Mono- and diazides of bismuth

Article abstract of DOI:10.1021/om1009796

Bis[2-((dimethylamino)methyl)phenyl]azidobismuthane, [2-(Me ₂NCH₂)C₆H₄]₂BiN ₃, and [2-((dimethylamino)methyl)phenyl]diazidobismuthane, [2-(Me₂NCH₂)C₆H₄]Bi(N ₃)₂, were synthesized and fully characterized. [2-(Me ₂NCH₂)C₆H₄]₂BiN ₃ and [2-(Me₂NCH₂)C₆H ₄]Bi(N₃)₂ represent rare examples of bismuth azides. The structures of both azide compounds were determined by single-crystal X-ray diffraction. While for the monoazide [2-(Me₂NCH ₂)C₆H₄]₂BiN₃ a monomeric species was found, the diazide [2-(Me₂NCH₂)C ₆H₄]Bi(N₃)₂ dimerizes in the solid state, exhibiting two bridging azido groups. Furthermore, weak van der Waals interactions between these centrosymmetric dimers lead to a chainlike structure in the crystal.

Full text of DOI:10.1021/om1009796

284 Organometallics 2011, 30, 284–289
DOI: 10.1021/om1009796
Mono- and Diazides of Bismuth
Axel Schulz*,†,‡ and Alexander Villinger*,†
†
€
€
Universitat Rostock, Institut fur Chemie, Albert-Einstein-Str.3a, 18059 Rostock, Germany, and
‡Leibniz-Institut fu€r Katalyse e.V. an der Universita€t Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
Received October 13, 2010
Bis[2-((dimethylamino)methyl)phenyl]azidobismuthane, [2-(Me2NCH2)C6H4]2BiN3, and [2-((di-
methylamino)methyl)phenyl]diazidobismuthane, [2-(Me2NCH2)C6H4]Bi(N3)2, were synthesized
and fully characterized. [2-(Me2NCH2)C6H4]2BiN3 and [2-(Me2NCH2)C6H4]Bi(N3)2 represent rare
examples of bismuth azides. The structures of both azide compounds were determined by single-
crystal X-ray diffraction. While for the monoazide [2-(Me2NCH2)C6H4]2BiN3 a monomeric species
was found, the diazide [2-(Me2NCH2)C6H4]Bi(N3)2 dimerizes in the solid state, exhibiting two
bridging azido groups. Furthermore, weak van der Waals interactions between these centrosym-
metric dimers lead to a chainlike structure in the crystal.
Introduction
gen compounds with a high nitrogen content,11 we describe
here the synthesis, isolation, and full characterization of diorga-
nomonoazido and organodiazido bismuth compounds.
Azides of group 15 elements form a class of highly
endothermic compounds. Numerous binary azides of the
heavier group 15 elements arsenic and antimony have been
reported and characterized (As(N3)3,1 [As(N3)4]þ,2 [As(N3)4]-,2
As(N3)5,3 [As(N3)6]-,2,4 Sb(N3)3,1c,5 [Sb(N3)4]þ,2 [Sb(N3)4]-,2
Sb(N3)5,3 [Sb(N3)6]-). Only recently binary bismuth azides
of the type Bi(N3)3, [Bi(N3)4]-, and [Bi(N3)6]3- been reported.6
There is little known about organobismuth azides. As early
as 1934 Challenger and Richards described the formation of
Ph3Bi(N3)2, which was obtained in the reaction of Ph3BiCl2 and
NaN3.7 When it is heated to 100 °C, Ph3Bi(N3)2 decomposes to
give Ph2BiN3. Almost 40 years later Me2BiN3 was observed in
the reaction of Me3Bi with HN3 and structurally charac-
terized.8 Dehnicke studied BiON3 obtained from Bi(NO3)3
and NaN3 in water by means of IR spectroscopy.9 Ph3Bi(I)N3
was observed when IN3 was added to a solution of Ph3Bi.10
We started the search for high-nitrogen-content organo-
bismuth-nitrogen compounds with mono- and diazido species,
which are additionally stabilized by an aryl organic group
bearing a donor Me2N donor function ([2-(Me2NCH2)-
C6H4]-). Following our interest in group 15 element nitro-
Results and Discussion
Synthesis. Ligands with the potential for supplemental
Lewis base interactions such as 2-((dimethylamino)methyl)-
phenyl12 are finding increasing utility for the stabilization of
electrophilic main-group species such as trivalent compounds of
the general formulas REX2 and R2EX (E = P, As, Sb, Bi;
R = [2,6-(Me2NCH2)2C6H3]; X = halogen).13 For the synthe-
sis of diorgano and monoorgano bismuth azide compounds
the 2-((dimethylamino)methyl)phenyl group was chosen,
which has already been successfully used for the generation
of halogeno compounds [2-(Me2NCH2)C6H4]2BiX and
[2-(Me2NCH2)C6H4]BiX2 (X = Cl, I), respectively.14-16
(11) (a) Schulz, A.; Villinger, A. Inorg. Chem. 2009, 48, 7359–7367.
(b) Baumann, W.; Schulz, A.; Villinger, A. Angew. Chem. 2008, 120,
9672-9675; Angew. Chem., Int. Ed. 2008, 47, 9530-9532. (c) Michalik,
D.; Schulz, A.; Villinger, A.; Weding, N. Angew. Chem. 2008, 120,
6565-6568; Angew. Chem., Int. Ed. 2008, 47, 6465-6468. (d) Schulz, A.;
Villinger, A. Angew. Chem. 2008, 120, 614-617; Angew. Chem., Int. Ed.
2008, 47, 603-606. (e) Mayer, P.; Schulz, A.; Villinger, A. Chem.
Commun. 2006, 1236–1238. (f) Herler, S.; Villinger, A.; Mayer, P.; Schulz,
A.; Weigand, J. J. Angew. Chem. 2005, 117, 7968-7971; Angew. Chem.,
Int. Ed. 2005, 44, 7790-7793.
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4389–4391. (c) Klein, K. P.; Hauser, C. R. J. Org. Chem. 1967, 32, 1479–1483.
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A. L.; Schoone, J. C. J. Organomet. Chem. 1978, 148, 233–245. (b) Cowley,
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F. P.; Jones, R. A.; Carrano, C. J.; Bond, M. R. J. Organomet. Chem. 1995, 489,
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R. J. Organometallics 1995, 14, 2400–2406. (e) Cowley, A. H.; Gabbai, F. P.;
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*Corresponding authors. E-mail: axel.schulz@uni-rostock.de.
€
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19953365–3366. (b) Geissler, P.; Klapotke, T. M.; Kroth, H.-J. Spectrochim.
Acta, Part A 1995, 51, 1075–1078. (c) Haiges, R.; Vij, A.; Boatz, J. A.; Schneider,
S.; Schroer, T.; Gerken, M.; Christe, K. O. Chem. Eur. J. 2004, 10, 508–517.
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r
pubs.acs.org/Organometallics
Published on Web 12/27/2010
2010 American Chemical Society

Article
Organometallics, Vol. 30, No. 2, 2011 285
Scheme 1. Synthesis of 1
Scheme 2. Synthesis of 2
Since the azido group should be introduced by an iodide-azide
exchange reaction, in a first reactionstepbis[2-((dimethylamino)-
methyl)phenyl]iodobismuthane, [2-(Me2NCH2)C6H4]2BiI
(1), and [2-((dimethylamino)methyl)phenyl]diiodobismuthane,
[2-(Me2NCH2)C6H4]BiI2 (2) were respectively prepared
(Schemes 1 and 2).
Both compounds 1 and 2 can easily be generated via the
chloro species.14-16 Compound 1 is obtained when, to a
stirred suspension of BiCl3, a suspension of [2-((dimethyl-
amino)methyl)phenyl]lithium, [2-(Me2NCH2)C6H4]Li, was
added in one portion at -80 °C followed by a chlorine-
iodine exchange (Scheme 1). The synthesis of 2 starts
from tris[2-((dimethylamino)methyl)phenyl]bismuthane, [2-
(Me2NCH2)C6H4]3Bi (3),14 which is obtained when BiCl3 is
treated with a suspension of [2-((dimethylamino)methyl)-
phenyl]lithium, [2-(Me2NCH2)C6H4]Li (Scheme 2). Reac-
tion of 3 with 2 equiv of BiCl3 results in the formation of
[2-(Me2NCH2)C6H4]BiCl2, which is easily transformed into
the diiodo 2 species by a chlorine-iodine exchange.
The reactions of [2-(Me2NCH2)C6H4]2BiI and [2-
(Me2NCH2)C6H4]BiI2 with a stoichiometric amount of sil-
ver azide, AgN3, in tetrahydrofuran (THF) solution at
ambient temperature result in complete iodide-azide exchange
and yield clear, colorless solutions of bis[2-((dimethyl-
amino)methyl)phenyl]azidobismuthane, [2-(Me2NCH2)C6H4]2-
BiN3 (4), and [2-((dimethylamino)methyl)phenyl]diazidobis-
muthane, [2-(Me2NCH2)C6H4]Bi(N3)2 (5), respectively
(Scheme 3). Filtration and removal of the solvent leads to
the isolation of pure 4 and 5 in very good yields (4, 87%; 5,
98%). Azide formation in 4 and 5 can easily be detected by
means of IR spectroscopy (νas(N3) 2022 (4), 2022 cm-1 (5))
and 14N NMR spectroscopy. Two well-resolved 14N NMR
resonances were found in the spectra run in different solvents
(due to low solubility) at 300 K for 4 (DMSO) and 5 (THF).
