Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034630/hk2293sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034630/hk2293Isup2.hkl |
CCDC reference: 657806
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.002 Å
- R factor = 0.040
- wR factor = 0.116
- Data-to-parameter ratio = 16.4
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
1-(2-hydroxyphenyl)-3-(4-methoxyphenyl)propane-1,3-dione (2.7 g, 10 mmol), prepared according to the reported procedure (Ahmed et al., 1990), was subjected to cyclo-condensation with phenylene diamine (1,08 g, 10 mmol) using toluene (100 ml) as solvent to get the title compound (yield; 62%, m.p.481–483 K). Yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of dichloromethane solution.
H1 (for OH) was located in difference syntheses and refined isotropically [O1—H1 = 0.92 (2) Å and Uiso(H) = 0.088 (6) Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H atoms, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
The title compound belongs to an important class of the pharmacologically pre-eminent 1,5-benzodiazepines which are extensively studied for medicinal activities (Krapcho & Turk, 1966). In recent years, benzodiazepines have replaced barbiturates which were used once for the purpose of hypnotic effects, owing to their less toxic and less severe withdrawal effects (Gringauz, 1999). The importance of 1,5-benzodiazepines, in particular is evident from the pharmaceutical application of Globazam (Butcher & Hamor, 1985). The difficulties encountered in the cyclization of these seven-membered heterocycles limited their structural studies. In view of the importance of this class of compounds, the title compound, (I), has been synthesized and its crystal structure is reported here.
A perspective view of (I) is shown in Fig. 1. Bond lengths and angles can be regarded as normal (Cambridge Structural Database, Version 5.28, November 2006; Allen, 2002; Mogul, Version 1.1; Bruno et al., 2004). The seven membered diazepine ring has a fragment N1—C10—C11—N2, which is conjugated with the adjacent benzene ring. Like azepines, diazepines are not planar and generally adopt boat conformation (Armarego, 1977).
The rings A (C1—C6), B (C10—C15) and C (C16—C21) are, of course, planar and dihedral angles between them are A/B = 39.22 (2)°, A/C = 87.31 (3)° and B/C = 54.42 (3)°. The seven membered ring D (N1/N2/C7—C11) is non-planar and adopts nearly boat conformation.
In the crystal structure, intramolecular O—H···N and intermolecular C—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.
