(1R,3S)-N-Benzhydryl-2-benzyl-6,7-dimeth­oxy-1-phenyl-1,2,3,4-tetra­hydro­isoquinoline-3-carbothio­amide

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

doi:10.1107/S1600536811049324

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3441

https://doi.org/10.1107/S1600536811049324

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(1R,3S)-N-Benzhydryl-2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carbothioamide

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

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

(Received 4 November 2011; accepted 18 November 2011; online 25 November 2011)

The title compound, C₃₈H₃₆N₂O₂S, has a heterocyclic ring that assumes a half-chair conformation. The phenyl rings of neighbouring molecules align forming alternating chains parallel to [100] within the crystal packing. The absolute stereochemistry of the crystal was confirmed to be R,S at the 1- and 3-positions, respectively, by proton NMR spectroscopy. A single intramolecular N—H⋯N hydrogen bond is observed.

Related literature

For background to chiral organocatalysts bearing a tetrahydroisoquinoline framework and for related structures, see: Naicker et al. (2010 , 2011a ,b ).

Experimental

Crystal data

C₃₈H₃₆N₂O₂S
M_r = 584.75
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.0463 (1) Å
b = 17.6687 (2) Å
c = 19.6178 (2) Å
V = 3135.64 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 173 K
0.34 × 0.32 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer
7464 measured reflections
7464 independent reflections
6545 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.090
S = 1.06
7464 reflections
394 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 3271 Friedel pairs
Flack parameter: −0.07 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯N1	0.903 (17)	2.139 (16)	2.6548 (15)	115.4 (12)

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811049324/hg5134sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049324/hg5134Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811049324/hg5134Isup3.cml

checkCIF report

Comment top

Chiral organocatalysts bearing a tetrahydroisoquinoline (TIQ) framework have proven to be very successful by our research group (Naicker et al., 2010 and 2011a). The title compound (Fig. 1) is a precursor in the synthesis of these novel chiral organocatalysts. The crystal structure contains a thioamide moiety at the C10 position making it the first example in this class to be reported.

The absolute stereochemistry of the molecule was confirmed to be R,S at C1 and C9 positions respectively by proton NMR spectroscopy.

The N-containing six membered ring assumes a half chair conformation [Q=0.5212 (12) Å, θ= 50.52 (14)° and φ=325.8 (18)°] similar to an analogous structure which has a methyl ester at the C10 position (Naicker et al., 2011b). This heterocyclic ring shape affects the position of the thioamide moiety relative to the phenyl ring at the C1 position. The torsion angle for C1—N1—C9—C10 is -157.6 (1)°. Also, in the analogous structure the torsion angle between C8—N1—C9—C10 is 44.1 (2)° while in the title structure this angle is -18.3 (2)°. This is probably due to the C═S bond which adopts a more planar orientation relative to the TIQ backbone as compared to the C═O bond orientation previously reported in this family of molecules (Naicker et al., 2011b). In addition, the N-benzyl and phenyl ring at C1 exist in a trans orientation along the N1—C9 bond with a dihedral angle of -153.3 (1)°.

The title compound contains four phenyl rings however, no intermolecular C—H···π or π···π interactions are evident. A single intramolecular hydrogen bond between atoms N2—H1N···N1 can be observed. The molecules within the crystal structure line up such that the phenyl rings face each other, this forms alternating chains parallel to the [100] plane (Fig. 2).

Related literature top

For background to chiral organocatalysts bearing a tetrahydroisoquinoline framework and for related structures, see: Naicker et al. (2010, 2011a,b).

Experimental top

To a solution of (1R,3S)-N-benzhydryl-2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxamide (0.1 g, 0.02 mmol) in dry THF (20 ml), Lawssons reagent (0.06 g, 0.15 mmol) was added. The mixture was allowed to stir at 50 °C for 16 h under a nitrogen atmosphere. Thereafter the solvent was evaporated in vacuo and the residue purified using silica column chromatography (hexane: ethyl acetate, 50:50, R_f = 0.8) to yield the pure product (0.1 g, 90%) as a yellow solid. M.p. = 458 K

Recrystallization from ethyl acetate at room temperature afforded crystals suitable for X-ray analysis.

Structure description top

The absolute stereochemistry of the molecule was confirmed to be R,S at C1 and C9 positions respectively by proton NMR spectroscopy.

For background to chiral organocatalysts bearing a tetrahydroisoquinoline framework and for related structures, see: Naicker et al. (2010, 2011a,b).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen atoms have been omitted for clarity.
	Fig. 2. A partial projection of the title compound, viewed along the [100] plane.

(1R,3S)-N-Benzhydryl-2-benzyl-6,7-dimethoxy-1-phenyl- 1,2,3,4-tetrahydroisoquinoline-3-carbothioamide top

Crystal data top

C₃₈H₃₆N₂O₂S	D_x = 1.239 Mg m⁻³
M_r = 584.75	Melting point: 458 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7464 reflections
a = 9.0463 (1) Å	θ = 2.4–27.9°
b = 17.6687 (2) Å	µ = 0.14 mm⁻¹
c = 19.6178 (2) Å	T = 173 K
V = 3135.64 (6) Å³	Block, colourless
Z = 4	0.34 × 0.32 × 0.30 mm
F(000) = 1240

Data collection top

Nonius KappaCCD diffractometer	6545 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.013
Graphite monochromator	θ_max = 27.9°, θ_min = 2.4°
1.2° φ scans and ω scans	h = −11→11
7464 measured reflections	k = −23→23
7464 independent reflections	l = −25→25

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0573P)² + 0.1291P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
7464 reflections	Δρ_max = 0.19 e Å⁻³
394 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 3271 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.07 (5)

Crystal data top

C₃₈H₃₆N₂O₂S	V = 3135.64 (6) Å³
M_r = 584.75	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.0463 (1) Å	µ = 0.14 mm⁻¹
b = 17.6687 (2) Å	T = 173 K
c = 19.6178 (2) Å	0.34 × 0.32 × 0.30 mm

Data collection top

Nonius KappaCCD diffractometer	6545 reflections with I > 2σ(I)
7464 measured reflections	R_int = 0.013
7464 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	Δρ_max = 0.19 e Å⁻³
S = 1.06	Δρ_min = −0.25 e Å⁻³
7464 reflections	Absolute structure: Flack (1983), 3271 Friedel pairs
394 parameters	Absolute structure parameter: −0.07 (5)
0 restraints

Special details top

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
S1	0.56498 (4)	0.31046 (3)	0.215098 (18)	0.04475 (11)
O1	1.39454 (9)	0.35968 (6)	−0.01266 (5)	0.0361 (2)
O2	1.15098 (11)	0.39105 (6)	−0.07511 (5)	0.0412 (3)
N1	0.98038 (11)	0.23680 (6)	0.21258 (5)	0.0254 (2)
H1N	0.8629 (19)	0.2485 (9)	0.3066 (8)	0.038 (4)*
N2	0.76795 (13)	0.26373 (7)	0.30274 (5)	0.0300 (2)
C1	1.12804 (13)	0.26381 (7)	0.19152 (6)	0.0258 (2)
H1	1.1954	0.2189	0.1909	0.031*
C2	1.12788 (13)	0.29751 (7)	0.11981 (6)	0.0252 (2)
C3	1.26341 (13)	0.31006 (7)	0.08659 (6)	0.0258 (2)
H3	1.3530	0.2963	0.1087	0.031*
C4	1.26841 (14)	0.34205 (7)	0.02236 (6)	0.0277 (3)
C5	1.13534 (14)	0.36025 (8)	−0.01141 (6)	0.0295 (3)
C6	1.00254 (14)	0.34772 (7)	0.02100 (6)	0.0296 (3)
H6	0.9130	0.3605	−0.0015	0.036*
C7	0.99719 (13)	0.31627 (7)	0.08690 (6)	0.0263 (2)
C8	0.84760 (13)	0.30508 (8)	0.12010 (6)	0.0281 (3)
H8A	0.7988	0.2595	0.1012	0.034*
H8B	0.7836	0.3494	0.1111	0.034*
C9	0.87122 (13)	0.29575 (7)	0.19647 (6)	0.0254 (3)
H9	0.9174	0.3443	0.2118	0.030*
C10	0.73303 (14)	0.28667 (7)	0.24034 (6)	0.0273 (3)
C11	0.66652 (15)	0.25452 (8)	0.36016 (6)	0.0307 (3)
H11	0.5659	0.2705	0.3447	0.037*
C12	0.66026 (16)	0.17078 (8)	0.37684 (7)	0.0365 (3)
C13	0.57712 (19)	0.12406 (10)	0.33433 (10)	0.0513 (4)
H13	0.5187	0.1457	0.2991	0.062*
C14	0.5791 (2)	0.04658 (12)	0.34297 (13)	0.0717 (6)
H14	0.5222	0.0151	0.3138	0.086*
C15	0.6627 (3)	0.01513 (11)	0.39351 (13)	0.0783 (7)
H15	0.6639	−0.0383	0.3991	0.094*
C16	0.7452 (3)	0.05997 (12)	0.43635 (10)	0.0724 (7)
H16	0.8025	0.0375	0.4715	0.087*
C17	0.7449 (2)	0.13879 (10)	0.42834 (8)	0.0519 (4)
H17	0.8020	0.1699	0.4578	0.062*
C18	0.71133 (15)	0.30534 (8)	0.41918 (7)	0.0355 (3)
C19	0.62417 (18)	0.30449 (10)	0.47767 (7)	0.0461 (4)
H19	0.5398	0.2725	0.4797	0.055*
C20	0.6594 (2)	0.34981 (12)	0.53304 (9)	0.0596 (5)
H20	0.5989	0.3490	0.5726	0.071*
C21	0.7820 (2)	0.39607 (13)	0.53074 (10)	0.0679 (6)
H21	0.8059	0.4270	0.5688	0.081*
C22	0.8697 (2)	0.39761 (14)	0.47359 (11)	0.0721 (6)
H22	0.9541	0.4296	0.4720	0.087*
C23	0.8343 (2)	0.35184 (11)	0.41767 (9)	0.0533 (4)
H23	0.8953	0.3527	0.3783	0.064*
C24	1.18222 (13)	0.31673 (8)	0.24787 (6)	0.0274 (3)
C25	1.21466 (16)	0.28510 (9)	0.31128 (7)	0.0377 (3)
H25	1.2090	0.2318	0.3171	0.045*
C26	1.25474 (18)	0.32987 (11)	0.36556 (7)	0.0494 (4)
H26	1.2770	0.3073	0.4083	0.059*
C27	1.2627 (2)	0.40751 (11)	0.35813 (8)	0.0525 (4)
H27	1.2896	0.4384	0.3957	0.063*
C28	1.23137 (18)	0.43995 (10)	0.29567 (8)	0.0461 (4)
H28	1.2370	0.4933	0.2902	0.055*
C29	1.19146 (15)	0.39432 (8)	0.24068 (7)	0.0347 (3)
H29	1.1704	0.4169	0.1978	0.042*
C30	0.94220 (15)	0.16198 (7)	0.18354 (6)	0.0311 (3)
H30A	0.9619	0.1621	0.1339	0.037*
H30B	0.8356	0.1519	0.1905	0.037*
C31	1.03199 (15)	0.10040 (7)	0.21717 (7)	0.0313 (3)
C32	1.00795 (17)	0.08224 (8)	0.28514 (7)	0.0369 (3)
H32	0.9328	0.1078	0.3099	0.044*
C33	1.09188 (18)	0.02740 (9)	0.31743 (9)	0.0449 (4)
H33	1.0739	0.0154	0.3639	0.054*
C34	1.20184 (17)	−0.00989 (8)	0.28199 (10)	0.0483 (4)
H34	1.2612	−0.0466	0.3044	0.058*
C35	1.22548 (19)	0.00598 (9)	0.21423 (10)	0.0535 (4)
H35	1.2999	−0.0203	0.1896	0.064*
C36	1.13978 (18)	0.06090 (9)	0.18180 (9)	0.0442 (4)
H36	1.1556	0.0713	0.1349	0.053*
C37	1.53137 (14)	0.34969 (9)	0.02154 (7)	0.0368 (3)
H37A	1.5315	0.3794	0.0637	0.055*
H37B	1.6122	0.3667	−0.0080	0.055*
H37C	1.5449	0.2960	0.0325	0.055*
