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Acta Cryst. (2008). E64, m1135-m1136    [ doi:10.1107/S1600536808023969 ]

[[mu]-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

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

Abstract top

The title compound, [Cu2(C16H20N6O4)(NO3)2(H2O)4]·3H2O, crystallizes with two dinuclear CuII 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 CuII 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 Cu...Cu 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-H...O hydrogen bonds formed by water molecules and carboxylate O atoms. N-H...O hydrogen bonds are also present.

Comment top

Several dinucleating ligands containing imidazole and amines condensed via the Mannich reaction have been recently described, as well as their dicopper complexes (Driessen et al., 2005; Gasque et al., 2005; Mendoza-Díaz et al., 2002; Sosa et al., 2005), which exhibit interesting magnetic properties and a significant catecholase activity (Gasque et al., 2008). The complex presented here is an analogue of the first dicopper complex of this family reported (Mendoza-Díaz et al., 2002), in which perchlorate ion has been substituted by nitrate. As nitrate ions have a stronger ability to coordinate metal ions, the present complex is found to have six-coordinated CuII centers, while perchlorate ions afforded a cationic complex including five-coordinated metal centers.

The asymmetric unit of the title compound is formed by two half-complexes, placed close to inversion centers, and three lattice water molecules, lying on general positions. The triclinic unit cell thus contains two dinuclar centrosymmetric complexes (Figs. 1 and 2), which have similar structures. The bis(aminoimidazole) ligand coordinates two CuII atoms, via imidazole and tertiary N atoms, and one carboxylate O atom. Each CuII atom completes its coordination environment with two water molecules and one monodentate nitrate ion. The resulting coordination geometry is octahedral, with a very strong distortion due to the Jahn-Teller effect: Cu—O axial bond lengths are in the range of 2.4221 (19)–2.607 (2) Å, while the longest equatorial bond measures 2.0690 (17) Å (Table 1). The central 1,6-diazecine 10-membered ring displays a chair conformation, with a total puckering amplitude of 1.441 (2) and 1.434 (2) Å for Cu1- and Cu2-complex, respectively. The Cu···Cu separations, 7.3580 (9) and 7.3341 (9) Å, are probably compatible with a catecholase activity for this molecular compound (Gasque et al., 2008).

Lattice water molecules are active into forming a number of rather strong hydrogen bonds (Table 2), connecting neighboring molecules in the crystal. Strongest hydrogen bonds involve all water molecules, as both donor and acceptor, and carboxylate O atoms as acceptor groups (Fig. 3).

Related literature top

For the X-ray characterized dinuclear CuII 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 top

The diazecine derivative was prepared as described previously (Mendoza-Díaz et al., 2002). To prepare the title compound, Cu(NO3)2.2.5H2O (0.232 g, 1 mmol) were dissolved in 20 ml of water, and an aqueous solution containing the ligand (0.251 g, 0.5 mmol) was added dropwise with stirring. The final pH was 2, at which the solution was left to stand. Blue crystals were collected after two days. Analysis, calculated for C16H34Cu2N8O17: C 26.05, H 4.61, N 15.20%; found: C 26.67, H 4.55, N 15.55%.

Refinement top

Water H atoms were located in a difference Fourier map and refined with distance restraints of O—H = 0.85 (1) and H···H = 1.34 (1) Å, and with Uiso(H) = 1.5Ueq(O). Other H atoms were positioned geometrically and refined as riding atoms, with N—H = 0.86 and C—H = 0.96 (CH3) and 0.97 Å (CH2), and with Uiso(H) = 1.2Ueq(C,N) or Uiso(H) = 1.5Ueq(methyl C).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Structure of the first independent molecule. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) -x, 2-y, 1-z.]
[Figure 2] Fig. 2. Structure of the second independent molecule. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (ii) 1-x, 2-y, -z.]
[Figure 3] Fig. 3. A part of the crystal packing, viewed down the [100] direction. C- and N–bonded H atoms have been omitted for clarity. Dashed lines represent hydrogen bonds involving water molecules and carboxylate O atoms.
[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 top
Crystal data top
[Cu2(C16H20N6O4)(NO3)2(H2O)4]·3H2OZ = 2
Mr = 737.59F000 = 760
Triclinic, P1Dx = 1.752 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.7983 (9) ÅCell parameters from 74 reflections
b = 8.7523 (11) Åθ = 3.8–12.5º
c = 22.509 (2) ŵ = 1.61 mm−1
α = 91.802 (10)ºT = 296 (1) K
β = 93.479 (9)ºPrism, blue
γ = 114.023 (11)º0.24 × 0.20 × 0.18 mm
V = 1398.0 (3) Å3
Data collection top
Bruker P4
diffractometer		Rint = 0.028
Radiation source: fine-focus sealed tubeθmax = 27.5º
Monochromator: graphiteθmin = 2.6º
T = 296(1) Kh = −9→7
2θ/ω scansk = −10→11
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)		l = −29→29
Tmin = 0.638, Tmax = 0.7503 standard reflections
12145 measured reflections every 97 reflections
6396 independent reflections intensity decay: 2.5%
5139 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.082  w = 1/[σ2(Fo2) + (0.0357P)2 + 0.6951P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.002
6396 reflectionsΔρmax = 0.50 e Å−3
433 parametersΔρmin = −0.48 e Å−3
22 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0028 (5)
Crystal data top
[Cu2(C16H20N6O4)(NO3)2(H2O)4]·3H2Oγ = 114.023 (11)º
Mr = 737.59V = 1398.0 (3) Å3
Triclinic, P1Z = 2
a = 7.7983 (9) ÅMo Kα
b = 8.7523 (11) ŵ = 1.61 mm−1
c = 22.509 (2) ÅT = 296 (1) K
α = 91.802 (10)º0.24 × 0.20 × 0.18 mm
β = 93.479 (9)º
Data collection top
Bruker P4
diffractometer		5139 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)		Rint = 0.028
Tmin = 0.638, Tmax = 0.7503 standard reflections
12145 measured reflections every 97 reflections
6396 independent reflections intensity decay: 2.5%
Refinement top
R[F2 > 2σ(F2)] = 0.03122 restraints
wR(F2) = 0.082H atoms treated by a mixture of
independent and constrained refinement
S = 1.02Δρmax = 0.50 e Å−3
6396 reflectionsΔρmin = −0.48 e Å−3
433 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.08644 (4)0.89792 (3)0.348009 (11)0.02579 (9)
N1−0.0982 (3)0.7671 (2)0.40361 (8)0.0248 (4)
C2−0.1523 (3)0.6214 (3)0.42879 (10)0.0256 (4)
N3−0.2240 (3)0.6329 (2)0.48134 (8)0.0258 (4)
H3A−0.26800.55350.50520.031*
C4−0.2147 (3)0.7941 (3)0.49036 (9)0.0238 (4)
C5−0.1392 (3)0.8745 (3)0.44130 (9)0.0231 (4)
C6−0.0845 (3)1.0489 (3)0.42218 (9)0.0234 (4)
H6A−0.08501.12280.45510.028*
H6B−0.17101.05130.38980.028*
N70.1104 (3)1.1013 (2)0.40212 (8)0.0236 (4)
C80.1656 (3)1.2389 (3)0.36114 (10)0.0275 (5)
H8A0.22461.34600.38380.033*
H8B0.05501.23580.33800.033*
C90.3037 (3)1.2185 (3)0.31942 (10)0.0294 (5)
O100.2858 (2)1.06789 (19)0.30833 (7)0.0303 (3)
O110.4199 (3)1.3415 (2)0.29801 (9)0.0502 (5)
C12−0.1377 (4)0.4685 (3)0.40444 (12)0.0388 (6)
H12A−0.02850.49960.38220.058*
H12B−0.24840.40380.37870.058*
H12C−0.12670.40280.43660.058*
C13−0.2580 (3)0.8638 (3)0.54610 (9)0.0262 (4)
H13A−0.37850.78520.55780.031*
H13B−0.27000.96730.53770.031*
O140.0602 (3)0.7270 (2)0.28594 (7)0.0337 (4)
H14A−0.048 (2)0.651 (3)0.2794 (12)0.051*
H14B0.087 (4)0.770 (3)0.2528 (7)0.051*
O15−0.1735 (3)0.9468 (2)0.28392 (8)0.0421 (4)
H15A−0.126 (4)0.955 (4)0.2509 (8)0.063*
H15B−0.263 (3)0.851 (2)0.2816 (14)0.063*
Cu20.35494 (4)0.83718 (3)0.145370 (11)0.02455 (8)
N210.5757 (3)0.8507 (2)0.10232 (8)0.0246 (4)
C220.6423 (3)0.7446 (3)0.08044 (10)0.0273 (5)
N230.7269 (3)0.8023 (2)0.03001 (8)0.0258 (4)
H23A0.78060.75420.00860.031*
C240.7128 (3)0.9526 (3)0.01846 (9)0.0225 (4)
C250.6218 (3)0.9813 (3)0.06424 (9)0.0218 (4)
C260.5580 (3)1.1153 (3)0.08005 (9)0.0225 (4)
H26A0.57081.18790.04740.027*
H26B0.63141.18270.11520.027*
N270.3561 (2)1.0257 (2)0.09200 (7)0.0213 (3)
C280.2817 (3)1.1241 (3)0.12900 (10)0.0267 (5)
H28A0.22821.18360.10360.032*
H28B0.38311.20590.15520.032*
C290.1307 (3)1.0060 (3)0.16603 (10)0.0278 (5)
O300.1386 (2)0.86562 (19)0.17597 (7)0.0293 (3)
O310.0133 (3)1.0514 (2)0.18558 (8)0.0415 (4)
C320.6350 (4)0.5899 (3)0.10759 (12)0.0416 (6)
H32A0.58640.58310.14600.062*
H32B0.75950.59270.11190.062*
H32C0.55440.49370.08230.062*
C330.7703 (3)1.0501 (3)−0.03551 (9)0.0248 (4)
H33A0.89681.0630−0.04270.030*
H33B0.77511.1612−0.02720.030*
O340.3272 (3)0.6462 (2)0.19384 (8)0.0351 (4)
H34A0.222 (2)0.564 (3)0.1904 (12)0.053*
H34B0.364 (4)0.668 (4)0.2303 (6)0.053*
O350.5368 (3)1.0386 (2)0.22603 (8)0.0393 (4)
H35A0.466 (3)1.044 (4)0.2520 (10)0.059*
H35B0.628 (3)1.029 (4)0.2450 (12)0.059*
N410.3385 (3)0.7364 (2)0.43818 (9)0.0332 (4)
O410.2854 (4)0.7699 (3)0.48506 (9)0.0635 (6)
O420.3741 (3)0.6098 (2)0.43267 (9)0.0426 (4)
O430.3583 (3)0.8284 (3)0.39489 (8)0.0487 (5)
N510.1540 (3)0.4932 (2)0.04767 (9)0.0320 (4)
O510.2721 (3)0.5612 (3)0.01204 (9)0.0540 (5)
O520.0845 (3)0.3372 (2)0.05034 (9)0.0449 (5)
O530.1045 (3)0.5808 (2)0.08235 (8)0.0425 (4)
O610.7678 (4)0.4526 (3)0.24970 (14)0.0846 (10)
H61A0.657 (3)0.398 (5)0.259 (2)0.127*
H61B0.819 (4)0.384 (3)0.250 (2)0.127*
O62−0.0134 (3)0.3570 (2)0.17744 (9)0.0484 (5)
H62A−0.015 (5)0.260 (2)0.1804 (14)0.073*
H62B−0.006 (5)0.371 (4)0.1406 (6)0.073*
O630.4948 (3)0.6773 (2)0.30304 (8)0.0404 (4)
H63A0.477 (5)0.5775 (18)0.3072 (14)0.061*
H63B0.448 (5)0.709 (4)0.3310 (11)0.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03386 (16)0.02060 (13)0.02290 (14)0.00971 (11)0.01201 (11)0.00325 (10)
N10.0294 (10)0.0231 (9)0.0225 (9)0.0105 (8)0.0069 (7)0.0032 (7)
C20.0292 (11)0.0233 (10)0.0246 (11)0.0104 (9)0.0057 (9)0.0047 (8)
N30.0300 (10)0.0217 (9)0.0246 (9)0.0082 (7)0.0082 (7)0.0066 (7)
C40.0232 (10)0.0216 (10)0.0250 (10)0.0069 (8)0.0054 (8)0.0026 (8)
C50.0225 (10)0.0228 (10)0.0233 (10)0.0081 (8)0.0043 (8)0.0021 (8)
C60.0256 (11)0.0249 (10)0.0220 (10)0.0119 (9)0.0060 (8)0.0038 (8)
N70.0294 (10)0.0211 (8)0.0214 (9)0.0103 (7)0.0089 (7)0.0046 (7)
C80.0361 (12)0.0221 (10)0.0256 (11)0.0117 (9)0.0111 (9)0.0064 (8)
C90.0338 (12)0.0280 (11)0.0265 (11)0.0114 (10)0.0102 (9)0.0064 (9)
O100.0363 (9)0.0257 (8)0.0298 (8)0.0116 (7)0.0150 (7)0.0051 (6)
O110.0573 (12)0.0308 (9)0.0619 (13)0.0124 (9)0.0368 (10)0.0140 (9)
C120.0554 (16)0.0271 (12)0.0382 (14)0.0197 (11)0.0143 (12)0.0054 (10)
C130.0254 (11)0.0285 (11)0.0248 (11)0.0101 (9)0.0085 (8)0.0034 (8)
O140.0437 (10)0.0272 (8)0.0259 (8)0.0088 (7)0.0127 (7)0.0000 (7)
O150.0395 (11)0.0469 (11)0.0327 (9)0.0092 (8)0.0114 (8)0.0047 (8)
Cu20.02862 (15)0.02653 (14)0.02214 (14)0.01350 (11)0.00965 (10)0.00828 (10)
N210.0261 (9)0.0271 (9)0.0228 (9)0.0123 (8)0.0054 (7)0.0070 (7)
C220.0281 (11)0.0315 (11)0.0257 (11)0.0148 (9)0.0056 (9)0.0064 (9)
N230.0288 (10)0.0296 (9)0.0242 (9)0.0163 (8)0.0076 (7)0.0040 (7)
C240.0211 (10)0.0252 (10)0.0218 (10)0.0098 (8)0.0032 (8)0.0037 (8)
C250.0205 (10)0.0237 (10)0.0209 (10)0.0086 (8)0.0026 (8)0.0044 (8)
C260.0230 (10)0.0224 (10)0.0220 (10)0.0085 (8)0.0055 (8)0.0035 (8)
N270.0230 (9)0.0220 (8)0.0201 (8)0.0097 (7)0.0067 (7)0.0032 (7)
C280.0314 (12)0.0297 (11)0.0243 (10)0.0166 (9)0.0099 (9)0.0052 (9)
C290.0300 (12)0.0333 (12)0.0226 (11)0.0145 (10)0.0075 (9)0.0046 (9)
O300.0343 (9)0.0302 (8)0.0265 (8)0.0146 (7)0.0128 (6)0.0076 (6)
O310.0460 (11)0.0491 (11)0.0446 (10)0.0310 (9)0.0265 (8)0.0172 (8)
C320.0576 (17)0.0428 (14)0.0415 (14)0.0350 (13)0.0172 (12)0.0187 (12)
C330.0215 (10)0.0290 (11)0.0228 (10)0.0083 (9)0.0061 (8)0.0053 (8)
O340.0404 (10)0.0308 (9)0.0314 (9)0.0109 (7)0.0053 (7)0.0111 (7)
O350.0399 (10)0.0510 (11)0.0328 (9)0.0241 (9)0.0069 (8)0.0005 (8)
N410.0346 (11)0.0308 (10)0.0348 (11)0.0136 (9)0.0039 (9)0.0068 (8)
O410.1023 (19)0.0726 (15)0.0410 (12)0.0576 (14)0.0303 (12)0.0161 (10)
O420.0498 (11)0.0284 (9)0.0530 (11)0.0177 (8)0.0129 (9)0.0093 (8)
O430.0711 (14)0.0503 (11)0.0392 (10)0.0368 (11)0.0161 (9)0.0207 (9)
N510.0358 (11)0.0319 (10)0.0311 (10)0.0174 (9)−0.0023 (8)−0.0005 (8)
O510.0574 (13)0.0541 (12)0.0461 (12)0.0165 (10)0.0171 (10)0.0033 (9)
O520.0558 (12)0.0292 (9)0.0502 (11)0.0183 (8)0.0008 (9)0.0021 (8)
O530.0532 (12)0.0388 (10)0.0416 (10)0.0249 (9)0.0074 (9)−0.0008 (8)
O610.0627 (16)0.0583 (15)0.101 (2)−0.0102 (12)0.0429 (15)−0.0296 (15)
O620.0574 (12)0.0403 (11)0.0497 (12)0.0196 (10)0.0189 (10)0.0102 (9)
O630.0469 (11)0.0366 (10)0.0365 (10)0.0144 (9)0.0103 (8)0.0094 (8)
Geometric parameters (Å, °) top
Cu1—O101.9484 (16)C33—N27ii1.514 (3)
Cu1—O141.9533 (16)N41—O411.226 (3)
Cu1—N11.9789 (18)N41—O421.251 (3)
Cu1—N72.0619 (17)N41—O431.260 (3)
Cu1—O152.601 (2)N51—O511.233 (3)
Cu1—O432.607 (2)N51—O521.253 (3)
N1—C21.327 (3)N51—O531.259 (3)
N1—C51.390 (3)N3—H3A0.8600
C2—N31.357 (3)C6—H6A0.9700
C2—C121.480 (3)C6—H6B0.9700
N3—C41.391 (3)C8—H8A0.9700
C4—C51.361 (3)C8—H8B0.9700
C4—C131.494 (3)C12—H12A0.9600
C5—C61.493 (3)C12—H12B0.9600
C6—N71.501 (3)C12—H12C0.9600
N7—C81.477 (3)C13—H13A0.9700
N7—C13i1.519 (3)C13—H13B0.9700
C8—C91.530 (3)O14—H14A0.84 (1)
C9—O111.226 (3)O14—H14B0.85 (1)
C9—O101.282 (3)O15—H15A0.84 (1)
C13—N7i1.519 (3)O15—H15B0.84 (1)
Cu2—O301.9632 (15)N23—H23A0.8600
Cu2—O341.9697 (17)C26—H26A0.9700
Cu2—N211.9903 (18)C26—H26B0.9700
Cu2—N272.0690 (17)C28—H28A0.9700
Cu2—O352.4221 (19)C28—H28B0.9700
Cu2—O532.5994 (19)C32—H32A0.9600
N21—C221.330 (3)C32—H32B0.9600
N21—C251.391 (3)C32—H32C0.9600
C22—N231.355 (3)C33—H33A0.9700
C22—C321.484 (3)C33—H33B0.9700
N23—C241.395 (3)O34—H34A0.84 (1)
C24—C251.359 (3)O34—H34B0.84 (1)
C24—C331.492 (3)O35—H35A0.84 (3)
C25—C261.490 (3)O35—H35B0.84 (3)
C26—N271.492 (3)O61—H61A0.84 (3)
N27—C281.480 (3)O61—H61B0.85 (3)
N27—C33ii1.514 (3)O62—H62A0.84 (1)
C28—C291.527 (3)O62—H62B0.84 (1)
C29—O311.234 (3)O63—H63A0.84 (1)
C29—O301.281 (3)O63—H63B0.84 (3)
O10—Cu1—O1491.21 (7)N27—C28—C29109.37 (17)
O10—Cu1—N1166.48 (7)O31—C29—O30124.2 (2)
O14—Cu1—N1102.13 (7)O31—C29—C28119.3 (2)
O10—Cu1—N782.87 (7)O30—C29—C28116.51 (19)
O14—Cu1—N7170.59 (7)C29—O30—Cu2114.94 (14)
N1—Cu1—N784.17 (7)C24—C33—N27ii115.46 (17)
O10—Cu1—O1591.86 (7)O41—N41—O42120.3 (2)
O14—Cu1—O1586.02 (7)O41—N41—O43120.8 (2)
N1—Cu1—O1591.24 (7)O42—N41—O43118.9 (2)
N7—Cu1—O1586.87 (7)N41—O43—Cu1122.73 (16)
O10—Cu1—O4384.37 (7)O51—N51—O52120.4 (2)
O14—Cu1—O4384.84 (7)O51—N51—O53120.0 (2)
N1—Cu1—O4394.57 (7)O52—N51—O53119.5 (2)
N7—Cu1—O43101.77 (7)N51—O53—Cu2120.63 (15)
O15—Cu1—O43170.03 (6)C2—N3—H3A125.6
C2—N1—C5106.92 (17)C4—N3—H3A125.6
C2—N1—Cu1139.08 (15)C5—C6—H6A110.6
C5—N1—Cu1109.98 (13)N7—C6—H6A110.6
N1—C2—N3109.50 (18)C5—C6—H6B110.6
N1—C2—C12126.2 (2)N7—C6—H6B110.6
N3—C2—C12124.3 (2)H6A—C6—H6B108.8
C2—N3—C4108.79 (17)N7—C8—H8A109.9
C5—C4—N3105.16 (18)C9—C8—H8A109.9
C5—C4—C13128.95 (19)N7—C8—H8B109.9
N3—C4—C13125.51 (19)C9—C8—H8B109.9
C4—C5—N1109.61 (18)H8A—C8—H8B108.3
C4—C5—C6134.29 (19)C2—C12—H12A109.5
N1—C5—C6116.00 (18)C2—C12—H12B109.5
C5—C6—N7105.46 (16)H12A—C12—H12B109.5
C8—N7—C6114.66 (17)C2—C12—H12C109.5
C8—N7—C13i111.73 (17)H12A—C12—H12C109.5
C6—N7—C13i112.48 (16)H12B—C12—H12C109.5
C8—N7—Cu1102.92 (12)C4—C13—H13A108.8
C6—N7—Cu1102.80 (12)N7i—C13—H13A108.8
C13i—N7—Cu1111.46 (13)C4—C13—H13B108.8
N7—C8—C9108.93 (17)N7i—C13—H13B108.8
O11—C9—O10124.0 (2)H13A—C13—H13B107.7
O11—C9—C8120.1 (2)Cu1—O14—H14A115.2 (19)
O10—C9—C8115.84 (19)Cu1—O14—H14B111 (2)
C9—O10—Cu1114.73 (14)H14A—O14—H14B105 (2)
C4—C13—N7i113.84 (18)Cu1—O15—H15A98 (2)
O30—Cu2—O3494.11 (7)Cu1—O15—H15B102 (2)
O30—Cu2—N21166.65 (7)H15A—O15—H15B105 (2)
O34—Cu2—N2199.21 (7)C22—N23—H23A125.6
O30—Cu2—N2782.21 (7)C24—N23—H23A125.6
O34—Cu2—N27174.38 (7)C25—C26—H26A110.6
N21—Cu2—N2784.44 (7)N27—C26—H26A110.6
O30—Cu2—O3584.72 (7)C25—C26—H26B110.6
O34—Cu2—O3592.25 (7)N27—C26—H26B110.6
N21—Cu2—O3595.62 (7)H26A—C26—H26B108.8
N27—Cu2—O3591.64 (7)N27—C28—H28A109.8
O30—Cu2—O5385.36 (6)C29—C28—H28A109.8
O34—Cu2—O5376.31 (7)N27—C28—H28B109.8
N21—Cu2—O5396.84 (7)C29—C28—H28B109.8
N27—Cu2—O5399.08 (6)H28A—C28—H28B108.2
O35—Cu2—O53164.27 (6)C22—C32—H32A109.5
C22—N21—C25106.61 (17)C22—C32—H32B109.5
C22—N21—Cu2137.21 (15)H32A—C32—H32B109.5
C25—N21—Cu2109.28 (13)C22—C32—H32C109.5
N21—C22—N23109.61 (19)H32A—C32—H32C109.5
N21—C22—C32126.3 (2)H32B—C32—H32C109.5
N23—C22—C32124.1 (2)C24—C33—H33A108.4
C22—N23—C24108.84 (18)N27ii—C33—H33A108.4
C25—C24—N23104.89 (18)C24—C33—H33B108.4
C25—C24—C33128.23 (19)N27ii—C33—H33B108.4
N23—C24—C33126.66 (19)H33A—C33—H33B107.5
C24—C25—N21110.02 (18)Cu2—O34—H34A117 (2)
C24—C25—C26134.12 (19)Cu2—O34—H34B117 (2)
N21—C25—C26115.81 (17)H34A—O34—H34B109 (2)
C25—C26—N27105.47 (16)Cu2—O35—H35A110 (2)
C28—N27—C26114.94 (16)Cu2—O35—H35B121 (2)
C28—N27—C33ii111.27 (17)H35A—O35—H35B105 (2)
C26—N27—C33ii112.37 (15)H61A—O61—H61B106 (2)
C28—N27—Cu2104.14 (12)H62A—O62—H62B103 (2)
C26—N27—Cu2103.68 (12)H63A—O63—H63B108 (2)
C33ii—N27—Cu2109.74 (12)
O10—Cu1—N1—C2−126.5 (3)N27—Cu2—N21—C254.30 (14)
O14—Cu1—N1—C244.1 (2)O35—Cu2—N21—C25−86.81 (14)
N7—Cu1—N1—C2−143.0 (2)O53—Cu2—N21—C25102.81 (14)
O15—Cu1—N1—C2130.3 (2)C25—N21—C22—N23−0.5 (2)
O43—Cu1—N1—C2−41.6 (2)Cu2—N21—C22—N23145.56 (18)
O10—Cu1—N1—C526.7 (4)C25—N21—C22—C32176.9 (2)
O14—Cu1—N1—C5−162.71 (14)Cu2—N21—C22—C32−37.1 (4)
N7—Cu1—N1—C510.21 (14)N21—C22—N23—C24−0.5 (3)
O15—Cu1—N1—C5−76.52 (14)C32—C22—N23—C24−178.0 (2)
O43—Cu1—N1—C5111.60 (14)C22—N23—C24—C251.3 (2)
C5—N1—C2—N3−0.7 (2)C22—N23—C24—C33−173.7 (2)
Cu1—N1—C2—N3152.96 (18)N23—C24—C25—N21−1.6 (2)
C5—N1—C2—C12179.5 (2)C33—C24—C25—N21173.3 (2)
Cu1—N1—C2—C12−26.8 (4)N23—C24—C25—C26−179.1 (2)
N1—C2—N3—C4−0.2 (3)C33—C24—C25—C26−4.2 (4)
C12—C2—N3—C4179.6 (2)C22—N21—C25—C241.3 (2)
C2—N3—C4—C51.1 (2)Cu2—N21—C25—C24−154.94 (15)
C2—N3—C4—C13−172.3 (2)C22—N21—C25—C26179.31 (18)
N3—C4—C5—N1−1.5 (2)Cu2—N21—C25—C2623.0 (2)
C13—C4—C5—N1171.5 (2)C24—C25—C26—N27129.3 (2)
N3—C4—C5—C6−177.7 (2)N21—C25—C26—N27−48.0 (2)
C13—C4—C5—C6−4.7 (4)C25—C26—N27—C28158.64 (17)
C2—N1—C5—C41.4 (2)C25—C26—N27—C33ii−72.8 (2)
Cu1—N1—C5—C4−160.57 (15)C25—C26—N27—Cu245.67 (16)
C2—N1—C5—C6178.42 (19)O30—Cu2—N27—C2830.55 (13)
Cu1—N1—C5—C616.4 (2)N21—Cu2—N27—C28−149.39 (14)
C4—C5—C6—N7131.6 (3)O35—Cu2—N27—C28−53.90 (13)
N1—C5—C6—N7−44.5 (2)O53—Cu2—N27—C28114.55 (13)
C5—C6—N7—C8158.05 (17)O30—Cu2—N27—C26151.13 (12)
C5—C6—N7—C13i−72.8 (2)N21—Cu2—N27—C26−28.80 (12)
C5—C6—N7—Cu147.16 (17)O35—Cu2—N27—C2666.69 (12)
O10—Cu1—N7—C831.67 (14)O53—Cu2—N27—C26−124.87 (12)
N1—Cu1—N7—C8−152.16 (14)O30—Cu2—N27—C33ii−88.64 (13)
O15—Cu1—N7—C8−60.59 (13)N21—Cu2—N27—C33ii91.42 (13)
O43—Cu1—N7—C8114.37 (13)O35—Cu2—N27—C33ii−173.09 (12)
O10—Cu1—N7—C6151.08 (13)O53—Cu2—N27—C33ii−4.64 (13)
N1—Cu1—N7—C6−32.75 (13)C26—N27—C28—C29−148.41 (18)
O15—Cu1—N7—C658.82 (12)C33ii—N27—C28—C2982.4 (2)
O43—Cu1—N7—C6−126.22 (12)Cu2—N27—C28—C29−35.70 (19)
O10—Cu1—N7—C13i−88.21 (13)N27—C28—C29—O31−158.3 (2)
N1—Cu1—N7—C13i87.95 (13)N27—C28—C29—O3023.4 (3)
O15—Cu1—N7—C13i179.52 (13)O31—C29—O30—Cu2−174.47 (19)
O43—Cu1—N7—C13i−5.51 (14)C28—C29—O30—Cu23.7 (2)
C6—N7—C8—C9−149.67 (18)O34—Cu2—O30—C29164.11 (16)
C13i—N7—C8—C980.8 (2)N21—Cu2—O30—C29−19.9 (4)
Cu1—N7—C8—C9−38.8 (2)N27—Cu2—O30—C29−20.16 (15)
N7—C8—C9—O11−152.6 (2)O35—Cu2—O30—C2972.23 (16)
N7—C8—C9—O1028.6 (3)O53—Cu2—O30—C29−120.00 (16)
O11—C9—O10—Cu1−179.2 (2)C25—C24—C33—N27ii−101.2 (3)
C8—C9—O10—Cu1−0.5 (3)N23—C24—C33—N27ii72.7 (3)
O14—Cu1—O10—C9154.16 (17)O41—N41—O43—Cu1−56.3 (3)
N1—Cu1—O10—C9−35.0 (4)O42—N41—O43—Cu1123.81 (19)
N7—Cu1—O10—C9−18.51 (16)O10—Cu1—O43—N41167.17 (19)
O15—Cu1—O10—C968.10 (17)O14—Cu1—O43—N41−101.09 (19)
O43—Cu1—O10—C9−121.15 (17)N1—Cu1—O43—N410.70 (19)
C5—C4—C13—N7i−99.9 (3)N7—Cu1—O43—N4185.68 (19)
N3—C4—C13—N7i71.9 (3)O51—N51—O53—Cu2−49.7 (3)
O30—Cu2—N21—C22−141.4 (3)O52—N51—O53—Cu2129.25 (19)
O34—Cu2—N21—C2234.5 (2)O30—Cu2—O53—N51179.93 (17)
N27—Cu2—N21—C22−141.1 (2)O34—Cu2—O53—N51−84.69 (17)
O35—Cu2—N21—C22127.8 (2)N21—Cu2—O53—N5113.17 (18)
O53—Cu2—N21—C22−42.6 (2)N27—Cu2—O53—N5198.60 (17)
O30—Cu2—N21—C254.0 (4)O35—Cu2—O53—N51−129.0 (2)
O34—Cu2—N21—C25179.99 (14)
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O42iii0.862.002.853 (3)173
N23—H23A···O52iv0.862.072.927 (3)173
O14—H14A···O61v0.84 (1)1.81 (1)2.613 (3)158 (3)
O14—H14B···O300.85 (1)1.94 (1)2.782 (2)178 (3)
O15—H15A···O310.84 (1)1.89 (1)2.701 (2)160 (3)
O15—H15B···O63v0.84 (1)1.98 (2)2.769 (3)155 (3)
O34—H34A···O620.84 (1)1.98 (1)2.819 (3)174 (3)
O34—H34B···O630.84 (1)1.86 (1)2.665 (3)160 (3)
O35—H35A···O100.84 (3)2.02 (3)2.855 (2)174 (3)
O35—H35B···O15vi0.84 (3)2.11 (3)2.938 (3)166 (3)
O61—H61A···O11vii0.84 (3)1.98 (2)2.787 (3)161 (4)
O61—H61B···O62vi0.85 (3)2.22 (4)2.770 (3)123 (4)
O62—H62A···O31vii0.84 (1)1.94 (1)2.777 (3)173 (4)
O62—H62B···O520.84 (1)2.24 (2)3.023 (3)154 (3)
O63—H63A···O11vii0.84 (1)1.93 (1)2.751 (3)167 (3)
O63—H63B···O430.84 (3)2.07 (3)2.898 (3)170 (3)
O63—H63B···O420.84 (3)2.49 (2)3.120 (3)133 (3)
Symmetry codes: (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x−1, y, z; (vi) x+1, y, z; (vii) x, y−1, z.
Table 1
Selected geometric parameters (Å) top
Cu1—O101.9484 (16)Cu2—O301.9632 (15)
Cu1—O141.9533 (16)Cu2—O341.9697 (17)
Cu1—N11.9789 (18)Cu2—N211.9903 (18)
Cu1—N72.0619 (17)Cu2—N272.0690 (17)
Cu1—O152.601 (2)Cu2—O352.4221 (19)
Cu1—O432.607 (2)Cu2—O532.5994 (19)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O42i0.862.002.853 (3)173
N23—H23A···O52ii0.862.072.927 (3)173
O14—H14A···O61iii0.84 (1)1.81 (1)2.613 (3)158 (3)
O14—H14B···O300.85 (1)1.94 (1)2.782 (2)178 (3)
O15—H15A···O310.84 (1)1.89 (1)2.701 (2)160 (3)
O15—H15B···O63iii0.84 (1)1.98 (2)2.769 (3)155 (3)
O34—H34A···O620.84 (1)1.98 (1)2.819 (3)174 (3)
O34—H34B···O630.84 (1)1.86 (1)2.665 (3)160 (3)
O35—H35A···O100.84 (3)2.02 (3)2.855 (2)174 (3)
O35—H35B···O15iv0.84 (3)2.11 (3)2.938 (3)166 (3)
O61—H61A···O11v0.84 (3)1.98 (2)2.787 (3)161 (4)
O61—H61B···O62iv0.85 (3)2.22 (4)2.770 (3)123 (4)
O62—H62A···O31v0.84 (1)1.94 (1)2.777 (3)173 (4)
O62—H62B···O520.84 (1)2.24 (2)3.023 (3)154 (3)
O63—H63A···O11v0.84 (1)1.93 (1)2.751 (3)167 (3)
O63—H63B···O430.84 (3)2.07 (3)2.898 (3)170 (3)
O63—H63B···O420.84 (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.
Acknowledgements top

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

references
References top

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.