Synthesis, structure, and catalytic activity of complexes of 1,1′-bisisoquinoline with PdCl2 and NiCl2

Article abstract of DOI:10.1007/s11172-014-0524-8

New complexes of 1,1′-bisisoquinoline with PdCl₂ and NiCl₂ were synthesized. The structures of the complexes were established by X-ray diffraction. The Pd^II complex acts as a catalyst for the Suzuki and Heck reactions and the hydroarylation of norbornene. As exemplified by the Suzuki reaction, the Ni^II complex can also be used as a catalyst.

Full text of DOI:10.1007/s11172-014-0524-8

Russian Chemical Bulletin, International Edition, Vol. 63, No. 4, pp. 883—889, April, 2014
883
Synthesis, structure, and catalytic activity of complexes
of 1,1´ꢀbisisoquinoline with PdCl2 and NiCl2*
N. S. Khrushcheva, L. A. Bulygina, Z. A. Starikova,† and V. I. Sokolov
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: stemos@ineos.ac.ru
New complexes of 1,1´ꢀbisisoquinoline with PdCl2 and NiCl2 were synthesized. The strucꢀ
tures of the complexes were established by Xꢀray diffraction. The PdII complex acts as a catalyst
for the Suzuki and Heck reactions and the hydroarylation of norbornene. As exemplified by the
Suzuki reaction, the NiII complex can also be used as a catalyst.
Key words: 1,1´ꢀbisisoquinoline, PdII complex, NiII complex, structure, axial chirality,
metal catalysis, Suzuki reaction, Heck reaction.
In molecules of the bisꢀaryl family, two aryl groups are
related by a structural axis, which, in the presence of cerꢀ
tain substituents, can be transformed into a chiral axis and
result in the existence of two enantiomers of the molecule.
In simple models, rotation about the axis is rather free, but
the rotational energy increases with increasing steric hinꢀ
drance, thus providing the optical activity even at room
temperature. The wellꢀknown example of bisꢀaryls is 1,1´ꢀbiꢀ
naphthyl; its derivatives are widely used in the enantioꢀ
selective synthesis.1 The replacement of two carbon atoms
in binaphthyl by nitrogen atoms affords the related heteroꢀ
cyclic structure, 1,1´ꢀbisisoquinoline (biq, 1). The latter is
the structural analog of ,ꢀbipyridine, the derivatives of
which form numerous metal organic complexes, includꢀ
ing complexes with NiCl2 and PdCl2.2 The chiral and
complexꢀforming properties of compound 1 and its derivꢀ
atives are much less studied than the corresponding propꢀ
erties of their structural analogs. In most of the known
metal complexes with platinum,3 ruthenium,4 iron,5 and
silver,6 1,1´ꢀbisisoquinoline acts as a bidentate ligand.
Nevertheless, compound 1 acts as a monodentate bridging
ligand at least in one complex, viz., in a complex with
palladium.7
In the present study, we report on the synthesis and
structures of the complexes of 1,1´ꢀbisisoquinoline 1 with
PdCl2 (2) and NiCl2 (3) (Scheme 1). The structures of
these two complexes are substantially different. In comꢀ
plex 2, like in the complex described earlier,3 1,1´ꢀbisisoꢀ
quinoline is the only bidentate ligand. Complex 3 includes
two ligand molecules. To the best of our knowledge, comꢀ
plexes with other metals having such structure have not
been described earlier.
We also investigated the catalytic activity of complex 2
in the Suzuki and Heck reactions and in the hydroarylaꢀ
Scheme 1
Reagents and conditions: i. [Pd(CN)2]Cl2, CH2Cl2, 21 C; ii. NiCl2•6 H2O, nꢀbutanol, 120 C.
* According to the materials of the International Conference "Organometallic and Coordination Chemistry: Fundamental and Apꢀ
plied Aspects" (September 1—7, 2013, Nizhny Novgorod).
† Deceased.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0883—0889, April, 2014.
1066ꢀ5285/14/6304ꢀ0883 © 2014 Springer Science+Business Media, Inc.

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Khrushcheva et al.
plex. A sample suitable for Xꢀray diffraction was obtained
by the crystallization from CHCl3.
The molecular structures of the complexes (biq)•PdCl2
(2) and (biq)2•NiCl2 (3) are shown in Figs 1 and 2, reꢀ
spectively.
The crystal of 2 contains two independent molecules,
A and B, which slightly differ only by the rotation of the
isoquinoline (quin) moieties (Fig. 3).
C(4)
C(2)
C(3)
C(5)
C(6)
C(1)
N(1)
C(8)
C(7)
Cl(1)
C(9)
Pd(1)
The coordination square {PdCl2N2} is weakly distortꢀ
ed. Principal geometric parameters of the molecules 2A
and 2B are given in Table 1.
C(10)
C(11)
C(15)
N(2)
C(12)
C(13)
The coordination octahedron {NiN4Cl2} is formed by
two chlorine atoms in cis positions and two bidentate biq
ligands. Selected geometric parameters of complex 3 are
given in Table 2.
Cl(2)
C(18)
C(16)
C(17)
C(14)
The Ni atom is displaced from the coordination plane
passing through the atoms N(1), N(2), N(3), and Cl(2) by
0.14 Å toward the Cl(1) atom. The axial bonds Ni—Cl(1) and
Ni—N(4) are longer than the equatorial bonds Ni—Cl(2),
Ni—N(1), Ni—N(2), and Ni—N(3). The Ni—N bonds in
the transꢀCl—Ni—N groups are elongated compared to
the bonds in the transꢀN—Ni—N groups. This can be
attributed to the trans effect of the chlorine atoms.
The structure of the biq ligand (L) in complex 2 is
similar to that in complex 3. In both complexes, the molꢀ
ecule has a twist conformation, in which the quinoline
moieties are bent in the opposite directions with respect to the
central Cquin—Cquin bond. The N—Cquin—Cquin—N diheꢀ
dral angles between the quin planes are 27.6(4) and 22.5(4)
(for 2A and 2B, respectively), 40(1) and 37(1) (for L1 and
L2 in structure 3). Each bicyclic system of quin is nonplaꢀ
nar. The dihedral angles between the phenyl and pyridine
rings are 9.1 (2A), 8.3 (2B), 9.1, 11.7 (L1), 8.3, 9.2
(L2). Selected geometric parameters are given in Table 3.
An analysis of the data listed in Table 3 shows that the
length of the central Cquin—Cquin bond (1.47—1.50 Å) is
substantially larger than the value characteristic of the
"nonconjugated" Csp2—Csp2 bond (1.455 Å). This is indicꢀ
Fig. 1. Structure of one independent molecule, 2A; the atoms
are represented by thermal ellipsoids at p = 50%.
tion of norbornene and examined the possibility of using
nickel complex 3 as a catalyst.
Palladium complex 2 was synthesized by the reaction
of compound 1 with bis(acetonitrile)palladium dichloride at
room temperature in CH2Cl2 (see Scheme 1). Complex 2
was isolated from the reaction mixture and characterized
by 1H NMR spectroscopy and microanalysis. In the NMR
spectrum of complex 2, all protons are shifted downfield
compared to the signals of the starting 1,1´ꢀbisisoquinoꢀ
line, which is indicative of the shift of the electron density
from the ligand to the metal atom. In order to prepare
a sample suitable for Xꢀray diffraction, complex 2 was
crystallized from MeCN.
Nickel complex 3 was synthesized by refluxing a mixꢀ
ture of compound 1 and hydrate NiCl2• 6 H2O in nꢀbutꢀ
anol and was characterized by microanalysis. Unforꢀ
tunately, we failed to measure the H NMR spectrum of
complex 3 because of strong paramagnetism of this comꢀ
1
C(141)
C(151)
C(52)
C(131)
C(161)
C(62)
C(42)
C(171)
C(181)
C(121)
C(111)
C(72)
C(32)
C(61)
C(71)
N(2)
C(101)
C(82)
C(22)
C(51)
C(12)
C(81)
C(92)
C(102)
C(91)
Cl(1)
N(4)
C(112)
C(122)
C(132)
C(41)
C(31)
N(3)
Ni(1)
N(1)
C(182)
C(172)
C(162)
C(21)
C(11)
C(152)
C(142)
Cl(2)
Fig. 2. Molecular structure of 3; the atoms are represented by thermal ellipsoids at p = 50%.

