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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o114.
Published online 2009 December 12. doi:  10.1107/S1600536809052106
PMCID: PMC2980043

Ethane-1,2-diyl bis­(pyridine-3-car­box­ylate)

Abstract

The title compound, C14H12N2O4, has twofold imposed crystallographic symmetry in the solid state. The asymmetric unit contains one half-mol­ecule. An intra­molecular C—H(...)O hydrogen bond is formed between the carboxyl­ate O group and one H atom of the aromatic ring such that a five-membered ring is formed. The angle between the planes of symmetry-related aromatic rings is 44.71 (19)°.

Related literature

For the synthesis of ditopic flexible linkers, see: Chatterjee et al. (2004 [triangle]). For the potential of coordination polymers based on this multitopic bridging ligand and metal centers as functional materials, see: Huang et al. (2007 [triangle]). For applications, see: Matsuda et al. (2005 [triangle]); Wu et al. (2005 [triangle]); Xiang et al. (2005 [triangle]). For bond-length data, see: Allen (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o114-scheme1.jpg

Experimental

Crystal data

  • C14H12N2O4
  • M r = 272.26
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o114-efi1.jpg
  • a = 4.0740 (14) Å
  • b = 21.3404 (7) Å
  • c = 7.395 (6) Å
  • V = 642.9 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 293 K
  • 0.19 × 0.10 × 0.08 mm

Data collection

  • Nonius KappaCCD area-detector diffractometer
  • 2298 measured reflections
  • 874 independent reflections
  • 694 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.131
  • S = 1.27
  • 874 reflections
  • 91 parameters
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: COLLECT (Nonius, 2000 [triangle]); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809052106/om2303sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052106/om2303Isup2.hkl

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

Acknowledgments

We thank the Spanish Research Council (CSIC) for providing us with a free-of-charge license for the CSD system. JV thanks the Universidad de Antofagasta for PhD fellowships.

supplementary crystallographic information

Comment

In the past decade, crystalline nanoporous coordination polymers have been extensively studied for their potential applications in magnetism (Xiang, et al., 2005), catalysis (Wu, et al., 2005), and gas adsorption or separation (Matsuda, et al., 2005). Ethanediyl pyridinecarboxylate ligands have beeen used as flexible linkers to generate metallocyclic ensembles, which showed hysteretic adsorption properties (Chatterjee et al., 2004). We report here the crystal structure of the title compound which has twofold imposed crystallographic symmetry in the solid state. The asymmetric unit contains one-half of the molecule (Fig. 1). This compound crystallizes in a chiral space group, P21212 despite the absence of a chiral center. This chirality arises from the crystal packing. A twofold rotation axis passes through the midpoint of C7 and C7(i). An intramolecular C—H···O hydrogen bond is formed between the carboxylate O group and one H-atom of the aromatic ring such that a five-membered ring is formed. The angle between the planes of symmetry-related aromatic rings is 44.71 (19). A search in the Cambridge Structural Database (version 5.30; Allen, 2002) for the title compound yielded two structures namely catena-(bis(µ2-1,2-ethanediyl bis(3-pyridinecarboxylate)-N,N')- bis(isothiocyanato)-cobalt(ii) trihydrate) and catena-(bis(µ2-1,2-ethanediyl bis(3-pyridinecarboxylate)-N,N')- bis(isothiocyanato)-cobalt(ii) tetrahydrofuran clathrate) (refcodes HEXKEB and HEXKIF, respectively) (Huang et al., 2007). The most obvious differences between these coordination polymers and the uncoordinated ligand reported here are the the angles between the planes of symmetry-related aromatic rings (66.80 (12)° and 44.71 (19)°, respectively) which is a consequence of the flexible organic components of the title compound.

Experimental

Nicotinic acid (15 g, 0.122 mol) was stirred in SOCl2 (40 ml) in the presence of DMF (0.6 ml) at 60 °C for 12 h. Excess thionyl chloride was removed in vacuo. Dried ethylene glycol (3.4 ml, 0.061 mol) was added. After the evolution of hydrogen chloride ended, the mixture was heated at 150 °C for 2 h. The mixture was dissolved in water, and NH4OH solution was added. After filtration, recrystallization in ethyl acetate gave colorless crystals. Yield 11.53 g (75%). Analysis calculated for C14H12N2O4: C: 61.76, H 4.44, N: 10.29; found: C: 61.25, H: 4.58, N: 10.15. IR (KBr, cm-1): (C═O) 1723 s, (C═C) 1589 m, (Ar C—C, C═N) 1424 s, (C—O) 1287 m.

Refinement

In the absence of anomalous scatterers, 488 Friedel pairs were merged.

H atoms were positioned geometrically at distances of 0.93 (CH) and 0.97 Å (CH2) from the parent C atoms and refined as riding with Uiso(H) = 1.2Ueq(C).

50 reflections were not included in the data set as they were either partially obscured by the beam stop or were eliminated during data reduction. The material was difficult to obtain in a suitable crystalline form.

Figures

Fig. 1.
A view of the molecular structure with the atom-numbering scheme. Displacemenent ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Intramolecular hydrogen bonds are indicated by dotted lines. ...

