4-Amino-12-methyl-sulfon-yloxy-[2.2]para-cyclo-phane.

The title compound, C17H19NO3S, was synthesized from 4-benzhydryl-idene-amino-12-hy-droxy-[2.2]para-cyclo-phane and methane-sulfonyl chloride. In the mol-ecule, the distance between the centroids of two aromatic rings is 2.960 (5) Å. In the crystal, weak N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into layers parallel to the ac plane.

Related literature

For background to [2.2]para­cyclo­phane, see: Cram et al. (1959 ▶); Liebman & Greenberg (1976 ▶); Dyson et al. (1998 ▶). For its synthesis and applications in catalysis, see: Hou et al. (2000 ▶); Duan et al. (2008 ▶, 2012 ▶). For a related structure, see: Ma et al. (2012 ▶).

Experimental

Crystal data

C17H19NO3S

M = 317.39

Orthorhombic,

a = 8.017 (7) Å

b = 11.734 (9) Å

c = 16.131 (13) Å

V = 1517 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 273 K

0.13 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.971, T max = 0.978

7769 measured reflections

2676 independent reflections

2266 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.084

S = 1.04

2676 reflections

200 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack (1983 ▶), 1122 Friedel pairs

Absolute structure parameter: 0.02 (9)

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: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813032595/cv5436sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813032595/cv5436Isup2.hkl

Additional supporting information: crystallographic information; 3D view; checkCIF report

C17H19NO3S	F(000) = 672
Mr = 317.39	Dx = 1.389 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2210 reflections
a = 8.017 (7) Å	θ = 2.8–23.1°
b = 11.734 (9) Å	µ = 0.23 mm−1
c = 16.131 (13) Å	T = 273 K
V = 1517 (2) Å3	Block, colourless
Z = 4	0.13 × 0.12 × 0.10 mm

Bruker SMART CCD diffractometer	2676 independent reflections
Radiation source: fine-focus sealed tube	2266 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
phi and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
Tmin = 0.971, Tmax = 0.978	k = −13→13
7769 measured reflections	l = −11→19

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)] = 0.038	H-atom parameters constrained
wR(F2) = 0.084	w = 1/[σ2(Fo2) + (0.0436P)2 + 0.0218P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2676 reflections	Δρmax = 0.15 e Å−3
200 parameters	Δρmin = −0.23 e Å−3
0 restraints	Absolute structure: Flack (1983), 1122 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (9)

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
C1	1.0276 (4)	0.2690 (2)	0.10319 (15)	0.0464 (7)
H1C	1.0358	0.1905	0.0849	0.056*
H1D	1.1386	0.3019	0.1019	0.056*
C2	0.9100 (3)	0.3373 (2)	0.04181 (16)	0.0484 (7)
H2A	0.9781	0.3785	0.0022	0.058*
H2B	0.8411	0.2839	0.0113	0.058*
C3	0.7987 (3)	0.4208 (2)	0.08747 (14)	0.0386 (6)
C4	0.6334 (4)	0.3938 (2)	0.10371 (16)	0.0478 (7)
H4	0.5785	0.3439	0.0682	0.057*
C5	0.5469 (3)	0.4382 (2)	0.17062 (18)	0.0492 (7)
H5	0.4357	0.4188	0.1794	0.059*
C6	0.6281 (3)	0.5120 (2)	0.22456 (16)	0.0412 (6)
C7	0.7798 (3)	0.5569 (2)	0.19893 (15)	0.0402 (6)
H7	0.8257	0.6175	0.2283	0.048*
C8	0.8654 (3)	0.5139 (2)	0.13052 (15)	0.0376 (6)
C9	0.5778 (4)	0.5230 (3)	0.31434 (17)	0.0551 (8)
H9A	0.4571	0.5206	0.3180	0.066*
H9B	0.6140	0.5967	0.3348	0.066*
C10	0.6529 (3)	0.4269 (2)	0.37183 (16)	0.0491 (7)
H10A	0.7088	0.4625	0.4185	0.059*
H10B	0.5624	0.3808	0.3935	0.059*
C11	0.7741 (3)	0.3510 (2)	0.32766 (15)	0.0359 (6)
C12	0.7184 (3)	0.2616 (2)	0.27724 (15)	0.0425 (7)
H12	0.6159	0.2280	0.2886	0.051*
C13	0.8110 (3)	0.2222 (2)	0.21135 (16)	0.0432 (7)
H13	0.7716	0.1612	0.1802	0.052*
C14	0.9620 (3)	0.27203 (19)	0.19075 (14)	0.0358 (6)
C15	1.0336 (3)	0.34300 (19)	0.24992 (15)	0.0336 (6)
H15	1.1437	0.3666	0.2440	0.040*
C16	0.9421 (3)	0.37825 (19)	0.31712 (14)	0.0304 (6)
C17	1.0148 (4)	0.3455 (2)	0.51017 (17)	0.0548 (8)
H17A	0.9649	0.2812	0.4830	0.082*
H17B	0.9287	0.3953	0.5303	0.082*
H17C	1.0816	0.3196	0.5558	0.082*
N1	1.0226 (3)	0.5546 (2)	0.11279 (15)	0.0610 (7)
H1A	1.0668	0.6060	0.1438	0.073*
H1B	1.0764	0.5286	0.0707	0.073*
O1	1.2545 (2)	0.34091 (17)	0.40407 (12)	0.0602 (6)
O2	1.2004 (2)	0.52194 (15)	0.47560 (11)	0.0553 (5)
O3	1.0125 (2)	0.46195 (13)	0.37118 (10)	0.0355 (4)
S1	1.14007 (8)	0.41905 (5)	0.43999 (4)	0.03807 (18)

	U11	U22	U33	U12	U13	U23
C1	0.0554 (18)	0.0443 (15)	0.0395 (15)	0.0054 (14)	0.0040 (13)	−0.0094 (12)
C2	0.059 (2)	0.0540 (16)	0.0325 (15)	−0.0026 (14)	0.0012 (12)	−0.0085 (12)
C3	0.0400 (15)	0.0459 (14)	0.0298 (13)	−0.0008 (13)	−0.0051 (10)	0.0041 (11)
C4	0.0484 (17)	0.0558 (17)	0.0393 (15)	−0.0035 (15)	−0.0172 (14)	−0.0016 (12)
C5	0.0306 (15)	0.0631 (18)	0.0538 (17)	0.0011 (14)	−0.0059 (13)	0.0068 (14)
C6	0.0382 (16)	0.0432 (15)	0.0421 (15)	0.0115 (13)	0.0007 (13)	0.0056 (11)
C7	0.0513 (17)	0.0289 (13)	0.0404 (15)	0.0050 (12)	−0.0003 (12)	−0.0003 (10)
C8	0.0431 (15)	0.0360 (13)	0.0338 (13)	−0.0012 (12)	0.0014 (12)	0.0090 (10)
C9	0.056 (2)	0.0561 (17)	0.0530 (18)	0.0177 (16)	0.0161 (14)	0.0021 (14)
C10	0.0341 (14)	0.0767 (19)	0.0365 (14)	0.0078 (15)	0.0061 (12)	0.0012 (14)
C11	0.0330 (15)	0.0466 (15)	0.0281 (13)	−0.0016 (12)	−0.0026 (11)	0.0087 (11)
C12	0.0351 (15)	0.0496 (16)	0.0429 (16)	−0.0107 (13)	−0.0067 (12)	0.0127 (12)
C13	0.0544 (19)	0.0347 (14)	0.0404 (15)	−0.0060 (13)	−0.0051 (13)	−0.0017 (11)
C14	0.0388 (16)	0.0315 (12)	0.0372 (14)	0.0068 (12)	−0.0027 (11)	0.0004 (11)
C15	0.0270 (14)	0.0386 (13)	0.0353 (13)	0.0041 (11)	−0.0025 (11)	0.0011 (11)
C16	0.0300 (14)	0.0328 (12)	0.0283 (13)	0.0000 (11)	−0.0044 (11)	0.0015 (10)
C17	0.064 (2)	0.0572 (17)	0.0435 (17)	−0.0100 (16)	−0.0063 (14)	0.0125 (13)
N1	0.0609 (17)	0.0645 (16)	0.0575 (15)	−0.0188 (14)	0.0172 (13)	−0.0116 (12)
O1	0.0347 (11)	0.0791 (13)	0.0669 (14)	0.0165 (11)	−0.0073 (10)	−0.0073 (10)
O2	0.0593 (13)	0.0522 (11)	0.0543 (12)	−0.0180 (10)	−0.0204 (9)	−0.0005 (9)
O3	0.0377 (10)	0.0345 (8)	0.0344 (9)	0.0015 (8)	−0.0078 (8)	−0.0002 (7)
S1	0.0327 (3)	0.0438 (3)	0.0377 (3)	−0.0030 (3)	−0.0080 (3)	0.0024 (3)

