One-pot synthesis, crystal structures and topology analysis of two nickel(II) complexes based on 1,3,5-benzenetricarboxylic acid

Article abstract of DOI:10.1007/s10870-013-0450-x

The one-pot solvothermal reaction of Ni(NO₃)₂ with 1,3,5-benzenetricarboxylic acid (H₃btc) and 4,4-bis(imidazol-1-yl) benzene (bibp) affords two coordination compounds. The H₃btc ligand is deprotonated step-by-s

Full text of DOI:10.1007/s10870-013-0450-x

J Chem Crystallogr (2013) 43:502–507
DOI 10.1007/s10870-013-0450-x
ORIGINAL PAPER
One-Pot Synthesis, Crystal Structures and Topology Analysis
of Two Nickel(II) Complexes Based on 1,3,5-Benzenetricarboxylic
Acid
•
•
•
Ying-Na Zhao Yan-Yan Wang Yan-Qin Zhao
Guang-Hua Cui
Received: 29 October 2012 / Accepted: 10 July 2013 / Published online: 20 July 2013
Ó Springer Science+Business Media New York 2013
Abstract The one-pot solvothermal reaction of Ni(NO3)2
with 1,3,5-benzenetricarboxylic acid (H3btc) and 4,40-
bis(imidazol-1-yl)benzene (bibp) affords two coordination
compounds. The H3btc ligand is deprotonated step-by-step,
and connects NiII ions into two different valence-bonded
structures (the binuclear molecule and 2D (4,4) grid) under
the cooperation of bibp. Hydrogen bonds have been deeply
investigated, and yield an interpenetrating binodal (3,5)-
structures and 2- or 3-D frameworks [5]. However, it is still
a great challenge in crystal engineering to obtain designed
and predictable frameworks with potential properties
assembled by coordination bonds and/or supramolecular
interactions such as hydrogen bonds, p–p stacking, and
charge-transfer interactions, etc. [6–10].
The combination of carboxylic acid and neutral imid-
azole-containing ligand offers a facile strategy to construct
mixed-ligand frameworks [11, 12]. 1,3,5-benzenetricarb-
oxylic acid (H3btc) has been extensively used in the self-
assembly of coordination polymer due to the versatile
coordination character [13]. This Y-shaped ligand presents
many potential coordination sites, which is just beneficial
to elucidate the multi-step process of deprotonation and
coordination, resulting into the polymorphism. On the
other hand, the coordination chemistry of rigid bis (imid-
azole) ligands has been deeply explored in our group, and
they are good candidates for the construction of mixed-
ligand frameworks owing to the stronger coordination
ability and linear feature [14]. In this paper, Ni(NO3)2,
H3btc, and 4,40-bis(imidazol-1-yl)biphenyl (bibp) have
been introduced into a one-pot solvothermal reaction to
afford two coordination compounds {[Ni(Hbtc)(bibp)1.5
(H2O)3]ꢀ(H2O)2}? (1) and [Ni(Hbtc)(bibp)(H2O)]? (2).
The crystal structures and supramolecular network topol-
ogies have been discussed.
¨
connected supramolecular network with the Schafli symbol
of [42.6]ꢀ[42.65.83] and interdigitating binodal (4,6)-con-
¨
nected supramolecular network with the Schafli symbol of
[44.52]ꢀ[44.56.64.7], respectively.
Keywords Complexes ꢀ One-pot synthesis ꢀ
Topology analysis ꢀ Supramolecular network
Introduction
The rational design and synthesis of coordination polymer
have currently attracted extensive attention, which is
propelled by the aesthetic architecture as well as their
tremendous potential applications in functional materials
[1–4]. The observation of coordination polymers derived
from organic ligands and metal ions through a self-
assembly route has been explored intensively, and many
efforts have been devoted to use of N- and O-donor organic
ligands as co-ligands to bridge metal ions to form infinite
network structures, such as one-dimensional (1D) chain
Experimental
Materials and Physical Measurements
Y.-N. Zhao ꢀ Y.-Y. Wang ꢀ Y.-Q. Zhao ꢀ G.-H. Cui (&)
College of Chemical Engineering, Hebei United University,
46 West Xinhua Road, Tangshan 063009, Hebei,
People’s Republic of China
All solvents and reagents for synthesis were commercially
available and used as received. The ligand bibp was syn-
thesized according to the reported procedure [15]. Elemental
e-mail: tscghua@126.com
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503
X-ray Crystallography
analyses of C, H, and N were performed on a Perkin-Elmer
240C analyzer. IR spectra were measured on a TENSOR 27
(Bruker) FT-IR spectrometer with KBr pellets. Compounds
1 and 2 were further characterized by X-ray crystallographic
analysis.
X-ray single-crystal diffraction data of 1–2 were collected
on a Rigaku MM-007/Saturn 70 with graphite monochro-
˚
matic Mo–Ka radiation (k = 0.71073 A). The program
SAINT [16] was used for integration of the diffraction
profiles. All the structures were solved by direct methods
using the SHELXS program of the SHELXTL package and
refined by full-matrix least-squares methods with SHELXL
[17]. Metal atoms in each complex were located from the
E-maps and other non-hydrogen atoms were located in
successive difference Fourier syntheses and refined with
anisotropic thermal parameters on F2. Hydrogen atoms of
organic ligands were generated theoretically onto the spe-
cific atoms and refined isotropically. However, hydrogen
atoms of water molecules were added by difference Fourier
maps, and refined using a riding model. Mercury software
offers a comprehensive range of tools for 3D structure
visualization [18]. In the structure of 1, the two lattice
water molecules are disordered, thus this structure was
refined by the SQUEEZE routine of PLATON program
[19]. Further details for structural analysis are summarized
in Table 2, and selected bond lengths and angles are listed
in Table 3.
Synthesis of {[Ni(Hbtc)(bibp)1.5(H2O)3]ꢀ(H2O)2}? (1)
and [Ni(Hbtc)(bibp)(H2O)]? (2)
Compounds 1–3 with the same ligand combination have
different compositions (and structures) were synthesized
from one-pot solvothermal reaction, however, the Ni(II)
complex 3 {[Ni3(btc)2(bibp)2(H2O)2]ꢀ3(H2O)2}? had been
reported by Zheng groups [13]. The suspension of
Ni(NO3)2ꢀ6H2O (0.12 mmol, 35 mg), H3btc (0.15 mmol,
32 mg) and bibp (0.10 mmol, 28 mg) in 12 mL component
solvent (H2O:CH3OH = 3:4) was sealed in a Teflon-lined
autoclave and heated to 120 °C for 3 days. Three kinds of
crystals with distinct differences in color (blue for 1, green
for 2 and yellow-green for 3), were obtained after the
autoclave was cooled to room temperature at 10°Ch-1
Approximate yields: ca. 5 % for 1, 5 % for 2, and 60 % for
3 based on bibp.
.
Anal. Calcd. for C72H70N12Ni2O22 (1): C, 54.98; H,
4.49; N, 10.69. Found: C, 54.74; H, 4.55; N, 10.77. IR
(KBr) for 1: 3739w, 3253s, 1901w, 1678m, 1612m,
1572m, 1514s, 1431m, 1365s, 1300w, 1242m, 1184m,
1101w, 1061m, 962w, 814m, 723w, 648m, 517w.
Anal. Calcd. for C27H20N4NiO7 (2): C, 56.78; H, 3.53;
N, 9.81. Found: C, 56.61; H, 3.58; N, 9.90. IR (KBr) for 2:
3624m, 3433s, 3161s, 1720m, 1620s, 1579m, 1514s,
1456m, 1423w, 1373s, 1315m, 1242m, 1176w, 1119w,
1061m, 937w, 822m, 764w, 723m, 648w, 508w.
Results and Discussion
Crystal structure
of {[Ni(Hbtc)(bibp)1.5(H2O)3]ꢀ(H2O)2}? (1)
Single-crystal X-ray diffraction analysis reveals that com-
pound 1 crystallizes in the monoclinic space group P21/c.
As shown in Fig. 1a, each NiII ion is coordinated by two
nitrogen atoms from individual bibp molecules and one
Hbtc2- oxygen atom. The octahedral coordination geom-
etry of NiII node is completed by three water molecules.
Anal. Calcd. for C54H44N8Ni3O17 (3): C, 51.76; H, 3.54;
N, 8.94. Found: C, 51.53; H, 3.59; N, 9.03. IR (KBr) for 3:
3616m, 3450s, 3120m, 1869w, 1612s, 1572m, 1514s,
1448m, 1365s, 1325m, 1257m, 1127w, 1068m, 930w,
822m, 771m, 731m, 658w, 517w, 442w.
˚
The Ni–N distances are 2.077(4) and 2.078(4) A, and Ni–O
˚
bond lengths range from 2.055(3) to 2.096(3) A, which are
Moreover, a series of solvothermal reactions have been
carried out under different crystallization time and tem-
perature (Table 1). Although the bulk products are
cocrystallized in one-pot, the yield of 3 (*60 %) is much
higher than that of 1 and 2 (both *5 %) when standing
3 days at 120 °C. However, a short time (1 day at 120 °C)
leads to higher yields of 1 and 2 (*50 and 20 % respec-
tively) without visible 3. It is also found that the yield of 3
is up to 75 % when standing 2 days at 140 °C, while
compounds 1 and 2 are invisible at the 809 microscope. If
the reaction standing 1 day at 140 °C, compounds 1 and 2
are overwhelming (*35 and 30 % respectively), while the
yield of 3 greatly decreases (*10 %). Furthermore, com-
pounds 1–3 are air-stable.
all in good agreement with those typically observed values
[20]. The partially deprotonated ligand Hbtc2- coordinates
Table 1 The yields of compounds 1–3 under different reaction time
and temperature
Complex
1
2
3
Time
120 °C 140 °Ca 120 °C 140 °C 120 °C 140 °C
1 day
50 %
35 %
0 %
20 %
30 %
0 %
0 %
10 %
75 %
2 days
3 days 5 %
5 %
60 %
a
Solvethermal reaction under 120 and 140 °C are shown by roman
and italics, respectively
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J Chem Crystallogr (2013) 43:502–507
˚
Table 3 Selected bond lengths (A) and angles (deg) for 1–2
Table 2 Crystal data and structure refinement for 1 and 2
Complex
1
2
Complex 1
Ni1–O1
2.055(3)
Ni1–O1W
2.057(3)
Empirical formula
Formula weight
Crystal size (mm3)
Crystal system
Space group
C72H70N12Ni2O22
1572.82
0.25 9 0.20 9 0.18
monoclinic
P21/c
C27H20N4NiO7
571.18
Ni1–N1
2.077(4)
Ni1–N5
2.078(4)
Ni1–O3W
2.101(3)
Ni1–O2W
2.096(3)
0.25 9 0.22 9 0.18
monoclinic
P21/c
O1W–Ni1–N1
O1–Ni1–N1
O1W–Ni1–O3W
O1–Ni1–O3W
N1–Ni1–O3W
O1W–Ni1–N5
O1–Ni1–N5
Complex 2
Ni1–O1
92.53(13)
95.24(13)
92.06(12)
87.37(12)
90.52(13)
93.22(14)
87.06(13)
O3W–Ni1–N5
O1W–Ni1–O2W
O1–Ni1–O2W
N1–Ni1–O2W
O3W–Ni1–O2W
N5–Ni1–O2W
N1–Ni1–N5
174.16(14)
87.46(12)
84.75(12)
176.72(13)
86.19(12)
91.56(14)
91.72(15)
˚
a (A)
13.564(3)
12.096(2)
21.708(4)
93.86(3)
3553.6 (12)
2
10.515(2)
10.101(2)
22.705(5)
102.84(3)
2351.2(8)
4
˚
b (A)
˚
c (A)
b (°)
3
˚
V (A )
Z
2.0361(16)
2.086(2)
2.1255(16)
97.68(8)
92.07(8)
92.99(8)
158.10(7)
95.27(7)
97.76(6)
87.61(7)
61.10(6)
Ni1–N1
2.052(2)
Dcalcd (g.cm-3
)
1.470
1.614
Ni1–N4A
Ni1–O1W
2.1091(18)
2.1883(16)
89.06(7)
F(000), e
1636
1176
Ni1–O3B
Ni1–O4B
Refl. measured
Refl. unique
Rint
29487
19889
O1–Ni1–N1
N1–Ni1–N4A
N1–Ni1–O1W
O1–Ni1–O3B
N4A–Ni1–O3B
O1–Ni1–O4B
N4A–Ni1–O4B
O3B–Ni1–O4B
a
O1–Ni1–N4A
O1–Ni1–O1W
N4A–Ni1–O1W
N1–Ni1–O3B
O1W–Ni1–O3B
N1–Ni1–O4B
O1W–Ni1–O4B
6261
4134
85.86(7)
0.0755
0.0296
173.27(7)
103.59(7)
87.86(7)
Goodness-of-fit
on F2
1.191
1.119
Final R indices
[I [ 2r(I)]a
R indices (all data)
R1 = 0.0716,
wR2 = 0.1425
R1 = 0.0346,
wR2 = 0.0738
164.55(7)
88.69(7)
R1 = 0.1000,
wR2 = 0.1532
R1 = 0.0397,
wR2 = 0.0758
Dqfin (max/min),
e A
1.123/- 0.605
0.579/-0.337
-3
˚
Symmetry mode for 2, A: x ? 1, -y ? 1/2, z ? 1/2; B: x, y ? 1, z
a
R1 = R||Fo|-|Fc||/R|Fo| and wR2 = {R[w(F 2o-F c2)2]/[w(F o2)2]}1/2
,
connected node. Therefore, the combination of nodes and
connectors affords a binodal (3,5)-connected network with
[Fo [ 4r(Fo)]
2
2
5
3
¨
the Schafli symbol of [4 .6]ꢀ[4 .6 .8 ] [22], which calcu-
lated by TOPOS 4.0 program [23] (Fig. 1c). Further
topological analysis suggests that such two independent
frameworks are interlocked with each other, and the most
fascinating structural feature is that 1 represents an inter-
penetrating supramolecular network (Fig. 1d). Free water
molecules are dispersed and further stabilize the 3D
supramolecular architecture.
