In the title compound, C
12H
9ClN
4O
5, both nitro groups are rotated significantly from the imidazole plane. The C-4—NO
2 bond length is only slightly shorter than the value for a normal single C
sp2—NO
2 bond and the C-5—NO
2 bond length is significantly shorter than C-4—NO
2. In consequence, the C-4-nitro group is easily replaced by morpholine, while the C-5-nitro group shows an extraordinary stability on treatment with the amine. In the crystal structure, the molecules are linked through C—H
O hydrogen bonds.
Supporting information
CCDC reference: 610708
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.038
- wR factor = 0.117
- Data-to-parameter ratio = 13.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N16
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 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
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); 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).
1-(4-Chlorophenacyl)-2-methyl-4,5-dinitro-1
H-imidazole
top
Crystal data top
C12H9ClN4O5 | F(000) = 1328 |
Mr = 324.68 | Dx = 1.572 Mg m−3 |
Monoclinic, C2/c | Melting point = 397 K–399 K K |
Hall symbol: -C 2yc | Cu Kα radiation, λ = 1.54178 Å |
a = 20.094 (3) Å | Cell parameters from 44 reflections |
b = 9.4907 (14) Å | θ = 14.8–30.3° |
c = 15.0418 (17) Å | µ = 2.78 mm−1 |
β = 106.953 (12)° | T = 293 K |
V = 2743.9 (7) Å3 | Prism, yellow |
Z = 8 | 0.60 × 0.30 × 0.28 mm |
Data collection top
Kuma KM-4 diffractometer | 2316 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 70.1°, θmin = 4.6° |
ω–2θ scans | h = −23→23 |
Absorption correction: ψ scan (North et al., 1968) | k = −11→11 |
Tmin = 0.203, Tmax = 0.459 | l = 0→18 |
5181 measured reflections | 2 standard reflections every 100 reflections |
2615 independent reflections | intensity decay: <2% |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0681P)2 + 0.8575P] where P = (Fo2 + 2Fc2)/3 |
2615 reflections | (Δ/σ)max = 0.001 |
200 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.21 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 | 0.94374 (3) | 0.53587 (7) | 0.64330 (3) | 0.0931 (2) | |
N1 | 0.64276 (7) | 0.44071 (14) | 0.14589 (9) | 0.0559 (3) | |
C2 | 0.59627 (9) | 0.33533 (18) | 0.14111 (12) | 0.0603 (4) | |
N3 | 0.55914 (7) | 0.30914 (16) | 0.05479 (10) | 0.0630 (3) | |
C4 | 0.58307 (8) | 0.39949 (18) | 0.00294 (11) | 0.0577 (4) | |
C5 | 0.63506 (8) | 0.48195 (17) | 0.05603 (11) | 0.0565 (4) | |
C6 | 0.68749 (8) | 0.49844 (18) | 0.23221 (11) | 0.0599 (4) | |
H6A | 0.6655 | 0.4853 | 0.2811 | 0.072* | |
H6B | 0.6930 | 0.5989 | 0.2247 | 0.072* | |
C7 | 0.75868 (8) | 0.42901 (16) | 0.26088 (11) | 0.0561 (4) | |
O8 | 0.77411 (7) | 0.34448 (14) | 0.20995 (9) | 0.0741 (4) | |
C9 | 0.80532 (8) | 0.46508 (16) | 0.35368 (11) | 0.0554 (4) | |
C10 | 0.78442 (9) | 0.55381 (18) | 0.41450 (12) | 0.0605 (4) | |
H10 | 0.7415 | 0.5986 | 0.3948 | 0.073* | |
C11 | 0.82703 (9) | 0.5755 (2) | 0.50357 (12) | 0.0660 (4) | |
H11 | 0.8131 | 0.6343 | 0.5443 | 0.079* | |
C12 | 0.89069 (10) | 0.50852 (19) | 0.53119 (12) | 0.0661 (4) | |
C13 | 0.91334 (9) | 0.4222 (2) | 0.47239 (14) | 0.0698 (5) | |
H13 | 0.9567 | 0.3788 | 0.4923 | 0.084* | |
C14 | 0.87061 (9) | 0.40142 (19) | 0.38360 (13) | 0.0648 (4) | |
H14 | 0.8855 | 0.3441 | 0.3430 | 0.078* | |
C15 | 0.58922 (13) | 0.2586 (3) | 0.22370 (15) | 0.0851 (6) | |
H15A | 0.5572 | 0.1819 | 0.2040 | 0.128* | |
H15B | 0.5721 | 0.3217 | 0.2619 | 0.128* | |
H15C | 0.6338 | 0.2226 | 0.2587 | 0.128* | |
N16 | 0.55417 (8) | 0.39464 (18) | −0.09698 (10) | 0.0701 (4) | |
O17 | 0.49124 (8) | 0.3855 (2) | −0.12742 (11) | 0.1021 (6) | |
O18 | 0.59485 (9) | 0.3921 (2) | −0.14309 (10) | 0.0983 (5) | |
N19 | 0.67354 (8) | 0.59358 (16) | 0.03119 (11) | 0.0680 (4) | |
O20 | 0.65071 (10) | 0.64037 (17) | −0.04737 (12) | 0.0972 (5) | |
O21 | 0.72564 (8) | 0.63469 (16) | 0.08906 (12) | 0.0891 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0902 (4) | 0.1076 (4) | 0.0618 (3) | −0.0054 (3) | −0.0086 (2) | 0.0119 (2) |
N1 | 0.0518 (7) | 0.0598 (7) | 0.0541 (7) | −0.0011 (5) | 0.0124 (5) | −0.0053 (5) |
C2 | 0.0596 (8) | 0.0638 (9) | 0.0584 (9) | −0.0055 (7) | 0.0184 (7) | −0.0040 (7) |
N3 | 0.0583 (7) | 0.0700 (8) | 0.0604 (8) | −0.0094 (6) | 0.0169 (6) | −0.0072 (6) |
C4 | 0.0535 (8) | 0.0641 (9) | 0.0541 (8) | 0.0005 (6) | 0.0137 (6) | −0.0039 (7) |
C5 | 0.0558 (8) | 0.0569 (8) | 0.0573 (8) | 0.0007 (6) | 0.0176 (7) | −0.0013 (6) |
C6 | 0.0540 (8) | 0.0650 (9) | 0.0572 (8) | 0.0004 (7) | 0.0106 (7) | −0.0112 (7) |
C7 | 0.0547 (8) | 0.0539 (8) | 0.0594 (8) | −0.0013 (6) | 0.0162 (7) | −0.0008 (7) |
O8 | 0.0697 (7) | 0.0766 (8) | 0.0720 (7) | 0.0123 (6) | 0.0144 (6) | −0.0173 (6) |
C9 | 0.0518 (8) | 0.0540 (8) | 0.0581 (8) | −0.0022 (6) | 0.0126 (6) | 0.0030 (6) |
C10 | 0.0554 (8) | 0.0656 (9) | 0.0572 (8) | 0.0006 (7) | 0.0111 (7) | 0.0001 (7) |
C11 | 0.0659 (10) | 0.0717 (10) | 0.0572 (9) | −0.0045 (8) | 0.0130 (7) | −0.0012 (8) |
C12 | 0.0637 (9) | 0.0683 (9) | 0.0580 (9) | −0.0097 (8) | 0.0045 (7) | 0.0128 (8) |
C13 | 0.0548 (9) | 0.0668 (10) | 0.0787 (12) | 0.0020 (7) | 0.0051 (8) | 0.0119 (9) |
C14 | 0.0555 (9) | 0.0629 (9) | 0.0729 (10) | 0.0012 (7) | 0.0141 (8) | 0.0002 (8) |
C15 | 0.0988 (14) | 0.0926 (14) | 0.0670 (11) | −0.0203 (12) | 0.0288 (10) | 0.0027 (10) |
N16 | 0.0700 (9) | 0.0788 (9) | 0.0569 (8) | 0.0009 (7) | 0.0112 (7) | −0.0039 (7) |
O17 | 0.0706 (9) | 0.1477 (16) | 0.0735 (9) | 0.0151 (9) | −0.0017 (7) | −0.0161 (9) |
O18 | 0.0978 (11) | 0.1401 (14) | 0.0626 (8) | −0.0269 (10) | 0.0324 (8) | −0.0060 (8) |
N19 | 0.0742 (9) | 0.0601 (8) | 0.0742 (9) | −0.0054 (7) | 0.0286 (8) | −0.0047 (7) |
O20 | 0.1273 (13) | 0.0823 (10) | 0.0847 (10) | −0.0141 (9) | 0.0351 (9) | 0.0163 (8) |
O21 | 0.0808 (9) | 0.0830 (9) | 0.1053 (11) | −0.0259 (7) | 0.0298 (8) | −0.0116 (8) |
Geometric parameters (Å, º) top
Cl—C12 | 1.7319 (18) | C9—C10 | 1.395 (2) |
N1—C2 | 1.356 (2) | C10—C11 | 1.379 (2) |
N1—C5 | 1.372 (2) | C10—H10 | 0.9300 |
N1—C6 | 1.454 (2) | C11—C12 | 1.380 (3) |
C2—N3 | 1.319 (2) | C11—H11 | 0.9300 |
C2—C15 | 1.482 (3) | C12—C13 | 1.377 (3) |
N3—C4 | 1.339 (2) | C13—C14 | 1.375 (3) |
C4—C5 | 1.362 (2) | C13—H13 | 0.9300 |
C4—N16 | 1.445 (2) | C14—H14 | 0.9300 |
C5—N19 | 1.424 (2) | C15—H15A | 0.9600 |
C6—C7 | 1.519 (2) | C15—H15B | 0.9600 |
C6—H6A | 0.9700 | C15—H15C | 0.9600 |
C6—H6B | 0.9700 | N16—O17 | 1.216 (2) |
C7—O8 | 1.210 (2) | N16—O18 | 1.217 (2) |
C7—C9 | 1.477 (2) | N19—O21 | 1.214 (2) |
C9—C14 | 1.394 (2) | N19—O20 | 1.220 (2) |
| | | |
C2—N1—C5 | 106.26 (13) | C11—C10—H10 | 119.8 |
C2—N1—C6 | 124.22 (14) | C9—C10—H10 | 119.8 |
C5—N1—C6 | 129.44 (14) | C10—C11—C12 | 118.82 (17) |
N3—C2—N1 | 112.00 (15) | C10—C11—H11 | 120.6 |
N3—C2—C15 | 124.59 (16) | C12—C11—H11 | 120.6 |
N1—C2—C15 | 123.40 (16) | C13—C12—C11 | 122.15 (16) |
C2—N3—C4 | 104.86 (14) | C13—C12—Cl | 119.32 (14) |
N3—C4—C5 | 111.76 (15) | C11—C12—Cl | 118.53 (15) |
N3—C4—N16 | 118.78 (14) | C14—C13—C12 | 118.65 (16) |
C5—C4—N16 | 129.42 (16) | C14—C13—H13 | 120.7 |
C4—C5—N1 | 105.12 (14) | C12—C13—H13 | 120.7 |
C4—C5—N19 | 130.98 (16) | C13—C14—C9 | 120.90 (18) |
N1—C5—N19 | 123.83 (15) | C13—C14—H14 | 119.5 |
N1—C6—C7 | 112.08 (13) | C9—C14—H14 | 119.5 |
N1—C6—H6A | 109.2 | C2—C15—H15A | 109.5 |
C7—C6—H6A | 109.2 | C2—C15—H15B | 109.5 |
N1—C6—H6B | 109.2 | H15A—C15—H15B | 109.5 |
C7—C6—H6B | 109.2 | C2—C15—H15C | 109.5 |
H6A—C6—H6B | 107.9 | H15A—C15—H15C | 109.5 |
O8—C7—C9 | 122.87 (15) | H15B—C15—H15C | 109.5 |
O8—C7—C6 | 120.12 (15) | O17—N16—O18 | 125.57 (17) |
C9—C7—C6 | 116.96 (14) | O17—N16—C4 | 116.89 (16) |
C14—C9—C10 | 118.99 (16) | O18—N16—C4 | 117.40 (15) |
C14—C9—C7 | 118.86 (15) | O21—N19—O20 | 125.42 (17) |
C10—C9—C7 | 122.03 (14) | O21—N19—C5 | 118.13 (16) |
C11—C10—C9 | 120.46 (16) | O20—N19—C5 | 116.45 (16) |
| | | |
C5—N1—C2—N3 | −1.07 (19) | C6—C7—C9—C14 | 178.65 (15) |
C6—N1—C2—N3 | 175.82 (14) | O8—C7—C9—C10 | −174.56 (16) |
C5—N1—C2—C15 | 178.30 (18) | C6—C7—C9—C10 | 2.8 (2) |
C6—N1—C2—C15 | −4.8 (3) | C14—C9—C10—C11 | −1.5 (2) |
N1—C2—N3—C4 | 0.58 (19) | C7—C9—C10—C11 | 174.34 (15) |
C15—C2—N3—C4 | −178.78 (19) | C9—C10—C11—C12 | 0.3 (3) |
C2—N3—C4—C5 | 0.15 (19) | C10—C11—C12—C13 | 0.8 (3) |
C2—N3—C4—N16 | 178.02 (15) | C10—C11—C12—Cl | −179.76 (13) |
N3—C4—C5—N1 | −0.78 (19) | C11—C12—C13—C14 | −0.6 (3) |
N16—C4—C5—N1 | −178.37 (16) | Cl—C12—C13—C14 | 179.95 (14) |
N3—C4—C5—N19 | −177.76 (16) | C12—C13—C14—C9 | −0.7 (3) |
N16—C4—C5—N19 | 4.7 (3) | C10—C9—C14—C13 | 1.7 (3) |
C2—N1—C5—C4 | 1.08 (18) | C7—C9—C14—C13 | −174.28 (16) |
C6—N1—C5—C4 | −175.60 (15) | N3—C4—N16—O17 | 44.8 (2) |
C2—N1—C5—N19 | 178.33 (15) | C5—C4—N16—O17 | −137.8 (2) |
C6—N1—C5—N19 | 1.7 (3) | N3—C4—N16—O18 | −131.22 (19) |
C2—N1—C6—C7 | 94.56 (18) | C5—C4—N16—O18 | 46.2 (3) |
C5—N1—C6—C7 | −89.3 (2) | C4—C5—N19—O21 | −167.24 (18) |
N1—C6—C7—O8 | 5.5 (2) | N1—C5—N19—O21 | 16.3 (2) |
N1—C6—C7—C9 | −171.95 (13) | C4—C5—N19—O20 | 13.0 (3) |
O8—C7—C9—C14 | 1.3 (2) | N1—C5—N19—O20 | −163.44 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···O21 | 0.97 | 2.34 | 2.803 (2) | 108 |
C6—H6B···O8i | 0.97 | 2.54 | 3.427 (2) | 152 |
C6—H6A···O18ii | 0.97 | 2.37 | 3.178 (2) | 140 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x, −y+1, z+1/2. |