Inclusion complexes of sodium perchlorate into [CuLSS] and [CuLrac]; H2LSS = bis(3-methoxy-2-hydroxy-1- benzylidene)-1S,2S-cyclohexanediamine, H2Lrac = its racemic form

Article abstract of DOI:10.1007/s10847-011-9980-z

Inclusion complexes of LiClO₄ or NaClO₄ into [CuL^SS] or [CuL^rac] are reported, where [CuL^SS] denotes bis(3-methoxy-2-oxy-1-benzylidene)-1S,2S-cyclohexanediaminecopper(II) and [CuL^rac] denot

Full text of DOI:10.1007/s10847-011-9980-z

J Incl Phenom Macrocycl Chem (2011) 71:463–469
DOI 10.1007/s10847-011-9980-z
ORIGINAL ARTICLE
SS
Inclusion complexes of sodium perchlorate into [CuL ]
rac SS
and [CuL ]; H L 5 bis(3-methoxy-2-hydroxy-1-
2
rac
benzylidene)-1S,2S-cyclohexanediamine, H L 5 its
racemic form
2
Takeshi Fujinami
Hirokazu Kawashima
Jack H. Harrowfield
•
Ryuichi Kinoshita
Naohide Matsumoto
Yang Kim
•
•
•
•
Received: 2 April 2011 / Accepted: 29 April 2011 / Published online: 25 May 2011
Ó Springer Science+Business Media B.V. 2011
Abstract Inclusion complexes of LiClO or NaClO into
4
Introduction
4
SS
CuL ] or [CuL ] are reported, where [CuL ] denotes
rac
SS
[
bis(3-methoxy-2-oxy-1-benzylidene)-1S,2S-cyclohexane-
rac
diaminecopper(II) and [CuL ] denotes the racemic com-
Coordination compounds exhibit well-defined stereochem-
istry and hence the compounds can be useful building blocks
for the construction of supramolecular assembly structures
[1, 2]. There are many synthetic strategies for the synthesis
of the functional supramolecular materials. There are many
examples that alkali ion is included into coordination com-
pound to influence the assembly reaction since the studies by
Sinn [3] and Lindoy [4]. We have reported that the alkali ion
plex. The inclusion reaction of LiClO and NaClO into
4
4
SS
SS
[
CuL ] gave the [1 ? 1] adduct of [CuL (H O)LiClO ]
2 4
SS
and the [2 ? 1] adduct of [(CuL ) Na(H O) ]ClO ,
rac
respectively, while that of NaClO into [CuL ] gave the
2
2
3
4
4
rac
SS
[
2 ? 2] adduct of [CuL NaClO ] ꢀCH CN ([(CuL Na
4
2
3
RR
ClO )(CuL NaClO )]ꢀCH CN).
4
4
3
II
III
?
in a p–d–f molecular system of M[(Cu L) Gd ] (M = Na ,
4
?
K , Cs ; H L = N-(4-methyl-6-oxo-3-azahept-4-enyl)
?
Keywords Alkali ion ꢀ Copper ꢀ Chiral coordination
complex ꢀ Crystal structure ꢀ Assembly structure
3
oxamic acid) can affect the assembly structures, in which the
alkali cation plays a role of connector between adjacent
II
(Cu L) Gd ] cores [5]. The sodium and potassium salts
III -
[
4
?
take a 1D chain structure bridged by Na or K ion, while the
?
?
cesium salt takes a cyclic cluster structure bridged by Cs
ion. The result demonstrated that the definitely different
assembly structures can be generated by the selection of the
size of alkali ion.
Chirality often plays a crucial role for the assembly
process. Many examples exist where molecular chirality
influences on the supramolecular stereochemistry of con-
tainers, helical fibers, micelles, bilayers, and crystals [6–10].
The assembly reactions involving chiral coordination com-
pounds have been reported and a number of functional
materials have been generated [6–10]. In our previous papers
Dedicated to Professor Len Lindoy, one of the originators of the field
of chemistry concerned in this article, on the occasion of his 75th
birthday.
T. Fujinami ꢀ R. Kinoshita ꢀ H. Kawashima ꢀ N. Matsumoto (&)
Graduate School of Science and Technology, Kumamoto
University, 2-39-1 Kurokami, Kumamoto 860-8555, Japan
e-mail: naohide@aster.sci.kumamoto-u.ac.jp
[
11, 12], we have examined the selective syntheses of cyclic
J. H. Harrowfield
cluster and one-dimensional chain d–f assembly structures
by introduction of chiral moiety, in which a chiral d-com-
ponent as ‘‘ligand-complex’’ and the f-component with
vacant coordination sites were used for the assembly reac-
tion. The results demonstrated that the chiral modification
is effective to generate the definitely different assembly
structures.
Institut de Science et d’Ing e´ nierie Supramol e´ culaires, Universit e´
de Strasbourg, 8, all e´ e Gaspard Monge, 67083 Strasbourg,
France
Y. Kim
Department of Chemistry and Advanced Materials,
Kosin University, 149-1, Dongsam-dong, Yeongdo-gu,
Busan 606-701, South Korea
123

4
64
J Incl Phenom Macrocycl Chem (2011) 71:463–469
These two examples described above demonstrate that the
mixture was stirred for 30 min at 50 °C, and then cooled to
room temperature. After several hours, fine crystalline
materials precipitated. They were collected by suction fil-
tration, washed with water and small amount of methanol,
and then recrystallized from acetonitrile. Anal. Calcd for
alkali ion and chirality can influence the assembly structures.
In this study, we have examined a simple molecular system
that involves a chiral moiety and suitable site for alkali ion at
the same time. In this study, the assembly reaction of LiClO
4
SS rac
or NaClO and chiral [CuL ] or racemic [CuL ] were
SS
[CuL (H O)]ꢀCH CNꢀH O=C H N O Cu: C, 55.32; H,
4
2
3
2
24 31 3 6
examined, in order to see whether or not the assembly reac-
tions give the definitely different supramolecular structures,
SS
6.00; N, 8.06. Found: C, 55.44; H, 5.85; N, 8.04.
rac
The racemic form [CuL ] was prepared by a similar
SS
where [CuL ] denotes bis(3-methoxy-2-oxy-1-benzylidene)-
method of [CuL ]ꢀCH CN.
3
rac
S,2S-cyclohexanediaminecopper(II) and [CuL ] denotes
1
SS
the racemic form. The assembly reactions of [CuL ] with
SS rac
Adducts of [CuL ] and [CuL ] with LiClO or NaClO
4
4
LiClO4 and NaClO4 gave the [1 ? 1] adduct of
SS SS
CuL (H O)LiClO ] and the [2 ? 1] adduct of [(CuL )
SS
[
[CuL (H O)LiClO ] (1:1 adduct). To a suspension of
2 4
SS
2
4
2-
rac
Na(H O) ]ClO ꢀCH CN, respectively, while that of [CuL ]
[CuL (H O)]ꢀCH CNꢀH O (0.111 g, 0.25 mmol) in a
2
3
4
3
2
3
2
rac
and NaClO gave the [2 ? 2]adductof[CuL NaClO ] . We
mixture of acetonitrile (20 mL) and dichloromethane
(10 mL) was added a solution of lithium perchlorate
(0.027 g, 0.25 mmol) in acetonitrile (1 mL). The mixture
was warmed at 70 °C with stirring for 10 min and filtered.
The filtrate was allowed to stand for a few hours, during
which time dark red, needle-like crystals precipitated.
4
4 2
reportherethesyntheses and crystal structuresofthe inclusion
SS rac
complexes of LiClO or NaClO into [CuL ] and [CuL ].
4
4
Materials and methods
These were collected by suction filtration, then recrystal-
SS
All chemicals and solvents used for the syntheses were
reagent grade and were obtained from Tokyo Kasei Co.,
Ltd. and Wako Co., Ltd. and used without further purifi-
cation. C, H and N elemental analyses were carried out at
the Instrumental Analysis Centre of Kumamoto University.
lized from acetonitrile. Anal. Calcd for [CuL (H O)
2
LiClO ]=C H N O ClCuLi: C, 46.49; H, 4.61; N, 4.93.
4 22 26 2 9
Found: C, 46.86; H, 4.69; N, 5.00.
SS
[(CuL ) Na(H O) ]ClO ꢀ3H O ([2 ? 1] adduct). This
2
2
3
4
2
SS
complex was prepared by mixing [Cu(L )(H O)]ꢀCH CN
2
3
and sodium perchlorate in 1:1 molar ratio in acetonitrile
SS
Synthesis
according to the similar procedure of the [CuL (H O)Li-
SS
2
ClO ]. Anal. Calcd for [(CuL ) Na(H O) ]ClO ꢀ3H O=
4
2
2
3
4
2
SS
Ligands H2L and H2L
rac
C H N O ClCu Naꢀ3H O: C, 47.25; H, 5.41; N, 5.00.
44
54
4
15
2
2
Found: C, 46.78; H, 5.05; N, 5.28.
rac
The two tetradentate Schiff-base ligands bis(3-methoxy-2-
SS
hydroxy-1-benzylidene)-1S,2S-cyclohexanediamine (H L )
[CuNa(L )(ClO )] ꢀCH CN ([2 ? 2] adduct). This com-
4
2
3
rac
plex was prepared by mixing [CuL ] and sodium perchlorate
in 1:1 molar ratio in acetonitrile according to the similar pro-
2
and bis(3-methoxy-2-hydroxy-1-benzylidene)-trans-1,2-cyc-
rac
lohexanediamine (H L ) were prepared according to the
SS
rac
cedure of the [(CuL ) Na(H O) ]ClO ꢀ3H O. [CuL
2
2
2
3
4
2
SS
RR
general synthetic methods described in the literature [13].
Both were obtained as yellow crystalline materials by the
NaClO ] ꢀCH CN=[Cu Na (L )(L )(ClO ) ]ꢀCH CN. Anal.
4
2
3
2
2
4 2
3
rac
Calcd for [CuL NaClO ] ꢀCH CN=C H N O Cl Cu
4
2
3
46 51
5
16
2
2
[
2 ? 1] condensation reactions of 3-methoxysalicylaldehyde
o-vanillin) with either 1S,2S-cyclohexanediamine or trans-
Na :C, 47.06;H, 4.38;N, 5.97. Found: C, 46.86;H, 4.32;N, 5.46.
2
(
1
,2-cyclohexanediamine in methanol, respectively. They
X-ray crystallography
were collected by suction filtration and used directly for the
II
syntheses of the Cu complexes.
Single-crystal X-ray structure determinations were
performed at ambient temperature for the precursor com-
SS
II SS
Cu complexes, [CuL ] and [CuL
rac
]
plex [CuL (H O)]ꢀCH CN as well as the three adducts
2
3
SS
SS
Cu(L )(H O)LiClO ], [(CuL ) Na(H O) ]ClO and [Cu
2 4 2 2 3 4 2
[
II
SS
rac
SS
RR
The Cu complexes [CuL ] and [CuL ] were prepared
by mixing the ligands and copper(II) acetate monohydrate
in methanol in 1:1 molar ratio, according to the general
literature method [13].
Na (L )(L )(ClO ) ]ꢀCH CN. The data were collected on a
2
4 2
3
Rigaku RAXIS RAPID imaging plate diffractometer using
˚
graphite-monochromated Mo Ka radiation (k = 0.71073 A).
All calculations were performed using the Crystal Structure
crystallographic software package [14]. The atomic scattering
factors and anomalous dispersion terms were taken from the
standard compilation. Crystal data and structure refinement
A solution of copper(II) acetate monohydrate (798 mg,
4 mmol) in 20 mL of methanol was added to a solution of
SS
H2L (456 mg, 4 mmol) in 50 mL of methanol. The
1
23

J Incl Phenom Macrocycl Chem (2011) 71:463–469
465
II
Structure of precursor Cu complex
details are given in Table 1, and selected bond lengths and
angles are presented in Table 2.
SS
[CuL (H
O)]ꢀCH
CN
3
2
II
SS
The precursor Cu complex [CuL (H O)]ꢀCH CN crys-
2
3
Results and discussion
tallizes in the noncentrosymmetric monoclinic space group
P2 (no. 4), the asymmetric unit consisting of a complex
1
SS
[CuL (H
Synthesis of the alkali metal ion adducts
2
O)]ꢀCH
CN and one acetonitrile molecule as
3
crystal solvent. The Flack parameter [15] refined to essen-
SS
rac
The tetradentate Schiff-base ligands H2L and H2L
were easily obtained by the 2:1 condensation reactions of
-methoxysalicylaldehyde (o-vanillin) with either 1S,2S-
tially zero for the assumed S,S configuration of the ligand.
