In the framework of a thorough study of the reactions of C-(2,4,6-trinitrophenyl)azomethines with various nucleophiles, the crystal and molecular structures of three compounds, namely 2,4-dinitro-N-phenyl-6-(phenylazo)benzamide, (I), N-(2-methoxyphenyl)-2-(2-methoxyphenylazo)-4,6-dinitrobenzamide, (II), and N-methyl-2,4-dinitro-N-phenyl-6-(phenylazo)benzamide, (III), were determined from low-resolution laboratory powder diffraction data. The crystal structure determination of (I), starting from erroneous two-dimensional structures, produced the correct solution as a result of the use of a combination of a systematic grid search and bond-restrained Rietveld refinement. The obtained molecular structure of (I) was quite unexpected. Based on the correct molecular structure of (I), the crystal structures of (II) and (III) were routinely solved by the grid search technique.
Supporting information
CCDC references: 199446; 199447; 199448
For all compounds, data collection: local program; cell refinement: LSPAID (Visser, 1986); program(s) used to solve structure: MRIA (Zlokazov & Chernyshev, 1992); program(s) used to refine structure: MRIA (Zlokazov & Chernyshev, 1992); molecular graphics: PLATON (Spek, 2001); software used to prepare material for publication: PARST (Nardelli, 1983).
(I) 2,4-dinitro-
N-phenyl-6-(phenyldiazenyl)-benzamide
top
Crystal data top
C19H13N5O5 | Z = 2 |
Mr = 391.34 | F(000) = 404 |
Monoclinic, P21 | Dx = 1.474 Mg m−3 |
a = 11.720 (6) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 6.831 (4) Å | T = 295 K |
c = 11.045 (6) Å | Particle morphology: needles |
β = 94.38 (2)° | yellow |
V = 881.7 (8) Å3 | flat_sheet, 25 × 25 mm |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Data collection mode: reflection |
Radiation source: X-ray sealed tube | Scan method: step |
Ni filtered monochromator | 2θmin = 6.00°, 2θmax = 70.0°, 2θstep = 0.02° |
Specimen mounting: pressed as a thin layer in the specimen holder | |
Refinement top
Refinement on Inet | 138 parameters |
Least-squares matrix: full with fixed elements per cycle | 51 restraints |
Rp = 0.065 | 1 constraint |
Rwp = 0.083 | H-atom parameters not refined |
Rexp = 0.021 | Weighting scheme based on measured s.u.'s |
χ2 = 16.322 | (Δ/σ)max = 0.01 |
3201 data points | Background function: Chebyshev polynomial up to the 5th order |
Profile function: split-type pseudo-Voigt (Toraya, 1986) | Preferred orientation correction: Spherical harmonics expansion (Ahtee et al., 1989) up to the 6th order. |
Crystal data top
C19H13N5O5 | β = 94.38 (2)° |
Mr = 391.34 | V = 881.7 (8) Å3 |
Monoclinic, P21 | Z = 2 |
a = 11.720 (6) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 6.831 (4) Å | T = 295 K |
c = 11.045 (6) Å | flat_sheet, 25 × 25 mm |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Scan method: step |
Specimen mounting: pressed as a thin layer in the specimen holder | 2θmin = 6.00°, 2θmax = 70.0°, 2θstep = 0.02° |
Data collection mode: reflection | |
Refinement top
Rp = 0.065 | 3201 data points |
Rwp = 0.083 | 138 parameters |
Rexp = 0.021 | 51 restraints |
χ2 = 16.322 | H-atom parameters not refined |
Special details top
Experimental. specimen was rotated in its plane |
Refinement. Hydrogen atoms were placed in calculated positions. The planarity of the
aromatic rings and nitrogroups was restrained. The only common atomic
displacement parameter was refined for all non-H atoms. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.5482 (8) | 0.0401 | 0.3273 (8) | 0.060 (2)* | |
C2 | 0.6418 (10) | 0.059 (5) | 0.2580 (8) | 0.060* | |
C3 | 0.7541 (8) | 0.033 (5) | 0.3112 (9) | 0.060* | |
C4 | 0.7654 (8) | 0.004 (5) | 0.4382 (8) | 0.060* | |
C5 | 0.6719 (8) | −0.021 (5) | 0.5098 (10) | 0.060* | |
C6 | 0.5622 (10) | 0.011 (5) | 0.4553 (8) | 0.060* | |
C7 | 0.4304 (10) | 0.068 (4) | 0.2728 (8) | 0.060* | |
N8 | 0.6246 (6) | 0.090 (4) | 0.1224 (7) | 0.060* | |
O9 | 0.5280 (6) | 0.110 (3) | 0.0801 (5) | 0.060* | |
O10 | 0.7054 (6) | 0.081 (3) | 0.0621 (6) | 0.060* | |
N11 | 0.8817 (6) | −0.019 (3) | 0.4993 (7) | 0.060* | |
O12 | 0.9648 (7) | 0.001 (3) | 0.4413 (6) | 0.060* | |
O13 | 0.8902 (6) | −0.068 (3) | 0.6054 (6) | 0.060* | |
N14 | 0.4620 (8) | 0.000 (5) | 0.5186 (8) | 0.060* | |
N15 | 0.4706 (7) | 0.053 (3) | 0.6259 (6) | 0.060* | |
C16 | 0.3748 (10) | 0.042 (5) | 0.6957 (8) | 0.060* | |
C17 | 0.3897 (8) | 0.022 (5) | 0.8243 (8) | 0.060* | |
C18 | 0.2933 (9) | 0.006 (5) | 0.8919 (8) | 0.060* | |
C19 | 0.1831 (8) | 0.015 (5) | 0.8357 (8) | 0.060* | |
C20 | 0.1675 (10) | 0.031 (5) | 0.7098 (8) | 0.060* | |
C21 | 0.2614 (8) | 0.047 (5) | 0.6407 (8) | 0.060* | |
N22 | 0.3707 (8) | −0.105 (3) | 0.2581 (7) | 0.060* | |
C23 | 0.2564 (8) | −0.109 (4) | 0.2098 (9) | 0.060* | |
C24 | 0.1849 (10) | 0.056 (5) | 0.2099 (10) | 0.060* | |
C25 | 0.0712 (10) | 0.042 (5) | 0.1622 (9) | 0.060* | |
C26 | 0.0271 (11) | −0.134 (4) | 0.1144 (10) | 0.060* | |
C27 | 0.0974 (11) | −0.297 (3) | 0.1132 (10) | 0.060* | |
C28 | 0.2100 (11) | −0.285 (4) | 0.1603 (11) | 0.060* | |
O29 | 0.4013 (7) | 0.236 (3) | 0.2419 (6) | 0.060* | |
H30 | 0.6861 | −0.0338 | 0.5936 | 0.051* | |
H31 | 0.8179 | 0.0461 | 0.2661 | 0.051* | |
H32 | 0.4628 | 0.0182 | 0.8618 | 0.051* | |
H33 | 0.3042 | −0.0042 | 0.9773 | 0.051* | |
H34 | 0.1189 | 0.0052 | 0.8820 | 0.051* | |
H35 | 0.0924 | 0.0369 | 0.6718 | 0.051* | |
H36 | 0.2518 | 0.0593 | 0.5558 | 0.051* | |
H37 | 0.4058 | −0.2158 | 0.2764 | 0.051* | |
H38 | 0.2133 | 0.1742 | 0.2427 | 0.051* | |
H39 | 0.0234 | 0.1532 | 0.1632 | 0.051* | |
H40 | −0.0493 | −0.1404 | 0.0804 | 0.051* | |
H41 | 0.0681 | −0.4179 | 0.0809 | 0.051* | |
H42 | 0.2580 | −0.3968 | 0.1616 | 0.051* | |
Geometric parameters (Å, º) top
C1—C2 | 1.39 (2) | C17—C18 | 1.41 (1) |
C1—C6 | 1.42 (1) | C17—H32 | 0.92 |
C1—C7 | 1.48 (1) | C18—C19 | 1.39 (1) |
C2—C3 | 1.41 (2) | C18—H33 | 0.94 |
C2—N8 | 1.51 (1) | C19—C20 | 1.39 (1) |
C3—C4 | 1.41 (1) | C19—H34 | 0.94 |
C3—H31 | 0.93 | C20—C21 | 1.39 (2) |
C4—C5 | 1.41 (2) | C20—H35 | 0.95 |
C4—N11 | 1.48 (1) | C21—H36 | 0.94 |
C5—C6 | 1.39 (2) | N22—C23 | 1.40 (1) |
C5—H30 | 0.93 | N22—H37 | 0.88 |
C6—N14 | 1.41 (2) | C23—C24 | 1.41 (3) |
C7—O29 | 1.24 (3) | C23—C28 | 1.41 (3) |
C7—N22 | 1.38 (3) | C24—C25 | 1.40 (2) |
N8—O9 | 1.20 (1) | C24—H38 | 0.93 |
N8—O10 | 1.20 (1) | C25—C26 | 1.40 (4) |
N11—O12 | 1.21 (1) | C25—H39 | 0.95 |
N11—O13 | 1.22 (1) | C26—C27 | 1.39 (3) |
N14—N15 | 1.24 (2) | C26—H40 | 0.95 |
N15—C16 | 1.41 (1) | C27—C28 | 1.38 (2) |
C16—C21 | 1.42 (1) | C27—H41 | 0.95 |
C16—C17 | 1.42 (1) | C28—H42 | 0.95 |
| | | |
C2—C1—C6 | 121.5 (5) | C16—C17—H32 | 119.3 |
C2—C1—C7 | 121.1 (8) | C19—C18—C17 | 121.1 (9) |
C6—C1—C7 | 117.1 (6) | C19—C18—H33 | 119.9 |
C1—C2—C3 | 120.6 (9) | C17—C18—H33 | 118.9 |
C1—C2—N8 | 120.5 (7) | C18—C19—C20 | 119.7 (9) |
C3—C2—N8 | 118.7 (8) | C18—C19—H34 | 120.5 |
C2—C3—C4 | 116.4 (9) | C20—C19—H34 | 119.8 |
C2—C3—H31 | 121.6 | C21—C20—C19 | 120.3 (8) |
C4—C3—H31 | 121.7 | C21—C20—H35 | 120.1 |
C5—C4—C3 | 123.8 (9) | C19—C20—H35 | 119.5 |
C5—C4—N11 | 117.4 (8) | C20—C21—C16 | 121 (1) |
C3—C4—N11 | 118.7 (8) | C20—C21—H36 | 121.0 |
C6—C5—C4 | 118.1 (9) | C16—C21—H36 | 117.8 |
C6—C5—H30 | 122.2 | C7—N22—C23 | 121 (1) |
C4—C5—H30 | 118.8 | C7—N22—H37 | 119.1 |
C5—C6—N14 | 124 (1) | C23—N22—H37 | 119.4 |
C5—C6—C1 | 118.9 (8) | N22—C23—C24 | 123 (1) |
N14—C6—C1 | 117.5 (7) | N22—C23—C28 | 119 (1) |
O29—C7—N22 | 130 (2) | C24—C23—C28 | 118 (2) |
O29—C7—C1 | 117 (1) | C25—C24—C23 | 120 (1) |
N22—C7—C1 | 113.0 (9) | C25—C24—H38 | 120.5 |
O9—N8—O10 | 123.5 (8) | C23—C24—H38 | 119.9 |
O9—N8—C2 | 116.9 (7) | C26—C25—C24 | 121 (1) |
O10—N8—C2 | 119.4 (7) | C26—C25—H39 | 119.7 |
O12—N11—O13 | 122.0 (8) | C24—C25—H39 | 119.1 |
O12—N11—C4 | 119.7 (8) | C27—C26—C25 | 119 (2) |
O13—N11—C4 | 118.2 (7) | C27—C26—H40 | 120.5 |
N15—N14—C6 | 116.7 (8) | C25—C26—H40 | 120.0 |
N14—N15—C16 | 119.8 (8) | C28—C27—C26 | 120 (1) |
N15—C16—C21 | 122 (1) | C28—C27—H41 | 119.9 |
N15—C16—C17 | 120.5 (8) | C26—C27—H41 | 120.1 |
C21—C16—C17 | 118.0 (8) | C27—C28—C23 | 122 (1) |
C18—C17—C16 | 119.7 (8) | C27—C28—H42 | 120.4 |
C18—C17—H32 | 121.0 | C23—C28—H42 | 118.0 |
(II)
N-(2-methoxyphenyl-2-(methoxyphenyldiazenyl)-4,6-dinitrobenzamide
top
Crystal data top
C21H17N5O7 | F(000) = 936 |
Mr = 451.40 | Dx = 1.461 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.5418 Å |
a = 22.788 (8) Å | T = 295 K |
b = 13.018 (6) Å | Particle morphology: needles |
c = 6.920 (3) Å | yellow |
V = 2052.8 (15) Å3 | flat_sheet, 25 × 25 mm |
Z = 4 | |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Data collection mode: reflection |
Radiation source: X-ray sealed tube | Scan method: step |
Ni filtered monochromator | 2θmin = 6.00°, 2θmax = 70.0°, 2θstep = 0.02° |
Specimen mounting: pressed as a thin layer in the specimen holder | |
Refinement top
Refinement on Inet | 144 parameters |
Least-squares matrix: full with fixed elements per cycle | 63 restraints |
Rp = 0.057 | 1 constraint |
Rwp = 0.080 | H-atom parameters not refined |
Rexp = 0.019 | Weighting scheme based on measured s.u.'s |
χ2 = 17.140 | (Δ/σ)max = 0.01 |
3201 data points | Background function: Chebyshev polynomial up to the 5th order |
