2-Hy­droxy-N-(4-methyl­phen­yl)benzamide

In the crystal structure of the title compound, C₁₄H₁₃NO₂, the mol­ecules are approximately planar, the r.m.s. deviation for all non-H atoms being 0.0435 Å; the dihedral angle between the two rings is 3.45 (12)°. The planarity is accounted for in terms of the presence of intra­molecular N—H...O and C—H...O hydrogen bonding, each of which completes an S(6) ring motif. The mol­ecules are stabilized in the form of supra­molecular chains extending along the crystallographic c axis due to inter­molecular O—H...O and C—H...O hydrogen bonding; each type leads to an R₂¹(6) ring motif.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.059
• wR factor = 0.159
• Data-to-parameter ratio = 17.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         45 Perc.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         29

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?

   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
   1 ALERT level G = General information/check it is not something unexpected

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

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S1. Comment

We have reported the crystal structures of (II) i.e. 2-hydroxy-N-(3-nitrophenyl)benzamide (Raza et al., 2010a), (III) i.e. N-(4-chlorophenyl)-2-hydroxybenzamide (Raza et al., 2010b) and (IV) i.e. N-(3-chlorophenyl)-2 -hydroxybenzamide (Raza et al., 2010c). In this connection, the title compound (I, Fig. 1) has been prepared as a precursor for the synthesis of symmetric as well as asymmetric benzoxazepines.

In (I), the 2-hydroxyphenyl group A (C1–C6/O1) and 4-methylanilinic group B (C8—C14/N1) are planar with r.m.s. deviations of 0.0048 and 0.0086 Å, respectively. The dihedral angle between A/B is 3.45 (12) °. There is intramolecular H-bonding of the type N—H···O and C—H···O types (Table 1, Fig. 1), each of which completes a S(6) ring motif (Bernstein et al., 1995). There is also intermolecular H-bonding of the type C—H···O and O—H···O (Table 1). These lead to the formation of two R₂¹(6) ring motifs and to supramolecular chains extending along the crystallographic c-axis (Fig. 2).

Related literature

For related benzamide structures, see: Raza et al. (2010a,b,c). For graph-set notation, see: Bernstein et al. (1995).

S2. Experimental

To a well stirred solution of 2-hydroxy benzoic acid (2.76 g, 0.02 mol, 1 equiv.) and SOCl₂ (1.74 mL, 2.84 g, 0.024 mol, 1.2 equiv.) in dry CHCl₃, 4-metylaniline (2.14 g, 0.02 mol, 1 equiv.) and Et₃N (4.16 mL, 3 g, 0.03 mol, 1.5 equiv.) were added slowly at room temperature followed by 3 h reflux. After completion of reaction, the reaction mixture was cooled to room temperature, neutralized with aqueous NaHCO₃ (10 %) and extracted with CHCl₃ (3×25 mL). The organic layers were combined, dried over anhydrous Na₂SO₄, filtered and concentrated under reduced pressure to afford a brown solid. The column chromatographic purification with 1%, 2% and 3% CHCl₃ in petrol (300 mL each) over a silica gel packed column (of 25.5 cm length) afforded white needles of (I) in the 96th-280th fractions (50 mL each).

S3. Refinement

Although H atoms appeared in difference Fourier maps they were positioned geometrically with (O–H = 0.82, N–H = 0.86 and C–H = 0.93-0.96 Å) and refined as riding with U_iso(H) = xU_eq(C), where x = 1.5 for hydroxy- & methyl-H atoms and x = 1.2 for other H atoms.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures

	Fig. 1. View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii. The dotted line indicate the intramolecular H-bonding.
	Fig. 2. The partial packing diagram which shows that molecules form supramolecular chains extending along the c-axis. The dotted line indicate the intramolecular H-bonding.

2-Hydroxy-N-(4-methylphenyl)benzamide

Crystal data

C14H13NO2	F(000) = 480
Mr = 227.25	Dx = 1.287 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1243 reflections
a = 19.4067 (17) Å	θ = 1.1–27.9°
b = 4.9122 (5) Å	µ = 0.09 mm^−1
c = 12.7261 (11) Å	T = 296 K
β = 104.793 (4)°	Needle, colorless
V = 1172.96 (19) Å^3	0.34 × 0.14 × 0.12 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer	2771 independent reflections
Radiation source: fine-focus sealed tube	1243 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
Detector resolution: 7.6 pixels mm^-1	θmax = 27.9°, θmin = 1.1°
ω scans	h = −25→25
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −4→6
Tmin = 0.979, Tmax = 0.988	l = −16→16
10416 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0648P)^2] where P = (Fo^2 + 2Fc^2)/3
2771 reflections	(Δ/σ)max < 0.001
156 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.29367 (9)	−0.2157 (4)	0.22720 (13)	0.0599 (7)
O2	0.29429 (9)	−0.0348 (3)	−0.09273 (12)	0.0598 (7)
N1	0.24804 (9)	0.0722 (4)	0.04697 (14)	0.0438 (7)
C1	0.33925 (11)	−0.2782 (5)	0.07185 (18)	0.0407 (8)
C2	0.33876 (12)	−0.3489 (5)	0.17802 (18)	0.0438 (8)
C3	0.38382 (13)	−0.5515 (5)	0.2327 (2)	0.0516 (9)
C4	0.42941 (13)	−0.6849 (5)	0.1833 (2)	0.0596 (11)
C5	0.43143 (13)	−0.6168 (6)	0.0796 (2)	0.0615 (11)
C6	0.38654 (13)	−0.4161 (5)	0.0249 (2)	0.0539 (10)
C7	0.29213 (12)	−0.0712 (5)	0.00262 (18)	0.0416 (8)
C8	0.19724 (12)	0.2725 (5)	−0.00178 (18)	0.0428 (8)
C9	0.18909 (14)	0.3743 (5)	−0.1055 (2)	0.0564 (10)
C10	0.13704 (14)	0.5697 (6)	−0.1449 (2)	0.0605 (11)
C11	0.09251 (13)	0.6670 (5)	−0.0859 (2)	0.0544 (10)
C12	0.10233 (14)	0.5654 (5)	0.0186 (2)	0.0592 (10)
C13	0.15368 (13)	0.3727 (5)	0.06023 (19)	0.0524 (9)
C14	0.03636 (15)	0.8783 (5)	−0.1313 (2)	0.0751 (11)
H1	0.29314	−0.29364	0.28396	0.0899*
H1A	0.25091	0.03812	0.11424	0.0525*
H3	0.38315	−0.59736	0.30329	0.0619*
H4	0.45896	−0.82174	0.22036	0.0714*
H5	0.46273	−0.70494	0.04648	0.0739*
H6	0.38794	−0.37165	−0.04556	0.0647*
H9	0.21810	0.31275	−0.14848	0.0677*
H10	0.13229	0.63728	−0.21461	0.0726*
H12	0.07355	0.62883	0.06158	0.0711*
H13	0.15915	0.30919	0.13074	0.0628*
H14A	0.03008	0.89281	−0.20839	0.1127*
H14B	0.05114	1.05104	−0.09782	0.1127*
H14C	−0.00787	0.82537	−0.11655	0.1127*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0753 (12)	0.0677 (13)	0.0429 (11)	0.0164 (10)	0.0262 (9)	0.0130 (9)
O2	0.0889 (13)	0.0586 (13)	0.0371 (10)	0.0035 (10)	0.0256 (9)	0.0009 (8)
N1	0.0496 (12)	0.0504 (14)	0.0318 (10)	0.0029 (10)	0.0111 (9)	0.0039 (9)
C1	0.0437 (13)	0.0379 (15)	0.0409 (14)	−0.0064 (11)	0.0117 (11)	−0.0060 (11)
C2	0.0449 (14)	0.0444 (16)	0.0438 (14)	−0.0034 (12)	0.0147 (12)	−0.0036 (12)
C3	0.0500 (14)	0.0479 (18)	0.0534 (16)	−0.0010 (13)	0.0070 (12)	0.0053 (13)
C4	0.0506 (16)	0.0481 (19)	0.077 (2)	0.0041 (13)	0.0109 (15)	0.0031 (14)
C5	0.0525 (16)	0.061 (2)	0.076 (2)	0.0033 (15)	0.0257 (15)	−0.0090 (16)
C6	0.0557 (16)	0.0571 (19)	0.0522 (16)	−0.0014 (14)	0.0197 (13)	−0.0048 (14)
C7	0.0494 (14)	0.0400 (16)	0.0365 (14)	−0.0101 (12)	0.0132 (11)	−0.0050 (11)
C8	0.0474 (14)	0.0383 (15)	0.0400 (14)	−0.0038 (12)	0.0062 (11)	0.0006 (11)
C9	0.0608 (16)	0.0616 (19)	0.0465 (16)	−0.0014 (15)	0.0130 (13)	0.0051 (14)
C10	0.0673 (18)	0.056 (2)	0.0515 (17)	−0.0024 (15)	0.0028 (14)	0.0110 (14)
C11	0.0544 (16)	0.0360 (16)	0.0628 (19)	−0.0060 (13)	−0.0031 (14)	−0.0021 (13)
C12	0.0613 (17)	0.0524 (19)	0.0615 (18)	0.0060 (14)	0.0112 (14)	−0.0038 (14)
C13	0.0599 (16)	0.0563 (18)	0.0397 (14)	0.0043 (14)	0.0105 (12)	0.0046 (12)
C14	0.0718 (19)	0.0511 (19)	0.086 (2)	0.0023 (16)	−0.0097 (16)	0.0010 (16)

Geometric parameters (Å, º)

O1—C2	1.366 (3)	C10—C11	1.368 (4)
O2—C7	1.238 (3)	C11—C12	1.387 (3)
O1—H1	0.8200	C11—C14	1.509 (4)
N1—C7	1.339 (3)	C12—C13	1.379 (4)
N1—C8	1.419 (3)	C3—H3	0.9300
N1—H1A	0.8600	C4—H4	0.9300
C1—C7	1.495 (3)	C5—H5	0.9300
C1—C6	1.392 (3)	C6—H6	0.9300
C1—C2	1.397 (3)	C9—H9	0.9300
C2—C3	1.389 (3)	C10—H10	0.9300
C3—C4	1.375 (4)	C12—H12	0.9300
C4—C5	1.372 (4)	C13—H13	0.9300
C5—C6	1.381 (4)	C14—H14A	0.9600
C8—C13	1.386 (3)	C14—H14B	0.9600
C8—C9	1.382 (3)	C14—H14C	0.9600
C9—C10	1.391 (4)
C2—O1—H1	109.00	C11—C12—C13	121.6 (2)
C7—N1—C8	128.90 (19)	C8—C13—C12	120.8 (2)
C8—N1—H1A	116.00	C2—C3—H3	120.00
C7—N1—H1A	116.00	C4—C3—H3	120.00
C2—C1—C6	117.5 (2)	C3—C4—H4	120.00
C2—C1—C7	125.8 (2)	C5—C4—H4	120.00
C6—C1—C7	116.7 (2)	C4—C5—H5	120.00
O1—C2—C3	120.6 (2)	C6—C5—H5	120.00
O1—C2—C1	119.2 (2)	C1—C6—H6	119.00
C1—C2—C3	120.3 (2)	C5—C6—H6	119.00
C2—C3—C4	120.6 (2)	C8—C9—H9	120.00
C3—C4—C5	120.2 (2)	C10—C9—H9	120.00
C4—C5—C6	119.3 (2)	C9—C10—H10	118.00
C1—C6—C5	122.1 (2)	C11—C10—H10	118.00
N1—C7—C1	118.03 (19)	C11—C12—H12	119.00
O2—C7—C1	120.5 (2)	C13—C12—H12	119.00
O2—C7—N1	121.5 (2)	C8—C13—H13	120.00
N1—C8—C9	124.5 (2)	C12—C13—H13	120.00
N1—C8—C13	117.0 (2)	C11—C14—H14A	109.00
C9—C8—C13	118.5 (2)	C11—C14—H14B	109.00
C8—C9—C10	119.3 (2)	C11—C14—H14C	109.00
C9—C10—C11	123.1 (2)	H14A—C14—H14B	109.00
C10—C11—C14	121.7 (2)	H14A—C14—H14C	109.00
C10—C11—C12	116.7 (2)	H14B—C14—H14C	109.00
C12—C11—C14	121.6 (2)
C8—N1—C7—O2	2.0 (4)	C1—C2—C3—C4	0.0 (4)
C8—N1—C7—C1	−178.1 (2)	C2—C3—C4—C5	0.8 (4)
C7—N1—C8—C9	−6.3 (4)	C3—C4—C5—C6	−1.0 (4)
C7—N1—C8—C13	174.3 (2)	C4—C5—C6—C1	0.4 (4)
C6—C1—C2—O1	179.2 (2)	N1—C8—C9—C10	179.6 (2)
C6—C1—C2—C3	−0.5 (4)	C13—C8—C9—C10	−1.0 (4)
C7—C1—C2—O1	−2.3 (4)	N1—C8—C13—C12	−179.2 (2)
C7—C1—C2—C3	177.9 (2)	C9—C8—C13—C12	1.4 (4)
C2—C1—C6—C5	0.3 (4)	C8—C9—C10—C11	−0.4 (4)
C7—C1—C6—C5	−178.3 (2)	C9—C10—C11—C12	1.4 (4)
C2—C1—C7—O2	−176.0 (2)	C9—C10—C11—C14	−179.7 (2)
C2—C1—C7—N1	4.1 (4)	C10—C11—C12—C13	−1.0 (4)
C6—C1—C7—O2	2.5 (3)	C14—C11—C12—C13	−179.9 (2)
C6—C1—C7—N1	−177.5 (2)	C11—C12—C13—C8	−0.4 (4)
O1—C2—C3—C4	−179.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.78	2.596 (2)	179
N1—H1A···O1	0.86	1.92	2.647 (2)	141
C3—H3···O2^i	0.93	2.51	3.179 (3)	129
C9—H9···O2	0.93	2.25	2.840 (3)	121

Symmetry code: (i) x, −y−1/2, z+1/2.