Mono- and Binuclear Chloride and Bromide Complexes of Bi(III) with Double-Charged Cations Based on Pyridine: Syntheses and Crystal Structures

Article abstract of DOI:10.1134/S1070328418080031

Abstract: The reactions of solutions obtained by the reactions of Bi₂O₃ with 2 M HCl and HBr with the salts containing bis(pyridyl)alkane cations afford mono- and binuclear halide complexes (Py-(CH₂)₃-Py)₃[Bi₂Br₉]₂ (I), (H₃O)(Py-(CH₂)₄-Py)[BiCl₆] ? 3H₂O (II), and (H₂Bpp)₂[Bi₂Br₁₀] ? 2H₂O (Bpp is 1,3-bis(4-pyridyl)propane) (III). The structures of the synthesized compounds are determined by X-ray diffraction analysis (СIF files CCDC no. 1583338–1583340, respectively).

Full text of DOI:10.1134/S1070328418080031

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2018, Vol. 44, No. 8, pp. 502–506. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © I.D. Gorokh, S.A. Adonin, D.G. Samsonenko, M.N. Sokolov, V.P. Fedin, 2018, published in Koordinatsionnaya Khimiya, 2018, Vol. 44, No. 4,
pp. 250–254.
Mono- and Binuclear Chloride and Bromide Complexes
of Bi(III) with Double-Charged Cations Based on Pyridine:
Syntheses and Crystal Structures
I. D. Gorokha, S. A. Adonina, b, *, D. G. Samsonenkoa, b, M. N. Sokolovb, c, and V. P. Fedina, b
aNovosibirsk State University, Novosibirsk, 630090 Russia
bNikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
cKazan (Volga region) Federal University, Kazan, Russia
*e-mail: adonin@niic.nsc.ru
Received November 3, 2017
Abstract—The reactions of solutions obtained by the reactions of Bi2O3 with 2 M HCl and HBr with the salts
containing bis(pyridyl)alkane cations afford mono- and binuclear halide complexes (Py-(CH2)3-
Py)3[Bi2Br9]2 (I), (H3O)(Py-(CH2)4-Py)[BiCl6] ⋅ 3H2O (II), and (H2Bpp)2[Bi2Br10] ⋅ 2H2O (Bpp is 1,3-
bis(4-pyridyl)propane) (III). The structures of the synthesized compounds are determined by X-ray diffrac-
tion analysis (СIF files CCDC no. 1583338–1583340, respectively).
Keywords: bismuth, chloride complexes, bromide complexes, crystal structure
DOI: 10.1134/S1070328418080031
INTRODUCTION
of the products are the properties of the solvent used
and, to a higher extent, the nature of the cation [11,
12]. At the same time, although the significant body of
experimental data on the structures of such com-
pounds has been obtained within the recent years [13–
18] and the overall number of deposited crystal struc-
tures exceeds 200 (for Bi(III)), it remains to be a per-
spective task to find correlations in this information
array. Evidently, to solve this problem, one has to
extend the number of described crystal structures and
also to specify boundary parameters, which, in partic-
ular, can be synthesis conditions. One of the popular
variants is the synthesis of halometalates in aqueous
solutions of HX (X = Cl, Br, I), i.e., in an acidic
medium in presence of a considerable excess of halide
anions.
In spite of the fact that halide complexes are among
the “classical” objects of investigation by coordination
chemistry, this area continues attracting attention of
researchers. For the compounds of post- and late-
transition metals, this is caused, to a significant extent,
by the physical properties interesting from the view-
point of materials science, such as photocatalysis [1–
4], ferroelectric properties [5–7], applicability in pho-
tovoltaic devices [8–10], and others. From the prepar-
ative point of view, these complexes are simple objects:
as a rule, they are synthesized by the addition of halide
salts of various metals to solutions containing anionic
species [MXn]a– (X = Cl, Br, I). This results in the for-
mation of crystals, whose quality is sufficient for X-ray
diffraction analysis. The main problem remaining
unsolved is the search for a relationship between the
synthesis conditions and the composition and struc-
ture of the anionic moiety of these compounds. This is
due to the fact that some metals (especially post-tran-
sition metals, in particular, Bi(III)) are characterized
by a relatively low energy of the M–X bond and the
fast kinetics of ligand substitution. Owing to this, solu-
tions containing halometallate anions can be consid-
ered as “virtual dynamic libraries” capable of forming
In this work, we synthesized and structurally charac-
terized three new halide complexes of Bi(III): (Py-
(CH2)3-Py)3[Bi2Br9]2 (I), (H3O)(Py-(CH2)4-Py)[BiCl6] ⋅
3H2O (II), and (H2Вpp)2[Bi2Br10] ⋅ 2H2O (Bpp is 1,3-
bis(4-pyridyl)propane) (III).
EXPERIMENTAL
Compounds I–III were synthesized in air.
polynuclear anions of diverse structures and composi- Reagents (reagent grade) were purchased from com-
tions upon the addition of a large organic cation to the mercial sources and used as received. Bromides of
system and solid phase precipitation. It is noted that bis(pyridyl)alkane cations were synthesized by the
the most important factors determining the structures reaction of pyridine (2 equiv) and 1,3-dibromopro-
502

MONO- AND BINUCLEAR CHLORIDE AND BROMIDE COMPLEXES
503
pane (1 equiv) or 1,4-dibromobutane in acetonitrile atomic displacements for compounds I–III were
(reflux, 18 h, yield >92%). The purity of the products deposited with the Cambridge Crystallographic Data
was monitored by 1H NMR spectroscopy and elemen-
tal analysis.
Centre (CIF files CCDC 1583338–1583340, respec-
tively; http://www.ccdc.cam.ac.uk/structures) and
also are available from the authors.
Synthesis of compound I. BiOBr (50 mg,
0.16 mmol) was dissolved in 2 M HBr (8 mL), and a
solution of (Py-(CH2)3-Py)Br2 (89 mg, 0.27 mmol) in
2 М HBr (7 mL) was added. A pale yellow crystalline
precipitate of compound I began to form within sev-
eral minutes. In 2 h, the product was separated by fil-
tration. The yield was 88%.
RESULTS AND DISCUSSION
A specific feature of the Bi(III) halide complexes is
a variety of structural types: discrete anions with the
nuclearity from 1 to 8 [22–28] and coordination poly-
mers of various topology (predominantly 1D) are
known. The formation of the mono- and binuclear
anions and chain polymers of the {[BiX5]n}2n– and
For C H N Br Bi
39 48
6
18
4
Found, %
Anal. calcd., %
C, 16.3
С, 16.3
H, 1.8
H, 1.7
N, 3.1
N, 2.9
{[BiX4]n}n– types [29] is observed most frequently.
Thus, from the structural viewpoint, compounds I–
III are fairly typical representatives of their class.
Synthesis of compound II. (Py-(CH2)4-Py)Br2
(50 mg, 0.13 mmol) was dissolved in water (4 mL), and
AgNO3 (45 mg, 0.27 mmol) was added with vigorous
stirring. In 15 min, the formed precipitate of AgBr was
The anionic moiety of complex I is presented by
the binuclear anions [Bi2Br9]3– consisting of two octa-
filtered off, and concentrated HCl was added to the hedral fragments {BiBr6} with the common face. This
mother liquor to achieve a concentration of 2 mol/L.
Then a solution of Bi2O3 (31 mg, 0.067 mmol) in 2 M
HCl (1 mL) was added. A gradual formation of color-
less crystals of compound II was observed for several
hours. The yield was 72%.
type is fairly abundant, although the number of bro-
mobismuthates [Bi2Br9]3– [30–32] is much lower than
that of similar chloride and especially iodide com-
plexes [29]. The Bi–Brterm distances (2.6955(8)–
2.7670(9) Å) are typical. At the same time, one of the
Bi–(μ2-Br) bonds (2.9626(9) Å) in compound I is
somewhat shorter than that in the complexes
described earlier (cf. 2.98 Å [31]). The crystal packing
in the structure of complex I is shown in Fig. 1. Inter-
estingly, the crystals in compound I are not isostruc-
tural to the crystals of the chlorobismuthate complex
(Py-(CH2)3-Py)3[Bi2Cl9]2 described by us previously
[33], despite the fact that both empirical composition
and structure of anionic moiety are the same.
The reaction with the salt of the pyridine derivative
bearing the long –(CH2)4– fragment (one additional
methylene group) affords mononuclear complex II
(the crystal packing is shown in Fig. 2). Unlike a sim-
ilar bromobismuthate [33], this compound is isolated
as a solvate (contains three crystallization molecules of
H2O) fairly stable at ambient temperature (according
to the elemental analysis data, the composition only
insignificantly changes within several days). In addi-
tion, the structure contains H3O+ cations, whose posi-
tions are difficult to determine because of disordering.
The Bi–Cl distances in the mononuclear [BiCl6]3–
anion vary in the range 2.726(1)–2.749(1) Å. Thus,
the coordination polyhedron (octahedron) of the Bi
atoms undergoes in compound II only insignificant
distortions.
For C H N O Cl Bi
14 27
2
4
6
Found, %
Anal. calcd., %
C, 23.9
C, 23.7
H, 3.7
H, 3.8
N, 4.1
N, 4.0
Synthesis of compound III. BiOBr (115 mg,
0.38 mmol) was dissolved in 2 M HBr (8 mL), and a
solution of Вpp (150 mg, 0.78 mmol) in 2 М HBr
(8 mL) was added. A yellow crystalline precipitate of
compound III began to form within several seconds.
In 2 h, the product was separated by filtration. The
yield was 90%.
For C H N O Br Bi
26 36
4
2
10
2
Found, %
Anal. calcd., %
C, 19.0
С, 18.9
H, 2.1
H, 2.2
N, 3.5
N, 3.4
X-ray diffraction analysis. Diffraction data for sin-
gle crystals of compounds I–III were obtained at
130 K on an Agilent Xcalibur diffractometer equipped
with an Atlas S2 two-coordinate detector (graphite
monochromator, λ(MoKα) = 0.71073 Å, ω scan
mode). Integration was performed, an absorption cor-
rection was applied, and unit cell parameters were
determined using the CrysAlisPro program package
[19]. The structures were solved using the SHELXT
program [20] and refined by full-matrix least
squares in the anisotropic approximation except for
hydrogen atoms (SHELXL) [21]. The positions of the
hydrogen atoms of the organic cations were calculated
geometrically and refined by the riding model. The
details of X-ray diffraction analyses and the main crys-
tallographic structural data are presented in Table 1.
The structure of complex III (Fig. 3) contains the
binuclear anions [Bi2Br10]4–. As in the case of
complex I, this structural type is very abundant (at
least 45 compounds for X = Cl, Br, and I and at least
five compounds for bromobismuthates [29]). The Bi–
Brterm and Bi–(μ2-Br) distances (2.7331(8)–2.8563(7)
The full tables of interatomic distances and bond
angles and the coordinates of atoms and parameters of and 2.9664(7)–3.0466(7) Å) are characteristic of this
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 44 No. 8 2018

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GOROKH et al.
Table 1. Crystallographic parameters and diffraction experimental details for compounds I–III
Value
Parameter
I
II
III
FW
2875.13
709.05
1653.65
Triclinic
Crystal system
Space group
Triclinic
Monoclinic
I2/a
P
P
1
1
a, Å
10.5254(2)
17.9486(4)
18.6680(4)
100.881(2)
100.408(2)
93.585(2)
10.6425(3)
14.2898(4)
17.4784(6)
90
11.7125(3)
13.0169(3)
13.7206(4)
89.131(2)
b, Å
c, Å
α, deg
β, deg
γ, deg
95.011(3)
90
88.059(2)
83.279(2)
2076.16(9)
V, Å3
3389.21(13)
2647.94(14)
Z
2
4
2
calc, g/cm3
2.817
1.779
2.645
ρ
μ, mm−1
20.996
7.283
18.117
F(000)
2572
1368
1504
Crystal size, mm
Scan range over θ, deg
Range of indices hkl
0.27 × 0.19 × 0.06
3.28–25.35
0.44 × 0.36 × 0.20
3.46–29.56
0.18 × 0.16 × 0.09
3.35–29.10
−13 < h < 13,
−21 < k < 22,
−23 < l < 23
−11 < h < 15,
−15 < k < 20,
−23 < l < 22
−15 < h < 12,
−13 < k < 17,
−13 < l < 17
Nhkl measured/independent
Rint
25242/12 380
0.0358
6593/3120
0.0153
2713
16823/9103
0.0490
7378
Nhkl with I > 2σ(I)
9854
GOOF for F 2
1.000
1.064
1.014
R factors (I > 2σ(I))
R1 = 0.0384,
wR2 = 0.0713
R1 = 0.0365,
wR2 = 0.1076
R1 = 0.0393,
wR2 = 0.0684
R factors (for all reflections)
Δρmax/Δρmin, e/Å3
R1 = 0.0568,
wR2 = 0.0771
R1 = 0.0426,
wR2 = 0.1123
R1 = 0.0545,
wR2 = 0.0754
2.477/−2.429
1.658/−1.720
1.983/−1.740
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MONO- AND BINUCLEAR CHLORIDE AND BROMIDE COMPLEXES
505
type [29]. The structure of complex III contains sol-
vate molecules of H2O, as in the case of complex II.
The compound is stable on storage for several days.
y
z
We have previously [33] mentioned that the struc-
tural type [Bi2X10]4– is most often met in structures of
the compounds bearing cations being N-protonated
nitrogenous bases. According to the results of analysis
of the data presented in the CCDC [33], this structural
type is characterized by solvate formation to a higher
extent than the [Bi2X9]3– complexes. The results
obtained in the present work are consistent with these
observations.
ACKNOWLEDGMENTS
This work was supported by the Russian Science
Foundation (project no. 14-23-00013). S.A. Adonin
acknowledges support from the Council for Grants of
the President of the Russian Federation (research
grant from the President of the Russian Federation).
Fig. 1. Molecular packing in the crystal of compound I.
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