For bond-length data, see: Allen (2002); Bruno et al. (2004). For general background, see: Krapcho & Turk (1966); Gringauz (1999); Butcher & Hamor (1985); Armarego (1977). For related literature, see: Ahmed et al. (1990).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
C22H18N2O2 | F(000) = 720 |
Mr = 342.38 | Dx = 1.337 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3874 reflections |
a = 9.8203 (7) Å | θ = 2.3–28.3° |
b = 16.2920 (12) Å | µ = 0.09 mm−1 |
c = 11.0178 (8) Å | T = 298 K |
β = 105.203 (1)° | Block, yellow |
V = 1701.1 (2) Å3 | 0.33 × 0.30 × 0.27 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4220 independent reflections |
Radiation source: fine-focus sealed tube | 3022 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω and φ scans | θmax = 28.3°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.897, Tmax = 0.980 | k = −21→20 |
9963 measured reflections | l = −14→7 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0582P)2 + 0.3204P] where P = (Fo2 + 2Fc2)/3 |
3928 reflections | (Δ/σ)max = 0.001 |
239 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C22H18N2O2 | V = 1701.1 (2) Å3 |
Mr = 342.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8203 (7) Å | µ = 0.09 mm−1 |
b = 16.2920 (12) Å | T = 298 K |
c = 11.0178 (8) Å | 0.33 × 0.30 × 0.27 mm |
β = 105.203 (1)° |
Bruker SMART CCD area-detector diffractometer | 4220 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3022 reflections with I > 2σ(I) |
Tmin = 0.897, Tmax = 0.980 | Rint = 0.017 |
9963 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.20 e Å−3 |
3928 reflections | Δρmin = −0.18 e Å−3 |
239 parameters |
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 | ||
O1 | −0.03533 (12) | 0.86806 (6) | 0.61876 (11) | 0.0555 (3) | |
H1 | 0.039 (2) | 0.8542 (13) | 0.5869 (19) | 0.088 (6)* | |
O2 | 0.72160 (11) | 1.13972 (6) | 1.11673 (10) | 0.0535 (3) | |
N1 | 0.51345 (11) | 0.89159 (7) | 0.66528 (10) | 0.0416 (3) | |
N2 | 0.19812 (11) | 0.87562 (7) | 0.55763 (11) | 0.0411 (3) | |
C1 | −0.00688 (14) | 0.94474 (8) | 0.66394 (13) | 0.0415 (3) | |
C2 | −0.10065 (16) | 0.98059 (9) | 0.72371 (15) | 0.0519 (4) | |
H2A | −0.1803 | 0.9517 | 0.7298 | 0.062* | |
C3 | −0.07683 (17) | 1.05816 (9) | 0.77385 (15) | 0.0560 (4) | |
H3A | −0.1393 | 1.0808 | 0.8150 | 0.067* | |
C4 | 0.03994 (17) | 1.10289 (9) | 0.76347 (14) | 0.0516 (4) | |
H4A | 0.0564 | 1.1552 | 0.7979 | 0.062* | |
C5 | 0.13119 (15) | 1.06868 (8) | 0.70144 (13) | 0.0433 (3) | |
H5A | 0.2078 | 1.0995 | 0.6926 | 0.052* | |
C6 | 0.11271 (13) | 0.98942 (8) | 0.65144 (11) | 0.0365 (3) | |
C7 | 0.21520 (12) | 0.95158 (8) | 0.59207 (12) | 0.0364 (3) | |
C8 | 0.34185 (13) | 0.99771 (8) | 0.57406 (12) | 0.0383 (3) | |
H8A | 0.3310 | 1.0562 | 0.5848 | 0.046* | |
