Syntheses and chemistry of methylantimony and methylbismuth dihalides: An extended two-dimensional framework in the crystal structure of CH3BiCl2 and molecular units in the structures of [CH3ECl2(2,2′-bipyridine

Article abstract of DOI:10.1021/om000749i

CH₃SbPh₂ reacts with HCl to give CH₃SbCl₂. CH₃BiCl₂ and CH₃BiBr₂ are formed by reaction of CH₃-BiPh₂ with HCl or HBr. The adducts [CH₃

Full text of DOI:10.1021/om000749i

5
86
Organometallics 2001, 20, 586-589
Syn th eses a n d Ch em istr y of Meth yla n tim on y a n d
Meth ylbism u th Dih a lid es: An Exten d ed
Tw o-Dim en sion a l F r a m ew or k in th e Cr ysta l Str u ctu r e of
CH BiCl a n d Molecu la r Un its in th e Str u ctu r es of
3
2
[
CH ECl (2,2′-bip yr id in e)] (E ) Sb, Bi)
3
2
Henrik Althaus, Hans J oachim Breunig,* and Enno Lork
Institut f u¨ r Anorganische und Physikalische Chemie (FB 02) der Universit a¨ t Bremen,
D-28334 Bremen, Germany
Received August 28, 2000
Summary: CH3SbPh2 reacts with HCl to give CH3SbCl2.
CH3BiCl2 and CH3BiBr2 are formed by reaction of CH3-
BiPh2 with HCl or HBr. The adducts [CH3ECl2(bipy)]
i.e., the reaction of (CH3)3Bi with BiX3 in a 1:2 molar
ratio, were reported by Marquardt already in 1887. The
8
2,2′-bipyridine ligand has been widely used before for
the complexation of inorganic and organometallic com-
pounds, including antimony(III) and bismuth(III) ha-
(E ) Sb, Bi, bipy ) 2,2′-bipyridine) are obtained by
combining the components in diethyl ether or tetrahy-
drofuran. The crystal structures of CH3BiCl2 and [CH3-
ECl2(bipy)] (E ) Sb, Bi) have been determined by single-
crystal X-ray diffraction.
9
lides. However, [PhSbCl2(bipy)] is the only bipyridine
complex of an organoantimony dihalide that was char-
acterized by X-ray crystallography. Crystal structures
of adducts of bipyridine with organobismuth halides
have not been reported before.
In tr od u ction
Alkylantimony and alkylbismuth dihalides REX2
R ) alkyl, E ) Sb, Bi; X ) Cl, Br, I) are amphoteric
Resu lts a n d Discu ssion
(
Pure samples of CH3SbCl2, CH3BiCl2, and CH3BiBr2
are obtained in a sequence of reactions (eq 1), starting
with the syntheses of diphenylantimony or diphenyl-
bismuth chloride, followed by alkylation with CH3MgI.
molecules with Lewis acidic sites at the metal atoms
trans to the metal-halogen bond and Lewis basic
functions mainly through the lone pairs of electrons of
the halogen atoms. In the absence of external donors
they coordinate with each other, forming dimers when
the alkyl groups are bulky or polymers when the alkyl
substituents are slim. Particularily strong extended
interactions exist in crystalline phases of the methyl
ECl3
CH MgI
3
HX
Ph E
8 Ph ECl
8 Ph ECH
8 CH EX2 (1)
3
2
2
3
3
E ) Sb, X ) Cl; E ) Bi, X ) Cl, Br
1
1
2
derivatives CH3SbCl2, CH3SbBr2, CH3SbI2, and CH3-
BiI2, which consist of infinite chains, [(CH3)E(µ-X)2]x
3
Action of gaseous HCl or HBr on CH SbPh or CH BiPh
3
2
3
2
in CHCl3 or CH2Cl2 results in the substitution of the
phenyl groups by halogen atoms. Methylantimony dichlo-
ride is obtained as a colorless liquid after removal of
the solvent. Methylbismuth dichloride and methylbis-
muth dibromide precipitate as white and yellow solids,
respectively, from the reaction mixture.
The yields of the last step of the reactions (1) are close
to 90% for the antimony compound and almost quanti-
tative for the bismuth derivatives. The overall yields lie
between 50 and 70%. Both bismuth halides are insoluble
in aromatic or aliphatic hydrocarbons. They are only
slightly soluble in dichloromethane, chloroform, and
diethyl ether and readily soluble in ethanol, tetrahy-
drofuran, or dimethyl sulfoxide. Methylbismuth dichlo-
ride is air-stable both in solution and in the solid state.
Single crystals were obtained by evaporation of a
solution in ethanol in the air at ambient temperature.
Methylbismuth dibromide decomposes in solution but
is air-stable as a solid.
(
E ) pnicogen; X ) halogen).
In the course of investigations of the structures and
the chemistry of alkylantimony(III) and alkylbismuth-
4
(III) halides we report here on new synthetic pathways
leading to CH3SbCl2, CH3BiCl2, or CH3BiBr2, on the
exceptional crystal structure of CH3BiCl2, and on the
syntheses and structures of 1:1 complexes of CH3SbCl2
and CH3BiCl2 with 2,2′-bipyridine (bipy). Methylanti-
mony dichloride was synthesized before by thermal
elimination of CH3Cl from (CH3)2SbCl3 or by reactions
of Sn(CH3)4, Pb(CH3)4, or (CH3)2SbCl with SbCl3. The
first methods for the syntheses of CH3BiX2 (X ) Cl, Br),
5
6
5
7
*
To whom correspondence should be addressed. E-mail: breunig@
chemie.uni-bremen.de. Fax: 494212184042.
1) Breunig, H. J .; Denker, M.; Ebert, K. H. J . Organomet. Chem.
994, 470, 87.
2) Breunig, H. J .; Ebert, K. H.; G u¨ lec, S.; Dr a¨ ger, M.; Sowerby, D.
B.; Begley, M. J .; Behrens, U. J . Organomet. Chem. 1992, 427, 39.
3) Mitzi, D. B.; Wang, S.; Landrum, G. A.; Genin, H.; Hoffman, R.
J . Am. Chem. Soc. 1997, 119, 724.
4) Althaus, H.; Breunig, H. J .; R o¨ sler, R.; Lork, E. Organometallics
999, 18, 328.
5) Wieber, M. Gmelin Handbook of Inorganic Chemistry; Springer-
Verlag: Berlin, 1981; Sb Organoantimony Compounds, part 2, p 92.
6) Wieber, M.; Wirth, D.; Fetzer, I. Z. Anorg. Allg. Chem. 1983, 505,
34.
(
1
(
(
(
The crystal structure of CH3BiCl2 consists of puckered
two-dimensional nets of methylbismuth units and chlo-
rine atoms. The methyl groups are directed to one side
1
(
(
1
(8) Marquardt, A. Ber. Dtsch. Chem. Ges. 1887, 20, 1516.
(9) Nunn, M.; Begley, M. J .; Sowerby, D. B.; Haiduc, I. Polyhedron
1996, 15 Nr. 19, 3167.
(7) Ates, M.; Breunig, H. J .; G u¨ lec, S. J . Organomet. Chem. 1989,
3
64, 67.
1
0.1021/om000749i CCC: $20.00 © 2001 American Chemical Society
Publication on Web 01/04/2001

Notes
Organometallics, Vol. 20, No. 3, 2001 587
F igu r e 3. View of a section of the double layers in the
crystal structure of CH BiCl .
3 2
F igu r e 1. View of a single layer in the crystal structure
of CH BiCl . Bi-Cl-Bi ) 122.60(10)°.
3 2
F igu r e 4. Representation of the molecular geometry and
the atom-numbering scheme for [CH SbCl (bipy)]. Impor-
tant bond lengths (Å) and angles (deg): Sb(1)-C(1) )
3
2
2
.130(4), Sb(1)-N(1) ) 2.379(3), Sb(1)-Cl(1) ) 2.6341(10),
N(1)-C(11) ) 1.347(4), N(1)-C(15) ) 1.338(4), C(11)-
C(11′) ) 1.477(6); C(1)-Sb(1)-N(1) ) 85.49(13), C(1)-Sb-
(
1)-Cl(1) ) 84.48(8), N(1)-Sb(1)-Cl(1) ) 90.15(7), N(1)-
Sb(1)-Cl(1′) ) 157.29(7), N(1)-Sb(1)-N(1′) ) 68.77(13),
Cl(1′)-Sb(1)-Cl(1) ) 109.05(4).
F igu r e 2. Coordination around the bismuth atom in the
crystal structure of CH BiCl . Important bond lengths (Å)
and angles (deg): Bi(1)-C(1) ) 2.225(12), Bi(1)-Cl(1) )
3
2
Addition of 2,2′-bipyridine to a solution of CH3SbCl2
in diethyl ether (1:1 molar ratio) results in the precipi-
tation of a solid containing the complex and diethyl
ether. Purification by sublimation at reduced pressure
gives yellow, air-stable crystals of [CH3SbCl2(bipy)] in
73% yield. The reaction of CH3BiCl2 with 2,2′-bipyridine
(1:1 molar ratio) is performed in tetrahydrofuran. The
complex [CH3BiCl2(bipy)] precipitates as a white air-
stable solid in 89% yield after the addition of the ligand.
Both bipyridine complexes are soluble in coordinating
solvents such as dimethyl sulfoxide (DMSO) or aceto-
nitrile but insoluble in hydrocarbons. NMR spectro-
scopic investigations indicate that the complexes are
labile in solution. Spectra obtained from crystals of the
complexes in (CD3)2SO show the signals of the free
bipyridine ligands. The coordination of the ligand is,
however, preserved under the conditions of mass spec-
trometry. Electron impact mass spectra show signals
2
3
8
.7411(15), Bi(1)-Cl(2) ) 2.7553(13), Bi(1)‚‚‚Cl(2b,c) )
.648(2); C(1)-Bi(1)-Cl(1) ) 85.4(2), C(1)-Bi(1)-Cl(2) )
7.8(2), Cl(1)-Bi(1)-Cl(2) ) 91.40(4), Cl(1)-Bi(1)-Cl(1a)
)
88.49(6), Cl(2)-Bi(1)-Cl(2a) ) 87.91(5).
of the array of the inorganic atoms. The chlorine atoms
occupy bridging positions between two bismuth atoms,
which have a square-pyramidal environment with apical
methyl groups and basal chlorine atoms. A view of the
puckered CH3BiCl2 net is given in Figure 1. The meshes
of the net consist of eight-membered [(CH3)Bi]4Cl4
heterocycles, where four bismuth atoms and four chlo-
rine atoms form regular Bi4 or Cl4 squares with dihedral
angles of 37.4° between the Bi4 planes and the Cl4
planes. The conformation of the heterocycles combines
aspects of saddle and crown conformations.
The coordination sphere of the bismuth atoms is
shown in Figure 2. The bond lengths around the
bismuth atom are Bi-C ) 2.225(12) Å and Bi-Cl )
+
of fragment ions [CH3ECl2(bipy) - CH3] (E ) Sb, Bi)
at highest mass.
2
.7411(15), 2.7553(13) Å. Similar values have
4
been reported for (Me3Si)2CHBiCl2‚0.5Et2O (Bi-C )
2
another polymeric alkylbismuth dichloride.
Single crystals of [CH3SbCl2(bipy)] were obtained by
gas-phase diffusion of diethyl ether into a solution of
the complex in acetonitrile. Single crystals of [CH3BiCl2-
(bipy)] grew in a solution in dichloromethane that was
exposed to the ambient atmosphere. The crystal struc-
tures of both complexes are depicted in Figures 4 and 5.
