3-Chloro­aceto­phenone 2,4-di­nitro­phenyl­hydrazone

Crystals of the title compound, C₁₄H₁₁ClN₄O₄, were obtained from a condensation reaction of m-chloro­aceto­phenone and 2,4-di­nitro­phenyl­hydrazine. The two benzene rings of the title mol­ecule have a dihedral angle of 16.17 (6)°. Within the di­nitro­phenyl moiety, the distances of 1.422 (3) and 1.415 (3) Å for the C—C bonds close to the imine group are appreciably longer than the average distance of 1.376 (3) Å for other aromatic C—C bonds in the same benzene ring. The overlapped arrangement of chloro­phenyl rings of neighbouring mol­ecules shows the existence of a π–π stacking interaction.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.050
• wR factor = 0.127
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT414_ALERT_2_C Short Intra D-H..H-X       H3     ..  H8A     ..       1.95 Ang.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C3     ..  O2      ..      99.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C3     ..  O3      ..      98.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C5     ..  O4      ..      98.00 Deg.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

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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); software used to prepare material for publication: WinGX (Farrugia, 1999).

3-Chloroacetophenone 2,4-dinitrophenylhydrazone

Crystal data

C14H11ClN4O4	F(000) = 688
Mr = 334.72	Dx = 1.518 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 10397 reflections
a = 13.221 (1) Å	θ = 2.8–27.0°
b = 15.1466 (11) Å	µ = 0.29 mm^−1
c = 7.5827 (6) Å	T = 295 K
β = 105.324 (2)°	Prism, orange
V = 1464.47 (19) Å^3	0.38 × 0.22 × 0.10 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2250 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 27.5°, θmin = 1.6°
Detector resolution: 10.00 pixels mm^-1	h = −17→17
ω scans	k = −19→19
13167 measured reflections	l = −9→9
3349 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)] = 0.050	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) + (0.0602P)^2 + 0.2883P] where P = (Fo^2 + 2Fc^2)/3
3349 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.30 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
Cl	0.38110 (6)	0.05556 (4)	0.13697 (10)	0.0806 (2)
O1	0.04370 (13)	0.57094 (9)	0.1734 (2)	0.0674 (4)
O2	−0.10555 (13)	0.58947 (10)	0.2322 (2)	0.0688 (4)
O3	−0.26870 (16)	0.36564 (13)	0.4921 (3)	0.0988 (7)
O4	−0.21499 (14)	0.23142 (12)	0.4958 (3)	0.0841 (6)
N1	−0.03099 (14)	0.54285 (10)	0.2284 (2)	0.0496 (4)
N2	−0.20686 (15)	0.31029 (14)	0.4682 (3)	0.0628 (5)
N3	0.13899 (13)	0.42009 (11)	0.2281 (2)	0.0513 (4)
H3	0.1467	0.4746	0.2029	0.062*
N4	0.21258 (13)	0.35870 (11)	0.2122 (2)	0.0500 (4)
C1	0.05462 (14)	0.39436 (12)	0.2834 (2)	0.0427 (4)
C2	−0.02939 (15)	0.45235 (12)	0.2873 (2)	0.0431 (4)
C3	−0.11432 (15)	0.42493 (12)	0.3492 (3)	0.0449 (4)
H3A	−0.1675	0.4642	0.3542	0.054*
C4	−0.11808 (15)	0.33948 (13)	0.4023 (3)	0.0473 (5)
C5	−0.03894 (16)	0.27967 (13)	0.3975 (3)	0.0488 (5)
H5	−0.0436	0.2215	0.4338	0.059*
C6	0.04545 (16)	0.30628 (12)	0.3396 (3)	0.0487 (5)
H6	0.0979	0.2658	0.3370	0.058*
C7	0.29240 (16)	0.38758 (14)	0.1620 (3)	0.0514 (5)
C8	0.3105 (2)	0.48285 (16)	0.1239 (4)	0.0728 (7)
H8A	0.2449	0.5100	0.0634	0.109*
H8B	0.3575	0.4865	0.0469	0.109*
H8C	0.3407	0.5129	0.2370	0.109*
C9	0.36883 (15)	0.31909 (15)	0.1423 (3)	0.0522 (5)
C10	0.34343 (16)	0.23037 (15)	0.1485 (3)	0.0542 (5)
H10	0.2786	0.2140	0.1645	0.065*
C11	0.41469 (18)	0.16637 (16)	0.1309 (3)	0.0593 (6)
C12	0.51120 (19)	0.18825 (19)	0.1065 (3)	0.0692 (7)
H12	0.5582	0.1446	0.0939	0.083*
C13	0.53633 (18)	0.2754 (2)	0.1012 (3)	0.0727 (7)
H13	0.6014	0.2911	0.0856	0.087*
C14	0.46650 (17)	0.34097 (17)	0.1186 (3)	0.0641 (6)
H14	0.4851	0.4000	0.1144	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0804 (5)	0.0743 (4)	0.0917 (5)	0.0210 (3)	0.0307 (4)	0.0031 (3)
O1	0.0725 (11)	0.0464 (8)	0.0905 (12)	−0.0036 (7)	0.0341 (9)	0.0089 (8)
O2	0.0682 (10)	0.0468 (8)	0.0939 (12)	0.0139 (7)	0.0258 (9)	0.0060 (8)
O3	0.0703 (12)	0.0931 (13)	0.156 (2)	0.0041 (10)	0.0704 (13)	0.0057 (13)
O4	0.0710 (11)	0.0752 (11)	0.1127 (15)	−0.0135 (9)	0.0357 (11)	0.0236 (11)
N1	0.0539 (10)	0.0394 (8)	0.0552 (10)	0.0006 (7)	0.0141 (8)	−0.0029 (7)
N2	0.0514 (11)	0.0694 (12)	0.0717 (12)	−0.0073 (9)	0.0233 (9)	0.0044 (10)
N3	0.0475 (9)	0.0450 (9)	0.0668 (11)	0.0012 (7)	0.0250 (8)	0.0007 (8)
N4	0.0430 (9)	0.0556 (9)	0.0545 (9)	0.0037 (7)	0.0182 (7)	−0.0018 (8)
C1	0.0439 (10)	0.0425 (9)	0.0434 (10)	−0.0010 (8)	0.0147 (8)	−0.0050 (8)
C2	0.0476 (10)	0.0374 (9)	0.0438 (10)	−0.0002 (8)	0.0113 (8)	−0.0039 (8)
C3	0.0411 (10)	0.0462 (10)	0.0479 (10)	0.0036 (8)	0.0129 (8)	−0.0055 (8)
C4	0.0445 (11)	0.0516 (11)	0.0482 (11)	−0.0045 (8)	0.0161 (8)	−0.0029 (9)
C5	0.0558 (12)	0.0396 (9)	0.0526 (11)	−0.0004 (8)	0.0171 (9)	0.0023 (9)
C6	0.0512 (12)	0.0426 (10)	0.0551 (12)	0.0072 (8)	0.0188 (9)	−0.0014 (9)
C7	0.0439 (11)	0.0624 (12)	0.0493 (11)	−0.0046 (9)	0.0147 (9)	−0.0056 (10)
C8	0.0636 (15)	0.0687 (15)	0.0927 (19)	−0.0118 (12)	0.0323 (14)	−0.0019 (13)
C9	0.0395 (11)	0.0747 (14)	0.0441 (10)	−0.0015 (10)	0.0143 (8)	−0.0034 (10)
C10	0.0414 (11)	0.0740 (14)	0.0503 (11)	0.0049 (10)	0.0174 (9)	−0.0028 (10)
C11	0.0512 (12)	0.0791 (15)	0.0485 (11)	0.0126 (11)	0.0146 (9)	0.0021 (11)
C12	0.0509 (13)	0.099 (2)	0.0608 (14)	0.0211 (13)	0.0211 (11)	0.0039 (13)
C13	0.0406 (12)	0.118 (2)	0.0654 (15)	0.0050 (13)	0.0239 (11)	0.0034 (15)
C14	0.0473 (12)	0.0882 (17)	0.0606 (13)	−0.0037 (11)	0.0211 (10)	−0.0008 (12)

Geometric parameters (Å, º)

Cl—C11	1.740 (3)	C5—H5	0.9300
O1—N1	1.244 (2)	C6—H6	0.9300
O2—N1	1.219 (2)	C7—C8	1.503 (3)
O3—N2	1.218 (3)	C7—C9	1.483 (3)
O4—N2	1.222 (2)	C8—H8A	0.9600
N1—C2	1.440 (2)	C8—H8B	0.9600
N2—C4	1.461 (3)	C8—H8C	0.9600
N3—N4	1.374 (2)	C9—C10	1.389 (3)
N3—C1	1.349 (2)	C9—C14	1.390 (3)
N3—H3	0.8600	C10—C11	1.383 (3)
N4—C7	1.290 (3)	C10—H10	0.9300
C1—C2	1.422 (3)	C11—C12	1.377 (3)
C1—C6	1.415 (3)	C12—C13	1.364 (4)
C2—C3	1.390 (3)	C12—H12	0.9300
C3—C4	1.360 (3)	C13—C14	1.386 (3)
C3—H3A	0.9300	C13—H13	0.9300
C4—C5	1.392 (3)	C14—H14	0.9300
C5—C6	1.363 (3)
O2—N1—O1	121.90 (17)	N4—C7—C9	115.15 (19)
O2—N1—C2	119.31 (17)	N4—C7—C8	124.5 (2)
O1—N1—C2	118.79 (16)	C9—C7—C8	120.31 (18)
O3—N2—O4	123.7 (2)	C7—C8—H8A	109.5
O3—N2—C4	118.33 (19)	C7—C8—H8B	109.5
O4—N2—C4	118.00 (19)	H8A—C8—H8B	109.5
C1—N3—N4	119.65 (16)	C7—C8—H8C	109.5
C1—N3—H3	120.2	H8A—C8—H8C	109.5
N4—N3—H3	120.2	H8B—C8—H8C	109.5
C7—N4—N3	116.74 (18)	C10—C9—C14	118.4 (2)
N3—C1—C6	120.64 (17)	C10—C9—C7	119.75 (18)
N3—C1—C2	122.86 (17)	C14—C9—C7	121.8 (2)
C6—C1—C2	116.50 (17)	C11—C10—C9	119.9 (2)
C3—C2—C1	121.83 (17)	C11—C10—H10	120.1
C3—C2—N1	116.25 (17)	C9—C10—H10	120.1
C1—C2—N1	121.92 (17)	C12—C11—C10	121.6 (2)
C4—C3—C2	118.70 (17)	C12—C11—Cl	119.18 (19)
C4—C3—H3A	120.7	C10—C11—Cl	119.25 (18)
C2—C3—H3A	120.7	C13—C12—C11	118.6 (2)
C3—C4—C5	121.68 (18)	C13—C12—H12	120.7
C3—C4—N2	119.00 (18)	C11—C12—H12	120.7
C5—C4—N2	119.32 (18)	C12—C13—C14	121.1 (2)
C6—C5—C4	120.05 (18)	C12—C13—H13	119.4
C6—C5—H5	120.0	C14—C13—H13	119.4
C4—C5—H5	120.0	C13—C14—C9	120.4 (2)
C5—C6—C1	121.21 (18)	C13—C14—H14	119.8
C5—C6—H6	119.4	C9—C14—H14	119.8
C1—C6—H6	119.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1	0.86	1.97	2.589 (2)	128
C5—H5···O1^i	0.93	2.42	3.205 (2)	142
C3—H3A···O2	0.93	2.35	2.658 (2)	99
C3—H3A···O3	0.93	2.42	2.705 (3)	98
C5—H5···O4	0.93	2.44	2.725 (3)	98
C6—H6···N4	0.93	2.44	2.752 (3)	100

Symmetry code: (i) −x, y−1/2, −z+1/2.