Crystal structures of binuclear Bi(III) chloride and bromide complexes with some cations — Alkylated pyridine derivatives

Article abstract of DOI:10.1134/S0022476617040114

By a reaction of [BiX₆]^3– with salts of various N-alkylated pyridine derivatives in 2M HX (X = Cl, Br), (N-BzPy)₄[Bi₂X₁₀] complexes (X = Cl (1), Br (2), (4-MePyH)₄[Bi₂Cl₁₀

Full text of DOI:10.1134/S0022476617040114

Journal of Structural Chemistry. Vol. 58, No. 4, pp. 718-723, 2017.
Original Russian Text © 2017 S. A. Adonin, I. D. Gorokh, D. G. Samsonenko, I. V. Korol`kov, M. N. Sokolov, V. P. Fedin.
CRYSTAL STRUCTURES OF BINUCLEAR Bi(III)
CHLORIDE AND BROMIDE COMPLEXES WITH
SOME CATIONS – ALKYLATED PYRIDINE
DERIVATIVES
S. A. Adonin1,2, I. D. Gorokh2,
UDC 546.87
D. G. Samsonenko1,2, I. V. Korol`kov1,2,
M. N. Sokolov1,2,3, and V. P. Fedin1,2
3–
By a reaction of [BiX6] with salts of various N-alkylated pyridine derivatives in 2M HX (X = Cl, Br), (N-
BzPy)4[Bi2X10] complexes (X = Cl (1), Br (2), (4-MePyH)4[Bi2Cl10] (3)) are obtained and structurally
characterized.
DOI: 10.1134/S0022476617040114
Keywords: bismuth, halide complexes, polynuclear complexes, aromatic cations.
One of the key problems in the chemistry of polynuclear halide complexes of bismuth(III) (polyhalide bismuthates,
PHBs) remains the establishment of the relationship between synthesis conditions, the composition and structure of the
anionic part of these compounds [1-3]. This is due to an important feature of PHBs, which consists in their high lability
because of a relatively low binding energy of Bi(III)–X (X = Cl, Br, I) and a rapid kinetics of ligand substitution in the Bi(III)
3–
coordination sphere. During crystallization, complex [BiX6] anions existing in the solution can transform into PHBs with
diverse geometries and nuclearities (from 1 to 8) [4-15]. It has previously been noted [1-3] that the nature of a solvent and
a cation used to extract PHB are the most significant factors affecting the product structure. Taking into account that single
crystal and powder XRD are the main methods for identifying PHB complexes (the use of other physical methods is very
limited because of low information content), it is an essential task to obtain new data on their crystal structure.
In this work, three new complexes are structurally characterized: (N-BzPy)4[Bi2X10] (X = Cl (1), Br (2), and (4-
MePyH)4[Bi2Cl10] (3).
EXPERIMENTAL
Synthesis was carried out in the air. Precursors (HBr, HCl, BiCl3, BiOBr, pyridine, 4-methylpyridine (4-picoline),
and benzyl bromide) were purchased and used as received. N-benzylpyridinium bromide (N-BzPyBr) was obtained by
a reaction of benzyl bromide and pyridine (1.1:1) in a benzene:acetone (1:1) mixture at room temperature [16] and identified
1
by the H NMR spectrum.
1
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia;
2
3
adonin@niic.nsc.ru. Novosibirsk National Research State University, Russia. Kazan Federal University, Butlerov Institute
of Chemistry, Kazan, Russia. Translated from Zhurnal Strukturnoi Khimii, Vol. 58, No. 4, pp. 751-756, July-August, 2017.
Original article submitted January 12, 2016.
718
0022-4766/17/5804-0718 © 2017 by Pleiades Publishing, Ltd.

