research communications
of diethyl 2-acetoxy-2-[3-(4-nitrophenyl)-3-oxo-1-phenylpropyl]malonate
aInstitute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, H-1519 Budapest, POB 206, Hungary, and bDepartment of Organic Chemistry and Technology, Budapest University of Technology and Economics, H-1521 Budapest, POB 91, Hungary
*Correspondence e-mail: may.nora@ttk.mta.hu
In the racemic title compound, C24H25NO9, the dihedral angle between the planes of the two benzene-ring systems is 80.16 (6)°, while the side-chain conformation is stabilized by a methylene–carboxyl C—H⋯O hydrogen bond. Weak intermolecular C—H⋯O hydrogen bonds form inversion dimers [graph set R22(16)] which are linked into chains extending along a. Further C—H⋯O hydrogen bonding extends the structure along b through cyclic R22(10) motifs. Although no π–π aromatic ring interactions are present in the structure, C—H⋯π ring interactions across c generate an overall three-dimensional supramolecular structure.
Keywords: crystal structure; phenylpropyl malonate; phase-transfer reaction; crown ether catalyst; hydrogen bonding; C—H⋯π ring interactions.
CCDC reference: 1449223
1. Chemical context
The formation of C—C bonds by the Michael addition of the appropriate carboanionic reagents to α,β-unsaturated carbonyl compounds is one of the most useful methods of remote functionalization in organic synthesis (Mather et al., 2006; Little et al., 1995). In particular, a much studied reaction is the conjugate addition of malonates to Compounds with the chalcone backbone were reported to possess a wide range of biological activities, such as nematicidal, antifungal, antiallergenic, antimicrobial, anticancer, antimalarial and antifeedant properties. Malonates are traditionally regarded as important materials for synthesizing the key intermediates of numerous active substances, but are rarely found as pharmacophores belonging to the target compounds (Lopez et al., 2001; Chen et al., 2016). Therefore, a catalytic version of the Michael addition of dialkyl malonates to in the presence of different catalysts has been studied extensively in recent years. Many phase-transfer-catalyzed methods that are simple and environmentally friendly have been developed for the Michael reaction (Shioiri, 1997). This new was prepared in a phase-transfer reaction using a sugar-based crown ether as the catalyst (Rapi et al., 2016).
2. Structural commentary
The molecular structure of the racemic title compound is shown in Fig. 1. In this molecule, the C4 atom is a chiral centre, but no resolution occurred upon crystal preparation, the crystallizing in the centrosymmetric P21/n. The dihedral angle between the planes of the two benzene rings is 80.16 (6)° and the molecular conformation is stabilized by an intramolecular methylene C5—H⋯O5 hydrogen bond (Table 1).
3. Supramolecular features
Because of the numerous C=O acceptor groups and the lack of primary donor groups in the molecule, the main intermolecular interactions in the crystal are weak C—H⋯Ocarboxyl hydrogen bonds (Table 1), having H⋯O distances equal to or less than 2.6 Å. However, one of the four interactions (C24—H⋯O8iii; see Table 1 for hydrogen-bond geometry details and symmetry codes) involves a nitro O-atom acceptor. Intermolecular C15—H⋯O7ii hydrogen bonds form centrosymmetric cyclic dimers (Fig. 2) having the graph-set descriptor (Bernstein et al., 1995) R22(16). These dimers are linked along the crystallographic a direction through C24—H⋯O8iii hydrogen bonds, forming a chain. These chains are further extended in the crystallographic b direction through C11—H⋯O4i and C12—H⋯O6i interactions, forming a cyclic motif with the graph-set descriptor of R22(10) (Fig. 3). Despite the presence of two aromatic rings in the molecule, there are no significant π–π interactions in the This can be explained by the diverse chain system of the molecule and, therefore, the steric preference of the C—H⋯O hydrogen bonds. However, there is a C16—H16⋯π interaction across c with the C7–C12 nitrophenyl ring (C⋯Cgiv = 2.81 Å and C—H⋯Cgiv = 149°; Cg is the centroid of the C7–C12 ring) (Fig. 4 and Table 1), resulting in an overall three-dimensional supramolecular structure. The relatively high calculated density (1.367 Mg m−3) and KPI index (Kitaigorodskii packing coefficient = 69.6%) (Spek, 2009) show efficient packing of the molecule, resulting in no residual solvent-accessible voids.
4. Database survey
The structures of different derivatives of 1,2-diphenylpentan-1-one, carrying methyl or nitrile substituents on the chiral C atom, have been reported, viz. Cambridge Structural Database (CSD; Groom & Allen, 2014) refcodes RULFIN [(S)-4-methyl-4-nitro-1,3-diphenylpentanone; Bakó et al., 1997], DULJOK (1,3-diphenylbutan-1-one; Bąkowicz & Turowska-Tyrk, 2010) and LAPKEU (4-oxo-2,4-diphenylbutanonitrile; Abdel-Aziz et al., 2012). RULFIN and DULJOK crystallized in the chiral P212121 and Pca21 space groups, respectively, and LAPKEU crystallized as a in the centrosymmetric P21/c Comparing the dihedral angles between the planes of the two benzene rings, the of the bulky substituents on atom C2 can be seen. This value is 62.5° for the methyl derivative (DULJOK) and 68.4° for the nitrile (LAPKEU), but significantly higher for the bulky methyl–nitro derivative (88.13°; RULFIN) or the title compound (80.2°).
