Ethyl 2-(4-benzoyl-2,5-dimethyl-phen-oxy)acetate.

The title compound, C(19)H(20)O(4), was synthesized via a Fries rearrangement of hydr-oxy benzophenone. The dihedral angle between the least-squares planes of the two benzene rings is 69.04 (11)°. The mol-ecular structure displays an intra-molecular non-classical C-H⋯O hydrogen bond.

Related literature

hydr­oxy benzophenones may obtained from natural products, see: Henry et al. (1999 ▶); Vidya et al. (2003 ▶); Cuesta-Rubio et al. (2002 ▶) and by synthetic methods, see: Hsieh et al. (2003 ▶); Revesz et al. (2004 ▶); Schlitzer et al. (2002 ▶). For their biological activity, see: Jiri et al. (1991 ▶); Palomer et al. (2000 ▶, 2002 ▶); Palaska et al. (2002 ▶); Khanum et al. (2004a ▶,b ▶). Benzophenone analogues with nitro substituents exhibit significant in vivo antitumor activity and they have been reported to show activity as immunomodulators, see: Leonard (1997 ▶). Nitro benzophenone derivatives show strong cytotoxic activity while the corresponding aminobenzophenone derivatives show weak activity, see: Kumazawa et al. (1997 ▶). For the antimicobial activity of benzophenone derivatives, see: Selvi et al. (2003 ▶).

Experimental

Crystal data

C19H20O4

M = 312.35

Triclinic,

a = 8.148 (4) Å

b = 8.635 (4) Å

c = 13.029 (7) Å

α = 84.054 (8)°

β = 81.176 (8)°

γ = 66.559 (7)°

V = 830.2 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 295 K

0.21 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.982, T max = 0.991

8847 measured reflections

3391 independent reflections

2630 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.173

S = 1.05

3391 reflections

209 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1999 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809043190/rk2174sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043190/rk2174Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C19H20O4	Z = 2
Mr = 312.35	F(000) = 332
Triclinic, P1	Dx = 1.250 Mg m−3
Hall symbol: -P 1	Melting point: 329 K
a = 8.148 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.635 (4) Å	Cell parameters from 3391 reflections
c = 13.029 (7) Å	θ = 1.6–26.4°
α = 84.054 (8)°	µ = 0.09 mm−1
β = 81.176 (8)°	T = 295 K
γ = 66.559 (7)°	Plate, colourless
V = 830.2 (7) Å3	0.21 × 0.20 × 0.10 mm

Bruker SMART CCD diffractometer	3391 independent reflections
Radiation source: fine-focus sealed tube	2630 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω and φ scans	θmax = 26.4°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
Tmin = 0.982, Tmax = 0.991	k = −10→10
8847 measured reflections	l = −16→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0848P)2 + 0.2822P] where P = (Fo2 + 2Fc2)/3
3391 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

	x	y	z	Uiso*/Ueq
O1	0.4354 (3)	0.82563 (19)	0.84149 (12)	0.0691 (5)
O2	0.14909 (19)	1.14174 (17)	0.41431 (11)	0.0546 (4)
O3	0.1127 (2)	1.37122 (19)	0.24885 (14)	0.0715 (5)
O4	0.1339 (2)	1.16785 (19)	0.14867 (12)	0.0662 (5)
C1	0.4303 (3)	0.5733 (2)	0.79154 (15)	0.0462 (5)
C2	0.5409 (3)	0.4695 (3)	0.86317 (18)	0.0642 (6)
H2	0.6073	0.5104	0.8967	0.077*
C3	0.5525 (4)	0.3051 (3)	0.8849 (2)	0.0760 (7)
H3	0.6276	0.2356	0.9324	0.091*
C4	0.4536 (4)	0.2448 (3)	0.8364 (2)	0.0731 (7)
H4	0.4611	0.1347	0.8516	0.088*
C5	0.3435 (4)	0.3461 (3)	0.7654 (2)	0.0667 (6)
H5	0.2761	0.3047	0.7331	0.080*
C6	0.3327 (3)	0.5103 (3)	0.74180 (17)	0.0537 (5)
H6	0.2600	0.5780	0.6927	0.064*
C7	0.4101 (3)	0.7530 (2)	0.77353 (15)	0.0476 (5)
C8	0.3509 (2)	0.8461 (2)	0.67388 (15)	0.0425 (4)
C9	0.4344 (2)	0.7866 (2)	0.57555 (14)	0.0413 (4)
C10	0.3660 (2)	0.8849 (2)	0.48841 (14)	0.0432 (4)
H10	0.4193	0.8466	0.4225	0.052*
C11	0.2199 (2)	1.0389 (2)	0.49763 (15)	0.0437 (4)
C12	0.1369 (2)	1.1014 (2)	0.59520 (16)	0.0449 (4)
C13	0.2055 (3)	1.0032 (2)	0.68133 (15)	0.0457 (4)
H13	0.1531	1.0430	0.7470	0.055*
C14	0.6014 (3)	0.6268 (2)	0.56025 (16)	0.0490 (5)
H14A	0.6369	0.6093	0.4872	0.074*
H14B	0.5765	0.5326	0.5935	0.074*
H14C	0.6970	0.6368	0.5902	0.074*
C15	−0.0212 (3)	1.2694 (2)	0.60437 (19)	0.0596 (6)
H15A	−0.0484	1.3174	0.5362	0.089*
H15B	0.0086	1.3446	0.6403	0.089*
H15C	−0.1241	1.2532	0.6425	0.089*
C16	0.2201 (3)	1.0816 (3)	0.31397 (16)	0.0523 (5)
H16A	0.1847	0.9904	0.3029	0.063*
H16B	0.3507	1.0388	0.3062	0.063*
C17	0.1474 (3)	1.2266 (3)	0.23580 (17)	0.0519 (5)
C18	0.0828 (4)	1.2910 (3)	0.06180 (19)	0.0752 (7)
H18A	0.1834	1.3212	0.0322	0.090*
H18B	−0.0173	1.3927	0.0856	0.090*
C19	0.0308 (5)	1.2153 (4)	−0.0163 (2)	0.0967 (10)
H19A	−0.0037	1.2947	−0.0742	0.145*
H19B	−0.0689	1.1860	0.0136	0.145*
H19C	0.1310	1.1153	−0.0398	0.145*

	U11	U22	U33	U12	U13	U23
O1	0.1070 (13)	0.0530 (9)	0.0549 (9)	−0.0327 (9)	−0.0290 (9)	−0.0015 (7)
O2	0.0530 (8)	0.0449 (8)	0.0511 (8)	−0.0028 (6)	−0.0123 (6)	0.0043 (6)
O3	0.0911 (12)	0.0458 (9)	0.0748 (11)	−0.0189 (8)	−0.0288 (9)	0.0057 (8)
O4	0.0907 (12)	0.0566 (9)	0.0522 (9)	−0.0281 (8)	−0.0194 (8)	0.0076 (7)
C1	0.0514 (11)	0.0412 (10)	0.0429 (10)	−0.0149 (8)	−0.0053 (8)	−0.0019 (8)
C2	0.0795 (16)	0.0530 (12)	0.0612 (13)	−0.0237 (11)	−0.0233 (12)	0.0062 (10)
C3	0.0950 (19)	0.0504 (13)	0.0734 (16)	−0.0189 (13)	−0.0212 (14)	0.0142 (11)
C4	0.0944 (19)	0.0442 (12)	0.0723 (16)	−0.0254 (12)	0.0105 (14)	−0.0030 (11)
C5	0.0800 (16)	0.0592 (13)	0.0688 (15)	−0.0373 (12)	0.0026 (12)	−0.0127 (11)
C6	0.0568 (12)	0.0522 (11)	0.0534 (12)	−0.0226 (10)	−0.0058 (9)	−0.0036 (9)
C7	0.0524 (11)	0.0426 (10)	0.0468 (11)	−0.0158 (9)	−0.0092 (9)	−0.0043 (8)
C8	0.0451 (10)	0.0354 (9)	0.0472 (10)	−0.0142 (8)	−0.0103 (8)	−0.0026 (7)
C9	0.0379 (9)	0.0346 (9)	0.0494 (10)	−0.0105 (7)	−0.0088 (8)	−0.0029 (7)
C10	0.0412 (10)	0.0391 (9)	0.0437 (10)	−0.0088 (8)	−0.0064 (8)	−0.0038 (8)
C11	0.0412 (9)	0.0384 (9)	0.0489 (11)	−0.0118 (8)	−0.0113 (8)	0.0027 (8)
C12	0.0402 (9)	0.0350 (9)	0.0552 (11)	−0.0092 (8)	−0.0066 (8)	−0.0044 (8)
C13	0.0491 (10)	0.0374 (9)	0.0473 (10)	−0.0132 (8)	−0.0018 (8)	−0.0084 (8)
C14	0.0439 (10)	0.0415 (10)	0.0532 (11)	−0.0060 (8)	−0.0095 (8)	−0.0038 (8)
C15	0.0524 (12)	0.0397 (10)	0.0711 (14)	−0.0017 (9)	−0.0052 (10)	−0.0056 (10)
C16	0.0562 (12)	0.0454 (10)	0.0509 (12)	−0.0142 (9)	−0.0131 (9)	0.0035 (9)
C17	0.0492 (11)	0.0502 (11)	0.0550 (12)	−0.0166 (9)	−0.0143 (9)	0.0045 (9)
C18	0.103 (2)	0.0683 (15)	0.0531 (13)	−0.0326 (15)	−0.0191 (13)	0.0145 (11)
C19	0.130 (3)	0.108 (2)	0.0701 (18)	−0.061 (2)	−0.0400 (18)	0.0194 (16)

O1—C7	1.222 (2)	C9—C14	1.508 (2)
O2—C11	1.373 (2)	C10—C11	1.389 (3)
O2—C16	1.408 (3)	C10—H10	0.9300
O3—C17	1.190 (3)	C11—C12	1.397 (3)
O4—C17	1.327 (3)	C12—C13	1.382 (3)
O4—C18	1.459 (3)	C12—C15	1.510 (3)
C1—C6	1.387 (3)	C13—H13	0.9300
C1—C2	1.389 (3)	C14—H14A	0.9600
C1—C7	1.491 (3)	C14—H14B	0.9600
C2—C3	1.387 (3)	C14—H14C	0.9600
C2—H2	0.9300	C15—H15A	0.9600
C3—C4	1.370 (4)	C15—H15B	0.9600
C3—H3	0.9300	C15—H15C	0.9600
C4—C5	1.375 (4)	C16—C17	1.512 (3)
C4—H4	0.9300	C16—H16A	0.9700
C5—C6	1.390 (3)	C16—H16B	0.9700
C5—H5	0.9300	C18—C19	1.461 (4)
C6—H6	0.9300	C18—H18A	0.9700
C7—C8	1.494 (3)	C18—H18B	0.9700
C8—C9	1.400 (3)	C19—H19A	0.9600
C8—C13	1.402 (3)	C19—H19B	0.9600
C9—C10	1.392 (3)	C19—H19C	0.9600
C11—O2—C16	117.92 (15)	C11—C12—C15	120.57 (18)
C17—O4—C18	116.19 (18)	C12—C13—C8	122.77 (18)
C6—C1—C2	119.25 (19)	C12—C13—H13	118.6
C6—C1—C7	120.90 (18)	C8—C13—H13	118.6
C2—C1—C7	119.76 (18)	C9—C14—H14A	109.5
C3—C2—C1	120.2 (2)	C9—C14—H14B	109.5
C3—C2—H2	119.9	H14A—C14—H14B	109.5
C1—C2—H2	119.9	C9—C14—H14C	109.5
C4—C3—C2	120.1 (2)	H14A—C14—H14C	109.5
C4—C3—H3	119.9	H14B—C14—H14C	109.5
C2—C3—H3	119.9	C12—C15—H15A	109.5
C3—C4—C5	120.3 (2)	C12—C15—H15B	109.5
C3—C4—H4	119.8	H15A—C15—H15B	109.5
C5—C4—H4	119.8	C12—C15—H15C	109.5
C4—C5—C6	120.1 (2)	H15A—C15—H15C	109.5
C4—C5—H5	119.9	H15B—C15—H15C	109.5
C6—C5—H5	119.9	O2—C16—C17	108.12 (16)
C1—C6—C5	120.0 (2)	O2—C16—H16A	110.1
C1—C6—H6	120.0	C17—C16—H16A	110.1
C5—C6—H6	120.0	O2—C16—H16B	110.1
O1—C7—C1	120.15 (18)	C17—C16—H16B	110.1
O1—C7—C8	120.08 (17)	H16A—C16—H16B	108.4
C1—C7—C8	119.71 (16)	O3—C17—O4	124.87 (19)
C9—C8—C13	119.31 (17)	O3—C17—C16	125.4 (2)
C9—C8—C7	123.67 (16)	O4—C17—C16	109.72 (18)
C13—C8—C7	117.01 (17)	O4—C18—C19	108.2 (2)
C10—C9—C8	118.21 (16)	O4—C18—H18A	110.1
C10—C9—C14	118.84 (17)	C19—C18—H18A	110.1
C8—C9—C14	122.83 (16)	O4—C18—H18B	110.1
C11—C10—C9	121.49 (17)	C19—C18—H18B	110.1
C11—C10—H10	119.3	H18A—C18—H18B	108.4
C9—C10—H10	119.3	C18—C19—H19A	109.5
O2—C11—C10	123.79 (17)	C18—C19—H19B	109.5
O2—C11—C12	115.21 (16)	H19A—C19—H19B	109.5
C10—C11—C12	120.99 (17)	C18—C19—H19C	109.5
C13—C12—C11	117.21 (16)	H19A—C19—H19C	109.5
C13—C12—C15	122.22 (18)	H19B—C19—H19C	109.5
C6—C1—C2—C3	−0.3 (4)	C8—C9—C10—C11	0.6 (3)
C7—C1—C2—C3	176.3 (2)	C14—C9—C10—C11	−175.62 (17)
C1—C2—C3—C4	−0.6 (4)	C16—O2—C11—C10	4.9 (3)
C2—C3—C4—C5	0.5 (4)	C16—O2—C11—C12	−176.40 (17)
C3—C4—C5—C6	0.4 (4)	C9—C10—C11—O2	179.02 (17)
C2—C1—C6—C5	1.3 (3)	C9—C10—C11—C12	0.4 (3)
C7—C1—C6—C5	−175.3 (2)	O2—C11—C12—C13	−179.07 (16)
C4—C5—C6—C1	−1.3 (3)	C10—C11—C12—C13	−0.4 (3)
C6—C1—C7—O1	151.5 (2)	O2—C11—C12—C15	1.0 (3)
C2—C1—C7—O1	−25.1 (3)	C10—C11—C12—C15	179.66 (18)
C6—C1—C7—C8	−25.8 (3)	C11—C12—C13—C8	−0.7 (3)
C2—C1—C7—C8	157.6 (2)	C15—C12—C13—C8	179.29 (18)
O1—C7—C8—C9	130.0 (2)	C9—C8—C13—C12	1.7 (3)
C1—C7—C8—C9	−52.7 (3)	C7—C8—C13—C12	−179.52 (17)
O1—C7—C8—C13	−48.7 (3)	C11—O2—C16—C17	−169.54 (16)
C1—C7—C8—C13	128.6 (2)	C18—O4—C17—O3	3.8 (3)
C13—C8—C9—C10	−1.6 (3)	C18—O4—C17—C16	−174.0 (2)
C7—C8—C9—C10	179.72 (16)	O2—C16—C17—O3	32.4 (3)
C13—C8—C9—C14	174.45 (17)	O2—C16—C17—O4	−149.82 (18)
C7—C8—C9—C14	−4.3 (3)	C17—O4—C18—C19	−165.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O2	0.96	2.28	2.751 (3)	110

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯O2	0.96	2.28	2.751 (3)	110