CN and the
3
SS
The molecular structure of [CuL (H
O)]ꢀCH
2
3
one-dimensional structure are shown in Fig. 1a, b, respec-
SS
cyclohexanediamine or trans-1,2-cyclohexanediamine as
yellow crystalline materials according to the literature
II SS
method [13]. The Cu complexes [CuL ] and [CuL
tively. The complex of [CuL (H
square pyramidal N coordination geometry, where the
equatorial coordination plane consists of N donor atoms
2
O)]ꢀCH
3
CN assumes a
O
2 3
rac
]
O
2 2
SS
were synthesized by the reaction of the ligands and cop-
per(II) acetate monohydrate in methanol [13]. The inclu-
sion complexes with LiClO or NaClO were obtained by
of the tetradentate ligand L and the axial coordination
site is occupied by a water oxygen atom with Cu–O(5) =
˚
2.427(7) A. The water molecule at the axial site is hydrogen
4
4
SS
rac
the mixed solution of [CuL ] or [CuL ] and LiClO or
4
bonded to two methoxy oxygen atoms of the adjacent unit
0
SS
[CuL (H
˚
NaClO with 1:1 molar ratio in methanol. The precipitates
4
2
O)]ꢀCH CN with O(5)ꢀꢀꢀO(3 ) = 2.939(9) A and
3
0
˚
were collected and recrystallized from acetonitrile and
O(5)ꢀꢀꢀO(4 ) = 2.932(10) A. The intermolecular hydrogen
bonds are repeated to form a one-dimensional structure
running along the a-axis as shown in Fig. 1b.
chloroform. The inclusion complexes, the [1 ? 1] adduct
SS
SS
of [CuL (H O)LiClO ], the [2 ? 1] adduct of [(CuL )
2
2
4
rac
Na(H O) ]ClO , and the [2 ? 2] adduct of [CuL
2
3
4
NaClO ] ꢀCH CN were obtained as block crystals suitable
Structure of the [1 ? 1] adduct with LiClO ,
4
SS
4
2
3
for single-crystal X-ray analyses. The inclusion reaction of
[CuL (H
2
O)LiClO
4
]
?
?
?
SS
perchlorate salts of K , Rb and Cs into [CuL ] gave the
fine needle-like crystals exhibiting colors different from
that of the precursor complex, but the suitable sized crys-
tals for the X-ray diffraction analyses have not been
obtained so far.
SS
[CuL (H
O)LiClO
] was obtained as thin plate-like small
2
4
crystals. Due to the small size of the crystal, the final
structural refinement was of less than optimal quality.
The complex crystallizes in the noncentrosymmetric
SS
Table 1 Crystallographic data of [CuL (H
96 K
SS
CN, [CuL (H
SS
rac
and [CuL NaClO
2
O)]ꢀCH
3
2
O)LiClO
4
], [(CuL
)
2
Na(H O)
2
3
]ClO
4
4 2
] ꢀCH
3
CN at
2
SS
[CuL (H
CH CN
SS
[CuL (H
SS
rac
[CuL NaClO
Complex
2
O)]ꢀ
2
O)
[(CuL
ClO
)
Na(H O)
2 2
3
]
4
]
2
ꢀ
3
4
LiClO ]
4
3
CH CN
Formula
24
C H
3
29CuN O
5
C
22
H26CuClLiN
2
O
9
C
44
H54Cu
2
ClNaN
O
4 15
46 2 2 2 5 16
C H51Cu Cl Na N O
Fw
503.06
568.40
1064.46
monoclinic
P2 (no. 4)
1173.90
monoclinic
P2 /n (no. 14)
Crystal System
Space group
monoclinic
triclinic
P1 (no. 1)
5.9618(16)
9.849(2)
11.399(3)
65.545(5)
81.527(7)
76.394(6)
591.2(3)
1
P2
1
(no. 4)
1
1
˚
a (A)
5.5020(12)
20.239(5)
10.499(3)
90.0000
100.257(6)
90.0000
1150.5(5)
2
12.6702(4)
13.9938(5)
12.7575(6)
90.0000
90.165(2)
90.0000
2261.9(2)
2
10.9353(3)
21.3615(6)
21.5400(7)
90.0000
95.6800(8)
90.0000
5006.9(3)
4
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
3
˚
V (A )
Z
-3
)
Dcalc (Mg m
1.452
1.596
1.563
1.530
-1
)
l(MoKa) (mm
9.896
1.0926
1.0838
1.0467
a
R
0.0826
0.0979
0.0383
0.0912
b
wR
