Bis[4-chloro-2-(imino­meth­yl)phenolato]copper(II)

In the title mononuclear copper(II) complex, [Cu(C₇H₅ClNO)₂], the Cu atom, situated on an inversion center, is four-coordinated, in a slightly distorted square-planar geometry, by the N- and O-donor atoms of two symmetry-related 4-chloro-2-(imino­meth­yl)phenolate Schiff base ligands.

Related literature

For the isotypic Ni(II) complex, see: Hong (2009). For bio-inorganic chemistry and the coordination chemistry of copper(II) complexes, see: Datta et al. (2008); Diallo et al. (2008); Khalaji et al. (2009).

Experimental

Crystal data

• [Cu(C₇H₅ClNO)₂]

• M_r = 372.68

• Monoclinic, P 2₁ /c

• a = 15.775 (4) Å

• b = 5.6949 (14) Å

• c = 7.886 (2) Å

• β = 93.932 (3)°

• V = 706.8 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 1.93 mm⁻¹

• T = 298 K

• 0.18 × 0.17 × 0.17 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.723, T_max = 0.735

• 3835 measured reflections

• 1488 independent reflections

• 1025 reflections with I > 2σ(I)

• R_int = 0.038

Refinement

• R[F² > 2σ(F²)] = 0.047

• wR(F²) = 0.139

• S = 1.01

• 1488 reflections

• 97 parameters

• H-atom parameters constrained

• Δρ_max = 0.48 e Å⁻³

• Δρ_min = −0.57 e Å⁻³

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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

S1. Comment

Copper(II) complexes have been widely investigated in both bioinorganic chemistry and coordination chemistry (Diallo et al., 2008; Datta et al., 2008; Khalaji et al., 2009). As a further study of the structures of such complexes, the crystal structure of the title mononuclear copper(II) complex is reported here. The title complex is isostructural with the nickel(II) complex of the same ligand, 4-Chloro-2-(iminomethyl)phenolate, reported on recently by (Hong, 2009).

The molecular structure of the title complex is illustrated in Fig. 1, and geometrical parameters are given in the archived CIF. The Cu^II atom lies on an inversion center and is four-coordinated in a square-planar geometry by the N-and O-donor atoms of two Schiff base ligands. The whole molecule of the complex is approximately coplanar with mean deviation from the least-squares plane of 0.021 (2) Å.

Related literature

For the isostructural nickel(II) complex of the same ligand, see: Hong (2009). For bio-inorganic chemistry and the coordination chemistry of copper(II) complexes, see: Datta et al. (2008); Diallo et al. (2008); Khalaji et al. (2009).

S2. Experimental

5-Chloro-2-hydroxybenzaldehyde (0.2 mmol, 31.3 mg), copper(II) acetate monohydrate (0.1 mmol, 20.0 mg) and three drops of ammonia (30%) were mixed in 10 ml of methanol. The final solution was stirred for 10 min and allowed to stand in air for two days, yielding blue needle-like crystals of the title compound.

S3. Refinement

The H-atoms were included in calculated positions and treated as riding: C-H = 0.93 Å, N-H = 0.86 Å, and U_iso(H) = 1.2U_eq(C,N).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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

Fig. 1. The structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level.

(I)

Crystal data

[Cu(C7H5ClNO)2]	F(000) = 374
Mr = 372.68	Dx = 1.751 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.775 (4) Å	Cell parameters from 811 reflections
b = 5.6949 (14) Å	θ = 2.5–24.3°
c = 7.886 (2) Å	µ = 1.93 mm^−1
β = 93.932 (3)°	T = 298 K
V = 706.8 (3) Å^3	Cut from needle, blue
Z = 2	0.18 × 0.17 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1488 independent reflections
Radiation source: fine-focus sealed tube	1025 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω scans	θmax = 26.7°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
Tmin = 0.723, Tmax = 0.735	k = −7→4
3835 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0757P)^2 + 0.0803P] where P = (Fo^2 + 2Fc^2)/3
1488 reflections	(Δ/σ)max < 0.001
97 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.5000	1.0000	1.0000	0.0394 (3)
Cl1	0.93518 (8)	0.8488 (3)	0.8060 (2)	0.0767 (5)
N1	0.5411 (2)	0.7404 (6)	0.8909 (4)	0.0407 (8)
H1	0.5043	0.6336	0.8631	0.049*
O1	0.60283 (17)	1.1520 (5)	1.0157 (4)	0.0418 (7)
C1	0.6875 (3)	0.8577 (7)	0.8857 (5)	0.0361 (9)
C2	0.6766 (3)	1.0747 (7)	0.9685 (5)	0.0369 (9)
C3	0.7494 (3)	1.2131 (8)	1.0047 (5)	0.0446 (11)
H3	0.7444	1.3543	1.0624	0.053*
C4	0.8280 (3)	1.1444 (8)	0.9568 (6)	0.0506 (12)
H4	0.8751	1.2397	0.9817	0.061*
C5	0.8372 (3)	0.9355 (8)	0.8721 (6)	0.0468 (11)
C6	0.7682 (3)	0.7904 (8)	0.8369 (6)	0.0460 (11)
H6	0.7749	0.6485	0.7811	0.055*
C7	0.6171 (3)	0.6979 (7)	0.8509 (5)	0.0411 (10)
H7	0.6274	0.5568	0.7967	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0443 (5)	0.0320 (4)	0.0413 (5)	−0.0014 (3)	−0.0013 (3)	−0.0036 (3)
Cl1	0.0436 (7)	0.0892 (11)	0.0988 (12)	0.0013 (7)	0.0152 (7)	−0.0162 (9)
N1	0.041 (2)	0.0338 (19)	0.047 (2)	−0.0048 (15)	−0.0007 (16)	−0.0067 (15)
O1	0.0398 (17)	0.0346 (17)	0.0509 (18)	−0.0019 (12)	0.0033 (13)	−0.0081 (13)
C1	0.041 (2)	0.031 (2)	0.036 (2)	−0.0007 (17)	−0.0005 (17)	0.0020 (17)
C2	0.046 (3)	0.031 (2)	0.033 (2)	−0.0010 (18)	−0.0024 (18)	−0.0008 (16)
C3	0.051 (3)	0.034 (2)	0.048 (3)	−0.0038 (19)	−0.003 (2)	−0.0040 (18)
C4	0.042 (3)	0.052 (3)	0.057 (3)	−0.008 (2)	−0.001 (2)	0.002 (2)
C5	0.037 (2)	0.052 (3)	0.051 (3)	0.003 (2)	0.004 (2)	0.001 (2)
C6	0.051 (3)	0.040 (3)	0.048 (3)	0.006 (2)	0.004 (2)	0.0001 (19)
C7	0.050 (3)	0.030 (2)	0.042 (2)	0.0008 (18)	−0.0004 (19)	−0.0048 (18)

Geometric parameters (Å, º)

Cu1—O1^i	1.835 (3)	C1—C7	1.447 (6)
Cu1—O1	1.835 (3)	C2—C3	1.406 (6)
Cu1—N1^i	1.850 (3)	C3—C4	1.378 (6)
Cu1—N1	1.850 (3)	C3—H3	0.9300
Cl1—C5	1.736 (5)	C4—C5	1.377 (7)
N1—C7	1.282 (5)	C4—H4	0.9300
N1—H1	0.8600	C5—C6	1.380 (6)
O1—C2	1.321 (5)	C6—H6	0.9300
C1—C6	1.408 (6)	C7—H7	0.9300
C1—C2	1.413 (6)
O1^i—Cu1—O1	180.00 (8)	C4—C3—C2	121.6 (4)
O1^i—Cu1—N1^i	94.10 (14)	C4—C3—H3	119.2
O1—Cu1—N1^i	85.90 (14)	C2—C3—H3	119.2
O1^i—Cu1—N1	85.90 (14)	C5—C4—C3	120.3 (4)
O1—Cu1—N1	94.10 (14)	C5—C4—H4	119.8
N1^i—Cu1—N1	180.000 (1)	C3—C4—H4	119.8
C7—N1—Cu1	128.9 (3)	C4—C5—C6	120.5 (4)
C7—N1—H1	115.5	C4—C5—Cl1	121.1 (4)
Cu1—N1—H1	115.5	C6—C5—Cl1	118.4 (4)
C2—O1—Cu1	128.0 (3)	C5—C6—C1	119.9 (4)
C6—C1—C2	120.3 (4)	C5—C6—H6	120.1
C6—C1—C7	118.3 (4)	C1—C6—H6	120.1
C2—C1—C7	121.4 (4)	N1—C7—C1	123.5 (4)
O1—C2—C3	118.6 (4)	N1—C7—H7	118.2
O1—C2—C1	124.0 (4)	C1—C7—H7	118.2
C3—C2—C1	117.4 (4)

Symmetry code: (i) −x+1, −y+2, −z+2.