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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): m850.
Published online 2008 May 30. doi:  10.1107/S1600536808015602
PMCID: PMC2961367

{4,4′-Dibromo-2,2′-[propane-1,3-diyl­bis(nitrilo­methyl­idyne)]diphenolato}zinc(II)

Abstract

The title mononuclear zinc(II) complex, [Zn(C17H14Br2N2O2)], possesses a crystallographically imposed C 2 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.

Related literature

For background on the chemistry of Schiff base zinc(II) complexes and their biological activity, see: Anderson et al. (1997 [triangle]); Chohan & Kausar (1992 [triangle], 1993 [triangle]); Chohan et al. (2003 [triangle]); Osowole et al. (2005 [triangle]); Yu et al., (2007 [triangle]). For related structures, see: Li & Zhang (2005 [triangle]); Wu et al. (2006 [triangle]); Xu et al. (2006 [triangle]); Ma et al. (2005 [triangle]); Ma, Gu et al. (2006 [triangle]); Ma, Lv et al. (2006 [triangle]); Ma, Wu et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m850-scheme1.jpg

Experimental

Crystal data

  • [Zn(C17H14Br2N2O2)]
  • M r = 503.49
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m850-efi1.jpg
  • a = 21.418 (6) Å
  • b = 8.161 (2) Å
  • c = 9.524 (3) Å
  • β = 92.910 (3)°
  • V = 1662.6 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.30 mm−1
  • T = 298 (2) K
  • 0.32 × 0.30 × 0.30 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.143, T max = 0.152
  • 4709 measured reflections
  • 1809 independent reflections
  • 1444 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.092
  • S = 1.05
  • 1809 reflections
  • 121 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.64 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015602/rz2218sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015602/rz2218Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The Scientific Research Foundation of Henan University of Science and Technology (Project No. 05-072) is gratefully acknowledged.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

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).

Figures

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 ...

Crystal data

[Zn(C17H14Br2N2O2)]F000 = 984
Mr = 503.49Dx = 2.011 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1595 reflections
a = 21.418 (6) Åθ = 2.5–26.3º
b = 8.161 (2) ŵ = 6.30 mm1
c = 9.524 (3) ÅT = 298 (2) K
β = 92.910 (3)ºBlock, colourless
V = 1662.6 (8) Å30.32 × 0.30 × 0.30 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1809 independent reflections
Radiation source: fine-focus sealed tube1444 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.036
T = 298(2) Kθmax = 27.0º
ω scansθmin = 1.9º
Absorption correction: multi-scan(SADABS; Bruker, 2000)h = −27→27
Tmin = 0.143, Tmax = 0.152k = −10→9
4709 measured reflectionsl = −12→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H 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 reflectionsΔρmax = 0.45 e Å3
121 parametersΔρmin = −0.64 e Å3
3 restraintsExtinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0078 (5)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Zn10.00000.01735 (7)0.25000.0347 (2)
Br10.23023 (2)0.25397 (6)0.81463 (5)0.0539 (2)
N10.04072 (14)−0.1416 (3)0.3803 (3)0.0343 (7)
O10.05877 (12)0.1867 (3)0.2995 (3)0.0370 (6)
C10.09920 (16)0.1906 (4)0.4060 (4)0.0310 (8)
C20.10887 (15)0.0587 (4)0.5015 (4)0.0298 (7)
C30.14983 (16)0.0782 (5)0.6219 (4)0.0362 (8)
H30.1557−0.00800.68510.043*
C40.18070 (17)0.2229 (5)0.6459 (4)0.0367 (8)
C50.17583 (18)0.3491 (5)0.5466 (4)0.0406 (9)
H50.19950.44390.55980.049*
C60.13625 (17)0.3329 (5)0.4299 (4)0.0376 (8)
H60.13360.41760.36450.045*
C70.08158 (16)−0.1003 (4)0.4779 (4)0.0332 (8)
H70.0949−0.18270.53990.040*
C80.0244 (3)−0.3170 (5)0.3736 (5)0.0577 (13)
H8A0.0119−0.34810.46520.069*
H8B0.0623−0.37520.35780.069*
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

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0395 (4)0.0264 (3)0.0374 (4)0.000−0.0056 (2)0.000
Br10.0500 (3)0.0645 (4)0.0453 (3)−0.0064 (2)−0.01642 (19)−0.0038 (2)
N10.0442 (17)0.0228 (15)0.0354 (17)0.0001 (13)−0.0019 (14)0.0015 (13)
O10.0465 (15)0.0277 (13)0.0354 (15)−0.0030 (11)−0.0111 (11)0.0031 (11)
C10.0307 (18)0.0281 (18)0.034 (2)0.0026 (14)0.0015 (14)−0.0022 (14)
C20.0269 (16)0.0318 (19)0.0304 (18)0.0034 (14)−0.0006 (13)−0.0008 (14)
C30.0334 (18)0.041 (2)0.034 (2)0.0074 (16)0.0008 (15)0.0032 (16)
C40.0270 (18)0.045 (2)0.037 (2)0.0001 (15)−0.0064 (15)−0.0041 (17)
C50.039 (2)0.036 (2)0.046 (2)−0.0077 (16)−0.0026 (17)−0.0016 (18)
C60.040 (2)0.0304 (19)0.042 (2)−0.0015 (16)−0.0026 (16)0.0028 (16)
C70.0371 (19)0.0305 (19)0.0317 (19)0.0077 (15)−0.0009 (15)0.0041 (15)
C80.097 (4)0.025 (2)0.051 (3)−0.009 (2)0.000 (3)0.0003 (19)
C90.045 (5)0.020 (3)0.047 (5)−0.001 (3)−0.003 (4)0.005 (3)

Geometric parameters (Å, °)

Zn1—O11.912 (3)C4—C51.398 (6)
Zn1—O1i1.912 (3)C5—C61.370 (5)
Zn1—N1i1.968 (3)C5—H50.9300
Zn1—N11.968 (3)C6—H60.9300
Br1—C41.897 (4)C7—H70.9300
N1—C71.289 (5)C8—C91.383 (9)
N1—C81.474 (5)C8—C9i1.509 (9)
O1—C11.301 (4)C8—H8A0.9600
C1—C21.417 (5)C8—H8B0.9599
C1—C61.419 (5)C9—C9i1.025 (15)
C2—C31.417 (5)C9—C8i1.509 (9)
C2—C71.436 (5)C9—H9A0.958 (10)
C3—C41.367 (5)C9—H9B0.960 (10)
C3—H30.9300
O1—Zn1—O1i87.42 (16)C5—C6—C1121.8 (4)
O1—Zn1—N1i153.75 (12)C5—C6—H6119.1
O1i—Zn1—N1i93.21 (12)C1—C6—H6119.1
O1—Zn1—N193.21 (12)N1—C7—C2127.3 (3)
O1i—Zn1—N1153.75 (12)N1—C7—H7116.4
N1i—Zn1—N197.53 (18)C2—C7—H7116.4
C7—N1—C8115.9 (3)C9—C8—N1121.7 (5)
C7—N1—Zn1123.0 (2)N1—C8—C9i110.9 (4)
C8—N1—Zn1121.1 (3)C9—C8—H8A107.4
C1—O1—Zn1127.9 (2)N1—C8—H8A107.1
O1—C1—C2123.5 (3)C9i—C8—H8A140.4
O1—C1—C6119.3 (3)C9—C8—H8B106.4
C2—C1—C6117.2 (3)N1—C8—H8B106.6
C1—C2—C3119.9 (3)C9i—C8—H8B72.7
C1—C2—C7122.7 (3)H8A—C8—H8B106.8
C3—C2—C7117.3 (3)C9i—C9—C876.0 (9)
C4—C3—C2120.4 (3)C9i—C9—C8i62.8 (8)
C4—C3—H3119.8C8—C9—C8i121.7 (6)
C2—C3—H3119.8C9i—C9—H9A95 (4)
C3—C4—C5120.3 (4)C8—C9—H9A112 (7)
C3—C4—Br1120.1 (3)C8i—C9—H9A111 (7)
C5—C4—Br1119.6 (3)C9i—C9—H9B160 (5)
C6—C5—C4120.0 (3)C8—C9—H9B105 (6)
C6—C5—H5120.0C8i—C9—H9B102 (6)
C4—C5—H5120.0H9A—C9—H9B103 (2)

Symmetry codes: (i) −x, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2218).

References

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