Poly[bis­(μ-2,6-dimethyl­pyridinium-3,5-dicarboxyl­ato-κ2O3:O5)copper(II)]

Zhang, H.-K.; Du, Y.-H.; Jiang, T.; Li, B.-Y.; Hou, G.-F.

doi:10.1107/S1600536808035873

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1510

doi:10.1107/S1600536808035873

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Poly[bis(μ-2,6-dimethylpyridinium-3,5-dicarboxylato-κ²O³:O⁵)copper(II)]

Hong-Kun Zhang,^a ^* Yu-Hong Du,^a Tao Jiang,^a Bai-Yan Li ^b and Guang-Feng Hou ^b

^aDepartment of Food and Environmental Engineering, Heilongjiang East College, Harbin 150086, People's Republic of China, and ^bCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: zhanghongkun2000@163.com

(Received 31 October 2008; accepted 1 November 2008; online 8 November 2008)

In the title coordination polymer, [Cu(C₉H₈NO₄)₂]_n, the Cu atom, located on a twofold rotation axis, is four coordinate in a distorted square-planar environment. Each 2,6-dimethylpyridinium-3,5-dicarboxylate anion bridges two Cu atoms, forming a two-dimensional coordination polymer. A three-dimensional supramolecular network is built from N—H⋯O hydrogen bonds involving the pyridinium NH and the carboxyl COO groups.

Related literature

For the synthesis of 2,6-dimethylpyridine-3,5-dicarboxylic acid, see: Checchi et al. (1959 ). For the crystal structures of some of its metal complexes, see: Gao et al. (2007 ); Shi et al. (2007 ); Zeng et al. (2000 , 2002 ).

Experimental

Crystal data

[Cu(C₉H₈N₂O₄)₂]
M_r = 451.87
Orthorhombic, P b c n
a = 8.2003 (16) Å
b = 16.234 (3) Å
c = 13.708 (3) Å
V = 1824.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.25 mm⁻¹
T = 291 (2) K
0.26 × 0.24 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.733, T_max = 0.801
16747 measured reflections
2097 independent reflections
1754 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.092
S = 1.09
2097 reflections
138 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H8⋯O3ⁱ	0.82 (3)	1.88 (3)	2.698 (2)	177 (3)
Symmetry code: (i) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035873/ng2511sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035873/ng2511Isup2.hkl

checkCIF report

Comment top

To the best of our knowledge, there have been few reports to date on the crystal structure of 2,6-dimethylpyrine-3,5-dicarboxylic acid ligand (Zeng et al., 2000; Zeng et al., 2002: Gao et al., 2007). The crystal structure of 2,6-dimethylpyridinium-3,5-dicarboxylate ligand and Cu atom complex have been reported, namely trans-tetraaquabis (2,6-dimethylpyrinium-3,5-dicarboxylate)cooper(II) tetrahydrate, which is a discrete compound (Shi et al., 2007). In this paper, we report the new two-dimensional title complex, (I), synthesized by the recation of 2,6-dimethylpyrine-3,5-dicarboxylic acid and copper(II) dinitrate in methanol solution.

In the title compound, (Fig. 1), the Cu atom is located on a twofold rotation axis is four coordinated in a square environment that is formed by four carboxylate O atoms from four 2,6-dimethylpyridinium-3,5- dicarboxylate ligands. Each 2,6-dimethylpyridinium-3,5-dicarboxylate ligand bridges two Cu atom to form a two-dimensional supramolecular network parallel the ab plane (Fig. 2). In addition, N1—H8···O3ⁱ hydrogen bonds link these adjacent plane into a three-dimensional supramolecular network (Table 1).

Related literature top

For the synthesis of 2,6-dimethylpyridine-3,5-dicarboxylic acid, see: Checchi et al. (1959). For the crystal structures of its metal complexes, see: Gao et al. (2007); Shi et al. (2007); Zeng et al. (2000, 2002).

Experimental top

2,6-Dimethylpyridine-3,5-dicarboxylic acid was prepared by basic hydrolysis of diethyl 2,6-dimethylpyridine-3,5-dicarboxylate, prepared according to Checchi (1959). Diethyl 2,6-dimethylpyridine-3,5-dicarboxylate (25.1 g, 0.1 mol) and potassium hydroxide (13.44 g, 0.24 mol) were dissolved in 150 ml e thanol and 150 ml water mixed solution, then stirred for three hours under reflux conditions. 10.5 g 2,6-Dimethylpyridine-3,5-dicarboxylic acid, a white precipitate, formed by adjusting pH of solution to 3 with 0.1 M HCl after evaporation of ethanol.

