catena-Poly[[aqua­bromidocopper(II)]-μ3-(picolinato N-oxide)]

Wang, X.-Y.; Zhang, X.-Q.; Wu, W.-S.

doi:10.1107/S1600536811001814

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page m225

doi:10.1107/S1600536811001814

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catena-Poly[[aquabromidocopper(II)]-μ₃-(picolinato N-oxide)]

Xin-Yu Wang,^a Xiao-Qing Zhang ^a and Wen-Shi Wu ^a ^*

^aCollege of Materials Science and Engineering, Huaqiao University, Xiamen, Fujian 361021, People's Republic of China
^*Correspondence e-mail: wws@hqu.edu.cn

(Received 23 December 2010; accepted 12 January 2011; online 22 January 2011)

The title complex, [CuBr(C₆H₄NO₃)(H₂O)]_n, exhibits a layered structure which is stabilized by intermolecular O—H⋯O and O—H⋯Br⁻ hydrogen bonds, van der Waals forces and π–π interactions [centroid–centroid distance = 3.747(4) Å] between the parallel pyridine rings from two neighboring layers.

Related literature

For the isotypic chlorido complex, see: Yang et al. (2004 ). For the synthesis, see: Wu et al. (2007 ).

Experimental

Crystal data

[CuBr(C₆H₄NO₃)(H₂O)]
M_r = 299.57
Monoclinic, P 2₁ /c
a = 9.7116 (3) Å
b = 10.0302 (2) Å
c = 9.4984 (3) Å
β = 110.821 (2)°
V = 864.81 (4) Å³
Z = 4
Mo Kα radiation
μ = 7.12 mm⁻¹
T = 173 K
0.52 × 0.35 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.095, T_max = 0.241
2584 measured reflections
1515 independent reflections
1420 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.127
S = 1.00
1515 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 1.09 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B2⋯O2ⁱ	0.85	1.97	2.738 (5)	149
O4—H4B2⋯Br1ⁱ	0.85	3.07	3.741 (4)	137
O4—H4B1⋯Br1ⁱⁱ	0.85	2.59	3.377 (4)	155
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: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); 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 global, I. DOI: 10.1107/S1600536811001814/hg2780sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001814/hg2780Isup2.hkl

checkCIF report

Comment top

The title complex, [(C₆H₄NO₃)(H₂O)BrCu]_n, is isomorphous with the chloro complex (Yang et al., 2004). The atoms of C1,C2,C3,C4,C5,C6,N1 and O1 lie in a plane with r.m.s. of 0.0095Å (Figure 1). The Cu(II) ion is 6-coordinated by a bidentate picolinate N-oxide chelating ligand (O1 and O2), a N-oxide oxygen atom and a carboxylate oxygen atom from two other ligands, an aqua ligand and a bromine anion (Figure 2). The two axial Cu—O bond lengths Cu-O1 and Cu-O3 are 2.449 (4) and 2.499 (4)Å and are longer than those reported for the chloride complex (Yang et al., 2004), while the Cu—O4 bond length of 1.990 (4)Å is shorter. The distance of Cu—Br is 2.403 (8)Å.

The complex exhibits a layered crystal structure which is stabilized by intermolecular O—H···O and O—H···Br^- hydrogen bonds, van der Waals forces and π-π interactions between parallel pyridine rings from two neighboring layers (Figure 2). The distances between the layers are 3.318 (2) Å. The title complex forms Cu₂O₂ units interconnected via 2-carboxylic acid-pyridine-N-oxide ligands, and such unit formed a parallelogram (Figure 2).

Related literature top

For the isostructural chloro complex, see: Yang et al. (2004). For the synthesis, see: Wu et al. (2007).

Experimental top

The title complex was synthesized according to the method of Wu et al., (2007). The CuBr₂ (0.1 g, 0.5 mmol) was dissolved in 20 ml methanol(20 ml), then 2-carboxylic acid-pyridine-N-oxide (0.07 g, 0.5 mmol) in THF (20 ml) was added slowly. The mixture was then stirred for a few hours. Brown crystals of the title complex were grown from the mother liquor by slow evapovation after three weeks.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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. ORTEP drawing (at 30% probability) of the compound structure. [Symmetry code: (A) 1-x, 1-y, 1-z (B) x, 0.5-y, -0.5+z (C) 1-x, 0.5+y, 1.5-z].
	Fig. 2. Crystal Packing diagram of the title compound, showing the H-bonded interactions (dashed lines),π-π interactions diagram. [Symmetry code: (A) 1-x, -0.5+y, 0.5-z (B) x, 0.5-y, -0.5+z].
	Fig. 3. Packing diagram.
	Fig. 4. Packing diagram.

Poly[[aquabromidocopper(II)]- µ₃-(picolinato N-oxide)] top

Crystal data top

[CuBr(C₆H₄NO₃)(H₂O)]	F(000) = 580
M_r = 299.57	D_x = 2.301 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1539 reflections
a = 9.7116 (3) Å	θ = 2.2–25.1°
b = 10.0302 (2) Å	µ = 7.12 mm⁻¹
c = 9.4984 (3) Å	T = 173 K
β = 110.821 (2)°	Prism, brown
V = 864.81 (4) Å³	0.52 × 0.35 × 0.22 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1515 independent reflections
Radiation source: fine-focus sealed tube	1420 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 0 pixels mm^-1	θ_max = 25.1°, θ_min = 2.2°
ϕ and ω scans	h = −8→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→11
T_min = 0.095, T_max = 0.241	l = −10→11
2584 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.081P)² + 5.867P] where P = (F_o² + 2F_c²)/3
1515 reflections	(Δ/σ)_max = 0.012
118 parameters	Δρ_max = 1.09 e Å⁻³
0 restraints	Δρ_min = −0.93 e Å⁻³

Crystal data top

[CuBr(C₆H₄NO₃)(H₂O)]	V = 864.81 (4) Å³
M_r = 299.57	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7116 (3) Å	µ = 7.12 mm⁻¹
b = 10.0302 (2) Å	T = 173 K
c = 9.4984 (3) Å	0.52 × 0.35 × 0.22 mm
β = 110.821 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1515 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1420 reflections with I > 2σ(I)
T_min = 0.095, T_max = 0.241	R_int = 0.027
2584 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.00	Δρ_max = 1.09 e Å⁻³
1515 reflections	Δρ_min = −0.93 e Å⁻³
118 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	0.49099 (7)	0.34456 (6)	0.41130 (7)	0.0175 (2)
N1	0.2180 (5)	0.4606 (4)	0.3842 (5)	0.0152 (9)
O1	0.3577 (4)	0.4929 (4)	0.4067 (4)	0.0184 (8)
O2	0.4245 (4)	0.2618 (4)	0.5602 (4)	0.0256 (9)
O3	0.2807 (5)	0.2489 (5)	0.6967 (5)	0.0294 (10)
C1	0.1845 (6)	0.3627 (6)	0.4668 (6)	0.0193 (12)
C2	0.0387 (7)	0.3350 (6)	0.4398 (7)	0.0238 (13)
H2A	0.0140	0.2691	0.4987	0.029*
C3	−0.0713 (6)	0.4001 (7)	0.3300 (7)	0.0315 (15)
H3A	−0.1715	0.3771	0.3092	0.038*
C4	−0.0343 (7)	0.5010 (7)	0.2490 (8)	0.0338 (15)
H4A	−0.1092	0.5496	0.1744	0.041*
C5	0.1116 (7)	0.5293 (6)	0.2782 (7)	0.0259 (13)
H5A	0.1377	0.5978	0.2232	0.031*
C6	0.3066 (6)	0.2862 (5)	0.5851 (6)	0.0180 (11)
Br1	0.67758 (6)	0.17677 (6)	0.45034 (7)	0.0260 (2)
O4	0.5513 (4)	0.4396 (4)	0.2586 (4)	0.0216 (8)
H4B2	0.5328	0.3904	0.1812	0.032*
H4B1	0.4763	0.4764	0.1945	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0175 (4)	0.0176 (4)	0.0202 (4)	0.0022 (2)	0.0101 (3)	0.0019 (2)
N1	0.013 (2)	0.015 (2)	0.018 (2)	0.0020 (16)	0.0062 (18)	0.0016 (17)
O1	0.0139 (19)	0.0198 (19)	0.023 (2)	−0.0029 (14)	0.0085 (16)	−0.0027 (15)
O2	0.023 (2)	0.030 (2)	0.028 (2)	0.0079 (18)	0.0140 (19)	0.0088 (18)
O3	0.031 (2)	0.037 (2)	0.027 (2)	0.0078 (19)	0.0185 (19)	0.0154 (19)
C1	0.023 (3)	0.018 (3)	0.018 (3)	−0.001 (2)	0.009 (2)	−0.002 (2)
C2	0.019 (3)	0.025 (3)	0.028 (3)	−0.003 (2)	0.009 (3)	−0.002 (2)
C3	0.015 (3)	0.042 (4)	0.034 (4)	−0.005 (3)	0.005 (3)	−0.004 (3)
C4	0.024 (3)	0.039 (4)	0.033 (3)	0.008 (3)	0.003 (3)	0.007 (3)
C5	0.023 (3)	0.028 (3)	0.024 (3)	0.004 (2)	0.005 (2)	0.007 (2)
C6	0.019 (3)	0.016 (3)	0.019 (3)	0.000 (2)	0.006 (2)	0.001 (2)
Br1	0.0240 (4)	0.0251 (4)	0.0299 (4)	0.0071 (2)	0.0110 (3)	0.0003 (2)
O4	0.021 (2)	0.025 (2)	0.018 (2)	−0.0014 (16)	0.0058 (16)	−0.0016 (16)

