Diacetonalkohol als Komplexligand. Die Kristallstrukturen von [MnBr2{O=C(Me)CH2–C(Me)2OH}2] und [M{O=C(Me)CH2–C(Me)2OH}2][MCl4] mit M = Fe, Co und Zn
Abstract
deDie Metalldihalogenide MnBr2 und MCl2 (M = Fe, Co, Zn) reagieren mit Diacetonalkohol (4-Hydroxy-4-methyl-2-pentanon) unter Bildung der Titelverbindungen, die durch IR-Spektroskopie und Kristallstrukturanalysen charakterisiert werden.
[MnBr2{O=C(Me)CH2–C(Me2)OH}2] (1): Raumgruppe C2/c, Z = 4, Gitterkonstanten bei 293 K: a = 1189,2(4); b = 1317,2(3); c = 1200,0(3) pm; β = 102,25(3)°, R1 = 0,0256. In 1 ist das Manganatom verzerrt oktaedrisch von den beiden cis-ständigen Bromatomen und von den vier O-Atomen der beiden Diacetonalkohol-Chelatmoleküle koordiniert. Die Abstände Mn–[OH] (223,8 pm) und Mn–[O=C] (222,1 pm) sind nur wenig verschieden.
[M{O=C(Me)CH2–C(Me)2OH}2][MCl4] [M = Fe (2), Co (3), Zn (4)]: 2 und 3 kristallisieren isotyp miteinander in der Raumgruppe Pc, Z = 4. Gitterkonstanten für 2 bei 293 K: a = 865,8(3); b = 926,3(2); c = 1401,5(1) pm; β = 104,19(2)°, R1 = 0,0421. Gitterkonstanten für 3 bei 293 K: a = 872,3(1); b = 925,7(1); c = 1394,2(3) pm; β = 104,79(2)°, R1 = 0,0481. Die Metallatome der [M{O=C(Me)CH2–C(Me)2OH}2]2+Ionen in 2 und 3 sind wie in 1 verzerrt oktaedrisch von zwei Diacetonalkohol-Molekülen chelatisiert und cis-ständig über zwei μ-Cl-Atome der [MCl4]2–-Anionen zu Strängen assoziiert.
[Zn{O=C(Me)CH2–C(Me)2OH}2][ZnCl4] (4): Raumgruppe C2/c, Z = 4. Gitterkonstanten bei 213 K: a = 1582,27(13); b = 1356,15(13); c = 941,93(7) pm; β = 107,283(10)°, R1 = 0,0328. Das Zinkatom des Dikations in 4 ist verzerrt oktaedrisch von den beiden Diacetonalkohol-Chelatmolekülen in den Äquatorialpositionen und trans-ständig von zwei μ-Cl-Atomen der [ZnCl4]2–-Ionen zu Strängen assoziiert.
Abstract
enDiacetone Alcohol as Complex Ligand. Crystal Structures of [MnBr2{O=C(Me)CH2–C(Me)2OH}2] and [M{O=C(Me)CH2–C(Me)2OH}2][MCl4] with M = Fe, Co, and Zn
The metal halides MnBr2 and MCl2 (M = Fe, Co, Zn) react with diacetone alcohol (4-hydroxy-4-methyl-2-pentanon) forming the title compounds, which are characterized by IR spectroscopy and crystal structure analyses.
[MnBr2{O=C(Me)CH2–C(Me2)OH}2] (1): Space group C2/c, Z = 4, lattice dimensions at 293 K: a = 1189.2(4), b = 1317.2(3), c = 1200.0(3) pm, β = 102.25(3)°, R1 = 0.0256. In 1 the manganese atom is coordinated in a distorted octahedral fashion by the two cis bromine atoms and by the four oxygen atoms of the two diacetone alcohol chelating molecules. The distances Mn–[OH] (223.8 pm) and Mn–[O=C] (222.1 pm) are only slightly different.
[M{O=C(Me)CH2–C(Me)2OH}2][MCl4] [M = Fe (2), Co (3), Zn (4)]: 2 and 3 crystallize isotypically with each other in the space group Pc, Z = 4. Lattice dimensions for 2 at 293 K: a = 865.8(3), b = 926.3(2), c = 1401.5(1) pm, β = 104.19(2)°, R1 = 0.0421. Lattice dimensions for 3 at 293 K: a = 872.3(1), b = 925.7(1), c = 1394.2(3) pm, β = 104.79(2)°, R1 = 0.0481. As in 1, the metal atoms of the [M{O=C(Me)CH2–C(Me)2OH}2]2+ ions in 2 and 3 are chelated in a distorted octahedral fashion by two diacetone alcohol molecules and associated cis via two μ-Cl atoms of the [MCl4]2– anions to form strands.
[Zn{O=C(Me)CH2–C(Me)2OH}2][ZnCl4] (4): Space group C2/c, Z = 4. Lattice dimensions at 213 K: a = 1582.27(13), b = 1356.15(13), c = 941.93(7) pm, β = 107.283(10)°, R1 = 0.0328. The zinc atom of the dication in 4 is associated in a distorted octahedral fashion by the two diacetone alcohol chelating molecules in the equatorial positions and trans by two μ-Cl atoms of the [ZnCl4]2– ions to form strands.
