Ethyl 3-[(3,5-dimethyl­phen­yl)amino­carbon­yl]propanoate

Gowda, B.T.; Foro, S.; Saraswathi, B.S.; Fuess, H.

doi:10.1107/S1600536809029511

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o2039

doi:10.1107/S1600536809029511

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Ethyl 3-[(3,5-dimethylphenyl)aminocarbonyl]propanoate

B. Thimme Gowda,^a ^* Sabine Foro,^b B. S. Saraswathi ^a and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 22 July 2009; accepted 24 July 2009; online 29 July 2009)

The non-H atoms in the title compound, C₁₄H₁₉NO₃, lie on a mirror plane. The amide O and ester carbonyl O atoms are trans to each other. Furthermore, the C=O and O—CH₂ bonds of the ester group are syn with respect to each other. In the crystal, molecules are packed into centrosymmetric dimers through intermolecular N—H⋯O hydrogen bonds.

Related literature

For related structures, see: Gowda et al. (2009a ,b ,c ).

Experimental

Crystal data

C₁₄H₁₉NO₃
M_r = 249.30
Tetragonal, I 4/m
a = 19.938 (2) Å
c = 7.0367 (9) Å
V = 2797.3 (5) Å³
Z = 8
Cu Kα radiation
μ = 0.67 mm⁻¹
T = 299 K
0.40 × 0.28 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
4040 measured reflections
1367 independent reflections
1201 reflections with I > 2σ(I)
R_int = 0.044
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.169
S = 1.11
1367 reflections
120 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.85 (3)	2.15 (3)	2.995 (3)	176 (3)
Symmetry code: (i) -x+1, -y, -z.

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809029511/tk2515sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029511/tk2515Isup2.hkl

checkCIF report

Comment top

As a part of studying the effect of ring and side chain substitutions on the structures of the substituted amides (Gowda et al., 2009a,b,c), the crystal structure of ethyl N-(3,5-dimethylphenyl)succinamate (I) has been determined. The non-hydrogen atoms lie on a crystallographic mirror plane. The conformations of N—H and C=O bonds in the amide segment of the structure are trans to each other (Fig. 1). Likewise, the amide-O atom and ester carbonyl-O atoms are trans to each other. The C=O and O—CH₂ bonds of the ester group are in syn positions to each other, similar to that observed between the C=O and O—H bonds in the crystal structures of N-(2,6-dimethylphenyl)succinamic acid (Gowda et al., 2009b) and N-(2-chlorophenyl)succinamic acid (Gowda et al., 2009a).

The presence of N—H···O hydrogen bonds connect the molecules into centrosymmetric dimers (Table 1).

Related literature top

For related structures, see: Gowda et al. (2009a,b,c).

Experimental top

A solution of succinic anhydride (0.025 mole) in toluene (25 ml) was treated dropwise with a solution of 3,5-dimethylaniline (0.025 mole) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about one hour and set aside for an additional hour at room temperature for the completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 3,5-dimethylaniline. The resultant solid N-(3,5-dimethylphenyl)succinamic acid was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. N-(3,5-Dimethylphenyl)succinamic acid was recrystallized into ethyl N-(3,5-dimethylphenyl)succinamate (I) from hot ethanol. The rod like colourless single crystals of (I) were grown in hot ethanolic solution by slow evaporation.

Computing details top

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC (Enraf–Nonius, 1996); data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom labelling and the displacement ellipsoids are at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of (I) with hydrogen bonds shown as dashed lines.

Ethyl 3-[(3,5-dimethylphenyl)aminocarbonyl]propanoate top

Crystal data top

C₁₄H₁₉NO₃	D_x = 1.184 Mg m⁻³
M_r = 249.30	Cu Kα radiation, λ = 1.54180 Å
Tetragonal, I4/m	Cell parameters from 25 reflections
Hall symbol: -I 4	θ = 4.4–20.5°
a = 19.938 (2) Å	µ = 0.67 mm⁻¹
c = 7.0367 (9) Å	T = 299 K
V = 2797.3 (5) Å³	Rod, colourless
Z = 8	0.40 × 0.28 × 0.25 mm
F(000) = 1072

