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Acta Cryst. (2007). E63, m1998    [ doi:10.1107/S1600536807030723 ]

[N,N'-Bis(6-methoxysalicylidene)-1,3-diaminopropane]copper(II)

M. H. Habibi, R. Mokhtari, R. W. Harrington and W. Clegg

Abstract top

The title compound, [Cu(C19H20N2O4)], is a mononuclear copper(II) Schiff base complex. The CuII ion is surrounded by two imine N and two phenolate O atoms of the tetradentate ligand in a square-planar coordination with a slight tetrahedral distortion. The dihedral angle between the CuN2 and CuO2 planes is 25.07 (9)°.

Comment top

Metal derivatives of Schiff bases have been studied extensively, and CuII and NiII complexes play a major role in both synthetic and structural research. The coordination of the metal cations is usually planar in the case of Ni, but for Cu a tetrahedral distortion is often observed (Garnovskii et al., 1993). We report here the results of the reaction of CuII with the tetradentate ligand N,N'-bis(6-methoxysalicylidene)-1,3-diaminopropane in a 1:1 molar ratio, forming the title compound, (I).

A view of the molecular structure of (I) is shown in Fig. 1. The crystal structure of the ligand (but without methoxy substituents) is known for a long time (Elerman et al., 1991), as are about 150 of its metal complexes (found in a search of the Cambridge Structural Database [version 5.28] plus two updates until May 2007; Allen, 2002). Structures of the CuII complex which are comparable with the title compound have been reported several times, the most recent given by Nathan et al. (2003). The title complex, however, is the first reported example of a Schiff base, as a ligand or uncomplexed, in which substituents in the 6 position of the benzene rings are present.

The CuII coordination polyhedron is approximately square planar, with a significant distortion towards tetrahedral, as indicated by the dihedral angle of 25.07 (9)° between the CuO2 and CuN2 planes. This, and the Cu—O and Cu—N distances (see Table), are similar to those observed in other CuII complexes of related Schiff bases.

Related literature top

A review on ligand environments and structures of Schiff base adducts and tetracoordinated metal chelates has been given by Garnovskii et al. (1993). The Cambridge Structural Database (Version 5.28, plus two updates until May 2007; Allen, 2002) was used as a source for searching for related structures. For comparable Schiff base complexes, see: Elerman et al. (1991); Nathan et al. (2003).

Experimental top

A mixture of 6-methoxysalicylaldehyde (2.0 mmol, 304 mg) and 1,3-diaminopropane (1.0 mmol, 74 mg) was dissolved in methanol (10 ml) with stirring for 30 min at room temperature, to give a clear yellow solution. A methanol solution (10 ml) of Cu(CH3COO)2.2H2O (1.0 mmol, 218 mg) was then added. The mixture was stirred for further 30 min and then filtered. After keeping the filtrate in air for 7 d, blue block-shaped crystals were formed at the bottom of the vessel on slow evaporation of the solvent, in about 65% yield.

