I found the following lemma in Lee's book on smooth manifolds.
Lemma 1.14 (One-Step Smooth Manifold Structure). Let M be a set, and suppose we are given a collection {Uα} of subsets of M, together with an injective map ϕα : Uα → Rn for each α, such that the following properties are satisfied.
(i) For each α, Ueα = ϕα(Uα) is an open subset of Rn.
(ii) For each α and β, ϕα(Uα ∩ Uβ) and ϕβ(Uα ∩ Uβ) are open in Rn.
(iii) Whenever Uα ∩ Uβ 6= ∅, ϕβ ◦ ϕ−1 α : ϕα(Uα ∩ Uβ) → ϕβ(Uα ∩ Uβ) is smooth.
(iv) Countably many of the sets Uα cover M.
(v) Whenever p, q are distinct points in M, either there exists some Uα containing both p and q or there exist disjoint sets Uα, Uβ with p ∈ Uα and q ∈ Uβ.Then M has a unique smooth manifold structure such that each (Uα, ϕα) is a smooth chart.
Is condition (v) different than saying that the collection $\{U_{\alpha} \}$ is a covering of $M$?