Four-layered [3.3]metacyclophane with ethenetetracarbonitrile

The title complex C₄₂H₄₈·2C₆N ₄ {systematic name: heptacyclo[21.13.1.1^5,19.1 ^6,18.1^10,14.1^24,36.1^28,32] dotetraconta-1(37),5(40),6(41),10(42),11,13,18,23,28,30,32(39),36(38) -dodecaene-ethenetetracarbonitrile (1/2)}, consisting of four-layered [3.3]metacyclophane (MCP) with two tetracyanoethylene (TCNE) molecules, was grown from a mixture of MCP and TCNE in chloroform solution. The four-layered [3.3]MCP has an S-shaped structure in which three [3.3]MCP moieties take syn-(chair-boat), anti-(chair-boat) and syn-(chair-boat) conformations. The two outer [3.3]MCP moieties with syn geometry contain benzene rings with a tilt of 32.95(7)°. The central [3.3]MCP moiety has an anti geometry, in which the two benzene rings are oriented parallel to each other at a transannular distance of 2.31Å. The TCNE molecules are stacked on either side of the outer [3.3]MCP units at a distance of 3.19Å on one side and 3.24Å on the other, and showed 0.80:0.20 and 0.44:0.56 disorder, respectively.