Dichlorido{N,N-dimethyl-N′-[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine-κ³ N,N′,N′′}copper(II)

Abstract

In the title compound, [CuCl₂(C₁₁H₁₇N₃)], the Cu^II ion is five-coordinated with a distorted square-pyramidal configuration. The three N atoms of the Schiff base ligand and one Cl atom are located in the basal plane, whereas the other Cl atom is apically positioned.

Related literature

For the crystal structures of similar copper (II) complexes, see: Wang et al. (2009 ▶); Yuan & Zhang (2005 ▶); Zhang et al. (2009 ▶). For a description of the geometry of five-coordinated metal complexes, see: Addison et al. (1984 ▶).

Experimental

Crystal data

• [CuCl₂(C₁₁H₁₇N₃)]

• M _r = 325.72

• Orthorhombic,

• a = 9.81448 (12) Å

• b = 9.90297 (13) Å

• c = 14.21414 (18) Å

• V = 1381.51 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 1.95 mm⁻¹

• T = 100 K

• 0.30 × 0.23 × 0.07 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.592, T _max = 0.876

• 10998 measured reflections

• 2439 independent reflections

• 2378 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.017

• wR(F ²) = 0.043

• S = 1.03

• 2439 reflections

• 157 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1022 Friedel pairs

• Flack parameter: 0.010 (9)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

The title compound was obtained by the reaction of N,N-dimethyl-N'-[methyl(2-pyridyl)methylene]ethane-1,2-diamine with copper(II) chloride. In the molecule of the complex, the metal ion is penta-coordinated by the tridentate Schiff base ligand and two chloride atoms (Fig. 1). The geometry of the complex can be determined by using the index τ = (β-α)/60, where β is the largest angle and α is the second one around the metal center. For an ideal square-pyramidal geometry τ is 0, while it is 1 in a perfect trigonal-bipyramid (Addison et al.,1984). The two largest angels in the title compound are 158.45 (6)° (N1—Cu—N3) and 154.98 (5)° (N2—Cu—Cl2) which give a τ value of 0.058. This value indicates a slightly distorted square pyramidal geometry in which the three N atoms of the Schiff base ligand and one chloride atom occupy the basal positions and the other chloride atom is placed in the apical position.

Experimental

The Schiff base ligand was prepared via condensation reaction of N,N-dimethylethyldiamine (0.44 g, 5 mmol) and 2-acetylpyridine (0.61 g, 5 mmol) by refluxing in ethanol (50 ml) for 2 h. For synthesis of the title complex a mixture of the Schiff base ligand (0.57 g, 3 mmol) and copper (II) chloride dihydrate (0.51 g, 3 mmol) in ethanol (50 ml) was stirred at room temperature for half an hour. The solvent was then evaporated partially to yield the title complex as a green solid. Suitable crystals for X-ray crystallography were obtained upon slow evaporation of an ethanolic solution at room temperature.

Refinement

Hydrogen atoms were placed at calculated positions (C—H 0.95-0.98 Å), and were treated as riding on their parent atoms, with U_iso(H) set to 1.2-1.5 times U_eq(C). An absolute structure was established using anomalous dispersion effects; 1021 Friedel pairs were not merged.

Figures

Fig. 1.

Thermal ellipsoid plot of the title compound at the 50% probability level.

Crystal data

[CuCl2(C11H17N3)]	F(000) = 668
Mr = 325.72	Dx = 1.566 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7155 reflections
a = 9.81448 (12) Å	θ = 2.5–30.4°
b = 9.90297 (13) Å	µ = 1.95 mm−1
c = 14.21414 (18) Å	T = 100 K
V = 1381.51 (2) Å3	Block, green
Z = 4	0.30 × 0.23 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer	2439 independent reflections
Radiation source: fine-focus sealed tube	2378 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.592, Tmax = 0.876	k = −11→11
10998 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)] = 0.017	H-atom parameters constrained
wR(F2) = 0.043	w = 1/[σ2(Fo2) + (0.0245P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2439 reflections	Δρmax = 0.21 e Å−3
157 parameters	Δρmin = −0.20 e Å−3
0 restraints	Absolute structure: Flack (1983), 1022 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.010 (9)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cu	0.80028 (2)	0.16329 (2)	0.099598 (15)	0.01175 (7)
Cl1	0.56577 (5)	0.08033 (5)	0.13120 (3)	0.01619 (11)
Cl2	0.92633 (5)	0.14346 (5)	0.23208 (3)	0.01790 (12)
N1	0.86920 (16)	−0.00757 (17)	0.03434 (12)	0.0139 (4)
N2	0.76828 (16)	0.20963 (16)	−0.03353 (11)	0.0124 (4)
N3	0.75938 (15)	0.36500 (16)	0.11931 (11)	0.0132 (4)
C1	0.9300 (2)	−0.11396 (19)	0.07379 (15)	0.0169 (4)
H1	0.9448	−0.1136	0.1398	0.020*
C2	0.9722 (2)	−0.2245 (2)	0.02225 (15)	0.0185 (5)
H2	1.0174	−0.2976	0.0522	0.022*
C3	0.9479 (2)	−0.2274 (2)	−0.07327 (15)	0.0200 (5)
H3	0.9737	−0.3036	−0.1098	0.024*
C4	0.8846 (2)	−0.1161 (2)	−0.11553 (15)	0.0175 (4)
H4	0.8666	−0.1155	−0.1812	0.021*
C5	0.84897 (19)	−0.0075 (2)	−0.06026 (13)	0.0131 (4)
C6	0.79321 (18)	0.12257 (18)	−0.09696 (13)	0.0129 (4)
C7	0.7771 (2)	0.1485 (2)	−0.20048 (13)	0.0200 (5)
H7A	0.6843	0.1805	−0.2132	0.030*
H7B	0.7935	0.0648	−0.2354	0.030*
H7C	0.8428	0.2173	−0.2204	0.030*
C8	0.71958 (19)	0.3470 (2)	−0.05216 (13)	0.0139 (4)
H8A	0.6464	0.3460	−0.1001	0.017*
H8B	0.7949	0.4047	−0.0751	0.017*
C9	0.6657 (2)	0.3992 (2)	0.04119 (14)	0.0158 (4)
H9A	0.6548	0.4985	0.0377	0.019*
H9B	0.5751	0.3592	0.0536	0.019*
C10	0.6923 (2)	0.3973 (2)	0.20995 (13)	0.0195 (4)
H10A	0.7533	0.3737	0.2620	0.029*
H10B	0.6076	0.3456	0.2154	0.029*
H10C	0.6718	0.4941	0.2124	0.029*
C11	0.8874 (2)	0.4429 (2)	0.11176 (15)	0.0200 (5)
H11A	0.9314	0.4230	0.0514	0.030*
H11B	0.9486	0.4176	0.1633	0.030*
H11C	0.8671	0.5396	0.1155	0.030*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu	0.01269 (12)	0.01237 (12)	0.01020 (12)	0.00077 (10)	−0.00026 (10)	0.00045 (10)
Cl1	0.0134 (2)	0.0185 (3)	0.0166 (2)	−0.0024 (2)	−0.00053 (18)	0.0027 (2)
Cl2	0.0177 (2)	0.0229 (3)	0.0130 (2)	0.0021 (2)	−0.00368 (19)	0.0008 (2)
N1	0.0115 (8)	0.0159 (9)	0.0143 (8)	−0.0012 (7)	0.0026 (7)	0.0014 (7)
N2	0.0107 (9)	0.0133 (8)	0.0131 (8)	0.0003 (6)	−0.0012 (7)	0.0033 (7)
N3	0.0137 (8)	0.0146 (8)	0.0114 (8)	0.0001 (6)	0.0009 (6)	0.0000 (7)
C1	0.0181 (10)	0.0146 (10)	0.0180 (11)	−0.0018 (8)	0.0028 (9)	0.0036 (8)
C2	0.0203 (11)	0.0136 (11)	0.0217 (12)	0.0004 (8)	0.0034 (9)	0.0057 (9)
C3	0.0229 (11)	0.0144 (10)	0.0227 (11)	−0.0009 (9)	0.0024 (9)	−0.0051 (9)
C4	0.0170 (10)	0.0184 (11)	0.0171 (11)	−0.0034 (8)	−0.0009 (9)	−0.0014 (9)
C5	0.0101 (10)	0.0148 (10)	0.0143 (10)	−0.0034 (8)	0.0011 (8)	−0.0012 (8)
C6	0.0093 (9)	0.0160 (9)	0.0134 (9)	−0.0037 (7)	−0.0012 (9)	−0.0009 (8)
C7	0.0223 (11)	0.0237 (11)	0.0139 (10)	0.0061 (10)	−0.0012 (8)	−0.0014 (9)
C8	0.0145 (10)	0.0136 (10)	0.0137 (10)	0.0008 (9)	−0.0019 (7)	0.0020 (8)
C9	0.0146 (10)	0.0144 (10)	0.0185 (10)	0.0017 (8)	−0.0009 (8)	0.0019 (9)
C10	0.0272 (11)	0.0176 (10)	0.0136 (10)	0.0018 (10)	0.0029 (10)	−0.0021 (8)
C11	0.0213 (11)	0.0183 (11)	0.0204 (12)	−0.0064 (8)	−0.0018 (9)	−0.0015 (10)

