7-Bromo-2-methyl-1-tosyl-naphtho[2,1-b]furan.

The title compound, C(20)H(15)BrO(3)S, was prepared by the oxidation of 7-bromo-2-methyl-1-(4-tolyl-sulfan-yl)naph-tho[2,1-b]furan with 3-chloro-peroxy-benzoic acid. The 4-tolyl ring makes a dihedral angle of 70.96 (6)° with the plane of the naphthofuran fragment. The crystal structure is stabilized by aromatic π-π stacking inter-actions, with centroid-centroid distances of 3.672 (3) and 3.858 (3) Å between the central benzene and furan rings, and between the brominated benzene and central benzene rings of the naphthofuran system of neighbouring mol-ecules, respectively. In addition, the stacked mol-ecules exhibit C-H⋯π and inter- and intra-molecular C-H⋯O inter-actions.

Related literature

For the crystal structures of similar 2-methyl-1-(phenyl­sulfon­yl)naphtho[2,1-b]furan compounds, see: Choi et al. (2008a ▶,b ▶).

Experimental

Crystal data

C20H15BrO3S

M = 415.29

Monoclinic,

a = 14.026 (2) Å

b = 8.225 (1) Å

c = 15.185 (2) Å

β = 102.826 (2)°

V = 1708.1 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.54 mm−1

T = 173 (2) K

0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.480, T max = 0.608

10014 measured reflections

3704 independent reflections

3368 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.082

S = 1.09

3704 reflections

228 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −1.04 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, 1997 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015286/at2569sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015286/at2569Isup2.hkl

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

C20H15BrO3S	F000 = 840
Mr = 415.29	Dx = 1.615 Mg m−3
Monoclinic, P21/n	Melting point = 480–481 K
Hall symbol: -P 2yn	Mo Kα radiation λ = 0.71073 Å
a = 14.026 (2) Å	Cell parameters from 6484 reflections
b = 8.225 (1) Å	θ = 2.2–28.3º
c = 15.185 (2) Å	µ = 2.55 mm−1
β = 102.826 (2)º	T = 173 (2) K
V = 1708.1 (4) Å3	Block, colourless
Z = 4	0.30 × 0.30 × 0.20 mm

Bruker SMART CCD diffractometer	3704 independent reflections
Radiation source: fine-focus sealed tube	3368 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.024
Detector resolution: 10 pixels mm-1	θmax = 27.0º
T = 173(2) K	θmin = 2.8º
φ and ω scans	h = −17→14
Absorption correction: multi-scan(SADABS; Sheldrick, 2000)	k = −10→9
Tmin = 0.480, Tmax = 0.608	l = −19→19
10014 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H-atom parameters constrained
wR(F2) = 0.082	w = 1/[σ2(Fo2) + (0.0373P)2 + 1.421P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
3704 reflections	Δρmax = 0.61 e Å−3
228 parameters	Δρmin = −1.04 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
Br	0.307602 (17)	1.04128 (3)	0.664085 (18)	0.04012 (10)
S	0.79201 (3)	0.59282 (6)	0.62949 (3)	0.01860 (11)
O1	0.64155 (11)	0.52776 (18)	0.38321 (9)	0.0264 (3)
O2	0.74469 (10)	0.61119 (18)	0.70363 (9)	0.0248 (3)
O3	0.85357 (11)	0.45249 (17)	0.62854 (11)	0.0276 (3)
C1	0.70375 (14)	0.5926 (2)	0.52785 (12)	0.0190 (4)
C2	0.60466 (14)	0.6593 (2)	0.50343 (12)	0.0184 (4)
C3	0.53912 (13)	0.7504 (2)	0.54485 (12)	0.0177 (4)
C4	0.56078 (14)	0.8095 (2)	0.63474 (13)	0.0214 (4)
H4	0.6233	0.7883	0.6723	0.026*
C5	0.49378 (15)	0.8966 (3)	0.66890 (14)	0.0245 (4)
H5	0.5102	0.9368	0.7290	0.029*
C6	0.40102 (15)	0.9256 (3)	0.61444 (15)	0.0249 (4)
C7	0.37592 (15)	0.8727 (3)	0.52738 (14)	0.0250 (4)
H7	0.3125	0.8947	0.4917	0.030*
C8	0.44413 (14)	0.7849 (2)	0.48995 (13)	0.0209 (4)
C9	0.41645 (15)	0.7306 (3)	0.39838 (14)	0.0266 (4)
H9	0.3529	0.7550	0.3638	0.032*
C10	0.47904 (16)	0.6451 (3)	0.35995 (13)	0.0264 (4)
H10	0.4611	0.6088	0.2991	0.032*
C11	0.57167 (15)	0.6128 (2)	0.41433 (13)	0.0219 (4)
C12	0.72149 (16)	0.5171 (2)	0.45281 (14)	0.0241 (4)
C13	0.86530 (13)	0.7660 (2)	0.62557 (12)	0.0181 (4)
C14	0.82844 (14)	0.9193 (2)	0.63701 (13)	0.0207 (4)
H14	0.7635	0.9315	0.6449	0.025*
C15	0.88778 (15)	1.0550 (2)	0.63683 (14)	0.0229 (4)
H15	0.8626	1.1602	0.6441	0.027*
C16	0.98325 (16)	1.0390 (2)	0.62625 (15)	0.0249 (4)
C17	1.01851 (17)	0.8839 (3)	0.61549 (19)	0.0361 (5)
H17	1.0837	0.8713	0.6083	0.043*
C18	0.96049 (16)	0.7473 (3)	0.61504 (17)	0.0309 (5)
H18	0.9856	0.6421	0.6076	0.037*
C19	0.80537 (19)	0.4294 (3)	0.43022 (17)	0.0359 (5)
H19A	0.8032	0.3148	0.4473	0.054*
H19B	0.8667	0.4782	0.4633	0.054*
H19C	0.8017	0.4374	0.3652	0.054*
C20	1.04846 (17)	1.1859 (3)	0.62979 (18)	0.0360 (5)
H20A	1.0081	1.2836	0.6153	0.054*
H20B	1.0896	1.1731	0.5858	0.054*
H20C	1.0901	1.1963	0.6906	0.054*

	U11	U22	U33	U12	U13	U23
Br	0.03043 (14)	0.04477 (17)	0.04947 (17)	0.01043 (10)	0.01810 (11)	−0.00261 (11)
S	0.0176 (2)	0.0165 (2)	0.0206 (2)	0.00131 (16)	0.00179 (17)	0.00252 (17)
O1	0.0320 (8)	0.0272 (8)	0.0197 (7)	0.0013 (6)	0.0050 (6)	−0.0045 (6)
O2	0.0238 (7)	0.0306 (8)	0.0191 (7)	−0.0015 (6)	0.0029 (5)	0.0053 (6)
O3	0.0259 (8)	0.0169 (7)	0.0370 (8)	0.0048 (6)	0.0009 (6)	0.0022 (6)
C1	0.0194 (9)	0.0179 (9)	0.0191 (9)	0.0000 (7)	0.0030 (7)	−0.0002 (7)
C2	0.0204 (9)	0.0149 (8)	0.0183 (9)	−0.0019 (7)	0.0008 (7)	0.0014 (7)
C3	0.0180 (9)	0.0155 (8)	0.0187 (8)	−0.0011 (7)	0.0021 (7)	0.0026 (7)
C4	0.0187 (9)	0.0241 (10)	0.0201 (9)	−0.0014 (7)	0.0015 (7)	−0.0001 (7)
C5	0.0242 (10)	0.0264 (10)	0.0233 (10)	−0.0020 (8)	0.0061 (8)	−0.0034 (8)
C6	0.0219 (10)	0.0225 (10)	0.0324 (11)	0.0021 (8)	0.0107 (8)	0.0020 (8)
C7	0.0189 (9)	0.0252 (10)	0.0288 (10)	0.0024 (8)	0.0009 (8)	0.0058 (8)
C8	0.0206 (9)	0.0189 (9)	0.0211 (9)	−0.0016 (7)	0.0003 (7)	0.0040 (7)
C9	0.0244 (10)	0.0276 (10)	0.0227 (10)	−0.0006 (8)	−0.0056 (8)	0.0040 (8)
C10	0.0323 (11)	0.0268 (10)	0.0159 (9)	−0.0024 (8)	−0.0041 (8)	−0.0007 (8)
C11	0.0259 (10)	0.0193 (9)	0.0205 (9)	−0.0012 (8)	0.0048 (8)	−0.0005 (7)
C12	0.0263 (10)	0.0219 (10)	0.0243 (10)	−0.0001 (8)	0.0059 (8)	0.0005 (8)
C13	0.0176 (9)	0.0179 (9)	0.0184 (8)	0.0008 (7)	0.0029 (7)	−0.0005 (7)
C14	0.0157 (9)	0.0213 (9)	0.0245 (9)	0.0040 (7)	0.0029 (7)	0.0011 (7)
C15	0.0224 (10)	0.0177 (9)	0.0274 (10)	0.0041 (7)	0.0030 (8)	0.0005 (7)
C16	0.0248 (10)	0.0216 (10)	0.0295 (10)	−0.0020 (8)	0.0085 (8)	−0.0016 (8)
C17	0.0246 (11)	0.0275 (12)	0.0625 (16)	0.0002 (9)	0.0231 (11)	−0.0077 (11)
C18	0.0260 (11)	0.0201 (10)	0.0507 (13)	0.0019 (8)	0.0170 (10)	−0.0063 (9)
C19	0.0361 (13)	0.0377 (13)	0.0379 (12)	0.0065 (10)	0.0166 (10)	−0.0062 (10)
C20	0.0276 (11)	0.0271 (11)	0.0563 (15)	−0.0058 (9)	0.0158 (11)	−0.0028 (10)

Br—C6	1.905 (2)	C9—H9	0.9500
S—O2	1.436 (2)	C10—C11	1.401 (3)
S—O3	1.443 (2)	C10—H10	0.9500
S—C1	1.751 (2)	C12—C19	1.483 (3)
S—C13	1.765 (2)	C13—C18	1.388 (3)
O1—C12	1.362 (3)	C13—C14	1.388 (3)
O1—C11	1.371 (3)	C14—C15	1.392 (3)
C1—C12	1.368 (3)	C14—H14	0.9500
C1—C2	1.463 (3)	C15—C16	1.390 (3)
C2—C11	1.383 (3)	C15—H15	0.9500
C2—C3	1.435 (3)	C16—C17	1.391 (3)
C3—C4	1.417 (3)	C16—C20	1.509 (3)
C3—C8	1.434 (3)	C17—C18	1.387 (3)
C4—C5	1.372 (3)	C17—H17	0.9500
C4—H4	0.9500	C18—H18	0.9500
C5—C6	1.399 (3)	C19—H19A	0.9800
C5—H5	0.9500	C19—H19B	0.9800
C6—C7	1.362 (3)	C19—H19C	0.9800
C7—C8	1.415 (3)	C20—H20A	0.9800
C7—H7	0.9500	C20—H20B	0.9800
C8—C9	1.430 (3)	C20—H20C	0.9800
C9—C10	1.354 (3)
O2—S—O3	118.26 (9)	O1—C11—C2	111.6 (2)
O2—S—C1	109.37 (9)	O1—C11—C10	122.3 (2)
O3—S—C1	107.33 (9)	C2—C11—C10	126.1 (2)
O2—S—C13	108.39 (9)	O1—C12—C1	110.3 (2)
O3—S—C13	106.92 (9)	O1—C12—C19	114.2 (2)
C1—S—C13	105.90 (9)	C1—C12—C19	135.5 (2)
C12—O1—C11	107.1 (2)	C18—C13—C14	120.7 (2)
C12—C1—C2	107.3 (2)	C18—C13—S	119.8 (2)
C12—C1—S	120.7 (2)	C14—C13—S	119.5 (1)
C2—C1—S	132.0 (2)	C13—C14—C15	119.2 (2)
C11—C2—C3	117.7 (2)	C13—C14—H14	120.4
C11—C2—C1	103.7 (2)	C15—C14—H14	120.4
C3—C2—C1	138.6 (2)	C16—C15—C14	121.1 (2)
C4—C3—C8	117.7 (2)	C16—C15—H15	119.5
C4—C3—C2	125.5 (2)	C14—C15—H15	119.5
C8—C3—C2	116.8 (2)	C15—C16—C17	118.5 (2)
C5—C4—C3	121.7 (2)	C15—C16—C20	120.8 (2)
C5—C4—H4	119.2	C17—C16—C20	120.7 (2)
C3—C4—H4	119.2	C18—C17—C16	121.4 (2)
C4—C5—C6	119.4 (2)	C18—C17—H17	119.3
C4—C5—H5	120.3	C16—C17—H17	119.3
C6—C5—H5	120.3	C17—C18—C13	119.2 (2)
C7—C6—C5	121.7 (2)	C17—C18—H18	120.4
C7—C6—Br	119.5 (2)	C13—C18—H18	120.4
C5—C6—Br	118.9 (2)	C12—C19—H19A	109.5
C6—C7—C8	120.1 (2)	C12—C19—H19B	109.5
C6—C7—H7	120.0	H19A—C19—H19B	109.5
C8—C7—H7	120.0	C12—C19—H19C	109.5
C7—C8—C9	119.2 (2)	H19A—C19—H19C	109.5
C7—C8—C3	119.4 (2)	H19B—C19—H19C	109.5
C9—C8—C3	121.4 (2)	C16—C20—H20A	109.5
C10—C9—C8	121.3 (2)	C16—C20—H20B	109.5
