catena-Poly[[bis­(nitrato-κO)copper(II)]-μ-1,4-bis­(4,5-dihydro-1,3-oxazol-2-yl)­benzene-κ2N:N′]

Wang, P.-N.; Yeh, C.-W.; Tsai, H.-A.; Wang, J.-C.; Suen, M.-C.

doi:10.1107/S1600536811020605

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m881

doi:10.1107/S1600536811020605

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catena-Poly[[bis(nitrato-κO)copper(II)]-μ-1,4-bis(4,5-dihydro-1,3-oxazol-2-yl)benzene-κ²N:N′]

Pin-Ning Wang,^a Chun-Wei Yeh,^b Hui-An Tsai,^a,^c Ju-Chun Wang ^d and Maw-Cherng Suen ^a ^*

^aDepartment of Materials and Fibers, Graduate School of Materials Applied Technology, Nanya Institute of Technology, Chung-Li 32091, Taiwan, ^bDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li 32023, Taiwan, ^cR&D Center for Membrane Technology, Chung-Yuan Christian University, Chung-Li 32023, Taiwan, and ^dDepartment of Chemistry, Soochow University, Taipei, Taiwan
^*Correspondence e-mail: sun@nanya.edu.tw

(Received 22 April 2011; accepted 30 May 2011; online 11 June 2011)

In the title coordination polymer, [Cu(NO₃)₂(C₁₂H₁₂N₂O₂)]_n, the Cu^II ion, situated on an inversion center, is coordinated by two O atoms from two nitrate anions and two N atoms from two 1,4-bis(4,5-dihydro-1,3-oxazol-2-yl)benzene (L) ligands in a distorted square-planar geometry. Each L ligand also lies across an inversion center and bridges two Cu^II ions, forming a polymeric chain running along the [101] direction. The three O atoms of the nitrate group are disordered over two positions in a 3:2 ratio.

Related literature

For background to coordination polymers with organic ligands, see: Kitagawa et al. (2004 ). For related structures, see: Wang et al. (2008 ).

Experimental

Crystal data

[Cu(NO₃)₂(C₁₂H₁₂N₂O₂)]
M_r = 403.80
Triclinic, $[P \overline 1]$
a = 6.5240 (8) Å
b = 7.5852 (8) Å
c = 8.3161 (8) Å
α = 90.393 (2)°
β = 103.556 (2)°
γ = 114.314 (2)°
V = 362.09 (7) Å³
Z = 1
Mo Kα radiation
μ = 1.56 mm⁻¹
T = 297 K
0.56 × 0.52 × 0.31 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.433, T_max = 0.616
2053 measured reflections
1392 independent reflections
1384 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.095
S = 1.08
1392 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu—N1	1.971 (2)
Cu—O2	2.005 (5)
Cu—O3′	1.994 (6)

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT and SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020605/xu5198sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020605/xu5198Isup2.hkl

checkCIF report

Comment top

The synthesis of metal coordination polymers has been a subject of intense research due to their interesting structural chemistry and potential applications in gas storage, separation, catalysis, magnetism, luminescence, and drug delivery (Kitagawa et al., 2004). The Ag^I complexes containing 1,4-bis(4,5-dihydro-2-oxazolyl)benzene ligands has been reported, which show various two-dimensional networks (Wang et al., 2008). The Cu···Cu distance separated by the bridging ligands is 9.289 (1) Å, while the ligands adopt the anti conformation in the structure. The 1-D chain of the title compound forms 3-D supramolecular structure which is interlinked by nitrate anions through C–H···O hydrogen bonds.

Related literature top

For background to coordination polymers with organic ligands, see: Kitagawa et al. (2004). For related structures, see: Wang et al. (2008).

