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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1408.
Published online 2010 May 22. doi:  10.1107/S1600536810017885
PMCID: PMC2979438

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

Abstract

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 [triangle]). For the microwave-assisted synthesis, see: Koizumi (2006 [triangle]). For a related structure, see: Saber et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1408-scheme1.jpg

Experimental

Crystal data

  • C10H10N2O·H2O
  • M r = 192.22
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1408-efi1.jpg
  • 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[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 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

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017885/nc2183Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

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.

Figures

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.

Crystal data

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

Bruker X8 APEXII diffractometer2417 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
graphiteθmax = 30.0°, θmin = 2.8°
[var phi] and ω scansh = −6→6
14168 measured reflectionsk = −10→10
2778 independent reflectionsl = −19→19

Refinement

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 = 1.01w = 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

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

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)

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, °)

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—C6−41.08 (13)C7—N2—C6—C5−147.70 (9)
C6—C1—C2—C30.11 (13)C7—N2—C6—C136.97 (13)
N1—C1—C2—C3173.89 (8)C6—N2—C7—O1−178.52 (8)
C1—C2—C3—C4−2.16 (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—C9−67.42 (10)
C4—C5—C6—C1−2.73 (13)C1—N1—C9—C10176.32 (9)
C4—C5—C6—N2−178.25 (8)C1—N1—C9—C8−2.65 (13)
C2—C1—C6—C52.31 (12)C7—C8—C9—N171.61 (11)
N1—C1—C6—C5−170.86 (8)C7—C8—C9—C10−107.38 (10)
C2—C1—C6—N2177.52 (7)

Hydrogen-bond geometry (Å, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2183).

References

  • Ahabchane, A. H., Keita, A. & Essassi, E. M. (1999). Comp. Rend. Ser. IIC, 2, 519–523.
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Koizumi, H. (2006). Chem. Lett.35, 1350–1351.
  • Saber, A., Zouihri, H., Essassi, E. M. & Ng, S. W. (2010). Acta Cryst. E66, o1409. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43 Submitted.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography