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

Ma, J.-Y.

doi:10.1107/S1600536808015602

metal-organic compounds

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Volume 64| Part 6| June 2008| Page m850

doi:10.1107/S1600536808015602

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

Jun-Ying Ma ^a ^*

^aChemical Engineering and Pharmaceutics College, Henan University of Science and Technology, Luoyang, Henan 471003, People's Republic of China, and Department of Chemistry, Pingdingshan University, Pingdingshan, Henan 467000, People's Republic of China
^*Correspondence e-mail: junying-ma@163.com

(Received 14 May 2008; accepted 23 May 2008; online 30 May 2008)

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.

Related literature

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

Experimental

Crystal data

[Zn(C₁₇H₁₄Br₂N₂O₂)]
M_r = 503.49
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.092
S = 1.05
1809 reflections
121 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—O1	1.912 (3)
Zn1—N1	1.968 (3)

O1—Zn1—O1ⁱ	87.42 (16)
O1—Zn1—N1ⁱ	153.75 (12)
O1—Zn1—N1	93.21 (12)
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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).

Figures top

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).

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

Crystal data top

[Zn(C₁₇H₁₄Br₂N₂O₂)]	F(000) = 984
M_r = 503.49	D_x = 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 = 2.5–26.3°
b = 8.161 (2) Å	µ = 6.30 mm⁻¹
c = 9.524 (3) Å	T = 298 K
β = 92.910 (3)°	Block, colourless
V = 1662.6 (8) Å³	0.32 × 0.30 × 0.30 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1809 independent reflections
Radiation source: fine-focus sealed tube	1444 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −27→27
T_min = 0.143, T_max = 0.152	k = −10→9
4709 measured reflections	l = −12→11

Refinement top

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(F_o²) + (0.0396P)² + 3.1273P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1809 reflections	Δρ_max = 0.45 e Å⁻³
121 parameters	Δρ_min = −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)

Crystal data top

[Zn(C₁₇H₁₄Br₂N₂O₂)]	V = 1662.6 (8) Å³
M_r = 503.49	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 21.418 (6) Å	µ = 6.30 mm⁻¹
b = 8.161 (2) Å	T = 298 K
c = 9.524 (3) Å	0.32 × 0.30 × 0.30 mm
β = 92.910 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1809 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1444 reflections with I > 2σ(I)
T_min = 0.143, T_max = 0.152	R_int = 0.036
4709 measured reflections

Refinement top

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	Δρ_max = 0.45 e Å⁻³
1809 reflections	Δρ_min = −0.64 e Å⁻³
121 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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 code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₁₇H₁₄Br₂N₂O₂)]
M_r	503.49
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	21.418 (6), 8.161 (2), 9.524 (3)
β (°)	92.910 (3)
V (Å³)	1662.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.30
Crystal size (mm)	0.32 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.143, 0.152
No. of measured, independent and observed [I > 2σ(I)] reflections	4709, 1809, 1444
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.092, 1.05
No. of reflections	1809
No. of parameters	121
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.64

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

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 code: (i) −x, y, −z+1/2.

Acknowledgements

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

References

Anderson, O. P., LaCour, A., Findeisen, M., Hennig, L., Simonsen, O., Taylor, L. F. & Toftlund, H. (1997). J. Chem. Soc. Dalton Trans. pp. 111–120. CSD CrossRef Web of Science Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chohan, Z. H. & Kausar, S. (1992). Chem. Pharm. Bull. 40, 2555–2556. CrossRef PubMed CAS Web of Science Google Scholar
Chohan, Z. H. & Kausar, S. (1993). Chem. Pharm. Bull. 41, 951–953. CrossRef CAS PubMed Web of Science Google Scholar
Chohan, Z. H., Scozzafava, A. & Supuran, C. T. (2003). J. Enzyme Inhib. Med. Chem. 18, 259–263. Web of Science CrossRef PubMed CAS Google Scholar
Li, Z.-X. & Zhang, X.-L. (2005). Acta Cryst. E61, m1755–m1756. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, J.-Y., Gu, S.-H., Guo, J.-W., Lv, B.-L. & Yin, W.-P. (2006). Acta Cryst. E62, m1437–m1438. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, J.-Y., Lv, B.-L., Gu, S.-H., Guo, J.-W. & Yin, W.-P. (2006). Acta Cryst. E62, m1322–m1323. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, J.-Y., Wu, T.-X., She, X.-G. & Pan, X.-F. (2005). Acta Cryst. E61, m695–m696. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, J.-Y., Wu, T.-X., She, X.-G. & Pan, X.-F. (2006). Z. Kristallogr. New Cryst. Struct. 221, 53–54. CAS Google Scholar
Osowole, A. A., Kolawole, G. A. & Fagade, O. E. (2005). Synth. React. Inorg. Met.-Org. Nano-Met. Chem. 35, 829–836. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, Y., Shi, S.-M., Jia, B. & Hu, Z.-Q. (2006). Acta Cryst. E62, m648–m649. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, H.-J., Liu, Z.-D. & Sheng, L.-Q. (2006). Acta Cryst. E62, m2695–m2697. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yu, Y.-Y., Zhao, G.-L. & Wen, Y.-H. (2007). Chin. J. Struct. Chem. 26, 1395–1402. CAS Google Scholar

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Volume 64| Part 6| June 2008| Page m850

doi:10.1107/S1600536808015602

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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