Binary bismuth(III) azides: Bi(N3)3 , [Bi(N 3)4]-, and [Bi(N3)6] 3-

Article abstract of DOI:10.1002/anie.201002179

Nitrogen finally meets bismuth: The synthesis of binary bismuth(III) azides Bi^III(N₃)₃, [Bi^III(N ₃)₄]^-, and [Bi^III(N ₃)₆]^3- along with

Full text of DOI:10.1002/anie.201002179

Angewandte
Chemie
DOI: 10.1002/anie.201002179
Bismuth Azides
Binary Bismuth(III) Azides: Bi(N3)3 , [Bi(N3)4]À, and [Bi(N3)6]3À**
Alexander Villinger* and Axel Schulz*
Binary azides of Group 15 elements form a class of highly
endothermic compounds. Whereas numerous binary azides of
the heavier Group 15 elements arsenic and antimony have
been reported and characterized, such as As(N3)3,[1]
[As(N3)4]+,[2]
[As(N3)4]À,[2]
As(N3)5,[3]
[As(N3)6]À,[2,4]
Sb(N3)3,[1c,5] [Sb(N3)4]+,[2] [Sb(N3)4]À,[2] Sb(N3)5,[3] and
[Sb(N3)6]À,[2,3] no binary bismuth azides have been isolated
to date. In the only report on binary bismuth triazide, the
authors assumed the formation of Bi(N3)3 in the reaction of
BiI3 with AgN3 in acetonitrile on the basis of IR data, but they
were not able to isolate Bi(N3)3 from the reaction mixture.[6]
Crystal structures of binary Group 15 azides are only
known for AsIII(N3)3,[1c] SbIII(N3)3,[1c] [AsV(N3)6]À,[4] and
[SbV(N3)6]À,[3] but no experimentally observed structural
data are available for binary bismuth azides and Group 15
azides of the type [E(III)(N3)4]À (E = pnictogen).
Scheme 1. Synthesis of 1.
solvent from the filtrate in vacuo gives Bi(N3)3·THF as a
colorless solid in low yields. The solvent molecule cannot be
removed at elevated temperatures in vacuo.
An improved synthesis starts from bismuth trifluoride
(BiF3) and an excess trimethylsilylazide (Me3SiN3) in THF,
and also yields Bi(N3)3·THF (yield > 98%). Solvent-free 1
(Figure 1) can be isolated when this reaction is carried out in
The energetic azido moiety adds about 70 kcalmolÀ1 to
the energy content of a molecule.[7] Thus we started the search
À
for high-nitrogen-content Bi N compounds with the synthesis
of bismuth triazide. In a second series of experiments, the
synthesis of binary tetra-, penta-, and hexaazido bismuth
compounds, which are highly endothermic polyazide com-
pounds, was carried out in which the energy content increases
with an increasing number of azido ligands. Following our
interest in Group 15 element nitrogen compounds with a high
nitrogen content,[8] we describe herein the synthesis, isolation,
and full characterization of binary tri-, tetra-, and hexaazido
bismuth compounds for the first time.
Figure 1. Calculated C3-symmetric structure of the lowest-lying isomer
of 1 in the gas phase. Selected bond lengths [ꢀ] and angles [8]: Bi–N1
2.195, N1–N2 1.234, N2–N3 1.143; N1-Bi-N1’ 98.1, N2-N1-Bi 120.1,
N3-N2-N1 175.5.
The synthesis of the binary compound Bi(N3)3 (1) was first
achieved in the reaction of a solution of bismuth triiodide
(BiI3) in tetrahydrofuran (THF) and neat, carefully dried
silver azide (AgN3) at ambient temperature (Scheme 1). The
resulting yellow suspension was stirred for two hours, result-
ing in an off-white suspension (mixture of AgI and 1).
Removal of solvent and drying in vacuo gives a pale brownish
residue. The major problem is the isolation of 1 from this
residue. The isolation procedure includes re-suspension and
extraction of the residue in THF at 508C. Finally, removal of
acetonitrile (Scheme 1). Both pure 1 and 1·THF are obtained
as colorless polycrystalline solids, which are not suitable for
single-crystal structure elucidation, and were characterized by
IR and Raman spectroscopy (Table 1). Although elemental
analysis was successfully carried out for 1·THF, an attempted
elemental analysis for pure 1 resulted in a violent detonation
within the apparatus. Both species 1 and 1·THF are air-stable
but hygroscopic and almost insoluble in common polar and
unpolar solvents, such as SO2, C6H6, THF, CH2Cl2, and
CH3CN. Azide 1·THF is heat- but not shock-sensitive and is
thermally stable up to over 2488C, whilst shock-sensitive 1
can only be heated to 1548C. At this temperature, a heavy
detonation occurs, releasing a green cloud of smoke.
[*] Dr. A. Villinger, Prof. Dr. A. Schulz
Universitꢁt Rostock, Institut fꢂr Chemie
Albert-Einstein-Strasse 3a, 18059 Rostock (Germany)
and
Leibniz-Institut fꢂr Katalyse e.V. an der Universitꢁt Rostock
Albert-Einstein-Strasse 29a, 18059 Rostock (Germany)
Fax: (+49)381-498-6382
E-mail: alexander.villinger@uni-rostock.de
axel.schulz@uni-rostock.de
Two synthetic routes are feasible to isolate salts
containing the binary [BiIII(N3)4]À ion (Figures 2 and 3).
1) (PPh4)[Bi(N3)4] (2) is readily obtained in the reaction of
1·THF with one equivalent of (PPh4)N3 in either THF,
CH2Cl2, or CH3CN, yielding yellow suspensions from which
2 was isolated as crystalline material (yield > 95%) in THF or
CH3CN, whereas 2·CH2Cl2 was isolated from the CH2Cl2
solution. The dichloromethane can be completely removed
by prolonged drying in vacuo at 608C (yield > 95%). The use
Homepage: http://www.chemie.uni-rostock.de/ac/schulz
[**] L. Knꢃpke and J. Thomas are gratefully acknowledged for Raman
and Dr. D. Michalik for NMR spectroscopy measurements.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201002179.
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8017

Communications
Table 1: Selected IR/Raman data [cmÀ1] and approximate assignment,[a] melting points/decomposition temperature [8C], and selected NPA partial
charges q [e].[b]
Bi(N3)3 (1)
(PPh4)[Bi(N3)4] (2)
(PPh4)3[Bi(N3)6](3)
n˜NN as,ip
n˜NN as,op
n˜NN s,ip
n˜NN s,op
,
,
,
,
2118(m)/2115(4)
2094(m),2051(s)/2084(1),2046(6)
1325(m)/1334(6)
1260(m)/1280(3)
2055(m,br)/2086(6)
2017(s,br)/2061(1),2035(8),2019(2)
1312(s)/1325(3)
1264(s)/1266(1)
650(s),641(s),614(m),599(m)/
651(1),640(1),614(1)
–/337(4)
–/318(2),286(2),249(1)
147/267
+1.71
2055(m)/2063(2)
1994(s,br)/2025(1),2007(1)
1312(s)/1325(3)
1261(m)/1264(3)
635(m),615(m)/
637(1),618(2)
–/396(1)
–/322(3),293(2),258(2)
179/285
+1.90
dNNN
655(w),646(m),602(w),589(w), 578(w)/
655(4),608(3)
–/395(4)
–/341(10)
–/154[c]
n˜BiÀN,ip
n˜BiÀN,op
m.p./Tdec
q(Bi)
+1.70
q(Na)
q(Nb)
À0.71
À0.68
À0.61
+0.22
+0.22
+0.22
q(Ng)
À0.08
À0.23
À0.43
[a] as=asymmetric, ip=in-phase, op=out-of-phase. [b] NPA natural population analysis.[9] [c] 1·THF: Tdec =2488C.
2·CH2Cl2 are also isolated as yellow crystals. (PPh4)[Bi(N3)4]
is less sensitive than Bi(N3)3 and does not explode. Both
azides were fully characterized by 14N NMR, IR, and Raman
spectroscopy, elemental analysis, and single-crystal structure
elucidation. Yellow crystals of 2 melt at 1478C and decom-
pose at 2548C without detonation. According to DSC
measurements, 2·CH2Cl2 releases CH2Cl2 at 1078C (1 atm),
forming pure 2 (Scheme 2).
Figure 2. ORTEP representation of the anion of 2 in the crystal at
173 K (thermal ellipsoids set at 50% probability). Selected bond
lengths [ꢀ] and angles: N1–Bi 2.377(2), N4–Bi 2.449(2), N7–Bi
2.291(2), N10–Bi 2.273(2), N1–N2 1.216(3), N7–N8 1.207(3), N4–N5
1.198(3), N10–N11 1.209(3), N2–N3 1.144(3), N5–N6 1.144(4),
N8–N9 1.148(4), N11–N12 1.149(3); N3-N2-N1 177.5(3), N6-N5-N4
178.5(3), N9-N8-N7 177.6(3), N12-N11-N10 176.7(3), N8-N7-Bi
114.7(2), N5-N4-Bi 122.9(2), N11-N10-Bi 115.4(2), N10-Bi-N7
86.95(9), N10-Bi-N1 80.46(8), N7-Bi-N1 86.64(9), N10-Bi-N4 83.06(8),
N7-Bi-N4 80.30(8), N1-Bi-N4 159.45(8).
Scheme 2. Synthesis of 2.
By reaction of (PPh4)[BiIII(N3)4] with two equivalents of
(PPh4)N3, the (PPh4)3[BiIII(N3)6] salt (3) is formed in almost
quantitative yield and was fully characterized (Table 1,
Figure 4). The reaction of [PPh4]3[BiIIII6] with AgN3 also
yields pure 3 (Scheme 3). Yellow crystalline 3 is neither heat-
nor shock-sensitive and melts at 1798C; decomposition starts
at 2858C. It is interesting to note that the attempted synthesis
of a salt containing the pentaazide anion [BiIII(N3)5]2À led to
the formation of a mixture of [BiIII(N3)4]À and [BiIII(N3)6]3À in
a 1:1 ratio (see the Supporting Information).
Table 1 summarizes the characterization of azides 1–3.
Two well-resolved 14N NMR signals were found in the spectra
run in different solvents (CH2Cl2, CH3CN, DMSO)[10] at 300 K
for 2 and 3, while it was not possible to obtain NMR data for 1
owing to its low solubility. As expected, both 14N spectra in
DMSO solution show a sharp signal at d = À136 (2, Du =
43 Hz) and À134 ppm (3, Du = 42 Hz) for the Nb atoms and a
medium-sharp signal at d = À253 (2, Du = 480 Hz) and
À260 ppm (3, Du = 390 Hz) for the Ng atoms in accord with
known values for covalently bound azido groups.[1–7,11] The
Figure 3. Section of the chain composed of [Bi(N3)4]À units in the
crystal. Symmetry codes: (’) Àx+2, Ày, Àz+2; (’’) Àx+1, Ày, Àz+2.
À
Three types of significantly different Bi N bond lengths are observed:
a) Bi–N10 2.273(2), Bi–N7 2.291(2); b) Bi-N1 2.377(2), Bi–N4
2.449(2); c) Bi–N1’ 2.684(2), Bi–N4’’ 2.717(2).
of 1·THF instead of pure 1 for the synthesis of 2 has the
advantage that it is less sensitive and thus minimizes the
danger of explosion. 2) By adding four equivalents of AgN3 to
a solution of (PPh4)[BiI4][10] in either THF or CH2Cl2, 2 and
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equatorial nitrogen atoms (15.1%) of the pseudo-trigonal
À
bipyramid, indicating larger covalent character for the Bi N
bonds within the trigonal plane. In 3, only 6–7% of the
À
electron density of the Bi N bonds is found at the bismuth
atom, indicating a predominantly ionic bonding situation for
all six azido ligands attached to the bismuth atom.
The charge distribution for all three azides is character-
ized by alternating net charges along the Bi(d+)–N(dÀ)–N(d+)
–
N(dÀ) units, with a large positive charge at the bismuth atom (1
+ 1.70, 2 + 1.71, 3 + 1.90 e; Table 1). A closer look at the
À
charges reveals that upon further N3 complexation, the
charge at the Bi, Na, and Nb atoms does not change much,
whilst the terminal Ng atoms feature a significantly larger
negative charge (1 À0.08, 2 À0.23, 3 À0.43 e).
Figure 4. ORTEP representation of the anion of 3 in the crystal at
173 K (thermal ellipsoids set at 50% probability). Selected bond
lengths [ꢀ] and angles [8]: Bi–N1 2.487(2), Bi–N4 2.32(2), Bi–N7
2.364(2), Bi–N10 2.478(2), Bi–N13 2.331(2), Bi–N16 2.719(5), N1–N2
1.188(3), N4–N5 1.27(3), N7–N8 1.194(3), N10–N11 1.188(3), N13–
N14 1.203(3), N2–N3 1.149(3), N5–N6 1.10(2), N8–N9 1.140(3),
N11–N12 1.158(3), N14–N15 1.150(3), N17–N18 1.19(2); N1-Bi-N4
94.4(5), N1-Bi-N10 89.03(7), N1-Bi-N13 85.59(7), N1-Bi-N16 108.8(2),
N4-Bi-N7 86.8(5), N4-Bi-N13 84.3(4), N4-Bi-N16 78.2(4), N7-Bi-N10
88.53(7), N7-Bi-N13 88.47(7), N7-Bi-N16 77.4(2), N10-Bi-N13
84.10(7), N10-Bi-N16 111.9(1), N1-Bi1-N7 173.78(8), N4-Bi-N10
167.6(4), N13-Bi1-N16 158.8(2), N2-N1-Bi 119.5(2), N5-N4-Bi
124.5(1), N8-N7-Bi 123.2(2), N11-N10-Bi 120.7(2), N14-N13-Bi
119.1(2), N17-N16-Bi 133.4(9), N3-N2-N1 177.0(3), N6-N5-N4
177.5(2), N9-N8-N7 175.8(2), N12-N11-N10 177.6(3), N15-N14-N13
177.2(2).
As it was not possible to obtain experimental structural
data, the structure of 1 was calculated for the gas phase at the
B3LYP level of theory. For nitrogen, a standard 6-31G(d)
basis set was used and a quasi-relativistic pseudopotential
(ECP78MWB) and a (4s4p1d)/[2s2p1d] basis set for the
bismuth atom. The lowest-lying C3 symmetric isomer with the
three azido ligands in an anti configuration with respect to the
lone pair (Figure 1) was characterized as a minimum at the
potential energy surface by a frequency analysis. It can be
assumed that in the solid state owing to strong intermolecular
interactions, such as in E(N3)3 (E = As, Sb), a three-dimen-
sional network also exists.[1c] As shown on numerous occa-
sions, the azido groups are almost linear, with N-N-N angles
of 175.58.[1–7,11] The tetrahedral angles at the bismuth atom
decrease from an ideal value of 109.58 to 98.18.
(PPh4)[Bi(N3)4] crystallizes in the monoclinic space group
P21/c with four formula units per cell, whereas
(PPh4)[Bi(N3)4]·CH2Cl2 crystallizes in the triclinic space
¯
group P1 with two formula units per cell. As the structural
parameters for both compounds are very similar, we focus
only on the data for (PPh4)[Bi(N3)4]. The asymmetric unit
consists of separated (PPh4)+ and [Bi(N3)4]À units with no
significant cation–anion contacts. The [Bi(N3)4]À ion
(Figure 2) adopts a distorted bisphenoidal geometry with
Scheme 3. Synthesis of 3.
observation of only one set of azide signals and the absence of
the Na signal indicates strong quadrupole relaxation effects
and a rapid ligand exchange on the NMR timescale.[12]
The vibrational spectra of all three azides feature the
presence of covalently bonded azido ligands, as shown by the
asymmetrical stretching mode in the range 2200–2000 cmÀ1,
the symmetrical stretching mode at 1400–1200 cmÀ1, and the
deformation mode at 700–600 cmÀ1. The bismuth Bi–N
stretching modes are found in the range 400–250 cmÀ1 (cf.
352 cmÀ1 in Me2BiN3).[13] The presence of more than one
azido ligand results in in-phase and out-of-phase coupling.
The most prominent structural feature in all three
bismuth(III) azides is the stereochemically active lone pair
localized according to NBO analysis[9] in a mainly s-type
atomic orbital. The s character of the lone pair (Table 1)
increases in the order 1 (87.6%) < 2 (88.5%) < 3 (99.5%). All
À
À
two shorter (Bi N10 2.273(2), Bi N7 2.291(2) ꢀ) and two
À
À
À
longer Bi N bonds (Bi N1 2.377(2), Bi N4 2.449(2) ꢀ;
[14]
À
ꢀrcov(Bi N) = 2.2 ꢀ),
in accord with the valence-shell
electron-pair repulsion model. Both N7 and N10 are part of
the trigonal plane with a N7-Bi-N10 angle of 86.95(9)8,
whereas N1 and N4 sit on the axis with an N1-Bi-N4 angle of
159.45(8)8. For all four azido ligands, the typical trans-bent
structure with N-N-N angles of about 176–1798 is observed.[11]
À
The Na Nb bonds are in the range 1.198(3)–1.216(3) ꢀ
À
(average 1.207 ꢀ), and an average Nb Ng bond length of
1.146 ꢀ is observed.[11]
A closer look at the interanionic interactions (Figure 3)
reveals an expansion of the bismuth coordination number by
the formation of nitrogen bridges involving the a-nitrogen
atoms (N1, N4) of two of the azido ligands. This bridging
mode results in the formation of four-membered rings
composed of two hexacoordinated bismuth and two bridging
Na atoms. These rings are interconnected, with adjacent rings
almost perpendicular to each other, thus forming infinite
À
of the Bi N bonds are highly polarized and can be considered
dominantly ionic. The degree of polarization increases in the
À
order 1 < 2 < 3. Although all three Bi N bonds in 1 are
localized to 19.7% at the bismuth atom, in bisphenoidal 2
there is a considerable difference between the nitrogen atoms
occupying the axial positions (8.5%) compared to the
À
zigzag chains in the crystal. The Bi Nbridge bonds amount to
’
À
À
Bi N1 2.684(2) and Bi N4’’ 2.717(2) ꢀ, which are consid-
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Communications
[2] K. Karaghiosoff, T. M. Klapꢁtke, B. Krumm, H. Nꢁth, T.
Schmitt, M. Suter, Inorg. Chem. 2002, 41, 170 – 179.
[3] R. Haiges, J. A. Boatz, A. Vij, V. Vij, M. Gerken, S. Schneider, T.
Schroer, M. Yousufuddin, K. O. Christe, Angew. Chem. 2004,
116, 6844 – 6848; Angew. Chem. Int. Ed. 2004, 43, 6676 – 6680.
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[6] T. M. Klapꢁtke, A. Schulz, Main Group Chem. 1997, 20, 325 –
339.
erably shorter than the sum of the van der Waals radii of
4.0 ꢀ.[14]
(PPh4)3[Bi(N3)6] crystallizes in the monoclinic space group
P21/n with four formula units per cell. The asymmetric unit
consists of one (PPh4)3[Bi(N3)6] unit without significant
cation–anion contacts and two disordered azido ligands.
Figure 4 shows the structure of the [Bi(N3)6]3À ion with a
strongly distorted BiN6 skeleton. It is well-known that
bismuth atoms can accommodate at least six closely packed
halide ligands, as in octahedral [BiIIIX6]3À (X = F, Cl, Br, I),
whilst for the [BiVX6]À ion, only the fluorine species is
known.[15] In contrast to the known pseudohalide complexes
[EV(N3)6]À, with E = P, As, Sb, the analogous bismuth com-
pound has not been reported, whilst for E = P, As, and Sb, the
trivalent [Bi(N3)6]3À analogues remain unknown.
[7] R. Haiges, J. A. Boatz, A. Vij, M. Gerken, S. Schneider, T.
Schroer, K. O. Christe, Angew. Chem. 2003, 115, 6027 – 6031;
Angew. Chem. Int. Ed. 2003, 42, 5847 – 5851.
[8] a) A. Schulz, A. Villinger, Inorg. Chem. 2009, 48, 7359 – 7367;
b) W. Baumann, A. Schulz, A. Villinger, Angew. Chem. 2008,
120, 9672 – 9675; Angew. Chem. Int. Ed. 2008, 47, 9530 – 9532;
c) D. Michalik, A. Schulz, A. Villinger, N. Weding, Angew.
Chem. 2008, 120, 6565 – 6568; Angew. Chem. Int. Ed. 2008, 47,
6465 – 6468; d) A. Schulz, A. Villinger, Angew. Chem. 2008, 120,
614 – 617; Angew. Chem. Int. Ed. 2008, 47, 603 – 606; e) P. Mayer,
A. Schulz, A. Villinger, Chem. Commun. 2006, 1236 – 1238; f) S.
Herler, A. Villinger, P. Mayer, A. Schulz, J. J. Weigand, Angew.
Chem. 2005, 117, 7968 – 7971; Angew. Chem. Int. Ed. 2005, 44,
7790 – 7793.
[9] a) Computational details are given in the Supporting Informa-
tion; b) E. D. Glendening, A. E. Reed, J. E. Carpenter, F.
Weinhold, NBO Version 3.1; c) J. E. Carpenter, F. Weinhold,
J. Mol. Struct. 1988, 169, 41 – 62; d) F. Weinhold, J. E. Carpenter,
The Structure of Small Molecules and Ions, Plenum, London,
1988, 227; e) F. Weinhold, C. Landis, Valency and Bonding. A
Natural Bond Orbital Donor–Acceptor Perspective, Cambridge
University Press, 2005, and references therein.
[10] a) Synthesis and full characterization, including X-ray structure
elucidation of (PPh4)[BiI4]; b) the full set of experimental data
for all of the bismuth azides considered can be found in the
Supporting Information.
[11] I. C. Tornieporth-Oetting, T. M. Klapꢁtke, Angew. Chem. 1995,
107, 559 – 568; Angew. Chem. Int. Ed. Engl. 1995, 34, 511 – 520.
[12] R. S. Berry, J. Chem. Phys. 1960, 32, 933 – 940.
[13] J. Mꢂller, Z. Anorg. Allg. Chem. 1971, 381, 103 – 115.
[14] Holleman Wiberg, Lehrbuch der Anorganischen Chemie, 102nd
Edition, Walter de Gruyter, Berlin, 2007, Appendix IV (in
German).
À
Interestingly, in 3 there is one significantly elongated Bi
À
N bond of 2.719(5) for Bi N16, whilst the other five bonds are
all in the range 2.32–2.49 ꢀ, in accord with those found in 2.
À
À
The Bi N16 bond compares well with the length of the Bi N
bridges in 2 (see above).
The electronic structure of [BiIII(N3)6]3À is best compared
to the [TeIV(N3)6]2À ion, which also features a sterically active
lone pair causing a strongly distorted octahedral symmetry of
the EN6 skeleton (E = Te, Bi).[16] Similar hexacoordinate
azido species are neutral W(N3)6,[17] singly negatively charged
[As(N3)6]À,[2,4] [Sb(N3)6]À,[3] [Nb(N3)6]À,[18] and [Ta(N3)6]À,[18]
and doubly negatively charged [Si(N3)6]2À [19] [Ge(N3)6]2À,[20]
,
and [Se(N3)6]2À.[21] However, for these species an almost
perfect S6 symmetry with an octahedral skeleton is observed.
In conclusion, we present herein the first synthesis and
isolation of binary bismuth(III) azides and their full charac-
terization. Although the structural elucidation of [BiIII(N3)4]À
and [BiIII(N3)6]3À salts fills a gap in main group chemistry,
Bi(N3)3·THF could qualify as a precursor for the generation of
binary BiN in detonation experiments owing to its low shock
and heat sensitivity.
Experimental Section
Caution! Covalent azides are potentially hazardous and can decom-
pose explosively under various conditions! In particular, Bi(N3)3
described herein is extremely shock-sensitive and can explode
violently upon the slightest provocation. Appropriate safety precau-
tions (safety shields, face shields, leather gloves, protective clothing)
should be taken, particularly when dealing with larger quantities.
Experimental details are found in the Supporting Information.[10]
[15] Holleman Wiberg, Lehrbuch der Anorganischen Chemie, 102nd
Edition, Walter de Gruyter, Berlin, 2007, p. 836 (in German).
[16] R. Haiges, J. A. Boatz, S. Schneider, T. Schroer, M. Yousufuddin,
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Keywords: azides · bismuth · natural bond orbitals ·
pseudohalogens · structure elucidation
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