Cost efficient synthesis of bismuth aminoalkoxides from bismuth oxide: Molecular structure of [Bi2(mdea)2(mdeaH)2](mdeaH2)2

Article abstract of DOI:10.1016/j.inoche.2006.09.012

Functional Bi alkoxides were prepared by reaction between the oxide and diols such as N-methyldiethanolamine (mdeaH₂), diethanolamine (deaH₂) and triethanolamine (teaH₃) in refluxing toluene in high yields. Similar reactions with polyols without N-donor site lead to oxo species. The derivative obtained with N-methyldiethanolamine was characterised by X-ray diffraction as a dimer [Bi₂(mdea)₂(mdeaH)₂] associated as chains through H-bonding with neutral diol molecules giving the title compound. Bismuth is pseudo 7-coordinate. Bi-O bond distances range from 2.150(5) to 3.093(5) ? with three short ones, whereas the transannular Bi-N bond distances are 2.737 ? av. Thermolysis and hydrolysis reactions are reported.

Full text of DOI:10.1016/j.inoche.2006.09.012

Inorganic Chemistry Communications 10 (2007) 80–83
www.elsevier.com/locate/inoche
Cost efficient synthesis of bismuth aminoalkoxides from bismuth
oxide: Molecular structure of [Bi (mdea) (mdeaH) ](mdeaH )
2
2
2
2 2
J e´ rome Le Bris , Liliane G. Hubert-Pfalzgraf , St e´ phane Daniele a,*,
a
a
b
Jacqueline Vaissermann
a
Universit e´ de Lyon1, IRC, 2 av. A. Einstein, 69626 Villeurbanne C e´ dex, France
Universit e´ de Paris 6, Laboratoire de Chimie Inorganique et des mat e´ riaux mol e´ culaires, UMR, 4 place Jussieu, 75552 Paris C e´ dex 5, France
b
Received 28 June 2006; accepted 12 September 2006
Available online 26 September 2006
Abstract
Functional Bi alkoxides were prepared by reaction between the oxide and diols such as N-methyldiethanolamine (mdeaH
2
), dietha-
nolamine (deaH ) and triethanolamine (teaH ) in refluxing toluene in high yields. Similar reactions with polyols without N-donor site
2
3
lead to oxo species. The derivative obtained with N-methyldiethanolamine was characterised by X-ray diffraction as a dimer [Bi (m-
2
2 2
dea) (mdeaH) ] associated as chains through H-bonding with neutral diol molecules giving the title compound. Bismuth is pseudo 7-
˚
coordinate. Bi–O bond distances range from 2.150(5) to 3.093(5) A with three short ones, whereas the transannular Bi–N bond distances
˚
are 2.737 A av. Thermolysis and hydrolysis reactions are reported.
ꢀ
2006 Published by Elsevier B.V.
Keywords: Bismuth; Functional alkoxides; Structure; Sol–gel; Aminoalkoxide; Oxide
The interest in bismuth compounds is motivated by their
wide applicability in bioinorganic chemistry [1], homoge-
neous and heterogeneous catalysis [2] and material science
muth nitrate pentahydrate by polyols afforded heteroleptic
derivatives [8], the most common Bi(III) alkoxides have
been prepared by metathesis reactions applied to halides
or by alcoholysis of amides [9,10]. The metathesis route
leads often to some halide or alkali metal contamination
of the alkoxides – an undesirable feature for high tech
materials – whereas alcoholysis of amides is quite expensive
for commercial use of metal alkoxides. A number of Bi
aryloxides have been reported but such compounds are
quite prone to reduction and/or a source of C contamina-
tion of oxide materials. Alternate, cost efficient synthetic
routes based on the reactions between anhydrous or
hydrated metal oxides and polyols have been reported for
a number of elements such as Si [11], Ti [12], and Pb [13].
Moreover, most reported bismuth alkoxides have a limited
shelf life due to their high susceptibility to moisture and/or
light. Functional bismuth alkoxides which usually show
improved hydrolytic stability remain limited to a few
[
3]. Materials based on bismuth include high T supercon-
c
ductors, ferroelectrics such as Bi Ti O , but also magnetic
4
3
12
ferroelectrics such as BiMO (M = Mn, Fe) [4]. Bismuth is
3
also considered nowadays as the least toxic heavy metal.
Bismuth trioxide in thin films is an interesting optical mate-
rial with a large energy gap, high value of refractive index
and dielectric permittivity, as well as remarkable photocon-
ductivity and photoluminescence [5]. Its various polymor-
phs a, b, x, c and d possess distinct physical properties
[
6]. The technological demands require thin films or nano-
particles. The most cost efficient routes to films are chemi-
cal solution deposition techniques (CSD), namely sol–gel
processing or metal–organic deposition (MOD) or vapour
phase techniques such as metal–organic vapour phase
decomposition (MOCVD) [7]. Although alcoholysis of bis-
alkoxyalkoxides such as [Bi (OC H OMe) ]
[14],
(Bi(mmp) [15] (mmp = OCMe CH OMe) = 1-methoxy-
2
2
4
3 1
*
Corresponding author. Tel./fax: + 33 4 72 44 53 60.
3
2
2
3
E-mail address: stephane.daniele@catalyse.cnrs.fr (S. Daniele).
2-methyl-2-propoxide), Bi(OCMe Et) (mmp) (x = 1 or
2 x
3ꢀx
1
387-7003/$ - see front matter ꢀ 2006 Published by Elsevier B.V.
doi:10.1016/j.inoche.2006.09.012

J.L. Bris et al. / Inorganic Chemistry Communications 10 (2007) 80–83
81
2
) [16] or aminoalkoxides Bi(OCHRCH NMe ) (R = H or
2 2 3
Me) [14] and Bi(tea) [17].
3
We wish to report herein the synthesis of Bi functional
aminoalkoxides, their characterisation and preliminary
0
data on their reactivity of the 2,2 -methyliminodiethanolate
derivative.
The reactions between Bi O and functional alcohols,
2
3
namely polyols such as N-methyldiethanolamine (mdeaH2),
diethanolamine (deaH ), diethyleneglycol (degH ), trietha-
2
2
nolamine (teaH ) or 2,2-dimethylpropane-1,3-diol (neol-
3
H = (OHCH ) CMe ) (stoichiometry 1:5–1:9), in refluxing
2
2 2
2
toluene lead to new bismuth derivatives (Eqs. (1)–(5)) [18].
The by-product, water, was trapped by molecular sieves.
The N-methylethanolamine derivative 1 was established by
single crystal X-ray diffraction to correspond to Bi2-
(
meda) (mdeaH) (mdeaH ) . The reactivity was similar for
2 2 2 2
Fig. 1. Molecular structure of the dimeric unit of 1, Bi (mdea) (mdeaH) ,
2
2
2
the various N-donor polyols deaH ꢁ teaH ꢁ mdeaH
showing the atom labelling scheme and thermal ellipsoids at 50%
probability level.
2
3
2
2
and was superior to that of the polyols degH > neol-H
2
without N-donor site. No reaction was observed between
Bi O and dimethylaminoethanol Me NC H OH in reflux-
2
3
2
2
4
Table 1
ing toluene even after 4 d. Bismuth oxide appears thus less
reactive than lead(II) oxide for synthesis of metal alkoxides
directly from the oxide [13]. The triethanoaminolate,
Selected bond lengths and angles of 1
˚
Bond lengths (A)
Angles (ꢁ)
Bi(1)–N(1)
Bi(1)–N(2)
Bi(1)–O(1)
Bi(1)–O(2)
2.729(5)
2.746(6)
2.150(5)
2.169(5)
2.692(5)
2.161(5)
3.976(5)
3.093(5)
O(1)–Bi(1)–O(2)
O(1)–Bi(1)–O(2 )
95.1(2)
165.2(2)
84.8(2)
69.12(2)
81.2(2)
85.7(2)
80.8(2)
70.7(2)
70.7(2)
151.8(2)
149.2(2)
88.9(2)
108.2(2)
109.3(2)
38.6(2)
138.7(2)
71.1(2)
129.8(2)
53.6(2)
54.6(2)
131.6(2)
109.3(2)
[
Bi(OCH CH ) N] . was obtained previously by reacting
0
2
2 3
1
freshly prepared Bi(OH) in alcohol with teaH and sodium
O(1)–Bi(1)–O(3)
O(1)–Bi(1)–N(1)
O(1)–Bi(1)–N(2)
O(1)–Bi(1)–O(4)
O(2)–Bi(1)–O(3)
3
3
but no yield was reported [16].
0
Bi(1)–O(2 )
Bi
2
O
3
þ 6mdeaH
2
! ½BiðmdeaÞðmdeaHÞðmdeaH
2
Þꢂ ð1Þ
2
Bi(1)–O(3)
Biꢃ ꢃ ꢃBi
þ 3H O
O
ð1Þ
ð2Þ
2
0
Bi(1)ꢃ ꢃ ꢃO(4)
O(2)–Bi(1)–O(2 )
Bi
2
3
þ 2teaH
3
! 2½BiðteaÞꢂ ð2Þ þ 3H
2
O
m
O(2)–Bi(1)–N(1)
O(2)–Bi(1)–N(2)
O(2)–Bi(1)–O(4)
O(2’)–Bi(1)–O(3)
O(2’)–Bi(1)–N(1)
O(2’)–Bi(1)–N(2)
O(2’)–Bi(1)–O(4)
O(3)–Bi(1)–N(1)
O(3)–Bi(1)–N(2)
O(3)–Bi(1)–O(4)
O(4)–Bi(1)–N(1)
O(4)–Bi(1)–N(2)
N(1)–Bi(1)–N(2)
Bi O þ 8deaH ! 2=mBiðdeaHÞ ðdeaH Þ ð3Þ
2
3
2
3
2
m
þ 3H
Bi
þ 6degH
Bi O þ 4neol-H ! 2=mBiOðneol-HÞðneol-H Þ2 ð5Þ
2
O
ð3Þ
ð4Þ
3
2
O
3
2
! 2Bi
3
O
2
ðOHÞ ðdegHÞ ð4Þ þ H
2
O
2
3
2
3
2
2
m
þ H
2
O
ð5Þ
The various compounds were obtained as white solids
showing no sensitivity to light, 1 and 3 hydrolyzed slowly
in the presence of moisture, while 2, 4 and 5 were air stable.
They were characterised by elemental analysis, FT-IR and
0
Bi(1)–O(2)–Bi(1 )
1
H NMR. The N-methyldiethanolate derivative 1 was
Equivalent positions’ = ꢀ x, 2 ꢀ y, 1 ꢀ z.
soluble in the reaction medium in contrast to the other
derivatives. The derivatives obtained with polyols without
N-donor site are either oxo or oxohydroxo species. Com-
pounds 3–5 are insoluble in usual organic solvents and
All bismuth atoms are surrounded by three short, primary
bonds Bi–O, two transannular Bi–N bonds and two longer
Bi–O bonds corresponding, respectively, to the association
of the monomeric units into dimers with asymmetrical
water. [Bi(tea)] was insoluble in the parent triol but solu-
1
ble in water. The FT-IR spectra of all compounds except 2
0
˚
show absorption bands of OH and/or NH groups around
bridges [Bi(1)–O(2 ) 2.692(5) vs Bi(1)–O(2) 2.169(5) A] as
well as to the partially deprotonated diol [Bi–O(4)(H)
ꢀ
1
3
300–3120 cm , indicating incomplete deprotonation of
˚
the various diols. Absorption bands of m vibrations
3.093(5) A]. Although long, this distance is significantly
Bi–O
ꢀ
1
˚
were observed below 600 cm , their value accounts in all
cases for the absence of contamination by residual bismuth
oxide.
shorter than the sum of the van der Waals radii (3.67 A)
and can be considered as a secondary bond as commonly
observed for molecular Bi derivatives. This leads to pseudo
7-coordinated bismuth atoms with a Biꢃ ꢃ ꢃBi distance of
The identity and the molecular structure of 1 were estab-
lished by single crystal X-ray diffraction (Fig. 1) [19].
Selected bond lengths and angles are collected in Table 1.
˚
3.976(5) A and Bi–O bond distances spreading over the
˚
range 2.150(5)–3.093(5) A. The Bi–O distances are in agree-

82
J.L. Bris et al. / Inorganic Chemistry Communications 10 (2007) 80–83
ment with those observed for other Bi alkoxides where the
metals have similar high coordination numbers [9,10]. With
the exception of the Bi–O(4) bond, these distances are in
the range of those observed for b-Bi O where the metal
Bi ðmdeaÞ ðmdeaHÞ ðmdeaH Þ þ TiðOiPrÞ
2
2
2
2
2
4
!
1a þ 1=2Ti
2
ðOiPrÞ ðmdeaÞ þ 2iPrOH
ð6Þ
6
Unfortunately, no suitable crystals could be grown for 3
or the oxo clusters 4 or 5 but the presence of bismutyl spe-
cies for the later is likely [22].
2
3
has a pseudo-octahedral geometry. The transannular
˚
Bi–N bond distances (av 2.737 A) of 1 are significantly
˚
longer than those of [Bi(tea)] (2.551 A av), where Bi is
1
also 7-coordinate [17]. They are close to the values found
Appendix A. Supplementary material
for Bi (l-ONep) (ONp) (py) [10a] or for Bi(III) com-
2
2
4
2
plexes with aminocarboxylate ligands where bismuth is,
respectively, 5- and 8-coordinate [20]. The Biꢃ ꢃ ꢃBi distances
are significantly longer than for the Bi (l-OC H OMe) -
Tables of coordinates, of thermal parameters, of bond
lengths and angles have been deposited at the Cambridge
Crystallographic Data Base Centre. CCDC 244547 contain
the supplementary crystallographic data for complex 1.
These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-
mail: deposit@ccdc.cam.ac.uk. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.inoche.2006.09.012.
2
2
4
4
˚
OC H OMe) dimer (3.6426(4) A) displaying also strongly
2 4 2
(
asymmetric bridges [9,14]. The Bi (mdea) (mdeaH) dimers
2
2
2
are further connected to each other via two neutral
mdeaH2 molecules by
H
bonds [O(3)ꢃ ꢃ ꢃO(5) and
˚
O(1)ꢃ ꢃ ꢃO(6) 2.684 A] forming thus polymeric chains. The
H bond lengths are close to the values found in the cyclic
˚
[
Bi(OEt) ] (7 + x)EtOH (2.46(3)–2.77(3) A) [10b]. The
3 8
bites angles have values around 70ꢁ. The lone pair of the
bismuth(III) centers appears stereochemically active and
located between O(2) and O(4).
1
References
The solubility of 1 allowed its characterisation by H
NMR. The spectra in CDCl at rt are quite uninformative
since they display only one set of resonances for the various
3
[
1] (a) H. Sun, P.J. Sadler, Topics in Biological Inorganic Chemistry,
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(
b) H. Wullens, E. Asato, K. Katsura, M. Mikuriya, U. Turpeinen, I.
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2
groups both with a 3:2:1 integration ratio, two for the
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(
(
c) M.J. Abrahams, B.A. Murrer, Science 12 (1993) 725;
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(
sharp peaks of the mdeaH molecules and their chemical
2
(
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2
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ꢀ4
ꢀ4
7
0 ꢁC/3 · 10
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(
(
(
b) T.J. Park, Y. Mao, S.S. Wong, Chem. Commun. (2004) 3;
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Compound 1a resulting from the elimination of the neutral
mdeaH molecules is insoluble in toluene and pyridine even
2
by heating, probably as a result of intermolecular H-bond-
Mater. 17 (2005) 1376.
ing due to the mdeaH ligand but remains soluble in CHCl3
[5] (a) D. Peng, D. Yao-Guo, X. Zi-Li, Chem. Res. Chin. Univ. 20 (2004)
717;
although dissolution is slow. TGA data of 1 under air indi-
(
b) Q. Yang, Y. Li, P. Wang, Y.B. Cheng, Mater. Lett. 55 (2002)
6.
6] (a) L. Leontie, M. Caraman, M. Delibas, G.I. Rusu, Mater. Res. Bull.
6 (2001) 129;
cate three decomposition steps: 130–225 ꢁC loss of mdeaH2
and mdeaH, 225–250 ꢁC loss of mdea and 250–360 ꢁC
decomposition into a quite reactive oxide since it is trans-
formed into the Bi O (CO ) phase at 246 ꢁC which decom-
4
[
3
2
2
3
(b) P. Shuk, H.D. Wiemhofer, U. Guth, W. Goepel, M. Greenblatt,
Solid State Ionics 89 (1996) 179.
poses into crystalline a-Bi O at 600 ꢁC, then a and x, and
2
3
[
[
[
7] L.G. Hubert-Pfalzgraf, Inorg. Chem. Commun. 6 (2003) 102;
L.G. Hubert-Pfalzgraf, J. Mater. Chem. 14 (2004) 3113.
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finally the b-Bi O polymorph above 900 ꢁC.
2
3
The reaction between 1 and Ti(OiPr) (1:1 stoichiome-
4
try) in toluene at rt is governed by redistribution reactions
(
1992) 2950, and 2960.
1
as shown by H NMR (Eq. (6)). The lability of the neutral
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mdeaH molecules leads to the formation of Ti (mdea)(l-
2
2
[
10] (a) T.J. Boyle, D.M. Pedrotty, B. Scott, J.W. Ziller, Polyhedron 17
OiPr) (OiPr) as identified by comparison with an authen-
4
5
(
(
1998) 19;
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2
b) V.G. Kessler, N. Ya Turova, E.P. Turevskaya, Inorg. Chem.
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between Ti(OiPr) and [Bi(tea)] in toluene even after heat-
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(c) C.M. Jones, M.D. Burkhart, R.E. Bachman, D.L. Serra, S.J. Hwu,
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4
1
ing at 70 ꢁC for 20 h.

J.L. Bris et al. / Inorganic Chemistry Communications 10 (2007) 80–83
83
(d) D. Mansfeld, M. Mehring, M. Schumann, Angew. Chem., Int. Ed.
(3): Same procedure as for 1 applied to 2 ml of deaH
3
(21.4 mmol),
4
4 (2005) 245.
bismuth oxide (1.25 g, 2.66 mmol) in toluene (25 ml). After 3 d, a grey
suspension was obtained. Compound 3 was insoluble in THF, CHCl
pyridine and acetonitrile. Anal. Calcd for BiC16 : C, 30.67; H,
6.60; N, 8.94. Found: C, 30.16; H 6.36; N 8.69%. FT-IR [cm ]:
3306s, 3260s, 3233s mO–H,N–H, 569m, 561m, 547w, 427w mBi–O,Bi–N
Bi (OH) (degH) (4): Same procedure as for 1 applied to 1.04 ml
de H deg (10.93 mmol), bismuth oxide (1.02 g, 2.19 mmol) in toluene
(70 ml). After 10 d, a pale yellow precipitate is obtained (1.17 g, 79
%). Anal. Calcd for Bi 13: C, 14.29; H, 2.89%. Found: C,
14.31; H, 2.93%. Compound 4 was insoluble in pyridine, CHCl and
water. FT-IR [cm ]: 3368s br mOH, 583w, 569m, 549m, 539m, 504w,
444w, 412m mBi–O. {BiO[(OCH )CMe (CH OH)][(OHCH C-
Me (5): Same procedure as for 1 applied to neol-H (3.19 g,
[
[
11] T. Kemmitt, W. Henderson, Aust. J. Chem. 51 (1998) 1031.
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3
,
41 4 8
H N O
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1
(
(
b) T. Kemmitt, N.I. Al-Salim, G.J. Gainsford, Eur. J. Inorg. Chem.
1999) 1847.
.
3
O
2
2
3
[
[
[
13] T. Kemmitt, L.G. Hubert-Pfalzgraf, G.J. Gainsford, P. Richard,
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3 12 29
C H O
3
58.
15] (a) W.A. Herrmann, N.W. Huber, P.T. Reiner, Chem. Ber. 126 (1993)
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3
ꢀ1
1
(
2
2
2
2 2
)
2
]
2
}
m
2
Bickley, A. Steiner, H.O. Davies, T.J. Leedham, G.W. Critchlow,
Chem. Vap. Deposition 7 (2001) 205.
30.59 mmol), bismuth oxide (1.78 g, 3.82 mmol) in toluene (70 ml).
After 10 d, the grey suspension was filtered. Compound 5 was
[
[
[
16] H. Kadokura, Y. Okuhara, M. Hijido, Jpn Kokai Tokkyo Koho, JP
insoluble in THF, CHCl
water. Anal. Calcd for BiC15H O
3
, acetonitrile, ethanol, nitromethane and
: C, 33.59; H, 6.58. Found: C,
33.90; H, 6.80%. FT-IR [cm ]: 3295m mOH, 582w, 565w, 537w, 526w,
472m, 433m mBi–O
2005060358, CAN 142:272329, 2005.
35 7
ꢀ1
17] R.E. Bachman, K.H. Whitmire, J.H. Thurston, A. Gulea, O. Stavila,
V. Satvila, Inorg. Chim. Acta 346 (2003) 249.
18] All reactions were done under inert atmosphere using Schlenk tubes
and vacuum line techniques. Solvents and reactants were purified by
.
[19] A suitable crystal of 1 was obtained by crystallisation in hot toluene
and was mounted on a Nonius Kappa CCD diffractometer equipped
standard methods. Syntheses. Bi
.2 ml of mdeaH (34.47 mmol) was added to a suspension of bismuth
oxide (2.83 g, 6.079 mmol) in toluene (140 ml). After refluxing for 6 d
water being trapped by molecular sieves), the medium was filtered.
Evaporation of the filtrate and recrystallisation in hot toluene gave
crystals of 1 at rt (4.71 g, 69%). Mp: 89 ꢁC. Calcd for BiC15
C, 31.98; H, 6.44; N, 7.46. Found: C, 32.05; H, 6.56; N, 7.63%.
2
(mdea)
2
(mdeaH)
2
(mdeaH
2
)
2
(1):
a
with MoK radiation. Accurate cell dimensions were obtained from
4
2
66 reflections collected at 150 K in the range 2 < h < 24ꢁ. The data
were corrected for Lorentz and polarization effects. Computations
were performed by using the PC version of CRYSTALS [23]. The
(
2
structure was solved by SHELXS [24] and refined on F by full-matrix
H
36
N
3
O :
6
least-squares with anisotropic displacement parameters for all non-
hydrogen atoms. Hydrogen atoms were introduced in calculated
positions in the last refinements with an overall isotropic displacement
ꢀ
1
Compound 1 is hygroscopic (4 h air). FT-IR [cm ]: 3137w mOH
,
1
1
610w dOH, 481w, 450w, 439w, 419m mBi–O. H NMR (CDCl
3
, 20 ꢁC,
N), 2.66 (t, J = 5.05 Hz, 24H, NCH ), 4.20
O, OH); ꢀ40 ꢁC; 2.27 (s, 6H, CH N [mdeaH
br, 12H, CH N [mdea, mdeaH]), 2.52 (m, 12H, NCH
[mdeaH ]), 3.1 (br, 4H, NCH
O [mdea, mdeaH]), 4.14 (br, 8H, CH O, mdeaH
O [mdeaH]), 4.83 (br, 2H, OH [mdeaH
36 3 6
parameter. Crystal data for 1: BiC15H N O , FW = 563.43, mono-
3
˚
˚
˚
ppm): 2.36 (s, 18H, CH
3
2
clinic, P2
1
/n, a = 10.5704(8) A, b = 16.802(2) A, c = 11.645(1) A,
˚
3
(
(
br, 28H, CH
2
3
2
]), 2.38
[mdea,
b = 100.19(1)ꢁ, V = 2035.6(4) A , Z = 4, T = 150 K, l = 86.95
1
ꢀ
3
2
cm , 21199 reflections were measured (5839 were unique)
a
b
mdeaH]), 2.9 br (8H, NCH
2
2
2
[mdeaH]),
R = 0.0457, wR = 0.1146, R = 0.0824, wR = 0.128 (all data), for
227 parameters. GOF = 0.9016.
3
4
2
5
.65 (m, 12H, CH
.54 (br, 4H, CH
H, OH [mdeaH]). C NMR (CDCl
9.83 (NCH , mdeaH ), 60.82 (NCH
2
2
2
),
2
2
]), 6.09 (br,
, 20 ꢁC) [ppm]: 41.55 (NCH
[20] H. Wullens, M. Devillers, B. Tinant, J.P. Declercq, Dalton (1996)
2023.
[21] T. Kemmitt, G.J. Gainsford, J. Aust. Chem. 55 (2002) 513.
[22] J.H. Thurston, D.C. Swenson, L. Messerle, Chem. Commun. (2005)
4228.
[23] D.J. Watkin, C.K. Prout, J.R. Carruthers, P.W. Betteridge, Crystals
Issue 10, Chemical Crystallography Laboratory, University of
Oxford, UK, 1996.
[24] G.M. Sheldrick, SHELXS86, Program for the solution of crystal
structures, University of Gottingen, Germany, 1986.
13
3
2
),
3
2
3
), 77.31 (OCH
(2): Same proce-
tea (10.46 mmol), bismuth oxide
0.97 g, 2.09 mmol) in toluene (60 ml). After 5 d, the precipitate was
separated (1.29 g, 87 %). Compound 2 was insoluble in pyridine but
can be recrystallized in water. Anal. Calcd for BiC 12NO : C, 20.29;
H, 3.40; N, 3.94. Found: C, 20.34, H, 3.47, N, 3.92%. FT-IR [cm ]:
2
). Compound
ꢀ1
(
1a) FT-IR [cm ]: 479w, 444w mBi–O. [Bi(tea)]
1
dure as for 1 applied to 1.4 ml of H
(
3
6
H
3
ꢀ1
1
6
08w, 575w, 552w, 448m, 410m mBi–O. H NMR (D
2
O, 20 ꢁC): 2.64 (t,
3
J = 6 Hz, 6H, NCH
2
), 3.64 (m, 6H, CH
2
O). {Bi(deaH) (deaH )}
3
2
m