0.1766
0.2198
0.0772
0.2558
123

4
66
J Incl Phenom Macrocycl Chem (2011) 71:463–469
SS
Table 2 Relevant coordination bond lengths (A) for [CuL (H
SS
CN, [CuL (H
SS
)
˚
2
O)]ꢀCH
3
2
O)LiClO
4
], [(CuL
2
Na(H
2
O)
3
]ClO
4
and
rac
CuL NaClO
[
4
]
2
ꢀCH
3
CN
SS
[CuL (H
CH CN
SS
[CuL (H
LiClO
SS
rac
[CuL NaClO
CH CN
Complex
2
O)]ꢀ
2
O)
[(CuL
ClO
)
Na(H O)
2 2
3
]
4
]
2
ꢀ
3
4
]
4
3
Cu(1)–O(1)
Cu(1)–O(2)
Cu(1)–O(5)
Cu(1)–O(15)
Cu(1)–N(1)
Cu(1)–N(2)
Cu(2)–O(5)
Cu(2)–O(6)
Cu(2)–N(3)
Cu(2)–N(4)
1.922(5)
1.911(6)
2.427(7)
1.89(2)
1.849(17)
2.702(14)
1.902(4)
1.900(3)
1.895(5)
1.884(6)
2.518(4)
1.927(4)
1.933(4)
1.894(3)
1.903(3)
1.931(4)
1.935(4)
2.343(4)
2.334(4)
2.753(4)
2.733(4)
1.948(7)
1.939(7)
1.966(16)
1.94(3)
1.922(7)
1.909(6)
1.888(5)
1.926(5)
1.919(6)
1.920(7)
2.337(7)
2.418(6)
2.570(6)
2.841(7)
2.521(7)
Cation(1)–O(1)
Cation(1)–O(2)
Cation(1)–O(3)
Cation(1)–O(4)
Cation(1)–O(6)
2.17(7)
2.09(10)
2.80(8)
2.73(7)
Cation(1)–O(13)
Cation(1)–O(14)
Cation(2)–O(4)
Cation(2)–O(5)
Cation(2)–O(6)
Cation(2)–O(7)
Cation(2)–O(8)
2.294(6)
2.296(5)
2.607(6)
2.290(6)
2.426(6)
2.563(7)
2.723(7)
Fig. 1 a Molecular structure of
precursor complex
SS
CuL (H
[
selected atom numbering
2
O)]ꢀCH
3
CN with the
scheme b One dimensional
structure of
SS
CuL (H
[
2
O)]ꢀCH
3
CN. The
3
CN is
crystal solvent CH
omitted for clarity
triclinic space group P1 (no. 1) and the crystallographic
SS
unique unit consists of a complex [CuL (H O)LiClO ].
to two methoxy oxygen atoms O(3)and O(4) with the distance
˚
of O(5)ꢀꢀꢀO(3) = 2.96(2) and O(5)ꢀꢀꢀO(4) = 2.93(2) A. The
2
4
?
water molecule O(5) is coordinated to Li ion of the adjacent
The Flack parameter is refined nearly to zero [15] and the
SS
SS
unit [CuL (H O)LiClO ] with Li–O(5) = 1.83(9) A. The
˚
configuration of the ligand is consistent with L . The
SS
2
4
molecular structure of [CuL (H O)LiClO ] and the one-
intermolecular Li–O coordination bond is repeated to form a
one-dimensional structure as shown in Fig. 2b. As shown in
? SS
Fig. 2a, Li ion is linked by[CuL ] through two Li–O(1) and
2
4
dimensional structure are shown in Fig. 2a, b, respectively.
SS
The coordination geometry of [CuL (H O)LiClO ] can be
2
4
described as a square pyramidal N O or square planar
3
Li–O(2) interaction consisting of two oxygen atoms (two
?
phenoxy). The Li ion is further linked by an oxygen atom
2
coordination geometry, where the equatorial coordination
plane consists of N O donor atoms of the tetradentate
SS
-
O(9)ofClO4 ion.AmongthefourLi–Odistances,Li–O(5)of
2
2
ligand L and the axial site is occupied by a water oxygen
1.83(9) is the shortest. The Li–O distances are Li–O(1) =
˚
atom with Cu–O(5) = 2.702(14) A. However, the distance
˚
2.17(7) A, Li–O(2) = 2.09(10) A Li–O(3) = 2.80(8) A,
˚
˚
˚
of Cu–O(5) = 2.702(14) A is appreciably longer than the
˚
and Li–O(4) = 2.73(7) A. The coordination environment of
?
Li ion is of a distorted tetrahedral form, with Li–O(1) =
normal coordination bond to the axial water oxygen and it
can be described that the water molecule O(5) is kept in
the cavity. The water molecule O(5) is hydrogen-bonded
2.17(7), Li–O(2) = 2.09(10), Li–O(5) = 1.89(9) and Li–O(9) =
˚
1.83(9) A.
