Bromobismuthates of 1,1'-(1,N-Alkanediyl)bis(picolines): Synthesis, Thermal Stability, Crystal Structures, and Optical Properties

Article abstract of DOI:10.1134/S1070328420020049

Abstract: Hybrid bromobismuthates of N-alkylated derivatives of 2- and 3-methylpyridine, (C₁₅H₂₀N₂)₂Bi₂Br₁₀ (I), (C₁₇H₂₄N₂)₂Bi₂Br₁₀ (II), (C₁₈H₂₆N₂)₃(Bi₂Br₉)₂ (III), (C₁₄H₁₈N₂)(H₃O)BiBr₆ ? 2H₂O (IV), (C₁₄H₁₈N₂)₂BiBr₆IBr₂ (V), (C₁₆H₂₂N₂)₃(Bi₂Br₉)₂ (VI), and (C₁₈H₂₆N₂)₃(Bi₂Br₉)₂ (VII), are synthesized in concentrated HBr and characterized by physicochemical methods. The structures of complexes I–VII are studied by X-ray structure analysis (CIF files CCDC nos. 1946844–1946850). Complexes I and II contain anions [Bi₂Br₁₀]^4–. Anions [Bi₂Br₉]^3– are found in the structures of compounds III, VI, and VII. Bis(3-methyl-1-pyridino)ethane bromobismuthate IV contains cations H₃O⁺ and anions [BiBr₆]^3– and, unlike other bromobismuthates, decomposes at low temperatures. In presence of HI vapors, double bromobismuthate V containing the [BiBr₆]^3– and IBr₂ ^– anions crystallizes along with compound IV.

Full text of DOI:10.1134/S1070328420020049

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2020, Vol. 46, No. 2, pp. 111–118. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Koordinatsionnaya Khimiya, 2020, Vol. 46, No. 2, pp. 104–111.
Bromobismuthates of 1,1'-(1,N-Alkanediyl)bis(picolines): Synthesis,
Thermal Stability, Crystal Structures, and Optical Properties
P. A . B ui kin a, b, *, A. Yu. Rudenkob, c, A. B. Ilyukhina, N. P. Simonenkoa, Kh. E. Yorova, d, and V. Yu. Kotova, e
aKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
bHigher Chemical College of Russian Academy of Sciences, Mendeleev University of Chemical Technology of Russia,
Moscow, Russia
cZelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
dDepartment of Chemistry, Moscow State University, Moscow, 119899 Russia
eNational Research University Higher School of Economics, Moscow, Russia
*е-mail: peterzzz@mail.ru
Received September 9, 2019; revised September 25, 2019; accepted September 28, 2019
Abstract—Hybrid bromobismuthates of N-alkylated derivatives of 2- and 3-methylpyridine,
(C15H20N2)2Bi2Br10 (I), (C17H24N2)2Bi2Br10 (II), (C18H26N2)3(Bi2Br9)2 (III), (C14H18N2)(H3O)BiBr6 ∙
2H2O (IV), (C14H18N2)2BiBr6IBr2 (V), (C16H22N2)3(Bi2Br9)2 (VI), and (C18H26N2)3(Bi2Br9)2 (VII), are syn-
thesized in concentrated HBr and characterized by physicochemical methods. The structures of complexes
I–VII are studied by X-ray structure analysis (CIF files CCDC nos. 1946844–1946850). Complexes I and II
contain anions [Bi2Br10]4–. Anions [Bi2Br9]3– are found in the structures of compounds III, VI, and VII.
Bis(3-methyl-1-pyridino)ethane bromobismuthate IV contains cations H3O+ and anions [BiBr6]3– and,
unlike other bromobismuthates, decomposes at low temperatures. In presence of HI vapors, double bromo-
bismuthate V containing the [BiBr6]3– and IBr2– anions crystallizes along with compound IV.
Keywords: hybrid halobismuthates, semiconductors, crystal structure, bromobismuthate anions
DOI: 10.1134/S1070328420020049
INTRODUCTION
in the structure of 1,1'-(1,4-phenylenebis(methy-
lene))bis(3-methylpyridin-1-ium) bromobismuthate.
The high values of Eg for this compound [12] and the
compounds with the zigzag polymeric anion
Hybrid halobismuthates are promising materials
for solar power engineering [1–4]. They are lowly
toxic and highly resistant to external actions, in partic-
ular, to high moisture contents. Among the readily
formed hybrid halobismuthates, one can find com-
pounds with low values of the optical band gap (Eg <
1.8 eV) [5–9]. Among the latter, mixed methyl violo-
gen chloroiodobismuthate [7] and methyl viologen
iodobismuthate [8] contain linear 1D chains
[BiBr5]2nn–
[11] are consistent with the conclusion that
only the presence of a linear anionic chain in the com-
pound is the condition for decreasing the optical band
gap of the semiconductor. Bromobismuthates, iodo-
bismuthates, and mixed bromoiodobismuthates of the
single-charge picoline derivatives are known [13–15].
However, no compounds with low Eg were found
among them.
[BiX5]2nn–
When searching for the compounds with
.
linear polymeric anions, we synthesized several
bromo- and iodobismuthates of N-substituted pico-
2n–
lines [9–12]. The linear
anion we are inter-
The purpose of this work is to investigate the earlier
[BiI5]n
ested in was found in the structure of iodobismuthate unstudied hybrid bromobismuthates of N-alkylated 2-
of the 4-methylpyridine derivative. The optical band
gap for this compound was 1.73 eV [9]. Isolated anions
[Bi2Br10]4–, [Bi2Br11]5–, and [BiBr6]3– [10], as well as
2n–
and 3-picoline dications.
EXPERIMENTAL
the zigzag polymeric anion
[11], were found
[BiI5]n
in the structures of the obtained bromobismuthates of
the picoline derivatives. An unusual linear anionic
agglomerate [(BiBr6)···(BiBr5)···(BiBr6)]8– is observed
Bis(2-methyl-1-pyridino)-1,1'-alkane bromide (a)
and bis(3-methyl-1-pyridino)-1,1'-alkane bromide
(b) were synthesized in air.
111

112
BUIKIN et al.
fraction analysis (XRD) data showed that the sub-
2Br−
2Br−
stance obtained after recrystallization was single-
phase. The details of the Rietveld refinement were the
following: P21/n, a = 11.1050(3), b = 10.0430(4), c =
19.9647(6) Å, β = 101.993(2)°, Rexp 3.10, Rwp 8.08, Rp
5.38%, GOОF 2.61.
N+ +nN
N+ +nN
H3C
CH3
CH3
CH3
(a)
(b)
Synthesis of (C17H24N2)2Bi2Br10 (II). A weighed
sample of bis(2-methyl-1-pyridino)pentane bromide
(0.50 g) was dissolved in a 4 M aqueous solution of
KBr (6.25 mL). A solution containing KBr (23.8 g)
and Bi(NO3)3 · 5H2O (4.75 g) in Н2О (75 mL) was
added to the reaction mixture. A formed greenish pre-
cipitate was filtered off in vacuo, washed with water
and ethanol, and dried in air. The yield was 0.635 g.
The obtained precipitate was dissolved in a minimum
amount of concentrated HBr, and the solution was left
to evaporate at room temperature. A finely crystalline
substance formed in several days was separated from
A mixture of methylpyridine taken in excess
(6 equiv) and dibromoalkane (1 equiv) was dissolved
in acetonitrile. The resulting solution was refluxed for
20 h. The formed precipitate was filtered off and
washed with acetonitrile. The purity of the formed
products was monitored by the 1Н NMR method.
Bis(2-methyl-1-pyridino)-1,1'-propane bromide:
1Н NMR (300 MHz; DMSO-d6; δ, ppm): 9.08 (d, J =
6.0 Hz, 2H), 8.46 (t, J = 7.8 Hz, 2H), 8.13 (d, J =
8.1 Hz, 2H), 8.05–7.95 (m, 2H), 4.57 (s, 4H), 2.87 (s,
6H), 1.95 (s, 2H).
Bis(2-methyl-1-pyridino)-1,1'-pentane bromide: the solution and dried in air. According to the X-ray
1Н NMR (300 MHz; DMSO-d6; δ, ppm): 9.18 (s,
2H), 8.50 (s, 2H), 8.11 (s, 2H), 7.99 (s, 2H), 4.64 (s,
4H), 2.90 (s, 6H), 1.97 (s, 4H), 1.51 (s, 2H).
structure analysis data, the obtained crystals had the
composition (C17H24N2)2Bi2Br10 (II). The XRD data
showed that the substance obtained after recrystalliza-
tion contained compound II as the major phase and
an unidentified impurity with the most intense peaks
at 2θ = 20.0, 30.1, and 40.3. The details of the Rietveld
refinement were the following: C2/m, a = 14.4137(6),
b = 18.0306(9), c = 9.8775(4) Å, β = 114.822(4)°,
Rexp = 3.49%, Rwp = 14.41%, Rp = 9.67%, GOОF 4.13.
Synthesis of crystals of (C18H26N2)3(Bi2Br9)2 (III).
A weighed sample of bis(2-methyl-1-pyridino)hexane
bromide (0.50 g) was dissolved in a 4 M aqueous solu-
tion of KBr (6.25 mL). A solution containing KBr
(23.8 g) and Bi(NO3)3 · 5H2O (4.75 g) in Н2О (75 mL)
was added to the reaction mixture. A formed greenish
precipitate was filtered off in vacuo, washed with water
and ethanol, and dried in air. The yield was 1.02 g. The
obtained precipitate was dissolved in a minimum
amount of concentrated HBr, and the solution was left
to evaporate at room temperature. A powder formed
in several days was separated from the solution and
dried in air. Several crystals of compound III suitable
for X-ray structure analysis were isolated from the
obtained powder. According to the XRD data, com-
pound III was not the major substance of the isolated
product.
Bis(2-methyl-1-pyridino)-1,1'-hexane bromide:
1Н NMR (300 MHz; DMSO-d6; δ, ppm): 9.11 (d, J =
6.1 Hz, 2H), 8.48 (t, J = 7.8 Hz, 2H), 8.14–7.90 (m,
2H), 4.70–4.49 (m, 4H), 2.87 (s, 6H), 1.88 (s, 4H),
1.45 (s, 4H).
Bis(3-methyl-1-pyridino)-1,1'-ethane bromide:
1Н NMR (300 MHz; DMSO-d6; δ, ppm): 9.15 (s,
2H), 8.88 (d, J = 5.9 Hz, 2H), 8.53 (d, J = 7.9 Hz,
2H), 8.06 (t, J = 7.0 Hz, 2H), 5.31 (s, 4H), 2.50
(s, 6H).
Bis(3-methyl-1-pyridino)-1,1'-butane bromide:
1Н NMR (300 MHz; DMSO-d6; δ, ppm): 9.18 (s,
2H), 9.05 (d, J = 5.8 Hz, 2H), 8.48 (d, J = 7.9 Hz,
2H), 8.07 (t, J = 6.9 Hz, 2H), 4.72 (s, 4H), 2.50 (s,
6H), 2.02 (s, 4H).
Bis(3-methyl-1-pyridino)-1,1'-hexane bromide:
1Н NMR (300 MHz; DMSO-d6; δ, ppm): 9.15 (s,
2H), 9.03 (d., J = 6.0 Hz, 2H), 8.46 (d, J = 8.0 Hz,
2H), 8.09–8.02 (m, 2H), 4.62 (t, J = 7.4 Hz), 2.51 (s,
6H), 1.99–1.91 (m, 4H), 1.34 (s, 4H).
