[μ-2,8-Dimethyl-1,4,5,6,7,10,11,12-octa­hydro­diimidazo[4,5-h;4′,5′-c][1,6]diaze­cine-5,11-diacetato]bis­[diaqua­nitrato­copper(II)] trihydrate

Luna-Ramírez, K.S.; Bernès, S.; Gasque, L.

doi:10.1107/S1600536808023969

Volume 64
Part 9
Pages m1135-m1136
September 2008

Received 16 July 2008
Accepted 28 July 2008
Online 6 August 2008

Key indicators
Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R = 0.031
wR = 0.083
Data-to-parameter ratio = 14.8
Details

[-2,8-Dimethyl-1,4,5,6,7,10,11,12-octahydrodiimidazo[4,5-h;4',5'-c][1,6]diazecine-5,11-diacetato]bis[diaquanitratocopper(II)] trihydrate

Karen S. Luna-Ramírez,^a Sylvain Bernès ^b ^* and Laura Gasque ^a

^aDepartamento de Química Inorgánica y Nuclear, Facultad de Química, UNAM, 04510 México, DF, Mexico, and ^bDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, NL, Mexico
Correspondence e-mail: sylvain_bernes@hotmail.com

The title compound, [Cu₂(C₁₆H₂₀N₆O₄)(NO₃)₂(H₂O)₄]·3H₂O, crystallizes with two dinuclear Cu^II complex molecules, each lying on an inversion center, and six solvent water molecules per unit cell. The central 1,6-diazecine ring adopts the common chair conformation invariably found in the family of complexes bearing such ligands. The Cu^II atoms have an octahedral geometry, with a very strong tetragonal distortion due to the Jahn-Teller effect. Axial sites are occupied by a nitrate ion and a water molecule. The CuCu separations [7.3580 (9) and 7.3341 (9) Å] are compatible with a potential catecholase activity. Neighboring molecules in the crystal structure are connected via O-HO hydrogen bonds formed by water molecules and carboxylate O atoms. N-HO hydrogen bonds are also present.

Related literature

For the X-ray characterized dinuclear Cu^II complexes based on related bis(aminoimidazole) ligands, which were designed as models of the catechol oxidaze active site, see: Driessen et al. (2005); Gasque et al. (2005, 2008); Mendoza-Díaz et al. (2002); Sosa et al. (2005).

Experimental

Crystal data

[Cu₂(C₁₆H₂₀N₆O₄)(NO₃)₂(H₂O)₄]·3H₂O
M_r = 737.59
Triclinic, $[P \overline 1]$
a = 7.7983 (9) Å
b = 8.7523 (11) Å
c = 22.509 (2) Å
= 91.802 (10)°
= 93.479 (9)°
= 114.023 (11)°
V = 1398.0 (3) Å³
Z = 2
Mo K radiation
= 1.61 mm^-1
T = 296 (1) K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker P4 diffractometer
Absorption correction: scan (XSCANS; Siemens, 1996) T_min = 0.638, T_max = 0.750
12145 measured reflections
6396 independent reflections
5139 reflections with I > 2(I)
R_int = 0.028
3 standard reflections every 97 reflections intensity decay: 2.5%

Refinement

R[F² > 2(F²)] = 0.030
wR(F²) = 0.082
S = 1.02
6396 reflections
433 parameters
22 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.50 e Å^-3
_min = -0.48 e Å^-3

Table 1
Selected bond lengths (Å)

Cu1-O10	1.9484 (16)
Cu1-O14	1.9533 (16)
Cu1-N1	1.9789 (18)
Cu1-N7	2.0619 (17)
Cu1-O15	2.601 (2)
Cu1-O43	2.607 (2)
Cu2-O30	1.9632 (15)
Cu2-O34	1.9697 (17)
Cu2-N21	1.9903 (18)
Cu2-N27	2.0690 (17)
Cu2-O35	2.4221 (19)
Cu2-O53	2.5994 (19)

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N3-H3AO42ⁱ	0.86	2.00	2.853 (3)	173
N23-H23AO52ⁱⁱ	0.86	2.07	2.927 (3)	173
O14-H14AO61ⁱⁱⁱ	0.84 (1)	1.81 (1)	2.613 (3)	158 (3)
O14-H14BO30	0.85 (1)	1.94 (1)	2.782 (2)	178 (3)
O15-H15AO31	0.84 (1)	1.89 (1)	2.701 (2)	160 (3)
O15-H15BO63ⁱⁱⁱ	0.84 (1)	1.98 (2)	2.769 (3)	155 (3)
O34-H34AO62	0.84 (1)	1.98 (1)	2.819 (3)	174 (3)
O34-H34BO63	0.84 (1)	1.86 (1)	2.665 (3)	160 (3)
O35-H35AO10	0.84 (3)	2.02 (3)	2.855 (2)	174 (3)
O35-H35BO15^iv	0.84 (3)	2.11 (3)	2.938 (3)	166 (3)
O61-H61AO11^v	0.84 (3)	1.98 (2)	2.787 (3)	161 (4)
O61-H61BO62^iv	0.85 (3)	2.22 (4)	2.770 (3)	123 (4)
O62-H62AO31^v	0.84 (1)	1.94 (1)	2.777 (3)	173 (4)
O62-H62BO52	0.84 (1)	2.24 (2)	3.023 (3)	154 (3)
O63-H63AO11^v	0.84 (1)	1.93 (1)	2.751 (3)	167 (3)
O63-H63BO43	0.84 (3)	2.07 (3)	2.898 (3)	170 (3)
O63-H63BO42	0.84 (3)	2.49 (2)	3.120 (3)	133 (3)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z; (iii) x-1, y, z; (iv) x+1, y, z; (v) x, y-1, z.

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2146 ).

Acknowledgements

SB thanks Universidad de Puebla, Mexico, for diffractometer time.

References

Driessen, W. L., Rehorst, D., Reedijk, J., Mutikainen, I. & Turpeinen, U. (2005). Inorg. Chim. Acta, 358, 2167-2173.
Gasque, L., Olguín, J. & Bernès, S. (2005). Acta Cryst. E61, m274-m276.
Gasque, L., Ugalde-Saldívar, V. M., Membrillo, I., Olguín, J., Mijangos, E., Bernès, S. & González, I. (2008). J. Inorg. Biochem. 102, 1227-1235.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.
Mendoza-Díaz, G., Driessen, W. L., Reedijk, J., Gorter, S., Gasque, L. & Thompson, K. R. (2002). Inorg. Chim. Acta, 339, 51-59.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Sosa, A. M., Ugalde-Saldívar, V. M., González, I. & Gasque, L. (2005). J. Electroanal. Chem. 579, 103-111.

metal-organic compounds