Transition metal coordination complexes based on V-shaped bis-triazole ligand: syntheses, structures, and properties

Article abstract of DOI:10.1080/00958972.2018.1457146

Hydrothermal reactions of 1,3-bis(1,2,4-triazol-1-yl)benzene (btb) and M(NO₃)₂ (M?=?Co²⁺ (1), Cu²⁺ (2)) afforded two new coordination polymers, [Co(btb)₂(NO₃)(H₂O)]_n·NO₃·H₂O (1) and [Cu(btb)₂(NO₃)₂]_n (2), respectively. Single-crystal X-ray diffraction reveals that 1 crystallizes in the space group P2₁/m and 2 crystallizes in the space group Pī, both showing a double-stranded chain structure. The 1-D chains are interconnected via π?π interactions to lead to 2-D ladder-like supramolecular architectures. In addition, magnetic behavior and thermal stability of 1 and 2 have been investigated. For 1, weak antiferromagnetic interactions are observed at low temperature, and the data obey the Curie–Weiss law χ_M?=?C/(T?θ), with C?=?3.22?cm³·mol^?1·K and θ?=??10.39?K. For 2, the decrease of the χT vs. T curve at low temperature is the result of intermolecular antiferromagnetic magnetic interactions.

Full text of DOI:10.1080/00958972.2018.1457146

Journal of Coordination Chemistry
ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://www.tandfonline.com/loi/gcoo20
Transition metal coordination complexes based on
V-shaped bis-triazole ligand: Syntheses, structures
and properties
Xiu Juan Shi, Peng Yun Chen, Ming Ze Wu, Dong Chen Cai & Li Tian
To cite this article: Xiu Juan Shi, Peng Yun Chen, Ming Ze Wu, Dong Chen Cai & Li
Tian (2018): Transition metal coordination complexes based on V-shaped bis-triazole
ligand: Syntheses, structures and properties, Journal of Coordination Chemistry, DOI:
10.1080/00958972.2018.1457146
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Publisher: Taylor & Francis
Journal: Journal of Coordination Chemistry
DOI: http://doi.org/10.1080/00958972.2018.1457146
Transition metal coordination complexes based on V-shaped bis-triazole ligand:
Syntheses, structures and properties
XIU JUAN SHI, PENG YUN CHEN, MING ZE WU, DONG CHEN CAI and LI TIAN
Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Key Laboratory of Inorganic-
Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Normal University, Tianjin 300387,
P. R. China
2
+
Hydrothermal reactions of 1,3-bis(1,2,4-triazol-1-yl)benzene (btb) and M(NO ) (M = Co (1),
3
2
2
+
Cu (2)) afforded two new coordination polymers, [Co(btb) (NO )(H O)] ·NO ·H O (1) and
2
3
2
n
3
2
[
Cu(btb) (NO ) ] (2), respectively. Single-crystal X-ray diffraction reveals that 1 crystallizes in
2 3 2 n
the space group P2 /m and 2 crystallizes in the space group Pī, both showing a double-stranded
1
chain structure. The 1D chains are interconnected via π···π interactions to lead to 2D ladder-like
supramolecular architectures. In addition, magnetic behavior and thermal stability of 1 and 2
have been investigated. For 1, weak antiferromagnetic interactions are observed at low
3
−1
temperature, and the data obey the Curie–Weiss law  = C/(T−θ), with C = 3.22 cm ·mol ·K
M
and θ = −10.39 K. For 2, the decrease of the χT vs. T curve at low temperature is the result of
intermolecular antiferromagnetic magnetic interactions.
Keywords: Crystal structure; 1,3-Bis(1,2,4-triazol-1-yl)benzene; Transition metal; Thermal
stability; Magnetic property
*
Corresponding author. Email: lilytianli@hotmail.com
1

1
. Introduction
Coordination polymers have attracted extensive interest not only due to the structural diversity
but also due to their fascinating properties, such as luminescence, chemical sensing, magnetism,
gas storage and separation, and catalysis [1-12]. The main step for preparing polymeric
coordination complexes with versatile topologies and fascinating properties is to select
multidentate organic ligands as building blocks [13-17]. A number of N-donor ligands (such as
pyridyl-type ligands and azole-type ligands) have been used to build coordination polymers with
attractive architectures and functional properties [18-25]. Among the various N-donor bridging
ligands, 1,2,4-triazole and its derivatives have proven to be good candidates for the construction
of coordination polymers with varied topologies and functional properties because of their
versatile bridging feature [26-29]. 1,3-Bis(1,2,4-triazol-1-yl)benzene (abbreviated as btb) is a
rigid ligand, which contains two 1,2,4-triazole rings and can act as a multidentate bridging
ligand. In this contribution, two new complexes, [Co(btb) (NO )(H O)] ·NO ·H O (1) and
2
3
2
n
3
2
[
Cu(btb) (NO ) ] (2), were isolated by reactions of btb with MNO ·3H O (M = Co, Cu). In
2 3 2 n 3 2
addition, the structural character, magnetic behavior and thermal stability of 1 and 2 have been
investigated.
2
2
. Experimental
.1. General considerations
Triazole and CuI were purchased from Tianjin Heowns Biochem LLC and 1,3-dibromobenzene
from Meryer Chemical Technology Co., Ltd. The solvent (CH ) SO for the reaction was dried
3
2
over 4 Å molecular sieve and distilled under reduced pressure. The elemental analyses (C, H and
1
N) were carried out on a Perkin–Elmer elemental analyzer. The H NMR spectrum was recorded
with Bruker 400 MHz spectrometer instruments in CDCl . Powder X-ray diffraction
3
measurements were recorded on a D/Max-2500 X-ray diffractometer using Cu-Ka radiation.
Thermogravimetric experiments were performed on a NETZSCH TG 209 instrument with a
-1
heating rate of 10 C·min under nitrogen conditions. Direct-current (dc) magnetic
2

susceptibilities of crystalline samples were measured on an MPMS-7 SQUID magnetometer. The
data were corrected for the diamagnetism of the samples using Pascal constants. Alternating-
current (ac) susceptibilities were performed on the same magnetometer.
2
.2. Synthesis of ligand 1,3-bis(1,2,4-triazol-1-yl)benzene (btb)
Triazole (2.18 g, 12.8 mmol), 1,3-dibromobenzene (0.75 g, 3.2 mmol), K CO (2.96 g,
2
3
2
1
1.0 mmol), CuI (0.03 g, 0.13 mmol) and 7 drops of N,N’-dimethylethanamine were mixed in
5 ml dry DMSO solution and heated at 150 C for 36 h under a nitrogen atmosphere. Then the
mixture was cooled to room temperature, filtered and the solid was washed with a few milliliters
of DMSO. The filtrate was distilled under reduced pressure to remove the solvent and the residue
was extracted with CH Cl (6×30 mL). The organic layer was dried over magnesium sulfate and
2
2
the solvent removed using a rotary evaporator to give the crude product, which was further
1
separated under column chromatography to give 0.54 g of btb. Yield: 79%; H NMR [CDCl ]:
3
8
.61 (s, 2H), 8.09 (s, 3H), 7.68 (t, 1H), 7.66 (d, 1H), 7.60 (dd, 1H) ppm; elemental analysis calcd
1
(
%) for C H N : C, 56.59; H, 3.80; N, 39.61. Found: C, 56.37; H, 3.68; N, 39.42. The H NMR
1
0
8
6
spectrum is shown in the Supporting Information section as figure S1.
2
.3. Synthesis of [Co(btb) (NO )(H O)] ·NO ·H O (di-1,3-bis(1,2,4-triazol-1-
2 3 2 n 3 2
yl)benzenemonoaquamononitratocobalt(II)monoaquanitrate (1))
A mixture of Co(NO ) ·6H O (29 mg, 0.1 mmol), btb (21 mg, 0.1 mmol), H O (4 mL) and
3
2
2
2
CH OH (2 mL) was added to a Parr Teflon-lined stainless steel vessel, and then the vessel was
3
sealed and heated to 120 C for 3 days. After that the autoclave was cooled to room temperature
-1
at a rate of 1.5 C/h , the mixture was filtered, and a pink crystalline product 1 (30.24 mg) was
obtained by evaporating the filtrate for about a week (yield 47% based on Co). Anal. Calc. for
C H CoN O (643.43): C, 43.55; H, 3.13; N, 19.31. Found: C, 43.26; H, 3.32; N, 19.18%.
2
0
20
14
8
3

2
.4. Synthesis of [Cu(btb) (NO ) ] (di-1,3-bis(1,2,4-triazol-1-yl)benzenedinitratocopper(II) (2))
2 3 2 n
Blue crystals of 2 (27.54 mg) were obtained by adopting the same synthetic procedure as 1 only
with the use of Cu(NO ) ·4H O instead of Co(NO )·6H O. Yield: 45% (based on Cu). Anal.
3
2
2
3
2
Calc. for C H CuN O (612): C, 39.25; H, 2.61; N, 32.05. Found: C, 39.08; H, 2.44; N,
20
16
14
6
3
1.88%.
2
.5. X-ray crystallography
Single-crystal X-ray diffraction measurements for 1 and 2 were carried out on a Bruker Smart
CCD diffractometer with a graphite crystal monochromator situated in the incident beam for data
collection at 296(2) K. Semi-empirical multiscan absorption corrections were applied by
SCALE3 ABSPACK, and the programs CrysAlisPro were used for integration of the diffraction
profiles [30, 31]. Structures were solved by direct methods and refined with the full-matrix least-
squares technique using the ShelXT and ShelXL programs for 1 [32-34] and the SHELXS-97
and SHELXL-97 programs for 2 [35]. Anisotropic thermal parameters were assigned to all non-
hydrogen atoms, and hydrogens were located and refined isotropically. Crystallographic data for
1
and 2 are summarized in table 1.
3
3
. Results and discussion
.1. Crystal structure of [Co(btb) (NO )(H O)] ·NO ·H O (1)
2
3
2
n
3
2
Single-crystal X-ray diffraction analyses show that 1 belongs to the monoclinic P2 /m space
1
group with Z = 2. As shown in figure 1, the asymmetric unit contains one crystallographically
2
+
unique Co ion, two btb ligands, a terminally coordinated NO anion, a coordinated water
3
II
molecule, one free NO anion and one crystal lattice water molecule. Each Co ion lies on a
3
crystallographic inversion center and adopts a slightly distorted octahedral {CoN O }
4
2
environment involving four nitrogen atoms from four btb ligands, one oxygen atom from a
monodentate nitrate and one oxygen atom from one aqua ligand. The Co–O bond distances are in
the range of 2.053(10)2.136(10) Å, and the Co–N bond lengths are 2.149(5) and 2.142(6) Å,
4

II
respectively. The Co nodes are connected to each other to form an infinite 1D chain that
consists of a 20-membered bimetallic macrocycle building block, in which the free water guest
-
molecules and NO anions are located. The Co···Co separation across the bridging btb ligand is
3
1
0.945(2) Å. Along the b direction, the π···π (3.547 Å, the distance between the two centers of
the benzene rings) interactions with a slip angle of 6.43 help to generate an extended 2D
framework (figure 1(c)). In addition, C1–H1···O4, C8–H8···O8, C1–H1···O4, C5–H5···O4 or

C5–H5···O6 non-classical hydrogen-bonding interactions from NO and aqua oxygen atoms
3
connect the chains to give a 3D supramolecular framework (figure S2). The crystal packing
figure is shown in the Supporting Information and the chains are parallel to each other in a and b
II
II
directions. The shortest distance of the Co ···Co between the chains is 8.951 Å. The
-
coordinated NO anions are disordered.
3
3
.2. Crystal structure of [Cu(btb) (NO ) ] (2)
2 3 2 n
Complex 2 crystallizes in the triclinic crystal system, space group Pī (table 1). As depicted in
-
figure 2, Cu1 is six-coordinate with four nitrogen atoms, and two NO oxygen atoms, forming a
3
distorted octahedral geometry. Every btb adopts a μ -bridging mode and the dihedral angles
2
between the benzene ring and the two triazole rings are 22.08 and 66.28, respectively, which
shows a certain degree of distortion. Acting as a bidentate bridging ligand, a pair of btb ligands
chelate the Cu1 centers by triazolyl N donors with the Cu···Cu separation being 10.588(3) Å,
which leads to a double-stranded chain (figure 2b). In the bc plane, the π···π (3.588 Å, the
distance between the two centers of the benzene rings) interactions with a slip angle of 9.90
help to generate an extended 2D framework. The chains are interlocked to each other through
-
NO and crosslinked by weak hydrogen bond interactions (C1–H2···O1, C2–H2···O2, C6–
3
H6···O2) to give 3D supramolecular structures as shown in figure S3. The shortest Cu···Cu
distance between the nearest chains is 7.376 Å.
Only one bis-imidazole benzene coordination polymer has been reported [36]. Li et al.
synthesized [Zn(dib)(CH COO) ]·2H O (dib, 1,4-di(1H-imidazol-1-yl)benzene) with a 1-D one-
3
2
2
5

stranded chain structure. In the compound, though the coordinating mode of the dib ligand is bis-
connected, the structure of the compound is different from 1 and 2 because of the angle of the
two imidazoles in the dib is 180.
3
.3. Magnetic properties of 1
The magnetic susceptibilities of 1 were measured under 1 kOe in the 2–300 K range and the
magnetic behaviors are shown in figure 3. At room temperature, the value of MT
3
−1
3
−1
(
3.12 cm ·mol ·K) is considerably higher than the spin-only value of 1.87 cm ·mol ·K for one
II
II
S = 3/2 Co ion, which is due to the spin-orbit coupling of high-spin Co ions in an octahedral
surrounding. Upon cooling, the  T product decreases slowly and reaches the value of
M
3
−1
3
−1
2
2
3
.88 cm ·mol ·K at 120 K. With further cooling,  T decreases linearly to 1.81 cm ·mol ·K at
M
K. The data in the range of 2–300 K obey the Curie–Weiss law  = C/(T−θ), with C =
M
3
−1
II
.22 cm ·mol ·K and θ = −10.39 K. The strong spin-orbital coupling of Co itself can lead to a
negative θ value and a decrease of  T at higher temperature, therefore the negative θ does not
M
necessarily indicate dominant antiferromagnetic interaction between the metal centers. In the low
temperature region, the rapid decrease of the value of  T is ascribed to the weak
M
antiferromagnetic intermolecular interaction through supramolecular contacts (stacking contacts
or H bonds). The M vs. H plot for 1 is shown in figure 3(b). M increases rapidly at low field, and
reaching about 2.07 Nβ at 20 kOe. In the high field region, the increase of magnetization is slow,
reaching 2.43 Nβ at 70 kOe, which is a little smaller than the value of 3 Nβ anticipated for one
II
independent Co with S = 3/2 ground state. In order to probe the magnetic dynamics behavior for
1
, alternating current (ac) magnetic susceptibilities were measured. As shown in figure 4, the
out-of-phase signals did not show frequency dependence and maximum, which excluded the
occurrence of magnetic ordering above 2.0 K.
6

