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.