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Acidic hydrogen containing 2-iso­cyano-4-methyl­phenyl di­phenyl­acetate, C22H17NO2, (I), was synthesized by the base-promoted reaction between 5-methyl­benzoxazole and di­phenyl­acetyl chloride. Achiral (I) crystallizes in the chiral P212121 space group. The C[triple bond]N bond length is 1.164 (2) Å and the angle between the OCO and 2-iso­cyano-4-methyl­phenyl planes is 69.10 (16)°. Mol­ecules are linked via C=O...Hphen­yl and bifurcated N[triple bond]C...Hphen­yl/N[triple bond]C...Hmethine hydrogen bonds, forming one-dimensional arrays.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615001588/cu3073sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615001588/cu3073Isup2.hkl
Contains datablock I

cdx

Chemdraw file https://doi.org/10.1107/S2053229615001588/cu3073Isup3.cdx
Supplementary material

cdx

Chemdraw file https://doi.org/10.1107/S2053229615001588/cu3073Isup4.cdx
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615001588/cu3073Isup5.cml
Supplementary material

CCDC reference: 1035106

Introduction top

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.

Experimental top

Synthesis and crystallization top

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).

Spectroscipic data and elemental analysis top

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(NC), 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%.

Refinement top

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.

Results and discussion top

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 N1C21 bond length of 1.164 (2) Å. The average length of the NC 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 NC 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 ππ 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).

Structure description top

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(NC), 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 N1C21 bond length of 1.164 (2) Å. The average length of the NC 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 NC 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 ππ 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).

Synthesis and crystallization top

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).

