For me it seems that it compiles correctly, if you move the \centering out of the tabular and change \hrule to \toprule. However, if you use four c-columns, the second column is wider than the other, and the third column is a little narrower. Therefore, the second heading (190cm) seems to be a little bit offset, but I think this is just an optical illusion. Maybe you should consider using four fixed width columns, as I do in the test example.
In the test example, I have set the tabular with fixed width columns (wc{<wd>}), to demonstrate that the alignment is correct. For the same reason, I added the vertical lines. They are there for illustration purposes and should be removed:
Example 1 – test version

\documentclass{article}
\usepackage{booktabs}
\usepackage{array}
\begin{document}
\centering
\begin{tabular}{*{4}{wc{1cm}|}}
\toprule
\multicolumn{2}{c}{290cm} & \multicolumn{2}{c}{190cm}\\
n & m & n & m\\
\cmidrule(lr){1-2}
\cmidrule(l){3-4}
14 & 100 & 6 & 50 \\
2 & 17 & 5 & 45\\
4 & 30 & & \\
9 & 80 & & \\
\end{tabular}
\end{document}
Example 2 – final version A

\documentclass{article}
\usepackage{booktabs}
\usepackage{array}
\begin{document}
\centering
%\begin{tabular}{*{4}{wc{1cm}|}}
\begin{tabular}{*{4}{c}}
\toprule
\multicolumn{2}{c}{290cm} & \multicolumn{2}{c}{190cm}\\
n & m & n & m\\
\cmidrule(r){1-2}
\cmidrule(l){3-4}
14 & 100 & 6 & 50 \\
2 & 17 & 5 & 45\\
4 & 30 & & \\
9 & 80 & & \\
\bottomrule
\end{tabular}
\end{document}
Example 3 – final version B
Here is a version with fixed width columns. 15 pt in minimum width before you get Overfull hboxes:

\documentclass{article}
\usepackage{booktabs}
\usepackage{array, caption}
\begin{document}
\begin{table}
\caption{A table\label{tab:a-table}}
\centering
\begin{tabular}{*{4}{Wc{15pt}}}
\toprule
\multicolumn{2}{c}{290cm} & \multicolumn{2}{c}{190cm}\\
\multicolumn{1}{c}{n} & \multicolumn{1}{c}{m} & \multicolumn{1}{c}{n} & \multicolumn{1}{c}{m}\\
\cmidrule(r){1-2}
\cmidrule(l){3-4}
14 & 100 & 6 & 50 \\
2 & 17 & 5 & 45\\
4 & 30 & & \\
9 & 80 & & \\
\bottomrule
\end{tabular}
\end{table}
\end{document}
\hrulecan't be used there; you shouldn't use\centeringwithin yourtabularenvironment; and you should mention that you're usingbooktabs. All that said, when the\hruleandcenteringare removed, your table appears precisely as it should, as far as I can tell, including the "290cm" being centered over its two columns. What precisely is going wrong? – dgoodmaniii Nov 23 '19 at 20:05\cmidruleis not a standard command for example) – David Carlisle Nov 23 '19 at 20:06190 cmis wider than the combined widths of the first and second column. The multicolumn entry will therefore appear os off center with respect to the corresponding columns. See also Table column widths disproportionate due to multicolumn cell being too long – leandriis Nov 23 '19 at 20:14