(1R,3S)-Methyl 2-benzyl-6,7-dimeth-oxy-1-phenyl-1,2,3,4-tetra-hydro-isoquinoline-3-carboxyl-ate.

In the title compound, C(26)H(27)NO(4), a precursor to novel chiral catalysts, the N-containing six-membered ring assumes a half-boat conformation. Various C-H⋯π interactions and intermolecular short contacts (C⋯H = 2.81-2.90 Å) link the mol-ecules together in the crystal structure.

Related literature

For the synthesis, see: Chakka et al. (2009 ▶). For crystallograhic details of analogous mol­ecules, see Alberch et al. (2004 ▶); Aubry et al. (2006 ▶).

Experimental

Crystal data

C26H27NO4

M = 417.49

Triclinic,

a = 6.0199 (1) Å

b = 9.2592 (2) Å

c = 11.0429 (2) Å

α = 73.365 (1)°

β = 74.694 (1)°

γ = 75.737 (1)°

V = 559.05 (2) Å3

Z = 1

Cu Kα radiation

μ = 0.67 mm−1

T = 173 K

0.22 × 0.12 × 0.08 mm

Data collection

Bruker Kappa Duo APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.692, T max = 0.753

7546 measured reflections

3561 independent reflections

3536 reflections with I > 2σ(I)

R int = 0.012

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.077

S = 1.07

3561 reflections

281 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Flack (1983 ▶), 1483 Friedel pairs

Flack parameter: −0.01 (14)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and X-SEED (Barbour, 2001 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: ORTEP-3.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050521/hg2607sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050521/hg2607Isup2.hkl

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

C26H27NO4	Z = 1
Mr = 417.49	F(000) = 222
Triclinic, P1	Dx = 1.240 Mg m−3
Hall symbol: P 1	Melting point: 420 K
a = 6.0199 (1) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.2592 (2) Å	Cell parameters from 7546 reflections
c = 11.0429 (2) Å	θ = 4.3–68.9°
α = 73.365 (1)°	µ = 0.67 mm−1
β = 74.694 (1)°	T = 173 K
γ = 75.737 (1)°	Needle, yellow
V = 559.04 (2) Å3	0.22 × 0.12 × 0.08 mm

Bruker Kappa Duo APEXII diffractometer	3561 independent reflections
Radiation source: fine-focus sealed tube	3536 reflections with I > 2σ(I)
graphite	Rint = 0.012
0.5° φ scans and ω scans	θmax = 68.9°, θmin = 4.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −6→7
Tmin = 0.692, Tmax = 0.753	k = −10→10
7546 measured reflections	l = −13→13

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.028	w = 1/[σ2(Fo2) + (0.0475P)2 + 0.0785P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.077	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.16 e Å−3
3561 reflections	Δρmin = −0.16 e Å−3
281 parameters	Extinction correction: SHELXS97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3 restraints	Extinction coefficient: 0.0426 (18)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1483 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.01 (14)

Experimental. Half sphere of data collected using SAINT strategy (Bruker, 2006). Crystal to detector distance = 50 mm; combination of φ and ω scans of 0.5°, 80 s per °, 2 iterations.

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
O1	0.2537 (2)	0.14310 (13)	0.46249 (10)	0.0396 (3)
O2	0.51646 (19)	0.27489 (12)	0.53134 (10)	0.0364 (3)
O3	−0.3602 (2)	0.20138 (13)	1.02179 (14)	0.0468 (3)
O4	−0.1914 (3)	0.23948 (15)	1.16480 (12)	0.0514 (4)
N1	−0.0675 (2)	−0.10502 (13)	1.05031 (11)	0.0262 (3)
C1	−0.1027 (2)	−0.07812 (15)	0.91791 (14)	0.0247 (3)
H1	−0.2641	−0.0179	0.9133	0.030*
C2	0.0745 (2)	0.01232 (15)	0.81875 (14)	0.0256 (3)
C3	0.0848 (3)	0.03078 (16)	0.68640 (14)	0.0283 (3)
H3	−0.0128	−0.0169	0.6612	0.034*
C4	0.2340 (3)	0.11668 (16)	0.59283 (14)	0.0298 (3)
C5	0.3790 (2)	0.18793 (15)	0.63010 (14)	0.0280 (3)
C6	0.3717 (2)	0.16708 (16)	0.75934 (14)	0.0270 (3)
H6	0.4725	0.2122	0.7846	0.032*
C7	0.2187 (2)	0.08063 (15)	0.85461 (13)	0.0252 (3)
C8	0.2148 (2)	0.06332 (17)	0.99497 (14)	0.0292 (3)
H8A	0.2370	0.1606	1.0067	0.035*
H8B	0.3468	−0.0180	1.0206	0.035*
C9	−0.0138 (3)	0.02263 (16)	1.08230 (14)	0.0269 (3)
H9	0.0152	−0.0155	1.1721	0.032*
C10	−0.2107 (3)	0.16235 (17)	1.08378 (14)	0.0308 (3)
C11	−0.3714 (5)	0.3725 (2)	1.1814 (2)	0.0633 (6)
H11A	−0.3393	0.4199	1.2422	0.095*
H11B	−0.5244	0.3412	1.2153	0.095*
H11C	−0.3725	0.4466	1.0979	0.095*
C12	−0.0842 (3)	−0.23317 (16)	0.89052 (13)	0.0263 (3)
C13	−0.2621 (3)	−0.26446 (17)	0.84954 (14)	0.0293 (3)
H13	−0.3966	−0.1876	0.8363	0.035*
C14	−0.2445 (3)	−0.40782 (18)	0.82777 (16)	0.0346 (3)
H14	−0.3673	−0.4285	0.7998	0.042*
C15	−0.0496 (3)	−0.52049 (17)	0.84649 (16)	0.0368 (4)
H15	−0.0378	−0.6184	0.8315	0.044*
C16	0.1286 (3)	−0.48936 (17)	0.88734 (16)	0.0382 (4)
H16	0.2632	−0.5662	0.9002	0.046*
C17	0.1116 (3)	−0.34743 (17)	0.90937 (16)	0.0330 (3)
H17	0.2344	−0.3274	0.9377	0.040*
C18	0.1052 (3)	0.0782 (2)	0.41938 (17)	0.0462 (4)
H18A	0.1349	0.1062	0.3247	0.069*
H18B	−0.0591	0.1176	0.4541	0.069*
H18C	0.1379	−0.0337	0.4497	0.069*
C19	0.6262 (3)	0.3736 (2)	0.56531 (18)	0.0429 (4)
H19A	0.7198	0.4294	0.4872	0.064*
H19B	0.7283	0.3123	0.6249	0.064*
H19C	0.5059	0.4469	0.6072	0.064*
C20	−0.2513 (3)	−0.17390 (17)	1.15037 (14)	0.0304 (3)
H20A	−0.2927	−0.2542	1.1219	0.037*
H20B	−0.3934	−0.0944	1.1635	0.037*
C21	−0.1694 (3)	−0.24341 (17)	1.27560 (14)	0.0311 (3)
C22	−0.2758 (3)	−0.1877 (2)	1.38479 (16)	0.0404 (4)
H22	−0.4093	−0.1075	1.3826	0.049*
C23	−0.1904 (4)	−0.2472 (2)	1.49690 (17)	0.0506 (5)
H23	−0.2661	−0.2086	1.5714	0.061*
C24	0.0038 (4)	−0.3620 (2)	1.50087 (18)	0.0536 (5)
H24	0.0642	−0.4016	1.5775	0.064*
C25	0.1101 (4)	−0.4193 (3)	1.39405 (19)	0.0553 (5)
H25	0.2436	−0.4994	1.3971	0.066*
C26	0.0240 (3)	−0.3612 (2)	1.28165 (17)	0.0442 (4)
H26	0.0980	−0.4022	1.2082	0.053*

