The spelling with cz- is against the usage of all Slavonic languages; the word was so spelt by Herberstein, Rerum Moscovit. Commentarii, 1549, the chief early source of knowledge as to Russia in Western Europe, whence it passed into the Western Languages generally; in some of these it is now old-fashioned; the usual Ger. form is now zar; French adopted tsar during the 19th c. This also became frequent in English towards the end of that century, having been adopted by the Times newspaper as the most suitable English spelling. [OED]
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