Four new deficient compounds in the R6B2C2QI4 family, LasCaSn2.75S4 1, Y6A10.67Ge2S14 2, Er5.33Si4S14 3 and Er4Ge4SI4 4, have been obtained via a precursor/flux method. Single-crystal analysis indicated that their crystal structures consist of three types of building blocks： RS7 （R = La/Ca for 1, R = Y for 2, R = Er for 3 and 4） mono-triangonal prism, CS6 （C = A1 for 1, C = Sn（2） for 2, C = Si（2） for 3, C = Ge（2） for 4） octahedron, and BS4 （B = Si for 1, B = Sn（1） for 2, B = Si（1） for 3, B = Ge（1） for 4） tetrahedron, as any other compounds belong to the R6B2C2Q14 family.
Two d10 metal-organic complexes, [ZnBr2（DICNQ）2] （1） and [AgCN（DICNQ）]2（2）, were prepared from ZnBr2 and AgCN with 6,7-dicyanodipyridoquinoxaline （DICNQ） by solvothermal reactions, respectively, and characterized by single-crystal X-ray diffraction analyses, IR spectroscopy, and photoluminescent measurement. Compound 1 crystallizes in monoclinic, space group C2/c with a=8.436（2）, b=13.011（3）, c=27.565（6）,β=97.90（3） , V=2997.0（1）3 , Z=4, Mr=789.73, Dc=1.750 g/cm3 ,μ=3.533 mm-1 , F（000）=1552, S=1.007 and T=293（2） K. The final R=0.0739 and wR=0.1380 for 1561 observed reflections with I 〉 2σ（I）. Compound 2 crystallizes in monoclinic, space group P21/c with a=24.202（6）, b=7.1619（17）, c=18.339（5）,β=111.8380（10） , V=2950.6（1）3 , Z=4, Mr=832.32, Dc=1.874 g/cm 3 ,μ=1.382 mm-1 , F（000）=1632, S=1.002 and T=293（2） K. The final R=0.0389 and wR=0.1257 for 4812 observed reflections with I 〉 2σ（I）. Both compounds form packing structures by π…π stacking interactions and C-H…N or C-H…Br hydrogen-bonding interactions. Compounds 1 and 2 show similar photoluminescent spectra with emission maxima at ca. 430 nm in diluted acetonitrile solution （1×10-5 mol L-1 ） at room temperature.
