(S)-1-Methyl-2-[1-(p-tolyl­sulfon­yl)­pyrrolidin-2-ylmethyl­sulfan­yl]-1H-imidazole

Chen, P.; Liu, X.; Luo, S.; Xu, D.

doi:10.1107/S1600536807047757

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(S)-1-Methyl-2-[1-(p-tolylsulfonyl)pyrrolidin-2-ylmethylsulfanyl]-1H-imidazole

P. Chen, X. Liu, S. Luo and D. Xu

The title compound, C₁₆H₂₁N₃O₂S₂, was synthesized from L-proline. The imidazole and toluene groups are positioned on opposite sides of the pyrrolidine ring. The absolute configuration of the chiral C atom is been determined as S. Weak C—H

O and C—H

π interactions stabilize the packing.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047757/dn2234sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047757/dn2234Isup2.hkl Contains datablock I

CCDC reference: 659718

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.007 Å
R factor = 0.072
wR factor = 0.144
Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4     ..  O1      ..       2.69 Ang.
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........        CT1

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               3000
           Count of symmetry unique reflns         1756
           Completeness (_total/calc)            170.84%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1244
           Fraction of Friedel pairs measured     0.708
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11    = .          S

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

   2 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
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The (S)-1-Methyl-2-(pyrrolidin-2-ylsulfanyl)-1H-imidazole is a new structural class of organocatalysts that derive from L-proline. By using the toluenesulfonyl to protect the NH group of the pyrrolidine the title compound could be synthesized

The pyrrolidine ring assumed a twisted envelope-like conformation that was similar to other reported L-proline derivative compounds (Wang et al., 2007). The absolute configuration of the chiral C11 atom has been determined to be S from the refinement of the Flack parameter (Flack, 1983). The Imidazole and the toluene groups are located on each side of the pyrrolidine ring (Fig. 1).

The occurrence of weak C—H···O hydrogen bonds and C—H···π interactions stabilize the structure (Table 1) (Fig. 2).

Related literature top

For related literature, see: Wang et al. (2007); Xu et al. (2006)

Experimental top

The title compound was readily synthesized by treating toluenesulfonyl Choilde (11 mmol), NaCO₃ (30 mmol) with (S)-1-Methyl-2-(pyrrolidin-2-ylsulfanyl)-1H-imidazole (10 mmol)in CHCl₃ (30 ml) with stirring at room teperature for 24 h with the yield of 95%. (S)-1-Methyl-2-(pyrrolidin-2-ylsulfanyl)-1H-imidazole was obtained from commercially available L-proline by reduction with NaBH₄—I₂, a bromination step with PBr₃ and thioether step with mercaptoimidazole successively (Xu et al.,2006). Suitable crystals were obtained by slow evaporation of ethanol at room temperature.

Structure description top

The occurrence of weak C—H···O hydrogen bonds and C—H···π interactions stabilize the structure (Table 1) (Fig. 2).

For related literature, see: Wang et al. (2007); Xu et al. (2006)

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. Molecular view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. A packing view of (I). Hydrogen bonds are illustrated as dashed lines.

(S)-1-Methyl-2-[1-(p-tolylsulfonyl)pyrrolidin-2-ylmethylsulfanyl]-1H-imidazole top

Crystal data top

C₁₆H₂₁N₃O₂S₂	F(000) = 744
M_r = 351.48	D_x = 1.372 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2004 reflections
a = 6.0881 (5) Å	θ = 2.9–24.8°
b = 14.7605 (11) Å	µ = 0.33 mm⁻¹
c = 18.9354 (14) Å	T = 298 K
V = 1701.6 (2) Å³	Block, colorless
Z = 4	0.39 × 0.10 × 0.09 mm

Data collection top

Bruker APEX area-detector diffractometer	3000 independent reflections
Radiation source: fine-focus sealed tube	2783 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −7→6
T_min = 0.884, T_max = 0.971	k = −17→17
8975 measured reflections	l = −9→22

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)] = 0.072	H-atom parameters constrained
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.0502P)² + 0.83P] where P = (F_o² + 2F_c²)/3
S = 1.27	(Δ/σ)_max = 0.018
3000 reflections	Δρ_max = 0.35 e Å⁻³
210 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1244 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (15)

Crystal data top

C₁₆H₂₁N₃O₂S₂	V = 1701.6 (2) Å³
M_r = 351.48	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0881 (5) Å	µ = 0.33 mm⁻¹
b = 14.7605 (11) Å	T = 298 K
c = 18.9354 (14) Å	0.39 × 0.10 × 0.09 mm

Data collection top

Bruker APEX area-detector diffractometer	3000 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2783 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.971	R_int = 0.043
8975 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	H-atom parameters constrained
wR(F²) = 0.144	Δρ_max = 0.35 e Å⁻³
S = 1.27	Δρ_min = −0.24 e Å⁻³
3000 reflections	Absolute structure: Flack (1983), 1244 Friedel pairs
210 parameters	Absolute structure parameter: −0.04 (15)
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	0.3383 (2)	0.67096 (9)	0.23080 (6)	0.0437 (3)
S2	0.1308 (2)	0.60811 (10)	0.42437 (6)	0.0475 (4)
O1	0.5722 (6)	0.6738 (3)	0.22838 (19)	0.0664 (11)
O2	0.2198 (7)	0.7429 (2)	0.2626 (2)	0.0617 (11)
N1	0.2711 (6)	0.5796 (3)	0.2731 (2)	0.0404 (10)
N2	−0.2291 (7)	0.5450 (3)	0.4949 (2)	0.0502 (12)
N3	−0.0441 (7)	0.6493 (2)	0.55296 (19)	0.0362 (9)
C1	0.0066 (9)	0.6334 (4)	−0.0688 (3)	0.0549 (15)
H1A	−0.1437	0.6528	−0.0708	0.082*
H1B	0.0165	0.5713	−0.0836	0.082*
H1C	0.0941	0.6705	−0.0995	0.082*
C2	0.0896 (8)	0.6419 (3)	0.0057 (2)	0.0360 (11)
C3	−0.0376 (8)	0.6812 (3)	0.0575 (3)	0.0399 (12)
H3	−0.1769	0.7022	0.0457	0.048*
C4	0.0342 (8)	0.6904 (3)	0.1260 (2)	0.0381 (11)
H4	−0.0551	0.7171	0.1600	0.046*
C5	0.2426 (7)	0.6592 (3)	0.1435 (2)	0.0324 (10)
C6	0.3746 (8)	0.6195 (3)	0.0924 (2)	0.0382 (11)
H6	0.5138	0.5982	0.1039	0.046*
C7	0.2972 (8)	0.6121 (3)	0.0246 (2)	0.0373 (11)
H7	0.3868	0.5863	−0.0097	0.045*
C8	0.3901 (9)	0.4944 (4)	0.2558 (3)	0.0536 (14)
H8A	0.4879	0.4773	0.2939	0.064*
H8B	0.4753	0.5014	0.2128	0.064*
C9	0.2129 (9)	0.4248 (4)	0.2460 (3)	0.0650 (17)
H9A	0.2645	0.3649	0.2591	0.078*
H9B	0.1621	0.4234	0.1975	0.078*
C10	0.0331 (10)	0.4565 (4)	0.2952 (3)	0.0564 (15)
H10A	0.0646	0.4392	0.3436	0.068*
H10B	−0.1078	0.4312	0.2816	0.068*
C11	0.0335 (8)	0.5598 (3)	0.2870 (2)	0.0409 (12)
H11	−0.0520	0.5760	0.2450	0.049*
C12	−0.0543 (9)	0.6107 (4)	0.3486 (2)	0.0488 (13)
H12A	−0.1945	0.5848	0.3623	0.059*
H12B	−0.0794	0.6731	0.3350	0.059*
C13	−0.0626 (8)	0.5992 (3)	0.4934 (2)	0.0381 (11)
C14	−0.3253 (9)	0.5614 (3)	0.5584 (3)	0.0528 (14)
H14	−0.4523	0.5330	0.5743	0.063*
C15	−0.2137 (8)	0.6236 (3)	0.5949 (3)	0.0438 (12)
H15	−0.2457	0.6449	0.6400	0.053*
C16	0.1183 (9)	0.7187 (4)	0.5690 (3)	0.0563 (14)
H16A	0.0685	0.7544	0.6082	0.084*
H16B	0.1381	0.7570	0.5286	0.084*
H16C	0.2554	0.6904	0.5808	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0450 (7)	0.0534 (8)	0.0329 (6)	−0.0060 (6)	−0.0042 (6)	−0.0057 (6)
S2	0.0395 (7)	0.0676 (9)	0.0352 (7)	−0.0031 (6)	0.0066 (6)	−0.0066 (7)
O1	0.051 (2)	0.091 (3)	0.058 (2)	−0.023 (2)	−0.0102 (19)	0.005 (2)
O2	0.088 (3)	0.050 (2)	0.047 (2)	−0.005 (2)	0.000 (2)	−0.0157 (18)
N1	0.039 (2)	0.057 (3)	0.025 (2)	0.0085 (19)	−0.0006 (17)	−0.0016 (19)
N2	0.055 (3)	0.041 (2)	0.054 (3)	−0.014 (2)	0.017 (2)	−0.019 (2)
N3	0.046 (2)	0.034 (2)	0.029 (2)	−0.0044 (18)	−0.0004 (18)	−0.0055 (17)
C1	0.070 (4)	0.053 (3)	0.041 (3)	−0.007 (3)	−0.012 (3)	0.008 (3)
C2	0.049 (3)	0.025 (2)	0.034 (2)	−0.008 (2)	−0.001 (2)	0.008 (2)
C3	0.035 (2)	0.036 (3)	0.049 (3)	0.003 (2)	0.000 (2)	0.014 (2)
C4	0.043 (3)	0.038 (3)	0.033 (3)	0.007 (2)	0.010 (2)	0.007 (2)
C5	0.041 (3)	0.029 (2)	0.028 (2)	−0.002 (2)	0.004 (2)	0.008 (2)
C6	0.037 (2)	0.041 (3)	0.036 (3)	0.002 (2)	0.003 (2)	0.002 (2)
C7	0.048 (3)	0.034 (3)	0.030 (2)	0.005 (2)	0.008 (2)	−0.001 (2)
C8	0.050 (3)	0.073 (4)	0.037 (3)	0.024 (3)	0.011 (3)	0.013 (3)
C9	0.070 (4)	0.067 (4)	0.058 (4)	0.016 (3)	−0.008 (3)	−0.010 (3)
C10	0.054 (3)	0.057 (3)	0.059 (3)	−0.004 (3)	−0.006 (3)	−0.009 (3)
C11	0.035 (2)	0.059 (3)	0.028 (3)	0.008 (2)	0.000 (2)	0.004 (2)
C12	0.048 (3)	0.062 (3)	0.037 (3)	0.011 (3)	−0.002 (2)	−0.001 (3)
C13	0.043 (3)	0.033 (2)	0.038 (3)	0.005 (2)	0.003 (2)	0.002 (2)
C14	0.056 (3)	0.042 (3)	0.060 (3)	−0.013 (3)	0.029 (3)	−0.011 (3)
C15	0.058 (3)	0.041 (3)	0.033 (3)	0.003 (2)	0.014 (2)	−0.004 (2)
C16	0.057 (3)	0.058 (3)	0.054 (3)	−0.003 (3)	−0.005 (3)	−0.013 (3)

Geometric parameters (Å, º) top

S1—O2	1.418 (4)	C5—C6	1.388 (6)
S1—O1	1.425 (4)	C6—C7	1.372 (6)
S1—N1	1.621 (4)	C6—H6	0.9300
S1—C5	1.761 (4)	C7—H7	0.9300
S2—C13	1.765 (5)	C8—C9	1.501 (8)
S2—C12	1.824 (5)	C8—H8A	0.9700
N1—C8	1.488 (6)	C8—H8B	0.9700
N1—C11	1.499 (6)	C9—C10	1.512 (7)
N2—C13	1.292 (6)	C9—H9A	0.9700
N2—C14	1.358 (6)	C9—H9B	0.9700
N3—C13	1.353 (6)	C10—C11	1.533 (7)
N3—C15	1.357 (6)	C10—H10A	0.9700
N3—C16	1.455 (6)	C10—H10B	0.9700
C1—C2	1.503 (7)	C11—C12	1.487 (6)
C1—H1A	0.9600	C11—H11	0.9800
C1—H1B	0.9600	C12—H12A	0.9700
C1—H1C	0.9600	C12—H12B	0.9700
C2—C3	1.378 (6)	C14—C15	1.336 (7)
C2—C7	1.386 (6)	C14—H14	0.9300
C3—C4	1.377 (7)	C15—H15	0.9300
C3—H3	0.9300	C16—H16A	0.9600
C4—C5	1.390 (6)	C16—H16B	0.9600
C4—H4	0.9300	C16—H16C	0.9600

O2—S1—O1	120.0 (3)	C9—C8—H8B	110.8
O2—S1—N1	106.6 (2)	H8A—C8—H8B	108.9
O1—S1—N1	107.0 (2)	C8—C9—C10	103.5 (4)
O2—S1—C5	107.7 (2)	C8—C9—H9A	111.1
O1—S1—C5	107.6 (2)	C10—C9—H9A	111.1
N1—S1—C5	107.3 (2)	C8—C9—H9B	111.1
C13—S2—C12	99.9 (2)	C10—C9—H9B	111.1
C8—N1—C11	110.1 (4)	H9A—C9—H9B	109.0
C8—N1—S1	118.1 (3)	C9—C10—C11	104.1 (5)
C11—N1—S1	119.5 (3)	C9—C10—H10A	110.9
C13—N2—C14	104.3 (4)	C11—C10—H10A	110.9
C13—N3—C15	105.8 (4)	C9—C10—H10B	110.9
C13—N3—C16	128.0 (4)	C11—C10—H10B	110.9
C15—N3—C16	126.2 (4)	H10A—C10—H10B	108.9
C2—C1—H1A	109.5	C12—C11—N1	112.8 (4)
C2—C1—H1B	109.5	C12—C11—C10	114.9 (4)
H1A—C1—H1B	109.5	N1—C11—C10	102.3 (4)
C2—C1—H1C	109.5	C12—C11—H11	108.9
H1A—C1—H1C	109.5	N1—C11—H11	108.9
H1B—C1—H1C	109.5	C10—C11—H11	108.9
C3—C2—C7	117.5 (4)	C11—C12—S2	112.6 (4)
C3—C2—C1	121.0 (4)	C11—C12—H12A	109.1
C7—C2—C1	121.5 (4)	S2—C12—H12A	109.1
C4—C3—C2	122.3 (4)	C11—C12—H12B	109.1
C4—C3—H3	118.8	S2—C12—H12B	109.1
C2—C3—H3	118.8	H12A—C12—H12B	107.8
C3—C4—C5	118.8 (4)	N2—C13—N3	112.7 (4)
C3—C4—H4	120.6	N2—C13—S2	125.9 (4)
C5—C4—H4	120.6	N3—C13—S2	121.4 (4)
C6—C5—C4	120.1 (4)	C15—C14—N2	111.2 (5)
C6—C5—S1	120.3 (3)	C15—C14—H14	124.4
C4—C5—S1	119.5 (3)	N2—C14—H14	124.4
C7—C6—C5	119.2 (4)	C14—C15—N3	106.0 (4)
C7—C6—H6	120.4	C14—C15—H15	127.0
C5—C6—H6	120.4	N3—C15—H15	127.0
C6—C7—C2	122.0 (4)	N3—C16—H16A	109.5
C6—C7—H7	119.0	N3—C16—H16B	109.5
C2—C7—H7	119.0	H16A—C16—H16B	109.5
N1—C8—C9	104.8 (4)	N3—C16—H16C	109.5
N1—C8—H8A	110.8	H16A—C16—H16C	109.5
C9—C8—H8A	110.8	H16B—C16—H16C	109.5
N1—C8—H8B	110.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O2ⁱ	0.93	2.49	3.365 (6)	157
C4—H4···O1ⁱⁱ	0.93	2.69	3.425 (6)	137
C16—H16B···Cg1ⁱⁱⁱ	0.96	2.77	3.643 (5)	152

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x−1, y, z; (iii) x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₂₁N₃O₂S₂
M_r	351.48
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	6.0881 (5), 14.7605 (11), 18.9354 (14)
V (Å³)	1701.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.39 × 0.10 × 0.09

Data collection
Diffractometer	Bruker APEX area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.884, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	8975, 3000, 2783
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.144, 1.27
No. of reflections	3000
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.24
Absolute structure	Flack (1983), 1244 Friedel pairs
Absolute structure parameter	−0.04 (15)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O2ⁱ	0.93	2.49	3.365 (6)	157.4
C4—H4···O1ⁱⁱ	0.93	2.69	3.425 (6)	136.5
C16—H16B···Cg1ⁱⁱⁱ	0.96	2.77	3.643 (5)	152.1

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x−1, y, z; (iii) x+1/2, −y+3/2, −z+1.

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