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