Principles of the Construction of Polymer Structures, Heteronuclear (13C, 15N) CP-MAS NMR, and Thermal Behavior of Heteroleptic Bismuth(III) Complexes of the General Composition [Bi(S2CNR2)2X] (X = NO3, Cl)

Article abstract of DOI:10.1134/S1070328419100038

Abstract: The crystalline heteroleptic bismuth(III) complexes, [Bi{S₂CN(iso-C₄H₉)₂}₂(NO₃)] (I) and [Bi{S₂CN(C₃H₇)₂}₂Cl] (II), are isolated in preparative yields. Both compounds form 1D polymer structures and are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1877115 (I) and 1876364 (II)) and (¹³C, ¹⁵N) CP-MAS NMR spectroscopy. The coordination mode of each of the dialkyldithiocarbamate ligands is S,S′-anisobidentately terminal. The inorganic anions performing the μ₂-bridging function participate in the binding of the adjacent metallic atoms to form zigzag polymer chains. A new mode of bismuth(III) binding involving all oxygen atoms (O,O'-anisobidentate coordination to each adjacent bismuth atom) is found for the bridging nitrate groups in compound I. The bismuth atoms in the studied compounds are characterized by the eightfold [BiS₄O₄] (I) or sixfold [BiS₄Cl₂] (II) environment. The thermal behavior of the synthesized complexes is characterized by the data of simultaneous thermal analysis, using parallel recording of thermogravimetry and differential scanning calorimetry curves. In both cases, Bi₂S₃ is the only final product of the thermal transformations of compounds I and II.

Full text of DOI:10.1134/S1070328419100038

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2019, Vol. 45, No. 10, pp. 695–705. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Koordinatsionnaya Khimiya, 2019, Vol. 45, No. 10, pp. 599–610.
Principles of the Construction of Polymer Structures, Heteronuclear
(13C, 15N) CP-MAS NMR, and Thermal Behavior
of Heteroleptic Bismuth(III) Complexes of the General Composition
[Bi(S2CNR2)2X] (X = NO3, Cl)
E. V. Novikovaa, A. V. Ivanova, *, I. V. Egorovab, R. S. Troshinab, N. A. Rodionovab,
A. I. Smolentsevc, d, and O. N. Antzutkine, f
aInstitute of Geology and Nature Management, Far East Branch, Russian Academy of Sciences,
Blagoveshchensk, 675000 Russia
bBlagoveshchensk State Pedagogical University, Blagoveshchensk, 675000 Russia
cNikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
dNovosibirsk State University, Novosibirsk, 630090 Russia
eLuleå University of Technology, Luleå, Sweden
fUniversity of Warwick, Coventry, United Kingdom
*e-mail: alexander.v.ivanov@chemist.com
Received March 29, 2019; revised April 8, 2019; accepted April 22, 2019
Abstract—The crystalline heteroleptic bismuth(III) complexes, [Bi{S2CN(iso-C4H9)2}2(NO3)] (I) and
[Bi{S2CN(C3H7)2}2Cl] (II), are isolated in preparative yields. Both compounds form 1D polymer structures
and are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1877115 (I) and 1876364 (II)) and
(13C, 15N) CP-MAS NMR spectroscopy. The coordination mode of each of the dialkyldithiocarbamate
ligands is S,S′-anisobidentately terminal. The inorganic anions performing the μ2-bridging function partici-
pate in the binding of the adjacent metallic atoms to form zigzag polymer chains. A new mode of bismuth(III)
binding involving all oxygen atoms (O,O'-anisobidentate coordination to each adjacent bismuth atom) is
found for the bridging nitrate groups in compound I. The bismuth atoms in the studied compounds are char-
acterized by the eightfold [BiS4O4] (I) or sixfold [BiS4Cl2] (II) environment. The thermal behavior of the syn-
thesized complexes is characterized by the data of simultaneous thermal analysis, using parallel recording of
thermogravimetry and differential scanning calorimetry curves. In both cases, Bi2S3 is the only final product
of the thermal transformations of compounds I and II.
Keywords: heteroleptic bismuth(III) complexes, dialkyldithiocarbamate ligands, 1D polymer structures,
thermal behavior, X-ray diffraction analysis, heteronuclear (13C, 15N) MAS NMR spectroscopy
DOI: 10.1134/S1070328419100038
INTRODUCTION
(X = Cl, Br, I) [25–28]. The latter can be used for
the production of materials based on the Bi2S3 films
and nanoparticles [24, 27].
The low toxicity of bismuth and its compounds
compared to other heavy metals, on the one hand,
predetermined a tendency in industry to replace
lead and antimony by bismuth and, on the other
hand, makes it possible to use the bismuth(III)
complexes in the production of drugs with antiulcer,
anti-inf lammatory, and antibacterial activity. The
bismuth complexes, including those with dial-
kyldithiocarbamate ligands, exhibit antibacterial
[1–4] and also anticancer activity [5–9]. In addi-
tion to the dithiocarbamate complexes [2–4, 9–18],
bismuth(III) also forms heteroleptic compounds,
whose inner sphere contains the inorganic anions
In this work, we preparatively isolated the crys-
talline heteroleptic bismuth(III) complexes of the
general composition [Bi(S2CNR2)2X] (R = iso-
C4H9, X = NO3 (I); R = C3H7, X = Cl (II)). Accord-
ing to the X-ray diffraction analysis data, the com-
plexes form 1D polymer structures. The synthesized
compounds were characterized by the data of (13C,
15N) CP-MAS NMR spectroscopy. Their thermal
behavior was studied by simultaneous thermal anal-
ysis (STA).
along with =NC(S)S– groups:
− [19–24] and X–
NO3
695

696
NOVIKOVA et al.
EXPERIMENTAL
The initial compounds Na{S2CN(C3H7)2} · H2O
and Na{S2CN(iso-C4H9)2} · 3H2O were synthesized by
the reactions of the corresponding dialkylamines,
HN(C3H7)2 (Merck) and HN(iso-C4H9)2 (Aldrich),
with carbon bisulfide (Merck) taken in equimolar
amounts in an alkaline medium [29].
1270 w, 1241 s, 1197 m, 1148 s, 1102 w, 1087 m, 1032 w,
962 m, 894 m, 765 w, 752 m, 619 w, 602 m, 536 w.
15
13С, N CP-MAS NMR for complex I (δ, ppm):
204.4, 199.9 (1 : 1, –S2CN=); 63.7, 61.9, 57.6 (1 : 1 : 2,
=NCH2–); 29.4, 28.2, 26.5 (1 : 1 : 2, –CH=); 23.6,
22.4, 21.8, 21.4, 20.8, 19.6, 19.0 (1 : 2 : 1 : 1 : 1 : 1 : 1,
–
–CH3); 146.4, 140.1 (1 : 1, –S2CN=); 336.5 (NO3 );
IR (KBr; ν, cm–1) for Na{S2CN(iso-C4H9)2} ·
3H2O: 3362 s.br, 2961 s, 2933 m, 2893 vw, 2867 m,
1641 m, 1596 m, 1477 s, 1463 w, 1424 w, 1400 m,
1382 m, 1367 w, 1355 m, 1337 w, 1290 m, 1233 s,
1202 m, 1169 w, 1150 m, 1090 s, 1009 w, 972 s, 936 m,
909 w, 868 m, 817 w, 805 w, 612 m, 557 w, 467 w; for
Na{S2CN(C3H7)2} · H2O: 3368 s.br, 2963 m, 2930 m,
2872 m, 2130 s, 1632 s, 1468 s, 1408 s, 1368 s, 1304 m,
1298 m, 1267 m, 1237 s, 1198 s, 1138 s, 1107 w, 1088 m,
1028 m, 970 s, 891 m, 864 m, 745 m, 602 w, 536 w [18].
13С CP-MAS NMR (δ, ppm) for Na{S2CN(iso-
C4H9)2} · 3H2O: 208.2 (−S2CN=); 66.7 (=NCH2−);
28.0, 27.1 (1 : 1, =CH−); 23.0, 22.4, 20.8 (1 : 1 : 2,
−CH3) [30]; for Na{S2CN(C3H7)2} · H2O: 208.3
(−S2CN=); 59.4, 57.9 (1 : 1, =NCH2−); 22.3, 21.5 (1 :
1, −CH2−); 12.6, 11.5 (1 : 1, −CH3) [30].
II: 200.1, 199.3 (1 : 1, –S2CN=); 57.7, 56.7, 55.6 (1 : 1 :
2, =NCH2–); 23.0, 20.8, 20.1 (1 : 2 : 1, –CH2–);
13.2, 12.7, 11.8 (1 : 2 : 1, –CH3); 143.7, 141.3 (1 : 1,
‒S2CN=).
13C/15N CP-MAS NMR spectra were recorded on
an Ascend Aeon (Bruker) with the working frequency
of 100.64/40.55 MHz a superconducting magnet
(В0 = 9.4 T) with the closed cycle of helium condensa-
tion through an external compressor, and the Fourier
transform. Proton cross polarization (CP) was used
with the contact time
1H−13C/1H−15N 2.0/1.5 ms.
The 13C−1H/15N−1H interaction suppression was
based on the decoupling effect using the radiofre-
quency field at the resonance proton frequency
(400.21 MHz) [31]. Polycrystalline samples of com-
pounds I (~61 mg) and II (~29 mg) were placed in a
4.0-mm ZrO2 ceramic rotor. For measuring the
Syntheses of the 1D polymer complexes, catena-
poly[(μ2-nitrato-O,{O',O"})bis(N,N-di-iso-butyldith-
iocarbamato-S,S')bismuth(III)] (I) and catena-po-
ly[(μ2-chloro)bis(N,N-dipropyldithiocarbamato-
S,S')bis-muth(III)] (II), were carried out via the fol-
lowing reaction:
13C/15N NMR spectra, the rotation of the samples
under the magic angle (MAS) was used at the fre-
quency 5000–10000/5000(1) Hz, the number of
acquisitions was 23400–30000/31648–78200, the
duration of the proton π/2 pulses was 2.7/2.7 μs, and
the interval between pulses was 2.0/2.0 s. The isotropic
chemical shifts δ(13C)/δ(15N) are given relative to one
of the components of crystalline adamantane as an
external standard (δ = 38.48 ppm relative to
tetramethylsilane)/crystalline NH4Cl (δ = 0.0 ppm, –
341 ppm in the absolute scale [32]) with a correction
to the drift of the magnetic field strength, the fre-
quency equivalent of which was 0.031/0.011 Hz/h.
The magnetic field homogeneity was controlled by the
width (2.6 Hz) of the reference line of adamantane.
The IR spectra of complexes I and II pressed in
KBr pellets were recorded on FSM–1201 and FSM–
2202 interference FTIR spectrometers in ranges of
450–7500 and 400–4000 cm–1. The instruments were
controlled and the spectra were processed using the
FSpec program (version 4.0.0.2 for Windows, OOO
Monitoring, Russia).
BiX + 2Na S CNR = Bi S CNR X + 2NaX.
(
)
(
)
2
2
[
]
3
2
2
2
For compounds I and II, the reaction between
Bi(NO3)3 · 5H2O and Na{S2CN(iso-C4H9)2} · 3H2O/
BiCl3 · H2O or Na{S2CN(C3H7)2} · H2O was carried
out in an acetone–ethanol (1 : 1) system or in an ace-
tone solution, respectively. The starting bismuth salts
were used in a 5% stoichiometric excess. The reaction
mixtures were magnetically stirred for 1 h and left to
stay at room temperature. Then the solutions were
separated from the formed precipitates by filtration
with additional washing of the target complexes from
the precipitate phase with the corresponding solvents.
Yellow plate-like crystals of complexes I or II were
obtained by the slow evaporation of the solvents at
room temperature (a minor amount CH2Cl2 was
added to the solution to improve the crystallization of
compound I). The yields of compounds I and II were
64.4 and 78.0%, respectively; and mp = 155–158 and
146–148°С for compounds I and II, respectively.
X-ray diffraction analyses of complexes I and II were
carried out from plate-like single crystals on Bruker-
Nonius X8 Apex CCD and Bruker SMART 1000 CCD
diffractometers at 150(2) and 120(2) K (MoKα radia-
tion, λ = 0.71073 Å, graphite monochromator). The
data were collected using a standard procedure: ϕ and
ω scan modes for narrow frames or in a hemisphere
range. An absorption correction was applied empiri-
cally (SADABS) [33]. The structures were determined
IR for complex I (KBr; ν, cm–1): 2962 s, 2930 m,
2898 vw, 2871 m, 1634 m, 1501 s, 1485 m, 1466 m,
1431 s, 1385 s, 1369 vw, 1358 m, 1339 m, 1311 s, 1249 s,
1195 m, 1171 w, 1149 s, 1128 w, 1122 w, 1090 w, 1032 m,
970 m, 921 m, 885 w, 818 w, 714 w, 707 vw, 628 w,
607 w, 532 w; for complex II: 2964 s, 2929 m, 2870 m,
1493 s, 1464 m, 1428 s, 1363 m, 1341 w, 1303 m, by a direct method and refined by least squares (for F2)
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PRINCIPLES OF THE CONSTRUCTION OF POLYMER STRUCTURES, HETERONUCLEAR
697
Table 1. Crystallographic data and experimental structure refinement parameters for compounds [Bi{S2CN(iso-
C4H9)2}2(NO3)] (I) and [Bi{S2CN(C3H7)2}2Cl] (II)
Value
Parameter
I
II
Empirical formula
FW
C18H36N3O3S4Bi
679.72
C14H28N2S4ClBi
597.05
Crystal system
Space group
a, Å
b, Å
c, Å
β, deg
V, Å3
Orthorhombic
Pca21
Monoclinic
P21/c
11.1947(7)
10.8399(6)
21.5113(11)
90
9.6492(12)
24.466(3)
9.2616(11)
95.514(3)
2176.4(5)
2610.4(3)
Z
4
4
ρ
calc, g/cm3
1.730
1.822
μ, mm–1
7.097
8.606
F(000)
1344
1160
Crystal size, mm3
0.25 × 0.25 × 0.06
0.25 × 0.21 × 0.10
Range of data collection over θ, deg
Ranges of reflection indices
2.62–27.50
2.12–28.00
–9 ≤ h ≤ 14,
–14 ≤ k ≤ 12,
–27 ≤ l ≤ 23
–12 ≤ h ≤ 12,
–32 ≤ k ≤ 32,
–12 ≤ l ≤ 12
Number of measured reflections
Number of independent reflections (Rint)
Number of reflections with I > 2σ(I)
Number of refinement variables
GOOF
15835
5637 (0.0267)
20874
5224 (0.0495)
5327
271
0.896
5224
203
1.007
R factors for F 2 > 2σ(F 2)
R1 = 0.0205
wR2 = 0.0453
R1 = 0.0274
wR2 = 0.0557
R factors for all reflections
R1 = 0.0223
R1 = 0.0350
wR2 = 0.0458
wR2 = 0.0585
Residual electron density (min/max), e/Å3
–0.945/2.221
–1.486/1.896
in the full-matrix anisotropic approximation of non- nos. 1877115 (I) and 1876364 (II); deposit@ccdc.cam.
ac.uk or http://www.ccdc.cam.ac.uk).
hydrogen atoms. The positions of hydrogen atoms
were calculated geometrically and included into
refinement in the riding model. The calculations on
structure determination and refinement were per-
formed using the SHELXTL program package [33,
34]. The main crystallographic data and results of
structure refinement for compounds I and II are pre-
sented in Table 1. Selected bond lengths and angles are
given in Table 2.
The thermal behavior of complexes I and II was
studied by the STA method with the simultaneous
detection of thermogravimetry (TG) and differential
scanning calorimetry (DSC) curves. The study was
conducted on an STA 449C Jupiter instrument
(NETZSCH) in corundum crucibles with a cap and a
hole providing a vapor pressure of 1 atm during ther-
molysis. The heating rate was 5°С/min to 400°С under
an argon atmosphere, and the weights of the samples
were 1.800–6.348 and 5.800–7.188 mg for complexes
I and II, respectively. The accuracy of the temperature
The coordinates of atoms, bond lengths, bond
angles, and temperature parameters for the synthe-
sized complexes were deposited with the Cambridge measurement was 0.7°С, and the accuracy of the
Crystallographic Data Centre (CIF files CCDC weight change was 1 × 10−4 mg.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 45 No. 10 2019

698
NOVIKOVA et al.
Table 2. Bond lengths (d, Å) and bond (ω, deg) and torsion (ϕ, deg) angles in the structures of compounds I and II*
Compound I
bond
d, Å
bond
S(4)–C(10)
N(1)–C(1)
N(1)–C(2)
N(1)–C(6)
N(2)–C(10)
N(2)–C(11)
d, Å
Bi(1)–S(1)
Bi(1)–S(2)
Bi(1)–S(3)
Bi(1)–S(4)
Bi(1)–O(1)
Bi(1)–O(1)a
Bi(1)–O(2)
Bi(1)–O(3)a
S(1)–C(1)
S(2)–C(1)
S(3)–C(10)
2.6309(10)
2.8012(8)
2.7335(8)
2.6199(9)
2.955(3)
2.961(3)
3.007(3)
2.850(3)
1.742(3)
1.720(4)
1.724(3)
1.742(3)
1.327(5)
1.474(4)
1.482(5)
1.334(4)
1.483(4)
1.461(4)
1.265(4)
1.240(4)
1.250(4)
N(2)–C(15)
O(1)–N(3)
O(2)–N(3)
O(3)–N(3)
angle
ω, deg
angle
ω, deg
O(1)aBi(1)S(4)
O(2)Bi(1)S(1)
O(2)Bi(1)S(2)
O(2)Bi(1)S(3)
O(2)Bi(1)S(4)
O(3)aBi(1)S(1)
O(3)aBi(1)S(2)
O(3)aBi(1)S(3)
O(3)aBi(1)S(4)
O(1)Bi(1)O(1)a
O(1)Bi(1)O(2)
O(1)Bi(1)O(3)a
O(2)Bi(1)O(1)a
O(2)Bi(1)O(3)a
S(1)C(1)S(2)
118.1(2)
68.41(5)
118.05(6)
126.79(6)
85.46(6)
141.24(6)
166.46(7)
S(1)Bi(1)S(2)
S(3)C(10)S(4)
S(3)Bi(1)S(4)
S(1)Bi(1)S(3)
S(1)Bi(1)S(4)
66.17(3)
117.55(16)
67.19(3)
85.90(3)
87.96(3)
S(2)Bi(1)S(3)
S(2)Bi(1)S(4)
O(1)Bi(1)S(1)
O(1)Bi(1)S(2)
144.16(3)
88.87(3)
77.24(6)
120.81(5)
70.28(5)
135.73(4)
130.27(6)
70.10(5)
119.88(5)
112.99(6)
88.86(5)
78.50(6)
148.65(9)
42.41(8)
112.64(8)
106.54(8)
73.86(9)
O(1)Bi(1)S(3)
O(1)Bi(1)S(4)
O(1)aBi(1)S(1)
O(1)aBi(1)S(2)
O(1)aBi(1)S(3)
angle
ϕ, deg
angle
ϕ, deg
Bi(1)S(1)S(2)C(1)
Bi(1)S(3)S(4)C(10)
S(1)Bi(1)C(1)S(2)
S(3)Bi(1)C(10)S(4)
S(1)C(1)N(1)C(2)
S(1)C(1)N(1)C(6)
163.5(2)
–178.2(2)
165.9(2)
–178.5(2)
173.6(2)
S(2)C(1)N(1)C(2)
S(2)C(1)N(1)C(6)
S(3)C(10)N(2)C(11)
S(3)C(10)N(2)C(15)
S(4)C(10)N(2)C(11)
S(4)C(10)N(2)C(15)
–7.2(5)
172.4(3)
–0.7(4)
175.9(2)
179.7(3)
–3.6(4)
–6.8(5)
Compound II
bond
d, Å
bond
d, Å
Bi(1)–S(1)
Bi(1)–S(2)
Bi(1)–S(3)
Bi(1)–S(4)
2.6369(9)
2.7207(9)
2.6180(10)
2.8290(10)
S(3)–C(2)
S(4)–C(2)
N(1)–C(1)
N(1)–C(3)
1.741(4)
1.714(4)
1.322(4)
1.477(4)
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PRINCIPLES OF THE CONSTRUCTION OF POLYMER STRUCTURES, HETERONUCLEAR
Table 2. (Contd.)
699
Compound II
bond
Bi(1)–Cl(1)
Bi(1)–Cl(1)а
S(1)–C(1)
S(2)–C(1)
d, Å
bond
N(1)–C(6)
N(2)–C(2)
d, Å
2.9010(9)
3.1276(10)
1.739(4)
1.474(4)
1.316(5)
1.475(5)
1.468(5)
N(2)–C(9)
N(2)–C(12)
1.723(4)
angle
ω, deg
angle
ω, deg
S(1)C(1)S(2)
S(1)Bi(1)S(2)
S(4)C(2)S(3)
S(3)Bi(1)S(4)
S(1)Bi(1)S(3)
S(1)Bi(1)S(4)
117.7(2)
67.13(3)
118.4(2)
65.90(3)
89.96(3)
84.76(3)
S(2)Bi(1)S(4)
S(1)Bi(1)Cl(1)
S(2)Bi(1)Cl(1)
S(3)Bi(1)Cl(1)
S(4)Bi(1)Cl(1)
Bi(1)Cl(1)Bi(1)a
Cl(1)Bi(1)Cl(1)а
angle
139.61(3)
150.91(3)
84.37(3)
81.54(3)
116.12(3)
109.10(3)
S(2)Bi(1)S(3)
84.95(3)
120.83(3)
angle
ϕ, deg
ϕ, deg
Bi(1)S(1)S(2)C(1)
Bi(1)S(3)S(4)C(2)
S(1)Bi(1)C(1)S(2)
S(3)Bi(1)C(2)S(4)
S(1)C(1)N(1)C(3)
S(1)C(1)N(1)C(6)
170.7(2)
–173.7(2)
172.0(2)
174.6(2)
–1.7(5)
S(2)C(1)N(1)C(3)
S(2)C(1)N(1)C(6)
S(3)C(2)N(2)C(9)
S(3)C(2)N(2)C(12)
S(4)C(2)N(2)C(9)
S(4)C(2)N(2)C(12)
177.6(3)
3.8(5)
2.0(5)
–179.1(3)
–178.7(3)
0.2(5)
–175.5(3)
a
a
* Symmetry transforms: 1/2 + x, –y, z (I); x, 1/2 – y, 1/2 + z (II).
RESULTS AND DICUSSION
the covalent bonding of the dithiocarbamate (Dtc)
ligands by bismuth(III).
In the IR spectra of complexes I and II, the absorp-
tion bands in a range of 2964–2870 cm–1 are caused by
stretching vibrations of the С–Н bonds of the alkyl
groups: νas(СН3) 2962 and 2964, νs(СН3) 2871 and
In addition, the IR spectrum of complex I exhibits
the nitrate group: the medium-intensity band of
νs(N=O) stretching vibrations at 1634 cm–1, the nar-
row high-intensity band (1385 cm–1) caused by
2870, and νas(СН2) 2930 and 2929 cm–1 for complexes
I and II, respectively (for complex I, the weakly
intense ν(СН) band is observed at 2898 cm–1) [35].
The high- (1149/1148 cm–1) and medium-intensity
(970/962 cm–1) absorption bands were assigned to the
νas(СS2) and νs(СS2) vibrations, respectively [36–38].
νas(NO2) stretching vibrations, the medium-intensity
band νs(NO2) at 1032 cm–1, and the band of the planar
δ(
–) bending vibration at 714 cm–1 (with a shoul-
NO3
der at 707 cm–1) [39–41]. The very significant differ-
ence (in 249 cm–1) between two high-frequency bands
indicates a complicated character of nitrate group
coordination [39–41].
An important feature of the intense absorption
bands at 1501 or 1493 cm–1 attributed to the stretching
vibrations of the ν(C–N) bond in the =NC(S)S–
group is their position between the ranges of vibrations
of the С=N double (1690–1640 cm–1) and С–N ordi-
nary (1360–1250 cm–1) bonds [29]. This fact directly
indicates the partially dual character of the С–N bond
in the dithiocarbamate group. The shift of the dis-
cussed absorption bands to the high-frequency range
for complexes I and II compared to the corresponding
X-ray diffraction analysis was used to establish the
structural organization of the obtained polymer com-
plexes. In both complexes I and II, the unit cell
includes four formula units (Figs. 1, 2). In both cases,
the central bismuth atom binds two terminal Dtc
ligands exhibiting the S,S'-anisobidentate coordina-
tion, where one of the Bi–S bonds (2.6199,
2.6309/2.6180, 2.6369 Å) is significantly shorter than
sodium dialkyl dithiocarbamates (1477/1468 cm–1) another bond (2.7335, 2.8012/2.7207, 2.8290 Å). The
indicates an increase in the contribution of double coordination mode discussed leads to the formation in
bonding to the formally ordinary N–C(S)S bond at the complexes of two small-size four-membered
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700
NOVIKOVA et al.
z
y
Fig. 1. Projection of the structure of compound I onto the yz plane. Polymer chains are directed along the x axis.
[BiS2C] metallocycles joined by the common metal C4H9)2}2(NO3)] and [Bi{S2CN(C3H7)2}2Cl] into poly-
atom. The mutual arrangement of the atoms in the
cycles is close to the coplanar one: the BiSSC and
SBiCS torsion angles are presented in Table 2. In each
complex, the most significant deviation from the pla-
nar configuration is manifested by only one metallo-
cycle, which can be presented by its inflection along
the S(1)–S(2) axis. The dihedral angle between the
root-mean-square planes of the cycles in complexes I
and II are 84.68° and 87.71°.
Two structural features caused by the mesomeric
effect of the =NC(S)S– groups are common for the
Dtc ligands in complexes I and II: (a) appreciably
shorter N–C(S)S bonds (1.316–1.334 Å) compared to
N–CH2 (1.461–1.483 Å), which shows the contribu-
tion of double bonding to the formally ordinary bond,
and (b) the configuration of the C2N–CS2 structural
fragment close to the planar one, which follows from
the values of the SCNC torsion angles (Table 2).
mer chains (Figs. 3, 4). The coordination of the bridg-
ing nitrate groups is performed unusually: involving all
–
three oxygen atoms. Therefore, the
groups act as
NO3
double bridges: one of the oxygen atoms (O(1)) partic-
ipates in binding with two adjacent Bi atoms, whereas
each oxygen atom of two others, O(2) and O(3), coor-
dinates only one of the metal atoms (Fig. 3). There-
fore, on the whole, the nitrate group is involved in the
bidentate coordination to each adjacent Bi atom.
Two types of the bridging coordination mode of
nitrate groups have previously been described for the
bismuth(III) dithiocarbamate nitrate complexes
involving one (μ2-nitrato-O: Bi–O(NO2)–Bi, the Bi–
O bond lengths are 2.694 and 2.725 Å [24]) or two oxy-
gen atoms (μ2-nitrate-O,O': Bi–O(NO)O–Bi, Bi–O
2.772 and 2.827 Å [21]; Bi–O 2.723 and 2.856 Å)
[24]).1 In our case, the Bi–O bonds (in a range of
In the studied complexes, the inorganic anions
1
NO3–
The data for the structure of the polymer complex
and Cl– perform the μ2-bridging structural func-
[Bi{S CN(CH ) } (NO )] studied at 299 K [21] and 100 K
2
2 5 2
3 n
tion joining the adjacent molecules [Bi{S2CN(iso-
[24] are presented.
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PRINCIPLES OF THE CONSTRUCTION OF POLYMER STRUCTURES, HETERONUCLEAR
701
y
z
Fig. 2. Projection of the structure of compound II onto the yz plane. Polymer chains are directed along the z axis.
2.850–3.007 Å (Table 2)) are much longer, and the (2.725–2.875 Å) Bi–O bonds [44] and joins three bis-
muth atoms are also described among the polynuclear
complexes with the purely oxygen environment of the
central bismuth atom.
structure formation of the polymer chain in com-
pound I differs basically due to a greater number of less
strong Bi–O bonds (Fig. 3). Only one more com-
pound in which the nitrate groups are involved in the
same way in binding of the adjacent bismuth com-
plexes is known: the heteroleptic complex additionally
including two-charge alkoxy groups of pentaethylene
glycol characterized by stronger Bi–O bonds (2.57–
The structural organization of complex II is close,
to the highest extent, to that described previously for
compounds [Bi{S2CN(CH2)4}2Cl] · CHCl3 [27] and
[Bi{S2CN(C2H5)(C2H4OH)}2Cl] [28]. In all these
cases, the complexes contain two nonequivalent S,S'-
3.00 Å) [42]. In addition, the compounds in which the anisobidentate Dtc ligands and the μ2-bridging chlo-
nitrate group forms four (2.621–2.903 Å) [43] or six rine atom asymmetrically binding the bismuth atoms.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 45 No. 10 2019

702
NOVIKOVA et al.
C(9)
C(7)
C(17)
C(18)
C(8)
C(16)
C(14)
C(6)
C(15)
C(12)
C(11)
N(1)
C(3)
C(2)
N(2)
C(5)
C(1)
S(1)
C(4)
O(1)
C(13)
C(10)
S(3)
S(4)
Bi(1)
S(2)
O(1)a
N(3)a
O(3)a
N(3)
O(2)a
O(2)
O(3)
Fig. 3. Two-link fragment of the polymer chain [Bi{S CN(iso-C H ) } (NO )] . Ellipsoids of 50% probability; symmetry trans-
2
4
9 2 2
3 n
a
form: 1/2 + x, –y, z. Hydrogen atoms are omitted.
C(14)
C(13)
C(12)
Cl(1)a
S(4)
Cl(1)
C(2)
C(9)
N(2)
C(10)
Bi(1)
S(1)
S(3)
C(11)
S(2)
C(1)
N(1)
C(3)
C(8)
C(7)
C(4)
C(5)
C(6)
Fig. 4. Two-link fragment of the polymer chain [Bi{S CN(C H ) } Cl] . Ellipsoids of 50% probability; symmetry transform:
2
3
7 2 2
n
a
x, 1/2 – y, 1/2 + z. Hydrogen atoms are omitted.
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PRINCIPLES OF THE CONSTRUCTION OF POLYMER STRUCTURES, HETERONUCLEAR
703
(а)
(c)
×2
×2
(b)
(d)
×4
205
195
65
55
30
20
10
345 335
150
140
δ, ppm
δ, ppm
13
15
Fig. 5. (a, b) C and (c, d) N CP-MAS NMR spectra of the polycrystalline samples of compounds (a, c) I and (b, d) II. The
number of acquisitions/rotation frequency of the samples (in Hz): (a) 23400/10000, (b) 30000/5000, (c) 31648/5000, and
(d) 78200/5000.
The Bi–Cl bond lengths (2.9010 and 3.1276 Å) in the covalent binding of the Dtc ligands by bismuth(III).
The 13C NMR spectra of complexes I/II (Figs. 5a, 5b)
containing the resonance signals of the =NC(S)S–
(1 : 1), =NCH2– (1 : 1 : 2), =CH– (1 : 1 : 2)/–CH2–
(1 : 2 : 1), and –CH3 (1 : 2 : 1 : 1 : 1 : 1 : 1)/(1 : 2 : 1)
groups are completely consistent with the X-ray dif-
fraction data indicating the presence of two Dtc
ligands in each complex. This shows their nonequiva-
lence concerning both the Dtc groups directly bonded
to the central bismuth atom and the structural groups
in the alkyl substituents. In turn, each 15N NMR spec-
trum is represented by two resonance signals (1 : 1) of
the =NC(S)S– groups and the additional low intense
signal of the NO3 group in dithiocarbamato-nitrato
complex I (Figs. 5c, 5d).
structure of compound II are consistent with the cor-
responding characteristics of μ2-Cl ligands also in
such inorganic anions as [Bi2Cl9]3– [18], [Bi2Cl10]4–
[45], and [Bi3Cl12]3– [46], as well as in polymer
([BiCl5]2–)n [47].
The value of the BiBiBi angle (163.436(4)°) in the
zigzag polymer chain of the structure of compound I
shows that the chain is smoothened. In the chain of
the structure of compound II (Fig. 4), the deviation
from linearity is much more pronounced: the BiBiBi
angle is 140.983(4)°. Using the overall coordination of
two terminal (Dtc) and two bridging (
–) ligands in
NO3
compound I, the central bismuth atom forms the
eightfold environment [BiS4O4]. In complex II, the
bridging chlorine atoms similarly build up the inner
sphere of the metal to [BiS4Cl2].
The thermal behavior of the synthesized complexes
was studied in argon by the STA method with the
simultaneous detection of the TG and DSC curves
(Figs. 6, 7). The first indications to the mass loss onset
by the samples of complexes I and II appear at 132 and
160°С, respectively, which determines the boundary
of their chemical stability. The endoeffects in the DSC
The 13C, 15N CP-MAS NMR spectra of complexes
I and II indicate the individual character of the syn-
thesized compounds (Fig. 5). The Dtc groups in the
studied complexes are characterized by substantially
lower 13С chemical shifts compared to the initial curves with extremes at 160.0 and 147.7°С correspond
sodium salts, which is a direct consequence of the to melting of the complexes: the extrapolated melting
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 45 No. 10 2019

704
TG, %
NOVIKOVA et al.
DSC, mW/mg ТG, %
DSC, mW/mg
4
а
а
100
90
80
70
60
50
100
90
80
70
60
50
40
14
12
10
8
–15.92%
–18.65%
c
160.0°C 283.5°C 334.3°C
3
266.7°C
267.5°C
–20.55%
2
–34.28%
6
220.8°C
241.0°C
4
1
100
300
–23.84%
145.5°C
43.13%
2
36.41%
b
b
–6.67%
246.8°C
0
0
147.7°C
100
200
300
T, °C
100
200
300
T, °C
Fig. 6. (a) TG and (b) DSC curves for complex I. (c) Inset:
the second derivative of the DSC curve.
Fig. 7. (a) TG and (b) DSC curves for complex II.
which is consistent with the data on studying the ther-
molysis of the solvated form of the bismuth(III) dith-
points are equal to 156.2 and 145.5°С, respectively.
(The following melting ranges were determined for the
samples by the independent determination in a glass
capillary: 155–158 and 146–148°C.) The double dif-
ferentiation was performed for the DSC curves of
complex I to reveal more distinctly the characteristic
points of the low intense thermal effects (Fig. 6c).
iocarbamate-chloride of [Bi{S2CN(CH2)4}2Cl]
∙
CHCl3 [27]. The DSC curve exhibits the endotherms
at 246.8 and 267.5°С (Fig. 7b) along with the thermal
effect of melting. The first endotherm is due to the
thermal decomposition of the substance (the extrapo-
lated temperature of the process is 241.0°С). The sec-
ond, narrow, and very low intense endotherm corre-
sponds to the melting of traces of reduced bismuth
(extrapolated mp = 266.7°С). Compact metallic bis-
muth melts at 271.442°С [49]. In our case, a decrease
in the melting point can be explained by two factors: a
small size of the metallic particles and the presence of
Bi2S3 as the major component [49], whose gray-black
finely dispersed powder was observed in the crucibles
in both cases.
The TG curve of compound I exhibits three inflec-
tion points indicating a complicated character of ther-
molysis. The initial region (before the first point at
246.0°С) is characterized by a mass loss of 18.65%.
Since the exoeffect at 220.8°C is projected onto this
region, it is reasonable to assume that the thermal
destruction at the initial stage involves the NO3 group
and one of the alkyl substituents (17.37%). Thermal
transformations in the range of relatively low tempera-
tures involving NO3 groups are fairly typical of the
dithiocarbamate nitrate complexes [48]. In the subse-
quent regions, the complex undergoes defragmenta-
tion at the remained alkyl substituents and Dtc groups
to form Вi2S3 (the residual weight of which equal to
36.41% is somewhat lower than the calculated weight
equal to 37.82%) as the major final product of the
thermal transformations of complex I. The DSC curve
includes two endotherms (at 283.5 and 334.3°C) cor-
responding to each of thermolysis stages discussed
(Fig. 6c).
ACKNOWLEDGMENTS
The authors are grateful to F.U. Shah (Luleå University
of Technology, Luleå, Sweden) for help in recording the 13C
CP-MAS NMR spectra.
CONFLICT OF INTEREST
The authors declare that they have no conflicts of
interest.
The thermolysis of complex II formally proceeds
via one stage (Fig. 7a). However, the differentiation of
the TG curve allows one to reveal the inflection point
at 236.0°С. The mass loss at the initial stage (before
this point) equal to 15.92% indicates the dissociation
of two –C3H7 groups (calcd. 14.43%). The subsequent
run of the TG curve includes the region (below
301.0°С) showing the main mass loss (34.28%) and
the final stage of the smooth desorption of volatile
thermolysis products (6.67%), which is completed by
the stabilization of the residual weight at 388.0°С
(43.13%). The latter with a high accuracy corresponds
to the expected weight for Bi2S3 (calcd. 43.06%),
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