Water molecules are slightly bent in a 105° angle, rather than the straight 180° angles of most other diatomic compounds. When most compunds freeze they settle into a compacted structure that rests completely stacked into itself (imagine a stack of uniform plates) which makes them more dense than their liquid form. Water molecules, however, form a tessalated structure that has large empty gaps in the middle between the different molecules that decreases the density of the solid form.
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