Novel infinite three-dimensional network of neutral fullerene molecules in (C60)8(twin-TDAS)6

Penicaud, A.; Boubekeur, K.; Kotov, A.I.; Yagubskii, E.B.

doi:10.1107/S0108768199016560

Novel infinite three-dimensional network of neutral fullerene molecules in (C₆₀)₈(twin-TDAS)₆

A. Penicaud, K. Boubekeur, A. I. Kotov and E. B. Yagubskii

The crystal structure of (C₆₀)₈(twin-TDAS)₆ [twin-TDAS = C₄S₆N₄ = 3,3',4,4'-tetrathiobis(1,2,5-thiadiazole)] has been redetermined at low temperature in the correct space group [I23, a = 18.849 (1) Å]. Structural analysis reveals a novel three-dimensional close-contact network of C₆₀ molecules with tetrahedral holes similar to pristine C₆₀.

Keywords: Fullerene; Three-dimensional.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768199016560/cf0010sup1.cif Contains datablocks tdasbt, global
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768199016560/cf0010tdasbtsup2.hkl Contains datablock tdasbt

CCDC reference: 117020

Computing details top

Data collection: EXPOSE (Stoe IPDS); cell refinement: SELECT (Stoe IPDS); data reduction: INTEGRATE (Stoe IPDS); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

(tdasbt) top

Crystal data top

C₅₀₄N₂₄S₃₆	D_x = 1.870 Mg m⁻³
M_r = 7543.44	Mo Kα radiation, λ = 0.71073 Å
Cubic, I2₃	Cell parameters from 5000 reflections
Hall symbol: I 2 2 3	θ = 1.5–25.2°
a = 18.8492 (10) Å	µ = 0.38 mm⁻¹
V = 6697.0 (6) Å³	T = 100 K
Z = 1	Plate-like, black
F(000) = 3768	0.37 × 0.27 × 0.23 mm

Data collection top

Stoe IPDS diffractometer	1764 independent reflections
Radiation source: fine-focus sealed tube	1243 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
Detector resolution: 6.66 pixels mm^-1	θ_max = 25.2°, θ_min = 2.2°
Rotation, Δϕ=1.2° scans	h = −14→14
Absorption correction: part of the refinement model (ΔF) ABSCOR (Stoe, IPDS)	k = 0→15
T_min = 0.871, T_max = 0.916	l = 2→21
12851 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)] = 0.046	Calculated w = 1/[σ²(F_o²) + (0.1321P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.116	(Δ/σ)_max = 0.001
S = 0.56	Δρ_max = 0.46 e Å⁻³
1764 reflections	Δρ_min = −0.22 e Å⁻³
213 parameters	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
0 restraints	Absolute structure parameter: −0.04 (15)

Crystal data top

C₅₀₄N₂₄S₃₆	Z = 1
M_r = 7543.44	Mo Kα radiation
Cubic, I2₃	µ = 0.38 mm⁻¹
a = 18.8492 (10) Å	T = 100 K
V = 6697.0 (6) Å³	0.37 × 0.27 × 0.23 mm

Data collection top

Stoe IPDS diffractometer	1764 independent reflections
Absorption correction: part of the refinement model (ΔF) ABSCOR (Stoe, IPDS)	1243 reflections with I > 2σ(I)
T_min = 0.871, T_max = 0.916	R_int = 0.014
12851 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.116	Δρ_max = 0.46 e Å⁻³
S = 0.56	Δρ_min = −0.22 e Å⁻³
1764 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
213 parameters	Absolute structure parameter: −0.04 (15)

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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
S1	1.0000	0.5000	0.77492 (8)	0.0218 (4)
S2	0.91245 (6)	0.45675 (7)	0.96721 (6)	0.0299 (4)
N1	1.0595 (2)	0.5267 (2)	0.8308 (2)	0.0241 (9)
C1	0.9651 (2)	0.4843 (2)	0.8958 (2)	0.0158 (9)
C2	0.8494 (3)	0.9308 (3)	0.9509 (3)	0.051 (2)
C3	0.8678 (4)	0.9719 (3)	0.8913 (4)	0.056 (2)
C4	0.7768 (3)	0.9162 (3)	0.9632 (3)	0.0373 (14)
C5	0.8135 (4)	0.9972 (3)	0.8409 (4)	0.053 (2)
C6	0.7680 (3)	0.8441 (3)	0.9913 (3)	0.043 (2)
C7	0.7455 (5)	0.9824 (3)	0.8520 (4)	0.063 (2)
C8	0.7237 (3)	0.9421 (3)	0.9154 (3)	0.0350 (14)
C9	0.7122 (4)	0.8044 (3)	0.9702 (3)	0.046 (2)
C10	0.6994 (3)	0.9602 (3)	0.7898 (4)	0.044 (2)
C11	0.6672 (3)	0.8984 (3)	0.8951 (3)	0.044 (2)
C12	1.1622 (3)	0.6678 (4)	0.5778 (3)	0.045 (2)
C13	0.7281 (3)	0.9549 (3)	0.7254 (3)	0.0421 (15)
C14	0.6515 (3)	0.9095 (4)	0.8185 (3)	0.043 (2)
C15	0.7087 (3)	0.8981 (3)	0.6810 (3)	0.0363 (15)
C16	0.7710 (4)	0.8757 (4)	0.6412 (3)	0.053 (2)
C17	0.6324 (3)	0.8535 (4)	0.7775 (4)	0.047 (2)
C18	0.6605 (3)	0.8484 (3)	0.7074 (3)	0.0341 (14)
C19	0.6267 (3)	0.7815 (4)	0.8078 (5)	0.059 (2)
C20	0.7304 (4)	0.7546 (4)	0.6533 (3)	0.056 (2)
C21	0.6719 (4)	0.7733 (4)	0.6919 (4)	0.050 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0260 (9)	0.0242 (9)	0.0150 (8)	0.0032 (8)	0.000	0.000
S2	0.0203 (7)	0.0497 (9)	0.0195 (7)	−0.0168 (6)	−0.0004 (5)	0.0062 (6)
N1	0.025 (2)	0.030 (2)	0.018 (2)	−0.005 (2)	0.005 (2)	−0.002 (2)
C1	0.016 (2)	0.016 (2)	0.015 (2)	−0.001 (2)	−0.002 (2)	0.001 (2)
C2	0.058 (4)	0.050 (4)	0.043 (4)	−0.005 (3)	−0.005 (3)	−0.037 (3)
C3	0.082 (5)	0.030 (3)	0.055 (4)	−0.035 (3)	0.009 (4)	−0.032 (3)
C4	0.038 (3)	0.048 (3)	0.026 (3)	0.000 (3)	0.009 (3)	−0.029 (3)
C5	0.079 (5)	0.016 (3)	0.065 (4)	−0.006 (3)	0.013 (4)	−0.010 (3)
C6	0.063 (4)	0.054 (4)	0.011 (3)	0.022 (3)	0.015 (3)	−0.004 (3)
C7	0.111 (7)	0.019 (4)	0.058 (4)	0.042 (4)	0.010 (4)	−0.003 (3)
C8	0.050 (4)	0.026 (3)	0.029 (3)	0.021 (3)	0.012 (3)	−0.013 (2)
C9	0.064 (4)	0.049 (4)	0.024 (3)	−0.008 (3)	0.030 (3)	0.000 (3)
C10	0.042 (4)	0.021 (3)	0.068 (5)	0.019 (3)	−0.011 (3)	−0.001 (3)
C11	0.029 (3)	0.062 (4)	0.040 (4)	0.023 (3)	0.008 (3)	−0.019 (3)
C12	0.035 (4)	0.061 (4)	0.039 (4)	−0.010 (3)	−0.025 (3)	0.002 (3)
C13	0.043 (3)	0.029 (3)	0.054 (4)	0.007 (3)	−0.009 (3)	0.017 (3)
C14	0.025 (3)	0.053 (4)	0.050 (4)	0.027 (3)	0.002 (3)	0.006 (3)
C15	0.031 (3)	0.050 (4)	0.028 (3)	0.014 (3)	−0.007 (2)	0.020 (3)
C16	0.044 (4)	0.091 (6)	0.023 (3)	0.018 (4)	−0.005 (3)	0.023 (4)
C17	0.018 (3)	0.060 (5)	0.062 (4)	0.015 (3)	−0.001 (3)	0.031 (4)
C18	0.023 (3)	0.033 (3)	0.047 (4)	0.008 (2)	−0.024 (3)	−0.001 (3)
C19	0.015 (3)	0.064 (5)	0.098 (6)	−0.010 (3)	0.001 (3)	0.022 (5)
C20	0.050 (4)	0.090 (6)	0.028 (3)	0.011 (4)	−0.024 (3)	−0.032 (3)
C21	0.047 (4)	0.050 (4)	0.052 (4)	−0.009 (4)	−0.030 (3)	−0.010 (3)

Geometric parameters (Å, º) top

S1—N1ⁱ	1.619 (4)	C10—C13	1.333 (9)
S1—N1	1.619 (4)	C10—C14	1.421 (9)
S2—C1	1.752 (4)	C11—C12^v	1.353 (8)
S2—S2ⁱⁱ	2.046 (3)	C11—C14	1.489 (9)
N1—C1ⁱ	1.326 (5)	C12—C11^vi	1.353 (8)
C1—N1ⁱ	1.327 (5)	C12—C9^vi	1.407 (9)
C1—C1ⁱ	1.442 (9)	C12—C16^vii	1.503 (10)
C2—C3	1.409 (9)	C13—C15	1.407 (9)
C2—C4	1.415 (8)	C13—C9^iv	1.488 (9)
C2—C3ⁱⁱⁱ	1.479 (9)	C14—C17	1.356 (10)
C3—C2^iv	1.479 (9)	C15—C18	1.396 (8)
C3—C5	1.475 (10)	C15—C16	1.455 (9)
C4—C8	1.431 (9)	C16—C19^iv	1.323 (10)
C4—C6	1.470 (8)	C16—C12^viii	1.503 (10)
C5—C7	1.329 (10)	C17—C18	1.426 (9)
C5—C6^iv	1.493 (8)	C17—C19	1.476 (9)
C6—C9	1.350 (9)	C18—C21	1.461 (9)
C6—C5ⁱⁱⁱ	1.493 (9)	C19—C16ⁱⁱⁱ	1.323 (10)
C7—C10	1.518 (10)	C19—C20ⁱⁱⁱ	1.479 (11)
C7—C8	1.474 (9)	C20—C21	1.367 (10)
C8—C11	1.400 (9)	C20—C21^iv	1.475 (10)
C9—C12^v	1.407 (9)	C20—C19^iv	1.479 (11)
C9—C13ⁱⁱⁱ	1.488 (9)	C21—C20ⁱⁱⁱ	1.475 (10)

N1ⁱ—S1—N1	98.8 (3)	C12^v—C11—C8	119.4 (6)
C1—S2—S2ⁱⁱ	103.2 (2)	C12^v—C11—C14	118.9 (6)
C1ⁱ—N1—S1	108.0 (3)	C8—C11—C14	109.6 (6)
N1ⁱ—C1—C1ⁱ	112.6 (3)	C11^vi—C12—C9^vi	122.7 (6)
N1ⁱ—C1—S2	117.7 (3)	C11^vi—C12—C16^vii	120.4 (6)
C1ⁱ—C1—S2	129.70 (14)	C9^vi—C12—C16^vii	105.5 (6)
C3—C2—C4	118.3 (6)	C10—C13—C15	119.6 (6)
C3—C2—C3ⁱⁱⁱ	121.7 (7)	C10—C13—C9^iv	122.0 (6)
C4—C2—C3ⁱⁱⁱ	108.5 (6)	C15—C13—C9^iv	107.4 (5)
C2—C3—C2^iv	118.3 (7)	C17—C14—C10	118.3 (6)
C2—C3—C5	121.4 (6)	C17—C14—C11	119.7 (6)
C2^iv—C3—C5	107.4 (6)	C10—C14—C11	109.6 (6)
C8—C4—C2	120.6 (6)	C18—C15—C13	117.8 (5)
C8—C4—C6	117.6 (5)	C18—C15—C16	121.0 (6)
C2—C4—C6	110.3 (5)	C13—C15—C16	108.6 (6)
C7—C5—C3	120.0 (6)	C19^iv—C16—C15	120.5 (7)
C7—C5—C6^iv	120.2 (7)	C19^iv—C16—C12^viii	120.2 (6)
C3—C5—C6^iv	107.5 (6)	C15—C16—C12^viii	108.3 (6)
C9—C6—C4	119.6 (6)	C14—C17—C18	118.8 (5)
C9—C6—C5ⁱⁱⁱ	121.6 (6)	C14—C17—C19	120.9 (6)
C4—C6—C5ⁱⁱⁱ	106.3 (6)	C18—C17—C19	108.9 (6)
C5—C7—C10	119.1 (6)	C15—C18—C17	121.8 (5)
C5—C7—C8	120.3 (7)	C15—C18—C21	118.8 (5)
C10—C7—C8	109.0 (7)	C17—C18—C21	107.8 (6)
C11—C8—C4	120.3 (5)	C16ⁱⁱⁱ—C19—C20ⁱⁱⁱ	119.2 (6)
C11—C8—C7	107.0 (6)	C16ⁱⁱⁱ—C19—C17	119.8 (7)
C4—C8—C7	119.4 (6)	C20ⁱⁱⁱ—C19—C17	108.2 (7)
C6—C9—C12^v	120.3 (6)	C21—C20—C21^iv	121.6 (8)
C6—C9—C13ⁱⁱⁱ	117.5 (6)	C21—C20—C19^iv	122.1 (7)
C12^v—C9—C13ⁱⁱⁱ	110.3 (6)	C21^iv—C20—C19^iv	105.4 (6)
C13—C10—C14	123.6 (6)	C20—C21—C20ⁱⁱⁱ	118.3 (8)
C13—C10—C7	119.5 (6)	C20—C21—C18	118.4 (6)
C14—C10—C7	104.8 (6)	C20ⁱⁱⁱ—C21—C18	109.7 (7)

Symmetry codes: (i) −x+2, −y+1, z; (ii) x, −y+1, −z+2; (iii) z, x, y; (iv) y, z, x; (v) x−1/2, −y+3/2, −z+3/2; (vi) x+1/2, −y+3/2, −z+3/2; (vii) z+1/2, −x+3/2, −y+3/2; (viii) −y+3/2, −z+3/2, x−1/2.

Experimental details

Crystal data
Chemical formula	C₅₀₄N₂₄S₃₆
M_r	7543.44
Crystal system, space group	Cubic, I2₃
Temperature (K)	100
a (Å)	18.8492 (10)
V (Å³)	6697.0 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.37 × 0.27 × 0.23

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	Part of the refinement model (ΔF) ABSCOR (Stoe, IPDS)
T_min, T_max	0.871, 0.916
No. of measured, independent and observed [I > 2σ(I)] reflections	12851, 1764, 1243
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.116, 0.56
No. of reflections	1764
No. of parameters	213
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.22
Absolute structure	Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter	−0.04 (15)

Computer programs: EXPOSE (Stoe IPDS), SELECT (Stoe IPDS), INTEGRATE (Stoe IPDS), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP (Johnson, 1976).

Selected bond lengths (Å) top

S1—N1ⁱ	1.619 (4)	C10—C13	1.333 (9)
S1—N1	1.619 (4)	C10—C14	1.421 (9)
S2—C1	1.752 (4)	C11—C12^v	1.353 (8)
S2—S2ⁱⁱ	2.046 (3)	C11—C14	1.489 (9)
N1—C1ⁱ	1.326 (5)	C12—C11^vi	1.353 (8)
C1—N1ⁱ	1.327 (5)	C12—C9^vi	1.407 (9)
C1—C1ⁱ	1.442 (9)	C12—C16^vii	1.503 (10)
C2—C3	1.409 (9)	C13—C15	1.407 (9)
C2—C4	1.415 (8)	C13—C9^iv	1.488 (9)
C2—C3ⁱⁱⁱ	1.479 (9)	C14—C17	1.356 (10)
C3—C2^iv	1.479 (9)	C15—C18	1.396 (8)
C3—C5	1.475 (10)	C15—C16	1.455 (9)
C4—C8	1.431 (9)	C16—C19^iv	1.323 (10)
C4—C6	1.470 (8)	C16—C12^viii	1.503 (10)
C5—C7	1.329 (10)	C17—C18	1.426 (9)
C5—C6^iv	1.493 (8)	C17—C19	1.476 (9)
C6—C9	1.350 (9)	C18—C21	1.461 (9)
C6—C5ⁱⁱⁱ	1.493 (9)	C19—C16ⁱⁱⁱ	1.323 (10)
C7—C10	1.518 (10)	C19—C20ⁱⁱⁱ	1.479 (11)
C7—C8	1.474 (9)	C20—C21	1.367 (10)
C8—C11	1.400 (9)	C20—C21^iv	1.475 (10)
C9—C12^v	1.407 (9)	C20—C19^iv	1.479 (11)
C9—C13ⁱⁱⁱ	1.488 (9)	C21—C20ⁱⁱⁱ	1.475 (10)

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		SGML
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