| Summary: | Two unique structures were isolated from the phosphorylation reaction of 10<i>H</i>-phenothiazine. The 5,5-dimethyl-2-(10<i>H</i>-phenothiazin-10-yl)-1,3,2-dioxaphosphinane 2-oxide (<b>2a</b>) illustrates the product of <i>N</i>-phosphorylation of phenothiazine. Moreover, a potential product of <b>2a</b> instability, a thiophosphoric acid <b>2b</b>, was successfully isolated and structurally characterized. Molecule <b>2a</b>, similarly to sulfoxide derivative <b>3</b>, possesses interesting phosphorescence properties due to the presence of d-pπ bonds. The X-ray, NMR, and DFT computational studies indicate that compound <b>2a</b> exhibits an anomeric effect. Additionally, the syntheses of selected symmetrical and unsymmetrical pyridine-embedded phenazines were elaborated. To compare the influence of phosphorus and sulfur atoms on the structural characteristics of 10<i>H</i>-phenothiazine derivatives, the high-quality crystals of (4a,12a-dihydro-12<i>H</i>-benzo[5,6][1,4]thiazino[2,3-<i>b</i>]quinoxalin-12-yl)(phenyl)methanone (<b>1</b>) and selected phenazines 5,12-diisopropyl-3,10-dimethyldipyrido[3,2-<i>a</i>:3′,2′-<i>h</i>]phenazine (<b>5</b>) and 5-isopropyl-<i>N,N</i>,3-trimethylpyrido[3,2-<i>a</i>]phenazin-10-amine (<b>6a</b>) were obtained. The structures of molecules <b>1</b>, <b>2a</b>, 2-mercapto-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (<b>2b</b>), 3,7-dinitro-10<i>H</i>-phenothiazine 5-oxide (<b>3</b>), <b>5</b> and <b>6a</b> were determined by single-crystal X-ray diffraction measurements.
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