As expected, both 14N solution spectra show a sharp signal
at δ -134 (4, Δν = 77 Hz) and -134 (5, Δν = 53 Hz) ppm for
the Nβ atoms (cf. Bi(N3)4- at -136 ppm (Δν = 43 Hz)) and
a medium-sharp resonance at δ -275 (4, Δν = 570 Hz)

286 Organometallics, Vol. 30, No. 2, 2011
Scheme 3. Synthesis of 4 (n = 2, x = 1) and 5 (n = 1, x = 2)
Schulz and Villinger
Figure 1. ORTEP drawing of the molecular structure of 1 in the
crystal form. Thermal ellipsoids are shown at the 50% probability
level, at 173 K. Selected bond lengths (A) and angles (deg): Bi-
C10 = 2.259(2), Bi-C1 = 2.265(2), Bi-N1 = 2.522(2), Bi-I =
3.078(1); C10-Bi-C1 = 95.02(8), C10-Bi-N1 = 92.95(7),
C1-Bi-N1 = 73.50(7), C10-Bi-I = 87.83(6), C1-Bi-I =
94.46(6), N1-Bi-I = 167.96(4).
Figure 2. ORTEP drawing of the molecular structure of 3 in the
crystal form. Thermal ellipsoids are shown at the 50% probability
level, at 173 K. Selected bond lengths (A) andangles(deg):Bi1-C1=
2.272(3), Bi1-C19 = 2.276(3), Bi1-C10 = 2.279(3), Bi-N1 =
3.052(3), Bi-N2 = 3.021(3), Bi-N3 = 3.074(2); C1-Bi1-C19 =
91.7(1), C1-Bi1-C10 = 95.5(1), C19-Bi1-C10 = 92.5(1).
˚
˚
-
and -262 (5, Δν = 390 Hz) ppm for the Nγ atoms (cf. Bi(N3)4
at -253 (Δν = 480 Hz) ppm), in accord with known lit-
erature values for polar covalently bound azido groups.6,17
The observation of only one set of azide signals and the absence
of the NR resonance indicate strong quadrupole relaxation
effects and a rapid ligand exchange on the NMR time scale.18
The degree of polarity can be studied with the help of the shift
for the Nγ atom, which indicates a larger degree of ionicity of
the Bi-N3 bond for 4 due to a better intrinsic (donor-
acceptor) stabilization of the R2Biþ fragment (cf. 4 (-275 ppm)
< 5 (-262 ppm) < Bi(N3)4- (-252 ppm)).6
Neither the mono- nor the diazide are heat or shock
sensitive, and both are thermally stable to over 155 °C
(4, 158 °C; 5, 159 °C). At this temperature decomposition
starts without explosion. Both species are air-stable and
soluble in common polar and nonpolar solvents. Compounds 4
and 5 can be prepared in bulk and are stable for long periods
when stored in a sealed tube.
X-ray Structure Analysis. The solid-state structures of the
starting materials 1-3 are known.15,14,16 For comparison,
and since we obtained considerably better data sets for 1 and
especially for 3, we include our structural data (for 1 and 3) in
the discussion. The molecular structures of 1 and 3 are shown
in Figures 1 and 2 (details are given in Table S1 in the
Supporting Information), and of the azide species 4 and 5
in Figures 3 and 4, respectively, along with selected bond
lengths and angles. Crystallographic details are given in
Table 1. More details are found in the Supporting Information.
Figure 3. ORTEP drawing of the molecular structure of 4 in
the crystal form. Thermal ellipsoids are shown at the 50%
˚
probability level, at 173 K. Selected bond lengths (A) and angles
(deg): Bi1-C10 = 2.244(3), Bi1-C1 = 2.248(3), Bi1-N1 =
2.413(2), Bi1-N5 = 2.555(2), Bi-N4 = 3.131(3), N1-N2 =
1.193(4), N2-N3 = 1.157(4), N4-C9 = 1.453(5), N4-C7 =
1.470(4), N4-C8 = 1.479(4), N5-C17 = 1.465(4), N5-C18 =
1.468(4), N5-C16 = 1.474(4); C10-Bi1-C1 = 95.1(1), C10-
Bi1-N1 = 87.3(1), C1-Bi1-N1 = 83.6(1), C10-Bi1-N5 =
73.01(9), C1-Bi1-N5 = 92.75(9), N1-Bi1-N5 = 159.58(9),
N2-N1-Bi1 = 120.6(2), N3-N2-N1 = 177.6(3).
[2-(Me2NCH2)C6H4]2BiI (1) crystallizes in the monoclinic
space group P21/n with four formula units per cell. The
structure consists of separated [2-(Me2NCH2)C6H4]2BiI
molecules with no significant intermolecular contacts.15
€
(17) Tornieporth-Oetting, I. C.; Klapotke, T. M. Angew. Chem.
1995, 107, 559-568; Angew. Chem., Int. Ed. 1995, 34, 511-520.
(18) Berry, R. S. J. Chem. Phys. 1960, 32, 933–940.
Only weak C-H I interactions are found. Formally, the
3 3 3

Article
Organometallics, Vol. 30, No. 2, 2011 287
Table 1. Crystallographic Details of Azides 4 and 5
4
5
chem formula
formula wt
color
C
18H24BiN5
C18H24Bi2N14
854.47
colorless
monoclinic
P21/c
11.895(6)
7.544(4)
14.235(8)
1244.3(12)
2
519.40
colorless
monoclinic
P21/n
8.558(4)
16.135(7)
13.864(6)
1914.3(15)
4
1.802
9.219
0.710 73
173(2)
8505
4154
3566
0.0197
1000
0.0198
0.0464
1.020
cryst syst
space group
˚
a (A)
˚
b (A)
˚
c (A)
3
V (A )
˚
Z
F
calcd (g cm-3
)
2.281
μ (mm-1
)
14.159
0.710 73
173(2)
18 391
4494
3882
0.0395
792
˚
Mo KR (A)
λ
T (K)
no. of measd rflns
no. of indep rflns
no. of rflns with I > 2σ(I )
Rint.