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.044
Radiation source: fine-focus sealed tube	θ_max = 67.0°, θ_min = 3.1°
Graphite monochromator	h = −16→23
ω/2θ scans	k = −16→23
4040 measured reflections	l = −3→8
1367 independent reflections	3 standard reflections every 120 min
1201 reflections with I > 2σ(I)	intensity decay: 1.0%

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)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.169	w = 1/[σ²(F_o²) + (0.1022P)² + 1.0554P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
1367 reflections	Δρ_max = 0.32 e Å⁻³
120 parameters	Δρ_min = −0.32 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: 0.0012 (3)

Crystal data top

C₁₄H₁₉NO₃	Z = 8
M_r = 249.30	Cu Kα radiation
Tetragonal, I4/m	µ = 0.67 mm⁻¹
a = 19.938 (2) Å	T = 299 K
c = 7.0367 (9) Å	0.40 × 0.28 × 0.25 mm
V = 2797.3 (5) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.044
4040 measured reflections	3 standard reflections every 120 min
1367 independent reflections	intensity decay: 1.0%
1201 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.32 e Å⁻³
1367 reflections	Δρ_min = −0.32 e Å⁻³
120 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	Occ. (<1)
C1	0.60839 (11)	0.20945 (11)	0.0000	0.0465 (6)
C2	0.67561 (12)	0.19085 (12)	0.0000	0.0513 (6)
H2	0.6869	0.1456	0.0000	0.062*
C3	0.72584 (12)	0.23863 (13)	0.0000	0.0532 (6)
C4	0.70778 (13)	0.30566 (14)	0.0000	0.0579 (7)
H4	0.7411	0.3383	0.0000	0.070*
C5	0.64153 (13)	0.32504 (12)	0.0000	0.0562 (7)
C6	0.59123 (12)	0.27666 (12)	0.0000	0.0522 (6)
H6	0.5464	0.2894	0.0000	0.063*
C7	0.49362 (12)	0.15957 (11)	0.0000	0.0506 (6)
C8	0.45900 (11)	0.09187 (12)	0.0000	0.0543 (7)
H8A	0.4728	0.0668	−0.1115	0.065*	0.50
H8B	0.4728	0.0668	0.1115	0.065*	0.50
C9	0.38416 (12)	0.09873 (11)	0.0000	0.0515 (6)
H9A	0.3708	0.1242	0.1113	0.062*	0.50
H9B	0.3708	0.1242	−0.1113	0.062*	0.50
C10	0.34741 (11)	0.03335 (12)	0.0000	0.0491 (6)
C11	0.23912 (14)	−0.01607 (15)	0.0000	0.0666 (8)
H11	0.2470 (10)	−0.0432 (11)	0.118 (3)	0.080*
C12	0.16867 (16)	0.0096 (2)	0.0000	0.0849 (10)
H12A	0.139 (2)	−0.029 (2)	0.0000	0.102*
H12B	0.1605 (12)	0.0349 (13)	0.126 (4)	0.102*
C13	0.79850 (13)	0.21804 (16)	0.0000	0.0652 (7)
H13A	0.8077	0.1916	−0.1110	0.078*	0.50
H13B	0.8078	0.1920	0.1118	0.078*	0.50
H13C	0.8263	0.2573	−0.0007	0.078*
C14	0.62237 (18)	0.39835 (14)	0.0000	0.0829 (10)
H14A	0.6403	0.4196	−0.1113	0.099*	0.50
H14B	0.6402	0.4196	0.1115	0.099*	0.50
H14C	0.5744	0.4024	−0.0003	0.099*
N1	0.56095 (10)	0.15635 (10)	0.0000	0.0519 (6)
H1N	0.5776 (15)	0.1170 (16)	0.0000	0.062*
O1	0.46202 (9)	0.21173 (9)	0.0000	0.0821 (8)
O2	0.37347 (9)	−0.02118 (8)	0.0000	0.0701 (7)
O3	0.28217 (8)	0.04272 (8)	0.0000	0.0614 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0444 (12)	0.0435 (12)	0.0516 (12)	−0.0050 (9)	0.000	0.000
C2	0.0475 (13)	0.0481 (13)	0.0583 (13)	−0.0009 (9)	0.000	0.000
C3	0.0465 (12)	0.0632 (15)	0.0498 (12)	−0.0103 (10)	0.000	0.000
C4	0.0567 (15)	0.0593 (15)	0.0578 (14)	−0.0177 (11)	0.000	0.000
C5	0.0621 (15)	0.0464 (13)	0.0601 (14)	−0.0105 (10)	0.000	0.000
C6	0.0494 (13)	0.0426 (12)	0.0645 (14)	−0.0036 (9)	0.000	0.000
C7	0.0433 (12)	0.0411 (12)	0.0673 (15)	0.0014 (9)	0.000	0.000
C8	0.0432 (13)	0.0422 (13)	0.0775 (16)	−0.0015 (9)	0.000	0.000
C9	0.0447 (13)	0.0425 (12)	0.0673 (15)	0.0006 (9)	0.000	0.000
C10	0.0430 (12)	0.0449 (12)	0.0594 (14)	0.0013 (9)	0.000	0.000
C11	0.0497 (14)	0.0559 (15)	0.094 (2)	−0.0124 (11)	0.000	0.000
C12	0.0490 (16)	0.094 (3)	0.112 (3)	−0.0109 (15)	0.000	0.000
C13	0.0460 (14)	0.0815 (19)	0.0681 (16)	−0.0094 (12)	0.000	0.000
C14	0.083 (2)	0.0443 (15)	0.121 (3)	−0.0118 (13)	0.000	0.000
N1	0.0424 (11)	0.0367 (10)	0.0768 (14)	−0.0013 (8)	0.000	0.000
O1	0.0481 (10)	0.0416 (10)	0.157 (2)	0.0021 (7)	0.000	0.000
O2	0.0514 (10)	0.0397 (10)	0.1193 (18)	0.0015 (7)	0.000	0.000
O3	0.0420 (9)	0.0458 (9)	0.0965 (14)	−0.0017 (7)	0.000	0.000

Geometric parameters (Å, º) top

C1—C6	1.383 (3)	C9—H9A	0.9700
C1—C2	1.391 (3)	C9—H9B	0.9700
C1—N1	1.420 (3)	C10—O2	1.205 (3)
C2—C3	1.382 (3)	C10—O3	1.314 (3)
C2—H2	0.9300	C11—H11ⁱ	1.00 (2)
C3—C4	1.384 (4)	C11—O3	1.453 (3)
C3—C13	1.506 (4)	C11—C12	1.495 (4)
C4—C5	1.376 (4)	C11—H11	1.00 (2)
C4—H4	0.9300	C12—H12Bⁱ	1.03 (3)
C5—C6	1.392 (3)	C12—H12A	0.98 (4)
C5—C14	1.511 (4)	C12—H12B	1.03 (3)
C6—H6	0.9300	C13—H13A	0.9600
C7—O1	1.216 (3)	C13—H13B	0.9600
C7—N1	1.344 (3)	C13—H13C	0.9600
C7—C8	1.516 (3)	C14—H14A	0.9600
C8—C9	1.498 (3)	C14—H14B	0.9600
C8—H8A	0.9700	C14—H14C	0.9600
C8—H8B	0.9700	N1—H1N	0.85 (3)
C9—C10	1.495 (3)

