organic compounds
2-Amino-N-(furan-2-ylmethyl)-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carboxamide
aDepartment of Engineering Physics, HKBK College of Engineering, Bengaluru 560 045, India, bDepartment of Physics, RV College of Engineering, Bengaluru 560 059, India, and cDepartment of Physics, The National Institute of Engineering (NIE), Mysore 570 008, India
*Correspondence e-mail: mychandru.10@gmail.com
In the title compound, C13H14N2O2S, the dihedral angle between the furan and cyclopentathiophene groups is 89.88 (14)°. The carboximidamide unit is in an anticlinal conformation with respect to the cycloheptathiophene moiety and an intramolecular N—H⋯O hydrogen bond closes an S(6) ring. In the crystal, N—H⋯O hydogen bonds link the molecules into [010] C(6) chains and a very weak C—H⋯O interaction is also observed.
CCDC reference: 1570199
Structure description
Tetrahydrothieno derivatives are studied extensively in medicinal chemistry due to their various biological activities (Lopez-Rodriguez et al., 2001). As part of our interest in these compounds, we have synthesized the title compound (Fig. 1) and determined its crystal structure.
The mean plane of the furan moiety (O1/C10–C13) is oriented at a dihedral angle of 89.88 (14)° with respect to the plane of the almost planar (r.m.s. deviation = 0.014 Å) cyclopentathiophene ring (S1–C7). The carboximidamide unit is in an antiperiplanar conformation with respect to the cycloheptathiophene moiety, as indicated by the torsion angle of 177.07 (18)° for N2—C8—C7—C6. An intramolecular N1—H1A⋯O2 hydrogen bond (Table 1) closes an S(6) ring.
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In the crystal, N1—H1B⋯O2i hydrogen bonds link the molecules into C(6) chains propagating in the [010] direction (Fig. 2). A very weak C—H⋯O interaction is also observed. The amide N2—H1N group does not participate in hydrogen bonding, perhaps due to steric crowding.
Synthesis and crystallization
Cyclopentanone (0.8 equivalents), diethylamine (0.9 equivalents) and N-(2-methoxyphenyl)acetamide (1.2 equivalents) were taken in 15 ml ethanol and mixed thoroughly in a microwave tube. The tube was sealed and irradiated at 325 K for 15 min. After cooling, ethyl acetate was added to the reaction mixture and the solid residue was removed by filtration. The reaction mixture was poured into ice-cold water, and the separated solid was filtered off and recrystallized from ethyl alcohol solution to give pale-yellow blocks of the title compound.
Refinement
Crystal data, data collection and structure . The H atoms were positioned geometrically and allowed to ride on their parent atom, with N—H = 0.86 Å and C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2–1.5Ueq(carrier) for all H atoms.
details are summarized in Table 2Structural data
CCDC reference: 1570199
https://doi.org/10.1107/S2414314617012111/hb4165sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617012111/hb4165Isup2.hkl
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C13H14N2O2S | F(000) = 1104 |
Mr = 262.32 | Dx = 1.443 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2375 reflections |
a = 21.694 (2) Å | θ = 2.4–26.0° |
b = 9.8547 (11) Å | µ = 0.26 mm−1 |
c = 15.1162 (16) Å | T = 273 K |
β = 131.661 (2)° | Block, pale yellow |
V = 2414.3 (4) Å3 | 0.28 × 0.25 × 0.22 mm |
Z = 8 |
Bruker APEXII CCD diffractometer | Rint = 0.026 |
Detector resolution: 18.4 pixels mm-1 | θmax = 26.0°, θmin = 2.4° |
ω and φ scans | h = −25→26 |
9118 measured reflections | k = −11→12 |
2375 independent reflections | l = −18→18 |
1950 reflections with I > 2σ(I) |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.120 | W = 1/[Σ2(FO2) + (0.0768P)2 + 1.5332P] WHERE P = (FO2 + 2FC2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
2375 reflections | Δρmax = 0.25 e Å−3 |
167 parameters | Δρmin = −0.27 e Å−3 |
0 restraints |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating -R-factor-obs 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 | 0.20078 (3) | 0.46023 (5) | 0.33918 (5) | 0.0417 (2) | |
O1 | −0.01010 (9) | 1.03238 (16) | 0.12373 (13) | 0.0494 (5) | |
O2 | 0.20894 (9) | 0.91283 (14) | 0.28657 (13) | 0.0419 (5) | |
N1 | 0.24893 (11) | 0.65497 (18) | 0.27274 (16) | 0.0460 (6) | |
N2 | 0.13634 (11) | 0.94561 (16) | 0.34213 (16) | 0.0369 (6) | |
C1 | 0.09466 (13) | 0.6855 (2) | 0.42005 (18) | 0.0387 (6) | |
C2 | 0.13894 (11) | 0.64691 (19) | 0.37874 (15) | 0.0315 (5) | |
C3 | 0.07541 (17) | 0.5480 (2) | 0.4461 (3) | 0.0579 (9) | |
C4 | 0.11271 (15) | 0.4340 (2) | 0.4249 (2) | 0.0481 (8) | |
C5 | 0.14820 (12) | 0.5112 (2) | 0.38300 (17) | 0.0374 (6) | |
C6 | 0.20996 (11) | 0.62804 (19) | 0.31246 (16) | 0.0323 (6) | |
C7 | 0.17454 (11) | 0.71866 (18) | 0.33821 (15) | 0.0296 (5) | |
C8 | 0.17492 (11) | 0.86383 (19) | 0.32061 (15) | 0.0307 (5) | |
C9 | 0.12394 (12) | 1.08935 (19) | 0.31397 (17) | 0.0357 (6) | |
C10 | 0.05629 (11) | 1.11794 (19) | 0.18473 (17) | 0.0341 (6) | |
C11 | 0.04371 (14) | 1.2137 (2) | 0.11172 (19) | 0.0488 (7) | |
C12 | −0.03482 (14) | 1.1888 (2) | −0.00186 (19) | 0.0520 (8) | |
C13 | −0.06404 (14) | 1.0795 (3) | 0.0094 (2) | 0.0530 (8) | |
H1A | 0.25426 | 0.73747 | 0.26020 | 0.0550* | |
H1B | 0.26842 | 0.58963 | 0.25995 | 0.0550* | |
H1D | 0.04431 | 0.73478 | 0.35898 | 0.0460* | |
H1E | 0.12945 | 0.74105 | 0.49084 | 0.0460* | |
H1N | 0.1123 (15) | 0.914 (2) | 0.359 (2) | 0.047 (7)* | |
H3A | 0.09891 | 0.54570 | 0.52755 | 0.0700* | |
H3B | 0.01619 | 0.53591 | 0.39458 | 0.0700* | |
H4A | 0.15513 | 0.38489 | 0.49735 | 0.0580* | |
H4B | 0.07068 | 0.37072 | 0.36516 | 0.0580* | |
H9A | 0.17493 | 1.12798 | 0.34037 | 0.0430* | |
H9B | 0.11115 | 1.13391 | 0.35731 | 0.0430* | |
H11 | 0.07968 | 1.28374 | 0.13150 | 0.0590* | |
H12 | −0.06040 | 1.23942 | −0.07033 | 0.0620* | |
H13 | −0.11455 | 1.03962 | −0.05200 | 0.0640* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0525 (3) | 0.0264 (3) | 0.0565 (4) | −0.0005 (2) | 0.0405 (3) | −0.0038 (2) |
O1 | 0.0473 (9) | 0.0544 (10) | 0.0507 (9) | −0.0160 (7) | 0.0344 (8) | −0.0103 (7) |
O2 | 0.0565 (9) | 0.0323 (7) | 0.0596 (9) | −0.0007 (6) | 0.0481 (8) | 0.0022 (6) |
N1 | 0.0646 (12) | 0.0324 (9) | 0.0711 (12) | 0.0011 (8) | 0.0578 (11) | −0.0032 (8) |
N2 | 0.0517 (10) | 0.0271 (9) | 0.0492 (10) | 0.0024 (7) | 0.0408 (9) | 0.0029 (7) |
C1 | 0.0446 (11) | 0.0370 (11) | 0.0448 (11) | −0.0010 (9) | 0.0340 (10) | −0.0001 (9) |
C2 | 0.0326 (9) | 0.0309 (10) | 0.0309 (9) | −0.0025 (7) | 0.0211 (8) | −0.0023 (7) |
C3 | 0.0780 (17) | 0.0436 (14) | 0.0860 (18) | −0.0057 (11) | 0.0687 (16) | 0.0008 (12) |
C4 | 0.0580 (13) | 0.0365 (12) | 0.0608 (14) | −0.0056 (10) | 0.0441 (12) | 0.0013 (10) |
C5 | 0.0424 (11) | 0.0311 (10) | 0.0430 (11) | −0.0037 (8) | 0.0302 (10) | −0.0023 (8) |
C6 | 0.0346 (10) | 0.0287 (10) | 0.0345 (9) | −0.0025 (7) | 0.0234 (8) | −0.0038 (7) |
C7 | 0.0314 (9) | 0.0283 (10) | 0.0306 (9) | −0.0017 (7) | 0.0213 (8) | −0.0022 (7) |
C8 | 0.0324 (9) | 0.0300 (10) | 0.0297 (9) | −0.0003 (7) | 0.0207 (8) | −0.0014 (7) |
C9 | 0.0449 (11) | 0.0256 (10) | 0.0430 (11) | 0.0003 (8) | 0.0319 (10) | −0.0029 (8) |
C10 | 0.0374 (10) | 0.0280 (9) | 0.0438 (11) | −0.0017 (8) | 0.0299 (9) | −0.0061 (8) |
C11 | 0.0503 (13) | 0.0365 (12) | 0.0469 (12) | −0.0049 (10) | 0.0270 (11) | 0.0013 (9) |
C12 | 0.0537 (14) | 0.0502 (14) | 0.0418 (12) | 0.0107 (11) | 0.0274 (11) | 0.0032 (10) |
C13 | 0.0396 (12) | 0.0718 (17) | 0.0449 (13) | −0.0038 (11) | 0.0269 (11) | −0.0131 (11) |
S1—C5 | 1.731 (3) | C6—C7 | 1.392 (3) |
S1—C6 | 1.745 (2) | C7—C8 | 1.456 (3) |
O1—C10 | 1.368 (3) | C9—C10 | 1.496 (3) |
O1—C13 | 1.372 (3) | C10—C11 | 1.335 (3) |
O2—C8 | 1.244 (3) | C11—C12 | 1.422 (3) |
N1—C6 | 1.349 (4) | C12—C13 | 1.317 (4) |
N2—C8 | 1.348 (4) | C1—H1D | 0.9700 |
N2—C9 | 1.452 (2) | C1—H1E | 0.9700 |
C1—C2 | 1.502 (4) | C3—H3A | 0.9700 |
C1—C3 | 1.544 (4) | C3—H3B | 0.9700 |
N1—H1A | 0.8600 | C4—H4A | 0.9700 |
N1—H1B | 0.8600 | C4—H4B | 0.9700 |
N2—H1N | 0.78 (4) | C9—H9A | 0.9700 |
C2—C5 | 1.348 (3) | C9—H9B | 0.9700 |
C2—C7 | 1.449 (4) | C11—H11 | 0.9300 |
C3—C4 | 1.538 (5) | C12—H12 | 0.9300 |
C4—C5 | 1.490 (4) | C13—H13 | 0.9300 |
C5—S1—C6 | 91.10 (12) | C10—C11—C12 | 107.4 (2) |
C10—O1—C13 | 106.0 (2) | C11—C12—C13 | 106.2 (2) |
C8—N2—C9 | 122.4 (2) | O1—C13—C12 | 111.0 (2) |
C2—C1—C3 | 103.9 (2) | C2—C1—H1D | 111.00 |
C6—N1—H1B | 120.00 | C2—C1—H1E | 111.00 |
H1A—N1—H1B | 120.00 | C3—C1—H1D | 111.00 |
C6—N1—H1A | 120.00 | C3—C1—H1E | 111.00 |
C1—C2—C5 | 110.4 (2) | H1D—C1—H1E | 109.00 |
C1—C2—C7 | 136.07 (18) | C1—C3—H3A | 110.00 |
C8—N2—H1N | 119.8 (18) | C1—C3—H3B | 110.00 |
C9—N2—H1N | 116.8 (19) | C4—C3—H3A | 110.00 |
C5—C2—C7 | 113.6 (2) | C4—C3—H3B | 110.00 |
C1—C3—C4 | 108.6 (3) | H3A—C3—H3B | 108.00 |
C3—C4—C5 | 102.0 (2) | C3—C4—H4A | 111.00 |
C2—C5—C4 | 115.1 (2) | C3—C4—H4B | 111.00 |
S1—C5—C2 | 112.6 (2) | C5—C4—H4A | 111.00 |
S1—C5—C4 | 132.26 (17) | C5—C4—H4B | 111.00 |
S1—C6—N1 | 119.41 (17) | H4A—C4—H4B | 109.00 |
S1—C6—C7 | 111.98 (19) | N2—C9—H9A | 109.00 |
N1—C6—C7 | 128.61 (19) | N2—C9—H9B | 109.00 |
C2—C7—C6 | 110.71 (17) | C10—C9—H9A | 109.00 |
C6—C7—C8 | 120.5 (2) | C10—C9—H9B | 109.00 |
C2—C7—C8 | 128.7 (2) | H9A—C9—H9B | 108.00 |
O2—C8—C7 | 122.3 (2) | C10—C11—H11 | 126.00 |
N2—C8—C7 | 117.6 (2) | C12—C11—H11 | 126.00 |
O2—C8—N2 | 120.13 (18) | C11—C12—H12 | 127.00 |
N2—C9—C10 | 113.35 (16) | C13—C12—H12 | 127.00 |
O1—C10—C9 | 116.34 (18) | O1—C13—H13 | 125.00 |
O1—C10—C11 | 109.48 (19) | C12—C13—H13 | 124.00 |
C9—C10—C11 | 134.2 (2) | ||
C6—S1—C5—C2 | −0.58 (17) | C1—C2—C7—C6 | 179.0 (2) |
C6—S1—C5—C4 | −179.9 (2) | C1—C2—C7—C8 | −2.5 (4) |
C5—S1—C6—N1 | −179.91 (18) | C1—C3—C4—C5 | −2.3 (3) |
C5—S1—C6—C7 | 0.76 (16) | C3—C4—C5—S1 | −179.6 (2) |
C13—O1—C10—C9 | 178.8 (2) | C3—C4—C5—C2 | 1.1 (3) |
C13—O1—C10—C11 | 0.3 (3) | S1—C6—C7—C2 | −0.7 (2) |
C10—O1—C13—C12 | −0.8 (3) | N1—C6—C7—C8 | 1.4 (3) |
C9—N2—C8—O2 | 7.5 (3) | S1—C6—C7—C8 | −179.33 (14) |
C9—N2—C8—C7 | −172.27 (18) | N1—C6—C7—C2 | −180.0 (2) |
C8—N2—C9—C10 | 76.0 (3) | C2—C7—C8—O2 | 179.03 (19) |
C2—C1—C3—C4 | 2.7 (3) | C2—C7—C8—N2 | −1.2 (3) |
C3—C1—C2—C5 | −2.1 (3) | C6—C7—C8—O2 | −2.7 (3) |
C3—C1—C2—C7 | 179.2 (2) | C6—C7—C8—N2 | 177.07 (18) |
C1—C2—C5—S1 | −178.78 (14) | N2—C9—C10—O1 | 35.1 (4) |
C1—C2—C5—C4 | 0.7 (3) | N2—C9—C10—C11 | −147.0 (3) |
C7—C2—C5—S1 | 0.3 (2) | O1—C10—C11—C12 | 0.2 (3) |
C7—C2—C5—C4 | 179.70 (18) | C9—C10—C11—C12 | −177.8 (3) |
C5—C2—C7—C8 | 178.76 (19) | C10—C11—C12—C13 | −0.7 (4) |
C5—C2—C7—C6 | 0.3 (2) | C11—C12—C13—O1 | 0.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.86 | 2.15 | 2.738 (3) | 125 |
N1—H1B···O2i | 0.86 | 2.06 | 2.902 (3) | 167 |
C9—H9B···O1ii | 0.97 | 2.59 | 3.224 (4) | 123 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x, y, −z+1/2. |
Acknowledgements
The authors thank HKBK College of Engineering, Bengaluru, R. V. College of Engineering, Bengaluru, and The National Institute of Engineering (NIE), Mysuru, for support.
References
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