Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010502874X/ta1509sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010502874X/ta1509Isup2.hkl |
CCDC reference: 288632
Thiocoumarin (1.0 eq) and N-benzoyl-N-methyl-alanine (1.2 eq) were reacted in dioxane (200 ml) after addition of acetic anhydride (5.0 eq), yielding (I), as described by Grassi et al. (2005). After purification, colourless crystals of (I) (m. p. 416–417 K) were obtained by slow evaporation from dioxane.
All H atoms were positioned geometrically and refined using a riding model, with C—H distances in the range 0.93–0.98 Å [Please check amended upper limit] and Uiso(H) values of 1.2Ueq(C) or 1.5Ueq(Cmethyl).
Data collection: X8 APEX software (Bruker, 2000); cell refinement: X8 APEX software (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (Bruker, 2000); software used to prepare material for publication: WinGX (Farrugia, 1999).
C27H21NO4S | Z = 2 |
Mr = 455.51 | F(000) = 476 |
Triclinic, P1 | Dx = 1.300 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6245 (7) Å | Cell parameters from 4015 reflections |
b = 11.6423 (10) Å | θ = 2.6–25° |
c = 13.1778 (11) Å | µ = 0.17 mm−1 |
α = 97.658 (3)° | T = 298 K |
β = 104.134 (3)° | Irregular, colourless |
γ = 110.821 (3)° | 0.58 × 0.4 × 0.32 mm |
V = 1163.44 (17) Å3 |
X8 CCD area detector diffractometer | 3329 reflections with I > 2σ(I) |
ϕ and ω scans | Rint = 0.040 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 25°, θmin = 2.6° |
Tmin = 0.789, Tmax = 0.95 | h = −10→10 |
17961 measured reflections | k = −13→13 |
4015 independent reflections | l = −15→15 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.0886P)2 + 0.5138P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.162 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.50 e Å−3 |
4015 reflections | Δρmin = −0.33 e Å−3 |
300 parameters |
C27H21NO4S | γ = 110.821 (3)° |
Mr = 455.51 | V = 1163.44 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6245 (7) Å | Mo Kα radiation |
b = 11.6423 (10) Å | µ = 0.17 mm−1 |
c = 13.1778 (11) Å | T = 298 K |
α = 97.658 (3)° | 0.58 × 0.4 × 0.32 mm |
β = 104.134 (3)° |
X8 CCD area detector diffractometer | 4015 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3329 reflections with I > 2σ(I) |
Tmin = 0.789, Tmax = 0.95 | Rint = 0.040 |
17961 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.50 e Å−3 |
4015 reflections | Δρmin = −0.33 e Å−3 |
300 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.3141 (2) | 1.01106 (18) | 0.40812 (14) | 0.0580 (5) | |
O2 | 0.3207 (2) | 0.81060 (18) | 0.12190 (14) | 0.0538 (5) | |
O3 | −0.1635 (2) | 0.8682 (2) | −0.00333 (15) | 0.0626 (5) | |
S1 | −0.18367 (8) | 0.59086 (6) | 0.12573 (5) | 0.0511 (2) | |
C2 | −0.1025 (3) | 0.7239 (2) | 0.25133 (18) | 0.0408 (5) | |
C3 | 0.0980 (3) | 0.7678 (2) | 0.28576 (18) | 0.0373 (5) | |
H3 | 0.1463 | 0.7995 | 0.3643 | 0.045* | |
C4 | 0.1399 (3) | 0.6572 (2) | 0.25229 (18) | 0.0409 (5) | |
C5 | 0.2961 (3) | 0.6451 (3) | 0.2947 (2) | 0.0499 (6) | |
H5 | 0.3848 | 0.7072 | 0.3526 | 0.06* | |
C6 | 0.3183 (4) | 0.5401 (3) | 0.2502 (3) | 0.0601 (7) | |
H6 | 0.4226 | 0.5317 | 0.2782 | 0.072* | |
C7 | 0.1868 (4) | 0.4474 (3) | 0.1643 (2) | 0.0636 (8) | |
H7 | 0.2043 | 0.3778 | 0.1343 | 0.076* | |
C8 | 0.0293 (4) | 0.4569 (3) | 0.1223 (2) | 0.0556 (7) | |
H8 | −0.0598 | 0.3937 | 0.0653 | 0.067* | |
C9 | 0.0072 (3) | 0.5622 (2) | 0.16688 (19) | 0.0442 (5) | |
C10 | −0.1743 (3) | 0.6773 (2) | 0.34018 (19) | 0.0441 (5) | |
C11 | −0.1997 (4) | 0.5576 (3) | 0.3555 (2) | 0.0603 (7) | |
H11 | −0.182 | 0.5012 | 0.3073 | 0.072* | |
C12 | −0.2514 (4) | 0.5206 (3) | 0.4422 (3) | 0.0715 (9) | |
H12 | −0.265 | 0.4406 | 0.4527 | 0.086* | |
C13 | −0.2823 (4) | 0.6011 (3) | 0.5119 (2) | 0.0680 (8) | |
H13 | −0.318 | 0.5755 | 0.5693 | 0.082* | |
C14 | −0.2608 (4) | 0.7190 (3) | 0.4975 (2) | 0.0613 (7) | |
H14 | −0.2848 | 0.7729 | 0.5441 | 0.074* | |
C15 | −0.2031 (3) | 0.7591 (3) | 0.4133 (2) | 0.0517 (6) | |
H15 | −0.1838 | 0.8409 | 0.406 | 0.062* | |
N16 | −0.1325 (2) | 0.8329 (2) | 0.22964 (16) | 0.0447 (5) | |
C17 | 0.0002 (3) | 0.9113 (2) | 0.18809 (18) | 0.0406 (5) | |
C18 | 0.1634 (3) | 0.8811 (2) | 0.23085 (17) | 0.0373 (5) | |
C19 | −0.3141 (3) | 0.8140 (3) | 0.1793 (3) | 0.0620 (8) | |
H19A | −0.3574 | 0.7607 | 0.1077 | 0.093* | |
H19B | −0.3193 | 0.8944 | 0.1759 | 0.093* | |
H19C | −0.3844 | 0.7744 | 0.2214 | 0.093* | |
C20 | 0.0251 (3) | 1.0489 (3) | 0.2171 (2) | 0.0546 (6) | |
H20A | −0.079 | 1.0572 | 0.1791 | 0.082* | |
H20B | 0.1218 | 1.1008 | 0.1971 | 0.082* | |
H20C | 0.0483 | 1.0757 | 0.2933 | 0.082* | |
C21 | 0.2046 (3) | 0.8390 (2) | 0.13019 (18) | 0.0412 (5) | |
O22 | 0.0807 (2) | 0.83481 (17) | 0.03821 (12) | 0.0481 (4) | |
C23 | −0.0440 (3) | 0.8698 (2) | 0.06548 (19) | 0.0457 (6) | |
C24 | 0.3196 (3) | 0.9927 (2) | 0.31661 (19) | 0.0428 (5) | |
C25 | 0.4745 (3) | 1.0749 (2) | 0.2905 (2) | 0.0461 (6) | |
C26 | 0.6335 (3) | 1.1253 (3) | 0.3730 (2) | 0.0597 (7) | |
H26 | 0.6392 | 1.1055 | 0.4395 | 0.072* | |
C27 | 0.7833 (4) | 1.2050 (3) | 0.3563 (3) | 0.0742 (9) | |
H27 | 0.8898 | 1.2379 | 0.4112 | 0.089* | |
C28 | 0.7744 (4) | 1.2352 (3) | 0.2588 (3) | 0.0749 (9) | |
H28 | 0.8752 | 1.2885 | 0.2477 | 0.09* | |
C29 | 0.6182 (4) | 1.1878 (3) | 0.1770 (3) | 0.0735 (9) | |
H29 | 0.6134 | 1.2102 | 0.1115 | 0.088* | |
C30 | 0.4676 (4) | 1.1065 (3) | 0.1920 (2) | 0.0589 (7) | |
H30 | 0.3621 | 1.0732 | 0.1362 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0573 (11) | 0.0605 (11) | 0.0448 (10) | 0.0123 (9) | 0.0134 (8) | 0.0139 (8) |
O2 | 0.0478 (10) | 0.0709 (12) | 0.0598 (11) | 0.0329 (9) | 0.0254 (8) | 0.0295 (9) |
O3 | 0.0476 (10) | 0.0881 (14) | 0.0542 (11) | 0.0294 (10) | 0.0068 (8) | 0.0361 (10) |
S1 | 0.0407 (4) | 0.0575 (4) | 0.0474 (4) | 0.0153 (3) | 0.0070 (3) | 0.0137 (3) |
C2 | 0.0292 (11) | 0.0508 (13) | 0.0462 (12) | 0.0156 (10) | 0.0144 (9) | 0.0208 (10) |
C3 | 0.0302 (11) | 0.0435 (12) | 0.0401 (11) | 0.0137 (10) | 0.0111 (9) | 0.0196 (9) |
C4 | 0.0392 (12) | 0.0450 (13) | 0.0455 (12) | 0.0169 (11) | 0.0181 (10) | 0.0250 (10) |
C5 | 0.0425 (13) | 0.0550 (15) | 0.0623 (15) | 0.0227 (12) | 0.0195 (11) | 0.0323 (12) |
C6 | 0.0603 (17) | 0.0699 (19) | 0.080 (2) | 0.0419 (16) | 0.0365 (15) | 0.0437 (16) |
C7 | 0.088 (2) | 0.0638 (18) | 0.0697 (18) | 0.0471 (18) | 0.0433 (17) | 0.0333 (15) |
C8 | 0.0707 (18) | 0.0521 (15) | 0.0507 (14) | 0.0242 (14) | 0.0277 (13) | 0.0197 (12) |
C9 | 0.0455 (13) | 0.0473 (13) | 0.0437 (12) | 0.0157 (11) | 0.0197 (10) | 0.0219 (10) |
C10 | 0.0323 (12) | 0.0537 (14) | 0.0496 (13) | 0.0158 (11) | 0.0155 (10) | 0.0230 (11) |
C11 | 0.0642 (17) | 0.0620 (17) | 0.0738 (18) | 0.0297 (15) | 0.0392 (15) | 0.0333 (14) |
C12 | 0.076 (2) | 0.072 (2) | 0.088 (2) | 0.0306 (17) | 0.0462 (18) | 0.0493 (17) |
C13 | 0.0550 (17) | 0.092 (2) | 0.0594 (17) | 0.0205 (16) | 0.0275 (14) | 0.0363 (16) |
C14 | 0.0496 (15) | 0.080 (2) | 0.0474 (14) | 0.0175 (14) | 0.0183 (12) | 0.0126 (13) |
C15 | 0.0425 (14) | 0.0572 (15) | 0.0531 (14) | 0.0157 (12) | 0.0160 (11) | 0.0172 (12) |
N16 | 0.0322 (10) | 0.0567 (12) | 0.0570 (12) | 0.0234 (9) | 0.0178 (9) | 0.0288 (10) |
C17 | 0.0341 (12) | 0.0486 (13) | 0.0441 (12) | 0.0198 (10) | 0.0114 (9) | 0.0198 (10) |
C18 | 0.0312 (11) | 0.0428 (12) | 0.0406 (11) | 0.0155 (10) | 0.0103 (9) | 0.0190 (9) |
C19 | 0.0362 (13) | 0.084 (2) | 0.0808 (19) | 0.0311 (14) | 0.0205 (13) | 0.0431 (16) |
C20 | 0.0507 (15) | 0.0538 (15) | 0.0670 (16) | 0.0286 (13) | 0.0165 (12) | 0.0225 (12) |
C21 | 0.0371 (12) | 0.0447 (13) | 0.0441 (12) | 0.0151 (11) | 0.0137 (10) | 0.0209 (10) |
O22 | 0.0441 (9) | 0.0626 (11) | 0.0401 (9) | 0.0227 (8) | 0.0112 (7) | 0.0205 (7) |
C23 | 0.0381 (13) | 0.0530 (14) | 0.0485 (13) | 0.0175 (11) | 0.0121 (10) | 0.0260 (11) |
C24 | 0.0377 (12) | 0.0439 (13) | 0.0457 (13) | 0.0161 (11) | 0.0078 (10) | 0.0184 (10) |
C25 | 0.0376 (12) | 0.0446 (13) | 0.0537 (14) | 0.0137 (11) | 0.0095 (10) | 0.0215 (11) |
C26 | 0.0428 (15) | 0.0609 (16) | 0.0636 (17) | 0.0139 (13) | 0.0049 (12) | 0.0187 (13) |
C27 | 0.0374 (15) | 0.0683 (19) | 0.098 (2) | 0.0072 (14) | 0.0104 (15) | 0.0197 (17) |
C28 | 0.0510 (18) | 0.0559 (18) | 0.120 (3) | 0.0129 (15) | 0.0377 (18) | 0.0325 (18) |
C29 | 0.073 (2) | 0.0675 (19) | 0.096 (2) | 0.0266 (17) | 0.0408 (19) | 0.0509 (18) |
C30 | 0.0480 (15) | 0.0614 (16) | 0.0684 (17) | 0.0179 (13) | 0.0152 (13) | 0.0372 (14) |
O1—C24 | 1.212 (3) | C14—H14 | 0.93 |
O2—C21 | 1.185 (3) | C15—H15 | 0.93 |
O3—C23 | 1.188 (3) | N16—C17 | 1.463 (3) |
S1—C9 | 1.765 (2) | N16—C19 | 1.466 (3) |
S1—C2 | 1.900 (2) | C17—C20 | 1.521 (3) |
C2—N16 | 1.432 (3) | C17—C23 | 1.533 (3) |
C2—C10 | 1.528 (3) | C17—C18 | 1.562 (3) |
C2—C3 | 1.544 (3) | C18—C21 | 1.518 (3) |
C3—C4 | 1.497 (3) | C18—C24 | 1.550 (3) |
C3—C18 | 1.583 (3) | C19—H19A | 0.96 |
C3—H3 | 0.98 | C19—H19B | 0.96 |
C4—C5 | 1.391 (3) | C19—H19C | 0.96 |
C4—C9 | 1.393 (3) | C20—H20A | 0.96 |
C5—C6 | 1.380 (4) | C20—H20B | 0.96 |
C5—H5 | 0.93 | C20—H20C | 0.96 |
C6—C7 | 1.382 (5) | C21—O22 | 1.389 (3) |
C6—H6 | 0.93 | O22—C23 | 1.383 (3) |
C7—C8 | 1.386 (4) | C24—C25 | 1.491 (3) |
C7—H7 | 0.93 | C25—C30 | 1.389 (4) |
C8—C9 | 1.384 (4) | C25—C26 | 1.392 (4) |
C8—H8 | 0.93 | C26—C27 | 1.386 (4) |
C10—C11 | 1.382 (4) | C26—H26 | 0.93 |
C10—C15 | 1.392 (4) | C27—C28 | 1.368 (5) |
C11—C12 | 1.390 (4) | C27—H27 | 0.93 |
C11—H11 | 0.93 | C28—C29 | 1.372 (5) |
C12—C13 | 1.364 (5) | C28—H28 | 0.93 |
C12—H12 | 0.93 | C29—C30 | 1.387 (4) |
C13—C14 | 1.364 (5) | C29—H29 | 0.93 |
C13—H13 | 0.93 | C30—H30 | 0.93 |
C14—C15 | 1.391 (4) | ||
C9—S1—C2 | 91.48 (10) | N16—C17—C20 | 110.25 (19) |
N16—C2—C10 | 112.05 (19) | N16—C17—C23 | 113.37 (19) |
N16—C2—C3 | 104.92 (18) | C20—C17—C23 | 108.22 (19) |
C10—C2—C3 | 110.96 (17) | N16—C17—C18 | 105.35 (16) |
N16—C2—S1 | 113.17 (15) | C20—C17—C18 | 117.16 (19) |
C10—C2—S1 | 111.59 (16) | C23—C17—C18 | 102.43 (17) |
C3—C2—S1 | 103.63 (15) | C21—C18—C24 | 113.68 (18) |
C4—C3—C2 | 108.84 (18) | C21—C18—C17 | 104.54 (17) |
C4—C3—C18 | 115.16 (17) | C24—C18—C17 | 113.78 (18) |
C2—C3—C18 | 104.73 (16) | C21—C18—C3 | 111.42 (18) |
C4—C3—H3 | 109.3 | C24—C18—C3 | 108.37 (17) |
C2—C3—H3 | 109.3 | C17—C18—C3 | 104.70 (16) |
C18—C3—H3 | 109.3 | N16—C19—H19A | 109.5 |
C5—C4—C9 | 119.5 (2) | N16—C19—H19B | 109.5 |
C5—C4—C3 | 126.6 (2) | H19A—C19—H19B | 109.5 |
C9—C4—C3 | 113.9 (2) | N16—C19—H19C | 109.5 |
C6—C5—C4 | 119.5 (3) | H19A—C19—H19C | 109.5 |
C6—C5—H5 | 120.3 | H19B—C19—H19C | 109.5 |
C4—C5—H5 | 120.3 | C17—C20—H20A | 109.5 |
C5—C6—C7 | 120.5 (3) | C17—C20—H20B | 109.5 |
C5—C6—H6 | 119.7 | H20A—C20—H20B | 109.5 |
C7—C6—H6 | 119.7 | C17—C20—H20C | 109.5 |
C6—C7—C8 | 120.7 (3) | H20A—C20—H20C | 109.5 |
C6—C7—H7 | 119.6 | H20B—C20—H20C | 109.5 |
C8—C7—H7 | 119.6 | O2—C21—O22 | 119.7 (2) |
C9—C8—C7 | 118.7 (3) | O2—C21—C18 | 129.6 (2) |
C9—C8—H8 | 120.7 | O22—C21—C18 | 110.65 (18) |
C7—C8—H8 | 120.7 | C23—O22—C21 | 110.53 (18) |
C8—C9—C4 | 121.0 (2) | O3—C23—O22 | 119.9 (2) |
C8—C9—S1 | 125.5 (2) | O3—C23—C17 | 128.5 (2) |
C4—C9—S1 | 113.49 (18) | O22—C23—C17 | 111.48 (18) |
C11—C10—C15 | 118.2 (2) | O1—C24—C25 | 119.9 (2) |
C11—C10—C2 | 121.5 (2) | O1—C24—C18 | 117.7 (2) |
C15—C10—C2 | 120.1 (2) | C25—C24—C18 | 122.4 (2) |
C10—C11—C12 | 120.7 (3) | C30—C25—C26 | 119.3 (2) |
C10—C11—H11 | 119.6 | C30—C25—C24 | 124.3 (2) |
C12—C11—H11 | 119.6 | C26—C25—C24 | 116.4 (2) |
C13—C12—C11 | 120.3 (3) | C27—C26—C25 | 120.2 (3) |
C13—C12—H12 | 119.9 | C27—C26—H26 | 119.9 |
C11—C12—H12 | 119.9 | C25—C26—H26 | 119.9 |
C12—C13—C14 | 120.1 (3) | C28—C27—C26 | 119.8 (3) |
C12—C13—H13 | 120 | C28—C27—H27 | 120.1 |
C14—C13—H13 | 120 | C26—C27—H27 | 120.1 |
C13—C14—C15 | 120.3 (3) | C27—C28—C29 | 120.8 (3) |
C13—C14—H14 | 119.8 | C27—C28—H28 | 119.6 |
C15—C14—H14 | 119.8 | C29—C28—H28 | 119.6 |
C14—C15—C10 | 120.4 (3) | C28—C29—C30 | 120.1 (3) |
C14—C15—H15 | 119.8 | C28—C29—H29 | 120 |
C10—C15—H15 | 119.8 | C30—C29—H29 | 120 |
C2—N16—C17 | 111.22 (17) | C29—C30—C25 | 119.9 (3) |
C2—N16—C19 | 117.0 (2) | C29—C30—H30 | 120.1 |
C17—N16—C19 | 117.56 (18) | C25—C30—H30 | 120.1 |
C9—S1—C2—N16 | 137.23 (16) | C19—N16—C17—C18 | −163.5 (2) |
C9—S1—C2—C10 | −95.29 (16) | N16—C17—C18—C21 | 124.21 (19) |
C9—S1—C2—C3 | 24.17 (15) | C20—C17—C18—C21 | −112.8 (2) |
N16—C2—C3—C4 | −149.03 (18) | C23—C17—C18—C21 | 5.4 (2) |
C10—C2—C3—C4 | 89.8 (2) | N16—C17—C18—C24 | −111.2 (2) |
S1—C2—C3—C4 | −30.11 (19) | C20—C17—C18—C24 | 11.8 (3) |
N16—C2—C3—C18 | −25.4 (2) | C23—C17—C18—C24 | 130.00 (19) |
C10—C2—C3—C18 | −146.57 (19) | N16—C17—C18—C3 | 6.9 (2) |
S1—C2—C3—C18 | 93.55 (17) | C20—C17—C18—C3 | 129.9 (2) |
C2—C3—C4—C5 | −159.0 (2) | C23—C17—C18—C3 | −111.85 (19) |
C18—C3—C4—C5 | 83.8 (3) | C4—C3—C18—C21 | 18.0 (2) |
C2—C3—C4—C9 | 23.8 (2) | C2—C3—C18—C21 | −101.5 (2) |
C18—C3—C4—C9 | −93.4 (2) | C4—C3—C18—C24 | −107.8 (2) |
C9—C4—C5—C6 | 1.2 (3) | C2—C3—C18—C24 | 132.71 (19) |
C3—C4—C5—C6 | −175.9 (2) | C4—C3—C18—C17 | 130.45 (19) |
C4—C5—C6—C7 | −0.1 (4) | C2—C3—C18—C17 | 10.9 (2) |
C5—C6—C7—C8 | −1.0 (4) | C24—C18—C21—O2 | 52.4 (3) |
C6—C7—C8—C9 | 1.1 (4) | C17—C18—C21—O2 | 177.0 (2) |
C7—C8—C9—C4 | 0.0 (4) | C3—C18—C21—O2 | −70.4 (3) |
C7—C8—C9—S1 | −179.37 (19) | C24—C18—C21—O22 | −128.18 (19) |
C5—C4—C9—C8 | −1.1 (3) | C17—C18—C21—O22 | −3.5 (2) |
C3—C4—C9—C8 | 176.3 (2) | C3—C18—C21—O22 | 109.0 (2) |
C5—C4—C9—S1 | 178.33 (17) | O2—C21—O22—C23 | 179.3 (2) |
C3—C4—C9—S1 | −4.3 (2) | C18—C21—O22—C23 | −0.2 (3) |
C2—S1—C9—C8 | 166.9 (2) | C21—O22—C23—O3 | −177.8 (2) |
C2—S1—C9—C4 | −12.49 (18) | C21—O22—C23—C17 | 4.1 (3) |
N16—C2—C10—C11 | 163.5 (2) | N16—C17—C23—O3 | 63.2 (3) |
C3—C2—C10—C11 | −79.6 (3) | C20—C17—C23—O3 | −59.4 (3) |
S1—C2—C10—C11 | 35.4 (3) | C18—C17—C23—O3 | 176.2 (3) |
N16—C2—C10—C15 | −21.5 (3) | N16—C17—C23—O22 | −119.0 (2) |
C3—C2—C10—C15 | 95.4 (2) | C20—C17—C23—O22 | 118.4 (2) |
S1—C2—C10—C15 | −149.59 (19) | C18—C17—C23—O22 | −6.0 (2) |
C15—C10—C11—C12 | −0.5 (4) | C21—C18—C24—O1 | −161.6 (2) |
C2—C10—C11—C12 | 174.6 (3) | C17—C18—C24—O1 | 78.8 (3) |
C10—C11—C12—C13 | 1.7 (5) | C3—C18—C24—O1 | −37.2 (3) |
C11—C12—C13—C14 | −0.7 (5) | C21—C18—C24—C25 | 17.3 (3) |
C12—C13—C14—C15 | −1.6 (4) | C17—C18—C24—C25 | −102.2 (2) |
C13—C14—C15—C10 | 2.9 (4) | C3—C18—C24—C25 | 141.8 (2) |
C11—C10—C15—C14 | −1.8 (4) | O1—C24—C25—C30 | −147.8 (3) |
C2—C10—C15—C14 | −177.0 (2) | C18—C24—C25—C30 | 33.2 (4) |
C10—C2—N16—C17 | 152.47 (19) | O1—C24—C25—C26 | 30.0 (3) |
C3—C2—N16—C17 | 32.0 (2) | C18—C24—C25—C26 | −149.0 (2) |
S1—C2—N16—C17 | −80.3 (2) | C30—C25—C26—C27 | −0.7 (4) |
C10—C2—N16—C19 | −68.5 (3) | C24—C25—C26—C27 | −178.6 (3) |
C3—C2—N16—C19 | 171.0 (2) | C25—C26—C27—C28 | 0.7 (5) |
S1—C2—N16—C19 | 58.8 (2) | C26—C27—C28—C29 | 0.2 (5) |
C2—N16—C17—C20 | −152.0 (2) | C27—C28—C29—C30 | −1.2 (5) |
C19—N16—C17—C20 | 69.2 (3) | C28—C29—C30—C25 | 1.1 (5) |
C2—N16—C17—C23 | 86.5 (2) | C26—C25—C30—C29 | −0.2 (4) |
C19—N16—C17—C23 | −52.3 (3) | C24—C25—C30—C29 | 177.5 (3) |
C2—N16—C17—C18 | −24.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C30—H30···O3i | 0.93 | 2.48 | 3.272 (3) | 143 |
C26—H26···O1ii | 0.93 | 2.60 | 3.484 (3) | 159 |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C27H21NO4S |
Mr | 455.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.6245 (7), 11.6423 (10), 13.1778 (11) |
α, β, γ (°) | 97.658 (3), 104.134 (3), 110.821 (3) |
V (Å3) | 1163.44 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.58 × 0.4 × 0.32 |
Data collection | |
Diffractometer | X8 CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.789, 0.95 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17961, 4015, 3329 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.162, 1.10 |
No. of reflections | 4015 |
No. of parameters | 300 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.33 |
Computer programs: X8 APEX software (Bruker, 2000), SAINT (Bruker, 2000), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), XPW (Bruker, 2000), WinGX (Farrugia, 1999).
O1—C24 | 1.212 (3) | S1—C2 | 1.900 (2) |
O2—C21 | 1.185 (3) | C3—C18 | 1.583 (3) |
O3—C23 | 1.188 (3) | C24—C25 | 1.491 (3) |
S1—C9 | 1.765 (2) | ||
C9—S1—C2 | 91.48 (10) | C2—N16—C19 | 117.0 (2) |
C2—N16—C17 | 111.22 (17) | C17—N16—C19 | 117.56 (18) |
S1—C2—N16—C17 | −80.3 (2) | O1—C24—C25—C30 | −147.8 (3) |
C2—N16—C17—C23 | 86.5 (2) | O1—C24—C25—C26 | 30.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C30—H30···O3i | 0.93 | 2.48 | 3.272 (3) | 143 |
C26—H26···O1ii | 0.93 | 2.60 | 3.484 (3) | 159 |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
Several syntheses of shape-specific molecules through heteroaromatic annulations in a cis–syn–cis mode have been achieved (Mehta et al., 1992). Often, U-shaped structures are obtained and are driven by stereospecific syntheses (Albrecht et al., 1992), and they are considered to be a new class of potential molecular hosts (Marchand et al., 1990; Mehta et al., 1989, 1998). Benzo[4,5]thieno[2,3-b]pyrrole derivatives have been produced in a domino cascade reaction starting from mesoionic 1,3-oxazolin-5-olates and thiocoumarins having an electron-withdrawing group at the 3-position (Grassi et al., 2005).
The crystal structure of the title compound contains molecules of (±)-3-benzoyl-1,2-dimethyl-8a-phenyl-2-benzothieno[2,3-b]pyrrole-1,2-dicarboxylic anhydride, (I), as a racemate. The main body of (I) consists of four consecutive ringsfused to each other by edge-sharing. The core pyrrolidine ring is flanked by a succinic anhydride on one side and a benzothiophene group on the other. These condensed rings confer on the structure a 'U-shaped' configuration (endo-form), with angles between the mean benzothiophene and pyrrolidine planes of 68.5 (1)°, and between pyrrolidine and succinic anhydride of 68.9 (1)° (Fig. 1). The succinic anhydride ring is close to planar [maximum deviation from the mean plane for C23 is 0.037 (3) Å], but the other five-membered rings show significant deviations from planarity.
Puckering analysis (Cremer & Pople, 1975) of the thiophene ring S1/C2/C3/C4/C9 shows an E (envelope) conformation, with Q = 0.316 (2) and ϕ = 4.3 (4)%. The same analysis of the pyrrolidine ring C18/C3/C2/N16/C17 shows a 3T2 (twist) conformation [Q = 0.281 (2) and ϕ = −95.1 (5)], where the pseudo twofold symmetry axis passes through C18. The four atoms on the contact edges of this ring are chiral [C2(R), C3(R), C17(S), C18(R)] and, since the space group is centrosymmetric, the molecule exists in the solid state as a racemic pair.
The phenyl and methyl substituents on C2 and C17 favour a flattening of the pyramid-like geometry around atom N16, resulting in the sum of the bond angles around N16 being 345.8 (6)°, compared with 335.31° measured for an analogous unsubstituted pyrrolidine moiety (Pedrosa et al., 2002). Atom C8 bears a benzoyl group which, because of steric hindrance, cannot maintain a stable planar conformation. The dihedral angle around O1—C24—C25—C26, and the short C24—O1 and long C24—C25 bond distances (Table 1), compared with the corresponding geometric parameters of a similar structural moiety [O—C—C—C = 0.32°, C═O = 1.223 Å and C—C = 1.501 Å; Nagendrappa & Begum, 1999], indicate a hampered conjugation among the pure p orbitals belonging to each atom of this fragment. The peripheral rings flanking the pyrrolidine occur on the same side and almost parallel to each other, thus causing a noteworthy steric hindrance; this is reflected in the C18—C3 bond distance, which is longer than expected (Table 2), as already shown in another `boat-like' structure in which the equivalent bond length is 1.573 Å (Huang et al., 2001).
The crystal packing of (I) features two weak cyclic hydrogen-bonding interactions both lying across crystallographic inversion centres (Table 2). The first interaction, C30—H30···O3i [C···O = 3.272 (3) Å; symmetry code: (i) −x, 2 − y, −z], involves one of the two anhydride O atoms as acceptor and an aromatic C—H as donor, leading to a R22(16) graph-set pattern (Bernstein et al., 1995). The second interaction, C26—H26···O1ii [C···O = 3.484 (3) Å; symmetry code: (ii) 1 − x, 2 − y, 1 − z], involves, uniquely, the benzoyl group of two enantiomeric units joined in an R22(10) graph-set pattern. These intermolecular connections combine to give a `chain of rings' ribbon polymer N2 = C22 [R22(16)R22(10)] (Bernstein et al., 1995) extending along the [101] crystallographic direction (Fig. 2). Other weak dipolar and hydrophobic interactions support the overall lattice.