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In the title compound, C12H7N5O8, the dihedral angle between the two benzene rings is 56.3 (2)°. The crystal packing is stabilized by intra­molecular N—H...O and inter­molecular C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046831/at2406sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046831/at2406Isup2.hkl
Contains datablock I

CCDC reference: 667260

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](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

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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).

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
Bis(2,4-Dinitrophenyl)amine top
Crystal data top
C12H7N5O8F(000) = 712
Mr = 349.23Dx = 1.657 Mg m3
Monoclinic, P21/nMelting point: 472.2 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.4987 (9) ÅCell parameters from 4779 reflections
b = 14.7982 (15) Åθ = 2.3–28.1°
c = 11.1828 (12) ŵ = 0.14 mm1
β = 95.395 (1)°T = 291 K
V = 1400.2 (3) Å3Block, orange
Z = 40.36 × 0.32 × 0.28 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2745 independent reflections
Radiation source: sealed tube2384 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
φ and ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.953, Tmax = 0.964k = 1818
7449 measured reflectionsl = 513
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-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 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C12H7N5O8V = 1400.2 (3) Å3
Mr = 349.23Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.4987 (9) ŵ = 0.14 mm1
b = 14.7982 (15) ÅT = 291 K
c = 11.1828 (12) Å0.36 × 0.32 × 0.28 mm
β = 95.395 (1)°
Data collection top
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 = 0.964Rint = 0.085
7449 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.01Δρmax = 0.19 e Å3
2745 reflectionsΔρmin = 0.36 e Å3
227 parameters
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
xyzUiso*/Ueq
C10.24828 (18)0.90522 (9)0.39789 (12)0.0352 (3)
C20.18191 (17)0.85746 (9)0.48995 (12)0.0345 (3)
C30.27475 (19)0.81680 (9)0.58238 (12)0.0383 (3)
H30.22930.78420.64140.046*
C40.43599 (19)0.82557 (9)0.58523 (13)0.0397 (3)
C50.5073 (2)0.87074 (10)0.49629 (14)0.0427 (4)
H50.61670.87500.49920.051*
C60.4129 (2)0.90907 (10)0.40393 (14)0.0417 (4)
H60.46020.93870.34320.050*
C70.19498 (17)0.96538 (9)0.19386 (12)0.0355 (3)
C80.14268 (17)1.04179 (9)0.12616 (12)0.0351 (3)
C90.18928 (18)1.05794 (10)0.01239 (13)0.0385 (3)
H90.15711.11000.02970.046*
C100.28348 (18)0.99575 (10)0.03651 (12)0.0390 (3)
C110.3306 (2)0.91681 (11)0.02370 (14)0.0424 (4)
H110.39030.87390.01270.051*
C120.2881 (2)0.90291 (10)0.13758 (14)0.0412 (4)
H120.32190.85070.17860.049*
N10.01119 (16)0.84928 (9)0.49229 (11)0.0415 (3)
N20.5346 (2)0.78806 (11)0.68694 (13)0.0556 (4)
N30.03468 (16)1.10760 (9)0.17095 (12)0.0426 (3)
N40.33458 (17)1.01266 (11)0.15575 (12)0.0480 (4)
N50.15513 (16)0.95046 (9)0.30872 (11)0.0412 (3)
H5'0.06960.97370.33340.066 (6)*
O10.07352 (14)0.91080 (9)0.45042 (11)0.0538 (3)
O20.03902 (16)0.78209 (9)0.53913 (13)0.0649 (4)
O30.4751 (2)0.73510 (14)0.75172 (17)0.1018 (7)
O40.67277 (18)0.81174 (12)0.70251 (14)0.0761 (5)
O50.04027 (15)1.08548 (9)0.25453 (11)0.0536 (3)
O60.0202 (2)1.18043 (9)0.12207 (15)0.0749 (5)
O70.2970 (2)1.08398 (12)0.20501 (13)0.0772 (5)
O80.41639 (18)0.95593 (10)0.19853 (11)0.0632 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0474 (8)0.0319 (7)0.0264 (6)0.0017 (5)0.0039 (6)0.0020 (5)
C20.0440 (8)0.0324 (6)0.0275 (6)0.0054 (5)0.0054 (6)0.0050 (5)
C30.0558 (9)0.0319 (7)0.0275 (6)0.0034 (6)0.0062 (6)0.0006 (5)
C40.0515 (9)0.0342 (7)0.0324 (7)0.0051 (6)0.0013 (6)0.0045 (6)
C50.0440 (8)0.0432 (8)0.0408 (8)0.0011 (6)0.0033 (6)0.0060 (6)
C60.0482 (9)0.0434 (8)0.0344 (7)0.0064 (6)0.0090 (6)0.0019 (6)
C70.0428 (8)0.0357 (7)0.0275 (7)0.0047 (6)0.0011 (6)0.0001 (5)
C80.0390 (7)0.0362 (7)0.0294 (7)0.0020 (6)0.0001 (6)0.0011 (5)
C90.0431 (8)0.0404 (7)0.0311 (7)0.0038 (6)0.0019 (6)0.0061 (6)
C100.0442 (8)0.0475 (8)0.0251 (7)0.0087 (6)0.0023 (6)0.0011 (6)
C110.0510 (9)0.0413 (7)0.0352 (8)0.0013 (6)0.0062 (7)0.0066 (6)
C120.0547 (9)0.0341 (7)0.0347 (8)0.0012 (6)0.0039 (7)0.0007 (6)
N10.0474 (7)0.0477 (7)0.0298 (6)0.0099 (6)0.0059 (5)0.0071 (5)
N20.0664 (10)0.0524 (8)0.0458 (8)0.0117 (7)0.0061 (7)0.0016 (7)
N30.0446 (7)0.0440 (7)0.0384 (7)0.0043 (5)0.0002 (6)0.0005 (6)
N40.0500 (8)0.0640 (9)0.0299 (7)0.0103 (7)0.0035 (6)0.0004 (6)
N50.0486 (7)0.0463 (7)0.0292 (6)0.0050 (6)0.0069 (5)0.0061 (5)
O10.0453 (7)0.0685 (8)0.0477 (7)0.0023 (6)0.0055 (5)0.0006 (6)
O20.0664 (8)0.0640 (8)0.0658 (8)0.0275 (7)0.0140 (7)0.0067 (7)
O30.1026 (13)0.1026 (13)0.0942 (13)0.0066 (11)0.0224 (10)0.0621 (11)
O40.0589 (9)0.0992 (12)0.0659 (9)0.0112 (8)0.0170 (7)0.0015 (8)
O50.0555 (7)0.0629 (7)0.0441 (7)0.0117 (6)0.0137 (6)0.0005 (5)
O60.0939 (11)0.0520 (8)0.0818 (10)0.0279 (7)0.0238 (9)0.0236 (7)
O70.0902 (11)0.0960 (11)0.0474 (8)0.0149 (9)0.0177 (7)0.0318 (8)
O80.0791 (9)0.0717 (8)0.0420 (7)0.0090 (7)0.0234 (6)0.0128 (6)
Geometric parameters (Å, º) top
C1—N51.386 (2)C9—C101.367 (2)
C1—C61.396 (2)C9—H90.9300
C1—C21.4095 (19)C10—C111.389 (2)
C2—C31.378 (2)C10—N41.4623 (18)
C2—N11.459 (2)C11—C121.372 (2)
C3—C41.374 (2)C11—H110.9300
C3—H30.9300C12—H120.9300
C4—C51.384 (2)N1—O21.2196 (18)
C4—N21.457 (2)N1—O11.2260 (19)
C5—C61.369 (2)N2—O31.210 (2)
C5—H50.9300N2—O41.222 (2)
C6—H60.9300N3—O61.2094 (19)
C7—N51.3766 (18)N3—O51.2240 (18)
C7—C121.404 (2)N4—O81.2163 (19)
C7—C81.409 (2)N4—O71.219 (2)
C8—C91.388 (2)N5—H5'0.8718
C8—N31.4590 (19)
N5—C1—C6121.15 (13)C8—C9—H9120.7
N5—C1—C2121.81 (14)C9—C10—C11121.70 (13)
C6—C1—C2116.96 (14)C9—C10—N4119.01 (14)
C3—C2—C1121.77 (14)C11—C10—N4119.29 (14)
C3—C2—N1116.78 (12)C12—C11—C10119.16 (14)
C1—C2—N1121.45 (13)C12—C11—H11120.4
C4—C3—C2118.40 (13)C10—C11—H11120.4
C4—C3—H3120.8C11—C12—C7121.76 (14)
C2—C3—H3120.8C11—C12—H12119.1
C3—C4—C5122.13 (14)C7—C12—H12119.1
C3—C4—N2118.75 (14)O2—N1—O1123.57 (14)
C5—C4—N2119.11 (15)O2—N1—C2117.65 (14)
C6—C5—C4118.51 (15)O1—N1—C2118.75 (12)
C6—C5—H5120.7O3—N2—O4123.38 (16)
C4—C5—H5120.7O3—N2—C4118.19 (17)
C5—C6—C1122.18 (14)O4—N2—C4118.43 (16)
C5—C6—H6118.9O6—N3—O5123.06 (15)
C1—C6—H6118.9O6—N3—C8118.69 (14)
N5—C7—C12120.75 (13)O5—N3—C8118.23 (13)
N5—C7—C8122.49 (13)O8—N4—O7123.72 (14)
C12—C7—C8116.75 (13)O8—N4—C10118.06 (14)
C9—C8—C7121.85 (14)O7—N4—C10118.19 (15)
C9—C8—N3116.27 (13)C7—N5—C1125.08 (13)
C7—C8—N3121.87 (13)C7—N5—H5'121.2
C10—C9—C8118.61 (14)C1—N5—H5'113.5
C10—C9—H9120.7
N5—C1—C2—C3176.25 (13)C10—C11—C12—C71.6 (2)
C6—C1—C2—C30.4 (2)N5—C7—C12—C11179.32 (15)
N5—C1—C2—N13.3 (2)C8—C7—C12—C112.0 (2)
C6—C1—C2—N1179.98 (12)C3—C2—N1—O229.46 (18)
C1—C2—C3—C41.6 (2)C1—C2—N1—O2150.96 (14)
N1—C2—C3—C4177.94 (12)C3—C2—N1—O1148.60 (14)
C2—C3—C4—C52.5 (2)C1—C2—N1—O130.98 (19)
C2—C3—C4—N2175.88 (13)C3—C4—N2—O315.0 (2)
C3—C4—C5—C61.2 (2)C5—C4—N2—O3166.57 (17)
N2—C4—C5—C6177.18 (14)C3—C4—N2—O4164.90 (16)
C4—C5—C6—C11.0 (2)C5—C4—N2—O413.5 (2)
N5—C1—C6—C5174.90 (14)C9—C8—N3—O616.4 (2)
C2—C1—C6—C51.8 (2)C7—C8—N3—O6164.47 (16)
N5—C7—C8—C9177.20 (13)C9—C8—N3—O5161.71 (14)
C12—C7—C8—C94.2 (2)C7—C8—N3—O517.4 (2)
N5—C7—C8—N33.7 (2)C9—C10—N4—O8178.92 (15)
C12—C7—C8—N3174.86 (13)C11—C10—N4—O80.6 (2)
C7—C8—C9—C102.6 (2)C9—C10—N4—O73.3 (2)
N3—C8—C9—C10176.46 (13)C11—C10—N4—O7177.19 (16)
C8—C9—C10—C111.2 (2)C12—C7—N5—C131.8 (2)
C8—C9—C10—N4179.33 (13)C8—C7—N5—C1149.61 (14)
C9—C10—C11—C123.3 (2)C6—C1—N5—C732.3 (2)
N4—C10—C11—C12177.26 (14)C2—C1—N5—C7151.20 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5···O10.872.092.6853 (18)125
N5—H5···O50.872.062.6321 (19)123
C6—H6···O8i0.932.543.464 (2)170
C11—H11···O2ii0.932.443.144 (2)132
Symmetry codes: (i) x+1, y+2, z; (ii) x+1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC12H7N5O8
Mr349.23
Crystal system, space groupMonoclinic, P21/n
Temperature (K)291
a, b, c (Å)8.4987 (9), 14.7982 (15), 11.1828 (12)
β (°) 95.395 (1)
V3)1400.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.36 × 0.32 × 0.28
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.953, 0.964
No. of measured, independent and
observed [I > 2σ(I)] reflections
7449, 2745, 2384
Rint0.085
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.135, 1.01
No. of reflections2745
No. of parameters227
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.36

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5'···O10.872.092.6853 (18)125
N5—H5'···O50.872.062.6321 (19)123
C6—H6···O8i0.932.543.464 (2)170
C11—H11···O2ii0.932.443.144 (2)132
Symmetry codes: (i) x+1, y+2, z; (ii) x+1/2, y+3/2, z1/2.
 

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