4-Amino-13-(1-naphth-yl)-[2,2]paracyclo-phane.

THE TITLE COMPOUND [SYSTEMATIC NAME: 1(2)-amino-4(2)-(1-naphth-yl)-1,4(1,4)-dibenzenacyclo-hexa-phane], C(26)H(23)N, was synthesized from 4-amino-13-bromo-[2,2]paracyclo-phane and 1-naphthalene-boronic acid in the presence of 1,4-dioxane. It is a new cyclo-phane-derived compound which can be regarded as a prospective ligand for asymmetric synthesis and catalysis. The benzene rings of the paracyclo-phane units are very slightly deformed from planarity as shallow boats.

Related literature

For related literature on paracyclo­phane chemistry, see: Cipiciani et al. (1997 ▶); on diphosphanes, see: Pye et al. (1997 ▶); on n class="Chemical">oxazoline-phosphanes, see: Wu et al. (2003 ▶); on oxazoline-imidazolium, see: Bolm et al. (2003 ▶); on oxazoline-selenides, see: Hou et al. (2000 ▶); on oxazoline-alcohols, see: Wu et al. (2001 ▶).

Experimental

Crystal data

C26H23N

M = 349.45

Orthorhombic,

a = 8.5261 (5) Å

b = 12.8123 (8) Å

c = 17.2065 (11) Å

V = 1879.6 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.07 mm−1

T = 293 (2) K

0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.990, T max = 0.993

9879 measured reflections

1901 independent reflections

1690 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.159

S = 1.00

1901 reflections

245 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536808005333/kj2079sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005333/kj2079Isup2.hkl

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

C26H23N	Dx = 1.235 Mg m−3
Mr = 349.45	Mo Kα radiation λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 3936 reflections
a = 8.5261 (5) Å	θ = 2.7–25.1º
b = 12.8123 (8) Å	µ = 0.07 mm−1
c = 17.2065 (11) Å	T = 293 (2) K
V = 1879.6 (2) Å3	Block, colorless
Z = 4	0.15 × 0.12 × 0.10 mm
F000 = 744

Bruker SMART APEXII CCD area-detector diffractometer	1901 independent reflections
Radiation source: fine-focus sealed tube	1690 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.026
T = 293(2) K	θmax = 25.0º
φ and ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −8→10
Tmin = 0.990, Tmax = 0.993	k = −14→15
9879 measured reflections	l = −12→20

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)] = 0.054	H-atom parameters constrained
wR(F2) = 0.159	w = 1/[σ2(Fo2) + (0.0986P)2 + 0.8216P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.005
1901 reflections	Δρmax = 0.37 e Å−3
245 parameters	Δρmin = −0.32 e Å−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (5)

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
N1	0.2691 (6)	0.4913 (3)	0.2196 (3)	0.0659 (12)
H1A	0.2007	0.5066	0.2545	0.079*
H1B	0.3499	0.5306	0.2131	0.079*
C1	0.2490 (5)	0.4028 (3)	0.1733 (2)	0.0497 (11)
C2	0.1199 (5)	0.3383 (4)	0.1826 (3)	0.0561 (12)
H2	0.0486	0.3532	0.2219	0.067*
C3	0.0935 (6)	0.2543 (4)	0.1365 (3)	0.0628 (13)
C4	0.1940 (7)	0.2352 (4)	0.0744 (3)	0.0683 (15)
H4	0.1728	0.1820	0.0392	0.082*
C5	0.3267 (7)	0.2972 (4)	0.0662 (3)	0.0628 (14)
H5	0.3937	0.2856	0.0244	0.075*
C6	0.3618 (6)	0.3758 (4)	0.1187 (2)	0.0515 (11)
C7	0.0003 (7)	0.1612 (5)	0.1707 (4)	0.0833 (19)
H7A	−0.0545	0.1263	0.1287	0.100*
H7B	−0.0782	0.1882	0.2063	0.100*
C8	0.1025 (7)	0.0790 (4)	0.2147 (4)	0.0692 (15)
H8A	0.0486	0.0596	0.2622	0.083*
H8B	0.1106	0.0169	0.1827	0.083*
C9	0.2692 (6)	0.1156 (3)	0.2358 (3)	0.0517 (11)
C10	0.3837 (6)	0.1093 (3)	0.1808 (3)	0.0539 (12)
H10	0.3753	0.0595	0.1417	0.065*
C11	0.5102 (6)	0.1742 (3)	0.1817 (3)	0.0515 (11)
H11	0.5909	0.1640	0.1461	0.062*
C12	0.5201 (5)	0.2548 (3)	0.2347 (2)	0.0417 (10)
C13	0.4179 (5)	0.2553 (3)	0.2981 (2)	0.0394 (9)
C14	0.2894 (5)	0.1865 (3)	0.2960 (2)	0.0465 (10)
H14	0.2162	0.1885	0.3361	0.056*
C15	0.6056 (5)	0.3547 (4)	0.2093 (3)	0.0504 (11)
H15A	0.7152	0.3386	0.2001	0.061*
H15B	0.6005	0.4055	0.2510	0.061*
C16	0.5336 (6)	0.4041 (4)	0.1335 (3)	0.0585 (13)
H16A	0.5423	0.4794	0.1370	0.070*
H16B	0.5955	0.3816	0.0892	0.070*
C17	0.4316 (5)	0.3268 (3)	0.3660 (2)	0.0442 (10)
C18	0.3029 (6)	0.3795 (4)	0.3928 (3)	0.0567 (12)
H18	0.2071	0.3686	0.3683	0.068*
C19	0.3088 (8)	0.4494 (5)	0.4558 (3)	0.0711 (16)
H19	0.2190	0.4849	0.4713	0.085*
C20	0.4445 (9)	0.4643 (5)	0.4931 (3)	0.0748 (18)
H20	0.4484	0.5109	0.5345	0.090*
C21	0.5830 (7)	0.4106 (4)	0.4706 (3)	0.0630 (15)
C22	0.5777 (6)	0.3395 (4)	0.4069 (2)	0.0479 (11)
C23	0.7156 (6)	0.2835 (4)	0.3886 (3)	0.0599 (13)
H23	0.7143	0.2352	0.3482	0.072*
C24	0.8502 (7)	0.2994 (5)	0.4293 (4)	0.0771 (18)
H24	0.9397	0.2614	0.4170	0.093*
C25	0.8549 (10)	0.3729 (6)	0.4899 (4)	0.091 (2)
H25	0.9485	0.3850	0.5162	0.109*
C26	0.7244 (9)	0.4258 (5)	0.5102 (3)	0.080 (2)
H26	0.7285	0.4732	0.5512	0.096*

	U11	U22	U33	U12	U13	U23
N1	0.069 (3)	0.048 (2)	0.081 (3)	0.005 (2)	−0.001 (2)	−0.009 (2)
C1	0.055 (3)	0.042 (2)	0.052 (2)	0.007 (2)	−0.010 (2)	0.009 (2)
C2	0.044 (2)	0.055 (3)	0.069 (3)	0.007 (2)	−0.011 (2)	0.005 (2)
C3	0.054 (3)	0.062 (3)	0.073 (3)	−0.001 (3)	−0.022 (3)	0.002 (3)
C4	0.084 (4)	0.060 (3)	0.061 (3)	−0.001 (3)	−0.033 (3)	−0.006 (3)
C5	0.081 (3)	0.072 (3)	0.036 (2)	−0.002 (3)	−0.005 (2)	0.002 (2)
C6	0.063 (3)	0.051 (2)	0.041 (2)	−0.006 (2)	−0.003 (2)	0.012 (2)
C7	0.059 (3)	0.075 (4)	0.116 (5)	−0.024 (3)	−0.026 (4)	0.002 (4)
C8	0.072 (3)	0.052 (3)	0.083 (3)	−0.026 (3)	−0.013 (3)	−0.002 (3)
C9	0.062 (3)	0.035 (2)	0.058 (2)	−0.008 (2)	−0.011 (2)	0.0041 (19)
C10	0.068 (3)	0.034 (2)	0.060 (3)	0.005 (2)	−0.011 (2)	−0.009 (2)
C11	0.055 (3)	0.044 (2)	0.055 (2)	0.011 (2)	0.000 (2)	−0.007 (2)
C12	0.0367 (19)	0.039 (2)	0.049 (2)	0.0018 (18)	−0.0046 (18)	−0.0019 (18)
C13	0.043 (2)	0.0339 (19)	0.042 (2)	0.0011 (17)	−0.0071 (17)	0.0002 (16)
C14	0.052 (2)	0.042 (2)	0.045 (2)	−0.006 (2)	−0.004 (2)	0.0073 (19)
C15	0.042 (2)	0.049 (2)	0.060 (3)	−0.008 (2)	0.010 (2)	−0.003 (2)
C16	0.065 (3)	0.062 (3)	0.049 (2)	−0.016 (3)	0.013 (2)	0.006 (2)
C17	0.054 (2)	0.039 (2)	0.040 (2)	−0.0040 (19)	−0.001 (2)	0.0009 (18)
C18	0.063 (3)	0.055 (3)	0.052 (2)	−0.003 (2)	0.009 (2)	−0.007 (2)
C19	0.087 (4)	0.066 (3)	0.060 (3)	0.004 (3)	0.015 (3)	−0.014 (3)
C20	0.117 (5)	0.060 (3)	0.047 (3)	−0.017 (3)	0.016 (3)	−0.013 (2)
C21	0.096 (4)	0.055 (3)	0.038 (2)	−0.028 (3)	−0.010 (3)	0.009 (2)
C22	0.061 (3)	0.043 (2)	0.040 (2)	−0.013 (2)	−0.009 (2)	0.0080 (18)
C23	0.061 (3)	0.061 (3)	0.057 (3)	−0.004 (2)	−0.017 (2)	0.009 (2)
C24	0.062 (3)	0.085 (4)	0.084 (4)	−0.012 (3)	−0.026 (3)	0.029 (3)
C25	0.101 (5)	0.105 (5)	0.068 (4)	−0.048 (5)	−0.044 (4)	0.026 (4)
C26	0.104 (5)	0.083 (4)	0.054 (3)	−0.035 (4)	−0.028 (3)	0.013 (3)

N1—C1	1.396 (6)	C12—C15	1.537 (6)
N1—H1A	0.8600	C13—C14	1.406 (6)
N1—H1B	0.8600	C13—C17	1.489 (6)
C1—C2	1.386 (7)	C14—H14	0.9300
C1—C6	1.389 (7)	C15—C16	1.574 (7)
C2—C3	1.354 (7)	C15—H15A	0.9700
C2—H2	0.9300	C15—H15B	0.9700
C3—C4	1.391 (8)	C16—H16A	0.9700
C3—C7	1.549 (8)	C16—H16B	0.9700
C4—C5	1.390 (8)	C17—C18	1.369 (6)
C4—H4	0.9300	C17—C22	1.440 (6)
C5—C6	1.385 (7)	C18—C19	1.406 (7)
C5—H5	0.9300	C18—H18	0.9300
C6—C16	1.530 (7)	C19—C20	1.337 (9)
C7—C8	1.563 (8)	C19—H19	0.9300
C7—H7A	0.9700	C20—C21	1.421 (9)
C7—H7B	0.9700	C20—H20	0.9300
C8—C9	1.539 (7)	C21—C26	1.398 (8)
C8—H8A	0.9700	C21—C22	1.426 (7)
C8—H8B	0.9700	C22—C23	1.413 (7)
C9—C10	1.362 (7)	C23—C24	1.360 (7)
C9—C14	1.390 (6)	C23—H23	0.9300
C10—C11	1.362 (7)	C24—C25	1.405 (10)
C10—H10	0.9300	C24—H24	0.9300
C11—C12	1.381 (6)	C25—C26	1.349 (10)
C11—H11	0.9300	C25—H25	0.9300
C12—C13	1.395 (6)	C26—H26	0.9300
C1—N1—H1A	120.0	C14—C13—C17	117.8 (4)
C1—N1—H1B	120.0	C9—C14—C13	121.7 (4)
H1A—N1—H1B	120.0	C9—C14—H14	119.2
C2—C1—C6	118.7 (4)	C13—C14—H14	119.2
C2—C1—N1	121.1 (5)	C12—C15—C16	112.7 (4)
C6—C1—N1	120.2 (4)	C12—C15—H15A	109.0
C3—C2—C1	122.6 (5)	C16—C15—H15A	109.0
C3—C2—H2	118.7	C12—C15—H15B	109.0
C1—C2—H2	118.7	C16—C15—H15B	109.0
C2—C3—C4	119.1 (5)	H15A—C15—H15B	107.8
C2—C3—C7	118.3 (5)	C6—C16—C15	114.6 (4)
C4—C3—C7	118.1 (5)	C6—C16—H16A	108.6
C5—C4—C3	118.6 (5)	C15—C16—H16A	108.6
C5—C4—H4	120.7	C6—C16—H16B	108.6
C3—C4—H4	120.7	C15—C16—H16B	108.6
C6—C5—C4	121.7 (5)	H16A—C16—H16B	107.6
C6—C5—H5	119.2	C18—C17—C22	118.2 (4)
C4—C5—H5	119.2	C18—C17—C13	120.4 (4)
C5—C6—C1	118.2 (5)	C22—C17—C13	121.4 (4)
C5—C6—C16	119.2 (5)	C17—C18—C19	123.1 (5)
C1—C6—C16	119.4 (4)	C17—C18—H18	118.5
C3—C7—C8	114.6 (4)	C19—C18—H18	118.5
C3—C7—H7A	108.6	C20—C19—C18	119.4 (6)
C8—C7—H7A	108.6	C20—C19—H19	120.3
C3—C7—H7B	108.6	C18—C19—H19	120.3
C8—C7—H7B	108.6	C19—C20—C21	121.3 (5)
H7A—C7—H7B	107.6	C19—C20—H20	119.3
C9—C8—C7	115.1 (4)	C21—C20—H20	119.3
C9—C8—H8A	108.5	C26—C21—C20	121.1 (5)
C7—C8—H8A	108.5	C26—C21—C22	119.5 (6)
C9—C8—H8B	108.5	C20—C21—C22	119.5 (5)
C7—C8—H8B	108.5	C23—C22—C21	118.0 (4)
H8A—C8—H8B	107.5	C23—C22—C17	123.6 (4)
C10—C9—C14	117.9 (4)	C21—C22—C17	118.4 (5)
C10—C9—C8	118.7 (4)	C24—C23—C22	120.7 (5)
C14—C9—C8	119.3 (5)	C24—C23—H23	119.6
C11—C10—C9	121.6 (4)	C22—C23—H23	119.6
C11—C10—H10	119.2	C23—C24—C25	120.5 (7)
C9—C10—H10	119.2	C23—C24—H24	119.8
C10—C11—C12	120.8 (4)	C25—C24—H24	119.8
C10—C11—H11	119.6	C26—C25—C24	120.3 (6)
C12—C11—H11	119.6	C26—C25—H25	119.8
C11—C12—C13	118.8 (4)	C24—C25—H25	119.8
C11—C12—C15	117.6 (4)	C25—C26—C21	120.9 (6)
C13—C12—C15	121.0 (4)	C25—C26—H26	119.5
C12—C13—C14	117.7 (4)	C21—C26—H26	119.5
C12—C13—C17	124.5 (4)
C6—C1—C2—C3	−5.0 (3)	C11—C12—C15—C16	56.6 (5)
N1—C1—C2—C3	177.2 (4)	C13—C12—C15—C16	−104.9 (5)
C1—C2—C3—C4	−4.0 (3)	C5—C6—C16—C15	−99.3 (5)
C1—C2—C3—C7	152.0 (4)	C1—C6—C16—C15	60.0 (6)
C2—C3—C4—C5	6.0 (5)	C12—C15—C16—C6	24.3 (6)
C7—C3—C4—C5	−150.0 (5)	C12—C13—C17—C18	132.4 (4)
C3—C4—C5—C6	1.0 (6)	C14—C13—C17—C18	−44.7 (5)
C4—C5—C6—C1	−9.9 (6)	C12—C13—C17—C22	−50.0 (6)
C4—C5—C6—C16	149.7 (4)	C14—C13—C17—C22	132.9 (4)
C2—C1—C6—C5	11.8 (5)	C22—C17—C18—C19	3.4 (7)
N1—C1—C6—C5	−170.4 (4)	C13—C17—C18—C19	−178.9 (4)
C2—C1—C6—C16	−147.8 (4)	C17—C18—C19—C20	−1.6 (8)
N1—C1—C6—C16	30.0 (6)	C18—C19—C20—C21	−0.3 (9)
C2—C3—C7—C8	−87.2 (6)	C19—C20—C21—C26	−179.5 (5)
C4—C3—C7—C8	69.0 (7)	C19—C20—C21—C22	0.3 (8)
C3—C7—C8—C9	15.1 (8)	C26—C21—C22—C23	2.8 (7)
C7—C8—C9—C10	−82.7 (6)	C20—C21—C22—C23	−176.9 (5)
C7—C8—C9—C14	74.1 (7)	C26—C21—C22—C17	−178.7 (4)
C14—C9—C10—C11	−3.8 (3)	C20—C21—C22—C17	1.6 (7)
C8—C9—C10—C11	153.4 (4)	C18—C17—C22—C23	175.1 (4)
C9—C10—C11—C12	−5.6 (3)	C13—C17—C22—C23	−2.6 (7)
C10—C11—C12—C13	14.2 (5)	C18—C17—C22—C21	−3.3 (6)
C10—C11—C12—C15	−147.7 (3)	C13—C17—C22—C21	179.0 (4)
C11—C12—C13—C14	−13.1 (5)	C21—C22—C23—C24	−1.8 (7)
C15—C12—C13—C14	148.2 (4)	C17—C22—C23—C24	179.8 (5)
C11—C12—C13—C17	169.7 (4)	C22—C23—C24—C25	−0.7 (8)
C15—C12—C13—C17	−29.0 (6)	C23—C24—C25—C26	2.4 (9)
C10—C9—C14—C13	4.5 (5)	C24—C25—C26—C21	−1.4 (9)
C8—C9—C14—C13	−152.5 (4)	C20—C21—C26—C25	178.5 (5)
C12—C13—C14—C9	4.0 (5)	C22—C21—C26—C25	−1.3 (8)
C17—C13—C14—C9	−178.7 (4)