Benzyl­idene­acetone 2,4-di­nitro­phenyl­hydrazone

Crystals of the title compound, C₁₆H₁₄N₄O₄, were obtained from a condensation reaction of benzyl­idene­acetone and 2,4-di­nitro­phenyl­hydrazine. The mol­ecule has a nearly planar structure with a dihedral angle of 7.57 (4)° between the di­nitro­phenyl and benzyl­idene mean planes. Within the di­nitro­phenyl moiety, the distances of 1.420 (2) and 1.411 (3) Å for the C-C bonds near the imine group are longer than the average distance of 1.374 (3) Å for the other C-C bonds in the same benzene ring. The short N-C distance of 1.338 (2) Å indicates electron delocalization between the imine group and di­nitro­phenyl ring.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.048
• wR factor = 0.127
• Data-to-parameter ratio = 12.4

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Computing details

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC & Rigaku Corporation, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Benzylideneacetone 2,4-dinitrophenylhydrazone

Crystal data

C16H14N4O4	F(000) = 680
Mr = 326.31	Dx = 1.392 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 7517 reflections
a = 7.3916 (3) Å	θ = 2.5–24.0°
b = 15.7043 (7) Å	µ = 0.10 mm^−1
c = 13.7350 (5) Å	T = 295 K
β = 102.4362 (13)°	Prism, red
V = 1556.95 (11) Å^3	0.27 × 0.15 × 0.13 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2072 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
Detector resolution: 10.00 pixels mm^-1	h = −8→8
ω scans	k = −18→18
10933 measured reflections	l = −16→16
2696 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0606P)^2 + 0.3839P] where P = (Fo^2 + 2Fc^2)/3
2696 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.8927 (3)	−0.03160 (10)	0.64656 (12)	0.0814 (5)
O2	0.8462 (2)	−0.07379 (9)	0.49397 (12)	0.0738 (5)
O3	0.3529 (3)	0.20670 (11)	0.26326 (11)	0.0824 (5)
O4	0.4949 (3)	0.09308 (11)	0.23551 (10)	0.0859 (6)
N1	0.4114 (2)	0.27207 (10)	0.44203 (11)	0.0503 (4)
H1	0.3584	0.2803	0.3806	0.060*
N2	0.3922 (2)	0.33200 (10)	0.51249 (11)	0.0479 (4)
N3	0.4550 (2)	0.14594 (11)	0.29266 (12)	0.0590 (5)
N4	0.8279 (2)	−0.02150 (11)	0.55723 (13)	0.0569 (4)
C1	0.5112 (2)	0.20133 (11)	0.46779 (13)	0.0429 (4)
C2	0.5347 (2)	0.13764 (11)	0.39821 (12)	0.0438 (4)
C3	0.6394 (2)	0.06561 (11)	0.42742 (13)	0.0456 (4)
H3	0.6529	0.0245	0.3808	0.055*
C4	0.7229 (2)	0.05550 (11)	0.52572 (13)	0.0460 (4)
C5	0.7077 (3)	0.11756 (13)	0.59574 (13)	0.0542 (5)
H5	0.7678	0.1104	0.6620	0.065*
C6	0.6052 (3)	0.18852 (12)	0.56755 (13)	0.0514 (5)
H6	0.5968	0.2297	0.6150	0.062*
C7	0.3195 (2)	0.40353 (12)	0.47725 (13)	0.0456 (4)
C8	0.2647 (3)	0.42339 (13)	0.36789 (14)	0.0567 (5)
H8A	0.3660	0.4105	0.3368	0.085*
H8B	0.2340	0.4827	0.3591	0.085*
H8C	0.1591	0.3896	0.3379	0.085*
C9	0.2960 (3)	0.46611 (12)	0.55142 (14)	0.0481 (4)
H9	0.3331	0.4507	0.6181	0.058*
C10	0.2256 (2)	0.54362 (12)	0.53139 (14)	0.0480 (5)
H10	0.1875	0.5571	0.4642	0.058*
C11	0.2003 (2)	0.61030 (11)	0.60129 (14)	0.0465 (4)
C12	0.2618 (3)	0.60357 (13)	0.70443 (15)	0.0562 (5)
H12	0.3207	0.5540	0.7317	0.067*
C13	0.2362 (3)	0.66937 (15)	0.76623 (17)	0.0673 (6)
H13	0.2794	0.6642	0.8348	0.081*
C14	0.1472 (3)	0.74283 (14)	0.7274 (2)	0.0718 (7)
H14	0.1294	0.7869	0.7696	0.086*
C15	0.0850 (3)	0.75077 (13)	0.6267 (2)	0.0673 (6)
H15	0.0244	0.8002	0.6003	0.081*
C16	0.1121 (3)	0.68547 (12)	0.56412 (17)	0.0563 (5)
H16	0.0705	0.6918	0.4956	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0995 (13)	0.0718 (11)	0.0632 (10)	0.0184 (9)	−0.0044 (9)	0.0132 (8)
O2	0.0872 (12)	0.0502 (9)	0.0810 (10)	0.0104 (8)	0.0116 (9)	−0.0096 (8)
O3	0.1068 (13)	0.0809 (11)	0.0473 (8)	0.0264 (10)	−0.0104 (8)	0.0005 (8)
O4	0.1254 (15)	0.0771 (11)	0.0465 (8)	0.0119 (10)	−0.0008 (9)	−0.0205 (8)
N1	0.0559 (10)	0.0507 (9)	0.0415 (8)	0.0035 (7)	0.0045 (7)	−0.0018 (7)
N2	0.0486 (9)	0.0485 (9)	0.0457 (8)	0.0037 (7)	0.0081 (7)	−0.0013 (7)
N3	0.0721 (12)	0.0570 (10)	0.0425 (9)	−0.0041 (9)	0.0003 (8)	−0.0059 (8)
N4	0.0552 (10)	0.0493 (10)	0.0643 (11)	−0.0007 (8)	0.0087 (8)	0.0034 (8)
C1	0.0407 (9)	0.0452 (10)	0.0433 (9)	−0.0031 (8)	0.0103 (8)	0.0009 (8)
C2	0.0452 (10)	0.0465 (10)	0.0377 (9)	−0.0077 (8)	0.0048 (8)	−0.0022 (7)
C3	0.0460 (10)	0.0441 (10)	0.0472 (10)	−0.0082 (8)	0.0108 (8)	−0.0062 (8)
C4	0.0410 (10)	0.0450 (10)	0.0507 (10)	−0.0014 (8)	0.0070 (8)	0.0032 (8)
C5	0.0597 (12)	0.0611 (12)	0.0396 (9)	0.0065 (10)	0.0057 (9)	0.0008 (9)
C6	0.0597 (12)	0.0554 (11)	0.0387 (9)	0.0052 (9)	0.0099 (9)	−0.0053 (8)
C7	0.0387 (9)	0.0502 (11)	0.0482 (10)	−0.0016 (8)	0.0100 (8)	0.0044 (8)
C8	0.0629 (13)	0.0582 (12)	0.0481 (10)	0.0054 (10)	0.0101 (9)	0.0048 (9)
C9	0.0477 (10)	0.0508 (11)	0.0461 (9)	0.0017 (8)	0.0110 (8)	0.0054 (8)
C10	0.0407 (10)	0.0529 (11)	0.0502 (10)	0.0004 (8)	0.0099 (8)	0.0080 (8)
C11	0.0388 (9)	0.0455 (10)	0.0570 (11)	−0.0002 (8)	0.0142 (8)	0.0072 (8)
C12	0.0571 (12)	0.0528 (12)	0.0608 (12)	0.0083 (9)	0.0170 (10)	0.0069 (9)
C13	0.0719 (15)	0.0708 (15)	0.0625 (13)	0.0001 (11)	0.0217 (11)	−0.0044 (11)
C14	0.0782 (16)	0.0542 (13)	0.0928 (18)	−0.0052 (11)	0.0403 (14)	−0.0100 (12)
C15	0.0651 (14)	0.0416 (12)	0.1030 (19)	0.0053 (10)	0.0354 (13)	0.0136 (12)
C16	0.0526 (12)	0.0490 (11)	0.0699 (13)	0.0025 (9)	0.0185 (10)	0.0137 (10)

Geometric parameters (Å, º)

O1—N4	1.228 (2)	C7—C8	1.502 (2)
O2—N4	1.224 (2)	C8—H8A	0.9600
O3—N3	1.230 (2)	C8—H8B	0.9600
O4—N3	1.221 (2)	C8—H8C	0.9600
N1—C1	1.338 (2)	C9—C10	1.329 (3)
N1—N2	1.379 (2)	C9—H9	0.9300
N1—H1	0.8600	C10—C11	1.460 (3)
N2—C7	1.293 (2)	C10—H10	0.9300
N3—C2	1.448 (2)	C11—C16	1.391 (3)
N4—C4	1.452 (2)	C11—C12	1.395 (3)
C1—C2	1.420 (2)	C12—C13	1.376 (3)
C1—C6	1.411 (3)	C12—H12	0.9300
C2—C3	1.380 (3)	C13—C14	1.377 (3)
C3—C4	1.368 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.367 (3)
C4—C5	1.391 (3)	C14—H14	0.9300
C5—C6	1.356 (3)	C15—C16	1.380 (3)
C5—H5	0.9300	C15—H15	0.9300
C6—H6	0.9300	C16—H16	0.9300
C7—C9	1.453 (3)
C1—N1—N2	121.02 (15)	C7—C8—H8A	109.5
C1—N1—H1	119.5	C7—C8—H8B	109.5
N2—N1—H1	119.5	H8A—C8—H8B	109.5
C7—N2—N1	115.31 (15)	C7—C8—H8C	109.5
O4—N3—O3	122.17 (17)	H8A—C8—H8C	109.5
O4—N3—C2	118.66 (17)	H8B—C8—H8C	109.5
O3—N3—C2	119.15 (16)	C10—C9—C7	125.11 (17)
O2—N4—O1	122.95 (18)	C10—C9—H9	117.4
O2—N4—C4	118.75 (17)	C7—C9—H9	117.4
O1—N4—C4	118.30 (17)	C9—C10—C11	128.37 (18)
N1—C1—C6	120.21 (16)	C9—C10—H10	115.8
N1—C1—C2	123.17 (16)	C11—C10—H10	115.8
C6—C1—C2	116.58 (16)	C16—C11—C12	117.47 (18)
C3—C2—C1	121.58 (16)	C16—C11—C10	118.92 (17)
C3—C2—N3	116.51 (16)	C12—C11—C10	123.61 (17)
C1—C2—N3	121.88 (16)	C13—C12—C11	120.76 (19)
C4—C3—C2	119.19 (17)	C13—C12—H12	119.6
C4—C3—H3	120.4	C11—C12—H12	119.6
C2—C3—H3	120.4	C12—C13—C14	120.5 (2)
C3—C4—C5	120.99 (17)	C12—C13—H13	119.7
C3—C4—N4	119.32 (17)	C14—C13—H13	119.7
C5—C4—N4	119.69 (17)	C15—C14—C13	119.8 (2)
C6—C5—C4	120.11 (17)	C15—C14—H14	120.1
C6—C5—H5	119.9	C13—C14—H14	120.1
C4—C5—H5	119.9	C14—C15—C16	120.0 (2)
C5—C6—C1	121.50 (17)	C14—C15—H15	120.0
C5—C6—H6	119.3	C16—C15—H15	120.0
C1—C6—H6	119.3	C15—C16—C11	121.4 (2)
N2—C7—C9	115.34 (16)	C15—C16—H16	119.3
N2—C7—C8	123.74 (17)	C11—C16—H16	119.3
C9—C7—C8	120.91 (16)
C1—N1—N2—C7	168.95 (16)	N4—C4—C5—C6	−178.02 (17)
N2—N1—C1—C6	−2.6 (3)	C4—C5—C6—C1	0.4 (3)
N2—N1—C1—C2	179.76 (15)	N1—C1—C6—C5	−179.88 (17)
N1—C1—C2—C3	179.72 (16)	C2—C1—C6—C5	−2.1 (3)
C6—C1—C2—C3	2.0 (3)	N1—N2—C7—C9	178.88 (14)
N1—C1—C2—N3	1.7 (3)	N1—N2—C7—C8	−2.2 (3)
C6—C1—C2—N3	−176.08 (16)	N2—C7—C9—C10	179.51 (17)
O4—N3—C2—C3	−5.2 (3)	C8—C7—C9—C10	0.5 (3)
O3—N3—C2—C3	176.37 (18)	C7—C9—C10—C11	−178.90 (16)
O4—N3—C2—C1	173.00 (18)	C9—C10—C11—C16	−175.85 (18)
O3—N3—C2—C1	−5.5 (3)	C9—C10—C11—C12	4.9 (3)
C1—C2—C3—C4	−0.2 (3)	C16—C11—C12—C13	−0.3 (3)
N3—C2—C3—C4	178.00 (16)	C10—C11—C12—C13	178.95 (18)
C2—C3—C4—C5	−1.7 (3)	C11—C12—C13—C14	0.8 (3)
C2—C3—C4—N4	177.94 (15)	C12—C13—C14—C15	−0.5 (3)
O2—N4—C4—C3	3.4 (3)	C13—C14—C15—C16	−0.2 (3)
O1—N4—C4—C3	−175.83 (18)	C14—C15—C16—C11	0.7 (3)
O2—N4—C4—C5	−177.02 (17)	C12—C11—C16—C15	−0.4 (3)
O1—N4—C4—C5	3.8 (3)	C10—C11—C16—C15	−179.77 (17)
C3—C4—C5—C6	1.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.86	1.98	2.610 (2)	130
C8—H8B···O4^i	0.96	2.57	3.410 (3)	146
C13—H13···O2^ii	0.93	2.56	3.406 (3)	151

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