Malaysian Journal of Analytical Sciences, Vol 27 No 4 (2023): 790 - 801

CRYSTAL STRUCTURE AND HIRSHFELD SURFACE ANALYSIS OF COMPOUND DI[2-((1E)-{2-(2-METHYLBENZYLSULFANYL) METHYLIDENE- HYDRAZIN-1-YLIDENE}METHYL)-6-

METHOXY- PHENOL]

(Struktur Hablur dan Analisis Permukaan Hirshfeld bagi sebatian Di[2-((1E)-{2-(2-Metilbenzilsulfanil)Metiliden-Hidrazin-1-Iliden}Metil)-6-Metoksi-Fenol])

Enis Nadia Md Yusof^1*, Suhana Arshad², Kwong Huey Chong³, and Siti Syaida Sirat^4,5

¹Chemical Sciences Programme, School of Distance Education, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia

²X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, Penang 11800, Malaysia

³Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia

⁴School of Chemistry and Environment, Faculty of Applied Sciences, Universiti Teknologi MARA, Cawangan Negeri Sembilan, Kampus Kuala Pilah, 72000 Kuala Pilah, Negeri Sembilan, Malaysia

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

42300 Bandar Puncak Alam, Selangor, Malaysia

^*Corresponding author: enisnadia@usm.my

Received: 19 June 2023; Accepted: 23 July 2023; Published: 22 August 2023

Abstract

In this work we report crystal structure and Hirshfeld surface analysis of compound di[2-((1E)-{2-(2- methylbenzylsulfanyl)methylidene- hydrazin-1-ylidene}methyl)-6-methoxy- phenol] (HL), which has a dimeric dithiocarbazate backbone. HL has a non-planar structure due to strong intra-bonds that create two S(6) graph-set motifs, preventing free rotation by locking its atoms in a nearly planar arrangement. The crystal packing involves intermolecular C—H···S and C—H···π interactions that form a two-dimensional sheet parallel to the ac-plane which extends into a three-dimensional network arrangement via π···π interactions involving the centroid of the phenyl ring. Hirshfeld surface analysis describes that the major contribution to the overall crystal packing is from H⋯H contacts, followed by H⋯C/C⋯H contacts, which signify the presence of C—H···π interactions. The presence of intermolecular C—H···S interactions can be confirmed through the involvement of S⋯H/H⋯S contacts.

Keywords: dithiocarbazate, dimeric, crystal structure, Hirshfeld surface analysis

Abstrak

Dalam kajian ini, kami melaporkan struktur hablur dan analisis permukaan Hirshfeld bagi sebatian di[2-((1E)-{2-(2-metilbenzilsulfanil)metilidena-hidrazin-1-ilidena}metil)-6-metoksi-fenol] (HL), yang mempunyai rangkaian dithiocarbazat berbentuk dimerik. HL mempunyai struktur tidak rata disebabkan oleh ikatan dalaman yang kuat yang membentuk dua motif set-graf S(6), menghalang putaran bebas dan mengunci atom-atomnya dalam susunan hampir rata. Penempatan hablur melibatkan interaksi intermolekul antara C—H···S dan C—H···π yang membentuk satu lapisan dua dimensi sejajar dengan satah ac dan meluas ke susunan rangkaian tiga dimensi melalui interaksi π···π yang melibatkan pusat gelang fenil. Analisis permukaan Hirshfeld menjelaskan bahawa sumbangan utama kepada penempatan kristal secara keseluruhan adalah daripada sentuhan H⋯H, diikuti oleh sentuhan H⋯C/C⋯H, yang menunjukkan kewujudan interaksi C—H···π. Kewujudan interaksi intermolekul antara C—H···S dapat disahkan melalui keterlibatan sentuhan S⋯H/H⋯S.

Kata kunci: dithiocarbazat, dimerik, struktur hablur, analisis permukaan Hirshfeld

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