The head-to-head photodimer of indeno­indene

Detert, H.; Jacobs, N.; Schollmeyer, D.

doi:10.1107/S2414314620003077

organic compounds

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ISSN: 2414-3146

Volume 5| Part 3| March 2020| x200307

https://doi.org/10.1107/S2414314620003077

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The head-to-head photodimer of indenoindene

Heiner Detert,^a ^* Nina Jacobs ^a and Dieter Schollmeyer ^a

^aJohannes Gutenberg University Mainz, Department of Chemistry, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 15 February 2020; accepted 4 March 2020; online 5 March 2020)

Irradiation of 1-(1-benzocyclobutenylidene)benzocyclobutene gives indenoindene and its head-to-head photodimer nonacyclo[9.7.7.7^2,10.0^1,11.0^2,10.0^3,8.0^12,17.0^19,24.0^26,31]dotriaconta-3,5,7,12,14,16,19,21,23,26,28,30-dodecaene, C₃₂H₂₄. The molecule is built from four essentially planar indane units attached to an elongated cyclobutane ring. In the crystal, C—H⋯π interactions connect molecules into layers parallel to the bc plane.

Keywords: crystal structure; polycyclic hydrocarbon; strain; cyclobutane.

CCDC reference: 1988066

Structure description

The photocycloaddition of 5,10-dihydroindeno[2,1-a]indene (Detert & Schollmeyer, 2019 ) has been studied by Shim (Shim et al., 1983 ) and Wolff (Wolff et al., 1992 ). Head-to-head and head-to-tail photodimers have been found in a 1: 2 ratio (Shim & Chae, 1982 ). As part of a project on strained (Detert et al., 2009 ; Dobryakov et al., 2016 ; Krohn et al., 2019 ) and polycyclic hydrocarbons (Krämer et al., 2009 ; Detert & Meier, 1997a ,b ), indenoindene was prepared in a photochemical rearrangement of 1-(1-benzocyclobutenylidene)benzocyclobutene; concomitant 2 + 2-cycloaddition of indenoindene produced the title compound as a byproduct.

The monoclinic unit cell of the title compound (Fig. 1) contains two centrosymmetrical molecules. The indane units, though containing sp³ carbons, are essentially planar with a maximum deviation of 0.043 (2) Å at C16 from the mean plane. An angle of 51.53 (5)° is opened by the least-squares planes of indanes annulated to the cyclobutane [C8, C16, C8ⁱ, C16ⁱ; symmetry code: (i) 1 − x, 1 − y, 1 − z], nearly identical to the angle of 52.28 (8)° between the planes of indanes on opposite sides of the cyclobutane. The C—C bonds in the central cyclobutane ring are largely elongated, the C8—C16 bond is 1.569 (3) Å long and the C8–C16ⁱ bond, connecting the indanoindane units, is even more stretched to 1.597 (3) Å. This is due to the ecliptic conformation of vicinal methylene groups, the minimal distance between C7—H and C15ⁱ—H is 1.95 Å, lower than the sum of the van der Waals radii. Bond angles in the cyclobutane are close to orthogonal, C8—C16—C8ⁱ = 90.41 (15) and C16—C8—C16ⁱ = 89.59 (15)°. Bond angles on the cyclobutane are much larger, C1—C16—C8ⁱ = 115.12 (17), C1—C16—C15 = 116.65 (19)° and C15—C16—C8ⁱ = 118.80 (19)°. In the crystal, molecules are linked by C—H⋯π interactions (Fig. 2, Table 1), forming layers parallel to the bc plane.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg1ⁱ	0.95	2.77	3.713 (3)	171
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
Perspective view of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The second part of the molecule is generated by the symmetry operation 1 − x, 1 − y, 1 − z.

Figure 2
Partial packing diagram of the title compound. View along the a axis.

Synthesis and crystallization

Indeno[2,1-a]indene (Detert & Schollmeyer, 2019) was prepared from benzocyclobutenone (Schiess & Heitzmann, 1977 ), according to literature procedures (Detert & Schollmeyer, 2018 ; Oelgemöller et al., 2002 ). The photochemical rearrangement was performed in a falling film photoreactor (Normag, Ilmenau) equipped with a medium pressure mercury lamp (TQ 718) in a diluted solution (0.1%) in petroleum ether. Contrary to the irradiation of indenoindene in benzene (Shim & Chae, 1982), the head-to-head isomer was the main dimerization product. Crystals were obtained by slow evaporation of a petroleum ether solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₃₂H₂₄
M_r	408.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	193
a, b, c (Å)	9.3106 (11), 8.7232 (8), 13.4776 (12)
β (°)	91.959 (8)
V (Å³)	1093.99 (19)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.40 × 0.32 × 0.17

