N-(4-Methyl­phen­yl)succinamic acid

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

doi:10.1107/S1600536810053298

organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o227

https://doi.org/10.1107/S1600536810053298

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N-(4-Methylphenyl)succinamic acid

B. S. Saraswathi,^a Sabine Foro,^b B. Thimme Gowda ^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 16 December 2010; accepted 19 December 2010; online 24 December 2010)

In the title compound, C₁₁H₁₃NO₃, the conformations of the N—H and C=O bonds in the amide segment are anti to each other. Further, the conformations of the amide and carbonyl O atoms of the acid segment are also anti to the adjacent –CH₂ groups. The C=O and O—H bonds of the acid group are syn to each other. In the crystal, molecules are packed into infinite chains along the b axis through intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For background to our study of the effect of ring and side-chain substitution on the solid state geometry of anilides, see: Gowda et al. (2009 , 2010a ,b ). For modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976 ). The packing of molecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed, see: Jagannathan et al. (1994 ).

Experimental

Crystal data

C₁₁H₁₃NO₃
M_r = 207.22
Triclinic, $[P \overline 1]$
a = 4.960 (1) Å
b = 8.090 (2) Å
c = 13.893 (2) Å
α = 83.52 (2)°
β = 80.08 (2)°
γ = 78.15 (1)°
V = 535.70 (19) Å³
Z = 2
Cu Kα radiation
μ = 0.78 mm⁻¹
T = 299 K
0.55 × 0.25 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.674, T_max = 0.940
2515 measured reflections
1888 independent reflections
1533 reflections with I > 2σ(I)
R_int = 0.024
3 standard reflections every 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.194
S = 1.06
1888 reflections
143 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.84 (2)	2.15 (2)	2.979 (2)	175 (3)
O3—H3O⋯O2ⁱⁱ	0.84 (2)	1.84 (2)	2.681 (3)	171 (4)
Symmetry codes: (i) x+1, y, z; (ii) -x, -y+1, -z+1.

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: https://doi.org/10.1107/S1600536810053298/ds2081sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810053298/ds2081Isup2.hkl

checkCIF report

Comment top

In the present work, as a part of studying the effect of ring and side chain substitutions on the solid state geometry of anilides (Gowda et al., 2009, 2010a, b), the crystal structure of N-(4-methylphenyl)- succinamic acid (I) has been determined. The conformations of N—H and C=O bonds in the amide segment are anti to each other. The conformation of the amide oxygen and the carbonyl oxygen of the acid segment are also anti to each other, similar to that observed in N-(4-Chlorophenyl)succinamic acid (II) (Gowda et al., 2009) and N-(2-methylphenyl)-succinamic acid (III)(Gowda et al., 2010b). but contrary to the syn conformation observed in N-(3-methylphenyl)-succinamic acid (IV) (Gowda et al., 2010a).

Further, the conformation of both the C=O bonds are anti to the H atoms of their adjacent –CH₂ groups (Fig. 1) and the C=O and O—H bonds of the acid group are in syn position to each other, similar to that observed in (II), (III) and (IV).

The N—H···O and O—H···O intermolecular hydrogen bonds pack the molecules into infinite chains in the structure (Table 1, Fig.2).

The modes of interlinking carboxylic acids by hydrogen bonds is described elsewhere (Leiserowitz, 1976). The packing of molecules involving dimeric hydrogen bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed (Jagannathan et al., 1994).

Related literature top

For background to our study of the effect of ring and side-chain substitution on the solid state geometry of anilides, see: Gowda et al. (2009, 2010a,b). For modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976). The packing of molecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed, see: Jagannathan et al. (1994);

Experimental top

The solution of succinic anhydride (0.01 mole) in toluene (25 ml) was treated dropwise with the solution of p-toluidine (0.01 mole) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about one h and set aside for an additional hour at room temperature for completion of the reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted p-toluidine. The resultant solid N-(4-methylphenyl)- succinamic acid was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. It 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 plate like colorless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.

Structure description top

The N—H···O and O—H···O intermolecular hydrogen bonds pack the molecules into infinite chains in the structure (Table 1, Fig.2).

For background to our study of the effect of ring and side-chain substitution on the solid state geometry of anilides, see: Gowda et al. (2009, 2010a,b). For modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976). The packing of molecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed, see: Jagannathan et al. (1994);

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 the title compound, showing the atom labelling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

3-[(4-methylphenyl)carbamoyl]propanoic acid top

Crystal data top

C₁₁H₁₃NO₃	Z = 2
M_r = 207.22	F(000) = 220
Triclinic, P1	D_x = 1.285 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 4.960 (1) Å	Cell parameters from 25 reflections
b = 8.090 (2) Å	θ = 6.3–21.3°
c = 13.893 (2) Å	µ = 0.78 mm⁻¹
α = 83.52 (2)°	T = 299 K
β = 80.08 (2)°	Plate, colourless
γ = 78.15 (1)°	0.55 × 0.25 × 0.08 mm
V = 535.70 (19) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1533 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 66.8°, θ_min = 3.2°
ω scans	h = −1→5
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
T_min = 0.674, T_max = 0.940	l = −16→16
2515 measured reflections	3 standard reflections every 120 min
1888 independent reflections	intensity decay: 1.0%

