In base R, you can use the following to create an index of "every 4 rows":
(seq_len(nrow(mydf))-1) %/% 4
# [1] 0 0 0 0 1 1 1 1 2 2 2 2
Using that, you can use ave
to get the desired result:
mydf$SD <- ave(mydf$Count, (seq_len(nrow(mydf))-1) %/% 4, FUN = sd)
mydf
# Obs Count SD
# 1 1 56 16.680827
# 2 2 29 16.680827
# 3 3 66 16.680827
# 4 4 62 16.680827
# 5 5 49 29.545163
# 6 6 12 29.545163
# 7 7 65 29.545163
# 8 8 81 29.545163
# 9 9 73 6.238322
# 10 10 66 6.238322
# 11 11 71 6.238322
# 12 12 59 6.238322