catena-Poly[copper(II)-bis­(μ-3-cyano-2-hydroxy­propionato)-κ3N:O1,O2;κ3O1,O2:N-copper(II)]

Wang, J.-D.; Han, S.-M.

doi:10.1107/S1600536810007129

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page m357

doi:10.1107/S1600536810007129

Open

access

catena-Poly[copper(II)-bis(μ-3-cyano-2-hydroxypropionato)-κ³N:O¹,O²;κ³O¹,O²:N-copper(II)]

Ji-Dong Wang ^a,^b and Shu-Min Han ^a,^c ^*

^aCollege of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, People's Republic of China, ^bCollege of Information Technology and Engineering, Yanshan University, Qinhuangdao 066004, People's Republic of China, and ^cState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People's Republic of China
^*Correspondence e-mail: JDWangYsu@gmail.com

(Received 22 January 2010; accepted 24 February 2010; online 3 March 2010)

The title compound, [Cu(C₄H₄NO₃)₂]_n, exhibits a double-chain structure extending along [100]. The Cu^II 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 ); Seo et al. (1994 ). For related structures, see: Klein et al. (1982 ); Wang et al. (2009 ).

Experimental

Crystal data

[Cu(C₄H₄NO₃)₂]
M_r = 291.71
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.023
wR(F²) = 0.064
S = 1.11
1031 reflections
83 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O2	1.9159 (12)
Cu1—O1	1.9579 (11)
Cu1—N1ⁱ	2.545 (2)
Symmetry code: (i) x-1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2ⁱⁱ	0.98	2.54	3.240 (2)	128
O1—H1W⋯O3ⁱⁱ	0.83 (2)	1.75 (2)	2.560 (2)	165 (4)
Symmetry code: (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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 Cu^II 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 Cu^II 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 Cu^II 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.

Related literature top

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

Experimental top

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).

Computing details top

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

Figures top

	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.

catena-Poly[copper(II)-bis(µ-3-cyano-2-hydroxypropionato)- κ³N:O¹,O²;κ³O¹,O²:N- copper(II)] top

Crystal data top

[Cu(C₄H₄NO₃)₂]	F(000) = 294
M_r = 291.71	D_x = 1.854 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2150 reflections
a = 6.3704 (7) Å	θ = 3.2–26.0°
b = 8.4382 (10) Å	µ = 2.11 mm⁻¹
c = 10.0412 (12) Å	T = 293 K
β = 104.492 (2)°	Block, blue
V = 522.59 (11) Å³	0.28 × 0.19 × 0.12 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	1031 independent reflections
Radiation source: sealed tube	973 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→7
T_min = 0.624, T_max = 0.776	k = −9→10
2803 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0477P)² + 0.2506P] where P = (F_o² + 2F_c²)/3
1031 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.32 e Å⁻³
1 restraint	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Cu(C₄H₄NO₃)₂]	V = 522.59 (11) Å³
M_r = 291.71	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.3704 (7) Å	µ = 2.11 mm⁻¹
b = 8.4382 (10) Å	T = 293 K
c = 10.0412 (12) Å	0.28 × 0.19 × 0.12 mm
β = 104.492 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	1031 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	973 reflections with I > 2σ(I)
T_min = 0.624, T_max = 0.776	R_int = 0.017
2803 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	1 restraint
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.32 e Å⁻³
1031 reflections	Δρ_min = −0.27 e Å⁻³
83 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.0000	0.0000	0.03130 (14)
N1	1.1980 (3)	0.1558 (3)	0.0646 (2)	0.0635 (6)
O1	0.69000 (19)	0.11889 (14)	0.15024 (11)	0.0264 (3)
H1W	0.671 (4)	0.117 (3)	0.2292 (14)	0.057 (7)*
O2	0.5444 (2)	0.17730 (15)	−0.10898 (11)	0.0364 (3)
O3	0.6908 (2)	0.41604 (15)	−0.09635 (12)	0.0384 (3)
C1	0.7140 (3)	0.28079 (19)	0.11473 (16)	0.0256 (3)
H1	0.6192	0.3473	0.1545	0.031*
C2	0.6441 (3)	0.2934 (2)	−0.04252 (16)	0.0274 (4)
C3	0.9491 (3)	0.3336 (2)	0.17056 (18)	0.0345 (4)
H3A	0.9641	0.4433	0.1454	0.041*
H3B	0.9880	0.3266	0.2701	0.041*
C4	1.0950 (3)	0.2340 (3)	0.1150 (2)	0.0419 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0435 (2)	0.0282 (2)	0.02069 (19)	−0.01409 (12)	0.00516 (14)	0.00079 (10)
N1	0.0422 (10)	0.0728 (14)	0.0791 (14)	−0.0038 (10)	0.0222 (10)	−0.0190 (12)
O1	0.0346 (6)	0.0251 (6)	0.0203 (5)	−0.0059 (5)	0.0080 (5)	−0.0001 (4)
O2	0.0537 (8)	0.0323 (7)	0.0217 (6)	−0.0152 (6)	0.0065 (5)	0.0008 (5)
O3	0.0626 (9)	0.0272 (7)	0.0284 (6)	−0.0107 (6)	0.0170 (6)	0.0016 (5)
C1	0.0333 (9)	0.0228 (8)	0.0232 (7)	−0.0030 (6)	0.0116 (6)	−0.0017 (6)
C2	0.0327 (8)	0.0276 (8)	0.0244 (8)	−0.0008 (7)	0.0120 (7)	0.0001 (6)
C3	0.0385 (10)	0.0351 (9)	0.0306 (8)	−0.0119 (8)	0.0099 (7)	−0.0069 (7)
C4	0.0307 (9)	0.0476 (11)	0.0465 (11)	−0.0109 (9)	0.0081 (8)	−0.0063 (9)

Geometric parameters (Å, º) top

Cu1—O2	1.9159 (12)	O3—C2	1.238 (2)
Cu1—O1	1.9579 (11)	C1—C3	1.528 (2)
Cu1—N1ⁱ	2.545 (2)	C1—C2	1.533 (2)
N1—C4	1.135 (3)	C1—H1	0.9800
O1—C1	1.4298 (19)	C3—C4	1.464 (3)
O1—H1W	0.832 (10)	C3—H3A	0.9700
O2—C2	1.264 (2)	C3—H3B	0.9700

O2ⁱⁱ—Cu1—O2	180.0	C3—C1—C2	111.28 (14)
O2ⁱⁱ—Cu1—O1	96.39 (5)	O1—C1—H1	109.3
O2—Cu1—O1	83.62 (5)	C3—C1—H1	109.3
O2—Cu1—O1ⁱⁱ	96.38 (5)	C2—C1—H1	109.3
O1—Cu1—O1ⁱⁱ	179.999 (1)	O3—C2—O2	124.17 (15)
O1—Cu1—N1ⁱ	84.25 (6)	O3—C2—C1	117.92 (14)
O2—Cu1—N1ⁱ	88.35 (6)	O2—C2—C1	117.90 (14)
O1ⁱⁱ—Cu1—N1ⁱ	95.74 (6)	C4—C3—C1	110.51 (15)
O2ⁱⁱ—Cu1—N1ⁱ	91.65 (6)	C4—C3—H3A	109.5
C1—O1—Cu1	112.43 (9)	C1—C3—H3A	109.5
C1—O1—H1W	108.0 (19)	C4—C3—H3B	109.5
Cu1—O1—H1W	120.9 (19)	C1—C3—H3B	109.5
C2—O2—Cu1	115.49 (10)	H3A—C3—H3B	108.1
O1—C1—C3	110.09 (14)	N1—C4—C3	175.7 (2)
O1—C1—C2	107.56 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱⁱⁱ	0.98	2.54	3.240 (2)	128
O1—H1W···O3ⁱⁱⁱ	0.83 (2)	1.75 (2)	2.560 (2)	165 (4)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₄H₄NO₃)₂]
M_r	291.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.3704 (7), 8.4382 (10), 10.0412 (12)
β (°)	104.492 (2)
V (Å³)	522.59 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.11
Crystal size (mm)	0.28 × 0.19 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.624, 0.776
No. of measured, independent and observed [I > 2σ(I)] reflections	2803, 1031, 973
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.064, 1.11
No. of reflections	1031
No. of parameters	83
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.27

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—O2	1.9159 (12)	Cu1—N1ⁱ	2.545 (2)
Cu1—O1	1.9579 (11)

Symmetry code: (i) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱⁱ	0.98	2.54	3.240 (2)	128
O1—H1W···O3ⁱⁱ	0.832 (16)	1.747 (15)	2.560 (2)	165 (4)

Symmetry code: (ii) x, −y+1/2, z+1/2.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Conti, D., Rodriquez, M., Sega, A. & Taddei, M. (2003). Tetrahedron Lett. 44, 5327–5330. Web of Science CrossRef CAS Google Scholar
Klein, C. L., Majeste, R. J., Trefonas, L. M. & O'Connor, C. J. (1982). Inorg. Chem. 21, 1891–1897. CSD CrossRef CAS Web of Science Google Scholar
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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Seo, M.-H., Lee, Y.-Y. & Goo, Y.-M. (1994). Synth. Commun. 24, 1433–1439. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, G.-H., Li, Z.-G., Jia, H.-Q., Hu, N.-H. & Xu, J.-W. (2009). CrystEngComm, 11, 292–297. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.