supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

Acta Cryst. (2008). E64, o2322-o2323    [ doi:10.1107/S1600536808036313 ]

N-Butyl-4-chlorobenzamide

A. Saeed, R. A. Khera, N. Abbas, J. Simpson and R. G. Stanley

Abstract top

In the title benzamide derivative, C11H14ClNO, the chlorobenzene and butylamine groups are each planar, with mean deviations from the planes of 0.013 and 0.030 Å, respectively, and a dihedral angle of 2.54 (9)° between the two planes. In the crystal structure, N-H...O hydrogen bonds link molecules in rows along a. Short intermolecular Cl...Cl interactions [3.4225 (5) Å] link these rows into sheets in the ac plane. Additional weak C-H...O and C-H...[pi] interactions generate a three-dimensional network.

Comment top

The benzanilide core is present in compounds with such a wide range of biological activities that it has been called a privileged structure. 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). Various N-substituted benzamides exhibit potent antiemetic activity (Vega-noverola et al., 1989), while heterocyclic analogs of benzanilide derivatives are potassium channel activators (Calderone et al., 2006). o-Aryloxylation of N-substituted benzamides induced by the copper(II)/trimethylamine N-oxide system has been studied (Reinaud et al., 1991). 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). A one-pot conversion of 2-nitro-n-arylbenzamides to 2,3-dihydro-1H-quinazoline-4-ones has also been reported (Yoo et al., 2005). The anomalous dual fluorescence of benzanilides has been assigned to the two lowest benzanilide singlet states (Lewis & Long, 1998)

As part of our work on the structure of benzanildes and related compounds, we report here the structure of the title benzamide derivative, I, Fig. 1. The C1···C7/Cl system is planar with a maximum deviation of 0.0161 (7) Å from the least squares plane. The carbonyl oxygen atom O1 is displaced by 0.6102 (10) Å from this plane. The butylamine N1/C8···C11 fragment is also planar, maximum deviation 0.0365 (7) Å for C9. The dihedral angle between these two planes is 2.54 (9) °. Bond distances within the molecule are normal (Allen et al., 1987) and similar to those found in the structures of related 4-chlorobenzamide derivatives (Saeed et al., 2008, Hempel et al., 2005).

In the crystal structure N1—HN1···O1 hydrogen bonds, Table 1, link molecules into rows along a. Cl1···Cl1 interactions at 3.4225 (5) Å bridge these rows to form sheets in the ac plane, Fig. 2. The sheets are interconnected by weak C3—H3···O1 hydrogen bonds and C8—H8···π interactions involving the C2···C7 benzene ring to generate a three dimensional network, Fig. 3.

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: Reinaud et al. (1991); Zhichkin et al. (2007); Beccalli et al. (2005); For the fluorescence properties of benzanilides, see: (Lewis & Long, 1998). For related structures see: Saeed et al. (2008); Hempel et al. (2005). For reference structural data, see: Allen et al. (1987). For related literature, see: Vega-noverola et al. (1989); Yoo et al. (2005). Cg1 is the centroid of the C2–C7 benzene ring.

Experimental top

2-Fluorobenzoyl chloride (1 mmol) in CHCl3 was treated with cyclohexyl amine (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 ethanol afforded the title compound (79 %) as white needles: Anal. calcd. for C11H14ClNO: C 62.41, H 6.67, N 6.62%; found: C 62.34, H 7.16, N 6.57%.

