Acta Cryst. (2007). E63, m2629 [ doi:10.1107/S1600536807047022 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-thiocyanato-![[kappa]](/logos/entities/kappa_rmgif.gif)
4N:N-bis({2-[2-(methylamino)ethyliminomethyl]phenolato}copper(II))The asymmetric unit of the title compound, [Cu2(NCS)2(C10H13N2O)2], contains one-half of the centrosymmetric dinuclear complex, which exhibits a Cu
Cu separation of 3.255 (2) Å. In the complex, each CuII ion is pentacoordinated in a square-pyramidal geometry. The basal plane is formed by one phenol O [Cu-O = 1.910 (4) Å], one imine N [Cu-N = 1.922 (5) Å] and one amine N [Cu-N = 2.041 (5) Å] atoms from the Schiff base ligand, and by the N atom [Cu-N = 1.940 (6) Å] from a thiocyanate ligand. The apical position is occupied by the N atom [Cu-N = 2.768 (6) Å] of another thiocyanate ligand. There are intramolecular N-HO hydrogen bonds linking the two ligands.
Salicyaldehyde (1.0 mmol, 122.1 mg), N-methylethane-1,2-diamine (1.0 mmol, 74.0 mg), NH4NCS (1.0 mmol, 7.6 mg) and Cu(CH3COO)2·H2O (1.0 mmol, 199.1 mg) were dissolved in a methanol solution (150 ml). The mixture was refluxed at 340 K for about 1 h to give a clear blue solution. After keeping the cooled resulting solution in dark for five days, blue needle-shaped crystals were formed.
Atom H2 attached to N2 was located from a difference Fourier map and refined isotropically, with N–H distance restrained to 0.90 (3) Å. Other H atoms were placed geometrically, with C–H distances in the range 0.93–0.97 Å, and with Uiso(H) set to 1.2Ueq(C) and 1.5Ueq(methyl C).
Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
![[Figure 1]](./cv2307fig1thm.gif)
| Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. Unlabelled atoms are related with labelled ones by symmetry code (−x + 2, −y, −z + 1). |
| [Cu2(NCS)2(C10H13N2O)2] | F000 = 612 |
| Mr = 597.69 | Dx = 1.602 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| a = 8.3305 (19) Å | Cell parameters from 944 reflections |
| b = 16.982 (4) Å | θ = 2.3–24.9º |
| c = 9.137 (2) Å | µ = 1.92 mm−1 |
| β = 106.562 (3)º | T = 298 (2) K |
| V = 1239.0 (5) Å3 | Needle, blue |
| Z = 2 | 0.20 × 0.07 × 0.06 mm |
| Bruker SMART CCD area-detector diffractometer | 2431 independent reflections |
| Radiation source: fine-focus sealed tube | 1510 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.087 |
| T = 298(2) K | θmax = 26.0º |
| ω scans | θmin = 2.4º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
| Tmin = 0.700, Tmax = 0.894 | k = −20→20 |
| 9340 measured reflections | l = −11→11 |
| 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)] = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.160 | w = 1/[σ2(Fo2) + (0.0643P)2 + 0.4135P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 2431 reflections | Δρmax = 0.45 e Å−3 |
| 158 parameters | Δρmin = −0.67 e Å−3 |
| 1 restraint | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [Cu2(NCS)2(C10H13N2O)2] | V = 1239.0 (5) Å3 |
| Mr = 597.69 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 8.3305 (19) Å | µ = 1.92 mm−1 |
| b = 16.982 (4) Å | T = 298 (2) K |
| c = 9.137 (2) Å | 0.20 × 0.07 × 0.06 mm |
| β = 106.562 (3)º |
| Bruker SMART CCD area-detector diffractometer | 2431 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1510 reflections with I > 2σ(I) |
| Tmin = 0.700, Tmax = 0.894 | Rint = 0.087 |
| 9340 measured reflections |
| R[F2 > 2σ(F2)] = 0.064 | 1 restraint |
| wR(F2) = 0.160 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | Δρmax = 0.45 e Å−3 |
| 2431 reflections | Δρmin = −0.67 e Å−3 |
| 158 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 | 0.96892 (9) | 0.04411 (4) | 0.33613 (8) | 0.0410 (3) | |
| S1 | 1.4907 (3) | 0.09746 (15) | 0.6792 (3) | 0.1066 (10) | |
| O1 | 1.0498 (5) | −0.0513 (2) | 0.2719 (4) | 0.0443 (10) | |
| N1 | 0.7859 (6) | 0.0530 (3) | 0.1529 (5) | 0.0398 (12) | |
| N2 | 0.8447 (7) | 0.1282 (3) | 0.4207 (5) | 0.0463 (13) | |
| N3 | 1.1753 (7) | 0.0566 (3) | 0.4992 (6) | 0.0558 (15) | |
| C1 | 0.8475 (8) | −0.0616 (3) | 0.0253 (7) | 0.0412 (14) | |
| C2 | 0.9862 (7) | −0.0881 (3) | 0.1430 (6) | 0.0372 (14) | |
| C3 | 1.0614 (9) | −0.1608 (4) | 0.1219 (8) | 0.0530 (17) | |
| H3 | 1.1495 | −0.1808 | 0.2000 | 0.064* | |
| C4 | 1.0052 (10) | −0.2015 (4) | −0.0123 (9) | 0.066 (2) | |
| H4 | 1.0556 | −0.2491 | −0.0237 | 0.079* | |
| C5 | 0.8739 (10) | −0.1731 (5) | −0.1324 (9) | 0.070 (2) | |
| H5 | 0.8393 | −0.2008 | −0.2238 | 0.084* | |
| C6 | 0.7964 (9) | −0.1042 (4) | −0.1144 (7) | 0.0562 (18) | |
| H6 | 0.7093 | −0.0851 | −0.1944 | 0.067* | |
| C7 | 0.7571 (7) | 0.0073 (3) | 0.0369 (6) | 0.0406 (14) | |
| H7 | 0.6687 | 0.0207 | −0.0475 | 0.049* | |
| C8 | 0.6778 (8) | 0.1198 (4) | 0.1574 (7) | 0.0503 (16) | |
| H8A | 0.5665 | 0.1106 | 0.0896 | 0.060* | |
| H8B | 0.7224 | 0.1672 | 0.1243 | 0.060* | |
| C9 | 0.6698 (8) | 0.1295 (4) | 0.3187 (7) | 0.0554 (17) | |
| H9A | 0.6163 | 0.1791 | 0.3295 | 0.066* | |
| H9B | 0.6054 | 0.0871 | 0.3451 | 0.066* | |
| C10 | 0.9218 (9) | 0.2060 (4) | 0.4491 (8) | 0.072 (2) | |
| H10A | 0.9340 | 0.2272 | 0.3554 | 0.108* | |
| H10B | 1.0299 | 0.2018 | 0.5224 | 0.108* | |
| H10C | 0.8521 | 0.2403 | 0.4881 | 0.108* | |
| C11 | 1.3052 (9) | 0.0744 (4) | 0.5740 (7) | 0.0510 (17) | |
| H2 | 0.841 (9) | 0.110 (4) | 0.512 (4) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0387 (4) | 0.0473 (5) | 0.0355 (4) | 0.0051 (4) | 0.0082 (3) | −0.0031 (4) |
| S1 | 0.0748 (16) | 0.1044 (19) | 0.1027 (17) | −0.0400 (14) | −0.0359 (13) | 0.0478 (15) |
| O1 | 0.050 (3) | 0.049 (3) | 0.033 (2) | 0.011 (2) | 0.0107 (19) | −0.0028 (19) |
| N1 | 0.034 (3) | 0.045 (3) | 0.041 (3) | 0.008 (2) | 0.011 (2) | 0.010 (2) |
| N2 | 0.054 (3) | 0.044 (3) | 0.042 (3) | 0.003 (3) | 0.017 (3) | −0.010 (2) |
| N3 | 0.047 (3) | 0.072 (4) | 0.047 (3) | 0.007 (3) | 0.011 (3) | −0.007 (3) |
| C1 | 0.040 (4) | 0.044 (4) | 0.046 (4) | −0.014 (3) | 0.021 (3) | −0.006 (3) |
| C2 | 0.041 (4) | 0.045 (4) | 0.032 (3) | −0.004 (3) | 0.020 (3) | 0.006 (3) |
| C3 | 0.069 (5) | 0.042 (4) | 0.057 (4) | 0.006 (3) | 0.034 (4) | 0.003 (3) |
| C4 | 0.085 (6) | 0.049 (4) | 0.078 (5) | −0.008 (4) | 0.048 (5) | −0.013 (4) |
| C5 | 0.087 (6) | 0.076 (5) | 0.064 (5) | −0.036 (5) | 0.050 (5) | −0.037 (4) |
| C6 | 0.059 (4) | 0.077 (5) | 0.039 (4) | −0.017 (4) | 0.024 (3) | −0.009 (4) |
| C7 | 0.042 (4) | 0.050 (4) | 0.026 (3) | −0.003 (3) | 0.004 (3) | 0.002 (3) |
| C8 | 0.048 (4) | 0.056 (4) | 0.044 (4) | 0.010 (3) | 0.009 (3) | 0.006 (3) |
| C9 | 0.042 (4) | 0.059 (4) | 0.067 (5) | 0.011 (3) | 0.018 (3) | −0.003 (4) |
| C10 | 0.078 (6) | 0.058 (5) | 0.084 (5) | 0.001 (4) | 0.032 (4) | −0.016 (4) |
| C11 | 0.050 (4) | 0.056 (4) | 0.041 (4) | −0.001 (3) | 0.005 (3) | 0.008 (3) |
| Cu1—O1 | 1.910 (4) | C3—C4 | 1.369 (9) |
| Cu1—N1 | 1.922 (5) | C3—H3 | 0.9300 |
| Cu1—N3 | 1.940 (6) | C4—C5 | 1.396 (10) |
| Cu1—N2 | 2.041 (5) | C4—H4 | 0.9300 |
| S1—C11 | 1.617 (7) | C5—C6 | 1.368 (10) |
| O1—C2 | 1.305 (6) | C5—H5 | 0.9300 |
| N1—C7 | 1.280 (7) | C6—H6 | 0.9300 |
| N1—C8 | 1.457 (7) | C7—H7 | 0.9300 |
| N2—C10 | 1.459 (8) | C8—C9 | 1.503 (8) |
| N2—C9 | 1.490 (8) | C8—H8A | 0.9700 |
| N2—H2 | 0.90 (4) | C8—H8B | 0.9700 |
| N3—C11 | 1.144 (8) | C9—H9A | 0.9700 |
| C1—C2 | 1.410 (8) | C9—H9B | 0.9700 |
| C1—C7 | 1.411 (8) | C10—H10A | 0.9600 |
| C1—C6 | 1.423 (8) | C10—H10B | 0.9600 |
| C2—C3 | 1.422 (8) | C10—H10C | 0.9600 |
| O1—Cu1—N1 | 93.47 (18) | C6—C5—C4 | 119.5 (6) |
| O1—Cu1—N3 | 90.91 (19) | C6—C5—H5 | 120.3 |
| N1—Cu1—N3 | 165.9 (2) | C4—C5—H5 | 120.3 |
| O1—Cu1—N2 | 166.3 (2) | C5—C6—C1 | 120.8 (7) |
| N1—Cu1—N2 | 85.0 (2) | C5—C6—H6 | 119.6 |
| N3—Cu1—N2 | 93.8 (2) | C1—C6—H6 | 119.6 |
| C2—O1—Cu1 | 126.6 (4) | N1—C7—C1 | 125.9 (5) |
| C7—N1—C8 | 121.6 (5) | N1—C7—H7 | 117.0 |
| C7—N1—Cu1 | 126.0 (4) | C1—C7—H7 | 117.0 |
| C8—N1—Cu1 | 112.3 (4) | N1—C8—C9 | 108.3 (5) |
| C10—N2—C9 | 113.6 (5) | N1—C8—H8A | 110.0 |
| C10—N2—Cu1 | 117.1 (4) | C9—C8—H8A | 110.0 |
| C9—N2—Cu1 | 106.5 (4) | N1—C8—H8B | 110.0 |
| C10—N2—H2 | 106 (5) | C9—C8—H8B | 110.0 |
| C9—N2—H2 | 107 (5) | H8A—C8—H8B | 108.4 |
| Cu1—N2—H2 | 105 (5) | N2—C9—C8 | 107.7 (5) |
| C11—N3—Cu1 | 165.6 (6) | N2—C9—H9A | 110.2 |
| C2—C1—C7 | 123.1 (5) | C8—C9—H9A | 110.2 |
| C2—C1—C6 | 119.5 (6) | N2—C9—H9B | 110.2 |
| C7—C1—C6 | 117.4 (6) | C8—C9—H9B | 110.2 |
| O1—C2—C1 | 124.7 (5) | H9A—C9—H9B | 108.5 |
| O1—C2—C3 | 117.2 (5) | N2—C10—H10A | 109.5 |
| C1—C2—C3 | 118.1 (5) | N2—C10—H10B | 109.5 |
| C4—C3—C2 | 120.6 (6) | H10A—C10—H10B | 109.5 |
| C4—C3—H3 | 119.7 | N2—C10—H10C | 109.5 |
| C2—C3—H3 | 119.7 | H10A—C10—H10C | 109.5 |
| C3—C4—C5 | 121.4 (7) | H10B—C10—H10C | 109.5 |
| C3—C4—H4 | 119.3 | N3—C11—S1 | 178.6 (7) |
| C5—C4—H4 | 119.3 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1i | 0.90 (4) | 2.17 (3) | 2.993 (6) | 153 (6) |
| Symmetry codes: (i) −x+2, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1i | 0.90 (4) | 2.17 (3) | 2.993 (6) | 153 (6) |
| Symmetry codes: (i) −x+2, −y, −z+1. |
This work was supported by the Education Office of Anhui Province (grant No. 2004kj326).
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In continuation of our study of copper complexes with Shiff base ligands (Wei, 2005a,b; Wei & Wang, 2006), we report here the crystal structure of the title compound− a new dinuclear copper(II) complex (Fig. 1).
Each Cu atom in the complex is pentacoordinate in a square pyramidal geometry, with one phenolic O, one imine N, and one amine N atoms of one Schiff base ligand, and with one N atom of a thiocyanate ligand defining the basal plane, and with one N atom of another thiocyanate ligand occupying the apical position. The thiocyanate ligands adopt end-on coordination mode, with the Cu···Cu distance of 3.255 (2) Å. The coordinate bond lengths and angles are comparable with those observed in other Schiff base copper(II) complexes (Diao, Shu et al., 2007; Diao & Li, 2007).