Condensation of N-aryl-C-(ethoxycarbonyl)nitrilimines with 4-phenyl-1,2-dihydro-3H-1,5-benzodiazepine-2-thione lead to the title compounds, C25H21ClN4O2S, (IIIa), and C26H23N5O4S, (IIIb), respectively. Crystals of both compounds were obtained by evaporation of ethanol solutions at room temperature. In the structures of both compounds, a non-bonding interaction is observed between the S atom and the imino N atom. It is established that 1,3-dipolar cycloaddition occurs on the C=S double bond of the 1,5-benzodiazepine-2-thione.
Supporting information
CCDC references: 195635; 195636
A une solution de 1,5-benzodiazépine-2-thione, (I) (1.98 mmole), et de
N-arylhydrazono-a-bromoglyoxylate d'éthyle, (II) (1.98 mmole), dans
benzène anhydre (20 ml), on ajoute lentement et sous agitation une solution
de triéthylamine (0.5 ml) contenue dans benzène (2 ml). Après agitation
à température ambiante pendant 48 h, le mélange réactionnel est lavé
plusieurs fois à l'eau distillée. Ensuite, la phase organique séchée
sur sulfate de sodium est évaporée sous pression réduite pour éliminer
le solvant et l'excès de triéthylamine. Le résidu obtenu est purifié
par chromatographie sur gel de silice avec un gradient d'éluant
hexane-acétate d'éthyle. Le produit isolé, (III), est
recristallisé dans l'éthanol pour conduire aux composés étudiés
[p.f. 439–441 K pour (IIIa) et 435–437 K pour (IIIb).
Please provide brief details of constraints used for H atoms.
For both compounds, data collection: KappaCCD Reference Manual (Nonius, 1998); cell refinement: KappaCCD Reference Manual; data reduction: DENZO et SCALEPACK (Otwinoski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
(IIIa) Ethyl 5-[2-(2-aminophenylimino)-2-phenylethylidene]-
4-(4-chlorophenyl)-4,5-dihydro-1,3,4-thiadiazole-2-carboxylate
top
Crystal data top
C25H21ClN4O2S | F(000) = 992 |
Mr = 476.97 | Dx = 1.332 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 26069 reflections |
a = 9.9826 (1) Å | θ = 3.0–25.1° |
b = 9.5040 (2) Å | µ = 0.28 mm−1 |
c = 25.079 (1) Å | T = 293 K |
β = 90.667 (5)° | Prism, red |
V = 2379.3 (1) Å3 | 0.35 × 0.25 × 0.20 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 3903 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 25.1°, θmin = 3.0° |
ϕ scans | h = −3→11 |
26069 measured reflections | k = −9→11 |
4247 independent reflections | l = −29→30 |
Refinement top
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.23 | w = 1/[σ2(Fo2) + (0.067P)2 + 0.7595P] where P = (Fo2 + 2Fc2)/3 |
4247 reflections | (Δ/σ)max < 0.001 |
298 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
C25H21ClN4O2S | V = 2379.3 (1) Å3 |
Mr = 476.97 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.9826 (1) Å | µ = 0.28 mm−1 |
b = 9.5040 (2) Å | T = 293 K |
c = 25.079 (1) Å | 0.35 × 0.25 × 0.20 mm |
β = 90.667 (5)° | |
Data collection top
Nonius KappaCCD diffractometer | 3903 reflections with I > 2σ(I) |
26069 measured reflections | Rint = 0.039 |
4247 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.23 | Δρmax = 0.27 e Å−3 |
4247 reflections | Δρmin = −0.30 e Å−3 |
298 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.39057 (8) | 0.44576 (11) | 0.59178 (4) | 0.0919 (3) | |
S1 | 1.14515 (5) | 0.15588 (5) | 0.492347 (19) | 0.04240 (17) | |
O29 | 1.1594 (2) | 0.0109 (2) | 0.64135 (7) | 0.0748 (6) | |
O30 | 1.29502 (16) | −0.01495 (17) | 0.57121 (7) | 0.0552 (4) | |
N3 | 0.92569 (16) | 0.23524 (17) | 0.53462 (6) | 0.0395 (4) | |
N4 | 0.98853 (18) | 0.16191 (17) | 0.57447 (6) | 0.0418 (4) | |
N8 | 1.13385 (19) | 0.2502 (2) | 0.39102 (7) | 0.0505 (4) | |
N15 | 1.2142 (3) | 0.0176 (3) | 0.33324 (11) | 0.0855 (8) | |
H15A | 1.1303 | 0.0153 | 0.3471 | 0.103* | |
H15B | 1.2258 | −0.0560 | 0.3099 | 0.103* | |
C2 | 0.99095 (19) | 0.24284 (19) | 0.48607 (7) | 0.0370 (4) | |
C5 | 1.1025 (2) | 0.1164 (2) | 0.55829 (8) | 0.0413 (4) | |
C6 | 0.9427 (2) | 0.3049 (2) | 0.44103 (7) | 0.0417 (4) | |
H6 | 0.8555 | 0.3471 | 0.4420 | 0.050* | |
C7 | 1.0178 (2) | 0.3097 (2) | 0.39246 (7) | 0.0408 (4) | |
C9 | 1.2198 (2) | 0.2686 (3) | 0.34702 (8) | 0.0519 (5) | |
C10 | 1.2707 (3) | 0.3993 (3) | 0.33380 (10) | 0.0611 (6) | |
H10 | 1.2377 | 0.4817 | 0.3515 | 0.073* | |
C11 | 1.3678 (3) | 0.4127 (4) | 0.29511 (13) | 0.0800 (8) | |
H11 | 1.4063 | 0.5025 | 0.2868 | 0.096* | |
C12 | 1.4110 (3) | 0.2940 (4) | 0.26860 (13) | 0.0888 (10) | |
H12 | 1.4778 | 0.3011 | 0.2415 | 0.107* | |
C13 | 1.3591 (3) | 0.1647 (4) | 0.28033 (12) | 0.0782 (9) | |
H13 | 1.3883 | 0.0828 | 0.2614 | 0.094* | |
C14 | 1.2630 (3) | 0.1487 (3) | 0.31950 (9) | 0.0619 (7) | |
C16 | 0.9523 (2) | 0.3850 (2) | 0.34670 (7) | 0.0416 (4) | |
C17 | 0.9295 (3) | 0.3169 (3) | 0.29856 (9) | 0.0584 (6) | |
H17 | 0.9596 | 0.2218 | 0.2938 | 0.070* | |
C18 | 0.8637 (3) | 0.3882 (3) | 0.25742 (10) | 0.0735 (8) | |
H18 | 0.8464 | 0.3412 | 0.2241 | 0.088* | |
C19 | 0.8241 (3) | 0.5261 (3) | 0.26377 (11) | 0.0719 (8) | |
H19 | 0.7769 | 0.5742 | 0.2356 | 0.086* | |
C20 | 0.8500 (3) | 0.5936 (3) | 0.31084 (11) | 0.0679 (7) | |
H20 | 0.8255 | 0.6907 | 0.3148 | 0.081* | |
C21 | 0.9125 (2) | 0.5232 (2) | 0.35239 (9) | 0.0542 (5) | |
H21 | 0.9284 | 0.5701 | 0.3858 | 0.065* | |
C22 | 0.79537 (19) | 0.2877 (2) | 0.54588 (7) | 0.0388 (4) | |
C23 | 0.7605 (2) | 0.4244 (2) | 0.53387 (8) | 0.0442 (4) | |
H23 | 0.8227 | 0.4857 | 0.5164 | 0.053* | |
C24 | 0.6339 (2) | 0.4728 (2) | 0.54702 (9) | 0.0539 (5) | |
H24 | 0.6063 | 0.5669 | 0.5385 | 0.065* | |
C25 | 0.5470 (2) | 0.3849 (3) | 0.57253 (9) | 0.0566 (6) | |
C26 | 0.5822 (3) | 0.2496 (3) | 0.58504 (12) | 0.0681 (7) | |
H26 | 0.5192 | 0.1904 | 0.6030 | 0.082* | |
C27 | 0.7066 (2) | 0.1994 (3) | 0.57114 (11) | 0.0575 (6) | |
H27 | 0.7314 | 0.1042 | 0.5793 | 0.069* | |
C28 | 1.1870 (2) | 0.0327 (2) | 0.59589 (8) | 0.0479 (5) | |
C31 | 1.3844 (3) | −0.1040 (3) | 0.60327 (11) | 0.0650 (7) | |
H31A | 1.4225 | −0.0486 | 0.6317 | 0.078* | |
H31B | 1.3339 | −0.1802 | 0.6181 | 0.078* | |
C32 | 1.4901 (3) | −0.1541 (3) | 0.56716 (14) | 0.0840 (10) | |
H32A | 1.5521 | −0.2132 | 0.5863 | 0.101* | |
H32B | 1.5371 | −0.0753 | 0.5524 | 0.101* | |
H32C | 1.4485 | −0.2070 | 0.5389 | 0.101* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0518 (5) | 0.1405 (7) | 0.0840 (5) | 0.0379 (4) | 0.0215 (3) | 0.0085 (5) |
S1 | 0.0385 (3) | 0.0508 (3) | 0.0379 (3) | 0.01371 (18) | 0.00110 (18) | 0.00082 (18) |
O29 | 0.0809 (14) | 0.0970 (13) | 0.0464 (10) | 0.0325 (10) | −0.0028 (9) | 0.0179 (9) |
O30 | 0.0477 (10) | 0.0602 (9) | 0.0574 (9) | 0.0202 (7) | −0.0065 (7) | 0.0105 (7) |
N3 | 0.0370 (9) | 0.0478 (9) | 0.0336 (8) | 0.0116 (6) | 0.0012 (6) | 0.0053 (6) |
N4 | 0.0440 (10) | 0.0465 (9) | 0.0349 (8) | 0.0100 (6) | −0.0019 (6) | 0.0046 (6) |
N8 | 0.0495 (11) | 0.0693 (11) | 0.0327 (8) | 0.0191 (8) | 0.0027 (7) | 0.0021 (7) |
N15 | 0.125 (2) | 0.0682 (14) | 0.0641 (14) | 0.0287 (14) | 0.0220 (15) | 0.0048 (11) |
C2 | 0.0357 (10) | 0.0415 (9) | 0.0337 (9) | 0.0057 (7) | 0.0009 (7) | −0.0021 (7) |
C5 | 0.0421 (11) | 0.0435 (9) | 0.0383 (9) | 0.0080 (8) | −0.0030 (7) | 0.0015 (7) |
C6 | 0.0377 (11) | 0.0520 (10) | 0.0353 (9) | 0.0102 (8) | −0.0002 (7) | 0.0020 (7) |
C7 | 0.0412 (11) | 0.0492 (10) | 0.0321 (9) | 0.0068 (8) | −0.0028 (7) | −0.0010 (7) |
C9 | 0.0437 (13) | 0.0793 (15) | 0.0326 (9) | 0.0201 (10) | −0.0006 (8) | 0.0011 (9) |
C10 | 0.0550 (15) | 0.0804 (16) | 0.0480 (12) | 0.0034 (11) | 0.0062 (10) | −0.0039 (11) |
C11 | 0.069 (2) | 0.104 (2) | 0.0679 (17) | −0.0086 (15) | 0.0181 (14) | 0.0001 (15) |
C12 | 0.071 (2) | 0.129 (3) | 0.0670 (18) | 0.0141 (18) | 0.0329 (15) | 0.0000 (18) |
C13 | 0.079 (2) | 0.101 (2) | 0.0551 (15) | 0.0373 (17) | 0.0191 (14) | −0.0034 (14) |
C14 | 0.0674 (17) | 0.0786 (16) | 0.0397 (11) | 0.0298 (12) | 0.0051 (10) | 0.0033 (10) |
C16 | 0.0338 (11) | 0.0557 (11) | 0.0352 (9) | −0.0001 (8) | −0.0020 (7) | 0.0068 (8) |
C17 | 0.0711 (17) | 0.0609 (13) | 0.0428 (11) | −0.0149 (11) | −0.0138 (10) | 0.0036 (9) |
