(1S,4S)-2-(2,4-Difluoro­phen­yl)-5-[(4-methyl­phen­yl)sulfon­yl]-2,5-diaza­bicyclo­[2.2.1]hepta­ne

Wu, C.; Zhang, J.; Li, P.; Zhang, J.; Wu, J.

doi:10.1107/S1600536810054541

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o272

doi:10.1107/S1600536810054541

Open

access

(1S,4S)-2-(2,4-Difluorophenyl)-5-[(4-methylphenyl)sulfonyl]-2,5-diazabicyclo[2.2.1]heptane

Chunli Wu,^a,^b Jingyu Zhang,^c Pan Li,^b Junxia Zhang ^b and Jizhou Wu ^a ^*

^aSchool of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, People's Republic of China, ^bSchool of Pharmaceutical Sciences, Zhengzhou Univresity, Zhengzhou 450001, People's Republic of China, and ^cSchool of Pharmaceutical Sciences, Henan University of TCM, Zhengzhou 450008, People's Republic of China
^*Correspondence e-mail: wcllaoshi@yahoo.com.cn

(Received 21 December 2010; accepted 28 December 2010; online 8 January 2011)

In the title molecule, C₁₈H₁₈F₂N₂O₂S, the two benzene rings, which are oriented in opposite directions with respect to the rigid 2,5-diazabicyclo[2.2.1]heptane core, form a dihedral angle of 17.2 (1)°. Weak intermolecular C—H⋯O, C—H⋯F and C—H⋯N contacts consolidate the crystal packing.

Related literature

For details of the synthesis, see: Portoghese et al. (1966 ); Braish & Fox (1990 ); Ulrich et al. (1990 ). For a recent study of the biological activity of 2,5-diazabicyclo[2.2.1]heptane derivatives, see: Li et al. (2010 ).

Experimental

Crystal data

C₁₈H₁₈F₂N₂O₂S
M_r = 364.40
Monoclinic, P 2₁
a = 9.9615 (11) Å
b = 7.6586 (8) Å
c = 11.3461 (14) Å
β = 98.979 (1)°
V = 855.00 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 298 K
0.38 × 0.33 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.920, T_max = 0.967
4425 measured reflections
2891 independent reflections
2045 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.103
S = 1.00
2891 reflections
227 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 1569 Friedel pairs
Flack parameter: 0.00 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O2ⁱ	0.97	2.63	3.445 (5)	141
C5—H5A⋯O2ⁱ	0.97	2.70	3.550 (5)	147
C10—H10⋯F1ⁱⁱ	0.93	2.63	3.445 (4)	147
C18—H18⋯O1ⁱⁱⁱ	0.93	2.43	3.342 (5)	166
C15—H15⋯N2^iv	0.93	2.66	3.412 (5)	139
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810054541/cv5024sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810054541/cv5024Isup2.hkl

checkCIF report

Comment top

2,5-Diazabicyclo[2.2.1]heptane derivatives, the synthesis of which is known for a long time (Portoghese et al., 1966; Braish & Fox, 1990), are still under intensive studies. For example, Li et al. (2010) used them as novel α7 neuronal nicotinic receptor ligands. Herewith we report the synthesis and crystal structure of the title compound (I) (Fig. 1) prepared in enantiomerically pure form from trans-4-hydroxy-L-proline (Ulrich et al., 1990).

In (I), the angles C2—C5—C4, C4—N1—C1 and C3—N2—C2 are 92.9 (3), 107.2 (3) and 106.1 (3)°, respectively. The two benzene rings are oriented in opposite directions in reference to the rigid 2,5-diazabicyclo[2.2.1]heptane core, and they form a dihedral angle with the value of 17.2 (1)°. In the crystal structure, weak intramolecular C—H···O, C—H···F and C—H···N hydrogen bonds(Table 1) consolidate the crystal packing.

Related literature top

For details of the synthesis, see: Portoghese et al. (1966); Braish & Fox (1990); Ulrich et al. (1990). For a recent study of the biological activity of 2,5-diazabicyclo[2.2.1]heptane derivatives, see: Li et al. (2010).

Experimental top

All reagents and solvents were used as obtained without further purification. (1S,4S)-5-(2,4-difluorophenyl)- 2-tosyl-2,5-diazabicyclo[2.2.1]heptane was synthesized from (2S,4R)-N-tosyl-4-tosyloxy-2-tosyloxymethylpyrrolidine as described previously by Ulrich and Fritz, whose started material was trans-4-hydroxy-L-proline. A solution of 2,4-difluoroaniline(1.5 mL,9.01 mmol) and (2S,4R)-N-tosyl- 4-tosyloxy-2-tosyloxymethylpyrrolidine (0.5 g,0.86 mmol) was refluxed for about 2 h in a 10 ml three-neck bottle until the material was consumed. The resulting mixture was cooled to room tempeature, before ethyl acetate was added. Then the mixture was heated to be able to be stirred and filtered to get the the title compound. m.p.:187–192°C. Crystals suitable for X-ray analysis were grown by slow evaporation from ethyl acetate solution at room temperature for two weeks. The crystals were separated manually. 1H NMR(400 MHz, CDCl3)σ: 7.702–7.681(d,J=8 Hz,2H), 7.282–7.263(d,J=7.6 Hz,2H), 6.719–6.700(m,J=7.6 Hz,2H), 6.448–6.387(m,J=24 Hz,1H), 4.463(s,1H), 4.339(s,1H),3.563–3.539(d,J=9.6 Hz,2H), 3.263–3.239(m,J=9.6 Hz,6H), 2.415(s,3H), 1.845–1.820(d,J=10 Hz,1H), 1.374–1.349(d,J=10 Hz,2H); 13 C NMR(100.6 MHz,CDCl3)σ: 156.32, 153.94, 143.71, 135.37, 131.70, 129.79, 127.39, 115.76, 110.89, 104.85, 59.87, 59.29, 58.18, 52.31, 36.38, 21.51.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) showing the atomic labels and 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram.

(1S,4S)-2-(2,4-Difluorophenyl)-5-[(4-methylphenyl)sulfonyl]- 2,5-diazabicyclo[2.2.1]heptane top

Crystal data top

C₁₈H₁₈F₂N₂O₂S	F(000) = 380
M_r = 364.40	D_x = 1.415 Mg m⁻³
Monoclinic, P2₁	Melting point = 460–465 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.9615 (11) Å	Cell parameters from 1315 reflections
b = 7.6586 (8) Å	θ = 3.0–20.7°
c = 11.3461 (14) Å	µ = 0.22 mm⁻¹
β = 98.979 (1)°	T = 298 K
V = 855.00 (17) Å³	Block, colourless
Z = 2	0.38 × 0.33 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2891 independent reflections
Radiation source: fine-focus sealed tube	2045 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
phi and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
T_min = 0.920, T_max = 0.967	k = −9→8
4425 measured reflections	l = −11→13

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0457P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2891 reflections	Δρ_max = 0.17 e Å⁻³
227 parameters	Δρ_min = −0.28 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1569 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (10)

Crystal data top

C₁₈H₁₈F₂N₂O₂S	V = 855.00 (17) Å³
M_r = 364.40	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.9615 (11) Å	µ = 0.22 mm⁻¹
b = 7.6586 (8) Å	T = 298 K
c = 11.3461 (14) Å	0.38 × 0.33 × 0.15 mm
β = 98.979 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2891 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2045 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.967	R_int = 0.028
4425 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.103	Δρ_max = 0.17 e Å⁻³
S = 1.00	Δρ_min = −0.28 e Å⁻³
2891 reflections	Absolute structure: Flack (1983), 1569 Friedel pairs
227 parameters	Absolute structure parameter: 0.00 (10)
1 restraint

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
F1	0.4098 (2)	0.6800 (3)	−0.03940 (17)	0.0765 (8)
F2	0.8825 (2)	0.6799 (4)	0.0177 (2)	0.1001 (9)
N1	0.2867 (3)	0.7976 (4)	0.3031 (2)	0.0461 (8)
N2	0.4040 (3)	0.5378 (4)	0.1917 (2)	0.0433 (7)
O1	0.2878 (3)	0.9129 (4)	0.5023 (2)	0.0763 (10)
O2	0.2841 (2)	1.1122 (3)	0.3288 (3)	0.0727 (9)
S1	0.24048 (8)	0.95563 (13)	0.38078 (9)	0.0536 (3)
C1	0.2683 (4)	0.8049 (5)	0.1708 (3)	0.0542 (10)
H1A	0.3421	0.8665	0.1425	0.065*
H1B	0.1824	0.8583	0.1375	0.065*
C2	0.2704 (3)	0.6110 (5)	0.1432 (3)	0.0521 (10)
H2	0.2384	0.5815	0.0595	0.063*
C3	0.4094 (3)	0.5309 (5)	0.3233 (3)	0.0469 (9)
H3A	0.4851	0.5981	0.3643	0.056*
H3B	0.4158	0.4117	0.3525	0.056*
C4	0.2756 (3)	0.6122 (5)	0.3370 (3)	0.0501 (9)
H4	0.2454	0.5921	0.4140	0.060*
C5	0.1836 (4)	0.5390 (6)	0.2296 (3)	0.0607 (10)
H5A	0.1793	0.4125	0.2293	0.073*
H5B	0.0928	0.5885	0.2188	0.073*
C6	0.0621 (3)	0.9624 (5)	0.3636 (3)	0.0417 (8)
C7	−0.0068 (4)	0.8662 (5)	0.4375 (3)	0.0516 (9)
H7	0.0408	0.7962	0.4968	0.062*
C8	−0.1472 (4)	0.8740 (5)	0.4234 (3)	0.0552 (10)
H8	−0.1931	0.8059	0.4720	0.066*
C9	−0.2197 (3)	0.9795 (5)	0.3395 (3)	0.0512 (9)
C10	−0.1492 (4)	1.0745 (5)	0.2650 (3)	0.0556 (10)
H10	−0.1971	1.1452	0.2063	0.067*
C11	−0.0098 (4)	1.0664 (5)	0.2761 (3)	0.0528 (10)
H11	0.0358	1.1306	0.2250	0.063*
C12	−0.3720 (3)	0.9925 (7)	0.3276 (4)	0.0750 (13)
H12A	−0.4128	0.9366	0.2550	0.112*
H12B	−0.3983	1.1132	0.3258	0.112*
H12C	−0.4021	0.9360	0.3944	0.112*
C13	0.5230 (3)	0.5761 (4)	0.1463 (3)	0.0415 (9)
C14	0.5274 (4)	0.6452 (5)	0.0333 (3)	0.0494 (9)
C15	0.6459 (4)	0.6818 (5)	−0.0094 (3)	0.0578 (11)
H15	0.6443	0.7309	−0.0845	0.069*
C16	0.7645 (4)	0.6445 (6)	0.0606 (4)	0.0609 (11)
C17	0.7683 (4)	0.5735 (6)	0.1699 (4)	0.0633 (12)
H17	0.8514	0.5473	0.2162	0.076*
C18	0.6496 (4)	0.5398 (5)	0.2126 (3)	0.0518 (9)
H18	0.6537	0.4913	0.2882	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0681 (16)	0.109 (2)	0.0488 (13)	0.0138 (14)	−0.0023 (11)	0.0168 (13)
F2	0.0703 (17)	0.134 (3)	0.104 (2)	−0.0124 (16)	0.0408 (14)	0.0063 (17)
N1	0.0493 (18)	0.0448 (19)	0.0458 (18)	0.0052 (16)	0.0121 (14)	0.0034 (15)
N2	0.0394 (16)	0.0426 (17)	0.0466 (17)	0.0031 (13)	0.0027 (13)	−0.0024 (14)
O1	0.0636 (18)	0.099 (3)	0.0592 (17)	0.0166 (16)	−0.0120 (13)	−0.0166 (16)
O2	0.0501 (17)	0.0422 (17)	0.128 (2)	−0.0106 (14)	0.0201 (16)	−0.0099 (17)
S1	0.0412 (5)	0.0511 (6)	0.0669 (7)	−0.0008 (5)	0.0035 (4)	−0.0114 (5)
C1	0.049 (2)	0.056 (3)	0.056 (2)	0.015 (2)	0.0062 (18)	0.012 (2)
C2	0.046 (2)	0.057 (3)	0.049 (2)	−0.0056 (19)	−0.0040 (17)	−0.0054 (19)
C3	0.052 (2)	0.043 (2)	0.046 (2)	0.0041 (17)	0.0080 (17)	0.0080 (16)
C4	0.051 (2)	0.046 (2)	0.056 (2)	0.0032 (18)	0.0165 (18)	0.0146 (18)
C5	0.041 (2)	0.056 (2)	0.083 (3)	−0.0127 (18)	0.004 (2)	0.002 (2)
C6	0.0401 (18)	0.0419 (19)	0.0434 (18)	−0.001 (2)	0.0075 (15)	−0.006 (2)
C7	0.056 (2)	0.046 (2)	0.053 (2)	0.0065 (19)	0.0103 (18)	0.0060 (19)
C8	0.053 (2)	0.051 (2)	0.065 (3)	−0.0021 (19)	0.019 (2)	0.002 (2)
C9	0.0420 (19)	0.053 (3)	0.058 (2)	−0.005 (2)	0.0054 (17)	−0.011 (2)
C10	0.042 (2)	0.063 (3)	0.060 (2)	0.000 (2)	0.0004 (18)	0.006 (2)
C11	0.054 (2)	0.053 (3)	0.051 (2)	−0.0060 (19)	0.0105 (19)	0.0052 (19)
C12	0.046 (2)	0.083 (3)	0.096 (3)	−0.009 (2)	0.010 (2)	−0.014 (3)
C13	0.044 (2)	0.038 (2)	0.042 (2)	0.0035 (16)	0.0062 (16)	−0.0026 (16)
C14	0.055 (2)	0.043 (2)	0.047 (2)	0.0085 (19)	−0.0013 (18)	−0.0001 (19)
C15	0.071 (3)	0.054 (3)	0.051 (2)	−0.001 (2)	0.021 (2)	0.0008 (19)
C16	0.051 (3)	0.063 (3)	0.073 (3)	−0.002 (2)	0.023 (2)	−0.004 (2)
C17	0.041 (2)	0.084 (3)	0.064 (3)	0.003 (2)	0.0040 (19)	0.000 (2)
C18	0.050 (2)	0.059 (2)	0.047 (2)	0.0077 (19)	0.0060 (17)	0.0014 (18)

Geometric parameters (Å, º) top

F1—C14	1.350 (4)	C6—C7	1.378 (4)
F2—C16	1.367 (4)	C6—C11	1.382 (5)
N1—C4	1.480 (4)	C7—C8	1.383 (5)
N1—C1	1.485 (4)	C7—H7	0.9300
N1—S1	1.606 (3)	C8—C9	1.366 (5)
N2—C13	1.395 (4)	C8—H8	0.9300
N2—C2	1.470 (4)	C9—C10	1.387 (5)
N2—C3	1.486 (4)	C9—C12	1.506 (4)
O1—S1	1.424 (3)	C10—C11	1.376 (5)
O2—S1	1.434 (3)	C10—H10	0.9300
S1—C6	1.758 (3)	C11—H11	0.9300
C1—C2	1.518 (5)	C12—H12A	0.9600
C1—H1A	0.9700	C12—H12B	0.9600
C1—H1B	0.9700	C12—H12C	0.9600
C2—C5	1.509 (5)	C13—C18	1.391 (5)
C2—H2	0.9800	C13—C14	1.394 (4)
C3—C4	1.501 (4)	C14—C15	1.372 (5)
C3—H3A	0.9700	C15—C16	1.348 (5)
C3—H3B	0.9700	C15—H15	0.9300
C4—C5	1.514 (5)	C16—C17	1.349 (5)
C4—H4	0.9800	C17—C18	1.371 (5)
C5—H5A	0.9700	C17—H17	0.9300
C5—H5B	0.9700	C18—H18	0.9300

C4—N1—C1	107.2 (3)	C7—C6—C11	119.6 (3)
C4—N1—S1	122.8 (2)	C7—C6—S1	120.5 (3)
C1—N1—S1	121.7 (2)	C11—C6—S1	119.9 (3)
C13—N2—C2	123.6 (3)	C6—C7—C8	119.8 (3)
C13—N2—C3	118.6 (3)	C6—C7—H7	120.1
C2—N2—C3	106.1 (3)	C8—C7—H7	120.1
O1—S1—O2	120.99 (18)	C9—C8—C7	121.4 (3)
O1—S1—N1	106.15 (17)	C9—C8—H8	119.3
O2—S1—N1	105.85 (14)	C7—C8—H8	119.3
O1—S1—C6	106.89 (15)	C8—C9—C10	118.2 (3)
O2—S1—C6	107.21 (17)	C8—C9—C12	121.2 (4)
N1—S1—C6	109.44 (16)	C10—C9—C12	120.6 (4)
N1—C1—C2	99.7 (3)	C11—C10—C9	121.4 (3)
N1—C1—H1A	111.8	C11—C10—H10	119.3
C2—C1—H1A	111.8	C9—C10—H10	119.3
N1—C1—H1B	111.8	C10—C11—C6	119.6 (3)
C2—C1—H1B	111.8	C10—C11—H11	120.2
H1A—C1—H1B	109.6	C6—C11—H11	120.2
N2—C2—C5	101.2 (3)	C9—C12—H12A	109.5
N2—C2—C1	109.7 (3)	C9—C12—H12B	109.5
C5—C2—C1	101.3 (3)	H12A—C12—H12B	109.5
N2—C2—H2	114.4	C9—C12—H12C	109.5
C5—C2—H2	114.4	H12A—C12—H12C	109.5
C1—C2—H2	114.4	H12B—C12—H12C	109.5
N2—C3—C4	101.3 (2)	C18—C13—C14	114.7 (3)
N2—C3—H3A	111.5	C18—C13—N2	120.6 (3)
C4—C3—H3A	111.5	C14—C13—N2	124.7 (3)
N2—C3—H3B	111.5	F1—C14—C15	117.1 (3)
C4—C3—H3B	111.5	F1—C14—C13	119.2 (3)
H3A—C3—H3B	109.3	C15—C14—C13	123.6 (3)
N1—C4—C3	105.5 (3)	C16—C15—C14	118.2 (3)
N1—C4—C5	101.9 (3)	C16—C15—H15	120.9
C3—C4—C5	101.5 (3)	C14—C15—H15	120.9
N1—C4—H4	115.4	C15—C16—C17	121.6 (4)
C3—C4—H4	115.4	C15—C16—F2	118.1 (4)
C5—C4—H4	115.4	C17—C16—F2	120.3 (4)
C2—C5—C4	92.9 (3)	C16—C17—C18	119.9 (4)
C2—C5—H5A	113.1	C16—C17—H17	120.0
C4—C5—H5A	113.1	C18—C17—H17	120.0
C2—C5—H5B	113.1	C17—C18—C13	122.0 (3)
C4—C5—H5B	113.1	C17—C18—H18	119.0
H5A—C5—H5B	110.5	C13—C18—H18	119.0

C4—N1—S1—O1	42.5 (3)	O2—S1—C6—C11	21.9 (3)
C1—N1—S1—O1	−173.3 (3)	N1—S1—C6—C11	−92.5 (3)
C4—N1—S1—O2	172.2 (3)	C11—C6—C7—C8	0.2 (5)
C1—N1—S1—O2	−43.5 (3)	S1—C6—C7—C8	179.5 (3)
C4—N1—S1—C6	−72.6 (3)	C6—C7—C8—C9	−2.0 (5)
C1—N1—S1—C6	71.7 (3)	C7—C8—C9—C10	2.5 (6)
C4—N1—C1—C2	−8.7 (3)	C7—C8—C9—C12	−177.7 (4)
S1—N1—C1—C2	−157.7 (2)	C8—C9—C10—C11	−1.3 (5)
C13—N2—C2—C5	−175.9 (3)	C12—C9—C10—C11	178.9 (3)
C3—N2—C2—C5	−33.6 (3)	C9—C10—C11—C6	−0.4 (5)
C13—N2—C2—C1	−69.4 (4)	C7—C6—C11—C10	0.9 (5)
C3—N2—C2—C1	72.9 (4)	S1—C6—C11—C10	−178.4 (3)
N1—C1—C2—N2	−63.7 (3)	C2—N2—C13—C18	163.7 (3)
N1—C1—C2—C5	42.7 (3)	C3—N2—C13—C18	25.7 (5)
C13—N2—C3—C4	141.8 (3)	C2—N2—C13—C14	−18.8 (5)
C2—N2—C3—C4	−2.7 (3)	C3—N2—C13—C14	−156.8 (3)
C1—N1—C4—C3	77.7 (3)	C18—C13—C14—F1	178.0 (3)
S1—N1—C4—C3	−133.7 (3)	N2—C13—C14—F1	0.4 (5)
C1—N1—C4—C5	−28.0 (3)	C18—C13—C14—C15	−2.4 (5)
S1—N1—C4—C5	120.6 (3)	N2—C13—C14—C15	180.0 (3)
N2—C3—C4—N1	−67.9 (3)	F1—C14—C15—C16	−178.5 (3)
N2—C3—C4—C5	38.0 (3)	C13—C14—C15—C16	1.8 (6)
N2—C2—C5—C4	54.4 (3)	C14—C15—C16—C17	−0.1 (6)
C1—C2—C5—C4	−58.5 (3)	C14—C15—C16—F2	179.6 (4)
N1—C4—C5—C2	51.9 (3)	C15—C16—C17—C18	−0.9 (6)
C3—C4—C5—C2	−56.9 (3)	F2—C16—C17—C18	179.4 (4)
O1—S1—C6—C7	−26.3 (3)	C16—C17—C18—C13	0.2 (6)
O2—S1—C6—C7	−157.4 (3)	C14—C13—C18—C17	1.3 (5)
N1—S1—C6—C7	88.2 (3)	N2—C13—C18—C17	179.0 (3)
O1—S1—C6—C11	153.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O2ⁱ	0.97	2.63	3.445 (5)	141
C5—H5A···O2ⁱ	0.97	2.70	3.550 (5)	147
C10—H10···F1ⁱⁱ	0.93	2.63	3.445 (4)	147
C18—H18···O1ⁱⁱⁱ	0.93	2.43	3.342 (5)	166
C15—H15···N2^iv	0.93	2.66	3.412 (5)	139

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈F₂N₂O₂S
M_r	364.40
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	9.9615 (11), 7.6586 (8), 11.3461 (14)
β (°)	98.979 (1)
V (Å³)	855.00 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.38 × 0.33 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.920, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	4425, 2891, 2045
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.103, 1.00
No. of reflections	2891
No. of parameters	227
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.28
Absolute structure	Flack (1983), 1569 Friedel pairs
Absolute structure parameter	0.00 (10)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O2ⁱ	0.97	2.63	3.445 (5)	141
C5—H5A···O2ⁱ	0.97	2.70	3.550 (5)	147
C10—H10···F1ⁱⁱ	0.93	2.63	3.445 (4)	147
C18—H18···O1ⁱⁱⁱ	0.93	2.43	3.342 (5)	166
C15—H15···N2^iv	0.93	2.66	3.412 (5)	139

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

Acknowledgements

We thank Xiufang Shi and Hongmin Liu (Zhengzhou University) for the data analysis.

References

Braish, T. F. & Fox, D. E. (1990). J. Org. Chem. 55, 1684–1687. CrossRef CAS Web of Science Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Li, T., Bunnelle, W. H., Ryther, K. B., Anderson, D. J., Malysz, J., Helfrich, R., Granlien, J. H., Håkerud, M., Peters, D., Schrimpf, M. R., Gopalakrishnan, M. & Ji, J. G. (2010). Bioorg. Med. Chem. Lett. 20, 3636–3639. Web of Science CrossRef CAS PubMed Google Scholar
Portoghese, P. S., Larson, D. L. & Takemori, A. E. (1966). Eur. J. Pharmacol. 4, 445–451. Google Scholar
Sheldrick, G. M. (1996). 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
Ulrich, J., Fritz, S., Suhaib, M. S., Bernhard, K. & Kaberi, B. (1990). Synthesis, 11, 925–930. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o272

doi:10.1107/S1600536810054541

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

(1S,4S)-2-(2,4-Di­fluoro­phen­yl)-5-[(4-methyl­phen­yl)sulfon­yl]-2,5-di­aza­bi­cyclo­[2.2.1]hepta­ne

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(1S,4S)-2-(2,4-Difluorophenyl)-5-[(4-methylphenyl)sulfonyl]-2,5-diazabicyclo[2.2.1]heptane