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Acta Cryst. (2002). C58, o36-o38
https://doi.org/10.1107/S0108270101017632
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2,2'-[2,3-Di­hydro-2-(prop-2-enyl)-1H-isoindole-1,3-diyl­idene]bis(propane­di­nitrile)-tetra­thia­fulvalene (1/1), TCPI-TTF

C. Crean, J. F. Gallagher and A. C. Pratt
The title complex, C17H9N5·C6H4S4, contains [pi]-deficient bis(di­nitrile) and TTF mol­ecules stacked alternately in columns along the a-axis direction; the interplanar angle between the TTF molecule and the isoindolinyl C4N[C(CN)2]2 moiety is 1.21 (4)°. The N-allyl moiety in the TCPI mol­ecule is oriented at an angle of 87.10 (10)° with respect to the five-membered C4N ring, and the four C[triple bond]N bond lengths range from 1.134 (3) to 1.142 (3) Å, with C-C[triple bond]N angles in the range 174.3 (3)-176.9 (2)°. In the TTF system, the S-C bond lengths are 1.726 (3)-1.740 (3) and 1.751 (2)-1.763 (2) Å for the external S-C(H) and internal S-C(S) bonds, respectively.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101017632/sk1518sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101017632/sk1518Isup2.hkl
Contains datablock I

CCDC reference: 180166

Comment top

Organic conductors are currently an important research area in materials science (Martin et al., 1997; Yamashita & Tomura, 1998; Bryce, 2000) of which the organic metal system, TTF–TCNQ is exemplary (TCNQ is tetracyanoquinodimethane). Such complexes can be divided into (i) donor (D)–acceptor (A) systems derived from closed-shell electron donor and acceptor organic molecules and (ii) radical salts comprising a radical ion of an organic donor or acceptor molecule and a closed-shell counter ion. Our interest is with the former type D–A complexes and in the interaction of π-deficient and π-excessive materials in 1:1 complexes e.g. TCNQ–TTF, with the purpose of studying weak interactions. Herein, we report the crystal structure of 2,2'-[N-(allyl)isoindolin-1,3-diylidene]bispropanedinitrile:tetrathiafulvalene (1/1), TCPI–TTF (I) (Fig. 1).

The bond lengths and angles in the heterocyclic ring of TCPI are similar to those reported in the molecular structure of 2,2'-(cinnamylisoindolin-1,3-diylidene)bispropanedinitrile (II) (Crean et al., 2001). As TCPI analogues are rare, analysis of TCNQ molecules (III) for comparison purposes was undertaken using the April 2001 CONQUEST 1.2 version of the Cambridge Structural Database (CSD) (Allen & Kennard, 1993). In TCNQ systems (280 examples, 401 hits), the mean exocyclic Csp2═ Csp2 and Csp2—Csp1 bond lengths are 1.394 Å (range 1.33 to 1.45 Å) and 1.425 Å (range 1.36 to 1.55 Å), respectively, (full details deposited). In (I), the exocyclic indolinyl ring C═C bond lengths C4═C6A and C5═C6B are 1.372 (3) and 1.374 (3) Å, respectively, and longer than typical double bonds: the C6A—C7A/C6A—C8A, and C6B—C7B/C6B—C8B bond lengths are in the range 1.430 (3) to 1.440 (3) Å and similar to those reported for (II) (Crean et al., 2001) and in the CSD (Allen & Kennard, 1993). The four nitrile C≡N values range from 1.134 (3) to 1.142 (3) Å and are comparable with the average literature C≡N length 1.144 (8) Å (Orpen et al., 1994). The angles which the C(C≡N)2 groups make with the C4N ring are 7.56 (10) (C6A) and 6.57 (10)° (C6B), respectively, demonstrating a small twist from co-planarity about the C4—C6A/C5—C6B bonds and similar to the values of 7.01 (10) and 2.33 (10)° in (II). The N-allyl moiety is oriented at an angle of 87.10 (10)° to the C4N heterocyclic ring with bond lengthsalong the N1—C1—C2=C3 group of 1.471 (2), 1.496 (3) and 1.296 (3) Å, and analogous to 1.469 (2), 1.495 (2) and 1.319 (2) Å in (II) (Crean et al., 2001): the C═C bond length is shorter in (I). A search for N—CH2—CH=CH2 systems in the CSD (Allen & Kennard, 1993), with the terminal C═C atoms limited to 3-coordination yielded 109 examples, 151 hits, and gave mean bond lengths of 1.476, 1.480 and 1.275 Å, and angles of 112.9 and 126.6° along the chain.

The S—C bond lengths in the TTF molecule of (I) are in the range 1.726 (3) to 1.740 (3) Å for the external S—CH, and 1.751 (2) to 1.763 (2) Å for the internal S—CS. The mean CSD value is 1.735 Å for TTF systems (IV) (91 entries, 164 examples), for all of the exo-/endo- C—S bond lengths. The C=C bond lengths of 1.344 (3) and 1.314 (4)/1.325 (4) Å (exo) are shorter than the CSD values of 1.37 and 1.34 Å. This suggests that the TTF and TCPI molecules experience little perturbation on forming the [TCPI/TTF] 1:1 complex.

The hydrogen-bonding in (I) is dominated by intramolecular C—H···N interactions and close contacts, details in Table 3. This results in angles at C6A and C6B of 121.10 (17), 127.01 (18)° and 120.75 (18), 127.29 (19)°, respectively, the smaller angle reflecting the favourable effect of the intramolecular C12—H12···C7A≡N2A and C15—H15···C7B≡N2A interactions in the TCPI system. This difference is also present in (II) with an average difference of 7° between the two Csp2=Csp2—Csp angles. The TTF and TCPI isoindolinyl moiety C4N[C(CN)2]2 are essentially co-planar, 1.21 (4)°, and they stack in an alternate fashion along the a axis direction with a mean interplanar spacing between the ligands of ca 3.5 Å. Columns of [TCPI/TTF]n molecules are linked by two weak (TTF)C—H···N interactions, Table 3. A close contact N3A···S2iii, (symmetry operator iii = -x,1 - y,1 - z) is also present.

