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

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

doi:10.1107/S160053681201937X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1644-o1645

doi:10.1107/S160053681201937X

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

Suchada Chantrapromma,^a ^*‡ Boonlerd Nilwanna,^a Thawanrat Kobkeatthawin,^a Patcharaporn Jansrisewangwong ^a and Hoong-Kun Fun ^b §

^aCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 8 April 2012; accepted 30 April 2012; online 5 May 2012)

The molecule of the title hydrazone derivative, C₁₄H₁₁FN₄O₄, is nearly planar, with a dihedral angle between the benzene rings of 3.71 (7)°. The central ethylidenehydrazine N—N=C—C plane makes dihedral angles of 5.32 (10) and 9.02 (10)° with the 2,4-dinitro- and 3-fluoro-substituted benzene rings, respectively. An intramolecular N—H⋯O bond generates an S(6) ring motif. In the crystal, molecules are linked by weak C—H⋯O interactions into a sheet parallel to (10-1). The molecules are further stacked along the a axis by π–π interactions with centroid–centroid distances of 3.6314 (9) and 3.7567 (10) Å. A C⋯F short contact [2.842 (3) Å] is observed. The 3-fluorophenyl group is disordered over two orientations with a site-occupancy ratio of 0.636 (3):0.364 (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. (2011 ); Fun et al. (2011 , 2012 ); Nilwanna et al. (2011 ). For background to and the biological activity of hydrozones, see: Cui et al. (2010 ); Gokce et al. (2009 ); Krishnamoorthy et al. (2011 ); Molyneux (2004 ); Wang et al. (2009 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₄H₁₁FN₄O₄
M_r = 318.27
Monoclinic, P 2₁ /c
a = 7.0165 (6) Å
b = 13.3336 (11) Å
c = 14.4498 (12) Å
β = 94.791 (2)°
V = 1347.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 100 K
0.39 × 0.15 × 0.14 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.952, T_max = 0.982
15079 measured reflections
3874 independent reflections
3126 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.155
S = 1.07
3874 reflections
223 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 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
N2—H1N2⋯O1	0.89 (2)	1.90 (2)	2.6038 (18)	135 (2)
C9—H9A⋯O1ⁱ	0.93	2.58	3.413 (2)	150
C13—H13A⋯O4ⁱⁱ	0.93	2.44	3.176 (2)	137
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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/S160053681201937X/is5116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201937X/is5116Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681201937X/is5116Isup3.cml

checkCIF report

Comment top

The variety of interesting biological activities of hydrazones and their complexes such as antibacterial, antifungal, anti-inflammatory as well as antioxidant properties (Cui et al., 2010; Gokce et al., 2009; Krishnamoorthy et al., 2011; Wang et al., 2009) has prompted us to synthesize several hydrazone derivatives and to study for their biological activities. However the title compound (I) which was synthesized for 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 the molecular structure of (I), C₁₄H₁₁FN₄O₄, the F atoms of the 3-fluorophenyl group is disordered over two positions with the major component A and the minor B component rotated by 180° about the C7—C8 bond and having a refined site-occupancy ratio of 0.636 (3):0.364 (3) (Fig. 1). The molecule is nearly planar with a dihedral angle between the two benzene rings being 3.71 (7)°. The middle ethylidenehydrazine bridge is planar with the torsion angle N2–N1–C7–C14 = 0.8 (2)°. The mean plane through this middle bridge makes dihedral angles of 5.32 (10) and 9.02 (10)° with the 2,4-dinitrophenyl and 3-fluorophenyl rings, respectively. The two nitro groups of the 2,4-dinitrophenyl unit are slightly twisted with the attached benzene ring as indicated by the torsion angles O1–N3–C2–C1 = -3.8 (2)°, O2–N3–C2–C1 = 176.52 (15)°, O3–N4–C4–C3 = -8.3 (2)° and O4–N4–C4–C3 = 171.96 (16)°. An intramolecular N2—H1N2···O1 hydrogen bond (Fig.1 and Table 1) generates an S(6) ring motif (Bernstein et al., 1995). The bond distances are in normal ranges (Allen et al., 1987) and are comparable with the closely 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 a sheet parallel to the (101) plane and these sheets are stacked along the a axis by π–π interactions with centroid-to-centroid distances Cg1···Cg2 = 3.7567 (10)ⁱⁱⁱ and 3.6314 (9)^iv Å [symmetry codes (iii) = -x, 1-y, 1-z and (iv) = 1-x, 1-y, 1-z)]. A C14···F1B^v [2.905 (3) Å ; symmetry code (v) = -x, -1/2+y, 1/2-z] short contact is observed.

