(E)-1-(Pyridin-4-yl)propan-1-one O-tosyl oxime

Eitel, M.; Schollmeyer, D.; Koch, P.

doi:10.1107/S2414314617016029

organic compounds

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ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171602

https://doi.org/10.1107/S2414314617016029

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(E)-1-(Pyridin-4-yl)propan-1-one O-tosyl oxime

Michael Eitel,^a Dieter Schollmeyer ^b and Pierre Koch ^a ^*

^aInstitute of Pharmaceutical Sciences, Department of Pharmaceutical and Medicinal Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany, and ^bDepartment of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, D-55099 Mainz, Germany
^*Correspondence e-mail: pierre.koch@uni-tuebingen.de

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 2 November 2017; accepted 6 November 2017; online 17 November 2017)

The title compound, C₁₅H₁₆N₂O₃S, was obtained by the reaction of (E)-1-(pyridin-4-yl)propan-1-one oxime and para-toluenesulfonic acid. The pyridine ring makes a dihedral angle of 54.70 (10)° with the benzene ring. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming a chain along the c-axis direction.

Keywords: crystal structure; pyridine; tosyl oxime; hydrogen bonding.

CCDC reference: 1584082

Structure description

The title compound (Fig. 1) was synthesized by the reaction of (E)-1-(pyridin-4-yl)propan-1-one oxime and para-toluenesulfonyl chloride. For the crystal structure of the starting material, see Eitel et al. (2016 ). The pyridine ring makes dihedral angles of 54.70 (10) and 14.06 (17)° with the benzene ring and the oxime plane, respectively. The dihedral angle between the benzene ring and the oxime plane is 68.38 (17)°. The orientation of the benzene ring is stabilized by an intramolecular C—H⋯O contact (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O13ⁱ	0.94	2.53	3.138 (3)	122
C3—H3⋯O13ⁱ	0.94	2.58	3.171 (3)	122
C20—H20⋯O14	0.94	2.56	2.929 (3)	104
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
Molecular structure of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level. The intramolecular C—H⋯O contact is drawn with a dashed line.

In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming a chain along the c-axis direction (Table 1, Fig. 2).

Figure 2
Partial packing diagram viewed along the a axis. Intramolecular C—H⋯O hydrogen bonds are shown with open dashed bonds. Intermolecular hydrogen bonds are indicated by dashed lines.

Synthesis and crystallization

para-Toluenesulfonyl chloride (6.76 g, 35.48 mmol) was added to a solution of (E)-4-propionylpyridine oxime (4.44 g, 29.56 mmol) in anhydrous pyridine (20 ml). After reaction for 21.5 h at 298 K, the solution was diluted with ice–water (100 ml) and stirred for a further 3 h. The resulting white solid was filtered off, washed with cold water and dried under vacuum (yield: 78%, 7.05 g). Crystals of the title compound suitable for X-ray determination were obtained by slow evaporation of a solution of the solid in methanol at 298 K.

¹H NMR (400 MHz, DMSO-d₆) δ 0.99 (t, ³J = 7.6 Hz, 3H), 2.41 (s, 3H), 2.81 (q, ³J = 7.6 Hz, 2H), 7.50 (d, ³J = 8.1 Hz, 2H), 7.56 (d, ³J = 5.8 Hz, 2H), 7.91 (d, ³J = 8.3 Hz, 2H), 8.67 (d, ³J = 5.8 Hz, 2H); ¹³C NMR (100 MHz, DMSO-d₆) δ 10.6, 20.5, 21.1, 121.1, 128.5, 130.1, 131.6, 139.5, 145.7, 150.5, 167.5.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₆N₂O₃S
M_r	304.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	213
a, b, c (Å)	14.9385 (12), 10.6630 (7), 9.7701 (7)
β (°)	100.044 (6)
V (Å³)	1532.4 (2)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.98
Crystal size (mm)	0.16 × 0.09 × 0.04

Data collection
Diffractometer	STOE IPDS 2T
Absorption correction	Integration (X-RED32; Stoe & Cie, 2006 )
No. of measured, independent and observed [I > 2σ(I)] reflections	10273, 2695, 1913
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.098, 0.98
No. of reflections	2695
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.36
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2006), SIR2004 (Burla et al., 2005 ) and SHELXL2013 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1584082

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314617016029/bt4065sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617016029/bt4065Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617016029/bt4065Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2006); cell refinement: X-AREA (Stoe & Cie, 2006); data reduction: X-RED32 (Stoe & Cie, 2006); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015).

(E)-1-(Pyridin-4-yl)propan-1-one O-tosyl oxime top

Crystal data top

C₁₅H₁₆N₂O₃S	F(000) = 640
M_r = 304.36	D_x = 1.319 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 14.9385 (12) Å	Cell parameters from 11862 reflections
b = 10.6630 (7) Å	θ = 3.0–67.8°
c = 9.7701 (7) Å	µ = 1.98 mm⁻¹
β = 100.044 (6)°	T = 213 K
V = 1532.4 (2) Å³	Plate, colourless
Z = 4	0.16 × 0.09 × 0.04 mm

Data collection top

STOE IPDS 2T diffractometer	2695 independent reflections
Radiation source: Incoatec microSource Cu	1913 reflections with I > 2σ(I)
X-ray mirror monochromator	R_int = 0.049
Detector resolution: 6.67 pixels mm^-1	θ_max = 67.5°, θ_min = 3.0°
rotation method scans	h = −16→17
Absorption correction: integration (X-RED32; Stoe & Cie, 2006)	k = −12→11
	l = −11→11
10273 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.059P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
2695 reflections	Δρ_max = 0.16 e Å⁻³
192 parameters	Δρ_min = −0.36 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
C1	0.89270 (13)	0.47865 (18)	0.5899 (2)	0.0378 (4)
C2	0.85364 (15)	0.5811 (2)	0.6446 (2)	0.0508 (6)
H2	0.8009	0.6182	0.5945	0.061*
C3	0.89270 (16)	0.6283 (2)	0.7731 (2)	0.0564 (6)
H3	0.8646	0.6973	0.8080	0.068*
N4	0.96781 (13)	0.58192 (18)	0.85057 (19)	0.0532 (5)
C5	1.00375 (15)	0.4829 (2)	0.7992 (2)	0.0523 (6)
H5	1.0559	0.4470	0.8527	0.063*
C6	0.96963 (14)	0.4280 (2)	0.6714 (2)	0.0446 (5)
H6	0.9984	0.3576	0.6407	0.054*
C7	0.85434 (12)	0.42844 (18)	0.4487 (2)	0.0370 (4)
C8	0.88195 (13)	0.30317 (18)	0.3995 (2)	0.0427 (5)
H8A	0.9445	0.2846	0.4442	0.051*
H8B	0.8802	0.3062	0.2989	0.051*
C9	0.81924 (17)	0.1994 (2)	0.4332 (3)	0.0588 (6)
H9A	0.8192	0.1982	0.5325	0.088*
H9B	0.8406	0.1192	0.4048	0.088*
H9C	0.7580	0.2146	0.3839	0.088*
N10	0.79590 (11)	0.50387 (16)	0.37916 (16)	0.0414 (4)
O11	0.75806 (9)	0.44884 (12)	0.24519 (13)	0.0446 (4)
S12	0.69674 (4)	0.55354 (5)	0.15352 (5)	0.04410 (17)
O13	0.74961 (11)	0.66367 (15)	0.14888 (17)	0.0594 (4)
O14	0.66291 (11)	0.48672 (16)	0.02890 (14)	0.0575 (4)
C15	0.60796 (14)	0.58428 (18)	0.2447 (2)	0.0397 (5)
C16	0.61762 (15)	0.67382 (19)	0.3494 (2)	0.0487 (6)
H16	0.6721	0.7191	0.3730	0.058*
C17	0.54569 (16)	0.6953 (2)	0.4183 (2)	0.0533 (6)
H17	0.5523	0.7549	0.4902	0.064*
C18	0.46367 (15)	0.6310 (2)	0.3839 (2)	0.0499 (5)
C19	0.45625 (16)	0.5429 (2)	0.2783 (2)	0.0534 (6)
H19	0.4013	0.4988	0.2531	0.064*
C20	0.52712 (15)	0.5181 (2)	0.2093 (2)	0.0491 (5)
H20	0.5209	0.4570	0.1390	0.059*
C21	0.38537 (18)	0.6580 (3)	0.4576 (3)	0.0722 (8)
H21A	0.4066	0.7077	0.5400	0.108*
H21B	0.3602	0.5797	0.4843	0.108*
H21C	0.3388	0.7041	0.3960	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0354 (10)	0.0375 (11)	0.0398 (10)	−0.0010 (8)	0.0050 (8)	0.0063 (8)
C2	0.0493 (12)	0.0450 (13)	0.0520 (13)	0.0080 (9)	−0.0081 (10)	−0.0068 (10)
C3	0.0612 (14)	0.0496 (14)	0.0524 (13)	0.0021 (11)	−0.0070 (11)	−0.0078 (10)
N4	0.0531 (11)	0.0562 (12)	0.0454 (10)	−0.0067 (9)	−0.0049 (9)	0.0039 (9)
C5	0.0438 (11)	0.0648 (16)	0.0445 (12)	−0.0008 (11)	−0.0029 (10)	0.0139 (11)
C6	0.0405 (11)	0.0498 (13)	0.0432 (11)	0.0056 (9)	0.0064 (9)	0.0107 (9)
C7	0.0348 (10)	0.0368 (11)	0.0396 (10)	0.0015 (8)	0.0073 (8)	0.0029 (8)
C8	0.0414 (11)	0.0405 (12)	0.0460 (12)	0.0071 (8)	0.0072 (9)	0.0013 (9)
C9	0.0687 (15)	0.0399 (13)	0.0725 (16)	0.0007 (11)	0.0256 (13)	0.0015 (11)
N10	0.0430 (9)	0.0414 (10)	0.0366 (9)	0.0012 (7)	−0.0021 (7)	−0.0042 (7)
O11	0.0497 (8)	0.0421 (8)	0.0380 (7)	0.0065 (6)	−0.0030 (6)	−0.0032 (6)
S12	0.0470 (3)	0.0438 (3)	0.0385 (3)	0.0016 (2)	−0.0009 (2)	0.0049 (2)
O13	0.0589 (10)	0.0530 (10)	0.0644 (10)	−0.0093 (7)	0.0053 (8)	0.0152 (8)
O14	0.0606 (9)	0.0725 (11)	0.0357 (8)	0.0066 (8)	−0.0019 (7)	−0.0085 (7)
C15	0.0439 (10)	0.0331 (11)	0.0382 (10)	0.0030 (8)	−0.0039 (8)	0.0026 (8)
C16	0.0495 (12)	0.0333 (11)	0.0575 (13)	0.0011 (9)	−0.0071 (10)	−0.0068 (10)
C17	0.0588 (13)	0.0425 (13)	0.0554 (14)	0.0104 (10)	0.0013 (11)	−0.0113 (10)
C18	0.0519 (12)	0.0478 (13)	0.0483 (12)	0.0140 (10)	0.0040 (10)	0.0084 (10)
C19	0.0456 (12)	0.0599 (15)	0.0522 (13)	−0.0089 (10)	0.0017 (10)	0.0020 (11)
C20	0.0541 (13)	0.0480 (13)	0.0419 (11)	−0.0076 (10)	−0.0012 (10)	−0.0076 (9)
C21	0.0684 (17)	0.0771 (19)	0.0743 (18)	0.0219 (14)	0.0213 (14)	0.0099 (14)

Geometric parameters (Å, º) top

C1—C6	1.388 (3)	N10—O11	1.4557 (19)
C1—C2	1.388 (3)	O11—S12	1.6129 (13)
C1—C7	1.497 (3)	S12—O13	1.4204 (16)
C2—C3	1.384 (3)	S12—O14	1.4250 (15)
C2—H2	0.9400	S12—C15	1.752 (2)
C3—N4	1.334 (3)	C15—C16	1.388 (3)
C3—H3	0.9400	C15—C20	1.389 (3)
N4—C5	1.323 (3)	C16—C17	1.383 (3)
C5—C6	1.392 (3)	C16—H16	0.9400
C5—H5	0.9400	C17—C18	1.393 (3)
C6—H6	0.9400	C17—H17	0.9400
C7—N10	1.290 (2)	C18—C19	1.386 (3)
C7—C8	1.501 (3)	C18—C21	1.504 (3)
C8—C9	1.522 (3)	C19—C20	1.376 (3)
C8—H8A	0.9800	C19—H19	0.9400
C8—H8B	0.9800	C20—H20	0.9400
C9—H9A	0.9700	C21—H21A	0.9700
C9—H9B	0.9700	C21—H21B	0.9700
C9—H9C	0.9700	C21—H21C	0.9700

C6—C1—C2	116.52 (18)	N10—O11—S12	108.31 (11)
C6—C1—C7	122.35 (19)	O13—S12—O14	120.16 (10)
C2—C1—C7	121.12 (16)	O13—S12—O11	108.96 (9)
C3—C2—C1	119.8 (2)	O14—S12—O11	102.17 (9)
C3—C2—H2	120.1	O13—S12—C15	109.62 (10)
C1—C2—H2	120.1	O14—S12—C15	109.92 (9)
N4—C3—C2	124.0 (2)	O11—S12—C15	104.72 (8)
N4—C3—H3	118.0	C16—C15—C20	120.4 (2)
C2—C3—H3	118.0	C16—C15—S12	120.83 (16)
C5—N4—C3	115.96 (19)	C20—C15—S12	118.73 (16)
N4—C5—C6	124.5 (2)	C17—C16—C15	118.9 (2)
N4—C5—H5	117.8	C17—C16—H16	120.6
C6—C5—H5	117.8	C15—C16—H16	120.6
C1—C6—C5	119.2 (2)	C16—C17—C18	121.8 (2)
C1—C6—H6	120.4	C16—C17—H17	119.1
C5—C6—H6	120.4	C18—C17—H17	119.1
N10—C7—C1	112.18 (17)	C19—C18—C17	117.8 (2)
N10—C7—C8	125.77 (18)	C19—C18—C21	121.2 (2)
C1—C7—C8	122.04 (16)	C17—C18—C21	121.0 (2)
C7—C8—C9	111.33 (18)	C20—C19—C18	121.8 (2)
C7—C8—H8A	109.4	C20—C19—H19	119.1
C9—C8—H8A	109.4	C18—C19—H19	119.1
C7—C8—H8B	109.4	C19—C20—C15	119.4 (2)
C9—C8—H8B	109.4	C19—C20—H20	120.3
H8A—C8—H8B	108.0	C15—C20—H20	120.3
C8—C9—H9A	109.5	C18—C21—H21A	109.5
C8—C9—H9B	109.5	C18—C21—H21B	109.5
H9A—C9—H9B	109.5	H21A—C21—H21B	109.5
C8—C9—H9C	109.5	C18—C21—H21C	109.5
H9A—C9—H9C	109.5	H21A—C21—H21C	109.5
H9B—C9—H9C	109.5	H21B—C21—H21C	109.5
C7—N10—O11	110.08 (16)

C6—C1—C2—C3	1.0 (3)	N10—O11—S12—O14	−178.64 (12)
C7—C1—C2—C3	−177.5 (2)	N10—O11—S12—C15	−64.00 (13)
C1—C2—C3—N4	0.5 (4)	O13—S12—C15—C16	−29.48 (19)
C2—C3—N4—C5	−1.7 (4)	O14—S12—C15—C16	−163.63 (16)
C3—N4—C5—C6	1.5 (3)	O11—S12—C15—C16	87.28 (17)
C2—C1—C6—C5	−1.3 (3)	O13—S12—C15—C20	149.92 (16)
C7—C1—C6—C5	177.30 (19)	O14—S12—C15—C20	15.77 (19)
N4—C5—C6—C1	0.0 (3)	O11—S12—C15—C20	−93.32 (16)
C6—C1—C7—N10	−166.03 (19)	C20—C15—C16—C17	0.4 (3)
C2—C1—C7—N10	12.5 (3)	S12—C15—C16—C17	179.80 (16)
C6—C1—C7—C8	14.8 (3)	C15—C16—C17—C18	−1.0 (3)
C2—C1—C7—C8	−166.7 (2)	C16—C17—C18—C19	0.6 (3)
N10—C7—C8—C9	−87.7 (3)	C16—C17—C18—C21	−178.4 (2)
C1—C7—C8—C9	91.4 (2)	C17—C18—C19—C20	0.4 (3)
C1—C7—N10—O11	−177.79 (15)	C21—C18—C19—C20	179.4 (2)
C8—C7—N10—O11	1.3 (3)	C18—C19—C20—C15	−1.0 (3)
C7—N10—O11—S12	−171.97 (13)	C16—C15—C20—C19	0.6 (3)
N10—O11—S12—O13	53.22 (14)	S12—C15—C20—C19	−178.83 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O13ⁱ	0.94	2.53	3.138 (3)	122
C3—H3···O13ⁱ	0.94	2.58	3.171 (3)	122
C20—H20···O14	0.94	2.56	2.929 (3)	104

Symmetry code: (i) x, −y+3/2, z+1/2.

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Eitel, M., Schollmeyer, D. & Koch, P. (2016). IUCrData, 1, x160803. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (2006). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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(E)-1-(Pyridin-4-yl)propan-1-one O-tosyl oxime

Structure description

Synthesis and crystallization

Refinement

Structural data

References

organic compounds