supplementary materials
Propane-1,3-diyl bis(pyridine-4-carboxylate)
The title compound. C15H14N2O4, (I), has a gauche-gauche (O/C/C/C-O/C/C/C or GG) conformation and is a positional isomer of propane-1,3-diyl bis(pyridine-3-carboxylate), (II). The molecule of (I) lies on a twofold rotation axis, which passes through the central C atom of the aliphatic chain, giving one half-molecule per asymmetric unit. There is excellent agreement of the geometric parameters of (I) and (II). The most obvious differences between them are the O/C/C/C-O/C/C/C torsion angles [56.6 (2)° in (I) and 174.0 (3)/70.2 (3)° in (II) for GG and TG conformations, respectively] and the dihedral angle between the planes of the aromatic rings [80.3 (10)° in (I) and 76.5 (3)° in (II)]. The crystal structure is stabilized by weak C-H
N and C-H O hydrogen bonding.
Isonicotinic 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 1,3-Propanediol (4.9 ml, 0.061 mol) was added. After
the evolution of hydrogen chloride ended, the mixture was heated at 110°C for
2 h. The mixture was then dissolved in water, and NH4OH was added. After
filtration, recrystallization in ethyl acetate gave colorless crystals
suitable for X-ray analysis. Yield 8.23 g(24%). Analysis calculated for
C15H14N2O4:C: 62.9, H: 4.89, N: 9.68; found: C: 62.45, H: 4.85,
N: 9.85. IR (KBr, cm-1):(C=O) 1727 s, (C=C) 1596 s, (Ar C—C, C=N) 1408 s,
(C—O) 1278 m.
H atoms were placed in idealized positions and treated as riding atoms with
C—H distances in the range 0.95-0.99 Å and Uiso(H) = 1.2Ueq(C).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Propane-1,3-diyl bis(pyridine-4-carboxylate)
top
Crystal data top
| C15H14N2O4 | F(000) = 600 |
| Mr = 286.28 | Dx = 1.414 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2383 reflections |
| a = 23.022 (4) Å | θ = 3.5–25.9° |
| b = 4.9336 (5) Å | µ = 0.10 mm−1 |
| c = 11.9604 (18) Å | T = 173 K |
| β = 98.118 (13)° | Plate, colourless |
| V = 1344.9 (3) Å3 | 0.18 × 0.15 × 0.09 mm |
| Z = 4 | |
Data collection top
Stoe IPDS II two-circle
diffractometer | 799 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.070 |
| graphite | θmax = 25.6°, θmin = 3.4° |
| ω scans | h = −22→28 |
| 4231 measured reflections | k = −5→5 |
| 1251 independent reflections | l = −14→14 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.094 | H-atom parameters constrained |
| S = 0.87 | w = 1/[σ2(Fo2) + (0.0427P)2]
where P = (Fo2 + 2Fc2)/3 |
| 1251 reflections | (Δ/σ)max < 0.001 |
| 96 parameters | Δρmax = 0.16 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
| C15H14N2O4 | V = 1344.9 (3) Å3 |
| Mr = 286.28 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 23.022 (4) Å | µ = 0.10 mm−1 |
| b = 4.9336 (5) Å | T = 173 K |
| c = 11.9604 (18) Å | 0.18 × 0.15 × 0.09 mm |
| β = 98.118 (13)° | |
Data collection top
Stoe IPDS II two-circle
diffractometer | 799 reflections with I > 2σ(I) |
| 4231 measured reflections | Rint = 0.070 |
| 1251 independent reflections | θmax = 25.6° |
Refinement top
| R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
| wR(F2) = 0.094 | Δρmax = 0.16 e Å−3 |
| S = 0.87 | Δρmin = −0.21 e Å−3 |
| 1251 reflections | Absolute structure: ? |
| 96 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell esds are taken into
account individually in the estimation of esds in distances, angles and
torsion angles; correlations between esds in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | Uiso*/Ueq | |
| O1 | 0.43077 (7) | 0.6064 (3) | 0.47123 (12) | 0.0356 (4) | |
| C1 | 0.41465 (9) | 0.5769 (4) | 0.56249 (16) | 0.0270 (5) | |
| O2 | 0.43693 (6) | 0.7138 (3) | 0.65570 (11) | 0.0300 (4) | |
| C3 | 0.48573 (9) | 0.8943 (4) | 0.64276 (16) | 0.0287 (5) | |
| H3A | 0.4748 | 1.0166 | 0.5775 | 0.034* | |
| H3B | 0.5204 | 0.7871 | 0.6291 | 0.034* | |
| C4 | 0.5000 | 1.0584 (6) | 0.7500 | 0.0292 (7) | |
| H4 | 0.4661 | 1.1769 | 0.7579 | 0.035* | |
| C11 | 0.36822 (9) | 0.3801 (4) | 0.58462 (16) | 0.0276 (5) | |
| C12 | 0.34752 (9) | 0.1948 (4) | 0.50109 (17) | 0.0299 (5) | |
| H12 | 0.3621 | 0.1949 | 0.4307 | 0.036* | |
| C13 | 0.30531 (10) | 0.0107 (4) | 0.52223 (17) | 0.0323 (5) | |
| H13 | 0.2921 | −0.1177 | 0.4651 | 0.039* | |
| N14 | 0.28183 (8) | 0.0018 (4) | 0.61815 (14) | 0.0337 (5) | |
| C15 | 0.30185 (10) | 0.1843 (5) | 0.69753 (18) | 0.0360 (5) | |
| H15 | 0.2857 | 0.1832 | 0.7663 | 0.043* | |
| C16 | 0.34464 (10) | 0.3735 (4) | 0.68496 (17) | 0.0326 (5) | |
| H16 | 0.3577 | 0.4971 | 0.7441 | 0.039* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| O1 | 0.0412 (9) | 0.0404 (9) | 0.0264 (7) | −0.0035 (8) | 0.0090 (6) | −0.0045 (7) |
| C1 | 0.0279 (11) | 0.0268 (11) | 0.0257 (10) | 0.0040 (9) | 0.0018 (8) | −0.0001 (8) |
| O2 | 0.0321 (8) | 0.0326 (8) | 0.0247 (7) | −0.0054 (7) | 0.0021 (6) | −0.0008 (6) |
| C3 | 0.0268 (11) | 0.0321 (11) | 0.0274 (10) | −0.0021 (9) | 0.0045 (8) | 0.0024 (9) |
| C4 | 0.0307 (16) | 0.0280 (16) | 0.0286 (14) | 0.000 | 0.0034 (12) | 0.000 |
| C11 | 0.0281 (11) | 0.0283 (11) | 0.0256 (9) | 0.0053 (9) | 0.0010 (8) | 0.0019 (8) |
| C12 | 0.0352 (12) | 0.0314 (11) | 0.0227 (9) | 0.0009 (10) | 0.0033 (8) | 0.0007 (8) |
| C13 | 0.0338 (12) | 0.0309 (11) | 0.0308 (10) | −0.0012 (10) | −0.0001 (9) | −0.0029 (9) |
| N14 | 0.0343 (11) | 0.0326 (10) | 0.0338 (10) | −0.0010 (9) | 0.0029 (8) | 0.0013 (8) |
| C15 | 0.0396 (13) | 0.0401 (13) | 0.0294 (11) | −0.0008 (11) | 0.0085 (9) | −0.0004 (10) |
| C16 | 0.0364 (13) | 0.0333 (12) | 0.0280 (10) | −0.0018 (10) | 0.0042 (9) | −0.0050 (9) |
Geometric parameters (Å, °) top
| O1—C1 | 1.210 (2) | C11—C12 | 1.388 (3) |
| C1—O2 | 1.342 (2) | C12—C13 | 1.379 (3) |
| C1—C11 | 1.495 (3) | C12—H12 | 0.9500 |
| O2—C3 | 1.459 (2) | C13—N14 | 1.336 (3) |
| C3—C4 | 1.513 (2) | C13—H13 | 0.9500 |
| C3—H3A | 0.9900 | N14—C15 | 1.342 (3) |
| C3—H3B | 0.9900 | C15—C16 | 1.381 (3) |
| C4—C3i | 1.513 (2) | C15—H15 | 0.9500 |
| C4—H4 | 0.9900 | C16—H16 | 0.9500 |
| C11—C16 | 1.386 (3) | | |
| | | |
| O1—C1—O2 | 124.0 (2) | C12—C11—C1 | 118.80 (18) |
| O1—C1—C11 | 123.76 (18) | C13—C12—C11 | 118.75 (19) |
| O2—C1—C11 | 112.26 (17) | C13—C12—H12 | 120.6 |
| C1—O2—C3 | 115.39 (15) | C11—C12—H12 | 120.6 |
| O2—C3—C4 | 108.35 (15) | N14—C13—C12 | 124.04 (19) |
| O2—C3—H3A | 110.0 | N14—C13—H13 | 118.0 |
| C4—C3—H3A | 110.0 | C12—C13—H13 | 118.0 |
| O2—C3—H3B | 110.0 | C13—N14—C15 | 116.44 (19) |
| C4—C3—H3B | 110.0 | N14—C15—C16 | 123.7 (2) |
| H3A—C3—H3B | 108.4 | N14—C15—H15 | 118.1 |
| C3i—C4—C3 | 115.3 (2) | C16—C15—H15 | 118.1 |
| C3i—C4—H4 | 108.3 | C15—C16—C11 | 118.88 (19) |
| C3—C4—H4 | 108.5 | C15—C16—H16 | 120.6 |
| C16—C11—C12 | 118.1 (2) | C11—C16—H16 | 120.6 |
| C16—C11—C1 | 123.08 (18) | | |
| | | |
| O1—C1—O2—C3 | −3.7 (3) | C16—C11—C12—C13 | −1.0 (3) |
| C11—C1—O2—C3 | 175.34 (17) | C1—C11—C12—C13 | 179.05 (19) |
| C1—O2—C3—C4 | 172.61 (16) | C11—C12—C13—N14 | 1.4 (3) |
| O2—C3—C4—C3i | 56.56 (11) | C12—C13—N14—C15 | −0.7 (3) |
| O1—C1—C11—C16 | −171.1 (2) | C13—N14—C15—C16 | −0.5 (3) |
| O2—C1—C11—C16 | 9.9 (3) | N14—C15—C16—C11 | 0.8 (3) |
| O1—C1—C11—C12 | 8.9 (3) | C12—C11—C16—C15 | 0.0 (3) |
| O2—C1—C11—C12 | −170.21 (18) | C1—C11—C16—C15 | 179.9 (2) |
| Symmetry codes: (i) −x+1, y, −z+3/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C13—H13···N14ii | 0.95 | 2.65 | 3.505 (3) | 151 |
| C15—H15···N14iii | 0.95 | 2.72 | 3.496 (3) | 139 |
| C3—H3A···O1iv | 0.99 | 2.98 | 3.516 (3) | 115 |
| C3—H3B···O1v | 0.99 | 2.62 | 3.521 (3) | 152 |
| Symmetry codes: (ii) −x+1/2, −y−1/2, −z+1; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C13—H13···N14i | 0.95 | 2.65 | 3.505 (3) | 151 |
| C15—H15···N14ii | 0.95 | 2.72 | 3.496 (3) | 139 |
| C3—H3A···O1iii | 0.99 | 2.98 | 3.516 (3) | 115 |
| C3—H3B···O1iv | 0.99 | 2.62 | 3.521 (3) | 152 |
| Symmetry codes: (i) −x+1/2, −y−1/2, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1, −y+2, −z+1; (iv) −x+1, −y+1, −z+1. |
We thank the Spanish Research Council (CSIC) for providing us with a
free-of-charge licence for the CSD system. JV thanks the Universidad de
Antofagasta for PhD fellowships.
Brito, I., Vallejos, J., Bolte, M. & López-Rodríguez, M. (2010). Acta Cryst. E66, o792.
Carlucci, L., Ciani, G., Proserpio, D. M. & Rizzato, S. (2002). CrystEngComm, 22, 121–129.
Chatterjee, B., Noveron, J. C., Resendiz, M., Liu, J., Yamamoto, T., Parker, D., Cinke, M., Nguyen, C., Arif, A. & Stang, P. (2004). J. Am. Chem. Soc. 126, 10645–10656.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.
![[Figure 1]](./fl2297fig1thm.gif)
![[Figure 2]](./fl2297fig2thm.gif)
![[Figure 3]](./fl2297fig3thm.gif)
The propanediyl group can adopt four possible conformations: trans-trans (TT), trans-gauche (TG), gauche-gauche (GG), and gauche-gauche' (GG') (Carlucci et al., 2002). The title compound C15H14N2O4, (I) has a gauche-gauche (GG) conformation and is a positional isomer of the previously reported propane-1,3-diyl bis(pyridine-3-carboxylate), (II), (Brito et al., 2010). Similar compounds have also been reported by Chatterjee et al. (2004).
The molecules of the title compound lie on a twofold rotation axis passing through the central carbon atom of the aliphatic chain such that one half of the title compound forms the asymmetric unit (Fig. 1). Both compounds shows excellent agreement of their geometric parameters. The most obvious differences between them are in the torsion angles O/C/C/C—O/C/C/C[56.6 (2)° in (I) and 174.0 (3);70.2 (3)° in (II), GG and TG conformation, respectively] and the angle between the planes of aromatics rings [80.3 (10)° (I) and 76.5 (3)° (II)]. The crystal structure is stabilized by weak C—H··· N and C—H··· O hydrogen bonding (Table 1, Fig. 2). The title compound can be used as a nucleophilic tecton in self-assembly reactions with metal centres of varying lability.