(1S,4S)-2-(2,4-Difluoro-phen-yl)-5-[(4-methyl-phen-yl)sulfon-yl]-2,5-diaza-bicyclo-[2.2.1]hepta-ne.

In the title mol-ecule, C(18)H(18)F(2)N(2)O(2)S, the two benzene rings, which are oriented in opposite directions with respect to the rigid 2,5-diaza-bicyclo-[2.2.1]heptane core, form a dihedral angle of 17.2 (1)°. Weak inter-molecular 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 = 364.40

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.103

S = 1.00

2891 reflections

227 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.28 e Å−3

Absolute structure: Flack (1983 ▶), 1569 Friedel pairs

Flack parameter: 0.00 (10)

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C18H18F2N2O2S	F(000) = 380
Mr = 364.40	Dx = 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

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

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(Fo2) + (0.0457P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2891 reflections	Δρmax = 0.17 e Å−3
227 parameters	Δρmin = −0.28 e Å−3
1 restraint	Absolute structure: Flack (1983), 1569 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (10)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···N2iv	0.93	2.66	3.412 (5)	139

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⋯N2iv	0.93	2.66	3.412 (5)	139

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .