Malaysian Journal of Analytical Sciences, Vol 27 No 3 (2023): 510 - 520

THE CRYSTAL STRUCTURE OF Os₃(CO)₁₁(PPh₂(C₁₀H₇)).H₂O: A COMBINED HIRSHFELD SURFACE ANALYSIS AND DFT CALCULATIONS

(Struktur Hablur Os₃(CO)₁₁(PPh₂(C₁₀H₇)).H₂O: Gabungan Analisis Permukaan Hirshfeld

dan Pengiraan DFT)

Husna Izzati Muhammad Nor Azharan¹, Enis Nadia Md Yusof², Suhana Arshad³,

Omar Bin Shawkataly⁴, and Siti Syaida Sirat^1,5*

¹Faculty of Applied Sciences, Universiti Teknologi MARA, Cawangan Negeri Sembilan, Kampus Kuala Pilah,

72000 Kuala Pilah, Negeri Sembilan, Malaysia

²Chemistry Section, School of Distance Education, Universiti Sains Malaysia, 11800, Minden, Penang, Malaysia

³X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, USM, Penang, 11800, Malaysia

⁴Academy of Sciences Malaysia, Level 20, West Wing, MATRADE Tower, Jalan Sultan Haji Ahmad Shah,
off Jalan Tuanku Abdul Halim, 50480 Kuala Lumpur, Malaysia

⁵Atta-ur-Rahman Institute for Natural Product Discovery (AuRIns), Universiti Teknologi MARA, Kampus Puncak Alam,

42300 Bandar Puncak Alam, Selangor, Malaysia

^*Corresponding author: sitisyaida@uitm.edu.my

Received: 25 January 2023; Accepted: 8 May 2023; Published:  23 June 2023

Abstract

The molecular structure of Os₃(CO)₁₁(PPh₂(C₁₀H₇)).H₂O was investigated by a single crystal X-ray diffraction. The compound crystallizes in the triclinic, P-1 space group with unit cell parameters a = 12.4377(14), b = 12.4413(13), c = 12.4718(13) Å, α = 87.3030(19), β = 63.7889(17) and γ =79.3982(19)°. The asymmetric unit of this structure consists of one-triangulo-triosmium complex molecule and one water molecules. The crystal packing of the title compound is stabilized by O–H···O and C–H···O hydrogen bonds as well as C–H···π interaction. The intermolecular interactions were investigated by Hirshfeld surfaces analysis, showing high contribution of O···H/H···O contacts. The molecular electrostatic potential and frontier molecular orbitals of the title compound were further investigated using Density Functional Theory (DFT), revealing that the nucleophilic regions are located at the carbonyl group. There is a large energy gap (6.095 eV) between HOMO and LUMO.

Keywords: triosmium, phosphine ligand, Hirschfeld surface analysis, crystal structure

Abstrak

Struktur molekul Os₃(CO)₁₁(PPh₂(C₁₀H₇)).H₂O telah disiasat melalui pembelauan sinar-X hablur tunggal. Sebatian itu menghablur dalam kumpulan ruang triklinik, P-1 dengan parameter sel unit a = 12.4377(14), b = 12.4413(13), c = 12.4718(13) Å, α = 87.3030(19), β = 63.7889(17) dan γ =79.3982(19)°. Unit asimetri struktur ini terdiri daripada satu molekul komplek triangulo-triosmium dan satu molekul air. Pembungkusan hablur sebatian distabilkan oleh ikatan hidrogen O–H···O dan C–H···O serta interaksi C–H···π. Interaksi antara molekul telah disiasat oleh analisis permukaan Hirshfeld, menunjukkan O···H/H···O adalah penyumbang utama interaksi. Potensi elektrostatik molekul dan orbital molekul sempadan bagi sebatian ini telah disiasat selanjutnya menggunakan Teori Fungsian Ketumpatan (DFT), mendedahkan bahawa kawasan nukleofilik terletak pada kumpulan karbonil. Terdapat jurang tenaga yang besar (6.095 eV) antara HOMO dan LUMO.

Kata kunci: triosmium, ligan fosfina, analisis permukaan Hirshfeld, struktur hablur

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