Literature DB >> 22589995

9-(Dicyano-methyl-idene)fluorene-tetra-thia-fulvalene (1/1).

Amparo Salmerón-Valverde, Sylvain Bernès.   

Abstract

The title compound, C(16)H(8)N(2)·C(6)H(4)S(4), crystallizes with the fluorene derivative placed in a general position and two half tetra-thia-fulvalene (TTF) mol-ecules, each completed to a whole mol-ecule through an inversion center. The fluorene ring system is virtually planar (r.m.s. deviation from the mean plane = 0.027 Å) and the dicyano group is twisted from the fluorene plane by only 3.85 (12)°. The TTF mol-ecules are also planar, and their central C=C bond lengths [1.351 (8) and 1.324 (7) Å] compare well with the same bond length in neutral TTF (ca 1.35 Å). These features indicate that no charge transfer occurs between mol-ecules in the crystal; the compound should thus be considered a cocrystal rather than an organic complex. This is confirmed by the crystal structure, in which no significant stacking inter-actions are observed between mol-ecules.

Entities:  

Year:  2012        PMID： 22589995      PMCID： PMC3343914          DOI： 10.1107/S1600536812008124

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For organic conductors based on TTF and a π*-acceptor mol­ecule, see: Saito & Ferraris (1980 ▶); Wright (1995 ▶). For structures of dicyano­fulvenes, see: Andrew et al. (2010 ▶). For the accurate structure of TTF, see: Batsanov (2006 ▶). For charge-transfer complexes related to the title cocrystal, see: Salmerón-Valverde et al. (2003 ▶); Salmerón-Valverde (2008 ▶).

Experimental

Crystal data

C16H8N2·C6H4S4 M = 432.58 Triclinic, a = 7.9919 (11) Å b = 9.3696 (14) Å c = 14.195 (2) Å α = 94.525 (12)° β = 103.687 (12)° γ = 103.252 (12)° V = 995.3 (2) Å3 Z = 2 Mo Kα radiation μ = 0.49 mm−1 T = 296 K 0.22 × 0.20 × 0.03 mm

Data collection

Bruker P4 diffractometer Absorption correction: ψ scan (XSCANS; Siemens, 1996 ▶) T min = 0.650, T max = 0.688 5766 measured reflections 3493 independent reflections 1541 reflections with I > 2σ(I) R int = 0.062 2 standard reflections every 48 reflections intensity decay: 14%

Refinement

R[F 2 > 2σ(F 2)] = 0.048 wR(F 2) = 0.119 S = 0.95 3493 reflections 254 parameters H-atom parameters constrained Δρmax = 0.21 e Å−3 Δρmin = −0.21 e Å−3 Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL-Plus. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812008124/qm2055sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008124/qm2055Isup2.hkl Supplementary material file. DOI: 10.1107/S1600536812008124/qm2055Isup3.mol Supplementary material file. DOI: 10.1107/S1600536812008124/qm2055Isup4.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C16H8N2·C6H4S4Z = 2
Mr = 432.58F(000) = 444
Triclinic, P1Dx = 1.443 Mg m−3
Hall symbol: -P 1Melting point: 403 K
a = 7.9919 (11) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.3696 (14) ÅCell parameters from 57 reflections
c = 14.195 (2) Åθ = 4.0–12.2°
α = 94.525 (12)°µ = 0.49 mm−1
β = 103.687 (12)°T = 296 K
γ = 103.252 (12)°Plate, green
V = 995.3 (2) Å30.22 × 0.20 × 0.03 mm
Bruker P4 diffractometer1541 reflections with I > 2σ(I)
Radiation source: X-rayRint = 0.062
Graphite monochromatorθmax = 25.0°, θmin = 2.3°
2θ/ω scansh = −9→3
Absorption correction: ψ scan (XSCANS; Siemens, 1996)k = −10→10
Tmin = 0.650, Tmax = 0.688l = −16→16
5766 measured reflections2 standard reflections every 48 reflections
3493 independent reflections intensity decay: 14%
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.119w = 1/[σ2(Fo2) + (0.0414P)2] where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max < 0.001
3493 reflectionsΔρmax = 0.21 e Å−3
254 parametersΔρmin = −0.21 e Å−3
0 restraintsExtinction correction: SHELXTL-Plus (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.0125 (17)
Primary atom site location: structure-invariant direct methods
xyzUiso*/Ueq
C10.0179 (5)0.9147 (5)0.3451 (3)0.0587 (11)
H1A−0.00580.99880.32010.070*
C2−0.0704 (6)0.7737 (5)0.2941 (3)0.0718 (14)
H2A−0.15430.76350.23450.086*
C3−0.0341 (7)0.6488 (5)0.3318 (4)0.0767 (14)
H3A−0.09350.55570.29670.092*
C40.0888 (6)0.6601 (5)0.4206 (4)0.0694 (13)
H4A0.11160.57550.44520.083*
C4A0.1776 (5)0.7992 (5)0.4723 (3)0.0538 (11)
C4B0.3151 (5)0.8434 (5)0.5651 (3)0.0521 (11)
C50.3937 (6)0.7596 (5)0.6298 (4)0.0643 (12)
H5A0.35700.65670.61880.077*
C60.5283 (6)0.8334 (6)0.7112 (4)0.0721 (14)
H6A0.58440.77830.75410.087*
C70.5818 (6)0.9857 (6)0.7309 (3)0.0676 (13)
H7A0.67121.03190.78690.081*
C80.5017 (5)1.0703 (5)0.6668 (3)0.0589 (11)
H8A0.53721.17320.67990.071*
C8A0.3686 (5)1.0006 (5)0.5833 (3)0.0495 (10)
C90.2619 (5)1.0585 (5)0.5019 (3)0.0448 (10)
C9A0.1426 (5)0.9265 (4)0.4344 (3)0.0485 (10)
C100.2732 (5)1.2023 (5)0.4915 (3)0.0489 (10)
C110.1603 (6)1.2507 (4)0.4121 (3)0.0545 (11)
N120.0739 (5)1.2952 (4)0.3509 (3)0.0719 (11)
C130.3997 (6)1.3228 (5)0.5590 (3)0.0577 (12)
N140.5000 (5)1.4216 (4)0.6109 (3)0.0782 (12)
S150.28023 (18)0.60731 (16)−0.03391 (10)0.0884 (5)
C160.1970 (7)0.6242 (6)0.0666 (4)0.0943 (17)
H16A0.09930.66330.06380.113*
C170.2751 (7)0.5805 (6)0.1473 (4)0.0866 (16)
H17A0.23300.58670.20280.104*
S180.45887 (18)0.51072 (15)0.14801 (9)0.0832 (5)
C190.4457 (5)0.5248 (5)0.0235 (3)0.0636 (13)
S200.26100 (15)1.13111 (14)0.99343 (9)0.0784 (4)
C210.3288 (6)1.0451 (6)0.9025 (3)0.0742 (14)
H21A0.43891.08450.89090.089*
C220.2207 (6)0.9222 (5)0.8498 (3)0.0693 (13)
H22A0.25250.87250.80010.083*
S230.01752 (15)0.85519 (14)0.87520 (8)0.0661 (4)
C240.0573 (5)0.9972 (4)0.9734 (3)0.0517 (11)
U11U22U33U12U13U23
C10.062 (3)0.048 (3)0.066 (3)0.012 (2)0.016 (3)0.008 (2)
C20.072 (3)0.063 (3)0.068 (3)0.007 (3)0.010 (3)−0.002 (3)
C30.086 (4)0.050 (3)0.086 (4)0.004 (3)0.024 (3)−0.007 (3)
C40.081 (3)0.051 (3)0.078 (4)0.020 (3)0.022 (3)0.012 (3)
C4A0.060 (3)0.041 (3)0.068 (3)0.017 (2)0.028 (2)0.008 (2)
C4B0.050 (3)0.060 (3)0.054 (3)0.018 (2)0.024 (2)0.013 (2)
C50.072 (3)0.061 (3)0.076 (3)0.031 (3)0.031 (3)0.028 (3)
C60.068 (3)0.098 (4)0.073 (4)0.042 (3)0.032 (3)0.040 (3)
C70.062 (3)0.088 (4)0.058 (3)0.025 (3)0.018 (2)0.023 (3)
C80.057 (3)0.061 (3)0.063 (3)0.017 (2)0.019 (2)0.016 (3)
C8A0.048 (2)0.054 (3)0.056 (3)0.018 (2)0.022 (2)0.016 (2)
C90.045 (2)0.048 (3)0.049 (2)0.017 (2)0.020 (2)0.007 (2)
C9A0.049 (2)0.047 (3)0.053 (3)0.014 (2)0.020 (2)0.006 (2)
C100.047 (3)0.049 (3)0.049 (3)0.012 (2)0.009 (2)0.004 (2)
C110.064 (3)0.041 (3)0.059 (3)0.012 (2)0.022 (3)−0.002 (2)
N120.087 (3)0.057 (3)0.066 (3)0.023 (2)0.005 (2)0.004 (2)
C130.065 (3)0.051 (3)0.062 (3)0.018 (3)0.020 (3)0.015 (2)
N140.080 (3)0.064 (3)0.077 (3)0.011 (2)0.005 (2)0.002 (2)
S150.0775 (9)0.0981 (11)0.0898 (10)0.0303 (8)0.0098 (8)0.0282 (8)
C160.072 (4)0.096 (4)0.103 (4)0.022 (3)0.005 (3)0.002 (4)
C170.075 (4)0.089 (4)0.086 (4)0.004 (3)0.022 (3)−0.005 (3)
S180.0863 (10)0.0853 (10)0.0709 (9)0.0159 (8)0.0105 (7)0.0185 (7)
C190.064 (3)0.049 (3)0.063 (3)0.000 (2)0.000 (2)0.015 (2)
S200.0612 (8)0.0889 (10)0.0702 (9)−0.0083 (7)0.0218 (7)−0.0093 (7)
C210.052 (3)0.101 (4)0.069 (3)0.012 (3)0.022 (3)0.012 (3)
C220.061 (3)0.091 (4)0.065 (3)0.026 (3)0.029 (3)0.013 (3)
S230.0628 (8)0.0728 (9)0.0583 (7)0.0136 (6)0.0153 (6)−0.0042 (6)
C240.049 (3)0.052 (3)0.052 (3)0.012 (2)0.0123 (19)0.002 (2)
C1—C9A1.394 (5)C9—C101.352 (5)
C1—C21.395 (5)C9—C9A1.482 (5)
C1—H1A0.9300C10—C131.436 (6)
C2—C31.386 (6)C10—C111.442 (6)
C2—H2A0.9300C11—N121.144 (5)
C3—C41.382 (6)C13—N141.147 (5)
C3—H3A0.9300S15—C161.722 (6)
C4—C4A1.386 (5)S15—C191.752 (4)
C4—H4A0.9300C16—C171.312 (6)
C4A—C9A1.404 (5)C16—H16A0.9300
C4A—C4B1.460 (6)C17—S181.737 (5)
C4B—C51.386 (5)C17—H17A0.9300
C4B—C8A1.421 (5)S18—C191.762 (4)
C5—C61.384 (6)C19—C19i1.351 (8)
C5—H5A0.9300S20—C211.726 (5)
C6—C71.378 (6)S20—C241.759 (4)
C6—H6A0.9300C21—C221.317 (6)
C7—C81.392 (5)C21—H21A0.9300
C7—H7A0.9300C22—S231.734 (4)
C8—C8A1.388 (5)C22—H22A0.9300
C8—H8A0.9300S23—C241.766 (4)
C8A—C91.483 (5)C24—C24ii1.324 (7)
C9A—C1—C2118.5 (4)C10—C9—C9A127.4 (4)
C9A—C1—H1A120.8C10—C9—C8A126.8 (4)
C2—C1—H1A120.8C9A—C9—C8A105.8 (3)
C3—C2—C1120.4 (4)C1—C9A—C4A120.6 (4)
C3—C2—H2A119.8C1—C9A—C9130.8 (4)
C1—C2—H2A119.8C4A—C9A—C9108.5 (4)
C4—C3—C2121.2 (4)C9—C10—C13123.1 (4)
C4—C3—H3A119.4C9—C10—C11123.8 (4)
C2—C3—H3A119.4C13—C10—C11113.1 (4)
C3—C4—C4A119.1 (4)N12—C11—C10177.1 (5)
C3—C4—H4A120.4N14—C13—C10178.0 (5)
C4A—C4—H4A120.4C16—S15—C1994.7 (2)
C4—C4A—C9A120.1 (4)C17—C16—S15118.3 (5)
C4—C4A—C4B130.7 (4)C17—C16—H16A120.9
C9A—C4A—C4B109.2 (4)S15—C16—H16A120.9
C5—C4B—C8A120.8 (4)C16—C17—S18118.5 (5)
C5—C4B—C4A131.0 (4)C16—C17—H17A120.8
C8A—C4B—C4A108.2 (4)S18—C17—H17A120.8
C6—C5—C4B118.1 (4)C17—S18—C1993.8 (2)
C6—C5—H5A120.9C19i—C19—S15123.0 (5)
C4B—C5—H5A120.9C19i—C19—S18122.5 (5)
C7—C6—C5122.2 (4)S15—C19—S18114.6 (2)
C7—C6—H6A118.9C21—S20—C2494.8 (2)
C5—C6—H6A118.9C22—C21—S20118.2 (4)
C6—C7—C8119.9 (4)C22—C21—H21A120.9
C6—C7—H7A120.1S20—C21—H21A120.9
C8—C7—H7A120.1C21—C22—S23118.4 (4)
C8A—C8—C7119.7 (4)C21—C22—H22A120.8
C8A—C8—H8A120.1S23—C22—H22A120.8
C7—C8—H8A120.1C22—S23—C2494.4 (2)
C8—C8A—C4B119.3 (4)C24ii—C24—S20123.1 (4)
C8—C8A—C9132.4 (4)C24ii—C24—S23122.8 (4)
C4B—C8A—C9108.3 (4)S20—C24—S23114.1 (2)
C9A—C1—C2—C3−0.1 (6)C4—C4A—C9A—C10.4 (6)
C1—C2—C3—C40.5 (7)C4B—C4A—C9A—C1178.9 (3)
C2—C3—C4—C4A−0.3 (7)C4—C4A—C9A—C9−177.2 (4)
C3—C4—C4A—C9A−0.1 (6)C4B—C4A—C9A—C91.3 (4)
C3—C4—C4A—C4B−178.2 (4)C10—C9—C9A—C11.4 (6)
C4—C4A—C4B—C5−2.0 (7)C8A—C9—C9A—C1−178.0 (4)
C9A—C4A—C4B—C5179.7 (4)C10—C9—C9A—C4A178.7 (4)
C4—C4A—C4B—C8A176.8 (4)C8A—C9—C9A—C4A−0.7 (4)
C9A—C4A—C4B—C8A−1.4 (4)C9A—C9—C10—C13−176.9 (4)
C8A—C4B—C5—C6−1.5 (6)C8A—C9—C10—C132.3 (6)
C4A—C4B—C5—C6177.3 (4)C9A—C9—C10—C113.1 (6)
C4B—C5—C6—C71.9 (6)C8A—C9—C10—C11−177.6 (3)
C5—C6—C7—C8−1.1 (6)C19—S15—C16—C171.9 (5)
C6—C7—C8—C8A−0.2 (6)S15—C16—C17—S180.8 (6)
C7—C8—C8A—C4B0.6 (5)C16—C17—S18—C19−3.0 (5)
C7—C8—C8A—C9−179.0 (4)C16—S15—C19—C19i175.8 (5)
C5—C4B—C8A—C80.3 (5)C16—S15—C19—S18−3.9 (3)
C4A—C4B—C8A—C8−178.7 (3)C17—S18—C19—C19i−175.6 (5)
C5—C4B—C8A—C9179.9 (3)C17—S18—C19—S154.2 (3)
C4A—C4B—C8A—C90.9 (4)C24—S20—C21—C221.5 (4)
C8—C8A—C9—C100.1 (6)S20—C21—C22—S230.1 (6)
C4B—C8A—C9—C10−179.5 (4)C21—C22—S23—C24−1.5 (4)
C8—C8A—C9—C9A179.4 (4)C21—S20—C24—C24ii178.3 (5)
C4B—C8A—C9—C9A−0.2 (4)C21—S20—C24—S23−2.4 (3)
C2—C1—C9A—C4A−0.3 (6)C22—S23—C24—C24ii−178.3 (5)
C2—C1—C9A—C9176.7 (4)C22—S23—C24—S202.4 (3)
  4 in total

1.  Synthesis, reactivity, and electronic properties of 6,6-dicyanofulvenes.

Authors:  Trisha L Andrew; Jason R Cox; Timothy M Swager
Journal:  Org Lett       Date:  2010-10-29       Impact factor: 6.005

2.  Tetrathiafulvalene revisited.

Authors:  Andrei S Batsanov
Journal:  Acta Crystallogr C       Date:  2006-07-22       Impact factor: 1.172

3.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

4.  Structure and degree of charge transfer of two polymorphs of a 1:1 molecular complex: [2,2'-bis-1,3-dithiole][9-dicyanomethylene-4,5,7-trinitrofluorene-2-carboxylic acid methyl ester] (TTF-MeDC2TNF).

Authors:  Amparo Salmerón-Valverde; Sylvain Bernès; Juan Gerardo Robles-Martínez
Journal:  Acta Crystallogr B       Date:  2003-07-25
  4 in total

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