Chlorido(pyridine-2-carbaldehyde oximato-κ² N,N′)(pyridine-2-carbaldehyde oxime-κ² N,N′)copper(II)

Abstract

In the title compound, [Cu(C₆H₅N₂O)Cl(C₆H₆N₂O)], the Cu atom is coordinated by one neutral and one deprotonated pyridine-2-carboxaldehyde oxime (pco) ligand, resulting in the formation of two five-membered CuN₂C₂ rings. Together with the additional coordinating chloride anion, the coordination polyhedron of copper is best described as a distorted square-pyramid, the distortion parameter being 0.288. The two organic ligands are linked by an intramolecular O—H⋯O hydrogen bond.

Related literature

For related literature, see: Addison et al. (1984 ▶); Afrati et al. (2005 ▶); Korpi et al. (2005 ▶); Pearse et al. (1989 ▶); Stamatatos et al. (2006 ▶).

Experimental

Crystal data

• [Cu(C₆H₅N₂O)Cl(C₆H₆N₂O)]

• M _r = 342.24

• Monoclinic,

• a = 16.686 (2) Å

• b = 12.064 (2) Å

• c = 13.805 (1) Å

• β = 109.02 (1)°

• V = 2627.3 (5) ų

• Z = 8

• Mo Kα radiation

• μ = 1.87 mm⁻¹

• T = 293 (2) K

• 0.22 × 0.18 × 0.15 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008 ▶) T _min = 0.488, T _max = 0.594 (expected range = 0.620–0.755)

• 6487 measured reflections

• 2318 independent reflections

• 1788 reflections with I > 2σ(I)

• R _int = 0.034

Refinement

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.110

• S = 1.01

• 2318 reflections

• 181 parameters

• H-atom parameters constrained

• Δρ_max = 0.40 e Å⁻³

• Δρ_min = −0.39 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O2	0.82	1.70	2.488 (5)	162

supplementary crystallographic information

Comment

Pyridine-2-carbaldehyde oxime ligands usually bind to metals in a bidentate fashion, either chelating one metal center or bridging two metals. Their complexes find application in diverse areas such as functional supramolecular design, magnetic materials and catalysis (Korpi et al., 2005; Pearse et al., 1989; Afrati et al., 2005; Stamatatos et al., 2006). The title compound is a new copper complex from the reaction of CuCl₂ with pyridine-2-carbaldehyde oxime (pco). The compound consists of two N,N-chelating ligands and one chloride anion. The two pco ligands are coordinated to copper to form two five-membered CuC₂N₂ rings. The copper atom adopts a distorted 4 + 1 square-pyramidal coordination mode with the distortion parameter being 0.288 (Addison et al., 1984) and the angles around copper ion ranging from 79.07 (1)° for N3—Cu1—N4 to 168.37 (1)° for N2—Cu1—N3. From the viewpoint of charge balance, it is presumed there exists one deprotonated and one protonated oxime ligand with a strong intramolecular hydrogen bond between the OH group and the negatively charged oxygen of the other ligand (O1···O2 = 2.488 Å) which would also give an explanation for the rather unusal cis-arrangement of the ligands (Scheme 1, Figure 1. ).

Experimental

A methanolic solution (15 ml) containing pco (0.1 mmol, 0.012 g) was added to an methanolic solution (10 ml) containing CuCl₂ × 2 H₂O (0.1 mmol, 0.017 g). After stirring for 2 h, the solution was filtered. Dark green needle-like crystals suitable for single-crystal X-ray diffraction were obtained by evaporating the resulting filtrate in air for several days (yield 65.6% based on the ligand).

Refinement

H atoms were placed geometrically and allowed to ride during refinement with C—H = 0.93–0.96 Å and O—H = 0.82 Å with U_iso(H) = 1.2 or 1.5Ueq(C or O).

Figures

Fig. 1.

The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.

Crystal data

[Cu(C6H5N2O)Cl(C6H6N2O)]	F000 = 1384
Mr = 342.24	Dx = 1.730 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2343 reflections
a = 16.686 (2) Å	θ = 2.4–26.6º
b = 12.064 (2) Å	µ = 1.87 mm−1
c = 13.805 (1) Å	T = 293 (2) K
β = 109.02 (1)º	Block, dark green
V = 2627.3 (5) Å3	0.22 × 0.18 × 0.15 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	2318 independent reflections
Radiation source: fine-focus sealed tube	1788 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.034
T = 293(2) K	θmax = 25.0º
φ and ω scans	θmin = 2.1º
Absorption correction: multi-scan(SHELXTL; Sheldrick, 2008)	h = −14→19
Tmin = 0.488, Tmax = 0.594	k = −14→13
6487 measured reflections	l = −16→16

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H-atom parameters constrained
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.065P)2 + 1.2P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
2318 reflections	Δρmax = 0.40 e Å−3
181 parameters	Δρmin = −0.39 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	0.45583 (2)	0.75857 (3)	0.08754 (3)	0.03490 (18)
Cl1	0.39133 (6)	0.74459 (6)	−0.09737 (7)	0.0452 (3)
N2	0.39301 (17)	0.8985 (2)	0.1014 (2)	0.0365 (6)
N3	0.53622 (18)	0.6345 (2)	0.0978 (2)	0.0432 (7)
N4	0.39418 (17)	0.6311 (2)	0.1352 (2)	0.0386 (7)
O2	0.60997 (16)	0.6484 (2)	0.0801 (2)	0.0594 (7)
C1	0.3107 (2)	0.9115 (3)	0.0892 (3)	0.0445 (9)
H1A	0.2761	0.8491	0.0764	0.053*
N1	0.54953 (17)	0.8713 (2)	0.1156 (2)	0.0431 (7)
C11	0.4316 (2)	0.5328 (3)	0.1314 (3)	0.0427 (9)
C5	0.4419 (2)	0.9892 (3)	0.1166 (3)	0.0433 (8)
O1	0.63020 (15)	0.8491 (3)	0.1224 (2)	0.0666 (8)
H1B	0.6346	0.7834	0.1100	0.100*
C2	0.2750 (3)	1.0126 (4)	0.0946 (3)	0.0585 (11)
H2A	0.2177	1.0187	0.0866	0.070*
C9	0.3236 (3)	0.4362 (4)	0.1762 (3)	0.0647 (12)
H9A	0.3002	0.3707	0.1903	0.078*
C7	0.3232 (2)	0.6295 (3)	0.1599 (3)	0.0457 (9)
H7A	0.2973	0.6968	0.1638	0.055*
C12	0.5115 (2)	0.5390 (3)	0.1109 (3)	0.0463 (9)
H12A	0.5426	0.4760	0.1076	0.056*
C6	0.5299 (2)	0.9703 (3)	0.1257 (3)	0.0483 (9)
H6A	0.5692	1.0276	0.1381	0.058*
C10	0.3975 (3)	0.4349 (3)	0.1509 (3)	0.0579 (11)
H10A	0.4239	0.3680	0.1471	0.069*
C8	0.2865 (3)	0.5352 (4)	0.1798 (3)	0.0593 (11)
H8A	0.2365	0.5388	0.1957	0.071*
C4	0.4094 (3)	1.0927 (3)	0.1215 (3)	0.0636 (12)
H4A	0.4440	1.1550	0.1313	0.076*
C3	0.3253 (3)	1.1034 (3)	0.1118 (4)	0.0718 (13)
H3A	0.3029	1.1729	0.1171	0.086*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu1	0.0277 (3)	0.0340 (3)	0.0441 (3)	0.00547 (15)	0.0132 (2)	−0.00158 (17)
Cl1	0.0482 (6)	0.0432 (5)	0.0407 (5)	0.0035 (4)	0.0094 (4)	−0.0023 (4)
N2	0.0355 (16)	0.0317 (15)	0.0418 (16)	0.0041 (12)	0.0118 (13)	−0.0026 (12)
N3	0.0398 (17)	0.0480 (19)	0.0432 (17)	0.0156 (14)	0.0152 (14)	0.0003 (14)
N4	0.0385 (16)	0.0366 (16)	0.0392 (16)	0.0031 (12)	0.0107 (13)	0.0023 (12)
O2	0.0440 (16)	0.0712 (19)	0.0731 (19)	0.0207 (14)	0.0327 (14)	0.0047 (15)
C1	0.040 (2)	0.044 (2)	0.049 (2)	0.0096 (16)	0.0142 (17)	0.0009 (16)
N1	0.0286 (16)	0.0516 (19)	0.0505 (18)	−0.0040 (13)	0.0147 (14)	−0.0005 (14)
C11	0.052 (2)	0.0372 (19)	0.032 (2)	0.0057 (16)	0.0044 (17)	−0.0001 (15)
C5	0.052 (2)	0.038 (2)	0.040 (2)	0.0022 (16)	0.0157 (18)	−0.0024 (16)
O1	0.0326 (15)	0.077 (2)	0.092 (2)	−0.0025 (13)	0.0241 (15)	−0.0042 (17)
C2	0.051 (2)	0.066 (3)	0.059 (3)	0.029 (2)	0.019 (2)	0.002 (2)
C9	0.069 (3)	0.058 (3)	0.058 (3)	−0.024 (2)	0.009 (2)	0.009 (2)
C7	0.041 (2)	0.051 (2)	0.047 (2)	−0.0006 (17)	0.0166 (17)	0.0022 (17)
C12	0.052 (2)	0.044 (2)	0.040 (2)	0.0195 (18)	0.0113 (18)	−0.0006 (17)
C6	0.045 (2)	0.045 (2)	0.056 (2)	−0.0115 (17)	0.0177 (18)	−0.0050 (18)
C10	0.071 (3)	0.036 (2)	0.053 (2)	−0.0020 (19)	0.002 (2)	0.0001 (18)
C8	0.052 (3)	0.067 (3)	0.057 (3)	−0.014 (2)	0.016 (2)	0.006 (2)
C4	0.080 (3)	0.031 (2)	0.079 (3)	0.0027 (19)	0.025 (3)	−0.0044 (19)
C3	0.088 (4)	0.044 (3)	0.084 (3)	0.033 (2)	0.029 (3)	−0.004 (2)

Geometric parameters (Å, °)

Cu1—N3	1.984 (3)	C5—C4	1.371 (5)
Cu1—N1	2.012 (3)	C5—C6	1.451 (5)
Cu1—N2	2.029 (3)	O1—H1B	0.8200
Cu1—N4	2.072 (3)	C2—C3	1.352 (6)
Cu1—Cl1	2.4316 (10)	C2—H2A	0.9300
N2—C1	1.338 (4)	C9—C8	1.354 (6)
N2—C5	1.340 (4)	C9—C10	1.385 (6)
N3—C12	1.256 (5)	C9—H9A	0.9300
N3—O2	1.341 (3)	C7—C8	1.361 (5)
N4—C7	1.335 (4)	C7—H7A	0.9300
N4—C11	1.350 (4)	C12—H12A	0.9300
C1—C2	1.370 (5)	C6—H6A	0.9300
C1—H1A	0.9300	C10—H10A	0.9300
N1—C6	1.258 (4)	C8—H8A	0.9300
N1—O1	1.345 (3)	C4—C3	1.371 (6)
C11—C10	1.375 (5)	C4—H4A	0.9300
C11—C12	1.453 (5)	C3—H3A	0.9300
N3—Cu1—N1	91.79 (14)	C4—C5—C6	123.0 (4)
N3—Cu1—N2	168.29 (12)	N1—O1—H1B	109.5
N1—Cu1—N2	79.19 (11)	C3—C2—C1	118.4 (4)
N3—Cu1—N4	79.15 (12)	C3—C2—H2A	120.8
N1—Cu1—N4	151.07 (12)	C1—C2—H2A	120.8
N2—Cu1—N4	105.21 (11)	C8—C9—C10	118.3 (4)
N3—Cu1—Cl1	94.60 (9)	C8—C9—H9A	120.9
N1—Cu1—Cl1	107.40 (9)	C10—C9—H9A	120.9
N2—Cu1—Cl1	95.22 (8)	N4—C7—C8	124.0 (4)
N4—Cu1—Cl1	100.71 (8)	N4—C7—H7A	118.0
C1—N2—C5	118.1 (3)	C8—C7—H7A	118.0
C1—N2—Cu1	128.8 (2)	N3—C12—C11	116.1 (3)
C5—N2—Cu1	112.8 (2)	N3—C12—H12A	121.9
C12—N3—O2	120.3 (3)	C11—C12—H12A	121.9
C12—N3—Cu1	117.1 (2)	N1—C6—C5	115.7 (3)
O2—N3—Cu1	122.1 (2)	N1—C6—H6A	122.2
C7—N4—C11	117.2 (3)	C5—C6—H6A	122.2
C7—N4—Cu1	131.7 (2)	C11—C10—C9	119.9 (4)
C11—N4—Cu1	110.9 (2)	C11—C10—H10A	120.0
N2—C1—C2	122.9 (4)	C9—C10—H10A	120.0
N2—C1—H1A	118.5	C9—C8—C7	119.2 (4)
C2—C1—H1A	118.5	C9—C8—H8A	120.4
C6—N1—O1	118.2 (3)	C7—C8—H8A	120.4
C6—N1—Cu1	116.6 (2)	C5—C4—C3	119.3 (4)
O1—N1—Cu1	125.2 (2)	C5—C4—H4A	120.4
N4—C11—C10	121.4 (4)	C3—C4—H4A	120.4
N4—C11—C12	115.3 (3)	C2—C3—C4	119.8 (4)
C10—C11—C12	123.2 (3)	C2—C3—H3A	120.1
N2—C5—C4	121.4 (4)	C4—C3—H3A	120.1
N2—C5—C6	115.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O2	0.82	1.70	2.488 (5)	162