Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046831/at2406sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046831/at2406Isup2.hkl |
CCDC reference: 667260
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.002 Å
- R factor = 0.046
- wR factor = 0.135
- Data-to-parameter ratio = 12.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general background, see Elliot & Smith (2000); Espinoza & Thornton (1994); Farrell et al. (1985); Chattanathan & Kalidas (1971); Southgate & Hall (1971); Stewart & O'Donnell (1964). For reference bond-length data, see: Allen et al. (1987).
2,4-Dinitroaniline (0.183 g, 1 mmol) was added to a solution of 1-chloro-2,4-dinitrobenzene (0.202 g, 1 mmol) in DMF (2 ml). The resulting solution was applied to a column of basic alumina (5 g) with DMF (20 ml) as eluent. The dark red eluent was concentrated and dissolved in acetone (15 ml). Crude product was obtained by the addition of water (20 ml). Recrystallization from glacial acetic acid (8 ml) furnished the title compound (I) as yellow needles (2.41 g), in yield of 67.5%. Single crystals of (I) were obtained by slow evaporation from a petroleum ether–ethyl acetate (2:1 v/v) solution system.
The H atoms were geometrically placed and were treated as riding, with C—H = 0.93 Å, N—H = 0.87 Å, and with Uiso(H) = 1.2Ueq(C) or 1.6Ueq(N).
The title compound, (I), is a derivative of nitrodiphenylamines which were used in nonlinear optical materials (Southgate & Hall, 1971). They were known as stabilizers incorporated into propellant formulations and smokeless gunpowder (Elliot & Smith, 2000; Espinoza & Thornton, 1994). And they were acted as indicators to study the H acidity function in ethylene and propylene glycols (Chattanathan & Kalidas, 1971). Their structure–acidity correlation test indicated that the effect of substituents on the acidity of diphenylamines (Stewart & O'Donnell 1964). Simultaneously, the study on the effects of solvation upon the acidities of nitroaromatics shows that the nitrobenzyl anions are suggested to be essentially charge-delocalized (Farrell et al., 1985).
The bond lengths and angles in (I) (Table 1) are in good agree with expected values (Allen et al., 1987). The dihedral angle between the two benzene rings is 56.3 (2)°. The packing is stabilized by intramolecular N—H···O and intermolecular C—H···O interactions in the crystal structure (Table 2).
For general background, see Elliot & Smith (2000); Espinoza & Thornton (1994); Farrell et al. (1985); Chattanathan & Kalidas (1971); Southgate & Hall (1971); Stewart & O'Donnell (1964). For reference bond-length data, see: Allen et al. (1987).
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000) and PLATON (Spek, 2003).
Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. |
C12H7N5O8 | F(000) = 712 |
Mr = 349.23 | Dx = 1.657 Mg m−3 |
Monoclinic, P21/n | Melting point: 472.2 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4987 (9) Å | Cell parameters from 4779 reflections |
b = 14.7982 (15) Å | θ = 2.3–28.1° |
c = 11.1828 (12) Å | µ = 0.14 mm−1 |
β = 95.395 (1)° | T = 291 K |
V = 1400.2 (3) Å3 | Block, orange |
Z = 4 | 0.36 × 0.32 × 0.28 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2745 independent reflections |
Radiation source: sealed tube | 2384 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.085 |
φ and ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→10 |
Tmin = 0.953, Tmax = 0.964 | k = −18→18 |
7449 measured reflections | l = −5→13 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0813P)2 + 0.2007P] where P = (Fo2 + 2Fc2)/3 |
2745 reflections | (Δ/σ)max < 0.001 |
227 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C12H7N5O8 | V = 1400.2 (3) Å3 |
Mr = 349.23 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.4987 (9) Å | µ = 0.14 mm−1 |
b = 14.7982 (15) Å | T = 291 K |
c = 11.1828 (12) Å | 0.36 × 0.32 × 0.28 mm |
β = 95.395 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 2745 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2384 reflections with I > 2σ(I) |
Tmin = 0.953, Tmax = 0.964 | Rint = 0.085 |
7449 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.19 e Å−3 |
2745 reflections | Δρmin = −0.36 e Å−3 |
227 parameters |
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 | ||
C1 | 0.24828 (18) | 0.90522 (9) | 0.39789 (12) | 0.0352 (3) | |
C2 | 0.18191 (17) | 0.85746 (9) | 0.48995 (12) | 0.0345 (3) | |
C3 | 0.27475 (19) | 0.81680 (9) | 0.58238 (12) | 0.0383 (3) | |
H3 | 0.2293 | 0.7842 | 0.6414 | 0.046* | |
C4 | 0.43599 (19) | 0.82557 (9) | 0.58523 (13) | 0.0397 (3) | |
C5 | 0.5073 (2) | 0.87074 (10) | 0.49629 (14) | 0.0427 (4) | |
H5 | 0.6167 | 0.8750 | 0.4992 | 0.051* | |
C6 | 0.4129 (2) | 0.90907 (10) | 0.40393 (14) | 0.0417 (4) | |
H6 | 0.4602 | 0.9387 | 0.3432 | 0.050* | |
C7 | 0.19498 (17) | 0.96538 (9) | 0.19386 (12) | 0.0355 (3) | |
C8 | 0.14268 (17) | 1.04179 (9) | 0.12616 (12) | 0.0351 (3) | |
C9 | 0.18928 (18) | 1.05794 (10) | 0.01239 (13) | 0.0385 (3) | |
H9 | 0.1571 | 1.1100 | −0.0297 | 0.046* | |
C10 | 0.28348 (18) | 0.99575 (10) | −0.03651 (12) | 0.0390 (3) | |
C11 | 0.3306 (2) | 0.91681 (11) | 0.02370 (14) | 0.0424 (4) | |
H11 | 0.3903 | 0.8739 | −0.0127 | 0.051* | |
C12 | 0.2881 (2) | 0.90291 (10) | 0.13758 (14) | 0.0412 (4) | |
H12 | 0.3219 | 0.8507 | 0.1786 | 0.049* | |
N1 | 0.01119 (16) | 0.84928 (9) | 0.49229 (11) | 0.0415 (3) | |
N2 | 0.5346 (2) | 0.78806 (11) | 0.68694 (13) | 0.0556 (4) | |
N3 | 0.03468 (16) | 1.10760 (9) | 0.17095 (12) | 0.0426 (3) | |
N4 | 0.33458 (17) | 1.01266 (11) | −0.15575 (12) | 0.0480 (4) | |
