Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615001588/cu3073sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615001588/cu3073Isup2.hkl | |
Chemdraw file https://doi.org/10.1107/S2053229615001588/cu3073Isup3.cdx | |
Chemdraw file https://doi.org/10.1107/S2053229615001588/cu3073Isup4.cdx | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615001588/cu3073Isup5.cml |
CCDC reference: 1035106
Isocyanide (isonitrile) chemistry began in 1859 when Lieke synthesized the first compound of this type (Lieke, 1859) by the reaction of allyl iodide and silver cyanide. In 1958, isocyanides bacame generally available by dehydration of formamides prepared from primary amines (Ugi & Meyr, 1958). This synthesis and many other important investigations concerning the chemistry of isocyanides have been attributed to Ugi. For scientists who are unfamiliar with this chemistry, the main issue rests with the isocyanide synthesis: there have been concerns over their (wrongly) suspected toxicity and the strongly unpleasant smell associated with the most representative examples. With a few exceptions, isocyanides exhibit no appreciable toxicity to mammals. Some isocyanides have been isolated from natural sources (Garson & Simpson, 2004). In general, these compounds have been identified in marine invertebrates, such as sponges and nudibranch mollusks, and less frequently in fungi or cyanobacteria. Marine derivatives display almost exclusively a terpene-derived skeleton (sesqui- or diterpenes) and, in some cases, also interesting biological properties, such as antimalarial activity, antibiotic properties and cytotoxicity. The main methods of isocyanide preparation are the dehydration of N-monosubstituted formamides (Ugi & Meyr, 1958), the alkylation of cyanides (Lieke, 1859) and the reaction between dichlorocarbene and amine (Feuer et al., 1958). Isocyanides are versatile species in organic and organometallic syntheses (Ryu et al., 1996). They play a key role in several multicomponent processes, such as the Ugi and Passerini reactions (Ugi et al., 1991), and in metal-mediated transformations of ligands of metal complexes. Therefore, isocyanides and their derivatives can be used in inorganic, coordination, organic, polymeric, combinatorial and medicinal chemistry. However, isocyanides have a characteristic piercing odour. As a result, only the simplest commercially available isocyanides are used routinely and a relatively small amount of crystallographic data concerning isocyanides is known. Rather recently, a new family of unsaturated isocyanides, which do not have the objectionable odours, has been prepared by the base-promoted ring opening of oxazoles (Pirrung & Ghorai, 2006; Pirrung et al., 2009) (see Scheme 1). This method is useful in the preparation of ortho-acyloxy-substituted aryl isocyanides. We have expanded this method to include the more active acyl chlorides, which have acidic H atoms in the structure. The base-promoted reaction between 5-methylbenzoxazole and diphenylacetyl chloride was performed and 2-isocyano-4-methylphenyl diphenylacetate, (I), was isolated in 47% yield. The crystal structure of the prepared compound is described.
2-Isocyano-4-methylphenyl diphenylacetate, (I), was prepared according to the method used previously for the preparation of isocyanides, which do not have acidic H atoms (see Scheme 2). The reaction proceeds under N2. A 50 ml Schlenk tube equipped with a magnetic stirrer bar and charged with 5-methylbenzoxazole (1.00 g, 7.51 mmol) and tetrahydrofuran (THF; 18 ml) was cooled to 195 K for 5 min prior to addition of n-BuLi (1.6 M solution in hexanes, 5.15 ml, 8.24 mmol). The reaction mixture was stirred at this temperature for 1.5 h. Diphenylacetyl chloride (1.90 g, 8.24 mmol) was dissolved in THF (4 ml) and added dropwise to the reaction mixture. The resulting solution was heated to room temperature and stirred for 2 h. The reaction mixture was poured onto a mixture of ether (100 ml) and saturated aqueous NaHCO3 (50 ml). The organic layer was washed with water (2 × 50 ml), dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The resulting residue was dissolved in a minimal amount of chloroform and purified by silica-gel column chromatography [eluting with 49:1 v/v, petroleum ether (b.p. 313–333 K)/ethyl acetate] to provide the title compound as a yellow solid (yield 1.16 g, 47%). Crystals of (I) suitable for single-crystal X-ray diffraction were prepared by slow crystallization from a chloroform solution at room temperature (m.p. 395–397 K).
1H NMR (400 MHz, CDCl3): δ 7.45–7.47 (m, 4H), 7.39–7.42 (m, 4H), 7.34–7.36 (m, 2H), 7.25 (s, 1H), 7.20 (d, J = 8 Hz, 1H), 7.05 (d, J = 8 Hz, 1H), 5.39 (s, 1H), 2.36 (s, 3H).
IR (KBr, selected bands): 2125 s ν(N≡C), 1761 vs ν(C=O), 1110 vs ν(C—O) cm-1.
Elemental analysis calculated for C22H17NO2·0.5C4H8O2: C 77.61, H 5.70, N 3.77%; found: C 77.60, H 5.64, N 3.12%.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms on C atoms were placed in calculated positions and were included in the refinement in the riding model approximation, with Uiso(H) values set at 1.2Ueq(C) and with C—H = 0.93 Å for the CH groups, and Uiso(H) values set at 1.5Ueq(C) and C—H = 0.96 Å for methyl groups.
The first example of 2-isocyanophenyl carboxylate, which contains the acidic hydrogen, was synthesized by the base-promoted reaction between 5-methylbenzoxazole and diphenylacetyl chloride. Despite the possibility of a condensation reaction between the molecules of diphenylacetyl chloride, the formation of 2-isocyano-4-methylphenyl diphenylacetate was observed in basic media. In contrast to the previously obtained 2-isocyanophenyl carboxylates (Pirrung & Ghorai, 2006; Pirrung et al., 2009), which have pleasant fruity odours, and the commercially available isocyanides, which have strong objectionable odours, 2-isocyano-4-methylphenyl diphenylacetate has a faint odour of rubber.
As we mentioned above, a new class of isocyanides, namely, 2-isocyanophenyl carboxylates, was synthesized only recently and therefore crystallographic data for these compounds are unknown. Only one crystal structure, that of a PdII complex with 2-isocyanophenyl carboxylate ligands, viz. cis-[PdCl2{2-CN—C6H4OOCC6H4-4-(OMe)}2], has been described (Tskhovrebov & Haukka, 2012). We report the first single-crystal X-ray structure of a 2-isocyanophenyl carboxylate. Achiral 2-isocyano-4-methylphenyl diphenylacetate, (I), crystallizes in a chiral fashion (space group P212121), owing to intra- and intermolecular interactions, as well as the steric effect of the diphenylacetate group. The molecule is not symmetric in the crystal even though it is achiral. Crystallization of achiral molecules in a chiral space group are known. Achiral 4-nitrophenyl isocyanide crystallizes in the orthorhombic chiral space group P212121 (Zeller & Hunter, 2004) due to the intermolecular interactions between neighbouring molecules.
Fig. 1 shows the structure of (I), in which the —C(═O)O— group lies out of the plane of the 2-isocyano-4-methylphenyl group. The C1—O1—C15—C16 torsion angle is 69.10 (16)°. The isocyanide group has a N1≡C21 bond length of 1.164 (2) Å. The average length of the N≡C bond in the known structures of organic isocyanides is 1.151 Å (Skodje et al., 2012). Also, we compared the structure of (I) with that of 2-benzyloxyphenyl isocyanide because of their structural similarities. The N≡C bond length for (I) is longer than that for 2-benzyloxyphenyl isocyanide [1.140 (2) Å; Hahn & Lugger, 1997]. The bond distance of the N—C bond adjacent to the isocyanide group is 1.391 (2) Å. A similar N—C bond distance [1.388 (2) Å] was observed for 2-benzyloxyphenyl isocyanide (Hahn & Lugger, 1997). The average C—N bond distance adjacent to the isocyanide group is 1.422 Å (Skodje et al., 2012). Compound (I) displays a nearly linear isocyanide bond angle [177.97 (15)°] (Fig. 1). The average angle in the known isocyanide structures is 177.65° (Skodje et al., 2012). The –C(═O)O– group lies out of the plane of the 2-isocyano-4-methylphenyl group.
The structure of (I) displays column packing, which runs along the a axis (Fig. 2). No face-to-face aromatic π–π interactions were found, the distances between the aromatic ring centroids in the columns are 6.290 (2) Å (Fig. 3), but several weak interactions were observed. The shortest among these are 2.621 (1) (C22—H22A···O1), 2.686 (1) (H6···O2), 2.700 (1) (H10···O2), 2.748 (2) (H4···C21), 2.778 (2) (H2···C21), 2.793 (2) (H7···benzene ring centroid) and 2.850 (2) Å (C22—H22C···C11).
Isocyanide (isonitrile) chemistry began in 1859 when Lieke synthesized the first compound of this type (Lieke, 1859) by the reaction of allyl iodide and silver cyanide. In 1958, isocyanides bacame generally available by dehydration of formamides prepared from primary amines (Ugi & Meyr, 1958). This synthesis and many other important investigations concerning the chemistry of isocyanides have been attributed to Ugi. For scientists who are unfamiliar with this chemistry, the main issue rests with the isocyanide synthesis: there have been concerns over their (wrongly) suspected toxicity and the strongly unpleasant smell associated with the most representative examples. With a few exceptions, isocyanides exhibit no appreciable toxicity to mammals. Some isocyanides have been isolated from natural sources (Garson & Simpson, 2004). In general, these compounds have been identified in marine invertebrates, such as sponges and nudibranch mollusks, and less frequently in fungi or cyanobacteria. Marine derivatives display almost exclusively a terpene-derived skeleton (sesqui- or diterpenes) and, in some cases, also interesting biological properties, such as antimalarial activity, antibiotic properties and cytotoxicity. The main methods of isocyanide preparation are the dehydration of N-monosubstituted formamides (Ugi & Meyr, 1958), the alkylation of cyanides (Lieke, 1859) and the reaction between dichlorocarbene and amine (Feuer et al., 1958). Isocyanides are versatile species in organic and organometallic syntheses (Ryu et al., 1996). They play a key role in several multicomponent processes, such as the Ugi and Passerini reactions (Ugi et al., 1991), and in metal-mediated transformations of ligands of metal complexes. Therefore, isocyanides and their derivatives can be used in inorganic, coordination, organic, polymeric, combinatorial and medicinal chemistry. However, isocyanides have a characteristic piercing odour. As a result, only the simplest commercially available isocyanides are used routinely and a relatively small amount of crystallographic data concerning isocyanides is known. Rather recently, a new family of unsaturated isocyanides, which do not have the objectionable odours, has been prepared by the base-promoted ring opening of oxazoles (Pirrung & Ghorai, 2006; Pirrung et al., 2009) (see Scheme 1). This method is useful in the preparation of ortho-acyloxy-substituted aryl isocyanides. We have expanded this method to include the more active acyl chlorides, which have acidic H atoms in the structure. The base-promoted reaction between 5-methylbenzoxazole and diphenylacetyl chloride was performed and 2-isocyano-4-methylphenyl diphenylacetate, (I), was isolated in 47% yield. The crystal structure of the prepared compound is described.
1H NMR (400 MHz, CDCl3): δ 7.45–7.47 (m, 4H), 7.39–7.42 (m, 4H), 7.34–7.36 (m, 2H), 7.25 (s, 1H), 7.20 (d, J = 8 Hz, 1H), 7.05 (d, J = 8 Hz, 1H), 5.39 (s, 1H), 2.36 (s, 3H).
IR (KBr, selected bands): 2125 s ν(N≡C), 1761 vs ν(C=O), 1110 vs ν(C—O) cm-1.
Elemental analysis calculated for C22H17NO2·0.5C4H8O2: C 77.61, H 5.70, N 3.77%; found: C 77.60, H 5.64, N 3.12%.
The first example of 2-isocyanophenyl carboxylate, which contains the acidic hydrogen, was synthesized by the base-promoted reaction between 5-methylbenzoxazole and diphenylacetyl chloride. Despite the possibility of a condensation reaction between the molecules of diphenylacetyl chloride, the formation of 2-isocyano-4-methylphenyl diphenylacetate was observed in basic media. In contrast to the previously obtained 2-isocyanophenyl carboxylates (Pirrung & Ghorai, 2006; Pirrung et al., 2009), which have pleasant fruity odours, and the commercially available isocyanides, which have strong objectionable odours, 2-isocyano-4-methylphenyl diphenylacetate has a faint odour of rubber.
As we mentioned above, a new class of isocyanides, namely, 2-isocyanophenyl carboxylates, was synthesized only recently and therefore crystallographic data for these compounds are unknown. Only one crystal structure, that of a PdII complex with 2-isocyanophenyl carboxylate ligands, viz. cis-[PdCl2{2-CN—C6H4OOCC6H4-4-(OMe)}2], has been described (Tskhovrebov & Haukka, 2012). We report the first single-crystal X-ray structure of a 2-isocyanophenyl carboxylate. Achiral 2-isocyano-4-methylphenyl diphenylacetate, (I), crystallizes in a chiral fashion (space group P212121), owing to intra- and intermolecular interactions, as well as the steric effect of the diphenylacetate group. The molecule is not symmetric in the crystal even though it is achiral. Crystallization of achiral molecules in a chiral space group are known. Achiral 4-nitrophenyl isocyanide crystallizes in the orthorhombic chiral space group P212121 (Zeller & Hunter, 2004) due to the intermolecular interactions between neighbouring molecules.
Fig. 1 shows the structure of (I), in which the —C(═O)O— group lies out of the plane of the 2-isocyano-4-methylphenyl group. The C1—O1—C15—C16 torsion angle is 69.10 (16)°. The isocyanide group has a N1≡C21 bond length of 1.164 (2) Å. The average length of the N≡C bond in the known structures of organic isocyanides is 1.151 Å (Skodje et al., 2012). Also, we compared the structure of (I) with that of 2-benzyloxyphenyl isocyanide because of their structural similarities. The N≡C bond length for (I) is longer than that for 2-benzyloxyphenyl isocyanide [1.140 (2) Å; Hahn & Lugger, 1997]. The bond distance of the N—C bond adjacent to the isocyanide group is 1.391 (2) Å. A similar N—C bond distance [1.388 (2) Å] was observed for 2-benzyloxyphenyl isocyanide (Hahn & Lugger, 1997). The average C—N bond distance adjacent to the isocyanide group is 1.422 Å (Skodje et al., 2012). Compound (I) displays a nearly linear isocyanide bond angle [177.97 (15)°] (Fig. 1). The average angle in the known isocyanide structures is 177.65° (Skodje et al., 2012). The –C(═O)O– group lies out of the plane of the 2-isocyano-4-methylphenyl group.
The structure of (I) displays column packing, which runs along the a axis (Fig. 2). No face-to-face aromatic π–π interactions were found, the distances between the aromatic ring centroids in the columns are 6.290 (2) Å (Fig. 3), but several weak interactions were observed. The shortest among these are 2.621 (1) (C22—H22A···O1), 2.686 (1) (H6···O2), 2.700 (1) (H10···O2), 2.748 (2) (H4···C21), 2.778 (2) (H2···C21), 2.793 (2) (H7···benzene ring centroid) and 2.850 (2) Å (C22—H22C···C11).
2-Isocyano-4-methylphenyl diphenylacetate, (I), was prepared according to the method used previously for the preparation of isocyanides, which do not have acidic H atoms (see Scheme 2). The reaction proceeds under N2. A 50 ml Schlenk tube equipped with a magnetic stirrer bar and charged with 5-methylbenzoxazole (1.00 g, 7.51 mmol) and tetrahydrofuran (THF; 18 ml) was cooled to 195 K for 5 min prior to addition of n-BuLi (1.6 M solution in hexanes, 5.15 ml, 8.24 mmol). The reaction mixture was stirred at this temperature for 1.5 h. Diphenylacetyl chloride (1.90 g, 8.24 mmol) was dissolved in THF (4 ml) and added dropwise to the reaction mixture. The resulting solution was heated to room temperature and stirred for 2 h. The reaction mixture was poured onto a mixture of ether (100 ml) and saturated aqueous NaHCO3 (50 ml). The organic layer was washed with water (2 × 50 ml), dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The resulting residue was dissolved in a minimal amount of chloroform and purified by silica-gel column chromatography [eluting with 49:1 v/v, petroleum ether (b.p. 313–333 K)/ethyl acetate] to provide the title compound as a yellow solid (yield 1.16 g, 47%). Crystals of (I) suitable for single-crystal X-ray diffraction were prepared by slow crystallization from a chloroform solution at room temperature (m.p. 395–397 K).
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms on C atoms were placed in calculated positions and were included in the refinement in the riding model approximation, with Uiso(H) values set at 1.2Ueq(C) and with C—H = 0.93 Å for the CH groups, and Uiso(H) values set at 1.5Ueq(C) and C—H = 0.96 Å for methyl groups.
Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: Dolomanov et al. (2009).
C22H17NO2 | Dx = 1.323 Mg m−3 |
Mr = 327.37 | Cu Kα radiation, λ = 1.54184 Å |
Orthorhombic, P212121 | Cell parameters from 22040 reflections |
a = 6.2897 (1) Å | θ = 3.9–75.6° |
b = 17.0161 (3) Å | µ = 0.67 mm−1 |
c = 15.3522 (3) Å | T = 100 K |
V = 1643.08 (5) Å3 | Prism, colourless |
Z = 4 | 0.15 × 0.11 × 0.08 mm |
F(000) = 688 |
Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer | 3263 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 3156 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.065 |
Detector resolution: 10.3829 pixels mm-1 | θmax = 72.4°, θmin = 3.9° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −21→21 |
Tmin = 0.707, Tmax = 1.000 | l = −18→17 |
36611 measured reflections |
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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3263 reflections | Δρmax = 0.16 e Å−3 |
227 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1365 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.1 (2) |
C22H17NO2 | V = 1643.08 (5) Å3 |
Mr = 327.37 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 6.2897 (1) Å | µ = 0.67 mm−1 |
b = 17.0161 (3) Å | T = 100 K |
c = 15.3522 (3) Å | 0.15 × 0.11 × 0.08 mm |
Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer | 3263 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 3156 reflections with I > 2σ(I) |
Tmin = 0.707, Tmax = 1.000 | Rint = 0.065 |
36611 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.116 | Δρmax = 0.16 e Å−3 |
S = 1.05 | Δρmin = −0.18 e Å−3 |
3263 reflections | Absolute structure: Flack (1983), 1365 Friedel pairs |
227 parameters | Absolute structure parameter: 0.1 (2) |
0 restraints |
Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.16660 (16) | 0.57295 (5) | 0.55343 (7) | 0.0215 (2) | |
O2 | −0.05220 (16) | 0.46785 (6) | 0.54245 (7) | 0.0246 (3) | |
N1 | −0.2448 (2) | 0.62610 (7) | 0.59380 (9) | 0.0231 (3) | |
C1 | 0.0985 (2) | 0.49918 (8) | 0.57558 (10) | 0.0198 (3) | |
C4 | 0.2584 (2) | 0.53470 (8) | 0.79385 (10) | 0.0227 (3) | |
H4 | 0.3951 | 0.5507 | 0.7790 | 0.027* | |
C15 | 0.0488 (2) | 0.61572 (8) | 0.49291 (10) | 0.0198 (3) | |
C16 | −0.1534 (2) | 0.64412 (8) | 0.51375 (9) | 0.0198 (3) | |
C20 | 0.1414 (2) | 0.63590 (8) | 0.41423 (10) | 0.0210 (3) | |
H20 | 0.2761 | 0.6173 | 0.4001 | 0.025* | |
C3 | 0.1403 (2) | 0.48914 (8) | 0.73538 (9) | 0.0200 (3) | |
C19 | 0.0320 (2) | 0.68421 (8) | 0.35650 (10) | 0.0220 (3) | |
H19 | 0.0956 | 0.6980 | 0.3040 | 0.026* | |
C17 | −0.2625 (2) | 0.69192 (8) | 0.45525 (10) | 0.0213 (3) | |
H17 | −0.3975 | 0.7102 | 0.4694 | 0.026* | |
C9 | 0.2853 (2) | 0.37969 (8) | 0.63380 (10) | 0.0213 (3) | |
C7 | −0.1490 (2) | 0.48809 (9) | 0.83927 (10) | 0.0249 (3) | |
H7 | −0.2855 | 0.4722 | 0.8544 | 0.030* | |
