Ethyl 2-[(E)-4-(dimethyl­amino)benzyl­idenehydrazino]-5-nitro­benzoate

Fun, H.-K.; Adhikari, A.; Patil, P.S.; Kalluraya, B.; Chantrapromma, S.

doi:10.1107/S1600536808035939

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Pages o2286-o2287

doi:10.1107/S1600536808035939

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Ethyl 2-[(E)-4-(dimethylamino)benzylidenehydrazino]-5-nitrobenzoate

Hoong-Kun Fun,^a ^* Adithya Adhikari,^b P. S. Patil,^c ‡ B. Kalluraya ^b and Suchada Chantrapromma ^d §

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India, ^cDepartment of Physics, K.L.E. Society's K.L.E. Institute of Technology, Gokul Road, Hubli 590 030, India, and ^dCrystal 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 29 October 2008; accepted 1 November 2008; online 8 November 2008)

The title compound, C₁₈H₂₀N₄O₄, exists in the E configuration with respect to the C=N bond of the methylidine unit. The dihedral angle between the two benzene rings is 9.01 (6)°. An intramolecular N—H⋯O hydrogen bond involving the benzoate unit generates an S(6) ring motif. In the crystal, the molecules are linked by weak C—H⋯O interactions into infinite chains along the b axis. These chains are further connected into sheets parallel to the ab plane which are stacked approximately along the c axis. A C—H⋯π interaction is also observed.

Related literature

For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 ). For bond-length data, see: Allen et al. (1987 ). For background to the applications of hydrazones, see, for example: Barton et al. (1962 ); Bedia et al. (2006 ); Buu-Hoi et al. (1953 ); Paquette (1995 ); Rollas et al. (2002 ); Terzioglu & Gürsoy (2003 ).

Experimental

Crystal data

C₁₈H₂₀N₄O₄
M_r = 356.38
Monoclinic, P 2₁ /c
a = 10.8216 (4) Å
b = 15.9175 (6) Å
c = 10.4136 (4) Å
β = 107.091 (2)°
V = 1714.56 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100.0 (1) K
0.44 × 0.41 × 0.31 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.957, T_max = 0.970
16368 measured reflections
3929 independent reflections
3275 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.105
S = 1.04
3929 reflections
242 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O4	0.875 (18)	1.978 (17)	2.6736 (14)	135.6 (14)
C7—H7A⋯O1ⁱ	0.93	2.49	3.3599 (16)	156
C12—H12A⋯O4ⁱⁱ	0.93	2.59	3.3961 (16)	145
C16—H16C⋯O2ⁱⁱⁱ	0.96	2.59	3.5116 (19)	162
C17—H17B⋯Cg1ⁱⁱⁱ	0.96	2.64	3.4629 (14)	144
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ . Cg1 is the centroid of the C1–C6 ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035939/is2354sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035939/is2354Isup2.hkl

checkCIF report

Comment top

Hydrazine is widely used as a reagent in synthetic organic chemistry but is probably most frequently associated with the transformation of carbonyl-containing compounds to the corresponding hydrazones (Paquette, 1995). These are intermediates in the Wolff-Kishner reduction as well as many other reactions of synthetic utility, such as the Barton vinyl iodide preparation (Barton et al., 1962). Hydrazones have been demonstrated to possess antimicrobial, anticonvulsant, analgesic, antiinflammatory, antiplatelet, antitubercular, anticancer and antitumoral activities (Bedia et al., 2006; Rollas et al., 2002; Terzioglu & Gürsoy, 2003). Hydrazones possessing an azometine –NHN=CH– proton constitute an important class of compounds for new drug development. Therefore, many researchers have synthesized these compounds as target structures to evaluate their biological activities. These observations have been the guides for the development of new hydrazones that possess varied biological activities. Some synthesized hydrazide-hydrazones were reported to have lower toxicity than hydrazides because of the blockage of –NH2 group (Buu-Hoi et al., 1953). These findings further support the growing importance of the synthesis of hydrazide-hydrazones compounds.

