organic compounds
3-(3-Chloropropyl)-7,8-dimethoxy-1H-3-benzazepin-2(3H)-one at 125 K
aZhejiang Police College Experience Center, Zhejiang Police College, Hangzhou 310053, People's Republic of China
*Correspondence e-mail: zpccxw@126.com
In the title compound, C15H18ClNO3, the seven-membered ring has a mirror plane passing through the methylene C atom and bisecting the C=C bond. It adopts a bent conformation, intermediate between the boat and chair forms. Both methoxy groups are coplanar with the attached benzene ring [C—C—O—C = −0.5 (3) and 2.2 (3)°]. In the inversion-related molecules are linked via C—H⋯O hydrogen bonds and π–π interactions involving the benzene ring [centroid–centroid distance = 3.6393 (12)Å].
Related literature
For the synthesis, see: Reiffen et al. (1990). For general background, see: Franke et al. (1987); Ishihara et al. (1994). For a related structure, see: Cheng (2008). For asymmetry parameters, see: Duax et al. (1976).
Experimental
Crystal data
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Refinement
|
Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808011264/ci2582sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011264/ci2582Isup2.hkl
The title compound was prepared according to the literature method (Reiffen et al., 1990). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at 295 K.
H atoms were positioned geometrically (C-H = 0.93-0.97 Å) and refined using a riding model, with Uiso(H) = 1.2–1.5Ueq(C).
Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C15H18ClNO3 | Z = 2 |
Mr = 295.75 | F(000) = 312 |
Triclinic, P1 | Dx = 1.319 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3141 (17) Å | Cell parameters from 2574 reflections |
b = 9.5924 (17) Å | θ = 2.2–25.0° |
c = 9.6359 (17) Å | µ = 0.26 mm−1 |
α = 103.667 (6)° | T = 123 K |
β = 114.701 (6)° | Block, yellow |
γ = 94.460 (6)° | 0.29 × 0.26 × 0.21 mm |
V = 744.7 (2) Å3 |
Bruker SMART CCD area-detector diffractometer | 2574 independent reflections |
Radiation source: fine-focus sealed tube | 2092 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −11→11 |
Tmin = 0.928, Tmax = 0.947 | k = −11→10 |
7023 measured reflections | l = −11→11 |
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: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0542P)2 + 0.2173P] where P = (Fo2 + 2Fc2)/3 |
2574 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C15H18ClNO3 | γ = 94.460 (6)° |
Mr = 295.75 | V = 744.7 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.3141 (17) Å | Mo Kα radiation |
b = 9.5924 (17) Å | µ = 0.26 mm−1 |
c = 9.6359 (17) Å | T = 123 K |
α = 103.667 (6)° | 0.29 × 0.26 × 0.21 mm |
β = 114.701 (6)° |
Bruker SMART CCD area-detector diffractometer | 2574 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2092 reflections with I > 2σ(I) |
Tmin = 0.928, Tmax = 0.947 | Rint = 0.019 |
7023 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.21 e Å−3 |
2574 reflections | Δρmin = −0.34 e Å−3 |
181 parameters |
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. |
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 > 2sigma(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 | ||
Cl1 | 0.40282 (11) | −0.14655 (9) | 0.18804 (11) | 0.1048 (3) | |
O1 | −0.20936 (16) | 0.23306 (15) | 0.46481 (17) | 0.0598 (4) | |
O2 | −0.31187 (14) | 0.39739 (15) | 0.28346 (16) | 0.0535 (3) | |
O3 | 0.15852 (19) | 0.32805 (18) | −0.03080 (19) | 0.0722 (4) | |
N1 | 0.31547 (18) | 0.24927 (17) | 0.17583 (19) | 0.0513 (4) | |
C2 | −0.16173 (19) | 0.37032 (18) | 0.3119 (2) | 0.0422 (4) | |
C4 | 0.0877 (2) | 0.39343 (19) | 0.2909 (2) | 0.0445 (4) | |
C6 | 0.0472 (2) | 0.2518 (2) | 0.4511 (2) | 0.0476 (4) | |
H6 | 0.0858 | 0.1949 | 0.5196 | 0.057* | |
C1 | −0.1044 (2) | 0.28198 (19) | 0.4125 (2) | 0.0447 (4) | |
C10 | 0.1945 (2) | 0.4592 (2) | 0.2308 (3) | 0.0557 (5) | |
H10A | 0.2980 | 0.5093 | 0.3203 | 0.067* | |
H10B | 0.1452 | 0.5306 | 0.1797 | 0.067* | |
C3 | −0.0662 (2) | 0.42458 (19) | 0.2514 (2) | 0.0450 (4) | |
H3 | −0.1046 | 0.4823 | 0.1839 | 0.054* | |
C5 | 0.1450 (2) | 0.30533 (19) | 0.3888 (2) | 0.0455 (4) | |
C7 | 0.3048 (2) | 0.2705 (2) | 0.4297 (2) | 0.0536 (5) | |
H7 | 0.3613 | 0.2625 | 0.5321 | 0.064* | |
C9 | 0.2193 (2) | 0.3412 (2) | 0.1127 (3) | 0.0540 (5) | |
C8 | 0.3789 (2) | 0.2489 (2) | 0.3359 (2) | 0.0556 (5) | |
H8 | 0.4831 | 0.2318 | 0.3815 | 0.067* | |
C11 | 0.3610 (2) | 0.1450 (2) | 0.0693 (3) | 0.0623 (6) | |
H11A | 0.4657 | 0.1257 | 0.1324 | 0.075* | |
H11B | 0.3707 | 0.1894 | −0.0078 | 0.075* | |
C15 | −0.3741 (2) | 0.4838 (2) | 0.1797 (3) | 0.0607 (5) | |
H15A | −0.4794 | 0.4958 | 0.1684 | 0.091* | |
H15B | −0.3814 | 0.4361 | 0.0768 | 0.091* | |
H15C | −0.3037 | 0.5780 | 0.2234 | 0.091* | |
C14 | −0.1591 (3) | 0.1435 (3) | 0.5654 (4) | 0.0892 (8) | |
H14A | −0.2426 | 0.1169 | 0.5934 | 0.134* | |
H14B | −0.0630 | 0.1957 | 0.6607 | 0.134* | |
H14C | −0.1373 | 0.0566 | 0.5107 | 0.134* | |
C12 | 0.2402 (3) | 0.0012 (3) | −0.0196 (3) | 0.0729 (7) | |
H12A | 0.1358 | 0.0215 | −0.0819 | 0.088* | |
H12B | 0.2723 | −0.0581 | −0.0940 | 0.088* | |
C13 | 0.2220 (3) | −0.0865 (3) | 0.0846 (3) | 0.0822 (7) | |
H13A | 0.1351 | −0.1710 | 0.0188 | 0.099* | |