F(000)
R1 (R(F2 > 2σ(F2)))
0.0201
0.0503
1.051
wR2(F2)
GOF
no. of params
Figure 4. ORTEP drawing of the molecular structure of 5 in the
crystal form. Thermal ellipsoids are shown at the 50% prob-
221
156
˚
ability level, at 173 K. Selected bond lengths (A) and angles
both independent molecules of 3 possess approximate C3
symmetry. The primary coordination sphere consists of a
trigonal-pyramidal BiC3 skeleton with three secondary inter-
actions between the pendant amines and the bismuth center.
(deg):Bi-C1= 2.249(2), Bi-N2= 2.295(2), Bi-N5= 2.387(2),
Bi-N1 = 2.568(2), Bi-N50 = 2.726(2), N1-C9 = 1.462(4),
N1-C8 = 1.471(4), N1-C7 = 1.473(4), N2-N3 = 1.156(3),
N3-N4 = 1.159(3), N5-N6 = 1.199(3), N6-N7 = 1.143(3);
C1-Bi-N2 = 91.62(8), C1-Bi-N5 = 89.19(9), N2-Bi-N5 =
84.53(8), C1-Bi-N1 = 72.34(9), N2-Bi-N1 = 82.14(8), N5-
Bi-N1 = 156.79(7), C1-Bi-N50 = 88.35(8), N2-Bi-N50 =
152.43(7). N5;Bi-N50=67.90(8), N1-Bi-N50=123.78(7), N3-
N2-Bi = 123.9(2), N6-N5-Bi = 115.7(2), N6-N5-Bi0 =
125.4(2), Bi-N5-Bi0 = 112.10(8), N2-N3-N4 = 176.4(3), N7-
N6-N5 = 178.9(3). Symmetry code (0): -x þ 1, -y þ 1, -z þ 2.
˚
While the average Bi-C bond length of 2.276 A lies in
P
the range of a typical covalent bond (cf. rcov(Bi-C) =
17
2.27 A), the Bi N distances between 3.02 and 3.08 A
˚
˚
3 3 3
indicate only van der Waals interactions; however, these
contacts are slightly shorter compared to that found in 1 at
˚
3.158(2) A and are significantly longer compared to the short
Bi-N1 donor-acceptor bond in 1 (d(Bi-N1) = 2.522 (2) A;
see Figures 1 and 2).
˚
The monoazide 4 crystallizes in the monoclinic space
group P21/n with four formula units per cell. The asymmetric
unit consists of a [2-(Me2NCH2)C6H4]2BiN3 molecule. As
depicted in Figure 3, the BiC2N2 core of 4 is distorted
bisphenoidal with a N1-Bi-N5 angle of 159.58(9)° and a
C1-Bi-C10 angle of 95.09(1)°. As already discussed, two
significantly different Bi-NMe2 distances with d(Bi1-N5) =
central bismuth atom is tetracoordinated (Figure 1); however,
˚
the Bi-I distance amounts to 3.078(1) A, which is rather
P
long compared to the sum of the covalent radii rcov
19
-
˚
(Bi-I) = 2.83 A.
In BiI3(s) a Bi-I distance of
3.07 A is found with Bi in an octahedral environment
20
˚
21
˚
(cf. 2.807(6) A in BiI3(g)). Hence, an ionic situation as
found for BiI3(s),22 that is, [R2Bi]þ[I]-, might also be dis-
cussed. Here the [R2Bi]þ cation is stabilized by an additional
Bi-N1 donor-acceptor bond with one of the adjacent
NMe2 groups, as indicated by a short Bi-N1 distance
˚
˚
˚
2.555(2) A (cf. 1 at 2.522(2) A) and d(Bi-N4) = 3.131 A (cf. 1
˚
at 3.158(2) A and 3 at an average of 3.049 A) are observed,
˚
displaying a strong donor-acceptor bond for Bi-N5 and a
P
van der Waals contact for Bi-N4 (cf. rvdW(Bi-N) = 4.0
P
17
17
˚
˚
˚
(d(Bi-N1) = 2.522 (2), cf.
r
cov(Bi-N) = 2.2 A). This
A). The Bi-Nazide distance (d(Bi-N1) = 2.413(2) A)
P
Bi-N1 bond is considerably longer than the sum of the
represents the shortest Bi-N bond length in 4 (cf. rcov
-
P
˚
covalent radii
than the sum of the van der Waals radii
r
cov(Bi-N) but still significantly shorter
(Bi-N) = 2.2 A). Similar structural features are found for
P
the [Bi(N3)4]- ion, which also adopts a distorted-bisphenoi-
rvdW(Bi-N) =
4.0 A. For the second NMe2 moiety only weak van der
17
˚
˚
dal geometry with two shorter (2.273(2) and 2.291(2) A) and
6
˚
Waals interactions can be assumed, since the Bi-N2 distance
two longer Bi-N bond lengths (2.377(2) and 2.449(2) A). As
shown on numerous occasions,23 covalently bound azide
groups such as in 4 display a trans-bent configuration
(regarding the Bi atom, Bi-NNN) with N-N-N bond
˚
is found at 3.158(2) A. The angles around the trigonal-
pyramidal Bi center are all between 75 and 95° (C1-Bi-
N1 = 73.50(7) to C10-Bi-C1 = 95.02(8)°).
