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Synthesis of compound 1: A well-ground mixture of [NH 4]2[WO2S2, 0.174 g, 0.5 mmol and CuI (0.382 g, 2.0 mmol) was added to a mixture of DMF and CH3CN (15 mL; 2:1, v/v) under a purified nitrogen atmosphere. After stirring for 10 h, 4,4′-bipy (0.312 g, 2 mmol) was added and the mixture was stirred for another 2 h. The filtrate was layered with diethyl ether. Red block-shaped single crystals suitable for XRD were obtained several days later in 12% yield. Crystal data for 1: G40H46Cu6I 3N9O7S6W2, M r, 2086.96, monoclinic, space group C2/c, a, 17.927(4) Å, b, 24.839(5) Å, c, 16.881(3) Å, β, 103.615(3)°, V, 7306(2) Å3, Z, 4, μ, 6.327 mm-1, ρcalcd, 1.897 g cm-3, GOF, 1.041, R1
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int = 0.042) independent reflections out of a total of 19 658 reflections with 353 parameters)].
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