Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054013/ci2481sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054013/ci2481Isup2.hkl |
CCDC reference: 623908
The title compound was prepared according to the literature procedure of Liu et al. (2006) and suitable crystals were obtained by evaporation of a dichoromethane solution (m.p. 563–565 K). Analysis, calculated for C27H20Cl5N3O2S: C 51.66, H 3.31, N 6.69%; found: C 51.71, H 3.40, N 6.78%. IR (KBr, ν, cm-1): 3125(Ph—H), 2931,2863(C—H), 1705(C=O), 1620, 1562, 1517, 1490, 1365, 1252, 1092, 843. 1H NMR(CDCl3, TMS, 400 MHz): 1.62–1.80(m, 4H, 2CH2), 2.34–2.79(m, 4H, 2CH2), 3.03(s, 3H, CH3), 7.15–7.58(m, 7H, Ar—H). MS(EI, %): 544 (100), 543(M+ 90), 396 (16), 380 (20).
The dichloromethane molecule is disordered over two positions, with refined occupancies of 0.775 (6) and 0.225 (6). The disorder was modelled with a C—Cl distance restraint of 1.732 (9) Å, and the Cl···Cl distance in both disorder components were restrained to be equal. The displacement parameters of disordered atoms were restrained to an approximate isotropic behaviour. H atoms were placed in geometrically idealized positions (C—H = 0.93–0.97 Å) and constrained to ride on their parent atoms, with Uiso(H) = kUeq(C) (k=1.5 for methyl and 1.2 for the other C atoms).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title compound, showing 50% probablity displacement ellipsoids. |
C26H18Cl3N3O2S·CH2Cl2 | F(000) = 2560 |
Mr = 627.77 | Dx = 1.495 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3031 reflections |
a = 18.295 (6) Å | θ = 2.2–19.0° |
b = 10.851 (4) Å | µ = 0.63 mm−1 |
c = 28.097 (9) Å | T = 292 K |
V = 5578 (3) Å3 | Block, colourless |
Z = 8 | 0.20 × 0.16 × 0.12 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5488 independent reflections |
Radiation source: fine-focus sealed tube | 3296 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −21→22 |
Tmin = 0.885, Tmax = 0.929 | k = −13→13 |
29034 measured reflections | l = −22→34 |
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)] = 0.078 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.234 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1242P)2 + 1.4543P] where P = (Fo2 + 2Fc2)/3 |
5488 reflections | (Δ/σ)max = 0.001 |
372 parameters | Δρmax = 0.64 e Å−3 |
41 restraints | Δρmin = −0.52 e Å−3 |
C26H18Cl3N3O2S·CH2Cl2 | V = 5578 (3) Å3 |
Mr = 627.77 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 18.295 (6) Å | µ = 0.63 mm−1 |
b = 10.851 (4) Å | T = 292 K |
c = 28.097 (9) Å | 0.20 × 0.16 × 0.12 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5488 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3296 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.929 | Rint = 0.079 |
29034 measured reflections |
R[F2 > 2σ(F2)] = 0.078 | 41 restraints |
wR(F2) = 0.234 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.64 e Å−3 |
5488 reflections | Δρmin = −0.52 e Å−3 |
372 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) | |
S1 | 0.21511 (7) | 0.80443 (11) | 0.23989 (5) | 0.0657 (4) | |
O1 | 0.3537 (2) | 0.4856 (4) | 0.05713 (12) | 0.0791 (11) | |
O2 | 0.49710 (15) | 0.3654 (3) | 0.17882 (10) | 0.0512 (7) | |
N1 | 0.2325 (2) | 0.7211 (4) | 0.15028 (16) | 0.0623 (11) | |
N2 | 0.42421 (19) | 0.4285 (3) | 0.11922 (12) | 0.0476 (9) | |
N3 | 0.40778 (18) | 0.5042 (3) | 0.19699 (11) | 0.0427 (8) | |
Cl1 | 0.60808 (11) | 0.10969 (19) | −0.00222 (6) | 0.1144 (7) | |
Cl2 | 0.61639 (11) | 0.41703 (16) | 0.37059 (5) | 0.1062 (7) | |
Cl3 | 0.61136 (8) | 0.55092 (12) | 0.18665 (5) | 0.0791 (5) | |
C1 | 0.3714 (2) | 0.5894 (4) | 0.29686 (16) | 0.0510 (11) | |
H1A | 0.4207 | 0.6198 | 0.2920 | 0.061* | |
H1B | 0.3707 | 0.5026 | 0.2886 | 0.061* | |
C2 | 0.3508 (3) | 0.6043 (5) | 0.34868 (18) | 0.0732 (15) | |
H2A | 0.3103 | 0.5496 | 0.3556 | 0.088* | |
H2B | 0.3918 | 0.5785 | 0.3681 | 0.088* | |
C3 | 0.3304 (3) | 0.7282 (5) | 0.3624 (2) | 0.0808 (16) | |
H3A | 0.3719 | 0.7825 | 0.3578 | 0.097* | |
H3B | 0.3182 | 0.7289 | 0.3960 | 0.097* | |
C4 | 0.2656 (3) | 0.7775 (5) | 0.33410 (19) | 0.0667 (13) | |
H4A | 0.2205 | 0.7449 | 0.3472 | 0.080* | |
H4B | 0.2640 | 0.8666 | 0.3366 | 0.080* | |
C5 | 0.2719 (2) | 0.7413 (4) | 0.28293 (17) | 0.0541 (11) | |
C6 | 0.3202 (2) | 0.6575 (3) | 0.26505 (16) | 0.0460 (10) | |
C7 | 0.3112 (2) | 0.6435 (4) | 0.21415 (15) | 0.0447 (10) | |
C8 | 0.2551 (2) | 0.7161 (4) | 0.19556 (17) | 0.0536 (11) | |
C9 | 0.2674 (2) | 0.6507 (5) | 0.11937 (17) | 0.0609 (13) | |
C10 | 0.3273 (2) | 0.5734 (4) | 0.13337 (15) | 0.0494 (11) | |
C11 | 0.2414 (3) | 0.6608 (7) | 0.06876 (19) | 0.0904 (19) | |
H11A | 0.2814 | 0.6845 | 0.0487 | 0.136* | |
H11B | 0.2035 | 0.7217 | 0.0668 | 0.136* | |
H11C | 0.2226 | 0.5826 | 0.0585 | 0.136* | |
C12 | 0.3655 (2) | 0.4967 (4) | 0.09934 (17) | 0.0559 (11) | |
C13 | 0.3492 (2) | 0.5717 (3) | 0.18081 (14) | 0.0423 (10) | |
C14 | 0.4672 (2) | 0.3507 (4) | 0.08798 (15) | 0.0507 (11) | |
C15 | 0.4589 (3) | 0.2252 (4) | 0.08967 (17) | 0.0594 (12) | |
H15 | 0.4249 | 0.1902 | 0.1102 | 0.071* | |
C16 | 0.5012 (3) | 0.1510 (5) | 0.06094 (18) | 0.0699 (14) | |
H16 | 0.4957 | 0.0658 | 0.0616 | 0.084* | |
C17 | 0.5513 (3) | 0.2048 (6) | 0.03150 (18) | 0.0717 (15) | |
C18 | 0.5596 (3) | 0.3282 (6) | 0.02942 (18) | 0.0747 (15) | |
H18 | 0.5939 | 0.3626 | 0.0089 | 0.090* | |
C19 | 0.5168 (3) | 0.4039 (5) | 0.05788 (17) | 0.0650 (13) | |
H19 | 0.5218 | 0.4891 | 0.0565 | 0.078* | |
C20 | 0.4402 (2) | 0.4372 (4) | 0.16607 (15) | 0.0445 (10) | |
C21 | 0.5227 (2) | 0.3813 (4) | 0.22526 (14) | 0.0427 (10) | |
C22 | 0.4961 (2) | 0.3099 (4) | 0.26109 (16) | 0.0540 (11) | |
H22 | 0.4590 | 0.2534 | 0.2553 | 0.065* | |
C23 | 0.5249 (3) | 0.3223 (5) | 0.30592 (17) | 0.0631 (13) | |
H23 | 0.5068 | 0.2749 | 0.3309 | 0.076* | |
C24 | 0.5799 (3) | 0.4040 (5) | 0.31384 (17) | 0.0627 (13) | |
C25 | 0.6071 (3) | 0.4726 (4) | 0.27805 (19) | 0.0623 (13) | |
H25 | 0.6455 | 0.5269 | 0.2837 | 0.075* | |
C26 | 0.5783 (2) | 0.4624 (4) | 0.23344 (16) | 0.0528 (11) | |
C27 | 0.6539 (11) | 0.7036 (15) | 0.0314 (6) | 0.249 (11) | 0.775 (6) |
H27A | 0.6307 | 0.6766 | 0.0022 | 0.298* | 0.775 (6) |
H27B | 0.6912 | 0.7639 | 0.0237 | 0.298* | 0.775 (6) |
Cl4 | 0.5897 (7) | 0.7657 (11) | 0.0703 (3) | 0.335 (6) | 0.775 (6) |
Cl5 | 0.6906 (2) | 0.5827 (6) | 0.06091 (14) | 0.211 (3) | 0.775 (6) |
C27' | 0.6306 (10) | 0.731 (2) | 0.0331 (7) | 0.072 (7) | 0.225 (6) |
H27C | 0.6128 | 0.7420 | 0.0009 | 0.086* | 0.225 (6) |
H27D | 0.6482 | 0.6468 | 0.0368 | 0.086* | 0.225 (6) |
Cl5' | 0.6977 (11) | 0.838 (2) | 0.0475 (7) | 0.267 (11) | 0.225 (6) |
Cl4' | 0.5647 (6) | 0.7663 (8) | 0.0747 (3) | 0.085 (3) | 0.225 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0499 (7) | 0.0544 (7) | 0.0928 (10) | 0.0157 (6) | 0.0065 (6) | 0.0087 (6) |
O1 | 0.082 (3) | 0.109 (3) | 0.047 (2) | 0.015 (2) | −0.0146 (17) | 0.0038 (19) |
O2 | 0.0472 (17) | 0.0563 (17) | 0.0500 (18) | 0.0139 (14) | −0.0046 (13) | −0.0038 (14) |
N1 | 0.044 (2) | 0.071 (3) | 0.071 (3) | 0.0063 (19) | −0.001 (2) | 0.024 (2) |
N2 | 0.046 (2) | 0.053 (2) | 0.043 (2) | 0.0004 (16) | −0.0011 (16) | 0.0026 (16) |
N3 | 0.0421 (19) | 0.0427 (18) | 0.043 (2) | 0.0042 (15) | −0.0007 (15) | 0.0063 (16) |
Cl1 | 0.1140 (14) | 0.1339 (15) | 0.0954 (13) | 0.0158 (11) | 0.0231 (10) | −0.0474 (11) |
Cl2 | 0.1456 (16) | 0.1045 (12) | 0.0685 (10) | 0.0484 (11) | −0.0462 (9) | −0.0280 (8) |
Cl3 | 0.0886 (10) | 0.0617 (8) | 0.0870 (10) | −0.0128 (7) | 0.0238 (7) | 0.0028 (7) |
C1 | 0.050 (2) | 0.043 (2) | 0.061 (3) | 0.0013 (19) | −0.004 (2) | −0.001 (2) |
C2 | 0.089 (4) | 0.072 (3) | 0.059 (3) | 0.007 (3) | −0.006 (3) | 0.002 (3) |
C3 | 0.084 (4) | 0.089 (4) | 0.069 (4) | 0.000 (3) | 0.007 (3) | −0.018 (3) |
C4 | 0.057 (3) | 0.057 (3) | 0.085 (4) | 0.002 (2) | 0.009 (3) | −0.012 (3) |
C5 | 0.050 (3) | 0.048 (2) | 0.064 (3) | −0.004 (2) | 0.009 (2) | 0.003 (2) |
C6 | 0.038 (2) | 0.033 (2) | 0.067 (3) | −0.0028 (17) | 0.0056 (19) | 0.0030 (19) |
C7 | 0.033 (2) | 0.043 (2) | 0.058 (3) | −0.0026 (18) | 0.0029 (18) | 0.014 (2) |
C8 | 0.042 (2) | 0.048 (2) | 0.071 (3) | −0.0013 (19) | 0.005 (2) | 0.017 (2) |
C9 | 0.045 (3) | 0.075 (3) | 0.062 (3) | 0.001 (2) | −0.006 (2) | 0.023 (3) |
C10 | 0.041 (2) | 0.055 (3) | 0.052 (3) | −0.001 (2) | −0.0029 (19) | 0.015 (2) |
C11 | 0.064 (3) | 0.138 (5) | 0.070 (4) | 0.026 (4) | −0.014 (3) | 0.030 (3) |
C12 | 0.048 (3) | 0.067 (3) | 0.052 (3) | −0.004 (2) | −0.003 (2) | 0.016 (2) |
C13 | 0.037 (2) | 0.039 (2) | 0.051 (3) | −0.0041 (17) | −0.0036 (18) | 0.0141 (18) |
C14 | 0.048 (3) | 0.062 (3) | 0.042 (2) | −0.006 (2) | −0.0007 (19) | −0.001 (2) |
C15 | 0.061 (3) | 0.060 (3) | 0.058 (3) | −0.013 (2) | 0.004 (2) | −0.002 (2) |
C16 | 0.070 (3) | 0.071 (3) | 0.069 (3) | −0.009 (3) | −0.002 (3) | −0.018 (3) |
C17 | 0.070 (3) | 0.091 (4) | 0.053 (3) | 0.000 (3) | 0.000 (3) | −0.025 (3) |
C18 | 0.069 (3) | 0.102 (5) | 0.053 (3) | −0.001 (3) | 0.018 (3) | −0.003 (3) |
C19 | 0.071 (3) | 0.064 (3) | 0.060 (3) | −0.007 (3) | 0.013 (3) | 0.004 (2) |
C20 | 0.041 (2) | 0.044 (2) | 0.049 (3) | −0.0026 (19) | −0.0001 (19) | 0.005 (2) |
C21 | 0.043 (2) | 0.043 (2) | 0.042 (2) | 0.0144 (19) | −0.0028 (18) | −0.0020 (18) |
C22 | 0.050 (3) | 0.053 (3) | 0.058 (3) | 0.008 (2) | −0.001 (2) | 0.004 (2) |
C23 | 0.078 (3) | 0.059 (3) | 0.053 (3) | 0.019 (3) | 0.004 (2) | 0.011 (2) |
C24 | 0.077 (3) | 0.057 (3) | 0.055 (3) | 0.027 (3) | −0.017 (3) | −0.015 (2) |
C25 | 0.057 (3) | 0.055 (3) | 0.075 (4) | 0.007 (2) | −0.012 (3) | −0.014 (3) |
C26 | 0.050 (3) | 0.045 (2) | 0.064 (3) | 0.007 (2) | 0.008 (2) | −0.004 (2) |
C27 | 0.278 (14) | 0.259 (13) | 0.208 (13) | −0.023 (10) | 0.037 (10) | 0.018 (9) |
Cl4 | 0.387 (12) | 0.353 (10) | 0.266 (8) | 0.012 (9) | −0.060 (8) | −0.009 (8) |
Cl5 | 0.132 (3) | 0.355 (7) | 0.148 (3) | −0.034 (3) | −0.025 (2) | −0.082 (4) |
C27' | 0.070 (10) | 0.098 (11) | 0.047 (9) | −0.004 (8) | 0.040 (8) | −0.002 (8) |
Cl5' | 0.300 (19) | 0.288 (18) | 0.213 (15) | −0.001 (15) | −0.024 (13) | 0.008 (13) |
Cl4' | 0.127 (6) | 0.092 (5) | 0.037 (4) | 0.006 (4) | 0.029 (4) | −0.001 (3) |
S1—C8 | 1.733 (5) | C9—C11 | 1.504 (7) |
S1—C5 | 1.735 (5) | C10—C13 | 1.392 (6) |
O1—C12 | 1.211 (5) | C10—C12 | 1.447 (7) |
O2—C20 | 1.349 (5) | C11—H11A | 0.96 |
O2—C21 | 1.397 (5) | C11—H11B | 0.96 |
N1—C9 | 1.321 (6) | C11—H11C | 0.96 |
N1—C8 | 1.338 (6) | C14—C19 | 1.369 (6) |
N2—C20 | 1.352 (5) | C14—C15 | 1.372 (6) |
N2—C12 | 1.419 (6) | C15—C16 | 1.377 (7) |
N2—C14 | 1.449 (5) | C15—H15 | 0.93 |
N3—C20 | 1.279 (5) | C16—C17 | 1.367 (8) |
N3—C13 | 1.375 (5) | C16—H16 | 0.93 |
Cl1—C17 | 1.744 (5) | C17—C18 | 1.349 (8) |
Cl2—C24 | 1.735 (5) | C18—C19 | 1.387 (7) |
Cl3—C26 | 1.737 (5) | C18—H18 | 0.93 |
C1—C6 | 1.490 (6) | C19—H19 | 0.93 |
C1—C2 | 1.513 (7) | C21—C22 | 1.360 (6) |
C1—H1A | 0.97 | C21—C26 | 1.364 (6) |
C1—H1B | 0.97 | C22—C23 | 1.372 (6) |
C2—C3 | 1.447 (7) | C22—H22 | 0.93 |
C2—H2A | 0.97 | C23—C24 | 1.358 (7) |
C2—H2B | 0.97 | C23—H23 | 0.93 |
C3—C4 | 1.525 (7) | C24—C25 | 1.347 (7) |
C3—H3A | 0.97 | C25—C26 | 1.364 (6) |
C3—H3B | 0.97 | C25—H25 | 0.93 |
C4—C5 | 1.495 (7) | C27—Cl5 | 1.691 (9) |
C4—H4A | 0.97 | C27—Cl4 | 1.739 (9) |
C4—H4B | 0.97 | C27—H27A | 0.97 |
C5—C6 | 1.364 (6) | C27—H27B | 0.97 |
C6—C7 | 1.448 (6) | C27'—Cl4' | 1.724 (9) |
C7—C8 | 1.396 (6) | C27'—Cl5' | 1.740 (9) |
C7—C13 | 1.403 (6) | C27'—H27C | 0.97 |
C9—C10 | 1.435 (6) | C27'—H27D | 0.97 |
C8—S1—C5 | 91.7 (2) | O1—C12—C10 | 128.2 (4) |
C20—O2—C21 | 115.8 (3) | N2—C12—C10 | 113.9 (4) |
C9—N1—C8 | 116.9 (4) | N3—C13—C10 | 123.2 (4) |
C20—N2—C12 | 120.7 (4) | N3—C13—C7 | 117.5 (4) |
C20—N2—C14 | 120.9 (3) | C10—C13—C7 | 119.3 (4) |
C12—N2—C14 | 118.4 (4) | C19—C14—C15 | 120.8 (4) |
C20—N3—C13 | 116.1 (3) | C19—C14—N2 | 119.3 (4) |
C6—C1—C2 | 111.6 (4) | C15—C14—N2 | 119.8 (4) |
C6—C1—H1A | 109.3 | C14—C15—C16 | 119.9 (5) |
C2—C1—H1A | 109.3 | C14—C15—H15 | 120.0 |
C6—C1—H1B | 109.3 | C16—C15—H15 | 120.0 |
C2—C1—H1B | 109.3 | C17—C16—C15 | 118.8 (5) |
H1A—C1—H1B | 108.0 | C17—C16—H16 | 120.6 |
C3—C2—C1 | 114.9 (4) | C15—C16—H16 | 120.6 |
C3—C2—H2A | 108.6 | C18—C17—C16 | 121.7 (5) |
C1—C2—H2A | 108.5 | C18—C17—Cl1 | 119.8 (4) |
C3—C2—H2B | 108.5 | C16—C17—Cl1 | 118.4 (5) |
C1—C2—H2B | 108.5 | C17—C18—C19 | 119.9 (5) |
H2A—C2—H2B | 107.5 | C17—C18—H18 | 120.0 |
C2—C3—C4 | 112.8 (5) | C19—C18—H18 | 120.0 |
C2—C3—H3A | 109.0 | C14—C19—C18 | 118.8 (5) |
C4—C3—H3A | 109.0 | C14—C19—H19 | 120.6 |
C2—C3—H3B | 109.0 | C18—C19—H19 | 120.6 |
C4—C3—H3B | 109.0 | N3—C20—O2 | 120.4 (4) |
H3A—C3—H3B | 107.8 | N3—C20—N2 | 126.9 (4) |
C5—C4—C3 | 110.5 (4) | O2—C20—N2 | 112.6 (4) |
C5—C4—H4A | 109.6 | C22—C21—C26 | 120.6 (4) |
C3—C4—H4A | 109.6 | C22—C21—O2 | 120.1 (4) |
C5—C4—H4B | 109.6 | C26—C21—O2 | 119.2 (4) |
C3—C4—H4B | 109.6 | C21—C22—C23 | 119.1 (5) |
H4A—C4—H4B | 108.1 | C21—C22—H22 | 120.4 |
C6—C5—C4 | 125.4 (4) | C23—C22—H22 | 120.4 |
C6—C5—S1 | 113.2 (4) | C24—C23—C22 | 119.9 (5) |
C4—C5—S1 | 121.4 (3) | C24—C23—H23 | 120.0 |
C5—C6—C7 | 111.1 (4) | C22—C23—H23 | 120.0 |
C5—C6—C1 | 121.1 (4) | C25—C24—C23 | 120.8 (5) |
C7—C6—C1 | 127.7 (4) | C25—C24—Cl2 | 119.9 (4) |
C8—C7—C13 | 115.4 (4) | C23—C24—Cl2 | 119.3 (4) |
C8—C7—C6 | 113.2 (4) | C24—C25—C26 | 119.8 (5) |
C13—C7—C6 | 131.4 (4) | C24—C25—H25 | 120.1 |
N1—C8—C7 | 127.2 (4) | C26—C25—H25 | 120.1 |
N1—C8—S1 | 122.1 (3) | C21—C26—C25 | 119.7 (4) |
C7—C8—S1 | 110.7 (4) | C21—C26—Cl3 | 119.2 (4) |
N1—C9—C10 | 121.8 (4) | C25—C26—Cl3 | 121.0 (4) |
N1—C9—C11 | 115.3 (4) | Cl5—C27—Cl4 | 105.1 (9) |
C10—C9—C11 | 122.9 (5) | Cl5—C27—H27A | 110.7 |
C13—C10—C9 | 119.3 (4) | Cl4—C27—H27A | 110.7 |
C13—C10—C12 | 119.1 (4) | Cl5—C27—H27B | 110.7 |
C9—C10—C12 | 121.6 (4) | Cl4—C27—H27B | 110.7 |
C9—C11—H11A | 109.5 | H27A—C27—H27B | 108.8 |
C9—C11—H11B | 109.5 | Cl4'—C27'—Cl5' | 100.7 (10) |
H11A—C11—H11B | 109.5 | Cl4'—C27'—H27C | 111.6 |
C9—C11—H11C | 109.5 | Cl5'—C27'—H27C | 111.6 |
H11A—C11—H11C | 109.5 | Cl4'—C27'—H27D | 111.6 |
H11B—C11—H11C | 109.5 | Cl5'—C27'—H27D | 111.6 |
O1—C12—N2 | 117.9 (4) | H27C—C27'—H27D | 109.4 |
C6—C1—C2—C3 | −43.0 (6) | C9—C10—C13—C7 | 1.3 (6) |
C1—C2—C3—C4 | 58.8 (7) | C12—C10—C13—C7 | −178.4 (4) |
C2—C3—C4—C5 | −40.6 (6) | C8—C7—C13—N3 | 176.2 (3) |
C3—C4—C5—C6 | 11.5 (7) | C6—C7—C13—N3 | −3.0 (6) |
C3—C4—C5—S1 | −169.1 (4) | C8—C7—C13—C10 | −2.5 (5) |
C8—S1—C5—C6 | 0.8 (3) | C6—C7—C13—C10 | 178.3 (4) |
C8—S1—C5—C4 | −178.7 (4) | C20—N2—C14—C19 | −103.7 (5) |
C4—C5—C6—C7 | 179.5 (4) | C12—N2—C14—C19 | 75.4 (5) |
S1—C5—C6—C7 | 0.1 (4) | C20—N2—C14—C15 | 74.8 (5) |
C4—C5—C6—C1 | 2.1 (7) | C12—N2—C14—C15 | −106.1 (5) |
S1—C5—C6—C1 | −177.4 (3) | C19—C14—C15—C16 | 0.2 (7) |
C2—C1—C6—C5 | 12.5 (6) | N2—C14—C15—C16 | −178.2 (4) |
C2—C1—C6—C7 | −164.5 (4) | C14—C15—C16—C17 | 0.7 (7) |
C5—C6—C7—C8 | −1.2 (5) | C15—C16—C17—C18 | −1.0 (8) |
C1—C6—C7—C8 | 176.1 (4) | C15—C16—C17—Cl1 | 176.4 (4) |
C5—C6—C7—C13 | 178.1 (4) | C16—C17—C18—C19 | 0.4 (9) |
C1—C6—C7—C13 | −4.7 (7) | Cl1—C17—C18—C19 | −177.0 (4) |
C9—N1—C8—C7 | −0.7 (7) | C15—C14—C19—C18 | −0.8 (7) |
C9—N1—C8—S1 | 179.3 (3) | N2—C14—C19—C18 | 177.6 (4) |
C13—C7—C8—N1 | 2.3 (6) | C17—C18—C19—C14 | 0.5 (8) |
C6—C7—C8—N1 | −178.3 (4) | C13—N3—C20—O2 | −178.3 (3) |
C13—C7—C8—S1 | −177.6 (3) | C13—N3—C20—N2 | 1.9 (6) |
C6—C7—C8—S1 | 1.7 (4) | C21—O2—C20—N3 | −7.7 (5) |
C5—S1—C8—N1 | 178.6 (4) | C21—O2—C20—N2 | 172.2 (3) |
C5—S1—C8—C7 | −1.4 (3) | C12—N2—C20—N3 | −0.7 (6) |
C8—N1—C9—C10 | −0.7 (7) | C14—N2—C20—N3 | 178.3 (4) |
C8—N1—C9—C11 | −178.9 (4) | C12—N2—C20—O2 | 179.5 (3) |
N1—C9—C10—C13 | 0.4 (7) | C14—N2—C20—O2 | −1.5 (5) |
C11—C9—C10—C13 | 178.4 (5) | C20—O2—C21—C22 | 92.4 (4) |
N1—C9—C10—C12 | −179.9 (4) | C20—O2—C21—C26 | −92.6 (4) |
C11—C9—C10—C12 | −1.8 (7) | C26—C21—C22—C23 | 1.4 (6) |
C20—N2—C12—O1 | 179.8 (4) | O2—C21—C22—C23 | 176.4 (4) |
C14—N2—C12—O1 | 0.7 (6) | C21—C22—C23—C24 | −0.9 (7) |
C20—N2—C12—C10 | 0.5 (6) | C22—C23—C24—C25 | −0.5 (7) |
C14—N2—C12—C10 | −178.6 (4) | C22—C23—C24—Cl2 | −179.2 (3) |
C13—C10—C12—O1 | 179.3 (5) | C23—C24—C25—C26 | 1.5 (7) |
C9—C10—C12—O1 | −0.4 (8) | Cl2—C24—C25—C26 | −179.9 (3) |
C13—C10—C12—N2 | −1.6 (6) | C22—C21—C26—C25 | −0.5 (6) |
C9—C10—C12—N2 | 178.7 (4) | O2—C21—C26—C25 | −175.6 (4) |
C20—N3—C13—C10 | −3.0 (6) | C22—C21—C26—Cl3 | 179.4 (3) |
C20—N3—C13—C7 | 178.3 (3) | O2—C21—C26—Cl3 | 4.4 (5) |
C9—C10—C13—N3 | −177.3 (4) | C24—C25—C26—C21 | −0.9 (7) |
C12—C10—C13—N3 | 2.9 (6) | C24—C25—C26—Cl3 | 179.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C27—H27A···O1i | 0.97 | 2.44 | 3.23 (2) | 138 |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C26H18Cl3N3O2S·CH2Cl2 |
Mr | 627.77 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 292 |
a, b, c (Å) | 18.295 (6), 10.851 (4), 28.097 (9) |
V (Å3) | 5578 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.63 |
Crystal size (mm) | 0.20 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.885, 0.929 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29034, 5488, 3296 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.078, 0.234, 1.04 |
No. of reflections | 5488 |
No. of parameters | 372 |
No. of restraints | 41 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.52 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C27—H27A···O1i | 0.97 | 2.44 | 3.23 (2) | 138 |
Symmetry code: (i) −x+1, −y+1, −z. |
The pyridopyrimidine scaffold is a well known pharmacophore in drug design and it is associated with a wide range of biological properties. For example, many pyrido[4,3-d]pyrimidines have been described as inhibitors of tyrosine kinases of the epidermal growth factor receptor family (Bridges et al., 1997). An important synthetic route to pyrido[4,3-d]pyrimidine is the condensation reaction of 4-aminonicotinic acid and amines (Ismail & Wibberley, 1967). However, this method often require long reaction time. Recently, we have developed a new and facile regioselective annulation process, which proceeds smoothly under mild condition via a tandem aza-Wittig and cyclization reaction, to synthesize novel pyrido[4,3-d]pyrimidine derivates (Liu et al., 2006). In this paper, the crystal structure of the title compound is reported. The structure of the title compound was also characterized by 1H NMR, MS and elemental analysis.
The molecular structure of (1) is shown in Fig. 1. The C—S bond lengths in the thiophene ring [1.733 (5) and 1.735 (5) Å] are almost equal and long compared with the values observed in free thiophene (1.714 Å; Bonham & Momany, 1963). The C8—S1—C5 [91.7 (2)°] angle is comparable to that observed in free thiophene [92.2 (2)°]. The C8—N1—C9 angle of 116.9 (4)° is typical of a non-protonated ring system, being smaller than 120° (Ghosh & Simonsen, 1993). The central thienopyridine ring system is nearly planar and the dihedral angle between the thiophene and pyridine planes is 1.6 (2)°. The pyrimidinone ring forms a dihedral angle of 3.1 (2)° with the pyridine ring. The chloro- and dichloro-phenyl rings form dihedral angles of 75.2 (2) and 85.5 (2)°, respectively, with the pyrimidinone ring. The dihedral angle between the chlorophenyl rings is 69.7 (2)°. The cyclohexene ring adopts a half-chair conformation. There exists a C27—H27A—O1 hydrogen bond between the main molecule and the dichoromethane molecule.