Synthesis of the large-ring thiacyclophanes HT[9.9]MC, 13, and HT[9.9]OC, 14, containing two meta- or orthoxylyl groups and six sulfur atoms are reported. These compounds were obtained in good yields via a stepwise procedure, employing hydroxy and chloro intermediates, as opposed to a one-pot approach. The crystal structures of both compounds were determined. 13 crystallized in the space group P2(1)/c with a = 9.397(2) angstrom, b = 17.157(4) angstrom, c = 9.770(2) angstrom, beta = 124.36(1)degrees, V = 1300(1) angstrom3, and Z = 2. The structure refined to R = 5.24% and R(w) = 6.47% for 920 reflections with F(o)2 > 3sigma(F(o)2). 14 crystallized in the space group P2(1)/c with a 5.032(3) angstrom, b = 8.567(7) angstrom, c = 29.87(2) angstrom, beta = 98.29(7)degrees, V = 1275(2) angstrom3, and Z = 2. The structure refined to R = 3.11% and R(w) = 3.78% for 1319 reflections with F(o)2 > 3sigma(F(o)2). The effect of the xylyl groups on the conformation of the macrocycles are described. HT[9.9]OC acts as a ditopic S6 ligand binding to two [M(CH3CN)]+ (M = Cu, Ag) moieties to yield the dinuclear complexes [Cu2(CH3CN)2(HT[9.9]OC)][ClO4]2 and [Ag2(CH3CN)2(HT-[9.9]OC)][BF4]2. [Ag2(CH3CN)2(HT[9.9]OC)][BF4]2 crystallized in the space group C2/c with a = 27.257(4) angstrom, b = 10.809(4) angstrom, c = 14.287(4) angstrom, beta = 104.60(2)degrees, V = 4073(2) angstrom3, and Z = 4. The structure refined to R = 4.81% and R(w) = 5.16% for 1352 reflections with F(o)2 > 3sigma(F(o)2). The two Ag atoms are each coordinated by three S atoms and an CH3CN group with the o-xylyl group chelating rather than bridging. The CH3CN ligands are oriented on opposite sides of the macrocyclic ring in an anti-conformation.