to one NiII ion adopting a monodentate mode and leaving
an uncoordinated deprotonated carboxylate group, which is
relatively uncommon [21]. For the bibp ligand, there are
two coordination modes, i.e. monodentate terminal group
and bidentate linker. Hereinto, one third of bibp takes
bidentate mode to connect two metal-coordinated spheres
into a binuclear molecule (Scheme 1)
The discrete binuclear motifs are cross-linked by
hydrogen-bond interaction among coordinated water mol-
ecules, Hbtc2- oxygen atoms and bibp nitrogen atoms
[O1W–H1BꢀꢀꢀO3, O2W–H2AꢀꢀꢀO4 and O1W–H1AꢀꢀꢀN4
Crystal Structure of [Ni(Hbtc)(bibp)(H2O)]? (2)
Similar to 1, compound 2 also crystallizes in the mono-
clinic space group P21/c, containing four symmetry-related
NiII ions in each unit cell. As shown in Fig. 2a, the
geometry of NiII ion is surrounded by two nitrogen atoms
from individual bibp molecules, three oxygen atoms from
two partially deprotonated Hbtc2- ions and a water mole-
cule, which gives a distortedly octahedral coordination
environment. The Ni–N distances are 2.052(2) and
˚
for 2.751(3), 2.714(4) and 2.814(5) A, respectively], thus
leading the formation of 2D supramolecular network
(Fig. 1b). Interestingly, adjacent 2D layers are further
connected through hydrogen bonds O6–H6ꢀꢀꢀO4 and O2W–
˚
H2BꢀꢀꢀO5 [2.592(4) and 2.880(4) A] into a 3D supramo-
lecular framework. The topological method was applied to
explore the nature of this fascinating framework. The
Hbtc2- ligand is three-connected by linking to three NiII
ions and could be simplified as a three-connected node.
Except for three Hbtc2- nodes, the NiII center is also
connected with two equivalent NiII ions by bibp or double-
bibp connectors; the NiII ion is considered as a five-
˚
2.086(2) A, and Ni–O bond lengths span a narrow range
˚
[2.0361(16)–2.1883(16) A], which are in accord with
above reported values of 1. In 2, the bibp ligand bridges
adjacent NiII nodes to form a W-type 1D chain, and the
partially deprotonated Hbtc2- ligand also links NiII ions to
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505
Fig. 1 a View of the octahedral coordination environment in 1
(hydrogen atoms except carboxyl group omitted for clarity); b view of
the 2D supramolecular layer based on a binuclear motif in 1; c view
of the bimodal (3,5)-connected framework in 1; d view of the
interpenetrating supramolecular network in 1
COOH
interactions with the centroid–centroid separation of ca. 3.7
´
˚
and 4.2 A (Fig. 2d) [19].
HOOC
N
N
N
N
Structural Comparison of 1, 2 and 3
COOH
bibp
H3btc
The reaction system of NiII-H3btc-bibp has been previ-
ously studied by a pH-adjusting hydrothermal method,
which only affords compound 3 with 3D (4, 4)-connected
framework, and complexes 1–2 have not been observed
[13]. Interestingly, in this paper, three compounds 1–3 have
been synthesized from the identical system by one-pot
solvothermal reaction, which provides an ideal example to
study on the complexes. The great difference may be due to
the pH value: in the preceding hydrothermal reaction, the
additive NaOH causes a complete deprotonation of H3btc
to give an exclusive btc3- ion, which further participates in
the coordination assembly to afford 3. However, in our
solvothermal reaction, different deprotonated styles of
H3btc are available, and thus various coordination poly-
mers could be generated.
