Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103015713/gd1263sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103015713/gd1263Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103015713/gd1263IIsup3.hkl |
CCDC references: 221081; 221082
Crystals of (I) were obtained in a manner similar to that to that described for (III) by Forrester et al. (1992). Zinc dust (1.0 g) was added in portions over a period of 2 h to a stirred mixture of 2'-nitro-4,6-dimethoxy-2-hydroxybenzophenone, (Ia) (1.0 g), in ethanol (200 cm3) and NH4Cl (1.0 g) in water (10 cm3). After stirring overnight at room temperature, work-up in the usual manner yielded 813 mg of solid in the form of a mixture of products. The solid was dissolved in ethyl acetate and the components were separated by preparative thin-layer chromatography (TLC) with silica gel as the stationary phase and ethyl acetate/benzene as eluant. Two comparatively immobile phases (minor components) were not isolated. The most mobile phase, elluted with EtOAc/Bz in a 2:1 ratio, was the aniline, (Ib), resulting from complete reduction of the nitro group of the original benzophenone. The fraction containing (I), the major component, which constituted approximately 75% by weight of the total solids recovered, was obtained by further elution with EtOAc/Bz in a 4:1 ratio. Recovery of the solid and recrystallization from CHCl3 provided crystals of (I) (m.p. 431–434 K) suitable for analysis. 1H NMR (CDCl3): δ 7.67–6.90 (ArH), 6.28 and 6.19 (both d, J = 3 Hz, 3 or 5H), 3.85 (OMe), 3.83 (OMe), 7.11 (OH); m/e: 271 (100%), 256, 254, 242, 240, 212, 200, 196, 120. Reduction of o-nitrobenzophenone, (IIa), in precisely the same manner afforded (II) in admixture with 2-aminobenzophenone (IIb). Compound (II) was isolated by preparative TLC as before and recrystallized from light petroleum (boiling range 333–353 K), yielding orange–yellow prisms (m.p. 323–326 K; literature 326 K; Smith et al., 1953). The melting point of (II) demanded low-temperature (<323 K) manipulation for its recovery and recrystallization. 1H NMR (CDCl3): δ 6.45–8.00 (ArH); m/e: 195 (100%), 188, 167, 139, 118, 105, 92, 77, 63, 51, 39.
In the final stages of refinement of both structures, H atoms were placed in calculated positions and refined using a riding model, with X—H distances of 0.82, 0.93 and 0.96 Å and Uiso(H) values equal to 1.5Ueq, 1.2Ueq and 1.5Ueq for hydroxyl, phenyl and methyl H atoms, respectively. In the case of (I), in the absence of species of atomic number higher than that of oxygen, no significant anomolous dispersion is observed. Thus Friedel pairs were merged; the Flack (1983) parameter is in this case meaningless and the absolute structure is indeterminate. At an appropriate point prior to the final refinement of (II), the essentially planar representation of molecule C as two superposed images was resolved by application of the shape of molecule A (FRAG, FEND and AFIX instructions in SHELXL97; Sheldrick, 1997) to an appropriate selection of atoms from the compound image. Thereafter refinement was continued with the SHELXL97 SAME instruction in place, in order to constrain the bond lengths and angles of molecule C, but not the dihedral angle between the planar fragments, to be the same as those of molecule A.
For both compounds, data collection: Nicolet P3 Software (Nicolet, 1980); cell refinement: Nicolet P3 Software; data reduction: RDNIC (Howie, 1980). Program(s) used to solve structure: SHELXS86 (Sheldrick, 1990) for (I); SHELXS97 (Sheldrick, 1997) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
C15H13NO4 | F(000) = 568 |
Mr = 271.26 | Dx = 1.350 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 15 reflections |
a = 6.941 (3) Å | θ = 9.0–12.4° |
b = 7.277 (3) Å | µ = 0.10 mm−1 |
c = 26.418 (10) Å | T = 298 K |
V = 1334.4 (9) Å3 | Block, orange–yellow |
Z = 4 | 0.70 × 0.60 × 0.60 mm |
Nicolet P3 diffractometer | Rint = 0.002 |
Radiation source: normal-focus sealed tube | θmax = 25.0°, θmin = 1.5° |
Graphite monochromator | h = 0→8 |
θ–2θ scans | k = 0→8 |
1403 measured reflections | l = 0→31 |
1402 independent reflections | 2 standard reflections every 50 reflections |
1251 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.046P)2 + 0.1144P] where P = (Fo2 + 2Fc2)/3 |
1402 reflections | (Δ/σ)max < 0.001 |
184 parameters | Δρmax = 0.11 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C15H13NO4 | V = 1334.4 (9) Å3 |
Mr = 271.26 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.941 (3) Å | µ = 0.10 mm−1 |
b = 7.277 (3) Å | T = 298 K |
c = 26.418 (10) Å | 0.70 × 0.60 × 0.60 mm |
Nicolet P3 diffractometer | Rint = 0.002 |
1403 measured reflections | 2 standard reflections every 50 reflections |
1402 independent reflections | intensity decay: none |
1251 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.11 e Å−3 |
1402 reflections | Δρmin = −0.14 e Å−3 |
184 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 6.2053 (0.0044) x + 2.5464 (0.0075) y − 7.3922 (0.0285) z = 0.9908 (0.0062) * 0.0018 (0.0012) O1 * −0.0005 (0.0013) N1 * −0.0009 (0.0014) C1 * 0.0019 (0.0013) C6 * −0.0023 (0.0012) C7 − 0.0448 (0.0039) C2 − 0.0487 (0.0039) C5 − 0.0105 (0.0037) C8 0.9340 (0.0045) C9 1.8483 (0.0040) O2 − 0.9800 (0.0045) C13 − 1.9110 (0.0037) O4 − 3.0551 (0.0050) C15 Rms deviation of fitted atoms = 0.0016 3.8587 (0.0058) x + 2.2979 (0.0066) y + 20.3132 (0.0182) z = 3.9935 (0.0050) Angle to previous plane (with approximate e.s.d.) = 53.01 (0.09) * −0.0175 (0.0014) C8 * 0.0112 (0.0016) C9 * 0.0030 (0.0016) C10 * −0.0111 (0.0016) C11 * 0.0043 (0.0016) C12 * 0.0100 (0.0014) C13 0.7573 (0.0041) C6 − 0.0242 (0.0033) C7 − 0.9865 (0.0036) O1 0.0148 (0.0035) O2 − 0.0427 (0.0035) O3 − 0.0266 (0.0057) C14 0.0470 (0.0031) O4 0.3268 (0.0049) C15 Rms deviation of fitted atoms = 0.0107 − 6.2386 (0.0035) x + 2.6016 (0.0052) y − 6.7006 (0.0134) z = 1.1394 (0.0034) Angle to previous plane (with approximate e.s.d.) = 54.42 (0.07) * −0.0266 (0.0014) O1 * −0.0070 (0.0016) N1 * 0.0271 (0.0020) C1 * 0.0166 (0.0019) C2 * −0.0224 (0.0020) C3 * −0.0262 (0.0019) C4 * 0.0157 (0.0019) C5 * 0.0317 (0.0019) C6 * −0.0089 (0.0016) C7 − 0.0356 (0.0030) C8 0.9179 (0.0036) C9 1.8579 (0.0032) O2 − 1.0312 (0.0036) C13 − 1.9683 (0.0029) O4 − 3.1331 (0.0039) C15 Rms deviation of fitted atoms = 0.0218 |
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. Anisotropic displacement parameters refined for all non-H atoms. H atoms in calculated positions and refined with a riding model. No atom of atomic number higher than that of O present and Friedel pairs therefore merged (MERG 3). As a consequence the absolute structure is indeterminate and the Flack x parameter meaningless. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.1625 (2) | 0.3863 (2) | 0.13520 (5) | 0.0468 (4) | |
O2 | −0.2585 (3) | 0.9037 (2) | 0.14420 (7) | 0.0629 (5) | |
H2 | −0.2620 | 1.0145 | 0.1497 | 0.094* | |
O3 | 0.2292 (3) | 1.0727 (3) | 0.02961 (7) | 0.0768 (6) | |
O4 | 0.2156 (2) | 0.4687 (2) | 0.10493 (6) | 0.0588 (5) | |
N1 | −0.2519 (3) | 0.2728 (3) | 0.17145 (7) | 0.0503 (5) | |
C1 | −0.2593 (3) | 0.3753 (3) | 0.21300 (8) | 0.0447 (5) | |
C2 | −0.3314 (4) | 0.3239 (4) | 0.26178 (8) | 0.0573 (7) | |
H2A | −0.3880 | 0.2098 | 0.2673 | 0.069* | |
C3 | −0.3136 (4) | 0.4481 (4) | 0.29921 (9) | 0.0653 (8) | |
H3 | −0.3570 | 0.4171 | 0.3314 | 0.078* | |
C4 | −0.2313 (4) | 0.6242 (4) | 0.29159 (8) | 0.0626 (7) | |
H4 | −0.2221 | 0.7043 | 0.3189 | 0.075* | |
C5 | −0.1658 (3) | 0.6795 (4) | 0.24576 (8) | 0.0524 (6) | |
H5 | −0.1147 | 0.7964 | 0.2410 | 0.063* | |
C6 | −0.1782 (3) | 0.5517 (3) | 0.20531 (7) | 0.0422 (5) | |
C7 | −0.1187 (3) | 0.5508 (3) | 0.15564 (7) | 0.0402 (5) | |
C8 | −0.0236 (3) | 0.6840 (3) | 0.12284 (7) | 0.0400 (5) | |
C9 | −0.0968 (3) | 0.8624 (3) | 0.11798 (8) | 0.0453 (5) | |
C10 | −0.0091 (4) | 0.9892 (3) | 0.08658 (8) | 0.0537 (6) | |
H10 | −0.0601 | 1.1067 | 0.0832 | 0.064* | |
C11 | 0.1551 (4) | 0.9397 (3) | 0.06028 (8) | 0.0511 (6) | |
C12 | 0.2349 (4) | 0.7671 (3) | 0.06542 (8) | 0.0489 (6) | |
H12 | 0.3467 | 0.7360 | 0.0480 | 0.059* | |
C13 | 0.1462 (3) | 0.6413 (3) | 0.09678 (7) | 0.0428 (5) | |
C14 | 0.4028 (6) | 1.0292 (5) | 0.00236 (13) | 0.1065 (14) | |
H14A | 0.5037 | 1.0009 | 0.0260 | 0.160* | |
H14B | 0.4402 | 1.1326 | −0.0180 | 0.160* | |
H14C | 0.3803 | 0.9249 | −0.0191 | 0.160* | |
C15 | 0.4046 (4) | 0.4288 (5) | 0.08733 (13) | 0.0815 (9) | |
H15A | 0.4050 | 0.4264 | 0.0510 | 0.122* | |
H15B | 0.4444 | 0.3112 | 0.1000 | 0.122* | |
H15C | 0.4920 | 0.5217 | 0.0991 | 0.122* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0534 (9) | 0.0436 (8) | 0.0434 (7) | −0.0012 (8) | 0.0028 (8) | −0.0020 (7) |
O2 | 0.0611 (10) | 0.0452 (8) | 0.0823 (12) | 0.0048 (9) | 0.0301 (10) | −0.0005 (9) |
O3 | 0.1018 (15) | 0.0642 (11) | 0.0643 (10) | 0.0044 (13) | 0.0402 (11) | 0.0156 (9) |
O4 | 0.0487 (10) | 0.0579 (10) | 0.0699 (10) | 0.0140 (9) | 0.0130 (8) | 0.0121 (9) |
N1 | 0.0522 (11) | 0.0432 (10) | 0.0555 (11) | −0.0049 (10) | 0.0053 (10) | 0.0080 (9) |
C1 | 0.0368 (10) | 0.0541 (12) | 0.0432 (11) | 0.0007 (12) | −0.0013 (10) | 0.0067 (11) |
C2 | 0.0427 (13) | 0.0757 (17) | 0.0535 (13) | −0.0030 (13) | 0.0026 (11) | 0.0218 (13) |
C3 | 0.0486 (13) | 0.106 (2) | 0.0409 (12) | 0.0040 (17) | 0.0010 (11) | 0.0122 (14) |
C4 | 0.0527 (14) | 0.0960 (19) | 0.0391 (11) | −0.0005 (17) | −0.0010 (12) | −0.0097 (13) |
C5 | 0.0454 (13) | 0.0679 (15) | 0.0438 (11) | −0.0047 (13) | −0.0028 (11) | −0.0103 (11) |
C6 | 0.0352 (10) | 0.0553 (13) | 0.0362 (10) | −0.0009 (11) | −0.0020 (9) | 0.0010 (10) |
C7 | 0.0376 (10) | 0.0425 (11) | 0.0407 (10) | −0.0002 (10) | −0.0036 (9) | −0.0022 (9) |
C8 | 0.0409 (11) | 0.0459 (12) | 0.0332 (10) | −0.0011 (10) | −0.0010 (9) | −0.0028 (9) |
C9 | 0.0458 (12) | 0.0452 (12) | 0.0449 (11) | 0.0015 (11) | 0.0065 (10) | −0.0060 (10) |
C10 | 0.0667 (15) | 0.0431 (12) | 0.0513 (12) | 0.0059 (12) | 0.0120 (12) | 0.0050 (11) |
C11 | 0.0672 (16) | 0.0504 (14) | 0.0358 (11) | −0.0025 (14) | 0.0097 (11) | 0.0014 (10) |
C12 | 0.0479 (13) | 0.0610 (14) | 0.0379 (10) | 0.0009 (13) | 0.0078 (11) | −0.0030 (10) |
C13 | 0.0448 (12) | 0.0482 (12) | 0.0355 (9) | 0.0035 (11) | −0.0020 (10) | −0.0011 (10) |
C14 | 0.134 (3) | 0.089 (2) | 0.096 (2) | 0.000 (2) | 0.077 (3) | 0.020 (2) |
C15 | 0.0470 (14) | 0.084 (2) | 0.113 (2) | 0.0213 (16) | 0.0110 (16) | 0.011 (2) |
O1—C7 | 1.348 (3) | C5—H5 | 0.9300 |
O1—N1 | 1.408 (2) | C6—C7 | 1.375 (3) |
O2—C9 | 1.352 (3) | C7—C8 | 1.458 (3) |
O2—H2 | 0.8200 | C8—C13 | 1.400 (3) |
O3—C11 | 1.363 (3) | C8—C9 | 1.400 (3) |
O3—C14 | 1.439 (4) | C9—C10 | 1.382 (3) |
O4—C13 | 1.363 (3) | C10—C11 | 1.382 (3) |
O4—C15 | 1.422 (3) | C10—H10 | 0.9300 |
N1—C1 | 1.328 (3) | C11—C12 | 1.380 (3) |
C1—C6 | 1.417 (3) | C12—C13 | 1.379 (3) |
C1—C2 | 1.432 (3) | C12—H12 | 0.9300 |
C2—C3 | 1.345 (4) | C14—H14A | 0.9600 |
C2—H2A | 0.9300 | C14—H14B | 0.9600 |
C3—C4 | 1.417 (4) | C14—H14C | 0.9600 |
C3—H3 | 0.9300 | C15—H15A | 0.9600 |
C4—C5 | 1.355 (3) | C15—H15B | 0.9600 |
C4—H4 | 0.9300 | C15—H15C | 0.9600 |
C5—C6 | 1.419 (3) | ||
C7—O1—N1 | 110.34 (16) | C9—C8—C7 | 120.45 (19) |
C9—O2—H2 | 109.5 | O2—C9—C10 | 121.7 (2) |
C11—O3—C14 | 117.2 (2) | O2—C9—C8 | 117.4 (2) |
C13—O4—C15 | 117.6 (2) | C10—C9—C8 | 120.9 (2) |
C1—N1—O1 | 104.47 (17) | C9—C10—C11 | 119.4 (2) |
N1—C1—C6 | 112.03 (18) | C9—C10—H10 | 120.3 |
N1—C1—C2 | 127.6 (2) | C11—C10—H10 | 120.3 |
C6—C1—C2 | 120.3 (2) | O3—C11—C12 | 123.6 (2) |
C3—C2—C1 | 117.0 (2) | O3—C11—C10 | 115.2 (2) |
C3—C2—H2A | 121.5 | C12—C11—C10 | 121.2 (2) |
C1—C2—H2A | 121.5 | C13—C12—C11 | 118.9 (2) |
C2—C3—C4 | 122.7 (2) | C13—C12—H12 | 120.5 |
C2—C3—H3 | 118.7 | C11—C12—H12 | 120.5 |
C4—C3—H3 | 118.7 | O4—C13—C12 | 123.3 (2) |
C5—C4—C3 | 122.1 (2) | O4—C13—C8 | 115.13 (19) |
C5—C4—H4 | 119.0 | C12—C13—C8 | 121.6 (2) |
C3—C4—H4 | 119.0 | O3—C14—H14A | 109.5 |
C4—C5—C6 | 117.3 (2) | O3—C14—H14B | 109.5 |
C4—C5—H5 | 121.4 | H14A—C14—H14B | 109.5 |
C6—C5—H5 | 121.4 | O3—C14—H14C | 109.5 |
C7—C6—C1 | 104.57 (19) | H14A—C14—H14C | 109.5 |
C7—C6—C5 | 134.7 (2) | H14B—C14—H14C | 109.5 |
C1—C6—C5 | 120.66 (19) | O4—C15—H15A | 109.5 |
O1—C7—C6 | 108.58 (19) | O4—C15—H15B | 109.5 |
O1—C7—C8 | 117.03 (17) | H15A—C15—H15B | 109.5 |
C6—C7—C8 | 134.4 (2) | O4—C15—H15C | 109.5 |
C13—C8—C9 | 117.78 (19) | H15A—C15—H15C | 109.5 |
C13—C8—C7 | 121.73 (19) | H15B—C15—H15C | 109.5 |
C7—O1—N1—C1 | 0.2 (2) | O1—C7—C8—C9 | 128.2 (2) |
O1—N1—C1—C6 | 0.0 (2) | C6—C7—C8—C9 | −51.9 (3) |
O1—N1—C1—C2 | −177.9 (2) | C13—C8—C9—O2 | −178.54 (19) |
N1—C1—C2—C3 | 176.2 (2) | C7—C8—C9—O2 | −0.8 (3) |
C6—C1—C2—C3 | −1.6 (3) | C13—C8—C9—C10 | 3.0 (3) |
C1—C2—C3—C4 | 1.3 (4) | C7—C8—C9—C10 | −179.3 (2) |
C2—C3—C4—C5 | 0.3 (4) | O2—C9—C10—C11 | −179.5 (2) |
C3—C4—C5—C6 | −1.5 (4) | C8—C9—C10—C11 | −1.1 (3) |
N1—C1—C6—C7 | −0.3 (3) | C14—O3—C11—C12 | −1.5 (4) |
C2—C1—C6—C7 | 177.8 (2) | C14—O3—C11—C10 | 178.6 (3) |
N1—C1—C6—C5 | −177.6 (2) | C9—C10—C11—O3 | 178.9 (2) |
C2—C1—C6—C5 | 0.5 (3) | C9—C10—C11—C12 | −1.0 (4) |
C4—C5—C6—C7 | −175.3 (2) | O3—C11—C12—C13 | −178.7 (2) |
C4—C5—C6—C1 | 1.1 (3) | C10—C11—C12—C13 | 1.2 (3) |
N1—O1—C7—C6 | −0.4 (2) | C15—O4—C13—C12 | 11.3 (3) |
N1—O1—C7—C8 | 179.57 (18) | C15—O4—C13—C8 | −168.5 (2) |
C1—C6—C7—O1 | 0.4 (2) | C11—C12—C13—O4 | −178.9 (2) |
C5—C6—C7—O1 | 177.2 (2) | C11—C12—C13—C8 | 0.9 (3) |
C1—C6—C7—C8 | −179.6 (2) | C9—C8—C13—O4 | 176.89 (19) |
C5—C6—C7—C8 | −2.8 (4) | C7—C8—C13—O4 | −0.8 (3) |
O1—C7—C8—C13 | −54.2 (3) | C9—C8—C13—C12 | −2.9 (3) |
C6—C7—C8—C13 | 125.8 (3) | C7—C8—C13—C12 | 179.4 (2) |
C13H9NO | F(000) = 1632 |
Mr = 195.21 | Dx = 1.297 Mg m−3 |
Monoclinic, I2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -I 2yc | Cell parameters from 14 reflections |
a = 12.027 (13) Å | θ = 7.7–11.6° |
b = 10.706 (14) Å | µ = 0.08 mm−1 |
c = 31.76 (3) Å | T = 298 K |
β = 102.11 (8)° | Block, pale brown |
V = 3998 (8) Å3 | 0.70 × 0.50 × 0.50 mm |
Z = 16 |
Nicolet P3 diffractometer | Rint = 0.041 |
Radiation source: normal-focus sealed tube | θmax = 25.1°, θmin = 1.3° |
Graphite monochromator | h = 0→14 |
θ–2θ scans | k = 0→12 |
3726 measured reflections | l = −37→36 |
3551 independent reflections | 2 standard reflections every 50 reflections |
1555 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0333P)2 + 0.6711P] where P = (Fo2 + 2Fc2)/3 |
3551 reflections | (Δ/σ)max = 0.001 |
348 parameters | Δρmax = 0.10 e Å−3 |
40 restraints | Δρmin = −0.12 e Å−3 |
C13H9NO | V = 3998 (8) Å3 |
Mr = 195.21 | Z = 16 |
Monoclinic, I2/c | Mo Kα radiation |
a = 12.027 (13) Å | µ = 0.08 mm−1 |
b = 10.706 (14) Å | T = 298 K |
c = 31.76 (3) Å | 0.70 × 0.50 × 0.50 mm |
β = 102.11 (8)° |
Nicolet P3 diffractometer | Rint = 0.041 |
3726 measured reflections | 2 standard reflections every 50 reflections |
3551 independent reflections | intensity decay: none |
1555 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.054 | 40 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.10 e Å−3 |
3551 reflections | Δρmin = −0.12 e Å−3 |
348 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 8.0081 (0.0127) x + 2.4908 (0.0092) y + 26.4497 (0.0399) z = 9.2028 (0.0174) * 0.0048 (0.0027) C1A * −0.0084 (0.0027) C2A * −0.0076 (0.0028) C3A * 0.0099 (0.0025) C4A * 0.0063 (0.0024) C5A * −0.0063 (0.0024) C6A * −0.0121 (0.0021) C7A * 0.0101 (0.0024) N1A * 0.0034 (0.0020) O1A Rms deviation of fitted atoms = 0.0081 − 7.1999 (0.0154) x + 4.7965 (0.0143) y + 24.6083 (0.0424) z = 9.3468 (0.0191) Angle to previous plane (with approximate e.s.d.) = 13.21 (0.16) * −0.0023 (0.0021) C8A * −0.0011 (0.0021) C9A * 0.0037 (0.0023) C10A * −0.0029 (0.0025) C11A * −0.0006 (0.0025) C12A * 0.0031 (0.0023) C13A Rms deviation of fitted atoms = 0.0025 7.1136 (0.0137) x − 2.0490 (0.0119) y + 20.3827 (0.0382) z = 14.8148 (0.0271) Angle to previous plane (with approximate e.s.d.) = 85.39 (0.11) * 0.0125 (0.0029) C1B * 0.0211 (0.0024) C2B * 0.0103 (0.0028) C3B * −0.0248 (0.0025) C4B * −0.0085 (0.0020) C5B * 0.0164 (0.0025) C6B * 0.0043 (0.0030) C7B * −0.0510 (0.0043) N1B_b * 0.0198 (0.0064) O1B Rms deviation of fitted atoms = 0.0228 7.0827 (0.0139) x + 2.1968 (0.0117) y + 20.3514 (0.0378) z = 15.7554 (0.0304) Angle to previous plane (with approximate e.s.d.) = 22.87 (0.15) * 0.0104 (0.0018) C1B_$1 * −0.0017 (0.0021) C2B_$1 * −0.0090 (0.0022) C3B_$1 * 0.0110 (0.0020) C4B_$1 * −0.0022 (0.0018) C5B_$1 * −0.0084 (0.0018) C6B_$1 Rms deviation of fitted atoms = 0.0081 7.0827 (0.0139) x − 2.1968 (0.0117) y + 20.3514 (0.0377) z = 14.7717 (0.0265) Angle to previous plane (with approximate e.s.d.) = 23.68 (0.15) * −0.0104 (0.0019) C1B * 0.0017 (0.0021) C2B * 0.0090 (0.0022) C3B * −0.0110 (0.0020) C4B * 0.0022 (0.0018) C5B * 0.0084 (0.0018) C6B −0.0098 (0.0031) C7B −0.0901 (0.0058) N1B_b −0.0137 (0.0105) O1B Rms deviation of fitted atoms = 0.0081 8.0913 (0.0319) x + 4.7304 (0.0615) y + 13.9454 (0.1760) z = 6.8218 (0.0402) Angle to previous plane (with approximate e.s.d.) = 39.70 (0.40) * −0.0152 (0.0256) C1C * 0.0081 (0.0226) C2C * −0.0033 (0.0140) C3C * −0.0083 (0.0155) C4C * 0.0114 (0.0190) C5C * 0.0098 (0.0118) C6C * −0.0102 (0.0093) C7C * 0.0068 (0.0111) N1C * 0.0009 (0.0067) O1C Rms deviation of fitted atoms = 0.0091 7.3689 (0.0966) x + 6.2888 (0.1018) y + 12.3365 (0.3155) z = 6.5687 (0.0382) Angle to previous plane (with approximate e.s.d.) = 9.77 (1.36) * −0.0044 (0.0134) C8C * 0.0132 (0.0148) C9C * −0.0208 (0.0276) C10C * 0.0199 (0.0277) C11C * −0.0115 (0.0188) C12C * 0.0036 (0.0174) C13C Rms deviation of fitted atoms = 0.0140 |
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. Anisotropic displacement parameters refined for all non-H atoms. H atoms placed in calculated positions with C—H 0.93 A and refined riding with Uiso 1.2Ueq of the attached atom. Molecule C extracted from a composite image of a pair of molecules close to and related by a crystallographic centre of symmetry. Its geometry optimized using molecule A as a model (SHELXL97 FRAG and FEND) then refined with 1–2 (bond) and 1–3 (angle) distances constrained (SHELXL97 SAME) to match those of molecule A. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1A | 0.8157 (3) | 0.2153 (3) | 0.57481 (10) | 0.0796 (9) | |
C2A | 0.9203 (3) | 0.2458 (4) | 0.60310 (10) | 0.0973 (11) | |
H2A | 0.9618 | 0.1858 | 0.6210 | 0.117* | |
C3A | 0.9569 (3) | 0.3643 (4) | 0.60306 (11) | 0.1095 (13) | |
H3A | 1.0252 | 0.3863 | 0.6212 | 0.131* | |
C4A | 0.8942 (3) | 0.4571 (4) | 0.57600 (11) | 0.1095 (12) | |
H4A | 0.9220 | 0.5384 | 0.5773 | 0.131* | |
C5A | 0.7947 (3) | 0.4303 (3) | 0.54827 (9) | 0.0886 (10) | |
H5A | 0.7548 | 0.4917 | 0.5306 | 0.106* | |
C6A | 0.7539 (3) | 0.3063 (3) | 0.54710 (9) | 0.0682 (8) | |
C7A | 0.6611 (3) | 0.2435 (3) | 0.52470 (9) | 0.0695 (8) | |
C8A | 0.5628 (3) | 0.2735 (3) | 0.49107 (9) | 0.0687 (8) | |
C9A | 0.5582 (3) | 0.3836 (3) | 0.46832 (9) | 0.0852 (9) | |
H9A | 0.6181 | 0.4401 | 0.4748 | 0.102* | |
C10A | 0.4648 (3) | 0.4108 (3) | 0.43588 (10) | 0.1003 (11) | |
H10A | 0.4623 | 0.4857 | 0.4209 | 0.120* | |
C11A | 0.3766 (3) | 0.3290 (4) | 0.42578 (11) | 0.1011 (11) | |
H11A | 0.3146 | 0.3476 | 0.4038 | 0.121* | |
C12A | 0.3794 (3) | 0.2190 (4) | 0.44813 (12) | 0.1037 (11) | |
H12A | 0.3192 | 0.1630 | 0.4414 | 0.124* | |
C13A | 0.4719 (3) | 0.1916 (3) | 0.48065 (11) | 0.0945 (10) | |
H13A | 0.4731 | 0.1171 | 0.4958 | 0.113* | |
N1A | 0.7671 (3) | 0.1048 (3) | 0.57071 (9) | 0.1077 (10) | |
O1A | 0.66755 (19) | 0.1233 (2) | 0.53857 (7) | 0.0978 (7) | |
C1B | 0.1341 (3) | 0.2688 (3) | 0.70768 (9) | 0.0698 (8) | |
H1B | 0.1314 | 0.3514 | 0.7165 | 0.084* | 0.50 |
C2B | 0.2049 (3) | 0.2359 (4) | 0.68008 (10) | 0.0866 (10) | |
H2B | 0.2506 | 0.2954 | 0.6707 | 0.104* | |
C3B | 0.2060 (3) | 0.1158 (4) | 0.66708 (10) | 0.0932 (11) | |
H3B | 0.2538 | 0.0928 | 0.6489 | 0.112* | |
C4B | 0.1369 (3) | 0.0254 (3) | 0.68040 (10) | 0.0810 (9) | |
H4B | 0.1377 | −0.0560 | 0.6702 | 0.097* | |
C5B | 0.0685 (2) | 0.0549 (3) | 0.70801 (9) | 0.0694 (8) | |
H5B | 0.0239 | −0.0060 | 0.7172 | 0.083* | |
C6B | 0.0665 (2) | 0.1788 (3) | 0.72240 (8) | 0.0574 (7) | |
