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Propane-1,3-diyl bis­­(pyridine-3-carboxyl­ate)

aDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, bInstitut für Anorganische Chemie der Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany, and cInstituto de Bio-Orgánica 'Antonio González', Universidad de La Laguna, Astrofísico Francisco Sánchez N°2, La Laguna, Tenerife, Spain
*Correspondence e-mail: ivanbritob@yahoo.com

(Received 2 March 2010; accepted 8 March 2010; online 13 March 2010)

The title compound, C15H14N2O4, has a trans–gauche [O/C/C/C–O/C/C/C] (TG) conformation. The angle between the planes of aromatic rings is 76.4 (3)°. The crystal structure is stabilized by van der Waals inter­actions and C—H⋯O hydrogen bonds. The crystal used was a non-merohedral twin with a fractional contribution of the minor component of 0.443 (5).

Related literature

For conformation definitions, see: Carlucci et al. (2002[Carlucci, L., Ciani, G., Proserpio, D. M. & Rizzato, S. (2002). CrystEngComm, 22, 121-129.]). For applications of crystalline nanoporous coordination polymers, see Matsuda et al. (2005[Matsuda, R., Kitaura, R., Kitagawa, S., Kubota, Y., Belosludov, R. V., Kobayashi, T. C., Sakamoto, H., Chiba, T., Takata, M., Kawazoe, Y. & Mita, Y. (2005). Nature (London), 436, 238-241.]); Wu et al. (2005[Wu, C. D., Hu, A., Zhang, L. & Lin, W. (2005). J. Am. Chem. Soc. 127, 8940-8941.]); Xiang et al. (2005[Xiang, S., Wu, X., Zhang, J., Fu, R., Hu, S. & Zhang, X. (2005). J. Am. Chem. Soc. 127, 16352-16353.]).

[Scheme 1]

Experimental

Crystal data
  • C15H14N2O4

  • Mr = 286.28

  • Triclinic, [P \overline 1]

  • a = 4.4797 (11) Å

  • b = 10.911 (3) Å

  • c = 14.842 (4) Å

  • α = 104.41 (2)°

  • β = 95.90 (2)°

  • γ = 100.90 (2)°

  • V = 681.3 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 173 K

  • 0.22 × 0.14 × 0.07 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • 8629 measured reflections

  • 2558 independent reflections

  • 1382 reflections with I > 2σ(I)

  • Rint = 0.119

Refinement
  • R[F2 > 2σ(F2)] = 0.109

  • wR(F2) = 0.276

  • S = 1.49

  • 2558 reflections

  • 191 parameters

  • H-atom parameters constrained

  • Δρmax = 0.43 e Å−3

  • Δρmin = −0.46 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3A⋯O4i 0.99 2.49 3.341 (8) 144
C16—H16⋯O2ii 0.95 2.45 3.198 (10) 136
C24—H24⋯O2iii 0.95 2.45 3.218 (10) 138
Symmetry codes: (i) -x+3, -y+1, -z+1; (ii) -x+1, -y, -z; (iii) -x+1, -y, -z+1.

Data collection: X-AREA (Stoe & Cie, 2001[Stoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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). The propanediyl group in the crystal structure can adopt four possible conformations: trans-trans (TT), trans-gauche (TG), gauche-gauche (GG), gauche-gauche' (GG') (Carlucci et al., 2002). The propanediyl group in the title compound has a trans-gauche (TG) [O1/C2/C3/C4 - O3/C4/C3/C2] conformation (Fig. 1). The angle between the planes of aromatics rings is 76.4 (3)°. The crystal structure is stabilized by van der Waals interactions and C—H···O hydrogen bonds (Table 1). To the best of our knowledge coordination polymer with this ligand still remain unknown.

Related literature top

For conformation definitions, see: Carlucci et al. (2002). For applications of crystalline nanoporous coordination polymers, see Matsuda et al. (2005); Wu et al. (2005); Xiang et al. (2005).

Experimental top

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 propanediol (4.3 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 crystal. Yield 11.53 g (80 %). Analysis calculated for C15H14N2O4: C:62.9 , H:4.89 , N:9.68 ; found: C: 62.25, H: 4.68, N:9.52 . IR (KBr, cm-1): (CO) 1715 s, (CC) 1591 m, (Ar C—C, CN) 1429 s,(C—O) 1277 m.

Refinement top

The crystal turned out to be a non-merohedral twin (twin law: -1 0 0/0 -0.476 -0.740/ 0 -1 0.478) with a fractional contribution of the minor component of 0.443 (5). 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). The material was difficult to obtain in a suitable crystalline form.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure with the atom-numbering scheme. Displacemenent ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
Propane-1,3-diyl bis(pyridine-3-carboxylate) top
Crystal data top
C15H14N2O4Z = 2
Mr = 286.28F(000) = 300
Triclinic, P1Dx = 1.395 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.4797 (11) ÅCell parameters from 3924 reflections
b = 10.911 (3) Åθ = 3.9–25.8°
c = 14.842 (4) ŵ = 0.10 mm1
α = 104.41 (2)°T = 173 K
β = 95.90 (2)°Plate, colourless
γ = 100.90 (2)°0.22 × 0.14 × 0.07 mm
V = 681.3 (3) Å3
Data collection top
Stoe IPDS II two-circle
diffractometer
1382 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.119
Graphite monochromatorθmax = 26.0°, θmin = 3.8°
ω scansh = 55
8629 measured reflectionsk = 1312
2558 independent reflectionsl = 1217
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.109Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.276H-atom parameters constrained
S = 1.49 w = 1/[σ2(Fo2) + (0.090P)2]
where P = (Fo2 + 2Fc2)/3
2558 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
C15H14N2O4γ = 100.90 (2)°
Mr = 286.28V = 681.3 (3) Å3
Triclinic, P1Z = 2
a = 4.4797 (11) ÅMo Kα radiation
b = 10.911 (3) ŵ = 0.10 mm1
c = 14.842 (4) ÅT = 173 K
α = 104.41 (2)°0.22 × 0.14 × 0.07 mm
β = 95.90 (2)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1382 reflections with I > 2σ(I)
8629 measured reflectionsRint = 0.119
2558 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.1090 restraints
wR(F2) = 0.276H-atom parameters constrained
S = 1.49Δρmax = 0.43 e Å3
2558 reflectionsΔρmin = 0.46 e Å3
191 parameters
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
xyzUiso*/Ueq
O10.8187 (10)0.2723 (4)0.2445 (4)0.0458 (12)
O20.6697 (13)0.0749 (5)0.1430 (4)0.0637 (16)
O31.1653 (9)0.2272 (4)0.5109 (3)0.0405 (11)
O41.2061 (11)0.4252 (4)0.6081 (4)0.0540 (14)
C10.6560 (14)0.1865 (6)0.1644 (5)0.0434 (17)
C21.0002 (15)0.2161 (6)0.3054 (5)0.0434 (16)
H2A1.12960.16480.26880.052*
H2B0.86290.15870.33340.052*
C31.2023 (14)0.3317 (6)0.3827 (5)0.0448 (17)
H3A1.35150.38380.35430.054*
H3B1.07180.38810.41350.054*
C41.3748 (14)0.2826 (7)0.4557 (5)0.0445 (17)
H4A1.47950.21600.42340.053*
H4B1.53390.35540.49810.053*
C51.0994 (13)0.3111 (6)0.5848 (5)0.0439 (17)
C110.4701 (14)0.2473 (6)0.1081 (5)0.0420 (16)
C120.4516 (15)0.3777 (6)0.1359 (5)0.0451 (17)
H120.56460.43080.19480.054*
N130.2835 (15)0.4308 (6)0.0838 (5)0.0568 (17)
C140.1172 (16)0.3544 (7)0.0009 (6)0.0538 (19)
H140.00700.39040.03670.065*
C150.1253 (17)0.2229 (7)0.0306 (6)0.055 (2)
H150.01210.17120.08990.066*
C160.2940 (17)0.1699 (7)0.0235 (6)0.0516 (19)
H160.29230.08000.00370.062*
C210.8829 (13)0.2446 (6)0.6378 (5)0.0386 (15)
C220.7613 (14)0.1126 (6)0.6107 (6)0.0472 (18)
H220.81920.06260.55600.057*
N230.5693 (13)0.0501 (6)0.6553 (4)0.0505 (16)
C240.4879 (17)0.1254 (7)0.7329 (6)0.0526 (19)
H240.34860.08430.76610.063*
C250.5981 (16)0.2594 (6)0.7660 (5)0.0470 (17)
H250.53690.30860.82050.056*
C260.7973 (14)0.3177 (6)0.7173 (5)0.0446 (17)
H260.87720.40890.73810.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.045 (2)0.027 (2)0.054 (3)0.0010 (19)0.005 (2)0.001 (2)
O20.095 (4)0.041 (3)0.047 (3)0.020 (3)0.005 (3)0.001 (2)
O30.036 (2)0.035 (2)0.043 (3)0.0023 (18)0.005 (2)0.004 (2)
O40.051 (3)0.032 (3)0.066 (4)0.004 (2)0.006 (2)0.003 (2)
C10.043 (3)0.033 (4)0.048 (5)0.002 (3)0.003 (3)0.008 (3)
C20.044 (3)0.033 (3)0.053 (4)0.006 (3)0.006 (3)0.014 (3)
C30.037 (3)0.031 (3)0.056 (4)0.008 (3)0.001 (3)0.009 (3)
C40.041 (3)0.040 (4)0.054 (5)0.002 (3)0.015 (3)0.020 (3)
C50.034 (3)0.027 (3)0.062 (5)0.002 (3)0.001 (3)0.002 (3)
C110.046 (3)0.025 (3)0.046 (4)0.004 (3)0.005 (3)0.002 (3)
C120.053 (4)0.027 (3)0.048 (5)0.007 (3)0.003 (3)0.001 (3)
N130.072 (4)0.039 (3)0.051 (4)0.013 (3)0.006 (3)0.003 (3)
C140.057 (4)0.041 (4)0.057 (5)0.012 (3)0.009 (4)0.008 (4)
C150.059 (4)0.043 (4)0.049 (5)0.008 (3)0.007 (4)0.010 (3)
C160.066 (4)0.030 (3)0.051 (5)0.006 (3)0.009 (4)0.001 (3)
C210.031 (3)0.029 (3)0.044 (4)0.001 (2)0.007 (3)0.002 (3)
C220.045 (3)0.024 (3)0.063 (5)0.001 (3)0.003 (3)0.003 (3)
N230.054 (3)0.041 (3)0.048 (4)0.002 (3)0.004 (3)0.008 (3)
C240.058 (4)0.040 (4)0.055 (5)0.004 (3)0.011 (4)0.010 (4)
C250.050 (4)0.034 (3)0.047 (4)0.006 (3)0.002 (3)0.002 (3)
C260.042 (3)0.028 (3)0.051 (5)0.004 (3)0.000 (3)0.008 (3)
Geometric parameters (Å, º) top
O1—C11.353 (8)C12—N131.329 (10)
O1—C21.472 (8)C12—H120.9500
O2—C11.194 (8)N13—C141.353 (10)
O3—C51.340 (8)C14—C151.402 (10)
O3—C41.452 (7)C14—H140.9500
O4—C51.193 (8)C15—C161.349 (12)
C1—C111.475 (10)C15—H150.9500
C2—C31.537 (9)C16—H160.9500
C2—H2A0.9900C21—C221.379 (8)
C2—H2B0.9900C21—C261.384 (9)
C3—C41.528 (10)C22—N231.328 (9)
C3—H3A0.9900C22—H220.9500
C3—H3B0.9900N23—C241.364 (10)
C4—H4A0.9900C24—C251.393 (9)
C4—H4B0.9900C24—H240.9500
C5—C211.504 (10)C25—C261.368 (10)
C11—C161.389 (10)C25—H250.9500
C11—C121.400 (8)C26—H260.9500
C1—O1—C2114.8 (5)N13—C12—C11123.2 (7)
C5—O3—C4116.2 (5)N13—C12—H12118.4
O2—C1—O1122.4 (6)C11—C12—H12118.4
O2—C1—C11125.2 (6)C12—N13—C14118.4 (7)
O1—C1—C11112.4 (6)N13—C14—C15121.1 (7)
O1—C2—C3105.9 (5)N13—C14—H14119.5
O1—C2—H2A110.6C15—C14—H14119.5
C3—C2—H2A110.6C16—C15—C14119.9 (7)
O1—C2—H2B110.6C16—C15—H15120.0
C3—C2—H2B110.6C14—C15—H15120.0
H2A—C2—H2B108.7C15—C16—C11119.8 (7)
C4—C3—C2109.8 (6)C15—C16—H16120.1
C4—C3—H3A109.7C11—C16—H16120.1
C2—C3—H3A109.7C22—C21—C26117.6 (7)
C4—C3—H3B109.7C22—C21—C5123.1 (6)
C2—C3—H3B109.7C26—C21—C5119.3 (6)
H3A—C3—H3B108.2N23—C22—C21125.0 (7)
O3—C4—C3111.0 (5)N23—C22—H22117.5
O3—C4—H4A109.4C21—C22—H22117.5