C18 | 0.0765 (19) | 0.100 (2) | 0.0436 (12) | −0.0312 (16) | −0.0210 (12) | 0.0106 (13) |
C19 | 0.0508 (16) | 0.101 (2) | 0.0638 (16) | 0.0008 (13) | −0.0078 (11) | 0.0373 (15) |
C20 | 0.0600 (17) | 0.0817 (17) | 0.0622 (15) | 0.0236 (12) | 0.0112 (12) | 0.0257 (13) |
C21 | 0.0524 (14) | 0.0645 (13) | 0.0459 (11) | 0.0170 (10) | 0.0068 (9) | 0.0066 (9) |
C22 | 0.0350 (11) | 0.0464 (10) | 0.0349 (8) | 0.0075 (7) | 0.0018 (7) | 0.0015 (7) |
C23 | 0.0431 (12) | 0.0453 (10) | 0.0442 (10) | 0.0081 (8) | 0.0060 (8) | −0.0004 (8) |
C24 | 0.0536 (14) | 0.0565 (12) | 0.0519 (12) | 0.0209 (10) | 0.0062 (9) | −0.0012 (9) |
C25 | 0.0386 (13) | 0.0819 (15) | 0.0494 (12) | 0.0156 (10) | 0.0066 (9) | −0.0017 (11) |
C26 | 0.0464 (15) | 0.0820 (17) | 0.0761 (17) | 0.0022 (11) | 0.0167 (12) | 0.0195 (13) |
C27 | 0.0475 (14) | 0.0564 (12) | 0.0691 (15) | 0.0073 (9) | 0.0109 (10) | 0.0170 (11) |
C28 | 0.0476 (13) | 0.0510 (11) | 0.0449 (11) | 0.0114 (9) | −0.0070 (9) | 0.0035 (8) |
C31 | 0.0615 (17) | 0.0611 (14) | 0.0720 (16) | 0.0258 (11) | −0.0212 (12) | 0.0053 (11) |
C32 | 0.073 (2) | 0.0857 (19) | 0.092 (2) | 0.0425 (15) | −0.0267 (17) | −0.0159 (16) |
Geometric parameters (Å, º) top
Cl1—C25 | 1.739 (2) | C13—H13 | 0.9590 |
S1—C2 | 1.7526 (19) | C16—C21 | 1.380 (3) |
S1—C5 | 1.753 (2) | C16—C17 | 1.386 (3) |
O29—C28 | 1.194 (3) | C17—C18 | 1.393 (4) |
O30—C28 | 1.329 (3) | C17—H17 | 0.9604 |
O30—C31 | 1.463 (2) | C18—C19 | 1.378 (5) |
N3—N4 | 1.365 (2) | C18—H18 | 0.9614 |
N3—C2 | 1.389 (2) | C19—C20 | 1.366 (4) |
N3—C22 | 1.425 (2) | C19—H19 | 0.9606 |
N4—C5 | 1.287 (3) | C20—C21 | 1.381 (3) |
N8—C7 | 1.290 (3) | C20—H20 | 0.9602 |
N8—C9 | 1.417 (3) | C21—H21 | 0.9604 |
N15—C14 | 1.383 (4) | C22—C23 | 1.377 (3) |
N15—H15A | 0.9112 | C22—C27 | 1.380 (3) |
N15—H15B | 0.9196 | C23—C24 | 1.388 (3) |
C2—C6 | 1.358 (3) | C23—H23 | 0.9608 |
C5—C28 | 1.488 (3) | C24—C25 | 1.369 (4) |
C6—C7 | 1.439 (3) | C24—H24 | 0.9591 |
C6—H6 | 0.9590 | C25—C26 | 1.368 (4) |
C7—C16 | 1.497 (3) | C26—C27 | 1.379 (4) |
C9—C10 | 1.384 (4) | C26—H26 | 0.9600 |
C9—C14 | 1.403 (3) | C27—H27 | 0.9595 |
C10—C11 | 1.385 (4) | C31—C32 | 1.478 (4) |
C10—H10 | 0.9604 | C31—H31A | 0.9609 |
C11—C12 | 1.381 (5) | C31—H31B | 0.9597 |
C11—H11 | 0.9599 | C32—H32A | 0.9605 |
C12—C13 | 1.367 (5) | C32—H32B | 0.9601 |
C12—H12 | 0.9599 | C32—H32C | 0.9592 |
C13—C14 | 1.390 (4) | | |
| | | |
C2—S1—C5 | 87.89 (9) | C19—C18—C17 | 120.7 (3) |
C28—O30—C31 | 115.71 (19) | C19—C18—H18 | 119.6 |
N4—N3—C2 | 116.86 (16) | C17—C18—H18 | 119.8 |
N4—N3—C22 | 116.52 (15) | C20—C19—C18 | 119.7 (2) |
C2—N3—C22 | 126.45 (15) | C20—C19—H19 | 119.9 |
C5—N4—N3 | 109.96 (16) | C18—C19—H19 | 120.4 |
C7—N8—C9 | 121.31 (17) | C19—C20—C21 | 120.2 (3) |
C14—N15—H15A | 116.4 | C19—C20—H20 | 119.7 |
C14—N15—H15B | 118.6 | C21—C20—H20 | 120.1 |
H15A—N15—H15B | 110.4 | C16—C21—C20 | 120.7 (2) |
C6—C2—N3 | 125.89 (18) | C16—C21—H21 | 119.1 |
C6—C2—S1 | 125.61 (15) | C20—C21—H21 | 120.1 |
N3—C2—S1 | 108.49 (13) | C23—C22—C27 | 120.82 (19) |
N4—C5—C28 | 118.45 (18) | C23—C22—N3 | 121.05 (18) |
N4—C5—S1 | 116.76 (14) | C27—C22—N3 | 118.08 (17) |
C28—C5—S1 | 124.78 (15) | C22—C23—C24 | 119.3 (2) |
C2—C6—C7 | 122.35 (18) | C22—C23—H23 | 120.6 |
C2—C6—H6 | 118.3 | C24—C23—H23 | 120.2 |
C7—C6—H6 | 119.4 | C25—C24—C23 | 119.5 (2) |
N8—C7—C6 | 119.12 (17) | C25—C24—H24 | 119.4 |
N8—C7—C16 | 124.96 (18) | C23—C24—H24 | 121.0 |
C6—C7—C16 | 115.92 (17) | C26—C25—C24 | 121.2 (2) |
C10—C9—C14 | 119.7 (2) | C26—C25—Cl1 | 118.5 (2) |
C10—C9—N8 | 121.7 (2) | C24—C25—Cl1 | 120.18 (19) |
C14—C9—N8 | 118.4 (2) | C25—C26—C27 | 119.8 (2) |
C9—C10—C11 | 120.8 (3) | C25—C26—H26 | 119.4 |
C9—C10—H10 | 119.5 | C27—C26—H26 | 120.8 |
C11—C10—H10 | 119.7 | C26—C27—C22 | 119.4 (2) |
C12—C11—C10 | 119.2 (3) | C26—C27—H27 | 120.2 |
C12—C11—H11 | 119.6 | C22—C27—H27 | 120.4 |
C10—C11—H11 | 121.2 | O29—C28—O30 | 125.65 (19) |
C13—C12—C11 | 120.6 (3) | O29—C28—C5 | 124.2 (2) |
C13—C12—H12 | 118.9 | O30—C28—C5 | 110.10 (18) |
C11—C12—H12 | 120.4 | O30—C31—C32 | 106.6 (2) |
C12—C13—C14 | 121.1 (3) | O30—C31—H31A | 108.9 |
C12—C13—H13 | 120.3 | C32—C31—H31A | 110.6 |
C14—C13—H13 | 118.5 | O30—C31—H31B | 109.2 |
N15—C14—C13 | 121.5 (2) | C32—C31—H31B | 112.1 |
N15—C14—C9 | 119.9 (2) | H31A—C31—H31B | 109.4 |
C13—C14—C9 | 118.5 (3) | C31—C32—H32A | 110.0 |
C21—C16—C17 | 119.35 (19) | C31—C32—H32B | 109.9 |
C21—C16—C7 | 119.96 (18) | H32A—C32—H32B | 109.5 |
C17—C16—C7 | 120.68 (19) | C31—C32—H32C | 108.4 |
C16—C17—C18 | 119.3 (2) | H32A—C32—H32C | 109.5 |
C16—C17—H17 | 120.0 | H32B—C32—H32C | 109.5 |
C18—C17—H17 | 120.8 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N15—H15A···N4i | 0.91 | 2.86 | 3.532 (3) | 132 |
N15—H15A···O29i | 0.91 | 2.92 | 3.801 (3) | 162 |
Symmetry code: (i) −x+2, −y, −z+1. |
(IIIb) Ethyl 5-{2-[2-(methylamino)phenylimino]-2-phenylethylidene}-
4-(4-nitrophenyl)-4,5-dihydro-1,3,4-thiadiazole-2-carboxylate
top
Crystal data top
C26H23N5O4S | Z = 2 |
Mr = 501.55 | F(000) = 524 |
Triclinic, P1 | Dx = 1.355 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7619 (2) Å | Cell parameters from 17984 reflections |
b = 10.7465 (3) Å | θ = 2.0–25.9° |
c = 12.1924 (2) Å | µ = 0.18 mm−1 |
α = 87.137 (2)° | T = 293 K |
β = 83.151 (2)° | Prism, red |
γ = 75.469 (1)° | 0.35 × 0.15 × 0.10 mm |
V = 1229.1 (1) Å3 | |
Data collection top
Nonius KappaCCD diffractometer | 4003 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 25.9°, θmin = 2.0° |
ϕ scans | h = −11→12 |
17984 measured reflections | k = −12→13 |
4642 independent reflections | l = −13→14 |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.1021P)2 + 0.2297P] where P = (Fo2 + 2Fc2)/3 |
4642 reflections | (Δ/σ)max < 0.001 |
325 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
Crystal data top
C26H23N5O4S | γ = 75.469 (1)° |
Mr = 501.55 | V = 1229.1 (1) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.7619 (2) Å | Mo Kα radiation |
b = 10.7465 (3) Å | µ = 0.18 mm−1 |
c = 12.1924 (2) Å | T = 293 K |
α = 87.137 (2)° | 0.35 × 0.15 × 0.10 mm |
β = 83.151 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 4003 reflections with I > 2σ(I) |
17984 measured reflections | Rint = 0.039 |
4642 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.36 e Å−3 |
4642 reflections | Δρmin = −0.55 e Å−3 |
325 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | −0.16164 (5) | 0.06197 (5) | 0.12082 (4) | 0.03578 (18) | |
O30 | 0.4718 (4) | 0.4284 (4) | 0.3144 (2) | 0.1291 (13) | |
O31 | 0.5504 (3) | 0.4262 (3) | 0.1427 (3) | 0.1181 (11) | |
O33 | −0.2123 (2) | 0.31727 (18) | −0.12886 (15) | 0.0634 (5) | |
O34 | −0.32142 (16) | 0.16124 (16) | −0.06770 (13) | 0.0465 (4) | |
N3 | 0.03640 (17) | 0.17858 (15) | 0.12328 (14) | 0.0334 (4) | |
N4 | −0.03416 (17) | 0.23641 (15) | 0.03665 (14) | 0.0351 (4) | |
N8 | −0.12750 (18) | −0.10683 (16) | 0.27964 (14) | 0.0376 (4) | |
N15 | −0.1320 (2) | −0.33740 (18) | 0.18938 (15) | 0.0474 (5) | |
H15 | −0.0634 | −0.2872 | 0.1713 | 0.057* | |
N29 | 0.4684 (3) | 0.4023 (3) | 0.2190 (2) | 0.0798 (8) | |
C2 | −0.00964 (19) | 0.07709 (17) | 0.17717 (16) | 0.0311 (4) | |
C5 | −0.1378 (2) | 0.18571 (18) | 0.02621 (16) | 0.0350 (4) | |
C6 | 0.0547 (2) | −0.00127 (17) | 0.25688 (16) | 0.0335 (4) | |
H6 | 0.1436 | 0.0085 | 0.2770 | 0.040* | |
C7 | −0.0081 (2) | −0.09875 (17) | 0.31167 (16) | 0.0314 (4) | |
C9 | −0.2175 (2) | −0.18124 (18) | 0.33199 (16) | 0.0333 (4) | |
C10 | −0.3123 (2) | −0.1363 (2) | 0.42328 (18) | 0.0438 (5) | |
H10 | −0.3047 | −0.0602 | 0.4575 | 0.053* | |
C11 | −0.4150 (2) | −0.1993 (2) | 0.4659 (2) | 0.0517 (6) | |
H11 | −0.4795 | −0.1666 | 0.5300 | 0.062* | |
C12 | −0.4247 (2) | −0.3082 (2) | 0.4149 (2) | 0.0482 (5) | |
H12 | −0.4988 | −0.3524 | 0.4419 | 0.058* | |
C13 | −0.3316 (2) | −0.35462 (19) | 0.32341 (18) | 0.0398 (5) | |
H13 | −0.3420 | −0.4306 | 0.2888 | 0.048* | |
C14 | −0.2259 (2) | −0.29352 (18) | 0.28045 (16) | 0.0339 (4) | |
C16 | −0.1072 (3) | −0.4663 (2) | 0.1511 (2) | 0.0659 (7) | |
H16A | −0.0414 | −0.4788 | 0.0871 | 0.079* | |
H16B | −0.1982 | −0.4803 | 0.1325 | 0.079* | |
H16C | −0.0761 | −0.5259 | 0.2087 | 0.079* | |
C17 | 0.06749 (19) | −0.17966 (17) | 0.39955 (16) | 0.0324 (4) | |
C18 | 0.0722 (2) | −0.31039 (19) | 0.41198 (19) | 0.0425 (5) | |
H18 | 0.0239 | −0.3494 | 0.3627 | 0.051* | |
C19 | 0.1431 (3) | −0.3829 (2) | 0.4948 (2) | 0.0516 (6) | |
H19 | 0.1434 | −0.4729 | 0.5023 | 0.062* | |
C20 | 0.2079 (2) | −0.3265 (2) | 0.5663 (2) | 0.0500 (6) | |
H20 | 0.2529 | −0.3771 | 0.6241 | 0.060* | |
C21 | 0.2045 (2) | −0.1979 (2) | 0.55457 (18) | 0.0434 (5) | |
H21 | 0.2482 | −0.1590 | 0.6049 | 0.052* | |
C22 | 0.1361 (2) | −0.12521 (19) | 0.47100 (17) | 0.0359 (4) | |
H22 | 0.1365 | −0.0361 | 0.4615 | 0.043* | |
C23 | 0.1488 (2) | 0.23049 (17) | 0.15018 (16) | 0.0321 (4) | |
C24 | 0.1614 (2) | 0.25275 (19) | 0.25859 (17) | 0.0394 (5) | |
H24 | 0.0988 | 0.2284 | 0.3167 | 0.047* | |
C25 | 0.2670 (3) | 0.3093 (2) | 0.2817 (2) | 0.0493 (5) | |
H25 | 0.2817 | 0.3269 | 0.3558 | 0.059* | |
C26 | 0.3557 (2) | 0.3426 (2) | 0.1946 (2) | 0.0498 (6) | |
C27 | 0.3433 (3) | 0.3225 (3) | 0.0868 (2) | 0.0538 (6) | |
H27 | 0.4107 | 0.3479 | 0.0299 | 0.065* | |
C28 | 0.2392 (2) | 0.2647 (2) | 0.06381 (18) | 0.0431 (5) | |
H28 | 0.2309 | 0.2491 | −0.0113 | 0.052* | |
C32 | −0.2279 (2) | 0.2318 (2) | −0.06558 (18) | 0.0412 (5) | |
C35 | −0.4081 (3) | 0.1871 (2) | −0.1601 (2) | 0.0503 (6) | |
H35A | −0.4761 | 0.2674 | −0.1489 | 0.060* | |
H35B | −0.3453 | 0.1927 | −0.2268 | 0.060* | |
C36 | −0.4759 (3) | 0.0777 (3) | −0.1633 (3) | 0.0648 (7) | |
H36A | −0.5333 | 0.0886 | −0.2230 | 0.078* | |
H36B | −0.5335 | 0.0739 | −0.0945 | 0.078* | |
H36C | −0.4027 | −0.0008 | −0.1723 | 0.078* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0361 (3) | 0.0390 (3) | 0.0388 (3) | −0.0189 (2) | −0.0128 (2) | 0.00708 (19) |
O30 | 0.165 (3) | 0.192 (3) | 0.093 (2) | −0.146 (3) | −0.057 (2) | 0.0243 (19) |
O31 | 0.0950 (18) | 0.177 (3) | 0.119 (2) | −0.106 (2) | 0.0000 (16) | −0.0086 (19) |
O33 | 0.0764 (12) | 0.0653 (11) | 0.0594 (12) | −0.0323 (9) | −0.0320 (9) | 0.0292 (9) |
O34 | 0.0421 (8) | 0.0608 (9) | 0.0429 (9) | −0.0194 (7) | −0.0205 (6) | 0.0104 (7) |
N3 | 0.0361 (8) | 0.0329 (8) | 0.0361 (9) | −0.0157 (7) | −0.0124 (6) | 0.0090 (6) |
N4 | 0.0380 (9) | 0.0356 (8) | 0.0348 (9) | −0.0128 (7) | −0.0114 (7) | 0.0077 (6) |
N8 | 0.0416 (9) | 0.0365 (8) | 0.0424 (10) | −0.0211 (7) | −0.0156 (7) | 0.0117 (7) |
N15 | 0.0600 (12) | 0.0468 (10) | 0.0406 (11) | −0.0255 (9) | 0.0008 (8) | −0.0024 (8) |
N29 | 0.0788 (17) | 0.098 (2) | 0.089 (2) | −0.0646 (16) | −0.0301 (15) | 0.0140 (15) |
C2 | 0.0326 (9) | 0.0295 (9) | 0.0344 (10) | −0.0131 (7) | −0.0056 (7) | 0.0019 (7) |
C5 | 0.0367 (10) | 0.0360 (10) | 0.0346 (11) | −0.0120 (8) | −0.0087 (8) | 0.0037 (7) |
C6 | 0.0332 (9) | 0.0320 (9) | 0.0397 (11) | −0.0142 (7) | −0.0106 (8) | 0.0054 (7) |
C7 | 0.0344 (9) | 0.0287 (9) | 0.0337 (10) | −0.0120 (7) | −0.0075 (7) | 0.0030 (7) |
C9 | 0.0346 (10) | 0.0352 (9) | 0.0355 (11) | −0.0160 (8) | −0.0140 (7) | 0.0097 (7) |
C10 | 0.0470 (12) | 0.0428 (11) | 0.0457 (13) | −0.0160 (9) | −0.0105 (9) | −0.0017 (9) |
C11 | 0.0447 (12) | 0.0611 (14) | 0.0485 (14) | −0.0161 (10) | 0.0028 (10) | 0.0013 (10) |
C12 | 0.0387 (11) | 0.0519 (13) | 0.0581 (15) | −0.0218 (10) | −0.0043 (9) | 0.0125 (10) |
C13 | 0.0428 (11) | 0.0328 (10) | 0.0503 (12) | −0.0185 (8) | −0.0170 (9) | 0.0113 (8) |
C14 | 0.0386 (10) | 0.0325 (9) | 0.0346 (11) | −0.0144 (8) | −0.0127 (8) | 0.0097 (7) |
C16 | 0.089 (2) | 0.0429 (13) | 0.0577 (17) | −0.0087 (13) | 0.0068 (14) | −0.0010 (11) |
C17 | 0.0310 (9) | 0.0322 (9) | 0.0349 (10) | −0.0101 (7) | −0.0055 (7) | 0.0054 (7) |
C18 | 0.0466 (12) | 0.0329 (10) | 0.0518 (13) | −0.0133 (8) | −0.0161 (9) | 0.0069 (8) |
C19 | 0.0563 (14) | 0.0346 (11) | 0.0660 (16) | −0.0132 (10) | −0.0192 (11) | 0.0176 (10) |
C20 | 0.0456 (12) | 0.0541 (13) | 0.0506 (14) | −0.0118 (10) | −0.0171 (10) | 0.0201 (10) |
C21 | 0.0389 (11) | 0.0528 (12) | 0.0419 (13) | −0.0150 (9) | −0.0132 (9) | 0.0055 (9) |
C22 | 0.0349 (10) | 0.0360 (10) | 0.0392 (11) | −0.0122 (8) | −0.0082 (8) | 0.0044 (7) |
C23 | 0.0318 (9) | 0.0286 (9) | 0.0394 (11) | −0.0124 (7) | −0.0100 (7) | 0.0054 (7) |
C24 | 0.0447 (11) | 0.0394 (10) | 0.0394 (12) | −0.0202 (9) | −0.0072 (8) | 0.0039 (8) |
C25 | 0.0599 (14) | 0.0522 (13) | 0.0467 (14) | −0.0290 (11) | −0.0181 (10) | 0.0019 (9) |
C26 | 0.0471 (13) | 0.0532 (13) | 0.0608 (15) | −0.0307 (11) | −0.0172 (10) | 0.0079 (10) |
C27 | 0.0447 (12) | 0.0702 (16) | 0.0555 (15) | −0.0335 (12) | −0.0040 (10) | 0.0084 (11) |
C28 | 0.0425 (11) | 0.0544 (12) | 0.0374 (12) | −0.0220 (9) | −0.0043 (8) | 0.0028 (9) |
C32 | 0.0412 (11) | 0.0447 (11) | 0.0400 (12) | −0.0121 (9) | −0.0127 (9) | 0.0059 (8) |
C35 | 0.0450 (12) | 0.0601 (14) | 0.0471 (14) | −0.0069 (10) | −0.0250 (10) | 0.0018 (10) |
C36 | 0.0545 (15) | 0.0682 (17) | 0.0769 (19) | −0.0116 (12) | −0.0358 (14) | −0.0011 (13) |
Geometric parameters (Å, º) top
S1—C2 | 1.7537 (18) | C13—H13 | 0.9708 |
S1—C5 | 1.7582 (19) | C16—H16A | 0.9419 |
O30—N29 | 1.216 (4) | C16—H16B | 0.9908 |
O31—N29 | 1.214 (4) | C16—H16C | 0.9508 |
O33—C32 | 1.198 (3) | C17—C22 | 1.391 (3) |
O34—C32 | 1.328 (3) | C17—C18 | 1.395 (3) |
O34—C35 | 1.463 (2) | C18—C19 | 1.387 (3) |
N3—N4 | 1.367 (2) | C18—H18 | 0.9752 |
N3—C2 | 1.388 (2) | C19—C20 | 1.379 (3) |
N3—C23 | 1.426 (2) | C19—H19 | 0.9663 |
N4—C5 | 1.285 (2) | C20—C21 | 1.375 (3) |
N8—C7 | 1.296 (2) | C20—H20 | 0.9492 |
N8—C9 | 1.410 (2) | C21—C22 | 1.384 (3) |
N15—C14 | 1.374 (3) | C21—H21 | 0.9542 |
N15—C16 | 1.437 (3) | C22—H22 | 0.9595 |
N15—H15 | 0.9601 | C23—C24 | 1.380 (3) |
N29—C26 | 1.471 (3) | C23—C28 | 1.387 (3) |
C2—C6 | 1.359 (3) | C24—C25 | 1.383 (3) |
C5—C32 | 1.494 (3) | C24—H24 | 0.9501 |
C6—C7 | 1.440 (2) | C25—C26 | 1.380 (3) |
C6—H6 | 0.9611 | C25—H25 | 0.9665 |
C7—C17 | 1.491 (2) | C26—C27 | 1.366 (4) |
C9—C10 | 1.383 (3) | C27—C28 | 1.379 (3) |
C9—C14 | 1.413 (3) | C27—H27 | 0.9751 |
C10—C11 | 1.384 (3) | C28—H28 | 0.9557 |
C10—H10 | 0.9591 | C35—C36 | 1.492 (4) |
C11—C12 | 1.381 (3) | C35—H35A | 0.9521 |
C11—H11 | 0.9642 | C35—H35B | 0.9672 |
C12—C13 | 1.380 (3) | C36—H36A | 0.9557 |
C12—H12 | 0.9784 | C36—H36B | 0.9576 |
C13—C14 | 1.395 (3) | C36—H36C | 0.9604 |
| | | |
C2—S1—C5 | 87.68 (8) | C22—C17—C7 | 119.99 (17) |
C32—O34—C35 | 116.13 (17) | C18—C17—C7 | 121.45 (17) |
N4—N3—C2 | 117.05 (14) | C19—C18—C17 | 120.0 (2) |
N4—N3—C23 | 116.34 (14) | C19—C18—H18 | 120.7 |
C2—N3—C23 | 126.60 (15) | C17—C18—H18 | 119.2 |
C5—N4—N3 | 109.68 (15) | C20—C19—C18 | 120.5 (2) |
C7—N8—C9 | 125.54 (16) | C20—C19—H19 | 121.2 |
C14—N15—C16 | 122.14 (19) | C18—C19—H19 | 118.3 |
C14—N15—H15 | 112.8 | C21—C20—C19 | 120.01 (19) |
C16—N15—H15 | 121.6 | C21—C20—H20 | 120.8 |
O31—N29—O30 | 123.5 (3) | C19—C20—H20 | 119.2 |
O31—N29—C26 | 118.4 (3) | C20—C21—C22 | 119.9 (2) |
O30—N29—C26 | 118.1 (3) | C20—C21—H21 | 119.7 |
C6—C2—N3 | 126.21 (16) | C22—C21—H21 | 120.4 |
C6—C2—S1 | 125.30 (14) | C21—C22—C17 | 120.98 (18) |
N3—C2—S1 | 108.43 (13) | C21—C22—H22 | 119.8 |
N4—C5—C32 | 119.09 (17) | C17—C22—H22 | 119.2 |
N4—C5—S1 | 116.95 (14) | C24—C23—C28 | 121.36 (18) |
C32—C5—S1 | 123.94 (14) | C24—C23—N3 | 120.63 (17) |
C2—C6—C7 | 121.09 (17) | C28—C23—N3 | 117.90 (17) |
C2—C6—H6 | 119.4 | C23—C24—C25 | 119.34 (19) |
C7—C6—H6 | 119.5 | C23—C24—H24 | 120.2 |
N8—C7—C6 | 115.97 (16) | C25—C24—H24 | 120.5 |
N8—C7—C17 | 126.00 (16) | C26—C25—C24 | 118.4 (2) |
C6—C7—C17 | 118.03 (16) | C26—C25—H25 | 118.3 |
C10—C9—N8 | 120.86 (18) | C24—C25—H25 | 123.3 |
C10—C9—C14 | 119.45 (17) | C27—C26—C25 | 122.89 (19) |
N8—C9—C14 | 118.98 (18) | C27—C26—N29 | 118.7 (2) |
C11—C10—C9 | 121.4 (2) | C25—C26—N29 | 118.5 (2) |
C11—C10—H10 | 120.2 | C26—C27—C28 | 118.8 (2) |
C9—C10—H10 | 118.3 | C26—C27—H27 | 118.0 |
C12—C11—C10 | 119.3 (2) | C28—C27—H27 | 123.2 |
C12—C11—H11 | 120.7 | C27—C28—C23 | 119.3 (2) |
C10—C11—H11 | 120.0 | C27—C28—H28 | 119.2 |
C11—C12—C13 | 120.3 (2) | C23—C28—H28 | 121.5 |
C11—C12—H12 | 120.6 | O33—C32—O34 | 126.38 (19) |
C13—C12—H12 | 119.0 | O33—C32—C5 | 123.62 (19) |
C12—C13—C14 | 121.18 (19) | O34—C32—C5 | 109.96 (16) |
C12—C13—H13 | 118.3 | O34—C35—C36 | 107.01 (19) |
C14—C13—H13 | 120.5 | O34—C35—H35A | 108.7 |
N15—C14—C13 | 122.45 (18) | C36—C35—H35A | 112.6 |
N15—C14—C9 | 119.22 (17) | O34—C35—H35B | 107.6 |
C13—C14—C9 | 118.32 (19) | C36—C35—H35B | 111.4 |
N15—C16—H16A | 110.4 | H35A—C35—H35B | 109.3 |
N15—C16—H16B | 108.9 | C35—C36—H36A | 111.0 |
H16A—C16—H16B | 108.4 | C35—C36—H36B | 108.2 |
N15—C16—H16C | 109.6 | H36A—C36—H36B | 109.9 |
H16A—C16—H16C | 111.9 | C35—C36—H36C | 109.0 |
H16B—C16—H16C | 107.4 | H36A—C36—H36C | 109.4 |
C22—C17—C18 | 118.56 (18) | H36B—C36—H36C | 109.3 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N15—H15···O33i | 0.96 | 2.62 | 3.413 (5) | 140 |
N15—H15···N4i | 0.96 | 2.68 | 3.305 (6) | 123 |
Symmetry code: (i) −x, −y, −z. |
Experimental details
| (IIIa) | (IIIb) |
Crystal data |
Chemical formula | C25H21ClN4O2S | C26H23N5O4S |
Mr | 476.97 | 501.55 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 9.9826 (1), 9.5040 (2), 25.079 (1) | 9.7619 (2), 10.7465 (3), 12.1924 (2) |
α, β, γ (°) | 90, 90.667 (5), 90 | 87.137 (2), 83.151 (2), 75.469 (1) |
V (Å3) | 2379.3 (1) | 1229.1 (1) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.28 | 0.18 |
Crystal size (mm) | 0.35 × 0.25 × 0.20 | 0.35 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26069, 4247, 3903 | 17984, 4642, 4003 |
Rint | 0.039 | 0.039 |
(sin θ/λ)max (Å−1) | 0.597 | 0.614 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.145, 1.23 | 0.043, 0.163, 1.17 |
No. of reflections | 4247 | 4642 |
No. of parameters | 298 | 325 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.30 | 0.36, −0.55 |
Selected geometric parameters (Å, º) for (IIIa) topS1—C2 | 1.7526 (19) | N8—C7 | 1.290 (3) |
S1—C5 | 1.753 (2) | N8—C9 | 1.417 (3) |
N3—N4 | 1.365 (2) | C2—C6 | 1.358 (3) |
N3—C2 | 1.389 (2) | C6—C7 | 1.439 (3) |
N4—C5 | 1.287 (3) | | |
| | | |
C2—S1—C5 | 87.89 (9) | N3—C2—S1 | 108.49 (13) |
N4—N3—C2 | 116.86 (16) | N4—C5—S1 | 116.76 (14) |
C5—N4—N3 | 109.96 (16) | C2—C6—C7 | 122.35 (18) |
C7—N8—C9 | 121.31 (17) | N8—C7—C6 | 119.12 (17) |
Hydrogen-bond geometry (Å, º) for (IIIa) top
D—H···A | D—H | H···A | D···A | D—H···A |
N15—H15A···N4i | 0.91 | 2.86 | 3.532 (3) | 132 |
N15—H15A···O29i | 0.91 | 2.92 | 3.801 (3) | 162 |
Symmetry code: (i) −x+2, −y, −z+1. |
Selected geometric parameters (Å, º) for (IIIb) topS1—C2 | 1.7537 (18) | N8—C7 | 1.296 (2) |
S1—C5 | 1.7582 (19) | N8—C9 | 1.410 (2) |
N3—N4 | 1.367 (2) | C2—C6 | 1.359 (3) |
N3—C2 | 1.388 (2) | C6—C7 | 1.440 (2) |
N4—C5 | 1.285 (2) | | |
| | | |
C2—S1—C5 | 87.68 (8) | N3—C2—S1 | 108.43 (13) |
N4—N3—C2 | 117.05 (14) | N4—C5—S1 | 116.95 (14) |
C5—N4—N3 | 109.68 (15) | C2—C6—C7 | 121.09 (17) |
C7—N8—C9 | 125.54 (16) | N8—C7—C6 | 115.97 (16) |
Hydrogen-bond geometry (Å, º) for (IIIb) top
D—H···A | D—H | H···A | D···A | D—H···A |
N15—H15···O33i | 0.96 | 2.62 | 3.413 (5) | 140 |
N15—H15···N4i | 0.96 | 2.68 | 3.305 (6) | 123 |
Symmetry code: (i) −x, −y, −z. |
Depuis des années, chimistes et pharmacologues (Gaignault & Bidet, 1985a,b; Sternbach, 1978) accordent une grande importance à la série des benzodiazépines dont de nombreux dérivés présentent des activités tranquillisantes, hypnotiques et antiépileptiques. A la suite du diazépam, principe actif du Valium qui est utilisé en thérapeutique depuis 1963, un grand nombre de molécules actives ont été synthétisées. Récemment, on a vu apparaître sur le marché des tranquillisants de nouveaux dérivés présentant un cycle triazole accolé au cycle diazépinique qui sont aussi des hypnotiques. De même, il a été montré que l'introduction d'un nouvel hétérocycle pentagonal sur les différentes positions du cycle diazépinique accroît notablement l'activité biologique (Hester et al., 1971; Peet & Sunder, 1977).
Dans ce cadre, notre équipe de recherche (Baouid et al., 1994; Chiaroni et al., 1995; Benelbaghdadi et al., 1997; Essaber et al., 1998; Aatif et al., 2000; El Hazazi et al., 2000) s'est intéressée à la synthèse des systèmes hétérocycliques ayant des structures similaires à celles des molécules biologiquement actives construites à partir des diazépines et des benzodiazépines. Poursuivant cet axe de recherche, nous avons effectué des réactions de cycloaddition dipolaire-1,3 sur des 1,5-benzodiazépine-2-thiones, (I) (Cortès et al., 1991; Nardi et al., 1973), avec les N-aryl-C-éthoxycarbonylnitrilimines générées in situ à partir de leurs précurseurs correspondants, (II) (Sharp & Hamilton, 1946), en présence de la triéthylamine et à température ambiante pendant 48 h. Notons que les deux 1,5-benzodiazépines, (Ia) et (Ib), possèdent deux sites dipolarophiles différents carbone-azote et carbone-soufre pouvant intervenir dans des réactions de cycloaddition dipolaire-1,3. Par conséquent, il sera possible d'examiner la péri et la régiosélectivité de ces réactions. \sch
Après traitement et purification sur gel de silice du mélange réactionnel, les structures des produits obtenus, (IIIa) et (IIIb), ont été étudiées par spectroscopie de masse et RMN 1H et 13C. La spectroscopie de masse nous indique que ceux-ci résultent d'une monocondensation du dipôle sur l'une des deux doubles liaisons C═N ou C═S. Cependant, les analyses spectrales de RMN 1H et 13C ne permettent pas d'élucider leurs structures.
L'étude cristallographique des monocristaux nous a permis de déterminer sans ambiguité les structures des composés (IIIa) et (IIIb) (figures 1 e t 3) compatibles avec les données spectrales de RMN 1H et 13C. Ces structures résultent d'une monocondensation du dipôle sur le site dipolarophile carbone-soufre conduisant à des monocycloadduits spiraniques instables qui se réarrangent pour aboutir aux produits ouverts (IIIa) et (IIIb) (schéma) avec de bons rendements. Cela montre que ces réactions sont totalement péri et régiosélectives puisque seul le site dipolarophile C═S est affecté par ce type de dipôle-1,3 quelque soit la quantité du dipôle utilisée et que le sens de l'addition est unique.
Les structures des composés (IIIa) et (IIIb) sont semblables. Dans les deux cas, le cycle thiadiazole porte trois substituants: (i) un bras éthylcarboxylate, (ii) un chlorophényle [(IIIa)] ou nitrophényle [(IIIb)], et (iii) un fragment aminophénylimino-phényléthylidène [(IIIa)] ou (méthylamino)phénylimino-nitrophényl [(IIIb)].
Le bras éthylcarboxylate et le fragment C2/C6/C7/N8 qui porte les deux doubles liaisons C2═C6 et C7═N8 (tableaux 1 e t 3) sont coplanaires avec le plan du cycle thiadiazole. Ce dernier fait un angle dièdre de 47,1(3)° avec le chlorophényle en (IIIa) et de 42,9(4)° avec le nitrophényle en (IIIb). Dans la structure (IIIa), l'angle dièdre entre cycle phényle C16—C21 et l'aminophényle C9—C14/N15 est 68,8(3)°; cet angle, entre C17—C22 et le (méthylamino)phényl C9—C14/N15/C16, est 78,8(3)° dans la structure (IIIb).
Dans les deux structures, la conformation du fragment S1/C2/C6/C7/N8 entraîne une interaction de non-liaison entre le soufre S1 et l'azote N8; la distance S1—N8 est égale à 2.696 (3) Å e t 2.579 (2) Å dans (IIIa) et (IIIb) respectivement, contre 2,558 (3) e t 2,601 (2) Å pour les distances intracycliques S1—N3 et S1—N4.
On notera que, dans les deux structures, l'atome d'azote N15 établit deux liasons hydrogène longues (tableaux 2 e t 4) avec l'atome d'azote N4 et l'atome d'oxygène O29(O33) de la molécule voisine obtenue par inversion du centre de symétrie. Il s'établit ainsi dans ces structures des dimères centrosymétriques liés par liaisons hydrogène (figures 2 e t 4). Cette interaction est nettement plus faible dans (IIIa) que dans (IIIb).
Tableau 1. Distances et angles de laisons (Å, °) pour (IIIa). Tableau 2. Liaisons hydrog`ene (Å, °) pour (IIIa). Tableau 3. Distances et angles de laisons (Å, °) pour (IIIb). Tableau 4. Liaisons hydrog`ene (Å, °) pour (IIIb).