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

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

doi:10.1107/S1600536810008810

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o792

doi:10.1107/S1600536810008810

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

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

^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 ). For applications of crystalline nanoporous coordination polymers, see Matsuda et al. (2005 ); Wu et al. (2005 ); Xiang et al. (2005 ).

Experimental

Crystal data

C₁₅H₁₄N₂O₄
M_r = 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)
R_int = 0.119

Refinement

R[F² > 2σ(F²)] = 0.109
wR(F²) = 0.276
S = 1.49
2558 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); 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: 10.1107/S1600536810008810/om2324sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008810/om2324Isup2.hkl

checkCIF report

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): (C═O) 1715 s, (C═C) 1591 m, (Ar C—C, C═N) 1429 s,(C—O) 1277 m.

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. 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

C₁₅H₁₄N₂O₄	Z = 2
M_r = 286.28	F(000) = 300
Triclinic, P1	D_x = 1.395 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.4797 (11) Å	Cell parameters from 3924 reflections
b = 10.911 (3) Å	θ = 3.9–25.8°
c = 14.842 (4) Å	µ = 0.10 mm⁻¹
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 tube	R_int = 0.119
Graphite monochromator	θ_max = 26.0°, θ_min = 3.8°
ω scans	h = −5→5
8629 measured reflections	k = −13→12
2558 independent reflections	l = −12→17

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)] = 0.109	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.276	H-atom parameters constrained
S = 1.49	w = 1/[σ²(F_o²) + (0.090P)²] where P = (F_o² + 2F_c²)/3
2558 reflections	(Δ/σ)_max < 0.001
191 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₅H₁₄N₂O₄	γ = 100.90 (2)°
M_r = 286.28	V = 681.3 (3) Å³
Triclinic, P1	Z = 2
a = 4.4797 (11) Å	Mo Kα radiation
b = 10.911 (3) Å	µ = 0.10 mm⁻¹
c = 14.842 (4) Å	T = 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 reflections	R_int = 0.119
2558 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.109	0 restraints
wR(F²) = 0.276	H-atom parameters constrained
S = 1.49	Δρ_max = 0.43 e Å⁻³
2558 reflections	Δρ_min = −0.46 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O1	0.8187 (10)	0.2723 (4)	0.2445 (4)	0.0458 (12)
O2	0.6697 (13)	0.0749 (5)	0.1430 (4)	0.0637 (16)
O3	1.1653 (9)	0.2272 (4)	0.5109 (3)	0.0405 (11)
O4	1.2061 (11)	0.4252 (4)	0.6081 (4)	0.0540 (14)
C1	0.6560 (14)	0.1865 (6)	0.1644 (5)	0.0434 (17)
C2	1.0002 (15)	0.2161 (6)	0.3054 (5)	0.0434 (16)
H2A	1.1296	0.1648	0.2688	0.052*
H2B	0.8629	0.1587	0.3334	0.052*
C3	1.2023 (14)	0.3317 (6)	0.3827 (5)	0.0448 (17)
H3A	1.3515	0.3838	0.3543	0.054*
H3B	1.0718	0.3881	0.4135	0.054*
C4	1.3748 (14)	0.2826 (7)	0.4557 (5)	0.0445 (17)
H4A	1.4795	0.2160	0.4234	0.053*
H4B	1.5339	0.3554	0.4981	0.053*
C5	1.0994 (13)	0.3111 (6)	0.5848 (5)	0.0439 (17)
C11	0.4701 (14)	0.2473 (6)	0.1081 (5)	0.0420 (16)
C12	0.4516 (15)	0.3777 (6)	0.1359 (5)	0.0451 (17)
H12	0.5646	0.4308	0.1948	0.054*
N13	0.2835 (15)	0.4308 (6)	0.0838 (5)	0.0568 (17)
C14	0.1172 (16)	0.3544 (7)	0.0009 (6)	0.0538 (19)
H14	−0.0070	0.3904	−0.0367	0.065*
C15	0.1253 (17)	0.2229 (7)	−0.0306 (6)	0.055 (2)
H15	0.0121	0.1712	−0.0899	0.066*
C16	0.2940 (17)	0.1699 (7)	0.0235 (6)	0.0516 (19)
H16	0.2923	0.0800	0.0037	0.062*
C21	0.8829 (13)	0.2446 (6)	0.6378 (5)	0.0386 (15)
C22	0.7613 (14)	0.1126 (6)	0.6107 (6)	0.0472 (18)
H22	0.8192	0.0626	0.5560	0.057*
N23	0.5693 (13)	0.0501 (6)	0.6553 (4)	0.0505 (16)
C24	0.4879 (17)	0.1254 (7)	0.7329 (6)	0.0526 (19)
H24	0.3486	0.0843	0.7661	0.063*
C25	0.5981 (16)	0.2594 (6)	0.7660 (5)	0.0470 (17)
H25	0.5369	0.3086	0.8205	0.056*
C26	0.7973 (14)	0.3177 (6)	0.7173 (5)	0.0446 (17)
H26	0.8772	0.4089	0.7381	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.045 (2)	0.027 (2)	0.054 (3)	0.0010 (19)	−0.005 (2)	0.001 (2)
O2	0.095 (4)	0.041 (3)	0.047 (3)	0.020 (3)	−0.005 (3)	−0.001 (2)
O3	0.036 (2)	0.035 (2)	0.043 (3)	−0.0023 (18)	0.005 (2)	0.004 (2)
O4	0.051 (3)	0.032 (3)	0.066 (4)	−0.004 (2)	0.006 (2)	0.003 (2)
C1	0.043 (3)	0.033 (4)	0.048 (5)	0.002 (3)	0.003 (3)	0.008 (3)
C2	0.044 (3)	0.033 (3)	0.053 (4)	0.006 (3)	0.006 (3)	0.014 (3)
C3	0.037 (3)	0.031 (3)	0.056 (4)	−0.008 (3)	−0.001 (3)	0.009 (3)
C4	0.041 (3)	0.040 (4)	0.054 (5)	0.002 (3)	0.015 (3)	0.020 (3)
C5	0.034 (3)	0.027 (3)	0.062 (5)	0.002 (3)	−0.001 (3)	0.002 (3)
C11	0.046 (3)	0.025 (3)	0.046 (4)	0.004 (3)	0.005 (3)	−0.002 (3)
C12	0.053 (4)	0.027 (3)	0.048 (5)	0.007 (3)	0.003 (3)	0.001 (3)
N13	0.072 (4)	0.039 (3)	0.051 (4)	0.013 (3)	−0.006 (3)	0.003 (3)
C14	0.057 (4)	0.041 (4)	0.057 (5)	0.012 (3)	−0.009 (4)	0.008 (4)
C15	0.059 (4)	0.043 (4)	0.049 (5)	0.008 (3)	0.007 (4)	−0.010 (3)
C16	0.066 (4)	0.030 (3)	0.051 (5)	0.006 (3)	0.009 (4)	0.001 (3)
C21	0.031 (3)	0.029 (3)	0.044 (4)	0.001 (2)	−0.007 (3)	−0.002 (3)
C22	0.045 (3)	0.024 (3)	0.063 (5)	0.001 (3)	0.003 (3)	0.003 (3)
N23	0.054 (3)	0.041 (3)	0.048 (4)	−0.002 (3)	0.004 (3)	0.008 (3)
C24	0.058 (4)	0.040 (4)	0.055 (5)	0.004 (3)	0.011 (4)	0.010 (4)
C25	0.050 (4)	0.034 (3)	0.047 (4)	0.006 (3)	−0.002 (3)	−0.002 (3)
C26	0.042 (3)	0.028 (3)	0.051 (5)	0.004 (3)	0.000 (3)	−0.008 (3)

Geometric parameters (Å, º) top

O1—C1	1.353 (8)	C12—N13	1.329 (10)
O1—C2	1.472 (8)	C12—H12	0.9500
O2—C1	1.194 (8)	N13—C14	1.353 (10)
O3—C5	1.340 (8)	C14—C15	1.402 (10)
O3—C4	1.452 (7)	C14—H14	0.9500
O4—C5	1.193 (8)	C15—C16	1.349 (12)
C1—C11	1.475 (10)	C15—H15	0.9500
C2—C3	1.537 (9)	C16—H16	0.9500
C2—H2A	0.9900	C21—C22	1.379 (8)
C2—H2B	0.9900	C21—C26	1.384 (9)
C3—C4	1.528 (10)	C22—N23	1.328 (9)
C3—H3A	0.9900	C22—H22	0.9500
C3—H3B	0.9900	N23—C24	1.364 (10)
C4—H4A	0.9900	C24—C25	1.393 (9)
C4—H4B	0.9900	C24—H24	0.9500
C5—C21	1.504 (10)	C25—C26	1.368 (10)
C11—C16	1.389 (10)	C25—H25	0.9500
C11—C12	1.400 (8)	C26—H26	0.9500

C1—O1—C2	114.8 (5)	N13—C12—C11	123.2 (7)
C5—O3—C4	116.2 (5)	N13—C12—H12	118.4
O2—C1—O1	122.4 (6)	C11—C12—H12	118.4
O2—C1—C11	125.2 (6)	C12—N13—C14	118.4 (7)
O1—C1—C11	112.4 (6)	N13—C14—C15	121.1 (7)
O1—C2—C3	105.9 (5)	N13—C14—H14	119.5
O1—C2—H2A	110.6	C15—C14—H14	119.5
C3—C2—H2A	110.6	C16—C15—C14	119.9 (7)
O1—C2—H2B	110.6	C16—C15—H15	120.0
C3—C2—H2B	110.6	C14—C15—H15	120.0
H2A—C2—H2B	108.7	C15—C16—C11	119.8 (7)
C4—C3—C2	109.8 (6)	C15—C16—H16	120.1
C4—C3—H3A	109.7	C11—C16—H16	120.1
C2—C3—H3A	109.7	C22—C21—C26	117.6 (7)
C4—C3—H3B	109.7	C22—C21—C5	123.1 (6)
C2—C3—H3B	109.7	C26—C21—C5	119.3 (6)
H3A—C3—H3B	108.2	N23—C22—C21	125.0 (7)
O3—C4—C3	111.0 (5)	N23—C22—H22	117.5
O3—C4—H4A	109.4	C21—C22—H22	117.5
C3—C4—H4A	109.4	C22—N23—C24	115.8 (6)
O3—C4—H4B	109.4	N23—C24—C25	123.6 (7)
C3—C4—H4B	109.4	N23—C24—H24	118.2
H4A—C4—H4B	108.0	C25—C24—H24	118.2
O4—C5—O3	124.4 (6)	C26—C25—C24	117.7 (7)
O4—C5—C21	123.4 (7)	C26—C25—H25	121.2
O3—C5—C21	112.2 (5)	C24—C25—H25	121.2
C16—C11—C12	117.6 (7)	C25—C26—C21	120.3 (6)
C16—C11—C1	118.2 (6)	C25—C26—H26	119.8
C12—C11—C1	124.1 (6)	C21—C26—H26	119.8

C2—O1—C1—O2	−3.1 (9)	N13—C14—C15—C16	1.9 (12)
C2—O1—C1—C11	177.9 (5)	C14—C15—C16—C11	−2.9 (11)
C1—O1—C2—C3	171.4 (5)	C12—C11—C16—C15	3.2 (10)
O1—C2—C3—C4	173.9 (5)	C1—C11—C16—C15	−178.9 (7)
C5—O3—C4—C3	−84.3 (7)	O4—C5—C21—C22	−179.8 (7)
C2—C3—C4—O3	−70.1 (7)	O3—C5—C21—C22	−1.8 (9)
C4—O3—C5—O4	−1.7 (10)	O4—C5—C21—C26	0.8 (10)
C4—O3—C5—C21	−179.6 (6)	O3—C5—C21—C26	178.7 (6)
O2—C1—C11—C16	0.4 (11)	C26—C21—C22—N23	−0.4 (11)
O1—C1—C11—C16	179.4 (6)	C5—C21—C22—N23	−179.9 (7)
O2—C1—C11—C12	178.2 (7)	C21—C22—N23—C24	0.9 (11)
O1—C1—C11—C12	−2.8 (9)	C22—N23—C24—C25	−0.9 (11)
C16—C11—C12—N13	−2.5 (10)	N23—C24—C25—C26	0.3 (12)
C1—C11—C12—N13	179.7 (7)	C24—C25—C26—C21	0.2 (10)
C11—C12—N13—C14	1.4 (11)	C22—C21—C26—C25	−0.2 (10)
C12—N13—C14—C15	−1.1 (11)	C5—C21—C26—C25	179.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₂O₄
M_r	286.28
Crystal system, space group	Triclinic, 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)
V (Å³)	681.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.22 × 0.14 × 0.07

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8629, 2558, 1382
R_int	0.119
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.109, 0.276, 1.49
No. of reflections	2558
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
C3—H3A···O4ⁱ	0.9900	2.4900	3.341 (8)	144.00
C16—H16···O2ⁱⁱ	0.9500	2.4500	3.198 (10)	136.00
C24—H24···O2ⁱⁱⁱ	0.9500	2.4500	3.218 (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

Carlucci, L., Ciani, G., Proserpio, D. M. & Rizzato, S. (2002). CrystEngComm, 22, 121-129. CSD CrossRef Google Scholar
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. Web of Science CrossRef PubMed CAS 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 and X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wu, 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
Xiang, 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