Experimental top

An aqueous solution (5.0 ml) of copper nitrate (1.0 mmol) was layered carefully over a methanolic solution (5.0 ml) of 1,4-bis(4,5-dihydro-2-oxazolyl)benzene (1.0 mmol) in a tube. Blue crystals were obtained after several weeks. These were washed with methanol and collected in 55.0% yield.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997) and SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A portion of the chain structure. Ellipsoids are drawn at 30% probability level, and H atoms of spheres of arbitrary radius. Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) -x, 1 - y, -z. The disorder is not shown for clarity.

catena-Poly[[bis(nitrato-κO)copper(II)]- µ-1,4-bis(4,5-dihydro-1,3-oxazol-2-yl)benzene-κ²N:N'] top

Crystal data top

[Cu(NO₃)₂(C₁₂H₁₂N₂O₂)]	Z = 1
M_r = 403.80	F(000) = 205
Triclinic, P1	D_x = 1.852 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5240 (8) Å	Cell parameters from 1976 reflections
b = 7.5852 (8) Å	θ = 2.5–26.0°
c = 8.3161 (8) Å	µ = 1.56 mm⁻¹
α = 90.393 (2)°	T = 297 K
β = 103.556 (2)°	Parallelepiped, blue
γ = 114.314 (2)°	0.56 × 0.52 × 0.31 mm
V = 362.09 (7) Å³

Data collection top

Bruker SMART 1000 diffractometer	1392 independent reflections
Radiation source: fine-focus sealed tube	1384 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −8→7
T_min = 0.433, T_max = 0.616	k = −8→9
2053 measured reflections	l = −7→10

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) = 0.095	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0698P)² + 0.1776P] where P = (F_o² + 2F_c²)/3
1392 reflections	(Δ/σ)_max = 0.001
142 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Cu(NO₃)₂(C₁₂H₁₂N₂O₂)]	γ = 114.314 (2)°
M_r = 403.80	V = 362.09 (7) Å³
Triclinic, P1	Z = 1
a = 6.5240 (8) Å	Mo Kα radiation
b = 7.5852 (8) Å	µ = 1.56 mm⁻¹
c = 8.3161 (8) Å	T = 297 K
α = 90.393 (2)°	0.56 × 0.52 × 0.31 mm
β = 103.556 (2)°

