AbstractLiquid water exhibits unconventional behaviour across its wide range of stability – from its unusually high liquid-vapour critical point down to its melting point and below where it reaches a density maximum and exhibits negative thermal expansion allowing ice to float. Understanding the molecular underpinnings of these anomalies presents a challenge motivating the study of water for well over a century. Here we examine the molecular structure of liquid water across its range of stability, from mild supercooling to the negative pressure and high temperature regimes. We use a recently-developed, electronically-responsive model of water, constructed from gas-phase molecular properties and incorporating many-body, long-range interactions to all orders; as a result the model has been shown to have high transferability from ice to the supercritical regime. We report a link between the anomalous thermal expansion of water and the behaviour of its second coordination shell and an anomaly in hydrogen bonding, which persists throughout liquid water’s range of stability – from the high temperature limit of liquid water to its supercooled regime.