Cyclo­hexanone 2,4-di­nitro­phenyl­hydrazone

Crystals of the title compound, C₁₂H₁₄N₄O₄ were obtained by a condensation reaction between cyclo­hexanone and 2,4-di­nitro­phenyl­hydrazine. Within the di­nitro­phenyl group, the distances of 1.420 (2) and 1.422 (2) Å for the C—C bonds close to the imino group are appreciably longer than the average distance of 1.377 (2) Å for the rest of the C—C bonds in the ring. The overlapped arrangement and separation of 3.379 (8) Å between parallel aromatic rings suggest the existence of a π–π-stacking interaction between neighboring mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.047
• wR factor = 0.123
• Data-to-parameter ratio = 15.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

---

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 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); software used to prepare material for publication: WinGX (Farrugia, 1999).

(I)

Crystal data

C12H14N4O4	Z = 2
Mr = 278.27	F(000) = 292
Triclinic, P1	Dx = 1.433 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9700 (11) Å	Cell parameters from 2694 reflections
b = 8.0438 (10) Å	θ = 1.8–27.4°
c = 11.8063 (13) Å	µ = 0.11 mm^−1
α = 87.910 (2)°	T = 296 K
β = 79.862 (4)°	Plate, yellow
γ = 81.879 (3)°	0.51 × 0.45 × 0.09 mm
V = 645.01 (15) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	1988 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 27.4°, θmin = 1.8°
Detector resolution: 10.00 pixels mm^-1	h = −8→9
ω scans	k = −10→10
4526 measured reflections	l = −15→15
2883 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0573P)^2 + 0.0918P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2883 reflections	Δρmax = 0.21 e Å^−3
182 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (4)

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	0.14406 (18)	0.09224 (17)	0.54658 (11)	0.0571 (4)
O2	0.2134 (2)	0.0879 (2)	0.71724 (11)	0.0681 (4)
O3	0.7503 (2)	0.3175 (2)	0.80779 (11)	0.0669 (4)
O4	0.94536 (19)	0.43607 (18)	0.67674 (12)	0.0617 (4)
N1	0.24982 (19)	0.12339 (18)	0.61488 (12)	0.0434 (3)
N2	0.8044 (2)	0.35901 (19)	0.70775 (13)	0.0470 (4)
N3	0.3746 (2)	0.21389 (18)	0.37246 (11)	0.0431 (3)
H3	0.2682	0.1691	0.3904	0.052*
N4	0.4436 (2)	0.25567 (19)	0.25912 (12)	0.0465 (4)
C1	0.4784 (2)	0.24515 (19)	0.45436 (13)	0.0362 (4)
C2	0.4225 (2)	0.20425 (19)	0.57250 (13)	0.0369 (4)
C3	0.5299 (2)	0.2407 (2)	0.65450 (13)	0.0393 (4)
H3A	0.4907	0.2134	0.7315	0.047*
C4	0.6942 (2)	0.3174 (2)	0.62082 (14)	0.0398 (4)
C5	0.7564 (2)	0.3574 (2)	0.50522 (14)	0.0420 (4)
H5	0.8693	0.4083	0.4837	0.050*
C6	0.6522 (2)	0.3221 (2)	0.42437 (14)	0.0417 (4)
H6	0.6954	0.3488	0.3477	0.050*
C7	0.3472 (3)	0.2189 (2)	0.18323 (14)	0.0452 (4)
C8	0.4325 (3)	0.2582 (3)	0.06035 (15)	0.0607 (5)
H8A	0.4994	0.1554	0.0231	0.073*
H8B	0.5292	0.3340	0.0598	0.073*
C9	0.2766 (3)	0.3378 (3)	−0.00747 (16)	0.0633 (6)
H9A	0.2260	0.4500	0.0208	0.076*
H9B	0.3352	0.3473	−0.0879	0.076*
C10	0.1091 (3)	0.2344 (3)	0.00317 (17)	0.0674 (6)
H10A	0.1583	0.1234	−0.0277	0.081*
H10B	0.0116	0.2873	−0.0409	0.081*
C11	0.0153 (3)	0.2196 (3)	0.12850 (17)	0.0650 (6)
H11A	−0.0926	0.1539	0.1344	0.078*
H11B	−0.0382	0.3307	0.1580	0.078*
C12	0.1634 (3)	0.1366 (3)	0.20139 (17)	0.0619 (5)
H12A	0.1035	0.1432	0.2820	0.074*
H12B	0.1977	0.0188	0.1817	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0471 (7)	0.0731 (9)	0.0579 (8)	−0.0265 (6)	−0.0142 (6)	0.0028 (7)
O2	0.0642 (9)	0.0960 (11)	0.0494 (8)	−0.0377 (8)	−0.0063 (6)	0.0178 (7)
O3	0.0747 (9)	0.0904 (11)	0.0438 (8)	−0.0270 (8)	−0.0207 (6)	0.0034 (7)
O4	0.0583 (8)	0.0693 (9)	0.0664 (9)	−0.0281 (7)	−0.0191 (7)	−0.0040 (7)
N1	0.0365 (7)	0.0453 (9)	0.0485 (8)	−0.0101 (6)	−0.0049 (6)	0.0044 (7)
N2	0.0462 (8)	0.0485 (9)	0.0503 (9)	−0.0105 (7)	−0.0154 (6)	−0.0047 (7)
N3	0.0417 (8)	0.0511 (9)	0.0397 (8)	−0.0144 (6)	−0.0106 (6)	0.0042 (6)
N4	0.0465 (8)	0.0564 (9)	0.0388 (7)	−0.0127 (7)	−0.0097 (6)	0.0033 (7)
C1	0.0348 (8)	0.0334 (8)	0.0408 (9)	−0.0026 (6)	−0.0089 (6)	−0.0003 (7)
C2	0.0336 (8)	0.0339 (8)	0.0430 (9)	−0.0062 (6)	−0.0055 (6)	0.0026 (7)
C3	0.0424 (9)	0.0396 (9)	0.0358 (8)	−0.0051 (7)	−0.0069 (6)	0.0018 (7)
C4	0.0379 (8)	0.0399 (9)	0.0440 (9)	−0.0057 (7)	−0.0126 (7)	−0.0019 (7)
C5	0.0362 (8)	0.0449 (10)	0.0464 (9)	−0.0120 (7)	−0.0066 (7)	0.0010 (7)
C6	0.0422 (9)	0.0449 (10)	0.0377 (8)	−0.0093 (7)	−0.0040 (7)	0.0035 (7)
C7	0.0477 (10)	0.0482 (10)	0.0415 (9)	−0.0096 (8)	−0.0107 (7)	0.0013 (7)
C8	0.0593 (12)	0.0817 (15)	0.0422 (10)	−0.0182 (10)	−0.0045 (8)	−0.0026 (10)
C9	0.0801 (14)	0.0745 (15)	0.0365 (9)	−0.0162 (11)	−0.0102 (9)	0.0053 (9)
C10	0.0800 (15)	0.0804 (15)	0.0497 (11)	−0.0147 (12)	−0.0295 (10)	−0.0011 (10)
C11	0.0591 (12)	0.0859 (16)	0.0586 (12)	−0.0269 (11)	−0.0214 (9)	0.0064 (11)
C12	0.0708 (13)	0.0737 (14)	0.0526 (11)	−0.0348 (11)	−0.0252 (9)	0.0136 (10)

Geometric parameters (Å, º)

O1—N1	1.2380 (17)	C6—H6	0.93
O2—N1	1.2221 (17)	C7—C12	1.503 (2)
O3—N2	1.2242 (18)	C7—C8	1.508 (2)
O4—N2	1.2298 (18)	C8—C9	1.518 (3)
N1—C2	1.4516 (19)	C8—H8A	0.97
N2—C4	1.460 (2)	C8—H8B	0.97
N3—C1	1.355 (2)	C9—C10	1.511 (3)
N3—N4	1.3860 (18)	C9—H9A	0.97
N3—H3	0.86	C9—H9B	0.97
N4—C7	1.276 (2)	C10—C11	1.517 (3)
C1—C2	1.420 (2)	C10—H10A	0.97
C1—C6	1.422 (2)	C10—H10B	0.97
C2—C3	1.386 (2)	C11—C12	1.526 (3)
C3—C4	1.368 (2)	C11—H11A	0.97
C3—H3A	0.93	C11—H11B	0.97
C4—C5	1.398 (2)	C12—H12A	0.97
C5—C6	1.357 (2)	C12—H12B	0.97
C5—H5	0.93
O2—N1—O1	121.96 (13)	C7—C8—C9	112.45 (16)
O2—N1—C2	118.82 (14)	C7—C8—H8A	109.1
O1—N1—C2	119.23 (13)	C9—C8—H8A	109.1
O3—N2—O4	123.44 (14)	C7—C8—H8B	109.1
O3—N2—C4	118.41 (14)	C9—C8—H8B	109.1
O4—N2—C4	118.14 (14)	H8A—C8—H8B	107.8
C1—N3—N4	118.61 (13)	C10—C9—C8	111.09 (17)
C1—N3—H3	120.7	C10—C9—H9A	109.4
N4—N3—H3	120.7	C8—C9—H9A	109.4
C7—N4—N3	117.28 (14)	C10—C9—H9B	109.4
N3—C1—C2	123.04 (14)	C8—C9—H9B	109.4
N3—C1—C6	120.41 (14)	H9A—C9—H9B	108.0
C2—C1—C6	116.54 (14)	C9—C10—C11	109.92 (16)
C3—C2—C1	121.62 (14)	C9—C10—H10A	109.7
C3—C2—N1	116.02 (14)	C11—C10—H10A	109.7
C1—C2—N1	122.36 (14)	C9—C10—H10B	109.7
C4—C3—C2	119.24 (14)	C11—C10—H10B	109.7
C4—C3—H3A	120.4	H10A—C10—H10B	108.2
C2—C3—H3A	120.4	C10—C11—C12	111.58 (18)
C3—C4—C5	121.06 (15)	C10—C11—H11A	109.3
C3—C4—N2	119.07 (14)	C12—C11—H11A	109.3
C5—C4—N2	119.86 (14)	C10—C11—H11B	109.3
C6—C5—C4	120.08 (15)	C12—C11—H11B	109.3
C6—C5—H5	120.0	H11A—C11—H11B	108.0
C4—C5—H5	120.0	C7—C12—C11	111.84 (16)
C5—C6—C1	121.44 (15)	C7—C12—H12A	109.2
C5—C6—H6	119.3	C11—C12—H12A	109.2
C1—C6—H6	119.3	C7—C12—H12B	109.2
N4—C7—C12	127.84 (16)	C11—C12—H12B	109.2
N4—C7—C8	115.74 (15)	H12A—C12—H12B	107.9
C12—C7—C8	116.39 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1	0.86	2.01	2.6268 (19)	128
C5—H5···O4	0.93	2.41	3.292 (2)	143