Synthesis and characterization of one-dimensional nickel(II) macrocyclic complexes with bridging organic ligands

Article abstract of DOI:10.1016/S0277-5387(00)00593-3

Reactions of [Ni(L)]Cl₂·2H₂O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,0^1.18,0^7.12]docosane with 1,3,5-benzenetricarboxylate (BTC), 1,4-benzenedicarboxylate (BDC) and 2,5-pyridinedicarboxylate (PDC) in CHCl₃/water solution yield the one-dimensional nickel(II) complexes [Ni(L)]₃[BTC]₂·8H₂O (1), [Ni(L)(BDC)]·2H₂O (2) and [Ni(L)(PDC)]·H₂O (3). The structures were characterized by X-ray crystallography, magnetic susceptibility and thermogravimetry. Complex 1 reveals a geometrically symmetric core with a {4/6} coordination number set. The geometry around the four-coordinate Ni(3) is depicted as square planar, while the coordination geometry around the Ni(1) and Ni(2) ions is a tetragonally distorted octahedron in the direction of the chain. The crystal structures of the chain compounds 2 and 3 show an elongated octahedral trans arrangement about each nickel(II) ion. The magnetic behavior of all three compounds exhibits weak intrachain antiferromagnetic interactions with J values of - 1.13 cm^-1 for 1, - 1.37 cm^-1 for - 2 and 1.47 cm^-1 for 3. Compounds 1-3 thermally decompose to form the same products. The identities of the decomposition products are discussed. The hydrogen-bonding interaction in compounds 1-3 plays a significant role in aligning the molecules and the polymer strands in the crystalline solids.

Full text of DOI:10.1016/S0277-5387(00)00593-3

www.elsevier.nl/locate/poly
Polyhedron 20 (2001) 57–65
Synthesis and characterization of one-dimensional nickel(II)
macrocyclic complexes with bridging organic ligands
Ki-Young Choi a,*, Kang Moon Chun a, Il-Hwan Suh b
a Department of Cultural Heritage Conser6ation Science, Kongju National Uni6ersity, Kongju 314-701, South Korea
b Department of Physics, Chungnam National Uni6ersity, Taejon 305-764, South Korea
Received 14 July 2000; accepted 12 September 2000
Abstract
Reactions of [Ni(L)]Cl2·2H2O (L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane with 1,3,5-benzenetricar-
boxylate (BTC), 1,4-benzenedicarboxylate (BDC) and 2,5-pyridinedicarboxylate (PDC) in CHCl3/water solution yield the
one-dimensional nickel(II) complexes [Ni(L)]3[BTC]2·8H2O (1), [Ni(L)(BDC)]·2H2O (2) and [Ni(L)(PDC)]·H2O (3). The structures
were characterized by X-ray crystallography, magnetic susceptibility and thermogravimetry. Complex 1 reveals a geometrically
symmetric core with a {4/6} coordination number set. The geometry around the four-coordinate Ni(3) is depicted as square
planar, while the coordination geometry around the Ni(1) and Ni(2) ions is a tetragonally distorted octahedron in the direction
of the chain. The crystal structures of the chain compounds 2 and 3 show an elongated octahedral trans arrangement about each
nickel(II) ion. The magnetic behavior of all three compounds exhibits weak intrachain antiferromagnetic interactions with J values
of −1.13 cm−1 for 1, −1.37 cm−1 for 2 and −1.47 cm−1 for 3. Compounds 1–3 thermally decompose to form the same
products. The identities of the decomposition products are discussed. The hydrogen-bonding interaction in compounds 1–3 plays
a significant role in aligning the molecules and the polymer strands in the crystalline solids. © 2001 Published by Elsevier Science
B.V. All rights reserved.
Keywords: Crystal structures; Nickel(II) complexes; Macrocycle; Organic ligands; Chain complexes
polymers. Fujita et al. unprecedentedly observed the
appearance of quite different network patterns from
1. Introduction
almost the same crystallographic molecules. Upon com-
plexation with Cd(NO3)2, the ligand N,N%-diphenyl-1,4-
phenylenediamine [5] gave an infinite molecular ladder,
whilst fluorination of this ligand [6] afforded an infinite
molecular brick, despite the very similar unit crystal
structures of these complexes. However, macrocyclic
complexes have seldom been used as building blocks in
the construction of multidimensional networks [7]. The
multidentate macrocycle 1,3,5-benzenetricarboxylate
(BTC) is a good candidate for a molecular building
block because of its rigidity and stability in the result-
ing porous framework. In polymeric structures contain-
ing 1,3,5-benzenetricarboxylate (BTC3−), several
factors influence the specific framework structure that is
formed. For example [7a], the two-dimensional network
The self-assembly and self-organization of infinite
metal complexes with specific network topologies have
been of great interest due to their potential for
supramolecular chemistry and crystal engineering [1,2].
