Crystal structures of (S)-(+)-5-(3-bromo/chloro-4-isopropoxyphen­yl)-5-methyl­imidazolidine-2,4-dione

Ohba, S.; Koura, M.; Sumida, H.; Shibuya, K.

doi:10.1107/S2056989015023014

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ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 184-187

doi:10.1107/S2056989015023014

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Crystal structures of (S)-(+)-5-(3-bromo/chloro-4-isopropoxyphenyl)-5-methylimidazolidine-2,4-dione

Shigeru Ohba,^a ^* Minoru Koura,^b Hisashi Sumida ^b and Kimiyuki Shibuya ^b

^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

Edited by J. Simpson, University of Otago, New Zealand (Received 25 November 2015; accepted 1 December 2015; online 16 January 2016)

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.

CCDC references: 1436066; 1439808

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 chirality of the hydantoin unit is crucial to the LXR activation and β selectivity (Koura et al., 2016 ). In the present study, the absolute configuration 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 refinement (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.

Figure 1
The molecular structure of (I)

, showing displacement ellipsoids at the 50% probability level.

Figure 2
The molecular structure of (II)

, showing displacement ellipsoids at the 50% probability level.

3. Supramolecular features

The crystal structure 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 = ½ along a. Groups of four molecules are linked by these N—H⋯O hydrogen bonds, generating $[R_{4}^{4}]$ (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.

Table 1
Hydrogen-bond geometry (Å, °) for (I)

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) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 3
The crystal structure of (I)

, projected along a. Hydrogen bonds are shown as dashed lines.

Figure 4
A schematic drawing of the N—H⋯O hydrogen-bonding network in (I)

. The arrows indicate the twofold screw axes along a.

Both (I) and (II) crystallize in space group 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 crystal structure 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.

Table 2
Hydrogen-bond geometry (Å, °) for (II)

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⋯Cl1^iv	1.00	2.83	3.831 (2)	175
C18—H18B⋯O4^iv	0.98	2.50	3.409 (2)	154
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 5
The crystal structure of (II)

, projected along a. Hydrogen bonds are shown as dashed lines.

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 absolute configuration 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 permethylated β-cyclodextrin based on the known absolute configuration 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 absolute configuration 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 absolute configuration of such compounds determined from anomalous-dispersion effects.

5. Synthesis and crystallization

Compounds (I) and (II) were prepared from the corresponding (+)-non-halogeno-derivatives, which were separated from a racemic mixture (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 refinement details are summarized in Table 3. 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 U_iso(H) = 1.2U_eq(C/N) and U_iso(H) = 1.5U_eq(C_methyl). 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.

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₃H₁₅BrN₂O₃	C₁₃H₁₅ClN₂O₃
M_r	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)
T_min, T_max	0.482, 0.631	0.916, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	31000, 3271, 3206	32943, 3425, 3350
R_int	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
Δρ_max, Δρ_min (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 and SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1436066; 1439808

Crystal structure: contains datablocks I, II, global. DOI: 10.1107/S2056989015023014/sj5484sup1.cif

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

checkCIF report

Chemical context top

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 chirality of the hydantoin unit is crucial to the LXR activation and β selectivity (Koura, Sumida et al., 2015). In the present study, the absolute configuration 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.

Structural commentary top

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 refinement (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.

Supramolecular features top

The crystal structure 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 space group 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 crystal structure 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.

Database survey top

Structures of 5-phenyl-5-alkylhydantoin derivatives have been investigated to review the relationships between the absolute configuration 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 permethylated β-cyclodextrin based on the known absolute configuration 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 absolute configuration 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 absolute configuration of such compounds determined from anomalous-dispersion effects.

Synthesis and crystallization top

Compounds (I) and (II) were prepared from the corresponding (+)-non-halogeno-derivatives, which were separated from a racemic mixture (Koura, Sumida et al., 2015). 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).

Refinement top

Crystal data, data collection and structure refinement 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 U_iso(H) = 1.2U_eq(C/N) and U_iso(H) = 1.5U_eq(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.

Related literature top

Several 2-oxochromene derivatives of chiral hydantoin molecules show liver X receptor β-selective agonists activity (Matsuda et al., 2015; Koura, Matsuda et al., 2015).

Structure description top

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 refinement (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.

Both (I) and (II) crystallize in space group 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 crystal structure 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.

Structures of 5-phenyl-5-alkylhydantoin derivatives have been investigated to review the relationships between the absolute configuration 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 permethylated β-cyclodextrin based on the known absolute configuration 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 absolute configuration 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 absolute configuration of such compounds determined from anomalous-dispersion effects.

Several 2-oxochromene derivatives of chiral hydantoin molecules show liver X receptor β-selective agonists activity (Matsuda et al., 2015; Koura, Matsuda et al., 2015).

Synthesis and crystallization top

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).

Refinement details top

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2014); cell refinement: 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).

Figures top

	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.

(I) (S)-(+)-5-(3-Bromo-4-isopropoxyphenyl)-5-methylimidazolidine-2,4-dione top

Crystal data top

C₁₃H₁₅BrN₂O₃	D_x = 1.576 Mg m⁻³
M_r = 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

Data collection top

Bruker D8 VENTURE diffractometer	3206 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.028
Absorption correction: integration (SADABS; Bruker, 2014)	θ_max = 27.9°, θ_min = 2.3°
T_min = 0.482, T_max = 0.631	h = −8→8
31000 measured reflections	k = −12→12
3271 independent reflections	l = −30→30

Refinement top

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(F_o²) + (0.0213P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.047	(Δ/σ)_max = 0.009
S = 1.29	Δρ_max = 0.41 e Å⁻³
3271 reflections	Δρ_min = −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)

Crystal data top

C₁₃H₁₅BrN₂O₃	V = 1379.10 (11) Å³
M_r = 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

Data collection top

Bruker D8 VENTURE diffractometer	3271 independent reflections
Absorption correction: integration (SADABS; Bruker, 2014)	3206 reflections with I > 2σ(I)
T_min = 0.482, T_max = 0.631	R_int = 0.028
31000 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	H-atom parameters constrained
wR(F²) = 0.047	Δρ_max = 0.41 e Å⁻³
S = 1.29	Δρ_min = −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

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

(II) (S)-(+)-5-(3-Chloro-4-isopropoxyphenyl)-5-methylimidazolidine-2,4-dione top

Crystal data top

C₁₃H₁₅ClN₂O₃	D_x = 1.311 Mg m⁻³
M_r = 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

Data collection top

Bruker D8 VENTURE diffractometer	3350 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.023
Absorption correction: integration (SADABS; Bruker, 2014)	θ_max = 28.0°, θ_min = 2.3°
T_min = 0.916, T_max = 0.954	h = −9→9
32943 measured reflections	k = −13→13
3425 independent reflections	l = −26→26

Refinement top

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(F_o²) + (0.0389P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max = 0.001
S = 1.68	Δρ_max = 0.28 e Å⁻³
3425 reflections	Δρ_min = −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)

Crystal data top

C₁₃H₁₅ClN₂O₃	V = 1432.85 (10) Å³
M_r = 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

Data collection top

Bruker D8 VENTURE diffractometer	3425 independent reflections
Absorption correction: integration (SADABS; Bruker, 2014)	3350 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.954	R_int = 0.023
32943 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.079	Δρ_max = 0.28 e Å⁻³
S = 1.68	Δρ_min = −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

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cl1^iv	1.00	2.83	3.831 (2)	175
C18—H18B···O4^iv	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.

Hydrogen-bond geometry (Å, º) for (I) top

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.

Hydrogen-bond geometry (Å, º) for (II) top

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···Cl1^iv	1.00	2.83	3.831 (2)	175.0
C18—H18B···O4^iv	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
M_r	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)
T_min, T_max	0.482, 0.631	0.916, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	31000, 3271, 3206	32943, 3425, 3350
R_int	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
Δρ_max, Δρ_min (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).

References

Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Coquerel, G., Petit, M. N. & Robert, F. (1993). Acta Cryst. C49, 824–825. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
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Koura, M., Matsuda, T., Okuda, A., Watanabe, Y., Yamaguchi, Y., Kurobuchi, S., Matsumoto, Y. & Shibuya, K. (2015). Bioorg. Med. Chem. Lett. 25, 2668–2674. Web of Science CrossRef CAS PubMed Google Scholar
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Matsuda, T., Okuda, A., Watanabe, Y., Miura, T., Ozawa, H., Tosaka, A., Yamazaki, K., Yamaguchi, Y., Kurobuchi, S., Koura, M. & Shibuya, K. (2015). Bioorg. Med. Chem. Lett. 25, 1274–1278. Web of Science CrossRef CAS PubMed Google Scholar
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Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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Volume 72| Part 2| February 2016| Pages 184-187

doi:10.1107/S2056989015023014

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of (S)-(+)-5-(3-bromo/chloro-4-isopropoxyphen­yl)-5-methyl­imidazolidine-2,4-dione

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

References

research communications

Crystal structures of (S)-(+)-5-(3-bromo/chloro-4-isopropoxyphenyl)-5-methylimidazolidine-2,4-dione

3. Supramolecular features