A mononuclear cobalt(III) 3-(2-pyridyl)-5-phenyl-1,2,4-triazolato complex: Hydrothermal synthesis, crystal structure, thermostability, and DFT calculations

Article abstract of DOI:10.1515/znb-2015-0039

Starting with 1H-3-phenyl-5-(pyridin-2-yl)-1,2,4-triazole (1-Hppt), a Co(III) complex, [Co(ppt)₃] (1), has been synthesized by reaction with CoF₃ under hydrothermal conditions and characterized by its infrared spectrum and elemental

Full text of DOI:10.1515/znb-2015-0039

Z. Naturforsch. 2015; aop
Huaixian Liua, Lin Suna, Huiliang Zhou, Peipei Cen, Xiaoyong Jin, Xiangyu Liu* and Qilin Hu
A mononuclear cobalt(III) 3-(2-pyridyl)-5-phenyl-
1,2,4-triazolato complex: hydrothermal synthesis,
crystal structure, thermostability, and DFT
calculations
DOI 10.1515/znb-2015-0039
Received March 3, 2015; accepted April 2, 2015
intriguing variety of topologies and structural motifs [11–14].
However, it is still a great challenge to rationally design and
control the exact structure of CPs. Generally, the structure of
target CPs is influenced by several factors, such as counter
Abstract: Starting with 1H-3-phenyl-5-(pyridin-2-yl)-1,2,4- ions, pH, reaction temperature, and solvent system [15]. In
triazole (1-Hppt), a Co(III) complex, [Co(ppt)3] (1), has addition to controlling the reaction conditions, using theoret-
been synthesized by reaction with CoF3 under hydrother- ical calculations to predict and guide experimental research
mal conditions and characterized by its infrared spectrum has long been a target for scientists [16]. What is even more
and elemental analysis. The structure was determined important is conducting research on the reaction systems
by single-crystal and powder X-ray diffraction. Density based on the combination of theory and experiment, which
functional theory (DFT) was employed to determine the is conducive to revealing the preferred geometry and con-
optimized geometry and preferred conformation of the structing a structural model of the compounds [17, 18].
free ligand. A supramolecular network is formed via π–π
Pyridine-based triazole ligands have been proved as
stacking interactions. The conformation and geometry of a type of excellent connectors to engender a wide range
the ligands correspond with the calculated results.
of CPs resulting from the following advantages: (i) the
abundant nitrogen donor atoms in the molecule can be
Keywords:
1H-3-phenyl-5-(pyridin-2-yl)-1,2,4-triazole; selectively coordinated to metal ions, facilitating the gen-
Co(III) complex; crystal structure; DFT calculation.
eration of CPs [19] and (ii) the ligand can adopt various
coordination modes, such as multidentate or bridging
[20–22]. In this work, we have adopted the 3-phenyl-
5-(pyridin-2-yl)-1,2,4-triazolato anion (ppt–) as a ligand to
Co(III) to assemble a supramolecular architecture.
1 Introduction
In recent years, experimental and theoretical efforts have
Based on the above considerations, we have inferred
been extensively devoted to crystal engineering of coordi- the optimized structure and conformation of the 1H-3-
nation polymers (CPs) from predesigned bridging ligands phenyl-5-(pyridin-2-yl)-1,2,4-triazole (1-Hppt) molecule
and metal ions, because such hybrid materials display a using the density functional theory (DFT) method. The
variety of regulated architectures and thus many potential coordination polymer, [Co(ppt)3] (1), has been obtained
functions [1–5]. The interest in polymer architectures arises under the hydrothermal condition, and its structure
not only from their potential applications in luminescence, and thermostability were measured. The theoretical and
magnetism, sorption, gas adsorption, nonlinear optics, experimental results are compared and discussed.
catalytic materials, and medicine [6–10], but also from their
a
Huaixian Liu and Lin Sun: These authors contributed equally to this
2 Results and discussion
work.
*Corresponding author: Xiangyu Liu, School of Chemistry and
Chemical Engineering, Ningxia University, Yinchuan 750021,
2.1 Computational results of the 1-Hppt
P. R. China, Tel.: +86-951-2062004, Fax: +86-951-2062860,
molecule
E-mail: xiangyuliu432@126.com; l_xy@nxu.edu.cn
Huaixian Liu, Lin Sun, Huiliang Zhou, Peipei Cen, Xiaoyong Jin and
The optimized geometries of two different conformations
shown in Fig. 1 have been obtained. The calculated bond
Qilin Hu: School of Chemistry and Chemical Engineering, Ningxia
University, Yinchuan 750021, P. R. China
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ꢀꢀꢀꢁ
2ꢀ ꢀH. Liu et al.: A mononuclear Co(III) 3-(2-pyridyl)-5-phenyl-1,2,4-triazolato complex
Fig. 1:ꢀTwo different conformations of 1-Hppt.
lengths N1–C2, N1–N2, C2–C3, and N4–C3 are 1.335, 1.351, atoms are obtained as negative values. The natural charge
1.477, and 1.404 Å, respectively.
of N3 (−0.52) is more negative than that of the N1 (−0.36)
The molecular total energies (Etotal), frontier orbital and N2 (−0.26) atoms in the triazole ring. The natural
energy levels (EHOMO and ELUMO), and the gaps (ΔE(LUMO–HOMO) charge of N4 in the pyridine ring is −0.43. The results dem-
)
of the two different conformations have been calculated, onstrate that all four N atoms provide donor position to
and the results are listed in Table 1. Compared with the coordinate with metal ions.
trans-conformation I, the cis-conformation II displays
lower total energies, representing the preferred geom-
etry. The surfaces of highest occupied molecular orbital 2.2 Synthesis of complex 1
(HOMO) and lowest unoccupied molecular orbital (LUMO)
for the two conformations are shown in Fig. 2. According The Co(III) complex 1 was synthesized from CoF3 and
MO theory, the HOMO and LUMO are the most important 1-Hppt in water by hydrothermal reaction at 140 °C for
factors that influence the properties of a compound [23].
3 days in the presence of terephthalic acid. The latter
The natural charges and electron configuration for was not found to be incorporated in the final product
the conformation II have been calculated by using natural which proved to be [Co(ppt)3] (1) as dark red crystals. The
bond orbital (NBO) analysis. As shown in Table 2, Mulliken phase purity of bulk 1 was proved by a comparison of the
charges and natural charges of the N1, N2, N3, and N4 observed and simulated powder X-ray diffraction (PXRD)
diagrams as described below.
Table 1:ꢀCalculated energies and frontier orbital energies for two
conformations of 1-Hppt.
2.3 Structural description of complex 1
ꢁ
Conformation I
ꢁ Conformation II
E, hartree
ꢂ
ꢂ
ꢂ
−720.4099
−0.22443
−0.04197
4.97
ꢂ
ꢂ
ꢂ
ꢂ
−720.4109
−0.22513
−0.04388
4.93
Single-crystal X-ray diffraction analysis reveals that the
E
E
HOMO, hartree
LUMO, hartree
̅
complex crystallizes in the triclinic system, space group P1
with Z ꢀ=ꢀ 2 (Table 3). The asymmetric unit of the complex
consists of one crystallographically independent Co(III) ion
and three [ppt]– anions. The auxiliary ligand (terephthalic
acid) did not take part in coordination. As shown in Fig. 3a,
the six-coordinated Co(III) center presents a slightly dis-
torted octahedral geometry. The four equatorial positions
are occupied by three nitrogen atoms from triazole rings of
three different ligands (Co1–N1 1.874(3), Co1–N5 1.900(3),
Co1–N9 1.883(3) Å) and one nitrogen atom from a pyridine
ring (Co1–N12 1.976(3) Å). Two nitrogen atoms from pyridine
rings of two different ligands are located at the axial posi-
tions (Co1–N4 1.953(3), Co1–N8 1.954(3) Å) (Table 4). Com-
pared to the previous reports, the Co–N bond lengths of
the title complex are similar to those of Co(III) complexes
(ꢀ<ꢀ2.0 Å [24]), and deviate from the range of Co(II)–N bond
ΔE(LUMO–HOMO), eVꢂ
Fig. 2:ꢀIsodensity surfaces of HOMO and LUMO for 1-Hppt (left:
conformation I, right: conformation II).
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ꢁꢀꢀꢀ
H. Liu et al.: A mononuclear Co(III) 3-(2-pyridyl)-5-phenyl-1,2,4-triazolato complexꢃ ꢃ3
Table 2:ꢀNatural configurations and natural and Mulliken charges of conformation II of 1-Hppt.
Atomꢁ
Natural electron configuration
ꢁ
Natural charge
ꢁ Mulliken charge
N1
N2
N3
N4
C2
C3
C6
C7
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
[core]2S(1.44)2p(3.84)3p(0.01)3d(0.01)ꢂ
[core]2S(1.44)2p(3.79)3p(0.01)3d(0.01)ꢂ
[core]2S(1.40)2p(4.10)3p(0.01)3d(0.01)ꢂ
[core]2S(1.41)2p(4.01)3p(0.01)3d(0.01)ꢂ
[core]2S(0.82)2p(2.83)3p(0.02)3d(0.01)ꢂ
−0.36286
−0.25581
−0.51760
−0.43053
0.31229
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
−0.49234
−0.29671
−0.57613
−0.49547
0.41707
[core]2S(0.85)2p(2.97)3p(0.02)
[core]2S(0.98)2p(3.28)3p(0.01)
[core]2S(0.96)2p(3.01)3p(0.01)
ꢂ
ꢂ
ꢂ
0.16323
0.25091
−0.27183
0.01968
−0.14027
0.04239
Table 3:ꢀCrystallographic data and data collection and structure
refinement details for complex 1.
lengths (2.037–2.187 Å [25]). For the ligand, the bond lengths
of N1–C2, N1–N2, C2–C3, and N4–C3 are 1.332(5), 1.345(4),
1.453(5), and 1.360(5) Å, respectively, in accordance with
the calculated values. Adjacent units are connected to each
other via two kinds of π−π stacking interactions between
benzene and pyridine rings (Fig. 3b). The distance between
two benzene rings is 3.909 Å, but 3.720 Å between benzene
and pyridine rings, which is close to the π–π interaction
distances reported in [26].
Formula
Mr
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
C39H27CoN12
722.66
Crystal size, mm3
Crystal system
Space group
a, Å
0.17 ꢂ×ꢂ 0.15 ꢂ×ꢂ 0.10
Triclinic
̅
P1
12.4949(12)
12.6369(12)
13.3796(17)
107.975(2)
106.025(2)
110.876(3)
1691.2(3)
2
b, Å
c, Å
It is interesting to note that all [ppt]– ligands exhibit
conformation II in the structure of the complex, confirm-
ing that the preferred conformation calculated by DFT is
correct. The ligands display uniform coordination modes
with pyridine N4 and triazole N1 atoms chelating the
Co(III) ions. The coordination ability of N3 with the most
negative charge is probably restricted by steric hindrance.
α, deg
β, deg
γ, deg
V, Å3
Z
D
−3
calcd, g cm
1.42
−1
μ(CuKα), cm
F(000), e
43.8
744
hkl range
14, −14→7, 15
3.9–66.2
0.523/0.669
10 294/5905/0.058
469
θ range, deg
T
min/Tmax
2.4 Thermogravimetric analysis and PXRD
of complex 1
Refl. measured/unique/Rintꢂ
Param. refined
ꢂ
R(F)/wR(F2) (all reflexions) ꢂ
0.0937/0.1444
1.007
GoF (F2)
Δρfin (max/min), e Å
ꢂ
ꢂ
The thermal behavior of 1 was studied by thermal gravi-
metric (TG) measurements under nitrogen atmosphere
−3
0.46/−0.34
Fig. 3:ꢀ(a) Coordination environment of the Co(III) ion in complex 1; (b) intermolecular π–π stacking in the crystal structure of complex 1.
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ꢀꢀꢀꢁ
4ꢀ ꢀH. Liu et al.: A mononuclear Co(III) 3-(2-pyridyl)-5-phenyl-1,2,4-triazolato complex
Table 4:ꢀSelected bond lengths (Å) and bond angles (deg) of complex 1.
Bond
ꢁ
ꢁ
Bond
ꢁ
ꢁ
Bond
ꢁ
Co(1)–N(1)
Co(1)–N(4)
ꢂ
ꢂ
1.874(3)
1.953(3)
ꢂ
ꢂ
Co(1)–N(5)
Co(1)–N(8)
ꢂ
ꢂ
1.900(3)
1.954(3)
ꢂ
ꢂ
Co(1)–N(9)
Co(1)–N(12)
ꢂ
ꢂ
1.883(3)
1.976(3)
Angle
ꢁ
ꢁ
Angle
ꢁ
ꢁ
Angle
ꢁ
N1–Co1–N9
N1–Co1–N4
N1–Co1–N8
N4–Co1–N8
ꢂ
ꢂ
ꢂ
ꢂ
92.42(14)
82.33(14)
90.78(14)
ꢂ
ꢂ
ꢂ
N1–Co1–N5
N9–Co1–N4
N9–Co1–N8
N1–Co1–N12 ꢂ
N4–Co1–N12 ꢂ
ꢂ
ꢂ
ꢂ
90.11(14)
88.31(13)
94.83(14)
173.69(14)ꢂ
96.84(13)
ꢂ
ꢂ
ꢂ
N9–Co1–N5
N5–Co1–N4
N5–Co1–N8
N9–Co1–N12ꢂ
N8–Co1–N12ꢂ
ꢂ
ꢂ
ꢂ
176.23(14)
94.80(13)
82.34(14)
81.29(14)
90.32(13)
172.55(14)ꢂ
N5–Co1–N12ꢂ
96.19(14)
ꢂ
ꢂ
−1
with a heating rate of 10 °C min . In order to confirm the
phase purity of the compound, a PXRD experiment was
carried out (Fig. 4). The experimental pattern matches
with the simulated pattern, indicating the phase purity of
the compound within the limits of experimental error. The
sample was heated to 800 °C (Fig. 5). The TG curve shows
that a continuous weight loss of 92.3 % is observed in the
temperature range from 263 to 660 °C, due to the decom-
position of the ligands (calcd. 91.84 %). The final residue
mass is 7.7 % of the initial mass, which coincides with the
calculated value of elemental cobalt (8.2 %), determined
by PXRD (PDF 05-0727).
Fig. 5:ꢀTGA curve for complex 1.
3 Conclusions
A Co(III) complex with the 3-phenyl-5-(pyridin-2-yl)-1,2,4-
triazolato ligand has been determined under hydrother-
mal conditions. Single-crystal structure analysis has
revealed that the title complex features a 0D mononu-
clear structure, but forms a 3D supramolecular network
through π–π stacking. TG analyses showed that the
complex possesses high thermostability with decomposi-
tion standing at 263 °C. The observed geometric param-
eters and preferred conformation of the [ppt]– ligand are
consistent with the DFT calculated results for the present
molecule. The present work is an example of the combina-
tion of experiment and theory, providing the guidance for
the design and synthesis of coordination polymers.
4 Experimental section
4.1 Materials and instruments
Commercially available solvents, such as 2-cyanopyridine,
phenyl hydrazide, absolute methanol, sodium metal, tere-
phthalic acid, and CoF3, were used as received without
1
further purification (Xi’an Haixin Company, China). H
and 13C nuclear magnetic resonance (NMR; Beijing Oxford
Instrument Company, China) spectra were taken with a
Fig. 4:ꢀObserved and simulated PXRD diagrams of complex 1.
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H. Liu et al.: A mononuclear Co(III) 3-(2-pyridyl)-5-phenyl-1,2,4-triazolato complexꢃ ꢃ5
Varian 400 spectrometer using tetramethylsilane as an (based on Co). – Analysis for C39H27CoN12: calcd. C 64.81, H
internal standard. NMR spectra were obtained from solu- 3.77, N 23.26; found C 64.75, H 3.73, N 23.20 %. – IR (film):
tions in dimethyl sulfoxide (DMSO). Elemental analyses 3599(s), 3447(s), 3063(m), 2822(m), 2662(s), 2548(s),
(C, H, and N) were performed on a Vario EL III analyzer 1690(w), 1618(s), 1576(s), 1464(w), 1425(m), 1287(m),
(Nanjing Hua Xin Analysis Instrument Manufacturing 1111(m), 941(w), 785(w), 735(w), 696(w), 529(w).
