Bis(4-carb­oxy­pyridine-2-carboxyl­ato-κ2N,O2)copper(II) dimethyl sulfoxide disolvate

Aghabozorg, H.; Goodarzi, S.; Mirzaei, M.; Notash, B.

doi:10.1107/S1600536811003424

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page m290

doi:10.1107/S1600536811003424

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Bis(4-carboxypyridine-2-carboxylato-κ²N,O²)copper(II) dimethyl sulfoxide disolvate

Hossein Aghabozorg,^a ^* Saba Goodarzi,^a Masoud Mirzaei ^b and Behrouz Notash ^c

^aFaculty of Chemistry, Islamic Azad University, North Tehran Branch, Tehran, Iran, ^bDepartment of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran, and ^cDepartment of Chemistry, Shahid Beheshti University, G.C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 16 January 2011; accepted 26 January 2011; online 29 January 2011)

In the title complex, [Cu(C₇H₄NO₄)₂]·2C₂H₆OS, the Cu^II atom is situated on an inversion centre and is N,O-chelated by two monoanionic 4-carboxypyridine-2-carboxylate ligands in a slightly distorted square-planar coordination geometry. The dimethyl sulfoxide solvent molecules and Cu^II complex molecules are linked by O—H⋯O hydrogen bonding. In addition, C—H⋯O contacts and π–π interactions [centroid–centroid distance = 3.590 (1) Å] occur.

Related literature

For the design and synthesis of coordination compounds and complexes derived from pyridine-2,4-dicarboxylic acid, see: Aghabozorg et al. (2008 ); Noro et al. (2005 ).

Experimental

Crystal data

[Cu(C₇H₄NO₄)₂]·2C₂H₆OS
M_r = 552.05
Triclinic, $[P \overline 1]$
a = 6.8831 (14) Å
b = 7.5218 (15) Å
c = 11.719 (2) Å
α = 102.95 (3)°
β = 91.86 (3)°
γ = 111.12 (3)°
V = 547.3 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.25 mm⁻¹
T = 298 K
0.2 × 0.10 × 0.05 mm

Data collection

Stoe IPDS II diffractometer
6125 measured reflections
2928 independent reflections
2428 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.092
S = 1.08
2928 reflections
157 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O5ⁱ	0.84 (4)	1.68 (4)	2.518 (3)	173 (4)
C4—H4⋯O3ⁱⁱ	0.93	2.55	3.427 (3)	158
C5—H5⋯O5ⁱⁱⁱ	0.93	2.55	3.370 (3)	147
C8—H8B⋯O2^iv	0.96	2.38	3.223 (3)	147
C9—H9C⋯O4	0.96	2.51	3.448 (4)	164
Symmetry codes: (i) x+1, y, z; (ii) -x+3, -y+1, -z+1; (iii) -x+2, -y+1, -z+1; (iv) -x+1, -y+1, -z.

Data collection: X-AREA (Stoe & Cie, 2005 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003424/bt5466sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003424/bt5466Isup2.hkl

checkCIF report

Comment top

Great interest has been focused on the rapidly expanding field of supramolecular chemistry and crystal engineering of the coordination compounds in recent years because of their intriguing network topologies as well as their potential application as functional materials in many areas (Aghabozorg et al., 2008). Pyridine-2,4-dicarboxylic acid (2,4-pydcH₂) is a good building block for constructing complexes. However, plenty of researches have focused on the supramolecular chemistry and coordination polymers which only include single carboxylic acid ligands, (Noro et al., 2005). In this paper, we report the crystal structure of the title compound prepared from Cu(NO₃)₂.3H₂O, 2,4-pydcH₂ and acridine.

The structure of title complex is shown in Fig. 1. In the complex, 2,4-pydcH ligands are bound to one Cu^II ion through pyridine N and deprotonated carboxylate O atoms at 2-positions, leading to a distorted square planar geometry around the metal ion. The carboxylic groups at the 4-position of 2,4-pydcH ligands are not coordinating. [Cu(C₁₄H₈N₂O₈)] complex is connected into two-dimensional layers through H-bonding interactions (Table 1). The crystal packing is additionally stabilized by π-π stacking interactions (Fig. 2).

Related literature top

For the design and synthesis of coordination compounds and complexes of pyridine-2,4-dicarboxylic acid, see: Aghabozorg et al. (2008); Noro et al. (2005).

