supplementary materials


hg5324 scheme

Acta Cryst. (2013). E69, o1148    [ doi:10.1107/S1600536813016978 ]

7-Bromo-2-(4-methylphenyl)-1-(methylsulfinyl)naphtho[2,1-b]furan

H. D. Choi, P. J. Seo and U. Lee

Abstract top

In the title compound, C20H15BrO2S, the dihedral angle between the mean plane [r.m.s. deviation = 0.030 (2) Å] of the naphthofuran ring system and the 4-methylphenyl ring is 38.49 (9)°. In the crystal, molecules are linked by C-H...[pi] and C-Br...[pi] [3.871 (2) Å] interactions into stacks along the b-axis direction. These stacks are further linked by weak C-H...O hydrogen bonds, forming a three-dimensional network.

Comment top

As a part of our ongoing study of 7-bromo-1-(methylsulfinyl)naphtho[2,1-b] furan derivatives containing phenyl (Choi et al., 2009) and 4-fluorophenyl (Choi et al., 2010) substituents in 2-position, we report herein the crystal structure of the title compound.

In the title molecule (Fig. 1), the naphthofuran unit is essentially planar, with a mean deviation of 0.030 (2) Å from the least-squares plane defined by the thirteen constituent atoms. The dihedral angle between the mean plane of the naphthofuran ring system and the 4-methylphenyl ring is 38.49 (9)°. In the crystal structure (Fig. 2), molecules are connected by C–H···π (Table 1), and C6–Br1···π [3.871 (2) Å] interactions between the bromine atom and the central benzene ring of a neighbouring molecule with a Br1···Cg1iii being 3.871 (2) Å (Cg1 is the centroid of the C2/C3/C8/C9/C10/C11 benzene ring), into stacks along the b-axis direction. These stacks are further packed by weak C–H···O hydrogen bonds (Table 1), forming a three-dimensional network.

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2009, 2010).

Experimental top

3-Chloroperoxybenzoic acid (77%, 202 mg, 0.9 mmol) was added in small portions to a stirred solution of 7-bromo-2-(4-methylphenyl)-1-(methylsulfanyl)naphtho[2,1-b]furan (306 mg, 0.8 mmol) in dichloromethane (40 mL) at 273 K. After being stirred at room temperature for 6h, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated at reduced pressure. The residue was purified by column chromatography (hexane-ethyl acetate, 2:1 v/v) to afford the title compound as a colorless solid [yield 61%, m.p. 485-486 K; Rf = 0.46 (hexane-ethyl acetate, 2:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in acetone at room temperature.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C–H = 0.95 Å for aryl and 0.98Å for methyl H atoms. Uiso(H) = 1.2Ueq(C) for aryl and 1.5Ueq(C) for methyl H atoms. The positions of methyl hydrogens were optimized rotationally. The highest peak in the difference map is 1.38 Å from S1 and the largest hole is 0.70 Å from Br1.

Computing details top

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 (Farrugia, 2012) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
[Figure 2] Fig. 2. A view of the C–H···O, C–H···π and C–Br···π interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. [Symmetry codes: (i) x + 1, - y + 3/2, z - 1/2; (ii) x+ 1, y, z; (iii) x - 1, y, z; (iv) x - 1, - y + 3/2, z + 1/2.]
7-Bromo-2-(4-methylphenyl)-1-(methylsulfinyl)naphtho[2,1-b]furan top
Crystal data top
C20H15BrO2SF(000) = 808
Mr = 399.29Dx = 1.623 Mg m3
Monoclinic, P21/cMelting point = 485–486 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 6.2198 (11) ÅCell parameters from 3620 reflections
b = 23.234 (4) Åθ = 2.5–27.0°
c = 11.344 (2) ŵ = 2.65 mm1
β = 94.733 (12)°T = 173 K
V = 1633.7 (5) Å3Block, colourless
Z = 40.27 × 0.19 × 0.11 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
4083 independent reflections
Radiation source: rotating anode3135 reflections with I > 2σ(I)
Graphite multilayer monochromatorRint = 0.070
Detector resolution: 10.0 pixels mm-1θmax = 28.4°, θmin = 1.8°
φ and ω scansh = 88
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
k = 3030
Tmin = 0.472, Tmax = 0.746l = 1515
16182 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: difference Fourier map
wR(F2) = 0.117H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0557P)2 + 0.6314P]
where P = (Fo2 + 2Fc2)/3
4083 reflections(Δ/σ)max = 0.001
219 parametersΔρmax = 1.16 e Å3
0 restraintsΔρmin = 0.63 e Å3
Crystal data top
C20H15BrO2SV = 1633.7 (5) Å3
Mr = 399.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.2198 (11) ŵ = 2.65 mm1
b = 23.234 (4) ÅT = 173 K
c = 11.344 (2) Å0.27 × 0.19 × 0.11 mm
β = 94.733 (12)°
Data collection top
Bruker SMART APEXII CCD
diffractometer
4083 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
3135 reflections with I > 2σ(I)
Tmin = 0.472, Tmax = 0.746Rint = 0.070
16182 measured reflectionsθmax = 28.4°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.117Δρmax = 1.16 e Å3
S = 1.04Δρmin = 0.63 e Å3
4083 reflectionsAbsolute structure: ?
219 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
Br10.08040 (5)0.625454 (16)1.02806 (3)0.03661 (13)
S10.99799 (11)0.71743 (3)0.64298 (6)0.02279 (16)
O11.0693 (3)0.54998 (8)0.62255 (17)0.0226 (4)
O20.9682 (3)0.74231 (8)0.76168 (19)0.0299 (5)
C10.9742 (4)0.64212 (12)0.6514 (2)0.0198 (5)
C20.8386 (4)0.60547 (11)0.7188 (2)0.0198 (5)
C30.6611 (4)0.61296 (12)0.7902 (2)0.0216 (6)
C40.5747 (4)0.66676 (12)0.8204 (2)0.0235 (6)
H40.63690.70110.79320.028*
C50.4029 (5)0.67024 (13)0.8883 (3)0.0267 (6)
H50.34610.70670.90750.032*
C60.3116 (4)0.61977 (13)0.9291 (3)0.0259 (6)
C70.3880 (4)0.56710 (13)0.9027 (2)0.0264 (6)
H70.32200.53350.93100.032*
C80.5663 (4)0.56194 (12)0.8330 (2)0.0236 (6)
C90.6476 (4)0.50695 (12)0.8070 (2)0.0253 (6)
H90.58210.47380.83740.030*
C100.8171 (4)0.50023 (12)0.7395 (2)0.0253 (6)
H100.87150.46320.72220.030*
C110.9068 (4)0.55038 (12)0.6971 (2)0.0213 (5)
C121.1077 (4)0.60658 (12)0.5948 (2)0.0207 (5)
C131.2659 (4)0.61466 (11)0.5080 (2)0.0206 (5)
C141.4444 (4)0.57774 (12)0.5083 (2)0.0214 (5)
H141.46750.54950.56850.026*
C151.5871 (4)0.58234 (12)0.4214 (3)0.0231 (6)
H151.70880.55750.42350.028*
C161.5555 (5)0.62264 (12)0.3308 (3)0.0239 (6)
C171.3798 (4)0.65974 (12)0.3322 (2)0.0252 (6)
H171.35810.68830.27250.030*
C181.2359 (4)0.65572 (12)0.4190 (2)0.0239 (6)
H181.11620.68120.41760.029*
C191.7039 (5)0.62599 (13)0.2328 (3)0.0309 (7)
H19A1.80060.65910.24600.046*
H19B1.61830.63050.15690.046*
H19C1.78940.59060.23160.046*
C200.7540 (5)0.73215 (13)0.5513 (3)0.0318 (7)
H20A0.63050.71580.58810.048*
H20B0.76350.71480.47320.048*
H20C0.73500.77390.54280.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03055 (19)0.0514 (2)0.02954 (18)0.00701 (13)0.01237 (13)0.00111 (14)
S10.0252 (3)0.0159 (3)0.0275 (4)0.0011 (2)0.0034 (3)0.0017 (3)
O10.0257 (9)0.0171 (10)0.0262 (10)0.0019 (7)0.0083 (8)0.0005 (8)
O20.0372 (11)0.0225 (11)0.0302 (11)0.0008 (9)0.0029 (9)0.0079 (9)
C10.0216 (13)0.0176 (13)0.0203 (12)0.0008 (10)0.0021 (10)0.0009 (10)
C20.0215 (13)0.0179 (13)0.0202 (13)0.0009 (10)0.0032 (10)0.0013 (10)
C30.0237 (13)0.0229 (14)0.0183 (12)0.0007 (10)0.0032 (10)0.0037 (11)
C40.0249 (14)0.0213 (14)0.0245 (14)0.0017 (11)0.0025 (11)0.0016 (11)
C50.0262 (14)0.0259 (16)0.0282 (15)0.0042 (11)0.0027 (11)0.0040 (12)
C60.0215 (13)0.0361 (17)0.0204 (13)0.0013 (11)0.0035 (11)0.0035 (12)
C70.0256 (14)0.0316 (16)0.0226 (14)0.0043 (12)0.0060 (11)0.0021 (12)
C80.0284 (14)0.0237 (15)0.0189 (13)0.0015 (11)0.0027 (10)0.0032 (11)
C90.0316 (15)0.0193 (14)0.0257 (14)0.0062 (11)0.0072 (11)0.0017 (11)
C100.0323 (15)0.0174 (14)0.0267 (14)0.0019 (11)0.0048 (12)0.0010 (11)
C110.0215 (12)0.0215 (14)0.0209 (13)0.0026 (10)0.0022 (10)0.0002 (11)
C120.0224 (13)0.0199 (14)0.0197 (13)0.0007 (10)0.0009 (10)0.0003 (10)
C130.0222 (13)0.0181 (13)0.0220 (13)0.0016 (10)0.0039 (10)0.0022 (10)
C140.0242 (13)0.0172 (13)0.0232 (13)0.0003 (10)0.0034 (10)0.0005 (11)
C150.0210 (13)0.0195 (14)0.0293 (14)0.0005 (10)0.0041 (11)0.0020 (11)
C160.0265 (14)0.0202 (14)0.0254 (14)0.0060 (11)0.0050 (11)0.0006 (11)
C170.0316 (15)0.0204 (14)0.0238 (14)0.0003 (11)0.0028 (11)0.0038 (11)
C180.0264 (14)0.0198 (14)0.0256 (14)0.0027 (11)0.0036 (11)0.0009 (11)
C190.0328 (16)0.0291 (17)0.0320 (16)0.0043 (12)0.0103 (13)0.0023 (13)
C200.0398 (17)0.0244 (16)0.0302 (16)0.0060 (13)0.0032 (13)0.0007 (13)
Geometric parameters (Å, º) top
Br1—C61.900 (3)C9—H90.9500
S1—O21.491 (2)C10—C111.395 (4)
S1—C11.759 (3)C10—H100.9500
S1—C201.801 (3)C12—C131.460 (4)
O1—C111.370 (3)C13—C181.390 (4)
O1—C121.378 (3)C13—C141.403 (4)
C1—C121.368 (4)C14—C151.384 (4)
C1—C21.459 (4)C14—H140.9500
C2—C111.377 (4)C15—C161.392 (4)
C2—C31.433 (4)C15—H150.9500
C3—C41.414 (4)C16—C171.393 (4)
C3—C81.427 (4)C16—C191.504 (4)
C4—C51.370 (4)C17—C181.388 (4)
C4—H40.9500C17—H170.9500
C5—C61.399 (4)C18—H180.9500
C5—H50.9500C19—H19A0.9800
C6—C71.355 (4)C19—H19B0.9800
C7—C81.419 (4)C19—H19C0.9800
C7—H70.9500C20—H20A0.9800
C8—C91.414 (4)C20—H20B0.9800
C9—C101.362 (4)C20—H20C0.9800
O2—S1—C1108.63 (13)O1—C11—C10122.9 (2)
O2—S1—C20106.64 (14)C2—C11—C10125.3 (3)
C1—S1—C2098.61 (14)C1—C12—O1110.2 (2)
C11—O1—C12106.6 (2)C1—C12—C13135.0 (3)
C12—C1—C2107.1 (2)O1—C12—C13114.6 (2)
C12—C1—S1121.2 (2)C18—C13—C14118.7 (3)
C2—C1—S1131.6 (2)C18—C13—C12121.3 (3)
C11—C2—C3118.5 (2)C14—C13—C12119.8 (2)
C11—C2—C1104.4 (2)C15—C14—C13120.3 (3)
C3—C2—C1137.0 (3)C15—C14—H14119.9
C4—C3—C8118.4 (2)C13—C14—H14119.9
C4—C3—C2124.8 (3)C14—C15—C16121.2 (3)
C8—C3—C2116.8 (2)C14—C15—H15119.4
C5—C4—C3121.2 (3)C16—C15—H15119.4
C5—C4—H4119.4C15—C16—C17118.1 (3)
C3—C4—H4119.4C15—C16—C19121.5 (3)
C4—C5—C6119.6 (3)C17—C16—C19120.4 (3)
C4—C5—H5120.2C18—C17—C16121.3 (3)
C6—C5—H5120.2C18—C17—H17119.4
C7—C6—C5121.6 (3)C16—C17—H17119.4
C7—C6—Br1119.3 (2)C17—C18—C13120.4 (3)
C5—C6—Br1119.0 (2)C17—C18—H18119.8
C6—C7—C8120.3 (3)C13—C18—H18119.8
C6—C7—H7119.9C16—C19—H19A109.5
C8—C7—H7119.9C16—C19—H19B109.5
C9—C8—C7120.1 (3)H19A—C19—H19B109.5
C9—C8—C3121.0 (2)C16—C19—H19C109.5
C7—C8—C3118.9 (3)H19A—C19—H19C109.5
C10—C9—C8121.8 (3)H19B—C19—H19C109.5
C10—C9—H9119.1S1—C20—H20A109.5
C8—C9—H9119.1S1—C20—H20B109.5
C9—C10—C11116.6 (3)H20A—C20—H20B109.5
C9—C10—H10121.7S1—C20—H20C109.5
C11—C10—H10121.7H20A—C20—H20C109.5
O1—C11—C2111.7 (2)H20B—C20—H20C109.5
O2—S1—C1—C12139.7 (2)C12—O1—C11—C20.1 (3)
C20—S1—C1—C12109.4 (2)C12—O1—C11—C10176.8 (2)
O2—S1—C1—C235.1 (3)C3—C2—C11—O1176.7 (2)
C20—S1—C1—C275.8 (3)C1—C2—C11—O10.5 (3)
C12—C1—C2—C110.8 (3)C3—C2—C11—C100.1 (4)
S1—C1—C2—C11174.6 (2)C1—C2—C11—C10177.2 (3)
C12—C1—C2—C3175.5 (3)C9—C10—C11—O1176.0 (2)
S1—C1—C2—C39.1 (5)C9—C10—C11—C20.5 (4)
C11—C2—C3—C4179.6 (3)C2—C1—C12—O10.9 (3)
C1—C2—C3—C44.5 (5)S1—C1—C12—O1175.08 (18)
C11—C2—C3—C80.6 (4)C2—C1—C12—C13174.0 (3)
C1—C2—C3—C8175.3 (3)S1—C1—C12—C1310.0 (5)
C8—C3—C4—C50.5 (4)C11—O1—C12—C10.6 (3)
C2—C3—C4—C5179.3 (3)C11—O1—C12—C13175.4 (2)
C3—C4—C5—C60.3 (4)C1—C12—C13—C1835.4 (5)
C4—C5—C6—C70.4 (5)O1—C12—C13—C18139.3 (3)
C4—C5—C6—Br1177.7 (2)C1—C12—C13—C14149.3 (3)
C5—C6—C7—C80.6 (4)O1—C12—C13—C1436.0 (3)
Br1—C6—C7—C8177.4 (2)C18—C13—C14—C150.1 (4)
C6—C7—C8—C9179.1 (3)C12—C13—C14—C15175.4 (3)
C6—C7—C8—C30.8 (4)C13—C14—C15—C161.2 (4)
C4—C3—C8—C9179.2 (2)C14—C15—C16—C172.2 (4)
C2—C3—C8—C91.0 (4)C14—C15—C16—C19177.0 (3)
C4—C3—C8—C70.8 (4)C15—C16—C17—C182.0 (4)
C2—C3—C8—C7179.1 (2)C19—C16—C17—C18177.2 (3)
C7—C8—C9—C10179.4 (3)C16—C17—C18—C130.8 (4)
C3—C8—C9—C100.7 (4)C14—C13—C18—C170.3 (4)
C8—C9—C10—C110.1 (4)C12—C13—C18—C17175.1 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C2/C3/C8/C9/C10/C11 benzene ring.
D—H···AD—HH···AD···AD—H···A
C19—H19A···O2i0.982.523.476 (4)166
C14—H14···Cg1ii0.952.683.342 (4)127
Symmetry codes: (i) x+1, y+3/2, z1/2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC20H15BrO2S
Mr399.29
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)6.2198 (11), 23.234 (4), 11.344 (2)
β (°) 94.733 (12)
V3)1633.7 (5)
Z4
Radiation typeMo Kα
µ (mm1)2.65
Crystal size (mm)0.27 × 0.19 × 0.11
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.472, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
16182, 4083, 3135
Rint0.070
(sin θ/λ)max1)0.670
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.117, 1.04
No. of reflections4083
No. of parameters219
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.16, 0.63

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C2/C3/C8/C9/C10/C11 benzene ring.
D—H···AD—HH···AD···AD—H···A
C19—H19A···O2i0.982.523.476 (4)166.0
C14—H14···Cg1ii0.952.683.342 (4)127.0
Symmetry codes: (i) x+1, y+3/2, z1/2; (ii) x+1, y, z.
Acknowledgements top

This work was supported by the Blue-Bio Industry Regional Innovation Center (RIC08-06-07) at Dongeui University as an RIC program under the Ministry of Knowledge Economy and Busan City.

references
References top

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2009). Acta Cryst. E65, o1956.

Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010). Acta Cryst. E66, o1012.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.