Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105005044/gd1369sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105005044/gd1369IVsup2.hkl |
CCDC reference: 269043
Single crystals of (IV) in the form of bright-yellow needles suitable for X-ray studies were prepared by the following procedure. To a solution of 1,1-dimethyl hydrazine (0.120 g, 2 mmol) in anhydrous tetrahydrofuran (5 ml) was added, dropwise, acridin-9-yl isothiocyanate, (I) (Mazagová et al., 1994) (0.473 g, 2 mmol), dissolved in anhydrous tetrahydrofurane (5 ml). The reaction mixture was stirred at room temperature until isothiocyanate disappeared (monitored by thin-layer chromatography, eluant cyclohexane/ethyl acetate, 3:1); a precipitate of 1,1-dimethyl-4-(acridin-9-yl)-thiosemicarbazide, (II), was filtered off, dried and recrystallized from methanol/diethyl ether. Yield 60%, m.p. 466–469 K. 1H NMR (DMSO-d6): δ 2.76 (s, 6H, 2 × CH3), 7.50–8.25 (m, 8H, AcrH), 9.59 (br s, 1H, NH), 10.40 (br s, 1H, NH). To a suspension of thiosemicarbazide (II) (0.2 g, 0.67 mmol) in dry benzene (5 ml), methyl bromoacetate (0.103 g, 0.063 ml, 0.67 mmol) was slowly added. The solution was stirred at room temperature for 5 h, triethylamine (0.137 g, 0.188 ml, 1.35 mmol) was added, and stirring was continued for the next 2 h. The solution was filtered, the filtrate was evaporated and the residue was chromatographed using a column filled with silica gel (Merck 109385, 0.040–0.063 mm, 230–400 mesh, eluant ethyl acetate/cyclohexane, 4:1). To a saturated solution of crude (IV) in hot ethyl acetate, n-heptane was added to first turbidity and the product was left to crystallize for 2 h. Yield 31%, m.p. 475–477 K. 1H NMR (DMSO-d6): δ 3.16 (s, 6H, H-17,18), 3.93 (s, 2H, H-15), 7.53, 7.81, 8.00, 8.12 (m, 8H, AcrH); 13C NMR: δ: 30.8 (C-15), 42.7 (C-17,18), 117.0 (C-10,13), 123.9, 125.0, 129.2, 130.4 (AcrCH), 148.9 (C-11,12), 150.4 (C-9), 155.0? (C-14), 169.3 (C-16).
H atoms were freely refined with isotropic displacement parameters [C—H = 0.927 (19)–0.99 (3) Å).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 2000); software used to prepare material for publication: program (reference)?.
Fig. 1. A view of title compound, showing displacement ellipsoids at the 30% probability level. |
C18H16N4OS | F(000) = 704 |
Mr = 336.42 | Dx = 1.368 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 3118 reflections |
a = 7.282 (5) Å | θ = 2.1–25.0° |
b = 19.456 (5) Å | µ = 0.21 mm−1 |
c = 11.954 (5) Å | T = 298 K |
β = 105.326 (5)° | Prism, yellow |
V = 1633.4 (14) Å3 | 0.40 × 0.12 × 0.11 mm |
Z = 4 |
Bruker SMART 1000 diffractometer | 2867 independent reflections |
Radiation source: fine-focus sealed tube | 1776 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Detector resolution: 8.192 pixels/mm pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Bruker 1999) | k = −23→15 |
Tmin = 0.787, Tmax = 0.977 | l = −14→13 |
8245 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | All H-atom parameters refined |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0351P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.87 | (Δ/σ)max < 0.001 |
2867 reflections | Δρmax = 0.17 e Å−3 |
282 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0023 (5) |
C18H16N4OS | V = 1633.4 (14) Å3 |
Mr = 336.42 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.282 (5) Å | µ = 0.21 mm−1 |
b = 19.456 (5) Å | T = 298 K |
c = 11.954 (5) Å | 0.40 × 0.12 × 0.11 mm |
β = 105.326 (5)° |
Bruker SMART 1000 diffractometer | 2867 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker 1999) | 1776 reflections with I > 2σ(I) |
Tmin = 0.787, Tmax = 0.977 | Rint = 0.043 |
8245 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.079 | All H-atom parameters refined |
S = 0.87 | Δρmax = 0.17 e Å−3 |
2867 reflections | Δρmin = −0.26 e Å−3 |
282 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 | 0.30409 (8) | 0.33825 (3) | 0.10522 (5) | 0.04651 (19) | |
O1 | 0.0638 (2) | 0.46877 (7) | −0.13032 (13) | 0.0483 (4) | |
N1 | 0.9133 (2) | 0.19210 (9) | 0.24539 (16) | 0.0469 (5) | |
N2 | 0.5803 (2) | 0.32560 (9) | −0.00933 (15) | 0.0429 (5) | |
N3 | 0.3238 (2) | 0.39793 (8) | −0.08672 (13) | 0.0366 (4) | |
N4 | 0.3830 (2) | 0.41895 (9) | −0.18407 (15) | 0.0455 (5) | |
C1 | 0.8163 (3) | 0.37932 (12) | 0.2086 (2) | 0.0454 (6) | |
H1 | 0.746 (3) | 0.4113 (10) | 0.1552 (19) | 0.053 (7)* | |
C2 | 0.9333 (3) | 0.40223 (14) | 0.3084 (2) | 0.0534 (6) | |
H2 | 0.937 (3) | 0.4497 (11) | 0.3278 (18) | 0.054 (7)* | |
C3 | 1.0400 (4) | 0.35528 (15) | 0.3900 (2) | 0.0590 (7) | |
H3 | 1.118 (3) | 0.3742 (10) | 0.4576 (18) | 0.051 (7)* | |
C4 | 1.0306 (3) | 0.28751 (14) | 0.3688 (2) | 0.0545 (7) | |
H4 | 1.101 (3) | 0.2557 (11) | 0.4238 (18) | 0.053 (6)* | |
C5 | 0.8044 (3) | 0.09588 (12) | 0.1220 (2) | 0.0524 (6) | |
H5 | 0.880 (3) | 0.0693 (10) | 0.1806 (17) | 0.043 (6)* | |
C6 | 0.6941 (4) | 0.06853 (14) | 0.0237 (2) | 0.0577 (7) | |
H6 | 0.698 (3) | 0.0202 (12) | 0.013 (2) | 0.071 (8)* | |
C7 | 0.5741 (4) | 0.11024 (14) | −0.0614 (2) | 0.0579 (7) | |
H7 | 0.500 (3) | 0.0891 (11) | −0.132 (2) | 0.071 (8)* | |
C8 | 0.5700 (3) | 0.17908 (14) | −0.0456 (2) | 0.0503 (6) | |
H8 | 0.490 (3) | 0.2086 (10) | −0.1031 (19) | 0.055 (7)* | |
C10 | 0.6839 (3) | 0.21028 (11) | 0.05681 (18) | 0.0401 (5) | |
C11 | 0.8028 (3) | 0.16762 (11) | 0.14404 (19) | 0.0425 (5) | |
C12 | 0.9123 (3) | 0.26043 (11) | 0.26361 (19) | 0.0430 (5) | |
C13 | 0.8002 (3) | 0.30799 (11) | 0.18189 (18) | 0.0382 (5) | |
C9 | 0.6831 (3) | 0.28118 (11) | 0.07814 (17) | 0.0390 (5) | |
C14 | 0.4236 (3) | 0.35167 (10) | −0.00316 (17) | 0.0360 (5) | |
C15 | 0.1063 (3) | 0.39156 (14) | 0.0298 (2) | 0.0475 (6) | |
H15A | 0.084 (3) | 0.4243 (10) | 0.0830 (17) | 0.049 (6)* | |
H15B | −0.002 (3) | 0.3631 (12) | 0.006 (2) | 0.074 (8)* | |
C16 | 0.1567 (3) | 0.42451 (11) | −0.07050 (18) | 0.0375 (5) | |
C17 | 0.5622 (4) | 0.45742 (17) | −0.1534 (3) | 0.0620 (7) | |
H17A | 0.672 (4) | 0.4260 (14) | −0.124 (2) | 0.104 (11)* | |
H17B | 0.577 (3) | 0.4775 (13) | −0.221 (2) | 0.088 (9)* | |
H17C | 0.555 (4) | 0.4913 (14) | −0.096 (3) | 0.101 (11)* | |
C18 | 0.3777 (4) | 0.36265 (17) | −0.2658 (2) | 0.0614 (8) | |
H18A | 0.254 (4) | 0.3391 (14) | −0.279 (2) | 0.101 (10)* | |
H18B | 0.396 (4) | 0.3843 (13) | −0.332 (2) | 0.089 (9)* | |
H18C | 0.485 (3) | 0.3316 (12) | −0.236 (2) | 0.074 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0474 (3) | 0.0548 (4) | 0.0396 (3) | 0.0042 (3) | 0.0155 (3) | 0.0075 (3) |
O1 | 0.0462 (8) | 0.0419 (9) | 0.0533 (10) | 0.0114 (8) | 0.0070 (8) | 0.0025 (8) |
N1 | 0.0419 (10) | 0.0473 (12) | 0.0483 (12) | 0.0060 (9) | 0.0062 (10) | 0.0068 (9) |
N2 | 0.0399 (10) | 0.0490 (11) | 0.0394 (11) | 0.0099 (9) | 0.0100 (9) | 0.0082 (8) |
N3 | 0.0349 (9) | 0.0414 (10) | 0.0344 (10) | 0.0050 (8) | 0.0107 (8) | 0.0058 (8) |
N4 | 0.0438 (10) | 0.0550 (12) | 0.0395 (11) | 0.0016 (9) | 0.0141 (9) | 0.0091 (9) |
C1 | 0.0446 (13) | 0.0468 (16) | 0.0451 (15) | 0.0034 (12) | 0.0122 (12) | 0.0079 (12) |
C2 | 0.0570 (15) | 0.0489 (17) | 0.0545 (17) | −0.0058 (13) | 0.0151 (14) | −0.0017 (13) |
C3 | 0.0520 (15) | 0.067 (2) | 0.0509 (17) | −0.0079 (14) | 0.0012 (13) | −0.0029 (14) |
C4 | 0.0495 (15) | 0.0572 (18) | 0.0472 (16) | 0.0059 (13) | −0.0038 (12) | 0.0094 (13) |
C5 | 0.0519 (15) | 0.0474 (17) | 0.0562 (18) | 0.0094 (13) | 0.0115 (14) | 0.0080 (14) |
C6 | 0.0627 (16) | 0.0482 (17) | 0.0639 (19) | 0.0026 (14) | 0.0198 (15) | −0.0017 (14) |
C7 | 0.0568 (16) | 0.0616 (19) | 0.0530 (17) | −0.0028 (14) | 0.0108 (14) | −0.0090 (14) |
C8 | 0.0422 (13) | 0.0606 (18) | 0.0462 (16) | 0.0084 (12) | 0.0084 (12) | 0.0009 (13) |
C10 | 0.0338 (11) | 0.0462 (14) | 0.0418 (14) | 0.0048 (10) | 0.0124 (11) | 0.0047 (10) |
C11 | 0.0368 (11) | 0.0437 (14) | 0.0492 (14) | 0.0053 (11) | 0.0150 (11) | 0.0068 (11) |
C12 | 0.0339 (11) | 0.0503 (15) | 0.0446 (14) | 0.0020 (11) | 0.0102 (10) | 0.0070 (11) |
C13 | 0.0325 (11) | 0.0438 (14) | 0.0399 (13) | 0.0043 (10) | 0.0126 (10) | 0.0068 (10) |
C9 | 0.0312 (11) | 0.0480 (14) | 0.0402 (13) | 0.0068 (10) | 0.0139 (10) | 0.0095 (10) |
C14 | 0.0368 (11) | 0.0382 (13) | 0.0320 (12) | 0.0002 (10) | 0.0073 (9) | −0.0001 (10) |
C15 | 0.0454 (14) | 0.0500 (16) | 0.0504 (16) | 0.0054 (13) | 0.0185 (13) | 0.0002 (12) |
C16 | 0.0359 (11) | 0.0361 (13) | 0.0389 (13) | 0.0000 (10) | 0.0073 (10) | −0.0047 (10) |
C17 | 0.0623 (18) | 0.064 (2) | 0.065 (2) | −0.0158 (16) | 0.0255 (16) | 0.0042 (16) |
C18 | 0.0565 (18) | 0.089 (2) | 0.0413 (16) | −0.0088 (17) | 0.0165 (14) | −0.0089 (15) |
S1—C14 | 1.761 (2) | C5—C11 | 1.421 (3) |
S1—C15 | 1.810 (2) | C5—H5 | 0.927 (19) |
O1—C16 | 1.206 (2) | C6—C7 | 1.410 (3) |
N1—C12 | 1.347 (2) | C6—H6 | 0.95 (2) |
N1—C11 | 1.352 (3) | C7—C8 | 1.354 (3) |
N2—C14 | 1.269 (2) | C7—H7 | 0.97 (2) |
N2—C9 | 1.409 (2) | C8—C10 | 1.421 (3) |
N3—C16 | 1.383 (2) | C8—H8 | 0.96 (2) |
N3—C14 | 1.397 (2) | C10—C9 | 1.403 (3) |
N3—N4 | 1.404 (2) | C10—C11 | 1.431 (3) |
N4—C18 | 1.461 (3) | C12—C13 | 1.434 (3) |
N4—C17 | 1.465 (3) | C13—C9 | 1.407 (3) |
C1—C2 | 1.346 (3) | C15—C16 | 1.488 (3) |
C1—C13 | 1.422 (3) | C15—H15A | 0.94 (2) |
C1—H1 | 0.94 (2) | C15—H15B | 0.94 (2) |
C2—C3 | 1.410 (3) | C17—H17A | 0.99 (3) |
C2—H2 | 0.95 (2) | C17—H17B | 0.93 (3) |
C3—C4 | 1.341 (3) | C17—H17C | 0.96 (3) |
C3—H3 | 0.93 (2) | C18—H18A | 0.99 (3) |
C4—C12 | 1.424 (3) | C18—H18B | 0.94 (3) |
C4—H4 | 0.95 (2) | C18—H18C | 0.98 (2) |
C5—C6 | 1.345 (3) | ||
C14—S1—C15 | 91.81 (11) | N1—C11—C5 | 118.7 (2) |
C12—N1—C11 | 117.71 (18) | N1—C11—C10 | 123.4 (2) |
C14—N2—C9 | 120.77 (17) | C5—C11—C10 | 117.9 (2) |
C16—N3—C14 | 116.84 (17) | N1—C12—C4 | 118.7 (2) |
C16—N3—N4 | 118.78 (16) | N1—C12—C13 | 123.6 (2) |
C14—N3—N4 | 124.38 (16) | C4—C12—C13 | 117.7 (2) |
N3—N4—C18 | 112.08 (18) | C9—C13—C1 | 123.70 (19) |
N3—N4—C17 | 112.91 (19) | C9—C13—C12 | 117.69 (19) |
C18—N4—C17 | 114.5 (2) | C1—C13—C12 | 118.6 (2) |
C2—C1—C13 | 121.2 (2) | C10—C9—C13 | 119.62 (19) |
C2—C1—H1 | 119.1 (13) | C10—C9—N2 | 119.67 (19) |
C13—C1—H1 | 119.7 (13) | C13—C9—N2 | 120.40 (19) |
C1—C2—C3 | 120.2 (3) | N2—C14—N3 | 121.46 (18) |
C1—C2—H2 | 120.5 (13) | N2—C14—S1 | 127.64 (16) |
C3—C2—H2 | 119.1 (13) | N3—C14—S1 | 110.90 (14) |
C4—C3—C2 | 121.0 (3) | C16—C15—S1 | 108.36 (16) |
C4—C3—H3 | 122.7 (13) | C16—C15—H15A | 112.0 (12) |
C2—C3—H3 | 116.3 (13) | S1—C15—H15A | 107.8 (12) |
C3—C4—C12 | 121.3 (2) | C16—C15—H15B | 111.7 (15) |
C3—C4—H4 | 121.2 (13) | S1—C15—H15B | 107.8 (14) |
C12—C4—H4 | 117.4 (13) | H15A—C15—H15B | 109.0 (19) |
C6—C5—C11 | 121.2 (2) | O1—C16—N3 | 124.10 (19) |
C6—C5—H5 | 122.7 (12) | O1—C16—C15 | 124.47 (19) |
C11—C5—H5 | 116.1 (12) | N3—C16—C15 | 111.43 (18) |
C5—C6—C7 | 121.0 (3) | N4—C17—H17A | 110.8 (15) |
C5—C6—H6 | 118.8 (15) | N4—C17—H17B | 107.5 (16) |
C7—C6—H6 | 120.2 (15) | H17A—C17—H17B | 107 (2) |
C8—C7—C6 | 120.1 (3) | N4—C17—H17C | 108.3 (16) |
C8—C7—H7 | 121.0 (14) | H17A—C17—H17C | 111 (2) |
C6—C7—H7 | 118.9 (14) | H17B—C17—H17C | 112 (2) |
C7—C8—C10 | 120.9 (2) | N4—C18—H18A | 108.2 (16) |
C7—C8—H8 | 121.4 (12) | N4—C18—H18B | 104.1 (16) |
C10—C8—H8 | 117.7 (12) | H18A—C18—H18B | 114 (2) |
C9—C10—C8 | 123.2 (2) | N4—C18—H18C | 110.1 (14) |
C9—C10—C11 | 117.9 (2) | H18A—C18—H18C | 112 (2) |
C8—C10—C11 | 118.9 (2) | H18B—C18—H18C | 108 (2) |
C16—N3—N4—C18 | −113.6 (2) | N1—C12—C13—C1 | −177.58 (19) |
C14—N3—N4—C18 | 66.9 (3) | C4—C12—C13—C1 | 1.5 (3) |
C16—N3—N4—C17 | 115.3 (2) | C8—C10—C9—C13 | 179.95 (18) |
C14—N3—N4—C17 | −64.2 (3) | C11—C10—C9—C13 | 1.3 (3) |
C13—C1—C2—C3 | −1.3 (3) | C8—C10—C9—N2 | −6.5 (3) |
C1—C2—C3—C4 | 1.6 (4) | C11—C10—C9—N2 | 174.81 (16) |
C2—C3—C4—C12 | −0.2 (4) | C1—C13—C9—C10 | 176.76 (19) |
C11—C5—C6—C7 | 0.5 (4) | C12—C13—C9—C10 | −1.8 (3) |
C5—C6—C7—C8 | 0.7 (4) | C1—C13—C9—N2 | 3.3 (3) |
C6—C7—C8—C10 | −0.7 (4) | C12—C13—C9—N2 | −175.31 (17) |
C7—C8—C10—C9 | −179.2 (2) | C14—N2—C9—C10 | 105.3 (2) |
C7—C8—C10—C11 | −0.5 (3) | C14—N2—C9—C13 | −81.2 (2) |
C12—N1—C11—C5 | 178.82 (18) | C9—N2—C14—N3 | 177.41 (18) |
C12—N1—C11—C10 | −0.9 (3) | C9—N2—C14—S1 | −1.5 (3) |
C6—C5—C11—N1 | 178.6 (2) | C16—N3—C14—N2 | −178.60 (18) |
C6—C5—C11—C10 | −1.7 (3) | N4—N3—C14—N2 | 1.0 (3) |
C9—C10—C11—N1 | 0.1 (3) | C16—N3—C14—S1 | 0.5 (2) |
C8—C10—C11—N1 | −178.61 (19) | N4—N3—C14—S1 | −179.95 (14) |
C9—C10—C11—C5 | −179.59 (18) | C15—S1—C14—N2 | −177.0 (2) |
C8—C10—C11—C5 | 1.7 (3) | C15—S1—C14—N3 | 4.03 (16) |
C11—N1—C12—C4 | −178.78 (19) | C14—S1—C15—C16 | −7.05 (18) |
C11—N1—C12—C13 | 0.3 (3) | C14—N3—C16—O1 | 174.02 (19) |
C3—C4—C12—N1 | 177.8 (2) | N4—N3—C16—O1 | −5.6 (3) |
C3—C4—C12—C13 | −1.3 (3) | C14—N3—C16—C15 | −6.0 (2) |
C2—C1—C13—C9 | −178.8 (2) | N4—N3—C16—C15 | 174.34 (18) |
C2—C1—C13—C12 | −0.2 (3) | S1—C15—C16—O1 | −171.51 (17) |
N1—C12—C13—C9 | 1.1 (3) | S1—C15—C16—N3 | 8.5 (2) |
C4—C12—C13—C9 | −179.86 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 (2) | 2.42 (2) | 3.311 (4) | 161.7 (17) |
C15—H15A···O1ii | 0.94 (2) | 2.48 (2) | 3.339 (4) | 152.1 (16) |
C18—H18B···Cgiii | 0.94 (3) | 2.97 (3) | 3.645 (4) | 131 (2) |
Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) −x, −y+1, −z; (iii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H16N4OS |
Mr | 336.42 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.282 (5), 19.456 (5), 11.954 (5) |
β (°) | 105.326 (5) |
V (Å3) | 1633.4 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.40 × 0.12 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker 1999) |
Tmin, Tmax | 0.787, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8245, 2867, 1776 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.079, 0.87 |
No. of reflections | 2867 |
No. of parameters | 282 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.17, −0.26 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), DIAMOND (Crystal Impact, 2000), program (reference)?.
S1—C14 | 1.761 (2) | N2—C9 | 1.409 (2) |
S1—C15 | 1.810 (2) | N3—C16 | 1.383 (2) |
O1—C16 | 1.206 (2) | N3—C14 | 1.397 (2) |
N1—C12 | 1.347 (2) | N3—N4 | 1.404 (2) |
N1—C11 | 1.352 (3) | N4—C18 | 1.461 (3) |
N2—C14 | 1.269 (2) | N4—C17 | 1.465 (3) |
C14—S1—C15 | 91.81 (11) | C14—N3—N4 | 124.38 (16) |
C12—N1—C11 | 117.71 (18) | N3—N4—C18 | 112.08 (18) |
C14—N2—C9 | 120.77 (17) | N3—N4—C17 | 112.91 (19) |
C16—N3—C14 | 116.84 (17) | C18—N4—C17 | 114.5 (2) |
C16—N3—N4 | 118.78 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 (2) | 2.42 (2) | 3.311 (4) | 161.7 (17) |
C15—H15A···O1ii | 0.94 (2) | 2.48 (2) | 3.339 (4) | 152.1 (16) |
C18—H18B···Cgiii | 0.94 (3) | 2.97 (3) | 3.645 (4) | 131 (2) |
Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) −x, −y+1, −z; (iii) x, −y+1/2, z−1/2. |
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Thiazole derivates, particularly 1,3-thiazolidin-4-ones, have a broad spectrum of biological activity (Singh et al., 1998; Liu & Anthonsen, 2000). Our continuing interest in 9-substituted acridine compounds, which may possess anticancer, chemiluminescent and intercalating properties (Kristian et al., 1998; Klika et al., 2001; Bernát et al., 2004; Demeunynck et al., 2001), led us to the synthesis of new acridin-9-yl-thiosemicarbazides and thiazolidinone derivatives. Besides the synthetic goal of this work, a presumed synergism of biological effects of both heterocyclic skeletons was another interesting point to study.
To obtain the target compounds, the reaction of acridin-9-yl isothiocyanate, (I), with 1,1- and 1,2-disubstituted hydrazines was used to give intermediate thiosemicarbazides, which were further cyclized with bromoacetic acid ester or bromide to obtain products of type IV (Fig. 1), (Vilková et al., 2005). Because of the presence of four nucleophilic centres in thiosemicarbazides, at least six types of isomeric five-membered heterocyclic structures could possibly be formed from the terminal cyclization step and/or subsequent possible rearrangements of the Dimroth type. An NMR proof of these structures is questionable because of ambiguities in assignments of cross peaks from two-dimensional H,C-correlation and NOESY spectra. Hence we have determined the structure of the selected model compound (IV), obtained by the reaction of 1,1-dimethyl-4-(acridin-9-yl)-thiosemicarbazide, (II), with methyl bromoacetate. The preparation of the studied compound involved the alkylation of the thiosemicarbazide to afford 1,1-dimethyl-4-(acridin-9-yl)-S-methoxycarbonylmethylene- isothiosemicarbazide hydrobromide, (III), by the attachment of the S atom of the thiosemicarbazide to a bromomethylene C atom (see scheme below).
A search of the Cambridge Structural Database (release of August 2004; Allen, 2002) showed that the title compound is the first example of a compound in which both acridine and thiazole ring systems are linked by an imine N atom. On the other hand, three derivatives of N-(acridin-9-yl)-1,4-benzoquinone monoimines have been structurally characterized (Clark et al., 1993), and there are two entries containing an imino-1,3-thiazolidin-4-one ring (Deepthi et al., 2001).
The acridine and thiazoline ring systems in (IV) both deviate significantly from planarity. Atom C2 exhibits the highest deviation, of 0.050 (3) Å from the mean plane through the 14 atoms of the acridine ring system, while in the thiazolidine ring, atom C15 deviates most from the mean plane [0.079 (3) Å]. The geometric parameters for the acridine ring system are similar to those found in phenyl-(acridin-9-yl)-amine (Leardini et al., 1998). The N2—C14 bond in the imine group is clearly shorter than the C9—N2 bond, indicating the double-bond character of the former. Similar distances were found in N-(9-acridinyl)-2-methoxy-1,4-benzoquinone monoimine (Clark et al., 1993). Owing to steric effects, the ring systems linked by imine atom N2 are almost perpendicular; the angle between the mean planes through the rings is 99.69 (6)°. The geometric parameters in the 1,3-thiazolidin-4-one ring are normal (Deepthi et al., 2001).
The packing of the individual molecules in the solid state is governed by two intermolecular C—H···O hydrogen bonds (Table 2) and a C—H···π(arene) hydrogen bond. Pairs of molecules of (IV) are linked by C15—H15···O1i [symmetry code: (i) −x, 1 − y, −z] hydrogen bonds, forming a ring that can be described by graph-set descriptor R22(8) (Berstein et al., 1995); moreover, each O1 atom participates in a C5—H5···O1ii [symmetry code: (ii) 1 + x, 1/2 − y, 1/2 + z] hydrogen bond, linking pairs of molecules into deformed planes. Finally, the planes interact by C18—H18···π(arene) hydrogen bonds.