Assembly of hydrogen-bonded organic layers with macrocyclic complexes acting as pillars

Article abstract of DOI:10.1002/ejic.200390178

Novel supramolecular networks of 2D {[Ni(cyclam)][C6Hg- (COOH)₂(COO)]₂}_n (1) and 3D {[Ni(cyclam)][C₆H₃(OH)₂- (COO)]₂}_n (2) have been constructed by the self-assembly of [Ni(cyclam)](ClO₄)₂ with cis, cis-1,3,5-cyclohexanetricarboxylic acid (H3CTC) and 3,5-dihydroxybenzoic acid (HDHB), respectively, in py/MeCN/H₂O. In the crystal structure of 1, each nickel(II) macrocyclic complex binds two H₂CTC^- ions at the axial sites. The coordinated H₂CTC^- ions form hydrogen bonds with one another, which results in organic bilayers having macrocyclic complexes as pillars. In the crystal structure of 2, each nickel(II) macrocyclic complex binds two DHB- ions in the trans position. Two free hydroxyl groups and one carbonyl oxygen atom of the coordinated DHB^- ion are extensively hydrogen-bonded with the DHB^- ligand of the neighboring complexes, which results in a 3D network where 2D organic layers are linked by the macrocyclic complexes acting as pillars. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Full text of DOI:10.1002/ejic.200390178

FULL PAPER
Assembly of Hydrogen-Bonded Organic Layers with Macrocyclic Complexes
Acting as Pillars
Myunghyun Paik Suh,*[a] Kil Sik Min,[a] Jung Woo Ko,[a] and Hye Jin Choi[a]
Keywords: Hydrogen bonds / Layered compounds / Macrocyclic ligands / Nickel / Self-assembly
Novel supramolecular networks of 2D {[Ni(cyclam)][C6H9-
(COOH)2(COO)]2}n (1) and 3D {[Ni(cyclam)][C6H3(OH)2-
(COO)]2}n (2) have been constructed by the self-assembly of
ture of 2, each nickel(II) macrocyclic complex binds two
DHB− ions in the trans position. Two free hydroxyl groups
and one carbonyl oxygen atom of the coordinated DHB− ion
[Ni(cyclam)](ClO4)2 with cis,cis-1,3,5-cyclohexanetricarbox- are extensively hydrogen-bonded with the DHB− ligand of
ylic acid (H3CTC) and 3,5-dihydroxybenzoic acid (HDHB),
respectively, in py/MeCN/H2O. In the crystal structure of 1,
each nickel(II) macrocyclic complex binds two H2CTC− ions
at the axial sites. The coordinated H2CTC− ions form hydro-
gen bonds with one another, which results in organic bilayers
having macrocyclic complexes as pillars. In the crystal struc-
the neighboring complexes, which results in a 3D network
where 2D organic layers are linked by the macrocyclic com-
plexes acting as pillars.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
Supramolecular solids with various network topologies
and with interesting properties have been prepared by the
self-assembly of transition metal ions and organic building
blocks.[1,2] In the self-assembly of supramolecules, hydrogen
bonding,[3] metal-ligand coordination,[4] and π-π interac-
tions[5] are involved in multidimensional intermolecular in-
teractions. In particular, directional hydrogen-bonding in-
teractions are important for materials design[6] and molecu-
lar recognition.[7,8] It has been demonstrated that extensive
hydrogen-bonding interactions in organic compounds result
in remarkably robust three-dimensional networks.[9] In ad-
dition, frameworks with different topologies can be con-
structed by changing the hydrogen-bonding mode.[10,11]
Macrocyclic complexes have been rarely employed as metal
building blocks in the self-assembly of supramolecular net-
works.[12,13] Recently, a molecular floral lace with 1D chan-
nels, [Ni(cyclam)(H2O)2]3[C6H3(COO)3]2·24H2O (A), was
assembled by the extensive hydrogen-bonding interactions
boxylic acid (H3CTC) and 3,5-dihydroxybenzoic acid
(HDHB), respectively, in the presence of pyridine. Multidi-
mensional networks 1 and 2 are generated by the extensive
hydrogen-bonding interactions between the organic build-
ing blocks, giving rise to 2D layers with the macrocyclic
complexes acting as pillars connecting the organic layers.
To the best of our knowledge, this is the first example where
macrocyclic complexes are involved as pillars linking the
organic layers in the supramolecular networks. This syn-
thetic strategy can be applied to construct hybrid materials
that consist of alternately packed organic-inorganic layers.
between
the
coordinated
water
molecules
of
[Ni(cyclam)(H2O)2]2ϩ and 1,3,5-benzenetricarboxylate.[12]
Here we report 2D {[Ni(cyclam)][C6H9(COOH)2-
(COO)]2}n (1) and 3D {[Ni(cyclam)][C6H3(OH)2(COO)]2}n
(2) supramolecular networks, which are assembled from
[Ni(cyclam)](ClO4)2 with cis,cis-1,3,5-cyclohexanetricar-
[a]
School of Chemistry and Molecular Engineering, and Center
for Molecular Catalysis, Seoul National University,
Seoul 151-747, Republic of Korea
Results and Discussion
Fax: (internat.) ϩ82-2/886-8516
E-mail: mpsuh@snu.ac.kr
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Self-Assembly and Properties of 2D and 3D Networks
Our synthetic strategy to build multidimensional net-
works was based on the hydrogen-bonding interactions be-
1373
Eur. J. Inorg. Chem. 2003, 1373Ϫ1379  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0407Ϫ1373 $ 20.00ϩ.50/0

M. P. Suh, K. S. Min, J. W. Ko, H. J. Choi
FULL PAPER
Scheme 1. Synthetic strategy for 1 and 2
Figure 1. (a) An ORTEP view of 1 with atomic numbering scheme; the atoms are represented by 40% probability thermal ellipsoids; (b)
the 2D organic layer, showing 26-membered supramolecular synthons constructed by the hydrogen bonding interactions between the
coordinated H2CTCϪ ions; metal ions are indicated as filled black circles and intermolecular hydrogen bonds are indicated as dotted
lines; (c) a view from the bc plane, showing the bilayer network where macrocyclic complexes act as pillars
1374
Eur. J. Inorg. Chem. 2003, 1373Ϫ1379

Hydrogen-Bonded Organic Layers with Macrocyclic Complexes as Pillars
FULL PAPER
[a]
˚
tween organic ligands, which led to 2D organic layers with
Table 1. Selected bond lengths (A) and angles (°) for 1
the macrocyclic complexes linking the organic layers as pil-
[14]
Ni1ϪN1
Ni1ϪN2
Ni1ϪO1
O1ϪC6
O2ϪC6
2.042(2)
2.042(2)
2.171(1)
1.241(2)
1.266(2)
1.314(3)
1.200(3)
1.317(3)
1.199(3)
1.458(3)
1.471(3)
1.458(3)
1.475(3)
85.82(9)
89.44(7)
90.72(7)
180.00(7)
132.12(12)
114.1(2)
105.27(15)
116.57(16)
114.1(2)
105.33(15)
116.56(16)
113.1(2)
108.9(2)
108.8(2)
113.0(2)
115.4(2)
124.30(17)
117.66(16)
118.04(16)
C1ϪC5Ј
C2ϪC3
C4ϪC5
1.501(5)
1.498(4)
1.498(5)
1.526(2)
1.507(3)
1.504(3)
1.527(2)
1.528(2)
1.530(2)
1.520(3)
1.518(3)
1.530(2)
lars. For this, [Ni(cyclam)](ClO4)2
and the carboxylate
anions derived from cis,cis-1,3,5-cyclohexanetricarboxylic
acid (H3CTC) and 3,5-dihydroxybenzoic acid (HDHB)
were used as the building blocks (Scheme 1).
C6ϪC9
C7ϪC11
C8ϪC13
C9ϪC10
C9ϪC14
C10ϪC11
C11ϪC12
C12ϪC13
C13ϪC14
When [Ni(cyclam)](ClO4)2 was reacted in MeCN/H2O O3ϪC7
O4ϪC7
(1:1 v/v) with cis,cis-1,3,5-cyclohexanetricarboxylic acid
O5ϪC8
(H3CTC) in the presence of pyridine, only one proton of
O6ϪC8
H3CTC was removed and [Ni(cyclam)]2ϩ was coordinated
N1ϪC2
N1ϪC1
N2ϪC3
N2ϪC4
N1ϪNi1ϪN2
N1ϪNi1ϪO1
N2ϪNi1ϪO1
by two H2CTCϪ anions to form {[Ni(cyclam)][C6H9-
(COOH)2(COO)]2}n (1). When [Ni(cyclam)](ClO4)2 was re-
acted in MeCN/H2O (1:1 v/v) with 3,5-dihydroxybenzoic
acid (HDHB) in the presence of pyridine, the carboxylic
acid group of HDHB was deprotonated and [Ni(cyclam)]2ϩ
O4ϪC7ϪO3
122.43(19)
124.64(18)
112.86(17)
122.27(19)
124.74(18)
112.92(17)
110.17(14)
110.29(14)
111.21(15)
111.28(14)
110.50(15)
10.13(15)
110.15(15)
110.59(15)
110.61(15)
110.46(15)
109.89(15)
111.58(15)
O4ϪC7ϪC11
O3ϪC7ϪC11
O6ϪC8ϪO5
was coordinated with two DHBϪ anions to form O1ЈϪNi1ϪO1
C6ϪO1ϪNi1
O6ϪC8ϪC13
O5ϪC8ϪC13
C6ϪC9ϪC10
C6ϪC9ϪC14
C10ϪC9ϪC14
C9ϪC10ϪC11
C7ϪC11ϪC12
C7ϪC11ϪC101
C12ϪC11ϪC10
C13ϪC12ϪC11
C8ϪC13ϪC12
C8ϪC13ϪC14
C12ϪC13ϪC14
C9ϪC14ϪC13
{[Ni(cyclam)][C6H3(OH)2(COO)]2}n (2).
C2ϪN1ϪC1
The supramolecular compounds 1 and 2 are pink and
C2ϪN1ϪNi1
air-stable. They are insoluble in all solvents except water.
C1ϪN1ϪNi1
In water, they are dissociated into the building blocks, as
evidenced by the UV/Vis spectra, which exhibit the charac-
teristic chromophore (λmax ϭ 445 nm) of the starting mate-
rial [Ni(cyclam)]2ϩ. The diffuse reflectance spectrum meas-
ured for a powdered sample of 1 shows maximum absorp-
C3ϪN2ϪC4
C3ϪN2ϪNi1
C4ϪN2ϪNi1
N1ϪC1ϪC5Ј
N1ϪC2ϪC3
N2ϪC3ϪC2
tions at 332, 505, and 648 nm and that of 2 at 300, 511, and N2ϪC4ϪC5
C4ϪC5ϪC1Ј
661 nm, which correspond to the chromophores of nickel()
O1ϪC6ϪO2
ions coordinated by N4O2 donors.[15] The TGA and DSC
O1ϪC6ϪC9
traces of 1 and 2 (Figures S1 and S2) show that decompo-
O2ϪC6ϪC9
sition starts at 240 and 220 °C, respectively.
[a]
Symmetry transformations used to generate equivalent atoms:
X-ray Crystal Structure of 1
Ј: Ϫx, Ϫy, Ϫz.
An ORTEP[16] drawing of 1 is shown in Figure 1a.
Table 1 shows selected bond lengths and angles. In the crys-
tal structure of 1, the nickel() ion of the macrocyclic com-
plex [Ni(cyclam)]2ϩ is coordinated to two carboxylate oxy-
gen atoms of H2CTCϪ ions at the axial sites (Figure 1a).
The complex has an inversion center at the nickel() ion.
˚
coordinated CϪO bond length [C6ϪO1, 1.241(2) A]. Since
both of the H2CTCϪ ions coordinating a nickel() macro-
cyclic complex are involved in the formation of two differ-
ent 2D organic layers, the structure becomes a bilayer con-
taining nickel() macrocycles acting as pillars (Figure 1c).
The interlayer distance within the bilayer is 5.692(4) A and
the shortest distance between two adjacent bilayers (C···O)
˚
The average NiϪN bond length is 2.042(1) A and the aver-
˚
˚
age NiϪO bond length is 2.171(1) A, similar to those of
open-framework A.[12] The coordinated H2CTCϪ ligands
are linked to one another by the extensive hydrogen-bond-
ing interactions. Each carbonyl oxygen atom of the coordi-
nated carboxylate group of H2CTCϪ behaves as a hydrogen
acceptor to form bifurcated hydrogen bonds with two car-
˚
is 3.399(3) A.
X-ray Crystal Structure of 2
An ORTEP[16] drawing of 2 is shown in Figure 2a.
boxylic acid groups belonging to two different H2CTCϪ Table 2 shows selected bond lengths and angles. In the crys-
ions of the adjacent macrocyclic complexes [O2···O3Ј(x Ϫ tal structure of 2, the nickel() ion of the macrocyclic com-
1, y, z): 2.701(2) A; O2···H3ЈϪO3Ј: 172.73°; O2···O5ЈЈ(x, y plex binds two carboxylate oxygen atoms of DHBϪ ions at
˚
˚
Ϫ 1, z): 2.700(2) A; O2···H5ЈЈϪO5ЈЈ: 172.74°), and two free the axial sites (Figure 2a). The complex has an inversion
carboxylic acid groups of the H2CTCϪ ligand behave as center at the nickel() ion. The average NiϪN and NiϪO
˚
hydrogen donors and form hydrogen bonds with the car- bond lengths are 2.065(1) and 2.130(1) A, respectively,
bonyl oxygen atoms of the H2CTCϪ ligands belonging to which are similar to those of 1. The aromatic ring of the
two different adjacent complexes. The extensive hydrogen- DHBϪ ion is tilted with respect to the square coordination
bonding interactions between H2CTCϪ ligands construct plane of the macrocycle [dihedral angle ϭ 51.3(1)°]. The
26-membered supramolecular synthons that propagate infi- DHBϪ ligand is not planar since the dihedral angle between
nitely parallel to the crystallographic ab plane to give rise the carboxylate group and the aromatic ring of DHBϪ ion
to a 2D organic network (Figure 1b). Due to the hydrogen- is 29.9(3)°. Within the molecule, there are hydrogen-bond-
bonding interactions, the free CϭO bond length of ing interactions between the carbonyl oxygen atoms of the
H2CTCϪ [C6ϪO2, 1.266(2) A] is longer than that of the carboxylate ions and the secondary amines of the macrocy-
˚
Eur. J. Inorg. Chem. 2003, 1373Ϫ1379
1375

M. P. Suh, K. S. Min, J. W. Ko, H. J. Choi
FULL PAPER
Figure 2. (a) An ORTEP view of 2 with atomic numbering scheme; the atoms are represented by 40% probability thermal ellipsoids;
intramolecular hydrogen bonds are indicated as dotted lines; (b) a 2D organic layer constructed by the hydrogen-bonding interactions
between the coordinated DHBϪ ligands; (c) a view of the 3D network on the ab plane, showing how the thick 2D organic layers are
linked by the macrocyclic complexes acting as pillars, interlayer hydrogen bonds are indicated as ·····
˚
˚
cle to form six-membered rings (O2···N1: 2.980(3) A; A; O2···H4(#2)ϪO4(#2): 175°]. There are π-π interactions
O2···H1ϪN1: 162°). The six-coordinate nickel() macro- between the phenyl rings of DHBϪ belonging to the adjac-
˚
cyclic complexes are linked together by extensive hydrogen- ent chains [centroid···centroid distance: 6.032 A; closest
bonding interactions between the DHBϪ ligands. Each C···C distance: 3.917(4) A]. Since the interchain hydrogen-
˚
DHBϪ ion coordinating the metal above the plane forms bonding interactions extend along the b direction and un-
hydrogen bonds with two neighboring DHBϪ ligands, via dulate in the a direction, the DHBϪ ligands construct a
hydroxyl groups [O3···O4(#1) (#1: x, Ϫy Ϫ 0.5, z ϩ 0.5):
˚
2.763(2) A; O3ϪH3(#1)···O4(#1): 164°], to build a 1D
chain that extends along the crystallographic c axis, undul-
ating in the b and a directions (Figure 2b; A in Scheme 2).
Similarly, each DHBϪ ligand coordinating a metal below
the macrocyclic coordination plane also forms hydrogen
bonds with two adjacent DHBϪ ligands to construct an-
other undulating 1D chain that also extends along the c
direction (B in Scheme 2). These two kinds of chains are
alternately aligned toward the b direction, and they are con-
nected to one another by the hydrogen-bonding interactions
via the free carbonyl oxygen atom of the coordinated car-
boxylate group of DHBϪ belonging to one chain and the
hydroxyl group of DHBϪ belong to the other chain
[O2···O4(#2) (#2 ϭ Ϫx Ϫ 1, y ϩ 0.5, Ϫz ϩ 0.5): 2.610(2) Scheme 2. Schematic drawing of formation of 2D organic layer in 2
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Eur. J. Inorg. Chem. 2003, 1373Ϫ1379

Hydrogen-Bonded Organic Layers with Macrocyclic Complexes as Pillars
FULL PAPER
[a]
˚
ses were performed by the analytical laboratory of Seoul National
University. UV/Vis diffuse reflectance spectra were recorded with a
Cary 300 Bio UV/Vis spectrophotometer. Thermogravimetric
analysis (TGA) and differential scanning calorimetry (DSC) were
performed at a scan rate of 5 °C/min using a DuPont TGA 2050
and a DuPont DSC 2100 TA instrument, respectively.
Table 2. Selected bond lengths (A) and angles (°) for 2
NiϪN1
NiϪN2
2.065(2)
2.065(2)
C1ϪC5Ј
C1ϪC2
1.515(4)
1.517(4)
1.513(4)
1.498(3)
1.389(3)
1.393(3)
1.386(3)
1.388(3)
1.387(3)
1.392(3)
NiϪO1
N1ϪC3
2.130(2)
1.465(3)
C3ϪC4
C6ϪC7
N1ϪC2
N2ϪC5
1.478(3)
1.469(3)
C7ϪC12
C7ϪC8
Safety Note: Perchlorate salts of metal complexes with organic li-
gands are often explosive and should be handled with great caution,
although we have experienced no problem with the compounds re-
ported in this work.
N2ϪC4
O1ϪC6
O2ϪC6
O3ϪC9
1.482(3)
1.258(3)
1.258(3)
1.360(3)
C8ϪC9
C9ϪC10
C10ϪC11
C11ϪC12
O4ϪC11
1.368(3)
85.23(8)
92.00(7)
92.92(7)
113.62(19)
106.20(14)
116.08(14)
114.4(2)
115.88(16)
106.24(15)
132.68(14)
115.8(2)
{[Ni(cyclam)][C6H9(COOH)2(COO)]2}n (1): An MeCN solution
(6 mL) of cis,cis-1,3,5-cyclohexanetricarboxylic acid (H3CTC;
0.14 g, 0.76 mmol) mixed with pyridine (1 mL) was added dropwise
to an MeCN/H2O (1:1 v/v, 12 mL) solution of [Ni(cyclam)](ClO4)2
(0.17 g, 0.38 mmol). The yellow color of the nickel() solution
turned to pale pink. The solution was allowed to stand at room
temperature until pale pink crystals of {[Ni(cyclam)][C6H9-
(COOH)2(COO)]2}n formed, which were filtered, washed with
MeCN/H2O (1:1 v/v), and dried in air. There is no other form of
aggregation present in the solution. Yield: 0.20 g (77%).
C28H46N4NiO12: calcd. C 48.78, H 6.73, N 8.13; found C 48.60, H
6.55, N 8.50. FT-IR (Nujol mull): ν˜ ϭ 3300 (s), 3123 (s), 3084 (s),
1721 (s), 1548 (s), 1251 (s), 1177 (s), 954 (s), 870 (s), 730 (s), 649
(s) cmϪ1. UV/Vis (diffuse reflectance spectrum): λmax ϭ 332, 505,
648 nm.
N2ϪNiϪN1
N2ϪNiϪO1
N1ϪNiϪO1
C3ϪN1ϪC2
C3ϪN1ϪNi
C2ϪN1ϪNi
C5ϪN2ϪC4
C5ϪN2ϪNi
C4ϪN2ϪNi
C6ϪO1ϪNi
C5ЈϪC1ϪC2
N1ϪC2ϪC1
N1ϪC3ϪC4
N2ϪC4ϪC3
N2ϪC5ϪC1Ј
O1ϪC6ϪO2
O1ϪC6ϪC7
O2ϪC6ϪC7
C12ϪC7ϪC8
C12ϪC7ϪC6
C8ϪC7ϪC6
C9ϪC8ϪC7
O3ϪC9ϪC8
O3ϪC9ϪC10
C8ϪC9ϪC10
C11ϪC10ϪC9
O4ϪC11ϪC10
O4ϪC11ϪC12
C10ϪC11ϪC12
C7ϪC12ϪC11
124.4(2)
116.47(17)
119.05(19)
120.12(19)
119.92(18)
119.83(19)
119.8(2)
116.7(2)
122.55(19)
120.73(19)
119.02(19)
122.09(19)
116.91(19)
120.99(19)
119.33(19)
112.45(19)
109.08(19)
108.9(2)
111.77(19)
[a]
Symmetry transformations used to generate equivalent atoms:
{[Ni(cyclam)][C6H3(OH)2(COO)]2}n (2): An MeCN solution (6 mL)
of 3,5-dihydroxybenzoic acid (0.14 g, 0.88 mmol) and pyridine
(1 mL) was added dropwise to an MeCN/H2O (1:1 v/v, 12 mL)
solution of [Ni(cyclam)](ClO4)2 (0.20 g, 0.44 mmol). The yellow
Ј: Ϫx, Ϫy, Ϫz.
thick 2D organic layer (Figure 2b and 2c). The thickness of
the organic layer is 4.872(3) A. These thick 2D organic lay- color of the nickel() solution turned to pale pink. The solution
˚
was allowed to stand at room temperature until pale pink crystals
of {[Ni(cyclam)][C6H3(OH)2(COO)]2}n formed, which were filtered
off, washed with MeCN/H2O (1:1 v/v), and dried in air. There is
no other form of aggregation present in the solution. Yield: 0.19 g
(75%). C24H34N4NiO8: calcd. C 51.00, H 6.06, N 9.91; found C
50.27, H 6.17, N 9.98. FT-IR (Nujol mull): ν˜ ϭ 3306 (s), 3200 (s),
3062 (s), 2554 (s, br), 1558 (s), 1393 (s), 1284 (s), 1156 (s), 1025 (s),
958 (s), 792 (s), 689 (s) cmϪ1. UV/Vis (diffuse reflectance spec-
trum): λmax ϭ 248, 300, 511, 661 nm.
ers are linked by the macrocyclic complexes located on a
plane parallel to the bc plane, and thus the whole structure
can be viewed as a 3D network where macrocyclic com-
plexes act as pillars (Figure 2c).
Conclusion
A 2D bilayered framework (1) and a 3D supramolecular
network (2), where macrocyclic complexes behave as pillars
linking 2D organic layers, have been prepared by the self-
assembly of the nickel() macrocyclic complex
[Ni(cyclam)]2ϩ with cis,cis-1,3,5-cyclohexanetricarboxylate
(H2CTCϪ) and 3,5-dihydroxybenzoate (DHBϪ), respec-
X-ray Crystallographic Study: Single crystals of 1 and 2 were
mounted on an EnrafϪNonius CAD4 diffractometer. The unit-cell
parameters were determined from 25 machine-centered reflections
with 22° Ͻ 2θ Ͻ 28° for 1 and 22° Ͻ 2θ Ͻ 27° for 2. Intensities
were collected with graphite-monochromated Mo-Kα radiation
˚
(λ ϭ 0.71069 A), using the ω-2θ scan. Three standard reflections
tively. The multi-dimensional networks are constructed by were measured every 2 h for the orientation and intensity control;
no significant intensity decay was observed. The data were cor-
rected for Lorentz and polarization effects. No absorption correc-
tion was made. For 1, among 2618 reflections measured in the
range 3.78 Ͻ 2θ Ͻ 49.88, 2552 were assumed to be observed [F Ͼ
4σ(F)]. For 2, among 2193 reflections measured in the range 4.80
Ͻ 2θ Ͻ 49.94, 1842 were assumed to be observed [F Ͼ 4σ(F)]. The
crystal structures were solved by direct methods[17] and refined by
full-matrix least-squares methods using the SHELXL-97 computer
program.[18] For 1 and 2, the positions of all non-hydrogen atoms
were refined with anisotropic displacement factors. The carboxylic
acid protons and hydroxyl protons were located from the difference
Fourier maps and refined with isotropic thermal parameters. The
the extensive hydrogen-bonding interactions between the
organic ligands coordinating the nickel() ions. The syn-
thetic strategy can be applied to construct hybrid materials
that consist of organic layers and layers of transition metal
complexes packed alternately.
Experimental Section
General Remarks: All chemicals and solvents used in the synthesis
were of reagent grade and used without further purification.
[Ni(cyclam)](ClO4)2 was prepared according to the literature pro- remaining hydrogen atoms were allowed to ride on their bonded
cedures previously reported.[14] Infrared spectra were recorded with
a PerkinϪElmer 2000 FT-IR spectrophotometer. Elemental analy-
atoms with the isotropic displacement factors fixed with values of
1.2-times those of the bonded atoms. ORTEP drawings were made
Eur. J. Inorg. Chem. 2003, 1373Ϫ1379
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M. P. Suh, K. S. Min, J. W. Ko, H. J. Choi
FULL PAPER
Table 3. Crystallographic data for 1 and 2
1
2
Formula
M
C28H46N4NiO12
689.40
C24H34N4NiO8
565.26
Crystal system
Space group
Triclinic
P1
Monoclinic
P21/c
8.563(1)
13.079(2)
11.283(3)
90
98.74(1)
90
1249.0(4)
2
¯
˚
a (A)
8.349(2)
8.361(3)
10.803(4)
85.75(3)
85.82(2)
88.23(2)
749.8(4)
1
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
3
˚
V (A )
Z
µ (mmϪ1
T (K)
)
0.719
293(2)
0.834
293(2)
Total measured reflections
Total unique reflections
Observed reflections [I Ͼ 2σ(I)]
R1 (all data)[a]
2857
2372
2618 (Rint ϭ 0.0069)
2552
0.0348
2193 (Rint ϭ 0.0127)
1842
0.0412
wR2 (all data)[b]
0.0931
0.0860
[a]
[b]
R1 ϭ Σ||F0| Ϫ |Fc||/Σ|F0|. wR2 ϭ [Σ[w(|F0|2 Ϫ |Fc|2)2]/Σ[w(|F0|)4]1/2
.
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Eur. J. Inorg. Chem. 2003, 1373Ϫ1379

Hydrogen-Bonded Organic Layers with Macrocyclic Complexes as Pillars
FULL PAPER
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