Profile function: split-type pseudo-Voigt (Toraya, 1986) | Preferred orientation correction: Spherical harmonics expansion (Ahtee et al., 1989) up to the 6th order. |
Crystal data top
C21H17N5O7 | V = 2052.8 (15) Å3 |
Mr = 451.40 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.5418 Å |
a = 22.788 (8) Å | T = 295 K |
b = 13.018 (6) Å | flat_sheet, 25 × 25 mm |
c = 6.920 (3) Å | |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Scan method: step |
Specimen mounting: pressed as a thin layer in the specimen holder | 2θmin = 6.00°, 2θmax = 70.0°, 2θstep = 0.02° |
Data collection mode: reflection | |
Refinement top
Rp = 0.057 | 3201 data points |
Rwp = 0.080 | 144 parameters |
Rexp = 0.019 | 63 restraints |
χ2 = 17.140 | H-atom parameters not refined |
Special details top
Experimental. specimen was rotated in its plane |
Refinement. Hydrogen atoms were placed in calculated positions. The planarity of the
aromatic rings and nitrogroups was restrained. The only common atomic
displacement parameter was refined for all non-H atoms. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.3077 (4) | 0.1227 (8) | 0.065 (3) | 0.035 (1)* | |
C2 | 0.3655 (4) | 0.1415 (9) | 0.067 (3) | 0.035* | |
C3 | 0.4090 (4) | 0.0624 (7) | 0.057 (3) | 0.035* | |
C4 | 0.3872 (4) | −0.0383 (7) | 0.041 (3) | 0.035* | |
C5 | 0.3268 (4) | −0.0607 (8) | 0.037 (3) | 0.035* | |
C6 | 0.2868 (4) | 0.0149 (8) | 0.047 (3) | 0.035* | |
C7 | 0.2573 (5) | 0.1913 (9) | 0.070 (3) | 0.035* | |
N8 | 0.3892 (4) | 0.2508 (8) | 0.083 (3) | 0.035* | |
O9 | 0.3527 (3) | 0.3163 (6) | 0.105 (2) | 0.035* | |
O10 | 0.4401 (3) | 0.2632 (5) | 0.059 (2) | 0.035* | |
N11 | 0.4282 (3) | −0.1255 (7) | 0.030 (3) | 0.035* | |
O12 | 0.4783 (2) | −0.1019 (6) | 0.042 (2) | 0.035* | |
O13 | 0.4114 (3) | −0.2128 (5) | 0.002 (2) | 0.035* | |
N14 | 0.2250 (4) | 0.0116 (8) | 0.045 (3) | 0.035* | |
N15 | 0.2009 (3) | −0.0681 (7) | 0.102 (3) | 0.035* | |
C16 | 0.1394 (3) | −0.0749 (8) | 0.074 (3) | 0.035* | |
C17 | 0.1130 (4) | −0.1735 (8) | 0.094 (3) | 0.035* | |
C18 | 0.0528 (4) | −0.1805 (7) | 0.066 (3) | 0.035* | |
C19 | 0.0194 (3) | −0.0946 (9) | 0.022 (3) | 0.035* | |
C20 | 0.0452 (4) | 0.0021 (7) | 0.005 (3) | 0.035* | |
C21 | 0.1050 (4) | 0.0117 (7) | 0.032 (3) | 0.035* | |
N22 | 0.2415 (4) | 0.2398 (6) | −0.098 (2) | 0.035* | |
C23 | 0.1927 (4) | 0.3052 (8) | −0.117 (3) | 0.035* | |
C24 | 0.1449 (4) | 0.2997 (8) | 0.012 (3) | 0.035* | |
C25 | 0.0962 (4) | 0.3634 (9) | −0.004 (3) | 0.035* | |
C26 | 0.0935 (4) | 0.4342 (9) | −0.153 (3) | 0.035* | |
C27 | 0.1390 (4) | 0.4398 (9) | −0.287 (3) | 0.035* | |
C28 | 0.1885 (4) | 0.3766 (9) | −0.271 (3) | 0.035* | |
O29 | 0.2347 (3) | 0.3838 (6) | −0.405 (2) | 0.035* | |
O30 | 0.1482 (3) | −0.2562 (5) | 0.136 (2) | 0.035* | |
C31 | 0.2186 (4) | 0.4368 (9) | −0.574 (3) | 0.035* | |
O32 | 0.2361 (3) | 0.2095 (6) | 0.2347 (17) | 0.035* | |
C33 | 0.1198 (5) | −0.352 (1) | 0.118 (3) | 0.035* | |
H34 | 0.3148 | −0.1302 | 0.0271 | 0.051* | |
H35 | 0.4488 | 0.0765 | 0.0599 | 0.051* | |
H36 | 0.0344 | −0.2443 | 0.0768 | 0.051* | |
H37 | −0.0209 | −0.1017 | 0.0053 | 0.051* | |
H38 | 0.0224 | 0.0595 | −0.0230 | 0.051* | |
H39 | 0.1228 | 0.0757 | 0.0199 | 0.051* | |
H40 | 0.2689 | 0.2432 | −0.1850 | 0.051* | |
H41 | 0.1475 | 0.2535 | 0.1142 | 0.051* | |
H42 | 0.0657 | 0.3579 | 0.0846 | 0.051* | |
H43 | 0.0605 | 0.4756 | −0.1664 | 0.051* | |
H44 | 0.1367 | 0.4867 | −0.3868 | 0.051* | |
H45 | 0.2498 | 0.4342 | −0.6663 | 0.051* | |
H46 | 0.2100 | 0.5072 | −0.5416 | 0.051* | |
H47 | 0.1838 | 0.4059 | −0.6281 | 0.051* | |
H48 | 0.1467 | −0.4059 | 0.1515 | 0.051* | |
H49 | 0.1072 | −0.3610 | −0.0136 | 0.051* | |
H50 | 0.0864 | −0.3541 | 0.2018 | 0.051* | |
Geometric parameters (Å, º) top
C1—C2 | 1.34 (1) | C19—C20 | 1.39 (1) |
C1—C7 | 1.46 (2) | C19—H37 | 0.93 |
C1—C6 | 1.49 (2) | C20—C21 | 1.38 (1) |
C2—C3 | 1.43 (1) | C20—H38 | 0.93 |
C2—N8 | 1.53 (1) | C21—H39 | 0.93 |
C3—C4 | 1.41 (1) | N22—C23 | 1.41 (1) |
C3—H35 | 0.93 | N22—H40 | 0.87 |
C4—C5 | 1.41 (1) | C23—C24 | 1.41 (2) |
C4—N11 | 1.47 (1) | C23—C28 | 1.42 (2) |
C5—C6 | 1.34 (1) | C24—C25 | 1.39 (1) |
C5—H34 | 0.95 | C24—H41 | 0.93 |
C6—N14 | 1.41 (1) | C25—C26 | 1.38 (2) |
C7—O32 | 1.26 (2) | C25—H42 | 0.93 |
C7—N22 | 1.37 (2) | C26—C27 | 1.39 (2) |
N8—O10 | 1.18 (1) | C26—H43 | 0.93 |
N8—O9 | 1.20 (1) | C27—C28 | 1.40 (1) |
N11—O12 | 1.185 (9) | C27—H44 | 0.93 |
N11—O13 | 1.22 (1) | C28—O29 | 1.41 (2) |
N14—N15 | 1.24 (2) | O29—C31 | 1.41 (2) |
N15—C16 | 1.42 (1) | O30—C33 | 1.41 (1) |
C16—C21 | 1.40 (1) | C31—H45 | 0.96 |
C16—C17 | 1.42 (1) | C31—H46 | 0.96 |
C17—O30 | 1.37 (1) | C31—H47 | 0.96 |
C17—C18 | 1.39 (1) | C33—H48 | 0.96 |
C18—C19 | 1.39 (1) | C33—H49 | 0.96 |
C18—H36 | 0.93 | C33—H50 | 0.96 |
| | | |
C2—C1—C7 | 131.6 (9) | C21—C20—C19 | 119.1 (8) |
C2—C1—C6 | 119.2 (9) | C21—C20—H38 | 120.4 |
C7—C1—C6 | 109.2 (9) | C19—C20—H38 | 120.5 |
C1—C2—C3 | 123.3 (9) | C20—C21—C16 | 120.4 (8) |
C1—C2—N8 | 121.3 (9) | C20—C21—H39 | 120.0 |
C3—C2—N8 | 115.4 (9) | C16—C21—H39 | 119.6 |
C4—C3—C2 | 115.5 (9) | C7—N22—C23 | 124 (1) |
C4—C3—H35 | 122.2 | C7—N22—H40 | 115.0 |
C2—C3—H35 | 122.4 | C23—N22—H40 | 118.2 |
C3—C4—C5 | 122.7 (8) | N22—C23—C24 | 121.4 (9) |
C3—C4—N11 | 119.9 (8) | N22—C23—C28 | 121 (1) |
C5—C4—N11 | 117.4 (8) | C24—C23—C28 | 117 (1) |
C6—C5—C4 | 120.7 (9) | C25—C24—C23 | 122.4 (9) |
C6—C5—H34 | 120.5 | C25—C24—H41 | 119.8 |
C4—C5—H34 | 118.8 | C23—C24—H41 | 117.7 |
C5—C6—N14 | 130.9 (9) | C26—C25—C24 | 120 (1) |
C5—C6—C1 | 119 (1) | C26—C25—H42 | 120.6 |
N14—C6—C1 | 110.5 (8) | C24—C25—H42 | 119.9 |
O32—C7—N22 | 125 (2) | C25—C26—C27 | 120 (1) |
O32—C7—C1 | 116 (1) | C25—C26—H43 | 120.0 |
N22—C7—C1 | 118 (1) | C27—C26—H43 | 120.2 |
O10—N8—O9 | 126.9 (9) | C26—C27—C28 | 121.2 (9) |
O10—N8—C2 | 117.7 (9) | C26—C27—H44 | 119.4 |
O9—N8—C2 | 115.2 (9) | C28—C27—H44 | 119.4 |
O12—N11—O13 | 123.9 (8) | C27—C28—O29 | 121 (1) |
O12—N11—C4 | 114.1 (7) | C27—C28—C23 | 120 (1) |
O13—N11—C4 | 122.0 (8) | O29—C28—C23 | 119 (1) |
N15—N14—C6 | 117.7 (9) | C31—O29—C28 | 113 (1) |
N14—N15—C16 | 116.4 (8) | C17—O30—C33 | 113.9 (8) |
C21—C16—N15 | 122.1 (7) | O29—C31—H45 | 110.1 |
C21—C16—C17 | 120.6 (9) | O29—C31—H46 | 109.0 |