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.1156P)² + 0.1448P] where P = (F_o² + 2F_c²)/3
1888 reflections	(Δ/σ)_max = 0.017
143 parameters	Δρ_max = 0.24 e Å⁻³
2 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₁H₁₃NO₃	γ = 78.15 (1)°
M_r = 207.22	V = 535.70 (19) Å³
Triclinic, P1	Z = 2
a = 4.960 (1) Å	Cu Kα radiation
b = 8.090 (2) Å	µ = 0.78 mm⁻¹
c = 13.893 (2) Å	T = 299 K
α = 83.52 (2)°	0.55 × 0.25 × 0.08 mm
β = 80.08 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1533 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.024
T_min = 0.674, T_max = 0.940	3 standard reflections every 120 min
2515 measured reflections	intensity decay: 1.0%
1888 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	2 restraints
wR(F²) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.24 e Å⁻³
1888 reflections	Δρ_min = −0.33 e Å⁻³
143 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
C1	0.0934 (5)	0.7741 (3)	−0.07532 (16)	0.0507 (5)
C2	−0.1340 (6)	0.8882 (3)	−0.10364 (19)	0.0650 (6)
H2	−0.2788	0.9345	−0.0567	0.078*
C3	−0.1439 (7)	0.9328 (4)	−0.2025 (2)	0.0786 (8)
H3	−0.2988	1.0075	−0.2211	0.094*
C4	0.0703 (7)	0.8692 (4)	−0.27428 (19)	0.0761 (8)
C5	0.2991 (7)	0.7575 (4)	−0.2444 (2)	0.0802 (8)
H5	0.4466	0.7135	−0.2912	0.096*
C6	0.3100 (6)	0.7110 (3)	−0.14645 (19)	0.0677 (7)
H6	0.4650	0.6363	−0.1279	0.081*
C7	−0.0863 (4)	0.6981 (3)	0.09714 (16)	0.0538 (6)
C8	0.0133 (5)	0.6313 (3)	0.19407 (17)	0.0603 (6)
H8A	0.0707	0.5091	0.1952	0.072*
H8B	0.1748	0.6782	0.1992	0.072*
C9	−0.2087 (5)	0.6752 (3)	0.28162 (17)	0.0603 (6)
H9A	−0.2574	0.7974	0.2830	0.072*
H9B	−0.3747	0.6347	0.2745	0.072*
C10	−0.1152 (5)	0.5994 (3)	0.37648 (17)	0.0588 (6)
C11	0.0523 (11)	0.9182 (6)	−0.3816 (2)	0.1183 (15)
H11A	0.0186	1.0394	−0.3932	0.142*
H11B	−0.0976	0.8753	−0.3993	0.142*
H11C	0.2245	0.8709	−0.4206	0.142*
N1	0.1202 (4)	0.7230 (2)	0.02421 (14)	0.0533 (5)
H1N	0.278 (4)	0.719 (3)	0.0386 (19)	0.064*
O1	−0.3349 (3)	0.7206 (3)	0.08761 (13)	0.0727 (6)
O2	0.1144 (4)	0.5108 (3)	0.38248 (14)	0.0853 (7)
O3	−0.3025 (4)	0.6364 (3)	0.45282 (14)	0.0935 (8)
H3O	−0.231 (8)	0.598 (5)	0.504 (2)	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0523 (12)	0.0537 (11)	0.0487 (11)	−0.0180 (9)	−0.0068 (9)	−0.0023 (9)
C2	0.0656 (15)	0.0657 (14)	0.0593 (14)	−0.0061 (11)	−0.0098 (11)	0.0021 (11)
C3	0.088 (2)	0.0785 (17)	0.0699 (18)	−0.0168 (14)	−0.0264 (15)	0.0148 (13)
C4	0.111 (2)	0.0768 (17)	0.0508 (14)	−0.0433 (16)	−0.0182 (14)	0.0068 (12)
C5	0.103 (2)	0.0806 (17)	0.0537 (15)	−0.0238 (16)	0.0073 (14)	−0.0088 (13)
C6	0.0662 (15)	0.0722 (15)	0.0590 (14)	−0.0096 (12)	0.0006 (11)	−0.0032 (11)
C7	0.0464 (12)	0.0669 (13)	0.0505 (12)	−0.0183 (10)	−0.0089 (9)	0.0014 (9)
C8	0.0447 (12)	0.0842 (16)	0.0522 (13)	−0.0163 (10)	−0.0102 (10)	0.0061 (11)
C9	0.0529 (13)	0.0755 (15)	0.0514 (13)	−0.0124 (11)	−0.0098 (10)	0.0031 (10)
C10	0.0568 (13)	0.0705 (14)	0.0477 (12)	−0.0142 (11)	−0.0052 (10)	0.0006 (10)
C11	0.188 (4)	0.126 (3)	0.0569 (19)	−0.068 (3)	−0.030 (2)	0.0139 (18)
N1	0.0414 (9)	0.0713 (12)	0.0485 (10)	−0.0151 (8)	−0.0080 (7)	−0.0007 (8)
O1	0.0438 (9)	0.1125 (15)	0.0629 (11)	−0.0234 (9)	−0.0138 (7)	0.0128 (9)
O2	0.0686 (12)	0.1219 (17)	0.0518 (10)	0.0074 (11)	−0.0100 (8)	0.0047 (10)
O3	0.0740 (13)	0.1372 (19)	0.0504 (11)	0.0077 (12)	−0.0024 (9)	0.0096 (11)

