organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

N-(3,5-Di­methyl­phen­yl)succinamic acid

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 17 December 2010; online 24 December 2010)

In the title compound, C12H15NO3, the N—H and C=O bonds are anti to each other. The C=O and O—H bonds of the acid group display an anti­periplanar orientation relative to each other. The crystal packing features a three-dimensional network of molecules held together by O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For our study of the effect of ring and side-chain substitutions on the crystal structures of anilides, see: Gowda et al. (2009[Gowda, B. T., Foro, S., Saraswathi, B. S., Terao, H. & Fuess, H. (2009). Acta Cryst. E65, o466.] 2010a[Gowda, B. T., Foro, S., Saraswathi, B. S. & Fuess, H. (2010a). Acta Cryst. E66, o394.],b[Gowda, B. T., Foro, S., Saraswathi, B. S. & Fuess, H. (2010b). Acta Cryst. E66, o436.]). For modes of inter­linking carb­oxy­lic acids by hydrogen bonds, see: Leiserowitz (1976[Leiserowitz, L. (1976). Acta Cryst. B32, 775-802.]). 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[Jagannathan, N. R., Rajan, S. S. & Subramanian, E. (1994). J. Chem. Crystallogr. 24, 75-78.]).

[Scheme 1]

Experimental

Crystal data
  • C12H15NO3

  • Mr = 221.25

  • Monoclinic, P 21 /n

  • a = 14.346 (2) Å

  • b = 5.0225 (9) Å

  • c = 17.860 (3) Å

  • β = 112.00 (2)°

  • V = 1193.2 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 293 K

  • 0.45 × 0.08 × 0.05 mm

Data collection
  • Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.961, Tmax = 0.996

  • 4452 measured reflections

  • 2419 independent reflections

  • 1593 reflections with I > 2σ(I)

  • Rint = 0.019

Refinement
  • R[F2 > 2σ(F2)] = 0.054

  • wR(F2) = 0.147

  • S = 1.03

  • 2419 reflections

  • 153 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N⋯O2i 0.88 (2) 2.01 (2) 2.881 (2) 171 (2)
O3—H3O⋯O1ii 0.86 (3) 1.77 (3) 2.630 (2) 172 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: CrysAlis CCD (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

As a part of studying the effect of ring and side chain substitutions on the crystal structures of anilides (Gowda et al., 2009, 2010a,b), in the present work, the crystal structure of N-(3,5-dimethylphenyl)- succinamic acid (I) has been determined. The conformations of N—H and C O bonds in the amide segment are anti to each other (Fig. 1). The conformation of the amide oxygen and the carbonyl oxygen of the acid segment are anti to each other, similar to the anti conformation observed in N-(2,6-dimethylphenyl)-succinamic acid (II) (Gowda et al., 2009), but in contrast to the the syn conformation observed in N-(3-methylphenyl)succinamic acid (III) (Gowda et al., 2010a) and N-(3,4-dimethylphenyl)- succinamic acid (IV) (Gowda et al., 2010b).

But, the conformations of the amide oxygen and the carbonyl oxygen of the acid segment are anti to the adjacent –CH2 groups in the above compounds. The conformation of the amide hydrogen is syn to one of the meta–methyl groups in the benzene ring and anti to the other.

Further, the CO and O—H bonds of the acid group in (I) are in anti position to each other, in contrast to the syn conformation observed in (II), (III) and (IV).

The intermolecular O—H···O and N—H···O hydrogen bonds pack the molecules into a three-dimensional network (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 our study of the effect of ring and side-chain substitutions on the crystal structures 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 3,5-dimethylaniline (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 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. 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.

Needle like colorless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.

Refinement top

The H atoms of the NH and OH group were located in a difference map and their coordinates were refined. The other H atoms were positioned with idealized geometry using a riding model with C—H = 0.93–0.97 Å. All H atoms were refined with isotropic displacement parameters set to 1.2 times of the Ueq of the parent atom.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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
[Figure 1] 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.
[Figure 2] Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.
N-(3,5-Dimethylphenyl)succinamic acid top
Crystal data top
C12H15NO3F(000) = 472
Mr = 221.25Dx = 1.232 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1372 reflections
a = 14.346 (2) Åθ = 2.9–27.7°
b = 5.0225 (9) ŵ = 0.09 mm1
c = 17.860 (3) ÅT = 293 K
β = 112.00 (2)°Needle, colourless
V = 1193.2 (3) Å30.45 × 0.08 × 0.05 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
2419 independent reflections
Radiation source: fine-focus sealed tube1593 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
Rotation method data acquisition using ω scansθmax = 26.4°, θmin = 3.1°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
h = 1717
Tmin = 0.961, Tmax = 0.996k = 64
4452 measured reflectionsl = 2212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0672P)2 + 0.3965P]
where P = (Fo2 + 2Fc2)/3
2419 reflections(Δ/σ)max = 0.018
153 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C12H15NO3V = 1193.2 (3) Å3
Mr = 221.25Z = 4
Monoclinic, P21/nMo Kα radiation
a = 14.346 (2) ŵ = 0.09 mm1
b = 5.0225 (9) ÅT = 293 K
c = 17.860 (3) Å0.45 × 0.08 × 0.05 mm
β = 112.00 (2)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
2419 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
1593 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.996Rint = 0.019
4452 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.20 e Å3
2419 reflectionsΔρmin = 0.18 e Å3
153 parameters
Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2009) 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
xyzUiso*/Ueq
C10.59923 (15)0.1845 (4)0.36154 (12)0.0429 (5)
C20.56185 (17)0.3031 (5)0.28576 (13)0.0490 (6)
H20.50050.24830.24760.059*
C30.61608 (19)0.5031 (5)0.26700 (15)0.0555 (6)
C40.70735 (19)0.5819 (5)0.32444 (17)0.0627 (7)
H40.74370.71570.31170.075*
C50.74574 (18)0.4675 (5)0.40004 (16)0.0583 (7)
C60.69101 (16)0.2678 (5)0.41832 (14)0.0506 (6)
H60.71590.18870.46910.061*
C70.45744 (14)0.1217 (4)0.34799 (11)0.0390 (5)
C80.42783 (15)0.3396 (4)0.39303 (12)0.0419 (5)
H8A0.43140.27060.44480.050*
H8B0.47590.48410.40350.050*
C90.32429 (15)0.4476 (4)0.34847 (12)0.0477 (6)
H9A0.31900.50390.29510.057*
H9B0.27570.30630.34180.057*
C100.29831 (15)0.6774 (4)0.39033 (11)0.0417 (5)
C110.5745 (2)0.6330 (6)0.18462 (17)0.0773 (9)
H11A0.52060.52670.14890.093*
H11B0.54990.80740.18930.093*
H11C0.62680.64710.16350.093*
C120.8446 (2)0.5577 (7)0.46246 (19)0.0861 (10)
H12A0.83250.69060.49640.103*
H12B0.87840.40840.49480.103*
H12C0.88580.63160.43590.103*
N10.54859 (13)0.0184 (4)0.38637 (10)0.0446 (5)
H1N0.5825 (17)0.090 (5)0.4335 (14)0.054*
O10.40041 (11)0.0430 (3)0.28096 (9)0.0557 (5)
O20.35474 (12)0.7710 (3)0.45287 (9)0.0593 (5)
O30.20787 (12)0.7838 (3)0.35458 (9)0.0563 (5)
H3O0.1771 (19)0.695 (5)0.3110 (16)0.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0391 (11)0.0465 (13)0.0432 (11)0.0005 (10)0.0154 (9)0.0049 (10)
C20.0464 (12)0.0548 (14)0.0461 (12)0.0005 (11)0.0178 (10)0.0002 (11)
C30.0628 (15)0.0543 (14)0.0601 (14)0.0069 (12)0.0352 (13)0.0027 (12)
C40.0632 (16)0.0578 (15)0.0810 (19)0.0093 (13)0.0429 (15)0.0059 (14)
C50.0473 (13)0.0631 (16)0.0691 (16)0.0074 (12)0.0271 (12)0.0175 (13)
C60.0446 (12)0.0580 (14)0.0477 (12)0.0015 (11)0.0158 (10)0.0075 (11)
C70.0361 (10)0.0416 (12)0.0323 (10)0.0043 (9)0.0050 (8)0.0001 (9)
C80.0390 (11)0.0449 (12)0.0345 (10)0.0036 (9)0.0053 (8)0.0026 (9)
C90.0436 (12)0.0479 (13)0.0375 (11)0.0041 (10)0.0010 (9)0.0059 (10)