Compound 3 crystallizes in the space group P21 with four
molecules per unit cell and two independent molecules per
asymmetric unit.14 Although not required crystallographically,
€
(23) For example: (a) Muller, U. Chem. Ber. 1977, 110, 788–791.
(b) Roesky, H. W.; Noltemeyer, M.; Sheldrick, G. M. Z. Naturforsch., B
1986, 41, 803–807. (c) Schomburg, D.; Wermuth, U.; Schmutzler, R. Chem.
Ber. 1987, 120, 1713–1718. (d) Cowley, A. H.; Gabbai, F.; Schluter, R.;
Atwood, D. J. Am. Chem. Soc. 1992, 114, 3142–3144. (e) Englert, U.;
Paetzold, P.; Eversheim, E. Z. Kristallogr. 1993, 208, 307–309. (f) Cowley,
A. H.; Gabbai, F. P.; Bertrand, G.; Carrano, C. J.; Bond, M. R. J. Organomet.
(19) Holleman Wiberg. Lehrbuch der Anorganischen Chemie, 102nd
ed.; Walter de Gruyter: Berlin, 2007; Suppl. IV.
(20) Trotter, J.; Zobel, T. Z. Kristallogr. 1966, 123, 67–72.
(21) Molnar, J.; Kolonits, M.; Hargittai, M.; Konings, R. J. M.;
Booij, A. S. Inorg. Chem. 1996, 35, 7639–7642.
(22) Margaritondo, G.; Stoffel, N. G.; Levy, F. Solid State Commun.
1979, 29, 797–799.
€
Chem. 1995, 493, 95–99. (g) Larbig, M.; Nieger, M.; v. d. Gonna, V.; Ruban,
A. V.; Niecke, E. Angew. Chem., Int. Ed. Engl. 1995, 34, 460–462.
(h) Schranz, I.; Grocholl, L. P.; Stahl, L.; Staples, R. J.; Johnson, A. Inorg.
Chem. 2000, 39, 3037–3041.

288 Organometallics, Vol. 30, No. 2, 2011
Schulz and Villinger
for the first time. While the monoazide compound 4 crystal-
lizes as a [2-(Me2NCH2)C6H4]2BiN3 molecule with no sig-
nificant intermolecular contacts, the diazido species can be
best described as a polymer of weakly bound centrosym-
metric dimers. In both azide compounds one strong intra-
molecular donor-acceptor interaction between the bismuth
center and the nitrogen atom of one adjacent NMe2 moiety is
observed. Moreover, for 4 only very weak van der Waals
interactions can be assumed between the second NMe2 group
and the Bi center. If this second (weak) intramolecular NfBi
interaction is considered, the overall coordination becomes
distorted square pyramidal ((C,N)2BiN3 core); otherwise, it
is distorted bisphenoidal. For 5 a distorted-octahedral environ-
ment can be discussed.
Figure 5. View of the molecular structure of 5 showing the
chains of dimers.
angles of 177.6(3) and 120.6(2)° along the N2-N1-Bi
moiety.
Experimental Section
Diazido compound 5 crystallizes in the monoclinic space
group P21/c with four formula units per cell. The asymmetric
unit consists of a [2-(Me2NCH2)C6H4]Bi(N3)2 molecule;
however, in contrast to 4 it has significant symmetric inter-
General Information. All manipulations were carried out
under oxygen- and moisture-free conditions under argon using
standard Schlenk or drybox techniques.
=
molecular interactions (d(Bi-N50)
2.726(2) A) leading
˚
Dichloromethane was purified according to a literature pro-
cedure,27 dried over P4O10, and freshly distilled prior to use.
Tetrahydrofuran (THF), toluene, and diethyl ether were dried
over Na/benzophenone and freshly distilled prior to use. n-Pentane
and n-hexane were dried over Na/benzophenone/tetraglyme
and freshly distilled prior to use. Ethanol was freshly distilled
prior to use. Bismuth triiodide, BiI3 (99%, Merck), was dried at
120 °C prior to use. Bismuth trichloride (BiCl3; 99%, anhy-
drous, Alfa Aesar), NaI (Fluka, 99%), silver nitrate (AgNO3;
99%, VEB Feinchemie Sebnitz), sodium azide (99%, Acros),
and tetraphenylphosphonium iodide ([Ph4P]I; 99%, Aldrich)
were used as received. Silver azide (AgN3) was dried at 70 °C for
several days prior to use. [2-((Dimethylamino)methyl)phenyl]-
lithium ([2-(Me2NCH2)C6H4]Li) was prepared according to
literature procedures;12 bis[2-((dimethylamino)methyl)phenyl]-
chlorobismuthane ([2-(Me2NCH2)C6H4]2BiCl),14 bis[2-((dimethyl-
amino)methyl)phenyl]iodobismuthane ([2-(Me2NCH2)C6H4]2-
BiI),15 tris[2-((dimethylamino)methyl)phenyl]bismuthane ([2-
(Me2NCH2)C6H4]3Bi),16 [2-((dimethylamino)methyl)phenyl]-
dichlorobismuthane ([2-(Me2NCH2)C6H4]BiCl2),14 and [2-
((dimethylamino)methyl)phenyl]diiodobismuthane ([2-(Me2-
NCH2)C6H4]Bil2)14 have been reported previously and were
prepared according to modified procedures.
