Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004595/fr1267sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004595/fr1267Isup2.hkl |
CCDC reference: 147651
The title compound was obtained as a colorless plate from a coarsely crystalline sample in Dr M. S. Newman's chemical collection. The experimental sample was cut from this plate. A synthesis of (I) is described by Newman (1984).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN and PLATON (Spek, 1990).
Fig. 1. Labelling scheme and displacement ellipsoids at the 50% probability level. | |
Fig. 2. Packing stereodiagram of (I). The finer interatomic lines depict the intramolecular hydrogen bonds. |
C23H16O4S | F(000) = 808 |
Mr = 388.44 | Dx = 1.377 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.478 (1) Å | Cell parameters from 25 reflections |
b = 10.406 (1) Å | θ = 16.1–17.5° |
c = 21.336 (1) Å | µ = 0.20 mm−1 |
β = 95.701 (9)° | T = 296 K |
V = 1873.2 (4) Å3 | Cut plate, colorless |
Z = 4 | 0.42 × 0.35 × 0.27 mm |
AFC5S diffractometer | Rint = 0.010 |
Radiation source: X-ray tube | θmax = 27.6°, θmin = 2.8° |
Graphite monochromator | h = 0→11 |
ω scans | k = 0→13 |
4618 measured reflections | l = −27→27 |
4333 independent reflections | 6 standard reflections every 150 reflections |
3246 reflections with I > 2.0σI | intensity decay: −1.8% |
Refinement on F2 | 257 parameters |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2cs + (0.012I)2] |
wR(F2) = 0.083 | (Δ/σ)max = 0.001 |
S = 1.44 | Δρmax = 0.39 e Å−3 |
4331 reflections | Δρmin = −0.47 e Å−3 |
C23H16O4S | V = 1873.2 (4) Å3 |
Mr = 388.44 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.478 (1) Å | µ = 0.20 mm−1 |
b = 10.406 (1) Å | T = 296 K |
c = 21.336 (1) Å | 0.42 × 0.35 × 0.27 mm |
β = 95.701 (9)° |
AFC5S diffractometer | Rint = 0.010 |
4618 measured reflections | 6 standard reflections every 150 reflections |
4333 independent reflections | intensity decay: −1.8% |
3246 reflections with I > 2.0σI |
R[F2 > 2σ(F2)] = 0.046 | 257 parameters |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.44 | Δρmax = 0.39 e Å−3 |
4331 reflections | Δρmin = −0.47 e Å−3 |
Experimental. Scan widths were (1.50 + 0.35 tanθ)° in ω, with background/scan time-ratio of 0.5. The data were corrected for Lorentz and polarization effects. A linear decay (growth) correction was applied. Due to mis-labelling of (I) in the Newman collection, it was not known to contain sulfur prior to data acquisition and data required for absorption correction were not obtained. The Laue group assignment, systematic absences and centrosymmetric intensity statistics indicated uniquely space group P21/n (No. 14). Since refinement proceeded well, it was adopted. Fourier difference methods were used to locate initial H atom positions, and the H atoms were then refined isotropically. Refined C—H distances ranged from 0.91 (2) to 1.02 (2) Å, with a mean value 0.95 (3) Å. Subsequently, these H atoms were made canonical with C—H = 0.98 Å and Uiso = 1.2 × Ueq of the attached C atom. The refined hydroxyl group O—H distance is 0.90 (2) Å. In late stages of refinement, the extinction coefficient was predicted to be negative, and was not included in the model; however, two intense reflections, 1 0 − 1 and 0 1 4, appeared to suffer from extinction and were excluded from further refinements. The maximum positive residual peak is located ~0.7 Å from C16 and 1.1 Å from S1; the maximum negative peak is located ~0.7 Å from S1. |
Geometry. TABLE of LEAST SQUARES PLANES ————– Plane number 1 ————— Atoms Defining Plane Distance e.s.d. C1 (1) −0.0025 0.0019 C2 (1) 0.0071 0.0021 C3 (1) −0.0037 0.0021 C4 (1) −0.0044 0.0020 C10 (1) −0.0030 0.0017 C11 (1) 0.0059 0.0017 Mean deviation from plane is 0.0044 angstroms Chi-squared: 34.6 ————– Plane number 2 ————— Atoms Defining Plane Distance e.s.d. C5 (1) 0.0018 0.0021 C6 (1) 0.0014 0.0023 C7 (1) −0.0015 0.0021 C8 (1) −0.0014 0.0019 C12 (1) −0.0034 0.0018 C13 (1) 0.0031 0.0017 Mean deviation from plane is 0.0021 angstroms Chi-squared: 8.7 Dihedral angles between least-squares planes plane plane angle 2 1 2.19 ————– Plane number 3 ————— Atoms Defining Plane Distance e.s.d. C9 (1) −0.0176 0.0017 C10 (1) 0.0153 0.0016 C11 (1) −0.0076 0.0017 C12 (1) −0.0063 0.0018 C13 (1) 0.0151 0.0017 Mean deviation from plane is 0.0124 angstroms Chi-squared: 293.0 Dihedral angles between least-squares planes plane plane angle 3 1 2.07 3 2 0.62 ————– Plane number 4 ————— Atoms Defining Plane Distance e.s.d. C9 (1) 0.0251 0.0017 C14 (1) −0.0153 0.0018 C15 (1) −0.0048 0.0017 C16 (1) 0.0183 0.0016 C17 (1) −0.0326 0.0019 Mean deviation from plane is 0.0192 angstroms Chi-squared: 735.7 Dihedral angles between least-squares planes plane plane angle 4 1 91.93 4 2 89.76 4 3 90.05 ————– Plane number 5 ————— Atoms Defining Plane Distance e.s.d. C18 (1) 0.0035 0.0016 C19 (1) −0.0045 0.0020 C20 (1) 0.0018 0.0022 C21 (1) 0.0015 0.0022 C22 (1) −0.0009 0.0024 C23 (1) −0.0030 0.0021 Mean deviation from plane is 0.0025 angstroms Chi-squared: 12.4 Dihedral angles between least-squares planes plane plane angle 5 1 77.38 5 2 77.03 5 3 76.49 5 4 89.11 ————– Plane number 6 ————— Atoms Defining Plane Distance e.s.d. C9 (2) 0.0176 0.0017 C10 (2) −0.0153 0.0016 C11 (2) 0.0076 0.0017 C12 (2) 0.0063 0.0018 C13 (2) −0.0151 0.0017 Mean deviation from plane is 0.0124 angstroms Chi-squared: 293.0 Dihedral angles between least-squares planes plane plane angle 6 1 133.01 6 2 130.87 6 3 130.94 6 4 45.36 6 5 82.60 |
x | y | z | Uiso*/Ueq | ||
S1 | 0.17658 (5) | 0.18786 (5) | 0.55526 (2) | 0.0419 (1) | |
O1 | 0.0276 (2) | −0.0717 (1) | 0.61194 (7) | 0.0575 (5) | |
O2 | 0.1509 (2) | 0.0750 (1) | 0.51599 (6) | 0.0618 (5) | |
O3 | 0.0870 (1) | 0.3021 (1) | 0.53870 (6) | 0.0584 (4) | |
O4 | 0.0327 (2) | −0.0693 (1) | 0.74399 (6) | 0.0606 (5) | |
C1 | 0.4418 (2) | 0.0642 (2) | 0.77549 (9) | 0.0491 (6) | |
C2 | 0.5588 (2) | 0.0450 (2) | 0.8251 (1) | 0.0599 (7) | |
C3 | 0.5309 (3) | 0.0739 (2) | 0.8860 (1) | 0.0613 (7) | |
C4 | 0.3885 (2) | 0.1241 (2) | 0.89966 (9) | 0.0520 (6) | |
C5 | 0.0316 (3) | 0.2487 (2) | 0.89869 (9) | 0.0554 (7) | |
C6 | −0.1195 (3) | 0.2971 (2) | 0.8842 (1) | 0.0633 (7) | |
C7 | −0.1888 (2) | 0.2992 (2) | 0.8233 (1) | 0.0581 (7) | |
C8 | −0.1082 (2) | 0.2527 (2) | 0.77468 (9) | 0.0486 (6) | |
C9 | 0.1518 (2) | 0.1454 (2) | 0.74426 (7) | 0.0346 (5) | |
C10 | 0.2985 (2) | 0.1146 (2) | 0.78904 (8) | 0.0356 (5) | |
C11 | 0.2713 (2) | 0.1456 (2) | 0.85065 (8) | 0.0384 (5) | |
C12 | 0.1132 (2) | 0.2013 (2) | 0.85033 (8) | 0.0393 (5) | |
C13 | 0.0428 (2) | 0.2044 (2) | 0.78847 (7) | 0.0360 (5) | |
C14 | 0.0808 (2) | 0.0201 (2) | 0.71580 (8) | 0.0382 (5) | |
C15 | 0.0837 (2) | 0.0283 (2) | 0.64629 (8) | 0.0372 (5) | |
C16 | 0.1443 (2) | 0.1410 (2) | 0.63130 (7) | 0.0329 (5) | |
C17 | 0.1850 (2) | 0.2282 (2) | 0.68670 (8) | 0.0403 (5) | |
C18 | 0.3794 (2) | 0.2269 (2) | 0.56277 (8) | 0.0378 (5) | |
C19 | 0.4904 (2) | 0.1303 (2) | 0.56594 (9) | 0.0524 (6) | |
C20 | 0.6499 (2) | 0.1627 (2) | 0.5745 (1) | 0.0635 (7) | |
C21 | 0.6948 (2) | 0.2891 (2) | 0.5803 (1) | 0.0641 (7) | |
C22 | 0.5830 (3) | 0.3844 (2) | 0.5775 (1) | 0.0691 (8) | |
C23 | 0.4233 (2) | 0.3539 (2) | 0.5688 (1) | 0.0542 (6) | |
H1 | 0.4606 | 0.0425 | 0.7322 | 0.059* | |
H1O1 | 0.039 (3) | −0.059 (2) | 0.571 (1) | 0.11 (1)* | |
H2 | 0.6622 | 0.0105 | 0.8166 | 0.072* | |
H3 | 0.6144 | 0.0584 | 0.9203 | 0.074* | |
H4 | 0.3700 | 0.1444 | 0.9432 | 0.062* | |
H5 | 0.0802 | 0.2478 | 0.9423 | 0.067* | |
H6 | −0.1781 | 0.3306 | 0.9180 | 0.076* | |
H7 | −0.2961 | 0.3338 | 0.8142 | 0.070* | |
H8 | −0.1577 | 0.2540 | 0.7312 | 0.058* | |
H17B | 0.1178 | 0.3051 | 0.6837 | 0.048* | |
H17A | 0.2966 | 0.2539 | 0.6894 | 0.048* | |
H19 | 0.4575 | 0.0401 | 0.5622 | 0.063* | |
H20 | 0.7307 | 0.0951 | 0.5764 | 0.076* | |
H21 | 0.8076 | 0.3113 | 0.5864 | 0.077* | |
H22 | 0.6160 | 0.4745 | 0.5817 | 0.083* | |
H23 | 0.3429 | 0.4218 | 0.5670 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0340 (2) | 0.0635 (3) | 0.0276 (2) | −0.0106 (2) | 0.0011 (2) | −0.0022 (2) |
O1 | 0.074 (1) | 0.0521 (9) | 0.0457 (8) | −0.0240 (8) | 0.0036 (8) | −0.0164 (7) |
O2 | 0.0617 (9) | 0.086 (1) | 0.0385 (7) | −0.0310 (8) | 0.0077 (7) | −0.0234 (7) |
O3 | 0.0416 (7) | 0.083 (1) | 0.0485 (8) | 0.0071 (8) | −0.0041 (6) | 0.0234 (8) |
O4 | 0.080 (1) | 0.0500 (9) | 0.0493 (8) | −0.0252 (8) | −0.0052 (7) | 0.0105 (7) |
C1 | 0.045 (1) | 0.044 (1) | 0.059 (1) | −0.002 (1) | 0.008 (1) | −0.006 (1) |
C2 | 0.038 (1) | 0.046 (1) | 0.094 (2) | 0.003 (1) | −0.003 (1) | −0.004 (1) |
C3 | 0.052 (1) | 0.051 (1) | 0.075 (2) | 0.002 (1) | −0.024 (1) | −0.002 (1) |
C4 | 0.057 (1) | 0.051 (1) | 0.044 (1) | 0.002 (1) | −0.014 (1) | −0.002 (1) |
C5 | 0.066 (1) | 0.064 (1) | 0.037 (1) | 0.004 (1) | 0.009 (1) | −0.005 (1) |
C6 | 0.067 (2) | 0.066 (2) | 0.061 (1) | 0.010 (1) | 0.026 (1) | −0.003 (1) |
C7 | 0.044 (1) | 0.057 (1) | 0.075 (2) | 0.010 (1) | 0.013 (1) | 0.008 (1) |
C8 | 0.043 (1) | 0.052 (1) | 0.049 (1) | 0.002 (1) | −0.0021 (9) | 0.007 (1) |
C9 | 0.040 (1) | 0.035 (1) | 0.0285 (8) | −0.0041 (8) | 0.0006 (7) | −0.0007 (7) |
C10 | 0.0351 (9) | 0.031 (1) | 0.0397 (9) | −0.0046 (8) | 0.0000 (8) | −0.0010 (8) |
C11 | 0.043 (1) | 0.034 (1) | 0.0360 (9) | −0.0038 (8) | −0.0048 (8) | −0.0004 (8) |
C12 | 0.043 (1) | 0.041 (1) | 0.0335 (9) | −0.0022 (9) | 0.0028 (8) | 0.0005 (8) |
C13 | 0.0383 (9) | 0.036 (1) | 0.0332 (9) | −0.0012 (8) | 0.0021 (7) | 0.0032 (8) |
C14 | 0.038 (1) | 0.038 (1) | 0.037 (1) | −0.0037 (8) | −0.0029 (8) | 0.0023 (8) |
C15 | 0.036 (1) | 0.040 (1) | 0.0354 (9) | −0.0038 (8) | 0.0005 (8) | −0.0067 (8) |
C16 | 0.0308 (9) | 0.041 (1) | 0.0266 (8) | −0.0023 (8) | 0.0022 (7) | −0.0025 (7) |
C17 | 0.051 (1) | 0.038 (1) | 0.0318 (9) | −0.0057 (9) | 0.0044 (8) | −0.0020 (8) |
C18 | 0.0313 (9) | 0.052 (1) | 0.0308 (9) | −0.0057 (9) | 0.0057 (7) | −0.0052 (8) |
C19 | 0.045 (1) | 0.050 (1) | 0.062 (1) | −0.002 (1) | 0.007 (1) | −0.008 (1) |
C20 | 0.040 (1) | 0.070 (2) | 0.080 (2) | 0.009 (1) | 0.004 (1) | −0.009 (1) |
C21 | 0.036 (1) | 0.083 (2) | 0.074 (2) | −0.011 (1) | 0.004 (1) | −0.012 (1) |
C22 | 0.049 (1) | 0.059 (1) | 0.099 (2) | −0.018 (1) | 0.006 (1) | −0.012 (1) |
C23 | 0.042 (1) | 0.050 (1) | 0.071 (1) | −0.003 (1) | 0.006 (1) | −0.007 (1) |
S1—O2 | 1.4462 (13) | C8—H8 | 0.98 |
S1—O3 | 1.4358 (14) | C9—C10 | 1.525 (2) |
S1—C16 | 1.742 (2) | C9—C13 | 1.515 (2) |
S1—C18 | 1.759 (2) | C9—C14 | 1.536 (2) |
O1—C15 | 1.333 (2) | C9—C17 | 1.549 (2) |
O1—H1O1 | 0.90 (2) | C10—C11 | 1.395 (2) |
O4—C14 | 1.201 (2) | C11—C12 | 1.460 (2) |
C1—C2 | 1.391 (3) | C12—C13 | 1.394 (2) |
C1—C10 | 1.380 (2) | C14—C15 | 1.488 (2) |
C1—H1 | 0.98 | C15—C16 | 1.332 (2) |
C2—C3 | 1.377 (3) | C16—C17 | 1.503 (2) |
C2—H2 | 0.98 | C17—H17B | 0.98 |
C3—C4 | 1.373 (3) | C17—H17A | 0.98 |
C3—H3 | 0.98 | C18—C19 | 1.374 (2) |
C4—C11 | 1.387 (2) | C18—C23 | 1.376 (2) |
C4—H4 | 0.98 | C19—C20 | 1.388 (3) |
C5—C6 | 1.383 (3) | C19—H19 | 0.98 |
C5—C12 | 1.389 (2) | C20—C21 | 1.371 (3) |
C5—H5 | 0.98 | C20—H20 | 0.98 |
C6—C7 | 1.371 (3) | C21—C22 | 1.369 (3) |
C6—H6 | 0.98 | C21—H21 | 0.98 |
C7—C8 | 1.385 (3) | C22—C23 | 1.385 (3) |
C7—H7 | 0.98 | C22—H22 | 0.98 |
C8—C13 | 1.380 (2) | C23—H23 | 0.98 |
O1···H7i | 2.8146 | O3···C4viii | 3.599 (2) |
O1···O2ii | 2.987 (2) | O4···H7i | 2.4674 |
O1···C4iii | 3.258 (2) | O4···H17Aiii | 2.6625 |
O1···C11iii | 3.453 (2) | O4···C7i | 3.407 (2) |
O1···C7i | 3.572 (2) | O4···C17iii | 3.413 (2) |
O2···H1O1ii | 2.34 (3) | C1···H17Biii | 2.8929 |
O2···H6iv | 2.8357 | C2···H17Biii | 2.9078 |
O2···H20v | 2.9011 | C2···C7ix | 3.405 (3) |
O2···O2ii | 3.018 (2) | C4···H23iii | 3.0107 |
O3···H4vi | 2.6652 | C6···H19viii | 3.0460 |
O3···H21vii | 2.6716 | C20···H5iv | 2.9727 |
O3···H3vi | 2.9433 | C21···H5iv | 3.0310 |
O3···C4vi | 3.351 (2) | H3···H22x | 2.4506 |
O3···C3viii | 3.451 (3) | H3···H21x | 2.6624 |
O3···C3vi | 3.493 (3) | H1O1···O1 | 0.90 (2) |
O3···C21vii | 3.528 (2) | ||
O2—S1—O3 | 118.96 (8) | C4—C11—C12 | 131.0 (2) |
O2—S1—C16 | 106.50 (8) | C10—C11—C12 | 109.0 (1) |
O2—S1—C18 | 109.26 (8) | C5—C12—C11 | 131.5 (2) |
O3—S1—C16 | 109.44 (8) | C5—C12—C13 | 119.8 (2) |
O3—S1—C18 | 108.63 (9) | C11—C12—C13 | 108.7 (1) |
C16—S1—C18 | 102.85 (8) | C8—C13—C9 | 128.7 (2) |
C15—O1—H1O1 | 111 (2) | C8—C13—C12 | 120.8 (2) |
C2—C1—C10 | 118.1 (2) | C9—C13—C12 | 110.5 (1) |
C2—C1—H1 | 120.9 | O4—C14—C9 | 126.8 (2) |
C10—C1—H1 | 120.9 | O4—C14—C15 | 125.7 (2) |
C1—C2—C3 | 120.6 (2) | C9—C14—C15 | 107.51 (14) |
C1—C2—H2 | 119.7 | O1—C15—C14 | 117.6 (2) |
C3—C2—H2 | 119.7 | O1—C15—C16 | 132.9 (2) |
C2—C3—C4 | 121.4 (2) | C14—C15—C16 | 109.53 (15) |
C2—C3—H3 | 119.3 | S1—C16—C15 | 124.75 (13) |
C4—C3—H3 | 119.3 | S1—C16—C17 | 121.25 (13) |
C3—C4—C11 | 118.7 (2) | C15—C16—C17 | 114.00 (14) |
C3—C4—H4 | 120.7 | C9—C17—C16 | 104.02 (14) |
C11—C4—H4 | 120.7 | C9—C17—H17B | 110.8 |
C6—C5—C12 | 118.8 (2) | C9—C17—H17A | 110.8 |
C6—C5—H5 | 120.6 | C16—C17—H17B | 110.8 |
C12—C5—H5 | 120.6 | C16—C17—H17A | 110.8 |
C5—C6—C7 | 121.2 (2) | H17B—C17—H17A | 109.5 |
C5—C6—H6 | 119.4 | S1—C18—C19 | 119.6 (1) |
C7—C6—H6 | 119.4 | S1—C18—C23 | 118.9 (1) |
C6—C7—C8 | 120.5 (2) | C19—C18—C23 | 121.4 (2) |
C6—C7—H7 | 119.7 | C18—C19—C20 | 118.8 (2) |
C8—C7—H7 | 119.7 | C18—C19—H19 | 120.6 |
C7—C8—C13 | 118.9 (2) | C20—C19—H19 | 120.6 |
C7—C8—H8 | 120.5 | C19—C20—C21 | 120.2 (2) |
C13—C8—H8 | 120.5 | C19—C20—H20 | 119.9 |
C10—C9—C13 | 101.83 (13) | C21—C20—H20 | 119.9 |
C10—C9—C14 | 109.41 (14) | C20—C21—C22 | 120.4 (2) |
C10—C9—C17 | 114.39 (14) | C20—C21—H21 | 119.8 |
C13—C9—C14 | 110.53 (14) | C22—C21—H21 | 119.8 |
C13—C9—C17 | 116.01 (14) | C21—C22—C23 | 120.2 (2) |
C14—C9—C17 | 104.70 (13) | C21—C22—H22 | 119.9 |
C1—C10—C9 | 129.0 (2) | C23—C22—H22 | 119.9 |
C1—C10—C11 | 121.1 (2) | C18—C23—C22 | 119.0 (2) |
C9—C10—C11 | 110.0 (1) | C18—C23—H23 | 120.5 |
C4—C11—C10 | 120.0 (2) | C22—C23—H23 | 120.5 |
S1—C16—C15—O1 | −3.2 (3) | C6—C5—C12—C11 | 179.7 (2) |
S1—C16—C15—C14 | 177.3 (1) | C6—C5—C12—C13 | 0.6 (3) |
S1—C16—C17—C9 | −175.2 (1) | C6—C7—C8—C13 | −0.1 (3) |
S1—C18—C19—C20 | −177.4 (2) | C7—C6—C5—C12 | −0.1 (3) |
S1—C18—C23—C22 | 177.2 (2) | C7—C8—C13—C9 | 178.2 (2) |
O1—C15—C14—O4 | 0.3 (3) | C7—C8—C13—C12 | 0.5 (3) |
O1—C15—C14—C9 | 179.7 (2) | C8—C13—C9—C10 | 179.2 (2) |
O1—C15—C16—C17 | 177.0 (2) | C8—C13—C9—C14 | −64.6 (2) |
O2—S1—C16—C15 | −9.5 (2) | C8—C13—C9—C17 | 54.4 (3) |
O2—S1—C16—C17 | 170.3 (1) | C8—C13—C12—C11 | 179.9 (2) |
O2—S1—C18—C19 | −35.8 (2) | C9—C10—C11—C12 | −2.0 (2) |
O2—S1—C18—C23 | 147.7 (2) | C9—C13—C12—C11 | 1.9 (2) |
O3—S1—C16—C15 | 120.3 (2) | C9—C14—C15—C16 | −0.8 (2) |
O3—S1—C16—C17 | −59.9 (2) | C9—C17—C16—C15 | 4.6 (2) |
O3—S1—C18—C19 | −167.0 (1) | C10—C9—C13—C12 | −2.9 (2) |
O3—S1—C18—C23 | 16.5 (2) | C10—C9—C14—C15 | −119.5 (2) |
O4—C14—C9—C10 | 59.8 (2) | C10—C9—C17—C16 | 115.1 (2) |
O4—C14—C9—C13 | −51.5 (2) | C10—C11—C12—C13 | 0.1 (2) |
O4—C14—C9—C17 | −177.1 (2) | C11—C10—C9—C13 | 3.0 (2) |
O4—C14—C15—C16 | 179.8 (2) | C11—C10—C9—C14 | −114.0 (2) |
C1—C2—C3—C4 | −1.0 (3) | C11—C10—C9—C17 | 128.9 (2) |
C1—C10—C9—C13 | −176.8 (2) | C12—C13—C9—C14 | 113.2 (2) |
C1—C10—C9—C14 | 66.2 (2) | C12—C13—C9—C17 | −127.8 (2) |
C1—C10—C9—C17 | −50.9 (2) | C13—C9—C14—C15 | 129.1 (1) |
C1—C10—C11—C4 | −0.9 (3) | C13—C9—C17—C16 | −126.8 (1) |
C1—C10—C11—C12 | 177.8 (2) | C14—C9—C17—C16 | −4.7 (2) |
C2—C1—C10—C9 | 179.8 (2) | C14—C15—C16—C17 | −2.5 (2) |
C2—C1—C10—C11 | 0.0 (3) | C15—C14—C9—C17 | 3.5 (2) |
C2—C3—C4—C11 | 0.0 (3) | C15—C16—S1—C18 | −124.3 (2) |
C3—C2—C1—C10 | 0.9 (3) | C16—S1—C18—C19 | 77.0 (2) |
C3—C4—C11—C10 | 0.9 (3) | C16—S1—C18—C23 | −99.4 (2) |
C3—C4—C11—C12 | −177.5 (2) | C17—C16—S1—C18 | 55.5 (2) |
C4—C11—C10—C9 | 179.2 (2) | C18—C19—C20—C21 | 0.7 (3) |
C4—C11—C12—C5 | −0.6 (4) | C18—C23—C22—C21 | −0.3 (3) |
C4—C11—C12—C13 | 178.6 (2) | C19—C18—C23—C22 | 0.8 (3) |
C5—C6—C7—C8 | −0.1 (4) | C19—C20—C21—C22 | −0.2 (4) |
C5—C12—C11—C10 | −179.1 (2) | C20—C19—C18—C23 | −1.0 (3) |
C5—C12—C13—C8 | −0.8 (3) | C20—C21—C22—C23 | 0.0 (4) |
C5—C12—C13—C9 | −178.8 (2) |
Symmetry codes: (i) −x−1/2, y−1/2, −z+3/2; (ii) −x, −y, −z+1; (iii) −x+1/2, y−1/2, −z+3/2; (iv) x+1/2, −y+1/2, z−1/2; (v) −x+1, −y, −z+1; (vi) x−1/2, −y+1/2, z−1/2; (vii) x−1, y, z; (viii) −x+1/2, y+1/2, −z+3/2; (ix) x+1, y, z; (x) −x+3/2, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···O2 | 0.90 (2) | 2.11 (2) | 2.836 (2) | 137 (2) |
O1—H1O1···O2ii | 0.90 (2) | 2.34 (3) | 2.987 (2) | 129 (2) |
C7—H7···O4xi | 0.98 | 2.47 | 3.407 (3) | 161 |
C17—H17A···O4viii | 0.98 | 2.66 | 3.413 (2) | 134 |
C4—H4···O3xii | 0.98 | 2.67 | 3.351 (2) | 127 |
C21—H21···O3ix | 0.98 | 2.67 | 3.528 (3) | 146 |
C7—H7···O1xi | 0.98 | 2.81 | 3.572 (3) | 135 |
C6—H6···O2xiii | 0.98 | 2.84 | 3.816 (2) | 179 |
Symmetry codes: (ii) −x, −y, −z+1; (viii) −x+1/2, y+1/2, −z+3/2; (ix) x+1, y, z; (xi) −x−1/2, y+1/2, −z+3/2; (xii) x+1/2, −y+1/2, z+1/2; (xiii) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C23H16O4S |
Mr | 388.44 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 8.478 (1), 10.406 (1), 21.336 (1) |
β (°) | 95.701 (9) |
V (Å3) | 1873.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.42 × 0.35 × 0.27 |
Data collection | |
Diffractometer | AFC5S diffractometer |
Absorption correction | – |
No. of measured, independent and observed (I > 2.0σI) reflections | 4618, 4333, 3246 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.083, 1.44 |
No. of reflections | 4331 |
No. of parameters | 257 |
No. of restraints | ? |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.47 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1995), SHELXS86 (Sheldrick, 1990), ORTEPII (Johnson, 1976), TEXSAN and PLATON (Spek, 1990).
S1—O2 | 1.4462 (13) | C9—C14 | 1.536 (2) |
S1—O3 | 1.4358 (14) | C9—C17 | 1.549 (2) |
S1—C16 | 1.742 (2) | C14—C15 | 1.488 (2) |
S1—C18 | 1.759 (2) | C15—C16 | 1.332 (2) |
O1—C15 | 1.333 (2) | C16—C17 | 1.503 (2) |
O4—C14 | 1.201 (2) | ||
O2—S1—O3 | 118.96 (8) | C14—C9—C17 | 104.70 (13) |
O2—S1—C16 | 106.50 (8) | O4—C14—C9 | 126.8 (2) |
O2—S1—C18 | 109.26 (8) | O4—C14—C15 | 125.7 (2) |
O3—S1—C16 | 109.44 (8) | C9—C14—C15 | 107.51 (14) |
O3—S1—C18 | 108.63 (9) | O1—C15—C14 | 117.6 (2) |
C16—S1—C18 | 102.85 (8) | O1—C15—C16 | 132.9 (2) |
C10—C9—C13 | 101.83 (13) | C14—C15—C16 | 109.53 (15) |
C10—C9—C14 | 109.41 (14) | S1—C16—C15 | 124.75 (13) |
C10—C9—C17 | 114.39 (14) | S1—C16—C17 | 121.25 (13) |
C13—C9—C14 | 110.53 (14) | C15—C16—C17 | 114.00 (14) |
C13—C9—C17 | 116.01 (14) | C9—C17—C16 | 104.02 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···O2 | 0.90 (2) | 2.11 (2) | 2.836 (2) | 137 (2) |
O1—H1O1···O2i | 0.90 (2) | 2.34 (3) | 2.987 (2) | 129 (2) |
C7—H7···O4ii | 0.98 | 2.47 | 3.407 (3) | 161 |
C17—H17A···O4iii | 0.98 | 2.66 | 3.413 (2) | 134 |
C4—H4···O3iv | 0.98 | 2.67 | 3.351 (2) | 127 |
C21—H21···O3v | 0.98 | 2.67 | 3.528 (3) | 146 |
C7—H7···O1ii | 0.98 | 2.81 | 3.572 (3) | 135 |
C6—H6···O2vi | 0.98 | 2.84 | 3.816 (2) | 179 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x−1/2, y+1/2, −z+3/2; (iii) −x+1/2, y+1/2, −z+3/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x+1, y, z; (vi) x−1/2, −y+1/2, z+1/2. |
a | b | c | d | e | f | g | h | |
a | S(6) | D22(6) | C22(15)[S(6)] | C22(10)[S(6)] | R44(24)[S(6)] | C22(13)[S(6)] | C22(11)[S(6)] | C21(11)[S(6)] |
b | R22(12) | C22(14) | C22(10) | C22(12) | C22(13) | C22(11) | C21(11) | |
c | C(7) | C21(8) | R44(28) | C22(19) | C12(7)[R12(5) | R44(20) | ||
d | C(5) | R44(24) | C22(15) | C22(12) | R44(20) | |||
e | C(9) | C21(14) | R44(26) | C22(10) | ||||
f | C(7) | C22(18) | C22(17) | |||||
g | C(8) | R44(18) | ||||||
h | C(10) |
This report on the title enol, (I), is one of a series on hydrogen bonding in organic solids, and the third structural report on a spirocyclopentyl-1,9'-[9H]fluorene compound. (I) crystallized in the centrosymmetric space group P21/n with one molecule as the asymmetric unit. The refined molecule and the labelling scheme are shown in Fig. 1. The hydroxyl-H atom is ordered and participates in a single intramolecular hydrogen bond and in a single intermolecular hydrogen bond, the geometric parameters of which are given in Table 2. The intermolecular hydrogen bond forms a first-level (Bernstein et al., 1995) cyclic dimer, with descriptor R22(12), about a center of symmetry. In addition, there are six leading C—H···O interactions (Taylor & Kennard, 1982; Steiner & Desiraju, 1998) whose parameters also are given in Table 2. Each molecule is linked directly by these interactions to eleven neighbors. The results of basic first- and second-level graph-set analysis involving all of these interactions, labelled a-h for this purpose in the order of their appearance in Table 2, are given in Table 3. The dominant patterns are rings (8) and chains (26). The chains propagate variously along [100] (6), [010] (10), [101] (4), [101] (3), [210] (2) and [110], and generate a richly three-dimensional network of interactions. It may be noted that, if only those C—H···O interactions having an H···O distance less than the corresponding Bondi (1964) van der Waals radius sum are considered, the resulting interaction network remains three-dimensional. A packing stereodiagram of the structure is given in Fig. 2. \sch
As for the fluorene cores in fluorene carboxylic acids (Blackburn et al., 1996a,b,c), best-fit planes for atoms C1—C4, C10 and C11 and atoms C5—C8, C12 and C13 have been chosen to define the fluorene core dihedral angle in (I). The maximum distance of any of these atoms from the best-fit plane including that atom is 0.007 (2) Å, and the dihedral angle is 2.10 (10)°. For structural comparisons, tetrabenzodispiro[4.0.4.3]tridecatetraene [hereafter, (II)] (Fritze et al., 1995), which can be viewed in the present context as a double spirocyclopentane-1,9'-[9H]fluorene, is particularly appropriate. In (II), there are four independent fluorene cores and for them the maximum deviation of an atom from the corresponding best-fit planes is 0.023 (3) Å, and the dihedral angles are 10.60 (11), 9.19 (8), 8.32 (10) and 6.68 (9)°, all considerably larger than in (I). The central ring of the fluorene core is less nearly planar than the outer rings in (I), the maximum atom deviation from the best-fit plane being 0.018 (2) Å; for (II), the quite similar corresponding values are 0.025 (2), 0.022 (2), 0.027 (2) and 0.020 (2) Å. A second notable difference between (I) and (II) is that the cyclopentyl ring has a 0.033 (2) Å maximum atom deviation from the best-fit plane in (I), but 0.245 (2) and 0.225 (2) Å in (II). A further similarity of (I) and (II) is that the dihedral angles between the best-fit planes describing the spiro-connected five-membered rings are, as expected, close to 90°, being 89.95 (10)° in (I) and 89.67 (10), 88.68 (9), 89.46 (10) and 90.00 (10) ° in (II). For the phenyl ring of (I), C18—C23, the maximum deviation of an atom from the best-fit plane describing them is 0.004 (2) Å.
Selected distances and angles for (I) are given in Table 1. A l l distances and angles fall within normal ranges. The r.m.s. deviation within the seven pairs of chemically equivalent bond distances in the fluorene core is 0.006 Å for (I), while for the four cores in (II) it is 0.007, 0.002, 0.006 and 0.006 Å. Overall, the mean values of the seven chemically equivalent bond distances in the fluorene core of (I) are in good agreement with the corresponding seven grand mean values for the four fluorene cores of (II): C4—C11, 1.388 (2) versus 1.392 (3); C3—C4, 1.378 (3) versus 1.375 (5); C2—C3, 1.374 (3) versus 1.379 (6); C1—C2, 1.388 (3) versus 1.391 (4); C1—C10, 1.380 (2) versus 1.386 (4); C10—C11, 1.394 (2) versus 1.399 (3); and C9—C10, 1.520 (5) versus 1.525 (3) Å. The bond distance for the unique bond of the fluorene core, C11—C12, is 1.460 (2) Å for (I), 1.462 (3) Å (grand mean) for (II). Excluding pairs of atoms in hydrogen-bonded groups or tabulated C—H···O interactions, the closest intermolecular approaches are between C1 and H17Bvii (vii = 1/2 − x, −1/2 + y, 3/2 − z), and are 0.01 Å less than the corresponding Bondi (1964) van der Waals radius sum.