Synthesis, characterization, and crystal structure of three coordination polymers from 5-(pyridin-2-ylmethyl)aminoisophthalic acid

Article abstract of DOI:10.1002/zaac.201100160

Three new complexes: [M(L)(H₂O)] [M = Zn (1), Co (2), Ni (3); H₂L = 5-(pyridin-2-ylmethyl)aminoisophthalic acid] were synthesized under hydrothermal conditions at 180 °C and were characterized by elemental analysis, FT-IR spectroscopy, single-crystal X-ray diffraction, and thermogravimetric analysis (TGA). The results of X-ray diffraction analysis reveal that complexes 1-3 are isostructural and crystallize in the monoclinic system with space group P2₁/c. Each of the complexes displays a (3,3′)-connected two-dimensional (2D) wave-like network with (4,8 ²) topology, within which five-membered uncoplanar N,N-chelated metallacycles are shaped. Delicate N-H...O and O-H...O hydrogen bonding interactions exist in complexes 1-3. Adjacent 2D layers are linked by intermolecular interactions, resulting in the construction of extended metal-organic frameworks (MOFs) in complexes 1 and 2. Copyright

Full text of DOI:10.1002/zaac.201100160

ARTICLE
DOI: 10.1002/zaac.201100160
Synthesis, Characterization, and Crystal Structure of Three Coordination
Polymers from 5-(Pyridin-2-ylmethyl)aminoisophthalic Acid
Hai-Wei Kuai,*[a] Xiao-Chun Cheng,*[a] Liang-Dong Feng,[a] and Xiao-Hong Zhu[a]
Keywords: Zinc; Cobalt; Nickel; N,N-chelating; Metal-organic frameworks
Abstract. Three new complexes: [M(L)(H2O)] [M = Zn (1), Co (2), the complexes displays a (3,3')-connected two-dimensional (2D) wave-
Ni (3); H2L = 5-(pyridin-2-ylmethyl)aminoisophthalic acid] were syn- like network with (4,82) topology, within which five-membered unco-
thesized under hydrothermal conditions at 180 °C and were character- planar N,N-chelated metallacycles are shaped. Delicate N–H···O and
ized by elemental analysis, FT-IR spectroscopy, single-crystal X-ray O–H···O hydrogen bonding interactions exist in complexes 1–3. Adja-
diffraction, and thermogravimetric analysis (TGA). The results of X- cent 2D layers are linked by intermolecular interactions, resulting in
ray diffraction analysis reveal that complexes 1–3 are isostructural and the construction of extended metal-organic frameworks (MOFs) in
crystallize in the monoclinic system with space group P21/c. Each of complexes 1 and 2.
sign and synthesis of a carboxylic- and (2-pyridyl)-containing
1 Introduction
ligand: [H2L = 5-(pyridin-2-ylmethyl)aminoisophthalic acid] to
During the past few decades, the rational design, synthesis,
achieve new MOFs. One of the goals is to investigate the influ-
and characterization of metal-organic frameworks (MOFs)
ence of the intrinsic features of the H2L ligand on the structure
with well-defined sizes, beautiful shapes, and chemical envi-
and functional properties of the resultant complexes. Com-
ronments have attracted more and more attention, which is jus-
pared with other N or O donor ligands, the arene-cored ligand
tified by their fascinating architectures and tremendous poten-
H2L has several distinctive traits. In the first place, H2L con-
tial applications in heterogeneous catalysis, ion-recognition,
tains (pyridin-2-ylmethyl)amino groups. This type of N,N bi-
nonlinear optics, and molecular adsorption.[1] Hitherto, a great
dentate donor groups are always inclined to shape an N,N-
number of open frameworks with abundant structural motifs
chelated metallacycle, which could play a very important role
and interesting properties were developed and discussed in
in inducing a structural evolution and maintaining a specific
some comprehensive reviews.[2] An effective strategy for the
coordinating configuration.[5] Secondly, as an aromatic dicar-
construction of such complexes is to select suitable organic
boxylate-containing ligand, on account of the fine coordinating
ligands as building blocks that enable the control of structural
performance of carboxylate groups,[6] H2L could reliably act
motifs and functional properties.[3] Among popularly em-
as a bridging rod. Thirdly, due to the presence of N–H groups
ployed ligands, rigid or flexible N, O multidentate donor li-
as potential hydrogen-bonding groups, hydrogen bonding in-
gands are always regarded as excellent candidates for building
the blocks of desirable frameworks.[4]
teractions may be available to extend the coordinating net-
works and direct overall 3D metal-organic frameworks
(MOFs).[7] Thus, the structural prediction of resulting poly-
meric species may be possible to some extent. Because of the
above considerations, we selected 5-(pyridin-2-ylmethyl)ami-
noisophthalic acid as organic ligand rather than (pyridin-3-yl-
methyl)amino-containing or (pyridin-4-ylmethyl)amino-con-
taining ones that could build higher-dimensional architectures
and shape more complicated structural motifs.[8]
However, due to the complexity of self-assembly processes,
it is impossible to regulate coordinating processes for most
organic ligands and to predict the structure of the resultant
complexes. Therefore, it is still a great challenge to rationally
design and synthesize desired complexes. With this back-
ground in mind, recently we focused our attention on the de-
* Dr. H.-W. Kuai
Herein, we describe the synthesis, characterization, and crys-
tal structure of three complexes: {[Zn(L)(H2O)] (1),
[Co(L)(H2O)] (2), and [Ni(L)(H2O)] (3)} in order to explore
the essence of coordinating behaviors of the H2L ligand. As
expected, the results of the X-ray crystallographic analysis re-
vealed that the these complexes have similar architectures: a
five-membered noncoplanar N,N-chelated metallacycle is gen-
erated via the (pyridin-2-ylmethyl)amino groups coordinating
towards the MII ions; the L2– ligand unsurprisingly acts as
Fax: +86-517-83559044
E-Mail: hyitshy@126.com
* Dr. X.-C. Cheng
Fax: +86-517-83559044
E-Mail: chengxc126@126.com
[a] Faculty of Life Science and Chemical Engineering,
Huaiyin Institute of Technology,
Meicheng Road Campus
Huaian 223003, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201100160 or from the
author.
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Coordination Polymers from 5-(Pyridin-2-ylmethyl)aminoisophthalic Acid
bridging rod, leading to the formation of a 2D wave-like net- coordinated water molecule, and three oxygen atoms from two
work (Scheme 1); besides, delicate N–H···O and O–H···O hy- carboxylate groups of two different L2– ligands to furnish a
drogen bonding interactions also exist in the three complexes, distorted octahedral coordination arrangement [ZnN2O4] [Fig-
which superpose adjacent layers to construct the three-dimen- ure 1(B)]. Two carboxylate groups of the L2– ligand exhibit
sional (3D) supramolecular structures in complexes 1 and 2. different coordination mode in complex 1, one adopts a κ2-
Complexes 1–3 were characterized by elemental analysis, FT- O,O-chelating coordination mode [the value of angle sub-
IR spectroscopy, single-crystal X-ray diffraction, and thermo- tended at ZnII ion by them being 54.29(13)°], whereas the
gravimetric analysis (TGA).
other carboxylate group shows a κ1-O-monodentate coordina-
tion. The obvious difference in bond lengths [Zn1–O1 =
1.951(3) Å, Zn1–O2 = 2.675(4) Å, Zn1–O4(c) = 2.051(3) Å]
is just the reflection of the overall molecular distortion. Two
nitrogen atoms from the (pyridin-2-ylmethyl)amino group co-
ordinate towards one ZnII ion to generate a five-membered un-
coplanar N,N-chelated metallacycle [Zn(1)–N1(b)
=
2.382(5) Å, Zn(1)–N2(b) = 2.061(4) Å]: one nitrogen atom is
located in the equatorial plane of the octahedral coordination
arrangement; the other nitrogen atom occupies the apex
[N1(b)–Zn1–N2(b) = 75.25(15)°]. The dihedral angle between
the pyridyl ring of the flexible arm and the central benzene ring
is about 79.02°. Selected bond lengths and angles are listed in
Table 2.
Scheme 1. Molecular structure and coordination mode of the H2L li-
gand in complexes 1–3.
Scheme 2. Schematic representation of distorted octahedral coordina-
tion arrangements of [MN2O4] in complexes 1–3.
2 Results and Discussion
2.1 Preparation
The hydrothermal reaction at 180 °C of stoichiometric
amounts of M(NO3)2·6H2O [M = Zn (1), Co (2), and Ni (3)]
with H2L in the presence of NaOH provided single crystals of
complexes 1–3 analyzed as [M(L)(H2O)] by single-crystal X-
ray diffraction analysis, which are stable in air.
Figure 1. (A) Coordination arrangement of the ZnII ion in complex 1
with 30 % probability displacement ellipsoids. Hydrogen atoms were
omitted for clarity. Symmetry transformations: b: –x, 1 – y, –z; c: x,
0.5 – y, 0.5 + z. (B) Polyhedral representation of [ZnN2O4].
2.2 Structural Description
Determination of the structures of complexes 1–3 by X-ray
crystallography revealed that the molecular structures of the
As described above, each L2– ligand bridges three different
three complexes are similar. The three complexes crystallize in ZnII ions and every ZnII ion is coordinated by three different
the monoclinic system with space group P21/c (Table 3). Thus, L2– ligands. This kind of connection extend the coordination
only complex 1 is discussed in detail herein.
and makes complex 1 a neutral infinite 2D wave-like network
As shown in Figure 1(A), in the asymmetric unit of complex [Figure 2(B)]. Both ZnII ion and L2– ligand can be considered
1, there are one ZnII ion, one L2– ligand, and one coordinated as three-connected nodes in a ratio of 1:1 in complex 1. There-
water molecule. Each ZnII ion is six-coordinate by two nitro- fore, complex 1 exhibits a (3,3')-connected 2D network with a
gen atoms from one L2– ligand, one oxygen atom from the (4,82) topology [Figure 2(C)]. Within the 2D layer, two L2–
Z. Anorg. Allg. Chem. 2011, 1560–1565
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H.-W. Kuai, X.-C. Cheng, L.-D. Feng, X.-H. Zhu
ARTICLE
Table 1. Varying extent of distorted octahedral coordination arrangements of [MN2O4].
Complex
a /Å
b /Å
c /Å
d /Å
e /Å
f /Å
Sa) /Å
ZnII
CoII
NiII
2.051(3)
2.065(2)
2.015(1)
2.382(5)
2.306(1)
2.024(2)
1.951(3)
2.010(2)
2.284(1)
2.024(4)
2.406(2)
2.044(2)
2.061(4)
2.087(2)
2.147(2)
2.675(4)
2.076(2)
2.052(2)
1.018(3)
0.626(1)
–0.326(2)
a) S = (b – a) + (d – c) + (f – e).
Table 2. Selected bond lengths /Å and angles /° for complexes 1–3.
1
Zn(1)–O(1)
1.951(3)
Zn(1)–O(2)
2.675(4)
Zn(1)–N(1)#1
2.382(5)
Zn(1)–N(2)#1
2.061(4)
Zn(1)–O(5W)
2.024(4)
Zn(1)–O(4)#2
2.051(3)
O(4)#2–Zn(1)–N(2)#1
O(5W)–Zn(1)–O(4)#2
O(1)–Zn(1)–N(1)#1
N(2)#1–Zn(1)–N(1)#1
O(1)–Zn(1)–O(2)
O(1)–Zn(1)–O(5W)
O(4)#2–Zn(1)–N(1)#1
97.75(15)
95.05(16)
88.65(15)
75.25(15)
54.29(13)
109.30(18)
172.20(14)
O(4)#2–Zn(1)–O(2)
O(1)–Zn(1)–O(4)#2
N(1)#1–Zn(1)–O(2)
O(5W)–Zn(1)–N(1)#1
N(2)#1–Zn(1)–O(2)
O(5W)–Zn(1)–N(2)#1
85.79(13)
96.48(15)
92.51(13)
88.75(16)
103.79(14)
92.47(19)
2
Co(1)–O(1)
2.0102(16)
2.3066(19)
2.0654(15)
96.38(7)
Co(1)–O(2)
2.4069(19)
2.0878(19)
2.0760(19)
92.82(7)
Co(1)–N(1)#3
Co(1)–N(2)#3
Co(1)–O(4)#4
Co(1)–O(5W)
O(4)#4–Co(1)–O(1)
O(4)#4–Co(1)–N(2)#3
O(1)–Co(1)–N(1)#3
N(2)#3–Co(1)–N(1)#3
O(1)–Co(1)–O(2)
O(5W)–Co(1)–N(2)#3
O(4)#4–Co(1)–N(1)#3
O(4)#4–Co(1)–O(5W)
O(4)#4–Co(1)–O(2)
O(5W)–Co(1)–N(1)#3
N(1)#3–Co(1)–O(2)
O(1)–Co(1)–O(5W)
N(2)#3–Co(1)–O(2)
97.65(7)
87.47(6)
89.39(7)
87.07(7)
76.42(7)
94.35(6)
59.07(6)
104.23(8)
108.32(7)
88.34(8)
174.07(7)
3
Ni(1)–O(1)
2.0158(17)
2.0437(15)
2.147(2)
87.19(7)
93.41(8)
92.56(7)
88.78(7)
60.51(6)
99.85(7)
174.99(8)
Ni(1)–N(2)#5
2.024(2)
2.0518(16)
2.2843(16)
92.89(7)
91.27(7)
91.87(7)
81.64(8)
110.76(6)
88.87(7)
Ni(1)–O(4)#6
Ni(1)–O(5W)
Ni(1)–N(1)#5
Ni(1)–O(3)#6
O(1)–Ni(1)–O(4)#6
O(1)–Ni(1)–N(1)#5
N(2)#5–Ni(1)–O(3)#6
N(2)#5–Ni(1)–O(5W)
O(4)#6–Ni(1)–O(3)#6
O(5W)–Ni(1)–N(1)#5
O(1)–Ni(1)–N(2)#5
O(1)–Ni(1)–O(5W)
O(1)–Ni(1)–O(3)#6
N(2)#5–Ni(1)–O(4)#6
N(2)#5–Ni(1)–N(1)#5
O(5W)–Ni(1)–O(3)#6
O(4)#6–Ni(1)–N(1)#5
Symmetry transformations used to generate equivalent atoms: #1: –x, 1 – y, –z; #2: x, 1/2 –y, –1/2 + z; #3: 2 – x, –y, 2 – z; #4: x, 1/2 – y, 1/2
+ z; #5: –x, 1 – y, 1 – z; #6: –x, –1/2 + y, 1/2 – z.
ligands doubly connect two different ZnII ions to form a sec-
ondary building unit (SBU) [Zn2(L)2(H2O)2] [Figure 2(A)].
Although the three complexes are isostructural, there is still
a little difference among them: (1) the tortuosity of five-mem-
Delicate N–H···O and O–H···O hydrogen bonding interac- bered uncoplanar N,N-chelated metallacycles in each complex
tions exist in complex 1. There are two kinds of intermolecular is different, which is the reflection of varying degrees of the
hydrogen bonding: (1) the hydrogen bonding (N1–H1N···O2) molecular distortion. The detailed torsion angles are listed in
between the hydrogen atom (H1N) from a (pyridin-2-yl- Table S2 (Supporting Information); (2) despite showing the
methyl)amino group and the oxygen atom (O2) of the carbox- same coordination arrangement [MN2O4] (Scheme 2, Table 1),
ylate unit (O1C7O2); (2) the hydrogen bonding (O5W– the six coordinating atoms array in different spatial order. For
H5WB···O4) between the hydrogen atom (H5WB) of the coor- example, in complexes 1 and 2, the nitrogen atom of amino
dinated water molecules and the oxygen atom (O4) from car- group (–NH–) is located at the axial position of the octahedral
boxylate (O3C8O4) [Figure 3(A); Table S1, Supporting Infor- polyhedron, and the nitrogen atom from the pyridyl ring is
mation]. More significantly, this system of intermolecular located in the equatorial plane. However, the case is just re-
strong hydrogen bonding superposes adjacent layers to con- verse for complex 3. The molecular structures of 2 and 3 are
struct a three-dimensional framework [Figure 3(B)].
presented in Figure S1 and S2 (Supporting Information).
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Coordination Polymers from 5-(Pyridin-2-ylmethyl)aminoisophthalic Acid
Table 3. Crystallographic data and structure refinement details for complexes 1–3.
1
2
3
Empirical formula
Formula weight
Temperature /K
Crystal system
Space group
C14H12N2O5Zn
353.63
C14H12CoN2O5
347.19
C14H12N2NiO5
346.97
293(2)
293(2)
293(2)
monoclinic
P21/c
monoclinic
P21/c
monoclinic
P21/c
8.9619(6)
a /Å
5.5356(7)
14.4821(19)
16.449(2)
93.329(2)
1316.4(3)
4, 1.784
5.4613(7)
14.681(2)
16.443(2)
92.457(2)
1317.1(3)
4, 1.751
b /Å
12.0053(8)
14.7534(7)
123.762(3)
1319.62(14)
4, 1.746
c /Å
β /°
V /Å3
Z, Dcalc /Mg·m–3
Absorption coefficient
F(000)
1.511
720
1.330
708
1.497
712
θ range /°
1.87–25.01
6453/2310 (Rint = 0.0213)
2310/0/193
1.353
1.86–28.00
8138/3125 (Rint = 0.0379)
3125/0/199
1.029
2.37–26.95
8114/3143 (Rint = 0.0381)
3143/0/193
1.004
Reflections collected / unique
Data / restraints / parameters
GOF on F2
R1 / wR2 [I > 2σ (I)]
R1 / wR2 [all data]
0.0581 / 0.1168
0.0595 / 0.1173
0.0365 / 0.0784
0.0484 / 0.0814
0.0337 / 0.0812
0.0450 / 0.0842
was readily prepared according to the literature.[9] Elemental analyses
(C, H, and N) were performed with a Perkin–Elmer 240C Elemental
analyzer. Analysis of thermal stability was carried out with a simulta-
neous SDT 2960 thermal analyzer under nitrogen with a heating rate
of 10 °C·min–1. FT-IR spectra were recorded in the range of 400–
4000cm–1 with a Bruker Vector22 FT-IR spectrophotometer using KBr
pellets.
2.3 Thermogravimetric Analyses
Thermogravimetric analyses (TGA) of complexes 1–3 were
recorded in a nitrogen atmosphere with a heating rate of
10 °C·min–1 in order to study their thermal stability. The three
complexes were heated from 20 to 680 °C. The TGA curves
of compounds 1–3 exhibit similar thermal behaviors (Fig-
ure 4). The first step (224–253 °C for 1, 205–247 °C for 2,
and 206–249 °C for 3) corresponds to the release of one coor-
dinated water molecule and the observed weight losses of
5.36 % for 1, 4.90 % for 2, and 5.48 % for 3 are very close to
the calculated value (5.09 %, 5.18 %, and 5.19 % for 1, 2, and
3, respectively). The second step occurs at 383 °C for 1,
375 °C for 2, and 347 °C for 3 and is associated with the com-
bustion of the L2– ligands. The continuous decomposition of
complexes 1 and 2 does not end above 680 °C, so the final
residuals are not characterized. But in the TGA curve of com-
plex 3, the second step terminates at 471 °C with a total weight
loss of 78.3 %, which is in agreement with the total weight
loss calculated for the decomposition of complex 3 leading to
the formation of NiO (78.5 %) as final residuals.
4.2 Syntheses
4.2.1 Synthesis of H2L[9]
Triethylamine (6 mL) was added to a stirred mixture of 5-aminoisoph-
thalic acid (2.90 g, 16.0 mmol), 4-pyridinecarboxaldehyde (1.80 g,
16.8 mmol), and dry methanol (100 mL). After 10 h, the mixture be-
came limpid, and an excess of NaBH4 (4 equiv.) was slowly added at
4 °C. After 10 h at 4 °C, the solvent was concentrated in vacuo. The
residue was dissolved in water (100 mL) and acidified with AcOH to
pH 5–6. After filtration, the product was obtained as a pale-yellowish
solid (3.83 g, 87.9 %). Physical data: M.p. 162 °C. Elemental analysis:
C14H12N2O4 (272.08): C 61.52 (calcd. 61.76); H 4.68 (4.44); N 10.58
(10.29) %. 1H NMR (500 MHz, [D6]DMSO, 25 °C): δ = 13.19–12.64
3
(br., s, 2 H, -COOH), 8.54 [d, J(H,H) = 4.57 Hz, 1 H, pyridine ring];
7.73–7.76 (m, 1 H pyridine ring); 7.69 (s, 1 H, benzene ring); 7.37 (s,
2 H, benzene ring); 7.34 (s, 1 H, pyridine ring); 7.25–7.27 (m, 1 H,
3 Conclusion
3
The arene-cored ligand H2L, which has several distinctive
properties, was synthesized. Three new 2D complexes from the
H2L ligand were synthesized and characterized by elemental
analysis, FT-IR spectroscopy, single-crystal X-ray diffraction,
and thermogravimetric analysis. N–H···O and O–H···O hydro-
gen bonding interactions exist in complexes 1–3. Adjacent 2D
layers are linked by intermolecular interactions, which results
in the construction of extended metal-organic frameworks
(MOFs) in complexes 1 and 2.
pyridine ring); 6.94–6.96 [t, J(H,H) = 5.5 Hz, 1 H, –NH–]; 4.44 [d,
3J(H,H) = 4.9 Hz, 2 H, -CH2-]. ESI-MS (methanol) m/z: 272.08 (calcd.
for C14H12N2O4, 272.03).
4.2.2 Synthesis of [Zn(L)(H2O)] (1)
A mixture of Zn(NO3)2·6H2O (29.7 mg, 0.100 mmol), H2L (27.2 mg,
0.100 mmol), and NaOH (8.00 mg, 0.200 mmol) in water (12 mL)
was stirred for 10 min in air. Subsequently, the mixture was transferred
to a 16 mL Teflon lined stainless steel container and heated at 180 °C
for 3 days. After the mixture was cooled to room temperature, complex
1 was isolated from the mixture in colorless block crystalline form by
filtration and washed with water and ethanol several times with a yield
4 Experimental Section
4.1 Materials and Characterization
All commercially available chemicals and solvents were of reagent of 23.3 mg (0.0659 mmol, 65.9 % based on the H2L ligand). Analyti-
grade and used as received without further purification. The H2L ligand cal data: C14H12N2O5Zn (353.6): C 47.16 (calcd. 47.51); H 3.66 (3.39);
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H.-W. Kuai, X.-C. Cheng, L.-D. Feng, X.-H. Zhu
ARTICLE
Figure 3. (A) Hydrogen bonding interactions existing in complex 1.
Symmetry transformations: #1 = –1 + x, 0.5 + y, 0.5 – z; #2 = 1 – x,
1 – y, –z. (B) View of the three-dimensional supramolecular framework
of complex 1 constructed by hydrogen bonding interactions.
Figure 2. (A) Two L2– ligands doubly bridge two different ZnII ions
to form a secondary building unit (SBU) [Zn2(L)2(H2O)2] in complex
1. (B) View of the 2D wave-like networks of complex 1. (C) Schematic
representation of the 2D net topology (4,82) of complex 1.
N 7.56 (7.92) %. IR (KBr): ν = 3407 (br., m), 3260 (m), 1574 (s),
˜
1498(m), 1417 (s), 1351 (s), 1086 (w), 958 (w), 891 (w), 773 (m), 726
(m), 593 (w) cm–1.
Figure 4. TGA curves of complexes 1–3.
4.2.3 Synthesis of [Co(L)(H2O)] (2)
Complex 2 was synthesized by the same procedure as for the prepara- with a yield of 20.1 mg (0.0579 mmol, 57.9 % based on the H2L li-
tion of complex 1, except that Co(NO3)2·6H2O (29.1 mg, 0.100 mmol) gand). Analytical data: C14H12CoN2O5 (347.2): C 48.02 (calcd. 48.39);
was used instead of Zn(NO3)2·6H2O as the starting material. A few H 3.79 (3.46); N 7.98 (8.36) %. IR (KBr): ν = 3421 (br., m), 3260
˜
red block single crystals and some red powders of complex 2 were (m), 1602 (m), 1555 (s), 1448(m), 1417 (s), 1356 (s), 1161 (w), 1105
isolated by filtration and washed with water and ethanol several times (w), 773 (m), 721 (m), 602 (w) cm–1.
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Coordination Polymers from 5-(Pyridin-2-ylmethyl)aminoisophthalic Acid
4.2.4 Synthesis of [Ni(L)(H2O)] (3)
References
Complex 3 was also synthesized by the same procedure as for the
preparation of complex 1, except that Ni(NO3)2·6H2O (29.1 mg,
0.100 mmol) was used instead of Zn(NO3)2·6H2O as the starting mate-
rial. Green block crystals of complex 3 were obtained by filtration and
washed with water and ethanol several times with a yield of 16.6 mg
(0.0478 mmol, 47.8 % based on the H2L ligand). Analytical data:
C14H12N2NiO5 (346.9): C 48.78 (calcd. 48.42); H 3.44 (3.46); N 8.36
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˜
1441 (s), 1422 (s), 1403 (s), 1370 (s), 1285 (m), 1048 (m), 915 (m),
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4.3 X-ray Crystallography Study
The crystallographic data collections for complexes 1–3 were carried
out with a Bruker Smart Apex CCD area-detector diffractometer with
graphite-monochromated (Mo-Kα) radiation (λ
= 0.71073 Å) at
293(2) K using the ω-scan technique. The diffraction data were inte-
grated by using the SAINT program, which was also used for the
intensity corrections for the Lorentz and polarization effects. Multi-
scan absorption correction was applied using the SADABS program.
The structures of complexes 1–3 were solved by direct methods and
all non-hydrogen atoms were refined anisotropically on F2 by the full-
matrix least-squares technique using the SHELXL-97 crystallographic
software package.[10] Hydrogen atoms except the ones in the (–NH–
) of the (pyridin-2-ylmethyl)amino group and the coordinated water
molecules in complexes 1–3 were added geometrically and allowed to
ride on its parent atom. The hydrogen atoms in (–NH–) of the (pyridin-
2-ylmethyl)amino group and the coordinated water molecules in com-
plexes 1–3 were located from Fourier map directly. The contribution
of these hydrogen atoms was included in the structure factor calcula-
tions. The crystallographic details and selected bond lengths and bond
angles are provided in Table 2 and Table 3, respectively.
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge Crystal-
lographic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ,
UK. Copies of the data can be obtained free of charge on quoting the
depository numbers CCDC-811705 (for 2), CCDC-811706 (for 3),
and CCDC-811707 (for 1) (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk)
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Supporting Information (see footnote on the first page of this article):
Figure S1 and S2 describe the molecular structures of complexes 2
and 3, respectively. Table S1 reveals hydrogen bonding geometries of
complexes 1–2; Table S2 contains the detailed torsion angles of the
five-membered uncoplanar metallacycle in complexes 1–3.
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University of Göttingen, Germany, 1997.
Acknowledgement
The authors gratefully acknowledge the Natural Science Foundation
of Jiangsu Province of China (BK2008195) and the Science Research
Foundation of Huaiyin Institute of Technology (HGQ0649) for finan-
cial support of this work.
Received: April 12, 2011
Published Online: June 28, 2011
Z. Anorg. Allg. Chem. 2011, 1560–1565
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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