (fcc) unit cell and the axial axis of
the octahedrons are oriented (alternating along c) in two different
directions cutting the b axis at angles of 27.13(3) and -47.31(2) .
The two amino groups in the ligands participate in the formation
of medium to weak hydrogen bonds with the nitrotetrazolate ring
nitrogen atoms and the nitro-group oxygen atoms, which link
the octahedrons formed by the coordination around the copper
atoms together (Table 2). Fig. 3a shows the hydrogen bonding in

Fig. 2 View of the unit cell of 4 along the a axis (the hydrogen atoms have
been left out for simplicity).

1838 | Dalton Trans., 2009, 18351841

Fig. 3 (a) Hydrogen bonding in the structure of 4 (the copper atoms and
some of the hydrogen bonds have been omitted for simplicity). (b) View of
an R4,4(10) hydrogen bonding network. Symmetry codes: (i) 1 - x, -y, 1
- z; (ii) -x + 3/2, y - 1/2, z; (iii) x + 1/2, -y + 1/2, -z + 1; (iv) -x + 1/2,
y - 1/2, z; (v) 2 - x, -y, 1 - z; (vi) 1/2 + x, 1/2 - y, 1 - z; (vii) 1 - x, 1 - y,
1 - z; (viii) -1/2 + x, 1/2 - y, 1 - z; (ix) -x + 3/2, y + 1/2, z.

the structure of the compound. Both amino groups in the ligand

(N6H2 and N7H2 ) participate in the formation of three hydrogen
bonds so that in total six different (weak) hydrogen bonds are
found in the structure. The NT- anions interact via hydrogen
bonding by using all nitrogen atoms but N5,7,18 N1 (involved in
coordination to the copper cations) and N2. The next atom to
N2 is the hydrogen atom labelled as H6A (attached to N6) placed
, whereas the rest of the interactions summarized in
at 2.86(2) A
Table 3 have distances between the hydrogen and the acceptor
(sum of the van der Waals radii: rH + rN =
atoms below 2.6 A
).33
and rH + rO = 2.72 A
2.75 A
Using graph-set analysis as introduced by Bernstein34 the computer program RPLUTO35 allows to identify hydrogen bonding
patterns in molecules.8,36 The program nds the six hydrogen bonds
tabulated in Table 3 to form common dimmeric interactions of the
type D1,1(2) (Table 4). The hydrogen bond between N6 and O2iv
(symmetry code: (iv) -x + 1/2, y - 1/2, z) combines with the rest
at the secondary level to form exclusively chain motifs of the type
C2,2(X) where X = 6, 7, 10 and 11. The remainder of hydrogen
bonds interact forming (mainly) ring graph-sets of variable sizes,
which take the following labels: R2,1(X) (X = 3, 5), R2,4(X) (X =
8, 14) and R4,4(X) (X = 10, 16, 20, 22). Fig. 3b show some of
these hydrogen bonding networks. The R2,1(5) motif is formed
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Table 5 Physical properties and initial safety testing of the NT transition metal salts and comparison with lead azide

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Formula
MW
T m / Ca
T dec / Cb
N (%)c
X (%)d
Impact/Je
Friction/Ne
ESD ()f
Thermal shock

Pb(N3 )2

CN5 O2 Ag
221.91

273
31.56
-7.2
<1
<5
+
Explodes

C3 H5 N15 O8 Cu
441.47

230
51.66
-5.9
<3
<5
+
Explodes

C3 H8 N7 O2 Ag
282.01

212
34.77
-51.1
>40
<240
Explodes

C6 H16 N14 O4 Cu
411.83

225
47.62
-66.0
<7
<252
Explodes

C2 H9 N13 O4 Cu
342.02

245
53.22
-25.7
<2
<18
Explodes

N6 Pb
291.24

315360g
28.86
-5.5
2.54.0h
0.11.0h
+
Explodes

Melting point (DSC onset) from measurement with b = 5 C min-1 (NT salts) and from ref. 42 (lead azide). b Decomposition point (DSC onset) from
measurement with b = 5 C min-1 (NT salts) and from ref. 42 (lead azide). c Nitrogen content. d Oxygen balance, according to ref. 43. e Impact and friction
sensitivities determined by standard BAM methods (see ref. 3739). f Rough sensitivity to 20 kV electrostatic discharge (ESD), + sensitive, - insensitive
from an HF-Vacuum-Tester type VP 24. g Deagration point. h Values for technically pure compound.

by chelation of one of the amino group protons in the en ligand

; symmetry code:
(N6 N4iv = 3.199(2), N6 O2iv = 3.226(1) A
(iv) -x + 1/2, y - 1/2, z) whereas the R2,2(10) network is formed
by the side-on interaction of two NT- anions and two en ligands
; symmetry codes:
(N7 N3ii = 3.128(1), N7 N4iii = 3.371(1) A
(ii) -x + 3/2, y - 1/2, z; (iii) x + 1/2, -y + 1/2, -z + 1) and they
both have been observed before in nitrogen-rich NT salts.8
Energetic properties
In order to assess the energetic properties of the NT salts, the thermal stability (decomposition points from DSC measurements),
sensitivity to friction, impact, electrostatic discharge and thermal
shock of each material was experimentally determined (Table 5).
DSC measurements made on samples of ~1 mg of each energetic
compound in this study, show no melting points and high thermal
stabilities above 210 C, which are above those values for nitrogenrich salts with the same anion.8 In addition to DSC analysis, all
compounds were tested by placing a small sample (~0.51.0 mg)
of compound in the ame. In all ve cases this resulted in a loud
explosion. Commonly used primary explosives such as AgN3 and
Pb(N3 )2 also explode upon rapid heating. The data collected for
friction, impact and electrostatic discharge sensitivity testing are
also summarized in Table 5.3739 The compounds in this study
are (in general) signicantly more sensitive to friction and impact
than known nitrogen-rich salts of the NT- anion,7,8 similar to
other metal salts with the same anion.18,40,41 Also, each compound
was roughly tested for sensitivity to electrostatic discharge (ESD
testing) by spraying sparks across a small (35 crystals) sample
of material using a Tesla coil (~20 kV electrostatic discharge
from an HF-Vacuum-Tester type VP 24). The sensitivity towards
electrostatic discharge seems to correlate well with the sensitivity
towards friction and the most friction sensitive compounds 1 and
2 gave a positive test whereas the en adducts (3 and 4) and the
copper complex 5 failed to explode. From these results it seems
like the en adducts (3 and 4) are safer to handle than the pure
5-nitrotetrazolate salts (1 and 2), which puts into perspective
their potential as NT- anion transfer reagents (see Discussion
above and Experimental). Note that, interestingly, compound 5
can be easily initiated by impact, similar to lead azide (both
~2 J)42 but is much less sensitive to friction, which has led to many
accidental explosions associated with the use of lead azide in the
This journal is The Royal Society of Chemistry 2009

past. In addition, a radiation of ~300 mW can be used to detonate

compound 5 (copper salt 2 also explodes under these conditions).
Lastly, from the sensitivity values reported here it can be derived
that 1 and 2 fall under the category of primary explosives, i.e., they
can easily be initiated by impact, friction or heat. On the other
hand, 3 is safe for transport under the UN recommendations on
the transport of dangerous goods,39 whereas the diethylenamine
adduct 4 is much less sensitive to impact and friction than copper
salt 2. Also compound 5 can easily be initiated by impact and an
X-ray beam and therefore, this material has potential as a safer
and more environmentally-friendly alternative to lead-based salts
in initiating systems.

Experimental
Caution!
All compounds described here are energetic materials, which might
explode under certain conditions. Although we had no difculties
during the preparation and handling of the compounds described
below, they are nevertheless powerful explosives and their synthesis
should be carried out by experienced personnel, specially that of
compounds 1, 2 and 5. In any case, proper protective measures
such as Kevlar gloves, ear protection, safety shoes and plastic
spatulas, should be taken at all times especially when working on
a large scale (>1 g).
General
All chemical reagents and solvents of analytical grade were obtrained from Sigma-Aldrich Inc. and used as supplied. 5-Amino1H-tetrazolium bromide44 and 1,3-dimethyl-5-aminotetrazolium
iodide7a were prepared according to literature procedures. 1 H, 13 C
and 14 N NMR spectra were recorded on a JEOL Eclipse 400
instrument. The spectra were measured in DMSO-d6 at 25 C.
The chemical shifts are given relative to tetramethylsilane (1 H,
13
C) or nitromethane (14 N) as external standards. Infrared (IR)
spectra were recorded on a Perkin-Elmer Spectrum One FT-IR
instrument as KBr pellets at room temperature.45 Raman spectra
were recorded on a Perkin-Elmer Spectrum 2000R NIR FTRaman instrument equipped with a Nd:YAG laser (1064 nm).
The intensities are reported in percentages relative to the most
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intense peak and are given in parentheses. Elemental analyses were

performed with a Netsch Simultanous Thermal Analyzer STA
429. Melting points were either determined using a melting point
apparatus (uncorrected) or by differential scanning calorimetry
(Linseis DSC PT-10 instrument, calibrated with standard pure
indium and zinc).46 Measurements were performed at a heating
rate of b = 2 C min-1 in closed aluminium containers with a hole
(1 mm) on the top for gas release with a nitrogen ow of 20 mL
min-1 . The reference sample was a closed aluminium container.
Silver 5-nitrotetrazolate (1). Sodium 5-nitrotetrazolate dihydrate (0.173 g, 1.00 mmol)9 was dissolved in 10 mL water and a
small excess of silver nitrate was added portion-wise (0.187 g,
1.10 mmol) causing the precipitation of a white powder. The
reaction mixture was carefully stirred for 30 min under the
exclusion of light and the insoluble solid was ltered off, washed
with water and left to air dry (0.212 g, 95%). CN5 O2 Ag (221.91 g
mol-1 , calcd/found): C 5.41/5.22, H/0.04, N 31.56/31.42, Ag
48.61/48.25%; DSC (5 C min-1 / C): 273 (dec.); m/z (FAB- ,
xenon, 6 keV, m-NBA matrix): 114.0 [CN5 O2 ]- . Raman (relative intensities) n /cm-1 : 1567(5), 1432(100), 1414(50), 1330(21),
1203(32), 1089(34), 1070(58), 1017(12), 837(18), 738(2), 545(9),
256(2), 168(7). IR (KBr, relative intensities) n /cm-1 : 1648 (w),
1537 (vs), 1508 (w), 1446 (m), 1422 (s), 1384 (m), 1319 (m), 1187
(w), 1170 (w), 1060 (w), 1050 (w), 1035 (w), 841 (m), 669 (w), 476
(w).
Copper(II) 5-nitrotetrazolate 5-nitrotetrazole dihydrate (2). A
small amount of 2 was isolated during the synthesis of sodium 5nitrotetrazolate dihydrate18 and carefully analyzed. C3 H5 N15 O8 Cu
(441.97 g mol-1 , calcd/found): C 8.14/7.91, H 1.14/1.29, N
47.52/47.41, Cu 14.24/13.88%; DSC (5 C min-1 / C): ~230 (dec.).
Raman (relative intensities) n /cm-1 : 3063(2), 2822(26), 1885(30),
1871(33), 1435(100), 1130(56), 776(44), 420(46). IR (KBr, relative
intensities) n /cm-1 : 3565 (s), 3478 (m), 1614 (w), 1565 (vs), 1445
(m), 1435 (m), 1384 (m), 1328 (m), 1236 (w), 1065 (w), 842 (s), 664
(w), 565 (w), 475 (w).
Silver(ethylendiamine) 5-nitrotetrazolate (3). Sodium 5nitrotetrazolate dihydrate (0.173 g, 1.00 mmol) was dissolved
in 5 mL ethanol and a solution of ethylendiamine (0.085 g,
1.41 mmol) in 2 mL ethanol was added at 60 C. The solution
was heated to boiling and a saturated solution of silver nitrate
(0.170 g, 1.00 mmol) in 10 mL hot ethanol was added slowly. The
solution turned brown immediately and it was stirred at reux for
2.5 h. After this time, the brown precipitate formed was ltered
and discarded yielding a clear colourless solution from which
crystals separated out upon cooling (0.221 g, 78%). C3 H8 N7 O2 Ag
(282.01 g mol-1 , calcd/found): C 12.78/12.68, H 2.86/2.77, N
34.77/34.59, Ag 38.25/37.91%; DSC (5 C min-1 / C): 108.1
(-en), ~212 (dec.); m/z (FAB+ , xenon, 6 keV, m-NBA matrix):
60.1 [Ag(en)]+ ; m/z (FAB- , xenon, 6 keV, m-NBA matrix):
114.0 [CN5 O2 ]- ; 1 H NMR (DMSO-d6 , 400.18 MHz, 25 C,
TMS) d/ppm: 3.4 (s, 4H, NH2 ), 2.7 (s, 4H, CH2 ); 13 C{1 H} NMR
(DMSO-d6 , 100.63 MHz, 25 C, TMS) d/ppm: 168.4 (1C, C-NT),
43.3 (2C, CH2 ); 14 N{1 H} NMR (DMSO-d6 , 40.55 MHz, 25 C,
MeNO2 ) d/ppm: +19 (2 N, n 1/2 ~420 Hz, N2/3), -21 (1 N, n 1/2
~60 Hz, NO2 ), -62 (2 N, n 1/2 ~400 Hz, N1/4). Raman (relative
intensities) n /cm-1 : 3284(3), 2986(36), 2946(5), 2877(1), 1600(3),
1534(7), 1453(6), 1444(6), 1407(100), 1371(7), 1309(5), 1239(4),
1840 | Dalton Trans., 2009, 18351841