The structures feature molecular units, [CH3ECl2-
(bipy)] (E ) Sb, Bi), with tetragonal-pyramidal coordi-
nation of the antimony or bismuth atom. The methyl
groups occupy the apical positions. The nitrogen atoms
of the bipyridyl ligands and the chlorine atoms are in
basal sites. The Sb-N and Sb-Cl bond lengths of [CH3-
SbCl2(bipy)] compare well with the analogous phenyl-
antimony compound: ([CH3SbCl2(bipy)], Sb-N ) 2.379-
.237(14) Å, Bi-Cl (bridging) 2.704(5), 2.824(4) Å),
The bismuth center in CH3BiCl2 lies 0.168 Å beneath
the basal square. It is directed toward two chlorine
atoms of an adjacent net. The inter-net Bi‚‚‚Cl contact
distances of 3.648(2) Å are shorter than the sum of the
corresponding van der Waals radii (∑(rvdW)Bi,Cl ) 4.2
Å). Such close interactions between two nets lead to an
inorganic layer of bismuth and chlorine atoms which is
confined by the organic layer of the methyl groups. A
section of the layers is presented in Figure 3. Inorganic
and organic layers can also be distinguished in the chain
structures of CH3BiI23 and CH3SbX2 (X ) Cl, Br, I).
1,2

5
88 Organometallics, Vol. 20, No. 3, 2001
Notes
1
molecular character of CH3SbCl2, where the crystal
structure consists of chains of associated molecules with
short Sb-Cl bonds and longer Sb‚‚‚Cl contacts. In
contrast, the Bi-Cl bond lengths in CH3BiCl2 are almost
equal and the molecular character is completely lost.
Both compounds exist, however, as molecules in solu-
tions with donor solvents or in complexes with the bipy
ligand. Another consequence of the relatively high Lewis
acidity of the bismuth centers in both the structures of
CH3BiCl2 and [CH3BiCl2(bipy)] is the tendency to
increase the coordination beyond the coordination num-
ber 5 through Bi‚‚‚Cl contacts to neighboring chains or
molecules.
The square-pyramidal geometry and the position of
the central pnicogen atom below the basal plane in
particular observed in the structures of CH3BiCl2 and
F igu r e 5. Representation of the molecular geometry and
the atom-numbering scheme for [CH BiCl (bipy)]. Impor-
tant bond lengths (Å) and angles (deg): Bi(1)-C(1) )
.230(11), Bi(1)-N(1) ) 2.483(9), Bi(1)-N(2) ) 2.486(8),
[CH3ECl2(bipy)] (E ) Sb, Bi) are not uncommon in the
3
2
structural chemistry of the organo dihalides of Sb or Bi
and their derivatives. Often these features are discussed
in terms of the VSEPR model, and in fact it is tempting
to envisage a stereochemical activity of the lone pair of
electrons at the antimony or bismuth atoms trans to
the organic groups. However, the assumption of an s
character of the orbital with the lone pair of electrons
at Sb or Bi would also account for the general square-
pyramidal geometry, and the observed distortions may
rather result from the intermolecular contacts or from
the small bite angle of the bipyridine ligands than from
the lone pair activity.
