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A novel coordination polymer of Ni(II) based on 1,3,5-benzenetricarboxylic acid synthesis, characterization, crystal structure, thermal study, and luminescent properties
Accepted Manuscript A novel coordination polymer of Ni(II) based on 1,3,5-benzenetricarboxylic acid synthesis, characterization, crystal structure, thermal study, and luminescent properties Sania Saheli, Alireza Rezvani PII:
S0022-2860(16)30843-2
DOI:
10.1016/j.molstruc.2016.08.013
Reference:
MOLSTR 22839
To appear in:
Journal of Molecular Structure
Received Date: 30 May 2016 Revised Date:
2 August 2016
Accepted Date: 6 August 2016
Please cite this article as: S. Saheli, A. Rezvani, A novel coordination polymer of Ni(II) based on 1,3,5benzenetricarboxylic acid synthesis, characterization, crystal structure, thermal study, and luminescent properties, Journal of Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.08.013. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
A novel coordination polymer of Ni(II) based on 1,3,5-benzenetricarboxylic acid Synthesis, Characterization, Crystal Structure, Thermal Study, and luminescent Properties Sania Saheli, Alireza Rezvani*
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Department of Chemistry, University of Sistan and Baluchestan, P. O. Box 98135-674, Zahedan, Iran *E-mail address: [email protected]
Abstract
A new metal-organic framework (MOF) formulated as [Ni(H2btc)(OH)(H2O)2] (1) (H3btc =
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1,3,5-benzenetricarboxylic acid) was synthesized using the hydrothermal technique. The complex 1 was characterized by elemental analysis, infrared spectroscopy, and powder X-ray
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diffraction in addition to single crystal X-ray diffraction. X-ray crystal structural analysis displayed that the compound belonged to the monoclinic space group P21/n with cell parameters a= 6.8658(14) Å, b= 18.849(4) Å, c= 8.5608(17) Å. In the title complex, ligand is linked to metal centers through two µ-oxo bridges and forming a 2D layer which is led to form an interesting geometry. The thermal stability and fluorescence property of 1 have also been investigated.
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Keywords: Metal-organic framework, Coordination polymers, 1,3,5-Benzenetricarboxylic acid, Nickel complex, Crystal structure. 1. Introduction
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In recent years, metal–organic frameworks (MOFs) or coordination polymers (CPs) have attracted attention due to their potential applications for gas storage [1−4], catalysis [5−7],
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molecular magnetism [8−11], and sensors [12]. The combinations of metal ions and organic ligands are designed in the form of one-dimensional (1D), two-dimensional (2D) and threedimensional (3D) frameworks. The coordination geometry of the metal ions and the organic ligand geometry affect the structure and topology of the MOFs. In this context, carboxylate ligands, as organic linkers, are attractive for variety in binding modes of the carboxylate groups to metal atoms [13−16]. In particular, amid organic ligands, 1,3,5-benzenetricarboxylic acid is a rigid ligand which can construct diversity coordination polymers[17−22].
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Furthermore, MOFs have received considerable attention because of their ability to construct new topologies with different properties. Obviously, rational designs of the assembled process and control of reaction conditions are extremely important to obtain intriguing topologies and architectures. Apart from the nature of metal and ligand, their ratio, as well as other factors such
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as solvent, pH, and temperature can affect strongly the outcomes of reactions. Therefore, by changing reaction conditions, new MOfs with novel properties can be obtained. Up to now, various nickel coordination polymers, based on 1,3,5-benzenetricarboxylic acid, have been reported [23−25], in most of which, the metal centers have similar geometry. However, in this
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work attempt has been made to optimize the reaction conditions most notably pH and temperature, to attain new coordination polymer with different geometry and unique property.
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This has been accomplished after several experiments.
In the present work, we report hydrothermal syntheses, crystal structure and characterization of a new Ni coordination polymer with bridged 1,3,5-benzenetricarboxylic acid ligand. Furthermore, the thermal treatment and fluorescence property of [Ni(H2btc)(OH)(H2O)2] (1) are investigated. 2. Experimental
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2.1. Materials and Instruments
All purchased chemicals were of reagent grade and used without further purification. IR spectrum was recorded using FT-IR spectrum JASCO 460 spectrophotometer with KBr pellets in the 4000–400 cm−1 regions at room temperature. Elemental analyses were performed by using a
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Leco, CHNS-932 elemental analyzer. Simultaneous Thermal Analysis (STA) was recorded by using NETZSCH STA 409 PC/PG equipment. The sample (8.298 mg) was placed in alumina cell
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and heated from 30 - 800 °C at a heating rate of 10 °C min-1 with nitrogen as flowing gas with rate of 50 ml min-1. XRD data were collected on a Bruker D8 advance by considering 2θ range from 5° to 70°. The fluorescence study of compound was carried out on a Varian Cary Eclipse fluorescence spectrophotometer. 2.2. Synthesis of complex 1 1,3,5-benzenetricarboxylic acid (105 mg , 0.5 mmol) was dissolved in 15 ml distilled water containing NaOH (60 mg , 1.5 mmol) and stirred 30 min, at room temperature. An aqueous solution of Ni(NO3)2 .6H2O (290 mg , 1.0 mmol) was added to the above -mentioned solution. 2
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The reaction mixture was placed in a Parr-Teflon lined stainless steel vessel. It was sealed and heated to 130 °C for 3 days. The reaction mixture was cooled by slow cooling to the room temperature. Blue crystals of 1 suitable for single crystal X-ray diffraction analysis were collected from the final reaction mixture by filtration and air dried at the ambient temperature.
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The yield was 63%. Anal. Calc. for C9H10NiO9: C, 33.69; H, 3.14. Found: C, 33.31; H, 3.19%. IR (cm-1): 3498-3279 (m, br), 2920(w), 1710(s), 1617(s), 1570(s), 1385(s), 1365(s), 749(m), 743(m).
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2.3. X-ray structure determination
X-ray diffraction data of the single crystal with a dimension of 0.09 mm × 0.09 mm × 0.4 mm
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was collected on a STOE-IPDS 2T diffractometer using a graphite monochromated Mo Kα radiation (λ=0.71073 Å). A total of 4287 reflections were collected in the range of 3.2°<θ<25° at 293(2) K, of which 1937 independent ones (R(int)=0.1059) were used. The structure was solved by direct methods and refined by full-matrix least squares on F2 using the programs SHELXL2014 [26] and WinGX-2013.3 [27]. All non- hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were placed in ideal positions and refined as riding
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atoms with relative isotropic displacement parameters. A summary of the crystallographic data and processing parameters is given in Table 1.
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3. Results and Discussion
The title complex, [Ni(H2btc)(OH)(H2O)2] 1, was prepared by the reaction of Ni(NO3)2 .6H2O with 1,3,5-benzenetricarboxylic acid and NaOH in the aqueous solution under the hydrothermal
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condition (Scheme 1).
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COOH COOH + NaOH + Ni(NO3)2
O
HO
OH2 OH
2
Ni
O
COOH
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HOOC
O
O
OH
n
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Scheme 1 Synthesis and chemical structure of [Ni(H2btc)(OH)(H2O)2]
Crystal Structure
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The complex crystallizes in the monoclinic space group P21/n and consists of a coordination polymer with bridged carboxyl and carboxylate groups. The base structural features of the complex are illustrated in Fig. 1a. The metal centers are connected to two neighboring ones, through two µ-oxo bridges, to form infinite metal-metal chain running in a zigzag fashion, as shown in Fig. 1b.
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Each metal ion center is five coordinate and Ni‒O bond lengths and bond angles (Ni1‒O1 1.934(3), Ni1‒O3 1.918(3), Ni1‒O7 1.972(4), Ni1‒O9 1.981(4), Ni1‒O8 2.243(4), O1‒Ni1‒O3
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174.45(15)°, O7‒Ni1‒O9 169.59 (16), O1‒Ni1‒O7 89.05(17)°, O1‒Ni1‒O9 91.14(16)°) show that the coordination geometry of complex 1 is a distorted square pyramidal. Selected bond
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lengths and bond angles are listed in Table 2. The equatorial plane is defined by four oxygen atoms of one coordinated water molecule together with one hydroxyl ion and two O atoms from carboxylate and carboxyl groups of two different H3btc ligands. The rest of the one coordination site is occupied by one oxygen atom of one coordinated water molecule. Crystallographically there is only one type of btc ligand in the crystal structure, which bridges two Ni(II) ions on either side of the ring, forming a 2D sheet, Fig. 2. The H3btc ligand is not fully deprotonated and only one of the carboxyl groups is deprotonated which is connected in a 4
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monodentate manner to Ni1. On the other hand, there are two different sets of the carboxyl groups. In one set, one carboxyl group connects to monodentate coordination mode to Ni1. In
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other set, one carboxyl group is uncoordinated.
The Ni‒O bond distances and bond angles are in the range of 1.918(3)-2.243(4) Å and
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86.23(12)-174.45(15)°, respectively. All bond distances and bond angles agree well with those reported in other nickel(II) complexes having the same coordinating atoms [28−31]. In this
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compound, a number of hydrogen bonds exist, which are listed in Table 3. The carboxyl and carboxylate groups, hydrogen’s of benzene rings are participated to form hydrogen bonds. These hydrogen bonds are involved in the stabilization and formation of an interesting supramolecular structure, depicted in Fig. 3.
FT-IR spectrum
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The FT-IR spectrum of compound 1 is shown in Fig. 4. The broad band observed at 3498–3279
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cm–1 is caused by the stretching vibrations of the coordinated water molecules. Their high intensity and wide broadness is representative of an intensive hydrogen bonding. The three adjacent hydrogen atoms around the benzene ring of H3Btc give rise to two C-H stretching
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modes, two C-H in-plane bending and one C-H out-of-plane bending modes. The bands observed at 3105 and 3070 cm–1 are assigned to C-H stretching vibrations [32]. The C-H in-plane bending vibrations are appeared at 1187 and 1181 cm–1 , moreover, the band at 890 cm–1 attributed to CH out-of-plane bending mode [33,34]. The strong band at 1617 cm–1 illustrates the deprotonated of carboxyl group. The vibration band at 1710 cm–1 is assigned to the carbonyl functional group, which confirms that carboxyl groups are not fully deprotonated. The carboxylate group can be coordinated to a metal ion through one of the three modes of monodentate, bidentate and bridging ligand. The mode of (COO)-bonding to metal ion is correlated with its vibration
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frequency. The various ∆ν values (∆ν = νa(OCO) – νs(OCO)) demonstrate different coordination modes of the carboxylate group to metal ions [35]. Therefore, the difference between (∆ν =185) asymmetric stretching vibrational mode, νa(OCO) appears at 1570 cm–1 while symmetric stretching νs(OCO), which emerges at 1385 cm–1, can be assigned to unidentate coordination of
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the carboxylate group, which is in agreement with the single-crystal X-ray analysis. The absorption bands observed at 1246 and 1244 cm–1 are imputed to ν(C‒O) vibrations. The δ(COO) mode emerges in the spectrum of the complex at 749 cm–1. The band appearing at 692 cm–1
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Simultaneous thermal analysis
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belongs to ring out of-plane deformation vibration.
The thermal behavior of complex 1 was investigated by thermogravimetric analysis (TGA) and result is shown in Fig. 5. The complex displayed four steps of weight loss. The first and second degradation stage in the temperature region of 20-260 °C is attributed to the elimination of coordinated water molecules and hydroxyl groups, which corresponds to weight losses of about 11.7% (calcd. 11.2%) and 4.6% (calcd. 5.3%), respectively. Upon raising the temperature to
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620℃, the two final steps of weight loss occur, which are assigned to the decomposition of H3btc ligands, leading to the collapse of the entire structure. The weight remains constant up to 800°C and residue is associated with stable oxide phase. Differential scanning calorimetry (DSC) analysis was also carried out in order to obtain further
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evidence for the various stages and appraise their thermal behavior. Several endo- and exothermic effects are emerged in the DSC curve (Fig. 5) which they are in agreement with TGA
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results. Two endothermic peaks are observed in the temperature range of 40- 280 °C which are attributed to the evolution of coordinated water molecules and hydroxyl ion. Two exothermic peaks at the temperature reign 300- 640 °C are probably due to crystallization of nickel oxide.
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X-ray powder diffraction The simulated XRD pattern and experimental XRD pattern of complex 1 are shown in Fig. 6. The location of the diffraction peaks in the simulated and experimental patterns shows good
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agreement with each other and confirms the high purity of compound.
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Luminescent Property
The fluorescence spectra of the ligand and complex 1 were recorded in acetonitrile at room temperature (Fig. 7). The free H3btc ligand displays a maximum emission peak at 425 nm and
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two broad emission peaks at 487 and 511 nm when is excited at 208 nm which can be attributed to the π* → π transitions of the ligand [36]. On the other hand, when the complex is illuminated at 200 nm, it presents a main emission band at 428 nm and two shoulders emission peaks at 488 and 512 nm. The emission spectra are similar; however, they are different in terms of emission intensity. Therefore, the enhancement emission peak of the complex through complexation is assigned to increase rigidity in the structure of complex [37] and prevent the photoinduced
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electron transfer (PET) process [38, 39]. The prepared complex can probably be used as a fluorescence material in fabrication of optoelectronic devices.
Conclusions
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In conclusion, a new nickel coordination polymer based on 1,3,5-benzenetricarboxylic acid ligand was successfully synthesized under hydrothermal conditions. X-Ray diffraction analysis of compound 1 shows that each metal center has distorted square pyramidal geometry and µ-oxo bridges from H3btc ligand linking the centers to each other. The photoluminescence property of complex 1 was investigated, and an enhancement of fluorescence intensity was observed.
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Supplementary Material Further information can be obtained free of charge on application to the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K. [Fax: +44 (1223)336-
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033; E-mail: [email protected]] quoting the depository number CCDC 1438953. Acknowledgements
The authors are grateful to University of Sistan and Bluchestan for the support of this work.
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Table 1 Crystallography data for [Ni(H2btc)(OH)(H2O)2].
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Empirical formula Formula Weight Crystal system Space group Crystal size (mm) a[Å] b[Å] c[Å] β[°] Volume/Å3 Z Dcalcd.[g cm–3] F(000) Temperature [K] Reflections collected /unique wR2 R S Limiting indices
C9H10NiO9 320.86 Monoclinic P21/n 0.09 × 0.09 × 0.40 6.8658(14) 18.849(4) 8.5608(17) 92.98(3) 1106.4(4) 4 1.926 656 293(2) 4287/1937 0.0920 0.0429 0.87 -8 ≤ h≤ 6 -20 ≤ k≤ 22 -10 ≤ l≤ 10
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Complex
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Table 2 Selected bond lengths (Å) and bond angles (°) for [Ni(H2btc)(OH)(H2O)2].
a: 3/2-x,-1/2+y,3/2-z
174.45(15) 89.05(17) 86.23(12) 91.14(16) 86.85(17) 90.39(14) 93.57(16) 94.76(16) 169.59(16) 95.64(15) 116.8(2) 120.9(3) 157.00 113.00 88.00 128.00 105.00 103.00 124.00 141(3) 114.00
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Bond Angels O1‒Ni1‒O3 O1‒Ni1‒O7 O1‒Ni1‒O8 O1‒Ni1‒O9 O3‒Ni1‒O7 O3‒Ni1‒O8 O3‒Ni1‒O9 O7‒Ni1‒O8 O7‒Ni1‒O9 O8‒Ni1‒O9 Ni1‒O1‒C1 Ni1‒O3‒C5 Ni1‒O7‒H5 Ni1‒O7‒H6 H5‒O7‒H6 Ni1‒O8‒H7 Ni1‒O8‒H8 H7‒O8‒H8 Ni1‒O9‒H9 C5‒O4‒H11 C8‒O6‒H1
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1.934(3) 1.918(3) 1.972(4) 2.243(4) 1.981(4) 1.288(5) 1.235(6) 1.261(6) 1.247(5) 1.211(5) 1.336(5) 1.509(6) 1.503(5) 1.460(6) 0.87(3) 0.9400 0.9000 0.8600 0.8900 0.7800 0.9100
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Bond Lengths Ni1‒O1 Ni1‒O3 Ni1‒O7 Ni1‒O8 Ni1‒O9 O1‒C1 O2‒C1 O3‒C5 O4‒C5 O5‒C8 O6‒C8 C1‒C2 C4‒C5a C7‒C8 O4‒H11 O6‒H1 O7‒H5 O7‒H6 O8‒H8 O8‒H7 O9‒H9
d(D–H) 0.9400 0.9000 0.8600 0.7800 0.8900 0.9100 0.87(3) 0.9300 0.9300
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D–H⋯A O6‒H1⋯O2 O7‒H5⋯O6 O7‒H6⋯O4 O8‒H7⋯O2 O8‒H8⋯O5 O9‒H9⋯O4 O4‒H11⋯O9 C9‒H2⋯O1 C6‒H3⋯O8
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Table 3 Hydrogen bonds data for [Ni(H2btc)(OH)(H2O)2] (Å,°).
d(H⋯A) 1.6600 2.3800 1.9700 2.3900 1.9600 1.8500 1.93(4) 2.4000 2.5700
d(D⋯A) 2.554(5) 2.877(5) 2.723(5) 3.086(6) 2.799(5) 2.720(5) 2.720(5) 2.727(5) 3.428(5)
<(DHA) 156.00 115.00 146.00 150.00 155.00 159.00 151(4) 101.00 153.00
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Fig. 1. (a) A general view of compound 1. (b) A view of infinite 1D zigzag chain of Ni(II) linked by H2btc‒ in 1.
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Fig. 2. A polyhedral representation of the 2D layer of Ni(II) linked by H2btc‒ in 1.
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Fig. 3. The view of hydrogen bonding network connecting neighboring 1D chains in 1.
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70 60
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T(%)
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Wavenumber cm‒1
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Fig. 4. The FT-IR spectrum of compound 1.
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4
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1.5 1
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40 30 20 20
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Temperature (℃ ℃)
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Fig. 5. TGA (a) and (b) DSC plots of complex (1).
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TG (%)
2
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DSC (mW/mg)
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2.5
80
(b) 0.5 0 (a)
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Intensity
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(a)
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(b) 40
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2 Tetha
Free ligand Complex 1
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Intensity
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Fig. 6. The XRD patterns of compound (1) (a) simulated from the single-crystal X-ray data and (b) as experimental.
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Wavelenght (nm)
Fig. 7. Fluorescence spectra of complex 1 and free ligand at room temperature.
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Highlights
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Hydrothermal synthesis of a new coordination polymer of Ni(II) with 1,3,5benzenetricarboxylic acid. Investigation by elemental analysis, FT- IR spectroscopy, single crystal X-ray The complex shows 2D layer which is led to form an interesting geometry. Stabilization of the crystal structure as a result of the hydrogen bonds. Photoluminescence property of the complex has also been investigated.
S0022-2860(16)30843-2
DOI:
10.1016/j.molstruc.2016.08.013
Reference:
MOLSTR 22839
To appear in:
Journal of Molecular Structure
Received Date: 30 May 2016 Revised Date:
2 August 2016
Accepted Date: 6 August 2016
Please cite this article as: S. Saheli, A. Rezvani, A novel coordination polymer of Ni(II) based on 1,3,5benzenetricarboxylic acid synthesis, characterization, crystal structure, thermal study, and luminescent properties, Journal of Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.08.013. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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A novel coordination polymer of Ni(II) based on 1,3,5-benzenetricarboxylic acid Synthesis, Characterization, Crystal Structure, Thermal Study, and luminescent Properties Sania Saheli, Alireza Rezvani*
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Department of Chemistry, University of Sistan and Baluchestan, P. O. Box 98135-674, Zahedan, Iran *E-mail address: [email protected]
Abstract
A new metal-organic framework (MOF) formulated as [Ni(H2btc)(OH)(H2O)2] (1) (H3btc =
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1,3,5-benzenetricarboxylic acid) was synthesized using the hydrothermal technique. The complex 1 was characterized by elemental analysis, infrared spectroscopy, and powder X-ray
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diffraction in addition to single crystal X-ray diffraction. X-ray crystal structural analysis displayed that the compound belonged to the monoclinic space group P21/n with cell parameters a= 6.8658(14) Å, b= 18.849(4) Å, c= 8.5608(17) Å. In the title complex, ligand is linked to metal centers through two µ-oxo bridges and forming a 2D layer which is led to form an interesting geometry. The thermal stability and fluorescence property of 1 have also been investigated.
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Keywords: Metal-organic framework, Coordination polymers, 1,3,5-Benzenetricarboxylic acid, Nickel complex, Crystal structure. 1. Introduction
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In recent years, metal–organic frameworks (MOFs) or coordination polymers (CPs) have attracted attention due to their potential applications for gas storage [1−4], catalysis [5−7],
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molecular magnetism [8−11], and sensors [12]. The combinations of metal ions and organic ligands are designed in the form of one-dimensional (1D), two-dimensional (2D) and threedimensional (3D) frameworks. The coordination geometry of the metal ions and the organic ligand geometry affect the structure and topology of the MOFs. In this context, carboxylate ligands, as organic linkers, are attractive for variety in binding modes of the carboxylate groups to metal atoms [13−16]. In particular, amid organic ligands, 1,3,5-benzenetricarboxylic acid is a rigid ligand which can construct diversity coordination polymers[17−22].
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Furthermore, MOFs have received considerable attention because of their ability to construct new topologies with different properties. Obviously, rational designs of the assembled process and control of reaction conditions are extremely important to obtain intriguing topologies and architectures. Apart from the nature of metal and ligand, their ratio, as well as other factors such
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as solvent, pH, and temperature can affect strongly the outcomes of reactions. Therefore, by changing reaction conditions, new MOfs with novel properties can be obtained. Up to now, various nickel coordination polymers, based on 1,3,5-benzenetricarboxylic acid, have been reported [23−25], in most of which, the metal centers have similar geometry. However, in this
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work attempt has been made to optimize the reaction conditions most notably pH and temperature, to attain new coordination polymer with different geometry and unique property.
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This has been accomplished after several experiments.
In the present work, we report hydrothermal syntheses, crystal structure and characterization of a new Ni coordination polymer with bridged 1,3,5-benzenetricarboxylic acid ligand. Furthermore, the thermal treatment and fluorescence property of [Ni(H2btc)(OH)(H2O)2] (1) are investigated. 2. Experimental
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2.1. Materials and Instruments
All purchased chemicals were of reagent grade and used without further purification. IR spectrum was recorded using FT-IR spectrum JASCO 460 spectrophotometer with KBr pellets in the 4000–400 cm−1 regions at room temperature. Elemental analyses were performed by using a
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Leco, CHNS-932 elemental analyzer. Simultaneous Thermal Analysis (STA) was recorded by using NETZSCH STA 409 PC/PG equipment. The sample (8.298 mg) was placed in alumina cell
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and heated from 30 - 800 °C at a heating rate of 10 °C min-1 with nitrogen as flowing gas with rate of 50 ml min-1. XRD data were collected on a Bruker D8 advance by considering 2θ range from 5° to 70°. The fluorescence study of compound was carried out on a Varian Cary Eclipse fluorescence spectrophotometer. 2.2. Synthesis of complex 1 1,3,5-benzenetricarboxylic acid (105 mg , 0.5 mmol) was dissolved in 15 ml distilled water containing NaOH (60 mg , 1.5 mmol) and stirred 30 min, at room temperature. An aqueous solution of Ni(NO3)2 .6H2O (290 mg , 1.0 mmol) was added to the above -mentioned solution. 2
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The reaction mixture was placed in a Parr-Teflon lined stainless steel vessel. It was sealed and heated to 130 °C for 3 days. The reaction mixture was cooled by slow cooling to the room temperature. Blue crystals of 1 suitable for single crystal X-ray diffraction analysis were collected from the final reaction mixture by filtration and air dried at the ambient temperature.
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The yield was 63%. Anal. Calc. for C9H10NiO9: C, 33.69; H, 3.14. Found: C, 33.31; H, 3.19%. IR (cm-1): 3498-3279 (m, br), 2920(w), 1710(s), 1617(s), 1570(s), 1385(s), 1365(s), 749(m), 743(m).
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2.3. X-ray structure determination
X-ray diffraction data of the single crystal with a dimension of 0.09 mm × 0.09 mm × 0.4 mm
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was collected on a STOE-IPDS 2T diffractometer using a graphite monochromated Mo Kα radiation (λ=0.71073 Å). A total of 4287 reflections were collected in the range of 3.2°<θ<25° at 293(2) K, of which 1937 independent ones (R(int)=0.1059) were used. The structure was solved by direct methods and refined by full-matrix least squares on F2 using the programs SHELXL2014 [26] and WinGX-2013.3 [27]. All non- hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were placed in ideal positions and refined as riding
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atoms with relative isotropic displacement parameters. A summary of the crystallographic data and processing parameters is given in Table 1.
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3. Results and Discussion
The title complex, [Ni(H2btc)(OH)(H2O)2] 1, was prepared by the reaction of Ni(NO3)2 .6H2O with 1,3,5-benzenetricarboxylic acid and NaOH in the aqueous solution under the hydrothermal
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condition (Scheme 1).
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COOH COOH + NaOH + Ni(NO3)2
O
HO
OH2 OH
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Ni
O
COOH
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HOOC
O
O
OH
n
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Scheme 1 Synthesis and chemical structure of [Ni(H2btc)(OH)(H2O)2]
Crystal Structure
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The complex crystallizes in the monoclinic space group P21/n and consists of a coordination polymer with bridged carboxyl and carboxylate groups. The base structural features of the complex are illustrated in Fig. 1a. The metal centers are connected to two neighboring ones, through two µ-oxo bridges, to form infinite metal-metal chain running in a zigzag fashion, as shown in Fig. 1b.
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Each metal ion center is five coordinate and Ni‒O bond lengths and bond angles (Ni1‒O1 1.934(3), Ni1‒O3 1.918(3), Ni1‒O7 1.972(4), Ni1‒O9 1.981(4), Ni1‒O8 2.243(4), O1‒Ni1‒O3
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174.45(15)°, O7‒Ni1‒O9 169.59 (16), O1‒Ni1‒O7 89.05(17)°, O1‒Ni1‒O9 91.14(16)°) show that the coordination geometry of complex 1 is a distorted square pyramidal. Selected bond
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lengths and bond angles are listed in Table 2. The equatorial plane is defined by four oxygen atoms of one coordinated water molecule together with one hydroxyl ion and two O atoms from carboxylate and carboxyl groups of two different H3btc ligands. The rest of the one coordination site is occupied by one oxygen atom of one coordinated water molecule.
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monodentate manner to Ni1. On the other hand, there are two different sets of the carboxyl groups. In one set, one carboxyl group connects to monodentate coordination mode to Ni1. In
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other set, one carboxyl group is uncoordinated.
The Ni‒O bond distances and bond angles are in the range of 1.918(3)-2.243(4) Å and
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86.23(12)-174.45(15)°, respectively. All bond distances and bond angles agree well with those reported in other nickel(II) complexes having the same coordinating atoms [28−31]. In this
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compound, a number of hydrogen bonds exist, which are listed in Table 3. The carboxyl and carboxylate groups, hydrogen’s of benzene rings are participated to form hydrogen bonds. These hydrogen bonds are involved in the stabilization and formation of an interesting supramolecular structure, depicted in Fig. 3.
FT-IR spectrum
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The FT-IR spectrum of compound 1 is shown in Fig. 4. The broad band observed at 3498–3279
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cm–1 is caused by the stretching vibrations of the coordinated water molecules. Their high intensity and wide broadness is representative of an intensive hydrogen bonding. The three adjacent hydrogen atoms around the benzene ring of H3Btc give rise to two C-H stretching
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modes, two C-H in-plane bending and one C-H out-of-plane bending modes. The bands observed at 3105 and 3070 cm–1 are assigned to C-H stretching vibrations [32]. The C-H in-plane bending vibrations are appeared at 1187 and 1181 cm–1 , moreover, the band at 890 cm–1 attributed to CH out-of-plane bending mode [33,34]. The strong band at 1617 cm–1 illustrates the deprotonated of carboxyl group. The vibration band at 1710 cm–1 is assigned to the carbonyl functional group, which confirms that carboxyl groups are not fully deprotonated. The carboxylate group can be coordinated to a metal ion through one of the three modes of monodentate, bidentate and bridging ligand. The mode of (COO)-bonding to metal ion is correlated with its vibration
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frequency. The various ∆ν values (∆ν = νa(OCO) – νs(OCO)) demonstrate different coordination modes of the carboxylate group to metal ions [35]. Therefore, the difference between (∆ν =185) asymmetric stretching vibrational mode, νa(OCO) appears at 1570 cm–1 while symmetric stretching νs(OCO), which emerges at 1385 cm–1, can be assigned to unidentate coordination of
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the carboxylate group, which is in agreement with the single-crystal X-ray analysis. The absorption bands observed at 1246 and 1244 cm–1 are imputed to ν(C‒O) vibrations. The δ(COO) mode emerges in the spectrum of the complex at 749 cm–1. The band appearing at 692 cm–1
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Simultaneous thermal analysis
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belongs to ring out of-plane deformation vibration.
The thermal behavior of complex 1 was investigated by thermogravimetric analysis (TGA) and result is shown in Fig. 5. The complex displayed four steps of weight loss. The first and second degradation stage in the temperature region of 20-260 °C is attributed to the elimination of coordinated water molecules and hydroxyl groups, which corresponds to weight losses of about 11.7% (calcd. 11.2%) and 4.6% (calcd. 5.3%), respectively. Upon raising the temperature to
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620℃, the two final steps of weight loss occur, which are assigned to the decomposition of H3btc ligands, leading to the collapse of the entire structure. The weight remains constant up to 800°C and residue is associated with stable oxide phase. Differential scanning calorimetry (DSC) analysis was also carried out in order to obtain further
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evidence for the various stages and appraise their thermal behavior. Several endo- and exothermic effects are emerged in the DSC curve (Fig. 5) which they are in agreement with TGA
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results. Two endothermic peaks are observed in the temperature range of 40- 280 °C which are attributed to the evolution of coordinated water molecules and hydroxyl ion. Two exothermic peaks at the temperature reign 300- 640 °C are probably due to crystallization of nickel oxide.
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X-ray powder diffraction The simulated XRD pattern and experimental XRD pattern of complex 1 are shown in Fig. 6. The location of the diffraction peaks in the simulated and experimental patterns shows good
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agreement with each other and confirms the high purity of compound.
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Luminescent Property
The fluorescence spectra of the ligand and complex 1 were recorded in acetonitrile at room temperature (Fig. 7). The free H3btc ligand displays a maximum emission peak at 425 nm and
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two broad emission peaks at 487 and 511 nm when is excited at 208 nm which can be attributed to the π* → π transitions of the ligand [36]. On the other hand, when the complex is illuminated at 200 nm, it presents a main emission band at 428 nm and two shoulders emission peaks at 488 and 512 nm. The emission spectra are similar; however, they are different in terms of emission intensity. Therefore, the enhancement emission peak of the complex through complexation is assigned to increase rigidity in the structure of complex [37] and prevent the photoinduced
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electron transfer (PET) process [38, 39]. The prepared complex can probably be used as a fluorescence material in fabrication of optoelectronic devices.
Conclusions
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In conclusion, a new nickel coordination polymer based on 1,3,5-benzenetricarboxylic acid ligand was successfully synthesized under hydrothermal conditions. X-Ray diffraction analysis of compound 1 shows that each metal center has distorted square pyramidal geometry and µ-oxo bridges from H3btc ligand linking the centers to each other. The photoluminescence property of complex 1 was investigated, and an enhancement of fluorescence intensity was observed.
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Supplementary Material Further information can be obtained free of charge on application to the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K. [Fax: +44 (1223)336-
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033; E-mail: [email protected]] quoting the depository number CCDC 1438953. Acknowledgements
The authors are grateful to University of Sistan and Bluchestan for the support of this work.
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Table 1 Crystallography data for [Ni(H2btc)(OH)(H2O)2].
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Empirical formula Formula Weight Crystal system Space group Crystal size (mm) a[Å] b[Å] c[Å] β[°] Volume/Å3 Z Dcalcd.[g cm–3] F(000) Temperature [K] Reflections collected /unique wR2 R S Limiting indices
C9H10NiO9 320.86 Monoclinic P21/n 0.09 × 0.09 × 0.40 6.8658(14) 18.849(4) 8.5608(17) 92.98(3) 1106.4(4) 4 1.926 656 293(2) 4287/1937 0.0920 0.0429 0.87 -8 ≤ h≤ 6 -20 ≤ k≤ 22 -10 ≤ l≤ 10
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Complex
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Table 2 Selected bond lengths (Å) and bond angles (°) for [Ni(H2btc)(OH)(H2O)2].
a: 3/2-x,-1/2+y,3/2-z
174.45(15) 89.05(17) 86.23(12) 91.14(16) 86.85(17) 90.39(14) 93.57(16) 94.76(16) 169.59(16) 95.64(15) 116.8(2) 120.9(3) 157.00 113.00 88.00 128.00 105.00 103.00 124.00 141(3) 114.00
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Bond Angels O1‒Ni1‒O3 O1‒Ni1‒O7 O1‒Ni1‒O8 O1‒Ni1‒O9 O3‒Ni1‒O7 O3‒Ni1‒O8 O3‒Ni1‒O9 O7‒Ni1‒O8 O7‒Ni1‒O9 O8‒Ni1‒O9 Ni1‒O1‒C1 Ni1‒O3‒C5 Ni1‒O7‒H5 Ni1‒O7‒H6 H5‒O7‒H6 Ni1‒O8‒H7 Ni1‒O8‒H8 H7‒O8‒H8 Ni1‒O9‒H9 C5‒O4‒H11 C8‒O6‒H1
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1.934(3) 1.918(3) 1.972(4) 2.243(4) 1.981(4) 1.288(5) 1.235(6) 1.261(6) 1.247(5) 1.211(5) 1.336(5) 1.509(6) 1.503(5) 1.460(6) 0.87(3) 0.9400 0.9000 0.8600 0.8900 0.7800 0.9100
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Bond Lengths Ni1‒O1 Ni1‒O3 Ni1‒O7 Ni1‒O8 Ni1‒O9 O1‒C1 O2‒C1 O3‒C5 O4‒C5 O5‒C8 O6‒C8 C1‒C2 C4‒C5a C7‒C8 O4‒H11 O6‒H1 O7‒H5 O7‒H6 O8‒H8 O8‒H7 O9‒H9
d(D–H) 0.9400 0.9000 0.8600 0.7800 0.8900 0.9100 0.87(3) 0.9300 0.9300
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D–H⋯A O6‒H1⋯O2 O7‒H5⋯O6 O7‒H6⋯O4 O8‒H7⋯O2 O8‒H8⋯O5 O9‒H9⋯O4 O4‒H11⋯O9 C9‒H2⋯O1 C6‒H3⋯O8
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Table 3 Hydrogen bonds data for [Ni(H2btc)(OH)(H2O)2] (Å,°).
d(H⋯A) 1.6600 2.3800 1.9700 2.3900 1.9600 1.8500 1.93(4) 2.4000 2.5700
d(D⋯A) 2.554(5) 2.877(5) 2.723(5) 3.086(6) 2.799(5) 2.720(5) 2.720(5) 2.727(5) 3.428(5)
<(DHA) 156.00 115.00 146.00 150.00 155.00 159.00 151(4) 101.00 153.00
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Fig. 1. (a) A general view of compound 1. (b) A view of infinite 1D zigzag chain of Ni(II) linked by H2btc‒ in 1.
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Fig. 2. A polyhedral representation of the 2D layer of Ni(II) linked by H2btc‒ in 1.
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Fig. 3. The view of hydrogen bonding network connecting neighboring 1D chains in 1.
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70 60
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Wavenumber cm‒1
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Fig. 4. The FT-IR spectrum of compound 1.
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Temperature (℃ ℃)
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Fig. 5. TGA (a) and (b) DSC plots of complex (1).
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TG (%)
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Intensity
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2 Tetha
Free ligand Complex 1
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Intensity
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Fig. 6. The XRD patterns of compound (1) (a) simulated from the single-crystal X-ray data and (b) as experimental.
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Fig. 7. Fluorescence spectra of complex 1 and free ligand at room temperature.
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Highlights
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Hydrothermal synthesis of a new coordination polymer of Ni(II) with 1,3,5benzenetricarboxylic acid. Investigation by elemental analysis, FT- IR spectroscopy, single crystal X-ray The complex shows 2D layer which is led to form an interesting geometry. Stabilization of the crystal structure as a result of the hydrogen bonds. Photoluminescence property of the complex has also been investigated.