C7B | 0.0000 | 0.2284 (4) | 0.7500 | 0.0624 (10) | |
N1B | 0.1089 (4) | 0.3804 (4) | 0.72455 (16) | 0.0802 (14) | 0.50 |
O1B | 0.0320 (4) | 0.3527 (3) | 0.7521 (4) | 0.078 (2) | 0.50 |
C1C | 0.2011 (19) | 0.1413 (17) | 0.3235 (7) | 0.063 (4) | 0.50 |
C2C | 0.138 (2) | 0.1563 (19) | 0.3565 (8) | 0.082 (4) | 0.50 |
H2C | 0.1409 | 0.0949 | 0.3774 | 0.098* | 0.50 |
C3C | 0.0747 (11) | 0.2601 (10) | 0.3574 (4) | 0.098 (4) | 0.50 |
H3C | 0.0322 | 0.2697 | 0.3784 | 0.118* | 0.50 |
C4C | 0.0735 (17) | 0.3551 (10) | 0.3255 (5) | 0.090 (4) | 0.50 |
H4C | 0.0288 | 0.4256 | 0.3263 | 0.109* | 0.50 |
C5C | 0.1343 (19) | 0.3467 (17) | 0.2945 (7) | 0.066 (4) | 0.50 |
H5C | 0.1328 | 0.4109 | 0.2746 | 0.080* | 0.50 |
C6C | 0.2001 (9) | 0.2388 (11) | 0.2928 (3) | 0.060 (3) | 0.50 |
C7C | 0.2686 (7) | 0.1954 (8) | 0.2663 (3) | 0.071 (2) | 0.50 |
C8C | 0.3051 (11) | 0.2398 (11) | 0.2276 (3) | 0.065 (3) | 0.50 |
C9C | 0.2575 (8) | 0.3430 (9) | 0.2048 (3) | 0.083 (3) | 0.50 |
H9C | 0.2044 | 0.3905 | 0.2152 | 0.099* | 0.50 |
C10C | 0.288 (3) | 0.377 (2) | 0.1664 (8) | 0.117 (12) | 0.50 |
H10C | 0.2508 | 0.4439 | 0.1505 | 0.141* | 0.50 |
C11C | 0.372 (3) | 0.315 (2) | 0.1516 (9) | 0.135 (12) | 0.50 |
H11C | 0.3965 | 0.3410 | 0.1272 | 0.162* | 0.50 |
C12C | 0.4171 (15) | 0.2128 (15) | 0.1739 (5) | 0.113 (6) | 0.50 |
H12C | 0.4703 | 0.1659 | 0.1633 | 0.135* | 0.50 |
C13C | 0.388 (2) | 0.1753 (19) | 0.2117 (8) | 0.098 (9) | 0.50 |
H13C | 0.4237 | 0.1066 | 0.2266 | 0.118* | 0.50 |
N1C | 0.2671 (7) | 0.0481 (6) | 0.3184 (3) | 0.105 (3) | 0.50 |
O1C | 0.3087 (4) | 0.0839 (4) | 0.28169 (16) | 0.0892 (13) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.083 (2) | 0.086 (3) | 0.069 (2) | 0.021 (2) | 0.0154 (19) | 0.003 (2) |
C2A | 0.096 (3) | 0.114 (3) | 0.079 (2) | 0.029 (3) | 0.012 (2) | 0.012 (2) |
C3A | 0.105 (3) | 0.146 (4) | 0.069 (2) | 0.001 (3) | −0.002 (2) | 0.004 (3) |
C4A | 0.120 (3) | 0.118 (3) | 0.081 (2) | −0.027 (3) | 0.000 (2) | 0.009 (2) |
C5A | 0.103 (3) | 0.093 (3) | 0.065 (2) | −0.008 (2) | 0.0063 (19) | 0.0129 (19) |
C6A | 0.077 (2) | 0.078 (2) | 0.0522 (18) | 0.012 (2) | 0.0179 (16) | 0.0053 (18) |
C7A | 0.082 (2) | 0.066 (2) | 0.0656 (19) | 0.012 (2) | 0.0260 (18) | 0.0047 (17) |
C8A | 0.073 (2) | 0.071 (2) | 0.0653 (19) | 0.0026 (18) | 0.0199 (17) | −0.0001 (18) |
C9A | 0.092 (2) | 0.091 (2) | 0.068 (2) | −0.012 (2) | 0.0061 (19) | 0.0071 (19) |
C10A | 0.112 (3) | 0.100 (3) | 0.080 (2) | −0.012 (2) | −0.001 (2) | 0.017 (2) |
C11A | 0.089 (3) | 0.115 (3) | 0.092 (3) | −0.004 (3) | 0.002 (2) | 0.012 (2) |
C12A | 0.082 (3) | 0.112 (3) | 0.113 (3) | −0.019 (2) | 0.010 (2) | 0.003 (3) |
C13A | 0.090 (3) | 0.089 (3) | 0.104 (3) | −0.004 (2) | 0.018 (2) | 0.019 (2) |
N1A | 0.114 (3) | 0.087 (2) | 0.114 (2) | 0.027 (2) | 0.003 (2) | 0.0098 (19) |
O1A | 0.1034 (18) | 0.0743 (16) | 0.1092 (17) | 0.0118 (14) | 0.0073 (14) | 0.0067 (14) |
C1B | 0.078 (2) | 0.064 (2) | 0.0630 (19) | −0.0052 (19) | 0.0058 (17) | −0.0008 (17) |
C2B | 0.074 (2) | 0.113 (3) | 0.074 (2) | −0.016 (2) | 0.0179 (18) | −0.001 (2) |
C3B | 0.068 (2) | 0.132 (3) | 0.082 (2) | 0.007 (3) | 0.0210 (18) | −0.014 (3) |
C4B | 0.088 (2) | 0.074 (2) | 0.076 (2) | 0.012 (2) | 0.0072 (19) | −0.0133 (18) |
C5B | 0.075 (2) | 0.071 (2) | 0.0580 (18) | −0.0014 (17) | 0.0045 (16) | 0.0044 (17) |
C6B | 0.0543 (17) | 0.0612 (19) | 0.0525 (17) | 0.0026 (16) | 0.0016 (14) | −0.0001 (15) |
C7B | 0.075 (3) | 0.047 (3) | 0.061 (3) | 0.000 | 0.004 (2) | 0.000 |
N1B | 0.092 (4) | 0.071 (3) | 0.080 (4) | −0.015 (3) | 0.023 (3) | −0.001 (3) |
O1B | 0.100 (7) | 0.059 (2) | 0.078 (3) | −0.006 (2) | 0.023 (7) | −0.010 (3) |
C1C | 0.070 (7) | 0.072 (8) | 0.047 (8) | −0.001 (6) | 0.013 (7) | 0.003 (6) |
C2C | 0.071 (9) | 0.084 (8) | 0.092 (12) | −0.014 (6) | 0.022 (8) | −0.018 (7) |
C3C | 0.096 (7) | 0.102 (9) | 0.100 (9) | −0.014 (6) | 0.027 (6) | −0.024 (7) |
C4C | 0.087 (7) | 0.090 (8) | 0.085 (8) | −0.003 (8) | 0.000 (6) | 0.002 (7) |
C5C | 0.061 (8) | 0.065 (6) | 0.071 (8) | 0.004 (7) | 0.008 (8) | −0.003 (7) |
C6C | 0.050 (5) | 0.060 (7) | 0.060 (7) | 0.004 (5) | −0.008 (5) | 0.003 (6) |
C7C | 0.064 (5) | 0.055 (5) | 0.086 (7) | −0.002 (5) | 0.000 (4) | −0.005 (4) |
C8C | 0.057 (6) | 0.066 (6) | 0.064 (7) | −0.008 (5) | −0.005 (6) | −0.005 (7) |
C9C | 0.087 (7) | 0.062 (7) | 0.096 (9) | 0.008 (6) | 0.011 (6) | −0.008 (6) |
C10C | 0.16 (3) | 0.097 (15) | 0.079 (15) | −0.056 (13) | −0.019 (13) | 0.020 (10) |
C11C | 0.15 (3) | 0.18 (3) | 0.070 (11) | −0.074 (18) | 0.009 (14) | −0.014 (17) |
C12C | 0.085 (8) | 0.174 (19) | 0.081 (9) | −0.007 (14) | 0.022 (8) | −0.023 (12) |
C13C | 0.068 (11) | 0.135 (16) | 0.083 (10) | 0.002 (9) | −0.008 (8) | −0.022 (9) |
N1C | 0.138 (6) | 0.071 (5) | 0.107 (6) | 0.013 (4) | 0.026 (5) | 0.012 (5) |
O1C | 0.105 (4) | 0.066 (3) | 0.097 (4) | 0.013 (3) | 0.022 (3) | 0.014 (3) |
C1A—N1A | 1.314 (4) | C4B—C5B | 1.359 (4) |
C1A—C6A | 1.415 (4) | C4B—H4B | 0.9300 |
C1A—C2A | 1.422 (4) | C5B—C6B | 1.405 (4) |
C2A—C3A | 1.343 (5) | C5B—H5B | 0.9300 |
C2A—H2A | 0.9300 | C6B—C7B | 1.409 (3) |
C3A—C4A | 1.422 (4) | C7B—O1B | 1.383 (5) |
C3A—H3A | 0.9300 | N1B—O1B | 1.432 (12) |
C4A—C5A | 1.359 (4) | C1C—N1C | 1.305 (12) |
C4A—H4A | 0.9300 | C1C—C6C | 1.425 (14) |
C5A—C6A | 1.413 (4) | C1C—C2C | 1.426 (14) |
C5A—H5A | 0.9300 | C2C—C3C | 1.352 (15) |
C6A—C7A | 1.369 (4) | C2C—H2C | 0.9300 |
C7A—O1A | 1.357 (3) | C3C—C4C | 1.433 (16) |
C7A—C8A | 1.453 (4) | C3C—H3C | 0.9300 |
C8A—C9A | 1.377 (4) | C4C—C5C | 1.347 (14) |
C8A—C13A | 1.387 (4) | C4C—H4C | 0.9300 |
C9A—C10A | 1.386 (4) | C5C—C6C | 1.408 (13) |
C9A—H9A | 0.9300 | C5C—H5C | 0.9300 |
C10A—C11A | 1.361 (4) | C6C—C7C | 1.376 (12) |
C10A—H10A | 0.9300 | C7C—O1C | 1.340 (9) |
C11A—C12A | 1.372 (4) | C7C—C8C | 1.468 (10) |
C11A—H11A | 0.9300 | C8C—C9C | 1.378 (11) |
C12A—C13A | 1.381 (4) | C8C—C13C | 1.392 (14) |
C12A—H12A | 0.9300 | C9C—C10C | 1.396 (15) |
C13A—H13A | 0.9300 | C9C—H9C | 0.9300 |
N1A—O1A | 1.415 (3) | C10C—C11C | 1.376 (17) |
C1B—N1B | 1.369 (5) | C10C—H10C | 0.9300 |
C1B—C2B | 1.390 (4) | C11C—C12C | 1.350 (16) |
C1B—C6B | 1.403 (4) | C11C—H11C | 0.9300 |
C1B—H1B | 0.9300 | C12C—C13C | 1.378 (15) |
C2B—C3B | 1.351 (4) | C12C—H12C | 0.9300 |
C2B—H2B | 0.9300 | C13C—H13C | 0.9300 |
C3B—C4B | 1.398 (4) | N1C—O1C | 1.415 (8) |
C3B—H3B | 0.9300 | ||
N1A—C1A—C6A | 113.2 (3) | C3B—C4B—H4B | 119.6 |
N1A—C1A—C2A | 125.8 (3) | C4B—C5B—C6B | 118.9 (3) |
C6A—C1A—C2A | 121.0 (4) | C4B—C5B—H5B | 120.5 |
C3A—C2A—C1A | 117.6 (3) | C6B—C5B—H5B | 120.5 |
C3A—C2A—H2A | 121.2 | C1B—C6B—C5B | 119.3 (3) |
C1A—C2A—H2A | 121.2 | C1B—C6B—C7B | 113.1 (3) |
C2A—C3A—C4A | 121.9 (4) | C5B—C6B—C7B | 127.5 (3) |
C2A—C3A—H3A | 119.1 | O1B—C7B—C6B | 101.8 (5) |
C4A—C3A—H3A | 119.1 | O1B—C7B—C6Bi | 121.4 (5) |
C5A—C4A—C3A | 121.8 (4) | C6B—C7B—C6Bi | 135.7 (4) |
C5A—C4A—H4A | 119.1 | C1B—N1B—O1B | 106.4 (4) |
C3A—C4A—H4A | 119.1 | C7B—O1B—N1B | 112.3 (6) |
C4A—C5A—C6A | 118.0 (3) | N1C—C1C—C6C | 113.2 (10) |
C4A—C5A—H5A | 121.0 | N1C—C1C—C2C | 127.3 (12) |
C6A—C5A—H5A | 121.0 | C6C—C1C—C2C | 119.4 (10) |
C7A—C6A—C5A | 135.8 (3) | C3C—C2C—C1C | 119.7 (14) |
C7A—C6A—C1A | 104.5 (3) | C3C—C2C—H2C | 120.1 |
C5A—C6A—C1A | 119.7 (3) | C1C—C2C—H2C | 120.1 |
O1A—C7A—C6A | 108.2 (3) | C2C—C3C—C4C | 119.4 (11) |
O1A—C7A—C8A | 115.6 (3) | C2C—C3C—H3C | 120.3 |
C6A—C7A—C8A | 136.2 (3) | C4C—C3C—H3C | 120.3 |
C9A—C8A—C13A | 118.2 (3) | C5C—C4C—C3C | 122.9 (12) |
C9A—C8A—C7A | 120.8 (3) | C5C—C4C—H4C | 118.6 |
C13A—C8A—C7A | 121.0 (3) | C3C—C4C—H4C | 118.6 |
C8A—C9A—C10A | 120.5 (3) | C4C—C5C—C6C | 118.5 (12) |
C8A—C9A—H9A | 119.8 | C4C—C5C—H5C | 120.7 |
C10A—C9A—H9A | 119.8 | C6C—C5C—H5C | 120.7 |
C11A—C10A—C9A | 120.6 (3) | C7C—C6C—C5C | 135.6 (12) |
C11A—C10A—H10A | 119.7 | C7C—C6C—C1C | 104.5 (10) |
C9A—C10A—H10A | 119.7 | C5C—C6C—C1C | 119.9 (9) |
C10A—C11A—C12A | 119.8 (3) | O1C—C7C—C6C | 107.1 (9) |
C10A—C11A—H11A | 120.1 | O1C—C7C—C8C | 116.5 (8) |
C12A—C11A—H11A | 120.1 | C6C—C7C—C8C | 136.4 (11) |
C11A—C12A—C13A | 119.9 (3) | C9C—C8C—C13C | 117.2 (12) |
C11A—C12A—H12A | 120.1 | C9C—C8C—C7C | 122.4 (12) |
C13A—C12A—H12A | 120.1 | C13C—C8C—C7C | 120.4 (11) |
C12A—C13A—C8A | 121.0 (3) | C8C—C9C—C10C | 121.1 (13) |
C12A—C13A—H13A | 119.5 | C8C—C9C—H9C | 119.5 |
C8A—C13A—H13A | 119.5 | C10C—C9C—H9C | 119.5 |
C1A—N1A—O1A | 103.7 (3) | C11C—C10C—C9C | 121.0 (17) |
C7A—O1A—N1A | 110.4 (2) | C11C—C10C—H10C | 119.5 |
N1B—C1B—C2B | 133.1 (4) | C9C—C10C—H10C | 119.5 |
N1B—C1B—C6B | 106.2 (3) | C12C—C11C—C10C | 117.3 (16) |
C2B—C1B—C6B | 120.7 (3) | C12C—C11C—H11C | 121.4 |
C2B—C1B—H1B | 119.6 | C10C—C11C—H11C | 121.4 |
C6B—C1B—H1B | 119.6 | C11C—C12C—C13C | 123.0 (15) |
C3B—C2B—C1B | 118.7 (3) | C11C—C12C—H12C | 118.5 |
C3B—C2B—H2B | 120.6 | C13C—C12C—H12C | 118.5 |
C1B—C2B—H2B | 120.6 | C12C—C13C—C8C | 120.3 (15) |
C2B—C3B—C4B | 121.4 (3) | C12C—C13C—H13C | 119.8 |
C2B—C3B—H3B | 119.3 | C8C—C13C—H13C | 119.8 |
C4B—C3B—H3B | 119.3 | C1C—N1C—O1C | 102.9 (8) |
C5B—C4B—C3B | 120.9 (3) | C7C—O1C—N1C | 112.3 (6) |
C5B—C4B—H4B | 119.6 | ||
N1A—C1A—C2A—C3A | −179.8 (4) | C5B—C6B—C7B—O1B | −179.1 (5) |
C6A—C1A—C2A—C3A | 1.2 (5) | C1B—C6B—C7B—C6Bi | −168.7 (2) |
C1A—C2A—C3A—C4A | 0.2 (5) | C5B—C6B—C7B—C6Bi | 13.4 (2) |
C2A—C3A—C4A—C5A | −1.0 (6) | C2B—C1B—N1B—O1B | −178.3 (5) |
C3A—C4A—C5A—C6A | 0.4 (5) | C6B—C1B—N1B—O1B | 4.3 (6) |
C4A—C5A—C6A—C7A | 179.9 (3) | C6B—C7B—O1B—N1B | 4.0 (7) |
C4A—C5A—C6A—C1A | 0.9 (4) | C1B—N1B—O1B—C7B | −5.5 (8) |
N1A—C1A—C6A—C7A | −0.2 (4) | N1C—C1C—C2C—C3C | 179 (2) |
C2A—C1A—C6A—C7A | 179.0 (3) | C6C—C1C—C2C—C3C | 3 (5) |
N1A—C1A—C6A—C5A | 179.1 (3) | C1C—C2C—C3C—C4C | −1 (4) |
C2A—C1A—C6A—C5A | −1.7 (4) | C2C—C3C—C4C—C5C | −1 (3) |
C5A—C6A—C7A—O1A | −178.7 (3) | C3C—C4C—C5C—C6C | 1 (3) |
C1A—C6A—C7A—O1A | 0.4 (3) | C4C—C5C—C6C—C7C | 177.9 (16) |
C5A—C6A—C7A—C8A | 1.8 (6) | C4C—C5C—C6C—C1C | 0 (3) |
C1A—C6A—C7A—C8A | −179.1 (3) | N1C—C1C—C6C—C7C | 3 (2) |
O1A—C7A—C8A—C9A | −166.6 (3) | C2C—C1C—C6C—C7C | 179 (2) |
C6A—C7A—C8A—C9A | 12.8 (5) | N1C—C1C—C6C—C5C | −179.0 (19) |
O1A—C7A—C8A—C13A | 12.5 (4) | C2C—C1C—C6C—C5C | −2 (4) |
C6A—C7A—C8A—C13A | −168.0 (3) | C5C—C6C—C7C—O1C | 180.0 (19) |
C13A—C8A—C9A—C10A | −0.1 (4) | C1C—C6C—C7C—O1C | −2.0 (15) |
C7A—C8A—C9A—C10A | 179.1 (3) | C5C—C6C—C7C—C8C | 0 (3) |
C8A—C9A—C10A—C11A | −0.5 (5) | C1C—C6C—C7C—C8C | 177.7 (14) |
C9A—C10A—C11A—C12A | 0.7 (5) | O1C—C7C—C8C—C9C | 170.1 (9) |
C10A—C11A—C12A—C13A | −0.2 (5) | C6C—C7C—C8C—C9C | −10 (2) |
C11A—C12A—C13A—C8A | −0.3 (5) | O1C—C7C—C8C—C13C | −7.8 (18) |
C9A—C8A—C13A—C12A | 0.5 (5) | C6C—C7C—C8C—C13C | 172.6 (16) |
C7A—C8A—C13A—C12A | −178.7 (3) | C13C—C8C—C9C—C10C | 3 (3) |
C6A—C1A—N1A—O1A | 0.0 (4) | C7C—C8C—C9C—C10C | −175 (2) |
C2A—C1A—N1A—O1A | −179.2 (3) | C8C—C9C—C10C—C11C | −5 (5) |
C6A—C7A—O1A—N1A | −0.4 (3) | C9C—C10C—C11C—C12C | 5 (6) |
C8A—C7A—O1A—N1A | 179.2 (2) | C10C—C11C—C12C—C13C | −4 (5) |
C1A—N1A—O1A—C7A | 0.3 (3) | C11C—C12C—C13C—C8C | 3 (4) |
N1B—C1B—C2B—C3B | −176.0 (4) | C9C—C8C—C13C—C12C | −2 (3) |
C6B—C1B—C2B—C3B | 1.1 (4) | C7C—C8C—C13C—C12C | 176.1 (17) |
C1B—C2B—C3B—C4B | 0.7 (5) | C6C—C1C—N1C—O1C | −2 (2) |
C2B—C3B—C4B—C5B | −2.0 (5) | C2C—C1C—N1C—O1C | −179 (3) |
C3B—C4B—C5B—C6B | 1.3 (4) | C6C—C7C—O1C—N1C | 1.0 (8) |
N1B—C1B—C6B—C5B | 176.0 (3) | C8C—C7C—O1C—N1C | −178.8 (7) |
C2B—C1B—C6B—C5B | −1.8 (4) | C1C—N1C—O1C—C7C | 0.6 (14) |
N1B—C1B—C6B—C7B | −2.1 (3) | O1B—C7B—C6Bi—C1Bi | 25.7 (5) |
C2B—C1B—C6B—C7B | −179.9 (2) | O1B—C7B—C6Bi—C5Bi | −152.3 (5) |
C4B—C5B—C6B—C1B | 0.5 (4) | C6B—C7B—C6Bi—C1Bi | −168.7 (2) |
C4B—C5B—C6B—C7B | 178.4 (2) | C6B—C7B—C6Bi—C5Bi | 13.4 (2) |
C1B—C6B—C7B—O1B | −1.1 (5) |
Symmetry code: (i) −x, y, −z+3/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C15H13NO4 | C13H9NO |
Mr | 271.26 | 195.21 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, I2/c |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 6.941 (3), 7.277 (3), 26.418 (10) | 12.027 (13), 10.706 (14), 31.76 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 102.11 (8), 90 |
V (Å3) | 1334.4 (9) | 3998 (8) |
Z | 4 | 16 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.08 |
Crystal size (mm) | 0.70 × 0.60 × 0.60 | 0.70 × 0.50 × 0.50 |
Data collection | ||
Diffractometer | Nicolet P3 diffractometer | Nicolet P3 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1403, 1402, 1251 | 3726, 3551, 1555 |
Rint | 0.002 | 0.041 |
(sin θ/λ)max (Å−1) | 0.595 | 0.596 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.082, 1.09 | 0.054, 0.123, 1.02 |
No. of reflections | 1402 | 3551 |
No. of parameters | 184 | 348 |
No. of restraints | 0 | 40 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.11, −0.14 | 0.10, −0.12 |
Computer programs: Nicolet P3 Software (Nicolet, 1980), Nicolet P3 Software, RDNIC (Howie, 1980), SHELXS86 (Sheldrick, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
I | IIA | IIBa | IIC | |
O1—N1 | 1.408 (2) | 1.415 (3) | 1.432 (12) | 1.415 (8) |
N1—C1 | 1.328 (3) | 1.314 (4) | 1.369 (5) | 1.305 (12) |
C1—C6 | 1.417 (3) | 1.415 (4) | 1.403 (4) | 1.425 (14) |
C1—C2 | 1.432 (3) | 1.422 (4) | 1.390 (4) | 1.426 (14) |
C2—C3 | 1.345 (4) | 1.343 (5) | 1.351 (4) | 1.352 (15) |
C3—C4 | 1.417 (4) | 1.422 (4) | 1.398 (4) | 1.433 (16) |
C4—C5 | 1.355 (3) | 1.359 (4) | 1.359 (4) | 1.347 (14) |
C5—C6 | 1.419 (3) | 1.413 (4) | 1.405 (4) | 1.408 (13) |
C6—C7 | 1.375 (3) | 1.369 (4) | 1.409 (3) | 1.376 (12) |
C7—O1 | 1.348 (3) | 1.357 (3) | 1.383 (5) | 1.340 (9) |
C7—C8 | 1.458 (3) | 1.453 (4) | 1.409 (3) | 1.468 (10) |
C7—O1—N1 | 110.34 (16) | 110.4 (2) | 112.3 (6) | 112.3 (6) |
O1—N1—C1 | 104.47 (17) | 103.7 (3) | 106.4 (4) | 102.9 (8) |
N1—C1—C2 | 127.6 (2) | 125.8 (3) | 133.1 (4) | 127.3 (12) |
N1—C1—C6 | 112.03 (18) | 113.2 (3) | 106.2 (3) | 113.2 (10) |
C2—C1—C6 | 120.3 (2) | 121.0 (4) | 120.7 (3) | 119.4 (10) |
C1—C2—C3 | 117.0 (2) | 117.6 (3) | 118.7 (3) | 119.7 (14) |
C2—C3—C4 | 122.7 (2) | 121.9 (4) | 121.4 (3) | 119.4 (11) |
C3—C4—C5 | 121.1 (2) | 121.8 (4) | 120.9 (3) | 122.9 (12) |
C4—C5—C6 | 117.3 (2) | 118.0 (3) | 118.9 (3) | 118.5 (12) |
C5—C6—C7 | 134.7 (2) | 135.8 (3) | 127.5 (3) | 135.6 (12) |
C5—C6—C1 | 120.66 (19) | 119.7 (3) | 119.3 (3) | 119.9 (9) |
C1—C6—C7 | 104.57 (19) | 104.5 (3) | 113.1 (3) | 104.5 (10) |
C6—C7—C8 | 134.4 (2) | 136.2 (3) | 135.7 (4) | 136.4 (11) |
C6—C7—O1 | 108.58 (19) | 108.2 (3) | 101.8 (5) | 107.1 (9) |
O1—C7—C8 | 117.03 (17) | 115.6 (3) | 121.4 (5) | 116.5 (8) |
C6—C7—C8—C9 | -51.9 (3) | 12.8 (5) | 13.4 (2) | -10 (2) |
C6—C7—C8—C13 | 125.8 (3) | -168.0 (3) | -168.7 (2) | 172.6 (16) |
O1—C7—C8—C9b | 128.2 (2) | -166.6 (3) | -152.3 (5) | 170.1 (9) |
O1—C7—C8—C13b | -54.2 (3) | 12.5 (4) | 25.7 (5) | -7.8 (18) |
a. The atom designations are correct and unambiguous for all except molecule IIB, where C8, C9 and C13 should be read as C6i, C5i and C1i [symmetry code: (i) −x,y,3/2 − z], respectively. b. These values are of dubious significance with regard to the twist about the C7—C8 bond for molecule IIB as a result, in this case, of the disorder of O1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1i | 0.82 | 1.97 | 2.782 (3) | 172 |
C10—H10···O1i | 0.93 | 2.56 | 3.337 (3) | 142 |
Symmetry code (i) x,1 + y,z. |
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The title compounds, (I) and (II), are products, along with the corresponding anilines, (Ib) or (IIb), of the zinc-dust reduction of a mixture of aqueous ammonium chloride and an ethanol solution of the appropriate 2'-nitrobenzophenone, (Ia) or (IIa). Forrester et al. (1992) have already shown that a similar reduction of the 2'-nitrobenzophenone (IIIa) results in the formation of the hydroxylamine spirodienone (III) [Cambridge Structural Database (CSD; Allen, 2002) refcode KUJHUS] rather than a benzisoxazole and point out that such compounds as (I), (II) and (III) can be regarded as intermediates in the reduction of the nitro compound to the corresponding aniline.
In the structure of (I), the asymmetric unit consists of a single complete molecule (Fig. 1). In (II), with space group I2/c, the situation is more complex. The asymmetric unit now comprises three distinct molecules, which are, as far as possible, labelled in the same manner as the molecule of (I) but distinguished one from another by the suffixes A, B or C. The `normal' molecule A of (II) in the 8c general positions is shown in Fig. 2. Precisely the same labelling scheme but with a change of suffix applies to molecules C, which occur pairwise and which are centrosymmetrically related about the 4a sites, each member of the pair being a complete molecule but having an occupancy of 0.5. Atom C7 of molecule B in the 2 b sites (Fig. 3) coincides with a crystallographic twofold axis. Consequently, the six-membered C1–C6 and C18–C13 rings of the other molecules are now related by symmetry as shown in Fig. 3, and atoms N1, O1 and H1 are distributed over pairs of sites, all of occupancy 0.5 (only one member of each pair is shown). For convenience, the individual molecules are denoted (I), (IIA), (IIB) and (IIC).
Bond lengths and angles for the benzisoxazolyl residue comprising atoms O1, N1 and C1–C7 and the torsion angles involving the C7—C8 bonds of all four molecules are given in Table 1. Ignoring for the moment the torsion angles, which are discussed later, the bond lengths and angles are similar for all four molecules and are entirely consistent with the distribution of single and double bonds indicated in the chemical structural drawings of (I) and (II). Agreement is particularly good for molecules (I) and (IIA), but less so for (IIC) and especially (IIB), where the crystallographically induced pseudo-symmetry and disorder noted above are seen to have a deleterious effect.
All of the molecules consist of two essentially planar fragments, namely the benzisoxazolyl residue discussed above and the substituent phenyl ring [C8–C13 or its equivalent in molecule (IIB)]. In all four cases, these fragments are related by rotation about the C7—C8 bond joining them [or its equivalent in molecule (IIB)] by angles computed from the relevant torsion angles (Table 1) as 53.02 (14), 12.58 (15), 12.3 (2) and 8.4 (8)° for molecules (I), (IIA), (IIB) and (IIC), respectively. These rotations can occur in either a clockwise or an anticlockwise sense and consequently render the molecules handed. In the non-centrosymmetric structure of (I), where the twist is greatest, presumably because of the steric requirement of the o-methoxy substituents, all of the molecules in a given crystal are of the same hand, while crystals of opposite hand are presumably present in the bulk sample. In the absence of atoms of atomic number higher than that of O, the absolute structure is, however, indeterminate. The centrosymmetric structure of (II), in which the twist is much less, is, of course, racemic.
The phenol residue of (I) merits further comment. The substituent atoms O2–O4 are not significantly displaced from the plane defined by the C8–C13 ring nucleus, and neither is atom C7. The displacement of the methyl C14 group is only 0.027 (6) Å, while that of atom C15 is much greater at 0.327 (5) Å.
A feature of the packing of the molecules in the cell of (I) (Fig. 4) is the presence of O2—H2···N1 and ancilliary C10—H10···O1 hydrogen bonds (Table 2). These connect the molecules into chains propagated in the b direction, in which adjacent molecules within the chain are related by cell translation. No equivalent intermolecular interaction is observed in (II).
Compounds (I) and (II) have also been characterized to some extent by spectroscopy (see below). Thus, while the 1H NMR spectrum of (II) shows only multiple aryl H-atom? chemical shifts, that of (I) can be analyzed more specifically, with the alkoxy groups being seen to bring the resonances of the H atoms adjacent to them up field (to δ = 6.19 and 6.28). Mass spectral fragmentation is also consistent with previous observations (Dyall & Karpa, 1989) that loss of CO and HCN is coupled to fragments C7H4N, C7H5N and C7H4NO, which are also found in the spectrum of (I). Fragmentation of (II) shows a pattern similar to that of (I).