{4,4′,6,6′-Tetra­bromo-2,2′-[(2,2-dimethyl­propane-1,3-di­yl)bis­(nitrilo­methanylyl­idene)]diphenolato}copper(II)

Kargar, H.; Kia, R.; Haghshenas, M.; Tahir, M.N.

doi:10.1107/S1600536812009397

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m392

doi:10.1107/S1600536812009397

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{4,4′,6,6′-Tetrabromo-2,2′-[(2,2-dimethylpropane-1,3-diyl)bis(nitrilomethanylylidene)]diphenolato}copper(II)

Hadi Kargar,^a ^* Reza Kia,^b Mahbubeh Haghshenas ^a and Muhammad Nawaz Tahir ^c ^*

^aDepartment of Chemistry, Payame Noor University, PO Box 19395-3697 Tehran, I. R. of IRAN, ^bX-ray Crystallography Laboratory, Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran, Iran, and, Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, and ^cDepartment of Physics, University of Sargodha, Punjab, Pakistan
^*Correspondence e-mail: h.kargar@pnu.ac.ir, dmntahir_uos@yahoo.com

(Received 6 January 2012; accepted 2 March 2012; online 10 March 2012)

In the title compound, [Cu(C₁₉H₁₆Br₄N₂O₂)], the Cu^II ion and the substituted C atom of the diamine fragment lie on a crystallographic twofold rotation axis. The geometry around the Cu^II ion is distorted square-planar, which is defined by the N₂O₂ donor atoms of the coordinated Schiff base ligand. The dihedral angle between the symmetry-related substituted benzene rings is 25.33 (14)°. The crystal structure is stabilized by an intermolecular π–π interaction [centroid–centroid distance = 3.8891 (18) Å].

Related literature

For standard bond lengths, see: Allen et al. (1987 ). For applications of Schiff base ligands in coordination chemistry, see: Granovski et al. (1993 ); Blower (1998 ). For a related structure, see: Kargar et al. (2008 ).

Experimental

Crystal data

[Cu(C₁₉H₁₆Br₄N₂O₂)]
M_r = 687.52
Orthorhombic, P b c n
a = 16.3594 (8) Å
b = 15.5106 (8) Å
c = 8.4686 (4) Å
V = 2148.86 (18) Å³
Z = 4
Mo Kα radiation
μ = 8.47 mm⁻¹
T = 291 K
0.21 × 0.12 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.269, T_max = 0.551
9913 measured reflections
2537 independent reflections
1625 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.078
S = 1.00
2537 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812009397/bv2199sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009397/bv2199Isup2.hkl

checkCIF report

Comment top

Schiff base complexes are one of the most important stereochemical models in transition metal coordination chemistry, with the ease of preparation and structural variations (Granovski et al., 1993; Blower (1998)).

The asymmetric unit of the title compound, Fig. 1, comprises half of a potentially tetradentate Schiff base ligand. The bond lengths (Allen et al., 1987) and angles are within the normal ranges. The Cu1 and C9 atoms lie on crystallographic two-fold rotation axis. The crystal structure is further stabilized by the intermolecular π-π interaction, (Fig. 2), [Cg1···Cg1ⁱ = 3.8891 (18)Å; (i) 1 - X, 1 - Y, -Z; Cg1 is the centroid of Cu(1)/O(1)/C(1)/C(6)/C(7)/N(1) ring].

Related literature top

For standard bond lengths, see: Allen et al. (1987). For applications of Schiff base ligands in coordination chemistry, see: Granovski et al. (1993); Blower (1998). For a related structure, see: Kargar et al. (2008).

Experimental top

The title compound was synthesized by adding 3,5-dibromo-salicylaldehyde-2,2-dimethyl-1,3- propanediamine (2 mmol) to a solution of CuCl₂. 4H₂O (2.1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for half an hour. The resultant solution was filtered. Green single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.

Structure description top

For standard bond lengths, see: Allen et al. (1987). For applications of Schiff base ligands in coordination chemistry, see: Granovski et al. (1993); Blower (1998). For a related structure, see: Kargar et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The ORTEP plot of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. The packing diagram of the title compound viewed down the b-axis showing linking of molecules through the intermolecular π-π intearctions (dashed lines). The hydrogen atoms omitted for clarity.

{4,4',6,6'-Tetrabromo-2,2'-[(2,2-dimethylpropane-1,3- diyl)bis(nitrilomethanylylidene)]diphenolato}copper(II) top

Crystal data top

[Cu(C₁₉H₁₆Br₄N₂O₂)]	F(000) = 1316
M_r = 687.52	D_x = 2.125 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1535 reflections
a = 16.3594 (8) Å	θ = 2.5–27.5°
b = 15.5106 (8) Å	µ = 8.47 mm⁻¹
c = 8.4686 (4) Å	T = 291 K
V = 2148.86 (18) Å³	Block, green
Z = 4	0.21 × 0.12 × 0.08 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2537 independent reflections
Radiation source: fine-focus sealed tube	1625 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
φ and ω scans	θ_max = 28.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −21→18
T_min = 0.269, T_max = 0.551	k = −20→13
9913 measured reflections	l = −10→7

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0202P)² + 1.7635P] where P = (F_o² + 2F_c²)/3
2537 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Cu(C₁₉H₁₆Br₄N₂O₂)]	V = 2148.86 (18) Å³
M_r = 687.52	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 16.3594 (8) Å	µ = 8.47 mm⁻¹
b = 15.5106 (8) Å	T = 291 K
c = 8.4686 (4) Å	0.21 × 0.12 × 0.08 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2537 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1625 reflections with I > 2σ(I)
T_min = 0.269, T_max = 0.551	R_int = 0.052
9913 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.00	Δρ_max = 0.58 e Å⁻³
2537 reflections	Δρ_min = −0.59 e Å⁻³
128 parameters

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
Br1	0.33450 (3)	0.74146 (3)	0.18143 (5)	0.05098 (16)
Br2	0.10313 (3)	0.54552 (4)	−0.15415 (7)	0.0733 (2)
Cu1	0.5000	0.48415 (4)	0.2500	0.03410 (18)
N1	0.4444 (2)	0.39656 (19)	0.1258 (3)	0.0332 (7)
O1	0.42323 (17)	0.57112 (16)	0.1958 (3)	0.0395 (7)
C1	0.3547 (2)	0.5618 (2)	0.1192 (4)	0.0341 (9)
C2	0.3023 (2)	0.6335 (2)	0.0965 (4)	0.0341 (9)
C3	0.2301 (2)	0.6285 (3)	0.0162 (4)	0.0406 (10)
H3	0.1982	0.6776	0.0030	0.049*
C4	0.2042 (2)	0.5504 (3)	−0.0458 (5)	0.0417 (10)
C5	0.2520 (3)	0.4788 (3)	−0.0299 (4)	0.0425 (10)
H5	0.2348	0.4267	−0.0730	0.051*
C6	0.3270 (2)	0.4831 (2)	0.0511 (4)	0.0342 (9)
C7	0.3757 (3)	0.4058 (2)	0.0534 (4)	0.0368 (10)
H7	0.3560	0.3585	−0.0022	0.044*
C8	0.4911 (3)	0.3163 (2)	0.1017 (4)	0.0404 (10)
H8A	0.5453	0.3310	0.0635	0.048*
H8B	0.4644	0.2825	0.0204	0.048*
C9	0.5000	0.2606 (3)	0.2500	0.0390 (14)
C10	0.5749 (3)	0.2038 (3)	0.2270 (5)	0.0574 (13)
H10A	0.6231	0.2391	0.2253	0.086*
H10B	0.5703	0.1733	0.1288	0.086*
H10C	0.5786	0.1633	0.3123	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0710 (3)	0.0317 (2)	0.0503 (3)	0.0104 (2)	−0.0024 (2)	−0.0063 (2)
Br2	0.0527 (3)	0.0645 (4)	0.1027 (4)	0.0055 (3)	−0.0303 (3)	0.0001 (3)
Cu1	0.0387 (4)	0.0275 (3)	0.0361 (4)	0.000	−0.0012 (3)	0.000
N1	0.041 (2)	0.0256 (17)	0.0334 (17)	0.0063 (16)	0.0008 (15)	−0.0012 (14)
O1	0.0416 (17)	0.0295 (14)	0.0475 (16)	0.0014 (13)	−0.0063 (13)	−0.0027 (13)
C1	0.042 (3)	0.031 (2)	0.030 (2)	0.002 (2)	0.0088 (18)	0.0010 (18)
C2	0.043 (2)	0.029 (2)	0.031 (2)	0.0058 (19)	0.0072 (18)	−0.0018 (18)
C3	0.044 (3)	0.039 (2)	0.039 (2)	0.013 (2)	0.0078 (19)	0.002 (2)
C4	0.035 (2)	0.046 (3)	0.045 (2)	0.006 (2)	−0.0028 (19)	0.001 (2)
C5	0.045 (3)	0.039 (2)	0.043 (2)	−0.002 (2)	−0.002 (2)	−0.002 (2)
C6	0.041 (2)	0.029 (2)	0.032 (2)	0.005 (2)	0.0022 (17)	0.0001 (18)
C7	0.049 (3)	0.029 (2)	0.032 (2)	0.001 (2)	0.0022 (19)	−0.0042 (18)
C8	0.052 (3)	0.031 (2)	0.038 (2)	0.012 (2)	−0.0001 (19)	−0.0050 (19)
C9	0.047 (4)	0.026 (3)	0.044 (3)	0.000	−0.007 (3)	0.000
C10	0.064 (3)	0.046 (3)	0.062 (3)	0.017 (3)	−0.013 (2)	0.005 (2)

Geometric parameters (Å, º) top

Br1—C2	1.897 (4)	C4—C5	1.364 (6)
Br2—C4	1.893 (4)	C5—C6	1.407 (5)
Cu1—O1ⁱ	1.899 (3)	C5—H5	0.9300
Cu1—O1	1.899 (3)	C6—C7	1.440 (5)
Cu1—N1ⁱ	1.944 (3)	C7—H7	0.9300
Cu1—N1	1.944 (3)	C8—C9	1.531 (5)
N1—C7	1.288 (5)	C8—H8A	0.9700
N1—C8	1.475 (5)	C8—H8B	0.9700
O1—C1	1.303 (5)	C9—C10ⁱ	1.522 (5)
C1—C2	1.418 (5)	C9—C10	1.522 (5)
C1—C6	1.425 (5)	C9—C8ⁱ	1.531 (5)
C2—C3	1.364 (5)	C10—H10A	0.9600
C3—C4	1.387 (6)	C10—H10B	0.9600
C3—H3	0.9300	C10—H10C	0.9600

O1ⁱ—Cu1—O1	89.50 (16)	C5—C6—C1	121.0 (4)
O1ⁱ—Cu1—N1ⁱ	93.23 (12)	C5—C6—C7	116.8 (4)
O1—Cu1—N1ⁱ	159.45 (11)	C1—C6—C7	122.1 (4)
O1ⁱ—Cu1—N1	159.45 (11)	N1—C7—C6	125.6 (4)
O1—Cu1—N1	93.23 (12)	N1—C7—H7	117.2
N1ⁱ—Cu1—N1	91.32 (18)	C6—C7—H7	117.2
C7—N1—C8	118.7 (3)	N1—C8—C9	114.3 (3)
C7—N1—Cu1	126.0 (3)	N1—C8—H8A	108.7
C8—N1—Cu1	115.0 (3)	C9—C8—H8A	108.7
C1—O1—Cu1	127.6 (2)	N1—C8—H8B	108.7
O1—C1—C2	120.1 (4)	C9—C8—H8B	108.7
O1—C1—C6	124.8 (4)	H8A—C8—H8B	107.6
C2—C1—C6	115.1 (4)	C10ⁱ—C9—C10	109.2 (5)
C3—C2—C1	123.2 (4)	C10ⁱ—C9—C8ⁱ	107.3 (2)
C3—C2—Br1	118.7 (3)	C10—C9—C8ⁱ	110.8 (2)
C1—C2—Br1	118.2 (3)	C10ⁱ—C9—C8	110.8 (2)
C2—C3—C4	120.2 (4)	C10—C9—C8	107.3 (2)
C2—C3—H3	119.9	C8ⁱ—C9—C8	111.3 (4)
C4—C3—H3	119.9	C9—C10—H10A	109.5
C5—C4—C3	119.9 (4)	C9—C10—H10B	109.5
C5—C4—Br2	121.1 (3)	H10A—C10—H10B	109.5
C3—C4—Br2	119.0 (3)	C9—C10—H10C	109.5
C4—C5—C6	120.6 (4)	H10A—C10—H10C	109.5
C4—C5—H5	119.7	H10B—C10—H10C	109.5
C6—C5—H5	119.7