C3—C4—H4A109.4C22—N23—C24115.8 (6)
O3—C4—H4B109.4N23—C24—C25123.6 (7)
C3—C4—H4B109.4N23—C24—H24118.2
H4A—C4—H4B108.0C25—C24—H24118.2
O4—C5—O3124.4 (6)C26—C25—C24117.7 (7)
O4—C5—C21123.4 (7)C26—C25—H25121.2
O3—C5—C21112.2 (5)C24—C25—H25121.2
C16—C11—C12117.6 (7)C25—C26—C21120.3 (6)
C16—C11—C1118.2 (6)C25—C26—H26119.8
C12—C11—C1124.1 (6)C21—C26—H26119.8
C2—O1—C1—O23.1 (9)N13—C14—C15—C161.9 (12)
C2—O1—C1—C11177.9 (5)C14—C15—C16—C112.9 (11)
C1—O1—C2—C3171.4 (5)C12—C11—C16—C153.2 (10)
O1—C2—C3—C4173.9 (5)C1—C11—C16—C15178.9 (7)
C5—O3—C4—C384.3 (7)O4—C5—C21—C22179.8 (7)
C2—C3—C4—O370.1 (7)O3—C5—C21—C221.8 (9)
C4—O3—C5—O41.7 (10)O4—C5—C21—C260.8 (10)
C4—O3—C5—C21179.6 (6)O3—C5—C21—C26178.7 (6)
O2—C1—C11—C160.4 (11)C26—C21—C22—N230.4 (11)
O1—C1—C11—C16179.4 (6)C5—C21—C22—N23179.9 (7)
O2—C1—C11—C12178.2 (7)C21—C22—N23—C240.9 (11)
O1—C1—C11—C122.8 (9)C22—N23—C24—C250.9 (11)
C16—C11—C12—N132.5 (10)N23—C24—C25—C260.3 (12)
C1—C11—C12—N13179.7 (7)C24—C25—C26—C210.2 (10)
C11—C12—N13—C141.4 (11)C22—C21—C26—C250.2 (10)
C12—N13—C14—C151.1 (11)C5—C21—C26—C25179.3 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O4i0.992.493.341 (8)144
C16—H16···O2ii0.952.453.198 (10)136
C24—H24···O2iii0.952.453.218 (10)138
Symmetry codes: (i) x+3, y+1, z+1; (ii) x+1, y, z; (iii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC15H14N2O4
Mr286.28
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)4.4797 (11), 10.911 (3), 14.842 (4)
α, β, γ (°)104.41 (2), 95.90 (2), 100.90 (2)
V3)681.3 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.22 × 0.14 × 0.07
Data collection
DiffractometerStoe IPDS II two-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8629, 2558, 1382
Rint0.119
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.109, 0.276, 1.49
No. of reflections2558
No. of parameters191
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.46

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O4i0.99002.49003.341 (8)144.00
C16—H16···O2ii0.95002.45003.198 (10)136.00
C24—H24···O2iii0.95002.45003.218 (10)138.00
Symmetry codes: (i) x+3, y+1, z+1; (ii) x+1, y, z; (iii) x+1, y, z+1.
 

Acknowledgements

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.

References

First citationCarlucci, L., Ciani, G., Proserpio, D. M. & Rizzato, S. (2002). CrystEngComm, 22, 121-129.  CSD CrossRef Google Scholar
First citationMatsuda, R., Kitaura, R., Kitagawa, S., Kubota, Y., Belosludov, R. V., Kobayashi, T. C., Sakamoto, H., Chiba, T., Takata, M., Kawazoe, Y. & Mita, Y. (2005). Nature (London), 436, 238–241.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationWu, C. D., Hu, A., Zhang, L. & Lin, W. (2005). J. Am. Chem. Soc. 127, 8940–8941.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationXiang, S., Wu, X., Zhang, J., Fu, R., Hu, S. & Zhang, X. (2005). J. Am. Chem. Soc. 127, 16352–16353.  Web of Science CSD CrossRef PubMed CAS Google Scholar

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