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

Abstract

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 [11].

Related literature

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

Experimental

Crystal data

• C₁₂H₈N₂O₄

• M _r = 244.20

• Triclinic,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.071

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were placed in calculated positions and included in a riding-model approximation, with C—H = 0.93 Å, O-H = 0.82Å and U_iso(H)= 1.2U_eq(C) or 1.5U_eq(O).

Figures

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].

Crystal data

C12H8N2O4	Z = 1
Mr = 244.20	F(000) = 126
Triclinic, P1	Dx = 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

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

Refinement

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(Fo2) + (0.1116P)2 + 0.1159P] where P = (Fo2 + 2Fc2)/3
893 reflections	(Δ/σ)max < 0.001
82 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

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

Symmetry codes: (ii) −x+1, −y, −z+2.