Synthesis and crystal structure of 2-[(2,3,5,6-tetra­fluoro­pyridin-4-yl)amino]­ethyl methacrylate

Overstreet, S.M.J.; Genzia, I.M.; Nguyen, A.; Auleciems, Z.J.; Jennings, A.R.; Peloquin, A.J.

doi:10.1107/S2056989023004334

research communications

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ISSN: 2056-9890

Volume 79| Part 6| June 2023| Pages 571-574

https://doi.org/10.1107/S2056989023004334

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Synthesis and crystal structure of 2-[(2,3,5,6-tetrafluoropyridin-4-yl)amino]ethyl methacrylate

Shayla M. J. Overstreet,^a Ian M. Genzia,^a Alexander Nguyen,^a Zachary J. Auleciems,^a Abby R. Jennings ^a ^* and Andrew J. Peloquin ^a ^*

^aDepartment of Chemistry, United States Air Force Academy, Colorado Springs, CO 80840, USA
^*Correspondence e-mail: abby.jennings@afacademy.af.edu, andrew.j.peloquin4.mil@mail.mil

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 9 May 2023; accepted 18 May 2023; online 26 May 2023)

In the title compound, C₁₁H₁₀F₄N₂O₂, the conformation about the N—C—C—O bond is gauche [torsion angle = 61.84 (13)°]. In the crystal, N—H⋯O hydrogen bonds link the molecules into [010] chains, which are cross-linked by C—H⋯F and C—H⋯π contacts. Hirshfeld surface analysis was conducted to aid in the visualization of these various influences on the packing. This analysis showed that the largest contribution to the surface contacts arises from F⋯H/H⋯F interactions (35.6%), followed by O⋯H/H⋯O (17.8%) and H⋯H (12.7%).

Keywords: crystal structure; perfluoropyridine; C—H⋯F interaction.

CCDC reference: 2263932

1. Chemical context

Perfluoropyridine (C₅NF₅; PFPy) is an ideal candidate to use in the preparation of complex fluorinated compounds and materials as PFPy is reactive towards nucleophilic addition (Sandford, 2012 ). Furthermore, our group and others have demonstrated that this addition can be regio-selectively controlled, with stoichiometric addition to the 4-(para-) position being exclusive with a broad range of nucleophiles (Brittain & Cobb, 2019 ; Peloquin et al., 2020 ; Seyb & Kerres, 2013 ). Sequential addition can also be accomplished at the 3,5-(meta-) positions (Corley et al., 2019 ; Houck et al., 2021 ). As part of our ongoing work in this area, the synthesis and single-crystal structure of the title compound, C₁₁H₁₀F₄N₂O₂, is reported herein.

2. Structural commentary

The title compound (Fig. 1) crystallizes in the monoclinic space group P2₁/n with one molecule in the asymmetric unit. The N2—C6 bond is rotated by only 15.81 (8)° from the C1–C5/N1 ring plane, presumably to encourage conjugation of the nitrogen atom lone pair with the aromatic ring π system, which is reflected in the C3—N2 bond length of 1.3522 (16) Å; the C3—N2—C6—C7 torsion angle is −81.68 (16)°. The amine nitrogen atom (N2) and ester oxygen atom (O1) are gauche to one another, with N2—C6—C7—O1 = 61.84 (13)°. The C10 methyl group is oriented in such a fashion as to enable a weak C—H⋯π interaction with the aromatic ring of an adjacent molecule (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg11 is the centroid of the C1–C5/N1 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—HN2⋯O2ⁱ	0.811 (18)	2.119 (17)	2.8296 (15)	146.3 (15)
C6—H6B⋯F3	0.99	2.23	2.9004 (15)	124
C7—H7B⋯F3ⁱⁱ	0.99	2.57	3.5368 (15)	167
C7—H7B⋯F4ⁱⁱ	0.99	2.63	3.3646 (16)	131
C7—H7A⋯Cg1ⁱⁱⁱ	0.99	2.89	3.6047 (15)	130
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound (a) and the unit-cell packing (b). Displacement ellipsoids are shown at the 50% probability level.

3. Supramolecular features

The main directional interactions in the crystal structure of the title compound are of the type C—H⋯F, N—H⋯O and C—H⋯π (Table 1). The N—H⋯O hydrogen bonds link the molecules into [010] chains, with adjacent molecules related by a 2₁ screw axis. Weak hydrogen-bonding interactions are observed between one hydrogen atom bound to each carbon atom of the two-carbon (C6/C7) linker unit between the amine nitrogen atom and the ester, and F3 as acceptor. One of these interactions is intramolecular (C6—H6A⋯F3) with the other being intermolecular (C7—H7A⋯F3). A hydrogen-bonding interaction occurs between the secondary amine and the carbonyl oxygen atom (N2—H1N2⋯O2). Finally, a weak C—H⋯π interaction is observed between H7B and the pyridine ring π system.

Hirshfeld surface analysis was used to investigate the presence of hydrogen bonds and intermolecular interactions in the crystal structure. The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (Spackman & McKinnon, 2002 ) were generated by CrystalExplorer17.5 (Turner et al., 2017 ), using standard surface resolution with the three-dimensional d_norm surfaces plotted over a fixed color scale of −0.025 (red) to 1.38 (blue) a.u.; the pale-red spots symbolize short contacts and negative d_norm values on the corresponding surface plots shown in Fig. 2, associated with their relative contributions to the Hirshfeld surface.

Figure 2
Map of d_norm (a) and shape index (b) onto the Hirshfeld surface for the title compound.

The largest contribution to the overall crystal packing is from F⋯H/H⋯F interactions (35.6%) (Table 2). However, the spike in the fingerprint plot (Fig. 3) associated with this contact is masked by that of the O⋯H/H⋯O contacts, which appears in the plot at 0.80 Å < (d_i + d_e) < 1.15 Å. The H⋯H and C⋯H/H⋯C contacts have the second and third largest contributions, at 17.8 and 12.7%, respectively. Smaller spikes on the shoulder of the fingerprint plot, appearing at 1.15 Å < (d_i + d_e) < 1.160 Å, correspond to the N⋯H/H⋯N contacts.

Table 2
Percentage contribution of inter-atomic contacts to the Hirshfeld surface of the title compound

Contact	Percentage contribution
F⋯H/H⋯F	35.6
H⋯H	17.8
C⋯H/H⋯C	12.7
N⋯H/H⋯N	8.7
O⋯H/H⋯O	8.7
F⋯F	6.3
O⋯C/C⋯O	2.5
F⋯O/O⋯F	2.4
F⋯N/N⋯F	1.8
C⋯F/F⋯C	1.7
C⋯C	1.4
N⋯C/C⋯N	0.3

Figure 3
The overall two-dimensional fingerprint plot for the title compound.

4. Database survey

A search of the November 2019 release of the Cambridge Structure Database (Groom et al., 2016 ), with updates through November 2012, was performed using the program ConQuest (Bruno et al., 2002 ). The search was limited to 2,3,5,6-tetrafluoropyridine-based compounds with a secondary amine nitrogen atom bound to the ring in the 4-position. This search resulted in 19 hits: the C—C—N—C torsion angles indicate planarity, presumably due to conjugation of the nitrogen atom lone pair into the pyridine ring π system, in the majority of cases. In cases of non-planarity, this is typically due to steric factors of the substituent on the nitrogen atom or conjugation of that nitrogen lone pair into the π system of the substituent. For example, in CSD refcode NIXMEN (Ranjbar-Karimi et al., 2008 ), the bulk of a phenyl ring attached to the nitrogen atom subsitutent discourages planarity, resulting in a torsion angle of 37.4°. In TAPRAD (Yamaguchi et al., 1992 ), the conjugation of the nitrogen lone pair is into a urea substituent, vice the pyridine ring, with a torsion angle of 38.7°.

