The three title quinoxaline derivatives, (E)-2-(4-methylbenzylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline, C30H28N2O4S2, (II), (E)-2-(4-methoxybenzylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline, C30H28N2O5S2, (III), and (E)-2-(3-chlorobenzylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline, C29H25ClN2O4S2, (IV), were synthesized by palladium-catalyzed hetero-annulation. The E configuration of the exocyclic double bond in the three compounds has been established by the present X-ray study. The saturated part of the quinoxaline moiety in all three compounds assumes a distorted chair conformation. The numerical descriptors indicate a high degree of isostructurality between compounds (II) and (III), but no isostructurality with compound (IV).
Supporting information
CCDC references: 169955; 169956; 169957
The compounds (II), (III) and (IV) were synthesized in the following way. A
mixture of aryl iodide [4-methyliodobenzene for (II), 4-methoxyiodobenzene for
(III) and 3-chloroiodobenzene for (IV)] (1.15 mmol), palladium(II) acetate (5 mol%), anhydrous potassium carbonate (4.40 mmol) and tetrabutylammonium
bromide (4.40 mmol) was stirred in 10 ml of dimethylformamide(DMF) for half an
hour. The acetylenic compound,
N-(prop-2-ynyl)-N,N'-1,2-phenylene-di-p-tosylamide (0.88 mmol) was added to it and the mixture was further stirred
for 24 h at room temperature. After usual workup, the crude product purified
by column chromatography through silica gel using chloroform as eluant yielded
the title compounds (II), (III) and (IV). Single crystals of (II), (III) and
(IV) suitable for X-ray analyses were obtained from chloroform/light petroleum
(333–353 K) mixture (1:1). Compound (II): m.p. 428 (1) K, analysis found: C
66.43, H 5.23, N 4.87%; calculated for C30H28N2S2O4: C 66.17, H
5.14, N 5.14%. Compound (III): m.p. 425 (1) K, analysis found: C 64.04, H 5.06,
N 4.88%; calculated for C30H28N2S2O5: C 64.28, H 5.14, N 5.10%.
Compound (IV): m.p. 418 (1) K, analysis found C 61.94, N 4.36, N 4.78%;
calculated for C29H25N2S2O4Cl: C 61.65, H 4.42, N 4.46%.
For all compounds, data collection: XSCANS (Siemens, 1995); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: MULTAN 88 (Debaerdemaeker et al., 1988); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: SHELXL97 and PARST 95 (Nardelli, 1995).
(II) 2-[(4-methylphenyl)methylidene]-1,4-di-
p-tosyl-1,2,3,4-tetrahydroquinoxaline
top
Crystal data top
C30H28N2O4S2 | Dx = 1.290 Mg m−3 |
Mr = 544.66 | Melting point: 428(1) K K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.559 (4) Å | Cell parameters from 37 reflections |
b = 11.658 (4) Å | θ = 1.9–16.3° |
c = 23.169 (7) Å | µ = 0.23 mm−1 |
β = 100.54 (3)° | T = 293 K |
V = 2803.9 (17) Å3 | Block, colourless |
Z = 4 | 0.64 × 0.52 × 0.48 mm |
F(000) = 1144 | |
Data collection top
Siemens P4 diffractometer | 3664 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −1→12 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −1→13 |
Tmin = 0.866, Tmax = 0.896 | l = −27→27 |
6386 measured reflections | 3 standard reflections every 97 reflections |
4923 independent reflections | intensity decay: <2% |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0604P)2 + 0.6663P] where P = (Fo2 + 2Fc2)/3 |
4923 reflections | (Δ/σ)max = 0.003 |
346 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
C30H28N2O4S2 | V = 2803.9 (17) Å3 |
Mr = 544.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.559 (4) Å | µ = 0.23 mm−1 |
b = 11.658 (4) Å | T = 293 K |
c = 23.169 (7) Å | 0.64 × 0.52 × 0.48 mm |
β = 100.54 (3)° | |
Data collection top
Siemens P4 diffractometer | 3664 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.027 |
Tmin = 0.866, Tmax = 0.896 | 3 standard reflections every 97 reflections |
6386 measured reflections | intensity decay: <2% |
4923 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.21 e Å−3 |
4923 reflections | Δρmin = −0.31 e Å−3 |
346 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.30086 (6) | 0.25747 (5) | 0.15874 (4) | 0.0788 (2) | |
N1 | 0.14136 (17) | 0.23239 (15) | 0.15816 (9) | 0.0638 (5) | |
O1 | 0.30516 (18) | 0.33353 (16) | 0.11065 (12) | 0.1101 (8) | |
O2 | 0.35635 (19) | 0.2907 (2) | 0.21676 (11) | 0.1189 (9) | |
S2 | −0.18201 (5) | 0.01590 (5) | 0.11171 (3) | 0.06174 (19) | |
N2 | −0.02264 (16) | 0.03468 (14) | 0.13007 (8) | 0.0548 (4) | |
O3 | −0.21918 (16) | −0.05499 (16) | 0.15587 (9) | 0.0875 (6) | |
O4 | −0.20392 (16) | −0.02169 (14) | 0.05199 (8) | 0.0783 (5) | |
C1 | 0.1090 (2) | 0.1597 (2) | 0.20364 (10) | 0.0628 (6) | |
C2 | 0.1501 (3) | 0.1889 (3) | 0.26257 (13) | 0.0868 (9) | |
H2 | 0.1956 | 0.2566 | 0.2722 | 0.104* | |
C3 | 0.1239 (3) | 0.1186 (4) | 0.30619 (14) | 0.1105 (12) | |
H3 | 0.1504 | 0.1396 | 0.3453 | 0.133* | |
C4 | 0.0584 (3) | 0.0169 (4) | 0.29266 (14) | 0.1076 (11) | |
H4 | 0.0454 | −0.0325 | 0.3225 | 0.129* | |
C5 | 0.0122 (3) | −0.0115 (3) | 0.23484 (12) | 0.0822 (8) | |
H5 | −0.0328 | −0.0797 | 0.2259 | 0.099* | |
C6 | 0.0326 (2) | 0.0615 (2) | 0.18956 (10) | 0.0593 (5) | |
C7 | 0.0387 (2) | 0.09056 (17) | 0.08535 (10) | 0.0561 (5) | |
H7A | −0.0179 | 0.0853 | 0.0474 | 0.067* | |
H7B | 0.1183 | 0.0510 | 0.0827 | 0.067* | |
C8 | 0.06717 (19) | 0.21462 (17) | 0.10031 (10) | 0.0557 (5) | |
C9 | 0.0305 (2) | 0.30615 (18) | 0.06680 (11) | 0.0638 (6) | |
H9 | 0.0497 | 0.3769 | 0.0848 | 0.077* | |
C10 | −0.0360 (2) | 0.31014 (18) | 0.00546 (11) | 0.0622 (6) | |
C11 | −0.0157 (3) | 0.2325 (2) | −0.03727 (12) | 0.0813 (8) | |
H11 | 0.0436 | 0.1735 | −0.0274 | 0.098* | |
C12 | −0.0820 (4) | 0.2414 (3) | −0.09396 (13) | 0.0945 (9) | |
H12 | −0.0670 | 0.1878 | −0.1217 | 0.113* | |
C13 | −0.1707 (3) | 0.3282 (3) | −0.11085 (12) | 0.0834 (8) | |
C14 | −0.1890 (3) | 0.4070 (2) | −0.06887 (13) | 0.0768 (7) | |
H14 | −0.2474 | 0.4666 | −0.0791 | 0.092* | |
C15 | −0.1227 (2) | 0.39927 (19) | −0.01235 (12) | 0.0686 (6) | |
H15 | −0.1357 | 0.4547 | 0.0148 | 0.082* | |
C16 | −0.2420 (4) | 0.3373 (4) | −0.17354 (13) | 0.1192 (12) | |
H16A | −0.1909 | 0.3037 | −0.1994 | 0.179* | |
H16B | −0.2577 | 0.4165 | −0.1836 | 0.179* | |
H16C | −0.3226 | 0.2973 | −0.1774 | 0.179* | |
C17 | 0.36745 (19) | 0.12593 (19) | 0.14356 (10) | 0.0576 (5) | |
C18 | 0.4110 (2) | 0.0497 (2) | 0.18827 (11) | 0.0711 (6) | |
H18 | 0.4082 | 0.0689 | 0.2270 | 0.085* | |
C19 | 0.4583 (3) | −0.0543 (2) | 0.17511 (13) | 0.0787 (7) | |
H19 | 0.4873 | −0.1056 | 0.2054 | 0.094* | |
C20 | 0.4644 (2) | −0.0855 (2) | 0.11845 (13) | 0.0708 (7) | |
C21 | 0.4215 (2) | −0.0086 (2) | 0.07457 (12) | 0.0749 (7) | |
H21 | 0.4251 | −0.0280 | 0.0360 | 0.090* | |
C22 | 0.3731 (2) | 0.0970 (2) | 0.08624 (11) | 0.0686 (6) | |
H22 | 0.3446 | 0.1483 | 0.0559 | 0.082* | |
C23 | 0.5167 (3) | −0.2009 (3) | 0.10473 (18) | 0.1132 (12) | |
H23A | 0.5571 | −0.2373 | 0.1406 | 0.170* | |
H23B | 0.5789 | −0.1906 | 0.0797 | 0.170* | |
H23C | 0.4475 | −0.2481 | 0.0852 | 0.170* | |
C24 | −0.25481 (19) | 0.15097 (19) | 0.11401 (10) | 0.0572 (5) | |
C25 | −0.2946 (2) | 0.2117 (2) | 0.06328 (11) | 0.0696 (6) | |
H25 | −0.2838 | 0.1819 | 0.0273 | 0.084* | |
C26 | −0.3511 (2) | 0.3180 (2) | 0.06639 (14) | 0.0798 (7) | |
H26 | −0.3788 | 0.3589 | 0.0319 | 0.096* | |
C27 | −0.3675 (2) | 0.3649 (2) | 0.11888 (16) | 0.0812 (8) | |
C28 | −0.3270 (3) | 0.3020 (3) | 0.16894 (15) | 0.0987 (10) | |
H28 | −0.3367 | 0.3323 | 0.2050 | 0.118* | |
C29 | −0.2722 (3) | 0.1950 (3) | 0.16707 (12) | 0.0840 (8) | |
H29 | −0.2473 | 0.1530 | 0.2014 | 0.101* | |
C30 | −0.4278 (3) | 0.4826 (2) | 0.1217 (2) | 0.1225 (14) | |
H30A | −0.4716 | 0.5044 | 0.0832 | 0.184* | |
H30B | −0.3617 | 0.5376 | 0.1357 | 0.184* | |
H30C | −0.4883 | 0.4802 | 0.1480 | 0.184* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0496 (3) | 0.0506 (3) | 0.1297 (6) | −0.0030 (3) | −0.0005 (3) | −0.0133 (4) |
N1 | 0.0488 (10) | 0.0500 (10) | 0.0879 (13) | 0.0041 (8) | 0.0004 (9) | −0.0115 (10) |
O1 | 0.0652 (11) | 0.0557 (10) | 0.208 (2) | −0.0022 (8) | 0.0202 (13) | 0.0383 (13) |
O2 | 0.0637 (11) | 0.1138 (16) | 0.167 (2) | −0.0072 (11) | −0.0120 (12) | −0.0788 (16) |
S2 | 0.0455 (3) | 0.0496 (3) | 0.0859 (4) | −0.0014 (2) | 0.0009 (3) | 0.0042 (3) |
N2 | 0.0453 (9) | 0.0484 (9) | 0.0682 (11) | 0.0009 (7) | 0.0037 (8) | 0.0032 (8) |
O3 | 0.0571 (10) | 0.0759 (11) | 0.1266 (15) | −0.0089 (8) | 0.0090 (10) | 0.0376 (11) |
O4 | 0.0651 (10) | 0.0660 (10) | 0.0942 (12) | 0.0022 (8) | −0.0107 (9) | −0.0255 (9) |
C1 | 0.0485 (12) | 0.0615 (13) | 0.0738 (15) | 0.0158 (10) | −0.0007 (10) | −0.0098 (12) |
C2 | 0.0697 (16) | 0.097 (2) | 0.0852 (19) | 0.0249 (15) | −0.0079 (14) | −0.0256 (17) |
C3 | 0.094 (2) | 0.161 (4) | 0.0707 (19) | 0.041 (2) | −0.0014 (17) | −0.011 (2) |
C4 | 0.087 (2) | 0.158 (4) | 0.077 (2) | 0.022 (2) | 0.0107 (16) | 0.024 (2) |
C5 | 0.0634 (15) | 0.099 (2) | 0.0811 (18) | 0.0086 (14) | 0.0062 (13) | 0.0202 (16) |
C6 | 0.0448 (11) | 0.0621 (13) | 0.0689 (14) | 0.0130 (10) | 0.0053 (10) | 0.0018 (11) |
C7 | 0.0511 (11) | 0.0451 (11) | 0.0709 (13) | 0.0002 (9) | 0.0081 (10) | −0.0016 (10) |
C8 | 0.0457 (11) | 0.0456 (11) | 0.0746 (14) | 0.0012 (9) | 0.0082 (10) | −0.0034 (10) |
C9 | 0.0569 (13) | 0.0430 (11) | 0.0928 (17) | 0.0030 (10) | 0.0173 (12) | 0.0004 (11) |
C10 | 0.0630 (13) | 0.0457 (11) | 0.0811 (15) | 0.0022 (10) | 0.0216 (12) | 0.0091 (11) |
C11 | 0.103 (2) | 0.0639 (15) | 0.0847 (18) | 0.0247 (14) | 0.0369 (16) | 0.0159 (14) |
C12 | 0.136 (3) | 0.0761 (18) | 0.0794 (19) | 0.0126 (18) | 0.0405 (18) | 0.0097 (15) |
C13 | 0.096 (2) | 0.0749 (17) | 0.0808 (17) | −0.0080 (15) | 0.0207 (15) | 0.0211 (15) |
C14 | 0.0700 (15) | 0.0600 (15) | 0.100 (2) | 0.0043 (12) | 0.0138 (14) | 0.0225 (14) |
C15 | 0.0670 (14) | 0.0452 (12) | 0.0950 (18) | 0.0015 (11) | 0.0187 (13) | 0.0066 (12) |
C16 | 0.135 (3) | 0.134 (3) | 0.084 (2) | −0.016 (2) | 0.008 (2) | 0.026 (2) |
C17 | 0.0415 (11) | 0.0552 (12) | 0.0718 (14) | −0.0002 (9) | −0.0013 (10) | 0.0017 (11) |
C18 | 0.0680 (15) | 0.0767 (16) | 0.0631 (14) | 0.0133 (13) | −0.0022 (11) | 0.0047 (12) |
C19 | 0.0709 (16) | 0.0693 (16) | 0.0904 (19) | 0.0158 (13) | 0.0003 (13) | 0.0224 (14) |
C20 | 0.0464 (12) | 0.0608 (14) | 0.104 (2) | −0.0007 (11) | 0.0095 (12) | −0.0074 (14) |
C21 | 0.0590 (14) | 0.0906 (19) | 0.0753 (16) | 0.0020 (13) | 0.0126 (12) | −0.0143 (15) |
C22 | 0.0563 (13) | 0.0786 (16) | 0.0684 (15) | 0.0013 (12) | 0.0046 (11) | 0.0167 (13) |
C23 | 0.0759 (18) | 0.0706 (18) | 0.192 (4) | 0.0041 (15) | 0.022 (2) | −0.032 (2) |
C24 | 0.0405 (11) | 0.0578 (12) | 0.0713 (14) | 0.0021 (9) | 0.0053 (10) | 0.0020 (11) |
C25 | 0.0626 (14) | 0.0661 (14) | 0.0788 (16) | 0.0094 (12) | 0.0092 (12) | 0.0049 (13) |
C26 | 0.0631 (15) | 0.0665 (16) | 0.108 (2) | 0.0090 (12) | 0.0105 (14) | 0.0177 (15) |
C27 | 0.0462 (13) | 0.0610 (15) | 0.136 (3) | 0.0024 (11) | 0.0147 (14) | −0.0119 (17) |
C28 | 0.088 (2) | 0.103 (2) | 0.105 (2) | 0.0233 (18) | 0.0190 (17) | −0.0307 (19) |
C29 | 0.0805 (18) | 0.098 (2) | 0.0742 (17) | 0.0228 (16) | 0.0149 (13) | −0.0001 (15) |
C30 | 0.0707 (18) | 0.0667 (17) | 0.227 (4) | 0.0082 (15) | 0.018 (2) | −0.027 (2) |
Geometric parameters (Å, º) top
S1—O2 | 1.419 (2) | C13—C16 | 1.512 (4) |
S1—O1 | 1.431 (2) | C14—C15 | 1.370 (4) |
S1—N1 | 1.707 (2) | C14—H14 | 0.9300 |
S1—C17 | 1.749 (2) | C15—H15 | 0.9300 |
N1—C8 | 1.439 (3) | C16—H16A | 0.9600 |
N1—C1 | 1.441 (3) | C16—H16B | 0.9600 |
S2—O3 | 1.4250 (18) | C16—H16C | 0.9600 |
S2—O4 | 1.4293 (18) | C17—C18 | 1.378 (3) |
S2—N2 | 1.6729 (18) | C17—C22 | 1.382 (3) |
S2—C24 | 1.757 (2) | C18—C19 | 1.368 (4) |
N2—C6 | 1.430 (3) | C18—H18 | 0.9300 |
N2—C7 | 1.471 (3) | C19—C20 | 1.375 (4) |
C1—C2 | 1.397 (4) | C19—H19 | 0.9300 |
C1—C6 | 1.405 (3) | C20—C21 | 1.370 (4) |
C2—C3 | 1.368 (5) | C20—C23 | 1.510 (4) |
C2—H2 | 0.9300 | C21—C22 | 1.378 (4) |
C3—C4 | 1.379 (5) | C21—H21 | 0.9300 |
C3—H3 | 0.9300 | C22—H22 | 0.9300 |
C4—C5 | 1.380 (4) | C23—H23A | 0.9600 |
C4—H4 | 0.9300 | C23—H23B | 0.9600 |
C5—C6 | 1.398 (3) | C23—H23C | 0.9600 |
C5—H5 | 0.9300 | C24—C25 | 1.371 (3) |
C7—C8 | 1.505 (3) | C24—C29 | 1.375 (3) |
C7—H7A | 0.9700 | C25—C26 | 1.383 (4) |
C7—H7B | 0.9700 | C25—H25 | 0.9300 |
C8—C9 | 1.335 (3) | C26—C27 | 1.373 (4) |
C9—C10 | 1.466 (3) | C26—H26 | 0.9300 |
C9—H9 | 0.9300 | C27—C28 | 1.373 (4) |
C10—C11 | 1.387 (3) | C27—C30 | 1.519 (4) |
C10—C15 | 1.396 (3) | C28—C29 | 1.378 (4) |
C11—C12 | 1.374 (4) | C28—H28 | 0.9300 |
C11—H11 | 0.9300 | C29—H29 | 0.9300 |
C12—C13 | 1.386 (4) | C30—H30A | 0.9600 |
C12—H12 | 0.9300 | C30—H30B | 0.9600 |
C13—C14 | 1.378 (4) | C30—H30C | 0.9600 |
| | | |
O2—S1—O1 | 120.14 (15) | C15—C14—C13 | 121.2 (2) |
O2—S1—N1 | 106.87 (13) | C15—C14—H14 | 119.4 |
O1—S1—N1 | 105.77 (11) | C13—C14—H14 | 119.4 |
O2—S1—C17 | 108.57 (12) | C14—C15—C10 | 121.6 (2) |
O1—S1—C17 | 108.38 (13) | C14—C15—H15 | 119.2 |
N1—S1—C17 | 106.30 (9) | C10—C15—H15 | 119.2 |
C8—N1—C1 | 115.81 (18) | C13—C16—H16A | 109.5 |
C8—N1—S1 | 113.60 (16) | C13—C16—H16B | 109.5 |
C1—N1—S1 | 117.41 (14) | H16A—C16—H16B | 109.5 |
O3—S2—O4 | 120.01 (12) | C13—C16—H16C | 109.5 |
O3—S2—N2 | 106.84 (10) | H16A—C16—H16C | 109.5 |
O4—S2—N2 | 105.28 (10) | H16B—C16—H16C | 109.5 |
O3—S2—C24 | 108.57 (12) | C18—C17—C22 | 119.9 (2) |
O4—S2—C24 | 108.05 (11) | C18—C17—S1 | 120.32 (19) |
N2—S2—C24 | 107.47 (9) | C22—C17—S1 | 119.78 (18) |
C6—N2—C7 | 115.32 (17) | C19—C18—C17 | 119.3 (2) |
C6—N2—S2 | 119.20 (14) | C19—C18—H18 | 120.4 |
C7—N2—S2 | 115.54 (14) | C17—C18—H18 | 120.4 |
C2—C1—C6 | 119.2 (3) | C18—C19—C20 | 122.0 (2) |
C2—C1—N1 | 120.0 (2) | C18—C19—H19 | 119.0 |
C6—C1—N1 | 120.8 (2) | C20—C19—H19 | 119.0 |
C3—C2—C1 | 120.5 (3) | C21—C20—C19 | 117.9 (2) |
C3—C2—H2 | 119.7 | C21—C20—C23 | 120.8 (3) |
C1—C2—H2 | 119.7 | C19—C20—C23 | 121.3 (3) |
C2—C3—C4 | 120.5 (3) | C20—C21—C22 | 121.6 (2) |
C2—C3—H3 | 119.8 | C20—C21—H21 | 119.2 |
C4—C3—H3 | 119.8 | C22—C21—H21 | 119.2 |
C3—C4—C5 | 120.1 (3) | C21—C22—C17 | 119.3 (2) |
C3—C4—H4 | 120.0 | C21—C22—H22 | 120.4 |
C5—C4—H4 | 120.0 | C17—C22—H22 | 120.4 |
C4—C5—C6 | 120.5 (3) | C20—C23—H23A | 109.5 |
C4—C5—H5 | 119.8 | C20—C23—H23B | 109.5 |
C6—C5—H5 | 119.8 | H23A—C23—H23B | 109.5 |
C5—C6—C1 | 118.9 (2) | C20—C23—H23C | 109.5 |
C5—C6—N2 | 119.9 (2) | H23A—C23—H23C | 109.5 |
C1—C6—N2 | 121.2 (2) | H23B—C23—H23C | 109.5 |
N2—C7—C8 | 111.01 (18) | C25—C24—C29 | 120.2 (2) |
N2—C7—H7A | 109.4 | C25—C24—S2 | 120.27 (18) |
C8—C7—H7A | 109.4 | C29—C24—S2 | 119.50 (19) |
N2—C7—H7B | 109.4 | C24—C25—C26 | 119.1 (3) |
C8—C7—H7B | 109.4 | C24—C25—H25 | 120.5 |
H7A—C7—H7B | 108.0 | C26—C25—H25 | 120.5 |
C9—C8—N1 | 118.5 (2) | C27—C26—C25 | 121.9 (3) |
C9—C8—C7 | 127.6 (2) | C27—C26—H26 | 119.1 |
N1—C8—C7 | 113.88 (18) | C25—C26—H26 | 119.1 |
C8—C9—C10 | 128.7 (2) | C26—C27—C28 | 117.7 (2) |
C8—C9—H9 | 115.6 | C26—C27—C30 | 121.3 (3) |
C10—C9—H9 | 115.6 | C28—C27—C30 | 121.0 (3) |
C11—C10—C15 | 117.0 (2) | C27—C28—C29 | 121.6 (3) |
C11—C10—C9 | 124.2 (2) | C27—C28—H28 | 119.2 |
C15—C10—C9 | 118.8 (2) | C29—C28—H28 | 119.2 |
C12—C11—C10 | 121.0 (3) | C24—C29—C28 | 119.4 (3) |
C12—C11—H11 | 119.5 | C24—C29—H29 | 120.3 |
C10—C11—H11 | 119.5 | C28—C29—H29 | 120.3 |
C11—C12—C13 | 121.6 (3) | C27—C30—H30A | 109.5 |
C11—C12—H12 | 119.2 | C27—C30—H30B | 109.5 |
C13—C12—H12 | 119.2 | H30A—C30—H30B | 109.5 |
C14—C13—C12 | 117.6 (3) | C27—C30—H30C | 109.5 |
C14—C13—C16 | 121.5 (3) | H30A—C30—H30C | 109.5 |
C12—C13—C16 | 121.0 (3) | H30B—C30—H30C | 109.5 |
| | | |
N1—C8—C9—C10 | 174.7 (2) | N1—S1—C17—C18 | −86.3 (2) |
N2—C7—C8—N1 | 53.9 (2) | N2—S2—C24—C25 | 99.5 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C30—H30C···O1i | 0.96 | 2.78 | 3.282 (4) | 113 |
C23—H23B···O3ii | 0.96 | 2.96 | 3.296 (4) | 102 |
C14—H14···O1iii | 0.93 | 2.49 | 3.340 (3) | 153 |
C21—H21···O4iv | 0.93 | 2.86 | 3.397 (3) | 118 |
C19—H19···O2v | 0.93 | 2.52 | 3.402 (4) | 159 |
C11—H11···O4iv | 0.93 | 2.58 | 3.438 (4) | 153 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x, −y+1, −z; (iv) −x, −y, −z; (v) −x+1, y−1/2, −z+1/2. |
(III) 2-[(4-methoxyphenyl)methylidene]-1,4-di-
p-tosyl-1,2,3,4-tetrahydroquinoxaline
top
Crystal data top
C30H28N2O5S2 | Dx = 1.383 Mg m−3 |
Mr = 560.66 | Melting point: 425(1) K K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.546 (1) Å | Cell parameters from 57 reflections |
b = 11.844 (1) Å | θ = 6.7–38.5° |
c = 21.985 (3) Å | µ = 0.24 mm−1 |
β = 101.25 (1)° | T = 160 K |
V = 2693.3 (5) Å3 | Block, colourless |
Z = 4 | 0.36 × 0.32 × 0.16 mm |
F(000) = 1176 | |
Data collection top
Siemens P4 diffractometer | 3531 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.038 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −1→12 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −1→14 |
Tmin = 0.932, Tmax = 0.962 | l = −25→25 |
6072 measured reflections | 3 standard reflections every 97 reflections |
4693 independent reflections | intensity decay: <2% |
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) = 0.110 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0447P)2 + 1.4501P] where P = (Fo2 + 2Fc2)/3 |
4693 reflections | (Δ/σ)max < 0.001 |
355 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C30H28N2O5S2 | V = 2693.3 (5) Å3 |
Mr = 560.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.546 (1) Å | µ = 0.24 mm−1 |
b = 11.844 (1) Å | T = 160 K |
c = 21.985 (3) Å | 0.36 × 0.32 × 0.16 mm |
β = 101.25 (1)° | |
Data collection top
Siemens P4 diffractometer | 3531 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.038 |
Tmin = 0.932, Tmax = 0.962 | 3 standard reflections every 97 reflections |
6072 measured reflections | intensity decay: <2% |
4693 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.52 e Å−3 |
4693 reflections | Δρmin = −0.36 e Å−3 |
355 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S2 | −0.17858 (6) | 0.02598 (5) | 0.10863 (3) | 0.02493 (16) | |
S1 | 0.30568 (6) | 0.25535 (5) | 0.15383 (3) | 0.02862 (17) | |
O1 | 0.31578 (17) | 0.32301 (15) | 0.10120 (9) | 0.0377 (5) | |
O2 | 0.36249 (18) | 0.29369 (16) | 0.21464 (9) | 0.0408 (5) | |
O3 | −0.21816 (17) | −0.03498 (15) | 0.15782 (9) | 0.0348 (4) | |
O4 | −0.20330 (16) | −0.01990 (15) | 0.04704 (8) | 0.0326 (4) | |
O5 | −0.25420 (18) | 0.32024 (16) | −0.19143 (8) | 0.0363 (4) | |
N1 | 0.14431 (18) | 0.24013 (16) | 0.15224 (9) | 0.0249 (5) | |
N2 | −0.01757 (18) | 0.04089 (16) | 0.12811 (9) | 0.0231 (4) | |
C1 | 0.1100 (2) | 0.1757 (2) | 0.20220 (11) | 0.0258 (5) | |
C2 | 0.1488 (2) | 0.2125 (2) | 0.26324 (12) | 0.0332 (6) | |
H2 | 0.1927 | 0.2807 | 0.2711 | 0.040* | |
C3 | 0.1229 (3) | 0.1494 (3) | 0.31197 (13) | 0.0406 (7) | |
H3 | 0.1478 | 0.1757 | 0.3524 | 0.049* | |
C4 | 0.0595 (3) | 0.0464 (3) | 0.30073 (13) | 0.0429 (7) | |
H4 | 0.0459 | 0.0019 | 0.3337 | 0.052* | |
C5 | 0.0167 (2) | 0.0104 (2) | 0.24054 (12) | 0.0331 (6) | |
H5 | −0.0256 | −0.0586 | 0.2332 | 0.040* | |
C6 | 0.0362 (2) | 0.0763 (2) | 0.19036 (11) | 0.0245 (5) | |
C7 | 0.0426 (2) | 0.09252 (19) | 0.07916 (11) | 0.0232 (5) | |
H7A | −0.0144 | 0.0829 | 0.0392 | 0.028* | |
H7B | 0.1233 | 0.0541 | 0.0778 | 0.028* | |
C8 | 0.0686 (2) | 0.2164 (2) | 0.09109 (11) | 0.0232 (5) | |
C9 | 0.0289 (2) | 0.3039 (2) | 0.05437 (11) | 0.0255 (5) | |
H9 | 0.0497 | 0.3744 | 0.0721 | 0.031* | |
C10 | −0.0431 (2) | 0.3058 (2) | −0.01015 (11) | 0.0237 (5) | |
C11 | −0.1221 (2) | 0.3986 (2) | −0.02959 (12) | 0.0263 (5) | |
H11 | −0.1265 | 0.4566 | −0.0016 | 0.032* | |
C12 | −0.1946 (2) | 0.4071 (2) | −0.08959 (12) | 0.0274 (5) | |
H12 | −0.2464 | 0.4699 | −0.1013 | 0.033* | |
C13 | −0.1885 (2) | 0.3208 (2) | −0.13162 (11) | 0.0274 (5) | |
C14 | −0.1085 (2) | 0.2274 (2) | −0.11357 (12) | 0.0295 (6) | |
H14 | −0.1041 | 0.1695 | −0.1417 | 0.035* | |
C15 | −0.0363 (2) | 0.2211 (2) | −0.05417 (11) | 0.0273 (6) | |
H15 | 0.0180 | 0.1595 | −0.0430 | 0.033* | |
C16 | −0.3261 (3) | 0.4203 (3) | −0.21311 (13) | 0.0487 (8) | |
H16A | −0.3660 | 0.4110 | −0.2560 | 0.073* | |
H16B | −0.2687 | 0.4839 | −0.2088 | 0.073* | |
H16C | −0.3916 | 0.4327 | −0.1891 | 0.073* | |
C17 | 0.3652 (2) | 0.1192 (2) | 0.14378 (11) | 0.0248 (5) | |
C18 | 0.4030 (2) | 0.0912 (2) | 0.08884 (12) | 0.0304 (6) | |
H18 | 0.3954 | 0.1432 | 0.0567 | 0.036* | |
C19 | 0.4522 (3) | −0.0156 (2) | 0.08263 (12) | 0.0324 (6) | |