C38	1.01921 (18)	0.40522 (12)	−0.11254 (8)	0.0523 (4)
H38A	0.9625	0.3582	−0.1168	0.078*
H38B	1.0446	0.4240	−0.1580	0.078*
H38C	0.9597	0.4432	−0.0886	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02261 (15)	0.0813 (3)	0.03029 (17)	0.00153 (17)	−0.00103 (14)	0.01267 (18)
O1	0.0218 (4)	0.0640 (6)	0.0226 (4)	−0.0016 (4)	0.0025 (3)	0.0056 (5)
O2	0.0294 (5)	0.0712 (7)	0.0230 (5)	−0.0013 (5)	−0.0009 (4)	0.0162 (5)
N1	0.0222 (5)	0.0317 (5)	0.0222 (5)	0.0003 (4)	0.0004 (4)	0.0019 (4)
N2	0.0229 (5)	0.0445 (6)	0.0227 (5)	0.0020 (5)	0.0021 (4)	0.0030 (4)
C1	0.0216 (6)	0.0343 (6)	0.0215 (6)	0.0009 (5)	−0.0017 (5)	0.0020 (5)
C2	0.0250 (6)	0.0323 (6)	0.0183 (5)	0.0005 (5)	0.0010 (5)	−0.0018 (5)
C3	0.0208 (5)	0.0355 (6)	0.0212 (5)	0.0016 (5)	−0.0012 (5)	−0.0014 (5)
C4	0.0243 (6)	0.0380 (6)	0.0208 (6)	−0.0013 (5)	0.0024 (5)	−0.0020 (5)
C5	0.0281 (6)	0.0423 (7)	0.0180 (5)	−0.0022 (5)	−0.0009 (5)	0.0035 (5)
C6	0.0243 (6)	0.0422 (7)	0.0224 (6)	0.0009 (5)	−0.0038 (5)	0.0040 (5)
C7	0.0231 (6)	0.0353 (6)	0.0204 (5)	−0.0001 (5)	0.0004 (5)	0.0007 (5)
C8	0.0219 (6)	0.0407 (7)	0.0216 (6)	0.0018 (5)	−0.0007 (5)	0.0039 (5)
C9	0.0200 (5)	0.0355 (6)	0.0207 (6)	−0.0001 (5)	−0.0004 (4)	0.0021 (5)
C10	0.0238 (6)	0.0351 (6)	0.0230 (6)	−0.0022 (5)	0.0002 (5)	0.0013 (5)
C11	0.0255 (6)	0.0458 (8)	0.0206 (6)	0.0015 (6)	0.0038 (5)	0.0012 (5)
C12	0.0341 (7)	0.0478 (8)	0.0275 (6)	0.0034 (6)	0.0126 (6)	0.0038 (6)
C13	0.0409 (9)	0.0509 (9)	0.0622 (11)	−0.0062 (7)	0.0103 (8)	−0.0039 (8)
C14	0.0596 (12)	0.0533 (11)	0.1023 (18)	−0.0122 (9)	0.0277 (13)	−0.0074 (12)
C15	0.1006 (17)	0.0443 (10)	0.0899 (16)	0.0067 (11)	0.0567 (15)	0.0114 (11)
C16	0.1033 (17)	0.0658 (12)	0.0480 (10)	0.0370 (13)	0.0324 (12)	0.0247 (10)
C17	0.0691 (11)	0.0576 (9)	0.0289 (7)	0.0223 (9)	0.0124 (7)	0.0087 (7)
C18	0.0349 (7)	0.0471 (8)	0.0244 (6)	0.0062 (6)	−0.0002 (5)	−0.0011 (6)
C19	0.0486 (9)	0.0604 (9)	0.0294 (7)	0.0029 (8)	0.0071 (7)	−0.0055 (7)
C20	0.0639 (11)	0.0822 (13)	0.0326 (8)	0.0110 (10)	0.0034 (8)	−0.0154 (8)
C21	0.0647 (12)	0.0924 (14)	0.0466 (10)	0.0085 (11)	−0.0098 (9)	−0.0324 (10)
C22	0.0525 (11)	0.0978 (15)	0.0660 (13)	−0.0125 (10)	−0.0053 (10)	−0.0334 (12)
C23	0.0420 (9)	0.0742 (11)	0.0438 (9)	−0.0045 (8)	0.0056 (7)	−0.0170 (8)
C24	0.0192 (5)	0.0433 (7)	0.0198 (6)	0.0003 (5)	0.0000 (4)	−0.0005 (5)
C25	0.0329 (7)	0.0549 (8)	0.0254 (6)	−0.0070 (6)	−0.0057 (6)	0.0076 (6)
C26	0.0445 (9)	0.0813 (12)	0.0225 (6)	−0.0125 (8)	−0.0070 (6)	0.0035 (7)
C27	0.0495 (9)	0.0759 (12)	0.0322 (8)	−0.0116 (9)	−0.0053 (7)	−0.0157 (8)
C28	0.0455 (8)	0.0502 (8)	0.0427 (9)	−0.0019 (7)	−0.0066 (7)	−0.0112 (7)
C29	0.0319 (7)	0.0438 (7)	0.0284 (7)	0.0000 (6)	−0.0050 (5)	−0.0002 (6)
C30	0.0314 (6)	0.0367 (7)	0.0252 (6)	−0.0026 (5)	−0.0017 (5)	−0.0004 (5)
C31	0.0324 (7)	0.0307 (6)	0.0307 (6)	−0.0050 (5)	−0.0009 (5)	−0.0019 (5)
C32	0.0453 (8)	0.0353 (7)	0.0300 (7)	0.0008 (6)	−0.0027 (6)	−0.0012 (6)
C33	0.0562 (10)	0.0364 (7)	0.0421 (8)	−0.0038 (7)	−0.0116 (8)	0.0052 (6)
C34	0.0419 (8)	0.0338 (7)	0.0693 (11)	−0.0036 (6)	−0.0122 (8)	0.0103 (7)
C35	0.0433 (9)	0.0411 (8)	0.0762 (12)	0.0069 (7)	0.0152 (9)	0.0040 (8)
C36	0.0484 (9)	0.0402 (7)	0.0439 (8)	0.0014 (7)	0.0117 (7)	0.0035 (7)
C37	0.0231 (6)	0.0587 (9)	0.0285 (6)	0.0000 (6)	0.0012 (5)	0.0009 (6)
C38	0.0369 (8)	0.0890 (12)	0.0310 (7)	−0.0062 (8)	−0.0069 (6)	0.0259 (8)