Data collection
Diffractometer	Stoe IPDS 2T
No. of measured, independent and observed [I > 2σ(I)] reflections	5905, 2604, 1416
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.196, 0.97
No. of reflections	2604
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.22
Computer programs: X-AREA and X-RED (Stoe & Cie, 1996 ), SIR2004 (Burla et al., 2005 ), SHELXL2018/3 (Sheldrick, 2015 ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 1988066

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314620003077/rz4037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620003077/rz4037Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620003077/rz4037Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 1996); cell refinement: X-AREA (Stoe & Cie, 1996); data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020).

Nonacyclo[9.7.7.7^2,10.0^1,11.0^2,10.0^3,8.0^12,17.0^19,24.0^26,31]dotriaconta-3,5,7,12,14,16,19,21,23,26,28,30-dodecaene top

Crystal data top

C₃₂H₂₄	F(000) = 432
M_r = 408.51	D_x = 1.240 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3106 (11) Å	Cell parameters from 4760 reflections
b = 8.7232 (8) Å	θ = 2.8–28.4°
c = 13.4776 (12) Å	µ = 0.07 mm⁻¹
β = 91.959 (8)°	T = 193 K
V = 1093.99 (19) Å³	Block, colourless
Z = 2	0.40 × 0.32 × 0.17 mm

Data collection top

Stoe IPDS 2T diffractometer	1416 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	R_int = 0.051
Detector resolution: 6.67 pixels mm^-1	θ_max = 28.0°, θ_min = 2.8°
rotation method scans	h = −12→12
5905 measured reflections	k = −11→11
2604 independent reflections	l = −17→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.196	w = 1/[σ²(F_o²) + (0.1156P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
2604 reflections	Δρ_max = 0.19 e Å⁻³
145 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Hydrogen atoms attached to carbons were placed at calculated positions and were refined in the riding-model approximation with C–H = 0.95–0.99 Å, and with U_iso(H) = 1.2 U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.4266 (2)	0.5319 (2)	0.65609 (14)	0.0434 (5)
C2	0.3996 (3)	0.4508 (3)	0.74264 (16)	0.0586 (7)
H2	0.455901	0.363472	0.760360	0.070*
C3	0.2908 (4)	0.4981 (3)	0.80229 (18)	0.0738 (9)
H3	0.271851	0.442967	0.861199	0.089*
C4	0.2099 (3)	0.6238 (4)	0.77730 (18)	0.0675 (8)
H4	0.134797	0.654571	0.818923	0.081*
C5	0.2357 (3)	0.7075 (3)	0.69200 (18)	0.0566 (7)
H5	0.179057	0.794881	0.675228	0.068*
C6	0.3453 (2)	0.6613 (3)	0.63188 (15)	0.0450 (5)
C7	0.3945 (3)	0.7366 (3)	0.53776 (17)	0.0553 (6)
H7A	0.435041	0.839524	0.551922	0.066*
H7B	0.313791	0.746705	0.488456	0.066*
C8	0.5100 (2)	0.6283 (2)	0.49985 (14)	0.0399 (5)
C9	0.6561 (2)	0.6969 (2)	0.48827 (14)	0.0384 (5)
C10	0.6955 (3)	0.8137 (2)	0.42436 (16)	0.0490 (6)
H10	0.625938	0.861017	0.381202	0.059*
C11	0.8370 (3)	0.8597 (3)	0.42464 (19)	0.0635 (7)
H11	0.865113	0.939744	0.381628	0.076*
C12	0.9381 (3)	0.7905 (3)	0.48689 (19)	0.0618 (7)
H12	1.035286	0.823562	0.486287	0.074*
C13	0.9004 (3)	0.6743 (3)	0.54978 (18)	0.0521 (6)
H13	0.970946	0.626587	0.591988	0.063*
C14	0.7580 (2)	0.6277 (2)	0.55081 (16)	0.0429 (5)
C15	0.6931 (3)	0.5091 (3)	0.6165 (2)	0.0581 (7)
H15A	0.700371	0.541016	0.686992	0.070*
H15B	0.741669	0.408951	0.609403	0.070*
C16	0.5354 (2)	0.4997 (2)	0.57990 (15)	0.0419 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0536 (13)	0.0476 (12)	0.0287 (10)	−0.0135 (10)	−0.0022 (8)	0.0010 (9)
C2	0.091 (2)	0.0540 (14)	0.0302 (11)	−0.0209 (13)	0.0020 (11)	0.0007 (10)
C3	0.120 (3)	0.0679 (18)	0.0344 (12)	−0.0366 (18)	0.0200 (14)	−0.0072 (13)
C4	0.081 (2)	0.0788 (19)	0.0440 (13)	−0.0325 (16)	0.0233 (13)	−0.0229 (13)
C5	0.0526 (15)	0.0684 (16)	0.0492 (13)	−0.0105 (12)	0.0069 (11)	−0.0150 (12)
C6	0.0465 (13)	0.0534 (13)	0.0350 (10)	−0.0082 (10)	0.0017 (9)	−0.0040 (9)
C7	0.0527 (15)	0.0652 (15)	0.0483 (12)	0.0166 (12)	0.0070 (10)	0.0127 (11)
C8	0.0440 (12)	0.0416 (11)	0.0342 (10)	0.0045 (9)	0.0033 (8)	0.0083 (9)
C9	0.0483 (13)	0.0309 (10)	0.0363 (10)	0.0003 (9)	0.0061 (8)	−0.0011 (8)
C10	0.0686 (17)	0.0380 (11)	0.0406 (11)	−0.0071 (11)	0.0058 (10)	0.0011 (9)
C11	0.082 (2)	0.0577 (15)	0.0518 (14)	−0.0284 (14)	0.0125 (13)	−0.0015 (12)
C12	0.0597 (17)	0.0669 (16)	0.0597 (15)	−0.0245 (13)	0.0148 (12)	−0.0135 (12)
C13	0.0468 (14)	0.0509 (13)	0.0587 (14)	−0.0052 (11)	0.0030 (11)	−0.0090 (11)
C14	0.0435 (13)	0.0358 (11)	0.0494 (12)	−0.0013 (9)	0.0017 (9)	−0.0015 (9)
C15	0.0492 (14)	0.0524 (14)	0.0719 (16)	−0.0063 (12)	−0.0124 (12)	0.0219 (12)
C16	0.0439 (12)	0.0439 (11)	0.0377 (11)	−0.0032 (9)	−0.0024 (9)	0.0117 (9)

