organic compounds
6,7-Diphenyl-5-thia-7-azaspiro[2.6]nonan-8-one
aDepartment of Chemistry, Pennsylvania State University, University Park, PA 16802, USA, and bPenn State University, Schuylkill Campus, 200 University Drive, Schuylkill Haven, PA 17972, USA
*Correspondence e-mail: ljs43@psu.edu
The 19H19NOS, contains two independent molecules (A and B), in both of which the 1,3-thiazepan-4-one ring adopts a chair-type conformation. The dihedral angles between the two phenyl rings are 65.28 (8) and 60.31 (9)° for molecules A and B, respectively. In the crystal, molecules are linked by weak C—H⋯O interactions, resulting in a three-dimensional network.
of the title compound, CCCDC reference: 966047
Related literature
For amide bond formation using 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane–2,4,6-trioxide (T3P), see: Dunetz et al. (2011). For preparation of various heterocycles using and T3P, see: Unsworth et al. (2013). For omapatrilat, see: Graul et al. (1999); Robl et al. (1997); Tabrizchi (2001).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 966047
10.1107/S1600536813027979/lx2289sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813027979/lx2289Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813027979/lx2289Isup3.mol
Supporting information file. DOI: 10.1107/S1600536813027979/lx2289Isup4.cml
A two-necked 25 ml pear flask was oven-dried, cooled under N2, and charged with a stir bar and N-[phenylmethylidene]aniline (1.087 g, 6 mmol). Tetrahydrofuran (2.3 mL) was added, the solid dissolved, and the solution was stirred. Pyridine (1.95 ml, 24 mmol) was added and then [1-(sulfanylmethyl)cyclopropyl] acetic acid (0.877 g, 6 mmol) was added. Finally, 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide in 2-methyltetrahydrofuran (50 weight percent, 7.1 ml, 12 mmol) was added. The reaction was stirred at room temperature for 20 h, then poured into a separatory funnel with dichloromethane. The mixture was washed with saturated sodium bicarbonate. The aqueous solution was then extracted twice with dichloromethane. The organics were combined and washed twice with saturated sodium bicarbonate, and once each with water and saturated sodium chloride. The organic was dried over sodium sulfate, concentrated in vacuo and chromatographed on 29 g flash silica gel, eluting with mixtures of ethyl acetate and hexanes. The product eluted with 30-50% EtOAc/hexanes and was concentrated in vacuo to a white solid (0.4594 g). Recrystallization from ethanol gave white crystals (0.2366 g, 12.7%). m.p.: 418-420 K. Crystals for X-Ray Crystallography were grown by slow evaporation from ethanol.
The C-bound H atoms were geometrically placed, with C—H = 0.93–0.97 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C)
Data collection: APEX2 (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C19H19NOS | Z = 4 |
Mr = 309.41 | F(000) = 656 |
