Dichlorido{N,N-dimethyl-N′-[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine-κ3N,N′,N′′}copper(II)

Saleh Salga, M.; Khaledi, H.; Mohd Ali, H.; Puteh, R.

doi:10.1107/S1600536810011712

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page m508

https://doi.org/10.1107/S1600536810011712

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Dichlorido{N,N-dimethyl-N′-[1-(2-pyridyl)ethylidene]ethane-1,2-diamine-κ³N,N′,N′′}copper(II)

Muhammad Saleh Salga,^a Hamid Khaledi,^a ^* Hapipah Mohd Ali ^a and Rustam Puteh ^b

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^bDepartment of Physics, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: khaledi@perdana.um.edu.my

(Received 13 March 2010; accepted 29 March 2010; online 10 April 2010)

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, P 2₁ 2₁ 2₁
a = 9.81448 (12) Å
b = 9.90297 (13) Å
c = 14.21414 (18) Å
V = 1381.51 (2) Å³
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[F² > 2σ(F²)] = 0.017
wR(F²) = 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810011712/pv2266sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810011712/pv2266Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

Fig. 1. Thermal ellipsoid plot of the title compound at the 50% probability level.

Dichlorido{N,N-dimethyl-N'-[1-(2- pyridyl)ethylidene]ethane-1,2-diamine- κ³N,N',N''}copper(II) top

Crystal data top

[CuCl₂(C₁₁H₁₇N₃)]	F(000) = 668
M_r = 325.72	D_x = 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 top

Bruker APEXII CCD diffractometer	2439 independent reflections
Radiation source: fine-focus sealed tube	2378 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.592, T_max = 0.876	k = −11→11
10998 measured reflections	l = −16→16

Refinement top

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(F_o²) + (0.0245P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2439 reflections	Δρ_max = 0.21 e Å⁻³
157 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1022 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.010 (9)

Crystal data top

[CuCl₂(C₁₁H₁₇N₃)]	V = 1381.51 (2) Å³
M_r = 325.72	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.81448 (12) Å	µ = 1.95 mm⁻¹
b = 9.90297 (13) Å	T = 100 K
c = 14.21414 (18) Å	0.30 × 0.23 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	2439 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2378 reflections with I > 2σ(I)
T_min = 0.592, T_max = 0.876	R_int = 0.026
10998 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	H-atom parameters constrained
wR(F²) = 0.043	Δρ_max = 0.21 e Å⁻³
S = 1.03	Δρ_min = −0.20 e Å⁻³
2439 reflections	Absolute structure: Flack (1983), 1022 Friedel pairs
157 parameters	Absolute structure parameter: 0.010 (9)
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₁H₁₇N₃)]
M_r	325.72
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	9.81448 (12), 9.90297 (13), 14.21414 (18)
V (Å³)	1381.51 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.95
Crystal size (mm)	0.30 × 0.23 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.592, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	10998, 2439, 2378
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.043, 1.03
No. of reflections	2439
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20
Absolute structure	Flack (1983), 1022 Friedel pairs
Absolute structure parameter	0.010 (9)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

The authors thank the University of Malaya for funding this study (FRGS grant No. FP009/2008 C).

References

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