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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 [sigma](C-C) = 0.004 Å
Disorder in main residue
R = 0.072
wR = 0.246
Data-to-parameter ratio = 16.2
Details
Open access

(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)

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-H...N 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-CuII occurred in the recrystallization process.

Related literature

For the first synthesis of free-base corrphycene, see: Sessler et al. (1994[Sessler, J. L., Brucker, E. A., Weghorn, S. J., Michael Kisters, D.-C., Martin Schäfer, D.-C., Lex, J. & Vogel, E. (1994). Angew. Chem. Int. Ed. 33, 2308-2312.]). For some related metal corrphycene compounds, see: Sessler et al. (2000[Sessler, J. L., Gebauer, A. & Vogel, E. (2000). The Porphyrin Handbook, Vol. 2, pp. 1-54. New York: Academic Press.]). For related porphyrin analogues such as porphycene, N-confused porphyrins, corroles etc. see: Chmielewski et al. (1994[Chmielewski, P. J., Latos-Grazynski, L., Rachlewicz, K. & Glowiak, T. (1994). Angew. Chem. Int. Ed. Engl. 33, 779-781.]); Erben et al. (2000[Erben, C., Will, S. & Kadish, K. M. (2000). The Porphyrin Handbook, Vol. 2, edited by K. M. Kadish, K. M. Smith & R. Guilard, pp. 233-300. San Diego: Academic Press.]); Furuta et al. (1994[Furuta, H., Asano, T. & Ogawa, T. (1994). J. Am. Chem. Soc. 116, 767-768.]); Gross et al. (2000[Gross, Z., Golubkov, G. & Simkhovich, L. (2000). Angew. Chem. Int. Ed. 39, 4045-4047.]). For structures of five-coordinated halide-ligated iron(III) porphyrin, porphycene and corrphycene complexes, see: Ohgo, Neya, Funasaki et al. (2001[Ohgo, Y., Neya, S., Funasaki, N. & Nakamura, M. (2001). Acta Cryst. C57, 694-695.]); Ohgo, Neya, Ikeue et al. (2001[Ohgo, Y., Neya, S., Ikeue, T., Funasaki, N. & Nakamura, M. (2001). Acta Cryst. C57, 1046-1047.]); Ohgo et al. (2002[Ohgo, Y., Neya, S., Ikeue, T., Funasaki, N., Takahashi, M., Takeda, M. & Nakamura, M. (2002). Inorg. Chem. 41, 4627-4629.]). For the synthesis of the starting materials, see: Neya et al. (1998[Neya, S., Nishinaga, K., Ohyama, K. & Funasaki, N. (1998). Tetrahedron Lett. 39, 5217-5220.]); Hombrecher & Horter (1992[Hombrecher, H. K. & Horter, G. (1992). Synthesis, pp. 389-391.]). For the structure of the corresponding porphyrin free-base, see: Lauher & Ibers (1973[Lauher, J. W. & Ibers, J. A. (1973). J. Am. Chem. Soc. 95, 5148-5152.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(C36H36N4O4)]0.034·0.966C36H38N4O4

  • Mr = 592.80

  • Triclinic, [P \overline 1]

  • a = 8.8759 (5) Å

  • b = 13.2493 (8) Å

  • c = 13.2891 (7) Å

  • [alpha] = 108.496 (2)°

  • [beta] = 90.708 (2)°

  • [gamma] = 98.142 (2)°

  • V = 1464.4 (1) Å3

  • Z = 2

  • Mo K[alpha] radiation

  • [mu] = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.788, Tmax = 0.923

  • 14734 measured reflections

  • 6677 independent reflections

  • 3707 reflections with I > 2[sigma](I)

  • Rint = 0.044

Refinement
  • R[F2 > 2[sigma](F2)] = 0.072

  • wR(F2) = 0.246

  • S = 1.15

  • 6677 reflections

  • 412 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 1.69 e Å-3

  • [Delta][rho]min = -0.58 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N3-H3...N2 0.85 2.33 2.777 (4) 113
N1-H1...N4 0.89 2.11 2.774 (4) 131

Data collection: CrystalClear (Rigaku/MSC, 2005[Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., Texas, USA.]); cell refinement: HKL-2000 (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: HKL-2000; program(s) used to solve structure: SIR2004 (Burla et al., 2005[Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); 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

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.  [ISI] [CrossRef] [ChemPort] [details]
Chmielewski, P. J., Latos-Grazynski, L., Rachlewicz, K. & Glowiak, T. (1994). Angew. Chem. Int. Ed. Engl. 33, 779-781.  [CrossRef] [ISI]
Erben, C., Will, S. & Kadish, K. M. (2000). The Porphyrin Handbook, Vol. 2, edited by K. M. Kadish, K. M. Smith & R. Guilard, pp. 233-300. San Diego: Academic Press.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  [CrossRef] [details]
Furuta, H., Asano, T. & Ogawa, T. (1994). J. Am. Chem. Soc. 116, 767-768.  [CrossRef] [ChemPort] [ISI]
Gross, Z., Golubkov, G. & Simkhovich, L. (2000). Angew. Chem. Int. Ed. 39, 4045-4047.  [ChemPort]
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Hombrecher, H. K. & Horter, G. (1992). Synthesis, pp. 389-391.
Lauher, J. W. & Ibers, J. A. (1973). J. Am. Chem. Soc. 95, 5148-5152.  [CrossRef] [ChemPort] [PubMed] [ISI]
Neya, S., Nishinaga, K., Ohyama, K. & Funasaki, N. (1998). Tetrahedron Lett. 39, 5217-5220.  [ISI] [CrossRef] [ChemPort]
Ohgo, Y., Neya, S., Funasaki, N. & Nakamura, M. (2001). Acta Cryst. C57, 694-695.  [CSD] [CrossRef] [ChemPort] [details]
Ohgo, Y., Neya, S., Ikeue, T., Funasaki, N. & Nakamura, M. (2001). Acta Cryst. C57, 1046-1047.  [CSD] [CrossRef] [ChemPort] [details]
Ohgo, Y., Neya, S., Ikeue, T., Funasaki, N., Takahashi, M., Takeda, M. & Nakamura, M. (2002). Inorg. Chem. 41, 4627-4629.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., Texas, USA.
Sessler, J. L., Brucker, E. A., Weghorn, S. J., Michael Kisters, D.-C., Martin Schäfer, D.-C., Lex, J. & Vogel, E. (1994). Angew. Chem. Int. Ed. 33, 2308-2312.
Sessler, J. L., Gebauer, A. & Vogel, E. (2000). The Porphyrin Handbook, Vol. 2, pp. 1-54. New York: Academic Press.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]


Acta Cryst (2012). E68, m23-m24   [ doi:10.1107/S1600536811052214 ]

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