Synthesis, spectroscopic, crystal structure and DFT investigation of the Cu(II) complex with mixed 2,2’-dimethylmalonate/2,2'-bipyridine ligands

Yıl 2025, Cilt: 27 Sayı: 1, 297 - 314

Mustafa Serkan Soylu

https://doi.org/10.25092/baunfbed.1538657

Öz

In this study; a mixed ligand Cu(II) complex, [Cu(Me2mal)(bpy)(H2O)]∙H2O (Me2mal-2= Dimethylmalonate dianion, bpy=2,2'-bipyridine) was synthesized and characterized experimentally and theoretically by IR, UV and single crystal X-ray diffraction. The complex crystallizes in the orthorhombic system with space group Pnnm. In the complex, the Cu center is coordinated by a Me2mal-2 dianion and a bpy molecule, and the N2O2 exhibits square-planar geometry. The axial position was occupied by the water molecule. The crystal packing of the complex is stabilized by O-H…O hydrogen bonds and  interactions. The contribution of hydrogen bonding and  stacking interactions to crystal packing was also investigated. Theoretical calculations using the DFT method were also carried out in this study. DFT (B3LYP/6-31G) and TD-DFT (B3LYP/LanL2DZ) calculation methods were used to obtain the geometric, vibrational and electronic properties of the synthesized complex and the obtained theoretical calculation results and experimental results are presented comparatively in this study.

Anahtar Kelimeler

Dimethylmalonate, Cu(II) Coordination Complex, Quantum Chemical Computation, Crystal Structure, IR, UV-Vis

Proje Numarası

Grant No:2010K120480 and FEN-BAP-C-220413-22

Karışık 2,2'-dimetilmalonat/2,2'-bipiridin ligandlı Cu(II) kompleksinin sentezi, spektroskopik, kristal yapı ve DFT incelemesi

Öz

Bu çalışmada; karışık ligantlı Cu(II) kompleksi, [Cu(Me2mal)(bpy)(H2O)]∙H2O (Me2mal-2= Dimetilmalonat dianyonu, bpy=2,2'-bipiridin) sentezlenmiştir. Sentezlenen kompleks IR, UV ve tek kristal X-ışını kırınımı yöntemleri ile deneysel ve kuantum mekaniksel hesaplama yöntemleri kullanılarak teorik olarak karakterize edilmiştir. Kompleks, Pnnm uzay grubunda ortorombik kristal sisteminde kristallenmiştir. Komplekste Cu merkezi; bir Me2mal-2 dianyonu ve bir bpy molekülü tarafından koordine edilmiştir ve N2O2 kare-düzlemsel geometri sergilemektedir. Eksensel pozisyonda ise su molekülü bulunmaktadır. Kompleksin kristal paketlenmesi O-H...O hidrojen bağları ve etkileşimleri ile kararlı bir yapı oluşturmuştur. Çalışmada hidrojen bağlarının ve  istifleme etkileşimlerinin kristal paketlenmeye katkısı da araştırılmıştır. Bu çalışmada DFT yöntemi kullanılarak teorik hesaplamalar da yapılmıştır. Sentezlenen kompleksin geometrik, titreşimsel ve elektronik özelliklerini elde etmek için DFT (B3LYP/6-31G) ve TD-DFT (B3LYP/LanL2DZ) hesaplama yöntemleri kullanılmıştır. Elde edilen teorik hesaplama sonuçları ve deneysel sonuçlar karşılaştırmalı olarak verilmiştir.

Anahtar Kelimeler

Dimetilmalonat, Cu(II) Koordinasyon Kompleksi, Kuantum Kimyasal Hesaplama, Kristal Yapı, IR, UV-Vis

Destekleyen Kurum

State of Planning Organization, Aksaray University Science and Technology Application and Research Center in Aksaray, Turkey, (Grant No:2010K120480 ) and The Research Fund of Giresun University (BAP) under the project FEN-BAP-C-220413-22

Proje Numarası

Grant No:2010K120480 and FEN-BAP-C-220413-22

Teşekkür

The author expresses sincere gratitude to Dr. Nefise Dilek for her invaluable contribution in collecting X-ray data. Additionally, we extend our acknowledgments to the Aksaray University Science and Technology Application and Research Center in Aksaray, Turkey, for generously providing access to the Bruker SMART BREEZE CCD diffractometer

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