3-Methyl-2,2,4,4-tetrakis(methylamino)-1-phenyl-[1,3,2,4]diazadisiletidine (1), 1,3-Dichloro- 2-phenyl-1,1,3,3-tetrakis(dimethylamino)disilazane (2), 3-Methyl-2,2,4,4-tetrakis(dimethylamino)- 1-phenyl-[1,3,2,4]diazadisiletidine (3) and 2,2,4,4-Tetrakis(dimethylamino)-1-phenyl-[ 1,3,2,4]diazadisiletidine (4) have been synthesized as potential precursors for the preparation of porous oxygen-free solids. All compounds were characterized by crystal structure analysis. 1 crystallizes monoclinically, P21/c, a = 8.44(1), b = 19.56(1), c = 10.68(1) Å, β = 109.4(1)° and Z = 4 (R1 = 8.7%, wR2 = 20.7%, 1545 independent reflections). 2 crystallizes triclinically, P1̄, a = 8.011(2), b = 8.424(2), c = 16.082(2) Å, β = 91.08(1)°, β = 93.89(1)°, γ= 105.71(1)° and Z = 2 (R1 = 3.0%, wR2 = 7.9%, 3657 independent reflections). 3 crystallizes monoclinically, P21/c, a = 29.746(2), b = 21.590(2), c = 13.331(2) ) Å, β = 102.95(1)° and Z = 16 (R1 = 4.3%, wR2 = 9.3%, 6667 independent reflections). 4 crystallizes triclinically, P1̄, a = 10.450(1), b = 10.467(1), c = 17.948(1) ) Å, α = 97.43(1)°, β = 98.73(1)°, γ = 90.08(1)° and Z = 4 (R1 = 10.2%, wR2 = 25.8%, 3586 independent reflections). Polycondensation of 1 and ammonolysis and polycondensation of 2 yield amorphous solids with different porosities.