Crystal structure of (Z)-7,8-di­chloro-4-(2-oxo­propyl­idene)-4,5-di­hydro-1H-1,5-benzodiazepin-2(3H)-one

Sanae Lahmidi; Abdelhanine Essaghouani; El Mokhtar Essassi; Mohamed Saadi; Lahcen El Ammari

doi:10.1107/S2056989015023750

. 2015 Dec 16;71(Pt 12):o1059–o1060. doi: 10.1107/S2056989015023750

Crystal structure of (Z)-7,8-dichloro-4-(2-oxopropylidene)-4,5-dihydro-1H-1,5-benzodiazepin-2(3H)-one

Sanae Lahmidi ^a,^*, Abdelhanine Essaghouani ^a, El Mokhtar Essassi ^a, Mohamed Saadi ^b, Lahcen El Ammari ^b

PMCID: PMC4719978 PMID: 26870497

Abstract

In the title compound, C₁₂H₁₀Cl₂N₂O₂, the seven-membered heterocycle displays a half-chair conformation. The mean plane through the oxopropylidene group makes a dihedral angle of 36.44 (9)° with the fused benzene ring. An intramolecular N—H⋯O hydrogen bond to close an S(6) loop is noted. An important feature of the molecular packing are N—H⋯O hydrogen bonds that lead to the formation of helical supramolecular chains along the b axis.

Keywords: crystal structure; 2-oxopropylidene; 1,5-benzodiazepinone; hydrogen bonding

Related literature

For the pharmaceutical and biochemical properties of 1,5-benzodiazepine and their derivatives, see: El Azzaoui et al. (1999 ▸); Gringauz (1999 ▸); Swamy et al. (2008 ▸). For related structures, see: El Abbassi et al. (1997 ▸); Akkurt et al. (2006 ▸).

Experimental

Crystal data

C₁₂H₁₀Cl₂N₂O₂
M _r = 285.12
Monoclinic,
a = 7.6789 (4) Å
b = 13.2199 (6) Å
c = 12.4129 (7) Å
β = 102.561 (3)°
V = 1229.93 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 296 K
0.36 × 0.33 × 0.24 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.672, T _max = 0.746
25693 measured reflections
3299 independent reflections
2692 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.112
S = 1.02
3298 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT-Plus (Bruker, 2009 ▸); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015023750/tk5415sup1.cif

e-71-o1059-sup1.cif^{(877.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023750/tk5415Isup2.hkl

e-71-o1059-Isup2.hkl^{(263.4KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015023750/tk5415Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015023750/tk5415fig1.tif

Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

Click here for additional data file.^{(1.6MB, tif)}

. DOI: 10.1107/S2056989015023750/tk5415fig2.tif

Structure of the title compound, showing molecules linked through N1—H1⋯O1 hydrogen bonds and the intramolecular hydrogen bond N2—H2⋯O2 (dashed lines).

CCDC reference: 1441702

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.86	1.96	2.6410 (18)	135
N1—H1⋯O2ⁱ	0.86	1.95	2.8010 (19)	173

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and the University Mohammed V, Rabat, Morocco, for financial support.

supplementary crystallographic information

S1. Comment

1,5-Benzodiazepines are used as starting materials in the synthesis of several heterocyclic compounds studied for potential biological activities (El Azzaoui et al. 1999). They are used for the purpose of hypnotic effects, owing to their less toxic and less severe withdrawal effects when compared with barbiturates (Gringauz, 1999). Some benzodiazepine derivatives have been widely used as anti-bacterial, anti-fungal, analgesic and anti-convulsant agents (Swamy et al., 2008). In our laboratory we were interested in the synthesis of new 1,5-benzodiazepine derivatives (El Abbassi et al., 1997; Akkurt et al., 2006). The purpose of this work is to synthesize (Z)-7,8-dichloro-4,5-dihydro-4-(2-oxopropylidene)-1H-benzo[b][1,4] diazepin-2(3H)-one by condensation of 4,5-dichloro-o-phenylenediamine with 4-hydroxy-6-methyl-2H-pyran-2-one.

The molecule of the title compound, Fig. 1, is build up from two fused six- and seven-membered rings linked to a 2-oxopropylidene group. The seven-membered ring displays a half-chair conformation as indicated by the puckering amplitude QT = 0.811 (2) Å and spherical polar angle θ2 = 73.9 (2)°, φ2 = 129.07 (12)° and φ3 = −76.3 (4)°. Moreover, the dihedral angle between the mean plane through the oxopropylidene group and the dichlorobenzene ring is of 36.44 (9)°.

In the crystal, the molecules are linked by hydrogen bonds in the way to build an helical chain along the b axis as shown in Fig. 2 and Table 1. An intramolecular hydrogen bond N2—H2···O2 is also observed in this structure.

S2. Experimental

A mixture of 4,5-dichloro-o-phenylenediamine (1.13 g) and of 4-hydroxy-6-methyl-2H- pyran-2-one (0.25 g) in xylene (30 ml) was heated at reflux for 4 h with azeotropic distillation. The completion of the reaction was confirmed by TLC. The solid obtained upon cooling the mixture was recrystallized from ethanol to afford colourless crystals in 75% yield.