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

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ISSN: 2056-9890
Volume 67| Part 5| May 2011| Page o1050

2-Methyl-4-(2-methyl­benzamido)­benzoic acid

aCollege of Food Science and Light Industry, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and bCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 22 February 2011; accepted 25 March 2011; online 7 April 2011)

In the crystal structure of the title compound, C16H15NO3, inter­molecular N—H⋯O hydrogen bonds link the mol­ecules into chains parallel to the b axis and pairs of inter­molecular O—H⋯O hydrogen bonds between inversion-related carb­oxy­lic acid groups link the mol­ecules into dimers. The dihedral angle between the two benzene rings is 82.4 (2)°.

Related literature

For the use of the title compound as an inter­mediate in the preparation of pharmaceutically active benzazepine compounds that have vasopressin antagonistic activity, see: Yasuhiro et al. (2007[Yasuhiro, T., Takuya, F. & Takao, N. (2007). Bioorg. Med. Chem. Lett. 17, 6455-6458.]). For the preparation of the title compound, see: Yasuhiro et al. (2000[Yasuhiro, T., Takao, N. & Jun-Ichi, M. (2000). Bioorg. Med. Chem. Lett. 10, 2493-2495.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C16H15NO3

  • Mr = 269.29

  • Monoclinic, C 2/c

  • a = 23.318 (9) Å

  • b = 10.230 (2) Å

  • c = 13.901 (3) Å

  • β = 125.50 (3)°

  • V = 2699.7 (16) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 293 K

  • 0.20 × 0.10 × 0.10 mm

Data collection
  • Enraf–Nonius CAD-4 diffractometer

  • Absorption correction: ψ scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.982, Tmax = 0.991

  • 4968 measured reflections

  • 2493 independent reflections

  • 1641 reflections with I > 2σ(I)

  • Rint = 0.034

  • 3 standard reflections every 120 min intensity decay: 1%

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.138

  • S = 1.00

  • 2493 reflections

  • 184 parameters

  • H-atom parameters constrained

  • Δρmax = 0.19 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
N—H0A⋯O1i 0.86 2.23 3.076 (3) 169
O2—H2A⋯O3ii 0.82 1.82 2.636 (4) 174
Symmetry codes: (i) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) -x+1, -y+2, -z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989[Enraf-Nonius (1989). CAD-4 EXPRESS. Enraf-Nonius, Delft. The Netherlands.]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PLATON (Spek, 2009)[Spek, A. L. (2009). Acta Cryst. D65, 148-155.].

Supporting information


Comment top

The title compound, 2-methyl-4-(2-methylbenzamido)benzoic acid, or salts thereof are useful as intermediates for preparing pharmaceutically active benzazepine compounds that have vasopressin antagonistic activity. (Yasuhiro et al. 2007).

In the molecule of 2-methyl-4-(2-methylbenzamido)benzoic acid (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Intermolecular N-H···O hydrogen bonds link the molecules parallel to the b axis and pairs of intermolecular N-H···O hydrogen bonds link the molecules parallel to the b axis and pairs of intermolecular O-H···O hydrogen bonds between inversion related (x,y,z & 1-x,2-y,-z) carboxylic acid groups link the molecules into dimers. The dihedral angle between the two benzene rings is 82.39 (19) ° (Fig. 2).

Related literature top

For the use of the title compound as an intermediate in the preparation of pharmaceutically active benzazepine compounds that have vasopressin antagonistic activity, see: Yasuhiro et al. (2007). For the preparation of the title compound, see: Yasuhiro et al. (2000). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, 2-methyl-4-(2-methylbenzamido)benzoic acid was prepared by the literature method (Yasuhiro et al. 2000). Recrystallization of the of the crude crystalline product gave a yield of 81%. Crystals suitable for X-ray analysis were obtained by slow evaporation of a solution in methanol.