2
Bi(1)-Cl(1) ) 2.709(3), Bi(1)-Cl(2) ) 2.678(3); C(1)-Bi-
(
(
1)-N(1) ) 86.6(3), C(1)-Bi(1)-N(2) ) 83.3(4), C(1)-Bi-
1)-Cl(1) ) 85.7(4), C(1)-Bi(1)-Cl(2) ) 86.2(3), N(1)-
Bi(1)-N(2) ) 65.6(3), N(1)-Bi(1)-Cl(2) ) 156.6(2), N(2)-
Bi(1)-Cl(2) ) 91.4(2), N(1)-Bi(1)-Cl(1) ) 88.9(2), N(2)-
Bi(1)-Cl(1) ) 152.8(2), Cl(2)-Bi(1)-Cl(1) ) 112.65(9);
Bi(2)-C(2) ) 2.233(10), Bi(2)-N(3) ) 2.521(9), Bi(2)-N(4)
)
2.548(9), Bi(2)-Cl(3) ) 2.675(3), Bi(2)-Cl(4) )
2
8
8
9
1
1
.649(3); C(2)-Bi(2)-N(3) ) 83.5(4), C(2)-Bi(2)-N(4) )
7.4(4), C(2)-Bi(2)-Cl(3) ) 86.3(3), C(2)-Bi(2)-Cl(4) )
6.5(3), N(3)-Bi(2)-N(4) ) 64.8(3), N(3)-Bi(2)-Cl(4) )
1.9(2), N(4)-Bi(2)-Cl(4) ) 156.3(2), N(3)-Bi(2)-Cl(3) )
55.8(2), N(4)-Bi(2)-Cl(3) ) 93.0(2), Cl(4)-Bi(2)-Cl(3) )
09.40(10).
Exp er im en ta l Section
The reactions and manipulations were performed under an
atmosphere of dry argon. Chemical shifts are reported in δ
9
(
2
3) Å, Sb-Cl ) 2.6341(10) Å; [PhSbCl2(bipy)], Sb-N )
1
units (ppm) referenced to CHCl
3
(7.25 ppm, H), C
6 5
D H (7.15
.43(1) Å, Sb-Cl ) 2.556(5) Å). The antimony centers
1
13
13
ppm, H), C
6
D
6
(128.0 ppm, C), (CD SO (39.43 ppm, C),
3 2
)
1
of both complexes lie below the plane of the basal
ligands ([CH3SbCl2(bipy)], 0.225 Å; [PhSbCl2(bipy)], 0.16
and (CD )(CD H)SO (2.50 ppm, H).
3
2
P r ep a r a tion of CH
3 2
SbCl . A gentle flow of dry HCl is
9
Å ). The Bi-Cl bonds in [CH3BiCl2(bipy)] (Bi-Cl )
introduced into a solution of 36.19 g (124.4 mmol) of CH -
3
1
1
SbPh
2
3
in 150 mL of CHCl for 80 min followed by a flow of
2
.709(3), 2.678(3) Å) are only slightly shorter than in
argon (20 min). The resulting mixture is stirred for 12 h at
room temperature, and the solvent is removed at 40 mbar.
CH3BiCl2. The Bi-N bond lengths in [CH3BiCl2(bipy)]
Bi-N ) 2.521(9), 2.548(9) Å) are in the range of the
corresponding distances in [(BiCl3)2(bipy)3] (Bi-N )
.51(3)-2.71(3) Å).10 Crystals of [CH3BiCl2(bipy)] consist
(
Distillation of the slight yellow residue at 25 mbar (bp 95-
1
1
05 °C) gives 22.97 g (88.9%) of CH
3
SbCl
2
. H NMR (C
6
D
6
, 200
, 50
2
7
13
MHz, 23 °C): 1.06 (s, 3 H, CH
MHz, 23 °C): 27.33 (CH ).
P r ep a r a tion of [CH SbCl
3
) (lit. 1.1). C NMR (C
6
D
6
of molecular dimers. The [CH3BiCl2(bipy)] molecules are
associated on the basal plane through intermolecular
Bi‚‚‚Cl (3.639(33), 3.945(52) Å) and Bi‚‚‚Bi (4.203(6) Å)
contacts, which are shorter than the sum of the respec-
tive van der Waals radii ∑(rvdW)Bi,Cl ) 4.2; ∑(rvdW)Bi,Bi
3
3
2
(bip y)]. Dropwise addition of
a solution of 1.05 g (6.72 mmol) of 2,2′-bipyridine in 30 mL of
diethyl ether at 25 °C to a stirred solution of 1.24 g (5.96 mmol)
of CH SbCl in 10 mL of diethyl ether gives a yellow solid.
3 2
The mixture is stirred for 12 h to complete the reaction and
the solution removed with a syringe. The solid is washed two
times with 20 mL of diethyl ether, dried at reduced pressure,
)
4.8 Å). The bismuth atoms lie 0.203 Å (Bi(1)) or 0.182
Å (Bi(2)) below the basal plane.
A comparison of the novel structures presented here
with related compounds of antimony or bismuth reveals
some interesting aspects. The two-dimensional net
structure of CH3BiCl2 is unusual, because the four other
known crystal structures of methylantimony and me-
thylbismuth dihalides consist of one-dimensional chains.
A common feature of all the dihalides is the (distorted)
square-planar environment of the heavy pnicogen cen-
ters. It is well-known that as a consequence of the larger
atomic radius and the more metallic character of
bismuth compared with antimony, the Lewis acidity of
Sb(III) compounds is lower than that of related Bi(III)
compounds. This trend is reflected in the predominantly
-
3
and sublimed at 120 °C and 10 mbar to give 1.72 g (73.0%)
of [CH SbCl (bipy)] (mp 202-205 °C). Anal. Calcd for C11
Cl
3
2
11
H -
2
N
2
Sb (363.88): C, 36.31; H, 3.05. Found: C, 35.93; H, 2.90.
+
+
+
MS (EI, 70 eV): 347 (15) [M - CH
91 (24) [SbCl
78 (25) [C H N ].
3
+
], 206 (3) [CH
SbCl ], 156 (100) [C10
3
SbCl
H N
8
2
],
],
+
+
1
2
], 171 (12) [CH
3
2
5
4
P r ep a r a tion of CH
mmol) of Ph
BiCl12 in 250 mL of THF is added dropwise at
room temperature with stirring to a Grignard solution pre-
pared from 7.413 g (52.223 mmol) of CH I and 1.475 g
60.675mmol) of magnesium filings in 80 mL of diethyl ether.
The suspension is stirred overnight at room temperature. The
3 2
BiP h . A solution of 18.90 g (47.41
2
3
(
(
11) Gr u¨ ttner, G.; Wiernik, M. Ber. Dtsch. Chem. Ges. 1915, 48,
759.
(12) Barton, D. H. R.; Bhatnagar, N. V.; Finet, J .-P.; Motherwell,
W. B. Tetrahedron 1986, 42, 3111.
1
(10) Bowmaker, G. A.; Hannaway, F. M. M.; J unk, P. C.; Lee, A.
M.; Skelton, B. W.; White, A. H. Aust. J . Chem. 1998, 51, 331.

Notes
Organometallics, Vol. 20, No. 3, 2001 589
Ta ble 1. Cr ysta l Da ta , Da ta Collection , a n d Str u ctu r e Refin em en t P a r a m eter s for CH
CH SbCl (bip y)], a n d [CH BiCl (bip y)]
3 2
BiCl ,
[
3
2
3
2
CH3BiCl2
[CH3SbCl2(bipy)]
[CH3BiCl2(bipy)]
formula
fw
CH3BiCl2
294.91
C11H11Cl2N2Sb
363.87
C11H11BiCl2N2
451.10
color
yellow
173(2)
yellow
173(2)
colorless
173(2)
0.6 × 0.4 × 0.1
triclinic
P1h
9.340(2)
11.052(5)
13.420(2)
91.74(2)
91.15(2)
107.89(2)
1317.1(7)
4
temp, K
cryst size, mm
cryst syst
space group
a, Å
0.7 × 0.4 × 0.3
0.5 × 0.3 × 0.15
monoclinic
P21/m
5.5520(10)
16.092(4)
7.0970(10)
90
92.775(13)
90
633.3(2)
2
orthorhombic
Pbcm
10.211(3)
6.255(2)
7.650(3)
90
90
90
488.6(3)
b, Å
c, Å
R, deg
â, deg
γ, deg
3
V, Å
Z
4
-
3
dcalcd, g cm
4.009
36.978
ω /2θ
504
1.908
2.573
ω /2θ
352
2.275
13.766
ω /2θ
832
-
1
µ(Mo KR), mm
scan method
F(000)
scan range, deg
3.82 e θ e 27.54
2.53 e θ e 27.49
2.50 e θ e 27.49
no. of measd data
no. of unique data
no. of params
3942
2110
6904
608 (Rint ) 0.0879)
26
1497 (Rint ) 0.0395)
80
5866 (Rint ) 0.0318)
294
no. of data with I > 2σ(I)
608
1497
DIFABS
0.0691
0.0318
0.0652
0.0262
1.050
+0.670; -0.893
5866
DIFABS
0.1516
0.0697
0.1398
0.0536
1.027
+3.200; -2.733
1
7
17
17
abs cor
DIFABS
0.0979
0.0417
0.0954
0.0384
1.078
a
wR2(all data)
R1(all data)
a
a
wR2(I > 2σ(I))
a
R1(I > 2σ(I))
2
GOF on F
-
3
residual density, e Å
+2.966; -3.448
a
Definition of the R values: R1 ) (∑||Fo| - |Fc||)/∑|Fo|; wR2 ) {∑[w(Fo - Fc ) ]/∑[w(Fo ) ]} with w-1 ) σ (Fo ) + (aP) + bP.
2
2
2
2
2
1/2
2
2
2
solvent is removed at reduced pressure, and the residue is
residue washed two times with 10 mL of thf. Removal of the
extracted with petroleum ether. Removal of the solvent gives
solvent at reduced pressure gives 1.45 g (89.2%) of [CH
(bipy)] (mp 208-210 °C). Anal. Calcd for C11
3
BiCl
Bi
2
-
1
1
1
2
7
3
1.88 g (66.3%) of colorless, liquid CH
00 MHz): 1.50 (s, 3 H, CH
3
BiPh
2
. H NMR (CDCl
3
,
),
H
11Cl
2
N
2
3
), 7.28-7.54 (m, 6 H, m- + p-C
6
H
5
+
(451.10): C, 29.29; H, 2.46. Found: C, 29.41; H, 2.42. MS (EI,
+
+
.73-7.95 (m, 4 H, o-C
6
H
5
). MS (EI, 70 eV): 378 (0.8) [M ],
70 eV): 435 (0.9) [M - CH
3
], 415 (0.1) [M - Cl], 400 (0.5)
+
+
+
+
+
63 (38) [M - CH
3
], 301 (4) [M - C
6
H
5
], 286 (10) [M
-
[M - Cl - CH
3
], 365 (0.3) [M - CH
3
3
- 2 Cl], 294 (11) [CH -
BiCl ], 244 (14) [BiCl ],
+
+
+
+
+
+
CH
(C
3
- C
6
+
H
5
], 224 (6) [M - 2 C
6
H
5
], 209 (100) [Bi ], 154 (3)
BiCl
2
], 279 (42) [BiCl
2
], 259 (19) [CH
3
+
+
+
+
[
6
H
5
)
2
], 77 (2) [C
6
H
5
].
BiCl
introduced at 0 °C into a solution of 10.0 g (26.44 mmol) of
CH BiPh in 120 mL of CHCl for 2 h followed by a flow of
argon for 20 min. The solvent is removed from the white
suspension, and 7.58 g (97.4%) of white solid CH BiCl remains
224 (3) [CH
3
Bi ], 209 (21) [Bi ], 156 (100) [C10
H
8
N
2
], 78 (8)
+
P r ep a r a tion of CH
3
2
. A gentle flow of dry HCl is
[C
5
H
4
N ].
