Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803018804/ya6172sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803018804/ya6172Isup2.hkl |
CCDC reference: 222916
A mixture of 5-(4-chlorobenzylidene)-3-ethylthiazolidine-2,4-dione (2 mmol), prepared according to Lo et al. (1958), isatin (2 mmol), and sarcosine (2 mmol) was refluxed in dioxane (30 ml) until the disappearance of the starting material (as monitored by thin-layer chromatography). When the reaction was complete, the solvent was removed in vacuo and the residue was separated by column chromatography (silica gel, petroleum ether/ethyl acetate 5:1) to give the title compound, (I). M.p. 476 K; IR (KBr): 3358.3 (–NH), 1750.2, 1718.7, 1685.9 (C═O) cm−1; 1H NMR (CDCl3, p.p.m.): 0.87 (t, 3H, CH3), 2.26 (s, 3H, N—CH3), 3.40–3.50 (m, 2H, –CH2), 3.61 (dd, J = 9.3, 7.8 Hz, 1H, Hc), 4.03 (dd, J = 10.2, 9.3 Hz, 1H), 4.58 (dd, J = 10.2, 7.8 Hz, 1H), 6.82–7.38 (m, 8H, ArH), 7.41 (br, 1H, –NH); 13C NMR (p.p.m.): 12.68, 35.18, 36.95, 51.33, 58.29, 72.12, 79.90, 110.31, 123.13, 123.22, 127.01, 128.81, 130.61, 131.46,133.69,136.16, 142.39, 169.38, 175.42, 177.50. 20 mg of (I) was dissolved in 15 ml of benzene andthe solution was kept at room temperature for 15 d. Slow evaporation of the solvent gave colorless single crystals of (I) suitable for X-ray analysis.
All H atoms were placed in calculated positions, with C—H distances ranging from 0.93 to 0.98 Å and an N—H distance of 0.86 Å. They were included in the refinement in the riding-motion approximation, with Uiso = 1.2 (1.5 for methyl) times Ueq of the carrier atom. Both solvate benzene molecules refined poorly. In the final model, the benzene molecule in the general position was included with the fixed geometry of a regular hexagon (C—C = 1.39 Å). The solvate benzene molecule in the inversion centre was represented as two-component disorder with approximately equal occupancy factors, which refined to 0.49 (3) and 0.51 (3). The bond lengths in both components of the disordered benzene were constrained to 1.39±0.01 Å.
Data collection: Bruker SMART (Bruker,1997); cell refinement: Bruker SMART; data reduction: Bruker SAINT (Bruker,1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL (Bruker,1997); software used to prepare material for publication: Bruker SHELXTL.
C22H20ClN3O3S·1.5C6H6 | F(000) = 1172 |
Mr = 559.08 | Dx = 1.266 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.132 (3) Å | Cell parameters from 886 reflections |
b = 22.785 (7) Å | θ = 2.7–23.1° |
c = 12.515 (4) Å | µ = 0.24 mm−1 |
β = 112.477 (5)° | T = 293 K |
V = 2933.2 (15) Å3 | Parallelepiped, colorless |
Z = 4 | 0.42 × 0.40 × 0.34 mm |
Bruker SMART CCD area detector diffractometer | 5070 independent reflections |
