Advances in Chemistry
Volume 2015 (2015), Article ID 625310, 7 pages
http://dx.doi.org/10.1155/2015/625310

Research Article

Synthesis and Structural Studies of a New Complex of Di[hexabromobismuthate (III)] 2,5-Propylaminepyrazinium [C₁₀H₂₈N₄]Bi₂Br₁₀

Mohamed El Mehdi Touati and Habib Boughzala

Laboratoire de Matériaux et Cristallochimie, Faculté des Sciences, Université de Tunis El Manar, 2092 Tunis, Tunisia

Received 29 September 2014; Revised 15 December 2014; Accepted 20 December 2014

Academic Editor: Jolanta N. Latosinska

Copyright © 2015 Mohamed El Mehdi Touati and Habib Boughzala. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

A new organic-inorganic hybrid material, [C₁₀H₂₈N₄]Bi₂Br₁₀, has been synthesized and characterized. The compound crystallizes in monoclinic P2₁/c space group with a = 11.410(4) Å, b = 11.284(4) Å, c = 12.599(3) Å, β = 115.93(2)°, and V = 1458.8(8) Å³. The structure consists of discrete dinuclear [Bi₂Br₁₀]⁴⁻ anions and [C₁₀H₂₈N₄]⁴⁺ cations. It consists of a 0-D anion built up of edge-sharing bioctahedron. The crystal net contains N–H⋯Br hydrogen bonds. The differential scanning calorimetry (DSC) reveals an irreversible phase transition at −17°C. The frontier molecular orbital and the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) calculation allow the classification of the material as an insulator.

1. Introduction

The results of systematic structural investigations of halobismuthate (III) compounds reveal a great variety of different anionic frameworks. Most of these compounds are described by a general formula    (where R is organic cations, M is Bi, and X is Cl, Br, and I) and have a tendency to constitute bi- or polynuclear anions in the crystalline state.

Generally, in these compounds, the coordination sphere of bismuth appears to be dominated by the tendency towards hexacoordination with polybismuthate species arising from corner, edges, or faces sharing BiX₆ distorted octahedra.

The formation of the anionic sublattice is clearly determined by the counteractions, but the effects of their most evident properties such as charge, size, and shape are almost not predictable. The organic moiety can be used as physical and electronic barrier, contributing to original electrical and optical behaviour. In addition, since, in the crystal state, important contribution to the lattice stabilization is due to hydrogen bonding interactions, it should be possible to influence the bismuth coordination geometry acting on the number and orientation of the hydrogen bond donor sites of the cations [1–4].

2. Synthesis Experimental Protocol

The title compound was synthesized by dissolving stoichiometric amounts of bismuth (III) bromide in piperazine in a mixture of water and HBr. The resulting solution was stirred well and then kept at room temperature. Few weeks later, transparent crystals, as bright-yellow prism, were grown by slow evaporation. The purity of synthesized compound was improved by successive recrystallization process.

3. Results and Discussion

3.1. X-Ray Data Collection

The X-ray diffraction intensities from a single crystal of about (0.3 × 0.3 × 0.1) mm³ were collected with a CAD-4 (Enraf Nonius) diffractometer using the Mo Kα radiation (λ = 0.71073 Å). The crystal structure was solved by direct methods using SHELXS-97 [5]. Full-matrix least-squares refinement and subsequent Fourier synthesis procedures were performed using SHELXL-97 [6]. Molecular graphics were prepared using Diamond 3 [7]. CCDC-1008226 contains the supplementary crystallographic data for this compound. These data can be obtained free of charge at http://www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK.

Hydrogen atoms were located at their idealized positions using appropriate HFIX instructions in SHELXL-97 and included in subsequent least-squares refinement cycles in riding-motion approximation. Crystal data and parameters of the final refinement are reported in Table 1.

Table 1: Experimental data for C₁₀H₂₈N₄Bi₂Br₁₀.

Crystal data
Data collection

Empirical formula
C₁₀H₂₈N₄Bi₂Br₁₀
Diffractometer
Enraf-Nonius CAD-4

Formula weight
1417.42 (g·mol⁻¹)
Wavelength:
0.71073 Å

Crystal system
Monoclinic
range
2.55° ≤ ≤ 26.97°

Space group
P2₁/c
Temperature
298 (2) K

Unit cell
dimensions
= 11.410 (4) Å
= 11.284 (4) Å
= 12.599 (3) Å
= 115.93 (2)°
Limiting indices , , and
−14 ≤ ≤ 13
0 ≤ ≤ 14
0 ≤ ≤ 16

Crystal habit
Yellow prism
Absorption correction
Psi scan

Volume
= 1458.8 (8) Å³
Standard reflection
2 every 120 min

= 4
Measured reflections
3697

Absorption
coefficient
= 25.75 mm⁻¹
Independent reflections
3177

(000)
1264
Observed reflections >
2352

Crystal size (mm³)
(0.3 0.3 0.1)

0.062

Densitycalc
= 3.236
/
0.001/0.074

Refinement

Refinement
Least square on

4.95 eÅ⁻³

>
0.066

−7,09 eÅ⁻³

1.06
wR
0.169

3.2. Crystal Morphology

Crystal morphology is a key element in many industrial processes and has an enormous impact in the materials processing stages. Thus, rationalization of the relationships between crystal morphology and the arrangement of atoms in the bulk crystal lattice is of great interest in many areas of science.

The crystal morphology prediction was obtained by BFDH (Bravais-Fridel and Donnay-Harker) [8–10] algorithm calculation using Mercury (CSD 3.0.1) [11].

The program uses the crystal lattice parameters and the symmetry space group to generate a list of possible growth faces and their relative growth rates.

The qualitative analysis result obtained by energy dispersive X-ray spectroscopy (EDX) is presented in Figure 1. It reveals the presence of the chemical elements identified by the single crystal X-ray diffraction.

Figure 1: Qualitative analysis by EDX of C₁₀H₂₈N₄Bi₂Br₁₀.

The scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) high resolution images of the surface topography produces an image of the focused crystal. The view of the observed and calculated crystal morphologies reveals a similarity between the two shapes (Figure 2). This result allows identifying the crystallographic axis and shows the absence of preferential orientation of crystallites.

(a)

(b)

Figure 2: Observed and calculated morphologies of C₁₀H₂₈N₄Bi₂Br₁₀ crystals.

3.3. Structure Description

At room temperature, the present compound crystallizes in the monoclinic P2₁/c space group. The asymmetric unit contains two bromobismuthate [Bi₂Br₁₀]⁴⁻ anions and [C₁₀H₂₈N₄]⁴⁺ cation, as shown in Figure 3.

(a)

(b)

Figure 3: ORTEP of the inorganic part [Bi₂Br₁₀]⁴⁻ in (a) and the organic moiety [C₁₀H₂₈N₄]⁴⁺ in (b) with 50% of probability level.

The organic and inorganic moieties are linked by N–H⋯Br hydrogen bonds ensuring the structure cohesion.

The 1 : 5 stoichiometry of anionic part [Bi₂Br₁₀]⁴⁻ can be realized by different types of anionic sublattices.

In this compound, two BiBr₆ octahedra share two bridging Br atoms and consequently form dinuclear [Bi₂Br₁₀]⁴⁻ anion. One bismuth (III) ion is surrounded by six bromine anions; however, Bi–Br distances fall into two ranges: 2.793(2) to 2.894(2) Å for terminal Br and 2.981(4) to 3.079(2) Å for the bridging ones (Table 2). Lower than the sum of Van der Waals radii (4.35 Å according Pauling [12]), we deduce that the bismuth-bromine bonds have a dominant covalent character.

Table 2: Selected interatomic distances (Å) and angles (°) in the structure of C₁₀H₂₈N₄Bi₂Br₁₀.

(a) Octahedra BiBr₆

Bi–Br4
2.744 (2)
Br5–Bi–Br2
169.15 (6)

Bi–Br3
2.748 (3)
Br4–Bi–Br1
98.30 (6)

Bi–Br5
2.793 (2)
Br3–Bi–Br1
170.84 (6)

Bi–Br2
2.894 (2)
Br5–Bi–Br1
84.48 (7)

Bi–Br1
2.981 (4)
Br2–Bi–Br1
91.96 (6)

Bi–Br1i
3.079 (2)
Br4–Bi–Br1i
170.99 (5)

Br1–Bii
3.079 (2)
Br3–Bi–Br1i
82.72 (6)

Br4–Bi–Br3
90.61 (7)
Br5–Bi–Br1i
90.14 (6)

Br4–Bi–Br5
84.30 (6)
Br2–Bi–Br1i
100.00 (6)

Br3–Bi–Br5
94.36 (7)
Br1–Bi–Br1i
88.19 (5)

Br4–Bi–Br2
86.09 (6)
Bi–Br1–Bii
91.81 (5)

Br3–Bi–Br2
90.75 (7)

(b) Organic group

C1–N2
1.490 (2)
N2–C1–C2
111.30 (1)

C1–C2
1.500 (2)
C1–C2–C3
109.00 (1)

C2–C3
1.500 (2)
C2–C3–N1
113.30 (1)

C3–N1
1.501 (2)
N1–C4–C5ii
113.60 (1)

C4–N1
1.454 (2)
N1–C5–C4ii
112.50 (1)

C4–C5ii
1.520 (2)
C4–N1–C3
115.10 (1)

C5–N1
1.510 (2)
C4–N1–C5
110.00 (1)

C5–C4ii
1.520 (2)
C3–N1–C5
109.50 (1)

Symmetry codes: (i) – + 1, , + 2; (ii) – + 1, , + 1.

The BiBr₆ octahedra are somewhat distorted. As described by Shannon [13], the distortion index of this polyhedra ( = 1.88 10⁻³) indicates a significant dissymmetry in the dinuclear entity [Bi₂Br₁₀]⁴⁻ where is the average value of the Bi–Br bond length. The bond angles values (see Table 3) confirm the octahedral distortion since they are, in some cases, 10° less than the ideal values.

Table 3: Hydrogen bonds for C₁₀H₂₈N₄Bi₂Br₁₀ (D: donor; A: acceptor).

D–H⋯A
D–H (Å)
H⋯A (Å)
D⋯A (Å)
D–H⋯A (°)

N1–H1⋯Br5
0.909
2.779 (3)
3.534 (1)
141.27 (7)

N2–HA⋯Br3
0.890
2.703 (2)
3.537 (2)
156.38 (1)

N2–HB⋯Br2
0.890
2.792 (2)
3.521 (2)
149.03 (1)

N2–HB⋯Br4
0.890
2.829 (2)
3.487 (2)
131.92 (1)

The intermolecular N–H⋯Br hydrogen bonds can be also the reason of geometrical distortion of [Bi₂Br₁₀]⁴⁻ anion, due to possibility of shifting of the halogen atoms in the direction of the positive charge located on the cations.

The protonation of [C₁₀H₂₈N₄] leads to [C₁₀H₂₈N₄]⁴⁺. These cations are stacked between the planes containing the bioctahedrons [Bi₂Br₁₀]⁴⁻.

Each bioctahedron is sandwiched between two sheets of organic cations, setting out its 6 vertices Br⁻ where three links to the higher plane and the others with the lower one by hydrogen bonds involve the terminal amino group of the organic cations.

Hydrogen bonds are linking the organic and inorganic moieties (Table 3). This fact can explain the observed fragility of the crystals. The hydrogen bonds ensure the crystal cohesion by connecting the alternating organic-inorganic layers and building a three-dimensional framework.

3.4. Infrared Spectroscopy

The IR spectrum of C₁₀H₂₈N₄Bi₂Br₁₀ (Figure 4 and Table 4) was recorded at room temperature in the range of 400 to 4000 cm⁻¹ using the VERTEX 80/80 v FT-IR research spectrometer, by dispersing 2% of the studied compound in KBr discs. We have calculated the vibrational spectrum by using semiempirical PM3 geometry optimization by “CAChe” program [14].

Table 4: Infrared bands observed and assigned to vibration modes for C₁₀H₂₈N₄Bi₂Br₁₀.

Observed frequencies (cm⁻¹)
Attributions

3470
Stretching (N–H)

2925
Stretching (C–H)

1640
Bending (N–H)

1389
Bending (C–H) and stretching (C–C)

1114
Stretching (C–N)

Figure 4: Observed IR spectrum of the compound C₁₀H₂₈N₄Bi₂Br₁₀.

After an optimization of the molecular configuration, the calculated spectrum, presented in Figure 5, is very helpful for the attribution of the observed spectroscopic bands. On the other hand, the observed bands assignment becomes easier by comparing the observed frequencies and those calculated.

Figure 5: Calculated IR spectrum of the compound C₁₀H₂₈N₄Bi₂Br₁₀.

Based on the previous literature results and the theoretical simulation of the IR spectrum, the large band around 3470 cm⁻¹ is attributed to the stretching modes of (N–H) in the amine group. The out of plane bending mode of this group is probably responsible for the band located at 1640 cm⁻¹. The (C–H) stretching of methylene group is centered on 2925 cm⁻¹.

The band around 1389 cm⁻¹ is probably the result of the bending vibration of (C–H) and the stretching of (C–C). The stretching modes of (C–N) are probably observed around 1114 cm⁻¹.

3.5. Thermal Properties

The differential scanning calorimetry (DSC) thermogram, shown in Figure 6 was performed with a DSC EVO131 instrument under nitrogen atmosphere. Firstly, no phase transition was observed when the sample was under cooling until −45°C; then, during heating from −45 to 20°C, we observed an energetic effect that reveals a phase transition in the temperature range of (−17/−12)°C accompanied by a significant enthalpy transition () evaluated at 2.732 Jg⁻¹. Comparing the heating and the cooling curves, the observed phenomenon seems to be irreversible. Further treatments are scheduled to know the structural behaviour of the resulting compound after the DSC experiment.

(a)

(b)

(c)

Figure 6: Differential scanning calorimetry curves of C₁₀H₂₈N₄Bi₂Br₁₀.

3.6. X-Ray Powder Diffraction

The X-ray powder diffraction technique (XRD) was used to control the crystalline phase purity. The diffraction pattern was obtained on a D8 ADVANCE Bruker diffractometer with a Lynxeye accelerator using Cu (Kα ₁/α ₂ = 1.54060/1.54439 Å) wavelength. The measurement was performed in spinning mode (60 tr·mn⁻¹) in order to minimize the preferential orientation effect of the crystallites with step-scanning (Δ2θ = 0.02°) constant time interval of 0.1 s. The quantitative criteria of goodness of fits are the following agreement factors: where and are the observed and calculated intensities at the ith step in the pattern, respectively. is the reciprocal of the variance of each observation; the summation is carried out over all the observations and “” is a scale factor.

The refinements were carried out using TOPAS program [15].

The basic structural model for the C₁₀H₂₈N₄Bi₂Br₁₀ was taken from Topa et al. output [16]. Details of the refinement are given in Table 5.

Table 5: Unit cell parameters and details of Rietveld refinement of C₁₀H₂₈N₄Bi₂Br₁₀.

Formula
C₁₀H₂₈N₄Bi₂Br₁₀

System
Monoclinic

Space group
P2₁/c

4

Unit cell

    /Å
11.387 (1)

    /Å
11.260 (1)

    /Å
12.577 (1)

    /(°)
115.925 (3)

Volume/Å³
1450.45 (2)

Density
3.245 (5)

Zero point 2/(°)
0.0182 (8)

Reliability factors (%)

3.85

5.89

4.917

2.22

Figure 7 shows good agreement between the observed and calculated XRD patterns which confirms the crystalline purity of the prepared compound with an experimental error of 3% of mass. Furthermore, the XRPD raw diffraction is marked with the presence of a large hump centered around 2θ = 13°, signature of an amorphous part. The TOPAS degree of crystallinity calculation gives about 86%.

Figure 7: Experimental and calculated X-ray diffraction patterns and their difference for C₁₀H₂₈N₄Bi₂Br₁₀.

3.7. The HOMO-LUMO Gap

Crystalline materials can be classified according to their band gap. The C₁₀H₂₈N₄Bi₂Br₁₀ exhibits absorption bands around  eV calculated by the program “CAChe” using the semiempirical PM3 method and corresponding to the electronic transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied one (LUMO). The atomic orbital compositions of the frontier molecular orbital are sketched in Figure 8.

Figure 8: Calculated frontier molecular orbital of the title compound.

We can note the HOMO contribution coming from the halogen. In the LUMO, the percentage of contribution from the bromine atoms is dominant. These calculations show that the electronic properties are roughly imposed by the inorganic part. The Bi coordination geometry is the dominant structural factor influencing the electronic structure of studied compound [17].

4. Conclusion

The present paper has shown that the new organic-inorganic hybrid C₁₀H₂₈N₄Bi₂Br₁₀ was synthesized by slow evaporation. Its structure is built up by dibutylpyrazinium dications and discrete (0-D) bromobismuthate anions. Several experimental techniques have been used to characterize the new compound.

The crystal structure was solved by single crystal X-ray diffraction. The vibrational properties were studied by Raman scattering and infrared spectroscopy; the crystal morphology was carries out using the Bravais-Freidel and Donnay-Harker model, and the X-ray powder diffraction measurement was carried out to check the title compound’s purity.

The crystal structure of C₁₀H₂₈N₄Bi₂Br₁₀ consists of discrete [Bi₂Br₁₀]⁴⁻ anions with dinuclear geometry of two BiBr₆ octahedra sharing two bridging Br atoms and [C₁₀H₂₈N₄]⁴⁺. The cohesion is assumed by hydrogen bonds. The title compound undergoes one low-temperature phase transitions at −17°C identified by differential scanning calorimetry.

Conflict of Interests

The authors declare that there is no conflict of interests regarding the publication of this paper.

References

A. Piecha, V. Kinzhybalo, R. Jakubas, J. Baran, and W. Medycki, “Structural characterization, molecular dynamics, dielectric and spectroscopic properties of tetrakis(pyrazolium) bis(μ ₂-bromo-tetrabromobismuthate(III)) dihydrate, [C₃N₂H₅]₄[Bi₂Br₁₀].2H₂O,” Journal of Coordination Chemistry, vol. 9, pp. 1036–1048, 2007.

G. A. Bowmaker, P. C. Junk, M. Lee Aaron, B. W. Skelton, and A. H. White, “Synthetic, structural and vibrational spectroscopic studies in bismuth(III) halide/N,N ′-Aromatic bidentate base systems. I large-cation (2,2′-bipyridinium and 1,10-phenanthrolinium) salts of polyhalobismuthate (III) ions,” Australian Journal of Chemistry, vol. 51, no. 4, pp. 293–309, 1998.

F. Benetollo, G. Bombieri, G. Alonzo, N. Bertazzi, and G. A. Casella, “Synthesis and crystal structure of [(PhenH)(PhenH₂)][BiCl₆]·2H₂O with different o-phenanthroline protonations,” Journal of Chemical Crystallography, vol. 28, no. 11, pp. 791–796, 1998.

G. Alonzo, F. Benetollo, N. Bertazzi, and G. Bombieri, “Synthesis and crystal structures of 4,4′-bipyridinium and 2,2′-bipyridinium pentachloro complexes containing the polynuclear anions [Bi2Cl10]4- and [Bi4Cl20]8-,” Journal of Chemical Crystallography, vol. 29, no. 8, pp. 913–919, 1999.

G. M. Sheldrick, SHELXS-97, Program for Crystal Structure Solution, University of Göttingen, Göttingen, Germany, 1997.

G. Sheldrick M, SHELXL-97: Program for the Refinement of Crystal Structures, University of Göttingen, Göttingen, Germany, 1997.

K. Brandenburg, Diamond, Crystal Impact GbR, Bonn, Germany, 2008.

A. Bravais, Etudes Cristallographiques, Gauthier-Villars, Paris, France, 1913.

G. Fridel, “Crystal habits of minerals,” Bulletin de la Société Chimique de France, pp. 326–455, 1907.

J. D. Donnay and H. Harker D, Springer Handbook of Crystal Growth, American Mineralogist, 1937.

(CCDC), Mercury CSD 3. 0. 1 (Build RC6), Cambridge Crystallographic Data Centre (CCDC), 2011.

L. Pauling, The Nature of Chemical Bond, Cornell University Press, Ithaca, NY, USA, 1960.

R. D. Shannon, “Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides,” Acta Crystallographica A, vol. 32, part 5, pp. 751–767, 1976.

Cache: Worksystem 7.5.0.85, Fujitsu Limited, Oxford, UK, 2000–2006.

A. A. Coelho, TOPAS, Version 4.2 (Computer Software), Coelho Software, Brisbane, Australia, 2009.

D. Topa, E. Makovicky, H. J. Schimper et al., “The crystal structure of SnSb4S7, A new member of the meneghinite homologous series,” Canadian Mineralogist, vol. 48, no. 5, pp. 1119–1126, 2010.

J. E. Monat, J. H. Rodriguez, and J. K. McCusker, “Ground- and excited-state electronic structures of the solar cell sensitizer bis(4,4′-dicarboxylato-2,2′-bipyridine)bis(isothiocyanato)ruthenium(II),” Journal of Physical Chemistry A, vol. 106, no. 32, pp. 7399–7406, 2002.