Refinement top

The H atom bound to N1 was located in a difference electron density map and refined freely with an isotropic displacement parameter. All other H-atoms were refined using a riding model with d(C—H) = 0.95 Å, Uiso= 1.2Ueq (C) for aromatic, 0.99Å, Uiso = 1.2Ueq (C) for CH2, and 0.98 Å, Uiso = 1.5Ueq (C) for CH3 H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006) and SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. The structure of I showing the atom numbering with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Sheets of molecules of I formed in the ac plane by N—H···O hydrogen bonds and Cl···Cl interactions.
[Figure 3] Fig. 3. Crystal packing of I viewed down the b axis.
N-Butyl-4-chlorobenzamide top
Crystal data top
C11H14ClNOZ = 2
Mr = 211.68F(000) = 224
Triclinic, P1Dx = 1.333 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.1702 (4) ÅCell parameters from 3494 reflections
b = 7.8979 (5) Åθ = 5.3–66.2°
c = 13.2978 (9) ŵ = 0.33 mm−1
α = 89.275 (3)°T = 81 K
β = 84.863 (4)°Irregular fragment, colourless
γ = 77.165 (4)°0.42 × 0.30 × 0.08 mm
V = 527.29 (6) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3445 independent reflections
Radiation source: fine-focus sealed tube3050 reflections with I > 2σ(I)
graphiteRint = 0.017
ω scansθmax = 33.1°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2006)		h = −7→6
Tmin = 0.820, Tmax = 0.974k = −11→11
6632 measured reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0471P)2 + 0.125P]
where P = (Fo2 + 2Fc2)/3
3445 reflections(Δ/σ)max = 0.002
132 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.22 e Å−3
Crystal data top
C11H14ClNOγ = 77.165 (4)°
Mr = 211.68V = 527.29 (6) Å3
Triclinic, P1Z = 2
a = 5.1702 (4) ÅMo Kα radiation
b = 7.8979 (5) ŵ = 0.33 mm−1
c = 13.2978 (9) ÅT = 81 K
α = 89.275 (3)°0.42 × 0.30 × 0.08 mm
β = 84.863 (4)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3445 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2006)		3050 reflections with I > 2σ(I)
Tmin = 0.820, Tmax = 0.974Rint = 0.017
6632 measured reflectionsθmax = 33.1°
Refinement top
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090Δρmax = 0.43 e Å−3
S = 1.04Δρmin = −0.22 e Å−3
3445 reflectionsAbsolute structure: ?
132 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
N10.51637 (16)0.82511 (10)−0.10915 (6)0.01587 (15)
HN10.662 (3)0.8260 (18)−0.0876 (11)0.026 (3)*
C10.31476 (17)0.79695 (10)−0.04475 (6)0.01281 (15)
O10.08420 (13)0.81551 (8)−0.06861 (5)0.01616 (14)
C20.38267 (17)0.73835 (10)0.05917 (6)0.01257 (15)
C30.18549 (19)0.78474 (11)0.13885 (7)0.01611 (17)
H30.01690.85450.12620.019*
C40.2331 (2)0.73001 (12)0.23650 (7)0.01847 (18)
H40.09950.76310.29080.022*
C50.4800 (2)0.62579 (11)0.25329 (7)0.01667 (17)
Cl10.54360 (5)0.55693 (3)0.375283 (17)0.02530 (8)
C60.67765 (19)0.57568 (12)0.17528 (7)0.01740 (17)
H60.84390.50270.18790.021*
C70.62886 (18)0.63406 (11)0.07801 (7)0.01532 (16)
H70.76420.60260.02410.018*
C80.47533 (19)0.87979 (13)−0.21289 (7)0.01730 (17)
H8A0.42811.0082−0.21520.021*
H8B0.32420.8363−0.23520.021*
C90.72100 (18)0.81319 (12)−0.28494 (7)0.01526 (16)
H9A0.76640.6847−0.28400.018*
H9B0.87330.8549−0.26230.018*
C100.67469 (19)0.87506 (12)−0.39261 (7)0.01705 (17)
H10A0.51120.8435−0.41230.020*
H10B0.64581.0032−0.39430.020*
C110.9070 (2)0.79692 (14)−0.46899 (8)0.02213 (19)
H11A1.06960.8277−0.45000.033*
H11B0.86910.8425−0.53630.033*
H11C0.93170.6703−0.46980.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0106 (3)0.0251 (4)0.0134 (3)−0.0064 (3)−0.0033 (3)0.0048 (3)
C10.0120 (4)0.0133 (3)0.0131 (4)−0.0024 (3)−0.0018 (3)0.0006 (3)
O10.0097 (3)0.0217 (3)0.0170 (3)−0.0028 (2)−0.0029 (2)0.0024 (2)
C20.0115 (4)0.0138 (3)0.0131 (4)−0.0038 (3)−0.0025 (3)0.0013 (3)
C30.0132 (4)0.0188 (4)0.0154 (4)−0.0017 (3)−0.0005 (3)0.0009 (3)
C40.0185 (4)0.0224 (4)0.0140 (4)−0.0043 (3)0.0006 (3)0.0006 (3)
C50.0213 (4)0.0170 (4)0.0138 (4)−0.0074 (3)−0.0055 (3)0.0036 (3)
Cl10.03326 (15)0.02986 (13)0.01517 (12)−0.00986 (10)−0.00874 (9)0.00705 (8)
C60.0160 (4)0.0180 (4)0.0184 (4)−0.0030 (3)−0.0058 (3)0.0038 (3)
C70.0117 (4)0.0177 (4)0.0159 (4)−0.0019 (3)−0.0015 (3)0.0016 (3)
C80.0121 (4)0.0261 (4)0.0137 (4)−0.0040 (3)−0.0022 (3)0.0059 (3)
C90.0115 (4)0.0202 (4)0.0143 (4)−0.0034 (3)−0.0028 (3)0.0018 (3)
C100.0138 (4)0.0230 (4)0.0139 (4)−0.0032 (3)−0.0020 (3)0.0029 (3)
C110.0185 (5)0.0300 (5)0.0170 (4)−0.0043 (4)0.0006 (3)−0.0014 (3)
Geometric parameters (Å, °) top
N1—C11.3446 (12)C6—H60.9500
N1—C81.4598 (11)C7—H70.9500
N1—HN10.831 (15)C8—C91.5185 (13)
C1—O11.2378 (11)C8—H8A0.9900
C1—C21.4984 (12)C8—H8B0.9900
C2—C31.3952 (12)C9—C101.5290 (12)
C2—C71.3955 (12)C9—H9A0.9900
C3—C41.3891 (13)C9—H9B0.9900
C3—H30.9500C10—C111.5242 (13)
C4—C51.3918 (13)C10—H10A0.9900
C4—H40.9500C10—H10B0.9900
C5—C61.3848 (14)C11—H11A0.9800
C5—Cl11.7405 (9)C11—H11B0.9800
C6—C71.3931 (12)C11—H11C0.9800
C1—N1—C8121.48 (8)N1—C8—C9112.18 (7)
C1—N1—HN1119.5 (10)N1—C8—H8A109.2
C8—N1—HN1118.4 (10)C9—C8—H8A109.2
O1—C1—N1122.89 (8)N1—C8—H8B109.2
O1—C1—C2120.60 (8)C9—C8—H8B109.2
N1—C1—C2116.51 (8)H8A—C8—H8B107.9
C3—C2—C7119.40 (8)C8—C9—C10111.15 (7)
C3—C2—C1117.87 (8)C8—C9—H9A109.4
C7—C2—C1122.67 (8)C10—C9—H9A109.4
C4—C3—C2120.71 (8)C8—C9—H9B109.4
C4—C3—H3119.6C10—C9—H9B109.4
C2—C3—H3119.6H9A—C9—H9B108.0
C3—C4—C5118.78 (9)C11—C10—C9112.75 (8)
C3—C4—H4120.6C11—C10—H10A109.0
C5—C4—H4120.6C9—C10—H10A109.0
C6—C5—C4121.65 (8)C11—C10—H10B109.0
C6—C5—Cl1118.96 (7)C9—C10—H10B109.0
C4—C5—Cl1119.39 (7)H10A—C10—H10B107.8
C5—C6—C7118.95 (8)C10—C11—H11A109.5
C5—C6—H6120.5C10—C11—H11B109.5
C7—C6—H6120.5H11A—C11—H11B109.5
C6—C7—C2120.49 (9)C10—C11—H11C109.5
C6—C7—H7119.8H11A—C11—H11C109.5
C2—C7—H7119.8H11B—C11—H11C109.5
C8—N1—C1—O1−0.14 (13)C3—C4—C5—Cl1179.68 (7)
C8—N1—C1—C2179.00 (8)C4—C5—C6—C71.22 (14)
O1—C1—C2—C3−30.72 (12)Cl1—C5—C6—C7−178.56 (7)
N1—C1—C2—C3150.11 (8)C5—C6—C7—C2−1.35 (13)
O1—C1—C2—C7146.41 (9)C3—C2—C7—C60.37 (13)
N1—C1—C2—C7−32.76 (12)C1—C2—C7—C6−176.72 (8)
C7—C2—C3—C40.79 (13)C1—N1—C8—C9−149.00 (8)
C1—C2—C3—C4178.01 (8)N1—C8—C9—C10−178.91 (7)
C2—C3—C4—C5−0.92 (14)C8—C9—C10—C11−174.52 (8)
C3—C4—C5—C6−0.10 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—HN1···O1i0.831 (15)2.203 (15)3.0164 (10)166.3 (13)
C3—H3···O1ii0.952.663.3146 (11)127
C8—H8A···Cg1iii0.992.843.697 (16)145
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+2, −z; (iii) −x+1, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—HN1···O1i0.831 (15)2.203 (15)3.0164 (10)166.3 (13)
C3—H3···O1ii0.952.663.3146 (11)127
C8—H8A···Cg1iii0.992.843.697 (16)145
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+2, −z; (iii) −x+1, −y, −z.
Acknowledgements top

NA gratefully acknowledges financial support for a PhD programme by the Higher Education Commission of Pakistan. We also thank the University of Otago for purchase of the diffractometer.

references
References top

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338.

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Beccalli, E. M., Broggini, G., Paladinoa, G. & Zonia, C. (2005). Tetrahedron, 61, 61–68.

Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Calderone, V., Fiamingo, F. L., Giorgi, I., Leonardi, M., Livi, O., Martelli, A. & Martinotti, E. (2006). Eur. J. Med. Chem. 41, 761–767

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Hempel, A., Camerman, N., Mastropaolo, D. & Camerman, A. (2005). Acta Cryst. E61, o2283–o2285.

Hunter, K. A. & Simpson, J. (1999). TITAN2000. University of Otago, New Zealand.

Lewis, F. D. & Long, T. M. (1998). J. Phys. Chem. A, 102, 5327–5332

Lindgren, H., Pero, R. W., Ivars, F. & Leanderson, T. (2001). Mol. Immunol. 38, 267–277.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.

Olsson, A. R., Lindgren, H., Pero, R. W. & Leanderson, T. (2002). Br. J. Cancer, 86, 971–978.

Reinaud, O., Capdevielle, P. & Maumy, M. (1991). J. Chem. Soc. Perkin Trans. 1, pp. 2129–2134,

Saeed, A., Khera, R. A., Abbas, N., Simpson, J. & Stanley, R. G. (2008). Acta Cryst. E64, o1976.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Vega-noverola, A. P., Soto, J. M., Noguera, F. P., Mauri, J. M. & Spickett, G. W. R. (1989). US Patent No. 4 877 780.

Westrip, S. P. (2008). publCIF. In preparation.

Yoo, C. L., Fettinger, J. C. & Kurth, M. J. (2005). J. Org. Chem. 70, 6941–6943.

Zhichkin, P., Kesicki, E., Treiberg, J., Bourdon, L., Ronsheim, M., Ooi, H. C., White, S., Judkins, A. & Fairfax, D. (2007). Org. Lett. 9, 1415–1418.