Lewis Base Adducts of Group 1B Metal(I) Compounds. 9. Synthesis and crystal structures of adducts of copper(I) thiocyanate with substituted pyridine bases

Abstract

The crystal structures of the title compounds, Cu(SCN)L, L = 2-methylpyridme (l),2 ,6-dimethylpyridine (2), and Cu(SCN)b, L = 2-, 3-, and 4-methylpyridine (3-5, respectively), 2,4-dimethylpyridine (6), quinoline (7), have been established by single-crystal X-ray diffraction at 295 K and refined by full-matrix least squares to residuals of 0.026,0.039,0.048,0.032, 0.054,0.058, and 0.029 for 1164, 1339, 1499, 1731, 903, 1748 and 468 independent "observed" reflections, respectively. Crystals of 1 are triclinic, PI, with a = 9.452 (3) A, b = 8.077 (3) A, c = 5.779 (1) A, a = 104.33 (2)O, @ = 96.64 (2)O, y = 100.83 (3)O, and 2 = 2; the structure is a polymer consisting of pairs of CuL(SCN)CuL(SCN) strands linked by centrosymmetric four-membered Cu2S2a nd eight-membered CU(SCN)~CrUin gs. Crystals of 2 are monoclinic, P2,/c, with a = 7.721 (2) A, b = 7.753 (2) A, c = 16.1 13 (4) A, @ = 90.67 (2)O, and 2 = 4; the structure is a single-stranded polymer-CuL(SCN)CuL(SCN). Crystals of 3 are orthorhombic, Fdd2, with a = 43.68 (1) A, b = 16.402 (4) A, c = 8.064 (3) A, and 2 = 16. Crystals of 4 are monoclinic, P2]/n, with a = 17.68 (1) A, b = 5.874 (4) A, c = 14.367 (8) A, @ = 112.91 (4)O, and 2 = 4. Crystals of 5 are monoclinic, El, with a = 14.59 (2) A, b = 5.823 (6) A, c = 8.953 (10) A, @ = 106.44 (lo)', and 2 = 2. Crystals of 6 are monoclinic, P21/c, with a = 28.93 (3) A, b = 5.867 (4) A, c = 20.19 (3) A, @ = 112.70 ( 8 ) O , and 2 = 8. Crystals of 7 are orthorhombic,P 212121wr ith a = 16.219 (4) A, b = 12.838 (3) A, c = 8.032 (2) A, and 2 = 4. In spite of the diverse crystal symmetries found for 3-7, all contain single-stranded CuL2(SCN)CuLz(SCN)CuLpzo lymers, with different conformational types. All complexes were synthesized by reaction of copper(1) thiocyanate with the parent base, with or without the presence of acetonitrile as solvent.