Lewis-base adducts of Group 11 metal(I) compounds .68. Synthesis and structural systematics of some 1:3 adducts of silver(I) compounds with triphenylstibine, [(Ph3Sb)(3)AgX], X = Cl, I, SCN, NCS, CN, ONO2

The syntheses and room-temperature single-crystal X-ray structural characterization of 1:3 adducts formed between silver(I) (pseudo-) halides, AgX, and triphenylstibine, SbPh3, are described for X = Cl, I, SCN, NCS, CN, NO3 (1)-(6). The chloride, as its methanol solvate (la), is isomorphous with the arsine analogue: triclinic, <P(1)over bar>, a 13.373(4), b 14.148(6), c 14.702(3) Angstrom, alpha 83.49(3), beta 87.76(2), gamma 76.45(3)degrees; Z = 2, conventional R on \F\ being 0.046 for N-0 5514 independent 'observed' reflections (I > 3 sigma(I)). A new form (1b) of the chloride has also been authenticated: monoclinic, P2(1)/c, a 12.832(2), b 54.24(1), c 18.519(8) Angstrom, beta 129.68(3)degrees; Z = 8 (R 0.065 for N-0 5612). No bromide has been obtained; the iodide (2) is described as monoclinic, P2(1)/n, a 19.611(4), b 14.473(6), c 17.74(1) Angstrom, beta 98.28(3)degrees; Z = 4 (R 0.036 for N-0 6769). The thiocyanate crystallizes from acetonitrile or pyridine as an S-bonded form (3) isomorphous with the arsine analogue: monoclinic, P2(1)/n, a 19.143(7), b 14.288(5), c 18.694(6) Angstrom, beta 98.81(2)degrees; Z=4 (R 0.037 for N-0 4482). From 2-methylpyridine, remarkably, a solvate is obtained in which the thiocyanate is N-bonded (4): triclinic, <P(1)over bar>, a 27.261(5), b 14.767(3), c 13.319(1) Angstrom, alpha 91.53(1), beta 101.58(1), gamma 92.29(2)degrees; Z = 4 (R 0.045 for N-0 6900). The cyanide is also monoclinic, P 2(1)/n, a 19.442(7), b 14.267(3), c 17.741(6) Angstrom, beta 97.63(3)degrees, Z = 4; R 0.057 for N-0 2487. The unsolvated 1:3 nitrate complex (6a) is monoclinic, P 2(1)/n, a 19.602(5), b 14.455(1), c 17.727(2) Angstrom, beta 97.19(2)degrees, Z = 4; R was 0.034 for N-0 6522. The complex is isomorphous with the arsenic and phosphorus analogues, being mononuclear [(Ph3Sb)(3)Ag(O2NO)]. The ethanol solvate (6b) is triclinic, <P(1)over bar>, a 13.352(5), b 14.548(9), c 14.701(4) Angstrom, alpha 81.64(4), beta 84.45(3), gamma 75.32(4)degrees, Z = 2; R was 0.058 for N-0 4702. Ag-Sb range between 2.6980(8) and 2.843(3) Angstrom in the precise determinations; Ag-X are 2.481(4) and 2.52(1) Angstrom (the two chlorides), 2.757(1) (I), 2.533(3)(SCN), 2.21(1) (NCS), 2.09(3) (CN), 2.377(7) Angstrom (unidentate ONO2).