C10 | 0.4883 (2) | 0.35715 (9) | 0.60772 (10) | 0.0246 (3) | |
H10 | 0.5928 | 0.3951 | 0.5997 | 0.030* | |
C18 | −0.1715 (2) | 0.71258 (8) | 0.37573 (10) | 0.0217 (3) | |
C8 | −0.0657 (2) | 0.46722 (8) | 0.75913 (10) | 0.0230 (3) | |
H8 | −0.1481 | 0.4382 | 0.7205 | 0.028* | |
C2 | 0.2392 (2) | 0.46703 (8) | 0.64753 (9) | 0.0201 (3) | |
H2 | 0.3756 | 0.4947 | 0.6436 | 0.024* | |
C11 | 0.5367 (2) | 0.27819 (10) | 0.59345 (11) | 0.0284 (3) | |
H11 | 0.6724 | 0.2640 | 0.5753 | 0.034* | |
C5 | 0.1737 (3) | 0.55624 (8) | 0.87379 (10) | 0.0254 (3) | |
H5 | 0.2536 | 0.5867 | 0.9120 | 0.030* | |
C6 | −0.0299 (3) | 0.53260 (8) | 0.89707 (10) | 0.0251 (3) | |
H6 | −0.0858 | 0.5465 | 0.9510 | 0.030* | |
C14 | 0.1319 (2) | 0.32166 (9) | 0.64535 (11) | 0.0268 (3) | |
H14 | −0.0049 | 0.3358 | 0.6621 | 0.032* | |
C12 | 0.3833 (3) | 0.22089 (9) | 0.60619 (11) | 0.0293 (3) | |
H12 | 0.4157 | 0.1682 | 0.5974 | 0.035* | |
C13 | 0.1805 (3) | 0.24310 (10) | 0.63228 (12) | 0.0306 (4) | |
H13 | 0.0767 | 0.2050 | 0.6410 | 0.037* | |
C22 | −0.2885 (3) | 0.76499 (9) | 0.31347 (11) | 0.0272 (3) | |
H22A | −0.2632 | 0.8189 | 0.3285 | 0.041* | |
H22B | −0.4381 | 0.7542 | 0.3168 | 0.041* | |
H22C | −0.2391 | 0.7554 | 0.2553 | 0.041* | |
C21 | −0.3237 (3) | 0.61327 (10) | 0.66088 (12) | 0.0317 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0247 (4) | 0.0234 (5) | 0.0163 (5) | −0.0009 (4) | −0.0018 (4) | 0.0022 (4) |
O2 | 0.0255 (5) | 0.0259 (5) | 0.0224 (6) | −0.0038 (4) | −0.0038 (4) | 0.0024 (4) |
N1 | 0.0243 (6) | 0.0240 (6) | 0.0209 (7) | 0.0000 (5) | 0.0028 (5) | 0.0019 (5) |
C1 | 0.0208 (6) | 0.0241 (6) | 0.0144 (7) | 0.0011 (5) | 0.0028 (5) | 0.0003 (5) |
C4 | 0.0243 (7) | 0.0242 (6) | 0.0194 (8) | −0.0034 (5) | −0.0008 (5) | 0.0041 (5) |
C15 | 0.0226 (6) | 0.0202 (6) | 0.0166 (7) | −0.0013 (5) | −0.0042 (5) | −0.0012 (5) |
C16 | 0.0239 (6) | 0.0216 (6) | 0.0138 (7) | −0.0016 (5) | 0.0021 (5) | −0.0021 (5) |
C20 | 0.0228 (6) | 0.0219 (6) | 0.0185 (7) | −0.0011 (5) | 0.0021 (5) | −0.0035 (5) |
C3 | 0.0254 (7) | 0.0208 (6) | 0.0138 (7) | 0.0014 (5) | −0.0017 (5) | 0.0041 (5) |
C19 | 0.0298 (7) | 0.0225 (6) | 0.0136 (7) | −0.0018 (5) | 0.0019 (5) | −0.0005 (5) |
C17 | 0.0222 (6) | 0.0219 (6) | 0.0198 (8) | −0.0004 (5) | 0.0003 (5) | −0.0025 (5) |
C9 | 0.0239 (7) | 0.0281 (7) | 0.0121 (7) | 0.0008 (5) | −0.0017 (5) | 0.0019 (5) |
C7 | 0.0245 (7) | 0.0275 (6) | 0.0226 (8) | −0.0001 (5) | 0.0027 (6) | 0.0037 (6) |
C10 | 0.0257 (7) | 0.0355 (7) | 0.0127 (7) | −0.0003 (6) | −0.0007 (5) | 0.0037 (6) |
C18 | 0.0274 (7) | 0.0199 (5) | 0.0178 (7) | −0.0001 (5) | −0.0019 (6) | −0.0035 (5) |
C8 | 0.0249 (7) | 0.0265 (6) | 0.0177 (8) | −0.0011 (5) | −0.0031 (5) | 0.0008 (5) |
