Hydrazones, ArNHN=CRCH2COX, from Reactions of Arylhydrazines, ArNHNH2, with 1,3-Dicarbonyl Compounds, RCOCH2COX(X = OR1 or NHPh): Crystal Structures of (E)-4-O2NC6H4NHN=CMeCH2CO2R1 (R1 = Me or Et) and (E)-PhNHN=CPhCH2CONHPh

Abstract

The molecular and crystal structures of (E)-4-O2NC6H4NHN=CMeCH2CO2R1 (4: R1 = Me; 5: R1 = Et) and (E)-PhNHN=CPhCH2CONHPh (6) are reported from data collected at 120(2) K. The major intermolecular interactions in both 4 and 5 involve the hydazonyl NH and the carbonyl oxygen, with formation of symmetric dimers. Due to 4 and 5 each having different sets of additional intermolecular interactions, different supramolecular arrays are produced: molecules of 4 are linked into a three-dimension structure, while zig-zag chains of molecules of 5 are obtained. Chains of molecules of 6, prepared from PhNHNH2 and PhCOCH2CONHPh, are obtained from intermolecular hydrogen bonds involving amido NH and carbonyl oxygen moieties. Further interactions, C–H–π(arene), C–H–O and π–π stacking interactions in 6 produces a three dimensional array. Compound 4 crystallizes in the triclinic space group P − 1 with a = 7.7027(2) Ǻ, b = 7.8103(2) Ǻ, c = 11.1761(3) Ǻ, α = 77.054(2)°, β = 79.425(2)°, γ = 81.097(2)°. Compound 5 crystallizes in the triclinic space group P − 1 with a = 5.6323(2)Ǻ, b = 9.9695(3)Ǻ, c = 11.0286(4)Ǻ, α = 91.859(2)°, β = 102.034(2)°, γ = 98.898(3)°. Compound 6 crystallizes in the monoclinic space group P21/c with a = 10.4255(8)Ǻ, b = 10.4255(8)Ǻ, c = 9.3368(5)Ǻ, β = 113.780(4) °. Controlled reactions of arylhydrazines, ArNHNH2 with RCOCH2COX (X = OR or NHPh) produce ArNHN=CRCH2COX. The molecular and crystal structures of three such non-cyclised products are reported. While the major intermolecular interactions in each case involve the hydazonyl NH and the carbonyl oxygen, different three dimensional supramolecular arrangements are found.