organic compounds
2,5-Dimethyl-3-phenylsulfonyl-1-benzofuran
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
The title compound, C16H14O3S, was prepared by the oxidation of 2,5-dimethyl-3-phenylsulfanyl-1-benzofuran with 3-chloroperoxybenzoic acid. The phenyl ring makes a dihedral angle of 76.98 (9)° with the plane of the benzofuran fragment. The is stabilized by π–π interactions between furan and benzene rings of neighbouring molecules [centroid–centroid distance = 3.775 (4) Å]. In addition, the exhibits intra- and intermolecular C—H⋯O interactions.
Related literature
For the crystal structures of similar 3-phenylsulfonyl-1-benzofuran derivatives, see: Choi et al. (2008a,b).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: SMART (Bruker, 2001); cell 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
10.1107/S1600536808009811/sj2482sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808009811/sj2482Isup2.hkl
3-Chloroperoxybenzoic acid (77%, 717 mg, 3.2 mmol) was added in small portions to a stirred solution of 2,5-dimethyl 3-phenylsulfanyl-1-benzofuran (381 mg, 1.5 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 4 h at room temperature, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by δ 2.45 (s, 3H), 2.79 (s, 3H), 7.10 (d, J = 8.44 Hz, 1H), 7.29 (d, J = 8.44 Hz, 1H), 7.47–7.60 (m, 3H), 7.67 (s, 1H), 7.97–8.03 (m, 2H); EI—MS 286 [M+].
(hexane-ethyl acetate, 2: 1 v/v) to afford the title compound as a colorless solid [yield 83%, m.p. 411–412 K; Rf = 0.67 (hexane-ethyl acetate, 2: 1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in benzene at room temperature. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz)All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms and 0.96 Å for methyl H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic and 1.5Ueq(C) for methyl H atoms.
Data collection: SMART (Bruker, 2001); cell
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).C16H14O3S | Z = 2 |
Mr = 286.33 | F(000) = 300 |
Triclinic, P1 | Dx = 1.362 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.476 (4) Å | Cell parameters from 2576 reflections |
b = 9.448 (5) Å | θ = 2.5–28.2° |
c = 11.283 (6) Å | µ = 0.24 mm−1 |
α = 110.834 (8)° | T = 298 K |
β = 95.651 (9)° | Block, colorless |
γ = 106.122 (9)° | 0.40 × 0.40 × 0.20 mm |
V = 698.0 (6) Å3 |
Bruker SMART CCD diffractometer | 1967 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.077 |
Graphite monochromator | θmax = 25.5°, θmin = 2.0° |
Detector resolution: 10.0 pixels mm-1 | h = −9→9 |
ϕ and ω scans | k = −11→11 |
4916 measured reflections | l = −13→13 |
2560 independent 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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0708P)2 + 0.3092P] where P = (Fo2 + 2Fc2)/3 |
2560 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C16H14O3S | γ = 106.122 (9)° |
Mr = 286.33 | V = 698.0 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.476 (4) Å | Mo Kα radiation |
b = 9.448 (5) Å | µ = 0.24 mm−1 |
c = 11.283 (6) Å | T = 298 K |
α = 110.834 (8)° | 0.40 × 0.40 × 0.20 mm |
β = 95.651 (9)° |
Bruker SMART CCD diffractometer | 1967 reflections with I > 2σ(I) |
