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The title compounds, C15H13NO4, (I), and C13H9NO, (II), are produced, along with the corresponding anilines, by the reduction of the appropriate o-nitro­benzo­phenones. In (I), the planar benz­isoxazole and phenol fragments are tilted relative to one another by a rotation of 53.02 (14)° about the bond joining them, and the mol­ecules are linked into chains by phenol O—H...N and phenyl C—H...Ooxazole hydrogen bonds. The cell of (II) (space group I2/c) contains eight mol­ecules in general positions, four more in the 2b sites, with twofold axial symmetry that induces a degree of disorder, and a further four as centrosymmetric pairs of complete mol­ecules, each with an occupancy of one-half. The relative tilt of the planar fragments varies slightly from one mol­ecule to another but is much less than that in (I), ranging from 8.8 (8) to 12.58 (15)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103015713/gd1263sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103015713/gd1263Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103015713/gd1263IIsup3.hkl
Contains datablock II

CCDC references: 221081; 221082

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I), showing the atomic labelling scheme. Non-H atoms are shown as 50% probability displacement ellipsoids and H atoms are shown as small circles of arbitrary radii.
[Figure 2] Fig. 2. A view of molecule A of (II). The representation is the same as in Fig. 1. The atom labels, from which the suffices have been omitted, apply equally to molecule C.
[Figure 3] Fig. 3. A view of molecule B of (II). The representation is the same as in Fig. 1. [Symmetry code: (i) −x,y,3/2 − z.]
[Figure 4] Fig. 4. A view of the unit cell of (I), in the same representation as in Fig. 1 except that all H atoms other than those involved in hydrogen-bond formation (dashed lines) have been omitted and only selected atoms are labelled. The view is along a. [Symmetry codes: (i) x, y − 1, z; (ii) −x, 1/2 + y, 1/2 − z; (iii) −x, y − 1/2, 1/2 − z; (iv) 1/2 − x, 1 − y,1/2 + z; (v) 1/2 − x, 2 − y, 1/2 + z; (vi) 1/2 + x, 1/2 − y,1 − z; (vii) 1/2 + x, 3/2 − y, 1 − z.]
(I) 2-(2,1-Benzoxazol-3-yl)-3,5-dimethoxyphenol top
Crystal data top
C15H13NO4F(000) = 568
Mr = 271.26Dx = 1.350 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ac 2abCell parameters from 15 reflections
a = 6.941 (3) Åθ = 9.0–12.4°
b = 7.277 (3) ŵ = 0.10 mm1
c = 26.418 (10) ÅT = 298 K
V = 1334.4 (9) Å3Block, orange–yellow
Z = 40.70 × 0.60 × 0.60 mm
Data collection top
Nicolet P3
diffractometer
Rint = 0.002
Radiation source: normal-focus sealed tubeθmax = 25.0°, θmin = 1.5°
Graphite monochromatorh = 08
θ–2θ scansk = 08
1403 measured reflectionsl = 031
1402 independent reflections2 standard reflections every 50 reflections
1251 reflections with I > 2σ(I) intensity decay: none
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H-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 parametersΔρmax = 0.11 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C15H13NO4V = 1334.4 (9) Å3
Mr = 271.26Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.941 (3) ŵ = 0.10 mm1
b = 7.277 (3) ÅT = 298 K
c = 26.418 (10) Å0.70 × 0.60 × 0.60 mm
Data collection top
Nicolet P3
diffractometer
Rint = 0.002
1403 measured reflections2 standard reflections every 50 reflections
1402 independent reflections intensity decay: none
1251 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.082H-atom parameters constrained
S = 1.09Δρmax = 0.11 e Å3
1402 reflectionsΔρmin = 0.14 e Å3
184 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.1625 (2)0.3863 (2)0.13520 (5)0.0468 (4)
O20.2585 (3)0.9037 (2)0.14420 (7)0.0629 (5)
H20.26201.01450.14970.094*
O30.2292 (3)1.0727 (3)0.02961 (7)0.0768 (6)
O40.2156 (2)0.4687 (2)0.10493 (6)0.0588 (5)
N10.2519 (3)0.2728 (3)0.17145 (7)0.0503 (5)
C10.2593 (3)0.3753 (3)0.21300 (8)0.0447 (5)
C20.3314 (4)0.3239 (4)0.26178 (8)0.0573 (7)
H2A0.38800.20980.26730.069*
C30.3136 (4)0.4481 (4)0.29921 (9)0.0653 (8)
H30.35700.41710.33140.078*
C40.2313 (4)0.6242 (4)0.29159 (8)0.0626 (7)
H40.22210.70430.31890.075*
C50.1658 (3)0.6795 (4)0.24576 (8)0.0524 (6)
H50.11470.79640.24100.063*
C60.1782 (3)0.5517 (3)0.20531 (7)0.0422 (5)
C70.1187 (3)0.5508 (3)0.15564 (7)0.0402 (5)
C80.0236 (3)0.6840 (3)0.12284 (7)0.0400 (5)
C90.0968 (3)0.8624 (3)0.11798 (8)0.0453 (5)
C100.0091 (4)0.9892 (3)0.08658 (8)0.0537 (6)
H100.06011.10670.08320.064*
C110.1551 (4)0.9397 (3)0.06028 (8)0.0511 (6)
C120.2349 (4)0.7671 (3)0.06542 (8)0.0489 (6)
H120.34670.73600.04800.059*
C130.1462 (3)0.6413 (3)0.09678 (7)0.0428 (5)
C140.4028 (6)1.0292 (5)0.00236 (13)0.1065 (14)
H14A0.50371.00090.02600.160*
H14B0.44021.13260.01800.160*
H14C0.38030.92490.01910.160*
C150.4046 (4)0.4288 (5)0.08733 (13)0.0815 (9)
H15A0.40500.42640.05100.122*
H15B0.44440.31120.10000.122*
H15C0.49200.52170.09910.122*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0534 (9)0.0436 (8)0.0434 (7)0.0012 (8)0.0028 (8)0.0020 (7)
O20.0611 (10)0.0452 (8)0.0823 (12)0.0048 (9)0.0301 (10)0.0005 (9)
O30.1018 (15)0.0642 (11)0.0643 (10)0.0044 (13)0.0402 (11)0.0156 (9)
O40.0487 (10)0.0579 (10)0.0699 (10)0.0140 (9)0.0130 (8)0.0121 (9)
N10.0522 (11)0.0432 (10)0.0555 (11)0.0049 (10)0.0053 (10)0.0080 (9)
C10.0368 (10)0.0541 (12)0.0432 (11)0.0007 (12)0.0013 (10)0.0067 (11)
C20.0427 (13)0.0757 (17)0.0535 (13)0.0030 (13)0.0026 (11)0.0218 (13)
C30.0486 (13)0.106 (2)0.0409 (12)0.0040 (17)0.0010 (11)0.0122 (14)
C40.0527 (14)0.0960 (19)0.0391 (11)0.0005 (17)0.0010 (12)0.0097 (13)
C50.0454 (13)0.0679 (15)0.0438 (11)0.0047 (13)0.0028 (11)0.0103 (11)
C60.0352 (10)0.0553 (13)0.0362 (10)0.0009 (11)0.0020 (9)0.0010 (10)
C70.0376 (10)0.0425 (11)0.0407 (10)0.0002 (10)0.0036 (9)0.0022 (9)
C80.0409 (11)0.0459 (12)0.0332 (10)0.0011 (10)0.0010 (9)0.0028 (9)
C90.0458 (12)0.0452 (12)0.0449 (11)0.0015 (11)0.0065 (10)0.0060 (10)
C100.0667 (15)0.0431 (12)0.0513 (12)0.0059 (12)0.0120 (12)0.0050 (11)
C110.0672 (16)0.0504 (14)0.0358 (11)0.0025 (14)0.0097 (11)0.0014 (10)
C120.0479 (13)0.0610 (14)0.0379 (10)0.0009 (13)0.0078 (11)0.0030 (10)
C130.0448 (12)0.0482 (12)0.0355 (9)0.0035 (11)0.0020 (10)0.0011 (10)
C140.134 (3)0.089 (2)0.096 (2)0.000 (2)0.077 (3)0.020 (2)
C150.0470 (14)0.084 (2)0.113 (2)0.0213 (16)0.0110 (16)0.011 (2)
Geometric parameters (Å, º) top
O1—C71.348 (3)C5—H50.9300
O1—N11.408 (2)C6—C71.375 (3)
O2—C91.352 (3)C7—C81.458 (3)
O2—H20.8200C8—C131.400 (3)
O3—C111.363 (3)C8—C91.400 (3)
O3—C141.439 (4)C9—C101.382 (3)
O4—C131.363 (3)C10—C111.382 (3)
O4—C151.422 (3)C10—H100.9300
N1—C11.328 (3)C11—C121.380 (3)
C1—C61.417 (3)C12—C131.379 (3)
C1—C21.432 (3)C12—H120.9300
C2—C31.345 (4)C14—H14A0.9600
C2—H2A0.9300C14—H14B0.9600
C3—C41.417 (4)C14—H14C0.9600
C3—H30.9300C15—H15A0.9600
C4—C51.355 (3)C15—H15B0.9600
C4—H40.9300C15—H15C0.9600
C5—C61.419 (3)
C7—O1—N1110.34 (16)C9—C8—C7120.45 (19)
C9—O2—H2109.5O2—C9—C10121.7 (2)
C11—O3—C14117.2 (2)O2—C9—C8117.4 (2)
C13—O4—C15117.6 (2)C10—C9—C8120.9 (2)
C1—N1—O1104.47 (17)C9—C10—C11119.4 (2)
N1—C1—C6112.03 (18)C9—C10—H10120.3
N1—C1—C2127.6 (2)C11—C10—H10120.3
C6—C1—C2120.3 (2)O3—C11—C12123.6 (2)
C3—C2—C1117.0 (2)O3—C11—C10115.2 (2)
C3—C2—H2A121.5C12—C11—C10121.2 (2)
C1—C2—H2A121.5C13—C12—C11118.9 (2)
C2—C3—C4122.7 (2)C13—C12—H12120.5
C2—C3—H3118.7C11—C12—H12120.5
C4—C3—H3118.7O4—C13—C12123.3 (2)
C5—C4—C3122.1 (2)O4—C13—C8115.13 (19)
C5—C4—H4119.0C12—C13—C8121.6 (2)
C3—C4—H4119.0O3—C14—H14A109.5
C4—C5—C6117.3 (2)O3—C14—H14B109.5
C4—C5—H5121.4H14A—C14—H14B109.5
C6—C5—H5121.4O3—C14—H14C109.5
C7—C6—C1104.57 (19)H14A—C14—H14C109.5
C7—C6—C5134.7 (2)H14B—C14—H14C109.5
C1—C6—C5120.66 (19)O4—C15—H15A109.5
O1—C7—C6108.58 (19)O4—C15—H15B109.5
O1—C7—C8117.03 (17)H15A—C15—H15B109.5
C6—C7—C8134.4 (2)O4—C15—H15C109.5
C13—C8—C9117.78 (19)H15A—C15—H15C109.5
C13—C8—C7121.73 (19)H15B—C15—H15C109.5
C7—O1—N1—C10.2 (2)O1—C7—C8—C9128.2 (2)
O1—N1—C1—C60.0 (2)C6—C7—C8—C951.9 (3)
O1—N1—C1—C2177.9 (2)C13—C8—C9—O2178.54 (19)
N1—C1—C2—C3176.2 (2)C7—C8—C9—O20.8 (3)
C6—C1—C2—C31.6 (3)C13—C8—C9—C103.0 (3)
C1—C2—C3—C41.3 (4)C7—C8—C9—C10179.3 (2)
C2—C3—C4—C50.3 (4)O2—C9—C10—C11179.5 (2)
C3—C4—C5—C61.5 (4)C8—C9—C10—C111.1 (3)
N1—C1—C6—C70.3 (3)C14—O3—C11—C121.5 (4)
C2—C1—C6—C7177.8 (2)C14—O3—C11—C10178.6 (3)
N1—C1—C6—C5177.6 (2)C9—C10—C11—O3178.9 (2)
C2—C1—C6—C50.5 (3)C9—C10—C11—C121.0 (4)
C4—C5—C6—C7175.3 (2)O3—C11—C12—C13178.7 (2)
C4—C5—C6—C11.1 (3)C10—C11—C12—C131.2 (3)
N1—O1—C7—C60.4 (2)C15—O4—C13—C1211.3 (3)
N1—O1—C7—C8179.57 (18)C15—O4—C13—C8168.5 (2)
C1—C6—C7—O10.4 (2)C11—C12—C13—O4178.9 (2)
C5—C6—C7—O1177.2 (2)C11—C12—C13—C80.9 (3)
C1—C6—C7—C8179.6 (2)C9—C8—C13—O4176.89 (19)
C5—C6—C7—C82.8 (4)C7—C8—C13—O40.8 (3)
O1—C7—C8—C1354.2 (3)C9—C8—C13—C122.9 (3)
C6—C7—C8—C13125.8 (3)C7—C8—C13—C12179.4 (2)
(II) 3-Phenyl-2,1-benzoxazole top
Crystal data top
C13H9NOF(000) = 1632
Mr = 195.21Dx = 1.297 Mg m3
Monoclinic, I2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ycCell parameters from 14 reflections
a = 12.027 (13) Åθ = 7.7–11.6°
b = 10.706 (14) ŵ = 0.08 mm1
c = 31.76 (3) ÅT = 298 K
β = 102.11 (8)°Block, pale brown
V = 3998 (8) Å30.70 × 0.50 × 0.50 mm
Z = 16
Data collection top
Nicolet P3
diffractometer
Rint = 0.041
Radiation source: normal-focus sealed tubeθmax = 25.1°, θmin = 1.3°
Graphite monochromatorh = 014
θ–2θ scansk = 012
3726 measured reflectionsl = 3736
3551 independent reflections2 standard reflections every 50 reflections
1555 reflections with I > 2σ(I) intensity decay: none
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-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 parametersΔρmax = 0.10 e Å3
40 restraintsΔρmin = 0.12 e Å3
Crystal data top
C13H9NOV = 3998 (8) Å3
Mr = 195.21Z = 16
Monoclinic, I2/cMo Kα radiation
a = 12.027 (13) ŵ = 0.08 mm1
b = 10.706 (14) ÅT = 298 K
c = 31.76 (3) Å0.70 × 0.50 × 0.50 mm
β = 102.11 (8)°
Data collection top
Nicolet P3
diffractometer
Rint = 0.041
3726 measured reflections2 standard reflections every 50 reflections
3551 independent reflections intensity decay: none
1555 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.05440 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 1.02Δρmax = 0.10 e Å3
3551 reflectionsΔρmin = 0.12 e Å3
348 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C1A0.8157 (3)0.2153 (3)0.57481 (10)0.0796 (9)
C2A0.9203 (3)0.2458 (4)0.60310 (10)0.0973 (11)
H2A0.96180.18580.62100.117*
C3A0.9569 (3)0.3643 (4)0.60306 (11)0.1095 (13)
H3A1.02520.38630.62120.131*
C4A0.8942 (3)0.4571 (4)0.57600 (11)0.1095 (12)
H4A0.92200.53840.57730.131*
C5A0.7947 (3)0.4303 (3)0.54827 (9)0.0886 (10)
H5A0.75480.49170.53060.106*
C6A0.7539 (3)0.3063 (3)0.54710 (9)0.0682 (8)
C7A0.6611 (3)0.2435 (3)0.52470 (9)0.0695 (8)
C8A0.5628 (3)0.2735 (3)0.49107 (9)0.0687 (8)
C9A0.5582 (3)0.3836 (3)0.46832 (9)0.0852 (9)
H9A0.61810.44010.47480.102*
C10A0.4648 (3)0.4108 (3)0.43588 (10)0.1003 (11)
H10A0.46230.48570.42090.120*
C11A0.3766 (3)0.3290 (4)0.42578 (11)0.1011 (11)
H11A0.31460.34760.40380.121*
C12A0.3794 (3)0.2190 (4)0.44813 (12)0.1037 (11)
H12A0.31920.16300.44140.124*
C13A0.4719 (3)0.1916 (3)0.48065 (11)0.0945 (10)
H13A0.47310.11710.49580.113*
N1A0.7671 (3)0.1048 (3)0.57071 (9)0.1077 (10)
O1A0.66755 (19)0.1233 (2)0.53857 (7)0.0978 (7)
C1B0.1341 (3)0.2688 (3)0.70768 (9)0.0698 (8)
H1B0.13140.35140.71650.084*0.50
C2B0.2049 (3)0.2359 (4)0.68008 (10)0.0866 (10)
H2B0.25060.29540.67070.104*
C3B0.2060 (3)0.1158 (4)0.66708 (10)0.0932 (11)
H3B0.25380.09280.64890.112*
C4B0.1369 (3)0.0254 (3)0.68040 (10)0.0810 (9)
H4B0.13770.05600.67020.097*
C5B0.0685 (2)0.0549 (3)0.70801 (9)0.0694 (8)
H5B0.02390.00600.71720.083*
C6B0.0665 (2)0.1788 (3)0.72240 (8)0.0574 (7)
C7B0.00000.2284 (4)0.75000.0624 (10)
N1B0.1089 (4)0.3804 (4)0.72455 (16)0.0802 (14)0.50
O1B0.0320 (4)0.3527 (3)0.7521 (4)0.078 (2)0.50
C1C0.2011 (19)0.1413 (17)0.3235 (7)0.063 (4)0.50
C2C0.138 (2)0.1563 (19)0.3565 (8)0.082 (4)0.50
H2C0.14090.09490.37740.098*0.50
C3C0.0747 (11)0.2601 (10)0.3574 (4)0.098 (4)0.50
H3C0.03220.26970.37840.118*0.50
C4C0.0735 (17)0.3551 (10)0.3255 (5)0.090 (4)0.50
H4C0.02880.42560.32630.109*0.50
C5C0.1343 (19)0.3467 (17)0.2945 (7)0.066 (4)0.50
H5C0.13280.41090.27460.080*0.50
C6C0.2001 (9)0.2388 (11)0.2928 (3)0.060 (3)0.50
C7C0.2686 (7)0.1954 (8)0.2663 (3)0.071 (2)0.50
C8C0.3051 (11)0.2398 (11)0.2276 (3)0.065 (3)0.50
C9C0.2575 (8)0.3430 (9)0.2048 (3)0.083 (3)0.50
H9C0.20440.39050.21520.099*0.50
C10C0.288 (3)0.377 (2)0.1664 (8)0.117 (12)0.50
H10C0.25080.44390.15050.141*0.50
C11C0.372 (3)0.315 (2)0.1516 (9)0.135 (12)0.50
H11C0.39650.34100.12720.162*0.50
C12C0.4171 (15)0.2128 (15)0.1739 (5)0.113 (6)0.50
H12C0.47030.16590.16330.135*0.50
C13C0.388 (2)0.1753 (19)0.2117 (8)0.098 (9)0.50
H13C0.42370.10660.22660.118*0.50
N1C0.2671 (7)0.0481 (6)0.3184 (3)0.105 (3)0.50
O1C0.3087 (4)0.0839 (4)0.28169 (16)0.0892 (13)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.083 (2)0.086 (3)0.069 (2)0.021 (2)0.0154 (19)0.003 (2)
C2A0.096 (3)0.114 (3)0.079 (2)0.029 (3)0.012 (2)0.012 (2)
C3A0.105 (3)0.146 (4)0.069 (2)0.001 (3)0.002 (2)0.004 (3)
C4A0.120 (3)0.118 (3)0.081 (2)0.027 (3)0.000 (2)0.009 (2)
C5A0.103 (3)0.093 (3)0.065 (2)0.008 (2)0.0063 (19)0.0129 (19)
C6A0.077 (2)0.078 (2)0.0522 (18)0.012 (2)0.0179 (16)0.0053 (18)
C7A0.082 (2)0.066 (2)0.0656 (19)0.012 (2)0.0260 (18)0.0047 (17)
C8A0.073 (2)0.071 (2)0.0653 (19)0.0026 (18)0.0199 (17)0.0001 (18)
C9A0.092 (2)0.091 (2)0.068 (2)0.012 (2)0.0061 (19)0.0071 (19)
C10A0.112 (3)0.100 (3)0.080 (2)0.012 (2)0.001 (2)0.017 (2)
C11A0.089 (3)0.115 (3)0.092 (3)0.004 (3)0.002 (2)0.012 (2)
C12A0.082 (3)0.112 (3)0.113 (3)0.019 (2)0.010 (2)0.003 (3)
C13A0.090 (3)0.089 (3)0.104 (3)0.004 (2)0.018 (2)0.019 (2)
N1A0.114 (3)0.087 (2)0.114 (2)0.027 (2)0.003 (2)0.0098 (19)
O1A0.1034 (18)0.0743 (16)0.1092 (17)0.0118 (14)0.0073 (14)0.0067 (14)
C1B0.078 (2)0.064 (2)0.0630 (19)0.0052 (19)0.0058 (17)0.0008 (17)
C2B0.074 (2)0.113 (3)0.074 (2)0.016 (2)0.0179 (18)0.001 (2)
C3B0.068 (2)0.132 (3)0.082 (2)0.007 (3)0.0210 (18)0.014 (3)
C4B0.088 (2)0.074 (2)0.076 (2)0.012 (2)0.0072 (19)0.0133 (18)
C5B0.075 (2)0.071 (2)0.0580 (18)0.0014 (17)0.0045 (16)0.0044 (17)
C6B0.0543 (17)0.0612 (19)0.0525 (17)0.0026 (16)0.0016 (14)0.0001 (15)
C7B0.075 (3)0.047 (3)0.061 (3)0.0000.004 (2)0.000
N1B0.092 (4)0.071 (3)0.080 (4)0.015 (3)0.023 (3)0.001 (3)
O1B0.100 (7)0.059 (2)0.078 (3)0.006 (2)0.023 (7)0.010 (3)
C1C0.070 (7)0.072 (8)0.047 (8)0.001 (6)0.013 (7)0.003 (6)
C2C0.071 (9)0.084 (8)0.092 (12)0.014 (6)0.022 (8)0.018 (7)
C3C0.096 (7)0.102 (9)0.100 (9)0.014 (6)0.027 (6)0.024 (7)
C4C0.087 (7)0.090 (8)0.085 (8)0.003 (8)0.000 (6)0.002 (7)
C5C0.061 (8)0.065 (6)0.071 (8)0.004 (7)0.008 (8)0.003 (7)
C6C0.050 (5)0.060 (7)0.060 (7)0.004 (5)0.008 (5)0.003 (6)
C7C0.064 (5)0.055 (5)0.086 (7)0.002 (5)0.000 (4)0.005 (4)
C8C0.057 (6)0.066 (6)0.064 (7)0.008 (5)0.005 (6)0.005 (7)
C9C0.087 (7)0.062 (7)0.096 (9)0.008 (6)0.011 (6)0.008 (6)
C10C0.16 (3)0.097 (15)0.079 (15)0.056 (13)0.019 (13)0.020 (10)
C11C0.15 (3)0.18 (3)0.070 (11)0.074 (18)0.009 (14)0.014 (17)
C12C0.085 (8)0.174 (19)0.081 (9)0.007 (14)0.022 (8)0.023 (12)
C13C0.068 (11)0.135 (16)0.083 (10)0.002 (9)0.008 (8)0.022 (9)
N1C0.138 (6)0.071 (5)0.107 (6)0.013 (4)0.026 (5)0.012 (5)
O1C0.105 (4)0.066 (3)0.097 (4)0.013 (3)0.022 (3)0.014 (3)
Geometric parameters (Å, º) top
C1A—N1A1.314 (4)C4B—C5B1.359 (4)
C1A—C6A1.415 (4)C4B—H4B0.9300
C1A—C2A1.422 (4)C5B—C6B1.405 (4)
C2A—C3A1.343 (5)C5B—H5B0.9300
C2A—H2A0.9300C6B—C7B1.409 (3)
C3A—C4A1.422 (4)C7B—O1B1.383 (5)
C3A—H3A0.9300N1B—O1B1.432 (12)
C4A—C5A1.359 (4)C1C—N1C1.305 (12)
C4A—H4A0.9300C1C—C6C1.425 (14)
C5A—C6A1.413 (4)C1C—C2C1.426 (14)
C5A—H5A0.9300C2C—C3C1.352 (15)
C6A—C7A1.369 (4)C2C—H2C0.9300
C7A—O1A1.357 (3)C3C—C4C1.433 (16)
C7A—C8A1.453 (4)C3C—H3C0.9300
C8A—C9A1.377 (4)C4C—C5C1.347 (14)
C8A—C13A1.387 (4)C4C—H4C0.9300
C9A—C10A1.386 (4)C5C—C6C1.408 (13)
C9A—H9A0.9300C5C—H5C0.9300
C10A—C11A1.361 (4)C6C—C7C1.376 (12)
C10A—H10A0.9300C7C—O1C1.340 (9)
C11A—C12A1.372 (4)C7C—C8C1.468 (10)
C11A—H11A0.9300C8C—C9C1.378 (11)
C12A—C13A1.381 (4)C8C—C13C1.392 (14)
C12A—H12A0.9300C9C—C10C1.396 (15)
C13A—H13A0.9300C9C—H9C0.9300
N1A—O1A1.415 (3)C10C—C11C1.376 (17)
C1B—N1B1.369 (5)C10C—H10C0.9300
C1B—C2B1.390 (4)C11C—C12C1.350 (16)
C1B—C6B1.403 (4)C11C—H11C0.9300
C1B—H1B0.9300C12C—C13C1.378 (15)
C2B—C3B1.351 (4)C12C—H12C0.9300
C2B—H2B0.9300C13C—H13C0.9300
C3B—C4B1.398 (4)N1C—O1C1.415 (8)
C3B—H3B0.9300
N1A—C1A—C6A113.2 (3)C3B—C4B—H4B119.6
N1A—C1A—C2A125.8 (3)C4B—C5B—C6B118.9 (3)
C6A—C1A—C2A121.0 (4)C4B—C5B—H5B120.5
C3A—C2A—C1A117.6 (3)C6B—C5B—H5B120.5
C3A—C2A—H2A121.2C1B—C6B—C5B119.3 (3)
C1A—C2A—H2A121.2C1B—C6B—C7B113.1 (3)
C2A—C3A—C4A121.9 (4)C5B—C6B—C7B127.5 (3)
C2A—C3A—H3A119.1O1B—C7B—C6B101.8 (5)
C4A—C3A—H3A119.1O1B—C7B—C6Bi121.4 (5)
C5A—C4A—C3A121.8 (4)C6B—C7B—C6Bi135.7 (4)
C5A—C4A—H4A119.1C1B—N1B—O1B106.4 (4)
C3A—C4A—H4A119.1C7B—O1B—N1B112.3 (6)
C4A—C5A—C6A118.0 (3)N1C—C1C—C6C113.2 (10)
C4A—C5A—H5A121.0N1C—C1C—C2C127.3 (12)
C6A—C5A—H5A121.0C6C—C1C—C2C119.4 (10)
C7A—C6A—C5A135.8 (3)C3C—C2C—C1C119.7 (14)
C7A—C6A—C1A104.5 (3)C3C—C2C—H2C120.1
C5A—C6A—C1A119.7 (3)C1C—C2C—H2C120.1
O1A—C7A—C6A108.2 (3)C2C—C3C—C4C119.4 (11)
O1A—C7A—C8A115.6 (3)C2C—C3C—H3C120.3
C6A—C7A—C8A136.2 (3)C4C—C3C—H3C120.3
C9A—C8A—C13A118.2 (3)C5C—C4C—C3C122.9 (12)
C9A—C8A—C7A120.8 (3)C5C—C4C—H4C118.6
C13A—C8A—C7A121.0 (3)C3C—C4C—H4C118.6
C8A—C9A—C10A120.5 (3)C4C—C5C—C6C118.5 (12)
C8A—C9A—H9A119.8C4C—C5C—H5C120.7
C10A—C9A—H9A119.8C6C—C5C—H5C120.7
C11A—C10A—C9A120.6 (3)C7C—C6C—C5C135.6 (12)
C11A—C10A—H10A119.7C7C—C6C—C1C104.5 (10)
C9A—C10A—H10A119.7C5C—C6C—C1C119.9 (9)
C10A—C11A—C12A119.8 (3)O1C—C7C—C6C107.1 (9)
C10A—C11A—H11A120.1O1C—C7C—C8C116.5 (8)
C12A—C11A—H11A120.1C6C—C7C—C8C136.4 (11)
C11A—C12A—C13A119.9 (3)C9C—C8C—C13C117.2 (12)
C11A—C12A—H12A120.1C9C—C8C—C7C122.4 (12)
C13A—C12A—H12A120.1C13C—C8C—C7C120.4 (11)
C12A—C13A—C8A121.0 (3)C8C—C9C—C10C121.1 (13)
C12A—C13A—H13A119.5C8C—C9C—H9C119.5
C8A—C13A—H13A119.5C10C—C9C—H9C119.5
C1A—N1A—O1A103.7 (3)C11C—C10C—C9C121.0 (17)
C7A—O1A—N1A110.4 (2)C11C—C10C—H10C119.5
N1B—C1B—C2B133.1 (4)C9C—C10C—H10C119.5
N1B—C1B—C6B106.2 (3)C12C—C11C—C10C117.3 (16)
C2B—C1B—C6B120.7 (3)C12C—C11C—H11C121.4
C2B—C1B—H1B119.6C10C—C11C—H11C121.4
C6B—C1B—H1B119.6C11C—C12C—C13C123.0 (15)
C3B—C2B—C1B118.7 (3)C11C—C12C—H12C118.5
C3B—C2B—H2B120.6C13C—C12C—H12C118.5
C1B—C2B—H2B120.6C12C—C13C—C8C120.3 (15)
C2B—C3B—C4B121.4 (3)C12C—C13C—H13C119.8
C2B—C3B—H3B119.3C8C—C13C—H13C119.8
C4B—C3B—H3B119.3C1C—N1C—O1C102.9 (8)
C5B—C4B—C3B120.9 (3)C7C—O1C—N1C112.3 (6)
C5B—C4B—H4B119.6
N1A—C1A—C2A—C3A179.8 (4)C5B—C6B—C7B—O1B179.1 (5)
C6A—C1A—C2A—C3A1.2 (5)C1B—C6B—C7B—C6Bi168.7 (2)
C1A—C2A—C3A—C4A0.2 (5)C5B—C6B—C7B—C6Bi13.4 (2)
C2A—C3A—C4A—C5A1.0 (6)C2B—C1B—N1B—O1B178.3 (5)
C3A—C4A—C5A—C6A0.4 (5)C6B—C1B—N1B—O1B4.3 (6)
C4A—C5A—C6A—C7A179.9 (3)C6B—C7B—O1B—N1B4.0 (7)
C4A—C5A—C6A—C1A0.9 (4)C1B—N1B—O1B—C7B5.5 (8)
N1A—C1A—C6A—C7A0.2 (4)N1C—C1C—C2C—C3C179 (2)
C2A—C1A—C6A—C7A179.0 (3)C6C—C1C—C2C—C3C3 (5)
N1A—C1A—C6A—C5A179.1 (3)C1C—C2C—C3C—C4C1 (4)
C2A—C1A—C6A—C5A1.7 (4)C2C—C3C—C4C—C5C1 (3)
C5A—C6A—C7A—O1A178.7 (3)C3C—C4C—C5C—C6C1 (3)
C1A—C6A—C7A—O1A0.4 (3)C4C—C5C—C6C—C7C177.9 (16)
C5A—C6A—C7A—C8A1.8 (6)C4C—C5C—C6C—C1C0 (3)
C1A—C6A—C7A—C8A179.1 (3)N1C—C1C—C6C—C7C3 (2)
O1A—C7A—C8A—C9A166.6 (3)C2C—C1C—C6C—C7C179 (2)
C6A—C7A—C8A—C9A12.8 (5)N1C—C1C—C6C—C5C179.0 (19)
O1A—C7A—C8A—C13A12.5 (4)C2C—C1C—C6C—C5C2 (4)
C6A—C7A—C8A—C13A168.0 (3)C5C—C6C—C7C—O1C180.0 (19)
C13A—C8A—C9A—C10A0.1 (4)C1C—C6C—C7C—O1C2.0 (15)
C7A—C8A—C9A—C10A179.1 (3)C5C—C6C—C7C—C8C0 (3)
C8A—C9A—C10A—C11A0.5 (5)C1C—C6C—C7C—C8C177.7 (14)
C9A—C10A—C11A—C12A0.7 (5)O1C—C7C—C8C—C9C170.1 (9)
C10A—C11A—C12A—C13A0.2 (5)C6C—C7C—C8C—C9C10 (2)
C11A—C12A—C13A—C8A0.3 (5)O1C—C7C—C8C—C13C7.8 (18)
C9A—C8A—C13A—C12A0.5 (5)C6C—C7C—C8C—C13C172.6 (16)
C7A—C8A—C13A—C12A178.7 (3)C13C—C8C—C9C—C10C3 (3)
C6A—C1A—N1A—O1A0.0 (4)C7C—C8C—C9C—C10C175 (2)
C2A—C1A—N1A—O1A179.2 (3)C8C—C9C—C10C—C11C5 (5)
C6A—C7A—O1A—N1A0.4 (3)C9C—C10C—C11C—C12C5 (6)
C8A—C7A—O1A—N1A179.2 (2)C10C—C11C—C12C—C13C4 (5)
C1A—N1A—O1A—C7A0.3 (3)C11C—C12C—C13C—C8C3 (4)
N1B—C1B—C2B—C3B176.0 (4)C9C—C8C—C13C—C12C2 (3)
C6B—C1B—C2B—C3B1.1 (4)C7C—C8C—C13C—C12C176.1 (17)
C1B—C2B—C3B—C4B0.7 (5)C6C—C1C—N1C—O1C2 (2)
C2B—C3B—C4B—C5B2.0 (5)C2C—C1C—N1C—O1C179 (3)
C3B—C4B—C5B—C6B1.3 (4)C6C—C7C—O1C—N1C1.0 (8)
N1B—C1B—C6B—C5B176.0 (3)C8C—C7C—O1C—N1C178.8 (7)
C2B—C1B—C6B—C5B1.8 (4)C1C—N1C—O1C—C7C0.6 (14)
N1B—C1B—C6B—C7B2.1 (3)O1B—C7B—C6Bi—C1Bi25.7 (5)
C2B—C1B—C6B—C7B179.9 (2)O1B—C7B—C6Bi—C5Bi152.3 (5)
C4B—C5B—C6B—C1B0.5 (4)C6B—C7B—C6Bi—C1Bi168.7 (2)
C4B—C5B—C6B—C7B178.4 (2)C6B—C7B—C6Bi—C5Bi13.4 (2)
C1B—C6B—C7B—O1B1.1 (5)
Symmetry code: (i) x, y, z+3/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC15H13NO4C13H9NO
Mr271.26195.21
Crystal system, space groupOrthorhombic, P212121Monoclinic, I2/c
Temperature (K)298298
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, 9090, 102.11 (8), 90
V3)1334.4 (9)3998 (8)
Z416
Radiation typeMo KαMo Kα
µ (mm1)0.100.08
Crystal size (mm)0.70 × 0.60 × 0.600.70 × 0.50 × 0.50
Data collection
DiffractometerNicolet P3
diffractometer
Nicolet P3
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1403, 1402, 1251 3726, 3551, 1555
Rint0.0020.041
(sin θ/λ)max1)0.5950.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.082, 1.09 0.054, 0.123, 1.02
No. of reflections14023551
No. of parameters184348
No. of restraints040
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.11, 0.140.10, 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.

IIIAIIBaIIC
O1—N11.408 (2)1.415 (3)1.432 (12)1.415 (8)
N1—C11.328 (3)1.314 (4)1.369 (5)1.305 (12)
C1—C61.417 (3)1.415 (4)1.403 (4)1.425 (14)
C1—C21.432 (3)1.422 (4)1.390 (4)1.426 (14)
C2—C31.345 (4)1.343 (5)1.351 (4)1.352 (15)
C3—C41.417 (4)1.422 (4)1.398 (4)1.433 (16)
C4—C51.355 (3)1.359 (4)1.359 (4)1.347 (14)
C5—C61.419 (3)1.413 (4)1.405 (4)1.408 (13)
C6—C71.375 (3)1.369 (4)1.409 (3)1.376 (12)
C7—O11.348 (3)1.357 (3)1.383 (5)1.340 (9)
C7—C81.458 (3)1.453 (4)1.409 (3)1.468 (10)
C7—O1—N1110.34 (16)110.4 (2)112.3 (6)112.3 (6)
O1—N1—C1104.47 (17)103.7 (3)106.4 (4)102.9 (8)
N1—C1—C2127.6 (2)125.8 (3)133.1 (4)127.3 (12)
N1—C1—C6112.03 (18)113.2 (3)106.2 (3)113.2 (10)
C2—C1—C6120.3 (2)121.0 (4)120.7 (3)119.4 (10)
C1—C2—C3117.0 (2)117.6 (3)118.7 (3)119.7 (14)
C2—C3—C4122.7 (2)121.9 (4)121.4 (3)119.4 (11)
C3—C4—C5121.1 (2)121.8 (4)120.9 (3)122.9 (12)
C4—C5—C6117.3 (2)118.0 (3)118.9 (3)118.5 (12)
C5—C6—C7134.7 (2)135.8 (3)127.5 (3)135.6 (12)
C5—C6—C1120.66 (19)119.7 (3)119.3 (3)119.9 (9)
C1—C6—C7104.57 (19)104.5 (3)113.1 (3)104.5 (10)
C6—C7—C8134.4 (2)136.2 (3)135.7 (4)136.4 (11)
C6—C7—O1108.58 (19)108.2 (3)101.8 (5)107.1 (9)
O1—C7—C8117.03 (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—C13125.8 (3)-168.0 (3)-168.7 (2)172.6 (16)
O1—C7—C8—C9b128.2 (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.
Hydrogen-bonding geometry (Å, °) in (I) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N1i0.821.972.782 (3)172
C10—H10···O1i0.932.563.337 (3)142
Symmetry code (i) x,1 + y,z.
 

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