Refinement top

All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2 or 1.5 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2005b); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. The molecular structure with atom labels, drawn with ellipsoids at the 50% probability level for all non-H atoms. H atoms are given as spheres of arbitrary radius.
{2,2'-[propane-1,3-diylbis(nitrilomethylidyne)]diphenolato}copper(II) top
Crystal data top
[Cu(C19H20N2O4)]F000 = 836
Mr = 403.91Dx = 1.542 Mg m−3
Orthorhombic, Pca21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 9351 reflections
a = 13.7911 (14) Åθ = 2.2–28.3º
b = 12.7032 (13) ŵ = 1.28 mm−1
c = 9.9329 (10) ÅT = 150 (2) K
V = 1740.2 (3) Å3Block, blue
Z = 40.30 × 0.30 × 0.20 mm
Data collection top
Bruker SMART 1K CCD
diffractometer		4157 independent reflections
Radiation source: fine-focus sealed tube3766 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 150(2) Kθmax = 28.3º
ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2005a)		h = −17→17
Tmin = 0.700, Tmax = 0.785k = −16→16
14731 measured reflectionsl = −13→13
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.024  w = 1/[σ2(Fo2) + (0.0332P)2 + 0.2389P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.063(Δ/σ)max = 0.001
S = 1.04Δρmax = 0.33 e Å−3
4157 reflectionsΔρmin = −0.44 e Å−3
237 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 1916 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.013 (12)
Secondary atom site location: difference Fourier map
Crystal data top
[Cu(C19H20N2O4)]V = 1740.2 (3) Å3
Mr = 403.91Z = 4
Orthorhombic, Pca21Mo Kα
a = 13.7911 (14) ŵ = 1.28 mm−1
b = 12.7032 (13) ÅT = 150 (2) K
c = 9.9329 (10) Å0.30 × 0.30 × 0.20 mm
Data collection top
Bruker SMART 1K CCD
diffractometer		4157 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2005a)		3766 reflections with I > 2σ(I)
Tmin = 0.700, Tmax = 0.785Rint = 0.028
14731 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.063Δρmax = 0.33 e Å−3
S = 1.04Δρmin = −0.44 e Å−3
4157 reflectionsAbsolute structure: Flack (1983), 1916 Friedel pairs
237 parametersFlack parameter: 0.013 (12)
1 restraint
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu0.174992 (13)0.252482 (15)0.36441 (5)0.01625 (6)
N10.23946 (12)0.12304 (12)0.42218 (15)0.0194 (3)
N20.28978 (10)0.32088 (11)0.28765 (16)0.0171 (3)
O10.13783 (12)−0.12408 (11)0.62238 (16)0.0321 (3)
O20.06371 (10)0.22063 (11)0.47204 (15)0.0239 (3)
O30.08904 (9)0.34212 (10)0.26854 (13)0.0210 (3)
O40.30881 (10)0.53932 (12)0.00073 (16)0.0298 (3)
C10.1202 (2)−0.20841 (18)0.7155 (3)0.0402 (6)
H1A0.1723−0.26050.70850.060*
H1B0.0580−0.24190.69420.060*
H1C0.1181−0.18030.80740.060*
C20.07334 (16)−0.04266 (15)0.6220 (2)0.0244 (4)
C3−0.01325 (16)−0.04319 (16)0.6918 (2)0.0284 (5)
H3A−0.0321−0.10250.74380.034*
C4−0.07236 (16)0.04570 (17)0.6838 (2)0.0292 (4)
H4A−0.13190.04600.73200.035*
C5−0.04815 (15)0.13287 (16)0.6092 (2)0.0258 (4)
H5A−0.09130.19110.60520.031*
C60.04105 (14)0.13626 (15)0.53826 (18)0.0208 (4)
C70.10334 (15)0.04696 (15)0.54488 (19)0.0205 (4)
C80.19971 (14)0.04821 (15)0.49065 (19)0.0210 (4)
H8A0.2384−0.01240.50680.025*
C90.34254 (14)0.11051 (14)0.38763 (19)0.0221 (4)
H9A0.34950.10060.28920.027*
H9B0.36910.04750.43320.027*
C100.39877 (15)0.20812 (16)0.4319 (2)0.0227 (4)
H10A0.37360.23230.51990.027*
H10B0.46790.18930.44390.027*
C110.39108 (13)0.29754 (15)0.33088 (19)0.0207 (4)
H11A0.41940.36180.37120.025*
H11B0.43000.27950.25040.025*
C120.28636 (14)0.39154 (14)0.19369 (18)0.0182 (4)
H12A0.34710.41450.15950.022*
C130.20214 (13)0.43938 (14)0.13492 (18)0.0178 (4)
C140.21461 (13)0.51992 (15)0.03636 (19)0.0204 (4)
C150.13649 (14)0.57306 (15)−0.0176 (2)0.0226 (4)
H15A0.14560.6263−0.08350.027*
C160.04276 (14)0.54632 (15)0.0277 (2)0.0241 (4)
H16A−0.01160.5824−0.00870.029*
C170.02793 (14)0.46998 (15)0.1223 (2)0.0226 (4)
H17A−0.03630.45410.15030.027*
C180.10671 (13)0.41422 (14)0.17916 (19)0.0184 (4)
C190.32782 (15)0.62249 (17)−0.0922 (2)0.0295 (5)
H19A0.39790.6284−0.10680.044*
H19B0.30300.6889−0.05560.044*
H19C0.29560.6073−0.17800.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.01746 (10)0.01431 (10)0.01697 (10)0.00117 (8)0.00155 (11)0.00191 (8)
N10.0246 (8)0.0166 (7)0.0170 (7)0.0037 (6)0.0008 (6)−0.0003 (6)
N20.0165 (7)0.0159 (7)0.0191 (8)0.0017 (6)−0.0019 (6)−0.0002 (6)
O10.0434 (9)0.0202 (7)0.0328 (8)−0.0012 (6)0.0019 (7)0.0100 (6)
O20.0252 (7)0.0188 (6)0.0278 (7)0.0011 (6)0.0083 (6)0.0043 (6)
O30.0168 (6)0.0202 (6)0.0258 (7)0.0017 (5)0.0021 (5)0.0066 (6)
O40.0179 (6)0.0328 (8)0.0388 (9)−0.0034 (6)0.0008 (6)0.0191 (7)
C10.0548 (16)0.0247 (11)0.0412 (14)−0.0029 (11)−0.0002 (11)0.0160 (10)
C20.0350 (11)0.0190 (9)0.0193 (9)−0.0079 (8)−0.0060 (8)0.0005 (8)
C30.0362 (11)0.0273 (10)0.0217 (10)−0.0148 (9)−0.0026 (8)0.0045 (8)
C40.0291 (11)0.0356 (11)0.0230 (10)−0.0119 (9)0.0008 (8)0.0000 (9)
C50.0261 (10)0.0278 (10)0.0235 (10)−0.0024 (8)0.0026 (8)0.0014 (8)
C60.0275 (10)0.0203 (9)0.0147 (8)−0.0035 (7)0.0006 (7)−0.0008 (7)
C70.0296 (10)0.0168 (9)0.0151 (9)−0.0037 (7)−0.0018 (7)0.0002 (7)
C80.0306 (10)0.0152 (9)0.0173 (9)0.0007 (7)−0.0023 (7)−0.0020 (7)
C90.0247 (9)0.0191 (8)0.0224 (11)0.0057 (7)0.0033 (7)0.0010 (7)
C100.0216 (9)0.0236 (9)0.0230 (10)0.0053 (8)−0.0035 (8)0.0038 (8)
C110.0149 (9)0.0222 (9)0.0250 (11)0.0016 (7)−0.0033 (7)0.0028 (7)
C120.0160 (8)0.0181 (8)0.0203 (9)−0.0007 (7)0.0001 (6)−0.0002 (7)
C130.0177 (8)0.0160 (8)0.0196 (9)0.0005 (7)−0.0016 (7)0.0023 (7)
C140.0174 (8)0.0202 (9)0.0236 (9)−0.0020 (7)−0.0003 (7)0.0031 (7)
C150.0244 (9)0.0183 (9)0.0252 (9)0.0015 (7)−0.0011 (8)0.0062 (8)
C160.0215 (9)0.0206 (10)0.0301 (10)0.0053 (7)−0.0043 (8)0.0038 (8)
C170.0162 (9)0.0221 (9)0.0295 (10)0.0018 (7)0.0019 (7)0.0029 (8)
C180.0193 (9)0.0160 (8)0.0198 (9)0.0005 (7)0.0017 (7)−0.0013 (7)
C190.0267 (10)0.0298 (11)0.0321 (11)−0.0056 (8)0.0026 (8)0.0125 (9)
Geometric parameters (Å, °) top
Cu—N11.9554 (15)C6—C71.425 (3)
Cu—N21.9602 (15)C7—C81.434 (3)
Cu—O21.9136 (14)C8—H8A0.950
Cu—O31.8996 (13)C9—H9A0.990
N1—C81.291 (2)C9—H9B0.990
N1—C91.471 (2)C9—C101.527 (3)
N2—C111.491 (2)C10—H10A0.990
N2—C121.296 (2)C10—H10B0.990
O1—C11.436 (3)C10—C111.519 (3)
O1—C21.364 (3)C11—H11A0.990
O2—C61.296 (2)C11—H11B0.990
O3—C181.299 (2)C12—H12A0.950
O4—C141.369 (2)C12—C131.435 (3)
O4—C191.427 (2)C13—C141.426 (2)
C1—H1A0.980C13—C181.424 (3)
C1—H1B0.980C14—C151.380 (3)
C1—H1C0.980C15—H15A0.950
C2—C31.381 (3)C15—C161.410 (3)
C2—C71.433 (3)C16—H16A0.950
C3—H3A0.950C16—C171.366 (3)
C3—C41.395 (3)C17—H17A0.950
C4—H4A0.950C17—C181.415 (3)
C4—C51.373 (3)C19—H19A0.980
C5—H5A0.950C19—H19B0.980
C5—C61.419 (3)C19—H19C0.980
N1—Cu—N296.88 (6)N1—C9—H9B109.7
N1—Cu—O291.31 (6)N1—C9—C10109.62 (15)
N1—Cu—O3159.21 (6)H9A—C9—H9B108.2
N2—Cu—O2163.48 (6)H9A—C9—C10109.7
N2—Cu—O392.48 (6)H9B—C9—C10109.7
O2—Cu—O384.63 (6)C9—C10—H10A109.1
Cu—N1—C8125.50 (14)C9—C10—H10B109.1
Cu—N1—C9117.51 (11)C9—C10—C11112.44 (17)
C8—N1—C9116.98 (16)H10A—C10—H10B107.8
Cu—N2—C11123.81 (12)H10A—C10—C11109.1
Cu—N2—C12123.91 (13)H10B—C10—C11109.1
C11—N2—C12112.28 (15)N2—C11—C10113.84 (16)
C1—O1—C2117.18 (19)N2—C11—H11A108.8
Cu—O2—C6130.69 (13)N2—C11—H11B108.8
Cu—O3—C18130.41 (12)C10—C11—H11A108.8
C14—O4—C19118.35 (15)C10—C11—H11B108.8
O1—C1—H1A109.5H11A—C11—H11B107.7
O1—C1—H1B109.5N2—C12—H12A116.0
O1—C1—H1C109.5N2—C12—C13128.01 (18)
H1A—C1—H1B109.5H12A—C12—C13116.0
H1A—C1—H1C109.5C12—C13—C14119.04 (16)
H1B—C1—H1C109.5C12—C13—C18121.84 (17)
O1—C2—C3123.98 (18)C14—C13—C18118.96 (16)
O1—C2—C7114.55 (19)O4—C14—C13114.90 (16)
C3—C2—C7121.5 (2)O4—C14—C15123.54 (17)
C2—C3—H3A120.9C13—C14—C15121.56 (17)
C2—C3—C4118.23 (19)C14—C15—H15A120.8
