Four-layered [3.3]meta­cyclo­phane with ethene­tetra­carbo­nitrile

Masahiko Shibahara; Motonori Watanabe; Kenta Goto; Teruo Shinmyozu

doi:10.1107/S1600536814009362

. 2014 Apr 30;70(Pt 5):o625–o626. doi: 10.1107/S1600536814009362

Four-layered [3.3]metacyclophane with ethenetetracarbonitrile

Masahiko Shibahara ^a,^*, Motonori Watanabe ^b, Kenta Goto ^c, Teruo Shinmyozu ^c

PMCID: PMC4011271 PMID: 24860414

Abstract

The title complex C₄₂H₄₈·2C₆N₄ {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 2.31 Å. The TCNE molecules are stacked on either side of the outer [3.3]MCP units at a distance of 3.19 Å on one side and 3.24 Å on the other, and showed 0.80:0.20 and 0.44:0.56 disorder, respectively.

Related literature

For the previously reported C₄₂H₄₈·C₆N₄ (1:1) complex, see: Shibahara et al. (2011a ▶). For the free ligand C₄₂H₄₈, see: Shibahara et al. (2007 ▶). For multilayered [3.3]paracyclophanes, see: Shibahara et al. (2008 ▶, 2011a ▶,b ▶). For cyclophanes, see: Vögtle (1993 ▶).

Experimental

Crystal data

C₄₂H₄₈·2C₆N₄
M _r = 809.03
Triclinic,
a = 9.563 (3) Å
b = 10.101 (4) Å
c = 11.679 (4) Å
α = 96.365 (14)°
β = 99.134 (13)°
γ = 107.683 (13)°
V = 1045.9 (6) Å³
Z = 1
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 123 K
0.35 × 0.16 × 0.09 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
17470 measured reflections
4775 independent reflections
4141 reflections with F ² > 2σ(F ²)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.178
S = 1.00
4775 reflections
394 parameters
Only H-atom coordinates refined
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXD (Schneider & Sheldrick, 2002 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536814009362/gw2145sup1.cif

e-70-0o625-sup1.cif^{(41.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009362/gw2145Isup2.hkl

e-70-0o625-Isup2.hkl^{(261.8KB, hkl)}

CCDC reference: 999480

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was partially supported by a Grant-in-Aid for Science Research (C 25410050) from the Japan Society for the Promotion of Science (JSPS), Japan, and was performed under the Cooperative Research Program of the Network Joint Research Center for Materials and Devices (IMCE, Kyushu University). MW thanks the World Premier International Research Center Initiative (WPI), Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT), Japan.

supplementary crystallographic information

1. Comment

The title complex consists of four-layered [3.3]metacyclophane (MCP) with two tetracyanoethylene molecules (TCNE). The TCNE molecules are stacked on either side of the outer [3.3]MCP units at a distance of 3.19 Å on one side and 3.24 Å on the other, and showed 0.80:0.20 and 0.44:0.56 disorder, respectively.

2. Experimental

The complex of single-crystal C₄₂H₄₈.2C₆N₄, consisting of four-layered [3.3]metacyclophane (MCP) with two tetracyanoethylene (TCNE) molecules, was synthesized. The black block crystals were obtained by slow diffusion from 2 mM of four-layered [3.3]MCP with 20 mM of TCNE in chloroform solution.