A century of structures: historical fidelity and computational fitness in the Inorganic Crystal Structure Database (ICSD).

Abstract

The earliest entries in the Inorganic Crystal Structure Database (ICSD) are both primary historical documents and active computational inputs. They record how the Braggs, Goldschmidt, Vegard, and others established the structural foundations of inorganic chemistry; they are also served, without distinction, to automated pipelines, machine-learning training sets, and high-throughput workflows. We assess 464 ICSD structures from 1913 to 1929 using two independent tools: Eir v1.4.2 (bond valence sums, global instability index) and MaplePy (Madelung part of lattice energy). The pre-1925 median global instability index is 0.077 valence unit (v.u.), below that of modern rock salt reference data (mean 0.192 v.u.); the Braggs' 1913 NaCl gives 0.005 v.u., Bragg's 1922 corundum 0.001 v.u. Early crystallographers were doing simple structures and getting them right. The problem is not quality but metadata. A small number of entries carry genuine topological errors (BeO in NaCl type, SnTe in zinc blende) whose corrective information already exists in database Comments fields but is not machine-readable, not reflected in quality classifications, and relatively invisible to downstream users. We propose six automated fitness-for-purpose flags that surface these cases without removing or modifying any historical record.