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The formation of liquid crystalline transitions in the phase sequences of many metal carboxylate systems has been the center of tremendous research interests in this area for several decades. Their fascinating structural features, dominated by extensive polymorphism and three dimensional self-assembly lamellar type packing have also attracted researchers to them. However, though these compounds have been known for several decades, there still remain numerous unanswered questions where the phase behaviour-molecular structure correlation is concerned for a family of compounds. Therefore, in this discussion, the structures for a family of long chain (8 - 18 carbons, inclusive) monovalent (Li, Na, K and Ag) metal n-alkanoates are discussed at length based on X-ray powder diffraction, Fourier Transform Infrared and Solid State NMR spectroscopies. Their properties are also assessed comprehensively and correlated to their phase behaviours.