1
23

J Incl Phenom Macrocycl Chem (2011) 71:463–469
467
RR
[CuL ], two ClO4 anions, and one acetonitrile molecule as
-
Structure of the [2 ? 1] adduct with NaClO ,
4
SS
(CuL ) Na(H O) ]ClO
2 2 3 4
[
crystal solvent and the unique unit can be described as
RR
SS
[
Cu Na (L )(L )(ClO ) ]ꢀCH CN. The structure is shown
2
2
4 2
3
SS RR
in Fig. 4. Each complex of [CuL ] and [CuL ] includes one
?
Na ion at the O site provided by two phenoxy and two
SS
The [2 ? 1] adduct of [(CuL ) Na(H O) ]ClO crystallizes
2
2
3
4
in a monoclinic noncentrosymmetric space group P2 (no. 4)
1
4
?
and the crystallographic unique unit consists of one Na
SS
cation, two complexes [CuL ], three water molecules, and
methoxy groups, in which Na–O distances are Na(1)–O(1) =
2.337(7), Na(1)–O(2) = 2.418(6), Na(1)–O(3) = 2.570(6),
˚
Na(1)–O(4) = 2.841(7) A for Cu(1) site and Na(2)–O(5) =
?
one perchlorate anion, in which one Na cation, two
SS
complexes [CuL ], and three water molecules construct a
2.290(6), Na(2)–O(6) = 2.426(6), Na(2)–O(7) = 2.563(7),
˚
Na(2)–O(8) = 2.723(7) A for Cu(2) site, respectively. These
SS
2 ? 1] inclusion complex of [(CuL ) Na(H O) ] and one
?
[
2
2
3
?
Na–O distances indicate that the Na ion is shifted to one side
perchlorate anion exists as a discrete counter anion. The
SS
molecular structure of [(CuL ) Na(H O) ] is shown in
?
?
of two 3-methoxysalicylaldimine moieties. The Na ion is
2
2
3
SS
Fig. 3a, b. The [2 ? 1] complex [(CuL ) Na(H O) ]
?
2
2
3
further coordinated by O atoms of a perchlorate ion as a
2
SS
bidentate chelate ligand. Thus, each complex of [CuL ] and
forms a dimer structure bridged by a water molecule O(15),
SS
where two [CuL ] complexes are stacked to array in the
RR
[CuL ] gives an inclusion species of [CuL NaClO ] and
SS
4
RR
[CuL NaClO ]. These two species are linked through
same direction with a stepped structure. The Cu(2) site has a
square planar N O coordination geometry and Cu(1) site
4
˚
Na(1)–O(6) = 2.521(7) A (O(6) is a phenoxy oxygen atom
2
2
˚
of Cu(1) site) and Na(2)–O(4) = 2.607(6) A (O(4) is a
has an elongated tetragonal pyramidal N O geometry
2
3
with the axial coordination of O(15) with Cu(1)–
˚
O(15) = 2.518(4) A. The bridging water molecule O(15) is
methoxy oxygen atom of Cu(1) site) to give a dimer structure
SS
RR
of [(CuL NaClO )(CuL NaClO )], where the equatorial
4 4
SS
coordination planes of [CuL NaClO ] and[CuL NaClO4]
RR
hydrogen bonded to two phenoxy and two methoxy oxygen
˚
4
atoms of Cu(2) site with O(15)ꢀꢀꢀO(5) = 2.989(5) A,
are stacked nearly parallel but the planes are rotated
nearly to perpendicular to each other. The dimer structure of
˚
˚
O(15)ꢀꢀꢀO(6) = 2.941(5) A, O(15)ꢀꢀꢀO(7) = 2.862(5) A, and
?
SS RR
[(CuL NaClO )(CuL NaClO )] represented by the differ-
˚
O(15)ꢀꢀꢀO(8) = 2.837(5) A. The Na ion is coordinated
4
4
by two phenoxy and two methoxy oxygen atoms of Cu1
ent colors are shown in Fig. 5.
