From one to three dimensions - corrugated 1D-NiGe ribbons as building block in alkaline-earth metal Ae-Ni-Ge phases. Crystal structure and chemical bonding in AeNiGe (Ae - Mg, Sr, Ba)

TL;DR

This study synthesizes and characterizes new MgNiGe, SrNiGe, and BaNiGe compounds, revealing how increasing cation size reduces the dimensionality of [NiGe] polyanions from 3D networks to 1D ribbons, supported by structural and electronic analyses.

Contribution

It provides the first detailed structural and bonding analysis of equiatomic alkaline-earth nickel germanides, highlighting the dimensionality transition in [NiGe] polyanions with cation size.

Findings

MgNiGe has a 3D [NiGe] network with magnesium in channels.

SrNiGe and BaNiGe feature 1D [NiGe] ribbons separated by Sr/Ba atoms.

Electronic structure calculations support the observed structural trends.

Abstract

New equiatomic nickel germanides MgNiGe, SrNiGe, and BaNiGe have been synthesized from the elements in sealed tantalum tubes using a high-frequency furnace. The compounds were investigated by X-ray diffraction both on powders and single crystals. MgNiGe crystallizes with TiNiSi structure type, space group Pnma, Z = 4, a = 6.4742(2) A, b = 4.0716(1) A, c = 6.9426(2) A, wR2 = 0.033, 305 F2 values, 20 variable parameters. SrNiGe and BaNiGe are isotypic and crystallize with anti-SnFCl structure type (Z = 4, Pnma) with a = 5.727(1) A, b = 4.174(1) A, c = 11.400(3) A, wR2 = 0.078, 354 F2 values, 20 variable parameters for SrNiGe and a = 5.969(4) A, b = 4.195(1) A, c = 11.993(5) A, wR2 = 0.048, 393 F2 values, 20 variable parameters for BaNiGe. The increase of the cation size leads to a reduction of the dimensionality of [NiGe] polyanions. In the MgNiGe structure the nickel and germanium atoms build a three-dimensional 3D-[NiGe] network with magnesium atoms in the channels. In contrast, in Sr(Ba)NiGe one-dimensional 1D-[NiGe] ribbons, running parallel to the b-axis, are separated by strontium/barium atoms. The crystal chemistry and chemical bonding in equiatomic alkaline-earth nickel germanides AeNiGe (Ae = Mg, Ca, Sr, Ba) is discussed. The experimental results are reconciled with electronic structure calculations performed using the tight-binding linear muffin-tin orbital (TB-LMTO-ASA) method.