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A new bis-TTF donor (TTF is tetra­thia­fulvalene) containing a pyridine diester spacer, namely bis­{2-[(6,7-tetra­methyl­ene-3-methyl­sulfanyl­tetra­thia­fulvalen-2-yl)sulfan­yl]eth­yl} pyridine-2,6-dicarboxyl­ate–tetra­cyano­quinodimethane–dichloromethane (2/1/2), 2C33H33NO4S12·C12H4N4·2CH2Cl2, has been synthesized and its electron-donating ability determined by cyclic voltammetry. The electrical conductivity and crystal structure of this donor–acceptor (DA) complex with TCNQ (tetra­cyano­quinodimethane) as the acceptor are presented. The TCNQ moiety lies across a crystallographic inversion centre. In the crystal structure, TTF and TCNQ entities are arranged in alternate stacks; this feature, together with the bond lengths of the TCNQ mol­ecule, suggest that the expected charge transfer has not occurred and that the D and A entities are in the neutral state, in agreement with the poor conductivity of the material (σRT = 2 × 10−6 S cm−1).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110028155/gt3021sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110028155/gt3021Isup2.hkl
Contains datablock I

CCDC reference: 790652

Comment top

It is now clearly established that the metallic state observed in organic conducting materials of the TTF type (TTF = tetrathiafulvalene) (Fabre, 2002) can be strongly stabilized by increasing their structural and electronic dimensionality (Williams et al., 1992; Fabre, 2000). Such a result can be attained by introducing, on the TTF ring, a functional group able to provide supplementary molecular interactions (Batsanov et al., 1995; Heuzé et al., 2000; Legros et al., 2000; Lorcy et al., 2009). In the past decade, extended TTF systems have received much attention as building blocks potentially able to enhance the dimensionality in derived conducting materials (Bryce, 1995; Iyoda, 2004; Lorcy et al., 2009). Following a similar strategy, we have developed a research programme based mainly on bis-TTF, in which the TTF cores are linked by various functionalized spacers (Bouguessa et al., 2003; Carcel et al., 2006; Kaboub et al., 2008; Kaboub, 2009). As part of this research programme, we have synthesised a new bis-TTF donor compound, (3) (see scheme), in which ester functionalities have been created within the covalent spacer linking the two TTF units to give bis[(6,7-tetramethylene-3-methylsulfanyltetrathiafulvalenyl)-2-ethylsulfanyl]pyridine-2,6-dicarboxylate [abridged name hereinafter: bis-TTF(pyridine-bi-ester)]. Moreover, the presence of a pyridine ring in (3) can allow the coordination of paramagnetic metals, leading to potential precursors of magnetic conducting solids (Iwahori et al., 2001; Ouahab et al., 2003; Lorcy et al., 2009). In the present work, we describe the preparation and electrochemical behaviour of (3). Since the electrochemical properties of this new donor are promising (see Experimental), we have prepared the title donor–acceptor (DA) complex, (I), with TCNQ (tetracyanoquinodimethane) as the π-acceptor. The structural properties and electrical conductivity of this material are also given and discussed below.

The crystal structure of complex (I) was determined from single-crystal X-ray diffraction data. The TCNQ acceptor lies on a centre of symmetry, with the donor and a solvent molecule adopting general positions. Thus, the content of the asymmetric unit is [bis-TTF(pyridine-bi-ester)][TCNQ]0.5.CH2Cl2 or (C33H33NO4S12)(C12H4N4)0.5.CH2Cl2 (see scheme). The atomic numbering scheme is shown in Fig. 1.

Each TTF unit of the donor molecule of (I) bears a tetramethylene substituent at one end and a sulfanylmethyl substituent at the other. The two TTF cores, D1 and D2 (see Fig. 1), are connected by the pyridine-bi-ester spacer. D1 is not planar and shows a boat conformation. The two C3S2 rings are folded around the S1···S2 and S3···S4 hinges. With respect to the central mean plane defined by S1/S2/S3/S4/C1/C2, the mean planes defined by S1/S2/C3/C4 and S3/S4/C5/C6 make dihedral angles of 7.30 (9) and 22.11 (5)°, respectively. D2 is closer to planarity but the two C3S2 rings of the TTF core are not in exactly the same plane because of a torsion angle of 3.96 (8)° around the central C7—C8 bond. The TCNQ molecule is almost planar [maximum deviation from its mean plane is 0.032 (3) Å for atom C39]. The mean planes and main axes of D1 and D2 are almost parallel [dihedral angle between the mean planes of D1 and D2 is 6.01 (4)°]. The mean plane of TCNQ makes dihedral angles of 12.26 (6) and 6.40 (7)° with the mean planes of D1 and D2, respectively.

In the crystal structure of (I), D2 and TCNQ are arranged in stacks along the [100] direction (Fig. 2) according to the pattern ···D2–AD2iD2–AD2i···, where A stands for TCNQ and D2 and D2i are related by the centre of inversion located at the centre of A. Fig. 3 is a projection onto the molecular plane of TCNQ and shows a partial overlap of D2 and TCNQ. This packing induces three intermolecular contacts less than the sum of the van der Waals radii (S···C = 3.50 Å; Reference?): S10···C35i = 3.349 (4) Å, S10···C37i = 3.335 (4) Å and S10···C38i = 3.483 (4) Å [symmetry code: (i) -x + 1, -y + 1, -z + 1].

The TTF moieties D1 are also stacked along the [100] direction, according to the pattern ···D1–D1i–py–D1–D1i···, with the pyridine ring of the spacer being located half-way between D1–D1i stacks. In addition, within the D1 TTF core, there is only one intermolecular S···S contact shorter than the sum of the van der Waals radii (3.7 Å; Reference?): S6···S6ii = 3.232 (2) Å [symmetry code: (ii) -x, -y, -z + 2].

Most of the DA compounds that crystallize with an alternate stacking of the D and A entities usually exhibit low electrical conductivity (Cassoux & Valade, 1996). Examples with TCNQ as the acceptor are given by Chasseau et al. (1982), Imaeda et al. (1991) and Legros et al. (2000). In addition, the lack of efficient overlap between the molecules of the stacks is another factor unfavourable to electronic delocalization. It is thus not surprising that the compound studied here exhibits a rather low conductivity of σRT = 2 × 10-6 S cm-1 [room-temperature measurement on a single crystal by a four-probe method (Coleman, 1975)]. An estimation of the charge of the TCNQ entity can be drawn from the bond lengths, according to the method developed by Flandrois & Chasseau (1977). According to this method, the TCNQ unit in (I) is in the neutral state, indicating that the expected charge transfer between the bis-TTF(pyridine-bi-ester) (3) and TCNQ has not occurred, in spite of the promising electrochemical properties of the new donor.

Related literature top

For related literature, see: Batsanov et al. (1995); Binet & Fabre (1997); Bouguessa et al. (2003); Bryce (1995); Bryce et al. (1998, 2001); Carcel et al. (2000, 2006); Cassoux & Valade (1996); Chasseau et al. (1982); Coleman (1975); Fabre (2000, 2002); Flandrois & Chasseau (1977); Griffiths et al. (2003); Heuzé et al. (2000); Imaeda et al. (1991); Iwahori et al. (2001); Iyoda (2004); Kaboub (2009); Kaboub et al. (2008); Legros et al. (1999, 2000); Lorcy et al. (2009); Ouahab et al. (2003); Spanggaard et al. (2000); Williams et al. (1992).

Experimental top

The synthesis of the singly bridged symmetric bis-TTF(pyridine-bi-ester), (3), and the characterization of its electrochemical behaviour were carried out as follows. The synthesis is outlined in the scheme. The mono-hydroxyl-TTF, (1), was obtained following a synthesis procedure previously described (Binet & Fabre, 1997; Legros et al., 1999, 2000). To incorporate the two ester functions in the link between the TTF units, a reaction involving one equivalent of (1) and half an equivalent of 2,6-pyridinecarbonyldichloride, (2) (Aldrich), in dry CH2Cl2 in the presence of triethylamine, was used (Bryce et al., 1998, 2001; Griffiths et al., 2003; Carcel et al., 2006). The bi-functionalized bis-TTF(pyridine-bi-ester), (3) (m.p. 348 K), was isolated in 35% yield after purification by column chromatography (SiO2, CH2Cl2–AcOEt 9:1) followed by recrystallization from CH2Cl2–MeOH (8:2 v/v).

