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Acta Cryst. (2009). E65, m439    [ doi:10.1107/S1600536809010149 ]

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

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

Abstract top

The title complex, [CuCl2(C9H13N3)], is mononuclear and contains a five-coordinate CuII atom. The geometry of the CuII atom can be described as tetragonal-pyramidal derived from the calculation of the value [tau] = 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.

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 CuII 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.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model, with C—H = 0.90–0.97 Å, and N—H (amino) 0.90 Å, with Uiso(H) =1.2Ueq(C).

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
[Figure 1] Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] 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
Mr = 297.66F(000) = 302
Triclinic, P1Dx = 1.675 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2701 (10) ÅCell parameters from 1739 reflections
b = 8.8008 (12) Åθ = 2.3–27.9°
c = 9.5773 (15) ŵ = 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 tube1549 reflections with I > 2σ(I)
graphiteRint = 0.034
φ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −5→8
Tmin = 0.396, Tmax = 0.699k = −10→10
2903 measured reflectionsl = −9→11
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0888P)2 + 0.8983P]
where P = (Fo2 + 2Fc2)/3
2021 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.91 e Å−3
0 restraintsΔρmin = −0.81 e Å−3
Crystal data top
[CuCl2(C9H13N3)]γ = 85.751 (2)°
Mr = 297.66V = 590.16 (15) Å3
Triclinic, P1Z = 2
a = 7.2701 (10) ÅMo Kα radiation
b = 8.8008 (12) ŵ = 2.27 mm−1
c = 9.5773 (15) ÅT = 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)
Tmin = 0.396, Tmax = 0.699Rint = 0.034
2903 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.160Δρmax = 0.91 e Å−3
S = 1.04Δρmin = −0.81 e Å−3
2021 reflectionsAbsolute structure: ?
136 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cu10.53050 (9)0.78810 (8)0.77470 (7)0.0327 (3)
Cl10.7011 (2)0.53529 (17)0.80166 (16)0.0397 (4)
Cl20.7438 (2)0.9433 (2)0.81435 (18)0.0476 (4)
N10.6029 (6)0.8157 (6)0.5531 (5)0.0341 (11)
N20.3090 (6)0.7056 (6)0.7282 (5)0.0347 (11)
N30.3644 (7)0.7751 (6)0.9746 (5)0.0357 (11)
H3A0.40220.69331.02880.043*
H3B0.37430.85971.01590.043*
C10.1667 (9)0.6172 (9)0.5489 (7)0.0527 (18)
H1A0.06580.58720.63020.079*
H1B0.22250.52830.50320.079*
H1C0.11710.68830.48090.079*
C20.3123 (8)0.6909 (7)0.5987 (6)0.0343 (13)
C30.4844 (8)0.7519 (7)0.4929 (6)0.0326 (13)
C40.5180 (9)0.7429 (8)0.3465 (6)0.0427 (15)
H40.43420.69660.30700.051*
C50.6828 (10)0.8058 (9)0.2596 (7)0.0561 (19)
H50.71080.80230.16010.067*
C60.8026 (10)0.8725 (9)0.3213 (7)0.0531 (18)
H60.91250.91550.26460.064*
C70.7586 (9)0.8752 (7)0.4685 (7)0.0416 (15)
H70.84080.92030.51050.050*
C80.1613 (8)0.6561 (8)0.8557 (6)0.0412 (15)
H8A0.18670.55040.89110.049*
H8B0.03810.66450.83210.049*
C90.1656 (8)0.7610 (8)0.9685 (7)0.0406 (14)
H9A0.10950.86110.94360.049*
H9B0.09310.71921.06220.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0302 (4)0.0363 (5)0.0324 (4)−0.0047 (3)−0.0096 (3)0.0001 (3)
Cl10.0404 (8)0.0339 (8)0.0412 (8)0.0017 (6)−0.0079 (6)0.0048 (6)
Cl20.0403 (9)0.0487 (10)0.0580 (10)−0.0096 (7)−0.0133 (7)−0.0145 (8)
N10.031 (2)0.035 (3)0.033 (3)−0.004 (2)−0.007 (2)0.007 (2)
N20.027 (2)0.053 (3)0.025 (2)−0.009 (2)−0.0086 (19)0.002 (2)
N30.040 (3)0.033 (3)0.035 (3)−0.001 (2)−0.011 (2)−0.001 (2)
C10.038 (3)0.081 (5)0.043 (4)−0.016 (4)−0.008 (3)−0.015 (4)
C20.029 (3)0.037 (3)0.037 (3)0.001 (2)−0.012 (2)0.001 (3)
C30.034 (3)0.033 (3)0.031 (3)−0.002 (2)−0.010 (2)0.003 (2)
C40.042 (3)0.051 (4)0.036 (3)−0.007 (3)−0.013 (3)0.001 (3)
C50.057 (4)0.077 (5)0.031 (3)−0.009 (4)−0.008 (3)0.008 (3)
C60.044 (4)0.060 (5)0.047 (4)−0.015 (3)−0.003 (3)0.015 (3)
C70.039 (3)0.038 (3)0.046 (4)−0.009 (3)−0.008 (3)0.004 (3)
C80.033 (3)0.053 (4)0.037 (3)−0.011 (3)−0.007 (3)0.001 (3)
C90.034 (3)0.045 (4)0.040 (3)0.001 (3)−0.006 (3)−0.001 (3)
Geometric parameters (Å, °) top
Cu1—N21.977 (5)C1—H1C0.9600
Cu1—N32.002 (5)C2—C31.498 (8)
Cu1—N12.050 (5)C3—C41.376 (8)
Cu1—Cl22.2659 (17)C4—C51.396 (9)
Cu1—Cl12.4812 (16)C4—H40.9300
N1—C71.327 (7)C5—C61.363 (10)
N1—C31.333 (7)C5—H50.9300
N2—C21.257 (7)C6—C71.372 (9)
N2—C81.467 (7)C6—H60.9300
N3—C91.475 (7)C7—H70.9300
N3—H3A0.9000C8—C91.512 (9)
N3—H3B0.9000C8—H8A0.9700
C1—C21.479 (8)C8—H8B0.9700
C1—H1A0.9600C9—H9A0.9700
C1—H1B0.9600C9—H9B0.9700
N2—Cu1—N382.95 (19)N2—C2—C3114.1 (5)
N2—Cu1—N178.71 (18)C1—C2—C3120.6 (5)
N3—Cu1—N1158.54 (19)N1—C3—C4122.8 (5)
N2—Cu1—Cl2164.66 (16)N1—C3—C2114.0 (5)
N3—Cu1—Cl296.66 (15)C4—C3—C2123.2 (5)
N1—Cu1—Cl298.10 (14)C3—C4—C5117.5 (6)
N2—Cu1—Cl195.01 (16)C3—C4—H4121.3
N3—Cu1—Cl196.91 (15)C5—C4—H4121.3
N1—Cu1—Cl195.69 (14)C6—C5—C4119.6 (6)
Cl2—Cu1—Cl1100.26 (6)C6—C5—H5120.2
C7—N1—C3118.8 (5)C4—C5—H5120.2
C7—N1—Cu1127.4 (4)C5—C6—C7119.0 (6)
C3—N1—Cu1113.5 (4)C5—C6—H6120.5
C2—N2—C8126.8 (5)C7—C6—H6120.5
C2—N2—Cu1119.1 (4)N1—C7—C6122.4 (6)
C8—N2—Cu1113.9 (4)N1—C7—H7118.8
C9—N3—Cu1109.9 (4)C6—C7—H7118.8
C9—N3—H3A109.7N2—C8—C9106.3 (5)
Cu1—N3—H3A109.7N2—C8—H8A110.5
C9—N3—H3B109.7C9—C8—H8A110.5
Cu1—N3—H3B109.7N2—C8—H8B110.5
H3A—N3—H3B108.2C9—C8—H8B110.5
C2—C1—H1A109.5H8A—C8—H8B108.7
C2—C1—H1B109.5N3—C9—C8108.7 (5)
H1A—C1—H1B109.5N3—C9—H9A109.9
C2—C1—H1C109.5C8—C9—H9A109.9
H1A—C1—H1C109.5N3—C9—H9B109.9
H1B—C1—H1C109.5C8—C9—H9B109.9
N2—C2—C1125.3 (5)H9A—C9—H9B108.3
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···Cl1i0.902.473.248 (5)145
N3—H3B···Cl2ii0.902.493.322 (5)154
C6—H6···Cl2iii0.932.773.666 (7)161
C4—H4···Cl1iv0.932.743.612 (7)156
C1—H1A···Cl1v0.962.803.726 (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.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N21.977 (5)Cu1—Cl22.2659 (17)
Cu1—N32.002 (5)Cu1—Cl12.4812 (16)
Cu1—N12.050 (5)
N3—Cu1—N1158.54 (19)N2—Cu1—Cl2164.66 (16)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···Cl1i0.902.473.248 (5)145
N3—H3B···Cl2ii0.902.493.322 (5)154
C6—H6···Cl2iii0.932.773.666 (7)161
C4—H4···Cl1iv0.932.743.612 (7)156
C1—H1A···Cl1v0.962.803.726 (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.
Acknowledgements top

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
References top

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356.

Coles, S. J., Hursthouse, M. B., Kelly, D. G., Toner, A. J. & Walker, N. M. (1998). J. Chem. Soc. Dalton Trans. pp. 3489–3593.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.