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Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003826/qa0247sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003826/qa0247Isup2.hkl |
CCDC reference: 144721
To a solution of 4-acetonylidene-1,5-benzodiazepin-2-one (1 mmol), in benzene (60 ml), tetra-n-butylammonium bromide (20 mmol) in NaOH (30 ml) was added as an alkylating agent. After dilution and decantation, the organic phase was washed with a hydrochloric acid solution (10%) and dried. The benzene was evaporated under reduced pressure and the residue was chromatographied on a silicate column with hexane as eluant. Analysis measured (calculated): C 68.83 (68.85), H 6.52 (6.56), N 11.43% (11.47%).
All H atoms were initially located by difference Fourier synthesis. Subsequently their positions were idealized and constrained to ride on their parent atoms with C—H(aromatic) = 0.95, C—H(secondary) = 0.99, C—H(methyl) = 0.98 or N—H = 0.88 Å, and fixed individual displacement parameters [U(H) = 1.5Ueq(Cmethyl), U(H) = 1.2Ueq(C) or U(H) = 1.2Ueq(N)]. The C23 methyl group was allowed to rotate about its local threefold axis.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
| C14H16N2O2 | F(000) = 520 |
| Mr = 244.29 | Dx = 1.249 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.730 (1) Å | Cell parameters from 8192 reflections |
| b = 10.052 (1) Å | θ = 1–25° |
| c = 14.998 (2) Å | µ = 0.09 mm−1 |
| β = 99.36 (1)° | T = 173 K |
| V = 1298.6 (3) Å3 | Block, colourless |
| Z = 4 | 0.60 × 0.40 × 0.30 mm |
| Siemens CCD three-circle diffractometer | 3350 independent reflections |
| Radiation source: fine-focus sealed tube | 2865 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.034 |
| ω scans | θmax = 28.7°, θmin = 2.5° |
| Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −11→11 |
| Tmin = 0.951, Tmax = 0.975 | k = −13→13 |
| 28486 measured reflections | l = −20→20 |
| 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.113 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0635P)2 + 0.2665P] where P = (Fo2 + 2Fc2)/3 |
| 3350 reflections | (Δ/σ)max < 0.001 |
| 164 parameters | Δρmax = 0.29 e Å−3 |
| 0 restraints | Δρmin = −0.26 e Å−3 |
| C14H16N2O2 | V = 1298.6 (3) Å3 |
| Mr = 244.29 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 8.730 (1) Å | µ = 0.09 mm−1 |
| b = 10.052 (1) Å | T = 173 K |
| c = 14.998 (2) Å | 0.60 × 0.40 × 0.30 mm |
| β = 99.36 (1)° |
| Siemens CCD three-circle diffractometer | 3350 independent reflections |
| Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2865 reflections with I > 2σ(I) |
| Tmin = 0.951, Tmax = 0.975 | Rint = 0.034 |
| 28486 measured reflections |
| R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
| wR(F2) = 0.113 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.29 e Å−3 |
| 3350 reflections | Δρmin = −0.26 e Å−3 |
| 164 parameters |
Experimental. The data collection nominally covered a sphere of reciprocal space, by a combination of seven sets of exposures; each set had a different ϕ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 4.0 cm. Coverage of the unique set is complete to at least 28.7° in θ. Crystal decay was monitored by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. |
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. |
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.46534 (10) | 0.43203 (9) | 0.62495 (6) | 0.02222 (19) | |
| H1 | 0.5259 | 0.3625 | 0.6229 | 0.027* | |
| C2 | 0.33404 (11) | 0.43767 (10) | 0.56246 (6) | 0.0205 (2) | |
| C21 | 0.29564 (12) | 0.33991 (10) | 0.49863 (7) | 0.0232 (2) | |
| H21 | 0.1986 | 0.3458 | 0.4596 | 0.028* | |
| C22 | 0.39557 (12) | 0.22904 (10) | 0.48821 (7) | 0.0244 (2) | |
| O22 | 0.52661 (9) | 0.21479 (8) | 0.53529 (5) | 0.03016 (19) | |
| C23 | 0.33998 (16) | 0.12815 (13) | 0.41531 (8) | 0.0363 (3) | |
| H23A | 0.3754 | 0.1543 | 0.3591 | 0.054* | |
| H23B | 0.2263 | 0.1244 | 0.4054 | 0.054* | |
| H23C | 0.3822 | 0.0404 | 0.4342 | 0.054* | |
| C3 | 0.23137 (12) | 0.55702 (10) | 0.56690 (7) | 0.0228 (2) | |
| H3A | 0.1519 | 0.5615 | 0.5118 | 0.027* | |
| H3B | 0.2942 | 0.6394 | 0.5705 | 0.027* | |
| C4 | 0.15309 (11) | 0.54497 (10) | 0.64994 (7) | 0.0235 (2) | |
| O41 | 0.01369 (9) | 0.52173 (9) | 0.64299 (6) | 0.0341 (2) | |
| N5 | 0.24869 (10) | 0.55525 (9) | 0.73144 (6) | 0.0250 (2) | |
| C51 | 0.18245 (14) | 0.53172 (14) | 0.81505 (8) | 0.0339 (3) | |
| H51A | 0.0737 | 0.5013 | 0.7986 | 0.041* | |
| H51B | 0.1816 | 0.6165 | 0.8486 | 0.041* | |
| C52 | 0.27324 (17) | 0.42926 (16) | 0.87568 (10) | 0.0452 (3) | |
| H52A | 0.2247 | 0.4161 | 0.9295 | 0.068* | |
| H52B | 0.3802 | 0.4603 | 0.8939 | 0.068* | |
| H52C | 0.2737 | 0.3449 | 0.8430 | 0.068* | |
| C6 | 0.40960 (11) | 0.59090 (10) | 0.74124 (7) | 0.0222 (2) | |
| C7 | 0.46775 (13) | 0.68533 (11) | 0.80699 (7) | 0.0286 (2) | |
| H7 | 0.3979 | 0.7322 | 0.8380 | 0.034* | |
| C8 | 0.62531 (14) | 0.71142 (12) | 0.82744 (8) | 0.0306 (2) | |
| H8 | 0.6629 | 0.7747 | 0.8728 | 0.037* | |
| C9 | 0.72842 (12) | 0.64477 (11) | 0.78152 (7) | 0.0282 (2) | |
| H9 | 0.8368 | 0.6609 | 0.7964 | 0.034* | |
| C10 | 0.67276 (12) | 0.55482 (10) | 0.71398 (7) | 0.0237 (2) | |
| H10 | 0.7434 | 0.5113 | 0.6817 | 0.028* | |
| C11 | 0.51354 (11) | 0.52712 (10) | 0.69265 (6) | 0.0202 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0189 (4) | 0.0250 (4) | 0.0218 (4) | 0.0037 (3) | 0.0003 (3) | −0.0036 (3) |
| C2 | 0.0183 (4) | 0.0243 (5) | 0.0188 (4) | 0.0004 (3) | 0.0030 (3) | 0.0019 (3) |
| C21 | 0.0215 (5) | 0.0272 (5) | 0.0196 (4) | 0.0013 (4) | −0.0005 (4) | −0.0005 (4) |
| C22 | 0.0283 (5) | 0.0255 (5) | 0.0191 (4) | 0.0011 (4) | 0.0036 (4) | 0.0005 (4) |
| O22 | 0.0281 (4) | 0.0331 (4) | 0.0275 (4) | 0.0081 (3) | −0.0008 (3) | −0.0037 (3) |
| C23 | 0.0448 (7) | 0.0313 (6) | 0.0297 (6) | 0.0055 (5) | −0.0033 (5) | −0.0085 (5) |
| C3 | 0.0210 (5) | 0.0242 (5) | 0.0224 (5) | 0.0027 (4) | 0.0007 (4) | 0.0013 (4) |
| C4 | 0.0192 (5) | 0.0230 (5) | 0.0283 (5) | 0.0031 (4) | 0.0036 (4) | −0.0008 (4) |
| O41 | 0.0178 (4) | 0.0449 (5) | 0.0394 (5) | 0.0008 (3) | 0.0037 (3) | 0.0001 (4) |
| N5 | 0.0190 (4) | 0.0331 (5) | 0.0238 (4) | −0.0002 (3) | 0.0064 (3) | −0.0018 (3) |
| C51 | 0.0296 (6) | 0.0467 (7) | 0.0283 (5) | −0.0012 (5) | 0.0132 (4) | −0.0023 (5) |
| C52 | 0.0486 (8) | 0.0526 (8) | 0.0362 (7) | −0.0048 (6) | 0.0128 (6) | 0.0109 (6) |
| C6 | 0.0196 (5) | 0.0255 (5) | 0.0213 (4) | −0.0001 (4) | 0.0026 (3) | −0.0003 (4) |
| C7 | 0.0305 (5) | 0.0291 (5) | 0.0262 (5) | 0.0013 (4) | 0.0045 (4) | −0.0061 (4) |
| C8 | 0.0339 (6) | 0.0287 (5) | 0.0268 (5) | −0.0043 (4) | −0.0026 (4) | −0.0053 (4) |
| C9 | 0.0220 (5) | 0.0308 (6) | 0.0292 (5) | −0.0039 (4) | −0.0037 (4) | 0.0020 (4) |
| C10 | 0.0190 (5) | 0.0283 (5) | 0.0233 (5) | 0.0010 (4) | 0.0016 (4) | 0.0024 (4) |
| C11 | 0.0195 (4) | 0.0223 (4) | 0.0181 (4) | 0.0002 (3) | 0.0009 (3) | 0.0008 (3) |
| N1—C2 | 1.3587 (13) | N5—C6 | 1.4340 (13) |
| N1—C11 | 1.4082 (13) | N5—C51 | 1.4829 (14) |
| C2—C21 | 1.3747 (14) | C51—C52 | 1.5104 (19) |
| C2—C3 | 1.5055 (14) | C6—C7 | 1.4030 (14) |
| C21—C22 | 1.4394 (14) | C6—C11 | 1.4072 (14) |
| C22—O22 | 1.2510 (13) | C7—C8 | 1.3848 (16) |
| C22—C23 | 1.5123 (15) | C8—C9 | 1.3910 (17) |
| C3—C4 | 1.5198 (14) | C9—C10 | 1.3855 (15) |
| C4—O41 | 1.2268 (13) | C10—C11 | 1.4026 (13) |
| C4—N5 | 1.3672 (14) | ||
| C2—N1—C11 | 126.07 (8) | C4—N5—C51 | 118.60 (9) |
| N1—C2—C21 | 122.23 (9) | C6—N5—C51 | 117.61 (9) |
| N1—C2—C3 | 116.38 (9) | N5—C51—C52 | 112.29 (10) |
| C21—C2—C3 | 121.39 (9) | C7—C6—C11 | 118.82 (9) |
| C2—C21—C22 | 123.07 (9) | C7—C6—N5 | 118.52 (9) |
| O22—C22—C21 | 122.83 (9) | C11—C6—N5 | 122.45 (9) |
| O22—C22—C23 | 119.20 (10) | C8—C7—C6 | 121.11 (10) |
| C21—C22—C23 | 117.96 (9) | C7—C8—C9 | 119.90 (10) |
| C2—C3—C4 | 108.85 (8) | C10—C9—C8 | 119.87 (10) |
| O41—C4—N5 | 122.90 (10) | C9—C10—C11 | 120.86 (10) |
| O41—C4—C3 | 121.17 (10) | C10—C11—C6 | 119.34 (9) |
| N5—C4—C3 | 115.86 (9) | C10—C11—N1 | 117.91 (9) |
| C4—N5—C6 | 123.77 (9) | C6—C11—N1 | 122.71 (9) |
| C11—N1—C2—C21 | −179.87 (9) | C51—N5—C6—C7 | −43.84 (14) |
| C11—N1—C2—C3 | −0.16 (14) | C4—N5—C6—C11 | −50.70 (15) |
| N1—C2—C21—C22 | −4.66 (16) | C51—N5—C6—C11 | 130.89 (11) |
| C3—C2—C21—C22 | 175.64 (9) | C11—C6—C7—C8 | −3.15 (16) |
| C2—C21—C22—O22 | −1.58 (16) | N5—C6—C7—C8 | 171.78 (10) |
| C2—C21—C22—C23 | −179.94 (10) | C6—C7—C8—C9 | 0.91 (17) |
| N1—C2—C3—C4 | −71.37 (11) | C7—C8—C9—C10 | 1.53 (17) |
| C21—C2—C3—C4 | 108.34 (10) | C8—C9—C10—C11 | −1.70 (16) |
| C2—C3—C4—O41 | −109.24 (11) | C9—C10—C11—C6 | −0.57 (15) |
| C2—C3—C4—N5 | 67.76 (11) | C9—C10—C11—N1 | −178.32 (9) |
| O41—C4—N5—C6 | −175.75 (10) | C7—C6—C11—C10 | 2.94 (15) |
| C3—C4—N5—C6 | 7.31 (14) | N5—C6—C11—C10 | −171.78 (9) |
| O41—C4—N5—C51 | 2.65 (16) | C7—C6—C11—N1 | −179.42 (9) |
| C3—C4—N5—C51 | −174.29 (9) | N5—C6—C11—N1 | 5.86 (15) |
| C4—N5—C51—C52 | 127.04 (12) | C2—N1—C11—C10 | −142.55 (10) |
| C6—N5—C51—C52 | −54.47 (14) | C2—N1—C11—C6 | 39.78 (15) |
| C4—N5—C6—C7 | 134.57 (11) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10—H10···O41i | 0.95 | 2.52 | 3.3367 (13) | 144 |
| C21—H21···O41ii | 0.95 | 2.58 | 3.4457 (14) | 152 |
| C3—H3A···O41ii | 0.99 | 2.66 | 3.5948 (14) | 157 |
| N1—H1···O22 | 0.88 | 1.98 | 2.6640 (12) | 133 |
| Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C14H16N2O2 |
| Mr | 244.29 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 173 |
| a, b, c (Å) | 8.730 (1), 10.052 (1), 14.998 (2) |
| β (°) | 99.36 (1) |
| V (Å3) | 1298.6 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.09 |
| Crystal size (mm) | 0.60 × 0.40 × 0.30 |
| Data collection | |
| Diffractometer | Siemens CCD three-circle diffractometer |
| Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.951, 0.975 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 28486, 3350, 2865 |
| Rint | 0.034 |
| (sin θ/λ)max (Å−1) | 0.676 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.113, 1.07 |
| No. of reflections | 3350 |
| No. of parameters | 164 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.29, −0.26 |
Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10—H10···O41i | 0.95 | 2.52 | 3.3367 (13) | 143.8 |
| C21—H21···O41ii | 0.95 | 2.58 | 3.4457 (14) | 151.9 |
| C3—H3A···O41ii | 0.99 | 2.66 | 3.5948 (14) | 157.1 |
| N1—H1···O22 | 0.88 | 1.98 | 2.6640 (12) | 133.2 |
| Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1. |
As part of our research on the use of 4-hydroxy-6-methylpyran-2-one in heterocyclic synthesis (El Abassi et al., 1987, 1997; Essassi et al., 1987), we have reinspected the condensation of o-phenylenediamine with γ-pyrone with the aim of confirming the structure of the obtained product. In a previous work (El Abassi et al., 1987), we have shown that the reaction of o-phenylenediamine with γ-pyrone leads to 4-acetonylidene-1,5-benzodiazepin-2-one. In order to confirm the structure of the reaction product, we have converted 4-acetonylidene-1,5-benzodiazepin-2-one with ethyl bromide to afford the title compound, (I), and carried out an X-ray structure analysis.
The geometry of the title compound shows no unusual features. The diazepine ring shows a boat conformation. The seven-membered ring can be described as being composed of three planes: a bow plane (C2, C3 and C4), a central plane (N1, C2, C4 and N5; r.m.s. deviation 0.019 Å) and a stern plane (N1 C11, C6 and N5; r.m.s. deviation 0.013 Å). The dihedral angle between central and bow planes is 58.70 (8)°, and there is an angle of 36.31 (5)° between central and stern planes.
The title compound shows an intramolecular hydrogen bond between the NH group of the diazepine ring and a carbonyl O atom of one of the side chains. Furthermore, the other carbonyl O atom shows three short C—H···O contacts.