Cocrystals of diastereoisomers of 1,4-dihydro­pyridine derivatives

A mixture of the RR/SS and RS/SR diastereoisomeric pairs of methyl 4-(2,4-dichloro­phen­yl)-2,7-dimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate, C₁₉H₁₉Cl₂NO₃, forms cocrystals in which there is one unique mol­ecule in the asymmetric unit, but the mol­ecule displays disorder in the region of the 7-position of the quinoline ring system as a result of the random occurrence of the diastereoisomers at the same crystallographic site. A similar arrangement exists in the monohydrate cocrystals that form from a mixture of the RR/SS and RS/SR diastereoisomeric pairs of methyl 4-(2,4-dichloro­phen­yl)-2-methyl-7-phenyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate monohydrate, C₂₄H₂₁Cl₂NO₃·H₂O. These compounds belong to a class of 1,4-dihydro­pyridines whose members have calcium modulatory properties. The 1,4-dihydro­pyridine rings have the usual shallow boat conformation. In each structure, the 2,4-dichloro­phenyl ring is oriented such that the 2-chloro substituent is in a synperi­planar orientation with respect to the 1,4-dihydro­pyridine ring plane. In each crystal structure, the mol­ecules are linked into chains by N-H...O hydrogen-bonding inter­actions.

S1. Comment

1,4-Dihydropyridine (1,4-DHP) derivatives have yielded many drugs which act as calcium channel agonists or antagonists (Rose, 1989, 1990). Nifedipine is the prototype of this group, and both it and its structural analogues are used as antianginal and antihypertensive drugs (Janis & Triggle, 1984). Our interest is in the correlation between the three-dimensional structure and calcium antagonistic behaviour of condensed derivatives of 1,4-DHP (Linden et al., 1998, 2002, 2004, 2005; Şimşek et al., 2000, 2003; Kısmetli et al., 2004). Two new compounds have been prepared as further potentially active 1,4-DHP derivatives. These compounds differ only in the substituent at the 7-position on the oxocyclohexene ring and are methyl 4-(2,4-chlorophenyl)-2,7-dimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, (I), and methyl 4-(2,4-chlorophenyl)-2-methyl-7-phenyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate monohydrate, (II). The syntheses are not stereo-specific, so the reactions produced mixtures of the 4,7-diastereoisomers of the racemic compounds. The stereoisomers could not be separated readily and, as subsequently revealed by the crystal structure determinations, crystallization yielded cocrystals in which both diastereoisomers were incorporated, rather than crystals of a single compound forming preferentially.

Views of the asymmetric units in the structures of (I) and (II) are shown in Figs. 1 and 2, respectively. Compound (II) crystallizes as the monohydrate, in which the water molecule is disordered over two sites. The centrosymmetric space groups indicate that the compounds are racemic. Although there is only one formula unit in the asymmetric unit of each structure, the molecules are disordered at atom C7 of the oxocyclohexene rings [and at atom C6 in (II)] and the disorder extends through the substituents at C7 [methyl in (I) and phenyl in (II)]. The disorder manifests itself as alternate directions of folding of the flap of the C7-envelope [in (I)] or half-chair [in (II)] conformations of the oxocyclohexene rings, but inspection of the positions of the substituents indicates that the two arrangements are related by inversion of the configuration at atom C7. As the configuration at atom C4 is constant in both of the disordered arrangements, the disorder is actually a consequence of the presence of a mixture of diastereoisomers in the crystal. The diastereoisomers with the same configuration at atom C4 have been inserted randomly and in almost equal quantities in the crystal lattice and the centrosymmetric space group accommodates the enantiomers of the diastereoisomeric pair. If the diastereoisomers were incorporated into the crystal lattice in a regular sequence, one would find two molecules (at least) in the asymmetric unit. That a random distribution of diastereoisomers occurs in the crystal suggests that the shape of the volume occupied by the diastereoisomeric molecules is very similar.

Despite the disorder, most of the bond lengths and angles in (I) and (II) have normal values. There are small angular distortions about atoms C2 and C10 (Tables 1 and 3), which result from steric interactions between the methyl substituent at C2 and atom O1O of the ester substituent at C3 [O10···C9 = 2.790 (4) and 2.814 (5) Å for (I) and (II), respectively)]. The presence of π-electron conjugation keeps the ester group at C3 almost coplanar [C2═ C3—C10═O10 = −2.7 (4) and 0.6 (5)° for (I) and (II), respectively] with the endocyclic double bond and prevents the ester group from rotating into a sterically more amenable orientation. These properties are consistent with those of related compounds (Linden et al., 2005).

The switch from the 7-methyl substituent in compound (I) to the 7-phenyl substituent in compound (II) has no major influence on the conformations of the molecules. The 1,4-DHP rings have the shallow boat conformations generally observed for 4-aryl-1,4-DHP derivatives (Linden et al., 2005), although the conformations in (I) and (II) are among the shallowest examples. In compound (I), atoms N1 and C4 are 0.035 (2) and 0.115 (2) Å, respectively, from the plane defined by atoms C2, C3, C4A and C8A. The deviation of atom N1 from this plane is so small that the ring could almost be described as having a shallow envelope conformation. The corresponding displacements in compound (II) are 0.058 (3) and 0.200 (3) Å, respectively. The shallowness of the boat conformations is indicated by the small values of the total puckering amplitudes, Q (Cremer & Pople, 1975), of 0.090 (3) and 0.141 (3) Å for compounds (I) and (II), respectively. Three structures of 1,4-DHP derivatives with similarly shallow boat conformations were reported recently (Quesada et al., 2006) and several examples containing a planar ring are also known (Pastor et al., 1994; Duque et al., 2000; Low et al., 2001; Linden et al., 2002; Mahendra et al., 2003).

The plane of the 2,4-dichlorophenyl ring in each of the title compounds is, as frequently observed (Linden et al., 2005), essentially parallel to the N1···C4 axis. Compound (I) has a N1···C4—C13—C18 torsion angle of 2.6 (3)°, while the corresponding torsion angle in compound (II) is 1.8 (3)°. The 2-chloro substituent lies above the C4—H bond in the sterically most favourable synperiplanar orientation. The Cambridge Structural Database (Release 5.27 with January 2006 updates; Allen, 2002) contains five examples of 4-aryl-1,4-DHP compounds with 2,4-disubstitution in the phenyl ring. Three of these compounds are 4-(2,4-dichlorophenyl)-2,6-dimethyl-3,5-dicarboxy-1,4-DHP derivatives (Mehdi & Ravikumar, 1992; Sagar et al., 1999; Caignan & Holt, 2000), while there is one 4-(2-chloro-4-nitrophenyl)- (Rovnyak et al., 1988) and one 4-(2,4-dinitrophenyl)- analogue (Fossheim et al., 1982). In each of these compounds, the 2,4-disubstituted phenyl ring has a synperiplanar orientation with respect to the 1,4-DHP ring, although with the 4-(2,4-dinitrophenyl)- derivative and one of the 4-(2,4-dichloro)- derivatives (Sagar et al., 1999), the plane of the phenyl ring is rotated slightly to make angles of about 16 and 31°, respectively, with the N1···C4 axis.

The use of geometric restraints to handle the disordered atoms in the structures of (I) and (II) makes it unwise to analyse the conformations of the oxocyclohexene rings in any detail. It suffices to say that the oxocyclohexene ring in each diastereoisomer of compound (I) has a C7-envelope conformation, while the corresponding conformation in each diastereoisomer of compound (II) is that of a slightly distorted half-chair twisted about the C6—C7 bond. It has been noted previously that atom C7 is the atom that deviates most from the ring plane in structures involving the 5-oxoquinoline or 1,8-dioxoacridine moiety (Linden et al., 2005).

In compound (I), an intermolecular N—H···O hydrogen bond between the amine group and the carbonyl O atom of the oxocyclohexene ring of a neighbouring molecule (Table 2) links the molecules into extended chains which run parallel to the [101] direction and can be described by a graph-set motif of C(6) (Bernstein et al., 1995). The same C(6) motif has been observed in the crystal structures of several other closely related 1,4-DHP compounds (Linden et al., 1998, 2002, 2004, 2005; Şimşek et al., 2000). In compound (II), the major site of the disordered water molecule accepts the N—H···O hydrogen bond from the 1,4-DHP molecule and, in turn, forms another intermolecular hydrogen bond with the carbonyl O atom of the oxocyclohexene ring of a neighbouring 1,4-DHP molecule (Table 4). These interactions link the 1,4-DHP and water molecules alternately into extended chains which run parallel to the [100] direction and can be described by a binary graph-set motif of C₂²(8). The minor site of the water molecule (12% occupancy) has not been considered in this analysis.

S2. Experimental

For the synthesis of compounds (I) and (II), equimolar amounts of 2,4-dichlorobenzaldehyde, and 5-methyl-1,3-cyclohexanedione for (I) or 5-phenyl-1,3-cyclohexanedione for (II), together with methyl aminocrotonoate were refluxed in methanol for 8 h. The solution was then poured into water, and the precipitate which formed was filtered off, dried, and recrystallized from ethanol. The m.p. for the crystals containing the diastereoisomeric mixtures were 523 and 421 K, respectively.

S3. Refinement

For (I), the methyl-substituted atom of the oxocyclohexene ring and its associated methyl group are disordered, as a result of the occurrence of diastereoisomeric molecules at the same crystallographic site. Two sets of positions were defined for these atoms and the site occupation factor for the atoms corresponding to the major isomer refined to 0.512 (6). Similarity restraints were applied to the chemically equivalent bond lengths and angles involving all disordered C atoms, while neighbouring atoms within and between each conformation of the disordered groups were restrained to have similar atomic displacement parameters.

For (II), the disorder of the phenyl-substituted atom of the oxocyclohexene ring and its associated phenyl group, as well as an adjacent methylene group, was treated exactly as described above. The site occupation factor for the atoms corresponding to the major isomer refined to 0.505 (7). The asymmetric unit also contains a water molecule disordered over two adjacent positions and the site occupation factor of the more occupied site refined to 0.879 (6). The H atoms of the lesser occupied site were not included in the model.

For each structure, the position of the amine H atom, and the positions of the H atoms of the major occupied site of the water molecule in (II), were determined from a difference Fourier map and refined freely with individual isotropic displacement parameters. The methyl H atoms were constrained to an ideal geometry, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about their C—C bonds. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms at distances of 0.95, 0.99 or 1.00 Å for phenyl, methylene or methine groups, respectively, and with U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme and the disorder resulting from the occurrence of diastereoisomers at the same crystallographic site. Displacement ellipsoids are drawn at the 40% probability level. Some of the disordered H atoms have been omitted for clarity.
	Fig. 2. A view of the molecule of (II), showing the atom-labelling scheme and the disorder resulting from the occurrence of diastereoisomers at the same crystallographic site. Displacement ellipsoids are drawn at the 40% probability level. Some of the disordered H atoms have been omitted for clarity.

(I) (RR,SS)/(RS,SR)-methyl 4-(2,4-chlorophenyl)-2,7-dimethyl- 5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate

Crystal data

C19H19Cl2NO3	F(000) = 792
Mr = 380.27	Dx = 1.371 Mg m^−3
Monoclinic, P21/n	Melting point: 523 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.6670 (3) Å	Cell parameters from 13345 reflections
b = 13.7746 (4) Å	θ = 2.0–25.0°
c = 11.8897 (4) Å	µ = 0.37 mm^−1
β = 105.4328 (19)°	T = 160 K
V = 1841.88 (10) Å^3	Tablet, pale yellow
Z = 4	0.22 × 0.22 × 0.07 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3252 independent reflections
Radiation source: Nonius FR590 sealed tube generator	2469 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.072
Detector resolution: 9 pixels mm^-1	θmax = 25.0°, θmin = 2.2°
ω scans with κ offsets	h = −13→13
Absorption correction: multi-scan (Blessing, 1995)	k = −16→16
Tmin = 0.871, Tmax = 0.979	l = −14→14
23780 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom and difmap
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.073P)^2 + 1.1256P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3252 reflections	Δρmax = 0.71 e Å^−3
254 parameters	Δρmin = −0.30 e Å^−3
31 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Special details

Experimental. Solvent used: Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.491 (2) Frames collected: 194 Seconds exposure per frame: 26 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.22102 (6)	0.11917 (5)	0.91939 (6)	0.0436 (3)
Cl2	−0.04745 (8)	0.38039 (6)	1.06080 (7)	0.0573 (3)
O5	0.25975 (16)	0.26195 (16)	0.71309 (16)	0.0457 (5)
O10	−0.17030 (19)	−0.04887 (16)	0.64133 (19)	0.0551 (6)
O11	−0.00920 (17)	−0.00143 (14)	0.77785 (17)	0.0432 (5)
N1	−0.0879 (2)	0.17511 (17)	0.4283 (2)	0.0374 (6)
H1	−0.132 (3)	0.191 (2)	0.359 (3)	0.049 (9)*
C2	−0.1208 (2)	0.10291 (19)	0.4935 (2)	0.0334 (6)
C3	−0.0553 (2)	0.08602 (19)	0.6046 (2)	0.0318 (6)
C4	0.0522 (2)	0.14857 (18)	0.6638 (2)	0.0302 (6)
H4	0.1215	0.1044	0.6946	0.036*
C4A	0.0836 (2)	0.21715 (18)	0.5769 (2)	0.0302 (6)
C5	0.1923 (2)	0.2724 (2)	0.6137 (2)	0.0367 (6)
C6	0.2229 (3)	0.3432 (2)	0.5298 (3)	0.0514 (8)
H61	0.2768	0.3107	0.4898	0.062*	0.488 (6)
H62	0.2669	0.3983	0.5748	0.062*	0.488 (6)
H63	0.3105	0.3483	0.5468	0.062*	0.512 (6)
H64	0.1918	0.4080	0.5421	0.062*	0.512 (6)
C7A	0.1152 (4)	0.3832 (4)	0.4370 (4)	0.0505 (19)	0.488 (6)
H71	0.0671	0.4219	0.4791	0.061*	0.488 (6)
C19A	0.1413 (10)	0.4487 (7)	0.3452 (7)	0.086 (3)	0.488 (6)
H191	0.1792	0.4109	0.2951	0.129*	0.488 (6)
H192	0.1948	0.5009	0.3830	0.129*	0.488 (6)
H193	0.0669	0.4767	0.2977	0.129*	0.488 (6)
C7B	0.1730 (4)	0.3142 (4)	0.4037 (4)	0.0461 (16)	0.512 (6)
H72	0.2100	0.2512	0.3905	0.055*	0.512 (6)
C19B	0.2082 (7)	0.3908 (6)	0.3286 (6)	0.061 (2)	0.512 (6)
H194	0.1875	0.4551	0.3525	0.092*	0.512 (6)
H195	0.1660	0.3795	0.2467	0.092*	0.512 (6)
H196	0.2942	0.3875	0.3379	0.092*	0.512 (6)
C8	0.0394 (2)	0.2989 (2)	0.3806 (2)	0.0402 (7)
H81	−0.0365	0.3240	0.3303	0.048*	0.488 (6)
H82	0.0806	0.2637	0.3302	0.048*	0.488 (6)
H83	0.0003	0.3619	0.3860	0.048*	0.512 (6)
H84	0.0069	0.2732	0.3007	0.048*	0.512 (6)
C8A	0.0131 (2)	0.22939 (19)	0.4671 (2)	0.0322 (6)
C9	−0.2300 (2)	0.0493 (2)	0.4284 (3)	0.0453 (7)
H91	−0.2121	−0.0202	0.4275	0.068*
H92	−0.2557	0.0736	0.3481	0.068*
H93	−0.2935	0.0594	0.4670	0.068*
C10	−0.0871 (2)	0.00612 (19)	0.6710 (2)	0.0356 (6)
C12	−0.0352 (3)	−0.0761 (2)	0.8522 (3)	0.0499 (8)
H121	−0.1179	−0.0698	0.8557	0.075*
H122	0.0182	−0.0694	0.9308	0.075*
H123	−0.0237	−0.1400	0.8206	0.075*
C13	0.0305 (2)	0.20598 (18)	0.7668 (2)	0.0306 (6)
C14	0.1005 (2)	0.19828 (18)	0.8809 (2)	0.0326 (6)
C15	0.0781 (2)	0.25244 (19)	0.9711 (2)	0.0350 (6)
H15	0.1278	0.2466	1.0484	0.042*
C16	−0.0182 (3)	0.3151 (2)	0.9465 (2)	0.0379 (6)
C17	−0.0895 (2)	0.3261 (2)	0.8346 (2)	0.0401 (7)
H17	−0.1545	0.3701	0.8182	0.048*
C18	−0.0641 (2)	0.2712 (2)	0.7464 (2)	0.0357 (6)
H18	−0.1131	0.2784	0.6690	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0422 (4)	0.0492 (4)	0.0331 (4)	0.0138 (3)	−0.0011 (3)	0.0054 (3)
Cl2	0.0770 (6)	0.0613 (5)	0.0364 (4)	0.0174 (4)	0.0203 (4)	−0.0056 (4)
O5	0.0346 (10)	0.0656 (14)	0.0307 (11)	−0.0077 (9)	−0.0021 (8)	−0.0049 (9)
O10	0.0555 (13)	0.0543 (13)	0.0520 (13)	−0.0192 (11)	0.0084 (11)	0.0061 (11)
O11	0.0494 (11)	0.0390 (11)	0.0382 (11)	0.0014 (9)	0.0067 (9)	0.0104 (9)
N1	0.0335 (12)	0.0443 (14)	0.0275 (12)	−0.0053 (10)	−0.0037 (10)	0.0045 (10)
C2	0.0289 (13)	0.0358 (14)	0.0344 (15)	−0.0026 (11)	0.0063 (11)	−0.0038 (12)
C3	0.0316 (13)	0.0319 (13)	0.0313 (14)	−0.0004 (11)	0.0073 (11)	−0.0025 (11)
C4	0.0288 (13)	0.0338 (14)	0.0246 (13)	0.0032 (11)	0.0015 (10)	−0.0012 (11)
C4A	0.0286 (13)	0.0344 (13)	0.0255 (13)	0.0000 (11)	0.0036 (10)	−0.0032 (11)
C5	0.0343 (14)	0.0438 (16)	0.0292 (14)	−0.0043 (12)	0.0035 (12)	−0.0078 (12)
C6	0.0457 (17)	0.064 (2)	0.0395 (17)	−0.0250 (15)	0.0023 (14)	−0.0011 (15)
C7A	0.069 (4)	0.047 (3)	0.029 (3)	−0.022 (3)	0.002 (3)	0.002 (3)
C19A	0.110 (6)	0.075 (5)	0.056 (4)	−0.036 (4)	−0.010 (4)	0.010 (4)
C7B	0.049 (3)	0.054 (3)	0.036 (3)	−0.012 (3)	0.013 (2)	0.004 (3)
C19B	0.059 (4)	0.071 (4)	0.048 (4)	−0.020 (3)	0.004 (3)	0.020 (3)
C8	0.0426 (16)	0.0443 (16)	0.0295 (14)	−0.0040 (13)	0.0024 (12)	0.0052 (12)
C8A	0.0307 (13)	0.0362 (14)	0.0268 (14)	0.0012 (11)	0.0023 (11)	−0.0023 (11)
C9	0.0371 (15)	0.0503 (18)	0.0428 (17)	−0.0095 (13)	0.0003 (13)	−0.0036 (14)
C10	0.0369 (15)	0.0331 (14)	0.0367 (15)	0.0024 (12)	0.0093 (12)	−0.0009 (12)
C12	0.063 (2)	0.0442 (17)	0.0438 (18)	0.0044 (15)	0.0161 (15)	0.0138 (14)
C13	0.0339 (13)	0.0316 (13)	0.0255 (13)	0.0004 (11)	0.0067 (10)	0.0029 (11)
C14	0.0322 (13)	0.0333 (14)	0.0299 (14)	0.0027 (11)	0.0038 (11)	0.0050 (11)
C15	0.0430 (15)	0.0379 (15)	0.0220 (13)	−0.0004 (12)	0.0050 (11)	0.0048 (11)
C16	0.0481 (16)	0.0370 (15)	0.0315 (14)	0.0016 (13)	0.0157 (12)	−0.0009 (12)
C17	0.0397 (15)	0.0435 (16)	0.0371 (16)	0.0081 (13)	0.0104 (12)	0.0026 (13)
C18	0.0347 (14)	0.0415 (15)	0.0283 (14)	0.0071 (12)	0.0039 (11)	0.0017 (12)

Geometric parameters (Å, º)

Cl1—C14	1.741 (3)	C19A—H192	0.9800
Cl2—C16	1.737 (3)	C19A—H193	0.9800
O5—C5	1.242 (3)	C7B—C19B	1.508 (6)
O10—C10	1.208 (3)	C7B—C8	1.523 (4)
O11—C10	1.355 (3)	C7B—H72	1.0000
O11—C12	1.440 (3)	C19B—H194	0.9800
N1—C8A	1.367 (3)	C19B—H195	0.9800
N1—C2	1.377 (3)	C19B—H196	0.9800
N1—H1	0.88 (3)	C8—C8A	1.496 (4)
C2—C3	1.359 (4)	C8—H81	0.9900
C2—C9	1.497 (4)	C8—H82	0.9900
C3—C10	1.458 (4)	C8—H83	0.9900
C3—C4	1.530 (4)	C8—H84	0.9900
C4—C4A	1.515 (4)	C9—H91	0.9800
C4—C13	1.534 (3)	C9—H92	0.9800
C4—H4	1.0000	C9—H93	0.9800
C4A—C8A	1.356 (3)	C12—H121	0.9800
C4A—C5	1.444 (4)	C12—H122	0.9800
C5—C6	1.503 (4)	C12—H123	0.9800
C6—C7B	1.511 (4)	C13—C14	1.389 (4)
C6—C7A	1.537 (4)	C13—C18	1.393 (4)
C6—H61	0.9900	C14—C15	1.388 (4)
C6—H62	0.9900	C15—C16	1.385 (4)
C6—H63	0.9900	C15—H15	0.9500
C6—H64	0.9900	C16—C17	1.377 (4)
C7A—C8	1.505 (4)	C17—C18	1.388 (4)
C7A—C19A	1.508 (7)	C17—H17	0.9500
C7A—H71	1.0000	C18—H18	0.9500
C19A—H191	0.9800
C10—O11—C12	115.6 (2)	H194—C19B—H196	109.5
C2—N1—C8A	123.3 (2)	H195—C19B—H196	109.5
C8A—N1—H1	115 (2)	C8A—C8—C7A	113.1 (3)
C2—N1—H1	122 (2)	C8A—C8—C7B	110.6 (3)
N1—C2—C3	120.1 (2)	C8A—C8—H81	109.0
N1—C2—C9	113.1 (2)	C7A—C8—H81	109.0
C3—C2—C9	126.8 (2)	C8A—C8—H82	109.0
C2—C3—C10	119.8 (2)	C7A—C8—H82	109.0
C2—C3—C4	122.1 (2)	H81—C8—H82	107.8
C10—C3—C4	118.1 (2)	C8A—C8—H83	109.5
C3—C4—C4A	110.7 (2)	C7B—C8—H83	109.5
C4A—C4—C13	110.1 (2)	C8A—C8—H84	109.5
C3—C4—C13	111.6 (2)	C7B—C8—H84	109.5
C4A—C4—H4	108.1	H83—C8—H84	108.1
C3—C4—H4	108.1	N1—C8A—C4A	120.3 (2)
C13—C4—H4	108.1	C4A—C8A—C8	124.0 (2)
C8A—C4A—C5	119.0 (2)	N1—C8A—C8	115.7 (2)
C4—C4A—C8A	122.7 (2)	C2—C9—H91	109.5
C5—C4A—C4	118.3 (2)	C2—C9—H92	109.5
O5—C5—C4A	120.7 (3)	H91—C9—H92	109.5
O5—C5—C6	120.3 (2)	C2—C9—H93	109.5
C4A—C5—C6	119.0 (2)	H91—C9—H93	109.5
C5—C6—C7B	113.0 (3)	H92—C9—H93	109.5
C5—C6—C7A	114.6 (3)	O10—C10—O11	120.8 (3)
C5—C6—H61	108.6	O10—C10—C3	128.0 (3)
C7A—C6—H61	108.6	O11—C10—C3	111.2 (2)
C5—C6—H62	108.6	O11—C12—H121	109.5
C7A—C6—H62	108.6	O11—C12—H122	109.5
H61—C6—H62	107.6	H121—C12—H122	109.5
C5—C6—H63	109.0	O11—C12—H123	109.5
C7B—C6—H63	109.0	H121—C12—H123	109.5
C5—C6—H64	109.0	H122—C12—H123	109.5
C7B—C6—H64	109.0	C14—C13—C18	116.9 (2)
H63—C6—H64	107.8	C14—C13—C4	124.1 (2)
C8—C7A—C19A	110.3 (4)	C18—C13—C4	119.0 (2)
C8—C7A—C6	108.3 (3)	C15—C14—C13	122.1 (2)
C19A—C7A—C6	116.8 (5)	C15—C14—Cl1	116.0 (2)
C8—C7A—H71	107.0	C13—C14—Cl1	121.9 (2)
C19A—C7A—H71	107.0	C16—C15—C14	118.7 (2)
C6—C7A—H71	107.0	C16—C15—H15	120.6
C19B—C7B—C6	108.0 (4)	C14—C15—H15	120.6
C19B—C7B—C8	114.7 (4)	C17—C16—C15	121.4 (2)
C6—C7B—C8	108.7 (3)	C17—C16—Cl2	120.3 (2)
C19B—C7B—H72	108.4	C15—C16—Cl2	118.3 (2)
C6—C7B—H72	108.4	C16—C17—C18	118.4 (3)
C8—C7B—H72	108.4	C16—C17—H17	120.8
C7B—C19B—H194	109.5	C18—C17—H17	120.8
C7B—C19B—H195	109.5	C17—C18—C13	122.6 (2)
H194—C19B—H195	109.5	C17—C18—H18	118.7
C7B—C19B—H196	109.5	C13—C18—H18	118.7
C8A—N1—C2—C3	3.5 (4)	C5—C4A—C8A—C8	−1.3 (4)
C8A—N1—C2—C9	−175.8 (2)	C4—C4A—C8A—C8	177.9 (2)
N1—C2—C3—C10	−176.7 (2)	C2—N1—C8A—C4A	−3.4 (4)
C9—C2—C3—C10	2.5 (4)	C2—N1—C8A—C8	175.2 (2)
N1—C2—C3—C4	3.3 (4)	C7A—C8—C8A—C4A	−26.0 (4)
C9—C2—C3—C4	−177.5 (3)	C7B—C8—C8A—C4A	28.5 (4)
C2—C3—C4—C4A	−8.9 (3)	C7A—C8—C8A—N1	155.4 (3)
C10—C3—C4—C4A	171.1 (2)	C7B—C8—C8A—N1	−150.1 (3)
C2—C3—C4—C13	114.1 (3)	C12—O11—C10—O10	−1.8 (4)
C10—C3—C4—C13	−65.8 (3)	C12—O11—C10—C3	177.8 (2)
C3—C4—C4A—C8A	9.1 (3)	C2—C3—C10—O10	−2.7 (4)
C13—C4—C4A—C8A	−114.8 (3)	C4—C3—C10—O10	177.3 (3)
C3—C4—C4A—C5	−171.8 (2)	C2—C3—C10—O11	177.7 (2)
C13—C4—C4A—C5	64.3 (3)	C4—C3—C10—O11	−2.3 (3)
C8A—C4A—C5—O5	−179.0 (3)	C4A—C4—C13—C14	−115.5 (3)
C4—C4A—C5—O5	1.9 (4)	C3—C4—C13—C14	121.0 (3)
C8A—C4A—C5—C6	1.1 (4)	C4A—C4—C13—C18	63.7 (3)
C4—C4A—C5—C6	−178.1 (2)	C3—C4—C13—C18	−59.7 (3)
O5—C5—C6—C7B	151.2 (3)	C18—C13—C14—C15	0.1 (4)
C4A—C5—C6—C7B	−28.9 (4)	C4—C13—C14—C15	179.4 (2)
O5—C5—C6—C7A	−153.9 (3)	C18—C13—C14—Cl1	179.6 (2)
C4A—C5—C6—C7A	26.1 (4)	C4—C13—C14—Cl1	−1.2 (4)
C5—C6—C7A—C8	−50.4 (5)	C13—C14—C15—C16	0.9 (4)
C5—C6—C7A—C19A	−175.6 (5)	Cl1—C14—C15—C16	−178.6 (2)
C5—C6—C7B—C19B	179.4 (5)	C14—C15—C16—C17	−1.5 (4)
C5—C6—C7B—C8	54.4 (5)	C14—C15—C16—Cl2	178.5 (2)
C19A—C7A—C8—C8A	178.3 (6)	C15—C16—C17—C18	1.2 (4)
C6—C7A—C8—C8A	49.4 (5)	Cl2—C16—C17—C18	−178.8 (2)
C19B—C7B—C8—C8A	−174.1 (5)	C16—C17—C18—C13	−0.1 (4)
C6—C7B—C8—C8A	−53.2 (4)	C14—C13—C18—C17	−0.5 (4)
C5—C4A—C8A—N1	177.3 (2)	C4—C13—C18—C17	−179.8 (2)
C4—C4A—C8A—N1	−3.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5^i	0.88 (3)	1.96 (3)	2.835 (3)	173 (3)

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

(II) (RR,SS)/(RS,SR)-methyl 4-(2,4-chlorophenyl)-2-methyl- 7-phenyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate monohydrate

Crystal data

C24H21Cl2NO3·H2O	Z = 2
Mr = 460.35	F(000) = 480
Triclinic, P1	Dx = 1.353 Mg m^−3
Hall symbol: -P 1	Melting point: 421 K
a = 9.4543 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7947 (6) Å	Cell parameters from 24569 reflections
c = 13.4460 (9) Å	θ = 2.0–25.0°
α = 76.436 (3)°	µ = 0.32 mm^−1
β = 89.268 (4)°	T = 160 K
γ = 69.471 (3)°	Tablet, pale yellow
V = 1130.23 (12) Å^3	0.22 × 0.22 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3980 independent reflections
Radiation source: Nonius FR590 sealed tube generator	3043 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.046
Detector resolution: 9 pixels mm^-1	θmax = 25.0°, θmin = 2.3°
ω scans with κ offsets	h = −11→11
Absorption correction: multi-scan (Blessing, 1995)	k = −11→11
Tmin = 0.822, Tmax = 0.977	l = −15→16
14667 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom and difmap
R[F^2 > 2σ(F^2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.150	w = 1/[σ^2(Fo^2) + (0.0709P)^2 + 0.6095P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
3980 reflections	Δρmax = 0.28 e Å^−3
376 parameters	Δρmin = −0.35 e Å^−3
248 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.026 (6)

Special details

Experimental. Solvent used: Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 1.398 (4) Frames collected: 196 Seconds exposure per frame: 80 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.05915 (7)	0.70403 (8)	0.14084 (6)	0.0634 (3)
Cl2	0.16289 (11)	0.84845 (11)	0.48377 (8)	0.0914 (4)
O5	0.24207 (18)	0.3319 (2)	0.21871 (17)	0.0649 (6)
O10	0.5516 (3)	0.8073 (3)	0.0033 (2)	0.0958 (9)
O11	0.3256 (2)	0.7987 (2)	0.04186 (16)	0.0711 (6)
N1	0.7296 (3)	0.3496 (3)	0.1748 (2)	0.0569 (6)
H1	0.827 (5)	0.298 (4)	0.190 (3)	0.086 (11)*
C2	0.6793 (3)	0.4958 (3)	0.1162 (2)	0.0525 (7)
C3	0.5300 (3)	0.5789 (3)	0.1033 (2)	0.0510 (6)
C4	0.4113 (3)	0.5186 (3)	0.1554 (2)	0.0481 (6)
H4	0.3287	0.5382	0.1024	0.058*
C4A	0.4812 (3)	0.3508 (3)	0.2002 (2)	0.0478 (6)
C5	0.3815 (3)	0.2675 (3)	0.2317 (2)	0.0550 (7)
C6A	0.4561 (9)	0.0966 (5)	0.2631 (6)	0.052 (2)	0.505 (7)
H61	0.4758	0.0578	0.2006	0.062*	0.505 (7)
H62	0.3859	0.0536	0.3023	0.062*	0.505 (7)
C7A	0.6061 (5)	0.0449 (6)	0.3289 (5)	0.0521 (14)	0.505 (7)
H71	0.5849	0.0885	0.3901	0.063*	0.505 (7)
C19A	0.6779 (8)	−0.1226 (6)	0.3663 (7)	0.0511 (18)	0.505 (7)
C20A	0.7161 (13)	−0.1872 (9)	0.4701 (7)	0.0630 (19)	0.505 (7)
H20A	0.6917	−0.1247	0.5169	0.076*	0.505 (7)
C21A	0.7898 (15)	−0.3424 (10)	0.5076 (6)	0.070 (2)	0.505 (7)
H21A	0.8155	−0.3845	0.5791	0.084*	0.505 (7)
C22A	0.825 (3)	−0.4342 (8)	0.4399 (7)	0.060 (2)	0.505 (7)
H22A	0.8752	−0.5397	0.4646	0.072*	0.505 (7)
C23A	0.787 (2)	−0.3718 (8)	0.3369 (7)	0.057 (2)	0.505 (7)
H23A	0.8122	−0.4341	0.2899	0.069*	0.505 (7)
C24A	0.7131 (17)	−0.2182 (9)	0.3014 (6)	0.0575 (19)	0.505 (7)
H24A	0.6855	−0.1772	0.2300	0.069*	0.505 (7)
C6B	0.4452 (8)	0.1085 (6)	0.2998 (7)	0.055 (2)	0.495 (7)
H63	0.3763	0.0542	0.2938	0.067*	0.495 (7)
H64	0.4543	0.1120	0.3724	0.067*	0.495 (7)
C7B	0.6021 (5)	0.0262 (5)	0.2661 (5)	0.0492 (14)	0.495 (7)
H72	0.5865	0.0196	0.1942	0.059*	0.495 (7)
C19B	0.6757 (9)	−0.1317 (7)	0.3300 (7)	0.0524 (18)	0.495 (7)
C20B	0.6947 (13)	−0.1575 (9)	0.4355 (7)	0.062 (2)	0.495 (7)
H20B	0.6616	−0.0745	0.4661	0.075*	0.495 (7)
C21B	0.7615 (15)	−0.3029 (11)	0.4980 (6)	0.066 (2)	0.495 (7)
H21B	0.7697	−0.3187	0.5705	0.079*	0.495 (7)
C22B	0.816 (3)	−0.4236 (8)	0.4536 (7)	0.061 (2)	0.495 (7)
H22B	0.8623	−0.5227	0.4953	0.073*	0.495 (7)
C23B	0.801 (2)	−0.3992 (7)	0.3488 (7)	0.056 (2)	0.495 (7)
H23B	0.8400	−0.4812	0.3177	0.068*	0.495 (7)
C24B	0.7301 (16)	−0.2549 (8)	0.2884 (6)	0.0544 (17)	0.495 (7)
H24B	0.7185	−0.2403	0.2162	0.065*	0.495 (7)
C8	0.7082 (3)	0.1135 (3)	0.2640 (2)	0.0572 (7)
H81	0.7970	0.1010	0.3083	0.069*	0.505 (7)
H82	0.7460	0.0572	0.2110	0.069*	0.505 (7)
H83	0.7436	0.1035	0.3352	0.069*	0.495 (7)
H84	0.7980	0.0692	0.2275	0.069*	0.495 (7)
C8A	0.6331 (3)	0.2767 (3)	0.2121 (2)	0.0514 (6)
C9	0.8066 (3)	0.5428 (4)	0.0705 (2)	0.0633 (8)
H91	0.7941	0.6422	0.0804	0.095*
H92	0.8048	0.5471	−0.0030	0.095*
H93	0.9037	0.4696	0.1044	0.095*
C10	0.4765 (3)	0.7359 (4)	0.0452 (2)	0.0616 (8)
C12	0.2577 (5)	0.9594 (4)	0.0045 (3)	0.0976 (13)
H121	0.3369	1.0012	−0.0155	0.146*
H122	0.2030	1.0027	0.0588	0.146*
H123	0.1868	0.9836	−0.0551	0.146*
C13	0.3420 (3)	0.5993 (3)	0.23848 (19)	0.0435 (6)
C14	0.1895 (3)	0.6841 (3)	0.2385 (2)	0.0475 (6)
C15	0.1335 (3)	0.7587 (3)	0.3140 (2)	0.0539 (7)
H15	0.0284	0.8146	0.3129	0.065*
C16	0.2334 (3)	0.7501 (3)	0.3908 (2)	0.0552 (7)
C17	0.3854 (3)	0.6670 (3)	0.3956 (2)	0.0505 (6)
H17	0.4529	0.6618	0.4492	0.061*
C18	0.4370 (3)	0.5915 (3)	0.31999 (19)	0.0455 (6)
H18	0.5414	0.5317	0.3236	0.055*
O1A	0.0435 (3)	0.1849 (4)	0.2342 (3)	0.0950 (15)	0.879 (6)
H11	0.104 (6)	0.222 (6)	0.216 (4)	0.142*	0.879 (6)
H12	0.034 (7)	0.184 (8)	0.294 (3)	0.142*	0.879 (6)
O1B	0.0987 (14)	0.1256 (15)	0.1547 (11)	0.040 (5)	0.121 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0366 (4)	0.0753 (5)	0.0744 (5)	−0.0202 (3)	−0.0119 (3)	−0.0099 (4)
Cl2	0.0764 (6)	0.0996 (7)	0.1126 (8)	−0.0238 (5)	0.0157 (5)	−0.0652 (6)
O5	0.0309 (9)	0.0657 (12)	0.0973 (15)	−0.0244 (9)	0.0027 (9)	−0.0072 (11)
O10	0.0793 (16)	0.0812 (16)	0.125 (2)	−0.0428 (13)	0.0313 (15)	−0.0009 (15)
O11	0.0529 (12)	0.0768 (14)	0.0700 (13)	−0.0266 (10)	−0.0035 (10)	0.0134 (11)
N1	0.0344 (12)	0.0690 (16)	0.0766 (16)	−0.0297 (11)	0.0067 (11)	−0.0178 (13)
C2	0.0454 (14)	0.0737 (19)	0.0544 (15)	−0.0375 (13)	0.0074 (12)	−0.0206 (14)
C3	0.0459 (14)	0.0675 (17)	0.0507 (15)	−0.0334 (13)	0.0036 (11)	−0.0151 (13)
C4	0.0366 (12)	0.0626 (16)	0.0523 (15)	−0.0269 (12)	0.0014 (11)	−0.0131 (12)
C4A	0.0351 (12)	0.0573 (15)	0.0596 (16)	−0.0255 (11)	0.0053 (11)	−0.0165 (12)
C5	0.0316 (13)	0.0625 (17)	0.0734 (18)	−0.0234 (12)	0.0033 (12)	−0.0110 (14)
C6A	0.031 (3)	0.066 (3)	0.060 (4)	−0.026 (2)	0.013 (3)	−0.008 (3)
C7A	0.035 (2)	0.062 (3)	0.065 (3)	−0.023 (2)	0.007 (2)	−0.018 (3)
C19A	0.029 (2)	0.060 (3)	0.064 (4)	−0.020 (2)	0.011 (3)	−0.010 (3)
C20A	0.050 (4)	0.067 (4)	0.067 (4)	−0.017 (3)	−0.003 (4)	−0.013 (3)
C21A	0.050 (4)	0.071 (4)	0.073 (4)	−0.010 (3)	−0.007 (3)	−0.008 (3)
C22A	0.043 (4)	0.061 (3)	0.075 (4)	−0.021 (3)	0.002 (4)	−0.010 (3)
C23A	0.043 (4)	0.059 (3)	0.070 (3)	−0.021 (3)	0.005 (3)	−0.011 (3)
C24A	0.040 (4)	0.059 (4)	0.071 (3)	−0.022 (4)	0.006 (3)	−0.006 (3)
C6B	0.031 (3)	0.066 (3)	0.069 (5)	−0.023 (2)	0.017 (3)	−0.010 (3)
C7B	0.031 (2)	0.059 (3)	0.064 (3)	−0.0227 (19)	0.006 (2)	−0.016 (2)
C19B	0.034 (3)	0.060 (3)	0.065 (4)	−0.021 (2)	0.006 (3)	−0.010 (3)
C20B	0.046 (4)	0.060 (4)	0.073 (5)	−0.013 (3)	−0.002 (4)	−0.011 (4)
C21B	0.048 (4)	0.073 (4)	0.068 (3)	−0.017 (4)	−0.003 (3)	−0.011 (3)
C22B	0.042 (4)	0.061 (3)	0.077 (4)	−0.023 (3)	−0.001 (4)	−0.002 (3)
C23B	0.040 (4)	0.054 (3)	0.074 (4)	−0.022 (3)	−0.001 (3)	−0.003 (3)
C24B	0.037 (4)	0.055 (3)	0.073 (3)	−0.018 (3)	0.009 (3)	−0.014 (3)
C8	0.0310 (12)	0.0623 (17)	0.084 (2)	−0.0229 (12)	0.0048 (12)	−0.0200 (15)
C8A	0.0361 (13)	0.0626 (16)	0.0674 (17)	−0.0276 (12)	0.0087 (11)	−0.0229 (13)
C9	0.0522 (16)	0.091 (2)	0.0643 (18)	−0.0466 (16)	0.0125 (13)	−0.0200 (16)
C10	0.0587 (18)	0.080 (2)	0.0552 (17)	−0.0380 (16)	0.0086 (13)	−0.0125 (15)
C12	0.082 (2)	0.083 (2)	0.098 (3)	−0.022 (2)	0.006 (2)	0.023 (2)
C13	0.0356 (12)	0.0465 (13)	0.0518 (14)	−0.0223 (10)	−0.0003 (10)	−0.0064 (11)
C14	0.0326 (12)	0.0490 (14)	0.0591 (16)	−0.0176 (10)	−0.0048 (11)	−0.0047 (12)
C15	0.0373 (13)	0.0468 (15)	0.0746 (19)	−0.0126 (11)	0.0030 (12)	−0.0134 (13)
C16	0.0541 (16)	0.0498 (15)	0.0662 (17)	−0.0195 (12)	0.0080 (13)	−0.0214 (13)
C17	0.0458 (14)	0.0513 (15)	0.0565 (16)	−0.0219 (12)	−0.0021 (12)	−0.0099 (12)
C18	0.0328 (12)	0.0484 (14)	0.0543 (15)	−0.0174 (10)	0.0006 (10)	−0.0065 (11)
O1A	0.0345 (13)	0.089 (2)	0.157 (4)	−0.0373 (13)	−0.0025 (18)	0.001 (2)
O1B	0.027 (7)	0.056 (9)	0.046 (9)	−0.025 (6)	0.012 (6)	−0.015 (6)

