Crystal Structure Theory and Applications, 2013, 2, 28-33 Published Online March 2013 (
Synthesis and Structural Study of Triphenylbismuth
Bis (Salicylate)
Kheira Feham1, Abdelkarim Benkadari2, Abdelkader Chouaih2*, Abdellah Miloudi1,3,
Gérard Boyer4, Douniazed El Abed1
1Laboratoire de Chimie Fine (LCF), Université d’Oran, Es-Senia, Algérie
2Laboratoire SEA2M, Université de Mostaganem, Mostaganem, Algérie
3Département de Physique-Chimie, ENSET d’Oran, Oran, Algérie
4Laboratoire HIT, Université Paul Cezanne, Marseille, France
Email: *
Received October 29, 2012; revised December 5, 2012; accepted December 18, 2012
The crystal of triphenylbismuth bis (Salicylate) pentavalent was synthesized from the reaction of triphenylbismuth di-
chloride with salicylic acid dissolved in methylene chloride at room temperature. The molecular and crystal structures
of triphenylbismuth bis (Salicylate) were determined by X-ray diffraction analysis. This compound crystallizes in the
triclinic space group 1P with crystallographic parameters: a = 11.2937 (3) Å, b = 14.6516 (3) Å, c = 17.8253 (4) Å, α
= 78.2958 (7)˚, β = 76.232 (6)˚, γ = 85.351 (6)˚,6.332 mm
, V = 2803.59 (11) Å, 2
, 3
1.693g cmDc ,
. The final residual factor is 0.0602 for 5806 reflexions with
000 1392,F
293 2KT
. The bismuth
atom of the compound has a distorted trigonal-bipyramidal configuration.
Keywords: Organobismuth; Structure; X-Ray Diffraction; Salicylate; Synthesis
1. Introduction
Bismuth is nontoxic and relatively cheap, and bismuth
compounds have been widely used in catalysis and or-
ganic synthesis [1]. Inorganic bismuth compounds such
as bismuth halides have been used as Lewis acid cata-
lysts in a number of organic reactions [1-5]. However,
the utilization of organobismuth compounds trivalent
and pentavalent for organic synthesis is rarely reported
partly due to the unstable nature of the Bi-C bonds [6,7].
Recent developments show that the incorporation of a
bulky substituent in pentavalent organobismuth com-
plex can result of organobismuth compounds that have
stable Bi-C bonds [8-10]. In our research group, we
have been working on the synthesis of stable pentava-
lent organobismuth compounds. In previous works we
have synthesized organobismuth compounds such as
pentavalent triphenylbismuth dichloride, triphenylbis-
muth diacetate and triphenylbismuth bis (thiophene car-
boxylate) [7,11]. In this work, we report synthesis and
structure determination of the organobismuth compound
triphenylbismuth bis (salicylate), I, where I is the pen-
tavalent complex, bulky and more stable at room tem-
2. Materials and Methods
2.1. Synthesis
The compound triphenylbismuth bis (salicylate) I was
prepared from the triphenyl dichloride and salicylic acid
in solution of methylene chloride. The mixture is heated
to react for one hour of stirring. At the end of the reaction,
the mixture is removed and then recrystallized from di-
chloromethane/pentane (1.1) [12] (Scheme 1).
The obtained compound has the empirical formula
C32H25BiO6 containing an OH and carboxylate groups
that were chosen for our investigation for the following
considerations: 1) the hydroxyl group can act as both
proton acceptor to promote the formation of intermo-
lecular hydrogen bond; 2) the oxygen atoms of the car-
+RT / 1h
Scheme 1. The synthetic route of the triphenylbismuth bis
*Corresponding author. (salicylate) compound, I.
opyright © 2013 SciRes. CSTA
bismuth (V) centre, hence it could act as a proton
2.2. Single Crystal X-Ray Analysis
by single crys-
aining part exhibits
es in
acbonyl of carboxylate ligand is weakly associated with
theceptor and participate in the formation of hydrogen
bonds; 3) The oxygen atom of the carboxylate links to
the central atom of bismuth, forming a stable coordina-
tion bond. The resulting compound is studied using
X-ray diffraction to obtain molecular crystal structure.
The crystal structure of I was determined
tal X-ray diffraction method. X-ray data were collected at
room temperature (293 K) on a Kappa CCD diffracto-
meter (Bruker Nonius, 1998) [13] using MoK
(k = 0.71073 Å), at a voltage of 50 kV and current of 20
mA. Cell parameters were obtained from refinement of
25 reflections collected from a random searching. Data
reduction was performed with Denzo and Scalepack
software [14]. Data obtained were processed with the
WinGX integrated system software package for single
crystal X-ray diffraction data solution, refinement and
analysis [15]. The crystal structure was solved by direct
methods and was refined by full-matrix least-squares
refinement on F2 using the software package SHELX-97
[16]. Molecular graphics were done with ORTEP-3 [17].
In the absence of significant anomalous scattering effects
Friedel pairs have been merged. The crystal data and
structure refinement details are listed in Table 1.
3. Results and Discussion
3.1. Bond Length and Angles
In Figure 1, the central bismuth-cont
a distorted pseudo-trigonal-bipyramidal structure.
The average values of bond distances and angl
fferent aryl rings are in agreement with the literature
Figure 1. Perspective view of the molecule of triphenyl-
Chemical formula C32H25BiO6
bismuth bis (salicylate), I showing the labelling scheme.
Table 1. Crystal data and structure refinement details
C32H25BiO6 compound.
CCDC deposit 737,905
Colour colourless
Crystal dim)
mensions (m0.15 0.10 0.10
Formula weight
Crystal system riclinic
Space group 1P
Unit cell di
1.297 (3)
Cell volu3) 2803.
Temperre (K) 293 (2)
a (Å) 13
b (Å) 14.6516 (3)
c (Å) 17.8253 (4)
α (˚) 78.2958 (7)
β (˚) 76.232 (6)
γ (˚) 85.351 (6)
me 59 (11)
Z 2
tion coeff
mm 6.332
Diffractometer Kappa
Radiation, Mo
Reflections collected/unique 3274
Range of h, k, l
Absorption correction Sortav (Blessing, 1997)
Data/rs 5806/
λ (Å)K, 0.71073
Theta min-max (˚) 1.68 - 27.89
13 14,h
18 19,
Goodness of fit on F2 0.857
R indices
all data)
R indices (0.1564
alues [18]. The bond distances and valence angles of
ata of compound I
molecule I are shown in Table 2.
According to X-ray diffraction d
d as shown in Figure 2, Bi atom has distorted trigo-
nal-bipyramidal coordination with oxygen atoms in api-
cal positions. The O(1) and O(4) atoms are located at the
apical positions and the C(21), C(27) and C(15) atoms
are at the equatorial positions. The sum of angles in
Copyright © 2013 SciRes. CSTA
Table 2. Bond distances and bond angles for non-hydrogen
atoms (e.s.d.’s are given in parenthesis).
Bond distance (Å) Bond angles (˚)
Bi-O1 2.30 (6) 172.(2) 3 O1-Bi-O4 6
Bi-O4 2.313 (6) O1-Bi-C15 93.4 (3)
Bi-C15 2.215 (9) O1-Bi-C21 87.8 (3)
Bi-C21 2.238 (8) O1-Bi-C27 87.5 (3)
Bi-C27 2.200 (9) O4-Bi-C15 91.9 (3)
O1-C1 1.303 (11) O4-Bi-C21 86.0 (3)
O2-C1 1.246 (12) O4-Bi-C27 91.1 (3)
O3-C3 1.380 (14) C15-Bi-C21 104.1 (4)
O4-C8 1.289 (11) C15-Bi-C27 144.4 (4)
O5-C8 1.239 (11) C21-Bi-C27 111.5 (4)
O6-C10 1.358 (13) Bi-O1-C1 105.4 (6)
C1-C2 1.501 (14) B-O4-C8 107.9 (4)
C2-C3 1.415 (15) O1-C1-O2 121.0 (9)
C2-C7 1.386 (16) O1-C1-C2 114.5 (11)
C3-C4 1.395 (17) O2-C1-C2 124.3 (11)
C4-C5 1.33 (2) C1-C2-C3 117.0 (12)
C5-C6 1.36 (2) C1-C2-C7 122.8 (11)
The Bi atom does not almost extend from the equato-
rial plan as we can view in Figure 2.
9) Å) respectively.
ngles from 120˚ in the equatorial
o aromatic rings A and B are perpendicular to
1.365 (16) O3-C3-C2 121.7 (11)
C8-C9 1.472 (13) O3-C3-C4 119.0 (14)
C9-C10 1.368 (14) C2-C3-C4 119.3 (14)
C9-C14 1.403 (13) C3-C4-C5 119.5 (17)
C10-C11 1.393 (17) C4-C5-C6 120.5 (16)
C-C6-C7 123.9 (16)
C2-C7-C6 116.5 (14)
O4-C8-O5 120.5 (9)
O4-C8-C9 116.3 (10)
O5-C8-C9 123.2 (10)
C8-C9-C10 118.1 (10)
C10-C9-C14 119.6 (10)
quatorial plan and the axial angle O-Bi-O for the title e
compound are 360˚ (144.4˚, 104.1˚ and 111.5˚) and
172.6˚, respectively.
20.0437 2.0512P P
23PFo Fc .
However, the (Bi-C(15), Bi-C(21), Bi-C(27)) distances
are (2.215 (9), 2.238 (8) and 2.200 (
e Bi-O(1) and Bi-O(4) distances are (2.303 (6) Å) and
(2.313 (6) Å) respectively. We note that, from Figure 3
that the ligands of carboxylate groups are in cis-position
compared to the phenyl group. In the other hand, inter-
molecular interaction between the bismuth atom and the
two carbonyl groups forms the Van-Der-Waals bond.
The distances between valence-non-bonded Bi-O(2)
and Bi-O(5) are respectively 2.814 (4) and 2.861 (3)
igure 3) which indicate that oxygen atoms are weakly
coordinated with the bismuth atom and form a cis con-
formation together.
This conformation apparently causes significant devia-
tion of the C-Bi-C a
However, Figure 4 shows, in the equatorial plane, that
the tw
Figure 2. Three dimensional structure of compound I
showing different angles in equatorial plan.
Figure 3. Bond lengths of atoms surrounding the bismuth
Copyright © 2013 SciRes. CSTA
Figure 4. A, B and C rings compared to Bi-O bond apical
position. A and B rings are in the sam
is parallel to
n Table 3. We can see that,
n hydrogen and carbon, hy-
cial roles in the crystal pack-
e plan.
Bi-O bond while the third aromatic ring C
Bi-O. The axial positions are occupied by electronegative
atoms and the equatorial ones by carbon atoms of the
aromatic groups. The distortion of the coordination ge-
ometry at bismuth is mainly due to the restrictions im-
posed by the chelate rings.
The bond distances and valence angles of carbon (C15,
C21 and C27) and oxygen (O2 and O4) atoms surround-
ing the bismuth central atom are shown in Figure 5.
3.2. Dihedral Angles
Torsion angles are reported i
the carboxyl groups are coplanar (Bi-O(1)-C(1)-O(2) and
Bi-O(4)-C(8)-O(5)). These two dihedral angles are about
8.01˚ and 1.83˚ respectively (Table 3).
3.3. Hydrogen Bonds
The bond distance betwee
drogen and oxygen noted X-H (Å) and the possible in-
tramolecular interactions by hydrogen bonds noted X-H
(Å) of molecule I is shown in Table 4.
These different hydrogen bonds showed in Figure 6 are
responsible of the molecular packing in the unit cell.
3.4. Crystal Packing
Hydrogen bonds played cru
ing. Figure 7 shows the presence of two molecules in the
unit cell
2Z which corresponds to the centrosym-
metric triclinic space group P1 with two general posi-
yz and
yz .
4. Conclusions
The new pentavalent triphenylbismuth bis (salicylate)
was synthesized with a good yield and its crystal struc-
ture was determined by X-ray diffraction analysis at
room temperature. This work shows that coordination by
the salicylate group is more stable, when compared to
This is caused by rigidity of the ligand between the
bismuth and oxygen atoms, and the presence of hydrogen
nding and the Van-Der-Waals bonding. The three-di-
Table 3. Dihedral angles in degrees with e.s.d.’s given in
Dihedral angles (˚)
O4-Bi-O1-C1 148.12
C15-Bi-O1-C1 75
C21-Bi-O1-C1 179.52
C27-Bi-O1-C1 68.82
O1- Bi-O4-C8 155.21
C15-Bi-O4-C8 68.34
C21-Bi-O4-C8 172.36
C27-Bi-O4-C8 76.14
O1-Bi-C15-C16 101.51
O1-Bi-C15-C20 77.26
O4-Bi-C15-C16 83.58
O4-Bi-C15-C20 97.65
C21-Bi-C15-C16 169.89
C21-Bi-C15-C20 11.34
C27-Bi-C15-C16 11.01
C27-Bi-C15-C20 167.76
O1-Bi-C21-C22 165.63
O1-Bi-C21-C26 10.43
O4-Bi-C21-C22 18.32
O4-Bi-C21-C26 165.61
C15-Bi-C21-C22 72.63
C15-Bi-C21-C26 103.44
C27-Bi-C21-C22 107.94
C27-Bi-C21-C26 76.00
O1-Bi-C27-C32 76.02
O4-Bi-C27-C28 85.34
O4-Bi-C27-C32 96.72
C21-Bi-C27-C28 171.43
C21-Bi-C27-C32 10.62
Bi-O4-C8-O5 1.83
Bi-O4-C8-C9 178.75
O1-C1-C2-C3 177.38
O1-C1-C2-C7 4.16
O2-C1-C2-C3 1.62
O2-C1-C2-C7 179.92
C1-C2-C3-O3 3.34
C1-C2-C3-C4 179.12
C7-C2-C3-O3 175.16
C7-C2-C3-C4 2.37
C1-C2-C7-C6 178.78
C3-C2-C7-C6 2.81
O3-C3-C4-C5 175.31
C2-C3-C4-C5 2.29
Copyright © 2013 SciRes. CSTA
C3-C4-C5-C6 2.76
C4-C5-C6-C7 3.45
C5-C6-C7-C2 3.39
O4-C8-C9-C10 177.60
O4-C8-C9-C14 2.98
O5-C8-C9-C10 3.00
C8-C9-C10-O6 2.49
C8-C9-C10-C11 179.81
C14-C9-C10-O6 178.08
C14-C9-C10-C11 0.37
C8-C9-C14-C13 179.33
C10-C9-C14-C13 1.26
O6-C10-C11-C12 177.42
C9-C10-C11-C12 0.40
C10-C11-C12-C13 0.29
C11-C12-C13-C14 0.60
C12-C13-C14-C9 1.36
Bi-C15-C16-C17 179.16
C20-C15-C16-C17 2.17
Bi-C15-C20-C19 178.95
C16-C15-C20-C19 2.24
C15-C16-C17-C18 0.17
C16-C17-C18-C19 1.73
C17-C18-C19-C20 1.64
C18-C19-C20-C15 0.29
Bi-C21-C22-C23 75.91
C26-C21-C22-C23 0.20
Bi-C21-C26-C25 176.08
C22-C21-C26-C25 0.05
C21-C22-C23-C24 0.53
C22-C23-C24-C25 0.62
C23-C24-C25-C26 0.37
C24-C25-C26-C21 0.04
Bi-C27-C28-C29 78.00
Bi-C27-C32-C31 178.10
Figure 6. Hydrogen bonds representation ensuring the mo-
lecular packing in the unit cell of compound I.
Figure 7. Molecular packing in the unit cell showing two
molecules in symmetric positions (x, y, z) and (x, y, z).
Hydrogen atoms are shown as small spheres for clarity.
Table 4. Hydrogen bonds X-H and XH of molecule I.
Distance of virtual bond
XH (Å)
Distance of actual bond
X-H (Å)
H3O2 1.822 O3-H3 0.820
H6O5 1.798 O6-H6 0.820
H7O1 2.533 C7-H7 0.929
H14O4 2.513 C14-H14 0.930
H16O5 2.556 C16-H16 0.931
H22O4 2.369 C22-H22 0.930
H26O1 2.453 C26-H26 0.929
H28O2 2.777 C28-H28 0.930
H28O5 2.636
bondthe Vr-Waals g. The-di-
mensional representation of the m showsxial
position groups and the equatorial
posite threyls. This shows that the crystal
struciphenylbismuth biste) pelent
has a shape distorted trigonal-bipyramid.
ing and an-Debondin three
olecule the a
of the two salicylate
ion of the phen
ture of tr (Salicylantava
Figure 5. Bond distances and valence angles around the
bismuth atom.
Copyright © 2013 SciRes. CSTA
Copyright © 2013 SciRes. CSTA
[1] zuki aatano, anobis he-
rdam, 2
[2] mamot. IshihaAcid Ca
rganic sis, Wileinhe08.
[3] rd-Iloue and C. Le Roux, “Bismuth(III)
Triflate in Organic Synthesis,” European Journal of Or-
In: H. Sund Y. MEds., Orgmuth C
mistry, Elsevier, Amste001.
In: H. Ya
Modern O
o and H
ra, Eds.,
ey-VCH, W
im, 20
H. Gaspaghman
ganic Chemistry, Vol. 2004, No. 12, 2004, pp. 2517-2532.
[4] R. M. Hua, “Recent Advances in Bismuth-Catalyzed Or-
ganic Synthesis,” Current Organic Synthesis, Vol. 5, No.
