4-Methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one monohydrate

Saber, A.; Zouihri, H.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536810017885

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1408

https://doi.org/10.1107/S1600536810017885

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4-Methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one monohydrate

Asmaa Saber,^a Hafid Zouihri,^b El Mokhtar Essassi ^a and Seik Weng Ng ^c ^*

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, ^bCNRST Division UATRS, Angle Allal Fassi/FAR, BP 8027 Hay Riad, Rabat, Morocco, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 27 April 2010; accepted 14 May 2010; online 22 May 2010)

The seven-membered fused-ring in the title compound, C₁₀H₁₀N₂O·H₂O, adopts a boat conformation (with the two phenylene C atoms representing the stern and the methylene C atom the prow). In the crystal, two benzodiazepinone molecules are linked about a center of inversion by diazepine–carbonyl N—H⋯O hydrogen bonds. The dimers are further linked by water–diazepine O—H⋯N hydrogen bonds, forming a linear chain.

Related literature

For background to the synthesis and biological activity of benzodiazepines, see: Ahabchane et al. (1999 ). For the microwave-assisted synthesis, see: Koizumi (2006 ). For a related structure, see: Saber et al. (2010 ).

Experimental

Crystal data

C₁₀H₁₀N₂O·H₂O
M_r = 192.22
Triclinic, $[P \overline 1]$
a = 4.9013 (1) Å
b = 7.3148 (1) Å
c = 13.5688 (2) Å
α = 85.375 (1)°
β = 83.959 (1)°
γ = 83.807 (1)°
V = 479.76 (1) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.43 × 0.27 × 0.25 mm

Data collection

Bruker X8 APEXII diffractometer
14168 measured reflections
2778 independent reflections
2417 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.115
S = 1.01
2778 reflections
144 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.87 (1)	2.05 (1)	2.909 (1)	171 (1)
O1w—H11⋯N1	0.83 (1)	2.12 (1)	2.945 (1)	170 (2)
O1w—H13⋯O1wⁱⁱ	0.84 (1)	1.98 (1)	2.803 (2)	167 (5)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y+2, -z.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810017885/nc2183sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017885/nc2183Isup2.hkl

checkCIF report

Comment top

The compound is belongs to the class of benzodiazepine drugs; the compound is synthesized by condensing o-phenylenediamine with ethyl acetoacetate, two readily-available commerically chemicals. The chemical background of this class of precusor compounds is presented in an earlier report (Ahabchane et al., 1999). A more recent study reports the microwave-assisted synthesis of the title compound (Koizumi, 2006), which is presumably anhydrous. However, the compound crystallizes as a monohydrate (Scheme I, Fig. 1), as shown from the crystal structure analysis.

One of the two hydrogen atoms of the water molecule is disordered over two positions in a 1:1 ratio. That hydrogen atom near the center-of-inversion is hydrogen bonded to the inversion-related oxygen atom. As the benzodiazepinone molecule is N–H···O hydrogen bonded into a dimer, the water molecule then links adjacent dimers into a linear chain (Table 1).

Related literature top

For background to the synthesis and biological activity of benzodiazepines, see: Ahabchane et al. (1999). For the microwave-assisted synthesis, see: Koizumi (2006). For a related structure, see: Saber et al. (2010).

Experimental top

o-Phenylenediamine (1.0 g, 9 mmol) and ethyl acetoacetate (1.2 ml, 9 mmol) were heated in xylene (10 ml) for 1 hour. The mixture was set aside for the growth of colorless crystals of 4-methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one; yield 90%. When the heating time is lengthened to 6 hours, the product is N-isopropenyl 1,3-benzimidazol-2-one; details are given in another report (Saber et al., 2010).

Structure description top

For background to the synthesis and biological activity of benzodiazepines, see: Ahabchane et al. (1999). For the microwave-assisted synthesis, see: Koizumi (2006). For a related structure, see: Saber et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the molecule of C₁₀H₁₀N₂O^.H₂O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in one of the two the hydrogen atoms of the water molecule is not shown.