Geometric parameters (Å, º) top

S1—C10	1.6532 (13)	C18—C23	1.383 (2)
O1—C4	1.3679 (15)	C18—C19	1.392 (2)
O1—C37	1.4190 (15)	C19—C20	1.387 (2)
O2—C5	1.3704 (15)	C19—H19	0.9500
O2—C38	1.4223 (17)	C20—C21	1.379 (3)
N1—C9	1.4696 (16)	C20—H20	0.9500
N1—C1	1.4773 (15)	C21—C22	1.374 (3)
N1—C30	1.4804 (16)	C21—H21	0.9500
N2—C10	1.3276 (16)	C22—C23	1.400 (3)
N2—C11	1.4621 (16)	C22—H22	0.9500
N2—H1N	0.903 (17)	C23—H23	0.9500
C1—C2	1.5277 (16)	C24—C29	1.381 (2)
C1—C24	1.5286 (17)	C24—C25	1.3950 (18)
C1—H1	1.0000	C25—C26	1.375 (2)
C2—C7	1.3872 (16)	C25—H25	0.9500
C2—C3	1.4061 (17)	C26—C27	1.381 (3)
C3—C4	1.3817 (17)	C26—H26	0.9500
C3—H3	0.9500	C27—C28	1.382 (2)
C4—C5	1.4111 (18)	C27—H27	0.9500
C5—C6	1.3771 (18)	C28—C29	1.394 (2)
C6—C7	1.4080 (17)	C28—H28	0.9500
C6—H6	0.9500	C29—H29	0.9500
C7—C8	1.5148 (17)	C30—C31	1.5096 (19)
C8—C9	1.5223 (16)	C30—H30A	0.9900
C8—H8A	0.9900	C30—H30B	0.9900
C8—H8B	0.9900	C31—C36	1.385 (2)
C9—C10	1.5262 (17)	C31—C32	1.389 (2)
C9—H9	1.0000	C32—C33	1.384 (2)
C11—C12	1.516 (2)	C32—H32	0.9500
C11—C18	1.5202 (19)	C33—C34	1.381 (2)
C11—H11	1.0000	C33—H33	0.9500
C12—C17	1.388 (2)	C34—C35	1.375 (3)
C12—C13	1.394 (2)	C34—H34	0.9500
C13—C14	1.379 (3)	C35—C36	1.396 (2)
C13—H13	0.9500	C35—H35	0.9500
C14—C15	1.365 (4)	C36—H36	0.9500
C14—H14	0.9500	C37—H37A	0.9800
C15—C16	1.375 (4)	C37—H37B	0.9800
C15—H15	0.9500	C37—H37C	0.9800
C16—C17	1.401 (3)	C38—H38A	0.9800
C16—H16	0.9500	C38—H38B	0.9800
C17—H17	0.9500	C38—H38C	0.9800

C4—O1—C37	117.50 (10)	C23—C18—C11	123.29 (13)
C5—O2—C38	117.01 (11)	C19—C18—C11	118.05 (13)
C9—N1—C1	108.58 (9)	C20—C19—C18	120.62 (16)
C9—N1—C30	113.17 (10)	C20—C19—H19	119.7
C1—N1—C30	113.06 (10)	C18—C19—H19	119.7
C10—N2—C11	126.52 (11)	C21—C20—C19	120.09 (17)
C10—N2—H1N	113.2 (10)	C21—C20—H20	120.0
C11—N2—H1N	120.0 (10)	C19—C20—H20	120.0
N1—C1—C2	112.49 (9)	C22—C21—C20	120.22 (16)
N1—C1—C24	106.58 (10)	C22—C21—H21	119.9
C2—C1—C24	115.33 (10)	C20—C21—H21	119.9
N1—C1—H1	107.4	C21—C22—C23	119.72 (19)
C2—C1—H1	107.4	C21—C22—H22	120.1
C24—C1—H1	107.4	C23—C22—H22	120.1
C7—C2—C3	119.32 (10)	C18—C23—C22	120.69 (16)
C7—C2—C1	121.50 (10)	C18—C23—H23	119.7
C3—C2—C1	119.17 (11)	C22—C23—H23	119.7
C4—C3—C2	121.04 (11)	C29—C24—C25	118.44 (12)
C4—C3—H3	119.5	C29—C24—C1	123.56 (11)
C2—C3—H3	119.5	C25—C24—C1	117.86 (12)
O1—C4—C3	125.35 (11)	C26—C25—C24	121.03 (15)
O1—C4—C5	115.08 (10)	C26—C25—H25	119.5
C3—C4—C5	119.57 (11)	C24—C25—H25	119.5
O2—C5—C6	125.09 (12)	C25—C26—C27	120.22 (15)
O2—C5—C4	115.50 (11)	C25—C26—H26	119.9
C6—C5—C4	119.40 (11)	C27—C26—H26	119.9
C5—C6—C7	121.15 (11)	C26—C27—C28	119.65 (14)
C5—C6—H6	119.4	C26—C27—H27	120.2
C7—C6—H6	119.4	C28—C27—H27	120.2
C2—C7—C6	119.50 (11)	C27—C28—C29	119.95 (16)
C2—C7—C8	122.00 (10)	C27—C28—H28	120.0
C6—C7—C8	118.49 (11)	C29—C28—H28	120.0
C7—C8—C9	108.18 (10)	C24—C29—C28	120.71 (13)
C7—C8—H8A	110.1	C24—C29—H29	119.6
C9—C8—H8A	110.1	C28—C29—H29	119.6
C7—C8—H8B	110.1	N1—C30—C31	110.48 (10)
C9—C8—H8B	110.1	N1—C30—H30A	109.6
H8A—C8—H8B	108.4	C31—C30—H30A	109.6
N1—C9—C8	112.50 (10)	N1—C30—H30B	109.6
N1—C9—C10	110.78 (10)	C31—C30—H30B	109.6
C8—C9—C10	116.83 (10)	H30A—C30—H30B	108.1
N1—C9—H9	105.2	C36—C31—C32	118.35 (13)
C8—C9—H9	105.2	C36—C31—C30	121.53 (13)
C10—C9—H9	105.2	C32—C31—C30	120.13 (12)
N2—C10—C9	110.92 (10)	C33—C32—C31	121.00 (14)
N2—C10—S1	124.93 (10)	C33—C32—H32	119.5
C9—C10—S1	123.89 (9)	C31—C32—H32	119.5
N2—C11—C12	107.35 (11)	C34—C33—C32	119.92 (16)
N2—C11—C18	110.72 (11)	C34—C33—H33	120.0
C12—C11—C18	114.96 (11)	C32—C33—H33	120.0
N2—C11—H11	107.9	C35—C34—C33	120.09 (15)
C12—C11—H11	107.9	C35—C34—H34	120.0
C18—C11—H11	107.9	C33—C34—H34	120.0
C17—C12—C13	119.47 (15)	C34—C35—C36	119.74 (16)
C17—C12—C11	122.26 (14)	C34—C35—H35	120.1
C13—C12—C11	117.97 (14)	C36—C35—H35	120.1
C14—C13—C12	120.5 (2)	C31—C36—C35	120.86 (15)
C14—C13—H13	119.8	C31—C36—H36	119.6
C12—C13—H13	119.8	C35—C36—H36	119.6
C15—C14—C13	120.0 (2)	O1—C37—H37A	109.5
C15—C14—H14	120.0	O1—C37—H37B	109.5
C13—C14—H14	120.0	H37A—C37—H37B	109.5
C14—C15—C16	120.67 (18)	O1—C37—H37C	109.5
C14—C15—H15	119.7	H37A—C37—H37C	109.5
C16—C15—H15	119.7	H37B—C37—H37C	109.5
C15—C16—C17	120.2 (2)	O2—C38—H38A	109.5
C15—C16—H16	119.9	O2—C38—H38B	109.5
C17—C16—H16	119.9	H38A—C38—H38B	109.5
C12—C17—C16	119.16 (19)	O2—C38—H38C	109.5
C12—C17—H17	120.4	H38A—C38—H38C	109.5
C16—C17—H17	120.4	H38B—C38—H38C	109.5
C23—C18—C19	118.66 (14)

C9—N1—C1—C2	−47.06 (13)	N2—C11—C12—C13	−76.53 (16)
C30—N1—C1—C2	79.40 (12)	C18—C11—C12—C13	159.81 (13)
C9—N1—C1—C24	80.27 (11)	C17—C12—C13—C14	−0.3 (2)
C30—N1—C1—C24	−153.27 (10)	C11—C12—C13—C14	173.60 (15)
N1—C1—C2—C7	14.37 (17)	C12—C13—C14—C15	0.1 (3)
C24—C1—C2—C7	−108.15 (14)	C13—C14—C15—C16	0.2 (3)
N1—C1—C2—C3	−165.91 (11)	C14—C15—C16—C17	−0.4 (3)
C24—C1—C2—C3	71.57 (14)	C13—C12—C17—C16	0.1 (2)
C7—C2—C3—C4	1.25 (18)	C11—C12—C17—C16	−173.46 (15)
C1—C2—C3—C4	−178.48 (11)	C15—C16—C17—C12	0.2 (3)
C37—O1—C4—C3	−5.03 (19)	N2—C11—C18—C23	−1.5 (2)
C37—O1—C4—C5	173.83 (13)	C12—C11—C18—C23	120.33 (16)
C2—C3—C4—O1	176.79 (12)	N2—C11—C18—C19	178.80 (13)
C2—C3—C4—C5	−2.03 (19)	C12—C11—C18—C19	−59.35 (18)
C38—O2—C5—C6	−5.5 (2)	C23—C18—C19—C20	0.5 (2)
C38—O2—C5—C4	175.76 (14)	C11—C18—C19—C20	−179.80 (15)
O1—C4—C5—O2	1.68 (17)	C18—C19—C20—C21	−0.3 (3)
C3—C4—C5—O2	−179.38 (11)	C19—C20—C21—C22	0.1 (3)
O1—C4—C5—C6	−177.17 (12)	C20—C21—C22—C23	−0.1 (3)
C3—C4—C5—C6	1.76 (19)	C19—C18—C23—C22	−0.5 (3)
O2—C5—C6—C7	−179.48 (13)	C11—C18—C23—C22	179.80 (17)
C4—C5—C6—C7	−0.7 (2)	C21—C22—C23—C18	0.3 (3)
C3—C2—C7—C6	−0.20 (18)	N1—C1—C24—C29	−107.96 (13)
C1—C2—C7—C6	179.52 (11)	C2—C1—C24—C29	17.67 (17)
C3—C2—C7—C8	−179.26 (12)	N1—C1—C24—C25	67.68 (14)
C1—C2—C7—C8	0.47 (19)	C2—C1—C24—C25	−166.70 (11)
C5—C6—C7—C2	0.0 (2)	C29—C24—C25—C26	0.1 (2)
C5—C6—C7—C8	179.06 (12)	C1—C24—C25—C26	−175.77 (13)
C2—C7—C8—C9	17.38 (17)	C24—C25—C26—C27	0.4 (2)
C6—C7—C8—C9	−161.69 (11)	C25—C26—C27—C28	−0.5 (3)
C1—N1—C9—C8	69.61 (13)	C26—C27—C28—C29	0.2 (3)
C30—N1—C9—C8	−56.79 (13)	C25—C24—C29—C28	−0.4 (2)
C1—N1—C9—C10	−157.57 (10)	C1—C24—C29—C28	175.21 (13)
C30—N1—C9—C10	76.03 (12)	C27—C28—C29—C24	0.3 (2)
C7—C8—C9—N1	−52.47 (14)	C9—N1—C30—C31	−164.19 (10)
C7—C8—C9—C10	177.76 (10)	C1—N1—C30—C31	71.84 (13)
C11—N2—C10—C9	174.98 (12)	N1—C30—C31—C36	−111.71 (14)
C11—N2—C10—S1	0.6 (2)	N1—C30—C31—C32	68.10 (15)
N1—C9—C10—N2	36.60 (14)	C36—C31—C32—C33	1.6 (2)
C8—C9—C10—N2	167.18 (11)	C30—C31—C32—C33	−178.21 (13)
N1—C9—C10—S1	−148.92 (10)	C31—C32—C33—C34	0.3 (2)
C8—C9—C10—S1	−18.34 (16)	C32—C33—C34—C35	−1.7 (2)
C10—N2—C11—C12	113.87 (15)	C33—C34—C35—C36	1.2 (3)
C10—N2—C11—C18	−119.91 (14)	C32—C31—C36—C35	−2.1 (2)
N2—C11—C12—C17	97.16 (15)	C30—C31—C36—C35	177.71 (14)
C18—C11—C12—C17	−26.50 (19)	C34—C35—C36—C31	0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···N1	0.903 (17)	2.139 (16)	2.6548 (15)	115.4 (12)

Experimental details

Crystal data
Chemical formula	C₃₈H₃₆N₂O₂S
M_r	584.75
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	9.0463 (1), 17.6687 (2), 19.6178 (2)
V (Å³)	3135.64 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.34 × 0.32 × 0.30

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7464, 7464, 6545
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.090, 1.06
No. of reflections	7464
No. of parameters	394
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.25
Absolute structure	Flack (1983), 3271 Friedel pairs
Absolute structure parameter	−0.07 (5)

Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···N1	0.903 (17)	2.139 (16)	2.6548 (15)	115.4 (12)

Acknowledgements

The authors wish to thank Dr Hong Su from the Chemistry Department of the University of Cape Town for her assistance with the crystallographic data collection and refinement.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Naicker, T., Arvidsson, P. I., Kruger, H. G., Maguire, G. E. M. & Govender, T. (2011a). Eur. J. Org. Chem. doi:10.1002/ejoc.201100923. Google Scholar
Naicker, T., Govender, T., Kruger, H. G. & Maguire, G. E. M. (2011b). Acta Cryst. E67, o1403. Web of Science CSD CrossRef IUCr Journals Google Scholar
Naicker, T., Petzold, K., Singh, T., Arvidsson, P. I., Kruger, H. G., Maguire, G. E. M. & Govender, T. (2010). Tetrahedron Asymmetry, 21, 2859–2867. Web of Science CrossRef CAS Google Scholar
Nonius (2000). COLLECT Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. 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)-N-Benzhydryl-2-benzyl-6,7-dimeth­­oxy-1-phenyl-1,2,3,4-tetra­hydro­iso­quinoline-3-carbo­thio­amide

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(1R,3S)-N-Benzhydryl-2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carbothioamide