Hydrothermal synthesis of two Ni(II) metal-organic coordination polymers constructed from dicarboxylate and nitrogen-contained ligands

Article abstract of DOI:10.1080/15533174.2011.613080

Two new coordination polymers [Ni(2,4'-oba)(1,10-phen)]_n (1) and {[Ni(2,4'-Hoba)₂ (4,4'-bipy)(H₂O)₂]2H ₂O} n(2) have been synthesized [2,4-H₂oba=2-(4- carboxyphenoxy)benzoic acid, 1,10-phen=1,10-phenanthroline and 4,4'-bipy=4,4-bipyridine]. The framework structures of these polymeric complexes have been determined by single-crystal X-ray diffraction studies. Complex 1 exhibits double-helical chains formed by π-π stacking interactions from the phenyl rings of the 1,10-phen ligands. Complex 2 forms a two-dimensional supramolecular architecture directed by hydrogen bonding. In compounds 1 and 2, the oba² ligands exhibit two coordination modes to link metal ions: bidentate chelating and monodenate modes. Copyright Taylor & Francis Group, LLC.

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Hydrothermal Synthesis of Two Ni(II) Metal-Organic
Coordination Polymers Constructed From Dicarboxylate
and Nitrogen-Contained Ligands
Feng Guo a , Jian-Jun Li b , Xian-Jiang Li c , Bao-Yong Zhu a & Xiu-Ling Zhang a
a Department of Chemistry , De Zhou University , Shandong , P. R. China
b Weifang Entry-Exit Inspection and Quarantine Bureau , Shandong , P. R. China
c Shangdong ShengLi Co. Ltd , Shandong , P. R. China
Accepted author version posted online: 14 Mar 2012.Published online: 01 May 2012.
To cite this article: Feng Guo , Jian-Jun Li , Xian-Jiang Li , Bao-Yong Zhu & Xiu-Ling Zhang (2012) Hydrothermal Synthesis of
Two Ni(II) Metal-Organic Coordination Polymers Constructed From Dicarboxylate and Nitrogen-Contained Ligands, Synthesis
and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:4, 470-474, DOI: 10.1080/15533174.2011.613080
To link to this article: http://dx.doi.org/10.1080/15533174.2011.613080
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:470–474, 2012
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.613080
Hydrothermal Synthesis of Two Ni(II) Metal-Organic
Coordination Polymers Constructed From Dicarboxylate
and Nitrogen-Contained Ligands
Feng Guo,1 Jian-Jun Li,2 Xian-Jiang Li,3 Bao-Yong Zhu,1 and Xiu-Ling Zhang1
1Department of Chemistry, De Zhou University, Shandong, P. R. China
2Weifang Entry-Exit Inspection and Quarantine Bureau, Shandong, P. R. China
3Shangdong ShengLi Co. Ltd, Shandong, P. R. China
twist around the nonmetallic atom to meet the requirements of
Two new coordination polymers [Ni(2,4ꢀ-oba)(1,10-phen)]n (1)
and {[Ni(2,4ꢀ-Hoba)2 (4,4ꢀ- bipy)(H2O)2]·2H2O}n (2) have been
synthesized [2,4ꢀ-H2oba=2-(4-carboxyphenoxy)benzoic acid, 1,10-
phen=1,10-phenanthroline and 4,4ꢀ-bipy=4,4ꢀ-bipyridine]. The
framework structures of these polymeric complexes have been de-
termined by single-crystal X-ray diffraction studies. Complex 1
exhibits double-helical chains formed by π-π stacking interactions
from the phenyl rings of the 1,10-phen ligands. Complex 2 forms a
two-dimensional supramolecular architecture directed by hydro-
gen bonding. In compounds 1 and 2, the oba2− ligands exhibit two
coordination modes to link metal ions: bidentate chelating and
monodenate modes.
the coordination geometries of metal atoms in the assembly
process.[14–16]
In view of previous points, we chose 2-(4-carboxy
phenoxy)benzoic acid along with nitrogen-contained auxil-
iary ligands to construct two new metal coordination poly-
mers [Ni(2,4ꢁ-oba)(1,10-phen)]n (1) and {[Ni(2,4ꢁ-Hoba)2 (4,4ꢁ-
bipy)(H2O)2]·2H2O}n (2).
EXPERIMENTAL
Materials and Physical Measurements
Keywords crystal structure, hydrothermal syntheses, nickel(II)
All reagents and solvents employed were commercially avail-
able and were used as received without further purification.
Elemental analysis was carried out on a Carlo Erba 1106 full-
automatic trace organic elemental analyzer (Germany). FT-IR
spectra were recorded with a Bruker Equinox 55 FT-IR spec-
trometer (Germany) as a dry KBr pellet in the 400∼4000 cm−1
range.
complex
INTRODUCTION
The interest in the construction of metal-organic frameworks
(MOFs) is rapidly increasing in crystal engineering owing to
their ability to provide diverse assemblies with fascinating topo-
logical structures and material properties that make them poten-
tial applications relating to magnetism, porous materials, and lu-
minescence.[1–8] Selection of the appropriate multidentate ligand
to link metal ions is a key strategy for the building MOFs. There-
fore, a considerable number of transition metal compounds us-
ing carboxylates have been reported during the last decade due
to the diversity of bonding modes of carboxylate groups.[9–13]
Semirigid V-shaped multicarboxylate ligands with two ben-
zene rings of central molecular framework bridged by a non-
metallic atom (C, O, S, or N) are excellent ligands and can freely
Synthesis of [Ni(2,4ꢀ-oba)(1,10-phen)]n (1)
A mixture of NiCl2·6H2O (0.238 g, 1 mmol), H2oba (0.258 g,
1 mmol), NaOH (0.08 g, 2 mmol), 1,10ꢁ-phen(0.180 g, 1 mmol),
and distillated water (15 mL) was heated to 160◦C for 96 h in
a 25 mL stainless steel reactor with a Teflon liner. Green block
crystals of 1 were obtained with 42% yield on Ni basis. Ele-
mental Anal. Calcd. (%) for C26H16NiN2O5: C, 63.07; H, 3.26;
N,5.66. Found: C, 62.58; H, 3.24; N, 5.59. IR: 1543(s),1408(s),
1016(w),928(m),851(m),763(m).
Synthesis of [Ni(2,4ꢀ-Hoba)2 (4,4ꢀ-bipy)(H2O)2]
·2H2O} n(2)
Received 16 August 2010; accepted 7 August 2011.
The authors gratefully acknowledge financial support from the Na-
tional Natural Science Foundation of China (20971018) and also the
support from Dezhou University.
Address correspondence to Feng Guo, Department of Chem-
istry, De Zhou University, Shandong 253023, P. R. China. E-mail:
guofeng1510@yeah.net
A mixture of NiCl2·6H2O (0.238 g, 1 mmol), H2oba (0.258 g,
1 mmol), and 4,4ꢁ-bipy (0.156 g,1 mmol) and distillated water
(15 mL) was heated to 160◦C for 96 h in a 25 mL stainless
steel reactor with a Teflon liner. Green block crystals of 2 were
obtained with 65% yield on Ni basis. Elemental Anal. Calcd.
(%) for C38H34NiN2O14: C, 56.95; H, 4.28; N, 3.50. Found:
470

METAL-ORGANIC COORDINATION POLYMERS
471
C, 57.42; H, 4.26; N, 3.45. IR: 3360(br), 1639(s),1394(s),
1113(m),887(s),653(w).
Crystallographic Measurement
Diffraction intensity data of the single crystal of the two
compounds were collected on a Bruker SMART APEX CCD
diffractometer equipped with a graphite monochromated Mo-
Kα radiation (λ = 0.71073 Å) by using a ω-scan mode. Em-
pirical absorption correction was applied using the SADABS
programs.[17] All the structures were solved by direct methods
and refined by full-matrix least-squares methods on F2 using the
program SHEXL 97-[18] All non-hydrogen atoms were refined
anisotropically. The hydrogen atoms were located by geomet-
rically calculations, and their positions and thermal parameters
FIG. 1. The coordination environments of nickel(II) atoms in complex 1 with
50% thermal ellipsoids. All hydrogen atoms are omitted for clarity (color figure
available online).
TABLE 1
Crystallographic data and structure refinement summary for
complexes 1 and 2
were fixed during the structure refinement. The crystallographic
data and experimental details of structural analyses for coordi-
nation polymers are summarized in Table 1. Selected bond and
angle parameters are listed in Table 2.
Empirical formula
C26H16N2NiO5
C38H34N2NiO14
Formula weight
Crystal system
space group
Unit cell
495.12
801.38
Monoclinic P21/n Monoclinic P2/n
RESULTS AND DISCUSSION
a = 7.740(2) Å
b = 15.388(3)Å
c = 18.991(4) Å
α = 90.00◦
β = 98.107(2) ◦
γ = 90.00◦
2239.3(8)
a = 12.415 (2) Å
b = 111.269 (1) Å
c = 13.632 (2) Å
α = 90.00◦
β = 107.452 (1) ◦
γ = 90.00◦
1819.4 (4)
dimensions
Structure Description of 1
X-ray diffraction analysis shows that the asymmetric unit
of complex 1 contains one crystallographic independent Ni(II)
atom, one oba2− ligand, and one 1,10-phen ligand. A view of
the NiII atom coordination environment is presented in Figure 1.
Each Ni(II) atom is located in a distorted octahedral geometry
and is coordinated to four oxygen atoms of two oba2− ligands
and two nitrogen atoms of 1,10-phen. The Ni-O bond distances
vary from 2.076 Å to 2.142 Å, Ni-N bond lengths are 2.042 Å
and 2.056 Å. Each oba2− ligand adopts a bis(chelating biden-
tate)mode (Scheme 1a), linking two NiII ions.
Volume(Å3)
Z
4
2
Calculated
density(mg/m3)
Reflections
collected
1.469
1.463
5215
3203
The adjacent Ni(II) ions are bridged by V-shaped oba2–
ligands to form a helical chain b-axis (Figure 2). The he-
lix is generated around the crystallographic 21 axis with a
pitch of 15.464 Å. The two benzene rings of the oba2− lig-
and are bent (the dihedral angle of the two benzene rings is
∼77.27◦). The dihedral angles of carboxylate groups and the
corresponding linking rings are 12.62◦ and 34.27◦. Obviously,
this twist is an important factor is forming the helical structure.
Independent
reflections
(I > 2σ(I))
F(000)
θ range for data
collection
2993
1016
2.54–27.72
2782
832
2.39–24.99
Limiting indices
–10 ≤ h ≤ 9–
20 ≤ k ≤ 20
–24 ≤ l ≤ 24
–14 ≤ h ≤ 12
–10 ≤ k ≤ 13
–16 ≤ l ≤ 12
1.050
Goodness-of-fit on 1.000
F2
R1 ,wR2
a
b
R1 = 0.0546
wR2 = 0.0956
R1 = 0.1175
wR2 = 0.1144
R1 = 0.0304
wR2 = 0.0755
R1 = 0.0370
wR2 = 0.0779
[I > 2σ(I)]
R1,wR2 (all data)
Largest diff. peak 0.479 and –0.376 0.284 and –0.221
and hole (e/Å3)
FIG. 2. The helical chain of complex 1 along b-axis (color figure available
online).
2
aR = ꢀ(||F0|−|FC||)/ꢀ|F0|. bwR = [ꢀw(|F0|2−|FC|2)2/ꢀw(F0 )]1/2
.

472
F. GUO ET AL.
TABLE 2
Selected bond lengths (Å) and angles (◦) for complexes 1 and 2
Compound 1
Ni(1)—N(1)
Ni(1)—N(2)
Ni(1)—O(5)
N(1)—Ni(1)—N(2)
N(1)—Ni(1)—O(5)
N(2)—Ni(1)—O(5)
N(1)—Ni(1)—O(4)
N(2)—Ni(1)—O(4)
O(5)—Ni(1)—O(4)
N(1)—Ni(1)—O(3)
2.042 (3)
2.056 (3)
2.076 (2)
80.72 (11)
99.21 (9)
99.92 (10)
99.54 (9)
100.79 (10)
153.97 (9)
93.26 (10)
Ni(1)—O (4)
Ni(1)—O(3)
Ni(1)—O(2)
N(2)—Ni(1)—O(3)
O(5)—Ni(1)—O(3)
O(4)—Ni(1)—O(3)
N(1)—Ni(1)—O(2)
N(2)—Ni(1)—O(2)
O(5)—Ni(1)—O(2)
O(4)—Ni(1)—O(2)
2.083 (2)
2.124 (2)
2.142 (2)
161.54 (10)
98.26 (10)
62.79 (9)
161.09 (9)
97.15 (10)
62.46 (8)
99.32 (9)
Compound 2
Ni(1)—O(1W)#1
2.0659 (13)
2.0659 (13)
2.107 (2)
Ni(1)—O(4)#1
Ni(1)—O(4A)
Ni(1)—N(2)
2.0811 (12)
2.0811 (12)
2.085 (2)
92.82 (5)
92.82 (5)
87.45 (3)
87.45 (3)
90.02 (3)
90.02 (3)
92.55 (3)
Ni(1)—O(1WA)
Ni(1)—N(1)
O(1W)#1—Ni(1)—O(1WA)
O(1W)#1—Ni(1)—O(4A)
O(1WA)—Ni(1)—O(4)#1
O(1WA)—Ni(1)—N(1)
O(4A)—Ni(1)—N(1)
O(4)#1—Ni(1)—N(1)
N2—Ni(1)—N(1)
174.90 (7)
87.18 (5)
87.18 (5)
92.55 (3)
89.98 (3)
O(1WA)—Ni(1)—O(4A)
O(1W)#1—Ni(1)—O(4)#1
O1Wi—Ni(1)—N(2)
O(1WA)—Ni(1)—N(2)
O(4A)—Ni(1)—N(2)
O(4)#1—Ni(1)—N(2)
O(1W)#1—Ni(1)—N(1)
89.98 (3)
180.000 (1)
Symmetry code for compounds: (2)#1:−x+3/2, y, −z+3/2
The 1,10-phen ligands are alternately attached to both sides of stacking interactions that further stabilize the crystal structure
the helical chain, providing potential supramolecular recogni- (Figure 3).
tion sites for π-π stacking interactions. Two adjacent helical
chains with different handedness are assembled by intermolec-
Structure Description of 2
X-ray diffraction analysis reveals that complex 2 is a 2D
supramolecular assembly based on a 1D alternate polymeric
ular π-π stacking. The interchain distance between parallel
1,10-phen ligands is ∼3.447 Å and the corresponding centroid-
to-centroid distance is ∼3.826 Å, indicating face to face π-π
FIG. 3. The 2D supramolecular structure through π-π interceptions (color figure available online).

