catena-Poly[copper(II)-bis(μ-2,4-dichloro-6-formyl­phenolato)-κ3O,O′:Cl4;κ3Cl4:O,O′]

Fan, Y.; You, W.; Liu, J.-L.; Qian, H.-F.; Huang, W.

doi:10.1107/S1600536808020424

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1011

doi:10.1107/S1600536808020424

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catena-Poly[copper(II)-bis(μ-2,4-dichloro-6-formylphenolato)-κ³O,O′:Cl⁴;κ³Cl⁴:O,O′]

Ying Fan,^a Wei You,^a Jian-Lan Liu,^a Hui-Fen Qian ^a ^* and Wei Huang ^b ‡

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn

(Received 25 June 2008; accepted 3 July 2008; online 9 July 2008)

In the title compound, [Cu(C₇H₃Cl₂O₂)₂]_n, the Cu^II atom lies on a centre of inversion and adopts a [4+2] coordination mode, with two long axial Cu—Cl coordinative bonds complementing four Cu—O bonds from two 2,4-dichloro-6-formylphenolate ligands in a distorted square plane. π–π stacking interactions are also formed between neighbouring aromatic rings, with a centroid–centroid separation of 3.624 (2) Å.

Related literature

For related compounds, see: Duan et al. (2007 ); Fan, You, Liu et al. (2008 ); Fan, You, Qian et al. (2008 ); Harkat et al. (2008 ); Sun & Gao (2005 ); Zhang et al. (2006 ).

Experimental

Crystal data

[Cu(C₇H₃Cl₂O₂)₂]
M_r = 443.53
Orthorhombic, P b c a
a = 8.1564 (8) Å
b = 12.4746 (12) Å
c = 14.7296 (14) Å
V = 1498.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.19 mm⁻¹
T = 291 (2) K
0.14 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.750, T_max = 0.811
7424 measured reflections
1471 independent reflections
1215 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.103
S = 1.06
1471 reflections
106 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.906 (2)
Cu1—O2	1.943 (2)
Cu1—Cl2ⁱⁱ	3.207 (1)

O1—Cu1—O1ⁱ	180
O1—Cu1—O2ⁱ	87.13 (8)
O1—Cu1—O2	92.87 (8)
O2ⁱ—Cu1—O2	180
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) x+1, y, z; (iii) -x+1, -y+2, -z+1.

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/S1600536808020424/bi2288sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020424/bi2288Isup2.hkl

checkCIF report

Comment top

The design and synthesis of derivatives of salicylaldehyde and their metal complexes are fascinating areas of research, which can be used in a variety of studies such as drug design, life science, catalysis, and so on (Harkat et al., 2008; Duan et al., 2007). In our previous studies, we have reported the X-ray single-crystal structures of 3,5-dichloro-2-hydroxybenzaldehyde and 3,5-dibromo-2-hydroxybenzaldehyde (Fan et al., 2008a, b). In this paper, we report the X-ray single-crystal structure of the title Cu^II complex.

In the title compound (Fig. 1), the coordination geometry of the central Cu^II ion can be described as [4 + 2]. Four Cu—O bonds from two 3,5-dichloro-2-hydroxybenzaldehyde anions constitute a distorted square coordination plane with the bond lengths varying from 1.906 (2) to 1.943 (2) Å (Table 1), which are in good agreement with those found in similar Cu^II complexes (Sun & Gao, 2005; Zhang et al., 2006). Two adjacent Cl atoms from two 3,5-dichloro-2-hydroxybenzaldehyde anions (Cl2, symmetry codes: 1 + x, y, z and 1 - x, 2 - y, 1 - z) occupy two axial positions by weak coordinative bonds with the same Cu—Cl bond length of 3.207 (1) Å (Fig. 2). In addition, these molecules are further stabilized by π-π stacking interactions with the centroid-to-centroid separation of 3.624 (2) Å, forming one-dimensional chain motifs (Fig. 2). A dihedral angle of 45.3 (1) ° is formed between the planes of molecules in neighbouring chains.

Related literature top

For related compounds, see: Duan et al. (2007); Fan, You, Liu et al. (2008); Fan, You, Qian et al. (2008); Harkat et al. (2008); Sun & Gao (2005); Zhang et al. (2006).

Experimental top

A solution of Cu(OAc)₂.H₂O (0.1 mmol, 0.020 g) in methanol (5 ml) was added to a methanol solution (20 ml) of 3,5-dichloro-2-hydroxybenzaldehyde (0.2 mmol, 0.039 g). The resulting mixture was refluxed for 2 h, cooled and evaporated slowly at room temperature in air to give dark red single crystals suitable for X-ray diffraction measurement. Analysis calculated for C₁₄H₆O₄Cl₄Cu: C, 37.91. H, 1.36%; found: C, 37.85; H, 1.59%.

FT—IR (KBr pellets, cm^-1): 3058 (m), 1605 (vs), 1510 (s), 1438 (s), 1420 (s), 1337 (s), 1217 (s), 1162 (s), 887 (m), 766 (s), 720 (m), 600 (m) and 455 (m).

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. Molecular structure showing displacement ellipsoids at the 30% probability level for non-H atoms. Cu1 lies on a centre of inversion: unlabelled atoms are related to labelled atoms by the symmetry code 2-x, 2-y, 1-z.
	Fig. 2. A perspective view of one chain motif, showing long Cu—Cl coordinative bonds and π–π stacking interactions (dashed lines).

catena-Poly[copper(II)-bis(µ-2,4-dichloro-6-formylphenolato)-κ³O,O':Cl⁴;κ³Cl⁴:O,O'] top

Crystal data top

[Cu(C₇H₃Cl₂O₂)₂]	F(000) = 876
M_r = 443.53	D_x = 1.966 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3128 reflections
a = 8.1564 (8) Å	θ = 2.8–27.6°
b = 12.4746 (12) Å	µ = 2.19 mm⁻¹
c = 14.7296 (14) Å	T = 291 K
V = 1498.7 (3) Å³	Block, red
Z = 4	0.14 × 0.12 × 0.10 mm

Data collection top

Bruker SMART CCD diffractometer	1471 independent reflections
Radiation source: fine-focus sealed tube	1215 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.750, T_max = 0.811	k = −15→15
7424 measured reflections	l = −11→18

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0631P)² + 0.6132P] where P = (F_o² + 2F_c²)/3
1471 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.83 e Å⁻³

Crystal data top

[Cu(C₇H₃Cl₂O₂)₂]	V = 1498.7 (3) Å³
M_r = 443.53	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 8.1564 (8) Å	µ = 2.19 mm⁻¹
b = 12.4746 (12) Å	T = 291 K
c = 14.7296 (14) Å	0.14 × 0.12 × 0.10 mm

Data collection top

Bruker SMART CCD diffractometer	1471 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1215 reflections with I > 2σ(I)
T_min = 0.750, T_max = 0.811	R_int = 0.043
7424 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.06	Δρ_max = 0.41 e Å⁻³
1471 reflections	Δρ_min = −0.83 e Å⁻³
106 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
Cu1	1.0000	1.0000	0.5000	0.0350 (2)
C1	0.6397 (3)	0.9163 (2)	0.43110 (19)	0.0300 (6)
C2	0.6929 (3)	1.0203 (2)	0.4048 (2)	0.0283 (6)
C3	0.5807 (4)	1.0793 (2)	0.3514 (2)	0.0310 (6)
C4	0.4281 (4)	1.0410 (2)	0.3285 (2)	0.0348 (7)
H4	0.3569	1.0829	0.2943	0.042*
C5	0.3807 (3)	0.9390 (2)	0.3569 (2)	0.0334 (7)
C6	0.4844 (3)	0.8770 (2)	0.4061 (2)	0.0324 (7)
H6	0.4528	0.8083	0.4233	0.039*
C7	0.7396 (4)	0.8478 (3)	0.4859 (2)	0.0371 (7)
H7	0.6969	0.7805	0.4993	0.045*
Cl1	0.64045 (10)	1.20455 (6)	0.31242 (6)	0.0445 (3)
Cl2	0.18463 (10)	0.89331 (8)	0.33032 (6)	0.0473 (3)
O1	0.8330 (2)	1.06231 (16)	0.42655 (15)	0.0367 (5)
O2	0.8767 (3)	0.86838 (18)	0.51754 (15)	0.0413 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0256 (3)	0.0313 (3)	0.0481 (4)	0.0010 (2)	−0.0058 (2)	0.0057 (2)
C1	0.0251 (14)	0.0316 (15)	0.0332 (16)	0.0020 (11)	−0.0008 (12)	0.0006 (12)
C2	0.0244 (14)	0.0287 (14)	0.0318 (15)	0.0025 (11)	0.0021 (12)	0.0003 (11)
C3	0.0304 (15)	0.0287 (14)	0.0339 (15)	0.0033 (12)	0.0019 (13)	0.0006 (12)
C4	0.0309 (15)	0.0380 (16)	0.0356 (17)	0.0081 (14)	−0.0035 (13)	−0.0012 (13)
C5	0.0241 (13)	0.0436 (17)	0.0325 (15)	−0.0012 (13)	−0.0007 (12)	−0.0059 (13)
C6	0.0302 (15)	0.0319 (16)	0.0352 (16)	−0.0033 (12)	0.0001 (12)	−0.0019 (12)
C7	0.0322 (16)	0.0310 (15)	0.0481 (18)	−0.0002 (14)	−0.0035 (14)	0.0044 (13)
Cl1	0.0438 (5)	0.0313 (4)	0.0583 (5)	0.0029 (3)	−0.0019 (4)	0.0106 (3)
Cl2	0.0299 (4)	0.0576 (5)	0.0544 (5)	−0.0064 (4)	−0.0109 (3)	−0.0036 (4)
O1	0.0258 (10)	0.0321 (11)	0.0522 (13)	−0.0022 (9)	−0.0064 (9)	0.0076 (9)
O2	0.0302 (12)	0.0345 (12)	0.0592 (14)	−0.0006 (9)	−0.0110 (10)	0.0104 (10)

Geometric parameters (Å, º) top

Cu1—O1	1.906 (2)	C2—C3	1.413 (4)
Cu1—O1ⁱ	1.906 (2)	C3—C4	1.375 (4)
Cu1—O2ⁱ	1.943 (2)	C3—Cl1	1.735 (3)
Cu1—O2	1.943 (2)	C4—C5	1.394 (4)
Cu1—Cl2ⁱⁱ	3.207 (1)	C4—H4	0.930
Cu1—Cl2ⁱⁱⁱ	3.207 (1)	C5—C6	1.356 (4)
C1—C6	1.408 (4)	C5—Cl2	1.742 (3)
C1—C2	1.422 (4)	C6—H6	0.930
C1—C7	1.431 (4)	C7—O2	1.238 (4)
C2—O1	1.297 (3)	C7—H7	0.930

O1—Cu1—O1ⁱ	180	C3—C4—C5	119.7 (3)
O1—Cu1—O2ⁱ	87.13 (8)	C3—C4—H4	120.2
O1ⁱ—Cu1—O2ⁱ	92.87 (8)	C5—C4—H4	120.2
O1—Cu1—O2	92.87 (8)	C6—C5—C4	120.5 (3)
O1ⁱ—Cu1—O2	87.13 (8)	C6—C5—Cl2	120.4 (2)
O2ⁱ—Cu1—O2	180	C4—C5—Cl2	119.1 (2)
C6—C1—C2	121.4 (3)	C5—C6—C1	120.2 (3)
C6—C1—C7	116.9 (3)	C5—C6—H6	119.9
C2—C1—C7	121.7 (3)	C1—C6—H6	119.9
O1—C2—C3	119.8 (2)	O2—C7—C1	127.0 (3)
O1—C2—C1	124.7 (3)	O2—C7—H7	116.5
C3—C2—C1	115.4 (2)	C1—C7—H7	116.5
C4—C3—C2	122.8 (3)	C2—O1—Cu1	127.25 (18)
C4—C3—Cl1	119.1 (2)	C7—O2—Cu1	126.4 (2)
C2—C3—Cl1	118.1 (2)

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₃Cl₂O₂)₂]
M_r	443.53
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	291
a, b, c (Å)	8.1564 (8), 12.4746 (12), 14.7296 (14)
V (Å³)	1498.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.19
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.750, 0.811
No. of measured, independent and observed [I > 2σ(I)] reflections	7424, 1471, 1215
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.103, 1.06
No. of reflections	1471
No. of parameters	106
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.83

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

Selected geometric parameters (Å, º) top

Cu1—O1	1.906 (2)	Cu1—O2	1.943 (2)
Cu1—O1ⁱ	1.906 (2)	Cu1—Cl2ⁱⁱ	3.207 (1)
Cu1—O2ⁱ	1.943 (2)	Cu1—Cl2ⁱⁱⁱ	3.207 (1)

O1—Cu1—O1ⁱ	180	O1—Cu1—O2	92.87 (8)
O1—Cu1—O2ⁱ	87.13 (8)	O1ⁱ—Cu1—O2	87.13 (8)
O1ⁱ—Cu1—O2ⁱ	92.87 (8)	O2ⁱ—Cu1—O2	180

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1.

Footnotes

‡Additional correspondence author.

Acknowledgements

WH acknowledges financial aid from the National Natural Science Foundation of China (grant No. 20301009) and the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Duan, X. F., Zeng, J., Zhang, Z. B. & Zi, G. F. (2007). J. Org. Chem. 72, 10283–10286. Web of Science CrossRef PubMed CAS Google Scholar
Fan, Y., You, W., Liu, J.-L., Qian, H.-F. & Huang, W. (2008). Acta Cryst. E64, o1080. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fan, Y., You, W., Qian, H.-F., Liu, J.-L. & Huang, W. (2008). Acta Cryst. E64, o799. Web of Science CSD CrossRef IUCr Journals Google Scholar
Harkat, H., Blanc, A., Weibel, J. M. & Pale, P. (2008). J. Org. Chem. 73, 1620–1623. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, Y.-X. & Gao, G.-Z. (2005). Acta Cryst. E61, m354–m355. Web of Science CrossRef IUCr Journals Google Scholar
Zhang, G., Yang, G. & Ma, J. S. (2006). J. Chem. Res. pp. 19–21. CrossRef Google Scholar

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