Figure 1 shows the molecular structure of the title compound. The total molecule is not planar and exist in the E configuration with respect to the C═N bond of methylidine moiety. The dihedral angle between the two benzene rings is 9.01 (6)°. The methylidine is co-planar with the C1–C6 benzene ring [the most deviation of 0.044 (1) Å of atom C3] with the torsion angle N2–N1–C7–C6 = -179.18 (10)°. The dimethylamino group is slightly twisted from the plane C1–C6 ring as indicated by the torsions angle of C17–N3–C3–C4 = -6.57 (18)° and C18–N3–C3–C4 = -177.96 (12)°. The nitro group is slightly twisted from the C8–C13 benzene ring with the interplanar angle between the mean plane through N4/O1/O2/C11 and C8–C13 planes [8.17 (7)°]. The ethyl group is nearly perpendicularly attached to the benzoate unit which can be reflected by the torsion angle C14–O3–C15–C16 = 88.66 (13)°. An intramolecular N2—H1N2···O4 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995) (Fig. 1 and Table 1). Bond lengths and angles in the title compound are in normal ranges (Allen et al., 1987).

Figure 2 shows that the molecules are linked into infinite chains along the b axis through weak C7—H7A···O1 interaction (Table 1) and these chains are further connected through weak C—H···O interactions (Table 1) forming sheets parallel to the ab plane. These sheets are stacked approximately along the c axis (Fig. 3). The crystal is stabilized by intramolecular N—H···O hydrogen bond, weak C—H···O interactions (Table 1) and C—H···π interactions (Table 1); Cg1 is the centroid of the C1–C6 ring.

Related literature top

For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For background to the applications of hydrazones, see, for example: Barton et al. (1962); Bedia et al. (2006); Buu-Hoi et al. (1953); Paquette (1995); Rollas et al. (2002); Terzioglu & Gürsoy (2003). Cg1 is the centroid of the C1–C6 ring.

Experimental top

The title compound was obtained by refluxing ethyl 2-hydrazinyl-5-nitrobenzoate (0.01 mol) and 4-(dimethylamino) benzaldehyde (0.01 mol) in ethanol (40 ml) by adding 3 drops of concentrated sulfuric acid for 8 hrs. Excess ethanol was removed from the reaction mixture under reduced pressure. The solid product obtained was filtered, washed with water and dried. Red single crystals of the title compound suitable for x-ray structure determination were grown by slow evaporation of an ethanol solution at room temperature (m.p. 439 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 2003).

Figures top

	Fig. 1. The asymmetric unit of (I), showing 50% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. The crystal packing of (I), viewed along the a axis showing that the molecules are linked into infinite chains along the b axis. Hydrogen bonds are drawn as dashed lines.
	Fig. 3. The crystal packing of (I), viewed approximately along the c axis. Hydrogen bonds are drawn as dashed lines.

Ethyl 2-[(E)-4-(dimethylamino)benzylidenehydrazino]- 5-nitrobenzoate top

Crystal data top

C₁₈H₂₀N₄O₄	F(000) = 752
M_r = 356.38	D_x = 1.381 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 439 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.8216 (4) Å	Cell parameters from 3929 reflections
b = 15.9175 (6) Å	θ = 2.0–27.5°
c = 10.4136 (4) Å	µ = 0.10 mm⁻¹
β = 107.091 (2)°	T = 100 K
V = 1714.56 (11) Å³	Block, red
Z = 4	0.44 × 0.41 × 0.31 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3929 independent reflections
Radiation source: fine-focus sealed tube	3275 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 8.33 pixels mm^-1	θ_max = 27.5°, θ_min = 2.0°
ω scans	h = −14→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −20→19
T_min = 0.957, T_max = 0.970	l = −13→13
16368 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0493P)² + 0.6489P] where P = (F_o² + 2F_c²)/3
3929 reflections	(Δ/σ)_max = 0.001
242 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₈H₂₀N₄O₄	V = 1714.56 (11) Å³
M_r = 356.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.8216 (4) Å	µ = 0.10 mm⁻¹
b = 15.9175 (6) Å	T = 100 K
c = 10.4136 (4) Å	0.44 × 0.41 × 0.31 mm
β = 107.091 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3929 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3275 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.970	R_int = 0.029
16368 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.26 e Å⁻³
3929 reflections	Δρ_min = −0.27 e Å⁻³
242 parameters