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. (2011); Fun et al. (2011, 2012); Nilwanna et al. (2011). For background to and the biological activity of hydrozones, see: Cui et al. (2010); Gokce et al. (2009); Krishnamoorthy et al. (2011); Molyneux (2004); Wang et al. (2009). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

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-Fluoroacetophenone (0.25 ml, 2 mmol) was then added to the solution with continuous stirring. The solution was stirred for 1 hr yielding an yellow solid, which was filtered off and washed with methanol. Yellow block-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. 503-504 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 the title compound, with 45% probability displacement ellipsoids and the atom-numbering scheme. Open bonds show the minor component. The hydrogen bond is shown as a dashed line.
	Fig. 2. The crystal packing of the major component of the title compound viewed down the a axis. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₁₄H₁₁FN₄O₄	F(000) = 656
M_r = 318.27	D_x = 1.569 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 503–504 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.0165 (6) Å	Cell parameters from 3874 reflections
b = 13.3336 (11) Å	θ = 2.1–30.0°
c = 14.4498 (12) Å	µ = 0.13 mm⁻¹
β = 94.791 (2)°	T = 100 K
V = 1347.1 (2) Å³	Block, yellow
Z = 4	0.39 × 0.15 × 0.14 mm

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	3874 independent reflections
Radiation source: sealed tube	3126 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 30.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.952, T_max = 0.982	k = −18→18
15079 measured reflections	l = −20→19

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0567P)² + 0.806P] where P = (F_o² + 2F_c²)/3
3874 reflections	(Δ/σ)_max = 0.001
223 parameters	Δρ_max = 0.70 e Å⁻³
2 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₁₄H₁₁FN₄O₄	V = 1347.1 (2) Å³
M_r = 318.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0165 (6) Å	µ = 0.13 mm⁻¹
b = 13.3336 (11) Å	T = 100 K
c = 14.4498 (12) Å	0.39 × 0.15 × 0.14 mm
β = 94.791 (2)°