5. Synthesis and crystallization

2-[(Perfluoropyridin-4-yl)amino]ethan-1-ol was synthesized using a known method and used without further purification (Peloquin, et al., 2020). Methacryloyl chloride was purchased from Sigma and distilled under reduced pressure prior to use.

A 500 ml round-bottom flask equipped with an addition funnel was charged with 2-[(perfluoropyridin-4-yl)amino]ethan-1-ol (13.4 g, 62.3 mmol), trimethylamine (10.7 ml, 77.2 mmol) and diethyl ether (300 ml). The solution was stirred under nitrogen at 273–278 K for 15 minutes. Next, a solution of methacrylol chloride (7.50 ml, 76.8 mmol) in ether (10 ml) was added dropwise to the round-bottom flask using an addition funnel. The solution was allowed to gradually warm to room temperature and was stirred for 96 h under nitrogen. Precipitated salts were removed by vacuum filtration and the filtrate was concentrated under reduced pressure. Crystals of the title compound in the form of colorless needles were obtained by recrystallization from a solution in warm (∼328 K) hexanes (9.0 g, 50.7%): m.p. 335–336 K; ¹H NMR (500 MHz, CDCl₃): δ 6.01 (s, vinyl, 1H), 5.61 (s, vinyl, 1H), 4.90 (bs, –NHCH₂CH₂O–, 1H), 4.38 (t, –NHCH₂CH₂O–, 2H, ³J = 5.0 Hz), 3.86 (q, –NHCH₂CH₂O–, 2H, ³J = 5.3 Hz), 1.93 (s, CH₂=C(CH₃)–, 3H); ¹⁹F NMR (471 MHz, CDCl₃): δ −93.6 (bs, 2F), −163.4 (bs, 2F); ¹³C NMR (125 MHz, CDCl₃): δ 167.8 (C=O), 135.8 (CH₂=C(CH₃)-), 126.4 [CH₂=C(CH₃)–], 63.7 (–OCH₂CH₂NH–), 44.1 (–OCH₂CH₂NH–), 18.3 [CH₂=C(CH₃)–].

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. N-bound H atoms were refined freely. C-bound H atoms were positioned geometrically (C—H = 0.95–0.99 Å) and refined as riding with U_iso(H) = 1.2–1.5U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₁H₁₀F₄N₂O₂
M_r	278.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	106
a, b, c (Å)	6.8588 (1), 10.7797 (2), 15.7707 (2)
β (°)	91.251 (1)
V (Å³)	1165.74 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.15
Crystal size (mm)	0.44 × 0.18 × 0.17

Data collection
Diffractometer	XtaLAB Synergy, Single source at offset/far, HyPix3000
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.705, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	33062, 2583, 2211
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.090, 1.06
No. of reflections	2583
No. of parameters	177
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.21
Computer programs: APEX3 and SAINT (Bruker, 2017 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2263932

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004334/hb8066sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004334/hb8066Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023004334/hb8066Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 v2017.3-0 (Bruker, 2017); cell refinement: SAINT V8.38A (Bruker, 2017); data reduction: SAINT V8.38A (Bruker, 2017); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

2-[(2,3,5,6-Tetrafluoropyridin-4-yl)amino]ethyl 2-methylprop-2-enoate top

Crystal data top

C₁₁H₁₀F₄N₂O₂	F(000) = 568
M_r = 278.21	D_x = 1.585 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.8588 (1) Å	Cell parameters from 19836 reflections
b = 10.7797 (2) Å	θ = 2.3–27.2°
c = 15.7707 (2) Å	µ = 0.15 mm⁻¹
β = 91.251 (1)°	T = 106 K
V = 1165.74 (3) Å³	Needle, colourless
Z = 4	0.44 × 0.18 × 0.17 mm

Data collection top

XtaLAB Synergy, Single source at offset/far, HyPix3000 diffractometer	2211 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.035
φ and ω scans	θ_max = 27.4°, θ_min = 2.3°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2019)	h = −8→8
T_min = 0.705, T_max = 1.000	k = −13→13
33062 measured reflections	l = −19→20
2583 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0389P)² + 0.4834P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2583 reflections	Δρ_max = 0.28 e Å⁻³
177 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints

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
F1	0.76605 (14)	0.04660 (8)	0.49959 (5)	0.0400 (2)
F2	0.49913 (12)	0.06997 (8)	0.37165 (5)	0.0334 (2)
F3	0.92779 (11)	0.36294 (8)	0.24890 (5)	0.0301 (2)
F4	1.17024 (11)	0.32149 (9)	0.37827 (5)	0.0364 (2)
O1	0.53522 (13)	0.47979 (9)	0.28749 (6)	0.0261 (2)
O2	0.30721 (15)	0.62510 (10)	0.30633 (7)	0.0391 (3)
N1	0.96939 (17)	0.18455 (11)	0.43992 (7)	0.0296 (3)
N2	0.56174 (17)	0.22514 (11)	0.23936 (7)	0.0267 (3)
C1	0.8023 (2)	0.12386 (13)	0.43516 (8)	0.0293 (3)
C2	0.66735 (19)	0.13523 (12)	0.37096 (8)	0.0258 (3)
C3	0.69653 (18)	0.21724 (12)	0.30299 (8)	0.0228 (3)
C4	0.87510 (19)	0.28051 (12)	0.30859 (8)	0.0241 (3)
C5	0.99991 (19)	0.25973 (13)	0.37622 (8)	0.0274 (3)
C6	0.53726 (19)	0.32687 (13)	0.17900 (8)	0.0266 (3)
H6A	0.468848	0.295683	0.127349	0.032*
H6B	0.667341	0.356903	0.162348	0.032*
C7	0.42353 (19)	0.43344 (13)	0.21475 (8)	0.0272 (3)
H7A	0.406113	0.499531	0.171663	0.033*
H7B	0.293237	0.405086	0.232375	0.033*
C8	0.45919 (19)	0.57648 (13)	0.32828 (9)	0.0276 (3)
C9	0.5847 (2)	0.61826 (14)	0.40162 (9)	0.0306 (3)
C10	0.7559 (2)	0.54178 (16)	0.42728 (10)	0.0417 (4)
H10A	0.843816	0.534069	0.379396	0.063*
H10B	0.711927	0.459166	0.444381	0.063*
H10C	0.825125	0.581580	0.475012	0.063*
C11	0.5387 (3)	0.72537 (16)	0.43920 (10)	0.0430 (4)
H11A	0.617410	0.756041	0.484859	0.052*
H11B	0.427248	0.770700	0.420212	0.052*
HN2	0.467 (3)	0.1814 (16)	0.2450 (10)	0.032 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0534 (6)	0.0383 (5)	0.0284 (4)	0.0099 (4)	0.0041 (4)	0.0129 (4)
F2	0.0342 (5)	0.0303 (4)	0.0360 (5)	−0.0056 (3)	0.0052 (3)	0.0048 (3)
F3	0.0244 (4)	0.0381 (5)	0.0277 (4)	−0.0070 (3)	−0.0027 (3)	0.0070 (3)
F4	0.0247 (4)	0.0491 (5)	0.0351 (5)	−0.0030 (4)	−0.0091 (3)	−0.0017 (4)
O1	0.0213 (5)	0.0304 (5)	0.0264 (5)	0.0017 (4)	−0.0040 (4)	0.0011 (4)
O2	0.0270 (5)	0.0447 (6)	0.0453 (6)	0.0115 (5)	−0.0054 (4)	0.0008 (5)
N1	0.0328 (6)	0.0332 (6)	0.0228 (6)	0.0102 (5)	−0.0038 (5)	−0.0007 (5)
N2	0.0236 (6)	0.0292 (6)	0.0270 (6)	−0.0065 (5)	−0.0051 (4)	0.0039 (5)
C1	0.0382 (8)	0.0281 (7)	0.0216 (6)	0.0111 (6)	0.0035 (5)	0.0028 (5)
C2	0.0276 (7)	0.0241 (6)	0.0260 (6)	0.0012 (5)	0.0038 (5)	−0.0004 (5)
C3	0.0229 (6)	0.0238 (6)	0.0217 (6)	0.0024 (5)	−0.0001 (5)	−0.0018 (5)
C4	0.0242 (6)	0.0263 (6)	0.0217 (6)	0.0012 (5)	0.0001 (5)	0.0008 (5)
C5	0.0228 (6)	0.0329 (7)	0.0265 (7)	0.0043 (5)	−0.0034 (5)	−0.0047 (6)
C6	0.0243 (6)	0.0342 (7)	0.0211 (6)	−0.0043 (5)	−0.0051 (5)	0.0044 (5)
C7	0.0203 (6)	0.0345 (7)	0.0266 (7)	−0.0031 (5)	−0.0062 (5)	0.0062 (6)
C8	0.0227 (6)	0.0309 (7)	0.0295 (7)	0.0034 (5)	0.0021 (5)	0.0065 (6)
C9	0.0310 (7)	0.0341 (7)	0.0269 (7)	0.0055 (6)	0.0005 (5)	0.0016 (6)
C10	0.0419 (9)	0.0459 (9)	0.0369 (8)	0.0100 (7)	−0.0106 (7)	−0.0114 (7)
C11	0.0490 (10)	0.0442 (9)	0.0356 (8)	0.0130 (7)	−0.0057 (7)	−0.0044 (7)

