Acta Cryst. (2007). E63, m2960 [ doi:10.1107/S1600536807056048 ]
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3N,N',O}(thiocyanato-N)copper(II)In the title compound, [Cu(C11H14BrN2O)(NCS)], the Cu atom is four-coordinated by the NNO donor set of the Schiff base ligand and by the terminal N atom of the thiocyanate anion, forming a square-planar geometry. An N-H
S hydrogen bond helps to establish the packing.
5-Bromosalicylaldehyde (0.1 mmol, 20.1 mg), N-ethylethane-1,2-diamine (0.1 mmol, 8.8 mg), ammonium thiocyanate (0.1 mmol, 7.6 mg) and copper acetate (0.1 mmol, 20.0 mg) were mixed in a methanol solution (10 ml). The mixture was stirred at room temperature for 30 min to give a deep blue solution. Blue blocks of (I) were formed by slow evaporation of the solution in air.
The N-bound H atom was located in a difference map and freely refined.
The C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 or 1.5 times Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).
![[Figure 1]](./hb2616fig1thm.gif)
| Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids (arbitrary spheres for the H atoms). |
| [Cu(C11H14BrN2O)(NCS)] | F000 = 780 |
| Mr = 391.77 | Dx = 1.771 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1356 reflections |
| a = 6.3368 (12) Å | θ = 2.4–24.9º |
| b = 19.163 (4) Å | µ = 4.34 mm−1 |
| c = 12.308 (2) Å | T = 298 (2) K |
| β = 100.601 (3)º | Block, blue |
| V = 1469.1 (5) Å3 | 0.15 × 0.13 × 0.10 mm |
| Z = 4 |
| Bruker SMART APEXII CCD diffractometer | 3350 independent reflections |
| Radiation source: fine-focus sealed tube | 2054 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.073 |
| T = 298(2) K | θmax = 27.5º |
| ω scans | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −8→8 |
| Tmin = 0.562, Tmax = 0.671 | k = −24→24 |
| 12464 measured reflections | l = −15→15 |
| 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)] = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.148 | w = 1/[σ2(Fo2) + (0.0585P)2 + 0.919P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 3350 reflections | Δρmax = 0.74 e Å−3 |
| 176 parameters | Δρmin = −0.59 e Å−3 |
| 1 restraint | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [Cu(C11H14BrN2O)(NCS)] | V = 1469.1 (5) Å3 |
| Mr = 391.77 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 6.3368 (12) Å | µ = 4.34 mm−1 |
| b = 19.163 (4) Å | T = 298 (2) K |
| c = 12.308 (2) Å | 0.15 × 0.13 × 0.10 mm |
| β = 100.601 (3)º |
| Bruker SMART APEXII CCD diffractometer | 3350 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2054 reflections with I > 2σ(I) |
| Tmin = 0.562, Tmax = 0.671 | Rint = 0.073 |
| 12464 measured reflections |
| R[F2 > 2σ(F2)] = 0.061 | 1 restraint |
| wR(F2) = 0.148 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.02 | Δρmax = 0.74 e Å−3 |
| 3350 reflections | Δρmin = −0.59 e Å−3 |
| 176 parameters |
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 | 0.76392 (11) | 0.19400 (4) | 0.04069 (6) | 0.0411 (2) | |
| Br1 | 1.26434 (12) | −0.06356 (4) | −0.27110 (7) | 0.0665 (3) | |
| S1 | 0.0947 (3) | 0.28292 (10) | −0.10857 (15) | 0.0584 (5) | |
| O1 | 0.6977 (6) | 0.1300 (2) | −0.0701 (3) | 0.0427 (10) | |
| N1 | 1.0370 (7) | 0.1586 (2) | 0.0899 (4) | 0.0374 (11) | |
| N2 | 0.8306 (9) | 0.2596 (3) | 0.1625 (4) | 0.0514 (14) | |
| N3 | 0.4882 (8) | 0.2303 (3) | −0.0064 (4) | 0.0461 (13) | |
| C1 | 1.0482 (9) | 0.0795 (3) | −0.0614 (5) | 0.0367 (13) | |
| C2 | 0.8301 (9) | 0.0898 (3) | −0.1105 (4) | 0.0351 (13) | |
| C3 | 0.7508 (10) | 0.0525 (3) | −0.2095 (5) | 0.0497 (16) | |
| H3 | 0.6083 | 0.0578 | −0.2439 | 0.060* | |
| C4 | 0.8822 (10) | 0.0090 (3) | −0.2544 (6) | 0.0501 (16) | |
| H4 | 0.8279 | −0.0152 | −0.3190 | 0.060* | |
| C5 | 1.0960 (10) | 0.0003 (3) | −0.2050 (6) | 0.0471 (15) | |
| C6 | 1.1782 (10) | 0.0347 (3) | −0.1109 (5) | 0.0423 (14) | |
| H6 | 1.3217 | 0.0287 | −0.0787 | 0.051* | |
| C7 | 1.1358 (9) | 0.1143 (3) | 0.0405 (5) | 0.0433 (15) | |
| H7 | 1.2763 | 0.1034 | 0.0731 | 0.052* | |
| C8 | 1.1484 (10) | 0.1894 (3) | 0.1934 (5) | 0.0490 (16) | |
| H8A | 1.3019 | 0.1908 | 0.1947 | 0.059* | |
| H8B | 1.1224 | 0.1621 | 0.2559 | 0.059* | |
| C9 | 1.0620 (10) | 0.2614 (3) | 0.1986 (6) | 0.0549 (18) | |
| H9A | 1.0969 | 0.2789 | 0.2737 | 0.066* | |
| H9B | 1.1260 | 0.2923 | 0.1513 | 0.066* | |
| C10 | 0.7238 (12) | 0.3277 (4) | 0.1615 (6) | 0.0610 (19) | |
| H10A | 0.7791 | 0.3516 | 0.2303 | 0.073* | |
| H10B | 0.5714 | 0.3201 | 0.1584 | 0.073* | |
| C11 | 0.7524 (13) | 0.3740 (4) | 0.0674 (7) | 0.078 (2) | |
| H11A | 0.9028 | 0.3801 | 0.0674 | 0.117* | |
| H11B | 0.6881 | 0.4186 | 0.0755 | 0.117* | |
| H11C | 0.6848 | 0.3531 | −0.0011 | 0.117* | |
| C12 | 0.3270 (9) | 0.2526 (3) | −0.0482 (5) | 0.0391 (14) | |
| H2 | 0.801 (11) | 0.237 (3) | 0.222 (4) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0367 (4) | 0.0458 (5) | 0.0390 (4) | −0.0040 (3) | 0.0024 (3) | −0.0002 (3) |
| Br1 | 0.0680 (5) | 0.0485 (4) | 0.0901 (6) | −0.0006 (3) | 0.0334 (4) | −0.0116 (4) |
| S1 | 0.0429 (10) | 0.0786 (13) | 0.0543 (11) | 0.0118 (8) | 0.0104 (8) | 0.0249 (9) |
| O1 | 0.034 (2) | 0.043 (2) | 0.047 (2) | −0.0003 (18) | −0.0052 (18) | −0.0099 (19) |
| N1 | 0.034 (3) | 0.041 (3) | 0.035 (3) | −0.004 (2) | 0.000 (2) | 0.004 (2) |
| N2 | 0.052 (3) | 0.057 (3) | 0.042 (3) | −0.004 (3) | 0.001 (3) | −0.010 (3) |
| N3 | 0.034 (3) | 0.058 (3) | 0.045 (3) | 0.004 (2) | 0.004 (2) | −0.011 (2) |
| C1 | 0.033 (3) | 0.031 (3) | 0.046 (4) | −0.005 (2) | 0.008 (3) | 0.006 (3) |
| C2 | 0.038 (3) | 0.029 (3) | 0.035 (3) | −0.003 (2) | −0.001 (3) | 0.005 (2) |
| C3 | 0.045 (4) | 0.037 (3) | 0.059 (4) | 0.004 (3) | −0.010 (3) | −0.009 (3) |
| C4 | 0.047 (4) | 0.045 (4) | 0.055 (4) | −0.010 (3) | 0.001 (3) | −0.010 (3) |
| C5 | 0.051 (4) | 0.033 (3) | 0.059 (4) | 0.000 (3) | 0.015 (3) | 0.002 (3) |
| C6 | 0.041 (3) | 0.034 (3) | 0.054 (4) | 0.002 (3) | 0.014 (3) | 0.007 (3) |
| C7 | 0.032 (3) | 0.044 (4) | 0.051 (4) | −0.004 (3) | −0.001 (3) | 0.015 (3) |
| C8 | 0.048 (4) | 0.058 (4) | 0.037 (3) | −0.013 (3) | −0.003 (3) | 0.002 (3) |
| C9 | 0.048 (4) | 0.065 (4) | 0.050 (4) | −0.013 (3) | 0.003 (3) | −0.023 (3) |
| C10 | 0.068 (5) | 0.061 (5) | 0.056 (4) | 0.001 (4) | 0.015 (4) | −0.014 (4) |
| C11 | 0.090 (6) | 0.058 (5) | 0.080 (6) | 0.002 (4) | −0.001 (5) | −0.014 (4) |
| C12 | 0.034 (3) | 0.048 (4) | 0.038 (3) | −0.007 (3) | 0.013 (3) | −0.009 (3) |
| Cu1—O1 | 1.825 (4) | C3—H3 | 0.9300 |
| Cu1—N1 | 1.853 (5) | C4—C5 | 1.389 (8) |
| Cu1—N3 | 1.870 (5) | C4—H4 | 0.9300 |
| Cu1—N2 | 1.942 (5) | C5—C6 | 1.351 (8) |
| Br1—C5 | 1.902 (6) | C6—H6 | 0.9300 |
| S1—C12 | 1.629 (6) | C7—H7 | 0.9300 |
| O1—C2 | 1.304 (6) | C8—C9 | 1.491 (8) |
| N1—C7 | 1.274 (7) | C8—H8A | 0.9700 |
| N1—C8 | 1.462 (7) | C8—H8B | 0.9700 |
| N2—C9 | 1.452 (8) | C9—H9A | 0.9700 |
| N2—C10 | 1.471 (8) | C9—H9B | 0.9700 |
| N2—H2 | 0.90 (5) | C10—C11 | 1.496 (10) |
| N3—C12 | 1.140 (7) | C10—H10A | 0.9700 |
| C1—C6 | 1.404 (8) | C10—H10B | 0.9700 |
| C1—C2 | 1.417 (7) | C11—H11A | 0.9600 |
| C1—C7 | 1.438 (8) | C11—H11B | 0.9600 |
| C2—C3 | 1.422 (8) | C11—H11C | 0.9600 |
| C3—C4 | 1.364 (8) | ||
| O1—Cu1—N1 | 94.06 (19) | C5—C6—C1 | 120.4 (6) |
| O1—Cu1—N3 | 86.84 (19) | C5—C6—H6 | 119.8 |
| N1—Cu1—N3 | 179.0 (2) | C1—C6—H6 | 119.8 |
| O1—Cu1—N2 | 177.8 (2) | N1—C7—C1 | 125.5 (5) |
| N1—Cu1—N2 | 85.8 (2) | N1—C7—H7 | 117.3 |
| N3—Cu1—N2 | 93.3 (2) | C1—C7—H7 | 117.3 |
| C2—O1—Cu1 | 127.4 (3) | N1—C8—C9 | 106.8 (5) |
| C7—N1—C8 | 118.9 (5) | N1—C8—H8A | 110.4 |
| C7—N1—Cu1 | 126.8 (4) | C9—C8—H8A | 110.4 |
| C8—N1—Cu1 | 114.2 (4) | N1—C8—H8B | 110.4 |
| C9—N2—C10 | 114.7 (5) | C9—C8—H8B | 110.4 |
| C9—N2—Cu1 | 108.5 (4) | H8A—C8—H8B | 108.6 |
| C10—N2—Cu1 | 122.3 (4) | N2—C9—C8 | 108.8 (5) |
| C9—N2—H2 | 96 (5) | N2—C9—H9A | 109.9 |
| C10—N2—H2 | 105 (5) | C8—C9—H9A | 109.9 |
| Cu1—N2—H2 | 106 (5) | N2—C9—H9B | 109.9 |
| C12—N3—Cu1 | 171.2 (5) | C8—C9—H9B | 109.9 |
| C6—C1—C2 | 120.3 (5) | H9A—C9—H9B | 108.3 |
| C6—C1—C7 | 119.9 (5) | N2—C10—C11 | 114.3 (6) |
| C2—C1—C7 | 119.8 (5) | N2—C10—H10A | 108.7 |
| O1—C2—C1 | 124.4 (5) | C11—C10—H10A | 108.7 |
| O1—C2—C3 | 118.3 (5) | N2—C10—H10B | 108.7 |
| C1—C2—C3 | 117.3 (5) | C11—C10—H10B | 108.7 |
| C4—C3—C2 | 120.5 (6) | H10A—C10—H10B | 107.6 |
| C4—C3—H3 | 119.7 | C10—C11—H11A | 109.5 |
| C2—C3—H3 | 119.7 | C10—C11—H11B | 109.5 |
| C3—C4—C5 | 121.0 (6) | H11A—C11—H11B | 109.5 |
| C3—C4—H4 | 119.5 | C10—C11—H11C | 109.5 |
| C5—C4—H4 | 119.5 | H11A—C11—H11C | 109.5 |
| C6—C5—C4 | 120.5 (6) | H11B—C11—H11C | 109.5 |
| C6—C5—Br1 | 121.5 (5) | N3—C12—S1 | 178.8 (6) |
| C4—C5—Br1 | 117.9 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···S1i | 0.90 (5) | 2.68 (3) | 3.520 (6) | 155 (6) |
| Symmetry codes: (i) x+1/2, −y+1/2, z+1/2. |
| Cu1—O1 | 1.825 (4) | Cu1—N3 | 1.870 (5) |
| Cu1—N1 | 1.853 (5) | Cu1—N2 | 1.942 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···S1i | 0.90 (5) | 2.68 (3) | 3.520 (6) | 155 (6) |
| Symmetry codes: (i) x+1/2, −y+1/2, z+1/2. |
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Li, J.-X., Jiang, Y.-M. & Wang, J.-G. (2007). Acta Cryst. E63, m601–m603.
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Recently, we have reported a Schiff base-nickel(II) complex (Zhou & Xiao, 2007). As an extensive of our work, we report herein the crystal structure of the title mononuclear copper(II) complex, (I), (Fig. 1).
The Cu atom in (I) is four-coordinated by the NNO donor set of the Schiff base ligand and by the terminal N atom of the thiocyante anion, forming a square-planar geometry. The bond lengths and bond angles (Table 1) subtended at the metal centre are comparable to the values in similar copper(II) complexes (Xu et al., 2005; Wang & Li, 2005; Wang et al., 2006; Li et al., 2007).
An N—H···S hydrogen bond helps to establish the packing (Table 2).