We study the cohomology of a chiral supercharge
Q in the
N=4 super-Yang-Mills (SYM) theory at tree level. The cohomology classes correspond one-to-one to the
161 Bogomol'nyi-Prasad-Sommerfield (BPS) states at one-loop. We argue that monotone classes on the Coulomb branch respect the S-duality between the theories with
SO(2N+1) and
USp(2N) gauge groups, but find an explicit example of a pair of cohomology classes that "violate" the S-duality in the sense that the tree-level
Q-cohomologies are not isomorphic between the neighborhoods near the two free points. Within this pair, one is a fortuitous class and the other is a monotone chiral ring element. Assuming the non-perturbative validity of S-duality, our results disprove a long-standing conjecture on the one-loop exactness of the
161-BPS spectrum (including the
81-BPS chiral ring spectrum) in the
N=4 SYM. Mathematically, this shows that, the relative Lie algebra cohomology
H∙(g[A],g) is generally not graded-isomorphic to
H∙(Lg[A],Lg), where
g and
Lg are a pair of Langlands dual Lie algebras and
A=C[z+,z−]⊗Λ(θ1,θ2,θ3).