Essay: Hirshfeld Surfaces Analysis, Characterization, Thermal and Magnetic Properties of Mixed ligand Cu(II) Complex, Synthesis at Bulk and Nano Structure Size

Abstract:
New Copper(II) mixed ligand Structure at bulk single crystal and nanometer sized [Cu(8-HQ)2(Sacc)2], has been synthesized by the reaction of a mixture Cu(II) Acetate with 8-HQ and Saccharin solution in methanol/water by simple Branched tube, solvothermal and sonochemical methods. The nanopowders of Copper Oxide was prepared from the calcinations of the nanostructured of [Cu(8-HQ)2(Sacc)2] nano-Complex (NComplex) at air atmosphere. The structure of Cu(II) mixed ligand complex was determined by Single Crystal X-Ray Diffraction and its magnetic properties were analyzed by molar magnetic susceptibility measurements and e.p.r. spectrum. Nano-structural properties of Cu nano-Complex was characterized by Powder X-Ray Diffraction (PXRD), Thermal Gravimetric Analysis (TGA), Different Thermal Analysis (DTA) and Scanning Electron Microscopy (SEM).
Keywords: Nanopowders, Surface Analysis, Copper, Mixed-Ligand, Copper Oxide, Hirshfeld.
Abbreviations:
Saccharin = 1,1-dioxo-1,2-benzothiazol-3-one or o-sulfobenzimide; 1,2-benzothiazole-3(2H)-one 1,1 dioxide; Hsac, 8-HQ = 8-Hydroxy Quinoline, BT = Branched-Tube, SC = Single Crystals. NComplex = Nano Complex, XRPD = X-Ray Powder Diffraction, TGA/DTA = Thermal Gravimetric and Different Thermal Analysis. SEM = Scanning Electron Microscopy, nic = nicotinamide, py = pyridine, im = imidazole. bzim = benzimidazole, ea = monoethanolamine, L = different phosphine ligands. bipy = 2,2′-bipyridyl, pyet = 2-pyridylethanol. diet = diethanolamine.
Introduction:
Single Crystal Synthesis and Materials Science have contributed significantly to the design, development and optimization of new materials with special physicochemical properties suitable for specific and direct applications. In these case materials that synthesized in Single Crystalline phase are playing important role in modern science such as semiconductors, new drugs, medicine materials, ceramics, porous materials, gas sensing materials, new optic materials and other materials that have new and important applications in social. Crystallography of chemical materials such as metallic complexes with organic ligands as single molecule, coordination polymers, metal-organic frameworks and metal-organic polymers and big range of proteins, which is The most accurate study is on materials and chemical compounds. X-Ray crystallography and identification of the materials and mineral compounds, including single molecular single crystals and coordination polymers, have the potential to conduct extensive research on these materials and to identify their exact molecular structure and to investigate the interactions between atoms or molecules in chemical complexes. In addition, the determination of the new application on them has made the researchers interested in synthesizing this range of materials [1-13]. X-ray crystallography analysis of complexes and other compounds or proteins provides us with a variety of bands and interactions such as π-π interactions.
Weak interactions are play important role in solid-state properties and behavior of molecules. Hydrogen and coordination bonding can define interest and novelty properties to metallic complexes. Interactions of multiple hydrogen bonding between one or two Ligands or complexes impart enhanced stability to Complex structures. Hirshfeld surface analysis investigate all interactions between one by one atoms in complex molecules [25]. Different types of interactions such as H…H, C…H, N…H, O…H, π-based, halogen bonding and other bonds interaction in molecular structure pertinent to our structures [26-29]. By studying of Hirshfeld Surface Analysis particularly useful in studying how different functionalities and Crystal-packing behavior affected
On the other hand, nano-materials are at the leading edge of rapidly developing field of nanotechnology [30-33]. A reduction in particle size to nanometer scale results in various special and interesting properties compared to their bulk properties. Nanopowders of metallic compounds, specifically materials with Nano-scale features, have been the subject of numerous research efforts in fields such as gas sensors [34 and 35], fuel cells [36], solar cells [37 and 38] and electrodes for lithium ion batteries [39] to name a few. Also, Metal oxide nanometer sized materials, have been the subject of numerous research efforts in fields such as antibacterial, antifungal, anti-cancer, drug delivery, new drug designing, self-cleaning and other interest and novel properties to name.
