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Acta Cryst. (2008). E64, m660-m661    [ doi:10.1107/S160053680800932X ]

{2-[(3,5-Dichloro-2-oxidobenzylidene)amino-[kappa]2N,O]-3-methylpentanoato-[kappa]O}(N,N'-dimethylformamide-[kappa]O)copper(II)

J. H. Xia, Z. Liu, Y. Wang and X. Z. Feng

Abstract top

In the title compound, [Cu(C13H13Cl2NO3)(C3H7NO)], the CuII atom is coordinated in a slightly distorted square-planar geometry by two O atoms and one N atom from the tridentate chiral ligand 2-[(3,5-dichloro-2-oxidobenzylidene)amino]-3-methylpentanoate and by one O atom from dimethylformamide. In the crystal structure, the Cu atom forms contacts with Cl and O atoms of two units (Cu...Cl and Cu...O = 3.401 and 2.947 Å, respectively), thereby forming an approximately octahedral arrangement. A three-dimensional network is constructed through Cl...Cu, O...Cu, Cl...Cl contacts and C-H...O hydrogen bonds.

Comment top

Schiff bases is a kind of very important compounds in coordination chemistry. And Schiff base complexes have been increasing interest because of their antivial,anticancer and antibacterial activities.Just as the title compound, it's amino acid salicylicaldehyde of halogen substituent Schiff base. Meanwhile,we find some unusual bonds which look like hydrogen bond in this halogenated compound.

In (I),the CuII atom is coordinated by two O atoms, one N atom, which come from one tridentate ligand 2-[(3,5-dichloro-2-oxidobenzylidene)amino]-3-methylpentanoate and one O atom from N,N-Dimethyl-formamide, forming a slightly distorted planar square geometry (Fig. 1). In the unit one-dimensional chains, the distorted planar square with Cl and O which above or below of it form an approximately "octahedral". The weak interaction length of Cl–Cu and O–Cu is 3.401 Å. and 2.947 Å. These can be seen the reasults of Jahn-Teller effect. (Garcia-Orozco et al., 2002) People have interest in packing arrangements of halogenated compounds date back to what Schmidt called the 'chloro effect', where the presence of chloro substituents on aromatic compounds frequently arise from stacking arrangements with a short (ca 4 Å) crystallographic axis (Cohen et al., 1964; Zaman et al., 2004; Zordan et al., 2005). The title compound contains the dichloride ligand 2-[(3,5-dichloro-2-oxidobenzylidene)amino]-3-methylpentanoate, with two Cl atoms accessible at the periphery of the ligand. The three-dimensional network of (I) through short Cl–Cu, Cl–Cl, O–Cu contacts and C–H···O hydrogen bonds.(Fig.3). The weak interaction length of Cl–Cl is 3.349 Å. The final position parameters of the nonhydrogen atoms are given in Table 1. The selected bond lengths and bond angles are listed in Table 2.

Related literature top

For Schiff base complexes containing amino acids, see: Garcia-Raso et al. (1996); Dawes et al. (1982); Laurent et al. (1982); Zhang et al. (2006). For related literature, see: Cohen et al. (1964); Garcia-Orozco, Tapia-Benavides & Alvarez-Toledano (2002); Hu & Ulli Englert (2006); Royles & Sherrington (2000); Subramanian et al. (2000); Zaman et al. (2004); Zordan et al. (2005).

Experimental top

The title compound was produced from aqueous solution of copper chloride and A ethanol solution of (E)-2-(3,5-dichloro-2-hydroxybenzylideneamino)-3 -methylpentanoic acid with vapour volatilization of N,N-Dimethyl-formamide at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 asymmetric unit of (I), showing 30% probability displacement ellipsoids. Carbon-bound H atoms have been omitted.
[Figure 2] Fig. 2. The interactions of Cl···Cu and O···Cu in the asymmetric unit one-dimensional chains.
[Figure 3] Fig. 3. Three-dimensional network of (I), broken line showing Short Cl–Cl, Cl···Cu and O···Cu contacts, C–H···O hydrogen bonds.
{2-[(3,5-Dichloro-2-oxidobenzylidene)amino-κ2N,O]-3-methylpentanoato- κO}(N,N'-dimethylformamide-κO)copper(II) top
Crystal data top
[Cu(C13H13Cl2NO3)(C3H7NO)]Dx = 1.544 Mg m−3
Mr = 438.78Mo Kα radiation
λ = 0.71073 Å
Orthorhombic, P21212Cell parameters from 1991 reflections
a = 11.671 (2) Åθ = 2.3–20.3º
b = 27.465 (3) ŵ = 1.46 mm−1
c = 5.8890 (18) ÅT = 298 (2) K
V = 1887.7 (7) Å3Block, blue
Z = 40.43 × 0.15 × 0.13 mm
F000 = 900
Data collection top
Bruker SMART CCD area-detector
diffractometer		3260 independent reflections
Radiation source: fine-focus sealed tube2288 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.087
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 1.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→13
Tmin = 0.572, Tmax = 0.833k = −32→32
9274 measured reflectionsl = −6→6
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.095  w = 1/[σ2(Fo2) + (0.1179P)2 + 7.0901P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.242(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.54 e Å−3
3260 reflectionsΔρmin = −1.08 e Å−3
226 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1310 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.11 (6)
Crystal data top
[Cu(C13H13Cl2NO3)(C3H7NO)]V = 1887.7 (7) Å3
Mr = 438.78Z = 4
Orthorhombic, P21212Mo Kα
a = 11.671 (2) ŵ = 1.46 mm−1
b = 27.465 (3) ÅT = 298 (2) K
c = 5.8890 (18) Å0.43 × 0.15 × 0.13 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3260 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2288 reflections with I > 2σ(I)
Tmin = 0.572, Tmax = 0.833Rint = 0.087
9274 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.095H-atom parameters constrained
wR(F2) = 0.242Δρmax = 0.54 e Å−3
S = 1.05Δρmin = −1.08 e Å−3
3260 reflectionsAbsolute structure: Flack (1983), 1310 Friedel pairs
226 parametersFlack parameter: 0.11 (6)
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
Cu10.13255 (12)0.88233 (5)0.7191 (3)0.0369 (4)
Cl10.0068 (3)0.79870 (13)0.0644 (6)0.0481 (9)
Cl20.2946 (3)0.65124 (12)0.2389 (8)0.0671 (12)
N10.2606 (8)0.8445 (3)0.8257 (17)0.033 (2)
N2−0.1115 (10)0.9551 (4)0.3728 (17)0.043 (3)
O10.1585 (7)0.9174 (3)0.9935 (17)0.046 (2)
O20.2565 (10)0.9193 (4)1.3185 (19)0.063 (3)
O30.0957 (7)0.8388 (3)0.4856 (18)0.044 (2)
O40.0063 (7)0.9243 (3)0.6463 (15)0.039 (2)
C10.2446 (12)0.9026 (5)1.125 (2)0.038 (3)
C20.3198 (12)0.8638 (4)1.029 (2)0.035 (3)
H20.32940.83771.14110.042*
C30.4373 (11)0.8833 (7)0.960 (3)0.059 (4)
H30.47620.85840.86870.071*
C40.5115 (15)0.8947 (7)1.168 (3)0.067 (5)
H4A0.58740.90391.11620.080*
H4B0.47890.92261.24570.080*
C50.5232 (16)0.8529 (7)1.338 (3)0.077 (5)
H5A0.46510.85591.45230.115*
H5B0.59740.85421.40760.115*
H5C0.51450.82241.26000.115*
C60.4285 (13)0.9300 (7)0.818 (3)0.077 (6)
H6A0.37010.92610.70440.116*
H6B0.50070.93630.74530.116*
H6C0.40920.95680.91500.116*
C70.2818 (10)0.7995 (4)0.755 (2)0.040 (3)
H70.33220.78130.84260.047*
C80.2357 (11)0.7757 (4)0.557 (2)0.034 (3)
C90.1437 (12)0.7977 (4)0.428 (2)0.041 (3)
C100.1061 (8)0.7732 (4)0.235 (2)0.031 (3)
C110.1625 (11)0.7281 (4)0.181 (2)0.043 (3)
H110.14180.71230.04740.051*
C120.2427 (10)0.7075 (5)0.310 (3)0.043 (3)
C130.2807 (11)0.7309 (5)0.495 (3)0.044 (3)
H130.33800.71700.58360.053*
C14−0.0233 (13)0.9290 (4)0.448 (3)0.048 (4)
H140.02030.91280.33930.058*
C15−0.1907 (13)0.9786 (5)0.540 (3)0.053 (4)
H15A−0.24020.95440.60470.080*
H15B−0.23611.00280.46360.080*
H15C−0.14670.99380.65790.080*
C16−0.1495 (16)0.9579 (7)0.135 (3)0.063 (5)
H16A−0.08820.94780.03660.094*
H16B−0.17090.99080.09950.094*
H16C−0.21430.93680.11290.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0356 (7)0.0313 (6)0.0437 (9)0.0098 (6)−0.0076 (7)−0.0074 (7)
Cl10.0389 (18)0.061 (2)0.044 (2)−0.0044 (16)−0.0118 (16)0.0061 (17)
Cl20.081 (3)0.0460 (18)0.074 (3)−0.0011 (17)0.018 (3)−0.019 (2)
N10.039 (5)0.030 (5)0.028 (6)0.009 (4)−0.013 (5)−0.012 (4)
N20.044 (7)0.055 (7)0.030 (6)0.032 (6)0.002 (5)0.011 (5)
O10.024 (5)0.049 (5)0.066 (7)0.017 (4)−0.021 (4)−0.005 (5)
O20.069 (7)0.066 (7)0.055 (7)0.012 (6)−0.009 (6)−0.021 (6)
O30.040 (5)0.024 (4)0.069 (7)0.009 (4)−0.012 (4)−0.010 (4)
O40.026 (4)0.060 (6)0.031 (5)0.004 (4)0.004 (4)−0.002 (4)
C10.032 (7)0.042 (7)0.041 (8)−0.008 (6)0.012 (6)−0.014 (6)
C20.051 (8)0.034 (6)0.020 (6)0.007 (5)0.006 (6)−0.004 (5)
