The diastereoisomers 2-[(S/R)-2-chloro-3-quinol­yl]-2-[(R)-1-(4-meth­oxy­phenyl)ethyl­amino]­aceto­nitrile at 100 K

In the structures of the two enantiopure diastereoisomers of the title compound, C₂₀H₁₈ClN₃O, which crystallize in different space groups, the molecules are very similar as far as bond distances and angles are concerned, but more substantial differences are observed in some torsion angles. The crystal structures of both mol­ecules can be described as zigzag layers along the c axis. The packing is stabilized by hydrogen-bond inter­actions of N—H...O, C—H...Cl and C—H...π types for 2-[(R)-2-chloro-3-quinol­yl]-2-[(R)-1-(4-methoxy­phenyl)ethylamino]acetonitrile, and of N—H...N, C—H...O and C—H...π types for 2-[(S)-2-chloro-3-quinol­yl]-2-[(R)-1-(4-methoxy­phenyl)ethyl­amino]acetonitrile, re­sulting in the formation of two- and three-dimensional networks.

S1. Comment

Quinolines and their annulated derivatives are important compounds due to their presence in numerous natural products, along with their wide-ranging applications as drugs, pharmaceuticals and agrochemicals (Jones, 1996; Jackson & Meth-Cohn, 1995; Kansagra et al., 2000). Amino acid derivatives are broadly useful chiral building blocks, with especially important applications in complex natural-product and combinatorial syntheses (Burk et al., 1998; Williams, 1989). In recent years, we have developed a programme devoted to the synthesis and biological evaluation of quinolyl derivatives (Benzerka et al., 2008; Bouraiou et al., 2007, 2008). In previous work, we have reported the synthesis and stereostructure determination of 2-(S)-(2-chloroquinolin-3-yl)-2-[(S)-α-methylbenzylamino]acetonitrile (Belfaitah et al., 2006). We report here the synthesis and structure determinations of two diastereoisomers of the title compound at 100 K.

The Strecker reaction is one of the oldest and best known routes to racemic amino acids (Shuichi et al., 2004; Boesten et al., 2001). The use of optically active α-methylbenzylamine-derived aldimines has a significant role in the diastereoselective Strecker synthesis (Bhanu-Prasad et al., 2004). The title diastereoisomers were synthesized from (R,E)-N-[(2-chloroquinolin-3-yl)methylene]-1-(4-methoxyphenyl)ethanamine in the presence of tert-BuMe₂SiCN. A 45:55 ratio of the diastereoisomers (R,R) and (S,R), respectively, was observed by NMR spectroscopy. Since separation of the isomers by standard chromatographic methods failed, an attempt was made to crystallize the mixture directly by fractional crystallization from a CH₂Cl₂–petroleum ether (1:9) solution at 298 K.

Initially, microsphere crystals were obtained from the first crystallization and these were separated by hand, while after several recrystallizations good crystals were obtained in the form of long thin needles. The material of these needles was shown by NMR spectroscopy to be the minor component of the mixture. The different crystals obtained were analysed by single-crystal diffractometry, and it was be found that the long needles represent the (10R,12R) diastereoisomer, (I) (Fig. 1), while the microsphere crystals correspond to the (10S,12R) diastereoisomer, (II) (Fig. 2). Diastereoisomers (I) and (II) crystallize in different crystal systems, both in noncentrosymmetric space groups (P2₁2₁2₁ and P2₁). The structures were further elucidated by detailed NMR studies (see Experimental). It is clear that the difference between the isomers is the disposition of the H atom at the stereogenic centre at C10, which is confirmed by the torsion angles (Table 1).

Chemically equivalent bond distances in diastereoisomers (I) and (II) do not differ by more than 2 s.u.s from their mean values, while equivalent angles in some cases reach this limit. The largest difference is seen for N2—C10—C2 [109.65 (12) and 112.50 (15)° for (I) (atom labels with the suffix A) and (II) (atom labels with the suffix B), respectively]. The differences in the torsion angles are sometimes greater than 90°, in particular around the bonds C12A(B)—C14A(B), C10A(B)—N2A(B), C10A(B)—C2A(B) and N2A(B)—C12A(B). The maximum difference of 93.4° is seen for the torsion angle C14—C12—N2—C10 [63.88 (17) and 158.18 (14)° for (I) and (II), respectively] (Table 1). The two rings of the quinolyl unit are planar and form dihedral angles of 0.78 (5) and 1.65 (4)° for (I) and (II), respectively; this unit forms dihedral angles of 81.68 (5) and 53.51 (4)° with the benzene ring for (I) and (II), respectively.

In the packing of (I), a weak classical N—H···O hydrogen bond (PLATON; Spek, 2009) creates extended chains which run parallel to the [001] direction, and C—H···Cl interactions link these chains together to form a two-dimensional network. A C—H···π interaction involving the C4A–C9A phenyl ring of the quinoline group (ring centroid Cg1A) helps to stabilize the packing, resulting in the formation of a three-dimensional network (Table 2, Fig. 3).

