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

Tan, Z.; Bing, Y.; Fang, S.; Kai, Z.; Yan, Y.

doi:10.1107/S1600536809024799

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1758

doi:10.1107/S1600536809024799

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

Zhengde Tan,^a ^* Yi Bing,^a Shen Fang,^a Zhao Kai ^b and Yang Yan ^a

^aCollege of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, People's Republic of China, and ^bGuangxi Institute of Standards and Technology, Nanning 530022, People's Republic of China
^*Correspondence e-mail: tzd0517@163.com

(Received 7 June 2009; accepted 27 June 2009; online 4 July 2009)

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, P c a 2₁
a = 24.921 (2) Å
b = 4.3735 (6) Å
c = 11.1723 (14) Å
V = 1217.7 (2) Å³
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[F² > 2σ(F²)] = 0.051
wR(F²) = 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)

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

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024799/hg2522sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024799/hg2522Isup2.hkl

checkCIF report

Comment top

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)

Related literature top

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

Experimental top

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.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top

	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

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

Crystal data top

C₁₂H₇Cl₂FN₂O	F(000) = 576
M_r = 285.10	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0703P)² + 0.2751P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.140	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.21 e Å⁻³
1959 reflections	Δρ_min = −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	Absolute structure parameter: −0.04 (12)

Crystal data top

C₁₂H₇Cl₂FN₂O	V = 1217.7 (2) Å³
M_r = 285.10	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 24.921 (2) Å	µ = 0.53 mm⁻¹
b = 4.3735 (6) Å	T = 298 K
c = 11.1723 (14) Å	0.45 × 0.33 × 0.31 mm

Data collection top

Bruker SMART CCD diffractometer	1959 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1582 reflections with I > 2σ(I)
T_min = 0.796, T_max = 0.852	R_int = 0.066
5652 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.140	Δρ_max = 0.21 e Å⁻³
S = 1.08	Δρ_min = −0.20 e Å⁻³
1959 reflections	Absolute structure: Flack (1983), 826 Friedel pairs
163 parameters	Absolute structure parameter: −0.04 (12)
1 restraint

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₂H₇Cl₂FN₂O
M_r	285.10
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	298
a, b, c (Å)	24.921 (2), 4.3735 (6), 11.1723 (14)
V (Å³)	1217.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.45 × 0.33 × 0.31

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.796, 0.852
No. of measured, independent and observed [I > 2σ(I)] reflections	5652, 1959, 1582
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.140, 1.08
No. of reflections	1959
No. of parameters	163
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20
Absolute structure	Flack (1983), 826 Friedel pairs
Absolute structure parameter	−0.04 (12)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.86	2.17	2.606 (5)	111.4

Acknowledgements

The authors thank the Science Foundation of Hunan Institute of Engineering for support.

References

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Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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