  We investigate the evolution of entanglement in multiple-quantum (MQ) NMR
experiments in crystals with pairs of close nuclear spins-1/2. The initial
thermodynamic equilibrium state of the system in a strong external magnetic
field evolves under the non-secular part of the dipolar Hamiltonian. As a
result, MQ coherences of the zeroth and plus/minus second orders appear. A
simple condition for the emergence of entanglement is obtained. We show that
the measure of the spin pair entanglement, concurrence, coincides qualitatively
with the intensity of MQ coherences of the plus/minus second order and hence
the entanglement can be studied with MQ NMR methods. We introduce an
Entanglement Witness using MQ NMR coherences of the plus/minus second order.
