Synthesis and structure of diethylenetriammonium tetrachloroaurates(III)

Article abstract of DOI:10.1134/S0036023611050159

The (DienH₃)[AuCl₄]₃ ? H₂O (I) and (DienH₃)₂[AuCl₄]Cl₅ (II) compounds were obtained by the reaction of HAuCl₄ with diethylenetriamine trihydrochloride (DienH₃Cl₃) in hydrochloric acid. The compounds were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. Crystals of I and II are monoclinic with space group P2₁/n. For I, a = 12.2314(3) ?, b = 14.6077(5) ?, c = 13.2680(5) ?, β = 106.7350(10)°, V = 2270.22(13) ?³, Z = 8. For II, a = 6.62990(10) ?, b = 17.9026(5) ?, c = 10.3661(3) ?, β = 101.9230(10)°, V = 1203.83(5) ?³, Z = 2. Both structures are ionic. The gold atoms in I and II have a 4 + 2 coordination environment. The Au-Cl bond lengths are within 2.276-2.294 ?, and the axial Au...Cl contacts are within 3.315-3.405 ?. The diethylenetriammonium cation in I and II has different conformations.

Full text of DOI:10.1134/S0036023611050159

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2011, Vol. 56, No. 5, pp. 713–720. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © E.V. Makotchenko, I.A. Baidina, L.A. Sheludyakova, 2011, published in Zhurnal Neorganicheskoi Khimii, 2011, Vol. 56, No. 5, pp. 762–769.
COORDINATION
COMPOUNDS
Synthesis and Structure of Diethylenetriammonium
Tetrachloroaurates(III)
E. V. Makotchenkoa, b, I. A. Baidinaa, and L. A. Sheludyakovaa, b
a Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 3, Novosibirsk, 630090 Russia
b Novosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia
eꢀmail: com@niic.nsc.ru
Received December 4, 2009
Abstract—The (DienH3)[AuCl4]3
reaction of HAuCl4 with diethylenetriamine trihydrochloride (DienH3Cl3) in hydrochloric acid. The comꢀ
pounds were characterized by elemental analysis, Xꢀray diffraction, thermogravimetry, and IR spectroscopy.
⋅ H2O (I) and (DienH3)2[AuCl4]Cl5 (II) compounds were obtained by the
Crystals of
13.2680(5)
10.3661(3)
I
and II are monoclinic with space group
= 106.7350(10)
= 2270.22(13) Å3
= 101.9230(10)
= 1203.83(5) Å3
P
Z
21/
= 8. For II
= 2. Both structures are ionic. The gold atoms in I and
n
. For I,
a
= 12.2314(3)
= 6.62990(10)
Å
Å
,
b
= 14.6077(5)
= 17.9026(5) Å, c =
Å, c =
Å
,
β
β
°
,
V
,
,
a
,
b
Å,
°
,
V
,
Z
II have a 4 + 2 coordination environment. The Au–Cl bond lengths are within 2.276–2.294 Å, and the axial
Au···Cl contacts are within 3.315–3.405 Å. The diethylenetriammonium cation in
formations.
I and II has different conꢀ
DOI: 10.1134/S0036023611050159
By now, [AuCl4]– complexes with simple singly (intramolecular contact) or in neighboring complexes
charged inorganic and organic cations have been synꢀ or counterions (intermolecular contact) [15]. In genꢀ
thesized and structurally characterized [1–7]. The latꢀ eral, the extra coordination of gold(III) (4 + 1 or 4 + 2) is
dealt with when the Au···Lax distance is longer than the
sum of the Au and L covalent radii but shorter than the
sum of their van der Waals radii.