One of the most widely used and best-known artificial sweetening agents is Saccharin. Investigation of different transition metals or heavy metals interactions with saccharin In Complex attracted great interest due to the suspected carcinogenicity of this compound. Saccharinate anion have different sites to coordinate with different metals as i.e. one N, one carbonyl O and two sulfonic O atoms. Besides, a great number of mixed ligand complexes of these same metals interact also with saccharinate in the same way.
For the construction of a number of selective and efficient ionophores, (8-HQ) 8-Hydroxyquinoline moiety has received continuous attention as a platform [26]. The most interesting feature of 8-HQ is its very low quantum yield in aqueous or organic solutions but the fluorescence enhancement occurred from cation binding and many metal chelates of 8-HQ exhibit intense fluorescences [27-29].
As a part of our work on different metal-organic polymers, in this paper, we describe Solvothermal, and branched-tube for SCs and Solvothermal and sonochemical methods for nanopowders of a novel metal-organic polymers, namely [Cu(8-HQ)2(Sacc)2]. Furthermore, the characterizations of the nano-sized CuS and Copper Oxide obtained from the calcinations of Nano Complex at vacuum and atmosphere of air were also reported.
Experimental:
Materials and methods:
All reagents and solvents for the synthesis and analysis in this work were commercially available and were used as received. A multiwave ultrasonic generator (Bandlin Sonopuls Gerate-Typ: UW 3200, Germany), equipped with a converter/transducer and titanium oscillator (horn), 12.5 mm in diameter, operating at 24 kHz with a maximum power output of 600 W, was used for the ultrasonic irradiation. The ultrasonic generator automatically adjusts the power level. IR spectra were recorded using Perkin-Elmer 597 and Nicolet 510P spectrophotometers. The DTA and TGA data were obtained using a PL-STA 1500 apparatus and platinum crucibles with a heating rate of 5 ºCmin−1 in a vacuum. X-Ray Powder Diffraction (XRPD) measurements were performed using a Philips Diffractometer manufactured by X’pert with monochromatized CuKα radiation. Simulated XRPD patterns were calculated using Mercury based on the single crystal data. Particle sizes of selected samples were estimated using the Sherrer method. The samples were characterized with a scanning electron microscope (SEM) (Philips XL 30) with gold coating.
Synthesis of [Cu(8-HQ)2(Sacc)2]:
2.2.1. Branched Tube Method Synthesis of Single Crystalline Product:
To isolate single crystals [8-HQ (0.145 g, 1.0 mmol), Saccharin (0.171 g, 1.0 mmol) and Cu(II) Acetate (0.362 g, 2.0 mmol)] separately were placed in the main arm of a branched-tube. Methanol (MeOH) was carefully added to fill both arms. The tube was sealed and the ligands-containing arm immersed in an oil bath at 70ºC while the other arm was kept at ambient temperature. After 4 days, dark-green crystals that deposited in the cooler arm were isolated, filtered off, washed with acetone and ether and air-dried. Product: M p > 314℃. Anal. Calcd for this compound: C 53.51%, H 3.1%, N 7.8%, found: C 52.85%, H 2.84%, N 7.7%. IR (selected bands, cm-1): 115m, 162w, 188w, 711m, 972m, 1150w, 1255w, 1345vs, 1432v, 1537vs, 1617v, 2020vs and 3065w.Found: IR bands: 115m, 162w, 188w, 711m, 972m, 1150w, 1255w, 1345vs, 1432v, 1537vs, 1617v, 2020vs and 3065w. Mp > 381℃. After single crystal X-Ray analyzing, it became known that the structure of this crystal with precursor crystals is exactly in the same structure.
2.2.2. Solvothermal Method Synthesis of Single Crystalline Product:
To isolate single crystals [8-HQ (0.145 g, 1.0 mmol), Saccharin (0.171 g, 1.0 mmol) and Cu(II) Acetate (0.362 g, 2.0 mmol)] were placed in a 30 ml Teflon-lined, stainless-steel Parr autoclave together with Methanol (18 ml). The autoclave was heated to 150◦ C for one day. The autoclave was then slowly cooled to room temperature, furnishing dark-green crystals obtained and washed with acetone and methanol. Anal. Calcd for this compound: C 53.51%, H 3.1%, N 7.8%, found: C 52.70%, H 2.80%, N 7.5%. IR (selected bands, cm-1): 115m, 162w, 188w, 711m, 972m, 1150w, 1255w, 1345vs, 1432v, 1537vs, 1617v, 2020vs and 3065w.
Prepare the Nanostructures:
Sonochemical Synthesis of nanosized Product:
To prepare nanopowders of this complex by sonochemical method, 50 ml MeOH solution of Cu(II) Acetate (1.8 M) in a vessel was positioned in a high-density ultrasonic probe, operating at 24 kHz with a maximum power output of 800 W. Into this solution 25 ml solution of the (Saccharin) (0.29 M) and (Saccharin) (0.34 M) were added drop wise. These reactions were performed individually then the precipitates were filtered off, washed with Acetone/Deionized water and then dried in air. The different concentrations of metal and ligand solution (0.025, 0.05 and 0.1 M) with the same aging time (1h) were tested at different power of ultrasonic irradiation (60, 120 and 180 kHz).
Solvothermal Synthesis of nanosized Product:
To isolate nanopowders of this product by solvothermal method, [8-HQ (0.145 g, 1.0 mmol), Saccharin (0.171 g, 1.0 mmol) and Cu(II) Acetate (0.362 g, 2.0 mmol)] were placed in a 30 ml Teflon-lined, stainless-steel Parr autoclave together with Methanol (18 ml). The autoclave was heated to 150◦ C for one day. The autoclave was then fast cooled by ice in water in 2 minute, furnishing dark-green powders obtained and washed with acetone and methanol. Anal. Calcd for this compound: C 53.51%, H 3.1%, N 7.8%, found: C 52.70%, H 2.80%, N 7.5%. IR (selected bands, cm-1): 115m, 162w, 188w, 711m, 972m, 1150w, 1255w, 1345vs, 1432v, 1537vs, 1617v, 2020vs and 3065w.
Crystallographic Study
Single-crystal X-ray diffraction data of [Cu(8-HQ)2(Sacc)2] complex were collected with an Agilent XCalibur X-ray diffractometer with EOS CCD detector using Mo-Kα radiation (graphite crystal monochromator λ=0.71073Å). The crystal was kept at 295(2) K during data collection. The data collection, cell refinement and data reduction was executed using CrysAlisPro program [46]. The structure was solved with the olex2.solve and structure solution program using Charge Flipping and refined with the olex2.refine [47]. Refinement package using Levenberg-Marquardt minimization. Further details regarding crystallographic study may be found in Table 1 and supplementary material.
Results and discussion:
3.1. Crystal structures of [Cu(Sacc)(8-HQ)]
Reaction between Saccharin and 8-Hydroxy Quinoline with a mixture of Copper(II) acetate in methanol led to the formation of a new 3D metal-organic polymer. Nanopowders of this Metal-Organic Polymers were obtained by two methods 1) Ultrasonic Irradiation in a methanolic solution and 2) Solvothermal Conditions. while single crystals of Complex were obtained by using a heat gradient applied to a solution of the reagents (the “Branched-Tube and Solvothermal methods”). Scheme 1 gives an overview of the methods used for the synthesis of Complex and NComplex using the two different routes.
{■((1) ((Saccharin+8-Hydroxy Quinoline))/(Cu(OAc)_2 )→[■(Solvothermal Method□(→┴(Slow Cooling) Single Crystals)@Solvothermal Method□(→┴(Fast Cooling) Nanopowders))]@(2) ((Saccharin+8-Hydroxy Quinoline))/(Cu(OAc)_2 )→[■(Branced Tube Method □(→┴(at room T) ) Single Crystals@Sonochemical Method □(→┴(Ultrasonds ) ) Nanopowders)] )}
Scheme 1. Overview of the methods used for the synthesis of Complex and NComplex using the two different routes
Structure of the complex [Cu(8-HQ)2(Sacc)2] produced by the both branched-tube and Solvothermal methods were determined by single crystal X-ray diffraction analysis. A thermal ellipsoid view of [Cu(8-HQ)2(Sacc)2] is shown in Figure 1. To the best of our knowledge, this is the first study reporting a Cu(II) complex coordinated with sulfonyl group in saccharin. Figure 2 shows the formation of 2D H-bonded Structure of this compound. Selected bond lengths are given in Table 2. The complex exhibits a three-dimensional structure, in which the Cu(II) ion is six-coordinate and possesses an CuN2O4 coordination environment by two oxygen atoms from the Saccharin ligands, two nitrogen and two oxygen atoms from the 8-HQ. The O and N atoms of the 8-HQ ligands acts as both two dentate and oxygen atoms of saccharin are other dentate bridging grouping, yielding three-dimensional infinite chains. These chains are further bridged by the Saccharin ligands into a two-dimensional framework as illustrated in Figure 3. Bond length of Cu-Osulfonyl [Cu1-O1] is considerably longer than its corresponding value [2.567(3) Å] in Cu(II) complex with saccharinate ion [48].
The bond valences were calculated as v_ij = exp[(R_ij – d_ij)/B] [49], where R_ij is the bond-valence parameter formally regarded as single bond between atom i and j [50], d_ij is the distance between the atom i and j, and B is equal to 0.37 [51]. Here, the bond-valence parameters for RCu–N and RCu–O were taken as 1.713 [52] and 1.679 [53], respectively. For the complex [Cu(Sacc)(8-HQ)], the calculated bond valences of copper coordinating with 8-HQ are calculated as v_(Cu-N) = 0.514 v.u., v_(Cu-O) = 0.495 v.u., while bond valences of axial Cu-O bonds coordinating with sulfonyl group are obtained as v_(Cu-O) =0.05 v.u. (valence units). Considering valence summation rule, total valence of Cu center is obtained as 2.119. These results indicate that axial coordination bonds are weakened due to considerable bond strain from the presence of bulky monodentate Saccharin ligands. A Cambridge Structural Database (CSD v 5.39, August 2018 release) search [54] shows that elongation in axial Cu-O bonds is reasonable. Excluding Cu centers coordinating with H2O, there are 388 hits including Cu-O bonds of which lengths are in the interval 2.75-2.80 Å. These considerations have shown that complex [Cu(Sacc)(8-HQ)] having octahedral coordination environment at Cu(II) center was successfully synthesized.
Figure. 1. The coordination environment of the Cu(II) ion in [Cu(8-HQ)2(Sacc)2] complex, showing the atom-labelling scheme in asymmetric unit. Coordination environment of Cu center is completed by the atoms in neighbor asymmetric unit with symmetry code [1x, y, 1z]. Displacement ellipsoids are drawn at the 40% probability level.
Figure. 2. 2D structure fragment of the complex [Cu(8-HQ)2(Sacc)2].
Figure. 3. 3D structure fragment of the complex [Cu(8-HQ)2(Sacc)2].
XRD and Morphological study:
Figure 4 shows the XRPD patterns of typical samples of the Complex at nanostructured and single-crystals and the XRD patterns of simulated from single-crystal X-ray data’s. Acceptable matches are observed for all compounds indicating the presence of only one crystalline phase in the samples. The average size of the particles was found for [Cu(8-HQ)2(Sacc)2] to be respectively around 55 nm, 70 nm and 47 nm. Estimated from the Scherer formula for the calculation of particle sizes from the broadening of the XRD peaks (D = 0.891λ/β(cosθ), where D is the average grain size, 0.8911 is the X-ray wavelength (0.15405 nm), and b are the diffraction angle and full width at half maximum of an observed peak, respectively. The calculated value is in agreement with the value obtained from the SEM images shown in Figure 5.
Figure. 4. The XRPD patterns for [Cu(8-HQ)2(Sacc)2]: (a) Single Crystal structure, (b) nano-structured and (c) simulated from single crystals.
Figure 5 shows the SEM images of the Complex nanopowders obtained from calcinations of the compound under laboratory atomsphere, respectively. The morphology of the nanoparticles of this Complex is very similar to that of the compound. This point may be due to the direct removal of the L ligands without changing of morphology under the calcinations in air.
Figure. 5. SEM photographs for nanostructures of [Cu(8-HQ)2(Sacc)2].
Copper Oxide Nanoparticles Preparation Studies:
The final product upon calcinations of the [Cu(8-HQ)2(Sacc)2] prepared by sonochemical and solvothermal methods, based on their XRD patterns Figure 6 in both cases cubic Copper Oxide. The XRD patterns of Copper Oxide nanopowders prepared by calcinations at 600-700 °C of basically identical. The obtained patterns match with the standard patterns of cubic Copper Oxide with a =4.0862 A° and Z = 2. Figure 7 (a) and (b) show SEM images of Copper Oxide nanopowders, produced by calcinations of [Cu(8-HQ)2(Sacc)2] prepared by sonochemical and solvothermal methods in air atmosphere.
Figure 6. (a) XRPD patterns of Copper Oxide nanopowders prepared by calcinations of [Cu(8-HQ)2(Sacc)2] prepared by sonochemical and (b) Copper Oxide nanopowders prepared by calcinations of [Cu(8-HQ)2(Sacc)2] prepared by solvothermal methods.
(a)
(b)
Figure 7. (a) SEM photograph of Copper Oxide nanopowders produced by calcination of [Cu(8-HQ)2(Sacc)2] prepared by sonochemical and (b) Copper Oxide nanopowders produced by calcination of [Cu(8-HQ)2(Sacc)2] prepared by solvothermal methods under air atmosphere.
TGA/DTA Analysis:
To study thermal properties and thermal stability of single crystals of these Complex and NComplex, Thermal Gravimetric Analyses and Different Thermal Analysis (TGA-DTA) were carried out between 30 and 800°C in a static atmosphere of argon. To examine the thermal stability of the nano-structured and single crystals of [Cu(8-HQ)2(Sacc)2] Complex, TGA and DTA were carried out between 40 and 700°C in a static atmosphere of nitrogen. This Complex of [Cu(8-HQ)2(Sacc)2] Decomposed in two step. Single crystals of this Complex is stable and do not decompose up to a temperature of 230°C. Firstly, decomposition of the [Cu(8-HQ)2(Sacc)2] occurs between 230 and 287°C with a mass loss of 50.88% (calcd 50.50%) accordingly to remove of Saccharin ligands. Secondary decomposed of [Cu(8-HQ)2(Sacc)2] occurs between 445 to 573°C with mass loss of 40.30% (calcd 40.50%) accordingly to remove of 8-HQ ligands. Mass loss calculations show that the final decomposition product is Copper Oxide (Figure 8). Nano-structure of compound is somewhat less stable and starts to gradually decompose at 110°C. Decomposition ends at 610°C and the total mass loss is 91.18% (calcd 90.50%), but one-step decomposed of [Cu(8-HQ)2(Sacc)2] nanoparticles occurs between 110 to 610 °C and it indicating again Copper Oxide as the final decomposition product. Decomposition of compound nano-structure starts at about 100°C earlier than its single crystals, probably due to reduction of the particle size of the metal-organic complexes to a few dozen nanometers results in lower thermal stability when compared to the single crystalline samples. For single crystals of [Cu(8-HQ)2(Sacc)2] the DTA curve displays two distinct exothermic effect at 140°C and 498°C and one endothermic effects at 420°C. The TGA curves of the nanopowders have the same general appearance as those of their single crystalline counterparts and the endo and exothermic effects are retained for nanopowders. But the exothermic effect of [Cu(8-HQ)2(Sacc)2] nanoparticles occurred in 230°C. In agreement with the TGA results, some differences between the maximum intensities indicate the lower stability of the nanoparticles compared to those of their single crystals. Nano-structured Copper Oxide has been generated by thermal decomposition of nanoparticle.
Figure 8. TGA/DTA curves of [Cu(Sacc)(8-HQ)] Complex: (a) single crystals and (b) nanopowders.
