N-(2,6-Dimethyl­phen­yl)succinamic acid

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

doi:10.1107/S1600536809003833

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o466

doi:10.1107/S1600536809003833

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N-(2,6-Dimethylphenyl)succinamic acid

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

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany, and ^cFaculty of Integrated Arts and Sciences, Tokushima University, Minamijosanjima-cho, Tokushima 770-8502, Japan
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 31 January 2009; accepted 2 February 2009; online 6 February 2009)

In the amide segment of the title compound, C₁₂H₁₅NO₃ {systematic name: 3-[(2,6-dimethylphenyl)aminocarbonyl]propionic acid}, the N—H and C=O bonds are anti to each other. The molecules are packed into a two-dimensional array via N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For related structures, see: Gowda et al. (2007 , 2008 , 2009 ).

Experimental

Crystal data

C₁₂H₁₅NO₃
M_r = 221.25
Monoclinic, P 2₁ /n
a = 7.9633 (8) Å
b = 19.889 (2) Å
c = 7.9822 (8) Å
β = 111.16 (1)°
V = 1179.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 299 (2) K
0.50 × 0.48 × 0.40 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd, Köln, Germany.]$ ) T_min = 0.958, T_max = 0.966
6777 measured reflections
2391 independent reflections
1826 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.135
S = 1.05
2391 reflections
154 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.859 (18)	2.059 (19)	2.9120 (16)	171.8 (17)
O2—H2O⋯O3ⁱⁱ	0.88 (3)	1.79 (3)	2.6686 (18)	178 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x-1, -y+1, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2004 $[Oxford Diffraction (2004). CrysAlis CCD. Oxford Diffraction Ltd, Köln, Germany.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd, Köln, Germany.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003833/tk2369sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003833/tk2369Isup2.hkl

checkCIF report

Comment top

The amide moiety is an important constituent of many biologically significant compounds. Thus, structural studies of amides are of interest. As a part of an on-going investigation studying the effect of ring and side-chain substitutions on the structures of this class of compounds (Gowda et al., 2007, 2008; 2009), we have determined the crystal structure of N-(2,6-dimethylphenyl)-succinamic acid, (I), with systematic name: 3-[(2,6-dimethylphenyl)-aminocarbonyl]propionic acid, Fig. 1. The N-H and C=O bonds in the amide segment of the structure are anti to each other. The C1-N1-C7-C8, N1-C7-C8-C9, C7-C8-C9-C10 and C8-C9-C10-O2 torsion angles in the side chain are -176.2 (1)°, -145.4 (2)°, -175.5 (1)° and -161.1 (2)°, respectively, and compare to the corresponding values in the structure of i>N-(2-chlorophenyl)-succinamic acid, i.e. 177.5 (2)°, 173.2 (2)°, 178.9 (2)° and 167.7 (2)°, respectively (Gowda et al., 2009).

The presence of N-H···O, between the amide groups, and O-H···O, between the carboxylic acid residues, hydrogen bonding pack molecules into a 2D array (Table 1, Fig.2).

Related literature top

For related structures, see: Gowda et al. (2007, 2008, 2009).

Experimental top

A solution of succinic anhydride (0.025 mole) in toluene (25 ml) was treated dropwise with a solution of 2,6-dimethylaniline (0.025 mole) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about 1 h and set aside for an additional hour at room temperature to allow completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove unreacted 2,6-dimethylaniline. The resultant solid was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. The product was recrystallized to constant melting point from ethanol. The purity of the compound was checked by elemental analysis and characterized by its infrared and NMR spectra. The single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

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

3-[(2,6-dimethylphenyl)aminocarbonyl]propionic acid top

Crystal data top

C₁₂H₁₅NO₃	F(000) = 472
M_r = 221.25	D_x = 1.246 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3013 reflections
a = 7.9633 (8) Å	θ = 2.7–28.0°
b = 19.889 (2) Å	µ = 0.09 mm⁻¹
c = 7.9822 (8) Å	T = 299 K
β = 111.16 (1)°	Prism, colourless
V = 1179.0 (2) Å³	0.50 × 0.48 × 0.40 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2391 independent reflections
Radiation source: fine-focus sealed tube	1826 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Rotation method data acquisition using ω and ϕ scans	θ_max = 26.4°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −9→9
T_min = 0.958, T_max = 0.966	k = −24→24
6777 measured reflections	l = −8→9

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.0691P)² + 0.3248P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.03
2391 reflections	Δρ_max = 0.19 e Å⁻³
154 parameters	Δρ_min = −0.17 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: 0.017 (4)

Crystal data top

C₁₂H₁₅NO₃	V = 1179.0 (2) Å³
M_r = 221.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.9633 (8) Å	µ = 0.09 mm⁻¹
b = 19.889 (2) Å	T = 299 K
c = 7.9822 (8) Å	0.50 × 0.48 × 0.40 mm
β = 111.16 (1)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2391 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1826 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.966	R_int = 0.017
6777 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.19 e Å⁻³
2391 reflections	Δρ_min = −0.17 e Å⁻³
154 parameters

Special details top

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2007 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
C1	0.12966 (19)	0.18528 (8)	0.03678 (19)	0.0379 (4)
C2	0.0916 (2)	0.11993 (8)	0.0772 (2)	0.0480 (4)
C3	0.2273 (3)	0.07205 (10)	0.1098 (3)	0.0688 (6)
H3	0.2062	0.0282	0.1376	0.083*
C4	0.3924 (3)	0.08854 (14)	0.1016 (3)	0.0799 (8)
H4	0.4816	0.0559	0.1241	0.096*
C5	0.4251 (3)	0.15276 (13)	0.0604 (3)	0.0693 (6)
H5	0.5369	0.1632	0.0552	0.083*
C6	0.2949 (2)	0.20310 (10)	0.0260 (2)	0.0483 (4)
C7	0.00487 (18)	0.28812 (7)	0.11169 (19)	0.0353 (3)
C8	−0.1610 (2)	0.33204 (8)	0.0593 (2)	0.0434 (4)
H8A	−0.2293	0.3264	−0.0679	0.052*
H8B	−0.2363	0.3174	0.1245	0.052*
C9	−0.1168 (2)	0.40548 (8)	0.0976 (2)	0.0467 (4)
H9A	−0.0409	0.4109	0.2229	0.056*
H9B	−0.0499	0.4212	0.0250	0.056*
C10	−0.2830 (2)	0.44735 (8)	0.0582 (2)	0.0473 (4)
C11	−0.0877 (3)	0.10257 (10)	0.0884 (3)	0.0637 (5)
H11A	−0.1803	0.1074	−0.0280	0.076*
H11B	−0.1120	0.1323	0.1717	0.076*
H11C	−0.0854	0.0570	0.1287	0.076*
C12	0.3334 (3)	0.27264 (12)	−0.0218 (3)	0.0662 (6)
H12A	0.3733	0.3001	0.0843	0.079*
H12B	0.2258	0.2916	−0.1077	0.079*
H12C	0.4256	0.2709	−0.0727	0.079*
N1	−0.00837 (16)	0.23498 (6)	0.00415 (17)	0.0368 (3)
H1N	−0.111 (2)	0.2276 (9)	−0.079 (2)	0.044*
O1	0.13819 (13)	0.30009 (6)	0.24524 (15)	0.0469 (3)
O2	−0.25948 (19)	0.51129 (6)	0.0379 (2)	0.0750 (5)
H2O	−0.363 (4)	0.5325 (13)	0.012 (3)	0.090*
O3	−0.42763 (16)	0.42371 (6)	0.0464 (2)	0.0714 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0333 (7)	0.0407 (8)	0.0329 (7)	0.0075 (6)	0.0038 (6)	−0.0065 (6)
C2	0.0541 (10)	0.0393 (9)	0.0399 (9)	0.0074 (7)	0.0042 (7)	−0.0068 (7)
C3	0.0865 (16)	0.0462 (11)	0.0573 (12)	0.0256 (10)	0.0061 (10)	−0.0063 (8)
C4	0.0731 (15)	0.0875 (17)	0.0666 (13)	0.0504 (13)	0.0101 (11)	−0.0078 (12)
C5	0.0444 (10)	0.0996 (18)	0.0593 (12)	0.0256 (11)	0.0134 (9)	−0.0131 (11)
C6	0.0358 (8)	0.0675 (11)	0.0385 (8)	0.0078 (7)	0.0096 (7)	−0.0073 (8)
C7	0.0270 (7)	0.0371 (8)	0.0365 (8)	0.0034 (6)	0.0052 (6)	0.0009 (6)
C8	0.0307 (7)	0.0399 (8)	0.0491 (9)	0.0082 (6)	0.0018 (6)	−0.0039 (7)
C9	0.0341 (8)	0.0415 (9)	0.0577 (10)	0.0060 (6)	0.0084 (7)	−0.0013 (7)
C10	0.0385 (9)	0.0376 (8)	0.0576 (10)	0.0057 (7)	0.0075 (7)	−0.0053 (7)
C11	0.0671 (12)	0.0449 (10)	0.0697 (13)	−0.0105 (9)	0.0132 (10)	0.0004 (9)
C12	0.0486 (10)	0.0862 (15)	0.0702 (13)	−0.0092 (10)	0.0291 (10)	0.0006 (11)
N1	0.0258 (6)	0.0367 (7)	0.0384 (7)	0.0032 (5)	0.0001 (5)	−0.0047 (5)
O1	0.0325 (6)	0.0498 (7)	0.0436 (6)	0.0089 (5)	−0.0042 (5)	−0.0094 (5)
O2	0.0473 (8)	0.0376 (7)	0.1347 (15)	0.0076 (6)	0.0263 (8)	−0.0008 (8)
O3	0.0415 (7)	0.0434 (7)	0.1276 (13)	0.0085 (5)	0.0284 (8)	0.0044 (7)

Geometric parameters (Å, º) top

C1—C6	1.395 (2)	C8—H8A	0.9700
C1—C2	1.398 (2)	C8—H8B	0.9700
C1—N1	1.4306 (18)	C9—C10	1.498 (2)
C2—C3	1.393 (2)	C9—H9A	0.9700
C2—C11	1.503 (3)	C9—H9B	0.9700
C3—C4	1.379 (3)	C10—O3	1.216 (2)
C3—H3	0.9300	C10—O2	1.304 (2)
C4—C5	1.367 (4)	C11—H11A	0.9600
C4—H4	0.9300	C11—H11B	0.9600
C5—C6	1.395 (3)	C11—H11C	0.9600
C5—H5	0.9300	C12—H12A	0.9600
C6—C12	1.495 (3)	C12—H12B	0.9600
C7—O1	1.2260 (17)	C12—H12C	0.9600
C7—N1	1.3415 (19)	N1—H1N	0.859 (18)
C7—C8	1.5115 (19)	O2—H2O	0.88 (3)
C8—C9	1.508 (2)

C6—C1—C2	122.55 (15)	H8A—C8—H8B	107.8
C6—C1—N1	119.54 (15)	C10—C9—C8	111.83 (13)
C2—C1—N1	117.91 (14)	C10—C9—H9A	109.3
C3—C2—C1	117.43 (18)	C8—C9—H9A	109.3
C3—C2—C11	121.43 (18)	C10—C9—H9B	109.3
C1—C2—C11	121.12 (15)	C8—C9—H9B	109.3
C4—C3—C2	121.1 (2)	H9A—C9—H9B	107.9
C4—C3—H3	119.4	O3—C10—O2	122.82 (15)
C2—C3—H3	119.4	O3—C10—C9	122.82 (15)
C5—C4—C3	120.05 (18)	O2—C10—C9	114.37 (15)
C5—C4—H4	120.0	C2—C11—H11A	109.5
C3—C4—H4	120.0	C2—C11—H11B	109.5
C4—C5—C6	121.7 (2)	H11A—C11—H11B	109.5
C4—C5—H5	119.1	C2—C11—H11C	109.5
C6—C5—H5	119.1	H11A—C11—H11C	109.5
C1—C6—C5	117.12 (19)	H11B—C11—H11C	109.5
C1—C6—C12	122.35 (15)	C6—C12—H12A	109.5
C5—C6—C12	120.53 (18)	C6—C12—H12B	109.5
O1—C7—N1	123.55 (13)	H12A—C12—H12B	109.5
O1—C7—C8	121.63 (13)	C6—C12—H12C	109.5
N1—C7—C8	114.79 (12)	H12A—C12—H12C	109.5
C9—C8—C7	112.76 (12)	H12B—C12—H12C	109.5
C9—C8—H8A	109.0	C7—N1—C1	123.37 (12)
C7—C8—H8A	109.0	C7—N1—H1N	117.7 (12)
C9—C8—H8B	109.0	C1—N1—H1N	118.3 (12)
C7—C8—H8B	109.0	C10—O2—H2O	109.4 (16)

C6—C1—C2—C3	0.9 (2)	C4—C5—C6—C1	0.5 (3)
N1—C1—C2—C3	−179.61 (14)	C4—C5—C6—C12	−178.95 (19)
C6—C1—C2—C11	179.75 (15)	O1—C7—C8—C9	36.3 (2)
N1—C1—C2—C11	−0.8 (2)	N1—C7—C8—C9	−145.43 (15)
C1—C2—C3—C4	−0.3 (3)	C7—C8—C9—C10	−175.54 (14)
C11—C2—C3—C4	−179.12 (18)	C8—C9—C10—O3	19.1 (3)
C2—C3—C4—C5	−0.2 (3)	C8—C9—C10—O2	−161.05 (17)
C3—C4—C5—C6	0.1 (3)	O1—C7—N1—C1	2.0 (2)
C2—C1—C6—C5	−1.0 (2)	C8—C7—N1—C1	−176.22 (14)
N1—C1—C6—C5	179.54 (14)	C6—C1—N1—C7	−66.5 (2)
C2—C1—C6—C12	178.40 (16)	C2—C1—N1—C7	114.05 (17)
N1—C1—C6—C12	−1.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.859 (18)	2.059 (19)	2.9120 (16)	171.8 (17)
O2—H2O···O3ⁱⁱ	0.88 (3)	1.79 (3)	2.6686 (18)	178 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO₃
M_r	221.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	299
a, b, c (Å)	7.9633 (8), 19.889 (2), 7.9822 (8)
β (°)	111.16 (1)
V (Å³)	1179.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.48 × 0.40

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.958, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	6777, 2391, 1826
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.135, 1.05
No. of reflections	2391
No. of parameters	154
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17

Computer programs: CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.859 (18)	2.059 (19)	2.9120 (16)	171.8 (17)
O2—H2O···O3ⁱⁱ	0.88 (3)	1.79 (3)	2.6686 (18)	178 (3)

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

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions to his research fellowship.

References

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