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accessA monoclinic modification of propane-1,3-diyl bis(pyridine-3-carboxylate)
aDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, bDepartamento de Física, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, cInstituto de Bio-Orgánica 'Antonio González', Universidad de La Laguna, Astrofísico Francisco Sánchez N°2, La Laguna, Tenerife, Spain, and dInstitut für Anorganische Chemie der Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany
*Correspondence e-mail: ivanbritob@yahoo.com
In the title compound, C15H14N2O4, (I), the molecule lies on a twofold rotation axis which passes through the central C atom of the aliphatic chain, giving one half-molecule per The structure is a monoclinic polymorph of the triclinic structure previously reported [Brito, Vallejos, Bolte & López-Rodríguez (2010). Acta Cryst. E66, o792], (II). The most obvious difference between them is the O/C/C/C—O/C/C/C torsion angle [58.2 (7)° in (I) and 173.4 (3)/70.2 (3)° in (II) for GG and TG conformations, respectively]. Another important difference is observed in the dihedral angle between the planes of the aromatic rings [86.49 (7)° for (I) and 76.4 (3)° for (II)]. The features a weak π–π interaction [centroid–centroid distance = 4.1397 (10)Å]; this latter kind of interaction is not evident in the triclinic polymorph.
Related literature
For conformation definitions, see: Carlucci et al. (2002![[Carlucci, L., Ciani, G., Proserpio, D. M. & Rizzato, S. (2002). CrystEngComm, 22, 121-129.]](../../../../../../logos/arrows/e_arr.gif "Carlucci, L., Ciani, G., Proserpio, D. M. & Rizzato, S. (2002). CrystEngComm, 22, 121-129.")
). For the structure of the triclinic polymorph, see: Brito et al. (2010a). For the synthesis and structural characterization of coordination polymers, see: Brito et al. (2010b).
![[Scheme 1]](om2394scheme1.gif)
Experimental
Crystal data
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Data collection: X-AREA (Stoe & Cie, 2001); cell X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536810054309/om2394sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536810054309/om2394Isup2.hkl
All reactions were carried out under an atmosphere of purified nitrogen. Solvents were dried and distilled prior to use. 5,5'-dinitro-2,2'-dithiodipyridine and silver trifluoromethanesulfonate were purchased from Aldrich. The title compound was obtained as colourless block crystals, in an attempt to prepare coordination polymers with silver trifluoromethanesulfonate and the ligand (II). The compound (I) was obtained by a mixture of (II) (1 mmol, 27.3 mg) and silver trifluoromethanesulfonate (1 mmol, 25.6 mg) in CH3CN (5 ml). The title compound was filtered off and washed with CH3CN. FT–IR (KBr pellet, cm-1): ν (w, C—H) 3086, ν(s, N=O of NO2 asymmetric) 1581, ν (v.s. of NO2 symmetric) 1352, ν(w, C—H disubstitution 1,4) 1962, ν(s, C—H disubstitution 1,4) 852, ν (w, C—N) 1101, ν(s, C=C) 1603, ν (w, C—H) 1010, (s, C=N) 1510, ν (w, C—S) 740, ν(w S—S) 552.
All H atoms could be located by difference Fourier synthesis but were ultimately placed in calculated positions using a riding model with C— H = 0.95 - 1.00 Å and with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C)].
Data collection: X-AREA (Stoe & Cie, 2001); cell 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 in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./om2394fig1thm.gif) | Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 50% probability level. [symmetry code: A = 1 - x,y,1/2 - z] |
| C15H14N2O4 | F(000) = 600 |
| Mr = 286.28 | Dx = 1.418 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2928 reflections |
| a = 24.414 (3) Å | θ = 3.4–25.9° |
| b = 4.8328 (4) Å | µ = 0.11 mm−1 |
| c = 11.5667 (14) Å | T = 173 K |
| β = 100.671 (10)° | Block, colourless |
| V = 1341.1 (3) Å3 | 0.35 × 0.33 × 0.13 mm |
| Z = 4 |
| Stoe IPDS II two-circle diffractometer | 939 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.037 |
