catena-Poly[[[diaqua­copper(II)]-μ-2,2′-{[p-phenyl­enebis(oxymethyl­ene)]bis­(pyridinium-3,1-di­yl)}diacetate] dibromide]

Pan, W.-C.; Lian, H.-L.

doi:10.1107/S1600536810014510

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page m607

https://doi.org/10.1107/S1600536810014510

Open

access

catena-Poly[[[diaquacopper(II)]-μ-2,2′-{[p-phenylenebis(oxymethylene)]bis(pyridinium-3,1-diyl)}diacetate] dibromide]

Wei-Cheng Pan ^a and Hong-Lei Lian ^b ^*

^aCollege of Chemical Engineering and Foods, Zhongzhou University, Zhengzhou, Henan 450044, People's Republic of China, and ^bCollege of Chemical Engineering, Zhengzhou University, Zhengzhou, Henan 450001, People's Republic of China
^*Correspondence e-mail: zzulhl@yahoo.com.cn

(Received 15 March 2010; accepted 20 April 2010; online 8 May 2010)

The title centrosymmetric coordination polymer, {[Cu(C₂₂H₂₀N₂O₆)(H₂O)₂]Br₂}_n, formed by the reaction of the flexible double betaine ligand 2,2′-{[p-phenylenebis(oxymethylene)]bis(pyridine-3,1-diyl)}diacetic acid with CuBr₂, contains a Cu(II) atom ( $[\overline1]$ symmetry) which is surrounded by two water molecules and bridged by two anions in a square-planar coordination. In the crystal, polymeric zigzag chains are linked via O—H⋯Br interactions, forming a two-dimensional network extending parallel to (011).

Related literature

For double betaine coordination polymers, see: Zhang et al. (2004 ).

Experimental

Crystal data

[Cu(C₂₂H₂₀N₂O₆)(H₂O)₂]Br₂
M_r = 667.78
Triclinic, $[P \overline 1]$
a = 7.5422 (7) Å
b = 9.3001 (8) Å
c = 9.9890 (9) Å
α = 64.194 (2)°
β = 79.405 (2)°
γ = 77.000 (2)°
V = 611.66 (10) Å³
Z = 1
Mo Kα radiation
μ = 4.21 mm⁻¹
T = 293 K
0.52 × 0.30 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.218, T_max = 0.365
3313 measured reflections
2129 independent reflections
1746 reflections with I > 2σ(I)
R_int = 0.087

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.163
S = 1.03
2129 reflections
160 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.95 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯Br1	0.52	2.74	3.220 (9)	155
O1W—H1WA⋯Br1ⁱ	0.78	2.38	3.139 (9)	167
Symmetry code: (i) -x, -y+1, -z+1.

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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810014510/su2168sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810014510/su2168Isup2.hkl

checkCIF report

Comment top

Supramolecular assembly is a powerful tool in the design of metallo-organic based complex molecular architectures. Ligands of the double betaine type are known to be generators of variable coordination frameworks in organic-inorganic hybrid materials (Zhang et al., 2004).

The title complex is centrosymmetric and exists as infinite zigzag chains (Fig. 1). In the crystal the bromide serves as a hydrogen-bond acceptor and the coordinated water molecules as donors leading to the formation of a two-dimensional network (Fig. 2 and Table 1).

Related literature top

For double betaine coordination polymers, see: Zhang et al. (2004).

Experimental top

An aqueous solution (5 ml of H₂O) of 1,4-bis(3-picolyloxyl)benzene- N,N^'-diacetate) [0.08 g, 0.2 mmol] and CuBr₂ (0.067 g, 0.3 mmol) were mixed together and heated at 340 K for 10 min with continuous stirring. The mixture was then filtered and upon slow evaporation of the filtrate, at RT for several weeks, blue block-shaped crystals were obtained (Yield ca. 58% based on L).

Structure description top

For double betaine coordination polymers, see: Zhang et al. (2004).

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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A portion of the infinite chain of the title compound, with atom labels and 50% probability displacement ellipsoids (Symmetry codes: A: -x+2, -y+2, -z+2; B: -x+1, -y+1, -z+1).
	Fig. 2. A view of the two-dimensional network formed as a result of the O—H···Br hydrogen bonds (dashed lines); Symmetry codes: A: -x, -y + 1, -z + 1; B: -x + 1, -y + 1, -z + 1; C: x + 1, y, z; D: -x + 2, -y + 1, -z + 1; D: x + 2, y, z.

catena-Poly[[[diaquacopper(II)]-µ-2,2'-{[p- phenylenebis(oxymethylene)]bis(pyridinium-3,1-diyl)}diacetate] dibromide] top

Crystal data top

[Cu(C₂₂H₂₀N₂O₆)(H₂O)₂]Br₂	Z = 1
M_r = 667.78	F(000) = 333
Triclinic, P1	D_x = 1.813 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5422 (7) Å	Cell parameters from 126 reflections
b = 9.3001 (8) Å	θ = 2.0–27.5°
c = 9.9890 (9) Å	µ = 4.21 mm⁻¹
α = 64.194 (2)°	T = 293 K
β = 79.405 (2)°	Block, blue
γ = 77.000 (2)°	0.52 × 0.30 × 0.30 mm
V = 611.66 (10) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2129 independent reflections
Radiation source: fine-focus sealed tube	1746 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
phi and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.218, T_max = 0.365	k = −10→11
3313 measured reflections	l = −10→11

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1116P)²] where P = (F_o² + 2F_c²)/3
2129 reflections	(Δ/σ)_max < 0.001
160 parameters	Δρ_max = 0.82 e Å⁻³
3 restraints	Δρ_min = −0.95 e Å⁻³

Crystal data top

[Cu(C₂₂H₂₀N₂O₆)(H₂O)₂]Br₂	γ = 77.000 (2)°
M_r = 667.78	V = 611.66 (10) Å³
Triclinic, P1	Z = 1
a = 7.5422 (7) Å	Mo Kα radiation
b = 9.3001 (8) Å	µ = 4.21 mm⁻¹
c = 9.9890 (9) Å	T = 293 K
α = 64.194 (2)°	0.52 × 0.30 × 0.30 mm
β = 79.405 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2129 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1746 reflections with I > 2σ(I)
T_min = 0.218, T_max = 0.365	R_int = 0.087
3313 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	3 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.03	Δρ_max = 0.82 e Å⁻³
2129 reflections	Δρ_min = −0.95 e Å⁻³
160 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.5000	0.5000	0.5000	0.0266 (4)
Br1	−0.09111 (11)	0.71414 (10)	0.61132 (10)	0.0434 (4)
O1	0.4292 (7)	0.6175 (6)	0.6239 (5)	0.0288 (12)
O1W	0.2454 (8)	0.4936 (11)	0.5040 (10)	0.089 (3)
H1WA	0.1963	0.4563	0.4678	0.133*
H1WB	0.1830	0.5087	0.5306	0.133*
O2	0.4295 (9)	0.8338 (7)	0.4071 (6)	0.0462 (16)
O3	0.7158 (10)	0.8939 (9)	0.9512 (7)	0.0570 (19)
N1	0.3377 (9)	0.7917 (7)	0.7897 (7)	0.0290 (14)
C1	0.4042 (10)	0.7683 (9)	0.5435 (8)	0.0293 (16)
C2	0.3214 (11)	0.8765 (9)	0.6271 (8)	0.0315 (17)
H2A	0.3826	0.9702	0.5861	0.038*
H2B	0.1932	0.9148	0.6107	0.038*
C3	0.2186 (11)	0.6898 (10)	0.8751 (9)	0.0347 (18)
H3A	0.1288	0.6746	0.8321	0.042*
C4	0.2320 (11)	0.6095 (10)	1.0252 (9)	0.0375 (19)
H4A	0.1528	0.5373	1.0848	0.045*
C5	0.3618 (12)	0.6351 (10)	1.0880 (9)	0.0381 (19)
H5A	0.3681	0.5819	1.1907	0.046*
C6	0.4849 (11)	0.7399 (9)	1.0003 (8)	0.0313 (17)
C7	0.4693 (11)	0.8171 (9)	0.8479 (8)	0.0292 (16)
H7A	0.5501	0.8867	0.7856	0.035*
C8	0.6243 (13)	0.7737 (11)	1.0664 (10)	0.043 (2)
H8A	0.5654	0.8110	1.1431	0.051*
H8B	0.7109	0.6759	1.1117	0.051*
C9	0.8556 (11)	0.9412 (11)	0.9825 (10)	0.0377 (19)
C10	0.9060 (12)	0.8939 (11)	1.1252 (9)	0.040 (2)
H10A	0.8431	0.8239	1.2087	0.047*
C11	0.9504 (12)	1.0480 (11)	0.8589 (9)	0.039 (2)
H11A	0.9157	1.0805	0.7640	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0268 (7)	0.0331 (8)	0.0283 (7)	−0.0080 (5)	−0.0023 (5)	−0.0189 (6)
Br1	0.0384 (6)	0.0471 (6)	0.0532 (7)	−0.0103 (4)	−0.0074 (4)	−0.0258 (5)
O1	0.032 (3)	0.034 (3)	0.026 (3)	−0.006 (2)	−0.002 (2)	−0.018 (2)
O1W	0.028 (3)	0.140 (8)	0.172 (9)	−0.013 (4)	0.001 (4)	−0.136 (8)
O2	0.077 (5)	0.041 (3)	0.021 (3)	−0.016 (3)	0.001 (3)	−0.012 (2)
O3	0.063 (4)	0.075 (5)	0.038 (4)	−0.035 (4)	−0.015 (3)	−0.013 (3)
N1	0.036 (3)	0.028 (3)	0.027 (3)	−0.006 (3)	−0.001 (3)	−0.014 (3)
C1	0.031 (4)	0.032 (4)	0.032 (4)	−0.010 (3)	−0.005 (3)	−0.017 (3)
C2	0.042 (4)	0.025 (4)	0.028 (4)	−0.008 (3)	−0.005 (3)	−0.010 (3)
C3	0.035 (4)	0.037 (4)	0.037 (4)	−0.008 (3)	−0.002 (3)	−0.019 (4)
C4	0.038 (5)	0.041 (5)	0.031 (4)	−0.015 (4)	0.005 (3)	−0.012 (4)
C5	0.045 (5)	0.039 (4)	0.022 (4)	−0.002 (4)	−0.002 (3)	−0.007 (3)
C6	0.036 (4)	0.033 (4)	0.028 (4)	0.001 (3)	−0.007 (3)	−0.017 (3)
C7	0.035 (4)	0.026 (4)	0.029 (4)	−0.007 (3)	−0.003 (3)	−0.013 (3)
C8	0.050 (5)	0.047 (5)	0.034 (4)	−0.006 (4)	−0.011 (4)	−0.018 (4)
C9	0.036 (4)	0.046 (5)	0.042 (5)	−0.001 (4)	−0.014 (4)	−0.026 (4)
C10	0.042 (5)	0.042 (5)	0.035 (4)	−0.003 (4)	−0.004 (4)	−0.018 (4)
C11	0.041 (5)	0.053 (5)	0.032 (4)	−0.004 (4)	−0.012 (4)	−0.023 (4)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.919 (5)	C3—H3A	0.9300
Cu1—O1	1.919 (5)	C4—C5	1.368 (12)
Cu1—O1W	1.927 (6)	C4—H4A	0.9300
Cu1—O1Wⁱ	1.927 (6)	C5—C6	1.394 (12)
O1—C1	1.266 (9)	C5—H5A	0.9300
O1W—H1WA	0.7774	C6—C7	1.387 (11)
O1W—H1WB	0.5183	C6—C8	1.492 (12)
O2—C1	1.223 (9)	C7—H7A	0.9300
O3—C9	1.361 (11)	C8—H8A	0.9700
O3—C8	1.409 (11)	C8—H8B	0.9700
N1—C7	1.348 (10)	C9—C11	1.396 (12)
N1—C3	1.353 (10)	C9—C10	1.396 (12)
N1—C2	1.480 (9)	C10—C11ⁱⁱ	1.376 (13)
C1—C2	1.535 (10)	C10—H10A	0.9300
C2—H2A	0.9700	C11—C10ⁱⁱ	1.376 (13)
C2—H2B	0.9700	C11—H11A	0.9300
C3—C4	1.365 (11)

O1ⁱ—Cu1—O1	180	C3—C4—H4A	119.9
O1ⁱ—Cu1—O1W	91.4 (2)	C5—C4—H4A	119.9
O1—Cu1—O1W	88.6 (2)	C4—C5—C6	120.9 (7)
O1ⁱ—Cu1—O1Wⁱ	88.6 (2)	C4—C5—H5A	119.5
O1—Cu1—O1Wⁱ	91.4 (2)	C6—C5—H5A	119.5
O1W—Cu1—O1Wⁱ	180	C7—C6—C5	117.4 (7)
C1—O1—Cu1	110.1 (5)	C7—C6—C8	120.6 (7)
Cu1—O1W—H1WA	131.9	C5—C6—C8	122.0 (7)
Cu1—O1W—H1WB	138.6	N1—C7—C6	120.3 (7)
H1WA—O1W—H1WB	89.3	N1—C7—H7A	119.8
C9—O3—C8	119.4 (7)	C6—C7—H7A	119.8
C7—N1—C3	122.2 (7)	O3—C8—C6	108.1 (7)
C7—N1—C2	119.7 (6)	O3—C8—H8A	110.1
C3—N1—C2	118.1 (7)	C6—C8—H8A	110.1
O2—C1—O1	126.5 (7)	O3—C8—H8B	110.1
O2—C1—C2	117.8 (7)	C6—C8—H8B	110.1
O1—C1—C2	115.6 (6)	H8A—C8—H8B	108.4
N1—C2—C1	112.9 (6)	O3—C9—C11	115.3 (7)
N1—C2—H2A	109.0	O3—C9—C10	125.3 (8)
C1—C2—H2A	109.0	C11—C9—C10	119.4 (8)
N1—C2—H2B	109.0	C11ⁱⁱ—C10—C9	119.3 (8)
C1—C2—H2B	109.0	C11ⁱⁱ—C10—H10A	120.4
H2A—C2—H2B	107.8	C9—C10—H10A	120.4
N1—C3—C4	119.1 (8)	C10ⁱⁱ—C11—C9	121.3 (8)
N1—C3—H3A	120.5	C10ⁱⁱ—C11—H11A	119.3
C4—C3—H3A	120.5	C9—C11—H11A	119.3
C3—C4—C5	120.1 (8)

O1ⁱ—Cu1—O1—C1	112 (100)	C4—C5—C6—C8	178.2 (8)
O1W—Cu1—O1—C1	−91.2 (6)	C3—N1—C7—C6	−1.1 (11)
O1Wⁱ—Cu1—O1—C1	88.8 (6)	C2—N1—C7—C6	179.3 (7)
Cu1—O1—C1—O2	−3.7 (10)	C5—C6—C7—N1	0.9 (11)
Cu1—O1—C1—C2	171.9 (5)	C8—C6—C7—N1	−176.9 (7)
C7—N1—C2—C1	101.3 (8)	C9—O3—C8—C6	−177.3 (7)
C3—N1—C2—C1	−78.4 (9)	C7—C6—C8—O3	2.8 (11)
O2—C1—C2—N1	−166.3 (7)	C5—C6—C8—O3	−175.0 (7)
O1—C1—C2—N1	17.8 (9)	C8—O3—C9—C11	173.5 (8)
C7—N1—C3—C4	−0.1 (12)	C8—O3—C9—C10	−7.8 (13)
C2—N1—C3—C4	179.5 (7)	O3—C9—C10—C11ⁱⁱ	−179.5 (9)
N1—C3—C4—C5	1.4 (12)	C11—C9—C10—C11ⁱⁱ	−0.8 (14)
C3—C4—C5—C6	−1.5 (13)	O3—C9—C11—C10ⁱⁱ	179.6 (8)
C4—C5—C6—C7	0.4 (12)	C10—C9—C11—C10ⁱⁱ	0.8 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···Br1	0.52	2.74	3.220 (9)	155
O1W—H1WA···Br1ⁱⁱⁱ	0.78	2.38	3.139 (9)	167

Symmetry code: (iii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₂₂H₂₀N₂O₆)(H₂O)₂]Br₂
M_r	667.78
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5422 (7), 9.3001 (8), 9.9890 (9)
α, β, γ (°)	64.194 (2), 79.405 (2), 77.000 (2)
V (Å³)	611.66 (10)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	4.21
Crystal size (mm)	0.52 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.218, 0.365
No. of measured, independent and observed [I > 2σ(I)] reflections	3313, 2129, 1746
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.163, 1.03
No. of reflections	2129
No. of parameters	160
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.95

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), 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
O1W—H1WB···Br1	0.52	2.74	3.220 (9)	155
O1W—H1WA···Br1ⁱ	0.78	2.38	3.139 (9)	167

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

Financial support from Zhongzhou University is greatly appreciated.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison,Wisconsin, USA. 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
Zhang, L.-P., Lam, C.-K., Song, H.-B. & Mak, T. C. W. (2004). Polyhedron, 23, 2413–2425. 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.