(12,17-Dieth­oxy­carbonyl-11,18-dimethyl-2,3:6,7-dibutano­corrphycenato)copper(II)–12,17-dieth­oxy­carbonyl-11,18-dimethyl-2:3,6:7-dibutano­corrphycene (3/97)

Ohgo, Y.; Yokoyama, Y.; Hashizume, D.; Neya, S.; Nakamura, M.

doi:10.1107/S1600536811052214

Volume 68
Part 1
Pages m23-m24
January 2012

Received 29 November 2011
Accepted 3 December 2011
Online 10 December 2011

Key indicators
Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.004 Å
Disorder in main residue
R = 0.072
wR = 0.246
Data-to-parameter ratio = 16.2
Details

(12,17-Diethoxycarbonyl-11,18-dimethyl-2,3:6,7-dibutanocorrphycenato)copper(II)-12,17-diethoxycarbonyl-11,18-dimethyl-2:3,6:7-dibutanocorrphycene (3/97)

Yoshiki Ohgo,^a ^* Yuki Yokoyama,^b Daisuke Hashizume,^c Saburo Neya ^b and Mikio Nakamura ^a

^aDepartment of Chemistry, Faculty of Medicine, Toho University, Ota-ku Tokyo 143-8540, Japan,^bDepartment of Physical Chemistry, Graduate School of Pharmaceutical, Sciences, Chuoh-Inohana, Chiba, Chiba 260-8675, Japan, and ^cAdvanced Technology Support, Division, RIKEN Advanced Science, Institute, Wako, Saitama 351-0198, Japan
Correspondence e-mail: yohgo@med.toho-u.ac.jp

The corrphycene molecule of the title compound, [Cu(C₃₆H₃₆N₄O₄)]_0.034.0.966C₃₆H₃₈N₄O₄, has an essentially planar macrocyclic framwork with a slightly distorted trapezoidal N₄ core; the r.m.s. deviation of the peripheral 20 C atoms and four N atoms is 0.054 (3) Å. The surface area within the N₄-coordinating core (8.358 Å²) is significantly smaller than that (8.503 Å²) of the corresponding free-base porphyrin. Two intramolecular N-HN hydrogen bonds are observed. Detailed structure analysis clarified that the co-crystallization of the free-base corrphycene together with a quite minor component (ca 3%) of corrphycenato-Cu^II occurred in the recrystallization process.

Related literature

For the first synthesis of free-base corrphycene, see: Sessler et al. (1994). For some related metal corrphycene compounds, see: Sessler et al. (2000). For related porphyrin analogues such as porphycene, N-confused porphyrins, corroles etc. see: Chmielewski et al. (1994); Erben et al. (2000); Furuta et al. (1994); Gross et al. (2000). For structures of five-coordinated halide-ligated iron(III) porphyrin, porphycene and corrphycene complexes, see: Ohgo, Neya, Funasaki et al. (2001); Ohgo, Neya, Ikeue et al. (2001); Ohgo et al. (2002). For the synthesis of the starting materials, see: Neya et al. (1998); Hombrecher & Horter (1992). For the structure of the corresponding porphyrin free-base, see: Lauher & Ibers (1973).

Experimental

Crystal data

[Cu(C₃₆H₃₆N₄O₄)]_0.034·0.966C₃₆H₃₈N₄O₄
M_r = 592.80
Triclinic, $[P \overline 1]$
a = 8.8759 (5) Å
b = 13.2493 (8) Å
c = 13.2891 (7) Å
= 108.496 (2)°
= 90.708 (2)°
= 98.142 (2)°
V = 1464.4 (1) Å³
Z = 2
Mo K radiation
= 0.11 mm^-1
T = 296 K
0.31 × 0.25 × 0.10 mm

Data collection

Rigaku RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.788, T_max = 0.923
14734 measured reflections
6677 independent reflections
3707 reflections with I > 2(I)
R_int = 0.044

Refinement

R[F² > 2(F²)] = 0.072
wR(F²) = 0.246
S = 1.15
6677 reflections
412 parameters
H-atom parameters constrained
_max = 1.69 e Å^-3
_min = -0.58 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N3-H3N2	0.85	2.33	2.777 (4)	113
N1-H1N4	0.89	2.11	2.774 (4)	131

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: HKL-2000; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS5019 ).

Acknowledgements

This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan (No. 23550083 to YO). This work was also supported by the Research Center for Materials with Integrated Properties and Advanced Medical Research Center, Toho University.

References

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