3-Chloro-N-(4-hydr­oxy-3-methoxy­benz­yl)-2,2-dimethyl­propanamide

Huang, Y.-L.; Wang, W.-L.; Shan, S.

doi:10.1107/S1600536810009529

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o877

doi:10.1107/S1600536810009529

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3-Chloro-N-(4-hydroxy-3-methoxybenzyl)-2,2-dimethylpropanamide

Yan-Lan Huang,^a Wen-Long Wang ^a and Shang Shan ^a ^*

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
^*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 7 March 2010; accepted 12 March 2010; online 20 March 2010)

In the molecular structure of the title compound, C₁₃H₁₈ClNO₃, the amide group is nearly perpendicular to the benzene ring, making a dihedral angle of 85.66 (9)°. The C=O bond distance of 1.242 (3) Å and the C—N bond distance of 1.333 (3) Å suggest electron delocalization in the amide fragment. Intermolecular O—H⋯O and N—H⋯O hydrogen bonding helps to stabilize the crystal structure.

Related literature

The title compound is a derivative of capsaicin. For the biological activity of capsaicin, see: Kaga et al. (1989 ). For a related structure, see: Xia et al. (2009 ).

Experimental

Crystal data

C₁₃H₁₈ClNO₃
M_r = 271.73
Monoclinic, P 2₁ /c
a = 9.3074 (10) Å
b = 11.5585 (13) Å
c = 13.0652 (14) Å
β = 90.378 (4)°
V = 1405.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 294 K
0.40 × 0.38 × 0.32 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
15383 measured reflections
2732 independent reflections
2254 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.167
S = 1.05
2732 reflections
167 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ⁱ	0.93	1.76	2.685 (2)	175
N1—H1N⋯O2ⁱⁱ	0.92	2.25	3.093 (3)	152
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009529/xu2733sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009529/xu2733Isup2.hkl

checkCIF report

Comment top

Capsaicin, a pungent principle of capsicums, has been shown a variety of biological activities including mutagenicity (Kaga et al. 1989). During the investigation on syntheses of capsaicin derivatives, the title compound has recently been prepared in the labotory and its crystal structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The amide fragment is nearly perpendicular to the benzene ring [dihedral angle 85.66 (9))°]. The longer C9═O3 bond distance of 1.242 (3) Å and the shorter C9—N1 bond distance of 1.333 (3) Å suggest the electron delocalization in the amide fragment, which is comparable to that found in the related compound N-(4-Hydroxy-3-methoxybenzyl)benzamide (Xia et al. 2009).

Intermolecular O—H···O and N—H···O hydrogen bonding is present in the crystal structure (Table 1), which helps to stabilize the crystal structure.

Related literature top

The title compound is a derivative of capsaicin. For the biological activity of capsaicin, see: Kaga et al. (1989). For a related structure, see: Xia et al. (2009).

Experimental top

4-Hydroxy-3-methoxy benzylamine HCl salt (4.7 g, 25 mmol) and dimethylformamide (25 ml) were added to a 100 ml 3-necked flask equipped with an additional funnel, a thermometer and a magnetic stirrer. Water solution (10 ml) of NaOH (2.0 g) was added at room temperature. The mixture was stirred at 308 K for 30 min and then cooled to 273 K. An ether solution (10 ml) of 2,2-dimethyl-3-chloropropionyl chloride (3.9 g, 25 mmol) was added dropwise at about 273 K over 15 min. After stirred for 2 h at room temperature the mixture was poured into 1M HCl solution (120 ml) , and then extracted with ethyl acetate. The ethyl acetate extract was washed with saturated NaHCO₃ and brine. The extract was then dried over anhydrous Na₂SO₄ and filtered. Solvents were removed under vacuum at about 308 K to give a solid crude. Recrystallization was performed twice with an absolute ethyl acetate to obtain colourless single crystals of the title compound.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound with 30% probability displacement (arbitrary spheres for H atoms).

3-Chloro-N-(4-hydroxy-3-methoxybenzyl)-2,2-dimethylpropanamide top

Crystal data top

C₁₃H₁₈ClNO₃	F(000) = 576
M_r = 271.73	D_x = 1.284 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3466 reflections
a = 9.3074 (10) Å	θ = 2.2–24.0°
b = 11.5585 (13) Å	µ = 0.27 mm⁻¹
c = 13.0652 (14) Å	T = 294 K
β = 90.378 (4)°	Prism, colorless
V = 1405.5 (3) Å³	0.40 × 0.38 × 0.32 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2254 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 26.0°, θ_min = 2.2°
Detector resolution: 10.0 pixels mm^-1	h = −10→11
ω scans	k = −13→14
15383 measured reflections	l = −16→16
2732 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.167	w = 1/[σ²(F_o²) + (0.0726P)² + 1.051P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
2732 reflections	Δρ_max = 0.48 e Å⁻³
167 parameters	Δρ_min = −0.67 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (3)

Crystal data top

C₁₃H₁₈ClNO₃	V = 1405.5 (3) Å³
M_r = 271.73	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3074 (10) Å	µ = 0.27 mm⁻¹
b = 11.5585 (13) Å	T = 294 K
c = 13.0652 (14) Å	0.40 × 0.38 × 0.32 mm
β = 90.378 (4)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2254 reflections with I > 2σ(I)
15383 measured reflections	R_int = 0.042
2732 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.167	H-atom parameters constrained
S = 1.05	Δρ_max = 0.48 e Å⁻³
2732 reflections	Δρ_min = −0.67 e Å⁻³
167 parameters

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 > 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
Cl1	0.85692 (18)	0.09530 (8)	0.35770 (8)	0.1195 (6)
N1	0.7804 (2)	0.39529 (17)	0.22613 (15)	0.0410 (5)
H1N	0.7416	0.4356	0.2801	0.061*
O1	0.18986 (18)	0.14975 (16)	0.13257 (15)	0.0539 (5)
H1A	0.1120	0.1961	0.1482	0.081*
O2	0.43484 (18)	0.03920 (15)	0.14718 (15)	0.0542 (5)
O3	0.95555 (18)	0.27805 (16)	0.17024 (13)	0.0509 (5)
C1	0.3123 (2)	0.2148 (2)	0.12573 (18)	0.0409 (5)
C2	0.4447 (2)	0.1577 (2)	0.13548 (18)	0.0404 (5)
C3	0.5709 (2)	0.2199 (2)	0.13426 (18)	0.0431 (6)
H3	0.6581	0.1815	0.1422	0.052*
C4	0.5700 (2)	0.3402 (2)	0.12130 (17)	0.0400 (5)
C5	0.4394 (3)	0.3947 (2)	0.10673 (19)	0.0445 (6)
H5	0.4371	0.4741	0.0953	0.053*
C6	0.3112 (2)	0.3327 (2)	0.10891 (19)	0.0451 (6)
H6	0.2243	0.3710	0.0990	0.054*
C7	0.5646 (3)	−0.0248 (2)	0.1367 (2)	0.0572 (7)
H7A	0.6070	−0.0079	0.0715	0.086*
H7B	0.5441	−0.1061	0.1409	0.086*
H7C	0.6303	−0.0036	0.1904	0.086*
C8	0.7093 (3)	0.4073 (2)	0.12661 (18)	0.0445 (6)
H8A	0.7732	0.3799	0.0735	0.053*
H8B	0.6898	0.4885	0.1138	0.053*
C9	0.8956 (2)	0.32899 (19)	0.24198 (17)	0.0371 (5)
C10	0.9530 (2)	0.3193 (2)	0.35204 (17)	0.0410 (5)
C11	1.0014 (4)	0.1958 (3)	0.3707 (2)	0.0669 (9)
H11A	1.0419	0.1898	0.4391	0.080*
H11B	1.0761	0.1761	0.3223	0.080*
C12	0.8444 (3)	0.3548 (3)	0.4336 (2)	0.0599 (7)
H12A	0.7575	0.3111	0.4245	0.090*
H12B	0.8236	0.4358	0.4270	0.090*
H12C	0.8838	0.3398	0.5003	0.090*
C13	1.0859 (4)	0.3961 (3)	0.3605 (2)	0.0779 (11)
H13A	1.1292	0.3865	0.4268	0.117*
H13B	1.0586	0.4755	0.3513	0.117*
H13C	1.1535	0.3746	0.3086	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.2206 (15)	0.0570 (6)	0.0811 (7)	−0.0548 (7)	0.0203 (7)	−0.0059 (4)
N1	0.0349 (10)	0.0439 (11)	0.0441 (11)	0.0031 (8)	0.0016 (8)	−0.0048 (8)
O1	0.0314 (9)	0.0475 (10)	0.0829 (13)	0.0019 (7)	0.0038 (8)	−0.0097 (9)
O2	0.0373 (9)	0.0415 (10)	0.0838 (13)	0.0063 (7)	0.0059 (8)	0.0056 (9)
O3	0.0412 (10)	0.0648 (12)	0.0466 (10)	0.0112 (8)	0.0010 (7)	−0.0106 (8)
C1	0.0306 (12)	0.0464 (13)	0.0457 (12)	0.0014 (9)	0.0012 (9)	−0.0064 (10)
C2	0.0361 (12)	0.0403 (12)	0.0447 (12)	0.0060 (9)	0.0018 (9)	0.0004 (10)
C3	0.0334 (12)	0.0479 (14)	0.0480 (13)	0.0078 (10)	0.0009 (10)	0.0037 (10)
C4	0.0360 (12)	0.0466 (13)	0.0374 (11)	0.0020 (10)	−0.0009 (9)	0.0024 (9)
C5	0.0426 (14)	0.0401 (13)	0.0508 (14)	0.0043 (10)	−0.0033 (11)	0.0014 (10)
C6	0.0323 (12)	0.0461 (14)	0.0568 (14)	0.0087 (10)	−0.0050 (10)	−0.0034 (11)
C7	0.0478 (15)	0.0458 (15)	0.0780 (19)	0.0146 (12)	0.0061 (13)	0.0059 (13)
C8	0.0395 (13)	0.0484 (14)	0.0455 (13)	−0.0005 (10)	0.0000 (10)	0.0066 (10)
C9	0.0287 (11)	0.0374 (11)	0.0451 (12)	−0.0047 (9)	0.0023 (9)	−0.0013 (9)
C10	0.0382 (13)	0.0419 (13)	0.0429 (12)	−0.0041 (10)	−0.0008 (9)	−0.0005 (10)
C11	0.086 (2)	0.0616 (18)	0.0531 (16)	0.0212 (16)	−0.0002 (15)	0.0045 (13)
C12	0.0694 (19)	0.0669 (18)	0.0436 (14)	0.0124 (15)	0.0050 (12)	−0.0004 (12)
C13	0.072 (2)	0.102 (3)	0.0593 (18)	−0.0448 (19)	−0.0166 (15)	0.0090 (17)

Geometric parameters (Å, º) top

Cl1—C11	1.784 (4)	C6—H6	0.9300
N1—C9	1.333 (3)	C7—H7A	0.9600
N1—C8	1.462 (3)	C7—H7B	0.9600
N1—H1N	0.9206	C7—H7C	0.9600
O1—C1	1.369 (3)	C8—H8A	0.9700
O1—H1A	0.9252	C8—H8B	0.9700
O2—C2	1.382 (3)	C9—C10	1.535 (3)
O2—C7	1.424 (3)	C10—C11	1.516 (4)
O3—C9	1.242 (3)	C10—C13	1.526 (4)
C1—C6	1.380 (4)	C10—C12	1.530 (3)
C1—C2	1.403 (3)	C11—H11A	0.9700
C2—C3	1.378 (3)	C11—H11B	0.9700
C3—C4	1.400 (3)	C12—H12A	0.9600
C3—H3	0.9300	C12—H12B	0.9600
C4—C5	1.381 (3)	C12—H12C	0.9600
C4—C8	1.512 (3)	C13—H13A	0.9600
C5—C6	1.392 (3)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600

C9—N1—C8	123.50 (19)	C4—C8—H8A	109.2
C9—N1—H1N	119.4	N1—C8—H8B	109.2
C8—N1—H1N	117.1	C4—C8—H8B	109.2
C1—O1—H1A	110.5	H8A—C8—H8B	107.9
C2—O2—C7	116.58 (19)	O3—C9—N1	121.3 (2)
O1—C1—C6	123.2 (2)	O3—C9—C10	121.1 (2)
O1—C1—C2	117.8 (2)	N1—C9—C10	117.55 (19)
C6—C1—C2	119.0 (2)	C11—C10—C13	107.3 (3)
C3—C2—O2	125.2 (2)	C11—C10—C12	109.7 (2)
C3—C2—C1	120.2 (2)	C13—C10—C12	109.5 (2)
O2—C2—C1	114.7 (2)	C11—C10—C9	108.7 (2)
C2—C3—C4	121.0 (2)	C13—C10—C9	107.60 (19)
C2—C3—H3	119.5	C12—C10—C9	113.9 (2)
C4—C3—H3	119.5	C10—C11—Cl1	112.0 (2)
C5—C4—C3	118.3 (2)	C10—C11—H11A	109.2
C5—C4—C8	121.7 (2)	Cl1—C11—H11A	109.2
C3—C4—C8	119.9 (2)	C10—C11—H11B	109.2
C4—C5—C6	121.1 (2)	Cl1—C11—H11B	109.2
C4—C5—H5	119.5	H11A—C11—H11B	107.9
C6—C5—H5	119.5	C10—C12—H12A	109.5
C1—C6—C5	120.4 (2)	C10—C12—H12B	109.5
C1—C6—H6	119.8	H12A—C12—H12B	109.5
C5—C6—H6	119.8	C10—C12—H12C	109.5
O2—C7—H7A	109.5	H12A—C12—H12C	109.5
O2—C7—H7B	109.5	H12B—C12—H12C	109.5
H7A—C7—H7B	109.5	C10—C13—H13A	109.5
O2—C7—H7C	109.5	C10—C13—H13B	109.5
H7A—C7—H7C	109.5	H13A—C13—H13B	109.5
H7B—C7—H7C	109.5	C10—C13—H13C	109.5
N1—C8—C4	112.03 (19)	H13A—C13—H13C	109.5
N1—C8—H8A	109.2	H13B—C13—H13C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱ	0.93	1.76	2.685 (2)	175
N1—H1N···O2ⁱⁱ	0.92	2.25	3.093 (3)	152

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₈ClNO₃
M_r	271.73
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	9.3074 (10), 11.5585 (13), 13.0652 (14)
β (°)	90.378 (4)
V (Å³)	1405.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.40 × 0.38 × 0.32

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15383, 2732, 2254
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.167, 1.05
No. of reflections	2732
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.67

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱ	0.93	1.76	2.685 (2)	175
N1—H1N···O2ⁱⁱ	0.92	2.25	3.093 (3)	152

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

Acknowledgements

The work was supported by the Natural Science Foundation of Zhejiang Province of China (No. M203027).

References

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