˚
site with Na–O(1) = 2.343(4) A, Na–O(2) = 2.334(4) A,
˚
In summary, we have examined the inclusion reaction of
SS
alkali ions into chiral [CuL ] and racemic [CuL ] host
rac
˚
Na–O(3) = 2.753(4) A, and Na–O(4) = 2.733(4) A, and
˚
SS
compounds. The host compounds of [CuL ] and [CuL
rac
further by two water molecules with Na–O(13) =
]
˚
˚
.294(6) A and Na–O(14) = 2.296(5) A. The water mole-
2
have O cavity per component provided by two phenoxy
4
cule O(13) is further hydrogen bonded to the bridging O(15)
˚
and two methoxy oxygen atoms, which can permit the
accommodation of alkali ion. All the inclusion reactions
were performed by a similar method, where the alkali ion
with O(15)ꢀꢀꢀO(13) = 2.794(7) A to form a closed cyclic
structure as shown in Fig. 3b.
and the host compound are mixed in 1:1 mol ratio. Reac-
SS
tion of NaClO and [CuL ] gave the [2 ? 1] adduct
SS
4
Structure of the [2 ? 2] adduct,
rac
[(CuL ) Na(H O) ]ClO , while the reaction of NaClO
4
2
2
3
4
rac
and the racemic complex [CuL ] gave the [2 ? 2] adduct
rac
[
CuL NaClO ] ꢀCH CN
4
2
3
SS
RR
(
[Cu Na (L )(L )(ClO ) ]ꢀCH CN)
[CuL NaClO ] ꢀCH CN. The result demonstrates that the
2
2
4 2
3
4 2
3
chirality at the part of the ligand framework can produce
different assembly structures. The preferable assembly
structure may be obtained by the inclusion ratio of alkali
ion and host compound, in which the chirality can affect
significantly on the assembly structure.
rac
The [2 ? 2] adduct [CuL NaClO ] ꢀCH CN crystallizes in
4
2
3
the centrosymmetric monoclinic space group P2 /n (no. 14)
1
with Z = 4. The crystallographic unique unit consists of
?
SS
two Na cations, two complexes consisting of [CuL ] and
Fig. 2 a Molecular structure
SS
of [CuL (H O)LiClO ] with
2 4
the selected atom numbering
scheme. b One dimensional
structure of
SS
[
2 4
CuL (H O)LiClO ]
123

4
68
J Incl Phenom Macrocycl Chem (2011) 71:463–469
Fig. 3 a Molecular structure
of the [2 ? 1] complex
SS
?
[
(CuL
)
on the equatorial N
2
Na(H
2
O)
3
]
projected
2
O
2
coordination plane with
the selected atom numbering
scheme. b Side view of the
[
2 ? 1] complex showing the
SS
bridging manner of two [CuL
species
]
Fig. 4 a Molecular structure
of the [2 ? 2] adduct
rac
[
(
4 2
CuL NaClO ]
SS
RR
2 2 4 2
[Cu Na (L )(L )(ClO ) ])
projected on the equatorial
coordination plane with
the selected atom numbering
2 2
N O
scheme. b Side view of
SS
RR
[
showing the bridging manner
Cu
2 2 4 2
Na (L )(L )(ClO ) ]
SS
4
of two [CuL NaClO ] and
RR
[
4
CuL NaClO ]
Fig. 5 a Structure of the
2 ? 2] adduct
[
[
rac
CuL NaClO
4
]
2
consisting
] (red) and
4
CuL NaClO ] (blue). b Side
RR
of [CuL NaClO
[
4
SS
view of the [2 ? 2] adduct
showing the bridging manner
RR
of [CuL NaClO
4
] (red) and
SS
CuL NaClO ] (blue)
[
4
Supplementary data
CCDC 818117 - 818120 contain the supplementary crys-
References
1
2
. Lehn, J.M.: Toward self-organization and complex matter. Sci-
ence 295, 2400–2403 (2002)
. Seidel, S.R., Stang, P.J.: High-symmetry Coordination Cages via
Self-assembly. Acc. Chem. Res. 35, 972–983 (2002)
SS
SS
tallographic data for [CuL (H O)]ꢀCH CN, [CuL (H O)
2
3
2
SS
rac
LiClO ], [(CuL ) Na(H O) ]ClO , and [CuL NaClO ] ꢀ
4
2
2
3
4
4 2
CH CN. These data can be obtained free of charge via
3
3. Gruber, S.J., Harris, C.M., Sinn, E.: Metal complexes as ligands
bi- and tri-nuclear complexes containing similar and dissimilar
metal atoms. J. Inorg. Nucl. Chem. 3, 495–499 (1967)
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from
the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: (?44) 1223-336-
4
. Armstrong, L. G., Lip, H. C., Lindoy, L. F., McPartlin, M.,
Tasker, P. A.: Alkali-metal salt adducts of Ni(II) complexes of
quadridentate Schiff-base ligands. The X-ray structure of N,N’-
0
33; or e-mail: deposit@ccdc.cam.ac.uk.
1
23

J Incl Phenom Macrocycl Chem (2011) 71:463–469
469
ethylenebis(acetylacetoniminato)nickel(II). J. Chem. Soc. Dalton
Trans. 1771-1774 (1977)
10. Stefankiewicz, A. R., Walesa, M., jankowski, P, Ciesielski, A.,
Patroniak, V., Kubicki, M., Hnatejko, M., Harrowfield, J. M.,
Lehn, J-M.: Quetrpyridine Ligands forming Helical Complexes
of Mono- and Bi-nuclear (Helicate) Forms. Eur. J. Inorg. Chem.
2910–2920 (2008)
5
. Maruno, Y., Yabe, K., Hagiwara, H., Fujinami, T., Matsumoto,
N., Re, N., Mrozinski, J.: Cyclic and linear structures constructed
by ionic bonds between alkali ion and pinwheel pentanuclear
III
II
III
II
?
?
?
[Gd (Cu L)
Cs ; H
4
] core of M[Gd (Cu L) ] (M = Na , K , and
4
11. Shimogori, Y., Hamamatsu, T., Fujinami, T., Hagiwara, H., Mat-
sumoto, N., Re, N., Mrozinski, J., Ishikawa, Y., Igashira-Kamiy-
?
3
L = N-(4-methyl-6-oxo-3-azahept-4-enyl)oxamic acid).
II
ama, A., Konno, T.: Linear Cu -Gd -Cu -Gd complex derived
III
II
III
Bull. Chem. Soc. Jpn. 83, 1511–1517 (2010)
. Jiang, Z., Lu, H., Wu, D., Zhou, X., Shen, Z., Kobayashi, N.:
Color difference caused by chirality. Inorg. Chem. Commun. 14,
II
from assembly reaction of [NaCu H
dpen(meso)
III
6
7
3
L
] and [Gd (thd)
3
(H O) (H L = meso-1,2-diphenyl-1-(2-oxybenzamido)-2-(2-
2
2
]
3
1
3–1416 (2011)
oxy-3-ethoxybenzylideneamino)ethane and Hthd = 2,2,6,6-tetra-
methyl-3,5-heptanedione). Polyhedron 30, 1127–1133 (2011)
12. Hamamatsu, T., Matsumoto, N., Re, N., Mrozinski, J.: Chiral
ferromagnetic chain of Copper(II)–Gadolinium(III) complex.
Chem. Lett. 38, 762–763 (2009)
. Leung, D., Follmer-Andersen, J.F., Lynch, V.M., Anslyn, E.V.:
Using Enantioselective Indicator Displacement Assays to deter-
mine the Enantiomeric Excess of a-Amino-Acids. J. Am. Chem.
Soc. 130, 12318–12327 (2008)
8
. Mamdouh, W., Uji-i, H., Gesqui e` re, A., De Feyter, S., Amabilino,
D.B., Abdel-Mottaleb, M.M.S., Veciana, J., Schryver, F.C.: A
nanoscale view of supramolecular stereochemistry in self-
assembled monolayers of enantiomers and racemates. Langmuir
13. Szlyk, E., Surdykowski, A., Barwiolek, M., Larsen, E.: Spec-
troscopy and stereochemistry of the optically active copper(II),
0
cobalt(II) and Ni(II) complexes with Schiff Bases N, N -(1R, 2R)-
(-)-1, 2-cyclohexylenebis(3-methylbenzylideniminato) and N,
0
2
0, 9628–9635 (2004)
N -(1R, 2R)-(-)-1, 2-cyclohexylenebis(5-methylbenzylidenimi-
nato). Polyhedron 21, 2711–2717 (2002)
9
. Katsuki, I., Motoda, Y., Sunatsuki, Y., Matsumoto, N., Naka-
shima, T., Kojima, M.: Spontaneous resolution induced by self-
organization of chiral self-complementary cobalt (III) complexes
with achiral tripod-type ligands containing three imidazole
groups. J. Am. Chem. Soc. 124, 629–640 (2002)
14. CrystalStructure 4.0: Crystal Structure Analysis Package, Rigaku
Corporation (2000–2010). Tokyo 196-8666, Japan
15. Flack, H.D.: On enantiomorph-polarity estimation. Acta Cryst.
A39, 876–881 (1983)
123