Magnetic properties of Complex:
Magnetic properties of [Cu(8-HQ)2(Sacc)2] as a χMT vs. T plot (χM is the molar magnetic Susceptibility for two Cu(II) ions) are shown in Figure 9. The value of ΧMT at 300 K is 0.46 cm3mol-1 K, which is very small for two magnetically spin doublets (g >2.00). Starting from room temperature χMT values decrease consistently to 75 K and below 75 K the value is practically 0 cm3 mol-1 M K. This feature is characteristic of very strong antiferromagnetic interactions. The molar magnetization at 2K (as M/NχB) is practically 0 N clearly corroborating that the antiferromagnetic coupling is very strong. The most important factor in interpreting these magnetic data comes from the existence of the binuclear [Cu(8-HQ)2(Sacc)2] entity. The carboxylate group, Sacc is one of the most widely used bridging ligands for designing polynuclear complexes with interesting magnetic properties. Its versatility as a ligand is illustrated by the variety of its coordination modes while acting as a bridge [33-36], the most common being the so-called syn-syn, syn-anti and anti-anti modes. Focusing on the syn-syn coordination mode in Cu(II) Complex, there is a marked dependence of J on the number of carboxylate bridges (4 > 3 > 2 > 1) [37-40]. The J parameter may have a high value for n = 4 (|J| 300 cm-1) as happens in [Cu(8-HQ)2(Sacc)2].
Figure 9. Plot of χMT vs. T for [Cu(8-HQ)2(Sacc)2]. Solid line represents the best-fit calculation.
The fit of the χMT values vs. T (Figure 9) applying the H = -JS1S2 Hamiltonian and the known Bleaney-Bowers formula [38], gave the following values: J = -323.5 cm-1; g = 2.18 and R = 2.6×10-4 (R being the agreement factor defined as {χi[(χMT)obs–(χMT)calc]2/[χi[(χMT)obs]2}. The J value agrees perfectly with those values reported in the literature for this kind of complex [40]. In this calculation we have omitted the J’ value due to the Sacc ligand, because this J’ value is expected to be very small compared to the -323 cm-1. Indeed, in some recent papers reported on Sacc ligand linking isolated Cu ions, J values are not only much smaller than those for [Cu(Sacc)(8-HQ)] units [3] but in some cases the coupling is weakly ferromagnetic [41].
Finally, one of the best fingerprints of these [Cu(8-HQ)2(Sacc)2] Complex is the EPR spectrum. The EPR at 9.79 GHz and at room temperature is plotted in Figure 10, together with a rather good simulation, which gives the following values, assuming axial distortion of the Cu(II) ions: |D| = 0.43 cm-1 ; gǁ = 2.25 and g┴ = 2.10. This magnitude of D (absolute value) agrees with those reported in the literature for similar Complex where D is usually between 0.3 and 0.4 cm-1 [42].
Figure 10. Room temperature solid-state X-band (9.79 GHz) e.p.r. spectrum of [Cu(8-HQ)2(Sacc)2] (solid line). The best simulation is plotted in the dashed line.
Hirshfeld Surfaces Analysis:
The Hirshfeld surface enclosing a molecule is defined by points where the contribution to the electron density from the molecule of interest is equal to the contribution from all the other molecules. For each point on that isosurface two distances are defined: de (the distance from the point to the nearest nucleus external to the surface), and di (the distance to the nearest nucleus internal to the surface). The intermolecular interactions of the title compound are quantified using Hirshfeld surface analysis. The 2D-fingerprint plot of the Hirshfeld surface of the complex is shown in Figure 11. The molecular Hirshfeld surfaces (dnorm, curvedness, di, de and shape index) of the title molecule are shown in Figure 12.
Figure 11. Hirshfeld surface for [Cu(8-HQ)2(Sacc)2]. Percentage of various intermolecular contacts contributed to the Hirshfeld surface.
For comparison of intermolecular interactions scheme in crystal structure, the normalized contact distances, dnorm, based on van der Waals radii, are mapped into the Hirshfeld surfaces. In the color scale, negative values of dnorm are visualized by the red color, indicating contacts shorter than the sum of van der Waals radii. The white color denotes intermolecular distances close to van der Waals contacts with dnorm equal to zero. In turn, contacts longer than the sum of van der Waals radii with positive dnorm values are indicated by blue. The O∙∙∙H and C∙∙∙H contacts in the molecule can be seen in the Hirshfeld surface as the bright red areas. The other visible spots on the surface correspond to H∙∙∙H contacts. Shape index is a measure of ‘‘which shape’’ and it can be sensitive to very subtle changes in surface shape, particularly in areas where the total curvature is very low. The curvedness is the measurement of ‘‘how much shape’’, the flat areas of the surface correspond to low values of curvedness, while sharp curvature areas correspond to high values of curvedness and usually tend to divide the surface into patches, indicating interactions between neighboring molecules. The 2-D fingerprint plots can be decomposed to highlight particular atom pair close contacts. This decomposition enables separation of contributions from different interaction types, which overlap in the full fingerprint. The 2-D fingerprint plots, which analysis all of the intermolecular contacts at the same time, revealed that the main intermolecular interactions in the molecules are H∙∙∙H, H∙∙∙O, H∙∙∙C, H∙∙∙N and C∙∙∙C intermolecular interactions shown in Figure 13.
Figure 12. Hirshfeld surfaces of [Cu(8-HQ)2(Sacc)2] Complex mapped with dnorm, di, de, dnorm, Shape Index, Curvedness and Fragment Patch.
The Hirshfeld surfaces of the complex [Cu(8-HQ)2(Sacc)2] are illustrated in Figures 12-14, showing the surfaces that have been mapped over dnorm, di, de, Curvedness and shape-index. The information given summarized effectively in the Hirshfeld surfaces as the large circular colored areas marked with H∙∙∙H, O∙∙∙H, C∙∙∙H and N∙∙∙H, respectively. The other small extents of visible colored spots and light-white regions in the dnorm surfaces are indicative of weaker and longer contacts other than hydrogen bonds. H-bonds are also evident in shape-index by a colored concave region around the acceptor atom and a complementary blue convex region around the hydrogen bond donor. In [Cu(8-HQ)2(Sacc)2], the H∙∙∙H and O∙∙∙H/H∙∙∙O intermolecular interactions appear as a pair of symmetrical large sharp spikes in the fingerprint plots, for [Cu(8-HQ)2(Sacc)2] which comprise 58%, of the total Hirshfeld surfaces area. The N∙∙∙H/H∙∙∙N interactions comprise for [Cu(8-HQ)2(Sacc)2] 3%, of the total Hirshfeld surfaces and represent two small wings with di + de = 3.868 Å, which is longer than the rvdW separation and suggests the absence of any C/N-H∙∙∙N. Furthermore, the H∙∙∙H interactions are displayed in the distribution of scattered points in the fingerprint plots, which spread up to di = de = 1.08 Å and comprise for [Cu(Sacc)(8-HQ)] 29.1%, of the total Hirshfeld surfaces. Unlike, the O∙∙∙H/H∙∙∙O intermolecular interactions are longer in [Cu(8-HQ)2(Sacc)2] (di + de = 3.49 Å), with the smaller percentage of 12.0% and 13.1% for [Cu(8-HQ)2(Sacc)2], 25.1% to the total Hirshfeld surfaces, respectively. However, the N∙∙∙H/H∙∙∙N interactions are displayed in two sharp spikes in the fingerprint plots, which spread up to the shorter distance of di + de = 2.4 Å, respectively, and contribute for [Cu(8-HQ)2(Sacc)2] 12.5%, to the total Hirshfeld surfaces, respectively.
Figure 13. Fingerprint plots of [Cu(8-HQ)2(Sacc)2] complex showing the percentages of contacts contributions to the total Hirshfeld surface area of molecules.
Figure. 14. The solid state UV-vis absorption of (a) single crystal of [Cu(8-HQ)2(Sacc)2] metal-organic polymers (b) nanopowders of [Cu(8-HQ)2(Sacc)2] metal-organic polymers and (c) Copper Oxide nanoparticles prepared by calcination of [Cu(8-HQ)2(Sacc)2] nanopowders.
Solid-State UV-vis Spectra Studies of [Cu(Sacc)(8-HQ)].
Figure 14 shows the solid state UV-vis spectra of the complex of [Cu(8-HQ)2(Sacc)2] at single crystal form. [Cu(8-HQ)2(Sacc)2] particles at nanometric sized and Copper Oxide nanoparticles prepared by calcination of [Cu(8-HQ)2(Sacc)2]. Single crystals of [Cu(8-HQ)2(Sacc)2] Complex display two absorption wide band with the maximum intensity of 365 nm and 385 nm. Also Nanopowders of [Cu(8-HQ)2(Sacc)2] Complex display two absorption wide band with the maximum intensity of 363 nm and 396 nm. But the solid state UV-vis spectra of the Copper Oxide nanoparticles, prepared by calcination at 600-700 ºC of [Cu(8-HQ)2(Sacc)2] nanopowders shows three absorption band in 360, 372 and 392 nm accordingly to O-C, Cu-N and Cu-O bonds in this product.
Discussions:
A new Cu(II) mixed ligand complex, [Cu(8-HQ)2(Sacc)2] have been synthesized at single crystal by using a BT (Branched-Tube) and Solvothermal methods and nanopowders by ultrasound irradiation (Sonochemistry Method). The compound was structurally characterized by single-crystal X-Ray Diffraction. The crystal structure of the compound consists of a 1D, 2D and 3D view in which the Cu(II) ions is octahedral coordinated by 8-HQ and Saccharin ligands. TGA/DTA studies indicate that reduction of the particle size of the Complex of to a few dozen nanometers results in lower thermal stability when compared to the single crystalline samples. The calcinations of this compound under air atmospheres produce Copper Oxide nanopowders. This study demonstrates the Complex may be suitable precursors for the respectively and simple preparation of nanoscale. In summary, from this study, it can be deduced that the Hirshfeld Surface analysis and Magnetic Properties and also TGA/DTA studies of this [Cu(8-HQ)2(Sacc)2] Complex is interest.
Supplementary data:
CCDC 1889572 contains the supplementary crystallographic data for [Cu(8-HQ)2(Sacc)2] complex. The data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgements:
Supporting of this investigation by the Lorestan University, Khorram Abad, Lorestan, Islamic Republic of Iran, Uludag University, Bursa, Turkey and Ataturk University of Erzurum, Turkey, is gratefully acknowledged.
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Table 1. Crystallographic data of [Cu(Saccharin)(8-HQ)] complex.
Crystal data
Deposit Number CCDC 1889572
Chemical formula C32H22CuN4O8S2
Mr 718.23
Crystal system, space group Monoclinic, C2/c
Colour, habit Dark green, block
Temperature (K) 295
a, b, c (Å) 17.238 (1), 7.9958 (5), 21.625 (2)
 (°) 96.660 (7)
V (Å3) 2960.5 (4)
Z 4
Radiation type Mo K
 (mm-1) 0.94
Crystal size (mm) 0.36 × 0.27 × 0.18
Data collection
Diffractometer Xcalibur, Eos
Absorption correction Analytical
Tmin, Tmax 0.819, 0.881
No. of measured reflections 5302
No. of independent reflections 2790
No. of observed [I > 2(I)] reflections 1778
Rint 0.048
Index ranges -15 h  20, -5 k  9, -19 l  26
Refinement
R[F2 > 2(F2)], wR(F2), S 0.068, 0.198, 1.09
No. of parameters 214
H-atom treatment H-atom parameters constrained
max , min (e Å-3) 1.61, -1.42
Table. 2. Selected bond lengths (Å) of [Cu(Sacc)(8-HQ)] complex.
Cu1-O1 2.788(4) N1-C10 1.388(8) N2-C9 1.341(7)
Cu1-O4 1.939(3) C5-C6 1.400(8) C1-C2 1.419(7)
Cu1-N2 1.960(5) C6-C7 1.400(8) C1-C6 1.417(7)
S1-O1 1.464(4) C7-C8 1.348(9) C2-C3 1.371(7)
S1-O2 1.424(5) C8-C9 1.400(8) C3-C4 1.407(8)
S1-N1 1.645(5) C10-C11 1.492(7) C13-C14 1.366(8)
S1-C16 1.752(6) C11-C12 1.387(8) C14-C15 1.384(8)
O3-C10 1.192(7) C11-C16 1.363(7) C15-C16 1.376(7)
O4-C2 1.335(6) N2-C1 1.353(7)