2-[1-(Methyl­sulfan­yl)naphtho[2,1-b]furan-2-yl]acetic acid

Choi, H.D.; Seo, P.J.; Son, B.W.; Lee, U.

doi:10.1107/S1600536808000901

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o453

doi:10.1107/S1600536808000901

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2-[1-(Methylsulfanyl)naphtho[2,1-b]furan-2-yl]acetic acid

Hong Dae Choi,^a Pil Ja Seo,^a Byeng Wha Son ^b and Uk Lee ^b ^*

^aDepartment of Chemistry, Dongeui University, San 24 Kaya-dong Busanjin-gu, Busan 614-714, Republic of Korea, and ^bDepartment of Chemistry, Pukyong National University, 599-1 Daeyeon 3-dong, Nam-gu, Busan 608-737, Republic of Korea
^*Correspondence e-mail: uklee@pknu.ac.kr

(Received 6 January 2008; accepted 10 January 2008; online 16 January 2008)

The title compound, C₁₅H₁₂O₃S, was prepared by alkaline hydrolysis of ethyl 2-{1-(methylsulfanyl)naphtho[2,1-b]furan-2-yl}acetate. The crystal structure is stabilized by CH₂—H⋯π interactions between the methyl H atoms of the methylsulfanyl substituent and the central benzene ring of the naphthofuran system, and by inversion-related intermolecular O—H⋯O hydrogen bonds between the carboxyl groups.

Related literature

For the crystal structures of similar 1-(methylsulfanyl)naphtho[2,1-b]furan compounds, see: Choi et al. (2006 , 2007 ).

Experimental

Crystal data

C₁₅H₁₂O₃S
M_r = 272.32
Monoclinic, P 2₁ /n
a = 4.989 (2) Å
b = 14.265 (5) Å
c = 18.344 (7) Å
β = 90.18 (2)°
V = 1305.5 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 (2) K
0.45 × 0.28 × 0.09 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
8459 measured reflections
2209 independent reflections
1130 reflections with I > 2σ(I)
R_int = 0.115

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.224
S = 1.24
2209 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 1.09 e Å⁻³
Δρ_min = −1.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2/C3/C8–C11 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.82	1.91	2.711 (4)	167
C15—H15B⋯Cgⁱⁱ	0.96	3.03	3.949 (3)	161
Symmetry codes: (i) -x+2, -y+1, -z; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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, 1997 ) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000901/rk2074sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000901/rk2074Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies on the synthesis and structure of 1-(methylsulfanyl)naphtho[2,1-b]furan derivatives, we have recently described 7-bromo-1-methylsulfanyl-2-phenylnaphtho[2,1-b]furan (Choi et al., 2006) and 2-(4-bromophenyl)-1-(methylsulfanyl)naphtho[2,1-b]furan (Choi et al., 2007). Herein we report the molecular and crystal structure of the title compound, 2-{1-(methylsulfanyl)naphtho[2,1-b]furan-2-yl}acetic acid (Fig. 1).

The naphthofuran unit is essentially planar, with a mean deviation of 0.017Å from the least-squares plane defined by the thirteen constituent atoms. The crystal packing (Fig. 2) is stabilized by CH₂—H···π interactions, with a C15—H15B···Cg separation of 3.03Å (Cg is the centroid of the C2/C3/C8/C9/C10/C11 benzene ring; symmetry code as in Fig. 2). Classical inversion- related O3–H3···O2ⁱ hydrogen bonds link the carboxyl groups of adjacent molecules (Table and Fig. 2).

Related literature top

For the crystal structures of similar 1-(methylsulfanyl)naphtho[2,1-b]furan compounds, see: Choi et al. (2006, 2007).

Experimental top

Ethyl 2-{1-(methylsulfanyl)naphtho[2,1-b]furan-2-yl}acetate (600 mg, 2.0 mmol) was added to a solution of potassium hydroxide (561 mg, 10.0 mmol) in water (20 ml) and methanol (20 ml). The mixture was refluxed for 4 h and then cooled. Water was added, and the solution was washed with chloroform. The aqueous layer was acidified to pH 1 with concentrated hydrochloric acid and then extracted with chloroform, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was purified by column chromatography (hexane/ethyl-acetate, 1:1 v/v) to afford the title compound as a colourless solid [yield 82%, m.p. 436–437 K; R_f = 0.62 (hexane/ethyl-acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of the title compound in diisopropyl ether at room temperature.

Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 2.39 (s, 3H), 4.17 (s, 2H), 7.49–7.54 (m, 1H), 7.60–7.67 (m, 2H), 7.74 (d, J = 9.16 Hz, 1H), 7.95 (d, J = 7.68 Hz, 1H), 9.18 (d, J = 8.44 Hz, 1H), 11.02 (s, 1H); EI—MS 272 [M⁺].