5. Synthesis and crystallization
The title compound was synthesized by the reaction of 4′-nitrochalcone [(E)-3-(4-nitrophenyl)-1-phenylprop-2-en-1-one] with diethyl 2-acetoxymalonate. The reaction was carried out in a solid/liquid two-phase system [Na2CO3/tetrahydrofuran (THF)] in the presence of a glucopyranoside-based crown ether catalyst. The compound was isolated by preparative (TLC) (silica gel) in good yield. The structure of the compound was confirmed by 1H and 13C NMR and (m.p. 366–369 K). The details of the synthesis are presented in Rapi et al. (2016). Single crystals of the title compound suitable for X-ray were obtained by crystallization from ethanol.
6. Refinement
Crystal data, data collection and structure . All H atoms were located in difference electron-density maps. However, these atoms were included in the structure at calculated positions, with C—H = 0.95–1.00 Å, and allowed to ride, with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2
|
Supporting information
CCDC reference: 1449223
10.1107/S2056989016001432/zs2354sup1.cif
contains datablocks I, header. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016001432/zs2354Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016001432/zs2354Isup3.cml
The formation of C—C bonds by the Michael addition of the appropriate carboanionic reagents to α,β-unsaturated is one of the most useful methods of remote functionalization in organic synthesis (Mather et al., 2006; Little et al., 1995). In particular, a much studied reaction is the conjugate addition of malonates to Compounds with the chalcone backbone were reported to possess a wide range of biological activities, such as nematicidal, antifungal, antiallergenic, antimicrobial, anticancer, antimalarial and antifeedant properties. Malonates are traditionally regarded as important materials for synthesizing the key intermediates of numerous active substances, but are rarely found as pharmacophores belonging to the target compounds (Lopez et al., 2001; Chen et al., 2016). Therefore, a catalytic version of the Michael addition of dialkyl malonates to in the presence of different catalysts has been studied extensively in recent years. Many phase-transfer-catalyzed methods that are simple and environmentally friendly have been developed for the Michael reaction (Shioiri, 1997). This new was prepared in a phase-transfer reaction using a sugar-based crown ether as the catalyst (Rapi et al., 2016).
The molecular structure of the racemic title compound is shown in Fig. 1. In this molecule, the C4 atom is a chiral centre, but no resolution occurred upon crystal preparation, the
crystallizing in the centrosymmetric P21/n. The dihedral angle between the planes of the two benzene rings is 80.16 (6)° and the is stabilized by an intramolecular methylene C5—H···O5 hydrogen bond (Table 2).Because of the numerous C═O acceptor groups and the lack of primary donor groups in the molecule, the main intermolecular interactions in the crystal are weak C—H···Ocarboxyl hydrogen bonds (Table 1), having an H···O distance equal to or less than 2.6 Å. However, one of the four interactions (C24—H···O8iii; see Table 2 for hydrogen-bond geometric details and symmetry codes) involves a nitro O-atom acceptor. Intermolecular C15—H···O7ii hydrogen bonds form centrosymmetric cyclic dimers (Fig. 2) having the graph-set descriptor (Bernstein et al., 1995) R22(16). These dimers are linked along the crystallographic a direction through C24—H···O8iii hydrogen bonds, forming a chain. These chains are further extended in the crystallographic b direction through C11—H···O4i and C12—H···O6i interactions, forming a cyclic motif with the graph-set descriptor of R22(10) (Fig. 3). Despite the presence of two aromatic rings in the molecule, there are no significant π–π interactions in the This can be explained by the diverse chain system of the molecule and, therefore, the steric preference of the C—H···O hydrogen bonds. However, there is a C16—H16···π interaction across c with the C7–C12 nitrophenyl ring (C···Cgiv = 2.81 Å and C—H···Cgiv = 149°; Cg is the centroid of the C7–C12 ring) (Fig. 4), resulting in an overall three-dimensional supramolecular structure. The relatively high calculated density (1.367 Mg m−3) and K·P·I. index (Kitaigorodskii packing coefficient = 69.6%) (Spek, 2009) show efficient packing of the molecule resulting in no residual solvent-accessible voids.
