N-tert-Butyl-3-mesitylpropanamide

Maharramov, A.M.; Khalilov, A.N.; Gurbanov, A.V.; Brito, I.

doi:10.1107/S1600536811015856

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1307

doi:10.1107/S1600536811015856

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N-tert-Butyl-3-mesitylpropanamide

Abel M. Maharramov,^a Ali N. Khalilov,^a Atash V. Gurbanov ^a and Iván Brito ^b ^*

^aDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, and ^bDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta - Chile
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 18 April 2011; accepted 26 April 2011; online 7 May 2011)

In the title compound, C₁₆H₂₅NO, the N-tert-butylpropanamide fragment is essentially planar, with the exception of two C atoms of the tert-butyl group (r.m.s. deviation = 0.005 Å), forming a dihedral angle of 84.09 (10)° with the plane of the mesityl fragment (r.m.s. deviation = 0.002 Å). The crystal packing is stabilized by an intermolecular N—H⋯O hydrogen bond, which links the molecules into chains with graph-set notation C(4) running parallel to the c axis.

Related literature

For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₆H₂₅NO
M_r = 247.37
Monoclinic, P 2₁ /c
a = 12.8851 (11) Å
b = 13.3441 (11) Å
c = 9.4741 (8) Å
β = 106.540 (2)°
V = 1561.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.06 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.987, T_max = 0.987
11870 measured reflections
3870 independent reflections
1738 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.173
S = 1.00
3870 reflections
169 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.83	2.17	2.979 (2)	165
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2001 ); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015856/om2425sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015856/om2425Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811015856/om2425Isup3.cml

checkCIF report

Comment top

Fig. 1 shows the structure of title compound. Bond lengths and angles are unexceptional. The dihedral angle between the mesityl fragment and the C7/C6/C5/O1/N1/C4/C3 plane is 84.09 (10)°. Methyl groups of the benzene ring are into the same plane (r.m.s. deviation = 0.002 Å). In the crystal, molecules are linked by N— H···O interactions into chains with graph-set notation C(4) along [001], Figure 2, Table 1 (Bernstein et al., 1995).

Related literature top

For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A mixture of 0.001 mol of 1-chloro-3-(2,4,6-trimethylphenyl)propan-2-one and 0.001 mol of tert-butylamine was stirred in water in presence of sodium hydroxide (0.003 mol) for 35–40 minutes. The crystals were recrystallized from ethanol solution (Yield 86%, melting point 143°C).¹H NMRspectrum, DMSO-d₆, δ, p.p.m..: 1.25 (s, 9H, 3CH₃), 2.15 (s, 2H, CH₂CO),2.25 (s, 9H, 3CH₃), 2.75 (t, 2H, CH₂Ar), 6.75 (s, 2H, 2CH_Ar),7.45 (s, 1H, NHCO). ¹³C NMR spectrum, DMSO-d₆, δ, p.p.m..: 19 (2CH₃), 21 (CH₃), 23(CH₂CO), 25 [(CH₃)₃], 37 (CH₂Ar),50 (C_i), 129 (CH_Ar), 136 (C_i), 137 (C_i),162 (CONH). IR spectrum, ν (cm^-1)_: 3360,3170, 3005, 2928, 2878, 1645,1615, 1470, 1430, 715, 605.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are shown as circles of arbitrary radius.
	Fig. 2. Part of the crystal structure showing the formation of a C(4) chain along [001]. Hydrogen bond shown as dashed lines. Symmetry code: (a) x, 1/2 - y, -1/2 + z.

N-tert-Butyl-3-mesitylpropanamide top

Crystal data top

C₁₆H₂₅NO	F(000) = 544
M_r = 247.37	D_x = 1.052 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1996 reflections
a = 12.8851 (11) Å	θ = 2.3–28.0°
b = 13.3441 (11) Å	µ = 0.06 mm⁻¹
c = 9.4741 (8) Å	T = 296 K
β = 106.540 (2)°	Prism, colourless
V = 1561.6 (2) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3870 independent reflections
Radiation source: fine-focus sealed tube	1738 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
T_min = 0.987, T_max = 0.987	k = −15→17
11870 measured reflections	l = −12→12

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)] = 0.065	Hydrogen site location: difference Fourier map
wR(F²) = 0.173	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0732P)² + 0.0483P] where P = (F_o² + 2F_c²)/3
3870 reflections	(Δ/σ)_max = 0.001
169 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₆H₂₅NO	V = 1561.6 (2) Å³
M_r = 247.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.8851 (11) Å	µ = 0.06 mm⁻¹
b = 13.3441 (11) Å	T = 296 K
c = 9.4741 (8) Å	0.20 × 0.20 × 0.20 mm
β = 106.540 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3870 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1738 reflections with I > 2σ(I)
T_min = 0.987, T_max = 0.987	R_int = 0.052
11870 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.00	Δρ_max = 0.15 e Å⁻³
3870 reflections	Δρ_min = −0.14 e Å⁻³
169 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	0.13712 (13)	0.29736 (13)	0.94818 (15)	0.0737 (5)
N1	0.09333 (13)	0.20507 (13)	0.74037 (17)	0.0506 (5)
H1N	0.1102	0.1935	0.6635	0.076*
C1	0.0057 (2)	0.1074 (2)	0.8929 (3)	0.0898 (9)
H1A	0.0617	0.0580	0.9039	0.135*
H1B	−0.0606	0.0750	0.8940	0.135*
H1C	0.0263	0.1545	0.9727	0.135*
C2	−0.0933 (2)	0.2444 (2)	0.7318 (3)	0.0853 (8)
H2A	−0.0668	0.2942	0.8065	0.128*
H2B	−0.1597	0.2168	0.7417	0.128*
H2C	−0.1062	0.2746	0.6364	0.128*
C3	−0.0456 (2)	0.0878 (2)	0.6233 (3)	0.0851 (8)
H3A	0.0075	0.0357	0.6355	0.128*
H3B	−0.0529	0.1218	0.5316	0.128*
H3C	−0.1140	0.0592	0.6231	0.128*
C4	−0.01024 (17)	0.16181 (16)	0.7488 (2)	0.0521 (6)
C5	0.15762 (17)	0.26650 (16)	0.8371 (2)	0.0510 (5)
C6	0.25971 (18)	0.29603 (19)	0.8001 (2)	0.0676 (7)
H6A	0.2405	0.3213	0.7000	0.081*
H6B	0.3040	0.2368	0.8039	0.081*
C7	0.32616 (18)	0.37485 (17)	0.9021 (2)	0.0607 (6)
H7A	0.2826	0.4347	0.8977	0.073*
H7B	0.3454	0.3500	1.0025	0.073*
C8	0.42772 (17)	0.40167 (16)	0.8626 (2)	0.0505 (5)
C9	0.5242 (2)	0.35047 (15)	0.9257 (2)	0.0570 (6)
C10	0.61689 (19)	0.37656 (17)	0.8878 (2)	0.0611 (6)
H10	0.6810	0.3426	0.9316	0.073*
C11	0.61718 (18)	0.45079 (17)	0.7879 (3)	0.0587 (6)
C12	0.52139 (19)	0.49934 (17)	0.7257 (2)	0.0630 (6)
H12	0.5199	0.5495	0.6570	0.076*
C13	0.42684 (17)	0.47697 (17)	0.7607 (2)	0.0572 (6)
C14	0.3253 (2)	0.5357 (2)	0.6890 (3)	0.0936 (9)
H14A	0.3410	0.5858	0.6252	0.140*
H14B	0.2998	0.5676	0.7636	0.140*
H14C	0.2706	0.4912	0.6326	0.140*
C15	0.7201 (2)	0.4793 (2)	0.7516 (3)	0.0929 (9)
H15A	0.7026	0.5186	0.6631	0.139*
H15B	0.7576	0.4197	0.7374	0.139*
H15C	0.7655	0.5177	0.8311	0.139*
C16	0.5308 (2)	0.26788 (19)	1.0379 (3)	0.0885 (9)
H16A	0.6026	0.2403	1.0664	0.133*
H16B	0.4797	0.2162	0.9954	0.133*
H16C	0.5144	0.2949	1.1229	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0738 (12)	0.1073 (13)	0.0501 (8)	−0.0259 (10)	0.0340 (8)	−0.0230 (9)
N1	0.0494 (11)	0.0637 (11)	0.0448 (9)	−0.0096 (9)	0.0234 (8)	−0.0049 (9)
C1	0.088 (2)	0.106 (2)	0.0798 (17)	−0.0271 (17)	0.0309 (15)	0.0263 (16)
C2	0.0554 (16)	0.092 (2)	0.112 (2)	0.0023 (14)	0.0289 (15)	−0.0023 (16)
C3	0.0772 (18)	0.098 (2)	0.0874 (18)	−0.0387 (16)	0.0342 (15)	−0.0283 (16)
C4	0.0465 (13)	0.0615 (13)	0.0528 (12)	−0.0089 (11)	0.0211 (10)	0.0006 (11)
C5	0.0506 (13)	0.0637 (14)	0.0426 (11)	−0.0100 (11)	0.0193 (10)	−0.0045 (11)
C6	0.0587 (15)	0.0892 (17)	0.0620 (13)	−0.0250 (13)	0.0287 (12)	−0.0247 (13)
C7	0.0588 (15)	0.0677 (14)	0.0581 (13)	−0.0112 (12)	0.0204 (11)	−0.0143 (12)
C8	0.0481 (13)	0.0538 (12)	0.0503 (11)	−0.0108 (11)	0.0151 (10)	−0.0124 (11)
C9	0.0636 (16)	0.0493 (13)	0.0551 (12)	−0.0051 (12)	0.0120 (11)	−0.0082 (11)
C10	0.0482 (14)	0.0597 (14)	0.0708 (15)	0.0019 (11)	0.0097 (12)	−0.0091 (13)
C11	0.0501 (14)	0.0606 (14)	0.0681 (14)	−0.0077 (12)	0.0211 (11)	−0.0114 (12)
C12	0.0674 (17)	0.0595 (14)	0.0639 (14)	−0.0038 (13)	0.0216 (12)	0.0052 (12)
C13	0.0487 (13)	0.0610 (14)	0.0592 (13)	−0.0004 (11)	0.0113 (11)	−0.0035 (12)
C14	0.0691 (19)	0.103 (2)	0.101 (2)	0.0138 (16)	0.0129 (16)	0.0256 (18)
C15	0.0692 (18)	0.105 (2)	0.116 (2)	−0.0129 (16)	0.0455 (16)	−0.0076 (18)
C16	0.095 (2)	0.0770 (18)	0.0887 (18)	−0.0019 (16)	0.0175 (16)	0.0204 (15)

Geometric parameters (Å, º) top

O1—C5	1.226 (2)	C7—H7B	0.9700
N1—C5	1.329 (2)	C8—C13	1.391 (3)
N1—C4	1.477 (2)	C8—C9	1.395 (3)
N1—H1N	0.8310	C9—C10	1.386 (3)
C1—C4	1.508 (3)	C9—C16	1.517 (3)
C1—H1A	0.9600	C10—C11	1.371 (3)
C1—H1B	0.9600	C10—H10	0.9300
C1—H1C	0.9600	C11—C12	1.370 (3)
C2—C4	1.513 (3)	C11—C15	1.510 (3)
C2—H2A	0.9600	C12—C13	1.383 (3)
C2—H2B	0.9600	C12—H12	0.9300
C2—H2C	0.9600	C13—C14	1.511 (3)
C3—C4	1.512 (3)	C14—H14A	0.9600
C3—H3A	0.9600	C14—H14B	0.9600
C3—H3B	0.9600	C14—H14C	0.9600
C3—H3C	0.9600	C15—H15A	0.9600
C5—C6	1.507 (3)	C15—H15B	0.9600
C6—C7	1.517 (3)	C15—H15C	0.9600
C6—H6A	0.9700	C16—H16A	0.9600
C6—H6B	0.9700	C16—H16B	0.9600
C7—C8	1.503 (3)	C16—H16C	0.9600
C7—H7A	0.9700

C5—N1—C4	126.81 (16)	C8—C7—H7B	109.1
C5—N1—H1N	116.8	C6—C7—H7B	109.1
C4—N1—H1N	116.1	H7A—C7—H7B	107.9
C4—C1—H1A	109.5	C13—C8—C9	118.8 (2)
C4—C1—H1B	109.5	C13—C8—C7	120.6 (2)
H1A—C1—H1B	109.5	C9—C8—C7	120.6 (2)
C4—C1—H1C	109.5	C10—C9—C8	119.6 (2)
H1A—C1—H1C	109.5	C10—C9—C16	118.9 (2)
H1B—C1—H1C	109.5	C8—C9—C16	121.4 (2)
C4—C2—H2A	109.5	C11—C10—C9	122.2 (2)
C4—C2—H2B	109.5	C11—C10—H10	118.9
H2A—C2—H2B	109.5	C9—C10—H10	118.9
C4—C2—H2C	109.5	C12—C11—C10	117.4 (2)
H2A—C2—H2C	109.5	C12—C11—C15	121.7 (2)
H2B—C2—H2C	109.5	C10—C11—C15	121.0 (2)
C4—C3—H3A	109.5	C11—C12—C13	122.8 (2)
C4—C3—H3B	109.5	C11—C12—H12	118.6
H3A—C3—H3B	109.5	C13—C12—H12	118.6
C4—C3—H3C	109.5	C12—C13—C8	119.2 (2)
H3A—C3—H3C	109.5	C12—C13—C14	119.3 (2)
H3B—C3—H3C	109.5	C8—C13—C14	121.5 (2)
N1—C4—C1	110.16 (18)	C13—C14—H14A	109.5
N1—C4—C3	106.71 (16)	C13—C14—H14B	109.5
C1—C4—C3	109.3 (2)	H14A—C14—H14B	109.5
N1—C4—C2	109.41 (18)	C13—C14—H14C	109.5
C1—C4—C2	110.9 (2)	H14A—C14—H14C	109.5
C3—C4—C2	110.2 (2)	H14B—C14—H14C	109.5
O1—C5—N1	123.68 (19)	C11—C15—H15A	109.5
O1—C5—C6	121.82 (19)	C11—C15—H15B	109.5
N1—C5—C6	114.49 (17)	H15A—C15—H15B	109.5
C5—C6—C7	113.87 (17)	C11—C15—H15C	109.5
C5—C6—H6A	108.8	H15A—C15—H15C	109.5
C7—C6—H6A	108.8	H15B—C15—H15C	109.5
C5—C6—H6B	108.8	C9—C16—H16A	109.5
C7—C6—H6B	108.8	C9—C16—H16B	109.5
H6A—C6—H6B	107.7	H16A—C16—H16B	109.5
C8—C7—C6	112.32 (17)	C9—C16—H16C	109.5
C8—C7—H7A	109.1	H16A—C16—H16C	109.5
C6—C7—H7A	109.1	H16B—C16—H16C	109.5

C5—N1—C4—C1	−54.9 (3)	C7—C8—C9—C16	−1.2 (3)
C5—N1—C4—C3	−173.5 (2)	C8—C9—C10—C11	−0.9 (3)
C5—N1—C4—C2	67.3 (3)	C16—C9—C10—C11	−179.6 (2)
C4—N1—C5—O1	−1.4 (3)	C9—C10—C11—C12	0.1 (3)
C4—N1—C5—C6	178.5 (2)	C9—C10—C11—C15	178.5 (2)
O1—C5—C6—C7	−6.5 (3)	C10—C11—C12—C13	0.6 (3)
N1—C5—C6—C7	173.65 (19)	C15—C11—C12—C13	−177.8 (2)
C5—C6—C7—C8	179.5 (2)	C11—C12—C13—C8	−0.4 (3)
C6—C7—C8—C13	88.1 (2)	C11—C12—C13—C14	178.8 (2)
C6—C7—C8—C9	−90.9 (2)	C9—C8—C13—C12	−0.5 (3)
C13—C8—C9—C10	1.1 (3)	C7—C8—C13—C12	−179.47 (19)
C7—C8—C9—C10	−179.89 (18)	C9—C8—C13—C14	−179.6 (2)
C13—C8—C9—C16	179.8 (2)	C7—C8—C13—C14	1.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.83	2.17	2.979 (2)	165

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₂₅NO
M_r	247.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.8851 (11), 13.3441 (11), 9.4741 (8)
β (°)	106.540 (2)
V (Å³)	1561.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.06
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.987, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	11870, 3870, 1738
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.173, 1.00
No. of reflections	3870
No. of parameters	169
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.14

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.83	2.17	2.979 (2)	165

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

The authors are grateful to Baku State University for supporting this study. IB thanks the Spanish Research Council (CSIC) for the provision of a free-of-charge license to the Cambridge Structural Database.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2001). SAINT. . Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar