Acta Cryst. (2008). E64, m850 [ doi:10.1107/S1600536808015602 ]
The title mononuclear zinc(II) complex, [Zn(C17H14Br2N2O2)], possesses a crystallographically imposed C2 axis. The Zn atom is four-coordinated by two O and two N atoms from two Schiff base ligands, forming a severely distorted square-planar geometry. The central C atom of the propyl group is disordered over two positions about the twofold axis.
N,N'-Propane-1,3-diamine (0.1 mmol, 14.8 mg) and 5-bromosalicylaldehyde (0.1 mmol, 20.1 mg) were dissolved in methanol (20 ml). The mixture was stirred for 1 h to obtain a clear yellow solution. To the solution was added with stirring a methanol solution (20 ml) of zinc(II) acetate (0.1 mmol, 22.0 mg). After keeping the resulting solution in air for a few days, colourless block-shaped crystals were formed on slow evaporation of the solvent.
H9A and H9B were located from a difference Fourier map and refined freely, with C–H and H···H distances restrained to 0.96 (1) and 1.50 (2) respectively, and with an isotropic displacement parameter fixed to 0.08 Å2. %A. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93-96 Å and Uiso = 1.2 Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./rz2218fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Only one component of the disordered C9 atom is shown. H atoms are omitted for clarity. Unlabelled atoms are related to the labelled atoms by the symmetry operation (-x, y, 1/2-z). |
| [Zn(C17H14Br2N2O2)] | F000 = 984 |
| Mr = 503.49 | Dx = 2.011 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1595 reflections |
| a = 21.418 (6) Å | θ = 2.5–26.3º |
| b = 8.161 (2) Å | µ = 6.30 mm−1 |
| c = 9.524 (3) Å | T = 298 (2) K |
| β = 92.910 (3)º | Block, colourless |
| V = 1662.6 (8) Å3 | 0.32 × 0.30 × 0.30 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1809 independent reflections |
| Radiation source: fine-focus sealed tube | 1444 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.036 |
| T = 298(2) K | θmax = 27.0º |
| ω scans | θmin = 1.9º |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −27→27 |
| Tmin = 0.143, Tmax = 0.152 | k = −10→9 |
| 4709 measured reflections | l = −12→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)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0396P)2 + 3.1273P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 1809 reflections | Δρmax = 0.45 e Å−3 |
| 121 parameters | Δρmin = −0.64 e Å−3 |
| 3 restraints | Extinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0078 (5) |
| [Zn(C17H14Br2N2O2)] | V = 1662.6 (8) Å3 |
| Mr = 503.49 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 21.418 (6) Å | µ = 6.30 mm−1 |
| b = 8.161 (2) Å | T = 298 (2) K |
| c = 9.524 (3) Å | 0.32 × 0.30 × 0.30 mm |
| β = 92.910 (3)º |
| Bruker SMART CCD area-detector diffractometer | 1809 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1444 reflections with I > 2σ(I) |
| Tmin = 0.143, Tmax = 0.152 | Rint = 0.036 |
| 4709 measured reflections |
| R[F2 > 2σ(F2)] = 0.036 | 3 restraints |
| wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.05 | Δρmax = 0.45 e Å−3 |
| 1809 reflections | Δρmin = −0.64 e Å−3 |
| 121 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 | Occ. (<1) | |
| Zn1 | 0.0000 | 0.01735 (7) | 0.2500 | 0.0347 (2) | |
| Br1 | 0.23023 (2) | 0.25397 (6) | 0.81463 (5) | 0.0539 (2) | |
| N1 | 0.04072 (14) | −0.1416 (3) | 0.3803 (3) | 0.0343 (7) | |
| O1 | 0.05877 (12) | 0.1867 (3) | 0.2995 (3) | 0.0370 (6) | |
| C1 | 0.09920 (16) | 0.1906 (4) | 0.4060 (4) | 0.0310 (8) | |
| C2 | 0.10887 (15) | 0.0587 (4) | 0.5015 (4) | 0.0298 (7) | |
| C3 | 0.14983 (16) | 0.0782 (5) | 0.6219 (4) | 0.0362 (8) | |
| H3 | 0.1557 | −0.0080 | 0.6851 | 0.043* | |
| C4 | 0.18070 (17) | 0.2229 (5) | 0.6459 (4) | 0.0367 (8) | |
| C5 | 0.17583 (18) | 0.3491 (5) | 0.5466 (4) | 0.0406 (9) | |
| H5 | 0.1995 | 0.4439 | 0.5598 | 0.049* | |
| C6 | 0.13625 (17) | 0.3329 (5) | 0.4299 (4) | 0.0376 (8) | |
| H6 | 0.1336 | 0.4176 | 0.3645 | 0.045* | |
| C7 | 0.08158 (16) | −0.1003 (4) | 0.4779 (4) | 0.0332 (8) | |
| H7 | 0.0949 | −0.1827 | 0.5399 | 0.040* | |
| C8 | 0.0244 (3) | −0.3170 (5) | 0.3736 (5) | 0.0577 (13) | |
| H8A | 0.0119 | −0.3481 | 0.4652 | 0.069* | |
| H8B | 0.0623 | −0.3752 | 0.3578 | 0.069* | |
| C9 | −0.0202 (3) | −0.3766 (8) | 0.2766 (9) | 0.0375 (17) | 0.50 |
| H9A | −0.024 (4) | −0.4935 (16) | 0.280 (12) | 0.080* | 0.50 |
| H9B | −0.059 (2) | −0.340 (9) | 0.310 (11) | 0.080* | 0.50 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0395 (4) | 0.0264 (3) | 0.0374 (4) | 0.000 | −0.0056 (2) | 0.000 |
| Br1 | 0.0500 (3) | 0.0645 (4) | 0.0453 (3) | −0.0064 (2) | −0.01642 (19) | −0.0038 (2) |
| N1 | 0.0442 (17) | 0.0228 (15) | 0.0354 (17) | 0.0001 (13) | −0.0019 (14) | 0.0015 (13) |
| O1 | 0.0465 (15) | 0.0277 (13) | 0.0354 (15) | −0.0030 (11) | −0.0111 (11) | 0.0031 (11) |
| C1 | 0.0307 (18) | 0.0281 (18) | 0.034 (2) | 0.0026 (14) | 0.0015 (14) | −0.0022 (14) |
| C2 | 0.0269 (16) | 0.0318 (19) | 0.0304 (18) | 0.0034 (14) | −0.0006 (13) | −0.0008 (14) |
| C3 | 0.0334 (18) | 0.041 (2) | 0.034 (2) | 0.0074 (16) | 0.0008 (15) | 0.0032 (16) |
| C4 | 0.0270 (18) | 0.045 (2) | 0.037 (2) | 0.0001 (15) | −0.0064 (15) | −0.0041 (17) |
| C5 | 0.039 (2) | 0.036 (2) | 0.046 (2) | −0.0077 (16) | −0.0026 (17) | −0.0016 (18) |
| C6 | 0.040 (2) | 0.0304 (19) | 0.042 (2) | −0.0015 (16) | −0.0026 (16) | 0.0028 (16) |
| C7 | 0.0371 (19) | 0.0305 (19) | 0.0317 (19) | 0.0077 (15) | −0.0009 (15) | 0.0041 (15) |
| C8 | 0.097 (4) | 0.025 (2) | 0.051 (3) | −0.009 (2) | 0.000 (3) | 0.0003 (19) |
| C9 | 0.045 (5) | 0.020 (3) | 0.047 (5) | −0.001 (3) | −0.003 (4) | 0.005 (3) |
| Zn1—O1 | 1.912 (3) | C4—C5 | 1.398 (6) |
| Zn1—O1i | 1.912 (3) | C5—C6 | 1.370 (5) |
| Zn1—N1i | 1.968 (3) | C5—H5 | 0.9300 |
| Zn1—N1 | 1.968 (3) | C6—H6 | 0.9300 |
| Br1—C4 | 1.897 (4) | C7—H7 | 0.9300 |
| N1—C7 | 1.289 (5) | C8—C9 | 1.383 (9) |
| N1—C8 | 1.474 (5) | C8—C9i | 1.509 (9) |
| O1—C1 | 1.301 (4) | C8—H8A | 0.9600 |
| C1—C2 | 1.417 (5) | C8—H8B | 0.9599 |
| C1—C6 | 1.419 (5) | C9—C9i | 1.025 (15) |
| C2—C3 | 1.417 (5) | C9—C8i | 1.509 (9) |
| C2—C7 | 1.436 (5) | C9—H9A | 0.958 (10) |
| C3—C4 | 1.367 (5) | C9—H9B | 0.960 (10) |
| C3—H3 | 0.9300 | ||
| O1—Zn1—O1i | 87.42 (16) | C5—C6—C1 | 121.8 (4) |
| O1—Zn1—N1i | 153.75 (12) | C5—C6—H6 | 119.1 |
| O1i—Zn1—N1i | 93.21 (12) | C1—C6—H6 | 119.1 |
| O1—Zn1—N1 | 93.21 (12) | N1—C7—C2 | 127.3 (3) |
| O1i—Zn1—N1 | 153.75 (12) | N1—C7—H7 | 116.4 |
| N1i—Zn1—N1 | 97.53 (18) | C2—C7—H7 | 116.4 |
| C7—N1—C8 | 115.9 (3) | C9—C8—N1 | 121.7 (5) |
| C7—N1—Zn1 | 123.0 (2) | N1—C8—C9i | 110.9 (4) |
| C8—N1—Zn1 | 121.1 (3) | C9—C8—H8A | 107.4 |
| C1—O1—Zn1 | 127.9 (2) | N1—C8—H8A | 107.1 |
| O1—C1—C2 | 123.5 (3) | C9i—C8—H8A | 140.4 |
| O1—C1—C6 | 119.3 (3) | C9—C8—H8B | 106.4 |
| C2—C1—C6 | 117.2 (3) | N1—C8—H8B | 106.6 |
| C1—C2—C3 | 119.9 (3) | C9i—C8—H8B | 72.7 |
| C1—C2—C7 | 122.7 (3) | H8A—C8—H8B | 106.8 |
| C3—C2—C7 | 117.3 (3) | C9i—C9—C8 | 76.0 (9) |
| C4—C3—C2 | 120.4 (3) | C9i—C9—C8i | 62.8 (8) |
| C4—C3—H3 | 119.8 | C8—C9—C8i | 121.7 (6) |
| C2—C3—H3 | 119.8 | C9i—C9—H9A | 95 (4) |
| C3—C4—C5 | 120.3 (4) | C8—C9—H9A | 112 (7) |
| C3—C4—Br1 | 120.1 (3) | C8i—C9—H9A | 111 (7) |
| C5—C4—Br1 | 119.6 (3) | C9i—C9—H9B | 160 (5) |
| C6—C5—C4 | 120.0 (3) | C8—C9—H9B | 105 (6) |
| C6—C5—H5 | 120.0 | C8i—C9—H9B | 102 (6) |
| C4—C5—H5 | 120.0 | H9A—C9—H9B | 103 (2) |
| Symmetry codes: (i) −x, y, −z+1/2. |
| Zn1—O1 | 1.912 (3) | Zn1—N1 | 1.968 (3) |
| O1—Zn1—O1i | 87.42 (16) | O1—Zn1—N1 | 93.21 (12) |
| O1—Zn1—N1i | 153.75 (12) |
| Symmetry codes: (i) −x, y, −z+1/2. |
The Scientific Research Foundation of Henan University of Science and Technology (Project No. 05–072) is gratefully acknowledged.
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Zinc(II) complexes derived from Schiff bases have been widely studied (Anderson et al., 1997). Some of them have been found to have pharmacological and antitumor properties (Chohan & Kausar, 1992, 1993; Osowole et al., 2005; Chohan et al., 2003; Yu et al., 2007). Recently, we have reported some metal complexes derived from the Schiff base ligands (Ma, Lv et al., 2006; Ma, Gu et al., 2006; Ma, We et al., 2005, 2006). As part of a further investigation of the structures of such complexes, the title mononuclear zinc(II) complex (Fig 1) is reported in this paper.
The title compound possesses a crystallographically imposed C2 axis passing through the zinc(II) atom and the midpoint of the propyl group, causing the C9 atom to be disordered over two positions. The Zn atom is coordinated by two nitrogen atoms and two oxygen atoms from a Schiff base ligand, giving a severely distorted square planar geometry. Bond lengths and angles (Table 1) related to the Zn atom in the complex are within normal ranges, and comparable to the values observed in other Schiff base zinc(II) complexes (Li & Zhang, 2005; Xu et al., 2006; Wu et al., 2006).