2,2′-Bipyridine-5,5′-dicarboxylic acid

Wang, C.

doi:10.1107/S1600536809030207

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2081

doi:10.1107/S1600536809030207

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2,2′-Bipyridine-5,5′-dicarboxylic acid

Chongchen Wang ^a ^*

^aSchool of Environmental and Energy Engineering, Beijing University of Civil Engineering and Architecture, 100044 Beijing, People's Republic of China
^*Correspondence e-mail: chongchenwang@126.com

(Received 15 July 2009; accepted 29 July 2009; online 8 August 2009)

The title molecule, C₁₂H₈N₂O₄, lies on an inversion center. In the crystal structure, intermolecular O—H⋯O hydrogen bonds connect molecules into one-dimensional chains along [1 $[\overline{1}]$ 1].

Related literature

For synthetic applications of the title compound, see: Schokecht & Kempe (2004 ).

Experimental

Crystal data

C₁₂H₈N₂O₄
M_r = 244.20
Triclinic, $[P \overline 1]$
a = 3.7384 (5) Å
b = 6.3934 (8) Å
c = 10.7786 (13) Å
α = 98.774 (2)°
β = 92.567 (1)°
γ = 90.000 (1)°
V = 254.34 (6) Å³
Z = 1
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.15 × 0.11 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.982, T_max = 0.990
1343 measured reflections
893 independent reflections
657 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.214
S = 1.14
893 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.82	2.625 (3)	168
Symmetry code: (i) -x+1, -y, -z+2.

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) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030207/lh2868sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030207/lh2868Isup2.hkl

checkCIF report

Comment top

2,2'-bipyridine-5,5'-dicarboxylate acid is a potential multi-dentate ligand with a versatile coordination mode, which has been used in self-assembled porous coordination synthesis (Schokecht & Kempe, 2004). The crystals of the title compound were obtained unintentionally as the harvested product of the hydrothermal reaction of 2,2'-bipyridine-5,5'-dicarboxylate acid, Eu₂O₃ and 1,10-phenanthroline.

The molecular structure of the title compound is shown in Fig. 1. In the crystal structure, intermolecular O—H···O hydrogen bonds connect molecules into one-dimensional chains along [1 -1 1] (Fig. 2).

Related literature top

For synthetic applications of the title compound, see: Schokecht & Kempe (2004).

Experimental top

Yellow needle-like crystals of the title compound were obtained by hydrothermal reaction of 2,2'-bipyridine-5,5'-dicarboxylate acid (0.04884 g), 1,10-phenanthroline (0.0360 g), Eu₂O₃ (0.0702 g) and deionized water (15 ml) in a 23 ml teflon-lined reaction vesset at 433 K for 120 h, followed by slow cooling to room temperature.

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) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound shown with 30% probabilty ellipsoids [symmetry code: (a) -x, -y+1, -z+1].
	Fig. 2. Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines. The one-dimensional hydrogen-bonded chains propagate along [1-11].

2,2'-Bipyridine-5,5'-dicarboxylic acid top

Crystal data top

C₁₂H₈N₂O₄	Z = 1
M_r = 244.20	F(000) = 126
Triclinic, P1	D_x = 1.594 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.7384 (5) Å	Cell parameters from 528 reflections
b = 6.3934 (8) Å	θ = 3.2–27.6°
c = 10.7786 (13) Å	µ = 0.12 mm⁻¹
α = 98.774 (2)°	T = 298 K
β = 92.567 (1)°	Needle, yellow
γ = 90.000 (1)°	0.15 × 0.11 × 0.08 mm
V = 254.34 (6) Å³

Data collection top

Bruker SMART CCD diffractometer	893 independent reflections
Radiation source: fine-focus sealed tube	657 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.982, T_max = 0.990	k = −7→7
1343 measured reflections	l = −11→12

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.214	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.1116P)² + 0.1159P] where P = (F_o² + 2F_c²)/3
893 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₂H₈N₂O₄	γ = 90.000 (1)°
M_r = 244.20	V = 254.34 (6) Å³
Triclinic, P1	Z = 1
a = 3.7384 (5) Å	Mo Kα radiation
b = 6.3934 (8) Å	µ = 0.12 mm⁻¹
c = 10.7786 (13) Å	T = 298 K
α = 98.774 (2)°	0.15 × 0.11 × 0.08 mm
β = 92.567 (1)°

Data collection top

Bruker SMART CCD diffractometer	893 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	657 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.990	R_int = 0.023
1343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.214	H-atom parameters constrained
S = 1.14	Δρ_max = 0.33 e Å⁻³
893 reflections	Δρ_min = −0.36 e Å⁻³
82 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
N1	0.1979 (7)	0.2556 (4)	0.5341 (2)	0.0351 (8)
O1	0.5129 (7)	−0.0316 (4)	0.8383 (2)	0.0492 (8)
H1	0.5614	−0.0788	0.9036	0.074*
O2	0.2843 (7)	0.2274 (4)	0.9736 (2)	0.0536 (9)
C1	0.3541 (8)	0.1439 (5)	0.8636 (3)	0.0334 (8)
C2	0.2905 (8)	0.1631 (5)	0.6337 (3)	0.0347 (9)
H2	0.3922	0.0293	0.6197	0.042*
C3	0.2438 (7)	0.2552 (5)	0.7571 (3)	0.0307 (9)
C4	0.0964 (8)	0.4566 (5)	0.7784 (3)	0.0353 (9)
H4	0.0640	0.5238	0.8598	0.042*
C5	−0.0008 (8)	0.5548 (5)	0.6768 (3)	0.0332 (8)
H5	−0.1009	0.6892	0.6890	0.040*
C6	0.0520 (8)	0.4512 (5)	0.5562 (3)	0.0295 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0443 (16)	0.0333 (15)	0.0284 (15)	0.0064 (12)	−0.0011 (12)	0.0079 (12)
O1	0.0724 (18)	0.0463 (16)	0.0308 (14)	0.0208 (13)	−0.0006 (12)	0.0129 (11)
O2	0.083 (2)	0.0525 (17)	0.0267 (14)	0.0231 (14)	0.0056 (12)	0.0108 (11)
C1	0.0347 (17)	0.0366 (18)	0.0297 (17)	0.0043 (14)	−0.0014 (13)	0.0088 (14)
C2	0.0390 (18)	0.0339 (18)	0.0329 (18)	0.0076 (14)	−0.0009 (13)	0.0108 (14)
C3	0.0309 (16)	0.0350 (19)	0.0271 (18)	0.0003 (14)	−0.0020 (13)	0.0083 (14)
C4	0.0446 (19)	0.0375 (19)	0.0240 (16)	0.0068 (15)	0.0024 (13)	0.0047 (13)
C5	0.0393 (18)	0.0321 (17)	0.0296 (17)	0.0078 (14)	0.0009 (13)	0.0092 (14)
C6	0.0288 (15)	0.0318 (18)	0.0289 (17)	−0.0009 (13)	−0.0021 (12)	0.0088 (14)

Geometric parameters (Å, º) top

N1—C2	1.335 (4)	C2—H2	0.9300
N1—C6	1.357 (4)	C3—C4	1.391 (4)
O1—C1	1.267 (4)	C4—C5	1.378 (4)
O1—H1	0.8200	C4—H4	0.9300
O2—C1	1.263 (4)	C5—C6	1.388 (4)
C1—C3	1.484 (4)	C5—H5	0.9300
C2—C3	1.388 (4)	C6—C6ⁱ	1.482 (6)

C2—N1—C6	117.4 (3)	C4—C3—C1	120.8 (3)
C1—O1—H1	109.5	C5—C4—C3	118.9 (3)
O2—C1—O1	123.7 (3)	C5—C4—H4	120.5
O2—C1—C3	118.7 (3)	C3—C4—H4	120.5
O1—C1—C3	117.6 (3)	C4—C5—C6	119.3 (3)
N1—C2—C3	123.8 (3)	C4—C5—H5	120.3
N1—C2—H2	118.1	C6—C5—H5	120.3
C3—C2—H2	118.1	N1—C6—C5	122.4 (3)
C2—C3—C4	118.2 (3)	N1—C6—C6ⁱ	116.1 (3)
C2—C3—C1	121.0 (3)	C5—C6—C6ⁱ	121.5 (4)

C6—N1—C2—C3	0.4 (5)	C2—C3—C4—C5	0.8 (5)
N1—C2—C3—C4	−0.9 (5)	C1—C3—C4—C5	179.7 (3)
N1—C2—C3—C1	−179.8 (3)	C3—C4—C5—C6	−0.3 (5)
O2—C1—C3—C2	−175.3 (3)	C2—N1—C6—C5	0.2 (5)
O1—C1—C3—C2	4.4 (5)	C2—N1—C6—C6ⁱ	−179.3 (3)
O2—C1—C3—C4	5.9 (5)	C4—C5—C6—N1	−0.2 (5)
O1—C1—C3—C4	−174.4 (3)	C4—C5—C6—C6ⁱ	179.2 (3)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱⁱ	0.82	1.82	2.625 (3)	168

Symmetry code: (ii) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₂H₈N₂O₄
M_r	244.20
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	3.7384 (5), 6.3934 (8), 10.7786 (13)
α, β, γ (°)	98.774 (2), 92.567 (1), 90.000 (1)
V (Å³)	254.34 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.15 × 0.11 × 0.08

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.982, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	1343, 893, 657
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.214, 1.14
No. of reflections	893
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.36

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.82	2.625 (3)	167.9

Symmetry code: (i) −x+1, −y, −z+2.

Acknowledgements

The authors gratefully acknowledge the financial support of the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality and the Research Fund of Beijing University of Civil Engineering and Architecture..

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Schokecht, B. & Kempe, R. (2004). Z. Anorg. Allg. Chem. 630, 1377-1379. 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar