The search on new candidates for selective ligands of benzodiazepine receptors, and potential analgesics, stimulate us to synthesize the naphthalide- and heteronaphthalide-1,4-benzodiazepines. Condensation of 1,4-benzodiazepin-2-one 1 with 1- and 2-naphthalene, 9-anthracene and a number of quinoline and quinoxaline carbaldehydes resulted in 3-substituted 1,4-benzodiazepin-2-ones 2- 10. The structure of compounds 2-10 was confirmed by mass spectrometry and 1H NMR spectroscopy, and for (3Z)-7-bromo-5-phenyl-3-(quinoxalin-5-ylmethylene)-1,3-dihydro-2H-1,4- benzodiazepin-2-one 10 also by the X-ray diffraction method. The compound 10 crystallizes in the triclinic P-1 space group, a=7.9689(6), b=10.8434(8), c=12.5840(9) Å; α=80.627(6), β=75.074(6), =81.439(6), V=1030.1(1) Å3, Z=2 with one molecule per asymmetric unit. The seven-membered benzodiazepine ring in the molecule has the boat conformation. The N(1)–H•••O=C(2)=2.893(4) Å hydrogen bonds unite the molecules into centrosymmetric dimer forming R22(8) supramolecular synthon. The double C2=O2, N4=C5, and C3=C12 bond distances are equal to 1.221 (3), 1.276 (3), and 1.342 (4) Å, respectively. The planar quinoxaline fragments of neighboring center-symmetry related molecules reside in parallel planes with interplanar separation 3.501 Å, nevertheless they do not revealed the pronounced stacking interaction: the shortest centroid•••centroid benzene/benzene and benzene/pyrazine distances equal 4.093 and 4.242 Å, respectively. The C-H•••N6= 3.397 Å interactions unite the dimeric associates in the chain along crystallographic axis c.