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Dropwise addition of an aqueous 3 mL solution of NEt4CN (575 mg, 3.68 mmol) into a vigorously stirred 2 mL aqueous solution of Mn(O2CCH3)2 (210 mg, 1.21 mmol) ensuring that the drops land at the center of the vortex initially led to a yellow precipitate that turned light-green within 10 min. After stirring for 3 h the light-green product was collected by filtration, washed withH2O(2-10 mL), MeOH (2-10 mL), and Et2O(2-10 mL). The product was dried under vacuum for 3 h (yield: 233 mg, 91%). IR (KBr; ñ in cm-1): OH3630 (vw); CH3016 (w), 2992 (w), 2952 (w); CN 2081 (s, sh), 2062 (s); 1463 (m), 1404 (m), 1308 (vw), 1186 (m), 1080 (w), 1037 (m) 1008 (m), 793 (m), 466 (m). Calcd for [NEt4]2[MnII 3(CN)8]xH2O (x=0.25), C24H40.5Mn3N10O0.25 : C 45.18, H 6.40, N 21.96; found C 45.14, H 6.55, N 21.83. TGAwas also used to determine x, which varied from sample to sample, and it was 0.5 for the sample whose magnetic properties are reported herein
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Dropwise addition of an aqueous 3 mL solution of NEt4CN (575 mg, 3.68 mmol) into a vigorously stirred 2 mL aqueous solution of Mn(O2CCH3)2 (210 mg, 1.21 mmol) ensuring that the drops land at the center of the vortex initially led to a yellow precipitate that turned light-green within 10 min. After stirring for 3 h the light-green product was collected by filtration, washed withH2O(2 10 mL), MeOH (2 10 mL), and Et2O(2 10 mL). The product was dried under vacuum for 3 h (yield: 233 mg, 91%). IR (KBr; ñ in cm-1): OH3630 (vw); CH3016 (w), 2992 (w), 2952 (w); CN 2081 (s, sh), 2062 (s); 1463 (m), 1404 (m), 1308 (vw), 1186 (m), 1080 (w), 1037 (m) 1008 (m), 793 (m), 466 (m). Calcd for [NEt4]2[MnII 3(CN)8]xH2O (x=0.25), C24H40.5Mn3N10O0.25 : C 45.18, H 6.40, N 21.96; found C 45.14, H 6.55, N 21.83. TGAwas also used to determine x, which varied from sample to sample, and it was 0.5 for the sample whose magnetic properties are reported herein.
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8]: P3̄m1, a=7.9992(3), c=14.014(1)Ā; V=776.6(1)3̄ T=295 K; Z=1; Rwp=6.58%; c2=2.15
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8]: P3̄m1, a=7.9992(3), c=14.014(1)Ā; V=776.6(1)3̄ T=295 K; Z=1; Rwp=6.58%; c2=2.15.
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NEt4 + and H2O were disordered in the lattice. The refinements were performed with several pseudo-atoms within the voids.We believe that this procedure does not degrade the validity of the Mn: CN framework structure reported herein. The cations can be visualized by maximum entropy maps: J.-H. Her, Ph.D thesis, Department of Physics & Astronomy, Stony Brook University, Stony Brook, NY (2007). The disordered solvent does lead to unusually large error bars for the position of the terminal cyanide relative to the tetrahedral Mn site
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NEt4 + and H2O were disordered in the lattice. The refinements were performed with several pseudo-atoms within the voids.We believe that this procedure does not degrade the validity of the Mn: CN framework structure reported herein. The cations can be visualized by maximum entropy maps: J.-H. Her, Ph.D thesis, Department of Physics & Astronomy, Stony Brook University, Stony Brook, NY (2007). The disordered solvent does lead to unusually large error bars for the position of the terminal cyanide relative to the tetrahedral Mn site.
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