METAL-ORGANIC COORDINATION POLYMERS
473
FIG. 4. The coordination environments of nickel(II) atoms in complex 2 with 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity (color figure
available online).
chain substructure of Ni(Hoba)2 bridged by 4,4ꢁ-bipy. As il- rate 4,4ꢁ-bipy ligands in the equatorial plane, as well as two
lustrated in Figure 4, the six-coordinated center shows a oc- oxygen atoms from two water molecules in the axial position.
tahedral geometry [NiO4N2], with two oxygen atoms from The extended structure of 1 through 4,4ꢁ-bipy displays neutral
two different oba2− ligands and two nitrogen atoms of sepa- 1D linear [Zn(4,4ꢁ-bipy)]chains. H2oba is monodeprotonated
FIG. 5. 2D supramolecular network formed through hydrogen bonding (color figure available online).

474
F. GUO ET AL.
TABLE 3
Hydrogen bond lengths(Å) and bond angles (◦) for compound 2
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acetylpyridine)2: a weak-ferromagnet with a very big canting angle. Inorg.
Chem. 2008, 47, 5720–5726.
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organic replica of γ -Pu: the first uninodal 10-connected coordination
network based on pentanuclear cadmium clusters. Chem.Commun. 2009,
410–412.
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theses, crystal structures and magneto-structural correlations of novel CuII
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properties. Inorg. Chem. 2010, 49, 1539–1550.
D—H···A D—H H···A D···A D—H···A
O(2W)—H(22W)···O(1)#1 0.84 2.06 2.867 (2)
O(2W)—H(21W)···O(4)#2 0.85 1.92 2.733 (2)
O(1W)—H(12W)···O(2W)#3 0.84 2.34 2.888 (2)
160
160
123
152
175
O(1W)—H(11W)···O(5)
0.85 1.84 2.621 (2)
0.82 1.83 2.648 (2)
O(2)—H(2)···O(2W)#4
Symmetry codes: #1:−x+1, −y+2, −z+1; #2: −x+1, −y+1,
−z+1; #3:x+1/2, −y+1, z+1/2; #4:x, y+1, z+1.
to give Hoba−1 to meet the requirement of charge balance
requirement.
In compound 2, O2W of the guest water is involved in a “sat-
urated” hydrogen-bond pattern between the 1D chains (Table 3),
acting as a double donor and a double acceptor to three carboxy-
late oxygen atoms and one oxygen atom from a coordinated
water molecule (Figure 5).
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metal-organic frameworks based on aromatic polycarboxylateandflexible
bis(imidazole) ligands. Cryst. Growth Des. 2008, 8, 606–611.
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Organomet. Polym. 2010, 20, 38–45.
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assemble of new coordination polymers constructed from flexible-rigid
mixed ligands. J. Solid State Chem. 2007, 180, 3136–3145.
13. Biswas, C.; Jana, A.D.; Drew, M.G. B.; Mostafa, G.; Ghosh, A. Segre-
gated self-assembly and pillaring action of aliphatic dicarboxylic acids
in the super structure of Cu-picolinate complexes. Polyhedron 2009, 28,
653–660.
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L.J.; Jiang, J.Z.; Ni, Z.H. Co(II) metal-organic frameworks (MOFs) as-
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crystal structures, and magnetic properties. Cryst. Growth Des. 2009, 9,
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polymer constructed by triple-and double-helical chains. CrystEngComm
2010, 12, 1709–1711.
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L.J.; Jiang, J.Z. Diverse Ni(II) MOFs constructed from asymmetric semi-
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CONCLUSION
Two new Ni(II) metal coordination polymers assembled from
2,4ꢁ-H2oba and auxiliary ligands have been successfully pre-
pared under hydrothermal conditions. The differences of neutral
ligands and pH value affect the frameworks of the compounds.
SUPPLEMENTARY MATERIALS
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Center,
CCDC reference number 780021 and 780022. These data can
be obtained fee of charge at: http://www.ccdc.cam.ac.uk (or
Cambridge Crystallographic Data Center, 12 Union Road, Cam-
bridge CB2 1EZ, UK (fax: +44–1223–336–033; e-mail: deposit
@ccdc.cam.ac.uk).
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