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	3874 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3126 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.982	R_int = 0.054
15079 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	2 restraints
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.70 e Å⁻³
3874 reflections	Δρ_min = −0.59 e Å⁻³
223 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	Occ. (<1)
O1	0.16769 (19)	0.27587 (9)	0.33374 (8)	0.0286 (3)
O2	0.2526 (2)	0.12572 (9)	0.37606 (9)	0.0362 (3)
O3	0.4548 (2)	0.04192 (10)	0.68409 (10)	0.0395 (3)
O4	0.5525 (2)	0.15695 (12)	0.78252 (10)	0.0421 (4)
N1	0.22627 (19)	0.52482 (9)	0.47367 (9)	0.0204 (3)
N2	0.2316 (2)	0.42615 (10)	0.44717 (9)	0.0211 (3)
H1N2	0.187 (4)	0.4037 (18)	0.3918 (17)	0.039 (6)*
N3	0.2368 (2)	0.21543 (10)	0.39303 (9)	0.0239 (3)
N4	0.4801 (2)	0.13015 (11)	0.70636 (10)	0.0283 (3)
C1	0.2965 (2)	0.35508 (11)	0.50920 (10)	0.0190 (3)
C2	0.2999 (2)	0.25164 (11)	0.48499 (10)	0.0197 (3)
C3	0.3613 (2)	0.17866 (11)	0.54990 (11)	0.0212 (3)
H3A	0.3624	0.1113	0.5332	0.025*
C4	0.4199 (2)	0.20773 (12)	0.63873 (11)	0.0224 (3)
C5	0.4229 (2)	0.30902 (13)	0.66526 (11)	0.0231 (3)
H5A	0.4656	0.3272	0.7256	0.028*
C6	0.3626 (2)	0.38075 (12)	0.60177 (10)	0.0210 (3)
H6A	0.3649	0.4478	0.6196	0.025*
C7	0.1518 (2)	0.58571 (11)	0.41102 (10)	0.0202 (3)
C8	0.1511 (2)	0.69296 (11)	0.43865 (11)	0.0205 (3)
C9	0.1014 (2)	0.76901 (13)	0.37412 (12)	0.0264 (3)
H9A	0.0644	0.7534	0.3125	0.032*
C10	0.1085 (3)	0.86754 (13)	0.40379 (13)	0.0332 (4)
H10A	0.0755	0.9175	0.3605	0.040*	0.636 (4)
F1A	0.2507 (3)	0.84685 (12)	0.64414 (10)	0.0370 (5)	0.636 (4)
C11	0.1615 (3)	0.89560 (13)	0.49351 (14)	0.0310 (4)
H11A	0.1654	0.9626	0.5115	0.037*
C12	0.2086 (2)	0.81953 (12)	0.55571 (10)	0.0277 (3)
H12A	0.2449	0.8363	0.6171	0.033*	0.364 (4)
F1B	0.0366 (5)	0.9380 (2)	0.3455 (2)	0.0441 (10)	0.364 (4)
C13	0.2046 (2)	0.71958 (11)	0.53113 (11)	0.0227 (3)
H13A	0.2369	0.6704	0.5753	0.027*
C14	0.0737 (3)	0.55223 (14)	0.31617 (11)	0.0284 (4)
H14A	−0.0124	0.4970	0.3219	0.043*
H14B	0.1771	0.5314	0.2811	0.043*
H14C	0.0064	0.6068	0.2848	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0396 (7)	0.0257 (6)	0.0197 (5)	0.0008 (5)	−0.0015 (5)	−0.0019 (4)
O2	0.0563 (9)	0.0211 (6)	0.0306 (6)	0.0018 (6)	0.0001 (6)	−0.0088 (5)
O3	0.0511 (9)	0.0265 (6)	0.0403 (7)	−0.0014 (6)	−0.0006 (6)	0.0095 (5)
O4	0.0501 (9)	0.0426 (8)	0.0307 (7)	0.0046 (7)	−0.0129 (6)	0.0045 (6)
N1	0.0226 (6)	0.0174 (6)	0.0214 (6)	−0.0015 (5)	0.0035 (5)	−0.0011 (5)
N2	0.0264 (7)	0.0184 (6)	0.0183 (6)	−0.0002 (5)	0.0016 (5)	−0.0019 (4)
N3	0.0285 (7)	0.0220 (6)	0.0212 (6)	−0.0015 (5)	0.0027 (5)	−0.0042 (5)
N4	0.0263 (7)	0.0300 (7)	0.0285 (7)	0.0008 (6)	0.0015 (6)	0.0062 (6)
C1	0.0179 (6)	0.0197 (6)	0.0198 (6)	−0.0015 (5)	0.0037 (5)	−0.0013 (5)
C2	0.0191 (7)	0.0213 (7)	0.0188 (6)	−0.0017 (5)	0.0029 (5)	−0.0025 (5)
C3	0.0196 (7)	0.0195 (6)	0.0248 (7)	−0.0017 (5)	0.0034 (5)	−0.0002 (5)
C4	0.0192 (7)	0.0257 (7)	0.0223 (7)	−0.0008 (6)	0.0019 (5)	0.0039 (6)
C5	0.0205 (7)	0.0279 (8)	0.0207 (7)	−0.0027 (6)	0.0014 (5)	−0.0017 (5)
C6	0.0206 (7)	0.0218 (7)	0.0207 (7)	−0.0019 (5)	0.0013 (5)	−0.0033 (5)
C7	0.0197 (7)	0.0216 (7)	0.0197 (6)	0.0008 (5)	0.0037 (5)	−0.0017 (5)
C8	0.0184 (7)	0.0201 (7)	0.0233 (7)	0.0005 (5)	0.0029 (5)	0.0011 (5)
C9	0.0234 (7)	0.0276 (8)	0.0278 (8)	0.0030 (6)	0.0003 (6)	0.0044 (6)
C10	0.0272 (8)	0.0261 (8)	0.0454 (10)	0.0061 (7)	−0.0008 (7)	0.0070 (7)
F1A	0.0497 (11)	0.0250 (8)	0.0343 (9)	0.0030 (7)	−0.0078 (8)	−0.0097 (6)
C11	0.0257 (8)	0.0192 (7)	0.0478 (10)	0.0025 (6)	0.0020 (7)	−0.0024 (7)
C12	0.0258 (8)	0.0222 (7)	0.0353 (9)	−0.0019 (6)	0.0031 (7)	−0.0064 (6)
F1B	0.059 (2)	0.0236 (15)	0.048 (2)	0.0038 (14)	−0.0056 (16)	0.0141 (13)
C13	0.0247 (7)	0.0192 (7)	0.0241 (7)	−0.0009 (6)	0.0023 (6)	−0.0003 (5)
C14	0.0348 (9)	0.0297 (8)	0.0203 (7)	0.0060 (7)	−0.0011 (6)	−0.0033 (6)

Geometric parameters (Å, º) top

O1—N3	1.2447 (18)	C7—C8	1.485 (2)
O2—N3	1.2279 (18)	C7—C14	1.501 (2)
O3—N4	1.229 (2)	C8—C9	1.402 (2)
O4—N4	1.226 (2)	C8—C13	1.403 (2)
N1—C7	1.293 (2)	C9—C10	1.381 (3)
N1—N2	1.3716 (18)	C9—H9A	0.9300
N2—C1	1.357 (2)	C10—F1B	1.3322 (10)
N2—H1N2	0.89 (2)	C10—C11	1.371 (3)
N3—C2	1.4478 (19)	C10—H10A	0.9300
N4—C4	1.461 (2)	F1A—C12	1.3377 (10)
C1—C6	1.420 (2)	C11—C12	1.377 (2)
C1—C2	1.424 (2)	C11—H11A	0.9300
C2—C3	1.395 (2)	C12—C13	1.379 (2)
C3—C4	1.371 (2)	C12—H12A	0.9300
C3—H3A	0.9300	C13—H13A	0.9300
C4—C5	1.404 (2)	C14—H14A	0.9600
C5—C6	1.368 (2)	C14—H14B	0.9600
C5—H5A	0.9300	C14—H14C	0.9600
C6—H6A	0.9300

C7—N1—N2	115.18 (13)	C8—C7—C14	121.53 (14)
C1—N2—N1	120.07 (13)	C9—C8—C13	118.84 (15)
C1—N2—H1N2	115.7 (16)	C9—C8—C7	121.61 (14)
N1—N2—H1N2	124.1 (16)	C13—C8—C7	119.55 (13)
O2—N3—O1	121.97 (14)	C10—C9—C8	118.75 (16)
O2—N3—C2	118.85 (14)	C10—C9—H9A	120.6
O1—N3—C2	119.18 (13)	C8—C9—H9A	120.6
O4—N4—O3	123.64 (15)	F1B—C10—C11	117.6 (2)
O4—N4—C4	117.97 (15)	F1B—C10—C9	118.2 (2)
O3—N4—C4	118.39 (15)	C11—C10—C9	123.58 (15)
N2—C1—C6	121.26 (14)	C11—C10—H10A	118.2
N2—C1—C2	121.73 (13)	C9—C10—H10A	118.2
C6—C1—C2	117.01 (13)	C10—C11—C12	116.59 (15)
C3—C2—C1	121.42 (14)	C10—C11—H11A	121.7
C3—C2—N3	115.98 (13)	C12—C11—H11A	121.7
C1—C2—N3	122.59 (13)	F1A—C12—C11	116.40 (16)
C4—C3—C2	118.96 (14)	F1A—C12—C13	120.49 (16)
C4—C3—H3A	120.5	C11—C12—C13	123.03 (14)
C2—C3—H3A	120.5	C11—C12—H12A	118.5
C3—C4—C5	121.62 (14)	C13—C12—H12A	118.5
C3—C4—N4	118.27 (14)	C12—C13—C8	119.20 (14)
C5—C4—N4	120.11 (14)	C12—C13—H13A	120.4
C6—C5—C4	119.53 (14)	C8—C13—H13A	120.4
C6—C5—H5A	120.2	C7—C14—H14A	109.5
C4—C5—H5A	120.2	C7—C14—H14B	109.5
C5—C6—C1	121.44 (14)	H14A—C14—H14B	109.5
C5—C6—H6A	119.3	C7—C14—H14C	109.5
C1—C6—H6A	119.3	H14A—C14—H14C	109.5
N1—C7—C8	115.24 (13)	H14B—C14—H14C	109.5
N1—C7—C14	123.22 (14)

C7—N1—N2—C1	−176.16 (14)	C4—C5—C6—C1	0.1 (2)
N1—N2—C1—C6	−0.9 (2)	N2—C1—C6—C5	178.07 (14)
N1—N2—C1—C2	178.42 (13)	C2—C1—C6—C5	−1.3 (2)
N2—C1—C2—C3	−178.00 (14)	N2—N1—C7—C8	−178.27 (12)
C6—C1—C2—C3	1.4 (2)	N2—N1—C7—C14	0.8 (2)
N2—C1—C2—N3	0.7 (2)	N1—C7—C8—C9	170.45 (14)
C6—C1—C2—N3	−179.90 (13)	C14—C7—C8—C9	−8.6 (2)
O2—N3—C2—C3	−4.7 (2)	N1—C7—C8—C13	−8.4 (2)
O1—N3—C2—C3	174.98 (14)	C14—C7—C8—C13	172.56 (15)
O2—N3—C2—C1	176.52 (15)	C13—C8—C9—C10	0.5 (2)
O1—N3—C2—C1	−3.8 (2)	C7—C8—C9—C10	−178.31 (15)
C1—C2—C3—C4	−0.2 (2)	C8—C9—C10—F1B	−171.0 (2)
N3—C2—C3—C4	−178.96 (13)	C8—C9—C10—C11	−0.1 (3)
C2—C3—C4—C5	−1.2 (2)	F1B—C10—C11—C12	170.7 (2)
C2—C3—C4—N4	178.77 (13)	C9—C10—C11—C12	−0.3 (3)
O4—N4—C4—C3	171.96 (16)	C10—C11—C12—F1A	−176.64 (18)
O3—N4—C4—C3	−8.3 (2)	C10—C11—C12—C13	0.1 (3)
O4—N4—C4—C5	−8.1 (2)	F1A—C12—C13—C8	176.95 (17)
O3—N4—C4—C5	171.62 (16)	C11—C12—C13—C8	0.3 (3)
C3—C4—C5—C6	1.3 (2)	C9—C8—C13—C12	−0.6 (2)
N4—C4—C5—C6	−178.70 (14)	C7—C8—C13—C12	178.24 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1	0.89 (2)	1.90 (2)	2.6038 (18)	135 (2)
C9—H9A···O1ⁱ	0.93	2.58	3.413 (2)	150
C13—H13A···O4ⁱⁱ	0.93	2.44	3.176 (2)	137

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁FN₄O₄
M_r	318.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.0165 (6), 13.3336 (11), 14.4498 (12)
β (°)	94.791 (2)
V (Å³)	1347.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.39 × 0.15 × 0.14

Data collection
Diffractometer	Bruker APEX DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.952, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	15079, 3874, 3126
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.155, 1.07
No. of reflections	3874
No. of parameters	223
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)	0.70, −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
N2—H1N2···O1	0.89 (2)	1.90 (2)	2.6038 (18)	135 (2)
C9—H9A···O1ⁱ	0.93	2.58	3.413 (2)	150
C13—H13A···O4ⁱⁱ	0.93	2.44	3.176 (2)	137

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

Footnotes

‡Thomson Reuters ResearcherID: A-5085-2009

§Additional correspondence author, e-mail: hkfun@usm.my. Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

BN, TK and PJ 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

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