Wepresent synthesis, x-ray diffraction, magnetisation and specific heat studies on the quasi-twodimensional (2D) S=1/2 antiferromagnet (CuCl)LaNb2O7 and its doping analogues (Cu1xZnxCl) LaNb2O7 (0x0.05), (Cu0.95Mg0.05Cl)LaNb2O7, and (CuCl)La1yBayNb2O7 (0y0.10). The magnetic susceptibility and specific heat of the parent compound and its isovalent or hetereovalent counterparts do not display any signature of magnetic ordering down to 1.8 K. The parent compound and its doping variants exhibit spin-singlet behaviour with a finite gap in the spin excitation spectrum due to dimerisation of the dominant intradimer interactions as evidenced from our magnetic susceptibility and specific heat data. The systematic increase of magnetic susceptibility at low temperature with non-magnetic Zn2+ andMg2+ (S=0) substitution at the Cu2+ site reflect that impurities induce local moments around the non-magnetic sites. While heterovalent Ba2+ substitution at the La3+ site do not result in mobile holes but rather give rise to a Curie term in the susceptibility due to localisation. The low value of spin S=1/2, and absence of long range ordering or spin freezing, and the presence of competing exchange interactions hold special significance in hosting novel magnetic properties in this class of quasi-2D quantum material. © 2016 IOP Publishing Ltd.