Di-[mu]-acetato-bis­{[2,4-dichloro-6-(2-pyridylmethyl­imino­meth­yl)­phenol­ato]zinc(II)} and di-[mu]-thio­cyanato-bis­{[2,4-dichloro-6-(2-pyridylmethyl­imino­meth­yl)phenolato]copper(II)}

The two title complexes, [Zn₂(C₁₃H₉Cl₂N₂O)₂(C₂H₃O₂)₂], (I), and [Cu₂(C₁₃H₉Cl₂N₂O)₂(NCS)₂], (II), are dinuclear Schiff base compounds. Both mol­ecules are located on crystallographic centres of inversion. In (I), the Zn^II atom is five-coordinated in a trigonal-bipyramidal coordination, with one imine N atom of one Schiff base and two acetate O atoms defining the basal plane, and one O atom and one pyridine N atom of the Schiff base occupying the axial positions, while in (II), the Cu^II atom is five-coordinated in a square-pyramidal coordination, with one O and two N atoms of one Schiff base and one terminal N atom of a bridging thio­cyanate ligand defining the basal plane, and one terminal S atom of another bridging thio­cyanate ligand occupying the apical position. The different bridging ligands lead to the different coordinations of the complexes.

S1. Comment

Metal-organic complexes containing bridging ligands are of current interest because of their interesting molecular topologies and crystal-packing motifs, as well as the fact that they may be designed with specific functionalities (Mukherjee et al., 2001; Meyer & Pritzkow, 2001; Goher et al., 2002). The prime strategy for designing these polynuclear materials is to use suitable bridging ligands (Koner et al., 2003). Owing to the coordination modes of the acetate and thiocyanate anions, these ligands may act as bridging groups. A major obstacle to a more comprehensive study of such acetate- or thiocyanate-coordinated polynuclear complexes is the lack of rational synthetic procedures, since with the present state of knowledge it is hardly possible to determine which coordination mode will be adopted by the acetate anion or thiocyanate anion and whether the sought-after alternating structure will finally be formed (Bhaduri et al., 2003; Romero et al., 2002; Tercero et al., 2002; Ribas et al., 1999).

Our work is aimed at obtaining polynuclear complexes. On the basis of the above considerations, we used the rigid tridentate Schiff base ligand, 2,4-dichloro-6-(pyridin-2-ylmethyliminomethyl)phenol (DPMP), as the first ligand. The reason we use this ligand is that the rigid DPMP molecule can adopt an almost fixed coordination mode through the three N and O donor atoms (You, 2005a). The second ligand, viz. acetate or thiocyanate, is a well known bridging group. It readily bridges different metal ions through the donor atoms, forming polynuclear complexes. We report here two new dinuclear zinc(II) and copper(II) complexes, [Zn₂(C₁₃H₉Cl₂N₂O)₂(C₂H₃O₂)₂], (I), and [Cu₂(C₁₃H₉Cl₂N₂O)₂(NCS)₂], (II). The different bridging ligands lead to the different coordination modes of the metal ions.

Complexes (I) and (II) are dinuclear Schiff base compounds (Figs. 1 and 2). In (I), the Zn^II atom is five-coordinated in a trigonal-bipyramidal coordination, with one imine N atom of one Schiff base and two acetate O atoms defining the basal plane, and one O and one pyridine N atom of the Schiff base occupying the axial positions. In (II), the Cu^II atom is five-coordinated in a square-pyramidal coordination, with one O and two N atoms of one Schiff base and one terminal N atom of a bridging thiocyanate ligand defining the basal plane, and one terminal S atom of another bridging thiocyanate ligand occupying the apical position. The different coordinations in the two complexes are caused by the different bridging ligands between the metal ions. In (I), atoms O2 and O3 of the acetate group have almost the same coordination patterns, which respectively coordinate to the Zn1 and Zn1ⁱ atoms [symmetry code: (i) 2 − x, −y, −z]. The C14—O2 bond is longer by 0.010 (4) Å than the C14—O3 bond (Table 1), and the Zn1—O2 bond is shorter by 0.008 (2) Å than the of Zn1ⁱ—O3 bond, indicating that atom O3 adopts the ketonic coordination, while atom O2 adopt the enolic coordination. In (II), atoms N3 and S1 of the thiocyanate group have different coordination patterns. The N atom of the thiocyanate group preferably coordinates to the metal ions through linear coordination modes, while the S atom of the thiocyanate group preferably adopts the orthogonal coordination modes (You & Zhu, 2005; You, 2005b). The thiocyanate group in (II) is nearly linear and shows bent coordinations with the metal atoms [the angles N3—C14—S1, Cu1—N3—C14 and C14—S1—Cu1ⁱⁱ are 179.1 (4), 159.3 (3) and 84.4 (3)°, respectively; symmetry code: (ii) 1 − x, 2 − y, −z].

Each zinc(II) moiety of complex (I), and each copper(II) moiety of the complex (II), is nearly coplanar, with the mean deviations from the DPMP plane of 0.043 (3) Å in (I) and 0.021 (3) Å in (II). These planar configurations can decrease the steric repulsion of the two near planar moieties. The N1—Zn1—N2 bond angle [77.30 (10)°] in (I) and the N1—Cu1—N2 bond angle [82.47 (11)°] in (II) are much smaller than 90°, as a result, respectively, of the strain created by the five-membered chelate rings Zn1/N2/C9/C8/N1 in (I) and Cu1/N2/C9/C8/N1 in (II). The bond lengths subtended at the metal atoms in the complexes are within normal ranges and, as expected, the bonds involving the pyridine N atoms are longer than those involving the imine N atoms.

The distance between atoms Zn1 and Zn1ⁱ [4.117 (2) Å] is much shorter than that between Cu1 and Cu1ⁱⁱ [5.099 (2) Å], as a result of the different size of the bridging ligands. The distance [2.220 (4) Å] between atoms O2 and O3 of the acetate group in (I) is much shorter than that [2.784 (4) Å] between atoms S1 and N3 of the thiocyanate group in (II). The metal–metal distance in (I) is shorter than that in (II), resulting in more steric repulsion of the two near planar moieties, and further in the N2—Zn1—O1 bond angle [164.49 (10)°] in (I) deviating from 180° much more than the corresponding value [N2—Cu1—O1 = 175.35 (11)°] observed in (II).

In conclusion, the different bridging ligands can result in the different coordinations of the complexes.

S2. Experimental

For the preparation of complex (I), 3,5-dichlorosalicylaldehyde (0.1 mmol, 19.1 mg) and 2-aminomethylpyridine (0.1 mmol, 10.8 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 10 min to give a clear yellow solution, to which was added an MeOH solution (5 ml) of Zn(CH₃COO)₂·4H₂O (0.1 mmol, 25.6 mg) with stirring. The mixture was stirred for another 10 min at room temperature. After keeping the filtrate in air for 5 d, colourless block-shaped crystals were formed. Complex (II) was prepared by a procedure similar to that described for (I), with Zn(CH₃COO)₂·4H₂O replaced by Cu(CH₃COO)₂·H₂O (0.1 mmol, 19.9 mg) and NH₄NCS (0.1 mmol, 7.6 mg). Blue needle-shaped crystals of (II) were obtained after evaporating the solvents from the filtrate in air for 7 d.

S3. Refinement

All H atoms in (I) and (II) were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C).

Computing details

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labeled with the suffix A are at the symmetry position (2 − x, −y, −z).
	Fig. 2. The structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labeled with the suffix A are at the symmetry position (1 − x, 2 − y, −z).

(I) Di-µ-acetato-bis{[2,4-dichloro-6-(2- pyridylmethyliminomethyl)phenolato]zinc(II)}

Crystal data

[Zn2(C13H9Cl2N2O)2(C2H3O2)2]	Z = 1
Mr = 809.07	F(000) = 408
Triclinic, P1	Dx = 1.639 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.540 (1) Å	Cell parameters from 3662 reflections
b = 9.388 (1) Å	θ = 2.3–27.6°
c = 12.228 (1) Å	µ = 1.84 mm^−1
α = 76.208 (1)°	T = 298 K
β = 85.222 (1)°	Block, colourless
γ = 77.320 (1)°	0.25 × 0.22 × 0.11 mm
V = 819.67 (15) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3560 independent reflections
Radiation source: fine-focus sealed tube	2835 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scan	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.657, Tmax = 0.823	k = −11→11
7858 measured reflections	l = −15→15

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0612P)^2 + 0.463P] where P = (Fo^2 + 2Fc^2)/3
3560 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 1.03 e Å^−3
0 restraints	Δρmin = −0.30 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
Zn1	0.89936 (5)	0.21795 (4)	0.01275 (3)	0.03055 (13)
Cl1	0.7445 (2)	0.31616 (13)	−0.38103 (9)	0.0901 (5)
Cl2	0.40017 (15)	0.88217 (11)	−0.38379 (9)	0.0562 (3)
O1	0.8098 (4)	0.2969 (3)	−0.1452 (2)	0.0485 (6)
O2	0.7400 (4)	0.0713 (3)	0.0699 (2)	0.0534 (7)
O3	0.8439 (3)	−0.1577 (3)	0.0414 (3)	0.0564 (7)
N1	0.7998 (3)	0.4340 (3)	0.0404 (2)	0.0294 (5)
N2	0.9862 (4)	0.1970 (3)	0.1811 (2)	0.0331 (6)
C1	0.7210 (5)	0.4265 (3)	−0.1937 (3)	0.0332 (7)
C2	0.6722 (6)	0.4585 (4)	−0.3087 (3)	0.0439 (8)
C3	0.5769 (5)	0.5933 (4)	−0.3662 (3)	0.0454 (9)
H3	0.5507	0.6072	−0.4415	0.054*
C4	0.5197 (5)	0.7096 (4)	−0.3103 (3)	0.0374 (7)
C5	0.5634 (4)	0.6896 (4)	−0.2007 (3)	0.0346 (7)
H5	0.5268	0.7684	−0.1646	0.042*
C6	0.6628 (4)	0.5516 (3)	−0.1416 (3)	0.0290 (6)
C7	0.7075 (4)	0.5464 (3)	−0.0283 (3)	0.0302 (6)
H7	0.6652	0.6334	−0.0020	0.036*
C8	0.8302 (5)	0.4586 (3)	0.1503 (3)	0.0321 (7)
H8A	0.7138	0.4896	0.1870	0.039*
H8B	0.8963	0.5388	0.1398	0.039*
C9	0.9360 (4)	0.3192 (3)	0.2247 (3)	0.0315 (6)
C10	0.9799 (5)	0.3189 (4)	0.3324 (3)	0.0419 (8)
H10	0.9438	0.4047	0.3608	0.050*
C11	1.0786 (5)	0.1880 (5)	0.3973 (3)	0.0494 (9)
H11	1.1096	0.1849	0.4700	0.059*
C12	1.1294 (5)	0.0650 (4)	0.3537 (3)	0.0498 (9)
H12	1.1966	−0.0231	0.3960	0.060*
C13	1.0812 (5)	0.0708 (4)	0.2462 (3)	0.0445 (8)
H13	1.1151	−0.0150	0.2176	0.053*
C14	0.7367 (4)	−0.0637 (3)	0.0831 (3)	0.0327 (7)
C15	0.5810 (6)	−0.1170 (5)	0.1548 (4)	0.0618 (12)
H15A	0.5024	−0.1436	0.1086	0.093*
H15B	0.5137	−0.0384	0.1888	0.093*
H15C	0.6279	−0.2030	0.2127	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0387 (2)	0.02216 (19)	0.0315 (2)	−0.00701 (14)	0.00378 (14)	−0.00847 (14)
Cl1	0.1688 (15)	0.0531 (7)	0.0447 (6)	0.0119 (8)	−0.0228 (7)	−0.0295 (5)
Cl2	0.0673 (7)	0.0402 (5)	0.0524 (6)	−0.0061 (4)	−0.0176 (5)	0.0073 (4)
O1	0.0758 (18)	0.0290 (12)	0.0378 (13)	0.0031 (12)	−0.0079 (12)	−0.0124 (10)
O2	0.0587 (17)	0.0383 (14)	0.0695 (18)	−0.0244 (12)	0.0115 (14)	−0.0157 (13)
O3	0.0414 (15)	0.0556 (17)	0.0771 (19)	−0.0092 (12)	0.0198 (13)	−0.0327 (15)
N1	0.0359 (14)	0.0259 (12)	0.0277 (13)	−0.0082 (10)	0.0039 (10)	−0.0086 (10)
N2	0.0386 (15)	0.0278 (13)	0.0333 (14)	−0.0073 (11)	−0.0028 (11)	−0.0069 (11)
C1	0.0414 (18)	0.0295 (16)	0.0321 (16)	−0.0108 (13)	0.0024 (13)	−0.0114 (13)
C2	0.065 (2)	0.0319 (17)	0.0363 (18)	−0.0093 (16)	0.0000 (16)	−0.0123 (14)
C3	0.061 (2)	0.047 (2)	0.0319 (17)	−0.0183 (18)	−0.0093 (16)	−0.0063 (15)
C4	0.0414 (19)	0.0296 (16)	0.0379 (17)	−0.0089 (13)	−0.0016 (14)	0.0004 (13)
C5	0.0391 (18)	0.0288 (15)	0.0371 (17)	−0.0075 (13)	0.0001 (13)	−0.0096 (13)
C6	0.0327 (16)	0.0248 (14)	0.0314 (15)	−0.0095 (12)	0.0023 (12)	−0.0083 (12)
C7	0.0348 (17)	0.0237 (14)	0.0337 (16)	−0.0073 (12)	0.0037 (13)	−0.0104 (12)
C8	0.0448 (18)	0.0262 (15)	0.0282 (15)	−0.0099 (13)	0.0021 (13)	−0.0102 (12)
C9	0.0339 (16)	0.0317 (16)	0.0318 (16)	−0.0130 (13)	0.0024 (12)	−0.0078 (13)
C10	0.053 (2)	0.0411 (19)	0.0343 (18)	−0.0117 (16)	−0.0014 (15)	−0.0125 (15)
C11	0.056 (2)	0.055 (2)	0.0351 (19)	−0.0123 (18)	−0.0128 (16)	−0.0025 (17)
C12	0.055 (2)	0.042 (2)	0.046 (2)	−0.0073 (17)	−0.0144 (17)	0.0051 (17)
C13	0.050 (2)	0.0316 (17)	0.050 (2)	−0.0034 (15)	−0.0064 (16)	−0.0089 (16)
C14	0.0351 (17)	0.0330 (16)	0.0332 (16)	−0.0098 (13)	0.0015 (13)	−0.0126 (13)
C15	0.066 (3)	0.051 (2)	0.079 (3)	−0.028 (2)	0.034 (2)	−0.032 (2)

