There is no "set" day to breed.
To omit guess work with timing of ovulation, you should have progesterone testing done on the female. I would also suggest having a vaginal culture done to check for any higher than normal levels of bacteria, that would/could cause infertility in either the male or female....and lessen the chance of conception.
Also....please have your female tested for Brucellosis......most breeders will not allow a female to be bred to their stud dog without a negative test result.
I have had females ready to be bred as early as 8 days in...and as late as 26 days....each female is different, and each cycle is different.
Huerta Hof German Shepherds
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....where breeding is still considered an art....