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

He, F.-F.; Shi, Y.-B.; Xia, S.; Wang, H.-B.

doi:10.1107/S160053681101110X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1050

doi:10.1107/S160053681101110X

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

Fei-Fei He,^a,^b Ya-Bin Shi,^a,^b Song Xia ^a,^b and Hai-Bo Wang ^a ^*

^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 ). For the preparation of the title compound, see: Yasuhiro et al. (2000 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₅NO₃
M_r = 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 ) T_min = 0.982, T_max = 0.991
4968 measured reflections
2493 independent reflections
1641 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: CAD-4 EXPRESS; 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681101110X/pk2306sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101110X/pk2306Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
	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

C₁₆H₁₅NO₃	F(000) = 1136
M_r = 269.29	D_x = 1.325 Mg m⁻³
Monoclinic, C2/c	Melting point: 497 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.318 (9) Å	Cell parameters from 25 reflections
b = 10.230 (2) Å	θ = 9–13°
c = 13.901 (3) Å	µ = 0.09 mm⁻¹
β = 125.50 (3)°	T = 293 K
V = 2699.7 (16) Å³	Block, colourless
Z = 8	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1641 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 25.4°, θ_min = 2.2°
ω/2θ scans	h = −28→28
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
T_min = 0.982, T_max = 0.991	l = −16→16
4968 measured reflections	3 standard reflections every 120 min
2493 independent reflections	intensity decay: 1%

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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.138	w = 1/[σ²(F_o²) + (0.075P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2493 reflections	Δρ_max = 0.19 e Å⁻³
184 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0023 (5)

Crystal data top

C₁₆H₁₅NO₃	V = 2699.7 (16) Å³
M_r = 269.29	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 23.318 (9) Å	µ = 0.09 mm⁻¹
b = 10.230 (2) Å	T = 293 K
c = 13.901 (3) Å	0.20 × 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)	R_int = 0.034
T_min = 0.982, T_max = 0.991	3 standard reflections every 120 min
4968 measured reflections	intensity decay: 1%
2493 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.00	Δρ_max = 0.19 e Å⁻³
2493 reflections	Δρ_min = −0.18 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N	0.27879 (10)	1.06074 (17)	0.23814 (17)	0.0431 (5)
H0A	0.2725	1.1380	0.2547	0.052*
O1	0.25277 (9)	0.84642 (15)	0.23884 (17)	0.0573 (5)
C1	0.09320 (14)	0.8941 (3)	0.0956 (2)	0.0698 (8)
H1A	0.0432	0.8865	0.0559	0.105*
H1B	0.1141	0.8086	0.1159	0.105*
H1C	0.1026	0.9364	0.0445	0.105*
O2	0.45652 (10)	0.90523 (16)	0.04728 (17)	0.0639 (6)
H2A	0.4798	0.9040	0.0202	0.096*
C2	0.12408 (12)	0.9737 (2)	0.2061 (2)	0.0432 (6)
O3	0.46865 (10)	1.11880 (17)	0.03858 (18)	0.0662 (6)
C3	0.08066 (13)	1.0191 (2)	0.2371 (2)	0.0507 (7)
H3A	0.0328	1.0002	0.1884	0.061*
C4	0.10675 (14)	1.0914 (2)	0.3382 (2)	0.0496 (7)
H4A	0.0764	1.1214	0.3562	0.060*
C5	0.17705 (14)	1.1195 (2)	0.4121 (2)	0.0490 (6)
H5A	0.1949	1.1656	0.4818	0.059*
C6	0.22118 (12)	1.0787 (2)	0.3823 (2)	0.0440 (6)
H6A	0.2688	1.0997	0.4312	0.053*
C7	0.19543 (12)	1.0070 (2)	0.2804 (2)	0.0372 (5)
C8	0.24493 (12)	0.9618 (2)	0.2510 (2)	0.0400 (5)
C9	0.32340 (11)	1.0500 (2)	0.2002 (2)	0.0387 (5)
C10	0.32865 (11)	1.1578 (2)	0.1449 (2)	0.0420 (6)
H10A	0.3043	1.2335	0.1373	0.050*
C11	0.36888 (12)	1.1568 (2)	0.1007 (2)	0.0409 (6)
C12	0.40456 (11)	1.0408 (2)	0.1123 (2)	0.0404 (6)
C13	0.39995 (12)	0.9348 (2)	0.1700 (2)	0.0458 (6)
H13A	0.4244	0.8589	0.1787	0.055*
C14	0.36050 (12)	0.9378 (2)	0.2148 (2)	0.0459 (6)
H14A	0.3589	0.8657	0.2540	0.055*
C15	0.37002 (14)	1.2772 (2)	0.0391 (2)	0.0555 (7)
H15A	0.3369	1.3400	0.0312	0.083*
H15B	0.3574	1.2538	−0.0378	0.083*
H15C	0.4164	1.3144	0.0848	0.083*
C16	0.44573 (12)	1.0256 (2)	0.0627 (2)	0.0452 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0528 (12)	0.0369 (10)	0.0640 (13)	−0.0009 (9)	0.0480 (11)	−0.0035 (9)
O1	0.0742 (12)	0.0373 (9)	0.0957 (14)	−0.0002 (8)	0.0695 (12)	−0.0015 (9)
C1	0.0601 (18)	0.098 (2)	0.0525 (17)	−0.0085 (16)	0.0333 (15)	−0.0222 (16)
O2	0.0834 (13)	0.0489 (10)	0.1041 (15)	−0.0071 (9)	0.0799 (13)	−0.0164 (10)
C2	0.0471 (14)	0.0498 (14)	0.0434 (14)	−0.0013 (11)	0.0324 (12)	0.0026 (11)
O3	0.0883 (14)	0.0514 (11)	0.1102 (16)	−0.0040 (9)	0.0870 (14)	−0.0038 (10)
C3	0.0415 (14)	0.0655 (16)	0.0562 (16)	0.0015 (12)	0.0348 (13)	0.0037 (13)
C4	0.0609 (16)	0.0479 (14)	0.0690 (17)	0.0030 (12)	0.0542 (15)	0.0028 (13)
C5	0.0685 (17)	0.0427 (13)	0.0559 (16)	−0.0053 (12)	0.0476 (15)	−0.0077 (11)
C6	0.0479 (14)	0.0427 (13)	0.0512 (15)	−0.0059 (11)	0.0344 (13)	−0.0044 (11)
C7	0.0451 (13)	0.0355 (11)	0.0451 (13)	0.0019 (10)	0.0342 (12)	0.0042 (10)
C8	0.0438 (13)	0.0395 (13)	0.0471 (13)	−0.0004 (10)	0.0324 (12)	−0.0003 (10)
C9	0.0408 (12)	0.0395 (12)	0.0493 (14)	−0.0042 (10)	0.0339 (12)	−0.0061 (10)
C10	0.0490 (14)	0.0334 (12)	0.0606 (15)	−0.0011 (10)	0.0416 (13)	−0.0061 (11)
C11	0.0466 (13)	0.0371 (12)	0.0522 (14)	−0.0085 (10)	0.0362 (12)	−0.0096 (11)
C12	0.0412 (13)	0.0423 (13)	0.0511 (14)	−0.0057 (10)	0.0344 (12)	−0.0081 (11)
C13	0.0477 (14)	0.0400 (12)	0.0665 (17)	0.0055 (10)	0.0426 (14)	−0.0009 (11)
C14	0.0498 (14)	0.0413 (13)	0.0655 (16)	0.0021 (11)	0.0442 (14)	0.0040 (12)
C15	0.0724 (18)	0.0418 (14)	0.0803 (19)	0.0006 (12)	0.0603 (16)	0.0031 (13)
C16	0.0472 (14)	0.0442 (13)	0.0595 (16)	−0.0033 (11)	0.0398 (13)	−0.0101 (12)

Geometric parameters (Å, º) top

N—C8	1.357 (3)	C5—H5A	0.9300
N—C9	1.417 (3)	C6—C7	1.386 (3)
N—H0A	0.8600	C6—H6A	0.9300
O1—C8	1.221 (3)	C7—C8	1.503 (3)
C1—C2	1.501 (3)	C9—C14	1.380 (3)
C1—H1A	0.9600	C9—C10	1.389 (3)
C1—H1B	0.9600	C10—C11	1.389 (3)
C1—H1C	0.9600	C10—H10A	0.9300
O2—C16	1.300 (3)	C11—C12	1.404 (3)
O2—H2A	0.8200	C11—C15	1.509 (3)
C2—C3	1.391 (3)	C12—C13	1.388 (3)
C2—C7	1.398 (3)	C12—C16	1.481 (3)
O3—C16	1.230 (3)	C13—C14	1.379 (3)
C3—C4	1.378 (4)	C13—H13A	0.9300
C3—H3A	0.9300	C14—H14A	0.9300
C4—C5	1.367 (4)	C15—H15A	0.9600
C4—H4A	0.9300	C15—H15B	0.9600
C5—C6	1.378 (3)	C15—H15C	0.9600

C8—N—C9	126.85 (18)	O1—C8—C7	122.33 (19)
C8—N—H0A	116.6	N—C8—C7	113.80 (18)
C9—N—H0A	116.6	C14—C9—C10	119.50 (19)
C2—C1—H1A	109.5	C14—C9—N	122.87 (19)
C2—C1—H1B	109.5	C10—C9—N	117.63 (18)
H1A—C1—H1B	109.5	C11—C10—C9	122.6 (2)
C2—C1—H1C	109.5	C11—C10—H10A	118.7
H1A—C1—H1C	109.5	C9—C10—H10A	118.7
H1B—C1—H1C	109.5	C10—C11—C12	117.56 (19)
C16—O2—H2A	109.5	C10—C11—C15	118.97 (19)
C3—C2—C7	117.3 (2)	C12—C11—C15	123.43 (18)
C3—C2—C1	119.7 (2)	C13—C12—C11	119.16 (18)
C7—C2—C1	123.1 (2)	C13—C12—C16	118.4 (2)
C4—C3—C2	121.7 (2)	C11—C12—C16	122.4 (2)
C4—C3—H3A	119.1	C14—C13—C12	122.6 (2)
C2—C3—H3A	119.1	C14—C13—H13A	118.7
C5—C4—C3	120.4 (2)	C12—C13—H13A	118.7
C5—C4—H4A	119.8	C13—C14—C9	118.5 (2)
C3—C4—H4A	119.8	C13—C14—H14A	120.7
C4—C5—C6	119.3 (2)	C9—C14—H14A	120.7
C4—C5—H5A	120.4	C11—C15—H15A	109.5
C6—C5—H5A	120.4	C11—C15—H15B	109.5
C5—C6—C7	120.8 (2)	H15A—C15—H15B	109.5
C5—C6—H6A	119.6	C11—C15—H15C	109.5
C7—C6—H6A	119.6	H15A—C15—H15C	109.5
C6—C7—C2	120.50 (19)	H15B—C15—H15C	109.5
C6—C7—C8	119.7 (2)	O3—C16—O2	122.23 (19)
C2—C7—C8	119.8 (2)	O3—C16—C12	123.2 (2)
O1—C8—N	123.87 (19)	O2—C16—C12	114.6 (2)

C7—C2—C3—C4	−1.5 (3)	C8—N—C9—C10	152.9 (2)
C1—C2—C3—C4	179.4 (2)	C14—C9—C10—C11	1.5 (3)
C2—C3—C4—C5	−0.7 (4)	N—C9—C10—C11	−177.8 (2)
C3—C4—C5—C6	2.4 (4)	C9—C10—C11—C12	0.7 (3)
C4—C5—C6—C7	−1.8 (3)	C9—C10—C11—C15	178.4 (2)
C5—C6—C7—C2	−0.5 (3)	C10—C11—C12—C13	−2.0 (3)
C5—C6—C7—C8	−179.0 (2)	C15—C11—C12—C13	−179.6 (2)
C3—C2—C7—C6	2.1 (3)	C10—C11—C12—C16	176.5 (2)
C1—C2—C7—C6	−178.8 (2)	C15—C11—C12—C16	−1.2 (4)
C3—C2—C7—C8	−179.5 (2)	C11—C12—C13—C14	1.2 (4)
C1—C2—C7—C8	−0.4 (3)	C16—C12—C13—C14	−177.3 (2)
C9—N—C8—O1	5.4 (4)	C12—C13—C14—C9	0.9 (4)
C9—N—C8—C7	−173.8 (2)	C10—C9—C14—C13	−2.2 (4)
C6—C7—C8—O1	121.0 (3)	N—C9—C14—C13	177.0 (2)
C2—C7—C8—O1	−57.5 (3)	C13—C12—C16—O3	−160.2 (2)
C6—C7—C8—N	−59.8 (3)	C11—C12—C16—O3	21.4 (4)
C2—C7—C8—N	121.7 (2)	C13—C12—C16—O2	19.2 (3)
C8—N—C9—C14	−26.4 (4)	C11—C12—C16—O2	−159.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅NO₃
M_r	269.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	23.318 (9), 10.230 (2), 13.901 (3)
β (°)	125.50 (3)
V (Å³)	2699.7 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.982, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	4968, 2493, 1641
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.138, 1.00
No. of reflections	2493
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z.

References

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. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 EXPRESS. Enraf–Nonius, Delft. The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yasuhiro, T., Takao, N. & Jun-Ichi, M. (2000). Bioorg. Med. Chem. Lett. 10, 2493–2495. Web of Science PubMed Google Scholar
Yasuhiro, T., Takuya, F. & Takao, N. (2007). Bioorg. Med. Chem. Lett. 17, 6455–6458. Web of Science PubMed Google Scholar

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1050

doi:10.1107/S160053681101110X

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