3,6-Dichloro-N-(4-fluoro­phen­yl)picolinamide

Abstract

In the title compound, C₁₂H₇Cl₂FN₂O, the dihedral angle between the phenyl and pyridine rings is 42.5 (2) Å and an intramolecular N—H⋯N hydrogen bond occurs. The crystal structure is stabilized by C—H⋯O, C—H⋯F and C—Cl short contacts.

Related literature

For the chemical and pharmacological properties of amides, see: Liu et al. (2005 ▶); Sladowska & Sieklucka-Dziuba (1999 ▶).

Experimental

Crystal data

• C₁₂H₇Cl₂FN₂O

• M _r = 285.10

• Orthorhombic,

• a = 24.921 (2) Å

• b = 4.3735 (6) Å

• c = 11.1723 (14) Å

• V = 1217.7 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.53 mm⁻¹

• T = 298 K

• 0.45 × 0.33 × 0.31 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.796, T _max = 0.852

• 5652 measured reflections

• 1959 independent reflections

• 1582 reflections with I > 2σ(I)

• R _int = 0.066

Refinement

• R[F ² > 2σ(F ²)] = 0.051

• wR(F ²) = 0.140

• S = 1.08

• 1959 reflections

• 163 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

• Absolute structure: Flack (1983 ▶), 826 Friedel pairs

• Flack parameter: −0.04 (12)

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.86	2.17	2.606 (5)	111

supplementary crystallographic information

Comment

The chemical and pharmacological properties of acid amides have investigated extensively, owing to their chelating ability with metal ions and to their potentially beneficial chemical and biological activties (Liu et al.,2005; Sladowska et al., 1999). As part of our studies on the synthesis and characterization of these compounds, we report here the synthesis and crystal structure of 3,6-dichloro-N-(4-fluorophenyl)picolinamide. The C=O bond length is 1.200 (5) Å, indicating that the molecule is in the keto form. In the crystal structure, the molecules are stabilized by intramolecular N—H···N hydrogen bonds and C—H···O, C—H···F, C—Cl short contact.(Table 1 and Fig 2)

Experimental

A solution of 3,6-dichloropicolinoyl chloride(10 mmol) in 50 ml toluene was added to a solution of 4-fluorobenzenamine (10 mmol) in 10 ml toluene. The reaction mixture was refluxed for 1 h with stirring then the resulting white precipitate was obtained by filtration, washed several times with ethanol and dried in vacuo(yield 90%). Elemental analysis calculated:C, 50.55; H, 2.47; N, 9.83%; found: C, 50.52; H, 2.49; N, 9.82%. Crystals were obtained by slow evaporation of a solution in methanol after one week.

Refinement

H atoms were placed geometrically and refined using a riding model, with C—H=0.93 Å,N—H=0.86 Å, respectively, and U_iso(H) = 1.2U_eq(N) and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.

Fig. 2.

Crystal packing of the title compound, showing the hydrogen bonds as dashed lines

Crystal data

C12H7Cl2FN2O	F(000) = 576
Mr = 285.10	Dx = 1.555 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1638 reflections
a = 24.921 (2) Å	θ = 2.9–27.0°
b = 4.3735 (6) Å	µ = 0.53 mm−1
c = 11.1723 (14) Å	T = 298 K
V = 1217.7 (2) Å3	Block, colorless
Z = 4	0.45 × 0.33 × 0.31 mm

Data collection

Bruker SMART CCD diffractometer	1959 independent reflections
Radiation source: fine-focus sealed tube	1582 reflections with I > 2σ(I)
graphite	Rint = 0.066
φ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→26
Tmin = 0.796, Tmax = 0.852	k = −5→5
5652 measured reflections	l = −13→11

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.051	w = 1/[σ2(Fo2) + (0.0703P)2 + 0.2751P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.140	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.21 e Å−3
1959 reflections	Δρmin = −0.20 e Å−3
163 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
1 restraint	Extinction coefficient: 0.064 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 826 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.04 (12)

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
Cl1	0.29548 (4)	0.3691 (3)	0.97142 (12)	0.0657 (4)
Cl2	0.10409 (7)	0.8942 (4)	0.69084 (13)	0.0830 (5)
N1	0.14698 (14)	0.5722 (9)	0.8609 (3)	0.0479 (9)
N2	0.11700 (14)	0.2081 (9)	1.0330 (3)	0.0468 (9)
H2	0.0985	0.2817	0.9747	0.056*
F1	−0.00073 (16)	−0.4220 (10)	1.3695 (4)	0.1088 (14)
O1	0.20091 (13)	0.1700 (12)	1.1055 (4)	0.0917 (17)
C1	0.17010 (17)	0.2639 (11)	1.0316 (4)	0.0491 (11)
C2	0.18767 (17)	0.4557 (11)	0.9264 (4)	0.0449 (11)
C3	0.24053 (16)	0.5164 (10)	0.8958 (4)	0.0430 (10)
C4	0.2520 (2)	0.7023 (11)	0.7983 (4)	0.0523 (11)
H4	0.2873	0.7439	0.7771	0.063*
C5	0.2098 (2)	0.8244 (12)	0.7333 (5)	0.0566 (12)
H5	0.2157	0.9518	0.6680	0.068*
C6	0.15852 (18)	0.7482 (11)	0.7701 (4)	0.0493 (11)
C7	0.08862 (17)	0.0410 (10)	1.1205 (4)	0.0418 (10)
C8	0.1042 (2)	0.0484 (13)	1.2409 (5)	0.0595 (13)
H8	0.1342	0.1585	1.2654	0.071*
C9	0.0732 (2)	−0.1150 (15)	1.3226 (5)	0.0756 (17)
H9	0.0829	−0.1168	1.4030	0.091*
C10	0.0290 (2)	−0.2722 (14)	1.2864 (6)	0.0714 (16)
C11	0.0144 (2)	−0.2826 (13)	1.1691 (6)	0.0688 (15)
H11	−0.0155	−0.3947	1.1457	0.083*
C12	0.04429 (18)	−0.1262 (13)	1.0851 (5)	0.0559 (13)
H12	0.0346	−0.1332	1.0048	0.067*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0458 (6)	0.0924 (10)	0.0588 (7)	0.0066 (6)	0.0025 (6)	0.0119 (8)
Cl2	0.0762 (9)	0.0970 (11)	0.0756 (10)	−0.0019 (8)	−0.0244 (8)	0.0324 (9)
N1	0.052 (2)	0.050 (2)	0.042 (2)	−0.0034 (18)	0.0024 (18)	0.0056 (19)
N2	0.0447 (19)	0.055 (2)	0.040 (2)	−0.0029 (17)	−0.0053 (16)	0.0082 (18)
F1	0.110 (3)	0.108 (3)	0.108 (3)	−0.014 (2)	0.051 (2)	0.036 (2)
O1	0.048 (2)	0.148 (5)	0.079 (3)	0.003 (2)	−0.0076 (18)	0.068 (3)
C1	0.044 (2)	0.055 (3)	0.048 (3)	0.003 (2)	0.000 (2)	0.007 (2)
C2	0.047 (2)	0.055 (3)	0.032 (2)	0.005 (2)	0.0023 (18)	0.000 (2)
C3	0.049 (2)	0.043 (2)	0.037 (2)	−0.0003 (19)	0.0002 (19)	−0.0018 (18)
C4	0.056 (3)	0.058 (3)	0.043 (3)	−0.007 (2)	0.009 (2)	0.001 (2)
C5	0.071 (3)	0.057 (3)	0.042 (3)	−0.008 (2)	0.001 (2)	0.011 (2)
C6	0.054 (3)	0.052 (3)	0.042 (3)	−0.003 (2)	−0.006 (2)	0.001 (2)
C7	0.047 (2)	0.037 (2)	0.042 (3)	0.0010 (19)	0.009 (2)	0.0005 (19)
C8	0.054 (3)	0.073 (4)	0.052 (3)	−0.004 (3)	0.003 (2)	0.005 (3)
C9	0.082 (4)	0.096 (5)	0.049 (3)	0.008 (3)	0.017 (3)	0.018 (3)
C10	0.072 (4)	0.065 (4)	0.078 (4)	0.004 (3)	0.034 (3)	0.017 (3)
C11	0.053 (3)	0.062 (3)	0.092 (5)	−0.010 (2)	0.017 (3)	−0.001 (3)
C12	0.049 (3)	0.062 (3)	0.057 (3)	−0.007 (2)	0.003 (2)	−0.002 (2)

Geometric parameters (Å, °)

Cl1—C3	1.734 (4)	C4—H4	0.9300
Cl2—C6	1.741 (5)	C5—C6	1.383 (6)
N1—C6	1.305 (6)	C5—H5	0.9300
N1—C2	1.351 (6)	C7—C12	1.383 (7)
N2—C1	1.346 (5)	C7—C8	1.400 (7)
N2—C7	1.411 (6)	C8—C9	1.393 (7)
N2—H2	0.8600	C8—H8	0.9300
F1—C10	1.356 (6)	C9—C10	1.361 (9)
O1—C1	1.200 (5)	C9—H9	0.9300
C1—C2	1.508 (6)	C10—C11	1.360 (9)
C2—C3	1.387 (6)	C11—C12	1.379 (8)
C3—C4	1.389 (6)	C11—H11	0.9300
C4—C5	1.385 (7)	C12—H12	0.9300
C6—N1—C2	118.6 (4)	N1—C6—Cl2	116.1 (3)
C1—N2—C7	126.5 (4)	C5—C6—Cl2	118.7 (4)
C1—N2—H2	116.7	C12—C7—C8	120.6 (4)
C7—N2—H2	116.7	C12—C7—N2	118.4 (4)
O1—C1—N2	124.0 (4)	C8—C7—N2	120.9 (4)
O1—C1—C2	122.7 (4)	C9—C8—C7	117.6 (5)
N2—C1—C2	113.3 (4)	C9—C8—H8	121.2
N1—C2—C3	120.5 (4)	C7—C8—H8	121.2
N1—C2—C1	114.5 (4)	C10—C9—C8	120.9 (5)
C3—C2—C1	125.1 (4)	C10—C9—H9	119.5
C2—C3—C4	120.1 (4)	C8—C9—H9	119.5
C2—C3—Cl1	124.0 (3)	F1—C10—C11	119.9 (6)
C4—C3—Cl1	115.9 (3)	F1—C10—C9	118.9 (6)
C5—C4—C3	118.7 (4)	C11—C10—C9	121.3 (5)
C5—C4—H4	120.6	C10—C11—C12	119.7 (5)
C3—C4—H4	120.6	C10—C11—H11	120.2
C6—C5—C4	116.9 (5)	C12—C11—H11	120.2
C6—C5—H5	121.6	C11—C12—C7	119.9 (5)
C4—C5—H5	121.6	C11—C12—H12	120.0
N1—C6—C5	125.2 (5)	C7—C12—H12	120.0
C7—N2—C1—O1	1.7 (8)	C2—N1—C6—Cl2	−179.2 (3)
C7—N2—C1—C2	−178.8 (4)	C4—C5—C6—N1	0.2 (8)
C6—N1—C2—C3	−1.6 (7)	C4—C5—C6—Cl2	−179.6 (4)
C6—N1—C2—C1	178.1 (4)	C1—N2—C7—C12	−147.3 (5)
O1—C1—C2—N1	−172.2 (5)	C1—N2—C7—C8	33.9 (7)
N2—C1—C2—N1	8.3 (6)	C12—C7—C8—C9	−0.7 (8)
O1—C1—C2—C3	7.5 (8)	N2—C7—C8—C9	178.1 (5)
N2—C1—C2—C3	−172.0 (4)	C7—C8—C9—C10	−0.9 (9)
N1—C2—C3—C4	1.1 (7)	C8—C9—C10—F1	−178.5 (5)
C1—C2—C3—C4	−178.5 (4)	C8—C9—C10—C11	2.0 (10)
N1—C2—C3—Cl1	−178.1 (3)	F1—C10—C11—C12	179.1 (5)
C1—C2—C3—Cl1	2.3 (7)	C9—C10—C11—C12	−1.4 (9)
C2—C3—C4—C5	0.1 (7)	C10—C11—C12—C7	−0.2 (8)
Cl1—C3—C4—C5	179.3 (4)	C8—C7—C12—C11	1.3 (8)
C3—C4—C5—C6	−0.7 (7)	N2—C7—C12—C11	−177.5 (4)
C2—N1—C6—C5	0.9 (7)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.86	2.17	2.606 (5)	111