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The six different crystals of the versatile clathrate host racemic 1,1‘-binaphthyl-2,2‘-dicarboxylic acid (BNDA) that are obtained from its solution in 1,4-dioxane at varying crystallization temperatures from 15 to 35 °C are reported. They involve four solvates (1, 2BNDA/dioxane; 2, BNDA/dioxane; 3, 2BNDA/2dioxane; 4, BNDA/2dioxane), one mixed 1,4-dioxane solvate with water (5, BNDA/3dioxane/H3O+), and one guest-free form. The framework structures are characterized by 0D associates (1, 3, and 4) that either include (3, 4) or don't include (1) guest molecules and by 1D zigzag chains with (5) or without (2) participation of guest molecules. The pseudotetramorphic solvates 1−4 are formed in accordance with a previously formulated rule for pseudopolymorphic clathrates, which is as follows: (i) the guest:host ratio decreases as the crystallization temperature increases, and (ii) the higher the formation temperature of the clathrate modification, the closer the space occupied by guest molecules.

At room temperature trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid forms different clathrates with ethyl and butyl acetate in a 1:1 host-guest ratio. Increasing the formation temperature up to 40°C gives rise to pseudodimorphic clathrates with half the content of the guest component. All the clathrates studied feature intersecting channels of guest molecules within their structures.

Depending on crystallization conditions, dianilinegossypol and ethylacetate form low (ambient temperature, α-phase) and high temperature (t = 35°C, β-phase) clathrate modifications. The structure of the α-phase has been discussed earlier [1]. Crystals of the 1 : 1 β-phase complex, C42H40O6N2·C4O2H8, are monoclinic, space group P21/c, a = 11.362(6), b = 19.479(9), c = 19.085(9) A, β = 103.21(4)°, V = 4112(3)A3, Z = 4, R = 0.084 for 3210 observed reflections.

Crystal structures of the α- and β-phase inclusion complexes of dianilinegossypol with acetone obtained at 20° and 30 °C, respectively, have been determined by X-ray structure analysis. Crystal data of the α-phase complex are: C42H40O6N2⋅2C3H6O, orthorhombic, space group Pccn, a = 29.501(9), b = 10.866(2), c = 13.756(3) A, V = 4409(1) A3, Z = 4, Dx = 1.18 g cm-3. The structure has been refined to a final R value of 0.117 for 1401 observed reflections. The host–guest ratio for the β-phase complex is the same (1 : 2) and the crystals are monoclinic, space group C2/c, a = 28.352(6), b = 11.836(2), c = 13.196(1) A, β = 93.05(1)°, V = 4422(2) A3, Z = 4, Dx =1.18 g cm-3. The structure has been refined to a final R value of 0.077 for 1414 observed reflections.

Nonsymmetrical aldehyde derivatives of gossypol, a yellow polyphenolic pigment of cottonseed, were synthesized by reactions with ammonia, aniline, 4-aminoantipyrine, and barbituric acid. Their structures were determined by UV spectrophotometry and IR and (1)H NMR spectroscopy methods. Their acute toxicities in white mice were compared with those of gossypol and the corresponding symmetrical analogues. It was demonstrated that in general, the fewer free aldehyde groups that contained the gossypol derivative, the lower its acute toxicity. Only in the case of a nonsymmetrical gossypol derivative bearing a 4-aminoantipyrine residue did we observe a deviation from the above correlation: its symmetrical counterpart was even more toxic, but still less toxic than gossypol.

I. Ya. E. Leeis, A. Ya. Bruvere, and Yu. A. Bankovskii, Izv. Akad. Nauk Latv. SSR, 19 (1981). 2. Yu. A. Bankovskii, The Chemistry of Intracomplex Compounds of 8-Mercaptoquinoline and Its Derivatives [in Russian], Zinatne, Riga (1978). 3. D. Grdenic, Quart. Rev., 19, 303 (1965). 4. L. Pauling, The Nature of the Chemical Bond, 3rd edn., Cornell Univ. Press, Ithaca (1960). 5. A. D. Ozola, Ya. K. Ozols, and A. F. levin'sh, Izv. Akad. Nauk Latv. SSR, Ser. Khim., 8 (1973). 6. R. Cr~nbaek and J. D. Dunitz, Helv. Chim. Acta, 47, 1889 (1964). 7. A. J. Canty and G. B. Deacon, Inorg. Chim. Acta, 4_~5, 225 (1980). 8. Yu. V. Zefirov and P. M. Zorkii, Zh. Strukt. Khim., 15, 118 (1974). 9. M. A. Porai-Koshits, Koord. Khim., i, 842 (1978). I0. Yu. V. Zefirov and P. M. Zorkii, Zh. Strukt. Khim., 17, 994 (1976). II. D. B. Boyd, J. Phys. Chem., 82, 1407 (1978).