3
.4. Magnetic properties of 2
3
−1
The room temperature value of  T is 0.381 cm ·mol ·K (figure 5(a)), which coincides with the
M
3
−1
II
spin-only value of 0.375 cm ·mol ·K for one S = 1/2 Cu ion. As the temperature is lowered,
the  T product remains basically the same. The Cu···Cu distance across the long btb ligand is
M
1
0.59 Å, the magnetic interaction through btb bridge is expected to be very weak, so the complex
exhibits no obvious magnetic interaction at the high temperature. In the low temperature, the
abrupt fall of the value  T is ascribed to the weak antiferromagnetic intermolecular interaction.
M
The variation of the magnetization (M) vs. the field (H) at 2 K in figure 5(b) further confirms the
nature of the ground state in 2.
3
.5. The thermal analyses of 1 and 2
The thermal behaviors of 1 and 2 were studied by thermogravimetric analysis (TGA) under a
nitrogen atmosphere in the temperature range of 0–800 C. The experimental curves are shown
in figure 6. The TGA result of 1 displays two step weight losses. The first weight loss of 4.9%
from 90 to 125 C should be attributed to the loss of free and coordinated water (calcd. 5.59%),
and the second weight loss is ascribed to the loss of btb ligands and the nitrate ligand when the
temperature is above 265 C. The TG curve for 2 indicates that it is stable up to 275 C. Under
further heating, a rapid weight loss occurs, which is due to the departure of organic ligands and
nitrate ligand.
4
. Conclusion
Two new metal–organic frameworks have been constructed from btb and divalent transition
metals. Both 1 and 2 exhibit one-dimensional double-stranded chains. In both of the complexes,
the 1D chains assembled into 2D step-ladder supramolecular architectures interconnected by
π···π interactions, which are further constructed into 3D supramolecular structures by weak
hydrogen bond interactions. In both of the complexes, weak intermolecular antiferromagnetic
interactions exist at low temperature.
7

Supplementary material
CCDC 1587236 (2) and 1587237 (1) contain the supplementary crystallographic data. These data
can be obtained free of charge via www.ccdc.can.ac.uk/conts/retrieving.html (or from the
Cambridge Crystallographic Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (+44)
1
223-336033; or E-mail: deposit@ccdc.cam.ac.uk).
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China
(21371133).
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1
0

II
Figure 1. (a) Coordination environments of Co ions in 1. (b) The 1D double chain of 1,
–
encapsulating free NO anions and water as guest molecules. (c) Partial view of the 2D
3
supramolecular network.
1
1

II
Figure 2. (a) Coordination environments of Cu ions in 2. (b) Partial view of the 1D double-
stranded chain. (c) Packing in polymer direction along [001]. Hydrogens have been
omitted for clarity.
1
2

-1
Figure 3. (a) Temperature dependence of  T for 1 at 1000 Oe. The curve of  vs. T; the solid
M
M
line is the linear fitting of the Curie–Weiss law. (b) The M vs. H plot for 1 measured at 2 K.
Figure 4. Temperature dependence of the imaginary of the in-phase (′) and out-of-phase (″)
components of the AC magnetic susceptibility for 1 in a zero DC field with an oscillation of 3.5
Oe.
1
3

Figure 5. (a) Temperature dependence of  T for 2 at 1000 Oe. (b) The M vs. H plot for 2
M
measured at 2 K.
Figure 6. TGA curve for 1 and 2. The sample was heated to 800 °C at the heating rate of
1
.5 °C/min.
1
4

Table 1. Crystallographic data and structure refinement details for 1 and 2.
1
2
Formula
Mr
C H CoN O
C H CuN O
6
2
0
20
14
8
20 16
14
643.43
612.01
Crystal system
Space group
a (Å )
Monoclinic
Triclinic
Pī
P2 /m
1
7.0754(5)
7.376(2)
8.719(3)
9.581(3)
81.683(5)
74.957(5)
81.811(4)
585.2(3)
2
b (Å )
16.9645(11)
10.9454(6)
90
c (Å )
α (°)
β (°)
107.999(7)
90
γ (°)
V (Å3)
1249.49(14)
2
Z
ρcalc (Mg/m3)
1.710
1.737
-
1
μ (mm )
6.093
1.006
F(000)
658
311
θ range (°)
Limiting indices
4.247 – 67.076
-6 ≤ h ≤ 8
2.215 – 26.498
-9 ≤ h ≤ 9
-
20 ≤ k ≤ 20
13 ≤ l ≤ 12
-10 ≤ k ≤ 10
-5 ≤ l ≤ 12
-
Reflns. collected
GOF on F2
4743
3414
1.032
1.095
R /wR [I > 2σ(I )]
R = 0.0764,
1
R = 0.0344,
1
1
2
wR = 0.1920
wR = 0.0942
2
2
R /wR (all data)
R = 0.1050,
1
R = 0.0360,
1
1
2
wR = 0.2159
wR = 0.0956
2
2
1
5