4916 measured reflections | Rint = 0.077 |
2560 independent reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.33 e Å−3 |
2560 reflections | Δρmin = −0.33 e Å−3 |
181 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S | 0.48253 (10) | 0.09684 (9) | 0.28377 (7) | 0.0479 (3) | |
O1 | 0.7729 (3) | 0.5526 (2) | 0.3996 (2) | 0.0621 (6) | |
O2 | 0.3828 (3) | 0.0486 (3) | 0.37248 (19) | 0.0587 (6) | |
O3 | 0.3765 (3) | 0.0689 (3) | 0.1608 (2) | 0.0660 (6) | |
C1 | 0.6127 (4) | 0.2991 (3) | 0.3636 (3) | 0.0469 (7) | |
C2 | 0.6846 (4) | 0.3858 (3) | 0.5024 (3) | 0.0457 (7) | |
C3 | 0.6797 (4) | 0.3508 (3) | 0.6115 (3) | 0.0492 (7) | |
H3 | 0.6177 | 0.2466 | 0.6032 | 0.059* | |
C4 | 0.7678 (5) | 0.4719 (4) | 0.7328 (3) | 0.0585 (8) | |
C5 | 0.8626 (5) | 0.6271 (4) | 0.7433 (4) | 0.0672 (9) | |
H5 | 0.9217 | 0.7078 | 0.8254 | 0.081* | |
C6 | 0.8716 (5) | 0.6647 (4) | 0.6369 (4) | 0.0679 (10) | |
H6 | 0.9349 | 0.7686 | 0.6452 | 0.082* | |
C7 | 0.7827 (4) | 0.5416 (3) | 0.5174 (3) | 0.0523 (8) | |
C8 | 0.6696 (4) | 0.4052 (4) | 0.3078 (3) | 0.0551 (8) | |
C9 | 0.6558 (4) | 0.0025 (3) | 0.2563 (3) | 0.0453 (7) | |
C10 | 0.7288 (5) | −0.0414 (4) | 0.3494 (3) | 0.0573 (8) | |
H10 | 0.6869 | −0.0227 | 0.4266 | 0.069* | |
C11 | 0.8658 (6) | −0.1138 (4) | 0.3250 (5) | 0.0807 (12) | |
H11 | 0.9164 | −0.1452 | 0.3862 | 0.097* | |
C12 | 0.9277 (6) | −0.1397 (4) | 0.2115 (5) | 0.0897 (14) | |
H12 | 1.0212 | −0.1875 | 0.1965 | 0.108* | |
C13 | 0.8531 (6) | −0.0959 (5) | 0.1201 (4) | 0.0846 (13) | |
H13 | 0.8956 | −0.1144 | 0.0430 | 0.102* | |
C14 | 0.7170 (5) | −0.0252 (4) | 0.1413 (3) | 0.0609 (9) | |
H14 | 0.6658 | 0.0042 | 0.0789 | 0.073* | |
C15 | 0.7617 (6) | 0.4376 (5) | 0.8531 (3) | 0.0803 (11) | |
H15A | 0.8192 | 0.3571 | 0.8480 | 0.096* | |
H15B | 0.6315 | 0.3995 | 0.8596 | 0.096* | |
H15C | 0.8307 | 0.5343 | 0.9283 | 0.096* | |
C16 | 0.6474 (6) | 0.3918 (5) | 0.1724 (4) | 0.0784 (11) | |
H16A | 0.7708 | 0.4175 | 0.1517 | 0.094* | |
H16B | 0.5864 | 0.4652 | 0.1627 | 0.094* | |
H16C | 0.5708 | 0.2839 | 0.1146 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S | 0.0448 (4) | 0.0527 (4) | 0.0352 (4) | 0.0039 (3) | 0.0014 (3) | 0.0167 (3) |
O1 | 0.0632 (13) | 0.0498 (12) | 0.0805 (17) | 0.0183 (10) | 0.0197 (12) | 0.0338 (12) |
O2 | 0.0548 (12) | 0.0617 (13) | 0.0447 (13) | 0.0014 (10) | 0.0117 (10) | 0.0183 (10) |
O3 | 0.0587 (12) | 0.0829 (16) | 0.0470 (14) | 0.0146 (12) | −0.0054 (11) | 0.0268 (12) |
C1 | 0.0428 (14) | 0.0491 (16) | 0.0488 (18) | 0.0137 (12) | 0.0075 (13) | 0.0217 (14) |
C2 | 0.0395 (13) | 0.0424 (15) | 0.0505 (18) | 0.0135 (11) | 0.0072 (13) | 0.0141 (13) |
C3 | 0.0510 (15) | 0.0442 (15) | 0.0435 (18) | 0.0126 (13) | 0.0034 (14) | 0.0118 (13) |
C4 | 0.0577 (17) | 0.0580 (19) | 0.050 (2) | 0.0242 (15) | 0.0027 (15) | 0.0097 (15) |
C5 | 0.0649 (19) | 0.0506 (18) | 0.060 (2) | 0.0172 (16) | −0.0003 (17) | −0.0023 (16) |
C6 | 0.0588 (19) | 0.0379 (16) | 0.089 (3) | 0.0111 (14) | 0.0075 (19) | 0.0111 (17) |
C7 | 0.0473 (15) | 0.0450 (16) | 0.066 (2) | 0.0183 (13) | 0.0126 (15) | 0.0221 (15) |
C8 | 0.0525 (17) | 0.0607 (19) | 0.061 (2) | 0.0214 (15) | 0.0129 (15) | 0.0324 (17) |
C9 | 0.0481 (14) | 0.0387 (13) | 0.0333 (15) | 0.0015 (11) | −0.0006 (12) | 0.0089 (11) |
C10 | 0.0599 (18) | 0.0500 (17) | 0.0522 (19) | 0.0051 (15) | −0.0004 (15) | 0.0228 (15) |
C11 | 0.075 (2) | 0.052 (2) | 0.103 (3) | 0.0119 (18) | −0.013 (2) | 0.032 (2) |
C12 | 0.074 (2) | 0.051 (2) | 0.121 (4) | 0.0243 (19) | 0.013 (3) | 0.007 (2) |
C13 | 0.092 (3) | 0.064 (2) | 0.076 (3) | 0.023 (2) | 0.030 (2) | 0.002 (2) |
C14 | 0.072 (2) | 0.0576 (19) | 0.0381 (17) | 0.0135 (16) | 0.0081 (16) | 0.0098 (14) |
C15 | 0.098 (3) | 0.080 (3) | 0.047 (2) | 0.034 (2) | −0.003 (2) | 0.0103 (18) |
C16 | 0.087 (3) | 0.089 (3) | 0.078 (3) | 0.028 (2) | 0.020 (2) | 0.056 (2) |
S—O3 | 1.425 (2) | C8—C16 | 1.476 (4) |
S—O2 | 1.431 (2) | C9—C10 | 1.376 (4) |
S—C1 | 1.726 (3) | C9—C14 | 1.380 (4) |
S—C9 | 1.758 (3) | C10—C11 | 1.380 (5) |
O1—C8 | 1.353 (4) | C10—H10 | 0.9300 |
O1—C7 | 1.366 (4) | C11—C12 | 1.367 (6) |
C1—C8 | 1.359 (4) | C11—H11 | 0.9300 |
C1—C2 | 1.446 (4) | C12—C13 | 1.366 (6) |
C2—C3 | 1.385 (4) | C12—H12 | 0.9300 |
C2—C7 | 1.389 (4) | C13—C14 | 1.360 (6) |
C3—C4 | 1.381 (4) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.396 (5) | C15—H15A | 0.9600 |
C4—C15 | 1.505 (5) | C15—H15B | 0.9600 |
C5—C6 | 1.370 (5) | C15—H15C | 0.9600 |
C5—H5 | 0.9300 | C16—H16A | 0.9600 |
C6—C7 | 1.375 (5) | C16—H16B | 0.9600 |
C6—H6 | 0.9300 | C16—H16C | 0.9600 |
O3—S—O2 | 118.96 (14) | C10—C9—C14 | 121.2 (3) |
O3—S—C1 | 109.04 (14) | C10—C9—S | 119.9 (2) |
O2—S—C1 | 107.44 (13) | C14—C9—S | 119.0 (3) |
O3—S—C9 | 108.12 (14) | C9—C10—C11 | 118.3 (3) |
O2—S—C9 | 107.90 (14) | C9—C10—H10 | 120.9 |
C1—S—C9 | 104.45 (14) | C11—C10—H10 | 120.9 |
C8—O1—C7 | 107.4 (2) | C12—C11—C10 | 120.5 (4) |
C8—C1—C2 | 107.5 (3) | C12—C11—H11 | 119.8 |
C8—C1—S | 126.5 (3) | C10—C11—H11 | 119.8 |
C2—C1—S | 126.0 (2) | C13—C12—C11 | 120.4 (4) |
C3—C2—C7 | 119.1 (3) | C13—C12—H12 | 119.8 |
C3—C2—C1 | 136.9 (3) | C11—C12—H12 | 119.8 |
C7—C2—C1 | 104.0 (3) | C14—C13—C12 | 120.3 (4) |
C4—C3—C2 | 119.4 (3) | C14—C13—H13 | 119.8 |
C4—C3—H3 | 120.3 | C12—C13—H13 | 119.8 |
C2—C3—H3 | 120.3 | C13—C14—C9 | 119.4 (4) |
C3—C4—C5 | 119.4 (3) | C13—C14—H14 | 120.3 |
C3—C4—C15 | 120.5 (3) | C9—C14—H14 | 120.3 |
C5—C4—C15 | 120.1 (3) | C4—C15—H15A | 109.5 |
C6—C5—C4 | 122.4 (3) | C4—C15—H15B | 109.5 |
C6—C5—H5 | 118.8 | H15A—C15—H15B | 109.5 |
C4—C5—H5 | 118.8 | C4—C15—H15C | 109.5 |
C5—C6—C7 | 116.9 (3) | H15A—C15—H15C | 109.5 |
C5—C6—H6 | 121.6 | H15B—C15—H15C | 109.5 |
C7—C6—H6 | 121.6 | C8—C16—H16A | 109.5 |
O1—C7—C6 | 126.5 (3) | C8—C16—H16B | 109.5 |
O1—C7—C2 | 110.7 (3) | H16A—C16—H16B | 109.5 |
C6—C7—C2 | 122.8 (3) | C8—C16—H16C | 109.5 |
O1—C8—C1 | 110.4 (3) | H16A—C16—H16C | 109.5 |
O1—C8—C16 | 115.5 (3) | H16B—C16—H16C | 109.5 |
C1—C8—C16 | 134.1 (3) | ||
O3—S—C1—C8 | −24.0 (3) | C3—C2—C7—C6 | −1.8 (5) |
O2—S—C1—C8 | −154.2 (3) | C1—C2—C7—C6 | 178.9 (3) |
C9—S—C1—C8 | 91.3 (3) | C7—O1—C8—C1 | 0.0 (3) |
O3—S—C1—C2 | 157.4 (2) | C7—O1—C8—C16 | −178.4 (3) |
O2—S—C1—C2 | 27.2 (3) | C2—C1—C8—O1 | 0.3 (4) |
C9—S—C1—C2 | −87.2 (3) | S—C1—C8—O1 | −178.5 (2) |
C8—C1—C2—C3 | −179.4 (3) | C2—C1—C8—C16 | 178.2 (4) |
S—C1—C2—C3 | −0.6 (5) | S—C1—C8—C16 | −0.6 (6) |
C8—C1—C2—C7 | −0.4 (3) | O3—S—C9—C10 | −156.0 (2) |
S—C1—C2—C7 | 178.4 (2) | O2—S—C9—C10 | −26.2 (2) |
C7—C2—C3—C4 | 1.7 (4) | C1—S—C9—C10 | 87.9 (2) |
C1—C2—C3—C4 | −179.4 (3) | O3—S—C9—C14 | 24.4 (3) |
C2—C3—C4—C5 | −0.9 (5) | O2—S—C9—C14 | 154.3 (2) |
C2—C3—C4—C15 | 179.0 (3) | C1—S—C9—C14 | −91.6 (2) |
C3—C4—C5—C6 | 0.2 (6) | C14—C9—C10—C11 | 0.2 (4) |
C15—C4—C5—C6 | −179.8 (3) | S—C9—C10—C11 | −179.4 (2) |
C4—C5—C6—C7 | −0.2 (5) | C9—C10—C11—C12 | 0.5 (5) |
C8—O1—C7—C6 | −178.7 (3) | C10—C11—C12—C13 | −0.8 (6) |
C8—O1—C7—C2 | −0.2 (3) | C11—C12—C13—C14 | 0.3 (6) |
C5—C6—C7—O1 | 179.4 (3) | C12—C13—C14—C9 | 0.3 (5) |
C5—C6—C7—C2 | 1.1 (5) | C10—C9—C14—C13 | −0.6 (4) |
C3—C2—C7—O1 | 179.6 (2) | S—C9—C14—C13 | 179.0 (2) |
C1—C2—C7—O1 | 0.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O2i | 0.93 | 2.45 | 3.345 (4) | 160 |
C14—H14···O3ii | 0.93 | 2.50 | 3.263 (4) | 139 |
C16—H16C···O3 | 0.96 | 2.40 | 3.108 (4) | 130 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C16H14O3S |
Mr | 286.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.476 (4), 9.448 (5), 11.283 (6) |
α, β, γ (°) | 110.834 (8), 95.651 (9), 106.122 (9) |
V (Å3) | 698.0 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.40 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4916, 2560, 1967 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.165, 1.08 |
No. of reflections | 2560 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.33 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O2i | 0.93 | 2.45 | 3.345 (4) | 160.3 |
C14—H14···O3ii | 0.93 | 2.50 | 3.263 (4) | 138.9 |
C16—H16C···O3 | 0.96 | 2.40 | 3.108 (4) | 130.0 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z. |
References
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2008a). Acta Cryst. E64, o793. Web of Science CSD CrossRef IUCr Journals Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2008b). Acta Cryst. E64, o794. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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As a part of our ongoing studies on the synthesis and structure of 3-phenyl-sulfonyl-1-benzofuran analogues, the crystal structure of 5-bromo-2-methyl-3-phenylsulfonyl-1-benzofuran (Choi et al., 2008a) and 2,5,7-trimethyl-3-phenylsulfonyl-1-benzofuran (Choi et al., 2008b) have been described in the literature. Herein we report the molecular and crystal structure of the title compound, 2,5-dimethyl-3-phenylsulfonyl-1-benzofuran (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.065 Å from the least-squares plane defined by the nine constituent atoms. The phenyl ring (C9—C14) makes a dihedral angle of 76.98 (9)° with the plane of the benzofuran fragment. The crystal packing (Fig. 2) is stabilized by aromatic π—π stacking interactions between the furan ring and the benzene ring from neighbouring molecules. The Cg1···Cg2iii distance is 3.775 (4) Å (Cg1 and Cg2 are the centroids of the O1/C8/C1/C2/C7 furan and the C2—C7 benzene rings, respectively, symmetry code as in Fig. 2). The molecular packing (Fig. 2) is further stabilized by intra- and intermolecular C—H···O interactions (Table 1 and Fig. 2; symmetry codes as in Fig. 2).