Ethyl [5-(4-hydroxy­phen­yl)-3-methyl­sulfanyl-1-benzofuran-2-yl]acetate

The title compound, C₁₉H₁₈O₄S, was prepared by the Lewis acid-catalysed reaction of 4,4′-biphenol with ethyl 4-chloro-4-(methyl­sulfan­yl)acetoacetate. The 1-benzofuran ring system is nearly planar. The crystal structure is stabilized by inter­molecular O—H...O hydrogen bonds and H₂C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.062
• wR factor = 0.186
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C17    -   C18     ..       7.18 su

Author Response: Explained in the comment.

Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.62 mm

Author Response: Used collemeter size is 0.80 mm.

PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.41 Ratio

Author Response: I think no problem.

PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.95 Ratio

Author Response: I think no problem.

PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C17

Author Response: Explained in the comment.

PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16

Author Response: Explained in the comment.

PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C17    -   C18    ...       1.37 Ang.

Author Response: Explained in the comment.

PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      74.00 A   3 

Author Response: : We can't found any high electron density residue on the D-maps. Electron density synthesis with coefficients Fo-Fc. Highest peak 0.88 at 0.0066 0.2794 0.3238[0.95 A from O4]. Deepest hole -0.64 at 0.0971 0.2679 0.2085[0.64 A from H18C].

Alert level G
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.

Ethyl [5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate

Crystal data

C19H18O4S	F(000) = 1440
Mr = 342.39	Dx = 1.267 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4386 reflections
a = 31.778 (2) Å	θ = 2.6–27.6°
b = 7.7645 (4) Å	µ = 0.20 mm^−1
c = 15.6227 (8) Å	T = 173 K
β = 111.330 (1)°	Block, colorless
V = 3590.7 (3) Å^3	0.62 × 0.60 × 0.54 mm
Z = 8

Data collection

Bruker SMART CCD diffractometer	3226 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 27.0°, θmin = 2.6°
Detector resolution: 10.00 pixels mm^-1	h = −39→40
φ and ω scans	k = −9→9
14687 measured reflections	l = −19→19
3896 independent 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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.186	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0903P)^2 + 6.5673P] where P = (Fo^2 + 2Fc^2)/3
3896 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.88 e Å^−3
1 restraint	Δρmin = −0.64 e Å^−3

Special details

Experimental. IR (KBr): 3459 (OH), 1717 (CO) cm^-1; ¹H NMR (CDCl₃): δ 1.28 (t, J = 7.20 Hz, 3H), 2.33 (s, 3H), 4.03 (s, 2H), 4.24 (q, J = 7.20 Hz, 2H), 4.79 (s, 1H), 6.82 (d, J = 8.56 Hz, 2H), 7.38 (d, J = 8.56 Hz, 2H), 7.43 (d, J = 1.68 Hz, 1H), 7.45 (s, 1H), 7.71 (d, J = 2.40 Hz, 1H); ¹³C NMR (CDCl₃): δ 14.1, 18.7, 32.9, 61.7, 111.5, 112.1, 115.5, 117.6, 124.1, 128.5, 129.7, 133.9, 136.6, 153.7, 153.9, 155.1, 169.2; MS: 342 [M⁺].

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
S	0.15437 (3)	0.27097 (9)	0.42618 (5)	0.0472 (2)
O1	0.43558 (8)	0.7388 (3)	0.82256 (16)	0.0617 (6)
H1	0.4423	0.7840	0.8733	0.093*
O2	0.10810 (7)	0.7080 (3)	0.48878 (14)	0.0466 (5)
O3	0.04456 (9)	0.3648 (5)	0.49968 (17)	0.0952 (11)
O4	−0.00554 (9)	0.3472 (5)	0.35956 (17)	0.0866 (10)
C1	0.38932 (10)	0.7317 (4)	0.78089 (19)	0.0429 (6)
C2	0.36049 (10)	0.7943 (4)	0.82301 (18)	0.0427 (6)
H2	0.3724	0.8410	0.8818	0.051*
C3	0.31417 (10)	0.7866 (3)	0.77706 (17)	0.0395 (6)
H3	0.2952	0.8284	0.8057	0.047*
C4	0.29508 (9)	0.7172 (3)	0.68817 (17)	0.0346 (5)
C5	0.32507 (9)	0.6528 (3)	0.64841 (17)	0.0377 (6)
H5	0.3135	0.6048	0.5899	0.045*
C6	0.37136 (10)	0.6590 (3)	0.69395 (19)	0.0421 (6)
H6	0.3905	0.6144	0.6663	0.051*
C7	0.24556 (9)	0.7166 (3)	0.63742 (17)	0.0355 (5)
C8	0.22453 (9)	0.5806 (3)	0.57806 (16)	0.0354 (5)
H8	0.2414	0.4881	0.5705	0.042*
C9	0.17810 (9)	0.5861 (3)	0.53077 (16)	0.0366 (5)
C10	0.15330 (10)	0.7258 (4)	0.54248 (18)	0.0409 (6)
C11	0.17266 (10)	0.8637 (4)	0.60009 (19)	0.0445 (6)
H11	0.1555	0.9562	0.6067	0.053*
C12	0.21880 (9)	0.8557 (3)	0.64696 (18)	0.0403 (6)
H12	0.2329	0.9454	0.6864	0.048*
C13	0.14527 (9)	0.4752 (3)	0.46449 (17)	0.0403 (6)
C14	0.10482 (10)	0.5548 (4)	0.44173 (18)	0.0446 (6)
C15	0.05878 (10)	0.5085 (4)	0.37706 (19)	0.0512 (7)
H15A	0.0614	0.4479	0.3249	0.061*
H15B	0.0418	0.6134	0.3542	0.061*
C16	0.03301 (10)	0.3979 (5)	0.4200 (2)	0.0567 (8)
C17	−0.03437 (19)	0.2319 (10)	0.3923 (3)	0.118 (2)
H17A	−0.0212	0.1176	0.4047	0.141*
H17B	−0.0363	0.2771	0.4487	0.141*
C18	−0.0765 (2)	0.2237 (8)	0.3256 (4)	0.111 (2)
H18A	−0.0954	0.1501	0.3457	0.166*
H18B	−0.0744	0.1781	0.2702	0.166*
H18C	−0.0894	0.3371	0.3140	0.166*
C19	0.18624 (12)	0.3266 (4)	0.3547 (2)	0.0565 (8)
H19A	0.1935	0.2237	0.3289	0.085*
H19B	0.2136	0.3843	0.3912	0.085*
H19C	0.1685	0.4014	0.3060	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0684 (5)	0.0305 (4)	0.0434 (4)	−0.0141 (3)	0.0209 (3)	−0.0042 (3)
O1	0.0487 (12)	0.0790 (17)	0.0538 (13)	0.0024 (11)	0.0145 (10)	−0.0162 (11)
O2	0.0463 (11)	0.0496 (12)	0.0437 (10)	−0.0040 (9)	0.0161 (8)	−0.0061 (9)
O3	0.0634 (15)	0.160 (3)	0.0487 (14)	−0.0417 (18)	0.0047 (12)	0.0267 (17)
O4	0.0694 (16)	0.126 (3)	0.0501 (13)	−0.0411 (17)	0.0044 (12)	0.0031 (15)
C1	0.0476 (15)	0.0393 (14)	0.0414 (14)	−0.0007 (11)	0.0156 (12)	−0.0002 (11)
C2	0.0550 (16)	0.0404 (14)	0.0318 (12)	−0.0034 (12)	0.0149 (11)	−0.0043 (11)
C3	0.0524 (15)	0.0356 (13)	0.0338 (12)	−0.0028 (11)	0.0197 (11)	−0.0049 (10)
C4	0.0498 (14)	0.0245 (11)	0.0324 (12)	−0.0047 (10)	0.0184 (11)	−0.0002 (9)
C5	0.0550 (15)	0.0282 (12)	0.0333 (12)	−0.0051 (10)	0.0201 (11)	−0.0037 (9)
C6	0.0542 (16)	0.0351 (13)	0.0425 (14)	−0.0004 (11)	0.0242 (12)	−0.0035 (11)
C7	0.0506 (14)	0.0288 (12)	0.0318 (11)	−0.0061 (10)	0.0206 (10)	−0.0012 (9)
C8	0.0505 (14)	0.0263 (11)	0.0323 (12)	−0.0035 (10)	0.0186 (10)	−0.0003 (9)
C9	0.0513 (15)	0.0300 (12)	0.0318 (12)	−0.0067 (10)	0.0189 (11)	−0.0002 (9)
C10	0.0470 (15)	0.0417 (14)	0.0370 (13)	−0.0043 (11)	0.0189 (11)	−0.0013 (11)
C11	0.0542 (16)	0.0385 (14)	0.0471 (15)	−0.0004 (12)	0.0258 (13)	−0.0090 (12)
C12	0.0521 (15)	0.0340 (13)	0.0401 (13)	−0.0065 (11)	0.0229 (12)	−0.0098 (10)
C13	0.0537 (16)	0.0355 (13)	0.0326 (12)	−0.0096 (11)	0.0169 (11)	−0.0010 (10)
C14	0.0531 (16)	0.0460 (15)	0.0356 (13)	−0.0102 (12)	0.0172 (12)	−0.0026 (11)
C15	0.0545 (17)	0.0577 (18)	0.0362 (13)	−0.0098 (14)	0.0104 (12)	−0.0001 (13)
C16	0.0436 (16)	0.073 (2)	0.0448 (16)	−0.0103 (15)	0.0057 (12)	0.0038 (15)
C17	0.092 (3)	0.190 (7)	0.065 (3)	−0.063 (4)	0.021 (2)	0.007 (3)
C18	0.121 (5)	0.122 (5)	0.103 (4)	−0.051 (4)	0.056 (4)	−0.029 (3)
C19	0.078 (2)	0.0403 (16)	0.0598 (18)	−0.0062 (15)	0.0358 (17)	−0.0029 (14)

Geometric parameters (Å, º)

S—C13	1.756 (3)	C8—C9	1.390 (4)
S—C19	1.812 (3)	C8—H8	0.9300
O1—C1	1.376 (4)	C9—C10	1.392 (4)
O1—H1	0.8200	C9—C13	1.455 (4)
O2—C10	1.382 (3)	C10—C11	1.390 (4)
O2—C14	1.382 (3)	C11—C12	1.382 (4)
O3—C16	1.191 (4)	C11—H11	0.9300
O4—C16	1.306 (4)	C12—H12	0.9300
O4—C17	1.498 (5)	C13—C14	1.352 (4)
C1—C6	1.387 (4)	C14—C15	1.488 (4)
C1—C2	1.395 (4)	C15—C16	1.502 (4)
C2—C3	1.384 (4)	C15—H15A	0.9700
C2—H2	0.9300	C15—H15B	0.9700
C3—C4	1.405 (3)	C17—C18	1.367 (7)
C3—H3	0.9300	C17—H17A	0.9700
C4—C5	1.405 (4)	C17—H17B	0.9700
C4—C7	1.482 (4)	C18—H18A	0.9600
C5—C6	1.383 (4)	C18—H18B	0.9600
C5—H5	0.9300	C18—H18C	0.9600
C6—H6	0.9300	C19—H19A	0.9600
C7—C8	1.404 (3)	C19—H19B	0.9600
C7—C12	1.416 (4)	C19—H19C	0.9600
C13—S—C19	101.13 (13)	C11—C12—C7	122.7 (2)
C1—O1—H1	109.5	C11—C12—H12	118.6
C10—O2—C14	105.6 (2)	C7—C12—H12	118.6
C16—O4—C17	117.6 (3)	C14—C13—C9	106.5 (2)
O1—C1—C6	117.9 (2)	C14—C13—S	125.6 (2)
O1—C1—C2	122.3 (3)	C9—C13—S	127.8 (2)
C6—C1—C2	119.8 (3)	C13—C14—O2	111.9 (2)
C3—C2—C1	119.8 (2)	C13—C14—C15	132.4 (3)
C3—C2—H2	120.1	O2—C14—C15	115.7 (3)
C1—C2—H2	120.1	C14—C15—C16	113.3 (2)
C2—C3—C4	121.6 (2)	C14—C15—H15A	108.9
C2—C3—H3	119.2	C16—C15—H15A	108.9
C4—C3—H3	119.2	C14—C15—H15B	108.9
C3—C4—C5	117.1 (2)	C16—C15—H15B	108.9
C3—C4—C7	121.5 (2)	H15A—C15—H15B	107.7
C5—C4—C7	121.4 (2)	O3—C16—O4	122.8 (3)
C6—C5—C4	121.7 (2)	O3—C16—C15	125.4 (3)
C6—C5—H5	119.1	O4—C16—C15	111.7 (3)
C4—C5—H5	119.1	C18—C17—O4	108.6 (4)
C5—C6—C1	120.0 (2)	C18—C17—H17A	110.0
C5—C6—H6	120.0	O4—C17—H17A	110.0
C1—C6—H6	120.0	C18—C17—H17B	110.0
C8—C7—C12	118.9 (2)	O4—C17—H17B	110.0
C8—C7—C4	120.9 (2)	H17A—C17—H17B	108.4
C12—C7—C4	120.2 (2)	C17—C18—H18A	109.5
C9—C8—C7	119.1 (2)	C17—C18—H18B	109.5
C9—C8—H8	120.4	H18A—C18—H18B	109.5
C7—C8—H8	120.4	C17—C18—H18C	109.5
C8—C9—C10	119.7 (2)	H18A—C18—H18C	109.5
C8—C9—C13	135.1 (2)	H18B—C18—H18C	109.5
C10—C9—C13	105.1 (2)	S—C19—H19A	109.5
O2—C10—C11	126.0 (3)	S—C19—H19B	109.5
O2—C10—C9	110.8 (2)	H19A—C19—H19B	109.5
C11—C10—C9	123.2 (3)	S—C19—H19C	109.5
C12—C11—C10	116.3 (2)	H19A—C19—H19C	109.5
C12—C11—H11	121.9	H19B—C19—H19C	109.5
C10—C11—H11	121.9
O1—C1—C2—C3	178.8 (3)	O2—C10—C11—C12	−179.4 (2)
C6—C1—C2—C3	−1.3 (4)	C9—C10—C11—C12	−0.4 (4)
C1—C2—C3—C4	−0.2 (4)	C10—C11—C12—C7	0.4 (4)
C2—C3—C4—C5	1.1 (4)	C8—C7—C12—C11	−0.1 (4)
C2—C3—C4—C7	−177.1 (2)	C4—C7—C12—C11	178.8 (2)
C3—C4—C5—C6	−0.8 (4)	C8—C9—C13—C14	−178.2 (3)
C7—C4—C5—C6	177.5 (2)	C10—C9—C13—C14	0.5 (3)
C4—C5—C6—C1	−0.6 (4)	C8—C9—C13—S	5.9 (4)
O1—C1—C6—C5	−178.4 (2)	C10—C9—C13—S	−175.4 (2)
C2—C1—C6—C5	1.6 (4)	C19—S—C13—C14	112.7 (3)
C3—C4—C7—C8	−145.6 (2)	C19—S—C13—C9	−72.2 (3)
C5—C4—C7—C8	36.3 (3)	C9—C13—C14—O2	−1.0 (3)
C3—C4—C7—C12	35.6 (3)	S—C13—C14—O2	175.00 (18)
C5—C4—C7—C12	−142.6 (2)	C9—C13—C14—C15	179.0 (3)
C12—C7—C8—C9	−0.3 (3)	S—C13—C14—C15	−5.0 (5)
C4—C7—C8—C9	−179.1 (2)	C10—O2—C14—C13	1.1 (3)
C7—C8—C9—C10	0.3 (3)	C10—O2—C14—C15	−178.9 (2)
C7—C8—C9—C13	178.9 (3)	C13—C14—C15—C16	87.9 (4)
C14—O2—C10—C11	178.4 (3)	O2—C14—C15—C16	−92.1 (3)
C14—O2—C10—C9	−0.8 (3)	C17—O4—C16—O3	−4.6 (7)
C8—C9—C10—O2	179.1 (2)	C17—O4—C16—C15	178.5 (4)
C13—C9—C10—O2	0.2 (3)	C14—C15—C16—O3	8.8 (6)
C8—C9—C10—C11	0.0 (4)	C14—C15—C16—O4	−174.4 (3)
C13—C9—C10—C11	−179.0 (3)	C16—O4—C17—C18	167.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.82	1.98	2.792 (3)	172

Symmetry code: (i) −x+1/2, y+1/2, −z+3/2.