3-{1-[(2,4-Dinitrophenyl)hydrazino]-ethyl-idene}-5-(1-methylpropyl)pyrrolidine-2,4-dione.

In the title compound, C(16)H(19)N(5)O(6), two intramolecular N-H⋯O hydrogen bonds help to establish the conformation. In the crystal, intermolecular N-H⋯O links result in chains propagating in [010].

Related literature

For the use of the title compound in instrumental analytical chemistry, see: Siegel et al. (2009 ▶). For the crystal structure of the tenuazonic copper(II) salt, see: Dippenaar et al. (1977 ▶). For the structures of other 2,4-dinitro­phenyl­hydrazones, see: Tameem et al. (2006 ▶); Monfared et al. (2007 ▶); Valente et al. (2008 ▶); Yin et al. (2008 ▶). Solubilized tetra­mic acids and their hydrazones display a variety of tautomeric forms, see: Gelin et al. (1982 ▶); Nolte et al. (1980 ▶); Royles (1995 ▶); Yamaguchi et al. (1976a ▶, 1976b ▶). For the synthesis, see: Lebrun et al. (1988 ▶).

Experimental

Crystal data

C16H19N5O6

M = 377.36

Monoclinic,

a = 10.6710 (10) Å

b = 4.9387 (5) Å

c = 16.839 (2) Å

β = 107.363 (4)°

V = 846.98 (15) Å3

Z = 2

Cu Kα radiation

μ = 0.98 mm−1

T = 193 K

0.64 × 0.06 × 0.06 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ▶) T min = 0.78, T max = 0.94

3890 measured reflections

3282 independent reflections

3103 reflections with I > 2σ(I)

R int = 0.025

3 standard reflections frequency: 60 min intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.111

S = 0.99

3282 reflections

247 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: (Flack,1983 ▶)

Flack parameter: 0.1 (2)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012458/kj2118sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012458/kj2118Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H19N5O6	F(000) = 396
Mr = 377.36	Dx = 1.480 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 10.671 (1) Å	θ = 60–69°
b = 4.9387 (5) Å	µ = 0.98 mm−1
c = 16.839 (2) Å	T = 193 K
β = 107.363 (4)°	Needles, yellow
V = 846.98 (15) Å3	0.64 × 0.06 × 0.06 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	3103 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
graphite	θmax = 73.6°, θmin = 2.8°
ω/2θ scans	h = −13→13
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971)	k = −5→6
Tmin = 0.78, Tmax = 0.94	l = −20→20
3890 measured reflections	3 standard reflections every 60 min
3282 independent reflections	intensity decay: 2%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H-atom parameters constrained
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.0778P)2 + 0.1634P] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max < 0.001
3282 reflections	Δρmax = 0.24 e Å−3
247 parameters	Δρmin = −0.21 e Å−3
1 restraint	Absolute structure: (Flack,1983)
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.1 (2)

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.

	x	y	z	Uiso*/Ueq
O1	0.28853 (17)	1.4445 (4)	0.18665 (10)	0.0394 (4)
O2	0.38017 (15)	1.3663 (4)	0.31656 (10)	0.0373 (4)
O3	−0.1297 (2)	0.5644 (5)	0.06973 (11)	0.0559 (5)
O4	−0.07342 (18)	0.9300 (4)	0.01932 (9)	0.0444 (4)
O5	0.43857 (13)	0.4033 (3)	0.54411 (8)	0.0277 (3)
O6	0.13063 (14)	0.7678 (4)	0.66874 (9)	0.0348 (4)
N1	0.29520 (16)	1.3174 (4)	0.24909 (10)	0.0267 (4)
N2	−0.06562 (18)	0.7738 (4)	0.07614 (11)	0.0339 (4)
N3	0.27686 (16)	1.0106 (4)	0.39501 (10)	0.0280 (4)
H3N	0.3538	1.1087	0.4007	0.034*
N4	0.29331 (16)	0.8153 (4)	0.45682 (10)	0.0266 (4)
H4N	0.3584	0.6959	0.4627	0.032*
N5	0.39181 (16)	0.3303 (4)	0.66688 (9)	0.0262 (4)
H5N	0.4542	0.2158	0.6856	0.031*
C1	0.20134 (18)	1.0983 (4)	0.24520 (12)	0.0230 (4)
C2	0.11472 (18)	1.0434 (4)	0.16609 (11)	0.0254 (4)
H2	0.1175	1.1462	0.1190	0.030*
C3	0.02556 (19)	0.8361 (5)	0.15868 (12)	0.0265 (4)
C4	0.01923 (18)	0.6831 (4)	0.22646 (12)	0.0271 (4)
H4	−0.0428	0.5404	0.2195	0.032*
C5	0.10350 (19)	0.7399 (4)	0.30371 (12)	0.0266 (4)
H5	0.0984	0.6356	0.3500	0.032*
C6	0.19821 (17)	0.9503 (4)	0.31639 (11)	0.0240 (4)
C7	0.23382 (17)	0.8356 (4)	0.51605 (11)	0.0231 (4)
C8	0.27239 (16)	0.6612 (4)	0.58383 (11)	0.0221 (4)
C9	0.37640 (18)	0.4572 (4)	0.59406 (11)	0.0212 (4)
C10	0.30819 (18)	0.4349 (4)	0.71460 (11)	0.0242 (4)
H10	0.2515	0.2860	0.7250	0.029*
C11	0.22234 (17)	0.6447 (4)	0.65454 (11)	0.0246 (4)
C12	0.38790 (18)	0.5633 (4)	0.79844 (11)	0.0253 (4)
H12	0.4282	0.7347	0.7860	0.030*
C13	0.4990 (3)	0.3758 (6)	0.84642 (14)	0.0444 (6)
H13A	0.4600	0.2030	0.8572	0.053*
H13B	0.5552	0.3350	0.8106	0.053*
C14	0.5849 (3)	0.4865 (7)	0.92845 (14)	0.0501 (7)
H14A	0.5337	0.4985	0.9680	0.075*
H14B	0.6165	0.6671	0.9197	0.075*
H14C	0.6599	0.3656	0.9508	0.075*
C15	0.2971 (2)	0.6350 (9)	0.84970 (15)	0.0578 (9)
H15A	0.3448	0.7459	0.8974	0.087*
H15B	0.2664	0.4686	0.8696	0.087*
H15C	0.2216	0.7368	0.8152	0.087*
C16	0.12597 (18)	1.0397 (4)	0.50566 (12)	0.0278 (4)
H16A	0.0503	0.9865	0.4589	0.042*
H16B	0.1572	1.2181	0.4945	0.042*
H16C	0.0999	1.0476	0.5567	0.042*

	U11	U22	U33	U12	U13	U23
O1	0.0475 (9)	0.0367 (10)	0.0360 (8)	−0.0111 (7)	0.0159 (7)	0.0053 (7)
O2	0.0333 (7)	0.0348 (9)	0.0376 (7)	−0.0119 (7)	0.0012 (6)	0.0042 (7)
O3	0.0587 (11)	0.0619 (14)	0.0401 (9)	−0.0337 (11)	0.0039 (8)	−0.0078 (9)
O4	0.0529 (9)	0.0479 (11)	0.0256 (7)	−0.0039 (9)	0.0015 (6)	0.0023 (8)
O5	0.0263 (6)	0.0311 (8)	0.0265 (6)	0.0058 (6)	0.0092 (5)	−0.0005 (6)
O6	0.0290 (7)	0.0447 (10)	0.0320 (7)	0.0120 (7)	0.0111 (5)	−0.0006 (7)
N1	0.0266 (8)	0.0226 (9)	0.0316 (8)	−0.0008 (7)	0.0099 (6)	0.0016 (7)
N2	0.0334 (9)	0.0378 (12)	0.0279 (8)	−0.0041 (8)	0.0053 (7)	−0.0050 (8)
N3	0.0256 (7)	0.0300 (10)	0.0246 (8)	−0.0046 (7)	0.0020 (6)	0.0053 (7)
N4	0.0250 (7)	0.0276 (9)	0.0260 (8)	0.0049 (7)	0.0059 (6)	0.0050 (7)
N5	0.0311 (8)	0.0242 (9)	0.0226 (7)	0.0071 (7)	0.0073 (6)	0.0004 (6)
C1	0.0219 (8)	0.0195 (10)	0.0277 (9)	0.0018 (7)	0.0075 (7)	0.0015 (7)
C2	0.0262 (9)	0.0244 (10)	0.0257 (9)	0.0029 (8)	0.0082 (7)	0.0012 (8)
C3	0.0236 (8)	0.0290 (11)	0.0257 (9)	0.0016 (8)	0.0053 (7)	−0.0028 (8)
C4	0.0239 (9)	0.0249 (11)	0.0336 (9)	−0.0028 (8)	0.0104 (7)	−0.0028 (8)
C5	0.0280 (9)	0.0253 (11)	0.0276 (9)	−0.0003 (8)	0.0099 (7)	0.0031 (8)
C6	0.0210 (8)	0.0254 (11)	0.0254 (8)	0.0021 (7)	0.0064 (7)	−0.0011 (8)
C7	0.0204 (8)	0.0213 (9)	0.0239 (8)	−0.0048 (7)	0.0009 (6)	−0.0041 (7)
C8	0.0200 (8)	0.0209 (10)	0.0228 (8)	0.0004 (7)	0.0025 (6)	−0.0032 (7)
C9	0.0218 (8)	0.0175 (10)	0.0221 (8)	−0.0014 (7)	0.0030 (6)	−0.0026 (7)
C10	0.0254 (8)	0.0240 (10)	0.0237 (8)	−0.0011 (8)	0.0083 (7)	−0.0014 (8)
C11	0.0206 (8)	0.0266 (11)	0.0244 (8)	−0.0004 (8)	0.0031 (6)	−0.0037 (8)
C12	0.0274 (9)	0.0266 (11)	0.0209 (8)	0.0008 (8)	0.0056 (7)	−0.0016 (7)
C13	0.0492 (13)	0.0449 (16)	0.0314 (10)	0.0177 (12)	0.0005 (9)	0.0001 (10)
C14	0.0420 (13)	0.071 (2)	0.0305 (11)	0.0011 (13)	−0.0001 (9)	0.0054 (12)
C15	0.0391 (12)	0.102 (3)	0.0311 (11)	0.0168 (15)	0.0088 (9)	−0.0188 (14)
C16	0.0229 (8)	0.0242 (11)	0.0330 (10)	0.0017 (8)	0.0032 (7)	0.0003 (8)

