Crystal structure of 1,5-diethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-di­thione

Lamkaddem, A.; Harcharras, M.; Shaim, A.; Zouihri, H.; Echchahed, B.; Bi, W.

doi:10.1107/S205698901402790X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 2| February 2015| Page o83

doi:10.1107/S205698901402790X

Open

access

Crystal structure of 1,5-diethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-dithione

Abderrahman Lamkaddem,^a Mohamed Harcharras,^b Abdelillah Shaim,^c Hafid Zouihri,^d ^* Bousselham Echchahed ^e and Wenhua Bi ^f

^aLaboratoire de Synthèse Organique et des Procédés Éxtraction, Université Ibn Tofail, Faculté des Sciences, 14000 Kénitra, Morocco, ^bLaboratoire de Synthèse Organique et Organométallique et Théorique, Université Ibn Tofail, Faculté des Sciences, 14000 Kénitra, Morocco, ^cLaboratoire de Physico-chimie du Solide, Université Ibn Tofail, Faculté des Sciences, 14000 Kénitra, Morocco, ^dCentre Universtaire d'Analyse, d'Expertise, de Transfert de Technologie et d'Incubateur, Université Ibn Tofail, BP 242, Kénitra, Morocco, ^eLaboratoire d'Electrochimie, Corrosion et Environnement, Université Ibn Tofail, Faculté des Sciences, 14000 Kénitra, Morocco, and ^fDépartement de Chimie, Université Laval, Québec, QC, G1V 0A6, Canada
^*Correspondence e-mail: hafid.zouihri@gmail.com

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 20 December 2014; accepted 22 December 2014; online 3 January 2015)

In the title compound, C₁₃H₁₆N₂S₂, the seven-membered ring adopts a boat conformation, with the two phenylene C atoms representing the stern and the methylene C atom as the prow. The thione S atoms and N-bound ethyl groups lie on the opposite side of the molecule to the phenylene ring so that the molecule approximates mirror symmetry. In the crystal, supramolecular layers in the bc plane are sustained by a pair of C—H⋯S interactions to the same S atom acceptor.

Keywords: crystal structure; benzodiazepine; boat conformation..

CCDC reference: 1040593

1. Related literature

For the biological activity of benzodiazepine derivatives, see: Kumar et al. (2006 ); Swamy et al. (2008 ). For a related structure, see: Ourahou et al. (2010 ).

2. Experimental

2.1. Crystal data

C₁₃H₁₆N₂S₂
M_r = 264.40
Monoclinic, C 2/c
a = 19.8896 (2) Å
b = 8.8743 (1) Å
c = 15.5361 (2) Å
β = 104.087 (1)°
V = 2659.75 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 150 K
0.44 × 0.28 × 0.26 mm

2.2. Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.880, T_max = 0.906
14634 measured reflections
3312 independent reflections
2963 reflections with I > 2σ(I)
R_int = 0.022

2.3. Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.083
S = 1.05
3312 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯S1ⁱ	0.95	2.86	3.6474 (13)	141
C12—H12A⋯S1ⁱⁱ	0.99	2.87	3.4887 (13)	121
Symmetry codes: (i) $[x, -y+2, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1040593

Crystal structure: contains datablock I. DOI: 10.1107/S205698901402790X/tk5353sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901402790X/tk5353Isup2.hkl

Supporting information file. DOI: 10.1107/S205698901402790X/tk5353Isup3.cml

checkCIF report

Introduction top

Benzodiazepines and their derivatives are an important class of bioactive compound. They have attracted attention of chemists in the field of pharmaceuticals (Kumar et al., 2006). Some benzodiazepine derivatives have been widely used as anti-bacterial, anti-fungal, analgesic and anti-convulsant agents (Swamy et al. 2008).

Synthesis and crystallization top

In a round flask, the 1,5 dietthyl benzodiazepine-2,4-diones (2,22 g, 10 ml) and P₂S₅ (4.44 g, 20 ml) were mixed in acetonitrile (50 ml). The mixture was refluxed for 4 h. After this time, the solvent was evaporated, and the residue formed was washed with HCl (2 N) solution and distilled water, dried and recrystallised from toluene-chloroform (90/10). After some days, pale-yellow crystals were isolated (yield: 92.1 %, 2.34 g).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H-atoms were placed in calculated positions (C—H 0.95–0.99 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for all other H atoms.

Results and discussion top

The title compound crystallizes in the space group C2/c with one independent molecule in the asymmetric unit (Fig. 1). In the molecule, the diazepine ring system adopts a boat conformation with the two C1 and C6 atoms representing the stern and the C8 atom the prow with maximum deviation of 0.6626 (12)Å. The puckering parameters are: q2=0.9557 (11) Å, q3 = 0.2328 (11) Å, ϕ2 = 29.60 (7)° and ϕ3 = 128.4 (3)°. The mean plane of the diazepine ring is twisted with respect to that of the benzene ring by 32.27 (5)°. The geometric parameters of the title compound are comparable to those reported for similar structures (Ourahou et al., 2010).

Related literature top

For the biological activity of benzodiazepine derivatives, see: Kumar et al. (2006); Swamy et al. (2008). For a similar compound, see: Ourahou et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The structure of the title compound, showing atom labelling and 30% probability displacement ellipsoids.

1,5-Diethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-dithione top

Crystal data top

C₁₃H₁₆N₂S₂	F(000) = 1120
M_r = 264.40	D_x = 1.321 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7669 reflections
a = 19.8896 (2) Å	θ = 2.5–28.3°
b = 8.8743 (1) Å	µ = 0.38 mm⁻¹
c = 15.5361 (2) Å	T = 150 K
β = 104.087 (1)°	Block, pale-yellow
V = 2659.75 (5) Å³	0.44 × 0.28 × 0.26 mm
Z = 8

Data collection top

Bruker APEXII CCD area-detector diffractometer	3312 independent reflections
Radiation source: fine-focus sealed tube	2963 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −26→26
T_min = 0.880, T_max = 0.906	k = −11→9
14634 measured reflections	l = −20→20

Refinement top

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0451P)² + 1.6941P] where P = (F_o² + 2F_c²)/3
3312 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₁₆N₂S₂	V = 2659.75 (5) Å³
M_r = 264.40	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.8896 (2) Å	µ = 0.38 mm⁻¹
b = 8.8743 (1) Å	T = 150 K
c = 15.5361 (2) Å	0.44 × 0.28 × 0.26 mm
β = 104.087 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3312 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2963 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.906	R_int = 0.022
14634 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.05	Δρ_max = 0.39 e Å⁻³
3312 reflections	Δρ_min = −0.21 e Å⁻³
154 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.389586 (17)	0.69948 (4)	0.221477 (18)	0.02667 (9)
S2	0.401294 (17)	0.32244 (3)	0.37615 (2)	0.02698 (9)
N1	0.38266 (5)	0.81930 (10)	0.37619 (6)	0.01868 (19)
N2	0.38030 (5)	0.54640 (10)	0.48109 (6)	0.01790 (19)
C1	0.39904 (5)	0.82159 (12)	0.47124 (7)	0.0180 (2)
C2	0.41810 (6)	0.95882 (13)	0.51444 (8)	0.0236 (2)
H2	0.4222	1.0462	0.4808	0.028*
C3	0.43116 (6)	0.96826 (15)	0.60624 (8)	0.0270 (3)
H3	0.4443	1.0618	0.6353	0.032*
C4	0.42499 (6)	0.84098 (15)	0.65542 (8)	0.0258 (3)
H4	0.4323	0.8482	0.7180	0.031*
C5	0.40829 (6)	0.70361 (14)	0.61388 (7)	0.0217 (2)
H5	0.4055	0.6164	0.6483	0.026*
C6	0.39547 (5)	0.69179 (12)	0.52125 (7)	0.0176 (2)
C7	0.41267 (5)	0.49358 (12)	0.42024 (7)	0.0183 (2)
C8	0.45893 (6)	0.60552 (13)	0.38859 (7)	0.0196 (2)
H8A	0.4898	0.6575	0.4396	0.024*
H8B	0.4878	0.5541	0.3539	0.024*
C9	0.41007 (5)	0.71650 (12)	0.33112 (7)	0.0185 (2)
C10	0.32917 (6)	0.92648 (13)	0.32921 (8)	0.0255 (2)
H10A	0.3380	0.9521	0.2709	0.031*
H10B	0.3320	1.0205	0.3642	0.031*
C11	0.25747 (7)	0.85946 (17)	0.31559 (9)	0.0341 (3)
H11A	0.2230	0.9323	0.2846	0.051*
H11B	0.2485	0.8353	0.3733	0.051*
H11C	0.2544	0.7673	0.2801	0.051*
C12	0.32830 (6)	0.45201 (14)	0.50965 (8)	0.0245 (2)
H12A	0.3262	0.4814	0.5704	0.029*
H12B	0.3427	0.3450	0.5112	0.029*
C13	0.25706 (7)	0.46914 (18)	0.44750 (10)	0.0374 (3)
H13A	0.2239	0.4054	0.4681	0.056*
H13B	0.2588	0.4385	0.3875	0.056*
H13C	0.2424	0.5746	0.4467	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.03626 (18)	0.02858 (17)	0.01620 (14)	0.00172 (12)	0.00835 (11)	0.00226 (10)
S2	0.03522 (18)	0.01756 (15)	0.02775 (16)	0.00255 (11)	0.00685 (12)	−0.00303 (10)
N1	0.0206 (4)	0.0171 (5)	0.0179 (4)	0.0015 (3)	0.0039 (3)	0.0023 (3)
N2	0.0195 (4)	0.0165 (4)	0.0182 (4)	0.0003 (3)	0.0055 (3)	0.0014 (3)
C1	0.0159 (5)	0.0196 (5)	0.0186 (5)	0.0016 (4)	0.0044 (4)	−0.0005 (4)
C2	0.0233 (5)	0.0197 (5)	0.0279 (6)	−0.0003 (4)	0.0064 (4)	−0.0024 (4)
C3	0.0249 (6)	0.0270 (6)	0.0289 (6)	−0.0001 (5)	0.0062 (4)	−0.0108 (5)
C4	0.0221 (5)	0.0356 (7)	0.0196 (5)	0.0033 (5)	0.0047 (4)	−0.0066 (5)
C5	0.0193 (5)	0.0274 (6)	0.0191 (5)	0.0030 (4)	0.0059 (4)	0.0009 (4)
C6	0.0145 (5)	0.0192 (5)	0.0191 (5)	0.0019 (4)	0.0044 (4)	−0.0006 (4)
C7	0.0188 (5)	0.0180 (5)	0.0168 (4)	0.0043 (4)	0.0017 (4)	0.0031 (4)
C8	0.0181 (5)	0.0218 (5)	0.0198 (5)	0.0028 (4)	0.0063 (4)	0.0013 (4)
C9	0.0190 (5)	0.0185 (5)	0.0188 (5)	−0.0020 (4)	0.0065 (4)	0.0020 (4)
C10	0.0309 (6)	0.0198 (5)	0.0237 (5)	0.0078 (5)	0.0027 (4)	0.0046 (4)
C11	0.0255 (6)	0.0398 (8)	0.0349 (7)	0.0099 (6)	0.0035 (5)	0.0022 (6)
C12	0.0267 (6)	0.0230 (6)	0.0254 (5)	−0.0043 (5)	0.0097 (4)	0.0039 (4)
C13	0.0243 (6)	0.0473 (8)	0.0403 (7)	−0.0084 (6)	0.0071 (5)	0.0031 (6)

Geometric parameters (Å, º) top

S1—C9	1.6591 (11)	C5—H5	0.9500
S2—C7	1.6587 (11)	C7—C8	1.5150 (15)
N1—C9	1.3437 (15)	C8—C9	1.5131 (15)
N1—C1	1.4329 (13)	C8—H8A	0.9900
N1—C10	1.4803 (14)	C8—H8B	0.9900
N2—C7	1.3506 (14)	C10—C11	1.5118 (18)
N2—C6	1.4329 (14)	C10—H10A	0.9900
N2—C12	1.4805 (14)	C10—H10B	0.9900
C1—C2	1.3976 (15)	C11—H11A	0.9800
C1—C6	1.4008 (15)	C11—H11B	0.9800
C2—C3	1.3886 (17)	C11—H11C	0.9800
C2—H2	0.9500	C12—C13	1.5157 (17)
C3—C4	1.3858 (19)	C12—H12A	0.9900
C3—H3	0.9500	C12—H12B	0.9900
C4—C5	1.3815 (17)	C13—H13A	0.9800
C4—H4	0.9500	C13—H13B	0.9800
C5—C6	1.4030 (15)	C13—H13C	0.9800

C9—N1—C1	121.84 (9)	C9—C8—H8B	110.7
C9—N1—C10	120.88 (9)	C7—C8—H8B	110.7
C1—N1—C10	117.06 (9)	H8A—C8—H8B	108.8
C7—N2—C6	122.11 (9)	N1—C9—C8	114.72 (9)
C7—N2—C12	120.02 (10)	N1—C9—S1	124.58 (8)
C6—N2—C12	117.86 (9)	C8—C9—S1	120.56 (8)
C2—C1—C6	119.65 (10)	N1—C10—C11	110.88 (10)
C2—C1—N1	118.31 (10)	N1—C10—H10A	109.5
C6—C1—N1	122.03 (9)	C11—C10—H10A	109.5
C3—C2—C1	120.45 (11)	N1—C10—H10B	109.5
C3—C2—H2	119.8	C11—C10—H10B	109.5
C1—C2—H2	119.8	H10A—C10—H10B	108.1
C4—C3—C2	119.84 (11)	C10—C11—H11A	109.5
C4—C3—H3	120.1	C10—C11—H11B	109.5
C2—C3—H3	120.1	H11A—C11—H11B	109.5
C5—C4—C3	120.34 (11)	C10—C11—H11C	109.5
C5—C4—H4	119.8	H11A—C11—H11C	109.5
C3—C4—H4	119.8	H11B—C11—H11C	109.5
C4—C5—C6	120.55 (11)	N2—C12—C13	111.43 (10)
C4—C5—H5	119.7	N2—C12—H12A	109.3
C6—C5—H5	119.7	C13—C12—H12A	109.3
C1—C6—C5	119.09 (10)	N2—C12—H12B	109.3
C1—C6—N2	122.18 (9)	C13—C12—H12B	109.3
C5—C6—N2	118.72 (10)	H12A—C12—H12B	108.0
N2—C7—C8	115.48 (9)	C12—C13—H13A	109.5
N2—C7—S2	124.50 (9)	C12—C13—H13B	109.5
C8—C7—S2	119.93 (8)	H13A—C13—H13B	109.5
C9—C8—C7	105.35 (9)	C12—C13—H13C	109.5
C9—C8—H8A	110.7	H13A—C13—H13C	109.5
C7—C8—H8A	110.7	H13B—C13—H13C	109.5

C9—N1—C1—C2	131.40 (11)	C12—N2—C6—C5	47.51 (13)
C10—N1—C1—C2	−54.03 (14)	C6—N2—C7—C8	−7.63 (14)
C9—N1—C1—C6	−49.55 (15)	C12—N2—C7—C8	173.63 (9)
C10—N1—C1—C6	125.02 (11)	C6—N2—C7—S2	175.84 (8)
C6—C1—C2—C3	−2.23 (17)	C12—N2—C7—S2	−2.90 (14)
N1—C1—C2—C3	176.84 (10)	N2—C7—C8—C9	−71.66 (11)
C1—C2—C3—C4	−0.26 (18)	S2—C7—C8—C9	105.04 (9)
C2—C3—C4—C5	2.27 (18)	C1—N1—C9—C8	−0.07 (15)
C3—C4—C5—C6	−1.77 (17)	C10—N1—C9—C8	−174.43 (10)
C2—C1—C6—C5	2.70 (16)	C1—N1—C9—S1	175.67 (8)
N1—C1—C6—C5	−176.34 (10)	C10—N1—C9—S1	1.30 (15)
C2—C1—C6—N2	−176.18 (10)	C7—C8—C9—N1	77.46 (11)
N1—C1—C6—N2	4.78 (16)	C7—C8—C9—S1	−98.46 (10)
C4—C5—C6—C1	−0.73 (16)	C9—N1—C10—C11	87.54 (13)
C4—C5—C6—N2	178.20 (10)	C1—N1—C10—C11	−87.08 (12)
C7—N2—C6—C1	47.63 (15)	C7—N2—C12—C13	−85.53 (13)
C12—N2—C6—C1	−133.60 (11)	C6—N2—C12—C13	95.68 (12)
C7—N2—C6—C5	−131.26 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···S1ⁱ	0.95	2.86	3.6474 (13)	141
C12—H12A···S1ⁱⁱ	0.99	2.87	3.4887 (13)	121

Symmetry codes: (i) x, −y+2, z+1/2; (ii) x, −y+1, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···S1ⁱ	0.95	2.86	3.6474 (13)	141
C12—H12A···S1ⁱⁱ	0.99	2.87	3.4887 (13)	121

Symmetry codes: (i) x, −y+2, z+1/2; (ii) x, −y+1, z+1/2.

References

Bruker (2009). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kumar, R., Chaudhary, P., Nimesh, S., Verma, A. K. & Chandra, R. (2006). Green Chem. 8, 519–521. CrossRef CAS Google Scholar
Ourahou, S., Zouihri, H., Essassi, E. M. & Ng, S. W. (2010). Acta Cryst. E66, o1653. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Swamy, G. Y. S. K., Sridhar, B., Ravikumar, K., Reddy, K. S. & Reddy, V. V. N. (2008). J. Struct. Chem. 49, 775–779. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 2| February 2015| Page o83

doi:10.1107/S205698901402790X

Open

access