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

Nakanishi, W.; Xue, J.Y.; Yoshioka, T.; Isobe, H.

doi:10.1107/S1600536811023427

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages o1762-o1763

doi:10.1107/S1600536811023427

Open

access

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

Waka Nakanishi,^a Jing Yang Xue,^a Tomoaki Yoshioka ^a and Hiroyuki Isobe ^a ^*

^aDepartment of Chemistry, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan
^*Correspondence e-mail: isobe@m.tohoku.ac.jp

(Received 31 May 2011; accepted 16 June 2011; online 22 June 2011)

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 $[P\overline1]$ 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, C m c a
a = 34.224 (6) Å
b = 7.4629 (14) Å
c = 15.131 (3) Å
V = 3864.7 (12) Å³
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[F² > 2σ(F²)] = 0.066
wR(F²) = 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811023427/nr2007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023427/nr2007Isup2.hkl

checkCIF report

Comment top

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 C₂_h 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.

Related literature top

For the synthesis and preceding crystallographic analysis, see: Nakanishi et al. (2011). For the original method of recrystallization, see: Miyahara & Shimizu (2001). For the review of C—H···π contacts in crystals, see: Nishio (2004).

Experimental top

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).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2004); 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 (Sheldrick, 2008) and Yadokari-XG 2009 (Kabuto et al., 2009) and publCIF (Westrip, 2010).

Figures top

	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.

[6]Cyclo-2,7-naphthylene top

Crystal data top

C₆₀H₃₆	F(000) = 1584
M_r = 756.89	D_x = 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 top

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 monochromator	R_int = 0.035
Detector resolution: 8.333 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
ϕ and ω scans	h = −43→43
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→9
T_min = 0.686, T_max = 0.996	l = −19→19
20522 measured reflections

Refinement top

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(F_o²) + (0.0565P)² + 7.0687P] where P = (F_o² + 2F_c²)/3
2234 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₆₀H₃₆	V = 3864.7 (12) Å³
M_r = 756.89	Z = 4
Orthorhombic, Cmca	Mo Kα radiation
a = 34.224 (6) Å	µ = 0.07 mm⁻¹
b = 7.4629 (14) Å	T = 100 K
c = 15.131 (3) Å	0.40 × 0.12 × 0.06 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2234 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1667 reflections with I > 2σ(I)
T_min = 0.686, T_max = 0.996	R_int = 0.035
20522 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 1.06	Δρ_max = 0.20 e Å⁻³
2234 reflections	Δρ_min = −0.35 e Å⁻³
139 parameters

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
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 (Å²) top

	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, º) top

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.

Experimental details

Crystal data
Chemical formula	C₆₀H₃₆
M_r	756.89
Crystal system, space group	Orthorhombic, Cmca
Temperature (K)	100
a, b, c (Å)	34.224 (6), 7.4629 (14), 15.131 (3)
V (Å³)	3864.7 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.40 × 0.12 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.686, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	20522, 2234, 1667
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.181, 1.06
No. of reflections	2234
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.35

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and Yadokari-XG 2009 (Kabuto et al., 2009) and publCIF (Westrip, 2010).

Acknowledgements

This study was partly supported by KAKENHI (21685005, 20108015 to HI and 22550094 to WN). We thank Professor T. Iwamoto for the use of the X-ray instrument.

References

Bruker (2004). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kabuto, C., Akine, S., Nemoto, T. & Kwon, E. (2009). J. Cryst. Soc. Jpn, 51, 218–224. CrossRef Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Miyahara, T. & Shimizu, M. (2001). J. Cryst. Growth, 229, 553–557. CrossRef CAS Google Scholar
Nakanishi, W., Yoshioka, T., Taka, H., Xue, J. Y., Kita, H. & Isobe, H. (2011). Angew. Chem. Int. Ed. 50, 5323–5326. CrossRef CAS Google Scholar
Nishio, M. (2004). CrystEngComm, 6, 130–158. Web of Science CrossRef CAS 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
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar