2-[2-(4-Nitro­phen­yl)hydrazinyl­idene]-1,3-diphenyl­propane-1,3-dione

Bustos, C.; Alvarez-Thon, L.; Barría, D.; Garland, M.T.; Sánchez, C.

doi:10.1107/S1600536811021143

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1587

doi:10.1107/S1600536811021143

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2-[2-(4-Nitrophenyl)hydrazinylidene]-1,3-diphenylpropane-1,3-dione

Carlos Bustos,^a Luis Alvarez-Thon,^b ^* Daniela Barría,^a Maria Teresa Garland ^c and Christian Sánchez ^a

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

(Received 19 May 2011; accepted 1 June 2011; online 4 June 2011)

In the molecular structure of the title compound, C₂₁H₁₅N₃O₄, the interplanar angle between the benzoyl units is 89.7 (1)°. The corresponding angles between the phenylhydrazono and the benzoyl groups are 31.4 (3) and 60.8 (2)°, respectively. In the crystal, a strong resonance-assisted intramolecular hydrogen bond (N—H⋯O) and a weak intramolecular hydrogen bond (C—H⋯N) strongly affect the observed conformation of the molecule. The crystal packing is determined by a strong intermolecular hydrogen bond (N—H⋯O), giving rise to a helical chain along the a axis. In addition, two weak intermolecular contacts (C—H⋯O) are observed.

Related literature

For details of the synthesis, see: Bustos et al. (2007 , 2009 ); Yao (1964 ). For resonance-assisted hydrogen bonds and related structures, see: Bertolasi et al. (1993 , 1994 ); Bustos et al. (2011 ).

Experimental

Crystal data

C₂₁H₁₅N₃O₄
M_r = 373.36
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.2994 (7) Å
b = 8.6250 (7) Å
c = 25.018 (2) Å
V = 1790.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 150 K
0.30 × 0.28 × 0.12 mm

Data collection

Bruker D8 Discover with SMART CCD area-detector diffractometer
13939 measured reflections
2114 independent reflections
1826 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.084
S = 1.00
2114 reflections
257 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O2	0.96 (3)	2.25 (3)	2.793 (2)	115.3 (19)
N2—H1⋯O1ⁱ	0.96 (3)	2.15 (2)	2.956 (2)	142 (2)
C5—H5⋯O3ⁱⁱ	0.95	2.60	3.419 (3)	145
C15—H15⋯N1	0.95	2.42	2.849 (3)	107
C20—H20⋯O2ⁱⁱⁱ	0.95	2.44	3.352 (2)	161
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2000 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811021143/im2291sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021143/im2291Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811021143/im2291Isup3.cml

checkCIF report

Comment top

The crystal structure of 2-[(4-nitro-phenyl)-hydrazono]-1,3-diphenyl-propane-1,3-dione is reported. This compound belongs to a family that contain a six-membered π–conjugated ring closed via strong intramolecular resonance assisted hydrogen bonds, N–H···O, RAHB (Resonance Assisted Hydrogen Bond) which, inter alia, could have remarkable importance as bistate in molecular switches (Bertolasi et al., 1993; Bertolasi et al., 1994; Bustos et al., 2011). On the other hand, it is well known that the phenyl diazonium salts are capable of coupling with a series of β-diketonate anions to give β-diketohydrazones containing N–H···O moieties (Yao, 1964; Bustos et al., 2007; Bustos et al., 2009). Using this reaction (Yao, 1964) we have prepared the title compound.

The molecular structure of the title compound, C₂₁H₁₅N₃O₄, exhibits a strong intramolecular hydrogen bond (N2–H1···O2) and a weak intramolecular hydrogen bond (C15–H15···N1) (Fig. 1 and Tab. 1). In the crystal structure, strong intermolecular hydrogen bonds (N2–H1···O1ⁱ) link the molecules into helical chains along the a axis, which may be the reason why the title compound crystallizes in the chiral space group P2₁2₁2₁ (see Fig. 2 and Tab. 1), [symmetry code: (i) x + 1/2, -y + 3/2, -z]. On the other hand, weak intermolecular contacts of the type C5–H5···O3ⁱⁱ and C20–H20···O2ⁱⁱⁱ, further stabilize the crystal packing to construct the entire three-dimensional network, see Fig. 3 and Tab. 1, [symmetry codes: (ii) -x + 3/2, -y + 1, -1/2 + z; (iii) x + 1/2, -y + 1/2, -z]. The interplanar angle between the benzoyl moieties is 89.7 (1)°. The corresponding angles between the phenyl-hydrazono and the benzoyl groups, are 31.4 (3)° and 60.8 (2)°, respectively.

