2,2,2-Trichloro-N-(3-nitro­phen­yl)acetamide

Prabhu, A.N.; Upadhyaya, V.; Girisha, K.S.; Naveena, C.S.; Guru Row, T.N.

doi:10.1107/S1600536812036732

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2832

https://doi.org/10.1107/S1600536812036732

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2,2,2-Trichloro-N-(3-nitrophenyl)acetamide

A. N. Prabhu,^a V. Upadhyaya,^a ^* K. S. Girisha,^b C. S. Naveena ^c and T. N. Guru Row ^b

^aPhysics Department, Manipal Institute of Technology, Manipal University, Manipal 576 104, India, ^bSolid State and Sructural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India, and ^cDepartment of Chemistry, Mangalore University 575 199, Karnataka, India
^*Correspondence e-mail: v.upadhyaya@manipal.edu

(Received 27 July 2012; accepted 24 August 2012; online 1 September 2012)

In the title compound, C₈H₅Cl₃N₂O₃, the dihedral angle between the nitrophenyl ring and the acetamide group is 5.47 (6)°. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds link the molecules into chains running parallel to the b axis.

Related literature

For background to acetamides, see: Khan et al. (2010 ); Tahir & Shad (2011 ). For a related structure, see: Rosli et al. (2007 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₅Cl₃N₂O₃
M_r = 283.49
Orthorhombic, P b c a
a = 11.5164 (8) Å
b = 10.1427 (5) Å
c = 19.9054 (11) Å
V = 2325.1 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.18 mm

Data collection

Bruker SMART APEX CCD detector diffractometer
Absorption correction: multi-scan (SAINT-Plus; Bruker, 1998 ) T_min = 0.860, T_max = 0.872
8739 measured reflections
2532 independent reflections
1713 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.144
S = 1.07
2532 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1ⁱ	0.93	2.59	3.345 (4)	138
N2—H2N⋯O1ⁱ	0.86	2.15	2.990 (3)	164
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998) (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and CAMERON (Watkin et al., 1993 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812036732/pv2576sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812036732/pv2576Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812036732/pv2576Isup3.cml

checkCIF report

Comment top

In view of earlier studies and interest owing to the biological activity of acetamide (Khan et al., 2010; Tahir & Shad, 2011), we report herein the crystal structure of the title compound. In the title compound, the nitro phenyl ring makes a dihedral angle of 5.47 (6)° with acetamide group. Bond lengths and angles are within the normal ranges and are comparable with a related structure (Rosli et al., 2007). In the crystal, an S(6) ring motif (Bernstein et al., 1995) is formed via intramolecular C8—H8A···O1 hydrogen bond (Table 1). The C—H···O and C—H···N hydrogen bonding intractions (Table 1 and Figure 2) result in bifurcated bonds and link the molecules into chains along the b-axis.

Related literature top

For background to acetamides, see: Khan et al. (2010); Tahir & Shad (2011). For a related structure, see: Rosli et al. (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

3-Nitroaniline (1.0 g, 0.0072 mmol) was dissolved in 2M hydrochloric acid (5.0 ml), and added a little crushed ice. A solution of hydrated sodium acetate (5.0 g) in 25 ml of water was introduced, followed by trichloroacetic anhydride (4.5 g, 0.01457 mol). The mixture was shaken in the cold until the smell of trichloroacetic anhydride disappeared. The title compound was collected by filtration and recrystallized from an aqueous ethanol (75%) solution; yield: 1.52 g (75%), m.p. 376.15–378.15 K.

Structure description top

For background to acetamides, see: Khan et al. (2010); Tahir & Shad (2011). For a related structure, see: Rosli et al. (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. ORTEP (Farrugia, 1997) view of the title compound, showing 50% probability ellipsoids and the atom numbering scheme.
	Fig. 2. A unit cell packing of the title compound showing intermolecular interactions with dotted lines. H-atoms not involved in hydrogen bonding have been excluded.

2,2,2-Trichloro-N-(3-nitrophenyl)acetamide top

Crystal data top

C₈H₅Cl₃N₂O₃	F(000) = 1136
M_r = 283.49	D_x = 1.620 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2532 reflections
a = 11.5164 (8) Å	θ = 2.1–27.0°
b = 10.1427 (5) Å	µ = 0.78 mm⁻¹
c = 19.9054 (11) Å	T = 296 K
V = 2325.1 (2) Å³	Block, yellow
Z = 8	0.20 × 0.18 × 0.18 mm

Data collection top

Bruker SMART APEX CCD detector diffractometer	2532 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1713 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SAINT-Plus; Bruker, 1998)	h = −5→14
T_min = 0.860, T_max = 0.872	k = −10→12
8739 measured reflections	l = −14→25

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0695P)² + 0.9222P] where P = (F_o² + 2F_c²)/3
2532 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₈H₅Cl₃N₂O₃	V = 2325.1 (2) Å³
M_r = 283.49	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.5164 (8) Å	µ = 0.78 mm⁻¹
b = 10.1427 (5) Å	T = 296 K
c = 19.9054 (11) Å	0.20 × 0.18 × 0.18 mm

Data collection top

Bruker SMART APEX CCD detector diffractometer	2532 independent reflections
Absorption correction: multi-scan (SAINT-Plus; Bruker, 1998)	1713 reflections with I > 2σ(I)
T_min = 0.860, T_max = 0.872	R_int = 0.028
8739 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.07	Δρ_max = 0.46 e Å⁻³
2532 reflections	Δρ_min = −0.37 e Å⁻³
145 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.8599 (3)	0.8973 (3)	0.29007 (15)	0.0522 (8)
C2	0.7513 (2)	0.9294 (2)	0.33324 (13)	0.0390 (6)
C3	0.5939 (2)	0.8197 (2)	0.39617 (13)	0.0367 (6)
C4	0.5685 (3)	0.7018 (3)	0.42914 (16)	0.0520 (7)
H4	0.6196	0.6310	0.4260	0.062*
C5	0.4687 (3)	0.6897 (3)	0.4662 (2)	0.0705 (10)
H5	0.4522	0.6103	0.4876	0.085*
C6	0.3927 (3)	0.7935 (3)	0.47228 (18)	0.0621 (9)
H6	0.3243	0.7852	0.4968	0.074*
C7	0.4209 (2)	0.9099 (3)	0.44096 (14)	0.0429 (6)
C8	0.5197 (2)	0.9263 (2)	0.40254 (13)	0.0387 (6)
H8A	0.5358	1.0063	0.3817	0.046*
Cl1	0.82157 (11)	0.79451 (9)	0.22201 (5)	0.0843 (4)
Cl3	0.92258 (9)	1.04369 (8)	0.25994 (5)	0.0801 (4)
Cl2	0.96357 (8)	0.81360 (10)	0.34058 (6)	0.0828 (3)
N1	0.3404 (2)	1.0223 (3)	0.44728 (15)	0.0580 (7)
N2	0.6956 (2)	0.82155 (19)	0.35614 (12)	0.0433 (6)
H2N	0.7247	0.7464	0.3454	0.052*
O1	0.72365 (18)	1.04229 (16)	0.34446 (11)	0.0524 (5)
O2	0.3623 (2)	1.1225 (2)	0.41711 (16)	0.0858 (8)
O3	0.2570 (2)	1.0101 (3)	0.48485 (16)	0.0900 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0626 (19)	0.0350 (14)	0.0589 (18)	−0.0020 (13)	0.0223 (15)	0.0010 (12)
C2	0.0444 (14)	0.0307 (12)	0.0418 (14)	−0.0010 (11)	0.0055 (13)	0.0007 (10)
C3	0.0383 (14)	0.0318 (12)	0.0400 (13)	−0.0053 (10)	−0.0002 (12)	−0.0019 (10)
C4	0.0499 (17)	0.0353 (14)	0.071 (2)	0.0007 (12)	0.0134 (16)	0.0083 (13)
C5	0.064 (2)	0.0461 (18)	0.101 (3)	−0.0008 (15)	0.027 (2)	0.0226 (17)
C6	0.0453 (17)	0.0588 (19)	0.082 (2)	−0.0057 (14)	0.0193 (17)	0.0078 (16)
C7	0.0368 (14)	0.0433 (14)	0.0485 (15)	0.0011 (11)	−0.0027 (13)	−0.0063 (12)
C8	0.0412 (14)	0.0332 (13)	0.0416 (14)	−0.0015 (10)	−0.0005 (12)	−0.0017 (10)
Cl1	0.1194 (9)	0.0689 (6)	0.0645 (6)	−0.0233 (5)	0.0383 (6)	−0.0211 (4)
Cl3	0.0991 (8)	0.0439 (4)	0.0973 (7)	−0.0162 (4)	0.0522 (6)	0.0022 (4)
Cl2	0.0527 (5)	0.0816 (6)	0.1141 (8)	0.0127 (4)	0.0146 (5)	0.0168 (6)
N1	0.0462 (15)	0.0550 (16)	0.0728 (18)	0.0068 (12)	0.0062 (14)	−0.0033 (13)
N2	0.0482 (13)	0.0234 (10)	0.0584 (14)	0.0020 (9)	0.0148 (11)	0.0000 (9)
O1	0.0560 (12)	0.0243 (9)	0.0767 (14)	−0.0014 (8)	0.0169 (11)	−0.0020 (8)
O2	0.0786 (18)	0.0568 (15)	0.122 (2)	0.0245 (13)	0.0300 (16)	0.0152 (15)
O3	0.0544 (15)	0.0901 (18)	0.125 (2)	0.0202 (13)	0.0345 (16)	0.0105 (17)

Geometric parameters (Å, º) top

C1—C2	1.552 (4)	C5—C6	1.374 (4)
C1—Cl3	1.756 (3)	C5—H5	0.9300
C1—Cl1	1.766 (3)	C6—C7	1.374 (4)
C1—Cl2	1.777 (3)	C6—H6	0.9300
C2—O1	1.209 (3)	C7—C8	1.380 (4)
C2—N2	1.348 (3)	C7—N1	1.476 (4)
C3—C8	1.385 (3)	C8—H8A	0.9300
C3—C4	1.395 (3)	N1—O2	1.207 (3)
C3—N2	1.417 (3)	N1—O3	1.223 (4)
C4—C5	1.372 (4)	N2—H2N	0.8600
C4—H4	0.9300

C2—C1—Cl3	110.05 (18)	C6—C5—H5	119.6
C2—C1—Cl1	110.3 (2)	C7—C6—C5	117.9 (3)
Cl3—C1—Cl1	109.88 (16)	C7—C6—H6	121.1
C2—C1—Cl2	109.17 (19)	C5—C6—H6	121.1
Cl3—C1—Cl2	108.75 (18)	C6—C7—C8	123.4 (3)
Cl1—C1—Cl2	108.65 (15)	C6—C7—N1	118.5 (3)
O1—C2—N2	125.5 (2)	C8—C7—N1	118.1 (2)
O1—C2—C1	120.9 (2)	C7—C8—C3	117.7 (2)
N2—C2—C1	113.6 (2)	C7—C8—H8A	121.1
C8—C3—C4	119.8 (2)	C3—C8—H8A	121.1
C8—C3—N2	123.5 (2)	O2—N1—O3	123.6 (3)
C4—C3—N2	116.7 (2)	O2—N1—C7	118.5 (3)
C5—C4—C3	120.4 (3)	O3—N1—C7	117.8 (3)
C5—C4—H4	119.8	C2—N2—C3	126.5 (2)
C3—C4—H4	119.8	C2—N2—H2N	116.8
C4—C5—C6	120.8 (3)	C3—N2—H2N	116.8
C4—C5—H5	119.6

Cl3—C1—C2—O1	−3.2 (4)	C6—C7—C8—C3	−0.6 (4)
Cl1—C1—C2—O1	−124.6 (3)	N1—C7—C8—C3	−179.1 (2)
Cl2—C1—C2—O1	116.1 (3)	C4—C3—C8—C7	−1.2 (4)
Cl3—C1—C2—N2	177.6 (2)	N2—C3—C8—C7	177.4 (2)
Cl1—C1—C2—N2	56.2 (3)	C6—C7—N1—O2	−176.5 (3)
Cl2—C1—C2—N2	−63.1 (3)	C8—C7—N1—O2	2.1 (4)
C8—C3—C4—C5	1.9 (5)	C6—C7—N1—O3	6.1 (4)
N2—C3—C4—C5	−176.8 (3)	C8—C7—N1—O3	−175.3 (3)
C3—C4—C5—C6	−0.8 (6)	O1—C2—N2—C3	1.3 (5)
C4—C5—C6—C7	−1.0 (6)	C1—C2—N2—C3	−179.5 (3)
C5—C6—C7—C8	1.8 (5)	C8—C3—N2—C2	18.2 (4)
C5—C6—C7—N1	−179.7 (3)	C4—C3—N2—C2	−163.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1	0.93	2.32	2.870 (3)	117
C4—H4···O1ⁱ	0.93	2.59	3.345 (4)	138
N2—H2N···O1ⁱ	0.86	2.15	2.990 (3)	164

Symmetry code: (i) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₈H₅Cl₃N₂O₃
M_r	283.49
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	11.5164 (8), 10.1427 (5), 19.9054 (11)
V (Å³)	2325.1 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD detector
Absorption correction	Multi-scan (SAINT-Plus; Bruker, 1998)
T_min, T_max	0.860, 0.872
No. of measured, independent and observed [I > 2σ(I)] reflections	8739, 2532, 1713
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.144, 1.07
No. of reflections	2532
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.37

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1993), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.930	2.589	3.345 (4)	138
N2—H2N···O1ⁱ	0.860	2.154	2.990 (3)	164

Symmetry code: (i) −x+3/2, y−1/2, z.

Acknowledgements

ANP is thankful to Manipal Institute of Technology, Manipal University and Mohamed Ziaulla, Bangalore University.

References

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