(4Z,6Z,12Z,14Z)-2,10-Dimethyl-2,8,10,16-tetra­hydro­dipyrazolo[3,4-e:3′,4′-l][1,2,4,8,9,11]hexa­azacyclo­tetra­decine-4,12-diamine

Dolzhenko, A.V.; Pastorin, G.; Dolzhenko, A.V.; Tan, G.K.; Koh, L.L.

doi:10.1107/S1600536809022132

Volume 65
Part 7
Pages o1578-o1579
July 2009

Received 3 June 2009
Accepted 10 June 2009
Online 13 June 2009

Key indicators
Single-crystal X-ray study
T = 223 K
Mean (C-C) = 0.003 Å
R = 0.062
wR = 0.151
Data-to-parameter ratio = 14.1
Details

(4Z,6Z,12Z,14Z)-2,10-Dimethyl-2,8,10,16-tetrahydrodipyrazolo[3,4-e:3',4'-l][1,2,4,8,9,11]hexaazacyclotetradecine-4,12-diamine

Anton V. Dolzhenko,^a ^* Giorgia Pastorin,^a Anna V. Dolzhenko,^a Geok Kheng Tan ^b and Lip Lin Koh ^b

^aDepartment of Pharmacy, Faculty of Science, National University of Singapore, 18 Science Drive 4, Singapore 117543, Singapore, and ^bDepartment of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Correspondence e-mail: phada@nus.edu.sg

The title compound, C₁₂H₁₆N₁₂, is a centrosymmetric molecule which comprises of a hexaaza[14]annulene macrocyclic ring fused with two pyrazole rings. The macrocyclic ring is essentially planar, with an r.m.s. deviation of 0.0381 Å. The electron pairs of the amino groups are delocalized with the conjugated system of the macrocycle. Strong intramolecular N-HN hydrogen bonds arranged in an S₂²(10) graph-set motif are present in the macrocyclic ring. In the crystal, the amino groups act as donors for intermolecular N-HN interactions with the N atoms of the heterocyclic system, forming a network of two types of extended chains oriented parallel to the [101] and [011] directions. The crystal packing is also stabilized by weak intermolecular C-HN hydrogen bonds formed between pyrazole C-H groups and N atoms of the macrocyclic ring, running in the [10 $[\overline{1}]$ ] direction.

Related literature

The title compound was synthesized according to Dolzhenko et al. (2009). For the synthesis and crystal structure studies of related macrocyclic compounds (as nickel complexes), see: Gradinaru et al. (2001); Gerbeleu et al. (1991); Leovac et al. (1993) and references cited therein; Simonov et al. (1988). For a review of the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Experimental

Crystal data

C₁₂H₁₆N₁₂
M_r = 328.37
Monoclinic, P 2₁ /n
a = 7.1470 (6) Å
b = 7.5593 (7) Å
c = 13.9174 (13) Å
= 91.866 (3)°
V = 751.51 (12) Å³
Z = 2
Mo K radiation
= 0.10 mm^-1
T = 223 K
0.22 × 0.08 × 0.06 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) T_min = 0.978, T_max = 0.994
5126 measured reflections
1721 independent reflections
1272 reflections with I > 2(I)
R_int = 0.037

Refinement

R[F² > 2(F²)] = 0.062
wR(F²) = 0.151
S = 1.06
1721 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
_max = 0.26 e Å^-3
_min = -0.17 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N3-H3NN4	0.85 (3)	2.09 (3)	2.770 (3)	136 (2)
N5-H5AN1ⁱ	0.88 (3)	2.33 (3)	3.065 (3)	141 (2)
N5-H5BN6ⁱⁱ	0.85 (3)	2.61 (3)	3.466 (3)	174 (2)
C3-H3N6ⁱⁱ	0.94	2.51	3.402 (3)	158
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2181 ).

Acknowledgements

This work is supported by the National Medical Research Council, Singapore (NMRC/NIG/0020/2008) and the National University of Singapore (R-148-050-091-101/133).

References

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Dolzhenko, A. V., Pastorin, G., Dolzhenko, A. V. & Chui, W. K. (2009). Tetrahedron Lett. In the press.
Gerbeleu, N. V., Simonov, Y. A., Arion, V. B., Gredinaru, D. I., Zavodnik, V. E., Indrichan, K. M. & Malinovskii, T. I. (1991). Russ. J. Inorg. Chem. 36, 52-54.
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Simonov, Y. A., Bourosh, P. N., Arion, V. B., Mazus, M. D. & Gerbeleu, N. V. (1988). Kristallografiya, 33, 1535-1537.

organic compounds