H13B | 0.1932 | −0.0270 | 0.1618 | 0.099* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1226 (6) | 0.1022 (6) | 0.1229 (7) | 0.0475 (5) | 0.0735 (5) | 0.0491 (5) |
O1 | 0.0562 (8) | 0.0706 (9) | 0.0752 (10) | 0.0200 (7) | 0.0406 (7) | 0.0384 (8) |
O2 | 0.0394 (7) | 0.0670 (8) | 0.0629 (8) | 0.0175 (6) | 0.0249 (6) | 0.0286 (7) |
O3 | 0.0810 (10) | 0.0901 (11) | 0.0677 (10) | 0.0291 (9) | 0.0454 (9) | 0.0361 (9) |
N1 | 0.0452 (8) | 0.0567 (9) | 0.0566 (10) | 0.0119 (7) | 0.0297 (8) | 0.0114 (7) |
C2 | 0.0367 (9) | 0.0438 (9) | 0.0426 (10) | 0.0078 (7) | 0.0173 (8) | 0.0078 (8) |
C4 | 0.0442 (9) | 0.0422 (9) | 0.0490 (10) | 0.0096 (7) | 0.0248 (8) | 0.0092 (8) |
C6 | 0.0506 (10) | 0.0504 (10) | 0.0446 (10) | 0.0176 (8) | 0.0214 (8) | 0.0164 (8) |
C1 | 0.0455 (9) | 0.0452 (10) | 0.0460 (10) | 0.0091 (8) | 0.0240 (8) | 0.0112 (8) |
C10 | 0.0543 (11) | 0.0504 (11) | 0.0753 (14) | 0.0134 (9) | 0.0394 (10) | 0.0208 (10) |
C3 | 0.0485 (10) | 0.0426 (9) | 0.0468 (10) | 0.0129 (8) | 0.0232 (8) | 0.0141 (8) |
C5 | 0.0428 (9) | 0.0477 (10) | 0.0449 (10) | 0.0115 (8) | 0.0221 (8) | 0.0067 (8) |
C7 | 0.0459 (10) | 0.0654 (12) | 0.0476 (11) | 0.0191 (9) | 0.0196 (9) | 0.0135 (9) |
C9 | 0.0480 (10) | 0.0581 (12) | 0.0679 (14) | 0.0088 (9) | 0.0358 (10) | 0.0216 (10) |
C8 | 0.0384 (9) | 0.0649 (12) | 0.0582 (12) | 0.0154 (9) | 0.0199 (9) | 0.0111 (9) |
C11 | 0.0614 (12) | 0.0692 (13) | 0.0696 (14) | 0.0187 (10) | 0.0442 (11) | 0.0145 (11) |
C15 | 0.0469 (11) | 0.0752 (14) | 0.0683 (13) | 0.0253 (10) | 0.0250 (10) | 0.0335 (11) |
C14 | 0.0905 (18) | 0.111 (2) | 0.121 (2) | 0.0422 (15) | 0.0707 (17) | 0.0788 (19) |
C12 | 0.0688 (14) | 0.0743 (15) | 0.0642 (14) | 0.0169 (11) | 0.0305 (12) | −0.0015 (12) |
C13 | 0.0774 (16) | 0.0664 (14) | 0.0969 (19) | −0.0032 (12) | 0.0500 (15) | −0.0006 (13) |
Cl1—C13 | 1.783 (3) | C3—H3 | 0.93 |
O1—C1 | 1.372 (2) | C5—C7 | 1.460 (2) |
O1—C14 | 1.405 (3) | C7—C8 | 1.338 (3) |
O2—C2 | 1.367 (2) | C7—H7 | 0.93 |
O2—C15 | 1.416 (2) | C8—H8 | 0.93 |
O3—C9 | 1.225 (2) | C11—C12 | 1.515 (3) |
N1—C9 | 1.368 (3) | C11—H11A | 0.97 |
N1—C8 | 1.404 (3) | C11—H11B | 0.97 |
N1—C11 | 1.476 (2) | C15—H15A | 0.96 |
C2—C3 | 1.381 (2) | C15—H15B | 0.96 |
C2—C1 | 1.403 (2) | C15—H15C | 0.96 |
C4—C5 | 1.384 (3) | C14—H14A | 0.96 |
C4—C3 | 1.398 (2) | C14—H14B | 0.96 |
C4—C10 | 1.510 (3) | C14—H14C | 0.96 |
C6—C1 | 1.375 (2) | C12—C13 | 1.504 (4) |
C6—C5 | 1.409 (3) | C12—H12A | 0.97 |
C6—H6 | 0.93 | C12—H12B | 0.97 |
C10—C9 | 1.510 (3) | C13—H13A | 0.97 |
C10—H10A | 0.97 | C13—H13B | 0.97 |
C10—H10B | 0.97 | ||
C1—O1—C14 | 117.58 (15) | N1—C9—C10 | 115.85 (18) |
C2—O2—C15 | 116.59 (14) | C7—C8—N1 | 126.72 (17) |
