Bromobismuthates: Cation-induced structural diversity and Hirshfeld surface analysis of cation–anion contacts

Article abstract of DOI:10.1016/j.poly.2017.11.002

Reactions of [BiBr₆]^3? and bromide salts of various substituted pyridinium cations in excess of HBr result in a series of bromobismuthate anionic complexes of various geometry and nuclearity: [{BiBr₄}_n]^n?, [Bi₂Br₉]^3? and [Bi₂Br₁₀]^4?. Hirshfeld surface analysis for 19 crystal structure was performed; impact of various X-Br contacts on the crystal structures is discussed.

Full text of DOI:10.1016/j.poly.2017.11.002

Accepted Manuscript
Bromobismuthates: cation-induced structural diversity and Hirshfeld surface
analysis of cation-anion contacts
Sergey A. Adonin, Igor D. Gorokh, Alexander S. Novikov, Denis G.
Samsonenko, Ilya V. Korolkov, Maxim N. Sokolov, Vladimir P. Fedin
PII:
S0277-5387(17)30701-5
https://doi.org/10.1016/j.poly.2017.11.002
POLY 12903
DOI:
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
11 September 2017
2 November 2017
Please cite this article as: S.A. Adonin, I.D. Gorokh, A.S. Novikov, D.G. Samsonenko, I.V. Korolkov, M.N. Sokolov,
V.P. Fedin, Bromobismuthates: cation-induced structural diversity and Hirshfeld surface analysis of cation-anion
contacts, Polyhedron (2017), doi: https://doi.org/10.1016/j.poly.2017.11.002
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Bromobismuthates: cation-induced structural diversity and Hirshfeld surface
analysis of cation-anion contacts
a,b
Sergey A. Adonin, Igor D. Gorokh, Alexander S. Novikov, Denis G. Samsonenko, Ilya V.
b
c
a,b
a,b
Korolkov, Maxim N. Sokolov
a,b,d
a,b
and Vladimir P. Fedin
a) Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Lavrentieva St. 3, Novosibirsk,
Russia. E-mail: adonin@niic.nsc.ru
b) Novosibirsk State University, 630090 Pirogova St. 2, Novosibirsk, Russia
c) Saint Petersburg State University, Institute of Chemistry, 199034 Universitetskaya Nab. 7-9,
Saint Petersburg, Russia
d) Kazan Federal University, Alexander Butlerov Institute of Chemistry, Lobachevskogo str.
1
/29, 420008 Kazan, Russia
3
-
Abstract: Reactions of [BiBr
6
] and bromide salts of various substituted pyridinium cations in
excess of HBr result in a series of bromobismuthate anionic complexes of various geometry and
n-
3-
4-
4 n 2 9 2
nuclearity: [{BiBr } ] , [Bi Br ] and [Bi Br10] . Hirshfeld surface analysis for 19 crystal structure
was performed; impact of various X-Br contacts on the crystal structures is discussed.
Keywords: halometalate / halide complexes / bismuth / crystal structure / Hirshfeld surface
analysis
Introduction
Although halide complexes of late transition and p-block metals are known for over 100
years, the interest on this class of coordination compounds is persistent. Within the last
decade, it is mostly focused on their numerous applications in materials science,
particularly, for development of hybrid solar cells [1-7], ferroelectric and ferroelastic
materials [8-10], photocatalysts [11-14] etc. From simplistic point of view the
halometalates may be regarded as trivial objects for preparative chemist. Indeed, their
preparation protocols are straightforward [15], and usually result in crystalline solids
suitable for XRD. On the other hand, the price for the simplicity is extreme difficulty (or
even impossibility) of making any reliable predictions about the structure of a particular
complex forming under certain conditions. Depending on the nature of metal, p-block
elements form discrete polynuclear halide complexes of different nuclearity (up to 8 for

Bi(III) [16-18] or 18 for Pb(II) [19]), as well as one-, two- or three-dimensional polymers
15,20-24]. Usually, such reactions cannot be reliably controlled stoichiometrically; the
key factors governing the structure and composition of resulting halometalates are the
[
1
nature and geometry of counter cations and, in some cases, the solvent. In particular,
5
Benetollo et al. have shown [25] that reaction between Bi
2
O
3
and N-heterocyclic bases in
3
-
4-
Cl10] in the case of 8-
HCl solutions may result both in [BiCl
6
] and binuclear [Bi
2
hydroxyquinolinium and quinolinium or isoquinolinium, respectively [25]. Similar
observations were made by Junk et al. for the heteroligand Bi(III) halide complexes [26-
2
9]. It must be noted, however, that although there are a great number of polyclear
halobismuthates reported to date, only in a few cases the role of cation was
systematically analysed. Recently, Mercier et al. presented a very interesting highlights
paper [30] on the structural diversity of iodometalates, stating: “Unfortunately, metal
halide complexes are involved in fast dissociation and association processes due to the
labile halide ligands in solution, which means that the concept of pre-defined subunits
cannot be applied to these systems” [30]. In this article, authors tried to find some
cation-anion correlations in the compounds reported earlier. However, any general rules
allowing the directed synthesis of halometalates are still lacking. We proposed that one
of strategies that could make the search of such correlations possible, is to prepare a
series of certain halide complexes, e.g. bromobismuthates (III), using a kit of closely
related cations under identical conditions. For this purpose, we have chosen
substituted pyridines, since this class of compounds is readily available and can be easily
modified by N-alkylation reactions. In this work, we report a series of eight novel HB
(
halobismuthate) complexes with various pyridinium cations: (PyH){[BiBr
4
]} (
[Bi Br
) and (3-
was reported by us earlier [31]). From previously published
1
), (N-
MePy){[BiBr
1,4-MePy) [Bi
MePyH)[{BiBr
4
]} (
2
), (N-EtPy)
] ( ), (4-MePyH)
) (
3
[Bi
2
Br
9
] (
3
), (N-n-PrPy)
3
[Bi
2
Br
9
] (
4
), (N-n-BuPy)
3
2
9
] ( ),
5
(
3
2
Br
9
6
4
[Bi ), (4-EtPyH)
2
Br10] (
7
4
[Bi Br10] (8
2
4
}] (
9
2
relevant compounds, we have additionally selected a set of structurally characterized
bromobismuthates made in similar way. Using the whole set of these XRD data, we
applied Hirshfeld surface analysis (HSA), an approach which is extensively used in
analysis of crystal structures, enabling the evaluation of cation-anion interactions in solid
state [32-34].
Experimental section

General
All synthetic procedures were carried out in air. All precursors (reagent grade) were
obtained from commercial sources and used as purchased. N-alkylated derivatives of
pyridines were obtained according to the general scheme (pyridine + R-X (R = Me, X = I;
1
R = Et, n-Pr, n-Bu, X = Br) in acetonitrile) and identified by H NMR spectra and elemental
analysis (in all cases, yield was > 90%). Elemental analysis was performed on a Euro NA
3
000 Elemental Analyzer (EuroVector).
Synthesis of 1-9
2 3
General procedure. Bi O (75 mg/0.16 mmol in all cases) was dissolved in 2M HBr (solution A)
and then solution containing bromide of corresponding cation in 2M HBr (solution B) was
added, resulting in formation of yellow crystals. Details are summarized in Table 1.
Table 1. Preparation details and element analysis for 1 and 3-9
V(A), ml
CatBr or precursor, V(B), ml
mg or μl
Element analysis,
calcd/found
Yield, %
91
1
3
4
5
6
7
8
4
4
5
6
5
4
4
7 μl
45 mg
49 mg
52 mg
57 mg**
30 μl
1
4
4
4
3
2
2
C, 9.9/10.0; H, 1.0/1.1;
N, 2.3/2.3
C, 17.3/17.3; H, 2.1/2.2;
N, 2.9/3.0
79
C, 19.2/19.3; H, 2.4/2.5,
N, 2.8/3.0
83
C, 20.8/20.7; H, 2.7/2.5;
N, 3.6/3.6*
87*
85
C, 17.3/17.4; H, 2.1/2.2;
N, 2.9/3.1
C, 18.1/18.3; H, 2.0/2.3;
N, 3.5/3.6
92*
93*
35 μl
C, 20.4/20.5; H, 2.4/2.6;
N, 3.4/3.6

9
4
8 μl
1
C, 11.6/11.7; H, 1.3/1.4;
N, 2.2/2.4
90
*
For crude precipitate (see Results and Discussion for details). **iodide salt was taken, treated
with stoichiometric amount of AgNO in water and then concentrated HBr was added to reach
M concentration in final solution
3
2
X-ray diffractometry
Diffraction data for single crystals of 1 and 3-9 were obtained at 130 K on an automated Agilent
Xcalibur diffractometer equipped with an area AtlasS2 detector (graphite monochromator,
λ(MoKα) = 0.71073 Å, ω-scans). Integration, absorption correction, and determination of unit
cell parameters were performed using the CrysAlisPro program package [35]. The structures
were solved by dual space algorithm (SHELXT [36]) and refined by the full-matrix least squares
technique (SHELXL [37]) in the anisotropic approximation (except hydrogen atoms). Positions of
hydrogen atoms of organic ligands were calculated geometrically and refined in the riding
model. The crystallographic data and details of the structure refinements are summarized in
Table 2. CCDC 1573664–1573671 contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge Crystallographic Data
Center at http://www.ccdc.cam.ac.uk/data_request/cif.
Hirshfeld Surface analysis
The Hirshfeld molecular surfaces were generated by CrystalExplorer 3.1 program [38, 39]. The
normalized contact distances, dnorm [40] based on Bondi’s van der Waals radii [41] were
mapped into the Hirshfeld surface. In the color scale, negative values of dnorm are visualized by
the red color indicating contacts shorter than the sum of van der Waals radii. The white color
denotes intermolecular distances close to van der Waals contacts with dnorm equal to zero. In
turn, contacts longer than the sum of van der Waals radii with positive dnorm values are colored
with blue.

Compound
Empirical formula
Formula weight
Crystal system
Space group
a, Å
1
3
4
5
6
7
8
9
C
5
H
6
BiBr
4
N
C
21
H
30Bi
2
Br
9
N
3
C
24
H
36Bi
2
Br
9
N
3
C
27
H
42Bi
2
Br
9
N
3
C
21
H
30Bi
2
Br
9
N
3
C
24
H
32Bi
2
Br10
N
4
C
28
H
40Bi
2
Br10
N
4
C
6
H
8
4
BiBr N
608.73
1461.63
Monoclinic
P2 /c
1503.71
Monoclinic
P2 /c
1545.78
Monoclinic
P2 /c
1461.63
Monoclinic
P2 /n
1593.59
Triclinic
P−1
1649.70
Triclinic
P−1
622.75
Monoclinic
I2/a
Monoclinic
I2/a
1
1
1
1
7.39274(18)
13.6598(3)
11.5357(3)
90
11.3845(2)
19.5876(4)
16.2452(3)
90
12.4155(2)
21.8000(5)
14.1891(4)
90
12.12909(15)
18.7345(2)
18.9098(2)
90
18.5668(3)
9.2994(4)
9.3573(3)
7.4039(2)
13.2103(4)
12.9227(5)
90
b, Å
11.59641(12)
18.8011(3)
90
10.5376(6)
10.7560(5)
99.771(4)
109.269(4)
10.8128(4)
11.3710(4)
92.324(3)
109.415(3)
c, Å
α, deg.
β, deg.
96.774(2)
93.8552(18)
94.820(2)
98.2716(11)
117.8540(19)
93.133(3)
γ, deg
90
1156.78(5)
4
90
3614.41(13)
4
90
90
4252.22(9)
4
90
3579.03(11)
4
96.713(4)
963.45(9)
1
96.743(3)
1073.68(7)
1
90
1262.05(7)
4
3
V, Å
3826.81(15)
4
Z
3
D(calc.), g/cm
3.495
29.005
1064
2.686
2.610
2.415
16.744
2824
2.713
2.747
19.511
720
2.551
3.278
26.590
1096
−
1
μ, mm
19.690
2632
18.601
2728
19.885
2632
17.512
752
F(000)

Crystal size, mm
0.32 × 0.12 ×
.02
0.43 × 0.30 × 0.21 0.25 × 0.19 × 0.18 0.36 × 0.35 × 0.02 0.30 × 0.22 × 0.12
0.29 × 0.24 × 0.15
3.36–28.84
0.20 × 0.08 × 0.06
3.48–25.35
0.26 × 0.04 ×
0.03
0
θ range for data
collection, deg.
3.56–30.88
3.35–28.28
3.29–25.35
3.36–26.37
3.28–29.10
4.36–29.41
Index ranges
−10 ≤ h ≤ 10,
−15 ≤ h ≤ 13,
−26 ≤ k ≤ 18,
−21 ≤ l ≤ 21
−14 ≤ h ≤ 14,
−26 ≤ k ≤ 25,
−17 ≤ l ≤ 42
−11 ≤ h ≤ 15,
−22 ≤ k ≤ 23,
−23 ≤ l ≤ 23
−22 ≤ h ≤ 23,
−14 ≤ k ≤ 15,
−25 ≤ l ≤ 25
−12 ≤ h ≤ 12,
−14 ≤ k ≤ 14,
−14 ≤ l ≤ 14
−9 ≤ h ≤ 11,
−13 ≤ k ≤ 13,
−13 ≤ l ≤ 11
−7 ≤ h ≤ 9,
−17 ≤ k ≤ 8,
−13 ≤ l ≤ 16
−19 ≤ k ≤ 19,
−15 ≤ l ≤ 16
Reflections collected 9957 / 1730
independent
20851 / 8950
19045 / 6987
22799 / 8672
55313 / 8344
7171 / 4230
7160 / 3923
2894 / 1486
R
int
0.0468
1620
0.0325
7578
0.0404
5965
0.0733
6858
0.0312
7656
0.0258
3719
0.0214
3509
0.0166
1365
Reflections with
I > 2σ(I)
2
Goodness-of-fit on F
1.147
1.068
1.018
1.032
1.120
1.070
1.040
1.045
Final R indices
R
wR
1
= 0.0314,
R
1
1
= 0.0355, wR
2
=
=
R
1
1
= 0.0338, wR
2
=
=
R
1
= 0.0530, wR
2
=
=
R
1
= 0.0213, wR
2
=
=
R
1
1
= 0.0353, wR
0.0787
2
=
=
R
1
1
= 0.0318, wR
0.0799
2
=
=
1
R = 0.0182,
[I > 2σ(I)]
2
= 0.0896
0.0725
0.0667
0.1424
0.0456
wR
2
= 0.0360
R indices (all data)
R
1
wR
= 0.0343,
= 0.0932
R
= 0.0469, wR
2
R
= 0.0439, wR
2
R
1
= 0.0706 wR
2
R
1
= 0.0254 wR
2
R
= 0.0423, wR
2
R
= 0.0365, wR
2
R = 0.0215,
1
2
0.0764
0.0708
0.1570
0.0467
0.0826
0.0824
2
wR = 0.0373
Largest diff. peak / 2.200 / −2.710
2.544 / −3.453
2.352 / −1.921
2.827 / −2.421
1.244 / −1.744
1.742 / −2.503
3.679 / −2.057
0.754 / −0.818
3
hole, e/Å

Results and discussion
As we have noted before [15], the majority of HB complexes are synthesized by a simple
3 2 3
scheme: a source of Bi (usually BiX , BiOX or Bi O ) + source of halide ion + cation (which
may be also prepared in situ, for example, by protonation of corresponding N-bases or
N-alkylation of N-heterocycles, i.a. 4,4`-bipyridine). We followed this approach,
maximizing the similarity of synthetic conditions for all complexes. At the first stage, all
reactions were carried out at room temperature and the Bi/cation ratio was 1:1. We
found that the complexes 1-4 and
ray diffractometry (PXRD) data), although the cation/Bi ratio is 3/2 in the case of
and . Attempts to vary the stoichiometry did not lead to the formation of other
products, neither to a significant increase in the yields. It must be noted that the
isolation of 4, 6 and, in some extent, always require more time than those of and
-9, and the yields are generally lower. In our opinion, this behaviour is due to the
6 precipitate in pure form (according to the powder X-
3, 4
6
2
-
5
1
7
disability of N-alkylated pyridines to form stronger NH···X contacts that are common for
the HB with N-protonated bases as cations. Interestingly, according to the PXRD data,
the crude precipitates which can be isolated in the cases of
MePyH) [Bi Br10] and (4-EtPyH) [Bi Br10] as the predominant phases, correspondingly.
Attempts to promote the formation of pure and by mixing the precursors in the
stoichiometry appearing in the products (2:1 in both cases) were not helpful; moreover,
the ratio between the major phase and by-products seems to persist. Both and can
be recrystallized from hot 2M HBr, but this procedure does not lead to purification,
although and remain the major components, as it can be concluded from both PXRD
and element analysis data. For 5, we never succeeded in isolation of single pure phase;
the solid always contained a mixture of several unknown phases and as one of the
7 and 8 contain (4-
4
2
4
2
7
8
7
8
7
8
5
major components. Alteration of the initial stoichiometry was not helpful as well. These
observations strongly support the cautious conclusions made by us in the recent review
[15]: the reagent stoichiometry cannot be regarded as key factor in the synthesis of HB
in all cases. There are two scenarios, depending on how favourable is formation of
certain crystalline phase (and this is related to the lattice energy): either it is highly
preferable, suppressing the influence of stoichiometry, and this is what was observed for
1
-9
, or two or more phases crystallize equally well, and stoichiometry affects the
outcome [42].

Although the Br/Bi ratio may vary (4 for
1
,
2
and
9
, 4.5 for
3
-6
and 5 for
7
and
8
), the
3
-
-
] does never form, even with Br in excess. Variations in
“plenary” monomeric [BiBr
6
cation/Bi ratio do not affect the composition of the products as well.
From the point of view of stoichiometry – and structure – compounds
1
-9
belong to
-
]} (
3-
] (
4-
three groups: polymeric {[BiBr
4
1
,
2
and
9
), binuclear [Bi
2
Br
9
3
-6
) and [Bi
2
Br10] (
7
and 8) built of {BiBr
6
} octahedra with shared face or edge, respectively (Figure 1).
Examples of halobismuthates of all these structural types were reported earlier [15], and
analysis of Bi-Br bond lengths distribution did not reveal any anomalies. In order to
extend the number of crystal structures for Hirshfeld surface analysis, thus enhancing
the reliability of possible correlations, screening of relevant articles was undertaken,
aiming at only those compounds that were synthesized under similar conditions. As a
result, we have selected nine bromobismuthates belonging to the same types as 1-9;
3
-
6
additionally, we selected four mononuclear [BiBr ] complexes (Table 3). Unfortunately,
the structures
1
and
9
have to be excluded from the consideration due to strong
+
+
disorder of PyH or 3-MePyH cations. Therefore, 19 crystal structures were chosen in
total.
3
-
4-
-
Figure 1. Anionic parts of 1-9: discrete [Bi
2 9 2 4
Br ] , [Bi Br10] (above) and {[BiBr ]} (below). Bi
turquoise, Br olive

Table 3. Bromobismuthates selected for Hirshfeld Surface Analysis
Number
Cation
Anion
Source
[31]
n-
2
3
4
5
6
7
8
N-methylpyridinium
N-ethylpyridinium
N-n-propylpyridinium
N-n-butylpyridinium
1,4-dimethylpyridinium
4-methylpyridinium
4-ethylpyridinium
4
{[BiBr ]}
3
-
-
-
-
[Bi
[Bi
[Bi
[Bi
2
2
2
2
Br
9
9
9
9
]
]
]
]
This work
This work
This work
This work
This work
This work
[43]
3
3
3
Br
Br
Br
4
-
-
[Bi
[Bi
[Bi
[Bi
[Bi
[Bi
[Bi
2
Br10
Br10
Br10
Br10
Br10
Br10
Br10
]
]
]
]
]
]
]
4
2
2
2
2
2
2
2
+
4-
1
1
1
1
1
1
1
1
1
1
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
H (4,4`-bipy)
4
4
4
4
-
-
-
-
1,2-bis (pyridinium)ethane
1,1`-dimethoxy-4,4`-bipyridinium
Pyrazolium
[44]
[45]
[46]
2,6-diethylanilinium
[47]
n-
Morpholin-4-ium
{[BiBr
4
]}
[48]
4
-
-
N-benzylpyridinium
[Bi
2
Br10
]
[49]
3
3
3
3
Dimethylammonium
[BiBr
[BiBr
[BiBr
[BiBr
6
6
6
6
]
]
]
]
[50]
-
2,6-di-isopropylanilinium
Diethylenetriammonium
1,4-bis (pyridinium)butane
1,5-bis (pyridinium)pentane
[51]
-
[52]
-
[53]
3
-
[Bi
Br
2 9
]
[53]
We carried out the HSA for the X-ray structures of
2
-8
and 10
-21 in order to evaluate
which cation-anion contacts give the largest contributions in crystal packing. For the
visualization, we have used mapping of the normalized contact distance (dnorm); its
negative value enables identification of molecular regions of substantial importance for
detection of short contacts. Figures 2-5 depict the Hirshfeld surfaces of the anionic
elementary fragments. In these Hirshfeld surfaces, the regions of shortest
intermolecular contacts are visualized by red circle areas. For polymeric anions in
, calculations were restricted by dimeric and trimeric units. The results are
summarized in Table 4.
2 and
1
5

Table 4. Contributions of different contacts to the molecular Hirshfeld surface*
Number
**
H-Br, %
78.1
80.8
88.9
91.0
93.7
88.1
93.7
96.7
81.6
86.6
84.4
93.9
90.0
76.3
77.1
98.1
100
C-Br, %
3.2
3.4
8.3
7.0
4.3
7.4
1.7
-
Br-Br, %
9.0
8.5
1.8
-
Bi-Br, %
N-Br, %
O-Br, %
2
9.2
-
-
-
2
***
3
8.5
-
-
-
-
4
-
1.0
1.1
1.5
1.0
-
-
5
-
-
-
6
3.1
3.6
2.0
2.6
3.7
1.7
5.1
3.5
13.7
15.5
-
-
-
7
-
-
8
-
-
1
1
1
1
1
0
1
2
3
4
12.2
7.6
10.8
-
-
3.4
2.2
1.9
-
-
-
-
-
1.3
-
-
-
-
-
5.3
1
5**
-
9.5
-
-
-
-
-
-
-
-
-
1
5***
-
6.8
-
1
1
1
1
2
2
6
7
8
9
0
1
1.1
-
-
-
-
-
-
-
-
-
-
96.9
94.6
92.5
88.6
1.8
-
1.0
5.4
-
-
-
6.0
6.5
1.4
1.5
2.9
*contributions of all other intermolecular contacts do not exceed 1% in total for each of the
structures **dimer ***trimer
From the obtained data, following observations can be made. In all cases, the H-Br
contacts are by far predominant, playing major role (in the case of 17, these are the only
contacts which were found). Unfortunately, there seems to be no correlation between
3
-
the contributions of different contacts in preferential formation of binuclear [Bi
2
Br
Br10] anionic species: average impact of H-Br contacts for both groups is very
similar, as well as the ranges (88.1-93.7 and 81.6-98.1%, respectively). In the case of
9
] or
4-
[Bi
2
3-
6
mononuclear [BiBr ] , the contribution of these interactions is consistently higher (92.5-

1
00%). For all polymeric structures the calculations are complicated by appearing Bi-Br
contacts related to interactions between the oligomers chosen as models; however,
their contribution decreases when fragments of higher nuclearity are used (trimers vs
dimers).
Figure 2. Hirshfeld surfaces of the anionic fragments of 3-5 (above), 6 and 21 (below)
Figure 3. Hirshfeld surfaces of the anionic fragments of 7, 8, 10, 11 (above), 12-14 and 16
below)
(

Figure 4. Hirshfeld surfaces of the anionic fragments of 17-20
Figure 5. Hirshfeld surfaces of the dimeric and trimeric fragments in 2 and 15
Conclusions
Nine bromobismuthates containing cations of pyridinium family have been prepared and
structurally characterized. HSA conducted for an extended series of related 19 structures shows
that the H-Br contacts are by far predominant among the cation-anion contacts, playing major
3-
] . However, these contacts seem equally
role in all cases, in particular for mononuclear [BiBr
6
3-
] and [Bi
4-
favor the isolation of HB with binuclear [Bi
2
Br
9
2
Br10] anions. Overall, the question
“
why halometalate anions of certain nuclearity form in presence of certain cation” remains
open, and we at this stage may only conclude that the answer cannot be acquired from the HSA
data in a straightforward way. A possible solution of the problem may be based on
chemoinformatic approaches applied for a greater set of XRD data. Besides, it cautioned that,
although HSA data frequently occur in recent halometalate-focused articles [54-59], its use
appears excessive since very few new information can be extracted.
Appendix A. Supplementary data
CCDC 1573664–1573671 contains the supplementary crystallographic data for 1 and 3-9. These
data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.

PXRD patterns
Acknowledgements
This work has been supported by Russian Science Foundation (Grant No. 14-23-00013,
experimental work) and Russian Foundation for Basic Research (project 16-33-60063, theoretical
studies). SAA thanks the Grant Council of President of Russia for a research fellowship. ASN is thankful
to the Saint Petersburg State University and Santander Bank for the opportunity to conduct a scientific
internship at the Instituto Superior Técnico, Universidade de Lisboa (Lisbon, Portugal). The authors
thank one of the referees for his/her useful and sound arguments regarding the influence of
stoichiometry which we really appreciated.
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3
-
Reactions of [BiBr
6
] and bromide salts of various pyridinium cations in excess of HBr result in a
n-
3-
series of bromobismuthate complexes of various geometry and nuclearity: [{BiBr
4
}
n
] , [Bi
Br10] . Hirshfeld surface analysis for 19 crystal structure was performed; impact of
various X-Br contacts on the crystal structures is discussed.
2 9
Br ]
4
-
and [Bi
2