C1—C14	1.508 (4)	C10—H10A	0.9700
C1—C2	1.585 (4)	C10—H10B	0.9700
C1—H1C	0.9700	C11—C16	1.394 (3)
C1—H1D	0.9700	C11—C12	1.401 (4)
C2—C3	1.516 (4)	C12—C13	1.377 (4)
C2—H2A	0.9700	C12—H12	0.9300
C2—H2B	0.9700	C13—C14	1.384 (4)
C3—C4	1.387 (4)	C13—H13	0.9300
C3—C8	1.400 (3)	C14—C15	1.391 (3)
C4—C5	1.385 (4)	C15—C16	1.373 (3)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.390 (4)	C16—O3	1.430 (3)
C5—H5	0.9300	C17—S1	1.742 (3)
C6—C7	1.389 (4)	C17—H17A	0.9600
C6—C9	1.509 (4)	C17—H17B	0.9600
C7—C8	1.394 (4)	C17—H17C	0.9600
C7—H7	0.9300	N1—H1A	0.8600
C8—N1	1.377 (3)	N1—H1B	0.8600
C9—C10	1.579 (4)	O1—S1	1.421 (2)
C9—H9A	0.9700	O2—S1	1.422 (2)
C9—H9B	0.9700	O3—S1	1.5908 (18)
C10—C11	1.499 (4)
C14—C1—C2	111.5 (2)	C9—C10—H10A	109.0
C14—C1—H1C	109.3	C11—C10—H10B	109.0
C2—C1—H1C	109.3	C9—C10—H10B	109.0
C14—C1—H1D	109.3	H10A—C10—H10B	107.8
C2—C1—H1D	109.3	C16—C11—C12	114.1 (2)
H1C—C1—H1D	108.0	C16—C11—C10	123.2 (2)
C3—C2—C1	111.9 (2)	C12—C11—C10	120.9 (2)
C3—C2—H2A	109.2	C13—C12—C11	121.9 (2)
C1—C2—H2A	109.2	C13—C12—H12	119.1
C3—C2—H2B	109.2	C11—C12—H12	119.1
C1—C2—H2B	109.2	C12—C13—C14	121.0 (2)
H2A—C2—H2B	107.9	C12—C13—H13	119.5
C4—C3—C8	116.7 (2)	C14—C13—H13	119.5
C4—C3—C2	120.4 (2)	C13—C14—C15	116.7 (2)
C8—C3—C2	121.3 (2)	C13—C14—C1	121.3 (2)
C5—C4—C3	122.7 (3)	C15—C14—C1	120.9 (2)
C5—C4—H4	118.7	C16—C15—C14	120.1 (2)
C3—C4—H4	118.7	C16—C15—H15	119.9
C4—C5—C6	119.2 (3)	C14—C15—H15	120.0
C4—C5—H5	120.4	C15—C16—C11	122.9 (2)
C6—C5—H5	120.4	C15—C16—O3	118.5 (2)
C5—C6—C7	117.4 (2)	C11—C16—O3	117.7 (2)
C5—C6—C9	122.0 (3)	S1—C17—H17A	109.5
C7—C6—C9	119.2 (3)	S1—C17—H17B	109.5
C6—C7—C8	122.0 (3)	H17A—C17—H17B	109.5
C6—C7—H7	119.0	S1—C17—H17C	109.5
C8—C7—H7	119.0	H17A—C17—H17C	109.5
N1—C8—C7	119.3 (2)	H17B—C17—H17C	109.5
N1—C8—C3	121.1 (2)	C8—N1—H1A	120.0
C7—C8—C3	119.1 (3)	C8—N1—H1B	120.0
C6—C9—C10	113.6 (2)	H1A—N1—H1B	120.0
C6—C9—H9A	108.8	C16—O3—S1	117.52 (14)
C10—C9—H9A	108.8	O1—S1—O2	119.55 (14)
C6—C9—H9B	108.8	O1—S1—O3	109.55 (12)
C10—C9—H9B	108.8	O2—S1—O3	103.40 (10)
H9A—C9—H9B	107.7	O1—S1—C17	108.54 (14)
C11—C10—C9	113.1 (2)	O2—S1—C17	110.74 (14)
C11—C10—H10A	109.0	O3—S1—C17	103.86 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2i	0.86	2.43	3.262 (3)	163
C10—H10B···O1ii	0.97	2.52	3.390 (4)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2i	0.86	2.43	3.262 (3)	163
C10—H10B⋯O1ii	0.97	2.52	3.390 (4)	149

Symmetry codes: (i) ; (ii) .