| Graphite monochromator | θmax = 25.6°, θmin = 3.4° |
| ω scans | h = −29→29 |
| 3193 measured reflections | k = −5→5 |
| 1249 independent reflections | l = −14→13 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0497P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.92 | (Δ/σ)max = 0.001 |
| 1249 reflections | Δρmax = 0.17 e Å−3 |
| 97 parameters | Δρmin = −0.14 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0099 (13) |
| C15H14N2O4 | V = 1341.1 (3) Å3 |
| Mr = 286.28 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 24.414 (3) Å | µ = 0.11 mm−1 |
| b = 4.8328 (4) Å | T = 173 K |
| c = 11.5667 (14) Å | 0.35 × 0.33 × 0.13 mm |
| β = 100.671 (10)° |
| Stoe IPDS II two-circle diffractometer | 939 reflections with I > 2σ(I) |
| 3193 measured reflections | Rint = 0.037 |
| 1249 independent reflections |
| R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
| wR(F2) = 0.081 | H-atom parameters constrained |
| S = 0.92 | Δρmax = 0.17 e Å−3 |
| 1249 reflections | Δρmin = −0.14 e Å−3 |
| 97 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.57094 (4) | 0.5968 (2) | 0.53846 (8) | 0.0343 (3) | |
| C1 | 0.58554 (6) | 0.5710 (3) | 0.44442 (11) | 0.0250 (3) | |
| O2 | 0.56326 (4) | 0.7135 (2) | 0.34794 (7) | 0.0273 (3) | |
| C3 | 0.51676 (6) | 0.8926 (3) | 0.36128 (11) | 0.0272 (3) | |
| H3A | 0.5280 | 1.0184 | 0.4291 | 0.033* | |
| H3B | 0.4849 | 0.7795 | 0.3759 | 0.033* | |
| C4 | 0.5000 | 1.0583 (4) | 0.2500 | 0.0266 (5) | |
| H4A | 0.4679 | 1.1804 | 0.2599 | 0.032* | |
| C11 | 0.62930 (6) | 0.3744 (3) | 0.42290 (11) | 0.0254 (3) | |
| C12 | 0.65354 (6) | 0.2013 (3) | 0.51425 (12) | 0.0299 (4) | |
| H12 | 0.6415 | 0.2180 | 0.5875 | 0.036* | |
| N13 | 0.69262 (5) | 0.0130 (3) | 0.50556 (10) | 0.0342 (3) | |
| C14 | 0.70870 (6) | −0.0051 (3) | 0.40112 (12) | 0.0324 (4) | |
| H14 | 0.7368 | −0.1360 | 0.3930 | 0.039* | |
| C15 | 0.68699 (6) | 0.1548 (3) | 0.30476 (12) | 0.0317 (4) | |
| H15 | 0.6998 | 0.1327 | 0.2325 | 0.038* | |
| C16 | 0.64628 (6) | 0.3481 (3) | 0.31495 (11) | 0.0290 (3) | |
| H16 | 0.6303 | 0.4601 | 0.2499 | 0.035* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0395 (6) | 0.0414 (6) | 0.0238 (5) | 0.0043 (5) | 0.0102 (4) | 0.0026 (4) |
| C1 | 0.0281 (8) | 0.0259 (7) | 0.0199 (6) | −0.0060 (6) | 0.0013 (6) | 0.0007 (5) |
| O2 | 0.0313 (6) | 0.0290 (5) | 0.0220 (5) | 0.0045 (4) | 0.0062 (4) | 0.0017 (4) |
| C3 | 0.0274 (8) | 0.0293 (8) | 0.0260 (7) | 0.0015 (6) | 0.0080 (6) | −0.0020 (6) |
| C4 | 0.0259 (11) | 0.0260 (11) | 0.0281 (9) | 0.000 | 0.0057 (8) | 0.000 |
| C11 | 0.0268 (7) | 0.0248 (7) | 0.0238 (6) | −0.0053 (6) | 0.0030 (6) | −0.0014 (5) |
| C12 | 0.0355 (9) | 0.0308 (8) | 0.0232 (6) | −0.0007 (7) | 0.0049 (6) | −0.0009 (6) |
| N13 | 0.0378 (8) | 0.0339 (7) | 0.0303 (6) | 0.0037 (6) | 0.0045 (5) | 0.0008 (5) |
| C14 | 0.0306 (9) | 0.0315 (8) | 0.0354 (8) | 0.0008 (6) | 0.0067 (6) | −0.0042 (6) |
| C15 | 0.0335 (8) | 0.0346 (8) | 0.0282 (7) | −0.0043 (7) | 0.0091 (6) | −0.0037 (6) |
| C16 | 0.0321 (8) | 0.0312 (8) | 0.0231 (7) | −0.0052 (6) | 0.0037 (6) | 0.0009 (6) |
| O1—C1 | 1.2122 (14) | C11—C16 | 1.3925 (16) |
| C1—O2 | 1.3381 (16) | C12—N13 | 1.3355 (19) |
| C1—C11 | 1.4849 (19) | C12—H12 | 0.9500 |
| O2—C3 | 1.4585 (16) | N13—C14 | 1.3405 (17) |
| C3—C4 | 1.5069 (17) | C14—C15 | 1.379 (2) |
| C3—H3A | 0.9900 | C14—H14 | 0.9500 |
| C3—H3B | 0.9900 | C15—C16 | 1.385 (2) |
| C4—C3i | 1.5069 (17) | C15—H15 | 0.9500 |
| C4—H4A | 1.0042 | C16—H16 | 0.9500 |
| C11—C12 | 1.391 (2) | ||
| O1—C1—O2 | 123.62 (13) | C16—C11—C1 | 123.47 (12) |
| O1—C1—C11 | 123.82 (12) | N13—C12—C11 | 124.20 (12) |
| O2—C1—C11 | 112.54 (10) | N13—C12—H12 | 117.9 |
| C1—O2—C3 | 114.92 (9) | C11—C12—H12 | 117.9 |
| O2—C3—C4 | 108.59 (9) | C12—N13—C14 | 116.40 (13) |
| O2—C3—H3A | 110.0 | N13—C14—C15 | 123.98 (14) |
| C4—C3—H3A | 110.0 | N13—C14—H14 | 118.0 |
| O2—C3—H3B | 110.0 | C15—C14—H14 | 118.0 |
| C4—C3—H3B | 110.0 | C14—C15—C16 | 118.94 (12) |