Geometric parameters (Å, º)

Zn1—O2	1.989 (2)	C4—C5	1.365 (5)
Zn1—O3^i	1.997 (2)	C5—C6	1.407 (4)
Zn1—O1	2.013 (2)	C5—H5	0.9300
Zn1—N1	2.099 (2)	C6—C7	1.440 (4)
Zn1—N2	2.164 (3)	C7—H7	0.9300
Cl1—C2	1.740 (4)	C8—C9	1.508 (4)
Cl2—C4	1.745 (3)	C8—H8A	0.9700
O1—C1	1.282 (4)	C8—H8B	0.9700
O2—C14	1.244 (4)	C9—C10	1.384 (5)
O3—C14	1.234 (4)	C10—C11	1.387 (5)
O3—Zn1^i	1.997 (2)	C10—H10	0.9300
N1—C7	1.287 (4)	C11—C12	1.353 (6)
N1—C8	1.460 (4)	C11—H11	0.9300
N2—C9	1.346 (4)	C12—C13	1.378 (5)
N2—C13	1.350 (4)	C12—H12	0.9300
C1—C2	1.428 (5)	C13—H13	0.9300
C1—C6	1.436 (4)	C14—C15	1.509 (5)
C2—C3	1.369 (5)	C15—H15A	0.9600
C3—C4	1.395 (5)	C15—H15B	0.9600
C3—H3	0.9300	C15—H15C	0.9600
O2—Zn1—O3^i	122.65 (11)	C5—C6—C7	115.9 (3)
O2—Zn1—O1	99.18 (12)	C1—C6—C7	122.7 (3)
O3^i—Zn1—O1	92.55 (12)	N1—C7—C6	126.8 (3)
O2—Zn1—N1	115.73 (10)	N1—C7—H7	116.6
O3^i—Zn1—N1	120.68 (10)	C6—C7—H7	116.6
O1—Zn1—N1	87.82 (10)	N1—C8—C9	111.8 (2)
O2—Zn1—N2	91.31 (11)	N1—C8—H8A	109.3
O3^i—Zn1—N2	91.34 (12)	C9—C8—H8A	109.3
O1—Zn1—N2	164.49 (10)	N1—C8—H8B	109.3
N1—Zn1—N2	77.30 (10)	C9—C8—H8B	109.3
C1—O1—Zn1	130.7 (2)	H8A—C8—H8B	107.9
C14—O2—Zn1	141.9 (2)	N2—C9—C10	122.1 (3)
C14—O3—Zn1^i	144.5 (2)	N2—C9—C8	116.9 (3)
C7—N1—C8	116.2 (3)	C10—C9—C8	121.0 (3)
C7—N1—Zn1	126.5 (2)	C9—C10—C11	118.7 (3)
C8—N1—Zn1	117.29 (19)	C9—C10—H10	120.6
C9—N2—C13	118.0 (3)	C11—C10—H10	120.6
C9—N2—Zn1	116.7 (2)	C12—C11—C10	119.3 (3)
C13—N2—Zn1	125.3 (2)	C12—C11—H11	120.3
O1—C1—C2	121.2 (3)	C10—C11—H11	120.3
O1—C1—C6	125.2 (3)	C11—C12—C13	119.7 (3)
C2—C1—C6	113.6 (3)	C11—C12—H12	120.1
C3—C2—C1	124.8 (3)	C13—C12—H12	120.1
C3—C2—Cl1	118.1 (3)	N2—C13—C12	122.1 (3)
C1—C2—Cl1	117.1 (3)	N2—C13—H13	118.9
C2—C3—C4	119.0 (3)	C12—C13—H13	118.9
C2—C3—H3	120.5	O3—C14—O2	127.2 (3)
C4—C3—H3	120.5	O3—C14—C15	116.5 (3)
C5—C4—C3	120.1 (3)	O2—C14—C15	116.3 (3)
C5—C4—Cl2	120.8 (3)	C14—C15—H15A	109.5
C3—C4—Cl2	119.1 (3)	C14—C15—H15B	109.5
C4—C5—C6	121.1 (3)	H15A—C15—H15B	109.5
C4—C5—H5	119.5	C14—C15—H15C	109.5
C6—C5—H5	119.5	H15A—C15—H15C	109.5
C5—C6—C1	121.4 (3)	H15B—C15—H15C	109.5
O2—Zn1—O1—C1	112.2 (3)	C2—C3—C4—Cl2	179.4 (3)
O3^i—Zn1—O1—C1	−124.1 (3)	C3—C4—C5—C6	−1.3 (5)
N1—Zn1—O1—C1	−3.5 (3)	Cl2—C4—C5—C6	−178.8 (2)
N2—Zn1—O1—C1	−19.8 (6)	C4—C5—C6—C1	−0.4 (5)
O3^i—Zn1—O2—C14	−4.2 (5)	C4—C5—C6—C7	177.3 (3)
O1—Zn1—O2—C14	94.8 (4)	O1—C1—C6—C5	−179.1 (3)
N1—Zn1—O2—C14	−173.2 (4)	C2—C1—C6—C5	1.5 (4)
N2—Zn1—O2—C14	−96.7 (4)	O1—C1—C6—C7	3.4 (5)
O2—Zn1—N1—C7	−93.6 (3)	C2—C1—C6—C7	−176.1 (3)
O3^i—Zn1—N1—C7	97.2 (3)	C8—N1—C7—C6	178.6 (3)
O1—Zn1—N1—C7	5.6 (3)	Zn1—N1—C7—C6	−4.5 (4)
N2—Zn1—N1—C7	−178.8 (3)	C5—C6—C7—N1	−178.5 (3)
O2—Zn1—N1—C8	83.3 (2)	C1—C6—C7—N1	−0.9 (5)
O3^i—Zn1—N1—C8	−85.9 (2)	C7—N1—C8—C9	178.8 (3)
O1—Zn1—N1—C8	−177.5 (2)	Zn1—N1—C8—C9	1.6 (3)
N2—Zn1—N1—C8	−1.9 (2)	C13—N2—C9—C10	0.5 (5)
O2—Zn1—N2—C9	−114.0 (2)	Zn1—N2—C9—C10	178.6 (2)
O3^i—Zn1—N2—C9	123.3 (2)	C13—N2—C9—C8	180.0 (3)
O1—Zn1—N2—C9	18.8 (5)	Zn1—N2—C9—C8	−1.9 (4)
N1—Zn1—N2—C9	2.1 (2)	N1—C8—C9—N2	0.3 (4)
O2—Zn1—N2—C13	64.0 (3)	N1—C8—C9—C10	179.8 (3)
O3^i—Zn1—N2—C13	−58.7 (3)	N2—C9—C10—C11	0.0 (5)
O1—Zn1—N2—C13	−163.3 (4)	C8—C9—C10—C11	−179.5 (3)
N1—Zn1—N2—C13	−179.9 (3)	C9—C10—C11—C12	0.1 (6)
Zn1—O1—C1—C2	179.5 (3)	C10—C11—C12—C13	−0.6 (6)
Zn1—O1—C1—C6	0.0 (5)	C9—N2—C13—C12	−1.0 (5)
O1—C1—C2—C3	179.6 (4)	Zn1—N2—C13—C12	−178.9 (3)
C6—C1—C2—C3	−0.9 (5)	C11—C12—C13—N2	1.1 (6)
O1—C1—C2—Cl1	−1.9 (5)	Zn1^i—O3—C14—O2	30.6 (7)
C6—C1—C2—Cl1	177.5 (2)	Zn1^i—O3—C14—C15	−151.5 (4)
C1—C2—C3—C4	−0.7 (6)	Zn1—O2—C14—O3	−13.7 (7)
Cl1—C2—C3—C4	−179.2 (3)	Zn1—O2—C14—C15	168.4 (3)
C2—C3—C4—C5	1.9 (5)

Symmetry code: (i) −x+2, −y, −z.

(II) di-µ-thiocyanato-bis{[2,4-dichloro-6-(2- pyridylmethyliminomethyl)phenolato]copper(II)}

Crystal data

[Zn2(C13H9Cl2N2O)2(NCS)2]	F(000) = 804
Mr = 803.52	Dx = 1.732 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1836 reflections
a = 8.718 (1) Å	θ = 2.4–22.5°
b = 13.387 (2) Å	µ = 1.90 mm^−1
c = 13.564 (2) Å	T = 298 K
β = 103.305 (2)°	Needle, blue
V = 1540.5 (4) Å^3	0.15 × 0.07 × 0.04 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	3505 independent reflections
Radiation source: fine-focus sealed tube	2317 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
ω scan	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.763, Tmax = 0.928	k = −17→16
13079 measured reflections	l = −17→17

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) = 0.105	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.041P)^2] where P = (Fo^2 + 2Fc^2)/3
3505 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.30 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	0.60055 (5)	0.97449 (3)	0.19018 (3)	0.04162 (15)
Cl1	1.09808 (11)	1.13643 (8)	0.21840 (8)	0.0610 (3)
Cl2	1.35906 (12)	0.90239 (10)	0.53537 (10)	0.0817 (4)
S1	0.33475 (11)	1.18975 (8)	−0.05963 (7)	0.0521 (3)
O1	0.8097 (3)	1.02780 (17)	0.22243 (18)	0.0475 (6)
N1	0.6465 (3)	0.8785 (2)	0.2984 (2)	0.0410 (7)
N2	0.3818 (3)	0.9130 (2)	0.1674 (2)	0.0419 (7)
N3	0.5301 (4)	1.0824 (2)	0.0956 (2)	0.0479 (8)
C1	0.9219 (4)	0.9202 (3)	0.3628 (3)	0.0406 (8)
C2	0.9281 (4)	0.9979 (2)	0.2926 (3)	0.0408 (9)
C3	1.0783 (4)	1.0430 (3)	0.3031 (3)	0.0441 (9)
C4	1.2072 (4)	1.0162 (3)	0.3766 (3)	0.0519 (10)
H4	1.3028	1.0490	0.3817	0.062*
C5	1.1946 (4)	0.9401 (3)	0.4432 (3)	0.0507 (10)
C6	1.0551 (4)	0.8924 (3)	0.4363 (3)	0.0492 (10)
H6	1.0481	0.8407	0.4809	0.059*
C7	0.7793 (4)	0.8654 (3)	0.3612 (3)	0.0448 (9)
H7	0.7839	0.8160	0.4100	0.054*
C8	0.5186 (4)	0.8117 (3)	0.3065 (3)	0.0569 (11)
H8A	0.4996	0.8163	0.3741	0.068*
H8B	0.5482	0.7434	0.2959	0.068*
C9	0.3712 (4)	0.8378 (3)	0.2302 (3)	0.0439 (9)
C10	0.2324 (4)	0.7866 (3)	0.2252 (3)	0.0539 (10)
H10	0.2279	0.7352	0.2706	0.065*
C11	0.1027 (4)	0.8118 (3)	0.1535 (3)	0.0592 (11)
H11	0.0080	0.7783	0.1496	0.071*
C12	0.1123 (4)	0.8871 (3)	0.0869 (3)	0.0601 (11)
H12	0.0246	0.9049	0.0367	0.072*
C13	0.2533 (4)	0.9361 (3)	0.0952 (3)	0.0548 (10)
H13	0.2600	0.9868	0.0495	0.066*
C14	0.4499 (4)	1.1274 (3)	0.0310 (3)	0.0435 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0411 (3)	0.0406 (3)	0.0416 (3)	−0.0021 (2)	0.00621 (19)	0.0053 (2)
Cl1	0.0568 (6)	0.0508 (6)	0.0781 (7)	−0.0075 (5)	0.0208 (5)	0.0087 (5)
Cl2	0.0472 (6)	0.1039 (10)	0.0832 (9)	0.0037 (6)	−0.0075 (6)	0.0190 (7)
S1	0.0517 (6)	0.0558 (6)	0.0433 (6)	0.0109 (5)	−0.0005 (4)	0.0001 (5)
O1	0.0421 (14)	0.0454 (15)	0.0521 (16)	−0.0043 (12)	0.0047 (12)	0.0090 (12)
N1	0.0384 (16)	0.0434 (17)	0.0392 (17)	−0.0041 (14)	0.0047 (13)	0.0049 (14)
N2	0.0370 (16)	0.0399 (17)	0.0481 (18)	−0.0004 (13)	0.0085 (14)	0.0001 (15)
N3	0.0524 (19)	0.0384 (18)	0.0503 (19)	0.0007 (15)	0.0067 (16)	0.0030 (15)
C1	0.0373 (19)	0.045 (2)	0.040 (2)	−0.0007 (16)	0.0079 (16)	−0.0021 (17)
C2	0.044 (2)	0.035 (2)	0.045 (2)	−0.0034 (15)	0.0127 (17)	−0.0074 (16)
C3	0.044 (2)	0.038 (2)	0.050 (2)	0.0012 (16)	0.0109 (17)	0.0007 (17)
C4	0.040 (2)	0.055 (2)	0.061 (3)	−0.0050 (18)	0.0120 (19)	−0.011 (2)
C5	0.037 (2)	0.059 (3)	0.052 (2)	0.0053 (18)	0.0019 (18)	−0.001 (2)
C6	0.051 (2)	0.051 (2)	0.043 (2)	0.0073 (19)	0.0072 (18)	0.0026 (18)
C7	0.054 (2)	0.042 (2)	0.040 (2)	−0.0042 (18)	0.0132 (18)	0.0027 (17)
C8	0.049 (2)	0.060 (3)	0.058 (3)	−0.011 (2)	0.004 (2)	0.017 (2)
C9	0.044 (2)	0.046 (2)	0.043 (2)	−0.0026 (17)	0.0127 (17)	0.0007 (18)
C10	0.051 (2)	0.051 (2)	0.060 (3)	−0.0100 (19)	0.014 (2)	0.005 (2)
C11	0.042 (2)	0.064 (3)	0.071 (3)	−0.007 (2)	0.012 (2)	−0.003 (2)
C12	0.040 (2)	0.062 (3)	0.072 (3)	0.002 (2)	−0.001 (2)	0.004 (2)
C13	0.044 (2)	0.053 (2)	0.064 (3)	0.0009 (19)	0.007 (2)	0.013 (2)
C14	0.045 (2)	0.039 (2)	0.047 (2)	−0.0035 (17)	0.0119 (18)	−0.0089 (18)

Geometric parameters (Å, º)

Cu1—O1	1.913 (2)	C3—C4	1.368 (5)
Cu1—N1	1.922 (3)	C4—C5	1.383 (5)
Cu1—N3	1.936 (3)	C4—H4	0.9300
Cu1—N2	2.034 (3)	C5—C6	1.358 (5)
Cu1—S1^i	2.9577 (12)	C6—H6	0.9300
Cl1—C3	1.734 (4)	C7—H7	0.9300
Cl2—C5	1.746 (4)	C8—C9	1.494 (5)
S1—C14	1.627 (4)	C8—H8A	0.9700
O1—C2	1.296 (4)	C8—H8B	0.9700
N1—C7	1.281 (4)	C9—C10	1.379 (5)
N1—C8	1.454 (4)	C10—C11	1.353 (5)
N2—C9	1.336 (4)	C10—H10	0.9300
N2—C13	1.343 (4)	C11—C12	1.369 (5)
N3—C14	1.156 (4)	C11—H11	0.9300
C1—C6	1.396 (5)	C12—C13	1.376 (5)
C1—C2	1.419 (5)	C12—H12	0.9300
C1—C7	1.440 (5)	C13—H13	0.9300
C2—C3	1.418 (4)
O1—Cu1—N1	93.12 (11)	C5—C6—C1	120.5 (4)
O1—Cu1—N3	90.77 (11)	C5—C6—H6	119.7
N1—Cu1—N3	169.58 (12)	C1—C6—H6	119.7
O1—Cu1—N2	175.35 (11)	N1—C7—C1	125.8 (3)
N1—Cu1—N2	82.47 (11)	N1—C7—H7	117.1
N3—Cu1—N2	93.33 (12)	C1—C7—H7	117.1
C2—O1—Cu1	127.5 (2)	N1—C8—C9	110.8 (3)
C7—N1—C8	117.1 (3)	N1—C8—H8A	109.5
C7—N1—Cu1	126.7 (2)	C9—C8—H8A	109.5
C8—N1—Cu1	116.1 (2)	N1—C8—H8B	109.5
C9—N2—C13	118.1 (3)	C9—C8—H8B	109.5
C9—N2—Cu1	114.1 (2)	H8A—C8—H8B	108.1
C13—N2—Cu1	127.8 (3)	N2—C9—C10	122.2 (3)
C14—N3—Cu1	159.3 (3)	N2—C9—C8	116.3 (3)
C6—C1—C2	121.4 (3)	C10—C9—C8	121.5 (3)
C6—C1—C7	116.6 (3)	C11—C10—C9	119.3 (4)
C2—C1—C7	122.0 (3)	C11—C10—H10	120.3
O1—C2—C3	120.2 (3)	C9—C10—H10	120.3
O1—C2—C1	124.9 (3)	C10—C11—C12	119.3 (4)
C3—C2—C1	114.9 (3)	C10—C11—H11	120.3
C4—C3—C2	123.1 (4)	C12—C11—H11	120.3
C4—C3—Cl1	118.8 (3)	C11—C12—C13	119.1 (4)
C2—C3—Cl1	118.1 (3)	C11—C12—H12	120.4
C3—C4—C5	119.6 (3)	C13—C12—H12	120.4
C3—C4—H4	120.2	N2—C13—C12	122.0 (4)
C5—C4—H4	120.2	N2—C13—H13	119.0
C6—C5—C4	120.4 (3)	C12—C13—H13	119.0
C6—C5—Cl2	119.2 (3)	N3—C14—S1	179.1 (4)
C4—C5—Cl2	120.3 (3)
N1—Cu1—O1—C2	2.4 (3)	Cl1—C3—C4—C5	−178.3 (3)
N3—Cu1—O1—C2	172.7 (3)	C3—C4—C5—C6	−0.4 (6)
O1—Cu1—N1—C7	−1.0 (3)	C3—C4—C5—Cl2	178.3 (3)
N3—Cu1—N1—C7	−112.7 (7)	C4—C5—C6—C1	−0.8 (6)
N2—Cu1—N1—C7	−179.5 (3)	Cl2—C5—C6—C1	−179.4 (3)
O1—Cu1—N1—C8	−178.2 (3)	C2—C1—C6—C5	0.7 (6)
N3—Cu1—N1—C8	70.0 (7)	C7—C1—C6—C5	179.9 (3)
N2—Cu1—N1—C8	3.2 (3)	C8—N1—C7—C1	177.0 (3)
N1—Cu1—N2—C9	−2.1 (2)	Cu1—N1—C7—C1	−0.3 (5)
N3—Cu1—N2—C9	−172.5 (2)	C6—C1—C7—N1	−178.5 (3)
O1—Cu1—N3—C14	166.7 (9)	C2—C1—C7—N1	0.7 (6)
N1—Cu1—N2—C13	−178.7 (3)	C7—N1—C8—C9	178.7 (3)
N3—Cu1—N2—C13	10.9 (3)	Cu1—N1—C8—C9	−3.8 (4)
N1—Cu1—N3—C14	−81.3 (11)	C13—N2—C9—C10	−2.4 (5)
N2—Cu1—N3—C14	−15.5 (9)	Cu1—N2—C9—C10	−179.4 (3)
Cu1—O1—C2—C3	176.9 (2)	C13—N2—C9—C8	177.5 (3)
Cu1—O1—C2—C1	−2.6 (5)	Cu1—N2—C9—C8	0.5 (4)
C6—C1—C2—O1	180.0 (3)	N1—C8—C9—N2	2.0 (5)
C7—C1—C2—O1	0.8 (6)	N1—C8—C9—C10	−178.1 (3)
C6—C1—C2—C3	0.4 (5)	N2—C9—C10—C11	1.0 (6)
C7—C1—C2—C3	−178.8 (3)	C8—C9—C10—C11	−178.8 (4)
O1—C2—C3—C4	178.8 (3)	C9—C10—C11—C12	0.5 (6)
C1—C2—C3—C4	−1.6 (5)	C10—C11—C12—C13	−0.7 (6)
O1—C2—C3—Cl1	−1.3 (5)	C9—N2—C13—C12	2.2 (6)
C1—C2—C3—Cl1	178.3 (3)	Cu1—N2—C13—C12	178.7 (3)
C2—C3—C4—C5	1.6 (6)	C11—C12—C13—N2	−0.6 (6)

Symmetry code: (i) −x+1, −y+2, −z.