Geometric parameters (Å, º) top

C1—C6	1.392 (3)	C8—C16	1.569 (3)
C1—C2	1.395 (3)	C8—C16ⁱ	1.597 (3)
C1—C16	1.494 (3)	C9—C14	1.386 (3)
C2—C3	1.379 (4)	C9—C10	1.392 (3)
C2—H2	0.9500	C10—C11	1.376 (4)
C3—C4	1.366 (4)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.379 (4)
C4—C5	1.389 (4)	C11—H11	0.9500
C4—H4	0.9500	C12—C13	1.374 (3)
C5—C6	1.384 (3)	C12—H12	0.9500
C5—H5	0.9500	C13—C14	1.388 (3)
C6—C7	1.513 (3)	C13—H13	0.9500
C7—C8	1.532 (3)	C14—C15	1.501 (3)
C7—H7A	0.9900	C15—C16	1.535 (3)
C7—H7B	0.9900	C15—H15A	0.9900
C8—C9	1.500 (3)	C15—H15B	0.9900

C6—C1—C2	119.7 (2)	C14—C9—C10	120.4 (2)
C6—C1—C16	111.58 (18)	C14—C9—C8	111.53 (17)
C2—C1—C16	128.7 (2)	C10—C9—C8	128.0 (2)
C3—C2—C1	119.5 (3)	C11—C10—C9	119.0 (2)
C3—C2—H2	120.3	C11—C10—H10	120.5
C1—C2—H2	120.3	C9—C10—H10	120.5
C4—C3—C2	120.5 (2)	C10—C11—C12	120.5 (2)
C4—C3—H3	119.8	C10—C11—H11	119.8
C2—C3—H3	119.8	C12—C11—H11	119.8
C3—C4—C5	121.1 (3)	C13—C12—C11	121.0 (2)
C3—C4—H4	119.5	C13—C12—H12	119.5
C5—C4—H4	119.5	C11—C12—H12	119.5
C6—C5—C4	118.9 (3)	C12—C13—C14	119.1 (2)
C6—C5—H5	120.5	C12—C13—H13	120.4
C4—C5—H5	120.5	C14—C13—H13	120.4
C5—C6—C1	120.3 (2)	C9—C14—C13	120.0 (2)
C5—C6—C7	128.0 (2)	C9—C14—C15	112.24 (19)
C1—C6—C7	111.7 (2)	C13—C14—C15	127.7 (2)
C6—C7—C8	104.37 (18)	C14—C15—C16	104.30 (17)
C6—C7—H7A	110.9	C14—C15—H15A	110.9
C8—C7—H7A	110.9	C16—C15—H15A	110.9
C6—C7—H7B	110.9	C14—C15—H15B	110.9
C8—C7—H7B	110.9	C16—C15—H15B	110.9
H7A—C7—H7B	108.9	H15A—C15—H15B	108.9
C9—C8—C7	115.99 (18)	C1—C16—C15	115.65 (19)
C9—C8—C16	103.94 (16)	C1—C16—C8	104.37 (17)
C7—C8—C16	107.62 (17)	C15—C16—C8	107.63 (17)
C9—C8—C16ⁱ	115.41 (17)	C1—C16—C8ⁱ	115.12 (17)
C7—C8—C16ⁱ	118.91 (19)	C15—C16—C8ⁱ	118.80 (19)
C16—C8—C16ⁱ	89.59 (15)	C8—C16—C8ⁱ	90.41 (15)

C6—C1—C2—C3	1.2 (3)	C10—C9—C14—C13	−0.2 (3)
C16—C1—C2—C3	−178.4 (2)	C8—C9—C14—C13	179.10 (18)
C1—C2—C3—C4	−0.2 (4)	C10—C9—C14—C15	177.7 (2)
C2—C3—C4—C5	−0.5 (4)	C8—C9—C14—C15	−3.0 (3)
C3—C4—C5—C6	0.1 (4)	C12—C13—C14—C9	0.6 (3)
C4—C5—C6—C1	0.9 (3)	C12—C13—C14—C15	−176.9 (2)
C4—C5—C6—C7	−178.3 (2)	C9—C14—C15—C16	5.6 (3)
C2—C1—C6—C5	−1.6 (3)	C13—C14—C15—C16	−176.7 (2)
C16—C1—C6—C5	178.12 (19)	C6—C1—C16—C15	116.9 (2)
C2—C1—C6—C7	177.8 (2)	C2—C1—C16—C15	−63.4 (3)
C16—C1—C6—C7	−2.5 (3)	C6—C1—C16—C8	−1.1 (2)
C5—C6—C7—C8	−175.6 (2)	C2—C1—C16—C8	178.6 (2)
C1—C6—C7—C8	5.1 (3)	C6—C1—C16—C8ⁱ	−98.5 (2)
C6—C7—C8—C9	−121.4 (2)	C2—C1—C16—C8ⁱ	81.2 (3)
C6—C7—C8—C16	−5.5 (2)	C14—C15—C16—C1	−122.1 (2)
C6—C7—C8—C16ⁱ	94.1 (2)	C14—C15—C16—C8	−6.0 (2)
C7—C8—C9—C14	116.93 (19)	C14—C15—C16—C8ⁱ	94.6 (2)
C16—C8—C9—C14	−1.0 (2)	C9—C8—C16—C1	127.77 (17)
C16ⁱ—C8—C9—C14	−97.3 (2)	C7—C8—C16—C1	4.2 (2)
C7—C8—C9—C10	−63.9 (3)	C16ⁱ—C8—C16—C1	−116.11 (18)
C16—C8—C9—C10	178.2 (2)	C9—C8—C16—C15	4.4 (2)
C16ⁱ—C8—C9—C10	81.9 (3)	C7—C8—C16—C15	−119.2 (2)
C14—C9—C10—C11	−0.3 (3)	C16ⁱ—C8—C16—C15	120.5 (2)
C8—C9—C10—C11	−179.5 (2)	C9—C8—C16—C8ⁱ	−116.13 (18)
C9—C10—C11—C12	0.4 (4)	C7—C8—C16—C8ⁱ	120.3 (2)
C10—C11—C12—C13	0.1 (4)	C16ⁱ—C8—C16—C8ⁱ	−0.002 (1)
C11—C12—C13—C14	−0.6 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C9–C14 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg1ⁱⁱ	0.95	2.77	3.713 (3)	171

Symmetry code: (ii) −x+1, y−1/2, −z+3/2.

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

The head-to-head photodimer of indeno­indene

Structure description

Synthesis and crystallization

Refinement

Structural data

References

organic compounds

The head-to-head photodimer of indenoindene