organic compounds
2-(3-Chlorophenyl)-3,4-dihydrobenzo[f][1,4]oxazepin-5(2H)-one
aSichuan Academy of Medical Sciences & Sichuan Provincial People's Hospital, Hospital of the University of Electronic Science and Technology of China, Personalized Drug Therapy Key Laboratory of Sichuan Province, Chengdu, Sichuan Province 610072, People's Republic of China, and bDalian Lubricating Oil Research & Development Institute, PetroChina, Dalian 116032, People's Republic of China
*Correspondence e-mail: chengliang_rhy@petrochina.com.cn
In the title compound, C15H12ClNO2, the dihedral angle between the two benzene rings is 73.45 (11)°. The central seven-membered ring is in a psuedo-boat conformation. In the crystal, pairs of molecules are linked by N—H⋯O hydrogen bonds, forming inversion dimers.
CCDC reference: 1551778
Structure description
The development of benzo[f][1,4]oxazepinone derivatives for medical applications is a research topic of increasing interest because of their easy preparation, good stability and high nanomolar activity (Li et al., 2016). It is believed that the derivatives can be modified structurally by using different and (Krapcho & Turk, 1966). We report here the synthesis and the structure of the title compoun whose molecular structure is shown in Fig. 1. The dihedral angle between the two benzene rings (C2–C7 and C10–C15) is 73.45 (11)°. The central seven-membered ring is in a psuedo-boat conformation with C9 forming the prow and C2/C7 forming the stern. In the crystal, pairs of molecules are linked by N—H⋯O hydrogen bonds, forming inversion dimers (Table 1, Fig. 2).
Synthesis and crystallization
A 25 ml round-bottom flask was charged with 3-chlorobenzaldehyde (0.5 mmol), phenylamine (0.75 mmol), I2 (0.15 mmol) and 1-(2-hydroxyphenyl)ethan-1-one (0.6 mmol) and methanol (10 mL) and stirred at 318 K. After the reaction was complete (as determined by TLC), the solvent was evaporated and 10 mL of saturated Na2S2O3 was added. The solution was extracted with CH2Cl2 (three × 10 mL). The organic layers were washed with saturated NaCl solution and then with ice–water. The solution was dried over Na2SO4 and concentrated under vacuum to a crude solid. The crude solid (6 mmol) and NaN3 (500 mg) were added to a round-bottom flask with 9 mL of CH3COOH and stirred at 273 K. 3 mL of concentrated H2SO4 was then added and stirred at 318 K. After the reaction was complete (as determined by TLC), the solvent was neutralized with NaHCO3. The solution was extracted with ethyl acetate. This was chromatographed on flash silica gel, eluting with 75% cyclohexane and 25% ethyl acetate and concentrated to a solid, giving 1.0 g of product (69% yield), m.p. 352.2–354.3 K. Crystals for X-ray crystallography were grown by slow evaporation of a solution of the title compound in methanol and water.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1551778
https://doi.org/10.1107/S2414314618005874/lh5867sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618005874/lh5867Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314618005874/lh5867Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2414314618005874/lh5867Isup4.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2414314618005874/lh5867Isup5.cml
Data collection: CrysAlis PRO (Agilent, 2014); cell
CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C15H12ClNO2 | Z = 2 |
Mr = 273.71 | F(000) = 284 |
Triclinic, P1 | Dx = 1.377 Mg m−3 |
a = 7.2162 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.0068 (14) Å | Cell parameters from 1590 reflections |
c = 11.650 (3) Å | θ = 3.5–27.6° |
α = 80.123 (17)° | µ = 0.29 mm−1 |
β = 84.570 (18)° | T = 293 K |
γ = 88.084 (15)° | , colorless |
V = 660.0 (2) Å3 | 0.4 × 0.35 × 0.3 mm |
Agilent Xcalibur, Eos diffractometer | 2678 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2002 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 16.0874 pixels mm-1 | θmax = 26.4°, θmin = 3.2° |
ω scans | h = −9→8 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −7→9 |
Tmin = 0.896, Tmax = 1.000 | l = −14→14 |
4864 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.2184P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2678 reflections | Δρmax = 0.29 e Å−3 |
176 parameters | Δρmin = −0.32 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 1.11743 (9) | 0.53184 (10) | 0.26327 (7) | 0.0761 (3) | |
O1 | 0.52072 (19) | 0.63356 (16) | 0.32657 (12) | 0.0408 (4) | |
O2 | 0.3115 (2) | 1.0113 (2) | 0.10901 (13) | 0.0595 (5) | |
N1 | 0.5962 (3) | 0.8897 (2) | 0.13595 (14) | 0.0419 (4) | |
H1 | 0.668 (3) | 0.905 (2) | 0.0428 (18) | 0.045 (6)* | |
C1 | 0.4288 (3) | 0.9404 (3) | 0.17520 (17) | 0.0425 (5) | |
C2 | 0.3808 (3) | 0.9133 (3) | 0.30392 (17) | 0.0390 (5) | |
C3 | 0.2785 (3) | 1.0356 (3) | 0.3555 (2) | 0.0492 (5) | |
H3 | 0.2416 | 1.1353 | 0.3091 | 0.059* | |
C4 | 0.2312 (3) | 1.0108 (3) | 0.4745 (2) | 0.0507 (6) | |
H4 | 0.1646 | 1.0942 | 0.5083 | 0.061* | |
C5 | 0.2823 (3) | 0.8631 (3) | 0.54278 (19) | 0.0509 (6) | |
H5 | 0.2488 | 0.8460 | 0.6229 | 0.061* | |
C6 | 0.3830 (3) | 0.7394 (3) | 0.49404 (18) | 0.0450 (5) | |
H6 | 0.4171 | 0.6392 | 0.5410 | 0.054* | |
C7 | 0.4330 (3) | 0.7651 (2) | 0.37516 (17) | 0.0354 (4) | |
C8 | 0.7130 (3) | 0.6560 (2) | 0.28206 (16) | 0.0362 (4) | |
H8 | 0.7901 | 0.6389 | 0.3481 | 0.043* | |
C9 | 0.7429 (3) | 0.8348 (2) | 0.21354 (17) | 0.0406 (5) | |
H9A | 0.7467 | 0.9132 | 0.2681 | 0.049* | |
H9B | 0.8622 | 0.8383 | 0.1673 | 0.049* | |
C10 | 0.7614 (3) | 0.5194 (2) | 0.20902 (16) | 0.0342 (4) | |
C11 | 0.9417 (3) | 0.4563 (3) | 0.19450 (18) | 0.0426 (5) | |
C12 | 0.9891 (3) | 0.3338 (3) | 0.1260 (2) | 0.0522 (6) | |
H12 | 1.1112 | 0.2935 | 0.1179 | 0.063* | |
C13 | 0.8542 (4) | 0.2723 (3) | 0.0700 (2) | 0.0554 (6) | |
H13 | 0.8845 | 0.1900 | 0.0236 | 0.066* | |
C14 | 0.6739 (4) | 0.3327 (3) | 0.0825 (2) | 0.0551 (6) | |
H14 | 0.5826 | 0.2910 | 0.0443 | 0.066* | |
C15 | 0.6279 (3) | 0.4545 (3) | 0.15140 (19) | 0.0445 (5) | |
H15 | 0.5054 | 0.4939 | 0.1593 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0405 (4) | 0.0984 (6) | 0.0982 (6) | 0.0052 (3) | −0.0205 (3) | −0.0348 (4) |
O1 | 0.0441 (8) | 0.0336 (7) | 0.0422 (8) | 0.0024 (6) | 0.0056 (6) | −0.0054 (6) |
O2 | 0.0676 (11) | 0.0680 (11) | 0.0408 (9) | 0.0247 (9) | −0.0110 (8) | −0.0048 (8) |
N1 | 0.0568 (11) | 0.0367 (9) | 0.0304 (9) | 0.0036 (8) | −0.0024 (8) | −0.0020 (7) |
C1 | 0.0573 (14) | 0.0360 (11) | 0.0341 (10) | 0.0076 (10) | −0.0080 (10) | −0.0054 (9) |
C2 | 0.0426 (11) | 0.0397 (11) | 0.0352 (10) | 0.0050 (9) | −0.0057 (9) | −0.0074 (8) |
C3 | 0.0537 (14) | 0.0438 (12) | 0.0508 (13) | 0.0123 (10) | −0.0111 (11) | −0.0091 (10) |
C4 | 0.0486 (13) | 0.0533 (14) | 0.0530 (13) | 0.0093 (11) | −0.0001 (11) | −0.0210 (11) |
C5 | 0.0540 (14) | 0.0579 (14) | 0.0405 (12) | −0.0033 (11) | 0.0080 (11) | −0.0133 (11) |
C6 | 0.0493 (13) | 0.0441 (12) | 0.0389 (11) | 0.0008 (10) | 0.0018 (10) | −0.0032 (9) |
C7 | 0.0359 (10) | 0.0341 (10) | 0.0361 (10) | 0.0024 (8) | −0.0018 (8) | −0.0073 (8) |
C8 | 0.0395 (11) | 0.0366 (11) | 0.0325 (10) | 0.0033 (8) | −0.0059 (8) | −0.0053 (8) |
C9 | 0.0456 (12) | 0.0367 (11) | 0.0392 (11) | −0.0014 (9) | −0.0009 (9) | −0.0074 (9) |
C10 | 0.0373 (10) | 0.0315 (10) | 0.0314 (9) | 0.0024 (8) | −0.0015 (8) | 0.0001 (8) |
C11 | 0.0398 (11) | 0.0429 (12) | 0.0432 (11) | 0.0030 (9) | −0.0029 (9) | −0.0034 (9) |
C12 | 0.0510 (14) | 0.0461 (13) | 0.0550 (14) | 0.0153 (11) | 0.0076 (11) | −0.0053 (11) |
C13 | 0.0765 (18) | 0.0374 (12) | 0.0513 (13) | 0.0048 (12) | 0.0069 (13) | −0.0130 (10) |
C14 | 0.0655 (16) | 0.0495 (14) | 0.0549 (14) | −0.0079 (12) | −0.0089 (12) | −0.0188 (11) |
C15 | 0.0414 (12) | 0.0434 (12) | 0.0506 (12) | 0.0031 (9) | −0.0073 (10) | −0.0118 (10) |
Cl1—C11 | 1.739 (2) | C6—C7 | 1.380 (3) |
O1—C7 | 1.386 (2) | C8—H8 | 0.9800 |
O1—C8 | 1.441 (2) | C8—C9 | 1.527 (3) |
O2—C1 | 1.255 (3) | C8—C10 | 1.510 (3) |
N1—H1 | 1.14 (2) | C9—H9A | 0.9700 |
N1—C1 | 1.326 (3) | C9—H9B | 0.9700 |
N1—C9 | 1.464 (3) | C10—C11 | 1.386 (3) |
C1—C2 | 1.487 (3) | C10—C15 | 1.387 (3) |
C2—C3 | 1.391 (3) | C11—C12 | 1.383 (3) |
C2—C7 | 1.389 (3) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C12—C13 | 1.370 (3) |
C3—C4 | 1.378 (3) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C13—C14 | 1.376 (3) |
C4—C5 | 1.368 (3) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C14—C15 | 1.380 (3) |
C5—C6 | 1.378 (3) | C15—H15 | 0.9300 |
C6—H6 | 0.9300 | ||
C7—O1—C8 | 117.07 (14) | C9—C8—H8 | 108.8 |
C1—N1—H1 | 130.6 (11) | C10—C8—H8 | 108.8 |
C1—N1—C9 | 122.40 (17) | C10—C8—C9 | 113.14 (15) |
C9—N1—H1 | 105.8 (11) | N1—C9—C8 | 112.49 (16) |
O2—C1—N1 | 123.09 (19) | N1—C9—H9A | 109.1 |
O2—C1—C2 | 119.0 (2) | N1—C9—H9B | 109.1 |
N1—C1—C2 | 117.87 (19) | C8—C9—H9A | 109.1 |
C3—C2—C1 | 120.30 (19) | C8—C9—H9B | 109.1 |
C7—C2—C1 | 121.27 (18) | H9A—C9—H9B | 107.8 |
C7—C2—C3 | 118.42 (19) | C11—C10—C8 | 121.44 (18) |
C2—C3—H3 | 119.6 | C11—C10—C15 | 117.21 (18) |
C4—C3—C2 | 120.8 (2) | C15—C10—C8 | 121.34 (18) |
C4—C3—H3 | 119.6 | C10—C11—Cl1 | 120.02 (16) |
C3—C4—H4 | 120.1 | C12—C11—Cl1 | 117.79 (18) |
C5—C4—C3 | 119.8 (2) | C12—C11—C10 | 122.2 (2) |
C5—C4—H4 | 120.1 | C11—C12—H12 | 120.4 |
C4—C5—H5 | 119.7 | C13—C12—C11 | 119.3 (2) |
C4—C5—C6 | 120.7 (2) | C13—C12—H12 | 120.4 |
C6—C5—H5 | 119.7 | C12—C13—H13 | 120.0 |
C5—C6—H6 | 120.2 | C12—C13—C14 | 119.9 (2) |
C5—C6—C7 | 119.6 (2) | C14—C13—H13 | 120.0 |
C7—C6—H6 | 120.2 | C13—C14—H14 | 119.8 |
O1—C7—C2 | 120.41 (17) | C13—C14—C15 | 120.4 (2) |
C6—C7—O1 | 118.60 (18) | C15—C14—H14 | 119.8 |
C6—C7—C2 | 120.71 (19) | C10—C15—H15 | 119.5 |
O1—C8—H8 | 108.8 | C14—C15—C10 | 121.0 (2) |
O1—C8—C9 | 110.50 (16) | C14—C15—H15 | 119.5 |
O1—C8—C10 | 106.64 (15) | ||
Cl1—C11—C12—C13 | −179.61 (17) | C7—O1—C8—C10 | −166.47 (15) |
O1—C8—C9—N1 | −43.5 (2) | C7—C2—C3—C4 | 0.4 (3) |
O1—C8—C10—C11 | −152.15 (17) | C8—O1—C7—C2 | 74.4 (2) |
O1—C8—C10—C15 | 29.4 (2) | C8—O1—C7—C6 | −111.7 (2) |
O2—C1—C2—C3 | −38.0 (3) | C8—C10—C11—Cl1 | 1.2 (3) |
O2—C1—C2—C7 | 140.7 (2) | C8—C10—C11—C12 | −178.64 (19) |
N1—C1—C2—C3 | 141.2 (2) | C8—C10—C15—C14 | 178.42 (19) |
N1—C1—C2—C7 | −40.1 (3) | C9—N1—C1—O2 | 168.99 (19) |
C1—N1—C9—C8 | 76.9 (2) | C9—N1—C1—C2 | −10.1 (3) |
C1—C2—C3—C4 | 179.2 (2) | C9—C8—C10—C11 | 86.2 (2) |
C1—C2—C7—O1 | −4.4 (3) | C9—C8—C10—C15 | −92.3 (2) |
C1—C2—C7—C6 | −178.2 (2) | C10—C8—C9—N1 | 76.0 (2) |
C2—C3—C4—C5 | −1.1 (4) | C10—C11—C12—C13 | 0.2 (3) |
C3—C2—C7—O1 | 174.33 (18) | C11—C10—C15—C14 | −0.1 (3) |
C3—C2—C7—C6 | 0.6 (3) | C11—C12—C13—C14 | −0.1 (3) |
C3—C4—C5—C6 | 0.8 (4) | C12—C13—C14—C15 | −0.2 (4) |
C4—C5—C6—C7 | 0.1 (3) | C13—C14—C15—C10 | 0.2 (3) |
C5—C6—C7—O1 | −174.72 (19) | C15—C10—C11—Cl1 | 179.69 (15) |
C5—C6—C7—C2 | −0.8 (3) | C15—C10—C11—C12 | −0.1 (3) |
C7—O1—C8—C9 | −43.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 1.15 (2) | 1.78 (2) | 2.849 (2) | 153.9 (16) |
Symmetry code: (i) −x+1, −y+2, −z. |
Footnotes
‡Additional correspondance author: e-mail:blci@163.com. Lan Bai, Ling Zhong and Jianyou Shi contributed equally to this paper.
Funding information
Funding for this research was provided by: Construction of key specialty of national clinical pharmacy (award No. 30305030698); New type of antitumor drug
and research based Triptolide as lead compound targeted TFIIH protein subunit XPB (award No. 2016QN08).References
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