X-r a y Cr ysta llogr a p h y. The details of the crystal structure
3
2
3
determination and refinement are given in Table 1. Data were
collected on a Siemens P4 four-circle diffractometer using
graphite-monochromated Mo KR radiation (λ ) 0.710 73 Å).
For this purpose the crystals were attached with Kel-F oil to
a glass fiber and cooled under a nitrogen stream to 173 K.
The structures were solved, after Lp correction, by direct
methods. All non-hydrogen atoms were refined with anisotro-
pic thermal parameters. The hydrogen atoms were refined
with a riding model and a mutual isotropic thermal parameter.
For structure solving and refinement the software package
SHELX-97 was used.13 The drawings were created by the
Diamond program by Crystal Impact GbR.14
3
2
8
(
3
mp 246-249 °C dec; lit. mp 242 °C). Anal. Calcd for CH -
1
2
BiCl (294.92): C, 4.07; H, 1.03. Found: C, 4.13; H, 1.12. H
1
3
6 3
NMR (d -DMSO, 200 MHz, 23 °C): 1.56 (s, 3 H, CH ). C NMR
(
(
[
d
6
-DMSO, 50 MHz, 23 °C): 74.28 (CH
3
). MS (EI, 70 eV): 294
+
+
+
25) [M ], 279 (79) [M - CH
3
], 259 (48) [M - Cl], 244 (46)
+
- Cl], 224 (6) [M - 2 Cl], 209 (100) [Bi+].
BiBr . A gentle flow of dry HBr is
BiPh
+
M
- CH
P r ep a r a tion of CH
introduced into a solution of 3.375 g (8.923 mmol) of CH
in 40 mL of CH Cl for 1 h at 25 °C followed by a flow of argon
for 20 min. The solvent is removed from the yellow precipitate
3
3
2
3
2
2
2
Ack n ow led gm en t. The support of this work by the
Deutsche Forschungsgemeinschaft is gratefully acknowl-
edged.
by a syringe, and the residue is washed with 20 mL of CH
and dried under vacuum. A 3.35 g (97.8%) amount of CH
2
Cl
3
2
-
8
BiBr
2
remains as a yellow solid (mp 195-197 °C dec; lit. mp
BiBr (383.82): C, 3.13; H, 0.79.
Found: C, 3.35; H, 0.81. H NMR (d -DMSO, 200 MHz, 23
-DMSO, 50 MHz, 23 °C):
2
14 °C). Anal. Calcd for CH
3
2
1
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal
data and structure refinement details, atom coordinates and
U values, bond distances and angles, anisotropic thermal
parameters, and dihedral angles. This material is available
free of charge via the Internet at http://pubs.acs.org.
6
1
3
°
3 6
C): 1.77 (s, 3 H, CH ). C NMR (d
+
+
6
CH
9.29 (CH
3
+
3
). MS (EI, 70 eV): 382 (32) [M ], 369 (100) [M
-
], 303 (13) [M+ - Br], 288 (44) [M - CH
+
3
- Br], 224 (7)
+
[M
- 2 Br], 209 (85) [Bi ].
OM000749I
3 2
P r ep a r a tion of [CH BiCl (bip y)]. A solution of 0.58 g
(
3.69 mmol) of 2,2′-bipyridine in 20 mL of tetrahydrofuran (thf)
(
13) Sheldrick, G. M. SHELX-97; Universit a¨ t G o¨ ttingen, G o¨ ttingen,
Germany, 1997.
14) Brandenburg, K. Diamond, Version 2.1 c; Crystal Impact GbR,
999.
(15) Walker, N.; Stuart, D. Acta Crystallogr. 1983, A39, 158.
is added dropwise with stirring at 25 °C to a solution of 1.06
g (3.59 mmol) of CH BiCl in 10 mL of thf. A white solid
precipitates, and the suspension is stirred for 12 h to complete
the reaction. The solvent is removed with a syringe and the
3
2
(
1