research communications
Crystal structures of (S)-(+)-5-(3-bromo/chloro-4-isopropoxyphenyl)-5-methylimidazolidine-2,4-dione
aResearch and Education Center for Natural Sciences, Keio University, Hiyoshi 4-1-1, Kohoku-ku, Yokohama 223-8521, Japan, and bTokyo New Drug Research Laboratories, Pharmaceutical Division, Kowa Company, Ltd., 2-17-43, Noguchicho, Higashimurayama, Tokyo 189-0022, Japan
*Correspondence e-mail: ohba@a3.keio.jp
In (S)-(+)-5-(3-bromo-4-isopropoxyphenyl)-5-methylimidazolidine-2,4-dione, C13H15BrN2O3, (I), the hydantoin groups are connected via intermolecular N—H⋯O hydrogen bonds, forming a terraced sheet structure. In the chloro analogue, (S)-(+)-5-(3-chloro-4-isopropoxyphenyl)-5-methylimidazolidine-2,4-dione, C13H15ClN2O3, (II), the intermolecular N—H⋯O hydrogen-bonding network forms a flat sheet. Comparison of the crystal structures reveals that (II) is more loosely packed than (I).
Keywords: crystal structure; hydantoin; absolute configuration; hydrogen bonding.
1. Chemical context
In searching for a new synthetic β-selective agonist toward liver X receptors (LXR), a series of compounds having the hydantoin tail, which may act as a linker, were synthesized and examined (Matsuda et al., 2015; Koura et al., 2015). It has been revealed that the of the hydantoin unit is crucial to the LXR activation and β selectivity (Koura et al., 2016). In the present study, the of the (+)-hydantoin unit, which leads to pharmacological activity, has been determined definitely from anomalous-dispersion effects in diffraction measurements on crystals of the title bromo and chloro derivatives.
2. Structural commentary
The conformations of the molecules (I) and (II) are similar to one another (Figs. 1 and 2), although the inclination angles of the C11–C16 benzene rings to the hydantoin group around the C7—C11 bond axes differ somewhat, the N5—C7—C11—C16 torsion angles being 12.9 (3)° and −9.8 (2)° for (I) and (II), respectively. The configuration around the asymmetric carbon atom C7 of the (+)-isomer has been determined to S for both (I) and (II). It is worthwhile to compare the Flack parameters calculated by classical (Flack, 1983) and Parsons' quotient (Parsons et al., 2013) for these Br and Cl compounds which were measured with Mo Kα radiation. These values are 0.010 (7) and 0.018 (2) for (I), and 0.010 (50) and 0.009 (8) for (II), respectively. Flack parameters with much smaller s.u. values were obtained by Parsons' method.
3. Supramolecular features
The projected along a is shown in Fig. 3. The hydantoin ring systems are linked by two sets of N—H⋯O hydrogen bonds (Table 1) and are arranged in zigzag fashion along the twofold screw axes at z = 0 and z = ½ along a. Groups of four molecules are linked by these N—H⋯O hydrogen bonds, generating (20) ring motifs, forming terraced sheets parallel to (001) as shown schematically in Fig. 4. The 3-bromo-4-isopropoxyphenyl groups are accommodated between these sheets and linked by the C—H⋯Br and C—H⋯O hydrogen bonds, forming a three-dimensional architecture.
of (I)Both (I) and (II) crystallize in P212121 and the lattice constants are roughly similar for both. However, there are both similarities and significant differences in the packing modes between the two closely related molecules. The of (II) projected along a is shown in Fig. 5. The hydantoin ring systems again lie approximately on planes at z = 0 or z = ½, and are connected by N—H⋯O hydrogen bonds (Table 2), forming a flat sheet parallel to (001). Between these sheets 3-chloro-4-isopropoxyphenyl groups are linked by C—H⋯Cl and C—H⋯O hydrogen bonds, generating a three-dimensional structure of molecules stacked along a.
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Comparison of the crystal structures reveals that (II) is more loosely packed than (I). There are significant differences in the van der Waals radii of the Br and Cl atoms (1.85 and 1.75 Å, respectively; Bondi, 1964) which is reflected in the C—X bond distances [C13—Br1 = 1.8945 (18) Å in (I); C13—Cl1 1.7396 (16) Å in (II)]. However, the effective volume of the molecule in (II) estimated by V/Z is larger by ca 4% than that for (I). This suggests that the nearly coplanar arrangement of the hydantoin groups in (II) is favorable for the formation of N—H⋯O hydrogen bonds as seen from Table 2, but it also results in looser molecular packing.
4. Database survey
Structures of 5-phenyl-5-alkylhydantoin derivatives have been investigated to review the relationships between the ) determined the absolute configurations of 5,5-disubstituted hydantoins based on their chemical syntheses. According to this assignment, the structure of S-(+)-5-phenyl-5-ethylhydantoin was reported (Coquerel et al., 1993). Ferron et al. (2006) determined the configuration of (R)-(−)-5-p-methylphenyl-5-methylhydantoin in a chlathrate compound with permethylated β-cyclodextrin based on the known of the host. Martin et al. (2011) prepared the diastereomeric salt of (S)-(+)-5-phenyl-5-trifluoromethylhydantoin with (+)-α-methylbenzylamine to determine the configuration based on the known of the chiral amine. It is noted that the R and S notation remains unchanged when CH3 at the 5-position of the hydantoin is replaced with CF3, although the priorities of the substituents in the sequence rule are altered. To our knowledge, the present paper is the first to report the of such compounds determined from anomalous-dispersion effects.
and optical activity. Knabe & Wunn (19805. Synthesis and crystallization
Compounds (I) and (II) were prepared from the corresponding (+)-non-halogeno-derivatives, which were separated from a (Koura et al., 2016). Prismatic crystals of (I) were grown from ethylacetate solution. The specific rotation, [α]D, of (I) at 293 K is +79.7° (c = 0.98, MeOH, where c is the concentration of units gram per 100 cm−3).
Plate-like crystals of (II) were grown from ethylacetate solution. The specific rotation, [α]D, of (II) at 293 K is +81.4° (c = 1.0, MeOH).
6. Refinement
Crystal data, data collection and structure . All H atoms bound to C and N were positioned geometrically. They were refined as riding, with N—H = 0.88 Å, C—H = 0.95–0.98 Å, and Uiso(H) = 1.2Ueq(C/N) and Uiso(H) = 1.5Ueq(Cmethyl). The thermal displacement ellipsoids of the non-hydrogen atoms of the isopropoxy group in (II) are larger than those in (I), suggesting some positional disorder, which was not taken into account in the refinement.
details are summarized in Table 3
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Supporting information
10.1107/S2056989015023014/sj5484sup1.cif
contains datablocks I, II, global. DOI:Supporting information file. DOI: 10.1107/S2056989015023014/sj5484Isup4.cdx
Supporting information file. DOI: 10.1107/S2056989015023014/sj5484IIsup5.cdx
Supporting information file. DOI: 10.1107/S2056989015023014/sj5484Isup6.cml
Supporting information file. DOI: 10.1107/S2056989015023014/sj5484IIsup7.cml
In searching for a new synthetic β-selective agonist toward liver X receptors (LXR), a series of the compounds having the hydantoin tail, which may act as a linker, were synthesized and examined (Matsuda et al., 2015; Koura, Matsuda et al., 2015). It has been revealed that the of the hydantoin unit is crucial to the LXR activation and β selectivity (Koura, Sumida et al., 2015). In the present study, the of the (+)-hydantoin unit, which leads to pharmacological activity, has been determined definitely from anomalous-dispersion effects in diffraction measurements on crystals of the title bromo and chloro derivatives.
The conformations of the molecules (I) and (II) are similar to one another (Figs. 1 and 2), although the inclination angles of the C11–C16 benzene rings to the hydantoin group around the C7—C11 bond axes differ somewhat, the N5—C7—C11—C16 torsion angles being 12.9 (3)° and −9.8 (2)° for (I) and (II), respectively. The configuration around the asymmetric carbon atom C7 of the (+)-isomer has been determined to S for both (I) and (II). It is worthwhile to compare the Flack parameters calculated by classical α radiation. These values are 0.010 (7) and 0.018 (2) for (I), and 0.010 (50) and 0.009 (8) for (II), respectively. Flack parameters with much smaller s. u. values were obtained by Parsons' method.
(Flack, 1983) and Parsons' quotient (Parsons et al., 2013) for these Br and Cl compounds which were measured with Mo KThe
of (I) projected along a is shown in Fig. 3. The hydantoin ring systems are linked by two sets of N—H···O hydrogen bonds (Table 1) and are arranged in zigzag fashion along the twofold screw axes at z = 0 and z = 1/2 along a. Groups of four molecules are linked by these N—H···O hydrogen bonds, generating R44(20) ring motifs, forming terraced sheets parallel to (001) as shown schematically in Fig. 4. The 3-bromo-4-isopropoxyphenyl groups are accommodated between these sheets and linked by the C—H···Br and C—H···O hydrogen bonds, forming a three-dimensional architecture.Both (I) and (II) crystallize in
P212121 and the lattice constants are roughly similar for both. However, there are both similarities and significant differences in the packing modes between the two closely related molecules. The of (II) projected along a is shown in Fig. 5. The hydantoin ring systems again lie approximately on planes at z = 0 or z = 1/2, and are connected by N—H···O hydrogen bonds (Table 2), forming a flat sheet parallel to (001). Between these sheets 3-chloro-4-isopropoxyphenyl groups are linked by C—H···Cl and C—H···O hydrogen bonds, generating a three-dimensional network structure of molecules stacked along a.Comparison of crystal structures reveals that (II) is more loosely packed than (I). There are significant differences in the van der Waals radii of the Br and Cl atoms (1.85 and 1.75 Å, respectively; Bondi, 1964) which is reflected in the C—X bond distances [C13—Br1 = 1.8945 (18) Å in (I); C13—Cl1 1.7396 (16) Å in (II)]. However, the effective volume of the molecule in (II) estimated by V/Z is larger by ca 4% than that for (I). This suggests that the nearly coplanar arrangement of the hydantoin groups in (II) is favorable for the formation of N—H···O hydrogen bonds as seen from Table 2, but it also results in looser molecular packing.
Structures of 5-phenyl-5-alkylhydantoin derivatives have been investigated to review the relationships between the β-cyclodextrin based on the known of the host. Martin et al. (2011) prepared the diastereomeric salt of (S)-(+)-5-phenyl-5-trifluoromethylhydantoin with (+)-α-methylbenzylamine to determine the configuration based on the known of the chiral amine. It is noted that the R and S notation remains unchanged when CH3 at the 5-position of the hydantoin is replaced with CF3, although the priorities of the substituents in the sequence rule are altered. To our knowledge, the present paper is the first to report the of such compounds determined from anomalous-dispersion effects.
and optical activity. Knabe & Wunn (1980) determined the absolute configurations of 5,5-disubstituted hydantoins based on their chemical syntheses. According to this assignment, the structure of S-(+)-5-phenyl-5-ethylhydantoin was reported (Coquerel et al., 1993). Ferron et al. (2006) determined the configuration of (R)-(-)-5-p-methylphenyl-5-methylhydantoin in a chlathrate compound with permethylatedCompounds (I) and (II) were prepared from the corresponding (+)-non-halogeno-derivatives, which were separated from a α]D, of (I) at 293 K is +79.7° (c = 0.98, MeOH, where c is the concentration of units gram per 100 cm−3).
(Koura, Sumida et al., 2015). Prismatic crystals of (I) were grown from ethylacetate solution. The specific rotation, [Plate-like crystals of (II) were grown from ethylacetate solution. The specific rotation, [α]D, of (II) at 293 K is +81.4° (c = 1.0, MeOH).
Crystal data, data collection and structure
details are summarized in Table 3. Intensity data were collected in a full sphere. All H atoms bound to C and N were positioned geometrically. They were refined as riding, with N—H = 0.88 Å, C—H = 0.95–0.98 Å, and Uiso(H) = 1.2Ueq(C/N) and Uiso(H) = 1.5Ueq(C)for methyl hydrogen atoms. The thermal displacement ellipsoids of the non-hydrogen atoms of the isopropoxy group in (II) are larger than those in (I), suggesting some positional disorder, which was not taken into account in the refinement.In searching for a new synthetic β-selective agonist toward liver X receptors (LXR), a series of the compounds having the hydantoin tail, which may act as a linker, were synthesized and examined (Matsuda et al., 2015; Koura, Matsuda et al., 2015). It has been revealed that the of the hydantoin unit is crucial to the LXR activation and β selectivity (Koura, Sumida et al., 2015). In the present study, the of the (+)-hydantoin unit, which leads to pharmacological activity, has been determined definitely from anomalous-dispersion effects in diffraction measurements on crystals of the title bromo and chloro derivatives.
The conformations of the molecules (I) and (II) are similar to one another (Figs. 1 and 2), although the inclination angles of the C11–C16 benzene rings to the hydantoin group around the C7—C11 bond axes differ somewhat, the N5—C7—C11—C16 torsion angles being 12.9 (3)° and −9.8 (2)° for (I) and (II), respectively. The configuration around the asymmetric carbon atom C7 of the (+)-isomer has been determined to S for both (I) and (II). It is worthwhile to compare the Flack parameters calculated by classical α radiation. These values are 0.010 (7) and 0.018 (2) for (I), and 0.010 (50) and 0.009 (8) for (II), respectively. Flack parameters with much smaller s. u. values were obtained by Parsons' method.
(Flack, 1983) and Parsons' quotient (Parsons et al., 2013) for these Br and Cl compounds which were measured with Mo KThe
of (I) projected along a is shown in Fig. 3. The hydantoin ring systems are linked by two sets of N—H···O hydrogen bonds (Table 1) and are arranged in zigzag fashion along the twofold screw axes at z = 0 and z = 1/2 along a. Groups of four molecules are linked by these N—H···O hydrogen bonds, generating R44(20) ring motifs, forming terraced sheets parallel to (001) as shown schematically in Fig. 4. The 3-bromo-4-isopropoxyphenyl groups are accommodated between these sheets and linked by the C—H···Br and C—H···O hydrogen bonds, forming a three-dimensional architecture.Both (I) and (II) crystallize in
P212121 and the lattice constants are roughly similar for both. However, there are both similarities and significant differences in the packing modes between the two closely related molecules. The of (II) projected along a is shown in Fig. 5. The hydantoin ring systems again lie approximately on planes at z = 0 or z = 1/2, and are connected by N—H···O hydrogen bonds (Table 2), forming a flat sheet parallel to (001). Between these sheets 3-chloro-4-isopropoxyphenyl groups are linked by C—H···Cl and C—H···O hydrogen bonds, generating a three-dimensional network structure of molecules stacked along a.Comparison of crystal structures reveals that (II) is more loosely packed than (I). There are significant differences in the van der Waals radii of the Br and Cl atoms (1.85 and 1.75 Å, respectively; Bondi, 1964) which is reflected in the C—X bond distances [C13—Br1 = 1.8945 (18) Å in (I); C13—Cl1 1.7396 (16) Å in (II)]. However, the effective volume of the molecule in (II) estimated by V/Z is larger by ca 4% than that for (I). This suggests that the nearly coplanar arrangement of the hydantoin groups in (II) is favorable for the formation of N—H···O hydrogen bonds as seen from Table 2, but it also results in looser molecular packing.
Structures of 5-phenyl-5-alkylhydantoin derivatives have been investigated to review the relationships between the β-cyclodextrin based on the known of the host. Martin et al. (2011) prepared the diastereomeric salt of (S)-(+)-5-phenyl-5-trifluoromethylhydantoin with (+)-α-methylbenzylamine to determine the configuration based on the known of the chiral amine. It is noted that the R and S notation remains unchanged when CH3 at the 5-position of the hydantoin is replaced with CF3, although the priorities of the substituents in the sequence rule are altered. To our knowledge, the present paper is the first to report the of such compounds determined from anomalous-dispersion effects.
and optical activity. Knabe & Wunn (1980) determined the absolute configurations of 5,5-disubstituted hydantoins based on their chemical syntheses. According to this assignment, the structure of S-(+)-5-phenyl-5-ethylhydantoin was reported (Coquerel et al., 1993). Ferron et al. (2006) determined the configuration of (R)-(-)-5-p-methylphenyl-5-methylhydantoin in a chlathrate compound with permethylatedSeveral 2-oxochromene derivatives of chiral hydantoin molecules show liver X receptor β-selective agonists activity (Matsuda et al., 2015; Koura, Matsuda et al., 2015).
Compounds (I) and (II) were prepared from the corresponding (+)-non-halogeno-derivatives, which were separated from a α]D, of (I) at 293 K is +79.7° (c = 0.98, MeOH, where c is the concentration of units gram per 100 cm−3).
(Koura, Sumida et al., 2015). Prismatic crystals of (I) were grown from ethylacetate solution. The specific rotation, [Plate-like crystals of (II) were grown from ethylacetate solution. The specific rotation, [α]D, of (II) at 293 K is +81.4° (c = 1.0, MeOH).
detailsCrystal data, data collection and structure
details are summarized in Table 3. Intensity data were collected in a full sphere. All H atoms bound to C and N were positioned geometrically. They were refined as riding, with N—H = 0.88 Å, C—H = 0.95–0.98 Å, and Uiso(H) = 1.2Ueq(C/N) and Uiso(H) = 1.5Ueq(C)for methyl hydrogen atoms. The thermal displacement ellipsoids of the non-hydrogen atoms of the isopropoxy group in (II) are larger than those in (I), suggesting some positional disorder, which was not taken into account in the refinement.For both compounds, data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and publCIF (Westrip, 2010).Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 50% probability level. | |
Fig. 2. The molecular structure of (II), showing displacement ellipsoids at the 50% probability level. | |
Fig. 3. The crystal structure of (I), projected along a. Hydrogen bonds are shown as dotted lines. | |
Fig. 4. A schematic drawing of the N—H···O hydrogen-bonding network in (I). The arrows indicate the twofold screw axes along a. | |
Fig. 5. The crystal structure of (II), projected along a. Hydrogen bonds are shown as dotted lines. |
C13H15BrN2O3 | Dx = 1.576 Mg m−3 |
Mr = 327.17 | Melting point = 480–485 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1840 (3) Å | Cell parameters from 9747 reflections |
b = 9.6495 (4) Å | θ = 2.8–27.9° |
c = 23.1111 (10) Å | µ = 2.99 mm−1 |
V = 1379.10 (11) Å3 | T = 90 K |
Z = 4 | Prism, colorless |
F(000) = 664 | 0.25 × 0.25 × 0.10 mm |
Bruker D8 VENTURE diffractometer | 3206 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.028 |
Absorption correction: integration (SADABS; Bruker, 2014) | θmax = 27.9°, θmin = 2.3° |
Tmin = 0.482, Tmax = 0.631 | h = −8→8 |
31000 measured reflections | k = −12→12 |
3271 independent reflections | l = −30→30 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.017 | w = 1/[σ2(Fo2) + (0.0213P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max = 0.009 |
S = 1.29 | Δρmax = 0.41 e Å−3 |
3271 reflections | Δρmin = −0.30 e Å−3 |
175 parameters | Absolute structure: Flack x determined using 1301 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
0 restraints | Absolute structure parameter: 0.018 (2) |
C13H15BrN2O3 | V = 1379.10 (11) Å3 |
Mr = 327.17 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.1840 (3) Å | µ = 2.99 mm−1 |
b = 9.6495 (4) Å | T = 90 K |
c = 23.1111 (10) Å | 0.25 × 0.25 × 0.10 mm |
Bruker D8 VENTURE diffractometer | 3271 independent reflections |
Absorption correction: integration (SADABS; Bruker, 2014) | 3206 reflections with I > 2σ(I) |
Tmin = 0.482, Tmax = 0.631 | Rint = 0.028 |
31000 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
wR(F2) = 0.047 | Δρmax = 0.41 e Å−3 |
S = 1.29 | Δρmin = −0.30 e Å−3 |
3271 reflections | Absolute structure: Flack x determined using 1301 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
175 parameters | Absolute structure parameter: 0.018 (2) |
0 restraints |
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 | ||
Br1 | 0.51609 (3) | 0.26559 (2) | 0.22060 (2) | 0.01790 (7) | |
O2 | 0.9092 (2) | 0.43196 (15) | 0.19710 (6) | 0.0164 (3) | |
O3 | 0.9534 (2) | 0.63884 (14) | 0.53560 (6) | 0.0173 (3) | |
O4 | 0.6551 (2) | 0.25613 (14) | 0.45199 (6) | 0.0169 (3) | |
N5 | 0.7120 (3) | 0.61559 (17) | 0.45986 (7) | 0.0125 (3) | |
H5 | 0.6885 | 0.7037 | 0.4524 | 0.015* | |
N6 | 0.8462 (3) | 0.42583 (17) | 0.49936 (6) | 0.0128 (3) | |
H6 | 0.9303 | 0.3728 | 0.5206 | 0.015* | |
C7 | 0.6083 (3) | 0.5027 (2) | 0.42851 (8) | 0.0114 (4) | |
C8 | 0.8471 (3) | 0.5712 (2) | 0.50139 (8) | 0.0115 (4) | |
C9 | 0.7001 (3) | 0.3769 (2) | 0.46070 (8) | 0.0111 (4) | |
C10 | 0.3625 (3) | 0.5093 (3) | 0.43412 (9) | 0.0200 (5) | |
H10A | 0.3226 | 0.5117 | 0.4751 | 0.030* | |
H10B | 0.2982 | 0.4273 | 0.4159 | 0.030* | |
H10C | 0.3087 | 0.5930 | 0.4149 | 0.030* | |
C11 | 0.6865 (3) | 0.4922 (2) | 0.36572 (8) | 0.0112 (4) | |
C12 | 0.5853 (3) | 0.4017 (2) | 0.32744 (8) | 0.0124 (4) | |
H12 | 0.4623 | 0.3504 | 0.3396 | 0.015* | |
C13 | 0.6632 (3) | 0.38634 (19) | 0.27186 (8) | 0.0120 (4) | |
C14 | 0.8446 (4) | 0.4577 (2) | 0.25237 (8) | 0.0129 (4) | |
C15 | 0.9471 (3) | 0.5475 (2) | 0.29057 (8) | 0.0143 (4) | |
H15 | 1.0711 | 0.5978 | 0.2784 | 0.017* | |
C16 | 0.8682 (3) | 0.5640 (2) | 0.34672 (8) | 0.0127 (4) | |
H16 | 0.9400 | 0.6254 | 0.3725 | 0.015* | |
C17 | 1.0475 (3) | 0.5314 (2) | 0.16795 (8) | 0.0151 (4) | |
H17 | 1.1767 | 0.5521 | 0.1925 | 0.018* | |
C18 | 1.1172 (4) | 0.4592 (2) | 0.11306 (9) | 0.0216 (5) | |
H18A | 1.2027 | 0.3770 | 0.1229 | 0.032* | |
H18B | 1.2051 | 0.5225 | 0.0897 | 0.032* | |
H18C | 0.9891 | 0.4313 | 0.0910 | 0.032* | |
C19 | 0.9230 (4) | 0.6638 (2) | 0.15599 (9) | 0.0219 (5) | |
H19A | 0.7966 | 0.6428 | 0.1320 | 0.033* | |
H19B | 1.0166 | 0.7296 | 0.1356 | 0.033* | |
H19C | 0.8753 | 0.7046 | 0.1927 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01843 (11) | 0.02073 (11) | 0.01453 (11) | −0.00651 (8) | −0.00120 (7) | −0.00500 (7) |
O2 | 0.0215 (8) | 0.0166 (7) | 0.0111 (7) | −0.0051 (6) | 0.0047 (6) | −0.0007 (5) |
O3 | 0.0203 (8) | 0.0145 (6) | 0.0171 (7) | −0.0051 (6) | −0.0050 (6) | −0.0011 (5) |
O4 | 0.0232 (7) | 0.0104 (7) | 0.0171 (7) | −0.0064 (6) | 0.0049 (5) | −0.0012 (6) |
N5 | 0.0172 (9) | 0.0074 (8) | 0.0129 (8) | 0.0014 (7) | −0.0020 (7) | −0.0007 (6) |
N6 | 0.0138 (9) | 0.0097 (8) | 0.0147 (8) | 0.0011 (7) | −0.0025 (7) | 0.0020 (6) |
C7 | 0.0103 (9) | 0.0103 (10) | 0.0138 (9) | 0.0009 (8) | −0.0015 (7) | −0.0032 (8) |
C8 | 0.0102 (9) | 0.0110 (9) | 0.0131 (9) | −0.0011 (7) | 0.0018 (7) | 0.0011 (7) |
C9 | 0.0120 (9) | 0.0125 (9) | 0.0086 (8) | −0.0010 (7) | 0.0053 (7) | 0.0002 (7) |
C10 | 0.0118 (10) | 0.0313 (14) | 0.0170 (10) | 0.0040 (9) | −0.0005 (8) | −0.0040 (10) |
C11 | 0.0117 (9) | 0.0110 (9) | 0.0111 (9) | 0.0025 (8) | −0.0012 (7) | 0.0007 (7) |
C12 | 0.0103 (9) | 0.0124 (9) | 0.0145 (9) | −0.0008 (7) | −0.0004 (7) | 0.0009 (7) |
C13 | 0.0128 (9) | 0.0113 (9) | 0.0120 (9) | −0.0008 (7) | −0.0047 (7) | −0.0017 (7) |
C14 | 0.0144 (10) | 0.0121 (9) | 0.0123 (9) | 0.0014 (8) | −0.0002 (7) | 0.0006 (7) |
C15 | 0.0127 (9) | 0.0140 (9) | 0.0161 (9) | −0.0028 (7) | 0.0010 (7) | 0.0015 (7) |
C16 | 0.0125 (9) | 0.0113 (9) | 0.0144 (9) | −0.0005 (7) | −0.0028 (8) | −0.0017 (7) |
C17 | 0.0131 (10) | 0.0164 (9) | 0.0157 (9) | −0.0021 (8) | 0.0024 (8) | 0.0010 (7) |
C18 | 0.0244 (11) | 0.0216 (11) | 0.0187 (10) | 0.0010 (9) | 0.0079 (9) | 0.0008 (9) |
C19 | 0.0263 (12) | 0.0199 (11) | 0.0196 (10) | 0.0036 (9) | 0.0032 (9) | 0.0015 (8) |
Br1—C13 | 1.8945 (18) | C11—C12 | 1.392 (3) |
O2—C14 | 1.361 (2) | C12—C13 | 1.380 (3) |
O2—C17 | 1.451 (2) | C12—H12 | 0.9500 |
O3—C8 | 1.218 (2) | C13—C14 | 1.391 (3) |
O4—C9 | 1.215 (2) | C14—C15 | 1.390 (3) |
N5—C8 | 1.343 (2) | C15—C16 | 1.395 (3) |
N5—C7 | 1.457 (3) | C15—H15 | 0.9500 |
N5—H5 | 0.8800 | C16—H16 | 0.9500 |
N6—C9 | 1.355 (2) | C17—C18 | 1.510 (3) |
N6—C8 | 1.403 (2) | C17—C19 | 1.518 (3) |
N6—H6 | 0.8800 | C17—H17 | 1.0000 |
C7—C10 | 1.527 (3) | C18—H18A | 0.9800 |
C7—C9 | 1.532 (3) | C18—H18B | 0.9800 |
C7—C11 | 1.533 (2) | C18—H18C | 0.9800 |
C10—H10A | 0.9800 | C19—H19A | 0.9800 |
C10—H10B | 0.9800 | C19—H19B | 0.9800 |
C10—H10C | 0.9800 | C19—H19C | 0.9800 |
C11—C16 | 1.391 (3) | ||
C14—O2—C17 | 119.19 (16) | C12—C13—C14 | 121.99 (17) |
C8—N5—C7 | 112.98 (16) | C12—C13—Br1 | 118.72 (14) |
C8—N5—H5 | 123.5 | C14—C13—Br1 | 119.29 (14) |
C7—N5—H5 | 123.5 | O2—C14—C15 | 125.17 (19) |
C9—N6—C8 | 111.90 (16) | O2—C14—C13 | 116.75 (17) |
C9—N6—H6 | 124.1 | C15—C14—C13 | 118.06 (17) |
C8—N6—H6 | 124.1 | C14—C15—C16 | 120.16 (19) |
N5—C7—C10 | 111.38 (18) | C14—C15—H15 | 119.9 |
N5—C7—C9 | 100.82 (14) | C16—C15—H15 | 119.9 |
C10—C7—C9 | 111.14 (19) | C11—C16—C15 | 121.28 (18) |
N5—C7—C11 | 112.40 (17) | C11—C16—H16 | 119.4 |
C10—C7—C11 | 113.38 (17) | C15—C16—H16 | 119.4 |
C9—C7—C11 | 106.91 (15) | O2—C17—C18 | 104.66 (16) |
O3—C8—N5 | 128.94 (19) | O2—C17—C19 | 110.02 (17) |
O3—C8—N6 | 124.06 (18) | C18—C17—C19 | 112.35 (17) |
N5—C8—N6 | 107.00 (16) | O2—C17—H17 | 109.9 |
O4—C9—N6 | 126.56 (18) | C18—C17—H17 | 109.9 |
O4—C9—C7 | 126.47 (18) | C19—C17—H17 | 109.9 |
N6—C9—C7 | 106.94 (16) | C17—C18—H18A | 109.5 |
C7—C10—H10A | 109.5 | C17—C18—H18B | 109.5 |
C7—C10—H10B | 109.5 | H18A—C18—H18B | 109.5 |
H10A—C10—H10B | 109.5 | C17—C18—H18C | 109.5 |
C7—C10—H10C | 109.5 | H18A—C18—H18C | 109.5 |
H10A—C10—H10C | 109.5 | H18B—C18—H18C | 109.5 |
H10B—C10—H10C | 109.5 | C17—C19—H19A | 109.5 |
C16—C11—C12 | 118.35 (17) | C17—C19—H19B | 109.5 |
C16—C11—C7 | 121.39 (17) | H19A—C19—H19B | 109.5 |
C12—C11—C7 | 120.08 (17) | C17—C19—H19C | 109.5 |
C13—C12—C11 | 120.15 (18) | H19A—C19—H19C | 109.5 |
C13—C12—H12 | 119.9 | H19B—C19—H19C | 109.5 |
C11—C12—H12 | 119.9 | ||
C8—N5—C7—C10 | 120.1 (2) | C10—C7—C11—C12 | −44.5 (3) |
C8—N5—C7—C9 | 2.12 (19) | C9—C7—C11—C12 | 78.3 (2) |
C8—N5—C7—C11 | −111.41 (18) | C16—C11—C12—C13 | −1.0 (3) |
C7—N5—C8—O3 | −178.24 (19) | C7—C11—C12—C13 | −176.27 (17) |
C7—N5—C8—N6 | 1.4 (2) | C11—C12—C13—C14 | 0.9 (3) |
C9—N6—C8—O3 | 174.64 (18) | C11—C12—C13—Br1 | −178.41 (14) |
C9—N6—C8—N5 | −5.1 (2) | C17—O2—C14—C15 | −20.8 (3) |
C8—N6—C9—O4 | −175.63 (19) | C17—O2—C14—C13 | 160.16 (18) |
C8—N6—C9—C7 | 6.4 (2) | C12—C13—C14—O2 | 178.61 (17) |
N5—C7—C9—O4 | 176.99 (19) | Br1—C13—C14—O2 | −2.1 (2) |
C10—C7—C9—O4 | 58.8 (3) | C12—C13—C14—C15 | −0.5 (3) |
C11—C7—C9—O4 | −65.4 (2) | Br1—C13—C14—C15 | 178.87 (15) |
N5—C7—C9—N6 | −5.00 (18) | O2—C14—C15—C16 | −178.87 (18) |
C10—C7—C9—N6 | −123.16 (18) | C13—C14—C15—C16 | 0.1 (3) |
C11—C7—C9—N6 | 112.63 (17) | C12—C11—C16—C15 | 0.7 (3) |
N5—C7—C11—C16 | 12.9 (3) | C7—C11—C16—C15 | 175.87 (18) |
C10—C7—C11—C16 | 140.4 (2) | C14—C15—C16—C11 | −0.2 (3) |
C9—C7—C11—C16 | −96.8 (2) | C14—O2—C17—C18 | 170.47 (16) |
N5—C7—C11—C12 | −171.94 (16) | C14—O2—C17—C19 | −68.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O4i | 0.98 | 2.60 | 3.529 (3) | 158 |
C15—H15···Br1i | 0.95 | 3.02 | 3.939 (2) | 162 |
N6—H6···O4ii | 0.88 | 1.97 | 2.828 (2) | 165 |
N5—H5···O3iii | 0.88 | 2.12 | 2.861 (2) | 141 |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z+1; (iii) x−1/2, −y+3/2, −z+1. |
C13H15ClN2O3 | Dx = 1.311 Mg m−3 |
Mr = 282.72 | Melting point = 475–477 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1397 (3) Å | Cell parameters from 9929 reflections |
b = 10.0128 (4) Å | θ = 2.9–27.9° |
c = 20.0431 (8) Å | µ = 0.27 mm−1 |
V = 1432.85 (10) Å3 | T = 90 K |
Z = 4 | Plate, colorless |
F(000) = 592 | 0.27 × 0.27 × 0.21 mm |
Bruker D8 VENTURE diffractometer | 3350 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.023 |
Absorption correction: integration (SADABS; Bruker, 2014) | θmax = 28.0°, θmin = 2.3° |
Tmin = 0.916, Tmax = 0.954 | h = −9→9 |
32943 measured reflections | k = −13→13 |
3425 independent reflections | l = −26→26 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.027 | w = 1/[σ2(Fo2) + (0.0389P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.079 | (Δ/σ)max = 0.001 |
S = 1.68 | Δρmax = 0.28 e Å−3 |
3425 reflections | Δρmin = −0.22 e Å−3 |
175 parameters | Absolute structure: Flack x determined using 1385 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
0 restraints | Absolute structure parameter: 0.009 (8) |
C13H15ClN2O3 | V = 1432.85 (10) Å3 |
Mr = 282.72 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.1397 (3) Å | µ = 0.27 mm−1 |
b = 10.0128 (4) Å | T = 90 K |
c = 20.0431 (8) Å | 0.27 × 0.27 × 0.21 mm |
Bruker D8 VENTURE diffractometer | 3425 independent reflections |
Absorption correction: integration (SADABS; Bruker, 2014) | 3350 reflections with I > 2σ(I) |
Tmin = 0.916, Tmax = 0.954 | Rint = 0.023 |
32943 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.079 | Δρmax = 0.28 e Å−3 |
S = 1.68 | Δρmin = −0.22 e Å−3 |
3425 reflections | Absolute structure: Flack x determined using 1385 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
175 parameters | Absolute structure parameter: 0.009 (8) |
0 restraints |
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 | ||
Cl1 | 0.27670 (6) | 0.69656 (4) | 0.65403 (2) | 0.02286 (13) | |
O2 | 0.3090 (2) | 0.46523 (14) | 0.73500 (6) | 0.0401 (4) | |
O3 | 1.27973 (17) | 0.36910 (11) | 0.49720 (6) | 0.0240 (3) | |
O4 | 0.88769 (16) | 0.72460 (10) | 0.52129 (5) | 0.0149 (2) | |
N5 | 0.95990 (18) | 0.37992 (12) | 0.51449 (7) | 0.0153 (3) | |
H5 | 0.9349 | 0.2942 | 0.5184 | 0.018* | |
N6 | 1.11959 (17) | 0.56832 (12) | 0.50854 (6) | 0.0149 (3) | |
H6 | 1.2159 | 0.6228 | 0.5052 | 0.018* | |
C7 | 0.81752 (19) | 0.48393 (14) | 0.51642 (7) | 0.0122 (3) | |
C8 | 1.1342 (2) | 0.42885 (15) | 0.50598 (8) | 0.0160 (3) | |
C9 | 0.9406 (2) | 0.60975 (14) | 0.51672 (7) | 0.0121 (3) | |
C10 | 0.7029 (2) | 0.48536 (16) | 0.45165 (8) | 0.0178 (3) | |
H10A | 0.7874 | 0.4951 | 0.4134 | 0.027* | |
H10B | 0.6148 | 0.5604 | 0.4526 | 0.027* | |
H10C | 0.6331 | 0.4015 | 0.4476 | 0.027* | |
C11 | 0.6927 (2) | 0.47604 (15) | 0.57820 (7) | 0.0138 (3) | |
C12 | 0.5631 (2) | 0.57769 (15) | 0.58963 (7) | 0.0154 (3) | |
H12 | 0.5602 | 0.6531 | 0.5609 | 0.018* | |
C13 | 0.4397 (2) | 0.56974 (16) | 0.64193 (8) | 0.0176 (3) | |
C14 | 0.4386 (3) | 0.46071 (18) | 0.68561 (8) | 0.0250 (4) | |
C15 | 0.5703 (3) | 0.3610 (2) | 0.67485 (9) | 0.0308 (4) | |
H15 | 0.5750 | 0.2864 | 0.7041 | 0.037* | |
C16 | 0.6959 (2) | 0.36877 (17) | 0.62175 (8) | 0.0219 (3) | |
H16 | 0.7849 | 0.2994 | 0.6153 | 0.026* | |
C17 | 0.2730 (3) | 0.3480 (2) | 0.77469 (9) | 0.0359 (5) | |
H17 | 0.3949 | 0.3107 | 0.7907 | 0.043* | |
C18 | 0.1633 (3) | 0.4001 (3) | 0.83411 (10) | 0.0452 (6) | |
H18A | 0.2356 | 0.4701 | 0.8565 | 0.068* | |
H18B | 0.1397 | 0.3267 | 0.8654 | 0.068* | |
H18C | 0.0436 | 0.4370 | 0.8188 | 0.068* | |
C19 | 0.1706 (4) | 0.2430 (3) | 0.73698 (14) | 0.0619 (8) | |
H19A | 0.0587 | 0.2818 | 0.7164 | 0.093* | |
H19B | 0.1336 | 0.1712 | 0.7675 | 0.093* | |
H19C | 0.2522 | 0.2065 | 0.7021 | 0.093* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0193 (2) | 0.0269 (2) | 0.02235 (19) | 0.00684 (16) | 0.00608 (15) | −0.00032 (15) |
O2 | 0.0438 (9) | 0.0423 (8) | 0.0342 (7) | 0.0146 (7) | 0.0254 (7) | 0.0183 (6) |
O3 | 0.0127 (5) | 0.0138 (5) | 0.0455 (7) | 0.0033 (5) | 0.0032 (6) | −0.0029 (5) |
O4 | 0.0150 (5) | 0.0099 (5) | 0.0197 (5) | 0.0024 (4) | 0.0012 (4) | 0.0004 (4) |
N5 | 0.0117 (6) | 0.0068 (6) | 0.0276 (7) | 0.0001 (5) | 0.0028 (5) | 0.0005 (5) |
N6 | 0.0098 (6) | 0.0087 (6) | 0.0264 (6) | −0.0009 (5) | 0.0009 (5) | −0.0012 (5) |
C7 | 0.0099 (7) | 0.0097 (6) | 0.0169 (7) | −0.0002 (5) | 0.0005 (5) | 0.0004 (5) |
C8 | 0.0141 (7) | 0.0116 (7) | 0.0223 (7) | −0.0008 (6) | −0.0010 (6) | −0.0003 (6) |
C9 | 0.0119 (7) | 0.0125 (7) | 0.0120 (6) | −0.0020 (5) | 0.0002 (5) | 0.0008 (5) |
C10 | 0.0146 (7) | 0.0214 (8) | 0.0175 (7) | −0.0030 (6) | −0.0018 (6) | −0.0007 (6) |
C11 | 0.0106 (7) | 0.0153 (7) | 0.0156 (6) | −0.0015 (5) | 0.0003 (5) | 0.0010 (5) |
C12 | 0.0144 (7) | 0.0156 (7) | 0.0160 (7) | −0.0003 (6) | −0.0005 (6) | 0.0031 (6) |
C13 | 0.0141 (7) | 0.0192 (7) | 0.0195 (7) | 0.0036 (6) | 0.0008 (6) | 0.0007 (6) |
C14 | 0.0263 (9) | 0.0285 (9) | 0.0201 (8) | 0.0049 (8) | 0.0087 (7) | 0.0088 (7) |
C15 | 0.0338 (10) | 0.0295 (9) | 0.0292 (9) | 0.0090 (9) | 0.0097 (8) | 0.0167 (8) |
C16 | 0.0213 (8) | 0.0206 (8) | 0.0238 (8) | 0.0050 (7) | 0.0021 (7) | 0.0076 (6) |
C17 | 0.0293 (10) | 0.0476 (11) | 0.0307 (9) | 0.0059 (9) | 0.0117 (9) | 0.0219 (9) |
C18 | 0.0439 (13) | 0.0628 (15) | 0.0288 (10) | 0.0004 (11) | 0.0148 (9) | 0.0171 (10) |
C19 | 0.0543 (17) | 0.0669 (17) | 0.0646 (16) | −0.0140 (14) | 0.0265 (14) | −0.0055 (14) |
Cl1—C13 | 1.7396 (16) | C11—C12 | 1.395 (2) |
O2—C14 | 1.355 (2) | C12—C13 | 1.371 (2) |
O2—C17 | 1.441 (2) | C12—H12 | 0.9500 |
O3—C8 | 1.2121 (18) | C13—C14 | 1.399 (2) |
O4—C9 | 1.2139 (18) | C14—C15 | 1.389 (3) |
N5—C8 | 1.3479 (19) | C15—C16 | 1.394 (2) |
N5—C7 | 1.4558 (18) | C15—H15 | 0.9500 |
N5—H5 | 0.8800 | C16—H16 | 0.9500 |
N6—C9 | 1.3536 (19) | C17—C19 | 1.487 (3) |
N6—C8 | 1.4014 (19) | C17—C18 | 1.518 (3) |
N6—H6 | 0.8800 | C17—H17 | 1.0000 |
C7—C11 | 1.5277 (19) | C18—H18A | 0.9800 |
C7—C10 | 1.535 (2) | C18—H18B | 0.9800 |
C7—C9 | 1.5360 (19) | C18—H18C | 0.9800 |
C10—H10A | 0.9800 | C19—H19A | 0.9800 |
C10—H10B | 0.9800 | C19—H19B | 0.9800 |
C10—H10C | 0.9800 | C19—H19C | 0.9800 |
C11—C16 | 1.384 (2) | ||
C14—O2—C17 | 119.87 (16) | C12—C13—C14 | 121.82 (15) |
C8—N5—C7 | 112.83 (12) | C12—C13—Cl1 | 119.59 (12) |
C8—N5—H5 | 123.6 | C14—C13—Cl1 | 118.57 (12) |
C7—N5—H5 | 123.6 | O2—C14—C15 | 126.84 (16) |
C9—N6—C8 | 112.33 (13) | O2—C14—C13 | 115.78 (16) |
C9—N6—H6 | 123.8 | C15—C14—C13 | 117.37 (15) |
C8—N6—H6 | 123.8 | C14—C15—C16 | 120.93 (16) |
N5—C7—C11 | 113.08 (12) | C14—C15—H15 | 119.5 |
N5—C7—C10 | 110.89 (12) | C16—C15—H15 | 119.5 |
C11—C7—C10 | 112.02 (12) | C11—C16—C15 | 120.96 (16) |
N5—C7—C9 | 100.80 (11) | C11—C16—H16 | 119.5 |
C11—C7—C9 | 111.90 (11) | C15—C16—H16 | 119.5 |
C10—C7—C9 | 107.50 (12) | O2—C17—C19 | 112.53 (18) |
O3—C8—N5 | 129.09 (13) | O2—C17—C18 | 104.23 (17) |
O3—C8—N6 | 124.11 (14) | C19—C17—C18 | 112.8 (2) |
N5—C8—N6 | 106.80 (13) | O2—C17—H17 | 109.0 |
O4—C9—N6 | 126.38 (14) | C19—C17—H17 | 109.0 |
O4—C9—C7 | 126.82 (14) | C18—C17—H17 | 109.0 |
N6—C9—C7 | 106.75 (12) | C17—C18—H18A | 109.5 |
C7—C10—H10A | 109.5 | C17—C18—H18B | 109.5 |
C7—C10—H10B | 109.5 | H18A—C18—H18B | 109.5 |
H10A—C10—H10B | 109.5 | C17—C18—H18C | 109.5 |
C7—C10—H10C | 109.5 | H18A—C18—H18C | 109.5 |
H10A—C10—H10C | 109.5 | H18B—C18—H18C | 109.5 |
H10B—C10—H10C | 109.5 | C17—C19—H19A | 109.5 |
C16—C11—C12 | 118.27 (14) | C17—C19—H19B | 109.5 |
C16—C11—C7 | 122.80 (14) | H19A—C19—H19B | 109.5 |
C12—C11—C7 | 118.85 (12) | C17—C19—H19C | 109.5 |
C13—C12—C11 | 120.62 (13) | H19A—C19—H19C | 109.5 |
C13—C12—H12 | 119.7 | H19B—C19—H19C | 109.5 |
C11—C12—H12 | 119.7 | ||
C8—N5—C7—C11 | −126.78 (14) | C10—C7—C11—C12 | −60.26 (17) |
C8—N5—C7—C10 | 106.43 (14) | C9—C7—C11—C12 | 60.55 (17) |
C8—N5—C7—C9 | −7.18 (15) | C16—C11—C12—C13 | −1.3 (2) |
C7—N5—C8—O3 | −173.72 (17) | C7—C11—C12—C13 | 175.49 (14) |
C7—N5—C8—N6 | 5.83 (18) | C11—C12—C13—C14 | 0.0 (2) |
C9—N6—C8—O3 | 178.00 (15) | C11—C12—C13—Cl1 | −178.80 (11) |
C9—N6—C8—N5 | −1.57 (19) | C17—O2—C14—C15 | −12.6 (3) |
C8—N6—C9—O4 | 179.17 (14) | C17—O2—C14—C13 | 168.51 (17) |
C8—N6—C9—C7 | −2.93 (18) | C12—C13—C14—O2 | −179.76 (16) |
N5—C7—C9—O4 | −176.28 (14) | Cl1—C13—C14—O2 | −0.9 (2) |
C11—C7—C9—O4 | −55.83 (19) | C12—C13—C14—C15 | 1.2 (3) |
C10—C7—C9—O4 | 67.57 (18) | Cl1—C13—C14—C15 | −179.94 (15) |
N5—C7—C9—N6 | 5.83 (15) | O2—C14—C15—C16 | 179.90 (18) |
C11—C7—C9—N6 | 126.28 (13) | C13—C14—C15—C16 | −1.2 (3) |
C10—C7—C9—N6 | −110.32 (13) | C12—C11—C16—C15 | 1.3 (2) |
N5—C7—C11—C16 | −9.8 (2) | C7—C11—C16—C15 | −175.34 (16) |
C10—C7—C11—C16 | 116.38 (16) | C14—C15—C16—C11 | 0.0 (3) |
C9—C7—C11—C16 | −122.81 (15) | C14—O2—C17—C19 | −71.8 (2) |
N5—C7—C11—C12 | 173.55 (13) | C14—O2—C17—C18 | 165.63 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O3i | 0.88 | 2.00 | 2.8155 (16) | 154 |
N6—H6···O4ii | 0.88 | 2.03 | 2.8845 (16) | 163 |
C12—H12···O4 | 0.95 | 2.57 | 3.0679 (19) | 113 |
C12—H12···O4iii | 0.95 | 2.39 | 3.2294 (18) | 147 |
C17—H17···Cl1iv | 1.00 | 2.83 | 3.831 (2) | 175 |
C18—H18B···O4iv | 0.98 | 2.50 | 3.409 (2) | 154 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, −y+3/2, −z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) −x+1, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O4i | 0.98 | 2.60 | 3.529 (3) | 158.4 |
C15—H15···Br1i | 0.95 | 3.02 | 3.939 (2) | 162.4 |
N6—H6···O4ii | 0.88 | 1.97 | 2.828 (2) | 164.6 |
N5—H5···O3iii | 0.88 | 2.12 | 2.861 (2) | 141.2 |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z+1; (iii) x−1/2, −y+3/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O3i | 0.88 | 2.00 | 2.8155 (16) | 153.6 |
N6—H6···O4ii | 0.88 | 2.03 | 2.8845 (16) | 163.4 |
C12—H12···O4 | 0.95 | 2.57 | 3.0679 (19) | 112.9 |
C12—H12···O4iii | 0.95 | 2.39 | 3.2294 (18) | 146.6 |
C17—H17···Cl1iv | 1.00 | 2.83 | 3.831 (2) | 175.0 |
C18—H18B···O4iv | 0.98 | 2.50 | 3.409 (2) | 154.4 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, −y+3/2, −z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) −x+1, y−1/2, −z+3/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C13H15BrN2O3 | C13H15ClN2O3 |
Mr | 327.17 | 282.72 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 90 | 90 |
a, b, c (Å) | 6.1840 (3), 9.6495 (4), 23.1111 (10) | 7.1397 (3), 10.0128 (4), 20.0431 (8) |
V (Å3) | 1379.10 (11) | 1432.85 (10) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.99 | 0.27 |
Crystal size (mm) | 0.25 × 0.25 × 0.10 | 0.27 × 0.27 × 0.21 |
Data collection | ||
Diffractometer | Bruker D8 VENTURE | Bruker D8 VENTURE |
Absorption correction | Integration (SADABS; Bruker, 2014) | Integration (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.482, 0.631 | 0.916, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31000, 3271, 3206 | 32943, 3425, 3350 |
Rint | 0.028 | 0.023 |
(sin θ/λ)max (Å−1) | 0.659 | 0.660 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.047, 1.29 | 0.027, 0.079, 1.68 |
No. of reflections | 3271 | 3425 |
No. of parameters | 175 | 175 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.30 | 0.28, −0.22 |
Absolute structure | Flack x determined using 1301 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). | Flack x determined using 1385 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
Absolute structure parameter | 0.018 (2) | 0.009 (8) |
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a), Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015b) and publCIF (Westrip, 2010).
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