organic compounds
5-Dichloroacetyl-4-methyl-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one hemihydrate
aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and bDepartment of Chemistry, Government Arts College (Autonomous), Coimbatore 641 018, India
*Correspondence e-mail: mnpsy2004@yahoo.com
There are two crystallographically independent organic molecules in the 12H12Cl2N2O2·0.5H2O. The benzodiazepine ring adopts a distorted boat conformation in both molecules. The crystal packing is controlled by N—H⋯O, C—H⋯O and O—H⋯O intra- and intermolecular hydrogen bonds. A graph-set motif of R33(14) dimer formation by a combination of N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds stabilizes the molecules and extends along a axis.
of the title compound, CRelated literature
For the anticonvulsant activity of benzodiazepine, see: MacDonald (2002). For their hypnotic effect, see: Gringauz (1999). For their use in the treatment of gastrointestinal and central nervous system disorders, see: Rahbaek et al. (1999). For other therapeutic applications, see: Albright et al. (1998); Lee et al. (1999). For hydrogen-bond motifs, see: Bernstein et al. (1995). For puckering and asymmetry parameters, see: Cremer & Pople (1975); Nardelli (1983). For details of the preparation of the title compound, see: Venkatraj et al. (2008).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536809036940/bt5048sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809036940/bt5048Isup2.hkl
To a solution of tetrahydro-4-methyl-1,5-benzodiazepin-2-one (0.88 g) in anhydrous benzene (50 ml) was added triethylamine (2.8 ml) and dichloroacetyl chloride (1.90 ml). The contents were allowed to reflux on a water bath for 6hrs. The reaction mixture was washed with sodium bicarbonate solution (10%), water and dried. Evaporation of the solvent results a crude mass and further crystallization from ethanol gives colorless crystals (Venkatraj et al., 2008).
The Nitrogen and Oxygen H atoms were refined and the other H atoms positioned geometrically (C—H=0.93–0.98 Å) and allowed to ride on their parent atoms, with 1.5Ueq(C) for methyl H and 1.2 Ueq(C) for other H atoms.
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C12H12Cl2N2O2·0.5H2O | F(000) = 612 |
Mr = 592.29 | Dx = 1.441 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4629 reflections |
a = 8.5470 (3) Å | θ = 2.3–26.5° |
b = 18.0837 (6) Å | µ = 0.48 mm−1 |
c = 8.8697 (3) Å | T = 293 K |
β = 95.405 (2)° | Block, colourless |
V = 1364.82 (8) Å3 | 0.26 × 0.24 × 0.22 mm |
Z = 2 |
Bruker Kappa APEXII area-detector diffractometer | 5599 independent reflections |
Radiation source: fine-focus sealed tube | 4873 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω and ϕ scans | θmax = 26.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −10→10 |
Tmin = 0.884, Tmax = 0.901 | k = −22→22 |
14191 measured reflections | l = −11→10 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.7028P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.006 |
5599 reflections | Δρmax = 0.46 e Å−3 |
352 parameters | Δρmin = −0.62 e Å−3 |
1 restraint | Absolute structure: Flack (1983),2698 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.06 (6) |
C12H12Cl2N2O2·0.5H2O | V = 1364.82 (8) Å3 |
Mr = 592.29 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.5470 (3) Å | µ = 0.48 mm−1 |
b = 18.0837 (6) Å | T = 293 K |
c = 8.8697 (3) Å | 0.26 × 0.24 × 0.22 mm |
β = 95.405 (2)° |
Bruker Kappa APEXII area-detector diffractometer | 5599 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 4873 reflections with I > 2σ(I) |
Tmin = 0.884, Tmax = 0.901 | Rint = 0.022 |
14191 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.110 | Δρmax = 0.46 e Å−3 |
S = 1.04 | Δρmin = −0.62 e Å−3 |
5599 reflections | Absolute structure: Flack (1983),2698 Friedel pairs |
352 parameters | Absolute structure parameter: 0.06 (6) |
1 restraint |
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 | ||
Cl1A | 1.62028 (16) | −0.29670 (7) | 1.77856 (13) | 0.0941 (4) | |
Cl1B | 1.04826 (15) | 0.13662 (6) | 0.96558 (15) | 0.0906 (4) | |
Cl2A | 1.48485 (16) | −0.15064 (6) | 1.74118 (13) | 0.0858 (3) | |
Cl2B | 0.8172 (2) | 0.15716 (9) | 1.17529 (14) | 0.1300 (7) | |
O1A | 1.5519 (3) | −0.46993 (14) | 1.2925 (3) | 0.0594 (6) | |
O1B | 1.0719 (3) | −0.07368 (15) | 0.6539 (2) | 0.0573 (6) | |
O2A | 1.6504 (3) | −0.20942 (14) | 1.4809 (3) | 0.0635 (7) | |
O2B | 0.7429 (3) | 0.02505 (17) | 1.0049 (4) | 0.0852 (9) | |
O3 | 1.2224 (4) | −0.56267 (15) | 1.5161 (4) | 0.0677 (7) | |
H1W | 1.279 (6) | −0.601 (3) | 1.502 (6) | 0.108 (19)* | |
H2W | 1.140 (5) | −0.570 (2) | 1.467 (4) | 0.059 (11)* | |
N1A | 1.3405 (3) | −0.42583 (13) | 1.3919 (3) | 0.0403 (5) | |
H1A | 1.325 (4) | −0.469 (2) | 1.432 (4) | 0.057 (10)* | |
N1B | 1.2097 (3) | −0.03383 (14) | 0.8658 (3) | 0.0399 (5) | |
H1B | 1.261 (3) | −0.0095 (17) | 0.811 (3) | 0.031 (7)* | |
C2A | 1.4518 (3) | −0.42199 (16) | 1.2939 (3) | 0.0420 (6) | |
C2B | 1.1026 (3) | −0.07798 (16) | 0.7907 (3) | 0.0410 (6) | |
C3A | 1.4398 (4) | −0.35821 (17) | 1.1848 (3) | 0.0462 (7) | |
H3A | 1.3314 | −0.3539 | 1.1423 | 0.055* | |
H3B | 1.5028 | −0.3694 | 1.1023 | 0.055* | |
C3B | 1.0275 (4) | −0.13513 (16) | 0.8847 (3) | 0.0465 (7) | |
H3C | 1.1089 | −0.1594 | 0.9505 | 0.056* | |
H3D | 0.9773 | −0.1723 | 0.8178 | 0.056* | |
C4A | 1.4920 (3) | −0.28414 (16) | 1.2521 (3) | 0.0441 (7) | |
H4A | 1.6071 | −0.2832 | 1.2637 | 0.053* | |
C4B | 0.9057 (4) | −0.10270 (17) | 0.9813 (4) | 0.0490 (7) | |
H4B | 0.8130 | −0.0886 | 0.9140 | 0.059* | |
N5A | 1.4357 (2) | −0.27668 (12) | 1.4044 (2) | 0.0368 (5) | |
N5B | 0.9699 (3) | −0.03578 (14) | 1.0580 (2) | 0.0403 (5) | |
C6A | 1.2763 (3) | −0.29648 (16) | 1.4220 (3) | 0.0355 (5) | |
C6B | 1.1307 (3) | −0.03545 (15) | 1.1206 (3) | 0.0363 (6) | |
C7A | 1.1664 (3) | −0.24204 (17) | 1.4443 (3) | 0.0457 (7) | |
H7A | 1.1961 | −0.1926 | 1.4462 | 0.055* | |
C7B | 1.1690 (4) | −0.03548 (18) | 1.2758 (3) | 0.0485 (7) | |
H7B | 1.0906 | −0.0415 | 1.3407 | 0.058* | |
C8A | 1.0148 (3) | −0.2607 (2) | 1.4635 (4) | 0.0548 (8) | |
H8A | 0.9424 | −0.2242 | 1.4820 | 0.066* | |
C8B | 1.3225 (4) | −0.0267 (2) | 1.3344 (4) | 0.0587 (9) | |
H8B | 1.3482 | −0.0259 | 1.4386 | 0.070* | |
C9A | 0.9695 (3) | −0.3334 (2) | 1.4554 (4) | 0.0530 (8) | |
H9A | 0.8658 | −0.3458 | 1.4675 | 0.064* | |
C9B | 1.4383 (4) | −0.01891 (19) | 1.2369 (4) | 0.0571 (9) | |
H9B | 1.5418 | −0.0109 | 1.2758 | 0.069* | |
C10A | 1.0749 (3) | −0.38800 (17) | 1.4298 (4) | 0.0467 (7) | |
H10A | 1.0422 | −0.4370 | 1.4237 | 0.056* | |
C10B | 1.4017 (3) | −0.02294 (17) | 1.0826 (4) | 0.0461 (7) | |
H10B | 1.4812 | −0.0194 | 1.0182 | 0.055* | |
C11A | 1.2304 (3) | −0.37036 (15) | 1.4130 (3) | 0.0353 (5) | |
C11B | 1.2482 (3) | −0.03216 (15) | 1.0231 (3) | 0.0363 (5) | |
C12A | 1.4358 (6) | −0.2213 (2) | 1.1517 (4) | 0.0707 (11) | |
H12A | 1.3230 | −0.2210 | 1.1396 | 0.106* | |
H12B | 1.4751 | −0.2271 | 1.0544 | 0.106* | |
H12C | 1.4733 | −0.1755 | 1.1964 | 0.106* | |
C12B | 0.8546 (5) | −0.1577 (3) | 1.0958 (5) | 0.0806 (12) | |
H12D | 0.9429 | −0.1705 | 1.1660 | 0.121* | |
H12E | 0.8147 | −0.2015 | 1.0443 | 0.121* | |
H12F | 0.7738 | −0.1361 | 1.1498 | 0.121* | |
C13A | 1.5282 (3) | −0.23943 (16) | 1.5082 (3) | 0.0425 (6) | |
C13B | 0.8785 (3) | 0.02480 (19) | 1.0567 (3) | 0.0483 (7) | |
C14A | 1.4827 (4) | −0.2412 (2) | 1.6705 (3) | 0.0516 (7) | |
H14A | 1.3773 | −0.2624 | 1.6720 | 0.062* | |
C14B | 0.9587 (5) | 0.0969 (2) | 1.1152 (4) | 0.0651 (10) | |
H14B | 1.0379 | 0.0860 | 1.1995 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1A | 0.1134 (9) | 0.0939 (8) | 0.0740 (7) | 0.0444 (7) | 0.0047 (6) | 0.0100 (6) |
Cl1B | 0.1093 (9) | 0.0570 (6) | 0.1045 (8) | −0.0225 (6) | 0.0047 (7) | 0.0035 (6) |
Cl2A | 0.1158 (9) | 0.0691 (6) | 0.0740 (6) | 0.0202 (6) | 0.0169 (6) | −0.0282 (5) |
Cl2B | 0.1609 (13) | 0.1493 (13) | 0.0748 (7) | 0.1052 (12) | −0.0141 (7) | −0.0412 (8) |
O1A | 0.0640 (14) | 0.0558 (13) | 0.0609 (13) | 0.0228 (12) | 0.0193 (11) | 0.0018 (11) |
O1B | 0.0562 (13) | 0.0768 (16) | 0.0377 (11) | −0.0032 (12) | −0.0020 (9) | −0.0029 (11) |
O2A | 0.0445 (12) | 0.0707 (16) | 0.0778 (16) | −0.0228 (11) | 0.0190 (11) | −0.0222 (13) |
O2B | 0.0332 (12) | 0.087 (2) | 0.133 (3) | 0.0137 (13) | −0.0012 (14) | 0.0200 (19) |
O3 | 0.0578 (16) | 0.0485 (14) | 0.093 (2) | 0.0005 (13) | −0.0113 (15) | 0.0087 (13) |
N1A | 0.0465 (13) | 0.0319 (13) | 0.0435 (13) | 0.0045 (10) | 0.0100 (10) | 0.0037 (10) |
N1B | 0.0367 (12) | 0.0480 (13) | 0.0360 (12) | −0.0030 (11) | 0.0087 (10) | 0.0039 (11) |
C2A | 0.0474 (16) | 0.0378 (15) | 0.0408 (14) | 0.0031 (13) | 0.0035 (12) | −0.0043 (12) |
C2B | 0.0388 (14) | 0.0439 (16) | 0.0400 (15) | 0.0031 (12) | 0.0026 (11) | −0.0056 (12) |
C3A | 0.0575 (18) | 0.0471 (16) | 0.0348 (13) | 0.0020 (14) | 0.0083 (12) | −0.0023 (12) |
C3B | 0.0504 (17) | 0.0371 (15) | 0.0511 (16) | −0.0102 (13) | −0.0010 (13) | −0.0056 (12) |
C4A | 0.0461 (16) | 0.0472 (17) | 0.0404 (14) | −0.0062 (13) | 0.0108 (12) | −0.0014 (13) |
C4B | 0.0382 (15) | 0.0495 (18) | 0.0588 (19) | −0.0087 (13) | 0.0016 (13) | 0.0007 (14) |
N5A | 0.0328 (11) | 0.0392 (12) | 0.0394 (11) | −0.0022 (9) | 0.0082 (9) | −0.0032 (9) |
N5B | 0.0282 (11) | 0.0521 (14) | 0.0409 (12) | 0.0018 (10) | 0.0047 (9) | 0.0010 (11) |
C6A | 0.0277 (12) | 0.0417 (14) | 0.0367 (13) | 0.0022 (11) | 0.0010 (10) | 0.0018 (11) |
C6B | 0.0334 (13) | 0.0375 (13) | 0.0372 (13) | 0.0031 (11) | −0.0004 (10) | 0.0018 (11) |
C7A | 0.0420 (15) | 0.0402 (16) | 0.0552 (17) | 0.0070 (12) | 0.0057 (13) | 0.0037 (13) |
C7B | 0.0540 (17) | 0.0523 (17) | 0.0390 (14) | 0.0062 (14) | 0.0031 (12) | 0.0047 (13) |
C8A | 0.0372 (16) | 0.057 (2) | 0.071 (2) | 0.0182 (14) | 0.0091 (14) | 0.0025 (16) |
C8B | 0.071 (2) | 0.060 (2) | 0.0419 (16) | 0.0053 (18) | −0.0129 (15) | −0.0005 (15) |
C9A | 0.0292 (15) | 0.065 (2) | 0.0648 (19) | −0.0016 (14) | 0.0056 (13) | 0.0010 (17) |
C9B | 0.0434 (17) | 0.057 (2) | 0.066 (2) | −0.0052 (15) | −0.0182 (15) | 0.0001 (16) |
C10A | 0.0376 (15) | 0.0460 (17) | 0.0563 (17) | −0.0072 (12) | 0.0031 (13) | −0.0004 (13) |
C10B | 0.0328 (13) | 0.0472 (17) | 0.0568 (17) | −0.0013 (12) | −0.0033 (12) | 0.0023 (14) |
C11A | 0.0356 (13) | 0.0376 (14) | 0.0326 (12) | −0.0005 (11) | 0.0032 (10) | −0.0005 (11) |
C11B | 0.0342 (13) | 0.0347 (13) | 0.0393 (13) | 0.0007 (11) | 0.0009 (10) | 0.0015 (11) |
C12A | 0.104 (3) | 0.049 (2) | 0.061 (2) | −0.0015 (19) | 0.019 (2) | 0.0172 (17) |
C12B | 0.083 (3) | 0.075 (3) | 0.087 (3) | −0.036 (2) | 0.026 (2) | 0.004 (2) |
C13A | 0.0333 (14) | 0.0402 (15) | 0.0551 (16) | −0.0060 (12) | 0.0107 (12) | −0.0084 (13) |
C13B | 0.0353 (15) | 0.0581 (19) | 0.0525 (17) | 0.0096 (14) | 0.0086 (13) | 0.0103 (15) |
C14A | 0.0420 (15) | 0.064 (2) | 0.0482 (16) | 0.0011 (14) | 0.0015 (12) | −0.0146 (15) |
C14B | 0.073 (2) | 0.064 (2) | 0.0539 (19) | 0.0303 (18) | −0.0134 (17) | −0.0112 (16) |
Cl1A—C14A | 1.759 (3) | N5B—C13B | 1.345 (4) |
Cl1B—C14B | 1.748 (4) | N5B—C6B | 1.432 (3) |
Cl2A—C14A | 1.754 (3) | C6A—C7A | 1.388 (4) |
Cl2B—C14B | 1.748 (4) | C6A—C11A | 1.393 (4) |
O1A—C2A | 1.219 (4) | C6B—C7B | 1.385 (4) |
O1B—C2B | 1.220 (3) | C6B—C11B | 1.387 (4) |
O2A—C13A | 1.221 (3) | C7A—C8A | 1.365 (4) |
O2B—C13B | 1.206 (4) | C7A—H7A | 0.9300 |
O3—H1W | 0.86 (6) | C7B—C8B | 1.374 (5) |
O3—H2W | 0.80 (4) | C7B—H7B | 0.9300 |
N1A—C2A | 1.349 (4) | C8A—C9A | 1.370 (5) |
N1A—C11A | 1.400 (4) | C8A—H8A | 0.9300 |
N1A—H1A | 0.87 (4) | C8B—C9B | 1.381 (5) |
N1B—C2B | 1.343 (4) | C8B—H8B | 0.9300 |
N1B—C11B | 1.403 (3) | C9A—C10A | 1.370 (4) |
N1B—H1B | 0.81 (3) | C9A—H9A | 0.9300 |
C2A—C3A | 1.503 (4) | C9B—C10B | 1.376 (5) |
C2B—C3B | 1.508 (4) | C9B—H9B | 0.9300 |
C3A—C4A | 1.516 (4) | C10A—C11A | 1.389 (4) |
C3A—H3A | 0.9700 | C10A—H10A | 0.9300 |
C3A—H3B | 0.9700 | C10B—C11B | 1.378 (4) |
C3B—C4B | 1.527 (5) | C10B—H10B | 0.9300 |
C3B—H3C | 0.9700 | C12A—H12A | 0.9600 |
C3B—H3D | 0.9700 | C12A—H12B | 0.9600 |
C4A—N5A | 1.482 (3) | C12A—H12C | 0.9600 |
C4A—C12A | 1.495 (5) | C12B—H12D | 0.9600 |
C4A—H4A | 0.9800 | C12B—H12E | 0.9600 |
C4B—N5B | 1.469 (4) | C12B—H12F | 0.9600 |
C4B—C12B | 1.515 (5) | C13A—C14A | 1.526 (4) |
C4B—H4B | 0.9800 | C13B—C14B | 1.540 (5) |
N5A—C13A | 1.338 (4) | C14A—H14A | 0.9800 |
N5A—C6A | 1.431 (3) | C14B—H14B | 0.9800 |
H1W—O3—H2W | 106 (5) | C7A—C8A—C9A | 119.9 (3) |
C2A—N1A—C11A | 125.0 (2) | C7A—C8A—H8A | 120.1 |
C2A—N1A—H1A | 117 (2) | C9A—C8A—H8A | 120.1 |
C11A—N1A—H1A | 117 (2) | C7B—C8B—C9B | 119.4 (3) |
C2B—N1B—C11B | 126.2 (3) | C7B—C8B—H8B | 120.3 |
C2B—N1B—H1B | 114 (2) | C9B—C8B—H8B | 120.3 |
C11B—N1B—H1B | 119 (2) | C10A—C9A—C8A | 120.9 (3) |
O1A—C2A—N1A | 120.5 (3) | C10A—C9A—H9A | 119.6 |
O1A—C2A—C3A | 123.0 (3) | C8A—C9A—H9A | 119.6 |
N1A—C2A—C3A | 116.4 (3) | C10B—C9B—C8B | 120.5 (3) |
O1B—C2B—N1B | 121.9 (3) | C10B—C9B—H9B | 119.7 |
O1B—C2B—C3B | 122.0 (3) | C8B—C9B—H9B | 119.7 |
N1B—C2B—C3B | 116.1 (2) | C9A—C10A—C11A | 120.2 (3) |
C2A—C3A—C4A | 115.1 (2) | C9A—C10A—H10A | 119.9 |
C2A—C3A—H3A | 108.5 | C11A—C10A—H10A | 119.9 |
C4A—C3A—H3A | 108.5 | C9B—C10B—C11B | 120.4 (3) |
C2A—C3A—H3B | 108.5 | C9B—C10B—H10B | 119.8 |
C4A—C3A—H3B | 108.5 | C11B—C10B—H10B | 119.8 |
H3A—C3A—H3B | 107.5 | C10A—C11A—C6A | 118.8 (2) |
C2B—C3B—C4B | 113.3 (2) | C10A—C11A—N1A | 120.8 (3) |
C2B—C3B—H3C | 108.9 | C6A—C11A—N1A | 120.4 (2) |
C4B—C3B—H3C | 108.9 | C10B—C11B—C6B | 119.0 (3) |
C2B—C3B—H3D | 108.9 | C10B—C11B—N1B | 120.6 (3) |
C4B—C3B—H3D | 108.9 | C6B—C11B—N1B | 120.3 (2) |
H3C—C3B—H3D | 107.7 | C4A—C12A—H12A | 109.5 |
N5A—C4A—C12A | 111.1 (3) | C4A—C12A—H12B | 109.5 |
N5A—C4A—C3A | 109.3 (2) | H12A—C12A—H12B | 109.5 |
C12A—C4A—C3A | 111.8 (3) | C4A—C12A—H12C | 109.5 |
N5A—C4A—H4A | 108.2 | H12A—C12A—H12C | 109.5 |
C12A—C4A—H4A | 108.2 | H12B—C12A—H12C | 109.5 |
C3A—C4A—H4A | 108.2 | C4B—C12B—H12D | 109.5 |
N5B—C4B—C12B | 110.4 (3) | C4B—C12B—H12E | 109.5 |
N5B—C4B—C3B | 109.4 (2) | H12D—C12B—H12E | 109.5 |
C12B—C4B—C3B | 112.3 (3) | C4B—C12B—H12F | 109.5 |
N5B—C4B—H4B | 108.2 | H12D—C12B—H12F | 109.5 |
C12B—C4B—H4B | 108.2 | H12E—C12B—H12F | 109.5 |
C3B—C4B—H4B | 108.2 | O2A—C13A—N5A | 123.3 (3) |
C13A—N5A—C6A | 123.9 (2) | O2A—C13A—C14A | 119.7 (3) |
C13A—N5A—C4A | 116.8 (2) | N5A—C13A—C14A | 116.9 (2) |
C6A—N5A—C4A | 118.1 (2) | O2B—C13B—N5B | 122.9 (3) |
C13B—N5B—C6B | 122.4 (3) | O2B—C13B—C14B | 120.4 (3) |
C13B—N5B—C4B | 118.4 (2) | N5B—C13B—C14B | 116.5 (3) |
C6B—N5B—C4B | 119.1 (2) | C13A—C14A—Cl2A | 108.8 (2) |
C7A—C6A—C11A | 119.8 (2) | C13A—C14A—Cl1A | 108.0 (2) |
C7A—C6A—N5A | 120.2 (3) | Cl2A—C14A—Cl1A | 110.73 (17) |
C11A—C6A—N5A | 120.0 (2) | C13A—C14A—H14A | 109.7 |
C7B—C6B—C11B | 120.2 (2) | Cl2A—C14A—H14A | 109.7 |
C7B—C6B—N5B | 120.9 (3) | Cl1A—C14A—H14A | 109.7 |
C11B—C6B—N5B | 118.8 (2) | C13B—C14B—Cl2B | 109.4 (3) |
C8A—C7A—C6A | 120.4 (3) | C13B—C14B—Cl1B | 107.7 (2) |
C8A—C7A—H7A | 119.8 | Cl2B—C14B—Cl1B | 109.9 (2) |
C6A—C7A—H7A | 119.8 | C13B—C14B—H14B | 109.9 |
C8B—C7B—C6B | 120.2 (3) | Cl2B—C14B—H14B | 109.9 |
C8B—C7B—H7B | 119.9 | Cl1B—C14B—H14B | 109.9 |
C6B—C7B—H7B | 119.9 | ||
C11A—N1A—C2A—O1A | 173.3 (3) | C7B—C8B—C9B—C10B | −2.6 (5) |
C11A—N1A—C2A—C3A | −9.3 (4) | C8A—C9A—C10A—C11A | 0.6 (5) |
C11B—N1B—C2B—O1B | 177.0 (3) | C8B—C9B—C10B—C11B | 2.3 (5) |
C11B—N1B—C2B—C3B | −5.4 (4) | C9A—C10A—C11A—C6A | −0.2 (4) |
O1A—C2A—C3A—C4A | −106.8 (3) | C9A—C10A—C11A—N1A | 177.8 (3) |
N1A—C2A—C3A—C4A | 75.9 (3) | C7A—C6A—C11A—C10A | −1.4 (4) |
O1B—C2B—C3B—C4B | −107.2 (3) | N5A—C6A—C11A—C10A | −179.7 (2) |
N1B—C2B—C3B—C4B | 75.2 (3) | C7A—C6A—C11A—N1A | −179.4 (2) |
C2A—C3A—C4A—N5A | −40.6 (4) | N5A—C6A—C11A—N1A | 2.2 (4) |
C2A—C3A—C4A—C12A | −164.0 (3) | C2A—N1A—C11A—C10A | 138.6 (3) |
C2B—C3B—C4B—N5B | −46.2 (3) | C2A—N1A—C11A—C6A | −43.4 (4) |
C2B—C3B—C4B—C12B | −169.2 (3) | C9B—C10B—C11B—C6B | 1.6 (4) |
C12A—C4A—N5A—C13A | −90.1 (3) | C9B—C10B—C11B—N1B | 177.9 (3) |
C3A—C4A—N5A—C13A | 146.1 (3) | C7B—C6B—C11B—C10B | −5.2 (4) |
C12A—C4A—N5A—C6A | 78.1 (3) | N5B—C6B—C11B—C10B | 172.3 (3) |
C3A—C4A—N5A—C6A | −45.7 (3) | C7B—C6B—C11B—N1B | 178.5 (3) |
C12B—C4B—N5B—C13B | −102.0 (3) | N5B—C6B—C11B—N1B | −3.9 (4) |
C3B—C4B—N5B—C13B | 134.0 (3) | C2B—N1B—C11B—C10B | 141.2 (3) |
C12B—C4B—N5B—C6B | 83.0 (3) | C2B—N1B—C11B—C6B | −42.6 (4) |
C3B—C4B—N5B—C6B | −41.1 (3) | C6A—N5A—C13A—O2A | −164.1 (3) |
C13A—N5A—C6A—C7A | 58.9 (4) | C4A—N5A—C13A—O2A | 3.3 (4) |
C4A—N5A—C6A—C7A | −108.3 (3) | C6A—N5A—C13A—C14A | 21.3 (4) |
C13A—N5A—C6A—C11A | −122.8 (3) | C4A—N5A—C13A—C14A | −171.3 (3) |
C4A—N5A—C6A—C11A | 70.0 (3) | C6B—N5B—C13B—O2B | −179.7 (3) |
C13B—N5B—C6B—C7B | 75.4 (4) | C4B—N5B—C13B—O2B | 5.4 (4) |
C4B—N5B—C6B—C7B | −109.8 (3) | C6B—N5B—C13B—C14B | 4.5 (4) |
C13B—N5B—C6B—C11B | −102.1 (3) | C4B—N5B—C13B—C14B | −170.4 (3) |
C4B—N5B—C6B—C11B | 72.7 (3) | O2A—C13A—C14A—Cl2A | 53.9 (3) |
C11A—C6A—C7A—C8A | 2.6 (4) | N5A—C13A—C14A—Cl2A | −131.2 (2) |
N5A—C6A—C7A—C8A | −179.0 (3) | O2A—C13A—C14A—Cl1A | −66.3 (3) |
C11B—C6B—C7B—C8B | 4.9 (5) | N5A—C13A—C14A—Cl1A | 108.5 (3) |
N5B—C6B—C7B—C8B | −172.6 (3) | O2B—C13B—C14B—Cl2B | 27.4 (4) |
C6A—C7A—C8A—C9A | −2.3 (5) | N5B—C13B—C14B—Cl2B | −156.7 (2) |
C6B—C7B—C8B—C9B | −1.0 (5) | O2B—C13B—C14B—Cl1B | −92.0 (3) |
C7A—C8A—C9A—C10A | 0.7 (5) | N5B—C13B—C14B—Cl1B | 84.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4A—H4A···O2A | 0.98 | 2.34 | 2.694 (4) | 100 |
C4B—H4B···O2B | 0.98 | 2.31 | 2.715 (4) | 104 |
N1A—H1A···O3 | 0.87 (4) | 2.08 (4) | 2.927 (4) | 164 (3) |
O3—H2W···O1Bi | 0.80 (4) | 2.02 (4) | 2.815 (4) | 173 (4) |
C3A—H3A···O2Bi | 0.97 | 2.60 | 3.038 (4) | 108 |
C8A—H8A···O2Aii | 0.93 | 2.51 | 3.268 (4) | 139 |
C10B—H10B···O2Biii | 0.93 | 2.39 | 3.179 (4) | 143 |
Symmetry codes: (i) −x+2, y−1/2, −z+2; (ii) x−1, y, z; (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C12H12Cl2N2O2·0.5H2O |
Mr | 592.29 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 8.5470 (3), 18.0837 (6), 8.8697 (3) |
β (°) | 95.405 (2) |
V (Å3) | 1364.82 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.26 × 0.24 × 0.22 |
Data collection | |
Diffractometer | Bruker Kappa APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.884, 0.901 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14191, 5599, 4873 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.110, 1.04 |
No. of reflections | 5599 |
No. of parameters | 352 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.62 |
Absolute structure | Flack (1983),2698 Friedel pairs |
Absolute structure parameter | 0.06 (6) |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C4A—H4A···O2A | 0.98 | 2.34 | 2.694 (4) | 100.1 |
C4B—H4B···O2B | 0.98 | 2.31 | 2.715 (4) | 104.0 |
N1A—H1A···O3 | 0.87 (4) | 2.08 (4) | 2.927 (4) | 164 (3) |
O3—H2W···O1Bi | 0.80 (4) | 2.02 (4) | 2.815 (4) | 173 (4) |
C3A—H3A···O2Bi | 0.97 | 2.60 | 3.038 (4) | 107.9 |
C8A—H8A···O2Aii | 0.93 | 2.51 | 3.268 (4) | 138.8 |
C10B—H10B···O2Biii | 0.93 | 2.39 | 3.179 (4) | 142.6 |
Symmetry codes: (i) −x+2, y−1/2, −z+2; (ii) x−1, y, z; (iii) x+1, y, z. |
Acknowledgements
KR thanks Dr Babu Varghese, SAIF, IIT-Madras, India, for his help with the data collection and the management of Kandaswami Kandar's College, Velur, Namakkal, India, for their encouragement to pursue the programme.