We were interested in studying the structure of a
tetrachloroaurate(III) salt with a simple triply charged
cation, for example, protonated diethylenetriamine
[H3N(СН2)2NH2(CH2)2NH3]3+ (DienH33+). The
ter are, as a rule, protonated organic compounds of
different classes. We are not aware of any structural
data on tetrachloroaurates with simple doubly and triꢀ
ply charged cations. Meanwhile, such compounds are
of interest for extending notions of stoichiometric
types and structure of gold complexes. In addition,
there are double complex salts (DCSs) containing,
along with [AuCl4]– , a complex cation or complex
anion of gold or other metal (singly, doubly, or triply
charged ion) [1, 8–14]. In simple complexes, the
[AuCl4]– anion has mainly a squareꢀplanar configuraꢀ
tion. At the same time, in these structures, gold atoms
can be involved in weak contacts with axial atoms,
which leads to an increase in the CN of Au(III). This is
also typical of most DCSs containing [AuCl4]– [14]. In
particular, we have synthesized and structurally charꢀ
acterized DCSs containing [AuCl4]– and triply charged
cobalt(III) cations: [Co(N2C2H8)3][AuCl4]2Cl [12]
and [Co(NH3)6][AuCl4]Cl2 [13]. The square coordiꢀ
nation of the gold atom is completed to a tetragonal
pyramid by a chlorine atom of a neighboring complex
anion (Au···Cl 3.538 Å) in the former and to a prolate
square bipyramid (SBP) by two uncoordinated chloꢀ
rine atoms of a neighboring complex anion (Au···Cl
3.245 Å) in the latter. These estimates of ancillary conꢀ
tacts are comparable with the distances determined for
gold(III) complexes in which the coordination of the
synthesis of (DiеnH3)[AuCl4]3
⋅ H2O has been
reported [16], but no structural data on this compound
are available.
The aim of this work is to synthesize and study the
structure of the (DiеnH3)[AuCl4]3
⋅ H2O (I) and
(
DienH3)2[AuCl4]Cl5 (II) complexes.
EXPERIMENTAL
An HAuCl4 solution was prepared by dissolving
gold metal in aqua regia and successive evaporation of
the resulting solution with concentrated hydrochloric
acid for three times. Diethylenetriamine (Dien,
Merck) was used as purchased. Diethylenetriamine
trihydrochloride (DienH3Cl3) was obtained by neuꢀ
tralization of Dien with hydrochloric acid at ~0°С and
saltingꢀout by ethanol. The resulting salt was recrystalꢀ
lized from an aqueous ethanol solution.
Synthesis of I. A hydrochloric acid solution of Dien
central atom is completed with N, O, Cl, Br, I, and S (0.055 mL in 2.0 mL of 6.0 M HCl) was added porꢀ
atoms incorporated either in the complex itself tionwise under stirring to 3 mL of an HAuCl4 solution
713

714
MAKOTCHENKO et al.
(1.5 mmol). A precipitated appeared even after introꢀ formed with the SHELXꢀ97 program package [17].
ducing first drops of the Dien solution. The reaction The Xꢀray powder diffraction patterns (a DRONꢀ3M
mixture was kept at
0°С for 30 min for complete preꢀ diffractometer, CuKα radiation) were indexed on the
cipitation. The resulting yellow fine crystalline precipꢀ basis of singleꢀcrystal data. No extra peaks were
itate was filtered off, successively washed on a filter detected, which was evidence that products
with cold water, ethanol, and diethyl ether and dried in were singleꢀphase.
air. The yield was ~60% as calculated for gold.
I and II
For C4H18Au3Cl12N3O anal. calcd. (%): C, 4.21; H,
1.59; N, 3.6; Au, 51.81. Found (%): C, 4.6; H, 1.6; N,
RESULTS AND DISCUSSION
3.2; Au, 51.6.
Compounds
I and II were synthesized in strongly
acidic solution where diethylenetriamine exists as the
Synthesis II. A solution of tetrachloroauric acid
(0.6 mL of 1.5 M HAuCl4 + 0.6 mL of 11.6 M HCl)
was added portionwise under stirring to a hydrochloric
acid solution of Dien (0.30 mL in 2.0 mL of 11.6 M
HCl). A precipitate appeared after cooling the mixꢀ
3+
triply charged
cation. The ratio ([H+]3[Cl–]3)/
DienH3
[DienH33+] > 1.8 was maintained in reaction solutions to
rule out contamination of the compounds with the prodꢀ
ucts of substitution of Dien for chloride ions in [AuCl4]–
.
ture. The reaction mixture was kept at ~0°С for
30 min; then, a yellow fine crystalline precipitate was Compound
I was precipitated at cAu ~ 0.3 mol/L and
3+
filtered off, successively washed on a filter with ethanol
and diethyl ether and dried in air. The yield was ~95%
as calculated for gold.
[AuCl ]– :
= 3 : 1. Compound II was obtained
DienH3
4
3+
at cAu ~ 0.24 mol/L and [AuCl ]– :
= 1 : 3. It is
DienH3
4
worth noting that changing the molar ratio
[Co(En)3]3+ (or [Co(NH3)6]3+) : [AuCl4]– from 1 : 5 to
5 : 1 and the HCl concentration from 0.1 to 5.0 mol/L
did not lead to the DCS with Au : Co = 3 : 1 [12, 13].
For C8H32AuCl9N6 anal. calcd. (%): C, 13.19; H,
4.36; N, 11.54; Au, 27.04. Found (%): C, 13.1; H, 4.4;
N, 10.4; Au, 27.2.
Elemental analysis for C, H, and N was carried out
on a Euro EA 3000 CHN analyzer by a routine proceꢀ
dure. The gold content was determined spectrophotoꢀ
metrically.
IR spectra of fine powders were recorded on Scimꢀ
itar FTS 2000 and Vertex 80 spectrophotometers in the
range of 100–4000 cm–1 at temperatures of 25 and
Compounds
water and common organic solvents. Keeping comꢀ
pound in a desiccator over concentrated sulfuric acid
I and II are stable in air and are soluble in
I
for four months did not lead to removal of water, which
was indicated by the lack of weight loss and the conꢀ
stancy of the IR spectrum. Compounds
with decomposition (a Boetius hot stage) at temperaꢀ
tures 185–187 and 188–191 , respectively. Temperꢀ
atureꢀinduced transformations of and II in a helium
atmosphere were studied. For compound , the first
endotherm corresponding to water removal is
observed at 130–170 . The process cannot be
quenched at this stage since it is followed by complex
decomposition (below 300 ) in several inseparable
I and II melt
⎯
193°С. Samples were prepared as pellets with KBr
°С
(400–4000 cm–1) or polyethylene (100–600 cm–1).
I
TGA in a helium atmosphere in the temperature
range of 20–600°С was carried out on NETZSCH TG
209 F1 Iris thermal analyzer (sample weight, 24–40 mg;
Al2O3 crucible; helium flow rate, 30 mL/min; heating
rate, 10 K/min).
I
°
С
°
С
Xꢀray crystallography. Single crystals were
steps accompanied by endothermic events. The
decomposition of II is observed at 170–350°C and
occurs in several inseparable steps accompanied by
endoꢀ and exothermic events. Both compounds
decompose to gold metal. The weight of the ultimate
obtained by slow evaporation of dilute solutions of
and II in 2.0 and 5.0 M HCl, respectively. The unit cell
parameters and experimental intensities were meaꢀ
I
sures at room (20(2)
BrukerꢀNonius X8Apex automated fourꢀcircle difꢀ
fractometer (area CCD detector, MoKα radiation,
°С) and low temperatures on a
thermolysis products (heating to 600°С) somewhat
λ
=
exceeded the calculated weight of gold because of
incomplete removal of carbon in an inert gas atmoꢀ
sphere. Our data did not allow us to draw any concluꢀ
sions about the occurrence of the process of amine
migration from the outer sphere of the complex to the
inner one, previously revealed for some onium comꢀ
plexes of the (АН)[AuCl4] type (A = amines) [19].
0.71073 Å, graphite monochromator) by a routine
procedure. Crystallographic data and experimental
details for I and II are listed in Table 1. The coordiꢀ
nates of basis atoms were deposited with the Camꢀ
bridge Crystallographic data Centre (CCDC 747710
and CCDC 747699 for
I
and II, respectively).
The structures of compounds
I
and II were solved
According to Xꢀray crystallography, compounds
and II have ionic structures.
I
by direct methods and refined by fullꢀmatrix leastꢀ
squares calculation (on F2) in the anisotropic and isoꢀ
tropic (for H) approximation. The hydrogen atoms
were introduced into geometrically calculated posiꢀ
tions.
3+
The structure of
I
is composed of
cations,
DienH3 ,
[AuCl4]– anions, and crystal water molecules. The
structures of the ions with the atom numbering
Selected bond lengths and bond angles in I and II scheme are shown in Fig. 1. The gold anions occupy
are presented in Table 2. All calculations were perꢀ four crystallographically independent positions. The
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 5 2011

SYNTHESIS AND STRUCTURE OF DIETHYLENETRIAMMONIUM
715
Table 1. Crystallographic data and details of the diffraction experiment for (DienH3)[AuCl4]3 ⋅ H2O (I) and
(DienH3)2[AuCl4]Cl5 (II)
Characteristics
I
II
FW
, K
570.26
100(2)
728.41
90(2)
T
Symmetry system
Space group
Monoclinic
Monoclinic
P
2 /
n
P2 /n
1
1
a
, Å
, Å
12.2314(3)
14.6077(5)
13.2680(5)
90
6.62990(10)
17.9026(5)
10.3661(3)
90
b
c
, Å
, deg
, deg
α
β
106.7350(10)
90
101.9230(10)
90
γ, deg
3
V
Z
ρ
μ
, Å
4540.44(13)
8
1203.83(5)
2
3
, g/cm
3.337
2.010
calc
–1
, mm
(000)
20.753
7.116
F
2048
708
Crystal size, mm
θ range, deg
0.97
2.12–31.50
15, –20
×
0.03
×
0.02
1.07
3.04–31.35
8, –20 ≤ k ≤ 25,
× 0.09 × 0.05
Index range
–11
≤
h
≤
≤
k
≤
19,
–5
≤
h
≤
–18
≤
l
≤
16
–14
9355/3253 [R
int
≤
l
≤
14
Number of measured/unique reflections
Completeness of data collection
16630/5756 [
R
= 0.0264]
= 0.0229]
int
on
θ
= 25.00° 96.4%
219
on
θ
= 31.35° 82.3%
120
Number of refined parameters
2
GOOF on
value
F
0.947
1.096
R
ꢀ
[
I
> 2
σ(
I)]
R
R
= 0.0295, wR = 0.0534
R
R
= 0.0231, wR = 0.0378
2
1
1
2
1
R (for all reflections)
= 0.0514, wR = 0.0585
= 0.0280, wR = 0.0389
2
1
2
Extinction coefficien
Residual electron density (min/max), e Å–3
t
0.000284(10)
–1.793/1.842
0.00399(17)
–1.032/0.836
Au(1) and Au(2) atoms are in centers of symmetry, and respectively (Fig. 2a). The general view of structure
I
the Au(3) and Au(4) atoms are in general positions. is shown in Fig. 2b. There are shortened Cl···Cl conꢀ
The complex anions are slightly distorted squares. The tacts (3.22 and 3.41 Å) between complex anions. At
Au–Cl bond lengths are within 2.276–2.294 Å room temperature, structure
I was not refined since
3+
(av. 2.286 Å), and the bond angles differ from 90° by
no more than 1.37°. The square coordination of all
gold atoms is completed to a SBP (4 + 1 + 1) by chloꢀ
rine atoms of neighboring complex anions (Au···Cl
3.326–3.405 Å). These ancillary contacts combine the
[AuCl4]– anions into a threeꢀdimensional framework
the
cation in a channel is disordered over
DienH3
several positions.
3+
In the
cation of compound I, the N–C
DienH3
bond lengths for the terminal and central nitrogen
atoms are different (av. 1.493 Å). The C(1)–C(2) and
C(3)–C(4) distances are comparable (av. 1.525 Å).
(
Au···Au 4.012–4.123 Å). The channels of this frameꢀ
work accommodate the diethylenetriammonium catꢀ
ions and crystal water molecules combined by N–
H···Ow hydrogen bonds: 2.87 (1.96) and 2.89 (2.00) Å,
The NCC bond angles for the terminal (107.9
109.4 ) and central (111.2 , 112.4 ) nitrogen atoms
are considerably different. The cation located in the
°,
°
°
°
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 5 2011

716
MAKOTCHENKO et al.
Table 2. Selected bond lengths (d) and bond angles (ω) in the structures of (DienH3)[AuCl4]3 ⋅ H2O (I) and
(DienH3)2[AuCl4]Cl5 (II)
Bond
d
, Å
Angle
ω, deg
I
Au(1)–Cl(12)
Au(1)–Cl(11)
Au(2)–Cl(21)
Au(2)–Cl(22)
Au(3)–Cl(32)
Au(3)–Cl(33)
Au(3)–Cl(34)
Au(3)–Cl(31)
Au(4)–Cl(43)
Au(4)–Cl(41)
Au(4)–Cl(44)
Au(4)–Cl(42)
N(1)–C(1)
2.2862(12)
2.2863(13)
2.2843(13)
2.2854(12)
2.2808(12)
2.2854(12)
2.2865(12)
2.2901(13)
2.2759(13)
2.2784(12)
2.2925(12)
2.2937(13)
1.479(6)
Cl(12)Au(1)Cl(11)
Cl(21)Au(2)Cl(22)
Cl(32)Au(3)Cl(33)
Cl(32)Au(3)Cl(34)
Cl(33)Au(3)Cl(34)
Cl(32)Au(3)Cl(31)
Cl(33)Au(3)Cl(31)
Cl(34)Au(3)Cl(31)
Cl(43)Au(4)Cl(41)
Cl(43)Au(4)Cl(44)
Cl(41)Au(4)Cl(44)
Cl(43)Au(4)Cl(42)
Cl(41)Au(4)Cl(42)
Cl(44)Au(4)Cl(42)
C(4)N(2)C(2)
91.37(5)
90.97(4)
89.57(4)
91.08(4)
177.87(4)
178.12(5)
89.62(4)
89.79(4)
89.93(5)
90.31(5)
178.43(4)
177.96(5)
88.94(5)
90.86(5)
110.6(4)
109.4(4)
112.4(4)
107.9(4)
111.2(4)
N(2)–C(4)
1.497(6)
N(2)–C(2)
1.507(5)
N(3)–C(3)
1.488(6)
N(1)C(1)C(2)
C(1)–C(2)
1.520(6)
N(2)C(2)C(1)
C(3)–C(4)
1.530(6)
N(3)C(3)C(4)
N(2)C(4)C(3)
II
Au(1)–Cl(2)
Au(1)–Cl(1)
N(1)–C(1)
C(1)–C(2)
C(2)–N(2)
N(2)–C(3)
C(3)–C(4)
C(4)–N(3)
2.2893(6)
2.2963(6)
1.488(3)
1.509(4)
1.501(3)
1.506(3)
1.507(4)
1.490(3)
Cl(2)Au(1)Cl(1)
N(1)C(1)C(2)
N(2)C(2)C(1)
C(2)N(2)C(3)
N(2)C(3)C(4)
N(3)C(4)C(3)
89.46(2)
113.7(2)
114.0(2)
113.55(19)
112.8(2)
114.0(2)
channel is bound to complex anions by weak N– are only 0.54
°
smaller than 90°. The square coordinaꢀ
H···Cl and C–H···Cl hydrogen bonds (N···Cl
C···Cl 3.48 Å).