4-Methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one monohydrate top

Crystal data top

C₁₀H₁₀N₂O·H₂O	Z = 2
M_r = 192.22	F(000) = 204
Triclinic, P1	D_x = 1.331 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9013 (1) Å	Cell parameters from 7100 reflections
b = 7.3148 (1) Å	θ = 2.8–37.4°
c = 13.5688 (2) Å	µ = 0.10 mm⁻¹
α = 85.375 (1)°	T = 100 K
β = 83.959 (1)°	Block, colorless
γ = 83.807 (1)°	0.43 × 0.27 × 0.25 mm
V = 479.76 (1) Å³

Data collection top

Bruker X8 APEXII diffractometer	2417 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Graphite monochromator	θ_max = 30.0°, θ_min = 2.8°
φ and ω scans	h = −6→6
14168 measured reflections	k = −10→10
2778 independent reflections	l = −19→19

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0699P)² + 0.0787P] where P = (F_o² + 2F_c²)/3
2778 reflections	(Δ/σ)_max = 0.001
144 parameters	Δρ_max = 0.33 e Å⁻³
6 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₀H₁₀N₂O·H₂O	γ = 83.807 (1)°
M_r = 192.22	V = 479.76 (1) Å³
Triclinic, P1	Z = 2
a = 4.9013 (1) Å	Mo Kα radiation
b = 7.3148 (1) Å	µ = 0.10 mm⁻¹
c = 13.5688 (2) Å	T = 100 K
α = 85.375 (1)°	0.43 × 0.27 × 0.25 mm
β = 83.959 (1)°

Data collection top

Bruker X8 APEXII diffractometer	2417 reflections with I > 2σ(I)
14168 measured reflections	R_int = 0.025
2778 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	6 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.33 e Å⁻³
2778 reflections	Δρ_min = −0.23 e Å⁻³
144 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.50754 (15)	0.32480 (10)	0.41041 (5)	0.03282 (18)
O1W	0.7622 (2)	0.90681 (16)	0.01525 (8)	0.0615 (3)
H11	0.781 (4)	0.8214 (18)	0.0590 (11)	0.067 (5)*
H12	0.597 (3)	0.941 (5)	0.009 (3)	0.082 (13)*	0.50
H13	0.891 (6)	0.975 (4)	0.012 (3)	0.094 (15)*	0.50
N1	0.89510 (16)	0.62527 (11)	0.17532 (6)	0.02795 (18)
N2	0.74476 (15)	0.57576 (10)	0.39494 (5)	0.02466 (17)
H2	0.654 (3)	0.6122 (18)	0.4498 (8)	0.037 (3)*
C1	1.02194 (17)	0.70536 (12)	0.24757 (7)	0.02450 (18)
C2	1.21868 (19)	0.82648 (13)	0.21134 (8)	0.0313 (2)
H2A	1.2708	0.8399	0.1419	0.038*
C3	1.3380 (2)	0.92630 (13)	0.27404 (9)	0.0348 (2)
H3	1.4753	1.0043	0.2481	0.042*
C4	1.2567 (2)	0.91253 (13)	0.37537 (9)	0.0335 (2)
H4	1.3346	0.9837	0.4187	0.040*
C5	1.06207 (19)	0.79500 (13)	0.41311 (7)	0.02855 (19)
H5	1.0057	0.7871	0.4824	0.034*
C6	0.94708 (16)	0.68755 (11)	0.35054 (6)	0.02275 (18)
C7	0.69461 (17)	0.41042 (12)	0.36746 (6)	0.02391 (18)
C8	0.88337 (18)	0.33830 (12)	0.28103 (7)	0.02627 (19)
H81	0.8500	0.2101	0.2715	0.032*
H82	1.0783	0.3389	0.2940	0.032*
C9	0.82545 (18)	0.46102 (13)	0.18931 (7)	0.02720 (19)
C10	0.6764 (3)	0.38563 (18)	0.11355 (9)	0.0449 (3)
H10A	0.7754	0.2688	0.0934	0.067*
H10B	0.6667	0.4740	0.0555	0.067*
H10C	0.4893	0.3646	0.1421	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0366 (4)	0.0335 (4)	0.0295 (3)	−0.0160 (3)	0.0020 (3)	0.0010 (3)
O1W	0.0490 (6)	0.0668 (7)	0.0649 (6)	−0.0157 (5)	−0.0123 (5)	0.0400 (5)
N1	0.0277 (4)	0.0321 (4)	0.0230 (3)	−0.0036 (3)	−0.0011 (3)	0.0039 (3)
N2	0.0266 (3)	0.0232 (4)	0.0234 (3)	−0.0059 (3)	0.0027 (3)	0.0005 (3)
C1	0.0223 (4)	0.0226 (4)	0.0272 (4)	−0.0013 (3)	−0.0015 (3)	0.0047 (3)
C2	0.0265 (4)	0.0291 (5)	0.0356 (5)	−0.0040 (3)	0.0025 (3)	0.0091 (4)
C3	0.0253 (4)	0.0243 (4)	0.0534 (6)	−0.0063 (3)	−0.0016 (4)	0.0073 (4)
C4	0.0288 (4)	0.0231 (4)	0.0500 (6)	−0.0040 (3)	−0.0088 (4)	−0.0025 (4)
C5	0.0289 (4)	0.0244 (4)	0.0325 (4)	−0.0022 (3)	−0.0044 (3)	−0.0018 (3)
C6	0.0209 (3)	0.0192 (4)	0.0270 (4)	−0.0013 (3)	−0.0011 (3)	0.0030 (3)
C7	0.0256 (4)	0.0233 (4)	0.0227 (4)	−0.0047 (3)	−0.0037 (3)	0.0036 (3)
C8	0.0279 (4)	0.0222 (4)	0.0281 (4)	−0.0015 (3)	−0.0020 (3)	−0.0005 (3)
C9	0.0264 (4)	0.0314 (4)	0.0232 (4)	−0.0023 (3)	−0.0004 (3)	−0.0013 (3)
C10	0.0537 (7)	0.0509 (7)	0.0340 (5)	−0.0132 (5)	−0.0124 (5)	−0.0054 (5)

Geometric parameters (Å, º) top

O1—C7	1.2349 (10)	C3—H3	0.9500
O1W—H11	0.83 (1)	C4—C5	1.3836 (13)
O1W—H12	0.83 (1)	C4—H4	0.9500
O1W—H13	0.84 (1)	C5—C6	1.4000 (12)
N1—C9	1.2783 (12)	C5—H5	0.9500
N1—C1	1.4108 (12)	C7—C8	1.5086 (12)
N2—C7	1.3484 (11)	C8—C9	1.5081 (12)
N2—C6	1.4088 (10)	C8—H81	0.9900
N2—H2	0.871 (8)	C8—H82	0.9900
C1—C2	1.4038 (12)	C9—C10	1.4937 (14)
C1—C6	1.4061 (12)	C10—H10A	0.9800
C2—C3	1.3769 (15)	C10—H10B	0.9800
C2—H2A	0.9500	C10—H10C	0.9800
C3—C4	1.3894 (16)

H11—O1W—H12	112.1 (16)	C5—C6—C1	119.44 (8)
H11—O1W—H13	110.7 (16)	C5—C6—N2	116.97 (8)
H12—O1W—H13	126 (3)	C1—C6—N2	123.42 (8)
C9—N1—C1	121.45 (8)	O1—C7—N2	122.09 (8)
C7—N2—C6	127.19 (7)	O1—C7—C8	122.73 (8)
C7—N2—H2	116.4 (9)	N2—C7—C8	115.18 (7)
C6—N2—H2	116.0 (9)	C7—C8—C9	108.21 (7)
C2—C1—C6	118.40 (9)	C7—C8—H81	110.1
C2—C1—N1	116.10 (8)	C9—C8—H81	110.1
C6—C1—N1	125.17 (8)	C7—C8—H82	110.1
C3—C2—C1	121.59 (9)	C9—C8—H82	110.1
C3—C2—H2A	119.2	H81—C8—H82	108.4
C1—C2—H2A	119.2	N1—C9—C10	119.67 (9)
C2—C3—C4	119.72 (9)	N1—C9—C8	122.68 (8)
C2—C3—H3	120.1	C10—C9—C8	117.64 (8)
C4—C3—H3	120.1	C9—C10—H10A	109.5
C5—C4—C3	119.93 (9)	C9—C10—H10B	109.5
C5—C4—H4	120.0	H10A—C10—H10B	109.5
C3—C4—H4	120.0	C9—C10—H10C	109.5
C4—C5—C6	120.84 (9)	H10A—C10—H10C	109.5
C4—C5—H5	119.6	H10B—C10—H10C	109.5
C6—C5—H5	119.6

C9—N1—C1—C2	145.61 (9)	N1—C1—C6—N2	4.35 (13)
C9—N1—C1—C6	−41.08 (13)	C7—N2—C6—C5	−147.70 (9)
C6—C1—C2—C3	0.11 (13)	C7—N2—C6—C1	36.97 (13)
N1—C1—C2—C3	173.89 (8)	C6—N2—C7—O1	−178.52 (8)
C1—C2—C3—C4	−2.16 (15)	C6—N2—C7—C8	1.60 (13)
C2—C3—C4—C5	1.76 (14)	O1—C7—C8—C9	112.70 (9)
C3—C4—C5—C6	0.68 (14)	N2—C7—C8—C9	−67.42 (10)
C4—C5—C6—C1	−2.73 (13)	C1—N1—C9—C10	176.32 (9)
C4—C5—C6—N2	−178.25 (8)	C1—N1—C9—C8	−2.65 (13)
C2—C1—C6—C5	2.31 (12)	C7—C8—C9—N1	71.61 (11)
N1—C1—C6—C5	−170.86 (8)	C7—C8—C9—C10	−107.38 (10)
C2—C1—C6—N2	177.52 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.87 (1)	2.05 (1)	2.909 (1)	171 (1)
O1w—H11···N1	0.83 (1)	2.12 (1)	2.945 (1)	170 (2)
O1w—H13···O1wⁱⁱ	0.84 (1)	1.98 (1)	2.803 (2)	167 (5)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂O·H₂O
M_r	192.22
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	4.9013 (1), 7.3148 (1), 13.5688 (2)
α, β, γ (°)	85.375 (1), 83.959 (1), 83.807 (1)
V (Å³)	479.76 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.43 × 0.27 × 0.25

Data collection
Diffractometer	Bruker X8 APEXII
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14168, 2778, 2417
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.115, 1.01
No. of reflections	2778
No. of parameters	144
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.23

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.87 (1)	2.046 (9)	2.909 (1)	171 (1)
O1w—H11···N1	0.83 (1)	2.123 (9)	2.945 (1)	170 (2)
O1w—H13···O1wⁱⁱ	0.84 (1)	1.98 (1)	2.803 (2)	167 (5)

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

Acknowledgements

We thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

References

Ahabchane, A. H., Keita, A. & Essassi, E. M. (1999). Comp. Rend. Ser. IIC, 2, 519–523. CAS Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Koizumi, H. (2006). Chem. Lett. 35, 1350–1351. Web of Science CrossRef CAS Google Scholar
Saber, A., Zouihri, H., Essassi, E. M. & Ng, S. W. (2010). Acta Cryst. E66, o1409. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43. Submitted. Google Scholar