H3A—C3—C4120.9C14—C15—C16118.30 (18)
C3—C4—H4A118.6H15A—C15—C16120.8
C3—C4—C5122.8 (2)C15—C16—H16A119.1
H4A—C4—C5118.6C15—C16—C17121.85 (17)
C4—C5—H5A119.9H16A—C16—C17119.1
C4—C5—C6120.22 (19)C16—C17—H17A119.5
H5A—C5—C6119.9C16—C17—C18121.01 (17)
O2—C6—C5119.12 (18)H17A—C17—C18119.5
O2—C6—C7122.45 (17)O3—C18—C13122.87 (16)
C5—C6—C7118.42 (18)O3—C18—C17118.81 (16)
C2—C7—C6118.89 (18)C13—C18—C17118.31 (17)
C2—C7—C8118.50 (18)O4—C19—H19A109.5
C6—C7—C8122.19 (17)O4—C19—H19B109.5
N1—C8—C7126.84 (18)O4—C19—H19C109.5
N1—C8—H8A116.6H19A—C19—H19B109.5
C7—C8—H8A116.6H19A—C19—H19C109.5
N1—C9—H9A109.7H19B—C19—H19C109.5
N2—Cu—N1—C8174.63 (16)C3—C2—C7—C6−1.4 (3)
N2—Cu—N1—C9−3.89 (14)C3—C2—C7—C8171.33 (19)
O2—Cu—N1—C89.01 (16)Cu—N1—C8—C7−4.0 (3)
O2—Cu—N1—C9−169.52 (13)C9—N1—C8—C7174.53 (18)
O3—Cu—N1—C8−69.2 (3)C2—C7—C8—N1−178.13 (18)
O3—Cu—N1—C9112.24 (19)C6—C7—C8—N1−5.7 (3)
N1—Cu—N2—C11−25.55 (15)Cu—N1—C9—C1051.28 (18)
N1—Cu—N2—C12154.49 (15)C8—N1—C9—C10−127.38 (18)
O2—Cu—N2—C1193.6 (3)N1—C9—C10—C11−81.9 (2)
O2—Cu—N2—C12−86.3 (3)Cu—N2—C11—C105.3 (2)
O3—Cu—N2—C11173.05 (14)C12—N2—C11—C10−174.79 (16)
O3—Cu—N2—C12−6.91 (15)C9—C10—C11—N249.3 (2)
N1—Cu—O2—C6−8.50 (17)Cu—N2—C12—C135.1 (3)
N2—Cu—O2—C6−128.4 (2)C11—N2—C12—C13−174.83 (18)
O3—Cu—O2—C6151.08 (17)N2—C12—C13—C14176.99 (18)
N1—Cu—O3—C18−112.2 (2)N2—C12—C13—C181.7 (3)
N2—Cu—O3—C184.62 (16)C19—O4—C14—C13−176.82 (17)
O2—Cu—O3—C18168.31 (16)C19—O4—C14—C153.2 (3)
C1—O1—C2—C3−8.9 (3)C12—C13—C14—O44.0 (3)
C1—O1—C2—C7169.63 (19)C12—C13—C14—C15−176.04 (18)
O1—C2—C3—C4179.44 (19)C18—C13—C14—O4179.49 (17)
C7—C2—C3—C41.0 (3)C18—C13—C14—C15−0.6 (3)
C2—C3—C4—C50.4 (3)O4—C14—C15—C16−179.7 (2)
C3—C4—C5—C6−1.3 (3)C13—C14—C15—C160.3 (3)
Cu—O2—C6—C5−179.00 (14)C14—C15—C16—C17−0.1 (3)
Cu—O2—C6—C72.3 (3)C15—C16—C17—C180.0 (3)
C4—C5—C6—O2−177.84 (19)Cu—O3—C18—C130.2 (3)
C4—C5—C6—C70.9 (3)Cu—O3—C18—C17179.72 (13)
O2—C6—C7—C2179.10 (17)C16—C17—C18—O3−179.84 (18)
O2—C6—C7—C86.7 (3)C16—C17—C18—C13−0.3 (3)
C5—C6—C7—C20.4 (3)C12—C13—C18—O3−4.6 (3)
C5—C6—C7—C8−172.05 (18)C12—C13—C18—C17175.85 (18)
O1—C2—C7—C6−179.93 (17)C14—C13—C18—O3−179.93 (17)
O1—C2—C7—C8−7.2 (3)C14—C13—C18—C170.5 (3)
Selected geometric parameters (Å, °) top
Cu—N11.9554 (15)Cu—O21.9136 (14)
Cu—N21.9602 (15)Cu—O31.8996 (13)
N1—Cu—N296.88 (6)N2—Cu—O2163.48 (6)
N1—Cu—O291.31 (6)N2—Cu—O392.48 (6)
N1—Cu—O3159.21 (6)O2—Cu—O384.63 (6)
Acknowledgements top

We thank the EPSRC (UK) and Isfahan University for financial support.

references
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