1, 2008, pp. 1-27. doi:10.2174/157017908783497518
[5] R. M. A. Pinto, J. A. R. Salvador, C. L
Paixão, “Bismuth(III) Triflate-Catalyzed
e Roux and J. A.
Direct Conver-
sion of Corticosteroids into Highly Functionalized 17-Ke-
tosteroids by Cdroxyacetone Side
leavage of the C17-Dihy
Chain,” Journal of Organic Chemistry, Vol. 74, No. 21,
2009, pp. 8488-8491. doi:10.1021/jo9018478
[6] M. Bao, E. Hayashi and S. Shimada, “Cationic Organo-
nd Reactivity of Triphenyl-
bismuth Complex with 5,6,7,12-Tetra Hydrodibenz [c,f][1,5]
Azabismocine Framework and Its Coordination Com-
plexes with Neutral Molecules,” Organometallics, Vol.
26, No. 7, 2007, pp. 1816-1822.
[7] A. Miloudi, D. El-Abad, G. Boyer, J.-P., Galy and J.-P.,
Finet, “Synthesis, Structure a
bismuth Bis(2-Thiophenecarboxylate),” Main Group Metal
Chemistry, Vol. 24, No. 11, 2001, pp. 767-774.
[8] M. Chovancová, R. Jambor, A. Růžička, R. Jirásko, I.
Císařová and L. Dostál, “Synthesis, Structure, and Reac-
tivity of Intramolecularly Coordinated Organoantimony
and Organobismuth Sulfides,” Organometallics, Vol. 28,
No. 6, 2009, pp. 1934-1941. doi:10.1021/om801194h
[9] P. Simon, F. de Proft, R. Jambor, A. Ruzicka and L. Dos-
tál, “Monomeric Organoantimony(I) and Organobismuth(I)
Compounds Stabilized by an NCN Chelating Ligand: Syn-
theses and Structures,” Angewandte Chemie International
Edition, Vol. 49, No. 32, 2010, pp. 5468-5471.
[10] A. Soran, H. J. Breunig, V. Lippolis, M. Arca and C. Sil-
vestru, “Syntheses, Solid-State Structures, Solution Be-
havior of Hypervalent Organobismuth(III) Compounds
[2-(Et2NCH2)C6H4]nBiX3n and DFT Characterization of
[2-(Me2NCH2)C6H4]nBiX3n [X = Cl, Br, I; n = 1–3],”
Journal of Organometallic Chemistry, Vol. 695, No. 6,
2010, pp. 850-862. doi:10.1016/j.jorganchem.201
yer, J.-P., Galy, J.-P., Finet [11] A. Miloudi, D. ElAbad, G. Bo
and S. Didier, “Reactivity of 2-Aminothiazole and 2- or
6-Aminobenzothiazole Derivatives towards the Triphenyl-
bismuth Diacetate/Catalytic Copper Diacetate Phenyla-
tion System,” European Journal of Organic Chemistry,
Vol. 2004, No. 7, 2004, pp. 1509-1516.
[12] T. Arnauld, D. H. R. Barton and E. Doris, “The Che-
mistry of Pentavalent Organobismuth Reagents. Part 14.
Recent Advances in the Copper-Catalyzed Phenylation of
Amines,” Tetrahedron, Vol. 53, No. 12, 1997, pp. 4137-
[13] E. Nonius, “CAD-4 Express Software,” Delft, 1996.
[14] Z. Otwinowski and W. Minor, “Processing of X-Ray Dif-
fraction Data Collected in Oscillation Mode,” Methods in
Enzymology, Vol. 276, 1997, pp. 307-326.
[15] L. J. Farrugia, “WinGX Suite for Small-Molecule Single-
Crystal Crystallography,” Journal of Applied Crystallog-
raphy, Vol. 32, 1999, pp. 837-838.
[16] G. M. Sheldrick, “A Short History of SHELX,” Acta
Crystallographica, Vol. 64, No. 1, 2008, pp. 112-122.
[17] L. J. Farrugia, “ORTEP-3 for Windows—A Version of
ORTEP-III with a Graphical User Interface (GUI),” Jour-
nal of Applied Crystallography, Vol. 30, 1997, pp. 565-
567. doi:10.1107/S0021889897003117
[18] E. Prince and A. J. C. Wilson, “International Tables for
X-ray Crystallography,” 2nd Edition, Kluwer Academic
Press, Boston, 1992.