[6]Cyclo-2,7-naphthyl­ene: a redetermination

Abstract

Single crystals of a macrocyclic hydro­carbon, [6]cyclo-2,7-naphthyl­ene ([6]CNAP, C₆₀H₃₆) were prepared from anthracene melt with a prolonged time for the recrystallization. The crystal of improved quality led to the correction of the space-group assignment to Cmca from in the original determination [Nakanishi et al. (2011 ▶) Angew. Chem. Int. Ed. 50, 5323–5326] and the refinement of anisotropic displacement parameters of all C atoms. The refined mol­ecular structure with C _2h point symmetry indicated that the strain on the naphthyl rings of [6]CNAP is smallest among the congeners. Despite the large macrocyclic structure, mol­ecules are packed in a ubiquitous herringbone motif. A short C—C distance of 3.119 (4) Å was found in the stacking direction, and a short C—H distance of 2.80 Å was found in the inter­columnar contact.

Related literature

Superior quality crystals of the title compound were obtained by re-optimizing the crystallization conditions. For the synthesis and preceding crystallographic analysis, see: Nakanishi et al. (2011 ▶). For the original method of recrystallization, see: Miyahara & Shimizu (2001 ▶). For a review of C—H⋯π contacts in crystals, see: Nishio (2004 ▶).

Experimental

Crystal data

• C₆₀H₃₆

• M _r = 756.89

• Orthorhombic,

• a = 34.224 (6) Å

• b = 7.4629 (14) Å

• c = 15.131 (3) Å

• V = 3864.7 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 0.07 mm⁻¹

• T = 100 K

• 0.40 × 0.12 × 0.06 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.686, T _max = 0.996

• 20522 measured reflections

• 2234 independent reflections

• 1667 reflections with I > 2σ(I)

• R _int = 0.035

Refinement

• R[F ² > 2σ(F ²)] = 0.066

• wR(F ²) = 0.181

• S = 1.06

• 2234 reflections

• 139 parameters

• H-atom parameters constrained

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and Yadokari-XG 2009 (Kabuto et al., 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

Polycyclic aromatic hydrocarbons are important compounds for the development of organic electronics. As new bipolar carrier transport materials for organic light emitting diodes, we recently reported [n]cyclo-2,7-naphthylenes ([n]CNAP; Nakanishi et al., 2011). The unique macrocyclic structures of [n]CNAPs (n = 5, 6 and 7) were revealed by X-ray crystallographic analysis of the single crystals, but we deferred detailed discussion of the most abundant compounds, [6]CNAP, because of insufficient quality of available data mainly due to weak reflections from the previous crystals. We now obtained single crystals of [6]CNAP with superior quality by re-optimizing the crystallization conditions and successfully corrected the space group assignment to Cmca. The molecular structure of title compound is shown in Fig. 1, and the packing structure is shown in Fig. 2. Most importantly, the refined molecular structure with C_2h point symmetry shows that [6]CNAP has the smallest deformation in the planar naphthyl rings with the average bend angle of 2.3° which is smaller than 16° and 5° of [5]- and [7]CNAPs, respectively. To form the strain-free macrocycle, the naphthyl rings are twisted alternately with dihedral angles of 33.1 (3)° and 25.6 (4)°. Despite the large macrocyclic structure, molecules are packed in a ubiquitous herringbone motif. A short C—C distance of 3.119 (4) Å was found in the stacking direction, and a short C—H distance of 2.80 Å was found in the intercolumnar contact.

Experimental

The title compound was synthesized by a nickel promoted coupling reaction of 2,7-dibromonaphthalene and separated as reported in literature (Nakanishi et al., 2011). A single crystal suitable for X-ray crystallographic analysis was obtained by a solid solvent growth method, as reported except that the time for crystal growth was extended: A mixture of anthracene (200 mg) and [6]CNAP (4 mg) was sealed in a glass tube. The whole glass tube was heated at 350 °C for 2 h. The subsequent crystal-growing time at 210 °C was extended from 2 h to 3 h, and the tube was cooled gradually to ambient temperature. A half of the glass tube was then heated at 200 °C to eliminate anthracene and afford crystals of [6]CNAP. For the original method of recrystallization, see: Miyahara & Shimizu (2001).

Refinement

H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.95 Å (aromatic) and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) x, -y + 2, -z + 1; (ii) -x + 1, y, z; (iii) -x + 1, -y + 2, -z + 1.

Fig. 2.

The packing structure of the title compound, viewed along the a axis.

Crystal data

C60H36	F(000) = 1584
Mr = 756.89	Dx = 1.301 Mg m−3
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 5445 reflections
a = 34.224 (6) Å	θ = 2.4–27.2°
b = 7.4629 (14) Å	µ = 0.07 mm−1
c = 15.131 (3) Å	T = 100 K
V = 3864.7 (12) Å3	Plate, colourless
Z = 4	0.40 × 0.12 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2234 independent reflections
Radiation source: Bruker TXS fine-focus rotating anode	1667 reflections with I > 2σ(I)
Bruker Helios multilayer confocal mirror	Rint = 0.035
Detector resolution: 8.333 pixels mm-1	θmax = 27.5°, θmin = 2.4°
φ and ω scans	h = −43→43
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→9
Tmin = 0.686, Tmax = 0.996	l = −19→19
20522 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0565P)2 + 7.0687P] where P = (Fo2 + 2Fc2)/3
2234 reflections	(Δ/σ)max < 0.001
139 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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
C1	0.28550 (9)	0.7008 (6)	0.37933 (17)	0.0855 (12)
H1	0.2623	0.6634	0.3504	0.103*
C2	0.28488 (8)	0.8521 (5)	0.43007 (18)	0.0805 (11)
H2	0.2610	0.9154	0.4371	0.097*
C3	0.31917 (7)	0.9174 (4)	0.47282 (14)	0.0599 (7)
C4	0.35317 (7)	0.8204 (3)	0.46178 (14)	0.0521 (6)
H3	0.3764	0.8613	0.4897	0.062*
C5	0.35467 (8)	0.6627 (4)	0.41049 (14)	0.0546 (7)
C6	0.32004 (9)	0.5987 (5)	0.36887 (15)	0.0705 (9)
C7	0.32231 (11)	0.4362 (5)	0.32059 (16)	0.0842 (12)
H4	0.2997	0.3918	0.2916	0.101*
C8	0.35645 (11)	0.3425 (4)	0.31496 (15)	0.0777 (11)
H5	0.3570	0.2332	0.2828	0.093*
C9	0.39145 (9)	0.4048 (3)	0.35623 (14)	0.0599 (8)
C10	0.38962 (8)	0.5646 (3)	0.40197 (13)	0.0518 (6)
H6	0.4127	0.6100	0.4286	0.062*
C11	0.46345 (13)	0.0185 (3)	0.35550 (17)	0.0872 (12)
H7	0.4628	−0.1088	0.3562	0.105*
C12	0.42913 (13)	0.1103 (4)	0.35358 (16)	0.0781 (11)
H8	0.4052	0.0460	0.3522	0.094*
C13	0.42846 (10)	0.3024 (3)	0.35367 (14)	0.0602 (8)
C14	0.46407 (8)	0.3892 (3)	0.35413 (14)	0.0542 (7)
H9	0.4643	0.5165	0.3534	0.065*
C15	0.5000	0.2979 (4)	0.35555 (19)	0.0556 (10)
C16	0.5000	0.1066 (4)	0.3565 (2)	0.0708 (13)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0610 (18)	0.162 (4)	0.0339 (13)	−0.048 (2)	−0.0068 (12)	0.0195 (17)
C2	0.0528 (16)	0.151 (3)	0.0375 (13)	−0.0189 (18)	−0.0027 (11)	0.0297 (17)
C3	0.0481 (13)	0.100 (2)	0.0322 (11)	−0.0087 (13)	−0.0009 (9)	0.0234 (11)
C4	0.0553 (14)	0.0695 (15)	0.0314 (10)	−0.0175 (12)	−0.0064 (9)	0.0157 (10)
C5	0.0663 (16)	0.0706 (16)	0.0270 (10)	−0.0286 (13)	−0.0066 (10)	0.0130 (10)
C6	0.0719 (18)	0.114 (2)	0.0260 (10)	−0.0495 (17)	−0.0031 (10)	0.0138 (13)
C7	0.094 (2)	0.129 (3)	0.0301 (12)	−0.074 (2)	−0.0006 (13)	0.0028 (15)
C8	0.116 (3)	0.088 (2)	0.0281 (11)	−0.071 (2)	0.0065 (14)	−0.0042 (12)
C9	0.098 (2)	0.0553 (14)	0.0264 (10)	−0.0412 (15)	−0.0006 (11)	0.0023 (9)
C10	0.0732 (16)	0.0537 (13)	0.0286 (10)	−0.0308 (12)	−0.0056 (10)	0.0062 (9)
C11	0.197 (4)	0.0250 (12)	0.0396 (13)	−0.0237 (18)	0.0074 (18)	−0.0075 (10)
C12	0.160 (3)	0.0402 (14)	0.0340 (12)	−0.0427 (18)	0.0088 (16)	−0.0048 (10)
C13	0.114 (2)	0.0398 (12)	0.0267 (10)	−0.0318 (14)	0.0039 (12)	−0.0045 (9)
C14	0.106 (2)	0.0247 (9)	0.0321 (10)	−0.0139 (11)	0.0003 (11)	−0.0036 (8)
C15	0.114 (3)	0.0230 (14)	0.0300 (14)	0.000	0.000	−0.0045 (11)
C16	0.157 (4)	0.0237 (15)	0.0318 (16)	0.000	0.000	−0.0046 (12)

Geometric parameters (Å, °)

C1—C2	1.365 (5)	C8—H5	0.9500
C1—C6	1.416 (5)	C9—C10	1.381 (3)
C1—H1	0.9500	C9—C13	1.480 (4)
C2—C3	1.426 (4)	C10—H6	0.9500
C2—H2	0.9500	C11—C12	1.360 (5)
C3—C4	1.380 (3)	C11—C16	1.413 (4)
C3—C3i	1.482 (6)	C11—H7	0.9500
C4—C5	1.410 (4)	C12—C13	1.434 (4)
C4—H3	0.9500	C12—H8	0.9500
C5—C10	1.408 (4)	C13—C14	1.380 (4)
C5—C6	1.425 (3)	C14—C15	1.406 (3)
C6—C7	1.418 (5)	C14—H9	0.9500
C7—C8	1.364 (5)	C15—C14ii	1.406 (3)
C7—H4	0.9500	C15—C16	1.428 (4)
C8—C9	1.429 (4)	C16—C11ii	1.413 (4)
C2—C1—C6	121.4 (3)	C10—C9—C8	117.5 (3)
C2—C1—H1	119.3	C10—C9—C13	119.9 (2)
C6—C1—H1	119.3	C8—C9—C13	122.6 (3)
C1—C2—C3	121.7 (3)	C9—C10—C5	122.3 (2)
C1—C2—H2	119.2	C9—C10—H6	118.9
C3—C2—H2	119.2	C5—C10—H6	118.9
C4—C3—C2	117.4 (3)	C12—C11—C16	122.0 (2)
C4—C3—C3i	120.22 (15)	C12—C11—H7	119.0
C2—C3—C3i	122.4 (2)	C16—C11—H7	119.0
C3—C4—C5	122.3 (2)	C11—C12—C13	121.2 (3)
C3—C4—H3	118.8	C11—C12—H8	119.4
C5—C4—H3	118.8	C13—C12—H8	119.4
C10—C5—C4	121.0 (2)	C14—C13—C12	117.1 (3)
C10—C5—C6	119.4 (3)	C14—C13—C9	120.9 (2)
C4—C5—C6	119.5 (3)	C12—C13—C9	122.0 (3)
C1—C6—C7	124.3 (3)	C13—C14—C15	123.0 (2)
C1—C6—C5	117.7 (3)	C13—C14—H9	118.5
C7—C6—C5	118.0 (3)	C15—C14—H9	118.5
C8—C7—C6	121.2 (3)	C14ii—C15—C14	122.0 (3)
C8—C7—H4	119.4	C14ii—C15—C16	118.99 (13)
C6—C7—H4	119.4	C14—C15—C16	118.99 (13)
C7—C8—C9	121.6 (3)	C11ii—C16—C11	124.5 (4)
C7—C8—H5	119.2	C11ii—C16—C15	117.71 (19)
C9—C8—H5	119.2	C11—C16—C15	117.71 (19)
C6—C1—C2—C3	1.9 (4)	C4—C5—C10—C9	176.39 (19)
C1—C2—C3—C4	−0.7 (4)	C6—C5—C10—C9	−1.7 (3)
C1—C2—C3—C3i	179.2 (3)	C16—C11—C12—C13	−0.9 (4)
C2—C3—C4—C5	0.1 (3)	C11—C12—C13—C14	1.2 (4)
C3i—C3—C4—C5	−179.8 (2)	C11—C12—C13—C9	−176.8 (2)
C3—C4—C5—C10	−178.7 (2)	C10—C9—C13—C14	−33.1 (3)
C3—C4—C5—C6	−0.6 (3)	C8—C9—C13—C14	148.8 (2)
C2—C1—C6—C7	177.0 (2)	C10—C9—C13—C12	144.8 (2)
C2—C1—C6—C5	−2.3 (4)	C8—C9—C13—C12	−33.2 (3)
C10—C5—C6—C1	179.8 (2)	C12—C13—C14—C15	−0.8 (3)
C4—C5—C6—C1	1.7 (3)	C9—C13—C14—C15	177.2 (2)
C10—C5—C6—C7	0.4 (3)	C13—C14—C15—C14ii	178.65 (17)
C4—C5—C6—C7	−177.7 (2)	C13—C14—C15—C16	0.1 (4)
C1—C6—C7—C8	−178.5 (2)	C12—C11—C16—C11ii	−177.8 (2)
C5—C6—C7—C8	0.8 (4)	C12—C11—C16—C15	0.1 (4)
C6—C7—C8—C9	−0.9 (4)	C14ii—C15—C16—C11ii	−0.3 (4)
C7—C8—C9—C10	−0.3 (3)	C14—C15—C16—C11ii	178.3 (2)
C7—C8—C9—C13	177.8 (2)	C14ii—C15—C16—C11	−178.3 (2)
C8—C9—C10—C5	1.6 (3)	C14—C15—C16—C11	0.3 (4)
C13—C9—C10—C5	−176.57 (19)

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