Acta Cryst. (2008). E64, m33 [ doi:10.1107/S1600536807046260 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
N)[6-methoxy-2-(2-pyridylmethyliminomethyl)phenolato-3N,N',O1]copper(II)The title compound, [Cu(C14H13N2O2)(N3)], is a monomeric neutral complex with one unsymmetrical 6-methoxy-2-(2-pyridylmethyliminomethyl)phenolate Schiff base ligand and one azide ligand. The molecules are connected by a combination of two ![[pi]](/logos/entities/pi_rmgif.gif)
- interactions [centroid-centroid distances 3.359 (3) and 3.378 (2) Å] and one C-H
N hydrogen bond into a two-dimensional supramolecular network structure.
The Schiff base 6-Methoxy-2-(2-pyridylmethyliminomethyl)phenol (HL) was synthesized according to literature (Ni et al., 2007). The title complex was prepared as following: aquaous and methanol solution (6 ml, MeOH/H2O = 2:1 v/v) of NaN3 (52 mg, 0.8 mmol) was added into a MeOH and aquaous solution (20 ml, MeOH/H2O = 4:1 v/v) containing the HL ligand (48 mg, 0.2 mmol) and CuCl2.2H2O (34 mg, 0.2 mmol). The mixture was rapidly filtered and the resulting solution was kept at room temperature for about six hours, giving rise a to brown product. Yield: 60%. Elemental analysis [found (calculated)] for CuC14H13N5O2: C 48.35 (48.48), H 3.70 (3.78), N 20.12% (20.19%).
H atoms bound to C were placed using the HFIX commands in SHELXL-97. All H atoms were allowed for as riding atoms (C—H 0.97 Å, or 0.93 Å) with the constraint Uiso(H) = 1.5Ueq(methyl carrier) and 1.2Ueq(carrier) for all other H atoms.
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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and XP (Sheldrick, 1998).
![[Figure 1]](./si2035fig1thm.gif)
| Fig. 1. A view of (I) with the unique atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, solvate water molecules and all H atoms bonded to C atoms are omitted. |
![[Figure 2]](./si2035fig2thm.gif)
| Fig. 2. A stereoview of part of the crystal structure of (I), showing the two-dimensional supramolecular structure. For the sake of clarity, H atoms bonded to C atoms and not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (-x + 2, -y, -z + 1), (-x + 1, -y, -z + 1), (x, y + 1, z) and (x, y + 1, z), respectively. |
| [Cu(C14H13N2O2)(N3)] | Z = 2 |
| Mr = 346.83 | F000 = 354 |
| Triclinic, P1 | Dx = 1.646 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 6.7197 (2) Å | Cell parameters from 3207 reflections |
| b = 10.2820 (2) Å | θ = 2.0–27.5º |
| c = 10.5549 (5) Å | µ = 1.58 mm−1 |
| α = 86.130 (2)º | T = 293 (2) K |
| β = 81.155 (2)º | Tiny block, brown |
| γ = 76.289 (3)º | 0.10 × 0.06 × 0.04 mm |
| V = 699.69 (4) Å3 |
| Bruker APEXII CCD area-detector diffractometer | 3207 independent reflections |
| Radiation source: fine-focus sealed tube | 2815 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.020 |
| T = 293(2) K | θmax = 27.5º |
| φ and ω scans | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −8→8 |
| Tmin = 0.892, Tmax = 0.941 | k = −13→13 |
| 11804 measured reflections | l = −13→13 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.066P)2 + 0.0216P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.99 | (Δ/σ)max = 0.001 |
| 3207 reflections | Δρmax = 0.35 e Å−3 |
| 199 parameters | Δρmin = −0.29 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Cu(C14H13N2O2)(N3)] | γ = 76.289 (3)º |
| Mr = 346.83 | V = 699.69 (4) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.7197 (2) Å | Mo Kα |
| b = 10.2820 (2) Å | µ = 1.58 mm−1 |
| c = 10.5549 (5) Å | T = 293 (2) K |
| α = 86.130 (2)º | 0.10 × 0.06 × 0.04 mm |
| β = 81.155 (2)º |
| Bruker APEXII CCD area-detector diffractometer | 3207 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2815 reflections with I > 2σ(I) |
| Tmin = 0.892, Tmax = 0.941 | Rint = 0.020 |
| 11804 measured reflections |
| R[F2 > 2σ(F2)] = 0.028 | 199 parameters |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 0.99 | Δρmax = 0.35 e Å−3 |
| 3207 reflections | Δρmin = −0.29 e Å−3 |
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 | 0.71363 (3) | 0.01027 (2) | 0.64642 (2) | 0.03501 (10) | |
| O1 | 0.6949 (2) | 0.15473 (13) | 0.52246 (13) | 0.0419 (3) | |
| O2 | 0.6515 (3) | 0.38174 (15) | 0.38914 (16) | 0.0527 (4) | |
| N1 | 0.6386 (4) | 0.1355 (2) | 0.78607 (19) | 0.0566 (5) | |
| N2 | 0.7302 (3) | 0.21856 (17) | 0.79457 (17) | 0.0483 (4) | |
| N3 | 0.8155 (4) | 0.2994 (2) | 0.8096 (3) | 0.0735 (7) | |
| N4 | 0.7379 (2) | −0.15134 (16) | 0.76640 (16) | 0.0373 (3) | |
| N5 | 0.7842 (2) | −0.12500 (16) | 0.51834 (16) | 0.0357 (3) | |
| C5 | 0.7893 (3) | −0.26937 (19) | 0.7095 (2) | 0.0380 (4) | |
| C8 | 0.7789 (3) | 0.0241 (2) | 0.33149 (19) | 0.0381 (4) | |
| C12 | 0.7057 (3) | 0.2671 (2) | 0.3210 (2) | 0.0411 (4) | |
| C13 | 0.7266 (3) | 0.14646 (19) | 0.39683 (19) | 0.0369 (4) | |
| C1 | 0.7074 (3) | −0.1514 (2) | 0.8959 (2) | 0.0459 (5) | |
| H1 | 0.6707 | −0.0697 | 0.9363 | 0.055* | |
| C2 | 0.7285 (4) | −0.2665 (3) | 0.9697 (2) | 0.0553 (6) | |
| H2 | 0.7077 | −0.2630 | 1.0587 | 0.066* | |
| C3 | 0.7806 (4) | −0.3881 (2) | 0.9112 (2) | 0.0530 (6) | |
| H3 | 0.7940 | −0.4678 | 0.9599 | 0.064* | |
| C4 | 0.8128 (3) | −0.3895 (2) | 0.7786 (2) | 0.0472 (5) | |
| H4 | 0.8498 | −0.4703 | 0.7366 | 0.057* | |
| C7 | 0.8033 (3) | −0.1038 (2) | 0.3957 (2) | 0.0399 (4) | |
| H7 | 0.8357 | −0.1784 | 0.3448 | 0.048* | |
| C9 | 0.8117 (3) | 0.0253 (2) | 0.1950 (2) | 0.0467 (5) | |
| H9 | 0.8470 | −0.0553 | 0.1528 | 0.056* | |
| C10 | 0.7921 (3) | 0.1424 (2) | 0.1258 (2) | 0.0511 (5) | |
| H10 | 0.8144 | 0.1418 | 0.0367 | 0.061* | |
| C11 | 0.7386 (3) | 0.2640 (2) | 0.1881 (2) | 0.0460 (5) | |
| H11 | 0.7248 | 0.3439 | 0.1399 | 0.055* | |
| C6 | 0.8206 (3) | −0.26431 (19) | 0.5655 (2) | 0.0426 (4) | |
| H6A | 0.9607 | −0.3110 | 0.5335 | 0.051* | |
| H6B | 0.7257 | −0.3085 | 0.5347 | 0.051* | |
| C14 | 0.6187 (4) | 0.5071 (2) | 0.3204 (3) | 0.0576 (6) | |
| H14A | 0.5820 | 0.5784 | 0.3799 | 0.086* | |
| H14B | 0.5087 | 0.5137 | 0.2703 | 0.086* | |
| H14C | 0.7431 | 0.5138 | 0.2646 | 0.086* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.03917 (16) | 0.03307 (14) | 0.03272 (15) | −0.00818 (10) | −0.00430 (10) | −0.00288 (9) |
| O1 | 0.0541 (8) | 0.0374 (7) | 0.0338 (7) | −0.0092 (6) | −0.0065 (6) | −0.0025 (5) |
| O2 | 0.0669 (10) | 0.0411 (8) | 0.0486 (9) | −0.0096 (7) | −0.0097 (8) | 0.0030 (7) |
| N1 | 0.0808 (14) | 0.0462 (10) | 0.0410 (11) | −0.0179 (10) | 0.0068 (10) | −0.0107 (8) |
| N2 | 0.0719 (12) | 0.0295 (8) | 0.0380 (10) | 0.0006 (8) | −0.0104 (8) | 0.0000 (7) |
| N3 | 0.1041 (19) | 0.0387 (11) | 0.0809 (17) | −0.0149 (11) | −0.0245 (14) | −0.0045 (10) |
| N4 | 0.0354 (8) | 0.0380 (8) | 0.0394 (9) | −0.0103 (6) | −0.0063 (7) | 0.0002 (7) |
| N5 | 0.0347 (8) | 0.0356 (8) | 0.0373 (9) | −0.0081 (6) | −0.0056 (7) | −0.0028 (6) |
| C5 | 0.0308 (9) | 0.0383 (9) | 0.0460 (11) | −0.0102 (7) | −0.0071 (8) | 0.0020 (8) |
| C8 | 0.0348 (9) | 0.0458 (10) | 0.0343 (10) | −0.0103 (8) | −0.0047 (8) | −0.0024 (8) |
| C12 | 0.0353 (10) | 0.0441 (11) | 0.0444 (11) | −0.0095 (8) | −0.0083 (8) | 0.0021 (8) |
| C13 | 0.0306 (9) | 0.0443 (10) | 0.0364 (11) | −0.0092 (7) | −0.0063 (7) | 0.0007 (8) |
| C1 | 0.0487 (12) | 0.0496 (12) | 0.0393 (12) | −0.0124 (9) | −0.0057 (9) | 0.0013 (9) |
| C2 | 0.0554 (13) | 0.0672 (15) | 0.0434 (13) | −0.0178 (11) | −0.0073 (10) | 0.0111 (11) |
| C3 | 0.0510 (12) | 0.0501 (12) | 0.0586 (15) | −0.0169 (10) | −0.0101 (10) | 0.0175 (10) |
| C4 | 0.0432 (11) | 0.0391 (10) | 0.0608 (14) | −0.0130 (8) | −0.0094 (10) | 0.0055 (9) |
| C7 | 0.0393 (10) | 0.0425 (10) | 0.0387 (11) | −0.0090 (8) | −0.0040 (8) | −0.0108 (8) |
| C9 | 0.0495 (12) | 0.0569 (12) | 0.0345 (11) | −0.0123 (9) | −0.0060 (9) | −0.0072 (9) |
| C10 | 0.0501 (12) | 0.0724 (15) | 0.0308 (11) | −0.0144 (11) | −0.0072 (9) | 0.0029 (10) |
| C11 | 0.0412 (11) | 0.0548 (12) | 0.0432 (12) | −0.0140 (9) | −0.0107 (9) | 0.0108 (9) |
| C6 | 0.0483 (11) | 0.0344 (9) | 0.0454 (12) | −0.0087 (8) | −0.0068 (9) | −0.0056 (8) |
| C14 | 0.0596 (14) | 0.0430 (12) | 0.0701 (16) | −0.0115 (10) | −0.0144 (12) | 0.0093 (11) |
| Cu1—O1 | 1.9062 (14) | C7—C8 | 1.423 (3) |
| Cu1—N1 | 1.9504 (19) | C7—H7 | 0.93 |
| Cu1—N4 | 2.0106 (16) | C13—C8 | 1.419 (3) |
| Cu1—N5 | 1.9315 (16) | C13—C12 | 1.420 (3) |
| N1—N2 | 1.181 (3) | C5—C6 | 1.500 (3) |
| N2—N3 | 1.147 (3) | C1—C2 | 1.364 (3) |
| O1—C13 | 1.316 (2) | C1—H1 | 0.93 |
| O2—C12 | 1.368 (3) | C3—C2 | 1.377 (4) |
| O2—C14 | 1.423 (3) | C3—H3 | 0.93 |
| C11—C12 | 1.387 (3) | C9—C10 | 1.355 (3) |
| C11—C10 | 1.397 (3) | C9—C8 | 1.423 (3) |
| C11—H11 | 0.93 | C9—H9 | 0.93 |
| N5—C7 | 1.290 (3) | C6—H6A | 0.97 |
| N5—C6 | 1.461 (2) | C6—H6B | 0.97 |
| N4—C5 | 1.338 (3) | C14—H14A | 0.96 |
| N4—C1 | 1.351 (3) | C14—H14B | 0.96 |
| C4—C3 | 1.384 (3) | C14—H14C | 0.96 |
| C4—C5 | 1.380 (3) | C2—H2 | 0.93 |
| C4—H4 | 0.93 | C10—H10 | 0.93 |
| O1—Cu1—N1 | 90.95 (7) | C4—C5—C6 | 121.54 (18) |
| O1—Cu1—N5 | 93.59 (6) | N4—C1—C2 | 122.5 (2) |
| N1—Cu1—N5 | 175.35 (7) | N4—C1—H1 | 118.8 |
| O1—Cu1—N4 | 175.78 (5) | C2—C1—H1 | 118.8 |
| N4—Cu1—N5 | 82.20 (7) | C4—C3—C2 | 118.7 (2) |
| N1—Cu1—N4 | 93.26 (8) | C4—C3—H3 | 120.6 |
| N1—N2—N3 | 176.4 (2) | C2—C3—H3 | 120.6 |
| C13—O1—Cu1 | 127.21 (13) | C10—C9—C8 | 120.8 (2) |
| C12—O2—C14 | 118.41 (18) | C10—C9—H9 | 119.6 |
| C12—C11—C10 | 120.8 (2) | C8—C9—H9 | 119.6 |
| C12—C11—H11 | 119.6 | N2—N1—Cu1 | 122.36 (17) |
| C10—C11—H11 | 119.6 | N5—C6—C5 | 109.75 (16) |
| C7—N5—C6 | 117.27 (17) | N5—C6—H6A | 109.7 |
| C7—N5—Cu1 | 126.15 (14) | C5—C6—H6A | 109.7 |
| C6—N5—Cu1 | 116.57 (13) | N5—C6—H6B | 109.7 |
| C5—N4—C1 | 118.20 (18) | C5—C6—H6B | 109.7 |
| C5—N4—Cu1 | 115.20 (14) | H6A—C6—H6B | 108.2 |
| C1—N4—Cu1 | 126.61 (14) | C9—C8—C13 | 120.07 (19) |
| C3—C4—C5 | 119.0 (2) | C9—C8—C7 | 116.64 (19) |
| C3—C4—H4 | 120.5 | C13—C8—C7 | 123.29 (19) |
| C5—C4—H4 | 120.5 | O2—C14—H14A | 109.5 |
| N5—C7—C8 | 125.60 (18) | O2—C14—H14B | 109.5 |
| N5—C7—H7 | 117.2 | H14A—C14—H14B | 109.5 |
| C8—C7—H7 | 117.2 | O2—C14—H14C | 109.5 |
| O1—C13—C8 | 124.15 (18) | H14A—C14—H14C | 109.5 |
| O1—C13—C12 | 118.36 (17) | H14B—C14—H14C | 109.5 |
| C8—C13—C12 | 117.49 (18) | C1—C2—C3 | 119.4 (2) |
| O2—C12—C11 | 124.42 (19) | C1—C2—H2 | 120.3 |
| O2—C12—C13 | 114.87 (18) | C3—C2—H2 | 120.3 |
| C11—C12—C13 | 120.70 (19) | C9—C10—C11 | 120.1 (2) |
| N4—C5—C4 | 122.2 (2) | C9—C10—H10 | 119.9 |
| N4—C5—C6 | 116.27 (17) | C11—C10—H10 | 119.9 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···N3i | 0.93 | 2.49 | 3.189 (2) | 132 |
| Symmetry codes: (i) x, y−1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···N3i | 0.93 | 2.49 | 3.189 (2) | 132 |
| Symmetry codes: (i) x, y−1, z. |
Bruker (2001). SAINT-Plus and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Kannappan, R., Tanase, S., Mutikainen, I., Turpeinen, U. & Reedijk, J. (2005). Inorg. Chim. Acta, 358, 383–388.
Li, Z.-X. & Zhang, X.-L. (2004). Acta Cryst. E60, m1017–m1019.
Ni, Z.-H. & Wang, H.-L. (2007). Acta Cryst. E63, o3799–?.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (1998). XP. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.
Sun, Y.-X. (2005). Acta Cryst. E61, m338–m340.
Yang, D.-S. (2005). Acta Cryst. E61, m247–m248.
Some Schiff bases can be potential employed as in-plane ligands which usually exhibit beautiful supramolecular structures via π-π interactions (Kannappan et al., 2005; Li & Zhang, 2004; Yang, 2005). In addtion, the complexes based on these Schiff base ligands can form various hydrogen bonds through reasonable design and the introduction of suitable assistant groups (Sun, 2005).
The geometry and labelling scheme for the crystal structure of the title complex are depicted in Figure 1. The title compound is a monomeric neutral complex with one tridentate unsymmetric Schiff base 6-Methoxy-2-(2-pyridylmethyliminomethyl)phenol and one azide group, which are similar to its derivatives [Cu(C14H13N2O2)(Cl)] and [Cu(C14H13N2O2)(Br)] (Kannappan et al., 2005). The Cu(II) center of the title complex is coordinated by one pyridine and one imide nitrogen atoms and one phenoxo oxygen atom from Schiff base ligand and one terminal nitrogen atom from azide group, yielding a distorted square-planar coordinaton environment. All atoms in the title complex except N2 and N3 form a plane with the largest deviation value of 0.0514 (16) Å from the mean plane.
The Cu1—O1 bond distance is 1.9062 (14) Å. The Cu—Npyridine, Cu—Nimine and Cu—Nazide bond lengths are 2.0106 (16), 1.9315 (16) and 1.9504 (19) Å, which are similar to those in complexes [Cu(C14H13N2O2)(Cl)] and [Cu(C14H13N2O2)(Br)]. The bond angles O1—Cu1—N4 (175.78 (5) Å) and N1—Cu1—N5 (175.35 (7) Å) are nearly linear. The chelate bite angles for the five and six-membered rings formed by the Schiff base are 82.20 (7) ° and 93.59 (6) °, which are also similar to those in the Cl and Br complexes reported by Kannappan et al., (2005). The imide bond length (1.290 (3) Å for C7—N5) is slightly longer than that in ligand 6-Methoxy-2-(2-pyridylmethyliminomethyl)phenol (1.278 (2) Å) (Ni et al., 2007). The N—N bond distances are 1.181 (3) Å for N1—N2 and 1.147 (3) Å for N2—N3. The N1—N2—N3 bond angle is 176.4 (2) ° and the Cu1—N1—N2 bond angle is 122.36 (17) °.
The title compound shows various non-covalent intermolecular interactions and forms a very interesting two-dimensional supramolecular network structure (Figure 2). The units of the title complexes connect each other by two different π-π interactions with inter-unit distances 3.359 (3) Å and 3.378 (2) Å, resulting in one-dimensional supramolecular substructures. These substructures are linked by the C—H···N hydrogen bonds between the pyridine carbon atom and uncoordinated terminal azide nitrogen atom into a beautiful two-dimensional supramolecular structure.