Hydrogen-bonded supramolecular manganese(II) complexes with network and sheet structures bridged by terephthalate unit

Article abstract of DOI:10.1016/j.ica.2005.05.002

Two 1D complexes [Mn(4- methylpyrazole)₃(H₂O)(tp)] _n (2) and [Mn(4-methylpyrazole)₄(tp)]_n (3) (tp = terephthalate) were synthesized and characterized by means of X-ray analysis and magnetic studies. The molecular structure of 2 reveals that Mn(II) centers with asymmetric coordination surroundings are bridged by crystallographically different tp ligands, forming a 1D chain. The 1D coordination chains are interconnected by hydrogen bonds between free carboxylate oxygen atoms in a chain and hydrogens of pyrazole nitrogen atoms in neighboring chains, leading to a 3D framework. Compound 3 also exhibits a 1D coordination chain which is hydrogen-bonded to adjacent chains, providing a 2D sheet structure. Interestingly, the structures include intra- and interchain hydrogen bonds contributed from N-H groups of the capping 4-methylpyrazole ligands. Magnetic measurements show weak antiferromagnetic interactions with exchange coupling parameters of J = -0.018 cm^-1 for 2 and J = -0.062 cm^-1 for 3 through the extended tp ligand on the basis of an infinite chain model (H = -JΣS_i ? S_{i + 1}).

Full text of DOI:10.1016/j.ica.2005.05.002

Inorganica Chimica Acta 358 (2005) 3341–3346
www.elsevier.com/locate/ica
Hydrogen-bonded supramolecular manganese(II) complexes
with network and sheet structures bridged by terephthalate unit
*
Chang Seop Hong , Jung Hee Yoon, Young Sin You
Department of Chemistry and Center for Electro- and Photo-Responsive Molecules, Korea University, Seoul 136-701, Korea
Received 24 January 2005; received in revised form 12 April 2005; accepted 5 May 2005
Abstract
Two 1D complexes [Mn(4- methylpyrazole)3(H2O)(tp)]n (2) and [Mn(4-methylpyrazole)4(tp)]n (3) (tp = terephthalate) were syn-
thesized and characterized by means of X-ray analysis and magnetic studies. The molecular structure of 2 reveals that Mn(II) centers
with asymmetric coordination surroundings are bridged by crystallographically different tp ligands, forming a 1D chain. The 1D
coordination chains are interconnected by hydrogen bonds between free carboxylate oxygen atoms in a chain and hydrogens of pyr-
azole nitrogen atoms in neighboring chains, leading to a 3D framework. Compound 3 also exhibits a 1D coordination chain which is
hydrogen-bonded to adjacent chains, providing a 2D sheet structure. Interestingly, the structures include intra- and interchain
hydrogen bonds contributed from N–H groups of the capping 4-methylpyrazole ligands. Magnetic measurements show weak anti-
ferromagnetic interactions with exchange coupling parameters of J = ꢀ0.018 cmꢀ1 for 2 and J = ꢀ0.062 cmꢀ1 for 3 through the
P
extended tp ligand on the basis of an infinite chain model (H = ꢀJ Si Æ Si + 1).
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Manganese compounds; Terephthalate ligand; Hydrogen bonds; Magnetic properties
1. Introduction
the long separations between metal centers bridged by
tp, the ligand can mediate magnetic interactions ranging
from weak ferro- to weak antiferromagnetic interac-
tions. Special focus has been on copper(II) compounds,
which contain dinuclear [10], tetranuclear [11], 1D [12]
and 2D [13] systems. In particular, the systematic ap-
proaches in dinuclear copper(II) compounds with a var-
iation of metal–metal separations were carried out to
establish magnetic exchange mechanism which is trans-
mitted through tp bridges and/or hydrogen bonds. In re-
cent years, the use of the extended bridge has appeared
on other coordination compounds, composed of diva-
lent metal cations Cd(II), Zn(II), Ni(II), Co(II), and
Mn(II), with dinuclear, 1D chain, or 3D network struc-
tures [14–20].
The field of molecular magnetism has received great
attraction on account of its promising application [1–
4]. To grasp the basic concept in the magnetic phenom-
ena, the insight into magnetic coupling pathways based
on structural parameters of geometry and distance is of
importance. Many efforts have been directed in the past
decade to design magnetic systems with extended bridg-
ing ligands in order to search for the limiting distance
for magnetic exchange interactions between paramag-
netic metal centers [5–9]. In this respect, terephthalate
(=tp) ligand has played an important role in the elucida-
tion of the long-range exchange couplings. In spite of
*
The tuning of molecular dimensionality in a lattice
has been one of the interesting challenges in the research
Corresponding author. Tel.: +82232903138; fax: +82232903121.
E-mail address: cshong@korea.ac.kr (C.S. Hong).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.05.002

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C.S. Hong et al. / Inorganica Chimica Acta 358 (2005) 3341–3346
Table 1
Crystallographic data for [Mn(4-methylpyrazole)3(H2O)(tp)]n (2) and
[Mn(4-methylpyrazole)4(tp)]n (3)
of a magnetostructural relationship and in supramolec-
ular architectures of extended inorganic networks
[21–23]. A 1D tp-bridged Mn(II) compound including
2,20-bipyridine as a capping ligand was reported in order
to get some information about the influence of number
and symmetry of the magnetic orbitals on exchange cou-
pling [24]. With the aim of searching for the role of cap-
ping ligands on molecular dimension, we adopted a
nonchelating 3(5)-methylpyrazole as a capping ligand
instead of a bidentate ligand, 2,20-bipyridine, yielding
a tp-bridged 3D manganese(II) compound, [Mn(5-methyl
pyrazole)2(tp)]n (1) [20]. From this result, it is manifest
that the nonchelating capping ligand in the Mn(II) com-
pounds strongly affects molecular dimensionality. To
probe the influence of a minimal structural alteration
in the methyl position of the pyrazole ligand on
molecular structure, we attempted to employ 4-meth-
ylpyrazole as a capping ligand, in substitution for 3(5)-
methylpyrazole. Herein, we report the synthesis, crystal
structures, and magnetic properties of two new 1D
Mn(II) coordination polymers, [Mn(4-methylpyraz-
ole)3(H2O)(tp)]n (2) and [Mn(4-methylpyrazole)4(tp)]n
(3). The overall supramolecular structures for those
compounds incorporated by hydrogen bonds can be
viewed as a 3D network array (2) and a 2D sheet (3).
The magnetic data reveal that antiferromagnetic interac-
tions through the extended bridge tp are operative.
2
3
Molecular formula
Formula weight
Crystal system
Space group
C20H24MnN6O5
483.39
C12H14Mn0.5N4O2
273.74
triclinic
monoclinic
P21/c
ꢀ
P1
˚
a (A)
17.346(2)
12.000(3)
11.457(3)
90
8.753(2)
9.281(1)
9.859(1)
71.16(1)
65.14(2)
78.76(2)
686.1(2)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
102.81(2)
90
3
˚
V (A )
2325.4(8)
4
1.381
Z
Dcalc (g cmꢀ3
)
1.325
0.525
l (mmꢀ1
R1
)
0.610
0.0759
0.1630
0.0359
0.0991
wR2
netic corrections of 2 and 3 were estimated from
Pascalꢀs Tables.
2.3. Crystallographic data collection and structure
determination
X-ray data for 2 and 3 were collected at room temper-
ature on an Enraf-Nonius CAD4TSB diffractometer
equipped with graphite monochromated Mo Ka radia-
˚
tion (k = 0.71073 A). Cell dimensions and intensities
2. Experimental
were measured by x/2h scan modes. A total of 2568
(2) and 2389 (3) reflections were scanned in the ranges
2.08ꢁ < h < 25.07ꢁ (2) and 2.32ꢁ < h < 24.98ꢁ (3) with
2.1. Preparation of the compounds
0 6 h 6 20, 0 6 k 6 14, ꢀ13 6 l 6 13 for
2
and
2.1.1. [Mn(4-methylpyrazole)3(H2O)(tp)]n (2)
ꢀ10 6 h 6 0, ꢀ11 6 k 6 10, ꢀ11 6 l 6 10 for 3. From
these, 1162 (2) and 2307 (3) reflections were assumed
to be observed applying the condition Fo > 4r(Fo).
The structures were solved with SIR-92 and refined by
least-squares analysis using anisotropic thermal param-
eters for non-hydrogen atoms with SHELXL-97 in the
WINGX package [25]. All hydrogen atoms except for
hydrogens bound to water molecules were calculated
at idealized positions. The positions of water hydrogen
atoms in 2 determined from the difference Fourier maps
were not refined. Crystallographic data and details of
data collection are listed in Table 1.
Reaction of 4-methylpyrazole (1.0 mmol) with an
aqueous solution of manganese(II) acetate (0.5 mmol)
was followed by addition of dipotassium tp (0.50 mmol)
in water with 10 min stirring. Slow evaporation of the
filtrate afforded white crystalline 2 in 17 % yield based
on Mn. Calc. for C20H24MnN6O5: C, 49.70; H, 5.00;
N, 17.39. Found: C, 49.69; H, 5.07; N, 16.94%.
2.1.2. [Mn(4-methylpyrazole)4(tp)]n (3)
It was obtained with the same procedure as 2 by using
4 equiv. of 4-methylpyrazole instead of 2 equiv. in a
yield of 31 %. Calc. for C12H14Mn0.5N4O2: C, 52.65;
H, 5.15; N, 20.47. Found: C, 52.30; H, 5.13; N, 20.81%.
2.2. Physical measurements
3. Results and discussion
Elemental analyses for C, H, and N were performed
at the Elemental Analysis Service Center of the Korea
Basic Science Institute. Infrared spectra were obtained
from KBr pellets with an EQUINOX 55 spectrometer.
Magnetic susceptibilities were carried out using a Quan-
tum Design MPMS-7 SQUID susceptometer. Diamag-
3.1. Syntheses and characterization
A covalent-linked 3D Mn(II) compound (1) was pre-
pared by employing 2–4 equiv. of 3(5)-methylpyrazole
with respect to Mn(II) ion and tp ligand, which is con-
firmed by IR and X-ray analysis. In comparison, the

C.S. Hong et al. / Inorganica Chimica Acta 358 (2005) 3341–3346
3343
use of a ratio of Mn2+:4-methylpyrazole:tp = 1:2:1 pro-
duced a structurally quite different 1D coordination
polymer 2. Unlike 3(5)-methylpyrazole, the reaction
with 4 equiv. of 4-methylpyrazole yielded a new 1D
product 3 that is not identical to 2. Thus, a slight change
of the methyl positions in the capping ligands causes a
sizable variation of molecular structure in the solid state.
The most interesting aspects of the IR spectra of
these compounds deal with the possibility to determine
the nature of tp coordination to metal ions. The occur-
rence of two strong and broad bands in the region 1700–
1200 cmꢀ1 is assigned to the asymmetric ½¼ maðCO ꢀÞꢁ
2
and symmetric ½¼ msðCO2ꢀÞꢁ stretching frequencies of
the coordinated tp ligands [26]. These characteristic
peaks are observed at 1574, 1385 cmꢀ1 for 2 and 1557,
1383 cmꢀ1 for 3, respectively. The differeꢀn1ces (D) be-
tween maðCO2ꢀÞ and msðCO2ꢀÞ are 189 cm for 2 and
174 cmꢀ1 for 3. The calculated values, which compared
with the reference value (D = 170 cmꢀ1) of dipotassium
tp, fall in the borderline between the bridging and
monodentate modes [26]. From the structures described
below, it is found that compounds 2 and 3 possess tp li-
gands in the monodentate modes where the noncoordi-
nated carboxylate oxygens of tp are subject to
hydrogen bonds. The broad bands in the range 3000–
2600 cmꢀ1 are observed, reflecting the existence of
hydrogen bonds, in agreement with X-ray structure
analyses.
Fig. 1. (a) ORTEP drawing of 2 with the atom numbering scheme
(50% probability ellipsoids). (b) 1D chain involving hydrogen bonds
illustrated by the dotted lines.
