Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702377X/lh2388sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702377X/lh2388Isup2.hkl |
CCDC reference: 651510
The title compound was obtained by means of one pot method of synthesis, applying Thorpe-Ziegler-cyclization. The reaction was carried out in the methanol solution of potassium hydroxide (1.99 mmol), in which arylsulfonylacetonitrile (1.66 mmol) and arylisothiocyanate (1.66 mmol) were dissolved. The solution was treated with phenacylbromide (1.99 mmol) and potassium hydroxide (1.99 mmol). At reation completion the solid was acidified using mineral acid. Crystals for X-ray diffraction study were obtained by evaporation of methanol -dimethyl formamide solution (Vlasenko et al., 2005).
All hydrogen atoms were located from electron density difference maps but were included in the refinement in the riding motion approximation with C—H = 0.93–0.96Å and Uiso constrained to be 1.5 times the Ueq of the carrier atom for the methyl groups and 1.2 times Ueq of the carrier atom for the other atoms. The hydrogen atoms which are take part in the formation of hydrogen bonds were refined isotropically.
Thiophene is a very important pharmacophore in many biologically active compounds. Thiophene derivatives are used as antibiotics, anaesthetics, antiparasitics, resolvents, antihelmintic drugs, anticholinergic drugs, antiulcer agents, antihistamines, antitussives (Patent USA, 2000, Kovalenko & Victorova, 2005), therefore investigation of their molecular structure may provide useful information for the understanding of mechanisms of biological activity. In this paper we report the molecular and crystal structure of 2-aroyl-3-amino-4-arylsulfonyl-5-arylamino-thiophene (Fig.1). The carbonyl group is essentially coplanar with the thiophene ring (the C1—C4—C5—O3 torsion angle is 3.1 (4)°). Such a conformation of this group is stabilized by the weak intramolecular hydrogen bond N1—H1NA···O3 H···O 2.06 Å, N—H···O 141°. Atoms N1 and N2 have a planar configuration, the sum of the bond angles, centered at these atoms are 360° in both cases. The phenyl substituent at atom C5 atom is rotated with respect to the C4—C5 bond (the C4—C5—C6—C7 torsion angle is -47.9 (3) °). Such orientation of the phenyl ring indicates an interaction between phenyl ring and atom S1 (the short intramolecular contact C7···S1 is 2.71Å [van der Waals radii sum is 3.01 Å; Zefirov & Zorky (1995)]. The phenyl substituent at the S2 atom has an almost orthogonal orientation relative to the thiophene ring (the C20—S2—C2—C3 torsion angle is -84.4 (2) °) and with respect to the C2—S2 bond (the C2—S2—C20—C25 torsion angle is -83.3 (2)°). The conformation of sulfonyl group is stabilized by weak intramolecular hydrogen bonds N1—H1NB···O2 H···O 2.22 Å, N—H···O 124° and N2—H2NA···O1 H···O 2.25 Å, N—H···O 130°, respectively. The dimethylphenylamino substituent adopts an sp-conformation relative to the C3—S1 bond (the S1—C3—N2—C12 torsion angle is -3.9 (4) °) and it is rotated with respect to the C3—N2 bond (the C3—N2—C12—C17 torsion angle is 64.5 (4) °). The most interesting feature of the structure is difference in the S—C bond lengths within thiophene ring. The C4—S1 bond (1.758 (2) Å) is significantly longer than the S1—C3 bond (1.719 (2) Å) and the reported mean value is 1.712 Å (Bürgi & Dunitz, 1994). Comparison of bond lengths within the thiophene ring in the title compound and other 2,5-disubstituted thiophene compounds (Apinitis et al., 1984; Xu et al., 2004) indicates that elongation of the S1—C4 bond is observed when an electron-withdrawing substituent is at atom C4. This may lead to considerable asymmetry in conjugation interactions within the C—S—C fragment of thiophene ring. In the crystal structure, molecules of title compound form centrosymmetric dimers due to intermolecular hydrogen bond N1—H1NB···O2' (symmetry code (') -x + 1, -y + 1, -z + 2) H···O' 2.19 Å, N—H···O' 142 °.
For a comparison of the Csp2—S bond lengths in other related crystal structures, see: Apinitis et al., (1984); Xu et al. (2004).
For related literature, see: Bürgi & Dunitz (1994); Kovalenko & Victorova (2005); Patent (2000); Vlasenko et al. (2005); Zefirov & Zorky (1995).
Data collection: P3 (Siemens,1989); cell refinement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. View of the molecular structure of (I) with atomic numbering. All atoms are shown with displacement ellipsoids drawn at the 50% probability level. |
C25H22N2O3S2 | Z = 2 |
Mr = 462.57 | F(000) = 484 |
Triclinic, P1 | Dx = 1.296 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.497 (3) Å | Cell parameters from 36 reflections |
b = 11.451 (3) Å | θ = 8–22° |
c = 11.863 (3) Å | µ = 0.25 mm−1 |
α = 65.65 (2)° | T = 293 K |
β = 69.654 (19)° | Block, colourless |
γ = 70.18 (2)° | 0.40 × 0.20 × 0.20 mm |
V = 1185.6 (6) Å3 |
Siemens P3/PC diffractometer | 3150 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
Detector resolution: 16.1827 pixels mm-1 | h = −11→12 |
θ–2θ scans | k = −12→13 |
4246 measured reflections | l = −13→14 |
4042 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0604P)2 + 0.2736P] where P = (Fo2 + 2Fc2)/3 |
4042 reflections | (Δ/σ)max = 0.001 |
322 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C25H22N2O3S2 | γ = 70.18 (2)° |
Mr = 462.57 | V = 1185.6 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.497 (3) Å | Mo Kα radiation |
b = 11.451 (3) Å | µ = 0.25 mm−1 |
c = 11.863 (3) Å | T = 293 K |
α = 65.65 (2)° | 0.40 × 0.20 × 0.20 mm |
β = 69.654 (19)° |
Siemens P3/PC diffractometer | 3150 reflections with I > 2σ(I) |
4246 measured reflections | Rint = 0.048 |
4042 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.25 e Å−3 |
4042 reflections | Δρmin = −0.31 e Å−3 |
322 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 | 0.47589 (6) | 0.72106 (6) | 0.46973 (5) | 0.04259 (18) | |
S2 | 0.30992 (6) | 0.69038 (6) | 0.85957 (5) | 0.03452 (16) | |
N1 | 0.6086 (3) | 0.5073 (2) | 0.7787 (2) | 0.0498 (6) | |
H1NA | 0.681 (3) | 0.473 (3) | 0.750 (3) | 0.046 (8)* | |
H1NB | 0.575 (3) | 0.501 (3) | 0.866 (3) | 0.070 (9)* | |
N2 | 0.2320 (2) | 0.8339 (2) | 0.5927 (2) | 0.0473 (6) | |
H2NA | 0.177 (3) | 0.849 (3) | 0.653 (3) | 0.047 (8)* | |
O1 | 0.16388 (16) | 0.73500 (19) | 0.86151 (15) | 0.0497 (5) | |
O2 | 0.35524 (18) | 0.57316 (16) | 0.95816 (14) | 0.0443 (4) | |
O3 | 0.81054 (17) | 0.46304 (18) | 0.57554 (16) | 0.0525 (5) | |
C1 | 0.5382 (2) | 0.5893 (2) | 0.6897 (2) | 0.0329 (5) | |
C2 | 0.4011 (2) | 0.6711 (2) | 0.71376 (19) | 0.0332 (5) | |
C3 | 0.3543 (2) | 0.7472 (2) | 0.6033 (2) | 0.0350 (5) | |
C4 | 0.5941 (2) | 0.6049 (2) | 0.5602 (2) | 0.0355 (5) | |
C5 | 0.7306 (2) | 0.5429 (2) | 0.5067 (2) | 0.0365 (5) | |
C6 | 0.7839 (2) | 0.5752 (2) | 0.3652 (2) | 0.0347 (5) | |
C7 | 0.7075 (3) | 0.5789 (2) | 0.2888 (2) | 0.0420 (6) | |
H7 | 0.6175 | 0.5651 | 0.3244 | 0.052 (8)* | |
C8 | 0.7649 (3) | 0.6031 (3) | 0.1598 (2) | 0.0517 (7) | |
H8 | 0.7140 | 0.6038 | 0.1091 | 0.051 (7)* | |
C9 | 0.8971 (3) | 0.6262 (3) | 0.1057 (3) | 0.0547 (7) | |
H9 | 0.9347 | 0.6440 | 0.0184 | 0.067 (9)* | |
C10 | 0.9727 (3) | 0.6230 (3) | 0.1805 (3) | 0.0551 (7) | |
H10 | 1.0619 | 0.6388 | 0.1439 | 0.056 (8)* | |
C11 | 0.9177 (3) | 0.5966 (2) | 0.3100 (2) | 0.0466 (6) | |
H11 | 0.9706 | 0.5931 | 0.3605 | 0.064 (9)* | |
C12 | 0.1956 (2) | 0.9153 (2) | 0.4746 (2) | 0.0398 (6) | |
C13 | 0.1705 (3) | 1.0494 (3) | 0.4418 (3) | 0.0490 (6) | |
H13 | 0.1802 | 1.0854 | 0.4950 | 0.057 (8)* | |
C14 | 0.1303 (3) | 1.1318 (3) | 0.3284 (3) | 0.0559 (7) | |
C15 | 0.1194 (3) | 1.0741 (3) | 0.2517 (2) | 0.0522 (7) | |
H15 | 0.0926 | 1.1281 | 0.1762 | 0.090 (11)* | |
C16 | 0.1467 (3) | 0.9397 (3) | 0.2822 (2) | 0.0484 (6) | |
C17 | 0.1831 (3) | 0.8601 (3) | 0.3971 (2) | 0.0447 (6) | |
H17 | 0.1989 | 0.7691 | 0.4215 | 0.056 (8)* | |
C18 | 0.1001 (5) | 1.2791 (3) | 0.2929 (4) | 0.0915 (12) | |
H18B | 0.0676 | 1.3021 | 0.3690 | 0.17 (2)* | |
H18A | 0.0297 | 1.3198 | 0.2454 | 0.132 (17)* | |
H18C | 0.1838 | 1.3093 | 0.2418 | 0.17 (2)* | |
C19 | 0.1363 (5) | 0.8786 (4) | 0.1955 (4) | 0.0811 (11) | |
H19A | 0.0981 | 0.9464 | 0.1269 | 0.16 (2)* | |
H19C | 0.0765 | 0.8178 | 0.2432 | 0.19 (3)* | |
H19B | 0.2275 | 0.8326 | 0.1615 | 0.144 (19)* | |
C20 | 0.3623 (3) | 0.8199 (2) | 0.8620 (2) | 0.0411 (6) | |
C21 | 0.2846 (4) | 0.9460 (3) | 0.8255 (3) | 0.0666 (9) | |
H21 | 0.2015 | 0.9635 | 0.8038 | 0.086 (11)* | |
C22 | 0.3316 (6) | 1.0473 (4) | 0.8215 (4) | 0.0931 (13) | |
H22 | 0.2794 | 1.1334 | 0.7972 | 0.125 (16)* | |
C23 | 0.4522 (6) | 1.0221 (4) | 0.8525 (4) | 0.0916 (13) | |
H23 | 0.4838 | 1.0912 | 0.8473 | 0.116 (14)* | |
C24 | 0.5291 (4) | 0.8953 (4) | 0.8917 (4) | 0.0811 (10) | |
H24 | 0.6113 | 0.8788 | 0.9146 | 0.103 (13)* | |
C25 | 0.4848 (3) | 0.7929 (3) | 0.8970 (3) | 0.0599 (8) | |
H25 | 0.5362 | 0.7068 | 0.9237 | 0.071 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0381 (3) | 0.0532 (4) | 0.0214 (3) | 0.0055 (3) | −0.0114 (2) | −0.0074 (3) |
S2 | 0.0337 (3) | 0.0432 (3) | 0.0204 (3) | −0.0070 (2) | −0.0074 (2) | −0.0055 (2) |
N1 | 0.0429 (14) | 0.0621 (15) | 0.0295 (12) | 0.0092 (11) | −0.0175 (10) | −0.0107 (11) |
N2 | 0.0400 (12) | 0.0579 (14) | 0.0252 (10) | 0.0110 (10) | −0.0115 (9) | −0.0107 (10) |
O1 | 0.0325 (9) | 0.0755 (13) | 0.0309 (9) | −0.0087 (8) | −0.0057 (7) | −0.0127 (9) |
O2 | 0.0539 (10) | 0.0470 (10) | 0.0246 (8) | −0.0116 (8) | −0.0145 (7) | −0.0010 (7) |
O3 | 0.0383 (10) | 0.0603 (11) | 0.0418 (10) | 0.0065 (8) | −0.0169 (8) | −0.0092 (9) |
C1 | 0.0341 (12) | 0.0349 (12) | 0.0264 (11) | −0.0047 (9) | −0.0127 (9) | −0.0051 (9) |
C2 | 0.0373 (12) | 0.0362 (12) | 0.0232 (11) | −0.0057 (9) | −0.0117 (9) | −0.0057 (9) |
C3 | 0.0357 (12) | 0.0400 (12) | 0.0248 (11) | −0.0035 (10) | −0.0101 (9) | −0.0083 (10) |
C4 | 0.0336 (12) | 0.0413 (13) | 0.0265 (11) | −0.0012 (10) | −0.0132 (9) | −0.0076 (10) |
C5 | 0.0343 (12) | 0.0382 (12) | 0.0351 (12) | −0.0048 (10) | −0.0123 (10) | −0.0098 (10) |
C6 | 0.0342 (12) | 0.0315 (11) | 0.0336 (12) | −0.0039 (9) | −0.0065 (10) | −0.0105 (10) |
C7 | 0.0418 (14) | 0.0473 (14) | 0.0403 (13) | −0.0136 (11) | −0.0067 (11) | −0.0180 (11) |
C8 | 0.0677 (18) | 0.0548 (16) | 0.0406 (14) | −0.0151 (13) | −0.0179 (13) | −0.0185 (13) |
C9 | 0.0657 (18) | 0.0517 (16) | 0.0369 (15) | −0.0149 (14) | −0.0010 (13) | −0.0135 (12) |
C10 | 0.0426 (15) | 0.0651 (18) | 0.0445 (15) | −0.0172 (13) | 0.0035 (12) | −0.0135 (14) |
C11 | 0.0368 (13) | 0.0521 (15) | 0.0470 (15) | −0.0066 (11) | −0.0096 (11) | −0.0161 (12) |
C12 | 0.0317 (12) | 0.0470 (14) | 0.0269 (11) | 0.0058 (10) | −0.0112 (9) | −0.0078 (10) |
C13 | 0.0435 (14) | 0.0503 (15) | 0.0478 (15) | 0.0006 (11) | −0.0157 (12) | −0.0164 (13) |
C14 | 0.0486 (16) | 0.0439 (15) | 0.0528 (17) | 0.0011 (12) | −0.0166 (13) | −0.0006 (13) |
C15 | 0.0424 (14) | 0.0574 (17) | 0.0352 (14) | 0.0009 (12) | −0.0178 (11) | 0.0020 (13) |
C16 | 0.0403 (14) | 0.0619 (17) | 0.0349 (13) | −0.0016 (12) | −0.0154 (11) | −0.0112 (12) |
C17 | 0.0422 (14) | 0.0439 (14) | 0.0363 (13) | 0.0034 (11) | −0.0148 (11) | −0.0083 (11) |
C18 | 0.111 (3) | 0.0471 (19) | 0.096 (3) | −0.003 (2) | −0.042 (3) | −0.0024 (19) |
C19 | 0.096 (3) | 0.096 (3) | 0.063 (2) | −0.008 (2) | −0.042 (2) | −0.030 (2) |
C20 | 0.0474 (14) | 0.0486 (14) | 0.0244 (11) | −0.0107 (11) | −0.0053 (10) | −0.0125 (10) |
C21 | 0.091 (2) | 0.0486 (17) | 0.0590 (19) | −0.0016 (15) | −0.0334 (17) | −0.0154 (14) |
C22 | 0.158 (4) | 0.048 (2) | 0.072 (2) | −0.020 (2) | −0.039 (3) | −0.0120 (17) |
C23 | 0.146 (4) | 0.085 (3) | 0.060 (2) | −0.068 (3) | −0.006 (2) | −0.022 (2) |
C24 | 0.079 (2) | 0.103 (3) | 0.084 (3) | −0.044 (2) | −0.008 (2) | −0.044 (2) |
C25 | 0.0550 (17) | 0.071 (2) | 0.0635 (19) | −0.0158 (15) | −0.0109 (15) | −0.0333 (16) |
S1—C3 | 1.719 (2) | C12—C17 | 1.371 (3) |
S1—C4 | 1.758 (2) | C12—C13 | 1.372 (4) |
S2—O2 | 1.4337 (17) | C13—C14 | 1.399 (4) |
S2—O1 | 1.4372 (17) | C13—H13 | 0.9300 |
S2—C2 | 1.726 (2) | C14—C15 | 1.377 (4) |
S2—C20 | 1.761 (3) | C14—C18 | 1.506 (4) |
N1—C1 | 1.340 (3) | C15—C16 | 1.376 (4) |
N1—H1NA | 0.76 (3) | C15—H15 | 0.9300 |
N1—H1NB | 0.95 (3) | C16—C17 | 1.391 (3) |
N2—C3 | 1.340 (3) | C16—C19 | 1.511 (4) |
N2—C12 | 1.425 (3) | C17—H17 | 0.9300 |
N2—H2NA | 0.78 (3) | C18—H18B | 0.9600 |
O3—C5 | 1.244 (3) | C18—H18A | 0.9600 |
C1—C4 | 1.398 (3) | C18—H18C | 0.9600 |
C1—C2 | 1.432 (3) | C19—H19A | 0.9600 |
C2—C3 | 1.391 (3) | C19—H19C | 0.9600 |
C4—C5 | 1.418 (3) | C19—H19B | 0.9600 |
C5—C6 | 1.497 (3) | C20—C21 | 1.367 (4) |
C6—C7 | 1.385 (3) | C20—C25 | 1.385 (4) |
C6—C11 | 1.386 (3) | C21—C22 | 1.384 (5) |
C7—C8 | 1.380 (3) | C21—H21 | 0.9300 |
C7—H7 | 0.9300 | C22—C23 | 1.345 (6) |
C8—C9 | 1.378 (4) | C22—H22 | 0.9300 |
C8—H8 | 0.9300 | C23—C24 | 1.373 (6) |
C9—C10 | 1.365 (4) | C23—H23 | 0.9300 |
C9—H9 | 0.9300 | C24—C25 | 1.372 (4) |
C10—C11 | 1.380 (4) | C24—H24 | 0.9300 |
C10—H10 | 0.9300 | C25—H25 | 0.9300 |
C11—H11 | 0.9300 | ||
C3—S1—C4 | 92.08 (11) | C17—C12—N2 | 120.3 (2) |
O2—S2—O1 | 118.85 (11) | C13—C12—N2 | 118.6 (2) |
O2—S2—C2 | 108.58 (11) | C12—C13—C14 | 119.8 (3) |
O1—S2—C2 | 108.25 (10) | C12—C13—H13 | 120.1 |
O2—S2—C20 | 107.97 (11) | C14—C13—H13 | 120.1 |
O1—S2—C20 | 107.25 (12) | C15—C14—C13 | 118.1 (3) |
C2—S2—C20 | 105.11 (11) | C15—C14—C18 | 121.7 (3) |
C1—N1—H1NA | 112 (2) | C13—C14—C18 | 120.2 (3) |
C1—N1—H1NB | 123.6 (19) | C16—C15—C14 | 122.7 (2) |
H1NA—N1—H1NB | 124 (3) | C16—C15—H15 | 118.6 |
C3—N2—C12 | 124.4 (2) | C14—C15—H15 | 118.6 |
C3—N2—H2NA | 121 (2) | C15—C16—C17 | 118.0 (2) |
C12—N2—H2NA | 114 (2) | C15—C16—C19 | 121.8 (3) |
N1—C1—C4 | 122.4 (2) | C17—C16—C19 | 120.2 (3) |
N1—C1—C2 | 125.2 (2) | C12—C17—C16 | 120.3 (2) |
C4—C1—C2 | 112.35 (18) | C12—C17—H17 | 119.9 |
C3—C2—C1 | 112.82 (19) | C16—C17—H17 | 119.9 |
C3—C2—S2 | 122.23 (17) | C14—C18—H18B | 109.5 |
C1—C2—S2 | 124.52 (16) | C14—C18—H18A | 109.5 |
N2—C3—C2 | 127.8 (2) | H18B—C18—H18A | 109.5 |
N2—C3—S1 | 120.20 (17) | C14—C18—H18C | 109.5 |
C2—C3—S1 | 112.01 (16) | H18B—C18—H18C | 109.5 |
C1—C4—C5 | 125.2 (2) | H18A—C18—H18C | 109.5 |
C1—C4—S1 | 110.74 (16) | C16—C19—H19A | 109.5 |
C5—C4—S1 | 123.93 (17) | C16—C19—H19C | 109.5 |
O3—C5—C4 | 121.0 (2) | H19A—C19—H19C | 109.5 |
O3—C5—C6 | 118.2 (2) | C16—C19—H19B | 109.5 |
C4—C5—C6 | 120.7 (2) | H19A—C19—H19B | 109.5 |
C7—C6—C11 | 119.0 (2) | H19C—C19—H19B | 109.5 |
C7—C6—C5 | 122.7 (2) | C21—C20—C25 | 120.7 (3) |
C11—C6—C5 | 118.2 (2) | C21—C20—S2 | 120.0 (2) |
C8—C7—C6 | 120.0 (2) | C25—C20—S2 | 119.3 (2) |
C8—C7—H7 | 120.0 | C20—C21—C22 | 119.1 (3) |
C6—C7—H7 | 120.0 | C20—C21—H21 | 120.5 |
C9—C8—C7 | 120.4 (2) | C22—C21—H21 | 120.5 |
C9—C8—H8 | 119.8 | C23—C22—C21 | 120.5 (4) |
C7—C8—H8 | 119.8 | C23—C22—H22 | 119.8 |
C10—C9—C8 | 119.8 (2) | C21—C22—H22 | 119.8 |
C10—C9—H9 | 120.1 | C22—C23—C24 | 120.7 (4) |
C8—C9—H9 | 120.1 | C22—C23—H23 | 119.7 |
C9—C10—C11 | 120.4 (3) | C24—C23—H23 | 119.7 |
C9—C10—H10 | 119.8 | C25—C24—C23 | 120.1 (4) |
C11—C10—H10 | 119.8 | C25—C24—H24 | 120.0 |
C10—C11—C6 | 120.3 (2) | C23—C24—H24 | 120.0 |
C10—C11—H11 | 119.9 | C24—C25—C20 | 118.9 (3) |
C6—C11—H11 | 119.9 | C24—C25—H25 | 120.5 |
C17—C12—C13 | 121.0 (2) | C20—C25—H25 | 120.5 |
N1—C1—C2—C3 | 179.4 (2) | C6—C7—C8—C9 | −1.3 (4) |
C4—C1—C2—C3 | 0.2 (3) | C7—C8—C9—C10 | 1.1 (4) |
N1—C1—C2—S2 | 6.8 (4) | C8—C9—C10—C11 | 0.1 (4) |
C4—C1—C2—S2 | −172.34 (17) | C9—C10—C11—C6 | −1.1 (4) |
O2—S2—C2—C3 | 160.23 (19) | C7—C6—C11—C10 | 0.9 (4) |
O1—S2—C2—C3 | 29.9 (2) | C5—C6—C11—C10 | 178.2 (2) |
C20—S2—C2—C3 | −84.4 (2) | C3—N2—C12—C17 | 64.5 (4) |
O2—S2—C2—C1 | −27.9 (2) | C3—N2—C12—C13 | −116.9 (3) |
O1—S2—C2—C1 | −158.18 (19) | C17—C12—C13—C14 | 0.6 (4) |
C20—S2—C2—C1 | 87.5 (2) | N2—C12—C13—C14 | −178.0 (2) |
C12—N2—C3—C2 | 175.3 (2) | C12—C13—C14—C15 | −1.0 (4) |
C12—N2—C3—S1 | −3.9 (4) | C12—C13—C14—C18 | 178.9 (3) |
C1—C2—C3—N2 | −179.6 (2) | C13—C14—C15—C16 | −0.1 (4) |
S2—C2—C3—N2 | −6.9 (4) | C18—C14—C15—C16 | 179.9 (3) |
C1—C2—C3—S1 | −0.3 (3) | C14—C15—C16—C17 | 1.7 (4) |
S2—C2—C3—S1 | 172.41 (13) | C14—C15—C16—C19 | −179.0 (3) |
C4—S1—C3—N2 | 179.6 (2) | C13—C12—C17—C16 | 1.1 (4) |
C4—S1—C3—C2 | 0.29 (19) | N2—C12—C17—C16 | 179.6 (2) |
N1—C1—C4—C5 | −3.0 (4) | C15—C16—C17—C12 | −2.2 (4) |
C2—C1—C4—C5 | 176.2 (2) | C19—C16—C17—C12 | 178.6 (3) |
N1—C1—C4—S1 | −179.2 (2) | O2—S2—C20—C21 | −149.6 (2) |
C2—C1—C4—S1 | 0.0 (3) | O1—S2—C20—C21 | −20.4 (2) |
C3—S1—C4—C1 | −0.16 (19) | C2—S2—C20—C21 | 94.6 (2) |
C3—S1—C4—C5 | −176.4 (2) | O2—S2—C20—C25 | 32.5 (2) |
C1—C4—C5—O3 | 3.1 (4) | O1—S2—C20—C25 | 161.7 (2) |
S1—C4—C5—O3 | 178.77 (19) | C2—S2—C20—C25 | −83.3 (2) |
C1—C4—C5—C6 | −175.0 (2) | C25—C20—C21—C22 | 1.3 (4) |
S1—C4—C5—C6 | 0.7 (3) | S2—C20—C21—C22 | −176.5 (3) |
O3—C5—C6—C7 | 134.0 (2) | C20—C21—C22—C23 | 0.3 (6) |
C4—C5—C6—C7 | −47.9 (3) | C21—C22—C23—C24 | −1.6 (6) |
O3—C5—C6—C11 | −43.2 (3) | C22—C23—C24—C25 | 1.4 (6) |
C4—C5—C6—C11 | 134.9 (2) | C23—C24—C25—C20 | 0.2 (5) |
C11—C6—C7—C8 | 0.3 (4) | C21—C20—C25—C24 | −1.6 (4) |
C5—C6—C7—C8 | −176.9 (2) | S2—C20—C25—C24 | 176.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1NA···O3 | 0.76 (3) | 2.06 (3) | 2.699 (3) | 141 (3) |
N1—H1NB···O2 | 0.95 (3) | 2.22 (3) | 2.864 (3) | 124 (2) |
N2—H2NA···O1 | 0.78 (3) | 2.25 (3) | 2.820 (3) | 130 (2) |
N1—H1NB···O2i | 0.95 (3) | 2.19 (3) | 2.993 (3) | 142 (3) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C25H22N2O3S2 |
Mr | 462.57 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.497 (3), 11.451 (3), 11.863 (3) |
α, β, γ (°) | 65.65 (2), 69.654 (19), 70.18 (2) |
V (Å3) | 1185.6 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Siemens P3/PC |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4246, 4042, 3150 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.108, 1.02 |
No. of reflections | 4042 |
No. of parameters | 322 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.31 |
Computer programs: P3 (Siemens,1989), P3, XDISK (Siemens, 1991), SHELXTL (Sheldrick, 1998), SHELXTL.
S1—C3 | 1.719 (2) | S2—O1 | 1.4372 (17) |
S1—C4 | 1.758 (2) | S2—C2 | 1.726 (2) |
S2—O2 | 1.4337 (17) | S2—C20 | 1.761 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1NA···O3 | 0.76 (3) | 2.06 (3) | 2.699 (3) | 141 (3) |
N1—H1NB···O2 | 0.95 (3) | 2.22 (3) | 2.864 (3) | 124 (2) |
N2—H2NA···O1 | 0.78 (3) | 2.25 (3) | 2.820 (3) | 130 (2) |
N1—H1NB···O2i | 0.95 (3) | 2.19 (3) | 2.993 (3) | 142 (3) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Thiophene is a very important pharmacophore in many biologically active compounds. Thiophene derivatives are used as antibiotics, anaesthetics, antiparasitics, resolvents, antihelmintic drugs, anticholinergic drugs, antiulcer agents, antihistamines, antitussives (Patent USA, 2000, Kovalenko & Victorova, 2005), therefore investigation of their molecular structure may provide useful information for the understanding of mechanisms of biological activity. In this paper we report the molecular and crystal structure of 2-aroyl-3-amino-4-arylsulfonyl-5-arylamino-thiophene (Fig.1). The carbonyl group is essentially coplanar with the thiophene ring (the C1—C4—C5—O3 torsion angle is 3.1 (4)°). Such a conformation of this group is stabilized by the weak intramolecular hydrogen bond N1—H1NA···O3 H···O 2.06 Å, N—H···O 141°. Atoms N1 and N2 have a planar configuration, the sum of the bond angles, centered at these atoms are 360° in both cases. The phenyl substituent at atom C5 atom is rotated with respect to the C4—C5 bond (the C4—C5—C6—C7 torsion angle is -47.9 (3) °). Such orientation of the phenyl ring indicates an interaction between phenyl ring and atom S1 (the short intramolecular contact C7···S1 is 2.71Å [van der Waals radii sum is 3.01 Å; Zefirov & Zorky (1995)]. The phenyl substituent at the S2 atom has an almost orthogonal orientation relative to the thiophene ring (the C20—S2—C2—C3 torsion angle is -84.4 (2) °) and with respect to the C2—S2 bond (the C2—S2—C20—C25 torsion angle is -83.3 (2)°). The conformation of sulfonyl group is stabilized by weak intramolecular hydrogen bonds N1—H1NB···O2 H···O 2.22 Å, N—H···O 124° and N2—H2NA···O1 H···O 2.25 Å, N—H···O 130°, respectively. The dimethylphenylamino substituent adopts an sp-conformation relative to the C3—S1 bond (the S1—C3—N2—C12 torsion angle is -3.9 (4) °) and it is rotated with respect to the C3—N2 bond (the C3—N2—C12—C17 torsion angle is 64.5 (4) °). The most interesting feature of the structure is difference in the S—C bond lengths within thiophene ring. The C4—S1 bond (1.758 (2) Å) is significantly longer than the S1—C3 bond (1.719 (2) Å) and the reported mean value is 1.712 Å (Bürgi & Dunitz, 1994). Comparison of bond lengths within the thiophene ring in the title compound and other 2,5-disubstituted thiophene compounds (Apinitis et al., 1984; Xu et al., 2004) indicates that elongation of the S1—C4 bond is observed when an electron-withdrawing substituent is at atom C4. This may lead to considerable asymmetry in conjugation interactions within the C—S—C fragment of thiophene ring. In the crystal structure, molecules of title compound form centrosymmetric dimers due to intermolecular hydrogen bond N1—H1NB···O2' (symmetry code (') -x + 1, -y + 1, -z + 2) H···O' 2.19 Å, N—H···O' 142 °.