Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002489/cv6088sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002489/cv60883sup2.hkl |
CCDC reference: 182620
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.042
- wR factor = 0.128
- Data-to-parameter ratio = 16.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
ABSTY_01 Extra text has been found in the _exptl_absorpt_correction_type field, which should be only a single keyword. A literature citation should be included in the _exptl_absorpt_process_details field.
2-Nitrobenzoic acid, (1) (10 g), was added to benzene (10 ml) and thionyl chloride (10 ml). The mixture was refluxed on a steam bath for 1 h after which more thionyl chloride (10 ml) was added. The mixture was further refluxed for 2 h. The benzene was removed under reduced pressure. The resulting oil was treated with benzene (10 ml) in order to remove excess thionyl chloride. Benzene was removed under reduced pressure and the residue was cooled, leaving a dark brown oil, 2-nitrobenzoyl chloride, (2) (10.5 g). Aniline (10 ml) was added dropwise to (2) and the reaction mixture was left at room temperature for 1 h. Cold water (150 ml) was added and the contents were kept for half an hour. The solid was filtered, washed with water, dried and crystallized from ethanol to give N-phenyl-2-nitrobenzamide, (3) (12.04 g, 87.69%), in the form of colourless prisms suitable for XRD analysis.
The space group was determined uniquely from the systematic absences. The H atoms were located from difference Fourier synthesis and were included in the refinement at geometrically idealized positions with C—H = 0.93 Å and N—H = 0.86 Å, utilizing riding models.
Data collection: COLLECT (Hooft, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corportaion, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C13H10N2O3 | Dx = 1.373 Mg m−3 |
Mr = 242.23 | Melting point: 426-428 K K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9406 (1) Å | Cell parameters from 2949 reflections |
b = 9.4695 (2) Å | θ = 1.0–27.5° |
c = 31.1671 (5) Å | µ = 0.10 mm−1 |
V = 2343.56 (7) Å3 | T = 293 K |
Z = 8 | Prismatic, colorless |
F(000) = 1008 | 0.32 × 0.17 × 0.15 mm |
Nonius KappaCCD diffractometer | 2639 independent reflections |
Radiation source: fine-focus sealed tube | 1945 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω–2ϕ scans | θmax = 27.5°, θmin = 3.8° |
Absorption correction: multi-scan method (SORTAV: Blessing, 1995, 1997) | h = −10→10 |
Tmin = 0.97, Tmax = 0.99 | k = −12→12 |
4857 measured reflections | l = −40→40 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.065P)2 + 0.31P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2639 reflections | Δρmax = 0.14 e Å−3 |
164 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.035 (6) |
C13H10N2O3 | V = 2343.56 (7) Å3 |
Mr = 242.23 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.9406 (1) Å | µ = 0.10 mm−1 |
b = 9.4695 (2) Å | T = 293 K |
c = 31.1671 (5) Å | 0.32 × 0.17 × 0.15 mm |
Nonius KappaCCD diffractometer | 2639 independent reflections |
Absorption correction: multi-scan method (SORTAV: Blessing, 1995, 1997) | 1945 reflections with I > 2σ(I) |
Tmin = 0.97, Tmax = 0.99 | Rint = 0.022 |
4857 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.14 e Å−3 |
2639 reflections | Δρmin = −0.16 e Å−3 |
164 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.67464 (14) | 0.25815 (9) | 0.12636 (4) | 0.0575 (3) | |
O2 | 0.81040 (19) | −0.15887 (15) | 0.02559 (5) | 0.0861 (5) | |
O3 | 0.87071 (15) | 0.04153 (13) | 0.05372 (4) | 0.0671 (4) | |
N1 | 0.77326 (17) | −0.05512 (13) | 0.04633 (4) | 0.0515 (3) | |
N2 | 0.80030 (15) | 0.05103 (11) | 0.14434 (4) | 0.0444 (3) | |
H2 | 0.7933 | −0.0389 | 0.1410 | 0.053* | |
C1 | 0.56302 (18) | 0.04938 (13) | 0.09612 (4) | 0.0406 (3) | |
C2 | 0.39453 (19) | 0.06428 (16) | 0.10733 (5) | 0.0550 (4) | |
H2A | 0.3649 | 0.1262 | 0.1292 | 0.066* | |
C3 | 0.2705 (2) | −0.0113 (2) | 0.08651 (7) | 0.0682 (5) | |
H3 | 0.1583 | 0.0010 | 0.0942 | 0.082* | |
C4 | 0.3113 (2) | −0.1047 (2) | 0.05447 (6) | 0.0666 (5) | |
H4 | 0.2273 | −0.1569 | 0.0411 | 0.080* | |
C5 | 0.4765 (2) | −0.12086 (17) | 0.04223 (5) | 0.0567 (4) | |
H5 | 0.5047 | −0.1834 | 0.0204 | 0.068* | |
C6 | 0.60025 (18) | −0.04335 (13) | 0.06269 (4) | 0.0422 (3) | |
C7 | 0.68841 (17) | 0.13027 (13) | 0.12274 (5) | 0.0406 (3) | |
C8 | 0.92844 (17) | 0.10094 (13) | 0.17196 (4) | 0.0397 (3) | |
C9 | 1.0050 (2) | 0.23047 (15) | 0.16618 (5) | 0.0524 (4) | |
H9 | 0.9736 | 0.2880 | 0.1434 | 0.063* | |
C10 | 1.1289 (2) | 0.27446 (17) | 0.19454 (6) | 0.0654 (5) | |
H10 | 1.1797 | 0.3620 | 0.1907 | 0.078* | |
C11 | 1.1772 (2) | 0.19029 (18) | 0.22815 (6) | 0.0650 (5) | |
H11 | 1.2595 | 0.2208 | 0.2472 | 0.078* | |
C12 | 1.1025 (2) | 0.05965 (17) | 0.23334 (5) | 0.0588 (4) | |
H12 | 1.1353 | 0.0018 | 0.2560 | 0.071* | |
C13 | 0.9798 (2) | 0.01447 (15) | 0.20530 (5) | 0.0492 (4) | |
H13 | 0.9315 | −0.0742 | 0.2088 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0644 (7) | 0.0268 (5) | 0.0813 (8) | 0.0038 (4) | −0.0136 (6) | −0.0095 (5) |
O2 | 0.0914 (10) | 0.0793 (9) | 0.0877 (10) | 0.0056 (7) | 0.0279 (8) | −0.0350 (7) |
O3 | 0.0525 (7) | 0.0706 (8) | 0.0782 (8) | −0.0103 (6) | 0.0071 (6) | −0.0048 (6) |
N1 | 0.0571 (8) | 0.0501 (7) | 0.0474 (7) | 0.0016 (6) | 0.0041 (6) | −0.0052 (6) |
N2 | 0.0535 (7) | 0.0254 (5) | 0.0541 (7) | −0.0007 (5) | −0.0108 (5) | −0.0064 (4) |
C1 | 0.0432 (8) | 0.0298 (6) | 0.0488 (7) | 0.0017 (5) | −0.0046 (6) | −0.0015 (5) |
C2 | 0.0467 (9) | 0.0514 (8) | 0.0669 (10) | 0.0075 (7) | −0.0033 (7) | −0.0115 (7) |
C3 | 0.0427 (9) | 0.0787 (12) | 0.0831 (12) | −0.0004 (8) | −0.0076 (8) | −0.0063 (10) |
C4 | 0.0562 (11) | 0.0696 (11) | 0.0739 (11) | −0.0136 (8) | −0.0184 (9) | −0.0073 (9) |
C5 | 0.0672 (11) | 0.0510 (8) | 0.0518 (9) | −0.0066 (8) | −0.0107 (7) | −0.0102 (7) |
C6 | 0.0471 (8) | 0.0350 (7) | 0.0444 (7) | 0.0003 (6) | −0.0025 (6) | −0.0013 (5) |
C7 | 0.0455 (8) | 0.0279 (6) | 0.0484 (7) | 0.0007 (5) | 0.0000 (6) | −0.0047 (5) |
C8 | 0.0418 (7) | 0.0332 (6) | 0.0440 (7) | 0.0030 (5) | −0.0008 (6) | −0.0085 (5) |
C9 | 0.0586 (9) | 0.0403 (8) | 0.0582 (9) | −0.0066 (7) | −0.0121 (7) | 0.0013 (6) |
C10 | 0.0621 (10) | 0.0458 (9) | 0.0883 (13) | −0.0085 (8) | −0.0219 (9) | −0.0066 (8) |
C11 | 0.0612 (10) | 0.0593 (10) | 0.0746 (12) | 0.0082 (8) | −0.0261 (9) | −0.0183 (8) |
C12 | 0.0595 (10) | 0.0591 (10) | 0.0577 (9) | 0.0151 (8) | −0.0126 (8) | −0.0017 (7) |
C13 | 0.0495 (9) | 0.0400 (7) | 0.0582 (9) | 0.0054 (6) | −0.0011 (7) | 0.0005 (6) |
O1—C7 | 1.2212 (15) | C4—H4 | 0.9300 |
O2—N1 | 1.2124 (16) | C5—C6 | 1.383 (2) |
O3—N1 | 1.2205 (17) | C5—H5 | 0.9300 |
N1—C6 | 1.470 (2) | C8—C9 | 1.3808 (19) |
N2—C7 | 1.3436 (17) | C8—C13 | 1.385 (2) |
N2—C8 | 1.4142 (17) | C9—C10 | 1.387 (2) |
N2—H2 | 0.8600 | C9—H9 | 0.9300 |
C1—C2 | 1.390 (2) | C10—C11 | 1.371 (2) |
C1—C6 | 1.3942 (19) | C10—H10 | 0.9300 |
C1—C7 | 1.5056 (19) | C11—C12 | 1.382 (3) |
C2—C3 | 1.380 (2) | C11—H11 | 0.9300 |
C2—H2A | 0.9300 | C12—C13 | 1.376 (2) |
C3—C4 | 1.372 (3) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.375 (3) | ||
O2—N1—O3 | 123.65 (14) | C1—C6—N1 | 120.35 (13) |
O2—N1—C6 | 118.28 (13) | O1—C7—N2 | 124.52 (13) |
O3—N1—C6 | 118.05 (12) | O1—C7—C1 | 119.75 (12) |
C7—N2—C8 | 126.45 (11) | N2—C7—C1 | 115.42 (11) |
C7—N2—H2 | 116.8 | C9—C8—C13 | 119.57 (13) |
C8—N2—H2 | 116.8 | C9—C8—N2 | 122.29 (13) |
C2—C1—C6 | 117.12 (13) | C13—C8—N2 | 118.13 (12) |
C2—C1—C7 | 116.51 (12) | C8—C9—C10 | 119.73 (15) |
C6—C1—C7 | 126.31 (13) | C8—C9—H9 | 120.1 |
C3—C2—C1 | 121.07 (15) | C10—C9—H9 | 120.1 |
C3—C2—H2A | 119.5 | C11—C10—C9 | 120.74 (16) |
C1—C2—H2A | 119.5 | C11—C10—H10 | 119.6 |
C4—C3—C2 | 120.52 (17) | C9—C10—H10 | 119.6 |
C4—C3—H3 | 119.7 | C10—C11—C12 | 119.31 (15) |
C2—C3—H3 | 119.7 | C10—C11—H11 | 120.3 |
C3—C4—C5 | 119.95 (15) | C12—C11—H11 | 120.3 |
C3—C4—H4 | 120.0 | C13—C12—C11 | 120.53 (15) |
C5—C4—H4 | 120.0 | C13—C12—H12 | 119.7 |
C4—C5—C6 | 119.41 (15) | C11—C12—H12 | 119.7 |
C4—C5—H5 | 120.3 | C12—C13—C8 | 120.08 (14) |
C6—C5—H5 | 120.3 | C12—C13—H13 | 120.0 |
C5—C6—C1 | 121.89 (15) | C8—C13—H13 | 120.0 |
C5—C6—N1 | 117.66 (13) | ||
C6—C1—C2—C3 | 0.9 (2) | C8—N2—C7—C1 | −178.92 (13) |
C7—C1—C2—C3 | −176.39 (15) | C2—C1—C7—O1 | −56.26 (19) |
C1—C2—C3—C4 | 0.8 (3) | C6—C1—C7—O1 | 126.76 (16) |
C2—C3—C4—C5 | −1.5 (3) | C2—C1—C7—N2 | 117.69 (15) |
C3—C4—C5—C6 | 0.5 (3) | C6—C1—C7—N2 | −59.29 (19) |
C4—C5—C6—C1 | 1.2 (2) | C7—N2—C8—C9 | −30.2 (2) |
C4—C5—C6—N1 | −175.15 (15) | C7—N2—C8—C13 | 151.10 (14) |
C2—C1—C6—C5 | −1.9 (2) | C13—C8—C9—C10 | −1.9 (2) |
C7—C1—C6—C5 | 175.05 (13) | N2—C8—C9—C10 | 179.39 (14) |
C2—C1—C6—N1 | 174.38 (13) | C8—C9—C10—C11 | 0.5 (3) |
C7—C1—C6—N1 | −8.7 (2) | C9—C10—C11—C12 | 0.7 (3) |
O2—N1—C6—C5 | −22.0 (2) | C10—C11—C12—C13 | −0.4 (3) |
O3—N1—C6—C5 | 156.65 (14) | C11—C12—C13—C8 | −1.0 (2) |
O2—N1—C6—C1 | 161.55 (14) | C9—C8—C13—C12 | 2.2 (2) |
O3—N1—C6—C1 | −19.8 (2) | N2—C8—C13—C12 | −179.05 (14) |
C8—N2—C7—O1 | −5.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.86 | 1.99 | 2.8364 (13) | 167 |
Symmetry code: (i) −x+3/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C13H10N2O3 |
Mr | 242.23 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 7.9406 (1), 9.4695 (2), 31.1671 (5) |
V (Å3) | 2343.56 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.32 × 0.17 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan method (SORTAV: Blessing, 1995, 1997) |
Tmin, Tmax | 0.97, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4857, 2639, 1945 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.128, 1.06 |
No. of reflections | 2639 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.16 |
Computer programs: COLLECT (Hooft, 1998), HKL DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corportaion, 1994).
O1—C7 | 1.2212 (15) | N1—C6 | 1.470 (2) |
O2—N1 | 1.2124 (16) | N2—C7 | 1.3436 (17) |
O3—N1 | 1.2205 (17) | N2—C8 | 1.4142 (17) |
O2—N1—O3 | 123.65 (14) | O3—N1—C6 | 118.05 (12) |
O2—N1—C6 | 118.28 (13) | C7—N2—C8 | 126.45 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.86 | 1.99 | 2.8364 (13) | 167 |
Symmetry code: (i) −x+3/2, y−1/2, z. |
2,4,6-Trimethoxy-N-methylaminobenzophenone (tecleanone; Waterman, 1975; Khalid & Waterman, 1981) and 1,3-dimethoxy-N-methylacridone (Tillequim et al., 1980) have been isolated from different plants. These compounds have very similar structures and the former is thought to be a precursor in the biosynthesis of the latter. The isolation of both of these compounds from the same plants, Teclea verdoorniana and Oricio suareolens, has led to the proposal that aminobenzophenones are probable intermediates in the biosynthesis of acridone alkaloids (Adams et al., 1981). This step is of great importance in biological systems as acridone alkaloids have reported success as anticancer drugs (Adams et al., 1981). The conclusion that aminobenzophenones are likely intermediates in the synthesis of acridone alkaloids is further supported by the biomimetic synthesis of acronycine from benzophenone precursor. For this purpose, N-substituted-2-nitrobenzamide has been prepared from 2-nitrobenzoic acid as an intermediate. In this preparation, 2-nitrobenzoic acid, (1), was converted to its acid chloride, (2), followed by nucleophillic replacement of the chloride by the nitrogen on the aniline molecule, resulting in N-phenyl-2-nitrobenzamide, (3). The crystal structure of (3) has been determined by X-ray crystallographic method and reported in this paper.
The structure of (3) is presented in Fig. 1. The molecular dimensions in (3) are normal and lie within expected values (Orpen et al., 1994) for the corresponding bond distances and angles, with bond distances as follows: mean C—Caromatic 1.381 (2), N—O 1.217 (4), N—Caromatic (nitro) 1.470 (2), N—Caromatic (amino) 1.4142 (17), Csp2—N 1.3436 (17), Csp2—Csp2 1.5056 (19) and C═O 1.2212 (15) Å. Both the phenyl rings are essentially planar as expected and their mean planes are inclined at right angles, 89.41 (5)°, with respect to each other. The mean plane of the nitro group is oriented at 21.40 (10)° with the plane of the aromatic ring (C1—C6) to which it is attached. The atoms lying in between the two aromatic rings, i.e. atoms O1/N2/C1/C7/C8 are almost planar, with a maximum deviation of 0.103 (2) Å for C7 and the mean planes of the aromatic rings C1—C6 and C8—C13 form dihedral angles of 58.44 (6) and 31.94 (6)°, respectively, with the mean plane of these atoms.
The structure is stabilized by a strong hydrogen bond between the amido H and carbonyl O atoms [H2···O1 1.99 Å, N2···O1 2.8364 (13) Å and N2—H2···O1 167°], thus linking the molecules into chains along the b axis (Fig. 2). A search of the Cambridge Structural Database (Allen et al., 1993) for similar structures revealed a dozens or so phenylbenzamide derivatives closely related to the structure of (3).