Bis{(E)-4-chloro-2-[(2-chloro-3-pyrid-yl)imino-methyl-κN]phenolato-κO}copper(II).

In the title complex, [Cu(C(12)H(7)Cl(2)N(2)O)(2)], the Cu(II) center is tetra-coordinated by two phenolic O and two azomethine N atoms from two bidentate 4-chloro-2-[(2-chloro-3-pyrid-yl)imino-meth-yl]phenolate (L) ligands. In the crystal structure, the Cu(II) atom has a distorted square-planar coordination environment. The dihedral angles between the benzene and pyridyl rings are 54.39 (3) and 80.14 (4)°, indicating that the pyridine ring has a considerably weaker steric hindrance. The packing of the mol-ecule is controlled by C-H⋯π(Ph) inter-actions and short O⋯Cl inter-actions [3.196 (4) Å], linking the mol-ecules into a chain-like structure along the c axis.

Related literature

For background to Schiff bases, see: Soliman & Mohamed (2004 ▶); Abd El-Wahab et al. (2004 ▶). For the synthesis, see: Dong et al. (2009d ▶). For related structures, see: Dong et al. (2009 ▶).

Experimental

Crystal data

[Cu(C12H7Cl2N2O)2]

M = 595.73

Monoclinic,

a = 20.236 (2) Å

b = 11.4821 (14) Å

c = 10.5458 (9) Å

β = 90.132 (2)°

V = 2450.3 (4) Å3

Z = 4

Mo Kα radiation

μ = 1.36 mm−1

T = 298 K

0.40 × 0.14 × 0.09 mm

Data collection

Buker SMART 1000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.613, T max = 0.888

12294 measured reflections

4320 independent reflections

2614 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.065

S = 1.02

4320 reflections

316 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.39 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029651/at2850sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029651/at2850Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C12H7Cl2N2O)2]	F(000) = 1196
Mr = 595.73	Dx = 1.615 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2435 reflections
a = 20.236 (2) Å	θ = 26.2–25.3°
b = 11.4821 (14) Å	µ = 1.36 mm−1
c = 10.5458 (9) Å	T = 298 K
β = 90.132 (2)°	Needle-like, brown
V = 2450.3 (4) Å3	0.40 × 0.14 × 0.09 mm
Z = 4

Buker SMART 1000 CCD area-detector diffractometer	4320 independent reflections
Radiation source: fine-focus sealed tube	2614 reflections with I > 2σ(I)
graphite	Rint = 0.058
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→19
Tmin = 0.613, Tmax = 0.888	k = −13→13
12294 measured reflections	l = −12→12

