N-(4-Methoxy­phen­yl)pivalamide

Saeed, A.; Hussain, S.; Batool, M.; Flörke

doi:10.1107/S1600536809029535

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2067

doi:10.1107/S1600536809029535

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N-(4-Methoxyphenyl)pivalamide

Aamer Saeed,^a ^* Shahid Hussain,^a Mahira Batool ^a and Ulrich Flörke ^b

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstrasse 100, D-33098 Paderborn, Germany
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 6 July 2009; accepted 24 July 2009; online 8 August 2009)

In the title molecule, C₁₂H₁₇NO₂, the amide (N—C=O) plane is oriented at an angle of 33.9 (1)° with respect to the aromatic ring. This is accompanied by an intramolecular C—H⋯O hydrogen bond. The methoxy group lies almost in the plane of the benzene ring [C–O–C–C torsion angle = 2.7 (2)°]. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules into chains along [010].

Related literature

For details of the biological activity of benzanilides, see: Olsson et al. (2002 ); Lindgren et al. (2001 ); Calderone et al. (2006 ). For the use of benzamides in organic synthesis, see: Zhichkin et al. (2007 ); Beccalli et al. (2005 ). For related structures see: Gowda et al. (2007a ,b ); Saeed et al. (2008 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₂H₁₇NO₂
M_r = 207.27
Orthorhombic, P b c a
a = 9.5547 (13) Å
b = 10.0657 (15) Å
c = 24.575 (4) Å
V = 2363.5 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 120 K
0.40 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.969, T_max = 0.984
17959 measured reflections
2817 independent reflections
2158 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.120
S = 1.02
2817 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.88	2.09	2.9382 (15)	160
C3—H3A⋯O1	0.95	2.45	2.9063 (17)	109
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); 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 global, I. DOI: 10.1107/S1600536809029535/fl2254sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029535/fl2254Isup2.hkl

checkCIF report

Comment top

N-substituted benzamides are well known anticancer compounds and the mechanism of action for N-substituted benzamide-induced apoptosis has been studied, using declopramide as a lead compound (Olsson et al., 2002). N-substituted benzamides inhibit the activity of nuclear factor- B and nuclear factor of activated T cells activity while inducing activator protein 1 activity in T lymphocytes (Lindgren et al., 2001). Heterocyclic analogs of benzanilide derivatives are potassium channel activators (Calderone et al., 2006). N-Alkylated 2-nitrobenzamides are intermediates in the synthesis of dibenzo[b,e][1,4]diazepines (Zhichkin et al., 2007) and N-Acyl-2-nitrobenzamides are precursors of 2,3-disubstitued 3H-quinazoline-4-ones (Beccalli et al., 2005).

The molecular structure of the title compound (Fig. 1)is closely related to two other compounds (Gowda et al., 2007a; 2007b) that exhiibt a methyl or chloro ligand instead of the methoxy group (CCDC refcodes HIDVOG and QIFKAS (Allen, 2002)), respectively. The dihedral angles between the benzene ring and the amide group are 33.9 (1)° for the title molecule and 32.8 (1)° for HIDVOG and 31.3 (1)° for QIFKAS, respectively. The C8–O2–C5–C6 torsion angle of 2.7 (2)° shows almost in-plane orientation of the methoxy group with respect to the aromatic ring. In the cystal structure, intermolecular N–H···O hydrogen bonds (Table 1) link the molecules into infinite chains along the direction (Fig. 2). A somewhat longer intramolecular C–H···O hydrogen bond is associated with the twist of the amide plane.

Related literature top

For details of the biological activity of benzanilides, see: Olsson et al. (2002); Lindgren et al. (2001); Calderone et al. (2006). For the use of benzamides in organic synthesis, see: Zhichkin et al. (2007); Beccalli et al. (2005). For related structures see: Gowda et al. (2007a,b); Saeed et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Pivaloyl chloride (1 mmol) in CHCl₃ was treated with 4-methoxyaniline (3.5 mmol) under a nitrogen atmosphere at reflux for 5 h. Upon cooling, the reaction mixture was diluted with CHCl₃ and washed consecutively with 1 M aq HCl and saturated aq NaHCO₃. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Crystallization of the residue in methanol afforded the title compound (84%) as white needles: Anal. calcd. for C₁₂H₁₇NO₂: C 59.54, H 8.27, N 6.76%; found: 59.51, H 8.31, N 6.82%.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. Molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing viewed along [100] with intermolecular hydrogen bonding pattern indicated as dashed lines. H-atoms not involved in hydrogen bonding are omitted.

N-(4-Methoxyphenyl)pivalamide top

Crystal data top

C₁₂H₁₇NO₂	F(000) = 896
M_r = 207.27	D_x = 1.165 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 778 reflections
a = 9.5547 (13) Å	θ = 2.7–27.0°
b = 10.0657 (15) Å	µ = 0.08 mm⁻¹
c = 24.575 (4) Å	T = 120 K
V = 2363.5 (6) Å³	Block, colourless
Z = 8	0.40 × 0.25 × 0.20 mm

Data collection top

Bruker SMART APEX diffractometer	2817 independent reflections
Radiation source: sealed tube	2158 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 27.9°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→12
T_min = 0.969, T_max = 0.984	k = −13→13
17959 measured reflections	l = −31→32

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)] = 0.048	Hydrogen site location: difference Fourier map
wR(F²) = 0.120	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0527P)² + 0.8944P] where P = (F_o² + 2F_c²)/3
2817 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₂H₁₇NO₂	V = 2363.5 (6) Å³
M_r = 207.27	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.5547 (13) Å	µ = 0.08 mm⁻¹
b = 10.0657 (15) Å	T = 120 K
c = 24.575 (4) Å	0.40 × 0.25 × 0.20 mm

Data collection top

Bruker SMART APEX diffractometer	2817 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2158 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.984	R_int = 0.053
17959 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.02	Δρ_max = 0.32 e Å⁻³
2817 reflections	Δρ_min = −0.20 e Å⁻³
137 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
O1	0.23114 (10)	0.78822 (9)	0.15214 (4)	0.0261 (2)
O2	−0.30713 (11)	0.99245 (12)	0.02439 (5)	0.0353 (3)
N1	0.18414 (12)	1.00795 (11)	0.14651 (5)	0.0221 (3)
H1A	0.2122	1.0875	0.1566	0.027*
C1	0.26370 (14)	0.90357 (13)	0.16238 (5)	0.0196 (3)
C2	0.05959 (14)	1.00104 (13)	0.11504 (5)	0.0203 (3)
C3	−0.03786 (15)	0.89929 (13)	0.12087 (6)	0.0233 (3)
H3A	−0.0213	0.8293	0.1460	0.028*
C4	−0.15869 (15)	0.90042 (14)	0.09003 (6)	0.0264 (3)
H4A	−0.2249	0.8307	0.0940	0.032*
C5	−0.18439 (15)	1.00250 (15)	0.05324 (6)	0.0253 (3)
C6	−0.08911 (16)	1.10480 (14)	0.04785 (6)	0.0270 (3)
H6A	−0.1068	1.1757	0.0233	0.032*
C7	0.03299 (15)	1.10322 (13)	0.07865 (6)	0.0249 (3)
H7A	0.0991	1.1731	0.0747	0.030*
C8	−0.33901 (18)	1.09944 (18)	−0.01185 (7)	0.0375 (4)
H8A	−0.3448	1.1826	0.0088	0.056*
H8B	−0.4289	1.0823	−0.0298	0.056*
H8C	−0.2652	1.1067	−0.0394	0.056*
C9	0.39771 (15)	0.93998 (13)	0.19354 (6)	0.0227 (3)
C10	0.36095 (17)	1.02511 (15)	0.24320 (7)	0.0313 (4)
H10A	0.4468	1.0479	0.2629	0.047*
H10B	0.2983	0.9752	0.2672	0.047*
H10C	0.3143	1.1067	0.2312	0.047*
C11	0.46851 (17)	0.81265 (15)	0.21301 (7)	0.0337 (4)
H11A	0.5542	0.8351	0.2329	0.050*
H11B	0.4920	0.7571	0.1816	0.050*
H11C	0.4048	0.7640	0.2371	0.050*
C12	0.49651 (16)	1.01588 (16)	0.15543 (7)	0.0328 (4)
H12A	0.5824	1.0391	0.1751	0.049*
H12B	0.4504	1.0972	0.1428	0.049*
H12C	0.5199	0.9599	0.1241	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0257 (5)	0.0146 (5)	0.0380 (6)	−0.0001 (4)	−0.0074 (4)	−0.0020 (4)
O2	0.0262 (6)	0.0441 (7)	0.0356 (6)	−0.0021 (5)	−0.0122 (5)	0.0052 (5)
N1	0.0226 (6)	0.0141 (5)	0.0297 (6)	−0.0008 (4)	−0.0065 (5)	−0.0017 (5)
C1	0.0211 (7)	0.0177 (6)	0.0201 (6)	0.0008 (5)	−0.0003 (5)	0.0001 (5)
C2	0.0201 (7)	0.0184 (6)	0.0223 (6)	0.0026 (5)	−0.0026 (5)	−0.0024 (5)
C3	0.0237 (7)	0.0197 (6)	0.0266 (7)	0.0008 (5)	−0.0012 (6)	0.0018 (5)
C4	0.0226 (7)	0.0253 (7)	0.0315 (8)	−0.0035 (6)	−0.0006 (6)	−0.0012 (6)
C5	0.0195 (7)	0.0324 (8)	0.0240 (7)	0.0026 (6)	−0.0019 (5)	−0.0040 (6)
C6	0.0275 (8)	0.0269 (7)	0.0267 (8)	0.0040 (6)	−0.0023 (6)	0.0056 (6)
C7	0.0241 (7)	0.0201 (7)	0.0307 (8)	−0.0009 (5)	−0.0029 (6)	0.0026 (6)
C8	0.0318 (9)	0.0506 (10)	0.0301 (9)	0.0057 (8)	−0.0106 (7)	0.0047 (7)
C9	0.0230 (7)	0.0172 (6)	0.0278 (7)	0.0001 (5)	−0.0058 (6)	0.0009 (5)
C10	0.0346 (9)	0.0283 (7)	0.0310 (8)	−0.0007 (6)	−0.0095 (7)	−0.0052 (6)
C11	0.0326 (9)	0.0231 (7)	0.0453 (10)	0.0035 (6)	−0.0177 (7)	0.0017 (7)
C12	0.0209 (7)	0.0365 (8)	0.0409 (9)	−0.0025 (6)	−0.0036 (7)	0.0071 (7)

Geometric parameters (Å, º) top

O1—C1	1.2282 (16)	C7—H7A	0.9500
O2—C5	1.3741 (17)	C8—H8A	0.9800
O2—C8	1.4304 (19)	C8—H8B	0.9800
N1—C1	1.3542 (17)	C8—H8C	0.9800
N1—C2	1.4209 (17)	C9—C11	1.5262 (19)
N1—H1A	0.8800	C9—C10	1.532 (2)
C1—C9	1.5362 (19)	C9—C12	1.534 (2)
C2—C7	1.3866 (19)	C10—H10A	0.9800
C2—C3	1.3916 (19)	C10—H10B	0.9800
C3—C4	1.381 (2)	C10—H10C	0.9800
C3—H3A	0.9500	C11—H11A	0.9800
C4—C5	1.391 (2)	C11—H11B	0.9800
C4—H4A	0.9500	C11—H11C	0.9800
C5—C6	1.381 (2)	C12—H12A	0.9800
C6—C7	1.391 (2)	C12—H12B	0.9800
C6—H6A	0.9500	C12—H12C	0.9800

C5—O2—C8	116.59 (12)	O2—C8—H8C	109.5
C1—N1—C2	126.08 (11)	H8A—C8—H8C	109.5
C1—N1—H1A	117.0	H8B—C8—H8C	109.5
C2—N1—H1A	117.0	C11—C9—C10	108.76 (12)
O1—C1—N1	122.16 (13)	C11—C9—C12	109.69 (13)
O1—C1—C9	122.60 (12)	C10—C9—C12	110.42 (12)
N1—C1—C9	115.24 (11)	C11—C9—C1	108.99 (11)
C7—C2—C3	119.32 (13)	C10—C9—C1	109.84 (12)
C7—C2—N1	117.92 (12)	C12—C9—C1	109.12 (11)
C3—C2—N1	122.71 (12)	C9—C10—H10A	109.5
C4—C3—C2	119.79 (13)	C9—C10—H10B	109.5
C4—C3—H3A	120.1	H10A—C10—H10B	109.5
C2—C3—H3A	120.1	C9—C10—H10C	109.5
C3—C4—C5	120.70 (13)	H10A—C10—H10C	109.5
C3—C4—H4A	119.6	H10B—C10—H10C	109.5
C5—C4—H4A	119.6	C9—C11—H11A	109.5
O2—C5—C6	124.62 (13)	C9—C11—H11B	109.5
O2—C5—C4	115.58 (13)	H11A—C11—H11B	109.5
C6—C5—C4	119.80 (13)	C9—C11—H11C	109.5
C5—C6—C7	119.50 (13)	H11A—C11—H11C	109.5
C5—C6—H6A	120.3	H11B—C11—H11C	109.5
C7—C6—H6A	120.3	C9—C12—H12A	109.5
C2—C7—C6	120.88 (13)	C9—C12—H12B	109.5
C2—C7—H7A	119.6	H12A—C12—H12B	109.5
C6—C7—H7A	119.6	C9—C12—H12C	109.5
O2—C8—H8A	109.5	H12A—C12—H12C	109.5
O2—C8—H8B	109.5	H12B—C12—H12C	109.5
H8A—C8—H8B	109.5

C2—N1—C1—O1	−2.7 (2)	O2—C5—C6—C7	−178.91 (13)
C2—N1—C1—C9	176.75 (12)	C4—C5—C6—C7	1.2 (2)
C1—N1—C2—C7	−145.49 (14)	C3—C2—C7—C6	−0.3 (2)
C1—N1—C2—C3	37.0 (2)	N1—C2—C7—C6	−177.94 (13)
C7—C2—C3—C4	0.7 (2)	C5—C6—C7—C2	−0.6 (2)
N1—C2—C3—C4	178.23 (13)	O1—C1—C9—C11	−5.65 (19)
C2—C3—C4—C5	−0.2 (2)	N1—C1—C9—C11	174.89 (13)
C8—O2—C5—C6	−2.7 (2)	O1—C1—C9—C10	−124.71 (14)
C8—O2—C5—C4	177.17 (13)	N1—C1—C9—C10	55.83 (16)
C3—C4—C5—O2	179.31 (13)	O1—C1—C9—C12	114.12 (15)
C3—C4—C5—C6	−0.8 (2)	N1—C1—C9—C12	−65.34 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	2.09	2.9382 (15)	160
C3—H3A···O1	0.95	2.45	2.9063 (17)	109

Symmetry code: (i) −x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₇NO₂
M_r	207.27
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	9.5547 (13), 10.0657 (15), 24.575 (4)
V (Å³)	2363.5 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.969, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	17959, 2817, 2158
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.120, 1.02
No. of reflections	2817
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.20

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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
N1—H1A···O1ⁱ	0.88	2.09	2.9382 (15)	160.3
C3—H3A···O1	0.95	2.45	2.9063 (17)	109.2

Symmetry code: (i) −x+1/2, y+1/2, z.

Acknowledgements

AS gratefully acknowledges a research grant from Quaid-i-Azam University Islamabad under the URF program (DFNS/2009-36).

References

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