Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041761/bt2489sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041761/bt2489Isup2.hkl |
CCDC reference: 660375
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.048
- wR factor = 0.120
- Data-to-parameter ratio = 20.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT410_ALERT_2_B Short Intra H...H Contact H3B .. H12A .. 1.86 Ang.
Alert level C PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H8 .. S2 .. 2.93 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H9 .. S13 .. 3.00 Ang.
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 0 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was prepared by cyclization of 1,3-di(bromomethyl)naphthalene and 2,3-di(mercaptomethyl)naphthalene as described by Kuś (1991). Single crystals were obtained from DMF solution by very slow evaporation (5 years).
Hydrogen atoms were included using a riding model with C—H 0.95 (aromatic), 0.99 (methyene) Å; U(H) values were fixed at 1.2U(C) of the parent C atom.
We have reported the structures of 2,13-dithia[3]metacyclo[3](2,3)-naphthalenophane [(IIa); Jones & Kus, 1997], and 17-methyl-2,13-dithia[3]metacyclo[3](2,3)naphthalenophane [(IIb); Jones et al., 1996] as part of a series of ortho-meta dithiaphanes. Surprisingly, in the solid state both compounds exist in an anti conformation, in contrast to the simpler analogue 2,11-dithia[3.3]orthometacyclophane, which adopts a syn conformation (Bodwell et al., 1990). Here we report the next compound in the ortho-meta series, the title compound (I).
Compound (I) (Fig. 1) displays approximate mirror symmetry except, necessarily, for the second ring of the meta-substituted naphthalene system. Torsion angles of the central 11-membered ring are given in Table 1. These torsion angles, and thus the overall molecular conformations, are closely similar in all three compounds (I), (IIa) and (IIb) (Fig. 3). The ring systems of I are approximately parallel [interplanar angle 5.57 (8)°] and adopt anti conformation. The perpendicular distance between the ring planes (as given by the distance of atoms of the meta-substituted ring from the best plane of the ortho-substituted naphthalene) is 2.8–3.1 Å.
The crystal packing of the three compounds is different; they crystallize in different space groups. In (I), two weak C—H···S interactions (Table 2) combine with a short C—H···π contact from H12B to the centroid of the ring C16A–C20A [2.55 Å, angle 160°, operator 1 - x, 1 - y, -z)] to form columns of molecules parallel to the y axis (Fig. 2).
For related literature, see: Bodwell et al. (1990); Jones & Kus (1997); Jones et al. (1996); Kuś (1991).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS86 ??? (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
C24H20S2 | F(000) = 784 |
Mr = 372.52 | Dx = 1.372 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6839 (11) Å | Cell parameters from 9929 reflections |
b = 8.4014 (8) Å | θ = 2.4–29.1° |
c = 20.285 (2) Å | µ = 0.30 mm−1 |
β = 98.000 (5)° | T = 100 K |
V = 1803.0 (3) Å3 | Tablet, colourless |
Z = 4 | 0.26 × 0.18 × 0.12 mm |
Bruker APEXII CCD area-detector diffractometer | 4078 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 29.1°, θmin = 2.0° |
φ and ω scans | h = −14→14 |
34380 measured reflections | k = −11→11 |
4845 independent reflections | l = −27→27 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0421P)2 + 1.9877P] where P = (Fo2 + 2Fc2)/3 |
4845 reflections | (Δ/σ)max < 0.001 |
235 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C24H20S2 | V = 1803.0 (3) Å3 |
Mr = 372.52 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6839 (11) Å | µ = 0.30 mm−1 |
b = 8.4014 (8) Å | T = 100 K |
c = 20.285 (2) Å | 0.26 × 0.18 × 0.12 mm |
β = 98.000 (5)° |
Bruker APEXII CCD area-detector diffractometer | 4078 reflections with I > 2σ(I) |
34380 measured reflections | Rint = 0.042 |
4845 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.54 e Å−3 |
4845 reflections | Δρmin = −0.34 e Å−3 |
235 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 0.6768 (0.0048) x + 5.7973 (0.0030) y + 14.6617 (0.0072) z = 2.8381 (0.0041) * -0.0179 (0.0014) C4 * 0.0111 (0.0015) C5 * 0.0155 (0.0016) C5A * 0.0040 (0.0015) C6 * -0.0144 (0.0016) C7 * -0.0102 (0.0016) C8 * 0.0037 (0.0015) C9 * 0.0127 (0.0016) C9A * 0.0079 (0.0015) C10 * -0.0123 (0.0014) C11 Rms deviation of fitted atoms = 0.0118 - 0.2034 (0.0040) x + 5.2610 (0.0039) y + 15.7106 (0.0078) z = 5.7669 (0.0029) Angle to previous plane (with approximate e.s.d.) = 5.57 (0.08) * -0.0328 (0.0015) C15 * -0.0107 (0.0016) C16 * 0.0253 (0.0017) C16A * 0.0224 (0.0017) C17 * -0.0097 (0.0017) C18 * -0.0196 (0.0017) C19 * -0.0062 (0.0016) C20 * 0.0115 (0.0017) C20A * 0.0052 (0.0015) C21 * 0.0146 (0.0015) C22 Rms deviation of fitted atoms = 0.0180 |
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 | ||
C1 | 0.51333 (19) | 0.4411 (2) | 0.21556 (9) | 0.0215 (4) | |
H1A | 0.4539 | 0.4564 | 0.2483 | 0.026* | |
H1B | 0.5978 | 0.4182 | 0.2404 | 0.026* | |
S2 | 0.46141 (4) | 0.27093 (6) | 0.16196 (3) | 0.02078 (12) | |
C3 | 0.54841 (17) | 0.3050 (2) | 0.09254 (9) | 0.0191 (4) | |
H3A | 0.5197 | 0.2260 | 0.0575 | 0.023* | |
H3B | 0.5253 | 0.4117 | 0.0740 | 0.023* | |
C4 | 0.69170 (17) | 0.2959 (2) | 0.10727 (9) | 0.0161 (3) | |
C5 | 0.74674 (17) | 0.1893 (2) | 0.15396 (9) | 0.0165 (3) | |
H5 | 0.6939 | 0.1264 | 0.1776 | 0.020* | |
C5A | 0.87958 (17) | 0.1700 (2) | 0.16802 (9) | 0.0159 (3) | |
C6 | 0.93695 (18) | 0.0566 (2) | 0.21471 (9) | 0.0190 (4) | |
H6 | 0.8856 | −0.0083 | 0.2384 | 0.023* | |
C7 | 1.06536 (19) | 0.0402 (2) | 0.22588 (10) | 0.0210 (4) | |
H7 | 1.1026 | −0.0367 | 0.2569 | 0.025* | |
C8 | 1.14336 (18) | 0.1369 (2) | 0.19153 (10) | 0.0211 (4) | |
H8 | 1.2326 | 0.1250 | 0.1999 | 0.025* | |
C9 | 1.09126 (18) | 0.2473 (2) | 0.14642 (9) | 0.0187 (4) | |
