N-(5-Chloro-2-nitro­phen­yl)-2,2-di­methyl­propanamide

Zhang, F.; Fang, Z.; Zou, B.-H.; Kai, G.

doi:10.1107/S1600536812027730

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2771

doi:10.1107/S1600536812027730

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N-(5-Chloro-2-nitrophenyl)-2,2-dimethylpropanamide

Feng Zhang,^a Zheng Fang,^a Bao-Hua Zou ^a and Guo Kai ^b ^*

^aSchool of Pharmaceutical Sciences, Nanjing University of Technology, Puzhu South Road No. 30 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Puzhu South Road No. 30 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: kaiguo@njut.edu.cn

(Received 6 June 2012; accepted 19 June 2012; online 25 August 2012)

In the crystal structure of the title compound, C₁₁H₁₃ClN₂O₃, molecules are linked through C—H⋯O hydrogen bonds.

Related literature

For background to the biologically active molecule ezetimibe [systematic name: (3R,4S)-1-(4-fluorophenyl)-3-[(3S)-3-(4-fluorophenyl)-3-hydroxypropyl]-4-(4-hydroxyphenyl)azetidin-2-one, see: Rosenblum et al. (1998 ). For the preparation of the title compound, a derivative of an intermediate in the synthesis of ezetimibe, see: Wang et al. (2009). For a related structure, see: Zhu et al. (2007 ).

Experimental

Crystal data

C₁₁H₁₂ClN₂O₃
M_r = 255.68
Orthorhombic, P n m a
a = 10.401 (2) Å
b = 7.0280 (14) Å
c = 17.106 (3) Å
V = 1250.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.915, T_max = 0.970
2432 measured reflections
1244 independent reflections
643 reflections with I > 2σ(I)
R_int = 0.069
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.179
S = 1.00
1244 reflections
94 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O3ⁱ	0.96	2.35	3.294 (8)	167
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812027730/zj2083sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812027730/zj2083Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812027730/zj2083Isup3.cml

checkCIF report

Comment top

Ezetimibe is a biologically active molecule and reasearch has shown it to have the useful property of inhibiting the absorption of cholesterol from the intestine (Rosenblum et al., 1998) As part of our studies into the synthesis of Ezetimibe, the title compound N-(5-chloro-2-nitrophenyl)-2,2-dimethylpropanamide, (I), which is one of the derivates of a intermediate, is synthesized (Wang et al., 2009). In this paper we report the crystal structure of the title compound.

In the crystal structure,C—H···O hydrogen bonds interactions (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. It's just formed by the accumulation of Molecules.

Related literature top

For background to the biologically active molecule ezetimibe [systematic name: (3R,4S)-1-(4-fluorophenyl)-3-[(3S)-3-(4-fluorophenyl)-3-hydroxypropyl]-4-(4-hydroxyphenyl)azetidin-2-one, see: Rosenblum et al. (1998). For the preparation of the title compound, a derivative of an intermediate in the synthesis of ezetimibe, see: Wang et al. (2009). For a related structure, see: Zhu et al. (2007).

Experimental top

5-chloro-2-nitroaniline (C₆H₅ClN₂O₂, 20.64 g, 0.12 mol) in CH₂Cl₂(40 ml) was added 4-dimethylaminopyridine (C₇H₁₀N₂, 1.2 g, 0.01 mol) and Et₃N (42.3 ml, 0.31 mol) and cooled the reaction to 273 K. A solution of pivaloyl chloride (C₅H₉ClO, 14.4 g, 0.12 mol) in CH₂Cl₂ (150 ml) was added dropwise over 1 h and the mixture was heated to reflux. After 12 h, H₂O and H₂SO₄ (2 N, 75 ml) were added, separated the layers andwashed the organic layer sequentially with NaOH (10%), NaCl (satd) and water. Dried the organic layer over MgSO₄ and concentrated to obtain solid product as pure yellow solid. (Wang et al., 2009). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.

Fig. 2. A view of the unit cell packing of the title compound.

N-(5-Chloro-2-nitrophenyl)-2,2-dimethylpropanamide top

Crystal data top

C₁₁H₁₂ClN₂O₃	F(000) = 532
M_r = 255.68	D_x = 1.358 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 25 reflections
a = 10.401 (2) Å	θ = 9–12°
b = 7.0280 (14) Å	µ = 0.30 mm⁻¹
c = 17.106 (3) Å	T = 293 K
V = 1250.4 (4) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	643 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.069
Graphite monochromator	θ_max = 25.4°, θ_min = 2.3°
ω/2θ scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = −8→0
T_min = 0.915, T_max = 0.970	l = −20→20
2432 measured reflections	3 standard reflections every 200 reflections
1244 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.084P)²] where P = (F_o² + 2F_c²)/3
1244 reflections	(Δ/σ)_max < 0.001
94 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₁H₁₂ClN₂O₃	V = 1250.4 (4) Å³
M_r = 255.68	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 10.401 (2) Å	µ = 0.30 mm⁻¹
b = 7.0280 (14) Å	T = 293 K
c = 17.106 (3) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	643 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.069
T_min = 0.915, T_max = 0.970	3 standard reflections every 200 reflections
2432 measured reflections	intensity decay: 1%
1244 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 1.00	Δρ_max = 0.24 e Å⁻³
1244 reflections	Δρ_min = −0.22 e Å⁻³
94 parameters

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	Occ. (<1)
Cl	0.24447 (9)	0.2500	0.50682 (10)	0.0967 (6)
N1	0.7748 (5)	0.2500	0.3855 (3)	0.0880 (14)
C1	0.4982 (4)	0.2500	0.5237 (3)	0.0623 (11)
H1A	0.4794	0.2500	0.5769	0.075*
O1	0.7853 (5)	0.2500	0.3151 (3)	0.143 (2)
N2	0.7290 (3)	0.2500	0.5525 (2)	0.0706 (11)
H2A	0.8046	0.2500	0.5321	0.085*
O2	0.8711 (4)	0.2500	0.4258 (3)	0.1202 (15)
C2	0.4005 (4)	0.2500	0.4726 (3)	0.0664 (12)
O3	0.6267 (3)	0.2500	0.6688 (2)	0.1179 (16)
C3	0.4218 (5)	0.2500	0.3921 (3)	0.0824 (15)
H3A	0.3541	0.2500	0.3565	0.099*
C4	0.5469 (7)	0.2500	0.3681 (3)	0.0964 (18)
H4A	0.5640	0.2500	0.3147	0.116*
C5	0.6479 (4)	0.2500	0.4186 (3)	0.0732 (13)
C6	0.6275 (4)	0.2500	0.5004 (3)	0.0585 (11)
C7	0.7243 (4)	0.2500	0.6321 (3)	0.0720 (14)
C8	0.8531 (4)	0.2500	0.6754 (3)	0.0802 (15)
C9	0.9244 (4)	0.4286 (7)	0.6607 (3)	0.156
H9A	0.9438	0.4385	0.6060	0.233*
H9B	1.0029	0.4280	0.6902	0.233*
H9C	0.8726	0.5351	0.6763	0.233*
C10	0.8297 (7)	0.2500	0.7644 (4)	0.148 (3)
H10A	0.9098	0.2500	0.7922	0.222*
H10B	0.7814	0.3615	0.7780	0.222*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0576 (8)	0.0846 (10)	0.1478 (14)	0.000	−0.0208 (7)	0.000
N1	0.091 (3)	0.067 (3)	0.106 (4)	0.000	0.027 (3)	0.000
C1	0.066 (3)	0.043 (2)	0.078 (3)	0.000	−0.013 (3)	0.000
O1	0.168 (4)	0.172 (5)	0.089 (3)	0.000	0.042 (3)	0.000
N2	0.062 (2)	0.075 (3)	0.074 (3)	0.000	−0.001 (2)	0.000
O2	0.087 (3)	0.146 (4)	0.128 (4)	0.000	0.040 (3)	0.000
C2	0.053 (2)	0.045 (2)	0.101 (3)	0.000	−0.015 (2)	0.000
O3	0.060 (2)	0.215 (5)	0.078 (2)	0.000	−0.0037 (18)	0.000
C3	0.088 (4)	0.058 (3)	0.101 (4)	0.000	−0.038 (3)	0.000
C4	0.138 (5)	0.072 (4)	0.079 (4)	0.000	−0.017 (4)	0.000
C5	0.068 (3)	0.059 (3)	0.093 (4)	0.000	0.015 (3)	0.000
C6	0.061 (2)	0.041 (2)	0.074 (3)	0.000	0.000 (2)	0.000
C7	0.048 (2)	0.076 (4)	0.092 (4)	0.000	−0.011 (3)	0.000
C8	0.058 (3)	0.071 (3)	0.111 (4)	0.000	−0.012 (3)	0.000
C9	0.156	0.156	0.156	0.000	0.000	0.000
C10	0.132 (6)	0.175 (8)	0.136 (6)	0.000	−0.015 (5)	0.000

Geometric parameters (Å, º) top

Cl—C2	1.725 (4)	C3—H3A	0.9300
N1—O1	1.211 (6)	C4—C5	1.360 (7)
N1—O2	1.215 (6)	C4—H4A	0.9300
N1—C5	1.436 (6)	C5—C6	1.415 (6)
C1—C2	1.340 (6)	C7—C8	1.530 (6)
C1—C6	1.403 (6)	C8—C9	1.479 (5)
C1—H1A	0.9300	C8—C9ⁱ	1.479 (5)
N2—C7	1.363 (6)	C8—C10	1.540 (8)
N2—C6	1.381 (5)	C9—H9A	0.9600
N2—H2A	0.8600	C9—H9B	0.9600
C2—C3	1.396 (7)	C9—H9C	0.9600
O3—C7	1.194 (5)	C10—H10A	0.9600
C3—C4	1.365 (7)	C10—H10B	0.9600

O1—N1—O2	119.3 (5)	N2—C6—C1	123.3 (4)
O1—N1—C5	118.4 (6)	N2—C6—C5	121.6 (4)
O2—N1—C5	122.3 (5)	C1—C6—C5	115.1 (4)
C2—C1—C6	122.7 (4)	O3—C7—N2	123.8 (4)
C2—C1—H1A	118.6	O3—C7—C8	119.3 (5)
C6—C1—H1A	118.6	N2—C7—C8	116.9 (4)
C7—N2—C6	128.1 (4)	C9—C8—C9ⁱ	116.1 (5)
C7—N2—H2A	115.9	C9—C8—C7	110.8 (3)
C6—N2—H2A	115.9	C9ⁱ—C8—C7	110.8 (3)
C1—C2—C3	121.6 (4)	C9—C8—C10	104.3 (4)
C1—C2—Cl	119.5 (4)	C9ⁱ—C8—C10	104.3 (4)
C3—C2—Cl	118.9 (4)	C7—C8—C10	109.9 (5)
C4—C3—C2	116.6 (5)	C8—C9—H9A	109.5
C4—C3—H3A	121.7	C8—C9—H9B	109.5
C2—C3—H3A	121.7	H9A—C9—H9B	109.5
C5—C4—C3	123.0 (5)	C8—C9—H9C	109.5
C5—C4—H4A	118.5	H9A—C9—H9C	109.5
C3—C4—H4A	118.5	H9B—C9—H9C	109.5
C4—C5—C6	120.9 (4)	C8—C10—H10A	110.7
C4—C5—N1	117.3 (5)	C8—C10—H10B	108.8
C6—C5—N1	121.8 (5)	H10A—C10—H10B	109.5

C6—C1—C2—C3	0.000 (1)	C2—C1—C6—C5	0.000 (1)
C6—C1—C2—Cl	180.0	C4—C5—C6—N2	180.0
C1—C2—C3—C4	0.000 (1)	N1—C5—C6—N2	0.000 (1)
Cl—C2—C3—C4	180.0	C4—C5—C6—C1	0.0
C2—C3—C4—C5	0.000 (1)	N1—C5—C6—C1	180.0
C3—C4—C5—C6	0.000 (1)	C6—N2—C7—O3	0.000 (2)
C3—C4—C5—N1	180.000 (1)	C6—N2—C7—C8	180.000 (1)
O1—N1—C5—C4	0.000 (1)	O3—C7—C8—C9	−114.8 (4)
O2—N1—C5—C4	180.000 (1)	N2—C7—C8—C9	65.2 (4)
O1—N1—C5—C6	180.0	O3—C7—C8—C9ⁱ	114.8 (4)
O2—N1—C5—C6	0.000 (1)	N2—C7—C8—C9ⁱ	−65.2 (4)
C7—N2—C6—C1	0.000 (1)	O3—C7—C8—C10	0.000 (2)
C7—N2—C6—C5	180.000 (1)	N2—C7—C8—C10	180.000 (2)
C2—C1—C6—N2	180.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O3ⁱⁱ	0.96	2.35	3.294 (8)	167

Symmetry code: (ii) x+1/2, −y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂ClN₂O₃
M_r	255.68
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	10.401 (2), 7.0280 (14), 17.106 (3)
V (Å³)	1250.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.915, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	2432, 1244, 643
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.179, 1.00
No. of reflections	1244
No. of parameters	94
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O3ⁱ	0.96	2.35	3.294 (8)	167

Symmetry code: (i) x+1/2, −y+1/2, −z+3/2.

Acknowledgements

This research work was supported financially by the College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology and the 973 project (2011CB710803 and 2012CB721104) of the Key Basic Research Program of China.

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