catena-Poly[[aqua­bis­(pyridine-κN)copper(II)]-μ-2,2′-(p-phenyl­enedi­oxy)diacetato-κ2O:O′]

Zhang, X.-M.; Li, Y.-F.

doi:10.1107/S1600536810036469

metal-organic compounds

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Volume 66| Part 10| October 2010| Page m1283

doi:10.1107/S1600536810036469

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catena-Poly[[aquabis(pyridine-κN)copper(II)]-μ-2,2′-(p-phenylenedioxy)diacetato-κ²O:O′]

Xiu-Mei Zhang ^a and Ya-Feng Li ^b ^*

^aDepartment of X-ray, First Hospital, Jilin University, Changchun 130021, People's Republic of China, and ^bSchool of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: fly012345@sohu.com

(Received 6 September 2010; accepted 12 September 2010; online 18 September 2010)

In the title compound, [Cu(C₁₀H₈O₆)(C₅H₅N)₂(H₂O)]_n, the Cu atom is five-coordinated by two O atoms from two carboxylate groups of two different 2,2′-(p-phenylenedioxy)diacetate ligands, two N atoms from two pyridine molecules and one water O atom. The geometry is square-pyramidal with the water O atom occupying the apical position. The carboxylate group bridges adjacent Cu atoms, forming an infinite zigzag chain extending parallel to [001]. The chains are linked into layers by O—H⋯O hydrogen bonds. The Cu and water O atoms lie on special positions of site symmetry 2.

Related literature

For the isotypic zinc analog, see: Hong et al. (2005 ).

Experimental

Crystal data

[Cu(C₁₀H₈O₆)(C₅H₅N)₂(H₂O)]
M_r = 463.93
Monoclinic, C 2/c
a = 15.363 (4) Å
b = 6.0888 (12) Å
c = 21.896 (6) Å
β = 103.67 (3)°
V = 1990.2 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.14 mm⁻¹
T = 298 K
0.12 × 0.11 × 0.09 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.875, T_max = 0.907
7227 measured reflections
1737 independent reflections
1096 reflections with I > 2σ(I)
R_int = 0.119

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.123
S = 1.08
1737 reflections
140 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O2ⁱ	0.81 (6)	1.87 (6)	2.677 (5)	174 (7)
Symmetry code: (i) $[-x, y+1, -z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036469/ng5029sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810036469/ng5029Isup2.hkl

checkCIF report

Comment top

The metal-organic framework, which is formed by carboxylate ligand as the strut and transition metal as the node, has recently attracted more attentions owing to the potential applications of catalyst and H-storage. In this paper, flexible ligand-BDOA as the strut bridges the Cu cations to result in the formation of infinite zigzag chain of [Cu(py)₂(H₂O)BDOA]_n.

The asymmetrical unit of [Cu(py)₂(H₂O)BDOA]_n (py=pyridine, BDOA=benzene-1,4-dioxyacetate) which is isostructural with of [Zn(py)₂(H₂O)BDOA]_n (Hong, et al., 2005), is composed of one half of Cu cation, one half of BDOA, one half of water molecule and one pyridine molecule (Fig.1). Five-coordinated Cu cation lies in the basal position of pyramid constructed by two O atoms from two carboxyl groups of two different BDOA, two nitrogen atoms of two pyridines and one water oxygen atom situated at the apical position. The bond distances of Cu—N, Cu—O and Cu—Ow are 2.109 (23) Å, 1.965 (35) Å and 2.192 (6) Å, respectively. The bond angles of O—Cu—O and N—Cu—O are 179.85 (14)° and 167.68 (18)°, respectively. Cu and water oxygen lie at 2-fold axis and BDOA at the inversion center.

The monodentate µ₂-BDOA bridges the adjacent Cu cations to form the infinite zigzag chain along (001) direction. The H-bonds of Ow—H···O (free oxygen of carboxyl) link the adjacent chains to two-dimensional layer (bc planar), which is packed by the ver dan Waals force (Fig.2).

Related literature top

For the isotypiczinc analog, see: Hong et al. (2005).

Experimental top

(I) was synthesized under hydrothermal condition. In a typically route, H₂BDOA (0.22 g, 1 mmol) was dissolved in 10 ml deionized water under stirring, and then pyridine (1.6 ml, 20 mmol) and Cu(Ac)₂^.3H₂O (0.235 g, 1 mmol) were added to a blue solution. After continuously stirred for 1 h, the solution with the molar ratio of H₂BDOA: 20py: Cu(Ac)₂^.3H₂O: 555H₂O was transferred into 23 ml autoclave and heated at 438 K for 5 days. After naturally cooling to room temperature, blue block product was collected by filtration as a single phase.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The unit cell of (I), showing the atomic labelling scheme and displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) -x, y, 0.5 - z; (ii) -x, 1 - y, -z.]
	Fig. 2. The ball-stick plot of (I), displaying the zigzag chain along (001) direction composed of briging the Cu cation with monodentate µ₂-BDOA. Cu is shown in the cyan, O in red, N in blue and C in grey.

catena-Poly[[aquabis(pyridine-κN)copper(II)]-µ- 2,2'-(p-phenylenedioxy)diacetato-κ²O:O'] top

Crystal data top

[Cu(C₁₀H₈O₆)(C₅H₅N)₂(H₂O)]	F(000) = 956
M_r = 463.93	D_x = 1.548 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2000 reflections
a = 15.363 (4) Å	θ = 3.6–25°
b = 6.0888 (12) Å	µ = 1.14 mm⁻¹
c = 21.896 (6) Å	T = 298 K
β = 103.67 (3)°	Block, blue
V = 1990.2 (8) Å³	0.12 × 0.11 × 0.09 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1737 independent reflections
Radiation source: fine-focus sealed tube	1096 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.119
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.0°, θ_min = 3.6°
ω scans	h = −18→18
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −7→6
T_min = 0.875, T_max = 0.907	l = −25→25
7227 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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0254P)² + 4.0919P] where P = (F_o² + 2F_c²)/3
1737 reflections	(Δ/σ)_max < 0.001
140 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Cu(C₁₀H₈O₆)(C₅H₅N)₂(H₂O)]	V = 1990.2 (8) Å³
M_r = 463.93	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.363 (4) Å	µ = 1.14 mm⁻¹
b = 6.0888 (12) Å	T = 298 K
c = 21.896 (6) Å	0.12 × 0.11 × 0.09 mm
β = 103.67 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1737 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1096 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.907	R_int = 0.119
7227 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.32 e Å⁻³
1737 reflections	Δρ_min = −0.38 e Å⁻³
140 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	0.0000	1.02668 (15)	0.2500	0.0480 (4)
O1	−0.0864 (2)	1.0271 (7)	0.16798 (16)	0.0584 (10)
O2	−0.0691 (3)	0.6662 (7)	0.15674 (17)	0.0679 (12)
O3	−0.1479 (3)	0.6794 (7)	0.03254 (17)	0.0656 (12)
C1	−0.0948 (4)	0.8473 (11)	0.1365 (2)	0.0506 (15)
C2	−0.1406 (4)	0.8781 (10)	0.0675 (2)	0.0581 (16)
H2A	−0.2001	0.9377	0.0643	0.070*
H2B	−0.1070	0.9840	0.0493	0.070*
C3	−0.0715 (4)	0.5975 (10)	0.0191 (2)	0.0528 (15)
C4	0.0125 (4)	0.6894 (10)	0.0344 (3)	0.0618 (17)
H4	0.0218	0.8182	0.0579	0.074*
C5	−0.0824 (4)	0.4048 (10)	−0.0158 (3)	0.0605 (17)
H5	−0.1385	0.3387	−0.0266	0.073*
N1	0.0988 (3)	0.9911 (8)	0.20420 (18)	0.0503 (12)
C6	0.1565 (4)	0.8241 (10)	0.2156 (3)	0.0571 (16)
H6	0.1512	0.7228	0.2463	0.068*
C7	0.2226 (4)	0.7939 (11)	0.1847 (3)	0.0681 (18)
H7	0.2605	0.6731	0.1937	0.082*
C8	0.2327 (4)	0.9417 (13)	0.1405 (3)	0.0713 (19)
H8	0.2787	0.9270	0.1198	0.086*
C9	0.1732 (5)	1.1140 (12)	0.1271 (3)	0.075 (2)
H9	0.1771	1.2156	0.0962	0.090*
C10	0.1086 (4)	1.1333 (10)	0.1598 (3)	0.0659 (18)
H10	0.0693	1.2514	0.1508	0.079*
O1W	0.0000	1.3867 (10)	0.2500	0.085 (2)
H1A	0.023 (5)	1.463 (10)	0.280 (3)	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0449 (6)	0.0454 (6)	0.0508 (6)	0.000	0.0055 (4)	0.000
O1	0.047 (2)	0.067 (3)	0.055 (2)	0.003 (2)	0.0017 (18)	−0.007 (2)
O2	0.082 (3)	0.057 (3)	0.059 (3)	0.000 (2)	0.006 (2)	0.007 (2)
O3	0.052 (3)	0.080 (3)	0.062 (2)	−0.005 (2)	0.009 (2)	−0.016 (2)
C1	0.040 (4)	0.069 (5)	0.042 (3)	−0.005 (3)	0.008 (3)	0.001 (3)
C2	0.055 (4)	0.064 (4)	0.052 (3)	0.004 (3)	0.005 (3)	−0.001 (3)
C3	0.043 (4)	0.070 (4)	0.042 (3)	−0.001 (3)	0.004 (3)	−0.002 (3)
C4	0.057 (5)	0.065 (4)	0.060 (4)	−0.010 (3)	0.008 (3)	−0.015 (3)
C5	0.042 (4)	0.072 (4)	0.067 (4)	−0.012 (3)	0.013 (3)	−0.006 (3)
N1	0.042 (3)	0.057 (3)	0.048 (3)	−0.005 (3)	0.004 (2)	0.001 (2)
C6	0.051 (4)	0.062 (4)	0.057 (4)	0.005 (3)	0.010 (3)	0.011 (3)
C7	0.054 (5)	0.073 (5)	0.081 (5)	0.005 (4)	0.024 (4)	0.006 (4)
C8	0.049 (4)	0.103 (6)	0.066 (4)	−0.026 (4)	0.020 (3)	−0.020 (4)
C9	0.063 (5)	0.093 (5)	0.070 (4)	−0.018 (4)	0.018 (4)	0.017 (4)
C10	0.053 (4)	0.069 (4)	0.070 (4)	−0.004 (3)	0.004 (3)	0.015 (4)
O1W	0.114 (6)	0.041 (4)	0.078 (5)	0.000	−0.021 (4)	0.000

