catena-Poly[[aqua­glycolatocopper(II)]-μ-chlorido]

Fun, H.-K.; John, J.; Jebas, S.R.; Balasubramanian, T.

doi:10.1107/S1600536808012166

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m753

doi:10.1107/S1600536808012166

Open

access

catena-Poly[[aquaglycolatocopper(II)]-μ-chlorido]

Hoong-Kun Fun,^a ^* Jain John,^b Samuel Robinson Jebas ^a ‡ and T Balasubramanian ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Physics, National Institute of Technology, Tiruchirappalli 620 015, India
^*Correspondence e-mail: hkfun@usm.my

(Received 23 April 2008; accepted 27 April 2008; online 3 May 2008)

In the crystal structure of the title compound, [Cu(C₂H₃O₃)Cl(H₂O)]_n, the Cu^II ion is five-coordinate in a distorted square-pyramidal geometry. Two O atoms from a chelating glycolate anion, an O atom from a coordinated water molecule and a chloride anion comprise the basal plane. A chloride ion from a neighbouring unit occupies the apical position and these Cu—Cl—Cu bridges link the aquaglycolatocopper(II) units into one-dimensional chains along the [001] direction. These chains are connected by O—H⋯O and O—H⋯Cl hydrogen bonds, forming an infinite three-dimensional polymeric network.

Related literature

For background to the coordination chemistry of glycolic acid, see: Gao et al. (2004 ). For related structures, see: Dengel et al. (198 7); Lanfranchi et al. (1993 ); Medina et al. (2000 ); Prout et al. (1993 ).

Experimental

Crystal data

[Cu(C₂H₃O₃)Cl(H₂O)]
M_r = 192.05
Monoclinic, P 2₁ /c
a = 7.6296 (2) Å
b = 10.0896 (3) Å
c = 7.4603 (2) Å
β = 109.632 (1)°
V = 540.91 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.45 mm⁻¹
T = 100.0 (1) K
0.56 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.189, T_max = 0.512 (expected range = 0.174–0.470)
10874 measured reflections
2372 independent reflections
2147 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.058
S = 1.05
2372 reflections
93 parameters
All H-atom parameters refined
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯Cl1ⁱ	0.76 (3)	2.32 (3)	3.0654 (10)	166 (2)
O1W—H2W1⋯O3ⁱⁱ	0.82 (2)	1.98 (2)	2.7400 (12)	153 (2)
O1—H1O1⋯O3ⁱⁱⁱ	0.80 (2)	1.81 (2)	2.6086 (13)	177 (2)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x-1, y, z; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012166/sj2487sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012166/sj2487Isup2.hkl

checkCIF report

Comment top

Glycolic acid (2-hydroxyethanoic acid) is a biologically active compound and has versatile binding modes for metals. (Gao et al., 2004). A number of structures of metal complexes containing the glycolate ligand have been reported (Medina et al., 2000; Prout et al.1993) with the chelating glycolate ligand coordinating to metal ions through the hydroxy and carboxy groups. In some coordination modes, the hydroxy groups of the glycolate are deprotonated (Dengel et al.,1987; Lanfranchi et al., 1993). In this paper we report the structure of a novel three dimensional polymeric chloro-bridged copper complex with glycolate and water as auxiliary ligands.

In the asymmetric unit of the title compound, the Cu^II ion is five–coordinated with a distorted square–pyramidal geometry. The basal plane is formed by atoms O1 and O2 from the glycolate ligand in a chelating mode, a water oxygen and a chloride anion. Cl^- anions from neighbouring molecules link the [C₂H₅ClCuO₄] units into polymeric chains along the [0 0 1] direction. The five membered ring [Cu1—O2—C2—C1—O1] is essentially planar with the maximum deviation from planarity being 0.008 (2)Å for the atom O1. The atom Cu1 is displaced by -0.1603 (1)Å out of the basal plane of the square pyramid towards atom Cl1.

The molecules are linked into one dimensional polymeric chains along the [0 0 1] direction through bridging chloride ions. Adjacent chains are interconnected by O—H···O, and O—H···Cl hydrogen bonds to form an infinite three dimensional polymeric network.

Related literature top

For background to the coordination chemistry of glycolic acid, see: Gao et al. (2004). For related structures, see: Dengel et al. (1987); Lanfranchi et al. (1993); Medina et al. (2000); Prout et al. (1993).

Experimental top

Equimolar amounts of glycolic acid and CuCl₂ were dissolved in ethanol. The solution was refluxed at a temperature of 333°K for a period of 48 h. The clear blue colour solution was allowed to evaporate slowly yielding blue crystals of (I) after one month.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering scheme. Symmetry code for atoms labelled A: x, -y + 1/2, z + 1/2.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis, showing a polymeric chain along the c axis.

catena-Poly[[aquaglycolatocopper(II)]-µ-chlorido] top

Crystal data top

[Cu(C₂H₃O₃)Cl(H₂O)]	F(000) = 380
M_r = 192.05	D_x = 2.358 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6364 reflections
a = 7.6296 (2) Å	θ = 2.8–41.4°
b = 10.0896 (3) Å	µ = 4.45 mm⁻¹
c = 7.4603 (2) Å	T = 100 K
β = 109.632 (1)°	Block, blue
V = 540.91 (3) Å³	0.56 × 0.19 × 0.17 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2372 independent reflections
Radiation source: fine-focus sealed tube	2147 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 35.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
T_min = 0.189, T_max = 0.512	k = −15→16
10874 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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	All H-atom parameters refined
S = 1.05	w = 1/[σ²(F_o²) + (0.035P)² + 0.0909P] where P = (F_o² + 2F_c²)/3
2372 reflections	(Δ/σ)_max < 0.001
93 parameters	Δρ_max = 0.80 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Cu(C₂H₃O₃)Cl(H₂O)]	V = 540.91 (3) Å³
M_r = 192.05	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6296 (2) Å	µ = 4.45 mm⁻¹
b = 10.0896 (3) Å	T = 100 K
c = 7.4603 (2) Å	0.56 × 0.19 × 0.17 mm
β = 109.632 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2372 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2147 reflections with I > 2σ(I)
T_min = 0.189, T_max = 0.512	R_int = 0.025
10874 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.058	All H-atom parameters refined
S = 1.05	Δρ_max = 0.80 e Å⁻³
2372 reflections	Δρ_min = −0.66 e Å⁻³
93 parameters

Special details top

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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

	x	y	z	U_iso*/U_eq
Cu1	0.709943 (18)	0.143386 (14)	0.84591 (2)	0.01140 (5)
Cl1	0.55544 (4)	0.22147 (3)	0.48054 (4)	0.01285 (6)
O1	0.92698 (11)	0.26130 (9)	0.90217 (13)	0.01339 (15)
O2	0.87233 (11)	0.01710 (9)	0.78289 (13)	0.01408 (15)
O3	1.15672 (12)	−0.01023 (10)	0.76906 (14)	0.01787 (17)
C1	1.08255 (15)	0.20052 (12)	0.86756 (17)	0.01349 (19)
C2	1.03389 (15)	0.05935 (12)	0.80059 (16)	0.01302 (18)
O1W	0.52646 (12)	0.00559 (10)	0.80898 (13)	0.01492 (16)
H1A	1.114 (3)	0.2483 (19)	0.773 (3)	0.017 (4)*
H1B	1.183 (3)	0.2001 (19)	0.981 (3)	0.014 (4)*
H1W1	0.526 (3)	−0.050 (3)	0.740 (3)	0.033 (6)*
H2W1	0.422 (3)	0.026 (2)	0.809 (3)	0.034 (6)*
H1O1	0.904 (3)	0.331 (2)	0.849 (3)	0.025 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01055 (7)	0.00927 (8)	0.01456 (7)	−0.00050 (4)	0.00446 (5)	−0.00081 (4)
Cl1	0.01344 (10)	0.01174 (12)	0.01357 (10)	−0.00079 (9)	0.00481 (8)	0.00024 (8)
O1	0.0120 (3)	0.0100 (4)	0.0183 (4)	0.0004 (3)	0.0053 (3)	0.0003 (3)
O2	0.0115 (3)	0.0117 (4)	0.0188 (4)	−0.0006 (3)	0.0049 (3)	−0.0012 (3)
O3	0.0139 (3)	0.0142 (4)	0.0264 (4)	0.0003 (3)	0.0078 (3)	−0.0043 (3)
C1	0.0127 (4)	0.0117 (5)	0.0170 (4)	0.0001 (4)	0.0063 (4)	−0.0010 (4)
C2	0.0119 (4)	0.0122 (5)	0.0143 (4)	0.0003 (4)	0.0034 (3)	0.0009 (4)
O1W	0.0141 (3)	0.0129 (4)	0.0193 (4)	−0.0030 (3)	0.0076 (3)	−0.0037 (3)

Geometric parameters (Å, º) top

Cu1—O1W	1.9260 (9)	O2—C2	1.2686 (13)
Cu1—O2	1.9419 (8)	O3—C2	1.2548 (14)
Cu1—O1	1.9664 (9)	C1—C2	1.5138 (17)
Cu1—Cl1ⁱ	2.2480 (3)	C1—H1A	0.951 (19)
Cu1—Cl1	2.6983 (3)	C1—H1B	0.928 (19)
Cl1—Cu1ⁱⁱ	2.2479 (3)	O1W—H1W1	0.76 (3)
O1—C1	1.4344 (14)	O1W—H2W1	0.82 (2)
O1—H1O1	0.80 (2)

O1W—Cu1—O2	89.08 (4)	C2—O2—Cu1	115.53 (8)
O1W—Cu1—O1	170.67 (4)	O1—C1—C2	109.61 (9)
O2—Cu1—O1	83.61 (4)	O1—C1—H1A	110.3 (11)
O1W—Cu1—Cl1ⁱ	92.11 (3)	C2—C1—H1A	109.0 (12)
O2—Cu1—Cl1ⁱ	168.29 (3)	O1—C1—H1B	108.4 (11)
O1—Cu1—Cl1ⁱ	93.90 (3)	C2—C1—H1B	109.3 (12)
O1W—Cu1—Cl1	90.94 (3)	H1A—C1—H1B	110.2 (16)
O2—Cu1—Cl1	92.56 (3)	O3—C2—O2	123.59 (11)
O1—Cu1—Cl1	95.15 (3)	O3—C2—C1	118.20 (10)
Cl1ⁱ—Cu1—Cl1	99.065 (9)	O2—C2—C1	118.20 (10)
Cu1ⁱⁱ—Cl1—Cu1	120.780 (12)	Cu1—O1W—H1W1	118.1 (17)
C1—O1—Cu1	113.04 (7)	Cu1—O1W—H2W1	118.3 (16)
C1—O1—H1O1	109.9 (16)	H1W1—O1W—H2W1	114 (2)
Cu1—O1—H1O1	113.7 (16)

O1W—Cu1—Cl1—Cu1ⁱⁱ	−165.23 (3)	O1—Cu1—O2—C2	−0.62 (8)
O2—Cu1—Cl1—Cu1ⁱⁱ	−76.11 (3)	Cl1ⁱ—Cu1—O2—C2	−78.90 (16)
O1—Cu1—Cl1—Cu1ⁱⁱ	7.70 (3)	Cl1—Cu1—O2—C2	94.27 (8)
Cl1ⁱ—Cu1—Cl1—Cu1ⁱⁱ	102.489 (19)	Cu1—O1—C1—C2	−1.27 (11)
O1W—Cu1—O1—C1	39.6 (3)	Cu1—O2—C2—O3	178.65 (9)
O2—Cu1—O1—C1	1.08 (8)	Cu1—O2—C2—C1	0.04 (13)
Cl1ⁱ—Cu1—O1—C1	169.58 (7)	O1—C1—C2—O3	−177.86 (10)
Cl1—Cu1—O1—C1	−90.94 (7)	O1—C1—C2—O2	0.83 (15)
O1W—Cu1—O2—C2	−174.83 (8)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···Cl1ⁱⁱⁱ	0.76 (3)	2.32 (3)	3.0654 (10)	166 (2)
O1W—H2W1···O3^iv	0.82 (2)	1.98 (2)	2.7400 (12)	153 (2)
O1—H1O1···O3^v	0.80 (2)	1.81 (2)	2.6086 (13)	177 (2)

Symmetry codes: (iii) −x+1, −y, −z+1; (iv) x−1, y, z; (v) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₃O₃)Cl(H₂O)]
M_r	192.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.6296 (2), 10.0896 (3), 7.4603 (2)
β (°)	109.632 (1)
V (Å³)	540.91 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.45
Crystal size (mm)	0.56 × 0.19 × 0.17

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.189, 0.512
No. of measured, independent and observed [I > 2σ(I)] reflections	10874, 2372, 2147
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.058, 1.05
No. of reflections	2372
No. of parameters	93
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.66

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···Cl1ⁱ	0.76 (3)	2.32 (3)	3.0654 (10)	166 (2)
O1W—H2W1···O3ⁱⁱ	0.82 (2)	1.98 (2)	2.7400 (12)	153 (2)
O1—H1O1···O3ⁱⁱⁱ	0.80 (2)	1.81 (2)	2.6086 (13)	177 (2)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) −x+2, y+1/2, −z+3/2.

Footnotes

‡Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

Acknowledgements

HKF and SRJ thank the Malaysian Government and the Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks the Universiti Sains Malaysia for a post–doctoral research fellowship.

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dengel, A. C., Griffth, W. P., Powell, R. D. & Skapski, A. C. (1987). J. Chem. Soc. Dalton Trans. pp. 991–995. CSD CrossRef Web of Science Google Scholar
Gao, S., Huo, L.-H., Zhang, Z.-Y., Zhao, H. & Zhao, J.-G. (2004). Acta Cryst. E60, m1278–m1280. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lanfranchi, M., Prati, L., Rossi, M. & Tiripicchio, A. (1993). J. Chem. Soc. Chem. Commun. pp. 1698–1699. CrossRef Web of Science Google Scholar
Medina, G., Gasque, L. & Bernès, S. (2000). Acta Cryst. C56, 766–768. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Prout, K., Mtetwa, V. S. B. & Rossotti, F. J. C. (1993). Acta Cryst. B49, 73–79. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar