(1R,3S)-Methyl 2-benzyl-6,7-dimeth­oxy-1-phenyl-1,2,3,4-tetra­hydro­isoquinoline-3-carboxyl­ate

Naicker, T.; McKay, M.; Govender, T.; Kruger, H.G.; Maguire, G.E.M.

doi:10.1107/S1600536809050521

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3278

doi:10.1107/S1600536809050521

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(1R,3S)-Methyl 2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylate

Tricia Naicker,^a Michael McKay,^a Thavendran Govender,^b ^* Hendrik G. Kruger ^a and Glenn E. M. Maguire ^a

^aSchool of Chemistry, University of KwaZulu-Natal, Durban 4000, South Africa, and ^bSchool of Pharmacy and Pharmacology, University of KwaZulu-Natal, Durban 4000, South Africa
^*Correspondence e-mail: govenderthav@ukzn.ac.za

(Received 20 November 2009; accepted 24 November 2009; online 28 November 2009)

In the title compound, C₂₆H₂₇NO₄, 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 molecules 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_r = 417.49
Triclinic, P 1
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[F² > 2σ(F²)] = 0.028
wR(F²) = 0.077
S = 1.07
3561 reflections
281 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1483 Friedel pairs
Flack parameter: −0.01 (14)

Table 1
C—H⋯π interaction (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19A⋯Cgⁱ	0.98	2.82	3.639 (2)	148
Symmetry code: (i) x+1, y+1, z-1. Cg is the centroid of the C21–C26 ring.

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.

Supporting information

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

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

checkCIF report

Comment top

The title compound (2, Scheme 1) is a precursor in the synthesis of novel chiral ligands containing a tetrahydroisoquinoline backbone. We have recently reported the use of these ligands as successful catalysts for transfer hydrogenations reactions (Chakka et al., 2009).

Compound 2 was derived from commercially available L-DOPA and benzaldehyde. Diastereomers formed during the first step of the synthesis were separated to yield subsequent derivatives and the title compound and with the stereochemistry as illustrated in Figure 1. The absolute stereochemistry was confirmed to be R,S at C1 and C9 positions respectively.

From the crystal structure it is evident that the N-containing six membered ring assumes a half boat conformation (Figure 1). This differs from an analogous structure which assumes a half chair conformation (Aubry et al., 2006 and Alberch et al., 2004). A possible reason for this change in conformation could be either the introduction of a substitutent on the nitrogen or the trans position of the phenyl ring at the C1 position.

The molecule exhibits various intermolecular short contacts i.e. between the methyl ester hydrogen (H11C) and phenyl ring (C14) of a neighbouring molecule; H15 to C6 and C7 and H24 to C14 and C15.

The methoxy groups display different interactions. The first methoxy group at C4 position displays one interaction between H18B and O2, which is the ether oxygen of the other methoxy group. The second methoxy group at C5 position displays three interactions; the first being the above mentioned interaction with H18B and O2, the second being a short contact between O2 and H25, and the third being another CH-π the interaction between H19A and C25. The atoms involved in these short contacts are shown in Figure 2.

Related literature top

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

Experimental top

To a solution of 1 (Scheme 1) (500 mg, 1.52 mmol) in acetonitrile (20 ml), solid K₂CO₃(635 mg, 4.58 mmol) was added followed by benzyl bromide (286 mg, 1.67 mmol) at ambient temperature. There after the reaction mixture was refluxed for 3 h. Completion of the reaction was monitored with TLC using hexane/ethyl acetate (60:40, R_f 1/2). The solvent was evaporated and 30 ml of ethylacetate was added, washed with 2 × 10 ml of water, the organic layer was separated, and dried over anhydrous MgSO₄. The solvent was evaporated under reduced pressure to afford crude product, which was purified by column chromatography using hexane/ethyl acetate (60:40) as the eluent to yield pure benzyl ester 2 (0.44 g, 90%) as a white solid.

¹H NMR (400 MHz/CDCl₃): δ = 7.44 (d, J = 1.16 Hz, 2H), 7.32–7.10 (m, 14H), 7.0–6.88 (m, 6H), 6.69 (s, 1H), 6.38 (s, 1H), 4.74 (s,1H), 4.21 (d, J = 13.60 Hz, 1H), 4.14 (q, J = 3.70, 12.74 Hz, 1H), 3.89 (s, 3H), 3.72 (s, 3H), 3.57 (s, 1H), 3.30–3.18 (m, 2H), 2.60 (dd, J = 3.60, 16.48 Hz, 1H).

Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of 2 in dichloromethane at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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 for Windows (Farrugia, 1997).

Figures top

	Fig. 1. Molecular structure of the title compound 2 showing numbering scheme. Displacement elipsoids are drawn at the 30% probability level. Hydrogen atoms are omitted for clarity.
	Fig. 2. Intermolecular short contact interactions present in the crystal structure of the title compound 2. The atoms involved in the interactions (as discussed) are labelled. different interactions displayed by methoxy groups. Displacement ellipsoids are drawn at the 30% probability level, and the hydrogen atoms appear as speheres of arbitrary radii.
	Fig. 3. The formation of the title compound.

(1R,3S)-Methyl 2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4- tetrahydroisoquinoline-3-carboxylate top

Crystal data top

C₂₆H₂₇NO₄	Z = 1
M_r = 417.49	F(000) = 222
Triclinic, P1	D_x = 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 = 559.05 (2) Å³	0.22 × 0.12 × 0.08 mm

Data collection top

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

Refinement top

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(F_o²) + (0.0475P)² + 0.0785P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.077	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.16 e Å⁻³
3561 reflections	Δρ_min = −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	Absolute structure parameter: −0.01 (14)

Crystal data top

C₂₆H₂₇NO₄	γ = 75.737 (1)°
M_r = 417.49	V = 559.05 (2) Å³
Triclinic, P1	Z = 1
a = 6.0199 (1) Å	Cu Kα radiation
b = 9.2592 (2) Å	µ = 0.67 mm⁻¹
c = 11.0429 (2) Å	T = 173 K
α = 73.365 (1)°	0.22 × 0.12 × 0.08 mm
β = 74.694 (1)°

Data collection top

Bruker Kappa Duo APEXII diffractometer	3561 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	3536 reflections with I > 2σ(I)
T_min = 0.692, T_max = 0.753	R_int = 0.012
7546 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.077	Δρ_max = 0.16 e Å⁻³
S = 1.07	Δρ_min = −0.16 e Å⁻³
3561 reflections	Absolute structure: Flack (1983), 1483 Friedel pairs
281 parameters	Absolute structure parameter: −0.01 (14)
3 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) x+1, y+1, z−1.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₇NO₄
M_r	417.49
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.0199 (1), 9.2592 (2), 11.0429 (2)
α, β, γ (°)	73.365 (1), 74.694 (1), 75.737 (1)
V (Å³)	559.05 (2)
Z	1
Radiation type	Cu Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.22 × 0.12 × 0.08

Data collection
Diffractometer	Bruker Kappa Duo APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.692, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	7546, 3561, 3536
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.077, 1.07
No. of reflections	3561
No. of parameters	281
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16
Absolute structure	Flack (1983), 1483 Friedel pairs
Absolute structure parameter	−0.01 (14)

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and X-SEED (Barbour, 2001), ORTEP-3 (Farrugia, 1997), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) x+1, y+1, z−1.

Acknowledgements

The authors wish to thank Dr Hong Su of the Chemistry Department at the University of Cape Town for his assistance with the crystallographic data collection.

References

Alberch, L., Bailey, P. D., Clingan, P. D., Mills, T. J., Price, R. A. & Pritchard, R. G. (2004). Eur. J. Org. Chem. 9, 1887–1890. Web of Science CSD CrossRef Google Scholar
Aubry, S., Pellet-Rostaing, S., Faure, R. & Lemaire, M. (2006). J. Heterocycl. Chem. 43, 139–148. CrossRef CAS Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chakka, S., Andersson, P. G., Govender, T., Kruger, H. G. & Maguire, G. E. M. (2009). Eur. J. Org. Chem.. In the press. doi:10.1002/EJOC.200. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(1R,3S)-Methyl 2-benzyl-6,7-dimeth­­oxy-1-phenyl-1,2,3,4-tetra­hydro­iso­quinoline-3-carboxyl­ate

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Experimental

Crystal data

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Refinement

Supporting information

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organic compounds

(1R,3S)-Methyl 2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylate