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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.
Supporting information
CCDC reference: 242364
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (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
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
top
Crystal data top
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) Å3 | 0.38 × 0.22 × 0.10 mm |
Z = 4 | |
Data collection top
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 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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0602P)2 + 0.2883P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···O1i | 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. |
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