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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): m357.
Published online 2010 March 3. doi:  10.1107/S1600536810007129
PMCID: PMC2984082

catena-Poly[copper(II)-bis­(μ-3-cyano-2-hydroxy­propionato)-κ3 N:O 1,O 23 O 1,O 2:N-copper(II)]

Abstract

The title compound, [Cu(C4H4NO3)2]n, exhibits a double-chain structure extending along [100]. The CuII atom, lying on an inversion center, is coordinated by two cyano N atoms from two 3-cyano-2-hydroxy­propionate ligands and two hydr­oxy O atoms and two carboxyl­ate O atom from two other two ligands in a distorted octa­hedral geometry. Inter­molecular C—H(...)O and O—H(...)O hydrogen bonds connect the chains into a three-dimensional structure.

Related literature

For the synthesis and studies of β-hydroxy­nitriles, see: Conti et al. (2003 [triangle]); Seo et al. (1994 [triangle]). For related structures, see: Klein et al. (1982 [triangle]); Wang et al. (2009 [triangle]).

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Object name is e-66-0m357-scheme1.jpg

Experimental

Crystal data

  • [Cu(C4H4NO3)2]
  • M r = 291.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m357-efi1.jpg
  • a = 6.3704 (7) Å
  • b = 8.4382 (10) Å
  • c = 10.0412 (12) Å
  • β = 104.492 (2)°
  • V = 522.59 (11) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.11 mm−1
  • T = 293 K
  • 0.28 × 0.19 × 0.12 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.624, T max = 0.776
  • 2803 measured reflections
  • 1031 independent reflections
  • 973 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.064
  • S = 1.11
  • 1031 reflections
  • 83 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007129/hy2278sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007129/hy2278Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

β-Hydroxynitriles are potentially important intermediates in the synthesis of complex organic compounds (Seo et al., 1994). The study of coordination polymers with β-hydroxynitrile is rarely reported according to Cambridge Structural Database. Herein we report the structure of the title compound.

In the title compound, the CuII atom, lying on an inversion center, is six-coordinated in a distorted octahedral geometry defined by two carboxylate O atoms and two hydroxy O atoms in the equatorial plane and two N atoms from the cyano groups in the axial positions (Table 1 and Fig. 1). Weak coordination between the CuII atom and the N atoms is indicated by a Cu—N distance of 2.545 (2) Å, due to Jahn-Teller effects. The bond lengths and angles are in normal ranges (Klein et al., 1982; Wang et al., 2009). Adjacent CuII centers are bridged by two ligands, forming a double-chain structure, which is further extended by intermolecular C—H···O and O—H···O hydrogen bonds (Table 2) into a three-dimentional supramolecular structure.

Experimental

2-Isoxazoline-3,5-dicarboxylic acid was synthesized according to the previously reported procedure (Conti et al., 2003). 3-Cyano-2-hydroxypropionic acid was obtained from 2-isoxazoline-3,5-dicarboxylic acid by selective cleavage of the N—O bond and decarboxylation under basic condition (Seo et al., 1994). A solution of Cu(NO3)2.3H2O (0.048 g, 0.2 mmol) in H2O (4 ml) was added to a solution of 3-cyano-2-hydroxypropionic acid (0.046 g, 0.4 mmol) in H2O (8 ml), then aqueous triethylamine (0.07 ml) was added dropwise to the above solution accompanied with stirring. The mixture was flitered and placed at room temperature. Blue block crystals of the title compound were obtained in three days (yield 0.046 g, 78% based on Cu).

Refinement

C-bound H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.98 (CH) and 0.97 (CH2) Å and with Uiso(H) = 1.2Ueq(C). The hydroxy H atom was found in a difference Fourier map and refined isotropically.

Figures

Fig. 1.
The structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 1-x, -y, -z; (ii) x-1, y, z; (iii) 2-x, -y, -z.]
Fig. 2.
The one-dimensional double-chain in the title compound. Dashed lines denote hydrogen bonds.

Crystal data

[Cu(C4H4NO3)2]F(000) = 294
Mr = 291.71Dx = 1.854 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2150 reflections
a = 6.3704 (7) Åθ = 3.2–26.0°
b = 8.4382 (10) ŵ = 2.11 mm1
c = 10.0412 (12) ÅT = 293 K
β = 104.492 (2)°Block, blue
V = 522.59 (11) Å30.28 × 0.19 × 0.12 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer1031 independent reflections
Radiation source: sealed tube973 reflections with I > 2σ(I)
graphiteRint = 0.017
[var phi] and ω scansθmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −5→7
Tmin = 0.624, Tmax = 0.776k = −9→10
2803 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.11w = 1/[σ2(Fo2) + (0.0477P)2 + 0.2506P] where P = (Fo2 + 2Fc2)/3
1031 reflections(Δ/σ)max < 0.001
83 parametersΔρmax = 0.32 e Å3
1 restraintΔρmin = −0.27 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cu10.50000.00000.00000.03130 (14)
N11.1980 (3)0.1558 (3)0.0646 (2)0.0635 (6)
O10.69000 (19)0.11889 (14)0.15024 (11)0.0264 (3)
H1W0.671 (4)0.117 (3)0.2292 (14)0.057 (7)*
O20.5444 (2)0.17730 (15)−0.10898 (11)0.0364 (3)
O30.6908 (2)0.41604 (15)−0.09635 (12)0.0384 (3)
C10.7140 (3)0.28079 (19)0.11473 (16)0.0256 (3)
H10.61920.34730.15450.031*
C20.6441 (3)0.2934 (2)−0.04252 (16)0.0274 (4)
C30.9491 (3)0.3336 (2)0.17056 (18)0.0345 (4)
H3A0.96410.44330.14540.041*
H3B0.98800.32660.27010.041*
C41.0950 (3)0.2340 (3)0.1150 (2)0.0419 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0435 (2)0.0282 (2)0.02069 (19)−0.01409 (12)0.00516 (14)0.00079 (10)
N10.0422 (10)0.0728 (14)0.0791 (14)−0.0038 (10)0.0222 (10)−0.0190 (12)
O10.0346 (6)0.0251 (6)0.0203 (5)−0.0059 (5)0.0080 (5)−0.0001 (4)
O20.0537 (8)0.0323 (7)0.0217 (6)−0.0152 (6)0.0065 (5)0.0008 (5)
O30.0626 (9)0.0272 (7)0.0284 (6)−0.0107 (6)0.0170 (6)0.0016 (5)
C10.0333 (9)0.0228 (8)0.0232 (7)−0.0030 (6)0.0116 (6)−0.0017 (6)
C20.0327 (8)0.0276 (8)0.0244 (8)−0.0008 (7)0.0120 (7)0.0001 (6)
C30.0385 (10)0.0351 (9)0.0306 (8)−0.0119 (8)0.0099 (7)−0.0069 (7)
C40.0307 (9)0.0476 (11)0.0465 (11)−0.0109 (9)0.0081 (8)−0.0063 (9)

Geometric parameters (Å, °)

Cu1—O21.9159 (12)O3—C21.238 (2)
Cu1—O11.9579 (11)C1—C31.528 (2)
Cu1—N1i2.545 (2)C1—C21.533 (2)
N1—C41.135 (3)C1—H10.9800
O1—C11.4298 (19)C3—C41.464 (3)
O1—H1W0.832 (10)C3—H3A0.9700
O2—C21.264 (2)C3—H3B0.9700
O2ii—Cu1—O2180.0C3—C1—C2111.28 (14)
O2ii—Cu1—O196.39 (5)O1—C1—H1109.3
O2—Cu1—O183.62 (5)C3—C1—H1109.3
O2—Cu1—O1ii96.38 (5)C2—C1—H1109.3
O1—Cu1—O1ii179.999 (1)O3—C2—O2124.17 (15)
O1—Cu1—N1i84.25 (6)O3—C2—C1117.92 (14)
O2—Cu1—N1i88.35 (6)O2—C2—C1117.90 (14)
O1ii—Cu1—N1i95.74 (6)C4—C3—C1110.51 (15)
O2ii—Cu1—N1i91.65 (6)C4—C3—H3A109.5
C1—O1—Cu1112.43 (9)C1—C3—H3A109.5
C1—O1—H1W108.0 (19)C4—C3—H3B109.5
Cu1—O1—H1W120.9 (19)C1—C3—H3B109.5
C2—O2—Cu1115.49 (10)H3A—C3—H3B108.1
O1—C1—C3110.09 (14)N1—C4—C3175.7 (2)
O1—C1—C2107.56 (12)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1···O2iii0.982.543.240 (2)128
O1—H1W···O3iii0.83 (2)1.75 (2)2.560 (2)165 (4)

Symmetry codes: (iii) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2278).

References

  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Conti, D., Rodriquez, M., Sega, A. & Taddei, M. (2003). Tetrahedron Lett.44, 5327–5330.
  • Klein, C. L., Majeste, R. J., Trefonas, L. M. & O’Connor, C. J. (1982). Inorg. Chem.21, 1891–1897.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Seo, M.-H., Lee, Y.-Y. & Goo, Y.-M. (1994). Synth. Commun.24, 1433–1439.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, G.-H., Li, Z.-G., Jia, H.-Q., Hu, N.-H. & Xu, J.-W. (2009). CrystEngComm, 11, 292–297. [PMC free article] [PubMed]

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