Company, China). Infrared (IR) spectra were obtained
using KBr pellets on a BEQ VZNDX 550 FTIR (Shimadzu
−1
Corporation) instrument within the 400–4000 cm
4.4 X-ray crystallography
region. The phase purity of the bulk or polycrystalline
samples was confirmed by PXRD (Brucker Company, All diffraction data were collected on a Bruker Smart
Germany) measurements executed on a Rigaku RU200 Apex CCD diffractometer with graphite-monochromatized
diffractometer at 60 kV, 300 mA with CuKα radiation (λ ꢀ=ꢀ CuKα radiation (λ ꢀ=ꢀ 1.54178 Å) at 293(2) K. Absorption cor-
−1
1.5406 Å), with a scan speed of 5° min and a step size rections were applied using Sadabs [28]. The structure
of 0.02° in 2θ. TG analysis was performed on a SETARAM was solved by Direct Methods using the Shelxs program
Setsys16 (Nanjing Research Institute, China) instrument of the Shelxtl package and refined with Shelxl-97 [29].
−1
under N2 atmosphere with a heating rate of 10 °C min .
The hydrogen atoms were located geometrically. All non-
hydrogen atoms were refined anisotropically. Crystal data
and numbers pertinent to data collection and refinement
are given in Table 3. Selected bond lengths and bond
angles are listed in Tabel 4.
4.2 Synthesis of the 1-Hppt ligand
The ligand was synthesized according to [27]. Sodium
CCDC 1034723 contains the supplementary crystallo-
metal (0.1 g) was added (carefully) to 40 mL absolute graphic data for this paper. These data can be obtained
methanol followed by the addition of 2-cyanopyridine free of charge from the Cambridge Crystallographic Data
(2.1 g). The resulting reaction mixture was stirred with a Centre via www.ccdc.cam.ac.uk/data_request/cif.
magnetic stirrer for 80 min. Thereafter, it was allowed to
cool and phenyl hydrazide (2.1 g) was added. The solution
was refluxed for a further 3 h until a yellow solid complex 4.5 Computational details
precipitated. The precipitate was filtered off, washed with
hot absolute ethanol, and dried in vacuum. The white Geometry optimization was carried out at the all-electron
ligand was precipitated, yield 70 % (based on 2-cyanopyri- level using the Gaussian 03 quantum chemistry program
dine). M.p.: 191.8–192.6 °C. – Analysis for C13H10N3: calcd. C package [30] at the B3LYP/6-31G(d) [31, 32] level of theory.
74.97, H 4.85, N, 20.18; found C 74.92, H 4.83, N, 20.12 %. Mulliken population analysis, total molecular ener-
– IR (film): 3404(s), 3213(s), 3057(m), 2361(m), 1670(s), gies, and NBO calculations were also performed on the
1612(s), 1589(w), 1446(s), 1313(s), 1180(w), 1053(m), B3LYP/6-31G(d) level.
−1
792(m), 717(m), 696(w), 579(w) cm . – 1H NMR (400 MHz,
[D6]DMSO, 25 °C, ppm): δ ꢀ=ꢀ 6.95 (d, 1H, Ph-H4), 7.49–7.51 Acknowledgments: We gratefully acknowledge the finan-
(d, 2H, Ph-H2/H6), 7.55–7.57 (dd, 2H, Ph-H3/H5), 8.60–8.61 cial support from the National Natural Science Founda-
(dd, 1H, Pz-H3), 7.87–7.93 (d, 1H, Pz-H6), 7.53 (t, 1H, Pz-H4), tion of China (Grant Nos. 21463020 and 21365016).
8.17–8.19 (t, 1H, Pz-H5), 10.20 (s, 1H, triazole-H). – 13C NMR
(75 MHz, [D6]DMSO, 25 °C, ppm): δ ꢀ=ꢀ 163.24, 150.75, 148.20,
147.85, 137.04, 134.70, 131.13, 128.31, 127.76, 124.87, 120.81.
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Z. Naturforsch.ꢃ
ꢃ2015 | Volume x | Issue x(b)
Graphical synopsis
Huaixian Liu, Lin Sun, Huiliang Zhou,
Peipei Cen, Xiaoyong Jin, Xiangyu Liu
and Qilin Hu
A mononuclear cobalt(III)
3-(2-pyridyl)-5-phenyl-1,2,4-triazolato
complex: hydrothermal synthesis,
crystal structure, thermostability, and
DFT calculations
DOI 10.1515/znb-2015-0039
Z. Naturforsch. 2015; x(x)b: xxx–xxx
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Download Date | 8/6/15 11:36 PM