Synthesis and Structural Study of Triphenylbismuth Bis (Salicylate)

doi:10.4236/csta.2013.21004

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Crystal Structure Theory and Applications, 2013, 2, 28-33

http://dx.doi.org/10.4236/csta.2013.21004 Published Online March 2013 (http://www.scirp.org/journal/csta)

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: *[email protected]

Received October 29, 2012; revised December 5, 2012; accepted December 18, 2012

ABSTRACT

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-

perature.

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-

Cl OH

CH2Cl2Bi

+RT / 1h

Scheme 1. The synthetic route of the triphenylbismuth bis

*Corresponding author. (salicylate) compound, I.

K. FEHAM ET AL. 29

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



radiation

(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-

for

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)

1429

mensions (m0.15 0.10 0.10

Formula weight

Crystal system riclinic

Space group 1P

Unit cell di

1.297 (3)

Cell volu (Å3) 2803.

Temperre (K) 293 (2)

Density

mensions

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

atu





gcm

Absorpicient

1.693

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/

Final

CCD

λ (Å)K, 0.71073

Theta min-max (˚) 1.68 - 27.89

8/12722

13 14,h

18 19,

023





estraints/parameter0/712

Goodness of fit on F2 0.857

R indices





2RF











 0.

all data)

0602

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

K. FEHAM ET AL.

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)

C6-C7

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.



1wFo







20.0437 2.0512P P







where



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

an.

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

atom.

K. FEHAM ET AL. 31

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-

tions



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

pentaphenylbismuth.

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

parenthesis.

Dihedral angles (˚)

O4-Bi-O1-C1 −148.12

C15-Bi-O1-C1 75



.50

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

K. FEHAM ET AL.

Continued

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 X…H of molecule I.

Distance of virtual bond

X…H (Å)

Distance of actual bond

X-H (Å)

H3O2 1.822 O3-H3 0.820

H6O5 1.798 O6-H6 0.820

H7O1 2.533 C7-H7 0.929

H14O4 2.513 C14-H14 0.930

H16O5 2.556 C16-H16 0.931

H22O4 2.369 C22-H22 0.930

H26O1 2.453 C26-H26 0.929

H28O2 2.777 C28-H28 0.930

H28O5 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.

K. FEHAM ET AL.

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