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Acta Cryst. (2007). E63, m2982-m2983    [ doi:10.1107/S1600536807057376 ]

catena-Poly[[{2-[3-(dimethylamino)propyliminomethyl]-4-nitrophenolato}copper(II)]-[mu]-acetato]

W.-H. Li

Abstract top

The title compound, [Cu(C12H16N3O3)(CH3COO)]n or [Cu(CMP)(CH3COO)]n {CMP is 2-[3-(dimethylamino)propyliminomethyl]-4-nitrophenol}, was synthesized by the reaction of 2-hydroxy-5-nitrobenzaldehyde, N,N-dimethylpropane-1,3-diamine and copper(II) acetate monohydrate in a methanol solution. The compound is an acetate-bridged polymeric copper(II) complex. The CuII atom is coordinated in a square-pyramidal manner by one Schiff base CMP ligand and two acetate anions. The Schiff base molecule acts as a tridentate ligand, coordinating the CuII ion through its phenolate O atom, imine N atom and amine N atom. The acetate anion acts as a bridging group, coordinating two adjacent CuII ions through its two O atoms, one in the basal plane and the other in the apical position. The [Cu(CMP)] units are linked through the bridging acetate groups, forming chains running along the c axis.

Comment top

Polynuclear complexes are very interesting in both structures and properties in coordination chemistry. The azide, thiocyanate, and cyanide anions are often used to construct versatile polynuclear complexes (Escuer & Aromí, 2006; Massoud et al., 2007; Zhang et al., 2001; Dey et al., 2004; Liu et al., 2006; Mondal et al., 2001). In comparison, the acetato-bridged polynuclear complexes are rarely seen. Recently, we have reported the crystal structures of some Schiff base complexes (Li, 2007a,b). In order to investigate the coordination modes of the acetate anions, the author reports herein the crystal structure of an acetato-bridged polynuclear copper(II) complex with Schiff base ligand 4-chloro-2-[(3-dimethylaminopropylimino)methyl]phenol (CMP).

The Cu atom in the acetato-bridged polynuclear complex is square-pyramidal coordinated by one Schiff base ligand CMP and two acetate anions (Fig. 1). The Schiff base molecule acts as a tridentate ligand coordinating the copper ion through the phenolic O atom, imine N atom and amine N atom. The acetate anion acts as a bridging group coordinating adjacent two copper ions through the two O atoms, one at the basal plane and the other one at the apical position. All the coordinated bond lengths and angles (Table 1) are comparable to the values in other similar Schiff base copper(II) complexes (Hebbachi & Benali-Cherif, 2005; Wang & You, 2007; Diao et al., 2007; Usman et al., 2003).

In the crystal structure, the [Cu(CMP)] units are linked through the bridging acetate groups, forming chains running along the c axis (Fig. 2).

Related literature top

For azido-bridged polynuclear complexes, see: Escuer & Aromí (2006); Massoud et al. (2007). For thiocyanato-bridged polynuclear complexes, see: Zhang et al. (2001); Dey et al. (2004). For cyano-bridged polynuclear complexes, see: Liu et al. (2006); Mondal et al. (2001). For our previously reported Schiff base complexes, see: Li (2007a,b). For related structures, see: Hebbachi & Benali-Cherif (2005); Wang & You (2007); Diao et al. (2007); Usman et al. (2003).

Experimental top

5-Nitro-2-hydroxybenzaldehyde (0.1 mmol, 16.7 mg), N,N-dimethylpropane-1,3-diamine (0.1 mmol, 10.2 mg), and copper(II) acetate monohydrate (0.1 mmol, 19.9 mg) were mixed in methanol (20 ml) and the mixture was stirred for 30 min at room temperature. The reaction mixture was fitered. Blue block-shaped single crystals suitable for X-ray diffraction were formed from the filtrate after a week.

Refinement top

All H atom positions were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding, with Uiso(H) values set at 1.2Ueq(C) and 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), shown with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. Molecular packing of (I).
catena-Poly[[{2-[3-(dimethylamino)propyliminomethyl]-4- nitrophenolato}copper(II)]-µ-acetato] top
Crystal data top
[Cu(C12H16N3O3)(C2H3O2)]F000 = 772
Mr = 372.86Dx = 1.560 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1027 reflections
a = 13.834 (3) Åθ = 2.3–24.5º
b = 11.661 (2) ŵ = 1.41 mm−1
c = 9.988 (2) ÅT = 298 (2) K
β = 99.86 (3)ºBlock, blue
V = 1587.5 (6) Å30.27 × 0.23 × 0.20 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3522 independent reflections
Radiation source: fine-focus sealed tube2037 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.087
T = 298(2) Kθmax = 27.5º
ω scansθmin = 1.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −17→17
Tmin = 0.703, Tmax = 0.767k = −15→12
9081 measured reflectionsl = −12→12
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)] = 0.079H-atom parameters constrained
wR(F2) = 0.184  w = 1/[σ2(Fo2) + (0.0706P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
3522 reflectionsΔρmax = 0.85 e Å−3
211 parametersΔρmin = −0.61 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C12H16N3O3)(C2H3O2)]V = 1587.5 (6) Å3
Mr = 372.86Z = 4
Monoclinic, P21/cMo Kα
a = 13.834 (3) ŵ = 1.41 mm−1
b = 11.661 (2) ÅT = 298 (2) K
c = 9.988 (2) Å0.27 × 0.23 × 0.20 mm
β = 99.86 (3)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3522 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2037 reflections with I > 2σ(I)
Tmin = 0.703, Tmax = 0.767Rint = 0.087
9081 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.079211 parameters
wR(F2) = 0.184H-atom parameters constrained
S = 1.00Δρmax = 0.85 e Å−3
3522 reflectionsΔρmin = −0.61 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
Cu10.82621 (5)0.77042 (6)0.15549 (7)0.0297 (3)
O10.4913 (4)0.3131 (5)0.2555 (6)0.0722 (16)
O20.6056 (5)0.1905 (6)0.3039 (8)0.105 (3)
O30.8450 (3)0.6052 (4)0.1489 (4)0.0371 (11)
O40.9473 (3)0.7753 (4)0.2908 (4)0.0368 (10)
O50.8694 (3)0.7033 (4)0.4489 (4)0.0398 (11)
N10.6858 (4)0.7516 (4)0.0710 (5)0.0359 (13)
N20.8117 (4)0.9467 (4)0.1846 (5)0.0375 (13)
N30.5767 (5)0.2850 (6)0.2657 (7)0.0584 (17)
C10.6773 (4)0.5540 (5)0.1479 (6)0.0331 (14)
C20.7805 (4)0.5326 (5)0.1707 (5)0.0301 (14)
C30.8105 (5)0.4200 (6)0.2173 (6)0.0438 (17)
H30.87660.40060.22820.053*
C40.7456 (5)0.3407 (6)0.2461 (7)0.0453 (17)
H40.76770.26880.27810.054*
C50.6451 (5)0.3667 (6)0.2278 (6)0.0401 (16)
C60.6122 (5)0.4719 (5)0.1788 (6)0.0384 (15)
H60.54550.48840.16610.046*
C70.6381 (4)0.6600 (6)0.0865 (6)0.0363 (15)
H70.57080.66190.05470.044*
C80.6331 (5)0.8417 (6)−0.0144 (7)0.0504 (19)
H8A0.56440.8207−0.03620.061*
H8B0.65850.8453−0.09910.061*
C90.6408 (5)0.9577 (6)0.0489 (7)0.055 (2)
H9A0.61700.95390.13470.065*
H9B0.59861.0102−0.00990.065*
C100.7438 (5)1.0050 (6)0.0742 (7)0.0496 (18)
H10A0.77060.9991−0.00920.060*
H10B0.74101.08580.09640.060*
C110.7785 (6)0.9636 (6)0.3160 (6)0.057 (2)
H11A0.77021.04400.33110.085*
H11B0.82660.93290.38780.085*
H11C0.71720.92480.31470.085*
C120.9085 (5)1.0048 (6)0.1915 (8)0.056 (2)
H12A0.90201.08460.21190.084*
H12B0.93030.99720.10570.084*
H12C0.95560.97000.26150.084*
C131.0367 (5)0.7595 (6)0.5095 (7)0.054 (2)
H13A1.03490.83210.55450.081*
H13B1.09140.75810.46190.081*
H13C1.04370.69900.57570.081*
C140.9432 (5)0.7429 (5)0.4103 (6)0.0332 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0299 (4)0.0322 (5)0.0270 (4)−0.0009 (3)0.0052 (3)0.0021 (3)
O10.057 (4)0.059 (4)0.109 (5)−0.012 (3)0.038 (3)0.006 (3)
O20.086 (5)0.052 (4)0.183 (7)−0.002 (4)0.043 (5)0.040 (5)
O30.032 (2)0.032 (3)0.048 (3)−0.0026 (19)0.0119 (19)−0.008 (2)
O40.044 (2)0.041 (3)0.025 (2)−0.003 (2)0.0045 (17)0.004 (2)
O50.038 (2)0.054 (3)0.029 (2)−0.006 (2)0.0133 (18)0.001 (2)
N10.034 (3)0.040 (4)0.033 (3)−0.001 (2)0.006 (2)0.006 (2)
N20.050 (3)0.032 (3)0.033 (3)0.002 (2)0.013 (2)0.002 (2)
N30.059 (4)0.040 (4)0.081 (5)−0.002 (3)0.024 (4)0.000 (4)
C10.047 (4)0.028 (4)0.026 (3)−0.005 (3)0.009 (3)−0.007 (3)
C20.033 (3)0.030 (4)0.028 (3)−0.001 (3)0.006 (2)−0.010 (3)
C30.049 (4)0.036 (4)0.046 (4)0.005 (3)0.004 (3)0.001 (3)
C40.054 (4)0.029 (4)0.052 (4)0.000 (3)0.007 (3)0.001 (3)
C50.049 (4)0.031 (4)0.043 (4)−0.006 (3)0.015 (3)−0.005 (3)
C60.038 (3)0.036 (4)0.043 (4)−0.007 (3)0.012 (3)−0.010 (3)
C70.030 (3)0.046 (4)0.032 (3)−0.007 (3)0.001 (3)−0.003 (3)
C80.052 (4)0.051 (5)0.044 (4)0.003 (3)−0.004 (3)0.008 (4)
C90.052 (4)0.044 (5)0.061 (5)0.003 (4)−0.009 (4)0.022 (4)
C100.063 (5)0.035 (4)0.052 (4)0.007 (3)0.012 (4)0.011 (3)
C110.082 (6)0.055 (5)0.033 (4)0.021 (4)0.009 (4)0.006 (4)
C120.054 (4)0.035 (4)0.074 (5)−0.007 (3)0.000 (4)0.003 (4)
C130.051 (4)0.081 (6)0.031 (3)−0.003 (4)0.007 (3)−0.001 (4)
C140.036 (3)0.032 (4)0.031 (3)0.008 (3)0.005 (3)−0.001 (3)
Geometric parameters (Å, °) top
Cu1—O31.946 (4)C4—C51.404 (9)
Cu1—O41.965 (4)C4—H40.9300
Cu1—N11.992 (5)C5—C61.370 (9)
Cu1—N22.091 (5)C6—H60.9300
Cu1—O5i2.265 (4)C7—H70.9300
O1—N31.215 (8)C8—C91.490 (10)
