(E)-1-[1-(3-Chloro­phen­yl)ethyl­idene]-2-(2,4-dinitro­phen­yl)hydrazine

Fun, H.-K.; Chantrapromma, S.; Nilwanna, B.; Karalai, C.

doi:10.1107/S160053681200548X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o704-o705

doi:10.1107/S160053681200548X

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(E)-1-[1-(3-Chlorophenyl)ethylidene]-2-(2,4-dinitrophenyl)hydrazine

Hoong-Kun Fun,^a ^*‡ Suchada Chantrapromma,^b § Boonlerd Nilwanna ^b and Chatchanok Karalai ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: hkfun@usm.my

(Received 2 February 2012; accepted 7 February 2012; online 17 February 2012)

There are two crystallographically independent molecules in the asymmetric unit of the title compound, C₁₄H₁₁ClN₄O₄, with the same E conformation about the C=N double bond. The molecules are approximately planar, with a dihedral angle between the benzene rings of 10.24 (12)° in one molecule and 4.73 (12)° in the other. In both molecules, the ortho-nitro groups of the 2,4-dinitrophenyl units are coplanar to their bound benzene rings, whereas the para-nitro groups are slightly twisted. In each molecule, intramolecular N—H⋯O hydrogen bonds generate S(6) ring motifs. In the crystal, molecules are linked by weak C—H⋯O interactions into sheets parallel to the (-102) plane. These sheets are stacked by π–π interactions, with centroid–centroid distances of 3.7008 (14) and 3.7459 (14) Å. A Cl⋯O short contact [3.111 (2) Å] is observed.

Related literature

For bond-length data, see: Allen et al. (1987 ). For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related structures, see: Chantrapromma et al. (2011 ); Fun et al. (2011 , 2012 ); Nilwanna et al. (2011 ). For background to biological activities of hydrazones, see: Angelusiu et al. (2010 ); Cui et al. (2010 ); Gokce et al. (2009 ); Khan et al. (2007 ): Loncle et al. (2004 ); Wang et al. (2009 ).

Experimental

Crystal data

C₁₄H₁₁ClN₄O₄
M_r = 334.72
Monoclinic, P 2₁ /c
a = 13.4825 (13) Å
b = 15.1586 (15) Å
c = 16.1281 (12) Å
β = 116.815 (6)°
V = 2941.8 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.42 × 0.19 × 0.18 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.889, T_max = 0.951
32600 measured reflections
8629 independent reflections
4617 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.183
S = 1.01
8629 reflections
417 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O1A	0.82	1.95	2.598 (2)	135
N1B—H1NB⋯O1B	0.86	1.86	2.589 (2)	141
C5A—H5A⋯O1Aⁱ	0.93	2.52	3.251 (3)	136
C5B—H5B⋯O1Bⁱⁱ	0.93	2.33	3.196 (3)	154
C11A—H11A⋯O3Bⁱⁱⁱ	0.93	2.55	3.402 (3)	153
C11B—H11B⋯O3A^iv	0.93	2.58	3.429 (3)	153
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681200548X/rz2707sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200548X/rz2707Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200548X/rz2707Isup3.cml

checkCIF report

Comment top

Hydrazones are known to be bioactive compounds with antibacterial, antifungal, antitumor, anti-inflammatory as well as antioxidant (Angelusiu et al., 2010; Cui et al., 2010; Gokce et al., 2009; Khan et al., 2007; Loncle et al., 2004; Wang et al., 2009) activities. Within our on-going research on the bioactivity of hydrazones, the title compound (I) was synthesized in order to study and compare its biological activity with other related compounds (Chantrapromma et al., 2011; Fun et al., 2011; 2012; Nilwanna et al., 2011). Herein we report the synthesis and crystal structure of (I).

There are two crystallographic independent molecules A and B in the asymmetric unit of (I) with differences in bond angles (Fig. 1). The molecular structure of (I) is nearly planar with the dihedral angle between the two benzene rings of 10.24 (12)° in molecule A and 4.73 (12)° in molecule B. The central ethylidenehydrazine bridge (N1/N2/C7/C14) is planar with the torsion angles N1–N2–C7–C14 = 0.8 (3) and 0.5 (3)° in molecules A and B, repectively. The mean plane through this central bridge makes dihedral angles of 6.36 (17) and 3.90 (18)° with the 2,4-dinitrophenyl and 3-chlorophenyl rings, respectively in molecule A whereas the corresponding values are 5.37 (15) and 0.90 (15)° in molecule B. In both molecules, the ortho-nitro group of the 2,4-dinitrophenyl is coplanar with the attached benzene ring with the r.m.s. deviation of 0.0164 (2) Å for the nine non H-atoms (C1–C6/N3/O1/O2), and torsion angles O1–N3–C2–C3 = 176.84 (18)° and O2–N3–C2–C3 = -1.9 (3)°, whereas the para-nitro group is slightly twisted with the torsion angles O3–N4–C4–C5 = 168.8 (2)° and O4–N4–C4–C5 = -11.5 (3)° in molecule A; the corresponding values are 0.0176 (2) Å, -177.77 (18), 3.6 (3), 171.1 (2) and -8.9 (4)° in molecule B. In each molecule, intramolecular N—H···O hydrogen bond (Fig.1 and Table 1) generates S(6) ring motifs (Bernstein et al., 1995) The bond distances agree with the literature values (Allen et al., 1987) and are comparable with the related structures (Chantrapromma et al., 2011; Fun et al., 2011; 2012; Nilwanna et al., 2011).

In the crystal packing (Fig. 2), the molecules are linked by weak C—H···O interactions (Table 1) into sheets parallel to the (-102) plane. These sheets are further stacked along the a axis by π–π interactions with distances of Cg₁···Cg₂^v = 3.7459 (14) Å and Cg₁···Cg₃^vi = 3.7008 (14) Å [symmetry codes (v) = x, 3/2-y, 1/2+z; (vi) = 2-x, 2-y, 2-z]; Cg₁, Cg₂ and Cg₃ are the centroids of C1A–C6A, C8A–C13A and C8B–C13B benzene rings, respectively. A Cl1B···O1Bⁱⁱ [3.111 (2) Å] short contact is observed.

Related literature top

For bond-length data, see: Allen et al. (1987). For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Chantrapromma et al. (2011); Fun et al. (2011, 2012); Nilwanna et al. (2011). For background to biological activities of hydrazones, see: Angelusiu et al. (2010); Cui et al. (2010); Gokce et al. (2009); Khan et al. (2007): Loncle et al. (2004); Wang et al. (2009).

Experimental top

The title compound (I) was synthesized by dissolving 2,4-dinitrophenylhydrazine (0.40 g, 2 mmol) in ethanol (10.00 ml) and H₂SO₄ (conc.) (98 %, 0.50 ml) was slowly added with stirring. 3-Chloroacetophenone (0.26 ml, 2 mmol) was then added to the solution with continuous stirring. The solution was stirred for 1 h yielding an orange solid, which was filtered off and washed with methanol. Orange block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from ethanol by slow evaporation of the solvent at room temperature over several days. M.p. 478-479 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids. Intramolecular N—H···O hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal packing of (I) viewed approximately along the b axis. Hydrogen bonds are shown as dashed lines.

(E)-1-[1-(3-Chlorophenyl)ethylidene]-2-(2,4-dinitrophenyl)hydrazine top

Crystal data top

C₁₄H₁₁ClN₄O₄	F(000) = 1376
M_r = 334.72	D_x = 1.512 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 478–479 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.4825 (13) Å	Cell parameters from 8629 reflections
b = 15.1586 (15) Å	θ = 1.7–30.1°
c = 16.1281 (12) Å	µ = 0.29 mm⁻¹
β = 116.815 (6)°	T = 296 K
V = 2941.8 (5) Å³	Block, orange
Z = 8	0.42 × 0.19 × 0.18 mm

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	8629 independent reflections
Radiation source: sealed tube	4617 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 30.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→18
T_min = 0.889, T_max = 0.951	k = −21→19
32600 measured reflections	l = −22→22

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0916P)² + 0.289P] where P = (F_o² + 2F_c²)/3
8629 reflections	(Δ/σ)_max = 0.001
417 parameters	Δρ_max = 0.35 e Å⁻³
1 restraint	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₄H₁₁ClN₄O₄	V = 2941.8 (5) Å³
M_r = 334.72	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.4825 (13) Å	µ = 0.29 mm⁻¹
b = 15.1586 (15) Å	T = 296 K
c = 16.1281 (12) Å	0.42 × 0.19 × 0.18 mm
β = 116.815 (6)°

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	8629 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4617 reflections with I > 2σ(I)
T_min = 0.889, T_max = 0.951	R_int = 0.034
32600 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	1 restraint
wR(F²) = 0.183	H-atom parameters constrained
S = 1.01	Δρ_max = 0.35 e Å⁻³
8629 reflections	Δρ_min = −0.34 e Å⁻³
417 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.83654 (6)	0.45629 (4)	0.39055 (4)	0.0766 (2)
O1A	0.99997 (15)	0.97920 (10)	0.69823 (12)	0.0774 (5)
O2A	1.06555 (14)	0.99861 (10)	0.84524 (12)	0.0711 (5)
O3A	1.2204 (2)	0.76410 (15)	1.05861 (12)	0.1103 (8)
O4A	1.18161 (18)	0.63048 (13)	1.01190 (12)	0.0949 (6)
N1A	0.97877 (14)	0.82236 (11)	0.62719 (11)	0.0553 (4)
H1NA	0.9589	0.8744	0.6200	0.066*
N2A	0.94483 (14)	0.76046 (11)	0.55856 (11)	0.0536 (4)
N3A	1.03978 (14)	0.95052 (11)	0.77797 (13)	0.0545 (4)
N4A	1.18006 (17)	0.70917 (15)	0.99701 (13)	0.0688 (5)
C1A	1.02714 (15)	0.79618 (12)	0.71746 (13)	0.0457 (4)
C2A	1.05891 (15)	0.85647 (12)	0.79264 (13)	0.0449 (4)
C3A	1.10886 (15)	0.82829 (13)	0.88368 (13)	0.0481 (4)
H3A	1.1298	0.8685	0.9322	0.058*
C4A	1.12712 (16)	0.73977 (13)	0.90130 (13)	0.0502 (5)
C5A	1.09807 (17)	0.67883 (13)	0.82982 (14)	0.0556 (5)
H5A	1.1124	0.6192	0.8435	0.067*
C6A	1.04898 (18)	0.70614 (12)	0.74032 (14)	0.0533 (5)
H6A	1.0293	0.6647	0.6930	0.064*
C7A	0.90349 (17)	0.78840 (14)	0.47443 (14)	0.0534 (5)
C8A	0.86585 (16)	0.71840 (15)	0.40185 (13)	0.0514 (5)
C9A	0.87083 (16)	0.63003 (14)	0.42698 (13)	0.0525 (5)
H9A	0.8993	0.6143	0.4893	0.063*
C10A	0.83347 (17)	0.56618 (15)	0.35924 (14)	0.0558 (5)
C11A	0.79092 (17)	0.58681 (18)	0.26572 (14)	0.0636 (6)
H11A	0.7651	0.5428	0.2208	0.076*
C12A	0.78777 (18)	0.67358 (19)	0.24109 (15)	0.0678 (6)
H12A	0.7610	0.6885	0.1787	0.081*
C13A	0.82399 (18)	0.73955 (17)	0.30792 (14)	0.0614 (6)
H13A	0.8203	0.7982	0.2900	0.074*
C14A	0.8916 (3)	0.88420 (17)	0.44724 (17)	0.0849 (8)
H14A	0.9563	0.9159	0.4895	0.127*
H14B	0.8270	0.9082	0.4495	0.127*
H14C	0.8839	0.8896	0.3853	0.127*
Cl1B	0.60994 (6)	1.29099 (4)	1.10126 (4)	0.0783 (2)
O1B	0.58475 (15)	0.77573 (10)	0.80697 (11)	0.0683 (4)
O2B	0.51645 (18)	0.75501 (10)	0.66003 (13)	0.0860 (6)
O3B	0.35381 (19)	0.98474 (14)	0.44260 (11)	0.1013 (7)
O4B	0.3250 (2)	1.11127 (14)	0.48825 (13)	0.1090 (8)
N1B	0.58812 (13)	0.93100 (11)	0.87512 (11)	0.0490 (4)
H1NB	0.6001	0.8750	0.8796	0.059*
N2B	0.60588 (13)	0.99163 (11)	0.94310 (10)	0.0474 (4)
N3B	0.53830 (15)	0.80306 (11)	0.72640 (13)	0.0556 (4)
N4B	0.36352 (19)	1.03694 (14)	0.50342 (13)	0.0729 (6)
C1B	0.53726 (15)	0.95592 (12)	0.78481 (12)	0.0432 (4)
C2B	0.51113 (15)	0.89601 (11)	0.71062 (13)	0.0445 (4)
C3B	0.45551 (17)	0.92247 (13)	0.61880 (13)	0.0507 (5)
H3B	0.4394	0.8822	0.5709	0.061*
C4B	0.42477 (17)	1.00861 (13)	0.59995 (13)	0.0517 (5)
C5B	0.45036 (18)	1.07026 (13)	0.67045 (14)	0.0564 (5)
H5B	0.4293	1.1289	0.6559	0.068*
C6B	0.50633 (18)	1.04464 (12)	0.76078 (14)	0.0513 (5)
H6B	0.5245	1.0865	0.8076	0.062*
C7B	0.64883 (16)	0.96382 (13)	1.02719 (13)	0.0479 (4)
C8B	0.66519 (15)	1.03272 (14)	1.09812 (13)	0.0475 (4)
C9B	0.63316 (16)	1.11936 (14)	1.07065 (13)	0.0505 (5)
H9B	0.6015	1.1343	1.0080	0.061*
C10B	0.64837 (16)	1.18318 (15)	1.13627 (14)	0.0539 (5)
C11B	0.69611 (17)	1.16370 (17)	1.22983 (14)	0.0589 (5)
H11B	0.7068	1.2075	1.2734	0.071*
C12B	0.72749 (19)	1.07829 (18)	1.25720 (14)	0.0631 (6)
H12B	0.7595	1.0640	1.3200	0.076*
C13B	0.71201 (17)	1.01338 (15)	1.19250 (14)	0.0572 (5)
H13B	0.7332	0.9557	1.2123	0.069*
C14B	0.6820 (2)	0.86989 (15)	1.05689 (15)	0.0722 (7)
H14D	0.6413	0.8311	1.0056	0.108*
H14E	0.6656	0.8557	1.1074	0.108*
H14F	0.7602	0.8629	1.0766	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.0978 (5)	0.0648 (4)	0.0690 (4)	−0.0055 (3)	0.0391 (3)	−0.0079 (3)
O1A	0.1049 (13)	0.0437 (8)	0.0721 (11)	0.0150 (8)	0.0298 (10)	0.0122 (8)
O2A	0.0885 (12)	0.0463 (8)	0.0820 (11)	0.0005 (8)	0.0417 (10)	−0.0156 (8)
O3A	0.159 (2)	0.0944 (15)	0.0468 (10)	−0.0004 (14)	0.0199 (11)	0.0000 (10)
O4A	0.1274 (16)	0.0722 (12)	0.0691 (11)	0.0088 (11)	0.0301 (11)	0.0272 (9)
N1A	0.0674 (11)	0.0427 (9)	0.0489 (9)	0.0047 (8)	0.0200 (8)	0.0013 (7)
N2A	0.0591 (10)	0.0508 (9)	0.0439 (9)	0.0023 (8)	0.0170 (8)	0.0003 (7)
N3A	0.0582 (10)	0.0393 (8)	0.0657 (11)	0.0026 (7)	0.0278 (9)	−0.0008 (8)
N4A	0.0792 (13)	0.0687 (13)	0.0522 (11)	0.0052 (10)	0.0240 (10)	0.0111 (10)
C1A	0.0472 (10)	0.0407 (9)	0.0468 (10)	0.0006 (8)	0.0192 (8)	0.0013 (8)
C2A	0.0481 (10)	0.0346 (9)	0.0529 (10)	0.0007 (7)	0.0236 (8)	−0.0007 (8)
C3A	0.0483 (10)	0.0478 (10)	0.0485 (10)	−0.0041 (8)	0.0223 (8)	−0.0054 (8)
C4A	0.0537 (11)	0.0496 (11)	0.0446 (10)	−0.0004 (9)	0.0199 (9)	0.0039 (8)
C5A	0.0666 (13)	0.0363 (9)	0.0582 (12)	0.0001 (9)	0.0233 (10)	0.0042 (8)
C6A	0.0657 (12)	0.0369 (9)	0.0504 (11)	−0.0002 (8)	0.0199 (9)	−0.0035 (8)
C7A	0.0497 (11)	0.0563 (12)	0.0512 (11)	0.0054 (9)	0.0200 (9)	0.0077 (9)
C8A	0.0441 (10)	0.0649 (13)	0.0442 (10)	0.0063 (9)	0.0192 (8)	0.0061 (9)
C9A	0.0506 (11)	0.0646 (13)	0.0408 (10)	0.0008 (9)	0.0193 (8)	0.0008 (9)
C10A	0.0503 (11)	0.0668 (13)	0.0505 (11)	0.0014 (10)	0.0231 (9)	−0.0014 (10)
C11A	0.0521 (12)	0.0900 (18)	0.0467 (11)	−0.0003 (11)	0.0205 (10)	−0.0109 (11)
C12A	0.0616 (13)	0.0988 (19)	0.0394 (11)	0.0085 (13)	0.0194 (10)	0.0060 (11)
C13A	0.0604 (12)	0.0751 (15)	0.0459 (11)	0.0089 (11)	0.0214 (9)	0.0124 (10)
C14A	0.122 (2)	0.0617 (15)	0.0613 (15)	0.0093 (15)	0.0331 (15)	0.0130 (12)
Cl1B	0.1019 (5)	0.0664 (4)	0.0699 (4)	0.0174 (3)	0.0415 (4)	−0.0006 (3)
O1B	0.0926 (12)	0.0426 (8)	0.0695 (10)	0.0050 (7)	0.0364 (9)	0.0099 (7)
O2B	0.1302 (16)	0.0440 (8)	0.0760 (11)	0.0024 (9)	0.0396 (11)	−0.0144 (8)
O3B	0.159 (2)	0.0877 (14)	0.0431 (9)	0.0147 (13)	0.0329 (11)	0.0020 (9)
O4B	0.162 (2)	0.0778 (13)	0.0645 (11)	0.0374 (14)	0.0311 (12)	0.0214 (10)
N1B	0.0603 (10)	0.0419 (8)	0.0455 (8)	−0.0016 (7)	0.0246 (7)	−0.0001 (7)
N2B	0.0531 (9)	0.0474 (9)	0.0445 (8)	−0.0053 (7)	0.0245 (7)	−0.0007 (7)
N3B	0.0685 (11)	0.0395 (9)	0.0606 (11)	−0.0029 (8)	0.0307 (9)	−0.0032 (8)
N4B	0.0972 (15)	0.0665 (13)	0.0486 (11)	0.0051 (11)	0.0273 (10)	0.0099 (10)
C1B	0.0486 (10)	0.0414 (9)	0.0452 (10)	−0.0051 (7)	0.0260 (8)	0.0002 (7)
C2B	0.0517 (10)	0.0348 (9)	0.0504 (10)	−0.0048 (7)	0.0261 (9)	−0.0017 (7)
C3B	0.0636 (12)	0.0452 (10)	0.0470 (10)	−0.0059 (9)	0.0284 (9)	−0.0049 (8)
C4B	0.0663 (13)	0.0476 (11)	0.0425 (10)	−0.0020 (9)	0.0257 (9)	0.0028 (8)
C5B	0.0775 (14)	0.0387 (10)	0.0562 (12)	0.0016 (9)	0.0331 (11)	0.0065 (9)
C6B	0.0708 (13)	0.0386 (9)	0.0481 (10)	−0.0031 (9)	0.0301 (10)	−0.0033 (8)
C7B	0.0459 (10)	0.0526 (11)	0.0448 (10)	−0.0042 (8)	0.0202 (8)	0.0046 (8)
C8B	0.0440 (10)	0.0578 (12)	0.0419 (10)	−0.0066 (8)	0.0204 (8)	0.0019 (8)
C9B	0.0500 (11)	0.0621 (12)	0.0392 (9)	−0.0009 (9)	0.0200 (8)	0.0025 (9)
C10B	0.0508 (11)	0.0626 (13)	0.0513 (11)	−0.0009 (9)	0.0258 (9)	−0.0022 (9)
C11B	0.0598 (12)	0.0763 (15)	0.0458 (11)	−0.0061 (11)	0.0284 (10)	−0.0090 (10)
C12B	0.0655 (13)	0.0870 (17)	0.0378 (10)	−0.0071 (12)	0.0243 (9)	0.0029 (11)
C13B	0.0603 (12)	0.0664 (13)	0.0451 (10)	−0.0026 (10)	0.0240 (9)	0.0083 (10)
C14B	0.0949 (18)	0.0579 (14)	0.0520 (12)	0.0059 (12)	0.0228 (12)	0.0077 (10)

Geometric parameters (Å, º) top

Cl1A—C10A	1.736 (2)	Cl1B—C10B	1.730 (2)
O1A—N3A	1.228 (2)	O1B—N3B	1.232 (2)
O2A—N3A	1.220 (2)	O2B—N3B	1.216 (2)
O3A—N4A	1.220 (3)	O3B—N4B	1.221 (3)
O4A—N4A	1.215 (3)	O4B—N4B	1.218 (3)
N1A—C1A	1.359 (2)	N1B—C1B	1.354 (2)
N1A—N2A	1.363 (2)	N1B—N2B	1.366 (2)
N1A—H1NA	0.8247	N1B—H1NB	0.8610
N2A—C7A	1.284 (2)	N2B—C7B	1.282 (2)
N3A—C2A	1.449 (2)	N3B—C2B	1.449 (2)
N4A—C4A	1.454 (3)	N4B—C4B	1.460 (3)
C1A—C6A	1.410 (3)	C1B—C6B	1.410 (2)
C1A—C2A	1.421 (3)	C1B—C2B	1.414 (2)
C2A—C3A	1.378 (3)	C2B—C3B	1.384 (3)
C3A—C4A	1.371 (3)	C3B—C4B	1.362 (3)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.389 (3)	C4B—C5B	1.390 (3)
C5A—C6A	1.353 (3)	C5B—C6B	1.361 (3)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—H6A	0.9300	C6B—H6B	0.9300
C7A—C8A	1.489 (3)	C7B—C8B	1.490 (3)
C7A—C14A	1.505 (3)	C7B—C14B	1.504 (3)
C8A—C9A	1.392 (3)	C8B—C13B	1.391 (3)
C8A—C13A	1.395 (3)	C8B—C9B	1.391 (3)
C9A—C10A	1.374 (3)	C9B—C10B	1.379 (3)
C9A—H9A	0.9300	C9B—H9B	0.9300
C10A—C11A	1.386 (3)	C10B—C11B	1.379 (3)
C11A—C12A	1.369 (4)	C11B—C12B	1.372 (4)
C11A—H11A	0.9300	C11B—H11B	0.9300
C12A—C13A	1.388 (3)	C12B—C13B	1.380 (3)
C12A—H12A	0.9300	C12B—H12B	0.9300
C13A—H13A	0.9300	C13B—H13B	0.9300
C14A—H14A	0.9600	C14B—H14D	0.9600
C14A—H14B	0.9600	C14B—H14E	0.9600
C14A—H14C	0.9600	C14B—H14F	0.9600

C1A—N1A—N2A	119.48 (16)	C1B—N1B—N2B	119.72 (16)
C1A—N1A—H1NA	113.5	C1B—N1B—H1NB	110.5
N2A—N1A—H1NA	125.2	N2B—N1B—H1NB	129.6
C7A—N2A—N1A	117.24 (18)	C7B—N2B—N1B	117.36 (17)
O2A—N3A—O1A	122.28 (17)	O2B—N3B—O1B	122.21 (18)
O2A—N3A—C2A	118.97 (18)	O2B—N3B—C2B	119.09 (18)
O1A—N3A—C2A	118.74 (17)	O1B—N3B—C2B	118.69 (16)
O4A—N4A—O3A	123.2 (2)	O4B—N4B—O3B	123.8 (2)
O4A—N4A—C4A	118.6 (2)	O4B—N4B—C4B	118.1 (2)
O3A—N4A—C4A	118.2 (2)	O3B—N4B—C4B	118.1 (2)
N1A—C1A—C6A	120.38 (17)	N1B—C1B—C6B	120.37 (17)
N1A—C1A—C2A	122.72 (17)	N1B—C1B—C2B	122.88 (16)
C6A—C1A—C2A	116.90 (17)	C6B—C1B—C2B	116.75 (17)
C3A—C2A—C1A	121.59 (17)	C3B—C2B—C1B	121.82 (17)
C3A—C2A—N3A	116.37 (17)	C3B—C2B—N3B	116.22 (17)
C1A—C2A—N3A	122.03 (17)	C1B—C2B—N3B	121.94 (17)
C4A—C3A—C2A	118.68 (18)	C4B—C3B—C2B	118.70 (18)
C4A—C3A—H3A	120.7	C4B—C3B—H3B	120.6
C2A—C3A—H3A	120.7	C2B—C3B—H3B	120.6
C3A—C4A—C5A	121.47 (18)	C3B—C4B—C5B	121.59 (18)
C3A—C4A—N4A	119.25 (19)	C3B—C4B—N4B	119.28 (18)
C5A—C4A—N4A	119.27 (19)	C5B—C4B—N4B	119.14 (19)
C6A—C5A—C4A	120.08 (18)	C6B—C5B—C4B	119.81 (19)
C6A—C5A—H5A	120.0	C6B—C5B—H5B	120.1
C4A—C5A—H5A	120.0	C4B—C5B—H5B	120.1
C5A—C6A—C1A	121.27 (18)	C5B—C6B—C1B	121.28 (18)
C5A—C6A—H6A	119.4	C5B—C6B—H6B	119.4
C1A—C6A—H6A	119.4	C1B—C6B—H6B	119.4
N2A—C7A—C8A	115.29 (19)	N2B—C7B—C8B	114.92 (18)
N2A—C7A—C14A	124.4 (2)	N2B—C7B—C14B	125.14 (19)
C8A—C7A—C14A	120.33 (19)	C8B—C7B—C14B	119.94 (17)
C9A—C8A—C13A	118.7 (2)	C13B—C8B—C9B	118.04 (19)
C9A—C8A—C7A	120.14 (17)	C13B—C8B—C7B	121.96 (19)
C13A—C8A—C7A	121.2 (2)	C9B—C8B—C7B	120.00 (17)
C10A—C9A—C8A	119.60 (19)	C10B—C9B—C8B	120.03 (18)
C10A—C9A—H9A	120.2	C10B—C9B—H9B	120.0
C8A—C9A—H9A	120.2	C8B—C9B—H9B	120.0
C9A—C10A—C11A	122.0 (2)	C11B—C10B—C9B	121.6 (2)
C9A—C10A—Cl1A	119.52 (16)	C11B—C10B—Cl1B	118.84 (18)
C11A—C10A—Cl1A	118.49 (18)	C9B—C10B—Cl1B	119.55 (16)
C12A—C11A—C10A	118.4 (2)	C12B—C11B—C10B	118.6 (2)
C12A—C11A—H11A	120.8	C12B—C11B—H11B	120.7
C10A—C11A—H11A	120.8	C10B—C11B—H11B	120.7
C11A—C12A—C13A	120.9 (2)	C11B—C12B—C13B	120.7 (2)
C11A—C12A—H12A	119.6	C11B—C12B—H12B	119.7
C13A—C12A—H12A	119.6	C13B—C12B—H12B	119.7
C12A—C13A—C8A	120.4 (2)	C12B—C13B—C8B	121.1 (2)
C12A—C13A—H13A	119.8	C12B—C13B—H13B	119.5
C8A—C13A—H13A	119.8	C8B—C13B—H13B	119.5
C7A—C14A—H14A	109.5	C7B—C14B—H14D	109.5
C7A—C14A—H14B	109.5	C7B—C14B—H14E	109.5
H14A—C14A—H14B	109.5	H14D—C14B—H14E	109.5
C7A—C14A—H14C	109.5	C7B—C14B—H14F	109.5
H14A—C14A—H14C	109.5	H14D—C14B—H14F	109.5
H14B—C14A—H14C	109.5	H14E—C14B—H14F	109.5

C1A—N1A—N2A—C7A	−177.38 (18)	C1B—N1B—N2B—C7B	176.29 (17)
N2A—N1A—C1A—C6A	4.3 (3)	N2B—N1B—C1B—C6B	2.4 (3)
N2A—N1A—C1A—C2A	−176.33 (18)	N2B—N1B—C1B—C2B	−176.75 (17)
N1A—C1A—C2A—C3A	−179.36 (18)	N1B—C1B—C2B—C3B	177.62 (18)
C6A—C1A—C2A—C3A	0.1 (3)	C6B—C1B—C2B—C3B	−1.5 (3)
N1A—C1A—C2A—N3A	1.2 (3)	N1B—C1B—C2B—N3B	−0.6 (3)
C6A—C1A—C2A—N3A	−179.35 (18)	C6B—C1B—C2B—N3B	−179.79 (17)
O2A—N3A—C2A—C3A	−1.9 (3)	O2B—N3B—C2B—C3B	3.6 (3)
O1A—N3A—C2A—C3A	176.84 (18)	O1B—N3B—C2B—C3B	−177.77 (18)
O2A—N3A—C2A—C1A	177.57 (18)	O2B—N3B—C2B—C1B	−178.10 (19)
O1A—N3A—C2A—C1A	−3.7 (3)	O1B—N3B—C2B—C1B	0.6 (3)
C1A—C2A—C3A—C4A	−0.5 (3)	C1B—C2B—C3B—C4B	−0.4 (3)
N3A—C2A—C3A—C4A	178.92 (17)	N3B—C2B—C3B—C4B	177.93 (18)
C2A—C3A—C4A—C5A	1.0 (3)	C2B—C3B—C4B—C5B	1.6 (3)
C2A—C3A—C4A—N4A	179.80 (18)	C2B—C3B—C4B—N4B	−178.42 (19)
O4A—N4A—C4A—C3A	169.6 (2)	O4B—N4B—C4B—C3B	171.1 (2)
O3A—N4A—C4A—C3A	−10.0 (3)	O3B—N4B—C4B—C3B	−8.9 (3)
O4A—N4A—C4A—C5A	−11.5 (3)	O4B—N4B—C4B—C5B	−8.9 (4)
O3A—N4A—C4A—C5A	168.8 (2)	O3B—N4B—C4B—C5B	171.1 (2)
C3A—C4A—C5A—C6A	−1.1 (3)	C3B—C4B—C5B—C6B	−0.8 (3)
N4A—C4A—C5A—C6A	−179.8 (2)	N4B—C4B—C5B—C6B	179.3 (2)
C4A—C5A—C6A—C1A	0.6 (3)	C4B—C5B—C6B—C1B	−1.3 (3)
N1A—C1A—C6A—C5A	179.35 (19)	N1B—C1B—C6B—C5B	−176.77 (19)
C2A—C1A—C6A—C5A	−0.1 (3)	C2B—C1B—C6B—C5B	2.4 (3)
N1A—N2A—C7A—C8A	−179.01 (17)	N1B—N2B—C7B—C8B	−179.42 (15)
N1A—N2A—C7A—C14A	0.8 (3)	N1B—N2B—C7B—C14B	0.5 (3)
N2A—C7A—C8A—C9A	3.7 (3)	N2B—C7B—C8B—C13B	−179.25 (18)
C14A—C7A—C8A—C9A	−176.1 (2)	C14B—C7B—C8B—C13B	0.8 (3)
N2A—C7A—C8A—C13A	−177.09 (19)	N2B—C7B—C8B—C9B	0.8 (3)
C14A—C7A—C8A—C13A	3.1 (3)	C14B—C7B—C8B—C9B	−179.11 (19)
C13A—C8A—C9A—C10A	−0.8 (3)	C13B—C8B—C9B—C10B	0.1 (3)
C7A—C8A—C9A—C10A	178.49 (18)	C7B—C8B—C9B—C10B	−179.94 (18)
C8A—C9A—C10A—C11A	0.3 (3)	C8B—C9B—C10B—C11B	0.7 (3)
C8A—C9A—C10A—Cl1A	−178.40 (15)	C8B—C9B—C10B—Cl1B	179.10 (15)
C9A—C10A—C11A—C12A	0.8 (3)	C9B—C10B—C11B—C12B	−0.9 (3)
Cl1A—C10A—C11A—C12A	179.51 (17)	Cl1B—C10B—C11B—C12B	−179.32 (17)
C10A—C11A—C12A—C13A	−1.4 (3)	C10B—C11B—C12B—C13B	0.3 (3)
C11A—C12A—C13A—C8A	0.9 (3)	C11B—C12B—C13B—C8B	0.5 (3)
C9A—C8A—C13A—C12A	0.2 (3)	C9B—C8B—C13B—C12B	−0.7 (3)
C7A—C8A—C13A—C12A	−179.1 (2)	C7B—C8B—C13B—C12B	179.35 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1A	0.82	1.95	2.598 (2)	135
N1B—H1NB···O1B	0.86	1.86	2.589 (2)	141
C5A—H5A···O1Aⁱ	0.93	2.52	3.251 (3)	136
C5B—H5B···O1Bⁱⁱ	0.93	2.33	3.196 (3)	154
C11A—H11A···O3Bⁱⁱⁱ	0.93	2.55	3.402 (3)	153
C11B—H11B···O3A^iv	0.93	2.58	3.429 (3)	153

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y+1/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClN₄O₄
M_r	334.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.4825 (13), 15.1586 (15), 16.1281 (12)
β (°)	116.815 (6)
V (Å³)	2941.8 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.42 × 0.19 × 0.18

Data collection
Diffractometer	Bruker APEX DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.889, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	32600, 8629, 4617
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.183, 1.01
No. of reflections	8629
No. of parameters	417
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.34

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1A	0.82	1.95	2.598 (2)	135
N1B—H1NB···O1B	0.86	1.86	2.589 (2)	141
C5A—H5A···O1Aⁱ	0.93	2.52	3.251 (3)	136
C5B—H5B···O1Bⁱⁱ	0.93	2.33	3.196 (3)	154
C11A—H11A···O3Bⁱⁱⁱ	0.93	2.55	3.402 (3)	153
C11B—H11B···O3A^iv	0.93	2.58	3.429 (3)	153

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y+1/2, −z+5/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Additional correspondence author, e-mail: suchada.c@psu.ac.th. Thomson Reuters ResearcherID: A-5085-2009.

Acknowledgements

The authors thank the Prince of Songkla University for financial support through the Crystal Materials Research Unit. The authors also thank the Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160.

References

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