Hydrogen bonded supramolecular framework in inorganic-organic hybrid compound: Syntheses, crystal structure, thermal stability, and photoluminescent properties

Article abstract of DOI:10.1080/15533174.2013.791841

A novel compound [Mn(bip)₂Cl₂·4H₂O] (1) [bip = 2-(4-bromophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline] has been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR), XRD spectra (X-ray powder diffraction), and single-crystal X-ray diffraction. The title compound crystallizes in orthorhombic, space group pbcn with a = 1.4820, b = 0.8961, c = 2.8105 nm, β = 90°. Single-crystal X-ray diffraction reveals that compound 1 is zero-dimensional (0D) architecture, and the existence of hydrogen bonds and π-π interactions lead the 0D to 2D novel frameworks. Hydrogen bonds and π-π interactions are powerful interactions for directing supra-molecular architectures. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. The luminescent properties for the ligand bip and compound 1 are also discussed.

Full text of DOI:10.1080/15533174.2013.791841

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Hydrogen Bonded Supramolecular Framework in
Inorganic-Organic Hybrid Compound: Syntheses, Crystal
Structure, Thermal Stability, and Photoluminescent
Properties
Li Yan a , Chuanbi Li a , Jia Fu a & Mingzhe Sun b
a College of Chemistry , Jilin Normal University , Siping , P. R. China
b School of Food Production Technology , Changchun Vocational Institute of Technology ,
Changchun , P. R. China
Accepted author version posted online: 25 Nov 2013.Published online: 25 Feb 2014.
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To cite this article: Li Yan , Chuanbi Li , Jia Fu & Mingzhe Sun (2014) Hydrogen Bonded Supramolecular Framework
in Inorganic-Organic Hybrid Compound: Syntheses, Crystal Structure, Thermal Stability, and Photoluminescent
Properties, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:6, 814-818, DOI:
10.1080/15533174.2013.791841
To link to this article: http://dx.doi.org/10.1080/15533174.2013.791841
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:814–818, 2014
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.791841
Hydrogen Bonded Supramolecular Framework
in Inorganic-Organic Hybrid Compound: Syntheses,
Crystal Structure, Thermal Stability,
and Photoluminescent Properties
Li Yan,1 Chuanbi Li,1 Jia Fu,1 and Mingzhe Sun2
1College of Chemistry, Jilin Normal University, Siping, P. R. China
2School of Food Production Technology, Changchun Vocational Institute of Technology, Changchun,
P. R. China
also affect the results. A successful approach to build these
supramolecular frameworks is to select suitable multidentate
ligands as building blocks. Among them, multidentate ligands
such as N-heterocyclic ligands are widely used in the rational
design and controlled synthesis of coordination polymers.[8–10]
As for the N-heterocyclic ligand, we chose one long-conjugated
unsymmetrical aromatic N-heterocyclic ligands bip (bip =
2-(4-bromophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) in
view of the following characteristics: (a) it possesses extended
long-conjugated unsymmetrical aromatic system to provide
supramolecular interactions; (b) it has two nitrogen atoms,
which is similar with 2,2ꢁ-bipyridyl-like bidentate chelating
molecules; and (c) it possesses strong and rigidity of coordi-
nation ability to metal atoms to construct intriguing structures.
Manganese compounds with carboxylate are known to exist at
the active sites of some Mn(II)-containing metalloenzymes.[11]
Based on the previous reasons, we designed and synthesized
the compound, namely, [Mn(bip)2Cl2·4H2O] 1. The compound
1 exhibits zero-dimensional (0D) structures, and display novel
2D layer structures via hydrogen bonds and inter-chain π-π
stacking interactions. The research shows that 1 is luminescent
material.
A novel compound [Mn(bip)2Cl2·4H2O] (1) [bip = 2-(4-
bromophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline] has been
synthesized by hydrothermal reactions and characterized by el-
emental analysis, thermogravimetric (TG) analysis, infrared spec-
trum (IR), XRD spectra (X-ray powder diffraction), and single-
crystal X-ray diffraction. The title compound crystallizes in or-
thorhombic, space group pbcn with a = 1.4820, b = 0.8961, c =
2.8105 nm, β = 90◦. Single-crystal X-ray diffraction reveals that
compound 1 is zero-dimensional (0D) architecture, and the exis-
tence of hydrogen bonds and π-π interactions lead the 0D to 2D
novel frameworks. Hydrogen bonds and π-π interactions are pow-
erful interactions for directing supra-molecular architectures. TG
analysis shows clear courses of weight loss, which corresponds to
the decomposition of different ligands. The luminescent properties
for the ligand bip and compound 1 are also discussed.
Keywords coordination compound, fluorescence, hydrogen bond,
thermal stability analysis, XRD spectra
INTRODUCTION
Design and construction of metal-involved supra-molecular
architectures based on crystal engineering are currently of in-
terest.[1,2] The increasing interest in this field is justified not
only by their intriguing structural motifs, but also their po-
tential applications as various fields such as ion exchange,
microelectronics, catalysis, nonlinear optics, and porous ma-
terials.[3–7] Nowadays, the method of hydrothermal synthesis
is widely used to synthesis novel crystal structures, because
it can solve the problems of ligands solubility and enhance
the reactivity of reactants in the crystallization process to ob-
tain perfect crystal. In addition, H-bonds and π-π interactions
EXPERIMENTAL
Materials
The ligand bip was prepared according to the description
in the literature procedures.[12] The metallic salt, NaOH, were
purchased commercially and used without further purification.
Physical Measurements
The FT-IR spectrum was measured with KBr pellets in the
range of 4000–400 cm–1 on a Perkin-Elmer 240C spectrome-
ter. TGA was performed using a Perkin-Elmer TG-7 analyzer
at the rate of 10◦C/min rise of temperature in nitrogen atmo-
sphere. Crystal structures were determined on a Bruker SMART
APEX II CCD X-ray diffractometer. Carbon, hydrogen and
Received 5 March 2013; accepted 27 March 2013.
Address correspondence to Li Yan, College of Chemistry,
Jilin Normal University, Siping 136000, P. R. China. E-mail:
yanli820618@163.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.
814

COMPOUND SYNTHESES, CRYSTAL STRUCTURE, THERMAL STABILITY, AND PROPERTIES
815
SCH. 1. The synthesis of bip.
nitrogen elemental analyses were performed with a PE-2400 RESULTS AND DISCUSSION
elemental analyzer. X-ray powder diffraction (XRD) measure-
ments were performed using an X’pert diffractometer of Philips
Description of Crystal Structures
The molecular structure is shown in Figure 1, and the 2D
layer structure linked hydrogen bonds is suggested in Figure 2.
Selected important bond lengths and bond angles for compound
1 are shown in Table 3.
with monochromated Co-Kα radiation.
Syntheses
Synthesis of bip
A mixture of 4-bromobenzaldehyde, 1,10-phenanthroline-
5,6-dione (0.525 g, 2.5 mmol), ammonium acetate (3.88 g,
50 mmol) and glacial acetic acid was refluxed for 5 h, then
cooled to room temperature. Yellow precipitate was obtained
when addition of concentrated aqueous ammonia to neutralize,
which was collected and washed with water. The crude product
dissolved in ethanol was purified by filtration on silica gel. The
principal yellow band was obtained. Then evaporation of the
solution gave yellow products. Yield 0.66 g. m.p. 320–322◦C.
TABLE 1
Crystal data and details of structure refinement parameters for
1
1
Empirical formula
Formula weight
Crystal system
Space group
C38H30Br2Cl2MnN8O4
948.36
orthorhombic
pbcn
Synthesis of [Mn(bip)2Cl2·4H2O] (1)
A mixture of MnCl2 (0.037g, 0.3 mmol), bip (0.112 g,
0.3 mmol), and H2O (18 mL) was stirred at room tempera-
ture and adjusted the pH value to about 7.0 with NaOH. We put
the cloudy solution into a 30-mL Teflon-lined stainless vessel
under autogenous pressure at 443 K for 72 h, and afterwards
cooled to room temperature at a rate of 5◦C/h. Small yellow
crystals of compound 1 were collected in 89% yield based on
Mn. C38H30Br2Cl2MnN8O4: Anal. Calcd. (%) C 48.12, H 3.18,
N 11.81; Found: C 48.05, H 3.16, N 11.88%. IR (KBr, cm–1):
3369(s), 1509(s), 1277(s), 817(s), 665(m), 531(m), 442(m).
a (nm)
b (nm)
1.48201
0.89616
2.80158
90
3.7208
4
c (nm)
β (◦)
Volume (nm3)
Z
Density (Mg/m3)
(calculated)
1.693
Absorption coefficient
2.700
(mm–1)
F(000)
1900
X-Ray Crystallography
Crystal size (mm3)
Theta range (◦)
Reflections collected
Unique reflections [Rint]
Goodness-of-fit on F2
Final R indices [I > 2σ (I)]
0.433 × 0.371 × 0.308
2.00–26.02
24270
3654 [0.0657]
0.998
R1 = 0.0343
wR2 = 0.0728
R1 = 0.0577
wR2 = 0.0811
0.492, –0.288
Single-crystal X-ray diffraction data were collected at room
temperature with a Bruker SMART APEX II CCD diffractome-
ter equipped with a graphite-monochromatized MoKα radiation
(λ = 0.71073 Å) at 293(2) K in the range of 2.00 ≤ θ ≤ 26.02◦
for 1. Absorption corrections were applied using multi-scan
technique and all the structures were solved by direct meth-
ods with SHELXS-97[13] and refined with SHELXL-97[14] by
full-matrix least-squares techniques on F2. Non-hydrogen atoms
were refined with anisotropic temperature parameters. Experi-
mental details for crystallographic data and structure refinement
parameters for 1 are listed in Table 1.
R indices (all data)
Largest difference peak and
hole (e. Å−3
)

816
L. YAN ET AL.
As shown in Figure 1, the coordination compound 1 crystal-
lizes in orthorhombic, space group pbcn, and the asymmetric
unit of 1 consists of one Mn (II) atom, two bip ligands, two
chloride ions, and two lattice water molecules. The coordinated
chloride ions occupy two coordination points of Mn (II) atom.
The Mn (II) atom is hexa-coordinated with four nitrogen atoms
from two chelating bip ligands and two chloride ions from metal
salts, furnishing a slightly distorted octahedral geometry. The
bond distance of Mn–Cl in compound 1 is 2.5159 Å, and those
of Mn–N bond distance fall in the 2.275 to 2.288 Å range, which
are similar with the values reported.[15–18]
Hydrogen bonding interactions are usually important in the
synthesis of supramolecular architectures, there are six type
of hydrogen bonding interactions in compound 1: O H···O,
O H···Cl, N H···Cl, C H···Cl, and the most interesting
aspect of the structure in 1 concerns the intermolecular
C H···Cl [H(8A)···Cl(1) = 2.70 Å, C(8)···Cl(1) = 3.593 Å,
and C(8) H(8A)···Cl(1) = 161◦], N H···Cl [H(3A)···Cl(1) =
2.39 Å, N(3)···Cl(1) = 3.212 Å, and C(8) H(8A)···Cl(1) =
160◦] interactions, which helps in the construction of the 2D
structure (Figure 2). Moreover, there are π-π interactions be-
tween the aryl ring of bip ligands and symmetry of the two
adjacent equivalent of aromatic ring (symmetry codes: –x, –1
+ y, 1.5 – z, 0.5 + x, –1.5 + y, 1.5 – z). The distance between
cg(1)→cg(2) ring centroid is 3.6070 Å and cg(3)→cg(4) is
3.6441Å. Cg(1): C14→C15→C16→C17→C18→C19, Cg(2):
C1→C2→C3→C4→C5→N1, Cg(3): C4→C5→C6→C7→
C11→C12, Cg(4): C11→C12→C13→N3→N4.
FIG. 1. The molecular structure of compound 1 (hydrogen atoms were
omitted).
FIG. 2. 2D structure of compound 1 linked by hydrogen bonds (dotted lines represent hydrogen bonds).

COMPOUND SYNTHESES, CRYSTAL STRUCTURE, THERMAL STABILITY, AND PROPERTIES
817
TABLE 2
Selected bond lengths (Å) and bond angles (◦) for 1
Bond
Dist.
Bond
Mn(1)-N(2)
Dist.
Mn(1)-N(1)
Mn(1)-Cl(1)
Angle
2.288(2)
2.275(2)
2.5159(8)
(◦)
Angle
(◦)
N(2)-Mn(1)-N(1)
N(1)-Mn(1)-Cl(1)
N(1)#1-Mn(1)-N(1)
72.75(8)
90.57(6)
N(2)-Mn(1)-Cl(1) 103.93(6)
N(2)#1-Mn(1)-N(2) 156.62(12)
88.90(12) N(2)-Mn(1)-Cl(1)#1 92.06(6)
N(1)-Mn(1)-Cl(1)#1 164.80(6)
Cl(1)#1-Mn(1)-Cl(1) 93.87(4)
N(2)-Mn(1)-N(1)#1 90.42(8)
IR Spectra
In compound 1, the infrared spectrum exhibited absorption
at 3369 cm–1, which is assigned to O–H stretching vibration.
The spectrum of compound 1 shows the strong bands at 1509
and 817 cm–1 are due to C C and C N stretching vibrations
of the coordinated phenanthroline molecules. Below 700 cm–1
it seems to be a lot of bands, which correspond to the Mn–N
stretching mode. The IR results are good agreement with their
solid structural features from the results of their crystal struc-
tures.
FIG. 3. Experimental and simulated X-ray powder diffraction patterns of com-
pound 1.
Photoluminescent Properties
Luminescence property is very important in photochemistry
and photophysics. So in this study, we research the lumines-
cence of compounds 1 and free ligand bip (Figure 5). The free
ligand exhibits emission at 579 nm (excitation at 325 nm) for
bip. Compound 1 shows one broad emission band with the max-
imum intensity at 629 nm upon excitation at 325 nm, which is
red-shifted by 50 nm relative to the emission wavelength of free
ligand bip. The energy of the luminescence suggests that the
most possible assignment for the emissions of 1 originates from
ligand-to-metal charge transfer.[21] Compound 1 exhibits strong
emission, the reason of which may be attributed to the rigid-
ity of N-heterocyclic ligands. The rigidity is favor of energy
transfer and reduces the loss of energy through a radiationless
pathway. The compound 1 may be good candidate for potential
XRD Spectra
The simulated and experimental power XRD patterns of 1
are shown in Figure 3. The patterns calculated from the single-
crystal X-ray data of 1 are in good agreement with the observed
ones in almost identical peak position but with different peak
intensities, which indicates the phase purity of the products. The
differences in intensity may be due to the preferred orientation
of the powder samples.[19,20]
Thermal Analysis
To examine the stability of compound 1, we examined the
TG curves of crystalline samples in the flowing nitrogen atmo-
sphere at a heating rate of 10◦C/min (Figure 4). As expected, in
compound 1, the first weight loss of 16.53% corresponds to the
loss of chloride ions and two water molecules (calcd. 15.07%).
The second weight loss in the temperature range of 245–595◦C
can be ascribed to the release of bip ligands (obsvd. 77.21%,
calcd. 79.12%).
TABLE 3
Hydrogen bond lengths (nm) and angles (◦) for the compound 1
D–H···A
D–H
H···A
D···A D–H···A
O(1W)–H(1W) ···O(2W) 0.0960 0.1770 0.2709
167
171
160
161
O(2W)–H(3W)···Cl(1)
N(3)–H(3A)···Cl(1)
C(8)–H(8A)···Cl(1)
0.0900 0.2350 0.3243
0.0860 0.2390 0.3212
0.0930 0.2700 0.3593
FIG. 4. TG curve of compound 1.

818
L. YAN ET AL.
ence Foundation of China (No. 2005038561) for financial
support.
SUPPLEMENTAL MATERIAL
Supplemental data for this article can be accessed on the
publisher’s website. CCDC 927171 contains the supplementary
crystallographic data for 1, respectively. These data can be ob-
tained free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/datarequest.cif.
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CONCLUSIONS
In conclusion, one novel compound has been synthesized by
using plane multifunctional ligands bip and metallic salt. It is
worthy to note that the intermolecular hydrogen bonds play an
important role in the supramolecular structure. Here we studied
the syntheses, structures, XRD spectra, and TG analysis of com-
pound 1, and also we investigate the fluorescence properties of
title compound, as well as the free ligand bip. The results reveal
that the title compound is worthy of further study as candidate
of potential photoluminescent material. This material will give
new impetus to the construction of novel functional material
with potentially useful physical properties.
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FUNDING
The authors thank the National Natural Science Foun-
dation of China (No. 20971019) and the Postdoctoral Sci-