Cooperative intermolecular interactions such as coordi-
nation bonds, hydrogen bonds, and p–p stacking
provide supramolecular assemblies through the creation
of one-dimensional and multi-dimensional networks [3].
Recently, Atwood et al. [4] reported the crystal struc-
tures
of
[M(terephthalate)(4-picoline)2(H2O)2]·2(4-
picoline)
and
[M(terephthalate)(pyridine)2(H2O)2]·
2(pyridine)·2(H2O) (M=Co2+, Ni2+) which assemble
in the solid state to form one-dimensional coordination
[Ni(L)]3[BTC]2·18H2O
1,3,6,8,10,13-hexaazacyclotetradecane) results in a brick
wall structure, whilst a honeycomb structure is obtained
(L=1,8-bis(2-hydroxyethyl)-
* Corresponding author. Tel.: +82-41-8508541; fax: +82-41-
8508541.
E-mail address: kychoi@knu.kongju.ac.kr (K.-Y. Choi).
0277-5387/01/$ - see front matter © 2001 Published by Elsevier Science B.V. All rights reserved.
PII: S0277-5387(00)00593-3

58
K.-Y. Choi et al. / Polyhedron 20 (2001) 57–65
for [Ni(L)]3[BTC]2·18H2O·2C5H5N. The different
molecular topologies in these complexes arose from the
different coordination modes of the BTC3− anion.
In the present study, we report the preparation,
crystal structures and chemical properties of the one-di-
996(w), 952(w), 914(w), 806(m), 768(m), 726(s), 620(m).
UV–Vis (diffuse reflectance spectrum, umax): 523 nm.
FAB MS (m/z): 1888 (M+).
2.3. Synthesis of [Ni(L)(BDC)]·2H2O (2)
mensional
structures
[Ni(L)]3[BTC]2·8H2O
(1),
[Ni(L)(BDC)]·2H2O (2) and [Ni(L)(PDC)]·H2O (3)
(BTC3− =1,3,5-benzenetricarboxylate, BDC2− =1,4-
benzenedicarboxylate, PDC2− =2,5-pyridinedicarboxy-
This compound was prepared as pink crystals in a
reaction similar to that of 1, using Na2BDC (186 mg, 1
mmol) instead of Na3BTC. Yield: 63%. Anal. Found:
C, 56.4; H, 8.2; N, 9.5. Calc. for C28H48N4NiO6: C,
56.5; H, 8.1; N, 9.4%. IR (KBr, cm−1): 3421(s),
3257(m), 3147(m), 2930(s), 1613(s), 1570(s), 1431(m),
1372(s), 1304(m), 1154(m), 1110(s), 1062(m), 1014(m),
994(m), 948(m), 898(m), 813(s), 749(s), 638(w), 503(w).
UV–Vis (diffuse reflectance spectrum, umax): 524 nm.
FAB MS (m/z): 595 (M+).
late,
L=3,14-dimethyl-2,6,13,17-tetraazatricyclo-
[14,4,01.18,07.12]docosane). We also found that inter-
molecular hydrogen bonds in all compounds expand
the one-dimensional chain structures into two-dimen-
sional networks.
2. Experimental
2.4. Synthesis of [Ni(L)(PDC)]·H2O (3)
2.1. Materials and physical measurements
This compound was prepared as pink crystals in a
reaction similar to that of 1, using Na2PDC (187 mg, 1
mmol) instead of Na3BTC. Yield: 53%. Anal. Found:
C, 56.1; H, 7.8; N, 12.1. Calc. for C27H45N5NiO5: C,
56.1; H, 7.8; N, 12.1%. IR (KBr, cm−1): 3536(s),
3259(m), 3157(m), 2933(s), 2878(m), 1590(s), 1467(w),
1428(w), 1389(s), 1348(s), 1306(m), 1155(m), 1112(s),
1068(m), 1018(m), 995(m), 950(m), 902(m), 815(s),
764(m), 502(w). UV–Vis (diffuse reflectance spectrum,
umax): 518 nm. FAB MS (m/z): 578 (M+).
All chemicals and solvents used in the syntheses were
of reagent grade and were used without further purifi-
cation. The macrocycle L and [Ni(L)]Cl2·2H2O were
prepared according to the literature method [8]. IR
spectra were recorded with a Perkin–Elmer Paragon
1000 FT-IR spectrophotometer using KBr pellets. UV–
Vis diffuse reflectance spectra were recorded with a
Shimadzu UV2401 PC/DRS spectrophotometer. Mag-
netic susceptibility data on powder samples were col-
lected in the temperature range 2–300 K in an applied
field of 1 T with the use of a Quantum Design MPMS7
SQUID magnetometer. The diamagnetic corrections
were estimated from Pascal’s constants. Differential
thermal analysis and thermogravimetric analysis were
performed using a TGA 2050 Thermogravimetric Ana-
lyzer in flowing nitrogen at a heating rate of 10°C
min−1. High-resolution fast atom bombardment mass
spectrometry (FAB MS) were performed by using a
Jeol JMS-HA 110A/110A instrument. Elemental analy-
ses were carried out by the Korea Research Institute of
Chemical Technology, Taejon, Korea.
2.5. X-ray crystallography
Crystals
of
[Ni(L)]3[BTC]2·8H2O
(1),
[Ni(L)(BDC)]·2H2O (2) and [Ni(L)(PDC)]·H2O (3) were
used for data collection. Diffraction data were collected
on an Enraf-Nonius CAD4 diffractometer equipped
with graphite-monochromated Mo Ka radiation (u=
,
0.71069 A) at room temperature. Accurate cell parame-
ters and an orientation matrix were determined from
the least-squares fit of 25 reflections. An asymmetric
unit of intensity data was collected in the ꢀ-2q scan
mode. The intensity data were corrected for Lorentz
and polarization effects. Empirical absorption correc-
tion (c-scan) was applied. The crystal parameters and
details of the data collections and refinement for 1–3
are listed in Table 1. The structures were solved by
direct methods and successive cycles of difference
Fourier maps followed by least-squares refinements [9].
All non-hydrogen atoms were refined anisotropically.
All hydrogen atoms were placed in calculated positions
and allowed to ride upon the appropriate carbon and
nitrogen atoms and all their parameters were fixed. The
crystallographic data of 1–3 are summarized in Table 1
and the selected bond distances and angles in Tables
2–4.
2.2. Synthesis of [(NiL)3(BTC)2]·8H2O (1)
A chloroform solution (20 ml) of [Ni(L)]Cl2·2H2O
(502 mg, 1 mmol) was allowed to diffuse into an
aqueous solution (5 ml) of Na3BTC (276 mg, 1 mmol)
in a test tube for several days. A quantity of pink
crystals formed at the CHCl3/water interface. Crystals
were collected by filtration and washed with diethyl
ether, giving a yield of 62%. Anal. Found: C, 49.7; H,
8.5; N, 8.8. Calc. for C78H158N12Ni3O28: C, 49.6; H, 8.4;
N, 8.9%. IR (KBr, cm−1): 3411(s), 3352(s), 3053(s),