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) = 0.065	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0103P)2] where P = (Fo2 + 2Fc2)/3
4320 reflections	(Δ/σ)max = 0.001
316 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.75122 (2)	0.77649 (3)	0.42109 (4)	0.04479 (14)
Cl1	0.85318 (5)	0.19528 (7)	0.24296 (11)	0.0748 (4)
Cl2	0.69809 (5)	0.87831 (8)	0.16425 (10)	0.0715 (3)
Cl3	0.63434 (5)	1.36121 (8)	0.53290 (13)	0.0847 (4)
Cl4	0.87717 (5)	0.87627 (9)	0.20907 (10)	0.0712 (3)
N1	0.69574 (13)	0.6664 (2)	0.3246 (3)	0.0404 (7)
N2	0.5723 (2)	0.8484 (3)	0.1640 (4)	0.0824 (12)
N3	0.81090 (13)	0.9095 (2)	0.4590 (3)	0.0405 (7)
N4	0.97911 (16)	0.8403 (3)	0.3522 (3)	0.0580 (9)
O1	0.82307 (10)	0.67264 (18)	0.4291 (2)	0.0496 (7)
O2	0.67527 (11)	0.85984 (17)	0.4727 (2)	0.0475 (7)
C1	0.71125 (17)	0.5582 (3)	0.3021 (3)	0.0434 (9)
H1	0.6795	0.5116	0.2634	0.052*
C2	0.77345 (17)	0.5055 (3)	0.3324 (3)	0.0402 (9)
C3	0.82696 (17)	0.5658 (3)	0.3882 (3)	0.0387 (9)
C4	0.88764 (17)	0.5059 (3)	0.3980 (3)	0.0493 (10)
H4	0.9234	0.5434	0.4355	0.059*
C5	0.89566 (19)	0.3951 (3)	0.3546 (4)	0.0515 (10)
H5	0.9366	0.3587	0.3612	0.062*
C6	0.8432 (2)	0.3370 (3)	0.3011 (4)	0.0507 (11)
C7	0.78289 (18)	0.3887 (3)	0.2908 (3)	0.0479 (10)
H7	0.7476	0.3474	0.2564	0.057*
C8	0.62746 (19)	0.8039 (3)	0.2075 (4)	0.0560 (11)
C9	0.63246 (18)	0.7033 (3)	0.2809 (3)	0.0459 (10)
C10	0.5749 (2)	0.6457 (3)	0.3112 (4)	0.0635 (12)
H10	0.5757	0.5791	0.3614	0.076*
C11	0.5154 (2)	0.6894 (4)	0.2649 (5)	0.0825 (15)
H11	0.4756	0.6519	0.2810	0.099*
C12	0.5177 (3)	0.7896 (5)	0.1948 (5)	0.0967 (18)
H12	0.4777	0.8195	0.1661	0.116*
C13	0.79004 (17)	1.0141 (3)	0.4799 (3)	0.0432 (9)
H13	0.8221	1.0711	0.4922	0.052*
C14	0.72224 (17)	1.0512 (3)	0.4859 (3)	0.0398 (9)
C15	0.66883 (18)	0.9718 (3)	0.4849 (3)	0.0421 (9)
C16	0.60489 (17)	1.0190 (3)	0.5003 (3)	0.0522 (11)
H16	0.5688	0.9689	0.5007	0.063*
C17	0.59427 (18)	1.1356 (3)	0.5146 (4)	0.0575 (11)
H17	0.5515	1.1639	0.5245	0.069*
C18	0.64736 (19)	1.2118 (3)	0.5142 (4)	0.0531 (11)
C19	0.71064 (18)	1.1714 (3)	0.5010 (3)	0.0489 (10)
H19	0.7459	1.2233	0.5021	0.059*
C20	0.91648 (19)	0.8681 (3)	0.3548 (4)	0.0453 (10)
C21	0.88043 (17)	0.8917 (3)	0.4636 (4)	0.0403 (9)
C22	0.91409 (18)	0.8877 (3)	0.5758 (4)	0.0525 (10)
H22	0.8923	0.9029	0.6516	0.063*
C23	0.98051 (19)	0.8610 (3)	0.5768 (4)	0.0582 (11)
H23	1.0044	0.8594	0.6522	0.070*
C24	1.01031 (19)	0.8367 (3)	0.4626 (5)	0.0594 (12)
H24	1.0548	0.8166	0.4631	0.071*

	U11	U22	U33	U12	U13	U23
Cu1	0.0435 (3)	0.0421 (2)	0.0487 (3)	0.0027 (2)	−0.0027 (2)	−0.0051 (3)
Cl1	0.0885 (8)	0.0468 (6)	0.0891 (9)	0.0160 (6)	0.0088 (7)	−0.0087 (6)
Cl2	0.0949 (9)	0.0575 (6)	0.0622 (8)	0.0006 (6)	−0.0049 (6)	0.0104 (6)
Cl3	0.0771 (8)	0.0416 (5)	0.1354 (12)	0.0083 (5)	0.0144 (8)	−0.0066 (7)
Cl4	0.0742 (8)	0.0955 (7)	0.0439 (7)	0.0157 (6)	0.0002 (6)	−0.0041 (6)
N1	0.0402 (19)	0.0404 (17)	0.041 (2)	0.0038 (14)	−0.0034 (15)	−0.0013 (15)
N2	0.077 (3)	0.082 (3)	0.088 (3)	0.029 (2)	−0.037 (3)	−0.017 (2)
N3	0.0379 (19)	0.0411 (16)	0.042 (2)	0.0045 (14)	−0.0024 (15)	−0.0052 (15)
N4	0.047 (2)	0.067 (2)	0.060 (3)	0.0051 (18)	0.0065 (19)	−0.003 (2)
O1	0.0427 (15)	0.0416 (13)	0.0644 (19)	0.0052 (12)	−0.0101 (13)	−0.0088 (13)
O2	0.0440 (15)	0.0368 (13)	0.0616 (19)	0.0004 (12)	0.0039 (13)	−0.0083 (13)
C1	0.042 (2)	0.047 (2)	0.041 (3)	−0.0048 (19)	−0.0006 (19)	0.0013 (19)
C2	0.042 (2)	0.040 (2)	0.038 (2)	0.0023 (18)	0.0029 (19)	−0.0009 (19)
C3	0.038 (2)	0.044 (2)	0.035 (2)	0.0022 (18)	0.0044 (18)	0.0038 (19)
C4	0.041 (2)	0.056 (2)	0.051 (3)	0.006 (2)	−0.0053 (19)	0.002 (2)
C5	0.052 (3)	0.050 (2)	0.052 (3)	0.017 (2)	0.006 (2)	0.007 (2)
C6	0.062 (3)	0.040 (2)	0.050 (3)	0.014 (2)	0.008 (2)	0.000 (2)
C7	0.058 (3)	0.045 (2)	0.041 (3)	0.000 (2)	0.002 (2)	0.0018 (19)
C8	0.058 (3)	0.057 (3)	0.053 (3)	0.021 (2)	−0.010 (2)	−0.012 (2)
C9	0.044 (3)	0.052 (2)	0.042 (3)	0.010 (2)	−0.006 (2)	−0.011 (2)
C10	0.047 (3)	0.074 (3)	0.069 (3)	0.004 (2)	−0.003 (2)	−0.018 (2)
C11	0.047 (3)	0.107 (4)	0.094 (4)	0.001 (3)	−0.004 (3)	−0.031 (3)
C12	0.060 (4)	0.120 (5)	0.109 (5)	0.040 (4)	−0.035 (3)	−0.038 (4)
C13	0.044 (2)	0.045 (2)	0.041 (3)	−0.0035 (19)	0.0015 (19)	0.0000 (19)
C14	0.038 (2)	0.041 (2)	0.040 (2)	0.0049 (18)	0.0003 (18)	−0.0015 (18)
C15	0.040 (2)	0.048 (2)	0.038 (2)	0.0036 (19)	−0.0011 (18)	−0.0047 (19)
C16	0.041 (2)	0.048 (2)	0.067 (3)	−0.0001 (19)	0.002 (2)	−0.001 (2)
C17	0.046 (3)	0.053 (2)	0.074 (3)	0.006 (2)	−0.001 (2)	−0.004 (2)
C18	0.050 (3)	0.035 (2)	0.074 (3)	0.008 (2)	0.003 (2)	−0.006 (2)
C19	0.049 (2)	0.042 (2)	0.056 (3)	−0.0046 (19)	−0.001 (2)	0.003 (2)
C20	0.050 (3)	0.043 (2)	0.043 (3)	0.0017 (19)	0.001 (2)	−0.0012 (19)
C21	0.042 (2)	0.036 (2)	0.043 (3)	−0.0001 (18)	−0.001 (2)	−0.0007 (19)
C22	0.053 (3)	0.056 (2)	0.048 (3)	0.000 (2)	−0.002 (2)	0.000 (2)
C23	0.050 (3)	0.061 (2)	0.063 (3)	−0.003 (2)	−0.014 (2)	0.007 (2)
C24	0.044 (3)	0.057 (3)	0.077 (4)	−0.002 (2)	0.004 (3)	0.005 (3)

Cu1—O1	1.882 (2)	C6—C7	1.361 (4)
Cu1—O2	1.892 (2)	C7—H7	0.9300
Cu1—N1	1.972 (3)	C8—C9	1.394 (5)
Cu1—N3	1.987 (3)	C9—C10	1.379 (4)
Cl1—C6	1.751 (3)	C10—C11	1.391 (5)
Cl2—C8	1.727 (4)	C10—H10	0.9300
Cl3—C18	1.747 (3)	C11—C12	1.368 (6)
Cl4—C20	1.731 (4)	C11—H11	0.9300
N1—C1	1.303 (3)	C12—H12	0.9300
N1—C9	1.424 (4)	C13—C14	1.438 (4)
N2—C8	1.309 (4)	C13—H13	0.9300
N2—C12	1.336 (5)	C14—C19	1.409 (4)
N3—C13	1.292 (3)	C14—C15	1.414 (4)
N3—C21	1.422 (4)	C15—C16	1.413 (4)
N4—C20	1.307 (4)	C16—C17	1.365 (4)
N4—C24	1.324 (5)	C16—H16	0.9300
O1—C3	1.303 (3)	C17—C18	1.385 (4)
O2—C15	1.298 (3)	C17—H17	0.9300
C1—C2	1.432 (4)	C18—C19	1.369 (4)
C1—H1	0.9300	C19—H19	0.9300
C2—C3	1.413 (4)	C20—C21	1.388 (4)
C2—C7	1.423 (4)	C21—C22	1.365 (5)
C3—C4	1.411 (4)	C22—C23	1.379 (4)
C4—C5	1.362 (4)	C22—H22	0.9300
C4—H4	0.9300	C23—C24	1.376 (5)
C5—C6	1.374 (5)	C23—H23	0.9300
C5—H5	0.9300	C24—H24	0.9300
O1—Cu1—O2	159.31 (10)	C9—C10—H10	120.8
O1—Cu1—N1	93.20 (11)	C11—C10—H10	120.8
O2—Cu1—N1	90.63 (10)	C12—C11—C10	117.6 (5)
O1—Cu1—N3	90.50 (10)	C12—C11—H11	121.2
O2—Cu1—N3	92.70 (10)	C10—C11—H11	121.2
N1—Cu1—N3	160.32 (11)	N2—C12—C11	125.8 (5)
C1—N1—C9	116.2 (3)	N2—C12—H12	117.1
C1—N1—Cu1	124.6 (3)	C11—C12—H12	117.1
C9—N1—Cu1	119.1 (2)	N3—C13—C14	126.5 (3)
C8—N2—C12	115.0 (4)	N3—C13—H13	116.7
C13—N3—C21	116.8 (3)	C14—C13—H13	116.7
C13—N3—Cu1	123.4 (2)	C19—C14—C15	120.3 (3)
C21—N3—Cu1	119.8 (2)	C19—C14—C13	117.0 (3)
C20—N4—C24	116.7 (3)	C15—C14—C13	122.5 (3)
C3—O1—Cu1	129.0 (2)	O2—C15—C16	118.9 (3)
C15—O2—Cu1	127.7 (2)	O2—C15—C14	124.2 (3)
N1—C1—C2	125.1 (3)	C16—C15—C14	116.9 (3)
N1—C1—H1	117.5	C17—C16—C15	122.3 (3)
C2—C1—H1	117.5	C17—C16—H16	118.9
C3—C2—C7	119.1 (3)	C15—C16—H16	118.9
C3—C2—C1	123.9 (3)	C16—C17—C18	119.8 (3)
C7—C2—C1	116.6 (3)	C16—C17—H17	120.1
O1—C3—C4	119.2 (3)	C18—C17—H17	120.1
O1—C3—C2	123.6 (3)	C19—C18—C17	120.8 (3)
C4—C3—C2	117.3 (3)	C19—C18—Cl3	119.0 (3)
C5—C4—C3	122.3 (4)	C17—C18—Cl3	120.2 (3)
C5—C4—H4	118.8	C18—C19—C14	119.9 (3)
C3—C4—H4	118.8	C18—C19—H19	120.0
C4—C5—C6	119.9 (3)	C14—C19—H19	120.0
C4—C5—H5	120.0	N4—C20—C21	125.2 (4)
C6—C5—H5	120.0	N4—C20—Cl4	116.0 (3)
C7—C6—C5	120.9 (3)	C21—C20—Cl4	118.8 (3)
C7—C6—Cl1	118.8 (3)	C22—C21—C20	116.6 (3)
C5—C6—Cl1	120.3 (3)	C22—C21—N3	121.7 (3)
C6—C7—C2	120.5 (3)	C20—C21—N3	121.4 (4)
C6—C7—H7	119.8	C21—C22—C23	119.9 (4)
C2—C7—H7	119.8	C21—C22—H22	120.1
N2—C8—C9	125.4 (4)	C23—C22—H22	120.1
N2—C8—Cl2	114.8 (4)	C24—C23—C22	117.9 (4)
C9—C8—Cl2	119.8 (3)	C24—C23—H23	121.0
C10—C9—C8	117.8 (4)	C22—C23—H23	121.0
C10—C9—N1	122.8 (4)	N4—C24—C23	123.6 (4)
C8—C9—N1	119.4 (3)	N4—C24—H24	118.2
C9—C10—C11	118.4 (4)	C23—C24—H24	118.2
O1—Cu1—N1—C1	8.0 (3)	C1—N1—C9—C10	53.3 (5)
O2—Cu1—N1—C1	−151.7 (3)	Cu1—N1—C9—C10	−123.5 (3)
N3—Cu1—N1—C1	108.5 (4)	C1—N1—C9—C8	−128.7 (3)
O1—Cu1—N1—C9	−175.6 (3)	Cu1—N1—C9—C8	54.5 (4)
O2—Cu1—N1—C9	24.8 (3)	C8—C9—C10—C11	1.3 (5)
N3—Cu1—N1—C9	−75.0 (4)	N1—C9—C10—C11	179.3 (3)
O1—Cu1—N3—C13	−173.1 (3)	C9—C10—C11—C12	−1.9 (6)
O2—Cu1—N3—C13	−13.5 (3)	C8—N2—C12—C11	−0.6 (7)
N1—Cu1—N3—C13	85.9 (4)	C10—C11—C12—N2	1.7 (8)
O1—Cu1—N3—C21	7.2 (3)	C21—N3—C13—C14	−176.9 (3)
O2—Cu1—N3—C21	166.8 (3)	Cu1—N3—C13—C14	3.4 (5)
N1—Cu1—N3—C21	−93.7 (4)	N3—C13—C14—C19	−175.7 (4)
O2—Cu1—O1—C3	96.9 (4)	N3—C13—C14—C15	8.2 (6)
N1—Cu1—O1—C3	−3.4 (3)	Cu1—O2—C15—C16	167.6 (2)
N3—Cu1—O1—C3	−164.1 (3)	Cu1—O2—C15—C14	−13.5 (5)
O1—Cu1—O2—C15	117.5 (3)	C19—C14—C15—O2	−179.2 (3)
N1—Cu1—O2—C15	−141.7 (3)	C13—C14—C15—O2	−3.3 (6)
N3—Cu1—O2—C15	18.9 (3)	C19—C14—C15—C16	−0.3 (5)
C9—N1—C1—C2	176.8 (3)	C13—C14—C15—C16	175.6 (3)
Cu1—N1—C1—C2	−6.7 (5)	O2—C15—C16—C17	179.5 (3)
N1—C1—C2—C3	−1.7 (5)	C14—C15—C16—C17	0.5 (6)
N1—C1—C2—C7	−175.0 (3)	C15—C16—C17—C18	0.0 (6)
Cu1—O1—C3—C4	176.4 (2)	C16—C17—C18—C19	−0.7 (6)
Cu1—O1—C3—C2	−2.9 (5)	C16—C17—C18—Cl3	−179.8 (3)
C7—C2—C3—O1	−180.0 (3)	C17—C18—C19—C14	0.9 (6)
C1—C2—C3—O1	6.9 (5)	Cl3—C18—C19—C14	180.0 (3)
C7—C2—C3—C4	0.8 (5)	C15—C14—C19—C18	−0.3 (6)
C1—C2—C3—C4	−172.4 (3)	C13—C14—C19—C18	−176.5 (3)
O1—C3—C4—C5	−178.5 (3)	C24—N4—C20—C21	−1.3 (5)
C2—C3—C4—C5	0.8 (5)	C24—N4—C20—Cl4	178.3 (3)
C3—C4—C5—C6	−1.2 (6)	N4—C20—C21—C22	1.5 (5)
C4—C5—C6—C7	−0.1 (6)	Cl4—C20—C21—C22	−178.0 (3)
C4—C5—C6—Cl1	179.1 (3)	N4—C20—C21—N3	−173.4 (3)
C5—C6—C7—C2	1.7 (5)	Cl4—C20—C21—N3	7.1 (4)
Cl1—C6—C7—C2	−177.5 (3)	C13—N3—C21—C22	75.5 (4)
C3—C2—C7—C6	−2.0 (5)	Cu1—N3—C21—C22	−104.8 (3)
C1—C2—C7—C6	171.6 (3)	C13—N3—C21—C20	−109.9 (4)
C12—N2—C8—C9	−0.1 (6)	Cu1—N3—C21—C20	69.8 (4)
C12—N2—C8—Cl2	178.5 (3)	C20—C21—C22—C23	−0.1 (5)
N2—C8—C9—C10	−0.3 (6)	N3—C21—C22—C23	174.8 (3)
Cl2—C8—C9—C10	−178.9 (3)	C21—C22—C23—C24	−1.3 (5)
N2—C8—C9—N1	−178.4 (3)	C20—N4—C24—C23	−0.4 (6)
Cl2—C8—C9—N1	3.0 (4)	C22—C23—C24—N4	1.7 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···Cg1i	0.93	2.89	3.753 (3)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22⋯Cg1i	0.93	2.89	3.753 (3)	155

Symmetry code: (i) . Cg1 is the centroid of the C2–C7 ring.