The reaction of [Fe₂S₂(CO)₆] with one equiv. of o-OCH₃C₆H₄CH₂Br under the reduction of LiBHEt₃ in dry THF afforded a tetranuclear cluster [(µ₄-S){(µ-SCH₂(o- OCH₃)Ph)Fe₂(CO)₆}₂] (1). Complex 1 crystallizes in monoclinic, space group P2₁/n with a = 16.5623(6), b = 12.8265(5), c = 18.2702(7) Å, β = 115.95(1)º, V = 3489.9(4) ų, Z = 4, μ = 1.87 mm^-1, D_c = 1.709 Mg/m³, T = 296(2) K, C₂₈H₁₈Fe₄O₁₄S₃, M_r = 898.03, F(000) = 1800, S = 1.10, R = 0.032 and wR = 0.058. Complex 1 consists of two diiron fragments possessing a {Fe₂(CO)₆} core. The two diiron units are bridged by an inorganic sulfide in a µ₄-S binding mode and the sulfide is in a distorted tetrahedral geometry with the four iron atoms at each corner of the distorted tetrahedral. In its solid state, two types of non-classic intermolecular hydrogen bonding interactions plus a weak π-π stacking interaction led to a 2-D network.