Table 2
˚
Selected bond distances (A) and angles (ꢁ) for [Mn(4-methylpyraz-
ole)3(H2O)(tp)]n (2)
3.2. Description of Crystal Structures
Mn(1)–O(1)
Mn(1)–O(w)
Mn(1)–N(3)
Mn(1)–O(3)
Mn(1)–N(1)
Mn(1)–N(5)
2.150(10)
2.232(7)
2.244(13)
2.160(9)
2.238(10)
2.292(9)
3.2.1. [Mn(4-methylpyrazole)3(H2O)(tp)]n (2)
The crystal structure of 2 is shown in Fig. 1(a) together
with the atom-numbering scheme. Selected bond dis-
tances and angles are shown in Table 2. The local geom-
etry around each Mn(II) ion can be seen as distorted
octahedral, involving three nitrogen atoms from 4-meth-
ylpyrazole capping ligands, one oxygen atom from water
molecule, and two oxygen atoms from tp with an average
O(1)–Mn(1)–O(3)
O(3)–Mn(1)–O(w)
O(3)–Mn(1)–N(1)
O(1)–Mn(1)–N(3)
O(w)–Mn(1)–N(3)
O(1)–Mn(1)–N(5)
O(w)–Mn(1)–N(5)
N(3)–Mn(1)–N(5)
C(12)–N(1)–Mn(1)
N(4)–N(3)–Mn(1)
N(6)–N(5)–Mn(1)
C(5)–O(3)–Mn(1)
O(1)–Mn(1)–O(w)
O(1)–Mn(1)–N(1)
O(w)–Mn(1)–N(1)
O(3)–Mn(1)–N(3)
N(1)–Mn(1)–N(3)
O(3)–Mn(1)–N(5)
N(1)–Mn(1)–N(5)
N(2)–N(1)–Mn(1)
C(16)–N(3)–Mn(1)
C(18)–N(5)–Mn(1)
C(1)–O(1)–Mn(1)
163.7(3)
96.9(6)
87.7(5)
86.8(4)
˚
bond distance of 2.22(5) A. It deserves to be noted that
81.2(6)
83.7(6)
the chemical environment around the Mn(II) center is
asymmetric, which is not commonly encountered in the
crystal structures. The two 4-methylpyrazole ligands con-
taining the N1 and N3 atoms are almost planar with the
largest deviation from the least-squares planes of
ꢀ0.0232 at N1 and 0.0155 at N4, respectively, whereas
the rest with the N5 atom is slightly distorted exhibiting
the largest deviation from the least-squares plane of
176.9(6)
98.3(5)
135.4(10)
122.5(10)
129.6(11)
146.1(11)
99.3(6)
95.7(4)
82.2(6)
94.6(4)
˚
0.1063 A at C19. There exist two crystallographically dif-
ferent tp ligands since inversion centers lie at the centers
of the benzene rings of the tp ligands, resulting in a 1D
chain structure (Fig. 1). The dihedral angles of the car-
boxylate groups and benzene rings of the two different
tp are equal to 4.7ꢁ for O1-linked tp and 3.3ꢁ for O3-
linked tp. The benzene rings of the adjacent tp bridges
are tilted by 56.3ꢁ. The intrachain Mn. . .Mn distances
163.4(3)
80.1(5)
98.3(6)
122.8(10)
127.1(10)
125.4(13)
146.1(10)

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C.S. Hong et al. / Inorganica Chimica Acta 358 (2005) 3341–3346
˚
are 11.534 A through the O1 contained tp bridge and
˚
11.581 A through the O3 contained tp bridge.
bonding with an interchain Mn. . .Mn distance of
˚
7.062 A, eventually leading to the formation of a supra-
molecular extended 3D network structure.
Another interesting feature of this structure is the
presence of intrachain hydrogen bonds which are ob-
served between the 4-methylpyrazole N–H groups and
carboxylate oxygen atoms, as given in Table 3. More-
over, interchain hydrogen bonds occur between water
molecules bound to Mn(II) ions in one chain and the
noncoordinated oxygen atoms of tp bridges in other
chains, which are analogously found in a hydrogen-
bonded supramolecular Mn(II) complex [27]. These
hydrogen bonds thus appear to stabilize the asymmetry
molecular disposition around the Mn center. The tp li-
gand acts in the bridging mode in terms of one carbox-
ylate oxygen covalently linked to the metal ion and the
other hydrogen-bonded to the water molecule, as de-
picted in Fig. 2. The two shortest Mn(II) ions present
in adjacent chains are connected through hydrogen
3.2.2. [Mn(4-methylpyrazole)4(tp)]n (3)
An ORTEP drawing of the cationic part of 3 giving the
atom-numbering scheme is illustrated in Fig. 3(a).
