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 n
on-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.
