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

Abstract

The mol­ecule of the title compound, C₁₆H₁₆N₂O₄, lies about an inversion centre; the butane chain adopts an extended zigzag conformation. The dihedral angle between the pyridine ring and the adjacent COO group is 3.52 (s14)°.

Related literature

For a related structure, see: Brito et al. (2010 ▶).

Experimental

Crystal data

• C₁₆H₁₆N₂O₄

• M _r = 300.31

• Monoclinic,

• a = 7.8519 (5) Å

• b = 10.5284 (6) Å

• c = 8.9121 (4) Å

• β = 91.770 (5)°

• V = 736.39 (7) ų

• Z = 2

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 293 K

• 0.35 × 0.13 × 0.04 mm

Data collection

• Oxford Diffraction Xcalibur Eos diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.840, T _max = 1.000

• 2431 measured reflections

• 1303 independent reflections

• 754 reflections with I > 2σ(I)

• R _int = 0.018

Refinement

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.102

• S = 0.87

• 1303 reflections

• 100 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.13 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811023646/ng5184Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Pyridine containing compounds are the new class of anti-HIV molecules, which particularly inhibit RNA dependent DNA polymerase or reverse transcriptase, and hence it acts as non-nucleoside reverse transcriptase inhibitors. They also posses potent anti-bacterial activity. Pyridine containing ruthenium complexes exhibit cytotoxic, anti-cancer, anti-tumor or anti-metastatic activity. Considering the biological importances of the pyridine and its derivatives, a single-crystal of the title compound was prepared for X-ray diffraction studies. The molecular structure of title compound is shown in Fig. 1. The bond distances of pyridyl group in title compound is comparable to those observed in related structure namely propane-1,3-diyl bis(pyridine-4-carboxylate) (Brito et al., 2010). The pyridyl group (N1/C4/C3/C2/C6/C5) adopts a planar conformation (r.m.s. deviation = 0.0019 Å). Cremer & Pople puckering analysis fails, because of its weighted average absolute torsion angle is 0.4°, which is less than 5.0°. The 1,4-butanediyl ester group occupies an equatorial position, which adopt an extended zigzag conformation. Intermolecular π-π stacking interactions is normally found in aromatic compounds. However, in the title compound, the minimal distance between ring centroids is 4.357 (1) Å. Hence, intermolecular π-π stacking interactions are not present in the title compound. The classical hydrogen bonds are not observed. The packing diagram of title compound is shown in Fig. 2.

Experimental

Isonicotinoyl chloride hydrochloride (639 mg, 3.5 mmol) was taken in a 50 ml round bottom schlenk flask and fitted with a reflux condenser. The system was evacuated and purged with nitrogen. To this, dry dichloromethane 25 ml, 1,4-Butanediol (0.15 ml, 1.7 mmol) and 1 ml of triethylamine were added. The reaction mixture was heated at 40 °C for 5 h. After, the mixture was washed with saturated aqueous sodium bicarbonate solution (20 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 dichloromethane (Yield: 87%, Melting Point: 140 °C). 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 data of the title compound: IR (KBr): 3046 (w), 1728 (s), 1560 (w), 1476 (w), 1286 (s), 1127 (s), 755 (m), cm^{-1. 1}H NMR (400 MHz, CDCl₃): δ 8.77 (d, 4H), 7.83 (d, 4H), 4.43–4.42 (m, 4H), 1.97–1.94 (m, 4H). ¹³C NMR (100 MHz, CDCl₃): δ 165.2, 150.7, 137.4, 122.9, 65.2, 25.3.

Refinement

The non-hydrogen atoms were refined anisotropically whereas hydrogen atoms were refined isotropically. The hydrogen atoms were placed in calculated positions (C–H = 0.93–0.97 Å) and included in the refinement in riding-model approximation with U_iso(H) = 1.2Ueq(C).

Figures

Fig. 1.

The molecular structure of title compound, showing displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

Packing diagram of title compound.

Crystal data

C16H16N2O4	F(000) = 316
Mr = 300.31	Dx = 1.354 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 852 reflections
a = 7.8519 (5) Å	θ = 2.6–28.6°
b = 10.5284 (6) Å	µ = 0.10 mm−1
c = 8.9121 (4) Å	T = 293 K
β = 91.770 (5)°	Plate, colorless
V = 736.39 (7) Å3	0.35 × 0.13 × 0.04 mm
Z = 2

Data collection

Oxford Diffraction Xcalibur Eos diffractometer	1303 independent reflections
Radiation source: fine-focus sealed tube	754 reflections with I > 2σ(I)
graphite	Rint = 0.018
Detector resolution: 15.9821 pixels mm-1	θmax = 25.0°, θmin = 2.6°
ω scans	h = −9→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −12→7
Tmin = 0.840, Tmax = 1.000	l = −6→10
2431 measured reflections

Refinement

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102	H-atom parameters constrained
S = 0.87	w = 1/[σ2(Fo2) + (0.0561P)2] where P = (Fo2 + 2Fc2)/3
1303 reflections	(Δ/σ)max = 0.001
100 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.13 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.33092 (14)	0.50761 (11)	0.18817 (12)	0.0510 (4)
C2	0.21740 (19)	0.51211 (16)	−0.05823 (17)	0.0389 (4)
C1	0.2787 (2)	0.58307 (18)	0.0775 (2)	0.0466 (5)
O2	0.2806 (2)	0.69674 (13)	0.08561 (15)	0.0789 (5)
C3	0.1504 (2)	0.57907 (18)	−0.17878 (19)	0.0504 (5)
H3	0.1438	0.6672	−0.1753	0.060*
C6	0.2231 (2)	0.38214 (18)	−0.06986 (19)	0.0529 (5)
H6	0.2663	0.3327	0.0090	0.063*
N1	0.0981 (2)	0.39039 (17)	−0.31796 (17)	0.0607 (5)
C4	0.0936 (2)	0.5144 (2)	−0.3041 (2)	0.0546 (6)
H4	0.0491	0.5614	−0.3844	0.065*
C7	0.3923 (2)	0.57013 (18)	0.32514 (19)	0.0539 (6)
H7A	0.3001	0.6162	0.3705	0.065*
H7B	0.4819	0.6300	0.3026	0.065*
C8	0.4589 (2)	0.47077 (18)	0.42959 (18)	0.0465 (5)
H8A	0.5424	0.4195	0.3792	0.056*
H8B	0.3663	0.4156	0.4577	0.056*
C5	0.1632 (3)	0.3269 (2)	−0.2011 (2)	0.0645 (6)
H5	0.1688	0.2389	−0.2084	0.077*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0716 (8)	0.0474 (8)	0.0329 (7)	0.0001 (6)	−0.0175 (6)	−0.0006 (6)
C2	0.0430 (10)	0.0424 (10)	0.0310 (9)	−0.0030 (8)	−0.0023 (8)	−0.0006 (9)
C1	0.0597 (12)	0.0440 (11)	0.0356 (10)	−0.0006 (10)	−0.0063 (9)	0.0026 (10)
O2	0.1401 (14)	0.0422 (9)	0.0522 (9)	−0.0013 (9)	−0.0322 (8)	−0.0016 (7)
C3	0.0659 (13)	0.0436 (11)	0.0410 (11)	−0.0005 (10)	−0.0108 (10)	0.0029 (9)
C6	0.0726 (13)	0.0466 (12)	0.0386 (11)	0.0012 (10)	−0.0110 (10)	0.0022 (10)
N1	0.0755 (12)	0.0600 (12)	0.0454 (10)	−0.0034 (9)	−0.0162 (9)	−0.0042 (9)
C4	0.0683 (14)	0.0590 (13)	0.0353 (10)	0.0028 (11)	−0.0156 (9)	0.0027 (10)
C7	0.0710 (13)	0.0542 (13)	0.0353 (10)	−0.0022 (10)	−0.0185 (10)	−0.0059 (9)
C8	0.0540 (11)	0.0516 (11)	0.0331 (9)	−0.0001 (9)	−0.0111 (8)	−0.0010 (9)
C5	0.0927 (16)	0.0447 (12)	0.0553 (13)	−0.0060 (11)	−0.0134 (12)	−0.0084 (11)

Geometric parameters (Å, °)

O1—C1	1.322 (2)	N1—C4	1.312 (2)
O1—C7	1.4558 (19)	N1—C5	1.326 (2)
C2—C6	1.373 (2)	C4—H4	0.9300
C2—C3	1.376 (2)	C7—C8	1.485 (2)
C2—C1	1.489 (2)	C7—H7A	0.9700
C1—O2	1.199 (2)	C7—H7B	0.9700
C3—C4	1.371 (2)	C8—C8i	1.523 (3)
C3—H3	0.9300	C8—H8A	0.9700
C6—C5	1.376 (2)	C8—H8B	0.9700
C6—H6	0.9300	C5—H5	0.9300
C1—O1—C7	116.16 (14)	C3—C4—H4	117.9
C6—C2—C3	117.66 (16)	O1—C7—C8	107.95 (14)
C6—C2—C1	123.43 (17)	O1—C7—H7A	110.1
C3—C2—C1	118.91 (17)	C8—C7—H7A	110.1
O2—C1—O1	123.51 (18)	O1—C7—H7B	110.1
O2—C1—C2	123.57 (18)	C8—C7—H7B	110.1
O1—C1—C2	112.93 (16)	H7A—C7—H7B	108.4
C4—C3—C2	119.25 (17)	C7—C8—C8i	111.34 (19)
C4—C3—H3	120.4	C7—C8—H8A	109.4
C2—C3—H3	120.4	C8i—C8—H8A	109.4
C2—C6—C5	118.30 (18)	C7—C8—H8B	109.4
C2—C6—H6	120.9	C8i—C8—H8B	109.4
C5—C6—H6	120.9	H8A—C8—H8B	108.0
C4—N1—C5	115.97 (17)	N1—C5—C6	124.61 (18)
N1—C4—C3	124.21 (18)	N1—C5—H5	117.7
N1—C4—H4	117.9	C6—C5—H5	117.7
C7—O1—C1—O2	0.3 (3)	C3—C2—C6—C5	0.6 (3)
C7—O1—C1—C2	−179.81 (14)	C1—C2—C6—C5	−179.81 (17)
C6—C2—C1—O2	176.70 (18)	C5—N1—C4—C3	−0.3 (3)
C3—C2—C1—O2	−3.7 (3)	C2—C3—C4—N1	0.2 (3)
C6—C2—C1—O1	−3.2 (2)	C1—O1—C7—C8	−175.01 (15)
C3—C2—C1—O1	176.39 (15)	O1—C7—C8—C8i	174.67 (17)
C6—C2—C3—C4	−0.3 (3)	C4—N1—C5—C6	0.6 (3)
C1—C2—C3—C4	−179.94 (16)	C2—C6—C5—N1	−0.7 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1.