Solution.
Recall that S4 has 5 conjugacy classes. Thus, by Artin-Wedderburn and algebraic closure of C, we have
CS4≃Mn1(C)×⋯×Mn5(C)
with n1≤⋯≤n4 and 24=∣S4∣=n12+⋯+n52. If ni≤2 for each i, then n12+⋯+n52≤20<24, so at least one ni is larger than 2, say n5. Note that n5≤4, since 52>24, so there are two possibilities for n5: if n5=4, then we have n12+⋯+n42=24−16=8. At least one of these must be larger than 1, so n4=2, but then we'd have n12+n22+n32=4 so this case isn't possible.
If n5=3, then we have n12+⋯+n42=24−9=15. By quickly checking the possibilities, we see n4=2 isn't possible, so n4=3 also. From here, we see that we have n1=n2=1, n3=2, n4=n5=3. Thus, our character table is of the form
χ1χ2χ3χ4χ5id11233(1,2)1(1,2)(3,4)1(1,2,3)1(1,2,3,4)1
where χi is a character (with χ1 the trivial character).
Recall the sign homomorphism S4→{±1}, which gives a 1-dimensional character. This gives the row
χ2id1(1,2)−1(1,2)(3,4)1(1,2,3)1(1,2,3,4)−1
We also have a (reducible) representation ρ of S4 in C4 by sending each permutation to its corresponding permutation matrix. This representation is reducible: let V=span{e1+e2+e3+e4} and decompose C4≃V⊕W where W is the orthogonal complement to V. Note that ρ∣V is the trivial representation and that W=span{e1−e2,e1−e3,e1−e4}.
Let χ4=ρ∣W. Then
χ3(id)χ3((1,2))χ3((1,2)(3,4))χ3((1,2,3))χ3((1,2,3,4))=3=χ3((2,3))=1=χ3((1,4)(2,3))=−1=χ3((2,3,4))=0=−1
and
⟨χ4,χ4⟩=241(1⋅32+6⋅1+8⋅0+6⋅1+3⋅1)=1,
so χ4 is actually an irreducible 3-dimensional representation. This also gives χ5, since χ2χ4 is another character. We now have the table
χ1χ2χ3χ4χ5id11233(1,2)1−1a1−1(1,2)(3,4)11b−1−1(1,2,3)11c00(1,2,3,4)1−1d−11
Finally, to complete the table, we just need to use the orthogonality relations. Columns 1 and 2 give 2a=0, so a=0; columns 1 and 3 give 2+2b−6=0, so b=2; columns 1 and 4 give 2+2c=0, so c=−1; and columns 1 and 5 give 2d=0, so d=0. Thus, the character table is
χ1χ2χ3χ4χ5id11233(1,2)1−101−1(1,2)(3,4)112−1−1(1,2,3)11−100(1,2,3,4)1−10−11