Radiation source: fine-focus sealed tube | 2701 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −12→13 |
Tmin = 0.796, Tmax = 0.923 | k = −27→15 |
14461 measured reflections | l = −14→14 |
Refinement on F2 | 180 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.057 | w = 1/[σ2(Fo2) + (0.084P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.155 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.27 e Å−3 |
5070 reflections | Δρmin = −0.23 e Å−3 |
370 parameters |
C22H20ClN3O3S·1.5C6H6 | V = 2933.2 (15) Å3 |
Mr = 559.08 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.132 (3) Å | µ = 0.24 mm−1 |
b = 22.785 (7) Å | T = 293 K |
c = 12.515 (4) Å | 0.42 × 0.40 × 0.34 mm |
β = 112.477 (5)° |
Bruker SMART CCD area detector diffractometer | 5070 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 2701 reflections with I > 2σ(I) |
Tmin = 0.796, Tmax = 0.923 | Rint = 0.046 |
14461 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 180 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.27 e Å−3 |
5070 reflections | Δρmin = −0.23 e Å−3 |
370 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 | Occ. (<1) | |
Cl1 | −0.11610 (11) | 0.08563 (6) | −0.13037 (15) | 0.1291 (6) | |
S1 | 0.47701 (9) | 0.13010 (4) | −0.05396 (7) | 0.0594 (3) | |
N1 | 0.6453 (3) | 0.06854 (14) | 0.1099 (3) | 0.0637 (8) | |
N2 | 0.5755 (3) | 0.25291 (12) | 0.1866 (2) | 0.0503 (7) | |
N3 | 0.6599 (3) | 0.25950 (14) | −0.0504 (3) | 0.0663 (9) | |
H3 | 0.6546 | 0.2754 | −0.1143 | 0.080* | |
O1 | 0.5867 (3) | 0.03034 (14) | −0.0726 (3) | 0.0990 (10) | |
O2 | 0.6643 (2) | 0.11726 (12) | 0.2731 (2) | 0.0693 (7) | |
O3 | 0.4440 (3) | 0.26401 (12) | −0.07717 (19) | 0.0672 (7) | |
C1 | 0.5791 (4) | 0.06809 (18) | −0.0070 (4) | 0.0678 (11) | |
C2 | 0.6206 (3) | 0.11421 (16) | 0.1690 (3) | 0.0525 (9) | |
C3 | 0.5314 (3) | 0.16081 (15) | 0.0914 (2) | 0.0467 (8) | |
C4 | 0.4222 (3) | 0.17704 (15) | 0.1376 (3) | 0.0498 (8) | |
H4 | 0.4478 | 0.1589 | 0.2141 | 0.060* | |
C5 | 0.4373 (3) | 0.24282 (15) | 0.1574 (3) | 0.0557 (9) | |
H5A | 0.3852 | 0.2642 | 0.0882 | 0.067* | |
H5B | 0.4121 | 0.2547 | 0.2203 | 0.067* | |
C6 | 0.6081 (3) | 0.22009 (14) | 0.1005 (2) | 0.0460 (8) | |
C7 | 0.5563 (4) | 0.25067 (16) | −0.0208 (3) | 0.0538 (9) | |
C8 | 0.7316 (4) | 0.01967 (19) | 0.1680 (4) | 0.0923 (14) | |
H8A | 0.6943 | −0.0169 | 0.1303 | 0.111* | |
H8B | 0.7395 | 0.0174 | 0.2478 | 0.111* | |
C9 | 0.8621 (5) | 0.0278 (3) | 0.1643 (5) | 0.1184 (18) | |
H9A | 0.8550 | 0.0272 | 0.0854 | 0.178* | |
H9B | 0.9185 | −0.0033 | 0.2064 | 0.178* | |
H9C | 0.8974 | 0.0648 | 0.1987 | 0.178* | |
C10 | 0.2874 (3) | 0.15539 (16) | 0.0676 (3) | 0.0544 (9) | |
C11 | 0.2412 (4) | 0.10599 (18) | 0.1058 (4) | 0.0721 (11) | |