C2 | 0.0202 (6) | 0.0253 (6) | 0.0149 (7) | −0.0026 (5) | −0.0006 (5) | 0.0026 (5) |
C11 | 0.0261 (7) | 0.0392 (8) | 0.0198 (8) | 0.0086 (6) | −0.0013 (6) | −0.0020 (6) |
C5 | 0.0333 (7) | 0.0234 (6) | 0.0195 (8) | −0.0029 (6) | −0.0046 (6) | −0.0005 (6) |
C6 | 0.0342 (8) | 0.0260 (7) | 0.0150 (8) | 0.0043 (6) | 0.0019 (6) | 0.0007 (5) |
C14 | 0.0220 (7) | 0.0304 (7) | 0.0280 (8) | 0.0004 (5) | 0.0002 (6) | −0.0009 (6) |
C12 | 0.0348 (8) | 0.0280 (7) | 0.0251 (9) | 0.0064 (6) | −0.0027 (6) | −0.0027 (6) |
C13 | 0.0310 (7) | 0.0295 (7) | 0.0312 (9) | −0.0010 (6) | −0.0009 (7) | −0.0008 (6) |
C22 | 0.0354 (8) | 0.0281 (7) | 0.0180 (8) | 0.0048 (6) | −0.0029 (6) | 0.0007 (6) |
C21 | 0.0319 (7) | 0.0357 (8) | 0.0274 (9) | 0.0027 (6) | 0.0075 (6) | 0.0058 (7) |
O1—C1 | 1.3691 (16) | C9—C2 | 1.5287 (19) |
O1—C15 | 1.3935 (17) | C7—C8 | 1.383 (2) |
O2—C1 | 1.2007 (18) | C7—C6 | 1.386 (2) |
N1—C21 | 1.164 (2) | C7—H7 | 0.9300 |
N1—C16 | 1.3908 (19) | C10—C11 | 1.395 (2) |
C1—C2 | 1.517 (2) | C10—H10 | 0.9300 |
C4—C5 | 1.387 (2) | C18—C22 | 1.500 (2) |
C4—C3 | 1.400 (2) | C8—H8 | 0.9300 |
C4—H4 | 0.9300 | C2—H2 | 0.9800 |
C15—C20 | 1.384 (2) | C11—C12 | 1.386 (2) |
C15—C16 | 1.398 (2) | C11—H11 | 0.9300 |
C16—C17 | 1.392 (2) | C5—C6 | 1.389 (2) |
C20—C19 | 1.391 (2) | C5—H5 | 0.9300 |
C20—H20 | 0.9300 | C6—H6 | 0.9300 |
C3—C8 | 1.397 (2) | C14—C13 | 1.386 (2) |
C3—C2 | 1.532 (2) | C14—H14 | 0.9300 |
C19—C18 | 1.400 (2) | C12—C13 | 1.389 (2) |
C19—H19 | 0.9300 | C12—H12 | 0.9300 |
C17—C18 | 1.394 (2) | C13—H13 | 0.9300 |
C17—H17 | 0.9300 | C22—H22A | 0.9600 |
C9—C14 | 1.392 (2) | C22—H22B | 0.9600 |
C9—C10 | 1.392 (2) | C22—H22C | 0.9600 |
C1—O1—C15 | 118.57 (11) | C17—C18—C22 | 120.44 (13) |
C21—N1—C16 | 177.97 (15) | C19—C18—C22 | 121.29 (14) |
O2—C1—O1 | 123.28 (13) | C7—C8—C3 | 120.98 (14) |
O2—C1—C2 | 127.50 (13) | C7—C8—H8 | 119.5 |
O1—C1—C2 | 109.21 (11) | C3—C8—H8 | 119.5 |
C5—C4—C3 | 120.64 (14) | C1—C2—C9 | 111.15 (11) |
C5—C4—H4 | 119.7 | C1—C2—C3 | 108.38 (11) |
C3—C4—H4 | 119.7 | C9—C2—C3 | 115.91 (11) |
C20—C15—O1 | 119.17 (13) | C1—C2—H2 | 107.0 |
C20—C15—C16 | 119.80 (13) | C9—C2—H2 | 107.0 |
O1—C15—C16 | 120.79 (13) | C3—C2—H2 | 107.0 |
N1—C16—C17 | 119.68 (13) | C12—C11—C10 | 120.26 (14) |
N1—C16—C15 | 120.13 (13) | C12—C11—H11 | 119.9 |
C17—C16—C15 | 120.18 (13) | C10—C11—H11 | 119.9 |
C15—C20—C19 | 119.63 (13) | C4—C5—C6 | 120.36 (14) |
C15—C20—H20 | 120.2 | C4—C5—H5 | 119.8 |
C19—C20—H20 | 120.2 | C6—C5—H5 | 119.8 |
C8—C3—C4 | 118.23 (14) | C7—C6—C5 | 119.44 (15) |
C8—C3—C2 | 122.75 (13) | C7—C6—H6 | 120.3 |
C4—C3—C2 | 119.00 (13) | C5—C6—H6 | 120.3 |
C20—C19—C18 | 121.46 (14) | C13—C14—C9 | 120.88 (14) |
C20—C19—H19 | 119.3 | C13—C14—H14 | 119.6 |
C18—C19—H19 | 119.3 | C9—C14—H14 | 119.6 |
