tert-Butyl 3-(4-bromo­phenyl­sulfon­yl)­pyrrolidine-1-carboxyl­ate

In the title compound, C₁₅H₂₀BrNO₄S, the crystal packing is stabilized by C—H...O hydrogen bonds and van der Waals inter­actions. The pyrrolidine ring adopts an envelope conformation.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.073
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.46
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  O1      ..       3.13 Ang.

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           26.05
           From the CIF: _reflns_number_total               3390
           Count of symmetry unique reflns         1908
           Completeness (_total/calc)            177.67%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1482
           Fraction of Friedel pairs measured     0.777
           Are heavy atom types Z>Si present        yes
PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero.      -0.02
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT792_ALERT_1_G Check the Absolute Configuration of C7     = ...          R

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound, (I), is an intermediate in potential drug synthesis. The pyrrolidine ring adopts an envelope conformation (Fig. 1) with the atom C8 as the flap atom whereas the four atoms are coplanar. The crystal structure is stabilized by C—H···O hydrogen bonds (Fig. 2 and Table 1) and Br···O van der Waals interactions with the distance of 3.126 Å which is shorter than the sum of radii (3.37 Å).

Related literature

The preparation of a similar compound, 4-(4-bromobenzene)sulfonylpiperidine-1-carboxylic acid tert-butyl ester, was reported by Fletcher et al. (2002).

S2. Experimental

Methanesulfonyl chloride (1.26 g, 11 mmol) was added into a mixture of 3-hydroxypyrrolidine-1-carboxylic acid tert-butyl ester (1.87 g, 10 mmol) and triethylamine (1.21 g, 12 mmol) in dichloromethane (20 ml) with stirring in an ice bath. The mixture was stirred at 273 K for 1 h, and then warmed to room temperature, stirred for additional 8 h, then partitioned between ethyl acetate (3×15 ml) and water (15 ml). The organic phase was dried and concentrated to give 3-(methylsulfonyloxy)pyrrolidine-1-carboxylic acid tert-butyl ester 2.44 g (yield 92%) that was added into a mixture of 4-bromothiophenol (2.27 g, 12 mmol) and potassium carbonate (2.21 g, 16 mmol) in acetonitrile (20 ml), and the resulting slurry was heated at reflux for 24 h. After cooling to room temperature, the reaction mixture was partitioned between water and dichloromethane. The organic phase was washed with brine, dried, and concentrated to give 3-(4-bromobenzene)thiopyrrolidine-1-carboxylic acid tert-butyl ester 2.40 g (yield 67%) and then dissolved in 10 ml of methanol; potassium peroxymonosulfate (18.54 g, 30 mmol) was added to a methanol solution. After stirring over 24 h, the solvent was evaporated. The residue was partitioned between chloroform and water. The organic phase was dried and concentrated to give the aimed product as a white solid 2.49 g (yield 92%). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a dichloromethane solution at room temperature.

S3. Refinement

H atoms were found in difference Fourier maps and refined as riding, with C—H distance of 0.93 (aromatic), 0.98 (CH), 0.97 (CH₂) and 0.96 Å (CH₃), and with U_iso(H) =kU_eq(C,N), where k=1.5 for the methyl groups and k=1.2 for all other H atoms.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of (I) with the atom-labeling scheme and the 30% probability displacement ellipsoids.
	Fig. 2. Crystal packing of (I) viewed along the c axes with hydrogen bonding. For the sake of clarity, H atoms not involved in the hydrogen bonding have been omitted.

tert-Butyl 3-(4-bromophenylsulfonyl)pyrrolidine-1-carboxylate

Crystal data

C15H20BrNO4S	Dx = 1.511 Mg m^−3
Mr = 390.29	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421c	Cell parameters from 5667 reflections
a = 18.424 (1) Å	θ = 2.3–23.3°
c = 10.1082 (11) Å	µ = 2.53 mm^−1
V = 3431.2 (5) Å^3	T = 293 K
Z = 8	Block, colourless
F(000) = 1600	0.33 × 0.26 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3390 independent reflections
Radiation source: fine-focus sealed tube	2760 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
φ and ω scans	θmax = 26.1°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −22→12
Tmin = 0.493, Tmax = 0.707	k = −20→22
18794 measured reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0351P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
3390 reflections	Δρmax = 0.42 e Å^−3
202 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1482 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.021 (8)

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.620575 (19)	0.59671 (2)	−0.04350 (4)	0.06539 (13)
S	0.66889 (4)	0.63796 (4)	0.57777 (8)	0.0515 (2)
C1	0.63226 (15)	0.60962 (17)	0.1410 (3)	0.0468 (7)
O1	0.61910 (12)	0.59169 (13)	0.6474 (2)	0.0652 (6)
O3	0.83317 (15)	0.59393 (12)	0.9922 (2)	0.0746 (7)
C3	0.68573 (17)	0.67391 (17)	0.3186 (3)	0.0510 (8)
H3	0.7146	0.7115	0.3502	0.061*
O2	0.66995 (16)	0.71375 (13)	0.6072 (2)	0.0772 (7)
O4	0.80675 (12)	0.47438 (10)	0.9672 (2)	0.0591 (6)
C9	0.75873 (19)	0.49303 (17)	0.7196 (3)	0.0564 (8)
H9A	0.7084	0.4848	0.7434	0.068*
H9B	0.7854	0.4479	0.7282	0.068*
C4	0.65312 (15)	0.62685 (16)	0.4064 (3)	0.0459 (7)
N1	0.79046 (14)	0.54924 (13)	0.7999 (3)	0.0508 (6)
C6	0.59860 (17)	0.56282 (18)	0.2270 (3)	0.0538 (8)
H6	0.5690	0.5258	0.1952	0.065*
C5	0.60938 (17)	0.57141 (16)	0.3618 (3)	0.0513 (8)
H5	0.5873	0.5400	0.4216	0.062*
C8	0.7650 (2)	0.52323 (18)	0.5805 (3)	0.0630 (9)
H8A	0.8112	0.5102	0.5411	0.076*
H8B	0.7261	0.5051	0.5248	0.076*
C12	0.83221 (17)	0.45220 (17)	1.0991 (3)	0.0534 (8)
C11	0.81189 (17)	0.54343 (16)	0.9263 (3)	0.0527 (8)
C7	0.75911 (16)	0.60457 (18)	0.5981 (3)	0.0534 (8)
H7	0.7910	0.6286	0.5339	0.064*
C10	0.78683 (18)	0.62034 (18)	0.7381 (3)	0.0562 (8)
H10A	0.8343	0.6430	0.7356	0.067*
H10B	0.7536	0.6519	0.7854	0.067*
C2	0.67588 (17)	0.66560 (17)	0.1851 (3)	0.0512 (8)
H2	0.6981	0.6970	0.1255	0.061*
C14	0.8185 (2)	0.37114 (18)	1.0985 (4)	0.0701 (10)
H14A	0.7677	0.3621	1.0850	0.105*
H14B	0.8333	0.3508	1.1817	0.105*
H14C	0.8459	0.3491	1.0284	0.105*
C13	0.7871 (2)	0.4881 (2)	1.2038 (4)	0.0810 (11)
H13A	0.8001	0.5385	1.2097	0.121*
H13B	0.7957	0.4650	1.2874	0.121*
H13C	0.7367	0.4839	1.1812	0.121*
C15	0.9123 (2)	0.4685 (3)	1.1138 (5)	0.0936 (14)
H15A	0.9379	0.4509	1.0374	0.140*
H15B	0.9306	0.4448	1.1916	0.140*
H15C	0.9192	0.5199	1.1216	0.140*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0659 (2)	0.0847 (3)	0.04548 (16)	0.00603 (17)	−0.00009 (17)	0.00048 (18)
S	0.0526 (5)	0.0572 (5)	0.0447 (4)	0.0067 (4)	0.0066 (4)	−0.0020 (3)
C1	0.0444 (17)	0.0557 (19)	0.0402 (14)	0.0114 (16)	0.0003 (13)	0.0023 (14)
O1	0.0509 (12)	0.0935 (17)	0.0512 (12)	0.0015 (15)	0.0106 (11)	0.0073 (12)
O3	0.1084 (18)	0.0532 (13)	0.0621 (15)	−0.0231 (14)	−0.0227 (13)	0.0004 (11)
C3	0.0526 (18)	0.0429 (17)	0.0577 (19)	0.0007 (15)	0.0012 (15)	0.0030 (16)
O2	0.105 (2)	0.0596 (15)	0.0674 (16)	0.0173 (15)	−0.0021 (15)	−0.0141 (12)
O4	0.0740 (15)	0.0450 (12)	0.0584 (14)	−0.0080 (10)	−0.0145 (12)	0.0049 (11)
C9	0.068 (2)	0.0424 (16)	0.0587 (19)	0.0013 (16)	−0.0070 (17)	−0.0107 (16)
C4	0.0426 (17)	0.0482 (18)	0.0468 (16)	0.0082 (15)	0.0050 (13)	0.0002 (14)
N1	0.0574 (15)	0.0424 (13)	0.0526 (15)	−0.0097 (12)	−0.0044 (13)	0.0019 (12)
C6	0.0514 (19)	0.0591 (19)	0.0510 (18)	−0.0020 (16)	0.0006 (15)	−0.0031 (15)
C5	0.0499 (19)	0.0507 (18)	0.0534 (18)	−0.0031 (15)	0.0074 (15)	0.0090 (14)
C8	0.061 (2)	0.071 (2)	0.056 (2)	0.0140 (17)	−0.0035 (16)	−0.0140 (17)
C12	0.0533 (19)	0.0502 (18)	0.0566 (19)	0.0048 (16)	−0.0085 (15)	0.0051 (15)
C11	0.0588 (19)	0.0431 (17)	0.056 (2)	−0.0081 (15)	−0.0050 (16)	−0.0003 (15)
C7	0.0474 (17)	0.065 (2)	0.0472 (16)	−0.0050 (16)	0.0070 (14)	0.0041 (15)
C10	0.0614 (19)	0.0516 (18)	0.0556 (19)	−0.0159 (17)	−0.0039 (15)	0.0101 (16)
C2	0.0493 (17)	0.0537 (18)	0.0506 (18)	0.0014 (16)	0.0062 (15)	0.0129 (15)
C14	0.080 (2)	0.050 (2)	0.080 (3)	0.0036 (19)	−0.017 (2)	0.0083 (17)
C13	0.099 (3)	0.074 (2)	0.070 (2)	0.016 (2)	0.015 (2)	0.010 (2)
C15	0.054 (2)	0.102 (3)	0.125 (4)	−0.004 (2)	−0.022 (2)	0.013 (3)

Geometric parameters (Å, º)

Br1—C1	1.893 (3)	C5—H5	0.9300
S—O2	1.428 (2)	C8—C7	1.513 (5)
S—O1	1.437 (2)	C8—H8A	0.9700
S—C4	1.768 (3)	C8—H8B	0.9700
S—C7	1.784 (3)	C12—C13	1.499 (5)
C1—C6	1.372 (4)	C12—C15	1.513 (5)
C1—C2	1.381 (4)	C12—C14	1.515 (5)
O3—C11	1.210 (4)	C7—C10	1.533 (4)
C3—C2	1.370 (5)	C7—H7	0.9800
C3—C4	1.378 (4)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
O4—C11	1.341 (4)	C2—H2	0.9300
O4—C12	1.472 (4)	C14—H14A	0.9600
C9—N1	1.440 (4)	C14—H14B	0.9600
C9—C8	1.516 (4)	C14—H14C	0.9600
C9—H9A	0.9700	C13—H13A	0.9600
C9—H9B	0.9700	C13—H13B	0.9600
C4—C5	1.377 (4)	C13—H13C	0.9600
N1—C11	1.342 (4)	C15—H15A	0.9600
N1—C10	1.452 (4)	C15—H15B	0.9600
C6—C5	1.386 (4)	C15—H15C	0.9600
C6—H6	0.9300
O2—S—O1	119.13 (16)	O4—C12—C14	102.5 (3)
O2—S—C4	108.65 (15)	C13—C12—C14	110.2 (3)
O1—S—C4	107.84 (14)	C15—C12—C14	111.0 (3)
O2—S—C7	107.49 (17)	O3—C11—O4	125.7 (3)
O1—S—C7	109.51 (14)	O3—C11—N1	123.9 (3)
C4—S—C7	103.05 (13)	O4—C11—N1	110.4 (3)
C6—C1—C2	121.9 (3)	C8—C7—C10	105.8 (3)
C6—C1—Br1	119.6 (2)	C8—C7—S	113.2 (2)
C2—C1—Br1	118.6 (2)	C10—C7—S	110.6 (2)
C2—C3—C4	120.4 (3)	C8—C7—H7	109.0
C2—C3—H3	119.8	C10—C7—H7	109.0
C4—C3—H3	119.8	S—C7—H7	109.0
C11—O4—C12	121.4 (2)	N1—C10—C7	104.0 (3)
N1—C9—C8	103.2 (3)	N1—C10—H10A	111.0
N1—C9—H9A	111.1	C7—C10—H10A	111.0
C8—C9—H9A	111.1	N1—C10—H10B	111.0
N1—C9—H9B	111.1	C7—C10—H10B	111.0
C8—C9—H9B	111.1	H10A—C10—H10B	109.0
H9A—C9—H9B	109.1	C3—C2—C1	118.6 (3)
C5—C4—C3	120.7 (3)	C3—C2—H2	120.7
C5—C4—S	120.2 (2)	C1—C2—H2	120.7
C3—C4—S	119.1 (2)	C12—C14—H14A	109.5
C11—N1—C9	126.8 (3)	C12—C14—H14B	109.5
C11—N1—C10	119.6 (3)	H14A—C14—H14B	109.5
C9—N1—C10	112.8 (3)	C12—C14—H14C	109.5
C1—C6—C5	119.1 (3)	H14A—C14—H14C	109.5
C1—C6—H6	120.5	H14B—C14—H14C	109.5
C5—C6—H6	120.5	C12—C13—H13A	109.5
C4—C5—C6	119.4 (3)	C12—C13—H13B	109.5
C4—C5—H5	120.3	H13A—C13—H13B	109.5
C6—C5—H5	120.3	C12—C13—H13C	109.5
C7—C8—C9	104.4 (3)	H13A—C13—H13C	109.5
C7—C8—H8A	110.9	H13B—C13—H13C	109.5
C9—C8—H8A	110.9	C12—C15—H15A	109.5
C7—C8—H8B	110.9	C12—C15—H15B	109.5
C9—C8—H8B	110.9	H15A—C15—H15B	109.5
H8A—C8—H8B	108.9	C12—C15—H15C	109.5
O4—C12—C13	109.9 (3)	H15A—C15—H15C	109.5
O4—C12—C15	110.2 (3)	H15B—C15—H15C	109.5
C13—C12—C15	112.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1	0.93	2.54	2.916 (3)	105
C7—H7···O3^i	0.98	2.27	3.129 (3)	145
C13—H13A···O3	0.96	2.50	3.016 (4)	114
C15—H15C···O3	0.96	2.47	2.996 (6)	115

Symmetry code: (i) −y+3/2, −x+3/2, z−1/2.