N-(4-Bromo­phen­yl)acetamide: a new polymorph

Jasinski, J.P.; Guild, C.J.; Yathirajan, H.S.; Narayana, B.; Samshuddin, S.

doi:10.1107/S1600536813005448

organic compounds

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Volume 69| Part 3| March 2013| Page o461

doi:10.1107/S1600536813005448

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N-(4-Bromophenyl)acetamide: a new polymorph

Jerry P. Jasinski,^a ^* Curtis J. Guild,^a H. S. Yathirajan,^b B. Narayana ^c and S. Samshuddin ^c

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, 574 199, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 24 February 2013; accepted 25 February 2013; online 28 February 2013)

A new polymorph of the title compound, C₈H₈BrNO, has been determined at 173 K in the space group P2₁/c. The previous room-temperature structure was reported to crystallize in the orthorhombic space group Pna2₁ [Andreetti et al. (1968 ). Acta Cryst. B24, 1195–1198]. In the crystal, molecules are linked by N—H⋯O hydrogen bonds forming chains along [010]. Weak C—H⋯π interactions are also present.

Related literature

For 2-arylacetamides, see: Mijin & Marinkovic (2006 ); Mijin et al. (2008 ) and for amides, see: Wu et al. (2008 , 2010 ). For the structure of the orthorhombic polymorph, see: Andreetti et al. (1968). For related structures, see: Praveen et al. (2011a ,b ,c ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₈BrNO
M_r = 214.06
Monoclinic, P 2₁ /c
a = 6.7250 (7) Å
b = 9.3876 (11) Å
c = 14.4434 (14) Å
β = 117.750 (4)°
V = 806.96 (15) Å³
Z = 4
Mo Kα radiation
μ = 5.03 mm⁻¹
T = 173 K
0.32 × 0.22 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.296, T_max = 0.465
10902 measured reflections
2689 independent reflections
2099 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.073
S = 1.04
2689 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.89	2.00	2.885 (2)	174
C1—H1B⋯Cg1ⁱⁱ	0.98	2.84	3.761 (3)	157
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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 global, I. DOI: 10.1107/S1600536813005448/su2566sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813005448/su2566Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813005448/su2566Isup3.cml

checkCIF report

Comment top

Substituted 2-arylacetamides are very interesting compounds because of their structural similarity to the lateral chain of natural benzyl penicillin (Mijin et al., 2006, 2008). Amides are also used as ligands due to their excellent coordination abilities (Wu et al., 2008, 2010). The room temperature crystal structure of the title compound was reported without hydrogen atom coordinates in the orthorhombic space group Pna2₁ (Andreetti et al., 1968). We report herein on the crystal structure of the monoclinic polymorph that crystallized in space group P2₁/c.

The molecular structure of the title compound is illustrated in Fig. 1. Bond lengths are in normal ranges (Allen et al., 1987) but show slight changes from those reported for some similar acetamide derivatives viz., N-(4-chloro-1,3-benzothiazol-2-yl)-2-(3-methylphenyl)acetamide monohydrate (Praveen et al., 2011a), N-(3-chloro-4-fluorophenyl)-2,2-diphenylacetamide (Praveen et al., 2011b) and N-(3-chloro-4-fluorophenyl)-2-(naphthalen-1-yl)acetamide (Praveen et al., 2011c). The differences observed are primarily in the acetamide and bromophenyl regions [C1–C2 1.501 (3) Å versus 1.53 (4) Å; N1–C2 1.347 (2) Å versus 1.30 (3) Å; N1–C3 1.401 (2) Å versus 1.44 (3) Å and C6–Br 1.8907 (19) versus 1.91 (1) Å].

In the crystal, molecules are linked by N—H···O hydrogen bonds forming chains along [010] [Table 1 and Fig. 2]. Weak C—H···π interactions are also present (Table 1) and contribute to the crystal packing stability.

Related literature top

For 2-arylacetamides, see: Mijin & Marinkovic (2006); Mijin et al. (2008) and for amides, see: Wu et al. (2008, 2010). For the structure of the orthorhombic polymorph, see: Andreetti et al. (1968). For related structures, see: Praveen et al. (2011a,b,c). For standard bond lengths, see: Allen et al. (1987).

Experimental top

4-Bromo aniline (0.172 g, 1 mmol) was dissolved in acetic acid (20 ml) and refluxed for 4 h. The solution was then cooled and poured into 100 ml of ice-cold water with stirring. The precipitate obtained was filtered, washed with water and dried. Block-like yellow crystals were grown from a solution in ethyl acetate by slow evaporation of the solvent (M.p.: 430 K).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); 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 molecule, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing diagram of the title compound viewed along the c axis. Dashed lines indicate N—H···O hydrogen bonds linking the molecules into chains along [010]. C-bound H atoms have been omitted for clarity.

N-(4-Bromophenyl)acetamide top

Crystal data top

C₈H₈BrNO	F(000) = 424
M_r = 214.06	D_x = 1.762 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3269 reflections
a = 6.7250 (7) Å	θ = 3.4–32.3°
b = 9.3876 (11) Å	µ = 5.03 mm⁻¹
c = 14.4434 (14) Å	T = 173 K
β = 117.750 (4)°	Block, yellow
V = 806.96 (15) Å³	0.32 × 0.22 × 0.18 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer	2689 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2099 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 16.1500 pixels mm^-1	θ_max = 32.3°, θ_min = 3.4°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction 2010)	k = −13→13
T_min = 0.296, T_max = 0.465	l = −20→19
10902 measured reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0329P)² + 0.1779P] where P = (F_o² + 2F_c²)/3
2689 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₈H₈BrNO	V = 806.96 (15) Å³
M_r = 214.06	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7250 (7) Å	µ = 5.03 mm⁻¹
b = 9.3876 (11) Å	T = 173 K
c = 14.4434 (14) Å	0.32 × 0.22 × 0.18 mm
β = 117.750 (4)°

Data collection top

Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer	2689 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction 2010)	2099 reflections with I > 2σ(I)
T_min = 0.296, T_max = 0.465	R_int = 0.035
10902 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.04	Δρ_max = 0.54 e Å⁻³
2689 reflections	Δρ_min = −0.44 e Å⁻³
101 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
Br1	−0.12616 (4)	0.70900 (2)	0.493749 (17)	0.03329 (8)
O1	0.4333 (2)	0.63844 (14)	0.19611 (11)	0.0286 (3)
N1	0.3872 (3)	0.85329 (15)	0.25584 (12)	0.0212 (3)
H1	0.4358	0.9432	0.2658	0.025*
C1	0.5678 (4)	0.8449 (2)	0.14665 (17)	0.0283 (4)
H1A	0.5162	0.8041	0.0767	0.042*
H1B	0.7312	0.8344	0.1869	0.042*
H1C	0.5281	0.9462	0.1404	0.042*
C2	0.4570 (3)	0.76819 (19)	0.20162 (15)	0.0213 (4)
C3	0.2696 (3)	0.81333 (18)	0.31030 (14)	0.0199 (3)
C4	0.2647 (3)	0.91062 (19)	0.38173 (15)	0.0240 (4)
H4	0.3428	0.9985	0.3931	0.029*
C5	0.1473 (3)	0.8806 (2)	0.43633 (16)	0.0265 (4)
H5	0.1435	0.9475	0.4849	0.032*
C6	0.0351 (3)	0.7520 (2)	0.41948 (15)	0.0233 (4)
C7	0.0369 (3)	0.6541 (2)	0.34821 (15)	0.0247 (4)
H7	−0.0407	0.5662	0.3374	0.030*
C8	0.1522 (3)	0.68544 (19)	0.29313 (15)	0.0235 (4)
H8	0.1518	0.6195	0.2431	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03360 (13)	0.03978 (14)	0.03455 (13)	−0.00199 (9)	0.02264 (10)	0.00392 (9)
O1	0.0383 (8)	0.0163 (6)	0.0388 (8)	0.0038 (6)	0.0242 (7)	−0.0003 (5)
N1	0.0257 (8)	0.0132 (7)	0.0290 (8)	−0.0018 (6)	0.0163 (7)	−0.0016 (6)
C1	0.0328 (11)	0.0252 (9)	0.0350 (11)	0.0002 (8)	0.0226 (9)	−0.0001 (8)
C2	0.0214 (9)	0.0189 (9)	0.0260 (9)	0.0025 (7)	0.0129 (7)	0.0009 (7)
C3	0.0207 (9)	0.0161 (8)	0.0237 (9)	0.0028 (6)	0.0109 (7)	0.0020 (6)
C4	0.0296 (10)	0.0159 (8)	0.0288 (10)	−0.0009 (7)	0.0157 (8)	−0.0008 (7)
C5	0.0331 (11)	0.0219 (9)	0.0285 (10)	0.0009 (8)	0.0176 (9)	−0.0028 (7)
C6	0.0213 (9)	0.0263 (9)	0.0239 (9)	0.0019 (7)	0.0119 (8)	0.0050 (7)
C7	0.0239 (9)	0.0204 (8)	0.0301 (10)	−0.0038 (7)	0.0129 (8)	−0.0001 (7)
C8	0.0257 (9)	0.0182 (8)	0.0281 (10)	−0.0014 (7)	0.0138 (8)	−0.0027 (7)

Geometric parameters (Å, º) top

Br1—C6	1.8906 (19)	C3—C8	1.394 (2)
O1—C2	1.226 (2)	C4—C5	1.380 (3)
N1—C2	1.347 (2)	C4—H4	0.9500
N1—C3	1.401 (2)	C5—C6	1.384 (3)
N1—H1	0.8922	C5—H5	0.9500
C1—C2	1.501 (3)	C6—C7	1.384 (3)
C1—H1A	0.9800	C7—C8	1.377 (3)
C1—H1B	0.9800	C7—H7	0.9500
C1—H1C	0.9800	C8—H8	0.9500
C3—C4	1.390 (2)

C2—N1—C3	127.45 (15)	C5—C4—C3	120.52 (17)
C2—N1—H1	117.0	C5—C4—H4	119.7
C3—N1—H1	115.1	C3—C4—H4	119.7
C2—C1—H1A	109.5	C4—C5—C6	119.17 (17)
C2—C1—H1B	109.5	C4—C5—H5	120.4
H1A—C1—H1B	109.5	C6—C5—H5	120.4
C2—C1—H1C	109.5	C5—C6—C7	121.18 (18)
H1A—C1—H1C	109.5	C5—C6—Br1	119.76 (15)
H1B—C1—H1C	109.5	C7—C6—Br1	119.06 (15)
O1—C2—N1	123.83 (17)	C8—C7—C6	119.33 (18)
O1—C2—C1	121.58 (17)	C8—C7—H7	120.3
N1—C2—C1	114.59 (16)	C6—C7—H7	120.3
C4—C3—C8	119.39 (18)	C7—C8—C3	120.39 (18)
C4—C3—N1	117.09 (16)	C7—C8—H8	119.8
C8—C3—N1	123.46 (17)	C3—C8—H8	119.8

C3—N1—C2—O1	−3.1 (3)	C4—C5—C6—C7	−0.7 (3)
C3—N1—C2—C1	176.68 (18)	C4—C5—C6—Br1	179.88 (15)
C2—N1—C3—C4	164.06 (18)	C5—C6—C7—C8	0.0 (3)
C2—N1—C3—C8	−18.6 (3)	Br1—C6—C7—C8	179.37 (15)
C8—C3—C4—C5	0.8 (3)	C6—C7—C8—C3	1.2 (3)
N1—C3—C4—C5	178.23 (17)	C4—C3—C8—C7	−1.6 (3)
C3—C4—C5—C6	0.3 (3)	N1—C3—C8—C7	−178.81 (18)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.89	2.00	2.885 (2)	174
C1—H1B···Cg1ⁱⁱ	0.98	2.84	3.761 (3)	157

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₈H₈BrNO
M_r	214.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	6.7250 (7), 9.3876 (11), 14.4434 (14)
β (°)	117.750 (4)
V (Å³)	806.96 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.03
Crystal size (mm)	0.32 × 0.22 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction 2010)
T_min, T_max	0.296, 0.465
No. of measured, independent and observed [I > 2σ(I)] reflections	10902, 2689, 2099
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.753

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.073, 1.04
No. of reflections	2689
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.44

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.89	2.00	2.885 (2)	174
C1—H1B···Cg1ⁱⁱ	0.98	2.84	3.761 (3)	157

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x+1, y, z.

Acknowledgements

BN thanks the UGC, New Delhi, and the Government of India for the purchase of chemicals through the SAP–DRS-Phase-1 programme and a BSR one-time grant. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o461

doi:10.1107/S1600536813005448

Open

access