Geometric parameters (Å, °)

Cu—N2	1.9723 (16)	C4—C5	1.377 (3)
Cu—N1	2.0447 (17)	C4—H4	0.9500
Cu—N3	2.0567 (16)	C5—C6	1.494 (3)
Cu—Cl2	2.2617 (5)	C6—C7	1.502 (3)
Cu—Cl1	2.4848 (5)	C7—H7A	0.9800
N1—C1	1.334 (3)	C7—H7B	0.9800
N1—C5	1.359 (2)	C7—H7C	0.9800
N2—C6	1.271 (2)	C8—C9	1.519 (3)
N2—C8	1.466 (3)	C8—H8A	0.9900
N3—C11	1.478 (2)	C8—H8B	0.9900
N3—C10	1.482 (2)	C9—H9A	0.9900
N3—C9	1.481 (2)	C9—H9B	0.9900
C1—C2	1.381 (3)	C10—H10A	0.9800
C1—H1	0.9500	C10—H10B	0.9800
C2—C3	1.379 (3)	C10—H10C	0.9800
C2—H2	0.9500	C11—H11A	0.9800
C3—C4	1.401 (3)	C11—H11B	0.9800
C3—H3	0.9500	C11—H11C	0.9800
N2—Cu—N1	79.04 (7)	N1—C5—C6	113.54 (17)
N2—Cu—N3	82.74 (6)	C4—C5—C6	124.56 (17)
N1—Cu—N3	158.45 (6)	N2—C6—C5	114.06 (16)
N2—Cu—Cl2	154.98 (5)	N2—C6—C7	123.94 (18)
N1—Cu—Cl2	97.17 (5)	C5—C6—C7	121.90 (16)
N3—Cu—Cl2	94.45 (4)	C6—C7—H7A	109.5
N2—Cu—Cl1	95.91 (5)	C6—C7—H7B	109.5
N1—Cu—Cl1	96.59 (5)	H7A—C7—H7B	109.5
N3—Cu—Cl1	96.65 (4)	C6—C7—H7C	109.5
Cl2—Cu—Cl1	109.113 (18)	H7A—C7—H7C	109.5
C1—N1—C5	118.77 (18)	H7B—C7—H7C	109.5
C1—N1—Cu	127.64 (14)	N2—C8—C9	105.76 (15)
C5—N1—Cu	113.59 (13)	N2—C8—H8A	110.6
C6—N2—C8	124.33 (16)	C9—C8—H8A	110.6
C6—N2—Cu	119.47 (13)	N2—C8—H8B	110.6
C8—N2—Cu	116.17 (12)	C9—C8—H8B	110.6
C11—N3—C10	109.14 (15)	H8A—C8—H8B	108.7
C11—N3—C9	110.72 (15)	N3—C9—C8	111.17 (16)
C10—N3—C9	109.07 (15)	N3—C9—H9A	109.4
C11—N3—Cu	109.33 (12)	C8—C9—H9A	109.4
C10—N3—Cu	114.53 (12)	N3—C9—H9B	109.4
C9—N3—Cu	103.96 (12)	C8—C9—H9B	109.4
N1—C1—C2	122.50 (19)	H9A—C9—H9B	108.0
N1—C1—H1	118.8	N3—C10—H10A	109.5
C2—C1—H1	118.8	N3—C10—H10B	109.5
C3—C2—C1	119.1 (2)	H10A—C10—H10B	109.5
C3—C2—H2	120.4	N3—C10—H10C	109.5
C1—C2—H2	120.4	H10A—C10—H10C	109.5
C2—C3—C4	118.9 (2)	H10B—C10—H10C	109.5
C2—C3—H3	120.6	N3—C11—H11A	109.5
C4—C3—H3	120.6	N3—C11—H11B	109.5
C5—C4—C3	118.86 (19)	H11A—C11—H11B	109.5
C5—C4—H4	120.6	N3—C11—H11C	109.5
C3—C4—H4	120.6	H11A—C11—H11C	109.5
N1—C5—C4	121.81 (19)	H11B—C11—H11C	109.5