N15—C16—C17 | 117.4 (7) | H45—C31—H46 | 109.9 |
O30—C17—C18 | 123.7 (8) | O29—C31—H47 | 109.4 |
O30—C17—C16 | 118.7 (9) | H45—C31—H47 | 109.8 |
C18—C17—C16 | 117.5 (8) | H46—C31—H47 | 108.7 |
C19—C18—C17 | 121.3 (8) | O30—C33—H48 | 109.3 |
C19—C18—H36 | 119.3 | O30—C33—H49 | 109.3 |
C17—C18—H36 | 119.4 | H48—C33—H49 | 109.4 |
C18—C19—C20 | 121 (1) | O30—C33—H50 | 109.5 |
C18—C19—H37 | 119.3 | H48—C33—H50 | 109.7 |
C20—C19—H37 | 119.7 | H49—C33—H50 | 109.5 |
(III)
N-methyl-2,4-dinitro-
N-phenyl-6-(phenyldiazenyl)-benzamide
top
Crystal data top
C20H15N5O5 | Z = 4 |
Mr = 405.37 | F(000) = 840 |
Monoclinic, P21/c | Dx = 1.382 Mg m−3 |
a = 8.676 (4) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 18.560 (7) Å | T = 295 K |
c = 12.098 (6) Å | Particle morphology: needles |
β = 90.38 (2)° | yellow |
V = 1948.1 (15) Å3 | flat_sheet, 25 × 25 mm |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Data collection mode: reflection |
Radiation source: X-ray sealed tube | Scan method: step |
Ni filtered monochromator | 2θmin = 8.00°, 2θmax = 72.0°, 2θstep = 0.02° |
Specimen mounting: pressed as a thin layer in the specimen holder | |
Refinement top
Refinement on Inet | 142 parameters |
Least-squares matrix: full with fixed elements per cycle | 53 restraints |
Rp = 0.050 | 1 constraint |
Rwp = 0.066 | H-atom parameters not refined |
Rexp = 0.022 | Weighting scheme based on measured s.u.'s |
χ2 = 9.364 | (Δ/σ)max = 0.01 |
3201 data points | Background function: Chebyshev polynomial up to the 5th order |
Profile function: split-type pseudo-Voigt (Toraya, 1986) | Preferred orientation correction: Spherical harmonics expansion (Ahtee et al., 1989) up to the 6th order. |
Crystal data top
C20H15N5O5 | β = 90.38 (2)° |
Mr = 405.37 | V = 1948.1 (15) Å3 |
Monoclinic, P21/c | Z = 4 |
a = 8.676 (4) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 18.560 (7) Å | T = 295 K |
c = 12.098 (6) Å | flat_sheet, 25 × 25 mm |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Scan method: step |
Specimen mounting: pressed as a thin layer in the specimen holder | 2θmin = 8.00°, 2θmax = 72.0°, 2θstep = 0.02° |
Data collection mode: reflection | |
Refinement top
Rp = 0.050 | 3201 data points |
Rwp = 0.066 | 142 parameters |
Rexp = 0.022 | 53 restraints |
χ2 = 9.364 | H-atom parameters not refined |
Special details top
Experimental. specimen was rotated in its plane |
Refinement. Hydrogen atoms were placed in calculated positions. The planarity of the
aromatic rings and nitrogroups was restrained. The only common atomic
displacement parameter was refined for all non-H atoms. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.078 (2) | 0.4394 (6) | 0.3423 (8) | 0.073 (1)* | |
C2 | 0.038 (2) | 0.3678 (7) | 0.3334 (9) | 0.073* | |
C3 | 0.091 (2) | 0.3160 (6) | 0.4124 (9) | 0.073* | |
C4 | 0.1790 (18) | 0.3409 (6) | 0.5018 (9) | 0.073* | |
C5 | 0.2190 (19) | 0.4133 (6) | 0.5128 (9) | 0.073* | |
C6 | 0.167 (2) | 0.4635 (7) | 0.4352 (9) | 0.073* | |
C7 | 0.022 (2) | 0.4981 (6) | 0.2654 (8) | 0.073* | |
N8 | 0.2353 (19) | 0.2899 (7) | 0.5882 (10) | 0.073* | |
O9 | 0.2047 (14) | 0.2294 (4) | 0.5706 (6) | 0.073* | |
O10 | 0.2975 (17) | 0.3172 (6) | 0.6674 (8) | 0.073* | |
N11 | −0.0542 (18) | 0.3403 (6) | 0.2374 (8) | 0.073* | |
O12 | −0.0791 (17) | 0.2774 (5) | 0.2353 (7) | 0.073* | |
O13 | −0.0820 (14) | 0.3863 (4) | 0.1676 (6) | 0.073* | |
N14 | 0.2048 (14) | 0.5381 (5) | 0.4432 (6) | 0.073* | |
N15 | 0.2882 (14) | 0.5530 (5) | 0.5234 (6) | 0.073* | |
C16 | 0.3310 (18) | 0.6248 (6) | 0.5423 (9) | 0.073* | |
C17 | 0.434 (2) | 0.6415 (6) | 0.6296 (9) | 0.073* | |
C18 | 0.477 (2) | 0.7123 (6) | 0.6476 (9) | 0.073* | |
C19 | 0.419 (2) | 0.7671 (5) | 0.5785 (9) | 0.073* | |
C20 | 0.320 (2) | 0.7505 (6) | 0.4913 (9) | 0.073* | |
C21 | 0.2761 (18) | 0.6807 (6) | 0.4729 (9) | 0.073* | |
N22 | 0.1203 (16) | 0.5315 (5) | 0.1918 (7) | 0.073* | |
O23 | −0.1139 (13) | 0.5184 (4) | 0.2799 (5) | 0.073* | |
C24 | 0.2722 (19) | 0.5111 (6) | 0.1767 (8) | 0.073* | |
C25 | 0.393 (2) | 0.5578 (6) | 0.2091 (8) | 0.073* | |
C26 | 0.5455 (19) | 0.5371 (6) | 0.1916 (8) | 0.073* | |
C27 | 0.5776 (19) | 0.4707 (6) | 0.1437 (8) | 0.073* | |
C28 | 0.460 (2) | 0.4237 (6) | 0.1126 (8) | 0.073* | |
C29 | 0.3063 (19) | 0.4434 (6) | 0.1285 (8) | 0.073* | |
C30 | 0.070 (3) | 0.5933 (10) | 0.1248 (13) | 0.073* | |
H31 | 0.2791 | 0.4283 | 0.5732 | 0.051* | |
H32 | 0.0648 | 0.2681 | 0.4044 | 0.051* | |
H33 | 0.4728 | 0.6050 | 0.6746 | 0.051* | |
H34 | 0.5441 | 0.7238 | 0.7051 | 0.051* | |
H35 | 0.4469 | 0.8148 | 0.5912 | 0.051* | |
H36 | 0.2827 | 0.7870 | 0.4461 | 0.051* | |
H37 | 0.2102 | 0.6696 | 0.4144 | 0.051* | |
H38 | 0.3707 | 0.6031 | 0.2383 | 0.051* | |
H39 | 0.6254 | 0.5675 | 0.2126 | 0.051* | |
H40 | 0.6798 | 0.4572 | 0.1326 | 0.051* | |
H41 | 0.4831 | 0.3794 | 0.0806 | 0.051* | |
H42 | 0.2268 | 0.4128 | 0.1070 | 0.051* | |
H43 | −0.0360 | 0.6034 | 0.1405 | 0.051* | |
H44 | 0.0851 | 0.5837 | 0.0491 | 0.051* | |
H45 | 0.1322 | 0.6346 | 0.1474 | 0.051* | |
Geometric parameters (Å, º) top
C1—C2 | 1.38 (2) | C18—C19 | 1.41 (2) |
C1—C6 | 1.43 (2) | C18—H34 | 0.93 |
C1—C7 | 1.51 (2) | C19—C20 | 1.39 (2) |
C2—C3 | 1.43 (2) | C19—H35 | 0.93 |
C2—N11 | 1.50 (2) | C20—C21 | 1.37 (2) |
C3—C4 | 1.40 (2) | C20—H36 | 0.93 |
C3—H32 | 0.92 | C21—H37 | 0.93 |
C4—C5 | 1.39 (2) | N22—C24 | 1.38 (2) |
C4—N8 | 1.49 (2) | N22—C30 | 1.47 (2) |
C5—C6 | 1.40 (2) | C24—C25 | 1.41 (2) |
C5—H31 | 0.94 | C24—C29 | 1.42 (2) |
C6—N14 | 1.43 (2) | C25—C26 | 1.40 (2) |
C7—O23 | 1.25 (2) | C25—H38 | 0.93 |
C7—N22 | 1.38 (2) | C26—C27 | 1.39 (2) |
N8—O9 | 1.17 (2) | C26—H39 | 0.93 |
N8—O10 | 1.21 (2) | C27—C28 | 1.39 (2) |
N11—O12 | 1.19 (1) | C27—H40 | 0.93 |
N11—O13 | 1.22 (1) | C28—C29 | 1.39 (3) |
N14—N15 | 1.24 (1) | C28—H41 | 0.93 |
N15—C16 | 1.40 (1) | C29—H42 | 0.93 |
C16—C17 | 1.41 (2) | C30—H43 | 0.95 |
C16—C21 | 1.42 (2) | C30—H44 | 0.94 |
C17—C18 | 1.38 (2) | C30—H45 | 0.98 |
C17—H33 | 0.93 | | |
| | | |
C2—C1—C6 | 120 (1) | C19—C18—H34 | 120 |
C2—C1—C7 | 125 (1) | C20—C19—C18 | 120 (1) |
C6—C1—C7 | 115 (1) | C20—C19—H35 | 120 |
C1—C2—C3 | 121 (1) | C18—C19—H35 | 120 |
C1—C2—N11 | 122 (1) | C21—C20—C19 | 120 (1) |
C3—C2—N11 | 117 (1) | C21—C20—H36 | 120 |
C4—C3—C2 | 118 (1) | C19—C20—H36 | 120 |
C4—C3—H32 | 122 | C20—C21—C16 | 120 (1) |
C2—C3—H32 | 120 | C20—C21—H37 | 120 |
C5—C4—C3 | 122 (1) | C16—C21—H37 | 120 |
C5—C4—N8 | 118 (1) | C7—N22—C24 | 124 (1) |
C3—C4—N8 | 121 (1) | C7—N22—C30 | 121 (1) |
C4—C5—C6 | 120 (1) | C24—N22—C30 | 115 (1) |
C4—C5—H31 | 120 | N22—C24—C25 | 120 (1) |
C6—C5—H31 | 120 | N22—C24—C29 | 120 (1) |
C5—C6—N14 | 122 (1) | C25—C24—C29 | 120 (1) |
C5—C6—C1 | 119 (1) | C26—C25—C24 | 119 (1) |
N14—C6—C1 | 119 (1) | C26—C25—H38 | 120 |
O23—C7—N22 | 123 (1) | C24—C25—H38 | 120 |
O23—C7—C1 | 115 (1) | C27—C26—C25 | 120 (1) |
N22—C7—C1 | 121.5 (9) | C27—C26—H39 | 120 |
O9—N8—O10 | 130 (1) | C25—C26—H39 | 120 |
O9—N8—C4 | 114 (1) | C26—C27—C28 | 121 (1) |
O10—N8—C4 | 116 (1) | C26—C27—H40 | 119 |
O12—N11—O13 | 130 (1) | C28—C27—H40 | 119 |
O12—N11—C2 | 117 (1) | C27—C28—C29 | 120 (1) |
O13—N11—C2 | 113.6 (9) | C27—C28—H41 | 120 |
N15—N14—C6 | 113.9 (9) | C29—C28—H41 | 120 |
N14—N15—C16 | 119.5 (9) | C28—C29—C24 | 119 (1) |
N15—C16—C17 | 120 (1) | C28—C29—H42 | 121 |
N15—C16—C21 | 121 (1) | C24—C29—H42 | 120 |
C17—C16—C21 | 119 (1) | N22—C30—H43 | 109 |
C18—C17—C16 | 120 (1) | N22—C30—H44 | 110 |
C18—C17—H33 | 120 | H43—C30—H44 | 112 |
C16—C17—H33 | 120 | N22—C30—H45 | 107 |
C17—C18—C19 | 120 (1) | H43—C30—H45 | 109 |
C17—C18—H34 | 120 | H44—C30—H45 | 110 |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C19H13N5O5 | C21H17N5O7 | C20H15N5O5 |
Mr | 391.34 | 451.40 | 405.37 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 | Monoclinic, P21/c |
Temperature (K) | 295 | 295 | 295 |
a, b, c (Å) | 11.720 (6), 6.831 (4), 11.045 (6) | 22.788 (8), 13.018 (6), 6.920 (3) | 8.676 (4), 18.560 (7), 12.098 (6) |
α, β, γ (°) | 90, 94.38 (2), 90 | 90, 90, 90 | 90, 90.38 (2), 90 |
V (Å3) | 881.7 (8) | 2052.8 (15) | 1948.1 (15) |
Z | 2 | 4 | 4 |
Radiation type | Cu Kα, λ = 1.5418 Å | Cu Kα, λ = 1.5418 Å | Cu Kα, λ = 1.5418 Å |
Specimen shape, size (mm) | Flat_sheet, 25 × 25 | Flat_sheet, 25 × 25 | Flat_sheet, 25 × 25 |
|
Data collection |
Diffractometer | DRON-3M diffractometer (Burevestnik, Russia) | DRON-3M diffractometer (Burevestnik, Russia) | DRON-3M diffractometer (Burevestnik, Russia) |
Specimen mounting | Pressed as a thin layer in the specimen holder | Pressed as a thin layer in the specimen holder | Pressed as a thin layer in the specimen holder |
Data collection mode | Reflection | Reflection | Reflection |
Scan method | Step | Step | Step |
2θ values (°) | 2θmin = 6.00 2θmax = 70.0 2θstep = 0.02 | 2θmin = 6.00 2θmax = 70.0 2θstep = 0.02 | 2θmin = 8.00 2θmax = 72.0 2θstep = 0.02 |
|
Refinement |
R factors and goodness of fit | Rp = 0.065, Rwp = 0.083, Rexp = 0.021, χ2 = 16.322 | Rp = 0.057, Rwp = 0.080, Rexp = 0.019, χ2 = 17.140 | Rp = 0.050, Rwp = 0.066, Rexp = 0.022, χ2 = 9.364 |
No. of data points | 3201 | 3201 | 3201 |
No. of parameters | 138 | 144 | 142 |
No. of restraints | 51 | 63 | 53 |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined | H-atom parameters not refined |