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

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

Experimental

Crystal data

• C₁₄H₁₂N₂O₄

• M_r = 272.26

• Orthorhombic, P 2₁ 2₁ 2

• a = 4.0740 (14) Å

• b = 21.3404 (7) Å

• c = 7.395 (6) Å

• V = 642.9 (6) ų

• 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[F² > 2σ(F²)] = 0.049

• wR(F²) = 0.131

• S = 1.27

• 874 reflections

• 91 parameters

• H-atom parameters constrained

• Δρ_max = 0.16 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1	0.93	2.40	2.735 (5)	101

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

Supporting information

S1. 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.

Related literature

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

S2. 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.

S3. 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 U_iso(H) = 1.2U_eq(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.

Computing details

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

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. Unlabeled atoms are related to labeled atoms by the symmetry code (-x, 1 - y, z).

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

Crystal data

C14H12N2O4	F(000) = 284
Mr = 272.26	Dx = 1.406 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 1704 reflections
a = 4.0740 (14) Å	θ = 1.9–27.5°
b = 21.3404 (7) Å	µ = 0.11 mm^−1
c = 7.395 (6) Å	T = 293 K
V = 642.9 (6) Å^3	Prismatic, colourless
Z = 2	0.19 × 0.10 × 0.08 mm

Data collection

Nonius KappaCCD area-detector diffractometer	694 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 27.6°, θmin = 1.9°
ϕ scans, and ω scans with κ offsets	h = −5→0
2298 measured reflections	k = −27→27
874 independent reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.27	w = 1/[σ^2(Fo^2) + (0.0408P)^2 + 0.2469P] where P = (Fo^2 + 2Fc^2)/3
874 reflections	(Δ/σ)max = 0.002
91 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

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 (Ų)

	x	y	z	Uiso*/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	−0.3207	0.454	0.2458	0.055*
C3	−0.6491 (10)	0.34439 (17)	0.4541 (5)	0.0497 (10)
H3	−0.7497	0.3355	0.564	0.06*
C4	−0.6241 (11)	0.29697 (17)	0.3305 (4)	0.0462 (10)
H4	−0.7058	0.2573	0.3562	0.055*
C5	−0.4756 (10)	0.30923 (15)	0.1671 (4)	0.0416 (9)
H5	−0.451	0.2778	0.0812	0.05*
C6	−0.2039 (9)	0.38335 (15)	−0.0413 (4)	0.0365 (8)
C7	0.0000 (10)	0.46502 (15)	−0.2299 (4)	0.0408 (9)
H7A	−0.1124	0.4492	−0.3362	0.049*
H7B	0.2233	0.4493	−0.2306	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0527 (15)	0.0300 (12)	0.0371 (11)	−0.0025 (11)	0.0110 (13)	−0.0014 (10)
O2	0.102 (2)	0.0365 (13)	0.0474 (13)	0.0018 (16)	0.0250 (17)	−0.0097 (12)
N1	0.077 (2)	0.051 (2)	0.0441 (16)	−0.0096 (19)	0.015 (2)	−0.0089 (15)
C1	0.038 (2)	0.0291 (15)	0.0321 (15)	0.0021 (15)	−0.0016 (16)	−0.0008 (12)
C2	0.058 (3)	0.0334 (18)	0.0457 (19)	−0.0051 (19)	0.008 (2)	−0.0066 (15)
C3	0.057 (3)	0.054 (2)	0.0380 (18)	−0.009 (2)	0.008 (2)	0.0021 (17)
C4	0.055 (3)	0.0358 (18)	0.0478 (19)	−0.0023 (18)	0.003 (2)	0.0044 (15)
C5	0.049 (2)	0.0331 (17)	0.0423 (17)	−0.0009 (18)	0.0011 (19)	−0.0043 (15)
C6	0.042 (2)	0.0318 (17)	0.0360 (16)	0.0001 (16)	−0.0020 (17)	−0.0014 (14)
C7	0.047 (2)	0.0460 (18)	0.0294 (15)	−0.0102 (19)	0.0023 (18)	−0.0013 (14)

Geometric parameters (Å, º)

O1—C6	1.339 (4)	C3—C4	1.368 (5)
O1—C7	1.449 (4)	C3—H3	0.93
O2—C6	1.198 (4)	C4—C5	1.376 (5)
N1—C2	1.330 (5)	C4—H4	0.93
N1—C3	1.335 (5)	C5—H5	0.93
C1—C5	1.380 (4)	C7—C7^i	1.493 (7)
C1—C2	1.387 (4)	C7—H7A	0.97
C1—C6	1.478 (4)	C7—H7B	0.97
C2—H2	0.93
C6—O1—C7	117.3 (2)	C5—C4—H4	120.7
C2—N1—C3	116.3 (3)	C4—C5—C1	118.7 (3)
C5—C1—C2	118.2 (3)	C4—C5—H5	120.6
C5—C1—C6	119.6 (3)	C1—C5—H5	120.6
C2—C1—C6	122.2 (3)	O2—C6—O1	123.1 (3)
N1—C2—C1	123.8 (3)	O2—C6—C1	124.9 (3)
N1—C2—H2	118.1	O1—C6—C1	112.0 (3)
C1—C2—H2	118.1	O1—C7—C7^i	107.1 (3)
N1—C3—C4	124.3 (3)	O1—C7—H7A	110.3
N1—C3—H3	117.8	C7^i—C7—H7A	110.3
C4—C3—H3	117.8	O1—C7—H7B	110.3
C3—C4—C5	118.6 (3)	C7^i—C7—H7B	110.3
C3—C4—H4	120.7	H7A—C7—H7B	108.6
C3—N1—C2—C1	−0.2 (6)	C7—O1—C6—O2	−2.0 (5)
C5—C1—C2—N1	−0.9 (6)	C7—O1—C6—C1	177.0 (3)
C6—C1—C2—N1	−179.3 (4)	C5—C1—C6—O2	−13.3 (6)
C2—N1—C3—C4	0.7 (6)	C2—C1—C6—O2	165.1 (4)
N1—C3—C4—C5	0.1 (7)	C5—C1—C6—O1	167.8 (3)
C3—C4—C5—C1	−1.3 (6)	C2—C1—C6—O1	−13.9 (5)
C2—C1—C5—C4	1.7 (6)	C6—O1—C7—C7^i	178.5 (4)
C6—C1—C5—C4	−179.9 (4)

Symmetry code: (i) −x, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1	0.93	2.40	2.735 (5)	101