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Acta Cryst. (2008). E64, m559    [ doi:10.1107/S1600536808006934 ]

Chlorido{2-[1-(2-pyridylmethylimino)ethyl]pyrrolato-[kappa]3N,N',N''}copper(II)

R. Li, P. Zhao, G. Tang and Y. Tao

Abstract top

The potential tridentate Schiff base ligand 2-[1-(2-pyridylmethylimino)ethyl]pyrrole (HL) was synthesized from the condensation of 2-acetylpyrrole with 2-aminomethylpyridine. The title compound, [Cu(C12H12N3)Cl], was synthesized from HL and copper(II) chloride using triethylamine as a base to deprotonate the pyrrole NH group. The title compound is a monomer and the central copper(II) ion is bound to three N atoms of the deprotonated tridentate ligand and to one chloride ion in a square-planar N3Cl coordination.

Comment top

Many efforts have been made to investigate complexes of wide range of acyclic Schiff base ligands, in particular the pyridine containing systems. However, Much less interest has been attracted in complexes of pyrrole-analogues of such ligands. Recently, our attention has been turned to the copper(II) chemistry of N3 tridentate Schiff base ligands. Ligand L-, the deprotonated form of HL, used for the synthesis of the title complex is of this type.

The structure of the title compound consists of isolated neutral monomeric [CuLCl] molecules (Fig. 1). The copper(II) ion is bound to three nitrogen atoms (comprised of one deprotonated pyrrole nitrogen donor, one pyridine nitrogen donor and one imine nitrogen donor) of the deprotonated tridentate ligand and to one chloride ion, giving an N3Cl coordination sphere. The geometry of the coordination polyhedron around the copper(II) ion is square planar (Σangles at Cu = 360.0°). Of the three Cu—N bond distances, the shortest one occurs between the copper atom and the deprotonated negatively charged pyrrole nitrogen atom (N1—Cu1) and the longest one forms between the copper atom and the pyridine nitrogen donor which is trans to the pyrrole nitrogen (Cu1—N3). The two cis N—Cu—N angles are very similar and are both smaller than 90°. This is as expected as both of the angles are part of five-membered, pyrrole-imine or pyridine-imine, chelate rings. The two cis N—Cu—Cl angles are similar to one another but are both bigger than a right angle. The Cu—N1 (pyrrole nitrogen) bond distance is very similar to that reported for the related copper(II) complexes (Bertrand & Kirkwood, 1972; Brooker & Carter, 1995). Cu—N (pyridine nitrogen) bonds are usually 2.00–2.05 Å long (Brown et al., 1988; Garland et al., 1996), so the Cu—N3 (pyridine nitrogen) distance in this complex [2.007 (4) Å] is normal.

Related literature top

For related literature, see: Bertrand & Kirkwood (1972); Brooker & Carter (1995); Brown et al. (1988); Garland et al. (1996).

Experimental top

Ligand HL was synthesized from the condensation of 2-acetylpyrrole with 2-aminomethylpyridine.

To a solution of Ligand HL (0.375 mmol) in methanol (5 ml) was added triethylamine (0.385 mmol) in methanol (5 ml). To this resulting solution was added a green solution of copper(II) chloride dihydrate (0.375 mmol) in methanol (5 ml), over which time a precipitate formed. The resulting mixture was stirred for 3 hr after which the green solid was collected by filtration, washed with methanol and dried in vacuo. Yield: 0.093 g (80% based on copper(II) chloride used). Single crystals of [CuLCl] were obtained by vapour diffusion of diethyl ether into a dichloromethane solution. Analysis: found C 48.74, H 3.97, N 14.18; calculated for C12H12N3CuCl C 48.49, H 4.07, N, 14.14%. IR: ν, cm-1, 1601 (C?N).

Refinement top

Hydrogen atoms were positioned geometrically and refined using a riding model, with C—H bonds = 0.93–0.97 Å and with Uiso (H) = 1.2Ueq (C) [1.5Ueq (C) for the methyl group].

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the title compound [CuLCl]. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
[Figure 2] Fig. 2. View of the crystal packing along b axis of the unit cell of the monomeric title complex [CuLCl].
Chlorido{2-[1-(2-pyridylmethylimino)ethyl]pyrrolato-κ3N,N',N''}copper(II) top
Crystal data top
[Cu(C12H12N3)Cl]F000 = 604
Mr = 297.24Dx = 1.666 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71070 Å
Hall symbol: -P 2ybcCell parameters from 3740 reflections
a = 8.830 (2) Åθ = 2.1–25.6º
b = 7.2806 (15) ŵ = 2.05 mm−1
c = 18.750 (4) ÅT = 213 (2) K
β = 100.448 (4)ºBlock, green
V = 1185.4 (4) Å30.24 × 0.18 × 0.16 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		2164 independent reflections
Radiation source: sealed tube1840 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
T = 213(2) Kθmax = 25.4º
φ and ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −10→10
Tmin = 0.642, Tmax = 0.719k = −7→8
11059 measured reflectionsl = −22→22
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.124  w = 1/[σ2(Fo2) + (0.06P)2 + 1.99P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2164 reflectionsΔρmax = 0.38 e Å−3
156 parametersΔρmin = −0.43 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C12H12N3)Cl]V = 1185.4 (4) Å3
Mr = 297.24Z = 4
Monoclinic, P21/cMo Kα
a = 8.830 (2) ŵ = 2.05 mm−1
b = 7.2806 (15) ÅT = 213 (2) K
c = 18.750 (4) Å0.24 × 0.18 × 0.16 mm
β = 100.448 (4)º
Data collection top
Bruker SMART APEX CCD
diffractometer		2164 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1840 reflections with I > 2σ(I)
Tmin = 0.642, Tmax = 0.719Rint = 0.045
11059 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.049156 parameters
wR(F2) = 0.124H-atom parameters constrained
S = 1.05Δρmax = 0.38 e Å−3
2164 reflectionsΔρmin = −0.43 e Å−3
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
Cu10.50155 (6)0.79633 (7)0.42653 (3)0.0312 (2)
Cl10.64180 (13)0.80713 (16)0.33884 (6)0.0431 (3)
N10.6561 (4)0.6909 (5)0.5025 (2)0.0378 (9)
N20.3797 (4)0.7939 (5)0.50388 (19)0.0331 (8)
N30.3055 (4)0.9028 (5)0.37105 (17)0.0303 (8)
C10.8039 (6)0.6345 (6)0.5150 (3)0.0479 (12)
H10.86850.63600.48100.057*
C20.8452 (7)0.5741 (8)0.5857 (3)0.0648 (16)
H20.94120.52910.60730.078*
C30.7176 (7)0.5928 (7)0.6184 (3)0.0593 (15)
H30.71070.56260.66590.071*
C40.6022 (6)0.6658 (6)0.5659 (2)0.0423 (11)
C50.4452 (6)0.7218 (6)0.5646 (2)0.0413 (11)
C60.2223 (5)0.8562 (6)0.4865 (2)0.0374 (10)
H6A0.20820.96290.51560.045*
H6B0.15340.76010.49700.045*
C70.1863 (5)0.9048 (6)0.4073 (2)0.0327 (9)
C80.0406 (5)0.9525 (7)0.3731 (3)0.0434 (12)
H8−0.04100.94850.39820.052*
C90.0156 (6)1.0060 (7)0.3019 (3)0.0514 (13)
H9−0.08291.03740.27830.062*
C100.1382 (6)1.0128 (7)0.2655 (3)0.0471 (12)
H100.12491.05340.21780.057*
C110.2804 (5)0.9580 (6)0.3018 (2)0.0371 (10)
H110.36280.95930.27710.045*
C120.3689 (7)0.6982 (7)0.6292 (3)0.0551 (14)
H12A0.29950.79870.63150.083*
H12B0.44580.69600.67250.083*
H12C0.31240.58490.62490.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0315 (3)0.0342 (3)0.0282 (3)−0.0016 (2)0.0058 (2)0.0003 (2)
Cl10.0374 (6)0.0497 (7)0.0463 (7)0.0016 (5)0.0183 (5)0.0013 (5)
N10.038 (2)0.032 (2)0.039 (2)−0.0039 (16)−0.0028 (17)0.0009 (16)
N20.044 (2)0.0289 (18)0.0278 (19)−0.0009 (16)0.0090 (16)−0.0006 (15)
N30.0331 (18)0.0318 (18)0.0275 (18)−0.0058 (16)0.0094 (15)−0.0027 (15)
C10.043 (3)0.037 (3)0.057 (3)−0.003 (2)−0.010 (2)−0.007 (2)
C20.065 (4)0.051 (3)0.064 (4)0.008 (3)−0.028 (3)−0.009 (3)
C30.094 (4)0.035 (3)0.036 (3)0.005 (3)−0.022 (3)−0.002 (2)
C40.066 (3)0.025 (2)0.032 (2)−0.003 (2)−0.003 (2)−0.0036 (18)
C50.066 (3)0.025 (2)0.034 (2)−0.008 (2)0.010 (2)−0.0033 (19)
C60.045 (3)0.036 (2)0.037 (2)−0.005 (2)0.021 (2)−0.001 (2)
C70.038 (2)0.031 (2)0.031 (2)−0.0075 (19)0.0108 (18)−0.0060 (19)
C80.033 (2)0.050 (3)0.048 (3)−0.004 (2)0.011 (2)−0.005 (2)
C90.036 (3)0.057 (3)0.056 (3)0.006 (2)−0.003 (2)−0.009 (3)
C100.053 (3)0.053 (3)0.031 (2)−0.003 (2)−0.002 (2)−0.002 (2)
C110.034 (2)0.047 (3)0.031 (2)−0.004 (2)0.0074 (19)−0.005 (2)
C120.094 (4)0.042 (3)0.032 (3)−0.005 (3)0.018 (3)0.004 (2)
Geometric parameters (Å, °) top
Cu1—N11.943 (4)C4—C51.441 (7)
Cu1—N21.956 (3)C5—C121.499 (7)
Cu1—N32.006 (3)C6—C71.503 (6)
Cu1—Cl12.2319 (12)C6—H6A0.9700
N1—C11.347 (6)C6—H6B0.9700
N1—C41.370 (6)C7—C81.374 (6)
N2—C51.291 (6)C8—C91.369 (7)
N2—C61.442 (6)C8—H80.9300
N3—C111.339 (5)C9—C101.381 (7)
N3—C71.354 (5)C9—H90.9300
C1—C21.381 (7)C10—C111.374 (6)
C1—H10.9300C10—H100.9300
C2—C31.384 (8)C11—H110.9300
C2—H20.9300C12—H12A0.9600
C3—C41.388 (7)C12—H12B0.9600
C3—H30.9300C12—H12C0.9600
N1—Cu1—N281.98 (16)C4—C5—C12121.7 (4)
N1—Cu1—N3163.31 (15)N2—C6—C7108.7 (3)
N2—Cu1—N381.33 (14)N2—C6—H6A110.0
N1—Cu1—Cl198.29 (12)C7—C6—H6A110.0
N2—Cu1—Cl1178.47 (10)N2—C6—H6B110.0
N3—Cu1—Cl198.40 (10)C7—C6—H6B110.0
C1—N1—C4106.6 (4)H6A—C6—H6B108.3
C1—N1—Cu1141.0 (4)N3—C7—C8121.0 (4)
C4—N1—Cu1112.4 (3)N3—C7—C6116.7 (4)
C5—N2—C6125.9 (4)C8—C7—C6122.3 (4)
C5—N2—Cu1116.0 (3)C9—C8—C7119.9 (4)
C6—N2—Cu1117.8 (3)C9—C8—H8120.0
C11—N3—C7118.5 (4)C7—C8—H8120.0
C11—N3—Cu1126.5 (3)C8—C9—C10119.3 (5)
C7—N3—Cu1114.8 (3)C8—C9—H9120.3
N1—C1—C2110.1 (5)C10—C9—H9120.3
N1—C1—H1125.0C11—C10—C9118.2 (5)
C2—C1—H1125.0C11—C10—H10120.9
C1—C2—C3107.4 (5)C9—C10—H10120.9
C1—C2—H2126.3N3—C11—C10122.9 (4)
C3—C2—H2126.3N3—C11—H11118.6
C2—C3—C4105.9 (5)C10—C11—H11118.6
C2—C3—H3127.0C5—C12—H12A109.5
C4—C3—H3127.0C5—C12—H12B109.5
N1—C4—C3109.9 (5)H12A—C12—H12B109.5
N1—C4—C5115.6 (4)C5—C12—H12C109.5
C3—C4—C5134.5 (5)H12A—C12—H12C109.5
N2—C5—C4113.9 (4)H12B—C12—H12C109.5
N2—C5—C12124.3 (5)
Table 1
Selected geometric parameters (Å, °) top
Cu1—N11.943 (4)Cu1—N32.006 (3)
Cu1—N21.956 (3)Cu1—Cl12.2319 (12)
N1—Cu1—N281.98 (16)N1—Cu1—Cl198.29 (12)
N1—Cu1—N3163.31 (15)N2—Cu1—Cl1178.47 (10)
N2—Cu1—N381.33 (14)N3—Cu1—Cl198.40 (10)
Acknowledgements top

This work was supported by the Natural Science Foundation of the Department of Education of Jiangsu Province (No. 05KJD150037) and Jiangsu Key Laboratory for the Chemistry of Low-Dimensional Materials (No. JSKC06025).

references
References top

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Brown, S. J., Tao, X., Wark, T. A., Stephan, D. W. & Mascharak, P. K. (1988). Inorg. Chem. 27, 1581–1587.

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Garland, M. T., Manzur, J., Moreno, Y., Spodine, E., Baggio, R. & González, O. (1996). Acta Cryst. C52, 1405–1407.

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