(E)-1-(2,4-Dinitro­phen­yl)-2-[1-(3-meth­oxy­phen­yl)ethyl­idene]hydrazine

Fun, H.-K.; Chantrapromma, S.; Nilwanna, B.; Kobkeatthawin, T.

doi:10.1107/S1600536812026979

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages o2144-o2145

https://doi.org/10.1107/S1600536812026979

Open

access

(E)-1-(2,4-Dinitrophenyl)-2-[1-(3-methoxyphenyl)ethylidene]hydrazine

Hoong-Kun Fun,^a ^*‡ Suchada Chantrapromma,^b § Boonlerd Nilwanna ^b and Thawanrat Kobkeatthawin ^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 28 May 2012; accepted 14 June 2012; online 20 June 2012)

There are two crystallographically independent molecules in the asymmetric unit of the title compound, C₁₅H₁₄N₄O₅, with different conformations for the methoxy groups. The molecules are both slightly twisted, the dihedral angles between two benzene rings being 8.37 (18)° in one and 7.31 (18)° in the other. In both molecules, the two nitro groups are essentially coplanar with their bound benzene ring, with the r.m.s. deviation of the dinitrobenzene plane being 0.0310 (3) Å in one molecule and 0.0650 (3) Å in the other. In each molecule, an intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked by weak C—H⋯O interactions and stacked along the a axis through π–π interactions, with centroid–centroid distances of 3.651 (2) and 3.721 (2) Å. The crystal studied was a non-merohedral twin with a refined minor component of 20.1 (3)%.

Related literature

For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related structures, see: Chantrapromma et al. (2012 ); Fun et al. (2010 ); Nilwanna et al. (2011 ). For background to the biological activity of hydrozones, see: Bendre et al. (1998 ); El-Sherif (2009 ); Gokce et al. (2009 ); Molyneux (2004 ); Sathyadevi et al. (2012 ); Xia et al. (2008 ).

Experimental

Crystal data

C₁₅H₁₄N₄O₅
M_r = 330.30
Triclinic, $[P \overline 1]$
a = 7.5612 (13) Å
b = 10.4517 (18) Å
c = 19.516 (3) Å
α = 76.034 (4)°
β = 89.531 (4)°
γ = 84.052 (4)°
V = 1488.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.33 × 0.14 × 0.05 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.964, T_max = 0.994
7846 measured reflections
7846 independent reflections
5592 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.086
wR(F²) = 0.296
S = 1.11
7846 reflections
444 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O1A	0.87 (3)	1.94 (4)	2.611 (4)	133 (3)
N1B—H1NB⋯O1B	0.88 (4)	1.96 (3)	2.611 (4)	130 (4)
C5B—H5B⋯O3Aⁱ	0.93	2.59	3.462 (5)	156
C6B—H6B⋯O4Aⁱ	0.93	2.50	3.277 (4)	141
C8A—H8C⋯O3Bⁱⁱ	0.96	2.57	3.376 (5)	142
C8B—H8E⋯O4Bⁱⁱⁱ	0.96	2.45	3.402 (5)	170
C12B—H12B⋯O2A^iv	0.93	2.57	3.447 (5)	157
C13A—H13A⋯O3Bⁱⁱⁱ	0.93	2.48	3.204 (5)	135
C13B—H13B⋯O3A^iv	0.93	2.55	3.448 (5)	162
C14B—H14B⋯O4Bⁱⁱⁱ	0.93	2.47	3.338 (5)	155
C15B—H15E⋯O3A^v	0.96	2.57	3.301 (5)	133
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y, -z+1; (iii) x-1, y+1, z; (iv) x-1, y+1, z-1; (v) -x+1, -y+1, -z+1.

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: https://doi.org/10.1107/S1600536812026979/is5147sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026979/is5147Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812026979/is5147Isup3.cml

checkCIF report

Comment top

Hydrazones are important compounds which have considerable interesting applications involving biological activities such as antibacterial (El-Sherif et al., 2009), antioxidant (Sathyadevi et al., 2012), anticancer (Xia et al., 2008), anti-inflammatory (Gokce et al., 2009) and tyrosinase inhibitory (Bendre et al., 1998) activities. With our on-going research on crystal structures, bioactivity and antioxidant activity of hydrazones (Chantrapromma et al., 2012; Fun et al., 2010; Nilwanna et al., 2011), the title compound (I) was synthesized. The evaluation of its antioxidant activity by DPPH scavenging (Molyneux, 2004) was found to be inactive. Herein we report the synthesis and crystal structure of (I).

In Fig. 1, there are two crystallographically independent molecules A and B in the asymmetric unit of (I), C₁₅H₁₄N₄O₅, with differences in bond angles and conformations of the methoxy groups in which in molecule A the methoxy group is co-planar with its bound benzene ring and pointed toward the central ethylidenehydrazine (N1/N2/C7/C8) as indicated by the torsion angle C15A–O5A–C11A–C10A = -2.6 (5)°, whereas in molecule B it is twisted and pointed away from the central ethylidenehydrazine with the torsion angle C15B–O5B–C11B–C10B = 167.7 (3)°. The molecular structure of (I) is twisted with the dihedral angle between the two benzene rings being 8.37 (18)° in molecule A and 7.31 (18)° in molecule B. The central ethylidenehydrazine bridge is planar with the torsion angles N1–N2–C7–C8 = -1.3 (5) and 1.7 (5)° in molecules A and B, respectively. The mean plane through this central bridge makes dihedral angles of 9.0 (2) and 1.5 (2)° with the 2,4-dinitro- and 3-methoxy-substituted benzene rings, respectively, in molecule A, whereas the corresponding values are 7.8 (2) and 1.0 (2)° in molecule B. In both molecules, the two nitro groups are co-planar with their bound benzene rings with r.m.s. deviations of 0.0310 (3) and 0.0650 (3) Å in molecules A and B, respectively, for the twelve non H-atoms (C1–C6/N3/N4/O1–O4). In each molecule, intramolecular N—H···O hydrogen bonds (Fig. 1 and Table 1) generate two S(6) ring motifs (Bernstein et al., 1995). The bond distances are in normal ranges (Allen et al., 1987) and are comparable with the related structures (Chantrapromma et al., 2012; Fun et al., 2010; Nilwanna et al., 2011).

In the crystal packing (Fig. 2), the molecules are linked by weak C—H···O interactions (Table 1) and stacked along the a axis by π–π interactions with distances of Cg1···Cg4^v = 3.721 (2) Å and Cg2···Cg3^v = 3.651 (2) Å; Cg1, Cg2, Cg3 and Cg4 are the centroids of C1A–C6A, C9A–C14A, C1B–C6B and C9B–C14B benzene rings, respectively.

Related literature top

For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Chantrapromma et al. (2012); Fun et al. (2010); Nilwanna et al. (2011). For background to the biological activity of hydrozones, see: Bendre et al. (1998); El-Sherif (2009); Gokce et al. (2009); Molyneux (2004); Sathyadevi et al. (2012); Xia et al. (2008).

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-Methoxyacetophenone (0.33 ml, 2 mmol) was then added to the solution with continuous stirring. The solution was stirred for 1 hr yielding an orange solid, which was filtered off and washed with methanol. Orange plate-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvent at room temperature over several days (m.p. 459-460 K).

Structure description top

For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Chantrapromma et al. (2012); Fun et al. (2010); Nilwanna et al. (2011). For background to the biological activity of hydrozones, see: Bendre et al. (1998); El-Sherif (2009); Gokce et al. (2009); Molyneux (2004); Sathyadevi et al. (2012); Xia et al. (2008).

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 the title compound, showing 60% probability displacement ellipsoids and the atom-numbering scheme. Intramolecular N—H···O hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal packing of the title compound, viewed approximately along the a axis. Hydrogen bonds are shown as dashed lines.

(E)-1-(2,4-Dinitrophenyl)-2-[1-(3-methoxyphenyl)ethylidene]hydrazine top

Crystal data top

C₁₅H₁₄N₄O₅	Z = 4
M_r = 330.30	F(000) = 688
Triclinic, P1	D_x = 1.474 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5612 (13) Å	Cell parameters from 7846 reflections
b = 10.4517 (18) Å	θ = 1.1–29.0°
c = 19.516 (3) Å	µ = 0.11 mm⁻¹
α = 76.034 (4)°	T = 100 K
β = 89.531 (4)°	Plate, orange
γ = 84.052 (4)°	0.33 × 0.14 × 0.05 mm
V = 1488.4 (4) Å³

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	7846 independent reflections
Radiation source: fine-focus sealed tube	5592 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
φ and ω scans	θ_max = 29.0°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
T_min = 0.964, T_max = 0.994	k = −13→14
7846 measured reflections	l = −12→26

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)] = 0.086	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.296	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.1531P)² + 2.363P] where P = (F_o² + 2F_c²)/3
7846 reflections	(Δ/σ)_max = 0.001
444 parameters	Δρ_max = 0.53 e Å⁻³
2 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₁₅H₁₄N₄O₅	γ = 84.052 (4)°
M_r = 330.30	V = 1488.4 (4) Å³
Triclinic, P1	Z = 4
a = 7.5612 (13) Å	Mo Kα radiation
b = 10.4517 (18) Å	µ = 0.11 mm⁻¹
c = 19.516 (3) Å	T = 100 K
α = 76.034 (4)°	0.33 × 0.14 × 0.05 mm
β = 89.531 (4)°

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	7846 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5592 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.994	R_int = 0.000
7846 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.086	2 restraints
wR(F²) = 0.296	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.53 e Å⁻³
7846 reflections	Δρ_min = −0.59 e Å⁻³
444 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
O1A	0.5983 (4)	0.0757 (3)	0.79029 (14)	0.0199 (6)
O2A	0.7040 (4)	−0.0325 (3)	0.89291 (14)	0.0181 (6)
O3A	0.6439 (4)	0.1398 (3)	1.09429 (14)	0.0196 (6)
O4A	0.4793 (4)	0.3241 (3)	1.09095 (15)	0.0233 (6)
O5A	−0.0748 (4)	0.8559 (3)	0.67880 (16)	0.0231 (6)
N1A	0.4046 (4)	0.3030 (3)	0.77458 (15)	0.0128 (6)
H1NA	0.442 (6)	0.238 (3)	0.756 (2)	0.019*
N2A	0.3056 (4)	0.4176 (3)	0.73966 (16)	0.0146 (6)
N3A	0.6176 (4)	0.0642 (3)	0.85475 (16)	0.0136 (6)
N4A	0.5456 (4)	0.2375 (3)	1.06297 (16)	0.0154 (6)
C1A	0.4380 (5)	0.2851 (4)	0.84447 (18)	0.0127 (7)
C2A	0.5381 (4)	0.1691 (4)	0.88527 (18)	0.0125 (6)
C3A	0.5721 (4)	0.1543 (4)	0.95672 (18)	0.0126 (7)
H3A	0.6389	0.0787	0.9827	0.015*
C4A	0.5064 (4)	0.2520 (4)	0.98843 (18)	0.0128 (7)
C5A	0.4078 (5)	0.3681 (4)	0.95041 (19)	0.0152 (7)
H5A	0.3643	0.4335	0.9730	0.018*
C6A	0.3764 (5)	0.3842 (4)	0.87965 (18)	0.0139 (7)
H6A	0.3131	0.4620	0.8542	0.017*
C7A	0.2916 (5)	0.4404 (4)	0.67163 (18)	0.0131 (7)
C8A	0.3760 (5)	0.3548 (4)	0.62647 (19)	0.0183 (7)
H8A	0.4529	0.2834	0.6552	0.027*
H8B	0.4442	0.4068	0.5905	0.027*
H8C	0.2853	0.3194	0.6048	0.027*
C9A	0.1823 (5)	0.5658 (4)	0.63623 (18)	0.0138 (7)
C10A	0.1036 (5)	0.6493 (4)	0.67685 (19)	0.0157 (7)
H10A	0.1173	0.6256	0.7257	0.019*
C11A	0.0055 (5)	0.7671 (4)	0.6442 (2)	0.0168 (7)
C12A	−0.0155 (5)	0.8030 (4)	0.5704 (2)	0.0207 (8)
H12A	−0.0797	0.8830	0.5483	0.025*
C13A	0.0596 (6)	0.7191 (4)	0.5309 (2)	0.0227 (8)
H13A	0.0440	0.7424	0.4821	0.027*
C14A	0.1580 (5)	0.6005 (4)	0.56287 (19)	0.0189 (8)
H14A	0.2075	0.5445	0.5357	0.023*
C15A	−0.0621 (5)	0.8217 (4)	0.7541 (2)	0.0223 (8)
H15A	−0.1352	0.8862	0.7723	0.033*
H15B	0.0593	0.8200	0.7686	0.033*
H15C	−0.1019	0.7358	0.7720	0.033*
O1B	0.3655 (4)	0.3835 (3)	0.45297 (14)	0.0202 (6)
O2B	0.4931 (4)	0.1929 (3)	0.51179 (14)	0.0258 (7)
O3B	0.8328 (4)	−0.0989 (3)	0.39840 (15)	0.0215 (6)
O4B	0.7842 (4)	−0.0858 (3)	0.28765 (15)	0.0234 (6)
O5B	0.1203 (4)	0.6180 (3)	−0.00270 (14)	0.0187 (6)
N1B	0.3221 (4)	0.4301 (3)	0.31624 (16)	0.0150 (6)
H1NB	0.288 (6)	0.456 (5)	0.3542 (17)	0.022*
N2B	0.2573 (4)	0.4970 (3)	0.25056 (16)	0.0140 (6)
N3B	0.4467 (4)	0.2707 (3)	0.45574 (16)	0.0161 (6)
N4B	0.7603 (4)	−0.0432 (3)	0.34084 (17)	0.0167 (6)
C1B	0.4252 (4)	0.3144 (4)	0.32377 (18)	0.0124 (7)
C2B	0.4874 (5)	0.2337 (4)	0.39022 (18)	0.0121 (6)
C3B	0.5970 (5)	0.1153 (4)	0.39627 (19)	0.0136 (7)
H3B	0.6383	0.0645	0.4402	0.016*
C4B	0.6422 (4)	0.0759 (4)	0.33599 (18)	0.0128 (7)
C5B	0.5822 (5)	0.1513 (4)	0.26873 (19)	0.0145 (7)
H5B	0.6129	0.1218	0.2285	0.017*
C6B	0.4787 (5)	0.2677 (4)	0.26357 (18)	0.0131 (7)
H6B	0.4418	0.3185	0.2191	0.016*
C7B	0.1651 (4)	0.6103 (4)	0.24548 (18)	0.0129 (7)
C8B	0.1308 (5)	0.6726 (4)	0.3065 (2)	0.0193 (8)
H8D	0.1039	0.6061	0.3475	0.029*
H8E	0.0319	0.7399	0.2952	0.029*
H8F	0.2345	0.7117	0.3160	0.029*
C9B	0.0979 (5)	0.6790 (4)	0.17307 (19)	0.0136 (7)
C10B	0.1345 (5)	0.6197 (4)	0.11704 (19)	0.0144 (7)
H10B	0.2000	0.5369	0.1250	0.017*
C11B	0.0731 (5)	0.6842 (4)	0.0492 (2)	0.0147 (7)
C12B	−0.0255 (5)	0.8084 (4)	0.0359 (2)	0.0170 (7)
H12B	−0.0668	0.8509	−0.0095	0.020*
C13B	−0.0604 (5)	0.8667 (4)	0.0919 (2)	0.0183 (7)
H13B	−0.1250	0.9498	0.0838	0.022*
C14B	−0.0003 (5)	0.8030 (4)	0.1601 (2)	0.0166 (7)
H14B	−0.0259	0.8434	0.1971	0.020*
C15B	0.0306 (6)	0.6672 (4)	−0.0701 (2)	0.0216 (8)
H15D	0.0630	0.6079	−0.0998	0.032*
H15E	0.0645	0.7535	−0.0919	0.032*
H15F	−0.0957	0.6730	−0.0635	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0298 (14)	0.0200 (14)	0.0094 (12)	0.0053 (11)	−0.0047 (10)	−0.0060 (10)
O2A	0.0204 (13)	0.0123 (13)	0.0192 (13)	0.0049 (10)	−0.0053 (10)	−0.0018 (10)
O3A	0.0217 (13)	0.0195 (14)	0.0148 (12)	0.0016 (11)	−0.0053 (10)	−0.0002 (11)
O4A	0.0352 (16)	0.0217 (15)	0.0124 (12)	0.0048 (12)	−0.0008 (11)	−0.0064 (11)
O5A	0.0258 (14)	0.0187 (15)	0.0221 (14)	0.0074 (11)	−0.0007 (11)	−0.0040 (12)
N1A	0.0162 (14)	0.0105 (14)	0.0102 (14)	0.0036 (11)	−0.0039 (11)	−0.0015 (11)
N2A	0.0177 (14)	0.0137 (15)	0.0113 (14)	0.0022 (12)	−0.0046 (11)	−0.0023 (12)
N3A	0.0145 (14)	0.0131 (15)	0.0129 (14)	0.0011 (11)	−0.0005 (11)	−0.0038 (12)
N4A	0.0208 (15)	0.0144 (15)	0.0106 (14)	−0.0020 (12)	0.0000 (11)	−0.0021 (12)
C1A	0.0143 (15)	0.0129 (17)	0.0114 (16)	−0.0030 (13)	0.0018 (12)	−0.0031 (13)
C2A	0.0142 (15)	0.0134 (17)	0.0103 (15)	0.0000 (12)	0.0020 (12)	−0.0045 (13)
C3A	0.0116 (15)	0.0131 (17)	0.0123 (16)	−0.0022 (12)	0.0000 (12)	−0.0012 (13)
C4A	0.0129 (15)	0.0132 (17)	0.0106 (15)	−0.0007 (13)	−0.0003 (12)	0.0001 (13)
C5A	0.0189 (17)	0.0141 (18)	0.0124 (16)	−0.0002 (13)	0.0016 (13)	−0.0036 (13)
C6A	0.0174 (16)	0.0116 (17)	0.0114 (16)	0.0028 (13)	−0.0007 (12)	−0.0020 (13)
C7A	0.0159 (16)	0.0121 (17)	0.0110 (15)	−0.0006 (13)	−0.0008 (12)	−0.0026 (13)
C8A	0.0268 (19)	0.0173 (19)	0.0099 (16)	0.0026 (15)	−0.0002 (13)	−0.0037 (14)
C9A	0.0156 (16)	0.0128 (17)	0.0111 (16)	−0.0013 (13)	−0.0036 (12)	0.0005 (13)
C10A	0.0178 (16)	0.0157 (18)	0.0129 (16)	−0.0044 (14)	−0.0027 (13)	−0.0011 (14)
C11A	0.0150 (16)	0.0164 (18)	0.0191 (18)	−0.0014 (14)	0.0014 (13)	−0.0047 (15)
C12A	0.0229 (19)	0.0181 (19)	0.0172 (18)	0.0029 (15)	−0.0048 (14)	0.0015 (15)
C13A	0.029 (2)	0.025 (2)	0.0107 (17)	−0.0002 (16)	−0.0047 (14)	0.0008 (15)
C14A	0.0234 (18)	0.021 (2)	0.0103 (16)	0.0003 (15)	−0.0016 (13)	−0.0021 (14)
C15A	0.0220 (18)	0.024 (2)	0.0209 (19)	0.0018 (16)	0.0050 (15)	−0.0076 (16)
O1B	0.0289 (14)	0.0166 (14)	0.0147 (13)	0.0064 (11)	0.0003 (10)	−0.0066 (11)
O2B	0.0438 (18)	0.0211 (15)	0.0091 (12)	0.0063 (13)	0.0032 (11)	−0.0009 (11)
O3B	0.0248 (14)	0.0194 (14)	0.0169 (13)	0.0063 (11)	−0.0050 (11)	−0.0012 (11)
O4B	0.0310 (15)	0.0211 (15)	0.0178 (14)	0.0088 (12)	−0.0018 (11)	−0.0089 (12)
O5B	0.0233 (13)	0.0187 (14)	0.0136 (13)	0.0026 (11)	−0.0026 (10)	−0.0051 (11)
N1B	0.0193 (15)	0.0147 (15)	0.0098 (14)	0.0031 (12)	−0.0009 (11)	−0.0029 (12)
N2B	0.0140 (13)	0.0140 (15)	0.0118 (14)	0.0018 (11)	0.0000 (11)	−0.0001 (12)
N3B	0.0212 (15)	0.0158 (16)	0.0106 (14)	0.0002 (12)	0.0018 (11)	−0.0026 (12)
N4B	0.0182 (14)	0.0141 (16)	0.0171 (15)	0.0020 (12)	0.0006 (11)	−0.0040 (12)
C1B	0.0127 (15)	0.0120 (17)	0.0126 (16)	−0.0002 (12)	0.0004 (12)	−0.0034 (13)
C2B	0.0152 (15)	0.0137 (17)	0.0075 (15)	−0.0005 (13)	0.0015 (12)	−0.0029 (13)
C3B	0.0153 (16)	0.0132 (17)	0.0110 (15)	−0.0008 (13)	−0.0004 (12)	−0.0007 (13)
C4B	0.0132 (15)	0.0102 (16)	0.0136 (16)	0.0026 (12)	−0.0008 (12)	−0.0019 (13)
C5B	0.0146 (16)	0.0168 (18)	0.0130 (16)	−0.0019 (13)	−0.0016 (12)	−0.0048 (14)
C6B	0.0165 (16)	0.0121 (17)	0.0088 (15)	0.0003 (13)	−0.0015 (12)	0.0005 (13)
C7B	0.0114 (14)	0.0128 (17)	0.0137 (16)	0.0007 (12)	0.0006 (12)	−0.0024 (13)
C8B	0.0223 (18)	0.0192 (19)	0.0165 (17)	0.0050 (15)	−0.0016 (14)	−0.0075 (15)
C9B	0.0122 (15)	0.0140 (17)	0.0134 (16)	−0.0010 (13)	0.0002 (12)	−0.0015 (13)
C10B	0.0131 (15)	0.0128 (17)	0.0160 (17)	0.0012 (13)	0.0000 (12)	−0.0019 (14)
C11B	0.0137 (15)	0.0126 (17)	0.0181 (17)	−0.0028 (13)	0.0001 (13)	−0.0035 (14)
C12B	0.0149 (16)	0.0154 (18)	0.0193 (18)	0.0004 (13)	−0.0034 (13)	−0.0019 (14)
C13B	0.0192 (17)	0.0120 (17)	0.0211 (19)	0.0021 (14)	0.0010 (14)	−0.0006 (14)
C14B	0.0169 (16)	0.0155 (18)	0.0160 (17)	0.0005 (13)	0.0025 (13)	−0.0022 (14)
C15B	0.026 (2)	0.024 (2)	0.0146 (17)	−0.0027 (16)	−0.0031 (14)	−0.0044 (15)

Geometric parameters (Å, º) top

O1A—N3A	1.243 (4)	O1B—N3B	1.261 (4)
O2A—N3A	1.229 (4)	O2B—N3B	1.224 (4)
O3A—N4A	1.232 (4)	O3B—N4B	1.236 (4)
O4A—N4A	1.228 (4)	O4B—N4B	1.230 (4)
O5A—C11A	1.367 (5)	O5B—C11B	1.383 (5)
O5A—C15A	1.427 (5)	O5B—C15B	1.438 (5)
N1A—C1A	1.353 (4)	N1B—C1B	1.347 (5)
N1A—N2A	1.374 (4)	N1B—N2B	1.370 (4)
N1A—H1NA	0.868 (19)	N1B—H1NB	0.873 (19)
N2A—C7A	1.294 (5)	N2B—C7B	1.293 (5)
N3A—C2A	1.447 (5)	N3B—C2B	1.444 (4)
N4A—C4A	1.456 (4)	N4B—C4B	1.439 (5)
C1A—C6A	1.414 (5)	C1B—C6B	1.418 (5)
C1A—C2A	1.425 (5)	C1B—C2B	1.419 (5)
C2A—C3A	1.388 (5)	C2B—C3B	1.397 (5)
C3A—C4A	1.367 (5)	C3B—C4B	1.367 (5)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.402 (5)	C4B—C5B	1.409 (5)
C5A—C6A	1.370 (5)	C5B—C6B	1.360 (5)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—H6A	0.9300	C6B—H6B	0.9300
C7A—C9A	1.492 (5)	C7B—C9B	1.489 (5)
C7A—C8A	1.496 (5)	C7B—C8B	1.498 (5)
C8A—H8A	0.9600	C8B—H8D	0.9600
C8A—H8B	0.9600	C8B—H8E	0.9600
C8A—H8C	0.9600	C8B—H8F	0.9600
C9A—C14A	1.398 (5)	C9B—C14B	1.393 (5)
C9A—C10A	1.401 (5)	C9B—C10B	1.394 (5)
C10A—C11A	1.382 (5)	C10B—C11B	1.393 (5)
C10A—H10A	0.9300	C10B—H10B	0.9300
C11A—C12A	1.402 (5)	C11B—C12B	1.395 (5)
C12A—C13A	1.380 (6)	C12B—C13B	1.384 (6)
C12A—H12A	0.9300	C12B—H12B	0.9300
C13A—C14A	1.386 (6)	C13B—C14B	1.394 (5)
C13A—H13A	0.9300	C13B—H13B	0.9300
C14A—H14A	0.9300	C14B—H14B	0.9300
C15A—H15A	0.9600	C15B—H15D	0.9600
C15A—H15B	0.9600	C15B—H15E	0.9600
C15A—H15C	0.9600	C15B—H15F	0.9600

C11A—O5A—C15A	117.4 (3)	C11B—O5B—C15B	116.8 (3)
C1A—N1A—N2A	118.3 (3)	C1B—N1B—N2B	119.4 (3)
C1A—N1A—H1NA	117 (3)	C1B—N1B—H1NB	118 (3)
N2A—N1A—H1NA	125 (3)	N2B—N1B—H1NB	122 (3)
C7A—N2A—N1A	117.6 (3)	C7B—N2B—N1B	117.2 (3)
O2A—N3A—O1A	122.0 (3)	O2B—N3B—O1B	122.2 (3)
O2A—N3A—C2A	119.2 (3)	O2B—N3B—C2B	119.4 (3)
O1A—N3A—C2A	118.7 (3)	O1B—N3B—C2B	118.4 (3)
O4A—N4A—O3A	123.7 (3)	O4B—N4B—O3B	122.7 (3)
O4A—N4A—C4A	117.9 (3)	O4B—N4B—C4B	118.6 (3)
O3A—N4A—C4A	118.3 (3)	O3B—N4B—C4B	118.6 (3)
N1A—C1A—C6A	120.4 (3)	N1B—C1B—C6B	120.2 (3)
N1A—C1A—C2A	122.4 (3)	N1B—C1B—C2B	123.3 (3)
C6A—C1A—C2A	117.2 (3)	C6B—C1B—C2B	116.4 (3)
C3A—C2A—C1A	121.1 (3)	C3B—C2B—C1B	122.0 (3)
C3A—C2A—N3A	116.2 (3)	C3B—C2B—N3B	115.6 (3)
C1A—C2A—N3A	122.7 (3)	C1B—C2B—N3B	122.3 (3)
C4A—C3A—C2A	119.3 (3)	C4B—C3B—C2B	118.3 (3)
C4A—C3A—H3A	120.3	C4B—C3B—H3B	120.8
C2A—C3A—H3A	120.3	C2B—C3B—H3B	120.8
C3A—C4A—C5A	121.7 (3)	C3B—C4B—C5B	122.0 (3)
C3A—C4A—N4A	119.2 (3)	C3B—C4B—N4B	119.2 (3)
C5A—C4A—N4A	119.1 (3)	C5B—C4B—N4B	118.8 (3)
C6A—C5A—C4A	119.2 (3)	C6B—C5B—C4B	119.0 (3)
C6A—C5A—H5A	120.4	C6B—C5B—H5B	120.5
C4A—C5A—H5A	120.4	C4B—C5B—H5B	120.5
C5A—C6A—C1A	121.4 (3)	C5B—C6B—C1B	122.2 (3)
C5A—C6A—H6A	119.3	C5B—C6B—H6B	118.9
C1A—C6A—H6A	119.3	C1B—C6B—H6B	118.9
N2A—C7A—C9A	115.5 (3)	N2B—C7B—C9B	115.1 (3)
N2A—C7A—C8A	126.2 (3)	N2B—C7B—C8B	123.7 (3)
C9A—C7A—C8A	118.2 (3)	C9B—C7B—C8B	121.2 (3)
C7A—C8A—H8A	109.5	C7B—C8B—H8D	109.5
C7A—C8A—H8B	109.5	C7B—C8B—H8E	109.5
H8A—C8A—H8B	109.5	H8D—C8B—H8E	109.5
C7A—C8A—H8C	109.5	C7B—C8B—H8F	109.5
H8A—C8A—H8C	109.5	H8D—C8B—H8F	109.5
H8B—C8A—H8C	109.5	H8E—C8B—H8F	109.5
C14A—C9A—C10A	119.8 (3)	C14B—C9B—C10B	119.1 (3)
C14A—C9A—C7A	120.5 (3)	C14B—C9B—C7B	120.9 (3)
C10A—C9A—C7A	119.7 (3)	C10B—C9B—C7B	119.9 (3)
C11A—C10A—C9A	119.9 (3)	C11B—C10B—C9B	120.1 (3)
C11A—C10A—H10A	120.0	C11B—C10B—H10B	120.0
C9A—C10A—H10A	120.0	C9B—C10B—H10B	120.0
O5A—C11A—C10A	124.5 (3)	O5B—C11B—C10B	115.3 (3)
O5A—C11A—C12A	115.4 (3)	O5B—C11B—C12B	123.6 (3)
C10A—C11A—C12A	120.2 (4)	C10B—C11B—C12B	121.0 (3)
C13A—C12A—C11A	119.6 (4)	C13B—C12B—C11B	118.4 (3)
C13A—C12A—H12A	120.2	C13B—C12B—H12B	120.8
C11A—C12A—H12A	120.2	C11B—C12B—H12B	120.8
C12A—C13A—C14A	121.0 (4)	C12B—C13B—C14B	121.1 (4)
C12A—C13A—H13A	119.5	C12B—C13B—H13B	119.4
C14A—C13A—H13A	119.5	C14B—C13B—H13B	119.4
C13A—C14A—C9A	119.5 (4)	C9B—C14B—C13B	120.2 (4)
C13A—C14A—H14A	120.2	C9B—C14B—H14B	119.9
C9A—C14A—H14A	120.2	C13B—C14B—H14B	119.9
O5A—C15A—H15A	109.5	O5B—C15B—H15D	109.5
O5A—C15A—H15B	109.5	O5B—C15B—H15E	109.5
H15A—C15A—H15B	109.5	H15D—C15B—H15E	109.5
O5A—C15A—H15C	109.5	O5B—C15B—H15F	109.5
H15A—C15A—H15C	109.5	H15D—C15B—H15F	109.5
H15B—C15A—H15C	109.5	H15E—C15B—H15F	109.5

C1A—N1A—N2A—C7A	172.4 (3)	C1B—N1B—N2B—C7B	−177.2 (3)
N2A—N1A—C1A—C6A	−1.9 (5)	N2B—N1B—C1B—C6B	5.4 (5)
N2A—N1A—C1A—C2A	179.5 (3)	N2B—N1B—C1B—C2B	−175.2 (3)
N1A—C1A—C2A—C3A	179.2 (3)	N1B—C1B—C2B—C3B	−178.8 (3)
C6A—C1A—C2A—C3A	0.5 (5)	C6B—C1B—C2B—C3B	0.7 (5)
N1A—C1A—C2A—N3A	2.5 (5)	N1B—C1B—C2B—N3B	−0.9 (5)
C6A—C1A—C2A—N3A	−176.2 (3)	C6B—C1B—C2B—N3B	178.5 (3)
O2A—N3A—C2A—C3A	2.4 (5)	O2B—N3B—C2B—C3B	−7.3 (5)
O1A—N3A—C2A—C3A	−176.6 (3)	O1B—N3B—C2B—C3B	172.1 (3)
O2A—N3A—C2A—C1A	179.2 (3)	O2B—N3B—C2B—C1B	174.7 (3)
O1A—N3A—C2A—C1A	0.2 (5)	O1B—N3B—C2B—C1B	−5.9 (5)
C1A—C2A—C3A—C4A	0.8 (5)	C1B—C2B—C3B—C4B	−1.2 (5)
N3A—C2A—C3A—C4A	177.7 (3)	N3B—C2B—C3B—C4B	−179.1 (3)
C2A—C3A—C4A—C5A	−1.1 (5)	C2B—C3B—C4B—C5B	0.3 (5)
C2A—C3A—C4A—N4A	−178.7 (3)	C2B—C3B—C4B—N4B	177.7 (3)
O4A—N4A—C4A—C3A	−177.2 (3)	O4B—N4B—C4B—C3B	171.9 (3)
O3A—N4A—C4A—C3A	3.2 (5)	O3B—N4B—C4B—C3B	−7.7 (5)
O4A—N4A—C4A—C5A	5.2 (5)	O4B—N4B—C4B—C5B	−10.6 (5)
O3A—N4A—C4A—C5A	−174.4 (3)	O3B—N4B—C4B—C5B	169.8 (3)
C3A—C4A—C5A—C6A	0.0 (5)	C3B—C4B—C5B—C6B	1.1 (5)
N4A—C4A—C5A—C6A	177.6 (3)	N4B—C4B—C5B—C6B	−176.3 (3)
C4A—C5A—C6A—C1A	1.3 (5)	C4B—C5B—C6B—C1B	−1.7 (5)
N1A—C1A—C6A—C5A	179.7 (3)	N1B—C1B—C6B—C5B	−179.8 (3)
C2A—C1A—C6A—C5A	−1.5 (5)	C2B—C1B—C6B—C5B	0.8 (5)
N1A—N2A—C7A—C9A	179.8 (3)	N1B—N2B—C7B—C9B	179.9 (3)
N1A—N2A—C7A—C8A	−1.3 (5)	N1B—N2B—C7B—C8B	1.7 (5)
N2A—C7A—C9A—C14A	180.0 (3)	N2B—C7B—C9B—C14B	−178.8 (3)
C8A—C7A—C9A—C14A	1.0 (5)	C8B—C7B—C9B—C14B	−0.5 (5)
N2A—C7A—C9A—C10A	0.1 (5)	N2B—C7B—C9B—C10B	0.6 (5)
C8A—C7A—C9A—C10A	−179.0 (3)	C8B—C7B—C9B—C10B	178.9 (3)
C14A—C9A—C10A—C11A	−1.4 (5)	C14B—C9B—C10B—C11B	0.0 (5)
C7A—C9A—C10A—C11A	178.5 (3)	C7B—C9B—C10B—C11B	−179.4 (3)
C15A—O5A—C11A—C10A	−2.6 (5)	C15B—O5B—C11B—C10B	167.7 (3)
C15A—O5A—C11A—C12A	178.0 (3)	C15B—O5B—C11B—C12B	−13.8 (5)
C9A—C10A—C11A—O5A	−179.3 (3)	C9B—C10B—C11B—O5B	178.6 (3)
C9A—C10A—C11A—C12A	0.1 (5)	C9B—C10B—C11B—C12B	0.0 (5)
O5A—C11A—C12A—C13A	−179.4 (3)	O5B—C11B—C12B—C13B	−178.2 (3)
C10A—C11A—C12A—C13A	1.1 (6)	C10B—C11B—C12B—C13B	0.3 (5)
C11A—C12A—C13A—C14A	−1.0 (6)	C11B—C12B—C13B—C14B	−0.6 (5)
C12A—C13A—C14A—C9A	−0.3 (6)	C10B—C9B—C14B—C13B	−0.2 (5)
C10A—C9A—C14A—C13A	1.5 (6)	C7B—C9B—C14B—C13B	179.2 (3)
C7A—C9A—C14A—C13A	−178.4 (3)	C12B—C13B—C14B—C9B	0.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1A	0.87 (3)	1.94 (4)	2.611 (4)	133 (3)
N1B—H1NB···O1B	0.88 (4)	1.96 (3)	2.611 (4)	130 (4)
C5B—H5B···O3Aⁱ	0.93	2.59	3.462 (5)	156
C6B—H6B···O4Aⁱ	0.93	2.50	3.277 (4)	141
C8A—H8C···O3Bⁱⁱ	0.96	2.57	3.376 (5)	142
C8B—H8E···O4Bⁱⁱⁱ	0.96	2.45	3.402 (5)	170
C12B—H12B···O2A^iv	0.93	2.57	3.447 (5)	157
C13A—H13A···O3Bⁱⁱⁱ	0.93	2.48	3.204 (5)	135
C13B—H13B···O3A^iv	0.93	2.55	3.448 (5)	162
C14B—H14B···O4Bⁱⁱⁱ	0.93	2.47	3.338 (5)	155
C15B—H15E···O3A^v	0.96	2.57	3.301 (5)	133

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₄O₅
M_r	330.30
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.5612 (13), 10.4517 (18), 19.516 (3)
α, β, γ (°)	76.034 (4), 89.531 (4), 84.052 (4)
V (Å³)	1488.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.33 × 0.14 × 0.05

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.964, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	7846, 7846, 5592
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.086, 0.296, 1.11
No. of reflections	7846
No. of parameters	444
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.59

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	0.87 (3)	1.94 (4)	2.611 (4)	133 (3)
N1B—H1NB···O1B	0.88 (4)	1.96 (3)	2.611 (4)	130 (4)
C5B—H5B···O3Aⁱ	0.93	2.59	3.462 (5)	156
C6B—H6B···O4Aⁱ	0.93	2.50	3.277 (4)	141
C8A—H8C···O3Bⁱⁱ	0.96	2.57	3.376 (5)	142
C8B—H8E···O4Bⁱⁱⁱ	0.96	2.45	3.402 (5)	170
C12B—H12B···O2A^iv	0.93	2.57	3.447 (5)	157
C13A—H13A···O3Bⁱⁱⁱ	0.93	2.48	3.204 (5)	135
C13B—H13B···O3A^iv	0.93	2.55	3.448 (5)	162
C14B—H14B···O4Bⁱⁱⁱ	0.93	2.47	3.338 (5)	155
C15B—H15E···O3A^v	0.96	2.57	3.301 (5)	133

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

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

Acknowledgements

BN and TK thank the Crystal Materials Research Unit, Prince of Songkla University, for financial support. The authors thank Prince of Songkla University and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bendre, R., Murugkar, A., Padhye, S., Kulkarni, P. & Karve, M. (1998). Met. Based Drugs, 5, 59–66. CrossRef PubMed CAS 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 (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chantrapromma, S., Nilwanna, B., Kobkeatthawin, T., Jansrisewangwong, P. & Fun, H.-K. (2012). Acta Cryst. E68, o1644–o1645. CSD CrossRef IUCr Journals Google Scholar
El-Sherif, A. A. (2009). Inorg. Chim. Acta, 362, 4991–5000. Web of Science CrossRef CAS Google Scholar
Fun, H.-K., Jansrisewangwong, P. & Chantrapromma, S. (2010). Acta Cryst. E66, o2401–o2402. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Gokce, M., Utku, S. & Kupeli, E. (2009). Eur. J. Med. Chem. 44, 3760–3764. Web of Science CrossRef PubMed Google Scholar
Molyneux, P. (2004). Songklanakarin J. Sci. Technol. 26, 211–219. CAS Google Scholar
Nilwanna, B., Chantrapromma, S., Jansrisewangwong, P. & Fun, H.-K. (2011). Acta Cryst. E67, o3084–o3085. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sathyadevi, P., Krishnamoorthy, P., Alagesan, M., Thanigaimani, K., Thomas, M. P. & Dharmaraj, N. (2012). Polyhedron, 31, 294–306. Web of Science CSD CrossRef CAS 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
Xia, Y., Fan, C.-D., Zhao, B.-X., Zhao, J., Shin, D.-S. & Miao, J.-Y. (2008). Eur. J. Med. Chem. 43, 2347–2353. Web of Science CrossRef PubMed CAS Google Scholar