Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004585/ci6018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004585/ci6018Isup2.hkl |
CCDC reference: 162824
Dry ammonia gas was introduced with ice cooling, to a solution of N-(3-benzoyl-4,5-dimethyl-thiophen-2-yl)-2-iodoacetamide (3.2 g, 8.0 mmol) in CHCl3 (dry, 10 ml) and methanol (dry, 1 ml) over a period of 40 min. The mixture was then stirred at room temperature for a further 5 h. After this time, ice and water were added. The organic phase was washed with NaHCO3 solution (saturated, 10 ml), H2O (3 × 10 ml) and dried with MgSO4. Subsequent removal of solvent under reduced pressure gave 2.024 g of crude product which was purified with silica chromatography. Hexane–ethyl acetate (1:1) as eluent gave the product (1.158 g, 53%) which was recrystallized from ethyl acetate to give clear crystals, m.p. (decomposition) 511–514 K. 1H NMR (DMSO-d6) δ 1.50 (s, 3H, CH3), 2.24 (s, 3H, CH3), 3.80 (d, 1H, CH2), 4.50 (d, 1H, CH2), 7.39–7.45 (m, 5H, C6H5), 11.03 (br, s, 1H, NH). 13C NMR (DMSO-d6) δ 12.43, 14.09, 57.85, 125.02, 125.94, 128.26, 128.34, 128.98, 129.93, 138.48, 142.48, 166.36, 168.29.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); data reduction: TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level (ORTEPII; Johnson, 1976). |
C15H14N2OS | Dx = 1.348 Mg m−3 |
Mr = 270.34 | Mo Kα radiation, λ = 0.7107 Å |
Orthorhombic, Pbca | Cell parameters from 24 reflections |
a = 34.115 (6) Å | θ = 7.4–10.3° |
b = 10.4377 (17) Å | µ = 0.24 mm−1 |
c = 7.484 (3) Å | T = 173 K |
V = 2664.7 (13) Å3 | Block, colourless |
Z = 8 | 0.50 × 0.31 × 0.18 mm |
F(000) = 1136 |
Rigaku AFC-7R diffractometer | Rint = 0.030 |
Radiation source: rotating anode | θmax = 27.5°, θmin = 3.1° |
Graphite monochromator | h = 0→44 |
ω scans | k = −13→10 |
5860 measured reflections | l = −8→9 |
3057 independent reflections | 3 standard reflections every 400 reflections |
2084 reflections with I > 2σ(I) | intensity decay: 0.6% |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
3057 reflections | (Δ/σ)max = 0.002 |
173 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C15H14N2OS | V = 2664.7 (13) Å3 |
Mr = 270.34 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 34.115 (6) Å | µ = 0.24 mm−1 |
b = 10.4377 (17) Å | T = 173 K |
c = 7.484 (3) Å | 0.50 × 0.31 × 0.18 mm |
Rigaku AFC-7R diffractometer | Rint = 0.030 |
5860 measured reflections | 3 standard reflections every 400 reflections |
3057 independent reflections | intensity decay: 0.6% |
2084 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.40 e Å−3 |
3057 reflections | Δρmin = −0.25 e Å−3 |
173 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 | ||
S8 | 0.955883 (15) | −0.08457 (5) | 0.50528 (7) | 0.02942 (18) | |
O2 | 0.98056 (5) | 0.15129 (16) | −0.0480 (2) | 0.0359 (4) | |
N1 | 0.96128 (5) | 0.01871 (17) | 0.1742 (2) | 0.0279 (4) | |
H1 | 0.9790 | −0.0383 | 0.1423 | 0.084 (3)* | |
N4 | 0.88856 (5) | 0.16611 (18) | 0.0892 (2) | 0.0290 (4) | |
C2 | 0.95891 (6) | 0.1303 (2) | 0.0795 (3) | 0.0280 (5) | |
C3 | 0.92695 (6) | 0.2212 (2) | 0.1387 (3) | 0.0293 (5) | |
H3a | 0.9283 | 0.2338 | 0.2697 | 0.084 (3)* | |
H3b | 0.9304 | 0.3054 | 0.0801 | 0.084 (3)* | |
C8a | 0.93706 (6) | −0.0093 (2) | 0.3191 (3) | 0.0254 (4) | |
C5a | 0.89758 (6) | 0.01687 (19) | 0.3362 (3) | 0.0260 (4) | |
C5 | 0.87560 (6) | 0.0755 (2) | 0.1876 (3) | 0.0279 (5) | |
C6' | 0.84207 (7) | 0.0070 (3) | 0.5753 (4) | 0.0418 (6) | |
H6a | 0.8269 | 0.0477 | 0.4795 | 0.084 (3)* | |
H6b | 0.8437 | 0.0653 | 0.6777 | 0.084 (3)* | |
H6c | 0.8291 | −0.0725 | 0.6119 | 0.084 (3)* | |
C6 | 0.88275 (6) | −0.0227 (2) | 0.5089 (3) | 0.0284 (5) | |
C7 | 0.91090 (7) | −0.0793 (2) | 0.6114 (3) | 0.0293 (5) | |
C7' | 0.90801 (8) | −0.1298 (3) | 0.7991 (3) | 0.0422 (6) | |
H7a | 0.9334 | −0.1654 | 0.8353 | 0.084 (3)* | |
H7b | 0.8880 | −0.1970 | 0.8042 | 0.084 (3)* | |
H7c | 0.9008 | −0.0599 | 0.8801 | 0.084 (3)* | |
C51 | 0.83687 (6) | 0.0197 (2) | 0.1352 (3) | 0.0313 (5) | |
C52 | 0.82830 (7) | −0.1093 (2) | 0.1632 (4) | 0.0411 (6) | |
H52 | 0.8464 | −0.1618 | 0.2256 | 0.084 (3)* | |
C53 | 0.79324 (7) | −0.1622 (3) | 0.1004 (4) | 0.0499 (7) | |
H53 | 0.7877 | −0.2503 | 0.1198 | 0.084 (3)* | |
C54 | 0.76674 (7) | −0.0859 (3) | 0.0099 (4) | 0.0521 (8) | |
H54 | 0.7430 | −0.1218 | −0.0338 | 0.084 (3)* | |
C55 | 0.77466 (7) | 0.0421 (3) | −0.0170 (4) | 0.0497 (7) | |
H55 | 0.7562 | 0.0943 | −0.0784 | 0.084 (3)* | |
C56 | 0.80937 (7) | 0.0953 (3) | 0.0451 (3) | 0.0403 (6) | |
H56 | 0.8145 | 0.1837 | 0.0264 | 0.084 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S8 | 0.0274 (3) | 0.0309 (3) | 0.0300 (3) | 0.0002 (2) | −0.0057 (2) | 0.0043 (2) |
O2 | 0.0311 (9) | 0.0408 (9) | 0.0357 (8) | 0.0024 (7) | 0.0054 (7) | 0.0082 (7) |
N1 | 0.0240 (8) | 0.0309 (10) | 0.0288 (9) | 0.0015 (7) | 0.0010 (7) | 0.0015 (7) |
N4 | 0.0264 (9) | 0.0321 (9) | 0.0285 (9) | 0.0079 (7) | −0.0015 (7) | −0.0015 (8) |
C2 | 0.0249 (10) | 0.0310 (11) | 0.0281 (11) | −0.0032 (8) | −0.0045 (8) | 0.0016 (9) |
C3 | 0.0313 (10) | 0.0293 (11) | 0.0272 (10) | 0.0010 (8) | −0.0013 (9) | 0.0007 (9) |
C8a | 0.0253 (10) | 0.0267 (10) | 0.0242 (10) | 0.0008 (8) | −0.0029 (8) | −0.0002 (8) |
C5a | 0.0235 (10) | 0.0267 (10) | 0.0278 (11) | 0.0004 (8) | −0.0020 (8) | −0.0023 (8) |
C5 | 0.0240 (10) | 0.0313 (11) | 0.0282 (10) | 0.0054 (8) | −0.0011 (8) | −0.0048 (9) |
C6' | 0.0337 (13) | 0.0490 (15) | 0.0428 (14) | 0.0034 (11) | 0.0132 (11) | 0.0033 (11) |
C6 | 0.0274 (10) | 0.0279 (11) | 0.0301 (11) | −0.0021 (8) | 0.0017 (9) | −0.0022 (9) |
C7 | 0.0329 (11) | 0.0273 (11) | 0.0276 (10) | −0.0027 (8) | −0.0008 (9) | −0.0009 (9) |
C7' | 0.0529 (15) | 0.0424 (14) | 0.0314 (12) | −0.0053 (11) | −0.0006 (11) | 0.0053 (11) |
C51 | 0.0230 (10) | 0.0409 (13) | 0.0300 (11) | 0.0059 (9) | −0.0024 (9) | −0.0060 (10) |
C52 | 0.0270 (11) | 0.0450 (14) | 0.0514 (15) | 0.0018 (10) | −0.0066 (11) | −0.0059 (12) |
C53 | 0.0313 (13) | 0.0495 (15) | 0.0689 (19) | −0.0031 (11) | −0.0019 (13) | −0.0134 (14) |
C54 | 0.0241 (11) | 0.073 (2) | 0.0591 (18) | −0.0003 (12) | −0.0074 (11) | −0.0219 (16) |
C55 | 0.0277 (12) | 0.0731 (19) | 0.0483 (16) | 0.0124 (12) | −0.0074 (11) | −0.0052 (15) |
C56 | 0.0296 (12) | 0.0479 (15) | 0.0433 (13) | 0.0099 (10) | −0.0061 (10) | −0.0046 (11) |
S8—C8a | 1.723 (2) | C5—C51 | 1.496 (3) |
S8—C7 | 1.729 (2) | C6'—C6 | 1.506 (3) |
O2—C2 | 1.227 (3) | C6—C7 | 1.364 (3) |
N1—C2 | 1.365 (3) | C7—C7' | 1.503 (3) |
N1—C8a | 1.394 (3) | C51—C52 | 1.394 (3) |
N4—C5 | 1.278 (3) | C51—C56 | 1.398 (3) |
N4—C3 | 1.477 (3) | C52—C53 | 1.399 (3) |
C2—C3 | 1.512 (3) | C53—C54 | 1.382 (4) |
C8a—C5a | 1.380 (3) | C54—C55 | 1.378 (5) |
C5a—C6 | 1.448 (3) | C55—C56 | 1.388 (4) |
C5a—C5 | 1.474 (3) | ||
C8a—S8—C7 | 91.50 (11) | C5a—C5—C51 | 119.06 (18) |
C2—N1—C8a | 123.19 (18) | C7—C6—C5a | 112.32 (19) |
C5—N4—C3 | 116.76 (17) | C7—C6—C6' | 123.6 (2) |
O2—C2—N1 | 121.4 (2) | C5a—C6—C6' | 123.9 (2) |
O2—C2—C3 | 123.4 (2) | C6—C7—C7' | 129.1 (2) |
N1—C2—C3 | 115.20 (18) | C6—C7—S8 | 112.36 (17) |
N4—C3—C2 | 108.75 (17) | C7'—C7—S8 | 118.45 (18) |
C5a—C8a—N1 | 127.48 (19) | C52—C51—C56 | 118.4 (2) |
C5a—C8a—S8 | 112.28 (16) | C52—C51—C5 | 121.44 (19) |
N1—C8a—S8 | 120.23 (15) | C56—C51—C5 | 120.0 (2) |
C8a—C5a—C6 | 111.51 (19) | C51—C52—C53 | 120.7 (2) |
C8a—C5a—C5 | 120.59 (19) | C54—C53—C52 | 119.8 (3) |
C6—C5a—C5 | 127.88 (19) | C55—C54—C53 | 120.1 (2) |
N4—C5—C5a | 124.46 (19) | C54—C55—C56 | 120.4 (3) |
N4—C5—C51 | 116.26 (19) | C51—C56—C55 | 120.6 (3) |
Experimental details
Crystal data | |
Chemical formula | C15H14N2OS |
Mr | 270.34 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 173 |
a, b, c (Å) | 34.115 (6), 10.4377 (17), 7.484 (3) |
V (Å3) | 2664.7 (13) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.50 × 0.31 × 0.18 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5860, 3057, 2084 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.152, 1.02 |
No. of reflections | 3057 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.25 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996), TEXSAN (Molecular Structure Corporation, 1997), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Compounds related to the title compound, (I), are known to enhance agonist binding to the A1 adenosine receptor (Tranberg et al., 2001). In this context, the conformation of the seven-membered ring is of some interest as this determines the conformation of the N atoms which, in turn, influences activity.
The structure of (I) is shown in Fig. 1 from which it can be seen that the seven-membered ring adopts a boat conformation. In this description, the N1, N4, C2 and C5 atoms are essentially coplanar, so that the N1—H, C2═O2 and phenyl groups lie to one side of the molecule, and the thienyl ring and methylene group to the other. Centrosymmetrically related pairs of molecules associate via hydrogen bonding between the amide groups: N1—H1 0.88 Å, H1···O2i 1.95 Å, N1···O2i 2.824 (3) Å and N1—H1···O2i 173° [symmetry code: (i) 2 - x, -y, -z]. Interactions of the type C—H···π also operate in the structure such that C3—H3b···Cgii is 2.62 Å (Cg is the centroid of the thienyl ring), with the angle subtended at H3b being 162° [symmetry code: (ii) x, 1/2 - y, -1/2 + z].