O1ⁱ—Cu1—N1—C7	−102.7 (4)	C2—C3—C4—Br2	179.2 (3)
O1—Cu1—N1—C7	−5.5 (3)	C3—C4—C5—C6	1.0 (6)
N1ⁱ—Cu1—N1—C7	154.5 (4)	Br2—C4—C5—C6	−179.9 (3)
O1ⁱ—Cu1—N1—C8	70.7 (4)	C4—C5—C6—C1	0.3 (6)
O1—Cu1—N1—C8	167.9 (2)	C4—C5—C6—C7	−176.2 (4)
N1ⁱ—Cu1—N1—C8	−32.2 (2)	O1—C1—C6—C5	180.0 (3)
O1ⁱ—Cu1—O1—C1	167.4 (3)	C2—C1—C6—C5	−0.9 (5)
N1ⁱ—Cu1—O1—C1	−94.7 (4)	O1—C1—C6—C7	−3.7 (6)
N1—Cu1—O1—C1	7.8 (3)	C2—C1—C6—C7	175.4 (3)
Cu1—O1—C1—C2	176.5 (2)	C8—N1—C7—C6	−173.3 (3)
Cu1—O1—C1—C6	−4.5 (5)	Cu1—N1—C7—C6	−0.1 (6)
O1—C1—C2—C3	179.4 (3)	C5—C6—C7—N1	−177.5 (4)
C6—C1—C2—C3	0.2 (5)	C1—C6—C7—N1	6.1 (6)
O1—C1—C2—Br1	−0.4 (5)	C7—N1—C8—C9	−115.0 (4)
C6—C1—C2—Br1	−179.5 (3)	Cu1—N1—C8—C9	71.1 (4)
C1—C2—C3—C4	1.0 (6)	N1—C8—C9—C10ⁱ	83.8 (4)
Br1—C2—C3—C4	−179.2 (3)	N1—C8—C9—C10	−157.0 (4)
C2—C3—C4—C5	−1.7 (6)	N1—C8—C9—C8ⁱ	−35.6 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₉H₁₆Br₄N₂O₂)]
M_r	687.52
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	291
a, b, c (Å)	16.3594 (8), 15.5106 (8), 8.4686 (4)
V (Å³)	2148.86 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.47
Crystal size (mm)	0.21 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.269, 0.551
No. of measured, independent and observed [I > 2σ(I)] reflections	9913, 2537, 1625
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.078, 1.00
No. of reflections	2537
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.59

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

HK and MH thank PNU for financial support. MNT thanks GC University of Sargodha, Pakistan, for the research facility.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Blower, P. J. (1998). Transition Met. Chem., 23, 109–112. CrossRef CAS Google Scholar
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Granovski, A. D., Nivorozhkin, A. L. & Minkin, V. I. (1993). Coord. Chem. Rev. 126, 1–69. Google Scholar
Kargar, H., Fun, H.-K. & Kia, R. (2008). Acta Cryst. E64, m1541–m1542. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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