	U11	U22	U33	U12	U13	U23
O1	0.0486 (7)	0.0478 (7)	0.0253 (5)	−0.0190 (5)	−0.0072 (5)	−0.0048 (5)
O2	0.0368 (6)	0.0380 (6)	0.0331 (6)	−0.0168 (5)	−0.0028 (5)	−0.0019 (4)
O3	0.0365 (6)	0.0370 (6)	0.0757 (9)	0.0013 (5)	−0.0246 (6)	−0.0222 (6)
O4	0.0722 (10)	0.0442 (7)	0.0412 (6)	0.0050 (6)	−0.0192 (6)	−0.0217 (5)
N1	0.0261 (6)	0.0264 (6)	0.0261 (6)	−0.0075 (5)	−0.0070 (5)	−0.0023 (5)
C1	0.0222 (7)	0.0244 (7)	0.0275 (7)	−0.0042 (5)	−0.0065 (6)	−0.0050 (5)
C2	0.0230 (7)	0.0222 (6)	0.0291 (7)	−0.0020 (5)	−0.0053 (6)	−0.0044 (5)
C3	0.0290 (7)	0.0276 (7)	0.0295 (7)	−0.0058 (6)	−0.0086 (6)	−0.0058 (6)
C4	0.0312 (8)	0.0294 (8)	0.0275 (7)	−0.0033 (6)	−0.0076 (6)	−0.0052 (6)
C5	0.0250 (7)	0.0236 (7)	0.0311 (7)	−0.0033 (5)	−0.0040 (6)	−0.0027 (5)
C6	0.0230 (7)	0.0245 (7)	0.0337 (8)	−0.0024 (5)	−0.0085 (6)	−0.0065 (6)
C7	0.0228 (7)	0.0222 (7)	0.0297 (7)	−0.0006 (5)	−0.0088 (6)	−0.0049 (6)
C8	0.0263 (8)	0.0325 (7)	0.0302 (7)	−0.0075 (6)	−0.0081 (6)	−0.0058 (6)
C9	0.0275 (7)	0.0291 (7)	0.0250 (6)	−0.0072 (5)	−0.0069 (6)	−0.0050 (5)
C10	0.0316 (8)	0.0305 (7)	0.0298 (7)	−0.0109 (6)	−0.0013 (6)	−0.0065 (6)
C11	0.0849 (16)	0.0475 (11)	0.0494 (11)	0.0069 (10)	−0.0024 (11)	−0.0257 (9)
C12	0.0268 (7)	0.0247 (7)	0.0253 (7)	−0.0068 (5)	−0.0022 (6)	−0.0040 (5)
C13	0.0283 (8)	0.0314 (7)	0.0285 (7)	−0.0065 (6)	−0.0038 (6)	−0.0085 (6)
C14	0.0344 (8)	0.0366 (8)	0.0369 (8)	−0.0141 (6)	−0.0029 (7)	−0.0126 (6)
C15	0.0429 (9)	0.0267 (7)	0.0385 (8)	−0.0109 (7)	0.0038 (7)	−0.0115 (6)
C16	0.0353 (8)	0.0269 (8)	0.0444 (9)	−0.0015 (6)	−0.0021 (7)	−0.0057 (6)
C17	0.0285 (7)	0.0303 (8)	0.0387 (8)	−0.0053 (6)	−0.0058 (6)	−0.0069 (6)
C18	0.0482 (10)	0.0640 (12)	0.0332 (8)	−0.0173 (8)	−0.0102 (8)	−0.0148 (8)
C19	0.0440 (9)	0.0401 (9)	0.0446 (9)	−0.0217 (7)	−0.0066 (8)	−0.0005 (7)
C20	0.0289 (7)	0.0335 (7)	0.0287 (7)	−0.0100 (6)	−0.0052 (6)	−0.0042 (6)
C21	0.0307 (8)	0.0308 (8)	0.0297 (7)	−0.0122 (6)	−0.0048 (6)	0.0001 (6)
C22	0.0433 (9)	0.0407 (9)	0.0340 (8)	−0.0071 (7)	−0.0067 (7)	−0.0055 (7)
C23	0.0641 (13)	0.0568 (11)	0.0323 (8)	−0.0186 (9)	−0.0081 (8)	−0.0083 (8)
C24	0.0515 (11)	0.0696 (13)	0.0350 (9)	−0.0169 (10)	−0.0173 (8)	0.0073 (8)
C25	0.0405 (10)	0.0633 (12)	0.0423 (10)	0.0024 (8)	−0.0087 (8)	0.0080 (9)
C26	0.0414 (10)	0.0460 (10)	0.0322 (8)	0.0004 (7)	−0.0032 (7)	−0.0005 (7)

O1—C4	1.3668 (18)	C12—C17	1.393 (2)
O1—C18	1.428 (2)	C13—C14	1.390 (2)
O2—C5	1.3681 (17)	C13—H13	0.9500
O2—C19	1.428 (2)	C14—C15	1.382 (2)
O3—C10	1.197 (2)	C14—H14	0.9500
O4—C10	1.3363 (19)	C15—C16	1.385 (3)
O4—C11	1.446 (2)	C15—H15	0.9500
N1—C9	1.4538 (18)	C16—C17	1.379 (2)
N1—C20	1.4667 (18)	C16—H16	0.9500
N1—C1	1.4743 (18)	C17—H17	0.9500
C1—C12	1.5222 (19)	C18—H18A	0.9800
C1—C2	1.5285 (19)	C18—H18B	0.9800
C1—H1	1.0000	C18—H18C	0.9800
C2—C7	1.381 (2)	C19—H19A	0.9800
C2—C3	1.408 (2)	C19—H19B	0.9800
C3—C4	1.378 (2)	C19—H19C	0.9800
C3—H3	0.9500	C20—C21	1.505 (2)
C4—C5	1.412 (2)	C20—H20A	0.9900
C5—C6	1.375 (2)	C20—H20B	0.9900
C6—C7	1.402 (2)	C21—C22	1.384 (2)
C6—H6	0.9500	C21—C26	1.387 (2)
C7—C8	1.506 (2)	C22—C23	1.381 (3)
C8—C9	1.521 (2)	C22—H22	0.9500
C8—H8A	0.9900	C23—C24	1.374 (3)
C8—H8B	0.9900	C23—H23	0.9500
C9—C10	1.525 (2)	C24—C25	1.369 (3)
C9—H9	1.0000	C24—H24	0.9500
C11—H11A	0.9800	C25—C26	1.385 (3)
C11—H11B	0.9800	C25—H25	0.9500
C11—H11C	0.9800	C26—H26	0.9500
C12—C13	1.386 (2)
C4—O1—C18	117.43 (12)	C17—C12—C1	119.97 (13)
C5—O2—C19	116.91 (12)	C12—C13—C14	120.24 (14)
C10—O4—C11	116.59 (16)	C12—C13—H13	119.9
C9—N1—C20	111.85 (11)	C14—C13—H13	119.9
C9—N1—C1	116.21 (11)	C15—C14—C13	120.45 (15)
C20—N1—C1	113.54 (11)	C15—C14—H14	119.8
N1—C1—C12	108.07 (11)	C13—C14—H14	119.8
N1—C1—C2	111.52 (11)	C14—C15—C16	119.39 (14)
C12—C1—C2	111.33 (11)	C14—C15—H15	120.3
N1—C1—H1	108.6	C16—C15—H15	120.3
C12—C1—H1	108.6	C17—C16—C15	120.36 (14)
C2—C1—H1	108.6	C17—C16—H16	119.8
C7—C2—C3	119.04 (13)	C15—C16—H16	119.8
C7—C2—C1	122.20 (12)	C16—C17—C12	120.60 (15)
C3—C2—C1	118.73 (13)	C16—C17—H17	119.7
C4—C3—C2	121.22 (14)	C12—C17—H17	119.7
C4—C3—H3	119.4	O1—C18—H18A	109.5
C2—C3—H3	119.4	O1—C18—H18B	109.5
O1—C4—C3	125.46 (14)	H18A—C18—H18B	109.5
O1—C4—C5	115.04 (12)	O1—C18—H18C	109.5
C3—C4—C5	119.50 (13)	H18A—C18—H18C	109.5
O2—C5—C6	125.15 (14)	H18B—C18—H18C	109.5
O2—C5—C4	115.76 (13)	O2—C19—H19A	109.5
C6—C5—C4	119.09 (13)	O2—C19—H19B	109.5
C5—C6—C7	121.42 (14)	H19A—C19—H19B	109.5
C5—C6—H6	119.3	O2—C19—H19C	109.5
C7—C6—H6	119.3	H19A—C19—H19C	109.5
C2—C7—C6	119.71 (13)	H19B—C19—H19C	109.5
C2—C7—C8	120.93 (12)	N1—C20—C21	110.54 (12)
C6—C7—C8	119.36 (13)	N1—C20—H20A	109.5
C7—C8—C9	112.16 (12)	C21—C20—H20A	109.5
C7—C8—H8A	109.2	N1—C20—H20B	109.5
C9—C8—H8A	109.2	C21—C20—H20B	109.5
C7—C8—H8B	109.2	H20A—C20—H20B	108.1
C9—C8—H8B	109.2	C22—C21—C26	118.49 (15)
H8A—C8—H8B	107.9	C22—C21—C20	121.50 (15)
N1—C9—C8	109.50 (12)	C26—C21—C20	119.94 (15)
N1—C9—C10	115.01 (12)	C23—C22—C21	120.77 (17)
C8—C9—C10	112.26 (12)	C23—C22—H22	119.6
N1—C9—H9	106.5	C21—C22—H22	119.6
C8—C9—H9	106.5	C24—C23—C22	120.14 (18)
C10—C9—H9	106.5	C24—C23—H23	119.9
O3—C10—O4	123.72 (15)	C22—C23—H23	119.9
O3—C10—C9	126.64 (14)	C25—C24—C23	119.84 (18)
O4—C10—C9	109.64 (13)	C25—C24—H24	120.1
O4—C11—H11A	109.5	C23—C24—H24	120.1
O4—C11—H11B	109.5	C24—C25—C26	120.33 (18)
H11A—C11—H11B	109.5	C24—C25—H25	119.8
O4—C11—H11C	109.5	C26—C25—H25	119.8
H11A—C11—H11C	109.5	C25—C26—C21	120.42 (17)
H11B—C11—H11C	109.5	C25—C26—H26	119.8
C13—C12—C17	118.96 (13)	C21—C26—H26	119.8
C13—C12—C1	121.05 (13)
C9—N1—C1—C12	163.45 (12)	C1—N1—C9—C10	65.95 (16)
C20—N1—C1—C12	−64.73 (15)	C7—C8—C9—N1	49.38 (16)
C9—N1—C1—C2	40.77 (16)	C7—C8—C9—C10	−79.63 (15)
C20—N1—C1—C2	172.59 (11)	C11—O4—C10—O3	3.4 (2)
N1—C1—C2—C7	−10.29 (17)	C11—O4—C10—C9	−177.57 (15)
C12—C1—C2—C7	−131.08 (14)	N1—C9—C10—O3	−28.2 (2)
N1—C1—C2—C3	171.92 (11)	C8—C9—C10—O3	97.86 (18)
C12—C1—C2—C3	51.13 (17)	N1—C9—C10—O4	152.77 (13)
C7—C2—C3—C4	−0.7 (2)	C8—C9—C10—O4	−81.16 (15)
C1—C2—C3—C4	177.19 (12)	N1—C1—C12—C13	125.53 (14)
C18—O1—C4—C3	0.9 (2)	C2—C1—C12—C13	−111.68 (14)
C18—O1—C4—C5	−177.87 (13)	N1—C1—C12—C17	−53.04 (16)
C2—C3—C4—O1	−178.91 (14)	C2—C1—C12—C17	69.75 (16)
C2—C3—C4—C5	−0.1 (2)	C17—C12—C13—C14	0.0 (2)
C19—O2—C5—C6	−12.4 (2)	C1—C12—C13—C14	−178.56 (13)
C19—O2—C5—C4	167.07 (13)	C12—C13—C14—C15	−0.1 (2)
O1—C4—C5—O2	0.83 (18)	C13—C14—C15—C16	0.1 (2)
C3—C4—C5—O2	−178.07 (12)	C14—C15—C16—C17	0.1 (2)
O1—C4—C5—C6	−179.67 (13)	C15—C16—C17—C12	−0.2 (2)
C3—C4—C5—C6	1.4 (2)	C13—C12—C17—C16	0.2 (2)
O2—C5—C6—C7	177.51 (12)	C1—C12—C17—C16	178.75 (14)
C4—C5—C6—C7	−1.9 (2)	C9—N1—C20—C21	−64.04 (15)
C3—C2—C7—C6	0.19 (19)	C1—N1—C20—C21	162.04 (12)
C1—C2—C7—C6	−177.59 (12)	N1—C20—C21—C22	115.75 (16)
C3—C2—C7—C8	−179.65 (13)	N1—C20—C21—C26	−61.09 (19)
C1—C2—C7—C8	2.57 (19)	C26—C21—C22—C23	0.5 (3)
C5—C6—C7—C2	1.1 (2)	C20—C21—C22—C23	−176.41 (16)
C5—C6—C7—C8	−179.02 (13)	C21—C22—C23—C24	0.7 (3)
C2—C7—C8—C9	−22.20 (18)	C22—C23—C24—C25	−1.2 (3)
C6—C7—C8—C9	157.96 (12)	C23—C24—C25—C26	0.6 (3)
C20—N1—C9—C8	165.87 (12)	C24—C25—C26—C21	0.6 (3)
C1—N1—C9—C8	−61.53 (16)	C22—C21—C26—C25	−1.1 (3)
C20—N1—C9—C10	−66.65 (15)	C20—C21—C26—C25	175.85 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19A···Cgi	0.98	2.82	3.639 (2)	148

Table 1

C—H⋯π interaction (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19A⋯Cg i	0.98	2.82	3.639 (2)	148

Symmetry code: (i) . Cg is the centroid of the C21–C26 ring.