Experimental top

A mixture of 2,4-pydcH₂ (83 mg, 0.50 mmol), Cu(NO₃)₂.3H₂O (120 mg, 0.50 mmol), acridine (179 mg, 1.0 mmol) in 18 ml me thanol/DMSO were heated and stirred for 2 hrs, and then cooled to room temperature. The reaction yielded purple plate crystals of the title compound after 2 months.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at 50% probability level (symmetry code: i: 1 - x,-y,1 - z).
	Fig. 2. Packing diagram of the title compound. The intermolecular O—H···O, and C—H···O hydrogen bonds and π···π contacts are shown as blue and orange dashed lines, respectively.

Bis(4-carboxypyridine-2-carboxylato-κ²N,O²)copper(II) dimethyl sulfoxide disolvate top

Crystal data top

[Cu(C₇H₄NO₄)₂]·2C₂H₆OS	Z = 1
M_r = 552.05	F(000) = 283
Triclinic, P1	D_x = 1.675 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8831 (14) Å	Cell parameters from 2928 reflections
b = 7.5218 (15) Å	θ = 3.0–29.1°
c = 11.719 (2) Å	µ = 1.25 mm⁻¹
α = 102.95 (3)°	T = 298 K
β = 91.86 (3)°	Plate, purple
γ = 111.12 (3)°	0.2 × 0.1 × 0.05 mm
V = 547.3 (2) Å³

Data collection top

Stoe IPDS II diffractometer	2428 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 29.1°, θ_min = 3.0°
Detector resolution: 0.15 mm pixels mm^-1	h = −9→9
rotation method scans	k = −10→10
6125 measured reflections	l = −16→15
2928 independent 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0365P)² + 0.2725P] where P = (F_o² + 2F_c²)/3
2928 reflections	(Δ/σ)_max = 0.002
157 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Cu(C₇H₄NO₄)₂]·2C₂H₆OS	γ = 111.12 (3)°
M_r = 552.05	V = 547.3 (2) Å³
Triclinic, P1	Z = 1
a = 6.8831 (14) Å	Mo Kα radiation
b = 7.5218 (15) Å	µ = 1.25 mm⁻¹
c = 11.719 (2) Å	T = 298 K
α = 102.95 (3)°	0.2 × 0.1 × 0.05 mm
β = 91.86 (3)°

Data collection top

Stoe IPDS II diffractometer	2428 reflections with I > 2σ(I)
6125 measured reflections	R_int = 0.034
2928 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.38 e Å⁻³
2928 reflections	Δρ_min = −0.30 e Å⁻³
157 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
O5	0.7477 (3)	0.7579 (3)	0.25725 (15)	0.0572 (5)
S1	0.74093 (10)	0.67910 (10)	0.12483 (5)	0.04660 (16)
Cu1	0.5000	0.0000	0.5000	0.03607 (12)
O1	0.3689 (2)	0.0279 (3)	0.36230 (14)	0.0448 (4)
C6	0.4947 (3)	0.1284 (4)	0.30111 (19)	0.0383 (5)
C2	0.8846 (3)	0.3107 (3)	0.29424 (18)	0.0362 (4)
H2	0.8551	0.3418	0.2249	0.043*
C1	0.7250 (3)	0.2025 (3)	0.34780 (18)	0.0339 (4)
O2	0.4440 (3)	0.1668 (3)	0.21140 (16)	0.0540 (5)
N1	0.7628 (3)	0.1553 (3)	0.44860 (15)	0.0331 (4)
C7	1.2654 (4)	0.4892 (4)	0.28672 (19)	0.0387 (5)
C5	0.9603 (3)	0.2151 (3)	0.49832 (18)	0.0358 (4)
H5	0.9857	0.1825	0.5678	0.043*
C4	1.1283 (3)	0.3242 (3)	0.44914 (19)	0.0368 (4)
H4	1.2648	0.3647	0.4853	0.044*
C3	1.0910 (3)	0.3727 (3)	0.34541 (19)	0.0355 (4)
O3	1.4430 (3)	0.5841 (3)	0.35694 (15)	0.0481 (4)
O4	1.2395 (3)	0.4936 (3)	0.18477 (15)	0.0526 (5)
C8	0.6304 (5)	0.8138 (5)	0.0578 (2)	0.0612 (7)
H8A	0.4882	0.7847	0.0744	0.092*
H8B	0.6323	0.7782	−0.0260	0.092*
H8C	0.7104	0.9522	0.0883	0.092*
C9	1.0046 (5)	0.7850 (6)	0.0982 (3)	0.0713 (9)
H9A	1.0577	0.9246	0.1323	0.107*
H9B	1.0111	0.7597	0.0147	0.107*
H9C	1.0879	0.7280	0.1332	0.107*
H3	1.538 (6)	0.645 (5)	0.320 (3)	0.076 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O5	0.0428 (9)	0.0775 (13)	0.0357 (9)	0.0011 (9)	0.0015 (7)	0.0208 (9)
S1	0.0437 (3)	0.0481 (4)	0.0400 (3)	0.0059 (3)	0.0025 (2)	0.0150 (3)
Cu1	0.03021 (19)	0.0481 (2)	0.03117 (19)	0.01310 (16)	0.00208 (14)	0.01565 (16)
O1	0.0315 (8)	0.0623 (11)	0.0408 (8)	0.0127 (7)	−0.0007 (6)	0.0226 (8)
C6	0.0351 (11)	0.0454 (12)	0.0332 (10)	0.0140 (9)	−0.0016 (8)	0.0110 (9)
C2	0.0378 (11)	0.0411 (11)	0.0286 (9)	0.0131 (9)	−0.0010 (8)	0.0105 (8)
C1	0.0341 (10)	0.0378 (11)	0.0288 (9)	0.0133 (8)	−0.0010 (8)	0.0077 (8)
O2	0.0437 (9)	0.0719 (12)	0.0461 (10)	0.0140 (9)	−0.0067 (7)	0.0293 (9)
N1	0.0336 (8)	0.0394 (9)	0.0272 (8)	0.0142 (7)	0.0019 (6)	0.0096 (7)
C7	0.0362 (11)	0.0479 (13)	0.0343 (10)	0.0167 (10)	0.0045 (8)	0.0134 (9)
C5	0.0359 (10)	0.0437 (12)	0.0296 (9)	0.0161 (9)	−0.0002 (8)	0.0117 (8)
C4	0.0321 (10)	0.0452 (12)	0.0324 (10)	0.0149 (9)	−0.0008 (8)	0.0089 (9)
C3	0.0354 (10)	0.0402 (11)	0.0302 (9)	0.0146 (9)	0.0032 (8)	0.0072 (8)
O3	0.0342 (8)	0.0658 (12)	0.0363 (8)	0.0073 (8)	0.0045 (7)	0.0169 (8)
O4	0.0450 (10)	0.0746 (13)	0.0379 (9)	0.0159 (9)	0.0047 (7)	0.0249 (9)
C8	0.0671 (18)	0.079 (2)	0.0426 (14)	0.0313 (16)	0.0007 (13)	0.0185 (14)
C9	0.0473 (16)	0.109 (3)	0.0604 (18)	0.0251 (17)	0.0136 (14)	0.0325 (18)

Geometric parameters (Å, º) top

O5—S1	1.5247 (19)	C7—O4	1.212 (3)
S1—C8	1.760 (3)	C7—O3	1.313 (3)
S1—C9	1.770 (3)	C7—C3	1.499 (3)
Cu1—O1	1.9123 (16)	C5—C4	1.384 (3)
Cu1—O1ⁱ	1.9123 (16)	C5—H5	0.9300
Cu1—N1	1.9657 (19)	C4—C3	1.387 (3)
Cu1—N1ⁱ	1.9657 (19)	C4—H4	0.9300
O1—C6	1.284 (3)	O3—H3	0.84 (4)
C6—O2	1.223 (3)	C8—H8A	0.9600
C6—C1	1.514 (3)	C8—H8B	0.9600
C2—C1	1.376 (3)	C8—H8C	0.9600
C2—C3	1.392 (3)	C9—H9A	0.9600
C2—H2	0.9300	C9—H9B	0.9600
C1—N1	1.351 (3)	C9—H9C	0.9600
N1—C5	1.334 (3)

O5—S1—C8	105.52 (14)	O3—C7—C3	113.21 (19)
O5—S1—C9	104.03 (14)	N1—C5—C4	121.70 (19)
C8—S1—C9	99.68 (17)	N1—C5—H5	119.2
O1—Cu1—O1ⁱ	180.00 (5)	C4—C5—H5	119.2
O1—Cu1—N1	84.57 (7)	C5—C4—C3	119.3 (2)
O1ⁱ—Cu1—N1	95.43 (7)	C5—C4—H4	120.4
O1—Cu1—N1ⁱ	95.43 (7)	C3—C4—H4	120.4
O1ⁱ—Cu1—N1ⁱ	84.57 (7)	C4—C3—C2	118.7 (2)
N1—Cu1—N1ⁱ	180.0	C4—C3—C7	122.2 (2)
C6—O1—Cu1	115.22 (14)	C2—C3—C7	119.08 (19)
O2—C6—O1	125.9 (2)	C7—O3—H3	111 (2)
O2—C6—C1	119.3 (2)	S1—C8—H8A	109.5
O1—C6—C1	114.78 (18)	S1—C8—H8B	109.5
C1—C2—C3	118.97 (19)	H8A—C8—H8B	109.5
C1—C2—H2	120.5	S1—C8—H8C	109.5
C3—C2—H2	120.5	H8A—C8—H8C	109.5
N1—C1—C2	121.90 (19)	H8B—C8—H8C	109.5
N1—C1—C6	114.33 (19)	S1—C9—H9A	109.5
C2—C1—C6	123.77 (18)	S1—C9—H9B	109.5
C5—N1—C1	119.41 (19)	H9A—C9—H9B	109.5
C5—N1—Cu1	129.51 (15)	S1—C9—H9C	109.5
C1—N1—Cu1	111.07 (14)	H9A—C9—H9C	109.5
O4—C7—O3	124.8 (2)	H9B—C9—H9C	109.5
O4—C7—C3	122.0 (2)

N1—Cu1—O1—C6	−0.79 (18)	O1ⁱ—Cu1—N1—C5	0.0 (2)
N1ⁱ—Cu1—O1—C6	179.21 (18)	O1—Cu1—N1—C1	−0.07 (15)
Cu1—O1—C6—O2	−178.7 (2)	O1ⁱ—Cu1—N1—C1	179.93 (15)
Cu1—O1—C6—C1	1.4 (3)	C1—N1—C5—C4	−0.1 (3)
C3—C2—C1—N1	0.1 (3)	Cu1—N1—C5—C4	179.81 (16)
C3—C2—C1—C6	179.5 (2)	N1—C5—C4—C3	−0.1 (3)
O2—C6—C1—N1	178.6 (2)	C5—C4—C3—C2	0.4 (3)
O1—C6—C1—N1	−1.5 (3)	C5—C4—C3—C7	−179.5 (2)
O2—C6—C1—C2	−0.8 (4)	C1—C2—C3—C4	−0.4 (3)
O1—C6—C1—C2	179.2 (2)	C1—C2—C3—C7	179.5 (2)
C2—C1—N1—C5	0.1 (3)	O4—C7—C3—C4	162.8 (2)
C6—C1—N1—C5	−179.27 (19)	O3—C7—C3—C4	−17.7 (3)
C2—C1—N1—Cu1	−179.83 (17)	O4—C7—C3—C2	−17.1 (4)
C6—C1—N1—Cu1	0.8 (2)	O3—C7—C3—C2	162.4 (2)
O1—Cu1—N1—C5	180.0 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5ⁱⁱ	0.84 (4)	1.68 (4)	2.518 (3)	173 (4)
C4—H4···O3ⁱⁱⁱ	0.93	2.55	3.427 (3)	158
C5—H5···O5^iv	0.93	2.55	3.370 (3)	147
C8—H8B···O2^v	0.96	2.38	3.223 (3)	147
C9—H9C···O4	0.96	2.51	3.448 (4)	164

Symmetry codes: (ii) x+1, y, z; (iii) −x+3, −y+1, −z+1; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₄NO₄)₂]·2C₂H₆OS
M_r	552.05
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.8831 (14), 7.5218 (15), 11.719 (2)
α, β, γ (°)	102.95 (3), 91.86 (3), 111.12 (3)
V (Å³)	547.3 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.25
Crystal size (mm)	0.2 × 0.1 × 0.05

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6125, 2928, 2428
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.092, 1.08
No. of reflections	2928
No. of parameters	157
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.30

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5ⁱ	0.84 (4)	1.68 (4)	2.518 (3)	173 (4)
C4—H4···O3ⁱⁱ	0.93	2.55	3.427 (3)	158
C5—H5···O5ⁱⁱⁱ	0.93	2.55	3.370 (3)	147
C8—H8B···O2^iv	0.96	2.38	3.223 (3)	147
C9—H9C···O4	0.96	2.51	3.448 (4)	164

Symmetry codes: (i) x+1, y, z; (ii) −x+3, −y+1, −z+1; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z.

Acknowledgements

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

References

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