Triclinic, P1 | Dx = 1.248 Mg m−3 |
Hall symbol: -P 1 | Melting point = 418–420 K |
a = 9.9954 (18) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.695 (2) Å | Cell parameters from 5499 reflections |
c = 16.397 (3) Å | θ = 2.4–27.9° |
α = 79.764 (3)° | µ = 0.20 mm−1 |
β = 83.659 (3)° | T = 298 K |
γ = 73.048 (3)° | Block, colorless |
V = 1646.8 (5) Å3 | 0.29 × 0.28 × 0.12 mm |
Bruker SMART APEX CCD diffractometer | 7089 independent reflections |
Radiation source: fine-focus sealed tube | 5751 reflections with I > 2σ(I) |
Parallel,graphite monochromator | Rint = 0.017 |
Detector resolution: 8.34 pixels mm-1 | θmax = 27.0°, θmin = 2.0° |
ϕ and ω scans | h = −11→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | k = −13→13 |
Tmin = 0.559, Tmax = 1 | l = −20→20 |
14502 measured 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)] = 0.047 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0761P)2 + 0.240P] where P = (Fo2 + 2Fc2)/3 |
7089 reflections | (Δ/σ)max < 0.001 |
397 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C19H19NOS | γ = 73.048 (3)° |
Mr = 309.41 | V = 1646.8 (5) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.9954 (18) Å | Mo Kα radiation |
b = 10.695 (2) Å | µ = 0.20 mm−1 |
c = 16.397 (3) Å | T = 298 K |
α = 79.764 (3)° | 0.29 × 0.28 × 0.12 mm |
β = 83.659 (3)° |
Bruker SMART APEX CCD diffractometer | 7089 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 5751 reflections with I > 2σ(I) |
Tmin = 0.559, Tmax = 1 | Rint = 0.017 |
14502 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.22 e Å−3 |
7089 reflections | Δρmin = −0.19 e Å−3 |
397 parameters |
Experimental. 1H NMR (CDCl3): 7.547-7.241 (10 H), 6.161 (s, 1 H), 3.120-3.094 (bd, 1H), 2.730-2.701 (bd, 1H), 2.524 (bs, 2H), 0.888 (bp, 1H), 0.763-0.609 (m, 3H). |
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 | ||
C1 | 0.85001 (16) | 0.37226 (15) | 0.11160 (9) | 0.0395 (3) | |
C2 | 0.91058 (17) | 0.31239 (15) | 0.19446 (9) | 0.0412 (3) | |
H2A | 0.8945 | 0.3818 | 0.2283 | 0.049* | |
H2B | 1.0111 | 0.2762 | 0.1858 | 0.049* | |
C3 | 0.84951 (18) | 0.20409 (16) | 0.24162 (10) | 0.0460 (4) | |
C4 | 0.9200 (2) | 0.06671 (16) | 0.22199 (11) | 0.0532 (4) | |
H4A | 0.8826 | 0.0042 | 0.2613 | 0.064* | |
H4B | 1.0193 | 0.0459 | 0.2297 | 0.064* | |
C5 | 0.97945 (16) | 0.16374 (15) | 0.05328 (9) | 0.0416 (3) | |
H5 | 0.9842 | 0.1423 | −0.0028 | 0.050* | |
C6 | 1.13156 (17) | 0.14856 (16) | 0.06834 (10) | 0.0445 (4) | |
C7 | 1.18570 (19) | 0.25627 (19) | 0.05273 (11) | 0.0529 (4) | |
H7 | 1.1274 | 0.3401 | 0.0354 | 0.063* | |
C8 | 1.3261 (2) | 0.2407 (2) | 0.06263 (14) | 0.0688 (5) | |
H8 | 1.3608 | 0.3141 | 0.0530 | 0.083* | |
C9 | 1.4136 (2) | 0.1172 (3) | 0.08663 (16) | 0.0824 (7) | |
H9 | 1.5077 | 0.1065 | 0.0934 | 0.099* | |
C10 | 1.3612 (2) | 0.0091 (3) | 0.10063 (17) | 0.0831 (7) | |
H10 | 1.4208 | −0.0748 | 0.1162 | 0.100* | |
C11 | 1.2211 (2) | 0.0236 (2) | 0.09179 (13) | 0.0629 (5) | |
H11 | 1.1870 | −0.0502 | 0.1015 | 0.075* | |
C12 | 0.81582 (16) | 0.35078 (15) | −0.02817 (9) | 0.0420 (3) | |
C13 | 0.67364 (19) | 0.3669 (2) | −0.02791 (12) | 0.0556 (4) | |
H13 | 0.6234 | 0.3463 | 0.0213 | 0.067* | |
C14 | 0.6062 (2) | 0.4137 (2) | −0.10098 (14) | 0.0681 (6) | |
H14 | 0.5103 | 0.4252 | −0.1008 | 0.082* | |
C15 | 0.6806 (2) | 0.4433 (2) | −0.17398 (13) | 0.0685 (6) | |
H15 | 0.6350 | 0.4760 | −0.2230 | 0.082* | |
C16 | 0.8219 (2) | 0.4245 (3) | −0.17412 (12) | 0.0746 (6) | |
H16 | 0.8725 | 0.4425 | −0.2237 | 0.090* | |
C17 | 0.89034 (19) | 0.3790 (2) | −0.10144 (11) | 0.0604 (5) | |
H17 | 0.9863 | 0.3675 | −0.1020 | 0.073* | |
C18 | 0.7963 (2) | 0.2142 (2) | 0.33049 (12) | 0.0688 (6) | |
H18A | 0.8083 | 0.1328 | 0.3695 | 0.083* | |
H18B | 0.8035 | 0.2894 | 0.3535 | 0.083* | |
C19 | 0.6963 (2) | 0.2399 (2) | 0.26482 (14) | 0.0671 (6) | |
H19A | 0.6423 | 0.3306 | 0.2481 | 0.081* | |
H19B | 0.6472 | 0.1742 | 0.2641 | 0.081* | |
C20 | 0.63401 (16) | 0.86157 (15) | 0.38230 (10) | 0.0409 (3) | |
C21 | 0.57843 (17) | 0.87198 (15) | 0.29878 (9) | 0.0425 (3) | |
H21A | 0.5910 | 0.9514 | 0.2637 | 0.051* | |
H21B | 0.4787 | 0.8804 | 0.3061 | 0.051* | |
C22 | 0.65069 (17) | 0.75300 (16) | 0.25537 (10) | 0.0431 (4) | |
C23 | 0.58698 (19) | 0.63898 (17) | 0.27661 (11) | 0.0497 (4) | |
H23A | 0.6275 | 0.5769 | 0.2381 | 0.060* | |
H23B | 0.4873 | 0.6721 | 0.2689 | 0.060* | |
C24 | 0.51975 (16) | 0.68075 (15) | 0.44372 (10) | 0.0411 (3) | |
H24 | 0.5180 | 0.6330 | 0.5005 | 0.049* | |
C25 | 0.36604 (16) | 0.74436 (16) | 0.42803 (9) | 0.0421 (3) | |
C26 | 0.30000 (18) | 0.87250 (18) | 0.44207 (11) | 0.0531 (4) | |
H26 | 0.3517 | 0.9230 | 0.4576 | 0.064* | |
C27 | 0.1571 (2) | 0.9260 (2) | 0.43309 (13) | 0.0671 (5) | |
H27 | 0.1140 | 1.0126 | 0.4419 | 0.081* | |
C28 | 0.0790 (2) | 0.8517 (3) | 0.41122 (14) | 0.0724 (6) | |
H28 | −0.0167 | 0.8875 | 0.4054 | 0.087* | |
C29 | 0.1442 (2) | 0.7237 (3) | 0.39810 (14) | 0.0725 (6) | |
H29 | 0.0917 | 0.6728 | 0.3838 | 0.087* | |
C30 | 0.28607 (19) | 0.6703 (2) | 0.40589 (12) | 0.0568 (5) | |
H30 | 0.3287 | 0.5840 | 0.3963 | 0.068* | |
C31 | 0.67344 (18) | 0.75204 (17) | 0.52198 (10) | 0.0470 (4) | |
C32 | 0.8144 (2) | 0.6878 (2) | 0.52163 (15) | 0.0738 (6) | |
H32 | 0.8629 | 0.6598 | 0.4734 | 0.089* | |
C33 | 0.8830 (3) | 0.6655 (3) | 0.5937 (2) | 0.1034 (10) | |
H33 | 0.9781 | 0.6213 | 0.5944 | 0.124* | |
C34 | 0.8105 (4) | 0.7087 (3) | 0.66459 (19) | 0.1085 (11) | |
H34 | 0.8575 | 0.6955 | 0.7126 | 0.130* | |
C35 | 0.6711 (3) | 0.7703 (3) | 0.66487 (15) | 0.0974 (9) | |
H35 | 0.6225 | 0.7971 | 0.7134 | 0.117* | |
C36 | 0.6012 (2) | 0.7933 (2) | 0.59327 (12) | 0.0684 (5) | |
H36 | 0.5058 | 0.8364 | 0.5932 | 0.082* | |
C37 | 0.80546 (19) | 0.72194 (19) | 0.23689 (12) | 0.0572 (5) | |
H37A | 0.8538 | 0.7791 | 0.2534 | 0.069* | |
H37B | 0.8585 | 0.6295 | 0.2411 | 0.069* | |
C38 | 0.7103 (2) | 0.7778 (2) | 0.16753 (11) | 0.0596 (5) | |
H38A | 0.7053 | 0.7191 | 0.1298 | 0.072* | |
H38B | 0.7006 | 0.8688 | 0.1421 | 0.072* | |
N1 | 0.88793 (13) | 0.30028 (12) | 0.04720 (8) | 0.0398 (3) | |
N2 | 0.60091 (13) | 0.77434 (13) | 0.44779 (8) | 0.0406 (3) | |
O1 | 0.76816 (14) | 0.48252 (11) | 0.10230 (8) | 0.0553 (3) | |
O2 | 0.70900 (14) | 0.92934 (12) | 0.39130 (8) | 0.0564 (3) | |
S1 | 0.89821 (5) | 0.04462 (4) | 0.11782 (3) | 0.05310 (14) | |
S2 | 0.61188 (5) | 0.55158 (4) | 0.38153 (3) | 0.05175 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0417 (8) | 0.0372 (8) | 0.0412 (8) | −0.0133 (6) | −0.0005 (6) | −0.0074 (6) |
C2 | 0.0484 (9) | 0.0394 (8) | 0.0380 (8) | −0.0135 (7) | −0.0009 (7) | −0.0104 (6) |
C3 | 0.0539 (10) | 0.0412 (8) | 0.0419 (8) | −0.0143 (7) | 0.0049 (7) | −0.0067 (7) |
C4 | 0.0671 (12) | 0.0396 (8) | 0.0484 (9) | −0.0129 (8) | 0.0057 (8) | −0.0035 (7) |
C5 | 0.0443 (9) | 0.0386 (8) | 0.0405 (8) | −0.0067 (7) | −0.0010 (7) | −0.0116 (6) |
C6 | 0.0427 (9) | 0.0484 (9) | 0.0381 (8) | −0.0056 (7) | 0.0009 (7) | −0.0093 (7) |
C7 | 0.0458 (9) | 0.0575 (10) | 0.0513 (10) | −0.0121 (8) | 0.0016 (8) | −0.0042 (8) |
C8 | 0.0521 (11) | 0.0857 (15) | 0.0699 (13) | −0.0261 (11) | 0.0023 (10) | −0.0077 (11) |
C9 | 0.0423 (11) | 0.109 (2) | 0.0902 (17) | −0.0129 (12) | −0.0071 (11) | −0.0121 (14) |
C10 | 0.0531 (12) | 0.0779 (15) | 0.1000 (18) | 0.0089 (11) | −0.0135 (12) | −0.0060 (13) |
C11 | 0.0537 (11) | 0.0524 (10) | 0.0732 (13) | −0.0014 (9) | −0.0056 (9) | −0.0066 (9) |
C12 | 0.0397 (8) | 0.0455 (8) | 0.0402 (8) | −0.0090 (7) | −0.0046 (6) | −0.0087 (7) |
C13 | 0.0430 (9) | 0.0745 (12) | 0.0529 (10) | −0.0214 (9) | −0.0018 (8) | −0.0109 (9) |
C14 | 0.0445 (10) | 0.0924 (15) | 0.0718 (13) | −0.0186 (10) | −0.0175 (9) | −0.0166 (11) |
C15 | 0.0672 (13) | 0.0852 (15) | 0.0533 (11) | −0.0169 (11) | −0.0242 (10) | −0.0062 (10) |
C16 | 0.0642 (13) | 0.1120 (18) | 0.0427 (10) | −0.0242 (13) | −0.0038 (9) | 0.0008 (11) |
C17 | 0.0408 (9) | 0.0904 (14) | 0.0452 (10) | −0.0141 (9) | −0.0019 (7) | −0.0049 (9) |
C18 | 0.0964 (16) | 0.0564 (11) | 0.0489 (10) | −0.0207 (11) | 0.0187 (11) | −0.0109 (9) |
C19 | 0.0631 (12) | 0.0542 (11) | 0.0835 (15) | −0.0214 (9) | 0.0233 (11) | −0.0176 (10) |
C20 | 0.0396 (8) | 0.0381 (8) | 0.0452 (8) | −0.0127 (6) | 0.0048 (7) | −0.0085 (6) |
C21 | 0.0460 (9) | 0.0389 (8) | 0.0412 (8) | −0.0128 (7) | 0.0034 (7) | −0.0045 (6) |
C22 | 0.0428 (9) | 0.0442 (8) | 0.0436 (8) | −0.0143 (7) | 0.0055 (7) | −0.0112 (7) |
C23 | 0.0496 (10) | 0.0506 (9) | 0.0547 (10) | −0.0197 (8) | 0.0072 (8) | −0.0198 (8) |
C24 | 0.0401 (8) | 0.0423 (8) | 0.0424 (8) | −0.0181 (7) | 0.0015 (6) | −0.0020 (6) |
C25 | 0.0373 (8) | 0.0523 (9) | 0.0372 (8) | −0.0174 (7) | 0.0038 (6) | −0.0039 (7) |
C26 | 0.0460 (10) | 0.0578 (10) | 0.0552 (10) | −0.0166 (8) | 0.0067 (8) | −0.0102 (8) |
C27 | 0.0503 (11) | 0.0664 (12) | 0.0701 (13) | −0.0030 (10) | 0.0111 (10) | −0.0039 (10) |
C28 | 0.0372 (10) | 0.1025 (18) | 0.0692 (13) | −0.0149 (11) | −0.0012 (9) | −0.0005 (12) |
C29 | 0.0471 (11) | 0.1038 (18) | 0.0773 (14) | −0.0349 (12) | −0.0018 (10) | −0.0197 (13) |
C30 | 0.0472 (10) | 0.0675 (12) | 0.0627 (11) | −0.0259 (9) | 0.0024 (8) | −0.0150 (9) |
C31 | 0.0441 (9) | 0.0521 (9) | 0.0480 (9) | −0.0211 (7) | −0.0066 (7) | −0.0008 (7) |
C32 | 0.0497 (11) | 0.0854 (15) | 0.0829 (15) | −0.0173 (11) | −0.0134 (11) | −0.0006 (12) |
C33 | 0.0674 (16) | 0.119 (2) | 0.122 (3) | −0.0301 (16) | −0.0475 (17) | 0.016 (2) |
C34 | 0.126 (3) | 0.135 (3) | 0.0827 (19) | −0.067 (2) | −0.0608 (19) | 0.0192 (18) |
C35 | 0.119 (2) | 0.132 (2) | 0.0551 (13) | −0.052 (2) | −0.0197 (14) | −0.0131 (14) |
C36 | 0.0685 (13) | 0.0908 (15) | 0.0495 (11) | −0.0253 (12) | −0.0055 (9) | −0.0134 (10) |
C37 | 0.0448 (10) | 0.0526 (10) | 0.0742 (13) | −0.0167 (8) | 0.0136 (9) | −0.0151 (9) |
C38 | 0.0691 (12) | 0.0647 (11) | 0.0480 (10) | −0.0261 (10) | 0.0150 (9) | −0.0152 (8) |
N1 | 0.0399 (7) | 0.0400 (7) | 0.0371 (6) | −0.0048 (5) | −0.0042 (5) | −0.0092 (5) |
N2 | 0.0396 (7) | 0.0452 (7) | 0.0403 (7) | −0.0194 (6) | −0.0011 (5) | −0.0029 (5) |
O1 | 0.0651 (8) | 0.0390 (6) | 0.0549 (7) | 0.0005 (6) | −0.0076 (6) | −0.0120 (5) |
O2 | 0.0652 (8) | 0.0551 (7) | 0.0601 (7) | −0.0360 (6) | −0.0013 (6) | −0.0068 (6) |
S1 | 0.0614 (3) | 0.0428 (2) | 0.0607 (3) | −0.0205 (2) | 0.0047 (2) | −0.01759 (19) |
S2 | 0.0507 (3) | 0.0371 (2) | 0.0660 (3) | −0.01365 (18) | 0.0064 (2) | −0.00759 (19) |
C1—C2 | 1.506 (2) | C20—C21 | 1.508 (2) |
C1—N1 | 1.3718 (18) | C20—N2 | 1.3706 (19) |
C1—O1 | 1.2183 (19) | C20—O2 | 1.2199 (18) |
C2—H2A | 0.9700 | C21—H21A | 0.9700 |
C2—H2B | 0.9700 | C21—H21B | 0.9700 |
C2—C3 | 1.517 (2) | C21—C22 | 1.523 (2) |
C3—C4 | 1.508 (2) | C22—C23 | 1.506 (2) |
C3—C18 | 1.506 (2) | C22—C37 | 1.493 (2) |
C3—C19 | 1.489 (3) | C22—C38 | 1.505 (2) |
C4—H4A | 0.9700 | C23—H23A | 0.9700 |
C4—H4B | 0.9700 | C23—H23B | 0.9700 |
C4—S1 | 1.8100 (18) | C23—S2 | 1.8118 (19) |
C5—H5 | 0.9800 | C24—H24 | 0.9800 |
C5—C6 | 1.524 (2) | C24—C25 | 1.518 (2) |
C5—N1 | 1.4726 (19) | C24—N2 | 1.4744 (19) |
C5—S1 | 1.8267 (17) | C24—S2 | 1.8297 (16) |
C6—C7 | 1.383 (2) | C25—C26 | 1.385 (2) |
C6—C11 | 1.390 (2) | C25—C30 | 1.391 (2) |
C7—H7 | 0.9300 | C26—H26 | 0.9300 |
C7—C8 | 1.388 (3) | C26—C27 | 1.389 (3) |
C8—H8 | 0.9300 | C27—H27 | 0.9300 |
C8—C9 | 1.372 (3) | C27—C28 | 1.376 (3) |
C9—H9 | 0.9300 | C28—H28 | 0.9300 |
C9—C10 | 1.377 (4) | C28—C29 | 1.378 (3) |
C10—H10 | 0.9300 | C29—H29 | 0.9300 |
C10—C11 | 1.384 (3) | C29—C30 | 1.377 (3) |
C11—H11 | 0.9300 | C30—H30 | 0.9300 |
C12—C13 | 1.380 (2) | C31—C32 | 1.376 (3) |
C12—C17 | 1.376 (2) | C31—C36 | 1.376 (3) |
C12—N1 | 1.4391 (19) | C31—N2 | 1.433 (2) |
C13—H13 | 0.9300 | C32—H32 | 0.9300 |
C13—C14 | 1.381 (3) | C32—C33 | 1.380 (3) |
C14—H14 | 0.9300 | C33—H33 | 0.9300 |
C14—C15 | 1.375 (3) | C33—C34 | 1.379 (4) |
C15—H15 | 0.9300 | C34—H34 | 0.9300 |
C15—C16 | 1.367 (3) | C34—C35 | 1.356 (4) |
C16—H16 | 0.9300 | C35—H35 | 0.9300 |
C16—C17 | 1.380 (3) | C35—C36 | 1.380 (3) |
C17—H17 | 0.9300 | C36—H36 | 0.9300 |
C18—H18A | 0.9700 | C37—H37A | 0.9700 |
C18—H18B | 0.9700 | C37—H37B | 0.9700 |
C18—C19 | 1.485 (3) | C37—C38 | 1.491 (3) |
C19—H19A | 0.9700 | C38—H38A | 0.9700 |
C19—H19B | 0.9700 | C38—H38B | 0.9700 |
N1—C1—C2 | 118.89 (13) | C20—C21—H21B | 109.0 |
O1—C1—C2 | 120.36 (13) | C20—C21—C22 | 112.84 (13) |
O1—C1—N1 | 120.74 (14) | H21A—C21—H21B | 107.8 |
C1—C2—H2A | 108.8 | C22—C21—H21A | 109.0 |
C1—C2—H2B | 108.8 | C22—C21—H21B | 109.0 |
C1—C2—C3 | 113.86 (13) | C23—C22—C21 | 115.21 (13) |
H2A—C2—H2B | 107.7 | C37—C22—C21 | 118.26 (14) |
C3—C2—H2A | 108.8 | C37—C22—C23 | 117.80 (14) |
C3—C2—H2B | 108.8 | C37—C22—C38 | 59.63 (12) |
C4—C3—C2 | 115.73 (14) | C38—C22—C21 | 118.20 (14) |
C18—C3—C2 | 117.56 (14) | C38—C22—C23 | 116.52 (14) |
C18—C3—C4 | 116.33 (15) | C22—C23—H23A | 108.7 |
C19—C3—C2 | 117.76 (15) | C22—C23—H23B | 108.7 |
C19—C3—C4 | 118.35 (15) | C22—C23—S2 | 114.33 (12) |
C19—C3—C18 | 59.44 (13) | H23A—C23—H23B | 107.6 |
C3—C4—H4A | 108.7 | S2—C23—H23A | 108.7 |
C3—C4—H4B | 108.7 | S2—C23—H23B | 108.7 |
C3—C4—S1 | 114.30 (13) | C25—C24—H24 | 103.9 |
H4A—C4—H4B | 107.6 | C25—C24—S2 | 115.68 (11) |
S1—C4—H4A | 108.7 | N2—C24—H24 | 103.9 |
S1—C4—H4B | 108.7 | N2—C24—C25 | 114.89 (13) |
C6—C5—H5 | 103.9 | N2—C24—S2 | 112.78 (10) |
C6—C5—S1 | 116.07 (11) | S2—C24—H24 | 103.9 |
N1—C5—H5 | 103.9 | C26—C25—C24 | 121.14 (14) |
N1—C5—C6 | 114.66 (13) | C26—C25—C30 | 118.65 (16) |
N1—C5—S1 | 112.51 (11) | C30—C25—C24 | 119.99 (15) |
S1—C5—H5 | 103.9 | C25—C26—H26 | 119.8 |
C7—C6—C5 | 121.04 (15) | C25—C26—C27 | 120.44 (18) |
C7—C6—C11 | 118.82 (17) | C27—C26—H26 | 119.8 |
C11—C6—C5 | 119.94 (16) | C26—C27—H27 | 119.8 |
C6—C7—H7 | 119.6 | C28—C27—C26 | 120.4 (2) |
C6—C7—C8 | 120.74 (18) | C28—C27—H27 | 119.8 |
C8—C7—H7 | 119.6 | C27—C28—H28 | 120.4 |
C7—C8—H8 | 119.9 | C27—C28—C29 | 119.28 (19) |
C9—C8—C7 | 120.1 (2) | C29—C28—H28 | 120.4 |
C9—C8—H8 | 119.9 | C28—C29—H29 | 119.6 |
C8—C9—H9 | 120.2 | C30—C29—C28 | 120.8 (2) |
C8—C9—C10 | 119.5 (2) | C30—C29—H29 | 119.6 |
C10—C9—H9 | 120.2 | C25—C30—H30 | 119.8 |
C9—C10—H10 | 119.6 | C29—C30—C25 | 120.46 (19) |
C9—C10—C11 | 120.9 (2) | C29—C30—H30 | 119.8 |
C11—C10—H10 | 119.6 | C32—C31—N2 | 119.67 (17) |
C6—C11—H11 | 120.0 | C36—C31—C32 | 120.55 (19) |
C10—C11—C6 | 119.9 (2) | C36—C31—N2 | 119.77 (16) |
C10—C11—H11 | 120.0 | C31—C32—H32 | 120.4 |
C13—C12—N1 | 120.51 (15) | C31—C32—C33 | 119.2 (3) |
C17—C12—C13 | 119.90 (16) | C33—C32—H32 | 120.4 |
C17—C12—N1 | 119.56 (15) | C32—C33—H33 | 120.0 |
C12—C13—H13 | 120.1 | C34—C33—C32 | 119.9 (3) |
C12—C13—C14 | 119.84 (17) | C34—C33—H33 | 120.0 |
C14—C13—H13 | 120.1 | C33—C34—H34 | 119.7 |
C13—C14—H14 | 119.9 | C35—C34—C33 | 120.5 (2) |
C15—C14—C13 | 120.17 (18) | C35—C34—H34 | 119.7 |
C15—C14—H14 | 119.9 | C34—C35—H35 | 120.0 |
C14—C15—H15 | 120.2 | C34—C35—C36 | 120.1 (3) |
C16—C15—C14 | 119.70 (18) | C36—C35—H35 | 120.0 |
C16—C15—H15 | 120.2 | C31—C36—C35 | 119.6 (2) |
C15—C16—H16 | 119.6 | C31—C36—H36 | 120.2 |
C15—C16—C17 | 120.72 (19) | C35—C36—H36 | 120.2 |
C17—C16—H16 | 119.6 | C22—C37—H37A | 117.7 |
C12—C17—C16 | 119.66 (18) | C22—C37—H37B | 117.7 |
C12—C17—H17 | 120.2 | H37A—C37—H37B | 114.8 |
C16—C17—H17 | 120.2 | C38—C37—C22 | 60.61 (12) |
C3—C18—H18A | 117.8 | C38—C37—H37A | 117.7 |
C3—C18—H18B | 117.8 | C38—C37—H37B | 117.7 |
H18A—C18—H18B | 114.9 | C22—C38—H38A | 117.8 |
C19—C18—C3 | 59.69 (13) | C22—C38—H38B | 117.8 |
C19—C18—H18A | 117.8 | C37—C38—C22 | 59.76 (12) |
C19—C18—H18B | 117.8 | C37—C38—H38A | 117.8 |
C3—C19—H19A | 117.7 | C37—C38—H38B | 117.8 |
C3—C19—H19B | 117.7 | H38A—C38—H38B | 114.9 |
C18—C19—C3 | 60.87 (13) | C1—N1—C5 | 124.94 (13) |
C18—C19—H19A | 117.7 | C1—N1—C12 | 118.35 (13) |
C18—C19—H19B | 117.7 | C12—N1—C5 | 115.82 (11) |
H19A—C19—H19B | 114.8 | C20—N2—C24 | 125.52 (13) |
N2—C20—C21 | 119.50 (13) | C20—N2—C31 | 117.58 (13) |
O2—C20—C21 | 120.25 (14) | C31—N2—C24 | 115.62 (12) |
O2—C20—N2 | 120.24 (15) | C4—S1—C5 | 102.63 (8) |
C20—C21—H21A | 109.0 | C23—S2—C24 | 102.03 (8) |
C1—C2—C3—C4 | 87.12 (18) | C25—C24—N2—C20 | −68.64 (19) |
C1—C2—C3—C18 | −129.09 (17) | C25—C24—N2—C31 | 124.65 (15) |
C1—C2—C3—C19 | −61.01 (19) | C25—C24—S2—C23 | 57.87 (12) |
C2—C1—N1—C5 | 3.3 (2) | C25—C26—C27—C28 | 0.9 (3) |
C2—C1—N1—C12 | 171.94 (13) | C26—C25—C30—C29 | 0.0 (3) |
C2—C3—C4—S1 | −67.20 (18) | C26—C27—C28—C29 | −0.2 (3) |
C2—C3—C18—C19 | 107.58 (18) | C27—C28—C29—C30 | −0.6 (3) |
C2—C3—C19—C18 | −107.24 (17) | C28—C29—C30—C25 | 0.7 (3) |
C3—C4—S1—C5 | 60.62 (15) | C30—C25—C26—C27 | −0.8 (3) |
C4—C3—C18—C19 | −108.84 (18) | C31—C32—C33—C34 | −0.7 (4) |
C4—C3—C19—C18 | 105.47 (18) | C32—C31—C36—C35 | 0.2 (3) |
C5—C6—C7—C8 | −176.77 (16) | C32—C31—N2—C20 | −68.0 (2) |
C5—C6—C11—C10 | 176.14 (19) | C32—C31—N2—C24 | 99.79 (19) |
C6—C5—N1—C1 | −67.81 (19) | C32—C33—C34—C35 | 1.7 (5) |
C6—C5—N1—C12 | 123.27 (14) | C33—C34—C35—C36 | −1.7 (5) |
C6—C5—S1—C4 | 56.71 (12) | C34—C35—C36—C31 | 0.7 (4) |
C6—C7—C8—C9 | 1.3 (3) | C36—C31—C32—C33 | −0.2 (3) |
C7—C6—C11—C10 | 1.2 (3) | C36—C31—N2—C20 | 112.91 (19) |
C7—C8—C9—C10 | 0.1 (4) | C36—C31—N2—C24 | −79.3 (2) |
C8—C9—C10—C11 | −0.8 (4) | C37—C22—C23—S2 | 77.21 (18) |
C9—C10—C11—C6 | 0.1 (4) | C38—C22—C23—S2 | 145.15 (14) |
C11—C6—C7—C8 | −1.9 (3) | N1—C1—C2—C3 | −73.44 (18) |
C12—C13—C14—C15 | 0.5 (3) | N1—C5—C6—C7 | −18.2 (2) |
C13—C12—C17—C16 | 0.6 (3) | N1—C5—C6—C11 | 167.02 (15) |
C13—C12—N1—C1 | −62.6 (2) | N1—C5—S1—C4 | −78.17 (12) |
C13—C12—N1—C5 | 107.12 (17) | N1—C12—C13—C14 | −179.08 (17) |
C13—C14—C15—C16 | 0.9 (4) | N1—C12—C17—C16 | 178.48 (19) |
C14—C15—C16—C17 | −1.5 (4) | N2—C20—C21—C22 | −72.77 (18) |
C15—C16—C17—C12 | 0.8 (4) | N2—C24—C25—C26 | −18.8 (2) |
C17—C12—C13—C14 | −1.2 (3) | N2—C24—C25—C30 | 166.66 (15) |
C17—C12—N1—C1 | 119.57 (18) | N2—C24—S2—C23 | −77.24 (12) |
C17—C12—N1—C5 | −70.7 (2) | N2—C31—C32—C33 | −179.3 (2) |
C18—C3—C4—S1 | 148.55 (15) | N2—C31—C36—C35 | 179.3 (2) |
C19—C3—C4—S1 | 80.74 (19) | O1—C1—C2—C3 | 106.17 (17) |
C20—C21—C22—C23 | 87.61 (17) | O1—C1—N1—C5 | −176.34 (15) |
C20—C21—C22—C37 | −59.3 (2) | O1—C1—N1—C12 | −7.7 (2) |
C20—C21—C22—C38 | −128.05 (16) | O2—C20—C21—C22 | 106.51 (17) |
C21—C20—N2—C24 | 3.7 (2) | O2—C20—N2—C24 | −175.58 (15) |
C21—C20—N2—C31 | 170.18 (14) | O2—C20—N2—C31 | −9.1 (2) |
C21—C22—C23—S2 | −69.90 (17) | S1—C5—C6—C7 | −152.08 (13) |
C21—C22—C37—C38 | −107.87 (17) | S1—C5—C6—C11 | 33.10 (19) |
C21—C22—C38—C37 | 107.97 (17) | S1—C5—N1—C1 | 67.73 (17) |
C22—C23—S2—C24 | 62.03 (13) | S1—C5—N1—C12 | −101.19 (13) |
C23—C22—C37—C38 | 106.03 (17) | S2—C24—C25—C26 | −152.98 (13) |
C23—C22—C38—C37 | −108.16 (17) | S2—C24—C25—C30 | 32.50 (19) |
C24—C25—C26—C27 | −175.41 (16) | S2—C24—N2—C20 | 66.84 (18) |
C24—C25—C30—C29 | 174.70 (17) | S2—C24—N2—C31 | −99.88 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18A···O2i | 0.97 | 2.60 | 3.364 (2) | 136 |
C38—H38A···O1 | 0.97 | 2.53 | 3.384 (2) | 146 |
Symmetry code: (i) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18A···O2i | 0.97 | 2.60 | 3.364 (2) | 136.0 |
C38—H38A···O1 | 0.97 | 2.53 | 3.384 (2) | 146.3 |
Symmetry code: (i) x, y−1, z. |
Acknowledgements
We acknowledge NSF funding (CHEM-0131112) for the X-ray diffractometer. We also express gratitude to Oakwood Products, Inc. for the gift of [1-(sulfanylmethyl)cyclopropyl]acetic acid, and to Euticals for the gift of T3P in 2-methyltetrahydrofuran.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The seven-membered 1,3-thiazepan-4-one ring system is of biological interest, as exemplified by the investigational compound omapatrilat (Graul et al., 1999; Robl et al., 1997; Tabrizchi, 2001). As part of our studies of cyclic 1,3-thiaza-4-one compounds, we report the synthesis and structure of the novel title compound. The title molecule was synthesized by condensation of N-[phenylmethylidene]aniline with [1-(sulfanylmethyl)cyclopropyl]acetic acid in the presence of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P) and pyridine (Dunetz et al., 2011; Unsworth et al., 2013). We report here the crystal structure of the title compound which crystallizes with two independent molecules, A & B, in the asymmetric unit. In the title compound (Fig. 1), the 1,3-thiazepan-4-one ring adopts a chair type conformation. The dihedral angles formed by the two benzene rings are 65.28 (8)° for molecule A and 60.31 (9)° for molecule B, respectively. In the crystal packing (Fig. 2), molecules are connected by weak C–H···O interactions (Table 1), resulting in a three-dimensional network.