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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 4| April 2012| Page o932
doi:10.1107/S1600536812008124

9-(Di­cyano­methyl­­idene)fluorene–tetra­thia­fulvalene (1/1)

Amparo Salmerón-Valverdea and Sylvain Bernèsb*

aCentro de Química del Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Ciudad Universitaria, San Manuel, 72570 Puebla, Pue., Mexico, and bDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, N.L., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com

(Received 17 February 2012; accepted 23 February 2012; online 3 March 2012)

The title compound, C16H8N2·C6H4S4, crystallizes with the fluorene derivative placed in a general position and two half tetra­thia­fulvalene (TTF) mol­ecules, each completed to a whole mol­ecule 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 mol­ecules 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 mol­ecules 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 inter­actions are observed between mol­ecules.

Related literature

For organic conductors based on TTF and a π*-acceptor mol­ecule, see: Saito & Ferraris (1980[Saito, G. & Ferraris, J. P. (1980). Bull. Chem. Soc. Jpn, 53, 2141-2145.]); Wright (1995[Wright, J. D. (1995). Molecular Crystals, 2nd ed., pp. 22-49. Cambridge: Cambridge University Press.]). For structures of dicyano­fulvenes, see: Andrew et al. (2010[Andrew, T. L., Cox, J. R. & Swager, T. M. (2010). Org. Lett. 12, 5302-5305.]). For the accurate structure of TTF, see: Batsanov (2006[Batsanov, A. S. (2006). Acta Cryst. C62, o501-o504.]). For charge-transfer complexes related to the title cocrystal, see: Salmerón-Valverde et al. (2003[Salmerón-Valverde, A., Bernès, S. & Robles-Martínez, J. G. (2003). Acta Cryst. B59, 505-511.]); Salmerón-Valverde (2008[Salmerón-Valverde (2008). PhD thesis, Benemérita Universidad Autónoma de Puebla, Mexico.]).

[Scheme 1]

Experimental

Crystal data

  • C16H8N2·C6H4S4

  • Mr = 432.58

  • Triclinic, [P \overline 1]

  • 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[Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]) Tmin = 0.650, Tmax = 0.688

  • 5766 measured reflections

  • 3493 independent reflections

  • 1541 reflections with I > 2σ(I)

  • Rint = 0.062

  • 2 standard reflections every 48 reflections intensity decay: 14%
Refinement

  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 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[Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus and Mercury (Macrae et al., 2008[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.]); software used to prepare material for publication: SHELXTL-Plus.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812008124/qm2055sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008124/qm2055Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008124/qm2055Isup3.mol

Supporting information file. DOI: 10.1107/S1600536812008124/qm2055Isup4.cml

checkCIF report


Comment top

There is a vast literature dealing with the organic charge-transfer complexes based on the emblematic π-donor tetrathiafulvalene (TTF) and TTF derivatives. Generally, research in this field is carried out with the hope of obtaining organic materials exhibiting metallic conductivity. It is now known that two essential conditions are required for obtaining such conductivity: i) partial oxidation and reduction of the donor and acceptor molecules, respectively. The difference between the redox potentials of the molecules should be less than ca. 0.34 V (Saito & Ferraris, 1980); ii) molecules must be stacked in the solid state, forming one-dimensional or pseudo one-dimensional crystal structures. The mode of stacking and distances separating molecules along a stack must be suitable for charge-transfer (Wright, 1995). The title compound was formed by mixing TTF and a potential π*-acceptor molecule derived from fluorene, namely 9-(dicyanomethylene)fluorene (DCF hereafter). The X-ray structure of the resulting compound, TTF.DCF, shows that condition ii) is not present in the structure.

The asymmetric unit includes one DCF molecule, placed in a general position, and two half-TTF molecules, each close to an inversion center, generating the TTF.DCF chemical composition (Fig. 1). The DCF moiety is almost planar, with a r.m.s. deviation of 0.027 Å for the mean plane of the fluorene ring (13 C atoms). The dicyanomethylene plane is twisted by 3.85 (12)° from the fluorene ring, and the C═C bond length in this group, 1.352 (5) Å, is similar to those found in other dicyanomethylene derivatives (e.g. Andrew et al., 2010). The same is observed for TTF molecules, giving r.m.s. deviations of 0.037 and 0.020 Å for TTF-1 (S15···C19 and symmetry related atoms) and TTF-2 (S20···C24 and symmetry related atoms), respectively. The central C═C bond lengths are 1.351 (8) and 1.324 (7) Å, no longer that the same bond in neutral TTF, ca. 1.35 Å (Batsanov, 2006). These features indicate that molecules are not involved in charge-transfer in the solid state. This is fully confirmed with the crystal structure (Fig. 2). TTF and DCF are segregated in different layers parallel to the (001) plane (Fig. 2, inset), the separation between planes being c/2 = 7.1 Å. In the TTF layers, molecules are arranged in a herringbone pattern, avoiding π-π interactions. In the DCF layers, two molecules related by inversion are parallel and the separation between mean-planes for each molecule is relatively short, 3.401 Å. However, DCF molecules are slipped along the stack, and the distance between the centroids of two inversion-related DCF is 3.834 (1) Å. Such an arrangement does not favor π-π interactions for this component.

Spectroscopic data (Salmerón-Valverde, 2008) are consistent with the observed crystal structure. In the solid state, the IR vibration of the cyano groups in TTF.DCF is not shifted with respect to the same vibration in pure DCF (2224 cm-1), while a significant shift is expected for an actual charge-transfer complex (Salmerón-Valverde et al., 2003). In the same way, the central C═C bond in TTF, which is known to be sensitive to charge-transfer, is also unaffected when the cocrystal TTF.DCF is formed (νC═C: 1527 cm-1). In solution, no charge-transfer band is observed in the visible region for TTF.DCF, at any dilution in CH3CN.

Related literature top

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 top

Solutions of DCF (7.8 mg, 0.034 mmol) in hot CH3CN (2.5 ml) and TTF (7 mg, 0.034 mmol) in CH3CN (1.8 ml) were mixed and transferred in a test tube (12 × 1.5 cm). Solvent was slowly evaporated in the dark, over 10 days. After all solvent had evaporated, most of the crystals collected on the wall of the test tube were starting components, which present characteristic colors: yellow for TTF and orange for DCF. However, few green crystals of TTF.DCF were produced, with an approximate yield of 25%.

Refinement top

All H atoms were placed in idealized positions and refined as riding to their carrier C atoms, with C—H bond lengths fixed to 0.93 Å. Isotropic displacement parameters for H atoms were calculated as Uiso(H) = 1.2Ueq(carrier C atom).

Structure description top

There is a vast literature dealing with the organic charge-transfer complexes based on the emblematic π-donor tetrathiafulvalene (TTF) and TTF derivatives. Generally, research in this field is carried out with the hope of obtaining organic materials exhibiting metallic conductivity. It is now known that two essential conditions are required for obtaining such conductivity: i) partial oxidation and reduction of the donor and acceptor molecules, respectively. The difference between the redox potentials of the molecules should be less than ca. 0.34 V (Saito & Ferraris, 1980); ii) molecules must be stacked in the solid state, forming one-dimensional or pseudo one-dimensional crystal structures. The mode of stacking and distances separating molecules along a stack must be suitable for charge-transfer (Wright, 1995). The title compound was formed by mixing TTF and a potential π*-acceptor molecule derived from fluorene, namely 9-(dicyanomethylene)fluorene (DCF hereafter). The X-ray structure of the resulting compound, TTF.DCF, shows that condition ii) is not present in the structure.

The asymmetric unit includes one DCF molecule, placed in a general position, and two half-TTF molecules, each close to an inversion center, generating the TTF.DCF chemical composition (Fig. 1). The DCF moiety is almost planar, with a r.m.s. deviation of 0.027 Å for the mean plane of the fluorene ring (13 C atoms). The dicyanomethylene plane is twisted by 3.85 (12)° from the fluorene ring, and the C═C bond length in this group, 1.352 (5) Å, is similar to those found in other dicyanomethylene derivatives (e.g. Andrew et al., 2010). The same is observed for TTF molecules, giving r.m.s. deviations of 0.037 and 0.020 Å for TTF-1 (S15···C19 and symmetry related atoms) and TTF-2 (S20···C24 and symmetry related atoms), respectively. The central C═C bond lengths are 1.351 (8) and 1.324 (7) Å, no longer that the same bond in neutral TTF, ca. 1.35 Å (Batsanov, 2006). These features indicate that molecules are not involved in charge-transfer in the solid state. This is fully confirmed with the crystal structure (Fig. 2). TTF and DCF are segregated in different layers parallel to the (001) plane (Fig. 2, inset), the separation between planes being c/2 = 7.1 Å. In the TTF layers, molecules are arranged in a herringbone pattern, avoiding π-π interactions. In the DCF layers, two molecules related by inversion are parallel and the separation between mean-planes for each molecule is relatively short, 3.401 Å. However, DCF molecules are slipped along the stack, and the distance between the centroids of two inversion-related DCF is 3.834 (1) Å. Such an arrangement does not favor π-π interactions for this component.

Spectroscopic data (Salmerón-Valverde, 2008) are consistent with the observed crystal structure. In the solid state, the IR vibration of the cyano groups in TTF.DCF is not shifted with respect to the same vibration in pure DCF (2224 cm-1), while a significant shift is expected for an actual charge-transfer complex (Salmerón-Valverde et al., 2003). In the same way, the central C═C bond in TTF, which is known to be sensitive to charge-transfer, is also unaffected when the cocrystal TTF.DCF is formed (νC═C: 1527 cm-1). In solution, no charge-transfer band is observed in the visible region for TTF.DCF, at any dilution in CH3CN.

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).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, with displacement ellipsoids at the 30% probability level. Unlabelled atoms are generated through inversion centers.
[Figure 2] Fig. 2. The crystal structure of the title compound, viewed in two orientations. The inset shows two layers of DCF molecules sandwiched by three layers of TTF molecules.
9-(Dicyanomethylidene)fluorene–2-(2H-1,3-dithiol-2-ylidene)-2H-1,3-dithiole (1/1) top
Crystal data top
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
Data collection top
Bruker P4
diffractometer		1541 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 top
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) = 0.119 w = 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
Crystal data top
C16H8N2·C6H4S4γ = 103.252 (12)°
Mr = 432.58V = 995.3 (2) Å3
Triclinic, P1Z = 2
a = 7.9919 (11) ÅMo Kα radiation
b = 9.3696 (14) ŵ = 0.49 mm−1
c = 14.195 (2) ÅT = 296 K
α = 94.525 (12)°0.22 × 0.20 × 0.03 mm
β = 103.687 (12)°
Data collection top
Bruker P4
diffractometer		1541 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)		Rint = 0.062
Tmin = 0.650, Tmax = 0.6882 standard reflections every 48 reflections
5766 measured reflections intensity decay: 14%
3493 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.119H-atom parameters constrained
S = 0.95Δρmax = 0.21 e Å−3
3493 reflectionsΔρmin = −0.21 e Å−3
254 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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)
Atomic displacement parameters (Å2) top
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)
Geometric parameters (Å, º) top
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)
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z+2.

Experimental details

Crystal data
Chemical formulaC16H8N2·C6H4S4
Mr432.58
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)7.9919 (11), 9.3696 (14), 14.195 (2)
α, β, γ (°)94.525 (12), 103.687 (12), 103.252 (12)
V (Å3)995.3 (2)
Z2
Radiation typeMo Kα
µ (mm−1)0.49
Crystal size (mm)0.22 × 0.20 × 0.03
Data collection
DiffractometerBruker P4
Absorption correctionψ scan
(XSCANS; Siemens, 1996)
Tmin, Tmax0.650, 0.688
No. of measured, independent and
observed [I > 2σ(I)] reflections		5766, 3493, 1541
Rint0.062
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.119, 0.95
No. of reflections3493
No. of parameters254
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.21, −0.21

Computer programs: XSCANS (Siemens, 1996), SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

 

Acknowledgements

SB thanks ICUAP (Instituto de Ciencias, BUAP, Mexico) for the use of the P4 diffractometer.

References

First citationAndrew, T. L., Cox, J. R. & Swager, T. M. (2010). Org. Lett. 12, 5302–5305.  Web of Science CSD CrossRef CAS PubMed Google Scholar
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 First citationWright, J. D. (1995). Molecular Crystals, 2nd ed., pp. 22–49. Cambridge: Cambridge University Press.  Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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ISSN: 2056-9890
Volume 68| Part 4| April 2012| Page o932
doi:10.1107/S1600536812008124
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