5-Dichloro­acetyl-4-methyl-2,3,4,5-tetra­hydro-1H-1,5-benzodiazepin-2-one hemihydrate

Ravichandran, K.; Sakthivel, P.; Ponnuswamy, S.; Shalini, M.; Ponnuswamy, M.N.

doi:10.1107/S1600536809036940

5-Dichloroacetyl-4-methyl-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one hemihydrate

K. Ravichandran, P. Sakthivel, S. Ponnuswamy, M. Shalini and M. N. Ponnuswamy

There are two crystallographically independent organic molecules in the asymmetric unit of the title compound, C₁₂H₁₂Cl₂N₂O₂·0.5H₂O. 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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809036940/bt5048sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809036940/bt5048Isup2.hkl Contains datablock I

CCDC reference: 750777

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.045
wR factor = 0.110
Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.90 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C14A
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C14B
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C12 H12 Cl2 N2 O2
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          9

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.48
           From the CIF: _reflns_number_total               5599
           Count of symmetry unique reflns         2913
           Completeness (_total/calc)            192.21%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2686
           Fraction of Friedel pairs measured     0.922
           Are heavy atom types Z>Si present        yes
PLAT917_ALERT_2_G The FCF is likely NOT based on a BASF/TWIN Flack          !
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT791_ALERT_4_G The Model has Chirality at C4A     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C4B     (Verify) ....          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

For the anticonvulsant activity of benzodiazepine, see: MacDonald (2002). For their hynotic 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 top

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).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: 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).

Figures top

	Fig. 1. Perspective view of the molecule showing the thermal ellipsoids are drawn at 30% probability level.
	Fig. 2. The crystal packing of the molecules viewed down c–axis. H atoms not involved in hydrogen bonding have been omitted for clarity.

5-Dichloroacetyl-4-methyl-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one hemihydrate top

Crystal data top

C₁₂H₁₂Cl₂N₂O₂·0.5H₂O	F(000) = 612
M_r = 592.29	D_x = 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

Data collection top

Bruker Kappa APEXII area-detector diffractometer	5599 independent reflections
Radiation source: fine-focus sealed tube	4873 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω and ϕ scans	θ_max = 26.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
T_min = 0.884, T_max = 0.901	k = −22→22
14191 measured reflections	l = −11→10

Refinement top

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(F_o²) + (0.0438P)² + 0.7028P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.006
5599 reflections	Δρ_max = 0.46 e Å⁻³
352 parameters	Δρ_min = −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)

Crystal data top

C₁₂H₁₂Cl₂N₂O₂·0.5H₂O	V = 1364.82 (8) Å³
M_r = 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)°

Data collection top

Bruker Kappa APEXII area-detector diffractometer	5599 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	4873 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.901	R_int = 0.022
14191 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	Δρ_max = 0.46 e Å⁻³
S = 1.04	Δρ_min = −0.62 e Å⁻³
5599 reflections	Absolute structure: Flack (1983),2698 Friedel pairs
352 parameters	Absolute structure parameter: 0.06 (6)
1 restraint

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.884, 0.901
No. of measured, independent and observed [I > 2σ(I)] reflections	14191, 5599, 4873
R_int	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
Δρ_max, Δρ_min (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).