organic compounds
(E)-2-Phenyl-4-styryl-2,3-dihydro-1H-1,5-benzodiazepine hemihydrate
aLaboratoire de Chimie Moléculaire, Département de Chimie, Faculté des Sciences Semlalia, BP 2390, Université Cadi Ayyad, 40001 Marrakech, Morocco, and bCristallographie, Résonance, Magnétique et Mod\'lisation (CRM2), Université Henri Poincaré, Nancy 1, Faculté des Sciences, BP 70239, 54506 Vandoeuvre le`s Nancy CEDEX, France
*Correspondence e-mail: loughzail@gmail.com
The 23H20N2·0.5H2O. The seven-membered diazepine ring adopts a twist-boat conformation and makes dihedral angles of 85.08 (7) and 32.79 (7)° with the phenyl and styryl substituents, respectively. In the crystal, the organic molecules are linked by C—H⋯N hydrogen bonds into chains running along the b-axis direction. The water molecule, located on a twofold rotation axis, forms hydrogen bridges, connecting two adjacent chains.
contains eight molecules of the title compound, with half a water molecule per main molecule, CKeywords: crystal structure; 1,5-benzodiazepine; dichalcone; hydrogen bonding.
CCDC reference: 1563375
Structure description
Benzodiazepines are ), antioxidant (Patil et al., 2015), anticancer (Chen et al., 2014), antimicrobial (El-Gaml et al., 2014) and antiviral (Nyanguile et al., 2008) substances and constitute the backbones of several marketed drugs. 1,5-Benzodiazepines are generally synthesized by the condensation of o-phenylenediamine with α,β-unsaturated (Claramunt et al., 2006), β-haloketones (Ilango et al., 2013), or with using acidic catalysts (Jeganathan & Pitchumani, 2014) or the microwave irradiation technique, which is critical to enhance the condensation process (Chikhale & Khedekar, 2013). We report here the synthesis and characterization of a new 1,5-benzodiazepine derivative.
that are considered to be `privileged structures' since they possess a wide range of biological activities. 1,5-Benzodiazepines have found applications in medicine, being one of the most important classes of the therapeutic agents with widespread biological activities. They are commonly used as anti-inflammatory (Bhat & Kumar, 2016The molecular structure of the title compound is illustrated in Fig. 1. In the molecule, which adopts an approximate U shape, the seven-membered diazepine ring displays a twist-boat conformation as indicated by the total puckering amplitude QT = 0.9442 (19)°, and spherical polar angle θ2 = 79.23 (11)°; φ2= 118.15 (13)° and φ3 = −104.5 (7)°. The benzodiazepine ring system makes dihedral angles of 85.08 (7) and 32.79 (7)° with the phenyl and styryl substituents, respectively.
In the crystal, the organic molecules are linked by C11—H11⋯N1 hydrogen bonds (Table 1, Fig. 2) into chains running along the b-axis direction. The water molecule, located on a twofold rotation axis, forms hydrogen bridges [N1⋯O01⋯N1( − x, y, −z); Fig. 3], connecting two adjacent chains.
Synthesis and crystallization
To a solution of 1,7-diphenylhepta-1,6-diene-3,5-dione (0.1 mol) in ethanol (30 ml) a few drops of triethylamine and 1,2-diaminobenzene (0.1 mol) were added. The mixture was heated under reflux for 12 h. The solvent was evaporated. The title compound was isolated by
on silica gel using hexane/ethyl acetate as The solid product was recrystallized in ethyl acetate to give crystals of the title compound.Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1563375
https://doi.org/10.1107/S2414314617010707/ff4018sup1.cif
contains datablocks I, block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010707/ff4018Isup2.hkl
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014(Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).C23H20N2·0.5H2O | F(000) = 1416 |
Mr = 333.42 | Dx = 1.248 Mg m−3 |
Monoclinic, I2/a | Cu Kα radiation, λ = 1.54184 Å |
a = 22.1001 (8) Å | Cell parameters from 3649 reflections |
b = 6.7624 (2) Å | θ = 3.7–74.5° |
c = 24.5714 (7) Å | µ = 0.58 mm−1 |
β = 104.835 (3)° | T = 100 K |
V = 3549.8 (2) Å3 | Plate, colourless |
Z = 8 | 0.21 × 0.16 × 0.04 mm |
Bruker X8 APEX diffractometer | 2831 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed X-ray tube | Rint = 0.148 |
φ and ω scans | θmax = 74.5°, θmin = 3.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −27→27 |
k = −8→8 | |
31210 measured reflections | l = −30→30 |
3649 independent reflections |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.058 | w = 1/[σ2(Fo2) + (0.0998P)2 + 0.8126P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.172 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.25 e Å−3 |
3649 reflections | Δρmin = −0.30 e Å−3 |
240 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00032 (11) |
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. All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.99 Å (methylene), 0.98 Å (methyl), 1.0Å (methine) with Uiso(H) = 1.2Ueq(CH and CH2). The coordinates of H atoms attached to N atoms were freely refined with Uiso(H) = 1.2Ueq(N) and the H attached to hydroxyl O atoms were fixed geometrically and treated as riding with O—H = 0.84Å and Uiso(H) = 1.5Ueq(O). |
x | y | z | Uiso*/Ueq | ||
O01 | 0.250000 | 0.4867 (3) | 0.000000 | 0.0395 (5) | |
H | 0.3281 (13) | 0.996 (4) | 0.2434 (12) | 0.037 (7)* | |
H01 | 0.2594 (15) | 0.572 (5) | 0.0303 (12) | 0.051 (8)* | |
C16 | 0.20259 (9) | 0.9411 (3) | 0.04598 (7) | 0.0244 (4) | |
H16 | 0.184023 | 0.819984 | 0.030619 | 0.029* | |
N2 | 0.31472 (8) | 0.9651 (2) | 0.20337 (6) | 0.0282 (4) | |
N1 | 0.28863 (8) | 0.7563 (2) | 0.09599 (6) | 0.0249 (4) | |
C18 | 0.10669 (9) | 1.1185 (3) | −0.00793 (6) | 0.0240 (4) | |
C17 | 0.16963 (9) | 1.1077 (3) | 0.03003 (7) | 0.0249 (4) | |
H17 | 0.188813 | 1.228920 | 0.044640 | 0.030* | |
C7 | 0.26467 (9) | 0.9315 (3) | 0.08503 (6) | 0.0227 (4) | |
C6 | 0.34457 (9) | 0.7303 (3) | 0.13831 (7) | 0.0231 (4) | |
C5 | 0.38511 (10) | 0.5796 (3) | 0.13048 (7) | 0.0249 (4) | |
H5 | 0.375753 | 0.509354 | 0.095850 | 0.030* | |
C10 | 0.23119 (9) | 1.2139 (3) | 0.17243 (6) | 0.0234 (4) | |
C21 | −0.01405 (11) | 1.1536 (3) | −0.07978 (8) | 0.0341 (5) | |
H21 | −0.054992 | 1.165117 | −0.103952 | 0.041* | |
C1 | 0.35798 (9) | 0.8318 (3) | 0.19049 (7) | 0.0252 (4) | |
C9 | 0.29638 (9) | 1.1477 (3) | 0.17111 (7) | 0.0236 (4) | |
H9 | 0.326737 | 1.254179 | 0.188115 | 0.028* | |
C8 | 0.29998 (9) | 1.1139 (3) | 0.11003 (7) | 0.0235 (4) | |
H8A | 0.282325 | 1.230251 | 0.086914 | 0.028* | |
H8B | 0.344362 | 1.100613 | 0.109275 | 0.028* | |
C2 | 0.41197 (10) | 0.7797 (3) | 0.23157 (7) | 0.0288 (4) | |
H2 | 0.421618 | 0.847780 | 0.266563 | 0.035* | |
C11 | 0.21281 (10) | 1.4043 (3) | 0.15406 (7) | 0.0283 (4) | |
H11 | 0.242354 | 1.491690 | 0.144851 | 0.034* | |
C4 | 0.43838 (10) | 0.5304 (3) | 0.17179 (8) | 0.0280 (4) | |
H4 | 0.465374 | 0.428633 | 0.165373 | 0.034* | |
C23 | 0.07520 (10) | 1.2995 (3) | −0.01512 (7) | 0.0287 (4) | |
H23 | 0.094978 | 1.412296 | 0.004770 | 0.034* | |
C12 | 0.15186 (11) | 1.4688 (3) | 0.14894 (8) | 0.0324 (4) | |
H12 | 0.139662 | 1.598047 | 0.135302 | 0.039* | |
C15 | 0.18828 (10) | 1.0901 (3) | 0.18831 (7) | 0.0271 (4) | |
H15 | 0.200434 | 0.960834 | 0.201990 | 0.033* | |
C22 | 0.01555 (11) | 1.3179 (3) | −0.05075 (8) | 0.0321 (4) | |
H22 | −0.004983 | 1.442502 | −0.055280 | 0.039* | |
C3 | 0.45205 (10) | 0.6315 (3) | 0.22288 (8) | 0.0293 (4) | |
H3 | 0.488507 | 0.599417 | 0.251574 | 0.035* | |
C19 | 0.07606 (10) | 0.9550 (3) | −0.03779 (7) | 0.0294 (4) | |
H19 | 0.096421 | 0.830136 | −0.033653 | 0.035* | |
C14 | 0.12768 (10) | 1.1559 (3) | 0.18410 (8) | 0.0329 (5) | |
H14 | 0.098747 | 1.071108 | 0.195262 | 0.039* | |
C13 | 0.10878 (10) | 1.3435 (3) | 0.16385 (8) | 0.0344 (5) | |
H13 | 0.066951 | 1.385892 | 0.160215 | 0.041* | |
C20 | 0.01653 (11) | 0.9730 (3) | −0.07325 (8) | 0.0357 (5) | |
H20 | −0.003486 | 0.860635 | −0.093225 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O01 | 0.0638 (16) | 0.0241 (9) | 0.0237 (9) | 0.000 | −0.0016 (9) | 0.000 |
C16 | 0.0288 (10) | 0.0296 (9) | 0.0128 (6) | −0.0014 (7) | 0.0019 (6) | −0.0005 (6) |
N2 | 0.0342 (9) | 0.0366 (8) | 0.0120 (6) | 0.0074 (7) | 0.0028 (6) | 0.0019 (6) |
N1 | 0.0291 (9) | 0.0289 (8) | 0.0146 (6) | −0.0020 (6) | 0.0014 (6) | 0.0009 (5) |
C18 | 0.0281 (10) | 0.0324 (9) | 0.0113 (7) | −0.0001 (7) | 0.0045 (6) | 0.0003 (6) |
C17 | 0.0315 (10) | 0.0289 (8) | 0.0136 (7) | −0.0005 (7) | 0.0044 (7) | −0.0003 (6) |
C7 | 0.0284 (10) | 0.0280 (8) | 0.0116 (7) | −0.0021 (7) | 0.0047 (6) | 0.0002 (6) |
C6 | 0.0255 (9) | 0.0258 (8) | 0.0156 (7) | −0.0029 (7) | 0.0005 (6) | 0.0016 (6) |
C5 | 0.0298 (10) | 0.0247 (8) | 0.0189 (7) | −0.0023 (7) | 0.0041 (7) | −0.0003 (6) |
C10 | 0.0283 (9) | 0.0289 (8) | 0.0113 (6) | −0.0018 (7) | 0.0019 (6) | −0.0037 (6) |
C21 | 0.0316 (11) | 0.0427 (11) | 0.0227 (8) | 0.0045 (9) | −0.0026 (7) | −0.0001 (7) |
C1 | 0.0294 (10) | 0.0285 (8) | 0.0166 (7) | 0.0008 (7) | 0.0040 (7) | 0.0022 (6) |
C9 | 0.0267 (10) | 0.0278 (9) | 0.0144 (7) | −0.0011 (7) | 0.0019 (6) | −0.0009 (6) |
C8 | 0.0286 (10) | 0.0269 (8) | 0.0144 (7) | −0.0002 (7) | 0.0043 (6) | 0.0014 (6) |
C2 | 0.0314 (10) | 0.0343 (9) | 0.0162 (7) | 0.0021 (8) | −0.0021 (7) | −0.0005 (7) |
C11 | 0.0354 (11) | 0.0304 (9) | 0.0183 (7) | 0.0005 (8) | 0.0056 (7) | −0.0001 (6) |
C4 | 0.0286 (10) | 0.0288 (9) | 0.0261 (8) | 0.0027 (7) | 0.0062 (7) | 0.0022 (7) |
C23 | 0.0365 (11) | 0.0309 (9) | 0.0171 (7) | −0.0006 (8) | 0.0042 (7) | −0.0004 (6) |
C12 | 0.0372 (11) | 0.0368 (10) | 0.0202 (8) | 0.0106 (9) | 0.0022 (7) | −0.0026 (7) |
C15 | 0.0322 (10) | 0.0307 (9) | 0.0174 (7) | −0.0034 (8) | 0.0047 (7) | −0.0022 (6) |
C22 | 0.0362 (11) | 0.0355 (10) | 0.0214 (8) | 0.0064 (8) | 0.0015 (8) | 0.0026 (7) |
C3 | 0.0276 (10) | 0.0344 (10) | 0.0222 (8) | 0.0013 (8) | −0.0007 (7) | 0.0021 (7) |
C19 | 0.0307 (10) | 0.0329 (9) | 0.0205 (8) | 0.0023 (8) | −0.0007 (7) | −0.0036 (7) |
C14 | 0.0313 (11) | 0.0430 (11) | 0.0248 (8) | −0.0082 (8) | 0.0078 (8) | −0.0098 (8) |
C13 | 0.0287 (11) | 0.0474 (12) | 0.0247 (8) | 0.0044 (9) | 0.0023 (7) | −0.0137 (8) |
C20 | 0.0356 (12) | 0.0396 (11) | 0.0252 (8) | −0.0009 (9) | −0.0044 (8) | −0.0064 (8) |
O01—H01 | 0.92 (3) | C9—C8 | 1.540 (2) |
C16—C17 | 1.344 (3) | C9—H9 | 1.0000 |
C16—C7 | 1.460 (3) | C8—H8A | 0.9900 |
C16—H16 | 0.9500 | C8—H8B | 0.9900 |
N2—C1 | 1.407 (2) | C2—C3 | 1.390 (3) |
N2—C9 | 1.467 (2) | C2—H2 | 0.9500 |
N2—H | 0.98 (3) | C11—C12 | 1.391 (3) |
N1—C7 | 1.297 (2) | C11—H11 | 0.9500 |
N1—C6 | 1.408 (2) | C4—C3 | 1.393 (3) |
C18—C23 | 1.397 (3) | C4—H4 | 0.9500 |
C18—C19 | 1.401 (3) | C23—C22 | 1.389 (3) |
C18—C17 | 1.465 (3) | C23—H23 | 0.9500 |
C17—H17 | 0.9500 | C12—C13 | 1.392 (3) |
C7—C8 | 1.505 (2) | C12—H12 | 0.9500 |
C6—C5 | 1.402 (3) | C15—C14 | 1.390 (3) |
C6—C1 | 1.417 (2) | C15—H15 | 0.9500 |
C5—C4 | 1.384 (3) | C22—H22 | 0.9500 |
C5—H5 | 0.9500 | C3—H3 | 0.9500 |
C10—C11 | 1.390 (3) | C19—C20 | 1.385 (3) |
C10—C15 | 1.394 (3) | C19—H19 | 0.9500 |
C10—C9 | 1.517 (3) | C14—C13 | 1.387 (3) |
C21—C20 | 1.385 (3) | C14—H14 | 0.9500 |
C21—C22 | 1.390 (3) | C13—H13 | 0.9500 |
C21—H21 | 0.9500 | C20—H20 | 0.9500 |
C1—C2 | 1.396 (3) | ||
C17—C16—C7 | 125.22 (17) | C7—C8—H8B | 109.3 |
C17—C16—H16 | 117.4 | C9—C8—H8B | 109.3 |
C7—C16—H16 | 117.4 | H8A—C8—H8B | 108.0 |
C1—N2—C9 | 121.80 (14) | C3—C2—C1 | 122.08 (17) |
C1—N2—H | 108.4 (16) | C3—C2—H2 | 119.0 |
C9—N2—H | 109.6 (16) | C1—C2—H2 | 119.0 |
C7—N1—C6 | 120.14 (16) | C10—C11—C12 | 121.05 (19) |
C23—C18—C19 | 117.82 (18) | C10—C11—H11 | 119.5 |
C23—C18—C17 | 119.03 (17) | C12—C11—H11 | 119.5 |
C19—C18—C17 | 123.15 (17) | C5—C4—C3 | 119.37 (18) |
C16—C17—C18 | 125.63 (17) | C5—C4—H4 | 120.3 |
C16—C17—H17 | 117.2 | C3—C4—H4 | 120.3 |
C18—C17—H17 | 117.2 | C22—C23—C18 | 121.34 (18) |
N1—C7—C16 | 116.24 (16) | C22—C23—H23 | 119.3 |
N1—C7—C8 | 121.51 (17) | C18—C23—H23 | 119.3 |
C16—C7—C8 | 122.23 (16) | C11—C12—C13 | 119.81 (19) |
C5—C6—N1 | 117.42 (15) | C11—C12—H12 | 120.1 |
C5—C6—C1 | 118.90 (17) | C13—C12—H12 | 120.1 |
N1—C6—C1 | 123.25 (17) | C14—C15—C10 | 119.89 (18) |
C4—C5—C6 | 121.84 (16) | C14—C15—H15 | 120.1 |
C4—C5—H5 | 119.1 | C10—C15—H15 | 120.1 |
C6—C5—H5 | 119.1 | C23—C22—C21 | 119.86 (19) |
C11—C10—C15 | 118.97 (18) | C23—C22—H22 | 120.1 |
C11—C10—C9 | 117.83 (17) | C21—C22—H22 | 120.1 |
C15—C10—C9 | 123.11 (17) | C2—C3—C4 | 119.53 (18) |
C20—C21—C22 | 119.6 (2) | C2—C3—H3 | 120.2 |
C20—C21—H21 | 120.2 | C4—C3—H3 | 120.2 |
C22—C21—H21 | 120.2 | C20—C19—C18 | 120.93 (19) |
C2—C1—N2 | 120.20 (16) | C20—C19—H19 | 119.5 |
C2—C1—C6 | 118.27 (17) | C18—C19—H19 | 119.5 |
N2—C1—C6 | 121.12 (17) | C13—C14—C15 | 121.03 (19) |
N2—C9—C10 | 111.69 (15) | C13—C14—H14 | 119.5 |
N2—C9—C8 | 109.02 (14) | C15—C14—H14 | 119.5 |
C10—C9—C8 | 110.54 (14) | C14—C13—C12 | 119.2 (2) |
N2—C9—H9 | 108.5 | C14—C13—H13 | 120.4 |
C10—C9—H9 | 108.5 | C12—C13—H13 | 120.4 |
C8—C9—H9 | 108.5 | C19—C20—C21 | 120.46 (19) |
C7—C8—C9 | 111.64 (14) | C19—C20—H20 | 119.8 |
C7—C8—H8A | 109.3 | C21—C20—H20 | 119.8 |
C9—C8—H8A | 109.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
O01—H01···N1 | 0.92 (3) | 2.01 (3) | 2.9300 (19) | 174 (3) |
C11—H11···N1i | 0.95 | 2.51 | 3.426 (3) | 161 |
Symmetry code: (i) x, y+1, z. |
Acknowledgements
The authors thank Professor M. Berraho for his help and discussions in order to finalize this paper.
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