Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104016014/de1249sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104016014/de1249Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104016014/de1249IIsup3.hkl |
CCDC references: 251309; 251310
The title compound was synthesized using the Gewald reaction (Gewald et al., 1966). For (I), m-cyanotoluidine was refluxed with cyclohexanone in the presence of sulfur, dimethylamine and ethanol at 313–323 K for 1 h. The resulting product was treated with 4-methoxybenzaldehyde in an equimolar ratio in the presence of ethanol, yielding (I). Compound (I) was recrystallized from a solution of N,N-dimethylformamide and ethanol (1:2) by slow evaporation. Crystals were obtained after four weeks and used for single-crystal data collection. For the preparation of (II), a similar procedure was followed using p-cyanotoluidine, and later 4-methylbenzaldehyde was added. The compound was purified and crystallized using the same procedure as for (I).
For (I), the methyl H atoms were constrained to an ideal geometry [C—H= 0.96 Å and Uiso(H)=1.5Ueq(C)] but were allowed to rotate freely about the C—C bond. All other H atoms were located from a difference Fourier map and their parameters were refined freely. For (II), the methyl H atoms were constrained to an ideal geometry [C—H= 0.96 Å and Uiso(H)=1.5Ueq(C)], but were allowed to rotate freely about the C—C bond. The H atoms of the cyclohexene ring (C—H = 0.93–0.97 Å) and phenyl atom H22 (C—H= 0.93 Å) were placed in idealized positions and constrained to ride on their parent atoms [Uiso(H)=1.2Ueq(C)]. All other H atoms were located from a difference Fourier map and their parameters were refined freely.
For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).
C24H24N2O2S | F(000) = 856 |
Mr = 404.52 | Dx = 1.297 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 265 reflections |
a = 8.184 (5) Å | θ = 1.5–26.4° |
b = 19.786 (11) Å | µ = 0.18 mm−1 |
c = 12.884 (7) Å | T = 293 K |
β = 96.994 (10)° | Block, yellow |
V = 2071 (2) Å3 | 0.33 × 0.28 × 0.14 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4130 independent reflections |
Radiation source: fine-focus sealed tube | 3501 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −10→10 |
Tmin = 0.927, Tmax = 0.975 | k = −24→24 |
15741 measured reflections | l = −15→15 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.83 | w = 1/[σ2(Fo2) + (0.0928P)2 + 0.6468P] where P = (Fo2 + 2Fc2)/3 |
4130 reflections | (Δ/σ)max < 0.001 |
336 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C24H24N2O2S | V = 2071 (2) Å3 |
Mr = 404.52 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.184 (5) Å | µ = 0.18 mm−1 |
b = 19.786 (11) Å | T = 293 K |
c = 12.884 (7) Å | 0.33 × 0.28 × 0.14 mm |
β = 96.994 (10)° |
Bruker SMART CCD area-detector diffractometer | 4130 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 3501 reflections with I > 2σ(I) |
Tmin = 0.927, Tmax = 0.975 | Rint = 0.016 |
15741 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.119 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.83 | Δρmax = 0.21 e Å−3 |
4130 reflections | Δρmin = −0.21 e Å−3 |
336 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.31834 (5) | 1.09418 (2) | 0.66002 (3) | 0.04950 (15) | |
N1 | 0.26063 (17) | 0.90929 (7) | 0.43964 (10) | 0.0431 (3) | |
N2 | 0.18060 (15) | 1.04305 (6) | 0.47033 (9) | 0.0408 (3) | |
O1 | 0.46000 (15) | 0.86340 (6) | 0.55710 (9) | 0.0559 (3) | |
O2 | −0.26098 (17) | 1.15638 (7) | 0.06445 (10) | 0.0671 (4) | |
C1 | 0.6648 (2) | 1.01489 (11) | 0.88427 (15) | 0.0631 (5) | |
C2 | 0.6072 (3) | 0.94259 (11) | 0.86943 (13) | 0.0613 (5) | |
C3 | 0.5615 (2) | 0.92420 (9) | 0.75396 (12) | 0.0470 (4) | |
C4 | 0.45939 (17) | 0.97889 (7) | 0.69551 (11) | 0.0397 (3) | |
C5 | 0.44588 (19) | 1.04090 (8) | 0.73918 (11) | 0.0450 (3) | |
C6 | 0.5293 (3) | 1.06461 (11) | 0.84331 (13) | 0.0587 (5) | |
C7 | 0.36684 (17) | 0.97358 (7) | 0.59301 (10) | 0.0374 (3) | |
C8 | 0.28054 (18) | 1.03229 (7) | 0.56420 (11) | 0.0395 (3) | |
C9 | 0.36850 (18) | 0.91046 (7) | 0.52908 (11) | 0.0390 (3) | |
C10 | 0.22774 (18) | 0.85674 (7) | 0.36638 (11) | 0.0398 (3) | |
C11 | 0.3089 (2) | 0.79443 (8) | 0.37271 (14) | 0.0511 (4) | |
C12 | 0.2640 (2) | 0.74679 (9) | 0.29545 (16) | 0.0605 (5) | |
C13 | 0.1442 (2) | 0.75931 (9) | 0.21289 (15) | 0.0590 (5) | |
C14 | 0.0628 (2) | 0.82092 (9) | 0.20525 (12) | 0.0509 (4) | |
C15 | 0.1051 (2) | 0.86859 (8) | 0.28341 (12) | 0.0453 (3) | |
C16 | −0.0675 (3) | 0.83685 (12) | 0.11502 (16) | 0.0750 (6) | |
C17 | 0.09460 (19) | 1.09680 (7) | 0.45389 (12) | 0.0431 (3) | |
C18 | −0.00336 (18) | 1.11176 (7) | 0.35466 (11) | 0.0411 (3) | |
C19 | −0.0968 (2) | 1.17075 (8) | 0.34186 (13) | 0.0492 (4) | |
C20 | −0.1848 (2) | 1.18775 (8) | 0.24655 (14) | 0.0521 (4) | |
C21 | −0.18149 (19) | 1.14495 (8) | 0.16207 (12) | 0.0486 (4) | |
C22 | −0.0914 (2) | 1.08498 (8) | 0.17380 (14) | 0.0530 (4) | |
C23 | −0.0046 (2) | 1.06899 (8) | 0.26805 (13) | 0.0469 (4) | |
C24 | −0.3444 (4) | 1.21875 (12) | 0.04489 (19) | 0.0945 (8) | |
H1N | 0.210 (2) | 0.9460 (10) | 0.4253 (13) | 0.048 (5)* | |
H1A | 0.695 (3) | 1.0242 (11) | 0.9556 (19) | 0.074 (6)* | |
H1B | 0.764 (3) | 1.0242 (10) | 0.8420 (17) | 0.069 (6)* | |
H2A | 0.510 (3) | 0.9373 (11) | 0.9035 (16) | 0.068 (6)* | |
H2B | 0.696 (3) | 0.9111 (11) | 0.8987 (18) | 0.080 (7)* | |
H3A | 0.501 (2) | 0.8822 (10) | 0.7473 (14) | 0.053 (5)* | |
H3B | 0.664 (2) | 0.9175 (9) | 0.7196 (14) | 0.051 (5)* | |
H6A | 0.444 (3) | 1.0669 (11) | 0.8892 (16) | 0.069 (6)* | |
H6B | 0.581 (3) | 1.1096 (12) | 0.8331 (17) | 0.078 (6)* | |
H11 | 0.394 (2) | 0.7860 (10) | 0.4288 (16) | 0.064 (5)* | |
H12 | 0.318 (2) | 0.7058 (11) | 0.2997 (15) | 0.065 (5)* | |
H13 | 0.116 (2) | 0.7257 (11) | 0.1608 (17) | 0.072 (6)* | |
H15 | 0.050 (2) | 0.9108 (9) | 0.2819 (14) | 0.048 (5)* | |
H16A | −0.0158 | 0.8529 | 0.0567 | 0.112* | |
H16B | −0.1401 | 0.8710 | 0.1360 | 0.112* | |
H16C | −0.1294 | 0.7967 | 0.0951 | 0.112* | |
H17 | 0.093 (2) | 1.1307 (10) | 0.5055 (14) | 0.056 (5)* | |
H19 | −0.099 (2) | 1.1988 (10) | 0.4030 (14) | 0.060 (5)* | |
H20 | −0.248 (2) | 1.2285 (10) | 0.2418 (15) | 0.066 (5)* | |
H22 | −0.094 (2) | 1.0551 (11) | 0.1102 (17) | 0.073 (6)* | |
H23 | 0.056 (2) | 1.0278 (10) | 0.2743 (15) | 0.061 (5)* | |
H24A | −0.4330 | 1.2217 | 0.0871 | 0.142* | |
H24B | −0.3877 | 1.2214 | −0.0277 | 0.142* | |
H24C | −0.2689 | 1.2554 | 0.0620 | 0.142* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0613 (3) | 0.0445 (2) | 0.0409 (2) | 0.00384 (17) | −0.00092 (17) | −0.01009 (15) |
N1 | 0.0533 (7) | 0.0358 (7) | 0.0379 (7) | 0.0037 (5) | −0.0041 (5) | −0.0046 (5) |
N2 | 0.0464 (7) | 0.0379 (6) | 0.0370 (6) | −0.0003 (5) | 0.0005 (5) | −0.0001 (5) |
O1 | 0.0697 (7) | 0.0483 (6) | 0.0456 (6) | 0.0140 (5) | −0.0104 (5) | −0.0045 (5) |
O2 | 0.0793 (9) | 0.0609 (8) | 0.0546 (7) | 0.0138 (6) | −0.0180 (6) | 0.0023 (6) |
C1 | 0.0641 (11) | 0.0803 (13) | 0.0409 (9) | −0.0018 (9) | −0.0103 (8) | −0.0133 (9) |
C2 | 0.0683 (12) | 0.0745 (13) | 0.0376 (9) | 0.0022 (10) | −0.0073 (8) | 0.0013 (8) |
C3 | 0.0496 (9) | 0.0527 (9) | 0.0367 (8) | −0.0012 (7) | −0.0031 (6) | 0.0010 (7) |
C4 | 0.0417 (7) | 0.0465 (8) | 0.0309 (7) | −0.0050 (6) | 0.0040 (5) | −0.0014 (6) |
C5 | 0.0487 (8) | 0.0524 (9) | 0.0336 (7) | −0.0027 (7) | 0.0033 (6) | −0.0048 (6) |
C6 | 0.0642 (11) | 0.0709 (12) | 0.0390 (8) | 0.0001 (9) | −0.0017 (8) | −0.0167 (8) |
C7 | 0.0407 (7) | 0.0395 (7) | 0.0317 (7) | −0.0037 (6) | 0.0035 (5) | −0.0005 (5) |
C8 | 0.0447 (8) | 0.0399 (7) | 0.0335 (7) | −0.0045 (6) | 0.0037 (6) | −0.0037 (5) |
C9 | 0.0440 (7) | 0.0395 (7) | 0.0332 (7) | −0.0034 (6) | 0.0034 (6) | 0.0001 (5) |
C10 | 0.0452 (8) | 0.0362 (7) | 0.0381 (7) | −0.0060 (6) | 0.0058 (6) | −0.0043 (6) |
C11 | 0.0558 (9) | 0.0428 (8) | 0.0531 (9) | 0.0010 (7) | 0.0001 (7) | −0.0054 (7) |
C12 | 0.0693 (11) | 0.0400 (9) | 0.0713 (12) | 0.0024 (8) | 0.0050 (9) | −0.0133 (8) |
C13 | 0.0710 (11) | 0.0495 (9) | 0.0565 (10) | −0.0117 (8) | 0.0074 (8) | −0.0208 (8) |
C14 | 0.0560 (9) | 0.0548 (9) | 0.0411 (8) | −0.0120 (7) | 0.0026 (7) | −0.0085 (7) |
C15 | 0.0524 (9) | 0.0412 (8) | 0.0409 (8) | −0.0020 (7) | 0.0007 (6) | −0.0039 (6) |
C16 | 0.0839 (14) | 0.0835 (14) | 0.0523 (10) | −0.0080 (11) | −0.0133 (10) | −0.0149 (10) |
C17 | 0.0493 (8) | 0.0377 (8) | 0.0418 (8) | −0.0027 (6) | 0.0036 (6) | −0.0036 (6) |
C18 | 0.0423 (7) | 0.0360 (7) | 0.0443 (8) | −0.0021 (6) | 0.0027 (6) | 0.0003 (6) |
C19 | 0.0560 (9) | 0.0398 (8) | 0.0504 (9) | 0.0034 (7) | 0.0006 (7) | −0.0056 (7) |
C20 | 0.0560 (9) | 0.0403 (8) | 0.0578 (10) | 0.0089 (7) | −0.0021 (7) | 0.0005 (7) |
C21 | 0.0468 (8) | 0.0461 (9) | 0.0501 (9) | 0.0004 (6) | −0.0047 (7) | 0.0027 (7) |
C22 | 0.0603 (10) | 0.0474 (9) | 0.0483 (9) | 0.0051 (7) | −0.0054 (7) | −0.0075 (7) |
C23 | 0.0523 (9) | 0.0376 (8) | 0.0491 (9) | 0.0065 (7) | −0.0016 (7) | −0.0017 (6) |
C24 | 0.124 (2) | 0.0772 (15) | 0.0719 (14) | 0.0388 (14) | −0.0281 (14) | 0.0094 (11) |
S1—C5 | 1.7268 (17) | C23—C22 | 1.367 (2) |
S1—C8 | 1.7397 (16) | C23—H23 | 0.95 (2) |
N1—C9 | 1.3638 (19) | C5—C6 | 1.504 (2) |
N1—C10 | 1.4080 (19) | C3—C2 | 1.533 (2) |
N1—H1N | 0.844 (19) | C3—H3B | 1.005 (19) |
O1—C9 | 1.2215 (18) | C3—H3A | 0.967 (19) |
N2—C17 | 1.279 (2) | C22—H22 | 1.01 (2) |
N2—C8 | 1.3914 (19) | C13—C12 | 1.379 (3) |
C7—C8 | 1.386 (2) | C13—C14 | 1.387 (3) |
C7—C4 | 1.444 (2) | C13—H13 | 0.95 (2) |
C7—C9 | 1.497 (2) | C11—C12 | 1.387 (2) |
C18—C19 | 1.394 (2) | C11—H11 | 0.953 (19) |
C18—C23 | 1.400 (2) | C1—C2 | 1.511 (3) |
C18—C17 | 1.454 (2) | C1—C6 | 1.528 (3) |
C4—C5 | 1.360 (2) | C1—H1B | 1.05 (2) |
C4—C3 | 1.511 (2) | C1—H1A | 0.94 (2) |
C10—C15 | 1.394 (2) | C14—C16 | 1.512 (3) |
C10—C11 | 1.398 (2) | C6—H6A | 0.97 (2) |
C17—H17 | 0.946 (19) | C6—H6B | 1.00 (2) |
C19—C20 | 1.387 (2) | C16—H16A | 0.9600 |
C19—H19 | 0.967 (19) | C16—H16B | 0.9600 |
O2—C21 | 1.363 (2) | C16—H16C | 0.9600 |
O2—C24 | 1.418 (2) | C2—H2A | 0.96 (2) |
C21—C20 | 1.382 (2) | C2—H2B | 1.00 (2) |
C21—C22 | 1.395 (2) | C12—H12 | 0.92 (2) |
C15—C14 | 1.392 (2) | C24—H24A | 0.9600 |
C15—H15 | 0.947 (17) | C24—H24B | 0.9600 |
C20—H20 | 0.95 (2) | C24—H24C | 0.9600 |
C5—S1—C8 | 91.83 (8) | C4—C3—H3A | 109.0 (11) |
C9—N1—C10 | 129.07 (13) | C2—C3—H3A | 110.6 (11) |
C9—N1—H1N | 114.8 (12) | H3B—C3—H3A | 107.2 (15) |
C10—N1—H1N | 116.1 (12) | C23—C22—C21 | 120.24 (15) |
C17—N2—C8 | 121.65 (13) | C23—C22—H22 | 123.0 (12) |
C8—C7—C4 | 112.17 (12) | C21—C22—H22 | 116.8 (12) |
C8—C7—C9 | 126.17 (12) | C12—C13—C14 | 120.20 (15) |
C4—C7—C9 | 121.67 (13) | C12—C13—H13 | 120.5 (12) |
O1—C9—N1 | 123.17 (13) | C14—C13—H13 | 119.3 (12) |
O1—C9—C7 | 121.31 (13) | C12—C11—C10 | 118.36 (16) |
N1—C9—C7 | 115.51 (13) | C12—C11—H11 | 121.9 (12) |
C7—C8—N2 | 125.97 (12) | C10—C11—H11 | 119.7 (12) |
C7—C8—S1 | 111.04 (11) | C2—C1—C6 | 111.34 (16) |
N2—C8—S1 | 122.96 (11) | C2—C1—H1B | 110.5 (11) |
C19—C18—C23 | 117.46 (14) | C6—C1—H1B | 106.5 (11) |
C19—C18—C17 | 120.67 (14) | C2—C1—H1A | 110.6 (13) |
C23—C18—C17 | 121.84 (14) | C6—C1—H1A | 107.7 (13) |
C5—C4—C7 | 112.59 (13) | H1B—C1—H1A | 110.1 (17) |
C5—C4—C3 | 120.52 (14) | C13—C14—C15 | 117.97 (16) |
C7—C4—C3 | 126.89 (13) | C13—C14—C16 | 121.71 (16) |
C15—C10—C11 | 119.04 (14) | C15—C14—C16 | 120.32 (17) |
C15—C10—N1 | 116.80 (13) | C5—C6—C1 | 109.79 (15) |
C11—C10—N1 | 124.16 (14) | C5—C6—H6A | 106.2 (12) |
N2—C17—C18 | 123.26 (14) | C1—C6—H6A | 111.4 (12) |
N2—C17—H17 | 121.9 (11) | C5—C6—H6B | 108.3 (13) |
C18—C17—H17 | 114.8 (11) | C1—C6—H6B | 108.3 (13) |
C20—C19—C18 | 121.73 (15) | H6A—C6—H6B | 112.9 (18) |
C20—C19—H19 | 121.5 (11) | C14—C16—H16A | 109.5 |
C18—C19—H19 | 116.8 (11) | C14—C16—H16B | 109.5 |
C21—O2—C24 | 118.29 (15) | H16A—C16—H16B | 109.5 |
O2—C21—C20 | 124.91 (15) | C14—C16—H16C | 109.5 |
O2—C21—C22 | 115.32 (15) | H16A—C16—H16C | 109.5 |
C20—C21—C22 | 119.77 (15) | H16B—C16—H16C | 109.5 |
C14—C15—C10 | 122.22 (15) | C1—C2—C3 | 112.53 (16) |
C14—C15—H15 | 120.4 (11) | C1—C2—H2A | 107.9 (13) |
C10—C15—H15 | 117.4 (11) | C3—C2—H2A | 107.5 (13) |
C21—C20—C19 | 119.39 (15) | C1—C2—H2B | 110.1 (13) |
C21—C20—H20 | 121.9 (12) | C3—C2—H2B | 107.5 (14) |
C19—C20—H20 | 118.7 (12) | H2A—C2—H2B | 111.4 (18) |
C22—C23—C18 | 121.39 (15) | C13—C12—C11 | 122.19 (17) |
C22—C23—H23 | 118.8 (12) | C13—C12—H12 | 119.6 (12) |
C18—C23—H23 | 119.8 (12) | C11—C12—H12 | 118.2 (12) |
C4—C5—C6 | 126.84 (15) | O2—C24—H24A | 109.5 |
C4—C5—S1 | 112.35 (11) | O2—C24—H24B | 109.5 |
C6—C5—S1 | 120.81 (13) | H24A—C24—H24B | 109.5 |
C4—C3—C2 | 111.63 (15) | O2—C24—H24C | 109.5 |
C4—C3—H3B | 108.4 (10) | H24A—C24—H24C | 109.5 |
C2—C3—H3B | 109.8 (10) | H24B—C24—H24C | 109.5 |
C10—N1—C9—O1 | 2.4 (3) | O2—C21—C20—C19 | −179.21 (16) |
C10—N1—C9—C7 | −176.79 (14) | C22—C21—C20—C19 | 0.7 (3) |
C8—C7—C9—O1 | 173.33 (15) | C18—C19—C20—C21 | 0.6 (3) |
C4—C7—C9—O1 | −6.8 (2) | C19—C18—C23—C22 | 1.3 (2) |
C8—C7—C9—N1 | −7.4 (2) | C17—C18—C23—C22 | −177.08 (16) |
C4—C7—C9—N1 | 172.38 (13) | C7—C4—C5—C6 | −178.14 (16) |
C4—C7—C8—N2 | 179.84 (13) | C3—C4—C5—C6 | 2.4 (3) |
C9—C7—C8—N2 | −0.3 (2) | C7—C4—C5—S1 | 1.31 (17) |
C4—C7—C8—S1 | 2.01 (15) | C3—C4—C5—S1 | −178.12 (12) |
C9—C7—C8—S1 | −178.15 (11) | C8—S1—C5—C4 | −0.14 (13) |
C17—N2—C8—C7 | 174.02 (15) | C8—S1—C5—C6 | 179.34 (15) |
C17—N2—C8—S1 | −8.4 (2) | C5—C4—C3—C2 | 13.0 (2) |
C5—S1—C8—C7 | −1.10 (12) | C7—C4—C3—C2 | −166.35 (15) |
C5—S1—C8—N2 | −179.01 (12) | C18—C23—C22—C21 | −0.1 (3) |
C8—C7—C4—C5 | −2.16 (18) | O2—C21—C22—C23 | 178.93 (16) |
C9—C7—C4—C5 | 177.99 (13) | C20—C21—C22—C23 | −1.0 (3) |
C8—C7—C4—C3 | 177.22 (15) | C15—C10—C11—C12 | 0.2 (2) |
C9—C7—C4—C3 | −2.6 (2) | N1—C10—C11—C12 | 179.68 (16) |
C9—N1—C10—C15 | 177.45 (15) | C12—C13—C14—C15 | −0.6 (3) |
C9—N1—C10—C11 | −2.0 (3) | C12—C13—C14—C16 | 179.09 (19) |
C8—N2—C17—C18 | 176.09 (13) | C10—C15—C14—C13 | 1.5 (3) |
C19—C18—C17—N2 | 178.99 (15) | C10—C15—C14—C16 | −178.16 (17) |
C23—C18—C17—N2 | −2.7 (2) | C4—C5—C6—C1 | 13.2 (3) |
C23—C18—C19—C20 | −1.6 (2) | S1—C5—C6—C1 | −166.24 (14) |
C17—C18—C19—C20 | 176.81 (15) | C2—C1—C6—C5 | −43.9 (2) |
C24—O2—C21—C20 | 4.7 (3) | C6—C1—C2—C3 | 62.1 (2) |
C24—O2—C21—C22 | −175.2 (2) | C4—C3—C2—C1 | −44.6 (2) |
C11—C10—C15—C14 | −1.3 (2) | C14—C13—C12—C11 | −0.5 (3) |
N1—C10—C15—C14 | 179.16 (15) | C10—C11—C12—C13 | 0.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.84 (2) | 2.03 (2) | 2.766 (2) | 145 (2) |
C13—H13···O1i | 0.95 (2) | 2.47 (2) | 3.385 (2) | 160 (2) |
Symmetry code: (i) x−1/2, −y+3/2, z−1/2. |
C24H24N2OS | Z = 2 |
Mr = 388.52 | F(000) = 412 |
Triclinic, P1 | Dx = 1.273 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.658 (7) Å | Cell parameters from 650 reflections |
b = 12.365 (11) Å | θ = 1.4–26.2° |
c = 12.569 (11) Å | µ = 0.18 mm−1 |
α = 108.490 (13)° | T = 293 K |
β = 103.745 (14)° | Block, yellow |
γ = 106.020 (13)° | 0.16 × 0.11 × 0.10 mm |
V = 1013.6 (16) Å3 |
Bruker SMART CCD area-detector diffractometer | 4011 independent reflections |
Radiation source: fine-focus sealed tube | 3363 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −9→9 |
Tmin = 0.936, Tmax = 0.983 | k = −14→15 |
10561 measured reflections | l = −15→15 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.192 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.87 | w = 1/[σ2(Fo2) + (0.1622P)2 + 0.394P] where P = (Fo2 + 2Fc2)/3 |
4011 reflections | (Δ/σ)max = 0.001 |
295 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
C24H24N2OS | γ = 106.020 (13)° |
Mr = 388.52 | V = 1013.6 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.658 (7) Å | Mo Kα radiation |
b = 12.365 (11) Å | µ = 0.18 mm−1 |
c = 12.569 (11) Å | T = 293 K |
α = 108.490 (13)° | 0.16 × 0.11 × 0.10 mm |
β = 103.745 (14)° |
Bruker SMART CCD area-detector diffractometer | 4011 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 3363 reflections with I > 2σ(I) |
Tmin = 0.936, Tmax = 0.983 | Rint = 0.018 |
10561 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.192 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.87 | Δρmax = 0.43 e Å−3 |
4011 reflections | Δρmin = −0.43 e Å−3 |
295 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 | ||
S2 | 0.20767 (9) | 0.92406 (5) | 1.13384 (5) | 0.0487 (2) | |
N1 | 0.0513 (3) | 0.85417 (18) | 0.73254 (16) | 0.0466 (5) | |
N2 | 0.0252 (3) | 0.75400 (16) | 0.89770 (16) | 0.0416 (4) | |
O1 | 0.2644 (3) | 1.05120 (16) | 0.80431 (16) | 0.0681 (6) | |
C1 | 0.4990 (6) | 1.2970 (3) | 1.2772 (3) | 0.0857 (11) | |
C2 | 0.5700 (5) | 1.3021 (3) | 1.1812 (3) | 0.0831 (10) | |
C3 | 0.4365 (3) | 1.2083 (2) | 1.0540 (2) | 0.0484 (5) | |
C4 | 0.3299 (3) | 1.08540 (19) | 1.05226 (19) | 0.0399 (5) | |
C5 | 0.3388 (3) | 1.0722 (2) | 1.15687 (19) | 0.0428 (5) | |
C6 | 0.4477 (4) | 1.1720 (2) | 1.2821 (2) | 0.0534 (6) | |
C7 | 0.2115 (3) | 0.97178 (19) | 0.94773 (18) | 0.0389 (5) | |
C8 | 0.1373 (3) | 0.87557 (19) | 0.97860 (18) | 0.0392 (5) | |
C9 | 0.1798 (3) | 0.9639 (2) | 0.82254 (19) | 0.0417 (5) | |
C10 | −0.0006 (3) | 0.8170 (2) | 0.60747 (18) | 0.0411 (5) | |
C11 | 0.0780 (4) | 0.8905 (2) | 0.5539 (2) | 0.0526 (6) | |
C12 | 0.0205 (4) | 0.8443 (3) | 0.4294 (2) | 0.0545 (6) | |
C13 | −0.1144 (4) | 0.7274 (2) | 0.3550 (2) | 0.0474 (5) | |
C14 | −0.1970 (4) | 0.6563 (2) | 0.4092 (2) | 0.0579 (6) | |
C15 | −0.1412 (4) | 0.6998 (2) | 0.5332 (2) | 0.0561 (6) | |
C16 | −0.1699 (4) | 0.6794 (3) | 0.2204 (2) | 0.0624 (7) | |
C17 | −0.0384 (3) | 0.6692 (2) | 0.9324 (2) | 0.0448 (5) | |
C18 | −0.1488 (3) | 0.54040 (19) | 0.8489 (2) | 0.0419 (5) | |
C19 | −0.2431 (4) | 0.4564 (2) | 0.8888 (2) | 0.0517 (6) | |
C20 | −0.3505 (4) | 0.3339 (2) | 0.8107 (2) | 0.0538 (6) | |
C21 | −0.3661 (3) | 0.2915 (2) | 0.6913 (2) | 0.0476 (5) | |
C22 | −0.2689 (4) | 0.3758 (2) | 0.6526 (2) | 0.0521 (6) | |
C23 | −0.1623 (3) | 0.4971 (2) | 0.7291 (2) | 0.0477 (5) | |
C24 | −0.4861 (4) | 0.1589 (2) | 0.6065 (3) | 0.0658 (7) | |
H1N | 0.003 (4) | 0.792 (3) | 0.762 (3) | 0.074 (9)* | |
H1A | 0.3847 | 1.3178 | 1.2667 | 0.103* | |
H1B | 0.5978 | 1.3584 | 1.3533 | 0.103* | |
H2A | 0.6927 | 1.2910 | 1.1980 | 0.100* | |
H2B | 0.5967 | 1.3841 | 1.1828 | 0.100* | |
H3A | 0.3429 | 1.2395 | 1.0217 | 0.058* | |
H3B | 0.5133 | 1.1979 | 1.0031 | 0.058* | |
H6A | 0.5655 | 1.1618 | 1.3184 | 0.064* | |
H6B | 0.3678 | 1.1658 | 1.3310 | 0.064* | |
H11 | 0.177 (4) | 0.971 (3) | 0.602 (3) | 0.060 (7)* | |
H12 | 0.082 (5) | 0.892 (3) | 0.397 (3) | 0.082 (10)* | |
H14 | −0.294 (5) | 0.577 (3) | 0.365 (3) | 0.077 (9)* | |
H15 | −0.198 (4) | 0.651 (3) | 0.573 (3) | 0.077 (9)* | |
H16A | −0.1903 | 0.7415 | 0.1944 | 0.094* | |
H16B | −0.2873 | 0.6068 | 0.1827 | 0.094* | |
H16C | −0.0672 | 0.6594 | 0.1984 | 0.094* | |
H17 | −0.013 (4) | 0.690 (3) | 1.009 (3) | 0.060 (8)* | |
H19 | −0.231 (4) | 0.487 (3) | 0.970 (3) | 0.062 (8)* | |
H20 | −0.407 (4) | 0.279 (3) | 0.837 (2) | 0.058 (7)* | |
H22 | −0.2760 | 0.3489 | 0.5728 | 0.062* | |
H23 | −0.093 (3) | 0.553 (2) | 0.697 (2) | 0.046 (6)* | |
H24A | −0.4912 | 0.1083 | 0.6507 | 0.099* | |
H24B | −0.4282 | 0.1331 | 0.5481 | 0.099* | |
H24C | −0.6155 | 0.1508 | 0.5664 | 0.099* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S2 | 0.0632 (4) | 0.0426 (4) | 0.0343 (3) | 0.0144 (3) | 0.0145 (3) | 0.0157 (2) |
N1 | 0.0557 (11) | 0.0405 (10) | 0.0347 (9) | 0.0076 (8) | 0.0159 (8) | 0.0142 (8) |
N2 | 0.0470 (10) | 0.0358 (9) | 0.0377 (9) | 0.0121 (8) | 0.0145 (8) | 0.0137 (8) |
O1 | 0.0954 (14) | 0.0432 (10) | 0.0416 (10) | −0.0014 (9) | 0.0189 (9) | 0.0156 (8) |
C1 | 0.120 (3) | 0.0515 (16) | 0.0517 (17) | 0.0113 (17) | 0.0175 (18) | 0.0073 (13) |
C2 | 0.102 (2) | 0.0461 (15) | 0.0576 (17) | −0.0087 (15) | 0.0216 (16) | 0.0049 (13) |
C3 | 0.0548 (13) | 0.0361 (11) | 0.0451 (12) | 0.0107 (10) | 0.0164 (10) | 0.0118 (10) |
C4 | 0.0408 (10) | 0.0372 (11) | 0.0380 (11) | 0.0148 (9) | 0.0133 (9) | 0.0117 (9) |
C5 | 0.0463 (11) | 0.0387 (11) | 0.0358 (11) | 0.0152 (9) | 0.0103 (9) | 0.0101 (9) |
C6 | 0.0622 (14) | 0.0477 (13) | 0.0352 (12) | 0.0167 (11) | 0.0084 (10) | 0.0089 (10) |
C7 | 0.0418 (10) | 0.0383 (11) | 0.0355 (10) | 0.0151 (9) | 0.0142 (8) | 0.0137 (9) |
C8 | 0.0436 (11) | 0.0362 (10) | 0.0351 (10) | 0.0136 (9) | 0.0146 (8) | 0.0124 (9) |
C9 | 0.0476 (11) | 0.0363 (10) | 0.0383 (11) | 0.0122 (9) | 0.0162 (9) | 0.0141 (9) |
C10 | 0.0483 (11) | 0.0390 (11) | 0.0354 (11) | 0.0146 (9) | 0.0168 (9) | 0.0149 (9) |
C11 | 0.0581 (14) | 0.0465 (13) | 0.0413 (12) | 0.0039 (11) | 0.0171 (11) | 0.0175 (10) |
C12 | 0.0627 (15) | 0.0585 (15) | 0.0432 (13) | 0.0138 (12) | 0.0238 (11) | 0.0262 (12) |
C13 | 0.0576 (13) | 0.0524 (13) | 0.0365 (11) | 0.0253 (11) | 0.0195 (10) | 0.0179 (10) |
C14 | 0.0777 (17) | 0.0410 (13) | 0.0398 (12) | 0.0119 (12) | 0.0170 (12) | 0.0099 (10) |
C15 | 0.0777 (17) | 0.0385 (12) | 0.0415 (12) | 0.0086 (11) | 0.0209 (12) | 0.0155 (10) |
C16 | 0.0782 (17) | 0.0725 (18) | 0.0359 (12) | 0.0302 (14) | 0.0209 (12) | 0.0198 (12) |
C17 | 0.0537 (12) | 0.0422 (12) | 0.0385 (12) | 0.0153 (10) | 0.0184 (10) | 0.0177 (10) |
C18 | 0.0462 (11) | 0.0384 (11) | 0.0419 (11) | 0.0137 (9) | 0.0166 (9) | 0.0187 (9) |
C19 | 0.0630 (14) | 0.0471 (13) | 0.0492 (13) | 0.0164 (11) | 0.0250 (12) | 0.0252 (11) |
C20 | 0.0582 (14) | 0.0427 (12) | 0.0627 (15) | 0.0116 (11) | 0.0260 (12) | 0.0277 (12) |
C21 | 0.0433 (11) | 0.0384 (11) | 0.0554 (14) | 0.0125 (9) | 0.0132 (10) | 0.0182 (10) |
C22 | 0.0637 (15) | 0.0446 (13) | 0.0423 (13) | 0.0150 (11) | 0.0170 (11) | 0.0171 (11) |
C23 | 0.0581 (13) | 0.0392 (11) | 0.0465 (12) | 0.0133 (10) | 0.0211 (10) | 0.0212 (10) |
C24 | 0.0603 (15) | 0.0425 (13) | 0.0729 (18) | 0.0053 (11) | 0.0136 (13) | 0.0166 (13) |
S2—C5 | 1.720 (3) | C5—C6 | 1.507 (3) |
S2—C8 | 1.743 (3) | C11—C12 | 1.391 (4) |
N2—C17 | 1.279 (3) | C11—H11 | 0.96 (3) |
N2—C8 | 1.391 (3) | C12—H12 | 0.91 (3) |
N1—C9 | 1.360 (3) | C15—C14 | 1.387 (4) |
N1—C10 | 1.409 (3) | C15—H15 | 0.97 (3) |
N1—H1N | 0.97 (3) | C23—C22 | 1.369 (3) |
O1—C9 | 1.216 (3) | C23—H23 | 1.00 (3) |
C9—C7 | 1.501 (3) | C14—H14 | 0.94 (3) |
C7—C8 | 1.383 (3) | C19—C20 | 1.386 (4) |
C7—C4 | 1.443 (3) | C19—H19 | 0.94 (3) |
C18—C19 | 1.394 (3) | C22—H22 | 0.930 |
C18—C23 | 1.396 (3) | C20—H20 | 0.90 (3) |
C18—C17 | 1.459 (3) | C24—H24A | 0.9600 |
C10—C11 | 1.386 (3) | C24—H24B | 0.9600 |
C10—C15 | 1.390 (3) | C24—H24C | 0.9600 |
C17—H17 | 0.87 (3) | C16—H16A | 0.9600 |
C21—C20 | 1.386 (4) | C16—H16B | 0.9600 |
C21—C22 | 1.394 (4) | C16—H16C | 0.9600 |
C21—C24 | 1.505 (4) | C6—C1 | 1.511 (4) |
C4—C5 | 1.364 (3) | C6—H6A | 0.9700 |
C4—C3 | 1.504 (3) | C6—H6B | 0.9700 |
C13—C12 | 1.375 (4) | C2—C1 | 1.449 (5) |
C13—C14 | 1.384 (4) | C2—H2A | 0.9700 |
C13—C16 | 1.509 (3) | C2—H2B | 0.9700 |
C3—C2 | 1.529 (4) | C1—H1A | 0.9700 |
C3—H3A | 0.9700 | C1—H1B | 0.9700 |
C3—H3B | 0.9700 | ||
C5—S2—C8 | 91.42 (10) | C14—C15—H15 | 122.3 (19) |
C17—N2—C8 | 122.0 (2) | C10—C15—H15 | 116.6 (19) |
C9—N1—C10 | 128.94 (19) | C22—C23—C18 | 120.7 (2) |
C9—N1—H1N | 112.9 (19) | C22—C23—H23 | 118.0 (14) |
C10—N1—H1N | 117.7 (19) | C18—C23—H23 | 121.3 (14) |
O1—C9—N1 | 122.9 (2) | C13—C14—C15 | 121.4 (2) |
N1—C9—C7 | 115.81 (18) | C13—C14—H14 | 123 (2) |
C8—C7—C4 | 111.83 (19) | C15—C14—H14 | 116 (2) |
C8—C7—C9 | 126.10 (19) | C20—C19—C18 | 120.6 (2) |
C4—C7—C9 | 122.06 (19) | C20—C19—H19 | 122.5 (17) |
C19—C18—C23 | 118.2 (2) | C18—C19—H19 | 116.9 (17) |
C19—C18—C17 | 119.7 (2) | C23—C22—C21 | 121.5 (2) |
C23—C18—C17 | 122.1 (2) | C23—C22—H22 | 119.4 |
C7—C8—N2 | 125.1 (2) | C21—C22—H22 | 119.4 |
C7—C8—S2 | 111.53 (16) | C21—C20—H20 | 118.3 (18) |
N2—C8—S2 | 123.30 (16) | C19—C20—H20 | 120.6 (18) |
C11—C10—C15 | 118.0 (2) | C21—C24—H24A | 109.5 |
C11—C10—N1 | 124.0 (2) | C21—C24—H24B | 109.5 |
C15—C10—N1 | 117.9 (2) | H24A—C24—H24B | 109.5 |
N2—C17—C18 | 122.5 (2) | C21—C24—H24C | 109.5 |
N2—C17—H17 | 118 (2) | H24A—C24—H24C | 109.5 |
C18—C17—H17 | 120 (2) | H24B—C24—H24C | 109.5 |
C20—C21—C22 | 117.9 (2) | C13—C16—H16A | 109.5 |
C20—C21—C24 | 120.8 (2) | C13—C16—H16B | 109.5 |
C22—C21—C24 | 121.3 (2) | H16A—C16—H16B | 109.5 |
C5—C4—C7 | 112.5 (2) | C13—C16—H16C | 109.5 |
C5—C4—C3 | 120.6 (2) | H16A—C16—H16C | 109.5 |
C7—C4—C3 | 127.0 (2) | H16B—C16—H16C | 109.5 |
C12—C13—C14 | 116.9 (2) | C5—C6—C1 | 109.6 (2) |
C12—C13—C16 | 121.3 (2) | C5—C6—H6A | 109.7 |
C14—C13—C16 | 121.7 (2) | C1—C6—H6A | 109.7 |
C4—C3—C2 | 111.6 (2) | C5—C6—H6B | 109.7 |
C4—C3—H3A | 109.3 | C1—C6—H6B | 109.7 |
C2—C3—H3A | 109.3 | H6A—C6—H6B | 108.2 |
C4—C3—H3B | 109.3 | C1—C2—C3 | 116.7 (3) |
C2—C3—H3B | 109.3 | C1—C2—H2A | 108.1 |
H3A—C3—H3B | 108.0 | C3—C2—H2A | 108.1 |
C4—C5—C6 | 126.5 (2) | C1—C2—H2B | 108.1 |
C4—C5—S2 | 112.72 (17) | C3—C2—H2B | 108.1 |
C6—C5—S2 | 120.81 (18) | H2A—C2—H2B | 107.3 |
C10—C11—C12 | 119.8 (2) | C2—C1—C6 | 113.1 (3) |
C10—C11—H11 | 120.6 (17) | C2—C1—H1A | 109.0 |
C12—C11—H11 | 119.5 (17) | C6—C1—H1A | 109.0 |
C13—C12—C11 | 122.8 (2) | C2—C1—H1B | 109.0 |
C13—C12—H12 | 119 (2) | C6—C1—H1B | 109.0 |
C11—C12—H12 | 118 (2) | H1A—C1—H1B | 107.8 |
C14—C15—C10 | 121.1 (2) | ||
C10—N1—C9—O1 | 3.9 (4) | C3—C4—C5—S2 | −179.64 (16) |
C10—N1—C9—C7 | −176.4 (2) | C8—S2—C5—C4 | 0.22 (17) |
O1—C9—C7—C8 | −173.7 (2) | C8—S2—C5—C6 | −179.91 (19) |
N1—C9—C7—C8 | 6.5 (3) | C15—C10—C11—C12 | −2.4 (4) |
O1—C9—C7—C4 | 5.4 (3) | N1—C10—C11—C12 | 178.5 (2) |
N1—C9—C7—C4 | −174.32 (19) | C14—C13—C12—C11 | 1.6 (4) |
C4—C7—C8—N2 | −177.06 (18) | C16—C13—C12—C11 | −178.6 (2) |
C9—C7—C8—N2 | 2.2 (3) | C10—C11—C12—C13 | 0.6 (4) |
C4—C7—C8—S2 | 1.1 (2) | C11—C10—C15—C14 | 1.9 (4) |
C9—C7—C8—S2 | −179.64 (16) | N1—C10—C15—C14 | −178.9 (2) |
C17—N2—C8—C7 | 179.7 (2) | C19—C18—C23—C22 | 1.3 (4) |
C17—N2—C8—S2 | 1.8 (3) | C17—C18—C23—C22 | −179.3 (2) |
C5—S2—C8—C7 | −0.77 (17) | C12—C13—C14—C15 | −2.1 (4) |
C5—S2—C8—N2 | 177.44 (18) | C16—C13—C14—C15 | 178.2 (3) |
C9—N1—C10—C11 | 0.8 (4) | C10—C15—C14—C13 | 0.3 (4) |
C9—N1—C10—C15 | −178.3 (2) | C23—C18—C19—C20 | −1.3 (4) |
C8—N2—C17—C18 | −177.23 (19) | C17—C18—C19—C20 | 179.4 (2) |
C19—C18—C17—N2 | −168.7 (2) | C18—C23—C22—C21 | −0.5 (4) |
C23—C18—C17—N2 | 12.0 (4) | C20—C21—C22—C23 | −0.5 (4) |
C8—C7—C4—C5 | −1.0 (3) | C24—C21—C22—C23 | 178.8 (2) |
C9—C7—C4—C5 | 179.75 (18) | C22—C21—C20—C19 | 0.6 (4) |
C8—C7—C4—C3 | 179.05 (19) | C24—C21—C20—C19 | −178.7 (2) |
C9—C7—C4—C3 | −0.2 (3) | C18—C19—C20—C21 | 0.3 (4) |
C5—C4—C3—C2 | 8.4 (3) | C4—C5—C6—C1 | 16.4 (4) |
C7—C4—C3—C2 | −171.6 (2) | S2—C5—C6—C1 | −163.5 (2) |
C7—C4—C5—C6 | −179.5 (2) | C4—C3—C2—C1 | −37.1 (4) |
C3—C4—C5—C6 | 0.5 (3) | C3—C2—C1—C6 | 56.6 (5) |
C7—C4—C5—S2 | 0.4 (2) | C5—C6—C1—C2 | −43.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.98 (4) | 1.89 (4) | 2.752 (4) | 146 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C24H24N2O2S | C24H24N2OS |
Mr | 404.52 | 388.52 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.184 (5), 19.786 (11), 12.884 (7) | 7.658 (7), 12.365 (11), 12.569 (11) |
α, β, γ (°) | 90, 96.994 (10), 90 | 108.490 (13), 103.745 (14), 106.020 (13) |
V (Å3) | 2071 (2) | 1013.6 (16) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.18 | 0.18 |
Crystal size (mm) | 0.33 × 0.28 × 0.14 | 0.16 × 0.11 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.927, 0.975 | 0.936, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15741, 4130, 3501 | 10561, 4011, 3363 |
Rint | 0.016 | 0.018 |
(sin θ/λ)max (Å−1) | 0.625 | 0.625 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.119, 0.83 | 0.057, 0.192, 0.87 |
No. of reflections | 4130 | 4011 |
No. of parameters | 336 | 295 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.21 | 0.43, −0.43 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.84 (2) | 2.03 (2) | 2.766 (2) | 145 (2) |
C13—H13···O1i | 0.95 (2) | 2.47 (2) | 3.385 (2) | 160 (2) |
Symmetry code: (i) x−1/2, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.98 (4) | 1.89 (4) | 2.752 (4) | 146 (3) |
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The design of compounds that possess important pharmacological properties, such as antibacterial, anticancer, anti-inflamatory and anti-toxic activities, is an important area of research, and Schiff bases (Pellis & West, 1968; Cohen et al., 1977; Csaszar & Morvay, 1983; Lakshmi et al., 1985) and their thiophene derivatives (El Meghraby et al., 1984; Dzhurayev et al., 1992; Gewald et al., 1966) have been found to exhibit these activities. In this context, sulfur-containing Schiff bases are most effective. We have already reported the crystal structures of biologically active thiophene-3-carboxamide derivatives (Vasu et al., 2003). In view of the medicinal application of such classes of compounds, single-crystal studies have been carried out.
The two compounds 2-{[1(E)-4-methoxyphenyl)methylene]amino)-N-(3-methylphenyl) −4,5,6,7-tetrahydro-1-benzothiophene-3-carboxamide, C24H24N2O2S1, (I), and 2-{[1(E)-4-methylphenyl)methylene]amino}-N-(4-methylphenyl)-4,5,6,7- tetrahydro-1-benzothiophene-3-carboxamide, C24H24N2O1S1, (II), belong to the same series of compounds and show antibacterial and antifungal activities (Mohan & Saravanan, 2002, 2003).
Compounds (I) and (II) contain three different structural moieties, which will be discussed separately (Figs.1 and 2). The thiophene ring exhibits normal geometry and is planar, with a maximum deviation of 0.012 (1) and 0.007 (3) Å for atom C7 in (I) and (II), respectively. The six-membered cyclohexene ring adopts a half-chair conformation, with atoms C1 and C2 deviating +0.316 (2) and −0.340 (2) Å in (I), and +0.337 (5) and −0.250 (4) Å in (II), respectively.
The m-toluidine group in (I) and the p-toluidine moiety in (II) are coplanar with the plane of the thiophene ring, as indicated by the C9—N1—C10—C15 torsion angles [177.5 (2) and −178.3 (3)°, respectively]. The angle between the mean planes of the m-toluidine and thiophene rings is 8.2 (1)°, whereas those between the p-toluidine and thiophene rings is 9.7 (1)°. The dihedral angle between the planes containing the p-methoxyphenyl group and the thiophene ring is 13.03 (5)°, which implies that the whole molecule is planar. The corresponding dihedral angle between the planes passing through the p-toluidine group attached to the imine moiety and thiophene ring is 14.3 (1)°.
The C—N bond lengths in the carboxamide and imine moieties are significantly different; the C9—N1 and C8—N2 bond lengths are 1.364 (2) and 1.391 (2) Å in (I), and the corresponding bond lengths are 1.360 (2) and 1.391 (3) Å in (II), respectively, indicating that the electronic and steric environment around these moieties is different. The C23—C18—C19 [117.5 (1)°] and C22—C21—C20 [117.9 (3)°] angles in (I) and (II) deviate significantly from the ideal value of 120° for a phenyl ring, This deviation is due to the electron-donating resonance effect of the methoxy group attached to atom C21 in (I) and the electron-donating inductive effect of the methyl group in (II).
There are no significant intermolecular hydrogen-bonding interactions in the packing of (II). An intramolecular N—H···N hydrogen-bonding interaction in each structure locks the molecule into a rigid pseudo-six-membered-ring conformation and removes the conformational flexibility. Hence the free NH group is not available for participation in intermolecular interactions. In (I), intermolecular C—H···O molecular chains running parallel to the crystallographic c axis further stabilize the packing of molecules in the crystal structure.
The packing characteristics reveal interesting features as regards the orientation of the molecules in the crystalline environment. In (I), the molecules held together by C—H···O molecular chains are related by the n-glide plane (1/2 + x,1/2 − y,1/2 + z), and this feature of molecular recognition essentially steers the molecules to pack in a monoclinic centrosymmetric environment. In (II), replacement of the H atom that participates in an intermolecular interaction in (I) by a methyl group eliminates the formation of chains. This difference leads to remarkable differences in the crystal packing, and the molecules in (II) are stacked in layers that are parallel to each other and related by a center of inversion.