1161(5), 1121(3), 1069(5), 1050(36), 1029(43), 1003(5), 845(5),

832(9), 769(2), 537(3), 449(3), 262(3), 239(5). IR (KBr, relative
intensities) n /cm-1 : 3427 (s), 3308 (s), 1587 (m), 1543 (s), 1484
(m), 1444 (m), 1419 (m), 1384 (m), 1318 (m), 1172 (w), 1078 (w),
1001 (w), 840 (m), 670 (w), 522 (w).
Bis(ethylendiamine)copper(II) 5-nitrotetrazolate (4). Sodium
5-nitrotetrazolate dihydrate (0.177 g, 1.02 mmol) was dissolved
in 10 mL ethanol and a solution of ethylendiamine (0.100 g,
1.67 mmol) in 5 mL ethanol was added dropwise under stirring
at room temperature. The solution was heated to 70 C and
a solution of copper(II)chloride (0.068 g, 0.51 mmol) in 5 mL
ethanol was added causing immediate precipitation of a bluelilac solid. The reaction mixture was boiled for 1 h and the lilac
precipitate was ltered and boiled again in fresh ethanol. Lastly, it
was ltered, washed with boiling ethanol and ether and left to air
dry yielding the title compound (0.163 g, 77%). Crystals suitable
for X-ray analysis were obtained when an aqueous solution
of the compound was left to slowly evaporate. C6 H16 N14 O4 Cu
(411.83 g mol-1 , calcd/found): C 17.51/17.37, H 3.92/3.84, N
47.69/47.85, Cu 15.31/15.02%; DSC (5 C min-1 , C): ~225 (dec.);
m/z (FAB+ , xenon, 6 keV, m-NBA matrix): 183.2 [Cu(en)2 ]2+ ;
m/z (FAB- , xenon, 6 keV, m-NBA matrix): 114.1 [CN5 O2 ]- ;
Raman (relative intensities) n /cm-1 : 3282(3), 2956(4), 1605(4),
1535(7), 1460(8), 1442(6), 1407(100), 1319(7), 1284(5), 1174(3),
1155(4), 1113(7), 1054(42), 1032(44), 886(10), 862(3), 839(12),
774(2), 537(6), 476(8), 448(3), 299(7), 245(15). IR (KBr, relative
intensities) n /cm-1 : 3450 (s), 3331 (vs), 3278 (s), 3154 (m), 2979
(m), 2966 (m), 2893 (w), 2439 (w), 1593 (m), 1537 (vs), 1504 (w),
1459 (w), 1441 (s), 1410 (s), 1384 (m), 1316 (m), 1281 (w), 1268
(w), 1172 (w), 1155 (w), 1084 (w), 1053 (w), 1033 (s), 969 (w), 839
(m), 719 (w), 669 (w), 536 (m), 471 (w).
Triaminocopper(II) 5-nitrotetrazolate (5). Sodium 5-nitrotetrazolate dihydrate (0.346 g, 2.00 mmol) was dissolved in 3 mL
of ammonia 35% and slowly added to a solution of copper(II)
sulfate (0.160 g, 1.00 mmol) in 3 mL ammonia 35%. After
reuxing the reaction mixture for 15 min and stirring for further
1 h at room temperature, a blue solid precipitated that was
washed with water and ethanol and left to air dry (0.269 g,
79%). C2 H9 N13 O4 Cu (342.02 g mol-1 , calcd/found): C 7.02/7.07,
H 2.65/2.75, N 53.22/53.38, Cu 18.40/18.12%; DSC (5 C
min-1 / C): ~245 (dec.); m/z (FAB+ , xenon, 6 keV, m-NBA matrix):
177.6 [Cu(CN5 O2 ]+ ; m/z (FAB- , xenon, 6 keV, m-NBA matrix):
114.1 [CN5 O2 ]- , 405.7 [Cu(CN5 O2 )3 ]- . Raman (relative intensities)
n /cm-1 : 3351(3), 3282(12), 1540(10), 1445(15), 1416(100), 1317(6),
1236(2), 1098(10), 1056(52), 1031(37), 839(14), 772(3), 536(5),
449(4), 415(5), 264(4). IR (KBr, relative intensities) n /cm-1 : 3355
(s), 3278 (m), 2846 (w), 1612 (m), 1538 (vs), 1504 (w), 1442 (s),
1427 (m), 1416 (s), 1384 (m), 1318 (s), 1264 (s), 1247 (s), 1213 (w),
1186 (w), 1151 (w), 1054 (w), 1034 (w), 1021 (w), 840 (s), 772 (w),
701 (m), 684 (m), 667 (m), 534 (w).
5-Amino-1H-tetrazolium 5-nitrotetrazolate (6). An improved
method to that reported in ref. 6 is presented here. 5-Amino1H-tetrazolium bromide (110 mmol) was dissolved in water
and added to a suspension of 3 (1.0 equiv.) in the same solvent.
Immediate precipitation of yellow silver bromide was observed and
the reaction mixture was stirred for 0.52.0 h under the exclusion
of light. After this time the solvent was carefully evaporated
This journal is The Royal Society of Chemistry 2009

View Article Online

under vacuum and at 50 C leaving an off-white solid behind

(quantitative yield). C2 H4 N10 O2 (200.12 g mol-1 , calcd/found): C
12.00/11.73, H 2.01/1.72, N 69.99/69.45%; m.p. (uncorrected):
157.0158.7 C (literature: 159 C).

Published on 27 January 2009. Downloaded by RMIT Uni on 24/08/2014 12:59:01.

1,3-Dimethyl-5-aminotetrazolium 5-nitrotetrazolate (8). An

improved method to that reported in ref. 7a is presented here.
Compound 8 was obtained as described for 6 from 1,3-dimethyl5-aminotetrazolium iodide and 3 in an improved 94% yield.
C4 H8 N10 O2 (228.17 g mol-1 , calcd/found): C 21.05/20.84, H
3.53/3.32, N 61.39/61.07%; m.p. (uncorrected): 160.0161.4 C
(literature: 160.5 C).

Conclusions
The synthesis and characterization of two very sensitive transition
metal 5-nitrotetrazole (NT) salts (1 and 2) and that of the
corresponding adducts with ethylendiamine (3 and 4) is presented.
Compounds 1 and 2 have proofed to be very useful starting
materials for the synthesis of NT salts, however, their increased
sensitivity makes their use on a larger scale problematic. Compounds 3 and 4 are introduced here as safer NT- anion transfer
reagents and the potential of 3 for the synthesis of tetrazolium salts
is exemplied. In addition, we have prepared a copper complex
with amino ligands containing the NT- anion (5), which can be
easily initiated by impact and by laser induction and offers a safer
and more environmentally friendly alternative to commonly used
compounds (e.g., lead azide).

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