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s C11H8Br2N2OZn, monoclinic, P121/c1 (no. 14), a = 12.300(2) Å, b = 8.070(2) Å, c = 12.751(3) Å, = 103.229(3)°, V = 1232.1 Å, Z = 4, Rgt(F) = 0.041, wRref(F) = 0.101, T = 100 K. C11H8I2N2OZn, monoclinic, P121/c1 (no. 14), a = 12.6266(5) Å, b = 8.3959(3) Å, c = 13.1079(5) Å, = 103.649(1)°, V = 1350.4 Å, Z = 4, Rgt(F) = 0.027, wRref(F) = 0.071, T = 100 K. Source of material In modification of a previous report [1], di-2-pyridyl ketone (dpk) was reacted separately with zinc bromide (1.35 mmol dpk, 1.42 mmol ZnBr2) and zinc iodide (1.00 mmol dpk, 1.05 mmol ZnI2) in 40 mL of hot 1-butanol. Upon slow evaporation of the solutions after 12 hours, the ZnBr2 solution produced white crystals of Zn(dpk)Br2 and the ZnI2 solution produced yellow crystals of Zn(dpk)I2. Discussion Both complexes exhibit similar structures with distorted tetrahedral environment of the zinc atom and are isomorphous to a previously reported chloride complex [2]. Differences in the Zn—X (X = Cl, Br, I) bond distances and X–Zn–X angles follow a trend expected from order of size and electronegativity in the periodic table. Chloride, as the smallest ion, exhibits the shortest Zn—Cl distance (2.202 Å vs. 2.356(7) Å for Zn—Br and 2.542(5) Å for Zn—I); conversely, chlorine is the most electronegative of the three elements and thus the Cl–Zn–Cl angle is the largest (118.1° vs. 116.72(2)° for Br–Zn–Br, and 114.86(2)° for I–Zn–I). In the ORTEP drawings at the 50 % probability level (figure) hydrogen atoms have been omitted. Z. Kristallogr. NCS 219 (2004) 1 © by Oldenbourg Wissenschaftsverlag, München

Crystal structures of (di-2-pyridyl ketone)zinc dibromide and diiodide, Zn(C 11 H 8 N-O)X 2 (X = Br,I)