(4R)-4-(Biphenyl-4-yl)-7-chloro-1,2,3,4-tetra-hydro-quinoline.

The title compound, C(21)H(18)ClN, was synthesized by an enanti-oselective Brønsted acid-catalysed transfer hydrogenation reaction. The six-membered heterocycle adopts a half-chair conformation. It has the biphenyl residue in an axial position. The two rings of the biphenyl residue are almost coplanar [dihedral angle = 2.65 (9)°]. The crystal packing is stabilized by N-H⋯Cl hydrogen bonds, which connect the mol-ecules into chains running along the a axis.

Related literature

For organocatalysed processes, see: Rueping, Sugiono & Schoepke (2010 ▶); Rueping, Dufour & Schoepke (2011 ▶). For Brønsted acid-catalysed transfer hydrogenations, see: Rueping et al. (2008 ▶); Rueping, Stoeckel et al. (2010 ▶). For the synthesis of the title compound, see: Rueping, Theissmann et al. (2011 ▶).

Experimental

Crystal data

C21H18ClN

M = 319.81

Orthorhombic,

a = 5.5354 (4) Å

b = 8.0039 (4) Å

c = 35.8207 (17) Å

V = 1587.03 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 173 K

0.35 × 0.21 × 0.11 mm

Data collection

STOE IPDS II two-circle-diffractometer

Absorption correction: multi-scan (MULABS; Spek, 2009 ▶; Blessing, 1995 ▶) T min = 0.921, T max = 0.984

18042 measured reflections

3071 independent reflections

2867 reflections with I > 2σ(I)

R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.079

S = 1.05

3071 reflections

213 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983 ▶), 1240 Friedel pairs

Flack parameter: 0.01 (5)

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681103830X/lr2028sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681103830X/lr2028Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681103830X/lr2028Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H18ClN	F(000) = 672
Mr = 319.81	Dx = 1.339 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 18030 reflections
a = 5.5354 (4) Å	θ = 2.3–26.4°
b = 8.0039 (4) Å	µ = 0.24 mm−1
c = 35.8207 (17) Å	T = 173 K
V = 1587.03 (16) Å3	Plate, colourless
Z = 4	0.35 × 0.21 × 0.11 mm

STOE IPDS II two-circle-diffractometer	3071 independent reflections
Radiation source: fine-focus sealed tube	2867 reflections with I > 2σ(I)
graphite	Rint = 0.059
ω scans	θmax = 25.9°, θmin = 2.3°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −6→6
Tmin = 0.921, Tmax = 0.984	k = −9→9
18042 measured reflections	l = −43→44

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030	w = 1/[σ2(Fo2) + (0.0482P)2 + 0.1208P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.079	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.21 e Å−3
3071 reflections	Δρmin = −0.18 e Å−3
213 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.026 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1240 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.01 (5)

Experimental. ;

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.

	x	y	z	Uiso*/Ueq
Cl1	0.19210 (10)	0.59051 (5)	0.005768 (11)	0.04965 (15)
N1	0.1122 (3)	0.01504 (19)	0.06517 (4)	0.0428 (4)
H1	−0.002 (5)	0.000 (3)	0.0477 (7)	0.059 (6)*
C2	0.1862 (4)	−0.12356 (19)	0.08883 (4)	0.0407 (4)
H2A	0.1373	−0.2302	0.0771	0.049*
H2B	0.1034	−0.1151	0.1133	0.049*
C3	0.4575 (4)	−0.12319 (19)	0.09483 (5)	0.0406 (4)
H3A	0.5403	−0.1469	0.0709	0.049*
H3B	0.5017	−0.2120	0.1128	0.049*
C4	0.5406 (3)	0.04765 (18)	0.10990 (4)	0.0317 (3)
H4	0.7213	0.0481	0.1100	0.038*
C5	0.4573 (3)	0.18288 (17)	0.08315 (4)	0.0281 (3)
C6	0.2442 (3)	0.15963 (19)	0.06229 (4)	0.0308 (3)
C7	0.1654 (3)	0.28714 (19)	0.03814 (4)	0.0331 (3)
H7	0.0211	0.2739	0.0241	0.040*
C8	0.3000 (3)	0.43151 (18)	0.03507 (4)	0.0337 (3)
C9	0.5160 (3)	0.45488 (18)	0.05393 (4)	0.0349 (3)
H9	0.6092	0.5534	0.0506	0.042*
C10	0.5906 (3)	0.32869 (19)	0.07781 (4)	0.0327 (3)
H10	0.7381	0.3421	0.0910	0.039*
C11	0.4564 (3)	0.07013 (17)	0.15017 (4)	0.0277 (3)
C12	0.5861 (3)	−0.00906 (19)	0.17846 (4)	0.0319 (3)
H12	0.7295	−0.0682	0.1723	0.038*
C13	0.5108 (3)	−0.00350 (18)	0.21525 (4)	0.0311 (3)
H13	0.6035	−0.0590	0.2338	0.037*
C14	0.3006 (3)	0.08229 (16)	0.22576 (4)	0.0248 (3)
C15	0.1743 (3)	0.16460 (19)	0.19743 (4)	0.0304 (3)
H15	0.0325	0.2257	0.2035	0.037*
C16	0.2518 (3)	0.15902 (19)	0.16041 (4)	0.0310 (3)
H16	0.1628	0.2172	0.1418	0.037*
C21	0.2160 (3)	0.08270 (16)	0.26536 (4)	0.0249 (3)
C22	0.3477 (3)	0.00061 (19)	0.29322 (4)	0.0351 (4)
H22	0.4934	−0.0551	0.2868	0.042*
C23	0.2701 (3)	−0.0012 (2)	0.33005 (4)	0.0403 (4)
H23	0.3632	−0.0577	0.3484	0.048*
C24	0.0585 (3)	0.07846 (19)	0.34030 (4)	0.0357 (4)
H24	0.0048	0.0762	0.3655	0.043*
C25	−0.0739 (3)	0.1618 (2)	0.31320 (5)	0.0371 (4)
H25	−0.2188	0.2178	0.3199	0.045*
C26	0.0041 (3)	0.16382 (19)	0.27635 (4)	0.0321 (3)
H26	−0.0888	0.2217	0.2582	0.039*

	U11	U22	U33	U12	U13	U23
Cl1	0.0746 (3)	0.0413 (2)	0.0330 (2)	0.0169 (2)	0.0022 (2)	0.00881 (16)
N1	0.0445 (8)	0.0444 (8)	0.0394 (8)	−0.0146 (7)	−0.0043 (7)	0.0067 (6)
C2	0.0615 (11)	0.0297 (7)	0.0309 (8)	−0.0111 (8)	0.0079 (8)	−0.0035 (6)
C3	0.0623 (11)	0.0287 (8)	0.0309 (8)	0.0079 (8)	0.0097 (8)	−0.0005 (6)
C4	0.0329 (7)	0.0325 (7)	0.0296 (7)	0.0056 (6)	0.0058 (6)	0.0022 (6)
C5	0.0316 (8)	0.0290 (7)	0.0237 (7)	0.0038 (6)	0.0040 (6)	−0.0007 (5)
C6	0.0341 (8)	0.0337 (7)	0.0246 (7)	−0.0020 (6)	0.0060 (6)	−0.0018 (5)
C7	0.0337 (8)	0.0420 (8)	0.0237 (7)	0.0033 (7)	0.0008 (6)	−0.0011 (6)
C8	0.0473 (9)	0.0304 (7)	0.0235 (7)	0.0083 (7)	0.0045 (7)	0.0002 (5)
C9	0.0461 (9)	0.0271 (7)	0.0315 (7)	−0.0031 (7)	0.0041 (7)	−0.0018 (6)
C10	0.0351 (8)	0.0345 (7)	0.0284 (7)	−0.0023 (6)	0.0025 (6)	−0.0044 (6)
C11	0.0301 (7)	0.0250 (6)	0.0280 (7)	−0.0008 (6)	0.0016 (6)	0.0003 (6)
C12	0.0287 (7)	0.0335 (8)	0.0336 (8)	0.0093 (6)	0.0012 (6)	0.0005 (6)
C13	0.0312 (7)	0.0327 (7)	0.0294 (7)	0.0073 (6)	−0.0046 (6)	0.0016 (6)
C14	0.0253 (6)	0.0214 (6)	0.0278 (6)	−0.0025 (6)	−0.0017 (6)	−0.0012 (5)
C15	0.0278 (7)	0.0329 (7)	0.0306 (7)	0.0083 (6)	0.0009 (6)	−0.0003 (6)
C16	0.0312 (8)	0.0334 (7)	0.0285 (7)	0.0079 (6)	−0.0021 (6)	0.0037 (6)
C21	0.0281 (7)	0.0201 (6)	0.0266 (6)	−0.0038 (6)	−0.0018 (5)	−0.0023 (5)
C22	0.0377 (8)	0.0345 (8)	0.0330 (8)	0.0069 (7)	0.0011 (7)	0.0025 (6)
C23	0.0523 (10)	0.0389 (8)	0.0296 (8)	0.0077 (7)	−0.0025 (7)	0.0058 (6)
C24	0.0491 (9)	0.0307 (7)	0.0273 (7)	−0.0037 (7)	0.0057 (7)	−0.0027 (6)
C25	0.0374 (9)	0.0396 (8)	0.0344 (8)	0.0023 (7)	0.0045 (7)	−0.0068 (7)
C26	0.0317 (8)	0.0345 (7)	0.0302 (7)	0.0036 (7)	−0.0027 (6)	−0.0013 (6)

Cl1—C8	1.7545 (15)	C11—C16	1.387 (2)
N1—C6	1.372 (2)	C11—C12	1.394 (2)
N1—C2	1.455 (2)	C12—C13	1.383 (2)
N1—H1	0.90 (3)	C12—H12	0.9500
C2—C3	1.517 (3)	C13—C14	1.402 (2)
C2—H2A	0.9900	C13—H13	0.9500
C2—H2B	0.9900	C14—C15	1.397 (2)
C3—C4	1.540 (2)	C14—C21	1.4937 (19)
C3—H3A	0.9900	C15—C16	1.395 (2)
C3—H3B	0.9900	C15—H15	0.9500
C4—C5	1.5175 (19)	C16—H16	0.9500
C4—C11	1.5267 (19)	C21—C26	1.398 (2)
C4—H4	1.0000	C21—C22	1.399 (2)
C5—C10	1.394 (2)	C22—C23	1.388 (2)
C5—C6	1.409 (2)	C22—H22	0.9500
C6—C7	1.407 (2)	C23—C24	1.383 (2)
C7—C8	1.379 (2)	C23—H23	0.9500
C7—H7	0.9500	C24—C25	1.387 (2)
C8—C9	1.386 (2)	C24—H24	0.9500
C9—C10	1.386 (2)	C25—C26	1.389 (2)
C9—H9	0.9500	C25—H25	0.9500
C10—H10	0.9500	C26—H26	0.9500
C6—N1—C2	122.48 (15)	C5—C10—H10	118.8
C6—N1—H1	115.7 (15)	C16—C11—C12	117.50 (13)
C2—N1—H1	120.3 (15)	C16—C11—C4	124.03 (13)
N1—C2—C3	111.07 (14)	C12—C11—C4	118.41 (13)
N1—C2—H2A	109.4	C13—C12—C11	121.50 (13)
C3—C2—H2A	109.4	C13—C12—H12	119.2
N1—C2—H2B	109.4	C11—C12—H12	119.2
C3—C2—H2B	109.4	C12—C13—C14	121.44 (13)
H2A—C2—H2B	108.0	C12—C13—H13	119.3
C2—C3—C4	110.31 (13)	C14—C13—H13	119.3
C2—C3—H3A	109.6	C15—C14—C13	116.80 (13)
C4—C3—H3A	109.6	C15—C14—C21	122.13 (12)
C2—C3—H3B	109.6	C13—C14—C21	121.06 (12)
C4—C3—H3B	109.6	C16—C15—C14	121.43 (13)
H3A—C3—H3B	108.1	C16—C15—H15	119.3
C5—C4—C11	114.82 (12)	C14—C15—H15	119.3
C5—C4—C3	108.73 (13)	C11—C16—C15	121.28 (13)
C11—C4—C3	110.15 (12)	C11—C16—H16	119.4
C5—C4—H4	107.6	C15—C16—H16	119.4
C11—C4—H4	107.6	C26—C21—C22	117.03 (13)
C3—C4—H4	107.6	C26—C21—C14	122.11 (12)
C10—C5—C6	118.75 (14)	C22—C21—C14	120.86 (13)
C10—C5—C4	121.53 (14)	C23—C22—C21	121.44 (15)
C6—C5—C4	119.69 (13)	C23—C22—H22	119.3
N1—C6—C7	119.52 (15)	C21—C22—H22	119.3
N1—C6—C5	121.15 (14)	C24—C23—C22	120.65 (15)
C7—C6—C5	119.33 (14)	C24—C23—H23	119.7
C8—C7—C6	119.28 (14)	C22—C23—H23	119.7
C8—C7—H7	120.4	C23—C24—C25	118.89 (14)
C6—C7—H7	120.4	C23—C24—H24	120.6
C7—C8—C9	122.71 (14)	C25—C24—H24	120.6
C7—C8—Cl1	118.13 (13)	C24—C25—C26	120.44 (15)
C9—C8—Cl1	119.17 (12)	C24—C25—H25	119.8
C8—C9—C10	117.34 (14)	C26—C25—H25	119.8
C8—C9—H9	121.3	C25—C26—C21	121.54 (14)
C10—C9—H9	121.3	C25—C26—H26	119.2
C9—C10—C5	122.47 (15)	C21—C26—H26	119.2
C9—C10—H10	118.8
C6—N1—C2—C3	−25.4 (2)	C5—C4—C11—C12	−157.97 (14)
N1—C2—C3—C4	54.08 (17)	C3—C4—C11—C12	78.90 (17)
C2—C3—C4—C5	−55.71 (17)	C16—C11—C12—C13	1.8 (2)
C2—C3—C4—C11	70.92 (17)	C4—C11—C12—C13	−175.56 (15)
C11—C4—C5—C10	88.01 (17)	C11—C12—C13—C14	−0.1 (2)
C3—C4—C5—C10	−148.10 (14)	C12—C13—C14—C15	−1.3 (2)
C11—C4—C5—C6	−93.87 (16)	C12—C13—C14—C21	177.88 (14)
C3—C4—C5—C6	30.02 (18)	C13—C14—C15—C16	1.1 (2)
C2—N1—C6—C7	178.40 (14)	C21—C14—C15—C16	−178.13 (13)
C2—N1—C6—C5	−1.7 (2)	C12—C11—C16—C15	−2.0 (2)
C10—C5—C6—N1	176.93 (14)	C4—C11—C16—C15	175.14 (14)
C4—C5—C6—N1	−1.2 (2)	C14—C15—C16—C11	0.6 (2)
C10—C5—C6—C7	−3.2 (2)	C15—C14—C21—C26	0.8 (2)
C4—C5—C6—C7	178.64 (13)	C13—C14—C21—C26	−178.40 (13)
N1—C6—C7—C8	−179.37 (14)	C15—C14—C21—C22	−179.32 (14)
C5—C6—C7—C8	0.7 (2)	C13—C14—C21—C22	1.5 (2)
C6—C7—C8—C9	2.3 (2)	C26—C21—C22—C23	0.5 (2)
C6—C7—C8—Cl1	−178.17 (11)	C14—C21—C22—C23	−179.43 (14)
C7—C8—C9—C10	−2.6 (2)	C21—C22—C23—C24	0.1 (2)
Cl1—C8—C9—C10	177.80 (11)	C22—C23—C24—C25	−0.6 (2)
C8—C9—C10—C5	0.0 (2)	C23—C24—C25—C26	0.5 (2)
C6—C5—C10—C9	2.8 (2)	C24—C25—C26—C21	0.1 (2)
C4—C5—C10—C9	−179.01 (14)	C22—C21—C26—C25	−0.6 (2)
C5—C4—C11—C16	24.9 (2)	C14—C21—C26—C25	179.31 (14)
C3—C4—C11—C16	−98.23 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1i	0.90 (3)	2.66 (3)	3.5466 (17)	171 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1i	0.90 (3)	2.66 (3)	3.5466 (17)	171 (2)

Symmetry code: (i) .