\tikzmark always works both before and after a single cell or a \multirow, and also after a \multicolumn.
But before a \multicolumn it gives the error:
! Misplaced \omit.
\multispan ->\omit
\@multispan
l.55 \tikzmark{cmc}\multicolumn{2}{c}{A and B}
& C\tikzmark{dmc} \\
I expect to see \omit only after tab marks or the \cr of
an alignment. Proceed, and I'll ignore this case.
Here is a MWE:
\documentclass{book}
\usepackage{tikz}
\usetikzlibrary{tikzmark, calc}
\usepackage{array}
\usepackage{multirow}
\renewcommand{\arraystretch}{1.4}
\begin{document}
All these ones work:
\begin{tabular}{ccc}
\tikzmark{a}A & B & \tikzmark{b}C \\
D & E & F \\
\end{tabular}
\begin{tikzpicture}[overlay,remember picture]
\draw (pic cs:a) -- (pic cs:b);
\end{tikzpicture}
\begin{tabular}{ccc}
A\tikzmark{c} & B & C\tikzmark{d} \\
D & E & F \\
\end{tabular}
\begin{tikzpicture}[overlay,remember picture]
\draw (pic cs:c) -- (pic cs:d);
\end{tikzpicture}
\begin{tabular}{ccc}
\tikzmark{amr}\multirow{2}{*}{A and D} & B & \tikzmark{bmr}C \\
& E & F\\
\end{tabular}
\begin{tikzpicture}[overlay,remember picture]
\draw (pic cs:amr) -- (pic cs:bmr);
\end{tikzpicture}
\begin{tabular}{ccc}
\multirow{2}{*}{A and D}\tikzmark{cmr} & B & C\tikzmark{dmr} \\
& E & F\\
\end{tabular}
\begin{tikzpicture}[overlay,remember picture]
\draw (pic cs:cmr) -- (pic cs:dmr);
\end{tikzpicture}
\begin{tabular}{ccc}
\multicolumn{2}{c}{A and B}\tikzmark{amc} & C\tikzmark{bmc} \\
D & E & F \\
\end{tabular}
\begin{tikzpicture}[overlay,remember picture]
\draw (pic cs:amc) -- (pic cs:bmc);
\end{tikzpicture}
But this one doesn't work:
\begin{tabular}{ccc}
\tikzmark{cmc}\multicolumn{2}{c}{A and B} & C\tikzmark{dmc} \\
D & E & F \\
\end{tabular}
\begin{tikzpicture}[overlay,remember picture]
\draw (pic cs:cmc) -- (pic cs:dmc);
\end{tikzpicture}
\end{document}

\multicolumnmust be the first command in a row there. I think you need some\noalignsorcery. Our Black Sorcerers (David Carlisle and egreg) will find a way ;-) – Apr 21 '17 at 13:00\multicolumn: must it always be the first command in a cell? – CarLaTeX Apr 21 '17 at 13:06\relaxbefore it. – David Carlisle Apr 21 '17 at 16:28