References
Albright, J. D., Feich, M. F., Santos, E. G. D., Dusza, J. P., Sum, F.-W., Venkatesan, A. M., Coupet, J., Chan, P. S., Ru, X., Mazandarani, H. & Bailey, T. (1998). J. Med. Chem. 41, 2442–2444. Web of Science CrossRef CAS PubMed Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gringauz, A. (1999). Introduction to Medicinal Chemistry, pp. 578–580. New York: Wiley-VCH. Google Scholar
Lee, J., Gauthier, D. & Rivero, R. A. (1999). J. Org. Chem, 64, 3060–3064. Web of Science CrossRef PubMed CAS Google Scholar
MacDonald, R. L. (2002). Benzodiazepines Mechanisms of Action. In Antiepileptic Drugs, 5th ed., edited by R. H. Levy, R. H. Mattson, B. S. Meldrum & E. Perucca, pp. 179–186. Philadelphia: Lippincott Williams and Wilkins. Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Rahbaek, L., Breinholt, J., Frisvad, J. C. & Christophersen, C. (1999). J. Org. Chem. 64, 1689–1692. Web of Science CrossRef PubMed Google Scholar
Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. 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
Venkatraj, M., Ponnuswamy, S. & Jeyaraman, R. (2008). Indian J. Chem. Sect. B, 47, 129–135. 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.
The anticonvulsant activity of benzodiazepines has been utilized clinically in patients to treat specific seizure types or conditions, i.e., akinetic, myoclonic, absence variant seizures as well as to help terminate status epilepticusor serial seizures (MacDonald, 2002). Benzodiazepines are used for the purpose of hypnotic effects, owing to their less toxic and less severe withdrawal effects when compared with barbiturates (Gringauz, 1999). Benzodiazepines from aspergillus include asperlicin, which is used for treatment of gastrointestinal and central nervous system (CNS) disorders (Rahbaek et al.,1999). The other therapeutic applications (Lee et al., 1999) of benzodiazepines include vasopressin antagonists (Albright et al., 1998). In view of these importance and to ascertain the molecular conformation, crystallographic study of the title compound has been carried out.
The ORTEP diagram of the title compound is shown in Fig.1. There are two crystallographically independent molecules in the asymmetric unit. The benzodiazepine rings in the two molecules adopt a distorted boat conformation. The puckering parameters (Cremer & Pople, 1975) and the asymmetry parameters (Nardelli, 1983) for the ring in molecule A are: q2 = 0.959 (3) Å, q3 = 0.150 (3) Å, ϕ2 = 136.1 (2)°, ϕ3 = 359.8 (1)° and Δ2(C4A)= 8.1 (3)°; for the ring in molecule B are: q2 = 0.962 (3) Å, q3 = 0.168 (3) Å, ϕ2 = 141.4 (2)°, ϕ3 = 5.3 (1)° and Δ2(C4B)= 3.4 (3)°. The sum of the bond angles at N1A(359.0°), N1B(359.2), N5A(358.8) and N5B(359.9°) of the benzodiazepine rings in both the molecules are in accordance with sp2 hybridization.
The crystal packing is controlled by N—H···O, C—H···O and O—H···O types of intermolecular interactions in addition to van der Waals forces. The water molecule connects the molecules A and B through N1A—H1A···O3 and O3—H2W···O1B hydrogen bonds. Thus the combination of N1A—H1A···O3, O3—H2W···O1B and C3A—H3A···O2B hydrogen bonds form a graph set motif of R33(14) dimer (Bernstein et al., 1995) which stabilize the molecules. Atom C8A at (x, y, z) donates a proton to O2A (x - 1, y, z), which forms a C7 one dimensional chain running along a–axis. The intermolecular hydrogen bond C10B—H10B···O2B also connects the molecule into an another C7 chain running along b–axis (Fig. 2).