C100.0398 (11)0.0479 (12)0.0307 (10)0.0008 (10)0.0055 (8)0.0020 (9)
C110.090 (2)0.0774 (19)0.0780 (19)0.0079 (16)0.0473 (17)0.0227 (16)
C120.0632 (17)0.105 (2)0.090 (2)0.0334 (17)0.0282 (16)0.0258 (19)
N10.0390 (10)0.0513 (11)0.0343 (9)0.0019 (8)0.0032 (8)0.0051 (8)
O10.0458 (9)0.0639 (11)0.0397 (8)0.0063 (8)0.0042 (7)0.0135 (7)
O20.0572 (10)0.0654 (11)0.0380 (8)0.0020 (8)0.0021 (7)0.0156 (8)
O30.0492 (9)0.0673 (11)0.0414 (8)0.0137 (8)0.0043 (7)0.0070 (8)
Geometric parameters (Å, º) top
C1—C21.389 (3)C8—H8A0.9700
C1—C61.392 (3)C8—H8B0.9700
C1—N11.416 (3)C9—C101.496 (3)
C2—C31.386 (3)C9—H9A0.9700
C2—H20.9300C9—H9B0.9700
C3—C41.385 (3)C10—O21.203 (2)
C3—C111.513 (3)C10—O31.325 (2)
C4—C51.378 (4)C11—H11A0.9600
C4—H40.9300C11—H11B0.9600
C5—C61.386 (3)C11—H11C0.9600
C5—C121.508 (4)C12—H12A0.9600
C6—H60.9300C12—H12B0.9600
C7—O11.235 (2)C12—H12C0.9600
C7—N11.333 (3)N1—H1N0.88 (2)
C7—C81.510 (3)O3—H3O0.86 (3)
C8—C91.499 (3)
C2—C1—C6119.7 (2)H8A—C8—H8B107.7
C2—C1—N1123.88 (19)C10—C9—C8113.35 (17)
C6—C1—N1116.40 (19)C10—C9—H9A108.9
C3—C2—C1120.0 (2)C8—C9—H9A108.9
C3—C2—H2120.0C10—C9—H9B108.9
C1—C2—H2120.0C8—C9—H9B108.9
C4—C3—C2119.2 (2)H9A—C9—H9B107.7
C4—C3—C11121.1 (2)O2—C10—O3119.1 (2)
C2—C3—C11119.7 (2)O2—C10—C9123.95 (19)
C5—C4—C3121.8 (2)O3—C10—C9116.91 (17)
C5—C4—H4119.1C3—C11—H11A109.5
C3—C4—H4119.1C3—C11—H11B109.5
C4—C5—C6118.6 (2)H11A—C11—H11B109.5
C4—C5—C12121.3 (2)C3—C11—H11C109.5
C6—C5—C12120.1 (3)H11A—C11—H11C109.5
C5—C6—C1120.7 (2)H11B—C11—H11C109.5
C5—C6—H6119.6C5—C12—H12A109.5
C1—C6—H6119.6C5—C12—H12B109.5
O1—C7—N1122.7 (2)H12A—C12—H12B109.5
O1—C7—C8122.14 (18)C5—C12—H12C109.5
N1—C7—C8115.19 (17)H12A—C12—H12C109.5
C9—C8—C7113.56 (16)H12B—C12—H12C109.5
C9—C8—H8A108.9C7—N1—C1129.70 (18)
C7—C8—H8A108.9C7—N1—H1N114.7 (15)
C9—C8—H8B108.9C1—N1—H1N115.6 (15)
C7—C8—H8B108.9C10—O3—H3O107.7 (17)
C6—C1—C2—C30.1 (3)N1—C1—C6—C5179.3 (2)
N1—C1—C2—C3179.2 (2)O1—C7—C8—C90.1 (3)
C1—C2—C3—C40.1 (3)N1—C7—C8—C9179.09 (19)
C1—C2—C3—C11179.5 (2)C7—C8—C9—C10175.54 (18)
C2—C3—C4—C50.2 (4)C8—C9—C10—O21.1 (3)
C11—C3—C4—C5179.3 (2)C8—C9—C10—O3180.00 (19)
C3—C4—C5—C60.2 (4)O1—C7—N1—C11.5 (4)
C3—C4—C5—C12179.2 (2)C8—C7—N1—C1179.56 (19)
C4—C5—C6—C10.0 (4)C2—C1—N1—C74.9 (4)
C12—C5—C6—C1179.4 (2)C6—C1—N1—C7174.2 (2)
C2—C1—C6—C50.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.88 (2)2.01 (2)2.881 (2)171 (2)
O3—H3O···O1ii0.86 (3)1.77 (3)2.630 (2)172 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H15NO3
Mr221.25
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)14.346 (2), 5.0225 (9), 17.860 (3)
β (°) 112.00 (2)
V3)1193.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.45 × 0.08 × 0.05
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2009)
Tmin, Tmax0.961, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
4452, 2419, 1593
Rint0.019
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.147, 1.03
No. of reflections2419
No. of parameters153
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.18

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.88 (2)2.01 (2)2.881 (2)171 (2)
O3—H3O···O1ii0.86 (3)1.77 (3)2.630 (2)172 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y+1/2, z+1/2.
 

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

First citationGowda, B. T., Foro, S., Saraswathi, B. S. & Fuess, H. (2010a). Acta Cryst. E66, o394.  Web of Science CSD CrossRef IUCr Journals
First citationGowda, B. T., Foro, S., Saraswathi, B. S. & Fuess, H. (2010b). Acta Cryst. E66, o436.  Web of Science CSD CrossRef IUCr Journals
First citationGowda, B. T., Foro, S., Saraswathi, B. S., Terao, H. & Fuess, H. (2009). Acta Cryst. E65, o466.  Web of Science CSD CrossRef IUCr Journals
First citationJagannathan, N. R., Rajan, S. S. & Subramanian, E. (1994). J. Chem. Crystallogr. 24, 75–78.  CSD CrossRef CAS Web of Science
First citationLeiserowitz, L. (1976). Acta Cryst. B32, 775–802.  CrossRef CAS IUCr Journals Web of Science
First citationOxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds