Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043917/gg2041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043917/gg2041Isup2.hkl |
CCDC reference: 663755
4 g of 2,4-dinitrophenyl-hydrazine and 10.6 ml of acetophenone were gently heated for 10 min resulting in a red precipitate of the anti-isomer. After removal of the anti-isomer by vacuum filtration, and standing the residual solution in a refigerator for several days we obtained very thin plates of yellow crystals of the syn-isomer (m.p. 147°C.) These crystals are stable in air at room temperature, and a sample actually 42 years old, prepared in 1964, was used for the single-crystal XRD.
All hydrogen atoms were located in the final difference map without any difficulty. The positions of the methyl hydrogen atoms were refined independently and the aromatic C—H were constrained with a bond length of 0.95 Å and N—H constrained with 0.88 Å.
The structure of the anti-isomer of acetophenone-(2,4-dinitrophenyl)hydrazone has been previously reported by Shan et al. (2002). We have been aware of the existence of the syn-isomer since 1963 (Ramsay, 1963), with the molecular structure (I) as shown in Fig. 1. This syn-isomer is more difficult to prepare experimentally, and was first characterized by Khromov-Borisov (1955). Attempts to recrystallize the syn isomer at room temperature lead to conversion to the anti-isomer. We prepared our sample following the method of Khromov-Borisov. The crystals used for the analysis were extemely thin plates, obtained by slow growth in a refrigerator. These gave less diffraction data than optimal, but sufficient to establish the correctness of the molecular and crystal structure.
The molecule has a non-planar structure as expected, in contrast to the planar structure of the anti-isomer. There are no unusual bond lengths or angles, and comparison of the C—N—N=C region to the anti-isomer shows no significant differences, indicating the same level of delocalization with C9—N2 1.348 (4) Å (anti, 1.351 (3) Å), N2—N1 1.383 (4) Å (anti, 1.367 (3) Å) and N1=C7 1.282 (4) Å, (anti 1.286 (3) Å). The intra-molecular hydrogen bond length N2···O31 of 2.617 (4) Å is similar to that of the anti-isomer, 2.607 (3) Å.
The packing of the molecules (Fig. 2) shows stacking of the planar dinitrophenyl fragments along the short b axis.
For related literature, see: Khromov-Borisov (1955); Lomer et al. (1963); Rabinovich & Kraut (1964); Ramsay (1963); Shan et al. (2002).
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C14H12N4O4 | F(000) = 624 |
Mr = 300.28 | Dx = 1.439 Mg m−3 |
Monoclinic, P21/c | Melting point: 420 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3339 (5) Å | Cell parameters from 35234 reflections |
b = 6.4906 (3) Å | θ = 1.0–20.4° |
c = 25.6571 (15) Å | µ = 0.11 mm−1 |
β = 92.804 (2)° | T = 180 K |
V = 1386.18 (13) Å3 | Thin plate, yellow |
Z = 4 | 0.35 × 0.23 × 0.01 mm |
Nonius KappaCCD diffractometer | 1055 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.066 |
Thin slice ω and φ scans | θmax = 20.4°, θmin = 3.5° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −8→8 |
Tmin = 0.70, Tmax = 1.00 | k = −6→6 |
4331 measured reflections | l = −24→25 |
1346 independent reflections |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0434P)2 + 0.862P] where P = (Fo2 + 2Fc2)/3 |
1346 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C14H12N4O4 | V = 1386.18 (13) Å3 |
Mr = 300.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3339 (5) Å | µ = 0.11 mm−1 |
b = 6.4906 (3) Å | T = 180 K |
c = 25.6571 (15) Å | 0.35 × 0.23 × 0.01 mm |
β = 92.804 (2)° |
Nonius KappaCCD diffractometer | 1346 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1055 reflections with I > 2σ(I) |
Tmin = 0.70, Tmax = 1.00 | Rint = 0.066 |
4331 measured reflections | θmax = 20.4° |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.15 e Å−3 |
1346 reflections | Δρmin = −0.20 e Å−3 |
200 parameters |
Experimental. Small thin crystal, poor data (theta max 20 degrees). |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1144 (3) | 0.2778 (4) | 0.37811 (12) | 0.0364 (8) | |
C1 | 0.3611 (4) | 0.2247 (6) | 0.33049 (13) | 0.0368 (10) | |
N2 | 0.2113 (3) | 0.2447 (4) | 0.42264 (11) | 0.0357 (8) | |
H2N | 0.3147 | 0.2229 | 0.4199 | 0.043* | |
C2 | 0.4779 (4) | 0.3655 (7) | 0.34654 (14) | 0.0466 (11) | |
H2 | 0.4475 | 0.4952 | 0.3601 | 0.056* | |
C3 | 0.6392 (5) | 0.3179 (7) | 0.34289 (16) | 0.0558 (12) | |
H3 | 0.7191 | 0.4150 | 0.3539 | 0.067* | |
N3 | 0.4217 (3) | 0.2396 (5) | 0.51692 (14) | 0.0451 (9) | |
O31 | 0.4881 (3) | 0.2325 (5) | 0.47533 (11) | 0.0591 (9) | |
O32 | 0.4969 (3) | 0.2462 (5) | 0.55887 (12) | 0.0731 (10) | |
N4 | −0.0500 (4) | 0.2448 (5) | 0.61941 (12) | 0.0409 (8) | |
O41 | −0.1970 (3) | 0.2486 (4) | 0.62148 (9) | 0.0503 (8) | |
O42 | 0.0416 (3) | 0.2419 (4) | 0.65840 (10) | 0.0580 (8) | |
C4 | 0.6831 (5) | 0.1320 (8) | 0.32354 (18) | 0.0621 (13) | |
H4 | 0.7937 | 0.0991 | 0.3217 | 0.075* | |
C5 | 0.5681 (6) | −0.0085 (7) | 0.30668 (17) | 0.0664 (14) | |
H5 | 0.5995 | −0.1376 | 0.2930 | 0.080* | |
C6 | 0.4060 (5) | 0.0388 (6) | 0.30970 (15) | 0.0512 (12) | |
H6 | 0.3265 | −0.0568 | 0.2975 | 0.061* | |
C7 | 0.1861 (4) | 0.2723 (6) | 0.33503 (14) | 0.0390 (10) | |
C8 | 0.0899 (5) | 0.3143 (7) | 0.28589 (15) | 0.0590 (13) | |
H8A | −0.0211 | 0.3457 | 0.2940 | 0.089* | |
H8B | 0.0914 | 0.1928 | 0.2632 | 0.089* | |
H8C | 0.1360 | 0.4322 | 0.2680 | 0.089* | |
C9 | 0.1495 (4) | 0.2455 (5) | 0.47021 (13) | 0.0290 (9) | |
C10 | −0.0200 (4) | 0.2529 (5) | 0.47562 (14) | 0.0297 (9) | |
H10 | −0.0896 | 0.2593 | 0.4452 | 0.036* | |
C11 | −0.0838 (4) | 0.2511 (5) | 0.52317 (13) | 0.0291 (9) | |
H11 | −0.1970 | 0.2540 | 0.5259 | 0.035* | |
C12 | 0.0166 (4) | 0.2451 (5) | 0.56803 (13) | 0.0310 (9) | |
C13 | 0.1813 (4) | 0.2380 (5) | 0.56530 (14) | 0.0342 (10) | |
H13 | 0.2488 | 0.2322 | 0.5962 | 0.041* | |
C14 | 0.2463 (4) | 0.2395 (5) | 0.51691 (14) | 0.0298 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0337 (17) | 0.045 (2) | 0.030 (2) | −0.0033 (15) | 0.0000 (17) | 0.0008 (15) |
C1 | 0.034 (2) | 0.047 (3) | 0.029 (2) | −0.002 (2) | 0.0081 (18) | −0.002 (2) |
N2 | 0.0244 (15) | 0.048 (2) | 0.034 (2) | 0.0039 (15) | −0.0025 (15) | −0.0005 (16) |
C2 | 0.037 (2) | 0.051 (3) | 0.053 (3) | 0.000 (2) | 0.0086 (19) | −0.014 (2) |
C3 | 0.038 (3) | 0.066 (3) | 0.064 (3) | −0.006 (2) | 0.007 (2) | −0.011 (2) |
N3 | 0.032 (2) | 0.059 (2) | 0.044 (2) | 0.0022 (17) | −0.004 (2) | −0.0035 (18) |
O31 | 0.0313 (15) | 0.097 (2) | 0.0492 (19) | 0.0026 (15) | 0.0081 (14) | 0.0034 (17) |
O32 | 0.0339 (16) | 0.133 (3) | 0.051 (2) | 0.0041 (17) | −0.0101 (15) | −0.0187 (19) |
N4 | 0.043 (2) | 0.040 (2) | 0.040 (2) | 0.0040 (16) | 0.0015 (19) | 0.0015 (17) |
O41 | 0.0384 (18) | 0.065 (2) | 0.0486 (18) | −0.0044 (14) | 0.0117 (13) | 0.0014 (14) |
O42 | 0.0544 (17) | 0.087 (2) | 0.0320 (17) | 0.0142 (17) | −0.0024 (14) | −0.0018 (16) |
C4 | 0.045 (3) | 0.068 (3) | 0.075 (3) | 0.007 (3) | 0.023 (2) | 0.010 (3) |
C5 | 0.073 (3) | 0.049 (3) | 0.080 (4) | 0.007 (3) | 0.039 (3) | −0.001 (2) |
C6 | 0.052 (3) | 0.049 (3) | 0.054 (3) | −0.008 (2) | 0.021 (2) | −0.007 (2) |
C7 | 0.040 (2) | 0.044 (2) | 0.032 (2) | −0.0089 (19) | 0.001 (2) | −0.0011 (18) |
C8 | 0.045 (2) | 0.094 (4) | 0.038 (3) | −0.007 (2) | 0.002 (2) | 0.001 (2) |
C9 | 0.032 (2) | 0.024 (2) | 0.031 (2) | −0.0013 (16) | 0.0066 (18) | −0.0038 (17) |
C10 | 0.022 (2) | 0.033 (2) | 0.034 (2) | 0.0023 (16) | −0.0029 (16) | 0.0006 (17) |
C11 | 0.0245 (19) | 0.025 (2) | 0.038 (2) | 0.0008 (16) | −0.0005 (19) | −0.0045 (17) |
C12 | 0.031 (2) | 0.034 (2) | 0.029 (2) | 0.0009 (17) | 0.0049 (18) | −0.0007 (17) |
C13 | 0.035 (3) | 0.033 (2) | 0.034 (2) | 0.0020 (17) | −0.0081 (18) | −0.0036 (17) |
C14 | 0.022 (2) | 0.031 (2) | 0.036 (2) | 0.0020 (16) | 0.0002 (18) | −0.0046 (17) |
N1—N2 | 1.383 (4) | C4—H4 | 0.9500 |
N1—C7 | 1.282 (4) | C5—C6 | 1.391 (6) |
C1—C2 | 1.383 (5) | C5—H5 | 0.9500 |
C1—C6 | 1.378 (5) | C6—H6 | 0.9500 |
C1—C7 | 1.501 (5) | C7—C8 | 1.486 (5) |
N2—C9 | 1.348 (4) | C8—H8A | 0.9800 |
N2—H2N | 0.8800 | C8—H8B | 0.9800 |
C2—C3 | 1.387 (5) | C8—H8C | 0.9800 |
C2—H2 | 0.9500 | C9—C14 | 1.412 (5) |
C3—C4 | 1.361 (6) | C9—C10 | 1.427 (5) |
C3—H3 | 0.9500 | C10—C11 | 1.354 (4) |
N3—O31 | 1.227 (4) | C10—H10 | 0.9500 |
N3—O32 | 1.219 (4) | C11—C12 | 1.390 (5) |
N3—C14 | 1.462 (4) | C11—H11 | 0.9500 |
N4—O41 | 1.230 (4) | C12—C13 | 1.379 (4) |
N4—O42 | 1.228 (4) | C13—C14 | 1.378 (5) |
N4—C12 | 1.455 (4) | C13—H13 | 0.9500 |
C4—C5 | 1.377 (6) | ||
C7—N1—N2 | 115.4 (3) | N1—C7—C8 | 118.1 (3) |
C6—C1—C2 | 119.5 (3) | N1—C7—C1 | 124.6 (3) |
C6—C1—C7 | 119.6 (3) | C8—C7—C1 | 117.3 (3) |
C2—C1—C7 | 120.9 (3) | C7—C8—H8A | 109.5 |
C9—N2—N1 | 120.9 (3) | C7—C8—H8B | 109.5 |
C9—N2—H2N | 119.5 | H8A—C8—H8B | 109.5 |
N1—N2—H2N | 119.5 | C7—C8—H8C | 109.5 |
C1—C2—C3 | 120.2 (4) | H8A—C8—H8C | 109.5 |
C1—C2—H2 | 119.9 | H8B—C8—H8C | 109.5 |
C3—C2—H2 | 119.9 | N2—C9—C14 | 122.7 (3) |
C4—C3—C2 | 120.1 (4) | N2—C9—C10 | 120.8 (3) |
C4—C3—H3 | 120.0 | C14—C9—C10 | 116.5 (3) |
C2—C3—H3 | 120.0 | C11—C10—C9 | 121.4 (3) |
O32—N3—O31 | 122.3 (3) | C11—C10—H10 | 119.3 |
O32—N3—C14 | 118.1 (3) | C9—C10—H10 | 119.3 |
O31—N3—C14 | 119.6 (3) | C10—C11—C12 | 120.0 (3) |
O42—N4—O41 | 123.1 (3) | C10—C11—H11 | 120.0 |
O42—N4—C12 | 119.3 (3) | C12—C11—H11 | 120.0 |
O41—N4—C12 | 117.7 (3) | C13—C12—C11 | 121.3 (3) |
C3—C4—C5 | 120.4 (4) | C13—C12—N4 | 118.1 (3) |
C3—C4—H4 | 119.8 | C11—C12—N4 | 120.7 (3) |
C5—C4—H4 | 119.8 | C14—C13—C12 | 118.8 (3) |
C4—C5—C6 | 119.9 (4) | C14—C13—H13 | 120.6 |
C4—C5—H5 | 120.0 | C12—C13—H13 | 120.6 |
C6—C5—H5 | 120.0 | C13—C14—C9 | 122.1 (3) |
C1—C6—C5 | 119.8 (4) | C13—C14—N3 | 115.9 (3) |
C1—C6—H6 | 120.1 | C9—C14—N3 | 122.0 (3) |
C5—C6—H6 | 120.1 | ||
C7—N1—N2—C9 | −179.6 (3) | C9—C10—C11—C12 | 1.0 (5) |
C6—C1—C2—C3 | −1.5 (6) | C10—C11—C12—C13 | −0.9 (5) |
C7—C1—C2—C3 | 178.9 (4) | C10—C11—C12—N4 | 179.5 (3) |
C1—C2—C3—C4 | −0.1 (6) | O42—N4—C12—C13 | 1.2 (5) |
C2—C3—C4—C5 | 1.1 (7) | O41—N4—C12—C13 | −179.1 (3) |
C3—C4—C5—C6 | −0.4 (7) | O42—N4—C12—C11 | −179.1 (3) |
C2—C1—C6—C5 | 2.2 (6) | O41—N4—C12—C11 | 0.5 (5) |
C7—C1—C6—C5 | −178.3 (3) | C11—C12—C13—C14 | 0.8 (5) |
C4—C5—C6—C1 | −1.2 (6) | N4—C12—C13—C14 | −179.6 (3) |
N2—N1—C7—C8 | −177.8 (3) | C12—C13—C14—C9 | −0.8 (5) |
N2—N1—C7—C1 | 2.7 (5) | C12—C13—C14—N3 | 177.8 (3) |
C6—C1—C7—N1 | 108.2 (4) | N2—C9—C14—C13 | −179.2 (3) |
C2—C1—C7—N1 | −72.2 (5) | C10—C9—C14—C13 | 0.8 (5) |
C6—C1—C7—C8 | −71.3 (5) | N2—C9—C14—N3 | 2.3 (5) |
C2—C1—C7—C8 | 108.2 (4) | C10—C9—C14—N3 | −177.6 (3) |
N1—N2—C9—C14 | −171.5 (3) | O32—N3—C14—C13 | −2.7 (5) |
N1—N2—C9—C10 | 8.4 (5) | O31—N3—C14—C13 | 177.1 (3) |
N2—C9—C10—C11 | 179.1 (3) | O32—N3—C14—C9 | 175.9 (4) |
C14—C9—C10—C11 | −1.0 (5) | O31—N3—C14—C9 | −4.4 (5) |
Experimental details
Crystal data | |
Chemical formula | C14H12N4O4 |
Mr | 300.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 180 |
a, b, c (Å) | 8.3339 (5), 6.4906 (3), 25.6571 (15) |
β (°) | 92.804 (2) |
V (Å3) | 1386.18 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.35 × 0.23 × 0.01 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.70, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4331, 1346, 1055 |
Rint | 0.066 |
θmax (°) | 20.4 |
(sin θ/λ)max (Å−1) | 0.490 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.128, 1.15 |
No. of reflections | 1346 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.20 |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).
The structure of the anti-isomer of acetophenone-(2,4-dinitrophenyl)hydrazone has been previously reported by Shan et al. (2002). We have been aware of the existence of the syn-isomer since 1963 (Ramsay, 1963), with the molecular structure (I) as shown in Fig. 1. This syn-isomer is more difficult to prepare experimentally, and was first characterized by Khromov-Borisov (1955). Attempts to recrystallize the syn isomer at room temperature lead to conversion to the anti-isomer. We prepared our sample following the method of Khromov-Borisov. The crystals used for the analysis were extemely thin plates, obtained by slow growth in a refrigerator. These gave less diffraction data than optimal, but sufficient to establish the correctness of the molecular and crystal structure.
The molecule has a non-planar structure as expected, in contrast to the planar structure of the anti-isomer. There are no unusual bond lengths or angles, and comparison of the C—N—N=C region to the anti-isomer shows no significant differences, indicating the same level of delocalization with C9—N2 1.348 (4) Å (anti, 1.351 (3) Å), N2—N1 1.383 (4) Å (anti, 1.367 (3) Å) and N1=C7 1.282 (4) Å, (anti 1.286 (3) Å). The intra-molecular hydrogen bond length N2···O31 of 2.617 (4) Å is similar to that of the anti-isomer, 2.607 (3) Å.
The packing of the molecules (Fig. 2) shows stacking of the planar dinitrophenyl fragments along the short b axis.