to the formation of a centrosymmetric {[2-(Me2NCH2)-
C6H4]2BiN3}2 dimer (Figure 4). Moreover, these dimers
interact further via a weak symmetric interaction involving
17
P
00
˚
˚
N2 (d(Bi N2 ) = 3.080(2) A; cf. rvdW(Bi-N) = 4.0 A),
3 3 3
as shown in Figure 5; if these interactions are considered, the
overall Bi coordination geometry is strongly distorted octa-
hedral. Hence, the crystal structure of 5 can be described as a
weakly bound polymer of more strongly bound centrosym-
metric dimers. Also, for the [Bi(N3)4]- ion an expansion of
the Bi coordination number by the formation of nitrogen
bridges involving R-nitrogen atoms of two of the azido ligands is
observed, leading to infinite zigzag chains in the crystal. Here
˚
the Bi-Nbridge distances amount to 2.684(2) and 2.717(2) A,
respectively.6 Oligomeric structures have been previously
reported for bismuth halides of the type [{2-(6-Me)-
C5H3N}NSiMe3]BiCI24 and several heteroleptic and homo-
leptic bismuth(III) amidinate halide complexes.25,26
The [2-(Me2NCH2)C6H4]Bi(N3)2 molecule adopts a dis-
torted-bisphenoidal geometry. Upon dimerization via N5 a
˚
planar Bi2N2 ring with two shorter (d(Bi-N5) = 2.387(2) A)
0
˚
13C{1H}, 13C DEPT, and 1H NMR spectra were obtained on
a Bruker AVANCE 500 spectrometer and were referenced
internally to the deuterated solvent (13C: CD2Cl2, δreference 54
ppm; C4D8O, δreference 67.2 ppm) or to protic impurities in the
deuterated solvent (1H: CDHCl2, δreference 5.31 ppm; C4D7HO,
and two longer Bi-N bond lengths (d(Bi-N5 ) = 2.568(2) A;
P
˚
cf. rcov(Bi-N) = 2.2 A) is formed, which represents the
most prominent structural feature.17 The shortest Bi-N
˚
bond length is found for Bi-N2 at 2.295(2) A (cf. 4 at
˚
2.413(2) A). The Bi-NMe2 donor-acceptor bond
˚
δ
reference 3.57 ppm). CD2Cl2 was dried over P4O10, and C4D8O
(d(Bi-N1) = 2.568(2) A) is in the range of those found for
was dried over Na/benzophenone. IR spectra were obtained on
a Nicolet 380 FT-IR spectrometer with a Smart Orbit ATR
device. Raman spectra were obtained on a Bruker VERTEX 70
FT-IR spectrometer with a RAM II FT-Raman module, equipped
with a Nd:YAG laser (1064 nm). Solid samples were sealed off in
small glass tubes. CHN analyses were obtained with an Analy-
sator Flash EA 1112 instrument from Thermo Quest or a C/H/
N/S-Mikronalysator TruSpec-932 from Leco. Melting points
are uncorrected (EZ-Melt, Stanford Research Systems). The
heating rate was 20 °C/min (clearing points are reported). DSC
measurements were obtained on a DSC 823e instrument from
Mettler-Toledo (heating rate 5 °C/min). MS was obtained on
a Finnigan MAT 95-XP instrument from Thermo Electron.
HRMS was obtained on a 6210 time-of-flight LC/MS instru-
ment from Agilent Technologies (MeOH/0.1% HCOOH in
H2O 90/10).
˚
˚
4 (2.555(2) A) and 1 (2.522(2) A), respectively. For both
azido ligands the typical trans-bent structure with NNN
angles of about 176-179° is observed. The NR-Nβ bonds
˚
range between 1.156(3) and 1.199(3) A, and Nβ-Nγ bond
˚
lengths between 1.159(3) and 1.143(3) A are found, in accord
with our expectation.1-6
Conclusion
New organobismuth(III) monoazido and diazido com-
pounds containing the supplemental Lewis base arm ligand
2-(Me2NCH2)C6H4 were prepared and fully characterized
(24) Raston, C. L.; Skelton, B. W.; Tolhurst, V.-A.; White, A. H.
Polyhedron 1998, 935–942.
(25) Brym, M.; Forsyth, C. M.; Jones, C.; Junk, P. C.; Rose, R. P.;
Stascha, A.; Turner, D. R. Dalton Trans. 2007, 3282–3288.
€
(26) Lyhs, B.; Schulz, S.; Westphal, U.; Blaser, D.; Boese, R.; Bolte,
(27) Fischer, C. B.; Xu, S.; Zipse, H. Chem. Eur. J. 2006, 12, 5779–
M. Eur. J. Inorg. Chem. 2009, 2247–2253.
5784.

Article
X-ray Structure Determination. X-ray-quality crystals were
Organometallics, Vol. 30, No. 2, 2011 289
284 (2), 264 (4), 221 (1), 201 (4), 180 (5), 157 (6), 132 (2), 114 (4).
MS (EI, m/z, >5%): 42 (20.7), 43 (17.7), 58 (84.8) [NMe3 - H]þ,
65 (15.3), 91 (88.8) [C7H7]þ, 118 (11.9), 132 (36.5), 134 (100)
[C9H12N]þ, 178 (11.0), 209 (56.8) [Bi]þ, 342 (7.76), 343 (54.4)
[C9H12NBi]þ, 418 (5.91) [Bi2]þ, 477 (58.6) [(C9H12N)2Bi]þ, 627
(3.64) [Bi3]þ, 836 (5.99) [Bi4]þ. HRMS (ESIþ, m/z): calcd
(found) C9H11BiN [M - H - N3 - C9H12N]þ 343.069 53
(342.068 67), C18H24BiN2 [M -N3]þ 477.174 33 (477.179 64).
Crystals suitable for X-ray crystallographic analysis were
obtained directly from the above THF solution of 4.
selected in Fomblin YR-1800 perfluoroether (Alfa Aesar) at
ambient temperatures. The samples were cooled to 173(2) K
during measurement. The data were collected on a Bruker Apex
Kappa-II CCD diffractometer using graphite-monochromated
˚
Mo KR radiation (λ = 0.710 73 A). The structures were solved
by direct methods (SHELXS-97)28 and refined by full-matrix
least-squares procedures (SHELXL-97).29 Semiempirical absorp-
tion corrections were applied (SADABS).30 All non-hydrogen
atoms were refined anisotropically; hydrogen atoms were included
in the refinement at calculated positions using a riding model.
Synthesis of [2-(Me2NCH2)C6H4]2BiN3 (4). To a stirred solu-
tion of [2-(Me2NCH2)C6H4]2BiI (0.770 g, 1.27 mmol) in THF
(20 mL) was added silver azide (AgN3; neat, 0.210 g, 1.40 mmol)
in one portion at ambient temperature. The resulting yellowish
suspension was stirred for 15 h. The resulting off-white suspen-
sion was filtered (F4), and the solution was concentrated
in vacuo to an approximate volume of 3 mL. Slow cooling to -
25 °C resulted in the deposition of colorless crystals. Removal of
the supernatant by decantation and drying in vacuo yielded
0.578 g (1.11 mmol, 87%) of [2-(Me2NCH2)C6H4]2BiN3 (4) as
colorless crystals. Mp: 158 °C dec. Anal. Calcd (found): C, 41.62
(41.80); H, 4.66 (4.52); N, 13.48 (13.47). 1H NMR (25 °C,
CD2Cl2, 500.13 MHz): δ 2.33 (s, 12H, CH3), 3.67 (s, 4H,
Synthesis of [2-(Me2NCH2)C6H4]Bi(N3)2 (5). To a stirred
solution of [2-(Me2NCH2)C6H4]Bil2 (0.298 g, 0.5 mmol) in
THF (15 mL), was added silver azide (AgN3; neat, 0.165 g, 1.1
mmol) in one portion at ambient temperature. The resulting
yellow suspension was stirred for 12 h, resulting in an off-white
suspension. Filtration (F4) and removal of solvent in vacuo
yielded 0.210 g (0.492 mmol, 98%) of [2-(Me2NCH2)C6H4]-
Bi(N3)2 (5) as a colorless, microcrystalline solid. Mp: 159 °C dec.
