metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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 CuII 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[Gao, S., Huo, L.-H., Zhang, Z.-Y., Zhao, H. & Zhao, J.-G. (2004). Acta Cryst. E60, m1278-m1280.]). For related structures, see: Dengel et al. (198[Dengel, A. C., Griffth, W. P., Powell, R. D. & Skapski, A. C. (1987). J. Chem. Soc. Dalton Trans. pp. 991-995.]7); Lanfranchi et al. (1993[Lanfranchi, M., Prati, L., Rossi, M. & Tiripicchio, A. (1993). J. Chem. Soc. Chem. Commun. pp. 1698-1699.]); Medina et al. (2000[Medina, G., Gasque, L. & Bernès, S. (2000). Acta Cryst. C56, 766-768.]); Prout et al. (1993[Prout, K., Mtetwa, V. S. B. & Rossotti, F. J. C. (1993). Acta Cryst. B49, 73-79.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(C2H3O3)Cl(H2O)]

  • Mr = 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[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.189, Tmax = 0.512 (expected range = 0.174–0.470)

  • 10874 measured reflections

  • 2372 independent reflections

  • 2147 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.80 e Å−3

  • Δρmin = −0.66 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]).

Supporting information


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 CuII 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.

Refinement top

All the hydrogen atoms were located from the Fourier map and were allowed to refine freely.

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
[Figure 1] 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.
[Figure 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
Mr = 192.05Dx = 2.358 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6364 reflections
a = 7.6296 (2) Åθ = 2.8–41.4°
b = 10.0896 (3) ŵ = 4.45 mm1
c = 7.4603 (2) ÅT = 100 K
β = 109.632 (1)°Block, blue
V = 540.91 (3) Å30.56 × 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 tube2147 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ϕ and ω scansθmax = 35.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 1212
Tmin = 0.189, Tmax = 0.512k = 1516
10874 measured reflectionsl = 1212
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)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.035P)2 + 0.0909P]
where P = (Fo2 + 2Fc2)/3
2372 reflections(Δ/σ)max < 0.001
93 parametersΔρmax = 0.80 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
[Cu(C2H3O3)Cl(H2O)]V = 540.91 (3) Å3
Mr = 192.05Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.6296 (2) ŵ = 4.45 mm1
b = 10.0896 (3) ÅT = 100 K
c = 7.4603 (2) Å0.56 × 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)
Tmin = 0.189, Tmax = 0.512Rint = 0.025
10874 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.058All H-atom parameters refined
S = 1.05Δρmax = 0.80 e Å3
2372 reflectionsΔρmin = 0.66 e Å3
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
xyzUiso*/Ueq
Cu10.709943 (18)0.143386 (14)0.84591 (2)0.01140 (5)
Cl10.55544 (4)0.22147 (3)0.48054 (4)0.01285 (6)
O10.92698 (11)0.26130 (9)0.90217 (13)0.01339 (15)
O20.87233 (11)0.01710 (9)0.78289 (13)0.01408 (15)
O31.15672 (12)0.01023 (10)0.76906 (14)0.01787 (17)
C11.08255 (15)0.20052 (12)0.86756 (17)0.01349 (19)
C21.03389 (15)0.05935 (12)0.80059 (16)0.01302 (18)
O1W0.52646 (12)0.00559 (10)0.80898 (13)0.01492 (16)
H1A1.114 (3)0.2483 (19)0.773 (3)0.017 (4)*
H1B1.183 (3)0.2001 (19)0.981 (3)0.014 (4)*
H1W10.526 (3)0.050 (3)0.740 (3)0.033 (6)*
H2W10.422 (3)0.026 (2)0.809 (3)0.034 (6)*
H1O10.904 (3)0.331 (2)0.849 (3)0.025 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01055 (7)0.00927 (8)0.01456 (7)0.00050 (4)0.00446 (5)0.00081 (4)
Cl10.01344 (10)0.01174 (12)0.01357 (10)0.00079 (9)0.00481 (8)0.00024 (8)
O10.0120 (3)0.0100 (4)0.0183 (4)0.0004 (3)0.0053 (3)0.0003 (3)
O20.0115 (3)0.0117 (4)0.0188 (4)0.0006 (3)0.0049 (3)0.0012 (3)
O30.0139 (3)0.0142 (4)0.0264 (4)0.0003 (3)0.0078 (3)0.0043 (3)
C10.0127 (4)0.0117 (5)0.0170 (4)0.0001 (4)0.0063 (4)0.0010 (4)
C20.0119 (4)0.0122 (5)0.0143 (4)0.0003 (4)0.0034 (3)0.0009 (4)
O1W0.0141 (3)0.0129 (4)0.0193 (4)0.0030 (3)0.0076 (3)0.0037 (3)
Geometric parameters (Å, º) top
Cu1—O1W1.9260 (9)O2—C21.2686 (13)
Cu1—O21.9419 (8)O3—C21.2548 (14)
Cu1—O11.9664 (9)C1—C21.5138 (17)
Cu1—Cl1i2.2480 (3)C1—H1A0.951 (19)
Cu1—Cl12.6983 (3)C1—H1B0.928 (19)
Cl1—Cu1ii2.2479 (3)O1W—H1W10.76 (3)
O1—C11.4344 (14)O1W—H2W10.82 (2)
O1—H1O10.80 (2)
O1W—Cu1—O289.08 (4)C2—O2—Cu1115.53 (8)
O1W—Cu1—O1170.67 (4)O1—C1—C2109.61 (9)
O2—Cu1—O183.61 (4)O1—C1—H1A110.3 (11)
O1W—Cu1—Cl1i92.11 (3)C2—C1—H1A109.0 (12)
O2—Cu1—Cl1i168.29 (3)O1—C1—H1B108.4 (11)
O1—Cu1—Cl1i93.90 (3)C2—C1—H1B109.3 (12)
O1W—Cu1—Cl190.94 (3)H1A—C1—H1B110.2 (16)
O2—Cu1—Cl192.56 (3)O3—C2—O2123.59 (11)
O1—Cu1—Cl195.15 (3)O3—C2—C1118.20 (10)
Cl1i—Cu1—Cl199.065 (9)O2—C2—C1118.20 (10)
Cu1ii—Cl1—Cu1120.780 (12)Cu1—O1W—H1W1118.1 (17)
C1—O1—Cu1113.04 (7)Cu1—O1W—H2W1118.3 (16)
C1—O1—H1O1109.9 (16)H1W1—O1W—H2W1114 (2)
Cu1—O1—H1O1113.7 (16)
O1W—Cu1—Cl1—Cu1ii165.23 (3)O1—Cu1—O2—C20.62 (8)
O2—Cu1—Cl1—Cu1ii76.11 (3)Cl1i—Cu1—O2—C278.90 (16)
O1—Cu1—Cl1—Cu1ii7.70 (3)Cl1—Cu1—O2—C294.27 (8)
Cl1i—Cu1—Cl1—Cu1ii102.489 (19)Cu1—O1—C1—C21.27 (11)
O1W—Cu1—O1—C139.6 (3)Cu1—O2—C2—O3178.65 (9)
O2—Cu1—O1—C11.08 (8)Cu1—O2—C2—C10.04 (13)
Cl1i—Cu1—O1—C1169.58 (7)O1—C1—C2—O3177.86 (10)
Cl1—Cu1—O1—C190.94 (7)O1—C1—C2—O20.83 (15)
O1W—Cu1—O2—C2174.83 (8)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···Cl1iii0.76 (3)2.32 (3)3.0654 (10)166 (2)
O1W—H2W1···O3iv0.82 (2)1.98 (2)2.7400 (12)153 (2)
O1—H1O1···O3v0.80 (2)1.81 (2)2.6086 (13)177 (2)
Symmetry codes: (iii) x+1, y, z+1; (iv) x1, y, z; (v) x+2, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[Cu(C2H3O3)Cl(H2O)]
Mr192.05
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)7.6296 (2), 10.0896 (3), 7.4603 (2)
β (°) 109.632 (1)
V3)540.91 (3)
Z4
Radiation typeMo Kα
µ (mm1)4.45
Crystal size (mm)0.56 × 0.19 × 0.17
Data collection
DiffractometerBruker SMART APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.189, 0.512
No. of measured, independent and
observed [I > 2σ(I)] reflections
10874, 2372, 2147
Rint0.025
(sin θ/λ)max1)0.807
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.058, 1.05
No. of reflections2372
No. of parameters93
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1W—H1W1···Cl1i0.76 (3)2.32 (3)3.0654 (10)166 (2)
O1W—H2W1···O3ii0.82 (2)1.98 (2)2.7400 (12)153 (2)
O1—H1O1···O3iii0.80 (2)1.81 (2)2.6086 (13)177 (2)
Symmetry codes: (i) x+1, y, z+1; (ii) x1, 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

First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDengel, 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
First citationGao, 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
First citationLanfranchi, M., Prati, L., Rossi, M. & Tiripicchio, A. (1993). J. Chem. Soc. Chem. Commun. pp. 1698–1699.  CrossRef Web of Science Google Scholar
First citationMedina, G., Gasque, L. & Bernès, S. (2000). Acta Cryst. C56, 766–768.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationProut, 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
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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