Geometric parameters (Å, º) top

Cu1—O1	1.964 (3)	C4—H4	0.9300
Cu1—O1ⁱ	1.964 (3)	C5—C4ⁱⁱ	1.362 (8)
Cu1—N1	2.019 (4)	C5—H5	0.9300
Cu1—N1ⁱ	2.019 (4)	N1—C6	1.333 (7)
Cu1—O1W	2.192 (6)	N1—C10	1.338 (7)
O1—C1	1.284 (6)	C6—C7	1.359 (8)
O2—C1	1.219 (6)	C6—H6	0.9300
O3—C3	1.370 (6)	C7—C8	1.357 (8)
O3—C2	1.422 (6)	C7—H7	0.9300
C1—C2	1.520 (7)	C8—C9	1.377 (9)
C2—H2A	0.9700	C8—H8	0.9300
C2—H2B	0.9700	C9—C10	1.357 (8)
C3—C4	1.373 (7)	C9—H9	0.9300
C3—C5	1.388 (8)	C10—H10	0.9300
C4—C5ⁱⁱ	1.362 (8)	O1W—H1A	0.81 (6)

O1—Cu1—O1ⁱ	179.8 (3)	C5ⁱⁱ—C4—H4	119.4
O1—Cu1—N1	88.32 (15)	C3—C4—H4	119.4
O1ⁱ—Cu1—N1	91.70 (15)	C4ⁱⁱ—C5—C3	121.3 (6)
O1—Cu1—N1ⁱ	91.70 (15)	C4ⁱⁱ—C5—H5	119.4
O1ⁱ—Cu1—N1ⁱ	88.32 (15)	C3—C5—H5	119.4
N1—Cu1—N1ⁱ	167.7 (3)	C6—N1—C10	116.5 (5)
O1—Cu1—O1W	89.92 (13)	C6—N1—Cu1	122.2 (4)
O1ⁱ—Cu1—O1W	89.92 (13)	C10—N1—Cu1	121.3 (4)
N1—Cu1—O1W	96.16 (14)	N1—C6—C7	123.5 (6)
N1ⁱ—Cu1—O1W	96.16 (14)	N1—C6—H6	118.3
C1—O1—Cu1	116.8 (4)	C7—C6—H6	118.3
C3—O3—C2	117.5 (5)	C8—C7—C6	119.4 (6)
O2—C1—O1	126.4 (5)	C8—C7—H7	120.3
O2—C1—C2	120.4 (5)	C6—C7—H7	120.3
O1—C1—C2	113.1 (5)	C7—C8—C9	118.3 (6)
O3—C2—C1	113.0 (5)	C7—C8—H8	120.8
O3—C2—H2A	109.0	C9—C8—H8	120.8
C1—C2—H2A	109.0	C10—C9—C8	119.0 (6)
O3—C2—H2B	109.0	C10—C9—H9	120.5
C1—C2—H2B	109.0	C8—C9—H9	120.5
H2A—C2—H2B	107.8	N1—C10—C9	123.3 (6)
O3—C3—C4	127.1 (6)	N1—C10—H10	118.4
O3—C3—C5	115.3 (5)	C9—C10—H10	118.4
C4—C3—C5	117.6 (6)	Cu1—O1W—H1A	125 (5)
C5ⁱⁱ—C4—C3	121.1 (6)

N1—Cu1—O1—C1	66.8 (4)	O1ⁱ—Cu1—N1—C6	56.9 (4)
N1ⁱ—Cu1—O1—C1	−100.9 (4)	N1ⁱ—Cu1—N1—C6	−33.0 (4)
O1W—Cu1—O1—C1	162.9 (4)	O1W—Cu1—N1—C6	147.0 (4)
Cu1—O1—C1—O2	15.7 (8)	O1—Cu1—N1—C10	55.6 (4)
Cu1—O1—C1—C2	−163.2 (3)	O1ⁱ—Cu1—N1—C10	−124.3 (4)
C3—O3—C2—C1	−73.6 (6)	N1ⁱ—Cu1—N1—C10	145.9 (4)
O2—C1—C2—O3	−0.3 (8)	O1W—Cu1—N1—C10	−34.1 (4)
O1—C1—C2—O3	178.6 (5)	C10—N1—C6—C7	−0.1 (8)
C2—O3—C3—C4	−1.8 (8)	Cu1—N1—C6—C7	178.8 (4)
C2—O3—C3—C5	−179.3 (4)	N1—C6—C7—C8	1.3 (10)
O3—C3—C4—C5ⁱⁱ	−177.2 (5)	C6—C7—C8—C9	−2.2 (9)
C5—C3—C4—C5ⁱⁱ	0.3 (9)	C7—C8—C9—C10	2.0 (9)
O3—C3—C5—C4ⁱⁱ	177.5 (5)	C6—N1—C10—C9	−0.1 (8)
C4—C3—C5—C4ⁱⁱ	−0.3 (9)	Cu1—N1—C10—C9	−179.0 (5)
O1—Cu1—N1—C6	−123.2 (4)	C8—C9—C10—N1	−0.9 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2ⁱⁱⁱ	0.81 (6)	1.87 (6)	2.677 (5)	174 (7)

Symmetry code: (iii) −x, y+1, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₀H₈O₆)(C₅H₅N)₂(H₂O)]
M_r	463.93
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	15.363 (4), 6.0888 (12), 21.896 (6)
β (°)	103.67 (3)
V (Å³)	1990.2 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.12 × 0.11 × 0.09

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.875, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	7227, 1737, 1096
R_int	0.119
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.123, 1.08
No. of reflections	1737
No. of parameters	140
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.38

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2ⁱ	0.81 (6)	1.87 (6)	2.677 (5)	174 (7)

Symmetry code: (i) −x, y+1, −z+1/2.

Acknowledgements

This project was sponsored by the Scientific Research Foundation for Returned Overseas Chinese Scholars, Chinese Education Ministry (20071108) and the Scientific Research Foundation for the Returned Overseas Team, Chinese Education Ministry.

References

Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hong, X.-L., Li, Y.-Z. & Bai, J.-F. (2005). Acta Cryst. E61, m1863–m1865. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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