N-Cyclo­hexyl-3-fluoro­benzamide

Abstract

In the title mol­ecule, C₁₃H₁₆FNO, the amide (N—C=O) plane is oriented at an angle of 29.9 (2)° with respect to the aromatic ring. The cyclo­hexane ring adopts the usual chair conformation. In the crystal structure, inter­molecular N—H⋯O hydrogen bonds link the mol­ecules into chains along [100]. A weak C—H⋯F inter­action is also observed. The F atom is disordered over two positions with occupancy factors of 0.873 (3) and 0.127 (3).

Related literature

For related structures, see: Chopra & Guru Row (2005 ▶); Saeed et al. (2008a ▶,b ▶).

Experimental

Crystal data

• C₁₃H₁₆FNO

• M _r = 221.27

• Monoclinic,

• a = 5.267 (3) Å

• b = 6.599 (4) Å

• c = 16.755 (9) Å

• β = 90.090 (17)°

• V = 582.4 (6) ų

• Z = 2

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 120 (2) K

• 0.45 × 0.40 × 0.21 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.962, T _max = 0.978

• 5071 measured reflections

• 1492 independent reflections

• 1420 reflections with I > 2σ(I)

• R _int = 0.034

Refinement

• R[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 0.098

• S = 1.05

• 1492 reflections

• 150 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.25 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.88	2.25	3.050 (2)	152
C5—H5A⋯F1ii	0.95	2.58	3.310 (3)	134

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The background to this study has been described in an earlier paper (Saeed et al., 2008b).

The molecular structure of the title compound is related to that of the 2,4-dichloro compound (Saeed et al., 2008a). The cyclohexane ring is in the most stable chair conformation. In general, bond lengths and angles are within normal ranges. The aromatic ring C2–C7 is oriented with respect to the N1/O1/C1 plane at a dihedral angle of 29.9 (2)°. The N1–C1–C2–C7 torsion angle is 150.37 (15)°, for the reported dichloro compound the corresponding angle is 130.16 (18)°.

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into infinite chains along the [100] direction (Fig. 2), in which they may be effective in the stabilization of the structure. Another intermolecular interaction is C—H···F (Table 1), as found in 4-fluoro-N-(2-fluorophenyl)benzamide (Chopra & Row, 2005).

Experimental

3,5-Difluorobenzoyl chloride (5.4 mmol) in CHCl₃ was treated with cyclohexylamine (21.6 mmol) under a nitrogen atmosphere at reflux for 4 h. Upon cooling, the reaction mixture was diluted with CHCl₃ and washed consecutively with aq 1 M HCl and saturated aq NaHCO₃. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Crystallization of the residue in CHCl₃ afforded the title compound (84%). Analysis calculated for C₁₃H₁₅F₂NO: C 65.26, H 6.32, N 5.85%; found: C 65.31, H 6.39, N 5.77%.

Refinement

The F atom is disordered over two positions (F1 and F2) with site occupation factors of 0.873 (3) for F1 and 0.127 (3) for F2. H atoms were initially located in difference syntheses, but were then included in the refinement, at calculated positions, in the riding-model approximation, with N—H = 0.88 Å and C—H = 0.95–1.00 Å. The isotropic displacement parameters were set equal to 1.2Ueq of the carrier atom. In the absence of significant anomalous scattering effects, the Friedel pairs were merged.

Figures

Fig. 1.

Molecular structure of title compound, showing the rotational disorder of the fluorophenyl ring. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

Crystal packing viewed along [100] with intermolecular N–H···O hydrogen bonding pattern indicated as dashed lines. H-atoms not involved in hydrogen bonding are omitted.

Crystal data

C13H16FNO	F(000) = 236
Mr = 221.27	Dx = 1.262 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 796 reflections
a = 5.267 (3) Å	θ = 2.4–28.3°
b = 6.599 (4) Å	µ = 0.09 mm−1
c = 16.755 (9) Å	T = 120 K
β = 90.090 (17)°	Prism, colourless
V = 582.4 (6) Å3	0.45 × 0.40 × 0.21 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer	1492 independent reflections
Radiation source: sealed tube	1420 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 27.9°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −6→6
Tmin = 0.962, Tmax = 0.978	k = −8→8
5071 measured reflections	l = −22→19

Refinement

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)] = 0.035	Hydrogen site location: difference Fourier map
wR(F2) = 0.098	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0686P)2 + 0.0394P] where P = (Fo2 + 2Fc2)/3
1492 reflections	(Δ/σ)max = 0.001
150 parameters	Δρmax = 0.25 e Å−3
1 restraint	Δρmin = −0.17 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	0.9633 (3)	0.6562 (2)	0.49344 (8)	0.0376 (4)	0.873 (3)
F2	0.249 (2)	0.9837 (17)	0.3846 (6)	0.043 (3)*	0.127 (3)
O1	0.2561 (2)	0.2922 (2)	0.25636 (8)	0.0316 (3)
N1	0.6841 (3)	0.2208 (2)	0.25218 (8)	0.0206 (3)
H1A	0.8356	0.2505	0.2710	0.025*
C1	0.4794 (3)	0.3278 (2)	0.27778 (10)	0.0208 (3)
C2	0.5341 (3)	0.5002 (2)	0.33504 (9)	0.0198 (3)
C3	0.7409 (3)	0.4971 (3)	0.38818 (10)	0.0229 (3)
H3A	0.8556	0.3860	0.3894	0.027*
C4	0.7720 (3)	0.6615 (3)	0.43877 (10)	0.0269 (4)
H4A	0.9080	0.6591	0.4760	0.032*	0.127 (3)
C5	0.6128 (4)	0.8300 (3)	0.43745 (10)	0.0288 (4)
H5A	0.6419	0.9416	0.4721	0.035*
C6	0.4084 (4)	0.8306 (3)	0.38366 (11)	0.0295 (4)
H6A	0.2973	0.9439	0.3817	0.035*	0.873 (3)
C7	0.3671 (3)	0.6659 (3)	0.33314 (10)	0.0253 (4)
H7A	0.2265	0.6658	0.2976	0.030*
C8	0.6571 (3)	0.0567 (2)	0.19365 (9)	0.0195 (3)
H8A	0.4853	−0.0054	0.2003	0.023*
C9	0.6786 (4)	0.1391 (3)	0.10784 (10)	0.0275 (4)
H9A	0.5431	0.2403	0.0984	0.033*
H9B	0.8445	0.2074	0.1011	0.033*
C10	0.6542 (4)	−0.0336 (3)	0.04667 (10)	0.0299 (4)
H10A	0.4813	−0.0920	0.0497	0.036*
H10B	0.6781	0.0216	−0.0078	0.036*
C11	0.8501 (4)	−0.2007 (3)	0.06182 (11)	0.0291 (4)
H11A	1.0228	−0.1466	0.0524	0.035*
H11B	0.8212	−0.3136	0.0240	0.035*
C12	0.8313 (4)	−0.2802 (3)	0.14799 (11)	0.0272 (4)
H12A	0.6653	−0.3480	0.1555	0.033*
H12B	0.9664	−0.3818	0.1573	0.033*
C13	0.8582 (3)	−0.1078 (3)	0.20882 (11)	0.0232 (3)
H13A	1.0299	−0.0476	0.2047	0.028*
H13B	0.8379	−0.1624	0.2635	0.028*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
F1	0.0405 (8)	0.0402 (7)	0.0322 (7)	−0.0017 (6)	−0.0107 (5)	−0.0067 (6)
O1	0.0177 (6)	0.0310 (7)	0.0460 (8)	0.0009 (5)	−0.0028 (5)	−0.0113 (6)
N1	0.0172 (6)	0.0198 (6)	0.0247 (7)	0.0003 (5)	−0.0015 (5)	−0.0024 (5)
C1	0.0197 (8)	0.0181 (7)	0.0246 (7)	0.0002 (6)	0.0004 (6)	−0.0004 (6)
C2	0.0197 (8)	0.0180 (7)	0.0217 (7)	−0.0015 (6)	0.0045 (6)	0.0002 (6)
C3	0.0231 (8)	0.0221 (7)	0.0235 (7)	0.0014 (6)	0.0018 (6)	0.0010 (6)
C4	0.0270 (9)	0.0306 (9)	0.0229 (8)	−0.0040 (7)	0.0018 (6)	−0.0012 (7)
C5	0.0314 (9)	0.0259 (9)	0.0292 (8)	−0.0041 (7)	0.0075 (7)	−0.0081 (8)
C6	0.0268 (9)	0.0233 (8)	0.0385 (9)	0.0044 (7)	0.0076 (7)	−0.0052 (8)
C7	0.0214 (8)	0.0253 (8)	0.0293 (8)	0.0023 (7)	0.0013 (6)	−0.0015 (7)
C8	0.0169 (7)	0.0173 (7)	0.0243 (8)	−0.0005 (6)	−0.0003 (6)	−0.0017 (6)
C9	0.0376 (10)	0.0205 (8)	0.0242 (8)	0.0018 (7)	−0.0026 (7)	0.0000 (6)
C10	0.0367 (10)	0.0281 (9)	0.0250 (8)	−0.0007 (8)	−0.0034 (7)	−0.0043 (7)
C11	0.0290 (9)	0.0249 (8)	0.0334 (9)	−0.0032 (8)	0.0051 (7)	−0.0085 (8)
C12	0.0284 (9)	0.0177 (8)	0.0356 (9)	0.0023 (7)	−0.0016 (7)	−0.0027 (7)
C13	0.0221 (8)	0.0192 (8)	0.0285 (8)	0.0014 (6)	−0.0010 (6)	−0.0003 (6)

Geometric parameters (Å, °)

F1—C4	1.361 (2)	C8—C13	1.538 (2)
F2—C6	1.315 (11)	C8—C9	1.541 (2)
O1—C1	1.252 (2)	C8—H8A	1.00
N1—C1	1.359 (2)	C9—C10	1.538 (2)
N1—C8	1.468 (2)	C9—H9A	0.99
N1—H1A	0.88	C9—H9B	0.99
C1—C2	1.515 (2)	C10—C11	1.531 (3)
C2—C7	1.404 (2)	C10—H10A	0.99
C2—C3	1.406 (2)	C10—H10B	0.99
C3—C4	1.386 (3)	C11—C12	1.540 (3)
C3—H3A	0.95	C11—H11A	0.99
C4—C5	1.393 (3)	C11—H11B	0.99
C4—H4A	0.95	C12—C13	1.534 (2)
C5—C6	1.403 (3)	C12—H12A	0.99
C5—H5A	0.95	C12—H12B	0.99
C6—C7	1.394 (3)	C13—H13A	0.99
C6—H6A	0.95	C13—H13B	0.99
C7—H7A	0.95
C1—N1—C8	121.23 (14)	C13—C8—H8A	108.4
C1—N1—H1A	119.4	C9—C8—H8A	108.4
C8—N1—H1A	119.4	C10—C9—C8	110.76 (15)
O1—C1—N1	123.89 (15)	C10—C9—H9A	109.5
O1—C1—C2	120.02 (14)	C8—C9—H9A	109.5
N1—C1—C2	116.09 (14)	C10—C9—H9B	109.5
C7—C2—C3	120.72 (15)	C8—C9—H9B	109.5
C7—C2—C1	116.85 (14)	H9A—C9—H9B	108.1
C3—C2—C1	122.42 (15)	C11—C10—C9	111.55 (14)
C4—C3—C2	117.78 (16)	C11—C10—H10A	109.3
C4—C3—H3A	121.1	C9—C10—H10A	109.3
C2—C3—H3A	121.1	C11—C10—H10B	109.3
F1—C4—C3	118.55 (17)	C9—C10—H10B	109.3
F1—C4—C5	118.43 (16)	H10A—C10—H10B	108.0
C3—C4—C5	123.00 (16)	C10—C11—C12	110.90 (15)
C3—C4—H4A	118.5	C10—C11—H11A	109.5
C5—C4—H4A	118.5	C12—C11—H11A	109.5
C4—C5—C6	118.30 (16)	C10—C11—H11B	109.5
C4—C5—H5A	120.9	C12—C11—H11B	109.5
C6—C5—H5A	120.9	H11A—C11—H11B	108.0
F2—C6—C7	120.5 (5)	C13—C12—C11	111.33 (15)
F2—C6—C5	119.0 (5)	C13—C12—H12A	109.4
C7—C6—C5	120.42 (16)	C11—C12—H12A	109.4
C7—C6—H6A	119.8	C13—C12—H12B	109.4
C5—C6—H6A	119.8	C11—C12—H12B	109.4
C6—C7—C2	119.75 (15)	H12A—C12—H12B	108.0
C6—C7—H7A	120.1	C12—C13—C8	110.55 (13)
C2—C7—H7A	120.1	C12—C13—H13A	109.5
N1—C8—C13	110.16 (13)	C8—C13—H13A	109.5
N1—C8—C9	110.86 (13)	C12—C13—H13B	109.5
C13—C8—C9	110.58 (13)	C8—C13—H13B	109.5
N1—C8—H8A	108.4	H13A—C13—H13B	108.1
C8—N1—C1—O1	2.5 (2)	F2—C6—C7—C2	−177.6 (5)
C8—N1—C1—C2	−177.01 (13)	C5—C6—C7—C2	−1.2 (3)
O1—C1—C2—C7	−29.1 (2)	C3—C2—C7—C6	0.9 (2)
N1—C1—C2—C7	150.37 (15)	C1—C2—C7—C6	−179.27 (15)
O1—C1—C2—C3	150.71 (16)	C1—N1—C8—C13	−148.28 (15)
N1—C1—C2—C3	−29.8 (2)	C1—N1—C8—C9	89.00 (18)
C7—C2—C3—C4	0.6 (2)	N1—C8—C9—C10	179.17 (14)
C1—C2—C3—C4	−179.20 (14)	C13—C8—C9—C10	56.69 (18)
C2—C3—C4—F1	176.62 (15)	C8—C9—C10—C11	−55.8 (2)
C2—C3—C4—C5	−1.9 (3)	C9—C10—C11—C12	55.0 (2)
F1—C4—C5—C6	−176.95 (16)	C10—C11—C12—C13	−55.56 (19)
C3—C4—C5—C6	1.6 (3)	C11—C12—C13—C8	56.76 (19)
C4—C5—C6—F2	176.4 (6)	N1—C8—C13—C12	179.90 (13)
C4—C5—C6—C7	0.1 (3)	C9—C8—C13—C12	−57.21 (18)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.88	2.25	3.050 (2)	152
C5—H5A···F1ii	0.95	2.58	3.310 (3)	134

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