| H3A—C3—H3B | 108.4 | C14—C15—H15 | 120.5 |
| C3i—C4—C3 | 115.77 (17) | C16—C15—H15 | 120.5 |
| C3i—C4—H4A | 108.4 | C15—C16—C11 | 118.38 (13) |
| C3—C4—H4A | 108.0 | C15—C16—H16 | 120.8 |
| C12—C11—C16 | 118.09 (13) | C11—C16—H16 | 120.8 |
| C12—C11—C1 | 118.41 (11) | ||
| O1—C1—O2—C3 | −3.94 (19) | C16—C11—C12—N13 | 0.8 (2) |
| C11—C1—O2—C3 | 174.99 (11) | C1—C11—C12—N13 | 178.94 (14) |
| C1—O2—C3—C4 | 174.58 (12) | C11—C12—N13—C14 | 0.1 (2) |
| O2—C3—C4—C3i | 58.11 (8) | C12—N13—C14—C15 | −0.7 (2) |
| O1—C1—C11—C12 | 2.7 (2) | N13—C14—C15—C16 | 0.4 (2) |
| O2—C1—C11—C12 | −176.23 (13) | C14—C15—C16—C11 | 0.5 (2) |
| O1—C1—C11—C16 | −179.25 (13) | C12—C11—C16—C15 | −1.1 (2) |
| O2—C1—C11—C16 | 1.83 (19) | C1—C11—C16—C15 | −179.13 (13) |
| Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | C15H14N2O4 |
| Mr | 286.28 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 173 |
| a, b, c (Å) | 24.414 (3), 4.8328 (4), 11.5667 (14) |
| β (°) | 100.671 (10) |
| V (Å3) | 1341.1 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.11 |
| Crystal size (mm) | 0.35 × 0.33 × 0.13 |
| Data collection | |
| Diffractometer | Stoe IPDS II two-circle diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3193, 1249, 939 |
| Rint | 0.037 |
| (sin θ/λ)max (Å−1) | 0.608 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.081, 0.92 |
| No. of reflections | 1249 |
| No. of parameters | 97 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.17, −0.14 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008).
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 a PhD fellowship.
References
Brito, I., Vallejos, J., Bolte, M. & López-Rodríguez, M. (2010a). Acta Cryst. E66, o792. Web of Science CrossRef IUCr Journals Google Scholar
Brito, I., Vallejos, J., Mundaca, A., Cárdenas, A., Albanez, J., Vargas, D. & López-Rodríguez, M. (2010b). Mol. Cryst. Liq. Cryst. 521, 158–167. Web of Science CSD CrossRef CAS Google Scholar
Carlucci, L., Ciani, G., Proserpio, D. M. & Rizzato, S. (2002). CrystEngComm, 22, 121–129. CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
This paper forms part of our continuing study of the synthesis and structural characterization of coordination polymers (Brito et al., 2010b). We are particularly interested in the utility of the title compound of as a flexible ligand, and its binding modes, for the fabrication of different coordination polymers topologies. We report here the structure of a new polymorph of propane-1,3-diyl bis(pyridine-3-carboxylate) isolated during attempts to synthetize coordination polymers with silver trifluoromethanesulfonate of the ligand (Fig. 1, Table 1). In the title compound, (I) the molecule lies on a twofold rotation axis which passes through the central C atom of the aliphatic chain, giving one half-molecule per asymmetric unit. The structure is a monoclinic polymorph of the triclinic structure previously reported [Brito et al. (2010a). Acta Cryst. E66, o792], (II). There is excellent agreement between the geometric parameters of (I) and (II). The propanedyl group can adopt four possible conformations: trans-trans (TT), trans-gauche (TG), gauche-gauche (GG) and gauche-gauche' (GG') (Carlucci et al., 2002).The most obvious difference between them is the O/C/C/C—O/C/C/C torsion angle [58.2 (7)° in (I) and 173.4 (3)/70.2 (3)° in (II) for GG and TG conformations, respectively]. Another difference between them is the angle between the planes of aromatic rings [86.49 (7)° for (I) and 76.4 (3)° for triclinic modification]. The crystal structure of the title compound has one intramolecular C—O··· H and one weak π–π interaction (4.1397 (10)Å Cg1— Cg1(i), symmetry code (i) =3/2 - x, 1/2 - y 1 - z; Cg1= N13/C12/C11/C16/C15/C14), whereas this last kind of interaction is not evident in the triclinic polymorph.The triclinic modification is less compact, as noted from the lower density (1.395 Mg m-3 compared with 1.418 Mg m-3 for the monoclinic form).