N5 | 0.15513 (16) | 0.95046 (9) | 0.30872 (11) | 0.0412 (3) | |
H5' | 0.0696 | 0.9737 | 0.3334 | 0.066 (6)* | |
O1 | −0.07352 (14) | 0.91080 (9) | 0.45042 (11) | 0.0538 (3) | |
O2 | −0.03902 (16) | 0.78209 (9) | 0.53913 (13) | 0.0649 (4) | |
O3 | 0.4751 (2) | 0.73510 (14) | 0.75172 (17) | 0.1018 (7) | |
O4 | 0.67277 (18) | 0.81174 (12) | 0.70251 (14) | 0.0761 (5) | |
O5 | −0.04027 (15) | 1.08548 (9) | 0.25453 (11) | 0.0536 (3) | |
O6 | 0.0202 (2) | 1.18043 (9) | 0.12207 (15) | 0.0749 (5) | |
O7 | 0.2970 (2) | 1.08398 (12) | −0.20501 (13) | 0.0772 (5) | |
O8 | 0.41639 (18) | 0.95593 (10) | −0.19853 (11) | 0.0632 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0474 (8) | 0.0319 (7) | 0.0264 (6) | −0.0017 (5) | 0.0039 (6) | −0.0020 (5) |
C2 | 0.0440 (8) | 0.0324 (6) | 0.0275 (6) | −0.0054 (5) | 0.0054 (6) | −0.0050 (5) |
C3 | 0.0558 (9) | 0.0319 (7) | 0.0275 (6) | −0.0034 (6) | 0.0062 (6) | −0.0006 (5) |
C4 | 0.0515 (9) | 0.0342 (7) | 0.0324 (7) | 0.0051 (6) | −0.0013 (6) | −0.0045 (6) |
C5 | 0.0440 (8) | 0.0432 (8) | 0.0408 (8) | −0.0011 (6) | 0.0033 (6) | −0.0060 (6) |
C6 | 0.0482 (9) | 0.0434 (8) | 0.0344 (7) | −0.0064 (6) | 0.0090 (6) | 0.0019 (6) |
C7 | 0.0428 (8) | 0.0357 (7) | 0.0275 (7) | −0.0047 (6) | 0.0011 (6) | 0.0001 (5) |
C8 | 0.0390 (7) | 0.0362 (7) | 0.0294 (7) | −0.0020 (6) | −0.0001 (6) | −0.0011 (5) |
C9 | 0.0431 (8) | 0.0404 (7) | 0.0311 (7) | −0.0038 (6) | −0.0019 (6) | 0.0061 (6) |
C10 | 0.0442 (8) | 0.0475 (8) | 0.0251 (7) | −0.0087 (6) | 0.0023 (6) | −0.0011 (6) |
C11 | 0.0510 (9) | 0.0413 (7) | 0.0352 (8) | −0.0013 (6) | 0.0062 (7) | −0.0066 (6) |
C12 | 0.0547 (9) | 0.0341 (7) | 0.0347 (8) | 0.0012 (6) | 0.0039 (7) | 0.0007 (6) |
N1 | 0.0474 (7) | 0.0477 (7) | 0.0298 (6) | −0.0099 (6) | 0.0059 (5) | −0.0071 (5) |
N2 | 0.0664 (10) | 0.0524 (8) | 0.0458 (8) | 0.0117 (7) | −0.0061 (7) | 0.0016 (7) |
N3 | 0.0446 (7) | 0.0440 (7) | 0.0384 (7) | 0.0043 (5) | −0.0002 (6) | 0.0005 (6) |
N4 | 0.0500 (8) | 0.0640 (9) | 0.0299 (7) | −0.0103 (7) | 0.0035 (6) | 0.0004 (6) |
N5 | 0.0486 (7) | 0.0463 (7) | 0.0292 (6) | 0.0050 (6) | 0.0069 (5) | 0.0061 (5) |
O1 | 0.0453 (7) | 0.0685 (8) | 0.0477 (7) | 0.0023 (6) | 0.0055 (5) | −0.0006 (6) |
O2 | 0.0664 (8) | 0.0640 (8) | 0.0658 (8) | −0.0275 (7) | 0.0140 (7) | 0.0067 (7) |
O3 | 0.1026 (13) | 0.1026 (13) | 0.0942 (13) | −0.0066 (11) | −0.0224 (10) | 0.0621 (11) |
O4 | 0.0589 (9) | 0.0992 (12) | 0.0659 (9) | 0.0112 (8) | −0.0170 (7) | −0.0015 (8) |
O5 | 0.0555 (7) | 0.0629 (7) | 0.0441 (7) | 0.0117 (6) | 0.0137 (6) | −0.0005 (5) |
O6 | 0.0939 (11) | 0.0520 (8) | 0.0818 (10) | 0.0279 (7) | 0.0238 (9) | 0.0236 (7) |
O7 | 0.0902 (11) | 0.0960 (11) | 0.0474 (8) | 0.0149 (9) | 0.0177 (7) | 0.0318 (8) |
O8 | 0.0791 (9) | 0.0717 (8) | 0.0420 (7) | −0.0090 (7) | 0.0234 (6) | −0.0128 (6) |
C1—N5 | 1.386 (2) | C9—C10 | 1.367 (2) |
C1—C6 | 1.396 (2) | C9—H9 | 0.9300 |
C1—C2 | 1.4095 (19) | C10—C11 | 1.389 (2) |
C2—C3 | 1.378 (2) | C10—N4 | 1.4623 (18) |
C2—N1 | 1.459 (2) | C11—C12 | 1.372 (2) |
C3—C4 | 1.374 (2) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C12—H12 | 0.9300 |
C4—C5 | 1.384 (2) | N1—O2 | 1.2196 (18) |
C4—N2 | 1.457 (2) | N1—O1 | 1.2260 (19) |
C5—C6 | 1.369 (2) | N2—O3 | 1.210 (2) |
C5—H5 | 0.9300 | N2—O4 | 1.222 (2) |
C6—H6 | 0.9300 | N3—O6 | 1.2094 (19) |
C7—N5 | 1.3766 (18) | N3—O5 | 1.2240 (18) |
C7—C12 | 1.404 (2) | N4—O8 | 1.2163 (19) |
C7—C8 | 1.409 (2) | N4—O7 | 1.219 (2) |
C8—C9 | 1.388 (2) | N5—H5' | 0.8718 |
C8—N3 | 1.4590 (19) | ||
N5—C1—C6 | 121.15 (13) | C8—C9—H9 | 120.7 |
N5—C1—C2 | 121.81 (14) | C9—C10—C11 | 121.70 (13) |
C6—C1—C2 | 116.96 (14) | C9—C10—N4 | 119.01 (14) |
C3—C2—C1 | 121.77 (14) | C11—C10—N4 | 119.29 (14) |
C3—C2—N1 | 116.78 (12) | C12—C11—C10 | 119.16 (14) |
C1—C2—N1 | 121.45 (13) | C12—C11—H11 | 120.4 |
C4—C3—C2 | 118.40 (13) | C10—C11—H11 | 120.4 |
C4—C3—H3 | 120.8 | C11—C12—C7 | 121.76 (14) |
C2—C3—H3 | 120.8 | C11—C12—H12 | 119.1 |
C3—C4—C5 | 122.13 (14) | C7—C12—H12 | 119.1 |
C3—C4—N2 | 118.75 (14) | O2—N1—O1 | 123.57 (14) |
C5—C4—N2 | 119.11 (15) | O2—N1—C2 | 117.65 (14) |
C6—C5—C4 | 118.51 (15) | O1—N1—C2 | 118.75 (12) |
C6—C5—H5 | 120.7 | O3—N2—O4 | 123.38 (16) |
C4—C5—H5 | 120.7 | O3—N2—C4 | 118.19 (17) |
C5—C6—C1 | 122.18 (14) | O4—N2—C4 | 118.43 (16) |
C5—C6—H6 | 118.9 | O6—N3—O5 | 123.06 (15) |
C1—C6—H6 | 118.9 | O6—N3—C8 | 118.69 (14) |
N5—C7—C12 | 120.75 (13) | O5—N3—C8 | 118.23 (13) |
N5—C7—C8 | 122.49 (13) | O8—N4—O7 | 123.72 (14) |
C12—C7—C8 | 116.75 (13) | O8—N4—C10 | 118.06 (14) |
C9—C8—C7 | 121.85 (14) | O7—N4—C10 | 118.19 (15) |
C9—C8—N3 | 116.27 (13) | C7—N5—C1 | 125.08 (13) |
C7—C8—N3 | 121.87 (13) | C7—N5—H5' | 121.2 |
C10—C9—C8 | 118.61 (14) | C1—N5—H5' | 113.5 |
C10—C9—H9 | 120.7 | ||
N5—C1—C2—C3 | −176.25 (13) | C10—C11—C12—C7 | 1.6 (2) |
C6—C1—C2—C3 | 0.4 (2) | N5—C7—C12—C11 | −179.32 (15) |
N5—C1—C2—N1 | 3.3 (2) | C8—C7—C12—C11 | 2.0 (2) |
C6—C1—C2—N1 | 179.98 (12) | C3—C2—N1—O2 | −29.46 (18) |
C1—C2—C3—C4 | 1.6 (2) | C1—C2—N1—O2 | 150.96 (14) |
N1—C2—C3—C4 | −177.94 (12) | C3—C2—N1—O1 | 148.60 (14) |
C2—C3—C4—C5 | −2.5 (2) | C1—C2—N1—O1 | −30.98 (19) |
C2—C3—C4—N2 | 175.88 (13) | C3—C4—N2—O3 | 15.0 (2) |
C3—C4—C5—C6 | 1.2 (2) | C5—C4—N2—O3 | −166.57 (17) |
N2—C4—C5—C6 | −177.18 (14) | C3—C4—N2—O4 | −164.90 (16) |
C4—C5—C6—C1 | 1.0 (2) | C5—C4—N2—O4 | 13.5 (2) |
N5—C1—C6—C5 | 174.90 (14) | C9—C8—N3—O6 | −16.4 (2) |
C2—C1—C6—C5 | −1.8 (2) | C7—C8—N3—O6 | 164.47 (16) |
N5—C7—C8—C9 | 177.20 (13) | C9—C8—N3—O5 | 161.71 (14) |
C12—C7—C8—C9 | −4.2 (2) | C7—C8—N3—O5 | −17.4 (2) |
N5—C7—C8—N3 | −3.7 (2) | C9—C10—N4—O8 | −178.92 (15) |
C12—C7—C8—N3 | 174.86 (13) | C11—C10—N4—O8 | 0.6 (2) |
C7—C8—C9—C10 | 2.6 (2) | C9—C10—N4—O7 | 3.3 (2) |
N3—C8—C9—C10 | −176.46 (13) | C11—C10—N4—O7 | −177.19 (16) |
C8—C9—C10—C11 | 1.2 (2) | C12—C7—N5—C1 | 31.8 (2) |
C8—C9—C10—N4 | −179.33 (13) | C8—C7—N5—C1 | −149.61 (14) |
C9—C10—C11—C12 | −3.3 (2) | C6—C1—N5—C7 | 32.3 (2) |
N4—C10—C11—C12 | 177.26 (14) | C2—C1—N5—C7 | −151.20 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5′···O1 | 0.87 | 2.09 | 2.6853 (18) | 125 |
N5—H5′···O5 | 0.87 | 2.06 | 2.6321 (19) | 123 |
C6—H6···O8i | 0.93 | 2.54 | 3.464 (2) | 170 |
C11—H11···O2ii | 0.93 | 2.44 | 3.144 (2) | 132 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x+1/2, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H7N5O8 |
Mr | 349.23 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 291 |
a, b, c (Å) | 8.4987 (9), 14.7982 (15), 11.1828 (12) |
β (°) | 95.395 (1) |
V (Å3) | 1400.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.36 × 0.32 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.953, 0.964 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7449, 2745, 2384 |
Rint | 0.085 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.135, 1.01 |
No. of reflections | 2745 |
No. of parameters | 227 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.36 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5'···O1 | 0.87 | 2.09 | 2.6853 (18) | 125 |
N5—H5'···O5 | 0.87 | 2.06 | 2.6321 (19) | 123 |
C6—H6···O8i | 0.93 | 2.54 | 3.464 (2) | 170 |
C11—H11···O2ii | 0.93 | 2.44 | 3.144 (2) | 132 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x+1/2, −y+3/2, z−1/2. |
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The title compound, (I), is a derivative of nitrodiphenylamines which were used in nonlinear optical materials (Southgate & Hall, 1971). They were known as stabilizers incorporated into propellant formulations and smokeless gunpowder (Elliot & Smith, 2000; Espinoza & Thornton, 1994). And they were acted as indicators to study the H acidity function in ethylene and propylene glycols (Chattanathan & Kalidas, 1971). Their structure–acidity correlation test indicated that the effect of substituents on the acidity of diphenylamines (Stewart & O'Donnell 1964). Simultaneously, the study on the effects of solvation upon the acidities of nitroaromatics shows that the nitrobenzyl anions are suggested to be essentially charge-delocalized (Farrell et al., 1985).
The bond lengths and angles in (I) (Table 1) are in good agree with expected values (Allen et al., 1987). The dihedral angle between the two benzene rings is 56.3 (2)°. The packing is stabilized by intramolecular N—H···O and intermolecular C—H···O interactions in the crystal structure (Table 2).