Ammonothermal Synthesis, Crystal Structure, and Properties of the Ytterbium(II) and Ytterbium(III) Amides and the First Two Rare-Earth-Metal Guanidinates, YbC(NH)<sub>3</sub> and Yb(CN<sub>3</sub>H<sub>4</sub>)<sub>3</sub> Arno L. Görne Janine George Jan van Leusen Gerald Dück Philipp Jacobs Naveen Kumar Chogondahalli Muniraju Richard Dronskowski 10.1021/acs.inorgchem.6b00736.s005 https://acs.figshare.com/articles/dataset/Ammonothermal_Synthesis_Crystal_Structure_and_Properties_of_the_Ytterbium_II_and_Ytterbium_III_Amides_and_the_First_Two_Rare-Earth-Metal_Guanidinates_YbC_NH_sub_3_sub_and_Yb_CN_sub_3_sub_H_sub_4_sub_sub_3_sub_/3409033 We report the oxidation-controlled synthesis of the ytterbium amides Yb­(NH<sub>2</sub>)<sub>2</sub> and Yb­(NH<sub>2</sub>)<sub>3</sub> and the first rare-earth-metal guanidinates YbC­(NH)<sub>3</sub> and Yb­(CN<sub>3</sub>H<sub>4</sub>)<sub>3</sub> from liquid ammonia. For Yb­(NH<sub>2</sub>)<sub>2</sub>, we present experimental atomic displacement parameters from powder X-ray diffraction (PXRD) and density functional theory (DFT)-derived hydrogen positions for the first time. For Yb­(NH<sub>2</sub>)<sub>3</sub>, the indexing proposal based on PXRD arrives at <i>R</i>3̅, <i>a</i> = 6.2477(2) Å, <i>c</i> = 17.132(1) Å, <i>V</i> = 579.15(4) Å<sup>3</sup>, and <i>Z</i> = 6. The oxidation-controlled synthesis was also applied to make the first rare-earth guanidinates, namely, the doubly deprotonated YbC­(NH)<sub>3</sub> and the singly deprotonated Yb­(CN<sub>3</sub>H<sub>4</sub>)<sub>3</sub>. YbC­(NH)<sub>3</sub> is isostructural with SrC­(NH)<sub>3</sub>, as derived from PXRD (<i>P</i>6<sub>3</sub>/<i>m</i>, <i>a</i> = 5.2596(2) Å, <i>c</i> = 6.6704(2) Å, <i>V</i> = 159.81(1) Å<sup>3</sup>, and <i>Z</i> = 2). Yb­(CN<sub>3</sub>H<sub>4</sub>)<sub>3</sub> crystallizes in a structure derived from the [ReO<sub>3</sub>] type, as studied by powder neutron diffraction (<i>Pn</i>3̅, <i>a</i> = 13.5307(3) Å, <i>V</i> = 2477.22(8) Å<sup>3</sup>, and <i>Z</i> = 8 at 10 K). Electrostatic and hydrogen-bonding interactions cooperate to stabilize the structure with wide and empty channels. The IR spectra of the guanidinates are compared with DFT-calculated phonon spectra to identify the vibrational modes. SQUID magnetometry shows that Yb­(CN<sub>3</sub>H<sub>4</sub>)<sub>3</sub> is a paramagnet with isolated Yb<sup>3+</sup> (4f<sup>13</sup>) ions. A <i>CONDON 2.0</i> fit was used to extract all relevant parameters. 2016-06-01 19:03:54 Crystal Structure displacement parameters indexing proposal IR spectra vibrational modes CONDON 2.0 3 crystallizes 10 K Ammonothermal Synthesis ReO 3 PXRD DFT YbC Yb SQUID magnetometry powder neutron diffraction