Anal. Calcd (found): C, 25.30 (25.93); H, 2.83 (2.81); N, 22.95
(22.08). 1H NMR (25 °C, THF-d8, 500.13 MHz): δ 2.56 (s, 12H,
CH3), 4.12 (s, 4H, CH2), 7.44 (td, 2H, CH, 3J(1H-1H) =
7.4 Hz), 7.67 (td, 2H, CH, 3J(1H-1H) = 7.4 Hz), 7.78 (dd,
2H, CH, 3J(1H-1H) = 7.4 Hz), 8.71 (dd, 2H, CH, 3J(1H-1H) =
7.4 Hz). 13C{1H} NMR (25 °C, THF-d8, 125.76 MHz): δ 44.9
(CH3), 68.6 (CH2), 128.8 (CH), 129.4 (CH), 130.6 (CH), 131.4
(CH), 139.0, 150.6. IR (ATR, 32 scans, cm-1): 3328 (w), 3281
(w), 3055 (w), 3033 (w), 2995 (w), 2967 (w), 2862 (w), 2835 (m),
2793 (w), 2688 (w), 2640 (s), 2570 (w), 2513 (w), 2022 (s), 1458
(m), 1435 (m), 1407 (w), 1352 (w), 1310 (s), 1262 (s), 1196 (m),
1172 (m), 1155 (w), 1145 (w), 1109 (m), 1100 (m), 1033 (m), 1012
(s), 972 (m), 950 (w), 873 (w), 841 (s), 823 (s), 753 (s) 708 (w), 667
(w), 644 (s), 616 (w), 599 (s). Raman (50 mW, 25 °C, 107 scans,
cm-1): 3060 (3), 3036 (3), 3011 (2), 2970 (3), 2954 (2), 2943 (2),
2897 (3), 2870 (3), 2841 (3), 2798 (2), 2761 (1), 2071 (10), 2036 (5),
1581 (2), 1566 (2), 1461 (2), 1382 (2), 1354 (4), 1318 (1), 1291 (2),
1269 (2), 1244 (2), 1200 (2), 1176 (2), 1163 (1), 1043 (4), 1022 (2),
968 (1), 846 (1), 826 (1), 797 (1), 648 (3), 572 (1), 548 (1), 500 (2),
467 (2), 444 (2), 389 (1), 355 (4), 322 (6), 276 (3), 262 (3), 224 (2),
198 (6), 133 (9), 110 (5). MS (EI, m/z, >5%): 43 (18.1), 58 (21.1)
[NMe3 - H]þ, 91 (59.4) [C7H7]þ, 118 (7.67), 132 (37.7), 134 (100)
[C9H12N]þ, 209 (51.9) [Bi]þ, 336 (10.9), 343 (35.3) [C9H12NBi]þ,
378 (15.9), 385 (10.0), 418 (3.79) [Bi2]þ, 477 (46.7)
[(C9H12N)2Bi]þ, 627 (3.42) [Bi3]þ, 836 (5.22) [Bi4]þ.
3
4
CH2), 7.41 (td, 2H, CH, J(1H-1H) = 7.3 Hz, J(1H-1H) =
1.4 Hz), 7.45 (td, 2H, CH, 3J(1H-1H) = 7.3 Hz, 4J(1H-1H) = 1.4
3
4
Hz), 7.53 (dd, 2H, CH, J(1H-1H) = 7.3 Hz, J(1H-1H) =
1.4 Hz), 8.24 (dd, 2H, CH, 3J(1H-1H) = 7.3 Hz, 4J(1H-1H) =
1.4 Hz). 13C{1H} NMR (25 °C, CD2Cl2, 125.76 MHz): δ 46.0
(CH3), 68.3 (CH2), 128.8 (CH), 130.6 (CH), 131.4 (CH), 139.5
(CH), 147.0, 183.6. IR (ATR, 32 scans, cm-1): 3047 (w), 3009
(w), 2988 (w), 2957 (w), 2928 (w), 2894 (w), 2862 (m), 2837 (w),
2817 (m), 2784 (m), 2022 (s), 1471 (m), 1452 (s), 1437 (m), 1417
(w), 1406 (w), 1362 (w), 1352 (w), 1319 (s), 1299 (m), 1267 (m),
1246 (s), 1203 (m), 1171 (m), 1157 (m), 1146 (w), 1111 (m), 1070
(w), 1140 (m), 1031 (m), 1018 (s), 1006 (s), 974 (s), 948 (m), 882
(w), 842 (s), 829 (s), 759 (s), 722 (w), 709 (w), 668 (w), 647 (w), 639
(m), 610 (m). Raman (200 mW, 25 °C, 500 scans, cm-1): 3065
(5), 3049 (10), 3038 (7), 3020 (3), 3008 (3), 2998 (3), 2978 (6), 2958
(4), 2927 (3), 2893 (5), 2865 (5), 2838 (6), 2825 (5), 2785 (6), 2709
(1), 2683(1),2022(3), 1579(5),1566(3),1470(3), 1458(3),1439(4),
1406 (1), 1363 (1), 1353 (5), 1320 (2), 1302 (3), 1275 (2), 1249 (3),
1204 (3), 1167 (2), 1152 (2), 1112 (1), 1052 (5), 1042 (4), 1019 (5),
976 (1), 953 (1), 885 (1), 844 (2), 829 (1), 759 (1), 723 (1), 710 (1),
648 (6), 616 (1), 515 (2), 497 (1), 447 (4), 423 (1), 384 (1), 349 (8),
Crystals suitable for X-ray crystallographic analysis were
obtained by cooling a hot THF solution of 5 slowly to ambient
temperature.
(28) Sheldrick, G. M. SHELXS-97: Program for the Solution of
€
€
Crystal Structures; University of Gottingen: Gottingen, Germany, 1997.
(29) Sheldrick, G. M. SHELXL-97: Program for the Refinement of
Supporting Information Available: Text, figures, and tables
giving additional synthetic details and CIF files giving crystal
structure data. This material is available free of charge via the
Internet at http://pubs.acs.org.
€
€
Crystal Structures; University of Gottingen, Gottingen, Germany, 1997.
€
(30) Sheldrick, G. M. SADABS, Version 2; University of Gottingen,
€
Gottingen, Germany, 2004.