N-(5-Cyano­nonan-5-yl)benzamide

Song, X.; Li, W.

doi:10.1107/S2414314623006399

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 7| July 2023| x230639

https://doi.org/10.1107/S2414314623006399

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N-(5-Cyanononan-5-yl)benzamide

Xueqing Song ^a ^* and William Li ^a

^aUniversity of the District of Columbia, Chemistry, 4200 Connecticut Avenue, NW, Washington DC, 20008, USA
^*Correspondence e-mail: xsong@udc.edu

Edited by R. J. Butcher, Howard University, USA (Received 30 June 2023; accepted 21 July 2023; online 28 July 2023)

N-(5-Cyanononan-5-yl)benzamide, C₁₇H₂₄N₂O, synthesized from the reaction between benzoyl chloride and 2-amino-2-butylhexanenitrile, is an important intermediate in amino acid synthesis. Intermolecular N—H⋯O and C—H⋯O hydrogen bonds with N⋯O and C⋯O distances of 3.083 (2) and 3.304 (2) Å, respectively, link adjacent molecules into chains along the a axis. The dihedral angle between the mean plane of the phenyl group and the plane of the amide group is 19.504 (4)°.

Keywords: crystal structure; hydrogen bonding; strecker reaction; amino acid synthesis.

CCDC reference: 2283625

Structure description

The title compound was synthesized from the reaction between 2-amino-2-butylhexanenitrile and benzoyl chloride, and is an important intermediate in amino acid synthesis. Shu et al. (2008 ) reported that a benzamide was an intermediate in their five-step synthesis of Fmoc-α-methylvaline (Fmoc is the fluorenylmethoxycarbonyl protecting group). Paventi et al. (1987 ) found that the benzoyl group in the molecule had assisted the hydrolysis of the nitrile in the acid hydrolysis of benzoylaminonitrile to afford an α-amino acid. Some aminonitriles were difficult to convert into α-amino acids without introducing a benzoyl group. An oxazoline intermediate was proposed to ease the acid hydrolysis of the nitrile in 2-benzamidoadamantane-2-carbonitrile.

In the crystal of the title compound (Fig. 1), intermolecular N—H⋯O and C—H⋯O hydrogen bonds with N⋯O and C⋯O distances of 3.083 (2) and 3.304 (2) Å, respectively, link adjacent molecules into chains along the a axis (Table 1 and Figs. 2 and 3). The dihedral angle between the mean plane of the phenyl group and the plane of the amide O1/C1/N1/C12 group (r.m.s. deviation 0.002 Å) is 19.504 (4)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.93	2.52	3.3046 (17)	142
N2—H2N⋯O1ⁱ	0.860 (16)	2.229 (16)	3.0829 (13)	171.7 (13)
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Intermolecular N—H⋯O and N—H⋯O hydrogen bonds.

Figure 3
The crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

A two-step procedure was used to synthesize N-(5-cyanononan-5-yl)benzamide. The first step was the Strecker synthesis using nonan-5-one, ammonia, ammonium chloride and NaCN as starting materials to afford 2-amino-2-butylhexanenitrile. The second step was the reaction between 2-amino-2-butylhexanenitrile and benzoyl chloride in an aqueous solution of sodium bicarbonate to afford crude N-(5-cyanononan-5-yl)benzamide. This was then purified via column chromatography, and slow evaporation of a dilute solution in ethyl acetate afforded a needle-like crystal (m.p. 383–385 K).

¹H NMR (CDCl₃, ppm): δ 7.835–7.707 (2H, m), 7.621–7.526 (1H, m), 7.525–7.406 (2H, m), 6.145–5.982 (1H, s), 2.231–2.205 (4H, m), 1.656–1.339 (8H, m), 1.038–0.867 (6H, m). ¹³C NMR (CDCl₃, ppm): δ 166.7, 133.8, 132.0, 128.9, 127.0, 119.9, 55.4, 36.3, 26.4, 22.6, 13.7.

Refinement

The crystal data, data collection and structure refinement details are summarized in Table 2. The amide H atom was refined isotropically. All other H atoms were refined with isotropic displacement parameters, calculated as U_iso(H) = 1.5U_eq(C) for methyl groups and 1.2U_eq(C) otherwise.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₂₄N₂O
M_r	272.38
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	10.3939 (1), 17.6680 (2), 17.6653 (2)
V (Å³)	3244.05 (6)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	0.54
Crystal size (mm)	0.06 × 0.03 × 0.02

Data collection
Diffractometer	Rigaku XtaLAB Synergy diffractometer with a HyPix detector
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.852, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15515, 3322, 2883
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.112, 1.08
No. of reflections	3322
No. of parameters	188
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2283625

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006399/bv4049sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006399/bv4049Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314623006399/bv4049Isup3.png

Supporting information file. DOI: https://doi.org/10.1107/S2414314623006399/bv4049Isup4.mol

Supporting information file. DOI: https://doi.org/10.1107/S2414314623006399/bv4049Isup5.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2023); cell refinement: CrysAlis PRO (Rigaku OD, 2023); data reduction: CrysAlis PRO (Rigaku OD, 2023); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

N-(5-Cyanononan-5-yl)benzamide top

Crystal data top

C₁₇H₂₄N₂O	D_x = 1.115 Mg m⁻³
M_r = 272.38	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 10946 reflections
a = 10.3939 (1) Å	θ = 4.3–77.8°
b = 17.6680 (2) Å	µ = 0.54 mm⁻¹
c = 17.6653 (2) Å	T = 298 K
V = 3244.05 (6) Å³	Needle, clear light colourless
Z = 8	0.06 × 0.03 × 0.02 mm
F(000) = 1184

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix diffractometer	3322 independent reflections
Radiation source: micro-focus sealed X-ray tube	2883 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 78.0°, θ_min = 5.0°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2023)	h = −10→12
T_min = 0.852, T_max = 1.000	k = −17→22
15515 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0401P)² + 1.052P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3322 reflections	Δρ_max = 0.24 e Å⁻³
188 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL2018 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.00252 (16)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.68510 (9)	0.39486 (6)	0.24909 (6)	0.0447 (3)
N2	0.47630 (10)	0.42156 (6)	0.27067 (6)	0.0354 (3)
H2N	0.3976 (15)	0.4095 (8)	0.2635 (9)	0.039 (4)*
N3	0.63961 (13)	0.41287 (9)	0.43755 (8)	0.0585 (4)
C1	0.57087 (12)	0.38404 (7)	0.23375 (7)	0.0346 (3)
C2	0.53211 (12)	0.32919 (7)	0.17351 (7)	0.0370 (3)
C3	0.62231 (15)	0.27549 (8)	0.15148 (9)	0.0458 (3)
H3	0.702073	0.273870	0.175283	0.055*
C4	0.59447 (18)	0.22447 (8)	0.09449 (10)	0.0563 (4)
H4	0.655468	0.188838	0.079870	0.068*
C5	0.4763 (2)	0.22650 (9)	0.05942 (10)	0.0629 (5)
H5	0.457268	0.191991	0.021279	0.075*
C6	0.38608 (18)	0.27953 (10)	0.08067 (10)	0.0618 (4)
H6	0.306382	0.280710	0.056764	0.074*
C7	0.41359 (14)	0.33116 (9)	0.13756 (9)	0.0485 (4)
H7	0.352624	0.367046	0.151570	0.058*
C8	0.13369 (18)	0.42176 (12)	0.51281 (11)	0.0687 (5)
H8A	0.130708	0.369920	0.496635	0.103*
H8B	0.048757	0.438170	0.526484	0.103*
H8C	0.189651	0.426219	0.555814	0.103*
C9	0.18399 (14)	0.47054 (9)	0.44905 (9)	0.0487 (4)
H9A	0.190157	0.522524	0.466342	0.058*
H9B	0.123469	0.469132	0.407272	0.058*
C10	0.31508 (13)	0.44461 (8)	0.42125 (8)	0.0431 (3)
H10A	0.371536	0.437325	0.464367	0.052*
H10B	0.306043	0.396317	0.395690	0.052*
C11	0.37556 (13)	0.50125 (7)	0.36746 (8)	0.0388 (3)
H11A	0.390117	0.547983	0.394978	0.047*
H11B	0.314076	0.512110	0.327604	0.047*
C12	0.50346 (12)	0.47737 (7)	0.33020 (7)	0.0356 (3)
C13	0.57641 (13)	0.54701 (8)	0.29944 (8)	0.0433 (3)
H13A	0.595421	0.580531	0.341460	0.052*
H13B	0.657822	0.530128	0.278570	0.052*
C14	0.50566 (16)	0.59173 (8)	0.23929 (9)	0.0510 (4)
H14A	0.424038	0.608940	0.259590	0.061*
H14B	0.487752	0.558979	0.196493	0.061*
C15	0.58252 (18)	0.65952 (9)	0.21246 (11)	0.0601 (4)
H15A	0.604988	0.690289	0.255974	0.072*
H15B	0.661983	0.641748	0.189802	0.072*
C16	0.5124 (2)	0.70834 (11)	0.15573 (11)	0.0803 (6)
H16A	0.504894	0.681592	0.108633	0.120*
H16B	0.559606	0.754376	0.147875	0.120*
H16C	0.428131	0.720084	0.174612	0.120*
C17	0.58394 (13)	0.44031 (8)	0.38925 (8)	0.0413 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0285 (5)	0.0569 (6)	0.0487 (5)	0.0014 (4)	0.0003 (4)	−0.0047 (5)
N2	0.0269 (5)	0.0385 (6)	0.0409 (6)	−0.0016 (4)	0.0001 (4)	−0.0063 (4)
N3	0.0533 (8)	0.0720 (9)	0.0503 (7)	0.0081 (7)	−0.0086 (6)	−0.0002 (6)
C1	0.0304 (6)	0.0375 (6)	0.0359 (6)	0.0015 (5)	0.0029 (5)	0.0027 (5)
C2	0.0373 (7)	0.0361 (6)	0.0377 (6)	0.0003 (5)	0.0048 (5)	0.0007 (5)
C3	0.0473 (8)	0.0395 (7)	0.0506 (8)	0.0057 (6)	0.0068 (6)	0.0012 (6)
C4	0.0712 (11)	0.0392 (7)	0.0584 (9)	0.0067 (7)	0.0142 (8)	−0.0052 (7)
C5	0.0875 (13)	0.0489 (9)	0.0523 (9)	−0.0082 (8)	0.0043 (9)	−0.0148 (7)
C6	0.0600 (10)	0.0696 (11)	0.0558 (9)	−0.0041 (8)	−0.0106 (8)	−0.0160 (8)
C7	0.0430 (8)	0.0544 (8)	0.0482 (8)	0.0044 (6)	−0.0027 (6)	−0.0104 (6)
C8	0.0595 (10)	0.0813 (12)	0.0653 (11)	−0.0059 (9)	0.0233 (9)	0.0014 (9)
C9	0.0400 (8)	0.0557 (8)	0.0505 (8)	−0.0011 (6)	0.0079 (6)	−0.0062 (7)
C10	0.0412 (7)	0.0439 (7)	0.0442 (7)	0.0006 (6)	0.0068 (6)	−0.0020 (6)
C11	0.0358 (7)	0.0384 (7)	0.0422 (7)	0.0023 (5)	0.0031 (5)	−0.0042 (5)
C12	0.0314 (6)	0.0374 (6)	0.0380 (6)	−0.0012 (5)	0.0000 (5)	−0.0041 (5)
C13	0.0384 (7)	0.0405 (7)	0.0509 (8)	−0.0066 (6)	0.0051 (6)	−0.0052 (6)
C14	0.0580 (9)	0.0457 (8)	0.0491 (8)	−0.0105 (7)	0.0018 (7)	0.0016 (6)
C15	0.0675 (11)	0.0460 (8)	0.0668 (10)	−0.0092 (8)	0.0102 (9)	0.0051 (7)
C16	0.1201 (18)	0.0588 (11)	0.0620 (11)	−0.0232 (11)	−0.0118 (12)	0.0109 (9)
C17	0.0350 (7)	0.0459 (7)	0.0428 (7)	−0.0001 (6)	−0.0003 (6)	−0.0064 (6)

Geometric parameters (Å, º) top

O1—C1	1.2327 (15)	C9—H9A	0.9700
N2—C1	1.3531 (16)	C9—H9B	0.9700
N2—C12	1.4691 (16)	C10—C11	1.5164 (19)
N2—H2N	0.855 (16)	C10—H10A	0.9700
N3—C17	1.1393 (19)	C10—H10B	0.9700
C1—C2	1.4946 (18)	C11—C12	1.5422 (17)
C2—C7	1.386 (2)	C11—H11A	0.9700
C2—C3	1.3894 (19)	C11—H11B	0.9700
C3—C4	1.382 (2)	C12—C17	1.4888 (19)
C3—H3	0.9300	C12—C13	1.5439 (18)
C4—C5	1.376 (3)	C13—C14	1.515 (2)
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.377 (3)	C13—H13B	0.9700
C5—H5	0.9300	C14—C15	1.516 (2)
C6—C7	1.387 (2)	C14—H14A	0.9700
C6—H6	0.9300	C14—H14B	0.9700
C7—H7	0.9300	C15—C16	1.510 (3)
C8—C9	1.512 (2)	C15—H15A	0.9700
C8—H8A	0.9600	C15—H15B	0.9700
C8—H8B	0.9600	C16—H16A	0.9600
C8—H8C	0.9600	C16—H16B	0.9600
C9—C10	1.5191 (19)	C16—H16C	0.9600

C1—N2—C12	122.30 (11)	C9—C10—H10B	109.2
C1—N2—H2N	120.1 (10)	H10A—C10—H10B	107.9
C12—N2—H2N	117.2 (10)	C10—C11—C12	116.38 (11)
O1—C1—N2	121.18 (12)	C10—C11—H11A	108.2
O1—C1—C2	121.11 (11)	C12—C11—H11A	108.2
N2—C1—C2	117.71 (11)	C10—C11—H11B	108.2
C7—C2—C3	119.23 (13)	C12—C11—H11B	108.2
C7—C2—C1	123.33 (12)	H11A—C11—H11B	107.3
C3—C2—C1	117.41 (12)	N2—C12—C17	108.31 (10)
C4—C3—C2	120.54 (15)	N2—C12—C11	108.88 (10)
C4—C3—H3	119.7	C17—C12—C11	107.80 (11)
C2—C3—H3	119.7	N2—C12—C13	112.17 (11)
C5—C4—C3	119.85 (15)	C17—C12—C13	108.73 (11)
C5—C4—H4	120.1	C11—C12—C13	110.83 (10)
C3—C4—H4	120.1	C14—C13—C12	115.10 (11)
C4—C5—C6	120.18 (15)	C14—C13—H13A	108.5
C4—C5—H5	119.9	C12—C13—H13A	108.5
C6—C5—H5	119.9	C14—C13—H13B	108.5
C5—C6—C7	120.29 (16)	C12—C13—H13B	108.5
C5—C6—H6	119.9	H13A—C13—H13B	107.5
C7—C6—H6	119.9	C13—C14—C15	112.07 (14)
C2—C7—C6	119.91 (14)	C13—C14—H14A	109.2
C2—C7—H7	120.0	C15—C14—H14A	109.2
C6—C7—H7	120.0	C13—C14—H14B	109.2
C9—C8—H8A	109.5	C15—C14—H14B	109.2
C9—C8—H8B	109.5	H14A—C14—H14B	107.9
H8A—C8—H8B	109.5	C16—C15—C14	113.86 (16)
C9—C8—H8C	109.5	C16—C15—H15A	108.8
H8A—C8—H8C	109.5	C14—C15—H15A	108.8
H8B—C8—H8C	109.5	C16—C15—H15B	108.8
C8—C9—C10	112.28 (14)	C14—C15—H15B	108.8
C8—C9—H9A	109.1	H15A—C15—H15B	107.7
C10—C9—H9A	109.1	C15—C16—H16A	109.5
C8—C9—H9B	109.1	C15—C16—H16B	109.5
C10—C9—H9B	109.1	H16A—C16—H16B	109.5
H9A—C9—H9B	107.9	C15—C16—H16C	109.5
C11—C10—C9	112.05 (12)	H16A—C16—H16C	109.5
C11—C10—H10A	109.2	H16B—C16—H16C	109.5
C9—C10—H10A	109.2	N3—C17—C12	175.77 (15)
C11—C10—H10B	109.2

C12—N2—C1—O1	0.53 (19)	C8—C9—C10—C11	−169.86 (13)
C12—N2—C1—C2	−179.26 (11)	C9—C10—C11—C12	−174.73 (12)
O1—C1—C2—C7	−159.19 (14)	C1—N2—C12—C17	−55.56 (15)
N2—C1—C2—C7	20.60 (19)	C1—N2—C12—C11	−172.52 (11)
O1—C1—C2—C3	18.64 (18)	C1—N2—C12—C13	64.45 (15)
N2—C1—C2—C3	−161.57 (12)	C10—C11—C12—N2	75.12 (14)
C7—C2—C3—C4	−0.1 (2)	C10—C11—C12—C17	−42.17 (15)
C1—C2—C3—C4	−178.02 (13)	C10—C11—C12—C13	−161.06 (12)
C2—C3—C4—C5	−0.3 (2)	N2—C12—C13—C14	61.10 (15)
C3—C4—C5—C6	0.4 (3)	C17—C12—C13—C14	−179.14 (12)
C4—C5—C6—C7	−0.1 (3)	C11—C12—C13—C14	−60.82 (15)
C3—C2—C7—C6	0.4 (2)	C12—C13—C14—C15	179.43 (13)
C1—C2—C7—C6	178.21 (14)	C13—C14—C15—C16	−176.64 (15)
C5—C6—C7—C2	−0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.52	3.3046 (17)	142
N2—H2N···O1ⁱ	0.860 (16)	2.229 (16)	3.0829 (13)	171.7 (13)

Symmetry code: (i) x−1/2, y, −z+1/2.

Acknowledgements

Financial assistance from the National Science Foundation and the University of the District of Columbia (UDC) is gratefully acknowledged.

Funding information

Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (grant No. 2117621 to Xueqing Song); National Science Foundation, Directorate for Education and Human Resources (grant No. 1622811 to Freddie Dixon); National Science Foundation, Directorate for Education and Human Resources (grant No. 1833656 to Freddie Dixon).

References

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