(N-BzPy)4[Bi2Cl10] (1). 47 mg (0.15 mmol) of BiCl3 were dissolved in 4 ml of 2M HCl and added to a solution of
75 mg (0.3 mmol) of N-benzylpyridinium bromide in 2 ml of 2M HCl. In several hours a colorless crystalline precipitate
formed, from which crystals of 2 suitable for single crystal XRD were selected.
(N-BzPy)4[Bi2Br10] (2). 61 mg (0.2 mmol) of BiOBr were dissolved in 5 ml of 2M HBr and added to a solution of
100 mg (0.4 mmol) of N-benzylpyridinium bromide in 5 ml of 2M HBr. In several seconds a light yellow fine crystalline
precipitate formed, from which crystals of 2 suitable for single crystal XRD were selected.
(4-MePyH)4[Bi2Cl10] (3). 150 mg (0.48 mmol) of BiCl3 were dissolved in 4 ml of 2M HCl and added to a solution
of 93 µl (0.96 mmol) of 4-methylpyridinium in 3 ml of 2M HCl. After evaporation for five days large colorless crystals
suitable for single crystal XRD formed.
Single crystal XRD. Diffraction data on single crystals 1-3 were measured at 130 K on an automated Agilent
Xcalibur diffractometer equipped with a two-dimensional AtlasS2 detector (graphite monochromator, λ(MoKα) = 0.71073 Å,
ω-scanning). Integration, absorption correction, and determination of unit cell parameters were performed using the
CrysAlisPro program package [17]. The structure was solved by direct methods and refined by full-matrix LSM in the
anisotropic approximation (except hydrogen atoms) using the SHELX-2013/2014 program package [18]. Positions of
hydrogen atoms of the organic cation were calculated geometrically and refined in the riding model. Details of single crystal
XRD and the main crystal structural data are summarized in Table 1; the main interatomic distances and bond angles are
given in Tables 2-4. Full tables of interatomic distances and bond angles, atomic coordinates, and atom displacement
parameters have been deposited with the Cambridge Crystallographic Data Center (CCDC-1511679, 1511680, 1511681);
http://www.ccdc.cam.ac.uk/data_request/cif), and also can be received from the authors.
TABLE 1. Crystallographic Parameters and Details of Single Crystal XRD Experiments for 1-3
Parameter
1
2
3
Chemical formula
M, g/mol
Crystal symmetry
Space group
a, Å
C48H48Bi2Cl10N4
1453.36
C48H48Bi2Br10N4
1897.96
C24H32Bi2Cl10N4
1148.99
Monoclinic
P21/n
Monoclinic
P21/n
Triclinic
P–1
9.85463(9)
23.45377(16)
11.71389(10)
9.9742(2)
24.1623(7)
11.7437(3)
8.9652(7)
10.2539(8)
10.6852(9)
98.858(2)
109.666(2)
96.964(2)
897.99(13)
1; 2.125
b, Å
c, Å
α, deg
106.5606(9)
105.163(3)
β, deg
γ, deg
3
V, Å
2595.10(4)
2; 1.860
2731.69(13)
2; 2.307
3
Z; ρ(calc.), g/cm
–1
F(000); μ, mm
1400; 7.325
1760; 13.783
540; 10.552
Crystal dimensions, mm
θ scanning range, deg
Range of hkl indices
0.26×0.22×0.17
0.64×0.15×0.07
0.21×0.12×0.11
3.31–32.84
3.30–30.99
2.05–28.06
–15 < h < 15,
–35 < k < 36,
–17 < l < 17
–13 < h < 7,
–30 < k < 34,
–17 < l < 17
17567 / 7595
–12 < h < 12,
–14 < k < 14,
–15 < l < 15
24908 / 4339
Number of meas. / indep. reflections
Rint; number of reflections with I > 2σ(I)
GOOF on F2
57370 / 9041
0.0188; 8526
0.0467; 5991
0.0265; 4236
1.066
1.023
1.179
R1 = 0.0237,
wR2 = 0.0656
R1 = 0.0469,
wR2 = 0.1033
R1 = 0.0117,
wR2 = 0.0293
R-factors I > 2σ(I)
R-factors (over all reflections)
R1 = 0.0260,
wR2 = 0.0667
R1 = 0.0660,
wR2 = 0.1134
R1 = 0.0123,
wR2 = 0.0295
3
Res. electron density (max / min), e/Å
2.178 / –1.075
3.735 / –2.856
0.428 / –0.905
719