C16—C17—C18 | 120.66 (13) | C11—C12—C13 | 119.24 (15) |
C16—C17—H17 | 119.7 | C11—C12—H12 | 120.4 |
C18—C17—H17 | 119.7 | C13—C12—H12 | 120.4 |
C14—C9—C10 | 118.48 (14) | C14—C13—C12 | 120.43 (15) |
C14—C9—C2 | 122.74 (13) | C14—C13—H13 | 119.8 |
C10—C9—C2 | 118.77 (13) | C12—C13—H13 | 119.8 |
C8—C7—C6 | 120.33 (13) | C18—C22—H22A | 109.5 |
C8—C7—H7 | 119.8 | C18—C22—H22B | 109.5 |
C6—C7—H7 | 119.8 | H22A—C22—H22B | 109.5 |
C9—C10—C11 | 120.70 (14) | C18—C22—H22C | 109.5 |
C9—C10—H10 | 119.6 | H22A—C22—H22C | 109.5 |
C11—C10—H10 | 119.6 | H22B—C22—H22C | 109.5 |
C17—C18—C19 | 118.26 (14) | ||
C15—O1—C1—O2 | 3.65 (19) | C4—C3—C8—C7 | −1.7 (2) |
C15—O1—C1—C2 | −175.15 (11) | C2—C3—C8—C7 | 179.73 (12) |
C1—O1—C15—C20 | −116.54 (14) | O2—C1—C2—C9 | 40.8 (2) |
C1—O1—C15—C16 | 69.10 (16) | O1—C1—C2—C9 | −140.44 (12) |
C21—N1—C16—C17 | −37 (4) | O2—C1—C2—C3 | −87.66 (17) |
C21—N1—C16—C15 | 142 (4) | O1—C1—C2—C3 | 91.07 (13) |
C20—C15—C16—N1 | −178.00 (12) | C14—C9—C2—C1 | −71.37 (18) |
O1—C15—C16—N1 | −3.68 (19) | C10—C9—C2—C1 | 107.91 (15) |
C20—C15—C16—C17 | 0.66 (19) | C14—C9—C2—C3 | 52.96 (19) |
O1—C15—C16—C17 | 174.98 (13) | C10—C9—C2—C3 | −127.77 (15) |
O1—C15—C20—C19 | −174.54 (12) | C8—C3—C2—C1 | 57.80 (16) |
C16—C15—C20—C19 | −0.1 (2) | C4—C3—C2—C1 | −120.71 (14) |
C5—C4—C3—C8 | 1.1 (2) | C8—C3—C2—C9 | −67.94 (17) |
C5—C4—C3—C2 | 179.63 (12) | C4—C3—C2—C9 | 113.55 (14) |
C15—C20—C19—C18 | −0.6 (2) | C9—C10—C11—C12 | −0.8 (3) |
N1—C16—C17—C18 | 178.15 (12) | C3—C4—C5—C6 | 0.2 (2) |
C15—C16—C17—C18 | −0.5 (2) | C8—C7—C6—C5 | 0.1 (2) |
C14—C9—C10—C11 | 0.1 (2) | C4—C5—C6—C7 | −0.8 (2) |
C2—C9—C10—C11 | −179.25 (14) | C10—C9—C14—C13 | 0.8 (2) |
C16—C17—C18—C19 | −0.2 (2) | C2—C9—C14—C13 | −179.95 (14) |
C16—C17—C18—C22 | −179.16 (13) | C10—C11—C12—C13 | 0.8 (3) |
C20—C19—C18—C17 | 0.7 (2) | C9—C14—C13—C12 | −0.9 (3) |
C20—C19—C18—C22 | 179.70 (14) | C11—C12—C13—C14 | 0.1 (3) |
C6—C7—C8—C3 | 1.2 (2) |
Experimental details
Crystal data | |
Chemical formula | C22H17NO2 |
Mr | 327.37 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 6.2897 (1), 17.0161 (3), 15.3522 (3) |
V (Å3) | 1643.08 (5) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.15 × 0.11 × 0.08 |
Data collection | |
Diffractometer | Agilent SuperNova (Dual, Cu at zero, Atlas) |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.707, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36611, 3263, 3156 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.116, 1.05 |
No. of reflections | 3263 |
No. of parameters | 227 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.18 |
Absolute structure | Flack (1983), 1365 Friedel pairs |
Absolute structure parameter | 0.1 (2) |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Dolomanov et al. (2009).