Generation of pure spin states is an important step towards coherent control of single spin systems. Especially for nitrogen-vacancy defects in diamond, where readout of single spins using optical detection is available, fast initialization of spin is significant in the context of quantum computing applications. In this system the spin polarization is caused by an intersystem crossing process via the metastable singlet state 1A. The slowest relaxation rate is the intersystem to the triplet ground-state 3A on a timescale of 400 ns. The intersystem crossing process mainly populates the ms = 0 spin sublevels of the paramagnetic ground state. Although no direct nuclear spin polarization is seen for low magnetic fields, frequency selective microwave pulses can be used to transfer electron spin polarization to ¹³C nuclear spin states.