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

Wang, Q.; Bi, C.-F.; Wang, D.-Q.; Fan, Y.-H.

doi:10.1107/S1600536809010149

metal-organic compounds

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Volume 65| Part 4| April 2009| Page m439

doi:10.1107/S1600536809010149

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

Qiang Wang,^a Cai-Feng Bi,^a ^* Da-Qi Wang ^b and Yu-Hua Fan ^a

^aCollege of Chemistry and Chemical Engineering, Ocean University of China, Shandong 266100, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: bicaifeng9999@163.com

(Received 12 March 2009; accepted 19 March 2009; online 25 March 2009)

The title complex, [CuCl₂(C₉H₁₃N₃)], is mononuclear and contains a five-coordinate Cu^II atom. The geometry of the Cu^II atom can be described as tetragonal-pyramidal derived from the calculation of the value τ = 0.102. The three N atoms of the pyridine and ethane-1,2-diamine ligands and one Cl atom belong to the basal plane and the other Cl atom represents the axial position of the pyramid. The Cu atom is displaced by 0.2599 (2) Å from the basal plane towards the axial Cl atom. In the crystal, molecules are linked into chains by intermolecular N—H⋯Cl and C—H⋯Cl hydrogen bonds.

Related literature

For general background, see: Coles et al. (1998 ). For the calculation of the geometry parameter τ in five-coordinate complexes, see: Addison et al. (1984 ).

Experimental

Crystal data

[CuCl₂(C₉H₁₃N₃)]
M_r = 297.66
Triclinic, $[P \overline 1]$
a = 7.2701 (10) Å
b = 8.8008 (12) Å
c = 9.5773 (15) Å
α = 82.940 (2)°
β = 76.289 (1)°
γ = 85.751 (2)°
V = 590.16 (15) Å³
Z = 2
Mo Kα radiation
μ = 2.27 mm⁻¹
T = 298 K
0.50 × 0.42 × 0.17 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.396, T_max = 0.699
2903 measured reflections
2021 independent reflections
1549 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.160
S = 1.04
2021 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—N2	1.977 (5)
Cu1—N3	2.002 (5)
Cu1—N1	2.050 (5)
Cu1—Cl2	2.2659 (17)
Cu1—Cl1	2.4812 (16)

N3—Cu1—N1	158.54 (19)
N2—Cu1—Cl2	164.66 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl1ⁱ	0.90	2.47	3.248 (5)	145
N3—H3B⋯Cl2ⁱⁱ	0.90	2.49	3.322 (5)	154
C6—H6⋯Cl2ⁱⁱⁱ	0.93	2.77	3.666 (7)	161
C4—H4⋯Cl1^iv	0.93	2.74	3.612 (7)	156
C1—H1A⋯Cl1^v	0.96	2.80	3.726 (6)	161
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y+2, -z+2; (iii) -x+2, -y+2, -z+1; (iv) -x+1, -y+1, -z+1; (v) x-1, y, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809010149/si2162sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010149/si2162Isup2.hkl

checkCIF report

Comment top

Schiff-base ligands have played an integral role in the development of coordination chemistry since the late 19t h century. The finding that metal complexes of these ligands are ubiquitous is a reflection of their facile synthesis, wide application and the accessibility of diverse structural modifications (Coles et al., 1998). We report here the synthesis and crystal structure of the title complex, a new copper(II) complex, with a tridentate Schiff base ligand derived from the condensation of 2-acetylpyridine and diamine.

The molecular structure of the title complex is shown in Fig.1. The Cu^II atom is five-coordinated. The basal plane for a tetragonal-pyramidal geometry is defined by the atoms N1, N2, N3 and Cl2, their mean deviation from this plane is 0.025 Å, and the Cu atom juts out of this plane by 0.2599 (2) Å. The axial position of the pyramid is occupied by atom Cl1. For this point of view, a geometry parameter τ, which is defined τ = (β - α)/60, applicable to five-coordinate structures within the structural continuum between trigonal bipyramidal and tetragonal or rectangular pyramidal. For a perfect tetragonal symmetry τ is zero, and for a perfect trigonal-bipyramidal geometry τ becomes 1.0 (Addison et al. 1984). In the title compound, the largest angles within the four atoms N1, N2, N3, Cl2 are β = 164.66 (16)° for N2–Cu1–Cl2, and α = 158.54 (19)° for N1–Cu1–N3. Thus, τ is (164.66–158.54)/60 = 0.102, indicating a 90% rectangular pyramidal geometry. Selected geometric parameters are presented in Table 1. As seen in Fig. 2, the molecules are linked into chains by intermolecular N—H···Cl and C—H···Cl hydrogen bonds (Table 2).

Related literature top

For general background, see: Coles et al. (1998). For the calculation of the geometry parameter τ in five-coordinate complexes, see: Addison et al. (1984).

Experimental top

2-acetylpyridine (10 mmol, 1205 mg) was added dropwise to a absolute ethanol (20 ml) of diamine (10 mmol, 611 mg). The mixture was heated under reflux with stirring for 3 h. An absolute ethanol solution (10 ml) of cupric chloride dihydrate (10 mmol, 1700 mg) was then added dropwise, and the mixture was stirred at room temperature for another 13 h. The solution was filtered off, the filterate was kept at room temperature for about three weeks, after which large green block-shaped crystals of the title complex suitable for X-ray diffraction analysis were obtained.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title complex, viewed approximately along the c axis.

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

Crystal data top

[CuCl₂(C₉H₁₃N₃)]	Z = 2
M_r = 297.66	F(000) = 302
Triclinic, P1	D_x = 1.675 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2701 (10) Å	Cell parameters from 1739 reflections
b = 8.8008 (12) Å	θ = 2.3–27.9°
c = 9.5773 (15) Å	µ = 2.27 mm⁻¹
α = 82.940 (2)°	T = 298 K
β = 76.289 (1)°	Block, green
γ = 85.751 (2)°	0.50 × 0.42 × 0.17 mm
V = 590.16 (15) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	2021 independent reflections
Radiation source: fine-focus sealed tube	1549 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→8
T_min = 0.396, T_max = 0.699	k = −10→10
2903 measured reflections	l = −9→11

Refinement top

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0888P)² + 0.8983P] where P = (F_o² + 2F_c²)/3
2021 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.91 e Å⁻³
0 restraints	Δρ_min = −0.81 e Å⁻³

Crystal data top

[CuCl₂(C₉H₁₃N₃)]	γ = 85.751 (2)°
M_r = 297.66	V = 590.16 (15) Å³
Triclinic, P1	Z = 2
a = 7.2701 (10) Å	Mo Kα radiation
b = 8.8008 (12) Å	µ = 2.27 mm⁻¹
c = 9.5773 (15) Å	T = 298 K
α = 82.940 (2)°	0.50 × 0.42 × 0.17 mm
β = 76.289 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2021 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1549 reflections with I > 2σ(I)
T_min = 0.396, T_max = 0.699	R_int = 0.034
2903 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.04	Δρ_max = 0.91 e Å⁻³
2021 reflections	Δρ_min = −0.81 e Å⁻³
136 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.53050 (9)	0.78810 (8)	0.77470 (7)	0.0327 (3)
Cl1	0.7011 (2)	0.53529 (17)	0.80166 (16)	0.0397 (4)
Cl2	0.7438 (2)	0.9433 (2)	0.81435 (18)	0.0476 (4)
N1	0.6029 (6)	0.8157 (6)	0.5531 (5)	0.0341 (11)
N2	0.3090 (6)	0.7056 (6)	0.7282 (5)	0.0347 (11)
N3	0.3644 (7)	0.7751 (6)	0.9746 (5)	0.0357 (11)
H3A	0.4022	0.6933	1.0288	0.043*
H3B	0.3743	0.8597	1.0159	0.043*
C1	0.1667 (9)	0.6172 (9)	0.5489 (7)	0.0527 (18)
H1A	0.0658	0.5872	0.6302	0.079*
H1B	0.2225	0.5283	0.5032	0.079*
H1C	0.1171	0.6883	0.4809	0.079*
C2	0.3123 (8)	0.6909 (7)	0.5987 (6)	0.0343 (13)
C3	0.4844 (8)	0.7519 (7)	0.4929 (6)	0.0326 (13)
C4	0.5180 (9)	0.7429 (8)	0.3465 (6)	0.0427 (15)
H4	0.4342	0.6966	0.3070	0.051*
C5	0.6828 (10)	0.8058 (9)	0.2596 (7)	0.0561 (19)
H5	0.7108	0.8023	0.1601	0.067*
C6	0.8026 (10)	0.8725 (9)	0.3213 (7)	0.0531 (18)
H6	0.9125	0.9155	0.2646	0.064*
C7	0.7586 (9)	0.8752 (7)	0.4685 (7)	0.0416 (15)
H7	0.8408	0.9203	0.5105	0.050*
C8	0.1613 (8)	0.6561 (8)	0.8557 (6)	0.0412 (15)
H8A	0.1867	0.5504	0.8911	0.049*
H8B	0.0381	0.6645	0.8321	0.049*
C9	0.1656 (8)	0.7610 (8)	0.9685 (7)	0.0406 (14)
H9A	0.1095	0.8611	0.9436	0.049*
H9B	0.0931	0.7192	1.0622	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0302 (4)	0.0363 (5)	0.0324 (4)	−0.0047 (3)	−0.0096 (3)	0.0001 (3)
Cl1	0.0404 (8)	0.0339 (8)	0.0412 (8)	0.0017 (6)	−0.0079 (6)	0.0048 (6)
Cl2	0.0403 (9)	0.0487 (10)	0.0580 (10)	−0.0096 (7)	−0.0133 (7)	−0.0145 (8)
N1	0.031 (2)	0.035 (3)	0.033 (3)	−0.004 (2)	−0.007 (2)	0.007 (2)
N2	0.027 (2)	0.053 (3)	0.025 (2)	−0.009 (2)	−0.0086 (19)	0.002 (2)
N3	0.040 (3)	0.033 (3)	0.035 (3)	−0.001 (2)	−0.011 (2)	−0.001 (2)
C1	0.038 (3)	0.081 (5)	0.043 (4)	−0.016 (4)	−0.008 (3)	−0.015 (4)
C2	0.029 (3)	0.037 (3)	0.037 (3)	0.001 (2)	−0.012 (2)	0.001 (3)
C3	0.034 (3)	0.033 (3)	0.031 (3)	−0.002 (2)	−0.010 (2)	0.003 (2)
C4	0.042 (3)	0.051 (4)	0.036 (3)	−0.007 (3)	−0.013 (3)	0.001 (3)
C5	0.057 (4)	0.077 (5)	0.031 (3)	−0.009 (4)	−0.008 (3)	0.008 (3)
C6	0.044 (4)	0.060 (5)	0.047 (4)	−0.015 (3)	−0.003 (3)	0.015 (3)
C7	0.039 (3)	0.038 (3)	0.046 (4)	−0.009 (3)	−0.008 (3)	0.004 (3)
C8	0.033 (3)	0.053 (4)	0.037 (3)	−0.011 (3)	−0.007 (3)	0.001 (3)
C9	0.034 (3)	0.045 (4)	0.040 (3)	0.001 (3)	−0.006 (3)	−0.001 (3)

Geometric parameters (Å, º) top

Cu1—N2	1.977 (5)	C1—H1C	0.9600
Cu1—N3	2.002 (5)	C2—C3	1.498 (8)
Cu1—N1	2.050 (5)	C3—C4	1.376 (8)
Cu1—Cl2	2.2659 (17)	C4—C5	1.396 (9)
Cu1—Cl1	2.4812 (16)	C4—H4	0.9300
N1—C7	1.327 (7)	C5—C6	1.363 (10)
N1—C3	1.333 (7)	C5—H5	0.9300
N2—C2	1.257 (7)	C6—C7	1.372 (9)
N2—C8	1.467 (7)	C6—H6	0.9300
N3—C9	1.475 (7)	C7—H7	0.9300
N3—H3A	0.9000	C8—C9	1.512 (9)
N3—H3B	0.9000	C8—H8A	0.9700
C1—C2	1.479 (8)	C8—H8B	0.9700
C1—H1A	0.9600	C9—H9A	0.9700
C1—H1B	0.9600	C9—H9B	0.9700

N2—Cu1—N3	82.95 (19)	N2—C2—C3	114.1 (5)
N2—Cu1—N1	78.71 (18)	C1—C2—C3	120.6 (5)
N3—Cu1—N1	158.54 (19)	N1—C3—C4	122.8 (5)
N2—Cu1—Cl2	164.66 (16)	N1—C3—C2	114.0 (5)
N3—Cu1—Cl2	96.66 (15)	C4—C3—C2	123.2 (5)
N1—Cu1—Cl2	98.10 (14)	C3—C4—C5	117.5 (6)
N2—Cu1—Cl1	95.01 (16)	C3—C4—H4	121.3
N3—Cu1—Cl1	96.91 (15)	C5—C4—H4	121.3
N1—Cu1—Cl1	95.69 (14)	C6—C5—C4	119.6 (6)
Cl2—Cu1—Cl1	100.26 (6)	C6—C5—H5	120.2
C7—N1—C3	118.8 (5)	C4—C5—H5	120.2
C7—N1—Cu1	127.4 (4)	C5—C6—C7	119.0 (6)
C3—N1—Cu1	113.5 (4)	C5—C6—H6	120.5
C2—N2—C8	126.8 (5)	C7—C6—H6	120.5
C2—N2—Cu1	119.1 (4)	N1—C7—C6	122.4 (6)
C8—N2—Cu1	113.9 (4)	N1—C7—H7	118.8
C9—N3—Cu1	109.9 (4)	C6—C7—H7	118.8
C9—N3—H3A	109.7	N2—C8—C9	106.3 (5)
Cu1—N3—H3A	109.7	N2—C8—H8A	110.5
C9—N3—H3B	109.7	C9—C8—H8A	110.5
Cu1—N3—H3B	109.7	N2—C8—H8B	110.5
H3A—N3—H3B	108.2	C9—C8—H8B	110.5
C2—C1—H1A	109.5	H8A—C8—H8B	108.7
C2—C1—H1B	109.5	N3—C9—C8	108.7 (5)
H1A—C1—H1B	109.5	N3—C9—H9A	109.9
C2—C1—H1C	109.5	C8—C9—H9A	109.9
H1A—C1—H1C	109.5	N3—C9—H9B	109.9
H1B—C1—H1C	109.5	C8—C9—H9B	109.9
N2—C2—C1	125.3 (5)	H9A—C9—H9B	108.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1ⁱ	0.90	2.47	3.248 (5)	145
N3—H3B···Cl2ⁱⁱ	0.90	2.49	3.322 (5)	154
C6—H6···Cl2ⁱⁱⁱ	0.93	2.77	3.666 (7)	161
C4—H4···Cl1^iv	0.93	2.74	3.612 (7)	156
C1—H1A···Cl1^v	0.96	2.80	3.726 (6)	161

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+2, −z+2; (iii) −x+2, −y+2, −z+1; (iv) −x+1, −y+1, −z+1; (v) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₉H₁₃N₃)]
M_r	297.66
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.2701 (10), 8.8008 (12), 9.5773 (15)
α, β, γ (°)	82.940 (2), 76.289 (1), 85.751 (2)
V (Å³)	590.16 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.27
Crystal size (mm)	0.50 × 0.42 × 0.17

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.396, 0.699
No. of measured, independent and observed [I > 2σ(I)] reflections	2903, 2021, 1549
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.160, 1.04
No. of reflections	2021
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.81

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—N2	1.977 (5)	Cu1—Cl2	2.2659 (17)
Cu1—N3	2.002 (5)	Cu1—Cl1	2.4812 (16)
Cu1—N1	2.050 (5)

N3—Cu1—N1	158.54 (19)	N2—Cu1—Cl2	164.66 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1ⁱ	0.90	2.47	3.248 (5)	145.3
N3—H3B···Cl2ⁱⁱ	0.90	2.49	3.322 (5)	154.1
C6—H6···Cl2ⁱⁱⁱ	0.93	2.77	3.666 (7)	160.9
C4—H4···Cl1^iv	0.93	2.74	3.612 (7)	156.1
C1—H1A···Cl1^v	0.96	2.80	3.726 (6)	161.2

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+2, −z+2; (iii) −x+2, −y+2, −z+1; (iv) −x+1, −y+1, −z+1; (v) x−1, y, z.

Acknowledgements

The authors acknowledge financial support by the Shandong Provincial Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University, People's Republic of China.

References

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