Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034824/hk2294sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034824/hk2294Isup2.hkl |
CCDC reference: 657837
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.002 Å
- R factor = 0.041
- wR factor = 0.120
- Data-to-parameter ratio = 17.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for C25 - C26 .. 6.72 su PLAT410_ALERT_2_C Short Intra H...H Contact H31B .. H44A .. 1.98 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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
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).
1-(2-hydroxyphenyl)-3-(2-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 as solvent (100 ml) to get the title compound (yield; 69%, m.p. 439–440 K). Yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of dichloromethane solution.
H2 and H3 (for OH groups) were located in difference syntheses and refined isotropically [O2—H2 = 0.95 (2) Å, Uiso(H) = 0.098 (7) Å2 and O3—H3 = 0.97 (2) Å, Uiso(H) = 0.093 (7) 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.
The asymmetric unit of the title compound, (I), contains two crystallographicaly independent molecules (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 rings have fragments N1—C12—C11—N2 and N3—C34—C33—N4, which are conjugated with the adjacent benzene rings. Like azepines, diazepines are not planar and generally adopt boat conformation (Armarego, 1977).
The rings A (C2—C7), B (C11—C16), C (C17—C22) and A' (C24—C29), B' (C33—C38), C' (C39—C44) are, of course, planar and dihedral angles between them are A/B = 88.79 (3)°, A/C = 68.16 (3)°, B/C = 37.51 (2)° and A'/B' = 82.43 (3)°, A'/C' = 78.52 (2)°, B'/C' = 28.65 (3)°. The seven membered rings D (N1/N2/C8—C12) and D' (N3/N4/C30—C34) are not planar and adopt nearly boat conformations.
The intramolecular O—H···N and C—H···O hydrogen bonds (Table 1) 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.
Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. The formation of the title compound. |
C22H18N2O2 | F(000) = 1440 |
Mr = 342.38 | Dx = 1.301 Mg m−3 |
Monoclinic, P21/c | Melting point: 439(1) K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.3963 (6) Å | Cell parameters from 2164 reflections |
b = 19.0230 (8) Å | θ = 2.1–27.5° |
c = 12.7651 (6) Å | µ = 0.08 mm−1 |
β = 91.305 (1)° | T = 298 K |
V = 3495.0 (3) Å3 | Block, yellow |
Z = 8 | 0.32 × 0.28 × 0.26 mm |
Bruker SMART CCD area-detector diffractometer | 8356 independent reflections |
Radiation source: fine-focus sealed tube | 5640 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω and φ scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→19 |
Tmin = 0.924, Tmax = 0.977 | k = −21→24 |
21496 measured reflections | l = −9→16 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0559P)2 + 0.4964P] where P = (Fo2 + 2Fc2)/3 |
8356 reflections | (Δ/σ)max < 0.001 |
477 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C22H18N2O2 | V = 3495.0 (3) Å3 |
Mr = 342.38 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.3963 (6) Å | µ = 0.08 mm−1 |
b = 19.0230 (8) Å | T = 298 K |
c = 12.7651 (6) Å | 0.32 × 0.28 × 0.26 mm |
β = 91.305 (1)° |
Bruker SMART CCD area-detector diffractometer | 8356 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5640 reflections with I > 2σ(I) |
Tmin = 0.924, Tmax = 0.977 | Rint = 0.021 |
21496 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.17 e Å−3 |
8356 reflections | Δρmin = −0.19 e Å−3 |
477 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 | −0.03830 (7) | 0.34099 (6) | 0.70821 (9) | 0.0648 (3) | |
O2 | 0.41848 (8) | 0.44392 (7) | 0.86472 (11) | 0.0692 (3) | |
H2 | 0.4019 (15) | 0.4151 (11) | 0.8062 (18) | 0.098 (7)* | |
O3 | 0.02097 (8) | 0.52556 (7) | 0.61006 (10) | 0.0640 (3) | |
H3 | 0.0736 (15) | 0.5167 (11) | 0.5662 (16) | 0.093 (7)* | |
O4 | 0.43830 (8) | 0.65133 (7) | 0.77294 (10) | 0.0718 (3) | |
N1 | 0.19680 (7) | 0.25092 (6) | 0.69141 (9) | 0.0428 (3) | |
N2 | 0.32563 (8) | 0.37444 (6) | 0.72447 (9) | 0.0443 (3) | |
N3 | 0.35974 (8) | 0.60184 (6) | 0.48265 (10) | 0.0474 (3) | |
N4 | 0.18993 (7) | 0.52098 (5) | 0.54442 (9) | 0.0420 (3) | |
C1 | −0.12668 (13) | 0.37289 (13) | 0.69734 (18) | 0.0980 (7) | |
H1A | −0.1286 | 0.4016 | 0.6355 | 0.147* | |
H1B | −0.1379 | 0.4016 | 0.7576 | 0.147* | |
H1C | −0.1736 | 0.3371 | 0.6916 | 0.147* | |
C2 | −0.02081 (9) | 0.29743 (7) | 0.79152 (11) | 0.0461 (3) | |
C3 | −0.08829 (10) | 0.27298 (9) | 0.85813 (13) | 0.0585 (4) | |
H3A | −0.1497 | 0.2874 | 0.8489 | 0.070* | |
C4 | −0.06431 (12) | 0.22745 (9) | 0.93786 (13) | 0.0616 (4) | |
H4A | −0.1099 | 0.2115 | 0.9825 | 0.074* | |
C5 | 0.02575 (12) | 0.20512 (8) | 0.95271 (12) | 0.0578 (4) | |
H5A | 0.0414 | 0.1747 | 1.0074 | 0.069* | |
C6 | 0.09268 (10) | 0.22841 (7) | 0.88528 (11) | 0.0477 (3) | |
H6A | 0.1535 | 0.2127 | 0.8943 | 0.057* | |
C7 | 0.07119 (9) | 0.27470 (6) | 0.80432 (10) | 0.0398 (3) | |
C8 | 0.14392 (8) | 0.29780 (7) | 0.73142 (10) | 0.0396 (3) | |
C9 | 0.15782 (9) | 0.37523 (7) | 0.71038 (11) | 0.0433 (3) | |
H9A | 0.1612 | 0.3841 | 0.6357 | 0.052* | |
H9B | 0.1071 | 0.4025 | 0.7382 | 0.052* | |
C10 | 0.24804 (9) | 0.39396 (6) | 0.76502 (11) | 0.0417 (3) | |
C11 | 0.32698 (9) | 0.32981 (7) | 0.63671 (10) | 0.0419 (3) | |
C12 | 0.26806 (8) | 0.27080 (7) | 0.62375 (10) | 0.0410 (3) | |
C13 | 0.28398 (10) | 0.22507 (8) | 0.53994 (12) | 0.0508 (3) | |
H13A | 0.2489 | 0.1842 | 0.5336 | 0.061* | |
C14 | 0.35000 (10) | 0.23924 (9) | 0.46712 (12) | 0.0578 (4) | |
H14A | 0.3571 | 0.2096 | 0.4100 | 0.069* | |
C15 | 0.40615 (10) | 0.29817 (9) | 0.47921 (12) | 0.0574 (4) | |
H15A | 0.4503 | 0.3084 | 0.4294 | 0.069* | |
C16 | 0.39664 (9) | 0.34117 (8) | 0.56410 (12) | 0.0503 (3) | |
H16A | 0.4373 | 0.3787 | 0.5737 | 0.060* | |
C17 | 0.25098 (10) | 0.43259 (7) | 0.86479 (11) | 0.0462 (3) | |
C18 | 0.33617 (11) | 0.45524 (8) | 0.91028 (13) | 0.0543 (4) | |
C19 | 0.33710 (14) | 0.49073 (9) | 1.00579 (14) | 0.0688 (5) | |
H19A | 0.3932 | 0.5064 | 1.0349 | 0.083* | |
C20 | 0.25624 (16) | 0.50274 (9) | 1.05710 (15) | 0.0743 (5) | |
H20A | 0.2580 | 0.5261 | 1.1211 | 0.089* | |
C21 | 0.17215 (15) | 0.48061 (9) | 1.01487 (14) | 0.0705 (5) | |
H21A | 0.1174 | 0.4888 | 1.0502 | 0.085* | |
C22 | 0.16991 (12) | 0.44620 (8) | 0.91974 (13) | 0.0578 (4) | |
H22A | 0.1130 | 0.4317 | 0.8914 | 0.069* | |
C23 | 0.49355 (14) | 0.66690 (13) | 0.86386 (16) | 0.0896 (7) | |
H23A | 0.5130 | 0.6239 | 0.8969 | 0.134* | |
H23B | 0.4577 | 0.6940 | 0.9118 | 0.134* | |
H23C | 0.5472 | 0.6933 | 0.8441 | 0.134* | |
C24 | 0.40327 (10) | 0.70542 (8) | 0.71426 (14) | 0.0559 (4) | |
C25 | 0.40935 (12) | 0.77638 (10) | 0.74391 (17) | 0.0764 (6) | |
H25A | 0.4365 | 0.7888 | 0.8081 | 0.092* | |
C26 | 0.37478 (14) | 0.82749 (10) | 0.6770 (2) | 0.0852 (6) | |
H26A | 0.3787 | 0.8745 | 0.6968 | 0.102* | |
C27 | 0.33500 (13) | 0.81056 (9) | 0.58258 (18) | 0.0753 (5) | |
H27A | 0.3124 | 0.8457 | 0.5382 | 0.090* | |
C28 | 0.32851 (10) | 0.74105 (8) | 0.55344 (14) | 0.0571 (4) | |
H28A | 0.3012 | 0.7297 | 0.4889 | 0.068* | |
C29 | 0.36178 (9) | 0.68726 (7) | 0.61803 (12) | 0.0471 (3) | |
C30 | 0.35171 (9) | 0.61351 (7) | 0.58128 (11) | 0.0425 (3) | |
C31 | 0.32200 (9) | 0.55565 (7) | 0.65384 (11) | 0.0432 (3) | |
H31A | 0.3539 | 0.5121 | 0.6385 | 0.052* | |
H31B | 0.3345 | 0.5682 | 0.7264 | 0.052* | |
C32 | 0.21917 (9) | 0.54897 (6) | 0.63193 (10) | 0.0392 (3) | |
C33 | 0.25150 (9) | 0.49995 (7) | 0.46692 (10) | 0.0413 (3) | |
C34 | 0.33334 (9) | 0.53628 (7) | 0.44029 (11) | 0.0441 (3) | |
C35 | 0.38566 (11) | 0.51050 (8) | 0.35770 (12) | 0.0569 (4) | |
H35A | 0.4393 | 0.5342 | 0.3390 | 0.068* | |
C36 | 0.35971 (12) | 0.45104 (9) | 0.30367 (13) | 0.0637 (4) | |
H36A | 0.3974 | 0.4335 | 0.2516 | 0.076* | |
C37 | 0.27742 (12) | 0.41713 (8) | 0.32667 (13) | 0.0606 (4) | |
H37A | 0.2588 | 0.3777 | 0.2887 | 0.073* | |
C38 | 0.22379 (11) | 0.44208 (7) | 0.40568 (12) | 0.0519 (4) | |
H38A | 0.1676 | 0.4201 | 0.4191 | 0.062* | |
C39 | 0.15199 (9) | 0.57447 (7) | 0.70743 (11) | 0.0422 (3) | |
C40 | 0.05604 (10) | 0.56137 (8) | 0.69350 (12) | 0.0494 (3) | |
C41 | −0.00595 (11) | 0.58597 (10) | 0.76695 (14) | 0.0652 (4) | |
H41A | −0.0689 | 0.5761 | 0.7585 | 0.078* | |
C42 | 0.02448 (13) | 0.62447 (10) | 0.85140 (14) | 0.0698 (5) | |
H42A | −0.0180 | 0.6414 | 0.8990 | 0.084* | |
C43 | 0.11783 (13) | 0.63835 (9) | 0.86631 (14) | 0.0663 (4) | |
H43A | 0.1384 | 0.6645 | 0.9239 | 0.080* | |
C44 | 0.18026 (11) | 0.61337 (8) | 0.79572 (12) | 0.0538 (4) | |
H44A | 0.2432 | 0.6225 | 0.8068 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0438 (5) | 0.0878 (8) | 0.0628 (7) | 0.0181 (5) | 0.0026 (5) | 0.0208 (6) |
O2 | 0.0564 (7) | 0.0758 (8) | 0.0750 (8) | −0.0069 (6) | −0.0080 (6) | −0.0162 (7) |
O3 | 0.0425 (6) | 0.0874 (8) | 0.0620 (7) | −0.0059 (5) | −0.0029 (5) | −0.0114 (6) |
O4 | 0.0652 (7) | 0.0771 (8) | 0.0722 (8) | −0.0082 (6) | −0.0198 (6) | −0.0206 (6) |
N1 | 0.0391 (6) | 0.0400 (6) | 0.0493 (7) | −0.0002 (4) | 0.0022 (5) | 0.0001 (5) |
N2 | 0.0435 (6) | 0.0420 (6) | 0.0474 (7) | −0.0035 (5) | −0.0002 (5) | 0.0011 (5) |
N3 | 0.0473 (6) | 0.0432 (6) | 0.0521 (7) | −0.0064 (5) | 0.0072 (5) | −0.0041 (5) |
N4 | 0.0427 (6) | 0.0381 (6) | 0.0452 (6) | −0.0036 (4) | −0.0023 (5) | −0.0021 (5) |
C1 | 0.0623 (11) | 0.1324 (19) | 0.0994 (16) | 0.0450 (12) | 0.0042 (11) | 0.0306 (14) |
C2 | 0.0424 (7) | 0.0522 (8) | 0.0437 (8) | 0.0031 (6) | 0.0032 (6) | −0.0023 (6) |
C3 | 0.0435 (8) | 0.0716 (10) | 0.0607 (10) | 0.0048 (7) | 0.0122 (7) | −0.0038 (8) |
C4 | 0.0651 (10) | 0.0660 (10) | 0.0547 (9) | −0.0082 (8) | 0.0222 (8) | −0.0035 (8) |
C5 | 0.0714 (10) | 0.0551 (9) | 0.0472 (9) | −0.0060 (7) | 0.0047 (8) | 0.0063 (7) |
C6 | 0.0480 (7) | 0.0443 (7) | 0.0506 (8) | −0.0019 (6) | −0.0031 (6) | 0.0007 (6) |
C7 | 0.0396 (6) | 0.0369 (6) | 0.0429 (7) | −0.0017 (5) | 0.0002 (5) | −0.0038 (6) |
C8 | 0.0354 (6) | 0.0390 (6) | 0.0441 (7) | 0.0000 (5) | −0.0037 (5) | 0.0008 (6) |
C9 | 0.0417 (7) | 0.0383 (7) | 0.0497 (8) | 0.0034 (5) | −0.0006 (6) | 0.0040 (6) |
C10 | 0.0467 (7) | 0.0314 (6) | 0.0469 (8) | −0.0015 (5) | 0.0003 (6) | 0.0063 (6) |
C11 | 0.0370 (6) | 0.0454 (7) | 0.0432 (7) | 0.0030 (5) | −0.0022 (6) | 0.0035 (6) |
C12 | 0.0362 (6) | 0.0434 (7) | 0.0432 (7) | 0.0042 (5) | −0.0006 (5) | 0.0010 (6) |
C13 | 0.0413 (7) | 0.0551 (8) | 0.0557 (9) | 0.0036 (6) | −0.0019 (6) | −0.0099 (7) |
C14 | 0.0463 (8) | 0.0774 (11) | 0.0497 (9) | 0.0111 (7) | 0.0002 (7) | −0.0134 (8) |
C15 | 0.0419 (8) | 0.0804 (11) | 0.0503 (9) | 0.0075 (7) | 0.0088 (7) | 0.0053 (8) |
C16 | 0.0377 (7) | 0.0576 (9) | 0.0556 (9) | −0.0012 (6) | 0.0024 (6) | 0.0067 (7) |
C17 | 0.0566 (8) | 0.0346 (7) | 0.0475 (8) | 0.0002 (6) | 0.0013 (6) | 0.0043 (6) |
C18 | 0.0629 (9) | 0.0440 (8) | 0.0557 (9) | −0.0010 (7) | −0.0057 (8) | −0.0008 (7) |
C19 | 0.0870 (13) | 0.0557 (10) | 0.0631 (11) | −0.0022 (9) | −0.0127 (10) | −0.0091 (8) |
C20 | 0.1116 (16) | 0.0561 (10) | 0.0551 (10) | 0.0029 (10) | 0.0012 (11) | −0.0098 (8) |
C21 | 0.0915 (13) | 0.0573 (10) | 0.0635 (11) | 0.0058 (9) | 0.0200 (10) | −0.0020 (8) |
C22 | 0.0659 (10) | 0.0474 (8) | 0.0605 (10) | 0.0000 (7) | 0.0090 (8) | −0.0006 (7) |
C23 | 0.0719 (12) | 0.1237 (18) | 0.0724 (13) | 0.0040 (11) | −0.0153 (10) | −0.0411 (13) |
C24 | 0.0391 (7) | 0.0593 (9) | 0.0694 (10) | −0.0088 (6) | 0.0057 (7) | −0.0184 (8) |
C25 | 0.0629 (10) | 0.0737 (12) | 0.0928 (14) | −0.0171 (9) | 0.0091 (10) | −0.0399 (11) |
C26 | 0.0800 (13) | 0.0479 (10) | 0.1281 (19) | −0.0087 (9) | 0.0134 (13) | −0.0257 (12) |
C27 | 0.0713 (11) | 0.0462 (9) | 0.1090 (16) | −0.0036 (8) | 0.0178 (11) | −0.0067 (10) |
C28 | 0.0502 (8) | 0.0459 (8) | 0.0757 (11) | −0.0070 (6) | 0.0134 (8) | −0.0019 (8) |
C29 | 0.0354 (6) | 0.0460 (7) | 0.0604 (9) | −0.0094 (5) | 0.0117 (6) | −0.0106 (7) |
C30 | 0.0338 (6) | 0.0433 (7) | 0.0505 (8) | −0.0050 (5) | 0.0030 (6) | −0.0057 (6) |
C31 | 0.0431 (7) | 0.0414 (7) | 0.0450 (8) | −0.0022 (5) | −0.0051 (6) | −0.0006 (6) |
C32 | 0.0432 (7) | 0.0312 (6) | 0.0429 (7) | −0.0039 (5) | −0.0019 (6) | 0.0035 (5) |
C33 | 0.0445 (7) | 0.0372 (6) | 0.0418 (7) | 0.0027 (5) | −0.0055 (6) | −0.0009 (6) |
C34 | 0.0486 (7) | 0.0407 (7) | 0.0428 (7) | 0.0013 (6) | −0.0004 (6) | −0.0021 (6) |
C35 | 0.0570 (9) | 0.0615 (9) | 0.0523 (9) | 0.0014 (7) | 0.0078 (7) | −0.0054 (8) |
C36 | 0.0746 (11) | 0.0649 (10) | 0.0517 (9) | 0.0137 (8) | 0.0055 (8) | −0.0133 (8) |
C37 | 0.0765 (11) | 0.0498 (9) | 0.0551 (10) | 0.0038 (8) | −0.0088 (8) | −0.0147 (7) |
C38 | 0.0569 (8) | 0.0454 (8) | 0.0529 (9) | −0.0017 (6) | −0.0088 (7) | −0.0060 (7) |
C39 | 0.0472 (7) | 0.0376 (7) | 0.0416 (7) | −0.0015 (5) | 0.0015 (6) | 0.0058 (6) |
C40 | 0.0463 (8) | 0.0545 (8) | 0.0473 (8) | 0.0024 (6) | −0.0006 (6) | 0.0076 (7) |
C41 | 0.0482 (8) | 0.0863 (12) | 0.0614 (11) | 0.0079 (8) | 0.0052 (8) | 0.0049 (9) |
C42 | 0.0720 (11) | 0.0819 (12) | 0.0561 (10) | 0.0181 (9) | 0.0151 (9) | 0.0007 (9) |
C43 | 0.0770 (12) | 0.0682 (10) | 0.0539 (10) | 0.0026 (9) | 0.0079 (8) | −0.0107 (8) |
C44 | 0.0574 (9) | 0.0540 (9) | 0.0503 (9) | −0.0043 (7) | 0.0037 (7) | −0.0048 (7) |
C1—O1 | 1.4135 (19) | C23—H23A | 0.9600 |
C1—H1A | 0.9600 | C23—H23B | 0.9600 |
C1—H1B | 0.9600 | C23—H23C | 0.9600 |
C1—H1C | 0.9600 | C24—O4 | 1.363 (2) |
C2—O1 | 1.3670 (17) | C24—C29 | 1.397 (2) |
C2—C3 | 1.386 (2) | C24—C25 | 1.404 (2) |
C2—C7 | 1.3993 (18) | C25—C26 | 1.380 (3) |
C3—C4 | 1.375 (2) | C25—H25A | 0.9300 |
C3—H3A | 0.9300 | C26—C27 | 1.361 (3) |
C4—C5 | 1.373 (2) | C26—H26A | 0.9300 |
C4—H4A | 0.9300 | C27—C28 | 1.376 (2) |
C5—C6 | 1.380 (2) | C27—H27A | 0.9300 |
C5—H5A | 0.9300 | C28—C29 | 1.392 (2) |
C6—C7 | 1.3873 (19) | C28—H28A | 0.9300 |
C6—H6A | 0.9300 | C29—C30 | 1.4852 (18) |
C7—C8 | 1.4831 (18) | C30—N3 | 1.2863 (17) |
C8—N1 | 1.2859 (16) | C30—C31 | 1.5068 (19) |
C8—C9 | 1.5114 (18) | C31—C32 | 1.5057 (18) |
C9—C10 | 1.5030 (18) | C31—H31A | 0.9700 |
C9—H9A | 0.9700 | C31—H31B | 0.9700 |
C9—H9B | 0.9700 | C32—N4 | 1.2989 (16) |
C10—N2 | 1.2961 (17) | C32—C39 | 1.4636 (19) |
C10—C17 | 1.470 (2) | C33—N4 | 1.4015 (17) |
C11—C16 | 1.3978 (19) | C33—C38 | 1.4028 (19) |
C11—N2 | 1.4061 (17) | C33—C34 | 1.4140 (19) |
C11—C12 | 1.4144 (18) | C34—C35 | 1.398 (2) |
C12—C13 | 1.4019 (19) | C34—N3 | 1.4082 (17) |
C12—N1 | 1.4077 (17) | C35—C36 | 1.372 (2) |
C13—C14 | 1.371 (2) | C35—H35A | 0.9300 |
C13—H13A | 0.9300 | C36—C37 | 1.386 (2) |
C14—C15 | 1.389 (2) | C36—H36A | 0.9300 |
C14—H14A | 0.9300 | C37—C38 | 1.369 (2) |
C15—C16 | 1.367 (2) | C37—H37A | 0.9300 |
C15—H15A | 0.9300 | C38—H38A | 0.9300 |
C16—H16A | 0.9300 | C39—C44 | 1.401 (2) |
C17—C22 | 1.399 (2) | C39—C40 | 1.4108 (19) |
C17—C18 | 1.412 (2) | C40—O3 | 1.3524 (18) |
C18—O2 | 1.349 (2) | C40—C41 | 1.390 (2) |
C18—C19 | 1.393 (2) | C41—C42 | 1.367 (3) |
C19—C20 | 1.368 (3) | C41—H41A | 0.9300 |
C19—H19A | 0.9300 | C42—C43 | 1.379 (3) |
C20—C21 | 1.380 (3) | C42—H42A | 0.9300 |
C20—H20A | 0.9300 | C43—C44 | 1.372 (2) |
C21—C22 | 1.379 (2) | C43—H43A | 0.9300 |
C21—H21A | 0.9300 | C44—H44A | 0.9300 |
C22—H22A | 0.9300 | O2—H2 | 0.95 (2) |
C23—O4 | 1.423 (2) | O3—H3 | 0.97 (2) |
O1—C1—H1A | 109.5 | H23A—C23—H23C | 109.5 |
O1—C1—H1B | 109.5 | H23B—C23—H23C | 109.5 |
H1A—C1—H1B | 109.5 | O4—C24—C29 | 116.23 (13) |
O1—C1—H1C | 109.5 | O4—C24—C25 | 123.90 (16) |
H1A—C1—H1C | 109.5 | C29—C24—C25 | 119.84 (17) |
H1B—C1—H1C | 109.5 | C26—C25—C24 | 119.43 (18) |
O1—C2—C3 | 124.15 (13) | C26—C25—H25A | 120.3 |
O1—C2—C7 | 115.80 (12) | C24—C25—H25A | 120.3 |
C3—C2—C7 | 119.97 (14) | C27—C26—C25 | 121.33 (17) |
C4—C3—C2 | 119.87 (14) | C27—C26—H26A | 119.3 |
C4—C3—H3A | 120.1 | C25—C26—H26A | 119.3 |
C2—C3—H3A | 120.1 | C26—C27—C28 | 119.42 (19) |
C5—C4—C3 | 121.16 (15) | C26—C27—H27A | 120.3 |
C5—C4—H4A | 119.4 | C28—C27—H27A | 120.3 |
C3—C4—H4A | 119.4 | C27—C28—C29 | 121.72 (17) |
C4—C5—C6 | 119.02 (15) | C27—C28—H28A | 119.1 |
C4—C5—H5A | 120.5 | C29—C28—H28A | 119.1 |
C6—C5—H5A | 120.5 | C28—C29—C24 | 118.25 (14) |
C5—C6—C7 | 121.43 (14) | C28—C29—C30 | 118.52 (13) |
C5—C6—H6A | 119.3 | C24—C29—C30 | 123.23 (14) |
C7—C6—H6A | 119.3 | N3—C30—C29 | 117.51 (13) |
C6—C7—C2 | 118.53 (13) | N3—C30—C31 | 120.58 (12) |
C6—C7—C8 | 120.45 (12) | C29—C30—C31 | 121.52 (12) |
C2—C7—C8 | 121.00 (12) | C32—C31—C30 | 103.84 (10) |
N1—C8—C7 | 118.45 (11) | C32—C31—H31A | 111.0 |
N1—C8—C9 | 121.56 (12) | C30—C31—H31A | 111.0 |
C7—C8—C9 | 119.90 (11) | C32—C31—H31B | 111.0 |
C10—C9—C8 | 105.37 (10) | C30—C31—H31B | 111.0 |
C10—C9—H9A | 110.7 | H31A—C31—H31B | 109.0 |
C8—C9—H9A | 110.7 | N4—C32—C39 | 119.75 (11) |
C10—C9—H9B | 110.7 | N4—C32—C31 | 119.50 (12) |
C8—C9—H9B | 110.7 | C39—C32—C31 | 120.75 (12) |
H9A—C9—H9B | 108.8 | N4—C33—C38 | 116.16 (12) |
N2—C10—C17 | 118.76 (12) | N4—C33—C34 | 125.03 (12) |
N2—C10—C9 | 119.36 (12) | C38—C33—C34 | 118.52 (13) |
C17—C10—C9 | 121.87 (12) | C35—C34—N3 | 117.05 (13) |
C16—C11—N2 | 117.27 (12) | C35—C34—C33 | 118.42 (13) |
C16—C11—C12 | 118.85 (13) | N3—C34—C33 | 124.03 (12) |
N2—C11—C12 | 123.59 (12) | C36—C35—C34 | 121.53 (15) |
C13—C12—N1 | 115.82 (12) | C36—C35—H35A | 119.2 |
C13—C12—C11 | 118.28 (13) | C34—C35—H35A | 119.2 |
N1—C12—C11 | 125.80 (12) | C35—C36—C37 | 120.09 (15) |
C14—C13—C12 | 121.55 (14) | C35—C36—H36A | 120.0 |
C14—C13—H13A | 119.2 | C37—C36—H36A | 120.0 |
C12—C13—H13A | 119.2 | C38—C37—C36 | 119.59 (14) |
C13—C14—C15 | 119.61 (14) | C38—C37—H37A | 120.2 |
C13—C14—H14A | 120.2 | C36—C37—H37A | 120.2 |
C15—C14—H14A | 120.2 | C37—C38—C33 | 121.64 (15) |
C16—C15—C14 | 120.16 (14) | C37—C38—H38A | 119.2 |
C16—C15—H15A | 119.9 | C33—C38—H38A | 119.2 |
C14—C15—H15A | 119.9 | C44—C39—C40 | 117.41 (13) |
C15—C16—C11 | 121.30 (14) | C44—C39—C32 | 121.37 (12) |
C15—C16—H16A | 119.4 | C40—C39—C32 | 121.22 (12) |
C11—C16—H16A | 119.4 | O3—C40—C41 | 117.84 (14) |
C22—C17—C18 | 117.63 (14) | O3—C40—C39 | 122.34 (13) |
C22—C17—C10 | 121.25 (13) | C41—C40—C39 | 119.82 (14) |
C18—C17—C10 | 121.08 (13) | C42—C41—C40 | 120.87 (16) |
O2—C18—C19 | 117.61 (15) | C42—C41—H41A | 119.6 |
O2—C18—C17 | 122.49 (14) | C40—C41—H41A | 119.6 |
C19—C18—C17 | 119.90 (16) | C41—C42—C43 | 120.35 (16) |
C20—C19—C18 | 120.56 (17) | C41—C42—H42A | 119.8 |
C20—C19—H19A | 119.7 | C43—C42—H42A | 119.8 |
C18—C19—H19A | 119.7 | C44—C43—C42 | 119.61 (16) |
C19—C20—C21 | 120.72 (17) | C44—C43—H43A | 120.2 |
C19—C20—H20A | 119.6 | C42—C43—H43A | 120.2 |
C21—C20—H20A | 119.6 | C43—C44—C39 | 121.92 (15) |
C22—C21—C20 | 119.43 (18) | C43—C44—H44A | 119.0 |
C22—C21—H21A | 120.3 | C39—C44—H44A | 119.0 |
C20—C21—H21A | 120.3 | C8—N1—C12 | 120.24 (11) |
C21—C22—C17 | 121.74 (16) | C10—N2—C11 | 121.26 (11) |
C21—C22—H22A | 119.1 | C30—N3—C34 | 119.96 (12) |
C17—C22—H22A | 119.1 | C32—N4—C33 | 121.76 (11) |
O4—C23—H23A | 109.5 | C2—O1—C1 | 119.08 (13) |
O4—C23—H23B | 109.5 | C18—O2—H2 | 102.9 (13) |
H23A—C23—H23B | 109.5 | C40—O3—H3 | 105.1 (12) |
O4—C23—H23C | 109.5 | C24—O4—C23 | 118.95 (15) |
O1—C2—C3—C4 | 177.88 (14) | C25—C24—C29—C30 | −179.36 (14) |
C7—C2—C3—C4 | 1.2 (2) | C28—C29—C30—N3 | 35.31 (18) |
C2—C3—C4—C5 | −0.4 (2) | C24—C29—C30—N3 | −144.51 (14) |
C3—C4—C5—C6 | −0.8 (2) | C28—C29—C30—C31 | −137.55 (13) |
C4—C5—C6—C7 | 1.1 (2) | C24—C29—C30—C31 | 42.63 (19) |
C5—C6—C7—C2 | −0.4 (2) | N3—C30—C31—C32 | −75.57 (15) |
C5—C6—C7—C8 | −178.67 (13) | C29—C30—C31—C32 | 97.07 (14) |
O1—C2—C7—C6 | −177.77 (12) | C30—C31—C32—N4 | 72.36 (14) |
C3—C2—C7—C6 | −0.8 (2) | C30—C31—C32—C39 | −106.82 (13) |
O1—C2—C7—C8 | 0.54 (19) | N4—C33—C34—C35 | −177.08 (13) |
C3—C2—C7—C8 | 177.48 (13) | C38—C33—C34—C35 | −3.49 (19) |
C6—C7—C8—N1 | 47.73 (17) | N4—C33—C34—N3 | −5.4 (2) |
C2—C7—C8—N1 | −130.55 (14) | C38—C33—C34—N3 | 168.15 (13) |
C6—C7—C8—C9 | −128.98 (13) | N3—C34—C35—C36 | −172.87 (14) |
C2—C7—C8—C9 | 52.74 (17) | C33—C34—C35—C36 | −0.7 (2) |
N1—C8—C9—C10 | −68.35 (16) | C34—C35—C36—C37 | 3.5 (2) |
C7—C8—C9—C10 | 108.26 (13) | C35—C36—C37—C38 | −2.0 (2) |
C8—C9—C10—N2 | 74.87 (15) | C36—C37—C38—C33 | −2.3 (2) |
C8—C9—C10—C17 | −103.74 (13) | N4—C33—C38—C37 | 179.17 (13) |
C16—C11—C12—C13 | 1.80 (18) | C34—C33—C38—C37 | 5.0 (2) |
N2—C11—C12—C13 | −171.80 (12) | N4—C32—C39—C44 | −171.24 (12) |
C16—C11—C12—N1 | 177.98 (12) | C31—C32—C39—C44 | 7.94 (19) |
N2—C11—C12—N1 | 4.4 (2) | N4—C32—C39—C40 | 8.15 (19) |
N1—C12—C13—C14 | 178.51 (13) | C31—C32—C39—C40 | −172.67 (12) |
C11—C12—C13—C14 | −4.9 (2) | C44—C39—C40—O3 | 178.72 (13) |
C12—C13—C14—C15 | 3.6 (2) | C32—C39—C40—O3 | −0.7 (2) |
C13—C14—C15—C16 | 1.0 (2) | C44—C39—C40—C41 | −1.0 (2) |
C14—C15—C16—C11 | −4.2 (2) | C32—C39—C40—C41 | 179.63 (13) |
N2—C11—C16—C15 | 176.69 (13) | O3—C40—C41—C42 | −177.90 (15) |
C12—C11—C16—C15 | 2.7 (2) | C39—C40—C41—C42 | 1.8 (2) |
N2—C10—C17—C22 | −170.77 (13) | C40—C41—C42—C43 | −1.4 (3) |
C9—C10—C17—C22 | 7.85 (19) | C41—C42—C43—C44 | 0.1 (3) |
N2—C10—C17—C18 | 7.11 (19) | C42—C43—C44—C39 | 0.7 (3) |
C9—C10—C17—C18 | −174.27 (12) | C40—C39—C44—C43 | −0.3 (2) |
C22—C17—C18—O2 | 179.03 (14) | C32—C39—C44—C43 | 179.13 (14) |
C10—C17—C18—O2 | 1.1 (2) | C7—C8—N1—C12 | −178.55 (11) |
C22—C17—C18—C19 | −1.0 (2) | C9—C8—N1—C12 | −1.89 (18) |
C10—C17—C18—C19 | −178.93 (14) | C13—C12—N1—C8 | −143.21 (13) |
O2—C18—C19—C20 | −178.76 (16) | C11—C12—N1—C8 | 40.53 (19) |
C17—C18—C19—C20 | 1.3 (2) | C17—C10—N2—C11 | 171.77 (11) |
C18—C19—C20—C21 | −0.7 (3) | C9—C10—N2—C11 | −6.89 (18) |
C19—C20—C21—C22 | −0.2 (3) | C16—C11—N2—C10 | 144.76 (13) |
C20—C21—C22—C17 | 0.4 (3) | C12—C11—N2—C10 | −41.54 (18) |
C18—C17—C22—C21 | 0.2 (2) | C29—C30—N3—C34 | −167.67 (11) |
C10—C17—C22—C21 | 178.10 (14) | C31—C30—N3—C34 | 5.27 (19) |
O4—C24—C25—C26 | 177.51 (16) | C35—C34—N3—C30 | −145.17 (14) |
C29—C24—C25—C26 | −0.5 (2) | C33—C34—N3—C30 | 43.09 (19) |
C24—C25—C26—C27 | −0.2 (3) | C39—C32—N4—C33 | 175.85 (11) |
C25—C26—C27—C28 | 0.5 (3) | C31—C32—N4—C33 | −3.34 (18) |
C26—C27—C28—C29 | −0.1 (3) | C38—C33—N4—C32 | 148.59 (12) |
C27—C28—C29—C24 | −0.5 (2) | C34—C33—N4—C32 | −37.68 (19) |
C27—C28—C29—C30 | 179.65 (14) | C3—C2—O1—C1 | 10.8 (2) |
O4—C24—C29—C28 | −177.34 (13) | C7—C2—O1—C1 | −172.45 (16) |
C25—C24—C29—C28 | 0.8 (2) | C29—C24—O4—C23 | 170.62 (14) |
O4—C24—C29—C30 | 2.5 (2) | C25—C24—O4—C23 | −7.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N2 | 0.95 (2) | 1.69 (2) | 2.5749 (18) | 154 (2) |
O3—H3···N4 | 0.97 (2) | 1.71 (2) | 2.5921 (16) | 150.6 (18) |
C9—H9B···O1 | 0.97 | 2.42 | 2.8971 (17) | 110 |
C31—H31B···O4 | 0.97 | 2.25 | 2.8830 (18) | 122 |
Experimental details
Crystal data | |
Chemical formula | C22H18N2O2 |
Mr | 342.38 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 14.3963 (6), 19.0230 (8), 12.7651 (6) |
β (°) | 91.305 (1) |
V (Å3) | 3495.0 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.32 × 0.28 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.924, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21496, 8356, 5640 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.120, 1.00 |
No. of reflections | 8356 |
No. of parameters | 477 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.19 |
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 |
O2—H2···N2 | 0.95 (2) | 1.69 (2) | 2.5749 (18) | 154 (2) |
O3—H3···N4 | 0.97 (2) | 1.71 (2) | 2.5921 (16) | 150.6 (18) |
C9—H9B···O1 | 0.97 | 2.42 | 2.8971 (17) | 110 |
C31—H31B···O4 | 0.97 | 2.25 | 2.8830 (18) | 122 |
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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.
The asymmetric unit of the title compound, (I), contains two crystallographicaly independent molecules (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 rings have fragments N1—C12—C11—N2 and N3—C34—C33—N4, which are conjugated with the adjacent benzene rings. Like azepines, diazepines are not planar and generally adopt boat conformation (Armarego, 1977).
The rings A (C2—C7), B (C11—C16), C (C17—C22) and A' (C24—C29), B' (C33—C38), C' (C39—C44) are, of course, planar and dihedral angles between them are A/B = 88.79 (3)°, A/C = 68.16 (3)°, B/C = 37.51 (2)° and A'/B' = 82.43 (3)°, A'/C' = 78.52 (2)°, B'/C' = 28.65 (3)°. The seven membered rings D (N1/N2/C8—C12) and D' (N3/N4/C30—C34) are not planar and adopt nearly boat conformations.
The intramolecular O—H···N and C—H···O hydrogen bonds (Table 1) may be effective in the stabilization of the structure.