Scheme 1 Structures of the ligands used in this work
form a linear chain with two carboxylate groups, which
adopt monatomic and bidentate chelated modes, respec-
tively. Thus the extended structure illustrates a 2D wave-
like (4,4) grid (Fig. 2b).
Interestingly, two adjacent 2D grids are associated with
each other through hydrogen bonds O5–H5AꢀꢀꢀO4 and
˚
O1W–H1AꢀꢀꢀO2 [2.635(2) and 2.778(2) A], resulting in a
3D supramolecular framework. In this double-layer archi-
tecture, the Hbtc2- ligand bridges four NiII ions and could
be simplified as a four-connected node. Except for four
Hbtc2- nodes, the NiII center is also connected with two
equivalent NiII ions by bibp connectors; thus the NiII ion is
considered as a six-connected node. The topological
approach with TOPOS 4.0 program [23] reveals a binodal
(4,6)-connected supramolecular framework with the
In this study, the compounds 1–3 are obtained under
same conditions, displaying a diversity of discrete binu-
clear molecule, 2D (4,4) layer and 3D (4,4)-connected
network structures. As described above, the bibp act as
monodentate terminal group and bidentate linker, showing
the similar coordination modes in the three compounds. As
a comparison, it is easy to find that the complexities of the
title compounds 1–3 strongly rely on the various bridging
4
2
4
6
4
¨
Schafli symbol of [4 .5 ]ꢀ[4 .5 .6 .7] [22] (Fig. 2c). Further
topological analysis suggests that, along b axis, two adja-
cent double-layer architectures pack tightly in a staggered
mode to form an interdigitating network via weak p–p
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J Chem Crystallogr (2013) 43:502–507
Fig. 2 a View of the octahedral coordination environment in 2
(hydrogen atoms except carboxyl group omitted for clarity), symme-
try transformations used to generate equivalent atoms: A = x ? 1, -
y ? 0.5, z ? 0.5; B = x, y ? 1, z. b view of the 2D wave-like layer
in 2; c view of the binodal (4,6)-connected supramolecular framework
in 2; d view of the interdigitating network in 2
modes of the 1,3,5-benzenetricarboxylic acid, resulting
from completely or partially de-protonated sites. In com-
pound 1, the partially deprotonated ligand Hbtc2- coordi-
nates to one NiII ion adopting a monodentate mode,one
third of bibp ligand takes bidentate mode to connect two
metal-coordinated spheres into a binuclear molecule.
Whereas in 2, the Hbtc2- ligand links neighboring NiII ions
to form a linear chain with two carboxylate groups, which
adopt monatomic and bidentate chelated modes, respec-
tively. The bibp ligand further bridges adjacent NiII nodes
into 2D (4,4) network. In 3, the repeating basic secondary
building unit (SBU) in this complex consists of three nickel
ions, carboxylate oxygen atoms bonding to neighboring
nickel ions. The fully deprotonated btc and bibp ligands
link the trinuclear secondary building units to form a 3D
(4,4)-connected network.
Conclusion
Two complexes 1 and 2 have been synthesized from a one-
pot solvethermal reaction, compounds 1 and 2 illustrate
various valence-bonded architectures, i.e. discrete binu-
clear molecule, 2D (4,4) layer. Furthermore, hydrogen
bonds in 1 and 2 have been investigated to afford an
interpenetrating binodal (3,5)-connected supramolecular
2
2
5
3
¨
network with the Schafli symbol of [4 .6]ꢀ[4 .6 .8 ] and
interdigitating binodal (4,6)-connected supramolecular
4
2
4
6
4
¨
network with the Schafli symbol of [4 .5 ]ꢀ[4 .5 .6 .7],
respectively. The results demonstrate that the bridging
modes of the 1,3,5-benzenetricarboxylic acid and hydrogen
bonds interaction can exert significant influences on the
topologies of final nickel(II) complexes.
Interestingly, the number of coordination water mole-
cules combined with each metal ion shows the self-
assembly of coordination polymer. According to chemical
formulas, each NiII ion in 1–3 possesses three, one and 2/3
crystal coordination water molecules, respectively. From 1
to 3, the coordination crystal water molecule of complexes
1–3 is gradually squeezed by the organic ligand, and fur-
ther replaced by the hetero-atom, which clearly shows the
progress of self-assembly.
Supplementary Data
Crystallographic data (excluding structure factors) for the
structure in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre as the supplementary
publication no. CCDC 868356–868357. This data can
be obtained from the Cambridge Crystallographic Data
Center, 12 Union Road, Cambridge CB2 1EZ, UK;
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