O1—N1	1.208 (2)	C5—H5	0.9500
O2—N1	1.248 (2)	C7—C8	1.391 (3)
O3—N2	1.227 (3)	C7—C16	1.500 (3)
O4—N2	1.212 (3)	C8—C11	1.445 (3)
O5—C9	1.246 (2)	C8—C9	1.470 (3)
O6—C11	1.235 (2)	C10—C11	1.544 (3)
N1—C1	1.463 (3)	C10—C12	1.550 (2)
N2—C3	1.472 (2)	C10—H10	1.0000
N3—C6	1.372 (2)	C12—C15	1.519 (3)
N3—N4	1.391 (2)	C12—C13	1.531 (3)
N3—H3N	0.9328	C12—H12	1.0000
N4—C7	1.336 (2)	C13—C14	1.514 (3)
N4—H4N	0.8942	C13—H13A	0.9900
N5—C9	1.343 (2)	C13—H13B	0.9900
N5—C10	1.462 (2)	C14—H14A	0.9800
N5—H5N	0.8585	C14—H14B	0.9800
C1—C2	1.403 (3)	C14—H14C	0.9800
C1—C6	1.413 (3)	C15—H15A	0.9800
C2—C3	1.378 (3)	C15—H15B	0.9800
C2—H2	0.9500	C15—H15C	0.9800
C3—C4	1.387 (3)	C16—H16A	0.9800
C4—C5	1.372 (3)	C16—H16B	0.9800
C4—H4	0.9500	C16—H16C	0.9800
C5—C6	1.421 (3)
O1—N1—O2	121.99 (18)	N5—C9—C8	108.01 (16)
O1—N1—C1	118.93 (16)	N5—C10—C11	102.55 (14)
O2—N1—C1	119.08 (16)	N5—C10—C12	112.72 (16)
O4—N2—O3	124.19 (18)	C11—C10—C12	112.29 (17)
O4—N2—C3	118.86 (19)	N5—C10—H10	109.7
O3—N2—C3	116.95 (19)	C11—C10—H10	109.7
C6—N3—N4	118.40 (17)	C12—C10—H10	109.7
C6—N3—H3N	118.5	O6—C11—C8	129.87 (19)
N4—N3—H3N	111.9	O6—C11—C10	123.60 (17)
C7—N4—N3	121.63 (17)	C8—C11—C10	106.53 (16)
C7—N4—H4N	119.6	C15—C12—C13	111.46 (19)
N3—N4—H4N	117.4	C15—C12—C10	110.08 (17)
C9—N5—C10	114.12 (17)	C13—C12—C10	111.18 (18)
C9—N5—H5N	120.9	C15—C12—H12	108.0
C10—N5—H5N	124.4	C13—C12—H12	108.0
C2—C1—C6	122.02 (18)	C10—C12—H12	108.0
C2—C1—N1	115.71 (16)	C14—C13—C12	115.2 (2)
C6—C1—N1	122.27 (16)	C14—C13—H13A	108.5
C3—C2—C1	118.11 (18)	C12—C13—H13A	108.5
C3—C2—H2	120.9	C14—C13—H13B	108.5
C1—C2—H2	120.9	C12—C13—H13B	108.5
C2—C3—C4	122.15 (17)	H13A—C13—H13B	107.5
C2—C3—N2	119.00 (18)	C13—C14—H14A	109.5
C4—C3—N2	118.85 (19)	C13—C14—H14B	109.5
C5—C4—C3	119.32 (19)	H14A—C14—H14B	109.5
C5—C4—H4	120.3	C13—C14—H14C	109.5
C3—C4—H4	120.3	H14A—C14—H14C	109.5
C4—C5—C6	121.87 (18)	H14B—C14—H14C	109.5
C4—C5—H5	119.1	C12—C15—H15A	109.5
C6—C5—H5	119.1	C12—C15—H15B	109.5
N3—C6—C1	122.96 (18)	H15A—C15—H15B	109.5
N3—C6—C5	120.45 (17)	C12—C15—H15C	109.5
C1—C6—C5	116.52 (17)	H15A—C15—H15C	109.5
N4—C7—C8	118.42 (17)	H15B—C15—H15C	109.5
N4—C7—C16	118.82 (17)	C7—C16—H16A	109.5
C8—C7—C16	122.73 (17)	C7—C16—H16B	109.5
C7—C8—C11	128.27 (17)	H16A—C16—H16B	109.5
C7—C8—C9	123.28 (16)	C7—C16—H16C	109.5
C11—C8—C9	108.45 (16)	H16A—C16—H16C	109.5
O5—C9—N5	124.91 (18)	H16B—C16—H16C	109.5
O5—C9—C8	127.06 (17)
C6—N3—N4—C7	−105.2 (2)	N4—C7—C8—C11	−179.71 (18)
O1—N1—C1—C2	3.8 (3)	C16—C7—C8—C11	−1.4 (3)
O2—N1—C1—C2	−175.79 (18)	N4—C7—C8—C9	0.7 (3)
O1—N1—C1—C6	−176.46 (19)	C16—C7—C8—C9	178.93 (17)
O2—N1—C1—C6	4.0 (3)	C10—N5—C9—O5	179.12 (18)
C6—C1—C2—C3	−0.8 (3)	C10—N5—C9—C8	−2.4 (2)
N1—C1—C2—C3	179.01 (17)	C7—C8—C9—O5	−3.5 (3)
C1—C2—C3—C4	0.1 (3)	C11—C8—C9—O5	176.79 (19)
C1—C2—C3—N2	−179.57 (18)	C7—C8—C9—N5	178.00 (18)
O4—N2—C3—C2	−10.8 (3)	C11—C8—C9—N5	−1.7 (2)
O3—N2—C3—C2	169.4 (2)	C9—N5—C10—C11	5.1 (2)
O4—N2—C3—C4	169.5 (2)	C9—N5—C10—C12	−115.88 (19)
O3—N2—C3—C4	−10.3 (3)	C7—C8—C11—O6	4.6 (4)
C2—C3—C4—C5	0.5 (3)	C9—C8—C11—O6	−175.7 (2)
N2—C3—C4—C5	−179.82 (18)	C7—C8—C11—C10	−174.97 (18)
C3—C4—C5—C6	−0.5 (3)	C9—C8—C11—C10	4.7 (2)
N4—N3—C6—C1	−162.77 (18)	N5—C10—C11—O6	174.63 (19)
N4—N3—C6—C5	20.5 (3)	C12—C10—C11—O6	−64.1 (2)
C2—C1—C6—N3	−176.16 (18)	N5—C10—C11—C8	−5.7 (2)
N1—C1—C6—N3	4.1 (3)	C12—C10—C11—C8	115.53 (17)
C2—C1—C6—C5	0.7 (3)	N5—C10—C12—C15	−172.8 (2)
N1—C1—C6—C5	−179.02 (17)	C11—C10—C12—C15	72.0 (3)
C4—C5—C6—N3	176.88 (19)	N5—C10—C12—C13	−48.8 (2)
C4—C5—C6—C1	−0.1 (3)	C11—C10—C12—C13	−164.01 (19)
N3—N4—C7—C8	−168.70 (16)	C15—C12—C13—C14	−58.2 (3)
N3—N4—C7—C16	13.0 (3)	C10—C12—C13—C14	178.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.93	1.99	2.630 (2)	125
N4—H4N···O5	0.89	2.00	2.710 (2)	135
N3—H3N···O5i	0.93	2.36	2.949 (2)	121
N4—H4N···O5i	0.89	2.43	2.898 (2)	113
N5—H5N···O2ii	0.86	2.48	3.293 (2)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O2	0.93	1.99	2.630 (2)	125
N4—H4N⋯O5	0.89	2.00	2.710 (2)	135
N3—H3N⋯O5i	0.93	2.36	2.949 (2)	121
N4—H4N⋯O5i	0.89	2.43	2.898 (2)	113
N5—H5N⋯O2ii	0.86	2.48	3.293 (2)	159

Symmetry codes: (i) ; (ii) .