catena-Poly[[aqua­copper(II)]-μ2-imino­diacetato-κ4O,N,O′:O′]

Zhong, Q.; Wang, Y.-H.; Zhang, X.-T.

doi:10.1107/S1600536811041286

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1528

doi:10.1107/S1600536811041286

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catena-Poly[[aquacopper(II)]-μ₂-iminodiacetato-κ⁴O,N,O′:O′]

Qin Zhong,^a Yu-Hong Wang ^a ^* and Xue-Ting Zhang ^a

^aSchool of Chemistry and Bioengineering, Suzhou University of Science and Technology, Suzhou 215009, People's Republic of China
^*Correspondence e-mail: wangyuhong@mail.usts.edu.cn

(Received 29 September 2011; accepted 7 October 2011; online 12 October 2011)

In the title compound, [Cu(C₄H₅O₄)(H₂O)]_n, the iminodiacetate (ida) ligands link the Cu^II atoms into polymeric zigzag chains running along [010]. Each Cu^II ion is five-coordinated in a distorted square-pyramidal geometry by one N and two O atoms from an ida ligand, one O atom from the neighbouring ida ligand and one water O atom. In the crystal, the polymeric chains are held together via intermolecular O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For applications of coordination polymers containing bridging carboxylate groups, see: Dey et al. (2003 ); Wu et al. (2009 ); Zhang et al. (2008 ). For coordination polymers with iminodiacetic acid, see: Bresciani-Pahor et al. (1984 ); Ren et al. (2003 ); Song et al. (2011 ).

Experimental

Crystal data

[Cu(C₄H₅O₄)(H₂O)]
M_r = 212.65
Monoclinic, P 2₁ /c
a = 6.563 (3) Å
b = 9.870 (4) Å
c = 10.876 (4) Å
β = 99.802 (8)°
V = 694.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.12 mm⁻¹
T = 223 K
0.40 × 0.25 × 0.15 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.369, T_max = 0.652
3854 measured reflections
1571 independent reflections
1358 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.082
S = 1.02
1571 reflections
110 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O1ⁱ	0.87 (1)	2.08 (1)	2.936 (4)	168 (4)
O5—H5B⋯O2ⁱⁱ	0.87 (1)	1.99 (1)	2.860 (4)	171 (4)
N1—H11A⋯O2ⁱ	0.86 (1)	2.13 (1)	2.992 (3)	173 (3)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2001 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811041286/cv5163sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041286/cv5163Isup2.hkl

checkCIF report

Comment top

The syntheses of coordination polymers containing bridging carboxylate groups are of current interest due to potential applications in the areas of magnetism, ion exchange and photochemistry (Dey et al., 2003; Wu et al., 2009; Zhang et al., 2008). The iminodiacetic acid has been found to be useful ligand, and a lot of transition metal polymers of iminodiacetic acid have been reported (Bresciani-Pahor et al., 1984; Ren et al., 2003; Song et al., 2011). Here, we report the crystal structure of the title compound, (I), a one-dimensional Cu(II) coordination polymer obtained by the hydrothermal synthesis reaction of iminodiacetic acid and copper(II) chlorine.

The title complex (I) is a one-dimensional zigzag chain coordination polymer, which results from the fact that the copper(II) ions are bridged sequentially by syn-anti carboxylate groups. A perspective view of the mononuclear fragment of (I) is given in Fig. 1. Each copper(II) ion is in a distorted square pyramidal geometry with three donor atoms (O1, N1, O3) of the ida ligand, one oxygen atoms O4A (A -x + 2, y - 1/2, -z + 3/2) belonging to the carboxylate group of one adjacent ida ligand and one terminal O (O5) atom of H₂O molecule. Two five-membered chelate rings [–Cu1—O3—C4—C3—N1- and –Cu1—O1—C2—C1—N1-] are formed with the metal atoms, and the two fused ring systems are folded along the common Cu1—N1 axis by 101.5 (1)°. In (I), each ida ligand is tetradentate when the bridge involving atom O4A is considered. One of carboxylate groups of each ida ligand is in an syn-anti conformation with respect to the two copper centres. Thus, the carboxylate groups act as bridges and connect the copper(II) centers to form a 1-D zigzag chain coordination polymer.

The one-dimensional polymeric chains are packed through intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) to form three-dimensional structure (Fig. 2).

Related literature top

For applications of coordination polymers containing bridging carboxylate groups, see: Dey et al. (2003); Wu et al. (2009); Zhang et al. (2008). For coordination polymers with iminodiacetic acid, see: Bresciani-Pahor et al. (1984); Ren et al. (2003); Song et al. (2011).

Experimental top

CuCl₂^.2H₂O (0.0171 g, 0.1 mmol), iminodiacetic acid (0.0133 g, 0.1 mmol), NaOH (0.0084 g, 0.2 mmol), H₂O (0.5 mL) and ethanol (3 mL) were placed in a thick Pyrex tube and heated at 120°C for 3 days. After cooling at a rate of 5°C/h to the ambient temperature, blue block crystals were collected, washed with anhydrous ethanol, and then dried at room temperature. The yield is 76% based on iminodiacetic acid. Analysis found: C, 22.98; H, 3.36; N, 6.56%. Calculated for C₄H₇CuNO₅: C, 22.59; H, 3.32; N, 6.59%.

Computing details top

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalStructure (Rigaku, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A portion of the crystal structure of (I), showing the atomic numbering and 30% probabilty displacement ellipsoids [symmetry codes: (A) -x + 2, y - 1/2, -z + 3/2; (B) -x + 2, y + 1/2, -z + 3/2]
	Fig. 2. A portion of the crystal packing viewed approximately down the a axis. Dashed lines denote hydrogen bonds. H atoms with no hydrogen bond interactions have been omitted for clarity.

catena-Poly[[aquacopper(II)]-µ-iminodiacetato- κ⁴O,N,O':O'] top

Crystal data top

[Cu(C₄H₅O₄)(H₂O)]	F(000) = 428
M_r = 212.65	D_x = 2.035 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 3372 reflections
a = 6.563 (3) Å	θ = 3.1–27.5°
b = 9.870 (4) Å	µ = 3.12 mm⁻¹
c = 10.876 (4) Å	T = 223 K
β = 99.802 (8)°	Block, blue
V = 694.2 (5) Å³	0.40 × 0.25 × 0.15 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	1571 independent reflections
Radiation source: fine-focus sealed tube	1358 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −12→12
T_min = 0.369, T_max = 0.652	l = −9→14
3854 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.046P)² + 0.157P] where P = (F_o² + 2F_c²)/3
1571 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.45 e Å⁻³
3 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Cu(C₄H₅O₄)(H₂O)]	V = 694.2 (5) Å³
M_r = 212.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.563 (3) Å	µ = 3.12 mm⁻¹
b = 9.870 (4) Å	T = 223 K
c = 10.876 (4) Å	0.40 × 0.25 × 0.15 mm
β = 99.802 (8)°

Data collection top

Rigaku Saturn diffractometer	1571 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	1358 reflections with I > 2σ(I)
T_min = 0.369, T_max = 0.652	R_int = 0.026
3854 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	3 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.45 e Å⁻³
1571 reflections	Δρ_min = −0.48 e Å⁻³
110 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.85030 (5)	0.23532 (3)	0.75251 (3)	0.02015 (14)
O1	0.6802 (4)	0.2321 (2)	0.5873 (2)	0.0312 (5)
O2	0.4101 (3)	0.3228 (3)	0.4674 (2)	0.0378 (6)
O3	0.9803 (3)	0.4446 (2)	0.7449 (2)	0.0312 (5)
O4	0.9274 (3)	0.64968 (19)	0.8186 (2)	0.0265 (5)
O5	0.9679 (4)	0.1781 (3)	0.9246 (2)	0.0454 (6)
H5A	0.897 (6)	0.212 (4)	0.978 (3)	0.054*
H5B	1.1022 (18)	0.184 (5)	0.945 (4)	0.054*
N1	0.6164 (4)	0.3497 (2)	0.7986 (2)	0.0200 (5)
H11A	0.546 (4)	0.303 (3)	0.844 (3)	0.024*
C1	0.4669 (4)	0.3788 (3)	0.6828 (3)	0.0263 (6)
H1A	0.4639	0.4767	0.6674	0.032*
H1B	0.3282	0.3511	0.6949	0.032*
C2	0.5202 (5)	0.3069 (3)	0.5707 (3)	0.0256 (6)
C3	0.7073 (4)	0.4735 (3)	0.8622 (3)	0.0226 (6)
H3A	0.7568	0.4537	0.9505	0.027*
H3B	0.6011	0.5440	0.8571	0.027*
C4	0.8864 (4)	0.5246 (3)	0.8023 (3)	0.0208 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0235 (2)	0.0177 (2)	0.0204 (2)	0.00209 (13)	0.00672 (14)	0.00000 (13)
O1	0.0320 (12)	0.0387 (12)	0.0226 (12)	0.0087 (10)	0.0042 (9)	−0.0061 (9)
O2	0.0342 (12)	0.0540 (14)	0.0233 (13)	0.0085 (11)	−0.0003 (10)	−0.0008 (11)
O3	0.0306 (12)	0.0195 (10)	0.0491 (15)	−0.0004 (9)	0.0229 (10)	−0.0010 (9)
O4	0.0341 (11)	0.0187 (9)	0.0297 (12)	−0.0081 (9)	0.0138 (9)	−0.0055 (8)
O5	0.0394 (14)	0.0669 (18)	0.0307 (15)	0.0129 (14)	0.0085 (11)	0.0028 (12)
N1	0.0231 (12)	0.0185 (11)	0.0202 (13)	−0.0033 (10)	0.0085 (9)	−0.0004 (9)
C1	0.0233 (14)	0.0289 (15)	0.0263 (17)	0.0006 (13)	0.0030 (12)	−0.0012 (12)
C2	0.0284 (16)	0.0253 (14)	0.0235 (16)	−0.0030 (13)	0.0055 (12)	0.0000 (12)
C3	0.0265 (15)	0.0171 (12)	0.0263 (16)	−0.0019 (11)	0.0101 (12)	−0.0053 (11)
C4	0.0203 (14)	0.0199 (13)	0.0215 (15)	−0.0032 (11)	0.0016 (11)	0.0019 (11)

Geometric parameters (Å, º) top

Cu1—O1	1.948 (2)	O5—H5B	0.873 (10)
Cu1—O4ⁱ	1.955 (2)	N1—C3	1.478 (3)
Cu1—O5	1.981 (3)	N1—C1	1.486 (4)
Cu1—N1	2.036 (2)	N1—H11A	0.863 (10)
Cu1—O3	2.241 (2)	C1—C2	1.503 (4)
O1—C2	1.271 (4)	C1—H1A	0.9800
O2—C2	1.238 (4)	C1—H1B	0.9800
O3—C4	1.234 (3)	C3—C4	1.523 (4)
O4—C4	1.270 (3)	C3—H3A	0.9800
O4—Cu1ⁱⁱ	1.955 (2)	C3—H3B	0.9800
O5—H5A	0.873 (10)

O1—Cu1—O4ⁱ	88.70 (10)	C1—N1—H11A	104 (2)
O1—Cu1—O5	159.50 (11)	Cu1—N1—H11A	110 (2)
O4ⁱ—Cu1—O5	93.05 (10)	N1—C1—C2	112.6 (2)
O1—Cu1—N1	84.15 (10)	N1—C1—H1A	109.1
O4ⁱ—Cu1—N1	168.97 (9)	C2—C1—H1A	109.1
O5—Cu1—N1	96.58 (10)	N1—C1—H1B	109.1
O1—Cu1—O3	98.23 (9)	C2—C1—H1B	109.1
O4ⁱ—Cu1—O3	93.97 (8)	H1A—C1—H1B	107.8
O5—Cu1—O3	102.01 (11)	O2—C2—O1	122.9 (3)
N1—Cu1—O3	78.80 (8)	O2—C2—C1	119.7 (3)
C2—O1—Cu1	116.8 (2)	O1—C2—C1	117.4 (3)
C4—O3—Cu1	110.15 (17)	N1—C3—C4	110.7 (2)
C4—O4—Cu1ⁱⁱ	121.34 (19)	N1—C3—H3A	109.5
Cu1—O5—H5A	111 (3)	C4—C3—H3A	109.5
Cu1—O5—H5B	116 (3)	N1—C3—H3B	109.5
H5A—O5—H5B	116 (4)	C4—C3—H3B	109.5
C3—N1—C1	113.1 (2)	H3A—C3—H3B	108.1
C3—N1—Cu1	108.17 (17)	O3—C4—O4	125.4 (3)
C1—N1—Cu1	108.40 (17)	O3—C4—C3	119.5 (2)
C3—N1—H11A	113 (2)	O4—C4—C3	115.0 (2)

O4ⁱ—Cu1—O1—C2	−164.3 (2)	O3—Cu1—N1—C1	93.24 (18)
O5—Cu1—O1—C2	100.5 (3)	C3—N1—C1—C2	125.0 (3)
N1—Cu1—O1—C2	7.3 (2)	Cu1—N1—C1—C2	5.1 (3)
O3—Cu1—O1—C2	−70.5 (2)	Cu1—O1—C2—O2	173.5 (2)
O1—Cu1—O3—C4	100.6 (2)	Cu1—O1—C2—C1	−6.1 (3)
O4ⁱ—Cu1—O3—C4	−170.2 (2)	N1—C1—C2—O2	−179.3 (3)
O5—Cu1—O3—C4	−76.2 (2)	N1—C1—C2—O1	0.3 (4)
N1—Cu1—O3—C4	18.2 (2)	C1—N1—C3—C4	−82.1 (3)
O1—Cu1—N1—C3	−129.37 (18)	Cu1—N1—C3—C4	38.0 (3)
O4ⁱ—Cu1—N1—C3	−79.5 (5)	Cu1—O3—C4—O4	177.6 (2)
O5—Cu1—N1—C3	71.24 (19)	Cu1—O3—C4—C3	−1.3 (3)
O3—Cu1—N1—C3	−29.75 (17)	Cu1ⁱⁱ—O4—C4—O3	1.8 (4)
O1—Cu1—N1—C1	−6.38 (17)	Cu1ⁱⁱ—O4—C4—C3	−179.27 (19)
O4ⁱ—Cu1—N1—C1	43.5 (5)	N1—C3—C4—O3	−24.3 (4)
O5—Cu1—N1—C1	−165.77 (18)	N1—C3—C4—O4	156.6 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1ⁱⁱⁱ	0.87 (1)	2.08 (1)	2.936 (4)	168 (4)
O5—H5B···O2^iv	0.87 (1)	1.99 (1)	2.860 (4)	171 (4)
N1—H11A···O2ⁱⁱⁱ	0.86 (1)	2.13 (1)	2.992 (3)	173 (3)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₄H₅O₄)(H₂O)]
M_r	212.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	6.563 (3), 9.870 (4), 10.876 (4)
β (°)	99.802 (8)
V (Å³)	694.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.12
Crystal size (mm)	0.40 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.369, 0.652
No. of measured, independent and observed [I > 2σ(I)] reflections	3854, 1571, 1358
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.082, 1.02
No. of reflections	1571
No. of parameters	110
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.48

Computer programs: CrystalClear (Rigaku, 2001), CrystalStructure (Rigaku, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1ⁱ	0.873 (10)	2.076 (14)	2.936 (4)	168 (4)
O5—H5B···O2ⁱⁱ	0.873 (10)	1.994 (13)	2.860 (4)	171 (4)
N1—H11A···O2ⁱ	0.863 (10)	2.134 (11)	2.992 (3)	173 (3)

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

Acknowledgements

The authors thank Suzhou University of Science and Technology for financial support.

References

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