supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2351-m2352    [ doi:10.1107/S1600536807034691 ]

(2,2'-Bipyridine-[kappa]2N,N')[3-(2-oxidobenzylideneamino)propanoato-[kappa]3O,N,O']copper(II) dihydrate

J.-M. Xie, G.-Q. Zhao, M. Shao, H. Liu and X.-J. Lu

Abstract top

In the title compound, [Cu(C10H9NO3)(C10H8N2)]·2H2O, the CuII atom is five-coordinated in a distorted square-pyramidal geometry. The basal positions are occupied by three donor atoms from the tridentate Schiff base ligand and by one N atom from a 2,2'-bipyridine ligand. The apical position is occupied by the other N atom of the 2,2'-bipyridine ligand. The solvent water molecules link adjacent complex molecules through O-H...O hydrogen bonds into a chain running along the [\overline{1}01] direction.

Comment top

Considerable efforts have been devoted to copper(II) complexes of tridentate Schiff base ligands of N-alkylidene or N-arylidene aminoacidato type due to their structural richness, electrochemical properties as well as a potential model for a number of important biological systems (Raso et al., 1996, 1999). Several stuctural studies have been performed on Schiff base copper(II) complexes derived from salicylaldehyde and animo acids (Reddy et al., 2002; Wang et al., 2005; Warda, 1997, 1998a,b,c). We report here the crystal structure of the title CuII complex.

The structure consists of discrete monomeric square-pyramidal CuII complex (Fig. 1 and Table 1). The 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 2,2'-bipyridine ligand. The axial position is occupied by the other N atom of the 2,2'-bipyridine igand. The Cu atom is displaced from the O1/O2/N1/N3 basal plane toward the N2 atom by 0.2038 (2) Å.

The 2,2'-bipyridine ligand is essentially planar and it forms a dihedral angle of 81.95 (10)° with the benzene ring of the Schiff base ligand.

The crystal structure is stabilized by O—H···O type hydrogen bonds (Table 2). The lattice water molecules link adjacent complex molecules through O—H···O hydrogen bonds into a chain running along the [1 0 1] direction (Fig. 2). The closest Cu···Cu separation in the chain is 5.701 Å.

Related literature top

For synthesis, see: Plesch et al. (1997). For related literature, see: Raso et al. (1996, 1999). For related structures, see: Reddy et al. (2002); Wang et al. (2005); Warda (1997, 1998a,b,c).

Experimental top

The title compound was synthesized by a literature method (Plesch et al., 1997). The method of synthesis was as follows: To a solution of β-alanine (1 mmol) and lithium hydroxide monohydrate (1 mmol) in methanol (10 ml) was added a solution of salicylaldehyde (1 mmol) in methanol(10 ml). The yellow solution was stirred for 1 h at room temperature prior to cooling in an ice bath. The resultant mixture was added dropwise to a mixture of copper(II) acetate monohydrate (1 mmol) and 2,2'-bipyridine (1 mmol) in an aqueous methanolic solution (20 ml, 1:1 v/v), and heated with stirring for 2 h at 333 K. The dark green solution was filtered and left for several days. The resulting dark-blue crystals were filtered off, washed with water, and dried under vacuum. Analysis found: C 53.75, H 4.74, N 9.40%; calculated: C 53.29, H 4.56, N 9.77%.

Refinement top

The water H atoms were located in a difference Fourier map and were refined with distance restraints of O—H = 0.84 (1) Å and H···H = 1.37 (2) Å. C-bound H atoms were placed in geometrically idealized positions (C—H = 0.93 or 0.97 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. Part of a hydrogen-bonded (dashed lines) chain of the title compound.
(2,2'-Bipyridine-κ2N,N')[3-(2-oxidobenzylideneamino)propanoato- κ3O,N,O']copper(II) dihydrate top
Crystal data top
[Cu(C10H9NO3)(C10H8N2)]·2H2OF000 = 1848
Mr = 446.94Dx = 1.518 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4685 reflections
a = 15.1164 (14) Åθ = 2.3–26.8º
b = 13.1426 (12) ŵ = 1.16 mm−1
c = 19.6898 (19) ÅT = 298 (2) K
β = 91.204 (1)ºBlock, dark green
V = 3910.9 (6) Å30.30 × 0.20 × 0.20 mm
Z = 8
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		3427 independent reflections
Radiation source: fine-focus sealed tube2954 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −17→12
Tmin = 0.723, Tmax = 0.802k = −14→15
9940 measured reflectionsl = −23→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)] = 0.029H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.080  w = 1/[σ2(Fo2) + (0.0435P)2 + 2.2382P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
3427 reflectionsΔρmax = 0.21 e Å−3
279 parametersΔρmin = −0.30 e Å−3
6 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00067 (11)
Crystal data top
[Cu(C10H9NO3)(C10H8N2)]·2H2OV = 3910.9 (6) Å3
Mr = 446.94Z = 8
Monoclinic, C2/cMo Kα
a = 15.1164 (14) ŵ = 1.16 mm−1
b = 13.1426 (12) ÅT = 298 (2) K
c = 19.6898 (19) Å0.30 × 0.20 × 0.20 mm
β = 91.204 (1)º
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		3427 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2954 reflections with I > 2σ(I)
Tmin = 0.723, Tmax = 0.802Rint = 0.019
9940 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0296 restraints
wR(F2) = 0.080H atoms treated by a mixture of
independent and constrained refinement
S = 1.04Δρmax = 0.21 e Å−3
3427 reflectionsΔρmin = −0.30 e Å−3
279 parameters
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
Cu10.087909 (17)0.740584 (18)0.423632 (12)0.03594 (12)
C1−0.05975 (15)0.62930 (18)0.32611 (11)0.0488 (6)
H1−0.07670.69420.31230.059*
C2−0.10048 (18)0.5472 (2)0.29577 (13)0.0599 (7)
H2−0.14420.55600.26230.072*
C3−0.07487 (19)0.4520 (2)0.31624 (14)0.0643 (7)
H3−0.10100.39490.29650.077*
C4−0.01062 (18)0.44065 (18)0.36590 (13)0.0551 (6)
H40.00660.37620.38050.066*
C50.02824 (14)0.52682 (15)0.39396 (10)0.0379 (5)
C60.09825 (14)0.52231 (15)0.44798 (10)0.0369 (5)
C70.13000 (17)0.43154 (17)0.47509 (12)0.0517 (6)
H70.10830.36970.45880.062*
C80.19355 (17)0.4334 (2)0.52598 (13)0.0580 (7)
H80.21570.37290.54400.070*
C90.22382 (17)0.5243 (2)0.54970 (13)0.0598 (7)
H90.26620.52720.58450.072*
C100.19027 (16)0.61197 (19)0.52099 (12)0.0536 (6)
H100.21060.67420.53740.064*
C110.19829 (15)0.77373 (17)0.30493 (11)0.0424 (5)
C120.26208 (17)0.7385 (2)0.25875 (14)0.0548 (6)
H120.29240.67840.26810.066*
C130.28013 (18)0.7913 (3)0.20050 (13)0.0655 (7)
H130.32190.76570.17100.079*
C140.23770 (18)0.8812 (2)0.18480 (13)0.0660 (8)
H140.25180.91730.14590.079*
C150.17490 (17)0.9164 (2)0.22715 (12)0.0559 (6)
H150.14580.97690.21650.067*
C160.15252 (14)0.86370 (17)0.28690 (10)0.0418 (5)
C170.08414 (15)0.90614 (16)0.32727 (11)0.0440 (5)
H170.06040.96770.31240.053*
C18−0.01486 (18)0.93121 (18)0.41580 (12)0.0564 (7)
H18A−0.04450.97420.38230.068*
H18B0.01470.97520.44860.068*
C19−0.08308 (16)0.86842 (19)0.45159 (12)0.0537 (6)
H19A−0.13170.91220.46420.064*
H19B−0.10640.81740.42040.064*
C20−0.04692 (16)0.81623 (16)0.51415 (11)0.0458 (5)
N10.12982 (12)0.61166 (13)0.47065 (9)0.0392 (4)
N20.00289 (12)0.62053 (13)0.37434 (8)0.0386 (4)
N30.05187 (12)0.86882 (12)0.38171 (9)0.0397 (4)
O10.18482 (11)0.72290 (12)0.36108 (9)0.0495 (4)
O20.02817 (13)0.77239 (13)0.50911 (8)0.0566 (5)
O3−0.08925 (12)0.81717 (15)0.56686 (8)0.0650 (5)
O40.33568 (19)0.6129 (2)0.40144 (16)0.1006 (8)
O50.0196 (2)0.8368 (3)0.68258 (17)0.1303 (11)
H4A0.357 (3)0.636 (4)0.4383 (17)0.21 (3)*
H4B0.2906 (15)0.649 (2)0.3917 (17)0.109 (13)*
H5B−0.020 (2)0.842 (3)0.6523 (19)0.18 (2)*
H5A0.019 (2)0.7785 (12)0.6976 (15)0.175 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03707 (18)0.03392 (16)0.03682 (17)0.00184 (10)0.00015 (11)0.00119 (10)
C10.0478 (14)0.0539 (14)0.0445 (13)0.0022 (11)−0.0044 (11)0.0002 (10)
C20.0521 (16)0.0751 (18)0.0519 (15)−0.0081 (14)−0.0098 (12)−0.0098 (13)
C30.0676 (18)0.0602 (16)0.0647 (17)−0.0211 (14)−0.0041 (14)−0.0147 (13)
C40.0631 (16)0.0423 (13)0.0599 (15)−0.0082 (12)0.0027 (13)−0.0037 (11)
C50.0383 (12)0.0373 (11)0.0384 (11)−0.0011 (9)0.0103 (9)−0.0020 (9)
C60.0356 (11)0.0391 (11)0.0365 (11)0.0040 (9)0.0104 (9)0.0039 (9)
C70.0589 (15)0.0406 (12)0.0560 (15)0.0061 (11)0.0133 (12)0.0069 (10)
C80.0527 (15)0.0612 (16)0.0605 (16)0.0184 (13)0.0066 (13)0.0249 (13)
C90.0491 (15)0.0760 (18)0.0539 (15)0.0065 (14)−0.0047 (12)0.0183 (13)
C100.0502 (14)0.0593 (15)0.0508 (14)−0.0011 (12)−0.0094 (12)0.0054 (11)
C110.0356 (12)0.0519 (13)0.0398 (12)−0.0081 (10)0.0011 (10)−0.0061 (10)
C120.0384 (13)0.0690 (16)0.0571 (16)0.0005 (11)0.0072 (12)−0.0090 (12)
C130.0431 (15)0.107 (2)0.0465 (15)−0.0073 (16)0.0091 (12)−0.0115 (15)
C140.0566 (16)0.101 (2)0.0409 (14)−0.0149 (16)0.0046 (12)0.0101 (14)
C150.0558 (15)0.0680 (16)0.0439 (14)−0.0074 (13)−0.0002 (12)0.0093 (11)
C160.0421 (12)0.0479 (12)0.0353 (11)−0.0058 (10)0.0009 (10)−0.0019 (9)
C170.0521 (14)0.0374 (11)0.0424 (12)0.0003 (10)−0.0031 (10)0.0038 (9)
C180.0752 (18)0.0435 (13)0.0511 (14)0.0196 (12)0.0162 (13)0.0044 (11)
C190.0484 (14)0.0637 (15)0.0493 (14)0.0162 (12)0.0058 (11)−0.0034 (12)
C200.0558 (15)0.0395 (12)0.0426 (13)−0.0031 (11)0.0082 (11)−0.0034 (9)
N10.0394 (10)0.0391 (10)0.0390 (10)0.0013 (8)−0.0002 (8)0.0034 (7)
N20.0388 (10)0.0402 (10)0.0368 (9)0.0005 (8)−0.0002 (8)−0.0001 (7)
N30.0464 (11)0.0356 (9)0.0372 (10)0.0031 (8)0.0017 (8)−0.0008 (7)
O10.0432 (9)0.0496 (9)0.0561 (10)0.0093 (7)0.0124 (8)0.0095 (7)
O20.0693 (12)0.0632 (10)0.0374 (9)0.0224 (9)0.0069 (8)0.0048 (7)
O30.0732 (13)0.0702 (13)0.0526 (11)0.0028 (10)0.0231 (10)0.0038 (9)
O40.0858 (18)0.0991 (18)0.116 (2)0.0421 (15)−0.0096 (16)−0.0057 (16)
O50.097 (2)0.189 (4)0.104 (2)−0.011 (2)−0.0175 (18)0.046 (2)
Geometric parameters (Å, °) top
Cu1—O11.9475 (16)C11—C161.412 (3)
Cu1—N31.9492 (17)C11—C121.417 (3)
Cu1—O21.9715 (17)C12—C131.373 (4)
Cu1—N12.0261 (17)C12—H120.93
Cu1—N22.2429 (17)C13—C141.377 (4)
C1—N21.332 (3)C13—H130.93
C1—C21.373 (3)C14—C151.358 (4)
C1—H10.93C14—H140.93
C2—C31.368 (4)C15—C161.412 (3)
C2—H20.93C15—H150.93
C3—C41.372 (4)C16—C171.430 (3)
C3—H30.93C17—N31.284 (3)
C4—C51.385 (3)C17—H170.93
C4—H40.93C18—N31.473 (3)
C5—N21.344 (3)C18—C191.507 (3)
C5—C61.486 (3)C18—H18A0.97
C6—N11.341 (3)C18—H18B0.97
C6—C71.388 (3)C19—C201.503 (3)
C7—C81.374 (4)C19—H19A0.97
C7—H70.93C19—H19B0.97
C8—C91.359 (4)C20—O31.231 (3)
C8—H80.93C20—O21.279 (3)
C9—C101.376 (3)O4—H4A0.842 (10)
C9—H90.93O4—H4B0.847 (10)
C10—N11.334 (3)O5—H5B0.842 (10)
C10—H100.93O5—H5A0.822 (10)
C11—O11.311 (3)
O1—Cu1—N392.45 (7)C11—C12—H12119.3
O1—Cu1—O2158.33 (8)C12—C13—C14121.4 (3)
N3—Cu1—O292.82 (7)C12—C13—H13119.3
O1—Cu1—N187.53 (7)C14—C13—H13119.3
N3—Cu1—N1176.87 (7)C15—C14—C13118.9 (3)
O2—Cu1—N186.08 (7)C15—C14—H14120.6
O1—Cu1—N294.25 (7)C13—C14—H14120.6
N3—Cu1—N2105.81 (7)C14—C15—C16121.8 (3)
O2—Cu1—N2104.48 (7)C14—C15—H15119.1
N1—Cu1—N277.31 (7)C16—C15—H15119.1
N2—C1—C2123.2 (2)C11—C16—C15119.7 (2)
N2—C1—H1118.4C11—C16—C17122.9 (2)
C2—C1—H1118.4C15—C16—C17117.4 (2)
C3—C2—C1118.0 (2)N3—C17—C16127.3 (2)
C3—C2—H2121.0N3—C17—H17116.3
C1—C2—H2121.0C16—C17—H17116.3
C2—C3—C4120.1 (2)N3—C18—C19112.96 (19)
C2—C3—H3120.0N3—C18—H18A109.0
C4—C3—H3120.0C19—C18—H18A109.0
C3—C4—C5118.9 (2)N3—C18—H18B109.0
C3—C4—H4120.5C19—C18—H18B109.0
C5—C4—H4120.5H18A—C18—H18B107.8
N2—C5—C4121.2 (2)C20—C19—C18113.1 (2)
N2—C5—C6115.90 (17)C20—C19—H19A109.0
C4—C5—C6122.85 (19)C18—C19—H19A109.0
N1—C6—C7120.4 (2)C20—C19—H19B109.0
N1—C6—C5116.53 (17)C18—C19—H19B109.0
C7—C6—C5123.0 (2)H19A—C19—H19B107.8
C8—C7—C6119.7 (2)O3—C20—O2123.2 (2)
C8—C7—H7120.1O3—C20—C19120.0 (2)
C6—C7—H7120.1O2—C20—C19116.8 (2)
C9—C8—C7119.4 (2)C10—N1—C6118.93 (19)
C9—C8—H8120.3C10—N1—Cu1122.66 (15)
C7—C8—H8120.3C6—N1—Cu1118.33 (14)
C8—C9—C10118.5 (2)C1—N2—C5118.58 (19)
C8—C9—H9120.8C1—N2—Cu1129.79 (15)
C10—C9—H9120.8C5—N2—Cu1111.28 (13)
N1—C10—C9122.9 (2)C17—N3—C18116.33 (18)
N1—C10—H10118.5C17—N3—Cu1125.17 (15)
C9—C10—H10118.5C18—N3—Cu1118.45 (14)
O1—C11—C16123.7 (2)C11—O1—Cu1127.19 (14)
O1—C11—C12119.6 (2)C20—O2—Cu1125.81 (15)
C16—C11—C12116.7 (2)H4A—O4—H4B107 (2)
C13—C12—C11121.4 (3)H5B—O5—H5A108 (2)
C13—C12—H12119.3
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O2i0.842 (10)2.34 (3)3.075 (4)146 (5)
O4—H4B···O10.847 (10)1.96 (1)2.801 (3)174 (3)
O5—H5B···O30.842 (10)1.99 (2)2.794 (4)160 (5)
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.9475 (16)Cu1—N12.0261 (17)
Cu1—N31.9492 (17)Cu1—N22.2429 (17)
Cu1—O21.9715 (17)
O1—Cu1—N392.45 (7)O2—Cu1—N186.08 (7)
O1—Cu1—O2158.33 (8)O1—Cu1—N294.25 (7)
N3—Cu1—O292.82 (7)N3—Cu1—N2105.81 (7)
O1—Cu1—N187.53 (7)O2—Cu1—N2104.48 (7)
N3—Cu1—N1176.87 (7)N1—Cu1—N277.31 (7)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O2i0.842 (10)2.34 (3)3.075 (4)146 (5)
O4—H4B···O10.847 (10)1.96 (1)2.801 (3)174 (3)
O5—H5B···O30.842 (10)1.99 (2)2.794 (4)160 (5)
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1.
Acknowledgements top

This research was supported by the National Science Foundation of China (No. 20405011), the Social Development Foundation of Jiangsu Province of China (No. BS2006038) and the High Technology Research Foundation of Jiangsu Province of China (No. BG2007025).

references
References top

Bruker (2000). SMART (Version 5.625) and SAINT (Version 6.3). Bruker AXS Inc., Madison, Wisconsin, USA.

Plesch, G., Friebel, C., Warda, S. A., Sivý, J. & Švajlenová, O. (1997). Transit. Met. Chem. 22, 433–440.

Raso, A. G., Fiol, J. J., Badenas, F. & Quiros, M. (1996). Polyhedron, 18, 4407–4413.

Raso, A. G., Fiol, J. J., Zafra, A. L., Cabrero, A., Mata, I. & Molins, E. (1999). Polyhedron, 18, 871–878.

Reddy, P. A. N., Nethaji, M. & Chakravarty, A. R. (2002). Inorg. Chim. Acta, 337, 450–458.

Sheldrick, G. M. (1996). SADABS. Version 2.10. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (2000). SHELXTL. Version 6.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Wang, M. Z., Cai, G. L., Meng, Z. X. & Liu, B. L. (2005). J. Chem. Crystallogr. 35, 43–47.

Warda, S. A. (1997). Acta Cryst. C53, 1759–1761.

Warda, S. A. (1998a). Acta Cryst. C54, 1754–1755.

Warda, S. A. (1998b). Acta Cryst. C54, 187–189.

Warda, S. A. (1998c). Acta Cryst. C54, 768–770.