H8B | 0.3540 | 0.9879 | 0.4907 | 0.046* | |
C9 | 0.46674 (13) | 0.96498 (8) | 0.67378 (12) | 0.0375 (3) | |
C10 | 0.44695 (14) | 0.83856 (8) | 0.56771 (12) | 0.0401 (3) | |
C11 | 0.29969 (14) | 0.83181 (8) | 0.51475 (13) | 0.0409 (3) | |
C12 | 0.24887 (16) | 0.77175 (9) | 0.42316 (15) | 0.0513 (4) | |
H12A | 0.1520 | 0.7662 | 0.3899 | 0.062* | |
C13 | 0.33820 (17) | 0.72090 (9) | 0.38116 (16) | 0.0557 (4) | |
H13A | 0.3023 | 0.6837 | 0.3167 | 0.067* | |
C14 | 0.48251 (17) | 0.72541 (9) | 0.43547 (16) | 0.0548 (4) | |
H14A | 0.5434 | 0.6901 | 0.4091 | 0.066* | |
C15 | 0.53528 (15) | 0.78209 (9) | 0.52820 (14) | 0.0488 (3) | |
H15A | 0.6318 | 0.7832 | 0.5659 | 0.059* | |
C16 | 0.53499 (13) | 1.01454 (8) | 0.78517 (12) | 0.0375 (3) | |
C17 | 0.51971 (15) | 1.09936 (8) | 0.79032 (14) | 0.0457 (3) | |
H17A | 0.4673 | 1.1269 | 0.7195 | 0.055* | |
C18 | 0.58070 (15) | 1.14386 (8) | 0.89838 (14) | 0.0478 (3) | |
H18A | 0.5683 | 1.2004 | 0.9000 | 0.057* | |
C19 | 0.65993 (13) | 1.10332 (8) | 1.00349 (12) | 0.0411 (3) | |
C20 | 0.68271 (15) | 1.01928 (8) | 0.99855 (13) | 0.0451 (3) | |
H20A | 0.7404 | 0.9925 | 1.0677 | 0.054* | |
C21 | 0.62032 (13) | 0.97595 (8) | 0.89211 (12) | 0.0409 (3) | |
H21A | 0.6348 | 0.9196 | 0.8906 | 0.049* | |
C22 | 0.68065 (19) | 1.22061 (10) | 1.13736 (17) | 0.0611 (4) | |
H22A | 0.7318 | 1.2384 | 1.2197 | 0.092* | |
H22B | 0.5813 | 1.2218 | 1.1310 | 0.092* | |
H22C | 0.7010 | 1.2566 | 1.0753 | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0516 (6) | 0.0463 (6) | 0.0779 (8) | −0.0086 (5) | 0.0334 (6) | −0.0049 (5) |
O2 | 0.0569 (6) | 0.0490 (6) | 0.0512 (6) | 0.0015 (5) | 0.0083 (5) | −0.0068 (5) |
N1 | 0.0382 (6) | 0.0435 (6) | 0.0450 (6) | 0.0038 (5) | 0.0145 (5) | −0.0012 (5) |
N2 | 0.0369 (6) | 0.0407 (6) | 0.0487 (6) | 0.0002 (4) | 0.0167 (5) | −0.0025 (5) |
C1 | 0.0419 (7) | 0.0408 (7) | 0.0450 (7) | 0.0035 (5) | 0.0169 (6) | 0.0073 (6) |
C2 | 0.0490 (8) | 0.0510 (8) | 0.0648 (9) | 0.0061 (6) | 0.0313 (7) | 0.0131 (7) |
C3 | 0.0616 (9) | 0.0541 (9) | 0.0633 (10) | 0.0170 (7) | 0.0360 (8) | 0.0089 (7) |
C4 | 0.0619 (9) | 0.0415 (7) | 0.0558 (9) | 0.0115 (6) | 0.0233 (7) | 0.0014 (6) |
C5 | 0.0430 (7) | 0.0392 (7) | 0.0494 (8) | 0.0038 (5) | 0.0155 (6) | 0.0042 (6) |
C6 | 0.0351 (6) | 0.0379 (6) | 0.0377 (6) | 0.0056 (5) | 0.0119 (5) | 0.0059 (5) |
C7 | 0.0339 (6) | 0.0393 (6) | 0.0367 (6) | 0.0026 (5) | 0.0105 (5) | 0.0040 (5) |
C8 | 0.0379 (6) | 0.0390 (6) | 0.0401 (7) | 0.0000 (5) | 0.0143 (5) | 0.0037 (5) |
C9 | 0.0329 (6) | 0.0404 (7) | 0.0426 (7) | −0.0004 (5) | 0.0159 (5) | 0.0038 (5) |
C10 | 0.0415 (7) | 0.0391 (6) | 0.0425 (7) | 0.0025 (5) | 0.0163 (5) | 0.0012 (5) |
C11 | 0.0409 (7) | 0.0379 (6) | 0.0478 (7) | 0.0011 (5) | 0.0183 (6) | −0.0006 (5) |
C12 | 0.0453 (8) | 0.0456 (7) | 0.0636 (9) | −0.0032 (6) | 0.0156 (7) | −0.0091 (7) |
C13 | 0.0622 (9) | 0.0455 (8) | 0.0635 (10) | −0.0025 (7) | 0.0235 (8) | −0.0146 (7) |
C14 | 0.0593 (9) | 0.0464 (8) | 0.0671 (10) | 0.0065 (7) | 0.0316 (8) | −0.0072 (7) |
C15 | 0.0438 (7) | 0.0482 (8) | 0.0584 (9) | 0.0067 (6) | 0.0204 (6) | −0.0013 (7) |
C16 | 0.0326 (6) | 0.0402 (6) | 0.0428 (7) | −0.0004 (5) | 0.0153 (5) | 0.0025 (5) |
C17 | 0.0450 (7) | 0.0404 (7) | 0.0491 (8) | 0.0013 (6) | 0.0074 (6) | 0.0064 (6) |
C18 | 0.0491 (8) | 0.0343 (6) | 0.0588 (9) | 0.0006 (6) | 0.0122 (6) | 0.0003 (6) |
C19 | 0.0354 (6) | 0.0454 (7) | 0.0443 (7) | −0.0029 (5) | 0.0138 (5) | −0.0025 (6) |
C20 | 0.0443 (7) | 0.0460 (7) | 0.0448 (7) | 0.0063 (6) | 0.0116 (6) | 0.0055 (6) |
C21 | 0.0412 (7) | 0.0382 (6) | 0.0457 (7) | 0.0041 (5) | 0.0153 (6) | 0.0028 (6) |
C22 | 0.0650 (10) | 0.0555 (9) | 0.0642 (10) | 0.0023 (8) | 0.0194 (8) | −0.0144 (8) |
C1—O1 | 1.3467 (17) | C12—C13 | 1.372 (2) |
C1—C2 | 1.3931 (19) | C12—H12A | 0.9300 |
C1—C6 | 1.4188 (17) | C13—C14 | 1.388 (2) |
C2—C3 | 1.374 (2) | C13—H13A | 0.9300 |
C2—H2A | 0.9300 | C14—C15 | 1.374 (2) |
C3—C4 | 1.388 (2) | C14—H14A | 0.9300 |
C3—H3A | 0.9300 | C15—H15A | 0.9300 |
C4—C5 | 1.3791 (19) | C16—C17 | 1.3928 (18) |
C4—H4A | 0.9300 | C16—C21 | 1.4028 (18) |
C5—C6 | 1.3970 (18) | C17—C18 | 1.388 (2) |
C5—H5A | 0.9300 | C17—H17A | 0.9300 |
C6—C7 | 1.4718 (16) | C18—C19 | 1.3821 (19) |
C7—N2 | 1.2924 (16) | C18—H18A | 0.9300 |
C7—C8 | 1.5101 (17) | C19—O2 | 1.3707 (16) |
C8—C9 | 1.5129 (18) | C19—C20 | 1.3907 (19) |
C8—H8A | 0.9700 | C20—C21 | 1.3684 (19) |
C8—H8B | 0.9700 | C20—H20A | 0.9300 |
C9—N1 | 1.2927 (16) | C21—H21A | 0.9300 |
C9—C16 | 1.4751 (18) | C22—O2 | 1.4135 (18) |
C10—N1 | 1.4001 (17) | C22—H22A | 0.9600 |
C10—C15 | 1.4095 (18) | C22—H22B | 0.9600 |
C10—C11 | 1.4146 (19) | C22—H22C | 0.9600 |
C11—C12 | 1.4003 (19) | O1—H1 | 0.92 (2) |
C11—N2 | 1.4053 (16) | ||
O1—C1—C2 | 117.71 (12) | C11—C12—H12A | 119.1 |
O1—C1—C6 | 122.46 (11) | C12—C13—C14 | 119.56 (14) |
C2—C1—C6 | 119.83 (13) | C12—C13—H13A | 120.2 |
C3—C2—C1 | 120.77 (13) | C14—C13—H13A | 120.2 |
C3—C2—H2A | 119.6 | C15—C14—C13 | 119.96 (13) |
C1—C2—H2A | 119.6 | C15—C14—H14A | 120.0 |
C2—C3—C4 | 120.44 (13) | C13—C14—H14A | 120.0 |
C2—C3—H3A | 119.8 | C14—C15—C10 | 121.72 (14) |
C4—C3—H3A | 119.8 | C14—C15—H15A | 119.1 |
C5—C4—C3 | 119.13 (14) | C10—C15—H15A | 119.1 |
C5—C4—H4A | 120.4 | C17—C16—C21 | 117.23 (12) |
C3—C4—H4A | 120.4 | C17—C16—C9 | 123.14 (12) |
C4—C5—C6 | 122.33 (13) | C21—C16—C9 | 119.63 (11) |
C4—C5—H5A | 118.8 | C18—C17—C16 | 121.75 (13) |
C6—C5—H5A | 118.8 | C18—C17—H17A | 119.1 |
C5—C6—C1 | 117.46 (11) | C16—C17—H17A | 119.1 |
C5—C6—C7 | 121.95 (11) | C19—C18—C17 | 119.37 (13) |
C1—C6—C7 | 120.54 (11) | C19—C18—H18A | 120.3 |
N2—C7—C6 | 118.71 (11) | C17—C18—H18A | 120.3 |
N2—C7—C8 | 119.07 (11) | O2—C19—C18 | 124.97 (12) |
C6—C7—C8 | 122.19 (11) | O2—C19—C20 | 115.11 (12) |
C7—C8—C9 | 105.54 (10) | C18—C19—C20 | 119.91 (13) |
C7—C8—H8A | 110.6 | C21—C20—C19 | 120.07 (13) |
C9—C8—H8A | 110.6 | C21—C20—H20A | 120.0 |
C7—C8—H8B | 110.6 | C19—C20—H20A | 120.0 |
C9—C8—H8B | 110.6 | C20—C21—C16 | 121.54 (12) |
H8A—C8—H8B | 108.8 | C20—C21—H21A | 119.2 |
N1—C9—C16 | 118.30 (12) | C16—C21—H21A | 119.2 |
N1—C9—C8 | 120.58 (12) | O2—C22—H22A | 109.5 |
C16—C9—C8 | 121.08 (11) | O2—C22—H22B | 109.5 |
N1—C10—C15 | 116.04 (12) | H22A—C22—H22B | 109.5 |
N1—C10—C11 | 125.82 (11) | O2—C22—H22C | 109.5 |
C15—C10—C11 | 117.85 (12) | H22A—C22—H22C | 109.5 |
C12—C11—N2 | 116.55 (12) | H22B—C22—H22C | 109.5 |
C12—C11—C10 | 118.96 (12) | C9—N1—C10 | 121.56 (11) |
N2—C11—C10 | 124.11 (12) | C7—N2—C11 | 122.42 (11) |
C13—C12—C11 | 121.76 (14) | C1—O1—H1 | 105.1 (13) |
C13—C12—H12A | 119.1 | C19—O2—C22 | 118.25 (12) |
O1—C1—C2—C3 | 178.92 (14) | C13—C14—C15—C10 | −2.2 (2) |
C6—C1—C2—C3 | −1.7 (2) | N1—C10—C15—C14 | 178.36 (13) |
C1—C2—C3—C4 | 1.3 (2) | C11—C10—C15—C14 | 4.2 (2) |
C2—C3—C4—C5 | 0.4 (2) | N1—C9—C16—C17 | 163.12 (12) |
C3—C4—C5—C6 | −1.8 (2) | C8—C9—C16—C17 | −19.07 (18) |
C4—C5—C6—C1 | 1.4 (2) | N1—C9—C16—C21 | −16.64 (17) |
C4—C5—C6—C7 | −176.28 (13) | C8—C9—C16—C21 | 161.17 (11) |
O1—C1—C6—C5 | 179.68 (13) | C21—C16—C17—C18 | −2.89 (19) |
C2—C1—C6—C5 | 0.36 (19) | C9—C16—C17—C18 | 177.35 (12) |
O1—C1—C6—C7 | −2.6 (2) | C16—C17—C18—C19 | 0.6 (2) |
C2—C1—C6—C7 | 178.09 (12) | C17—C18—C19—O2 | −177.80 (12) |
C5—C6—C7—N2 | 174.04 (12) | C17—C18—C19—C20 | 2.7 (2) |
C1—C6—C7—N2 | −3.59 (18) | O2—C19—C20—C21 | 176.78 (12) |
C5—C6—C7—C8 | −3.92 (19) | C18—C19—C20—C21 | −3.64 (19) |
C1—C6—C7—C8 | 178.45 (11) | C19—C20—C21—C16 | 1.3 (2) |
N2—C7—C8—C9 | −73.70 (14) | C17—C16—C21—C20 | 1.90 (19) |
C6—C7—C8—C9 | 104.25 (13) | C9—C16—C21—C20 | −178.32 (11) |
C7—C8—C9—N1 | 71.22 (14) | C16—C9—N1—C10 | 174.75 (11) |
C7—C8—C9—C16 | −106.54 (12) | C8—C9—N1—C10 | −3.08 (18) |
N1—C10—C11—C12 | −175.71 (13) | C15—C10—N1—C9 | 148.84 (12) |
C15—C10—C11—C12 | −2.14 (19) | C11—C10—N1—C9 | −37.48 (19) |
N1—C10—C11—N2 | −3.1 (2) | C6—C7—N2—C11 | −171.94 (11) |
C15—C10—C11—N2 | 170.50 (12) | C8—C7—N2—C11 | 6.09 (19) |
N2—C11—C12—C13 | −174.98 (13) | C12—C11—N2—C7 | −147.30 (13) |
C10—C11—C12—C13 | −1.8 (2) | C10—C11—N2—C7 | 39.91 (19) |
C11—C12—C13—C14 | 3.8 (2) | C18—C19—O2—C22 | 12.9 (2) |
C12—C13—C14—C15 | −1.8 (2) | C20—C19—O2—C22 | −167.51 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.92 (2) | 1.71 (2) | 2.5563 (17) | 151.5 (19) |
C14—H14A···O2i | 0.93 | 2.53 | 3.406 (2) | 156 |
Symmetry code: (i) −x+3/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C22H18N2O2 |
Mr | 342.38 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 9.8203 (7), 16.2920 (12), 11.0178 (8) |
β (°) | 105.203 (1) |
V (Å3) | 1701.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.33 × 0.30 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.897, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9963, 4220, 3022 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.116, 1.01 |
No. of reflections | 3928 |
No. of parameters | 239 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.18 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.92 (2) | 1.71 (2) | 2.5563 (17) | 151.5 (19) |
C14—H14A···O2i | 0.93 | 2.53 | 3.406 (2) | 156 |
Symmetry code: (i) −x+3/2, y−1/2, −z+3/2. |
The title compound belongs to an important class of the pharmacologically pre-eminent 1,5-benzodiazepines which are extensively studied for medicinal activities (Krapcho & Turk, 1966). In recent years, benzodiazepines have replaced barbiturates which were used once for the purpose of hypnotic effects, owing to their less toxic and less severe withdrawal effects (Gringauz, 1999). The importance of 1,5-benzodiazepines, in particular is evident from the pharmaceutical application of Globazam (Butcher & Hamor, 1985). The difficulties encountered in the cyclization of these seven-membered heterocycles limited their structural studies. In view of the importance of this class of compounds, the title compound, (I), has been synthesized and its crystal structure is reported here.
A perspective view of (I) is shown in Fig. 1. Bond lengths and angles can be regarded as normal (Cambridge Structural Database, Version 5.28, November 2006; Allen, 2002; Mogul, Version 1.1; Bruno et al., 2004). The seven membered diazepine ring has a fragment N1—C10—C11—N2, which is conjugated with the adjacent benzene ring. Like azepines, diazepines are not planar and generally adopt boat conformation (Armarego, 1977).
The rings A (C1—C6), B (C10—C15) and C (C16—C21) are, of course, planar and dihedral angles between them are A/B = 39.22 (2)°, A/C = 87.31 (3)° and B/C = 54.42 (3)°. The seven membered ring D (N1/N2/C7—C11) is non-planar and adopts nearly boat conformation.
In the crystal structure, intramolecular O—H···N and intermolecular C—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.