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Because there are exceptions to that rule. The whole rule is actually "I before E except after C, or when spoken like ay as in neighbor and weigh".

More information from the Related link:

* The rule only applies to digraphs, so words like "deity" and "science" don't count. * The rule "i before e except after c" should be extended to include "except when said 'ay' as in 'neighbor' and 'weigh'". * The rule only applies to digraphs that have the /i:/ ('ee') pronunciation, as in 'piece'. (Note the conflict between this and the previous item.) * The rule doesn't apply to words that are recent imports from foreign languages, such as "gneiss", "dreidel", and "enceinte". * The rule doesn't apply to the large number of plurals of words ending in "cy" ("fallacies", "frequencies", "vacancies", ... ) because in the UK - in traditional RP - "cies" is pronounced with the "i" of "pin", even though it is pronounced with the "ee" of "feed" by most World-English speakers and by younger UK speakers.

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Q: Why does the I before E except after C rule not apply for Caffeine and Sleigh?
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