Ionic compounds containing radical anions of metal-free phthalocyanine (H2Pc˙(-)): (H2Pc˙(-))(cryptand[2,2,2][Na(+)])·1.5C6H4Cl2 (1) and (H2Pc˙(-))(TOA(+))·C6H4Cl2 (2) have been obtained as single crystals for the first time. Their crystal structures have been determined, and optical and magnetic properties have been investigated. The H2Pc˙(-) radical anions have a slightly bowl-like shape with four pyrrole nitrogen atoms located below the molecular plane, while four phenylene substituents are located above this plane. Changes in the average length of N-C and C-C bonds in H2Pc˙(-) in comparison with those in neutral H2Pc indicate that negative charge is mainly delocalized over the 24-atom phthalocyanine ring rather than the phenylene substituents. The H2Pc˙(-) formation is accompanied by a shift of up to 10 cm(-1) and disappearance of some intense IR-active bands whereas the band of the N-H stretching mode is shifted by 21-27 cm(-1) to larger wavenumbers. New bands attributed to H2Pc˙(-) appear in the NIR spectra of the salts with maxima at 1033 and 1028 nm for 1 and 2, respectively. The formation of H2Pc˙(-) is accompanied by the splitting of the Soret and Q-bands of H2Pc into several bands and their blue-shift up to 32 nm. Narrow EPR signals with g = 2.0033 and linewidth of 0.16-0.24 mT at room temperature in the spectra of the salts were attributed to the H2Pc˙(-) radical anions. According to SQUID measurements they have S = 1/2 spin states with effective magnetic moments of 1.73 (1) and 1.78 (2) μB at 300 K. Magnetic behavior of 1 and 2 follows the Curie-Weiss law with negative Weiss temperatures of -0.9 and -0.5 K, respectively, indicating weak antiferromagnetic interactions of spins. The EPR signal splits into two lines below 120 and 80 K for 1 and 2, respectively and these lines are noticeably broadened below 25 K.