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Acta Cryst. (2008). E64, m1228    [ doi:10.1107/S160053680802758X ]

(1H-Imidazole-[kappa]N3){N-[1-(2-oxidophenyl-[kappa]O)ethylidene]-L-phenylalaninato-[kappa]2N,O}copper(II)

Y.-J. Han, G.-Q. Zhao, X.-J. Zhao, W.-L. Song and J.-L. Shi

Abstract top

In the title compound, [Cu(C17H15NO3)(C3H4N2)], the CuII atom is four-coordinated by two O atoms and the N atom of the tridentate Schiff base ligand, and one N atom from the imidazole ligand in a distorted square-planar geometry. In the crystal structure, molecules are linked into dimers by intermolecular N-H...O hydrogen bonds.

Comment top

In the past decades, significant progress has been achieved in understanding the chemistry of transition metal complexes with Schiff base ligands composed of salicylaldehyde, 2-formylpyridine or their analogues, and α-amino acids (Vigato & Tamburini, 2004; Ganguly et al., 2008; Casella & Guillotti, 1983). A few stuctural studies have been performed on Schiff base complexes derived from 2-hydroxyacetophenone and animo acids (Usman et al., 2003; Basu Baul et al., 2007; Parekh et al., 2006). We report here the crystal structure of the title CuII complex.

The structure consists of discrete monomeric square-planar CuIIcomplex (Fig. 1 and Table 1). The four basal positions are occupied by three donor atoms from the tridentate Schiff base ligand, which furnishes an ONO donor set, with the fourth position occupied by one N atom from the imidazole ligand. The nitrogen heterocycle is planar and it forms an angle of 14.7 (2)° with the C1—C6 ring.

The crystal structure is stabilized by N—H···O type hydrogen bonds (Fig. 2 and Table 2). The H atom attached to N3 is hydrogen-bonded to the neighboring carboxylate oxygen O2 to form a dimer.

Related literature top

For related literature, see: Basu Baul et al. (2007); Casella & Guillotti (1983); Ganguly et al. (2008); Parekh et al. (2006); Plesch et al. (1997); Usman et al. (2003); Vigato & Tamburini (2004).

Experimental top

The title compound was synthesized as described in the literature (Plesch et al., 1997). To L-phenylalanine (1.00 mmol) and potassium hydroxide (1.00 mmol) in 10 ml of methanol was added 2-hydroxyacetophenone (1.00 mmol in 10 ml of methanol) dropwise. The yellow solution was stirred for 2 h at 333 K. The resultant mixture was added dropwise to copper(II) acetate monohydrate (1.00 mmol) and imidazole (1.00 mmol) in an aqueous methanol solution (20 ml, 1:1 v/v), and heated with stirring for 2 h at 333 K. The dark blue solution was filtered and left for several days; the resulting dark blue crystals were filtered off, washed with water, and dried under vacuum.

Refinement top

All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH) or 0.97 Å (CH2) and Uiso(H) = 1.2Ueq(C), C—H = 0.96 Å (CH3) and Uiso(H) = 1.5Ueq(C), and with N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. A view of the crystal packing along the c axis. Hydrogen bonds are shown as dashed lines.
(1H-Imidazole-κN3){N-[1-(2-oxidophenyl-κO)ethylidene]-L- phenylalaninato-κ2N,O}copper(II) top
Crystal data top
[Cu(C17H15NO3)(C3H4N2)]F(000) = 1704
Mr = 412.92Dx = 1.449 Mg m−3
Orthorhombic, C2221Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2Cell parameters from 3925 reflections
a = 16.8029 (16) Åθ = 2.4–23.2°
b = 19.8231 (19) ŵ = 1.18 mm−1
c = 11.3642 (11) ÅT = 291 K
V = 3785.3 (6) Å3Block, dark blue
Z = 80.43 × 0.34 × 0.25 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3534 independent reflections
Radiation source: fine-focus sealed tube3008 reflections with I > 2σ(I)
graphiteRint = 0.027
φ and ω scansθmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→16
Tmin = 0.630, Tmax = 0.759k = −24→23
10101 measured reflectionsl = −13→13
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)] = 0.028H-atom parameters constrained
wR(F2) = 0.067 w = 1/[σ2(Fo2) + (0.0324P)2 + 1.1795P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
3534 reflectionsΔρmax = 0.21 e Å−3
245 parametersΔρmin = −0.16 e Å−3
0 restraintsAbsolute structure: Flack (1983), 1557 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.029 (12)
Crystal data top
[Cu(C17H15NO3)(C3H4N2)]V = 3785.3 (6) Å3
Mr = 412.92Z = 8
Orthorhombic, C2221Mo Kα radiation
a = 16.8029 (16) ŵ = 1.18 mm−1
b = 19.8231 (19) ÅT = 291 K
c = 11.3642 (11) Å0.43 × 0.34 × 0.25 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3534 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3008 reflections with I > 2σ(I)
Tmin = 0.630, Tmax = 0.759Rint = 0.027
10101 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.067Δρmax = 0.21 e Å−3
S = 1.01Δρmin = −0.16 e Å−3
3534 reflectionsAbsolute structure: Flack (1983), 1557 Friedel pairs
245 parametersFlack parameter: −0.029 (12)
0 restraints
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
Cu10.10619 (2)0.367615 (16)0.77896 (3)0.04364 (11)
N10.13985 (13)0.27457 (10)0.80032 (19)0.0406 (5)
N20.10665 (16)0.46531 (10)0.75384 (17)0.0459 (5)
N30.13752 (15)0.57138 (11)0.7787 (3)0.0547 (6)
H3D0.15440.60780.81150.066*
O10.05861 (14)0.34996 (10)0.63167 (17)0.0624 (6)
O20.20326 (14)0.32527 (10)1.08596 (17)0.0577 (6)
O30.14173 (11)0.37985 (8)0.94100 (15)0.0470 (5)
C10.04519 (18)0.29043 (15)0.5868 (2)0.0485 (7)
C20.06894 (17)0.22761 (15)0.6360 (2)0.0461 (7)
C30.0429 (2)0.16858 (17)0.5793 (3)0.0615 (9)
H30.05640.12710.61170.074*
C4−0.0015 (2)0.1697 (2)0.4781 (4)0.0778 (11)
H4−0.01920.12960.44470.093*
C5−0.0197 (2)0.2304 (2)0.4260 (3)0.0704 (10)
H5−0.04750.23120.35530.084*
C60.0028 (2)0.28950 (16)0.4780 (3)0.0585 (8)
H6−0.00980.33010.44160.070*
C70.11970 (16)0.22199 (12)0.7394 (2)0.0444 (7)
C80.15118 (19)0.15280 (12)0.7715 (3)0.0580 (8)
H8A0.19010.15700.83280.087*
H8B0.17530.13250.70350.087*
H8C0.10810.12500.79840.087*
C90.19625 (17)0.27141 (13)0.8989 (2)0.0454 (7)
H90.18970.22840.94040.054*
C100.17829 (18)0.32911 (13)0.9830 (2)0.0439 (7)
C110.28234 (18)0.27726 (15)0.8539 (3)0.0563 (8)
H11A0.31850.27380.92010.068*
H11B0.29330.23980.80140.068*
C120.29811 (17)0.34248 (14)0.7897 (3)0.0520 (7)
C130.2807 (2)0.34864 (17)0.6704 (3)0.0656 (10)
H130.26060.31170.62960.079*
C140.2928 (3)0.4089 (2)0.6120 (3)0.0845 (12)
H140.28130.41220.53210.101*
C150.3216 (3)0.4640 (2)0.6713 (4)0.0921 (13)
H150.32920.50470.63210.110*
C160.3390 (3)0.45879 (18)0.7879 (5)0.0925 (14)
H160.35890.49600.82810.111*
C170.3274 (2)0.39883 (19)0.8466 (4)0.0814 (11)
H170.33960.39620.92630.098*
C180.13541 (19)0.51078 (14)0.8262 (3)0.0560 (9)
H180.15240.50130.90240.067*
C190.1082 (2)0.56540 (16)0.6691 (3)0.0731 (10)
H190.10250.59980.61400.088*
C200.0885 (2)0.49998 (17)0.6544 (3)0.0708 (11)
H200.06600.48160.58680.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0632 (2)0.03698 (15)0.03072 (15)0.00253 (17)−0.00760 (17)−0.00122 (14)
N10.0497 (13)0.0383 (11)0.0339 (13)0.0008 (10)0.0026 (10)−0.0022 (9)
N20.0637 (15)0.0421 (11)0.0319 (12)0.0013 (11)−0.0068 (12)0.0016 (9)
N30.0760 (18)0.0383 (12)0.0498 (14)0.0005 (11)−0.0040 (14)0.0027 (12)
O10.0910 (16)0.0539 (14)0.0424 (11)−0.0013 (11)−0.0241 (11)−0.0035 (10)
O20.0849 (16)0.0513 (12)0.0368 (10)0.0122 (11)−0.0180 (11)0.0010 (9)
O30.0702 (13)0.0376 (10)0.0333 (10)0.0094 (9)−0.0094 (8)−0.0010 (8)
C10.0508 (18)0.0605 (19)0.0342 (15)−0.0049 (15)0.0044 (13)−0.0126 (14)
C20.0489 (18)0.0522 (17)0.0374 (15)−0.0067 (14)0.0086 (13)−0.0135 (13)
C30.062 (2)0.0598 (19)0.062 (2)−0.0079 (16)0.0073 (17)−0.0249 (17)
C40.070 (2)0.084 (2)0.080 (3)−0.017 (2)−0.001 (2)−0.039 (2)
C50.057 (2)0.109 (3)0.046 (2)−0.010 (2)−0.0005 (17)−0.030 (2)
C60.0519 (19)0.084 (2)0.0400 (19)−0.0024 (19)0.0000 (13)−0.0078 (18)
C70.0538 (18)0.0392 (13)0.0400 (16)−0.0032 (12)0.0140 (13)−0.0051 (11)
C80.078 (2)0.0403 (15)0.0562 (18)0.0001 (13)0.0123 (18)−0.0059 (15)
C90.0586 (19)0.0357 (14)0.0419 (15)0.0043 (13)−0.0051 (14)0.0034 (12)
C100.0550 (19)0.0377 (15)0.0391 (15)−0.0003 (13)−0.0068 (14)0.0017 (12)
C110.056 (2)0.0505 (18)0.063 (2)0.0117 (15)−0.0050 (16)−0.0008 (16)
C120.0463 (18)0.0467 (16)0.063 (2)0.0048 (13)0.0034 (17)0.0049 (16)
C130.082 (3)0.061 (2)0.0542 (19)−0.0013 (17)0.0195 (18)−0.0042 (16)
C140.115 (3)0.079 (3)0.059 (2)−0.003 (2)0.022 (2)0.009 (2)
C150.111 (4)0.065 (3)0.100 (3)−0.008 (2)0.013 (3)0.018 (2)
C160.116 (4)0.055 (2)0.107 (4)−0.026 (2)−0.029 (3)0.010 (2)
C170.087 (3)0.073 (2)0.084 (3)−0.011 (2)−0.027 (2)0.009 (2)
C180.088 (3)0.0427 (16)0.0375 (16)0.0023 (15)−0.0107 (15)0.0019 (13)
C190.108 (3)0.0540 (19)0.057 (2)−0.002 (2)−0.013 (2)0.0230 (16)
C200.115 (3)0.0569 (19)0.0401 (17)−0.004 (2)−0.025 (2)0.0128 (15)
Geometric parameters (Å, °) top
Cu1—O11.8876 (19)C7—C81.514 (4)
Cu1—N11.945 (2)C8—H8A0.96
Cu1—O31.9511 (18)C8—H8B0.96
Cu1—N21.958 (2)C8—H8C0.96
N1—C71.296 (3)C9—C101.520 (4)
N1—C91.469 (3)C9—C111.539 (4)
N2—C181.312 (4)C9—H90.98
N2—C201.358 (4)C11—C121.508 (4)
N3—C181.317 (4)C11—H11A0.97
N3—C191.346 (4)C11—H11B0.97
N3—H3D0.86C12—C171.381 (4)
O1—C11.305 (3)C12—C131.392 (4)
O2—C101.246 (3)C13—C141.383 (5)
O3—C101.271 (3)C13—H130.93
C1—C21.422 (4)C14—C151.371 (6)
C1—C61.427 (4)C14—H140.93
C2—C31.405 (4)C15—C161.361 (6)
C2—C71.457 (4)C15—H150.93
C3—C41.371 (5)C16—C171.377 (5)
C3—H30.93C16—H160.93
C4—C51.376 (5)C17—H170.93
C4—H40.93C18—H180.93
C5—C61.365 (4)C19—C201.349 (4)
C5—H50.93C19—H190.93
C6—H60.93C20—H200.93
O1—Cu1—N193.33 (9)H8B—C8—H8C109.5
O1—Cu1—O3171.74 (9)N1—C9—C10108.6 (2)
N1—Cu1—O384.90 (8)N1—C9—C11110.4 (2)
O1—Cu1—N293.20 (9)C10—C9—C11109.8 (2)
N1—Cu1—N2162.84 (10)N1—C9—H9109.3
O3—Cu1—N290.77 (8)C10—C9—H9109.3
C7—N1—C9122.8 (2)C11—C9—H9109.3
C7—N1—Cu1128.33 (19)O2—C10—O3124.3 (3)
C9—N1—Cu1108.86 (16)O2—C10—C9118.5 (2)
C18—N2—C20104.9 (2)O3—C10—C9117.1 (2)
C18—N2—Cu1126.11 (19)C12—C11—C9113.0 (2)
C20—N2—Cu1128.4 (2)C12—C11—H11A109.0
C18—N3—C19106.8 (3)C9—C11—H11A109.0
C18—N3—H3D126.6C12—C11—H11B109.0
C19—N3—H3D126.6C9—C11—H11B109.0
C1—O1—Cu1125.97 (19)H11A—C11—H11B107.8
C10—O3—Cu1113.79 (16)C17—C12—C13117.4 (3)
O1—C1—C2126.1 (3)C17—C12—C11122.0 (3)
O1—C1—C6115.9 (3)C13—C12—C11120.6 (3)
C2—C1—C6118.0 (3)C14—C13—C12120.8 (3)
C3—C2—C1117.5 (3)C14—C13—H13119.6
C3—C2—C7119.2 (3)C12—C13—H13119.6
C1—C2—C7123.3 (2)C15—C14—C13120.2 (4)
C4—C3—C2122.7 (4)C15—C14—H14119.9
C4—C3—H3118.6C13—C14—H14119.9
C2—C3—H3118.6C16—C15—C14119.6 (4)
C3—C4—C5119.7 (3)C16—C15—H15120.2
C3—C4—H4120.1C14—C15—H15120.2
C5—C4—H4120.1C15—C16—C17120.4 (4)
C6—C5—C4120.2 (3)C15—C16—H16119.8
C6—C5—H5119.9C17—C16—H16119.8
C4—C5—H5119.9C16—C17—C12121.5 (4)
C5—C6—C1121.6 (3)C16—C17—H17119.3
C5—C6—H6119.2C12—C17—H17119.3
C1—C6—H6119.2N2—C18—N3112.3 (3)
N1—C7—C2121.5 (2)N2—C18—H18123.9
N1—C7—C8120.6 (3)N3—C18—H18123.9
C2—C7—C8117.9 (2)N3—C19—C20106.8 (3)
C7—C8—H8A109.5N3—C19—H19126.6
C7—C8—H8B109.5C20—C19—H19126.6
H8A—C8—H8B109.5C19—C20—N2109.2 (3)
C7—C8—H8C109.5C19—C20—H20125.4
H8A—C8—H8C109.5N2—C20—H20125.4
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3D···O2i0.861.952.789 (3)166
Symmetry codes: (i) x, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.8876 (19)Cu1—O31.9511 (18)
Cu1—N11.945 (2)Cu1—N21.958 (2)
O1—Cu1—N193.33 (9)O1—Cu1—N293.20 (9)
O1—Cu1—O3171.74 (9)N1—Cu1—N2162.84 (10)
N1—Cu1—O384.90 (8)O3—Cu1—N290.77 (8)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3D···O2i0.861.952.789 (3)166
Symmetry codes: (i) x, −y+1, −z+2.
Acknowledgements top

This research was supported by the National Science Foundation of China (grant No. 20676057).

references
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