The novel intermetallic compounds Na6ZnSn2 (1), Na4.24K1.76(1)ZnSn2 (2), and Na20Zn8Sn11 (3) were obtained from direct fusion of the pure elements, and their structures were determined by single crystal X-ray diffraction. All three compounds adopt new structure types and contain linear anionic {Sn-Zn-Sn}(6-) units with rather short Zn-Sn contacts (2.55-2.58 angstrom), separated by alkali metal counterions. Compound 3 comprises layers of interconnected heteroatomic {Zn7Sn5} icosahedra as an additional unique structural motif. The bonding situation in this 16 valence-electron anion is analyzed by quantum chemical methods. The results of NBO, AIM, and ELF calculations (Gaussian03 on HF/3-21G level) reveal covalent bonding between Sri and Zn. The relationship to isovalent CO2 is discussed. Band structure calculations on the density functional theory level (LMTO) show that 1 can be understood as a Zintl phase containing a {Sn-Zn-Sn}(6-) anion; however, Na-Sn contacts must also be considered. Magnetic susceptibility measurements show a temperature-independent, weak diamagnetism for Na6ZnSn2 (1).