The inner Zn atom of the [Zn2ClL] unit is coordinated by the imino N and phenolate O atoms of L and one azido N atom, forming a square pyramidal geometry. <...> The outer Zn atom of the [Zn2ClL] unit is coordinated by two phenolate O of L, one Cl ligand, and one N atom of the bridging azide group, forming a tetrahedral geometry. <...> The [Zn2ClL] units are linked through endon azido bridges, forming 1D chains running along the c axis. <...> Bis-Schiff bases derived from salicylaldehyde and its derivatives with diamines are a kind of versatile ligands in coordination chemistry. <...> The preferred way to construct polynuclear complexes is the use of suitable bridging groups, such as 3 N, NCS–, N 2(CH) , dicarboxylate, 4,4-bipy, and so on [ 4—7]. <...> Among the bridging groups, the azide ligand has received particular interest because it is very useful to design extended polynuclear complexes. <...> It can bind up to three metal atoms when acting as a monatomic bridge (end-on, EO) and up to six using the two terminal nitrogen atoms to bridge (end-to-end, EE) (Scheme 1) [ 8—10]. <...> A major obstacle to a more comprehensive study of such azide-based polymeric coordination complexes is the lack of rational synthetic procedures, since with the present state of knowledge it is hardly possible to determine which coordination mode will be adopted by the azide ligand and whether the sought-after alternating chain structure will finally be formed or not. <...> Schiff base H2L ligand analyses were performed on a Perkin-Elmer 240C elemental analyzer. <...> Single crystal structural X-ray diffraction was carried out on a Bruker D8 VENTURE PHOTON diffractometer. <...> Molar conductance of the complexes at a concentration of 10–3 M in absolute methanol was measured with a Shanghai DDS-11A conductometer. <...> Synthesis of the complex. 5-Fluorosalicylaldehyde (2.0 mmol, 0.28 g) and 1,3-diaminopropan2-ol (1.0 mmol, 0.09 g) were mixed and magnetically stirred in methanol (30 ml) for 30 min. Then, a methanol solution (20 ml) containing sodium azide (1.0 mmol, 0.065 g) and zinc chloride (1.0 mmol, 0.14 g) were added dropwise <...>