Multiple isomerization of structural units in ion-polymeric heteronuclear gold(III)–zinc(II) complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n: Chemisorption-based synthesis, supramolecular structure (self-organization of long-period cation–cationic polymer chains), and thermal behavior

Article abstract of DOI:10.1134/S1070328417080036

Chemisorption of gold(III) from solutions in 2 M HCl with freshly precipitated binuclear zinc dithiocarbamate [Zn₂{S₂CN(C₄H₉)₂}₄] resulted in the formation of a polymeric heteronuclear gold(III)–zinc(II) dithiocarbamato-chlorido complex ([Au{S₂CN(C₄H₉)₂}₂]₂[ZnCl₄])_n (I), which was characterized by MAS ¹³C NMR, X-ray diffraction (CIF file CCDC no. 1526616), and simultaneous thermal analysis. Compound I isolated on a preparative scale was found to have a highly intricate supramolecular structure composed of 13 centrosymmetric and non-centrosymmetric isomeric complex cations, [Au{S₂CN(C₄H₉)₂}₂]⁺, with 24 structurally non-equivalent BuDtc ligands, and six isomeric [ZnCl₄]^2– anions. The isomeric gold(III) cations perform different structural functions. Four and six cations are involved in the formation of two sorts of long-period cation–cationic chains (via pair non-valence secondary AuS bonds): (ABCDCB)_n and (FGHIJK)_n. The discrete E, L, and M cations and the [ZnCl₄]^2– complex anions are located alongside of the polymer chains and do not take part in the secondary interactions. According to simultaneous thermal analysis, thermolysis of I includes destruction of the dithiocarbamate moiety with reduction of gold to the metal in the cation and liberation of zinc chloride with partial conversion to ZnS in the anion.

Full text of DOI:10.1134/S1070328417080036

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2017, Vol. 43, No. 8, pp. 512–525. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.V. Ivanov, O.V. Loseva, T.A. Rodina, A.I. Smolentsev, 2017, published in Koordinatsionnaya Khimiya, 2017, Vol. 43, No. 8, pp. 482–495.
Multiple Isomerization of Structural Units in Ion-Polymeric
Heteronuclear Gold(III)–Zinc(II) Complex
(
[Au{S CN(C H ) } ] [ZnCl ]) : Chemisorption-Based Synthesis,
2
4
9 2 2 2
4
n
Supramolecular Structure (Self-Organization of Long-Period
Cation–Cationic Polymer Chains), and Thermal Behavior
a,
a
b
c, d
A. V. Ivanov *, O. V. Loseva , T. A. Rodina , and A. I. Smolentsev
a
Institute of Geology and Nature Management, Far East Branch, Russian Academy of Sciences,
Blagoveshchensk, 675000 Russia
b
Amur State University, Blagoveshchensk, 675027 Russia
c
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
d
Novosibirsk State University, Novosibirsk, 630090 Russia
*
e-mail: alexander.v.ivanov@chemist.com
Received January 12, 2017
Abstract—Chemisorption of gold(III) from solutions in 2 M HCl with freshly precipitated binuclear zinc
dithiocarbamate [Zn {S CN(C H ) } ] resulted in the formation of a polymeric heteronuclear gold(III)–
2
2
4
9 2 4
zinc(II) dithiocarbamato-chlorido complex ([Au{S CN(C H ) } ] [ZnCl ]) (I), which was characterized by
2
4
9 2 2 2
4 n
13
MAS C NMR, X-ray diffraction (CIF file CCDC no. 1526616), and simultaneous thermal analysis. Com-
pound I isolated on a preparative scale was found to have a highly intricate supramolecular structure com-
+
posed of 13 centrosymmetric and non-centrosymmetric isomeric complex cations, [Au{S CN(C H ) } ] ,
2
4
9 2 2
2–
with 24 structurally non-equivalent BuDtc ligands, and six isomeric [ZnCl ] anions. The isomeric
4
gold(III) cations perform different structural functions. Four and six cations are involved in the formation of
two sorts of long-period cation–cationic chains (via pair non-valence secondary Au⋅⋅⋅S bonds):
2–
(
···A···B···C···D···C···B···) and (···F···G···H···I···J···K···) . The discrete E, L, and M cations and the [ZnCl ]
n n 4
complex anions are located alongside of the polymer chains and do not take part in the secondary interac-
tions. According to simultaneous thermal analysis, thermolysis of I includes destruction of the dithiocarba-
mate moiety with reduction of gold to the metal in the cation and liberation of zinc chloride with partial con-
version to ZnS in the anion.
Keywords: zinc dialkyl dithiocarbamates, gold species extracted from solutions, heteronuclear gold(III)–
zinc(II) dithiocarbamato-chlorido complexes, crystal and supramolecular structures, X-ray diffraction,
13
C MAS NMR, simultaneous thermal analysis
DOI: 10.1134/S1070328417080036
INTRODUCTION
In addition, freshly precipitated zinc dithiocarba-
mates are capable of effective chemisorption-based
extraction of gold(III) from solutions to give heterome-
tallic dithiocarbamato-chlorido complexes of the ionic
type. Previously, we have prepared a series of heteronu-
clear gold(III)–zinc(II) complexes of various composi-
Zinc dithiocarbamates, which are most often binu-
clear [Zn (S CNR ) ] and incorporate two bridging
2
2
2 4
and two chelating ligands, offer a broad range of prac-
tical applications: in analytical chemistry [1], industry
(
rubber vulcanization) [2], agriculture (biocides) [3],
tion
and
structures,
namely,
and medicine (owing to antibacterial properties [4]
and pharmacological activity towards glaucoma [5, 6]
and diabetes mellitus [7]). Dithiocarbamate com-
plexes are also used as precursors of nanocrystalline
and film zinc sulfides, useful for their narrow bandgap
[
Au {S CN(CH ) } ][ZnCl ], ([Au{S CN(CH ) O} ] -
2
2
3 2 4
4
2
2 4
2 2
[
ZnCl ] ⋅ 2H O) , ([Au{S CN(C H ) } ] [ZnCl ] ⋅
4
2
n
2
2
5 2 2 2
4
1
/2C H O
⋅
1/2CHCl ) , ([H O][Au {S CN(iso-
3
6
3 n 3 3 2
C H ) } ][ZnCl ]
⋅
H O) ,
([H O][Au -
3
7 2 6
4 2
2
n
3
2
{S CN(CH ) } ][Au{S CN(CH ) } ][ZnCl ] ) ,
and
(
3.2–3.9 eV), in the semiconductor industry for man-
ufacturing of solar cells, luminescent materials, and ([NH
chemosensors [8–13].
2
2 6 4
2
2 6 2
4 2 n
(C H ) ][Au{S CN(C H ) } ][ZnCl ]) , and have
4 9 2 2 4 9 2 2 4 n
2
studied their structural organization and thermal behav-
12
5

MULTIPLE ISOMERIZATION OF STRUCTURAL UNITS
513
13
ior by X-ray diffraction, C MAS NMR, and simultane- which proceeded by the mechanism of chemisorption
ous thermal analysis (STA) [14–19]. The formation of with partial ion exchange:
the last-mentioned gold(III)–zinc(II)-dibutylammo-
nium complex is associated with irreversible decomposi-
tion of some of the dibutyl dithiocarbamate groups on
long-term contact of the chemisorbing complex with
[
Zn {S CN(C H ) } ] + 2H[AuCl ]
2 2 4 9 2 4 4
2 4 9 2 2 2 4 2
=
[Au{S CN(C H ) } ] [ZnCl ] + ZnCl + 2HCl.
A solution of AuCl in 2 M HCl (10 mL) containing
AuCl solutions of low concentration [19]. The intri- 41.5 mg of gold was added to freshly precipitated zinc
3
3
dibutyl dithiocarbamate (100 mg), and the mixture
was magnetically stirred for 1 h. The resulting homo-
geneous yellow-brown plastic paste was separated,
covered with water, then thoroughly triturated many
times to wash out water-soluble impurities, and dried
on the filter. For X-ray diffraction experiment, the
transparent yellow-orange square prismatic crystals of
cately organized supramolecular structures of these com-
+
plexes comprise mononuclear [Au(S CNR ) ] , binu-
2
2 2
2+
clear
[Au (S CNR ) ] ,
2 6
and
trinuclear
2
2
+
2 4
3
[
Au (S CNR ) ] complex cations and various cation–
cationic and cation–anionic polymer chains as structural
3
2
units.
In this study, devoted to the chemisorption activity I were obtained from an acetone solution by slow
of freshly precipitated zinc dibutyl dithiocarbamate evaporation of the solvent.
[
Zn {S CN(C H ) } ] towards a solution of H[AuCl ]
2 2 4 9 2 4 4
with Au content of 4.15 mg/mL), the polymeric
The identity of compound I was confirmed by
C MAS NMR data (δ, ppm):
3+
(
13
heteronuclear gold(III)–zinc(II)-dithiocarbamato-
chlorido complex ([Au{S CN(C H ) } ] [ZnCl ])
(
[Au{S CN(C H ) } ] [ZnCl ]) : 195.0, 194.7,
2 4 9 2 2 2 4 n
2
4
9 2 2 2
4
n
1
94.1 (~1 : 3 : 2, −S CN=); 53.5, 52.6, 50.2, 49.9,
2
(
I), characterized by multiple isomerization of the
4
2
2
9.7, 49.6, 49.4, 48.7 (=NCH −); 30.5, 29.8, 29.5,
2
ionic structural units with an intricate supramolecular
structure, was isolated as an individual gold(III) bind-
ing species. The structural organization and thermal
behavior of I were studied by X-ray diffraction,
9.4, 29.3, 29.1 (−CH −); 21.1, 20.9, 20.7, 20.6, 20.4,
2
0.1 (−CH −); 16.5, 15.7, 15.6, 15.1, 15.0, 14.4, 14.3
2
(
−CH ).
3
13
13
C MAS NMR, and STA.
C MAS NMR spectra were recorded on a CMX-
3
60 spectrometer (Agilent/Varian/Chemagnetics
InfinityPlus) operating at 90.52 MHz with a super-
EXPERIMENTAL
conducting magnet B = 8.46 T and Fourier transfor-
0
Sodium dibutyl dithiocarbamate was prepared by
13
1
mation. The proton cross-polarization and C− H
decoupling with a radiofrequency field at a proton res-
onance frequency were used [38]. A ~80 mg sample of
the reaction of carbon disulfide (Merck) with dibutyl-
amine (Aldrich) in an alkaline medium [20] and the
corresponding binuclear zinc complex was obtained
I was placed into 4.0 mm ZrO ceramic rotor. The
2
2+
by precipitation of Zn ions from the aqueous phase
13
C MAS NMR measurements were performed using
magic angle spinning at 5300(1) Hz, 1100–
with Na{S CN(C H ) } ⋅H O taken in a stoichiomet-
2
4
9 2
2
1
ric ratio [21]. The starting compounds were identified 1200 acquisitions, 4.9 μs proton π/2-pulses, 2.5 ms
13
1
13
using the C MAS NMR spectral data (δ, ppm):
H− C contact time, and 3.0–5.0 s gap between the
13
pulses. The isotropic C chemical shifts, δ (ppm),
were referred to a component of the external standard,
crystalline adamantane (δ = 38.48 ppm relative to
Na{S CN(C H ) } ⋅ H O: 208.3 (−S CN=), 55.2
2
4
9 2
2
2
(
=NCH −), 30.0, 21.0 (−CH −), 15.6, 14.9, 14.5 (2 :
2
2
1
: 1, −CH ).
3
13
tetramethylsilane). The isotropic C chemical shifts
were corrected for the magnetic field strength drift, the
frequency equivalent of which is 0.051 Hz/h.
[
Zn {S CN(C H ) } ]: 203.4, 200.4 (34)* (1 : 1,
2 2 4 9 2 4
S CN=); 61.5, 58.6 (1 : 3, =NCH −); 33.8, 32.9,
−
3
(
2 2
1.3, 30.0 (1 : 3 : 2 : 2, −CH −); 16.2, 14.7, 14.5, 14.1
1 : 1 : 1 : 1, −CH ) [21] (*asymmetric C− N dou-
blet, Hz).
2
X-ray diffraction analysis was carried out on a
13
14
3
Bruker-Nonius X8 Apex CCD diffractometer (MoK
α
radiation, λ = 0.71073 Å, graphite monochromator) at
Synthesis of I. The preparation of the polymeric
1
50(2) K. The data were collected by a standard proce-
bis(N,N-dibutyl dithiocarbamato-S,S')gold(III) tet-
rachlorozincate (I) was based on the heterogeneous
reaction of freshly precipitated zinc dibutyl dithiocar-
dure (narrow frame ϕ- and ω scan mode). The absorp-
tion corrections were applied empirically (SADABS)
[
39]. The structure was solved by direct methods and
bamate with a solution of H[AuCl ] in 2 M HCl,
2
4
refined by the least-squares method (on F ) in the
full-matrix anisotropic approximation of non-hydro-
gen atoms. The positions of hydrogen atoms were cal-
culated geometrically and included in the refinement
1
Apart from our publication [21], the structure of
[
Zn {S CN(C H ) } ] was reported somewhat later in [22].
2 2 4 9 2 4
Among the zinc dithiocarbamates structurally characterized by
now [7–11, 21–37], the non-centrosymmetric dibutyl dithio- in the riding model. In the disordered complex anion,
carbamate complex, like the dimethyl dithiocarbamate complex
2−
[
ZnCl ] , the A and B site occupancies by the ran-
4
[
23], is specially distinguished by stabilization of the central
Zn S C ] tricyclic structural fragment in a distorted boat con-
domly distributed Zn(4) and Cl(44) atoms were
refined as 0.693(5) and 0.307(5), respectively. The
[
2
4 2
formation.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 8 2017

5
14
IVANOV et al.
Table 1. Crystal data and X-ray experiment and structure refinement details for I
Parameter
Value
C H N S Cl ZnAu
2
Empirical formula
36
72
4
8
4
M
1418.56
System
Space group
a, Å
b, Å
c, Å
Monoclinic
C2/c
69.378(8)
22.907(3)
44.103(5)
107.930(2)
β, deg
V, Å3
66686(14)
Z
48
ρ(calcd.), g/cm3
μ, mm–1
1
.696
.216
33600
6
F(000)
Crystal size, mm
0.25 ꢀ 0.25 ꢀ 0.12
1.43–25.68
–84 ≤ h ≤ 79, –14 ≤ k ≤ 27, –53 ≤ l ≤ 53
θ Range for data collection, deg
Ranges of reflection indices
Number of measured reflections
Number of unique reflections (Rint)
Number of reflections with I > 2σ(I)
Number of refinement parameters
GOOF
196611
62 498 (0.0672)
33547
3011
1.068
2
2
R = 0.0729, wR = 0.1665
R-factors on F > 2σ(F )
R-factors (all reflections)
1
2
R =0.1620, wR = 0.1916
1
2
Residual electron density (max/min), e/Å3
3.829/–3.270
data collection and editing and refinement of unit cell ducted in aluminum crucibles. The sample weight was
parameters were carried out using the APEX2 [39] and 2.166−7.184 mg. The temperature and the weight
−4
SAINT [39] program packages. The structure solution changes were determined to ±0.8°C and ±1 ꢀ 10 mg
and refinement calculations were carried out using the accuracy, respectively. The TG and DSC curves were
SHELXTL program package [39]. Selected crystallo-
graphic data and structure refinement details for I are
summarized in Table 1 and bond lengths and angles
are in Table 2.
measured using the correction file and the tempera-
ture and sensitivity calibrations for the specified tem-
perature program and heating rate. An alternative
determination of the melting points of the complex
Atom coordinates and bond lengths and angles are was performed on a PTP(M) instrument (OJSC
deposited with the Cambridge Crystallographic Data Khimlaborpribor).
Centre (no. 1526616; http://www.ccdc.cam.ac.uk/
conts/retrieving.html).
RESULTS AND DISCUSSION
The thermal properties of I were studied by STA
including simultaneous recording of the thermogravi-
metric (TG) and differential scanning calorimetry
The reaction of freshly precipitated zinc dibutyl
dithiocarbamate [Zn {S CN(C H ) } ] (finely crystal-
(
DSC) curves. The study was carried out on an STA
2
2
4
9 2 4
line white precipitate) with a solution of AuCl is
4
49C Jupiter instrument (NETZSCH) in corundum
crucibles with a hole in the lid for maintaining the accompanied by the gradual change in the precipitate
atm vapor pressure during the thermal decomposi- color to yellow-brown (with the solution being com-
tion of the sample. Heating was conducted up to pletely decolorized) and coarsening of the precipitate
3
1
1
100°C under argon at a 5°C/min rate. For better particles followed by agglomeration into a uniform
identification of thermal effects in the low-tempera- plastic paste. These changes attest to the formation of
ture region, the measurements were additionally con- new compounds in the system.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
Vol. 43
No. 8
2017

MULTIPLE ISOMERIZATION OF STRUCTURAL UNITS
515
Table 2. Selected bond lengths (d), bond angles (ω), and torsion angles (ϕ) in I*
Bond
d, Å
Bond
d, Å
Cations
Au(1)–S(11)
Au(1)–S(12)
Au(1)···S(23)
2.332(3)
2.335(4)
3.656(3)
S(11)–C(1)
S(12)–C(1)
N(1)–C(1)
1.745(14)
1.699(14)
1.297(15)
Au(2)–S(21)
Au(2)–S(22)
Au(2)–S(23)
Au(2)–S(24)
Au(2)···S(11)
Au(2)···S(32)
Au(3)–S(31)
Au(3)–S(32)
Au(3)–S(33)
Au(3)–S(34)
Au(3)···S(22)
Au(3)···S(42)
2.340(3)
2.336(3)
2.327(3)
2.325(3)
3.462(4)
3.601(3)
2.331(3)
2.335(4)
2.327(4)
2.330(4)
3.781(3)
3.720(4)
S(21)–C(10)
S(22)–C(10)
S(23)–C(19)
S(24)–C(19)
N(2)–C(10)
N(3)–C(19)
S(31)–C(28)
S(32)–C(28)
S(33)–C(37)
S(34)–C(37)
N(4)–C(28)
N(5)–C(37)
S(41)–C(46)
S(42)–C(46)
N(6)–C(46)
S(52)–C(55)
S(53)–C(64)
S(54)–C(64)
N(7)–C(55)
N(8)–C(64)
S(61)–C(73)
S(62)–C(73)
1.692(12)
1.756(13)
1.707(11)
1.711(13)
1.323(15)
1.311(14)
1.745(15)
1.731(15)
1.735(15)
1.724(15)
1.310(18)
1.290(18)
Au(4)–S(41)
Au(4)–S(42)
Au(4)···S(34)
2.315(4)
2.343(4)
3.946(4)
1.744(16)
1.713(15)
1.313(15)
Au(5)–S(51)
Au(5)–S(52)
Au(5)–S(53)
Au(5)–S(54)
S(51)–C(55)
Au(6)–S(61)
Au(6)–S(62)
Au(6)–S(63)
2.332(4)
2.334(4)
2.255(5)
2.278(6)
1.680(17)
2.317(4)
2.344(3)
2.323(4)
1.718(15)
1.661(16)
1.765(15)
1.352(17)
1.318(17)
1.705(14)
1.712(15)
1.729(14)
S(63)–C(82)
S(64)–C(82)
N(9)–C(73)
N(10)–C(82)
S(71)–C(91)
S(72)–C(91)
S(73)–C(100)
S(74)–C(100)
N(11)–C(91)
N(12)–C(100)
Au(6)–S(64)
Au(6)···S(71)
2.331(3)
3.829(3)
1.710(14)
1.371(17)
1.323(16)
Au(6)···S(113)c
Au(7)–S(71)
Au(7)–S(72)
Au(7)–S(73)
Au(7)–S(74)
Au(7)···S(63)
Au(7)···S(84)
Au(8)–S(81)
3.531(4)
2.336(3)
2.338(3)
2.333(3)
2.332(3)
3.576(4)
3.590(4)
2.336(4)
1.731(12)
1.729(12)
1.739(14)
1.723(14)
1.288(14)
1.308(16)
1.719(13)
S(81)–C(109)
S(82)–C(109)
S(83)–C(118)
S(84)–C(118)
N(13)–C(109)
N(14)–C(118)
S(91)–C(127)
S(92)–C(127)
Au(8)–S(82)
Au(8)–S(83)
Au(8)–S(84)
Au(8)···S(74)
Au(8)···S(92)
Au(9)–S(91)
Au(9)–S(92)
2.327(4)
2.343(5)
2.311(4)
3.808(4)
3.628(4)
2.318(3)
2.330(3)
1.742(13)
1.65(2)
1.745(17)
1.298(14)
1.37(2)
1.698(14)
1.749(14)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 8 2017

5
16
IVANOV et al.
Cations
Table 2. (Contd.)