O2—N31.211 (8)C8—H8A0.9700
O3—C21.276 (7)C8—H8B0.9700
O4—C141.262 (7)C9—C101.509 (9)
O5—C141.241 (7)C9—H9A0.9700
O5—Cu1ii2.265 (4)C9—H9B0.9700
N1—C71.280 (7)C10—H10A0.9700
N1—C81.467 (8)C10—H10B0.9700
N2—C111.476 (8)C11—H11A0.9600
N2—C101.485 (8)C11—H11B0.9600
N2—C121.492 (8)C11—H11C0.9600
N3—C51.438 (9)C12—H12A0.9600
C1—C61.385 (8)C12—H12B0.9600
C1—C21.429 (8)C12—H12C0.9600
C1—C71.444 (9)C13—C141.502 (9)
C2—C31.431 (9)C13—H13A0.9600
C3—C41.353 (9)C13—H13B0.9600
C3—H30.9300C13—H13C0.9600
O3—Cu1—O487.07 (17)N1—C7—C1127.0 (6)
O3—Cu1—N190.17 (18)N1—C7—H7116.5
O4—Cu1—N1161.58 (19)C1—C7—H7116.5
O3—Cu1—N2173.93 (19)N1—C8—C9114.3 (5)
O4—Cu1—N288.09 (19)N1—C8—H8A108.7
N1—Cu1—N293.3 (2)C9—C8—H8A108.7
O3—Cu1—O5i92.62 (16)N1—C8—H8B108.7
O4—Cu1—O5i107.21 (17)C9—C8—H8B108.7
N1—Cu1—O5i91.10 (18)H8A—C8—H8B107.6
N2—Cu1—O5i92.32 (18)C8—C9—C10113.5 (6)
C2—O3—Cu1123.4 (4)C8—C9—H9A108.9
C14—O4—Cu1118.0 (4)C10—C9—H9A108.9
C14—O5—Cu1ii126.3 (4)C8—C9—H9B108.9
C7—N1—C8116.9 (5)C10—C9—H9B108.9
C7—N1—Cu1121.8 (4)H9A—C9—H9B107.7
C8—N1—Cu1121.3 (4)N2—C10—C9114.6 (5)
C11—N2—C10110.3 (5)N2—C10—H10A108.6
C11—N2—C12108.2 (5)C9—C10—H10A108.6
C10—N2—C12105.9 (5)N2—C10—H10B108.6
C11—N2—Cu1107.9 (4)C9—C10—H10B108.6
C10—N2—Cu1114.2 (4)H10A—C10—H10B107.6
C12—N2—Cu1110.2 (4)N2—C11—H11A109.5
O2—N3—O1122.4 (7)N2—C11—H11B109.5
O2—N3—C5119.3 (7)H11A—C11—H11B109.5
O1—N3—C5118.3 (6)N2—C11—H11C109.5
C6—C1—C2120.9 (6)H11A—C11—H11C109.5
C6—C1—C7118.3 (6)H11B—C11—H11C109.5
C2—C1—C7120.7 (6)N2—C12—H12A109.5
O3—C2—C1124.4 (6)N2—C12—H12B109.5
O3—C2—C3119.5 (6)H12A—C12—H12B109.5
C1—C2—C3116.0 (6)N2—C12—H12C109.5
C4—C3—C2122.0 (6)H12A—C12—H12C109.5
C4—C3—H3119.0H12B—C12—H12C109.5
C2—C3—H3119.0C14—C13—H13A109.5
C3—C4—C5120.2 (6)C14—C13—H13B109.5
C3—C4—H4119.9H13A—C13—H13B109.5
C5—C4—H4119.9C14—C13—H13C109.5
C6—C5—C4120.1 (6)H13A—C13—H13C109.5
C6—C5—N3119.6 (6)H13B—C13—H13C109.5
C4—C5—N3120.3 (6)O5—C14—O4125.4 (6)
C5—C6—C1120.7 (6)O5—C14—C13120.3 (5)
C5—C6—H6119.7O4—C14—C13114.3 (6)
C1—C6—H6119.7
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O31.946 (4)Cu1—N22.091 (5)
Cu1—O41.965 (4)Cu1—O5i2.265 (4)
Cu1—N11.992 (5)
O3—Cu1—O487.07 (17)N1—Cu1—N293.3 (2)
O3—Cu1—N190.17 (18)O3—Cu1—O5i92.62 (16)
O4—Cu1—N1161.58 (19)O4—Cu1—O5i107.21 (17)
O3—Cu1—N2173.93 (19)N1—Cu1—O5i91.10 (18)
O4—Cu1—N288.09 (19)N2—Cu1—O5i92.32 (18)
Symmetry codes: (i) x, −y+3/2, z−1/2.
Acknowledgements top

The author greatly acknowledges Jingchu University of Technology for financial support.

references
References top

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