H9 | 1.1446 | 0.3116 | 0.1237 | 0.022* | |
C9A | 0.95820 (17) | 0.2666 (2) | 0.13324 (9) | 0.0156 (3) | |
C10 | 0.89987 (17) | 0.3780 (2) | 0.08618 (9) | 0.0169 (3) | |
H10 | 0.9519 | 0.4439 | 0.0633 | 0.020* | |
C11 | 0.77070 (17) | 0.3943 (2) | 0.07241 (9) | 0.0161 (3) | |
C12 | 0.71529 (18) | 0.5127 (2) | 0.01978 (9) | 0.0187 (4) | |
H12A | 0.6271 | 0.5351 | 0.0268 | 0.022* | |
H12B | 0.7119 | 0.4610 | −0.0243 | 0.022* | |
S13 | 0.79701 (5) | 0.70201 (6) | 0.01669 (2) | 0.02253 (12) | |
C14 | 0.78066 (19) | 0.7904 (2) | 0.09742 (10) | 0.0227 (4) | |
H14A | 0.8450 | 0.7436 | 0.1318 | 0.027* | |
H14B | 0.7972 | 0.9061 | 0.0956 | 0.027* | |
C15 | 0.65157 (19) | 0.7646 (2) | 0.11739 (9) | 0.0198 (4) | |
C16 | 0.54634 (19) | 0.8478 (2) | 0.08957 (10) | 0.0211 (4) | |
H16 | 0.5557 | 0.9339 | 0.0603 | 0.025* | |
C16A | 0.42454 (19) | 0.8071 (2) | 0.10390 (9) | 0.0201 (4) | |
C17 | 0.3147 (2) | 0.8902 (3) | 0.07447 (10) | 0.0258 (4) | |
H17 | 0.3236 | 0.9786 | 0.0463 | 0.031* | |
C18 | 0.1969 (2) | 0.8455 (3) | 0.08588 (11) | 0.0299 (5) | |
H18 | 0.1248 | 0.9016 | 0.0651 | 0.036* | |
C19 | 0.1817 (2) | 0.7158 (3) | 0.12849 (11) | 0.0290 (5) | |
H19 | 0.0995 | 0.6856 | 0.1365 | 0.035* | |
C20 | 0.28544 (19) | 0.6332 (3) | 0.15835 (10) | 0.0237 (4) | |
H20 | 0.2741 | 0.5465 | 0.1870 | 0.028* | |
C20A | 0.40914 (18) | 0.6755 (2) | 0.14689 (9) | 0.0192 (4) | |
C21 | 0.51962 (18) | 0.5912 (2) | 0.17616 (9) | 0.0184 (4) | |
C22 | 0.63570 (18) | 0.6398 (2) | 0.16198 (9) | 0.0186 (4) | |
H22 | 0.7089 | 0.5868 | 0.1833 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0248 (10) | 0.0215 (9) | 0.0179 (9) | 0.0011 (7) | 0.0020 (7) | 0.0004 (7) |
S2 | 0.0159 (2) | 0.0197 (2) | 0.0270 (3) | −0.00133 (17) | 0.00408 (18) | 0.00062 (18) |
C3 | 0.0161 (8) | 0.0214 (9) | 0.0189 (9) | 0.0019 (7) | −0.0005 (7) | −0.0016 (7) |
C4 | 0.0156 (8) | 0.0160 (8) | 0.0162 (8) | 0.0015 (7) | 0.0002 (6) | −0.0034 (6) |
C5 | 0.0143 (8) | 0.0162 (8) | 0.0191 (9) | 0.0001 (6) | 0.0024 (7) | −0.0007 (7) |
C5A | 0.0153 (8) | 0.0167 (8) | 0.0154 (8) | 0.0011 (6) | 0.0011 (6) | −0.0014 (6) |
C6 | 0.0199 (9) | 0.0185 (8) | 0.0187 (9) | −0.0001 (7) | 0.0028 (7) | 0.0039 (7) |
C7 | 0.0212 (9) | 0.0220 (9) | 0.0187 (9) | 0.0044 (7) | −0.0011 (7) | 0.0036 (7) |
C8 | 0.0147 (8) | 0.0278 (10) | 0.0200 (9) | 0.0024 (7) | −0.0004 (7) | −0.0008 (8) |
C9 | 0.0178 (9) | 0.0226 (9) | 0.0159 (8) | −0.0006 (7) | 0.0035 (7) | −0.0004 (7) |
C9A | 0.0159 (8) | 0.0157 (8) | 0.0153 (8) | −0.0006 (6) | 0.0024 (6) | −0.0019 (6) |
C10 | 0.0199 (9) | 0.0166 (8) | 0.0143 (8) | 0.0001 (7) | 0.0030 (7) | 0.0004 (6) |
C11 | 0.0197 (9) | 0.0156 (8) | 0.0125 (8) | 0.0023 (7) | 0.0008 (6) | −0.0015 (6) |
C12 | 0.0215 (9) | 0.0195 (9) | 0.0146 (8) | 0.0031 (7) | 0.0007 (7) | 0.0009 (7) |
S13 | 0.0267 (3) | 0.0208 (2) | 0.0209 (2) | 0.00169 (19) | 0.00617 (19) | 0.00531 (18) |
C14 | 0.0226 (9) | 0.0207 (9) | 0.0247 (10) | −0.0032 (7) | 0.0027 (8) | −0.0016 (8) |
C15 | 0.0227 (9) | 0.0181 (9) | 0.0181 (9) | −0.0011 (7) | 0.0012 (7) | −0.0051 (7) |
C16 | 0.0275 (10) | 0.0168 (8) | 0.0192 (9) | 0.0009 (7) | 0.0034 (7) | −0.0006 (7) |
C16A | 0.0250 (10) | 0.0178 (8) | 0.0169 (9) | 0.0032 (7) | 0.0014 (7) | −0.0029 (7) |
C17 | 0.0292 (11) | 0.0218 (9) | 0.0255 (10) | 0.0082 (8) | 0.0013 (8) | 0.0000 (8) |
C18 | 0.0253 (11) | 0.0301 (11) | 0.0330 (12) | 0.0097 (9) | −0.0002 (9) | −0.0047 (9) |
C19 | 0.0209 (10) | 0.0326 (11) | 0.0343 (12) | 0.0026 (8) | 0.0067 (8) | −0.0058 (9) |
C20 | 0.0240 (10) | 0.0243 (10) | 0.0236 (10) | 0.0012 (8) | 0.0067 (8) | −0.0024 (8) |
C20A | 0.0217 (9) | 0.0194 (9) | 0.0167 (9) | 0.0016 (7) | 0.0031 (7) | −0.0041 (7) |
C21 | 0.0244 (9) | 0.0169 (8) | 0.0137 (8) | 0.0014 (7) | 0.0018 (7) | −0.0023 (6) |
C22 | 0.0209 (9) | 0.0176 (8) | 0.0158 (8) | 0.0022 (7) | −0.0020 (7) | −0.0040 (7) |
C1—C21 | 1.499 (3) | C18—C19 | 1.414 (3) |
C1—S2 | 1.835 (2) | C19—C20 | 1.375 (3) |
S2—C3 | 1.815 (2) | C20—C20A | 1.419 (3) |
C3—C4 | 1.520 (2) | C20A—C21 | 1.433 (3) |
C4—C5 | 1.375 (3) | C21—C22 | 1.374 (3) |
C4—C11 | 1.436 (3) | C1—H1A | 0.9900 |
C5—C5A | 1.418 (2) | C1—H1B | 0.9900 |
C5A—C6 | 1.421 (2) | C3—H3A | 0.9900 |
C5A—C9A | 1.424 (3) | C3—H3B | 0.9900 |
C6—C7 | 1.366 (3) | C5—H5 | 0.9500 |
C7—C8 | 1.415 (3) | C6—H6 | 0.9500 |
C8—C9 | 1.366 (3) | C7—H7 | 0.9500 |
C9—C9A | 1.419 (3) | C8—H8 | 0.9500 |
C9A—C10 | 1.418 (2) | C9—H9 | 0.9500 |
C10—C11 | 1.376 (3) | C10—H10 | 0.9500 |
C11—C12 | 1.518 (2) | C12—H12A | 0.9900 |
C12—S13 | 1.820 (2) | C12—H12B | 0.9900 |
S13—C14 | 1.828 (2) | C14—H14A | 0.9900 |
C14—C15 | 1.506 (3) | C14—H14B | 0.9900 |
C15—C16 | 1.376 (3) | C16—H16 | 0.9500 |
C15—C22 | 1.410 (3) | C17—H17 | 0.9500 |
C16—C16A | 1.414 (3) | C18—H18 | 0.9500 |
C16A—C17 | 1.423 (3) | C19—H19 | 0.9500 |
C16A—C20A | 1.432 (3) | C20—H20 | 0.9500 |
C17—C18 | 1.364 (3) | C22—H22 | 0.9500 |
C21—C1—S2 | 111.82 (13) | S2—C1—H1A | 109.3 |
C3—S2—C1 | 101.06 (9) | C21—C1—H1B | 109.3 |
C4—C3—S2 | 116.75 (13) | S2—C1—H1B | 109.3 |
C5—C4—C11 | 119.33 (16) | H1A—C1—H1B | 107.9 |
C5—C4—C3 | 119.37 (17) | C4—C3—H3A | 108.1 |
C11—C4—C3 | 121.28 (16) | S2—C3—H3A | 108.1 |
C4—C5—C5A | 122.23 (17) | C4—C3—H3B | 108.1 |
C5—C5A—C6 | 122.54 (17) | S2—C3—H3B | 108.1 |
C5—C5A—C9A | 118.57 (16) | H3A—C3—H3B | 107.3 |
C6—C5A—C9A | 118.89 (16) | C4—C5—H5 | 118.9 |
C7—C6—C5A | 120.56 (17) | C5A—C5—H5 | 118.9 |
C6—C7—C8 | 120.47 (18) | C7—C6—H6 | 119.7 |
C9—C8—C7 | 120.45 (17) | C5A—C6—H6 | 119.7 |
C8—C9—C9A | 120.55 (17) | C6—C7—H7 | 119.8 |
C10—C9A—C9 | 122.52 (17) | C8—C7—H7 | 119.8 |
C10—C9A—C5A | 118.41 (16) | C9—C8—H8 | 119.8 |
C9—C9A—C5A | 119.07 (16) | C7—C8—H8 | 119.8 |
C11—C10—C9A | 122.47 (17) | C8—C9—H9 | 119.7 |
C10—C11—C4 | 118.97 (16) | C9A—C9—H9 | 119.7 |
C10—C11—C12 | 119.34 (17) | C11—C10—H10 | 118.8 |
C4—C11—C12 | 121.68 (16) | C9A—C10—H10 | 118.8 |