A CSD search using CONQUEST version 1.2 (Allen & Kennard, 1993) for molecular systems containing the TTF group and bis(propanedinitrile) ligands reveals several related structures including PUMVOI, bis(2,5-bis(dicyanomethylene)thieno(3,4 - b)pyrazine):TTF (1:1), (Suzuki et al., 1998), SOLGUV, bis(tetracyano-3,5-diimino-3,5-dihydropyrrolizinide-N,N')Ni(II):TTF:THF solvate (1:1:2), (Bonamico et al., 1991) and TOKXUM, pentakis(bis{ethylenedioxy}TTF):tris(dicyanomethylene)cyclopropandiide: C6H5CN solvate, (Horiuchi et al., 1996).

Experimental top

Synthesis of 2,2'-(2-allylisoindolin-1,3-diylidene)bispropanedinitrile (TCPI):

Diisopropylazodicarboxylate (0.37 g, 1.9 mmol) and triphenylphosphine (0.49 g, 1.9 mmol) were shaken together in THF (40 cm3) for 30 s. Allyl alcohol (0.2 g, 3.4 mmol) was added and the mixture was allowed to stand for two minutes, then 2-(3-dicyanomethylene-2,3-dihydro-isoindol-1-ylidene)malononitrile (0.50 g, 2.1 mmol) was added. The reaction mixture was sealed under argon and allowed stand at ambient temperature for one week. The solvent was removed and the residue subject to chromatography. TCPI was isolated as a green solid, m.p. 240–242 K. Analysis for C17H9N5: Calc. C, 72.08: H, 3.20: N, 24.72: Found C, 71.83: H, 3.28: N, 24.60. IR (KBr, cm-1), 3106, 2222, 1560, 1459, 1332, 1222, 1162, 1111, 783. U.v.-Vis (CH3CN) λmax(ε), 414 (35589), 391 (35522), 291 (9394), 279 (10303), 269 (10202), 243 (19966) nm. 1H NMR (400 MHz, δ, CDCl3), 8.74 (m, 2H, aromatic), 7.85 (m, 2H, aromatic), 6.05 (m, 1H), 5.50 (d, J = 10.4 Hz, 1H), 5.35 (s, 2H), 5.05 (d, J = 17.2 Hz, 1H). 13C NMR (δC, DMSO), 157.81 [C=C(CN)2], 135.04 132.60, 125.30 (aromatic C), 114.52, 113.27 [CN], 60.60 [C=C(CN)2], 131.30, 116.69, 48.78 (N-allyl).

Synthesis of the TCPI–TTF complex:

TCPI (0.05 g, 0.2 mmol) and TTF were added to acetonitrile (15.0 cm3). The mixture was heated under reflux until all the solid material had dissolved. The resultant green solution was allowed to cool to ambient temperature and the TCPI-TTF (1:1) complex crystallized from solution as dark green needles. The needles were isolated by filtration and recrystallized from acetonitrile to give black-green needles (0.04 g, 41.0%). m.p. 169–172 K. Analysis for C17H9N5: C6H4S4 Calc. C, 56.65: H, 2.69: N, 14.36: S, 26.30: Found C, 56.61: H, 2.62: N, 14.24: S, 25.11. IR (KBr, cm-1), 2218, 1551, 1472, 1327, 1145, 975, 651.

Refinement top

Molecule (I) crystallized in the monoclinic system; space group P21/c from the systematic absences and confirmed by the analysis. All H atoms were allowed for as riding atoms with C—H distances in the range 0.93–0.97 Å using SHELXL97 defaults.

Structure description top

Organic conductors are currently an important research area in materials science (Martin et al., 1997; Yamashita & Tomura, 1998; Bryce, 2000) of which the organic metal system, TTF–TCNQ is exemplary (TCNQ is tetracyanoquinodimethane). Such complexes can be divided into (i) donor (D)–acceptor (A) systems derived from closed-shell electron donor and acceptor organic molecules and (ii) radical salts comprising a radical ion of an organic donor or acceptor molecule and a closed-shell counter ion. Our interest is with the former type D–A complexes and in the interaction of π-deficient and π-excessive materials in 1:1 complexes e.g. TCNQ–TTF, with the purpose of studying weak interactions. Herein, we report the crystal structure of 2,2'-[N-(allyl)isoindolin-1,3-diylidene]bispropanedinitrile:tetrathiafulvalene (1/1), TCPI–TTF (I) (Fig. 1).

The bond lengths and angles in the heterocyclic ring of TCPI are similar to those reported in the molecular structure of 2,2'-(cinnamylisoindolin-1,3-diylidene)bispropanedinitrile (II) (Crean et al., 2001). As TCPI analogues are rare, analysis of TCNQ molecules (III) for comparison purposes was undertaken using the April 2001 CONQUEST 1.2 version of the Cambridge Structural Database (CSD) (Allen & Kennard, 1993). In TCNQ systems (280 examples, 401 hits), the mean exocyclic Csp2═ Csp2 and Csp2—Csp1 bond lengths are 1.394 Å (range 1.33 to 1.45 Å) and 1.425 Å (range 1.36 to 1.55 Å), respectively, (full details deposited). In (I), the exocyclic indolinyl ring C═C bond lengths C4═C6A and C5═C6B are 1.372 (3) and 1.374 (3) Å, respectively, and longer than typical double bonds: the C6A—C7A/C6A—C8A, and C6B—C7B/C6B—C8B bond lengths are in the range 1.430 (3) to 1.440 (3) Å and similar to those reported for (II) (Crean et al., 2001) and in the CSD (Allen & Kennard, 1993). The four nitrile C≡N values range from 1.134 (3) to 1.142 (3) Å and are comparable with the average literature C≡N length 1.144 (8) Å (Orpen et al., 1994). The angles which the C(C≡N)2 groups make with the C4N ring are 7.56 (10) (C6A) and 6.57 (10)° (C6B), respectively, demonstrating a small twist from co-planarity about the C4—C6A/C5—C6B bonds and similar to the values of 7.01 (10) and 2.33 (10)° in (II). The N-allyl moiety is oriented at an angle of 87.10 (10)° to the C4N heterocyclic ring with bond lengthsalong the N1—C1—C2=C3 group of 1.471 (2), 1.496 (3) and 1.296 (3) Å, and analogous to 1.469 (2), 1.495 (2) and 1.319 (2) Å in (II) (Crean et al., 2001): the C═C bond length is shorter in (I). A search for N—CH2—CH=CH2 systems in the CSD (Allen & Kennard, 1993), with the terminal C═C atoms limited to 3-coordination yielded 109 examples, 151 hits, and gave mean bond lengths of 1.476, 1.480 and 1.275 Å, and angles of 112.9 and 126.6° along the chain.

The S—C bond lengths in the TTF molecule of (I) are in the range 1.726 (3) to 1.740 (3) Å for the external S—CH, and 1.751 (2) to 1.763 (2) Å for the internal S—CS. The mean CSD value is 1.735 Å for TTF systems (IV) (91 entries, 164 examples), for all of the exo-/endo- C—S bond lengths. The C=C bond lengths of 1.344 (3) and 1.314 (4)/1.325 (4) Å (exo) are shorter than the CSD values of 1.37 and 1.34 Å. This suggests that the TTF and TCPI molecules experience little perturbation on forming the [TCPI/TTF] 1:1 complex.

The hydrogen-bonding in (I) is dominated by intramolecular C—H···N interactions and close contacts, details in Table 3. This results in angles at C6A and C6B of 121.10 (17), 127.01 (18)° and 120.75 (18), 127.29 (19)°, respectively, the smaller angle reflecting the favourable effect of the intramolecular C12—H12···C7A≡N2A and C15—H15···C7B≡N2A interactions in the TCPI system. This difference is also present in (II) with an average difference of 7° between the two Csp2=Csp2—Csp angles. The TTF and TCPI isoindolinyl moiety C4N[C(CN)2]2 are essentially co-planar, 1.21 (4)°, and they stack in an alternate fashion along the a axis direction with a mean interplanar spacing between the ligands of ca 3.5 Å. Columns of [TCPI/TTF]n molecules are linked by two weak (TTF)C—H···N interactions, Table 3. A close contact N3A···S2iii, (symmetry operator iii = -x,1 - y,1 - z) is also present.

A CSD search using CONQUEST version 1.2 (Allen & Kennard, 1993) for molecular systems containing the TTF group and bis(propanedinitrile) ligands reveals several related structures including PUMVOI, bis(2,5-bis(dicyanomethylene)thieno(3,4 - b)pyrazine):TTF (1:1), (Suzuki et al., 1998), SOLGUV, bis(tetracyano-3,5-diimino-3,5-dihydropyrrolizinide-N,N')Ni(II):TTF:THF solvate (1:1:2), (Bonamico et al., 1991) and TOKXUM, pentakis(bis{ethylenedioxy}TTF):tris(dicyanomethylene)cyclopropandiide: C6H5CN solvate, (Horiuchi et al., 1996).

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 1998); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 1998).

Figures top
[Figure 1] Fig. 1. A view of (I) with our numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A view of the interactions and packing in the crystal structure.
2-[3-(1-cyano-2-nitriloethylidene)-2-prop-2-enyl-2,3-dihydro- 1H-isoindol-1-yliden]propanedinitrile tetrathiafulvalene (1:1) top
Crystal data top
C17H9N5·C6H4S4F(000) = 1000
Mr = 487.62Dx = 1.449 Mg m−3
Monoclinic, P21/cMelting point: 443 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.3982 (11) ÅCell parameters from 25 reflections
b = 31.854 (5) Åθ = 5.5–19.9°
c = 9.516 (2) ŵ = 0.45 mm−1
β = 94.608 (17)°T = 294 K
V = 2235.3 (7) Å3Block, red
Z = 40.50 × 0.50 × 0.35 mm
Data collection top
Bruker AXS P4
diffractometer		4247 reflections with I > 2σ(I)
Radiation source: X-ray tubeRint = 0.018
Graphite monochromatorθmax = 28.0°, θmin = 2.2°
ω scansh = −1→9
Absorption correction: ψ scan
(North et al., 1968)		k = −42→1
Tmin = 0.806, Tmax = 0.860l = −12→12
5764 measured reflections3 standard reflections every 296 reflections
5366 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0586P)2 + 0.6527P]
where P = (Fo2 + 2Fc2)/3
5366 reflections(Δ/σ)max = 0.001
289 parametersΔρmax = 0.71 e Å−3
0 restraintsΔρmin = −0.38 e Å−3
Crystal data top
C17H9N5·C6H4S4V = 2235.3 (7) Å3
Mr = 487.62Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.3982 (11) ŵ = 0.45 mm−1
b = 31.854 (5) ÅT = 294 K
c = 9.516 (2) Å0.50 × 0.50 × 0.35 mm
β = 94.608 (17)°
Data collection top
Bruker AXS P4
diffractometer		4247 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.018
Tmin = 0.806, Tmax = 0.8603 standard reflections every 296 reflections
5764 measured reflections intensity decay: 1%
5366 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.09Δρmax = 0.71 e Å−3
5366 reflectionsΔρmin = −0.38 e Å−3
289 parameters
Special details top

Geometry. Mean plane data ex-SHELXL97 for (I) ###################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

7.0155 (0.0023) x + 8.2548 (0.0125) y - 2.4642 (0.0033) z = 4.4742 (0.0043)

* -0.0099 (0.0010) S1 * -0.0012 (0.0010) S2 * -0.0287 (0.0011) S3 * -0.0193 (0.0011) S4 * -0.0136 (0.0018) C1T * -0.0147 (0.0019) C2T * 0.0175 (0.0020) C3T * 0.0165 (0.0020) C4T * 0.0269 (0.0021) C5T * 0.0265 (0.0021) C6T

Rms deviation of fitted atoms = 0.0193

7.0092 (0.0026) x + 8.0733 (0.0178) y - 2.5771 (0.0094) z = 4.3587 (0.0086)

Angle to previous plane (with approximate e.s.d.) = 0.76 (5)

* -0.0024 (0.0010) S1 * -0.0014 (0.0010) S2 * 0.0024 (0.0009) C1T * -0.0005 (0.0016) C3T * 0.0019 (0.0016) C4T 0.0132 (0.0036) S3 0.0305 (0.0036) S4 0.0944 (0.0057) C5T 0.0904 (0.0057) C6T

Rms deviation of fitted atoms = 0.0019

7.0268 (0.0026) x + 8.4986 (0.0194) y - 2.2760 (0.0102) z = 4.5602 (0.0067)

Angle to previous plane (with approximate e.s.d.) = 1.99 (6)

* -0.0139 (0.0011) S3 * -0.0125 (0.0011) S4 * 0.0163 (0.0010) C2T * 0.0035 (0.0017) C5T * 0.0067 (0.0018) C6T 0.0661 (0.0038) S1 0.0823 (0.0039) S2 0.1315 (0.0059) C3T 0.1271 (0.0059) C4T

Rms deviation of fitted atoms = 0.0116

7.0155 (0.0023) x + 8.2548 (0.0125) y - 2.4642 (0.0033) z = 4.4742 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 1.23 (5)

* -0.0099 (0.0010) S1 * -0.0012 (0.0010) S2 * -0.0287 (0.0011) S3 * -0.0193 (0.0011) S4 * -0.0136 (0.0018) C1T * -0.0147 (0.0019) C2T * 0.0175 (0.0020) C3T * 0.0165 (0.0020) C4T * 0.0269 (0.0021) C5T * 0.0265 (0.0021) C6T

Rms deviation of fitted atoms = 0.0193

6.9902 (0.0030) x + 8.1215 (0.0268) y - 2.6720 (0.0083) z = 0.8202 (0.0111)

Angle to previous plane (with approximate e.s.d.) = 1.31 (6)

* -0.0307 (0.0011) N1 * 0.0223 (0.0011) C4 * 0.0255 (0.0011) C5 * -0.0059 (0.0011) C11 * -0.0112 (0.0011) C16 0.4238 (0.0049) N2A 0.1623 (0.0052) N3A 0.3414 (0.0050) N2B 0.2791 (0.0049) N3B

Rms deviation of fitted atoms = 0.0212

7.0155 (0.0023) x + 8.2548 (0.0125) y - 2.4642 (0.0033) z = 4.4742 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 1.31 (6)

* -0.0099 (0.0010) S1 * -0.0012 (0.0010) S2 * -0.0287 (0.0011) S3 * -0.0193 (0.0011) S4 * -0.0136 (0.0018) C1T * -0.0147 (0.0019) C2T * 0.0175 (0.0020) C3T * 0.0165 (0.0020) C4T * 0.0269 (0.0021) C5T * 0.0265 (0.0021) C6T

Rms deviation of fitted atoms = 0.0193

7.0919 (0.0028) x + 6.5423 (0.0272) y - 2.6040 (0.0078) z = 0.2508 (0.0096)

Angle to previous plane (with approximate e.s.d.) = 3.24 (6)

* -0.0008 (0.0013) C11 * -0.0018 (0.0015) C12 * 0.0027 (0.0016) C13 * -0.0011 (0.0016) C14 * -0.0014 (0.0015) C15 * 0.0024 (0.0013) C16 - 0.2331 (0.0046) C1 1.1024 (0.0053) C2 2.2583 (0.0049) C3 - 0.1339 (0.0032) N1

Rms deviation of fitted atoms = 0.0018

0.5612 (0.0115) x + 9.2232 (0.0386) y + 8.9925 (0.0038) z = 5.9551 (0.0189)

Angle to previous plane (with approximate e.s.d.) = 86.79 (10)

* -0.0062 (0.0013) C1 * 0.0072 (0.0015) C2 * -0.0040 (0.0008) C3 * 0.0030 (0.0006) N1

Rms deviation of fitted atoms = 0.0054

6.9902 (0.0030) x + 8.1215 (0.0268) y - 2.6720 (0.0083) z = 0.8202 (0.0111)

Angle to previous plane (with approximate e.s.d.) = 87.10 (10)

* -0.0307 (0.0011) N1 * 0.0223 (0.0011) C4 * 0.0255 (0.0011) C5 * -0.0059 (0.0011) C11 * -0.0112 (0.0011) C16 0.4238 (0.0049) N2A 0.1623 (0.0052) N3A 0.3414 (0.0050) N2B 0.2791 (0.0049) N3B

Rms deviation of fitted atoms = 0.0212

7.0919 (0.0028) x + 6.5423 (0.0272) y - 2.6040 (0.0078) z = 0.2508 (0.0096)

Angle to previous plane (with approximate e.s.d.) = 2.99 (7)

* -0.0008 (0.0013) C11 * -0.0018 (0.0015) C12 * 0.0027 (0.0016) C13 * -0.0011 (0.0016) C14 * -0.0014 (0.0015) C15 * 0.0024 (0.0013) C16 - 0.2331 (0.0046) C1 1.1024 (0.0053) C2 2.2583 (0.0049) C3 - 0.1339 (0.0032) N1

Rms deviation of fitted atoms = 0.0018

0.5612 (0.0115) x + 9.2232 (0.0386) y + 8.9925 (0.0038) z = 5.9551 (0.0189)

Angle to previous plane (with approximate e.s.d.) = 86.79 (10)

* -0.0062 (0.0013) C1 * 0.0072 (0.0015) C2 * -0.0040 (0.0008) C3 * 0.0030 (0.0006) N1

Rms deviation of fitted atoms = 0.0054

6.9902 (0.0030) x + 8.1215 (0.0268) y - 2.6720 (0.0083) z = 0.8202 (0.0111)

Angle to previous plane (with approximate e.s.d.) = 87.10 (10)

* -0.0307 (0.0011) N1 * 0.0223 (0.0011) C4 * 0.0255 (0.0011) C5 * -0.0059 (0.0011) C11 * -0.0112 (0.0011) C16 0.4238 (0.0049) N2A 0.1623 (0.0052) N3A 0.3414 (0.0050) N2B 0.2791 (0.0049) N3B

Rms deviation of fitted atoms = 0.0212

7.0919 (0.0028) x + 6.5423 (0.0272) y - 2.6040 (0.0078) z = 0.2508 (0.0096)

Angle to previous plane (with approximate e.s.d.) = 2.99 (7)

* -0.0008 (0.0013) C11 * -0.0018 (0.0015) C12 * 0.0027 (0.0016) C13 * -0.0011 (0.0016) C14 * -0.0014 (0.0015) C15 * 0.0024 (0.0013) C16 - 0.2331 (0.0046) C1 1.1024 (0.0053) C2 2.2583 (0.0049) C3 - 0.1339 (0.0032) N1

Rms deviation of fitted atoms = 0.0018

0.5960 (0.0146) x + 8.6391 (0.1384) y + 9.0362 (0.0099) z = 5.6767 (0.0664)

Angle to previous plane (with approximate e.s.d.) = 86.77 (13)

* 0.0000 (0.0000) C1 * 0.0000 (0.0000) C2 * 0.0000 (0.0000) C3 0.0380 (0.0080) N1

Rms deviation of fitted atoms = 0.0000

0.5612 (0.0115) x + 9.2232 (0.0386) y + 8.9925 (0.0038) z = 5.9551 (0.0189)

Angle to previous plane (with approximate e.s.d.) = 1.1 (2)

* -0.0062 (0.0013) C1 * 0.0072 (0.0015) C2 * -0.0040 (0.0008) C3 * 0.0030 (0.0006) N1

Rms deviation of fitted atoms = 0.0054

7.0155 (0.0023) x + 8.2548 (0.0125) y - 2.4642 (0.0033) z = 4.4742 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 88.40 (9)

* -0.0099 (0.0010) S1 * -0.0012 (0.0010) S2 * -0.0287 (0.0011) S3 * -0.0193 (0.0011) S4 * -0.0136 (0.0018) C1T * -0.0147 (0.0019) C2T * 0.0175 (0.0020) C3T * 0.0165 (0.0020) C4T * 0.0269 (0.0021) C5T * 0.0265 (0.0021) C6T

Rms deviation of fitted atoms = 0.0193

6.7563 (0.0035) x + 7.5143 (0.0431) y - 3.8493 (0.0148) z = 0.1299 (0.0260)

Angle to previous plane (with approximate e.s.d.) = 8.87 (8)

* 0.0014 (0.0012) C6A * -0.0084 (0.0019) C7A * 0.0054 (0.0023) C8A * 0.0047 (0.0011) N2A * -0.0031 (0.0013) N3A 0.0605 (0.0047) C4 0.3584 (0.0087) C5

Rms deviation of fitted atoms = 0.0052

6.9902 (0.0030) x + 8.1215 (0.0268) y - 2.6720 (0.0083) z = 0.8202 (0.0111)

Angle to previous plane (with approximate e.s.d.) = 7.56 (10)

* -0.0307 (0.0011) N1 * 0.0223 (0.0011) C4 * 0.0255 (0.0011) C5 * -0.0059 (0.0011) C11 * -0.0112 (0.0011) C16 - 0.0538 (0.0032) C1 1.3150 (0.0038) C2 2.4394 (0.0035) C3 0.4238 (0.0049) N2A 0.1623 (0.0052) N3A 0.3414 (0.0050) N2B 0.2791 (0.0049) N3B

Rms deviation of fitted atoms = 0.0212

7.0817 (0.0029) x + 8.7257 (0.0233) y - 1.6161 (0.0176) z = 1.1787 (0.0095)

Angle to previous plane (with approximate e.s.d.) = 6.57 (9)

* -0.0004 (0.0012) C6B * -0.0006 (0.0020) C7B * 0.0014 (0.0019) C8B * 0.0004 (0.0011) N2B * -0.0008 (0.0011) N3B 0.2974 (0.0084) C4 0.0422 (0.0045) C5

Rms deviation of fitted atoms = 0.0008

7.0155 (0.0023) x + 8.2548 (0.0125) y - 2.4642 (0.0033) z = 4.4742 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 5.26 (7)

* -0.0099 (0.0010) S1 * -0.0012 (0.0010) S2 * -0.0287 (0.0011) S3 * -0.0193 (0.0011) S4 * -0.0136 (0.0018) C1T * -0.0147 (0.0019) C2T * 0.0175 (0.0020) C3T * 0.0165 (0.0020) C4T * 0.0269 (0.0021) C5T * 0.0265 (0.0021) C6T -3.5838 (0.0024) N1 - 3.5026 (0.0024) C4 - 3.5510 (0.0024) C5 - 3.5363 (0.0022) C11 - 3.5733 (0.0022) C16

Rms deviation of fitted atoms = 0.0193

7.0083 (0.0023) x + 7.9162 (0.0143) y - 2.6417 (0.0024) z = 0.9096 (0.0058)

Angle to previous plane (with approximate e.s.d.) = 1.24 (4)

* -0.0483 (0.0020) C6A * 0.1166 (0.0020) C7A * -0.0335 (0.0024) C8A * 0.2718 (0.0020) N2A * -0.0216 (0.0023) N3A * -0.0364 (0.0019) C6B * 0.0777 (0.0021) C7B * 0.0273 (0.0021) C8B * 0.1765 (0.0022) N2B * 0.0858 (0.0020) N3B * -0.1430 (0.0017) C4 * -0.1431 (0.0017) C5 * -0.1612 (0.0017) C11 * -0.1686 (0.0017) C16 3.3695 (0.0025) S1 3.3613 (0.0015) S2 3.4011 (0.0015) S3 3.4279 (0.0025) S4

Rms deviation of fitted atoms = 0.1291

7.0155 (0.0023) x + 8.2548 (0.0125) y - 2.4642 (0.0033) z = 4.4742 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 1.24 (4)

* -0.0099 (0.0010) S1 * -0.0012 (0.0010) S2 * -0.0287 (0.0011) S3 * -0.0193 (0.0011) S4 * -0.0136 (0.0018) C1T * -0.0147 (0.0019) C2T * 0.0175 (0.0020) C3T * 0.0165 (0.0020) C4T * 0.0269 (0.0021) C5T * 0.0265 (0.0021) C6T

Rms deviation of fitted atoms = 0.0193

7.0015 (0.0023) x + 8.0062 (0.0142) y - 2.6488 (0.0024) z = 0.9325 (0.0058)

Angle to previous plane (with approximate e.s.d.) = 1.21 (4)

* -0.0343 (0.0020) C6A * 0.1278 (0.0020) C7A * -0.0153 (0.0024) C8A * 0.2808 (0.0020) N2A * -0.0002 (0.0024) N3A * -0.0225 (0.0019) C6B * 0.0888 (0.0021) C7B * 0.0454 (0.0021) C8B * 0.1855 (0.0022) N2B * 0.1071 (0.0020) N3B * -0.1886 (0.0016) N1 * -0.1305 (0.0017) C4 * -0.1306 (0.0017) C5 * -0.1530 (0.0017) C11 * -0.1604 (0.0017) C16

Rms deviation of fitted atoms = 0.1346

###################################

A CSD search for all TCNQ systems yielded 282 'hits' and 402 structures.

The Csp2=Csp2 and Csp2-Csp1 bond lengths were analysed in the C(CN)2.

Restrictions included three-dimensional coordinates and R < 0.1, the two C(CN)2 atoms had to be bonded to three atoms only and the four N atoms one coordinate to minimize perturbation of the relevant bond lengths.

TCNQ derivatives ================ Nent 282 ========== Nobs 403 403 403 403 403 403 Mean 1.393 1.393 1.425 1.426 1.425 1.425 SDSample. 022. 022. 015. 013. 014. 014 SDMean. 001. 001. 001. 001. 001. 001 Minimum 1.248 1.248 1.356 1.373 1.364 1.356 Maximum 1.447 1.447 1.548 1.470 1.500 1.528

Nent 280 (two structures BCDPDQ01/BCDPDQ02 in error were deleted) ========== Nobs 401 401 401 401 401 401 Mean 1.394 1.394 1.425 1.426 1.425 1.425 SDSample. 020. 020. 015. 013. 013. 014 SDMean. 001. 001. 001. 001. 001. 001 Minimum 1.331 1.346 1.356 1.373 1.364 1.356 Maximum 1.447 1.447 1.548 1.470 1.500 1.528

Bonds Csp2=Csp2 (x2) and Csp2—Csp1 (x4)

#===================================================================

A CSD search for all TTF systems yielded 91 'hits' and 164 structures.

The C···S and C···C bond lengths were analysed in the TTF system.

Restrictions included three-dimensional coordinates and R < 0.1, the four sulfur atoms had to be bonded to two atoms only, thus limiting metal coordination etc.

TTF derivatives =============== Nent 91 ========= Nobs 164 164 164 164 164 164 164 164 164 164 164 Mean 1.732 1.735 1.735 1.731 1.737 1.735 1.735 1.736 1.367 1.342 1.341 SDSample. 021. 019. 019. 023. 036. 028. 030. 037. 027. 059. 059 SDMean. 002. 002. 002. 002. 003. 002. 002. 003. 002. 005. 005 Minimum 1.683 1.663 1.668 1.645 1.626 1.695 1.654 1.572 1.298 1.265 1.260 Maximum 1.790 1.782 1.798 1.790 1.832 1.812 1.812 1.832 1.418 1.520 1.520

Bonds C—S (x4), C—S (x4), C=C, C=C (x2) = 11 total.

#===================================================================

A search for all NAL (N-allyl) systems yielded 109 'hits' and 151 structures.

The N—C—C=C bond lengths and angles were analysed in these NAL systems.

Restrictions included three-dimensional coordinates and R < 0.1, the terminal C=C atoms had to be bonded to three atoms only, thus limiting metal coordination.

N-allyl derivatives =================== Nent 109 ================== Nobs 151 151 151 151 151 Mean 1.476 1.480 1.275 112.861 126.587 SDSample. 034. 040. 055 2.852 6.265 SDMean. 003. 003. 005. 232. 510 Minimum 1.390 1.204 1.045 97.034 111.459 Maximum 1.709 1.551 1.396 127.356 169.277

Removing the two structures which deviate the most from the mean does not change the mean parameter values (107/144).

###################################

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.42240 (8)0.311005 (18)0.43274 (6)0.05158 (15)
S20.29873 (8)0.397780 (17)0.36781 (6)0.04844 (14)
S30.20999 (8)0.372260 (17)0.04086 (6)0.05053 (15)
S40.33541 (9)0.285452 (17)0.10331 (6)0.05370 (16)
C1T0.3349 (3)0.34667 (6)0.3047 (2)0.0406 (4)
C2T0.2992 (3)0.33626 (6)0.1685 (2)0.0412 (4)
C3T0.3757 (4)0.38603 (9)0.5401 (2)0.0626 (6)
C4T0.4310 (4)0.34756 (9)0.5689 (2)0.0634 (6)
C5T0.2666 (4)0.29802 (9)−0.0692 (3)0.0635 (6)
C6T0.2110 (4)0.33689 (9)−0.0971 (2)0.0625 (6)
N1−0.2780 (2)0.41884 (5)0.25033 (16)0.0370 (3)
N2A−0.0196 (3)0.41153 (7)0.7339 (2)0.0666 (6)
N3A−0.2593 (4)0.51313 (7)0.5137 (3)0.0823 (8)
N2B−0.2645 (4)0.32291 (7)−0.1453 (2)0.0711 (6)
N3B−0.4189 (3)0.44801 (8)−0.1456 (2)0.0729 (6)
C1−0.3455 (3)0.46094 (6)0.2103 (2)0.0440 (4)
C2−0.1977 (3)0.48993 (7)0.1729 (2)0.0552 (6)
C3−0.0272 (4)0.48082 (8)0.1703 (3)0.0601 (6)
C4−0.2067 (2)0.40810 (6)0.38449 (19)0.0361 (4)
C5−0.2669 (2)0.38570 (6)0.15770 (19)0.0359 (4)
C11−0.1602 (2)0.36343 (5)0.3808 (2)0.0359 (4)
C12−0.0962 (3)0.33577 (6)0.4859 (2)0.0446 (4)
C13−0.0705 (3)0.29412 (7)0.4495 (2)0.0512 (5)
C14−0.1085 (3)0.28042 (6)0.3131 (2)0.0513 (5)
C15−0.1727 (3)0.30756 (6)0.2067 (2)0.0460 (4)
C16−0.1979 (2)0.34963 (6)0.24217 (19)0.0360 (4)
C6A−0.1806 (3)0.43472 (6)0.4976 (2)0.0420 (4)
C7A−0.0920 (3)0.42079 (6)0.6283 (2)0.0480 (5)
C8A−0.2266 (3)0.47860 (7)0.5015 (2)0.0541 (5)
C6B−0.3069 (3)0.38675 (6)0.0142 (2)0.0419 (4)
C7B−0.2814 (3)0.35038 (7)−0.0704 (2)0.0494 (5)
C8B−0.3692 (3)0.42203 (7)−0.0695 (2)0.0505 (5)
H3T0.37790.40640.61020.075*
H4T0.47370.34000.66000.076*
H5T0.26850.2781−0.14050.076*
H6T0.17340.3450−0.18870.075*
H1A−0.40530.47290.28810.053*
H1B−0.43480.45850.13030.053*
H2−0.23160.51730.14890.066*
H3A0.01360.45390.19340.072*
H3B0.05430.50120.14550.072*
H12−0.07120.34490.57830.054*
H13−0.02690.27520.51840.061*
H14−0.09070.25230.29190.062*
H15−0.19810.29810.11470.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0551 (3)0.0500 (3)0.0493 (3)0.0000 (2)0.0016 (2)0.0095 (2)
S20.0518 (3)0.0415 (3)0.0527 (3)−0.0018 (2)0.0085 (2)−0.0052 (2)
S30.0547 (3)0.0452 (3)0.0513 (3)0.0057 (2)0.0021 (2)0.0079 (2)
S40.0721 (4)0.0400 (3)0.0484 (3)0.0047 (2)0.0012 (3)−0.0020 (2)
C1T0.0390 (10)0.0382 (9)0.0450 (10)−0.0031 (8)0.0059 (8)0.0006 (8)
C2T0.0436 (10)0.0367 (9)0.0434 (10)−0.0014 (8)0.0044 (8)0.0026 (8)
C3T0.0694 (16)0.0723 (16)0.0463 (12)−0.0032 (13)0.0066 (11)−0.0135 (11)
C4T0.0669 (15)0.0818 (18)0.0405 (11)−0.0003 (13)−0.0004 (10)0.0024 (11)
C5T0.0734 (16)0.0682 (15)0.0469 (12)0.0133 (13)−0.0070 (11)−0.0110 (11)
C6T0.0700 (16)0.0729 (16)0.0431 (11)0.0134 (13)−0.0048 (11)0.0012 (11)
N10.0401 (8)0.0311 (7)0.0397 (8)0.0051 (6)0.0037 (6)0.0051 (6)
N2A0.0947 (16)0.0528 (11)0.0506 (11)0.0065 (11)−0.0055 (11)0.0038 (9)
N3A0.130 (2)0.0469 (12)0.0673 (14)0.0220 (13)−0.0099 (14)−0.0118 (10)
N2B0.1015 (18)0.0563 (12)0.0536 (11)0.0069 (12)−0.0058 (11)−0.0079 (10)
N3B0.0888 (16)0.0725 (14)0.0569 (12)0.0256 (12)0.0023 (11)0.0176 (11)
C10.0511 (11)0.0344 (9)0.0459 (10)0.0114 (8)0.0012 (8)0.0056 (8)
C20.0728 (16)0.0344 (10)0.0583 (13)0.0024 (10)0.0037 (11)0.0131 (9)
C30.0676 (15)0.0532 (13)0.0605 (14)−0.0105 (12)0.0118 (11)0.0106 (11)
C40.0353 (9)0.0334 (9)0.0401 (9)0.0011 (7)0.0068 (7)0.0066 (7)
C50.0315 (9)0.0337 (8)0.0429 (9)0.0014 (7)0.0056 (7)0.0037 (7)
C110.0339 (9)0.0301 (8)0.0442 (9)−0.0001 (7)0.0058 (7)0.0055 (7)
C120.0502 (11)0.0375 (10)0.0456 (10)0.0014 (8)0.0003 (9)0.0073 (8)
C130.0572 (13)0.0381 (10)0.0574 (12)0.0048 (9)−0.0001 (10)0.0140 (9)
C140.0610 (13)0.0309 (9)0.0623 (13)0.0061 (9)0.0068 (10)0.0048 (9)
C150.0545 (12)0.0340 (9)0.0494 (11)0.0030 (8)0.0040 (9)0.0021 (8)
C160.0340 (9)0.0315 (8)0.0427 (9)−0.0001 (7)0.0045 (7)0.0052 (7)
C6A0.0479 (11)0.0362 (9)0.0423 (9)0.0039 (8)0.0060 (8)0.0034 (7)
C7A0.0618 (13)0.0379 (10)0.0448 (10)0.0017 (9)0.0066 (9)0.0009 (8)
C8A0.0726 (15)0.0431 (11)0.0459 (11)0.0082 (10)0.0012 (10)−0.0041 (9)
C6B0.0412 (10)0.0419 (10)0.0424 (10)0.0016 (8)0.0029 (8)0.0038 (8)
C7B0.0552 (12)0.0482 (11)0.0437 (10)0.0022 (9)−0.0028 (9)0.0032 (9)
C8B0.0533 (12)0.0543 (12)0.0439 (10)0.0095 (10)0.0037 (9)0.0059 (9)
Geometric parameters (Å, º) top
S1—C1T1.751 (2)C6A—C7A1.430 (3)
S1—C4T1.740 (3)C6A—C8A1.440 (3)
S2—C1T1.763 (2)C6B—C7B1.432 (3)
S2—C3T1.733 (3)C6B—C8B1.432 (3)
S3—C2T1.760 (2)C11—C121.387 (3)
S3—C6T1.731 (3)C11—C161.398 (3)
S4—C2T1.761 (2)C12—C131.388 (3)
S4—C5T1.726 (3)C13—C141.377 (3)
C1T—C2T1.344 (3)C14—C151.387 (3)
C3T—C4T1.314 (4)C15—C161.398 (3)
C5T—C6T1.325 (4)C3T—H3T0.9300
N1—C11.471 (2)C4T—H4T0.9300
N1—C41.385 (2)C5T—H5T0.9300
N1—C51.382 (2)C6T—H6T0.9300
N2A—C7A1.139 (3)C1—H1A0.9700
N3A—C8A1.134 (3)C1—H1B0.9700
N2B—C7B1.142 (3)C2—H20.9300
N3B—C8B1.141 (3)C3—H3A0.9300
C1—C21.496 (3)C3—H3B0.9300
C2—C31.296 (3)C12—H120.9300
C4—C6A1.372 (3)C13—H130.9300
C4—C111.465 (2)C14—H140.9300
C5—C6B1.374 (3)C15—H150.9300
C5—C161.470 (2)
S1—C1T—S2114.83 (11)C11—C12—C13118.20 (19)
S3—C2T—S4114.51 (11)C12—C13—C14121.12 (19)
C1T—S1—C4T94.21 (11)C13—C14—C15121.54 (19)
C1T—S2—C3T94.32 (11)C14—C15—C16117.8 (2)
C2T—S3—C6T94.30 (11)C11—C16—C15120.62 (17)
C2T—S4—C5T94.60 (11)C11—C16—C5107.74 (16)
C2T—C1T—S1122.97 (16)C15—C16—C5131.62 (18)
C2T—C1T—S2122.20 (16)C4—C6A—C7A121.10 (17)
C1T—C2T—S3122.61 (16)C4—C6A—C8A127.01 (18)
C1T—C2T—S4122.88 (15)C5—C6B—C7B120.75 (18)
C3T—C4T—S1118.46 (19)C5—C6B—C8B127.29 (19)
C4T—C3T—S2118.18 (19)N2A—C7A—C6A176.9 (2)
C5T—C6T—S3118.47 (19)N3A—C8A—C6A175.5 (3)
C6T—C5T—S4118.06 (19)N2B—C7B—C6B175.6 (2)
S1—C4T—H4T120.8N3B—C8B—C6B174.3 (3)
S2—C3T—H3T120.9C7A—C6A—C8A111.82 (18)
S3—C6T—H6T120.8C7B—C6B—C8B111.92 (18)
S4—C5T—H5T121.0N1—C1—H1A109.1
C3T—C4T—H4T120.8C2—C1—H1A109.1
C4T—C3T—H3T120.9N1—C1—H1B109.1
C5T—C6T—H6T120.8C2—C1—H1B109.1
C6T—C5T—H5T121.0C3—C2—H2116.7
C1—N1—C4124.08 (16)C1—C2—H2116.7
C1—N1—C5124.61 (16)C2—C3—H3A120.0
C4—N1—C5111.20 (15)C2—C3—H3B120.0
N1—C1—C2112.65 (17)H3A—C3—H3B120.0
C1—C2—C3126.6 (2)H1A—C1—H1B107.8
C6A—C4—N1126.14 (17)C11—C12—H12120.9
C6A—C4—C11126.93 (17)C13—C12—H12120.9
N1—C4—C11106.91 (16)C14—C13—H13119.4
C6B—C5—N1126.59 (17)C12—C13—H13119.4
C6B—C5—C16126.88 (17)C13—C14—H14119.2
N1—C5—C16106.51 (15)C15—C14—H14119.2
C12—C11—C4131.83 (18)C14—C15—H15121.1
C16—C11—C4107.37 (15)C16—C15—H15121.1
C12—C11—C16120.77 (17)
S1—C1T—C2T—S3179.61 (11)C4—N1—C5—C165.4 (2)
S2—C1T—C2T—S3−1.0 (3)C6A—C4—C11—C126.5 (3)
S1—C1T—C2T—S40.3 (3)N1—C4—C11—C12−175.1 (2)
S2—C1T—C2T—S4179.70 (11)C6A—C4—C11—C16−175.68 (18)
S2—C3T—C4T—S1−0.2 (3)N1—C4—C11—C162.7 (2)
S4—C5T—C6T—S3−0.3 (3)C16—C11—C12—C130.1 (3)
C3T—S2—C1T—S10.27 (14)C4—C11—C12—C13177.7 (2)
C4T—S1—C1T—S2−0.36 (14)C11—C12—C13—C14−0.4 (3)
C5T—S4—C2T—S32.12 (15)C12—C13—C14—C150.4 (4)
C6T—S3—C2T—S4−2.24 (15)C13—C14—C15—C160.0 (3)
C4T—S1—C1T—C2T179.11 (19)C12—C11—C16—C150.3 (3)
C3T—S2—C1T—C2T−179.21 (19)C4—C11—C16—C15−177.86 (17)
C6T—S3—C2T—C1T178.37 (19)C12—C11—C16—C5178.64 (17)
C5T—S4—C2T—C1T−178.5 (2)C4—C11—C16—C50.5 (2)
C1T—S2—C3T—C4T0.0 (2)C14—C15—C16—C11−0.3 (3)
C1T—S1—C4T—C3T0.4 (2)C14—C15—C16—C5−178.2 (2)
C2T—S4—C5T—C6T−1.1 (3)C6B—C5—C16—C11174.54 (18)
C2T—S3—C6T—C5T1.6 (3)N1—C5—C16—C11−3.5 (2)
C4—N1—C1—C284.3 (2)C6B—C5—C16—C15−7.4 (3)
C5—N1—C1—C2−91.4 (2)N1—C5—C16—C15174.6 (2)
N1—C1—C2—C31.6 (3)N1—C4—C6A—C7A−174.86 (18)
C1—N1—C4—C6A−3.0 (3)C11—C4—C6A—C7A3.3 (3)
C5—N1—C4—C6A173.26 (18)N1—C4—C6A—C8A2.0 (3)
C1—N1—C4—C11178.58 (16)C11—C4—C6A—C8A−179.8 (2)
C5—N1—C4—C11−5.2 (2)N1—C5—C6B—C7B177.14 (19)
C1—N1—C5—C6B3.6 (3)C16—C5—C6B—C7B−0.6 (3)
C4—N1—C5—C6B−172.65 (18)N1—C5—C6B—C8B−0.4 (3)
C1—N1—C5—C16−178.33 (17)C16—C5—C6B—C8B−178.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···N2A0.932.603.391 (3)143
C12—H12···C7A0.932.473.027 (3)118
C15—H15···N2B0.932.613.399 (3)144
C15—H15···C7B0.932.473.020 (3)118
C4T—H4T···N2Bi0.932.633.479 (3)152
C6T—H6T···N2Aii0.932.633.273 (3)127
Symmetry codes: (i) x+1, y, z+1; (ii) x, y, z−1.

Experimental details

Crystal data
Chemical formulaC17H9N5·C6H4S4
Mr487.62
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)7.3982 (11), 31.854 (5), 9.516 (2)
β (°) 94.608 (17)
V (Å3)2235.3 (7)
Z4
Radiation typeMo Kα
µ (mm−1)0.45
Crystal size (mm)0.50 × 0.50 × 0.35
Data collection
DiffractometerBruker AXS P4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.806, 0.860
No. of measured, independent and
observed [I > 2σ(I)] reflections		5764, 5366, 4247
Rint0.018
(sin θ/λ)max (Å−1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.121, 1.09
No. of reflections5366
No. of parameters289
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.71, −0.38

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 1998), SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 1998).

Selected geometric parameters (Å, º) top
S1—C1T1.751 (2)C1T—C2T1.344 (3)
S1—C4T1.740 (3)C3T—C4T1.314 (4)
S2—C1T1.763 (2)C5T—C6T1.325 (4)
S2—C3T1.733 (3)N1—C11.471 (2)
S3—C2T1.760 (2)N1—C41.385 (2)
S3—C6T1.731 (3)N1—C51.382 (2)
S4—C2T1.761 (2)C1—C21.496 (3)
S4—C5T1.726 (3)C2—C31.296 (3)
N1—C1—C2112.65 (17)C1—C2—C3126.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···N2A0.932.603.391 (3)143
C12—H12···C7A0.932.473.027 (3)118
C15—H15···N2B0.932.613.399 (3)144
C15—H15···C7B0.932.473.020 (3)118
C4T—H4T···N2Bi0.932.633.479 (3)152
C6T—H6T···N2Aii0.932.633.273 (3)127
Symmetry codes: (i) x+1, y, z+1; (ii) x, y, z−1.
 

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