The following is taken from amsmath and uses \genfrac - a generic fraction function:

\documentclass{article}
\usepackage{amsmath}% http://ctan.org/pkg/amsmath
\DeclareRobustCommand{\stirling}{\genfrac\{\}{0pt}{}}
\begin{document}
% Source: http://en.wikipedia.org/wiki/Stirling_numbers_of_the_second_kind
In mathematics, particularly in combinatorics, a Stirling number of the second kind
is the number of ways to partition a set of $n$~objects into $k$~non-empty subsets and
is denoted by~$S(n,k)$ or~$\stirling{a}{b}$. Stirling numbers of the second kind occur
in the field of mathematics called combinatorics and the study of partitions.
\end{document}
How does this work? \genfrac takes five arguments to create a structure (from the amsmath documentation; section 4.11.3 The \genfrac command, p 14):
The last two correspond to \frac’s numerator and denominator; the
first two are optional delimiters [...]; the third is a line thickness
override [0 implies an invisible rule]; and the fourth argument is a
mathstyle override: integer values 0-3 select respectively
\displaystyle, \textstyle, \scriptstyle, and
\scriptscriptstyle. If the third argument is left empty, the line
thickness defaults to ‘normal’.
So \genfrac\{\}{0pt}{} creates a fraction with an invisible horizontal rule (third argument is 0pt), left and right delimiter given by \{ and \}, respectively and no specific math style (an empty {} fourth argument). \stirling doesn't include a fifth and sixth argument for \genfrac (numerator and denominator), because this is implicitly supplied by the user as the two "arguments" to \stirling.
In a similar manner (perhaps for reference), amsmath defines
\newcommand{\frac}[2]{\genfrac{}{}{}{}{#1}{#2}}
\newcommand{\tfrac}[2]{\genfrac{}{}{}{1}{#1}{#2}}
\newcommand{\binom}[2]{\genfrac{(}{)}{0pt}{}{#1}{#2}}
using \genfrac.
\atopis a bad choice as it left-aligns the "numerator" and "denominator", rather than centring them. – David Richerby Mar 28 '14 at 16:33{n \brace k}, but I guess it's not "real LaTeX" style. – Thomas Ahle Apr 01 '21 at 09:53atopcenters the numerator and denominator, unless you're doing something very wrong. ■ Related question: math mode - Multiset notation in LaTeX - TeX - LaTeX Stack Exchange, amsmath - On \atop again: how to obtain the same result without warning - TeX - LaTeX Stack Exchange – user202729 Dec 13 '22 at 06:54