Geometric parameters (Å, º) top

C1—C6	1.383 (3)	C7—C8	1.518 (3)
C1—C2	1.386 (3)	C8—C9	1.514 (3)
C1—N1	1.419 (3)	C8—H8A	0.9700
C2—C3	1.387 (4)	C8—H8B	0.9700
C2—H2	0.9300	C9—C10	1.497 (3)
C3—C4	1.383 (5)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.390 (5)	C10—O2	1.225 (3)
C4—C11	1.513 (4)	C10—O3	1.302 (3)
C5—C6	1.378 (4)	C11—H11A	0.9600
C5—H5	0.9300	C11—H11B	0.9600
C6—H6	0.9300	C11—H11C	0.9600
C7—O1	1.237 (3)	N1—H1N	0.836 (17)
C7—N1	1.340 (3)	O3—H3O	0.844 (19)

C6—C1—C2	119.1 (2)	C7—C8—H8A	109.0
C6—C1—N1	117.9 (2)	C9—C8—H8B	109.0
C2—C1—N1	123.0 (2)	C7—C8—H8B	109.0
C1—C2—C3	119.5 (2)	H8A—C8—H8B	107.8
C1—C2—H2	120.2	C10—C9—C8	112.4 (2)
C3—C2—H2	120.2	C10—C9—H9A	109.1
C4—C3—C2	121.8 (3)	C8—C9—H9A	109.1
C4—C3—H3	119.1	C10—C9—H9B	109.1
C2—C3—H3	119.1	C8—C9—H9B	109.1
C3—C4—C5	117.8 (2)	H9A—C9—H9B	107.9
C3—C4—C11	120.7 (3)	O2—C10—O3	122.9 (2)
C5—C4—C11	121.4 (3)	O2—C10—C9	123.8 (2)
C6—C5—C4	120.8 (3)	O3—C10—C9	113.4 (2)
C6—C5—H5	119.6	C4—C11—H11A	109.5
C4—C5—H5	119.6	C4—C11—H11B	109.5
C5—C6—C1	120.8 (3)	H11A—C11—H11B	109.5
C5—C6—H6	119.6	C4—C11—H11C	109.5
C1—C6—H6	119.6	H11A—C11—H11C	109.5
O1—C7—N1	124.4 (2)	H11B—C11—H11C	109.5
O1—C7—C8	121.9 (2)	C7—N1—C1	126.48 (19)
N1—C7—C8	113.68 (19)	C7—N1—H1N	118.0 (19)
C9—C8—C7	112.7 (2)	C1—N1—H1N	115.1 (19)
C9—C8—H8A	109.0	C10—O3—H3O	108 (3)

C6—C1—C2—C3	1.9 (4)	O1—C7—C8—C9	−27.7 (3)
N1—C1—C2—C3	179.6 (2)	N1—C7—C8—C9	154.7 (2)
C1—C2—C3—C4	−1.4 (4)	C7—C8—C9—C10	176.27 (19)
C2—C3—C4—C5	0.1 (4)	C8—C9—C10—O2	−0.5 (4)
C2—C3—C4—C11	179.2 (3)	C8—C9—C10—O3	179.6 (2)
C3—C4—C5—C6	0.5 (4)	O1—C7—N1—C1	−1.7 (4)
C11—C4—C5—C6	−178.6 (3)	C8—C7—N1—C1	175.8 (2)
C4—C5—C6—C1	0.1 (4)	C6—C1—N1—C7	−146.1 (2)
C2—C1—C6—C5	−1.4 (4)	C2—C1—N1—C7	36.3 (3)
N1—C1—C6—C5	−179.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (2)	2.15 (2)	2.979 (2)	175 (3)
O3—H3O···O2ⁱⁱ	0.84 (2)	1.84 (2)	2.681 (3)	171 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃NO₃
M_r	207.22
Crystal system, space group	Triclinic, P1
Temperature (K)	299
a, b, c (Å)	4.960 (1), 8.090 (2), 13.893 (2)
α, β, γ (°)	83.52 (2), 80.08 (2), 78.15 (1)
V (Å³)	535.70 (19)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.55 × 0.25 × 0.08

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.674, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	2515, 1888, 1533
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.194, 1.06
No. of reflections	1888
No. of parameters	143
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.33

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···O1ⁱ	0.836 (17)	2.145 (18)	2.979 (2)	175 (3)
O3—H3O···O2ⁱⁱ	0.844 (19)	1.84 (2)	2.681 (3)	171 (4)

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

Acknowledgements

BSS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement program.

References

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