C6—C1—C2	119.8 (2)	H9A—C9—H9B	107.6
C6—C1—N1	123.9 (2)	O2—C10—O3	123.7 (2)
C2—C1—N1	116.3 (2)	O2—C10—C9	125.1 (2)
C3—C2—C1	121.0 (2)	O3—C10—C9	111.17 (19)
C3—C2—H2	119.5	H11ⁱ—C11—O3	110.1 (12)
C1—C2—H2	119.5	H11ⁱ—C11—C12	109.4 (12)
C2—C3—C4	118.5 (2)	O3—C11—C12	106.2 (2)
C2—C3—C13	120.6 (3)	H11ⁱ—C11—H11	112 (3)
C4—C3—C13	120.9 (2)	O3—C11—H11	110.1 (12)
C5—C4—C3	121.4 (2)	C12—C11—H11	109.4 (12)
C5—C4—H4	119.3	H12Bⁱ—C12—C11	108.4 (14)
C3—C4—H4	119.3	H12Bⁱ—C12—H12A	106.9 (16)
C4—C5—C6	119.8 (2)	C11—C12—H12A	107 (2)
C4—C5—C14	121.0 (2)	H12Bⁱ—C12—H12B	118 (3)
C6—C5—C14	119.2 (3)	C11—C12—H12B	108.4 (14)
C1—C6—C5	119.6 (2)	H12A—C12—H12B	106.9 (16)
C1—C6—H6	120.2	C3—C13—H13A	109.5
C5—C6—H6	120.2	C3—C13—H13B	109.5
O1—C7—N1	123.9 (2)	H13A—C13—H13B	109.5
O1—C7—C8	121.7 (2)	C3—C13—H13C	109.5
N1—C7—C8	114.3 (2)	H13A—C13—H13C	109.5
C9—C8—C7	111.8 (2)	H13B—C13—H13C	109.5
C9—C8—H8A	109.2	C5—C14—H14A	109.5
C7—C8—H8A	109.2	C5—C14—H14B	109.5
C9—C8—H8B	109.2	H14A—C14—H14B	109.5
C7—C8—H8B	109.2	C5—C14—H14C	109.5
H8A—C8—H8B	107.9	H14A—C14—H14C	109.5
C10—C9—C8	114.1 (2)	H14B—C14—H14C	109.5
C10—C9—H9A	108.7	C7—N1—C1	129.0 (2)
C8—C9—H9A	108.7	C7—N1—H1N	116 (2)
C10—C9—H9B	108.7	C1—N1—H1N	115 (2)
C8—C9—H9B	108.7	C10—O3—C11	118.0 (2)

C6—C1—C2—C3	0.0	C7—C8—C9—C10	180.0
N1—C1—C2—C3	180.0	C8—C9—C10—O2	0.0
C1—C2—C3—C4	0.0	C8—C9—C10—O3	180.0
C1—C2—C3—C13	180.0	H11ⁱ—C11—C12—H12Bⁱ	−54 (2)
C2—C3—C4—C5	0.0	O3—C11—C12—H12Bⁱ	64.8 (16)
C13—C3—C4—C5	180.0	O1—C7—N1—C1	0.0
C3—C4—C5—C6	0.0	C8—C7—N1—C1	180.0
C3—C4—C5—C14	180.0	C6—C1—N1—C7	0.0
C2—C1—C6—C5	0.0	C2—C1—N1—C7	180.0
N1—C1—C6—C5	180.0	O2—C10—O3—C11	0.0
C4—C5—C6—C1	0.0	C9—C10—O3—C11	180.0
C14—C5—C6—C1	180.0	H11ⁱ—C11—O3—C10	−61.7 (13)
O1—C7—C8—C9	0.0	C12—C11—O3—C10	180.0
N1—C7—C8—C9	180.0

Symmetry code: (i) x, y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱⁱ	0.85 (3)	2.15 (3)	2.995 (3)	176 (3)

Symmetry code: (ii) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₉NO₃
M_r	249.30
Crystal system, space group	Tetragonal, I4/m
Temperature (K)	299
a, c (Å)	19.938 (2), 7.0367 (9)
V (Å³)	2797.3 (5)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.40 × 0.28 × 0.25

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4040, 1367, 1201
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.169, 1.11
No. of reflections	1367
No. of parameters	120
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.32

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.85 (3)	2.15 (3)	2.995 (3)	176 (3)

Symmetry code: (i) −x+1, −y, −z.

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for a resumption of his research fellowship.

References

Enraf–Nonius (1996). CAD-4-PC. Enraf–Nonius, Delft, The Netherlands. Google Scholar
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Gowda, B. T., Foro, S., Saraswathi, B. S., Terao, H. & Fuess, H. (2009c). Acta Cryst. E65, o873. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Stoe & Cie (1987). REDU4. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar