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The title compound, C19H13BrOS, was synthesized by the Lewis acid-catalyzed reaction of 2-naphthol with 4′-bromo-2-chloro-2-(methyl­sulfan­yl)acetophenone. The methyl group lies above the naphthofuran ring system and the benzene ring is rotated out of the naphthofuran plane with a dihedral angle of 42.29 (8)°. The crystal structure is stabilized by aromatic π–π stacking between the furan and benzene rings, C—H...O and C—H...Br hydrogen bonds, and a Br...Br inter­action.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022180/sj2304sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022180/sj2304Isup2.hkl
Contains datablock I

CCDC reference: 651571

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.026
  • wR factor = 0.071
  • Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.09 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 100 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT480_ALERT_4_C Long H...A H-Bond Reported H9 .. O .. 2.70 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H19A .. BR .. 3.01 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Naphthofuran compounds have attracted widespread interest in view of their biological and pharmacological activities (Goel & Dixit, 2004; Hagiwara et al., 1999; Piloto et al., 2005). As part of our ongoing work on the synthesis and structures of naphthofuran derivatives, the crystal structures of 1-methylsulfinyl-2-phenylnaphtho[2,1-b]furan (Choi, Seo, Kang et al., 2006) and 7-bromo-1-methylsulfanyl-2-phenylnaphtho[2,1-b]furan (Choi, Seo, Son & Lee, 2006) have been described to the literature. Herein we report the molecular and crystal structure of the title compound (I) (Fig. 1).

The naphthofuran unit is essentially planar, with a mean deviation of 0.049 Å from the least-squares plane defined by the thirteen constituent atoms. The dihedral angle in (I) formed by the plane of the naphthofuran ring and the plane of phenyl ring is 42.29 (8)°. The molecular packing (Fig. 2) is stabilized by aromatic ππ stacking interactions between adjacent naphthofuran units. The Cg1···Cg2 i distance is 3.649 (3) Å (Cg1 and Cg2 are the centroids of the C1/C2/O/C3/C12 and C6—C11 rings; symmetry code as in Fig. 2). Further stability comes from weak C—H···O and C—H···Br hydrogen bonds in Table 1, and a Br···Br interaction at 3.6890 (6) Å.

Related literature top

For the crystal structures of the isomers of the title compound, see: Choi, Seo, Kang et al. (2006) and Choi, Seo, Son & Lee (2006). For details of the biological and pharmacological activity of naphthofuran compounds, see: Goel & Dixit (2004); Hagiwara et al. (1999); Piloto et al. (2005).

Experimental top

Zinc chloride (273 mg, 2.0 mmol) was added at room temperature to a stirred solution of 2-naphthol (288 mg, 2.0 mmol) and 4'-bromo-2-chloro-2-(methylsulfanyl)acetophenone (559 mg, 2.0 mmol) in CH2Cl2 (30 ml), and stirred for 40 min. The mixture was quenched with water and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by column chromatography (CCl4) to afford the title compound as white needles (450 mg, 61%). M.p. 411–412 K). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of title compound (I) in benzene at room temperature.

Refinement top

All H atoms were geometrically located in ideal positions and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms and C—H=0.98 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and Uiso(H) = 1.5Ueq(C) for methyl H atoms. The highest peak in the difference map is 0.97 Å from Br and the largest hole is 1.00 Å from Br.

Structure description top

Naphthofuran compounds have attracted widespread interest in view of their biological and pharmacological activities (Goel & Dixit, 2004; Hagiwara et al., 1999; Piloto et al., 2005). As part of our ongoing work on the synthesis and structures of naphthofuran derivatives, the crystal structures of 1-methylsulfinyl-2-phenylnaphtho[2,1-b]furan (Choi, Seo, Kang et al., 2006) and 7-bromo-1-methylsulfanyl-2-phenylnaphtho[2,1-b]furan (Choi, Seo, Son & Lee, 2006) have been described to the literature. Herein we report the molecular and crystal structure of the title compound (I) (Fig. 1).

The naphthofuran unit is essentially planar, with a mean deviation of 0.049 Å from the least-squares plane defined by the thirteen constituent atoms. The dihedral angle in (I) formed by the plane of the naphthofuran ring and the plane of phenyl ring is 42.29 (8)°. The molecular packing (Fig. 2) is stabilized by aromatic ππ stacking interactions between adjacent naphthofuran units. The Cg1···Cg2 i distance is 3.649 (3) Å (Cg1 and Cg2 are the centroids of the C1/C2/O/C3/C12 and C6—C11 rings; symmetry code as in Fig. 2). Further stability comes from weak C—H···O and C—H···Br hydrogen bonds in Table 1, and a Br···Br interaction at 3.6890 (6) Å.