Crystal data

C14H12N2O4F(000) = 284
Mr = 272.26Dx = 1.406 Mg m3
Orthorhombic, P21212Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 1704 reflections
a = 4.0740 (14) Åθ = 1.9–27.5°
b = 21.3404 (7) ŵ = 0.11 mm1
c = 7.395 (6) ÅT = 293 K
V = 642.9 (6) Å3Prismatic, colourless
Z = 20.19 × 0.10 × 0.08 mm

Data collection

Nonius KappaCCD area-detector diffractometer694 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
graphiteθmax = 27.6°, θmin = 1.9°
[var phi] scans, and ω scans with κ offsetsh = −5→0
2298 measured reflectionsk = −27→27
874 independent reflectionsl = −9→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.27w = 1/[σ2(Fo2) + (0.0408P)2 + 0.2469P] where P = (Fo2 + 2Fc2)/3
874 reflections(Δ/σ)max = 0.002
91 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)

xyzUiso*/Ueq
O1−0.1685 (7)0.44509 (9)−0.0673 (3)0.0399 (6)
O2−0.1110 (9)0.34487 (11)−0.1477 (3)0.0619 (9)
N1−0.5385 (10)0.40255 (14)0.4274 (4)0.0574 (10)
C1−0.3638 (9)0.36912 (14)0.1334 (4)0.0330 (8)
C2−0.3991 (10)0.41380 (16)0.2682 (5)0.0458 (10)
H2−0.32070.4540.24580.055*
C3−0.6491 (10)0.34439 (17)0.4541 (5)0.0497 (10)
H3−0.74970.33550.5640.06*
C4−0.6241 (11)0.29697 (17)0.3305 (4)0.0462 (10)
H4−0.70580.25730.35620.055*
C5−0.4756 (10)0.30923 (15)0.1671 (4)0.0416 (9)
H5−0.4510.27780.08120.05*
C6−0.2039 (9)0.38335 (15)−0.0413 (4)0.0365 (8)
C70.0000 (10)0.46502 (15)−0.2299 (4)0.0408 (9)
H7A−0.11240.4492−0.33620.049*
H7B0.22330.4493−0.23060.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0527 (15)0.0300 (12)0.0371 (11)−0.0025 (11)0.0110 (13)−0.0014 (10)
O20.102 (2)0.0365 (13)0.0474 (13)0.0018 (16)0.0250 (17)−0.0097 (12)
N10.077 (2)0.051 (2)0.0441 (16)−0.0096 (19)0.015 (2)−0.0089 (15)
C10.038 (2)0.0291 (15)0.0321 (15)0.0021 (15)−0.0016 (16)−0.0008 (12)
C20.058 (3)0.0334 (18)0.0457 (19)−0.0051 (19)0.008 (2)−0.0066 (15)
C30.057 (3)0.054 (2)0.0380 (18)−0.009 (2)0.008 (2)0.0021 (17)
C40.055 (3)0.0358 (18)0.0478 (19)−0.0023 (18)0.003 (2)0.0044 (15)
C50.049 (2)0.0331 (17)0.0423 (17)−0.0009 (18)0.0011 (19)−0.0043 (15)
C60.042 (2)0.0318 (17)0.0360 (16)0.0001 (16)−0.0020 (17)−0.0014 (14)
C70.047 (2)0.0460 (18)0.0294 (15)−0.0102 (19)0.0023 (18)−0.0013 (14)

Geometric parameters (Å, °)

O1—C61.339 (4)C3—C41.368 (5)
O1—C71.449 (4)C3—H30.93
O2—C61.198 (4)C4—C51.376 (5)
N1—C21.330 (5)C4—H40.93
N1—C31.335 (5)C5—H50.93
C1—C51.380 (4)C7—C7i1.493 (7)
C1—C21.387 (4)C7—H7A0.97
C1—C61.478 (4)C7—H7B0.97
C2—H20.93
C6—O1—C7117.3 (2)C5—C4—H4120.7
C2—N1—C3116.3 (3)C4—C5—C1118.7 (3)
C5—C1—C2118.2 (3)C4—C5—H5120.6
C5—C1—C6119.6 (3)C1—C5—H5120.6
C2—C1—C6122.2 (3)O2—C6—O1123.1 (3)
N1—C2—C1123.8 (3)O2—C6—C1124.9 (3)
N1—C2—H2118.1O1—C6—C1112.0 (3)
C1—C2—H2118.1O1—C7—C7i107.1 (3)
N1—C3—C4124.3 (3)O1—C7—H7A110.3
N1—C3—H3117.8C7i—C7—H7A110.3
C4—C3—H3117.8O1—C7—H7B110.3
C3—C4—C5118.6 (3)C7i—C7—H7B110.3
C3—C4—H4120.7H7A—C7—H7B108.6
C3—N1—C2—C1−0.2 (6)C7—O1—C6—O2−2.0 (5)
C5—C1—C2—N1−0.9 (6)C7—O1—C6—C1177.0 (3)
C6—C1—C2—N1−179.3 (4)C5—C1—C6—O2−13.3 (6)
C2—N1—C3—C40.7 (6)C2—C1—C6—O2165.1 (4)
N1—C3—C4—C50.1 (7)C5—C1—C6—O1167.8 (3)
C3—C4—C5—C1−1.3 (6)C2—C1—C6—O1−13.9 (5)
C2—C1—C5—C41.7 (6)C6—O1—C7—C7i178.5 (4)
C6—C1—C5—C4−179.9 (4)

Symmetry codes: (i) −x, −y+1, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···O10.932.402.735 (5)101

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2303).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography