ISSN 00360236, Russian Journal of Inorganic Chemistry, 2015, Vol. 60, No. 7, pp. 832–842. © Pleiades Publishing, Ltd.

, 2015.
Original Russian Text © E.V. Makotchenko, I.A. Baidina, I.V. Korol’kov, 2015, published in Zhurnal Neorganicheskoi Khimii, 2015, Vol. 60, No. 7, pp. 917–928.

Synthesis and Structure of Double Complex Salts

[Pd(Dien)Cl][AuX4] (X = Cl, Br), [Pd(Dien)Br][AuBr4],
and Initial Complex [Pd(Dien)Cl]Cl
E. V. Makotchenkoa, b, I. A. Baidinaa, and I. V. Korol’kova, b
a
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 3, Novosibirsk, 630090 Russia
bNovosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia

email: evm@niic.nsc.ru
Received October 30, 2014

Abstract—New double complex salts were prepared: [Pd(Dien)Cl][AuCl4] (I), [Pd(Dien)Cl][AuBr4] (II),
and [Pd(Dien)Br][AuBr4] (III). The compounds were studied by elemental analysis, IR spectroscopy, Xray
powder diffraction, and Xray crystallography. Crystallographic data for I: a = 16.6661(5) Å, b = 12 7175(4) Å, c =
12.8936(4) Å, β = 97.621(1)°, space group C2/c, Z = 8, ρcalcd = 2.863 g/cm3, R = 0.015; for II: a = 8.1855(4) Å,
b = 21.509(1) Å, c = 8.7570(4) Å, β = 106.891(1)°, space group P21/c, Z = 4, ρcalcd = 3.429 g/cm3, R = 0.039;
for III: a = 7.3660(5) Å, b = 8.3330(4) Å, c = 12.4914(7) Å, α = 104.719(2)°, β = 95.674(3)°, γ = 92.281(3)° ,
space group P1, Z = 2, ρcalcd = 3.636 g/cm3, R = 0.061. The crystal structure of [Pd(Dien)Cl]Cl (IV) was estab
lished. The crystallographic data for IV: a = 13.935(3) Å, b = 4.823(1) Å, c = 13.249(3) Å, space group Pca21,
Z = 4, ρcalcd = 2.092 g/cm3, R = 0.044. Intermolecular interactions (metal–halide ion, halogen–halogen)
were revealed, which play an important role in constructing the general motif of crystal structures of com
pounds I–IV.
DOI: 10.1134/S0036023615050149

Double complex salts (DCS) containing complex
cation of one metal and complex anion of another
metal are of great interest for researchers. This is
explained in the first place by the fact that these com
pounds can behave as precursors of different bimetal
lic materials. The application of such systems is exem
plified by the preparation of finely dispersed particles of
solid solutions of metals on different supports for pre
paring highly efficient heterogeneous catalysts [1–5].
The possibility to use gold and goldcontaining cata
lysts is intensely studied in recent years [6, 7], there
fore DCS containing gold are of special interest. These
DCS may serve as convenient models for studying the
features of coordination chemistry, in particular, gold
chemistry. Complete data on DCS structure are neces
sary to reveal relationships between their chemical
composition and behavior under various conditions.
At present, the research of structure of coordina
tion compounds is focused on finding and analysis of
noncovalent interactions between structural units,
which are characterized by interatomic distances
longer than the sum of covalent radii but shorter than
the sum of van der Waals radii of the corresponding
pairs of atoms. These interactions called by Alcock
secondary bonds [8] are referred to weak interactions,
however, they play important role in formation of solid
phases [9]. The presence of secondary bonds was
revealed in the structural studies of a number of
gold(III) complexes [10–15], which allowed the
authors to claim gold coordination numbers of 4 + 1 or
4 + 2.
Halide gold(III) complexes М[AuX4] (X = Cl, Br;
M = H, Na, K) are used most frequently to prepare
different gold compounds [16]. It was tetrachloroau
rate anion that was used for the first place to obtain a
number of DCS and to study their structure:
[Co(NH3)6][AuCl4]Cl2 [17], [Co(En)3][AuCl4]2Cl
[18], M(NH3)5Cl][AuCl4]X ⋅ nH2O (M = Ir, Rh, Ru,
Cr, Pt; X = Cl, NO3; n = 0–2) [19, 20],
[Pd(NH3)4][AuCl4]2 [21]. Moreover, DCS that contain
[AuBr4]– anion were studied: [Co(NH3)6][AuBr4]Br2
[17], [Co(En)3][AuBr4]2Br [22], [M(NH3)5Br][AuBr4]2 ·
Н2О, where M = Ir, Rh [23, 24]. All the complex cat
ions here, except for palladium, with regular or dis
torted octahedral coordination of metal atom are
coordinatively saturated. The feature of these DCS is
the presence of weak intermolecular interactions of
gold(III) atoms with either halogen atoms of neigh
boring complex anions and cations or free halide ions.
These intermolecular interactions enable gold atom to
supplement its coordination to tetragonalpyramidal
or bipyramidal. In terms of structure, the effect of
intermolecular interactions is reflected in the forma
tion of different associates (pseudodimers, polymeric
chains, or stacks) of complex gold anions.

832
 SYNTHESIS AND STRUCTURE OF DOUBLE COMPLEX SALTS
This work is a continuation of structural studies of
DCS containing tetrahalide gold(III) complexes. The
aim of this work is to extend the scope of structurally
characterized DCS containing [AuCl4]– and [AuBr4]–
complex anions. We used [Pd(Dien)Cl]+ (Dien is
diethylenetriamine) as an initial complex cation.
Xray diffraction analysis of [Pd(Dien)Cl]Cl complex
was conducted supplementary.
EXPERIMENTAL
Initial complexes [Pd(Dien)Cl]Cl [25],Na[AuCl4] ⋅
2H2O, Na[AuBr4] ⋅ 2Н2О [26] [AuDienCl]Cl2 [27],
and K2[PdBr4] [28] were prepared using described
procedures.
Synthesis of [Pd(Dien)Cl][AuCl4] (I). A solution of
[Pd(Dien)Cl]Cl (0.142 g, 0.5 mmol) in 1.0 mL of
0.1 mol/L HCl was added on stirring to a solution of
Na[AuCl4] ⋅ 2H2O (0.200 g, 0.5 mmol) in 0.8 mL of
0.01 mol/L HCl. The resultant precipitate was quickly
separated by filtration, washed with small amounts of
water, ethyl alcohol and dried in air to give 0.246 g of
polycrystalline bright yellow powder (yield ~84%).
For C4H13AuCl5N3Pd anal. calcd. (%): C, 8.23;
H, 2.24; N, 7.20.
Found (%): C, 8.25; H, 2.3; N, 7.1.
IR (ν, cm–1): 3293, 3247, 3193, 2921, 1573, 1452,
1354, 1304, 1286, 1257, 1150, 1126, 1074, 1042, 982,
923, 893, 868, 836, 710, 571, 546, 512, 482, 445, 385,
354.5, 328, 284.8, 241.7, 192.7, 174, 140.5, 90.3.
Single crystals of I suitable for Xray diffraction
study were obtained by the slow evaporation of diluted
solution of I in acetone at ambient temperature.
Synthesis of [Pd(Dien)Cl][AuBr4] (II). A solution
of Na[AuBr4] ⋅ 2H2O (0.058 g, 0.1 mmol) in 0.5 mL of
H2O was added on stirring to a solution of
[Pd(Dien)Cl]Cl (0.056 g, 0.2 mmol) in 0.5 mL of
0.01 mol/L HCl. The resultant precipitate was quickly
separated by filtration, washed with small amounts of
water, ethyl alcohol and dried in air to give 0.063 g of
polycrystalline tile–red powder (yield toward gold
~83%).
For C4H13AuBr4ClN3Pd anal. calcd. (%): C, 6.31;
H, 1.72; N, 5.52.
Found (%): C, 6.5; H, 1.8; N, 5.6.
IR (ν, cm–1): 3283, 3227, 3181, 2931, 2854, 1576,
1455, 1305, 1255, 1142, 1123, 1074, 1046, 1033, 992,
926, 892, 864, 836, 565, 519, 488, 451, 382, 331, 248,
196.5, 150.8, 137.5, 116.7, 99.
Slow crystallization of the mother liquor after sep
aration of the main DCS phase afforded single crystals
of [Pd(Dien)Cl]Cl (IV). The slow evaporation of
diluted solution of DCS II in acetone resulted in prep
aration of single crystals of III suitable for Xray dif
fraction study. A single crystal of II was selected from
the total body of crystals upon the longterm keeping
of weakly acidic (0.022 mL/L HClO4) aqueous solu
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
833
tion containing [Au(Dien)Cl]Cl2 and K2[PdBr4] (ini
tial concentrations were 0.005 mo/L each) at ~5°C.
Synthesis of [Pd(Dien)Br][AuBr4] (III). A solution
of [Pd(Dien)Cl]Cl (0.0673 g, 0.24 mmol) in 0.5 mL of
water was added on stirring to a solution of Na[AuBr4] ⋅
2H2O (0.138 g, 0.24 mmol) + NaBr (0.025 g,
0.24 mmol) in 0.5 mL of HBr solution (0.01 mol/L).
The resultant precipitate was separated by filtration,
washed with small amounts of water, ethyl alcohol and
dried in air to give 0.170 g of polycrystalline dark
cherry powder (yield ~88%).
For C4H13AuBr5N3Pd anal. calcd. (%): C, 5.96;
H, 1.63; N, 5.21.
Found (%): C, 6.1; H, 1.75; N, 5.25.
IR (ν, cm–1): 3273, 3226, 3200, 3155, 2928, 2867,
1563, 1451, 1304, 1289, 1251, 1135, 1076, 1043, 1013,
990, 930, 892, 868, 837, 704, 655, 564, 507, 480, 446,
382, 340.6, 253, 246.5, 196.5, 177, 124, 98.5.
Single crystals of III were obtained by the slow
evaporation of its solution in aqueous acetone at ambi
ent temperature.
Elemental analysis for C, H, N was performed on
an Euro EA 3000 instrument by standard procedure.
The IR spectra of the studied compounds were
recorded on a Scimitar FTS 2000 and a Vertex 80 Fou
riertransform IR spectrometers in Nujol and fluori
nated oil (400–4000 cm–1) and polyethylene (100–
600 cm–1).
Xray diffraction analysis. Unit cell parameters and
experimental intensities for determination of crystal
structures of compounds I and II were measured at
low temperature on a BRUKER APEX DUO auto
mated fourcircle diffractometer, those for com
pounds III and IV were determined at ambient tem
perature on a BRUKER APEX2 diffractometer
(MoKα radiation, graphite monochromator, CCD
detector) by standard procedure. Table 1 displays the
crystallographic characteristics and main experimen
tal parameters for compounds I–IV. The structures of
the compounds were solved by direct methods and
refined by fullmatrix least squares on F 2 in anisotro
pic–isotropic (for H) approximation. Hydrogen
atoms were assigned idealized locations. The main val
ues of interatomic distances and valence angles of
complexes in structures I–IV are presented in Table 2.
The coordinates of basis atoms are deposited in the
Cambridge Structural Database: I, no. 1024039;
II, no. 1024038; III, no. 1024037; IV, no. 1024040. All
computations were performed using SHELX97 soft
ware package [29].
Xray powder diffraction was carried out on a Shi
madzu XRD7000 diffractometer (CuKα radiation, Ni
filter, 2θ range 5°–50°, step 0.03°, accumulation time
1 s) at ambient temperature and atmospheric pressure.
The products were ground in an agate mortar and the
powder was placed on the polished side of a standard
quartz cuvette coated with a thin layer of petrolatum.
Vol. 60 No. 7 2015
834 MAKOTCHENKO et al.

Table 1. Crystallographic characteristics and the main experimental parameters for compounds I–IV
Characteristic I II III IV
FW 583.79 761.63 806.09 280.47
T, K 150(2) 100(2) 296(2) 296(2)
Syngony Monoclinic Monoclinic Triclinic Rhombic
Space group C2/c P21/c P1 Pca21
a, Å 16.6661(5) 8.1855(4) 7.3660(5) 13.935(3)
b, Å 12.7175(4) 21.509(1) 8.3330(4) 4.823(1)
c, Å 12.8936(4) 8.7570(4) 12.4914(7) 13.249(3)
α, deg 90 90 104.719(2) 90
β, deg 97.621(1) 106.891(1) 95.674(3) 90
γ, deg 90 90 92.281(3) 90
V, Å3 2708.67(14) 1475.26(12) 736.26(7) 890.4(3)
Z 8 4 2 4
ρcalcd, g/cm3 2.863 3.429 3.636 2.092
μ, mm–1 13.102 22.139 24.712 2.618
F(000) 2144 1360 716 552
Crystal dimensions, mm 0.32 × 0.03 × 0.03 0.30 × 0.07 × 0.06 0.45 × 0.07 × 0.07 0.30 × 0.04 × 0.02
θ scan range 2.02–31.52 1.89–33.19 2.53–30.67 2.92–31.48
Index range –22 ≤ h ≤ 24, –10 ≤ h ≤ 12, –8 ≤ h ≤ 9, –20 ≤ h ≤ 20,
–18 ≤ k ≤ 18, –32 ≤ k ≤ 33, –11 ≤ k ≤ 11, –7 ≤ k ≤ 7,
–18 ≤ l ≤ 18 –13 ≤ l ≤ 13 –17 ≤ l ≤ 17 –18 ≤ l ≤ 19
Number of measured/ 12667/4521 20721/5633 9789/3603 9256/2672
independent reflections [R(int) = 0.0166] [R(int) = 0.0213] [R(int) = 0.0451] [R(int) = 0.0511]
Data acquisition complete 100.0 99.9 83.9 99.4
ness, %
Transmittance, max and min 0.6946 and 0.1022 0.3501 and 0.0577 0.2766 and 0.0318 0.9495 and 0.5072
Number of refined parameters 133 131 127 93
S factor on F 2 1.021 1.042 1.074 1.066
R factor [I > 2σ(I)] R1 = 0.015, R1 = 0.039, R1 = 0.061, R1 = 0.044,
wR2 = 0.0341 wR2 = 0.1128 wR2 = 0.1743 wR2 = 0.1117
R factor (all data) R1 = 0.0210, R1 = 0.0423, R1 = 0.1047, R1 = 0.0571,
wR2 = 0.0351 wR2 = 0.1144 wR2 = 0.1925 wR2 = 0.1178
Δρmax, Δρmin, e/Å3 1.146, –0.945 3.192, –5.900 2.293, –2.521 1.637, –1.140

The resulting specimens were layers ~100 μm thick.
Polycrystalline silicon prepared in similar manner was
used as an external reference. The monophase charac
ter of the obtained compounds was established by the
indication of Xray diffraction patterns by analogy
with theoretical diffractograms of complexes studied
by Xray diffraction analysis.
RESULTS AND DISCUSSION
Double complex salts in solid state are usually
obtained by exchange reaction by mixing aqueous
solutions of the corresponding complexes. The prepa
ration of pure complexes is possible in the absence or
minimal presence of any side reactions resulting in by
products that contaminate the target compound.
Thus, for example, salt [Pd(NH3)4][AuCl4]2 prepared
from [Pd(NH3)4]Cl2 and H[AuCl4] was contaminated
by small amount of palladosamine [Pd(NH3)2Cl2],
which formed during synthesis on account of side
reaction of substitution of innersphere NH3 mole
cules by Cl– ions in the initial palladium complex [21].
The authors prepared pure DCS in the absence of
excess HCl in reaction solution and with the use of
[Pd(NH3)4](NO3)2 (the lack of outersphere chloride
ions) as initial complex.
The presence of mobile equilibrium in solutions
containing gold(III) and palladium(II) complexes was
established, for example, in the course of preparation
of single crystals of compound II. The latter were

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

 SYNTHESIS AND STRUCTURE OF DOUBLE COMPLEX SALTS 835

Table 2. The main interatomic distances (d) and bond angles (ω) in structures I–IV
Bond d, Å Angle ω, deg
I
Au(1)–Cl(1) 2.2766(6) Cl(1)#1Au(1)Cl(1) 89.44(3)
Au(1)–Cl(2) 2.2864(6) Cl(1)Au(1)Cl(2)#1 179.14(2)
Au(2)–Cl(4) 2.2709(6) Cl(1)Au(1)Cl(2) 90.01(2)
Au(2)–Cl(3) 2.2815(7) Cl(2)#1Au(1)Cl(2) 90.55(3)
Pd(1)–N(1) 2.014(2) Cl(4)Au(2)Cl(3) 90.42(4)
Pd(1)–N(3) 2.037(2) N(1)Pd(1)N(3) 84.37(9)
Pd(1)–N(2) 2.049(2) N(1)Pd(1)N(2) 84.30(9)
Pd(1)–Cl(5) 2.3085(6) N(3)Pd(1)N(2) 166.67(8)
N(1)–C(1) 1.489(3) N(1)Pd(1)Cl(5) 177.68(6)
N(1)–C(3) 1.495(3) N(3)Pd(1)Cl(5) 94.21(6)
N(2)–C(2) 1.500(3) N(2)Pd(1)Cl(5) 96.87(6)
N(3)–C(4) 1.492(3) C(1)N(1)C(3) 117.37(19)
C(1)–C(2) 1.515(4) C(1)N(1)Pd(1) 108.51(15)
C(3)–C(4) 1.506(4) C(3)N(1)Pd(1) 105.48(15)
C(2)N(2)Pd(1) 108.70(15)
C(4)N(3)Pd(1) 108.74(16)
N(1)C(1)C(2) 107.4(2)
N(2)C(2)C(1) 107.5(2)
N(1)C(3)C(4) 105.77(19)
N(3)C(4)C(3) 108.3(2)
II
Au(1)–Br(4) 2.3875(9) Br(4)Au(1)Br(1) 178.43(3)
Au(1)–Br(1) 2.4106(8) Br(4)Au(1)Br(2) 90.76(3)
Au(1)–Br(2) 2.4188(7) Br(1)Au(1)Br(2) 89.65(3)
Au(1)–Br(3) 2.4297(8) Br(4)Au(1)Br(3) 88.33(3)
Pd(1)–N(1) 2.005(6) Br(1)Au(1)Br(3) 91.25(3)
Pd(1)–N(2) 2.040(6) Br(2)Au(1)Br(3) 179.09(3)
Pd(1)–N(3) 2.043(6) N(1)Pd(1)N(2) 84.4(2)
Pd(1)–Cl(1) 2.3362(14) N(1)Pd(1)N(3) 84.8(2)
N(1)–C(7) 1.485(9) N(2)Pd(1)N(3) 167.4(2)
N(1)–C(4) 1.489(9) N(1)Pd(1)Cl(1) 178.90(17)
N(2)–C(6) 1.505(9) N(2)Pd(1)Cl(1) 94.59(17)
N(3)–C(5) 1.494(10) N(3)Pd(1)Cl(1) 96.21(18)
C(4)–C(6) 1.512(10) C(7)N(1)C(4) 117.0(6)
C(5)–C(7) 1.530(11) C(7)N(1)Pd(1) 107.7(4)
C(4)N(1)Pd(1) 107.9(4)
C(6)N(2)Pd(1) 108.6(4)
C(5)N(3)Pd(1) 108.9(4)
N(1)C(4)C(6) 106.2(5)
N(3)C(5)C(7) 108.4(6)
N(2)C(6)C(4) 108.0(6)
N(1)C(7)C(5) 106.7(6)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

836 MAKOTCHENKO et al.

Table 2. (Contd.)

Bond d, Å Angle ω, deg

III
Au(1)–Br(2) 2.383(2) Br(2)Au(1)Br(4) 176.74(7)
Au(1)–Br(4) 2.411(2) Br(2)Au(1)Br(3) 89.75(7)
Au(1)–Br(3) 2.4278(14) Br(4)Au(1)Br(3) 89.91(7)
Au(1)–Br(1) 2.4285(13) Br(2)Au(1)Br(1) 89.90(6)
Pd(1)–N(1) 2.013(10) Br(4)Au(1)Br(1) 90.50(6)
Pd(1)–N(3) 2.033(11) Br(3)Au(1)Br(1) 178.96(6)
Pd(1)–N(2) 2.046(10) N(1)Pd(1)N(3) 85.8(4)
Pd(1)–Br(5) 2.393(2) N(1)Pd(1)N(2) 84.5(4)
N(1)–C(3) 1.457(16) N(3)Pd(1)N(2) 169.4(5)
N(1)–C(1) 1.459(19) N(1)Pd(1)Br(5) 178.5(3)
N(2)–C(2) 1.54(2) N(3)Pd(1)Br(5) 93.0(3)
N(3)–C(4) 1.619(19) N(2)Pd(1)Br(5) 96.7(3)
C(1)–C(2) 1.40(2) C(3)N(1)C(1) 124.4(14)
C(3)–C(4) 1.44(2) C(3)N(1)Pd(1) 108.8(8)
C(1)N(1)Pd(1) 108.3(8)
C(2)N(2)Pd(1) 106.3(8)
C(4)N(3)Pd(1) 107.0(8)
C(2)C(1)N(1) 110.5(17)
C(1)C(2)N(2) 112.3(13)
C(4)C(3)N(1) 112.3(14)
C(3)C(4)N(3) 107.8(12)
IV
Pd(1)–N(2) 1.989(5) N(2)Pd(1)N(3) 84.3(2)
Pd(1)–N(3) 2.046(6) N(2)Pd(1)N(1) 83.9(2)
Pd(1)–N(1) 2.047(6) N(3)Pd(1)N(1) 165.6(2)
Pd(1)–Cl(1) 2.3422(15) N(2)Pd(1)Cl(1) 172.87(16)
N(1)–C(1) 1.492(9) N(3)Pd(1)Cl(1) 96.48(17)
N(2)–C(2) 1.472(9) N(1)Pd(1)Cl(1) 96.24(18)
N(2)–C(3) 1.513(9) C(1)N(1)Pd(1) 107.4(4)
N(3)–C(4) 1.490(10) C(2)N(2)C(3) 116.7(5)
C(1)–C(2) 1.513(10) C(2)N(2)Pd(1) 109.4(4)
C(3)–C(4) 1.505(12) C(3)N(2)Pd(1) 108.1(4)
C(4)N(3)Pd(1) 108.1(4)
N(1)C(1)C(2) 108.6(6)
N(2)C(2)C(1) 104.6(5)
C(4)C(3)N(2 105.0(5)
N(3)C(4)C(3) 107.6(6)
Symmetry codes for equivalent atoms: #1 – x, y, –z + 1/2.

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

 SYNTHESIS AND STRUCTURE OF DOUBLE COMPLEX SALTS
obtained unexpectedly by longterm crystallization at
~5°С from aqueous weakly acidic solution containing
[Au(Dien)Cl]Cl2 and K2[PdBr4] complexes instead of
crystals of expected [ClAu(Dien*)PdBr3] complex
(Dien* is deprotonated diethylenetriamine). Previously,
we obtained binuclear complex [ClAu(Dien*)PdCl3],
where the central nitrogen atom of diethylenetriamine
behaves as a bridging ligand, from an aqueous solution
containing [Au(Dien)Cl]Cl2 and K2[PdCl4] [30].
According to the literature data, the complex
[Pd(Dien)Cl]Cl is stable at pH 1.0 and its hydrolysis is
negligible [31]. In aqueous solution, [AuCl4]– and
[AuBr4]– anions undergo hydrolysis, the concentration
of hydrolysis products is negligible at ratios pH + pCl ≤ 4.0
[32] and pH + pBr ≤ 6.5 [33]. Another possible side reac
tion, the substitution of bromide ion in labile [AuBr4]– by
Cl– (outersphere Cl– from [Pd(Dien)Cl]Cl), may result
in final products containing differentligand chlo
ride–bromide complexes [AuBr4 – xClx]–. It is known
that the maintenance of sole form [AuBr4]– in solution
containing bromide and chloride ions requires ratio of
equilibrium concentrations [Br]/[Cl] > 10 [34]. In the
presence of excess of bromide ions in reaction solution
during synthesis of III, a reaction of Cl substitution by
Br in [Pd(Dien)Cl]+ proceeds to give [Pd(Dien)Br]+
cation, which combines with [AuBr4]–. When synthe
sis of compound III was conducted in strongly acidic
medium (by mixing solution of H[AuBr4] + HBr with
solution of [Pd(Dien)Cl]Cl), the solution obtained
after precipitate separation produced next day single
crystals suitable for Xray diffraction analysis, the
crystals were found to be (DienH3)[AuBr4]3 ⋅ H2O
complex (DienH 33+ is a protonated diethylenetri
amine) previously studied by us [35]. Obviously, the
high concentrations of H+ and Br– in reaction solution
favor the reaction of ligand substitution in the inner
coordination sphere of [Pd(Dien)Cl]+ by bromide ions
to give DienH 33+ as one of reaction products. Taking
the mentioned above into account, the synthesis of
complexes I–III was conducted in weakly acidic
medium, therefore initial gold complexes used were
sodium salts of complex goldcontaining acids rather
than the acids themselves. The manipulations of pre
cipitation and separation of resultant precipitates of
DCS were conducted as quickly as possible.
The obtained compounds I–III are stable on stor
age in air, soluble in acetone, acetonitrile, poorly sol
uble in ethyl alcohol, insoluble in hexane and chloro
form.
According to Xray diffraction study, the crystals of
compounds I–III are not isostructural. The structures
of compounds I–III are built from complex cations
[Pd(Dien)Х]+ and complex anions [AuХ4]– (X = Cl,
Br) with ratio Pd : Au = 1 : 1. Figure 1 shows the struc
ture of constitutional units with atom numbering for
compounds I–III.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
837
The structure of compound I includes two crystal
lographically independent gold anions [AuCl4]–, one
of which is located on the axis 2, while the second
anion is centrosymmetrical. The planes of coordina
tion squares of two gold atoms are essentially perpen
dicular to each other. The average length of Au–Cl
bonds is 2.279 Å, the deviations of valence angles at the
central Au atoms from 90° are negligible (0.6° at max
imum). The coordination of gold atom in anions is
supplemented in different modes: for Au(2) up to
pyramidal (4 + 1) by weak contact with Cl atoms of
complex Pd cation (Au⋅⋅⋅Cl 3.305 Å), for Au(1) up to
bipyramidal (4 + 2) by Cl atoms of neighboring com
plex anions of Au(1) (Au⋅⋅⋅Cl 3.535 Å). The Au⋅⋅⋅Cl
distances in complex I are not longer than the sum of
the van der Waals radii of Au and Cl atoms (3.8 Å) [36].
The complex anions in the structure are united into
chains with Au⋅⋅⋅Au distance of 5.628 Å due to such
supplementary contacts. Intermolecular Cl⋅⋅⋅Cl con
tacts (3.16 Å), which are shorter than the double value
of the van der Waals radius of Cl atom (3.6 Å) [36], are
observed between the chains. The same contacts in
anionic layers were found in other DCS containing
[AuCl4]– anion, for example, [Co(NH3)6][AuCl4]Cl2
(3.44 Å) [17], [Co(En)3][AuCl4]2Cl (3.22, 3.49 Å) [18],
[Pd(NH3)4][AuCl4]2 (3.25, 3.36 Å) [21].
Palladium complex cations in structures I and II
have geometrical structure close to IV (its description
is given below). The valence angles at the central Pd
atoms differ from ideal 90° by no more than 6.9°. The
Pd–Cl distance is 2.308 Å in I and 2.336 Å in II, which
is slightly shorter than in IV (2.342(1) Å). Similar
Pd⎯Cl distances were found in akin complexes, for
example, 2.305(3) Å in [Pd(Bpma)Cl]Cl (Bpma is
bis(2pyridylmethyl)amine) [37], 2.331(3) Å in
[Pd(Me3Dpma)Cl]Cl (Me3Dpma is methylbis[(6
methyl2pyridyl)methyl]amine) [38]. The distances
of Pd–N bonds vary within 2.005–2.049 Å, the aver
age distance to terminal nitrogen atoms is 0.03 Å
longer than to the central ones. The Dien ligands in
complexes I and II provide tridentate chelate environ
ment. The resultant two fivemembered chelate rings
are nonplanar (have a gauche conformation). The dis
tances of N–C and C–C bonds have normal values
(average 1.494 and 1.515 Å, respectively) and are com
parable with those found for compound IV and
reported literature data for [Pd(Dien)(NO2)]NO3 [39].
Let us note that the Pd–Cl bonds in the series I, II,
and IV exhibit elongation (2.308, 2.336, and 2.342 Å,
respectively), while the Pd–N bonds in the trans posi
tion to Cl display shortening (2.014, 2.005, and
1.989 Å, respectively).
In the structure of compound I, the complex Pd
cations are close to each other and produce dimeric
associates. The square coordination of Pd atom is sup
plemented to pyramidal environment (4 + 1 + 1) by
contacts with Pd atom of neighboring complex cation
to form a dimer from one side, and by Cl atom from
Au(1) environment from another side (Pd⋅⋅⋅Pd and
Vol. 60 No. 7 2015
838 MAKOTCHENKO et al.

(a) (b)

Br(4) N(3)
Cl(5)
Cl(1)
Cl(4)
N(3) Au(2) C(5)
Br(2)
Pd(1) Pd(1) C(7)
C(4) Au(1)
Cl(3)
N(1) N(2) N(1)
C(3) Br(3)

Br(1) N(2) C(4)

C(1) Cl(2)
C(2)
C(6)
Au(1)

Cl(1)

(c)

N(3)
C(4)
Br(5)
Pd(1)

C(3) Br(2)

N(1)
Au(1)
Br(3)
N(2) Br(1)
C(1)

C(2)
Br(4)

Fig. 1. The structure of constitutional units with atom numbering for compounds [Pd(Dien)Cl][AuCl4] (a),
[Pd(Dien)Cl][AuBr4] (b), and [Pd(Dien)Br][AuBr4] (c).

Pd⋅⋅⋅Cl distances equal to 3.596 and 3.586 Å, respec
tively, the double value of the van der Waals radius of
Pd atom is 4.2 Å, while the sum of the van der Waals
radii of Pd and Cl atoms is 3.9 Å [36]). Square palla
dium(II) complexes like gold(III) complexes are
coordinatively unsaturated and palladium atom can
also produce a supplementary coordination. Thus, for
example, the square coordination of palladium atom is
supplemented to bipyramidal by contacts with chlo
rine atoms of neighboring gold and palladium complex
anions in [Pd(NH3)4][AuCl4]2 [21] and in
[Rh(NH3)5Cl][PdCl4] ⋅ H2O [40] (Pd⋅⋅⋅Cl is 3.58 and
3.17 Å, respectively).
One independent [AuBr4]– anion in the structure
of complex II occupies general position. The coordi
nation square of gold is flat within ±0.04 Å. The devi
ations of valence angles from 90° are mot larger than
1.7°, average Au–Br bond distance is 2.412 Å. Gold
coordination in [AuBr4]– anion is supplemented to
bipyramidal (4 + 1 + 1) by Cl atom of complex Pd cat
ion from one side and by Br atom of the neighboring
anion from the other side (Au⋅⋅⋅Cl and Au⋅⋅⋅Br are
3.438 and 3.646 Å, respectively, the sum of the van der
Waals radii of Au and Br atoms is 3.9 Å [36]). These
intermolecular contacts provide complex anions to
come close to reach Au⋅⋅⋅Pd distance of 4.630 Å.
Palladium cations in the structure II are united by
two symmetrical hydrogen bonds N–H⋅⋅⋅Cl and are
spaced from each other to Pd⋅⋅⋅Pd distance of 5.974 Å.
The coordination of Pd atoms is supplemented to
pyramidal (4 + 1) by bromine atom of the complex
anion (Pd⋅⋅⋅Br is 3.647 Å, the sum of the van der Waals
radii of Pd and Br atoms is 4.0 Å [36]). Figures 2 and 3
show the general view of crystal structures I and II and
bonding of complex anions in crystal.
In the structure III, the coordination square of
[AuBr4]– anion is flat within ±0.04 Å. The deviations
of valence angles from 90° are negligible (0.5°), Au–Br
bond distances vary in the range 2.383–2.429 Å (aver
age 2.412 Å). The main geometrical characteristics of
[AuBr4]– anion agree well with similar characteristics
of complex anion in the structure II and agree with

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

 SYNTHESIS AND STRUCTURE OF DOUBLE COMPLEX SALTS
0 b
c
a
(a)
Fig. 2. The general view of crystal structure of [Pd(Dien)Cl][AuCl4] (a) and formation of dimer from cations (b). Dashed lines
show Au⋅⋅⋅Cl, Pd⋅⋅⋅Cl, and Cl⋅⋅⋅Cl contacts.
those reported in the literature [17, 22]. Gold anions
in structure III, like palladium cations, come close
due to Au⋅⋅⋅Br (3.583 Å) supplementary contacts and
produce centrosymmetrical dimeric associates with
Au⋅⋅⋅Au distance of 4.132 Å. The bromine atoms of the
anions mutually supplement gold coordination to
pyramidal (4 + 1). Let us note that this type of dimer
ization of complex anions with Au⋅⋅⋅Au distance of
4.137 Å was revealed, for example, in DCS
[Co(En)3][AuBr4]2Br [22]. There are Br⋅⋅⋅Br noncova
lent contacts of 3.62 Å between neighboring [AuBr4]–
anions in the structure of III, which are shorter than
the double value of the van der Waals radius of Br atom
(3.80 Å) [36]. Such short contacts in anionic layers
were found in other DCS containing [AuBr4]– anion:
3.51 Å in [Co(NH3)6][AuBr4]Br2 [17], 3.48 Å in
[Co(En)3][AuBr4]2Br [22], 3.81 Å in
[Rh(NH3)5Br][AuBr4]2 ⋅ H2O [23].
The complex cation [Pd(Dien)Br]+ of structure III
involves coordination node (PdN3Br) as a distorted
square. Valence angles at the Pd atom differ from ideal
value of 90° by no more than 6.7°. The Pd–Br bond
(2.393 Å) is slightly shorter than the bond in [PdBr4]2–
(2.427 Å) [41]. The average Pd–N distance to the ter
minal nitrogen atoms in III is 2.040 Å, the distance to
the central nitrogen atom is 2.013 Å. The fivemem
bered chelate rings of Dien ligand are nonflat and have
a gauche conformation. The length of N–C bonds var
ies in the range 1.46–1.62 Å, average C–C distance is
1.42 Å. The bromine atoms of the cations mutually
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
839
(b)
supplement the coordination of Pd (Pd⋅⋅⋅Br 3.800 Å),
therefore the cations come close and produce cen
trosymmetrical dimeric associates with Pd⋅⋅⋅Pd dis
tance of 4.377 Å. Palladium coordination is supple
mented to distorted octahedral by Br atom of the gold
anion (Pd⋅⋅⋅Br 3.478 Å). Figure 4 shows the general
view of crystal structure of compound III and the
organization of dimeric associates of complex anions
in the structure.
Along with the supplementary contacts described
above, the complex anions in the studied DCS are
united by weak hydrogen bonds of type N–H⋅⋅⋅X and
C–H⋅⋅⋅X, the shortest assessed N–X and C–X dis
tances are 3.16 and 3.67 Å, respectively.
Since no structural data for initial complex IV were
available, we determined its structure. It is built of
[Pd(Dien)Cl]+ complex cations and outersphere Cl–
anions. Figure 5 shows the structure of cation IV and
the projection of the structure along the y axis. In the
complex cation, Pd atom coordinates three nitrogen
atoms of tridentate chelating Dien ligand and a Cl
atom to form PdN3Cl coordination node as a distorted
square. The valence angles at central Pd atoms differ
from ideal 90° by not more than 6.5°, Pd–Cl distance
is 2.342 Å. The lengths of Pd–N bonds to terminal
nitrogen atoms (2.046 Å) are 0.06 Å longer than to the
central N atom (1.989 Å). The lengths of N–C and C–
C bonds have normal values (1.492 and 1.509 Å on
average). The two fivemembered chelate rings formed
by Dien ligand are nonflat and have a gauche confor
Vol. 60 No. 7 2015
840 MAKOTCHENKO et al.

0 c

(a) (b)

Fig. 3. The general view of crystal structure of [Pd(Dien)Cl][AuBr4] (a) and connection of complex cations in crystal (b). Dashed
lines show Au⋅⋅⋅Cl, Au⋅⋅⋅Br, and Pd⋅⋅⋅Br supplementary contacts and N–H⋅⋅⋅Cl hydrogen bonds.

0 b

(a) (b)

Fig. 4. The general view of crystal structure of [Pd(Dien)Br][AuBr4] (a) and organization of dimeric associates from complex ions (b).
Dashed lines show Au⋅⋅⋅Br, Pd⋅⋅⋅Br, and Br⋅⋅⋅Br supplementary contacts and H–N⋅⋅⋅Br hydrogen bonds.

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

 SYNTHESIS AND STRUCTURE OF DOUBLE COMPLEX SALTS
C(2) C(3)
N(2)
C(1) C(4)
N(3)
N(1) Pd(1)
Cl(1)
(a)
Fig. 5. The structure of constitutional units with atom numbering (a) and projection along the y axis (b) for [Pd(Dien)Cl]Cl.
mation. The latter may include two forms that differ
only in the orientation of carbon atoms in the chelate
ring: symmetrical and asymmetrical. The obtained data
indicates the symmetrical arrangement of carbon atoms
in the coordinated diethylenetriamine molecule.
In the structure of compound IV, the flat palladium
coordination is supplemented to bipyramidal (4 + 1 + 1)
by weak contacts: Cl atom from one side and the
H atoms of neighboring complex cations from the
other side. The Pd⋅⋅⋅Cl and Pd⋅⋅⋅H distances equal to
3.868 and ~2.9 Å, respectively. Owing to these con
tacts, the complex cations are packed along the mon
oclinity axis into stacks with Pd⋅⋅⋅Pd distance equal to
translation b = 4.823 Å. The outersphere chloride
anions connect the palladium complex cations via
N⎯H⋅⋅⋅Cl hydrogen bonds (N⋅⋅⋅Cl 3.26 and 3.38 Å).
Each palladium complex cation is surrounded by six
Cl– anions at Pd⋅⋅⋅Cl distances of 4.555–6.116 Å. Let
us note that the crystallographic data for complex IV
are close to those for [Pt(Dien)Br]Br (V) [42].
The analysis of IR spectra of the obtained DCS in
the range 4000–600 cm–1 showed that the spectra of I
and II are similar to that of IV, while the spectrum of
III is similar to that of V reported in [43]. There is a
slight highfrequency shift of bands of stretching
vibrations ν(NH2) and ν(NH) as compared with the
spectrum of the initial complex. The longwavelength
region of spectrum of compound I (600–100 cm–1)
displays bands at 354, 328, and 512 cm–1, which
according to the literature data [43, 44] should be
referred to the stretching vibrations ν(Au–Cl),
ν(Pd⎯Cl), and ν(Pd–N), respectively. In the spec
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
841
c
0
(b)
trum of complex II, the bands at 248, 331, and
519 cm–1 can be assigned to the stretching vibrations
ν(Au–Br), ν(Pd–Cl), and ν(Pd–N), respectively. The
lack of band typical for Au–Cl in the spectrum of
compound II indicates that no gold(III) mixed chloro
bromo complexes are present in the sample. The spec
trum of compound III shows the bands of stretching
vibrations of Au–Br and Pd–Br bonds as a wide band
with maximum at 246.5 cm–1 and inflection at
253 cm–1 (the bands of stretching vibrations of Au–Br
and Pd–Br bonds seems to overlap with each other),
while the band at 507 cm–1 should be assigned to
ν(Pd–N). IR and Raman spectra of DCS
[Co(NH3)6][AuX4]X2 (X = Cl–, Br–) [17],
[Rh(NH3)5Cl][PdCl4] ⋅ H2O [40] were studied previ
ously to confirm the supplementary coordination of
halide ions to the square complexes of gold(III) and
palladium(II). But no pronounced spectral evidence
of supplementary coordination to gold and palladium
was revealed on account of weak interactions.
Thus, we prepared three new double complex salts
by reacting [PdDienCl]+ with [AuX4]–, the structure
of the salts differs. The structures are stabilized by sup
plementary interactions between the complex cations
and anions. The general feature of structures I, II, and
III is the presence of supplementary contacts of the
central atoms of cation and anion with halide ions,
which causes the coordination number of gold and
palladium atoms to become >4. Moreover, DCS struc
tures involve short contacts Cl⋅⋅⋅Cl, Br⋅⋅⋅Br, and weak
hydrogen bonds, which play an important role in the
formation of solid phases.
Vol. 60 No. 7 2015
842 MAKOTCHENKO et al.
REFERENCES
1. B. Michelot, A. Ouali, M.J. Blais, et al., New J. Chem.
12, 293 (1988).
2. A. M. Bol’shakov, V. V. Lapkin, L. D. Bol’shakova,
et al., Zh. Neorg. Khim. 39, 1464 (1994).
3. E. M. Churakova, S. D. Badmaev, P. V. Snytnikov, et al.,
Kinet. Catal. 51, 893 (2010).
4. R. V. Gulyaev, L. S. Kibis, O. A. Stonkus, et al.,
J. Struct. Chem. 52, 126 (2011).
5. D. I. Potemkin, E. Yu. Filatov, A. V. Zadesenets, et al.,
Chem. Eng. J. 207–208, 683 (2012).
6. M. Haruta, Gold Bull. 37, 27 (2004).
7. Z. Ma and S. Dai, Nano Res. 4, 3 (2011).
8. N. W. Alcock, Adv. Inorg. Chem. Radiochem. 15, 2
(1972).
9. Modern Supramolecular Gold Chemistry, Ed. by
A. Laguna, (WileyVCH, Weinheim, 2008).
10. H.N. Adams and J. Strahle, Z. Anorg. Allg. Chem.
485, 65 (1982).
11. G. Marangoni, B. Pitteri, V. Bertolasi, et al., J. Chem.
Soc., Dalton Trans., No. 9, 2235 (1987).
12. L. Kh. Minacheva, A. Sh. Gladkaya, V. G. Sakharova,
et al., Zh. Neorg. Khim. 33, 683 (1988).
13. I. A. Baidina, E. V. Makotchenko, E. A. Shusharina,
et al., J. Struct. Chem. 51, 526 (2010).
14. E. V. Makotchenko, I. A. Baidina, and L. A. Sheludya
kova, Russ. J. Inorg. Chem. 56, 713 (2011).
15. E. V. Makotchenko and I. A. Baidina, J. Struct. Chem.
52, 556 (2011).
16. Puddephatt, R.J., The Chemistry of Gold, (Elsevier,
Amsterdam, 1978).
17. E. V. Makotchenko, I. A. Baidina, and P. E. Plyusnin,
J. Struct. Chem. 48, 276 (2007).
18. E. V. Makotchenko, I. A. Baidina, and D. Yu. Naumov,
Zh. Strukt. Khim. 47, 512 (2006).
19. P. E. Plyusnin, I. A. Baidina, Yu. V. Shubin, and
S. V. Korenev, Russ. J. Inorg. Chem. 50, 1834 (2005).
20. P. E. Plyusnin, I. A. Baidina, Yu. V. Shubin, and
S. V. Korenev, Russ. J. Inorg. Chem. 53, 1724 (2008).
21. P. E. Plyusnin, I. A. Baidina, Yu. V. Shubin, and
S. V. Korenev, Russ. J. Inorg. Chem. 52, 371 (2007).
22. I. A. Baidina and E. V. Makotchenko, J. Struct. Chem.
51, 187 (2010).
23. P. E. Plyusnin, E. Yu. Semitut, I. A. Baidina, and
S. V. Korenev, J. Struct. Chem. 52, 383 (2011).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
24. E. Semitut, P. Plyusnin, I. Baidina, et al., Acta Crystal
logr., Sect. A: Found. Crystallogr. 67, 715 (2011).
25. F. Basolo, H. B. Gray, and R. G. Person, J. Am. Chem.
Soc. 82, 4200 (1960).
26. Gmelins Handbuch der anorganischen Chemie, 8
Aufl., Gold System 62, (Verlag Chemie, Weinheim,
1959), p. 732.
27. G. Nardin, L. Randaccio, G. Annibale, et al., J. Chem.
Soc., Dalton Trans., No. 2, 220 (1980).
28. Synthesis of Platinum Group Metal Complexes, Ed. by
I. I. Chernyaev (Nauka, Moscow, 1964) [in Russian].
29. G. M. Sheldrick, SHELX97, Release 971. Univ. of
Göttingen, Germany, 1999.
30. E. V. Makotchenko and I. A. Baidina, Koord. Khim. 35
(3), 210 (2009).
ˆ ˆ
31. Z. D. Bugarcic, D. M. Jancic, A. A. Shoukry, and
M. M. Shoukry, Monatsh. Chem. 135, 151 (2004).
32. L. Carlsson and G. Lundgren, Acta Chem. Scand. 21,
819 (1967).
33. H. Chateau, M. Gadet, and J. Pouradier, J. Chim.
Phys. Phys.Chim. Biol. 63, 269 (1966).
34. L. I. Elding and A.B. Groning, Acta Chem. Scand.
32A, 867 (1978).
35. E. V. Makotchenko, I. A. Baidina, and I. V. Korol’kov,
J. Struct. Chem. 55, 887 (2014).
36. S. S. Batsanov, Zh. Neorg. Khim. 36, 3015 (1991).
ˆ
37. Z. D. Bugarcic, G. Liehr, and R. van Eldik, J. Chem.
Soc., Dalton Trans., 951 (2002).
38. M. G. B. Drew, M. J. Riedl, and J. Rodgers, J. Chem.
Soc., Dalton Trans., 234 (1972).
39. N. BrescianiPahor, M. Calligaris, and L. Randaccio,
J. Chem. Soc., Dalton Trans., 725 (1976).
40. S. V. Korenev, Yu. V. Shubin, S. A. Gromilov, et al.,
Zh. Strukt. Khim. 43, 693 (2002).
41. A. V. Zadesenets, A. B. Venediktov, S. V. Korenev, et al.,
Zh. Strukt. Khim. 46, 1133 (2005).
42. R. Melanson, J. Hubert, and F. D. Rochon, Can. J.
Chem. 53, 1139 (1975).
43. G. W. Watt and D. S. Klett, Spectrochim. Acta 20, 1053
(1964).
44. Nakamoto, K. Infrared and Raman Spectra of Inorganic
and Coordination Compounds (Interscience, New York,
1986).
Translated by I. Kudryavtsev
Vol. 60 No. 7 2015