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoides are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. The C–H···π interaction and O–H···O hydrogen bond (dotted lines) in the title compound. Cg denotes ring centroids. [Symmetry code: (i) -x + 2, -y + 1, -z; (ii) -x + 3/2, y + 1/2, -z + 1/2; (iii) -x + 3/2, y - 1/2, -z + 1/2.]

2-{1-(Methylsulfanyl)naphtho[2,1-b]furan-2-yl}acetic acid top

Crystal data top

C₁₅H₁₂O₃S	F(000) = 568
M_r = 272.32	D_x = 1.385 Mg m⁻³
Monoclinic, P2₁/n	Melting point = 436–437 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 4.989 (2) Å	Cell parameters from 3886 reflections
b = 14.265 (5) Å	θ = 2.2–27.9°
c = 18.344 (7) Å	µ = 0.25 mm⁻¹
β = 90.18 (2)°	T = 296 K
V = 1305.5 (9) Å³	Plate, silver
Z = 4	0.45 × 0.28 × 0.09 mm

Data collection top

Bruker SMART CCD diffractometer	1130 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.115
Graphite monochromator	θ_max = 25.5°, θ_min = 1.8°
Detector resolution: 10.0 pixels mm^-1	h = −6→4
ϕ and ω scans	k = −17→17
8459 measured reflections	l = −22→21
2209 independent reflections

Refinement top

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.224	H-atom parameters constrained
S = 1.24	w = 1/[σ²(F_o²) + (0.1148P)²] where P = (F_o² + 2F_c²)/3
2209 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 1.09 e Å⁻³
0 restraints	Δρ_min = −1.45 e Å⁻³

Crystal data top

C₁₅H₁₂O₃S	V = 1305.5 (9) Å³
M_r = 272.32	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.989 (2) Å	µ = 0.25 mm⁻¹
b = 14.265 (5) Å	T = 296 K
c = 18.344 (7) Å	0.45 × 0.28 × 0.09 mm
β = 90.18 (2)°

Data collection top

Bruker SMART CCD diffractometer	1130 reflections with I > 2σ(I)
8459 measured reflections	R_int = 0.115
2209 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.224	H-atom parameters constrained
S = 1.24	Δρ_max = 1.09 e Å⁻³
2209 reflections	Δρ_min = −1.45 e Å⁻³
174 parameters

Special details top

Geometry. The s.u.'s (except the s.u.'s 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 > 2σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
S	0.7770 (3)	0.81307 (6)	0.19046 (5)	0.0475 (5)
O1	1.1260 (7)	0.57778 (15)	0.25355 (14)	0.0476 (9)
O2	0.8997 (7)	0.5410 (2)	0.08670 (16)	0.0591 (9)
O3	1.2812 (7)	0.5715 (2)	0.02196 (17)	0.0637 (10)
H3	1.2206	0.5315	−0.0056	0.096*
C1	0.8881 (9)	0.7104 (2)	0.23497 (18)	0.0371 (10)
C2	0.8115 (10)	0.6749 (2)	0.30727 (18)	0.0378 (11)
C3	0.6288 (10)	0.7029 (2)	0.36497 (19)	0.0417 (11)
C4	0.4543 (10)	0.7812 (3)	0.3628 (2)	0.0487 (12)
H4	0.4531	0.8190	0.3215	0.058*
C5	0.2867 (13)	0.8034 (3)	0.4195 (3)	0.0629 (15)
H5	0.1742	0.8551	0.4156	0.076*
C6	0.2828 (11)	0.7483 (3)	0.4842 (2)	0.0604 (13)
H6	0.1703	0.7641	0.5226	0.073*
C7	0.4471 (13)	0.6718 (3)	0.4889 (2)	0.0589 (16)
H7	0.4450	0.6353	0.5310	0.071*
C8	0.6247 (11)	0.6465 (2)	0.4295 (2)	0.0459 (12)
C9	0.7927 (11)	0.5650 (2)	0.4337 (2)	0.0529 (13)
H9	0.7865	0.5284	0.4757	0.063*
C10	0.9638 (12)	0.5385 (2)	0.3780 (2)	0.0520 (13)
H10	1.0721	0.4857	0.3820	0.062*
C11	0.9664 (10)	0.5950 (2)	0.31502 (19)	0.0402 (10)
C12	1.0731 (10)	0.6499 (2)	0.20589 (19)	0.0403 (11)
C13	1.2273 (9)	0.6483 (2)	0.1351 (2)	0.0457 (12)
H13A	1.4123	0.6325	0.1458	0.055*
H13B	1.2257	0.7110	0.1146	0.055*
C14	1.1236 (10)	0.5807 (2)	0.0778 (2)	0.0423 (11)
C15	0.9473 (11)	0.9017 (2)	0.2426 (3)	0.0734 (17)
H15A	0.8677	0.9062	0.2900	0.110*
H15B	0.9321	0.9609	0.2181	0.110*
H15C	1.1331	0.8853	0.2475	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0597 (9)	0.0476 (5)	0.0353 (6)	0.0031 (6)	−0.0090 (7)	0.0046 (3)
O1	0.0544 (19)	0.0403 (10)	0.0479 (15)	0.0044 (16)	−0.011 (2)	−0.0052 (10)
O2	0.0561 (19)	0.0729 (17)	0.0483 (17)	−0.019 (2)	0.002 (2)	−0.0139 (14)
O3	0.058 (2)	0.0800 (19)	0.0536 (18)	−0.010 (2)	0.000 (2)	−0.0234 (15)
C1	0.041 (2)	0.0385 (13)	0.0316 (16)	−0.001 (2)	−0.005 (2)	−0.0046 (12)
C2	0.041 (3)	0.0375 (14)	0.0344 (19)	−0.004 (2)	−0.009 (3)	−0.0031 (12)
C3	0.046 (3)	0.0429 (14)	0.0355 (18)	−0.009 (2)	−0.012 (3)	−0.0047 (13)
C4	0.048 (3)	0.0574 (18)	0.041 (2)	0.006 (3)	−0.008 (3)	−0.0054 (15)
C5	0.059 (3)	0.069 (2)	0.062 (3)	0.008 (3)	−0.015 (4)	−0.015 (2)
C6	0.053 (3)	0.079 (3)	0.049 (2)	−0.006 (4)	0.008 (3)	−0.019 (2)
C7	0.079 (4)	0.065 (2)	0.0334 (19)	−0.026 (3)	0.006 (3)	−0.0025 (15)
C8	0.052 (3)	0.0489 (16)	0.0368 (18)	−0.015 (2)	−0.008 (3)	−0.0018 (13)
C9	0.072 (4)	0.0483 (16)	0.0379 (19)	−0.008 (3)	−0.012 (3)	0.0079 (13)
C10	0.068 (3)	0.0392 (14)	0.049 (2)	0.003 (2)	−0.016 (3)	0.0025 (14)
C11	0.044 (2)	0.0384 (13)	0.0385 (18)	0.002 (2)	−0.006 (3)	−0.0056 (13)
C12	0.044 (3)	0.0403 (14)	0.0361 (18)	−0.006 (2)	−0.005 (3)	−0.0047 (12)
C13	0.044 (3)	0.0508 (17)	0.042 (2)	−0.008 (2)	0.003 (3)	−0.0109 (14)
C14	0.045 (3)	0.0474 (16)	0.0343 (18)	0.004 (2)	0.000 (3)	−0.0064 (14)
C15	0.082 (4)	0.0414 (16)	0.096 (3)	−0.006 (3)	−0.040 (4)	0.0067 (18)

Geometric parameters (Å, º) top

S—C1	1.766 (3)	C6—C7	1.368 (7)
S—C15	1.797 (4)	C6—H6	0.9300
O1—C12	1.375 (4)	C7—C8	1.453 (7)
O1—C11	1.404 (5)	C7—H7	0.9300
O2—C14	1.263 (5)	C8—C9	1.435 (6)
O3—C14	1.300 (5)	C9—C10	1.386 (7)
O3—H3	0.8200	C9—H9	0.9300
C1—C12	1.372 (6)	C10—C11	1.410 (5)
C1—C2	1.471 (5)	C10—H10	0.9300
C2—C11	1.384 (5)	C12—C13	1.512 (6)
C2—C3	1.455 (6)	C13—C14	1.516 (4)
C3—C4	1.417 (6)	C13—H13A	0.9700
C3—C8	1.431 (5)	C13—H13B	0.9700
C4—C5	1.373 (7)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.423 (7)	C15—H15C	0.9600
C5—H5	0.9300

C1—S—C15	100.99 (18)	C10—C9—C8	122.8 (3)
C12—O1—C11	105.7 (3)	C10—C9—H9	118.6
C14—O3—H3	109.5	C8—C9—H9	118.6
C12—C1—C2	108.2 (3)	C9—C10—C11	117.1 (4)
C12—C1—S	123.5 (3)	C9—C10—H10	121.4
C2—C1—S	128.3 (3)	C11—C10—H10	121.4
C11—C2—C3	120.1 (3)	C2—C11—O1	112.3 (3)
C11—C2—C1	103.2 (4)	C2—C11—C10	123.3 (4)
C3—C2—C1	136.7 (3)	O1—C11—C10	124.4 (4)
C4—C3—C8	117.1 (4)	C1—C12—O1	110.6 (4)
C4—C3—C2	125.6 (3)	C1—C12—C13	133.5 (3)
C8—C3—C2	117.3 (4)	O1—C12—C13	115.9 (3)
C5—C4—C3	122.4 (4)	C12—C13—C14	115.6 (4)
C5—C4—H4	118.8	C12—C13—H13A	108.4
C3—C4—H4	118.8	C14—C13—H13A	108.4
C4—C5—C6	121.0 (5)	C12—C13—H13B	108.4
C4—C5—H5	119.5	C14—C13—H13B	108.4
C6—C5—H5	119.5	H13A—C13—H13B	107.4
C7—C6—C5	118.9 (5)	O2—C14—O3	126.5 (3)
C7—C6—H6	120.5	O2—C14—C13	119.7 (4)
C5—C6—H6	120.5	O3—C14—C13	113.8 (4)
C6—C7—C8	121.2 (4)	S—C15—H15A	109.5
C6—C7—H7	119.4	S—C15—H15B	109.5
C8—C7—H7	119.4	H15A—C15—H15B	109.5
C3—C8—C9	119.4 (4)	S—C15—H15C	109.5
C3—C8—C7	119.4 (4)	H15A—C15—H15C	109.5
C9—C8—C7	121.2 (4)	H15B—C15—H15C	109.5

C15—S—C1—C12	−106.1 (4)	C3—C8—C9—C10	0.9 (6)
C15—S—C1—C2	72.4 (4)	C7—C8—C9—C10	179.8 (4)
C12—C1—C2—C11	1.0 (4)	C8—C9—C10—C11	−0.5 (6)
S—C1—C2—C11	−177.7 (3)	C3—C2—C11—O1	178.7 (3)
C12—C1—C2—C3	−178.8 (4)	C1—C2—C11—O1	−1.1 (4)
S—C1—C2—C3	2.5 (7)	C3—C2—C11—C10	−1.8 (6)
C11—C2—C3—C4	−178.0 (4)	C1—C2—C11—C10	178.4 (4)
C1—C2—C3—C4	1.7 (7)	C12—O1—C11—C2	0.9 (4)
C11—C2—C3—C8	2.0 (5)	C12—O1—C11—C10	−178.6 (4)
C1—C2—C3—C8	−178.3 (4)	C9—C10—C11—C2	1.0 (6)
C8—C3—C4—C5	0.0 (6)	C9—C10—C11—O1	−179.5 (3)
C2—C3—C4—C5	180.0 (4)	C2—C1—C12—O1	−0.5 (4)
C3—C4—C5—C6	0.6 (6)	S—C1—C12—O1	178.3 (3)
C4—C5—C6—C7	−0.7 (7)	C2—C1—C12—C13	−179.2 (4)
C5—C6—C7—C8	0.3 (7)	S—C1—C12—C13	−0.4 (6)
C4—C3—C8—C9	178.5 (4)	C11—O1—C12—C1	−0.2 (4)
C2—C3—C8—C9	−1.5 (5)	C11—O1—C12—C13	178.7 (3)
C4—C3—C8—C7	−0.4 (5)	C1—C12—C13—C14	−102.7 (5)
C2—C3—C8—C7	179.6 (4)	O1—C12—C13—C14	78.6 (4)
C6—C7—C8—C3	0.3 (6)	C12—C13—C14—O2	10.5 (5)
C6—C7—C8—C9	−178.6 (4)	C12—C13—C14—O3	−170.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	1.91	2.711 (4)	167
C15—H15B···Cgⁱⁱ	0.96	3.03	3.949 (3)	161

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂O₃S
M_r	272.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.989 (2), 14.265 (5), 18.344 (7)
β (°)	90.18 (2)
V (Å³)	1305.5 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.45 × 0.28 × 0.09

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8459, 2209, 1130
R_int	0.115
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.224, 1.24
No. of reflections	2209
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.09, −1.45

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	1.91	2.711 (4)	166.8
C15—H15B···Cgⁱⁱ	0.96	3.03	3.949 (3)	160.8

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

References

Brandenburg, K. (1998). DIAMOND. Version 2.1. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SMART (Version 5.625) and SAINT (Version 6.28a). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o453

doi:10.1107/S1600536808000901

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