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

Vallejos, J.; Brito, I.; Cárdenas, A.; Bolte, M.

doi:10.1107/S160053681202260X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2007

https://doi.org/10.1107/S160053681202260X

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

Javier Vallejos,^a ^* Iván Brito,^a Alejandro Cárdenas ^b and Michael Bolte ^c

^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, and ^cInstitut für Anorganische Chemie der Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 16 May 2012; accepted 17 May 2012; online 13 June 2012)

Molecules of the title compound (alternative name: butane-1,4-diyl dinicotinate), C₁₆H₁₆N₂O₄, lie on a inversion centre, located at the mid-point of the central C—C bond of the aliphatic chain, giving one half-molecule per asymmetric unit. The butane chain adopts an all-trans conformation. The dihedral angle between the mean plane of the butane-3-carboxylate group [for the non-H atoms, maximum deviation = 0.0871 (15) Å] and the pyridine ring is 10.83 (7)°. In the crystal, molecules lie in planes parallel to (122). The structure features weak π–π interactions with a centroid–centroid distance of 3.9281 (11) Å.

Related literature

For the crystal structures of compounds with related ligands, see: Brito et al. (2010a ,b ,c , 2011 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₄
M_r = 300.31
Triclinic, $[P \overline 1]$
a = 6.7186 (10) Å
b = 7.6942 (12) Å
c = 8.2462 (13) Å
α = 65.290 (11)°
β = 75.499 (12)°
γ = 68.207 (11)°
V = 357.28 (10) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.29 × 0.25 × 0.18 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (X-AREA and X-RED32; Stoe & Cie, 2001 ) T_min = 0.971, T_max = 0.982
6958 measured reflections
1347 independent reflections
1171 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.090
S = 1.13
1347 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681202260X/su2433sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202260X/su2433Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681202260X/su2433Isup3.cml

checkCIF report

Comment top

This paper forms part of our continuing study of the synthesis and structural characterization of coordination polymers (Brito et al., 2010a,b,c; 2011). We are particularly interested in the utility of the title compound as a flexible ligand and for its binding modes, in order to synthesis different coordination polymer topologies. Molecules of the title compound, (Fig. 1), lie on an inversion centre, which passes through middle point of the C4—C4A bond of the aliphatic chain, giving one half-molecule per asymmetric unit. The butane chain adopts an all trans conformation. The dihedral angle between the mean plane of the butane-3-carboxylate moiety [non-H atoms; max. deviation for atoms C3/C3A = 0.0871 (15) Å] and the pyridine ring is 10.83 (7)°.

The crystal structure is stabilized by weak π–π interactions with centroid-centroid distances of 3.9281 (11) Å. The molecules lie in planes parallel to (122) [Fig. 2].

Related literature top

For the crystal structures of related ligands, see: Brito et al. (2010a,b,c, 2011).

Experimental top

Isonicotinoyl chloride hydrochloride (354 mg, 2 mmol) was taken in a 50 ml round bottom schlenk flask and fitted with a reflux condenser. Dichloromethane 25 ml, 1,4-Butanediol (0.10 ml, 1.0 mmol) and 1 ml of triethylamine were added. The reaction mixture was heated at 323 K for 3 h. After, the mixture was washed with saturated aqueous sodium bicarbonate solution (50 ml), the organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was evaporated using vacuum and the white product was purified by recrystallization with acetonitrile (Yield: 87%). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in dichloromethane at room temperature.

Spectroscopic details are given in the archived CIF.

Structure description top

The crystal structure is stabilized by weak π–π interactions with centroid-centroid distances of 3.9281 (11) Å. The molecules lie in planes parallel to (122) [Fig. 2].

For the crystal structures of related ligands, see: Brito et al. (2010a,b,c, 2011).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of the title molecule, with the atom-numbering. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (A) = -x+2, -y+2, -z].
	Fig. 2. A partial view of the crystal packing of the title compound, showing the weak π–π stacking interactions [Cg = centroid of ring N13,C11,C12,C14-C16; symmetry code: (i) = -x+1, -y+1, -z+1; H atoms have been omitted for clarity].

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

Crystal data top

C₁₆H₁₆N₂O₄	Z = 1
M_r = 300.31	F(000) = 158
Triclinic, P1	D_x = 1.396 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7186 (10) Å	Cell parameters from 9708 reflections
b = 7.6942 (12) Å	θ = 3.3–26.0°
c = 8.2462 (13) Å	µ = 0.10 mm⁻¹
α = 65.290 (11)°	T = 173 K
β = 75.499 (12)°	Block, colourless
γ = 68.207 (11)°	0.29 × 0.25 × 0.18 mm
V = 357.28 (10) Å³

Data collection top

Stoe IPDS II two-circle diffractometer	1347 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	1171 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	R_int = 0.035
ω scans	θ_max = 25.6°, θ_min = 3.3°
Absorption correction: multi-scan (X-AREA and X-RED32; Stoe & Cie, 2001)	h = −7→8
T_min = 0.971, T_max = 0.982	k = −9→9
6958 measured reflections	l = −10→10

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0318P)² + 0.1244P] where P = (F_o² + 2F_c²)/3
1347 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₆H₁₆N₂O₄	γ = 68.207 (11)°
M_r = 300.31	V = 357.28 (10) Å³
Triclinic, P1	Z = 1
a = 6.7186 (10) Å	Mo Kα radiation
b = 7.6942 (12) Å	µ = 0.10 mm⁻¹
c = 8.2462 (13) Å	T = 173 K
α = 65.290 (11)°	0.29 × 0.25 × 0.18 mm
β = 75.499 (12)°

Data collection top

Stoe IPDS II two-circle diffractometer	1347 independent reflections
Absorption correction: multi-scan (X-AREA and X-RED32; Stoe & Cie, 2001)	1171 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.982	R_int = 0.035
6958 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.13	Δρ_max = 0.19 e Å⁻³
1347 reflections	Δρ_min = −0.14 e Å⁻³
100 parameters

Special details top

Experimental. Spectroscopic details for the title compound:

IR (KBr): 3087 (w), 1713 (s), 1589 (m), 1473 (w), 1294 (s), 1195 (s), 741(m), cm^-1.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.31502 (17)	1.03384 (16)	0.27815 (14)	0.0328 (3)
O2	0.66529 (16)	0.87068 (16)	0.31015 (13)	0.0279 (3)
C1	0.4547 (2)	0.8987 (2)	0.36257 (19)	0.0238 (3)
C3	0.7222 (2)	1.0083 (2)	0.13405 (19)	0.0260 (3)
H3A	0.6772	1.1460	0.1347	0.031*
H3B	0.6496	1.0104	0.0423	0.031*
C4	0.9628 (2)	0.9344 (2)	0.09306 (19)	0.0285 (4)
H4A	1.0063	0.7942	0.0991	0.034*
H4B	1.0334	0.9360	0.1842	0.034*
C11	0.4134 (2)	0.7418 (2)	0.53811 (19)	0.0242 (3)
C12	0.5775 (3)	0.6012 (2)	0.64157 (19)	0.0285 (3)
H12	0.7208	0.6067	0.5976	0.034*
N13	0.5455 (2)	0.4591 (2)	0.79911 (17)	0.0339 (3)
C14	0.3422 (3)	0.4555 (2)	0.8578 (2)	0.0325 (4)
H14	0.3158	0.3561	0.9703	0.039*
C15	0.1685 (3)	0.5879 (2)	0.7646 (2)	0.0320 (4)
H15	0.0269	0.5788	0.8116	0.038*
C16	0.2046 (2)	0.7336 (2)	0.6017 (2)	0.0286 (4)
H16	0.0883	0.8268	0.5342	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0257 (6)	0.0321 (6)	0.0288 (6)	−0.0071 (5)	−0.0041 (5)	−0.0009 (5)
O2	0.0222 (5)	0.0301 (6)	0.0229 (5)	−0.0088 (4)	−0.0001 (4)	−0.0023 (4)
C1	0.0231 (7)	0.0254 (7)	0.0224 (7)	−0.0086 (6)	−0.0017 (6)	−0.0075 (6)
C3	0.0264 (8)	0.0274 (7)	0.0194 (7)	−0.0117 (6)	0.0004 (6)	−0.0026 (6)
C4	0.0246 (8)	0.0301 (8)	0.0255 (8)	−0.0097 (6)	−0.0014 (6)	−0.0047 (7)
C11	0.0268 (8)	0.0216 (7)	0.0230 (7)	−0.0072 (6)	0.0006 (6)	−0.0090 (6)
C12	0.0260 (8)	0.0298 (8)	0.0248 (8)	−0.0075 (6)	0.0000 (6)	−0.0077 (6)
N13	0.0331 (7)	0.0303 (7)	0.0271 (7)	−0.0057 (6)	−0.0022 (6)	−0.0039 (6)
C14	0.0397 (9)	0.0266 (8)	0.0226 (8)	−0.0121 (7)	0.0039 (7)	−0.0032 (6)
C15	0.0293 (8)	0.0314 (8)	0.0308 (8)	−0.0135 (7)	0.0054 (6)	−0.0082 (7)
C16	0.0261 (8)	0.0264 (8)	0.0279 (8)	−0.0065 (6)	−0.0024 (6)	−0.0065 (6)

Geometric parameters (Å, º) top

O1—C1	1.2017 (18)	C11—C16	1.384 (2)
O2—C1	1.3342 (18)	C11—C12	1.389 (2)
O2—C3	1.4538 (17)	C12—N13	1.333 (2)
C1—C11	1.4886 (19)	C12—H12	0.9500
C3—C4	1.502 (2)	N13—C14	1.337 (2)
C3—H3A	0.9900	C14—C15	1.379 (2)
C3—H3B	0.9900	C14—H14	0.9500
C4—C4ⁱ	1.523 (3)	C15—C16	1.378 (2)
C4—H4A	0.9900	C15—H15	0.9500
C4—H4B	0.9900	C16—H16	0.9500

C1—O2—C3	115.98 (12)	C16—C11—C12	118.20 (14)
O1—C1—O2	124.15 (13)	C16—C11—C1	119.43 (13)
O1—C1—C11	123.99 (13)	C12—C11—C1	122.38 (13)
O2—C1—C11	111.87 (12)	N13—C12—C11	123.74 (14)
O2—C3—C4	106.96 (12)	N13—C12—H12	118.1
O2—C3—H3A	110.3	C11—C12—H12	118.1
C4—C3—H3A	110.3	C12—N13—C14	116.78 (14)
O2—C3—H3B	110.3	N13—C14—C15	123.82 (14)
C4—C3—H3B	110.3	N13—C14—H14	118.1
H3A—C3—H3B	108.6	C15—C14—H14	118.1
C3—C4—C4ⁱ	110.76 (16)	C16—C15—C14	118.61 (15)
C3—C4—H4A	109.5	C16—C15—H15	120.7
C4ⁱ—C4—H4A	109.5	C14—C15—H15	120.7
C3—C4—H4B	109.5	C15—C16—C11	118.86 (15)
C4ⁱ—C4—H4B	109.5	C15—C16—H16	120.6
H4A—C4—H4B	108.1	C11—C16—H16	120.6

C3—O2—C1—O1	−3.9 (2)	C16—C11—C12—N13	−0.3 (2)
C3—O2—C1—C11	175.89 (12)	C1—C11—C12—N13	−179.97 (15)
C1—O2—C3—C4	−173.02 (12)	C11—C12—N13—C14	−0.2 (2)
O2—C3—C4—C4ⁱ	177.89 (15)	C12—N13—C14—C15	0.5 (2)
O1—C1—C11—C16	7.7 (2)	N13—C14—C15—C16	−0.4 (3)
O2—C1—C11—C16	−172.10 (13)	C14—C15—C16—C11	−0.1 (2)
O1—C1—C11—C12	−172.59 (15)	C12—C11—C16—C15	0.4 (2)
O2—C1—C11—C12	7.61 (19)	C1—C11—C16—C15	−179.89 (14)

Symmetry code: (i) −x+2, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₄
M_r	300.31
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.7186 (10), 7.6942 (12), 8.2462 (13)
α, β, γ (°)	65.290 (11), 75.499 (12), 68.207 (11)
V (Å³)	357.28 (10)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.29 × 0.25 × 0.18

Data collection
Diffractometer	Stoe IPDS II two-circle
Absorption correction	Multi-scan (X-AREA and X-RED32; Stoe & Cie, 2001)
T_min, T_max	0.971, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	6958, 1347, 1171
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.090, 1.13
No. of reflections	1347
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

Computer programs: X-AREA (Stoe & Cie, 2001), X-RED32 (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

We are grateful to the Consejo Superior de Investigaciones Científicas (CSIC) of Spain for the award of a licence for the use of the Cambridge Structural Database (CSD). JV thanks the Universidad de Antofagasta for a PhD fellowship.

References

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