2929(s), 1624(s), 1558(s), 1446(m), 1430(s), 1363(s),
1306(w), 1273(w), 1188(w), 1093(s), 1050(m), 1019(m),

K.-Y. Choi et al. / Polyhedron 20 (2001) 57–65
59
Table 1
Crystallographic data
1
2
3
Empirical formula
Formula weight
Temperature (K)
C78H158N12Ni3O28
1888.29
291
C
595.41
293
28H48N4NiO6
C27H45N5NiO5
578.39
293
,
Wavelength (A)
0.71069
Triclinic
0.71069
Triclinic
0.71069
Monoclinic
P21
Crystal system
Space group
(
(
P1
P1
Unit cell dimensions
,
a (A)
9.473(2)
8.860(2)
9.777(2)
10.178(2)
66.17(2)
65.74(2)
11.442(3)
13.754(2)
9.994(1)
,
b (A)
16.403(2)
16.831(2)
68.26(1)
,
c (A)
h (°)
i (°)
85.16(1)
115.75(2)
k (°)
79.52(2)
2388.3(6)
1
1.313
0.664
76.25(2)
732.5(2)
1
1.350
0.709
320
3
,
V (A )
1416.6(5)
2
1.356
0.730
Z
Dcalc (Mg m−3
)
Absorption coefficient (mm−1
F(000)
)
1018
620
Crystal size (mm)
q range for data collection (°)
Index ranges
0.59×0.36×0.26
2.19–24.97
−115h511, −185k519,
05l519
0.23×0.13×0.10
2.29–24.97
−95h510, −105k511,
05l512
0.40×0.17×0.07
2.26–24.97
−135h512, 05k516,
05l511
Reflections collected
7776
2540
2763
Independent reflections
Absorption correction
Max./min. transmission
Refinement method
7492 (Rint=0.0727)
Empirical
0.829 and 0.582
2390 (Rint=0.0381)
Empirical
0.917 and 0.085
2607 (Rint=0.0307)
Empirical
0.948 and 0.463
Full-matrix least-squares on F2 Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices (I\2|(I))
R indices (all data)
7492/0/547
1.015
2390/0/178
1.124
R1=0.0540, wR2=0.1189
R1=0.0758, wR2=0.1240
0.603 and −0.890
2607/1/343
1.030
R1=0.0504, wR2=0.1141
R1=0.1042, wR2=0.1399
0.428 and −0.300
R1 a=0.0704, wR2 b=0.2242
R1=0.0969, wR2=0.2404
1.529 and −0.920
Largest difference peak and hole (e
−3
,
A
)
a R1=ꢀꢁꢁFoꢁ−ꢁFcꢁꢁ/ꢀꢁFoꢁ.
b wR2=[ꢀ[w(Fo2−Fc2)2]/ꢀ[w(Fo2)2]]1/2
.
3. Results and discussion
tances (Ni(1)ꢀO(1)=2.193(4) and Ni(2)ꢀO(3)=
,
2.163(4) A), giving an axially elongated octahedron in
the one-dimensional chain direction. The average
3.1. Description of the structures
,
Ni(3)ꢀN bond distance of 1.988(4) A is in the normal
range for NiꢀN (secondary amines) bond distances of
square-planar nickel(II) complexes with 14-membered
tetraaza macrocycles [8b,10]. Two nickel(II) macro-
cyclic complexes (Ni(1) and Ni(2)) are bridged by the
An ORTEP diagram of [(NiL)3(BTC)2]·8H2O (1) with
the atomic numbering scheme is shown in Fig. 1(a).
The compound 1 contains a mixture of polymeric and
monomeric ions. An inversion center exists on the
central nickel(II) ion. The complex has a geometrically
symmetric core with a {4/6} coordination number set.
The geometry around the four-coordinate Ni(3) is de-
picted as square planar with four secondary amines of
the macrocycle, while the coordination geometry
around the Ni(1) and Ni(2) ions is a tetragonally dis-
torted octahedron in which each nickel ion is coordi-
nated by four secondary amines of the macrocycle and
by two carboxylate oxygen atoms of the BTC ligands.
The two NiꢀN4 (secondary amines) distances
BTC3− unit with a separation of 11.347(3) A, whereas
,
the Ni(1)…Ni(3) and Ni(2)…Ni(3) distances between
the two complexes and uncoordinated Ni(3) complex
,
are 9.302(1) and 10.097(2) A, respectively. The coordi-
nation of the benzenetricarboxylato bridge is slightly
asymmetrical; the two Ni(1)ꢀO(1)ꢀC(35) and
Ni(2)ꢀO(3)ꢀC(31) angles are 132.8(4) and 134.9(4)°, the
larger angle corresponding to the shorter bond dis-
tance. The dihedral angles (h) between the plane of the
carboxylate group and benzene ring involving Ni(1)
and Ni(2) are 20.0 and 1.7°. Moreover, the dihedral
angles (i) between the plane of the carboxylate group
,
(Ni(1)ꢀNav=2.077(4) and Ni(2)ꢀNav=2.057(4) A) are
shorter than the two NiꢀO (carboxylate oxygens) dis-

60
K.-Y. Choi et al. / Polyhedron 20 (2001) 57–65
Table 4
and NiN2O2 plane involving Ni(1) and Ni(2) are 10.6
and 9.5°, respectively. The free carbonyl oxygen atoms
a
,
Selected bond lengths (A) and angles (°) for [Ni(L)(PDC)]·H2O (3)
of BTC form hydrogen bonds with the secondary
NiꢀN(1)
NiꢀN(2)
NiꢀN(3)
NiꢀN(4)
NiꢀO(1)
NiꢀO(3) b
2.031(13)
2.066(16)
2.129(16)
2.088(13)
2.137(10)
2.121(9)
O(1)ꢀC(21)
O(2)ꢀC(21)
O(3)ꢀC(27)
O(4)ꢀC(27)
1.263(14)
1.244(16)
1.254(15)
1.229(17)
11.465(4)
1
,
amines of the macrocycle (O(2) …N(2) 2.846(7) A,
2
,
163.0° and O(4) …N(3) 2.910(8) A, 154.6°. The water
molecules also forms hydrogen bonds with the sec-
b
Ni…Ni
ondary amine of the macrocycle (OW(4)3…N(1)
,
3.117(9) A, 167.0° with carboxylate oxygen atoms
N(1)ꢀNiꢀN(2)
N(1)ꢀNiꢀN(3)
N(1)ꢀNiꢀN(4)
N(2)ꢀNiꢀN(3)
N(2)ꢀNiꢀN(4)
N(3)ꢀNiꢀN(4)
O(1)ꢀNiꢀN(1)
O(1)ꢀNiꢀN(2)
O(1)ꢀNiꢀN(3)
O(1)ꢀNiꢀN(4)
86.3(6)
97.7(6)
178.7(10)
176.0(7)
94.9(6)
81.1(7)
92.4(4)
94.8(6)
84.7(5)
87.1(4)
O(3) bꢀNiꢀN(2)
O(3) bꢀNiꢀN(3)
O(3) bꢀNiꢀN(4)
O(1)ꢀNiꢀO(3) b
NiꢀO(1)ꢀC(21)
Ni cꢀO(3)ꢀC(27)
O(1)ꢀC(21)ꢀO(2)
O(1)ꢀC(21)ꢀC(22)
O(3)ꢀC(27)ꢀO(4)
O(3)ꢀC(27)ꢀC(24)
84.7(5)
95.7(5)
92.6(4)
179.4(7)
135.0(10)
134.7(9)
125.9(13)
112.8(13)
124.9(13)
117.7(13)
,
(OW(4)…O(2) 2.722(8) A and OW(5)…O(5) 2.760(9)
,
A) and with the other water inclusions (OW(1)…OW(2)
,
,
A,
2.861(6)
A,
OW(1)…OW(3)
2.859(6)
Table 2
,
Selected bond lengths (A) and angles (°) for [(NiL)3(BTC)2]·8H2O
(1) a
O(3) bꢀNiꢀN(1) 87.9(4)
Ni(1)ꢀN(1)
Ni(1)ꢀN(2)
Ni(1)ꢀO(1)
Ni(2)ꢀN(3)
Ni(2)ꢀN(4)
Ni(2)ꢀO(3)
Ni(3)ꢀN(5)
Ni(3)ꢀN(6)
Ni(1)…Ni(2)
2.092(5)
2.062(5)
2.193(4)
2.027(5)
2.087(5)
2.163(4)
1.951(5)
2.024(5)
11.347(2)
O(1)ꢀC(35)
O(2)ꢀC(35)
O(3)ꢀC(31)
O(4)ꢀC(31)
O(5)ꢀC(38)
O(6)ꢀC(38)
Ni(2)…Ni(3)
Ni(1)…Ni(3)
1.242(7)
1.233(7)
1.230(7)
1.265(7)
1.182(7)
1.310(8)
10.099(2)
9.302(1)
a Symmetry transformations used to generate equivalent atoms.
b x−1, y, z−1.
c x+1, y, z+1.
1
,
OW(1)…OW(8) 2.532(3) A, OW(2)…OW(3) 2.870(7)
2
,
,
A, OW(4)…OW(5) 2.963(9) A, and OW(6)…OW(7)
,
2.718(11) A). Interestingly, the secondary amines N(5)
N(1)ꢀNi(1)ꢀN(2)
N(1)ꢀNi(1)ꢀN(2)
O(1)ꢀNi(1)ꢀN(1)
O(1)ꢀNi(1)ꢀN(2)
N(3)ꢀNi(2)ꢀN(4)
82.4(2)
97.6(2)
87.75(18)
90.9(2)
80.9(2)
99.1(2)
88.2(2)
82.0(2)
94.5(2)
85.5(2)
132.8(4)
Ni(2)ꢀO(3)ꢀC(31)
O(1)ꢀC(35)ꢀO(2)
O(1)ꢀC(35)ꢀC(34) 117.1(6)
O(2)ꢀC(35)ꢀC(34) 114.9(6)
O(3)ꢀC(31)ꢀO(4)
O(3)ꢀC(31)ꢀC(32) 117.6(6)
O(4)ꢀC(31)ꢀC(32) 115.9(5)
O(5)ꢀC(38)ꢀO(6)
O(5)ꢀC(38)ꢀC(37) 125.4(6)
O(6)ꢀC(38)ꢀC(37) 113.9(6)
134.9(4)
128.0(6)
and N(6) of the macrocycle found in the lattice form
hydrogen bonds to an adjacent polymeric chain via
carboxylate oxygens O(5) and O(6) of the uncoordi-
nated BTC ligand, which gives rise to a two-dimen-
sional hydrogen-bonded network (O(5)…N(5) 3.149(9)
b
126.5(6)
N(3)ꢀNi(2)ꢀN(4) c
O(3)ꢀNi(2)ꢀN(3)
O(3)ꢀNi(2)ꢀN(4)
N(5)ꢀNi(3)ꢀN(6)
N(5)ꢀNi(3)ꢀN(6) d
Ni(1)ꢀO(1)ꢀC(35)
,
,
A, 128.4°, O(5)…N(6) 3.234(8) A, 127.9° and
120.2(7)
,
O(6)…N(6) 2.781(8) A, 177.0°) (Fig. 1(b)).
An ORTEP drawing of [Ni(L)(BDC)]·2H2O (2) with
the atomic numbering scheme is shown in Fig. 2(a).
The crystal structure of 2 has cationic [Ni(L)]2+ units,
BDC2− anion, and water molecules. The complex has
an inversion center at the midpoint of the benzene ring
of the BDC2− ligand. In the chain structure, the nick-
el(II) ion exists in a distorted octahedral coordination
environment in which the macrocycle and two trans
BDC ligands have assembled around the metal center.
Therefore, one-dimensional coordination polymers
have formed. The Ni…Ni% distance across the polymer
backbone is 11.528(3) A, whereas the closest Ni…Ni%
distance between neighboring strands is 10.898(3) A.
The average NiꢀN distance of 2.067(3) A is shorter
than the axial NiꢀO(1) distance of 2.116(3) A, indicat-
ing the axially elongated octahedron is in the chain
direction. The axial NiꢀO(1) bond is not perpendicular
to the NiN4 plane with N(1)ꢀNiꢀO(1) and
N(2)ꢀNiꢀO(1) angles of 88.2(1) and 83.2(1)°, respec-
tively. The NiꢀO(1)ꢀC(11) angle and C(11)ꢀO(1) dis-
tance relative to the BDC ligand are 136.1(3)° and
a Symmetry transformations used to generate equivalent atoms.
b −x, −y+1, −z+1.
c −x+2, −y, −z+1.
d −x+1, −y+1, −z.
Table 3
Selected bond lengths (A) and angles (°) for [Ni(L)(BDC)]·2H2O (2)
a
,
NiꢀN(1)
NiꢀN(2)
NiꢀO(1)
2.053(4)
2.080(4)
2.116(3)
O(1)ꢀC(11)
O(2)ꢀC(11)
1.235(5)
1.257(5)
11.528(3)
,
b
Ni…Ni
,
,
N(1)ꢀNiꢀN(2)
N(1)ꢀNiꢀN(2) c
O(1)ꢀNiꢀN(1)
O(1)ꢀNiꢀN(2)
84.5(2)
95.5(2)
88.2(1)
83.2(1)
NiꢀO(1)ꢀC(11)
136.1(3)
127.0(5)
117.5(4)
115.3(4)
,
O(1)ꢀC(11)ꢀO(2)
O(1)ꢀC(11)ꢀC(12)
O(2)ꢀC(11)ꢀC(12)
a Symmetry transformations used to generate equivalent atoms.
b −x, −y+1, −z+1.
c −x+1, −y, −z+1.
,
1.235(5) A, respectively. The values of the dihedral
angles (a and b) for this structure are 5.6 and 7.3°,
1 Symmetry code: -x, -y+1, -z+1.
2 Symmetry code: -x+2, -y, -z+1.
3 Symmetry code: -x+1, -y+1, -z+1.
respectively. Interestingly, the one-dimensional chain in

K.-Y. Choi et al. / Polyhedron 20 (2001) 57–65
61
Fig. 1. (a) An ORTEP drawing of [(NiL)3(BTC)2]·8H2O (1) with the atomic numbering scheme (30% probability ellipsoids shown). (b) Crystal
packing of 1, showing the intermolecular hydrogen bonds as dotted lines. The hydrogen atoms are omitted for clarity.
lattice also forms hydrogen bonds with the carboxylate
2 is linked by hydrogen bonds involving the carboxylate
,
oxygens of a BDC ion (OW…O(2) 2.883(5) A and
oxygen atoms of BDC ligand and the secondary amines
5
,
,
OW …O(2) 2.900(6) A. This interaction, as shown in
of the macrocycle (O(1)…N(2) 2.785(5) A, 107.5°,
O(1)4…N(1) 2.995(5) A, 100.6° and O(2)4…N(1)
,
Fig. 2(b), gives rise to a two-dimensional hydrogen-
bonded network.
,
2.932(5) A, 153.6°. The water molecule found in the
4 Symmetry code: -x+1, -y, -z+1.
5 Symmetry code: -x+1, -y+1, -z.

62
K.-Y. Choi et al. / Polyhedron 20 (2001) 57–65
Fig. 2. (a) An ORTEP drawing of [Ni(L)(BDC)]·2H2O (2) with the atomic numbering scheme (30% probability ellipsoids shown). (b) Crystal
packing of 2, showing the intermolecular hydrogen bonds as dotted lines. The hydrogen atoms are omitted for clarity.
,
of the PDC ligand (N(1)…O(2) 2.926(15) A, 156.1°,
An ORTEP drawing of [Ni(L)(PDC)]·H2O (3) with the
atomic numbering scheme is shown in Fig. 3(a). The
nickel atom occupies a distorted octahedral coordina-
tion environment in which the macrocycle, two water
molecules and two trans PDC2− ions have assembled
around each nickel center. Consequently, a one-dimen-
sional coordination polymer has formed. Each nickel
atom is coordinated by one macrocycle two PDC lig-
ands. The intramolecular Ni…Ni% distance is 11.465(4)
8
,
N(2)…O(3) 2.822(18) A, 105.9°, N(3)…O(1) 2.874(19)
8
,
,
A, 107.7° and N(4)…O(4) 2.908(16) A, 151.4°. Fur-
thermore, the water molecule OW(2) is linked to the
uncoordinated PDC oxygen atoms O(2) and O(4)
,
through hydrogen bonds (OW(2)…O(2) 2.954(15) A
9
,
and OW(2)…O(4) 2.851(14) A, to form the two-dimen-
sional hydrogen-bond system (Fig. 3(b)).
,
A, whereas the shorter intermolecular Ni…Ni% distance
3.2. Spectroscopic properties
,
,
is 8.947(3) A. The average NiꢀN distance of 2.079(7) A
is somewhat shorter than the two NiꢀO distances
(PDC) (NiꢀO(1)=2.137(10) and NiꢀO(3) =2.121(9) A
The electronic diffuse reflectance spectra of the com-
pounds exhibit maximum absorptions at 523 nm for 1,
524 nm for 2 and 518 nm for 3, which are characteristic
chromophores for the nickel(II) ion coordinated with
N4O2 donors [11]. However, all compounds dissolve in
water and decompose into the original building block
[Ni(L)]Cl2·2H2O, which is identified by the UV–Vis
spectra showing the characteristic chromophore
(umax=463 nm) [8].
6
,
), which is similar to that observed in 2. Furthermore,
the axial NiꢀO (BDC) linkage is bent slightly off the
perpendicular to the NiN4 plane by 2.1–5.7°. The
NiꢀO(1)ꢀC(21) and Ni7ꢀO(3)ꢀC(27) angles and
C(21)ꢀO(1) and C(27)ꢀO(3) distances relative to the
PDC
ligand
are
,
135.0(10)ꢀ134.7(9)°
and
1.263(14)ꢀ1.254(15) A, respectively. The values of the
dihedral angles (a and b) for 3 are 2.8, 3.6° and 5.7,
11.6°, respectively. The secondary amines of the macro-
cycle forms hydrogen bonds with carboxylate oxygens
6 symmetry code: x-1, y, z-1.
8 Symmetry code: x-1, y, z-1.
9 Symmetry code: x, y, z-1.
7 symmetry code: x+1, y, z+1.

K.-Y. Choi et al. / Polyhedron 20 (2001) 57–65
63
3.3. Magnetic properties
practically constant in this series and that the values of
the h dihedral angle do not follow the expected trend,
these factors may not play a significant role. However,
the values of the i dihedral angle of these complexes
does slightly decrease with increasing antiferromagnetic
coupling. Although the intermolecular Ni…Ni dis-
The temperature dependency of the magnetic suscep-
tibilities (m) and the effective magnetic moments (veff)
per nickel(II) ion for the compounds 1–3 are shown in
Fig. 4(a–c). The room temperature magnetic moments
(vB) are 2.89 for 1, 3.19 for 2, and 2.88 for 3. For all
compounds the veff values gradually decrease with de-
creasing temperature, suggesting the presence of an
antiferromagnetic interaction between the nickel(II)
,
tances vary from 8.9 to 10.9 A, the values of J are
insensitive to it indicating that the weak magnetic cou-
pling observed is of intramolecular nature.
centers. The  data are interpreted using the isotropic
m
3.4. Thermogra6imetric analysis
nickel(II) chain spin Hamiltonian (S=1 and Hchain
=
−JꢀSi·Si+1) and fitted to Eq. (1) by neglecting zero-
The compounds 1–3 were heated in the temperature
range 30–1000°C in nitrogen gas (Fig. 5(a–c)). The
TGA data for all compounds showed three separate
weight losses. For 1, the first weight loss is observed
from 30 to 67°C, which is due to the loss of eight water
molecules (observed 8.4%, calculated 8.3%). A second
weight loss corresponding to the three macrocycles and
two BTC ligands (observed 82.1%, calculated 81.6%) is
found in the temperature range 309–600°C. A final
weight loss is observed above 600°C corresponding to
the greenish black residue of NiO (observed 12.2%,
calculated 12.9%). For 2, the first weight loss of 6.0%,
from 30 to 129°C, corresponds to the loss of the two
water molecules (calculated 6.1%). On further heating,
2 lost weight between 274 and 600°C corresponding to
field splitting and the Haldane gap effect [2a,12].
Ni2g2S(S+1) (1+v)
m=
3kT
(1+v)
JS(S+1)
kT
JS(S+1)
ꢂ n ꢂ n
where v=coth
−
(1)
kT
The results of the best-fit are summarized in Table 5
together with some structural data. It can be seen that
the magnetic interaction is very weak (J5 −2 cm−1).
The weak coupling observed may be due to the large
,
intramolecular Ni…Ni distance (]11.3 A). The intra-
and intermolecular Ni…Ni distances and the values of
the dihedral angles (h and i) are included in Table 5.
Given that the intramolecular Ni…Ni distances are
Fig. 3. (a) An ORTEP drawing of [Ni(L)(PDC)]·H2O (3) with the atomic numbering scheme (30% probability ellipsoids shown). (b) Crystal packing
of 3, showing the intermolecular hydrogen bonds as dotted lines. The hydrogen atoms are omitted for clarity.

64
K.-Y. Choi et al. / Polyhedron 20 (2001) 57–65
Fig. 5. Thermogravimetric plots for (a) 1, (b) 2, and (c) 3.
calculated 84.1%). Further weight loss is observed
above 600°C corresponding to the greenish black
residue of NiO (observed 10.1%, calculated 10.3%). For
compound 3, the first weight loss occurred from 30 to
124°C, due to the loss of one water molecule (observed
Fig. 4. Plots of  vs T ( ) and veff vs T (ꢀ) for (a) 1, (b) 2, and (c)
3. The solid line represents the best fit of the experimental data to Eq.
(1).
m
one macrocycle and one BDC ligand (observed 85.1%,
Table 5
Structural and magnetic data of nickel(II) complexes
a
J (cm−1
)
105R
h (°)
i (°)
dintra (A)
dinter (A)
,
,
Complex
g
[(NiL)3(BTC)2]·8H2O (1)
[Ni(L)(BDC)]·2H2O (2)
[Ni(L)(PDC)]·H2O (3)
2.13
2.26
2.16
−1.13
−1.37
−1.47
6.4
3.2
4.8
1.7, 20.0
5.6
2.8, 3.6
9.5, 10.6
7.3
5.7, 11.6
11.3
11.5
11.5
10.6
10.9
8.9
2
obs
1/2
a R=[ꢀ(obs−calc)2/ꢀ
] .

K.-Y. Choi et al. / Polyhedron 20 (2001) 57–65
65
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(observed 81.3%, calculated 81.2%). The final weight
loss is completed above 600°C corresponding to the
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
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147 105 for compound 2, and 147 106 for compound 3.
Copies of this information may be obtained free of
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Acknowledgements
This work was supported by the Research Fund of
Kongju National University, 2000.
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