H19 | 0.4796 | −0.0342 | 0.0462 | 0.039* | |
C20 | 0.4618 (2) | −0.0957 (2) | 0.12942 (12) | 0.0274 (6) | |
C21 | 0.4212 (2) | −0.0662 (2) | 0.18368 (12) | 0.0301 (6) | |
H21 | 0.4259 | −0.1192 | 0.2153 | 0.036* | |
C22 | 0.3740 (2) | 0.0406 (2) | 0.19149 (12) | 0.0298 (6) | |
H22 | 0.3484 | 0.0598 | 0.2283 | 0.036* | |
C23 | 0.5168 (3) | −0.2112 (2) | 0.12197 (13) | 0.0374 (7) | |
H23A | 0.5635 | −0.2371 | 0.1614 | 0.056* | |
H23B | 0.5742 | −0.2072 | 0.0931 | 0.056* | |
H23C | 0.4477 | −0.2627 | 0.1067 | 0.056* | |
C24 | −0.2454 (2) | 0.1627 (2) | 0.10561 (11) | 0.0239 (5) | |
C25 | −0.2422 (2) | 0.2221 (2) | 0.16034 (12) | 0.0291 (6) | |
H25 | −0.2041 | 0.1906 | 0.1983 | 0.035* | |
C26 | −0.2962 (2) | 0.3287 (2) | 0.15776 (13) | 0.0332 (6) | |
H26 | −0.2943 | 0.3687 | 0.1943 | 0.040* | |
C27 | −0.3536 (2) | 0.3773 (2) | 0.10133 (13) | 0.0302 (6) | |
C28 | −0.3542 (2) | 0.3163 (2) | 0.04760 (12) | 0.0312 (6) | |
H28 | −0.3922 | 0.3478 | 0.0097 | 0.037* | |
C29 | −0.3000 (2) | 0.2097 (2) | 0.04868 (12) | 0.0273 (5) | |
H29 | −0.3002 | 0.1704 | 0.0120 | 0.033* | |
C30 | −0.4141 (3) | 0.4933 (2) | 0.09864 (15) | 0.0453 (8) | |
H30A | −0.3846 | 0.5316 | 0.1373 | 0.068* | |
H30B | −0.5065 | 0.4861 | 0.0914 | 0.068* | |
H30C | −0.3898 | 0.5358 | 0.0656 | 0.068* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S2 | 0.0197 (3) | 0.0190 (3) | 0.0336 (3) | 0.0001 (2) | −0.0008 (2) | 0.0004 (3) |
S1 | 0.0208 (3) | 0.0201 (3) | 0.0417 (4) | −0.0018 (2) | −0.0019 (3) | −0.0035 (3) |
O1 | 0.0274 (9) | 0.0240 (9) | 0.0599 (13) | −0.0040 (8) | 0.0040 (9) | 0.0090 (9) |
O2 | 0.0291 (10) | 0.0347 (11) | 0.0523 (12) | −0.0033 (9) | −0.0075 (9) | −0.0161 (9) |
O3 | 0.0258 (9) | 0.0294 (10) | 0.0476 (11) | −0.0024 (8) | 0.0033 (8) | 0.0127 (9) |
O4 | 0.0268 (9) | 0.0260 (9) | 0.0408 (11) | −0.0001 (8) | −0.0038 (8) | −0.0109 (8) |
O5 | 0.0394 (10) | 0.0382 (11) | 0.0283 (10) | 0.0095 (9) | −0.0006 (8) | 0.0029 (8) |
N1 | 0.0200 (10) | 0.0211 (10) | 0.0314 (11) | −0.0004 (8) | −0.0010 (8) | −0.0036 (9) |
N2 | 0.0194 (10) | 0.0210 (10) | 0.0273 (11) | 0.0008 (8) | 0.0007 (8) | 0.0005 (8) |
C1 | 0.0201 (12) | 0.0238 (12) | 0.0314 (14) | 0.0089 (10) | −0.0001 (10) | −0.0042 (11) |
C2 | 0.0275 (13) | 0.0336 (14) | 0.0347 (15) | 0.0119 (11) | −0.0028 (11) | −0.0081 (12) |
C3 | 0.0347 (15) | 0.0570 (19) | 0.0282 (15) | 0.0149 (14) | 0.0015 (12) | −0.0062 (14) |
C4 | 0.0360 (15) | 0.061 (2) | 0.0320 (15) | 0.0116 (15) | 0.0059 (12) | 0.0111 (14) |
C5 | 0.0257 (13) | 0.0379 (15) | 0.0350 (15) | 0.0036 (11) | 0.0041 (11) | 0.0075 (12) |
C6 | 0.0201 (11) | 0.0257 (12) | 0.0260 (13) | 0.0063 (10) | 0.0002 (10) | −0.0012 (10) |
C7 | 0.0228 (12) | 0.0190 (12) | 0.0262 (13) | 0.0003 (10) | 0.0007 (10) | −0.0010 (10) |
C8 | 0.0179 (11) | 0.0227 (12) | 0.0276 (13) | −0.0011 (10) | 0.0008 (9) | −0.0029 (10) |
C9 | 0.0220 (12) | 0.0183 (12) | 0.0352 (14) | −0.0014 (10) | 0.0031 (10) | −0.0031 (10) |
C10 | 0.0209 (11) | 0.0195 (12) | 0.0305 (13) | −0.0017 (10) | 0.0045 (10) | 0.0040 (10) |
C11 | 0.0272 (12) | 0.0191 (12) | 0.0329 (14) | −0.0020 (10) | 0.0068 (11) | 0.0000 (10) |
C12 | 0.0234 (12) | 0.0220 (12) | 0.0367 (14) | 0.0042 (10) | 0.0056 (11) | 0.0064 (11) |
C13 | 0.0234 (12) | 0.0285 (13) | 0.0296 (14) | −0.0001 (10) | 0.0036 (10) | 0.0045 (11) |
C14 | 0.0354 (14) | 0.0236 (13) | 0.0311 (14) | 0.0045 (11) | 0.0105 (11) | −0.0003 (11) |
C15 | 0.0280 (13) | 0.0222 (12) | 0.0321 (14) | 0.0065 (10) | 0.0070 (11) | 0.0050 (11) |
C16 | 0.0510 (19) | 0.061 (2) | 0.0327 (16) | 0.0299 (16) | 0.0050 (14) | 0.0082 (15) |
C17 | 0.0169 (11) | 0.0234 (12) | 0.0310 (13) | 0.0005 (10) | −0.0026 (10) | −0.0024 (10) |
C18 | 0.0280 (13) | 0.0303 (14) | 0.0330 (14) | −0.0008 (11) | 0.0065 (11) | 0.0067 (11) |
C19 | 0.0338 (14) | 0.0345 (15) | 0.0304 (14) | 0.0000 (12) | 0.0099 (11) | −0.0018 (12) |
C20 | 0.0181 (11) | 0.0264 (13) | 0.0355 (14) | 0.0003 (10) | −0.0005 (10) | −0.0047 (11) |
C21 | 0.0291 (13) | 0.0320 (14) | 0.0264 (13) | 0.0064 (11) | −0.0014 (11) | 0.0048 (11) |
C22 | 0.0270 (13) | 0.0348 (14) | 0.0260 (13) | 0.0082 (11) | 0.0014 (10) | 0.0012 (11) |
C23 | 0.0336 (14) | 0.0317 (15) | 0.0452 (17) | 0.0048 (12) | 0.0029 (12) | −0.0074 (13) |
C24 | 0.0187 (11) | 0.0218 (12) | 0.0309 (13) | −0.0012 (9) | 0.0045 (10) | −0.0006 (10) |
C25 | 0.0263 (12) | 0.0334 (14) | 0.0278 (13) | 0.0012 (11) | 0.0051 (10) | 0.0027 (11) |
C26 | 0.0311 (14) | 0.0322 (14) | 0.0376 (15) | 0.0005 (12) | 0.0098 (12) | −0.0073 (12) |
C27 | 0.0219 (12) | 0.0246 (13) | 0.0452 (16) | 0.0011 (10) | 0.0090 (11) | −0.0027 (12) |
C28 | 0.0248 (13) | 0.0295 (14) | 0.0373 (15) | 0.0047 (11) | 0.0013 (11) | 0.0076 (12) |
C29 | 0.0247 (12) | 0.0263 (13) | 0.0300 (13) | 0.0029 (10) | 0.0033 (10) | −0.0001 (11) |
C30 | 0.0379 (16) | 0.0303 (15) | 0.067 (2) | 0.0100 (13) | 0.0075 (15) | −0.0043 (14) |
Geometric parameters (Å, º) top
S2—O3 | 1.4286 (19) | C13—C14 | 1.401 (3) |
S2—O4 | 1.4349 (18) | C14—C15 | 1.380 (3) |
S2—N2 | 1.6776 (19) | C14—H14 | 0.9300 |
S2—C24 | 1.762 (2) | C15—H15 | 0.9300 |
S1—O2 | 1.428 (2) | C16—H16A | 0.9600 |
S1—O1 | 1.428 (2) | C16—H16B | 0.9600 |
S1—N1 | 1.705 (2) | C16—H16C | 0.9600 |
S1—C17 | 1.760 (2) | C17—C18 | 1.384 (4) |
O5—C13 | 1.361 (3) | C17—C22 | 1.392 (3) |
O5—C16 | 1.437 (3) | C18—C19 | 1.384 (4) |
N1—C1 | 1.440 (3) | C18—H18 | 0.9300 |
N1—C8 | 1.451 (3) | C19—C20 | 1.389 (4) |
N2—C6 | 1.438 (3) | C19—H19 | 0.9300 |
N2—C7 | 1.484 (3) | C20—C21 | 1.388 (4) |
C1—C2 | 1.394 (3) | C20—C23 | 1.507 (3) |
C1—C6 | 1.408 (3) | C21—C22 | 1.382 (4) |
C2—C3 | 1.377 (4) | C21—H21 | 0.9300 |
C2—H2 | 0.9300 | C22—H22 | 0.9300 |
C3—C4 | 1.390 (5) | C23—H23A | 0.9600 |
C3—H3 | 0.9300 | C23—H23B | 0.9600 |
C4—C5 | 1.380 (4) | C23—H23C | 0.9600 |
C4—H4 | 0.9300 | C24—C29 | 1.388 (3) |
C5—C6 | 1.399 (4) | C24—C25 | 1.389 (3) |
C5—H5 | 0.9300 | C25—C26 | 1.381 (4) |
C7—C8 | 1.506 (3) | C25—H25 | 0.9300 |
C7—H7A | 0.9700 | C26—C27 | 1.394 (4) |
C7—H7B | 0.9700 | C26—H26 | 0.9300 |
C8—C9 | 1.330 (3) | C27—C28 | 1.384 (4) |
C9—C10 | 1.473 (3) | C27—C30 | 1.511 (4) |
C9—H9 | 0.9300 | C28—C29 | 1.384 (4) |
C10—C11 | 1.395 (3) | C28—H28 | 0.9300 |
C10—C15 | 1.405 (3) | C29—H29 | 0.9300 |
C11—C12 | 1.393 (4) | C30—H30A | 0.9600 |
C11—H11 | 0.9300 | C30—H30B | 0.9600 |
C12—C13 | 1.387 (4) | C30—H30C | 0.9600 |
C12—H12 | 0.9300 | | |
| | | |
O3—S2—O4 | 119.79 (11) | C15—C14—C13 | 120.1 (2) |
O3—S2—N2 | 106.89 (10) | C15—C14—H14 | 120.0 |
O4—S2—N2 | 105.62 (10) | C13—C14—H14 | 120.0 |
O3—S2—C24 | 108.63 (11) | C14—C15—C10 | 121.4 (2) |
O4—S2—C24 | 108.35 (11) | C14—C15—H15 | 119.3 |
N2—S2—C24 | 106.85 (10) | C10—C15—H15 | 119.3 |
O2—S1—O1 | 119.72 (12) | O5—C16—H16A | 109.5 |
O2—S1—N1 | 106.71 (11) | O5—C16—H16B | 109.5 |
O1—S1—N1 | 105.94 (11) | H16A—C16—H16B | 109.5 |
O2—S1—C17 | 108.30 (11) | O5—C16—H16C | 109.5 |
O1—S1—C17 | 109.11 (12) | H16A—C16—H16C | 109.5 |
N1—S1—C17 | 106.25 (11) | H16B—C16—H16C | 109.5 |
C13—O5—C16 | 116.9 (2) | C18—C17—C22 | 120.6 (2) |
C1—N1—C8 | 115.44 (19) | C18—C17—S1 | 119.98 (19) |
C1—N1—S1 | 116.01 (15) | C22—C17—S1 | 119.42 (19) |
C8—N1—S1 | 113.98 (16) | C19—C18—C17 | 118.8 (2) |
C6—N2—C7 | 115.16 (19) | C19—C18—H18 | 120.6 |
C6—N2—S2 | 117.73 (16) | C17—C18—H18 | 120.6 |
C7—N2—S2 | 114.41 (15) | C18—C19—C20 | 121.7 (2) |
C2—C1—C6 | 119.2 (2) | C18—C19—H19 | 119.1 |
C2—C1—N1 | 119.9 (2) | C20—C19—H19 | 119.1 |
C6—C1—N1 | 120.9 (2) | C21—C20—C19 | 118.3 (2) |
C3—C2—C1 | 120.9 (3) | C21—C20—C23 | 120.8 (2) |
C3—C2—H2 | 119.5 | C19—C20—C23 | 120.9 (2) |
C1—C2—H2 | 119.5 | C22—C21—C20 | 121.0 (2) |
C2—C3—C4 | 120.0 (3) | C22—C21—H21 | 119.5 |
C2—C3—H3 | 120.0 | C20—C21—H21 | 119.5 |
C4—C3—H3 | 120.0 | C21—C22—C17 | 119.4 (2) |
C5—C4—C3 | 119.9 (3) | C21—C22—H22 | 120.3 |
C5—C4—H4 | 120.1 | C17—C22—H22 | 120.3 |
C3—C4—H4 | 120.1 | C20—C23—H23A | 109.5 |
C4—C5—C6 | 120.9 (3) | C20—C23—H23B | 109.5 |
C4—C5—H5 | 119.6 | H23A—C23—H23B | 109.5 |
C6—C5—H5 | 119.6 | C20—C23—H23C | 109.5 |
C5—C6—C1 | 118.8 (2) | H23A—C23—H23C | 109.5 |
C5—C6—N2 | 119.8 (2) | H23B—C23—H23C | 109.5 |
C1—C6—N2 | 121.4 (2) | C29—C24—C25 | 120.9 (2) |
N2—C7—C8 | 111.34 (19) | C29—C24—S2 | 119.66 (19) |
N2—C7—H7A | 109.4 | C25—C24—S2 | 119.40 (19) |
C8—C7—H7A | 109.4 | C26—C25—C24 | 119.2 (2) |
N2—C7—H7B | 109.4 | C26—C25—H25 | 120.4 |
C8—C7—H7B | 109.4 | C24—C25—H25 | 120.4 |
H7A—C7—H7B | 108.0 | C25—C26—C27 | 121.2 (2) |
C9—C8—N1 | 117.6 (2) | C25—C26—H26 | 119.4 |
C9—C8—C7 | 128.9 (2) | C27—C26—H26 | 119.4 |
N1—C8—C7 | 113.5 (2) | C28—C27—C26 | 118.2 (2) |
C8—C9—C10 | 129.7 (2) | C28—C27—C30 | 120.7 (3) |
C8—C9—H9 | 115.2 | C26—C27—C30 | 121.1 (2) |
C10—C9—H9 | 115.2 | C27—C28—C29 | 121.9 (2) |
C11—C10—C15 | 117.3 (2) | C27—C28—H28 | 119.0 |
C11—C10—C9 | 118.2 (2) | C29—C28—H28 | 119.0 |
C15—C10—C9 | 124.5 (2) | C28—C29—C24 | 118.6 (2) |
C12—C11—C10 | 122.1 (2) | C28—C29—H29 | 120.7 |
C12—C11—H11 | 118.9 | C24—C29—H29 | 120.7 |
C10—C11—H11 | 118.9 | C27—C30—H30A | 109.5 |
C13—C12—C11 | 119.3 (2) | C27—C30—H30B | 109.5 |
C13—C12—H12 | 120.4 | H30A—C30—H30B | 109.5 |
C11—C12—H12 | 120.4 | C27—C30—H30C | 109.5 |
O5—C13—C12 | 124.5 (2) | H30A—C30—H30C | 109.5 |
O5—C13—C14 | 115.7 (2) | H30B—C30—H30C | 109.5 |
C12—C13—C14 | 119.8 (2) | | |
| | | |
N1—C8—C9—C10 | 176.8 (2) | N1—S1—C17—C18 | 109.2 (2) |
N2—C7—C8—N1 | 54.1 (3) | N2—S2—C24—C25 | −71.2 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···O2i | 0.93 | 2.66 | 3.311 (3) | 128 |
C25—H25···O5ii | 0.93 | 2.58 | 3.324 (3) | 137 |
C16—H16B···O2iii | 0.96 | 2.81 | 3.409 (4) | 122 |
C12—H12···O1iii | 0.93 | 2.56 | 3.434 (3) | 157 |
C15—H15···O4iv | 0.93 | 2.57 | 3.454 (3) | 158 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z; (iv) −x, −y, −z. |
(IV) 2-[(4-chlorophenyl)methylidene]-1,4-di-
p-tosyl-1,2,3,4-tetrahydroquinoxaline
top
Crystal data top
C29H25ClN2O4S2 | Dx = 1.399 Mg m−3 |
Mr = 565.08 | Melting point: 418(1) K K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.5361 (10) Å | Cell parameters from 34 reflections |
b = 24.040 (3) Å | θ = 3.4–12.5° |
c = 10.6146 (10) Å | µ = 0.34 mm−1 |
β = 93.863 (10)° | T = 293 K |
V = 2682.4 (5) Å3 | Needle, colourless |
Z = 4 | 0.56 × 0.32 × 0.28 mm |
F(000) = 1176 | |
Data collection top
Siemens P4 diffractometer | 2437 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω scans | h = −1→12 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −28→1 |
Tmin = 0.866, Tmax = 0.910 | l = −12→12 |
5563 measured reflections | 3 standard reflections every 97 reflections |
4509 independent reflections | intensity decay: <2% |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0318P)2] where P = (Fo2 + 2Fc2)/3 |
4509 reflections | (Δ/σ)max = 0.007 |
345 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C29H25ClN2O4S2 | V = 2682.4 (5) Å3 |
Mr = 565.08 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.5361 (10) Å | µ = 0.34 mm−1 |
b = 24.040 (3) Å | T = 293 K |
c = 10.6146 (10) Å | 0.56 × 0.32 × 0.28 mm |
β = 93.863 (10)° | |
Data collection top
Siemens P4 diffractometer | 2437 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.050 |
Tmin = 0.866, Tmax = 0.910 | 3 standard reflections every 97 reflections |
5563 measured reflections | intensity decay: <2% |
4509 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.23 e Å−3 |
4509 reflections | Δρmin = −0.20 e Å−3 |
345 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.79678 (8) | 0.80715 (4) | 0.70774 (8) | 0.0515 (3) | |
S2 | 1.25270 (9) | 0.88794 (4) | 0.49271 (9) | 0.0551 (3) | |
Cl | 1.29786 (10) | 1.03411 (5) | 1.06057 (10) | 0.0794 (3) | |
N1 | 0.9534 (2) | 0.81839 (10) | 0.6901 (2) | 0.0405 (7) | |
N2 | 1.1048 (2) | 0.86253 (11) | 0.4948 (2) | 0.0442 (7) | |
O1 | 0.7743 (2) | 0.74912 (10) | 0.6882 (2) | 0.0666 (7) | |
O2 | 0.7714 (2) | 0.83227 (12) | 0.8241 (2) | 0.0692 (8) | |
O3 | 1.3113 (2) | 0.85966 (12) | 0.3922 (2) | 0.0740 (8) | |
O4 | 1.2390 (2) | 0.94674 (10) | 0.4888 (2) | 0.0696 (7) | |
C1 | 1.0208 (3) | 0.78266 (14) | 0.6095 (3) | 0.0410 (8) | |
C2 | 1.0228 (3) | 0.72568 (15) | 0.6330 (3) | 0.0537 (9) | |
H2 | 0.9791 | 0.7115 | 0.6992 | 0.064* | |
C3 | 1.0887 (4) | 0.68992 (16) | 0.5595 (4) | 0.0635 (10) | |
H3 | 1.0923 | 0.6521 | 0.5783 | 0.076* | |
C4 | 1.1493 (4) | 0.71043 (17) | 0.4582 (4) | 0.0637 (11) | |
H4 | 1.1891 | 0.6861 | 0.4053 | 0.076* | |
C5 | 1.1511 (3) | 0.76653 (17) | 0.4350 (3) | 0.0579 (10) | |
H5 | 1.1927 | 0.7799 | 0.3666 | 0.069* | |
C6 | 1.0913 (3) | 0.80387 (14) | 0.5125 (3) | 0.0402 (8) | |
C7 | 1.0123 (3) | 0.89753 (13) | 0.5596 (3) | 0.0454 (8) | |
H7A | 0.9321 | 0.8983 | 0.5092 | 0.054* | |
H7B | 1.0442 | 0.9353 | 0.5662 | 0.054* | |
C8 | 0.9901 (3) | 0.87636 (13) | 0.6887 (3) | 0.0383 (8) | |
C9 | 1.0014 (3) | 0.90398 (13) | 0.7972 (3) | 0.0435 (8) | |
H9 | 0.9824 | 0.8839 | 0.8684 | 0.052* | |
C10 | 1.0403 (3) | 0.96234 (13) | 0.8197 (3) | 0.0418 (8) | |
C11 | 0.9944 (3) | 1.00757 (14) | 0.7489 (3) | 0.0524 (9) | |
H11 | 0.9330 | 1.0022 | 0.6829 | 0.063* | |
C12 | 1.0395 (4) | 1.06075 (15) | 0.7761 (3) | 0.0599 (10) | |
H12 | 1.0065 | 1.0908 | 0.7293 | 0.072* | |
C13 | 1.1327 (4) | 1.06966 (16) | 0.8715 (3) | 0.0579 (10) | |
H13 | 1.1643 | 1.1052 | 0.8882 | 0.069* | |
C14 | 1.1778 (3) | 1.02504 (15) | 0.9414 (3) | 0.0489 (9) | |
C15 | 1.1309 (3) | 0.97212 (14) | 0.9175 (3) | 0.0445 (8) | |
H15 | 1.1607 | 0.9427 | 0.9680 | 0.053* | |
C16 | 0.7182 (3) | 0.84430 (14) | 0.5840 (3) | 0.0459 (8) | |
C17 | 0.7080 (3) | 0.82139 (14) | 0.4634 (3) | 0.0513 (9) | |
H17 | 0.7385 | 0.7858 | 0.4491 | 0.062* | |
C18 | 0.6519 (3) | 0.85249 (15) | 0.3650 (3) | 0.0549 (10) | |
H18 | 0.6446 | 0.8373 | 0.2842 | 0.066* | |
C19 | 0.6063 (3) | 0.90553 (15) | 0.3838 (3) | 0.0520 (9) | |
C20 | 0.6196 (3) | 0.92772 (14) | 0.5035 (4) | 0.0565 (10) | |
H20 | 0.5899 | 0.9635 | 0.5172 | 0.068* | |
C21 | 0.6763 (3) | 0.89795 (15) | 0.6041 (3) | 0.0547 (10) | |
H21 | 0.6861 | 0.9138 | 0.6841 | 0.066* | |
C22 | 0.5420 (4) | 0.93897 (16) | 0.2771 (4) | 0.0731 (12) | |
H22A | 0.4990 | 0.9142 | 0.2174 | 0.110* | |
H22B | 0.6047 | 0.9600 | 0.2359 | 0.110* | |
H22C | 0.4814 | 0.9639 | 0.3103 | 0.110* | |
C23 | 1.3329 (3) | 0.86890 (14) | 0.6368 (3) | 0.0460 (8) | |
C24 | 1.3838 (3) | 0.81639 (16) | 0.6513 (4) | 0.0619 (10) | |
H24 | 1.3782 | 0.7912 | 0.5847 | 0.074* | |
C25 | 1.4437 (3) | 0.80171 (16) | 0.7672 (4) | 0.0602 (10) | |
H25 | 1.4773 | 0.7661 | 0.7780 | 0.072* | |
C26 | 1.4545 (3) | 0.83865 (17) | 0.8667 (3) | 0.0554 (10) | |
C27 | 1.4046 (3) | 0.89139 (16) | 0.8488 (4) | 0.0588 (10) | |
H27 | 1.4125 | 0.9171 | 0.9143 | 0.071* | |
C28 | 1.3429 (3) | 0.90640 (15) | 0.7349 (4) | 0.0559 (10) | |
H28 | 1.3083 | 0.9418 | 0.7245 | 0.067* | |
C29 | 1.5181 (4) | 0.82181 (19) | 0.9927 (4) | 0.0798 (13) | |
H29A | 1.5429 | 0.7834 | 0.9896 | 0.120* | |
H29B | 1.4598 | 0.8268 | 1.0574 | 0.120* | |
H29C | 1.5921 | 0.8445 | 1.0110 | 0.120* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0455 (5) | 0.0625 (6) | 0.0474 (5) | −0.0109 (5) | 0.0101 (4) | 0.0032 (5) |
S2 | 0.0421 (5) | 0.0667 (7) | 0.0570 (6) | −0.0143 (5) | 0.0076 (4) | 0.0087 (5) |
Cl | 0.0668 (7) | 0.0947 (8) | 0.0752 (7) | −0.0125 (6) | −0.0062 (6) | −0.0280 (6) |
N1 | 0.0375 (15) | 0.0463 (17) | 0.0381 (15) | −0.0098 (13) | 0.0044 (12) | 0.0005 (13) |
N2 | 0.0357 (15) | 0.0551 (18) | 0.0419 (15) | −0.0071 (14) | 0.0036 (13) | 0.0017 (13) |
O1 | 0.0583 (16) | 0.0590 (17) | 0.0830 (19) | −0.0222 (13) | 0.0078 (14) | 0.0115 (14) |
O2 | 0.0546 (16) | 0.106 (2) | 0.0491 (15) | −0.0106 (15) | 0.0192 (12) | −0.0031 (14) |
O3 | 0.0542 (16) | 0.108 (2) | 0.0628 (16) | −0.0198 (16) | 0.0260 (14) | −0.0100 (15) |
O4 | 0.0586 (16) | 0.0628 (17) | 0.0872 (19) | −0.0151 (14) | 0.0031 (14) | 0.0250 (15) |
C1 | 0.0385 (19) | 0.048 (2) | 0.0354 (17) | −0.0041 (16) | −0.0018 (15) | −0.0047 (16) |
C2 | 0.052 (2) | 0.051 (2) | 0.058 (2) | −0.0125 (19) | 0.0013 (18) | −0.0060 (19) |
C3 | 0.063 (3) | 0.052 (2) | 0.075 (3) | −0.006 (2) | 0.001 (2) | −0.017 (2) |
C4 | 0.048 (2) | 0.071 (3) | 0.074 (3) | 0.000 (2) | 0.013 (2) | −0.025 (2) |
C5 | 0.043 (2) | 0.076 (3) | 0.055 (2) | −0.006 (2) | 0.0061 (18) | −0.015 (2) |
C6 | 0.0316 (17) | 0.051 (2) | 0.0375 (18) | −0.0038 (16) | −0.0013 (14) | −0.0061 (16) |
C7 | 0.0392 (19) | 0.052 (2) | 0.0444 (19) | −0.0016 (17) | −0.0029 (16) | 0.0093 (16) |
C8 | 0.0338 (17) | 0.042 (2) | 0.0393 (18) | 0.0002 (16) | −0.0004 (14) | 0.0056 (16) |
C9 | 0.040 (2) | 0.047 (2) | 0.0434 (19) | −0.0013 (16) | 0.0008 (16) | 0.0046 (16) |
C10 | 0.048 (2) | 0.044 (2) | 0.0340 (17) | 0.0024 (17) | 0.0072 (16) | −0.0008 (16) |
C11 | 0.061 (2) | 0.052 (2) | 0.044 (2) | 0.008 (2) | 0.0012 (18) | 0.0019 (18) |
C12 | 0.080 (3) | 0.049 (2) | 0.052 (2) | 0.015 (2) | 0.014 (2) | 0.0062 (19) |
C13 | 0.064 (3) | 0.051 (2) | 0.060 (2) | −0.001 (2) | 0.016 (2) | −0.007 (2) |
C14 | 0.044 (2) | 0.059 (2) | 0.0440 (19) | −0.0060 (19) | 0.0061 (17) | −0.0101 (19) |
C15 | 0.045 (2) | 0.049 (2) | 0.0396 (19) | 0.0063 (18) | 0.0057 (17) | 0.0029 (16) |
C16 | 0.0325 (19) | 0.052 (2) | 0.054 (2) | −0.0078 (17) | 0.0070 (16) | −0.0013 (18) |
C17 | 0.051 (2) | 0.047 (2) | 0.056 (2) | −0.0034 (18) | 0.0025 (18) | −0.0090 (18) |
C18 | 0.053 (2) | 0.059 (2) | 0.053 (2) | −0.005 (2) | 0.0027 (19) | −0.0080 (19) |
C19 | 0.043 (2) | 0.050 (2) | 0.064 (2) | −0.0056 (18) | 0.0094 (18) | −0.0012 (19) |
C20 | 0.052 (2) | 0.037 (2) | 0.082 (3) | 0.0044 (18) | 0.016 (2) | −0.013 (2) |
C21 | 0.046 (2) | 0.061 (3) | 0.057 (2) | −0.0043 (19) | 0.0088 (18) | −0.014 (2) |
C22 | 0.070 (3) | 0.069 (3) | 0.082 (3) | 0.003 (2) | 0.011 (2) | 0.017 (2) |
C23 | 0.0331 (18) | 0.049 (2) | 0.057 (2) | −0.0104 (17) | 0.0064 (16) | −0.0045 (18) |
C24 | 0.046 (2) | 0.057 (3) | 0.082 (3) | −0.003 (2) | −0.004 (2) | −0.019 (2) |
C25 | 0.043 (2) | 0.058 (2) | 0.079 (3) | 0.0032 (19) | −0.002 (2) | −0.006 (2) |
C26 | 0.035 (2) | 0.067 (3) | 0.065 (3) | −0.0043 (19) | 0.0102 (19) | 0.007 (2) |
C27 | 0.045 (2) | 0.065 (3) | 0.067 (3) | −0.005 (2) | 0.002 (2) | −0.013 (2) |
C28 | 0.038 (2) | 0.053 (2) | 0.076 (3) | −0.0013 (18) | 0.0016 (19) | −0.004 (2) |
C29 | 0.065 (3) | 0.099 (3) | 0.074 (3) | 0.003 (3) | −0.001 (2) | 0.010 (3) |
Geometric parameters (Å, º) top
S1—O2 | 1.417 (2) | C12—H12 | 0.9300 |
S1—O1 | 1.428 (3) | C13—C14 | 1.371 (5) |
S1—N1 | 1.695 (3) | C13—H13 | 0.9300 |
S1—C16 | 1.750 (3) | C14—C15 | 1.382 (5) |
S2—O4 | 1.421 (3) | C15—H15 | 0.9300 |
S2—O3 | 1.439 (3) | C16—C21 | 1.384 (5) |
S2—N2 | 1.675 (3) | C16—C17 | 1.391 (4) |
S2—C23 | 1.758 (3) | C17—C18 | 1.385 (5) |
Cl—C14 | 1.741 (3) | C17—H17 | 0.9300 |
N1—C1 | 1.434 (4) | C18—C19 | 1.382 (5) |
N1—C8 | 1.447 (4) | C18—H18 | 0.9300 |
N2—C6 | 1.431 (4) | C19—C20 | 1.376 (5) |
N2—C7 | 1.491 (4) | C19—C22 | 1.511 (5) |
C1—C2 | 1.392 (5) | C20—C21 | 1.387 (5) |
C1—C6 | 1.405 (4) | C20—H20 | 0.9300 |
C2—C3 | 1.380 (5) | C21—H21 | 0.9300 |
C2—H2 | 0.9300 | C22—H22A | 0.9600 |
C3—C4 | 1.378 (5) | C22—H22B | 0.9600 |
C3—H3 | 0.9300 | C22—H22C | 0.9600 |
C4—C5 | 1.371 (5) | C23—C28 | 1.376 (5) |
C4—H4 | 0.9300 | C23—C24 | 1.376 (5) |
C5—C6 | 1.396 (4) | C24—C25 | 1.390 (5) |
C5—H5 | 0.9300 | C24—H24 | 0.9300 |
C7—C8 | 1.494 (4) | C25—C26 | 1.378 (5) |
C7—H7A | 0.9700 | C25—H25 | 0.9300 |
C7—H7B | 0.9700 | C26—C27 | 1.381 (5) |
C8—C9 | 1.328 (4) | C26—C29 | 1.510 (5) |
C9—C10 | 1.476 (4) | C27—C28 | 1.382 (5) |
C9—H9 | 0.9300 | C27—H27 | 0.9300 |
C10—C15 | 1.383 (4) | C28—H28 | 0.9300 |
C10—C11 | 1.390 (4) | C29—H29A | 0.9600 |
C11—C12 | 1.387 (5) | C29—H29B | 0.9600 |
C11—H11 | 0.9300 | C29—H29C | 0.9600 |
C12—C13 | 1.380 (5) | | |
| | | |
O2—S1—O1 | 120.27 (17) | C14—C13—C12 | 118.7 (3) |
O2—S1—N1 | 105.71 (14) | C14—C13—H13 | 120.7 |
O1—S1—N1 | 107.04 (15) | C12—C13—H13 | 120.7 |
O2—S1—C16 | 109.24 (17) | C13—C14—C15 | 121.0 (3) |
O1—S1—C16 | 108.90 (16) | C13—C14—Cl | 120.2 (3) |
N1—S1—C16 | 104.51 (14) | C15—C14—Cl | 118.8 (3) |
O4—S2—O3 | 119.72 (17) | C14—C15—C10 | 121.0 (3) |
O4—S2—N2 | 105.69 (15) | C14—C15—H15 | 119.5 |
O3—S2—N2 | 106.46 (15) | C10—C15—H15 | 119.5 |
O4—S2—C23 | 109.06 (17) | C21—C16—C17 | 120.3 (3) |
O3—S2—C23 | 108.51 (17) | C21—C16—S1 | 120.0 (3) |
N2—S2—C23 | 106.65 (14) | C17—C16—S1 | 119.5 (3) |
C1—N1—C8 | 115.3 (2) | C18—C17—C16 | 118.9 (3) |
C1—N1—S1 | 119.7 (2) | C18—C17—H17 | 120.6 |
C8—N1—S1 | 114.7 (2) | C16—C17—H17 | 120.6 |
C6—N2—C7 | 114.9 (2) | C19—C18—C17 | 121.6 (3) |
C6—N2—S2 | 117.5 (2) | C19—C18—H18 | 119.2 |
C7—N2—S2 | 116.0 (2) | C17—C18—H18 | 119.2 |
C2—C1—C6 | 119.1 (3) | C20—C19—C18 | 118.5 (3) |
C2—C1—N1 | 119.0 (3) | C20—C19—C22 | 119.9 (3) |
C6—C1—N1 | 121.8 (3) | C18—C19—C22 | 121.7 (3) |
C3—C2—C1 | 120.9 (3) | C19—C20—C21 | 121.5 (3) |
C3—C2—H2 | 119.6 | C19—C20—H20 | 119.2 |
C1—C2—H2 | 119.6 | C21—C20—H20 | 119.2 |
C4—C3—C2 | 119.7 (4) | C16—C21—C20 | 119.2 (3) |
C4—C3—H3 | 120.1 | C16—C21—H21 | 120.4 |
C2—C3—H3 | 120.1 | C20—C21—H21 | 120.4 |
C5—C4—C3 | 120.3 (4) | C19—C22—H22A | 109.5 |
C5—C4—H4 | 119.8 | C19—C22—H22B | 109.5 |
C3—C4—H4 | 119.8 | H22A—C22—H22B | 109.5 |
C4—C5—C6 | 120.9 (4) | C19—C22—H22C | 109.5 |
C4—C5—H5 | 119.5 | H22A—C22—H22C | 109.5 |
C6—C5—H5 | 119.5 | H22B—C22—H22C | 109.5 |
C5—C6—C1 | 118.7 (3) | C28—C23—C24 | 120.5 (3) |
C5—C6—N2 | 120.2 (3) | C28—C23—S2 | 119.7 (3) |
C1—C6—N2 | 121.1 (3) | C24—C23—S2 | 119.8 (3) |
N2—C7—C8 | 112.2 (2) | C23—C24—C25 | 118.8 (4) |
N2—C7—H7A | 109.2 | C23—C24—H24 | 120.6 |
C8—C7—H7A | 109.2 | C25—C24—H24 | 120.6 |
N2—C7—H7B | 109.2 | C26—C25—C24 | 121.6 (4) |
C8—C7—H7B | 109.2 | C26—C25—H25 | 119.2 |
H7A—C7—H7B | 107.9 | C24—C25—H25 | 119.2 |
C9—C8—N1 | 118.8 (3) | C25—C26—C27 | 118.4 (3) |
C9—C8—C7 | 127.9 (3) | C25—C26—C29 | 121.0 (4) |
N1—C8—C7 | 113.3 (3) | C27—C26—C29 | 120.6 (4) |
C8—C9—C10 | 128.5 (3) | C26—C27—C28 | 120.8 (4) |
C8—C9—H9 | 115.7 | C26—C27—H27 | 119.6 |
C10—C9—H9 | 115.7 | C28—C27—H27 | 119.6 |
C15—C10—C11 | 118.1 (3) | C23—C28—C27 | 119.9 (3) |
C15—C10—C9 | 116.9 (3) | C23—C28—H28 | 120.0 |
C11—C10—C9 | 125.0 (3) | C27—C28—H28 | 120.0 |
C12—C11—C10 | 120.4 (3) | C26—C29—H29A | 109.5 |
C12—C11—H11 | 119.8 | C26—C29—H29B | 109.5 |
C10—C11—H11 | 119.8 | H29A—C29—H29B | 109.5 |
C13—C12—C11 | 120.8 (3) | C26—C29—H29C | 109.5 |
C13—C12—H12 | 119.6 | H29A—C29—H29C | 109.5 |
C11—C12—H12 | 119.6 | H29B—C29—H29C | 109.5 |
| | | |
N1—C8—C9—C10 | 178.4 (3) | N1—S1—C16—C17 | 80.0 (3) |
N2—C7—C8—N1 | −53.5 (3) | N2—S2—C23—C24 | 81.5 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C29—H29C···O2i | 0.96 | 2.85 | 3.321 (5) | 112 |
C20—H20···O4ii | 0.93 | 2.82 | 3.364 (4) | 119 |
C18—H18···O1iii | 0.93 | 2.72 | 3.388 (4) | 129 |
C17—H17···O1iii | 0.93 | 2.94 | 3.488 (4) | 119 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+2, −z+1; (iii) x, −y+3/2, z−1/2. |
Experimental details
| (II) | (III) | (IV) |
Crystal data |
Chemical formula | C30H28N2O4S2 | C30H28N2O5S2 | C29H25ClN2O4S2 |
Mr | 544.66 | 560.66 | 565.08 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 160 | 293 |
a, b, c (Å) | 10.559 (4), 11.658 (4), 23.169 (7) | 10.546 (1), 11.844 (1), 21.985 (3) | 10.5361 (10), 24.040 (3), 10.6146 (10) |
β (°) | 100.54 (3) | 101.25 (1) | 93.863 (10) |
V (Å3) | 2803.9 (17) | 2693.3 (5) | 2682.4 (5) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.23 | 0.24 | 0.34 |
Crystal size (mm) | 0.64 × 0.52 × 0.48 | 0.36 × 0.32 × 0.16 | 0.56 × 0.32 × 0.28 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer | Siemens P4 diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) | Empirical (using intensity measurements) (North et al., 1968) | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.866, 0.896 | 0.932, 0.962 | 0.866, 0.910 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6386, 4923, 3664 | 6072, 4693, 3531 | 5563, 4509, 2437 |
Rint | 0.027 | 0.038 | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 | 0.596 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.130, 1.03 | 0.042, 0.110, 1.02 | 0.049, 0.108, 0.96 |
No. of reflections | 4923 | 4693 | 4509 |
No. of parameters | 346 | 355 | 345 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.31 | 0.52, −0.36 | 0.23, −0.20 |
Selected geometric parameters (Å, º) for (II) topS1—O2 | 1.419 (2) | S2—O4 | 1.4293 (18) |
S1—O1 | 1.431 (2) | S2—N2 | 1.6729 (18) |
S1—N1 | 1.707 (2) | S2—C24 | 1.757 (2) |
S1—C17 | 1.749 (2) | N2—C7 | 1.471 (3) |
N1—C8 | 1.439 (3) | C7—C8 | 1.505 (3) |
S2—O3 | 1.4250 (18) | C8—C9 | 1.335 (3) |
| | | |
O2—S1—O1 | 120.14 (15) | O3—S2—O4 | 120.01 (12) |
O2—S1—N1 | 106.87 (13) | O3—S2—N2 | 106.84 (10) |
O1—S1—N1 | 105.77 (11) | O4—S2—N2 | 105.28 (10) |
N1—S1—C17 | 106.30 (9) | N2—S2—C24 | 107.47 (9) |
C8—N1—C1 | 115.81 (18) | C6—N2—C7 | 115.32 (17) |
C8—N1—S1 | 113.60 (16) | C6—N2—S2 | 119.20 (14) |
C1—N1—S1 | 117.41 (14) | C7—N2—S2 | 115.54 (14) |
| | | |
N1—C8—C9—C10 | 174.7 (2) | N1—S1—C17—C18 | −86.3 (2) |
N2—C7—C8—N1 | 53.9 (2) | N2—S2—C24—C25 | 99.5 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C30—H30C···O1i | 0.96 | 2.78 | 3.282 (4) | 113.3 |
C23—H23B···O3ii | 0.96 | 2.96 | 3.296 (4) | 101.7 |
C14—H14···O1iii | 0.93 | 2.49 | 3.340 (3) | 153.0 |
C21—H21···O4iv | 0.93 | 2.86 | 3.397 (3) | 117.6 |
C19—H19···O2v | 0.93 | 2.52 | 3.402 (4) | 158.5 |
C11—H11···O4iv | 0.93 | 2.58 | 3.438 (4) | 153.1 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x, −y+1, −z; (iv) −x, −y, −z; (v) −x+1, y−1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (III) topS2—O3 | 1.4286 (19) | S1—N1 | 1.705 (2) |
S2—O4 | 1.4349 (18) | S1—C17 | 1.760 (2) |
S2—N2 | 1.6776 (19) | N1—C8 | 1.451 (3) |
S2—C24 | 1.762 (2) | N2—C7 | 1.484 (3) |
S1—O2 | 1.428 (2) | C7—C8 | 1.506 (3) |
S1—O1 | 1.428 (2) | C8—C9 | 1.330 (3) |
| | | |
O3—S2—O4 | 119.79 (11) | N1—S1—C17 | 106.25 (11) |
O3—S2—N2 | 106.89 (10) | C1—N1—C8 | 115.44 (19) |
O4—S2—N2 | 105.62 (10) | C1—N1—S1 | 116.01 (15) |
N2—S2—C24 | 106.85 (10) | C8—N1—S1 | 113.98 (16) |
O2—S1—O1 | 119.72 (12) | C6—N2—C7 | 115.16 (19) |
O2—S1—N1 | 106.71 (11) | C6—N2—S2 | 117.73 (16) |
O1—S1—N1 | 105.94 (11) | C7—N2—S2 | 114.41 (15) |
| | | |
N1—C8—C9—C10 | 176.8 (2) | N1—S1—C17—C18 | 109.2 (2) |
N2—C7—C8—N1 | 54.1 (3) | N2—S2—C24—C25 | −71.2 (2) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···O2i | 0.93 | 2.66 | 3.311 (3) | 127.6 |
C25—H25···O5ii | 0.93 | 2.58 | 3.324 (3) | 136.9 |
C16—H16B···O2iii | 0.96 | 2.81 | 3.409 (4) | 121.5 |
C12—H12···O1iii | 0.93 | 2.56 | 3.434 (3) | 156.8 |
C15—H15···O4iv | 0.93 | 2.57 | 3.454 (3) | 158.0 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z; (iv) −x, −y, −z. |
Selected geometric parameters (Å, º) for (IV) topS1—O2 | 1.417 (2) | S2—C23 | 1.758 (3) |
S1—O1 | 1.428 (3) | Cl—C14 | 1.741 (3) |
S1—N1 | 1.695 (3) | N1—C8 | 1.447 (4) |
S1—C16 | 1.750 (3) | N2—C7 | 1.491 (4) |
S2—O4 | 1.421 (3) | C7—C8 | 1.494 (4) |
S2—O3 | 1.439 (3) | C8—C9 | 1.328 (4) |
S2—N2 | 1.675 (3) | C9—C10 | 1.476 (4) |
| | | |
O2—S1—O1 | 120.27 (17) | N2—S2—C23 | 106.65 (14) |
O2—S1—N1 | 105.71 (14) | C1—N1—C8 | 115.3 (2) |
O1—S1—N1 | 107.04 (15) | C1—N1—S1 | 119.7 (2) |
N1—S1—C16 | 104.51 (14) | C8—N1—S1 | 114.7 (2) |
O4—S2—O3 | 119.72 (17) | C6—N2—C7 | 114.9 (2) |
O4—S2—N2 | 105.69 (15) | C6—N2—S2 | 117.5 (2) |
O3—S2—N2 | 106.46 (15) | C7—N2—S2 | 116.0 (2) |
| | | |
N1—C8—C9—C10 | 178.4 (3) | N1—S1—C16—C17 | 80.0 (3) |
N2—C7—C8—N1 | −53.5 (3) | N2—S2—C23—C24 | 81.5 (3) |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
C29—H29C···O2i | 0.96 | 2.85 | 3.321 (5) | 111.6 |
C20—H20···O4ii | 0.93 | 2.82 | 3.364 (4) | 118.8 |
C18—H18···O1iii | 0.93 | 2.72 | 3.388 (4) | 129.3 |
C17—H17···O1iii | 0.93 | 2.94 | 3.488 (4) | 118.9 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+2, −z+1; (iii) x, −y+3/2, z−1/2. |
Table 7. Isostructurality indices (see text for definition)
calculated for compounds (II), (III) and (IV). topStructures | Π | A | Ii(37)% | Iv% | Ivmax% |
(II)-(III) | 0.023 | 1.13 | 60.9 | 82.4 | 98.8 |
(II)-(IV) | 0.002 | 20.16 | -732.2 | 13.4 | 99.9 |
(III)-(IV) | 0.021 | 208.68 | -741.6 | 13.1 | 98.7 |
The quinoxaline system (I) and its derivatives have been successfully used in medicinal chemistry, particularly as synthetic precursors of antihypertensives, analgesics and neurotransmitter antagonists (Fuente et al., 2000; Kher et al., 1995; Manca et al., 1992). Many of these compounds also exhibit anticancer activity in vitro (Loriga et al., 1995). Although some preliminary information concerning the substituent directing effects of quinoxaline derivatives is available (Porter, 1984), to our knowledge, no X-ray crystal structure of N-substituted quinoxaline has been reported previously. As part of an ongoing program on the synthesis and characterization of quinoxaline-containing heterocyclic systems, we synthesized three 2-alkylidene-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxalines via palladium-catalyzed reaction between N-(prop-2-ynyl)-N,N'-1,2-phenylene-di-p-tosylamide and aryl iodides. To establish the regio-and stereospecificities of the reaction and to build up a hierarchy for such systems, X-ray analyses of 2-(4-methylbenzylidene)-1,4-di-p-tosyl- 1,2,3,4-tetrahydroquinoxaline, (II), 2-(4-methoxybenzylidene)-1,4-di- p-tosyl-1,2,3,4-tetrahydroquinoxaline, (III), and 2-(3-chlorobenzylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline, (IV), were undertaken. \sch
The title compounds (Figs. 1, 2 and 3) consist of a quinoxaline system with two p-tosyl and one substituted phenylmethylidene group at the 1, 4 and 2 positions, respectively. The E configurations of the molecules of (II), (III) and (IV) are established by the torsion angle N1—C8—C9—C10 of 174.7 (2) for (II), 176.8 (2) for (III) and 178.4 (3)° for (IV). As expected, the pyrazine ring B(N1—C1—C6—N2—C7—C8) fused to the phenyl ring A(C1—C6) in the compounds deviates significantly from planarity with the ring puckering parameters (Cremer & Pople, 1975) Q = 0.410 (2), 0.411 (2) and 0.404 (3) Å, θ = 133.2 (3), 134.8 (3) and 47.1 (4)°, and ϕ = 82.9 (4), 88.0 (4) and -90.8 (5)° for (II), (III) and (IV), respectively. The heterocyclic ring (C4N2) in all three compounds assumes a distorted chair conformation with the C1 and C7 atoms deviating by -0.117 (2) and 0.566 (2) Å in (II), -0.147 (2) and 0.560 (2) Å in (III), and -0.127 (3) and 0.541 (3) Å in (IV), respectively, from the least-squares plane through the remaining endocyclic atoms.
A comparision of the molecular geometries of (II), (III) and (IV) reveals the similarity of all bond lengths among the three compounds (Tables 1, 3 and 5). The two N atoms of the pyrazine ring (N1 and N2) with the sum of bond angles deviating significantly from 360° [346.8 (2) and 350.0 (2)° in (II), 345.4 (2) and 347.3 (2)° in (III), and 349.7 (2) and 348.4 (2)° in (IV)] indicate pyramidal distortions and occupy axial orientations with respect to their substituents (Tables 1, 3 and 5). The geometry at the S atoms in the compounds deviate significantly from that of regular tetrahedron, with the largest deviation in the O—S—O angle (Tables 1, 3 and 5). The widening of the O—S—O angle [119.7 (1)–120.3 (2)°] from the ideal tetrahedral value is presumably the result of the repulsive interaction between the short S═O bonds. The tosyl groups in (II), (III) and (IV) adopt folded conformations, in which the phenyl rings C [atoms: C17—C22 in (II) and (III); C16—C21 in (IV)] and D [atoms: C24—C29 in (II) and (III); C23—C28 in (IV)] shield the quinoxaline moiety (AB). The dihedral angles between A/C and A/D are similar in all the three structures [53.5 (1) and 55.8 (1)° in (II), 52.2 (1) and 53.2 (1)° in (III), 50.5 (1) and 57.1 (1)° in (IV)].
In compounds (II) and (IV), the phenyl rings C and D are almost parallel to each other [the dihedral angle C/D 2.3 (1)° in (II) and 7.7 (1)° in (IV)] whereas in compound (III) the C and D rings are inclined by 27.2 (1)°. This is probably to minimize the steric hindrance introduced by the methoxyphenyl group in (III). The S—O [1.417 (3)–1.439 (3) Å], S—C [1.749 (2)–1.762 (2) Å] and S—N [1.673 (2)–1.707 (2) Å] bond distances (Tables 1, 3 and 5) are consistent with the corresponding values reported in International Tables for X-ray Crystallography (Allen et al., 1992). The lack of π bonding in the branches among the phenyl rings precludes any possible π conjugation across the whole molecule in (II), (III) and (IV). The aromatic nature of the rings is therefore localized within the rings and on their direct substituents.
The identical space groups and the similarity of lattice parameters of (II), (III) and (IV) suggest some degree of isostructurality among the compounds. The results of calculation (Table 7) of the unit-cell similarity descriptor Π (Ka'lma'n et al., 1993), the asphericity index A (Rutherford, 1997), the isostructurality index Ii (Ka'lma'n et al., 1993) and the volumetric isostructurality index Iv (Fa'via'n & Ka'lma'n, 1999) reveal a high degree of isostructurality between compounds (II) and (III).
The volumetric index of isostructurality between compounds (II) and (III) amounts to 82% for the whole unit cell, with four molecules indicating significant packing similarity of the related structures. The large values of the asphericity index (A) and the isostructurality index, Ii(37), between (II)-(IV) and (III)-(IV) (Table 7) indicate that the compound (IV) is not isostructural with compound (II) or (III). This is probably a consequence of the exchange of cell axis lengths in compound (IV) compared to those in (II) and (III), and the different positions of substituents in the phenylmethylidene moiety [4-methyl in (II), 4-methoxy in (III) and 3-chloro in (IV)] of the structures.
In all three compounds [(II), (III) and (IV)] the crystal packing is stabilized by weak C—H···O intermolecular interactions (Tables 2, 4 and 6) involving the sulfonyl and methoxy O atoms.