NiCl2 and PdCl2 complexes of 1,1ꢀbiisoquinoline
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 4, April, 2014
885
Table 1. Selected bond lengths (d), bond angles (), and torsion
angles () in the molecules 2A and 2B
Cl(2)
Cl(2A)
Cl(1)
Cl(1A)
Parameter
Bond
2A
2B
Pd(2)
Pd(1A)
C(18)
N(2A)
d/Å
N(1)
Pd—Cl(1)
Pd—Cl(2)
Pd—N(1)
Pd—N(2)
Bond angle
2.286(1)
2.289(1)
2.024(3)
2.025(3)
2.290(1)
2.2709(9)
2.025(3)
2.026(3)
C(18A)
N(2)
N(1A)
C(1A)
C(2A)
C(17)
C(10A)
C(10)
C(1)
C(2)
C(8A)
C(9A)
C(17A)
/deg
C(9)
C(16)
C(3A)
C(4A)
C(16A)
C(15A)
C(11A)
C(8)
N(1)—Pd—N(2)
Cl(1)—Pd—Cl(2)
Cl(1)—Pd—N(1)
Cl(2)—Pd—N(2)
Torsion angle
80.1(1)
80.4(1)
C(3)
C(7A)
C(6A)
C(11)
89.95(4)
95.41(9)
94.68(9)
90.77(4)
95.19(9)
93.90(9)
C(12)
C(4)
C(5A)
C(15)
C(13)
C(7)
C(12A)
/deg
C(14A)
C(6)
C(5)
C(13A)
С(8)—С(9)—С(10)—С(11)
N(1)—C(9)—C(10)—N(2)
–28.4(6)
–22.5
36.3(6)
27.6
C(14)
Fig. 3. Comparison of the structures of two independent moleꢀ
cules A and B in structure 2.
Table 2. Geometric parameters of the coordination sphere of the
Ni atom in complex 3
Since the crystal structures of 2 and 3 belong to the
centrosymmetric space group (P21/c), each structure conꢀ
tains a racemic mixture of two enantiomers.
Parameter
Bond
Value
Parameter
Bond
Value
d/Å
d/Å
The structure of complex 2 is similar to that of the
isostructural complex (biq)PtCl2 described earlier,3 in
which the angle of rotation of the quin moieties about the
central bond is 35.18 and 41.12 in two independent moleꢀ
cules. The authors of the cited study considered this fact
as a principal difference between the structures of two
independent molecules (dimorphism), although this conꢀ
clusion is hardly justified.
First, this difference in the angle of rotation of the quin
moieties in the molecules L is, on the whole, insignificant
and can be due to the different character of thermal vibraꢀ
tions of the molecules.
Ni—Cl(1)
Ni—N(1)
Ni—N(2)
2.423(2)
2.094(7)
2.115(7)
Ni—Cl(2)
Ni—N3
Ni—N4
2.346(2)
2.023(6)
2.230(7)
Bond angle
/deg
Bond angle
/deg
N(1)—Ni—N(3) 166.5(3)
N(2)—Ni—N(3)
N(4)—Ni—N(3)
N(2)—Ni—N(4)
N(3)—Ni—Cl(1)
N(3)—Ni—Cl(2)
98.5(3)
75.9(2)
83.4(2)
93.4(2)
90.9(2)
N(1)—Ni—N(2)
N(1)—Ni—N(4)
N(1)—Ni—Cl(1)
N(1)—Ni—Cl(2)
N(2)—Ni—Cl(1)
78.7(3)
90.7(3)
99.3(2)
91.5(2)
83.2(2)
N(4)—Ni—Cl(1) 161.3(2)
N(4)—Ni—Cl(2) 96.0(2)
N(2)—Ni—Cl(2) 170.1(2)
Second, this difference can be attributed to the packꢀ
ing effects of the molecules in the crystal, i.e., to the difꢀ
ference in the intermolecular contacts in the structure.
Thus, the Pd(1) atom in the molecule 2A of complex 2
ative of the absence of the  conjugation between the aroꢀ
matic systems. The other bond lengths have typical values.
Table 3. Selected bond lengths (d) and bond angles () in the biq ligand of molecules 2 and 3
PdCl2(L) (2)
2A
NiCl2(L)2CHCl3 (3)
Parameter
NiCl2(L)2CHCl3 (3)
Parameter
Parameter
Bond
2B
L1
L2
d/Å
Bond
d/Å
Bond
d/Å
N(1)—C(1)
N(1)—C(9)
N(2)—C(10)
N(2)—C(18)
C(9)—C(10)
1.357(5)
1.346(5)
1.343(5)
1.366(5)
1.482(5)
1.360(5)
1.340(5)
1.343(5)
1.360(5)
1.486(5)
N(1)—C(11)
N(1)—C(91)
N(2)—C(101)
N(2)—C(181)
C(91)—C(101)
1.35(1)
1.36(1)
1.30(1)
1.32(1)
1.47(1)
N(3)—C(102)
N(3)—C(182)
N(4)—C(92)
N(4)—C(12)
C(92)—C(102)
1.310(9)
1.42(1)
1.306(9)
1.35(1)
1.50(1)
Angle
/deg
120.3(3)
120.3(3)
Angle
/deg
Angle
/deg
C(1)—N(1)—C(9)
C(10)—N(2)—C(18) 120.2(3)
120.5(3)
С(11)—N(1)—C(91)
С(101)—N(2)—C(181) 120.9(7)
117.8(7)
С(12)—N(4)—C(92)
С(102)—N(3)—C(182) 116.5(7)
119.2(7)

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Khrushcheva et al.
C(6)
C(7)
N(2)
C(9)
C(17)
C(5)
C(8)
C(4)
C(14)
C(18)
C(16)
H(18A)
Pd(1)
C(3)
C(13)
Cl(2)
Cl(1)
N(1)
C(2)
C(12)
C(1)
C(11)
H(5AB)
C(5AA)
N(1AA)
N(2AA)
Pd(2A)
Cl(1B)
Fig. 4. Agostic Pd(1)...H interaction between the molecules 2A and 2B in structure 2.
Cl(2B)
forms an agostic intermolecular contact with the hydroꢀ
gen atom H(5) of the molecule 2B (3.02 Å) (Fig. 4), whereꢀ
as the Pd(2) atom of the molecule 2B is not involved in
such contacts.
In addition, the molecules 2A and 2B are linked toꢀ
gether to form dimeric associates via weak —ꢀstacking
interactions between the parallel phenyl rings (3.47 Å).
The shortest distances between atoms are shown in Fig. 5.
C(5) C(6)
C(7)
C(4)
C(3)
C(8)
N(1)
C(2)
C(9)
Pd(1)
N(2)
C(16)
C(1)
Cl(2A)
Cl(1)
C(10)
C(12)
Cl(2)
C(15)
C(14)
C(13)
Cl(1A)
H(5a´)
Pd(2)
C(7A)
C(8A)
C(6A)
N(1A)
C(3A)
C(5A)
C(4A)
Fig. 5. — Stacking interaction and the formation of the dimeric associate 2A...2B of two independent molecules in structure 2.

NiCl2 and PdCl2 complexes of 1,1ꢀbiisoquinoline
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 4, April, 2014
887
Scheme 2
Only one quin moiety of each independent molecule is
involved in this interaction. The different character of inꢀ
teratomic interactions of two halves of the biq ligand in
the crystal results in the different angles of rotation of the
quin rings about the central Cquin—Cquin bond in the molꢀ
ecules 2A and 2B.
It is impossible to analyze intermolecular interactions
in structure 3 because the solvent molecules, the chlorine
atoms of which may play an important structureꢀforming
role, were not localized. Nevertheless, in structure 3, like
in structure 2, only a half of the biq ligand is involved in
a weak —ꢀstacking interaction between the parallel
phenyl rings (3.37—3.50 Å). Figure 6 displays the interꢀ
molecular dimer formed by complex 3 along with the
shortest intermolecular contacts.
Therefore, the local —ꢀstacking interaction, in which
only a half of the molecule is involved, and the agostic
Pd(1)...H interaction are responsible for the difference in
the angle of rotation of the two halves of the biq ligands in
molecules 2 and 3. In addition, the chlorine atoms of both
molecules in structures 2 and 3 are involved in different
numbers of intermolecular Cl...H contacts shortened comꢀ
pared with the sum of the van der Waals contacts (2.97 Å).
For example, the chlorine atoms form contacts between
the layers in the layered structure of 2 (Fig. 7).
The catalytic potential of complex 2 was examined in
the Suzuki (i) and Heck (ii) reactions and the hydroarylaꢀ
tion of norbornene (iii) (Scheme 2, Table 4). In all cases,
the reactions were carried out under the same conditions
as in our earlier studies.8—10 As can be seen from Table 4,
complex 2 efficiently catalyzes the Suzuki reaction, and
the products were obtained in moderate yields both at
room temperature (see Table 4, runs 1 and 2) and upon
Compound
4a, 4d, 5a, 6a, 7d
4b, 5b
Ar
Ph
Compound
4c, 5c
Ar
4ꢀMeO—C6H4
4ꢀMe—C6H4
4ꢀMeCO—C6H4 4e, 7e
Reagents and conditions: i. 2 or 3, PhB(OH)2, K2CO3,
MeOH—H2O, 21 or 55 °C. ii. 2, CH2=CH—CO2Et, K2CO3,
DMF, 130 C. iii. 2, norbornene, HCOOH, Et3N, DMSO,
65 C.
slight heating to 55 C (see Table 4, run 3). However, as
the reaction mixture was heated, a darkening of the reacꢀ
tion mixture and the formation of a black precipitate, apꢀ
parently, of elemental palladium were observed in the Heck
reaction (see Table 4, run 4). The product was obtained in
a low yield. Evidently, complex 2 does not withstand seꢀ
vere conditions of the Heck reaction. The hydroarylation
of norbornene in the presence of 2 takes place efficiently,
and the corresponding products were obtained in fairly
high yields (see Table 4, runs 5 and 6).
The Suzuki reaction in the presence of nickel comꢀ
pounds, the activity of which is comparable with and, in
some cases, even higher than that of palladium catalꢀ
ysts,11,12 was dealt with in many publications. Besides, it
is very attractive that nickel is much cheaper as a metal
C(132)
C(122)
C(42)
C(142)
C(152)
C(22)
C(32)
Cl(2)
C(52)
C(12)
N(4)
Cl(2´)
C(82)
C(62)
C(72)
C(11)
C(21)
C(41)
C(31)
N(1)
C(81)
C(92)
N(3)
Ni(1)
C(182)
C(61)
C(71)
N(4´)
N(1´)
N(3´)
Cl(1´)
C(91)
C(181)
C(102´)
C(112´)
C(132´)
N(2)
Cl(1)
C(101)
C(111)
C(222´)
N(2´)
C(171)
C(121)
C(161)
C(151)
C(131)
C(141)
Fig. 6. — Stacking interaction in structure 3.

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Khrushcheva et al.
a
0
c
b
Fig. 7. Molecular packing in structure 2.
Table 4. Suzuki and Heck reactions and the hydroarylation of norbornene catalyzed by palladium complexes 2 and 3
Run
ArX
Catalyst
Product
Reagents partners
T/С
/h
Yield (%)
1
2
3
4
5
6
7
8
C6H5Br (4a)
4ꢀMeCOꢀC6H4 (4b)
4ꢀMeOꢀC6H4Br (4c)
C6H5Br (4a)
C6H5I (4d)
4ꢀMeꢀC6H4I (4e)
C6H5Br (4a)
2
2
2
2
2
2
3
3
5a
5b
5c
6a
7d
7e
5a
5a
PhB(OH)2
PhB(OH)2
PhB(OH)2
121
121
155
130
165
165
121
155
24
24
15
15
15
15
24
15
63
33
74
21
78
87
—
CH2=CHCOOEt
Norbornene
Norbornene
PhB(OH)2
C6H5Br (4a)
PhB(OH)2
80
N, 5.44. C18H12N2PdCl2•CH2Cl2. Calculated (%): C, 44.07;
H, 2.71; N, 5.41. Samples suitable for Xꢀray diffraction were
prepared by crystallizing complex 2 from CH3CN.
catalyst. Using the Suzuki reaction as an example, we
showed that complex 3 also can catalyze the C—C bond
formation. Although we failed to obtain the reaction prodꢀ
uct at room temperature (see Table 4, run 7), this product
was prepared in a good yield in the reaction performed at
55 C (see Table 4, run 8).
Di[(N,N)ꢀ1,1´ꢀbis(isoquinoline)]nickel dichloride, (biq)2NiCl2
(3). A mixture of compound 1 (0.54 g, 2.1 mmol) and NiCl2•6
H2O (0.45 g, 1.9 mmol) in nꢀbutanol (15 mL) was refluxed for
8 h, cooled, concentrated, and chromatographed on silica gel
((1) EtOAc; (2) CHCl3 : MeOH = 9 : 1). Complex 3 was obtainꢀ
ed as yellowꢀgreen powder in a yield of 0.49 g (67%). Found (%):
C, 57.26; H, 3.32; N, 7.60; Ni, 6.90. C36H24N4NiCl2•1.1 CHCl3.
Calculated (%): C, 57.61; H, 3.27; N, 7.24; Ni, 7.59. Samples
suitable for Xꢀray diffraction were prepared by crystallizing comꢀ
plex 3 from CHCl3.
Reaction of phenylboronic acid with aryl bromides (Suzuki
reaction). Phenylboronic acid (3 mmol), the corresponding ArBr
(2 mmol), and potassium carbonate (4 mmol) were added with
stirring to MeOH (8 mL) and water (4 mL). The mixture was
stirred for 5 min, and then 0.5 mol.% catalyst 2 or 3 was added.
The reaction mixture was stirred at room temperature overnight,
heated at 55 C for 5 h, diluted with water, extracted with diethyl
ether, dried with Na2SO4, concentrated, and chromatographed
on silica gel (hexane : CHCl3 = 9 : 1). The yields of products
5a—c are given in Table 4.
Experimental
The 1H NMR spectra were recorded on a Bruker instrument
(300 MHz). 1,1´ꢀBisisoquinoline (1) was synthesized according
to a known procedure.13
(N,N)ꢀ1,1´ꢀBis(isoquinoline)palladium dichloride, (biq)PdCl2 (2).
A solution of PdCl2(CH3CN)2 (0.52 g, 2 mmol) in CH2Cl2 (10 mL)
was added with stirring to a solution of compound 1 (0.50 g, 2 mmol)
in CH2Cl2 (30 mL). The reaction mixture was stirred for 1 h. Then
pentane (100 mL) was added, and the precipitate that formed
was filtered off and dried. Complex 2 was obtained as redꢀorange
crystals in a yield of 0.93 g (90%). 1H NMR (CD3CN), : 9.32—9.34
(m, 2 H); 8.24—8.29 (m, 4 H); 8.01—8.07 (m, 2 H); 7.90—7.93
(m, 2 H); 7.67—7.73 (m, 2 H). Found (%): C, 43.81; H, 2.77;

NiCl2 and PdCl2 complexes of 1,1ꢀbiisoquinoline
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 4, April, 2014
889
Reaction of ethyl acrylate with benzyl bromide (Heck reacꢀ
tion). Catalyst 2 (0.2 mol.%, 0.0061 g) was added to a mixture of
bromobenzene (0.62 mL, 5.9 mmol), ethyl acrylate (0.96 mL,
8.9 mmol), and K2CO3 (1.63 g, 11.8 mmol) in DMF (10 mL).
The reaction mixture was stirred at 140 C for 5 h, cooled, dilutꢀ
ed with water, extracted with diethyl ether, washed with water,
dried with sodium sulfate, concentrated, and chromatographed
on silica gel (hexane : EtOAc). Complex 6а was obtained in
a yield of 0.22 g (21%).
Reaction of norbornene with aryl iodides (hydroarylation).
Catalyst 2 (0.5 mol.%) was added to a solution of norbornene
(3.4 mmol), aryl iodide (0.92 mmol), formic acid (3 mmol), and
Et3N (3.8 mmol) in DMSO (5 mL). The reaction mixture was
stirred at 65 C for 5 h, cooled, diluted with water, extracted with
diethyl ether, washed with water, dried with sodium sulfate, conꢀ
centrated, and chromatographed on silica gel (hexane). The
yields of products 7d and 7e are given in Table 4.
ponents, which are related by a rotation of 179.9 about the c axis.
The data were corrected for absorption  using the TWINABS
program.14
In structure 3, there are cavities filled by highly disordered
solvent (CHCl3) molecules, which were not localized; the numꢀ
ber of such molecules was determined using the SQUEEZE/
PLATON program.
The structures were solved by direct methods. All nonhydroꢀ
gen atoms were located in difference electron density maps and
refined based on F2 with anisotropic displacement parameꢀ
hkl
ters. All hydrogen atoms were geometrically positioned and reꢀ
fined using a riding model with U(H) = 1.2 U(C), where U(C) is
the equivalent thermal parameter of the carbon atom, to which
the corresponding H atom is attached. All calculations were
carried our using the SHELXTL program package.15
Main crystallographic data and the Xꢀray diffraction data
collection and refinement statistics for complexes 2 and 3 are given
in Table 5. Complete tables of atomic coordinates, bond lengths,
bond angles, and anisotropic thermal displacement parameters
were deposited in the Cambridge Crystallographic Data Centre
(CCDC 872919 and 908930 for complexes 2 and 3, respectively).
Xꢀray diffraction study of complexes 2 and 3 was performed
on a Bruker SMART APEX II diffractometer (MoꢀK radiaꢀ
tion, graphite monochromator, ꢀscanning technique; the scan
step was 0.5) at 100 K.
Crystals of complex 2 are twins. The Xꢀray diffraction data set
was indexed using the Cell Now program and divided into two sepꢀ
arate data sets corresponding to individual singleꢀcrystal comꢀ
The present work was financially supported by the Rusꢀ
sian Foundation for Basic Research (Project No. 14ꢀ03ꢀ467).
We thank Dr. A. A. Khodak for providing 1,1´ꢀbisisoꢀ
quinoline.
Table 5. Main crystallographic data and the Xꢀray diffraction
data collection and refinement statistics for compounds 2 and 3
References
Parameter
2
3
1. S. G. Telfer, R. Kuroda, Coord. Chem. Rev., 2003, 242, 33.
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Y. Wang, Polyhedron, 1993, 12, 1201.
4. P. Frediani, C. Giannelli, A. Salvini, S. Ianelli, J. Organoꢀ
met. Chem., 2003, 667, 197.
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Acta, 2012, 386, 93.
7. L.ꢀX. Dai, Z.ꢀH. Zhow, Y.ꢀZ. Zhang, C.ꢀZ. Ni, Z.ꢀM.
Zhang, Y.ꢀF. Zhow, J. Chem. Soc., Chem. Commun., 1987, 1760.
8. V. I. Sokolov, L. A. Bulygina, N. S. Khrushcheva, N. S.
Ikonnikov, Russ. Chem. Bull. (Int. Ed.), 2010, 59, 1400 [Izv.
Akad. Nauk, Ser. Khim., 2010, 1370].
9. L. A. Bulygina, N. S. Khrushcheva, V. I. Sokolov, Russ.
Chem. Bull. (Int. Ed.), 2011, 60, 258 [Izv. Akad. Nauk, Ser.
Khim., 2011, 252].
10. N. S. Khrushcheva, L. A. Bulygina, V. I. Sokolov, Russ.
Chem. Bull. (Int. Ed.), 2010, 61, 1537 [Izv. Akad. Nauk, Ser.
Khim., 2012, 61, 1537].
11. C. Griffiths, N. E. Leadbeater, Tetrahedron Lett., 2000, 41, 2487.
12. C.ꢀC. Lee, W.ꢀC. Ke, K.ꢀT. Chan, C.ꢀL. Lai, C.ꢀH. Hu,
H. M. Lee, Chem. Eur. J., 2007, 13, 582.
PdCl2(biq)
C18H12Cl2N2Pd
433.60
Red, platelets
0.35×0.32×0.18
NiCl2(biq)2•CHCl3
C37H25Cl5N4Ni
761.57
Green, platelets
0.45×0.28×0.10
Molecular formula
Molecular weight
Color, shape
Crystal dimenꢀ
sions/mm
Crystal system
Space group
a/Å
Monoclinic
P21/c
Monoclinic
P21/c
14.449(1)
19.803(2)
11.0495(9)
101.79(2)
3094.8(4)
8
1712
1.861
1.543
15.456(4)
11.193(3)
21.809(4)
122.43(1)
3185(1)
4
1552
1.588
1.065
b/Å
c/Å
/deg
V/Å3
Z
F(000)

calc/g cm–3
/mm–1
Tmin/Tmax
/deg
Number of measured
reflections
0.540/0.767
1.77×30.00
8918
0.014/0.064
2.63×26.00
27835
Number of unique
8813 (0.0611)
8505
6208(0.2367)
2623
reflections (Rint
)
Number of reflections
with I > 2(I)
Number of parameters
in refinement
R1
13. M. T. Ashby, G. N. Govindan, A. K. Grafton, J. Am. Chem.
Soc., 1994, 116, 4801.
14. Bruker (2005). APEX2 Softwarwe Package, Bruker AXS Inc.,
5465, East Cheryl Parkway, Madison, WI 5317.
15. G. M. Sheldrick, Acta Crystallogr., Sect. A, 2008, 64, 112.
415
388
0.0347
0.0939
0.0978
0.1787
wR2
GOOF

1.009
3.118/–1.105
1.015
1.787/–0.687
max/min/e Å–3
Received June 25, 2013