Related literature top

For details of the synthesis, see: Bustos et al. (2007, 2009); Yao (1964). For resonance-assisted hydrogen bonds and related structures, see: Bertolasi et al. (1993, 1994); Bustos et al. (2011).

Experimental top

In a 500 ml flask, 2.24 g (0.01 mole) of 1,3-diphenylpropane-1,3-dione were dissolved in 100 ml of a ethanolic solution that contained 0.4 g (0.01 mole) of sodium hydroxide and 3.65 g (0.045 mole) of sodium acetate. The resulting β-diketonate solution was diluted with water to a final volume of about 220 ml, stirred and cooled at 268 K. In another 50 ml beaker a diazonium ion solution was prepared adding 1.39 g (0.01 mole) of 4-nitroaniline (99%) in 8 ml of hydrochloric acid (5 mol/L), cooling at 268 K, and adding a saturated aqueous solution containing 0.69 g (0.01 mole) of sodium nitrite. The diazonium salt solution was then added dropwise with vigorous stirring at 268 K into the β-diketonate solution. During the addition a yellow solid precipitate of the title compound was formed which was filtered by suction, washed with an abundant quantity of water and dried in the vacuum at 313 K (Yield: 91% of crude product). Single crystals suitable for X-ray studies were obtained by recrystallization from ethanol.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. The strong intramolecular hydrogen bond (N2–H1···O2) is depicted with dashed lines.
	Fig. 2. Perspective view along the b axis showing the formation of a zigzag chain, along the a axis, linked by strong intermolecular hydrogen bonds, N2–H1···O1ⁱ (dashed lines), [symmetry code: (i) x + 1/2, -y + 3/2, -z].
	Fig. 3. Perspective view along the b axis showing the formation of a chain, along the c axis, linked by weak intermolecular contacts (C5–H5···O3ⁱⁱ and C20–H20···O2ⁱⁱⁱ), [symmetry codes: (ii) -x + 3/2, -y + 1, -1/2 + z; (iii) x + 1/2, -y + 1/2, -z].

2-[2-(4-Nitrophenyl)hydrazinylidene]-1,3-diphenylpropane-1,3-dione top

Crystal data top

C₂₁H₁₅N₃O₄	F(000) = 776
M_r = 373.36	D_x = 1.385 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 999 reflections
a = 8.2994 (7) Å	θ = 1.6–26.4°
b = 8.6250 (7) Å	µ = 0.10 mm⁻¹
c = 25.018 (2) Å	T = 150 K
V = 1790.9 (3) Å³	Polyhedron, yellow
Z = 4	0.30 × 0.28 × 0.12 mm

Data collection top

Bruker D8 Discover with SMART CCD area-detector diffractometer	1826 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 26.4°, θ_min = 1.6°
ϕ and ω scans	h = −10→10
13939 measured reflections	k = −10→10
2114 independent reflections	l = −31→31

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0526P)²] where P = (F_o² + 2F_c²)/3
2114 reflections	(Δ/σ)_max < 0.001
257 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂₁H₁₅N₃O₄	V = 1790.9 (3) Å³
M_r = 373.36	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.2994 (7) Å	µ = 0.10 mm⁻¹
b = 8.6250 (7) Å	T = 150 K
c = 25.018 (2) Å	0.30 × 0.28 × 0.12 mm

Data collection top

Bruker D8 Discover with SMART CCD area-detector diffractometer	1826 reflections with I > 2σ(I)
13939 measured reflections	R_int = 0.034
2114 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.19 e Å⁻³
2114 reflections	Δρ_min = −0.16 e Å⁻³
257 parameters

Special details top

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

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.44608 (18)	0.97963 (18)	0.03744 (5)	0.0389 (5)
O2	0.5740 (2)	0.61910 (18)	−0.03732 (6)	0.0466 (6)
O3	1.0083 (2)	0.13731 (18)	0.24696 (6)	0.0465 (5)
O4	1.04378 (19)	−0.02554 (17)	0.18195 (6)	0.0388 (5)
N1	0.6619 (2)	0.65447 (19)	0.07404 (7)	0.0296 (5)
N2	0.7292 (2)	0.5252 (2)	0.05629 (7)	0.0334 (6)
N3	0.9963 (2)	0.1000 (2)	0.19940 (7)	0.0337 (6)
C1	0.6762 (2)	0.8692 (2)	−0.05394 (8)	0.0276 (6)
C2	0.7655 (2)	0.9941 (3)	−0.03441 (8)	0.0316 (6)
C3	0.8288 (3)	1.1021 (3)	−0.06939 (9)	0.0386 (7)
C4	0.8022 (3)	1.0870 (3)	−0.12373 (9)	0.0398 (8)
C5	0.7127 (3)	0.9651 (3)	−0.14324 (8)	0.0399 (7)
C6	0.6502 (3)	0.8551 (3)	−0.10873 (8)	0.0339 (7)
C7	0.6156 (3)	0.7439 (2)	−0.01897 (8)	0.0302 (6)
C8	0.6125 (2)	0.7616 (2)	0.04127 (7)	0.0289 (6)
C9	0.5292 (2)	0.8954 (2)	0.06604 (7)	0.0282 (6)
C10	0.5405 (2)	0.9243 (2)	0.12510 (7)	0.0272 (6)
C11	0.4112 (3)	0.9999 (3)	0.14872 (8)	0.0353 (7)
C12	0.4119 (3)	1.0314 (3)	0.20280 (8)	0.0436 (8)
C13	0.5415 (3)	0.9878 (3)	0.23385 (8)	0.0404 (7)
C14	0.6709 (3)	0.9125 (3)	0.21065 (8)	0.0348 (7)
C15	0.6721 (3)	0.8826 (2)	0.15632 (8)	0.0303 (6)
C16	0.7912 (3)	0.4192 (2)	0.09311 (8)	0.0300 (6)
C17	0.7726 (3)	0.4409 (2)	0.14817 (8)	0.0331 (7)
C18	0.8404 (3)	0.3353 (2)	0.18280 (8)	0.0331 (6)
C19	0.9223 (2)	0.2091 (2)	0.16230 (8)	0.0289 (6)
C20	0.9391 (3)	0.1843 (2)	0.10811 (8)	0.0336 (7)
C21	0.8739 (3)	0.2911 (2)	0.07362 (8)	0.0340 (7)
H1	0.752 (3)	0.511 (3)	0.0191 (10)	0.052 (7)*
H2	0.78270	1.00480	0.00290	0.0380*
H3	0.89040	1.18660	−0.05610	0.0460*
H4	0.84600	1.16120	−0.14770	0.0480*
H5	0.69380	0.95640	−0.18060	0.0480*
H6	0.58980	0.77020	−0.12230	0.0410*
H11	0.32160	1.03010	0.12750	0.0420*
H12	0.32290	1.08320	0.21870	0.0520*
H13	0.54190	1.00940	0.27110	0.0480*
H14	0.75950	0.88110	0.23210	0.0420*
H15	0.76270	0.83370	0.14040	0.0360*
H17	0.71400	0.52720	0.16150	0.0400*
H18	0.83090	0.34900	0.22030	0.0400*
H20	0.99430	0.09560	0.09500	0.0400*
H21	0.88550	0.27720	0.03610	0.0410*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0424 (8)	0.0457 (9)	0.0285 (8)	0.0103 (8)	−0.0056 (7)	0.0023 (7)
O2	0.0727 (12)	0.0396 (9)	0.0274 (8)	−0.0174 (9)	−0.0043 (8)	−0.0027 (7)
O3	0.0627 (11)	0.0466 (9)	0.0301 (8)	0.0086 (9)	−0.0044 (7)	0.0013 (8)
O4	0.0404 (8)	0.0306 (8)	0.0454 (9)	0.0061 (7)	0.0028 (7)	−0.0011 (7)
N1	0.0347 (10)	0.0272 (9)	0.0269 (9)	−0.0012 (8)	0.0029 (8)	−0.0008 (8)
N2	0.0467 (11)	0.0303 (10)	0.0233 (9)	0.0025 (9)	0.0042 (8)	−0.0018 (8)
N3	0.0341 (10)	0.0334 (10)	0.0337 (10)	−0.0014 (8)	0.0013 (8)	0.0006 (8)
C1	0.0298 (11)	0.0284 (11)	0.0245 (10)	0.0024 (9)	0.0007 (8)	−0.0015 (9)
C2	0.0380 (11)	0.0327 (11)	0.0241 (10)	0.0008 (10)	−0.0010 (9)	−0.0020 (10)
C3	0.0443 (13)	0.0333 (12)	0.0382 (12)	−0.0054 (11)	0.0038 (11)	−0.0016 (10)
C4	0.0497 (14)	0.0363 (13)	0.0333 (12)	−0.0016 (11)	0.0087 (11)	0.0063 (10)
C5	0.0500 (14)	0.0477 (14)	0.0221 (10)	−0.0011 (12)	0.0013 (10)	0.0009 (10)
C6	0.0390 (12)	0.0362 (12)	0.0264 (10)	−0.0011 (11)	−0.0004 (9)	−0.0039 (9)
C7	0.0324 (11)	0.0323 (11)	0.0259 (11)	−0.0023 (10)	−0.0030 (9)	−0.0023 (10)
C8	0.0325 (11)	0.0302 (11)	0.0240 (10)	−0.0036 (9)	0.0001 (9)	0.0007 (9)
C9	0.0273 (10)	0.0313 (11)	0.0259 (10)	−0.0028 (9)	−0.0010 (8)	0.0017 (9)
C10	0.0298 (10)	0.0256 (10)	0.0262 (10)	−0.0028 (9)	0.0012 (9)	0.0013 (9)
C11	0.0324 (11)	0.0431 (13)	0.0304 (11)	0.0050 (11)	−0.0039 (9)	−0.0004 (10)
C12	0.0352 (12)	0.0642 (16)	0.0315 (11)	0.0047 (12)	0.0038 (10)	−0.0072 (12)
C13	0.0428 (13)	0.0565 (14)	0.0218 (10)	−0.0043 (12)	0.0000 (9)	−0.0029 (10)
C14	0.0349 (12)	0.0398 (12)	0.0296 (11)	−0.0040 (10)	−0.0066 (9)	0.0035 (10)
C15	0.0322 (11)	0.0285 (11)	0.0302 (11)	−0.0016 (9)	−0.0013 (9)	−0.0015 (9)
C16	0.0377 (12)	0.0256 (11)	0.0268 (10)	−0.0048 (9)	0.0039 (9)	0.0014 (9)
C17	0.0433 (13)	0.0286 (11)	0.0275 (10)	0.0024 (10)	0.0073 (9)	−0.0012 (9)
C18	0.0451 (12)	0.0300 (11)	0.0241 (10)	−0.0003 (10)	0.0056 (10)	−0.0012 (9)
C19	0.0337 (11)	0.0242 (10)	0.0288 (10)	−0.0039 (9)	0.0021 (9)	0.0014 (9)
C20	0.0420 (12)	0.0271 (11)	0.0318 (11)	−0.0001 (10)	0.0055 (10)	−0.0035 (9)
C21	0.0470 (13)	0.0309 (11)	0.0242 (10)	−0.0020 (11)	0.0059 (10)	−0.0056 (9)

Geometric parameters (Å, º) top

O1—C9	1.231 (2)	C13—C14	1.383 (3)
O2—C7	1.220 (2)	C14—C15	1.384 (3)
O3—N3	1.237 (2)	C16—C21	1.389 (3)
O4—N3	1.232 (2)	C16—C17	1.399 (3)
N1—N2	1.324 (2)	C17—C18	1.377 (3)
N1—C8	1.302 (2)	C18—C19	1.382 (3)
N2—C16	1.396 (3)	C19—C20	1.380 (3)
N3—C19	1.457 (3)	C20—C21	1.373 (3)
N2—H1	0.96 (3)	C2—H2	0.9500
C1—C6	1.393 (3)	C3—H3	0.9500
C1—C7	1.479 (3)	C4—H4	0.9500
C1—C2	1.396 (3)	C5—H5	0.9500
C2—C3	1.382 (3)	C6—H6	0.9500
C3—C4	1.383 (3)	C11—H11	0.9500
C4—C5	1.377 (4)	C12—H12	0.9500
C5—C6	1.384 (3)	C13—H13	0.9500
C7—C8	1.515 (3)	C14—H14	0.9500
C8—C9	1.481 (2)	C15—H15	0.9500
C9—C10	1.501 (2)	C17—H17	0.9500
C10—C11	1.388 (3)	C18—H18	0.9500
C10—C15	1.390 (3)	C20—H20	0.9500
C11—C12	1.380 (3)	C21—H21	0.9500
C12—C13	1.379 (3)

O1···C1	3.128 (2)	C15···C19^xi	3.502 (3)
O1···C2	3.205 (2)	C15···O4^xi	3.249 (3)
O1···C7ⁱ	3.384 (3)	C15···N1	2.849 (3)
O1···O2ⁱ	3.203 (2)	C16···C6ⁱⁱⁱ	3.580 (3)
O1···N2ⁱ	2.956 (2)	C18···O3^xii	3.384 (2)
O2···N2	2.793 (2)	C19···C15^vi	3.502 (3)
O2···C2ⁱ	3.276 (2)	C19···C14^vi	3.516 (3)
O2···C20ⁱⁱ	3.352 (2)	C20···O2^viii	3.352 (2)
O2···N1	2.896 (2)	C3···H21^xi	3.0800
O2···O1ⁱⁱⁱ	3.203 (2)	C4···H13^xiii	3.0500
O3···C18^iv	3.384 (2)	C5···H13^xiii	2.9600
O3···C5^v	3.419 (3)	C7···H1	2.50 (3)
O4···C15^vi	3.249 (3)	C8···H15	2.8400
O4···C11^vii	3.168 (3)	C8···H2	2.7000
O4···C12^vii	3.138 (3)	C9···H2	2.7900
O4···C14^vi	3.222 (3)	C11···H4^xiv	2.9700
O1···H1ⁱ	2.15 (2)	C12···H4^xiv	3.0400
O1···H21ⁱ	2.8300	C15···H17	3.0900
O1···H11	2.5200	H1···O2	2.25 (3)
O2···H2ⁱ	2.7800	H1···C7	2.50 (3)
O2···H20ⁱⁱ	2.4400	H1···H21	2.3400
O2···H1	2.25 (3)	H1···O1ⁱⁱⁱ	2.15 (2)
O2···H6	2.5000	H2···C8	2.7000
O3···H14^iv	2.9000	H2···C9	2.7900
O3···H12^vii	2.7400	H2···O2ⁱⁱⁱ	2.7800
O3···H18	2.4400	H3···H21^xi	2.4400
O3···H5^v	2.6000	H4···C11^xv	2.9700
O4···H11^vii	2.7200	H4···C12^xv	3.0400
O4···H12^vii	2.6600	H5···O3^ix	2.6000
O4···H14^vi	2.7900	H5···H13^xiii	2.5200
O4···H15^vi	2.8300	H6···O2	2.5000
O4···H20	2.4500	H6···O4ⁱⁱ	2.6100
O4···H6^viii	2.6100	H11···O1	2.5200
O4···H18^iv	2.8700	H11···O4^x	2.7200
N1···O2	2.896 (2)	H12···O3^x	2.7400
N1···C15	2.849 (3)	H12···O4^x	2.6600
N2···O1ⁱⁱⁱ	2.956 (2)	H12···N3^x	2.7600
N2···O2	2.793 (2)	H13···C4^xvi	3.0500
N3···C14^vi	3.160 (3)	H13···C5^xvi	2.9600
N1···H15	2.4200	H13···H5^xvi	2.5200
N1···H17	2.4900	H14···O4^xi	2.7900
N3···H12^vii	2.7600	H14···N3^xi	2.8500
N3···H14^vi	2.8500	H14···O3^xii	2.9000
C1···O1	3.128 (2)	H15···O4^xi	2.8300
C2···O1	3.205 (2)	H15···N1	2.4200
C2···C9	3.299 (3)	H15···C8	2.8400
C2···O2ⁱⁱⁱ	3.276 (2)	H17···N1	2.4900
C5···O3^ix	3.419 (3)	H17···C15	3.0900
C6···C16ⁱ	3.580 (3)	H18···O3	2.4400
C7···O1ⁱⁱⁱ	3.384 (3)	H18···O4^xii	2.8700
C9···C2	3.299 (3)	H20···O4	2.4500
C11···O4^x	3.168 (3)	H20···O2^viii	2.4400
C12···O4^x	3.138 (3)	H21···C3^vi	3.0800
C14···O4^xi	3.222 (3)	H21···H1	2.3400
C14···N3^xi	3.160 (3)	H21···H3^vi	2.4400
C14···C19^xi	3.516 (3)	H21···O1ⁱⁱⁱ	2.8300

N2—N1—C8	121.30 (17)	C16—C17—C18	119.07 (18)
N1—N2—C16	119.06 (17)	C17—C18—C19	119.23 (18)
O3—N3—O4	122.94 (17)	N3—C19—C20	118.89 (16)
O3—N3—C19	118.60 (16)	N3—C19—C18	118.65 (18)
O4—N3—C19	118.46 (16)	C18—C19—C20	122.45 (18)
N1—N2—H1	121.1 (16)	C19—C20—C21	118.27 (18)
C16—N2—H1	119.0 (15)	C16—C21—C20	120.51 (19)
C2—C1—C6	119.61 (19)	C1—C2—H2	120.00
C2—C1—C7	122.52 (18)	C3—C2—H2	120.00
C6—C1—C7	117.76 (18)	C2—C3—H3	120.00
C1—C2—C3	120.03 (19)	C4—C3—H3	120.00
C2—C3—C4	119.9 (2)	C3—C4—H4	120.00
C3—C4—C5	120.4 (2)	C5—C4—H4	120.00
C4—C5—C6	120.3 (2)	C4—C5—H5	120.00
C1—C6—C5	119.7 (2)	C6—C5—H5	120.00
O2—C7—C8	117.28 (17)	C1—C6—H6	120.00
O2—C7—C1	121.23 (18)	C5—C6—H6	120.00
C1—C7—C8	121.38 (16)	C10—C11—H11	120.00
N1—C8—C9	115.89 (16)	C12—C11—H11	120.00
N1—C8—C7	123.35 (16)	C11—C12—H12	120.00
C7—C8—C9	120.18 (15)	C13—C12—H12	120.00
O1—C9—C10	120.60 (16)	C12—C13—H13	120.00
C8—C9—C10	120.79 (15)	C14—C13—H13	120.00
O1—C9—C8	118.57 (16)	C13—C14—H14	120.00
C11—C10—C15	119.33 (17)	C15—C14—H14	120.00
C9—C10—C11	116.66 (16)	C10—C15—H15	120.00
C9—C10—C15	123.99 (16)	C14—C15—H15	120.00
C10—C11—C12	120.5 (2)	C16—C17—H17	120.00
C11—C12—C13	120.1 (2)	C18—C17—H17	120.00
C12—C13—C14	119.83 (19)	C17—C18—H18	120.00
C13—C14—C15	120.4 (2)	C19—C18—H18	120.00
C10—C15—C14	119.9 (2)	C19—C20—H20	121.00
C17—C16—C21	120.44 (18)	C21—C20—H20	121.00
N2—C16—C17	121.43 (18)	C16—C21—H21	120.00
N2—C16—C21	118.12 (18)	C20—C21—H21	120.00

C8—N1—N2—C16	175.19 (18)	N1—C8—C9—C10	15.3 (2)
N2—N1—C8—C7	4.7 (3)	C7—C8—C9—O1	9.2 (3)
N2—N1—C8—C9	175.89 (16)	C7—C8—C9—C10	−173.16 (16)
N1—N2—C16—C17	5.0 (3)	O1—C9—C10—C11	26.0 (3)
N1—N2—C16—C21	−174.39 (19)	O1—C9—C10—C15	−152.83 (18)
O3—N3—C19—C18	−12.6 (3)	C8—C9—C10—C11	−151.62 (18)
O3—N3—C19—C20	166.19 (18)	C8—C9—C10—C15	29.6 (3)
O4—N3—C19—C18	167.23 (18)	C9—C10—C11—C12	−179.9 (2)
O4—N3—C19—C20	−14.0 (3)	C15—C10—C11—C12	−1.0 (3)
C6—C1—C2—C3	−0.6 (3)	C9—C10—C15—C14	−179.29 (19)
C7—C1—C2—C3	175.4 (2)	C11—C10—C15—C14	1.9 (3)
C2—C1—C6—C5	−0.2 (3)	C10—C11—C12—C13	0.0 (4)
C7—C1—C6—C5	−176.4 (2)	C11—C12—C13—C14	0.1 (4)
C2—C1—C7—O2	−161.6 (2)	C12—C13—C14—C15	0.9 (4)
C2—C1—C7—C8	14.5 (3)	C13—C14—C15—C10	−1.9 (3)
C6—C1—C7—O2	14.5 (3)	N2—C16—C17—C18	−178.0 (2)
C6—C1—C7—C8	−169.39 (19)	C21—C16—C17—C18	1.4 (3)
C1—C2—C3—C4	0.6 (3)	N2—C16—C21—C20	179.2 (2)
C2—C3—C4—C5	0.1 (4)	C17—C16—C21—C20	−0.3 (4)
C3—C4—C5—C6	−0.9 (4)	C16—C17—C18—C19	−1.3 (3)
C4—C5—C6—C1	0.9 (4)	C17—C18—C19—N3	178.75 (19)
O2—C7—C8—N1	42.0 (3)	C17—C18—C19—C20	0.0 (3)
O2—C7—C8—C9	−128.9 (2)	N3—C19—C20—C21	−177.62 (19)
C1—C7—C8—N1	−134.3 (2)	C18—C19—C20—C21	1.1 (3)
C1—C7—C8—C9	54.9 (3)	C19—C20—C21—C16	−1.0 (3)
N1—C8—C9—O1	−162.31 (17)

Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x−1/2, −y+1/2, −z; (iii) x+1/2, −y+3/2, −z; (iv) −x+2, y−1/2, −z+1/2; (v) −x+3/2, −y+1, z+1/2; (vi) x, y−1, z; (vii) x+1, y−1, z; (viii) x+1/2, −y+1/2, −z; (ix) −x+3/2, −y+1, z−1/2; (x) x−1, y+1, z; (xi) x, y+1, z; (xii) −x+2, y+1/2, −z+1/2; (xiii) −x+3/2, −y+2, z−1/2; (xiv) x−1/2, −y+5/2, −z; (xv) x+1/2, −y+5/2, −z; (xvi) −x+3/2, −y+2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O2	0.96 (3)	2.25 (3)	2.793 (2)	115.3 (19)
N2—H1···O1ⁱⁱⁱ	0.96 (3)	2.15 (2)	2.956 (2)	142 (2)
C5—H5···O3^ix	0.95	2.60	3.419 (3)	145
C15—H15···N1	0.95	2.42	2.849 (3)	107
C20—H20···O2^viii	0.95	2.44	3.352 (2)	161

Symmetry codes: (iii) x+1/2, −y+3/2, −z; (viii) x+1/2, −y+1/2, −z; (ix) −x+3/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₅N₃O₄
M_r	373.36
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	8.2994 (7), 8.6250 (7), 25.018 (2)
V (Å³)	1790.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.28 × 0.12

Data collection
Diffractometer	Bruker D8 Discover with SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13939, 2114, 1826
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.084, 1.00
No. of reflections	2114
No. of parameters	257
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL/PC (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O2	0.96 (3)	2.25 (3)	2.793 (2)	115.3 (19)
N2—H1···O1ⁱ	0.96 (3)	2.15 (2)	2.956 (2)	142 (2)
C5—H5···O3ⁱⁱ	0.95	2.60	3.419 (3)	145
C15—H15···N1	0.95	2.42	2.849 (3)	107
C20—H20···O2ⁱⁱⁱ	0.95	2.44	3.352 (2)	161

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

Acknowledgements

The authors thank the Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT; grant Nos. 11100446 and 1080269) and the Universidad Andrés Bello (grant No. DI-06-10-R) for financial assistance.

References

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