Data collection top

Bruker SMART 1000 diffractometer	1392 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1384 reflections with I > 2σ(I)
T_min = 0.433, T_max = 0.616	R_int = 0.019
2053 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.08	Δρ_max = 0.29 e Å⁻³
1392 reflections	Δρ_min = −0.44 e Å⁻³
142 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	Occ. (<1)
Cu	0.5000	0.5000	0.5000	0.02820 (18)
N1	0.5908 (3)	0.6368 (3)	0.3097 (2)	0.0301 (4)
N2	0.5360 (5)	0.1919 (3)	0.3813 (3)	0.0423 (5)
O1	0.6228 (3)	0.7793 (3)	0.0775 (2)	0.0392 (4)
O2	0.6917 (12)	0.3558 (9)	0.4788 (8)	0.0408 (11)	0.60
O3	0.3378 (13)	0.1675 (8)	0.3452 (9)	0.0520 (14)	0.60
O4	0.6161 (11)	0.0764 (7)	0.3539 (7)	0.0586 (12)	0.60
O2'	0.719 (2)	0.3108 (16)	0.4449 (13)	0.050 (2)	0.40
O3'	0.3542 (17)	0.2391 (10)	0.3667 (12)	0.0364 (15)	0.40
O4'	0.4801 (17)	0.0347 (11)	0.2945 (10)	0.0634 (19)	0.40
C1	0.8447 (4)	0.7532 (4)	0.3336 (4)	0.0412 (6)
H1A	0.9246	0.6695	0.3378	0.049*
H1B	0.9119	0.8426	0.4353	0.049*
C2	0.8593 (4)	0.8615 (4)	0.1836 (4)	0.0423 (6)
H2A	0.9139	0.9999	0.2149	0.051*
H2B	0.9643	0.8423	0.1273	0.051*
C3	0.4874 (4)	0.6623 (3)	0.1666 (3)	0.0282 (4)
C4	0.2358 (4)	0.5773 (3)	0.0837 (3)	0.0281 (4)
C5	0.0729 (4)	0.4320 (4)	0.1458 (3)	0.0430 (6)
H5A	0.1211	0.3858	0.2442	0.052*
C6	0.1608 (4)	0.6452 (4)	−0.0632 (3)	0.0398 (6)
H6A	0.2687	0.7432	−0.1060	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0260 (2)	0.0278 (2)	0.0279 (2)	0.01314 (17)	−0.00148 (15)	0.00318 (15)
N1	0.0231 (9)	0.0304 (10)	0.0319 (10)	0.0115 (8)	−0.0019 (7)	−0.0001 (7)
N2	0.0527 (16)	0.0355 (11)	0.0466 (13)	0.0223 (11)	0.0206 (11)	0.0115 (10)
O1	0.0270 (8)	0.0490 (10)	0.0338 (9)	0.0097 (7)	0.0056 (7)	0.0101 (8)
O2	0.036 (2)	0.038 (3)	0.050 (3)	0.0199 (18)	0.0077 (18)	0.005 (2)
O3	0.042 (3)	0.046 (4)	0.058 (3)	0.016 (3)	−0.0003 (19)	0.000 (3)
O4	0.088 (3)	0.049 (3)	0.062 (3)	0.045 (3)	0.031 (3)	0.013 (2)
O2'	0.042 (4)	0.056 (6)	0.055 (5)	0.028 (4)	0.005 (3)	0.009 (4)
O3'	0.035 (3)	0.025 (4)	0.044 (3)	0.012 (3)	0.000 (2)	−0.001 (3)
O4'	0.102 (6)	0.042 (3)	0.064 (5)	0.044 (4)	0.028 (4)	0.000 (3)
C1	0.0231 (11)	0.0453 (14)	0.0454 (14)	0.0103 (10)	−0.0007 (10)	0.0027 (11)
C2	0.0241 (11)	0.0472 (14)	0.0461 (14)	0.0084 (10)	0.0047 (10)	0.0041 (11)
C3	0.0254 (11)	0.0286 (10)	0.0288 (11)	0.0118 (8)	0.0036 (8)	0.0011 (8)
C4	0.0254 (10)	0.0317 (11)	0.0241 (10)	0.0122 (9)	0.0008 (8)	0.0013 (8)
C5	0.0308 (12)	0.0513 (15)	0.0354 (13)	0.0117 (11)	−0.0018 (10)	0.0199 (11)
C6	0.0272 (12)	0.0457 (14)	0.0354 (13)	0.0074 (10)	0.0028 (9)	0.0170 (11)

Geometric parameters (Å, º) top

Cu—N1ⁱ	1.971 (2)	O1—C3	1.337 (3)
Cu—N1	1.971 (2)	O1—C2	1.453 (3)
Cu—O2ⁱ	2.005 (5)	C1—C2	1.498 (4)
Cu—O2	2.005 (5)	C1—H1A	0.9700
Cu—O3'ⁱ	1.994 (6)	C1—H1B	0.9700
Cu—O3'	1.994 (6)	C2—H2A	0.9700
N1—C3	1.282 (3)	C2—H2B	0.9700
N1—C1	1.484 (3)	C3—C4	1.476 (3)
N2—O2'	1.152 (12)	C4—C5	1.383 (3)
N2—O3	1.190 (8)	C4—C6	1.390 (3)
N2—O4	1.234 (5)	C5—C6ⁱⁱ	1.381 (4)
N2—O4'	1.258 (7)	C5—H5A	0.9300
N2—O2	1.340 (7)	C6—C5ⁱⁱ	1.381 (4)
N2—O3'	1.354 (10)	C6—H6A	0.9300

N1ⁱ—Cu—N1	180.0	O4—N2—O3'	150.9 (5)
N1ⁱ—Cu—O3'ⁱ	92.7 (3)	O4'—N2—O3'	112.3 (6)
N1—Cu—O3'ⁱ	87.3 (3)	O2—N2—O3'	94.6 (4)
N1ⁱ—Cu—O3'	87.3 (3)	C3—O1—C2	106.60 (19)
N1—Cu—O3'	92.7 (3)	N2—O2—Cu	103.0 (4)
O3'ⁱ—Cu—O3'	180.000 (1)	N2—O3'—Cu	103.0 (5)
N1ⁱ—Cu—O2ⁱ	88.6 (2)	N1—C1—C2	103.7 (2)
N1—Cu—O2ⁱ	91.4 (2)	N1—C1—H1A	111.0
O3'ⁱ—Cu—O2ⁱ	59.4 (3)	C2—C1—H1A	111.0
O3'—Cu—O2ⁱ	120.6 (3)	N1—C1—H1B	111.0
N1ⁱ—Cu—O2	91.4 (2)	C2—C1—H1B	111.0
N1—Cu—O2	88.6 (2)	H1A—C1—H1B	109.0
O3'ⁱ—Cu—O2	120.6 (3)	O1—C2—C1	104.80 (19)
O3'—Cu—O2	59.4 (3)	O1—C2—H2A	110.8
O2ⁱ—Cu—O2	180.000 (2)	C1—C2—H2A	110.8
C3—N1—C1	107.4 (2)	O1—C2—H2B	110.8
C3—N1—Cu	137.12 (16)	C1—C2—H2B	110.8
C1—N1—Cu	115.40 (16)	H2A—C2—H2B	108.9
O2'—N2—O3	139.9 (5)	N1—C3—O1	116.8 (2)
O2'—N2—O4	91.9 (5)	N1—C3—C4	128.7 (2)
O3—N2—O4	128.1 (4)	O1—C3—C4	114.5 (2)
O2'—N2—O4'	129.2 (6)	C5—C4—C6	119.0 (2)
O3—N2—O4'	90.1 (6)	C5—C4—C3	122.5 (2)
O4—N2—O4'	39.0 (4)	C6—C4—C3	118.5 (2)
O2'—N2—O2	23.8 (4)	C6ⁱⁱ—C5—C4	120.6 (2)
O3—N2—O2	117.1 (4)	C6ⁱⁱ—C5—H5A	119.7
O4—N2—O2	114.4 (4)	C4—C5—H5A	119.7
O4'—N2—O2	152.8 (6)	C5ⁱⁱ—C6—C4	120.4 (2)
O2'—N2—O3'	117.1 (5)	C5ⁱⁱ—C6—H6A	119.8
O3—N2—O3'	22.9 (3)	C4—C6—H6A	119.8

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

Experimental details

Crystal data
Chemical formula	[Cu(NO₃)₂(C₁₂H₁₂N₂O₂)]
M_r	403.80
Crystal system, space group	Triclinic, P1
Temperature (K)	297
a, b, c (Å)	6.5240 (8), 7.5852 (8), 8.3161 (8)
α, β, γ (°)	90.393 (2), 103.556 (2), 114.314 (2)
V (Å³)	362.09 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.56
Crystal size (mm)	0.56 × 0.52 × 0.31

Data collection
Diffractometer	Bruker SMART 1000 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.433, 0.616
No. of measured, independent and observed [I > 2σ(I)] reflections	2053, 1392, 1384
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.095, 1.08
No. of reflections	1392
No. of parameters	142
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.44

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997) and SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu—N1	1.971 (2)	Cu—O3'	1.994 (6)
Cu—O2	2.005 (5)

Acknowledgements

The authors are grateful to the National Science Council of the Republic of China and Nanya Institute of Technology for support.

References

Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1997). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Y.-H., Lee, H.-T. & Suen, M.-C. (2008). Polyhedron, 27, 1177–1184. Web of Science CSD CrossRef Google Scholar

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