Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107006129/hj3030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107006129/hj3030Isup2.hkl |
CCDC reference: 649082
The starting material, (II), was prepared according to the previously reported procedure of Sonar et al. (2004). The title compound, (I), was prepared by the reaction of (II) with semicarbazide to afford a single geometric isomer. Crystallization from methanol afforded yellow crystals. 1H NMR (DMSO-d6, δ, p.p.m.): 1.70 (m, 4H), 2.81 (m, 2H), 3.16 (m, 2H), 3.40 (s, 1H), 6.51 (b, 2H), 7.13 (s, 1H), 7.34 (m, 2H), 7.59 (t, 2H), 7.69 (t, 1H), 7.92 (d, 3H) 8.07 (d, 1H), 8.42 (s, 1H), 9.54 (s, 1H); 13C NMR (DMSO-d6, δ, p.p.m.): 24.63, 25.13, 46.62, 105.47, 112.94, 117.65, 120.31, 123.33, 124.94, 125.99, 126.38, 129.77, 130.18, 133.52, 134.54, 136.59, 146.02, 148.47, 157.27.
H atoms were found in difference Fourier maps and subsequently placed in idealized positions, with constrained distances of 0.95 (Csp2), 0.99 (CH2), 1.00 (CH) and 0.88 Å (NH). Uiso(H) values were set to 1.2Ueq of the attached atom.
Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 and local programs.
C23H23N5O3S | F(000) = 944 |
Mr = 449.52 | Dx = 1.405 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5073 reflections |
a = 11.2058 (2) Å | θ = 1.0–27.5° |
b = 12.7677 (2) Å | µ = 0.19 mm−1 |
c = 15.0499 (3) Å | T = 90 K |
β = 99.3278 (9)° | Block, yellow |
V = 2124.75 (7) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 4851 independent reflections |
Radiation source: fine-focus sealed tube | 3681 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 18 pixels mm-1 | θmax = 27.5°, θmin = 1.8° |
ω scans at fixed χ = 55° | h = −14→14 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −16→16 |
Tmin = 0.945, Tmax = 0.963 | l = −19→19 |
9258 measured 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0574P)2 + 0.4741P] where P = (Fo2 + 2Fc2)/3 |
4851 reflections | (Δ/σ)max < 0.001 |
289 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C23H23N5O3S | V = 2124.75 (7) Å3 |
Mr = 449.52 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.2058 (2) Å | µ = 0.19 mm−1 |
b = 12.7677 (2) Å | T = 90 K |
c = 15.0499 (3) Å | 0.30 × 0.20 × 0.20 mm |
β = 99.3278 (9)° |
Nonius KappaCCD area-detector diffractometer | 4851 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 3681 reflections with I > 2σ(I) |
Tmin = 0.945, Tmax = 0.963 | Rint = 0.027 |
9258 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.32 e Å−3 |
4851 reflections | Δρmin = −0.38 e Å−3 |
289 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 | ||
S1 | 0.52629 (4) | 0.23309 (3) | 0.65312 (3) | 0.02064 (12) | |
O1 | 0.06361 (10) | −0.12945 (9) | −0.01015 (7) | 0.0228 (3) | |
N1 | 0.51618 (11) | 0.17182 (10) | 0.55438 (8) | 0.0184 (3) | |
C1 | 0.40908 (14) | 0.16767 (12) | 0.49169 (10) | 0.0185 (3) | |
H1 | 0.3330 | 0.1943 | 0.5013 | 0.022* | |
O2 | 0.62682 (11) | 0.18602 (9) | 0.70982 (7) | 0.0277 (3) | |
N2 | 0.18784 (12) | 0.21890 (11) | 0.34876 (9) | 0.0214 (3) | |
C2 | 0.43040 (13) | 0.11985 (12) | 0.41515 (10) | 0.0163 (3) | |
O3 | 0.40802 (11) | 0.22977 (10) | 0.67635 (8) | 0.0274 (3) | |
N3 | 0.18362 (11) | 0.01288 (11) | 0.18193 (9) | 0.0198 (3) | |
C3 | 0.55802 (13) | 0.09339 (12) | 0.42848 (10) | 0.0164 (3) | |
N4 | 0.10182 (12) | −0.01862 (11) | 0.10775 (9) | 0.0212 (3) | |
H4A | 0.0362 | 0.0184 | 0.0893 | 0.025* | |
C4 | 0.62985 (14) | 0.04215 (13) | 0.37463 (11) | 0.0201 (3) | |
H4 | 0.5960 | 0.0175 | 0.3164 | 0.024* | |
N5 | 0.21256 (12) | −0.17097 (11) | 0.10530 (9) | 0.0228 (3) | |
H5A | 0.2287 | −0.2303 | 0.0799 | 0.027* | |
H5B | 0.2539 | −0.1529 | 0.1578 | 0.027* | |
C5 | 0.75117 (15) | 0.02789 (13) | 0.40746 (11) | 0.0236 (4) | |
H5 | 0.8007 | −0.0082 | 0.3719 | 0.028* | |
C6 | 0.80220 (14) | 0.06584 (13) | 0.49234 (11) | 0.0237 (4) | |
H6 | 0.8865 | 0.0571 | 0.5123 | 0.028* | |
C7 | 0.73292 (14) | 0.11590 (12) | 0.54810 (11) | 0.0215 (3) | |
H7 | 0.7674 | 0.1406 | 0.6062 | 0.026* | |
C8 | 0.61085 (14) | 0.12816 (12) | 0.51490 (10) | 0.0175 (3) | |
C9 | 0.34470 (13) | 0.08920 (12) | 0.33617 (10) | 0.0170 (3) | |
H9 | 0.3691 | 0.0333 | 0.3016 | 0.020* | |
C10 | 0.23579 (14) | 0.13025 (12) | 0.30645 (10) | 0.0178 (3) | |
C11 | 0.15035 (16) | 0.30028 (13) | 0.27930 (12) | 0.0268 (4) | |
H11A | 0.2214 | 0.3217 | 0.2522 | 0.032* | |
H11B | 0.1210 | 0.3627 | 0.3083 | 0.032* | |
C12 | 0.04970 (17) | 0.26100 (14) | 0.20419 (12) | 0.0311 (4) | |
H12A | −0.0262 | 0.2999 | 0.2063 | 0.037* | |
H12B | 0.0737 | 0.2724 | 0.1444 | 0.037* | |
C13 | 0.03073 (14) | 0.14414 (14) | 0.21932 (11) | 0.0246 (4) | |
H13 | −0.0283 | 0.1134 | 0.1691 | 0.030* | |
C14 | −0.01258 (16) | 0.12963 (16) | 0.31082 (12) | 0.0322 (4) | |
H14A | −0.0182 | 0.0541 | 0.3244 | 0.039* | |
H14B | −0.0936 | 0.1613 | 0.3087 | 0.039* | |
C15 | 0.07947 (15) | 0.18361 (15) | 0.38475 (12) | 0.0289 (4) | |
H15A | 0.0406 | 0.2446 | 0.4089 | 0.035* | |
H15B | 0.1040 | 0.1339 | 0.4349 | 0.035* | |
C16 | 0.15120 (13) | 0.08962 (12) | 0.22868 (10) | 0.0177 (3) | |
C17 | 0.12469 (14) | −0.10794 (13) | 0.06382 (10) | 0.0194 (3) | |
C18 | 0.56295 (14) | 0.36276 (13) | 0.63079 (10) | 0.0186 (3) | |
C19 | 0.47539 (14) | 0.44052 (13) | 0.63028 (10) | 0.0218 (4) | |
H19 | 0.3961 | 0.4234 | 0.6402 | 0.026* | |
C20 | 0.50653 (15) | 0.54334 (14) | 0.61499 (11) | 0.0249 (4) | |
H20 | 0.4485 | 0.5975 | 0.6154 | 0.030* | |
C21 | 0.62182 (15) | 0.56746 (14) | 0.59919 (11) | 0.0256 (4) | |
H21 | 0.6427 | 0.6382 | 0.5893 | 0.031* | |
C22 | 0.70691 (15) | 0.48886 (13) | 0.59772 (12) | 0.0270 (4) | |
H22 | 0.7850 | 0.5057 | 0.5851 | 0.032* | |
C23 | 0.67862 (14) | 0.38589 (13) | 0.61449 (11) | 0.0227 (4) | |
H23 | 0.7372 | 0.3321 | 0.6148 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0274 (2) | 0.0202 (2) | 0.01356 (19) | −0.00139 (16) | 0.00103 (15) | −0.00125 (16) |
O1 | 0.0246 (6) | 0.0214 (6) | 0.0199 (6) | −0.0007 (5) | −0.0034 (5) | −0.0035 (5) |
N1 | 0.0196 (7) | 0.0188 (7) | 0.0159 (6) | −0.0007 (5) | 0.0002 (5) | −0.0019 (6) |
C1 | 0.0171 (8) | 0.0180 (8) | 0.0196 (8) | −0.0006 (6) | 0.0008 (6) | 0.0015 (6) |
O2 | 0.0381 (7) | 0.0237 (7) | 0.0179 (6) | 0.0035 (5) | −0.0061 (5) | 0.0012 (5) |
N2 | 0.0232 (7) | 0.0211 (8) | 0.0188 (7) | 0.0047 (6) | 0.0002 (5) | −0.0019 (6) |
C2 | 0.0171 (8) | 0.0149 (8) | 0.0167 (7) | 0.0000 (6) | 0.0021 (6) | 0.0026 (6) |
O3 | 0.0324 (7) | 0.0294 (7) | 0.0222 (6) | −0.0059 (5) | 0.0103 (5) | −0.0041 (5) |
N3 | 0.0187 (7) | 0.0216 (7) | 0.0175 (6) | −0.0025 (5) | −0.0021 (5) | −0.0022 (6) |
C3 | 0.0183 (8) | 0.0137 (8) | 0.0168 (7) | −0.0007 (6) | 0.0015 (6) | 0.0035 (6) |
N4 | 0.0174 (7) | 0.0231 (8) | 0.0207 (7) | 0.0018 (5) | −0.0045 (5) | −0.0046 (6) |
C4 | 0.0240 (8) | 0.0193 (9) | 0.0176 (7) | −0.0015 (6) | 0.0050 (6) | 0.0010 (6) |
N5 | 0.0259 (7) | 0.0213 (7) | 0.0190 (7) | 0.0019 (6) | −0.0029 (6) | −0.0038 (6) |
C5 | 0.0230 (8) | 0.0212 (9) | 0.0278 (9) | 0.0022 (7) | 0.0076 (7) | 0.0016 (7) |
C6 | 0.0167 (8) | 0.0207 (9) | 0.0330 (9) | −0.0021 (6) | 0.0014 (7) | 0.0049 (7) |
C7 | 0.0218 (8) | 0.0176 (8) | 0.0229 (8) | −0.0034 (6) | −0.0028 (6) | 0.0025 (7) |
C8 | 0.0200 (8) | 0.0143 (8) | 0.0181 (7) | −0.0007 (6) | 0.0031 (6) | 0.0024 (6) |
C9 | 0.0209 (8) | 0.0160 (8) | 0.0142 (7) | −0.0014 (6) | 0.0030 (6) | −0.0007 (6) |
C10 | 0.0206 (8) | 0.0183 (8) | 0.0145 (7) | −0.0001 (6) | 0.0028 (6) | −0.0001 (6) |
C11 | 0.0291 (9) | 0.0200 (9) | 0.0293 (9) | 0.0034 (7) | −0.0013 (7) | −0.0010 (7) |
C12 | 0.0340 (10) | 0.0274 (10) | 0.0276 (9) | 0.0102 (8) | −0.0078 (8) | −0.0016 (8) |
C13 | 0.0181 (8) | 0.0279 (9) | 0.0261 (8) | 0.0022 (7) | −0.0015 (6) | −0.0077 (7) |
C14 | 0.0240 (9) | 0.0380 (12) | 0.0370 (10) | −0.0009 (8) | 0.0123 (8) | −0.0104 (9) |
C15 | 0.0290 (9) | 0.0342 (11) | 0.0247 (9) | 0.0058 (8) | 0.0077 (7) | −0.0032 (8) |
C16 | 0.0177 (8) | 0.0176 (8) | 0.0177 (7) | −0.0012 (6) | 0.0030 (6) | 0.0009 (6) |
C17 | 0.0191 (8) | 0.0198 (8) | 0.0191 (8) | −0.0034 (6) | 0.0024 (6) | −0.0004 (7) |
C18 | 0.0228 (8) | 0.0180 (8) | 0.0138 (7) | −0.0002 (6) | −0.0010 (6) | −0.0016 (6) |
C19 | 0.0202 (8) | 0.0280 (9) | 0.0167 (7) | 0.0010 (7) | 0.0010 (6) | −0.0040 (7) |
C20 | 0.0289 (9) | 0.0232 (9) | 0.0205 (8) | 0.0080 (7) | −0.0029 (7) | −0.0042 (7) |
C21 | 0.0327 (10) | 0.0186 (9) | 0.0238 (8) | −0.0001 (7) | −0.0005 (7) | −0.0017 (7) |
C22 | 0.0247 (9) | 0.0243 (9) | 0.0313 (9) | −0.0042 (7) | 0.0020 (7) | −0.0037 (8) |
C23 | 0.0215 (8) | 0.0191 (9) | 0.0259 (8) | 0.0018 (6) | −0.0010 (7) | −0.0052 (7) |
S1—O3 | 1.4250 (12) | C7—H7 | 0.9500 |
S1—O2 | 1.4307 (12) | C9—C10 | 1.337 (2) |
S1—N1 | 1.6668 (13) | C9—H9 | 0.9500 |
S1—C18 | 1.7514 (17) | C10—C16 | 1.476 (2) |
O1—C17 | 1.2394 (18) | C11—C12 | 1.545 (2) |
N1—C1 | 1.4023 (19) | C11—H11A | 0.9900 |
N1—C8 | 1.4120 (19) | C11—H11B | 0.9900 |
C1—C2 | 1.359 (2) | C12—C13 | 1.529 (3) |
C1—H1 | 0.9500 | C12—H12A | 0.9900 |
N2—C10 | 1.444 (2) | C12—H12B | 0.9900 |
N2—C15 | 1.478 (2) | C13—C16 | 1.505 (2) |
N2—C11 | 1.485 (2) | C13—C14 | 1.544 (2) |
C2—C3 | 1.451 (2) | C13—H13 | 1.0000 |
C2—C9 | 1.455 (2) | C14—C15 | 1.551 (2) |
N3—C16 | 1.292 (2) | C14—H14A | 0.9900 |
N3—N4 | 1.3844 (17) | C14—H14B | 0.9900 |
C3—C4 | 1.394 (2) | C15—H15A | 0.9900 |
C3—C8 | 1.411 (2) | C15—H15B | 0.9900 |
N4—C17 | 1.363 (2) | C18—C23 | 1.389 (2) |
N4—H4A | 0.8800 | C18—C19 | 1.395 (2) |
C4—C5 | 1.381 (2) | C19—C20 | 1.387 (2) |
C4—H4 | 0.9500 | C19—H19 | 0.9500 |
N5—C17 | 1.344 (2) | C20—C21 | 1.386 (2) |
N5—H5A | 0.8800 | C20—H20 | 0.9500 |
N5—H5B | 0.8800 | C21—C22 | 1.387 (2) |
C5—C6 | 1.399 (2) | C21—H21 | 0.9500 |
C5—H5 | 0.9500 | C22—C23 | 1.385 (2) |
C6—C7 | 1.388 (2) | C22—H22 | 0.9500 |
C6—H6 | 0.9500 | C23—H23 | 0.9500 |
C7—C8 | 1.387 (2) | ||
O3—S1—O2 | 120.99 (7) | N2—C11—H11B | 109.2 |
O3—S1—N1 | 105.86 (7) | C12—C11—H11B | 109.2 |
O2—S1—N1 | 105.53 (7) | H11A—C11—H11B | 107.9 |
O3—S1—C18 | 109.37 (8) | C13—C12—C11 | 108.08 (14) |
O2—S1—C18 | 108.96 (7) | C13—C12—H12A | 110.1 |
N1—S1—C18 | 104.88 (7) | C11—C12—H12A | 110.1 |
C1—N1—C8 | 108.74 (12) | C13—C12—H12B | 110.1 |
C1—N1—S1 | 123.01 (11) | C11—C12—H12B | 110.1 |
C8—N1—S1 | 127.83 (10) | H12A—C12—H12B | 108.4 |
C2—C1—N1 | 109.79 (13) | C16—C13—C12 | 108.72 (14) |
C2—C1—H1 | 125.1 | C16—C13—C14 | 105.54 (14) |
N1—C1—H1 | 125.1 | C12—C13—C14 | 108.74 (15) |
C10—N2—C15 | 108.00 (13) | C16—C13—H13 | 111.2 |
C10—N2—C11 | 108.71 (12) | C12—C13—H13 | 111.2 |
C15—N2—C11 | 108.41 (13) | C14—C13—H13 | 111.2 |
C1—C2—C3 | 106.99 (13) | C13—C14—C15 | 108.54 (14) |
C1—C2—C9 | 129.03 (14) | C13—C14—H14A | 110.0 |
C3—C2—C9 | 123.73 (13) | C15—C14—H14A | 110.0 |
C16—N3—N4 | 116.84 (13) | C13—C14—H14B | 110.0 |
C4—C3—C8 | 119.21 (14) | C15—C14—H14B | 110.0 |
C4—C3—C2 | 132.66 (14) | H14A—C14—H14B | 108.4 |
C8—C3—C2 | 108.12 (13) | N2—C15—C14 | 111.29 (13) |
C17—N4—N3 | 118.83 (13) | N2—C15—H15A | 109.4 |
C17—N4—H4A | 120.6 | C14—C15—H15A | 109.4 |
N3—N4—H4A | 120.6 | N2—C15—H15B | 109.4 |
C5—C4—C3 | 118.77 (15) | C14—C15—H15B | 109.4 |
C5—C4—H4 | 120.6 | H15A—C15—H15B | 108.0 |
C3—C4—H4 | 120.6 | N3—C16—C10 | 119.82 (14) |
C17—N5—H5A | 120.0 | N3—C16—C13 | 128.82 (14) |
C17—N5—H5B | 120.0 | C10—C16—C13 | 111.26 (13) |
H5A—N5—H5B | 120.0 | O1—C17—N5 | 122.73 (15) |
C4—C5—C6 | 120.93 (15) | O1—C17—N4 | 120.07 (14) |
C4—C5—H5 | 119.5 | N5—C17—N4 | 117.18 (13) |
C6—C5—H5 | 119.5 | C23—C18—C19 | 121.55 (15) |
C7—C6—C5 | 121.71 (15) | C23—C18—S1 | 119.29 (12) |
C7—C6—H6 | 119.1 | C19—C18—S1 | 119.15 (12) |
C5—C6—H6 | 119.1 | C20—C19—C18 | 118.61 (15) |
C8—C7—C6 | 116.73 (15) | C20—C19—H19 | 120.7 |
C8—C7—H7 | 121.6 | C18—C19—H19 | 120.7 |
C6—C7—H7 | 121.6 | C21—C20—C19 | 120.36 (15) |
C7—C8—C3 | 122.60 (14) | C21—C20—H20 | 119.8 |
C7—C8—N1 | 131.09 (14) | C19—C20—H20 | 119.8 |
C3—C8—N1 | 106.30 (13) | C20—C21—C22 | 120.29 (17) |
C10—C9—C2 | 127.85 (14) | C20—C21—H21 | 119.9 |
C10—C9—H9 | 116.1 | C22—C21—H21 | 119.9 |
C2—C9—H9 | 116.1 | C23—C22—C21 | 120.37 (16) |
C9—C10—N2 | 122.99 (14) | C23—C22—H22 | 119.8 |
C9—C10—C16 | 124.17 (14) | C21—C22—H22 | 119.8 |
N2—C10—C16 | 112.84 (13) | C22—C23—C18 | 118.78 (15) |
N2—C11—C12 | 112.17 (14) | C22—C23—H23 | 120.6 |
N2—C11—H11A | 109.2 | C18—C23—H23 | 120.6 |
C12—C11—H11A | 109.2 | ||
O3—S1—N1—C1 | 27.83 (14) | C11—N2—C10—C16 | −54.35 (17) |
O2—S1—N1—C1 | 157.21 (12) | C10—N2—C11—C12 | 61.52 (18) |
C18—S1—N1—C1 | −87.77 (13) | C15—N2—C11—C12 | −55.65 (18) |
O3—S1—N1—C8 | −160.46 (13) | N2—C11—C12—C13 | −6.9 (2) |
O2—S1—N1—C8 | −31.08 (15) | C11—C12—C13—C16 | −51.93 (18) |
C18—S1—N1—C8 | 83.93 (14) | C11—C12—C13—C14 | 62.51 (18) |
C8—N1—C1—C2 | 2.20 (17) | C16—C13—C14—C15 | 61.99 (18) |
S1—N1—C1—C2 | 175.29 (11) | C12—C13—C14—C15 | −54.51 (19) |
N1—C1—C2—C3 | −1.00 (17) | C10—N2—C15—C14 | −53.66 (18) |
N1—C1—C2—C9 | 173.35 (15) | C11—N2—C15—C14 | 63.96 (18) |
C1—C2—C3—C4 | 178.39 (17) | C13—C14—C15—N2 | −8.0 (2) |
C9—C2—C3—C4 | 3.7 (3) | N4—N3—C16—C10 | −177.48 (13) |
C1—C2—C3—C8 | −0.55 (17) | N4—N3—C16—C13 | 6.5 (2) |
C9—C2—C3—C8 | −175.28 (14) | C9—C10—C16—N3 | −3.7 (2) |
C16—N3—N4—C17 | −171.07 (14) | N2—C10—C16—N3 | 177.31 (14) |
C8—C3—C4—C5 | −0.6 (2) | C9—C10—C16—C13 | 172.99 (15) |
C2—C3—C4—C5 | −179.45 (16) | N2—C10—C16—C13 | −6.05 (18) |
C3—C4—C5—C6 | −1.3 (2) | C12—C13—C16—N3 | −122.76 (18) |
C4—C5—C6—C7 | 2.2 (2) | C14—C13—C16—N3 | 120.73 (18) |
C5—C6—C7—C8 | −1.1 (2) | C12—C13—C16—C10 | 60.98 (17) |
C6—C7—C8—C3 | −0.8 (2) | C14—C13—C16—C10 | −55.53 (17) |
C6—C7—C8—N1 | 177.86 (15) | N3—N4—C17—O1 | −168.96 (14) |
C4—C3—C8—C7 | 1.7 (2) | N3—N4—C17—N5 | 12.8 (2) |
C2—C3—C8—C7 | −179.17 (14) | O3—S1—C18—C23 | 174.30 (12) |
C4—C3—C8—N1 | −177.26 (14) | O2—S1—C18—C23 | 40.05 (14) |
C2—C3—C8—N1 | 1.85 (16) | N1—S1—C18—C23 | −72.55 (13) |
C1—N1—C8—C7 | 178.68 (16) | O3—S1—C18—C19 | −5.35 (15) |
S1—N1—C8—C7 | 6.0 (2) | O2—S1—C18—C19 | −139.61 (12) |
C1—N1—C8—C3 | −2.46 (16) | N1—S1—C18—C19 | 107.79 (13) |
S1—N1—C8—C3 | −175.13 (11) | C23—C18—C19—C20 | −1.4 (2) |
C1—C2—C9—C10 | 25.1 (3) | S1—C18—C19—C20 | 178.23 (12) |
C3—C2—C9—C10 | −161.39 (15) | C18—C19—C20—C21 | 1.0 (2) |
C2—C9—C10—N2 | 3.1 (3) | C19—C20—C21—C22 | 0.6 (2) |
C2—C9—C10—C16 | −175.84 (14) | C20—C21—C22—C23 | −1.8 (3) |
C15—N2—C10—C9 | −115.97 (17) | C21—C22—C23—C18 | 1.4 (2) |
C11—N2—C10—C9 | 126.60 (16) | C19—C18—C23—C22 | 0.2 (2) |
C15—N2—C10—C16 | 63.08 (16) | S1—C18—C23—C22 | −179.42 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O1i | 0.88 | 2.06 | 2.8785 (17) | 154 |
N5—H5B···O2ii | 0.88 | 2.25 | 3.0651 (17) | 154 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C23H23N5O3S |
Mr | 449.52 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 90 |
a, b, c (Å) | 11.2058 (2), 12.7677 (2), 15.0499 (3) |
β (°) | 99.3278 (9) |
V (Å3) | 2124.75 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.945, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9258, 4851, 3681 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.111, 1.06 |
No. of reflections | 4851 |
No. of parameters | 289 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.38 |
Computer programs: COLLECT (Nonius, 1999), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1995), SHELXL97 and local programs.
S1—O2 | 1.4307 (12) | N3—C16 | 1.292 (2) |
S1—N1 | 1.6668 (13) | N3—N4 | 1.3844 (17) |
S1—C18 | 1.7514 (17) | N5—C17 | 1.344 (2) |
O1—C17 | 1.2394 (18) | C9—C10 | 1.337 (2) |
C2—C9 | 1.455 (2) | C10—C16 | 1.476 (2) |
C1—C2—C9 | 129.03 (14) | C9—C10—N2 | 122.99 (14) |
C10—C9—C2 | 127.85 (14) | N2—C10—C16 | 112.84 (13) |
O3—S1—N1—C1 | 27.83 (14) | C9—C10—C16—N3 | −3.7 (2) |
O2—S1—N1—C8 | −31.08 (15) | N1—S1—C18—C19 | 107.79 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O1i | 0.88 | 2.06 | 2.8785 (17) | 154.0 |
N5—H5B···O2ii | 0.88 | 2.25 | 3.0651 (17) | 153.7 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1. |
Radiotherapy is the treatment of cancer and other diseases with ionizing radiation. The technique is successful because ionizing radiation kills dividing cells and is thus slightly more toxic to fast-growing cancer cells than to normal cells. Radiotherapy may be used to treat localized solid tumours, such as cancers of the skin, tongue, larynx, brain, breast, uterus or cervix. Agents which are used to potentiate the effectiveness of radiation therapy in destroying unwanted cells are radio-sensitizing agents. Recently, we have reported (Sekhar et al., 2007) the radio-sensitizing activity of N-arylsubstituted (Z)-(±)-2-(1H-indol-3-ylmethylene)-1-azabicyclo[2.2.2]octan-3-ols. Systematic structural modification of the active molecule (Z)-2-(1-phenylsulfonyl-1H-indol-3-ylmethylene)-1-azabicyclo[2.2.2]octan-3-one, (II), was carried out and the title compound, (I), was synthesized as a structural analogue of (II). In order to confirm the double-bond geometry, and to determine the molecular conformation in the crystal structure, the X-ray crystallographic analysis of (I) has been carried out and the results are presented here.
X-ray crystallography confirmed the molecular structure and atom connectivity for (I), as illustrated in Fig. 1. Selected geometric parameters are presented in Table 1. The indole ring is planar, with bond distances and angles comparable with those previously reported for other indole derivatives (Mason et al., 2003; Zarza, et al., 1988).
In compound (I), atom N1 lies only very slightly [0.0555 (15) Å] out of the plane of the connecting atoms S1, C1 and C8, the sum of the angles about N1 being 359.58 (11)°. In a previous study, 21 structurally related indole analogues bearing N-arylsulphonate groupings were analyzed (Beddoes et al., 1986) (available in the Cambridge Structural Database; Allen, 2002), and the sums of the three angles around the N atom were determined, to assess planarity. It was found that only two of the 21 compounds had values that were outside the range 359.0–360°, the farthest value from the perfectly planar situation being 357.2°. This is in general agreement with our current observation with compound (I). However, it should be noted that in at least one case, i.e. in a moiety consisting of a pyrrolidine N atom bearing a toluene sulfonyl group, atom N1 can exist significantly out of the plane of the connecting atoms S1, C1 and C4 (335.1°), indicating pyrimidalization at the N atom (Helliwell et al., 1997).
The sulfonyl group of (I) has a distorted tetrahedral geometry, with widening of the O2—S1—O3 angle [120.99 (7)°] and the resultant narrowing of the N1—S1—C18 angle [104.88 (7)°] from ideal tetrahedral values. This type of deviation in the sulfonyl group has been reported previously (Beddoes et al., 1994; Govindasamy et al., 1998; Zhao et al., 1997, 1999), and is due to the repulsive interaction between the short S═ O bonds. The S—O, S—C and S—N distances are comparable with those found in N-phenylsulfonamides (Gomes et al., 1993). The orientation of the phenylsulfonyl group with respect to the planar indole moiety [r.m.s. deviation = 0.0172 (13) Å] is described by the torsion angles O3—S1—N1—C1, O2—S1—N1—C8 and N1—S1—C18—C19 (Table 1). The phenyl ring linked to the sulfonyl group is orthogonal to the indole moiety, forming a dihedral angle of 77.18 (4)°.
Compound (I) is the Z isomer and the C10—C16 bond is in a trans disposition with respect to the C2—C9 bond. The double bond has a nearly planar arrangement, since the r.m.s. deviation from the best plane passing through atoms N2/C10/C16/C9/C2 is 0.0195 (9) Å. Deviations from ideal geometry are observed in the bond angles around atoms C2, C9 and C10. While the C9—C10—C16 angle is close to the ideal value of 120°, the C1—C2—C9, C2—C9—C10 and N2—C10—C16 angles are more distorted, as a consequence of the strain induced by the double-bond linkage at C9—C10. The azabicyclic moiety presents very small distortions around atoms N2, C11, C12, C13, C14 and C15. The value of the C1—C2—C9—C10 torsion angle [25.1 (3)°] indicates a deviation of the indole ring from the plane of the double bond connected to the azabicyclic ring. However, the C2—C9 bond length [1.455 (2) Å], when compared with the standard value for a single bond connecting a Car atom to a Csp2 atom [1.470 (15) Å; Wilson, 1992], suggests extensive conjugation, beginning at atom N5 of the semicarbazone moiety and extending through to the indole ring in (I), which is also evident from the C10—C16 and C16—N3 bond lengths.
The mode of packing of (I), as viewed down the crystallographic b axis, is shown in Fig. 2. The molecules are linked by two types of hydrogen bonding. Atoms N4 and O1 are mutually hydrogen-bonded to an inversion-related molecule at (-x, -y, -z), leading to dimers, and atom N5 is hydrogen-bonded to sulfonyl atom O2 of a different inversion-related molecule at (-x + 1, -y, -z + 1). In addition to hydrogen bonding, π–π interactions between phenyl rings [3.433 (1) Å] of inversion-related molecules at (1 - x, 1 - y, 1 - z) and between different inversion-related indole rings at (1 - x, -y, 1 - z) (3.343 Å) link these dimers in an extended fashion parallel to the b axis.