Syntheses and Crystal Structures of Two New Sodium Borates [Na 2(H2O)3][B5O8(OH)2] and Na[enH2][B7O10(OH)4]. -Crystals of [Na 2(H2O)3][B5O8(OH)2] (I) are grown from stoichiometric aq. solutions of Na2B4O7 and H3BO3 (slow evaporation; 3 weeks; 60% yield). Na[enH2][B7O10(OH)4] (II) is prepared by solvothermal reaction of a 1:10:3 molar mixture of NaOH, H 3BO3, and en in Py/H 2O (autoclave, 200 C, 7 d; 63% yield). Compound (I) crystallizes in the monoclinic space group C2/c with Z = 4 (single crystal XRD). The structure contains {Na 2B5O8(OH)2·3H2O}n chains formed by the connection of [B5O8(OH)2] 2building blocks via common Na + ions. Compound (II) crystallizes in the triclinic space group P1 (Z = 2) and comprises infinite {Na[B7O10(OH)4]}n sheets which are formed by linkage of [B 7O10(OH)4] 3building blocks via Na cations. The compounds are further characterized by FT-IR and TG. -(WANG, Y.-J.; JIA, A.-Q.; CHEN, X.-S.; SHI, H.-T.; ZHANG*, Q.-F.; Z. Naturforsch., B: Chem. Sci. 71 (2016) 1, 15-22, http://dx.