Synthesis of (C15H20N2)2Bi2Br10 (I). A weighed
sample of bis(2-methyl-1-pyridino)propane bromide
(0.50 g) was dissolved in a 4 M aqueous solution of
KBr (6.25 mL). A solution containing KBr (23.8 g)
and Bi(NO3)3 · 5H2O (4.75 g) in Н2О (75 mL) was
Synthesis of (C14H18N2)(H3O)BiBr6 ∙ 2H2O (IV). A
weighed sample of bis(3-methyl-1-pyridino)ethane
bromide (0.50 g) was dissolved in a 4 M aqueous solu-
added to the reaction mixture. A formed greenish pre- tion of KBr (6.25 mL). A solution containing KBr
cipitate was filtered off in vacuo, washed with water (23.8 g) and Bi(NO3)3 · 5H2O (4.75 mL) in Н2О
and ethanol, and dried in air. The yield was 0.82 g. The
obtained precipitate was dissolved in a minimum
amount of concentrated HBr, and the solution was left
to evaporate at room temperature. A finely crystalline
substance formed in several days was separated from
the solution and dried in air. According to the X-ray
structure analysis data, the obtained crystals had the
composition (C15H20N2)2Bi2Br10 (I). The X-ray dif-
(75 mL) was added to the reaction mixture. A formed
colorless precipitate was filtered off in vacuo, washed
with water and ethanol, and dried in air. The yield was
1.57 g. The obtained precipitate was dissolved in a
minimum amount of concentrated HBr, and the solu-
tion was left to evaporate at room temperature. A mix-
ture formed in several days was separated from the
solution and dried in air. Crystals of two types suitable
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
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BROMOBISMUTHATES OF 1,1'-(1,N-ALKANEDIYL)BIS(PICOLINES)
113
for X-ray structure analysis were found in the mixture: were obtained at the ВМ01 diffraction station of the
compound IV and (C14H18N2)2BiBr6IBr2 (V). Accord- European
Synchrotron
Radiation
Facility
(PILATUS@SNBL diffractometer,
Grenoble,
ing to the XRD data, the products contained com-
pound IV as the major phase and an unidentified
impurity different from compound V with the most
intense peaks at 2θ = 9.4°, 10.6°, 11.8°, 12.1°, and
16.8°. The details of the Rietveld refinement were the
following: P21/n, a = 10.4093(4), b = 18.2135(8), c =
13.8881(6) Å, β = 99.444(5)°, Rexp 2.05, Rwp 12.72, Rp
8.70%, GOОF 6.21. The formation of the minor phase
of compound V was related, most likely, to the action
of HI vapors on the reaction mixture with the simulta-
neous storage of a series of solutions containing HBr
or HI in a fume hood.
France) [18]. The experimental data were processed
using the SNBL ToolBox [18] and CrysAlis software
(Rigaku Oxford Diffraction) programs. The structures
solved by a combination of a direct method and Fou-
rier syntheses and refined by full-matrix anisotropic–
isotropic least squares. The populations of the disor-
dered fragments in the structures of compounds IV
and VI were obtained by the isotropic refinement with
fixed thermal parameters of disordered atoms and
were fixed in the subsequent refinement. All calcula-
tions were performed using the SHELXS and
SHELXL programs [19]. Selected crystallographic
data are presented in Tables 1 and 2.
The experimental data for the structures of com-
pounds I–VII were deposited with the Cambridge
Crystallographic Data Centre (CIF files CCDC nos.
1946844–1946850); deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk).
XRD analysis was carried out on a Bruker D8
Advance diffractometer (CuKα, Ni filter, LYNXEYE
detector, reflection geometry). The full-profile analy-
sis of the powders was conducted using the TOPAS 4.2
program [20]. The Rietveld refinement was performed
using the structural models of compounds I, II, IV,
and VI.
Synthesis of (C16H22N2)3(Bi2Br9)2 (VI). A weighed
sample of bis(3-methyl-1-pyridino)butane (0.50 g)
was dissolved in a 4 M aqueous solution of KBr
(6.25 mL). A solution containing KBr (23.8 g) and
Bi(NO3)3 · 5H2O (4.75 g) in Н2О (75 mL) was added
to the reaction mixture. A formed pale green precipi-
tate was filtered off in vacuo, washed with water and
ethanol, and dried in air. The yield was 1.168 g. The
obtained precipitate was dissolved in a minimum
amount of concentrated HBr, and the solution was left
to evaporate at room temperature. The crystals formed
in several days were separated from the solution and
dried in air. The X-ray structure analysis data showed
that the obtained crystals had the composition
(C16H22N2)3(Bi2Br9)2 (VI). According to the XRD
data, the substance obtained after recrystallization was
single-phase. The details of the Rietveld refinement
were the following: P21/n, a = 16.4908(9), b =
11.3762(10), c = 41.7608(26) Å, β = 95.189(5)°, Rexp
2.88, Rwp 12.56, Rp 8.06%, GOОF 4.37.
Diffuse reflectance spectra were recorded on an
Ocean Optics spectrophotometer (model QE65000)
in a frequency range of 11000–50000 cm–1 at room
temperature. The spectra were reconstructed in the
coordinates of the dependence of the Kubelka–Munk
function [21] on the light energy. To obtain the
Kubelka–Munk function, the following equation was
used:
Synthesis of crystals of (C18H26N2)3(Bi2Br9)2 (VII).
A weighed sample of bis(3-methyl-1-pyridino)hexane
bromide (0.50 g) was dissolved in a 4 M aqueous solu-
tion of KBr (6.25 mL). A solution containing KBr
(23.8 g) and Bi(NO3)3 · 5H2O (4.75 g) in Н2О (75 mL)
was added to the reaction mixture. A formed pale
green precipitate was filtered off in vacuo, washed with
water and ethanol, and dried in air. The yield was
1.07 g. The obtained precipitate was dissolved in a
minimum amount of concentrated HBr, and the solu-
tion was left to evaporate at room temperature. A pre-
cipitate formed in several days were separated from the
solution and dried in air. Several crystals of compound
VII suitable for X-ray structure analysis were isolated
from the precipitate. According to the XRD data,
compound VII was not the major substance of the iso-
lated product.
(1 − Rd )2
F(Rd ) =
,
2Rd
where F(Rd) is the absolute reflection of the sample
layer. The optical band gap was estimated by the
extrapolation of the linear section of the correspond-
ing curve to F(Rd) = 0.
Thermogravimetric (TG) analysis of the samples
was carried out using an SDT Q600 V8.3 Build 101
Module DSC-TGA infrared scanner. The sample was
heated with a heating rate of 10°С/min from 25 to
300°C and an air flow rate of 250 mL/min in an open
aluminum ware.
1Н NMR spectra were recorded on a Bruker
AM300 spectrometer (300 MHz) in DMSO-d6.
X-ray structure analysis. Experimental data for
compounds I–VI were obtained on a Bruker SMART
APEX2 diffractometer (MoKα radiation, λ =
0.71073 Å, graphite monochromator) [16]. An absorp-
tion correction was applied semiempirically by equiv-
alents (SADABS) [17]. The data for compound VII
RESULTS AND DISCUSSION
The structure of compound I is formed by bis(2-
methyl-1-pyridino)propane cations and centrosym-
metric anions Bi2Br10 (Fig. 1a). The N(2) pyridine
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 46 No. 2 2020

114
BUIKIN et al.
Table 1. Selected crystallographic data and structure refinement results for compounds I–IV
Value
Parameter
I
II
III
IV
Formula
FW
C30H40N4Br10Bi2
1673.72
C34H48N4Br10Bi2
1729.82
C54H78N6Br18Bi4
3085.52
C14H25N2O3Br6Bi
957.80
T, K
150(2)
150(2)
150(2)
150(2)
Crystal system
Space group; Z
a, Å
b, Å
c, Å
β, deg
V, Å3
Monoclinic
P21/n; 2
Monoclinic
C2/m; 2
Monoclinic
P21/n; 2
Monoclinic
P21/n; 4
11.0210(4)
10.0180(4)
19.8331(7)
101.7340(10)
2143.98(14)
14.2567(5)
17.9650(6)
9.8582(3)
114.6920(10)
2294.04(13)
9.9964(4)
16.4091(7)
24.7686(11)
95.401(2)
4044.8(3)
10.3705(4)
18.0471(7)
13.8346(5)
99.5630(10)
2553.27(17)
calc, g/cm3
2.593
2.504
2.533
2.492
ρ
μ, mm–1
17.542
16.399
17.602
16.311
F(000)
1528
1592
2812
1760
Sample size, mm
Range of measuring over
0.28 × 0.28 × 0.14
2.098–31.022
0.24 × 0.24 × 0.12
2.267–31.512
0.2 × 0.1 × 0.08
2.278–26.058
0.32 × 0.32 × 0.28
2.257–30.058
θ, deg
Ranges of reflection
indices
–15 ≤ h ≤ 15,
–14 ≤ k ≤ 14,
–28 ≤ l ≤ 28
–20 ≤ h ≤ 20,
–26 ≤ k ≤ 25,
–13 ≤ l ≤ 14
–12 ≤ h ≤ 12,
–20 ≤ k ≤ 20,
–30 ≤ l ≤ 30
–14 ≤ h ≤ 14,
–25 ≤ k ≤ 25,
–19 ≤ l ≤ 19
Number of measured
reflections
Number of independent
54585
6793 (0.0644)
100.0
16735
3794 (0.0464)
100.0
43742
7987 (0.0870)
99.9
47092
7490 (0.0727)
100.0
reflections (Rint)
Completeness
to θ = 25.242°, %
Max, min transmission
Refinement method
0.1007, 0.0319
Least squares for F 2
0.1015, 0.0286
Least squares for F 2
0.0926, 0.0322
Least squares for F 2
0.099, 0.0314
Least squares for F 2
Number of restraints/
parameters
0/209
0/121
0/373
0/236
S
1.033
1.002
0.974
1.037
R1, wR2 (I > 2σ(I))
R1, wR2 (all data)
∆ρmax/∆ρmin, е/Å3
0.0269, 0.0564
0.0383, 0.0593
2.253/–0.942
0.0270, 0.0610
0.0366, 0.0643
1.703/–0.970
0.0369, 0.0617
0.0719, 0.0716
1.214/–1.522
0.0360, 0.0768
0.0537, 0.0830
2.532/–1.291
fragment is involved in the stacking interaction to form ments to form 2D layers. The shortest Br…Br contact
a centrosymmetric dimer (shortest contacts C…C
3.46, 3.53, 3.54 Å). The shortest Br…Br contacts are
4.15 and 4.16 Å.
is 4.20 Å.
The structure of compound III contains two crys-
tallographically independent bis(2-methyl-1-pyrid-
ino)hexane cations. One of them is localized in the
general position, the second cation lies on the inver-
sion center, and the Bi2Br9 anion is arranged in the
general position (Fig. 1c). The shortest Br…Br contact
In the structure of compound II, the bis(2-methyl-
1-pyridino)pentane cation lies on the axis 2, and the
Bi2Br10 anion has the crystallographic symmetry 2/m
(Fig. 1b). The pyridine fragment participates in the
stacking interaction (shortest contacts C…C 3.25,
3.35, 3.43 Å) with two symmetrically dependent frag- (3.92 Å) joins the anions into 1D chains.
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BROMOBISMUTHATES OF 1,1'-(1,N-ALKANEDIYL)BIS(PICOLINES)
115
Table 2. Selected crystallographic data and structure refinement results for compounds V–VII
Value
Parameter
V
VI
VII
Formula
C28H36N4Br8IBi
1403.77
C48H66N6Br18Bi4
3001.36
C54H78N6Br18Bi4
3085.52
FW
T, K
150(2)
100(2)
150(2)
Crystal system
Space group; Z
Triclinic
P–1; 1
Monoclinic
Monoclinic
P21/n; 4
16.4918(7)
11.2389(5)
41.1424(18)
90
94.7070(10)
90
7600.0(6)
P21/n; 2
10.6567(3)
16.5173(4)
23.2031(5)
90
92.411(3)
90
4080.59(18)
a, Å
b, Å
c, Å
α, deg
β, deg
γ, deg
9.7162(4)
10.1351(5)
11.5665(5)
82.1770(10)
65.5040(10)
68.6170(10)
964.99(8)
V, Å3
calc, g/cm3
2.416
2.623
2.511
ρ
μ, mm–1
13.674
18.732
15.261
F(000)
648
5432
2812
Sample size, mm
Range of measuring over θ, deg
Ranges of reflection indices
0.16 × 0.14 × 0.08
2.158–31.509
–13 ≤ h ≤ 14,
–14 ≤ k ≤ 14,
–16 ≤ l ≤ 16
0.24 × 0.16 × 0.12
2.066–27.118
–21 ≤ h ≤ 21,
–14 ≤ k ≤ 14,
–52 ≤ l ≤ 51
0.04 × 0.02 × 0.01
1.669–26.750
–13 ≤ h ≤ 13,
–22 ≤ k ≤ 22,
–30 ≤ l ≤ 30
Number of measured reflections
18762
63868
25299
Number of independent reflections
6095 (0.0459)
16731 (0.0791)
8782 (0.0421)
(Rint)
Completeness to θ = 25.242°, %
Max, min transmission
Refinement method
100.0
0.1015, 0.0342
Least squares for F2
99.9
0.0285, 0.0054
Least squares for F2
92.3
1, 0.39459
Least squares for F2
Number of restraints/parameters
S
0/195
1.019
9/695
0.990
0/370
1.016
R1, wR2 (I > 2σ(I))
R1, wR2 (all data)
∆ρmax/∆ρmin е/Å3
0.0332, 0.0812
0.0435, 0.0851
1.749/–2.333
0.0571, 0.1388
0.0881, 0.1546
2.028/–2.209
0.0658, 0.1590
0.0925, 0.1755
3.229/–3.492
The structure of compound IV is formed by the ters). One of the cations forms the 1D chain by stack-
bis(3-methyl-1-pyridino)ethane cations, BiBr6 anions ing interactions of the pyridine fragment. The I…Br
contact (4.16 Å) links the anions into the 1D chain.
(Fig. 1d), oxonium ions, and molecules of water of
crystallization. All positions of the O atoms of the oxo-
nium ions and water molecules are disordered (popu-
lation 0.24–0.76), which does not allow one to objec-
tively localize the H atoms.
The structure of compound VI contains two crys-
tallographically independent Bi2Br9 anions and four
independent bis(3-methyl-1-pyridino)butane cations
(Fig. 2b). One of the anions is disordered over two
positions in a ratio of 0.85 : 0.15, two cations are in the
general position, the third cation lies on the inversion
center, and the fourth cation is disordered about the
All structural units in the impurity phase V, two
crystallographically independent bis(3-methyl-1-pyr-
idino)ethane cations and BiBr6 and IBr2 anions
(Fig. 2a), are in the partial positions (inversion cen- inversion center. The disordered Br atom with a popu-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 46 No. 2 2020

116
BUIKIN et al.
(а)
(b)
Br(1)
C(1)
N(1)
Bi(1A)
Br(1)
N(2)
Bi(1)
Bi(1)
N(1)
C(1)
Bi(1A)
(c)
(d)
Bi(1)
Br(1)
Bi(2)
C(1)
N(1)
Bi(1)
Br(1)
N(2)
N(3)
C(19)
Fig. 1. Fragments of the structures of compounds (a) I, (b) II, (c) III, and (d) IV.
lation of 0.15 is involved in the shortest Br…Br contact one HBr molecule and two H2O molecules when the
(3.73 Å).
The structure of compound VII is formed by the
temperature reached 140°С. Other compounds are
more stable. Compound I remains stable to 270°С and
then undergoes melting with decomposition at 279°С.
The decomposition of compound II started already at
250°С. Compound III melts at 250°С, compound VI
melts at 234°С, and compound VII melts at 250°С.
Bi2Br9 anions and two crystallographically indepen-
dent bis(3-methyl-1-pyridino)hexane cations, one of
which is arranged on the inversion center (Fig. 2c).
Although the conformation of the aliphatic chains in
the cations can be described as ttttt, the range of abso-
lute values of the NCCC and CCCC torsion angles in
the centrosymmetric cation (174°–180°) and that
arranged in the general position (148°–174°) indicates
a less distorted conformation of the first cation. The
shortest Br…Br contact is 3.90 Å.
According to the data of diffuse reflectance spec-
troscopy, the optical band gaps for compounds I, II,
IV, and VI were 2.83, 2.85, 2.88, and 2.85 eV. The for-
mal values for the products containing compounds III
and VII are equal to each other being 2.86 eV. Thus,
the spectral characteristics of all isolated compounds
The thermal analysis of the crystalline powder of
compound IV (Fig. 3) showed that the compound lost are typical of the 0D hybrid bromobismuthates.
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2020

BROMOBISMUTHATES OF 1,1'-(1,N-ALKANEDIYL)BIS(PICOLINES)
117
(а)
(b)
Bi(1)
Br(1)
C(1)
N(1)
Br(1)
Bi(2)
N(3)
N(1A)
Bi(1)
C(17)
I(1)
(c)
C(19)
N(3)
Bi(2)
Br(1)
Bi(1)
Fig. 2. Fragments of the structures of compounds (a) V, (b) VI, and (c) VII.
Hybrid bromobismuthates of N-substituted 2- and we cannot assert that a tendency for changing the
3-picolines contain various anions, namely, [BiBr6]3–,
[Bi2Br9]3–, and [Bi2Br10]4–. We have also found previ-
organic cation to bismuth ratio was observed in the
series of the isolated compounds.
ously the
2n– and [Bi2Br11]5– anions in the struc-
[BiBr5]n
ACKNOWLEDGMENTS
tures of bromobismuthates of N-substituted 2- and
4-bromopicolines [10, 11]. Thus, we cannot predict
the possible composition and structure of the anionic
moiety of bromobismuthates in the series of N-substi-
tuted picolines even for the same initial stoichiometric
ratio of the reagents (doubly charged organic cation :
bismuth). We mentioned that the products with the
organic cation to bismuth ratio equal to 1 : 1 crystal-
lized for bromobismuthates of N-substituted 4-pico-
lines in all cases studied. For bromobismuthates of N-
substituted 2-picolines, the deviation from this ratio is
observed only for the compound in which the cation
contains the alkane chain bearing six carbon atoms,
while the alkane chain should already contain four and
six carbon atoms for bromobismuthates of N-substi-
tuted 3-picolines. However, since the products of the
reactions of bis(p-methyl-1-pyridino)hexane cations
with bromobismuthate anions are not single-phase,
The authors are grateful to D.Yu. Chernyshov for per-
forming experiments at the Swiss Norwegian Beam Lines
(SNBL) of the European Synchrotron Radiation Facility
(ESRF) (Grenoble, France). The studies were carried out
using the equipment of the Center for Collective Use of
Physical Methods of Investigation at the Kurnakov Institute
of General and Inorganic Chemistry (Russian Academy of
Sciences) functioning with the support of the state task of
the Kurnakov Institute of General and Inorganic Chemistry
(Russian Academy of Sciences) in the area of basic research.
FUNDING
This work was supported by the state task of the Kurna-
kov Institute of General and Inorganic Chemistry (Russian
Academy of Sciences) in the area of basic research.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 46 No. 2 2020

118
BUIKIN et al.
100
95
0.3
1.859%
2.449%
271.30°C
228.58°C
291.99°C
0.1
19.980%
7.940%
90
85
0.3892%
0.9262%
6.421%
–0.1
–0.3
129.45°C
80
0
50
100
150
200
250
300
Temperature, °С
Fig. 3. DSC–TG curves for compound IV.
CONFLICT OF INTEREST
11. Buikin, P.A., Rudenko, A.Y., Baranchikov, A.E., et al.,
Russ. J. Coord. Chem., 2018, vol. 44, p. 373.
The authors declare that they have no conflicts of
https://doi.org/10.1134/S1070328418060015
interest.
12. Kotov, V.Y., Safiullina, E.S., Ilyukhin, A.B., et al., J.
Mol. Struct., 2019, vol. 119, p. 944.
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RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
Vol. 46
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2020