Geometric parameters (Å, º) top

F1—C1	1.3413 (16)	C4—C5	1.3714 (18)
F2—C2	1.3516 (15)	C6—H6A	0.9900
F3—C4	1.3495 (15)	C6—H6B	0.9900
F4—C5	1.3444 (16)	C6—C7	1.505 (2)
O1—C7	1.4540 (15)	C7—H7A	0.9900
O1—C8	1.3367 (17)	C7—H7B	0.9900
O2—C8	1.2105 (16)	C8—C9	1.4961 (19)
N1—C1	1.3201 (19)	C9—C10	1.484 (2)
N1—C5	1.3111 (18)	C9—C11	1.339 (2)
N2—C3	1.3522 (16)	C10—H10A	0.9800
N2—C6	1.4594 (17)	C10—H10B	0.9800
N2—HN2	0.811 (18)	C10—H10C	0.9800
C1—C2	1.3625 (19)	C11—H11A	0.9500
C2—C3	1.4072 (18)	C11—H11B	0.9500
C3—C4	1.4030 (18)

C8—O1—C7	116.31 (10)	C7—C6—H6A	109.1
C5—N1—C1	114.56 (11)	C7—C6—H6B	109.1
C3—N2—C6	126.76 (11)	O1—C7—C6	106.82 (10)
C3—N2—HN2	114.8 (11)	O1—C7—H7A	110.4
C6—N2—HN2	115.4 (12)	O1—C7—H7B	110.4
F1—C1—C2	118.98 (13)	C6—C7—H7A	110.4
N1—C1—F1	116.09 (12)	C6—C7—H7B	110.4
N1—C1—C2	124.93 (13)	H7A—C7—H7B	108.6
F2—C2—C1	120.90 (12)	O1—C8—C9	112.50 (11)
F2—C2—C3	117.95 (11)	O2—C8—O1	122.86 (13)
C1—C2—C3	121.13 (12)	O2—C8—C9	124.62 (13)
N2—C3—C2	119.91 (12)	C10—C9—C8	118.83 (13)
N2—C3—C4	126.72 (12)	C11—C9—C8	117.68 (13)
C4—C3—C2	113.32 (11)	C11—C9—C10	123.46 (14)
F3—C4—C3	121.52 (11)	C9—C10—H10A	109.5
F3—C4—C5	118.55 (12)	C9—C10—H10B	109.5
C5—C4—C3	119.92 (12)	C9—C10—H10C	109.5
F4—C5—C4	117.72 (12)	H10A—C10—H10B	109.5
N1—C5—F4	116.16 (11)	H10A—C10—H10C	109.5
N1—C5—C4	126.12 (13)	H10B—C10—H10C	109.5
N2—C6—H6A	109.1	C9—C11—H11A	120.0
N2—C6—H6B	109.1	C9—C11—H11B	120.0
N2—C6—C7	112.48 (11)	H11A—C11—H11B	120.0
H6A—C6—H6B	107.8

F1—C1—C2—F2	−0.02 (19)	C1—N1—C5—C4	1.0 (2)
F1—C1—C2—C3	178.48 (11)	C1—C2—C3—N2	178.87 (12)
F2—C2—C3—N2	−2.59 (18)	C1—C2—C3—C4	1.25 (18)
F2—C2—C3—C4	179.79 (11)	C2—C3—C4—F3	179.97 (11)
F3—C4—C5—F4	−1.19 (18)	C2—C3—C4—C5	−0.49 (18)
F3—C4—C5—N1	178.86 (12)	C3—N2—C6—C7	−81.68 (16)
O1—C8—C9—C10	−8.07 (19)	C3—C4—C5—F4	179.25 (11)
O1—C8—C9—C11	170.13 (13)	C3—C4—C5—N1	−0.7 (2)
O2—C8—C9—C10	173.30 (15)	C5—N1—C1—F1	−179.66 (11)
O2—C8—C9—C11	−8.5 (2)	C5—N1—C1—C2	−0.2 (2)
N1—C1—C2—F2	−179.47 (12)	C6—N2—C3—C2	160.42 (13)
N1—C1—C2—C3	−1.0 (2)	C6—N2—C3—C4	−22.3 (2)
N2—C3—C4—F3	2.5 (2)	C7—O1—C8—O2	−0.88 (19)
N2—C3—C4—C5	−177.92 (13)	C7—O1—C8—C9	−179.54 (11)
N2—C6—C7—O1	61.78 (13)	C8—O1—C7—C6	179.42 (11)
C1—N1—C5—F4	−178.91 (11)

Hydrogen-bond geometry (Å, º) top

Cg11 is the centroid of the C1–C5/N1 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···O2ⁱ	0.811 (18)	2.119 (17)	2.8296 (15)	146.3 (15)
C6—H6B···F3	0.99	2.23	2.9004 (15)	124
C7—H7B···F3ⁱⁱ	0.99	2.57	3.5368 (15)	167
C7—H7B···F4ⁱⁱ	0.99	2.63	3.3646 (16)	131
C7—H7A···Cg1ⁱⁱⁱ	0.99	2.89	3.6047 (15)	130

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x−1, y, z; (iii) −x+3/2, y+1/2, −z+1/2.

Percentage contribution of inter-atomic contacts to the Hirshfeld surface of the title compound top

Contact	Percentage contribution
F···H/H···F	35.6
H···H	17.8
C···H/H···C	12.7
N···H/H···N	8.7
O···H/H···O	8.7
F···F	6.3
O···C/C···O	2.5
F···O/O···F	2.4
F···N/N···F	1.8
C···F/F···C	1.7
C···C	1.4
N···C/C···N	0.3

Funding information

Funding for this research was provided by: Air Force Office of Scientific Research.

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Volume 79| Part 6| June 2023| Pages 571-574

https://doi.org/10.1107/S2056989023004334

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Synthesis and crystal structure of 2-[(2,3,5,6-tetra­fluoro­pyridin-4-yl)amino]­ethyl methacrylate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Funding information

References

research communications

Synthesis and crystal structure of 2-[(2,3,5,6-tetrafluoropyridin-4-yl)amino]ethyl methacrylate

3. Supramolecular features