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Acta Cryst. (2007). E63, m1494    [ doi:10.1107/S1600536807019514 ]

catena-Poly[[[aquacopper(II)]-[mu]-[(E)-2-(4-oxopentan-2-ylideneamino)benzoato-[kappa]4O,N,O':O'']] monohydrate]

M.-N. Cao, S.-M. Shi, F.-H. Luo, C.-X. Cheng and Z.-Q. Hu

Abstract top

The ligand of the title compound, {[Cu(C12H11NO2)(H2O)]·H2O}n, has been synthesized from o-aminobenzoic acid and acetyl acetone. Bond lengths and angles show normal values. The crystal structure is stabilized by several hydrogen bonds.

Comment top

The crystal structure and some properties of a substituted benzoate-copper(II) complex were previously reported by Plesch et al., (1991) and Shi et al., (2006).

In the title compound, each Cu atom is five-coordinated by one oxygen atom of a water molecule, one carboxylate O atom and one amino N atom of the ligand ((E)-2-(4-oxopentan-2-ylideneamino)-benzoato) and one µ2-O atom from another ligand, forming a slightly distorted trigonal bipyramid (Fig. 1). The crystal structure is stabilized by several hydrogen bonds (Table 2).

Related literature top

For related literature, see: Plesch et al. (1991); Shi & Hu (2006).

Experimental top

To an ethanol solution of o-aminobenzic acid (6.85 g, 0.1 mol), acetylacetone (5 g, 0.05 mol) was slowly added with continuous stirring at reflux for 5 h. The reaction mixture was cooled to room temperature, and the Schiff base ligand, viz. (E)-2-(4-oxopentan-2-ylideneamino)benzoic acid, precipitated after one night as a yellow solid. White crystals of the ligand were recrystallized from ethanol. 1 mmol of the Schiff base ligand, 0.5 mmol Cu(OAc)2, dimethylformamide (15 ml) and 2 drops of triethylamine were stirred for 5 h at room temperature. The solution was filtered and allowed to stand at room temperature without disturbing, crystals of of the title compound were obtained after about 3 weeks.

