The design of new types of metal-organic networks and the search for unusual crystal architecture represents an important task for modern inorganic and materials chemistry research. A group of new monosubstituted phenylcyanoximes, containing F, Cl, and Br atoms at the 2, 3, or 4 positions, were synthesized using the high yield nitrosation reaction with CH3-ONO and were spectroscopically (H-1 NMR, C-13 NMR, UV-visible, IR, mass spectrometry) and structurally characterized. Results of X-ray analysis revealed nonplanar trans-anti geometry for 2-chlorophenyl(oximino)acetonitrile, H(2Cl-PhCO); a nonplanar anti configuration for 4-chlorophenyl(oximino)acetonitrile, H(4Cl-PhCO); and planar cis-syn geometry for 3-fluorophenyl(oximino)acetonitrile, H(3F-PhCO). All arylcyanoximes undergo deprotonation in solutions with the formation of colored anions exhibiting pronounced negative solvatochromism in a series of polar protic and aprotic solvents. Nine thallium(l) cyanoximates were obtained using the reaction between hot (similar to 95 degrees C) aqueous solutions of Tl2CO3 and solid powdery monohalogenated arylcyanoximes HL. Crystal structures of two Tl(l) cyanoximates [TI(2Cl-PhCO) and Tl(4Br-PhCO)] contained centrosymmetric dimeric units (TIL)(2) that are connected to a coordination polymer by means of an oxygen atom of the oxime group of the neighboring molecule. Cyanoxime anions act as bridging ligands in both structures where the polymeric motif consists of double-stranded TI-O chains interconnected with the formation of zigzagging Tl2O2 planar rhombes. Thallium atoms form infinite linear arrays with close intermetallic separations. The nearest Tl(l)Tl-..(l) distances are 3.838 and 4.058 angstrom in the Tl(2Cl-PhCO) and Tl(4Br-PhCO) structures, respectively, close to that in metallic thallium (3.456 angstrom). Monosubstituted phenyl groups are well aligned in pi-stacking columns that are perpendicular to the array of Tl(l) atoms and stabilize formed structures. Coordination polyhedrons of thallium(l) in these complexes represent distorted trigonal pyramids with stereoactive lone pair.