Geometric parameters (Å, º)

Cl1—C14	1.741 (3)	C6B—H63	0.9900
Cl2—C16	1.740 (3)	C6B—H64	0.9900
O5—C5	1.240 (3)	C7B—C19B	1.500 (5)
O10—C10	1.210 (3)	C7B—C8	1.526 (4)
O11—C10	1.337 (3)	C7B—H72	1.0000
O11—C12	1.439 (4)	C19B—C24B	1.380 (7)
N1—C8A	1.367 (3)	C19B—C20B	1.384 (8)
N1—C2	1.379 (4)	C20B—C21B	1.398 (7)
N1—H1	0.88 (4)	C20B—H20B	0.9500
C2—C3	1.348 (4)	C21B—C22B	1.385 (6)
C2—C9	1.508 (3)	C21B—H21B	0.9500
C3—C10	1.460 (4)	C22B—C23B	1.372 (6)
C3—C4	1.533 (3)	C22B—H22B	0.9500
C4—C4A	1.511 (4)	C23B—C24B	1.385 (6)
C4—C13	1.527 (4)	C23B—H23B	0.9500
C4—H4	1.0000	C24B—H24B	0.9500
C4A—C8A	1.355 (3)	C8—C8A	1.497 (4)
C4A—C5	1.449 (3)	C8—H81	0.9900
C5—C6B	1.521 (4)	C8—H82	0.9900
C5—C6A	1.525 (4)	C8—H83	0.9900
C6A—C7A	1.539 (6)	C8—H84	0.9900
C6A—H61	0.9900	C9—H91	0.9800
C6A—H62	0.9900	C9—H92	0.9800
C7A—C19A	1.499 (5)	C9—H93	0.9800
C7A—C8	1.518 (4)	C12—H121	0.9800
C7A—H71	1.0000	C12—H122	0.9800
C19A—C24A	1.381 (7)	C12—H123	0.9800
C19A—C20A	1.384 (7)	C13—C14	1.389 (3)
C20A—C21A	1.399 (7)	C13—C18	1.397 (3)
C20A—H20A	0.9500	C14—C15	1.381 (4)
C21A—C22A	1.384 (6)	C15—C16	1.377 (4)
C21A—H21A	0.9500	C15—H15	0.9500
C22A—C23A	1.372 (6)	C16—C17	1.374 (4)
C22A—H22A	0.9500	C17—C18	1.380 (4)
C23A—C24A	1.384 (6)	C17—H17	0.9500
C23A—H23A	0.9500	C18—H18	0.9500
C24A—H24A	0.9500	O1A—H11	0.79 (3)
C6B—C7B	1.539 (6)	O1A—H12	0.81 (3)
C10—O11—C12	117.9 (2)	C24B—C19B—C20B	117.3 (4)
C2—N1—C8A	122.6 (2)	C24B—C19B—C7B	123.1 (6)
C8A—N1—H1	116 (2)	C20B—C19B—C7B	119.5 (6)
C2—N1—H1	121 (2)	C19B—C20B—C21B	121.5 (5)
N1—C2—C3	120.2 (2)	C19B—C20B—H20B	119.3
N1—C2—C9	112.6 (2)	C21B—C20B—H20B	119.3
C3—C2—C9	127.2 (3)	C22B—C21B—C20B	119.5 (5)
C2—C3—C10	120.5 (2)	C22B—C21B—H21B	120.3
C2—C3—C4	122.2 (2)	C20B—C21B—H21B	120.3
C10—C3—C4	117.1 (2)	C23B—C22B—C21B	119.6 (4)
C4A—C4—C13	110.6 (2)	C23B—C22B—H22B	120.2
C3—C4—C4A	110.3 (2)	C21B—C22B—H22B	120.2
C13—C4—C3	110.8 (2)	C22B—C23B—C24B	120.0 (4)
C4A—C4—H4	108.3	C22B—C23B—H23B	120.0
C13—C4—H4	108.3	C24B—C23B—H23B	120.0
C3—C4—H4	108.3	C19B—C24B—C23B	122.0 (4)
C8A—C4A—C5	119.3 (2)	C19B—C24B—H24B	119.0
C4—C4A—C8A	122.1 (2)	C23B—C24B—H24B	119.0
C5—C4A—C4	118.5 (2)	C8A—C8—C7A	114.3 (3)
O5—C5—C4A	120.5 (2)	C8A—C8—H81	108.7
O5—C5—C6B	118.6 (3)	C7A—C8—H81	108.7
C4A—C5—C6B	119.8 (4)	C8A—C8—H82	108.7
O5—C5—C6A	122.2 (4)	C7A—C8—H82	108.7
C4A—C5—C6A	116.4 (4)	H81—C8—H82	107.6
C5—C6A—C7A	112.1 (4)	C8A—C8—H83	109.2
C5—C6A—H61	109.2	C7B—C8—H83	109.2
C7A—C6A—H61	109.2	C8A—C8—H84	109.2
C5—C6A—H62	109.2	C7B—C8—H84	109.2
C7A—C6A—H62	109.2	H83—C8—H84	107.9
H61—C6A—H62	107.9	N1—C8A—C4A	120.6 (3)
C19A—C7A—C8	112.4 (5)	C4A—C8A—C8	124.3 (2)
C19A—C7A—C6A	113.5 (3)	N1—C8A—C8	115.1 (2)
C8—C7A—C6A	106.3 (5)	C2—C9—H91	109.5
C19A—C7A—H71	108.1	C2—C9—H92	109.5
C8—C7A—H71	108.1	H91—C9—H92	109.5
C6A—C7A—H71	108.1	C2—C9—H93	109.5
C24A—C19A—C20A	117.2 (4)	H91—C9—H93	109.5
C24A—C19A—C7A	123.0 (6)	H92—C9—H93	109.5
C20A—C19A—C7A	119.7 (6)	O10—C10—O11	121.0 (3)
C19A—C20A—C21A	121.5 (5)	O10—C10—C3	127.7 (3)
C19A—C20A—H20A	119.3	O11—C10—C3	111.3 (2)
C21A—C20A—H20A	119.3	O11—C12—H121	109.5
C22A—C21A—C20A	119.6 (5)	O11—C12—H122	109.5
C22A—C21A—H21A	120.2	H121—C12—H122	109.5
C20A—C21A—H21A	120.2	O11—C12—H123	109.5
C23A—C22A—C21A	119.6 (4)	H121—C12—H123	109.5
C23A—C22A—H22A	120.2	H122—C12—H123	109.5
C21A—C22A—H22A	120.2	C14—C13—C18	116.5 (2)
C22A—C23A—C24A	120.0 (4)	C14—C13—C4	124.7 (2)
C22A—C23A—H23A	120.0	C18—C13—C4	118.8 (2)
C24A—C23A—H23A	120.0	C15—C14—C13	122.3 (2)
C19A—C24A—C23A	122.1 (4)	C15—C14—Cl1	116.55 (18)
C19A—C24A—H24A	118.9	C13—C14—Cl1	121.1 (2)
C23A—C24A—H24A	118.9	C16—C15—C14	118.5 (2)
C5—C6B—C7B	109.0 (4)	C16—C15—H15	120.8
C5—C6B—H63	109.9	C14—C15—H15	120.8
C7B—C6B—H63	109.9	C17—C16—C15	121.9 (3)
C5—C6B—H64	109.9	C17—C16—Cl2	119.8 (2)
C7B—C6B—H64	109.9	C15—C16—Cl2	118.3 (2)
H63—C6B—H64	108.3	C16—C17—C18	118.0 (2)
C19B—C7B—C8	110.2 (5)	C16—C17—H17	121.0
C19B—C7B—C6B	113.0 (3)	C18—C17—H17	121.0
C8—C7B—C6B	112.0 (6)	C17—C18—C13	122.7 (2)
C19B—C7B—H72	107.1	C17—C18—H18	118.6
C8—C7B—H72	107.1	C13—C18—H18	118.6
C6B—C7B—H72	107.1	H11—O1A—H12	107 (5)
C8A—N1—C2—C3	7.7 (4)	C24B—C19B—C20B—C21B	−2.2 (17)
C8A—N1—C2—C9	−171.0 (3)	C7B—C19B—C20B—C21B	179.4 (9)
N1—C2—C3—C10	177.2 (2)	C19B—C20B—C21B—C22B	3 (2)
C9—C2—C3—C10	−4.3 (4)	C20B—C21B—C22B—C23B	−1 (3)
N1—C2—C3—C4	2.4 (4)	C21B—C22B—C23B—C24B	−1 (4)
C9—C2—C3—C4	−179.1 (3)	C20B—C19B—C24B—C23B	0.0 (19)
C2—C3—C4—C4A	−12.4 (3)	C7B—C19B—C24B—C23B	178.3 (12)
C10—C3—C4—C4A	172.6 (2)	C22B—C23B—C24B—C19B	2 (3)
C2—C3—C4—C13	110.4 (3)	C19A—C7A—C8—C8A	171.3 (4)
C10—C3—C4—C13	−64.5 (3)	C6A—C7A—C8—C8A	46.6 (5)
C13—C4—C4A—C8A	−108.6 (3)	C5—C4A—C8A—N1	174.1 (3)
C3—C4—C4A—C8A	14.3 (4)	C4—C4A—C8A—N1	−6.3 (4)
C13—C4—C4A—C5	71.0 (3)	C5—C4A—C8A—C8	−5.0 (4)
C3—C4—C4A—C5	−166.1 (2)	C4—C4A—C8A—C8	174.6 (3)
C8A—C4A—C5—O5	−177.8 (3)	C2—N1—C8A—C4A	−5.8 (4)
C4—C4A—C5—O5	2.6 (4)	C2—N1—C8A—C8	173.4 (2)
C8A—C4A—C5—C6B	14.4 (6)	C7A—C8—C8A—C4A	−16.3 (5)
C4—C4A—C5—C6B	−165.2 (5)	C7B—C8—C8A—C4A	21.5 (5)
C8A—C4A—C5—C6A	−8.2 (5)	C7A—C8—C8A—N1	164.5 (3)
C4—C4A—C5—C6A	172.2 (4)	C7B—C8—C8A—N1	−157.6 (3)
O5—C5—C6A—C7A	−148.8 (5)	C12—O11—C10—O10	−11.6 (5)
C4A—C5—C6A—C7A	41.8 (8)	C12—O11—C10—C3	168.5 (3)
C5—C6A—C7A—C19A	176.5 (6)	C2—C3—C10—O10	0.6 (5)
C5—C6A—C7A—C8	−59.3 (8)	C4—C3—C10—O10	175.6 (3)
C8—C7A—C19A—C24A	−64.8 (10)	C2—C3—C10—O11	−179.5 (3)
C6A—C7A—C19A—C24A	55.9 (12)	C4—C3—C10—O11	−4.5 (4)
C8—C7A—C19A—C20A	113.1 (9)	C4A—C4—C13—C14	−118.3 (2)
C6A—C7A—C19A—C20A	−126.2 (9)	C3—C4—C13—C14	119.0 (3)
C24A—C19A—C20A—C21A	1.1 (16)	C4A—C4—C13—C18	63.1 (3)
C7A—C19A—C20A—C21A	−176.9 (9)	C3—C4—C13—C18	−59.6 (3)
C19A—C20A—C21A—C22A	0 (2)	C18—C13—C14—C15	0.7 (4)
C20A—C21A—C22A—C23A	0 (3)	C4—C13—C14—C15	−177.9 (2)
C21A—C22A—C23A—C24A	−1 (4)	C18—C13—C14—Cl1	179.57 (18)
C20A—C19A—C24A—C23A	−1.8 (19)	C4—C13—C14—Cl1	0.9 (3)
C7A—C19A—C24A—C23A	176.1 (12)	C13—C14—C15—C16	1.1 (4)
C22A—C23A—C24A—C19A	2 (3)	Cl1—C14—C15—C16	−177.8 (2)
O5—C5—C6B—C7B	153.3 (6)	C14—C15—C16—C17	−1.6 (4)
C4A—C5—C6B—C7B	−38.7 (10)	C14—C15—C16—Cl2	178.3 (2)
C5—C6B—C7B—C19B	179.2 (7)	C15—C16—C17—C18	0.3 (4)
C5—C6B—C7B—C8	54.0 (10)	Cl2—C16—C17—C18	−179.58 (19)
C8—C7B—C19B—C24B	−107.0 (11)	C16—C17—C18—C13	1.6 (4)
C6B—C7B—C19B—C24B	126.8 (11)	C14—C13—C18—C17	−2.0 (4)
C8—C7B—C19B—C20B	71.3 (9)	C4—C13—C18—C17	176.7 (2)
C6B—C7B—C19B—C20B	−54.9 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H11···O5	0.79 (3)	1.96 (4)	2.718 (3)	159 (6)
N1—H1···O1A^i	0.88 (4)	1.97 (4)	2.854 (4)	176 (3)

Symmetry code: (i) x+1, y, z.