Crystal structure of N-{4-[(6-chloro-pyridin-3-yl)meth-oxy]phen-yl}-2,6-di-fluoro-benzamide.

In the title compound, C19H13ClF2N2O2, the conformation of the N-H bond in the amide segment is anti to the C=O bond. The mol-ecule is not planar, with dihedral angles between the central benzene ring and the outer benzene and pyridyl rings of 73.35 (7) and 81.26 (6)°, respectively. A weak intra-molecular C-H⋯O hydrogen bond occurs. In the crystal, N-H⋯N, C-H⋯O and C-H⋯F hydrogen bonds lead to the formation of dimers. The N-H⋯N inversion dimers are linked by π-π contacts between adjacent pyridine rings [centroid-centroid = 3.8541 (12) Å] and C-H⋯π inter-actions. These contacts combine to stack the mol-ecules along the a axis.

Chemical context

Amide derivatives show diverse biological properties, acting as insecticides (Liu et al., 2004a ▸), fungicides (Liu et al., 2004b ▸) and acaricides (Shiga et al., 2003 ▸). Amides in regular commercial use include benzamide (flutolanil, fluopicolide), nicotinamide (boscalid) and thia­zole carboxamide (thifluzamide, ethaboxam). As a part of our work on the synthesis of novel fluorine-containing compounds with good biological activities, we report herein on the crystal structure of the title compound,(I), Fig. 1 ▸.

Figure 1

The structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Structural commentary

The conformation of the N—H and the C=O bonds in the amide segment are anti to one another, similar to the conformation observed in another amide compound (Gowda et al., 2010 ▸). The dihedral angle between the two benzene rings is 73.35 (6)° while that between the central benzene ring and the chloro-substituted pyridine ring is 81.26 (6). The amide residue C1/N1/C7/O1 lies close to the plane of the central benzene ring, making a dihedral angle of 8.73 (6)°. A weak intra­molecular C9—H9⋯O1 hydrogen bond (Table 1 ▸) contrib­utes to the planarity of this part of the mol­ecule.

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1	0.93	2.27	2.863 (2)	121
N1—H1⋯N2i	0.88 (2)	2.24 (2)	3.109 (2)	170.6 (18)
C19—H19⋯F2ii	0.93	2.54	3.309 (2)	140
C14—H14B⋯O1ii	0.97	2.42	3.344 (3)	160
C16—H16⋯Cg2iii	0.93	2.99	3.912 (2)	173

Symmetry codes: (i) ; (ii) ; (iii) .

Supra­molecular features

In the crystal structure, pairs of classical N1—H1⋯N2i hydrogen bonds, Table 1 ▸, link the mol­ecules into inversion dimers and generate (22) rings (Bernstein et al., 1995 ▸). C14—H14B⋯O1ii and C19—H19⋯F2ii hydrogen bonds also form dimers, which enclose an (10) ring motif, Fig. 2 ▸. The N—H⋯N dimers are linked into chains along the c-axis direction by π–π stacking inter­actions between adjacent pyridyl rings [Cg1⋯Cg1iv = 3.8541 (12) Å; symmetry code: (iv) 1 − x, 1 − y, 1 − z] augmented by a weak C16—H16⋯Cg2 contact (Cg2 is the centroid of the C1–C6 benzene ring), Table 1 ▸, Fig. 3 ▸. These contacts combine to stack the mol­ecules along the a axis, Fig. 4 ▸.

Figure 2

A pair of dimers with hydrogen bonds drawn as blue dashed lines.

Figure 3

Chains of inversion dimers along the c-axis direction. Hydrogen bonds are drawn as dashed lines with π–π and C—H⋯π contacts shown as green dotted lines.

Figure 4

The overall packing for (I) viewed along the a-axis direction.

Synthesis and crystallization

Tri­ethyl­amine (6mmol) was added dropwise to a stirred solution of 4-(6-chloro­pyridin-3-yl) meth­oxy aniline (5mmol) and 2,6-di­fluoro­benzoyl chloride (5mmol) in dry di­chloro­methane (20ml) at 275-277 K. The mixture was stirred at 283–288 K for 2 h, then washed with 0.5% hydro­chloric acid solution, and a saturated aqueous solution of sodium hydrogen carbonate, dried and evaporated. The residue was recrystallized from di­chloro­methane, giving colourless blocks of the title compound after three weeks.

Database survey

A search of the Cambridge Structural Database (Version 5.36 with three updates) (Groom & Allen, 2014 ▸) for N-(4-(pyridin-3-ylmeth­oxy)phen­yl)benzamide or its substituted derivatives gave no hits. However, structures of eight substituted 2,6-di­fluoro-N-phenyl­benzamide derivatives were found, see for example Cockroft et al. (2007 ▸); Spitaleri et al. (2004 ▸); Fun et al. (2010 ▸). Two structures of purely organic 3-(phen­oxy­meth­yl)pyridine derivatives have also been reported (Lakshminarayana et al., 2009 ▸; Liu et al., 2010 ▸) together with that of a cadmium complex of 4-[(6-chloro­pyridin-3-yl)meth­oxy]benz­oate, Li et al. (2007 ▸).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The NH H atom was located in a difference Fourier map and freely refined. The C-bound H atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93–0.97 Å and U iso(H) = 1.2U eq(C).

Table 2

Experimental details

Crystal data
Chemical formula	C19H13ClF2N2O2
M r	374.76
Crystal system, space group	Triclinic, P
Temperature (K)	298
a, b, c (Å)	8.8173 (11), 10.7036 (13), 10.8452 (14)
α, β, γ (°)	61.939 (2), 77.597 (2), 69.636 (2)
V (Å3)	845.15 (18)
Z	2
Radiation type	Mo Kα
μ (mm−1)	0.26
Crystal size (mm)	0.16 × 0.12 × 0.10
Data collection
Diffractometer	Bruker SMART APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001 ▸)
T min, T max	0.959, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	5474, 3271, 2886
R int	0.029
(sin θ/λ)max (Å−1)	0.617
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.045, 0.116, 1.06
No. of reflections	3271
No. of parameters	239
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.21, −0.23

Computer programs: SMART and SAINT (Bruker, 2000 ▸), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015023701/sj5486sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023701/sj5486Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015023701/sj5486Isup3.cml

CCDC reference: 1441555

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H13ClF2N2O2	Z = 2
Mr = 374.76	F(000) = 384
Triclinic, P1	Dx = 1.473 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8173 (11) Å	Cell parameters from 2810 reflections
b = 10.7036 (13) Å	θ = 2.3–28.3°
c = 10.8452 (14) Å	µ = 0.26 mm−1
α = 61.939 (2)°	T = 298 K
β = 77.597 (2)°	Block, colorless
γ = 69.636 (2)°	0.16 × 0.12 × 0.10 mm
V = 845.15 (18) Å3

Bruker SMART APEX CCD area-detector diffractometer	3271 independent reflections
Radiation source: fine-focus sealed tube	2886 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
Tmin = 0.959, Tmax = 0.974	k = −13→13
5474 measured reflections	l = −12→13

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0526P)2 + 0.196P] where P = (Fo2 + 2Fc2)/3
3271 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.7630 (2)	0.2167 (2)	−0.02643 (18)	0.0427 (4)
C2	0.8270 (2)	0.1167 (2)	−0.08394 (19)	0.0478 (4)
C3	0.9422 (3)	0.1317 (3)	−0.1918 (2)	0.0611 (6)
H3	0.9816	0.0618	−0.2276	0.073*
C4	0.9982 (3)	0.2526 (3)	−0.2461 (2)	0.0706 (7)
H4	1.0773	0.2644	−0.3195	0.085*
C5	0.9403 (3)	0.3566 (3)	−0.1949 (2)	0.0750 (7)
H5	0.9787	0.4388	−0.2327	0.090*
C6	0.8239 (3)	0.3360 (2)	−0.0861 (2)	0.0602 (5)
C7	0.6521 (2)	0.1886 (2)	0.10413 (18)	0.0432 (4)
C8	0.3644 (2)	0.21024 (17)	0.18987 (17)	0.0391 (4)
C9	0.3813 (2)	0.1688 (2)	0.32952 (18)	0.0462 (4)
H9	0.4817	0.1503	0.3590	0.055*
C10	0.2489 (2)	0.1551 (2)	0.42425 (18)	0.0461 (4)
H10	0.2609	0.1273	0.5176	0.055*
C11	0.0990 (2)	0.18196 (17)	0.38294 (18)	0.0408 (4)
C12	0.0809 (2)	0.2233 (2)	0.24416 (19)	0.0470 (4)
H12	−0.0198	0.2422	0.2149	0.056*
C13	0.2140 (2)	0.2363 (2)	0.14935 (18)	0.0461 (4)
H13	0.2019	0.2631	0.0563	0.055*
C14	−0.1851 (2)	0.2030 (2)	0.4525 (2)	0.0497 (5)
H14A	−0.2488	0.1521	0.5341	0.060*
H14B	−0.1861	0.1737	0.3806	0.060*
C15	−0.2607 (2)	0.36755 (19)	0.40005 (18)	0.0414 (4)
C16	−0.2680 (2)	0.4370 (2)	0.4829 (2)	0.0498 (5)
H16	−0.2264	0.3819	0.5710	0.060*
C17	−0.3362 (2)	0.5864 (2)	0.4347 (2)	0.0506 (5)
H17	−0.3418	0.6348	0.4885	0.061*
C18	−0.3961 (2)	0.6622 (2)	0.3043 (2)	0.0479 (4)
C19	−0.3260 (2)	0.4551 (2)	0.2721 (2)	0.0503 (5)
H19	−0.3230	0.4098	0.2161	0.060*
Cl1	−0.48341 (8)	0.85162 (6)	0.23999 (7)	0.0783 (2)
F1	0.77345 (18)	−0.00346 (13)	−0.02627 (13)	0.0741 (4)
F2	0.7661 (2)	0.43493 (16)	−0.03160 (16)	0.1031 (6)
N1	0.49454 (18)	0.22686 (16)	0.08547 (16)	0.0430 (4)
H1	0.468 (2)	0.265 (2)	−0.001 (2)	0.052*
N2	−0.3942 (2)	0.60203 (18)	0.22226 (16)	0.0537 (4)
O1	0.71012 (17)	0.1345 (2)	0.21658 (15)	0.0727 (5)
O2	−0.02172 (15)	0.16015 (14)	0.48849 (13)	0.0495 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0410 (9)	0.0482 (10)	0.0375 (9)	−0.0112 (8)	−0.0013 (7)	−0.0189 (8)
