Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029066/nc2040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029066/nc2040Isup2.hkl |
CCDC reference: 621740
Phenylenediamine (0.11 g, 1.0 mmol), montmorillonite K10 (0.3 g) and 4-chloroacetophenone (0.34 g, 2.2 mmol) were mixed and afterwards allowed to stay at room temperature for 24 h. On completion of the reaction, which was monitored by TLC, montmorillonite was filtered off and washed with 3.5 ml of acetone. The filtrate was evaporated to dryness and the residue was subjected to column chromatography over silica gel using petroleum ether-acetone (4:1) as eluent to afford compound I in 87% yield (0.33 g). The crystal was obtained by evaporation of the solvent from a solution of I in acetone-petroleum ether (1:1).1H NMR (CDCl3, 400 MHz): δ 1.74 (s, 3H, CH3), 2.88 (d, 1H, J=12.8 Hz), 3.07 (d, 1H, J=12 Hz), 3.43 (s, 1H, NH), 6.84–7.53 (m, 12H, ArH). 13C NMR (CDCl3, 100 MHz): δ 30.2, 43.3, 74.1, 122.0, 122.5, 127.1, 127.5, 128.7, 128.8, 129.0, 133.4, 136.5, 138.0, 140.3, 146.2, 166.6. UV λmax (EtOH): 262 nm, 365 nm. IR (KBr, cm-1): 3272 (s), 1590 (m), 1559(m), 1474(s), 1436(w), 1397(m), 1328(m), 1243(s), 1212(m), 1096(m), 1011(m).
C—H atoms were positioned with idealized geometry and were refined isotropic using a riding model with C—H = 0.94 Å for aromatic, C—H = 0.98 Å for methylene and C—H = 0.97 Å for methy H atoms and Uiso(H)=1.2Ueq(C) for aromatic and methylene H atoms and Uiso(H)=1.5Ueq(C) for methyl H atoms. The N—H H atom was located in difference map and was refined isotropic (Uiso(H)=1.2Ueq(N) with the N—H bond length restraint to 0.83 (2) Å.
1,5-benzodiazepine derivatives have been attracting great interest because of their potential pharmacological use as hypnotic agents (Landquist et al., 1984; Schutz et al., 1982), against cancer (Atwal et al., 1987; Merluzzi et al., 1990), viral infections (Merluzzi et al., 1990) and cardiovascular disorders (Di Braccio et al., 2001; Tranquillini et al., 1997). They are also of interest in the development of new classes of fused heterocyclic compounds, as exemplified by triazolo- (Aversa et al., 1986), oxadiazolo-(Chimirri et al., 1990), oxazino- (El-Sayed et al., 1999) or furanobenzodiazepines (Reddy et al., 2000). A literature search for 1,5-benzodiazepines substituted at C7 and C9 leads to (2-(4- Nitro-phenyl)-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepine) (Braun et al., 2000), (2,4-Bis-(2,5-dipropoxy-phenyl) -2,3-dihydro-1H-1,5-benzodiazepine) (Hormaza et al., 2004), 4,5:15,16-Dibenzo-2,7:13,18-dimethano-7,13-dimethyl-3,6,14, 17,23,24-hexa-azatricyclo(17.3.1.18,12) tetracosa-1(23),2,8, 11,12 (24),17,19,21-octaene (V) (de O. Cabral et al., 1982) and (VI) (4-(4-Methoxy-phenyl)-2-(4-nitro-phenyl)-2,3-dihydro- 1H-1,5-benzodiazepine) (Braun et al., 2004), which are related to the title compound. In view of the importance of such compounds we have determined the structure of the title compound (I).
In the crystal structure of the title compound (I) the seven-membered heterocyclic is in an boat-shaped conformation with an approximate mirror plane through C8 and the mid-point of the C1—C2 bond (Fig. 1). A similar boat structure is also observed in 1-Benzyl-4-(4-nitrophenyl)-2,3-dihydro-1H-1,5-benzodiazepine (Low et al., 2003) and 2,2,4-Trimethyl-2,3-dihydro-1H- 1,5-benzodiazepine (Samanta et al., 1999). The atoms N1 and N2 are not coplanar with the adjacent aryl ring, as shown both by the N1—C1—C2—N2 torsion angle (4.1 (3) °), and by the deviations of the two N atoms (-0.015 (1) Å for N1 and -0.154 (2) Å for N2) from the plane of the aryl ring (C1/C2/C3/C4/C5/C6).
The phenyl rings C10 to C15 and C16 to C21 are rotated out of the plane of the seven membered ring, which is probably due to the steric affects of the phenyl groups. This phenomenon is also found in 2,4-diphenyl-2,3-dihydro-1H-1,5-benzodiaze-pine (Kaluski et al., 1989).
The molecules are connected via intermolecular N—H···N hydrogen bonding between N2 which act as a donor and the H atom attached to N1 into chains that elongate in the [010] direction (Fig. 2).
For related structures see: Braun et al. (2000); Hormaza et al. (2004); Cabral et al. (1982); Braun & Muller (2004); Samanta et al. (1999); Kaluski et al. (1989). For related literature, see: Atwal et al. (1987); Aversa et al. (1986); Chimirri et al. (1990); Di Braccio, Grossi, Roma, Vargiu, Mura & Marongiu (2001); El-Sayed, Abdel-Ghany, Saghier & El (1999); Kaluski et al. (1989); Landquist (1984); Low et al. (2003); Merluzzi et al. (1990); Reddy et al. (2000); Schutz (1982); Tranquillini et al. (1997); Samanta (1999).
Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
C22H18Cl2N2 | F(000) = 792 |
Mr = 381.28 | Dx = 1.356 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 6453 reflections |
a = 14.095 (3) Å | θ = 3.1–25.3° |
b = 9.9845 (15) Å | µ = 0.36 mm−1 |
c = 14.859 (3) Å | T = 213 K |
β = 116.728 (3)° | Block, yellow |
V = 1867.7 (6) Å3 | 0.48 × 0.38 × 0.20 mm |
Z = 4 |
Rigaku Mercury diffractometer | 3404 independent reflections |
Radiation source: fine-focus sealed tube | 3103 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 7.31 pixels mm-1 | θmax = 25.4°, θmin = 3.1° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −12→12 |
Tmin = 0.834, Tmax = 0.921 | l = −17→16 |
17639 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0374P)2 + 0.8045P] where P = (Fo2 + 2Fc2)/3 |
3404 reflections | (Δ/σ)max = 0.001 |
241 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C22H18Cl2N2 | V = 1867.7 (6) Å3 |
Mr = 381.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.095 (3) Å | µ = 0.36 mm−1 |
b = 9.9845 (15) Å | T = 213 K |
c = 14.859 (3) Å | 0.48 × 0.38 × 0.20 mm |
β = 116.728 (3)° |
Rigaku Mercury diffractometer | 3404 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 3103 reflections with I > 2σ(I) |
Tmin = 0.834, Tmax = 0.921 | Rint = 0.028 |
17639 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.20 e Å−3 |
3404 reflections | Δρmin = −0.32 e Å−3 |
241 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 | ||
Cl1 | 0.45977 (4) | 0.38308 (5) | 0.58336 (4) | 0.05107 (17) | |
Cl2 | 0.49691 (4) | 0.97041 (7) | 0.31844 (4) | 0.0594 (2) | |
N1 | 0.00610 (12) | 0.71966 (15) | 0.37243 (11) | 0.0301 (3) | |
N2 | 0.00367 (12) | 0.97254 (17) | 0.27959 (12) | 0.0315 (4) | |
H2 | −0.0114 (17) | 1.033 (2) | 0.2376 (18) | 0.041 (6)* | |
C1 | −0.08515 (14) | 0.80205 (18) | 0.33118 (13) | 0.0296 (4) | |
C2 | −0.08722 (14) | 0.92813 (19) | 0.28826 (13) | 0.0312 (4) | |
C3 | −0.18201 (16) | 0.9998 (2) | 0.24741 (15) | 0.0409 (5) | |
H3 | −0.1844 | 1.0846 | 0.2189 | 0.049* | |
C4 | −0.27317 (16) | 0.9482 (2) | 0.24808 (16) | 0.0476 (5) | |
H4 | −0.3362 | 0.9986 | 0.2210 | 0.057* | |
C5 | −0.27147 (16) | 0.8233 (2) | 0.28832 (16) | 0.0453 (5) | |
H5 | −0.3332 | 0.7883 | 0.2887 | 0.054* | |
C6 | −0.17828 (15) | 0.7497 (2) | 0.32819 (14) | 0.0369 (4) | |
H6 | −0.1777 | 0.6634 | 0.3536 | 0.044* | |
C7 | 0.09696 (14) | 0.77208 (18) | 0.42989 (13) | 0.0281 (4) | |
C8 | 0.10919 (14) | 0.91792 (17) | 0.45824 (13) | 0.0286 (4) | |
H8A | 0.1795 | 0.9315 | 0.5151 | 0.034* | |
H8B | 0.0561 | 0.9413 | 0.4812 | 0.034* | |
C9 | 0.09695 (14) | 1.01437 (18) | 0.37237 (13) | 0.0287 (4) | |
C10 | 0.18912 (14) | 0.67966 (18) | 0.47382 (12) | 0.0281 (4) | |
C11 | 0.17155 (15) | 0.54254 (19) | 0.47762 (14) | 0.0330 (4) | |
H11 | 0.1020 | 0.5107 | 0.4562 | 0.040* | |
C12 | 0.25524 (15) | 0.45329 (19) | 0.51245 (14) | 0.0361 (4) | |
H12 | 0.2426 | 0.3612 | 0.5145 | 0.043* | |
C13 | 0.35711 (15) | 0.49938 (19) | 0.54418 (14) | 0.0347 (4) | |
C14 | 0.37761 (15) | 0.6339 (2) | 0.54494 (15) | 0.0387 (5) | |
H14 | 0.4478 | 0.6648 | 0.5690 | 0.046* | |
C15 | 0.29383 (15) | 0.72347 (19) | 0.50997 (14) | 0.0349 (4) | |
H15 | 0.3077 | 0.8156 | 0.5106 | 0.042* | |
C16 | 0.19604 (15) | 1.00558 (17) | 0.35502 (13) | 0.0298 (4) | |
C17 | 0.20002 (16) | 0.9223 (2) | 0.28171 (14) | 0.0357 (4) | |
H17 | 0.1393 | 0.8735 | 0.2391 | 0.043* | |
C18 | 0.29232 (17) | 0.9102 (2) | 0.27055 (15) | 0.0411 (5) | |
H18 | 0.2944 | 0.8527 | 0.2213 | 0.049* | |
C19 | 0.38053 (16) | 0.9830 (2) | 0.33215 (15) | 0.0383 (5) | |
C20 | 0.37924 (16) | 1.0662 (2) | 0.40541 (15) | 0.0391 (5) | |
H20 | 0.4401 | 1.1154 | 0.4473 | 0.047* | |
C21 | 0.28728 (15) | 1.07658 (19) | 0.41658 (14) | 0.0351 (4) | |
H21 | 0.2864 | 1.1329 | 0.4669 | 0.042* | |
C22 | 0.07973 (16) | 1.15650 (19) | 0.40215 (15) | 0.0358 (4) | |
H22A | 0.0843 | 1.2207 | 0.3553 | 0.054* | |
H22B | 0.1339 | 1.1763 | 0.4698 | 0.054* | |
H22C | 0.0101 | 1.1621 | 0.4002 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0413 (3) | 0.0425 (3) | 0.0614 (4) | 0.0102 (2) | 0.0160 (3) | −0.0041 (2) |
Cl2 | 0.0425 (3) | 0.0919 (5) | 0.0528 (4) | 0.0102 (3) | 0.0294 (3) | 0.0096 (3) |
N1 | 0.0302 (8) | 0.0306 (8) | 0.0304 (8) | −0.0029 (7) | 0.0143 (7) | −0.0013 (6) |
N2 | 0.0355 (9) | 0.0345 (9) | 0.0247 (8) | 0.0000 (7) | 0.0136 (7) | 0.0030 (7) |
C1 | 0.0294 (9) | 0.0332 (10) | 0.0263 (9) | −0.0017 (8) | 0.0126 (7) | −0.0062 (7) |
C2 | 0.0322 (10) | 0.0382 (10) | 0.0239 (9) | 0.0013 (8) | 0.0132 (8) | −0.0032 (8) |
C3 | 0.0412 (12) | 0.0471 (12) | 0.0336 (11) | 0.0102 (9) | 0.0161 (9) | 0.0033 (9) |
C4 | 0.0316 (11) | 0.0665 (15) | 0.0417 (12) | 0.0116 (10) | 0.0138 (9) | −0.0004 (11) |
C5 | 0.0319 (11) | 0.0618 (14) | 0.0450 (12) | −0.0034 (10) | 0.0198 (9) | −0.0064 (10) |
C6 | 0.0353 (11) | 0.0427 (11) | 0.0345 (10) | −0.0050 (9) | 0.0174 (8) | −0.0057 (8) |
C7 | 0.0319 (10) | 0.0311 (10) | 0.0249 (9) | −0.0026 (8) | 0.0161 (8) | 0.0013 (7) |
C8 | 0.0334 (10) | 0.0286 (9) | 0.0251 (9) | −0.0013 (8) | 0.0145 (8) | −0.0017 (7) |
C9 | 0.0353 (10) | 0.0274 (9) | 0.0255 (9) | −0.0031 (8) | 0.0155 (8) | −0.0021 (7) |
C10 | 0.0331 (9) | 0.0286 (9) | 0.0233 (9) | −0.0034 (8) | 0.0133 (7) | −0.0010 (7) |
C11 | 0.0329 (10) | 0.0312 (10) | 0.0337 (10) | −0.0052 (8) | 0.0141 (8) | 0.0000 (8) |
C12 | 0.0409 (11) | 0.0282 (10) | 0.0375 (11) | −0.0027 (8) | 0.0161 (9) | −0.0003 (8) |
C13 | 0.0342 (10) | 0.0366 (11) | 0.0322 (10) | 0.0037 (8) | 0.0139 (8) | −0.0005 (8) |
C14 | 0.0288 (10) | 0.0383 (11) | 0.0471 (12) | −0.0041 (8) | 0.0153 (9) | 0.0001 (9) |
C15 | 0.0368 (11) | 0.0289 (10) | 0.0382 (11) | −0.0052 (8) | 0.0163 (9) | 0.0001 (8) |
C16 | 0.0381 (10) | 0.0250 (9) | 0.0291 (9) | 0.0005 (8) | 0.0177 (8) | 0.0031 (7) |
C17 | 0.0398 (11) | 0.0367 (11) | 0.0332 (10) | −0.0024 (9) | 0.0187 (9) | −0.0033 (8) |
C18 | 0.0470 (12) | 0.0477 (12) | 0.0347 (11) | 0.0060 (10) | 0.0237 (9) | −0.0025 (9) |
C19 | 0.0367 (11) | 0.0463 (12) | 0.0367 (11) | 0.0072 (9) | 0.0207 (9) | 0.0109 (9) |
C20 | 0.0360 (11) | 0.0371 (11) | 0.0415 (11) | −0.0017 (9) | 0.0150 (9) | 0.0030 (9) |
C21 | 0.0398 (11) | 0.0310 (10) | 0.0355 (10) | −0.0017 (8) | 0.0178 (9) | −0.0044 (8) |
C22 | 0.0453 (11) | 0.0288 (10) | 0.0394 (11) | 0.0010 (8) | 0.0244 (9) | −0.0011 (8) |
Cl1—C13 | 1.7387 (19) | C10—C15 | 1.395 (3) |
Cl2—C19 | 1.746 (2) | C10—C11 | 1.397 (3) |
N1—C7 | 1.288 (2) | C11—C12 | 1.380 (3) |
N1—C1 | 1.413 (2) | C11—H11 | 0.9400 |
N2—C2 | 1.415 (2) | C12—C13 | 1.374 (3) |
N2—C9 | 1.474 (2) | C12—H12 | 0.9400 |
N2—H2 | 0.83 (2) | C13—C14 | 1.373 (3) |
C1—C6 | 1.395 (3) | C14—C15 | 1.383 (3) |
C1—C2 | 1.405 (3) | C14—H14 | 0.9400 |
C2—C3 | 1.392 (3) | C15—H15 | 0.9400 |
C3—C4 | 1.389 (3) | C16—C21 | 1.391 (3) |
C3—H3 | 0.9400 | C16—C17 | 1.391 (3) |
C4—C5 | 1.379 (3) | C17—C18 | 1.389 (3) |
C4—H4 | 0.9400 | C17—H17 | 0.9400 |
C5—C6 | 1.384 (3) | C18—C19 | 1.374 (3) |
C5—H5 | 0.9400 | C18—H18 | 0.9400 |
C6—H6 | 0.9400 | C19—C20 | 1.376 (3) |
C7—C10 | 1.484 (3) | C20—C21 | 1.383 (3) |
C7—C8 | 1.504 (2) | C20—H20 | 0.9400 |
C8—C9 | 1.545 (2) | C21—H21 | 0.9400 |
C8—H8A | 0.9800 | C22—H22A | 0.9700 |
C8—H8B | 0.9800 | C22—H22B | 0.9700 |
C9—C16 | 1.533 (2) | C22—H22C | 0.9700 |
C9—C22 | 1.538 (3) | ||
C7—N1—C1 | 119.37 (15) | C12—C11—C10 | 120.72 (17) |
C2—N2—C9 | 117.82 (14) | C12—C11—H11 | 119.6 |
C2—N2—H2 | 111.2 (15) | C10—C11—H11 | 119.6 |
C9—N2—H2 | 108.5 (15) | C13—C12—C11 | 119.85 (18) |
C6—C1—C2 | 119.58 (17) | C13—C12—H12 | 120.1 |
C6—C1—N1 | 117.11 (17) | C11—C12—H12 | 120.1 |
C2—C1—N1 | 123.18 (16) | C14—C13—C12 | 120.95 (18) |
C3—C2—C1 | 118.60 (18) | C14—C13—Cl1 | 120.68 (15) |
C3—C2—N2 | 122.00 (18) | C12—C13—Cl1 | 118.37 (15) |
C1—C2—N2 | 119.14 (16) | C13—C14—C15 | 119.25 (18) |
C4—C3—C2 | 121.1 (2) | C13—C14—H14 | 120.4 |
C4—C3—H3 | 119.5 | C15—C14—H14 | 120.4 |
C2—C3—H3 | 119.5 | C14—C15—C10 | 121.25 (17) |
C5—C4—C3 | 120.2 (2) | C14—C15—H15 | 119.4 |
C5—C4—H4 | 119.9 | C10—C15—H15 | 119.4 |
C3—C4—H4 | 119.9 | C21—C16—C17 | 117.94 (17) |
C4—C5—C6 | 119.57 (19) | C21—C16—C9 | 120.21 (16) |
C4—C5—H5 | 120.2 | C17—C16—C9 | 121.77 (16) |
C6—C5—H5 | 120.2 | C18—C17—C16 | 121.03 (18) |
C5—C6—C1 | 120.9 (2) | C18—C17—H17 | 119.5 |
C5—C6—H6 | 119.6 | C16—C17—H17 | 119.5 |
C1—C6—H6 | 119.6 | C19—C18—C17 | 119.32 (18) |
N1—C7—C10 | 116.84 (16) | C19—C18—H18 | 120.3 |
N1—C7—C8 | 122.24 (16) | C17—C18—H18 | 120.3 |
C10—C7—C8 | 120.76 (15) | C18—C19—C20 | 121.10 (18) |
C7—C8—C9 | 114.58 (14) | C18—C19—Cl2 | 120.02 (16) |
C7—C8—H8A | 108.6 | C20—C19—Cl2 | 118.88 (16) |
C9—C8—H8A | 108.6 | C19—C20—C21 | 119.11 (19) |
C7—C8—H8B | 108.6 | C19—C20—H20 | 120.4 |
C9—C8—H8B | 108.6 | C21—C20—H20 | 120.4 |
H8A—C8—H8B | 107.6 | C20—C21—C16 | 121.49 (18) |
N2—C9—C16 | 108.87 (14) | C20—C21—H21 | 119.3 |
N2—C9—C22 | 109.92 (15) | C16—C21—H21 | 119.3 |
C16—C9—C22 | 112.02 (15) | C9—C22—H22A | 109.5 |
N2—C9—C8 | 108.48 (14) | C9—C22—H22B | 109.5 |
C16—C9—C8 | 109.36 (14) | H22A—C22—H22B | 109.5 |
C22—C9—C8 | 108.12 (14) | C9—C22—H22C | 109.5 |
C15—C10—C11 | 117.90 (17) | H22A—C22—H22C | 109.5 |
C15—C10—C7 | 122.66 (16) | H22B—C22—H22C | 109.5 |
C11—C10—C7 | 119.42 (16) | ||
C7—N1—C1—C6 | −139.58 (17) | C8—C7—C10—C11 | 156.48 (16) |
C7—N1—C1—C2 | 44.5 (2) | C15—C10—C11—C12 | −2.5 (3) |
C6—C1—C2—C3 | 2.6 (3) | C7—C10—C11—C12 | 176.09 (16) |
N1—C1—C2—C3 | 178.39 (16) | C10—C11—C12—C13 | 0.3 (3) |
C6—C1—C2—N2 | −171.65 (16) | C11—C12—C13—C14 | 2.2 (3) |
N1—C1—C2—N2 | 4.1 (3) | C11—C12—C13—Cl1 | −177.79 (15) |
C9—N2—C2—C3 | 112.9 (2) | C12—C13—C14—C15 | −2.2 (3) |
C9—N2—C2—C1 | −73.0 (2) | Cl1—C13—C14—C15 | 177.73 (15) |
C1—C2—C3—C4 | −0.4 (3) | C13—C14—C15—C10 | −0.1 (3) |
N2—C2—C3—C4 | 173.62 (18) | C11—C10—C15—C14 | 2.4 (3) |
C2—C3—C4—C5 | −0.9 (3) | C7—C10—C15—C14 | −176.10 (17) |
C3—C4—C5—C6 | 0.1 (3) | N2—C9—C16—C21 | 160.02 (16) |
C4—C5—C6—C1 | 2.1 (3) | C22—C9—C16—C21 | 38.2 (2) |
C2—C1—C6—C5 | −3.5 (3) | C8—C9—C16—C21 | −81.6 (2) |
N1—C1—C6—C5 | −179.51 (16) | N2—C9—C16—C17 | −23.3 (2) |
C1—N1—C7—C10 | 177.88 (14) | C22—C9—C16—C17 | −145.10 (17) |
C1—N1—C7—C8 | 2.4 (2) | C8—C9—C16—C17 | 95.1 (2) |
N1—C7—C8—C9 | −73.0 (2) | C21—C16—C17—C18 | 0.2 (3) |
C10—C7—C8—C9 | 111.68 (18) | C9—C16—C17—C18 | −176.54 (17) |
C2—N2—C9—C16 | 158.23 (15) | C16—C17—C18—C19 | −0.8 (3) |
C2—N2—C9—C22 | −78.7 (2) | C17—C18—C19—C20 | 0.8 (3) |
C2—N2—C9—C8 | 39.3 (2) | C17—C18—C19—Cl2 | −179.33 (15) |
C7—C8—C9—N2 | 45.0 (2) | C18—C19—C20—C21 | −0.2 (3) |
C7—C8—C9—C16 | −73.60 (19) | Cl2—C19—C20—C21 | 179.98 (15) |
C7—C8—C9—C22 | 164.18 (15) | C19—C20—C21—C16 | −0.5 (3) |
N1—C7—C10—C15 | 159.47 (16) | C17—C16—C21—C20 | 0.5 (3) |
C8—C7—C10—C15 | −25.0 (2) | C9—C16—C21—C20 | 177.27 (17) |
N1—C7—C10—C11 | −19.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.83 (2) | 2.50 (2) | 3.306 (2) | 165 (2) |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C22H18Cl2N2 |
Mr | 381.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 213 |
a, b, c (Å) | 14.095 (3), 9.9845 (15), 14.859 (3) |
β (°) | 116.728 (3) |
V (Å3) | 1867.7 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.48 × 0.38 × 0.20 |
Data collection | |
Diffractometer | Rigaku Mercury |
Absorption correction | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | 0.834, 0.921 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17639, 3404, 3103 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.097, 1.14 |
No. of reflections | 3404 |
No. of parameters | 241 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.32 |
Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalClear, CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.83 (2) | 2.50 (2) | 3.306 (2) | 165 (2) |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
1,5-benzodiazepine derivatives have been attracting great interest because of their potential pharmacological use as hypnotic agents (Landquist et al., 1984; Schutz et al., 1982), against cancer (Atwal et al., 1987; Merluzzi et al., 1990), viral infections (Merluzzi et al., 1990) and cardiovascular disorders (Di Braccio et al., 2001; Tranquillini et al., 1997). They are also of interest in the development of new classes of fused heterocyclic compounds, as exemplified by triazolo- (Aversa et al., 1986), oxadiazolo-(Chimirri et al., 1990), oxazino- (El-Sayed et al., 1999) or furanobenzodiazepines (Reddy et al., 2000). A literature search for 1,5-benzodiazepines substituted at C7 and C9 leads to (2-(4- Nitro-phenyl)-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepine) (Braun et al., 2000), (2,4-Bis-(2,5-dipropoxy-phenyl) -2,3-dihydro-1H-1,5-benzodiazepine) (Hormaza et al., 2004), 4,5:15,16-Dibenzo-2,7:13,18-dimethano-7,13-dimethyl-3,6,14, 17,23,24-hexa-azatricyclo(17.3.1.18,12) tetracosa-1(23),2,8, 11,12 (24),17,19,21-octaene (V) (de O. Cabral et al., 1982) and (VI) (4-(4-Methoxy-phenyl)-2-(4-nitro-phenyl)-2,3-dihydro- 1H-1,5-benzodiazepine) (Braun et al., 2004), which are related to the title compound. In view of the importance of such compounds we have determined the structure of the title compound (I).
In the crystal structure of the title compound (I) the seven-membered heterocyclic is in an boat-shaped conformation with an approximate mirror plane through C8 and the mid-point of the C1—C2 bond (Fig. 1). A similar boat structure is also observed in 1-Benzyl-4-(4-nitrophenyl)-2,3-dihydro-1H-1,5-benzodiazepine (Low et al., 2003) and 2,2,4-Trimethyl-2,3-dihydro-1H- 1,5-benzodiazepine (Samanta et al., 1999). The atoms N1 and N2 are not coplanar with the adjacent aryl ring, as shown both by the N1—C1—C2—N2 torsion angle (4.1 (3) °), and by the deviations of the two N atoms (-0.015 (1) Å for N1 and -0.154 (2) Å for N2) from the plane of the aryl ring (C1/C2/C3/C4/C5/C6).
The phenyl rings C10 to C15 and C16 to C21 are rotated out of the plane of the seven membered ring, which is probably due to the steric affects of the phenyl groups. This phenomenon is also found in 2,4-diphenyl-2,3-dihydro-1H-1,5-benzodiaze-pine (Kaluski et al., 1989).
The molecules are connected via intermolecular N—H···N hydrogen bonding between N2 which act as a donor and the H atom attached to N1 into chains that elongate in the [010] direction (Fig. 2).