organic compounds
(4Z)-4-(2-Oxopropylidene)-1,3-bis(prop-2-en-1-yl)-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one
aLaboratoire de Chimie Organique Hétérocyclique, URAC 21, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Mohammed V University, Rabat, Morocco, and bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
*Correspondence e-mail: sebhaoui.jihad@gmail.com
In the title compound, C18H20N2O2, the diazepin-2-one ring adopts a The conformation of the acetyl group is partially determined by an intramolecular N—H⋯O hydrogen bond. In the crystal, pairwise C—H⋯O hydrogen bonds form inversion dimers.
Keywords: crystal structure; hydrogen bond; diazepine; crystal structure.
CCDC reference: 1541017
Structure description
1,5-Benzodiazepine derivatives have attracted much attention as they exhibit pronounced anxiolytic, sedative, hypnotic and anticonvulsant activities with low toxicity (Landquist et al., 1984; Hamor et al., 1984; Ben-Cherif et al., 2010). They are also used as an intermediates for the synthesis of new heterocyclic systems (Ahabchane et al., 2001; Minnih et al., 2014). In a continuation of our work on the synthesis and structure of 1,5-benzodiazepine derivatives (Sebhaoui et al., 2016), we report here the preparation and of the title compound.
The seven-membered ring adopts a Q(2) = 0.891 (1) Å, Q(3) = 0.295 (1) Å, φ(2) = 204.93 (7)° and φ(3) = 311.0 (2)° with a total puckering amplitude of 0.928 (1) Å. The orientation of the acetyl substituent is determined in part by the intramolecular N1—H1⋯O2 hydrogen bond (Table 1 and Fig. 1).
Puckering analysis of the conformation gave the parameters
|
In the crystal, molecules form inversion dimers through complementary C10—H10⋯O1i hydrogen bonds (Table 1 and Fig. 2).
Synthesis and crystallization
To a solution of (4Z)-4-(-2-oxopropylidene)-1,5-benzodiazepin-2-one (0.01 mol) in 60 ml of N,N-dimethylformamide were added K2CO3 (0.02 mol), allyl bromide (0.02 mol) and tetra n-butylammonium bromide (TBAB) (0.001 mol). The reaction mixture was stirred at room temperature for 48 h. The solution was filtered and the solvent removed under reduced pressure. The residue was chromatographed on a silica gel column using hexane and ethyl acetate (90/10) as eluents to afford the title compound as colourless crystals.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1541017
https://doi.org/10.1107/S241431461700493X/sj4101sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700493X/sj4101Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S241431461700493X/sj4101Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S241431461700493X/sj4101Isup4.cml
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C18H20N2O2 | Z = 2 |
Mr = 296.36 | F(000) = 316 |
Triclinic, P1 | Dx = 1.293 Mg m−3 |
a = 8.6864 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.9925 (6) Å | Cell parameters from 6420 reflections |
c = 10.9872 (7) Å | θ = 2.5–29.2° |
α = 110.653 (1)° | µ = 0.09 mm−1 |
β = 95.111 (1)° | T = 100 K |
γ = 104.723 (1)° | Block, colourless |
V = 761.42 (9) Å3 | 0.36 × 0.25 × 0.25 mm |
Bruker SMART APEX CCD diffractometer | 4041 independent reflections |
Radiation source: fine-focus sealed tube | 3219 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 8.3333 pixels mm-1 | θmax = 29.2°, θmin = 2.0° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −12→12 |
Tmin = 0.88, Tmax = 0.98 | l = −14→15 |
14767 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)] = 0.045 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.128 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0798P)2 + 0.0641P] where P = (Fo2 + 2Fc2)/3 |
4041 reflections | (Δ/σ)max < 0.001 |
279 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 10 sec/frame. |
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 | ||
O1 | 0.72540 (10) | 0.99583 (9) | 0.37759 (8) | 0.01874 (19) | |
O2 | 0.68608 (10) | 0.68232 (10) | 0.74999 (8) | 0.0219 (2) | |
N1 | 0.73630 (11) | 0.63488 (11) | 0.50839 (9) | 0.0149 (2) | |
H1 | 0.7503 (19) | 0.6185 (19) | 0.5852 (17) | 0.033 (4)* | |
N2 | 0.86150 (10) | 0.80420 (10) | 0.33693 (9) | 0.0134 (2) | |
C1 | 0.87072 (12) | 0.64209 (12) | 0.32073 (10) | 0.0137 (2) | |
C2 | 0.95114 (13) | 0.56478 (14) | 0.22408 (11) | 0.0183 (2) | |
H2 | 0.9908 (17) | 0.6174 (17) | 0.1664 (14) | 0.020 (3)* | |
C3 | 0.97350 (14) | 0.41321 (15) | 0.21084 (12) | 0.0218 (3) | |
H3 | 1.0298 (19) | 0.3623 (19) | 0.1449 (16) | 0.032 (4)* | |
C4 | 0.91651 (14) | 0.33589 (14) | 0.29426 (12) | 0.0205 (2) | |
H4 | 0.9307 (18) | 0.2294 (19) | 0.2830 (15) | 0.031 (4)* | |
C5 | 0.83713 (13) | 0.41063 (13) | 0.39037 (11) | 0.0171 (2) | |
H5 | 0.7977 (16) | 0.3598 (16) | 0.4529 (14) | 0.018 (3)* | |
C6 | 0.81244 (12) | 0.56313 (13) | 0.40477 (10) | 0.0137 (2) | |
C7 | 0.62363 (12) | 0.71296 (12) | 0.50155 (10) | 0.0137 (2) | |
C8 | 0.58137 (12) | 0.72269 (13) | 0.36870 (10) | 0.0144 (2) | |
H8 | 0.5736 (17) | 0.6142 (17) | 0.2981 (14) | 0.022 (4)* | |
C9 | 0.72664 (12) | 0.85397 (13) | 0.36026 (10) | 0.0135 (2) | |
C10 | 0.55651 (13) | 0.77944 (13) | 0.60908 (11) | 0.0157 (2) | |
H10 | 0.4772 (17) | 0.8366 (17) | 0.5993 (14) | 0.022 (3)* | |
C11 | 0.59228 (13) | 0.76065 (13) | 0.73184 (11) | 0.0173 (2) | |
C12 | 0.51378 (16) | 0.83951 (17) | 0.84424 (12) | 0.0249 (3) | |
H12A | 0.469 (2) | 0.760 (2) | 0.881 (2) | 0.059 (6)* | |
H12B | 0.435 (2) | 0.891 (2) | 0.8239 (16) | 0.037 (4)* | |
H12C | 0.605 (2) | 0.933 (2) | 0.916 (2) | 0.051 (5)* | |
C13 | 0.42116 (13) | 0.75818 (14) | 0.34215 (11) | 0.0178 (2) | |
H13A | 0.3311 (17) | 0.6712 (17) | 0.3594 (14) | 0.023 (3)* | |
H13B | 0.4255 (16) | 0.8713 (17) | 0.4069 (14) | 0.021 (3)* | |
C14 | 0.38388 (15) | 0.74770 (17) | 0.20244 (13) | 0.0248 (3) | |
H14 | 0.399 (2) | 0.850 (3) | 0.190 (2) | 0.065 (6)* | |
C15 | 0.3403 (2) | 0.6128 (2) | 0.09694 (15) | 0.0432 (4) | |
H15A | 0.318 (3) | 0.505 (3) | 0.102 (3) | 0.097 (8)* | |
H15B | 0.318 (2) | 0.616 (2) | 0.0088 (19) | 0.050 (5)* | |
C16 | 1.00249 (13) | 0.92304 (13) | 0.32234 (11) | 0.0162 (2) | |
H16A | 1.0122 (16) | 1.0332 (17) | 0.3896 (13) | 0.017 (3)* | |
H16B | 1.0997 (17) | 0.8951 (17) | 0.3466 (13) | 0.023 (4)* | |
C17 | 0.99218 (14) | 0.92956 (14) | 0.18704 (11) | 0.0195 (2) | |
H17 | 1.0916 (19) | 1.0012 (19) | 0.1798 (15) | 0.033 (4)* | |
C18 | 0.86578 (16) | 0.85178 (15) | 0.08827 (12) | 0.0234 (3) | |
H18A | 0.762 (2) | 0.7781 (19) | 0.0972 (16) | 0.034 (4)* | |
H18B | 0.8730 (19) | 0.8666 (18) | 0.0047 (16) | 0.029 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0221 (4) | 0.0158 (4) | 0.0216 (4) | 0.0089 (3) | 0.0064 (3) | 0.0084 (3) |
O2 | 0.0257 (4) | 0.0262 (4) | 0.0194 (4) | 0.0122 (3) | 0.0063 (3) | 0.0118 (3) |
N1 | 0.0165 (4) | 0.0167 (4) | 0.0158 (4) | 0.0082 (3) | 0.0050 (3) | 0.0088 (4) |
N2 | 0.0140 (4) | 0.0125 (4) | 0.0154 (4) | 0.0049 (3) | 0.0045 (3) | 0.0063 (3) |
C1 | 0.0132 (5) | 0.0134 (5) | 0.0147 (5) | 0.0056 (4) | 0.0010 (4) | 0.0050 (4) |
C2 | 0.0195 (5) | 0.0215 (5) | 0.0171 (5) | 0.0101 (4) | 0.0056 (4) | 0.0080 (4) |
C3 | 0.0236 (6) | 0.0237 (6) | 0.0197 (6) | 0.0147 (5) | 0.0057 (4) | 0.0048 (4) |
C4 | 0.0202 (5) | 0.0162 (5) | 0.0251 (6) | 0.0098 (4) | 0.0017 (4) | 0.0055 (4) |
C5 | 0.0154 (5) | 0.0151 (5) | 0.0220 (6) | 0.0050 (4) | 0.0021 (4) | 0.0086 (4) |
C6 | 0.0127 (4) | 0.0144 (5) | 0.0143 (5) | 0.0053 (4) | 0.0021 (4) | 0.0051 (4) |
C7 | 0.0121 (5) | 0.0123 (4) | 0.0166 (5) | 0.0026 (4) | 0.0024 (4) | 0.0066 (4) |
C8 | 0.0139 (5) | 0.0154 (5) | 0.0152 (5) | 0.0055 (4) | 0.0031 (4) | 0.0067 (4) |
C9 | 0.0159 (5) | 0.0158 (5) | 0.0101 (5) | 0.0062 (4) | 0.0028 (4) | 0.0055 (4) |
C10 | 0.0142 (5) | 0.0160 (5) | 0.0181 (5) | 0.0055 (4) | 0.0042 (4) | 0.0072 (4) |
C11 | 0.0165 (5) | 0.0159 (5) | 0.0179 (5) | 0.0025 (4) | 0.0045 (4) | 0.0062 (4) |
C12 | 0.0276 (6) | 0.0321 (7) | 0.0188 (6) | 0.0135 (5) | 0.0103 (5) | 0.0100 (5) |
C13 | 0.0151 (5) | 0.0201 (5) | 0.0197 (5) | 0.0077 (4) | 0.0025 (4) | 0.0082 (4) |
C14 | 0.0236 (6) | 0.0300 (6) | 0.0258 (6) | 0.0099 (5) | 0.0021 (5) | 0.0160 (5) |
C15 | 0.0613 (10) | 0.0369 (8) | 0.0230 (7) | 0.0013 (7) | 0.0004 (7) | 0.0135 (6) |
C16 | 0.0142 (5) | 0.0165 (5) | 0.0179 (5) | 0.0028 (4) | 0.0032 (4) | 0.0078 (4) |
C17 | 0.0223 (6) | 0.0203 (5) | 0.0212 (6) | 0.0085 (4) | 0.0103 (4) | 0.0115 (4) |
C18 | 0.0317 (6) | 0.0260 (6) | 0.0165 (6) | 0.0135 (5) | 0.0072 (5) | 0.0091 (5) |
O1—C9 | 1.2247 (13) | C8—H8 | 0.991 (14) |
O2—C11 | 1.2496 (14) | C10—C11 | 1.4343 (16) |
N1—C7 | 1.3527 (13) | C10—H10 | 0.977 (14) |
N1—C6 | 1.4081 (14) | C11—C12 | 1.5070 (16) |
N1—H1 | 0.910 (17) | C12—H12A | 0.96 (2) |
N2—C9 | 1.3701 (13) | C12—H12B | 0.965 (17) |
N2—C1 | 1.4290 (13) | C12—H12C | 1.02 (2) |
N2—C16 | 1.4690 (13) | C13—C14 | 1.5047 (17) |
C1—C2 | 1.3990 (15) | C13—H13A | 1.039 (14) |
C1—C6 | 1.4058 (15) | C13—H13B | 1.003 (14) |
C2—C3 | 1.3843 (16) | C14—C15 | 1.287 (2) |
C2—H2 | 0.954 (14) | C14—H14 | 0.96 (2) |
C3—C4 | 1.3871 (18) | C15—H15A | 0.97 (3) |
C3—H3 | 0.958 (16) | C15—H15B | 0.983 (19) |
C4—C5 | 1.3808 (16) | C16—C17 | 1.5039 (16) |
C4—H4 | 0.963 (15) | C16—H16A | 0.982 (13) |
C5—C6 | 1.3979 (15) | C16—H16B | 0.980 (14) |
C5—H5 | 0.991 (14) | C17—C18 | 1.3170 (17) |
C7—C10 | 1.3765 (15) | C17—H17 | 0.966 (16) |
C7—C8 | 1.5113 (15) | C18—H18A | 1.010 (16) |
C8—C9 | 1.5282 (14) | C18—H18B | 0.979 (16) |
C8—C13 | 1.5306 (14) | ||
C7—N1—C6 | 126.14 (9) | C7—C10—C11 | 122.55 (10) |
C7—N1—H1 | 113.1 (10) | C7—C10—H10 | 118.3 (8) |
C6—N1—H1 | 120.2 (10) | C11—C10—H10 | 119.0 (8) |
C9—N2—C1 | 124.02 (9) | O2—C11—C10 | 122.97 (10) |
C9—N2—C16 | 117.67 (9) | O2—C11—C12 | 118.49 (10) |
C1—N2—C16 | 118.26 (8) | C10—C11—C12 | 118.54 (10) |
C2—C1—C6 | 118.84 (10) | C11—C12—H12A | 109.2 (12) |
C2—C1—N2 | 118.71 (9) | C11—C12—H12B | 115.9 (10) |
C6—C1—N2 | 122.27 (9) | H12A—C12—H12B | 111.7 (15) |
C3—C2—C1 | 120.93 (11) | C11—C12—H12C | 106.4 (11) |
C3—C2—H2 | 119.7 (8) | H12A—C12—H12C | 107.0 (16) |
C1—C2—H2 | 119.4 (8) | H12B—C12—H12C | 106.3 (14) |
C2—C3—C4 | 120.12 (11) | C14—C13—C8 | 111.01 (9) |
C2—C3—H3 | 120.0 (9) | C14—C13—H13A | 111.2 (8) |
C4—C3—H3 | 119.8 (9) | C8—C13—H13A | 107.2 (8) |
C5—C4—C3 | 119.71 (10) | C14—C13—H13B | 109.9 (8) |
C5—C4—H4 | 120.8 (9) | C8—C13—H13B | 110.4 (8) |
C3—C4—H4 | 119.5 (9) | H13A—C13—H13B | 106.9 (11) |
C4—C5—C6 | 121.04 (11) | C15—C14—C13 | 125.60 (13) |
C4—C5—H5 | 121.5 (8) | C15—C14—H14 | 116.5 (13) |
C6—C5—H5 | 117.4 (8) | C13—C14—H14 | 117.8 (13) |
C5—C6—C1 | 119.36 (10) | C14—C15—H15A | 121.2 (16) |
C5—C6—N1 | 117.77 (10) | C14—C15—H15B | 120.8 (10) |
C1—C6—N1 | 122.80 (9) | H15A—C15—H15B | 117.7 (19) |
N1—C7—C10 | 121.64 (10) | N2—C16—C17 | 114.66 (9) |
N1—C7—C8 | 114.62 (9) | N2—C16—H16A | 106.5 (8) |
C10—C7—C8 | 123.73 (9) | C17—C16—H16A | 110.0 (8) |
C7—C8—C9 | 105.81 (8) | N2—C16—H16B | 107.8 (8) |
C7—C8—C13 | 115.83 (9) | C17—C16—H16B | 110.9 (8) |
C9—C8—C13 | 112.20 (9) | H16A—C16—H16B | 106.5 (11) |
C7—C8—H8 | 108.3 (8) | C18—C17—C16 | 126.31 (11) |
C9—C8—H8 | 107.4 (8) | C18—C17—H17 | 122.1 (10) |
C13—C8—H8 | 106.9 (8) | C16—C17—H17 | 111.6 (10) |
O1—C9—N2 | 121.96 (10) | C17—C18—H18A | 121.5 (9) |
O1—C9—C8 | 122.65 (9) | C17—C18—H18B | 118.9 (9) |
N2—C9—C8 | 115.34 (9) | H18A—C18—H18B | 119.6 (13) |
C9—N2—C1—C2 | 140.12 (10) | N1—C7—C8—C13 | 161.42 (9) |
C16—N2—C1—C2 | −37.25 (14) | C10—C7—C8—C13 | −19.55 (14) |
C9—N2—C1—C6 | −44.67 (15) | C1—N2—C9—O1 | 177.73 (9) |
C16—N2—C1—C6 | 137.96 (10) | C16—N2—C9—O1 | −4.89 (15) |
C6—C1—C2—C3 | −0.03 (16) | C1—N2—C9—C8 | 0.13 (14) |
N2—C1—C2—C3 | 175.35 (10) | C16—N2—C9—C8 | 177.51 (9) |
C1—C2—C3—C4 | −0.25 (18) | C7—C8—C9—O1 | −103.13 (11) |
C2—C3—C4—C5 | 0.12 (18) | C13—C8—C9—O1 | 24.08 (14) |
C3—C4—C5—C6 | 0.29 (17) | C7—C8—C9—N2 | 74.45 (11) |
C4—C5—C6—C1 | −0.56 (16) | C13—C8—C9—N2 | −158.34 (9) |
C4—C5—C6—N1 | −177.52 (10) | N1—C7—C10—C11 | −4.46 (16) |
C2—C1—C6—C5 | 0.43 (15) | C8—C7—C10—C11 | 176.57 (10) |
N2—C1—C6—C5 | −174.78 (9) | C7—C10—C11—O2 | −0.30 (17) |
C2—C1—C6—N1 | 177.22 (10) | C7—C10—C11—C12 | 179.43 (10) |
N2—C1—C6—N1 | 2.01 (15) | C7—C8—C13—C14 | −174.24 (9) |
C7—N1—C6—C5 | −139.68 (11) | C9—C8—C13—C14 | 64.13 (12) |
C7—N1—C6—C1 | 43.48 (15) | C8—C13—C14—C15 | 71.29 (18) |
C6—N1—C7—C10 | −179.89 (10) | C9—N2—C16—C17 | −81.22 (12) |
C6—N1—C7—C8 | −0.83 (14) | C1—N2—C16—C17 | 96.32 (11) |
N1—C7—C8—C9 | −73.60 (11) | N2—C16—C17—C18 | 6.42 (17) |
C10—C7—C8—C9 | 105.44 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.910 (17) | 1.878 (16) | 2.6308 (12) | 138.6 (14) |
C10—H10···O1i | 0.977 (14) | 2.567 (14) | 3.5316 (13) | 168.9 (11) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Acknowledgements
JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.
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