Selected bond distances and angles are summarized in
Table 4. This crystal structure is similar, apart from four
4-methylpyrazole capping ligands around a Mn atom, to
that of 2. The Mn(II) ion that sits in an inversion center
adopts a distorted octahedral arrangement with an aver-
˚
age bond length of 2.24(5) A. All the 4-methylpyrazole
rings retain planarity as indicated by the largest devia-
˚
tions from the mean planes of 0.0096 A at C12 and
˚
0.0183 A at C22. The 1D structure of 3 comprises the
neutral Mn(4-methylprazole)4(tp) units bridged by the
tp ligands, as illustrated in Fig. 3(b). The dihedral angle
of the carboxylate group and benzene ring of tp is found
to be 8.7ꢁ. The benzene rings of the neighboring tp ligands
Table 3
˚
Bond distances (A) and angles (ꢁ) of hydrogen bonds among NHꢂ ꢂ ꢂO
and OHꢂ ꢂ ꢂO for 2 (symmetry codes: (a) x, 3/2 ꢀ y, 1/2 + z; (b) x,
3/2 ꢀ y, ꢀ1/2 + z)
D–Hꢂ ꢂ ꢂA
d(D–H)
d(Hꢂ ꢂ ꢂA)
d(Dꢂ ꢂ ꢂA)
\(D–Hꢂ ꢂ ꢂA)
N2–H2ꢂ ꢂ ꢂO2
0.86
0.86
0.86
0.90
0.99
1.91
1.89
2.54
1.79
1.76
2.762
2.710
2.985
2.666
2.713
171
160
113
165
162
N4–H4ꢂ ꢂ ꢂO4
N6–H6ꢂ ꢂ ꢂO3
Ow–Hw1ꢂ ꢂ ꢂO2a
Ow–Hw2ꢂ ꢂ ꢂO4b
Fig. 3. (a) ORTEP drawing of 3 with the atom numbering scheme
(50% probability ellipsoids). (b) Segment of a chain of 3.
Table 4
˚
Selected bond distances (A) and angles (ꢁ) for [Mn(4-methylpyraz-
ole)4(tp)]n (3)
Mn(1)–O(1)
Mn(1)–N(21)
Mn(1)–N(11)
2.1774(14)
2.2766(16)
2.2635(18)
O(1)–Mn(1)–N(11)
N(11)–Mn(1)–N(21)
N(12)–N(11)–Mn(1)
N(22)–N(21)–Mn(1)
O(1)–Mn(1)–N(21)
C(11)–N(11)–Mn(1)
C(21)–N(21)–Mn(1)
C(1)–O(1)–Mn(1)
88.75(6)
91.21(7)
129.15(14)
123.13(13)
87.21(6)
Fig. 2. Extended view in the bc-plane of 2, showing a 3D network
formed by hydrogen bonds (dotted lines). The hydrogen bonds
between carboxylate oxygens and pyrazole NH groups are omitted
for clarity.
126.21(14)
131.82(15)
134.42(13)

C.S. Hong et al. / Inorganica Chimica Acta 358 (2005) 3341–3346
3345
are parallel. The intrachain separation between two neigh-
˚
boring Mn(II) atoms is 11.449 A, shorter than that of 2.
All the NH moieties of the four 4-methylpyrazole
groups coordinated to the Mn ion undergo hydrogen
bonds to unbound carboxylate oxygen atoms, as sum-
marized in Table 5. Namely, intrachain and interchain
hydrogen bonds take place between pyrazole NH
groups and free carboxylate oxygens of tp bridges in
the same and adjacent chains, respectively. Conse-
quently, the overall structural view can be described as
a 2D sheet with the shortest interchain Mn. . .Mn dis-
˚
tance of 8.753 A (Fig. 4).
3.3. Magnetic properties
The thermal variations of the molar magnetic suscep-
tibility (vm) shown in Figs. 5 and 6 were collected on
powdered samples of compounds 2 and 3 in the temper-
ature range 1.8–300 K. For 2, lowering the temperature
causes the vmT value to gradually decrease and finally go
down to 4.11 cm3 K molꢀ1 at 1.8 K. In the case of 3, the
vmT value behaves in a similar fashion to 2. At low tem-
peratures vmT decreases sharply and then reaches to a
value of 3.28 cm3 K molꢀ1 at 1.8 K. The Curie–Weiss
fits result in C = 4.53 cm3 K molꢀ1, h = ꢀ0.7 K for 2
and C = 4.53 cm3 K molꢀ1, h = ꢀ0.6 K for 3. Such mag-
netic behaviors represent the occurrence of weak antifer-
romagnetic interactions between magnetic centers.
The observed magnetic behavior can be interpreted
using the following modified analytical expression de-
Fig. 5. Plots of observed vm and vmT vs. T for 2. The solid lines
represent the best theoretical fits.
Table 5
˚
Bond distances (A) and angles (ꢁ) of hydrogen bonds between pyrazole
NH and carboxylate O atoms for 3 (symmetry codes: (a) ꢀx, ꢀy, 2ꢀ z;
(b) 1 + x, y, z)
D–Hꢂ ꢂ ꢂA
N12–H12ꢂ ꢂ ꢂO2a
N12–H12ꢂ ꢂ ꢂO2b
N22–H22ꢂ ꢂ ꢂO2b
d(D–H)
d(Hꢂ ꢂ ꢂA)
2.38
2.29
1.86
d(Dꢂ ꢂ ꢂA)
2.921
3.016
2.708
\(D–Hꢂ ꢂ ꢂA)
126
150
163
Fig. 6. Plots of observed vm and vmT vs. T for 3. The solid lines
represent the best theoretical fits.
0.81
0.81
0.88
rived from combining the infinite chain model
(H = ꢀJ Si Æ Si + 1) by Fisher and the molecular field
P
approximation (zJ0) [27]
vm ¼ Ng2b2F ðS; T Þ=f1 ꢀ zJ0F ðS; TÞg;
F ðS; TÞ ¼ SðS þ 1Þ=3kTfð1 þ uÞ=ð1 ꢀ uÞg;
u ¼ coth½JSðS þ 1Þ=kTꢁ ꢀ ½kT=JSðS þ 1Þꢁ.
ð1Þ
In view of the structure of 2, two possible exchange path-
ways are taken into account: one through the extended tp
ligand and the other through the hydrogen bonds. The
best least-squares fit to Eq. (1) for 2 gives parameters
g = 2.02, J = ꢀ0.018 cmꢀ1, zJ0 ꢃ 0 cmꢀ1, and TIP (tem-
perature independent paramagnetism) = 0.00031
cm3 molꢀ1. The measure of the goodness of fit R, defined
as R = U/(n ꢀ k) where n is the number of data points and
Fig. 4. Extended molecular representation of 3, depicting a 2D sheet
formed by hydrogen bonds (dotted lines). Hydrogen atoms are omitted
for clarity.
P
obs
k the number of parameters, and U ¼
½ðvmT Þi
i
calc 2
i
ꢀðvmTÞ ꢁ , corresponds to 1.0 · 10ꢀ4. For 3, the fitting

3346
C.S. Hong et al. / Inorganica Chimica Acta 358 (2005) 3341–3346
based on Eq. (1) leads to g = 2.03, J = ꢀ0.062 cmꢀ1
,
References
zJ0 ꢃ 0,
and
TIP = 0.00010
cm3 molꢀ1
with
R = 8.0 · 10ꢀ4. The J values are attributable to intrachain
magnetic interactions because they are not varied depend-
ing on the interchain Mn. . .Mn distances. Hence the ex-
change coupling constants (J), which are consistent with
that of a tp-bridged dinuclear complex, essentially arise
from intrachain magnetic couplings via the long tp
bridges between Mn(II) ions [14]. The smaller value of
the exchange parameter of 2 than that of 3 is expected
from the longer intrachain Mn. . .Mn separation in 2.
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We have prepared and characterized two new tp-
bridged 1D Mn(II) coordination complexes by employing
4-methylpyrazole as a capping ligand instead of 3(5)-
methylpyrazole that leads to a covalently linked 3D net-
work (1). The 1D coordination polymers are extended
via hydrogen bonds to a 3D network (2) and 2D sheet
(3), which display weak antiferromagnetic interactions
through tp bridges within a chain. It is noted that there ex-
ist intra- and interchain hydrogen bonds in both com-
pounds, which build up such supramolecular
frameworks. As a result it is evident that the subtle change
from 3-methyl to 4-methyl position on the capping ligand
gives rise to a substantial structural influence. Thus, it
may be very useful to adjust capping ligands to tune
molecular dimensionality in the supramolecular systems.
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Crystallographic data (excluding structure factors)
for 2 and 3 have been deposited with the Cambridge
Crystallographic Data Centre, CCDC Nos. 259501
and 259502, respectively. Copies of the data can be ob-
tained free of charge on application to The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(fax: (internat.) + 44 1223 336 033, e-mail: deposit
@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
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Acknowledgments
We thank an Operation Program on Shared Research
Equipment of KBSI and MOST. This work is financially
supported by the CRM-KOSEF.
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