(1S,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), the heterocyclic ring assumes a half-chair conformation and inter-molecular C-H⋯O inter-actions help to construct the three-dimensional network within the crystal packing.

Related literature

The title compound is a precursor to chiral catalysts bearing a tetra­hydro­isoquinoline (TIQ) backbone. TIQ catalyst precursors have shown to be efficient for several asymmetric transformations, see: Chakka et al. (2010 ▶); Kawthekar et al. (2010 ▶). For related structures, see: Naicker et al. (2009 ▶, 2010 ▶, 2011 ▶). For the assignment of the absolute stereochemisty by NMR, see: Aubry et al. (2006 ▶).

Experimental

Crystal data

C26H27NO4

M = 417.49

Monoclinic,

a = 9.7797 (7) Å

b = 5.4646 (4) Å

c = 20.6959 (15) Å

β = 96.986 (1)°

V = 1097.82 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 173 K

0.85 × 0.07 × 0.06 mm

Data collection

Bruker Kappa DUO APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.931, T max = 0.995

20624 measured reflections

3032 independent reflections

2764 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.087

S = 1.05

3032 reflections

280 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.19 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009) ▶; software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017430/gw2101sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017430/gw2101Isup2.hkl

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

C26H27NO4	F(000) = 444
Mr = 417.49	Dx = 1.263 Mg m−3
Monoclinic, P21	Melting point: 420 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.7797 (7) Å	Cell parameters from 20624 reflections
b = 5.4646 (4) Å	θ = 2.0–28.4°
c = 20.6959 (15) Å	µ = 0.09 mm−1
β = 96.986 (1)°	T = 173 K
V = 1097.82 (14) Å3	Needle, yellow
Z = 2	0.85 × 0.07 × 0.06 mm

Bruker Kappa DUO APEXII diffractometer	3032 independent reflections
Radiation source: fine-focus sealed tube	2764 reflections with I > 2σ(I)
graphite	Rint = 0.030
0.5° φ scans and ω	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −13→13
Tmin = 0.931, Tmax = 0.995	k = −7→7
20624 measured reflections	l = −27→27

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0488P)2 + 0.1593P] where P = (Fo2 + 2Fc2)/3
3032 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.21 e Å−3
1 restraint	Δρmin = −0.19 e Å−3

Experimental. Half sphere of data collected using the Bruker SAINT software package. Crystal to detector distance = 30 mm; combination of φ and ω scans of 0.5°, 50 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	0.59208 (12)	0.2130 (3)	0.07345 (6)	0.0400 (3)
O2	0.53131 (12)	−0.1159 (3)	0.15604 (6)	0.0370 (3)
O3	1.13983 (13)	0.2008 (3)	0.41963 (6)	0.0382 (3)
O4	1.06894 (12)	0.5827 (3)	0.43713 (6)	0.0371 (3)
N1	1.07939 (12)	0.4482 (3)	0.28290 (6)	0.0250 (3)
C1	0.99153 (14)	0.5106 (3)	0.22148 (7)	0.0248 (3)
H1	0.9572	0.6819	0.2252	0.030*
C2	0.86750 (14)	0.3416 (3)	0.20811 (7)	0.0241 (3)
C3	0.78789 (15)	0.3561 (3)	0.14696 (7)	0.0290 (3)
H3	0.8117	0.4713	0.1158	0.035*
C4	0.67576 (15)	0.2054 (4)	0.13156 (7)	0.0290 (3)
C5	0.64159 (15)	0.0305 (3)	0.17670 (7)	0.0278 (3)
C6	0.71774 (15)	0.0206 (3)	0.23736 (7)	0.0261 (3)
H6	0.6943	−0.0953	0.2684	0.031*
C7	0.82981 (14)	0.1801 (3)	0.25388 (7)	0.0238 (3)
C8	0.90596 (15)	0.1782 (3)	0.32152 (7)	0.0262 (3)
H8A	0.9673	0.0336	0.3267	0.031*
H8B	0.8390	0.1647	0.3536	0.031*
C9	0.99109 (14)	0.4091 (3)	0.33493 (7)	0.0246 (3)
H9	0.9278	0.5523	0.3364	0.030*
C10	1.07737 (14)	0.3815 (4)	0.40099 (7)	0.0279 (3)
C11	1.1481 (2)	0.5762 (5)	0.50083 (9)	0.0495 (5)
H11A	1.1357	0.7303	0.5236	0.074*
H11B	1.2459	0.5541	0.4961	0.074*
H11C	1.1165	0.4397	0.5259	0.074*
C12	1.17749 (15)	0.6521 (3)	0.29833 (8)	0.0291 (3)
H12A	1.1310	0.7808	0.3213	0.035*
H12B	1.1998	0.7234	0.2569	0.035*
C13	1.31095 (14)	0.5860 (3)	0.33944 (7)	0.0270 (3)
C14	1.38533 (17)	0.3781 (4)	0.32668 (9)	0.0355 (4)
H14	1.3478	0.2647	0.2945	0.043*
C15	1.51460 (19)	0.3358 (4)	0.36092 (11)	0.0469 (5)
H15	1.5656	0.1948	0.3516	0.056*
C16	1.56899 (19)	0.4983 (5)	0.40837 (11)	0.0501 (5)
H16	1.6573	0.4691	0.4317	0.060*
C17	1.4954 (2)	0.7017 (5)	0.42181 (10)	0.0482 (5)
H17	1.5325	0.8125	0.4547	0.058*
C18	1.36621 (17)	0.7465 (4)	0.38741 (9)	0.0369 (4)
H18	1.3158	0.8879	0.3969	0.044*
C19	1.07526 (15)	0.4993 (3)	0.16403 (8)	0.0280 (3)
C20	1.16294 (16)	0.3043 (3)	0.15664 (8)	0.0322 (4)
H20	1.1761	0.1814	0.1893	0.039*
C21	1.23198 (19)	0.2875 (4)	0.10159 (9)	0.0409 (4)
H21	1.2937	0.1558	0.0973	0.049*
C22	1.2103 (2)	0.4635 (5)	0.05320 (10)	0.0481 (5)
H22	1.2556	0.4504	0.0152	0.058*
C23	1.1231 (2)	0.6574 (5)	0.06006 (10)	0.0489 (5)
H23	1.1079	0.7772	0.0267	0.059*
C24	1.05718 (18)	0.6783 (4)	0.11589 (9)	0.0380 (4)
H24	0.9997	0.8153	0.1211	0.046*
C25	0.60475 (19)	0.4241 (4)	0.03433 (8)	0.0400 (4)
H25A	0.5409	0.4110	−0.0059	0.060*
H25B	0.6994	0.4361	0.0236	0.060*
H25C	0.5827	0.5705	0.0584	0.060*
C26	0.4896 (2)	−0.2845 (4)	0.20218 (9)	0.0442 (5)
H26A	0.4106	−0.3792	0.1821	0.066*
H26B	0.4636	−0.1948	0.2398	0.066*
H26C	0.5660	−0.3957	0.2164	0.066*

	U11	U22	U33	U12	U13	U23
O1	0.0368 (6)	0.0521 (9)	0.0288 (5)	−0.0133 (7)	−0.0052 (4)	0.0025 (6)
O2	0.0323 (6)	0.0430 (8)	0.0351 (6)	−0.0161 (6)	0.0015 (5)	−0.0048 (6)
O3	0.0354 (6)	0.0417 (8)	0.0358 (6)	0.0060 (6)	−0.0023 (5)	0.0019 (6)
O4	0.0308 (6)	0.0452 (8)	0.0345 (6)	0.0012 (6)	0.0007 (5)	−0.0165 (6)
N1	0.0212 (5)	0.0238 (7)	0.0298 (6)	−0.0033 (5)	0.0022 (4)	−0.0016 (5)
C1	0.0225 (6)	0.0217 (7)	0.0303 (7)	−0.0023 (6)	0.0035 (5)	−0.0001 (6)
C2	0.0204 (6)	0.0245 (8)	0.0276 (7)	−0.0022 (6)	0.0039 (5)	−0.0023 (6)
C3	0.0267 (6)	0.0321 (9)	0.0283 (7)	−0.0059 (7)	0.0041 (5)	0.0028 (7)
C4	0.0247 (6)	0.0364 (9)	0.0257 (7)	−0.0032 (7)	0.0018 (5)	−0.0022 (7)
C5	0.0232 (6)	0.0307 (9)	0.0301 (7)	−0.0066 (6)	0.0059 (5)	−0.0064 (7)
C6	0.0251 (6)	0.0262 (8)	0.0281 (7)	−0.0040 (6)	0.0072 (5)	−0.0010 (6)
C7	0.0213 (6)	0.0250 (7)	0.0257 (6)	−0.0006 (6)	0.0046 (5)	−0.0027 (6)
C8	0.0241 (6)	0.0280 (8)	0.0265 (6)	−0.0014 (6)	0.0030 (5)	0.0002 (7)
C9	0.0211 (6)	0.0251 (8)	0.0272 (6)	0.0028 (6)	0.0012 (5)	−0.0044 (6)
C10	0.0211 (6)	0.0339 (9)	0.0291 (7)	−0.0001 (6)	0.0046 (5)	−0.0046 (7)
C11	0.0402 (9)	0.0716 (16)	0.0348 (9)	−0.0054 (11)	−0.0031 (7)	−0.0192 (11)
C12	0.0232 (7)	0.0226 (8)	0.0403 (8)	−0.0013 (6)	−0.0003 (6)	−0.0016 (7)
C13	0.0211 (6)	0.0266 (8)	0.0338 (7)	−0.0012 (6)	0.0054 (5)	0.0013 (7)
C14	0.0328 (8)	0.0311 (9)	0.0430 (9)	0.0040 (7)	0.0056 (7)	−0.0025 (8)
C15	0.0338 (9)	0.0422 (12)	0.0649 (13)	0.0124 (9)	0.0070 (8)	0.0056 (10)
C16	0.0280 (8)	0.0554 (13)	0.0630 (12)	0.0030 (9)	−0.0095 (8)	0.0129 (11)
C17	0.0363 (9)	0.0501 (13)	0.0539 (11)	−0.0081 (10)	−0.0119 (8)	−0.0049 (11)
C18	0.0279 (7)	0.0333 (10)	0.0481 (9)	−0.0010 (7)	−0.0003 (7)	−0.0072 (8)
C19	0.0240 (7)	0.0270 (8)	0.0332 (7)	−0.0086 (6)	0.0047 (5)	−0.0008 (7)
C20	0.0303 (7)	0.0307 (9)	0.0360 (8)	−0.0057 (7)	0.0059 (6)	−0.0047 (7)
C21	0.0372 (9)	0.0410 (11)	0.0464 (10)	−0.0078 (8)	0.0129 (7)	−0.0133 (9)
C22	0.0468 (10)	0.0592 (14)	0.0421 (9)	−0.0157 (11)	0.0204 (8)	−0.0061 (10)
C23	0.0505 (11)	0.0531 (14)	0.0451 (10)	−0.0139 (10)	0.0135 (8)	0.0131 (10)
C24	0.0352 (8)	0.0349 (10)	0.0448 (9)	−0.0070 (8)	0.0085 (7)	0.0067 (8)
C25	0.0412 (9)	0.0465 (11)	0.0308 (8)	0.0035 (9)	−0.0019 (7)	0.0022 (9)
C26	0.0437 (9)	0.0465 (12)	0.0438 (9)	−0.0241 (10)	0.0108 (7)	−0.0077 (10)

O1—C4	1.3705 (17)	C12—H12A	0.9900
O1—C25	1.423 (3)	C12—H12B	0.9900
O2—C5	1.3688 (18)	C13—C18	1.384 (2)
O2—C26	1.422 (2)	C13—C14	1.391 (2)
O3—C10	1.200 (2)	C14—C15	1.391 (3)
O4—C10	1.338 (2)	C14—H14	0.9500
O4—C11	1.446 (2)	C15—C16	1.382 (3)
N1—C9	1.4755 (18)	C15—H15	0.9500
N1—C12	1.480 (2)	C16—C17	1.371 (3)
N1—C1	1.4849 (18)	C16—H16	0.9500
C1—C2	1.523 (2)	C17—C18	1.394 (2)
C1—C19	1.525 (2)	C17—H17	0.9500
C1—H1	1.0000	C18—H18	0.9500
C2—C7	1.378 (2)	C19—C20	1.388 (2)
C2—C3	1.405 (2)	C19—C24	1.392 (3)
C3—C4	1.377 (2)	C20—C21	1.396 (2)
C3—H3	0.9500	C20—H20	0.9500
C4—C5	1.405 (2)	C21—C22	1.386 (3)
C5—C6	1.381 (2)	C21—H21	0.9500
C6—C7	1.409 (2)	C22—C23	1.378 (4)
C6—H6	0.9500	C22—H22	0.9500
C7—C8	1.5035 (19)	C23—C24	1.395 (3)
C8—C9	1.519 (2)	C23—H23	0.9500
C8—H8A	0.9900	C24—H24	0.9500
C8—H8B	0.9900	C25—H25A	0.9800
C9—C10	1.524 (2)	C25—H25B	0.9800
C9—H9	1.0000	C25—H25C	0.9800
C11—H11A	0.9800	C26—H26A	0.9800
C11—H11B	0.9800	C26—H26B	0.9800
C11—H11C	0.9800	C26—H26C	0.9800
C12—C13	1.513 (2)
C4—O1—C25	116.09 (14)	C13—C12—H12A	108.4
C5—O2—C26	116.63 (13)	N1—C12—H12B	108.4
C10—O4—C11	115.28 (16)	C13—C12—H12B	108.4
C9—N1—C12	111.91 (12)	H12A—C12—H12B	107.4
C9—N1—C1	109.20 (11)	C18—C13—C14	119.07 (15)
C12—N1—C1	107.71 (12)	C18—C13—C12	119.12 (16)
N1—C1—C2	112.42 (12)	C14—C13—C12	121.58 (15)
N1—C1—C19	110.39 (11)	C15—C14—C13	120.17 (18)
C2—C1—C19	108.97 (12)	C15—C14—H14	119.9
N1—C1—H1	108.3	C13—C14—H14	119.9
C2—C1—H1	108.3	C16—C15—C14	120.2 (2)
C19—C1—H1	108.3	C16—C15—H15	119.9
C7—C2—C3	119.35 (13)	C14—C15—H15	119.9
C7—C2—C1	122.51 (13)	C17—C16—C15	119.92 (17)
C3—C2—C1	118.13 (13)	C17—C16—H16	120.0
C4—C3—C2	120.88 (15)	C15—C16—H16	120.0
C4—C3—H3	119.6	C16—C17—C18	120.29 (19)
C2—C3—H3	119.6	C16—C17—H17	119.9
O1—C4—C3	123.96 (15)	C18—C17—H17	119.9
O1—C4—C5	116.04 (14)	C13—C18—C17	120.35 (19)
C3—C4—C5	119.99 (13)	C13—C18—H18	119.8
O2—C5—C6	125.36 (15)	C17—C18—H18	119.8
O2—C5—C4	115.59 (13)	C20—C19—C24	119.15 (15)
C6—C5—C4	119.04 (14)	C20—C19—C1	121.00 (15)
C5—C6—C7	120.93 (14)	C24—C19—C1	119.72 (16)
C5—C6—H6	119.5	C19—C20—C21	120.48 (18)
C7—C6—H6	119.5	C19—C20—H20	119.8
C2—C7—C6	119.65 (13)	C21—C20—H20	119.8
C2—C7—C8	120.07 (13)	C22—C21—C20	119.81 (19)
C6—C7—C8	120.27 (13)	C22—C21—H21	120.1
C7—C8—C9	111.28 (13)	C20—C21—H21	120.1
C7—C8—H8A	109.4	C23—C22—C21	120.08 (17)
C9—C8—H8A	109.4	C23—C22—H22	120.0
C7—C8—H8B	109.4	C21—C22—H22	120.0
C9—C8—H8B	109.4	C22—C23—C24	120.2 (2)
H8A—C8—H8B	108.0	C22—C23—H23	119.9
N1—C9—C8	110.08 (12)	C24—C23—H23	119.9
N1—C9—C10	111.08 (11)	C19—C24—C23	120.3 (2)
C8—C9—C10	108.24 (14)	C19—C24—H24	119.9
N1—C9—H9	109.1	C23—C24—H24	119.9
C8—C9—H9	109.1	O1—C25—H25A	109.5
C10—C9—H9	109.1	O1—C25—H25B	109.5
O3—C10—O4	124.06 (14)	H25A—C25—H25B	109.5
O3—C10—C9	125.08 (16)	O1—C25—H25C	109.5
O4—C10—C9	110.79 (14)	H25A—C25—H25C	109.5
O4—C11—H11A	109.5	H25B—C25—H25C	109.5
O4—C11—H11B	109.5	O2—C26—H26A	109.5
H11A—C11—H11B	109.5	O2—C26—H26B	109.5
O4—C11—H11C	109.5	H26A—C26—H26B	109.5
H11A—C11—H11C	109.5	O2—C26—H26C	109.5
H11B—C11—H11C	109.5	H26A—C26—H26C	109.5
N1—C12—C13	115.70 (14)	H26B—C26—H26C	109.5
N1—C12—H12A	108.4
C9—N1—C1—C2	−46.18 (17)	C1—N1—C9—C10	−171.68 (14)
C12—N1—C1—C2	−167.91 (12)	C7—C8—C9—N1	−52.11 (16)
C9—N1—C1—C19	−168.08 (13)	C7—C8—C9—C10	−173.69 (12)
C12—N1—C1—C19	70.19 (16)	C11—O4—C10—O3	3.4 (2)
N1—C1—C2—C7	10.8 (2)	C11—O4—C10—C9	−179.57 (14)
C19—C1—C2—C7	133.55 (15)	N1—C9—C10—O3	−76.9 (2)
N1—C1—C2—C3	−170.35 (13)	C8—C9—C10—O3	44.1 (2)
C19—C1—C2—C3	−47.65 (19)	N1—C9—C10—O4	106.16 (15)
C7—C2—C3—C4	−2.2 (2)	C8—C9—C10—O4	−132.88 (14)
C1—C2—C3—C4	178.97 (15)	C9—N1—C12—C13	85.52 (16)
C25—O1—C4—C3	−14.8 (2)	C1—N1—C12—C13	−154.45 (13)
C25—O1—C4—C5	165.37 (15)	N1—C12—C13—C18	−140.47 (16)
C2—C3—C4—O1	178.63 (16)	N1—C12—C13—C14	45.0 (2)
C2—C3—C4—C5	−1.5 (3)	C18—C13—C14—C15	−1.3 (3)
C26—O2—C5—C6	2.6 (2)	C12—C13—C14—C15	173.24 (17)
C26—O2—C5—C4	−176.36 (16)	C13—C14—C15—C16	0.9 (3)
O1—C4—C5—O2	2.0 (2)	C14—C15—C16—C17	0.1 (3)
C3—C4—C5—O2	−177.87 (15)	C15—C16—C17—C18	−0.5 (3)
O1—C4—C5—C6	−177.02 (15)	C14—C13—C18—C17	0.8 (3)
C3—C4—C5—C6	3.1 (2)	C12—C13—C18—C17	−173.86 (17)
O2—C5—C6—C7	180.00 (15)	C16—C17—C18—C13	0.1 (3)
C4—C5—C6—C7	−1.1 (2)	N1—C1—C19—C20	45.6 (2)
C3—C2—C7—C6	4.2 (2)	C2—C1—C19—C20	−78.34 (17)
C1—C2—C7—C6	−177.02 (14)	N1—C1—C19—C24	−138.67 (15)
C3—C2—C7—C8	−174.44 (14)	C2—C1—C19—C24	97.42 (18)
C1—C2—C7—C8	4.3 (2)	C24—C19—C20—C21	−0.1 (2)
C5—C6—C7—C2	−2.6 (2)	C1—C19—C20—C21	175.66 (15)
C5—C6—C7—C8	176.03 (14)	C19—C20—C21—C22	−1.6 (3)
C2—C7—C8—C9	16.00 (19)	C20—C21—C22—C23	1.4 (3)
C6—C7—C8—C9	−162.63 (14)	C21—C22—C23—C24	0.5 (3)
C12—N1—C9—C8	−172.39 (12)	C20—C19—C24—C23	2.0 (3)
C1—N1—C9—C8	68.45 (16)	C1—C19—C24—C23	−173.83 (16)
C12—N1—C9—C10	−52.52 (18)	C22—C23—C24—C19	−2.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O3i	0.95	2.51	3.445 (2)	168
C25—H25A···O1ii	0.98	2.43	3.183 (2)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯O3i	0.95	2.51	3.445 (2)	168
C25—H25A⋯O1ii	0.98	2.43	3.183 (2)	133

Symmetry codes: (i) ; (ii) .