Condensation of N‐p‐nitrophenyl‐C‐ethoxycarbonylnitril­im­ine with 2‐methylthio‐4‐phenyl‐3H‐1,5‐benzodiazepine leads to the title compound, C26H23N5O4S. It has been established that 1,3‐dipolar cycloaddition occurs on the C4 =N5 double bond of the 1,5‐benzodiazepine.

Key indicatorsSingle-crystal X-ray study T = 293 K Mean '(C±C) = 0.004 A Ê R factor = 0.023 wR factor = 0.058 Data-to-parameter ratio = 8.3For details of how these key indicators were automatically derived from the article, see

Key indicatorsSingle-crystal X-ray study T = 293 K Mean '(C±C) = 0.004 A Ê R factor = 0.067 wR factor = 0.130 Data-to-parameter ratio = 16.0For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Condensation of N-aryl-C-(ethoxycarbonyl)nitrilimines with 4-phenyl-1,2-dihydro-3H-1,5-benzodiazepine-2-thione lead to the title compounds, C(25)H(21)ClN(4)O(2)S, (IIIa), and C(26)H(23)N(5)O(4)S, (IIIb), respectively. Crystals of both compounds were obtained by evaporation of ethanol solutions at room temperature. In the structures of both compounds, a non-bonding interaction is observed between the S atom and the imino N atom. It is established that 1,3-dipolar cycloaddition occurs on the C=S double bond of the 1,5-benzodiazepine-2-thione.