Refinement details top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram of (I), including the unit-cell axes. The view is down the a axis.
[Figure 3] Fig. 3. The centroid–centroid distances between the benzene rings in the 2-isocyano-4-methylphenyl diphenylacetate molecules packed in columns.
2-Isocyano-4-methylphenyl diphenylacetate top
Crystal data top
C22H17NO2Dx = 1.323 Mg m3
Mr = 327.37Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121Cell parameters from 22040 reflections
a = 6.2897 (1) Åθ = 3.9–75.6°
b = 17.0161 (3) ŵ = 0.67 mm1
c = 15.3522 (3) ÅT = 100 K
V = 1643.08 (5) Å3Prism, colourless
Z = 40.15 × 0.11 × 0.08 mm
F(000) = 688
Data collection top
Agilent SuperNova (Dual, Cu at zero, Atlas)
diffractometer
3263 independent reflections
Radiation source: SuperNova (Cu) X-ray Source3156 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.065
Detector resolution: 10.3829 pixels mm-1θmax = 72.4°, θmin = 3.9°
ω scansh = 77
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 2121
Tmin = 0.707, Tmax = 1.000l = 1817
36611 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-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 reflectionsΔρmax = 0.16 e Å3
227 parametersΔρmin = 0.18 e Å3
0 restraintsAbsolute structure: Flack (1983), 1365 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.1 (2)
Crystal data top
C22H17NO2V = 1643.08 (5) Å3
Mr = 327.37Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 6.2897 (1) ŵ = 0.67 mm1
b = 17.0161 (3) ÅT = 100 K
c = 15.3522 (3) Å0.15 × 0.11 × 0.08 mm
Data collection top
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 = 1.000Rint = 0.065
36611 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.116Δρmax = 0.16 e Å3
S = 1.05Δρmin = 0.18 e Å3
3263 reflectionsAbsolute structure: Flack (1983), 1365 Friedel pairs
227 parametersAbsolute structure parameter: 0.1 (2)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.16660 (16)0.57295 (5)0.55343 (7)0.0215 (2)
O20.05220 (16)0.46785 (6)0.54245 (7)0.0246 (3)
N10.2448 (2)0.62610 (7)0.59380 (9)0.0231 (3)
C10.0985 (2)0.49918 (8)0.57558 (10)0.0198 (3)
C40.2584 (2)0.53470 (8)0.79385 (10)0.0227 (3)
H40.39510.55070.77900.027*
C150.0488 (2)0.61572 (8)0.49291 (10)0.0198 (3)
C160.1534 (2)0.64412 (8)0.51375 (9)0.0198 (3)
C200.1414 (2)0.63590 (8)0.41423 (10)0.0210 (3)
H200.27610.61730.40010.025*
C30.1403 (2)0.48914 (8)0.73538 (9)0.0200 (3)
C190.0320 (2)0.68421 (8)0.35650 (10)0.0220 (3)
H190.09560.69800.30400.026*
C170.2625 (2)0.69192 (8)0.45525 (10)0.0213 (3)
H170.39750.71020.46940.026*
C90.2853 (2)0.37969 (8)0.63380 (10)0.0213 (3)
C70.1490 (2)0.48809 (9)0.83927 (10)0.0249 (3)
H70.28550.47220.85440.030*
C100.4883 (2)0.35715 (9)0.60772 (10)0.0246 (3)
H100.59280.39510.59970.030*
C180.1715 (2)0.71258 (8)0.37573 (10)0.0217 (3)
C80.0657 (2)0.46722 (8)0.75913 (10)0.0230 (3)
H80.14810.43820.72050.028*
C20.2392 (2)0.46703 (8)0.64753 (9)0.0201 (3)
H20.37560.49470.64360.024*
C110.5367 (2)0.27819 (10)0.59345 (11)0.0284 (3)
H110.67240.26400.57530.034*
C50.1737 (3)0.55624 (8)0.87379 (10)0.0254 (3)
H50.25360.58670.91200.030*
C60.0299 (3)0.53260 (8)0.89707 (10)0.0251 (3)
H60.08580.54650.95100.030*
C140.1319 (2)0.32166 (9)0.64535 (11)0.0268 (3)
H140.00490.33580.66210.032*
C120.3833 (3)0.22089 (9)0.60619 (11)0.0293 (3)
H120.41570.16820.59740.035*
C130.1805 (3)0.24310 (10)0.63228 (12)0.0306 (4)
H130.07670.20500.64100.037*
C220.2885 (3)0.76499 (9)0.31347 (11)0.0272 (3)
H22A0.26320.81890.32850.041*
H22B0.43810.75420.31680.041*
H22C0.23910.75540.25530.041*
C210.3237 (3)0.61327 (10)0.66088 (12)0.0317 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0247 (4)0.0234 (5)0.0163 (5)0.0009 (4)0.0018 (4)0.0022 (4)
O20.0255 (5)0.0259 (5)0.0224 (6)0.0038 (4)0.0038 (4)0.0024 (4)
N10.0243 (6)0.0240 (6)0.0209 (7)0.0000 (5)0.0028 (5)0.0019 (5)
C10.0208 (6)0.0241 (6)0.0144 (7)0.0011 (5)0.0028 (5)0.0003 (5)
C40.0243 (7)0.0242 (6)0.0194 (8)0.0034 (5)0.0008 (5)0.0041 (5)
C150.0226 (6)0.0202 (6)0.0166 (7)0.0013 (5)0.0042 (5)0.0012 (5)
C160.0239 (6)0.0216 (6)0.0138 (7)0.0016 (5)0.0021 (5)0.0021 (5)
C200.0228 (6)0.0219 (6)0.0185 (7)0.0011 (5)0.0021 (5)0.0035 (5)
C30.0254 (7)0.0208 (6)0.0138 (7)0.0014 (5)0.0017 (5)0.0041 (5)
C190.0298 (7)0.0225 (6)0.0136 (7)0.0018 (5)0.0019 (5)0.0005 (5)
C170.0222 (6)0.0219 (6)0.0198 (8)0.0004 (5)0.0003 (5)0.0025 (5)
C90.0239 (7)0.0281 (7)0.0121 (7)0.0008 (5)0.0017 (5)0.0019 (5)
C70.0245 (7)0.0275 (6)0.0226 (8)0.0001 (5)0.0027 (6)0.0037 (6)
C100.0257 (7)0.0355 (7)0.0127 (7)0.0003 (6)0.0007 (5)0.0037 (6)
C180.0274 (7)0.0199 (5)0.0178 (7)0.0001 (5)0.0019 (6)0.0035 (5)
C80.0249 (7)0.0265 (6)0.0177 (8)0.0011 (5)0.0031 (5)0.0008 (5)
C20.0202 (6)0.0253 (6)0.0149 (7)0.0026 (5)0.0006 (5)0.0026 (5)
C110.0261 (7)0.0392 (8)0.0198 (8)0.0086 (6)0.0013 (6)0.0020 (6)
C50.0333 (7)0.0234 (6)0.0195 (8)0.0029 (6)0.0046 (6)0.0005 (6)
C60.0342 (8)0.0260 (7)0.0150 (8)0.0043 (6)0.0019 (6)0.0007 (5)
C140.0220 (7)0.0304 (7)0.0280 (8)0.0004 (5)0.0002 (6)0.0009 (6)
C120.0348 (8)0.0280 (7)0.0251 (9)0.0064 (6)0.0027 (6)0.0027 (6)
C130.0310 (7)0.0295 (7)0.0312 (9)0.0010 (6)0.0009 (7)0.0008 (6)
C220.0354 (8)0.0281 (7)0.0180 (8)0.0048 (6)0.0029 (6)0.0007 (6)
C210.0319 (7)0.0357 (8)0.0274 (9)0.0027 (6)0.0075 (6)0.0058 (7)
Geometric parameters (Å, º) top
O1—C11.3691 (16)C9—C21.5287 (19)
O1—C151.3935 (17)C7—C81.383 (2)
O2—C11.2007 (18)C7—C61.386 (2)
N1—C211.164 (2)C7—H70.9300
N1—C161.3908 (19)C10—C111.395 (2)
C1—C21.517 (2)C10—H100.9300
C4—C51.387 (2)C18—C221.500 (2)
C4—C31.400 (2)C8—H80.9300
C4—H40.9300C2—H20.9800
C15—C201.384 (2)C11—C121.386 (2)
C15—C161.398 (2)C11—H110.9300
C16—C171.392 (2)C5—C61.389 (2)
C20—C191.391 (2)C5—H50.9300
C20—H200.9300C6—H60.9300
C3—C81.397 (2)C14—C131.386 (2)
C3—C21.532 (2)C14—H140.9300
C19—C181.400 (2)C12—C131.389 (2)
C19—H190.9300C12—H120.9300
C17—C181.394 (2)C13—H130.9300
C17—H170.9300C22—H22A0.9600
C9—C141.392 (2)C22—H22B0.9600
C9—C101.392 (2)C22—H22C0.9600
C1—O1—C15118.57 (11)C17—C18—C22120.44 (13)
C21—N1—C16177.97 (15)C19—C18—C22121.29 (14)
O2—C1—O1123.28 (13)C7—C8—C3120.98 (14)
O2—C1—C2127.50 (13)C7—C8—H8119.5
O1—C1—C2109.21 (11)C3—C8—H8119.5
C5—C4—C3120.64 (14)C1—C2—C9111.15 (11)
C5—C4—H4119.7C1—C2—C3108.38 (11)
C3—C4—H4119.7C9—C2—C3115.91 (11)
C20—C15—O1119.17 (13)C1—C2—H2107.0
C20—C15—C16119.80 (13)C9—C2—H2107.0
O1—C15—C16120.79 (13)C3—C2—H2107.0
N1—C16—C17119.68 (13)C12—C11—C10120.26 (14)
N1—C16—C15120.13 (13)C12—C11—H11119.9
C17—C16—C15120.18 (13)C10—C11—H11119.9
C15—C20—C19119.63 (13)C4—C5—C6120.36 (14)
C15—C20—H20120.2C4—C5—H5119.8
C19—C20—H20120.2C6—C5—H5119.8
C8—C3—C4118.23 (14)C7—C6—C5119.44 (15)
C8—C3—C2122.75 (13)C7—C6—H6120.3
C4—C3—C2119.00 (13)C5—C6—H6120.3
C20—C19—C18121.46 (14)C13—C14—C9120.88 (14)
C20—C19—H19119.3C13—C14—H14119.6
C18—C19—H19119.3C9—C14—H14119.6
C16—C17—C18120.66 (13)C11—C12—C13119.24 (15)
C16—C17—H17119.7C11—C12—H12120.4
C18—C17—H17119.7C13—C12—H12120.4
C14—C9—C10118.48 (14)C14—C13—C12120.43 (15)
C14—C9—C2122.74 (13)C14—C13—H13119.8
C10—C9—C2118.77 (13)C12—C13—H13119.8
C8—C7—C6120.33 (13)C18—C22—H22A109.5
C8—C7—H7119.8C18—C22—H22B109.5
C6—C7—H7119.8H22A—C22—H22B109.5
C9—C10—C11120.70 (14)C18—C22—H22C109.5
C9—C10—H10119.6H22A—C22—H22C109.5
C11—C10—H10119.6H22B—C22—H22C109.5
C17—C18—C19118.26 (14)
C15—O1—C1—O23.65 (19)C4—C3—C8—C71.7 (2)
C15—O1—C1—C2175.15 (11)C2—C3—C8—C7179.73 (12)
C1—O1—C15—C20116.54 (14)O2—C1—C2—C940.8 (2)
C1—O1—C15—C1669.10 (16)O1—C1—C2—C9140.44 (12)
C21—N1—C16—C1737 (4)O2—C1—C2—C387.66 (17)
C21—N1—C16—C15142 (4)O1—C1—C2—C391.07 (13)
C20—C15—C16—N1178.00 (12)C14—C9—C2—C171.37 (18)
O1—C15—C16—N13.68 (19)C10—C9—C2—C1107.91 (15)
C20—C15—C16—C170.66 (19)C14—C9—C2—C352.96 (19)
O1—C15—C16—C17174.98 (13)C10—C9—C2—C3127.77 (15)
O1—C15—C20—C19174.54 (12)C8—C3—C2—C157.80 (16)
C16—C15—C20—C190.1 (2)C4—C3—C2—C1120.71 (14)
C5—C4—C3—C81.1 (2)C8—C3—C2—C967.94 (17)
C5—C4—C3—C2179.63 (12)C4—C3—C2—C9113.55 (14)
C15—C20—C19—C180.6 (2)C9—C10—C11—C120.8 (3)
N1—C16—C17—C18178.15 (12)C3—C4—C5—C60.2 (2)
C15—C16—C17—C180.5 (2)C8—C7—C6—C50.1 (2)
C14—C9—C10—C110.1 (2)C4—C5—C6—C70.8 (2)
C2—C9—C10—C11179.25 (14)C10—C9—C14—C130.8 (2)
C16—C17—C18—C190.2 (2)C2—C9—C14—C13179.95 (14)
C16—C17—C18—C22179.16 (13)C10—C11—C12—C130.8 (3)
C20—C19—C18—C170.7 (2)C9—C14—C13—C120.9 (3)
C20—C19—C18—C22179.70 (14)C11—C12—C13—C140.1 (3)
C6—C7—C8—C31.2 (2)

Experimental details

Crystal data
Chemical formulaC22H17NO2
Mr327.37
Crystal system, space groupOrthorhombic, P212121
Temperature (K)100
a, b, c (Å)6.2897 (1), 17.0161 (3), 15.3522 (3)
V3)1643.08 (5)
Z4
Radiation typeCu Kα
µ (mm1)0.67
Crystal size (mm)0.15 × 0.11 × 0.08
Data collection
DiffractometerAgilent SuperNova (Dual, Cu at zero, Atlas)
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.707, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
36611, 3263, 3156
Rint0.065
(sin θ/λ)max1)0.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.116, 1.05
No. of reflections3263
No. of parameters227
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.18
Absolute structureFlack (1983), 1365 Friedel pairs
Absolute structure parameter0.1 (2)

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Dolomanov et al. (2009).

 

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