Five new complexes based on 1-phenyl-1H-tetrazole-5-thiol: Synthesis, structural characterization and properties

Article abstract of DOI:10.1016/j.molstruc.2016.09.053

Five new complexes based on 1-phenyl-1H-tetrazole-5-thiol (Hptt): 1,1′-diphenyl-5,5′- dithiodi-tetrazole (abbreviated as dptt) (1), {[Co₂(OH)₂(2,2′-bipy)₂(Hptt)₂]·(ptt)₂·(H₂O)₂}(2), [Cd₂I₂(2,2′-bipy)₂(ptt)₂] (3), [Co(ptt)₂]_n (4) and [Cd(ptt)₂]_n (5), have been synthesized and fully characterized by elemental analyses, thermogravimetric analysis, powder X-ray diffraction, IR spectra and single-crystal X-ray diffraction. Structural analysis indicated that compound 1 is an organic matter generated from in situ oxidative coupling reaction of Hptt ligands under the help of Fe³⁺ ion. In compound 2, two Hptt ligands adopting μ₂-κN, κS bridging mode and two μ₂-OHˉ bridge two Co(2,2′-bipy) fragments into a[Co₂(OH)₂(2,2′-bipy)₂(Hptt)₂]²⁺ core with short Co?Co distance (2.8185(10) ?). In compound 3, two Cd centers are joined into a dinuclear complex with short Cd?Cd distance (3.9282(14) ?) by two pttˉ anions in μ₂-κS, κS bridging mode. Compounds 4 and 5 are isostructural and both feature one-dimensional (1D) looped chain structures containing 8-membered [M₂S₂C₂N₂] rings (M?=?Co for 4, M?=?Cd for 5). Variable-temperature magnetic susceptibility measurement of compounds 2 and 4 reveal strong antiferromagnetic interactions between Co centers. The fluorescent properties of compounds 1, 3 and 5 are investigated in the solid state.

Full text of DOI:10.1016/j.molstruc.2016.09.053

Accepted Manuscript
Five new complexes based on 1-phenyl-1H-tetrazole-5-thiol: Synthesis, structural
characterization and properties
Jiang-Feng Song, Jun Wang, Si-Zhe Li, Yang Li, Rui-Sha Zhou
PII:
S0022-2860(16)30980-2
10.1016/j.molstruc.2016.09.053
MOLSTR 22965
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 25 July 2016
Revised Date: 19 September 2016
Accepted Date: 19 September 2016
Please cite this article as: J.-F. Song, J. Wang, S.-Z. Li, Y. Li, R.-S. Zhou, Five new complexes based on
1-phenyl-1H-tetrazole-5-thiol: Synthesis, structural characterization and properties, Journal of Molecular
Structure (2016), doi: 10.1016/j.molstruc.2016.09.053.
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ACCEPTED MANUSCRIPT
Five new complexes based on 1-phenyl-1H-tetrazole-5-thiol (Hptt) have been isolated and
characterized.

ACCEPTED MANUSCRIPT
Five new complexes based on 1-phenyl-1H-tetrazole-5-thiol: synthesis, structural
characterization and properties
Jiang-Feng Song*, Jun Wang, Si-Zhe Li, Yang Li, Rui-Sha Zhou
*
Department of Chemistry, North University of China, Taiyuan, Shanxi, 030051, P. R. China
Abstract
Five new complexes based on 1-phenyl-1H-tetrazole-5-thiol (Hptt): 1,1’-diphenyl-5,5’-
dithiodi-tetrazole (abbreviated as dptt) (1), {[Co2(OH)2(2,2'-bipy)2(Hptt)2]·(ptt)2·(H2O)2}(2),
[Cd2I2(2,2'-bipy)2(ptt)2] (3), [Co(ptt)2]n (4) and [Cd(ptt)2]n (5), have been synthesized and fully
characterized by elemental analyses, thermogravimetric analysis, powder X-ray diffraction, IR
spectra and single-crystal X-ray diffraction. Structural analysis indicated that compound 1 is an
organic matter generated from in situ oxidative coupling reaction of Hptt ligands under the help of
Fe3+ ion. In compound 2, two Hptt ligands adopting ꢀ2-κN, κS bridging mode and two ꢀ2-OH¯
bridge two Co(2,2'-bipy) fragments into a[Co2(OH)2(2,2'-bipy)2(Hptt)2]2+ core with short Co···Co
distance (2.8185(10) Å). In compound 3, two Cd centers are joined into a dinuclear complex with
short Cd···Cd distance (3.9282(14) Å) by two ptt¯ anions in ꢀ2-κS, κS bridging mode. Compounds
4 and 5 are isostructural and both feature one-dimensional (1D) looped chain structures containing
8-membered [M2S2C2N2] rings (M=Co for 4, M=Cd for 5). Variable-temperature magnetic
susceptibility measurement of compounds 2 and 4 reveal strong antiferromagnetic interactions
between Co centers. The fluorescent properties of compounds 1, 3 and 5 are investigated in the
solid state.
Keywords: coordination polymer; organic sulfur; in situ reaction; crystal structure.
1. Introduction
Coordination complexes have attracted increasing attention in the field of materials science
because of their versatile framework topologies as well as the interesting properties including
magnetism, gas sorption, catalysis, optics and molecular sensing [1-9]. As is well known, organic
ligands play crucial roles in constructing coordination complexes with novel topologies and
unique properties [10-11]. Recently, organic sulfur ligands such as pyrimidine-2-thiolate,
*Corresponding author: E-mail address: jfsong0129@nuc.edu.cn(J.-F Song); rszhou0713@nuc.edu.cn (R.-S Zhou)

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2-mercaptoimidazole,
2-mercaptopyridinate,
1H-1,2,4-triazole-3-thiol,
2-quinolinethiolate,
1-methyl-1H-imidazole-2-thiolate,
2-mercaptobenzothiazolate,
5-mercapto-1-methyltetrazolate etc. [12-21], were widely applied to assemble diversities of
coordination complexes with unique properties due to their diverse coordination modes and rich
redox chemistry such as the cleavage of C-S bonds and the formation of S-S bonds [21-26].
The thiol-substituted heterocycle ligand, 1-methyl-5-mercapto-1,2,3,4-tetrazole (Hmnt),
having one soft donor sulfur and three hard donor nitrogen atoms, is a tetrazole-based heterocyclic
thioamide, providing more coordination sites for metal ions to form metal coordination complexes.
Though some interesting coordination complexes based on Hmnt have been reported [26-28], we
found that the higher temperature or oxidizing agents easily result in the decomposition of Hmnt
ligand [21]. In order to obtain coordination complexes based on mercapo tetrazole, a more stable
mercapo tetrazole derivative, 1-phenyl-1H-tetrazole-5-thiol (Hptt), is introduced in the reaction
process. Compared with Hmnt, the introduced phenyl unit could improve conjugated effect
between benzene ring and tetrazole ring and enhance the stability of the ligand, moreover, the
phenyl unit might offer some supramolecuar recognition sites such as π···π, C-H···π interactions,
which are helpful to stabilize the targeted complexes. To the best of our knowledge, coordination
complexes comprised of Hptt are still rare, and most of reported compounds are zero-dimensional
oligo species [29-35], moreover, those showing anti-microbial potential have only been
recognized recently [35]. The above-mentioned analysis implies that there is still much deserving
study for such systems.
Following our interests regarding the synthesis of organic sulfur coordination compounds [19-21],
Hppt is chosen as an organic linker to construct five new complexes:
1,1'-diphenyl-5,5'-dithiodi-tetrazole
(abbreviated
as
dptt)
(1),
{[Co2(OH)2(bipy)2(Hptt)2]·(ptt)2·(H2O)2}(2), [Cd2I2(bipy)2(ptt)2] (3), [Co(ptt)2]n (4) and
[Cd(ptt)2]n (5). Compound 1 is an organic matter generated from in situ oxidative coupling
reaction of Hptt ligands under the help of Fe3+ ion. In compound 2, two Hptt ligands adopting
ꢀ2-N,S bridging mode and two OH¯ join two Co centers into a dinuclear complex with short
Co···Co distance (2.8185(10) Å). In compound 3, two Cd centers are joined into a dinuclear
complex with short Cd···Cd distance (3.9282(14) Å) by two ptt¯ anions in ꢀ2-S, S bridging mode.
Compounds 4 and 5 are isostructural and both feature one-dimensional (1D) looped chain

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structures. Magnetic properties of compounds 2 and 4 together with fluorescent properties of
compounds 1, 3 and 5 are investigated in the solid state. We hope that the syntheses of compounds
1-5 are helpful to deepen the research of organic sulfur coordination complexes.
2. Experimental Section
2.1. Materials and methods
All reagents and solvents for syntheses were commercially available and used as received without
further purification except Hptt ligand, which was purchased from Alfa Aesar and the
corresponding purity was higher than 99%. Elemental analysis (C, H, and N) were performed on a
Perkin–Elmer 240C elemental analyzer. Infrared (IR) spectra were recorded with KBr Pellets
using a Perkin Elmer Spectrum One FT–IR spectrometer in the range of 4000–400 cm-1 with the
resolution (4.0 cm-1) and the scan's numbers (10). The HNMR spectrum was recorded on a Bruker
400 MHz spectrometer. Powder X–ray diffraction (PXRD) patterns of the samples were recorded
by a RIGAKU–DMAX2500 X–ray diffractometer using Cu–Kα radiation (λ = 1.542 Å) with a
scanning rate of 10°/min and a step size of 0.02°. Thermal gravimetric analysis (TGA) was
carried out in a nitrogen stream on a Perkin Elmer TGA–7000 thermogravimetric analyser with a
heating rate of 10 °C·min–1. The solid-state photoluminescence spectra were recorded on Jobin
Yvon Fluoro Max-4 spectrophotometer equipped with a 150 W xenon lamp as the excitation
source at room temperature. Variable-temperature magnetic susceptibility measurements were
collected using SQUID magnetometer MPMS XL-7 (Quantum Design) at 1.0 kOe in the
temperature range of 2−300 K.
2.2. Synthesis of 1-5
2.2.1. Synthesis of dptt (1)
A mixture of Hptt (0.05mmol), Fe(NO3)3·9H2O (0.1mmol) was dissolved in 6mL mixed
solvents MeOH/H2O (v : v = 5 : 1), which was stirred in a 15 mL beaker for 30 min at room
temperature. Then the above-mentioned mixture was filtered and the filtrate was allowed to slowly
concentrate by evaporation at room temperature. After 12h, colorless block crystals were obtained.
Yield : 60% (based on Hptt). Elemental anal. Calcd C14H10S2N8 (354.42): C, 47.47; H, 5.60; N,

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31.65. Found: C, 47.40; H, 5.64; N, 31.60. IR Spectrum (cm-1, KBr pellet): 1594 (m), 1496 (s),
1460 (m), 1383 (s), 1265(m), 1226(s), 1095 (m), 1055 (m), 1014 (s), 975 (m), 761 (s), 690 (s), 540
(m), 492 (m). 1H NMR (400 MHz, [D6]DMSO): δ = 7.57 (2H), 7.65 (4H).
2.2.2. Synthesis of {[Co2(OH)2(bipy)2(Hptt)2]·(ptt)2·(H2O)2}(2)
A mixture of Hptt (0.1mmol), 2, 2’-bipy (0.1mmol), Co(Ac)2·4H2O (0.1mmol) and
MeOH/H2O (v : v = 5 : 1, 6ml) was stirred in a 15 mL beaker for 30 min at room temperature.
Then the above-mentioned mixture was allowed to slowly concentrate by evaporation at room
temperature. After two days, red crystals were obtained. Yield : 52% (based on Hptt). Elemental
anal. Calcd C48H44Co2N20O4S4 (1211.13): C, 47.56; H, 3.63; N, 23.12. Found: C, 47.53; H, 3.65; N,
23.10. IR Spectrum (cm-1, KBr pellet): 3459(m) 1598 (s), 1496(s), 1448(m), 1352(m), 1320(m),
1276(m), 1252 (m), 1216 (w), 1154(w), 1093 (m), 1016(m), 762(s), 691(s), 567(m), 483(m).
2.2.3. Synthesis of [Cd2I2(bipy)2(ptt)2] (3)
A mixture of Hptt (0.1mmol), 2, 2’-bipy (0.1mmol), Cd(Ac)2·4H2O (0.1mmol) and KI
(0.1mmol) was dissolved in 7mL mixed solvents MeOH/DMF/H2O (v : v = 5 : 1 : 1). Then the
resulted mixture was transferred into a Teflon-lined autoclave and kept under autogenous pressure
at 80 °C for 3 days. After slowly cooling to room temperature, light yellow crystals were obtained.
Yield: 25% (based on Hptt). Elemental anal. Calcd C34H26Cd2I2N12S2 (1145.39): C, 35.62; H, 2.27;
N, 14.67. Found: C, 35.60; H, 2.26; N, 14.69. IR Spectrum (cm-1, KBr pellet): 1650 (m), 1400 (s),
1238 (m), 1170 (m), 1091 (m), 1051 (m), 1020(m) 754 (m), 680 (m), 561 (m).
2.2.4. Synthesis of [Co(ptt)2]n (4)
A mixture of Hptt (0.1mmol) and Co(Ac)2·4H2O (0.1mmol) was dissolved in 5mL mixed
solvents H2O/DMF (v : v = 4 : 1). Then the resulted mixture was transferred into a Teflon-lined
autoclave and kept under autogenous pressure at 80 °C for 3 days. After slowly cooling to room
temperature, red crystals were obtained. Yield :32% (based on Hptt). Elemental anal. Calcd
C14H10CoN8S2 (413.35): C, 40.64; H, 2.42; N, 27.10. Found: C, 40.65; H, 2.40; N, 27.08. IR
Spectrum (cm-1, KBr pellet): 1594 (w), 1495 (m), 1378 (s), 1316 (m), 1243 (m), 1163 (w), 1095
(m), 1050 (m), 1025 (m), 755 (m), 683 (m), 562(m).
2.2.5. Synthesis of [Cd(ptt)2]n (5)
A mixture of Hptt (0.1mmol), Fe(NO3)3·9H2O (0.1mmol), CdSO4·8H2O (0.1mmol) and
MeOH/H2O (v : v = 5 : 2, 7ml) was stirred in a 15 mL beaker for 30 min at room temperature.

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Then the above-mentioned mixture was filtered and the filtrate was allowed to slowly concentrate
by evaporation at room temperature. After 3 days, colorless block crystals were obtained. Yield :
34% (based on Hptt). Elemental anal. Calcd C14H10CdN8S2 (419.83): C, 40.02; H, 2.38; N, 26.68.
Found: C, 40.06; H, 2.41; N, 26.72. IR Spectrum (cm-1, KBr pellet): 1594 (w), 1495 (m), 1398 (s),
1314 (m), 1239 (m), 1163 (w), 1089 (m), 1050 (m), 1023 (m), 755 (m), 685 (m), 561(m).
2.3. Crystal structure determination
X-ray diffraction data of compounds 1-5 were collected on a Bruker SMART CCD
area-detector diffractometer (MoKα radiation, graphite monochromator) at room temperature with
ω-scan mode. Adsorption corrections were applied using the SADABS routine. The structure was
solved by direct methods and refined by full-matrix least squares on F2 using SHELXTL 97
software [36]. Non-hydrogen atoms were refined anisotropically. All carbon-bound hydrogen
atoms were refined using a riding model. All calculations were carried out using SHELXTL 97.
For 2, the disordered lattice water molecule was treated by performing split and occupancies
refinement of the disordered atoms, and the corresponding hydrogen atoms were not located in a
difference Fourier map. The crystallographic data and pertinent information are given in table 1;
selected bond lengths and angles in table S1.
3. Results and discussion
3.1. Synthesis of compounds 1-5
The Hptt ligand was easily solved in common organic solvents such as methanol, ethanol,
acetonitrile and DMF. A series of experimental results show that compound 1 can be synthesized
in the presence of Fe3+ or H2O2, however, at the same reaction conditions, in situ oxidative
coupling reaction based on Hmnt didn’t occur. The crystals of compound 1 are difficult to
dissolve in common solvents as methanol, ethanol, acetonitrile, acetone and DMF at room
temperature, so we also tried to synthesize the coordination complexes based on compound 1
through one-pot reaction under the help of oxidizing agents such as Fe3+ or H2O2, only compound
5 was obtained, however, no targeted products were isolated to date. When metal ions (Co2+ or
Cd2+) react with Hptt ligands, compounds 4 and 5 with 1D chains were obtained, however, when
chelating 2, 2'-bipy with strong coordination activity was introduced into the reaction system,

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compounds 2 and 3 with binuclear structures were obtained, indicating the terminally chelating
ligands have an important influence on the topology structures. Compounds 2-5 are very stable in
air and insoluble in common solvents such as H2O, CH3OH, CH3CH2OH, CH3CN, DMF, DMSO
and CHCl3 etc.
3.2. Crystal structure
3.2.1. Crystal structure of compound 1
A single crystal X-ray diffraction analysis revealed that compound 1 is crystallized in the
triclinic space group, P-1. The asymmetric unit of compound 1 is composed of one dptt molecule,
which generated from in situ oxidative coupling reaction of two ptt- ligands (Fig.1). The S-S
distance is 2.0311(10) Å in dptt molecule, which is shorter than those in the photo-responsive
organodirhodium complexes with active S-S bonds [37]. The dihedral angles between the tetrazole
and phenyl rings in two ptt units are 42.708(83) and 54.540(87)° respectively. The C-S distances
of compound 1 are in the range of 1.7489(24)-1.7571(20) Å, which are shorter than the typical
C-S bonds (1.82 Å), indicating that the sulfur atom has double bond character [38]. The dptt
molecules were packed into a 3D supramolecular network thorough π···π interactions between ptt
units (Fig. S1).
3.2.2. Crystal structure of compound 2
Compound 2 crystallizes in the monoclinic space group, P21/n. The asymmetric unit contains
one Co (II) ion, one OH¯ , one ptt¯ anion, one lattice water and one Hptt molecule. The Co center
shows an octahedral geometry where the basal plane is occupied by two oxygens and two
nitrogens from two symmetrical equivalent OH¯ anions and one 2, 2'-bipy molecule, and the axial
positions are occupied by one nitrogen and one sulfur from two Hptt molecules (Fig. 2). The
Co-O/N bond distances around Co range from 1.8915(35) Å to 2.20224(37) Å, and the Co-S
distance is 2.2446 (17) Å. Notably, ptt- anions uncoordinates with Co center but acts as counter
anions. The C-S bond distances in Hptt and ptt- are 1.6884(50) and 1.6868(56) Å respectively,
which are shorter than that of compound 1, and their dihedral angles between the tetrazole and
phenyl rings are 54.15 and 67.48°, respectively.
Two Hptt ligands adopting ꢀ2-κN, κS bridging mode and two ꢀ2-OH¯ bridge two
Co(2,2'-bipy) fragments into a[Co2(OH)2(2,2'-bipy)2(Hptt)2]2+ core with short Co···Co distance

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(2.8185(10) Å), interestingly, two Co(2,2'-bipy) fragments and two ꢀ2-O are all coplanar. The
[Co2(OH)2(2,2'-bipy)2(Hptt)2]2+ core interact with two ptt- anions into a neutral molecule,
[Co2(OH)2(2,2'-bipy)2(Hptt)2]·(ptt)2, in which several supramolecuar recognition sites based on
п···п interactions are observed (Fig. S2). The [Co2(OH)2(2,2'-bipy)2(Hptt)2]·(ptt)2 molecules are
packed into a 3D supramolecular network with a 1D abnormal channel, in which lattice water
molecules are filled (Fig. 3).
3.2.3. Crystal structure of compound 3
A single crystal X-ray diffraction analysis revealed that compound 3 crystallized in the
monoclinic space group, P21/n. The asymmetric unit consists of one Cd (II) ion, one I¯ and one
ptt¯ anion. The Cd center with square pyramidal coordination environment is bound to two
nitrogens from one chelating 2,2'-bipy, two sulfurs from two independent ptt- ligands and one I¯
anion (Fig. 4). The Cd-N distances range from 2.3267(30) Å to 2.3292(26) Å, and the Cd-S
distances are 2.6395(10)-2.7504(11) Å, while the Cd-I distance is 2.7553(6) Å, and selected bond
lengths and angles in Table S1.
Two [CdI(2,2'-bipy)]fragments are bridged by two ptt- anions in ꢀ2-1 κS : 2 κS coordination
modes into a neutral dinuclear molecule, [Cd2I2(2,2'-bipy)2(ptt)2],in which a four-membered ring
of Cd2S2with short Cd···Cd distance (3.9282(14) Å) is observed. Notably, two 2,2'-bipy molecues,
two ptt –and two I¯ anions are all on the opposite sides of M2S2 rings so as to lower the steric
exclusion effect.
3.2.4. Crystal structure of compounds 4 and 5
Compounds 4 and 5 have the same crystal system, space group and isomorphic framework,
so only the structure of 5 will be described in detail as a representative example. The asymmetric
unit of compound 5 contains a Cd ion and a ꢀ2-ptt¯ ligand. The cadmium center located on a
twofold rotation axis is bounded to two S atoms and two N atoms from four independent ptt-
ligands (Fig. 5a), showing a distorted tetrahedral geometry with Cd-S and Cd-N distances of
2.5029(23) Å and 2.2456(70) Å, respectively.
The ptt¯ ligand adopting a ꢀ2-κN, κS coordination mode bridges two Cd centers into a
one-dimensional (1D) looped chain along the c axis (Fig. 5b), in which a 8-membered ring of

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[Cd2S2C2N2] is observed and the Cd···Cd distance is 4.1763(9) Å. Then the 1D chains are
interdigitated with each other into a 2D supramolecular layer via the π-π interactions among the
neighboring phenyl rings along the bc plane (Fig. 5c and 5d). Compared with compounds 2 -5,
we found that the terminally chelating ligands have an important influence on the topology
structures.
3.3. Characterization
The experimental PXRD patterns of compounds 1-5 are shown in Fig. S3, which matched
well with the corresponding simulated ones from their X-ray single-crystal diffraction data, as
indicated that the phase purities of the synthesized bulk materials. The IR spectra of compounds
1-5 as well as Hptt ligand are shown in Fig.6. Compound 2 with a broad peak at around 3459 cm-1
reveals the presence of the stretching vibrations of O-H bonds. In compounds 1-5, the peak at
about 3063 cm-1 belongs to the C-H stretching of aromatic rings. The peaks at 2220–2781 cm-1 in
Hptt ligand and compound 2 are attributed to the S-H stretching, however, the corresponding
peaks were absent in the spectra of compounds 1 and 3-5, indicating that the Hptt ligands are
deprotonated. The characteristic peaks at 1497 and 1463 cm-1 are assigned as the symmetric
stretching of C=C and C=N bonds, and 1320 cm-1 characteristic band corresponds to their
asymmetric stretching. The peaks appeared at 1100-985 cm-1 in Hptt ligand and compounds 1-5
correspond to the typical region for C=S double bonds. The peaks at 760-650 cm-1 are attributed to
the C-H bending vibration of aromatic rings.
To examine the thermal stability of compounds 1-5, their thermal behaviors were investigated
under nitrogen atmosphere. The thermogravimetric analysis (TGA) revealed that the
o
decomposition temperature of compound 2 (84.3 C) is much lower than that of the other
compounds due to the water molecules in the supramolecular channels. Compounds 1 and 3 start
to decompose at 210 °C, in comparison, compounds 4 and 5 are more stable and the
corresponding decomposition temperatures were 255 °C (Fig. S4).
3.4. The fluorescence curve of compounds 1, 3 and 5
The solid-state photoluminescence properties of compounds 1, 3, 5 together with 2, 2-bipy
and Hptt ligands were investigated at room temperature. The luminescence spectra of compounds

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1, 3 and 5, which are very similar in terms of position and band shape, all exhibit blue light
emission with the maximum at 415 nm when excited at 254 nm, similar to that of the Hptt ligand
but different from that of 2, 2-bipy. So the emission bands of compound 1, 3 and 5 are attributed
to the intraligand emission state, which may be due to π
→
π* or n-π* transition of the Hptt
ligands. Notably, the fluorescence intensity of compound 3 is much higher than the free Hptt
ligands, which may be attributed to the co-ligand (2, 2’-bipy) resulting in a more rigid structure.
3.5. The Magnetic properties of compounds 2 and 4
Variable-temperature magnetic susceptibilities for compounds 2 and 4 were measured in the
temperature range of 2–300 K under a 1000 Oe applied field. The χmT of per Co(II) ion versus T
curves are shown in Fig.S5 and Fig.S6, the χmT values at 300 K for compounds 2 and 4 are 2.13
and 2.28 cm3ꢁKꢁmol-1, respectively, which are higher than the spin-only value of 1.875
cm3ꢁKꢁmol-1 for CoII ion (CoII, S = 3/2 and g = 2.0), indicating the spin-orbit coupling contribution
of high-spin CoII. For compound 2, the χmT curve decreases successively with a decrease in
temperature and reach a minimum at 5.97 K (0.40 cm3ꢁKꢁmol-1), and then increase to a maximum
value (0.44 cm3ꢁKꢁmol-1 at 4.93 K). Further cooling, χmT values sharply drops at 2 K (0.15
cm3ꢁKꢁmol-1). The increase of the χmT at low temperatures is probably due to spin-canting
-1
behaviors [39, 40]. In χm versus T curve, the magnetic susceptibilities data follow the
Curie−Weiss law (χm = C/(T − θ)) above 30 K with Curie constant C = 2.44 cm3ꢁKꢁmol−1 and the
Weiss constant θ = −45.38 K. For compound 4, the χmT values decrease continuously along with
the decreasing temperature and reach a minimum of 0.073 cm3ꢁKꢁmol-1 at 2 K, and the
corresponding Curie and Weiss constants in the range of 50-300K are 2.70 cm3ꢁKꢁmol−1 and
−45.60 K, respectively. The larger negative value of θ and the decrease of χmT indicate strong
antiferromagnetic interactions between Co (II) centers in compounds 2 and 4 [41].
4. Conclusion
Five new compounds based on Hptt ligand have been synthesized under solvothermal
conditions and fully characterized. Compound 1 is an organic matter generated from in situ
oxidative coupling reaction of Hptt ligands. Compounds 2 and 3 are both dinuclear compounds in
the presence of chelating 2,2'-bipy ligand, interestingly, compounds 4 and 5 are isostructural and

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both feature one-dimensional (1D) looped chain structures without chelating 2,2'-bipy ligand. The
results revealed that the terminally chelating 2,2'-bipy ligand has an important influence on the
synthesis and structural diversification of the targeted complexes. Compounds 2 and 4 reveal
strong antiferromagnetic interactions between Co centers, however, compounds 1, 3 and 5 display
blue light emission in the solid state. These compounds are promising materials for magnetic and
fluorescent applications. The further research for the construction of new coordination compounds
based on dptt ligand is underway in our laboratory.
Acknowledgments
This work was supported by the National Natural Science Foundation of China (No:
21201155), the Natural Science Young Scholars Foundation of Shanxi Province (No:
2013021008-6), Program for the Top Young Academic Leaders of Higher Learning Institutions of
Shanxi and 131 Talent Plan of Higher Learning Institutions of Shanxi, respectively.
Appendix A. Supplementary material
Table S1, Figure S1-S8 and CCDC numbers 1495558-1495562 for compounds 4, 5, 1, 2, 3
contain the supplementary crystallographic data. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif.
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Table 1 Crystal data and structure refinement for compounds 1-5.
Complex
Empirical formula
Formula weight
Crystal system
Space group
a, Å
1
2
C48H44Co2N20O4S4
1211.13
Monoclinic
P21/n
3
C34H26Cd2I2N12S2
1145.39
Monoclinic
P21/n
4
C14H10CoN8S2
413.35
5
C14H10CdN8S2
466.85
C14H10N8S2
354.42
triclinic
P-1
Monoclinic
C2/c
Monoclinic
C2/c
7.2986(15)
9.3495(19)
11.977(2)
80.43(3)
89.36(3)
74.60(3)
776.5(3)
2
11.873(2)
13.022(3)
18.089(4)
90
8.9617(18)
22.559(5)
9.7089(19)
90
25.0104(16)
8.9264(5)
7.2366(4)
90.00
27.746(5)
9.1090(18)
7.4584(15)
90.00
b, Å
c, Å
α, deg
β, deg
93.35(3)
90
102.36(3)
90
96.828(5)
90.00
102.88(3)
90.00
γ, deg
Volume (Å3)
Z
2792.1(10)
2
1917.3(7)
2
1604.14(17)
4
1638.9(6)
4
ρcalc/gcm-3
1.516
1.441
1.984
1.712
1.892
Absorption
coef./mm-1
0.358
0.806
2.871
1.346
1.603
θ range (o )
3.09 to 27.48
3.13 to 25.15
3.34 to 27.48
0.58 x 0.15 x 0.10
3.28 to 25.35
0.35 x 0.25 x 0.20
3.38 to 27.48
0.22x 0.18 x 0.18
0.45 x 0.37 x
0.27
0.45 x 0.35 x
0.20
Crystal size (mm3)
Reflections
collected
7665
20507
18526
2901
7733
Unique reflections
(Rint)
3524 (Rint =
0.0213)
4956 (Rint =
0.0782)
4386 (Rint =
0.0336)
1463 (Rint =
0.0473)
1877 (Rint =
0.0229)
Completeness
98.9%
99.1 %
99.7 %
99.6 %
99.7 %
Goodness-of-fit on
F2
1.051
1.072
1.100
0.948
1.114
R indexes
[I>2σ(I)][a]
R1 = 0.0406
wR2 = 0. 1010
R1 = 0. 0572
wR2 = 0. 1136
R1 =0.0655
wR2 = 0.1902
R1 =0.0943
R1= 0.0313
wR2 = 0.0574
R1= 0.0405
R1= 0.0497
wR2 = 0.1060
R1= 0.0725
R1= 0.0230
wR2 = 0.0565
R1= 0.0249
R (all data)[a]
wR2 = 0.2108
wR2= 0.0600
2 2 1/2
wR2 = 0.1172
wR2= 0.0571
[a] R1 = Σ||Fo| – |Fc||/Σ|Fo|; wR = [Σw(Fo – Fc2)2/Σw(Fo ) ]
2

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Fig.1 The coordination environment of compound 1

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Fig.2 The coordination environment of Co centers in compound 2

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Fig. 3 The 3D supramolecular network of compound 2

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Fig. 4 The coordination environment of Cd in compound 3

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Fig. 5 (a) Coordination environment of Cd, (b) the1D looped chain along the c axis, (c) the 2D
supramolecular layer via the π-π interactions along the bc plane, (d) the 2D supramolecular layer
along the ab plane for 5.

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Fig. 6 The IR spectra of compounds 1-5 and Hptt ligand

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Fig. 7 The fluorescence spectra of compounds 1, 3, 5 as well as Hptt and 2,2-bipy ligands in solid
state at room temperature.

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ꢀ
ꢀ
ꢀ
ꢀ
Five new compounds based on Hptt have been isolated and characterized.
The magnetic properties of compounds 2 and 4 were described.
Photoluminescence properties of compounds 1, 3 and 5 have been studied.
The chelating ligands have an important influence on topology structures.