Phenyl 4-methyl­benzoate

The structure of the title compound, C₁₄H₁₂O₂, resembles those of phenyl benzoate and 4-methyl­phenyl benzoate, with similar bond parameters. The two aromatic rings make a dihedral angle of 76.0 (1)°. The plane of the central -C(=O)-O- group is twisted by 9.4 (2)° out of the plane of the benzoyl ring, and by 83.3 (1)° out of the plane of the phenyl ring. The crystal structure exhibits weak parallel stacking of the benzoyl rings, with an inter­planar distance of 3.65 Å and an offset of 1.84 Å. The methyl group shows orientational disorder.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.046
• wR factor = 0.145
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

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Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT331_ALERT_2_C Small Average Phenyl   C-C Dist. C1     -C6            1.37 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

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S1. Comment

In the present work, as a part of the study of the substituent effects on the crystal structures of aryl benzoates (Gowda et al., 2007a, b; 2008), the structure of phenyl-4-methylbenzoate (I) has been determined. The structure of (I) (Fig. 1) is similar to those of phenyl benzoate (II) (Adams & Morsi, 1976), 4-methylphenyl benzoate (III) (Gowda et al., 2007b), 4-methylphenyl 2-methylbenzoate (IV) (Gowda et al., 2008), 4-methylphenyl 4-methylbenzoate (V) (Gowda et al., 2007a) and other aryl benzoates. The two benzene rings make a dihedral angle of 76.0 (1)°, compared to the values of 55.7° for (II), 60.17 (7)° (III), 73.04 (8)° (IV) and 63.57 (5)° (V). The plane of the central –C(=O)–O– group in (I) is twisted 9.4 (2)° out of the plane of the benzoyl ring, and 83.3 (1)° out of the plane of the phenyl ring. The crystal structure exhibits weak parallel stacking of benzoyl rings, with interplanar distance of 3.65 Å and offset 1.84 Å. In the crystal structure, there are no classical hydrogen bonds. The molecules in the structure are packed into chains as viewed in the ac plane (Fig. 2).

Related literature

For preparation of the compound, see: Nayak & Gowda (2009). For background to our study of the effects of substituent on the crystal structures of aryl benzoates and for related structures, see: Gowda et al. (2007a,b, 2008). For phenyl

benzoate, see: Adams & Morsi (1976);

S2. Experimental

The title compound was prepared according to a literature method (Nayak & Gowda, 2009). The purity of the compound was checked by determination of its melting point. It was characterized by infrared and NMR spectra (Nayak & Gowda, 2009). Colorless single crystals of the title compound were obtained by slow evaporation of its ethanol solution.

S3. Refinement

All hydrogen atoms were placed in calculated positions with C–H distances 0.93 or 0.96 Å. The C14 methyl group shows orientational disorder in the hydrogen atom positions. The two sets of methyl hydrogen atoms were refined with equal occupancy. The U_iso(H) values were set at 1.2 U_eq(C-aromatic) or 1.5 U_eq(C-methyl).

Computing details

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: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Figures

	Fig. 1. Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound.

Phenyl 4-methylbenzoate

Crystal data

C14H12O2	F(000) = 448
Mr = 212.24	Dx = 1.237 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9248 reflections
a = 12.3440 (4) Å	θ = 3.1–29.3°
b = 8.1332 (2) Å	µ = 0.08 mm^−1
c = 12.1545 (4) Å	T = 295 K
β = 110.911 (4)°	Block, colourless
V = 1139.89 (6) Å^3	0.52 × 0.46 × 0.32 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini Mo) detector	2138 independent reflections
Graphite monochromator	1468 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm^-1	Rint = 0.027
ω scans	θmax = 25.6°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −15→15
Tmin = 0.96, Tmax = 0.98	k = −9→9
20946 measured reflections	l = −14→14

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0889P)^2 + 0.0575P] where P = (Fo^2 + 2Fc^2)/3
2138 reflections	(Δ/σ)max = 0.001
146 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.44050 (14)	0.7055 (2)	0.52718 (13)	0.0649 (4)
C2	0.42337 (16)	0.6054 (2)	0.60914 (16)	0.0826 (5)
H2	0.3509	0.559	0.5955	0.099*
C3	0.51407 (17)	0.5731 (2)	0.71233 (15)	0.0847 (6)
H3	0.503	0.5045	0.7686	0.102*
C4	0.61978 (16)	0.6415 (2)	0.73202 (15)	0.0809 (5)
H4	0.681	0.6201	0.8019	0.097*
C5	0.63602 (14)	0.7415 (2)	0.64933 (16)	0.0792 (5)
H5	0.7085	0.7882	0.6634	0.095*
C6	0.54637 (15)	0.7745 (2)	0.54505 (15)	0.0737 (5)
H6	0.5577	0.8419	0.4883	0.088*
C7	0.26747 (13)	0.84141 (18)	0.41132 (13)	0.0602 (4)
C8	0.17152 (12)	0.83643 (17)	0.29559 (12)	0.0558 (4)
C9	0.17601 (13)	0.74161 (18)	0.20301 (13)	0.0629 (4)
H9	0.2427	0.6822	0.2108	0.075*
C10	0.08196 (13)	0.73479 (19)	0.09922 (14)	0.0660 (4)
H10	0.0868	0.6716	0.0374	0.079*
C11	−0.01947 (13)	0.81929 (18)	0.08448 (13)	0.0633 (4)
C12	−0.02227 (14)	0.9156 (2)	0.17716 (15)	0.0718 (5)
H12	−0.0889	0.9754	0.1691	0.086*
C13	0.07132 (14)	0.92496 (18)	0.28101 (14)	0.0679 (4)
H13	0.0674	0.9911	0.3419	0.082*
C14	−0.12267 (15)	0.8048 (2)	−0.02748 (15)	0.0835 (5)
H14A	−0.1656	0.906	−0.042	0.125*	0.5
H14B	−0.1715	0.7167	−0.0203	0.125*	0.5
H14C	−0.097	0.7825	−0.0918	0.125*	0.5
H14D	−0.1924	0.8088	−0.0098	0.125*	0.5
H14E	−0.1192	0.7023	−0.0652	0.125*	0.5
H14F	−0.1224	0.8941	−0.0791	0.125*	0.5
O1	0.35063 (10)	0.72961 (15)	0.41782 (10)	0.0865 (4)
O2	0.27223 (9)	0.92969 (13)	0.49154 (9)	0.0758 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0612 (9)	0.0712 (10)	0.0534 (8)	0.0089 (8)	0.0095 (7)	−0.0108 (7)
C2	0.0734 (11)	0.0913 (12)	0.0790 (11)	−0.0181 (9)	0.0221 (9)	−0.0136 (10)
C3	0.1043 (15)	0.0767 (11)	0.0670 (11)	−0.0104 (10)	0.0230 (10)	0.0040 (8)
C4	0.0817 (12)	0.0714 (10)	0.0689 (11)	0.0066 (9)	0.0016 (9)	−0.0025 (8)
C5	0.0599 (10)	0.0815 (12)	0.0842 (12)	−0.0029 (8)	0.0110 (9)	−0.0022 (9)
C6	0.0729 (11)	0.0763 (11)	0.0705 (10)	0.0036 (9)	0.0238 (9)	0.0047 (8)
C7	0.0624 (9)	0.0576 (8)	0.0608 (9)	−0.0016 (7)	0.0222 (7)	−0.0014 (7)
C8	0.0562 (8)	0.0526 (8)	0.0581 (8)	−0.0029 (6)	0.0198 (7)	0.0001 (6)
C9	0.0572 (9)	0.0656 (9)	0.0629 (9)	0.0044 (7)	0.0178 (7)	−0.0038 (7)
C10	0.0642 (10)	0.0704 (10)	0.0597 (9)	−0.0018 (8)	0.0176 (8)	−0.0059 (7)
C11	0.0589 (9)	0.0602 (9)	0.0651 (9)	−0.0043 (7)	0.0153 (7)	0.0109 (7)
C12	0.0622 (10)	0.0683 (10)	0.0806 (11)	0.0143 (8)	0.0204 (8)	0.0094 (8)
C13	0.0733 (10)	0.0615 (9)	0.0697 (10)	0.0077 (8)	0.0264 (8)	−0.0012 (7)
C14	0.0669 (10)	0.0899 (12)	0.0778 (11)	−0.0072 (9)	0.0063 (9)	0.0131 (9)
O1	0.0739 (8)	0.1056 (9)	0.0623 (7)	0.0271 (7)	0.0024 (6)	−0.0195 (6)
O2	0.0821 (8)	0.0734 (7)	0.0660 (7)	0.0022 (6)	0.0193 (6)	−0.0148 (5)

Geometric parameters (Å, º)

C1—C2	1.361 (2)	C8—C13	1.387 (2)
C1—C6	1.366 (2)	C9—C10	1.377 (2)
C1—O1	1.4082 (18)	C9—H9	0.93
C2—C3	1.376 (2)	C10—C11	1.383 (2)
C2—H2	0.93	C10—H10	0.93
C3—C4	1.359 (2)	C11—C12	1.383 (2)
C3—H3	0.93	C11—C14	1.500 (2)
C4—C5	1.362 (2)	C12—C13	1.376 (2)
C4—H4	0.93	C12—H12	0.93
C5—C6	1.379 (2)	C13—H13	0.93
C5—H5	0.93	C14—H14A	0.96
C6—H6	0.93	C14—H14B	0.96
C7—O2	1.1954 (16)	C14—H14C	0.96
C7—O1	1.3524 (18)	C14—H14D	0.96
C7—C8	1.481 (2)	C14—H14E	0.96
C8—C9	1.381 (2)	C14—H14F	0.96
C2—C1—C6	121.27 (15)	C8—C9—H9	119.9
C2—C1—O1	119.90 (15)	C9—C10—C11	121.80 (14)
C6—C1—O1	118.65 (15)	C9—C10—H10	119.1
C1—C2—C3	119.54 (17)	C11—C10—H10	119.1
C1—C2—H2	120.2	C12—C11—C10	117.44 (14)
C3—C2—H2	120.2	C12—C11—C14	121.56 (15)
C4—C3—C2	120.02 (17)	C10—C11—C14	121.00 (15)
C4—C3—H3	120	C13—C12—C11	121.45 (15)
C2—C3—H3	120	C13—C12—H12	119.3
C3—C4—C5	119.96 (16)	C11—C12—H12	119.3
C3—C4—H4	120	C12—C13—C8	120.48 (15)
C5—C4—H4	120	C12—C13—H13	119.8
C4—C5—C6	120.86 (17)	C8—C13—H13	119.8
C4—C5—H5	119.6	C11—C14—H14A	109.5
C6—C5—H5	119.6	C11—C14—H14B	109.5
C1—C6—C5	118.34 (16)	H14A—C14—H14B	109.5
C1—C6—H6	120.8	C11—C14—H14C	109.5
C5—C6—H6	120.8	H14A—C14—H14C	109.5
O2—C7—O1	122.75 (13)	H14B—C14—H14C	109.5
O2—C7—C8	125.51 (14)	C11—C14—H14D	109.5
O1—C7—C8	111.72 (12)	C11—C14—H14E	109.5
C9—C8—C13	118.62 (14)	H14D—C14—H14E	109.5
C9—C8—C7	122.54 (13)	C11—C14—H14F	109.5
C13—C8—C7	118.79 (13)	H14D—C14—H14F	109.5
C10—C9—C8	120.18 (14)	H14E—C14—H14F	109.5
C10—C9—H9	119.9	C7—O1—C1	118.32 (11)
C6—C1—C2—C3	0.3 (3)	C7—C8—C9—C10	176.63 (14)
O1—C1—C2—C3	175.36 (15)	C8—C9—C10—C11	−0.9 (2)
C1—C2—C3—C4	0.2 (3)	C9—C10—C11—C12	1.8 (2)
C2—C3—C4—C5	−0.3 (3)	C9—C10—C11—C14	−177.47 (14)
C3—C4—C5—C6	−0.1 (3)	C10—C11—C12—C13	−1.2 (2)
C2—C1—C6—C5	−0.7 (3)	C14—C11—C12—C13	178.09 (15)
O1—C1—C6—C5	−175.82 (14)	C11—C12—C13—C8	−0.3 (2)
C4—C5—C6—C1	0.6 (3)	C9—C8—C13—C12	1.3 (2)
O2—C7—C8—C9	174.22 (14)	C7—C8—C13—C12	−176.12 (14)
O1—C7—C8—C9	−7.1 (2)	O2—C7—O1—C1	6.3 (2)
O2—C7—C8—C13	−8.5 (2)	C8—C7—O1—C1	−172.34 (13)
O1—C7—C8—C13	170.12 (13)	C2—C1—O1—C7	82.15 (19)
C13—C8—C9—C10	−0.6 (2)	C6—C1—O1—C7	−102.63 (18)