In the packing of (II), a C—H···O interaction forms zigzag chains along the c axis (Fig. 4a). An N—H···N hydrogen bond and a C—H···π interaction involving the C14B–C19B phenyl ring (ring centroid Cg2B) connect these chains together, resulting in the formation of a two-dimensional network parallel to the (100) plane and reinforcing the cohesion of the structure (Table 3, Fig. 4b)

S2. Experimental

Reaction of [Which?] chiral imine (1.0 g, 3.08 mmol), tert-butyldimethylsilyl cyanide (0.367 mg, 1.2 equivalents, 3.69 mmol), [acetonitrile shown in scheme?] and a few drops of water gave the title compound in a mixture of diasterioisomers, (I) [(R,R)] and (II) [(S,R)], in a 45:55 ratio as a yellow solid in 91% yield. IR (KBr, ν, cm^-1): 2212 (CN). Crystals of each diasterioisomer were obtained by fractional crystallization from a CH₂Cl₂–petroleum ether (1:9) solution of the mixture.

Analysis for (I): white crystals, m.p. 421 K; ¹H NMR (250 MHz, CDCl₃): 8.43 (s, 1H, H₄, quinolyl), 8.04 (dd, J = 8.4 and 1.1 Hz, 1H, H₈, quinolyl), 7.88 (dd, J = 8.1 and 1.0 Hz, 1H, H₅, quinolyl), 7.80 (ddd, J = 8.1, 7.0 and 1.0 Hz, 1H, H₇, quinolyl), 7.63 (ddd, J = 8.1, 7.0 and 1.0 Hz, 1H, H₆, quinolyl), 7.43 (dd, J = 6.6 and 2.0 Hz, 2H, H_arom), 6.95 (dd, J = 6.6 and 2.0 Hz, 2H, H_arom), 4.78 (br, 1H, Hα), 4.25 (q, J = 6.5 Hz, 1H, Hα'), 3.85 (s, 3H, OCH₃), 1.86 (br, 1H, NH), 1.47 (d, J = 6.5 Hz, 3H, CH₃); ¹³C NMR (62.9 MHz, CDCl₃): 159.4 (C), 148.9 (C), 147.4 (C), 137.8 (CH), 133.7 (C), 131.4 (CH), 128.4 (2 × CH), 128.3 (CH), 127.8 (CH), 127.7 (CH), 127.2 (C), 126.7 (C), 117.9(CN), 114.0 (2 × CH), 56.5 (OCH₃), 55.2 (CH), 50.1 (CH), 24.5 (CH₃).

Analysis for (II): yellow crystals, m.p. 418 K; ¹H NMR (250 MHz, CDCl₃): 8.27 (s, 1H, H₄, quinolyl), 8.05 (dd, J = 8.7 and 1.0 Hz, 1H, H₈, quinolyl), 7.95–7.75 (m, 2H, H7 and H₅, quinolyl), 7.62 (ddd, J = 8.2, 7.0 and 1.1 Hz, 1H, H₆, quinolyl), 7.25 (dd, J = 6.6 and 2.0 Hz, 2H, H_arom), 6.81 (dd, J = 6.6 and 2.0 Hz, 2H, H_arom), 5.24 (br, 1H, Hα), 4.08 (q, J = 6.4 Hz, 1H, Hα'), 3.74 (s, 3H, OCH₃), 2.04 (br, 1H, NH), 1.48 (d, J = 6.4 Hz, 3H, CH₃); ¹³C NMR (62.9 MHz, CDCl₃): 159.0 (C), 148.9 (C), 147.3 (C), 137.8 (CH), 135.5 (CH), 131.3 (CH), 128.3 (CH), 127.8 (2 × CH), 127.7 (CH), 126.9 (C), 126.6 (C), 117.7 (CN), 114.0 (2 × CH), 55.9 (OCH₃), 55.1 (CH), 49.9 (CH), 22.7 (CH₃).

S3. Refinement

Atoms H2N atoms in both structures were located in a difference Fourier map and refined isotropically. All remaining H atoms were located in difference Fourier maps but introduced in calculated positions, with C—H = 0.93, 0.96 and 0.98 Å for aromatic, methyl and tertiary H atoms, respectively, and refined using a riding model, with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) otherwise. The absolute configurations of the two isomers presented here are based on the values of the Flack (1983) parameters of 0.05 (5) for (I) and 0.03 (5) for (II); no Friedel reflections were used in these refinements.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. View of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. View of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. Part of the crystal packing of (I), showing classical hygrogen bonds and other interactions as dashed lines in the layers. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x + 1/2, -y + 1, z + 1/2; (ii) -x - 1/2, -y + 1, z + 1/2; (iii) -x + 3/2, -y + 1, z - 1/2.]
	Fig. 4. (a) Chains of C—H···O interactions (dashed lines) in the crystal packing of (II). [Symmetry codes: (i) x, y, -1 + z; (ii) 1 - x, 1/2 + y, -z; (iii) 1 - x, -1/2 + y, 1 - z.] (b) Part of the crystal packing of (II), showing the N—H···N and C—H···π interactions (dashed lines) between chains. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x, -1/2 + y, 1 - z; (ii) x, -1 + y, z.]

(I) 2-[(R)-2-chloro-3-quinolyl]-2-[(R)-1-(4- methoxyphenyl)ethylamino]acetonitrile

Crystal data

C20H18ClN3O	F(000) = 736
Mr = 351.82	Dx = 1.324 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6769 reflections
a = 8.7606 (7) Å	θ = 2.6–27.4°
b = 11.8494 (10) Å	µ = 0.23 mm^−1
c = 17.0002 (12) Å	T = 100 K
V = 1764.8 (2) Å^3	Block, white
Z = 4	0.59 × 0.50 × 0.37 mm

Data collection

Bruker APEXII diffractometer	Rint = 0.048
CCD rotation images, thick slices scans	θmax = 27.5°, θmin = 2.1°
15585 measured reflections	h = −11→11
4051 independent reflections	k = −15→15
3828 reflections with I > 2σ(I)	l = −16→22

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0363P)^2 + 0.3546P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.032	(Δ/σ)max = 0.001
wR(F^2) = 0.079	Δρmax = 0.23 e Å^−3
S = 1.03	Δρmin = −0.27 e Å^−3
4051 reflections	Absolute structure: Flack (Flack, 1983), based on 1733 Friedel pairs
229 parameters	Absolute structure parameter: 0.05 (5)
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.07921 (17)	0.48361 (12)	0.61467 (9)	0.0168 (3)
C2	0.02863 (16)	0.39485 (13)	0.60614 (8)	0.0152 (3)
C3	0.03086 (16)	0.31563 (13)	0.66440 (9)	0.0166 (3)
H3	0.0997	0.256	0.6616	0.02*
C4	−0.07067 (16)	0.32338 (12)	0.72906 (8)	0.0157 (3)
C5	−0.07363 (18)	0.24268 (14)	0.79069 (9)	0.0202 (3)
H5	−0.0044	0.1832	0.7908	0.024*
C6	−0.17865 (18)	0.25247 (15)	0.85015 (9)	0.0237 (3)
H6	−0.1818	0.1989	0.8901	0.028*
C7	−0.28185 (19)	0.34372 (16)	0.85060 (10)	0.0267 (4)
H7	−0.3531	0.3494	0.891	0.032*
C8	−0.27933 (18)	0.42400 (15)	0.79283 (10)	0.0256 (3)
H8	−0.3472	0.4843	0.7946	0.031*
C9	−0.17336 (16)	0.41510 (14)	0.73057 (9)	0.0182 (3)
C10	0.13877 (16)	0.39401 (12)	0.53738 (9)	0.0176 (3)
H10	0.0832	0.4186	0.4904	0.021*
C11	0.1971 (2)	0.27730 (14)	0.52290 (9)	0.0252 (4)
C12	0.37451 (16)	0.48417 (14)	0.48772 (9)	0.0187 (3)
H12	0.4148	0.4088	0.4762	0.022*
C13	0.50537 (18)	0.55780 (16)	0.51707 (10)	0.0281 (4)
H13A	0.4674	0.6317	0.5294	0.042*
H13B	0.582	0.5635	0.4769	0.042*
H13C	0.549	0.5246	0.5634	0.042*
C14	0.29951 (16)	0.52992 (13)	0.41392 (8)	0.0167 (3)
C15	0.24420 (17)	0.63973 (14)	0.40942 (9)	0.0200 (3)
H15	0.2508	0.6859	0.4535	0.024*
C16	0.17920 (18)	0.68285 (13)	0.34097 (9)	0.0208 (3)
H16	0.1441	0.7569	0.3392	0.025*
C17	0.16764 (17)	0.61333 (13)	0.27540 (9)	0.0191 (3)
C18	0.22029 (18)	0.50295 (14)	0.27852 (9)	0.0214 (3)
H18	0.2115	0.4564	0.2347	0.026*
C19	0.28598 (18)	0.46232 (13)	0.34708 (9)	0.0200 (3)
H19	0.3218	0.3885	0.3486	0.024*
C20	0.0455 (2)	0.75708 (16)	0.19849 (11)	0.0352 (5)
H20A	−0.0356	0.7665	0.2359	0.053*
H20B	0.0068	0.7692	0.1463	0.053*
H20C	0.1249	0.8107	0.2093	0.053*
N1	−0.17582 (14)	0.49561 (11)	0.67225 (8)	0.0196 (3)
N3	0.2519 (2)	0.19097 (14)	0.51158 (10)	0.0397 (4)
N2	0.26189 (14)	0.47432 (11)	0.55185 (8)	0.0166 (3)
O1	0.10535 (14)	0.64544 (10)	0.20439 (6)	0.0252 (3)
Cl1	−0.08760 (4)	0.58681 (3)	0.54210 (2)	0.02475 (10)
H2	0.311 (3)	0.454 (2)	0.5929 (13)	0.05*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0166 (6)	0.0163 (7)	0.0176 (7)	−0.0028 (6)	−0.0041 (6)	0.0021 (6)
C2	0.0140 (6)	0.0181 (7)	0.0137 (7)	−0.0023 (6)	−0.0009 (5)	−0.0020 (6)
C3	0.0157 (6)	0.0149 (7)	0.0192 (8)	0.0003 (6)	0.0008 (6)	−0.0016 (6)
C4	0.0151 (6)	0.0183 (7)	0.0138 (7)	−0.0038 (6)	−0.0016 (5)	−0.0025 (6)
C5	0.0184 (7)	0.0241 (8)	0.0181 (7)	−0.0009 (6)	−0.0019 (6)	0.0006 (6)
C6	0.0233 (7)	0.0344 (9)	0.0132 (7)	−0.0072 (7)	−0.0017 (6)	0.0035 (7)
C7	0.0233 (7)	0.0398 (10)	0.0170 (8)	−0.0038 (7)	0.0072 (6)	−0.0047 (7)
C8	0.0211 (7)	0.0300 (9)	0.0256 (8)	0.0031 (7)	0.0045 (6)	−0.0058 (7)
C9	0.0166 (7)	0.0198 (7)	0.0183 (7)	−0.0026 (6)	−0.0002 (5)	−0.0028 (6)
C10	0.0196 (6)	0.0187 (7)	0.0145 (7)	−0.0028 (5)	0.0012 (5)	0.0001 (6)
C11	0.0306 (8)	0.0242 (8)	0.0210 (8)	−0.0056 (7)	0.0112 (7)	−0.0032 (7)
C12	0.0157 (6)	0.0234 (8)	0.0171 (7)	0.0000 (6)	0.0028 (5)	0.0034 (6)
C13	0.0167 (7)	0.0437 (11)	0.0239 (8)	−0.0080 (7)	−0.0013 (6)	0.0051 (8)
C14	0.0142 (6)	0.0219 (8)	0.0141 (7)	−0.0018 (6)	0.0042 (5)	0.0020 (6)
C15	0.0225 (7)	0.0206 (8)	0.0170 (7)	−0.0026 (6)	0.0022 (6)	−0.0033 (6)
C16	0.0239 (8)	0.0164 (7)	0.0222 (8)	0.0016 (6)	0.0045 (6)	0.0012 (6)
C17	0.0201 (7)	0.0228 (8)	0.0146 (7)	0.0006 (6)	0.0036 (6)	0.0036 (6)
C18	0.0279 (8)	0.0204 (7)	0.0160 (8)	0.0010 (7)	0.0020 (6)	−0.0025 (6)
C19	0.0235 (7)	0.0168 (7)	0.0197 (8)	0.0028 (6)	0.0040 (6)	0.0000 (6)
C20	0.0471 (11)	0.0337 (10)	0.0247 (9)	0.0179 (9)	0.0054 (8)	0.0098 (8)
N1	0.0166 (6)	0.0180 (6)	0.0243 (7)	0.0001 (5)	0.0001 (5)	0.0006 (5)
N3	0.0508 (10)	0.0246 (8)	0.0439 (10)	−0.0018 (7)	0.0239 (8)	−0.0066 (7)
N2	0.0161 (5)	0.0203 (6)	0.0133 (6)	−0.0030 (5)	0.0006 (5)	0.0001 (5)
O1	0.0313 (6)	0.0284 (6)	0.0159 (5)	0.0088 (5)	0.0008 (5)	0.0031 (5)
Cl1	0.02157 (17)	0.02440 (18)	0.0283 (2)	0.00040 (15)	−0.00290 (15)	0.01054 (16)

Geometric parameters (Å, º)

C1—N1	1.3018 (19)	C12—C14	1.516 (2)
C1—C2	1.421 (2)	C12—C13	1.525 (2)
C1—Cl1	1.7386 (15)	C12—H12	0.98
C2—C3	1.365 (2)	C13—H13A	0.96
C2—C10	1.5157 (19)	C13—H13B	0.96
C3—C4	1.417 (2)	C13—H13C	0.96
C3—H3	0.93	C14—C15	1.391 (2)
C4—C9	1.411 (2)	C14—C19	1.395 (2)
C4—C5	1.419 (2)	C15—C16	1.393 (2)
C5—C6	1.372 (2)	C15—H15	0.93
C5—H5	0.93	C16—C17	1.390 (2)
C6—C7	1.409 (3)	C16—H16	0.93
C6—H6	0.93	C17—O1	1.3783 (19)
C7—C8	1.367 (2)	C17—C18	1.388 (2)
C7—H7	0.93	C18—C19	1.386 (2)
C8—C9	1.412 (2)	C18—H18	0.93
C8—H8	0.93	C19—H19	0.93
C9—N1	1.376 (2)	C20—O1	1.427 (2)
C10—N2	1.4592 (18)	C20—H20A	0.96
C10—C11	1.495 (2)	C20—H20B	0.96
C10—H10	0.98	C20—H20C	0.96
C11—N3	1.146 (2)	N2—H2	0.85 (2)
C12—N2	1.4749 (18)
N1—C1—C2	126.14 (14)	C14—C12—H12	108.4
N1—C1—Cl1	115.42 (11)	C13—C12—H12	108.4
C2—C1—Cl1	118.44 (11)	C12—C13—H13A	109.5
C3—C2—C1	116.39 (13)	C12—C13—H13B	109.5
C3—C2—C10	123.10 (13)	H13A—C13—H13B	109.5
C1—C2—C10	120.45 (13)	C12—C13—H13C	109.5
C2—C3—C4	120.63 (13)	H13A—C13—H13C	109.5
C2—C3—H3	119.7	H13B—C13—H13C	109.5
C4—C3—H3	119.7	C15—C14—C19	117.56 (14)
C9—C4—C3	117.66 (13)	C15—C14—C12	122.08 (14)
C9—C4—C5	119.61 (13)	C19—C14—C12	120.35 (14)
C3—C4—C5	122.73 (14)	C14—C15—C16	122.13 (15)
C6—C5—C4	119.96 (15)	C14—C15—H15	118.9
C6—C5—H5	120	C16—C15—H15	118.9
C4—C5—H5	120	C17—C16—C15	118.85 (14)
C5—C6—C7	119.93 (15)	C17—C16—H16	120.6
C5—C6—H6	120	C15—C16—H16	120.6
C7—C6—H6	120	O1—C17—C18	115.16 (14)
C8—C7—C6	121.30 (15)	O1—C17—C16	124.59 (14)
C8—C7—H7	119.3	C18—C17—C16	120.25 (14)
C6—C7—H7	119.3	C19—C18—C17	119.82 (15)
C7—C8—C9	119.80 (16)	C19—C18—H18	120.1
C7—C8—H8	120.1	C17—C18—H18	120.1
C9—C8—H8	120.1	C18—C19—C14	121.37 (15)
N1—C9—C4	122.06 (13)	C18—C19—H19	119.3
N1—C9—C8	118.56 (14)	C14—C19—H19	119.3
C4—C9—C8	119.37 (15)	O1—C20—H20A	109.5
N2—C10—C11	112.25 (12)	O1—C20—H20B	109.5
N2—C10—C2	109.65 (12)	H20A—C20—H20B	109.5
C11—C10—C2	110.52 (12)	O1—C20—H20C	109.5
N2—C10—H10	108.1	H20A—C20—H20C	109.5
C11—C10—H10	108.1	H20B—C20—H20C	109.5
C2—C10—H10	108.1	C1—N1—C9	117.12 (13)
N3—C11—C10	175.19 (18)	C10—N2—C12	114.93 (12)
N2—C12—C14	110.48 (11)	C10—N2—H2	108.8 (16)
N2—C12—C13	107.84 (12)	C12—N2—H2	106.9 (16)
C14—C12—C13	113.08 (13)	C17—O1—C20	117.59 (13)
N2—C12—H12	108.4
N1—C1—C2—C3	−0.5 (2)	N2—C12—C14—C15	67.47 (18)
Cl1—C1—C2—C3	−179.84 (11)	C13—C12—C14—C15	−53.51 (18)
N1—C1—C2—C10	−177.59 (14)	N2—C12—C14—C19	−113.54 (15)
Cl1—C1—C2—C10	3.06 (18)	C13—C12—C14—C19	125.48 (16)
C1—C2—C3—C4	0.3 (2)	C19—C14—C15—C16	−0.9 (2)
C10—C2—C3—C4	177.27 (13)	C12—C14—C15—C16	178.14 (14)
C2—C3—C4—C9	0.2 (2)	C14—C15—C16—C17	0.8 (2)
C2—C3—C4—C5	179.45 (14)	C15—C16—C17—O1	179.75 (14)
C9—C4—C5—C6	1.7 (2)	C15—C16—C17—C18	0.0 (2)
C3—C4—C5—C6	−177.48 (15)	O1—C17—C18—C19	179.58 (14)
C4—C5—C6—C7	−1.0 (2)	C16—C17—C18—C19	−0.6 (2)
C5—C6—C7—C8	−0.4 (2)	C17—C18—C19—C14	0.5 (2)
C6—C7—C8—C9	1.0 (3)	C15—C14—C19—C18	0.2 (2)
C3—C4—C9—N1	−0.5 (2)	C12—C14—C19—C18	−178.85 (13)
C5—C4—C9—N1	−179.79 (14)	C2—C1—N1—C9	0.2 (2)
C3—C4—C9—C8	178.18 (14)	Cl1—C1—N1—C9	179.56 (10)
C5—C4—C9—C8	−1.1 (2)	C4—C9—N1—C1	0.3 (2)
C7—C8—C9—N1	178.45 (15)	C8—C9—N1—C1	−178.39 (14)
C7—C8—C9—C4	−0.3 (2)	C11—C10—N2—C12	58.65 (17)
C3—C2—C10—N2	−99.63 (16)	C2—C10—N2—C12	−178.10 (12)
C1—C2—C10—N2	77.27 (16)	C14—C12—N2—C10	63.88 (17)
C3—C2—C10—C11	24.6 (2)	C13—C12—N2—C10	−172.08 (13)
C1—C2—C10—C11	−158.47 (14)	C18—C17—O1—C20	178.29 (15)
N2—C10—C11—N3	−9 (2)	C16—C17—O1—C20	−1.5 (2)
C2—C10—C11—N3	−132 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.85 (2)	2.35 (2)	3.1767 (17)	163 (2)
C7—H7···Cl1^ii	0.93	2.73	3.5474 (18)	147
C20—H20A···Cg1^iii	0.96	2.94	3.7513 (13)	143

Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −x−1/2, −y+1, z+1/2; (iii) −x+3/2, −y+1, z−1/2.

(II) 2-[(S)-2-chloro-3-quinolyl]-2-[(R)-1-(4- methoxyphenyl)ethylamino]acetonitrile

Crystal data

C20H18ClN3O	F(000) = 368
Mr = 351.82	Dx = 1.347 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 13007 reflections
a = 11.2728 (7) Å	θ = 3.1–27.4°
b = 5.7612 (4) Å	µ = 0.23 mm^−1
c = 13.3573 (9) Å	T = 100 K
β = 90.171 (4)°	Stick, yellow
V = 867.48 (10) Å^3	0.55 × 0.12 × 0.07 mm
Z = 2

Data collection

Bruker APEXII diffractometer	3630 reflections with I > 2σ(I)
CCD rotation images, thick slices scans	Rint = 0.049
Absorption correction: multi-scan SADABS (Sheldrick, 2002)	θmax = 27.4°, θmin = 3.1°
Tmin = 0.837, Tmax = 0.984	h = −14→14
13007 measured reflections	k = −7→7
3868 independent reflections	l = −17→17

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0401P)^2 + 0.1763P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.036	(Δ/σ)max < 0.001
wR(F^2) = 0.087	Δρmax = 0.27 e Å^−3
S = 1.03	Δρmin = −0.23 e Å^−3
3868 reflections	Absolute structure: Flack (Flack, 1983), based on 1698 Friedel pairs
231 parameters	Absolute structure parameter: 0.03 (5)
1 restraint

Special details

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
Cl1	0.40358 (4)	0.69953 (9)	0.27078 (3)	0.02690 (13)
O1	0.36109 (12)	0.7825 (2)	0.93882 (9)	0.0234 (3)
N2	0.23893 (13)	0.7582 (3)	0.47003 (11)	0.0166 (3)
N3	−0.04500 (14)	0.9359 (3)	0.42845 (12)	0.0214 (3)
N1	0.28490 (14)	0.3653 (3)	0.18859 (12)	0.0203 (3)
C2	0.17023 (15)	0.5950 (3)	0.30709 (12)	0.0157 (4)
C4	0.07505 (16)	0.2777 (3)	0.21734 (13)	0.0179 (4)
C1	0.27497 (17)	0.5341 (3)	0.25309 (13)	0.0182 (4)
C10	0.17076 (15)	0.8028 (3)	0.37793 (12)	0.0162 (4)
H10	0.2094	0.9317	0.3429	0.019*
C11	0.04697 (17)	0.8785 (3)	0.40252 (13)	0.0169 (4)
C8	0.19358 (18)	0.0515 (3)	0.09828 (14)	0.0236 (4)
H8	0.2655	0.0212	0.067	0.028*
C13	0.36715 (18)	1.1062 (4)	0.48142 (15)	0.0252 (4)
H13A	0.351	1.1355	0.412	0.038*
H13B	0.438	1.0147	0.4875	0.038*
H13C	0.3779	1.251	0.5158	0.038*
C9	0.18496 (16)	0.2345 (3)	0.16910 (13)	0.0182 (4)
C12	0.26269 (16)	0.9742 (3)	0.52776 (13)	0.0170 (4)
H12	0.192	1.0731	0.525	0.02*
C19	0.25684 (16)	1.0704 (3)	0.71275 (14)	0.0189 (4)
H19	0.2179	1.2075	0.6963	0.023*
C3	0.07167 (16)	0.4625 (3)	0.28855 (13)	0.0167 (4)
H3	0.0017	0.4933	0.3228	0.02*
C7	0.09567 (19)	−0.0803 (4)	0.07609 (14)	0.0261 (4)
H7	0.1015	−0.1992	0.0292	0.031*
C14	0.28851 (15)	0.9143 (3)	0.63646 (13)	0.0167 (4)
C16	0.37322 (16)	0.6602 (3)	0.76374 (13)	0.0209 (4)
H16	0.412	0.5231	0.7805	0.025*
C17	0.34086 (15)	0.8168 (3)	0.83822 (13)	0.0179 (4)
C6	−0.01452 (19)	−0.0371 (4)	0.12399 (15)	0.0249 (4)
H6	−0.0802	−0.1279	0.1084	0.03*
C5	−0.02458 (17)	0.1382 (3)	0.19330 (14)	0.0203 (4)
H5	−0.0969	0.1652	0.2245	0.024*
C18	0.28308 (16)	1.0223 (3)	0.81269 (14)	0.0198 (4)
H18	0.262	1.1275	0.8624	0.024*
C15	0.34696 (16)	0.7105 (4)	0.66344 (13)	0.0211 (4)
H15	0.369	0.6057	0.6139	0.025*
C20	0.42763 (19)	0.5816 (4)	0.96724 (15)	0.0275 (4)
H20A	0.5032	0.5838	0.9343	0.041*
H20B	0.3849	0.4444	0.948	0.041*
H20C	0.4394	0.5818	1.0384	0.041*
H2	0.195 (2)	0.664 (5)	0.506 (2)	0.05*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0193 (2)	0.0342 (3)	0.0272 (2)	−0.0074 (2)	0.00628 (17)	−0.0088 (2)
O1	0.0270 (7)	0.0282 (8)	0.0149 (6)	0.0066 (6)	−0.0036 (5)	−0.0037 (5)
N2	0.0194 (8)	0.0171 (8)	0.0131 (7)	−0.0016 (6)	−0.0009 (6)	−0.0007 (5)
N3	0.0236 (9)	0.0200 (8)	0.0205 (8)	0.0015 (7)	−0.0004 (7)	−0.0029 (6)
N1	0.0204 (8)	0.0242 (9)	0.0164 (7)	0.0005 (7)	0.0021 (6)	−0.0017 (6)
C2	0.0179 (9)	0.0183 (9)	0.0110 (8)	0.0011 (7)	0.0011 (7)	0.0024 (6)
C4	0.0232 (9)	0.0176 (9)	0.0130 (8)	0.0006 (7)	−0.0006 (7)	0.0028 (7)
C1	0.0179 (9)	0.0211 (10)	0.0157 (8)	−0.0027 (7)	−0.0018 (7)	0.0003 (7)
C10	0.0177 (8)	0.0158 (8)	0.0151 (8)	−0.0019 (7)	0.0018 (7)	0.0000 (7)
C11	0.0237 (10)	0.0159 (9)	0.0113 (7)	0.0001 (7)	−0.0031 (7)	−0.0001 (7)
C8	0.0277 (10)	0.0266 (11)	0.0167 (9)	0.0025 (8)	0.0031 (8)	−0.0012 (8)
C13	0.0322 (11)	0.0199 (10)	0.0236 (10)	−0.0077 (8)	0.0004 (8)	−0.0011 (8)
C9	0.0212 (9)	0.0190 (10)	0.0143 (8)	0.0013 (7)	−0.0003 (7)	0.0017 (7)
C12	0.0190 (9)	0.0160 (9)	0.0159 (8)	0.0023 (7)	−0.0014 (7)	−0.0023 (7)
C19	0.0170 (9)	0.0170 (9)	0.0227 (9)	0.0012 (7)	−0.0020 (7)	−0.0037 (7)
C3	0.0164 (9)	0.0191 (9)	0.0147 (8)	0.0027 (7)	0.0013 (7)	0.0021 (7)
C7	0.0375 (12)	0.0217 (10)	0.0191 (9)	0.0002 (9)	−0.0023 (8)	−0.0043 (8)
C14	0.0138 (8)	0.0183 (9)	0.0182 (8)	−0.0021 (7)	0.0016 (7)	−0.0021 (7)
C16	0.0208 (9)	0.0208 (10)	0.0211 (9)	0.0066 (7)	−0.0021 (7)	−0.0017 (7)
C17	0.0133 (8)	0.0242 (9)	0.0162 (8)	−0.0021 (7)	−0.0014 (7)	−0.0027 (7)
C6	0.0297 (11)	0.0224 (10)	0.0226 (9)	−0.0051 (8)	−0.0063 (8)	0.0007 (8)
C5	0.0211 (9)	0.0224 (10)	0.0173 (8)	−0.0015 (7)	−0.0017 (7)	0.0036 (7)
C18	0.0201 (9)	0.0206 (10)	0.0188 (9)	0.0018 (7)	0.0004 (7)	−0.0085 (7)
C15	0.0236 (9)	0.0210 (9)	0.0185 (8)	0.0042 (9)	−0.0006 (7)	−0.0066 (8)
C20	0.0341 (11)	0.0283 (11)	0.0201 (9)	0.0067 (9)	−0.0043 (8)	−0.0008 (8)

Geometric parameters (Å, º)

O1—C17	1.377 (2)	C13—H13B	0.96
O1—C20	1.430 (2)	C13—H13C	0.96
C1—Cl1	1.7505 (19)	C12—H12	0.98
N2—H2	0.88 (3)	C19—C18	1.394 (2)
N3—C11	1.143 (2)	C19—C14	1.406 (2)
N1—C1	1.304 (2)	C19—H19	0.93
N1—C9	1.379 (2)	C3—H3	0.93
C2—C3	1.370 (3)	C7—C6	1.421 (3)
C2—C1	1.429 (2)	C7—H7	0.93
C2—C10	1.526 (2)	C14—C15	1.393 (3)
C4—C5	1.417 (3)	C16—C17	1.392 (2)
C4—C9	1.420 (2)	C16—C15	1.401 (2)
C4—C3	1.428 (2)	C16—H16	0.93
C10—H10	0.98	C17—C18	1.393 (3)
C8—C7	1.372 (3)	C6—C5	1.375 (3)
C8—C9	1.420 (3)	C6—H6	0.93
C8—H8	0.93	C5—H5	0.93
C10—N2	1.471 (2)	C18—H18	0.93
C10—C11	1.499 (2)	C15—H15	0.93
C12—N2	1.488 (2)	C20—H20A	0.96
C12—C13	1.534 (3)	C20—H20B	0.96
C12—C14	1.520 (2)	C20—H20C	0.96
C13—H13A	0.96
C17—O1—C20	117.42 (14)	C13—C12—H12	108.8
N2—C10—C11	110.59 (14)	C18—C19—C14	120.87 (17)
N2—C10—C2	112.50 (15)	C18—C19—H19	119.6
C11—C10—C2	111.23 (14)	C14—C19—H19	119.6
N2—C12—C14	109.81 (14)	C2—C3—C4	120.83 (16)
N2—C12—C13	110.04 (15)	C2—C3—H3	119.6
C14—C12—C13	110.68 (15)	C4—C3—H3	119.6
C10—N2—C12	112.35 (14)	C8—C7—C6	120.63 (18)
C10—N2—H2	105.4 (17)	C8—C7—H7	119.7
C12—N2—H2	109.5 (18)	C6—C7—H7	119.7
C1—N1—C9	117.40 (15)	C15—C14—C19	118.19 (16)
C3—C2—C1	116.28 (16)	C15—C14—C12	121.85 (15)
C3—C2—C10	123.43 (15)	C19—C14—C12	119.92 (16)
C1—C2—C10	120.26 (15)	C17—C16—C15	119.62 (17)
C5—C4—C9	119.32 (17)	C17—C16—H16	120.2
C5—C4—C3	123.44 (17)	C15—C16—H16	120.2
C9—C4—C3	117.24 (16)	O1—C17—C16	124.17 (17)
N1—C1—C2	126.09 (17)	O1—C17—C18	115.90 (15)
N1—C1—Cl1	114.99 (14)	C16—C17—C18	119.92 (16)
C2—C1—Cl1	118.90 (13)	C5—C6—C7	120.40 (18)
N2—C10—H10	107.4	C5—C6—H6	119.8
C11—C10—H10	107.4	C7—C6—H6	119.8
C2—C10—H10	107.4	C6—C5—C4	120.15 (18)
N3—C11—C10	175.00 (18)	C6—C5—H5	119.9
C7—C8—C9	119.91 (18)	C4—C5—H5	119.9
C7—C8—H8	120	C17—C18—C19	120.07 (16)
C9—C8—H8	120	C17—C18—H18	120
C12—C13—H13A	109.5	C19—C18—H18	120
C12—C13—H13B	109.5	C14—C15—C16	121.32 (16)
H13A—C13—H13B	109.5	C14—C15—H15	119.3
C12—C13—H13C	109.5	C16—C15—H15	119.3
H13A—C13—H13C	109.5	O1—C20—H20A	109.5
H13B—C13—H13C	109.5	O1—C20—H20B	109.5
N1—C9—C8	118.27 (16)	H20A—C20—H20B	109.5
N1—C9—C4	122.13 (16)	O1—C20—H20C	109.5
C8—C9—C4	119.59 (16)	H20A—C20—H20C	109.5
N2—C12—H12	108.8	H20B—C20—H20C	109.5
C14—C12—H12	108.8
C9—N1—C1—C2	1.0 (3)	C10—C2—C3—C4	176.59 (16)
C9—N1—C1—Cl1	−177.73 (13)	C5—C4—C3—C2	−178.52 (17)
C3—C2—C1—N1	−0.1 (3)	C9—C4—C3—C2	1.6 (2)
C10—C2—C1—N1	−178.00 (17)	C9—C8—C7—C6	−0.5 (3)
C3—C2—C1—Cl1	178.61 (13)	C18—C19—C14—C15	−0.1 (3)
C10—C2—C1—Cl1	0.7 (2)	C18—C19—C14—C12	−177.95 (17)
C12—N2—C10—C11	−68.00 (18)	N2—C12—C14—C15	33.7 (2)
C12—N2—C10—C2	166.95 (14)	C13—C12—C14—C15	−88.0 (2)
C3—C2—C10—N2	110.05 (19)	N2—C12—C14—C19	−148.59 (16)
C1—C2—C10—N2	−72.2 (2)	C13—C12—C14—C19	89.7 (2)
C3—C2—C10—C11	−14.7 (2)	C20—O1—C17—C16	5.0 (3)
C1—C2—C10—C11	163.09 (15)	C20—O1—C17—C18	−175.64 (16)
N2—C10—C11—N3	4 (2)	C15—C16—C17—O1	179.10 (17)
C2—C10—C11—N3	130 (2)	C15—C16—C17—C18	−0.2 (3)
C1—N1—C9—C8	179.31 (17)	C8—C7—C6—C5	0.1 (3)
C1—N1—C9—C4	−0.6 (3)	C7—C6—C5—C4	0.2 (3)
C7—C8—C9—N1	−179.21 (17)	C9—C4—C5—C6	0.0 (3)
C7—C8—C9—C4	0.7 (3)	C3—C4—C5—C6	−179.89 (17)
C5—C4—C9—N1	179.47 (16)	O1—C17—C18—C19	−178.87 (16)
C3—C4—C9—N1	−0.6 (3)	C16—C17—C18—C19	0.5 (3)
C5—C4—C9—C8	−0.5 (2)	C14—C19—C18—C17	−0.3 (3)
C3—C4—C9—C8	179.44 (16)	C19—C14—C15—C16	0.4 (3)
C10—N2—C12—C14	158.18 (14)	C12—C14—C15—C16	178.19 (17)
C10—N2—C12—C13	−79.75 (18)	C17—C16—C15—C14	−0.2 (3)
C1—C2—C3—C4	−1.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N3^i	0.88 (3)	2.32 (3)	3.176 (2)	166 (2)
C8—H8···O1^ii	0.93	2.45	3.245 (2)	144
C5—H5···Cg2^i	0.93	2.76	3.646 (2)	159

Symmetry codes: (i) −x, y−1/2, −z+1; (ii) x, y−1, z−1.