organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Ahabchane, A. H., Keita, A. & Essassi, E. M. (1999). Comp. Rend. Ser. IIC, 2, 519-523.]). For the microwave-assisted synthesis, see: Koizumi (2006[Koizumi, H. (2006). Chem. Lett. 35, 1350-1351.]). For a related structure, see: Saber et al. (2010[Saber, A., Zouihri, H., Essassi, E. M. & Ng, S. W. (2010). Acta Cryst. E66, o1409.]).

[Scheme 1]

Experimental

Crystal data
  • C10H10N2O·H2O

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43. Submitted.]).

Supporting information


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).

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95–0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5Ueq(C).

One of the two hydrogen atoms of the water molecule is disordered over two positions. The hydrogen atom near the center-of-inversion should have only half occupancy; this is linked to the inversion-related water molecule. The O–H distances were restrained to 0.84±0.01 Å and the H···H distances to 1.37±0.01 Å; the isotropic temperature factors of the hydrogen atoms were freely refined.

The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.86±0.01 Å; its temperature factor was also freely refined.

Structure description 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).

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
[Figure 1] 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·H2OZ = 2
Mr = 192.22F(000) = 204
Triclinic, P1Dx = 1.331 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.9013 (1) ÅCell parameters from 7100 reflections
b = 7.3148 (1) Åθ = 2.8–37.4°
c = 13.5688 (2) ŵ = 0.10 mm1
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 tubeRint = 0.025
Graphite monochromatorθmax = 30.0°, θmin = 2.8°
φ and ω scansh = 66
14168 measured reflectionsk = 1010
2778 independent reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0699P)2 + 0.0787P]
where P = (Fo2 + 2Fc2)/3
2778 reflections(Δ/σ)max = 0.001
144 parametersΔρmax = 0.33 e Å3
6 restraintsΔρmin = 0.23 e Å3
Crystal data top
C10H10N2O·H2Oγ = 83.807 (1)°
Mr = 192.22V = 479.76 (1) Å3
Triclinic, P1Z = 2
a = 4.9013 (1) ÅMo Kα radiation
b = 7.3148 (1) ŵ = 0.10 mm1
c = 13.5688 (2) ÅT = 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 reflectionsRint = 0.025
2778 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0386 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.33 e Å3
2778 reflectionsΔρmin = 0.23 e Å3
144 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.50754 (15)0.32480 (10)0.41041 (5)0.03282 (18)
O1W0.7622 (2)0.90681 (16)0.01525 (8)0.0615 (3)
H110.781 (4)0.8214 (18)0.0590 (11)0.067 (5)*
H120.597 (3)0.941 (5)0.009 (3)0.082 (13)*0.50
H130.891 (6)0.975 (4)0.012 (3)0.094 (15)*0.50
N10.89510 (16)0.62527 (11)0.17532 (6)0.02795 (18)
N20.74476 (15)0.57576 (10)0.39494 (5)0.02466 (17)
H20.654 (3)0.6122 (18)0.4498 (8)0.037 (3)*
C11.02194 (17)0.70536 (12)0.24757 (7)0.02450 (18)
C21.21868 (19)0.82648 (13)0.21134 (8)0.0313 (2)
H2A1.27080.83990.14190.038*
C31.3380 (2)0.92630 (13)0.27404 (9)0.0348 (2)
H31.47531.00430.24810.042*
C41.2567 (2)0.91253 (13)0.37537 (9)0.0335 (2)
H41.33460.98370.41870.040*
C51.06207 (19)0.79500 (13)0.41311 (7)0.02855 (19)
H51.00570.78710.48240.034*
C60.94708 (16)0.68755 (11)0.35054 (6)0.02275 (18)
C70.69461 (17)0.41042 (12)0.36746 (6)0.02391 (18)
C80.88337 (18)0.33830 (12)0.28103 (7)0.02627 (19)
H810.85000.21010.27150.032*
H821.07830.33890.29400.032*
C90.82545 (18)0.46102 (13)0.18931 (7)0.02720 (19)
C100.6764 (3)0.38563 (18)0.11355 (9)0.0449 (3)
H10A0.77540.26880.09340.067*
H10B0.66670.47400.05550.067*
H10C0.48930.36460.14210.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0366 (4)0.0335 (4)0.0295 (3)0.0160 (3)0.0020 (3)0.0010 (3)
O1W0.0490 (6)0.0668 (7)0.0649 (6)0.0157 (5)0.0123 (5)0.0400 (5)
N10.0277 (4)0.0321 (4)0.0230 (3)0.0036 (3)0.0011 (3)0.0039 (3)
N20.0266 (3)0.0232 (4)0.0234 (3)0.0059 (3)0.0027 (3)0.0005 (3)
C10.0223 (4)0.0226 (4)0.0272 (4)0.0013 (3)0.0015 (3)0.0047 (3)
C20.0265 (4)0.0291 (5)0.0356 (5)0.0040 (3)0.0025 (3)0.0091 (4)
C30.0253 (4)0.0243 (4)0.0534 (6)0.0063 (3)0.0016 (4)0.0073 (4)
C40.0288 (4)0.0231 (4)0.0500 (6)0.0040 (3)0.0088 (4)0.0025 (4)
C50.0289 (4)0.0244 (4)0.0325 (4)0.0022 (3)0.0044 (3)0.0018 (3)
C60.0209 (3)0.0192 (4)0.0270 (4)0.0013 (3)0.0011 (3)0.0030 (3)
C70.0256 (4)0.0233 (4)0.0227 (4)0.0047 (3)0.0037 (3)0.0036 (3)
C80.0279 (4)0.0222 (4)0.0281 (4)0.0015 (3)0.0020 (3)0.0005 (3)
C90.0264 (4)0.0314 (4)0.0232 (4)0.0023 (3)0.0004 (3)0.0013 (3)
C100.0537 (7)0.0509 (7)0.0340 (5)0.0132 (5)0.0124 (5)0.0054 (5)
Geometric parameters (Å, º) top
O1—C71.2349 (10)C3—H30.9500
O1W—H110.83 (1)C4—C51.3836 (13)
O1W—H120.83 (1)C4—H40.9500
O1W—H130.84 (1)C5—C61.4000 (12)
N1—C91.2783 (12)C5—H50.9500
N1—C11.4108 (12)C7—C81.5086 (12)
N2—C71.3484 (11)C8—C91.5081 (12)
N2—C61.4088 (10)C8—H810.9900
N2—H20.871 (8)C8—H820.9900
C1—C21.4038 (12)C9—C101.4937 (14)
C1—C61.4061 (12)C10—H10A0.9800
C2—C31.3769 (15)C10—H10B0.9800
C2—H2A0.9500C10—H10C0.9800
C3—C41.3894 (16)
H11—O1W—H12112.1 (16)C5—C6—C1119.44 (8)
H11—O1W—H13110.7 (16)C5—C6—N2116.97 (8)
H12—O1W—H13126 (3)C1—C6—N2123.42 (8)
C9—N1—C1121.45 (8)O1—C7—N2122.09 (8)
C7—N2—C6127.19 (7)O1—C7—C8122.73 (8)
C7—N2—H2116.4 (9)N2—C7—C8115.18 (7)
C6—N2—H2116.0 (9)C7—C8—C9108.21 (7)
C2—C1—C6118.40 (9)C7—C8—H81110.1
C2—C1—N1116.10 (8)C9—C8—H81110.1
C6—C1—N1125.17 (8)C7—C8—H82110.1
C3—C2—C1121.59 (9)C9—C8—H82110.1
C3—C2—H2A119.2H81—C8—H82108.4
C1—C2—H2A119.2N1—C9—C10119.67 (9)
C2—C3—C4119.72 (9)N1—C9—C8122.68 (8)
C2—C3—H3120.1C10—C9—C8117.64 (8)
C4—C3—H3120.1C9—C10—H10A109.5
C5—C4—C3119.93 (9)C9—C10—H10B109.5
C5—C4—H4120.0H10A—C10—H10B109.5
C3—C4—H4120.0C9—C10—H10C109.5
C4—C5—C6120.84 (9)H10A—C10—H10C109.5
C4—C5—H5119.6H10B—C10—H10C109.5
C6—C5—H5119.6
C9—N1—C1—C2145.61 (9)N1—C1—C6—N24.35 (13)
C9—N1—C1—C641.08 (13)C7—N2—C6—C5147.70 (9)
C6—C1—C2—C30.11 (13)C7—N2—C6—C136.97 (13)
N1—C1—C2—C3173.89 (8)C6—N2—C7—O1178.52 (8)
C1—C2—C3—C42.16 (15)C6—N2—C7—C81.60 (13)
C2—C3—C4—C51.76 (14)O1—C7—C8—C9112.70 (9)
C3—C4—C5—C60.68 (14)N2—C7—C8—C967.42 (10)
C4—C5—C6—C12.73 (13)C1—N1—C9—C10176.32 (9)
C4—C5—C6—N2178.25 (8)C1—N1—C9—C82.65 (13)
C2—C1—C6—C52.31 (12)C7—C8—C9—N171.61 (11)
N1—C1—C6—C5170.86 (8)C7—C8—C9—C10107.38 (10)
C2—C1—C6—N2177.52 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.87 (1)2.05 (1)2.909 (1)171 (1)
O1w—H11···N10.83 (1)2.12 (1)2.945 (1)170 (2)
O1w—H13···O1wii0.84 (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 formulaC10H10N2O·H2O
Mr192.22
Crystal system, space groupTriclinic, 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)
V3)479.76 (1)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.43 × 0.27 × 0.25
Data collection
DiffractometerBruker X8 APEXII
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
14168, 2778, 2417
Rint0.025
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.115, 1.01
No. of reflections2778
No. of parameters144
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2···O1i0.87 (1)2.046 (9)2.909 (1)171 (1)
O1w—H11···N10.83 (1)2.123 (9)2.945 (1)170 (2)
O1w—H13···O1wii0.84 (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

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

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ISSN: 2056-9890
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