Crystal structure of 7-bromo-2-(3-fluoro-phen-yl)-1-(methyl-sulfin-yl)naphtho[2,1-b]furan.

In the title compound, C19H11BrFO2S, the dihedral angle between the plane of the naphtho-furan ring system [r.m.s. deviation = 0.043 (2) Å] and that of the 3-fluoro-benzene ring is 39.32 (8)°. In the crystal, mol-ecules are linked by C-H⋯O and C-Br⋯π [3.835 (1) Å] inter-actions into stacks along the c axis, forming a three-dimensional network. The F atom is disordered over two positions, with site-occupancy factors of 0.851 (3) and 0.149 (3).

Related literature

For the pharmacological activities of compounds containing a naphtho­furan ring, see: Debnath et al. (1993 ▶); Einhorn et al. (1984 ▶); Hranjec et al. (2003 ▶); Mahadevan & Vaidya (2003 ▶). For the fluorescence properties of compounds having a naphtho­furan skeleton, see: Piloto et al. (2005 ▶). For the synthesis of the starting material 7-bromo-2-(3-fluoro­phen­yl)-1-(methyl­sulf­an­yl)naphtho­[2,1-b]furan, see: Choi et al. (1999 ▶). For a related structure, see: Choi et al. (2013 ▶).

Experimental

Crystal data

C19H12BrFO2S

M = 403.26

Monoclinic,

a = 6.1340 (1) Å

b = 23.0602 (5) Å

c = 10.8806 (2) Å

β = 91.166 (1)°

V = 1538.76 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.83 mm−1

T = 173 K

0.74 × 0.45 × 0.38 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.229, T max = 0.413

14935 measured reflections

3834 independent reflections

3033 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.098

S = 1.04

3834 reflections

228 parameters

14 restraints

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.91 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681401808X/tk5335sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401808X/tk5335Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681401808X/tk5335Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S160053681401808X/tk5335fig1.tif

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. The F atom of the 3-fluoro­benzene ring is disordered over two positions with site occupancy factors, from refinement of 0.851 (3) (part A) and 0.149 (3) (part B).

Click here for additional data file.

x y z x y z x y z . DOI: 10.1107/S160053681401808X/tk5335fig2.tif

A view of the C—H⋯O and C—Br⋯π inter­actions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding are omitted for clarity [Symmetry codes: (i) x, − y + , z + ; (ii) x − 1, y, z; (iii) x, − y + , z − ].

CCDC reference: 1018271

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H12BrFO2S	F(000) = 808
Mr = 403.26	Dx = 1.741 Mg m−3
Monoclinic, P21/c	Melting point = 484 K–483 K K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.1340 (1) Å	Cell parameters from 5530 reflections
b = 23.0602 (5) Å	θ = 2.6–28.3°
c = 10.8806 (2) Å	µ = 2.83 mm−1
β = 91.166 (1)°	T = 173 K
V = 1538.76 (5) Å3	Block, colourless
Z = 4	0.74 × 0.45 × 0.38 mm

Bruker SMART APEXII CCD diffractometer	3834 independent reflections
Radiation source: rotating anode	3033 reflections with I > 2σ(I)
Graphite multilayer monochromator	Rint = 0.047
Detector resolution: 10.0 pixels mm-1	θmax = 28.4°, θmin = 1.8°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −30→19
Tmin = 0.229, Tmax = 0.413	l = −14→11
14935 measured reflections

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)] = 0.037	Hydrogen site location: difference Fourier map
wR(F2) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0539P)2 + 0.2694P] where P = (Fo2 + 2Fc2)/3
3834 reflections	(Δ/σ)max = 0.001
228 parameters	Δρmax = 0.47 e Å−3
14 restraints	Δρmin = −0.91 e Å−3

Experimental. 1H NMR (δ p.p.m., CDCl3, 400 Hz): 8.08-8.13 (m, 1H), 7.67-7.87 (m, 5H), 7.48-7.55 (m, 2H), 7.19-7.24 (m, 1H), 3.07 (s, 3H).

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	Occ. (<1)
Br1	−0.54910 (4)	0.387149 (11)	−0.05723 (2)	0.03031 (11)
S1	0.42612 (9)	0.27925 (2)	0.34599 (5)	0.01784 (14)
O1	0.5270 (3)	0.44696 (6)	0.37648 (14)	0.0183 (3)
O2	0.3848 (3)	0.25673 (7)	0.21917 (14)	0.0241 (4)
C1	0.4108 (4)	0.35599 (9)	0.34160 (19)	0.0149 (4)
C2	0.2686 (4)	0.39476 (9)	0.2724 (2)	0.0146 (5)
C3	0.0780 (4)	0.38989 (9)	0.1956 (2)	0.0153 (5)
C4	−0.0172 (4)	0.33718 (9)	0.1568 (2)	0.0184 (5)
H4	0.0479	0.3016	0.1821	0.022*
C5	−0.2012 (4)	0.33605 (10)	0.0835 (2)	0.0213 (5)
H5	−0.2627	0.3002	0.0574	0.026*
C6	−0.2975 (4)	0.38870 (9)	0.0474 (2)	0.0204 (5)
C7	−0.2122 (4)	0.44064 (10)	0.0813 (2)	0.0202 (5)
H7	−0.2804	0.4756	0.0548	0.024*
C8	−0.0216 (4)	0.44276 (9)	0.1562 (2)	0.0173 (5)
C9	0.0723 (4)	0.49734 (10)	0.1878 (2)	0.0208 (5)
H9	0.0030	0.5318	0.1595	0.025*
C10	0.2587 (4)	0.50152 (10)	0.2573 (2)	0.0206 (5)
H10	0.3233	0.5379	0.2767	0.025*
C11	0.3494 (4)	0.44945 (9)	0.2984 (2)	0.0169 (5)
C12	0.5593 (4)	0.38974 (9)	0.4033 (2)	0.0166 (5)
C13	0.7303 (4)	0.37854 (9)	0.4959 (2)	0.0170 (5)
C14	0.9160 (4)	0.41338 (10)	0.4996 (2)	0.0187 (5)
H14	0.9354	0.4434	0.4410	0.022*
C15A	1.0699 (4)	0.40315 (11)	0.5903 (2)	0.0253 (6)	0.851 (3)
F1A	1.2485 (3)	0.43617 (7)	0.59705 (16)	0.0334 (5)	0.851 (3)
C15B	1.0699 (4)	0.40315 (11)	0.5903 (2)	0.0253 (6)	0.15
H15B	1.1971	0.4267	0.5927	0.030*	0.149 (3)
C16	1.0499 (4)	0.36077 (11)	0.6776 (2)	0.0278 (6)
H16	1.1607	0.3544	0.7384	0.033*
C17A	0.8625 (4)	0.32773 (11)	0.6738 (2)	0.0273 (6)	0.851 (3)
H17A	0.8433	0.2984	0.7340	0.033*	0.851 (3)
C17B	0.8625 (4)	0.32773 (11)	0.6738 (2)	0.0273 (6)	0.15
F1B	0.8601 (17)	0.2943 (4)	0.7701 (6)	0.034 (3)	0.149 (3)
C18	0.7026 (4)	0.33614 (10)	0.5852 (2)	0.0204 (5)
H18	0.5741	0.3131	0.5850	0.025*
C19	0.1839 (4)	0.26492 (10)	0.4306 (2)	0.0236 (5)
H19A	0.0615	0.2866	0.3941	0.035*
H19B	0.2065	0.2770	0.5163	0.035*
H19C	0.1514	0.2233	0.4276	0.035*

	U11	U22	U33	U12	U13	U23
Br1	0.02564 (16)	0.03656 (18)	0.02825 (17)	−0.00225 (11)	−0.01109 (11)	0.00308 (11)
S1	0.0209 (3)	0.0138 (3)	0.0187 (3)	0.0028 (2)	−0.0025 (2)	−0.0023 (2)
O1	0.0201 (8)	0.0164 (8)	0.0184 (8)	−0.0024 (6)	−0.0026 (7)	−0.0005 (6)
O2	0.0306 (10)	0.0204 (8)	0.0213 (9)	0.0033 (7)	−0.0002 (7)	−0.0066 (7)
C1	0.0173 (11)	0.0149 (10)	0.0127 (11)	0.0003 (9)	0.0011 (8)	−0.0005 (8)
C2	0.0183 (12)	0.0142 (10)	0.0114 (11)	−0.0001 (8)	0.0016 (9)	−0.0015 (8)
C3	0.0174 (11)	0.0181 (11)	0.0105 (10)	0.0019 (8)	0.0015 (9)	−0.0012 (8)
C4	0.0219 (12)	0.0151 (11)	0.0183 (11)	−0.0002 (9)	−0.0008 (9)	0.0002 (9)
C5	0.0219 (13)	0.0218 (12)	0.0202 (12)	−0.0023 (10)	−0.0017 (9)	−0.0018 (10)
C6	0.0180 (12)	0.0287 (13)	0.0144 (11)	0.0000 (10)	−0.0023 (9)	−0.0002 (9)
C7	0.0220 (12)	0.0228 (12)	0.0156 (11)	0.0043 (10)	−0.0017 (9)	0.0031 (9)
C8	0.0211 (12)	0.0186 (11)	0.0123 (11)	0.0025 (9)	0.0003 (8)	0.0006 (9)
C9	0.0307 (14)	0.0140 (11)	0.0175 (11)	0.0038 (9)	−0.0011 (10)	0.0011 (9)
C10	0.0290 (13)	0.0138 (11)	0.0191 (12)	−0.0013 (9)	0.0025 (10)	−0.0003 (9)
C11	0.0171 (11)	0.0195 (11)	0.0141 (11)	−0.0009 (9)	0.0004 (9)	0.0009 (9)
C12	0.0189 (12)	0.0157 (11)	0.0151 (11)	0.0012 (9)	0.0025 (9)	0.0014 (8)
C13	0.0172 (12)	0.0191 (11)	0.0149 (11)	0.0017 (9)	0.0002 (9)	−0.0045 (9)
C14	0.0202 (12)	0.0184 (11)	0.0175 (12)	0.0003 (9)	0.0015 (9)	−0.0047 (9)
C15A	0.0181 (13)	0.0272 (13)	0.0304 (14)	−0.0002 (10)	−0.0025 (10)	−0.0156 (11)
F1A	0.0217 (10)	0.0360 (10)	0.0424 (11)	−0.0107 (8)	−0.0036 (8)	−0.0071 (8)
C15B	0.0181 (13)	0.0272 (13)	0.0304 (14)	−0.0002 (10)	−0.0025 (10)	−0.0156 (11)
C16	0.0300 (15)	0.0291 (14)	0.0240 (13)	0.0119 (11)	−0.0108 (11)	−0.0091 (11)
C17A	0.0320 (15)	0.0277 (13)	0.0219 (13)	0.0057 (11)	−0.0043 (11)	−0.0012 (11)
C17B	0.0320 (15)	0.0277 (13)	0.0219 (13)	0.0057 (11)	−0.0043 (11)	−0.0012 (11)
F1B	0.040 (6)	0.037 (5)	0.024 (5)	−0.005 (4)	−0.017 (4)	0.000 (4)
C18	0.0218 (13)	0.0219 (12)	0.0176 (12)	−0.0013 (10)	−0.0001 (9)	−0.0003 (9)
C19	0.0306 (14)	0.0180 (11)	0.0222 (13)	−0.0029 (10)	0.0011 (10)	0.0005 (10)

Br1—C6	1.899 (2)	C9—C10	1.361 (3)
S1—O2	1.4912 (16)	C9—H9	0.9500
S1—C1	1.773 (2)	C10—C11	1.393 (3)
S1—C19	1.795 (2)	C10—H10	0.9500
O1—C12	1.365 (2)	C12—C13	1.463 (3)
O1—C11	1.369 (3)	C13—C18	1.391 (3)
C1—C12	1.364 (3)	C13—C14	1.393 (3)
C1—C2	1.449 (3)	C14—C15A	1.373 (3)
C2—C11	1.382 (3)	C14—H14	0.9500
C2—C3	1.428 (3)	C15A—F1A	1.335 (3)
C3—C4	1.409 (3)	C15A—C16	1.370 (4)
C3—C8	1.426 (3)	C16—C17A	1.379 (4)
C4—C5	1.369 (3)	C16—H16	0.9500
C4—H4	0.9500	C17A—C18	1.375 (3)
C5—C6	1.403 (3)	C17A—H17A	0.9500
C5—H5	0.9500	C18—H18	0.9500
C6—C7	1.355 (3)	C19—H19A	0.9800
C7—C8	1.412 (3)	C19—H19B	0.9800
C7—H7	0.9500	C19—H19C	0.9800
C8—C9	1.424 (3)
O2—S1—C1	108.36 (10)	C9—C10—H10	121.9
O2—S1—C19	106.48 (11)	C11—C10—H10	121.9
C1—S1—C19	98.85 (11)	O1—C11—C2	111.47 (19)
C12—O1—C11	106.47 (17)	O1—C11—C10	122.9 (2)
C12—C1—C2	107.00 (18)	C2—C11—C10	125.6 (2)
C12—C1—S1	121.46 (17)	C1—C12—O1	110.71 (19)
C2—C1—S1	131.36 (16)	C1—C12—C13	134.5 (2)
C11—C2—C3	118.51 (19)	O1—C12—C13	114.64 (18)
C11—C2—C1	104.32 (19)	C18—C13—C14	119.8 (2)
C3—C2—C1	137.10 (19)	C18—C13—C12	120.6 (2)
C4—C3—C8	118.3 (2)	C14—C13—C12	119.5 (2)
C4—C3—C2	124.92 (19)	C15A—C14—C13	118.1 (2)
C8—C3—C2	116.73 (19)	C15A—C14—H14	120.9
C5—C4—C3	121.5 (2)	C13—C14—H14	120.9
C5—C4—H4	119.3	F1A—C15A—C16	117.0 (2)
C3—C4—H4	119.3	F1A—C15A—C14	119.6 (2)
C4—C5—C6	119.0 (2)	C16—C15A—C14	123.4 (2)
C4—C5—H5	120.5	C15A—C16—C17A	117.4 (2)
C6—C5—H5	120.5	C15A—C16—H16	121.3
C7—C6—C5	122.0 (2)	C17A—C16—H16	121.3
C7—C6—Br1	118.98 (17)	C18—C17A—C16	121.7 (2)
C5—C6—Br1	118.93 (17)	C18—C17A—H17A	119.2
C6—C7—C8	119.9 (2)	C16—C17A—H17A	119.2
C6—C7—H7	120.1	C17A—C18—C13	119.6 (2)
C8—C7—H7	120.1	C17A—C18—H18	120.2
C7—C8—C9	119.8 (2)	C13—C18—H18	120.2
C7—C8—C3	119.3 (2)	S1—C19—H19A	109.5
C9—C8—C3	121.0 (2)	S1—C19—H19B	109.5
C10—C9—C8	121.9 (2)	H19A—C19—H19B	109.5
C10—C9—H9	119.1	S1—C19—H19C	109.5
C8—C9—H9	119.1	H19A—C19—H19C	109.5
C9—C10—C11	116.3 (2)	H19B—C19—H19C	109.5
O2—S1—C1—C12	−136.65 (19)	C12—O1—C11—C2	−1.1 (3)
C19—S1—C1—C12	112.6 (2)	C12—O1—C11—C10	175.8 (2)
O2—S1—C1—C2	37.8 (2)	C3—C2—C11—O1	177.72 (19)
C19—S1—C1—C2	−73.0 (2)	C1—C2—C11—O1	0.1 (2)
C12—C1—C2—C11	0.9 (2)	C3—C2—C11—C10	1.0 (4)
S1—C1—C2—C11	−174.17 (18)	C1—C2—C11—C10	−176.6 (2)
C12—C1—C2—C3	−176.0 (3)	C9—C10—C11—O1	−175.0 (2)
S1—C1—C2—C3	9.0 (4)	C9—C10—C11—C2	1.4 (4)
C11—C2—C3—C4	177.0 (2)	C2—C1—C12—O1	−1.6 (3)
C1—C2—C3—C4	−6.4 (4)	S1—C1—C12—O1	174.03 (15)
C11—C2—C3—C8	−3.0 (3)	C2—C1—C12—C13	173.1 (2)
C1—C2—C3—C8	173.5 (2)	S1—C1—C12—C13	−11.2 (4)
C8—C3—C4—C5	−0.3 (3)	C11—O1—C12—C1	1.7 (3)
C2—C3—C4—C5	179.7 (2)	C11—O1—C12—C13	−174.20 (19)
C3—C4—C5—C6	−0.6 (4)	C1—C12—C13—C18	−34.8 (4)
C4—C5—C6—C7	1.0 (4)	O1—C12—C13—C18	139.7 (2)
C4—C5—C6—Br1	178.65 (18)	C1—C12—C13—C14	149.5 (3)
C5—C6—C7—C8	−0.6 (4)	O1—C12—C13—C14	−35.9 (3)
Br1—C6—C7—C8	−178.20 (17)	C18—C13—C14—C15A	2.0 (3)
C6—C7—C8—C9	177.6 (2)	C12—C13—C14—C15A	177.7 (2)
C6—C7—C8—C3	−0.3 (4)	C13—C14—C15A—F1A	−179.3 (2)
C4—C3—C8—C7	0.7 (3)	C13—C14—C15A—C16	−0.4 (4)
C2—C3—C8—C7	−179.2 (2)	F1A—C15A—C16—C17A	177.9 (2)
C4—C3—C8—C9	−177.1 (2)	C14—C15A—C16—C17A	−1.1 (4)
C2—C3—C8—C9	2.9 (3)	C15A—C16—C17A—C18	0.9 (4)
C7—C8—C9—C10	−178.4 (2)	C16—C17A—C18—C13	0.7 (4)
C3—C8—C9—C10	−0.6 (4)	C14—C13—C18—C17A	−2.2 (3)
C8—C9—C10—C11	−1.6 (3)	C12—C13—C18—C17A	−177.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O2i	0.95	2.48	3.260 (3)	139
C19—H19B···O2i	0.98	2.56	3.387 (3)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯O2i	0.95	2.48	3.260 (3)	139
C19—H19B⋯O2i	0.98	2.56	3.387 (3)	142

Symmetry code: (i) .