(S)-2-(Methoxy­di­phenyl­methyl)-1-(thio­phen-3-yl­methyl)­pyrrolidine

The crystal and molecular structure of the title compound, C₂₃H₂₅NOS, has been determined by means of X-ray diffraction. This compound is readily li­thia­ted with n-butyl­lithium at the 2-position of the thio­phene ring to give a chiral li­thio­thio­phene that can be used as a chiral template for enantioselective conjugate addition of an alkyl group to an enone.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.044
• wR factor = 0.121
• Data-to-parameter ratio = 9.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro .          ?
PLAT301_ALERT_3_C Main Residue  Disorder .........................      13.00 Perc.

Author Response: The various indicators (R factor, thermal ellipsoids, difference maps peaks) indicate that the model treating the disorder gives a better structure than a model without disorder treatment.

PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6

Author Response: Average C-C bond precisions for light-atom organic structures in the most recent issue of Acta Cryst. E are typically in the 0.004-0.005 range with values of 0.007 for two structures containing a disorder. I thus do not consider the 0.006 value for this structure to be exceptionally high.

PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Author Response: I assume that this refers to the SA and SB labels for the sulfur atom in the two disordered components of the thiophene ring. If these labels are unacceptable, they will be changed.

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           69.79
           From the CIF: _reflns_number_total               2178
           Count of symmetry unique reflns         2174
           Completeness (_total/calc)            100.18%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         4
           Fraction of Friedel pairs measured     0.002
           Are heavy atom types Z>Si present          yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(2)

Crystal data

C23H25NOS	F(000) = 776
Mr = 363.5	Dx = 1.226 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 7.473 (1) Å	θ = 13.5–21.4°
b = 8.082 (1) Å	µ = 1.53 mm^−1
c = 32.600 (5) Å	T = 298 K
V = 1968.9 (5) Å^3	Truncated octahedron, colourless
Z = 4	0.24 × 0.18 × 0.16 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0
Radiation source: normal-focus sealed tube	θmax = 69.8°, θmin = 2.7°
Graphite monochromator	h = 0→9
non–profiled ω/2θ scans	k = 0→9
2178 measured reflections	l = 0→39
2178 independent reflections	3 standard reflections every 70 reflections
1321 reflections with I > 2σ(I)	intensity decay: 10%

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0562P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.044	(Δ/σ)max = 0.001
wR(F^2) = 0.121	Δρmax = 0.19 e Å^−3
S = 1.01	Δρmin = −0.18 e Å^−3
2178 reflections	Absolute structure: Flack (1983)
243 parameters	Absolute structure parameter: −0.03 (5)
17 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.6913 (7)	0.8057 (5)	0.94379 (12)	0.0644 (15)
H1A	0.7321	0.6918	0.943	0.077*
H1B	0.5778	0.808	0.9582	0.077*
C2	0.8239 (7)	0.9074 (6)	0.96665 (13)	0.0538 (12)
C3A	1.0080 (7)	0.9170 (6)	0.95730 (14)	0.0674 (14)	0.880 (5)
H3A	1.0575	0.8602	0.9352	0.081*	0.880 (5)
C4A	1.105 (2)	1.010 (3)	0.9814 (5)	0.087 (3)	0.880 (5)
H4A	1.2284	1.0245	0.9794	0.105*	0.880 (5)
SA	0.9662 (3)	1.1056 (2)	1.01881 (5)	0.0777 (7)	0.880 (5)
C5A	0.7861 (8)	1.0058 (6)	0.99989 (13)	0.0683 (15)	0.880 (5)
H5A	0.672	1.0164	1.0109	0.082*	0.880 (5)
C3B	0.7861 (8)	1.0058 (6)	0.99989 (13)	0.0683 (15)	0.120 (5)
H3B	0.6694	1.0345	1.0068	0.082*	0.120 (5)
C4B	0.924 (4)	1.057 (7)	1.0214 (13)	0.0777 (7)	0.120 (5)
H4B	0.922	1.0912	1.0486	0.093*	0.120 (5)
SB	1.114 (4)	1.049 (6)	0.9888 (12)	0.087 (3)	0.120 (5)
C5B	1.0080 (7)	0.9170 (6)	0.95730 (14)	0.0674 (14)	0.120 (5)
H5B	1.0636	0.8577	0.9364	0.081*	0.120 (5)
O	0.5943 (3)	0.5537 (3)	0.82118 (8)	0.0463 (7)
C17	1.0328 (5)	0.5666 (5)	0.85339 (12)	0.0435 (10)
H17	1.0705	0.6411	0.8334	0.052*
C10	0.7104 (5)	0.6661 (5)	0.84344 (11)	0.0399 (10)
C18	0.7835 (5)	0.8006 (5)	0.81483 (11)	0.0384 (9)
C6	0.5764 (6)	0.7462 (5)	0.87446 (12)	0.0457 (11)
H6	0.5224	0.6582	0.891	0.055*
N	0.6650 (5)	0.8647 (4)	0.90219 (10)	0.0489 (9)
C23	0.9068 (5)	0.9168 (5)	0.82825 (12)	0.0459 (10)
H23	0.9532	0.9071	0.8546	0.055*
C12	0.8552 (5)	0.5642 (5)	0.86468 (11)	0.0397 (10)
C14	0.9295 (7)	0.3443 (6)	0.91181 (14)	0.0628 (13)
H14	0.8931	0.2689	0.9317	0.075*
C11	0.6808 (6)	0.4325 (5)	0.79636 (13)	0.0612 (13)
H11A	0.7724	0.4844	0.7802	0.092*
H11B	0.5946	0.3818	0.7785	0.092*
H11C	0.7335	0.3495	0.8136	0.092*
C13	0.8061 (6)	0.4482 (5)	0.89394 (13)	0.0527 (12)
H13	0.6866	0.4405	0.9017	0.063*
C15	1.1059 (7)	0.3517 (6)	0.90040 (14)	0.0600 (14)
H15	1.1898	0.2826	0.9127	0.072*
C20	0.7717 (6)	0.9504 (7)	0.75047 (13)	0.0613 (13)
H20	0.7251	0.9619	0.7242	0.074*
C16	1.1566 (6)	0.4608 (5)	0.87105 (13)	0.0554 (12)
H16	1.2755	0.4646	0.8627	0.067*
C21	0.8949 (6)	1.0617 (7)	0.76462 (14)	0.0631 (14)
H21	0.9328	1.1479	0.7478	0.076*
C7	0.4256 (6)	0.8451 (5)	0.85353 (14)	0.0581 (12)
H7A	0.4178	0.8177	0.8246	0.07*
H7B	0.3112	0.8224	0.8664	0.07*
C19	0.7157 (6)	0.8202 (6)	0.77513 (12)	0.0509 (11)
H19	0.6321	0.7452	0.7651	0.061*
C22	0.9630 (7)	1.0461 (5)	0.80392 (13)	0.0577 (13)
H22	1.0459	1.1222	0.8138	0.069*
C9	0.5678 (8)	1.0214 (6)	0.90055 (16)	0.0742 (16)
H9A	0.6495	1.114	0.9033	0.089*
H9B	0.4799	1.0273	0.9224	0.089*
C8	0.4777 (8)	1.0239 (6)	0.85928 (16)	0.0716 (15)
H8A	0.5593	1.0603	0.838	0.086*
H8B	0.3733	1.0953	0.8594	0.086*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.103 (4)	0.049 (3)	0.041 (2)	−0.022 (3)	0.004 (3)	−0.003 (2)
C2	0.072 (3)	0.042 (3)	0.047 (2)	0.001 (3)	0.000 (2)	0.006 (2)
C3A	0.084 (4)	0.067 (3)	0.052 (3)	0.004 (3)	0.002 (3)	0.006 (3)
C4A	0.098 (4)	0.089 (11)	0.075 (8)	−0.003 (4)	−0.015 (4)	0.015 (4)
SA	0.0973 (15)	0.0672 (13)	0.0687 (10)	0.0005 (10)	−0.0274 (10)	−0.0089 (9)
C5A	0.080 (4)	0.071 (3)	0.054 (3)	0.007 (3)	−0.002 (3)	−0.017 (3)
C3B	0.080 (4)	0.071 (3)	0.054 (3)	0.007 (3)	−0.002 (3)	−0.017 (3)
C4B	0.0973 (15)	0.0672 (13)	0.0687 (10)	0.0005 (10)	−0.0274 (10)	−0.0089 (9)
SB	0.098 (4)	0.089 (11)	0.075 (8)	−0.003 (4)	−0.015 (4)	0.015 (4)
C5B	0.084 (4)	0.067 (3)	0.052 (3)	0.004 (3)	0.002 (3)	0.006 (3)
O	0.0383 (16)	0.0451 (16)	0.0555 (16)	−0.0045 (15)	−0.0042 (14)	−0.0103 (15)
C17	0.038 (2)	0.042 (2)	0.050 (2)	−0.006 (2)	−0.005 (2)	−0.001 (2)
C10	0.038 (2)	0.035 (2)	0.046 (2)	−0.001 (2)	−0.002 (2)	0.0006 (19)
C18	0.034 (2)	0.040 (2)	0.041 (2)	0.001 (2)	0.0018 (19)	0.0006 (18)
C6	0.047 (3)	0.040 (2)	0.050 (2)	0.000 (2)	0.004 (2)	−0.001 (2)
N	0.061 (2)	0.0381 (19)	0.048 (2)	−0.002 (2)	0.0025 (19)	−0.0050 (16)
C23	0.045 (2)	0.042 (2)	0.051 (2)	−0.005 (2)	−0.002 (2)	0.001 (2)
C12	0.042 (2)	0.038 (2)	0.038 (2)	−0.002 (2)	−0.0018 (18)	0.0001 (19)
C14	0.074 (4)	0.054 (3)	0.061 (3)	−0.004 (3)	−0.002 (3)	0.019 (2)
C11	0.062 (3)	0.051 (3)	0.071 (3)	−0.001 (3)	−0.003 (3)	−0.024 (2)
C13	0.046 (3)	0.049 (3)	0.063 (3)	0.002 (3)	0.007 (2)	0.013 (2)
C15	0.064 (3)	0.058 (3)	0.058 (3)	0.008 (3)	−0.015 (3)	0.010 (3)
C20	0.060 (3)	0.074 (3)	0.050 (2)	−0.002 (3)	−0.001 (2)	0.013 (3)
C16	0.046 (3)	0.059 (3)	0.062 (3)	0.009 (3)	−0.002 (2)	0.002 (3)
C21	0.065 (3)	0.066 (3)	0.059 (3)	−0.003 (3)	0.013 (3)	0.018 (3)
C7	0.039 (2)	0.062 (3)	0.074 (3)	0.003 (3)	0.003 (3)	−0.004 (3)
C19	0.047 (3)	0.055 (3)	0.051 (2)	0.000 (2)	−0.004 (2)	−0.002 (2)
C22	0.059 (3)	0.048 (2)	0.066 (3)	−0.015 (3)	0.006 (3)	0.006 (2)
C9	0.083 (4)	0.044 (3)	0.096 (4)	0.007 (3)	−0.010 (4)	−0.013 (3)
C8	0.062 (3)	0.052 (3)	0.100 (4)	0.013 (3)	0.000 (3)	0.000 (3)

Geometric parameters (Å, º)

C1—N	1.451 (5)	C23—C22	1.378 (5)
C1—C2	1.488 (6)	C23—H23	0.93
C1—H1A	0.97	C12—C13	1.386 (5)
C1—H1B	0.97	C14—C15	1.371 (6)
C2—C5A	1.373 (5)	C14—C13	1.376 (6)
C2—C3A	1.411 (6)	C14—H14	0.93
C3A—C4A	1.310 (11)	C11—H11A	0.96
C3A—H3A	0.93	C11—H11B	0.96
C4A—SA	1.777 (12)	C11—H11C	0.96
C4A—H4A	0.93	C13—H13	0.93
SA—C5A	1.686 (6)	C15—C16	1.356 (6)
C5A—H5A	0.93	C15—H15	0.93
C4B—SB	1.77 (2)	C20—C21	1.367 (6)
C4B—H4B	0.93	C20—C19	1.388 (6)
O—C11	1.426 (5)	C20—H20	0.93
O—C10	1.450 (4)	C16—H16	0.93
C17—C12	1.377 (5)	C21—C22	1.384 (6)
C17—C16	1.385 (5)	C21—H21	0.93
C17—H17	0.93	C7—C8	1.508 (6)
C10—C12	1.526 (5)	C7—H7A	0.97
C10—C18	1.533 (5)	C7—H7B	0.97
C10—C6	1.563 (5)	C19—H19	0.93
C18—C23	1.386 (5)	C22—H22	0.93
C18—C19	1.399 (5)	C9—C8	1.505 (6)
C6—N	1.474 (5)	C9—H9A	0.97
C6—C7	1.541 (6)	C9—H9B	0.97
C6—H6	0.98	C8—H8A	0.97
N—C9	1.461 (6)	C8—H8B	0.97
N—C1—C2	112.1 (4)	C15—C14—C13	120.2 (5)
N—C1—H1A	109.2	C15—C14—H14	119.9
C2—C1—H1A	109.2	C13—C14—H14	119.9
N—C1—H1B	109.2	O—C11—H11A	109.5
C2—C1—H1B	109.2	O—C11—H11B	109.5
H1A—C1—H1B	107.9	H11A—C11—H11B	109.5
C5A—C2—C3A	109.8 (5)	O—C11—H11C	109.5
C5A—C2—C1	125.3 (5)	H11A—C11—H11C	109.5
C3A—C2—C1	124.8 (4)	H11B—C11—H11C	109.5
C4A—C3A—C2	116.2 (8)	C14—C13—C12	121.7 (4)
C4A—C3A—H3A	121.9	C14—C13—H13	119.1
C2—C3A—H3A	121.9	C12—C13—H13	119.1
C3A—C4A—SA	109.7 (9)	C16—C15—C14	119.2 (5)
C3A—C4A—H4A	125.1	C16—C15—H15	120.4
SA—C4A—H4A	125.1	C14—C15—H15	120.4
C5A—SA—C4A	90.5 (4)	C21—C20—C19	120.4 (4)
C2—C5A—SA	113.7 (4)	C21—C20—H20	119.8
C2—C5A—H5A	123.2	C19—C20—H20	119.8
SA—C5A—H5A	123.2	C15—C16—C17	120.6 (5)
SB—C4B—H4B	126.4	C15—C16—H16	119.7
C11—O—C10	116.3 (3)	C17—C16—H16	119.7
C12—C17—C16	121.6 (4)	C20—C21—C22	120.0 (5)
C12—C17—H17	119.2	C20—C21—H21	120
C16—C17—H17	119.2	C22—C21—H21	120
O—C10—C12	108.2 (3)	C8—C7—C6	104.7 (4)
O—C10—C18	110.7 (3)	C8—C7—H7A	110.8
C12—C10—C18	113.9 (3)	C6—C7—H7A	110.8
O—C10—C6	101.5 (3)	C8—C7—H7B	110.8
C12—C10—C6	112.6 (3)	C6—C7—H7B	110.8
C18—C10—C6	109.2 (3)	H7A—C7—H7B	108.9
C23—C18—C19	117.1 (4)	C20—C19—C18	120.8 (4)
C23—C18—C10	121.7 (3)	C20—C19—H19	119.6
C19—C18—C10	120.9 (4)	C18—C19—H19	119.6
N—C6—C7	105.2 (3)	C23—C22—C21	119.3 (4)
N—C6—C10	112.2 (3)	C23—C22—H22	120.3
C7—C6—C10	113.4 (3)	C21—C22—H22	120.3
N—C6—H6	108.6	N—C9—C8	105.5 (4)
C7—C6—H6	108.6	N—C9—H9A	110.6
C10—C6—H6	108.6	C8—C9—H9A	110.6
C1—N—C9	112.7 (4)	N—C9—H9B	110.6
C1—N—C6	114.8 (3)	C8—C9—H9B	110.6
C9—N—C6	108.5 (3)	H9A—C9—H9B	108.8
C22—C23—C18	122.3 (4)	C9—C8—C7	102.3 (4)
C22—C23—H23	118.8	C9—C8—H8A	111.3
C18—C23—H23	118.8	C7—C8—H8A	111.3
C17—C12—C13	116.7 (4)	C9—C8—H8B	111.3
C17—C12—C10	123.7 (4)	C7—C8—H8B	111.3
C13—C12—C10	119.3 (4)	H8A—C8—H8B	109.2