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Only six words hold S second and A third, and they arrive from several different languages.
USAGE is ordinary modern English and PSALM is familiar to anyone who has met a hymn book. Between them they cover almost everything a puzzle would reasonably ask for.
TSARS is the Russian title, and TSADE and TSADI are two transliterations of the same Hebrew letter. T opens three of the six, more than any other letter.
ASANA joins them from Sanskrit, where it names a posture in yoga. Almost every origin on this page lies outside English entirely.
PSALM hides two silent letters, the P at the front and the L before the M. TSARS and TSADE both open on a T that English speakers tend to swallow. Almost nothing here is spelled the way it sounds.
USAGE, since it appears in ordinary writing far more often. PSALM is well known but belongs to a narrower context.
Both spellings are accepted for the Russian emperor. Only the TSAR form puts S in the second box, so only TSARS fits here.
A letter of the Hebrew alphabet, also written tsadi and sadhe. Two of its spellings appear on this page.