Acta Cryst. (2007). E63, m2126 [ doi:10.1107/S1600536807033272 ]
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2N1,O]copper(II)In the mononuclear title complex, [Cu(C10H8BrN2O2)2], the Cu atom, which lies on a centre of symmetry, is in a square-planar geometry defined by a trans-N2O2 donor set.
1-(2-Bromobenzoyl)-3-(2-hydroxyethyl)thiourea was prepared according to literature (Douglass & Dains, 1934). This compound (2 mmol, 0.61 g) was dissolved in acetonitrile (20 ml). Dicyclohexylcarbodiimide (2 mmol, 0.22 g) and pyridine (0.02 mmol, 0.16 g), were added and the mixture was stirred for 12 h. The solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel to afford desired 2-bromo-N-(4,5-dihydrooxazol-2-yl)benzamide (yield 83%). To an ethanol solution (20 ml) of 2-bromo-N-(4,5-dihydrooxazol-2-yl)benzamide (1 mmol, 0.27 g) was added an ethanol solution (10 ml) of cupric(II) nitrate trihydrate (0.5 mmol, 0.12 g) with stirring. Black block-shaped crystals were formed at the bottom of the vessel upon slow evaporation of the solvent. The crystals were isolated, washed three times with ethanol and dried in a vacuum desiccator (yield 90%). Elemental analysis found: C 40.10, H 2.68, N 9.39%; C20H16Br2CuN4O4 requires: C 40.05, H 2.69.0, N 9.37%.
The H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances = 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
![[Figure 1]](./tk2176fig1thm.gif)
| Fig. 1. The structure of the title compound, (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. Unlabelled atoms are related to labelled atoms by 1 - x, -y, 2 - z. |
| [Cu(C10H8BrN2O2)2] | F(000) = 1180 |
| Mr = 599.73 | Dx = 1.955 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 4720 reflections |
| a = 11.4637 (9) Å | θ = 2.2–27.6° |
| b = 11.9265 (9) Å | µ = 5.03 mm−1 |
| c = 14.9016 (12) Å | T = 291 K |
| V = 2037.4 (3) Å3 | Block, blue |
| Z = 4 | 0.27 × 0.20 × 0.16 mm |
| Bruker SMART APEX CCD area-detector diffractometer | 2006 independent reflections |
| Radiation source: sealed tube | 1580 reflections with I > 2σ(I) |
| graphite | Rint = 0.059 |
| φ and ω scans | θmax = 26.0°, θmin = 2.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −14→14 |
| Tmin = 0.31, Tmax = 0.45 | k = −12→14 |
| 10306 measured reflections | l = −18→13 |
| 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.105 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0539P)2] where P = (Fo2 + 2Fc2)/3 |
| 2006 reflections | (Δ/σ)max < 0.001 |
| 142 parameters | Δρmax = 0.45 e Å−3 |
| 0 restraints | Δρmin = −0.65 e Å−3 |
| [Cu(C10H8BrN2O2)2] | V = 2037.4 (3) Å3 |
| Mr = 599.73 | Z = 4 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 11.4637 (9) Å | µ = 5.03 mm−1 |
| b = 11.9265 (9) Å | T = 291 K |
| c = 14.9016 (12) Å | 0.27 × 0.20 × 0.16 mm |
| Bruker SMART APEX CCD area-detector diffractometer | 2006 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1580 reflections with I > 2σ(I) |
| Tmin = 0.31, Tmax = 0.45 | Rint = 0.059 |
| 10306 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
| wR(F2) = 0.105 | Δρmax = 0.45 e Å−3 |
| S = 1.08 | Δρmin = −0.65 e Å−3 |
| 2006 reflections | Absolute structure: ? |
| 142 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 | ||
| Br1 | 0.55307 (4) | 0.37304 (4) | 0.91935 (4) | 0.04221 (18) | |
| C1 | 0.6284 (4) | −0.1319 (4) | 1.1432 (4) | 0.0517 (15) | |
| H1A | 0.5970 | −0.2010 | 1.1188 | 0.062* | |
| H1B | 0.5843 | −0.1113 | 1.1962 | 0.062* | |
| C2 | 0.7570 (4) | −0.1433 (4) | 1.1642 (4) | 0.0394 (11) | |
| H2A | 0.7695 | −0.1511 | 1.2283 | 0.047* | |
| H2B | 0.7900 | −0.2079 | 1.1340 | 0.047* | |
| C3 | 0.7293 (4) | 0.0068 (3) | 1.0760 (3) | 0.0273 (8) | |
| C4 | 0.7008 (4) | 0.1421 (3) | 0.9690 (3) | 0.0285 (9) | |
| C5 | 0.7599 (4) | 0.2323 (3) | 0.9150 (3) | 0.0284 (9) | |
| C6 | 0.7067 (4) | 0.3302 (4) | 0.8842 (3) | 0.0315 (9) | |
| C7 | 0.7635 (4) | 0.4066 (4) | 0.8315 (3) | 0.0395 (11) | |
| H7 | 0.7256 | 0.4713 | 0.8125 | 0.047* | |
| C8 | 0.8791 (5) | 0.3862 (5) | 0.8064 (4) | 0.0469 (13) | |
| H8 | 0.9185 | 0.4371 | 0.7700 | 0.056* | |
| C9 | 0.9347 (4) | 0.2900 (5) | 0.8359 (4) | 0.0457 (12) | |
| H9 | 1.0115 | 0.2757 | 0.8195 | 0.055* | |
| C10 | 0.8756 (4) | 0.2159 (4) | 0.8896 (3) | 0.0356 (10) | |
| H10 | 0.9143 | 0.1521 | 0.9098 | 0.043* | |
| Cu | 0.5000 | 0.0000 | 1.0000 | 0.0329 (2) | |
| N1 | 0.6269 (3) | −0.0407 (3) | 1.0754 (3) | 0.0360 (9) | |
| N2 | 0.7688 (3) | 0.0945 (3) | 1.0295 (3) | 0.0322 (8) | |
| O1 | 0.8085 (3) | −0.0406 (3) | 1.1313 (2) | 0.0365 (7) | |
| O2 | 0.5968 (3) | 0.1175 (2) | 0.9485 (2) | 0.0373 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0329 (3) | 0.0295 (3) | 0.0642 (4) | 0.00341 (19) | 0.0062 (2) | −0.0014 (2) |
| C1 | 0.035 (3) | 0.048 (3) | 0.073 (4) | −0.013 (2) | −0.015 (3) | 0.030 (3) |
| C2 | 0.037 (3) | 0.028 (2) | 0.053 (3) | 0.0020 (18) | −0.007 (2) | 0.008 (2) |
| C3 | 0.0254 (19) | 0.026 (2) | 0.031 (2) | 0.0027 (17) | −0.0070 (16) | −0.0004 (17) |
| C4 | 0.023 (2) | 0.0236 (19) | 0.039 (2) | −0.0005 (16) | −0.0003 (18) | 0.0049 (16) |
| C5 | 0.026 (2) | 0.027 (2) | 0.033 (2) | −0.0025 (16) | −0.0076 (18) | −0.0024 (16) |
| C6 | 0.029 (2) | 0.028 (2) | 0.037 (2) | −0.0023 (17) | 0.0001 (19) | 0.0004 (18) |
| C7 | 0.037 (2) | 0.027 (2) | 0.055 (3) | −0.0020 (19) | −0.001 (2) | 0.013 (2) |
| C8 | 0.037 (3) | 0.052 (3) | 0.052 (3) | −0.011 (2) | 0.010 (2) | 0.010 (2) |
| C9 | 0.028 (2) | 0.057 (3) | 0.052 (3) | −0.001 (2) | 0.002 (2) | 0.012 (3) |
| C10 | 0.025 (2) | 0.032 (2) | 0.050 (3) | −0.0009 (17) | −0.0042 (19) | 0.0025 (19) |
| Cu | 0.0224 (3) | 0.0276 (4) | 0.0486 (5) | −0.0066 (3) | −0.0093 (3) | 0.0110 (3) |
| N1 | 0.0219 (18) | 0.0317 (19) | 0.054 (3) | −0.0098 (15) | −0.0098 (16) | 0.0111 (18) |
| N2 | 0.0247 (18) | 0.0276 (17) | 0.044 (2) | −0.0064 (15) | −0.0043 (16) | 0.0052 (16) |
| O1 | 0.0267 (15) | 0.0387 (16) | 0.0442 (18) | −0.0036 (13) | −0.0134 (14) | 0.0090 (14) |
| O2 | 0.0254 (16) | 0.0268 (16) | 0.060 (2) | −0.0065 (12) | −0.0076 (15) | 0.0156 (14) |
| Br1—C6 | 1.907 (4) | C5—C10 | 1.393 (6) |
| C1—N1 | 1.484 (6) | C5—C6 | 1.395 (6) |
| C1—C2 | 1.513 (6) | C6—C7 | 1.368 (6) |
| C1—H1A | 0.9700 | C7—C8 | 1.399 (7) |
| C1—H1B | 0.9700 | C7—H7 | 0.9300 |
| C2—O1 | 1.446 (5) | C8—C9 | 1.385 (8) |
| C2—H2A | 0.9700 | C8—H8 | 0.9300 |
| C2—H2B | 0.9700 | C9—C10 | 1.371 (7) |
| C3—N1 | 1.304 (6) | C9—H9 | 0.9300 |
| C3—N2 | 1.333 (5) | C10—H10 | 0.9300 |
| C3—O1 | 1.350 (5) | Cu—N1i | 1.901 (4) |
| C4—O2 | 1.265 (5) | Cu—N1 | 1.901 (4) |
| C4—N2 | 1.319 (5) | Cu—O2 | 1.945 (3) |
| C4—C5 | 1.504 (6) | Cu—O2i | 1.945 (3) |
| N1—C1—C2 | 102.6 (4) | C6—C7—C8 | 119.3 (5) |
| N1—C1—H1A | 111.2 | C6—C7—H7 | 120.4 |
| C2—C1—H1A | 111.2 | C8—C7—H7 | 120.4 |
| N1—C1—H1B | 111.2 | C9—C8—C7 | 119.7 (5) |
| C2—C1—H1B | 111.2 | C9—C8—H8 | 120.2 |
| H1A—C1—H1B | 109.2 | C7—C8—H8 | 120.2 |
| O1—C2—C1 | 104.6 (4) | C10—C9—C8 | 119.5 (4) |
| O1—C2—H2A | 110.8 | C10—C9—H9 | 120.2 |
| C1—C2—H2A | 110.8 | C8—C9—H9 | 120.2 |
| O1—C2—H2B | 110.8 | C9—C10—C5 | 122.6 (4) |
| C1—C2—H2B | 110.8 | C9—C10—H10 | 118.7 |
| H2A—C2—H2B | 108.9 | C5—C10—H10 | 118.7 |
| N1—C3—N2 | 130.0 (4) | N1i—Cu—N1 | 180.000 (1) |
| N1—C3—O1 | 115.3 (4) | N1i—Cu—O2 | 91.11 (15) |
| N2—C3—O1 | 114.7 (4) | N1—Cu—O2 | 88.89 (15) |
| O2—C4—N2 | 128.4 (4) | N1i—Cu—O2i | 88.89 (15) |
| O2—C4—C5 | 117.4 (4) | N1—Cu—O2i | 91.11 (15) |
| N2—C4—C5 | 114.0 (4) | O2—Cu—O2i | 180.00 (12) |
| C10—C5—C6 | 116.4 (4) | C3—N1—C1 | 107.7 (4) |
| C10—C5—C4 | 118.3 (4) | C3—N1—Cu | 125.5 (3) |
| C6—C5—C4 | 125.3 (4) | C1—N1—Cu | 126.8 (3) |
| C7—C6—C5 | 122.5 (4) | C4—N2—C3 | 119.5 (4) |
| C7—C6—Br1 | 114.7 (3) | C3—O1—C2 | 106.7 (3) |
| C5—C6—Br1 | 122.6 (3) | C4—O2—Cu | 127.6 (3) |
| Symmetry codes: (i) −x+1, −y, −z+2. |
Bruker (2000). SMART (Version 5.618), SAINT (Version 6.02), SADABS (Version 2.03) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.
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Zhang, Y. M., Xian, L., Wei, T. B. & Yu, K. B. (2003). J. Chem. Res. pp. 798–799 [Is journal J. Chem. Res. (S) ?]
Oxazolines are important structural entities in natural products, can be used as protecting groups for carboxylic acids, and, as well, can be used as building blocks in organic synthesis (Wipf et al., 1992). In addition, oxazolines have been proven to powerful in transition metal-catalyzed organic synthesis (Paintner et al., 2005; Kato et al., 2004). Despite this interest, there are only two relevant structures that have been reported (Zhang et al., 2003; Jiang et al., 2006a,b). In order to extend the work on these complexes, the title mononuclear copper(II) complex, (I), is described herein.
The 2-bromo-N-(4,5-dihydrooxazol-2-yl)benzamide anion serves as a bidentate ligand and ligates the Cu atom through the carbonyl-O2 and oxazoline-N1 atoms. The Cu atom, which lies a centre of inversion, adopts a square planar geometry within a trans-N2O2 donor set.