The Crystal Structure of Zineb, Seventy-Five Years Later

Abstract

Ethylene bis­(dithiocarbamates) (EBDTCs) have been used as staple fungicides for over 75 years. The first industrially manufactured EBDTC was zineb, zinc ethylene bis­(dithiocarbamate), marketed under the trade name Dithane. Even though zineb has been used as a fungicide since the 1940s, its crystal structure has remained unknown. Herein, we describe the crystal structure of zineb (triclinic crystal system, space group P1̅, a = 7.5094(9) Å, b = 9.4356(9) Å, c = 7.4120(7) Å, α = 107.945(8)°, β = 100.989(7)°, γ = 105.365(8)°, V = 460.07(10) Å3). The inorganic fragment of the structure consists of two Zn2+ cations, coordinated by the thiocarbamate groups. There are four Zn–S bonds with lengths in the range of 2.325–2.426 Å, and one rather long Zn–S contact of 2.925(8) Å. Inorganic fragments are linked by organic EBDTC ligands to form extended, polymeric layers. The layers are packed in an ABAB manner, related by the inversion symmetry and held together by a hydrogen bonding network. In this article, in addition to describing the crystal structure, we correlate the structural features with the vibrational spectroscopic and thermal characteristics of zineb, and we provide a short summary of the major developments of fungicides in the 20th century.

A Structural Survey of Poly-Functional Dithiocarbamate Ligands and the Aggregation Patterns They Sustain

“…There is an isomorphous relationship between 43 and 44. The only coordination polymer is this section, which has only very recently been described, is formed in the crystal of 45, comprising [Zn(L 18 )]n [57]. The structure is notable for two additional reasons.…”

“…The thioamide-N-H atoms project to either side of the layer, enabling the formation of N-H … S hydrogen bonds, leading to a three-dimensional architecture. The only coordination polymer is this section, which has only very recently been described, is formed in the crystal of 45, comprising [Zn(L 18 )] n [57]. The structure is notable for two additional reasons.…”

Advances in the Detection of Dithiocarbamate Fungicides: Opportunities for Biosensors

“… Timeline of the development of fungicides, showing the appearance of DTFs from 1930s onwards. Reproduced from [ 1 ], with permission. …”

“…While the development of new pesticide molecules and formulations has continued over the years, currently used DTFs such as maneb, mancozeb, propineb, thiram, and ziram were introduced more than 50 years ago ( Figure 2 ) [ 1 ]. Mancozeb, propineb, and thiram are among the top selling fungicides, e.g., mancozeb sales are expected to reach $18 billion by 2025 [ 2 ].…”

Insights into the Antimicrobial Potential of Dithiocarbamate Anions and Metal-Based Species

“…. S (dithiocarbamate) hydrogen bonding [6]. These are but two examples of the prominent role that dithiocarbamates play in contemporary society with other biological roles summarized in the literature [7][8][9][10].…”