Geometric parameters (Å, º) top

Cu1—O2	1.938 (4)	C1—C6	1.520 (8)
Cu1—O1	1.963 (4)	C2—C3	1.365 (9)
Cu1—O4	1.990 (4)	C2—H2A	0.9500
Cu1—Br1	2.4034 (8)	C3—C4	1.393 (10)
N1—O1	1.336 (6)	C3—H3A	0.9500
N1—C5	1.348 (7)	C4—C5	1.373 (9)
N1—C1	1.366 (7)	C4—H4A	0.9500
O2—C6	1.272 (7)	C5—H5A	0.9500
O3—C6	1.232 (7)	O4—H4B2	0.8500
C1—C2	1.375 (8)	O4—H4B1	0.8500

O2—Cu1—O1	87.31 (16)	C1—C2—H2A	119.3
O2—Cu1—O4	176.34 (17)	C2—C3—C4	119.0 (6)
O1—Cu1—O4	89.04 (16)	C2—C3—H3A	120.5
O2—Cu1—Br1	90.90 (12)	C4—C3—H3A	120.5
O1—Cu1—Br1	171.71 (12)	C5—C4—C3	119.3 (6)
O4—Cu1—Br1	92.68 (12)	C5—C4—H4A	120.4
O1—N1—C5	117.5 (4)	C3—C4—H4A	120.4
O1—N1—C1	121.2 (4)	N1—C5—C4	120.5 (6)
C5—N1—C1	121.4 (5)	N1—C5—H5A	119.8
N1—O1—Cu1	116.3 (3)	C4—C5—H5A	119.8
C6—O2—Cu1	127.5 (4)	O3—C6—O2	125.1 (5)
N1—C1—C2	118.5 (5)	O3—C6—C1	116.4 (5)
N1—C1—C6	120.3 (5)	O2—C6—C1	118.5 (5)
C2—C1—C6	121.1 (5)	Cu1—O4—H4B2	109.1
C3—C2—C1	121.3 (6)	Cu1—O4—H4B1	109.3
C3—C2—H2A	119.3	H4B2—O4—H4B1	76.6

C5—N1—O1—Cu1	−131.2 (4)	C1—C2—C3—C4	−3.0 (10)
C1—N1—O1—Cu1	49.5 (5)	C2—C3—C4—C5	2.1 (10)
O2—Cu1—O1—N1	−52.2 (3)	O1—N1—C5—C4	179.8 (5)
O4—Cu1—O1—N1	128.0 (3)	C1—N1—C5—C4	−0.9 (9)
O1—Cu1—O2—C6	20.4 (5)	C3—C4—C5—N1	−0.1 (10)
Br1—Cu1—O2—C6	−167.7 (5)	Cu1—O2—C6—O3	−166.6 (4)
O1—N1—C1—C2	179.2 (5)	Cu1—O2—C6—C1	15.8 (7)
C5—N1—C1—C2	0.0 (8)	N1—C1—C6—O3	147.3 (5)
O1—N1—C1—C6	−1.1 (7)	C2—C1—C6—O3	−33.0 (8)
C5—N1—C1—C6	179.6 (5)	N1—C1—C6—O2	−34.8 (8)
N1—C1—C2—C3	2.0 (9)	C2—C1—C6—O2	144.8 (6)
C6—C1—C2—C3	−177.7 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B2···O2ⁱ	0.85	1.97	2.738 (5)	149
O4—H4B2···Br1ⁱ	0.85	3.07	3.741 (4)	137
O4—H4B1···Br1ⁱⁱ	0.85	2.59	3.377 (4)	155

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

Experimental details

Crystal data
Chemical formula	[CuBr(C₆H₄NO₃)(H₂O)]
M_r	299.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.7116 (3), 10.0302 (2), 9.4984 (3)
β (°)	110.821 (2)
V (Å³)	864.81 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.12
Crystal size (mm)	0.52 × 0.35 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.095, 0.241
No. of measured, independent and observed [I > 2σ(I)] reflections	2584, 1515, 1420
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.127, 1.00
No. of reflections	1515
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.09, −0.93

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), 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
O4—H4B2···O2ⁱ	0.85	1.97	2.738 (5)	149
O4—H4B2···Br1ⁱ	0.85	3.07	3.741 (4)	137
O4—H4B1···Br1ⁱⁱ	0.85	2.59	3.377 (4)	155

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

Acknowledgements

We are grateful for financial support from the National Science Foundation of Fujian Province of China (No. 2010 J01288, E0610017).

References

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