TABLE 2. Main Bond Lengths and Bond Angles in 1
Bond
d, Å
Angle
Angle
ω, deg
ω, deg
Bi(1)–Cl(1)
Bi(1)–Cl(2)
2.6283(6)
2.9034(6)
2.9881(6)
Cl(1)–Bi(1)–Cl(2)
91.959(19)
175.373(19)
90.50(2)
Cl(3)–Bi(1)–Cl(5)
176.01(2)
89.87(2)
i
i
Cl(1)–Bi(1)–Cl(2)
Cl(1)–Bi(1)–Cl(3)
Cl(1)–Bi(1)–Cl(4)
Cl(1)–Bi(1)–Cl(5)
Cl(4)–Bi(1)–Cl(2)
Cl(4)–Bi(1)–Cl(2)
Cl(4)–Bi(1)–Cl(3)
Cl(4)–Bi(1)–Cl(5)
Cl(5)–Bi(1)–Cl(2)
i
Bi(1)–Cl(2)
178.08(2)
93.02(2)
89.75(2)
89.03(2)
90.94(2)
i
Cl(2)–Bi(1)–Cl(2)
88.359(17)
84.913(19)
86.09(2)
89.968(19)
95.588(19)
91.643(16)
i
i
Cl(3)–Bi(1)–Cl(2)
Cl(3)–Bi(1)–Cl(2)
Cl(5)–Bi(1)–Cl(2)
Bi(1)–Cl(2)–Bi(1)
i
i
Coordinates of dependent atoms are obtained by the following symmetry operations: –x, 1–y, –z.
TABLE 3. Main Bond Lengths and Bond Angles in 2
Bond
d, Å
Angle
Angle
ω, deg
ω, deg
i
Bi(1)–Br(1)
Bi(1)–Br(2)
2.8863(6)
3.0621(6)
3.0160(7)
2.7533(6)
2.7971(6)
2.7514(7)
Br(1)–Bi(1)–Br(2)
88.522(18)
94.514(18)
88.379(17)
89.910(19)
91.261(19)
175.550(19)
90.69(2)
Br(4)–Bi(1)–Br(2)
84.858(18)
86.065(19)
91.53(2)
i
Br(1)–Bi(1)–Br(2)
Br(4)–Bi(1)–Br(2)
i
i
Br(2) –Bi(1)–Br(2)
Bi(1)–Br(2)
Bi(1)–Br(3)
Bi(1)–Br(4)
Bi(1)–Br(5)
Br(5)–Bi(1)–Br(1)
i
Br(3)–Bi(1)–Br(1)
Br(5)–Bi(1)–Br(2)
Br(5)–Bi(1)–Br(2)
Br(5)–Bi(1)–Br(3)
Br(5)–Bi(1)–Br(4)
177.83(2)
89.458(19)
90.90(2)
i
Br(3)–Bi(1)–Br(2)
Br(3)–Bi(1)–Br(2)
Br(3)–Bi(1)–Br(4)
Br(4)–Bi(1)–Br(1)
93.86(2)
i
Bi(1) –Br(2)–Bi(1)
174.57(2)
91.622(17)
i
Coordinates of dependent atoms are obtained by the following symmetry operations: 1–x, 1–y, 1–z.
TABLE 4. Main Bond Lengths and Bond Angles in 3
Bond
d, Å
Angle
Angle
ω, deg
ω, deg
Bi(1)–Cl(1)
Bi(1)–Cl(2)
Bi(1)–Cl(3)
Bi(1)–Cl(4)
Bi(1)–Cl(5)
2.5801(5)
2.6727(5)
2.5864(5)
2.7303(5)
2.8310(5)
2.9674(5)
Cl(1)–Bi(1)–Cl(2)
Cl(1)–Bi(1)–Cl(3)
Cl(1)–Bi(1)–Cl(4)
Cl(1)–Bi(1)–Cl(5)
89.696(17)
93.577(18)
90.528(17)
93.797(17)
175.121(14)
178.810(13)
87.845(14)
93.360(16)
Cl(3)–Bi(1)–Cl(2)
Cl(3)–Bi(1)–Cl(4)
91.886(15)
89.266(15)
90.125(15)
172.619(16)
90.975(14)
86.340(15)
82.529(14)
97.471(14)
i
Cl(3)–Bi(1)–Cl(5)
Cl(3)–Bi(1)–Cl(5)
Cl(4)–Bi(1)–Cl(5)
i
Cl(1)–Bi(1)–Cl(5)
Cl(2)–Bi(1)–Cl(4)
Cl(2)–Bi(1)–Cl(5)
i
i
Bi(1)–Cl(5)
Cl(4)–Bi(1)–Cl(5)
Cl(5)–Bi(1)–Cl(5)
Bi(1)–Cl(5)–Bi(1)
i
i
i
Cl(2)–Bi(1)–Cl(5)
i
Coordinates of dependent atoms are obtained by the following symmetry operations: 1–x, 1–y, 1–z.
Powder XRD. The powder XRD analysis of polycrystals was conducted on a Shimadzu XRD-7000 diffractometer
(room temperature, CuKα radiation, Ni filter, 2θ range 5-60°, step 0.03° 2θ, acquisition time 1 s). Samples for the study were
prepared as follows: polycrystals were ground in an agate mortar; powder was deposited on the polished side of the standard
quartz cuvette covered with a thin layer of vaseline oil. The fact that compounds are single phase was established by
a comparison of the indexed powder X-ray diffraction pattern by analogy with a theoretical diffraction pattern of the
complex, which was calculated from the structure of a single crystal obtained by single crystal XRD.
720

RESULTS AND DISCUSSION
Compounds 1 and 2 are isostructural and crystallize in the monoclinic symmetry (space group P21/n). The
asymmetric unit contains one Bi(III) cation. The Bi(III) cation is in the octahedral coordination environment composed of six
halide ligands. Two Bi(III) cations are linked with each other by two bridging halide ligands, forming a binuclear [Bi2(μ-
4–
X)2X8] anionic complex (X = Cl and Br for 1 and 2 respectively) (Fig. 1). The Bi–Cl(terminal) distances are in the range
2.6283(6)-2.7567(6) Å. The Bi–Cl(bridging) distances are 2.9034(6) Å and 2.9881(6) Å. In bromide complex 2 the Bi–
Br(terminal) distances are in the range 2.7514(7)-2.8863(6) Å, and the Bi–Br(bridging) distances are 3.0160(7) Å and
4–
3.0621(6) Å. The [Bi2(μ-X)2X8] anions are located in position 2c (one of the systems of inversion centers: 0, 1/2, 0;
1/2, 0, 1/2). Organic cations are located in general positions. The cation and anion packing is shown in Fig. 2. Complex
anions form layers parallel to the ac plane, and between them organic cations are located. Interactions between the
components of the structure have an exclusively van der Waals and ionic character. Between the organic cations there are π–
Fig. 1. Structure of the organic cation and the complex anion in 1 (a) and 2 (b). Hydrogen atoms are omitted.
50% probability ellipsoids. Coordinates of dependent atoms are obtained by the following symmetry
i
operations: –x, 1–y, –z; 1–x, 1–y, 1–z.
ii
Fig. 2. Cation and anion packing in the structure of 1
(view along the a axis). Hydrogen atoms are omitted.
721

π interactions; the shortest C…C distances are 3.282 Å and 3.335 Å, C…N distances are 3.169 Å and 3.216 Å for 1 and 2
respectively.
Compound 3 crystallizes in the triclinic symmetry (space group P–1). The asymmetric unit contains one Bi(III)
cation; it is in the octahedral coordination environment of six chloride ligands. Two Bi(III) cations are linked with each other
4–
by two bridging chloride ligands (μ-Cl), forming a binuclear [Bi2(μ-Cl)2Cl8] anionic complex (Fig. 3). The Bi–Cl(terminal)
distances are in the range 2.5801(5)-2.7303(5) Å. The Bi–Cl(bridging) distances are 2.8310(5) Å and 2.9674(5) Å. The
4–
[Bi2(μ-X)2X8] anions are located in position 1h (one of the systems of inversion centers: 1/2, 1/2, 1/2). Organic cations are
located in general positions. The cation and anion packing is shown in Fig. 4. Complex anions form layers (parallel to the bc
plane) between which the organic cations are located. The organic cations and complex anions form intermolecular
Fig. 3. Structure of the organic cation and the
complex anion in 3. Hydrogen atoms are omitted.
50% probability ellipsoids. Coordinates of
dependent atoms are obtained by the following
i
symmetry operations: 1–x, 1–y, 1–z.
Fig. 4. Cation and anion packing in the structure of 3
(view along the c axis). Hydrogen atoms are omitted.
722

N–H…Cl(terminal) contacts; the N…Cl distances are 3.130 Å and 3.204 Å (Fig. 4, shown by a dashed line). Between the
organic cations there are π–π interactions; the shortest C…C and C…N distances are 3.393 Å and 3.309 Å respectively.
According to the powder XRD data, compounds 1 and 3 are isolated in the pure form whereas in the solid phase of 2
an unidentified impurity is present (here 2 is the main component). Attempts to optimize the synthesis by changing the
reagent ratio were unsuccessful.
4–
The [Bi2X10] structure type is common for PHBs. In particular, the formation of anions with this structure is most
often observed when hydrohalic acid solutions serve simultaneously as a solvent and a source of halide ligands [2]. It should
3–
be noted, however, that, unlike chlorobismuthates, for bromide complexes the most often occurring type is [Bi2Br9] [2]. Not
4–
infrequently, the formation of [Bi2X10] occurs during the crystallization with cations that are the protonated forms of N-
containing bases. The crystal structure contains characteristic cation-anion contacts of the N–H⋯X type (compare, e.g., with
3). In the structures of 1 and 2, similar interactions are observed between hydrogen atoms belonging to methylene groups of
+
N-BzPy and terminal chloride and bromide ligands (average values of 2.63 Å and 2.77 Å respectively).
The authors acknowledge the support of RFBR (grant No. 14-23-00013).
S. A. Adonin is grateful to the President of the Russian Federation for support (grant of the President of the Russian
Federation for young scientists).
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