Bond
d, Å
Bond
d, Å
Au(9)–S(93)
2.346(3)
2.334(3)
3.552(4)
3.619(4)
2.326(4)
2.322(4)
2.322(4)
2.330(4)
3.822(4)
S(93)–C(136)
S(94)–C(136)
N(15)–C(127)
N(16)–C(136)
S(101)–C(145)
S(102)–C(145)
S(103)–C(154)
S(104)–C(154)
N(17)–C(145)
1.717(13)
1.740(13)
1.313(16)
1.312(15)
1.73(2)
1.700(16)
1.744(15)
1.729(18)
1.30(2)
Au(9)–S(94)
Au(9)···S(82)
Au(9)···S(101)
Au(10)–S(101)
Au(10)–S(102)
Au(10)–S(103)
Au(10)–S(104)
Au(10)···S(93)
Au(10)···S(111)
Au(11)–S(111)
Au(11)–S(112)
3.462(4)
2.332(5)
2.327(4)
N(18)–C(154)
S(111)–C(163)
S(112)–C(163)
1.30(2)
1.727(16)
1.682(18)
Au(11)–S(113)
Au(11)–S(114)
2.329(4)
2.333(4)
3.576(5)
3.713(4)
2.331(4)
2.331(4)
2.326(3)
2.315(4)
1.721(16)
2.331(4)
2.322(4)
2.333(4)
2.341(4)
1.743(17)
S(113)–C(172)
S(114)–C(172)
N(19)–C(163)
N(20)–C(172)
S(122)–C(181)
S(123)–C(190)
S(124)–C(190)
N(21)–C(181)
N(22)–C(190)
S(132)–C(199)
S(133)–C(208)
S(134)–C(208)
N(23)–C(199)
N(24)–C(208)
1.726(16)
1.722(17)
1.33(2)
Au(11)···S(61)d
Au(11)···S(103)
Au(12)–S(121)
Au(12)–S(122)
Au(12)–S(123)
Au(12)–S(124)
S(121)–C(181)
Au(13)–S(131)
Au(13)–S(132)
Au(13)–S(133)
Au(13)–S(134)
S(131)–C(199)
1.309(18)
1.716(17)
1.711(14)
1.719(14)
1.297(18)
1.329(16)
1.698(17)
1.698(16)
1.744(14)
1.300(18)
1.314(16)
Anions
Zn(1)–Cl(11)
Zn(1)–Cl(12)
Zn(2)–Cl(21)
Zn(2)–Cl(22)
Zn(3)–Cl(31)
Zn(3)–Cl(32)
Zn(4A)–Cl(41)
Zn(4A)–Cl(42)
Zn(4A)–Cl(43)
Zn(4A)–Cl(44A)
Zn(5)–Cl(51)
Zn(5)–Cl(52)
Zn(6)–Cl(61)
Zn(6)–Cl(62)
2.258(4)
2.283(4)
2.239(5)
2.273(4)
2.257(6)
2.262(5)
2.301(7)
2.270(4)
2.164(7)
2.274(8)
2.281(4)
2.264(4)
2.258(5)
2.279(5)
Zn(1)–Cl(13)
Zn(1)–Cl(14)
Zn(2)–Cl(23)
Zn(2)–Cl(24)
Zn(3)–Cl(33)
Zn(3)–Cl(34)
Zn(4B)–Cl(41)
Zn(4B)–Cl(42)
Zn(4B)–Cl(43)
2.264(5)
2.257(4)
2.273(4)
2.264(4)
2.234(6)
2.222(7)
2.219(9)
2.310(7)
2.454(9)
2.183(16)
2.255(5)
2.278(6)
2.267(6)
2.252(4)
Zn(4B)–Cl(44B)
Zn(5)–Cl(53)
Zn(5)–Cl(54)
Zn(6)–Cl(63)
Zn(6)–Cl(64)
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517
Table 2. (Contd.)
Angle
ω, deg
Angle
ω, deg
Cations
S(11)Au(1)S(12)
S(11)Au(1)S(12)a
Au(1)S(11)C(1)
74.72(13)
105.28(13)
86.6(5)
Au(1)S(12)C(1)
S(11)C(1)S(12)
87.6(5)
110.6(7)
S(21)Au(2)S(22)
S(21)Au(2)S(23)
S(21)Au(2)S(24)
S(22)Au(2)S(23)
S(22)Au(2)S(24)
S(23)Au(2)S(24)
75.78(11)
178.92(12)
104.13(12)
104.67(11)
177.27(12)
75.47(11)
Au(2)S(21)C(10)
Au(2)S(22)C(10)
Au(2)S(23)C(19)
Au(2)S(24)C(19)
S(21)C(10)S(22)
S(23)C(19)S(24)
86.4(4)
85.1(4)
85.8(4)
85.8(4)
112.8(7)
112.8(7)
S(31)Au(3)S(32)
S(31)Au(3)S(33)
S(31)Au(3)S(34)
S(32)Au(3)S(33)
S(32)Au(3)S(34)
S(33)Au(3)S(34)
75.60(14)
174.54(14)
104.29(14)
104.30(15)
178.68(14)
75.68(15)
Au(3)S(31)C(28)
Au(3)S(32)C(28)
Au(3)S(33)C(37)
Au(3)S(34)C(37)
S(31)C(28)S(32)
S(33)C(37)S(34)
86.7(5)
86.8(5)
86.0(5)
86.2(5)
110.7(9)
111.3(9)
S(41)Au(4)S(42)
S(41)Au(4)S(42)b
Au(4)S(41)C(46)
75.09(15)
104.91(15)
87.2(5)
Au(4)S(42)C(46)
S(41)C(46)S(42)
87.0(5)
110.4(7)
S(51)Au(5)S(52)
S(51)Au(5)S(53)
S(51)Au(5)S(54)
S(52)Au(5)S(53)
S(52)Au(5)S(54)
S(53)Au(5)S(54)
75.47(15)
176.82(16)
104.70(14)
104.26(15)
178.34(15)
75.67(15)
Au(5)S(51)C(55)
Au(5)S(52)C(55)
Au(5)S(53)C(64)
Au(5)S(54)C(64)
S(51)C(55)S(52)
S(53)C(64)S(54)
85.5(5)
84.6(5)
87.1(5)
84.5(5)
114.4(8)
112.7(7)
S(61)Au(6)S(62)
S(61)Au(6)S(63)
S(61)Au(6)S(64)
S(62)Au(6)S(63)
S(62)Au(6)S(64)
S(63)Au(6)S(64)
74.97(14)
176.70(16)
103.09(15)
105.70(13)
174.87(14)
75.96(14)
Au(6)S(61)C(73)
Au(6)S(62)C(73)
Au(6)S(63)C(82)
Au(6)S(64)C(82)
S(61)C(73)S(62)
S(63)C(82)S(64)
86.7(5)
85.7(5)
85.4(4)
85.6(4)
112.2(7)
112.7(6)
S(71)Au(7)S(72)
S(71)Au(7)S(73)
S(71)Au(7)S(74)
S(72)Au(7)S(73)
S(72)Au(7)S(74)
S(73)Au(7)S(74)
75.64(11)
177.03(13)
104.45(11)
104.68(11)
179.19(13)
75.28(12)
Au(7)S(71)C(91)
Au(7)S(72)C(91)
Au(7)S(73)C(100)
Au(7)S(74)C(100)
S(71)C(91)S(72)
S(73)C(100)S(74)
86.2(4)
86.2(4)
86.8(5)
87.2(5)
111.9(7)
110.8(8)
S(81)Au(8)S(82)
S(81)Au(8)S(83)
S(81)Au(8)S(84)
S(82)Au(8)S(83)
S(82)Au(8)S(84)
S(83)Au(8)S(84)
S(91)Au(9)S(92)
75.02(13)
178.01(17)
105.96(16)
103.65(17)
178.38(16)
75.4(2)
Au(8)S(81)C(109)
Au(8)S(82)C(109)
Au(8)S(83)C(118)
Au(8)S(84)C(118)
S(81)C(109)S(82)
S(83)C(118)S(84)
Au(9)S(91)C(127)
87.2(4)
87.0(4)
85.7(5)
84.7(6)
110.3(7)
113.8(8)
86.8(5)
75.90(12)
S(91)Au(9)S(93)
S(91)Au(9)S(94)
S(92)Au(9)S(93)
S(92)Au(9)S(94)
S(93)Au(9)S(94)
176.74(13)
103.37(12)
105.37(11)
179.09(13)
75.39(11)
Au(9)S(92)C(127)
Au(9)S(93)C(136)
Au(9)S(94)C(136)
S(91)C(127)S(92)
S(93)C(136)S(94)
85.3(5)
86.5(4)
86.3(4)
112.0(7)
111.8(7)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 8 2017

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Cations
Table 2. (Contd.)
Angle
ω, deg
Angle
ω, deg
S(101)Au(10)S(102)
75.11(18)
179.87(18)
104.8(2)
104.82(15)
174.22(15)
75.30(16)
Au(10)S(101)C(145)
Au(10)S(102)C(145)
Au(10)S(103)C(154)
Au(10)S(104)C(154)
S(101)C(145)S(102)
S(103)C(154)S(104)
86.3(5)
87.3(6)
87.3(6)
87.3(6)
111.1(8)
109.8(10)
S(101)Au(10)S(103)
S(101)Au(10)S(104)
S(102)Au(10)S(103)
S(102)Au(10)S(104)
S(103)Au(10)S(104)
S(111)Au(11)S(112)
S(111)Au(11)S(113)
S(111)Au(11)S(114)
S(112)Au(11)S(113)
S(112)Au(11)S(114)
S(113)Au(11)S(114)
74.58(16)
178.94(15)
105.15(16)
105.85(17)
178.99(18)
74.44(16)
Au(11)S(111)C(163)
Au(11)S(112)C(163)
Au(11)S(113)C(172)
Au(11)S(114)C(172)
S(111)C(163)S(112)
S(113)C(172)S(114)
86.1(6)
87.3(6)
87.6(5)
87.6(5)
111.8(9)
109.8(8)
S(121)Au(12)S(122)
S(121)Au(12)S(123)
S(121)Au(12)S(124)
S(122)Au(12)S(123)
S(122)Au(12)S(124)
S(123)Au(12)S(124)
75.09(15)
178.69(15)
103.94(15)
105.21(13)
178.94(15)
75.76(13)
Au(12)S(121)C(181)
Au(12)S(122)C(181)
Au(12)S(123)C(190)
Au(12)S(124)C(190)
S(121)C(181)S(122)
S(123)C(190)S(124)
86.6(5)
86.7(5)
85.8(5)
86.0(5)
111.5(8)
112.4(8)
S(131)Au(13)S(132)
S(131)Au(13)S(133)
S(131)Au(13)S(134)
S(132)Au(13)S(133)
S(132)Au(13)S(134)
S(133)Au(13)S(134)
75.91(17)
178.58(18)
105.53(16)
103.08(16)
176.58(16)
75.53(13)
Au(13)S(131)C(199)
Au(13)S(132)C(199)
Au(13)S(133)C(208)
Au(13)S(134)C(208)
S(131)C(199)S(132)
S(133)C(208)S(134)
85.1(5)
86.4(5)
86.6(5)
85.3(5)
112.6(8)
112.5(8)
Anions
Cl(11)Zn(1)Cl(12)
Cl(11)Zn(1)Cl(13)
Cl(11)Zn(1)Cl(14)
114.96(15)
108.6(2)
105.55(17)
Cl(12)Zn(1)Cl(13)
Cl(12)Zn(1)Cl(14)
Cl(13)Zn(1)Cl(14)
109.24(18)
106.18(15)
112.33(16)
Cl(21)Zn(2)Cl(22)
Cl(21)Zn(2)Cl(23)
Cl(21)Zn(2)Cl(24)
107.4(2)
111.0(2)
111.4(2)
Cl(22)Zn(2)Cl(23)
Cl(22)Zn(2)Cl(24)
Cl(23)Zn(2)Cl(24)
112.3(2)
107.90(17)
106.82(16)
Cl(31)Zn(3)Cl(32)
Cl(31)Zn(3)Cl(33)
107.0(2)
112.5(2)
Cl(32)Zn(3)Cl(33)
Cl(32)Zn(3)Cl(34)
109.8(3)
110.8(3)
Cl(31)Zn(3)Cl(34)
Cl(41)Zn(4A)Cl(42)
Cl(41)Zn(4A)Cl(43)
Cl(41)Zn(4A)Cl(44A)
Cl(42)Zn(4A)Cl(43)
Cl(42)Zn(4A)Cl(44A)
Cl(43)Zn(4A)Cl(44A)
Cl(51)Zn(5)Cl(52)
Cl(51)Zn(5)Cl(53)
Cl(51)Zn(5)Cl(54)
Cl(61)Zn(6)Cl(62)
Cl(61)Zn(6)Cl(63)
Cl(61)Zn(6)Cl(64)
110.9(3)
Cl(33)Zn(3)Cl(34)
Cl(41)Zn(4B)Cl(42)
Cl(41)Zn(4B)Cl(43)
Cl(41)Zn(4B)Cl(44B)
Cl(42)Zn(4B)Cl(43)
Cl(42)Zn(4B)Cl(44B)
Cl(43)Zn(4B)Cl(44B)
Cl(52)Zn(5)Cl(53)
Cl(52)Zn(5)Cl(54)
Cl(53)Zn(5)Cl(54)
Cl(62)Zn(6)Cl(63)
Cl(62)Zn(6)Cl(64)
Cl(63)Zn(6)Cl(64)
105.8(2)
120.6(4)
114.9(3)
101.7(5)
101.6(3)
114.1(4)
103.1(4)
108.2(2)
111.97(16)
107.0(2)
107.4(2)
106.46(18)
111.3(2)
110.8(2)
115.5(3)
105.3(3)
112.7(2)
110.8(2)
101.0(3)
106.23(16)
114.04(17)
109.5(2)
114.46(18)
112.3(2)
104.77(18)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
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519
Table 2. (Contd.)
Angle
ϕ, deg
Angle
ϕ, deg
Au(1)S(11)S(12)C(1)
S(11)Au(1)C(1)S(12)
S(11)C(1)N(1)C(2)
–172.7(8)
–173.4(7)
5.6(18)
S(11)C(1)N(1)C(6)
S(12)C(1)N(1)C(2)
S(12)C(1)N(1)C(6)
172.4(10)
–172.9(10)
–6(2)
Au(2)S(21)S(22)C(10)
178.8(8)
S(22)C(10)N(2)C(11)
180.0(9)
Au(2)S(23)S(24)C(19)
S(21)Au(2)C(10)S(22)
S(23)Au(2)C(19)S(24)
S(21)C(10)N(2)C(11)
S(21)C(10)N(2)C(15)
176.8(8)
179.0(7)
177.2(7)
1.5(17)
S(22)C(10)N(2)C(15)
S(23)C(19)N(3)C(20)
S(23)C(19)N(3)C(24)
S(24)C(19)N(3)C(20)
S(24)C(19)N(3)C(24)
4.8(16)
1.2(18)
–177.8(11)
–178.3(10)
2.7(18)
–173.7(9)
Au(3)S(31)S(32)C(28)
–175.6(8)
S(32)C(28)N(4)C(29)
173.7(12)
Au(3)S(33)S(34)C(37)
S(31)Au(3)C(28)S(32)
S(33)Au(3)C(37)S(34)
S(31)C(28)N(4)C(29)
S(31)C(28)N(4)C(33)
–170.2(8)
–176.1(7)
–171.3(7)
–6(2)
178.0(12)
S(32)C(28)N(4)C(33)
S(33)C(37)N(5)C(38)
S(33)C(37)N(5)C(42)
S(34)C(37)N(5)C(38)
S(34)C(37)N(5)C(42)
–2(2)
3(3)
–175.8(14)
179.9(14)
1(2)
Au(4)S(41)S(42)C(46)
–174.4(8)
S(41)C(46)N(6)C(51)
177.8(12)
S(41)Au(4)C(46)S(42)
S(41)C(46)N(6)C(47)
–174.9(7)
0(2)
S(42)C(46)N(6)C(47)
S(42)C(46)N(6)C(51)
–176.4(13)
1(2)
Au(5)S(51)S(52)C(55)
178.7(9)
S(52)C(55)N(7)C(56)
179.2(13)
Au(5)S(53)S(54)C(64)
S(51)Au(5)C(55)S(52)
S(53)Au(5)C(64)S(54)
S(51)C(55)N(7)C(56)
S(51)C(55)N(7)C(60)
176.4(9)
178.9(8)
176.8(8)
–6(2)
S(52)C(55)N(7)C(60)
S(53)C(64)N(8)C(65)
S(53)C(64)N(8)C(69)
S(54)C(64)N(8)C(65)
S(54)C(64)N(8)C(69)
2(2)
–2(2)
–164.0(16)
176.7(12)
14(2)
177.3(13)
Au(6)S(61)S(62)C(73)
–172.4(9)
S(62)C(73)N(9)C(74)
–163.2(13)
Au(6)S(63)S(64)C(82)
S(61)Au(6)C(73)S(62)
S(63)Au(6)C(82)S(64)
S(61)C(73)N(9)C(74)
S(61)C(73)N(9)C(78)
–173.4(8)
–173.3(8)
–174.3(7)
16(2)
S(62)C(73)N(9)C(78)
S(63)C(82)N(10)C(83)
S(63)C(82)N(10)C(87)
S(64)C(82)N(10)C(83)
S(64)C(82)N(10)C(87)
0(2)
–2(2)
–178.7(10)
178.1(12)
1(2)
179.8(10)
Au(7)S(71)S(72)C(91)
178.6(8)
S(72)C(91)N(11)C(92)
175.0(9)
Au(7)S(73)S(74)C(100)
S(71)Au(7)C(91)S(72)
S(73)Au(7)C(100)S(74)
177.7(8)
178.8(7)
177.9(7)
S(72)C(91)N(11)C(96)
S(73)C(100)N(12)C(101)
S(73)C(100)N(12)C(105)
–1.6(17)
–3(2)
–179.6(10)
S(71)C(91)N(11)C(92)
S(71)C(91)N(11)C(96)
Au(8)S(81)S(82)C(109)
–5.3(16)
178.1(9)
171.7(8)
S(74)C(100)N(12)C(101)
S(74)C(100)N(12)C(105)
S(82)C(109)N(13)C(110)
173.7(11)
–3(2)
171.1(10)
Au(8)S(83)S(84)C(118)
S(81)Au(8)C(109)S(82)
S(83)Au(8)C(118)S(84)
S(81)C(109)N(13)C(110)
–172.1(10)
172.5(7)
–173.2(9)
–8(2)
S(82)C(109)N(13)C(114)
S(83)C(118)N(14)C(119)
S(83)C(118)N(14)C(123)
S(84)C(118)N(14)C(119)
1.0(18)
10(2)
174.0(12)
–171.0(13)
S(81)C(109)N(13)C(114)
Au(9)S(91)S(92)C(127)
Au(9)S(93)S(94)C(136)
S(91)Au(9)C(127)S(92)
S(93)Au(9)C(136)S(94)
S(91)C(127)N(15)C(128)
S(91)C(127)N(15)C(132)
–177.7(10)
–177.6(8)
–177.7(8)
–177.9(7)
–178.0(7)
1(2)
S(84)C(118)N(14)C(123)
S(92)C(127)N(15)C(128)
S(92)C(127)N(15)C(132)
S(93)C(136)N(16)C(137)
S(93)C(136)N(16)C(141)
S(94)C(136)N(16)C(137)
S(94)C(136)N(16)C(141)
–7(2)
–178.8(12)
0(2)
2(2)
174.3(11)
–177.9(10)
–6(2)
179.5(14)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 8 2017

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Table 2. (Contd.)
Angle
ϕ, deg
175.6(10)
173.8(9)
176.1(9)
174.4(9)
–4(3)
Angle
ϕ, deg
178.2(14)
–2(3)
Au(10)S(101)S(102)C(145)
Au(10)S(103)S(104)C(154)
S(101)Au(10)C(145)S(102)
S(103)Au(10)C(154)S(104)
S(101)C(145)N(17)C(146)
S(101)C(145)N(17)C(150)
Au(11)S(111)S(112)C(163)
Au(11)S(113)S(114)C(172)
S(111)Au(11)C(163)S(112)
S(113)Au(11)C(172)S(114)
S(111)C(163)N(19)C(164)
S(111)C(163)N(19)C(168)
Au(12)S(121)S(122)C(181)
Au(12)S(123)S(124)C(190)
S(121)Au(12)C(181)S(122)
S(123)Au(12)C(190)S(124)
S(121)C(181)N(21)C(182)
S(121)C(181)N(21)C(186)
Au(13)S(131)S(132)C(199)
Au(13)S(133)S(134)C(208)
S(131)Au(13)C(199)S(132)
S(133)Au(13)C(208)S(134)
S(131)C(199)N(23)C(200)
S(102)C(145)N(17)C(146)
S(102)C(145)N(17)C(150)
S(103)C(154)N(18)C(155)
S(103)C(154)N(18)C(159)
S(104)C(154)N(18)C(155)
S(104)C(154)N(18)C(159)
S(112)C(163)N(19)C(164)
S(112)C(163)N(19)C(168)
S(113)C(172)N(20)C(173)
S(113)C(172)N(20)C(177)
S(114)C(172)N(20)C(173)
S(114)C(172)N(20)C(177)
S(122)C(181)N(21)C(182)
S(122)C(181)N(21)C(186)
S(123)C(190)N(22)C(191)
S(123)C(190)N(22)C(195)
S(124)C(190)N(22)C(191)
S(124)C(190)N(22)C(195)
S(132)C(199)N(23)C(200)
S(132)C(199)N(23)C(204)
S(133)C(208)N(24)C(209)
S(133)C(208)N(24)C(213)
S(134)C(208)N(24)C(209)
S(134)C(208)N(24)C(213)
9(2)
–176.0(14)
–171.1(14)
4(3)
175.8(14)
174.3(10)
–171.6(9)
174.9(9)
–172.3(8)
0(2)
175.8(14)
7(2)
4(2)
–177.0(12)
–174.1(12)
5(2)
–168.3(13)
177.7(10)
–178.2(8)
177.9(9)
–178.4(7)
15(3)
–164.9(16)
4(3)
7(2)
–169.3(11)
–176.4(11)
7(2)
–176.6(15)
–176.9(10)
179.7(9)
–177.3(9)
179.7(8)
15(3)
–166.6(17)
–10(2)
1(2)
178.7(11)
–178.8(12)
–1(2)
S(131)C(199)N(23)C(204)
172.0(14)
Symmetry codes: –x, –y, –z; b –x, 1 – y, –z; x, y – 1, z; x, 1 + y, z.
a
c
d
*
13
In the C MAS NMR spectrum of a polycrystal- binding of the BuDtc ligands by gold(III), the elec-
line sample of I (Fig. 1), the structural states of the tronic system of gold participates more efficiently in
the additional shielding of the carbon nuclei of the
BuDtc ligand carbon atoms (=NC(S)S–, =NCH –,
2
=
NC(S)S– groups). The foregoing attests to a com-
−
CH −, −CH ) give rise to multicomponent groups
2 3
plex structural organization of the new heteronuclear
gold(III)–zinc(II) complex, the supramolecular self-
organization of which was established by X-ray crys-
tallography.
of resonance signals (see the section Synthesis), which
reflects the multiple structural non-equivalence of the
dithio ligands in the complex. The mathematical
13
modeling of the asymmetric C signal of the
The unit cell of complex I includes 48 formula units
=
NC(S)S– groups provides more definite conclusion
[
Au{S CN(C H ) } ] [ZnCl ] (Fig. 2). The ionic
2 4 9 2 2 2 4
that the poorly resolved internal structure of the spec-
structural units are represented by thirteen non-equiv-
trum is caused by superposition of three resonance
+
alent complex cations [Au{S CN(C H ) } ] (below
referred to as cations A–M with the Au(1)–Au(13)
signals in an integrated intensity ratio of about 1 : 3 : 2.
2
4
9 2 2
This indicates that complex I has six (or a number
2–
divisible by 6) structurally non-equivalent BuDtc atoms, respectively) and six [ZnCl
] anions. Most of
4
13
gold(III) cations, except for A with Au(1) and D with
Au(4), are non-centrosymmetric and include pairs of
non-equivalent ligands. Thus, compound I includes
altogether 24 structurally non-equivalent BuDtc
ligands. The markedly lower δ( C) chemical shifts of
all =NC(S)S– groups in I in comparison with the ini-
tial zinc complex reflect the increasing electron
shielding of carbon nuclei, caused by complete redis-
tribution of the BuDtc ligands between the zinc and
13
ligands, which is consistent with the above C MAS
+
gold coordination spheres. (Thus, in the covalent NMR data. In all [Au{S CN(C H ) } ] cations, the
2 4 9 2 2
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MULTIPLE ISOMERIZATION OF STRUCTURAL UNITS
521
opposing gold and carbon atoms are indicative of
trans-annular interaction between them and reflect
high π-electron density within the rings. The deviation
of the AuSSC (170.2°–179.7°) and SAuCS torsion
angles (171.3°–179.7°) from 180° is associated with
some tetrahedral distortion of the essentially planar
[
AuS C] rings, which can be described as ring folding
2
along the S–S axis. In the [AuS ] chromophores, the
4
environment of gold atoms is approximately square
(
the diagonal SAuS angles are in the 174.22°–180°
range), which corresponds to the low-spin (intraor-
2
bital) dsp -hybrid state of the central gold atom. In the
C NCS fragments of the BuDtc ligands, the atoms
×2
2
2
are not strictly coplanar either, as indicated by the
SCNC torsion angles differing from 180° or 0°
(
(
Table 2). The greater strength of the N−C(S)S bonds
200
190
50
40
30
20
δ, ppm
1.288–1.371 Å) compared with the N−CH bonds
2
2
3
(
1.418–1.504 Å) is due to admixing of the sp - to sp -
hybrid state of carbon and nitrogen atoms, which
defines a contribution of double bonding to this for-
mally single bond as a result of mesomeric effect.
Fig. 1. 13C MAS NMR spectrum of complex I. Number of
acquisitions/spinning frequency: 1160/5.3 kHz.
The anionic part of structure I is composed of six
chelating BuDtc ligands are coordinated in an approx-
imately S,S'-anisobidentate fashion (Fig. 3), with the
Au–S bond length being in the 2.315–2.346 Å range
2−
non-equivalent [ZnCl4] anions shaped as distorted
tetrahedra (ClZnCl angles of 104.77°–114.96° notice-
ably deviate from an ideal tetrahedral value) with the
(
Table 2). The only exception is one of the ligands of
3
sp -hybrid state of the central zinc atom (Fig. 4). In
cation E with a reliably higher binding strength:
Au(5)–S(53), 2.255; Au(5)–S(54), 2.278 Å.
one anion, the Zn(4) and Cl(44) atoms are statistically
distributed between A and B sites with occupancies of
In each cation, the S,S'-bidentate terminal coordi- 0.693(5) and 0.307(5). The Cl atoms in all anions are
nation of the BuDtc ligands gives rise to the central non-equivalent, the Zn–Cl bond lengths (2.222–
bicyclic [CS AuS C] fragment in which the inter- 2.283 Å) being consistent with the data of [43, 44]. In
2
2
the disordered Zn(4) anion, the scatter in the Zn–Cl
bond lengths and ClZnCl angles is more pronounced:
.164–2.454 Å and 101.0°–120.6°. The type of struc-
atomic distances in the small four-membered [AuS C]
2
rings (Au⋅⋅⋅C, 2.763–2.840; S⋅⋅⋅S, 2.820–2.872 Å) are
much shorter than the sum of the van der Waals radii
of the corresponding pairs of atoms (3.36 and 3.60 Å)
2
tural
differences
between
non-equivalent
+
2−
[
40–42]. The considerably proximate positions of the [Au{S
2
CN(C
4
H
9
)
2
}
2
] complex cations and [ZnCl ]
4
z
x
Fig. 2. Projection of the structure of ([Au{S CN(C H ) } ] [ZnCl ]) (I) on the xz plane. The alkyl substituents of the dithio-
2
4
9 2 2 2
4 n
carbamate ligands are omitted.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 8 2017

5
22
IVANOV et al.
(а)
(b)
S(23)a
S(113)c
S(12)
S(61)
Au(6)
Au(1)
S(64)
S(11)
S(62)
S(121) S(124)
Au(12)
S(63)
Au(7)
S(24)
S(21)
S(32)
S(31)
Au(2)
S(23)
S(54)
S(51)
S(22)
S(72)
S(73)
S(71)
Au(5)
S(74)
S(122) S(123)
S(53)
S(81)
S(82)
Au(3)
S(52)
S(33)
S(34)
S(84)
Au(8)
S(83)
S(92)
S(42)
S(41)
Au(9)
Au(4)
S(91)
S(94)
S(131) S(134)
S(42)b
S(93)
S(34)b
Au(3)b
S(132)
Au(13)
S(133)
S(101)
S(102)
Au(10)
S(104)
S(103)
Au(5)b
S(32)b
Au(2)b
S(22)b
S(111)
S(114)
Au(11)
S(112)
S(113)
S(11)b
S(61)b
Fig. 3. (a, b) Full periods of two independent cation–cationic polymer chains with the accompanying discrete cations. The
dashed line shows the Au⋅⋅⋅S secondary bonds. The alkyl substituents of the dithiocarbamate ligands are omitted for clarity.
Cl(31)
Cl(11)
Cl(22)
Cl(21)
Cl(32)
Cl(12)
Zn(1)
Zn(2)
Zn(3)
Cl(14)
Cl(24)
Cl(13)
Cl(34)
Cl(23)
Cl(33)
Cl(41)
Cl(52)
Zn(5)
Cl(51)
Cl(62)
Cl(61)
Zn(6)
Zn(4B)
Cl(44B)
Zn(4A)
Cl(44A)
Cl(43)
Cl(54)
Cl(64)
Cl(63)
Cl(42)
Cl(53)
Fig. 4. Structure of six isomeric [ZnCl4]2– complex anions of compound I. Ellipsoids at 30% probability level.
anions allows them to be classified as conformers tural functions. Despite the presence of electrostatic
(
Table 2).
In
intercation repulsion forces, most of the
+
compound
I,
the
isomeric [Au{S CN(C H ) } ] cations are involved in the for-
2
4
9 2 2
+
[Au{S CN(C H ) } ] cations perform different struc- mation of two sorts of long-period cation–cationic
2
4
9 2 2
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
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MULTIPLE ISOMERIZATION OF STRUCTURAL UNITS
523
2
The unit cell comprises altogether four full periods
of first type chains and eight periods of second type
chains, including the accompanying discrete cations
polymer chains via pair non-valence secondary Au⋅⋅⋅S
bonds (Fig. 3). The discrete E, L, and M cations do
not participate in the secondary bonds. In each com-
plex cation, the Au⋅⋅⋅S bonds involve the central gold
atom and one sulfur atom of each of the two BuDtc
ligands. In most cases, these are sulfur atoms located
(
Fig. 2). In the neighboring chains of the second type,
an opposite sequence of isomeric cations F–K is
observed, i.e., the chains are antiparallel. The spatial
separation of the supramolecular cation–cationic
along a diagonal in [AuS ], but in three cations (B, G,
4
2
−
chains involves isomeric [ZnCl ] anions and discrete
and I), the binding involves cis-located sulfur atom
4
+
(
Fig. 3). Each of the gold atoms form two Au⋅⋅⋅S [Au{S
2
CN(C H
4
9
)
2
}
2
] cations: E, L, and M (Fig. 2).
bonds with neighboring cations, thus completing
the [AuS ] polygon to a distorted [AuS ] octahe-
The thermal behavior of I was studied by STA. The
TG curve (Fig. 5a) is composed of two sections, the
first one (~160–370°C) reflecting the intense weight
loss as a result of thermolysis of the complex, while the
other one (~370–860°C) corresponding to smooth
desorption and evaporation of volatile products of
thermolysis. The first steeply descending step reflects
the major weight loss of 59.66% caused by the thermal
destruction of the dithiocarbamate moiety with
reduction of gold to the metal in the cation and liber-
4
6
dron. Thus, each cation forms two pairs of Au⋅⋅⋅S
bonds with the close neighbors by participating in
the formation of one of the two independent supra-
molecular chains extended along the y crystallo-
graphic
(
(
axis, (···A···B···C···D···C···B···)
and
n
···F···G···H···I···J···K···) . The Au⋅⋅⋅S distances
n
3.462–3.946 Å) in these chains are equal to or
greater than the sum of the van der Waals radii of
gold and sulfur atoms (3.46 Å [40–42]).
3
ation of ZnCl (with partial transformation to ZnS ) in
2
The formation of chains of the first type (Fig. 3a)
involves four isomeric gold(III) cations: centrosym-
metric A and D and non-centrosymmetric B and C
cations. In the pairs of the latter cations repeated in the
the anion. The intricate pattern of the processes is sup-
ported by the presence of inflection points in the TG
curve.
chain period, the [AuS ] planes are antiparallel to each
The low-temperature region of the DSC curve
4
other. The neighboring cations in the chain are (Fig. 5b) shows two endotherms with extreme points at
160.7 and 243.7°C. The first, more intense endotherm
arranged in such a way that their bisecting planes
(
passing through the bicyclic [CS AuS C] fragments) is attributable to melting of the compound (extrapo-
2
2
lated mp = 159.0°C). According to an alternative
determination of mp in a glass capillary, melting
occurs in the temperature range of 158–160°C. The
second endotherm is caused by thermolysis and
almost coincides with the temperature of the maxi-
mum rate of weight loss (242.6°C) found by differen-
tiation of the TG curve.
form an angle close to 90°. Discrete non-centrosym-
metric cations E alternate on the left and on the right
of the polymer chain (Fig. 3a). The values for the
Au(1)Au(2)Au(3)
(133.90°),
Au(2)Au(3)Au(4)
b
a
(
(
151.11°), Au(3)Au(4)Au(3 ), and Au(2)Au(1)Au(2 )
180°) angles imply the presence of linear segments in
the zigzag-like chain having interatomic distances
Au(1)–Au(2), 3.924 Å; Au(2)–Au(3), 4.169 Å; and
Au(3)–Au(4), 4.085 Å.
The second, gently sloping step of the TG curve
(
Fig. 5a) is associated with desorption and gradual
evaporation of the products of thermolysis of I
8.58%) including ZnCl (mp = 317 and bp = 733°C
The polymer chains of the second type are formed
according to the same principles as the chains of the
(
2
first type, but they involve six isomeric non-cen- [47]). The residual weight at 1100°C (31.74% of the
trosymmetric cations F–K. The lower scatter of the initial one) exceeds that expected for reduced gold
values
for
Au(6)Au(7)Au(8)
(137.24°), (calcd. 27.77%) by 3.97%. This excess weight may be
Au(7)Au(8)Au(9) (174.35°), Au(8)Au(9)Au(10) due to the zinc sulfide formed (sublimed at 1185°C
138.00°), Au(9)Au(10)Au(11)
(154.10°), [47]). According to full calculation of the TG curve,
Au(10)Au(11)Au(6) (175.41°), and Au(11)Au(6)Au(7) this corresponds to conversion of 57.8% of zinc to
151.16°) reflects a smoother character of the second ZnS. The remaining 42.2% of zinc exists as ZnCl
(
(
2
zigzag-like chain, although there are no linear seg- accounting for 4.05% of the initial weight of I, which
ments in this case; the distances in the second type are included in the second stage of experimental
chains are as follows: Au(6)–Au(7), 4.214 Å; Au(7)– weight loss. The high-temperature region of the DSC
Au(8), 3.928 Å; Au(8)–Au(9), 3.912 Å; Au(9)– curve exhibits an endotherm due to gold melting with
Au(10), 4.125 Å; Au(10)–Au(11), 4.008 Å; and the extrapolated mp = 1063.2°C (Fig. 5b). After open-
Au(11)–Au(6), 4.016 Å. Discrete cations K are situ- ing of the crucible, gold beads of 10–60 μm diameter
ated strictly on one side of the chain and cations L are and white zinc sulfide were found on the bottom
on the other side (Fig. 3b).
(Fig. 5c).
2
3
The concept of secondary bonds was first proposed in [45] to
describe the interactions at distances comparable with the sum
of the van der Waals radii of the involved atoms.
The preferred formation of metal sulfides upon the thermolysis
of complexes with sulfur-containing ligands has been substanti-
ated from the thermodynamic standpoint [46].
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 8 2017

5
24
IVANOV et al.
ТG, %
DSC, mW/mg
а
c
100
8
6
4
2
90
80
70
60
50
40
30
2
36.8°C
1
b
59.0°C
2
0 kV ×110 100 μm 0101 10 52 SEI
1063.2°C
0
–
59.66%
1
60.7°C
–2
243.7°C
31.74%
–8.58%
–
4
6
1
064.5°C
–
200
400
600
800
1000
T, °C
Fig. 5. (a) TG and (b) DSC curves for complex I. (c) Final residue of thermolysis of I consisting of ZnS and Au beads.
ACKNOWLEDGMENTS
The authors are grateful to Professor O.N. Antzut-
kin (Luleå University of Technology, Luleå, Sweden)
for providing the possibility to record the C MAS
NMR spectra. The work was partially supported by
Presidium of the Far East Branch of the RAS (Far
East Program, project no. 15-I-3-001).
13. Prakasam, B.A., Lahtinen, M., Peuronen, A., et al.,
Mater. Lett., 2015, vol. 44, p. 19.
1
4. Loseva, O.V., Rodina, T.A., and Ivanov, A.V., Russ. J.
Coord. Chem., 2013, vol. 39, no. 6, p. 463.
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5. Ivanov, A.V., Rodina, T.A., and Loseva, O.V., Russ. J.
Coord. Chem., 2014, vol. 40, no. 12, p. 875.
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Translated by Z. Svitanko
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 8 2017