C2	0.0514 (11)	0.0483 (10)	0.0415 (10)	−0.0084 (8)	−0.0054 (8)	−0.0207 (8)
C3	0.0524 (12)	0.0763 (15)	0.0463 (11)	0.0010 (11)	−0.0033 (9)	−0.0335 (11)
C4	0.0484 (12)	0.116 (2)	0.0456 (12)	−0.0288 (13)	0.0066 (9)	−0.0342 (13)
C5	0.0860 (17)	0.1005 (19)	0.0517 (13)	−0.0615 (15)	0.0073 (12)	−0.0240 (13)
C6	0.0785 (15)	0.0630 (13)	0.0489 (11)	−0.0310 (11)	0.0043 (10)	−0.0278 (10)
C7	0.0470 (10)	0.0465 (9)	0.0385 (9)	−0.0125 (8)	−0.0001 (8)	−0.0220 (8)
C8	0.0434 (9)	0.0330 (8)	0.0364 (9)	−0.0069 (7)	0.0014 (7)	−0.0159 (7)
C9	0.0425 (10)	0.0540 (10)	0.0408 (10)	−0.0085 (8)	−0.0032 (8)	−0.0230 (8)
C10	0.0508 (11)	0.0483 (10)	0.0347 (9)	−0.0076 (8)	−0.0026 (8)	−0.0188 (8)
C11	0.0453 (10)	0.0322 (8)	0.0391 (9)	−0.0062 (7)	0.0016 (7)	−0.0160 (7)
C12	0.0423 (10)	0.0523 (10)	0.0444 (10)	−0.0092 (8)	−0.0041 (8)	−0.0219 (9)
C13	0.0512 (11)	0.0480 (10)	0.0355 (9)	−0.0090 (8)	−0.0030 (8)	−0.0188 (8)
C14	0.0457 (10)	0.0462 (10)	0.0515 (11)	−0.0141 (8)	0.0055 (8)	−0.0194 (9)
C15	0.0353 (9)	0.0447 (9)	0.0424 (9)	−0.0120 (7)	0.0045 (7)	−0.0198 (8)
C16	0.0479 (11)	0.0540 (11)	0.0457 (10)	−0.0101 (8)	−0.0079 (8)	−0.0214 (9)
C17	0.0483 (11)	0.0552 (11)	0.0573 (12)	−0.0160 (9)	0.0002 (9)	−0.0321 (10)
C18	0.0379 (9)	0.0427 (9)	0.0550 (11)	−0.0123 (7)	0.0062 (8)	−0.0179 (9)
C19	0.0544 (11)	0.0524 (11)	0.0444 (10)	−0.0118 (9)	0.0011 (8)	−0.0254 (9)
Cl1	0.0732 (4)	0.0415 (3)	0.0948 (5)	−0.0080 (2)	0.0032 (3)	−0.0186 (3)
F1	0.1111 (11)	0.0569 (7)	0.0632 (8)	−0.0301 (7)	0.0031 (7)	−0.0322 (6)
F2	0.1807 (18)	0.0716 (9)	0.0786 (10)	−0.0650 (11)	0.0283 (10)	−0.0444 (8)
N1	0.0453 (9)	0.0451 (8)	0.0327 (8)	−0.0082 (6)	−0.0008 (6)	−0.0161 (7)
N2	0.0541 (10)	0.0527 (9)	0.0428 (9)	−0.0079 (7)	−0.0019 (7)	−0.0173 (7)
O1	0.0500 (8)	0.1190 (14)	0.0444 (8)	−0.0210 (9)	−0.0008 (7)	−0.0348 (9)
O2	0.0436 (7)	0.0507 (7)	0.0411 (7)	−0.0063 (6)	0.0034 (5)	−0.0170 (6)

C1—C6	1.374 (3)	C11—O2	1.377 (2)
C1—C2	1.382 (2)	C11—C12	1.383 (2)
C1—C7	1.504 (2)	C12—C13	1.384 (2)
C2—F1	1.344 (2)	C12—H12	0.9300
C2—C3	1.361 (3)	C13—H13	0.9300
C3—C4	1.366 (3)	C14—O2	1.432 (2)
C3—H3	0.9300	C14—C15	1.508 (2)
C4—C5	1.368 (4)	C14—H14A	0.9700
C4—H4	0.9300	C14—H14B	0.9700
C5—C6	1.374 (3)	C15—C19	1.371 (3)
C5—H5	0.9300	C15—C16	1.391 (2)
C6—F2	1.347 (2)	C16—C17	1.368 (3)
C7—O1	1.217 (2)	C16—H16	0.9300
C7—N1	1.336 (2)	C17—C18	1.372 (3)
C8—C13	1.381 (3)	C17—H17	0.9300
C8—C9	1.390 (2)	C18—N2	1.316 (2)
C8—N1	1.423 (2)	C18—Cl1	1.7328 (19)
C9—C10	1.379 (2)	C19—N2	1.345 (2)
C9—H9	0.9300	C19—H19	0.9300
C10—C11	1.378 (3)	N1—H1	0.88 (2)
C10—H10	0.9300
C6—C1—C2	115.21 (17)	C11—C12—C13	119.36 (17)
C6—C1—C7	121.35 (16)	C11—C12—H12	120.3
C2—C1—C7	122.93 (16)	C13—C12—H12	120.3
F1—C2—C3	119.06 (18)	C8—C13—C12	121.47 (16)
F1—C2—C1	117.06 (16)	C8—C13—H13	119.3
C3—C2—C1	123.86 (19)	C12—C13—H13	119.3
C2—C3—C4	118.0 (2)	O2—C14—C15	111.33 (15)
C2—C3—H3	121.0	O2—C14—H14A	109.4
C4—C3—H3	121.0	C15—C14—H14A	109.4
C3—C4—C5	121.5 (2)	O2—C14—H14B	109.4
C3—C4—H4	119.3	C15—C14—H14B	109.4
C5—C4—H4	119.3	H14A—C14—H14B	108.0
C4—C5—C6	118.1 (2)	C19—C15—C16	116.97 (17)
C4—C5—H5	121.0	C19—C15—C14	122.83 (17)
C6—C5—H5	121.0	C16—C15—C14	120.19 (16)
F2—C6—C1	116.98 (18)	C17—C16—C15	119.99 (17)
F2—C6—C5	119.7 (2)	C17—C16—H16	120.0
C1—C6—C5	123.4 (2)	C15—C16—H16	120.0
O1—C7—N1	125.21 (17)	C16—C17—C18	117.59 (17)
O1—C7—C1	118.93 (16)	C16—C17—H17	121.2
N1—C7—C1	115.86 (15)	C18—C17—H17	121.2
C13—C8—C9	118.73 (16)	N2—C18—C17	124.97 (17)
C13—C8—N1	117.80 (15)	N2—C18—Cl1	116.22 (15)
C9—C8—N1	123.47 (16)	C17—C18—Cl1	118.81 (15)
C10—C9—C8	119.84 (17)	N2—C19—C15	124.31 (17)
C10—C9—H9	120.1	N2—C19—H19	117.8
C8—C9—H9	120.1	C15—C19—H19	117.8
C11—C10—C9	121.11 (16)	C7—N1—C8	127.66 (15)
C11—C10—H10	119.4	C7—N1—H1	116.4 (13)
C9—C10—H10	119.4	C8—N1—H1	115.9 (13)
O2—C11—C10	115.23 (15)	C18—N2—C19	116.17 (17)
O2—C11—C12	125.25 (16)	C11—O2—C14	118.83 (14)
C10—C11—C12	119.49 (16)
C6—C1—C2—F1	178.43 (17)	C10—C11—C12—C13	0.3 (3)
C7—C1—C2—F1	6.5 (3)	C9—C8—C13—C12	0.6 (3)
C6—C1—C2—C3	0.0 (3)	N1—C8—C13—C12	−179.67 (16)
C7—C1—C2—C3	−171.90 (18)	C11—C12—C13—C8	−0.6 (3)
F1—C2—C3—C4	−178.15 (19)	O2—C14—C15—C19	123.96 (19)
C1—C2—C3—C4	0.2 (3)	O2—C14—C15—C16	−56.7 (2)
C2—C3—C4—C5	−0.4 (3)	C19—C15—C16—C17	−0.8 (3)
C3—C4—C5—C6	0.3 (4)	C14—C15—C16—C17	179.80 (17)
C2—C1—C6—F2	−179.11 (18)	C15—C16—C17—C18	0.3 (3)
C7—C1—C6—F2	−7.1 (3)	C16—C17—C18—N2	0.6 (3)
C2—C1—C6—C5	−0.1 (3)	C16—C17—C18—Cl1	179.99 (14)
C7—C1—C6—C5	171.9 (2)	C16—C15—C19—N2	0.7 (3)
C4—C5—C6—F2	178.9 (2)	C14—C15—C19—N2	−179.97 (17)
C4—C5—C6—C1	0.0 (4)	O1—C7—N1—C8	−1.5 (3)
C6—C1—C7—O1	−77.8 (3)	C1—C7—N1—C8	178.76 (15)
C2—C1—C7—O1	93.7 (2)	C13—C8—N1—C7	−170.21 (16)
C6—C1—C7—N1	102.0 (2)	C9—C8—N1—C7	9.5 (3)
C2—C1—C7—N1	−86.6 (2)	C17—C18—N2—C19	−0.7 (3)
C13—C8—C9—C10	−0.3 (3)	Cl1—C18—N2—C19	179.84 (14)
N1—C8—C9—C10	−179.98 (16)	C15—C19—N2—C18	0.1 (3)
C8—C9—C10—C11	0.0 (3)	C10—C11—O2—C14	172.31 (14)
C9—C10—C11—O2	178.18 (16)	C12—C11—O2—C14	−9.6 (2)
C9—C10—C11—C12	0.0 (3)	C15—C14—O2—C11	−78.49 (19)
O2—C11—C12—C13	−177.66 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1	0.93	2.27	2.863 (2)	121
N1—H1···N2i	0.88 (2)	2.24 (2)	3.109 (2)	170.6 (18)
C19—H19···F2ii	0.93	2.54	3.309 (2)	140
C14—H14B···O1ii	0.97	2.42	3.344 (3)	160
C16—H16···Cg2iii	0.93	2.99	3.912 (2)	173