Aqua­{4,4′-dibromo-6,6′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}copper(II)

Xie, H.

doi:10.1107/S1600536809046212

metal-organic compounds

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Aqua{4,4′-dibromo-6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}copper(II)

Hai Xie ^a ^*

^aCollege of Chemistry & Chemical Engineering, Shanxi Datong University, Shanxi 037009, People's Republic of China
^*Correspondence e-mail: haixiedt@126.com

(Received 25 October 2009; accepted 3 November 2009; online 14 November 2009)

The title complex, [Cu(C₁₈H₁₆Br₂N₂O₄)(H₂O)], lies on a crystallographic mirror plane with the Cu^II ion coordinated by two N atoms and two O atoms of a tetradentate Schiff base ligand and one O atom from a water ligand in a slightly distorted square-pyramidal environment. The mirror plane, which coincides with the Cu—O_water bond, imposes disorder of the atoms of the ethylene group. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link complex molecules into extended chains along [100].

Related literature

For related structures, see: Nathan et al. (2003 ); Saha et al. (2007 ); Xing (2009 ). For general background to Schiff base compounds, see: Yu et al. (2007 ); Ghosh et al. (2006 ); Singh et al. (2007 ); Nayka et al. (2006 ).

Experimental

Crystal data

[Cu(C₁₈H₁₆Br₂N₂O₄)(H₂O)]
M_r = 565.70
Orthorhombic, P n m a
a = 8.7299 (13) Å
b = 27.968 (4) Å
c = 7.9900 (12) Å
V = 1950.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 5.25 mm⁻¹
T = 293 K
0.23 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.378, T_max = 0.452
8970 measured reflections
1759 independent reflections
1498 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.138
S = 1.13
1759 reflections
140 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.48 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱ	0.82	2.23	2.963 (5)	150
O3—H3A⋯O1ⁱ	0.82	2.27	2.936 (7)	139
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046212/lh2938sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046212/lh2938Isup2.hkl

checkCIF report

Comment top

Schiff-bases can readily form stable complexes with most transition metals, in which some may exhibit interesting properties (Yu et al., 2007; Ghosh et al., 2006; Singh et al., 2007; Nayka et al., 2006). Here, we report a Cu(II) complex based on the tetradentate Schiff-base ligand N,N'-ethylenebis(5-bromo-3-methoxysalicylaldimine.

The molecular structure of the title compound is shown in Fig. 1. The complex lies on a crystallographic mirror plane with the Cu^II ion coordinated in a slightly distorted square-pyramidal environment. The basal plane is occupied by two N atoms and two O atoms of the Schiff-base ligand, and the apical site is occupied by the O atom of the coordinated water molecule. The Cu^II ion is displaced towards the Cu—O_water bond from the plane formed by the two N atoms and two O atoms by 0.224 (4) Å. The Cu—N and Cu—O bond lengths are consistent with the corresponding distances found in other Cu Schiff base complexes (Nathan, et al., 2003; Saha, et al., 2007; Xing, 2009).

Related literature top

For related structures, see: Nathan et al. (2003); Saha et al. (2007); Xing (2009). For general background to Schiff base compounds, see: Yu et al. (2007); Ghosh et al. (2006); Singh et al. (2007); Nayka et al. (2006).

Experimental top

Condensation of ethyl diamine and 5-bromo-3-methoxyl-2-hydroxy-benzaldehyde with the ratio 1:2 in ethanol gave the Schiff base ligand. The title compound was synthesized by treatment Cu(ClO₄)₂.6H₂O and the schiff-base ligand (1:1, molar ratio) in methanol. After the mixture was stirred for for about 30 min at room temperature, it was filtered and the filtrate was allowed to partial evaporate in air for one week to produce crystals suitable for X-ray diffraction with a yield about 52%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (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 the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. All H-atoms are omitted for clarity. Only one disorder component is shown with open bonds [symmetry code (A): (x, -y+1/2, z).

Aqua{4,4'-dibromo-6,6'-dimethoxy-2,2'-[ethane-1,2- diylbis(nitrilomethylidyne)]diphenolato}copper(II) top

Crystal data top

[Cu(C₁₈H₁₆Br₂N₂O₄)(H₂O)]	F(000) = 1116
M_r = 565.70	D_x = 1.926 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2580 reflections
a = 8.7299 (13) Å	θ = 2.9–26.7°
b = 27.968 (4) Å	µ = 5.25 mm⁻¹
c = 7.9900 (12) Å	T = 293 K
V = 1950.8 (5) Å³	Block, blue
Z = 4	0.23 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1759 independent reflections
Radiation source: fine-focus sealed tube	1498 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→10
T_min = 0.378, T_max = 0.452	k = −33→27
8970 measured reflections	l = −8→9

Refinement top

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0394P)² + 13.8845P] where P = (F_o² + 2F_c²)/3
1759 reflections	(Δ/σ)_max = 0.001
140 parameters	Δρ_max = 1.48 e Å⁻³
1 restraint	Δρ_min = −1.02 e Å⁻³

Crystal data top

[Cu(C₁₈H₁₆Br₂N₂O₄)(H₂O)]	V = 1950.8 (5) Å³
M_r = 565.70	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 8.7299 (13) Å	µ = 5.25 mm⁻¹
b = 27.968 (4) Å	T = 293 K
c = 7.9900 (12) Å	0.23 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1759 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1498 reflections with I > 2σ(I)
T_min = 0.378, T_max = 0.452	R_int = 0.034
8970 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	1 restraint
wR(F²) = 0.138	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0394P)² + 13.8845P] where P = (F_o² + 2F_c²)/3
1759 reflections	Δρ_max = 1.48 e Å⁻³
140 parameters	Δρ_min = −1.02 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)
Br1	0.28985 (13)	0.50680 (3)	−0.14560 (14)	0.0802 (4)
Cu1	0.43677 (12)	0.2500	0.01791 (14)	0.0336 (3)
O1	0.2831 (5)	0.29928 (14)	0.0459 (6)	0.0394 (11)
O2	0.0393 (5)	0.35017 (16)	0.0910 (7)	0.0492 (12)
O3	0.5275 (7)	0.2500	0.2889 (8)	0.0446 (16)
H3A	0.5656	0.2746	0.3257	0.067*
N1	0.5856 (6)	0.2962 (2)	−0.0675 (8)	0.0515 (16)
C1	0.4226 (7)	0.3656 (2)	−0.0697 (8)	0.0385 (15)
C2	0.2929 (7)	0.3439 (2)	0.0005 (8)	0.0334 (13)
C3	0.1626 (7)	0.3736 (2)	0.0235 (8)	0.0387 (15)
C4	0.1622 (8)	0.4211 (2)	−0.0169 (9)	0.0436 (16)
H4	0.0754	0.4397	0.0006	0.052*
C5	0.2941 (9)	0.4410 (2)	−0.0848 (9)	0.0472 (17)
C6	0.4200 (9)	0.4150 (2)	−0.1124 (9)	0.0484 (18)
H6	0.5062	0.4291	−0.1596	0.058*
C7	0.5621 (8)	0.3402 (2)	−0.1013 (9)	0.0460 (17)
H7	0.6421	0.3571	−0.1505	0.055*
C8	−0.0958 (9)	0.3769 (3)	0.1200 (10)	0.058 (2)
H8A	−0.0753	0.4015	0.2011	0.087*
H8B	−0.1746	0.3561	0.1615	0.087*
H8C	−0.1290	0.3913	0.0172	0.087*
C9	0.7175 (16)	0.2701 (7)	−0.147 (2)	0.054 (5)	0.50
H9A	0.6948	0.2643	−0.2645	0.065*	0.50
H9B	0.8089	0.2897	−0.1413	0.065*	0.50
C9A	0.7457 (13)	0.2236 (7)	−0.061 (3)	0.052 (5)	0.50
H9A1	0.7812	0.2280	0.0527	0.063*	0.50
H9A2	0.8177	0.2037	−0.1222	0.063*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1002 (8)	0.0319 (4)	0.1084 (8)	0.0054 (4)	0.0121 (6)	0.0259 (4)
Cu1	0.0301 (5)	0.0275 (5)	0.0433 (6)	0.000	0.0040 (5)	0.000
O1	0.038 (2)	0.024 (2)	0.056 (3)	0.0025 (18)	0.006 (2)	0.010 (2)
O2	0.038 (3)	0.034 (2)	0.076 (3)	0.006 (2)	0.014 (2)	0.007 (2)
O3	0.053 (4)	0.032 (3)	0.049 (4)	0.000	−0.011 (3)	0.000
N1	0.035 (3)	0.044 (3)	0.076 (4)	0.000 (3)	0.013 (3)	0.020 (3)
C1	0.041 (4)	0.037 (4)	0.038 (3)	−0.002 (3)	0.001 (3)	0.008 (3)
C2	0.039 (3)	0.026 (3)	0.035 (3)	0.000 (3)	0.000 (3)	0.002 (3)
C3	0.041 (3)	0.035 (3)	0.040 (3)	−0.002 (3)	−0.001 (3)	0.002 (3)
C4	0.049 (4)	0.030 (3)	0.051 (4)	0.005 (3)	−0.004 (3)	0.007 (3)
C5	0.065 (5)	0.029 (3)	0.048 (4)	−0.001 (3)	−0.005 (4)	0.005 (3)
C6	0.054 (4)	0.039 (4)	0.052 (4)	−0.004 (3)	0.000 (4)	0.009 (3)
C7	0.038 (4)	0.043 (4)	0.057 (4)	−0.005 (3)	0.008 (3)	0.013 (3)
C8	0.052 (5)	0.053 (5)	0.069 (5)	0.015 (4)	0.011 (4)	0.009 (4)
C9	0.031 (8)	0.053 (9)	0.078 (14)	−0.001 (7)	0.009 (9)	0.021 (10)
C9A	0.023 (8)	0.067 (11)	0.066 (13)	0.004 (7)	−0.006 (8)	−0.011 (11)

Geometric parameters (Å, º) top

Br1—C5	1.903 (7)	C2—C3	1.420 (9)
Cu1—O1ⁱ	1.937 (4)	C3—C4	1.367 (9)
Cu1—O1	1.937 (4)	C4—C5	1.389 (10)
Cu1—N1	1.954 (5)	C4—H4	0.9300
Cu1—N1ⁱ	1.954 (5)	C5—C6	1.338 (10)
Cu1—O3	2.305 (6)	C6—H6	0.9300
O1—C2	1.303 (7)	C7—H7	0.9300
O2—C3	1.371 (8)	C8—H8A	0.9600
O2—C8	1.416 (8)	C8—H8B	0.9600
O3—H3A	0.8188	C8—H8C	0.9600
N1—C7	1.277 (9)	C9—C9A	1.491 (19)
N1—C9Aⁱ	1.504 (10)	C9—H9A	0.9700
N1—C9	1.505 (10)	C9—H9B	0.9700
C1—C2	1.402 (9)	C9A—N1ⁱ	1.504 (10)
C1—C6	1.421 (9)	C9A—H9A1	0.9700
C1—C7	1.433 (10)	C9A—H9A2	0.9700

O1ⁱ—Cu1—O1	90.8 (2)	C5—C4—H4	120.6
O1ⁱ—Cu1—N1	166.2 (3)	C6—C5—C4	121.8 (6)
O1—Cu1—N1	91.8 (2)	C6—C5—Br1	120.1 (6)
O1ⁱ—Cu1—N1ⁱ	91.8 (2)	C4—C5—Br1	118.1 (5)
O1—Cu1—N1ⁱ	166.2 (3)	C5—C6—C1	120.2 (7)
N1—Cu1—N1ⁱ	82.7 (4)	C5—C6—H6	119.9
O1ⁱ—Cu1—O3	97.45 (18)	C1—C6—H6	119.9
O1—Cu1—O3	97.45 (18)	N1—C7—C1	125.3 (6)
N1—Cu1—O3	95.7 (2)	N1—C7—H7	117.4
N1ⁱ—Cu1—O3	95.7 (2)	C1—C7—H7	117.4
C2—O1—Cu1	127.2 (4)	O2—C8—H8A	109.5
C3—O2—C8	117.8 (5)	O2—C8—H8B	109.5
Cu1—O3—H3A	118.5	H8A—C8—H8B	109.5
C7—N1—C9Aⁱ	120.7 (10)	O2—C8—H8C	109.5
C7—N1—C9	120.0 (9)	H8A—C8—H8C	109.5
C7—N1—Cu1	127.2 (5)	H8B—C8—H8C	109.5
C9Aⁱ—N1—Cu1	111.3 (9)	C9A—C9—N1	110.7 (14)
C9—N1—Cu1	109.7 (8)	C9A—C9—H9A	109.5
C2—C1—C6	120.2 (6)	N1—C9—H9A	109.5
C2—C1—C7	122.8 (6)	C9A—C9—H9B	109.5
C6—C1—C7	117.0 (6)	N1—C9—H9B	109.5
O1—C2—C1	125.4 (6)	H9A—C9—H9B	108.1
O1—C2—C3	118.1 (6)	C9—C9A—N1ⁱ	98.7 (12)
C1—C2—C3	116.5 (6)	C9—C9A—H9A1	112.0
C4—C3—O2	123.7 (6)	N1ⁱ—C9A—H9A1	112.0
C4—C3—C2	122.6 (6)	C9—C9A—H9A2	112.0
O2—C3—C2	113.7 (5)	N1ⁱ—C9A—H9A2	112.0
C3—C4—C5	118.7 (7)	H9A1—C9A—H9A2	109.7
C3—C4—H4	120.6

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱⁱ	0.82	2.23	2.963 (5)	150
O3—H3A···O1ⁱⁱ	0.82	2.27	2.936 (7)	139

Symmetry code: (ii) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₈H₁₆Br₂N₂O₄)(H₂O)]
M_r	565.70
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	8.7299 (13), 27.968 (4), 7.9900 (12)
V (Å³)	1950.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.25
Crystal size (mm)	0.23 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.378, 0.452
No. of measured, independent and observed [I > 2σ(I)] reflections	8970, 1759, 1498
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.138, 1.13
No. of reflections	1759
No. of parameters	140
No. of restraints	1
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0394P)² + 13.8845P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.48, −1.02

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.82	2.23	2.963 (5)	149.6
O3—H3A···O1ⁱ	0.82	2.27	2.936 (7)	139.4

Symmetry code: (i) x+1/2, y, −z+1/2.

Acknowledgements

This work was funded by a research grant from the Shanxi Datong University Foundation of Shanxi Province of the People's Republic of China (grant No. 2008 K1). We also thank Huazhong Normal University for supporting this study.

References

Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ghosh, R., Rahaman, S. H., Lin, C. N., Lu, T. H. & Ghosh, B. K. (2006). Polyhedron, 25, 3104–3112. Web of Science CSD CrossRef CAS Google Scholar
Nathan, L. C., Koehne, J. E., Gilmore, J. M., Hannibal, K. A., Dewhirst, W. E. & Mai, T. D. (2003). Polyhedron, 22, 887–894. Web of Science CSD CrossRef CAS Google Scholar
Nayka, M., Koner, R., Lin, H. H., Flörke, U., Wei, H. H. & Mohanta, S. (2006). Inorg. Chem.. 45, 10764–10773. Web of Science PubMed Google Scholar
Saha, P. K., Dutta, B., Jana, S., Bera, R., Saha, S., Okamoto, K. & Koner, S. (2007). Polyhedron, 26, 563–571. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Singh, K., Barwa, M. S. & Tyagi, P. (2007). Eur. J. Med. Chem. 42, 394–402. Web of Science CrossRef PubMed CAS Google Scholar
Xing, J. (2009). Acta Cryst. E65, m469. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yu, T. Z., Zhang, K., Zhao, Y. L., Yang, C. H., Zhang, H., Fan, D. W. & Dong, W. K. (2007). Inorg. Chem. Commun. 10, 401–403. Web of Science CSD CrossRef CAS Google Scholar

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doi:10.1107/S1600536809046212

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

Aqua­{4,4′-di­bromo-6,6′-dimeth­­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­­idyne)]diphenolato}copper(II)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Aqua{4,4′-dibromo-6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}copper(II)