C11—C12—S13 | 117.07 (13) | C11—C12—H12A | 108.0 |
C12—S13—C14 | 102.58 (9) | S13—C12—H12A | 108.0 |
C15—C14—S13 | 112.81 (14) | C11—C12—H12B | 108.0 |
C16—C15—C22 | 118.44 (18) | S13—C12—H12B | 108.0 |
C16—C15—C14 | 122.88 (18) | H12A—C12—H12B | 107.3 |
C22—C15—C14 | 118.41 (17) | C15—C14—H14A | 109.0 |
C15—C16—C16A | 121.04 (18) | S13—C14—H14A | 109.0 |
C16—C16A—C17 | 121.61 (18) | C15—C14—H14B | 109.0 |
C16—C16A—C20A | 119.91 (18) | S13—C14—H14B | 109.0 |
C17—C16A—C20A | 118.44 (19) | H14A—C14—H14B | 107.8 |
C18—C17—C16A | 121.3 (2) | C15—C16—H16 | 119.5 |
C17—C18—C19 | 120.2 (2) | C16A—C16—H16 | 119.5 |
C20—C19—C18 | 120.3 (2) | C18—C17—H17 | 119.3 |
C19—C20—C20A | 120.9 (2) | C16A—C17—H17 | 119.3 |
C20—C20A—C16A | 118.82 (18) | C17—C18—H18 | 119.9 |
C20—C20A—C21 | 122.72 (18) | C19—C18—H18 | 119.9 |
C16A—C20A—C21 | 118.45 (18) | C20—C19—H19 | 119.9 |
C22—C21—C20A | 118.81 (17) | C18—C19—H19 | 119.9 |
C22—C21—C1 | 118.07 (17) | C19—C20—H20 | 119.6 |
C20A—C21—C1 | 122.77 (18) | C20A—C20—H20 | 119.6 |
C21—C22—C15 | 123.24 (18) | C21—C22—H22 | 118.4 |
C21—C1—H1A | 109.3 | C15—C22—H22 | 118.4 |
C21—C1—S2—C3 | 41.41 (16) | C11—C12—S13—C14 | −63.60 (16) |
C1—S2—C3—C4 | 64.53 (16) | C12—S13—C14—C15 | −40.79 (16) |
S2—C3—C4—C5 | 34.4 (2) | S13—C14—C15—C16 | −75.2 (2) |
S2—C3—C4—C11 | −146.85 (15) | S13—C14—C15—C22 | 98.75 (18) |
C11—C4—C5—C5A | −1.5 (3) | C22—C15—C16—C16A | −1.5 (3) |
C3—C4—C5—C5A | 177.25 (17) | C14—C15—C16—C16A | 172.45 (17) |
C4—C5—C5A—C6 | −178.02 (17) | C15—C16—C16A—C17 | −178.77 (18) |
C4—C5—C5A—C9A | 1.1 (3) | C15—C16—C16A—C20A | −1.3 (3) |
C5—C5A—C6—C7 | 178.87 (18) | C16—C16A—C17—C18 | 176.7 (2) |
C9A—C5A—C6—C7 | −0.2 (3) | C20A—C16A—C17—C18 | −0.8 (3) |
C5A—C6—C7—C8 | 0.6 (3) | C16A—C17—C18—C19 | 1.0 (3) |
C6—C7—C8—C9 | −0.4 (3) | C17—C18—C19—C20 | −0.4 (3) |
C7—C8—C9—C9A | −0.1 (3) | C18—C19—C20—C20A | −0.3 (3) |
C8—C9—C9A—C10 | −179.07 (18) | C19—C20—C20A—C16A | 0.5 (3) |
C8—C9—C9A—C5A | 0.4 (3) | C19—C20—C20A—C21 | −179.02 (19) |
C5—C5A—C9A—C10 | 0.1 (3) | C16—C16A—C20A—C20 | −177.49 (18) |
C6—C5A—C9A—C10 | 179.25 (16) | C17—C16A—C20A—C20 | 0.1 (3) |
C5—C5A—C9A—C9 | −179.38 (17) | C16—C16A—C20A—C21 | 2.0 (3) |
C6—C5A—C9A—C9 | −0.2 (3) | C17—C16A—C20A—C21 | 179.59 (17) |
C9—C9A—C10—C11 | 178.57 (17) | C20—C20A—C21—C22 | 179.58 (18) |
C5A—C9A—C10—C11 | −0.9 (3) | C16A—C20A—C21—C22 | 0.1 (3) |
C9A—C10—C11—C4 | 0.5 (3) | C20—C20A—C21—C1 | 6.5 (3) |
C9A—C10—C11—C12 | −178.11 (16) | C16A—C20A—C21—C1 | −172.94 (17) |
C5—C4—C11—C10 | 0.7 (3) | S2—C1—C21—C22 | −99.84 (18) |
C3—C4—C11—C10 | −178.04 (16) | S2—C1—C21—C20A | 73.2 (2) |
C5—C4—C11—C12 | 179.27 (16) | C20A—C21—C22—C15 | −3.1 (3) |
C3—C4—C11—C12 | 0.6 (3) | C1—C21—C22—C15 | 170.29 (17) |
C10—C11—C12—S13 | −39.2 (2) | C16—C15—C22—C21 | 3.8 (3) |
C4—C11—C12—S13 | 142.21 (15) | C14—C15—C22—C21 | −170.44 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···S2i | 0.95 | 2.93 | 3.707 (2) | 140 |
C9—H9···S13ii | 0.95 | 3.00 | 3.6951 (19) | 131 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C24H20S2 |
Mr | 372.52 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.6839 (11), 8.4014 (8), 20.285 (2) |
β (°) | 98.000 (5) |
V (Å3) | 1803.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.26 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34380, 4845, 4078 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.685 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.120, 1.13 |
No. of reflections | 4845 |
No. of parameters | 235 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.34 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT, SHELXS86 ??? (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
C1—S2 | 1.835 (2) | C12—S13 | 1.820 (2) |
S2—C3 | 1.815 (2) | S13—C14 | 1.828 (2) |
C3—S2—C1 | 101.06 (9) | C12—S13—C14 | 102.58 (9) |
C21—C1—S2—C3 | 41.41 (16) | C12—S13—C14—C15 | −40.79 (16) |
C1—S2—C3—C4 | 64.53 (16) | S13—C14—C15—C22 | 98.75 (18) |
S2—C3—C4—C11 | −146.85 (15) | S2—C1—C21—C22 | −99.84 (18) |
C3—C4—C11—C12 | 0.6 (3) | C1—C21—C22—C15 | 170.29 (17) |
C4—C11—C12—S13 | 142.21 (15) | C14—C15—C22—C21 | −170.44 (17) |
C11—C12—S13—C14 | −63.60 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···S2i | 0.95 | 2.93 | 3.707 (2) | 139.6 |
C9—H9···S13ii | 0.95 | 3.00 | 3.6951 (19) | 131.1 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z. |
We have reported the structures of 2,13-dithia[3]metacyclo[3](2,3)-naphthalenophane [(IIa); Jones & Kus, 1997], and 17-methyl-2,13-dithia[3]metacyclo[3](2,3)naphthalenophane [(IIb); Jones et al., 1996] as part of a series of ortho-meta dithiaphanes. Surprisingly, in the solid state both compounds exist in an anti conformation, in contrast to the simpler analogue 2,11-dithia[3.3]orthometacyclophane, which adopts a syn conformation (Bodwell et al., 1990). Here we report the next compound in the ortho-meta series, the title compound (I).
Compound (I) (Fig. 1) displays approximate mirror symmetry except, necessarily, for the second ring of the meta-substituted naphthalene system. Torsion angles of the central 11-membered ring are given in Table 1. These torsion angles, and thus the overall molecular conformations, are closely similar in all three compounds (I), (IIa) and (IIb) (Fig. 3). The ring systems of I are approximately parallel [interplanar angle 5.57 (8)°] and adopt anti conformation. The perpendicular distance between the ring planes (as given by the distance of atoms of the meta-substituted ring from the best plane of the ortho-substituted naphthalene) is 2.8–3.1 Å.
The crystal packing of the three compounds is different; they crystallize in different space groups. In (I), two weak C—H···S interactions (Table 2) combine with a short C—H···π contact from H12B to the centroid of the ring C16A–C20A [2.55 Å, angle 160°, operator 1 - x, 1 - y, -z)] to form columns of molecules parallel to the y axis (Fig. 2).