Structure cristalline et moléculaire d'un nouveau metal organique: triméthylène-3,4 tétrathia-2,2',5,5' fulvalène–tétracyano-7,7,8,8 p-quinodimethane (TTTF–TCNQ)

Abstract

The 1 : 1 charge-transfer complex of 3,2',5,7,8, C2~H~2N4S4) crystallizes in the monoclinic system, space group C2. Lattice parameters are: a = 40.882 (8), b = 3.821 (3), c = 12.277 (5) A, fl = 100-94 (4) °, Z = 4, D c = 1.581 g cm -3. Data were collected by the 0--20 scan technique on a Siemens automatic diffractometer. The structure was solved by the standard heavy-atom method and refined by a least-squares method to a final R value of 0.053. The TCNQ and TTTF ions, stacked in a classic way, form segregated columns with interplanar spacings of 3.20 and 3.58 A respectively. The interchain coupling is stronger than in analogous S conductors; the columns are strongly bonded, the S...N distances being 3.21 and 3.11 tk (the shortest reported so far). There are also noteworthy CH...N hydrogen bonds. The effects of thermal motion upon interplanar spacings and S... N intermolecular bond lengths are investigated.

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

“…Fx and Qy correspond to derivatives of F and Q considered herein. F, F1‐F14 correspond to F derivatives co‐crystallized with Q, and Q, Q1, and Q2 correspond to Q derivatives co‐crystallized with F. F⋅Q, F1⋅Q, F2⋅Q, F3⋅Q, F4⋅Q, F5⋅Q, F6⋅Q, and F⋅Q1 exhibit Class 1 packing. F6a⋅Q, F7⋅Q, F8⋅Q, F9⋅Q, F10⋅Q, F11⋅Q, and F⋅Q2 show Class 2 packing.…”

“…Hirshfelds urface analysis [52] and 2D fingerprint plot analysis [65] were performed to investigate the perturbationsi ni ntermolecularc ontactso f Qc aused by variouss ubstituents on the Fu nit for the co-crystals Fx·Q (Figure2;T able S1 and Figure S1, Supporting Information). In co-crystals F·Qy,t he percentage of contacts were inspectedf or the Fu nit by altering Qy.A ll the Class 1c o-crystals of Fx·Q exhibited higher C···C, CÀH···C, C···N, H···H, andC ÀH···N contacts.X -ray crystal structure analysis of the co-crystals revealed the qualitative significance of intermolecularC ···C (all carbonsa re sp 2 -hybridized if not mentioned otherwise), C···C sp (in F·Q, F1·Q-F4·Q), andC sp 3ÀH···C (in F·Q1) interactions in driv-Scheme1.Scheme of search in CSD for co-crystals containingFand Qasc ore.F xa nd Qy correspond to derivatives of Fa nd Qc onsidered herein.F ,F 1-F14 correspond to Fd erivatives co-crystallized with Q, and Q, Q1, and Q2 correspond to Qderivatives co-crystallized with F. F·Q, [67] F1·Q, [68] F2·Q, [69] F3·Q, [70] F4·Q, [71] F5·Q, [72] F6·Q, [73] and F·Q1 [74] exhibitC lass 1p acking. F6a·Q, [75] F7·Q, [76] F8·Q, [77] F9·Q, [76] F10·Q, [76] F11·Q, [76] and F·Q2 [78] show Class 2p acking.C lass 3a type includes F12·Q [79] and F13·Q, [80] whereas F14·Q [81] displays Class3bp acking.…”

Intermolecular energy, structure and stability of regular stacks of tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ)

“…References: (a) Phillips, Kistenmacher, Ferraris & Cowan (1973); (b) Kistenmacher, Phillips & Cowan (1974); (c) Schultz, Stucky, Craven, Schaffman & Salamon (1976); (d) Berger, Dahm, Johnson, Miles & Wilson (1975); (e) Scott, La Placa, Torrance, Silverman & Welber (1977); (f) Dahm, Johnson, May, Miles & Wilson (1975); (g) Daly & Sanz (1975); (h) Johnson & Watson (1976); (i) Wudl, Schafer, Walsh, Rupp, DiSalvo, Waszczak, Kaplan & Thomas (1977); (j) Kobayashi & Kobayashi (1977); (k) Chasseau, Gaultier, Hauw, Fabre, Giral & Torreilles (1978); (l) Phillips, Kistenmacher, Bloch, Ferraris & Cowan (1977); (m) Bechgaard, Kistenmacher, Bloch & Cowan (1977); (n) Kistenmacher, Phillips, Cowan, Ferraris & Bloch (1976); (o) Chasseau, Comberton, Gaultier & Hauw (1978); (p) ; (q) Fritchie (1966); (r) Kobayashi, Fumiyuki & Yoshihiko (1971); (s) Hanson (1968); (t) Kobayashi (1974); (u) Shibaeva & Rozenberg (1976); (v) Shibaeva, Atovmyan & Orfonova (1969); (w) Filhol, Rovira, Hauw, Gaultier, Chasseau & Dupuis (1979); (x) van Bodegom, de Boer & Vos (1977); (y) Shirotani & Kobayashi (1973); (z) Kobayashi (1978); (aa) Konno & Saito (1975); (bb) Konno, Ishii & Saito (1977); (cc) Shibaeva, Atovmyan & Rozenberg (1969); (dd) Shibaeva & Yarochkina (1975).…”

Syntheses, Crystal Structures, Transport Properties and First-Principles Electronic Structure Study of the (tTTF)2X (X = Br, I) Low-Dimensional Antiferromagnets

“…Looking for such cation radical salts with an AF ground state, we were attracted by a salt of the unsymmetrically substituted trimethylene-tetrathiafulvalene (noted tTTF) with the bromide anion, that is, (tTTF) 2 Br, where a Néel temperature of 33 K was reported from electron paramagnetic resonance (EPR) characterizations. , This temperature is, to our knowledge, the highest one among cation radical salts derived from TTFs and indicates a strong stability of this ordered magnetic phase. Only a few salts have been described so far with tTTF, prepared either by electrocrystallization with small anions (ClO 4 − , ReO 4 − , PF 6 − , AsF 6 − , SbF 6 − ) or by chemical oxidation with TCNQ . However, the crystal structure of the bromide salt was unknown, because of the low quality of the crystals obtained then.…”