(Z)-1-(2-Chloro­phen­yl)-3-methyl-4-[2-(4-nitro­phen­yl)hydrazin-1-yl­idene]-1H-pyrazol-5(4H)-one

Bustos, C.; Escobar-Fuentealba, A.; Alvarez-Thon, L.; Faundez-Gutierrez, R.; Garland, M.T.

doi:10.1107/S1600536812029790

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages o2351-o2352

https://doi.org/10.1107/S1600536812029790

Open

access

(Z)-1-(2-Chlorophenyl)-3-methyl-4-[2-(4-nitrophenyl)hydrazin-1-ylidene]-1H-pyrazol-5(4H)-one

Carlos Bustos,^a Andrés Escobar-Fuentealba,^a Luis Alvarez-Thon,^b ^* Rodrigo Faundez-Gutierrez ^a and Maria Teresa Garland ^c

^aInstituto de Ciencias Químicas, Universidad Austral de Chile, Avenida Los Robles s/n, Campus Isla Teja, Casilla 567, Valdivia, Chile, ^bDepartamento de Ciencias Físicas, Universidad Andres Bello, Avenida República 220, Santiago de Chile, Chile, and ^cLaboratorio de Cristalografía, Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Avenida Blanco Encalada 2008, Santiago de Chile, Chile
^*Correspondence e-mail: lalvarez@unab.cl

(Received 7 June 2012; accepted 29 June 2012; online 7 July 2012)

There are two independent molecules, A and B, in the asymmetric unit of the title compound, C₁₆H₁₂ClN₅O₃. The relative orientations of the chlorophenyl ring with respect to the pyrazole ring in the two crystallographically independent molecules are different, and their corresponding dihedral angles are −53.3 (2) and 114.09 (18)° in molecules A and B, respectively. There are two strong intramolecular N—H⋯O hydrogen bonds, and two weak intramolecular C—H⋯O and C—H⋯Cl hydrogen bonds. The crystal packing is constructed by weak C—H⋯O and N—H⋯O interactions, and two π–π stacking interactions [centroid–centroid distances = 3.7894 (9) and 3.5719 (10) Å], forming a molecular ladder along the a axis.

Related literature

For synthesis and related literature, see: Abdel-Aziz et al. (2009 ); Bustos et al. (2006 , 2007 , 2009 , 2012 ). For the biological activity of this class of compounds, see: Castagnolo et al. (2009 ); Chauhan et al. (1993 ); El-Hawash et al. (2006 ); Gunasekaran et al. (2011 ); Himly et al. (2003 ); Jolly et al. (1991 ); Kalluraya et al. (2007 ); Kawai et al. (1997 ); Moreau et al. (2008 ); Pasha et al. (2009 ); Radi et al. (2009 ); Singh (1991 ); Wu et al. (2002 ).

Experimental

Crystal data

C₁₆H₁₂ClN₅O₃
M_r = 357.76
Triclinic, $[P \overline 1]$
a = 7.2715 (6) Å
b = 14.7757 (12) Å
c = 15.7609 (12) Å
α = 75.408 (1)°
β = 86.943 (1)°
γ = 79.774 (1)°
V = 1612.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 150 K
0.24 × 0.22 × 0.10 mm

Data collection

Bruker D8 Discover diffractometer with SMART CCD area-detector
13022 measured reflections
6469 independent reflections
4430 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.097
S = 0.91
6469 reflections
461 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H7⋯O1	0.910 (19)	2.084 (18)	2.777 (2)	132.1 (14)
N9—H8⋯O4	0.863 (19)	2.222 (18)	2.8647 (19)	131.2 (16)
C28—H28⋯O2	0.95	2.57	3.265 (2)	130
C15—H15⋯Cl2	0.95	2.93	3.4770 (18)	118
N9—H8⋯O2	0.86 (2)	2.654 (18)	3.266 (2)	129.0 (13)
N9—H8⋯O1ⁱ	0.863 (19)	2.478 (17)	3.094 (2)	128.9 (14)
C4—H4⋯O5ⁱⁱ	0.95	2.37	3.202 (3)	146
C10—H10B⋯O3ⁱⁱⁱ	0.98	2.52	3.392 (3)	148
C10—H10C⋯O6^iv	0.98	2.43	3.175 (3)	133
C32—H32⋯Cl2^v	0.95	2.80	3.6898 (18)	157
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x-1, y+1, z+1; (iii) -x+1, -y+1, -z+1; (iv) x, y, z+1; (v) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2000 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-PC (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812029790/ds2200sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812029790/ds2200Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812029790/ds2200Isup3.cml

checkCIF report

Comment top

In previous papers, we have informed preliminary results about the synthesis of a large library of pyrazoles by reaction of β-diketohydrazones with substituted arylhydrazines (Bustos et al., 2009) and three molecular structures of this type of compounds have been reported (Bustos et al., 2006, 2007, 2012). As a consequence of these studies we have found that α-hydrazo-β-ketoesters yield pyrazolones by reaction with substituted arylhydrazines. Now, we present the synthesis and the molecular structure of the title compound, prepared by reaction of (E)-ethyl 2-(2-(4-nitrophenyl)hydrazinylidene)-3-oxobutanoate with (2-chlorophenyl)hydrazine.

The title compound shown in Fig. 1, crystallizes with two independent molecules in the asymmetric unit, where the chlorophenyl ring display a different orientation with respect to the pyrazole ring in molecules A and B. The corresponding dihedral angles between the chlorophenyl and pyrazole rings, in molecule A and molecule B are -53.3 (2)° and 114.09 (18)° respectively. In the crystal, two strong intramolecular hydrogen bonds (N4—H7···O1 and N9—H8···O4) are observed (Fig. 1, Table 1). As shown in Fig. 1 and Table 1, there are three additional weak intramolecular contacts that link molecules A and B (N9—H8···O2, C15—H15···Cl2 and C28—H28···O2). The atoms in the C1—C6 ring are slightly disordered due to thermal motion.

The partial packing of (I), shows that the two molecules in the asymmetric unit form inversion dimers via a pair of weak C32—H32···Cl2^v bonds (Fig. 2, Table 1). There is another pair of weak C10—H10B···O3ⁱⁱⁱ bonds that form a dimer involving molecule A. In addition, there are two π–π stacking interactions, one with Cg···Cgⁱ distance of 3.6112 (9) Å and the other with Cg···Cgⁱⁱⁱ distance of 3.7894 (9) Å, where Cg is the centroid of the C11–C16 ring. These interactions form a molecular ladder that runs parallel to the a axis (Fig. 3, Table 1). Finally the crystal packing is completed with three weak contacts: C4—H4···O5ⁱⁱ, N9—H8···O1ⁱ and C10—H10C···O6^iv (Table 1). [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) x - 1, y + 1, z + 1; (iii) -x + 1, -y + 1, -z + 1; (iv) x, y, z + 1; (v) -x + 1, -y, -z + 1].

Related literature top

For synthesis and related literature, see: Abdel-Aziz et al. (2009); Bustos et al. (2006, 2007, 2009, 2012). For biological activity, see: Castagnolo et al. (2009); Chauhan et al. (1993); El-Hawash et al. (2006); Gunasekaran et al. (2011); Himly et al. (2003); Jolly et al. (1991); Kalluraya et al. (2007); Kawai et al. (1997); Moreau et al. (2008); Pasha et al. (2009); Radi et al. (2009); Singh (1991); Wu et al. (2002).

Experimental top

In a 100 ml round-bottomed flask were added 2.34 g (8.38 mmole) of (E)-ethyl 2-(2-(4-nitrophenyl)hydrazinylidene)-3-oxobutanoate, 1.60 g (8.94 mmole) 2-(2-chlorophenyl)hydrazine hydrochloride, 5 ml of glacial acetic acid and 50 ml of ethanol. The reaction mixture was magnetically stirred and heated under reflux during 36 h. Then, after cooling at room temperature, the precipitate was filtrated by suction and dried in a vacuum oven at 45°C during 24 h. Yield 78% of crude product. Single crystals suitable for X-ray studies were obtained by recrystallization from tetrahydrofuran. Melting point: 182–183 °C.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-PC (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. The strong intramolecular hydrogen bonds (N9—H8···O4 and N4—H7···O1) are depicted with dashed lines. The weak intramolecular contacts (N9—H8···O2, C15—H15···Cl2 and C28—H28···O2) are depicted with dotted lines.
	Fig. 2. Part of the crystal packing showing the formation of an invertion-related dimer via C12—H32···Cl2^v weak contacts (dashed lines). [Symmetry code: (v) -x + 1, -y, -z + 1].
	Fig. 3. Part of the crystal packing showing the formation of a dimer via C10—H10B···O3ⁱⁱⁱ weak contacts (dashed lines). In addition, there are two π–π stacking interactions (Cg···Cgⁱ and Cg···Cgⁱⁱⁱ) that form a molecular ladder along the a direction, where Cg is the centroid of the C11—C16 ring. [Symmetry codes: (i) -x, -y + 1, -z + 1; (iii) -x + 1, -y + 1, -z + 1].

(Z)-1-(2-Chlorophenyl)-3-methyl-4-[2-(4-nitrophenyl)hydrazin-1- ylidene]-1H-pyrazol-5(4H)-one top

Crystal data top

C₁₆H₁₂ClN₅O₃	Z = 4
M_r = 357.76	F(000) = 736
Triclinic, P1	D_x = 1.474 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2715 (6) Å	Cell parameters from 999 reflections
b = 14.7757 (12) Å	θ = 1.7–26.3°
c = 15.7609 (12) Å	µ = 0.26 mm⁻¹
α = 75.408 (1)°	T = 150 K
β = 86.943 (1)°	Polyhedron, orange
γ = 79.774 (1)°	0.24 × 0.22 × 0.10 mm
V = 1612.7 (2) Å³

Data collection top

Bruker D8 Discover diffractometer with SMART CCD area-detector	4430 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 26.3°, θ_min = 1.7°
φ and ω scans	h = −9→9
13022 measured reflections	k = −18→18
6469 independent reflections	l = −19→18

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ²(F_o²) + (0.0531P)²] where P = (F_o² + 2F_c²)/3
6469 reflections	(Δ/σ)_max = 0.001
461 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₁₆H₁₂ClN₅O₃	γ = 79.774 (1)°
M_r = 357.76	V = 1612.7 (2) Å³
Triclinic, P1	Z = 4
a = 7.2715 (6) Å	Mo Kα radiation
b = 14.7757 (12) Å	µ = 0.26 mm⁻¹
c = 15.7609 (12) Å	T = 150 K
α = 75.408 (1)°	0.24 × 0.22 × 0.10 mm
β = 86.943 (1)°

Data collection top

Bruker D8 Discover diffractometer with SMART CCD area-detector	4430 reflections with I > 2σ(I)
13022 measured reflections	R_int = 0.024
6469 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	Δρ_max = 0.44 e Å⁻³
6469 reflections	Δρ_min = −0.50 e Å⁻³
461 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Cl1	−0.01333 (8)	0.62030 (5)	1.02576 (4)	0.0783 (2)
O1	0.04690 (16)	0.71458 (8)	0.70638 (7)	0.0356 (4)
O2	0.39096 (19)	0.34058 (10)	0.33864 (9)	0.0506 (5)
O3	0.1869 (2)	0.45770 (10)	0.26804 (9)	0.0556 (5)
N1	0.3064 (2)	0.59306 (10)	0.89571 (9)	0.0348 (5)
N2	0.17363 (19)	0.66873 (10)	0.84708 (9)	0.0325 (5)
N3	0.2942 (2)	0.52887 (10)	0.69715 (9)	0.0337 (5)
N4	0.2057 (2)	0.57477 (11)	0.62260 (9)	0.0325 (5)
N5	0.2826 (2)	0.41611 (12)	0.33324 (11)	0.0427 (6)
C1	0.0966 (2)	0.74606 (13)	0.88317 (12)	0.0360 (6)
C2	0.1016 (3)	0.83741 (13)	0.83373 (15)	0.0472 (7)
C3	0.0258 (3)	0.91360 (16)	0.8665 (2)	0.0746 (10)
C4	−0.0534 (4)	0.8998 (2)	0.9486 (3)	0.0919 (14)
C5	−0.0606 (3)	0.8097 (2)	0.99852 (17)	0.0776 (10)
C6	0.0128 (3)	0.73186 (16)	0.96534 (13)	0.0509 (7)
C7	0.1476 (2)	0.65996 (12)	0.76493 (11)	0.0303 (6)
C8	0.2673 (2)	0.56924 (11)	0.76232 (11)	0.0303 (6)
C9	0.3580 (2)	0.53480 (12)	0.84638 (11)	0.0334 (6)
C10	0.4958 (3)	0.44607 (13)	0.87643 (13)	0.0461 (7)
C11	0.2284 (2)	0.53490 (12)	0.55094 (11)	0.0304 (6)
C12	0.1493 (2)	0.58808 (12)	0.47130 (11)	0.0345 (6)
C13	0.1677 (2)	0.54937 (13)	0.39973 (12)	0.0364 (6)
C14	0.2656 (2)	0.45854 (12)	0.40817 (11)	0.0337 (6)
C15	0.3460 (2)	0.40554 (12)	0.48640 (11)	0.0347 (6)
C16	0.3273 (2)	0.44349 (12)	0.55815 (11)	0.0328 (6)
Cl2	0.38569 (6)	0.19954 (3)	0.65477 (3)	0.0401 (2)
O4	0.14560 (16)	0.21654 (9)	0.47521 (7)	0.0372 (4)
O5	0.6349 (2)	0.07315 (9)	−0.02481 (8)	0.0530 (5)
O6	0.5293 (3)	0.22216 (11)	−0.05986 (9)	0.0832 (7)
N6	0.1295 (2)	0.08970 (10)	0.59660 (9)	0.0339 (5)
N7	0.16950 (19)	−0.01115 (10)	0.61679 (9)	0.0338 (5)
N8	0.31059 (18)	0.04899 (10)	0.39600 (9)	0.0291 (5)
N9	0.3055 (2)	0.13105 (11)	0.33806 (9)	0.0293 (5)
N10	0.5588 (2)	0.14595 (11)	−0.00578 (10)	0.0417 (6)
C17	0.0555 (2)	0.13690 (12)	0.66200 (11)	0.0338 (6)
C18	0.1585 (2)	0.19249 (12)	0.69232 (11)	0.0332 (6)
C19	0.0843 (3)	0.23988 (13)	0.75496 (12)	0.0417 (6)
C20	−0.0926 (3)	0.22971 (15)	0.78852 (12)	0.0495 (7)
C21	−0.1929 (3)	0.17270 (16)	0.76076 (12)	0.0503 (7)
C22	−0.1210 (3)	0.12697 (15)	0.69684 (12)	0.0443 (7)
C23	0.1699 (2)	0.13106 (13)	0.51121 (11)	0.0310 (6)
C24	0.2456 (2)	0.04932 (12)	0.47505 (10)	0.0284 (5)
C25	0.2384 (2)	−0.03413 (12)	0.54576 (11)	0.0303 (5)
C26	0.2990 (3)	−0.13494 (12)	0.54268 (12)	0.0379 (6)
C27	0.3760 (2)	0.13371 (12)	0.25320 (10)	0.0263 (5)
C28	0.3623 (2)	0.22144 (12)	0.19267 (11)	0.0306 (5)
C29	0.4246 (2)	0.22550 (12)	0.10800 (11)	0.0324 (6)
C30	0.4999 (2)	0.14203 (12)	0.08492 (11)	0.0306 (6)
C31	0.5177 (2)	0.05511 (12)	0.14479 (11)	0.0316 (6)
C32	0.4578 (2)	0.05063 (12)	0.22955 (11)	0.0302 (6)
H2	0.15770	0.84740	0.77700	0.0570*
H3	0.02820	0.97620	0.83220	0.0900*
H4	−0.10380	0.95290	0.97120	0.1100*
H5	−0.11540	0.80060	1.05550	0.0930*
H7	0.135 (2)	0.6333 (13)	0.6166 (11)	0.040 (5)*
H10A	0.53790	0.44200	0.93550	0.0690*
H10B	0.60330	0.44670	0.83620	0.0690*
H10C	0.43690	0.39110	0.87740	0.0690*
H12	0.08310	0.65070	0.46640	0.0410*
H13	0.11360	0.58480	0.34520	0.0440*
H15	0.41360	0.34340	0.49060	0.0420*
H16	0.38160	0.40760	0.61240	0.0390*
H8	0.252 (2)	0.1836 (13)	0.3497 (12)	0.040 (5)*
H19	0.15420	0.27900	0.77470	0.0500*
H20	−0.14490	0.26260	0.83110	0.0590*
H21	−0.31260	0.16450	0.78560	0.0600*
H22	−0.19250	0.08870	0.67670	0.0530*
H26A	0.27280	−0.17660	0.59930	0.0570*
H26B	0.43350	−0.14620	0.53010	0.0570*
H26C	0.23080	−0.14830	0.49650	0.0570*
H28	0.31030	0.27800	0.20970	0.0370*
H29	0.41610	0.28480	0.06590	0.0390*
H31	0.57090	−0.00110	0.12750	0.0380*
H32	0.47180	−0.00860	0.27180	0.0360*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0652 (4)	0.1022 (5)	0.0431 (3)	0.0082 (3)	0.0134 (3)	0.0083 (3)
O1	0.0404 (7)	0.0362 (7)	0.0283 (7)	−0.0009 (6)	−0.0055 (6)	−0.0072 (6)
O2	0.0640 (10)	0.0469 (9)	0.0502 (9)	−0.0167 (7)	0.0170 (7)	−0.0278 (7)
O3	0.0732 (10)	0.0675 (10)	0.0328 (8)	−0.0217 (8)	−0.0005 (7)	−0.0177 (7)
N1	0.0385 (9)	0.0318 (8)	0.0303 (8)	0.0003 (7)	−0.0039 (7)	−0.0042 (7)
N2	0.0385 (8)	0.0304 (8)	0.0274 (8)	0.0003 (6)	−0.0035 (7)	−0.0087 (6)
N3	0.0362 (8)	0.0349 (8)	0.0302 (8)	−0.0073 (7)	0.0034 (7)	−0.0083 (7)
N4	0.0374 (9)	0.0304 (9)	0.0294 (8)	−0.0020 (7)	0.0016 (7)	−0.0101 (7)
N5	0.0531 (11)	0.0469 (10)	0.0357 (10)	−0.0223 (9)	0.0117 (8)	−0.0168 (8)
C1	0.0342 (10)	0.0395 (11)	0.0364 (11)	0.0042 (8)	−0.0118 (8)	−0.0180 (9)
C2	0.0425 (12)	0.0357 (11)	0.0646 (14)	0.0002 (9)	−0.0204 (10)	−0.0152 (10)
C3	0.0645 (17)	0.0444 (14)	0.122 (2)	0.0115 (12)	−0.0504 (17)	−0.0375 (16)
C4	0.0711 (19)	0.093 (2)	0.129 (3)	0.0405 (16)	−0.0581 (19)	−0.085 (2)
C5	0.0541 (15)	0.123 (2)	0.0606 (16)	0.0365 (16)	−0.0269 (12)	−0.0621 (18)
C6	0.0436 (12)	0.0706 (15)	0.0355 (11)	0.0138 (10)	−0.0139 (9)	−0.0212 (11)
C7	0.0329 (10)	0.0316 (10)	0.0269 (9)	−0.0078 (8)	0.0020 (8)	−0.0071 (8)
C8	0.0337 (10)	0.0292 (9)	0.0286 (10)	−0.0057 (8)	0.0036 (7)	−0.0087 (8)
C9	0.0360 (10)	0.0316 (10)	0.0300 (10)	−0.0042 (8)	0.0028 (8)	−0.0046 (8)
C10	0.0519 (12)	0.0399 (11)	0.0392 (11)	0.0053 (9)	−0.0015 (9)	−0.0055 (9)
C11	0.0322 (10)	0.0320 (10)	0.0304 (10)	−0.0096 (8)	0.0061 (7)	−0.0122 (8)
C12	0.0350 (10)	0.0322 (10)	0.0359 (10)	−0.0047 (8)	0.0009 (8)	−0.0084 (8)
C13	0.0402 (11)	0.0401 (11)	0.0293 (10)	−0.0107 (9)	0.0024 (8)	−0.0072 (8)
C14	0.0390 (10)	0.0369 (10)	0.0307 (10)	−0.0154 (8)	0.0086 (8)	−0.0143 (8)
C15	0.0382 (10)	0.0291 (10)	0.0376 (11)	−0.0070 (8)	0.0085 (8)	−0.0107 (8)
C16	0.0364 (10)	0.0314 (10)	0.0303 (10)	−0.0061 (8)	0.0026 (8)	−0.0072 (8)
Cl2	0.0379 (3)	0.0390 (3)	0.0408 (3)	−0.0072 (2)	−0.0009 (2)	−0.0045 (2)
O4	0.0464 (8)	0.0364 (7)	0.0264 (7)	−0.0047 (6)	0.0047 (6)	−0.0062 (6)
O5	0.0758 (10)	0.0461 (8)	0.0401 (8)	−0.0067 (7)	0.0197 (7)	−0.0230 (7)
O6	0.1420 (16)	0.0506 (10)	0.0322 (9)	0.0191 (10)	0.0312 (9)	0.0043 (8)
N6	0.0407 (9)	0.0369 (9)	0.0240 (8)	−0.0084 (7)	0.0068 (7)	−0.0078 (7)
N7	0.0346 (8)	0.0387 (9)	0.0279 (8)	−0.0092 (7)	0.0018 (6)	−0.0063 (7)
N8	0.0271 (8)	0.0363 (8)	0.0240 (8)	−0.0066 (6)	−0.0010 (6)	−0.0068 (7)
N9	0.0341 (8)	0.0292 (8)	0.0238 (8)	−0.0014 (7)	0.0032 (6)	−0.0084 (7)
N10	0.0516 (10)	0.0410 (10)	0.0314 (9)	−0.0039 (8)	0.0125 (8)	−0.0125 (8)
C17	0.0376 (10)	0.0413 (11)	0.0204 (9)	−0.0029 (8)	0.0022 (7)	−0.0067 (8)
C18	0.0359 (10)	0.0345 (10)	0.0241 (9)	0.0012 (8)	−0.0012 (8)	−0.0028 (8)
C19	0.0504 (12)	0.0427 (11)	0.0298 (10)	0.0011 (9)	−0.0070 (9)	−0.0099 (9)
C20	0.0506 (13)	0.0653 (14)	0.0271 (11)	0.0139 (11)	−0.0031 (9)	−0.0173 (10)
C21	0.0360 (11)	0.0856 (16)	0.0260 (10)	−0.0011 (11)	0.0032 (8)	−0.0151 (11)
C22	0.0363 (11)	0.0712 (14)	0.0270 (10)	−0.0124 (10)	0.0019 (8)	−0.0134 (10)
C23	0.0306 (9)	0.0399 (11)	0.0225 (9)	−0.0065 (8)	0.0011 (7)	−0.0078 (8)
C24	0.0256 (9)	0.0367 (10)	0.0234 (9)	−0.0060 (7)	0.0007 (7)	−0.0083 (8)
C25	0.0267 (9)	0.0401 (10)	0.0253 (9)	−0.0106 (8)	−0.0007 (7)	−0.0067 (8)
C26	0.0420 (11)	0.0385 (11)	0.0329 (10)	−0.0102 (9)	0.0015 (8)	−0.0063 (9)
C27	0.0256 (9)	0.0338 (9)	0.0213 (9)	−0.0044 (7)	0.0009 (7)	−0.0107 (7)
C28	0.0361 (10)	0.0284 (9)	0.0273 (9)	−0.0013 (8)	0.0018 (8)	−0.0104 (8)
C29	0.0388 (10)	0.0298 (10)	0.0259 (9)	−0.0026 (8)	0.0034 (8)	−0.0050 (8)
C30	0.0347 (10)	0.0344 (10)	0.0234 (9)	−0.0057 (8)	0.0051 (7)	−0.0098 (8)
C31	0.0362 (10)	0.0293 (10)	0.0312 (10)	−0.0043 (8)	0.0060 (8)	−0.0133 (8)
C32	0.0344 (10)	0.0265 (9)	0.0286 (10)	−0.0044 (7)	0.0020 (7)	−0.0057 (8)

Geometric parameters (Å, º) top

Cl1—C6	1.721 (2)	C14—C15	1.380 (2)
Cl2—C18	1.7367 (16)	C15—C16	1.374 (2)
O1—C7	1.235 (2)	C2—H2	0.9500
O2—N5	1.233 (2)	C3—H3	0.9500
O3—N5	1.235 (2)	C4—H4	0.9500
O4—C23	1.232 (2)	C5—H5	0.9500
O5—N10	1.219 (2)	C10—H10A	0.9800
O6—N10	1.221 (2)	C10—H10B	0.9800
N1—C9	1.295 (2)	C10—H10C	0.9800
N1—N2	1.426 (2)	C12—H12	0.9500
N2—C1	1.417 (2)	C13—H13	0.9500
N2—C7	1.360 (2)	C15—H15	0.9500
N3—C8	1.302 (2)	C16—H16	0.9500
N3—N4	1.334 (2)	C17—C22	1.386 (3)
N4—C11	1.390 (2)	C17—C18	1.385 (2)
N5—C14	1.461 (2)	C18—C19	1.383 (3)
N4—H7	0.910 (19)	C19—C20	1.383 (3)
N6—C23	1.371 (2)	C20—C21	1.368 (3)
N6—N7	1.423 (2)	C21—C22	1.381 (3)
N6—C17	1.417 (2)	C23—C24	1.471 (3)
N7—C25	1.300 (2)	C24—C25	1.446 (2)
N8—N9	1.317 (2)	C25—C26	1.489 (3)
N8—C24	1.310 (2)	C27—C32	1.396 (2)
N9—C27	1.400 (2)	C27—C28	1.393 (2)
N10—C30	1.460 (2)	C28—C29	1.376 (2)
N9—H8	0.863 (19)	C29—C30	1.385 (3)
C1—C6	1.385 (3)	C30—C31	1.378 (2)
C1—C2	1.384 (3)	C31—C32	1.372 (2)
C2—C3	1.371 (3)	C19—H19	0.9500
C3—C4	1.370 (5)	C20—H20	0.9500
C4—C5	1.374 (5)	C21—H21	0.9500
C5—C6	1.392 (4)	C22—H22	0.9500
C7—C8	1.472 (2)	C26—H26A	0.9800
C8—C9	1.443 (2)	C26—H26B	0.9800
C9—C10	1.490 (3)	C26—H26C	0.9800
C11—C16	1.393 (2)	C28—H28	0.9500
C11—C12	1.394 (2)	C29—H29	0.9500
C12—C13	1.378 (3)	C31—H31	0.9500
C13—C14	1.381 (3)	C32—H32	0.9500

Cl1···N1	3.0568 (16)	C12···C14ⁱⁱⁱ	3.557 (2)
Cl1···N2	3.0352 (15)	C13···C12ⁱⁱⁱ	3.557 (2)
Cl2···O4	3.3366 (12)	C13···C11ⁱⁱⁱ	3.316 (2)
Cl2···N6	2.9917 (16)	C14···C12ⁱⁱⁱ	3.557 (2)
Cl2···C15	3.4770 (18)	C15···O4	3.417 (2)
Cl2···C16	3.5002 (19)	C15···Cl2	3.4770 (18)
Cl2···C21ⁱ	3.481 (2)	C15···C11^iv	3.348 (2)
Cl2···C22ⁱ	3.604 (2)	C15···C16^iv	3.468 (2)
Cl2···C23	3.2713 (18)	C16···C16^iv	3.451 (2)
Cl2···H15	2.9300	C16···Cl2	3.5002 (19)
Cl2···H16	2.9700	C16···C15^iv	3.468 (2)
Cl2···H21ⁱ	2.9800	C18···O4	3.355 (2)
Cl2···H32ⁱⁱ	2.8000	C20···C5^xiv	3.468 (3)
O1···C2	3.108 (2)	C21···Cl2^xvi	3.481 (2)
O1···O3ⁱⁱⁱ	3.2371 (19)	C22···Cl2^xvi	3.604 (2)
O1···N3	3.0341 (19)	C23···C26^xii	3.545 (3)
O1···N4	2.777 (2)	C23···Cl2	3.2713 (18)
O1···C28ⁱⁱⁱ	3.396 (2)	C25···N8ⁱⁱ	3.407 (2)
O1···O4ⁱⁱⁱ	3.1049 (16)	C26···C23^xii	3.545 (3)
O1···N9ⁱⁱⁱ	3.094 (2)	C28···O1ⁱⁱⁱ	3.396 (2)
O2···N9	3.266 (2)	C28···C1ⁱⁱⁱ	3.516 (2)
O2···C8^iv	3.189 (2)	C28···O2	3.265 (2)
O2···C28	3.265 (2)	C29···C1^iv	3.594 (2)
O2···O4	3.1526 (18)	C29···C2^iv	3.514 (3)
O2···N3^iv	3.188 (2)	C29···C6ⁱⁱⁱ	3.341 (3)
O3···C10^iv	3.392 (3)	C29···C5ⁱⁱⁱ	3.391 (3)
O3···O1ⁱⁱⁱ	3.2371 (19)	C30···C3^iv	3.481 (3)
O3···C7ⁱⁱⁱ	3.362 (2)	C30···C2^iv	3.322 (3)
O4···C15	3.417 (2)	C30···C5ⁱⁱⁱ	3.407 (3)
O4···O1ⁱⁱⁱ	3.1049 (16)	C30···C4ⁱⁱⁱ	3.502 (3)
O4···Cl2	3.3366 (12)	C31···O5^v	3.343 (2)
O4···N8	3.077 (2)	C31···C3^iv	3.421 (3)
O4···O2	3.1526 (18)	C31···C2^iv	3.497 (3)
O4···C18	3.355 (2)	C5···H20^xiv	3.0000
O4···N9	2.8647 (19)	C7···H7	2.476 (17)
O5···C31^v	3.343 (2)	C7···H2	2.8400
O5···C4^vi	3.202 (3)	C19···H13ⁱⁱⁱ	2.8500
O5···O5^v	3.102 (2)	C19···H5^xiv	2.9100
O6···C10^vii	3.175 (3)	C20···H13ⁱⁱⁱ	2.9900
O1···H7	2.084 (18)	C20···H5^xiv	2.8500
O1···H28ⁱⁱⁱ	2.8500	C21···H3^xi	3.0300
O1···H26A^viii	2.7200	C22···H3^xi	2.7700
O1···H8ⁱⁱⁱ	2.478 (17)	C23···H8	2.539 (18)
O1···H2	2.7400	C23···H26C^xii	2.8900
O2···H15	2.4200	C23···H26Bⁱⁱ	2.9600
O2···H8	2.654 (18)	C24···H26Bⁱⁱ	2.9300
O2···H28	2.5700	H2···O1	2.7400
O3···H10B^iv	2.5200	H2···N7^viii	2.8500
O3···H13	2.4500	H2···C7	2.8400
O4···H12ⁱⁱⁱ	2.6500	H3···C21^viii	3.0300
O4···H8	2.222 (18)	H3···C22^viii	2.7700
O4···H7ⁱⁱⁱ	2.876 (17)	H4···O5^xiii	2.3700
O5···H4^vi	2.3700	H4···H4^xvii	2.5600
O5···H31	2.4300	H5···C19^xiv	2.9100
O5···H31^v	2.7700	H5···C20^xiv	2.8500
O6···H10C^vii	2.4300	H5···H20^xiv	2.5600
O6···H20^ix	2.9100	H7···O1	2.084 (18)
O6···H21^ix	2.8900	H7···O4ⁱⁱⁱ	2.876 (17)
O6···H29	2.4400	H7···C7	2.476 (17)
N1···Cl1	3.0568 (16)	H7···H12	2.3600
N2···Cl1	3.0352 (15)	H8···O4	2.222 (18)
N3···O2^iv	3.188 (2)	H8···O1ⁱⁱⁱ	2.478 (17)
N3···O1	3.0341 (19)	H8···C23	2.539 (18)
N4···O1	2.777 (2)	H8···H28	2.3600
N6···Cl2	2.9917 (16)	H8···O2	2.654 (18)
N8···C25ⁱⁱ	3.407 (2)	H10A···N1^x	2.8400
N8···O4	3.077 (2)	H10B···O3^iv	2.5200
N9···O1ⁱⁱⁱ	3.094 (2)	H10C···O6^xv	2.4300
N9···O2	3.266 (2)	H12···H7	2.3600
N9···O4	2.8647 (19)	H12···O4ⁱⁱⁱ	2.6500
N1···H10A^x	2.8400	H13···O3	2.4500
N3···H16	2.4700	H13···C19ⁱⁱⁱ	2.8500
N7···H2^xi	2.8500	H13···C20ⁱⁱⁱ	2.9900
N8···H22^xii	2.8400	H15···Cl2	2.9300
N8···H32	2.4800	H15···O2	2.4200
C1···C28ⁱⁱⁱ	3.516 (2)	H16···Cl2	2.9700
C1···C29^iv	3.594 (2)	H16···N3	2.4700
C2···O1	3.108 (2)	H20···O6^xviii	2.9100
C2···C29^iv	3.514 (3)	H20···C5^xiv	3.0000
C2···C30^iv	3.322 (3)	H20···H5^xiv	2.5600
C2···C31^iv	3.497 (3)	H21···Cl2^xvi	2.9800
C3···C31^iv	3.421 (3)	H21···O6^xviii	2.8900
C3···C30^iv	3.481 (3)	H22···N8^xii	2.8400
C4···O5^xiii	3.202 (3)	H22···H32^xii	2.5300
C4···C30ⁱⁱⁱ	3.502 (3)	H26A···O1^xi	2.7200
C5···C29ⁱⁱⁱ	3.391 (3)	H26B···C23ⁱⁱ	2.9600
C5···C20^xiv	3.468 (3)	H26B···C24ⁱⁱ	2.9300
C5···C30ⁱⁱⁱ	3.407 (3)	H26C···C23^xii	2.8900
C6···C29ⁱⁱⁱ	3.341 (3)	H28···O2	2.5700
C7···O3ⁱⁱⁱ	3.362 (2)	H28···H8	2.3600
C8···O2^iv	3.189 (2)	H28···O1ⁱⁱⁱ	2.8500
C10···O6^xv	3.175 (3)	H29···O6	2.4400
C10···O3^iv	3.392 (3)	H31···O5	2.4300
C11···C15^iv	3.348 (2)	H31···O5^v	2.7700
C11···C13ⁱⁱⁱ	3.316 (2)	H32···N8	2.4800
C12···C13ⁱⁱⁱ	3.557 (2)	H32···Cl2ⁱⁱ	2.8000
C12···C12ⁱⁱⁱ	3.594 (2)	H32···H22^xii	2.5300

N2—N1—C9	106.83 (13)	H10A—C10—H10B	109.00
N1—N2—C1	119.93 (13)	H10A—C10—H10C	109.00
N1—N2—C7	112.75 (14)	C9—C10—H10A	110.00
C1—N2—C7	127.10 (15)	C11—C12—H12	120.00
N4—N3—C8	117.15 (15)	C13—C12—H12	120.00
N3—N4—C11	119.70 (15)	C14—C13—H13	120.00
O2—N5—O3	123.58 (17)	C12—C13—H13	120.00
O2—N5—C14	118.30 (15)	C14—C15—H15	120.00
O3—N5—C14	118.12 (16)	C16—C15—H15	120.00
C11—N4—H7	118.9 (11)	C11—C16—H16	120.00
N3—N4—H7	121.4 (11)	C15—C16—H16	120.00
C17—N6—C23	126.83 (15)	C18—C17—C22	119.34 (16)
N7—N6—C23	112.99 (14)	N6—C17—C22	119.98 (16)
N7—N6—C17	120.19 (13)	N6—C17—C18	120.68 (14)
N6—N7—C25	106.64 (13)	Cl2—C18—C17	120.02 (13)
N9—N8—C24	118.23 (15)	Cl2—C18—C19	119.47 (14)
N8—N9—C27	119.93 (15)	C17—C18—C19	120.47 (16)
O5—N10—O6	122.44 (16)	C18—C19—C20	119.38 (18)
O5—N10—C30	118.93 (15)	C19—C20—C21	120.46 (19)
O6—N10—C30	118.63 (16)	C20—C21—C22	120.3 (2)
N8—N9—H8	121.6 (12)	C17—C22—C21	120.0 (2)
C27—N9—H8	118.3 (12)	O4—C23—N6	127.09 (17)
C2—C1—C6	119.81 (19)	O4—C23—C24	129.70 (15)
N2—C1—C2	118.81 (16)	N6—C23—C24	103.21 (15)
N2—C1—C6	121.35 (18)	N8—C24—C23	128.65 (16)
C1—C2—C3	120.1 (2)	C23—C24—C25	106.06 (14)
C2—C3—C4	120.3 (3)	N8—C24—C25	125.28 (16)
C3—C4—C5	120.5 (3)	N7—C25—C26	121.74 (16)
C4—C5—C6	119.7 (3)	C24—C25—C26	127.17 (15)
C1—C6—C5	119.6 (2)	N7—C25—C24	111.09 (15)
Cl1—C6—C5	118.78 (17)	C28—C27—C32	120.65 (15)
Cl1—C6—C1	121.59 (17)	N9—C27—C28	118.40 (16)
O1—C7—C8	128.04 (16)	N9—C27—C32	120.95 (15)
O1—C7—N2	128.49 (16)	C27—C28—C29	119.44 (16)
N2—C7—C8	103.47 (14)	C28—C29—C30	119.11 (16)
C7—C8—C9	105.96 (14)	N10—C30—C31	119.01 (16)
N3—C8—C7	127.95 (15)	N10—C30—C29	119.11 (15)
N3—C8—C9	126.04 (15)	C29—C30—C31	121.87 (16)
N1—C9—C10	121.84 (15)	C30—C31—C32	119.33 (16)
C8—C9—C10	127.23 (16)	C27—C32—C31	119.53 (16)
N1—C9—C8	110.92 (15)	C18—C19—H19	120.00
N4—C11—C16	120.98 (15)	C20—C19—H19	120.00
C12—C11—C16	120.35 (16)	C19—C20—H20	120.00
N4—C11—C12	118.67 (16)	C21—C20—H20	120.00
C11—C12—C13	119.63 (16)	C20—C21—H21	120.00
C12—C13—C14	119.22 (16)	C22—C21—H21	120.00
N5—C14—C15	118.64 (16)	C17—C22—H22	120.00
C13—C14—C15	121.69 (16)	C21—C22—H22	120.00
N5—C14—C13	119.66 (15)	C25—C26—H26A	109.00
C14—C15—C16	119.39 (16)	C25—C26—H26B	109.00
C11—C16—C15	119.71 (16)	C25—C26—H26C	109.00
C1—C2—H2	120.00	H26A—C26—H26B	109.00
C3—C2—H2	120.00	H26A—C26—H26C	110.00
C4—C3—H3	120.00	H26B—C26—H26C	109.00
C2—C3—H3	120.00	C27—C28—H28	120.00
C5—C4—H4	120.00	C29—C28—H28	120.00
C3—C4—H4	120.00	C28—C29—H29	120.00
C4—C5—H5	120.00	C30—C29—H29	120.00
C6—C5—H5	120.00	C30—C31—H31	120.00
C9—C10—H10C	109.00	C32—C31—H31	120.00
C9—C10—H10B	109.00	C27—C32—H32	120.00
H10B—C10—H10C	110.00	C31—C32—H32	120.00

C9—N1—N2—C1	−177.60 (14)	C3—C4—C5—C6	−0.1 (4)
C9—N1—N2—C7	−2.68 (18)	C4—C5—C6—Cl1	−175.3 (2)
N2—N1—C9—C10	−179.42 (15)	C4—C5—C6—C1	1.6 (3)
N2—N1—C9—C8	1.49 (18)	N2—C7—C8—C9	−1.58 (16)
C7—N2—C1—C2	−45.7 (2)	N2—C7—C8—N3	−178.96 (16)
N1—N2—C1—C6	−53.3 (2)	O1—C7—C8—N3	1.4 (3)
C7—N2—C1—C6	132.57 (19)	O1—C7—C8—C9	178.79 (16)
C1—N2—C7—C8	177.05 (15)	N3—C8—C9—N1	177.47 (16)
N1—N2—C7—O1	−177.80 (16)	N3—C8—C9—C10	−1.6 (3)
C1—N2—C7—O1	−3.3 (3)	C7—C8—C9—C10	−179.01 (16)
N1—N2—C1—C2	128.42 (18)	C7—C8—C9—N1	0.03 (19)
N1—N2—C7—C8	2.58 (17)	N4—C11—C12—C13	−179.02 (15)
C8—N3—N4—C11	−179.70 (15)	N4—C11—C16—C15	179.38 (15)
N4—N3—C8—C7	1.0 (2)	C12—C11—C16—C15	−0.3 (2)
N4—N3—C8—C9	−175.90 (15)	C16—C11—C12—C13	0.7 (2)
N3—N4—C11—C16	6.4 (2)	C11—C12—C13—C14	−0.4 (2)
N3—N4—C11—C12	−173.89 (15)	C12—C13—C14—N5	178.73 (14)
O2—N5—C14—C15	−10.7 (2)	C12—C13—C14—C15	−0.2 (2)
O3—N5—C14—C13	−10.0 (2)	C13—C14—C15—C16	0.5 (2)
O2—N5—C14—C13	170.37 (15)	N5—C14—C15—C16	−178.37 (14)
O3—N5—C14—C15	168.98 (15)	C14—C15—C16—C11	−0.3 (2)
N7—N6—C17—C22	−65.3 (2)	C22—C17—C18—Cl2	175.76 (14)
C23—N6—C17—C18	−66.0 (2)	N6—C17—C18—Cl2	−3.7 (2)
C23—N6—C17—C22	114.6 (2)	C22—C17—C18—C19	−1.8 (3)
C17—N6—C23—C24	178.77 (15)	N6—C17—C18—C19	178.76 (16)
N7—N6—C17—C18	114.09 (18)	C18—C17—C22—C21	0.4 (3)
N7—N6—C23—O4	178.25 (15)	N6—C17—C22—C21	179.79 (18)
C17—N6—C23—O4	−1.7 (3)	C17—C18—C19—C20	1.3 (3)
N7—N6—C23—C24	−1.28 (17)	Cl2—C18—C19—C20	−176.25 (15)
C23—N6—N7—C25	1.31 (18)	C18—C19—C20—C21	0.6 (3)
C17—N6—N7—C25	−178.74 (14)	C19—C20—C21—C22	−2.1 (3)
N6—N7—C25—C24	−0.71 (17)	C20—C21—C22—C17	1.6 (3)
N6—N7—C25—C26	179.30 (15)	O4—C23—C24—N8	2.4 (3)
C24—N8—N9—C27	179.13 (14)	O4—C23—C24—C25	−178.71 (16)
N9—N8—C24—C25	179.09 (14)	N6—C23—C24—N8	−178.13 (16)
N9—N8—C24—C23	−2.2 (2)	N6—C23—C24—C25	0.80 (16)
N8—N9—C27—C28	177.73 (14)	N8—C24—C25—N7	178.93 (15)
N8—N9—C27—C32	−2.2 (2)	N8—C24—C25—C26	−1.1 (3)
O5—N10—C30—C31	−5.4 (2)	C23—C24—C25—N7	−0.05 (18)
O5—N10—C30—C29	175.80 (15)	C23—C24—C25—C26	179.94 (16)
O6—N10—C30—C29	−4.4 (2)	N9—C27—C28—C29	−177.71 (14)
O6—N10—C30—C31	174.38 (17)	C32—C27—C28—C29	2.2 (2)
N2—C1—C6—C5	179.79 (18)	N9—C27—C32—C31	176.99 (14)
C2—C1—C6—Cl1	174.84 (16)	C28—C27—C32—C31	−2.9 (2)
C6—C1—C2—C3	0.8 (3)	C27—C28—C29—C30	−0.1 (2)
C2—C1—C6—C5	−2.0 (3)	C28—C29—C30—N10	177.47 (14)
N2—C1—C6—Cl1	−3.4 (3)	C28—C29—C30—C31	−1.3 (2)
N2—C1—C2—C3	179.09 (19)	N10—C30—C31—C32	−178.19 (14)
C1—C2—C3—C4	0.7 (4)	C29—C30—C31—C32	0.6 (2)
C2—C3—C4—C5	−1.1 (4)	C30—C31—C32—C27	1.5 (2)

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z; (vi) x+1, y−1, z−1; (vii) x, y, z−1; (viii) x, y+1, z; (ix) x+1, y, z−1; (x) −x+1, −y+1, −z+2; (xi) x, y−1, z; (xii) −x, −y, −z+1; (xiii) x−1, y+1, z+1; (xiv) −x, −y+1, −z+2; (xv) x, y, z+1; (xvi) x−1, y, z; (xvii) −x, −y+2, −z+2; (xviii) x−1, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H7···O1	0.910 (19)	2.084 (18)	2.777 (2)	132.1 (14)
N9—H8···O4	0.863 (19)	2.222 (18)	2.8647 (19)	131.2 (16)
C28—H28···O2	0.95	2.57	3.265 (2)	130
C15—H15···Cl2	0.95	2.93	3.4770 (18)	118
N9—H8···O2	0.86 (2)	2.654 (18)	3.266 (2)	129.0 (13)
N9—H8···O1ⁱⁱⁱ	0.863 (19)	2.478 (17)	3.094 (2)	128.9 (14)
C4—H4···O5^xiii	0.95	2.37	3.202 (3)	146
C10—H10B···O3^iv	0.98	2.52	3.392 (3)	148
C10—H10C···O6^xv	0.98	2.43	3.175 (3)	133
C32—H32···Cl2ⁱⁱ	0.95	2.80	3.6898 (18)	157

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (xiii) x−1, y+1, z+1; (xv) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂ClN₅O₃
M_r	357.76
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	7.2715 (6), 14.7757 (12), 15.7609 (12)
α, β, γ (°)	75.408 (1), 86.943 (1), 79.774 (1)
V (Å³)	1612.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.24 × 0.22 × 0.10

Data collection
Diffractometer	Bruker D8 Discover diffractometer with SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13022, 6469, 4430
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.097, 0.91
No. of reflections	6469
No. of parameters	461
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.50

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-PC (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H7···O1	0.910 (19)	2.084 (18)	2.777 (2)	132.1 (14)
N9—H8···O4	0.863 (19)	2.222 (18)	2.8647 (19)	131.2 (16)
C28—H28···O2	0.95	2.57	3.265 (2)	130
C15—H15···Cl2	0.95	2.93	3.4770 (18)	118
N9—H8···O2	0.86 (2)	2.654 (18)	3.266 (2)	129.0 (13)
N9—H8···O1ⁱ	0.863 (19)	2.478 (17)	3.094 (2)	128.9 (14)
C4—H4···O5ⁱⁱ	0.95	2.37	3.202 (3)	146
C10—H10B···O3ⁱⁱⁱ	0.98	2.52	3.392 (3)	148
C10—H10C···O6^iv	0.98	2.43	3.175 (3)	133
C32—H32···Cl2^v	0.95	2.80	3.6898 (18)	157

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y+1, z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y, z+1; (v) −x+1, −y, −z+1.

Acknowledgements

The authors thank the Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT; grant Nos. 11100446 and 1080269) and the Universidad Andrés Bello (grant No. DI-27-12-R) for financial assistance.

References

Abdel-Aziz, M., Abuo-Rahma, G. E.-D. A. & Hassan, A. A. (2009). Eur. J. Med. Chem. 44, 3480–3487. Web of Science PubMed CAS Google Scholar
Bruker (2000). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bustos, C., Pérez-Cerda, M., Alvarez-Thon, L., Barrales-Salcedo, E. & Garland, M. T. (2012). Acta Cryst. E68, o353–o354. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bustos, C., Sánchez, C., Schott, E., Alvarez-Thon, L. & Fuentealba, M. (2007). Acta Cryst. E63, o1138–o1139. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bustos, C., Schott, E., Mac-Leod-Carey, D. A., Ibañez, A. & Alvarez-Thon, L. (2006). Acta Cryst. E62, o2499–o2501. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bustos, C., Schott, E., Rios, M., Sanchez, C. & Carcamo, J. G. (2009). J. Chil. Chem. Soc. 54, 267–268. CrossRef CAS Google Scholar
Castagnolo, D., Manetti, F., Radi, M., Bechi, B., Pagano, M., De Logu, A., Meleddu, R., Saddi, M. & Botta, M. (2009). Bioorg. Med. Chem. 17, 5716–5721. Web of Science CrossRef PubMed CAS Google Scholar
Chauhan, P. M. S., Singh, S. & Chatterjee, R. K. (1993). Indian J. Chem. 32, 858–861. Google Scholar
El-Hawash, S. A. M., Badawey, E. A. M. & El-Ashmawey, I. M. (2006). Eur. J. Med. Chem. 41, 155–165. Web of Science PubMed CAS Google Scholar
Gunasekaran, P., Perumal, S., Yogeeswari, P. & Sriram, D. (2011). Eur. J. Med. Chem. 46, 4530–4536. Web of Science CSD CrossRef CAS PubMed Google Scholar
Himly, M., Jahn-Schmid, B., Pittertschatscher, K., Bohle, B., Grubmayr, K., Ferreira, F., Ebner, H. & Ebner, C. (2003). J. Allergy Clin. Immunol. 111, 882–888. Web of Science CrossRef PubMed CAS Google Scholar
Jolly, V. S., Dalvi, M. Y. & Shrivastava, A. K. (1991). J. Indian Chem. Soc. 68, 513–514. CAS Google Scholar
Kalluraya, B., Lingappa, B. & Rai, N. S. (2007). Indian J. Heterocycl. Chem. 17, 67–70. CAS Google Scholar
Kawai, H., Nakai, H., Suga, M., Yuki, S., Watanabe, T. & Saito, K. I. (1997). J. Pharmacol. Exp. Ther. 281, 921–927. CAS PubMed Web of Science Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Moreau, F., Desroy, N., Genevard, J. M., Vongsouthi, V., Gerusz, V., Le Fralliec, G., Oliveira, C., Floquet, S., Denis, A., Escaich, S., Wolf, K., Busemann, M. & Aschenbrenner, A. (2008). Bioorg. Med. Chem. Lett. 18, 4022–4026. Web of Science CrossRef PubMed CAS Google Scholar
Pasha, F. A., Muddassar, M., Neaz, M. M. & Cho, S. J. (2009). J. Mol. Graph. Model. 28, 54–61. Web of Science CrossRef PubMed CAS Google Scholar
Radi, M., Bernardo, V., Bechi, B., Castagnolo, D., Pagano, M. & Botta, M. (2009). Tetrahedron Lett. 50, 6572–6575. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Singh, D. (1991). J. Indian Chem. Soc. 68, 165–167. CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, T. W., Zeng, L. H., Wu, J. & Fung, K. P. (2002). Life Sci. 71, 2249–2255. Web of Science CrossRef PubMed CAS 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages o2351-o2352

https://doi.org/10.1107/S1600536812029790

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(Z)-1-(2-Chloro­phen­yl)-3-methyl-4-[2-(4-nitro­phen­yl)hydrazin-1-yl­­idene]-1H-pyrazol-5(4H)-one

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(Z)-1-(2-Chlorophenyl)-3-methyl-4-[2-(4-nitrophenyl)hydrazin-1-ylidene]-1H-pyrazol-5(4H)-one