For the crystal structures of the isomers of the title compound, see: Choi, Seo, Kang et al. (2006) and Choi, Seo, Son & Lee (2006). For details of the biological and pharmacological activity of naphthofuran compounds, see: Goel & Dixit (2004); Hagiwara et al. (1999); Piloto et al. (2005).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97-2 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97-2 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97-2.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. ππ interactions in (I). Cg denotes ring centroids. [Symmetry code: (i) 2 - x, 1 - y, 1 - z.]
2-(4-Bromophenyl)-1-(methylsulfanyl)naphtho[2,1-b]furan top
Crystal data top
C19H13BrOSZ = 2
Mr = 369.26F(000) = 372
Triclinic, P1Dx = 1.645 Mg m3
Hall symbol: -P 1Melting point = 411–412 K
a = 9.359 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.487 (1) ÅCell parameters from 4258 reflections
c = 9.860 (1) Åθ = 2.3–28.2°
α = 94.352 (2)°µ = 2.90 mm1
β = 115.271 (2)°T = 173 K
γ = 105.312 (2)°Block, colorless
V = 745.50 (14) Å30.53 × 0.42 × 0.35 mm
Data collection top
Bruker SMART CCD
diffractometer
2878 independent reflections
Radiation source: fine-focus sealed tube2644 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
Detector resolution: 10.00 pixels mm-1θmax = 26.0°, θmin = 2.3°
φ and ω scansh = 1111
Absorption correction: multi-scan
SADABS (Sheldrick, 1999)
k = 1111
Tmin = 0.239, Tmax = 0.371l = 1212
5896 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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0402P)2 + 0.3452P]
where P = (Fo2 + 2Fc2)/3
2878 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.72 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C19H13BrOSγ = 105.312 (2)°
Mr = 369.26V = 745.50 (14) Å3
Triclinic, P1Z = 2
a = 9.359 (1) ÅMo Kα radiation
b = 9.487 (1) ŵ = 2.90 mm1
c = 9.860 (1) ÅT = 173 K
α = 94.352 (2)°0.53 × 0.42 × 0.35 mm
β = 115.271 (2)°
Data collection top
Bruker SMART CCD
diffractometer
2878 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 1999)
2644 reflections with I > 2σ(I)
Tmin = 0.239, Tmax = 0.371Rint = 0.021
5896 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.071H-atom parameters constrained
S = 1.04Δρmax = 0.72 e Å3
2878 reflectionsΔρmin = 0.35 e Å3
199 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Br0.20442 (3)0.97204 (2)0.56099 (3)0.03172 (10)
S0.91609 (6)0.70175 (5)0.72850 (6)0.02278 (13)
O0.56320 (17)0.44038 (16)0.80420 (16)0.0229 (3)
C10.7820 (2)0.5608 (2)0.7661 (2)0.0201 (4)
C20.6367 (2)0.5661 (2)0.7640 (2)0.0214 (4)
C30.6644 (2)0.3531 (2)0.8272 (2)0.0216 (4)
C40.6264 (3)0.2104 (2)0.8593 (2)0.0246 (4)
H40.53050.16870.87280.030*
C50.7350 (3)0.1345 (2)0.8700 (2)0.0263 (5)
H50.71220.03630.88860.032*
C60.8815 (3)0.1983 (2)0.8540 (2)0.0234 (4)
C70.9922 (3)0.1173 (2)0.8657 (2)0.0282 (5)
H70.96520.01740.87960.034*
C81.1365 (3)0.1793 (3)0.8574 (2)0.0304 (5)
H81.20990.12350.86760.037*
C91.1769 (3)0.3259 (3)0.8338 (2)0.0278 (5)
H91.27830.36930.82950.033*
C101.0704 (3)0.4066 (2)0.8168 (2)0.0241 (4)
H101.09810.50470.79880.029*
C110.9206 (2)0.3460 (2)0.8258 (2)0.0202 (4)
C120.8019 (2)0.4214 (2)0.8082 (2)0.0197 (4)
C130.5404 (2)0.6688 (2)0.7216 (2)0.0218 (4)
C140.4509 (3)0.6956 (2)0.7985 (2)0.0240 (4)
H140.45850.65150.88360.029*
C150.3515 (3)0.7858 (2)0.7518 (2)0.0253 (4)
H150.29180.80420.80480.030*
C160.3406 (2)0.8483 (2)0.6275 (2)0.0236 (4)
C170.4267 (3)0.8236 (2)0.5482 (2)0.0239 (4)
H170.41730.86730.46250.029*
C180.5266 (3)0.7343 (2)0.5961 (2)0.0239 (4)
H180.58660.71720.54300.029*
C190.8666 (3)0.6152 (3)0.5368 (3)0.0325 (5)
H19A0.93380.68290.49980.049*
H19B0.74750.59470.46790.049*
H19C0.89160.52110.53900.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.02759 (14)0.03285 (15)0.03671 (15)0.01813 (10)0.01196 (10)0.00744 (10)
S0.0213 (3)0.0187 (3)0.0288 (3)0.0045 (2)0.0135 (2)0.0039 (2)
O0.0213 (7)0.0222 (7)0.0292 (8)0.0080 (6)0.0147 (6)0.0064 (6)
C10.0203 (10)0.0186 (10)0.0220 (10)0.0057 (8)0.0110 (8)0.0027 (8)
C20.0223 (10)0.0193 (10)0.0228 (10)0.0057 (8)0.0116 (8)0.0029 (8)
C30.0219 (10)0.0214 (10)0.0211 (10)0.0078 (8)0.0095 (8)0.0027 (8)
C40.0240 (10)0.0236 (11)0.0233 (10)0.0032 (8)0.0112 (9)0.0039 (8)
C50.0317 (11)0.0193 (10)0.0240 (11)0.0055 (9)0.0111 (9)0.0053 (8)
C60.0267 (10)0.0227 (10)0.0182 (9)0.0092 (8)0.0078 (8)0.0026 (8)
C70.0394 (12)0.0236 (11)0.0227 (10)0.0162 (10)0.0116 (9)0.0061 (9)
C80.0356 (12)0.0365 (13)0.0268 (11)0.0238 (10)0.0140 (10)0.0079 (10)
C90.0251 (11)0.0377 (13)0.0259 (11)0.0154 (9)0.0135 (9)0.0071 (9)
C100.0256 (10)0.0247 (11)0.0241 (10)0.0107 (9)0.0118 (9)0.0060 (8)
C110.0219 (10)0.0196 (10)0.0182 (9)0.0079 (8)0.0083 (8)0.0012 (8)
C120.0227 (10)0.0173 (10)0.0184 (9)0.0057 (8)0.0098 (8)0.0014 (7)
C130.0188 (9)0.0201 (10)0.0257 (10)0.0065 (8)0.0101 (8)0.0020 (8)
C140.0229 (10)0.0258 (11)0.0256 (10)0.0082 (8)0.0133 (9)0.0048 (8)
C150.0211 (10)0.0287 (11)0.0285 (11)0.0092 (9)0.0134 (9)0.0028 (9)
C160.0180 (10)0.0203 (10)0.0283 (11)0.0062 (8)0.0079 (8)0.0004 (8)
C170.0229 (10)0.0229 (10)0.0241 (10)0.0071 (8)0.0100 (9)0.0034 (8)
C180.0233 (10)0.0243 (11)0.0264 (10)0.0084 (8)0.0135 (9)0.0028 (8)
C190.0343 (12)0.0369 (13)0.0283 (12)0.0069 (10)0.0196 (10)0.0039 (10)
Geometric parameters (Å, º) top
Br—C161.904 (2)C8—H80.9500
S—C11.757 (2)C9—C101.374 (3)
S—C191.810 (2)C9—H90.9500
O—C31.376 (2)C10—C111.412 (3)
O—C21.387 (2)C10—H100.9500
C1—C21.365 (3)C11—C121.431 (3)
C1—C121.449 (3)C13—C181.399 (3)
C2—C131.463 (3)C13—C141.402 (3)
C3—C121.377 (3)C14—C151.387 (3)
C3—C41.402 (3)C14—H140.9500
C4—C51.367 (3)C15—C161.378 (3)
C4—H40.9500C15—H150.9500
C5—C61.425 (3)C16—C171.388 (3)
C5—H50.9500C17—C181.385 (3)
C6—C71.419 (3)C17—H170.9500
C6—C111.432 (3)C18—H180.9500
C7—C81.363 (3)C19—H19A0.9800
C7—H70.9500C19—H19B0.9800
C8—C91.406 (3)C19—H19C0.9800
C1—S—C19100.23 (10)C11—C10—H10119.5
C3—O—C2105.97 (15)C10—C11—C12124.79 (19)
C2—C1—C12106.68 (17)C10—C11—C6118.69 (19)
C2—C1—S124.75 (16)C12—C11—C6116.51 (18)
C12—C1—S128.55 (15)C3—C12—C11119.16 (18)
C1—C2—O110.67 (17)C3—C12—C1105.39 (17)
C1—C2—C13134.46 (19)C11—C12—C1135.40 (18)
O—C2—C13114.78 (17)C18—C13—C14118.57 (19)
O—C3—C12111.26 (18)C18—C13—C2120.25 (18)
O—C3—C4123.56 (18)C14—C13—C2121.04 (19)
C12—C3—C4125.13 (19)C15—C14—C13120.83 (19)
C5—C4—C3116.29 (19)C15—C14—H14119.6
C5—C4—H4121.9C13—C14—H14119.6
C3—C4—H4121.9C16—C15—C14119.06 (19)
C4—C5—C6122.0 (2)C16—C15—H15120.5
C4—C5—H5119.0C14—C15—H15120.5
C6—C5—H5119.0C15—C16—C17121.69 (19)
C7—C6—C5120.9 (2)C15—C16—Br119.84 (16)
C7—C6—C11118.3 (2)C17—C16—Br118.46 (16)
C5—C6—C11120.81 (19)C18—C17—C16118.9 (2)
C8—C7—C6121.5 (2)C18—C17—H17120.5
C8—C7—H7119.2C16—C17—H17120.5
C6—C7—H7119.2C17—C18—C13120.94 (19)
C7—C8—C9120.0 (2)C17—C18—H18119.5
C7—C8—H8120.0C13—C18—H18119.5
C9—C8—H8120.0S—C19—H19A109.5
C10—C9—C8120.3 (2)S—C19—H19B109.5
C10—C9—H9119.8H19A—C19—H19B109.5
C8—C9—H9119.8S—C19—H19C109.5
C9—C10—C11121.0 (2)H19A—C19—H19C109.5
C9—C10—H10119.5H19B—C19—H19C109.5
C19—S—C1—C2104.63 (19)O—C3—C12—C11179.22 (16)
C19—S—C1—C1277.0 (2)C4—C3—C12—C111.8 (3)
C12—C1—C2—O0.9 (2)O—C3—C12—C11.5 (2)
S—C1—C2—O177.72 (14)C4—C3—C12—C1175.89 (19)
C12—C1—C2—C13175.2 (2)C10—C11—C12—C3176.75 (19)
S—C1—C2—C136.1 (3)C6—C11—C12—C33.4 (3)
C3—O—C2—C11.8 (2)C10—C11—C12—C16.5 (4)
C3—O—C2—C13175.11 (16)C6—C11—C12—C1173.4 (2)
C2—O—C3—C122.1 (2)C2—C1—C12—C30.4 (2)
C2—O—C3—C4175.38 (19)S—C1—C12—C3178.95 (15)
O—C3—C4—C5176.22 (18)C2—C1—C12—C11177.5 (2)
C12—C3—C4—C50.9 (3)S—C1—C12—C113.9 (3)
C3—C4—C5—C61.8 (3)C1—C2—C13—C1837.9 (3)
C4—C5—C6—C7180.0 (2)O—C2—C13—C18138.13 (19)
C4—C5—C6—C110.0 (3)C1—C2—C13—C14146.5 (2)
C5—C6—C7—C8177.0 (2)O—C2—C13—C1437.4 (3)
C11—C6—C7—C82.9 (3)C18—C13—C14—C150.3 (3)
C6—C7—C8—C91.3 (3)C2—C13—C14—C15175.99 (19)
C7—C8—C9—C100.9 (3)C13—C14—C15—C160.5 (3)
C8—C9—C10—C111.3 (3)C14—C15—C16—C170.1 (3)
C9—C10—C11—C12179.43 (19)C14—C15—C16—Br179.83 (15)
C9—C10—C11—C60.4 (3)C15—C16—C17—C180.3 (3)
C7—C6—C11—C102.4 (3)Br—C16—C17—C18179.75 (15)
C5—C6—C11—C10177.53 (19)C16—C17—C18—C130.4 (3)
C7—C6—C11—C12177.40 (18)C14—C13—C18—C170.1 (3)
C5—C6—C11—C122.6 (3)C2—C13—C18—C17175.60 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···Oi0.952.703.635 (3)170
C19—H19A···Bri0.983.013.885 (3)149
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC19H13BrOS
Mr369.26
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)9.359 (1), 9.487 (1), 9.860 (1)
α, β, γ (°)94.352 (2), 115.271 (2), 105.312 (2)
V3)745.50 (14)
Z2
Radiation typeMo Kα
µ (mm1)2.90
Crystal size (mm)0.53 × 0.42 × 0.35
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
SADABS (Sheldrick, 1999)
Tmin, Tmax0.239, 0.371
No. of measured, independent and
observed [I > 2σ(I)] reflections
5896, 2878, 2644
Rint0.021
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.071, 1.04
No. of reflections2878
No. of parameters199
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.72, 0.35

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97-2 (Sheldrick, 1997), SHELXL97-2 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXL97-2.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···Oi0.952.703.635 (3)169.5
C19—H19A···Bri0.983.013.885 (3)149.0
Symmetry code: (i) x+1, y, z.
 

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