The new ditopic heteroscorpionate ligand, (3-methoxy-4-hydroxyphenyl)bis(3,5-dimethylpyrazolyl)methane (L5v), and four coordination polymers of silver Ag(I) derived therefrom, have been synthesized and characterized by X-ray diffraction, ESI-MS, IR spectroscopy and elemental analysis. The presence of different anions (i.e. BF4−, CF3SO3−, NO3−, or SbF6−) lead to different crystal packing schemes due to different H-bonding patterns that depend on the relative charge delocalization and/or shape of the anion.