organic compounds
4-Phenyl-1H-1,5-benzodiazepin-2(3H)-one
aDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, bDepartment of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland, cDepartment of Chemistry, Faculty of Science, Sohag University, 82524 Sohag, Egypt, dChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, and eChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt
*Correspondence e-mail: akkurt@erciyes.edu.tr, a.r.Kennedy@strath.ac.uk
In the title compound, C15H12N2O, the phenyl ring makes a dihedral angle of 32.45 (9)° with the benzene ring of the 1,5-benzodiazepin-2-one unit. The seven-membered ring adopts a boat conformation with the methylene group as the prow and the fused benzene-ring C atoms as the stern. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R22(8) loops. The dimers are further linked by C—H⋯O hydrogen bonds, so forming a column along the a-axis direction.
Related literature
For background to benzodiazepine compounds, see: McKernan (2000); Thakur et al. (2003). For related structures, see: Benelbaghdadi et al. (2003); Višnjevac et al. (2002).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON.
Supporting information
10.1107/S160053681204651X/hb6983sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681204651X/hb6983Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681204651X/hb6983Isup3.cml
To a stirred boiling solution of 0.1 mol (10.8 g) benzene-1,2-diamine in 100 ml p-xylene, 0.12 mol (23.12 g) ethyl 3-oxo-3-phenylpropanoate was added in dropwise and refluxed for 2 h. The reaction mixture was left to stand at room temperature for 24 h. The precipitated solid was collected by filtration and recrystallized from benzene to give colourless rods in 90% yield (M.p. 480 K).
The amine H atom was located from a difference map and refined with a distance restraint of N—H = 0.91 (2) Å. H atoms bound to C atoms were positioned geometrically and refined using a riding model [C—H = 0.95–0.99 Å, and Uiso(H) = 1.2Ueq(C)].
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).C15H12N2O | Z = 2 |
Mr = 236.27 | F(000) = 248 |
Triclinic, P1 | Dx = 1.362 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.6894 (5) Å | Cell parameters from 1808 reflections |
b = 10.8353 (13) Å | θ = 3.6–28.6° |
c = 11.7540 (13) Å | µ = 0.09 mm−1 |
α = 77.721 (10)° | T = 123 K |
β = 83.805 (9)° | Rod, colourless |
γ = 82.112 (10)° | 0.35 × 0.09 × 0.06 mm |
V = 576.13 (12) Å3 |
Oxford Diffraction Xcalibur Eos CCD diffractometer | 2584 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1830 reflections with I > 2σI |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 16.0727 pixels mm-1 | θmax = 28.7°, θmin = 3.6° |
ω scans | h = −5→5 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −13→14 |
Tmin = 0.928, Tmax = 1.000 | l = −14→14 |
4335 measured reflections |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.0566P] where P = (Fo2 + 2Fc2)/3 |
2584 reflections | (Δ/σ)max < 0.001 |
167 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C15H12N2O | γ = 82.112 (10)° |
Mr = 236.27 | V = 576.13 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.6894 (5) Å | Mo Kα radiation |
b = 10.8353 (13) Å | µ = 0.09 mm−1 |
c = 11.7540 (13) Å | T = 123 K |
α = 77.721 (10)° | 0.35 × 0.09 × 0.06 mm |
β = 83.805 (9)° |
Oxford Diffraction Xcalibur Eos CCD diffractometer | 2584 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1830 reflections with I > 2σI |
Tmin = 0.928, Tmax = 1.000 | Rint = 0.034 |
4335 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.24 e Å−3 |
2584 reflections | Δρmin = −0.29 e Å−3 |
167 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.5985 (3) | 0.83316 (12) | −0.01502 (12) | 0.0240 (4) | |
N1 | 0.2761 (3) | 0.91004 (15) | 0.11765 (15) | 0.0196 (5) | |
N2 | 0.1807 (3) | 0.67999 (15) | 0.30340 (14) | 0.0208 (5) | |
C1 | 0.2541 (4) | 0.69700 (17) | 0.09252 (17) | 0.0198 (6) | |
C2 | 0.3919 (4) | 0.81833 (18) | 0.05942 (17) | 0.0189 (6) | |
C3 | 0.0429 (4) | 0.90428 (18) | 0.20457 (17) | 0.0191 (6) | |
C4 | −0.1284 (4) | 1.01875 (18) | 0.21167 (18) | 0.0223 (6) | |
C5 | −0.3538 (4) | 1.0235 (2) | 0.29689 (19) | 0.0265 (7) | |
C6 | −0.4128 (4) | 0.9137 (2) | 0.37674 (19) | 0.0264 (7) | |
C7 | −0.2380 (4) | 0.80156 (19) | 0.37327 (18) | 0.0238 (6) | |
C8 | −0.0060 (4) | 0.79387 (18) | 0.28803 (17) | 0.0198 (6) | |
C9 | 0.3135 (4) | 0.63570 (17) | 0.21650 (17) | 0.0188 (6) | |
C10 | 0.5331 (4) | 0.52265 (17) | 0.24188 (17) | 0.0187 (6) | |
C11 | 0.7291 (4) | 0.48274 (18) | 0.15578 (18) | 0.0219 (6) | |
C12 | 0.9357 (4) | 0.37853 (19) | 0.18455 (19) | 0.0255 (7) | |
C13 | 0.9510 (4) | 0.31567 (19) | 0.29879 (19) | 0.0263 (7) | |
C14 | 0.7573 (4) | 0.35380 (19) | 0.38557 (19) | 0.0265 (7) | |
C15 | 0.5496 (4) | 0.45695 (18) | 0.35707 (18) | 0.0230 (6) | |
H1A | 0.33500 | 0.63890 | 0.03940 | 0.0240* | |
H1B | 0.04320 | 0.71540 | 0.08580 | 0.0240* | |
H1N | 0.324 (4) | 0.990 (2) | 0.089 (2) | 0.038 (6)* | |
H4 | −0.08940 | 1.09410 | 0.15730 | 0.0270* | |
H5 | −0.46890 | 1.10190 | 0.30100 | 0.0320* | |
H6 | −0.57300 | 0.91620 | 0.43340 | 0.0320* | |
H7 | −0.27520 | 0.72760 | 0.42990 | 0.0290* | |
H11 | 0.72190 | 0.52680 | 0.07690 | 0.0260* | |
H12 | 1.06670 | 0.35070 | 0.12510 | 0.0310* | |
H13 | 1.09520 | 0.24570 | 0.31820 | 0.0320* | |
H14 | 0.76660 | 0.30960 | 0.46430 | 0.0320* | |
H15 | 0.41690 | 0.48320 | 0.41680 | 0.0280* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0232 (7) | 0.0258 (8) | 0.0206 (8) | −0.0022 (6) | 0.0039 (6) | −0.0025 (6) |
N1 | 0.0205 (8) | 0.0168 (8) | 0.0207 (10) | −0.0034 (6) | 0.0005 (7) | −0.0021 (7) |
N2 | 0.0188 (8) | 0.0212 (9) | 0.0216 (10) | −0.0027 (6) | 0.0008 (6) | −0.0033 (7) |
C1 | 0.0198 (9) | 0.0200 (10) | 0.0200 (11) | −0.0020 (7) | −0.0025 (7) | −0.0048 (8) |
C2 | 0.0188 (9) | 0.0197 (10) | 0.0175 (11) | −0.0005 (7) | −0.0061 (7) | −0.0008 (8) |
C3 | 0.0151 (9) | 0.0241 (10) | 0.0199 (11) | −0.0041 (7) | −0.0007 (7) | −0.0079 (8) |
C4 | 0.0225 (10) | 0.0191 (10) | 0.0251 (12) | −0.0032 (8) | −0.0028 (8) | −0.0033 (8) |
C5 | 0.0205 (10) | 0.0295 (11) | 0.0309 (13) | 0.0017 (8) | −0.0038 (8) | −0.0110 (10) |
C6 | 0.0183 (10) | 0.0351 (12) | 0.0276 (12) | −0.0023 (8) | 0.0015 (8) | −0.0125 (10) |
C7 | 0.0189 (10) | 0.0285 (11) | 0.0239 (12) | −0.0061 (8) | 0.0007 (8) | −0.0043 (9) |
C8 | 0.0161 (9) | 0.0224 (10) | 0.0221 (11) | −0.0028 (7) | −0.0028 (8) | −0.0065 (8) |
C9 | 0.0189 (9) | 0.0197 (10) | 0.0183 (11) | −0.0057 (7) | −0.0010 (7) | −0.0028 (8) |
C10 | 0.0178 (9) | 0.0188 (10) | 0.0211 (11) | −0.0047 (7) | −0.0022 (7) | −0.0054 (8) |
C11 | 0.0233 (10) | 0.0239 (11) | 0.0188 (11) | −0.0049 (8) | −0.0010 (8) | −0.0042 (8) |
C12 | 0.0221 (10) | 0.0271 (11) | 0.0284 (13) | −0.0021 (8) | 0.0020 (8) | −0.0106 (9) |
C13 | 0.0207 (10) | 0.0248 (11) | 0.0336 (13) | −0.0003 (8) | −0.0039 (8) | −0.0068 (9) |
C14 | 0.0278 (11) | 0.0270 (11) | 0.0229 (12) | −0.0022 (8) | −0.0033 (8) | −0.0012 (9) |
C15 | 0.0232 (10) | 0.0249 (11) | 0.0206 (11) | −0.0019 (8) | −0.0008 (8) | −0.0053 (9) |
O1—C2 | 1.237 (2) | C10—C11 | 1.390 (3) |
N1—C2 | 1.346 (3) | C11—C12 | 1.391 (3) |
N1—C3 | 1.412 (3) | C12—C13 | 1.375 (3) |
N2—C8 | 1.402 (3) | C13—C14 | 1.383 (3) |
N2—C9 | 1.285 (3) | C14—C15 | 1.387 (3) |
N1—H1N | 0.91 (2) | C1—H1A | 0.9900 |
C1—C9 | 1.506 (3) | C1—H1B | 0.9900 |
C1—C2 | 1.503 (3) | C4—H4 | 0.9500 |
C3—C8 | 1.405 (3) | C5—H5 | 0.9500 |
C3—C4 | 1.395 (3) | C6—H6 | 0.9500 |
C4—C5 | 1.379 (3) | C7—H7 | 0.9500 |
C5—C6 | 1.390 (3) | C11—H11 | 0.9500 |
C6—C7 | 1.375 (3) | C12—H12 | 0.9500 |
C7—C8 | 1.404 (3) | C13—H13 | 0.9500 |
C9—C10 | 1.488 (3) | C14—H14 | 0.9500 |
C10—C15 | 1.394 (3) | C15—H15 | 0.9500 |
C2—N1—C3 | 127.34 (17) | C12—C13—C14 | 120.27 (19) |
C8—N2—C9 | 122.03 (17) | C13—C14—C15 | 119.7 (2) |
C2—N1—H1N | 117.5 (14) | C10—C15—C14 | 120.81 (19) |
C3—N1—H1N | 113.8 (13) | C2—C1—H1A | 110.00 |
C2—C1—C9 | 108.46 (16) | C2—C1—H1B | 110.00 |
O1—C2—C1 | 122.81 (17) | C9—C1—H1A | 110.00 |
O1—C2—N1 | 122.06 (18) | C9—C1—H1B | 110.00 |
N1—C2—C1 | 115.13 (16) | H1A—C1—H1B | 108.00 |
N1—C3—C8 | 123.51 (17) | C3—C4—H4 | 120.00 |
C4—C3—C8 | 119.81 (18) | C5—C4—H4 | 120.00 |
N1—C3—C4 | 116.43 (17) | C4—C5—H5 | 120.00 |
C3—C4—C5 | 120.61 (19) | C6—C5—H5 | 120.00 |
C4—C5—C6 | 120.12 (19) | C5—C6—H6 | 120.00 |
C5—C6—C7 | 119.63 (19) | C7—C6—H6 | 120.00 |
C6—C7—C8 | 121.54 (19) | C6—C7—H7 | 119.00 |
C3—C8—C7 | 118.18 (18) | C8—C7—H7 | 119.00 |
N2—C8—C7 | 116.13 (17) | C10—C11—H11 | 120.00 |
N2—C8—C3 | 125.11 (17) | C12—C11—H11 | 120.00 |
N2—C9—C1 | 121.42 (17) | C11—C12—H12 | 120.00 |
N2—C9—C10 | 117.88 (17) | C13—C12—H12 | 120.00 |
C1—C9—C10 | 120.69 (16) | C12—C13—H13 | 120.00 |
C9—C10—C11 | 122.52 (18) | C14—C13—H13 | 120.00 |
C11—C10—C15 | 118.72 (18) | C13—C14—H14 | 120.00 |
C9—C10—C15 | 118.73 (17) | C15—C14—H14 | 120.00 |
C10—C11—C12 | 120.32 (19) | C10—C15—H15 | 120.00 |
C11—C12—C13 | 120.21 (19) | C14—C15—H15 | 120.00 |
C3—N1—C2—O1 | −179.53 (18) | C3—C4—C5—C6 | −0.1 (3) |
C3—N1—C2—C1 | −0.2 (3) | C4—C5—C6—C7 | 2.7 (3) |
C2—N1—C3—C4 | −149.39 (19) | C5—C6—C7—C8 | −2.3 (3) |
C2—N1—C3—C8 | 36.4 (3) | C6—C7—C8—N2 | 171.13 (18) |
C9—N2—C8—C3 | −40.1 (3) | C6—C7—C8—C3 | −0.6 (3) |
C9—N2—C8—C7 | 148.81 (19) | N2—C9—C10—C11 | −166.64 (18) |
C8—N2—C9—C1 | −6.0 (3) | N2—C9—C10—C15 | 11.0 (3) |
C8—N2—C9—C10 | 172.89 (17) | C1—C9—C10—C11 | 12.3 (3) |
C9—C1—C2—O1 | 112.8 (2) | C1—C9—C10—C15 | −170.04 (17) |
C9—C1—C2—N1 | −66.6 (2) | C9—C10—C11—C12 | 178.16 (18) |
C2—C1—C9—N2 | 74.3 (2) | C15—C10—C11—C12 | 0.5 (3) |
C2—C1—C9—C10 | −104.6 (2) | C9—C10—C15—C14 | −177.71 (18) |
N1—C3—C4—C5 | −177.32 (18) | C11—C10—C15—C14 | 0.0 (3) |
C8—C3—C4—C5 | −2.9 (3) | C10—C11—C12—C13 | −1.2 (3) |
N1—C3—C8—N2 | 6.3 (3) | C11—C12—C13—C14 | 1.4 (3) |
N1—C3—C8—C7 | 177.21 (18) | C12—C13—C14—C15 | −0.9 (3) |
C4—C3—C8—N2 | −167.75 (18) | C13—C14—C15—C10 | 0.1 (3) |
C4—C3—C8—C7 | 3.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.91 (2) | 1.99 (2) | 2.900 (2) | 175 (2) |
C1—H1B···O1ii | 0.99 | 2.56 | 3.468 (2) | 153 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C15H12N2O |
Mr | 236.27 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 4.6894 (5), 10.8353 (13), 11.7540 (13) |
α, β, γ (°) | 77.721 (10), 83.805 (9), 82.112 (10) |
V (Å3) | 576.13 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.09 × 0.06 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Eos CCD diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.928, 1.000 |
No. of measured, independent and observed (I > 2σI) reflections | 4335, 2584, 1830 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.675 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.140, 1.02 |
No. of reflections | 2584 |
No. of parameters | 167 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.29 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.91 (2) | 1.99 (2) | 2.900 (2) | 175 (2) |
C1—H1B···O1ii | 0.99 | 2.56 | 3.468 (2) | 153 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x−1, y, z. |
Acknowledgements
Manchester Metropolitan University, Erciyes University and University of Strathclyde are gratefully acknowledged for supporting this study.
References
Benelbaghdadi, R., Hasnaoui, R. A., Lavergne, J. P., Ait Itto, M. & Pierrot, M. (2003). Acta Cryst. E59, o143–o144. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
McKernan, R. M. (2000). Nat. Neurosci. 3, 587–592. Web of Science CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. 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
Thakur, A., Thakur, M. & Khadikar, P. V. (2003). Bioorg. Med. Chem. 11, 5203–5207. Web of Science CrossRef PubMed CAS Google Scholar
Višnjevac, A., Avdagić, A. & Kojić-Prodić, B. (2002). Acta Cryst. E58, o148–o150. Web of Science CSD CrossRef 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.
Due to their wide range of pharmacological activity in synthetic and industrial applications, benzodiazepines (BZDs) have attracted the interest of chemists and biologists. They are widely used as anti-inflammatory, analgesic, hypnotic, tranquillizers and anti-depressive agents (e.g. Thakur et al. 2003; McKernan, 2000).
In the title molecule (I), (Fig. 1), the C10–C15 phenyl and C3–C8 benzene rings make a dihedral angle of 32.45 (9)° with each other. All bond lengths and bond angles in (I) are comparable to those reported for similar compounds (Višnjevac et al., 2002; Benelbaghdadi et al., 2003).
The seven-membered ring (N1/N2/C1—C3/C8/C9) of the 1,3-dihydro-2H-1,5-benzodiazepin-2-one moiety exhibits a puckered conformation, with puckering parameters q2= 0.7977 (19) Å, ϕ2 = 337.34 (14)°, q3= 0.250 (2) Å, ϕ3 = 228.2 (5)°, and QT= 0.836 (2) Å.
In the crystal, a pair of N—H···O hydrogen bonds (Table 1) link two molecules into an inversion dimer with an R22(8) motif. Furhermore, C—H···O hydrogen bonds link the dimers, so forming a column along the a axis direction (Fig. 2).