Refinement top

After having located them in a difference map, all H-atoms were fixed geometrically at ideal positions and allowed to ride on their parent atoms with C—H = 0.93 Å, or Cmethyl—H = 0.96 Å. The O—H distances were kept as initially found in the difference map Uiso(H) was set to 1.2Ueq(C,O) or Uiso(H) = 1.5Ueq(Cmethyl). The methyl groups were allowed to rotate but not to tip.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing 30% probability displacement ellipsoids. [Symmetry codes: (a) 1/2 - x, -1/2 + y, z; (b) 1/2 - x, 1/2 + y, z].
catena-Poly[[[aquacopper(II)]-µ-[(E)-2-(4-oxopentan-2-ylideneamino)benzoato- κ4O,N,O':O''] monohydrate] top
Crystal data top
[Cu(C12H11NO2)(H2O)]·H2OF(000) = 1304
Mr = 316.79Dx = 1.655 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3438 reflections
a = 8.1933 (7) Åθ = 2.7–25.1°
b = 8.8144 (7) ŵ = 1.73 mm−1
c = 35.209 (3) ÅT = 292 K
V = 2542.7 (4) Å3Block, green
Z = 80.20 × 0.10 × 0.02 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3029 independent reflections
Radiation source: fine-focus sealed tube2209 reflections with I > 2σ(I)
graphiteRint = 0.110
φ and ω scansθmax = 28.0°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −10→10
Tmin = 0.723, Tmax = 0.966k = −11→9
17406 measured reflectionsl = −41→46
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0644P)2]
where P = (Fo2 + 2Fc2)/3
3029 reflections(Δ/σ)max < 0.001
174 parametersΔρmax = 0.55 e Å−3
0 restraintsΔρmin = −0.62 e Å−3
Crystal data top
[Cu(C12H11NO2)(H2O)]·H2OV = 2542.7 (4) Å3
Mr = 316.79Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.1933 (7) ŵ = 1.73 mm−1
b = 8.8144 (7) ÅT = 292 K
c = 35.209 (3) Å0.20 × 0.10 × 0.02 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3029 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		2209 reflections with I > 2σ(I)
Tmin = 0.723, Tmax = 0.966Rint = 0.110
17406 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.55 e Å−3
S = 0.99Δρmin = −0.62 e Å−3
3029 reflectionsAbsolute structure: ?
174 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Cu10.06114 (4)0.28463 (4)0.410032 (10)0.02286 (15)
C10.1120 (4)0.0753 (4)0.33769 (9)0.0251 (7)
C20.1813 (4)0.0274 (4)0.30336 (10)0.0377 (8)
H20.2658−0.04300.30390.045*
C30.1284 (5)0.0812 (5)0.26910 (10)0.0465 (10)
H30.17470.04590.24670.056*
C40.0047 (5)0.1891 (4)0.26804 (10)0.0408 (9)
H4−0.02880.22990.24500.049*
C5−0.0676 (4)0.2348 (4)0.30134 (11)0.0361 (8)
H5−0.15150.30580.30050.043*
C6−0.0183 (4)0.1776 (4)0.33641 (8)0.0246 (7)
C7−0.2511 (4)0.2408 (3)0.37425 (9)0.0249 (7)
C8−0.3701 (4)0.1592 (4)0.34817 (10)0.0398 (9)
H8A−0.42010.23120.33130.060*
H8B−0.45280.11040.36310.060*
H8C−0.31250.08430.33360.060*
C9−0.3244 (4)0.3229 (4)0.40459 (9)0.0276 (7)
H9−0.43730.31620.40670.033*
C10−0.2457 (4)0.4110 (4)0.43107 (9)0.0257 (7)
C11−0.3420 (4)0.4982 (4)0.45991 (9)0.0320 (8)
H11A−0.32480.45500.48460.048*
H11B−0.45590.49330.45360.048*
H11C−0.30700.60210.45990.048*
C120.1892 (4)0.0166 (4)0.37355 (9)0.0257 (7)
N1−0.0924 (3)0.2318 (3)0.37032 (7)0.0230 (6)
O1−0.0887 (2)0.4241 (3)0.43399 (7)0.0326 (6)
O20.1718 (3)0.0870 (2)0.40485 (6)0.0266 (5)
O30.2711 (3)−0.1019 (3)0.37077 (7)0.0399 (6)
O40.2098 (3)0.3404 (3)0.45295 (7)0.0393 (6)
H4A0.27860.28190.46030.059*
H4B0.20190.41850.46400.059*
O50.0519 (3)0.6591 (3)0.47715 (7)0.0411 (6)
H5A0.00320.59650.45900.062*
H5B0.00820.64770.49950.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0211 (2)0.0222 (2)0.0253 (2)0.00220 (15)−0.00185 (15)−0.00432 (15)
C10.0225 (15)0.0237 (16)0.0292 (18)−0.0017 (13)0.0015 (13)−0.0027 (13)
C20.0340 (19)0.043 (2)0.036 (2)0.0065 (16)0.0054 (16)−0.0098 (17)
C30.051 (2)0.063 (3)0.026 (2)−0.005 (2)0.0076 (17)−0.0108 (19)
C40.052 (2)0.049 (2)0.0209 (18)−0.0052 (19)−0.0057 (16)0.0011 (16)
C50.0362 (19)0.038 (2)0.034 (2)−0.0001 (16)−0.0036 (15)0.0015 (16)
C60.0258 (16)0.0248 (17)0.0233 (17)−0.0047 (13)−0.0016 (12)−0.0031 (13)
C70.0253 (15)0.0214 (16)0.0280 (17)0.0008 (13)−0.0049 (13)0.0019 (13)
C80.0289 (18)0.046 (2)0.044 (2)−0.0029 (17)−0.0074 (16)−0.0110 (19)
C90.0191 (15)0.0300 (18)0.0337 (18)0.0006 (13)0.0008 (13)−0.0016 (14)
C100.0235 (16)0.0229 (16)0.0306 (17)0.0049 (13)0.0002 (13)0.0031 (14)
C110.0261 (17)0.035 (2)0.0349 (19)0.0080 (14)0.0010 (14)−0.0064 (15)
C120.0194 (14)0.0257 (17)0.0320 (18)−0.0040 (13)0.0005 (13)−0.0006 (14)
N10.0238 (13)0.0196 (13)0.0257 (14)0.0016 (10)−0.0024 (10)−0.0007 (11)
O10.0221 (11)0.0309 (13)0.0449 (15)0.0026 (9)−0.0021 (10)−0.0164 (11)
O20.0324 (13)0.0205 (11)0.0268 (12)0.0041 (10)−0.0022 (9)−0.0027 (9)
O30.0448 (15)0.0365 (14)0.0385 (15)0.0230 (12)−0.0048 (12)−0.0094 (11)
O40.0385 (14)0.0382 (14)0.0411 (14)0.0152 (12)−0.0173 (11)−0.0181 (12)
O50.0456 (16)0.0429 (15)0.0349 (14)−0.0157 (12)0.0022 (11)0.0004 (12)
Geometric parameters (Å, °) top
Cu1—O11.931 (2)C7—C81.521 (4)
Cu1—N11.938 (3)C8—H8A0.9600
Cu1—O21.972 (2)C8—H8B0.9600
Cu1—O42.002 (2)C8—H8C0.9600
Cu1—O3i2.191 (2)C9—C101.374 (4)
C1—C61.399 (4)C9—H90.9300
C1—C21.400 (4)C10—O11.296 (4)
C1—C121.504 (4)C10—C111.498 (4)
C2—C31.367 (5)C11—H11A0.9600
C2—H20.9300C11—H11B0.9600
C3—C41.390 (6)C11—H11C0.9600
C3—H30.9300C12—O31.246 (4)
C4—C51.374 (5)C12—O21.273 (4)
C4—H40.9300O3—Cu1ii2.191 (2)
C5—C61.394 (5)O4—H4A0.8066
C5—H50.9300O4—H4B0.7933
C6—N11.422 (4)O5—H5A0.9344
C7—N11.310 (4)O5—H5B0.8690
C7—C91.423 (4)
O1—Cu1—N193.19 (10)C7—C8—H8A109.5
O1—Cu1—O2153.49 (10)C7—C8—H8B109.5
N1—Cu1—O291.10 (10)H8A—C8—H8B109.5
O1—Cu1—O484.30 (9)C7—C8—H8C109.5
N1—Cu1—O4176.97 (10)H8A—C8—H8C109.5
O2—Cu1—O490.40 (9)H8B—C8—H8C109.5
O1—Cu1—O3i112.57 (10)C10—C9—C7126.8 (3)
N1—Cu1—O3i93.54 (10)C10—C9—H9116.6
O2—Cu1—O3i93.23 (9)C7—C9—H9116.6
O4—Cu1—O3i89.00 (10)O1—C10—C9124.8 (3)
C6—C1—C2118.4 (3)O1—C10—C11115.0 (3)
C6—C1—C12124.7 (3)C9—C10—C11120.2 (3)
C2—C1—C12116.8 (3)C10—C11—H11A109.5
C3—C2—C1121.9 (3)C10—C11—H11B109.5
C3—C2—H2119.0H11A—C11—H11B109.5
C1—C2—H2119.0C10—C11—H11C109.5
C2—C3—C4119.5 (3)H11A—C11—H11C109.5
C2—C3—H3120.3H11B—C11—H11C109.5
C4—C3—H3120.3O3—C12—O2122.5 (3)
C5—C4—C3119.5 (4)O3—C12—C1116.7 (3)
C5—C4—H4120.3O2—C12—C1120.8 (3)
C3—C4—H4120.3C7—N1—C6122.2 (3)
C4—C5—C6121.6 (3)C7—N1—Cu1123.6 (2)
C4—C5—H5119.2C6—N1—Cu1114.16 (19)
C6—C5—H5119.2C10—O1—Cu1122.6 (2)
C5—C6—C1118.9 (3)C12—O2—Cu1124.2 (2)
C5—C6—N1119.9 (3)C12—O3—Cu1ii132.2 (2)
C1—C6—N1121.0 (3)Cu1—O4—H4A120.7
N1—C7—C9121.9 (3)Cu1—O4—H4B122.2
N1—C7—C8123.0 (3)H4A—O4—H4B117.0
C9—C7—C8115.0 (3)H5A—O5—H5B112.1
C6—C1—C2—C32.0 (5)C1—C6—N1—C7−135.7 (3)
C12—C1—C2—C3−175.6 (3)C5—C6—N1—Cu1−132.7 (3)
C1—C2—C3—C41.5 (6)C1—C6—N1—Cu142.7 (4)
C2—C3—C4—C5−3.0 (6)O1—Cu1—N1—C7−26.1 (3)
C3—C4—C5—C61.1 (6)O2—Cu1—N1—C7127.7 (3)
C4—C5—C6—C12.4 (5)O3i—Cu1—N1—C7−139.0 (3)
C4—C5—C6—N1177.8 (3)O1—Cu1—N1—C6155.5 (2)
C2—C1—C6—C5−3.8 (5)O2—Cu1—N1—C6−50.7 (2)
C12—C1—C6—C5173.5 (3)O3i—Cu1—N1—C642.6 (2)
C2—C1—C6—N1−179.2 (3)C9—C10—O1—Cu1−15.8 (5)
C12—C1—C6—N1−1.9 (5)C11—C10—O1—Cu1162.9 (2)
N1—C7—C9—C105.7 (5)N1—Cu1—O1—C1026.3 (3)
C8—C7—C9—C10−177.1 (3)O2—Cu1—O1—C10−72.6 (3)
C7—C9—C10—O1−5.2 (6)O4—Cu1—O1—C10−151.9 (3)
C7—C9—C10—C11176.2 (3)O3i—Cu1—O1—C10121.5 (3)
C6—C1—C12—O3160.9 (3)O3—C12—O2—Cu1174.0 (2)
C2—C1—C12—O3−21.7 (4)C1—C12—O2—Cu1−5.2 (4)
C6—C1—C12—O2−19.8 (5)O1—Cu1—O2—C12134.0 (2)
C2—C1—C12—O2157.6 (3)N1—Cu1—O2—C1234.6 (2)
C9—C7—N1—C6−166.8 (3)O4—Cu1—O2—C12−148.0 (2)
C8—C7—N1—C616.2 (5)O3i—Cu1—O2—C12−59.0 (2)
C9—C7—N1—Cu114.9 (4)O2—C12—O3—Cu1ii−10.7 (5)
C8—C7—N1—Cu1−162.1 (2)C1—C12—O3—Cu1ii168.5 (2)
C5—C6—N1—C748.9 (4)
Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1/2, y−1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5B···O4iii0.872.453.264 (3)156
O5—H5B···O1iii0.872.513.227 (3)140
O5—H5A···O10.931.912.815 (3)162
O4—H4B···O50.792.493.208 (4)150
O4—H4A···O5ii0.811.862.663 (3)176
Symmetry codes: (iii) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5B···O4i0.872.453.264 (3)156
O5—H5B···O1i0.872.513.227 (3)140
O5—H5A···O10.931.912.815 (3)162
O4—H4B···O50.792.493.208 (4)150
O4—H4A···O5ii0.811.862.663 (3)176
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, z.
Acknowledgements top

This work was supported by Hubei Education Government of China (grant No. 20040131).

references
References top

Bruker (2001). SAINT (Version 6.45), SMART (Version 5.628) and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Plesch, G., Friebel, C., Ŝvajlenová, O. & Krätsmár-Ŝmogroviĉ, J. (1991). Polyhedron, 10, 893–898.

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

Sheldrick, G. M. (2001). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Shi, S.-M. & Hu, Z.-Q. (2006). Acta Cryst. E62, m426–m428. Please check - these page numbers are for the reference Wu, X.-H., Ren, Y., Yu, G.-A. & Liu, S.-H.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.