C10—C9—H9	119.4	H20A—C20—H20B	109.5
C8—C9—H9	119.4	C16—C20—H20C	109.5
C9—C10—C11	116.7 (2)	H20A—C20—H20C	109.5
C9—C10—H10	121.6	H20B—C20—H20C	109.5
C11—C10—H10	121.6
O2—S—C1—C12	−154.52 (16)	C12—O1—C11—C2	0.4 (2)
O3—S—C1—C12	−25.06 (19)	C12—O1—C11—C10	−179.39 (19)
C13—S—C1—C12	88.88 (18)	C3—C2—C11—O1	179.65 (16)
O2—S—C1—C2	23.9 (2)	C1—C2—C11—O1	−0.9 (2)
O3—S—C1—C2	153.39 (18)	C3—C2—C11—C10	−0.6 (3)
C13—S—C1—C2	−92.7 (2)	C1—C2—C11—C10	178.83 (19)
C12—C1—C2—C11	1.1 (2)	C9—C10—C11—O1	−179.86 (19)
S—C1—C2—C11	−177.49 (16)	C9—C10—C11—C2	0.4 (3)
C12—C1—C2—C3	−179.6 (2)	C11—O1—C12—C1	0.4 (2)
S—C1—C2—C3	1.8 (4)	C11—O1—C12—C19	−179.30 (18)
C11—C2—C3—C4	−179.21 (18)	C2—C1—C12—O1	−1.0 (2)
C1—C2—C3—C4	1.6 (4)	S—C1—C12—O1	177.83 (14)
C11—C2—C3—C8	0.3 (3)	C2—C1—C12—C19	178.7 (2)
C1—C2—C3—C8	−178.8 (2)	S—C1—C12—C19	−2.5 (4)
C8—C3—C4—C5	0.1 (3)	O2—S—C13—C18	133.70 (17)
C2—C3—C4—C5	179.65 (19)	O3—S—C13—C18	5.2 (2)
C3—C4—C5—C6	1.2 (3)	C1—S—C13—C18	−109.04 (18)
C4—C5—C6—C7	−1.5 (3)	O2—S—C13—C14	−43.50 (17)
C4—C5—C6—Br	178.18 (16)	O3—S—C13—C14	−172.00 (15)
C5—C6—C7—C8	0.4 (3)	C1—S—C13—C14	73.77 (17)
Br—C6—C7—C8	−179.22 (15)	C18—C13—C14—C15	0.7 (3)
C6—C7—C8—C9	−179.87 (19)	S—C13—C14—C15	177.89 (15)
C6—C7—C8—C3	0.9 (3)	C13—C14—C15—C16	−0.6 (3)
C4—C3—C8—C7	−1.1 (3)	C14—C15—C16—C17	0.2 (3)
C2—C3—C8—C7	179.28 (17)	C14—C15—C16—C20	−177.6 (2)
C4—C3—C8—C9	179.64 (18)	C15—C16—C17—C18	0.1 (4)
C2—C3—C8—C9	0.1 (3)	C20—C16—C17—C18	177.9 (2)
C7—C8—C9—C10	−179.5 (2)	C16—C17—C18—C13	0.0 (4)
C3—C8—C9—C10	−0.2 (3)	C14—C13—C18—C17	−0.4 (3)
C8—C9—C10—C11	0.0 (3)	S—C13—C18—C17	−177.58 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cg1i	0.95	2.57	3.485 (3)	163
C4—H4···O2	0.95	2.21	3.035 (2)	145
C15—H15···O3ii	0.95	2.42	3.303 (2)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Cg1i	0.95	2.57	3.485 (3)	163
C4—H4⋯O2	0.95	2.21	3.035 (2)	145
C15—H15⋯O3ii	0.95	2.42	3.303 (2)	155

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C13–C18 benzene ring.