C30.022 (7)0.086 (11)0.068 (10)0.020 (8)−0.006 (7)−0.017 (11)
C40.054 (9)0.091 (13)0.056 (10)−0.008 (9)−0.011 (8)−0.011 (9)
C50.063 (11)0.091 (13)0.076 (13)0.003 (10)−0.028 (10)−0.010 (10)
C60.031 (8)0.111 (14)0.091 (14)−0.005 (8)0.008 (9)−0.028 (13)
C70.040 (7)0.049 (7)0.031 (8)0.014 (5)0.001 (6)−0.007 (7)
C80.040 (7)0.032 (6)0.030 (7)0.002 (5)−0.004 (6)−0.002 (5)
C90.048 (8)0.034 (6)0.041 (8)0.008 (6)0.006 (7)0.001 (6)
C100.022 (6)0.043 (6)0.029 (7)0.001 (4)0.004 (5)0.012 (6)
C110.051 (8)0.031 (6)0.046 (9)−0.021 (6)−0.002 (7)−0.004 (6)
C120.030 (6)0.042 (7)0.058 (9)−0.006 (6)0.016 (7)−0.025 (7)
C130.026 (7)0.039 (7)0.067 (10)0.000 (5)0.005 (6)−0.006 (7)
C140.059 (9)0.029 (7)0.056 (10)0.015 (6)0.005 (8)0.013 (7)
C150.052 (9)0.055 (8)0.053 (10)0.012 (7)−0.008 (8)−0.006 (7)
C160.059 (11)0.081 (11)0.048 (10)0.004 (9)0.015 (8)−0.010 (8)
Geometric parameters (Å, °) top
Cu1—O31.872 (9)C5—H5A0.9600
Cu1—O11.905 (9)C5—H5B0.9600
Cu1—O41.920 (9)C5—H5C0.9600
Cu1—N11.925 (10)C6—H6A0.9600
Cl1—C101.685 (11)C6—H6B0.9600
Cl2—C121.712 (12)C6—H6C0.9600
N1—C71.328 (14)C7—C81.442 (17)
N1—C21.482 (16)C7—H70.9300
N2—C141.329 (17)C8—C131.384 (16)
N2—C161.473 (19)C8—C91.444 (17)
N2—C151.497 (18)C9—C101.395 (17)
O1—C11.333 (17)C10—C111.438 (17)
O2—C11.233 (16)C11—C121.333 (19)
O3—C91.306 (14)C11—H110.9300
O4—C141.225 (17)C12—C131.341 (19)
C1—C21.493 (17)C13—H130.9300
C2—C31.53 (2)C14—H140.9300
C2—H20.9800C15—H15A0.9600
C3—C41.53 (2)C15—H15B0.9600
C3—C61.53 (3)C15—H15C0.9600
C3—H30.9800C16—H16A0.9600
C4—C51.53 (2)C16—H16B0.9600
C4—H4A0.9700C16—H16C0.9600
C4—H4B0.9700
O3—Cu1—O1169.2 (4)C3—C6—H6A109.5
O3—Cu1—O492.5 (4)C3—C6—H6B109.5
O1—Cu1—O490.5 (3)H6A—C6—H6B109.5
O3—Cu1—N194.2 (4)C3—C6—H6C109.5
O1—Cu1—N182.7 (4)H6A—C6—H6C109.5
O4—Cu1—N1173.1 (4)H6B—C6—H6C109.5
C7—N1—C2120.0 (10)N1—C7—C8127.5 (11)
C7—N1—Cu1122.9 (8)N1—C7—H7116.3
C2—N1—Cu1115.7 (7)C8—C7—H7116.3
C14—N2—C16125.3 (13)C13—C8—C7118.2 (11)
C14—N2—C15119.5 (12)C13—C8—C9121.1 (12)
C16—N2—C15114.6 (11)C7—C8—C9120.7 (10)
C1—O1—Cu1117.4 (7)O3—C9—C10119.5 (11)
C9—O3—Cu1130.0 (9)O3—C9—C8123.1 (11)
C14—O4—Cu1119.5 (8)C10—C9—C8117.4 (10)
O2—C1—O1120.6 (13)C9—C10—C11116.8 (10)
O2—C1—C2123.3 (14)C9—C10—Cl1120.2 (9)
O1—C1—C2116.1 (11)C11—C10—Cl1122.8 (10)
N1—C2—C1106.7 (11)C12—C11—C10124.2 (12)
N1—C2—C3109.0 (10)C12—C11—H11117.9
C1—C2—C3112.3 (11)C10—C11—H11117.9
N1—C2—H2109.6C11—C12—C13119.5 (12)
C1—C2—H2109.6C11—C12—Cl2119.4 (11)
C3—C2—H2109.6C13—C12—Cl2121.1 (12)
C2—C3—C4111.3 (13)C12—C13—C8120.8 (13)
C2—C3—C6112.3 (11)C12—C13—H13119.6
C4—C3—C6107.6 (15)C8—C13—H13119.6
C2—C3—H3108.5O4—C14—N2126.3 (14)
C4—C3—H3108.5O4—C14—H14116.9
C6—C3—H3108.5N2—C14—H14116.9
C5—C4—C3114.9 (15)N2—C15—H15A109.5
C5—C4—H4A108.5N2—C15—H15B109.5
C3—C4—H4A108.5H15A—C15—H15B109.5
C5—C4—H4B108.5N2—C15—H15C109.5
C3—C4—H4B108.5H15A—C15—H15C109.5
H4A—C4—H4B107.5H15B—C15—H15C109.5
C4—C5—H5A109.5N2—C16—H16A109.5
C4—C5—H5B109.5N2—C16—H16B109.5
H5A—C5—H5B109.5H16A—C16—H16B109.5
C4—C5—H5C109.5N2—C16—H16C109.5
H5A—C5—H5C109.5H16A—C16—H16C109.5
H5B—C5—H5C109.5H16B—C16—H16C109.5
O3—Cu1—N1—C7−10.6 (11)C6—C3—C4—C5176.2 (14)
O1—Cu1—N1—C7159.0 (11)C2—N1—C7—C8−177.5 (12)
O3—Cu1—N1—C2−177.3 (8)Cu1—N1—C7—C816.4 (19)
O1—Cu1—N1—C2−7.7 (8)N1—C7—C8—C13171.3 (12)
O3—Cu1—O1—C174 (2)N1—C7—C8—C9−10 (2)
O4—Cu1—O1—C1180.0 (9)Cu1—O3—C9—C10−175.0 (8)
N1—Cu1—O1—C10.4 (9)Cu1—O3—C9—C84.8 (19)
O1—Cu1—O3—C9−72 (2)C13—C8—C9—O3177.1 (12)
O4—Cu1—O3—C9−177.7 (11)C7—C8—C9—O3−2(2)
N1—Cu1—O3—C90.7 (12)C13—C8—C9—C10−3.1 (18)
O3—Cu1—O4—C14−34.2 (11)C7—C8—C9—C10178.0 (11)
O1—Cu1—O4—C14156.2 (11)O3—C9—C10—C11180.0 (11)
Cu1—O1—C1—O2−170.2 (10)C8—C9—C10—C110.1 (16)
Cu1—O1—C1—C27.0 (14)O3—C9—C10—Cl14.9 (16)
C7—N1—C2—C1−154.7 (12)C8—C9—C10—Cl1−175.0 (9)
Cu1—N1—C2—C112.4 (12)C9—C10—C11—C123.9 (18)
C7—N1—C2—C383.7 (14)Cl1—C10—C11—C12178.8 (10)
Cu1—N1—C2—C3−109.1 (11)C10—C11—C12—C13−5(2)
O2—C1—C2—N1164.9 (13)C10—C11—C12—Cl2174.6 (9)
O1—C1—C2—N1−12.2 (15)C11—C12—C13—C82(2)
O2—C1—C2—C3−75.7 (17)Cl2—C12—C13—C8−177.8 (10)
O1—C1—C2—C3107.2 (13)C7—C8—C13—C12−178.7 (12)
N1—C2—C3—C4−169.2 (13)C9—C8—C13—C122(2)
C1—C2—C3—C472.8 (17)Cu1—O4—C14—N2177.0 (11)
N1—C2—C3—C670.2 (15)C16—N2—C14—O4−176.1 (15)
C1—C2—C3—C6−47.9 (17)C15—N2—C14—O4−5(2)
C2—C3—C4—C552.8 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15B···O2i0.962.313.19 (2)150
Symmetry codes: (i) −x, −y+2, z−1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O31.872 (9)Cu1—O41.920 (9)
Cu1—O11.905 (9)Cu1—N11.925 (10)
O3—Cu1—O1169.2 (4)O3—Cu1—N194.2 (4)
O3—Cu1—O492.5 (4)O1—Cu1—N182.7 (4)
O1—Cu1—O490.5 (3)O4—Cu1—N1173.1 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15B···O2i0.962.313.19 (2)150
Symmetry codes: (i) −x, −y+2, z−1.
Acknowledgements top

We acknowledge financial support by the Key Laboratory of Non-ferrous Metal Material and New Processing Technology, Ministry of Education, China.

references
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