Supramolecular architectures of four new transition metal complexes with 3-[4-(carboxymethoxy)phenyl]propanoic acid and N-[4-(carboxymethoxy)phenyl] iminodiacetic acid

Article abstract of DOI:10.1002/zaac.201000228

Four new transition metal complexes: [Cu(Hcppa)₂(H ₂O)₂] (1), [Co₂(cppa)₂(H ₂O)₁₀] (2), [Co₃(cpia)₂(H ₂O)₈]·2H₂O (3) and [Ni ₃(cpia)₂(H₂O)₁₂]·6H ₂O (4) {H₂cppa = 3-(4-(carboxymethoxy)phenyl]propanoic acid; H₃cpia = N-[4-(carboxymethoxy)phenyl]iminodiacetic acid} were synthesized and characterized. Complexes 1 and 2 show mononuclear structures, complexes 3 and 4 exhibit dinuclear structures. All complexes extend to 3D supramolecular networks through hydrogen bonds, of which complexes 3 and 4 display microporous structures. In complexes 2-4 the water clusters are trapped by the cooperative association of coordinate interactions as well as hydrogen bonds, forming different 1D metal-water chain structures. Thermal stabilities of complexes 1-4 were discussed. Copyright

Full text of DOI:10.1002/zaac.201000228

ARTICLE
DOI: 10.1002/zaac.201000228
Supramolecular Architectures of Four New Transition Metal Complexes
with 3-[4-(Carboxymethoxy)phenyl]propanoic Acid and
N-[4-(Carboxymethoxy)phenyl]iminodiacetic Acid
Chong-Bo Liu,*[a] Hui-Liang Wen,[b] Yun-Nan Gong,[a] Xiao-Ming Liu,[a] and
Sheng-Shui Tan[b]
Keywords: 3-[4-(carboxymethoxy)phenyl]propanoic acid; N-[4-(carboxymethoxy)phenyl]iminodiacetic acid;
Supramolecular chemistry; Copper; Cobalt; Nickel
Abstract. Four new transition metal complexes: [Cu(Hcppa)2(H2O)2] structures. All complexes extend to 3D supramolecular networks
(1), [Co2(cppa)2(H2O)10] (2), [Co3(cpia)2(H2O)8]·2H2O (3) and through hydrogen bonds, of which complexes 3 and 4 display micropo-
[Ni3(cpia)2(H2O)12]·6H2O (4) {H2cppa = 3-(4-(carboxymethoxy)phe- rous structures. In complexes 2–4 the water clusters are trapped by the
nyl]propanoic acid; H3cpia = N-[4-(carboxymethoxy)phenyl]iminodia- cooperative association of coordinate interactions as well as hydrogen
cetic acid} were synthesized and characterized. Complexes 1 and 2 bonds, forming different 1D metal-water chain structures. Thermal sta-
show mononuclear structures, complexes 3 and 4 exhibit dinuclear bilities of complexes 1–4 were discussed.
characteristics: (1) Both contain one phenyl ring and one ox-
Introduction
yacetate group, in addition, the H2cppa ligand has one propion-
Recently, much attention has been paid to the design and
ate function and the H3cpia ligand has one –N(CH2COOH)2
synthesis of high-dimensional supramolecular complexes be-
group, so they not only display the characteristics of flexibility
cause of their ability to form frameworks with various struc-
and rigidity, but also have long spacers in comparison with the
tures, as well as their interesting magnetic, optical, and poros-
corresponding ring-shaped multidentate carboxylates [21–24],
ity properties [1–11]. Hydrogen bonding, as major
such as 1,4-benzenedicarboxylate, which will help to form po-
intermolecular force, is usually applied to increase the struc-
rous structures. (2) The two ligands have multiple coordination
tural dimensionality of supramolecular systems. Water molecu-
sites and can provide various bridging and chelating coordina-
les and carboxylic acids as good hydrogen-bond donors and
tion modes displayed by the –OCH2COOH, –CH2CH2COOH
acceptors have been widely used to construct supramolecular
and –N(CH2COOH)2 groups to construct different structures.
complexes. Up to now, much work has been done about the
(3) The coordination sites of the two ligands can be used as
research of hydrogen bonding in discrete water clusters (H2O)n
hydrogen-bond acceptors as well as hydrogen-bond donors,
which assist in the generation of high-dimensional supramolec-
ular networks.
(n = 2–18), as well as polymeric water clusters [12–14]. Unfor-
tunately, only very limited information has been obtained about
metal–water clusters not only including hydrogen bonding in-
teractions between water molecules, but also coordination in-
teraction between metal atoms and water clusters [15], al-
In view of these factors, we were working on the synthesis
of supramolecular complexes with H2cppa and H3cpia ligands,
though the structural study of them could provide valuable and reported the structures of three complexes containing the
information for unraveling the mechanism in energy-transduc-
tion or proton conduction.
On the other hand, exploiting flexible carboxylate ligands
with suitable spacers to construct supramolecular complexes
with porous structures also has been widely investigated [16–
20]. H2cppa and H3cpia ligands exhibit several interesting
H2cppa compound, [M(H2O)4(4,4'-bpy)][cppa] (M = Co, Ni,
Zn; 4,4'-bpy = 4,4'-bipyridine), in which the H2cppa com-
pounds are completely deprotonated but remain uncoordinated
to metal ions [25–27]. Except the above three complexes, no
other structural characterization of H2cppa complexes were re-
ported. To the best of our knowledge, up to now there are also
no reports of H3cpia ligand. Accordingly, in the present work,
we report the syntheses and characterizations of four new tran-
sition metal complexes with two kinds of multicarboxylate li-
gands: [Cu(Hcppa)2(H2O)2] (1), [Co2(cppa)2(H2O)10] (2),
[Co3(cpia)2 (H2O)8]·2H2O (3), and [Ni3(cpia)2(H2O)12]·6H2O
(4).
* Prof. Dr. C.-B. Liu
E-Mail: cbliu2002@163.com
[a] School of Environment and Chemical Engineering
Nanchang Hangkong University
Nanchang 330063, P. R. China
[b] State Key Laboratory of Food Science and Technology
Nanchang University
Nanchang 330047, P. R. China
122
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 637, 122–129

Supramolecular Architectures of Four New Transition Metal Complexes
to a 2D layer containing regular parallelogram grids with di-
mensions of 6.7 × 23.0 Å2 based on the Cu···Cu distance by
O6–H1W···O5 hydrogen bonds between uncoordinated car-
boxylate oxygen atoms and coordinated water molecules along
the a axis. Finally, O6–H2W···O5 and C6–H6A···O3 hydrogen
bonds among adjacent layers link complex 1 to a 3D supramo-
lecular structure, as shown in Figure 2.
Results and Discussion
Structural Descriptions
[Cu(Hcppa)2(H2O)2] (1)
Single crystal X-ray diffraction analysis reveals that complex
1 has a mononuclear structure, as shown in Figure 1. The CuII
ion is hexacoordinated by two carboxylate oxygen atoms and
two ether oxygen atoms from two Hcppa– anions, and two
water oxygen atoms. It lies on an inversion center and has a
slightly distorted octahedral arrangement. Every H2cppa ligand
loses one proton and coordinates to one CuII ion in a bidentate
mode (Scheme 1a). Through dual O3–H3···O2 hydrogen bonds
between unprotonated carboxyl groups adjacent [Cu(Hcppa)2]
units are linked to a 1D chain structure, which is further joined
Figure 2. 3D Supramolecular structure of complex 1 viewed along the
a axis, the hydrogen bonding interactions are represented by dashed
lines.
[Co2(cppa)2(H2O)10] (2)
As shown in Figure 3, each CoII ion in complex 2 is hexaco-
ordinated by one carboxylate oxygen atom from one cppa2–
anion and five water oxygen atoms, the coordination environ-
ments of Co(1) and Co(2) are similar, but the bond lengths of
Co(1)–O and Co(2)–O are different, the Co(1)–O distances are
in the range of 2.051–2.134 Å, and Co(2)–O distances are in
the range of 2.044–2.170 Å. Differing from 1, the carboxyl
groups of H2cppa ligand are completely deprotonated in 2, and
Figure 1. Coordination environment of the CuII ion in complex 1 with
50 % thermal ellipsoids. All hydrogen atoms except the one of the
carboxyl group are omitted for clarity. Symmetry operation: A = –
x+1, –y+2, –z+1.
the cppa2– anions display
a monodentate mode (see
Scheme 1b). The O–H···O hydrogen bonds between carboxyl-
ate oxygen atoms and coordinated water molecules link
[Co1(cppa)(H2O)5]2+ and [Co2(cppa)(H2O)5]2+ units to form
the 2D layer structures, which contain numerous parallelo-
grams with dimensions of ca. 5.1 × 18.2 Å2 and 5.1 × 17.3 Å2
based on the nearest distance of the CoII ions, respectively,
as shown in Figure 4a and Figure 4c. In [Co1(cppa)(H2O)5]2+
layers, O1, O2, O3, and Co12+ ions form a metal–water chain
by coordination interactions and hydrogen bonds; similarly in
[Co2(cppa)(H2O)5]2+ layers, O6, O7, O8, O9, and Co22+ ions
form a metal–water chain, too; these two metal–water chains
are linked through O3–H6···O7 hydrogen bonds, resulting in
an infinite ladder-like metal–water chain (Figure 5a), which
join the [M(cppa)(H2O)5] (M = Co1, Co2) layers to a 3D supra-
molecular structure, as shown in Figure 4b.
[Co3(cpia)2(H2O)8]·2H2O (3)
There are two crystallographically independent CoII ions in
the asymmetric unit of 3 (see Figure 6a). Each Co1 ion has a
center of symmetry and is coordinated by six water molecules,
Co2 is hexacoordinated by one nitrogen atom and four carbox-
ylate oxygen atoms of two cpia3– anions and one water oxygen
atom, the ratio of Co1:Co2 is 1:2. H3cpia ligands are com-
Scheme 1. Coordination modes of H2cppa and H3cpia ligands in com-
plexes 1–4.
Z. Anorg. Allg. Chem. 2011, 122–129
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
123

C.-B. Liu et al.
ARTICLE
Figure 3. Coordination environment of CoII ions in complex 2 with 50 % thermal ellipsoids. All hydrogen atoms except those of the O–H···O
groups are omitted for clarity.
Figure 5. (a) View of a 1D metal-water chain of complex 2; (b) View
of a 1D metal–water chain containing two single stranded helices in
complex 3. (c) View of a 1D metal–water chain containing four single
stranded helices in complex 4.
Figure 4. (a) Views of the 2D network constructed by Co2 ions along
the a axis; (b) The 3D supramolecular structure of complex 2 along
the b axis; (c) Views of the 2D network constructed by Co1 ions along
the a axis; the hydrogen bonding interactions are represented by
dashed lines.
[Co1(H2O)6]2+ are enclathrated in the cavities through Owater
–
H···Owater hydrogen bonds, as shown in Figure 6b. Co1–O3
and Co1–O2 coordination interactions combine with O3–
H6W···O12 and O12–H10W···O2 hydrogen bonds between un-
coordinated and coordinated water molecules, resulting in a
metal–water chain with two single stranded helices, as shown
in Figure 5b.
pletely deprotonated and show bis-N,O-chelating and O,O-che-
lating coordination modes (as shown in Scheme 1c). Intramo-
lecular O–H···O hydrogen bonds between carboxylate oxygen
atoms and coordinated water molecules link Co1 and Co2 ions
of an asymmetric unit, as shown in Figure 6a. Two H3cpia
ligands join two Co2+ ions to form a [Co22(cpia)2]2– building
block with Co2···Co2 distance of 10.31 Å. Every
[Co22(cpia)2]2– unit is bridged by six adjacent [Co22(cpia)2]2–
[Ni3(cpia)2(H2O)12]·6H2O (4)
As shown in Figure 7a, complex 4 has a dinuclear structure
units through O4–H7W···O10, O4–H8W···O10, C5–H5···O6, with two crystallographically independent NiII ions. Ni1 is
and C8–H8···O8 hydrogen bonds (see Table 3) to form a 3D hexacoordinated by one nitrogen atom and two carboxylate ox-
supramolecular network. The 3D supramolecular network ygen atoms of one cpia3– anion and three water oxygen atoms,
shows microporous structure with infinite cavities of ca. whereas Ni2 is hexacoordinated to six water molecules, the
5.7 × 9.7 Å2 defined by the nearest distance of the Co2(II) ratio of Ni1:Ni2 is 2:1. H3cpia ligands are completely deproto-
ions along the
a axis, and another building blocks nated and adopt a bis-N,O-chelating coordination mode, as
124 www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 122–129

Supramolecular Architectures of Four New Transition Metal Complexes
shown in Scheme 1d, one H3cpia ligand only links one NiII
ion. Through O–H···O hydrogen bonds between the carboxyl-
ate oxygen atoms and coordinated water molecules two H3cpia
ligands link two Ni1 ions to form a [Ni12(cpia)2]2– building
block (see Figure 7a) with a Ni1···Ni1 distance of 13.0 Å,
which is slightly longer than the Co2···Co2 distance (10.31 Å)
of [Co22(cpia)2]2– building block in complex 3. Similar to 3,
each [Ni12(cpia)2]2– unit is bridged by six adjacent
[Ni12(cpia)2]2– units through O2–H3W···O13, O2–H4W···O11,
and O3–H5W···O16 hydrogen bonds (see Table 3) to form a
3D supramolecular network, which has infinite cavities of ca.
8.3 × 10.2 Å2 along the a axis, and another kind of building
blocks [Ni2(H2O)6]2+ are enclathrated in the cavities through
hydrogen bonds, as shown in Figure 7b. Three uncoordinated
water molecules (O4, O5, and O6) and three coordinated water
molecules (O7, O8, and O9) are associated to discrete hexamer
clusters by O7–H13W···O6, O6···H7W–O4, O4–H7W···O9,
O9···H9W–O5, and O5···H15W–O8 hydrogen bonds with an
average O···O distance of 2.788 Å, which is close to corre-
sponding value of 2.759 Å in ice Ih [28]. Adjacent hexamers
are further linked to form a metal–water chain by Ni2–O7,
Ni2–O8, and Ni2–O9 coordination, where four single-stranded
helices can be observed, as shown in Figure 5c.
Figure 6. (a) Coordination environments of the CoII ions in complex 3
with 50 % thermal ellipsoids, all hydrogen atoms except those of the O–
H···O groups are omitted for clarity. Symmetry operations: A = –x+1, –
y+1, –z+1; B = –x+1, –y+1, –z+2. (b) The 3D supramolecular structure
of 3 along the a axis, indicating the cavities occupied by the building
blocks [Co(H2O)6]2+, which are displayed in space-filling model. The
hydrogen bonding interactions are represented by dashed lines.
Syntheses of the Complexes
The reaction conditions for the synthesis of complex 2 are
similar to those of the synthesis of [Co(H2O)4(4,4'-bpy)][cppa]
(5), which was reported previously to some extends [27]. The
difference is that 4,4'-bipyridine (0.1 mmol) in complex 5 was
Table 1. Crystal data for complexes 1–4.
1
2
3
4
Empirical formula
Formula weight /
g·mol–1
C22H26CuO12
545.97
C22H40Co2O20
742.40
C24H40Co3N2O24
917.36
C24H56N2Ni3O32
1060.84
T /K
291(2)
291(2)
Orthorhombic
Pca21
291(2)
291(2)
Crystal system
Space group
a /Å
Triclinic
Triclinic
Triclinic
¯
¯
¯
P1
P1
P1
5.337(11)
6.710(14)
16.386(3)
87.147(2)
82.173(2)
73.132(2)
556.3(2)
1
19.489(18)
5.115(5)
29.999(3)
90
7.626(12)
9.670(15)
12.494(19)
85.165(2)
76.429(2)
77.987(2)
875.4(2)
1
7.218(13)
10.478(18)
13.498(2)
96.500(2)
90.896(2)
96.512(2)
1007.2(3)
1
b /Å
c /Å
α /°
β /°
90
90
γ /°
V /Å3
2990.6(5)
4
Z
θ range /°
2.51–25.49
1.050
2.49–25.50
1.197
2.68–27.50
1.502
2.84–22.18
1.499
μ /mm–1
F(000)
283
1544
471
554
Dc /mg·m–3
Goodness-of-fit on
F2 /e·Å–3
No.data collected
No. unique data
Rint
1.630
1.649
1.740
1.749
1.090
0.990
1.000
1.021
4238
21098
7833
7597
2057
5543
3949
3730
0.0138
0.0422
0.0342
0.0448
R1, wR2[I > 2σ(I)]
R1, wR2(all data)
0.0253,0.0668
0.0268,0.0679
0.0516, 0.1213
0.0565, 0.1246
1.729, –0.393
0.0400, 0.0798
0.0694, 0.0946
0.434,-0.348
0.0449, 0.0873
0.0780, 0.1030
0.453, –0.600
Largest diff. peak and 0.248, –0.327
hole /e·Å–3
Z. Anorg. Allg. Chem. 2011, 122–129
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
125

C.-B. Liu et al.
ARTICLE
Table 2. Selected bond lengths /Å for complexes 1–4.
1
Cu(1)–O(1)
Cu(1)–O(6)
2.420(13)
1.948(14)
Cu(1)–O(4)
1.963(13)
2
Co(1)–O(1)
Co(1)–O(2)
Co(1)–O(3)
Co(1)–O(4)
Co(1)–O(5)
Co(1)–O(12)
2.103(3)
2.124(4)
2.132(4)
2.109(4)
2.087(4)
2.051(3)
Co(2)–O(6)
Co(2)–O(7)
Co(2)–O(8)
Co(1)–O(9)
Co(2)–O(10)
Co(2)–O(16)
2.134(3)
2.171(4)
2.097(4)
2.083(4)
2.066(4)
2.045(4)
3a)
Co(1)–O(1)
Co(1)–O(2)
Co(1)–O(3)
Co(2)–O(4)
Co(2)–O(5)#1
2.078(2)
2.102(2)
2.093(2)
2.030(2)
2.304(2)
Co(2)–O(6)#1
Co(2)–O(9)
Co(2)–O(11)
Co(2)–N(1)
2.081(2)
2.011(2)
1.997(2)
2.306(3)
4
Ni(1)–O(1)
Ni(1)–O(2)
Ni(1)–O(3)
Ni(1)–O(10)
Ni(1)–O(12)
2.028(3)
2.072(3)
2.047(3)
2.047(3)
2.023(3)
Ni(1)–N(1)
Ni(2)–O(7)
Ni(2)–O(8)
Ni(2)–O(9)
2.181(3)
2.022(3)
2.035(3)
2.085(3)
a) For 3: Symmetry operation: #1 –x+1, –y+1, –z+2.
replaced by NaOH (0.3 mL, 0.65 m) in complex 2, which led
to quite different structures. Although the carboxyl groups of
H2cppa ligands are completely deprotonated in complexes 2
and 5, in complex 2 one cppa2– ligand is coordinated to one
Co2+ ion, whereas in complex 5 the cppa2– ions only act as a
charge balance and hydrogen bonds acceptors to form O–H···O
hydrogen bonds with water molecules, which join the chain
structure of [Co(4,4'-bpy)·4H2O] blocks into a 3D supramolec-
ular structure.
Complex 1 was synthesized by a hydrothermal reaction un-
der high pressure, whereas complexes 2–4 were obtained under
autogenous pressure. Low pressure may be available for the
coordination of water molecules to metal ions in the reaction
systems: in complex 1 only two water molecules are involved
in coordination; whereas in complexes 2–4 ca. 8–12 water
molecules take part in coordination, different water clusters are
trapped by the cooperative association of coordinate interac-
tions as well as hydrogen bonds, which result in different 1D
metal–water chain structures in complexes 2–4.
From the structural descriptions of complexes 1–4, it can
be seen that although H2cppa and H3cpia ligands have similar
characteristics, and all metal ions in complexes 1–4 are hexa-
coordinate, complexes 1–4 display different supramolecular
networks, and only complexes 3 and 4 show microporous
structures. In complexes 1 and 2, the H2cppa ligands show
monodentate and bidentate coordination modes (as shown in
Scheme 1a and Scheme 1b), one H2cppa ligand only links one
metal ion. In complexes 3 and 4, the H3cpia ligands adopt
tridentate and pentadentate coordination modes (as shown in
Scheme 1c, Scheme 1d), one H3cpia ligand links one or two
metal ions, but two H3cpia ligands join two metal ions to form
a dimeric unit by coordination bonds and/or hydrogen bonds;
Figure 7. (a) Coordination environments of NiII ions in complex 4
with 50 % thermal ellipsoids, all hydrogen atoms except that of the
O–H···O groups are omitted for clarity. Symmetry operations: A = –
x+1, –y+2, –z; B = –x+2, –y, –z+1. (b) The 3D supramolecular structure
of complex 4 along the a axis, indicating the cavities occupied by
the building blocks [Ni(H2O)6]2+, which are displayed in space-filling
model. The hydrogen bonding interactions are represented by dashed
lines.
126
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 122–129

Supramolecular Architectures of Four New Transition Metal Complexes
other chemical reagents were obtained commercially and were used
without further purification. The elemental analysis of C, H, and N
were carried out with an Elementar Vario EL analyzer. The IR spectra
were recorded with a Nicolet Avatar 360 FT-IR spectrometer using the
KBr pellet technique. Thermogravimetric curves were recorded with a
ZRY-2P Thermal Analyzer.
with the help of hydrogen bonds with suitable direction. Each
dimeric unit is bridged with six adjacent units to form 3D su-
pramoleclar networks with microporous structure. So it can be
concluded that coordination modes of ligands and hydrogen
bonds have profound influences on the supramolecular archi-
tecture of the title complexes, and hydrogen bonds, especially
its direction is crucial to the microporous supramolecular con-
struction of complexes 3 and 4.
Synthesis of Complexes 1–4
[Cu(Hcppa)2(H2O)2] (1):
A mixture of CuSO4·5H2O (0.025 g,
Thermogravimetric Analyses
0.1 mmol), H2cppa (0.022 g, 0.1 mmol), NaOH (0.2 mL, 0.65 m), and
distilled water (10 mL) was sealed in a Teflon-lined stainless reactor
(23 mL) and heated 90 °C for 72 h under autogenous pressure. Blue
block crystals were obtained. Yield 32.5 %. C22H26CuO12: calcd. C
Thermogravimetric analyses of the four complexes were car-
ried out to examine their thermal stabilities. For complex 1, the
first weight loss of 6.4 % from 60 °C to 195 °C corresponds to
the loss of two coordinated water molecules per mononuclear
unit (calcd. 6.6 %). Increasing temperature led to further de-
composition and the final pyrolysis was completed at 758 °C,
to yield a powder of CuO (found 14.2 %, calcd. 14.6 %). For
complex 2, the first weight loss (ten coordinated water molecu-
les) of 23.8 % (calcd. 24.3 %) was observed from 50 °C to
121 °C, leaving a framework of [Co2(cppa)2]. The dehydrated
compound is stable up to 288 °C, the second weight loss of
54.9 % (calcd. 55.5 %) from 288 °C to 850 °C corresponds to
the burning of the organic groups, the final residual is CoO.
Complex 3 underwent the first weight loss of 19.1 % from
50 °C to 155 °C, corresponding to the loss of two lattice water
molecules and eight coordinated water molecules per formula
unit (calcd. 19.6 %), leaving a framework of [Co3(cpia)2]. Fur-
ther decomposition of 3 occurred above 370 °C, and was com-
pleted at 865 °C, to yield a powder of CoO (found 25.1 %,
calcd. 24.5 %). The TGA curve of complex 4 shows that the
first weight loss of 30.1 %, which occurred at 58 °C and ended
at 133 °C, corresponds to the loss of six lattice water molecu-
les and twelve coordinated water molecules (calcd. 30.5 %).
Afterwards, increasing temperature led to further decomposi-
tion, which began at 320 °C and the final pyrolysis was com-
pleted at 775 °C with the residual NiO in 20.9 % yield (calcd.
21.2 %).
48.40; H 4.80 %; found: C 48.71; H 4.95 %. IR (KBr): ν = 3032 w,
˜
1717 s, 1637 s, 1519 s, 1437 w, 1346 m, 1279 m, 1216 m, 1061 s,
949 s, 832 s, 793 w, 675 m cm–1.
[Co2(cppa)2(H2O)10] (2):
A mixture of CoCl2·6H2O (0.024 g,
0.1 mmol), H2cppa (0.022 g, 0.1 mmol), NaOH (0.2 mL, 0.65 m), and
distilled water was sealed in an undefiled test-tube (15 mL) and heated
at 90 °C for 5 h under autogenous pressure. Red tetragonal block crys-
tals were obtained. Yield 27.5 %. C22H40Co2O20: calcd. C 35.59; H
5.43 %; found: C 35.84; H 5.66 %. IR (KBr): ν = 3605 w, 1780 m,
˜
1650 m, 1580 w, 1466 vs, 1375 s, 1272 w, 1156 m, 1057 m, 950 w,
840 w, 722 vs, 630 w cm–1.
[Co3(cpia)2(H2O)8]·2H2O (3): The synthesis of 3 was similar to that
of 2, except that H3cpia (0.028 g, 0.1 mmol) was used instead of
H2cppa. Red block crystals were obtained. Yield 23.5 %.
C24H40N2Co3O24: calcd. C 31.42; H 4.40; N 3.05 %; found: C 31.72;
H 4.64; N 3.26 %. IR (KBr): ν = 3487 w, 1615 s, 1560 m, 1514 m,
˜
1420 s, 1334 m, 1234 s, 1186 w, 1118 w, 1074 m, 977 m, 912 m, 801
w, 685m cm–1.
[Ni3(cpia)2(H2O)12]·6H2O (4): The synthesis of 4 was the same as that
of 3, except that Ni(NO3)2·6H2O was used instead of CoCl2·6H2O.
Green stick crystals were obtained. Yield 25.5 %. C24H56N2Ni3O32:
calcd. C 27.33; H 5.32; N 2.64 %; found: C 27.35; H 5.59; N 2.95 %.
IR (KBr): ν = 3415 s, 1618 s, 1562m, 1513 w, 1419 m, 1331 w, 1242
˜
m, 1188 w, 1142 w, 1061 w, 917 w, 807 m, 701 w, 667 w cm–1.
Conclusions
X-ray Diffraction Analyses
Four new transition metal complexes with different supramo-
lecular networks were obtained by using the multicarboxylate
ligands with suitable spacers and characteristics of both flexi-
bility and rigidity. Water, H2cppa, and H3cpia ligands are ex-
cellent hydrogen bonding donors and acceptors, which help to
extend the 0D structures of complexes 1–4 to 3D supramolecu-
lar structures. The results of single-crystal X-ray diffraction
demonstrate that metal ions, coordination modes of ligands,
and hydrogen bonds have important effect on the supramolecu-
lar architectures of the title complexes. Thermogravimetric
analyses show that the thermal stabilities of complexes 1–4 are
relatively low.
The X-ray single-crystal data of 1–4 were collected with a Bruker
SMART 1000 CCD area detector diffractometer with graphite-mono-
chromated Mo-Kα radiation (λ = 0.71073 Å). Semi-empirical absorp-
tion corrections were applied to all four complexes using the SADABS
program. The structures were solved by direct methods using the pro-
gram SHELXS 97 [30] and refined by full-matrix least-squares on F2
using SHELXL 97 [31]. All non-hydrogen atoms were refined aniso-
tropically. Hydrogen atoms were placed in geometrically calculated
positions. Experimental details for X-ray data collection of 1–4 are
presented in Table 1, selected bond lengths are listed in Table 2, and
the types of hydrogen bonds are listed in Table 3.
The crystallographic data for the structures in this paper have been de-
posited with the Cambridge Crystallographic Data Centre, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK. Copies of the data can be ob-
tained free of charge on quoting the depository numbers CCDC-752379,
Experimental Section
Materials and Methods: The ligands H2cppa and H3cpia were synthe- -752380, -752381, and -752382 for 1–4 (Fax: +44-1223-336-033; E-
sized using an improved method described elsewhere [29]. All the Mail: deposit @ccdc.cam.ac.uk or www: http://www. ccdc.cam.ac.uk).
Z. Anorg. Allg. Chem. 2011, 122–129
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
127

C.-B. Liu et al.
ARTICLE
Table 3. Types of hydrogen bonds in complexes 1–4.
D–H
d(D–H)
d(H···A)
∠(DHA)
d(D···A)
A
1
O(3)–H(3)
0.82
0.81
0.81
0.93
1.83
1.85
2.06
2.45
173.7
173.3
170.2
149.0
2.651(2)
2.658(2)
2.857(2)
3.285(3)
O(2)[–x–1,–y+1, –z]
O(5) [x, y–1, z]
O(4) [–x+2, –y+2, –z+1]
O(3) [x+1, y+1, z]
O(6)–H(1W)
O(6)–H(2W)
C(6)–H(6A)
2
O(1)–H(1W)
O(1)–H(2W)
O(1)–H(2W)
O(2)–H(3W)
O(2)–H(4W)
O(3)–H(5W)
O(3)–H(6W)
O(4)–H(7W)
O(5)–H(9W)
O(5)–H(10W)
O(6)–H(11W)
O(6)-H(12W)
O(7)–H(13W)
O(7)–-H(14W)
O(7)–-H(14W)
O(8)–H(15W)
O(8)–H(16W)
O(9)–H(17W)
O(9)–H(18W)
O(10)–H(19W)
O(10)–H(20W)
C(6)–H(6A)
0.83
0.90
0.90
0.83
0.88
0.83
0.83
0.83
0.83
0.83
0.83
0.84
0.83
0.83
0.83
0.83
0.83
0.83
0.82
0.83
0.83
0.93
0.93
1.83
2.17
2.36
2.18
2.06
1.93
2.25
1.96
2.38
2.02
1.88
1.94
2.27
2.44
2.44
1.97
1.94
1.98
2.00
1.84
2.12
2.54
2.53
145.8
116.7
131.1
137.0
143.9
161.6
174.9
163.4
129.3
174.4
143.7
156.3
148.0
149.4
137.2
159.6
166.6
175.6
156.4
176.5
156.4
172.0
162.0
2.567(5)
2.698(5)
3.028(5)
2.841(5)
2.819(5)
2.727(5)
3.078(6)
2.768(5)
2.975(5)
2.847(5)
2.597(5)
2.723(5)
3.005(7)
3.176(6)
3.097(7)
2.763(5)
2.755(5)
2.808(6)
2.775(6)
2.666(6)
2.900(6)
3.466(7)
3.424(7)
O(11)
O(19) [–x, –y+2, z+1/2]
O(2)
O(1) [x, y+1, z]
O(14) [–x+1/2, y–1, z–1/2]
O(15) [–x+1/2, y–2, z–1/2]
O(7)
O(20) [–x+1/2, y–1, z+1/2]
O(20) [–x+1/2, y–1, z+1/2]
O(12) [x, y–1, z]
O(17)
O(15) [–x, –y+2, z–1/2]
O(14) [–x+1/2, y–2, z–1/2]
O(14) [–x+1/2, y–1, z–1/2]
O(9) [x, y+1, z]
O(6) [x, y+1, z]
O(20) [–x, –y+2, z+1/2]
O(16) [x, y–1, z]
O(14) [–x+1/2, y–2, z–1/2]
O(19) [–x, –y+2, z+1/2]
O(20) [–x, –y+1, z+1/2]
O(16)[1/2–x, 1+y, 1/2+z]
O(12) [1/2–x, y, –1/2+z]
C(19)–H(19)
3
O(1)–H(1W)
O(1)–H(2W)
O(2)–H(3W)
O(2)–H(4W)
O(3)–H(5W)
O(3)–H(6W)
O(4)–H(7W)
O(4)–H(8W)
O(12)–H(9W)
O(12)–H(10W)
C(5)–H(5)
0.83
0.83
0.83
0.83
0.87
0.83
0.83
0.83
0.83
0.83
0.93
0.93
1.98
1.95
1.92
1.99
1.97
1.92
2.14
1.82
2.64
2.47
2.39
2.35
163.6
165.2
164.7
169.9
172.6
174.6
154,3
169.6
112.2
147.2
166.0
152.0
2.782(3)
2.752(3)
2.730(3)
2.813(3)
2.835(3)
2.754(4)
2.904(3)
2.639(3
3.055(4)
3.204(4)
3.301(4)
3.209(4)
O(5) [–x+1, –y+1, –z+2]
O(8) [x, y–1, z]
O(9) [x, y–1, z]
O(11) [–x+1, –y+1, –z+1]
O(10)
O(12) [x–1, y, z]
O(10) [–x+1, –y+2, –z+1]
O(10) [x+1, y, z]
O(7) [x+1, y, z–1]
O(2) [–x+1, –y+1, –z+1]
O(6) [x, y+1, z]
C(8)–H(8)
O(8) [x, y–1, z]
4
O(1)–H(1W)
O(1)–H(2W)
O(2)–H(3W)
O(2)–H(4W)
O(2)–H(4W)
O(3)–H(5W)
O(3)–H(6W)
O(4)–H(7W)
O(4)–H(8W)
O(5)–H(9W)
O(5)–H(10W)
O(6)–H(12W)
O(6)–H(12W)
O(7)–H(13W)
O(7)–H(14W)
O(8)–H(15W)
O(8)–H(16W)
O(9)–H(17W)
O(9)–H(18W)
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
0.83
1.81
1.95
1.98
2.15
2.50
1.91
1.97
1.94
1.99
2.11
1.96
2.10
2.15
1.96
1.89
1.99
1.84
1.91
1.97
163.9
170.7
164.4
139.0
113.0
162.8
171.5
174.5
168.7
161.6
158.8
126.3
156.6
164.9
162.0
161.5
176.6
164.2
169.2
2.612(4)
2.768(4)
2.785(4)
2.825(4)
2.930(4)
2.714(4)
2.790(4)
2.762(4)
2.807(4)
2.904(4)
2.748(4)
2.678(5)
2.933(5)
2.765(4)
2.689(4)
2.788(4)
2.664(4)
2.718(4)
2.794(4)
O(15) [–x+2, –y,–z+1]
O(5) [–x+2, –y+1, –z+1]
O(13) [–x+2, –y+1, –z+2]
O(11) [x+1, y, z]
O(3)
O(16) [x, y+1, z]
O(16) [–x+2, –y, –z+1]
O(6) [x–1, y–1, z]
O(10) [–x+1, –y+1, –z+1]
O(9) [x + 1, y, z]
O(12) [x, y, z–1]
O(15) [x, y+1, z]
O(14) [x, y+1, z]
O(6)
O(11) [–x+1, –y+2, –z+1]
O(5)
O(13) [–x+1, –y+1, –z+1]
O(4) [x, y+1, z]
O(4) [–x, –y+1, –z]
128
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 122–129

Supramolecular Architectures of Four New Transition Metal Complexes
[14] R. Ludwig, Angew. Chem. Int. Ed. 2001, 40, 1809–1827.
[15] T. Li, F. Li, Y. Wang, W. Bi, X. Li, R. Cao, Inorg. Chim. Acta
2007, 360, 3771–3776.
[16] Y. C. Qiu, C. Daiguebonne, J. Q. Liu, R. H. Zeng, N. Kerbellec,
H. Deng, O. Guillou, Inorg. Chim. Acta 2007, 360, 3265–3271.
[17] S. Neogi, J. A. R. Navarro, P. K. Bharadwaj, Cryst. Growth Des.
2008, 8, 1554–1558.
[18] X. L. Hong, Y. Z. Li, H. M. Hu, Y. Pan, J. F. Bai, X. Z. You,
Cryst. Growth Des. 2006, 6, 1221–1226.
[19] L. Tang, D. S. Li, F. Fu, Y. P. Wu, Y. Y. Wang, H. M. Hu, E. B.
Wang, J. Mol. Struct. 2008, 888, 344–353.
Acknowledgement
This work is supported by National Natural Science Foundation of
China (20662007, 20961007).
References
[1] X. J. Luan, Y. C. Chu, Y. Y. Wang, D. S. Li, P. Liu, Q. Z. Shi,
Cryst. Growth Des. 2006, 6, 812–814.
[2] X. Y. Cao, J. Zhang, Z. J. Li, J. K. Cheng, Y. G. Yao, CrystEng-
Comm 2007, 9, 806–814.
[20] S. N. Wang, J. F. Bai, H. Xing, Y. Z. Li, Y. Song, Y. Pan, M.
Scheer, X. Z. You, Cryst. Growth Des. 2007, 7, 747–754.
[21] H. T. Xu, R. J. Wang, Y. D. Li, J. Mol. Struct. 2004, 688, 1–3.
[22] X. J. Zheng, L. P. Jin, S. Gao, Inorg. Chem. 2004, 43, 1600–1602.
[23] F. Q. Wang, X. J. Zheng, Y. H. Wan, C. Y. Sun, Z. M. Wang,
K. Z. Wang, L. P. Jin, Inorg. Chem. 2007, 46, 2956–2958.
[24] C. Serre, F. Millange, C. Thouvenot, M. Noguès, G. Marsolier,
D. Louër, G. Férey, J. Am. Chem. Soc. 2002, 124, 13519–13526.
[25] Y. N. Gong, C. B. Liu, D. H. Huang, Z. Q. Xiong, Z. Kristallogr.,
NCS 2009, 224, 421–422.
[3] H. L. Gao, L. Yi, B. Ding, H. S. Wang, P. Cheng, D. Z. Liao, S.-
P. Yan, Inorg. Chem. 2006, 45, 481–483.
[4] H. Ren, T. Y. Song, J. N. Xu, S. B. Jing, Y. Yu, P. Zhang, L. R.
Zhang, Cryst. Growth Des. 2009, 9, 105–112.
[5] F. Luo, Y. X. Che, J. M. Zheng, J. Mol. Struct. 2008, 873, 69–
72.
[6] X. Shi, G. S. Zhu, Q. R. Fang, G. Wu, G. Tian, R. W. Wang,
D. L. Zhang, M. Xue, S. L. Qiu, Eur. J. Inorg. Chem. 2004, 185–
191.
[26] C. Y. Ao, C. B. Liu, L. S. Yan, Z. Kristallogr., NCS 2009, 224,
179–180.
[7] S. Q. Ma, J. M. Simmons, D. F. Sun, D. Q. Yuan, H. C. Zhou,
Inorg. Chem. 2009, 48, 5263–5268.
[27] X. F. Wang, C. B. Liu, D. H. Huang, Z. Q. Xiong, Acta Crystal-
logr., Sect. E. 2009, 65, m764–m765.
[8] J. N. Moorthy, R. Natarajan, P. Venugopalan, J. Org. Chem. 2005,
70, 8568–8571.
[28] D. Eisenberg, W. Kauzmann, The Structure and Properties of Wa-
ter, Oxford University Press, New York, 1969.
[9] Y. H. Zhao, H. B. Xu, K. Z. Shao, Y. Xing, Z. M. Su, J. F. Ma,
Cryst. Growth Des. 2007, 7, 513–520.
[29] S. S. Tan, H. L. Wen, C. B. Liu, X. P. Peng, Z. Kristallogr., NCS
2007, 222, 137–138.
[10] R. H. Wang, F. L. Jiang, L. Han, Y. Q. Gong, Y. F. Zhou, M. C.
Hong, J. Mol. Struct. 2004, 699, 79–84.
[30] G. M. Sheldrick, SHELXS 97, Program for Crystal Structure Solu-
tion, University of Göttingen,Göttingen, Germany, 1997.
[31] G. M. Sheldrick, SHELXL 97, Program for Crystal Structure Re-
finement, University of Göttingen, Göttingen, Germany, 1997.
[11] X. D. Guo, G. S. Zhu, F. X. Sun, Z. Y. Li, X. J. Zhao, X. T. Li,
H. C. Wang, S. L. Qiu, Inorg. Chem. 2006, 45, 2581–2587.
[12] L. J. Barbour, G. W. Orr, J. L. Atwood, Nature 1998, 393, 671–
673.
[13] X. Luan, Y. Chu, Y. Wang, D. Li, P. Liu, Q. Shi, Cryst. Growth
Des. 2006, 6, 812–814.
Received: June 2, 2010
Published Online: October 21, 2010
Z. Anorg. Allg. Chem. 2011, 122–129
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
129