Special details top

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.79559 (10)	0.52119 (6)	−0.07387 (11)	0.0354 (3)
O2	0.69063 (9)	0.41140 (6)	−0.17045 (10)	0.0304 (2)
O3	0.81387 (8)	0.14041 (5)	−0.00146 (9)	0.0220 (2)
O4	0.93830 (9)	0.11554 (6)	0.20957 (9)	0.0263 (2)
N1	1.11000 (9)	0.28501 (7)	0.47925 (10)	0.0205 (2)
N2	1.03176 (10)	0.24883 (7)	0.36376 (10)	0.0200 (2)
N3	1.51942 (11)	0.31448 (7)	1.07252 (11)	0.0251 (3)
N4	0.77246 (10)	0.44519 (7)	−0.07681 (11)	0.0233 (2)
C1	1.27580 (12)	0.33820 (8)	0.74183 (12)	0.0211 (3)
H1A	1.2308	0.3810	0.6868	0.025*
C2	1.36107 (12)	0.35818 (8)	0.86484 (12)	0.0217 (3)
H2A	1.3724	0.4141	0.8915	0.026*
C3	1.43165 (11)	0.29502 (8)	0.95126 (12)	0.0199 (3)
C4	1.40814 (11)	0.21103 (8)	0.90855 (12)	0.0205 (3)
H4A	1.4511	0.1679	0.9641	0.025*
C5	1.32196 (11)	0.19195 (8)	0.78513 (12)	0.0204 (3)
H5A	1.3078	0.1360	0.7594	0.024*
C6	1.25546 (11)	0.25480 (8)	0.69791 (12)	0.0190 (3)
C7	1.16926 (11)	0.23101 (8)	0.56787 (12)	0.0200 (3)
H7A	1.1563	0.1742	0.5477	0.024*
C8	0.97180 (11)	0.29570 (8)	0.25563 (12)	0.0186 (2)
C9	0.89357 (11)	0.25738 (8)	0.13494 (12)	0.0185 (2)
C10	0.82866 (11)	0.30810 (8)	0.02772 (12)	0.0188 (2)
H10A	0.7750	0.2839	−0.0500	0.023*
C11	0.84340 (11)	0.39425 (8)	0.03584 (12)	0.0200 (3)
C12	0.92453 (12)	0.43263 (8)	0.15043 (13)	0.0227 (3)
H12A	0.9362	0.4906	0.1531	0.027*
C13	0.98667 (12)	0.38414 (8)	0.25861 (13)	0.0219 (3)
H13A	1.0396	0.4097	0.3355	0.026*
C14	0.88536 (11)	0.16499 (8)	0.12145 (12)	0.0197 (3)
C15	0.80366 (13)	0.05029 (8)	−0.02550 (13)	0.0235 (3)
H15A	0.8831	0.0233	0.0262	0.028*
H15B	0.7926	0.0394	−0.1199	0.028*
C16	0.69201 (16)	0.01346 (9)	0.01292 (16)	0.0362 (4)
H16A	0.6876	−0.0459	−0.0045	0.054*
H16B	0.6132	0.0396	−0.0389	0.054*
H16C	0.7038	0.0230	0.1068	0.054*
C17	1.57956 (12)	0.24807 (9)	1.16534 (13)	0.0243 (3)
H17A	1.6259	0.2111	1.1230	0.036*
H17B	1.5141	0.2169	1.1902	0.036*
H17C	1.6385	0.2722	1.2442	0.036*
C18	1.53899 (13)	0.40099 (8)	1.11646 (13)	0.0276 (3)
H18A	1.5651	0.4334	1.0511	0.041*
H18B	1.6051	0.4037	1.2012	0.041*
H18C	1.4598	0.4233	1.1262	0.041*
H1N2	1.0273 (15)	0.1942 (11)	0.3542 (16)	0.034 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0480 (6)	0.0165 (5)	0.0349 (6)	−0.0003 (4)	0.0017 (5)	0.0046 (4)
O2	0.0372 (5)	0.0261 (5)	0.0215 (5)	−0.0018 (4)	−0.0011 (4)	0.0025 (4)
O3	0.0290 (4)	0.0158 (4)	0.0178 (4)	−0.0011 (3)	0.0017 (4)	−0.0012 (3)
O4	0.0334 (5)	0.0205 (5)	0.0201 (5)	−0.0013 (4)	−0.0001 (4)	0.0025 (4)
N1	0.0205 (5)	0.0251 (5)	0.0149 (5)	−0.0033 (4)	0.0039 (4)	−0.0025 (4)
N2	0.0239 (5)	0.0194 (5)	0.0152 (5)	−0.0029 (4)	0.0036 (4)	−0.0024 (4)
N3	0.0307 (6)	0.0223 (6)	0.0174 (5)	−0.0018 (4)	−0.0006 (4)	0.0005 (4)
N4	0.0282 (5)	0.0195 (5)	0.0221 (6)	0.0014 (4)	0.0070 (4)	0.0018 (4)
C1	0.0239 (6)	0.0203 (6)	0.0180 (6)	0.0012 (5)	0.0043 (5)	0.0027 (5)
C2	0.0273 (6)	0.0167 (6)	0.0202 (6)	−0.0015 (5)	0.0057 (5)	−0.0005 (5)
C3	0.0220 (6)	0.0222 (6)	0.0150 (6)	−0.0018 (5)	0.0047 (5)	0.0006 (5)
C4	0.0233 (6)	0.0196 (6)	0.0182 (6)	0.0015 (4)	0.0054 (5)	0.0038 (5)
C5	0.0239 (6)	0.0181 (6)	0.0198 (6)	−0.0018 (5)	0.0075 (5)	−0.0005 (5)
C6	0.0199 (5)	0.0214 (6)	0.0163 (6)	−0.0017 (4)	0.0060 (5)	−0.0002 (5)
C7	0.0221 (5)	0.0198 (6)	0.0190 (6)	−0.0024 (5)	0.0076 (5)	−0.0019 (5)
C8	0.0186 (5)	0.0216 (6)	0.0166 (6)	−0.0004 (4)	0.0065 (5)	−0.0006 (5)
C9	0.0198 (5)	0.0188 (6)	0.0172 (6)	−0.0013 (4)	0.0059 (5)	−0.0006 (5)
C10	0.0215 (5)	0.0196 (6)	0.0154 (6)	−0.0015 (4)	0.0054 (5)	−0.0015 (5)
C11	0.0228 (6)	0.0194 (6)	0.0179 (6)	0.0014 (4)	0.0063 (5)	0.0026 (5)
C12	0.0270 (6)	0.0171 (6)	0.0244 (7)	−0.0019 (5)	0.0081 (5)	−0.0026 (5)
C13	0.0246 (6)	0.0218 (6)	0.0185 (6)	−0.0023 (5)	0.0050 (5)	−0.0045 (5)
C14	0.0204 (5)	0.0206 (6)	0.0172 (6)	−0.0017 (4)	0.0043 (5)	−0.0012 (5)
C15	0.0338 (7)	0.0145 (6)	0.0197 (6)	0.0004 (5)	0.0042 (5)	−0.0025 (5)
C16	0.0544 (9)	0.0263 (7)	0.0337 (8)	−0.0135 (6)	0.0218 (7)	−0.0090 (6)
C17	0.0249 (6)	0.0279 (7)	0.0172 (6)	0.0014 (5)	0.0018 (5)	0.0031 (5)
C18	0.0311 (7)	0.0266 (7)	0.0199 (7)	−0.0030 (5)	−0.0003 (5)	−0.0031 (5)

Geometric parameters (Å, º) top

O1—N4	1.2340 (14)	C7—H7A	0.9300
O2—N4	1.2316 (14)	C8—C13	1.4162 (17)
O3—C14	1.3445 (14)	C8—C9	1.4294 (16)
O3—C15	1.4548 (14)	C9—C10	1.3896 (17)
O4—C14	1.2170 (15)	C9—C14	1.4775 (17)
N1—C7	1.2861 (16)	C10—C11	1.3803 (17)
N1—N2	1.3770 (14)	C10—H10A	0.9300
N2—C8	1.3476 (16)	C11—C12	1.3973 (17)
N2—H1N2	0.874 (17)	C12—C13	1.3682 (18)
N3—C3	1.3739 (15)	C12—H12A	0.9300
N3—C18	1.4469 (17)	C13—H13A	0.9300
N3—C17	1.4511 (16)	C15—C16	1.499 (2)
N4—C11	1.4469 (16)	C15—H15A	0.9700
C1—C2	1.3779 (17)	C15—H15B	0.9700
C1—C6	1.4003 (17)	C16—H16A	0.9600
C1—H1A	0.9300	C16—H16B	0.9600
C2—C3	1.4141 (17)	C16—H16C	0.9600
C2—H2A	0.9300	C17—H17A	0.9600
C3—C4	1.4084 (17)	C17—H17B	0.9600
C4—C5	1.3817 (17)	C17—H17C	0.9600
C4—H4A	0.9300	C18—H18A	0.9600
C5—C6	1.3999 (17)	C18—H18B	0.9600
C5—H5A	0.9300	C18—H18C	0.9600
C6—C7	1.4509 (16)

C14—O3—C15	116.37 (9)	C11—C10—H10A	119.8
C7—N1—N2	113.34 (10)	C9—C10—H10A	119.8
C8—N2—N1	121.31 (10)	C10—C11—C12	121.27 (11)
C8—N2—H1N2	117.3 (11)	C10—C11—N4	118.87 (11)
N1—N2—H1N2	120.9 (11)	C12—C11—N4	119.86 (11)
C3—N3—C18	120.17 (11)	C13—C12—C11	119.34 (12)
C3—N3—C17	120.11 (11)	C13—C12—H12A	120.3
C18—N3—C17	119.16 (10)	C11—C12—H12A	120.3
O2—N4—O1	122.76 (11)	C12—C13—C8	121.17 (11)
O2—N4—C11	118.95 (10)	C12—C13—H13A	119.4
O1—N4—C11	118.29 (11)	C8—C13—H13A	119.4
C2—C1—C6	121.36 (11)	O4—C14—O3	122.77 (11)
C2—C1—H1A	119.3	O4—C14—C9	124.77 (11)
C6—C1—H1A	119.3	O3—C14—C9	112.45 (10)
C1—C2—C3	121.09 (12)	O3—C15—C16	111.47 (11)
C1—C2—H2A	119.5	O3—C15—H15A	109.3
C3—C2—H2A	119.5	C16—C15—H15A	109.3
N3—C3—C4	121.08 (11)	O3—C15—H15B	109.3
N3—C3—C2	121.52 (11)	C16—C15—H15B	109.3
C4—C3—C2	117.40 (11)	H15A—C15—H15B	108.0
C5—C4—C3	120.82 (11)	C15—C16—H16A	109.5
C5—C4—H4A	119.6	C15—C16—H16B	109.5
C3—C4—H4A	119.6	H16A—C16—H16B	109.5
C4—C5—C6	121.61 (11)	C15—C16—H16C	109.5
C4—C5—H5A	119.2	H16A—C16—H16C	109.5
C6—C5—H5A	119.2	H16B—C16—H16C	109.5
C5—C6—C1	117.65 (11)	N3—C17—H17A	109.5
C5—C6—C7	119.07 (11)	N3—C17—H17B	109.5
C1—C6—C7	123.27 (11)	H17A—C17—H17B	109.5
N1—C7—C6	122.92 (11)	N3—C17—H17C	109.5
N1—C7—H7A	118.5	H17A—C17—H17C	109.5
C6—C7—H7A	118.5	H17B—C17—H17C	109.5
N2—C8—C13	120.55 (11)	N3—C18—H18A	109.5
N2—C8—C9	120.92 (11)	N3—C18—H18B	109.5
C13—C8—C9	118.53 (11)	H18A—C18—H18B	109.5
C10—C9—C8	119.18 (11)	N3—C18—H18C	109.5
C10—C9—C14	119.99 (11)	H18A—C18—H18C	109.5
C8—C9—C14	120.79 (11)	H18B—C18—H18C	109.5
C11—C10—C9	120.39 (11)

C7—N1—N2—C8	−173.78 (11)	N2—C8—C9—C14	−5.29 (17)
C6—C1—C2—C3	0.22 (19)	C13—C8—C9—C14	173.76 (11)
C18—N3—C3—C4	−177.96 (12)	C8—C9—C10—C11	2.42 (17)
C17—N3—C3—C4	−6.57 (18)	C14—C9—C10—C11	−175.19 (11)
C18—N3—C3—C2	1.74 (19)	C9—C10—C11—C12	0.79 (18)
C17—N3—C3—C2	173.13 (12)	C9—C10—C11—N4	−178.88 (11)
C1—C2—C3—N3	178.24 (12)	O2—N4—C11—C10	7.77 (17)
C1—C2—C3—C4	−2.05 (18)	O1—N4—C11—C10	−173.19 (12)
N3—C3—C4—C5	−178.50 (11)	O2—N4—C11—C12	−171.90 (11)
C2—C3—C4—C5	1.79 (18)	O1—N4—C11—C12	7.14 (18)
C3—C4—C5—C6	0.30 (19)	C10—C11—C12—C13	−2.54 (19)
C4—C5—C6—C1	−2.13 (18)	N4—C11—C12—C13	177.12 (11)
C4—C5—C6—C7	178.08 (11)	C11—C12—C13—C8	1.02 (19)
C2—C1—C6—C5	1.87 (18)	N2—C8—C13—C12	−178.82 (11)
C2—C1—C6—C7	−178.35 (12)	C9—C8—C13—C12	2.13 (18)
N2—N1—C7—C6	−179.18 (10)	C15—O3—C14—O4	−0.73 (17)
C5—C6—C7—N1	−176.20 (11)	C15—O3—C14—C9	178.13 (10)
C1—C6—C7—N1	4.02 (19)	C10—C9—C14—O4	−179.76 (12)
N1—N2—C8—C13	−0.74 (17)	C8—C9—C14—O4	2.67 (19)
N1—N2—C8—C9	178.29 (10)	C10—C9—C14—O3	1.40 (16)
N2—C8—C9—C10	177.12 (11)	C8—C9—C14—O3	−176.17 (10)
C13—C8—C9—C10	−3.83 (17)	C14—O3—C15—C16	88.66 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O4	0.875 (18)	1.978 (17)	2.6736 (14)	135.6 (14)
C7—H7A···O1ⁱ	0.93	2.49	3.3599 (16)	156
C12—H12A···O4ⁱⁱ	0.93	2.59	3.3961 (16)	145
C16—H16C···O2ⁱⁱⁱ	0.96	2.59	3.5116 (19)	162
C17—H17B···Cg1ⁱⁱⁱ	0.96	2.64	3.4629 (14)	144

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

Experimental details

Crystal data
Chemical formula	C₁₈H₂₀N₄O₄
M_r	356.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.8216 (4), 15.9175 (6), 10.4136 (4)
β (°)	107.091 (2)
V (Å³)	1714.56 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.44 × 0.41 × 0.31

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.957, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	16368, 3929, 3275
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.105, 1.04
No. of reflections	3929
No. of parameters	242
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.27

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O4	0.875 (18)	1.978 (17)	2.6736 (14)	135.6 (14)
C7—H7A···O1ⁱ	0.93	2.49	3.3599 (16)	156
C12—H12A···O4ⁱⁱ	0.93	2.59	3.3961 (16)	145
C16—H16C···O2ⁱⁱⁱ	0.96	2.59	3.5116 (19)	162
C17—H17B···Cg1ⁱⁱⁱ	0.96	2.64	3.4629 (14)	144

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

Footnotes

‡Department of Studies in Physics, Mangalore University, Mangalagangotri, Mangalore 574 199, India.

§Additional correspondence author, e-mail: suchada.c@psu.ac.th.

Acknowledgements

This work is supported by the Department of Science and Technology (DST), Government of India, under grant No. SR/S2/LOP-17/2006. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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–S19. CrossRef Web of Science Google Scholar
Barton, D. H. R., OBrien, R. E. & Sternhell, S. (1962). J. Chem. Soc. pp. 470–476. CrossRef Web of Science Google Scholar
Bedia, K.-K., Elrin, O., Seda, U., Fatma, K., Nathaly, S., Sevim, R. & Dimoglo, A. (2006). Eur. J. Med. Chem. 41, 1253–1261. Web of Science 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 (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Buu-Hoi, P. H., Xuong, D., Nam, H., Binon, F. & Royer, R. (1953). J. Chem. Soc. pp. 1358–1364. CrossRef Web of Science Google Scholar
Paquette, L. A. (1995). Editor. Encyclopedia of Reagents for Organic Synthesis, Vol. 4, pp. 2680–2684. Chichester: John Wiley & Sons Ltd. Google Scholar
Rollas, S., Gülerman, N. & Erdeniz, H. (2002). Farmaco, 57, 171–174. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Terzioglu, N. & Gürsoy, A. (2003). Eur. J. Med. Chem. 38, 781–786. Web of Science CrossRef PubMed CAS Google Scholar