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

The title compound, C₁₅H₁₅NO₂, was obtained by the reaction of 2-chloro-4-methyl-benzoic acid and o-toluidine using 2-eth­oxy­ethanol as solvent. Crystals of the title compounds were obtained from crystallization in acetone. The mol­ecule in the crystal is twisted with a dihedral angle between the aromatic rings of 50.86 (5)°. In the crystal structure, the mol­ecules associate to form acid–acid hydrogen-bonded dimers linked by pairwise O—H...O hydrogen bonds.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.045
• wR factor = 0.131
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT761_ALERT_1_C CIF Contains no X-H Bonds ......................     Please Check
PLAT762_ALERT_1_C CIF Contains no X-Y-H or H-Y-H Angles ..........     Please Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          8 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT899_ALERT_4_G SHELXL2018 is Deprecated and Succeeded by SHELXL     2019/3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         41 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        1.9 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO 1.171.38.43f (Rigaku OD, 2015); cell refinement: CrysAlis PRO 1.171.38.43f (Rigaku OD, 2015); data reduction: CrysAlis PRO 1.171.38.43f (Rigaku OD, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009), Mercury (Macrae et al., 2020); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

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

Crystal data

C15H15NO2	F(000) = 512
Mr = 241.28	Dx = 1.296 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 9.6678 (8) Å	Cell parameters from 1387 reflections
b = 10.9294 (11) Å	θ = 9.3–69.0°
c = 11.7231 (8) Å	µ = 0.69 mm^−1
β = 93.395 (7)°	T = 293 K
V = 1236.53 (18) Å^3	Plate, clear light colourless
Z = 4	0.08 × 0.04 × 0.02 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	2285 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	1828 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.019
Detector resolution: 16.0733 pixels mm^-1	θmax = 70.0°, θmin = 4.6°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015)	k = −12→13
Tmin = 0.919, Tmax = 1.000	l = −13→10
4437 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0678P)^2 + 0.2398P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2285 reflections	Δρmax = 0.25 e Å^−3
166 parameters	Δρmin = −0.20 e Å^−3
0 restraints

Special details

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. The positions of H atoms in N1 and O1 were obtained from the difference Fourier map. Other H atoms were positioned geometrically with C—H = 0.93 for aromatic, and constrained to ride on their parent atoms with U_iso(H) = xU_eq(C,O), where x=1.5 for all H atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.32010 (13)	0.52719 (14)	0.45925 (9)	0.0527 (4)
H1	0.396573	0.509295	0.437474	0.079*
O2	0.44087 (12)	0.53328 (13)	0.62639 (9)	0.0487 (4)
N1	0.30228 (14)	0.58797 (15)	0.81250 (11)	0.0434 (4)
H1A	0.377666	0.564178	0.783957	0.052*
C1	0.19420 (15)	0.61667 (15)	0.73583 (13)	0.0332 (4)
C2	0.20410 (16)	0.59559 (14)	0.61709 (13)	0.0333 (4)
C3	0.09126 (17)	0.62616 (17)	0.54234 (13)	0.0409 (4)
H3	0.096893	0.611557	0.464602	0.049*
C4	−0.02712 (18)	0.67684 (17)	0.57997 (15)	0.0455 (4)
H4	−0.100826	0.695348	0.528272	0.055*
C5	−0.03698 (17)	0.70070 (16)	0.69615 (15)	0.0405 (4)
C6	0.07217 (16)	0.66986 (16)	0.77176 (13)	0.0375 (4)
H6	0.064581	0.684862	0.849231	0.045*
C7	0.33051 (17)	0.54979 (15)	0.57000 (13)	0.0365 (4)
C8	−0.1651 (2)	0.7593 (2)	0.73824 (18)	0.0614 (6)
H8A	−0.238018	0.699747	0.739025	0.092*
H8B	−0.193583	0.825546	0.688383	0.092*
H8C	−0.145628	0.790187	0.814164	0.092*
C9	0.30353 (16)	0.59315 (16)	0.93298 (13)	0.0357 (4)
C10	0.41723 (16)	0.64529 (16)	0.99389 (13)	0.0370 (4)
C11	0.41862 (18)	0.64593 (17)	1.11262 (14)	0.0452 (4)
H11	0.494677	0.678781	1.154221	0.054*
C12	0.3104 (2)	0.59922 (19)	1.17011 (14)	0.0492 (5)
H12	0.312562	0.602599	1.249460	0.059*
C13	0.19886 (19)	0.54745 (18)	1.10961 (15)	0.0475 (5)
H13	0.125187	0.516229	1.148058	0.057*
C14	0.19640 (18)	0.54187 (17)	0.99152 (14)	0.0426 (4)
H14	0.122853	0.503693	0.951043	0.051*
C17	0.53483 (18)	0.69949 (18)	0.93333 (16)	0.0495 (5)
H17A	0.582818	0.635765	0.895481	0.074*
H17B	0.597691	0.739472	0.987773	0.074*
H17C	0.499370	0.757976	0.877931	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0452 (7)	0.0860 (11)	0.0276 (6)	0.0073 (7)	0.0069 (5)	−0.0103 (6)
O2	0.0421 (7)	0.0745 (9)	0.0299 (6)	0.0147 (6)	0.0058 (5)	−0.0046 (6)
N1	0.0337 (7)	0.0716 (11)	0.0253 (7)	0.0098 (7)	0.0055 (5)	−0.0038 (6)
C1	0.0326 (8)	0.0379 (8)	0.0294 (8)	−0.0023 (6)	0.0041 (6)	0.0010 (6)
C2	0.0350 (8)	0.0363 (8)	0.0288 (8)	−0.0023 (6)	0.0046 (6)	−0.0002 (6)
C3	0.0455 (9)	0.0493 (10)	0.0279 (8)	−0.0026 (8)	0.0019 (7)	0.0000 (7)
C4	0.0381 (9)	0.0576 (11)	0.0403 (9)	0.0025 (8)	−0.0021 (7)	0.0065 (8)
C5	0.0374 (9)	0.0438 (9)	0.0407 (9)	0.0020 (7)	0.0076 (7)	0.0061 (7)
C6	0.0388 (9)	0.0450 (9)	0.0295 (8)	0.0025 (7)	0.0082 (6)	0.0001 (7)
C7	0.0419 (9)	0.0422 (9)	0.0260 (7)	−0.0010 (7)	0.0066 (6)	−0.0007 (6)
C8	0.0493 (11)	0.0798 (15)	0.0563 (12)	0.0212 (11)	0.0120 (9)	0.0121 (11)
C9	0.0347 (8)	0.0457 (9)	0.0269 (7)	0.0108 (7)	0.0038 (6)	−0.0002 (7)
C10	0.0364 (8)	0.0400 (9)	0.0347 (8)	0.0094 (7)	0.0029 (6)	−0.0011 (7)
C11	0.0490 (10)	0.0497 (10)	0.0361 (9)	0.0095 (8)	−0.0051 (7)	−0.0046 (8)
C12	0.0610 (11)	0.0618 (12)	0.0251 (8)	0.0175 (9)	0.0044 (8)	0.0031 (8)
C13	0.0463 (10)	0.0587 (11)	0.0390 (9)	0.0109 (9)	0.0151 (8)	0.0124 (8)
C14	0.0363 (8)	0.0560 (11)	0.0358 (9)	0.0029 (8)	0.0046 (7)	0.0026 (8)
C17	0.0411 (9)	0.0543 (11)	0.0531 (11)	−0.0015 (8)	0.0036 (8)	0.0009 (9)

Geometric parameters (Å, º)

O1—C7	1.3196 (18)	C5—C6	1.379 (2)
O2—C7	1.235 (2)	C5—C8	1.504 (2)
N1—C1	1.374 (2)	C9—C10	1.396 (2)
N1—C9	1.4129 (19)	C9—C14	1.394 (2)
C1—C2	1.420 (2)	C10—C11	1.391 (2)
C1—C6	1.402 (2)	C10—C17	1.498 (2)
C2—C3	1.399 (2)	C11—C12	1.376 (3)
C2—C7	1.459 (2)	C12—C13	1.377 (3)
C3—C4	1.368 (2)	C13—C14	1.385 (2)
C4—C5	1.396 (2)
C1—N1—C9	127.31 (13)	O1—C7—C2	114.81 (14)
N1—C1—C2	120.78 (14)	O2—C7—O1	120.84 (14)
N1—C1—C6	121.27 (14)	O2—C7—C2	124.35 (14)
C6—C1—C2	117.94 (14)	C10—C9—N1	119.17 (14)
C1—C2—C7	122.22 (14)	C14—C9—N1	120.90 (15)
C3—C2—C1	118.69 (14)	C14—C9—C10	119.86 (15)
C3—C2—C7	118.99 (14)	C9—C10—C17	121.04 (15)
C4—C3—C2	122.08 (15)	C11—C10—C9	118.32 (15)
C3—C4—C5	119.82 (15)	C11—C10—C17	120.64 (16)
C4—C5—C8	120.33 (16)	C12—C11—C10	121.71 (17)
C6—C5—C4	119.19 (15)	C11—C12—C13	119.69 (16)
C6—C5—C8	120.47 (16)	C12—C13—C14	119.98 (16)
C5—C6—C1	122.24 (15)	C13—C14—C9	120.36 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.84	2.6570 (17)	174
N1—H1A···O2	0.86	2.01	2.6942 (17)	136

Symmetry code: (i) −x+1, −y+1, −z+1.