C9—N1—C8 | 125.16 (16) | C7—C8—H8 | 116.6 |
C9—N1—C11 | 117.85 (17) | N1—C8—H8 | 116.6 |
C8—N1—C11 | 116.96 (16) | N1—C11—C12 | 112.93 (16) |
O2—C2—C3 | 124.88 (16) | N1—C11—H11A | 109.0 |
O2—C2—C1 | 115.42 (15) | C12—C11—H11A | 109.0 |
C3—C2—C1 | 119.69 (15) | N1—C11—H11B | 109.0 |
C5—C4—C3 | 120.30 (16) | C12—C11—H11B | 109.0 |
C5—C4—C10 | 119.48 (15) | H11A—C11—H11B | 107.8 |
C3—C4—C10 | 120.20 (16) | O2—C15—H15A | 109.5 |
C1—C6—C5 | 121.25 (17) | O2—C15—H15B | 109.5 |
C1—C6—H6 | 119.4 | H15A—C15—H15B | 109.5 |
C5—C6—H6 | 119.4 | O2—C15—H15C | 109.5 |
O1—C1—C6 | 125.56 (16) | H15A—C15—H15C | 109.5 |
O1—C1—C2 | 114.89 (15) | H15B—C15—H15C | 109.5 |
C6—C1—C2 | 119.54 (16) | O1—C14—H14A | 109.5 |
C4—C10—C9 | 110.38 (15) | O1—C14—H14B | 109.5 |
C4—C10—H10A | 109.6 | H14A—C14—H14B | 109.5 |
C9—C10—H10A | 109.6 | O1—C14—H14C | 109.5 |
C4—C10—H10B | 109.6 | H14A—C14—H14C | 109.5 |
C9—C10—H10B | 109.6 | H14B—C14—H14C | 109.5 |
H10A—C10—H10B | 108.1 | C13—C12—C11 | 115.1 (2) |
C2—C3—C4 | 120.54 (16) | C13—C12—H12A | 108.5 |
C2—C3—H3 | 119.7 | C11—C12—H12A | 108.5 |
C4—C3—H3 | 119.7 | C13—C12—H12B | 108.5 |
C4—C5—C6 | 118.65 (15) | C11—C12—H12B | 108.5 |
C4—C5—C7 | 120.94 (17) | H12A—C12—H12B | 107.5 |
C6—C5—C7 | 120.40 (17) | C12—C13—Cl1 | 111.93 (17) |
C8—C7—C5 | 127.12 (18) | C12—C13—H13A | 109.2 |
C8—C7—H7 | 116.4 | Cl1—C13—H13A | 109.2 |
C5—C7—H7 | 116.4 | C12—C13—H13B | 109.2 |
O3—C9—N1 | 121.47 (18) | Cl1—C13—H13B | 109.2 |
O3—C9—C10 | 122.68 (19) | H13A—C13—H13B | 107.9 |
C15—O2—C2—C3 | 2.2 (3) | C10—C4—C5—C7 | −2.4 (3) |
C15—O2—C2—C1 | −178.74 (16) | C1—C6—C5—C4 | 1.9 (3) |
C14—O1—C1—C6 | −0.5 (3) | C1—C6—C5—C7 | −179.24 (17) |
C14—O1—C1—C2 | 179.7 (2) | C4—C5—C7—C8 | −35.3 (3) |
C5—C6—C1—O1 | 178.90 (16) | C6—C5—C7—C8 | 145.9 (2) |
C5—C6—C1—C2 | −1.3 (3) | C8—N1—C9—O3 | −174.47 (18) |
O2—C2—C1—O1 | 1.4 (2) | C11—N1—C9—O3 | 7.6 (3) |
C3—C2—C1—O1 | −179.52 (15) | C8—N1—C9—C10 | 5.9 (3) |
O2—C2—C1—C6 | −178.43 (15) | C11—N1—C9—C10 | −172.03 (16) |
C3—C2—C1—C6 | 0.7 (3) | C4—C10—C9—O3 | 109.0 (2) |
C5—C4—C10—C9 | 68.9 (2) | C4—C10—C9—N1 | −71.4 (2) |
C3—C4—C10—C9 | −112.88 (19) | C5—C7—C8—N1 | −2.8 (4) |
O2—C2—C3—C4 | 178.40 (16) | C9—N1—C8—C7 | 37.8 (3) |
C1—C2—C3—C4 | −0.6 (3) | C11—N1—C8—C7 | −144.2 (2) |
C5—C4—C3—C2 | 1.2 (3) | C9—N1—C11—C12 | −88.5 (2) |
C10—C4—C3—C2 | −176.99 (16) | C8—N1—C11—C12 | 93.4 (2) |
C3—C4—C5—C6 | −1.8 (3) | N1—C11—C12—C13 | −63.4 (3) |
C10—C4—C5—C6 | 176.41 (16) | C11—C12—C13—Cl1 | −64.6 (2) |
C3—C4—C5—C7 | 179.33 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O3i | 0.93 | 2.56 | 3.473 (2) | 169 |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C15H18ClNO3 |
Mr | 295.75 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 9.3141 (17), 9.5924 (17), 9.6359 (17) |
α, β, γ (°) | 103.667 (6), 114.701 (6), 94.460 (6) |
V (Å3) | 744.7 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.29 × 0.26 × 0.21 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.928, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7023, 2574, 2092 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.115, 1.02 |
No. of reflections | 2574 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.34 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O3i | 0.93 | 2.56 | 3.473 (2) | 169 |
Symmetry code: (i) −x, −y+1, −z. |
Acknowledgements
The author acknowledges financial support from Zhejiang Police College, China.
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.
Benzazepine derivatives have been of considerable medicinal interest, partly because the skeleton is a component of amaryllydaceae alkaloids such as galanthamine as well as of ribasine alkaloids represented by ribasine (Ishihara et al., 1994). Many benzazepine derivatives have been reported to possess interesting biological activities. The title compound is an important intermediate of ivabradine, which was listed in market in 2006 as the representative of a novel pharmacological class termed reducing heart rate without concomitant negative inotropic or hypotensive effects (Franke et al., 1987). Rencently, in our previous research, a crystal structure of another important intermediate of ivabradine, 7,8-Dimethoxy-3-(3-chloropropyl)- 2,3,4,5-tetrahydro-1H-3-benzazepin-2-one was reported (Cheng, 2008). Here the crystal structure of the title compound is reported.
In the title molecule (Fig.1), the seven-membered ring adopts a bent conformation, intermediate between the boat and chair forms. The seven-membered ring possesses a mirror symmetry about the plane passing through atom C10 and bisecting the C7—C8 bond. The asymmetry parameter (Duax et al., 1976), ΔCs(C10), is 2.9 (2)°. The dihedral angle between the C1-C7/C10/C14/C15/O1/O2 and C8-C11/N1/O3 planes is 59.17 (6)°. The chloropropyl substituent group is in a (-)-synclinal conformation, as evidenced by the torsion angle N1—C11—C12—C13 of -63.4 (3)°, similar to that in a related structure (-68.9 (2)°, Cheng, 2008). The methoxy groups are coplanar with the benzene ring [C14—C1—O1—C6 = -0.5 (3)° and C15—C2—O2—C3 = 2.2 (3)°].
An intermolecular C—H···O hydrogen bond is observed in the crystal structure. Also, a π-π interaction involving the benzene ring is observed [centroid to centroid distance = 3.6393 (12) Å].