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This is due to hydrogen bonding and the shape of the structure formed. This bonding is a weak intermolecular attraction caused by the electrostatic attraction between the positive dipole on hydrogen atoms within a polar molecule (caused by electronegativity differences) and the lone pairs of electrons on another atom.

On cooling, empty spaces are created between structures of water molecules, which have arranged in a sort of hexagonal cross-sectioned tube. No further water molecules can fit in these gaps because of the size; this results in a large empty volume, decreasing the density of the solid or alternately expanding the volume of the substance.

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