The reactions of [PPh4][(Et-S)WS3] in THF with N-methyliminodiacetic acid produced a new trinuclear cluster [PPh4]2[(S)2W(m-S)2(O)W(THF)(m-S)2W(S)2] 1 and its crystal structure was characterized by single-crystal X-ray analysis. 1 (C52H48O2P2S8W3) crystallizes in the monoclinic space group Cc with a = 19.661(3), b = 11.059(7), c = 25.545(2) ? b = 107.493(8)? V = 5297.4(9) 3, Z = 4, Mr = 1574.93, Dc = 1.975 g/cm3, F(000) = 3024, m (MoKa) = 69.22 cm1 and T = 193 K. With the use of 8713 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.045 and Rw = 0.049. In the structure of the [(S)2W(m-S)2(O)W(THF)(m-S)2W(S)2]2 dianion, the central W(Ⅳ) atom is coordinated by two [WS4]2- ligands, one terminal O and one weakly bound THF molecule. The array of the three W atoms is bent (W(2)W(1)W(3) 156.63(3)?. The mean WW bond distance is 2.998(6) ? and the mean lengths of the WS bonds (those around the central W(1) atom, those bridging W(2) or W(3) atom, and the terminal ones) are 2.434(4), 2.263(4) and 2.150(4) ? respectively. The reactions of [PPh4] [(Et-S) WS3] in THF with N-methyliminodiacetic acid produced a new trinuclear cluster [PPh4] 2 [ (S52) 1 and its crystal structure characterized by single-crystal X-ray analysis. 1 (C52H48O2P2S8W3) crystallizes in the monoclinic space group Cc with a = 19.661 (3), b = 11.059 (7), c = 25.545 (2)? B = 107.493 (8)? V = 5297.4 (9) 3 Z = 4 Mr = 1574.93 Dc = 1.975 g / cm3 F000 = 3024 m MoKa = 69.22 cm1 and T = 193 K. With the use of 8713 observed reflections (I> 3.0s (I)), the structure was refined to R = 0.045 and Rw = 0.049. In the structure of the [(S) 2W (mS) 2 The central W (IV) atom is coordinated by two [WS4] 2-ligands, one terminal O and one weakly bound THF molecule. The array of the three (Ws) W mean is bent (W (2) W (1) W (3) 156.63 (3). The mean WW bond distance is 2.998 (6)? And the mean lengths of the WS bonds (those around the central W ) atom, those bridging W (2) or W (3) atom, and the terminal ones) are 2.434 (4), 2.263 (4) and 2.150 (4)? Respectively.