Crystal and Molecular Structure of Four Organic Salts Assembled from Cyclohexylamine and Organic acids

Four compounds, [(HL) (3) (3+) center dot (cba(-))(3)center dot 2H(2)O] (1, cba = o-chlorobenzoate), [(HL)(+)center dot(NSA(-))] (2, NSA(-) = 5-nitrosalicylate), [(HL) (2) (2+) center dot(3,5-dns(2-))] (3, 3,5-dns(2-) = 3,5-dinitrosalicylate), and [(HL) (2) (2+) center dot(nda(2-))] (4, nda(2-) = 1,5-naphthalenedisulfonate) were obtained from self-assembly of the corresponding acids with the cyclohexylamine, and their structures were fully characterized. All four compounds are organic salts, with proton transfer occurring to the NH2 of the cyclohexylamine moiety. All structures adopted hetero supramolecular synthons. Compound 1 crystallizes in the triclinic, space group P-1, with a = 10.151(3) , b = 13.160(4) , c = 17.172(5) , alpha = 72.159(4)A degrees, beta = 79.546(4)A degrees, gamma A = 78.285(4)A degrees, V = 2120.5(11) (3), Z = 2. Compound 2 crystallizes in the monoclinic, space group P2(1)/c, with a = 13.501(2) , b = 6.3144(15) , c = 19.601(3) , beta = 123.900(13)A degrees, V = 1386.9(4) (3), Z = 4. Compound 3 crystallizes in the monoclinic, space group P2(1)/n, with a = 14.6439(11) , b = 6.9231(4) , c = 21.3012(18) , beta = 96.4800(10)A degrees, V = 2145.7(3) (3), Z = 4. Compound 4 crystallizes in the monoclinic, space group P2(1)/n, with a = 5.3477(5) , b = 19.9238(16) , c = 11.1761(9) , beta = 95.7230(10)A degrees, V = 1184.84(17) (3), Z = 2. Analysis of the crystal packing of 1-4 displays that there are extensive N-H center dot center dot center dot O hydrogen bonds between the acids and the cyclohexylamine in all of the salts. Except the classical hydrogen bonding interactions, the secondary propagating interactions also play significant roles in structure extension. The four salts displayed 2D/3D framework structures for the synergistic effect of the various noncovalent interactions. The crystal structures of the cyclohexylamine salts with o-chlorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, and 1,5-naphthalenedisulfonic acid show extensive classical hydrogen bonding as well as C-H center dot center dot center dot O, CH2 center dot center dot center dot O, Cl center dot center dot center dot O, NH3 center dot center dot center dot pi, CH2 center dot center dot center dot pi, and pi center dot center dot center dot pi interactions, giving 2D sheets or 3D networks.