≥
3.32 tion of the Au atom in structure II is completed to a
≥
bipyramid (4 + 2) by uncoordinated Cl(4) atoms
(
Au···Cl 3.315 Å). These auxiliary contacts lead to forꢀ
3+
The structure of II is composed of
catꢀ
DienH3 ,
mation of infinite anionic chains ~([AuCl4]Cl)2–~
ions, [AuCl4]– anions, and uncoordinated Cl– anions
(Fig. 3). The Au atom located in the center of symmeꢀ
try has a square environment of the four Cl atoms (av.
along the shortest
x
axis with an Au···Au of 6.63 Å.
3+
In the
cation of compound II, the N–C
DienH3
Au–Cl, 2.293 Å). The bond angles in the cis position bond lengths for the terminal and central nitrogen
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 5 2011

SYNTHESIS AND STRUCTURE OF DIETHYLENETRIAMMONIUM
717
Cl(41)
Cl(42)
Au(4)
Cl(43)
N(1)
Cl(44)
C(1)
Au(2)
C(2)
Cl(21)
N(2)
Cl(22)
Cl(34)
Au(3)
Cl(32)
Cl(33)
C(4)
C(3)
Cl(31)
N(3)
Cl(11)
Cl(12)
Au(1)
O(1w)
Fig. 1. Structure of structural units and the atom numbering scheme in the crystal of I.
c
0
a
N(1A)
O(1w)
N(3)
C(4)
C(2)
N(1)
C(3)
N(2)
C(1)
b
(а)
(b)
3+
Fig. 2. (a) Arrangement of (DienH ) cations and H O molecules in channels and (b) general view of the crystal structure of
I
3
2
along the x axis. Dashed lines show ancillary Au···Cl and Cl···Cl contacts.
atoms, as well as the C–C bond lengths, are insignifiꢀ numerous N–H···Cl hydrogen bonds (N···Cl 3.08–
3.23 Å). At room temperature, one of the terminal
nitrogen atoms in II is disordered over two positions.
cantly different (av. 1.493 and 1.508 Å, respectively).
The bond angles are within 112.8 –114.0 . Figure 4
shows the crystal packing of II along the axis and
°
°
x
The geometric characteristics of the [AuCl4]– comꢀ
hydrogen bonds. In crystal, the ions are linked by plex anion in
I and II are consistent with those
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 5 2011

718
MAKOTCHENKO et al.
Cl(3)
C(2)
C(1)
N(2)
C(3)
C(4)
N(1)
Au(1)
N(3)
Cl(5)
Cl(4)
Cl(1)
Cl(2)
Fig. 3. Structure of structural units and the atom numbering scheme in the crystal of II
.
0
c
a
b
Fig. 4. Packing of structural units in the crystal of II along the
x axis.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 5 2011

SYNTHESIS AND STRUCTURE OF DIETHYLENETRIAMMONIUM
719
reported in the literature [4, 9–13]. The presence of III, which is indicative of the close character of hydroꢀ
the bulky cation capable of forming hydrogen bonds gen bonds in these compounds. Vibrations of the
[AuCl4]– anion are observed at 370 and 359 cm–1 (for
I)
with Cl atoms in the outer sphere of the complexes
and 362 and 355 cm–1 (for II) and are of the ν6
( )
Еu
type. In the IR spectrum, the ν7(Еu) and ν3(А2 ) vibraꢀ
u
entails no significant elongation of the Au–Cl bonds.
In both cases, the square coordination of the Au atom
is completed to a prolate SBP by chlorine atoms at
Au···Clax distances considerably exceeding the sum of
the gold and chlorine covalent radii (2.33 Å) and shorter
than the sum of their van der Waals radii (3.8 Å) [20].
Ancillary axial contacts involve chlorine atoms of
tions at, respectively, 170 and 150–140 cm–1 are also
active [28]. The latter were identified in the IR specꢀ
trum recorded at –193
and at 169, 162, and 140 cm–1 for II. It is worth noting
that the number of bands in the IR spectrum of is
°С I
: at 169 and 142 cm–1 for
I
neighboring complex anions in
I and uncoordinated
smaller than in spectrum II, which is evidence of a
lower symmetry of the latter.
chloride ions in II. Various variants of mutual arrangeꢀ
ment of prolate SBPs for some Au(III) complexes
have been reported in [15]. In our case, SBPs share
edges in I (such a variant is absent in [15]) and vertices
ACKNOWLEDGMENTS
in II (according to [15], such a variant is rare). It is
worth noting, that the structure of II differs signifiꢀ
cantly from that of (DiеnH3)2[PtCl4]Cl4, which has a
close stoichiometric composition [21]. Platinum(II)
has a weak tendency for extra coordination, so that the
structure lacks even weak interaction with free chloꢀ
ride ions.
We are grateful to I.V. Korol’kov for performing the
Xꢀray singleꢀcrystal and powder diffraction experiꢀ
ments and to P.E. Pluysnin for recording the thermal
curves.
REFERENCES
3+
1. R. L. Puddephatt, The Chemistry of Gold (Elsevier,
Amsterdam, 1978; Mir, Moscow, 1982).
2. P. F. Theobald and H. Omrani, Acta Crystallogr., Sect.
For
in
I
and II, the N–C distances are
are longer than in
II. The range of bond angles in II is somewhat larger
than in . In general, the geometric characteristics of
the complex cation in and II are similar to those
observed in known structures of metal complexes with
DienH3
close, whereas the C–C bonds in
I
B
36, 2932 (1980).
I
3. G. Dessy, C. Furlani, and F. M. Capece, Acta Crystalꢀ
logr., Sect. B 29, 1737 (1973).
4. H.ꢀN. Adams and J. Strahle, Z. Anorg. Allg. Chem.
485, 65 (1982).
5. N. G. B. Drew, L. R. Glaves, and M. J. Hudson,
J. Chem. Soc., Dalton Trans., No. 4, 771 (1985).
I
DienH33+
[21–26]. Another specific feature of and II
is that the cations in their structures have different
conformations. In , the core of the diethylenetriamꢀ
I
I
monium cation located in a channel has a planar
trans conformation. In this case, two NH3 groups lie
in the central NC2 plane. Such a cation conformaꢀ
tion is observed, for example, in (DiеnH3)Х3 and
(DiеnH3)[PtCl6]Х (X = Cl [22, 23], NO3 [24, 25]) and
(DiеnH3)[CuCl4]Cl [26]. In II, the arrangement of
NH3 groups is somewhat different: one group is perꢀ
pendicular to the central NC2 plane, and the other is
almost in this plane. Such a structure was found for the
cation, for example, in (DiеnH3)2[PtCl4]Cl4 [21].
6. M. S. Hussian and S. A. A. AlꢀHamoud, J. Chem. Soc.,
Dalton Trans., No. 4, 749 (1985).
7. H. Kiriyama, N. Matsushita, and Y. Yamagata, Acta
Crystallogr., Sect. C 42, 227 (1986).
8. K. I. Turte, S. G. Shova, V. M. Meriakure, et al.,
Zh. Strukt. Khim. 43 (1), 114 (2002).
9. P. E. Plyusnin, I. A. Baidina, Yu. V. Shubin, and
S. V. Korenev, Zh. Neorg. Khim. 50 (12), 1959 (2005)
[Russ. J. Inorg. Chem. 50 (12), 1834 (2005)].
10. P. E. Plyusnin, I. A. Baidina, Yu. V. Shubin, and
S. V. Korenev, Zh. Neorg. Khim. 52 (3), 421 (2007)
[Russ. J. Inorg. Chem. 52 (3), 371 (2007)].
11. P. E. Plyusnin, I. A. Baidina, Yu. V. Shubin, and
S. V. Korenev, Zh. Neorg. Khim. 53 (11), 1844 (2008)
[Russ. J. Inorg. Chem. 53 (11), 1724 (2008)].
We compared the IR spectra of compounds
I and II
with the spectrum of DiеnH3Cl3 (III . The spectrum of
)
III recorded at 25°С
in the range 3200–2000 cm–1
shows a broad strong absorption band at ~2700 cm–1
composed of a series of narrow bands and caused by
12. E. V. Makotchenko, I. A. Baidina, and D. Yu. Naumov,
Zh. Strukt. Khim. 47 (3), 512 (2006).
13. E. V. Makotchenko, I. A. Baidina, and P. E. Plyusnin,
NH3+ꢀ
NH2+ꢀ
stretching vibrations of
and
groups
involved in hydrogen bonds [27]. In the IR spectra of
complexes and II, the position of these bands
Zh. Strukt. Khim. 48 (2), 282 (2007).
I
14. I. A. Baidina, E. V. Makotchenko, P. E. Plyusnin, and
S. V. Korenev, Proceedings of XXIII International
Chugaev Conference on Coordination Chemistry, Kiev,
2007, p. 284.
15. G. Marangoni, B. Pitteri, V. Bertolasi, et al., J. Chem.
Soc., Dalton Trans., 2235 (1987).
remains unaltered, which is evidence that the cations
are not involved in the coordination with the gold
atoms. The same range in the IR spectrum of
clearly separated bands of H2O stretching vibrations at
3501 and 3445 cm–1 and structured
(NH) bands with
maxima at 3207, 3212, and 3010 cm–1. In contrast to
, the spectral pattern for II is nearly the same as for
I shows
ν
16. W. H. Baddley, F. Basolo, H. B. Gray, et al., Inorg.
I
Chem. 2 (5), 921 (1963).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 5 2011

720
MAKOTCHENKO et al.
17. G. M. Sheldrick, SHELXꢀ97, Univ. of Göttingen, Gerꢀ 23. E. V. Makotchenko, I. A. Baidina, and S. A. Gromilov,
many, 1997.
Zh. Strukt. Khim. 48 (6), 1222 (2007).
24. R. D. Rogers and C. D. Bauer, J. Chem. Cryst. 24 (4),
18. I. V. Mironov and L. D. Tsvelodub, Zh. Neorg. Khim.
45 (3), 425 (2000) [Russ. J. Inorg. Chem. 45 (3), 361
(2000)].
281 (1994).
25. E. V. Makotchenko, I. A. Baidina, P. E. Plyusnin, et al.,
Koord. Khim. 33 (1), 45 (2007) [Russ. J. Coord. Chem.
33 (1), 45 (2007)].
19. Yu. N. Kukushkin, L. I. Danilina, N. P. Fedyanin, and
A. V. Iretskii, Zh. Neorg. Khim. 26 (12), 3293 (1981).
26. T. J. Greenhough and M. F. C. Ladd, Acta Crystallogr.,
Sect. B 33, 1266 (1977).
20. S. S. Batsanov, Zh. Neorg. Khim. 36 (12), 3015 (1991).
27. A. J. Gordon and R. A. Ford, The Chemist’s Companion:
A Handbook of Practical Data, Techniques and Referꢀ
ences (Wiley, New York, 1972; Mir, Moscow, 1976).
21. J. Britten and C. J. L. Lock, Acta Crystallogr., Sect. B
35, 3065 (1979).
22. S. N. Golubev and Yu. D. Kondrashev, Zh. Strukt. 28. P. L. Goggin and J. Mink, J. Chem. Soc., Dalton
Khim. 22 (1), 80 (1981).
Trans., 1479 (1974).
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