Propane-1,3-diyl bis­(pyridine-4-carboxyl­ate)

Brito, I.; Vallejos, J.; Bolte, M.; López-Rodríguez, M.; Cárdenas, A.

doi:10.1107/S1600536810011700

organic compounds

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Volume 66| Part 5| May 2010| Page o1015

https://doi.org/10.1107/S1600536810011700

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Propane-1,3-diyl bis(pyridine-4-carboxylate)

Iván Brito,^a ^* Javier Vallejos,^a Michael Bolte,^b Matías López-Rodríguez ^c and Alejandro Cárdenas ^d

^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, ^cInstituto de Bio-Orgánica 'Antonio González', Universidad de La Laguna, Astrofísico Francisco Sánchez N°2, La Laguna, Tenerife, Spain, and ^dDepartamento de Física, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 16 March 2010; accepted 28 March 2010; online 2 April 2010)

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.

Related literature

The title compound can be used as a nucleophilic tecton in self-assembly reactions with metal centres of varying lability. For conformation definitions see: Carlucci et al. (2002 ). For related structures, see: Brito et al. (2010 ); Chatterjee et al. (2004 ).

Experimental

Crystal data

C₁₅H₁₄N₂O₄
M_r = 286.28
Monoclinic, C 2/c
a = 23.022 (4) Å
b = 4.9336 (5) Å
c = 11.9604 (18) Å
β = 98.118 (13)°
V = 1344.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.18 × 0.15 × 0.09 mm

Data collection

Stoe IPDS II two-circle diffractometer
4231 measured reflections
1251 independent reflections
799 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.094
S = 0.87
1251 reflections
96 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O1^iv	0.99	2.62	3.521 (3)	152
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+2, -z+1; (iv) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: 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 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810011700/fl2297sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810011700/fl2297Isup2.hkl

checkCIF report

Comment top

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 C₁₅H₁₄N₂O_4,(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.

Related literature top

The title compound can be used as a nucleophilic tecton in self-assembly reactions with metal centres of varying lability. For conformation definitions see: Carlucci et al. (2002). For related structures, see: Brito et al. (2010); Chatterjee et al. (2004).

Experimental top

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.

Structure description top

The title compound can be used as a nucleophilic tecton in self-assembly reactions with metal centres of varying lability. For conformation definitions see: Carlucci et al. (2002). For related structures, see: Brito et al. (2010); Chatterjee et al. (2004).

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

	Fig. 1. Displacement ellipsoid plot at the 50% probability level for the non-H atoms. Symmetry operator for generating equivalent atoms: (A) 1-x, y, -z+3/2.
	Fig. 2. Packing diagram of the title compound with view onto the ab plane.
	Fig. 3. Schematic representations of (I) and (II).

Propane-1,3-diyl bis(pyridine-4-carboxylate) top

Crystal data top

C₁₅H₁₄N₂O₄	F(000) = 600
M_r = 286.28	D_x = 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	R_int = 0.070
Graphite monochromator	θ_max = 25.6°, θ_min = 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(F_o²) + (0.0427P)²] where P = (F_o² + 2F_c²)/3
1251 reflections	(Δ/σ)_max < 0.001
96 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₅H₁₄N₂O₄	V = 1344.9 (3) Å³
M_r = 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	R_int = 0.070
1251 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 0.87	Δρ_max = 0.16 e Å⁻³
1251 reflections	Δρ_min = −0.21 e Å⁻³
96 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

	x	y	z	U_iso*/U_eq
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, º) 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 code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) 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···O1^iv	0.99	2.98	3.516 (3)	115
C3—H3B···O1^v	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.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₂O₄
M_r	286.28
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	23.022 (4), 4.9336 (5), 11.9604 (18)
β (°)	98.118 (13)
V (Å³)	1344.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.18 × 0.15 × 0.09

Data collection
Diffractometer	Stoe IPDS II two-circle
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4231, 1251, 799
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.094, 0.87
No. of reflections	1251
No. of parameters	96
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···N14ⁱ	0.95	2.65	3.505 (3)	150.6
C15—H15···N14ⁱⁱ	0.95	2.72	3.496 (3)	139.3
C3—H3A···O1ⁱⁱⁱ	0.99	2.98	3.516 (3)	115.1
C3—H3B···O1^iv	0.99	2.62	3.521 (3)	151.7

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.

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

Brito, I., Vallejos, J., Bolte, M. & López-Rodríguez, M. (2010). Acta Cryst. E66, o792. Web of Science CrossRef IUCr Journals Google Scholar
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