Refinement top

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and O-H =0.82 Å (for OH) and C-H = 0.93, 0.98 and 0.96 Å for aromatic, methine and methyl H, respectively. They were constrained to ride on their parent atoms, with Uiso(H) values set to either 1.2Ueq or 1.5Ueq (RCH3, OH) of the attached atom.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram of 2-methyl-4-(2-methylbenzamido)benzoic acid viewed down the b axis. Hydrogen bonds are shown as dashed lines.
2-Methyl-4-(2-methylbenzamido)benzoic acid top
Crystal data top
C16H15NO3F(000) = 1136
Mr = 269.29Dx = 1.325 Mg m3
Monoclinic, C2/cMelting point: 497 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 23.318 (9) ÅCell parameters from 25 reflections
b = 10.230 (2) Åθ = 9–13°
c = 13.901 (3) ŵ = 0.09 mm1
β = 125.50 (3)°T = 293 K
V = 2699.7 (16) Å3Block, colourless
Z = 80.20 × 0.10 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
1641 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
Graphite monochromatorθmax = 25.4°, θmin = 2.2°
ω/2θ scansh = 2828
Absorption correction: ψ scan
(North et al., 1968)
k = 012
Tmin = 0.982, Tmax = 0.991l = 1616
4968 measured reflections3 standard reflections every 120 min
2493 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.138 w = 1/[σ2(Fo2) + (0.075P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2493 reflectionsΔρmax = 0.19 e Å3
184 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0023 (5)
Crystal data top
C16H15NO3V = 2699.7 (16) Å3
Mr = 269.29Z = 8
Monoclinic, C2/cMo Kα radiation
a = 23.318 (9) ŵ = 0.09 mm1
b = 10.230 (2) ÅT = 293 K
c = 13.901 (3) Å0.20 × 0.10 × 0.10 mm
β = 125.50 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
1641 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.034
Tmin = 0.982, Tmax = 0.9913 standard reflections every 120 min
4968 measured reflections intensity decay: 1%
2493 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.138H-atom parameters constrained
S = 1.00Δρmax = 0.19 e Å3
2493 reflectionsΔρmin = 0.18 e Å3
184 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 > 2σ(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
N0.27879 (10)1.06074 (17)0.23814 (17)0.0431 (5)
H0A0.27251.13800.25470.052*
O10.25277 (9)0.84642 (15)0.23884 (17)0.0573 (5)
C10.09320 (14)0.8941 (3)0.0956 (2)0.0698 (8)
H1A0.04320.88650.05590.105*
H1B0.11410.80860.11590.105*
H1C0.10260.93640.04450.105*
O20.45652 (10)0.90523 (16)0.04728 (17)0.0639 (6)
H2A0.47980.90400.02020.096*
C20.12408 (12)0.9737 (2)0.2061 (2)0.0432 (6)
O30.46865 (10)1.11880 (17)0.03858 (18)0.0662 (6)
C30.08066 (13)1.0191 (2)0.2371 (2)0.0507 (7)
H3A0.03281.00020.18840.061*
C40.10675 (14)1.0914 (2)0.3382 (2)0.0496 (7)
H4A0.07641.12140.35620.060*
C50.17705 (14)1.1195 (2)0.4121 (2)0.0490 (6)
H5A0.19491.16560.48180.059*
C60.22118 (12)1.0787 (2)0.3823 (2)0.0440 (6)
H6A0.26881.09970.43120.053*
C70.19543 (12)1.0070 (2)0.2804 (2)0.0372 (5)
C80.24493 (12)0.9618 (2)0.2510 (2)0.0400 (5)
C90.32340 (11)1.0500 (2)0.2002 (2)0.0387 (5)
C100.32865 (11)1.1578 (2)0.1449 (2)0.0420 (6)
H10A0.30431.23350.13730.050*
C110.36888 (12)1.1568 (2)0.1007 (2)0.0409 (6)
C120.40456 (11)1.0408 (2)0.1123 (2)0.0404 (6)
C130.39995 (12)0.9348 (2)0.1700 (2)0.0458 (6)
H13A0.42440.85890.17870.055*
C140.36050 (12)0.9378 (2)0.2148 (2)0.0459 (6)
H14A0.35890.86570.25400.055*
C150.37002 (14)1.2772 (2)0.0391 (2)0.0555 (7)
H15A0.33691.34000.03120.083*
H15B0.35741.25380.03780.083*
H15C0.41641.31440.08480.083*
C160.44573 (12)1.0256 (2)0.0627 (2)0.0452 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N0.0528 (12)0.0369 (10)0.0640 (13)0.0009 (9)0.0480 (11)0.0035 (9)
O10.0742 (12)0.0373 (9)0.0957 (14)0.0002 (8)0.0695 (12)0.0015 (9)
C10.0601 (18)0.098 (2)0.0525 (17)0.0085 (16)0.0333 (15)0.0222 (16)
O20.0834 (13)0.0489 (10)0.1041 (15)0.0071 (9)0.0799 (13)0.0164 (10)
C20.0471 (14)0.0498 (14)0.0434 (14)0.0013 (11)0.0324 (12)0.0026 (11)
O30.0883 (14)0.0514 (11)0.1102 (16)0.0040 (9)0.0870 (14)0.0038 (10)
C30.0415 (14)0.0655 (16)0.0562 (16)0.0015 (12)0.0348 (13)0.0037 (13)
C40.0609 (16)0.0479 (14)0.0690 (17)0.0030 (12)0.0542 (15)0.0028 (13)
C50.0685 (17)0.0427 (13)0.0559 (16)0.0053 (12)0.0476 (15)0.0077 (11)
C60.0479 (14)0.0427 (13)0.0512 (15)0.0059 (11)0.0344 (13)0.0044 (11)
C70.0451 (13)0.0355 (11)0.0451 (13)0.0019 (10)0.0342 (12)0.0042 (10)
C80.0438 (13)0.0395 (13)0.0471 (13)0.0004 (10)0.0324 (12)0.0003 (10)
C90.0408 (12)0.0395 (12)0.0493 (14)0.0042 (10)0.0339 (12)0.0061 (10)
C100.0490 (14)0.0334 (12)0.0606 (15)0.0011 (10)0.0416 (13)0.0061 (11)
C110.0466 (13)0.0371 (12)0.0522 (14)0.0085 (10)0.0362 (12)0.0096 (11)
C120.0412 (13)0.0423 (13)0.0511 (14)0.0057 (10)0.0344 (12)0.0081 (11)
C130.0477 (14)0.0400 (12)0.0665 (17)0.0055 (10)0.0426 (14)0.0009 (11)
C140.0498 (14)0.0413 (13)0.0655 (16)0.0021 (11)0.0442 (14)0.0040 (12)
C150.0724 (18)0.0418 (14)0.0803 (19)0.0006 (12)0.0603 (16)0.0031 (13)
C160.0472 (14)0.0442 (13)0.0595 (16)0.0033 (11)0.0398 (13)0.0101 (12)
Geometric parameters (Å, º) top
N—C81.357 (3)C5—H5A0.9300
N—C91.417 (3)C6—C71.386 (3)
N—H0A0.8600C6—H6A0.9300
O1—C81.221 (3)C7—C81.503 (3)
C1—C21.501 (3)C9—C141.380 (3)
C1—H1A0.9600C9—C101.389 (3)
C1—H1B0.9600C10—C111.389 (3)
C1—H1C0.9600C10—H10A0.9300
O2—C161.300 (3)C11—C121.404 (3)
O2—H2A0.8200C11—C151.509 (3)
C2—C31.391 (3)C12—C131.388 (3)
C2—C71.398 (3)C12—C161.481 (3)
O3—C161.230 (3)C13—C141.379 (3)
C3—C41.378 (4)C13—H13A0.9300
C3—H3A0.9300C14—H14A0.9300
C4—C51.367 (4)C15—H15A0.9600
C4—H4A0.9300C15—H15B0.9600
C5—C61.378 (3)C15—H15C0.9600
C8—N—C9126.85 (18)O1—C8—C7122.33 (19)
C8—N—H0A116.6N—C8—C7113.80 (18)
C9—N—H0A116.6C14—C9—C10119.50 (19)
C2—C1—H1A109.5C14—C9—N122.87 (19)
C2—C1—H1B109.5C10—C9—N117.63 (18)
H1A—C1—H1B109.5C11—C10—C9122.6 (2)
C2—C1—H1C109.5C11—C10—H10A118.7
H1A—C1—H1C109.5C9—C10—H10A118.7
H1B—C1—H1C109.5C10—C11—C12117.56 (19)
C16—O2—H2A109.5C10—C11—C15118.97 (19)
C3—C2—C7117.3 (2)C12—C11—C15123.43 (18)
C3—C2—C1119.7 (2)C13—C12—C11119.16 (18)
C7—C2—C1123.1 (2)C13—C12—C16118.4 (2)
C4—C3—C2121.7 (2)C11—C12—C16122.4 (2)
C4—C3—H3A119.1C14—C13—C12122.6 (2)
C2—C3—H3A119.1C14—C13—H13A118.7
C5—C4—C3120.4 (2)C12—C13—H13A118.7
C5—C4—H4A119.8C13—C14—C9118.5 (2)
C3—C4—H4A119.8C13—C14—H14A120.7
C4—C5—C6119.3 (2)C9—C14—H14A120.7
C4—C5—H5A120.4C11—C15—H15A109.5
C6—C5—H5A120.4C11—C15—H15B109.5
C5—C6—C7120.8 (2)H15A—C15—H15B109.5
C5—C6—H6A119.6C11—C15—H15C109.5
C7—C6—H6A119.6H15A—C15—H15C109.5
C6—C7—C2120.50 (19)H15B—C15—H15C109.5
C6—C7—C8119.7 (2)O3—C16—O2122.23 (19)
C2—C7—C8119.8 (2)O3—C16—C12123.2 (2)
O1—C8—N123.87 (19)O2—C16—C12114.6 (2)
C7—C2—C3—C41.5 (3)C8—N—C9—C10152.9 (2)
C1—C2—C3—C4179.4 (2)C14—C9—C10—C111.5 (3)
C2—C3—C4—C50.7 (4)N—C9—C10—C11177.8 (2)
C3—C4—C5—C62.4 (4)C9—C10—C11—C120.7 (3)
C4—C5—C6—C71.8 (3)C9—C10—C11—C15178.4 (2)
C5—C6—C7—C20.5 (3)C10—C11—C12—C132.0 (3)
C5—C6—C7—C8179.0 (2)C15—C11—C12—C13179.6 (2)
C3—C2—C7—C62.1 (3)C10—C11—C12—C16176.5 (2)
C1—C2—C7—C6178.8 (2)C15—C11—C12—C161.2 (4)
C3—C2—C7—C8179.5 (2)C11—C12—C13—C141.2 (4)
C1—C2—C7—C80.4 (3)C16—C12—C13—C14177.3 (2)
C9—N—C8—O15.4 (4)C12—C13—C14—C90.9 (4)
C9—N—C8—C7173.8 (2)C10—C9—C14—C132.2 (4)
C6—C7—C8—O1121.0 (3)N—C9—C14—C13177.0 (2)
C2—C7—C8—O157.5 (3)C13—C12—C16—O3160.2 (2)
C6—C7—C8—N59.8 (3)C11—C12—C16—O321.4 (4)
C2—C7—C8—N121.7 (2)C13—C12—C16—O219.2 (3)
C8—N—C9—C1426.4 (4)C11—C12—C16—O2159.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H0A···O1i0.862.233.076 (3)169
O2—H2A···O3ii0.821.822.636 (4)174
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1, y+2, z.

Experimental details

Crystal data
Chemical formulaC16H15NO3
Mr269.29
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)23.318 (9), 10.230 (2), 13.901 (3)
β (°) 125.50 (3)
V3)2699.7 (16)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.20 × 0.10 × 0.10
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.982, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
4968, 2493, 1641
Rint0.034
(sin θ/λ)max1)0.604
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.138, 1.00
No. of reflections2493
No. of parameters184
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.18

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H0A···O1i0.862.233.076 (3)169
O2—H2A···O3ii0.821.822.636 (4)174
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1, y+2, z.
 

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationEnraf–Nonius (1989). CAD-4 EXPRESS. Enraf–Nonius, Delft. The Netherlands.  Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYasuhiro, T., Takao, N. & Jun-Ichi, M. (2000). Bioorg. Med. Chem. Lett. 10, 2493–2495.  Web of Science PubMed Google Scholar
First citationYasuhiro, T., Takuya, F. & Takao, N. (2007). Bioorg. Med. Chem. Lett. 17, 6455–6458.  Web of Science PubMed Google Scholar

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.

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ISSN: 2056-9890
Volume 67| Part 5| May 2011| Page o1050
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