H11 | 0.2941 | 0.0872 | 0.1734 | 0.086* | |
C12 | 0.1179 (4) | 0.08474 (19) | 0.0446 (4) | 0.0854 (13) | |
H12 | 0.0880 | 0.0518 | 0.0708 | 0.102* | |
C13 | 0.0402 (4) | 0.11219 (19) | −0.0541 (4) | 0.0763 (12) | |
C14 | 0.0815 (4) | 0.1606 (2) | −0.0946 (3) | 0.0714 (11) | |
H14 | 0.0271 | 0.1791 | −0.1620 | 0.086* | |
C15 | 0.2062 (4) | 0.18181 (18) | −0.0335 (3) | 0.0629 (10) | |
H15 | 0.2355 | 0.2144 | −0.0613 | 0.075* | |
C16 | 0.6115 (4) | 0.31501 (16) | 0.1955 (3) | 0.0715 (11) | |
H16A | 0.7031 | 0.3185 | 0.2131 | 0.107* | |
H16B | 0.5912 | 0.3330 | 0.2559 | 0.107* | |
H16C | 0.5639 | 0.3342 | 0.1234 | 0.107* | |
C17 | 0.7520 (3) | 0.21671 (14) | 0.1265 (3) | 0.0492 (8) | |
C18 | 0.7759 (4) | 0.24002 (17) | 0.0339 (3) | 0.0584 (9) | |
C19 | 0.8984 (4) | 0.2430 (2) | 0.0345 (4) | 0.0840 (13) | |
H19 | 0.9127 | 0.2579 | −0.0287 | 0.101* | |
C20 | 1.0003 (4) | 0.2236 (2) | 0.1307 (4) | 0.0866 (13) | |
H20 | 1.0844 | 0.2252 | 0.1320 | 0.104* | |
C21 | 0.9803 (4) | 0.20171 (18) | 0.2249 (4) | 0.0724 (11) | |
H21 | 1.0503 | 0.1891 | 0.2897 | 0.087* | |
C22 | 0.8551 (4) | 0.19856 (16) | 0.2228 (3) | 0.0577 (9) | |
H22 | 0.8410 | 0.1842 | 0.2866 | 0.069* | |
C23 | 0.0341 (7) | 0.1077 (3) | 0.5916 (7) | 0.180 (3) | |
H23A | −0.0323 | 0.1137 | 0.6182 | 0.216* | |
C24 | 0.1618 (9) | 0.1210 (3) | 0.6621 (4) | 0.176 (3) | |
H24A | 0.1808 | 0.1359 | 0.7360 | 0.212* | |
C25 | 0.2610 (5) | 0.1121 (3) | 0.6223 (6) | 0.166 (3) | |
H25A | 0.3464 | 0.1210 | 0.6695 | 0.199* | |
C26 | 0.2326 (7) | 0.0898 (3) | 0.5119 (6) | 0.174 (3) | |
H26A | 0.2990 | 0.0838 | 0.4853 | 0.209* | |
C27 | 0.1049 (9) | 0.0765 (3) | 0.4413 (4) | 0.243 (5) | |
H27A | 0.0859 | 0.0616 | 0.3675 | 0.292* | |
C28 | 0.0057 (5) | 0.0854 (3) | 0.4812 (7) | 0.217 (4) | |
H28A | −0.0798 | 0.0765 | 0.4339 | 0.261* | |
C29 | 0.410 (2) | −0.0334 (9) | 0.4133 (18) | 0.103 (6) | 0.51 (3) |
H29A | 0.3525 | −0.0567 | 0.3554 | 0.124* | 0.51 (3) |
C30 | 0.482 (3) | 0.0091 (10) | 0.3855 (10) | 0.088 (5) | 0.51 (3) |
H30A | 0.4683 | 0.0163 | 0.3085 | 0.106* | 0.51 (3) |
C31 | 0.576 (2) | 0.0411 (11) | 0.472 (2) | 0.109 (6) | 0.51 (3) |
H31A | 0.6293 | 0.0675 | 0.4543 | 0.131* | 0.51 (3) |
C29' | 0.404 (2) | −0.0430 (10) | 0.473 (3) | 0.113 (6) | 0.49 (3) |
H29B | 0.3396 | −0.0714 | 0.4561 | 0.135* | 0.49 (3) |
C30' | 0.430 (2) | −0.0158 (15) | 0.3852 (11) | 0.104 (6) | 0.49 (3) |
H30B | 0.3847 | −0.0266 | 0.3087 | 0.125* | 0.49 (3) |
C31' | 0.524 (3) | 0.0273 (11) | 0.412 (2) | 0.094 (5) | 0.49 (3) |
H31B | 0.5401 | 0.0462 | 0.3525 | 0.112* | 0.49 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0599 (7) | 0.0985 (10) | 0.1858 (14) | −0.0080 (7) | −0.0011 (8) | 0.0142 (10) |
S1 | 0.0606 (6) | 0.0695 (6) | 0.0469 (5) | −0.0056 (5) | 0.0191 (4) | −0.0109 (5) |
N1 | 0.0547 (19) | 0.057 (2) | 0.072 (2) | 0.0044 (16) | 0.0167 (17) | −0.0023 (17) |
N2 | 0.0579 (18) | 0.0563 (19) | 0.0434 (15) | −0.0043 (15) | 0.0268 (13) | −0.0077 (13) |
N3 | 0.076 (2) | 0.081 (2) | 0.0568 (18) | 0.0037 (18) | 0.0412 (18) | 0.0177 (16) |
O1 | 0.090 (2) | 0.086 (2) | 0.118 (2) | −0.0016 (18) | 0.0364 (18) | −0.047 (2) |
O2 | 0.0662 (16) | 0.086 (2) | 0.0552 (16) | 0.0067 (14) | 0.0222 (13) | 0.0222 (14) |
O3 | 0.0706 (18) | 0.086 (2) | 0.0480 (14) | 0.0125 (15) | 0.0261 (14) | 0.0139 (13) |
C1 | 0.055 (2) | 0.061 (3) | 0.092 (3) | −0.011 (2) | 0.033 (2) | −0.019 (2) |
C2 | 0.045 (2) | 0.061 (2) | 0.055 (2) | −0.0047 (18) | 0.0219 (18) | 0.0080 (19) |
C3 | 0.052 (2) | 0.055 (2) | 0.0359 (17) | −0.0016 (17) | 0.0198 (15) | 0.0010 (15) |
C4 | 0.050 (2) | 0.062 (2) | 0.0421 (18) | 0.0044 (17) | 0.0220 (16) | 0.0105 (16) |
C5 | 0.064 (2) | 0.064 (2) | 0.0477 (19) | 0.003 (2) | 0.0309 (17) | −0.0018 (17) |
C6 | 0.054 (2) | 0.051 (2) | 0.0376 (16) | −0.0045 (16) | 0.0233 (15) | −0.0023 (15) |
C7 | 0.065 (2) | 0.057 (2) | 0.050 (2) | −0.002 (2) | 0.0326 (19) | −0.0014 (17) |
C8 | 0.065 (3) | 0.065 (3) | 0.132 (4) | 0.012 (2) | 0.022 (3) | 0.003 (3) |
C9 | 0.074 (3) | 0.108 (4) | 0.151 (5) | 0.016 (3) | 0.018 (3) | −0.017 (3) |
C10 | 0.049 (2) | 0.061 (2) | 0.059 (2) | 0.0076 (18) | 0.0272 (18) | 0.0092 (19) |
C11 | 0.050 (2) | 0.069 (3) | 0.093 (3) | 0.007 (2) | 0.023 (2) | 0.028 (2) |
C12 | 0.058 (3) | 0.066 (3) | 0.128 (4) | 0.000 (2) | 0.031 (3) | 0.027 (3) |
C13 | 0.048 (2) | 0.063 (3) | 0.106 (3) | 0.001 (2) | 0.017 (2) | 0.003 (3) |
C14 | 0.053 (2) | 0.077 (3) | 0.076 (3) | 0.012 (2) | 0.015 (2) | 0.011 (2) |
C15 | 0.059 (2) | 0.070 (3) | 0.060 (2) | 0.002 (2) | 0.024 (2) | 0.0121 (19) |
C16 | 0.095 (3) | 0.057 (3) | 0.074 (3) | −0.011 (2) | 0.045 (2) | −0.016 (2) |
C17 | 0.057 (2) | 0.051 (2) | 0.0437 (19) | −0.0049 (17) | 0.0243 (18) | −0.0081 (16) |
C18 | 0.063 (2) | 0.067 (3) | 0.054 (2) | −0.005 (2) | 0.033 (2) | −0.0016 (19) |
C19 | 0.077 (3) | 0.111 (4) | 0.085 (3) | −0.002 (3) | 0.054 (3) | 0.009 (3) |
C20 | 0.063 (3) | 0.110 (4) | 0.100 (3) | −0.003 (3) | 0.045 (3) | −0.008 (3) |
C21 | 0.058 (3) | 0.082 (3) | 0.073 (3) | 0.001 (2) | 0.020 (2) | −0.012 (2) |
C22 | 0.060 (2) | 0.063 (2) | 0.053 (2) | −0.0067 (19) | 0.0247 (19) | −0.0075 (18) |
C23 | 0.148 (7) | 0.206 (9) | 0.183 (9) | 0.041 (6) | 0.061 (6) | 0.032 (7) |
C24 | 0.179 (8) | 0.190 (8) | 0.171 (7) | −0.011 (7) | 0.079 (7) | −0.052 (6) |
C25 | 0.184 (8) | 0.151 (6) | 0.154 (7) | −0.046 (6) | 0.057 (6) | −0.024 (5) |
C26 | 0.187 (8) | 0.209 (8) | 0.126 (6) | 0.043 (7) | 0.059 (6) | 0.008 (6) |
C27 | 0.201 (10) | 0.330 (13) | 0.130 (7) | 0.060 (10) | −0.013 (7) | −0.077 (7) |
C28 | 0.146 (7) | 0.297 (12) | 0.141 (8) | 0.025 (7) | −0.020 (6) | −0.033 (8) |
C29 | 0.137 (13) | 0.065 (11) | 0.106 (12) | −0.016 (8) | 0.045 (11) | 0.006 (11) |
C30 | 0.110 (16) | 0.060 (12) | 0.086 (7) | −0.019 (9) | 0.028 (8) | −0.003 (7) |
C31 | 0.133 (14) | 0.102 (13) | 0.070 (12) | −0.018 (9) | 0.014 (11) | 0.021 (11) |
C29' | 0.132 (14) | 0.092 (12) | 0.137 (18) | −0.004 (10) | 0.078 (15) | 0.011 (16) |
C30' | 0.115 (12) | 0.088 (17) | 0.122 (10) | −0.032 (10) | 0.060 (10) | −0.004 (11) |
C31' | 0.101 (15) | 0.087 (14) | 0.101 (13) | −0.035 (10) | 0.047 (12) | −0.007 (11) |
Cl1—C13 | 1.742 (4) | C15—H15 | 0.9300 |
S1—C1 | 1.767 (4) | C16—H16A | 0.9600 |
S1—C3 | 1.823 (3) | C16—H16B | 0.9600 |
N1—C1 | 1.363 (5) | C16—H16C | 0.9600 |
N1—C2 | 1.364 (4) | C17—C22 | 1.373 (5) |
N1—C8 | 1.469 (5) | C17—C18 | 1.390 (4) |
N2—C5 | 1.457 (4) | C18—C19 | 1.362 (5) |
N2—C16 | 1.463 (4) | C19—C20 | 1.374 (6) |
N2—C6 | 1.466 (4) | C19—H19 | 0.9300 |
N3—C7 | 1.354 (4) | C20—C21 | 1.375 (6) |
N3—C18 | 1.391 (5) | C20—H20 | 0.9300 |
N3—H3 | 0.8600 | C21—C22 | 1.385 (5) |
O1—C1 | 1.214 (4) | C21—H21 | 0.9300 |
O2—C2 | 1.206 (4) | C22—H22 | 0.9300 |
O3—C7 | 1.216 (4) | C23—C24 | 1.3900 |
C2—C3 | 1.523 (5) | C23—C28 | 1.3900 |
C3—C4 | 1.577 (4) | C23—H23A | 0.9300 |
C3—C6 | 1.578 (5) | C24—C25 | 1.3900 |
C4—C10 | 1.502 (5) | C24—H24A | 0.9300 |
C4—C5 | 1.518 (5) | C25—C26 | 1.3900 |
C4—H4 | 0.9800 | C25—H25A | 0.9300 |
C5—H5A | 0.9700 | C26—C27 | 1.3900 |
C5—H5B | 0.9700 | C26—H26A | 0.9300 |
C6—C17 | 1.510 (4) | C27—C28 | 1.3900 |
C6—C7 | 1.566 (5) | C27—H27A | 0.9300 |
C8—C9 | 1.483 (6) | C28—H28A | 0.9300 |
C8—H8A | 0.9700 | C29—C30 | 1.385 (8) |
C8—H8B | 0.9700 | C29—C31i | 1.390 (9) |
C9—H9A | 0.9600 | C29—H29A | 0.9300 |
C9—H9B | 0.9600 | C30—C31 | 1.392 (9) |
C9—H9C | 0.9600 | C30—H30A | 0.9300 |
C10—C15 | 1.381 (5) | C31—C29i | 1.390 (9) |
C10—C11 | 1.396 (5) | C31—H31A | 0.9300 |
C11—C12 | 1.378 (5) | C29'—C30' | 1.390 (9) |
C11—H11 | 0.9300 | C29'—C31'i | 1.398 (9) |
C12—C13 | 1.360 (6) | C29'—H29B | 0.9300 |
C12—H12 | 0.9300 | C30'—C31' | 1.380 (9) |
C13—C14 | 1.366 (6) | C30'—H30B | 0.9300 |
C14—C15 | 1.390 (5) | C31'—C29'i | 1.398 (9) |
C14—H14 | 0.9300 | C31'—H31B | 0.9300 |
C1—S1—C3 | 92.79 (18) | C13—C14—C15 | 118.9 (4) |
C1—N1—C2 | 116.7 (3) | C13—C14—H14 | 120.5 |
C1—N1—C8 | 120.5 (3) | C15—C14—H14 | 120.5 |
C2—N1—C8 | 122.6 (3) | C10—C15—C14 | 121.2 (4) |
C5—N2—C16 | 113.8 (3) | C10—C15—H15 | 119.4 |
C5—N2—C6 | 105.6 (2) | C14—C15—H15 | 119.4 |
C16—N2—C6 | 114.3 (2) | N2—C16—H16A | 109.5 |
C7—N3—C18 | 112.7 (3) | N2—C16—H16B | 109.5 |
C7—N3—H3 | 123.7 | H16A—C16—H16B | 109.5 |
C18—N3—H3 | 123.7 | N2—C16—H16C | 109.5 |
O1—C1—N1 | 125.6 (4) | H16A—C16—H16C | 109.5 |
O1—C1—S1 | 122.9 (4) | H16B—C16—H16C | 109.5 |
N1—C1—S1 | 111.5 (3) | C22—C17—C18 | 119.0 (3) |
O2—C2—N1 | 123.2 (3) | C22—C17—C6 | 131.8 (3) |
O2—C2—C3 | 123.0 (3) | C18—C17—C6 | 109.1 (3) |
N1—C2—C3 | 113.8 (3) | C19—C18—C17 | 121.7 (4) |
C2—C3—C4 | 109.6 (2) | C19—C18—N3 | 128.7 (3) |
C2—C3—C6 | 110.4 (3) | C17—C18—N3 | 109.6 (3) |
C4—C3—C6 | 104.1 (3) | C18—C19—C20 | 118.6 (4) |
C2—C3—S1 | 104.8 (2) | C18—C19—H19 | 120.7 |
C4—C3—S1 | 116.6 (2) | C20—C19—H19 | 120.7 |
C6—C3—S1 | 111.39 (19) | C19—C20—C21 | 121.2 (4) |
C10—C4—C5 | 116.3 (3) | C19—C20—H20 | 119.4 |
C10—C4—C3 | 116.6 (3) | C21—C20—H20 | 119.4 |
C5—C4—C3 | 103.8 (3) | C20—C21—C22 | 119.6 (4) |
C10—C4—H4 | 106.5 | C20—C21—H21 | 120.2 |
C5—C4—H4 | 106.5 | C22—C21—H21 | 120.2 |
C3—C4—H4 | 106.5 | C17—C22—C21 | 119.9 (3) |
N2—C5—C4 | 103.7 (3) | C17—C22—H22 | 120.0 |
N2—C5—H5A | 111.0 | C21—C22—H22 | 120.0 |
C4—C5—H5A | 111.0 | C24—C23—C28 | 120.0 |
N2—C5—H5B | 111.0 | C24—C23—H23A | 120.0 |
C4—C5—H5B | 111.0 | C28—C23—H23A | 120.0 |
H5A—C5—H5B | 109.0 | C25—C24—C23 | 120.0 |
N2—C6—C17 | 114.0 (3) | C25—C24—H24A | 120.0 |
N2—C6—C7 | 112.5 (3) | C23—C24—H24A | 120.0 |
C17—C6—C7 | 101.4 (2) | C26—C25—C24 | 120.0 |
N2—C6—C3 | 102.2 (2) | C26—C25—H25A | 120.0 |
C17—C6—C3 | 118.1 (3) | C24—C25—H25A | 120.0 |
C7—C6—C3 | 108.8 (3) | C25—C26—C27 | 120.0 |
O3—C7—N3 | 126.8 (3) | C25—C26—H26A | 120.0 |
O3—C7—C6 | 126.1 (3) | C27—C26—H26A | 120.0 |
N3—C7—C6 | 107.2 (3) | C28—C27—C26 | 120.0 |
N1—C8—C9 | 110.7 (4) | C28—C27—H27A | 120.0 |
N1—C8—H8A | 109.5 | C26—C27—H27A | 120.0 |
C9—C8—H8A | 109.5 | C27—C28—C23 | 120.0 |
N1—C8—H8B | 109.5 | C27—C28—H28A | 120.0 |
C9—C8—H8B | 109.5 | C23—C28—H28A | 120.0 |
H8A—C8—H8B | 108.1 | C30—C29—C31i | 120.1 (9) |
C8—C9—H9A | 109.5 | C30—C29—H29A | 120.0 |
C8—C9—H9B | 109.5 | C31i—C29—H29A | 120.0 |
H9A—C9—H9B | 109.5 | C29—C30—C31 | 120.2 (9) |
C8—C9—H9C | 109.5 | C29—C30—H30A | 119.9 |
H9A—C9—H9C | 109.5 | C31—C30—H30A | 119.9 |
H9B—C9—H9C | 109.5 | C29i—C31—C30 | 119.5 (9) |
C15—C10—C11 | 117.9 (3) | C29i—C31—H31A | 120.3 |
C15—C10—C4 | 123.3 (3) | C30—C31—H31A | 120.3 |
C11—C10—C4 | 118.8 (3) | C30'—C29'—C31'i | 119.5 (9) |
C12—C11—C10 | 120.8 (4) | C30'—C29'—H29B | 120.2 |
C12—C11—H11 | 119.6 | C31'i—C29'—H29B | 120.2 |
C10—C11—H11 | 119.6 | C31'—C30'—C29' | 119.8 (9) |
C13—C12—C11 | 119.7 (4) | C31'—C30'—H30B | 120.1 |
C13—C12—H12 | 120.1 | C29'—C30'—H30B | 120.1 |
C11—C12—H12 | 120.1 | C30'—C31'—C29'i | 120.7 (9) |
C12—C13—C14 | 121.4 (4) | C30'—C31'—H31B | 119.6 |
C12—C13—Cl1 | 119.6 (4) | C29'i—C31'—H31B | 119.6 |
C14—C13—Cl1 | 119.0 (3) | ||
C2—N1—C1—O1 | −178.2 (4) | N2—C6—C7—N3 | 123.5 (3) |
C8—N1—C1—O1 | −2.2 (6) | C17—C6—C7—N3 | 1.3 (3) |
C2—N1—C1—S1 | 1.3 (4) | C3—C6—C7—N3 | −124.0 (3) |
C8—N1—C1—S1 | 177.3 (3) | C1—N1—C8—C9 | 84.4 (5) |
C3—S1—C1—O1 | −177.9 (3) | C2—N1—C8—C9 | −99.8 (5) |
C3—S1—C1—N1 | 2.6 (3) | C5—C4—C10—C15 | 44.9 (4) |
C1—N1—C2—O2 | 173.7 (3) | C3—C4—C10—C15 | −78.2 (4) |
C8—N1—C2—O2 | −2.3 (5) | C5—C4—C10—C11 | −135.4 (3) |
C1—N1—C2—C3 | −5.7 (4) | C3—C4—C10—C11 | 101.6 (4) |
C8—N1—C2—C3 | 178.4 (3) | C15—C10—C11—C12 | −0.5 (6) |
O2—C2—C3—C4 | −46.6 (4) | C4—C10—C11—C12 | 179.7 (4) |
N1—C2—C3—C4 | 132.8 (3) | C10—C11—C12—C13 | −0.1 (7) |
O2—C2—C3—C6 | 67.5 (4) | C11—C12—C13—C14 | 0.1 (7) |
N1—C2—C3—C6 | −113.1 (3) | C11—C12—C13—Cl1 | −179.4 (3) |
O2—C2—C3—S1 | −172.4 (3) | C12—C13—C14—C15 | 0.4 (6) |
N1—C2—C3—S1 | 6.9 (3) | Cl1—C13—C14—C15 | 179.9 (3) |
C1—S1—C3—C2 | −5.2 (2) | C11—C10—C15—C14 | 1.1 (5) |
C1—S1—C3—C4 | −126.5 (3) | C4—C10—C15—C14 | −179.2 (3) |
C1—S1—C3—C6 | 114.2 (2) | C13—C14—C15—C10 | −1.0 (6) |
C2—C3—C4—C10 | −107.6 (3) | N2—C6—C17—C22 | 53.5 (5) |
C6—C3—C4—C10 | 134.3 (3) | C7—C6—C17—C22 | 174.7 (4) |
S1—C3—C4—C10 | 11.2 (4) | C3—C6—C17—C22 | −66.6 (5) |
C2—C3—C4—C5 | 123.1 (3) | N2—C6—C17—C18 | −122.6 (3) |
C6—C3—C4—C5 | 5.0 (3) | C7—C6—C17—C18 | −1.4 (3) |
S1—C3—C4—C5 | −118.1 (3) | C3—C6—C17—C18 | 117.4 (3) |
C16—N2—C5—C4 | 172.7 (3) | C22—C17—C18—C19 | 2.8 (6) |
C6—N2—C5—C4 | 46.5 (3) | C6—C17—C18—C19 | 179.4 (4) |
C10—C4—C5—N2 | −159.6 (2) | C22—C17—C18—N3 | −175.6 (3) |
C3—C4—C5—N2 | −30.2 (3) | C6—C17—C18—N3 | 1.0 (4) |
C5—N2—C6—C17 | −170.7 (3) | C7—N3—C18—C19 | −178.4 (4) |
C16—N2—C6—C17 | 63.5 (4) | C7—N3—C18—C17 | −0.2 (4) |
C5—N2—C6—C7 | 74.5 (3) | C17—C18—C19—C20 | −1.4 (6) |
C16—N2—C6—C7 | −51.4 (4) | N3—C18—C19—C20 | 176.6 (4) |
C5—N2—C6—C3 | −42.0 (3) | C18—C19—C20—C21 | −0.3 (7) |
C16—N2—C6—C3 | −167.9 (3) | C19—C20—C21—C22 | 0.7 (7) |
C2—C3—C6—N2 | −96.1 (3) | C18—C17—C22—C21 | −2.3 (5) |
C4—C3—C6—N2 | 21.5 (3) | C6—C17—C22—C21 | −178.0 (3) |
S1—C3—C6—N2 | 147.9 (2) | C20—C21—C22—C17 | 0.6 (6) |
C2—C3—C6—C17 | 29.9 (3) | C28—C23—C24—C25 | 0.0 |
C4—C3—C6—C17 | 147.5 (3) | C23—C24—C25—C26 | 0.0 |
S1—C3—C6—C17 | −86.1 (3) | C24—C25—C26—C27 | 0.0 |
C2—C3—C6—C7 | 144.7 (3) | C25—C26—C27—C28 | 0.0 |
C4—C3—C6—C7 | −97.7 (3) | C26—C27—C28—C23 | 0.0 |
S1—C3—C6—C7 | 28.7 (3) | C24—C23—C28—C27 | 0.0 |
C18—N3—C7—O3 | 179.1 (4) | C31i—C29—C30—C31 | 5 (4) |
C18—N3—C7—C6 | −0.7 (4) | C29—C30—C31—C29i | −5 (4) |
N2—C6—C7—O3 | −56.3 (5) | C31'i—C29'—C30'—C31' | −2 (5) |
C17—C6—C7—O3 | −178.5 (3) | C29'—C30'—C31'—C29'i | 2 (5) |
C3—C6—C7—O3 | 56.2 (4) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N2ii | 0.86 | 2.39 | 3.071 (3) | 136 |
Symmetry code: (ii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C22H20ClN3O3S·1.5C6H6 |
Mr | 559.08 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.132 (3), 22.785 (7), 12.515 (4) |
β (°) | 112.477 (5) |
V (Å3) | 2933.2 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.42 × 0.40 × 0.34 |
Data collection | |
Diffractometer | Bruker SMART CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.796, 0.923 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14461, 5070, 2701 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.155, 1.02 |
No. of reflections | 5070 |
No. of parameters | 370 |
No. of restraints | 180 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.23 |
Computer programs: Bruker SMART (Bruker,1997), Bruker SMART, Bruker SAINT (Bruker,1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Bruker SHELXTL (Bruker,1997), Bruker SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N2i | 0.86 | 2.39 | 3.071 (3) | 136 |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Spiro-compounds represent an important class of naturally occurring substances, which in many cases exhibit interesting biological properties (Kobayashi et al., 1991; James et al., 1991). 1,3-Dipolar cycloaddition reactions are widely used for the construction of spiro-compounds (Caramella & Grunanger, 1984). In this paper, the structure of the title compound, (I), is reported. The compound was synthesized by the intermolecular [3 + 2]-cycloaddition of azomethine ylide, derived from isatin and sarcosine by a decarboxylative route, and 5-(4-chloro-benzylidene)-3-ethylthiazolidine-2,4-dione.
The molecular structure of (I) is shown in Fig. 1. The molecule involves a chain of 2-oxindole, pyrrolidine, and thiazolidine moieties, joined via two spiro-junctions. The pyrrolidine ring N2—C5—C4—C3—C6 has an envelope conformation; atom N2 is displaced by 0.618 (3) Å from the mean plane of the C5/C4/C3/C6 atoms [plane A; maximum deviation of the C4 atom is 0.031 (3) Å]. The C5/N2/C6 plane forms a dihedral angle of 135.6 (2)° with plane A, whereas the dihedral angle of the latter with the mean plane of the phenyl ring (C10–C15) is 76.7 (3)°. Both bicyclic indole system and thiazolidine ring are almost planar [maximum deviations of atoms C17 and C2 from their respective mean planes are 0.035 (3) and 0.041 (4) Å]; their planes are approximately orthogonal to the bottom plane of the pyrrolidine cycle (plane A); the dihedral angles are equal to 78.3 (2) and 88.7 (3)°, respectively. Atoms O1 and O2 are displaced from the mean plane of the thiazolidine cycle by 0.027 (2) and −0.155 (2) Å, respectively.
There is one `active' H atom in the molecule which participates in the intermolecular N3—H3···N2i hydrogen bond [symmetry code: (i) x, −y + 1/2, z − 1/2] (Table 1). This hydrogen bond links the molecules of (I) in the crystal into infinite chains running along the c axis of the crystal (Fig. 2).