Acta Cryst. (2009). E65, m205 [ doi:10.1107/S1600536809001664 ]
The title complex, [Cu(C11H21N4)]ClO4, comprises [CuII(L)]+ (L = 11,13-dimethyl-1,4,7,10-tetraazacyclotrideca-10,12-dienate) cations and a perchlorate anion. The Cu atom is located on a twofold crystallographic symmetry axis and is coordinated by four N atoms in a slightly distorted square-planar geometry. Intermolecular N-H
O hydrogen bonds are present.
The title complex has been synthesized by the template method used commonly for synthesize metal complexes of macrocycle ligand. After the mixture, which is formed by acetylacetone, trien and Cu(ClO4)2.6H2O with a molar ratio 1:1:1 in methanol/water(v:v, 1:1), has been stirred for 6 h at 323 K, it was filtered and the filtrate was allowed to partial evaporate in air for one week to produce crystals suitable for X-ray diffraction with a yield of about 45%.
All the H atoms were constrained with C—H distances of 0.93, 0.96, 0.97 Å and N—H distances of 0.91 Å, respectively, and were allowed for as riding atoms with Uiso(H) = 1.2Ueq (C or N) and 1.5Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./hg2468fig1thm.gif)
| Fig. 1. A view of the cation of the title complex with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| [Cu(C11H21N4)]ClO4 | F(000) = 772 |
| Mr = 372.31 | Dx = 1.605 Mg m−3 Dm = 1.605 Mg m−3 Dm measured by not measured |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 1838 reflections |
| a = 12.530 (5) Å | θ = 3.2–24.7° |
| b = 14.469 (6) Å | µ = 1.61 mm−1 |
| c = 8.501 (4) Å | T = 293 K |
| V = 1541.2 (11) Å3 | Block, blue |
| Z = 4 | 0.15 × 0.13 × 0.11 mm |
| Bruker APEXII CCD area-detector diffractometer | 1349 independent reflections |
| Radiation source: fine-focus sealed tube | 950 reflections with I > 2σ(I) |
| graphite | Rint = 0.064 |
| φ and ω scans | θmax = 25.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −14→12 |
| Tmin = 0.794, Tmax = 0.843 | k = −15→17 |
| 6834 measured reflections | l = −9→10 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.216 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.144P)2 + 0.9336P] where P = (Fo2 + 2Fc2)/3 |
| 1349 reflections | (Δ/σ)max < 0.001 |
| 98 parameters | Δρmax = 1.10 e Å−3 |
| 0 restraints | Δρmin = −0.59 e Å−3 |
| [Cu(C11H21N4)]ClO4 | V = 1541.2 (11) Å3 |
| Mr = 372.31 | Z = 4 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 12.530 (5) Å | µ = 1.61 mm−1 |
| b = 14.469 (6) Å | T = 293 K |
| c = 8.501 (4) Å | 0.15 × 0.13 × 0.11 mm |
| Bruker APEXII CCD area-detector diffractometer | 1349 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 950 reflections with I > 2σ(I) |
| Tmin = 0.794, Tmax = 0.843 | Rint = 0.064 |
| 6834 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.067 | H-atom parameters constrained |
| wR(F2) = 0.216 | Δρmax = 1.10 e Å−3 |
| S = 1.05 | Δρmin = −0.59 e Å−3 |
| 1349 reflections | Absolute structure: ? |
| 98 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0.0000 | 0.32069 (5) | 0.2500 | 0.0431 (4) | |
| Cl1 | 0.0000 | 0.14239 (18) | 0.7500 | 0.0660 (7) | |
| O1 | 0.0525 (6) | 0.2000 (6) | 0.6429 (9) | 0.139 (3) | |
| O2 | 0.0806 (8) | 0.0904 (4) | 0.8238 (11) | 0.160 (3) | |
| N1 | 0.0904 (3) | 0.4014 (3) | 0.1568 (5) | 0.0481 (11) | |
| N2 | 0.0740 (3) | 0.2278 (3) | 0.1414 (5) | 0.0476 (11) | |
| H2 | 0.0427 | 0.2219 | 0.0453 | 0.057* | |
| C1 | 0.0000 | 0.5334 (6) | 0.2500 | 0.060 (2) | |
| H1 | 0.0000 | 0.5976 | 0.2500 | 0.072* | |
| C2 | 0.0803 (4) | 0.4932 (3) | 0.1651 (7) | 0.0579 (15) | |
| C3 | 0.1590 (5) | 0.5506 (4) | 0.0804 (9) | 0.078 (2) | |
| H3A | 0.2298 | 0.5334 | 0.1122 | 0.117* | |
| H3B | 0.1471 | 0.6146 | 0.1047 | 0.117* | |
| H3C | 0.1513 | 0.5412 | −0.0308 | 0.117* | |
| C4 | 0.1727 (4) | 0.3589 (4) | 0.0637 (7) | 0.0576 (14) | |
| H4A | 0.2396 | 0.3916 | 0.0780 | 0.069* | |
| H4B | 0.1537 | 0.3613 | −0.0469 | 0.069* | |
| C5 | 0.1840 (4) | 0.2618 (4) | 0.1151 (8) | 0.0597 (14) | |
| H5A | 0.2253 | 0.2581 | 0.2114 | 0.072* | |
| H5B | 0.2193 | 0.2254 | 0.0347 | 0.072* | |
| C6 | 0.0587 (5) | 0.1407 (4) | 0.2241 (7) | 0.0574 (15) | |
| H6A | 0.1056 | 0.1369 | 0.3147 | 0.069* | |
| H6B | 0.0732 | 0.0888 | 0.1552 | 0.069* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0446 (7) | 0.0320 (6) | 0.0526 (7) | 0.000 | −0.0004 (3) | 0.000 |
| Cl1 | 0.0883 (17) | 0.0572 (14) | 0.0526 (13) | 0.000 | 0.0019 (10) | 0.000 |
| O1 | 0.113 (5) | 0.182 (6) | 0.122 (6) | −0.012 (5) | −0.020 (4) | 0.056 (5) |
| O2 | 0.244 (10) | 0.106 (4) | 0.130 (6) | 0.077 (6) | −0.015 (7) | 0.003 (5) |
| N1 | 0.045 (2) | 0.039 (2) | 0.060 (3) | −0.0019 (17) | −0.004 (2) | 0.0077 (19) |
| N2 | 0.055 (3) | 0.038 (2) | 0.049 (2) | 0.0060 (18) | 0.0024 (19) | 0.0023 (17) |
| C1 | 0.069 (5) | 0.022 (3) | 0.090 (7) | 0.000 | −0.026 (5) | 0.000 |
| C2 | 0.058 (3) | 0.041 (3) | 0.075 (4) | −0.011 (3) | −0.031 (3) | 0.012 (3) |
| C3 | 0.078 (4) | 0.051 (3) | 0.104 (5) | −0.027 (3) | −0.026 (4) | 0.020 (3) |
| C4 | 0.048 (3) | 0.057 (3) | 0.068 (4) | −0.002 (2) | 0.006 (3) | 0.011 (3) |
| C5 | 0.053 (3) | 0.059 (3) | 0.068 (4) | 0.010 (2) | 0.002 (3) | 0.008 (3) |
| C6 | 0.070 (4) | 0.034 (3) | 0.068 (4) | 0.007 (3) | 0.002 (3) | 0.004 (2) |
| Cu1—N1i | 1.809 (4) | C1—C2i | 1.367 (7) |
| Cu1—N1 | 1.809 (4) | C1—H1 | 0.9300 |
| Cu1—N2i | 1.876 (4) | C2—C3 | 1.477 (8) |
| Cu1—N2 | 1.876 (4) | C3—H3A | 0.9600 |
| Cl1—O1ii | 1.399 (8) | C3—H3B | 0.9600 |
| Cl1—O1 | 1.399 (8) | C3—H3C | 0.9600 |
| Cl1—O2 | 1.407 (8) | C4—C5 | 1.479 (8) |
| Cl1—O2ii | 1.407 (8) | C4—H4A | 0.9700 |
| N1—C2 | 1.337 (6) | C4—H4B | 0.9700 |
| N1—C4 | 1.438 (7) | C5—H5A | 0.9700 |
| N2—C6 | 1.455 (7) | C5—H5B | 0.9700 |
| N2—C5 | 1.481 (7) | C6—C6i | 1.535 (13) |
| N2—H2 | 0.9100 | C6—H6A | 0.9700 |
| C1—C2 | 1.367 (7) | C6—H6B | 0.9700 |
| N1i—Cu1—N1 | 99.6 (3) | C1—C2—C3 | 120.7 (5) |
| N1i—Cu1—N2i | 86.43 (19) | C2—C3—H3A | 109.5 |
| N1—Cu1—N2i | 170.85 (17) | C2—C3—H3B | 109.5 |
| N1i—Cu1—N2 | 170.85 (17) | H3A—C3—H3B | 109.5 |
| N1—Cu1—N2 | 86.43 (19) | C2—C3—H3C | 109.5 |
| N2i—Cu1—N2 | 88.4 (2) | H3A—C3—H3C | 109.5 |
| O1ii—Cl1—O1 | 106.9 (7) | H3B—C3—H3C | 109.5 |
| O1ii—Cl1—O2 | 111.4 (5) | N1—C4—C5 | 108.2 (4) |
| O1—Cl1—O2 | 105.8 (5) | N1—C4—H4A | 110.1 |
| O1ii—Cl1—O2ii | 105.8 (5) | C5—C4—H4A | 110.1 |
| O1—Cl1—O2ii | 111.4 (5) | N1—C4—H4B | 110.1 |
| O2—Cl1—O2ii | 115.3 (7) | C5—C4—H4B | 110.1 |
| C2—N1—C4 | 121.5 (4) | H4A—C4—H4B | 108.4 |
| C2—N1—Cu1 | 124.0 (4) | C4—C5—N2 | 105.8 (4) |
| C4—N1—Cu1 | 114.5 (3) | C4—C5—H5A | 110.6 |
| C6—N2—C5 | 118.9 (4) | N2—C5—H5A | 110.6 |
| C6—N2—Cu1 | 108.5 (3) | C4—C5—H5B | 110.6 |
| C5—N2—Cu1 | 107.2 (3) | N2—C5—H5B | 110.6 |
| C6—N2—H2 | 107.2 | H5A—C5—H5B | 108.7 |
| C5—N2—H2 | 107.2 | N2—C6—C6i | 105.3 (4) |
| Cu1—N2—H2 | 107.2 | N2—C6—H6A | 110.7 |
| C2—C1—C2i | 129.7 (7) | C6i—C6—H6A | 110.7 |
| C2—C1—H1 | 115.1 | N2—C6—H6B | 110.7 |
| C2i—C1—H1 | 115.1 | C6i—C6—H6B | 110.7 |
| N1—C2—C1 | 121.3 (6) | H6A—C6—H6B | 108.8 |
| N1—C2—C3 | 118.0 (6) |
| Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···Cl1iii | 0.91 | 2.81 | 3.668 (5) | 157 |
| N2—H2···O1i | 0.91 | 2.02 | 2.917 (8) | 168 |
| Symmetry codes: (iii) x, y, z−1; (i) −x, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···Cl1i | 0.91 | 2.81 | 3.668 (5) | 157 |
| N2—H2···O1ii | 0.91 | 2.02 | 2.917 (8) | 168 |
| Symmetry codes: (i) x, y, z−1; (ii) −x, y, −z+1/2. |
Andrews, P. C., Atwood, J. L., Barbour, L. J., Croucher, P. D., Nichols, P. J., Smith, N. O., Skelton, B. W., White, A. H. & Raston, C. L. (1999). J. Chem. Soc. Dalton Trans. pp. 2927–2932.
Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Kim, D. I., Kim, E. H., Bae, Z. U., Na, H. G., Choi, J. H. & Park, Y. C. (2004). J. Inclus. Phenom. Macrocycl. Chem. 49, 107–113.
Richardson, M. F. & Sievers, R. E. (1972). J. Am. Chem. Soc. 94, 4134–4139.
Sheldrick, G. M. (1998). XP. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Macrocyclic ligands containing four N atoms located in a square planar coordination geometry have been intensly studied during the past several decades (Richardson, et al., 1972; Andrews, et al., 1999; Kim, et al., 2004). Here,we report a macrocycle tetraaza copper(II) complex based on the condensation of triethylenetetraamine (trien) with acetylacetone in the presence of copper(II) perchlorate.
The geometry and labelling scheme for the crystal structure of the title complex are depicted in Figure 1. The coordination sphere for the CuII ion in the title complex, which coordinates to four N atoms from triethylenetetraamine, is square planar with a mean deviation from the plane formed by the Cu atom and four N atoms of 0.0929Å . The bond lengths of Cu1—N1 and Cu1—N2 are 1.809 (4) and 1.876 (4)Å , respectively, which are slightly shorter than the corresponding distances found in another macrocycle copper complex 13,14-benzo-2,4,9,11-tetramethyl- 1,5,8,12-tetraazacyclotetradeca-1,3,9,11-tetraenato(2-)copper(II) (Kim, et al., 2004).