The complex (I) was synthesized with coppert(II) dinitrate (0.368 g, 2 mmol) and 2,6-dimethylpyridine-3,5-dicarboxylic acid (0.390 g, 2 mmol) were dissolved in methanol and the pH was adjusted to 6 with 0.01M sodium hydroxide. Black crystals were separated from the filtered solution after several days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms. [symmetry codes: (I): -x - 1, -y + 1, -z; (II): x - 1, 3/2 - y, -1/2 + z; (III): x, -1/2 - y, -1/2 + z]
	Fig. 2. Part of the polymeric structure of (I), showing a two-dimensional network.

Poly[bis(µ-2,6-dimethylpyridinium-3,5-dicarboxylato- κ²O³:O⁵)copper(II)] top

Crystal data top

[Cu(C₉H₈N₂O₄)₂]	F(000) = 924
M_r = 451.87	D_x = 1.645 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 12587 reflections
a = 8.2003 (16) Å	θ = 3.2–27.5°
b = 16.234 (3) Å	µ = 1.25 mm⁻¹
c = 13.708 (3) Å	T = 291 K
V = 1824.9 (6) Å³	Bluck, black
Z = 4	0.26 × 0.24 × 0.19 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2097 independent reflections
Radiation source: fine-focus sealed tube	1754 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scan	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.733, T_max = 0.801	k = −21→21
16747 measured reflections	l = −17→17

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0491P)² + 0.9342P] where P = (F_o² + 2F_c²)/3
2097 reflections	(Δ/σ)_max = 0.008
138 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Cu(C₉H₈N₂O₄)₂]	V = 1824.9 (6) Å³
M_r = 451.87	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 8.2003 (16) Å	µ = 1.25 mm⁻¹
b = 16.234 (3) Å	T = 291 K
c = 13.708 (3) Å	0.26 × 0.24 × 0.19 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2097 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1754 reflections with I > 2σ(I)
T_min = 0.733, T_max = 0.801	R_int = 0.051
16747 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.41 e Å⁻³
2097 reflections	Δρ_min = −0.29 e Å⁻³
138 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
C1	0.1149 (2)	0.35544 (11)	0.53558 (13)	0.0216 (4)
C2	0.1113 (2)	0.33765 (12)	0.43628 (14)	0.0226 (4)
C3	0.1706 (3)	0.39606 (12)	0.37198 (13)	0.0251 (4)
H1	0.1677	0.3849	0.3055	0.030*
C4	0.2345 (3)	0.47081 (12)	0.40328 (13)	0.0225 (4)
C5	0.2407 (3)	0.48643 (11)	0.50282 (13)	0.0211 (4)
C6	0.0406 (3)	0.25909 (13)	0.39516 (15)	0.0269 (4)
C7	0.2938 (3)	0.53108 (12)	0.32739 (14)	0.0257 (4)
C8	0.3043 (3)	0.56351 (13)	0.54895 (15)	0.0300 (5)
H5	0.2941	0.5595	0.6186	0.045*
H6	0.2427	0.6099	0.5259	0.045*
H7	0.4170	0.5706	0.5320	0.045*
C9	0.0530 (3)	0.30107 (14)	0.61494 (15)	0.0331 (5)
H2	0.1078	0.3142	0.6749	0.050*
H3	0.0736	0.2446	0.5984	0.050*
H4	−0.0621	0.3094	0.6227	0.050*
Cu1	0.0000	0.148168 (18)	0.2500	0.02018 (13)
H8	0.186 (3)	0.4388 (17)	0.621 (2)	0.042 (8)*
N1	0.1800 (2)	0.42800 (10)	0.56291 (12)	0.0225 (4)
O1	−0.0813 (2)	0.22887 (11)	0.43090 (13)	0.0466 (5)
O2	0.1169 (2)	0.23282 (9)	0.32017 (10)	0.0333 (4)
O3	0.2050 (3)	0.54134 (12)	0.25578 (11)	0.0442 (5)
O4	0.4295 (2)	0.56494 (9)	0.34300 (11)	0.0337 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0243 (10)	0.0224 (9)	0.0180 (9)	0.0001 (8)	−0.0003 (7)	0.0006 (7)
C2	0.0248 (10)	0.0226 (9)	0.0203 (9)	−0.0015 (8)	−0.0012 (7)	−0.0027 (7)
C3	0.0331 (11)	0.0271 (10)	0.0152 (8)	−0.0015 (8)	−0.0020 (7)	−0.0029 (7)
C4	0.0283 (10)	0.0217 (9)	0.0175 (8)	−0.0017 (8)	−0.0009 (7)	0.0015 (7)
C5	0.0239 (10)	0.0207 (9)	0.0186 (9)	0.0000 (8)	−0.0020 (7)	0.0002 (7)
C6	0.0319 (11)	0.0239 (10)	0.0250 (10)	−0.0044 (8)	−0.0064 (8)	−0.0013 (8)
C7	0.0382 (12)	0.0203 (9)	0.0186 (9)	0.0020 (9)	0.0036 (8)	0.0015 (7)
C8	0.0399 (12)	0.0254 (10)	0.0246 (10)	−0.0060 (9)	−0.0031 (8)	−0.0051 (8)
C9	0.0442 (13)	0.0325 (11)	0.0225 (10)	−0.0085 (10)	0.0067 (9)	0.0033 (8)
Cu1	0.0283 (2)	0.01488 (19)	0.01735 (19)	0.000	−0.00329 (12)	0.000
N1	0.0294 (9)	0.0249 (8)	0.0132 (7)	−0.0018 (7)	−0.0006 (6)	−0.0012 (6)
O1	0.0439 (11)	0.0449 (10)	0.0511 (10)	−0.0222 (9)	0.0102 (9)	−0.0123 (8)
O2	0.0440 (9)	0.0283 (7)	0.0277 (7)	−0.0087 (7)	−0.0004 (7)	−0.0095 (6)
O3	0.0507 (11)	0.0592 (12)	0.0228 (8)	−0.0022 (9)	−0.0051 (7)	0.0161 (7)
O4	0.0442 (10)	0.0279 (8)	0.0290 (8)	−0.0094 (7)	0.0034 (7)	0.0081 (6)

Geometric parameters (Å, º) top

C1—N1	1.346 (3)	C7—O4	1.259 (3)
C1—C2	1.392 (3)	C8—H5	0.9600
C1—C9	1.490 (3)	C8—H6	0.9600
C2—C3	1.383 (3)	C8—H7	0.9600
C2—C6	1.510 (3)	C9—H2	0.9600
C3—C4	1.390 (3)	C9—H3	0.9600
C3—H1	0.9300	C9—H4	0.9600
C4—C5	1.389 (3)	Cu1—O2	1.9322 (15)
C4—C7	1.509 (3)	Cu1—O2ⁱ	1.9322 (15)
C5—N1	1.351 (2)	Cu1—O4ⁱⁱ	1.9455 (15)
C5—C8	1.496 (3)	Cu1—O4ⁱⁱⁱ	1.9455 (15)
C6—O1	1.216 (3)	N1—H8	0.82 (3)
C6—O2	1.277 (3)	O4—Cu1^iv	1.9455 (15)
C7—O3	1.234 (3)

N1—C1—C2	117.53 (17)	C5—C8—H6	109.5
N1—C1—C9	116.75 (17)	H5—C8—H6	109.5
C2—C1—C9	125.72 (18)	C5—C8—H7	109.5
C3—C2—C1	118.26 (17)	H5—C8—H7	109.5
C3—C2—C6	118.44 (17)	H6—C8—H7	109.5
C1—C2—C6	123.26 (17)	C1—C9—H2	109.5
C2—C3—C4	122.31 (17)	C1—C9—H3	109.5
C2—C3—H1	118.8	H2—C9—H3	109.5
C4—C3—H1	118.8	C1—C9—H4	109.5
C5—C4—C3	118.47 (17)	H2—C9—H4	109.5
C5—C4—C7	123.17 (17)	H3—C9—H4	109.5
C3—C4—C7	118.36 (17)	O2—Cu1—O2ⁱ	89.32 (10)
N1—C5—C4	117.21 (17)	O2—Cu1—O4ⁱⁱ	165.38 (7)
N1—C5—C8	117.25 (16)	O2ⁱ—Cu1—O4ⁱⁱ	91.17 (7)
C4—C5—C8	125.51 (17)	O2—Cu1—O4ⁱⁱⁱ	91.17 (7)
O1—C6—O2	126.3 (2)	O2ⁱ—Cu1—O4ⁱⁱⁱ	165.38 (7)
O1—C6—C2	120.40 (19)	O4ⁱⁱ—Cu1—O4ⁱⁱⁱ	92.03 (10)
O2—C6—C2	113.20 (18)	C1—N1—C5	126.19 (16)
O3—C7—O4	126.7 (2)	C1—N1—H8	119 (2)
O3—C7—C4	116.5 (2)	C5—N1—H8	115 (2)
O4—C7—C4	116.80 (18)	C6—O2—Cu1	113.26 (14)
C5—C8—H5	109.5	C7—O4—Cu1^iv	117.02 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H8···O3^v	0.82 (3)	1.88 (3)	2.698 (2)	177 (3)

Symmetry code: (v) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₉H₈N₂O₄)₂]
M_r	451.87
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	291
a, b, c (Å)	8.2003 (16), 16.234 (3), 13.708 (3)
V (Å³)	1824.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.25
Crystal size (mm)	0.26 × 0.24 × 0.19

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.733, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	16747, 2097, 1754
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.092, 1.09
No. of reflections	2097
No. of parameters	138
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.29

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), 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
N1—H8···O3ⁱ	0.82 (3)	1.88 (3)	2.698 (2)	177 (3)

Symmetry code: (i) x, −y+1, z+1/2.

Acknowledgements

The authors thank the Project of the Science and Technology Foundation of Heilongjiang Provincial Education Department (grant No. 11523041) and Heilongjiang East College for supporting this study.

References

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