The structures of different derivatives of 1,2-diphenylpentan-1-one, carrying methyl or nitrile substituents on the chiral C atom, have been reported, viz. Cambridge Structural Database (CSD; Groom & Allen, 2014) refcodes RULFIN [(S)-4-methyl-4-nitro-1,3-diphenylpentanone [Bakó et al., 1997], DULJOK (1,3-diphenylbutan-1-one; Bakowicz & Turowska-Tyrk, 2010) and LAPKEU (4-oxo-2,4-diphenylbutanenitrile; Abdel-Aziz et al., 2012). RULFIN and DULJOK were crystallized in the chiral P212121 and Pca21 space groups, respectively, and LAPKEU crystallized as a
in the centrosymmetric P21/c Comparing the dihedral angles between the planes of the two benzene rings the of the bulky substituents on atom C2 can be seen. This value is 62.5° for the methyl derivative (DULJOK) and 68.4° for the nitrile (LAPKEU), but significantly higher for the bulky methyl–nitro derivative (88.13°; RULFIN) or the title compound (80.2°).The title compound was synthesized by the reaction of 4'-nitrochalcone [(E)-3-(4-nitrophenyl)-1-phenylprop-2-en-1-one] with diethyl 2-acetoxymalonate. The reaction was carried out in a solid/liquid two-phase system [Na2CO3/tetrahydrofuran (THF)] in the presence of a glucopyranoside-based crown ether catalyst. The compound was isolated by preparative
(TLC) (silica gel) in good yield. The structure of the compound was confirmed by 1H and 13C NMR and (m.p. 366–369 K). The details of the synthesis are presented in Rapi et al. (2016). Single crystals of the title compound suitable for X-ray were obtained by crystallization from ethanol.Crystal data, data collection and structure
details are summarized in Table 2. A l l H atoms were located in difference electron-density maps. However, these atoms were included in the structure at calculated positions, with C—H = 0.95–1.00 Å, and allowed to ride, with Uiso(H) = 1.2Ueq(C).The formation of C—C bonds by the Michael addition of the appropriate carboanionic reagents to α,β-unsaturated is one of the most useful methods of remote functionalization in organic synthesis (Mather et al., 2006; Little et al., 1995). In particular, a much studied reaction is the conjugate addition of malonates to Compounds with the chalcone backbone were reported to possess a wide range of biological activities, such as nematicidal, antifungal, antiallergenic, antimicrobial, anticancer, antimalarial and antifeedant properties. Malonates are traditionally regarded as important materials for synthesizing the key intermediates of numerous active substances, but are rarely found as pharmacophores belonging to the target compounds (Lopez et al., 2001; Chen et al., 2016). Therefore, a catalytic version of the Michael addition of dialkyl malonates to in the presence of different catalysts has been studied extensively in recent years. Many phase-transfer-catalyzed methods that are simple and environmentally friendly have been developed for the Michael reaction (Shioiri, 1997). This new was prepared in a phase-transfer reaction using a sugar-based crown ether as the catalyst (Rapi et al., 2016).
The molecular structure of the racemic title compound is shown in Fig. 1. In this molecule, the C4 atom is a chiral centre, but no resolution occurred upon crystal preparation, the
crystallizing in the centrosymmetric P21/n. The dihedral angle between the planes of the two benzene rings is 80.16 (6)° and the is stabilized by an intramolecular methylene C5—H···O5 hydrogen bond (Table 2).Because of the numerous C═O acceptor groups and the lack of primary donor groups in the molecule, the main intermolecular interactions in the crystal are weak C—H···Ocarboxyl hydrogen bonds (Table 1), having an H···O distance equal to or less than 2.6 Å. However, one of the four interactions (C24—H···O8iii; see Table 2 for hydrogen-bond geometric details and symmetry codes) involves a nitro O-atom acceptor. Intermolecular C15—H···O7ii hydrogen bonds form centrosymmetric cyclic dimers (Fig. 2) having the graph-set descriptor (Bernstein et al., 1995) R22(16). These dimers are linked along the crystallographic a direction through C24—H···O8iii hydrogen bonds, forming a chain. These chains are further extended in the crystallographic b direction through C11—H···O4i and C12—H···O6i interactions, forming a cyclic motif with the graph-set descriptor of R22(10) (Fig. 3). Despite the presence of two aromatic rings in the molecule, there are no significant π–π interactions in the This can be explained by the diverse chain system of the molecule and, therefore, the steric preference of the C—H···O hydrogen bonds. However, there is a C16—H16···π interaction across c with the C7–C12 nitrophenyl ring (C···Cgiv = 2.81 Å and C—H···Cgiv = 149°; Cg is the centroid of the C7–C12 ring) (Fig. 4), resulting in an overall three-dimensional supramolecular structure. The relatively high calculated density (1.367 Mg m−3) and K·P·I. index (Kitaigorodskii packing coefficient = 69.6%) (Spek, 2009) show efficient packing of the molecule resulting in no residual solvent-accessible voids.
The structures of different derivatives of 1,2-diphenylpentan-1-one, carrying methyl or nitrile substituents on the chiral C atom, have been reported, viz. Cambridge Structural Database (CSD; Groom & Allen, 2014) refcodes RULFIN [(S)-4-methyl-4-nitro-1,3-diphenylpentanone [Bakó et al., 1997], DULJOK (1,3-diphenylbutan-1-one; Bakowicz & Turowska-Tyrk, 2010) and LAPKEU (4-oxo-2,4-diphenylbutanenitrile; Abdel-Aziz et al., 2012). RULFIN and DULJOK were crystallized in the chiral P212121 and Pca21 space groups, respectively, and LAPKEU crystallized as a
in the centrosymmetric P21/c Comparing the dihedral angles between the planes of the two benzene rings the of the bulky substituents on atom C2 can be seen. This value is 62.5° for the methyl derivative (DULJOK) and 68.4° for the nitrile (LAPKEU), but significantly higher for the bulky methyl–nitro derivative (88.13°; RULFIN) or the title compound (80.2°).The title compound was synthesized by the reaction of 4'-nitrochalcone [(E)-3-(4-nitrophenyl)-1-phenylprop-2-en-1-one] with diethyl 2-acetoxymalonate. The reaction was carried out in a solid/liquid two-phase system [Na2CO3/tetrahydrofuran (THF)] in the presence of a glucopyranoside-based crown ether catalyst. The compound was isolated by preparative
(TLC) (silica gel) in good yield. The structure of the compound was confirmed by 1H and 13C NMR and (m.p. 366–369 K). The details of the synthesis are presented in Rapi et al. (2016). Single crystals of the title compound suitable for X-ray were obtained by crystallization from ethanol. detailsCrystal data, data collection and structure
details are summarized in Table 2. A l l H atoms were located in difference electron-density maps. However, these atoms were included in the structure at calculated positions, with C—H = 0.95–1.00 Å, and allowed to ride, with Uiso(H) = 1.2Ueq(C).Data collection: CrystalClear (Rigaku/MSC, 2008); cell
CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014/7.Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. A view of the column structure extending along the a axis, showing the C—H···O interactions as dashed lines. | |
Fig. 3. A view of the column expansion along the b axis, showing the C—H···O interactions as dashed lines. | |
Fig. 4. The arrangement of four molecules, showing the C—H···Cg interactions (dashed lines). |
C24H25NO9 | Dx = 1.367 Mg m−3 |
Mr = 471.46 | Melting point = 366–369 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.0111 (7) Å | Cell parameters from 39929 reflections |
b = 13.1762 (8) Å | θ = 3.0–31.5° |
c = 15.8196 (9) Å | µ = 0.11 mm−1 |
β = 93.802 (2)° | T = 103 K |
V = 2290.1 (2) Å3 | Block, colorless |
Z = 4 | 0.45 × 0.38 × 0.08 mm |
F(000) = 992 |
R-AXIS-RAPID diffractometer | 7609 independent reflections |
Radiation source: Sealed Tube | 6054 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 31.5°, θmin = 3.0° |
dtprofit.ref scans | h = −16→16 |
Absorption correction: empirical (using intensity measurements) Higashi (2002). Numerical Absorption Correction: NUMABS | k = −19→19 |
Tmin = 0.957, Tmax = 0.979 | l = −23→23 |
67635 measured reflections |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0518P)2 + 0.9253P] where P = (Fo2 + 2Fc2)/3 |
7609 reflections | (Δ/σ)max = 0.001 |
310 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C24H25NO9 | V = 2290.1 (2) Å3 |
Mr = 471.46 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.0111 (7) Å | µ = 0.11 mm−1 |
b = 13.1762 (8) Å | T = 103 K |
c = 15.8196 (9) Å | 0.45 × 0.38 × 0.08 mm |
β = 93.802 (2)° |
R-AXIS-RAPID diffractometer | 7609 independent reflections |
Absorption correction: empirical (using intensity measurements) Higashi (2002). Numerical Absorption Correction: NUMABS | 6054 reflections with I > 2σ(I) |
Tmin = 0.957, Tmax = 0.979 | Rint = 0.046 |
67635 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.49 e Å−3 |
7609 reflections | Δρmin = −0.38 e Å−3 |
310 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
O3 | 0.16456 (8) | 0.30912 (6) | 0.25349 (6) | 0.01897 (17) | |
O5 | 0.26884 (8) | 0.41900 (7) | 0.14208 (6) | 0.02136 (18) | |
O6 | 0.21898 (8) | 0.56611 (7) | 0.20333 (6) | 0.02246 (18) | |
O2 | 0.14316 (8) | 0.54562 (6) | 0.36420 (6) | 0.02048 (18) | |
O4 | 0.01727 (9) | 0.37984 (8) | 0.16696 (6) | 0.0278 (2) | |
O1 | 0.01500 (8) | 0.41220 (7) | 0.35300 (7) | 0.0267 (2) | |
C11 | 0.67021 (11) | 0.06374 (9) | 0.29676 (8) | 0.0205 (2) | |
H11 | 0.6453 | −0.0032 | 0.2816 | 0.025* | |
C5 | 0.40905 (10) | 0.31827 (9) | 0.29982 (8) | 0.0177 (2) | |
H5B | 0.3767 | 0.2484 | 0.3036 | 0.021* | |
H5A | 0.4138 | 0.3351 | 0.2391 | 0.021* | |
C8 | 0.74760 (11) | 0.25968 (9) | 0.34224 (8) | 0.0211 (2) | |
H8 | 0.7733 | 0.3264 | 0.3576 | 0.025* | |
O7 | 0.56808 (9) | 0.39344 (8) | 0.38850 (7) | 0.0299 (2) | |
C4 | 0.32199 (10) | 0.39265 (9) | 0.33974 (7) | 0.0165 (2) | |
H4 | 0.3639 | 0.4599 | 0.3448 | 0.020* | |
C10 | 0.79207 (11) | 0.08750 (9) | 0.31234 (8) | 0.0194 (2) | |
N1 | 0.88210 (10) | 0.00521 (8) | 0.30793 (7) | 0.0236 (2) | |
O8 | 0.98968 (9) | 0.02854 (9) | 0.30729 (9) | 0.0407 (3) | |
C1 | 0.10634 (10) | 0.45486 (9) | 0.33559 (8) | 0.0186 (2) | |
C2 | 0.20283 (10) | 0.40756 (8) | 0.28145 (7) | 0.0167 (2) | |
O9 | 0.84527 (10) | −0.08248 (8) | 0.30556 (8) | 0.0339 (2) | |
C16 | 0.23200 (12) | 0.30653 (10) | 0.59164 (8) | 0.0239 (2) | |
H16 | 0.2111 | 0.2884 | 0.6470 | 0.029* | |
C6 | 0.53495 (10) | 0.32257 (9) | 0.34362 (8) | 0.0192 (2) | |
C3 | 0.22914 (10) | 0.47531 (9) | 0.20474 (8) | 0.0179 (2) | |
C7 | 0.62319 (10) | 0.23832 (9) | 0.32841 (7) | 0.0180 (2) | |
C13 | 0.29301 (10) | 0.36000 (9) | 0.42848 (7) | 0.0180 (2) | |
C23 | 0.07300 (11) | 0.30567 (10) | 0.19098 (8) | 0.0220 (2) | |
C18 | 0.24448 (12) | 0.26431 (9) | 0.44386 (8) | 0.0231 (2) | |
H18 | 0.2321 | 0.2170 | 0.3988 | 0.028* | |
C14 | 0.31184 (11) | 0.42777 (9) | 0.49593 (8) | 0.0203 (2) | |
H14 | 0.3463 | 0.4925 | 0.4865 | 0.024* | |
C20 | 0.11540 (16) | 0.69755 (11) | 0.44259 (10) | 0.0331 (3) | |
H20C | 0.0675 | 0.7306 | 0.4848 | 0.040* | |
H20A | 0.1071 | 0.7358 | 0.3894 | 0.040* | |
H20B | 0.2012 | 0.6956 | 0.4633 | 0.040* | |
C9 | 0.83308 (11) | 0.18426 (10) | 0.33364 (8) | 0.0217 (2) | |
H9 | 0.9176 | 0.1983 | 0.3421 | 0.026* | |
C12 | 0.58535 (11) | 0.14101 (9) | 0.30400 (8) | 0.0200 (2) | |
H12 | 0.5012 | 0.1274 | 0.2922 | 0.024* | |
C24 | 0.05811 (13) | 0.20038 (11) | 0.15718 (10) | 0.0299 (3) | |
H24A | 0.1384 | 0.1711 | 0.1493 | 0.036* | |
H24C | 0.0103 | 0.2021 | 0.1027 | 0.036* | |
H24B | 0.0159 | 0.1588 | 0.1974 | 0.036* | |
C19 | 0.06994 (12) | 0.59136 (10) | 0.42759 (9) | 0.0252 (3) | |
H19A | 0.0781 | 0.5519 | 0.4809 | 0.030* | |
H19B | −0.0169 | 0.5923 | 0.4070 | 0.030* | |
C17 | 0.21419 (13) | 0.23829 (10) | 0.52514 (9) | 0.0257 (3) | |
H17 | 0.1810 | 0.1732 | 0.5352 | 0.031* | |
C15 | 0.28063 (12) | 0.40142 (10) | 0.57657 (8) | 0.0229 (2) | |
H15 | 0.2926 | 0.4486 | 0.6217 | 0.027* | |
C21 | 0.28528 (14) | 0.47311 (10) | 0.06304 (8) | 0.0270 (3) | |
H21A | 0.3402 | 0.4339 | 0.0282 | 0.032* | |
H21B | 0.3233 | 0.5400 | 0.0757 | 0.032* | |
C22 | 0.16416 (16) | 0.48792 (13) | 0.01442 (10) | 0.0390 (4) | |
H22B | 0.1765 | 0.5225 | −0.0392 | 0.047* | |
H22C | 0.1112 | 0.5292 | 0.0480 | 0.047* | |
H22A | 0.1261 | 0.4217 | 0.0028 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0175 (4) | 0.0147 (4) | 0.0243 (4) | −0.0015 (3) | −0.0016 (3) | −0.0012 (3) |
O5 | 0.0267 (4) | 0.0191 (4) | 0.0185 (4) | 0.0018 (3) | 0.0032 (3) | −0.0001 (3) |
O6 | 0.0272 (4) | 0.0168 (4) | 0.0233 (4) | 0.0016 (3) | 0.0016 (3) | 0.0011 (3) |
O2 | 0.0209 (4) | 0.0170 (4) | 0.0241 (4) | 0.0014 (3) | 0.0057 (3) | −0.0016 (3) |
O4 | 0.0223 (4) | 0.0271 (5) | 0.0331 (5) | 0.0028 (4) | −0.0049 (4) | −0.0010 (4) |
O1 | 0.0201 (4) | 0.0263 (5) | 0.0343 (5) | −0.0025 (3) | 0.0062 (4) | −0.0022 (4) |
C11 | 0.0201 (5) | 0.0181 (5) | 0.0232 (6) | −0.0002 (4) | 0.0013 (4) | −0.0003 (4) |
C5 | 0.0156 (5) | 0.0168 (5) | 0.0205 (5) | 0.0010 (4) | −0.0003 (4) | −0.0020 (4) |
C8 | 0.0174 (5) | 0.0205 (5) | 0.0249 (6) | −0.0002 (4) | −0.0010 (4) | −0.0023 (5) |
O7 | 0.0210 (4) | 0.0279 (5) | 0.0401 (6) | 0.0008 (4) | −0.0030 (4) | −0.0160 (4) |
C4 | 0.0153 (5) | 0.0161 (5) | 0.0181 (5) | 0.0005 (4) | 0.0003 (4) | −0.0011 (4) |
C10 | 0.0189 (5) | 0.0207 (5) | 0.0186 (5) | 0.0036 (4) | 0.0019 (4) | 0.0006 (4) |
N1 | 0.0219 (5) | 0.0233 (5) | 0.0257 (5) | 0.0054 (4) | 0.0012 (4) | 0.0010 (4) |
O8 | 0.0191 (5) | 0.0328 (6) | 0.0699 (8) | 0.0054 (4) | −0.0001 (5) | −0.0033 (5) |
C1 | 0.0160 (5) | 0.0170 (5) | 0.0226 (5) | 0.0022 (4) | −0.0007 (4) | 0.0014 (4) |
C2 | 0.0165 (5) | 0.0131 (5) | 0.0203 (5) | −0.0006 (4) | 0.0004 (4) | −0.0002 (4) |
O9 | 0.0326 (5) | 0.0206 (4) | 0.0494 (6) | 0.0044 (4) | 0.0099 (5) | 0.0007 (4) |
C16 | 0.0260 (6) | 0.0273 (6) | 0.0188 (5) | 0.0031 (5) | 0.0034 (4) | 0.0019 (5) |
C6 | 0.0161 (5) | 0.0196 (5) | 0.0217 (5) | 0.0000 (4) | 0.0005 (4) | −0.0022 (4) |
C3 | 0.0154 (5) | 0.0180 (5) | 0.0201 (5) | 0.0002 (4) | −0.0011 (4) | 0.0003 (4) |
C7 | 0.0167 (5) | 0.0186 (5) | 0.0185 (5) | 0.0002 (4) | −0.0005 (4) | −0.0007 (4) |
C13 | 0.0179 (5) | 0.0172 (5) | 0.0187 (5) | 0.0020 (4) | −0.0001 (4) | −0.0002 (4) |
C23 | 0.0177 (5) | 0.0233 (6) | 0.0250 (6) | −0.0025 (4) | 0.0003 (4) | −0.0023 (5) |
C18 | 0.0285 (6) | 0.0183 (5) | 0.0227 (6) | −0.0003 (4) | 0.0034 (5) | −0.0017 (5) |
C14 | 0.0194 (5) | 0.0196 (5) | 0.0216 (5) | 0.0010 (4) | −0.0015 (4) | −0.0007 (4) |
C20 | 0.0461 (9) | 0.0238 (6) | 0.0304 (7) | −0.0004 (6) | 0.0110 (6) | −0.0066 (5) |
C9 | 0.0156 (5) | 0.0240 (6) | 0.0252 (6) | 0.0004 (4) | −0.0017 (4) | −0.0013 (5) |
C12 | 0.0163 (5) | 0.0204 (5) | 0.0232 (6) | −0.0006 (4) | 0.0003 (4) | −0.0007 (4) |
C24 | 0.0253 (6) | 0.0257 (6) | 0.0382 (8) | −0.0053 (5) | −0.0023 (5) | −0.0080 (6) |
C19 | 0.0257 (6) | 0.0235 (6) | 0.0273 (6) | 0.0041 (5) | 0.0088 (5) | −0.0021 (5) |
C17 | 0.0318 (7) | 0.0204 (6) | 0.0255 (6) | −0.0013 (5) | 0.0060 (5) | 0.0024 (5) |
C15 | 0.0234 (6) | 0.0252 (6) | 0.0198 (5) | 0.0020 (5) | −0.0008 (4) | −0.0036 (5) |
C21 | 0.0379 (7) | 0.0244 (6) | 0.0191 (6) | 0.0015 (5) | 0.0058 (5) | 0.0016 (5) |
C22 | 0.0491 (9) | 0.0432 (9) | 0.0232 (7) | −0.0088 (7) | −0.0089 (6) | 0.0033 (6) |
O1—C1 | 1.2000 (15) | C16—C17 | 1.3879 (19) |
O2—C1 | 1.3323 (14) | C17—C18 | 1.3925 (19) |
O2—C19 | 1.4581 (16) | C19—C20 | 1.500 (2) |
O3—C2 | 1.4251 (13) | C21—C22 | 1.507 (2) |
O3—C23 | 1.3653 (15) | C23—C24 | 1.492 (2) |
O4—C23 | 1.2021 (17) | C4—H4 | 1.0000 |
O5—C3 | 1.3348 (15) | C5—H5A | 0.9900 |
O5—C21 | 1.4610 (16) | C5—H5B | 0.9900 |
O6—C3 | 1.2017 (15) | C8—H8 | 0.9500 |
O7—C6 | 1.2144 (16) | C9—H9 | 0.9500 |
O8—N1 | 1.2245 (15) | C11—H11 | 0.9500 |
O9—N1 | 1.2243 (15) | C12—H12 | 0.9500 |
N1—C10 | 1.4739 (16) | C14—H14 | 0.9500 |
C1—C2 | 1.5400 (16) | C15—H15 | 0.9500 |
C2—C3 | 1.5492 (16) | C16—H16 | 0.9500 |
C2—C4 | 1.5653 (16) | C17—H17 | 0.9500 |
C4—C5 | 1.5358 (16) | C18—H18 | 0.9500 |
C4—C13 | 1.5222 (16) | C19—H19A | 0.9900 |
C5—C6 | 1.5092 (16) | C19—H19B | 0.9900 |
C6—C7 | 1.5051 (16) | C20—H20A | 0.9800 |
C7—C8 | 1.4014 (16) | C20—H20B | 0.9800 |
C7—C12 | 1.3948 (17) | C20—H20C | 0.9800 |
C8—C9 | 1.3816 (17) | C21—H21A | 0.9900 |
C9—C10 | 1.3866 (18) | C21—H21B | 0.9900 |
C10—C11 | 1.3840 (17) | C22—H22A | 0.9800 |
C11—C12 | 1.3918 (17) | C22—H22B | 0.9800 |
C13—C14 | 1.3963 (17) | C22—H22C | 0.9800 |
C13—C18 | 1.3970 (17) | C24—H24A | 0.9800 |
C14—C15 | 1.3872 (18) | C24—H24B | 0.9800 |
C15—C16 | 1.3870 (19) | C24—H24C | 0.9800 |
C1—O2—C19 | 115.78 (9) | C4—C5—H5A | 109.00 |
C2—O3—C23 | 116.36 (9) | C4—C5—H5B | 109.00 |
C3—O5—C21 | 115.44 (10) | C6—C5—H5A | 109.00 |
O8—N1—O9 | 123.73 (12) | C6—C5—H5B | 109.00 |
O8—N1—C10 | 118.02 (11) | H5A—C5—H5B | 108.00 |
O9—N1—C10 | 118.25 (11) | C7—C8—H8 | 120.00 |
O1—C1—O2 | 125.68 (11) | C9—C8—H8 | 120.00 |
O1—C1—C2 | 123.90 (11) | C8—C9—H9 | 121.00 |
O2—C1—C2 | 110.28 (9) | C10—C9—H9 | 121.00 |
O3—C2—C1 | 109.89 (9) | C10—C11—H11 | 121.00 |
O3—C2—C3 | 110.37 (9) | C12—C11—H11 | 121.00 |
O3—C2—C4 | 106.72 (9) | C7—C12—H12 | 120.00 |
C1—C2—C3 | 111.98 (9) | C11—C12—H12 | 120.00 |
C1—C2—C4 | 107.79 (9) | C13—C14—H14 | 120.00 |
C3—C2—C4 | 109.93 (9) | C15—C14—H14 | 120.00 |
O5—C3—O6 | 125.05 (12) | C14—C15—H15 | 120.00 |
O5—C3—C2 | 110.42 (10) | C16—C15—H15 | 120.00 |
O6—C3—C2 | 124.49 (11) | C15—C16—H16 | 120.00 |
C2—C4—C5 | 111.07 (9) | C17—C16—H16 | 120.00 |
C2—C4—C13 | 111.10 (9) | C16—C17—H17 | 120.00 |
C5—C4—C13 | 111.94 (10) | C18—C17—H17 | 120.00 |
C4—C5—C6 | 111.51 (10) | C13—C18—H18 | 120.00 |
O7—C6—C5 | 121.90 (11) | C17—C18—H18 | 120.00 |
O7—C6—C7 | 119.24 (10) | O2—C19—H19A | 110.00 |
C5—C6—C7 | 118.82 (10) | O2—C19—H19B | 110.00 |
C6—C7—C8 | 117.49 (10) | C20—C19—H19A | 110.00 |
C6—C7—C12 | 122.56 (10) | C20—C19—H19B | 110.00 |
C8—C7—C12 | 119.92 (11) | H19A—C19—H19B | 109.00 |
C7—C8—C9 | 120.36 (11) | C19—C20—H20A | 109.00 |
C8—C9—C10 | 118.18 (11) | C19—C20—H20B | 109.00 |
N1—C10—C9 | 118.60 (11) | C19—C20—H20C | 109.00 |
N1—C10—C11 | 118.19 (10) | H20A—C20—H20B | 109.00 |
C9—C10—C11 | 123.20 (11) | H20A—C20—H20C | 109.00 |
C10—C11—C12 | 117.92 (11) | H20B—C20—H20C | 110.00 |
C7—C12—C11 | 120.36 (11) | O5—C21—H21A | 110.00 |
C4—C13—C14 | 119.63 (10) | O5—C21—H21B | 110.00 |
C4—C13—C18 | 121.45 (10) | C22—C21—H21A | 110.00 |
C14—C13—C18 | 118.90 (11) | C22—C21—H21B | 110.00 |
C13—C14—C15 | 120.63 (11) | H21A—C21—H21B | 108.00 |
C14—C15—C16 | 120.38 (12) | C21—C22—H22A | 109.00 |
C15—C16—C17 | 119.37 (12) | C21—C22—H22B | 109.00 |
C16—C17—C18 | 120.66 (12) | C21—C22—H22C | 109.00 |
C13—C18—C17 | 120.06 (11) | H22A—C22—H22B | 109.00 |
O2—C19—C20 | 107.49 (11) | H22A—C22—H22C | 109.00 |
O5—C21—C22 | 110.13 (12) | H22B—C22—H22C | 109.00 |
O3—C23—O4 | 122.60 (12) | C23—C24—H24A | 109.00 |
O3—C23—C24 | 110.42 (11) | C23—C24—H24B | 109.00 |
O4—C23—C24 | 126.94 (12) | C23—C24—H24C | 109.00 |
C2—C4—H4 | 107.00 | H24A—C24—H24B | 109.00 |
C5—C4—H4 | 108.00 | H24A—C24—H24C | 109.00 |
C13—C4—H4 | 107.00 | H24B—C24—H24C | 109.00 |
C19—O2—C1—O1 | 5.55 (18) | C1—C2—C3—O5 | −153.75 (9) |
C19—O2—C1—C2 | −170.22 (10) | C2—C4—C13—C14 | −109.31 (12) |
C1—O2—C19—C20 | −172.46 (11) | C5—C4—C13—C18 | −55.97 (14) |
C23—O3—C2—C3 | −50.41 (13) | C13—C4—C5—C6 | −69.13 (12) |
C23—O3—C2—C1 | 73.57 (12) | C2—C4—C5—C6 | 166.04 (9) |
C23—O3—C2—C4 | −169.83 (9) | C5—C4—C13—C14 | 125.88 (11) |
C2—O3—C23—C24 | 169.59 (10) | C2—C4—C13—C18 | 68.84 (14) |
C2—O3—C23—O4 | −8.34 (17) | C4—C5—C6—O7 | −17.48 (17) |
C3—O5—C21—C22 | −78.91 (13) | C4—C5—C6—C7 | 164.86 (10) |
C21—O5—C3—C2 | 174.18 (10) | C5—C6—C7—C8 | 156.98 (11) |
C21—O5—C3—O6 | −8.16 (17) | O7—C6—C7—C12 | 157.30 (12) |
O8—N1—C10—C9 | −13.61 (18) | C5—C6—C7—C12 | −24.98 (17) |
O9—N1—C10—C11 | −12.60 (18) | O7—C6—C7—C8 | −20.74 (17) |
O9—N1—C10—C9 | 166.02 (12) | C8—C7—C12—C11 | 2.74 (18) |
O8—N1—C10—C11 | 167.78 (13) | C12—C7—C8—C9 | −1.43 (18) |
O2—C1—C2—C4 | 62.12 (12) | C6—C7—C8—C9 | 176.67 (11) |
O1—C1—C2—C4 | −113.74 (13) | C6—C7—C12—C11 | −175.26 (11) |
O2—C1—C2—O3 | 178.06 (9) | C7—C8—C9—C10 | −0.93 (18) |
O1—C1—C2—C3 | 125.24 (13) | C8—C9—C10—C11 | 2.08 (19) |
O2—C1—C2—C3 | −58.90 (13) | C8—C9—C10—N1 | −176.45 (11) |
O1—C1—C2—O3 | 2.19 (16) | C9—C10—C11—C12 | −0.80 (19) |
O3—C2—C3—O5 | −30.98 (12) | N1—C10—C11—C12 | 177.74 (11) |
C1—C2—C4—C5 | 162.98 (9) | C10—C11—C12—C7 | −1.63 (18) |
C1—C2—C4—C13 | 37.68 (12) | C4—C13—C14—C15 | 176.90 (11) |
O3—C2—C3—O6 | 151.34 (11) | C18—C13—C14—C15 | −1.30 (18) |
C4—C2—C3—O6 | −91.21 (13) | C4—C13—C18—C17 | −177.30 (11) |
C3—C2—C4—C13 | 159.98 (9) | C14—C13—C18—C17 | 0.86 (18) |
O3—C2—C4—C13 | −80.32 (11) | C13—C14—C15—C16 | 1.06 (19) |
C3—C2—C4—C5 | −74.72 (11) | C14—C15—C16—C17 | −0.4 (2) |
C4—C2—C3—O5 | 86.48 (11) | C15—C16—C17—C18 | −0.1 (2) |
O3—C2—C4—C5 | 44.98 (12) | C16—C17—C18—C13 | −0.2 (2) |
C1—C2—C3—O6 | 28.57 (16) |
Cg is the centroid of the C7–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O5 | 0.99 | 2.41 | 3.1403 (15) | 130 |
C11—H11···O4i | 0.95 | 2.54 | 3.2588 (16) | 133 |
C12—H12···O6i | 0.95 | 2.56 | 3.4879 (15) | 165 |
C15—H15···O7ii | 0.95 | 2.60 | 3.2038 (17) | 122 |
C24—H24B···O8iii | 0.98 | 2.47 | 3.402 (2) | 158 |
C16—H16···Cgiv | 0.95 | 2.81 | 3.6550 (14) | 149 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) x−1/2, −y+1/2, z+1/2. |
Cg is the centroid of the C7–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O5 | 0.99 | 2.41 | 3.1403 (15) | 130 |
C11—H11···O4i | 0.95 | 2.54 | 3.2588 (16) | 133 |
C12—H12···O6i | 0.95 | 2.56 | 3.4879 (15) | 165 |
C15—H15···O7ii | 0.95 | 2.60 | 3.2038 (17) | 122 |
C24—H24B···O8iii | 0.98 | 2.47 | 3.402 (2) | 158 |
C16—H16···Cgiv | 0.95 | 2.81 | 3.6550 (14) | 149 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C24H25NO9 |
Mr | 471.46 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 103 |
a, b, c (Å) | 11.0111 (7), 13.1762 (8), 15.8196 (9) |
β (°) | 93.802 (2) |
V (Å3) | 2290.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.45 × 0.38 × 0.08 |
Data collection | |
Diffractometer | R-AXIS-RAPID |
Absorption correction | Empirical (using intensity measurements) Higashi (2002). Numerical Absorption Correction: NUMABS |
Tmin, Tmax | 0.957, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 67635, 7609, 6054 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.735 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.128, 1.12 |
No. of reflections | 7609 |
No. of parameters | 310 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.38 |
Computer programs: CrystalClear (Rigaku/MSC, 2008), CrystalClear, SHELXS97 (Sheldrick, 2008), SHELXL2014/7 (Sheldrick, 2015), Mercury (Macrae et al., 2006), SHELXL2014/7.
Acknowledgements
This work was supported financially by the Hungarian Scientific Research Found (OTKA K No. 115762 and PD No. 112166) and the New Széchenyi Development Plan (TÁMOP-4.2.1/B-09/1/KMR-2010-0002).
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