{2,2′-[4,5-Dibromo-o-phenyl­enebis(nitrilo­dimethyl­idyne)]diphenolato-κ4O,N,N′,O′}(methanol-κO)copper(II)

Xing, J.

doi:10.1107/S1600536809011179

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page m469

doi:10.1107/S1600536809011179

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{2,2′-[4,5-Dibromo-o-phenylenebis(nitrilodimethylidyne)]diphenolato-κ⁴O,N,N′,O′}(methanol-κO)copper(II)

Jianxin Xing ^a ^*

^aDepartment of Biology, Dezhou University, Dezhou 253023, People's Republic of China
^*Correspondence e-mail: jianxin_xing@163.com

(Received 21 March 2009; accepted 26 March 2009; online 31 March 2009)

In the title compound, [Cu(C₂₀H₁₂Br₂N₂O₂)(CH₃OH)], the Cu^II ion, and the C, O and hydroxy H atoms of the coordinated methanol molecule are located on a twofold rotation axis, while the methyl H atoms are disordered over two sites about the rotation axis. The Cu^II ion is coordinated by two N atoms [Cu—N = 1.960 (4) Å] and two O atoms [Cu—O = 1.908 (4) Å] from the tetradentate Schiff base ligand and by one O atom [Cu—O = 2.324 (6) Å] of the methanol molecule in a square-pyramidal geometry. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link complex molecules into extended chains along [001].

Related literature

For a related crystal structure, see Saha et al. (2007 ). For general background related to Schiff base compounds, see: Ghosh et al. (2006 ); Nayka et al. (2006 ); Singh et al. (2007 ); Yu et al. (2007 ).

Experimental

Crystal data

[Cu(C₂₀H₁₂Br₂N₂O₂)(CH₄O)]
M_r = 567.72
Orthorhombic, P n m a
a = 19.164 (4) Å
b = 19.416 (4) Å
c = 5.3287 (10) Å
V = 1982.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 5.16 mm⁻¹
T = 273 K
0.21 × 0.15 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.411, T_max = 0.554 (expected range = 0.379–0.511)
9881 measured reflections
2004 independent reflections
1517 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.111
S = 1.06
2004 reflections
137 parameters
242 restraints
H-atom parameters constrained
Δρ_max = 1.23 e Å⁻³
Δρ_min = −1.82 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1ⁱ	0.82	2.30	3.009 (6)	145
Symmetry code: (i) x, y, z-1.

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 global, I. DOI: 10.1107/S1600536809011179/lh2794sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011179/lh2794Isup2.hkl

checkCIF report

Comment top

Schiff-bases have played an important role in the development of coordination chemistry as they readily form stable complexes with most of the 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 new Cu(II) complex based on the tetradentate Schiff-base ligand 4,5-dibromo-1,2-diaminobenzene-N,N'-bis (salicylideneimine).

The molecular structure of the title compound is shown in Fig. 1. The Cu^II ion is pentacoordinated with the four basal sites occupied by two N atoms and two O atoms of the Schiff-base ligand, while the apical site is occupied by the O atom of the coordinated methanol molecule. The Cu^II ion is displaced towards the Cu—O_methanol bond from the plane formed by the two N atoms and two O atoms by 0.1017 Å,. The coordination geometry of the Cu^II ion is square-pyramidal. The Cu—N, Cu—O and Cu—O_methanol bond lengths are consistent with the corresponding distances in aqua-(N,N'-ethylenebis(3-methoxysalicylaldiminato)-N,N',O,O')copper(II) (Saha, et al., 2007).

Related literature top

For a related crystal structure, see Saha et al. (2007). For general background related to Schiff base compounds, see: Ghosh et al. (2006); Nayka et al. (2006); Singh et al. (2007); Yu et al. (2007).

Experimental top

The Schiff base ligand was synthesized by condensation of 4,5-dibromo-1,2-diaminobenzene and 2-hydroxy-benzaldehyde with the ratio 1:2 in ethanol. The synthesis of the title complex was carried out by reacting Cu(ClO₄)₂.6H₂O, and the schiff-base ligand (1:1, molar ratio) in methanol. After the stirring process was continued for about 10 min at room temperature, the mixture was filtered and the filtrate was allowed to partial evaporate in air for sevral days to produce crystals suitable for X-ray diffraction with a yield about 55%.

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. Unlabelled atoms are related by the symmetry operator (x, -y+3/2, z).

{2,2'-[4,5-Dibromo-o-phenylenebis(nitrilodimethylidyne)]diphenolato- κ⁴O,N,N',O'}(methanol-κO)copper(II) top

Crystal data top

[Cu(C₂₀H₁₂Br₂N₂O₂)(CH₄O)]	F(000) = 1116
M_r = 567.72	D_x = 1.902 Mg m⁻³ D_m = 1.902 Mg m⁻³ D_m measured by not measured
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1834 reflections
a = 19.164 (4) Å	θ = 3.0–22.2°
b = 19.416 (4) Å	µ = 5.16 mm⁻¹
c = 5.3287 (10) Å	T = 273 K
V = 1982.7 (6) Å³	Block, red
Z = 4	0.21 × 0.15 × 0.13 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2004 independent reflections
Radiation source: fine-focus sealed tube	1517 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→16
T_min = 0.411, T_max = 0.554	k = −23→23
9881 measured reflections	l = −6→6

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0453P)² + 5.5878P] where P = (F_o² + 2F_c²)/3
2004 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 1.23 e Å⁻³
242 restraints	Δρ_min = −1.82 e Å⁻³

Crystal data top

[Cu(C₂₀H₁₂Br₂N₂O₂)(CH₄O)]	V = 1982.7 (6) Å³
M_r = 567.72	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 19.164 (4) Å	µ = 5.16 mm⁻¹
b = 19.416 (4) Å	T = 273 K
c = 5.3287 (10) Å	0.21 × 0.15 × 0.13 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2004 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1517 reflections with I > 2σ(I)
T_min = 0.411, T_max = 0.554	R_int = 0.046
9881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	242 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.06	Δρ_max = 1.23 e Å⁻³
2004 reflections	Δρ_min = −1.82 e Å⁻³
137 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)
Cu1	0.12529 (5)	0.7500	1.11061 (15)	0.0314 (2)
Br1	−0.10466 (3)	0.66291 (3)	0.15521 (10)	0.0450 (2)
O1	0.1647 (2)	0.68206 (19)	1.3271 (6)	0.0423 (9)
O2	0.2119 (3)	0.7500	0.8053 (11)	0.0547 (10)
H2A	0.1990	0.7500	0.6587	0.066*
N1	0.0729 (2)	0.6827 (2)	0.9116 (7)	0.0301 (9)
C1	0.0321 (3)	0.7138 (3)	0.7227 (9)	0.0347 (9)
C2	−0.0080 (3)	0.6782 (3)	0.5479 (9)	0.0367 (9)
H2	−0.0076	0.6304	0.5456	0.044*
C3	−0.0485 (3)	0.7142 (3)	0.3777 (9)	0.0327 (10)
C4	0.0738 (3)	0.6172 (3)	0.9476 (10)	0.0394 (8)
H4	0.0472	0.5905	0.8391	0.047*
C5	0.1119 (3)	0.5817 (3)	1.1386 (9)	0.0392 (8)
C6	0.1546 (3)	0.6165 (3)	1.3181 (9)	0.0397 (9)
C7	0.1889 (3)	0.5735 (3)	1.4984 (10)	0.0416 (9)
H7	0.2177	0.5936	1.6182	0.050*
C8	0.1056 (3)	0.5104 (3)	1.1487 (10)	0.0425 (9)
H8	0.0772	0.4889	1.0308	0.051*
C9	0.1388 (3)	0.4700 (3)	1.3222 (10)	0.0441 (10)
H9	0.1339	0.4224	1.3226	0.053*
C10	0.1804 (3)	0.5040 (3)	1.4990 (11)	0.0433 (10)
H10	0.2030	0.4779	1.6207	0.052*
C11	0.2775 (5)	0.7500	0.8417 (18)	0.067 (2)
H11A	0.3003	0.7274	0.7040	0.101*	0.50
H11B	0.2878	0.7260	0.9947	0.101*	0.50
H11C	0.2938	0.7966	0.8539	0.101*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0344 (5)	0.0327 (5)	0.0269 (4)	0.000	−0.0054 (4)	0.000
Br1	0.0519 (4)	0.0464 (4)	0.0369 (3)	−0.0063 (3)	−0.0153 (2)	−0.0044 (2)
O1	0.053 (2)	0.039 (2)	0.036 (2)	0.0042 (18)	−0.0152 (17)	0.0006 (16)
O2	0.048 (2)	0.076 (2)	0.040 (2)	0.000	−0.0030 (18)	0.000
N1	0.031 (2)	0.032 (2)	0.027 (2)	0.0034 (18)	−0.0029 (17)	0.0005 (18)
C1	0.0348 (17)	0.0422 (17)	0.0272 (16)	0.0003 (15)	−0.0009 (15)	0.0008 (15)
C2	0.0377 (19)	0.042 (2)	0.0308 (18)	−0.0010 (17)	−0.0037 (17)	0.0007 (17)
C3	0.033 (2)	0.040 (2)	0.0252 (19)	−0.0030 (18)	−0.0033 (17)	−0.0008 (18)
C4	0.0398 (16)	0.0449 (17)	0.0336 (16)	0.0007 (15)	−0.0047 (14)	0.0008 (14)
C5	0.0406 (17)	0.0443 (17)	0.0327 (16)	0.0021 (15)	−0.0034 (15)	0.0009 (15)
C6	0.0397 (17)	0.0469 (18)	0.0326 (16)	0.0026 (16)	−0.0015 (15)	0.0020 (15)
C7	0.0446 (19)	0.0446 (19)	0.0355 (18)	0.0035 (18)	−0.0059 (17)	0.0017 (17)
C8	0.0452 (18)	0.0444 (18)	0.0380 (18)	0.0005 (17)	−0.0052 (16)	0.0017 (16)
C9	0.048 (2)	0.044 (2)	0.0400 (19)	0.0020 (18)	−0.0039 (17)	0.0039 (17)
C10	0.047 (2)	0.0451 (19)	0.0381 (19)	0.0044 (18)	−0.0044 (17)	0.0055 (17)
C11	0.052 (4)	0.090 (4)	0.060 (4)	0.000	0.002 (4)	0.000

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.908 (4)	C4—C5	1.430 (7)
Cu1—O1	1.908 (3)	C4—H4	0.9300
Cu1—N1ⁱ	1.960 (4)	C5—C8	1.390 (8)
Cu1—N1	1.960 (4)	C5—C6	1.429 (7)
Cu1—O2	2.324 (6)	C6—C7	1.432 (7)
Br1—C3	1.886 (5)	C7—C10	1.358 (8)
O1—C6	1.289 (7)	C7—H7	0.9300
O2—C11	1.271 (9)	C8—C9	1.368 (7)
O2—H2A	0.8199	C8—H8	0.9300
N1—C4	1.285 (7)	C9—C10	1.399 (8)
N1—C1	1.410 (6)	C9—H9	0.9300
C1—C2	1.392 (7)	C10—H10	0.9300
C1—C1ⁱ	1.405 (10)	C11—H11A	0.9600
C2—C3	1.383 (7)	C11—H11B	0.9600
C2—H2	0.9300	C11—H11C	0.9600
C3—C3ⁱ	1.388 (10)

O1ⁱ—Cu1—O1	87.5 (2)	N1—C4—H4	116.9
O1ⁱ—Cu1—N1ⁱ	93.95 (16)	C5—C4—H4	116.9
O1—Cu1—N1ⁱ	172.22 (18)	C8—C5—C6	119.6 (5)
O1ⁱ—Cu1—N1	172.22 (18)	C8—C5—C4	117.7 (5)
O1—Cu1—N1	93.95 (16)	C6—C5—C4	122.7 (5)
N1ⁱ—Cu1—N1	83.6 (2)	O1—C6—C5	125.3 (5)
O1ⁱ—Cu1—O2	98.09 (16)	O1—C6—C7	118.9 (5)
O1—Cu1—O2	98.09 (16)	C5—C6—C7	115.9 (5)
N1ⁱ—Cu1—O2	89.29 (16)	C10—C7—C6	121.7 (5)
N1—Cu1—O2	89.29 (16)	C10—C7—H7	119.1
C6—O1—Cu1	127.0 (3)	C6—C7—H7	119.1
C11—O2—Cu1	126.8 (6)	C9—C8—C5	123.8 (5)
C11—O2—H2A	116.4	C9—C8—H8	118.1
Cu1—O2—H2A	116.8	C5—C8—H8	118.1
C4—N1—C1	122.6 (4)	C8—C9—C10	116.7 (6)
C4—N1—Cu1	124.8 (3)	C8—C9—H9	121.6
C1—N1—Cu1	112.6 (3)	C10—C9—H9	121.6
C2—C1—C1ⁱ	119.8 (3)	C7—C10—C9	122.3 (5)
C2—C1—N1	124.8 (5)	C7—C10—H10	119.2
C1ⁱ—C1—N1	115.4 (3)	C9—C10—H10	118.5
C3—C2—C1	119.9 (5)	O2—C11—H11A	109.5
C3—C2—H2	120.1	O2—C11—H11B	109.5
C1—C2—H2	120.1	H11A—C11—H11B	109.5
C2—C3—C3ⁱ	120.3 (3)	O2—C11—H11C	109.5
C2—C3—Br1	117.7 (4)	H11A—C11—H11C	109.5
C3ⁱ—C3—Br1	121.90 (15)	H11B—C11—H11C	109.5
N1—C4—C5	126.3 (5)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱⁱ	0.82	2.30	3.009 (6)	145

Symmetry code: (ii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	[Cu(C₂₀H₁₂Br₂N₂O₂)(CH₄O)]
M_r	567.72
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	273
a, b, c (Å)	19.164 (4), 19.416 (4), 5.3287 (10)
V (Å³)	1982.7 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.16
Crystal size (mm)	0.21 × 0.15 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.411, 0.554
No. of measured, independent and observed [I > 2σ(I)] reflections	9881, 2004, 1517
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.111, 1.06
No. of reflections	2004
No. of parameters	137
No. of restraints	242
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.23, −1.82

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
O2—H2A···O1ⁱ	0.82	2.30	3.009 (6)	144.9

Symmetry code: (i) x, y, z−1.

References

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