The redox behavior of (3) was determined by cyclic voltammetry (CV) (Spanggaard et al., 2000) and by square-wave voltammetry (SQW) (Carcel et al., 2000; Bouguessa et al., 2003) in a CH2Cl2–NBu4PF6 (Ratio?) solution on a Pt working electrode/SCE (scan rate 0.1 V s-1). These measurements showed reversible redox waves by CV and two sharp bi-electronic oxidation waves by SQW, indicating two independent TTF units in (3). The oxidation values found at Eox1 = 600 mV and Eox2 = 1018 mV for (3) are similar to those of BEDT-TTF (Eox1 = 618 mV and Eox2= 1004 mV), a TTF-derived π-donor known to lead to many conducting and superconducting materials (Williams et al., 1992).

The title donor–acceptor complex, (I), of bis-TTF, (3), with TCNQ was prepared by mixing boiling solutions of two equivalents each of TCNQ and (3) in equimolar CH2Cl2–CH3CN mixtures. After one week of slow evaporation at room temperature, single crystals of complex (I) were isolated as black platelets [Block in CIF tables - please clarify], which were used for conductivity measurements and for structural study by single-crystal X-ray diffraction.

Refinement top

H atoms were positioned geometrically, with C—H = 0.97 (CH2), 0.96 (CH3) or 0.93 Å (aromatic), and refined in riding mode, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), CAMERON (Watkin et al., 1993) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. For clarity, the complete TCNQ molecule has been drawn and H atoms omitted. The symbols D1 and D2 denote the two TTF cores of the bis-TTF donor, as used in the text. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
[Figure 2] Fig. 2. A perspective view of the stacking of [bis-TTF(pyridine-bi-ester)]2[TCNQ] in the unit cell of (I). H atoms and solvent molecules have been omitted for clarity.
[Figure 3] Fig. 3. A projection of the repeat unit of a D2–AD2' stack onto the molecular plane of TCNQ. Bonds in TCNQ are drawn in black. Short S···C contacts (see text) are drawn as dashed lines. Only non-C atoms and atoms involved in the short S···C contacts are labelled. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
bis{2-[(6,7-tetramethylene-3-methylsulfanyltetrathiafulvalen-2- yl)sulfanyl]ethyl} pyridine-2,6-dicarboxylate–tetracyanoquinodimethane– dichloromethane (2/1/2) top
Crystal data top
C33H33NO4S12·0.5C12H4N4·CH2Cl2Z = 2
Mr = 1079.35F(000) = 1112
Triclinic, P1Dx = 1.544 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 11.3220 (15) ÅCell parameters from 7543 reflections
b = 12.9538 (16) Åθ = 2.8–24.9°
c = 17.659 (2) ŵ = 0.73 mm1
α = 71.165 (12)°T = 180 K
β = 84.364 (11)°Block, black
γ = 71.257 (12)°0.41 × 0.23 × 0.2 mm
V = 2321.2 (5) Å3
Data collection top
Oxford Xcalibur
diffractometer with a CCD detector
8164 independent reflections
Radiation source: fine-focus sealed tube5879 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ϕ/ω scansθmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan
(Blessing, 1995)
h = 1113
Tmin = 0.737, Tmax = 0.907k = 1415
15734 measured reflectionsl = 1920
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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0894P)2]
where P = (Fo2 + 2Fc2)/3
8164 reflections(Δ/σ)max = 0.003
550 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = 0.91 e Å3
Crystal data top
C33H33NO4S12·0.5C12H4N4·CH2Cl2γ = 71.257 (12)°
Mr = 1079.35V = 2321.2 (5) Å3
Triclinic, P1Z = 2
a = 11.3220 (15) ÅMo Kα radiation
b = 12.9538 (16) ŵ = 0.73 mm1
c = 17.659 (2) ÅT = 180 K
α = 71.165 (12)°0.41 × 0.23 × 0.2 mm
β = 84.364 (11)°
Data collection top
Oxford Xcalibur
diffractometer with a CCD detector
8164 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
5879 reflections with I > 2σ(I)
Tmin = 0.737, Tmax = 0.907Rint = 0.049
15734 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.151H-atom parameters constrained
S = 1.01Δρmax = 0.61 e Å3
8164 reflectionsΔρmin = 0.91 e Å3
550 parameters
Special details top

Experimental. Excalibur (Oxford Diffraction) four-circle Kappa geometry diffractometer equipped with an area CCD detector. Crystal-detector distance (mm): 70.0. Cooling Device: Oxford Instruments Cryojet.

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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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
xyzUiso*/Ueq
S10.16082 (9)0.14929 (8)0.56621 (5)0.0268 (2)
S20.10413 (9)0.08919 (7)0.56708 (5)0.0261 (2)
S30.09298 (9)0.22539 (8)0.75621 (5)0.0273 (2)
S40.04749 (9)0.01074 (8)0.75706 (5)0.0288 (2)
S50.11873 (9)0.32408 (8)0.93506 (5)0.0312 (2)
S60.07918 (12)0.05958 (9)0.93566 (6)0.0423 (3)
S70.83162 (9)0.38840 (8)0.50098 (5)0.0267 (2)
S80.82141 (9)0.62330 (8)0.49067 (5)0.0291 (2)
S90.78806 (10)0.33456 (8)0.69687 (5)0.0316 (2)
S100.76258 (9)0.57641 (8)0.67632 (5)0.0279 (2)
S110.77855 (11)0.27481 (9)0.87744 (6)0.0373 (3)
S120.71881 (10)0.55460 (9)0.84911 (6)0.0359 (3)
O10.3812 (2)0.2955 (2)0.86999 (14)0.0309 (6)
O20.4748 (4)0.2440 (3)0.95002 (18)0.0679 (11)
O30.5242 (3)0.1297 (2)0.85010 (17)0.0431 (7)
O40.4914 (3)0.2317 (3)0.72141 (19)0.0563 (9)
N10.4569 (3)0.0398 (3)0.82803 (18)0.0291 (7)
C10.1170 (3)0.0535 (3)0.6222 (2)0.0214 (7)
C20.0915 (3)0.0858 (3)0.7010 (2)0.0225 (8)
C30.1918 (3)0.0491 (3)0.4782 (2)0.0254 (8)
C40.1673 (3)0.0576 (3)0.4790 (2)0.0234 (8)
C50.1047 (3)0.2066 (3)0.8493 (2)0.0241 (8)
C60.0861 (3)0.0982 (3)0.8495 (2)0.0254 (8)
C70.8109 (3)0.4894 (3)0.5517 (2)0.0249 (8)
C80.7908 (3)0.4684 (3)0.6309 (2)0.0247 (8)
C90.8460 (3)0.4822 (3)0.4059 (2)0.0233 (8)
C100.8433 (3)0.5876 (3)0.4014 (2)0.0232 (8)
C110.7641 (3)0.3775 (3)0.7837 (2)0.0255 (8)
C120.7500 (3)0.4884 (3)0.7737 (2)0.0250 (8)
C130.2423 (4)0.0883 (3)0.4070 (2)0.0295 (8)
H13A0.19370.13280.39800.035*
H13B0.32780.13750.41770.035*
C140.2380 (4)0.0123 (3)0.3326 (2)0.0324 (9)
H14A0.15410.04480.31050.039*
H14B0.29360.01440.29280.039*
C150.2759 (4)0.1048 (4)0.3502 (2)0.0384 (10)
H15A0.36050.07280.37120.046*
H15B0.27470.16630.30090.046*
C160.1891 (4)0.1528 (3)0.4101 (2)0.0306 (9)
H16A0.22560.19810.42940.037*
H16B0.11020.20250.38430.037*
C170.8595 (4)0.4408 (3)0.3341 (2)0.0275 (8)
H17A0.80330.39620.33890.033*
H17B0.94410.39170.33180.033*
C180.8298 (4)0.5420 (3)0.2579 (2)0.0336 (9)
H18A0.74060.58040.25430.040*
H18B0.85450.51460.21190.040*
C190.8979 (4)0.6268 (3)0.2567 (2)0.0316 (9)
H19A0.88210.68790.20610.038*
H19B0.98700.58800.26140.038*
C200.8551 (4)0.6782 (3)0.3252 (2)0.0295 (8)
H20A0.91480.71350.33280.035*
H20B0.77510.73720.31150.035*
C210.2634 (3)0.4253 (3)0.9178 (2)0.0284 (8)
H21A0.26630.50160.95210.034*
H21B0.26470.42520.86270.034*
C220.3767 (4)0.3998 (3)0.9332 (2)0.0342 (9)
H22A0.37150.38830.98520.041*
H22B0.45100.46280.93210.041*
C230.4310 (4)0.2260 (3)0.8863 (2)0.0329 (9)
C240.4255 (3)0.1231 (3)0.8147 (2)0.0249 (8)
C250.3914 (3)0.1191 (3)0.7402 (2)0.0272 (8)
H250.36980.17930.73390.033*
C260.3902 (3)0.0246 (3)0.6760 (2)0.0285 (8)
H260.36890.02000.62520.034*
C270.4212 (3)0.0638 (3)0.6883 (2)0.0285 (8)
H270.42010.12950.64620.034*
C280.4539 (3)0.0523 (3)0.7647 (2)0.0267 (8)
C290.4913 (4)0.1483 (3)0.7756 (2)0.0325 (9)
C300.5714 (4)0.2155 (4)0.8631 (3)0.0424 (11)
H30A0.54290.22710.91420.051*
H30B0.54070.28810.82130.051*
C310.7114 (4)0.1736 (3)0.8619 (2)0.0358 (10)
H31A0.73890.16150.81080.043*
H31B0.74110.10070.90340.043*
C320.1353 (5)0.0616 (4)0.9031 (3)0.0497 (12)
H32A0.13520.08970.94720.060*
H32B0.08230.12080.86120.060*
H32C0.21880.03960.88340.060*
C330.8715 (5)0.5587 (5)0.8658 (3)0.0550 (13)
H33A0.86700.59360.90680.066*
H33B0.90090.60260.81720.066*
H33C0.92790.48200.88230.066*
N20.5575 (3)0.4372 (3)0.2530 (2)0.0437 (9)
N30.4924 (4)0.1594 (3)0.4655 (2)0.0452 (9)
C350.5174 (3)0.3611 (3)0.4042 (2)0.0272 (8)
C360.5086 (3)0.4288 (3)0.4516 (2)0.0250 (8)
C370.5397 (4)0.4010 (3)0.3195 (3)0.0315 (9)
C380.5047 (3)0.2483 (3)0.4366 (2)0.0308 (9)
C390.5183 (3)0.5438 (3)0.4175 (2)0.0292 (8)
H390.53000.57210.36270.035*
C400.4893 (3)0.3901 (3)0.5361 (2)0.0269 (8)
H400.48180.31710.55960.032*
Cl10.78455 (16)0.86497 (14)0.89202 (11)0.0887 (5)
Cl20.74472 (18)0.73013 (14)1.05223 (10)0.0938 (6)
C410.6801 (5)0.8558 (5)0.9721 (3)0.0687 (16)
H41A0.60210.85410.95490.082*
H41B0.66270.92270.98990.082*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0383 (6)0.0198 (5)0.0217 (5)0.0083 (4)0.0014 (4)0.0065 (4)
S20.0349 (5)0.0182 (4)0.0226 (5)0.0046 (4)0.0014 (4)0.0060 (4)
S30.0403 (6)0.0211 (5)0.0218 (5)0.0103 (4)0.0020 (4)0.0070 (4)
S40.0401 (6)0.0206 (5)0.0241 (5)0.0055 (4)0.0006 (4)0.0088 (4)
S50.0390 (6)0.0293 (5)0.0225 (5)0.0127 (4)0.0054 (4)0.0036 (4)
S60.0764 (8)0.0357 (6)0.0243 (5)0.0254 (6)0.0067 (5)0.0155 (4)
S70.0355 (5)0.0190 (5)0.0249 (5)0.0101 (4)0.0013 (4)0.0046 (4)
S80.0425 (6)0.0222 (5)0.0253 (5)0.0138 (4)0.0060 (4)0.0086 (4)
S90.0511 (6)0.0237 (5)0.0243 (5)0.0189 (5)0.0014 (4)0.0054 (4)
S100.0388 (6)0.0219 (5)0.0237 (5)0.0131 (4)0.0014 (4)0.0047 (4)
S110.0586 (7)0.0342 (6)0.0248 (5)0.0291 (5)0.0072 (5)0.0002 (4)
S120.0465 (6)0.0369 (6)0.0317 (6)0.0195 (5)0.0119 (4)0.0172 (5)
O10.0395 (16)0.0287 (14)0.0265 (14)0.0182 (12)0.0069 (11)0.0016 (11)
O20.114 (3)0.081 (3)0.0290 (18)0.068 (2)0.0177 (18)0.0002 (17)
O30.064 (2)0.0411 (17)0.0395 (17)0.0325 (16)0.0055 (14)0.0183 (14)
O40.094 (3)0.0341 (17)0.048 (2)0.0361 (18)0.0093 (17)0.0026 (15)
N10.0277 (17)0.0334 (18)0.0296 (17)0.0144 (15)0.0030 (13)0.0103 (14)
C10.0210 (18)0.0195 (18)0.0230 (19)0.0063 (15)0.0026 (14)0.0048 (14)
C20.0253 (19)0.0175 (18)0.0230 (19)0.0047 (15)0.0035 (14)0.0049 (14)
C30.028 (2)0.026 (2)0.0191 (18)0.0066 (16)0.0008 (15)0.0040 (15)
C40.0243 (19)0.0237 (19)0.0198 (18)0.0070 (15)0.0002 (14)0.0036 (15)
C50.029 (2)0.0243 (19)0.0196 (18)0.0093 (16)0.0016 (15)0.0067 (15)
C60.028 (2)0.027 (2)0.0230 (19)0.0109 (16)0.0031 (15)0.0098 (16)
C70.0254 (19)0.0219 (19)0.029 (2)0.0097 (16)0.0023 (15)0.0076 (15)
C80.0235 (19)0.0235 (19)0.027 (2)0.0095 (16)0.0004 (15)0.0054 (15)
C90.0216 (18)0.0249 (19)0.0230 (19)0.0080 (15)0.0028 (14)0.0067 (15)
C100.0251 (19)0.0201 (18)0.0236 (19)0.0053 (15)0.0050 (14)0.0086 (15)
C110.029 (2)0.027 (2)0.0230 (19)0.0156 (16)0.0007 (15)0.0030 (15)
C120.028 (2)0.028 (2)0.0215 (19)0.0152 (16)0.0016 (15)0.0047 (15)
C130.030 (2)0.026 (2)0.030 (2)0.0039 (17)0.0027 (16)0.0103 (16)
C140.034 (2)0.035 (2)0.028 (2)0.0099 (18)0.0082 (16)0.0115 (17)
C150.038 (2)0.042 (2)0.034 (2)0.018 (2)0.0100 (18)0.0069 (19)
C160.036 (2)0.023 (2)0.031 (2)0.0120 (17)0.0016 (17)0.0025 (16)
C170.035 (2)0.0223 (19)0.029 (2)0.0097 (16)0.0018 (16)0.0117 (16)
C180.042 (2)0.037 (2)0.025 (2)0.0178 (19)0.0028 (17)0.0095 (17)
C190.042 (2)0.027 (2)0.026 (2)0.0149 (18)0.0045 (17)0.0055 (17)
C200.040 (2)0.0210 (19)0.028 (2)0.0111 (17)0.0062 (17)0.0081 (16)
C210.037 (2)0.0164 (18)0.028 (2)0.0079 (16)0.0006 (16)0.0014 (15)
C220.044 (2)0.024 (2)0.028 (2)0.0105 (18)0.0069 (17)0.0034 (16)
C230.035 (2)0.037 (2)0.032 (2)0.0175 (19)0.0001 (17)0.0108 (18)
C240.0231 (19)0.0257 (19)0.030 (2)0.0114 (16)0.0040 (15)0.0117 (16)
C250.0244 (19)0.0248 (19)0.034 (2)0.0083 (16)0.0015 (16)0.0105 (17)
C260.0219 (19)0.033 (2)0.028 (2)0.0041 (16)0.0037 (15)0.0093 (17)
C270.024 (2)0.0227 (19)0.034 (2)0.0051 (16)0.0036 (16)0.0060 (16)
C280.0212 (19)0.026 (2)0.032 (2)0.0077 (16)0.0032 (15)0.0096 (17)
C290.031 (2)0.033 (2)0.039 (2)0.0150 (18)0.0056 (17)0.0153 (19)
C300.060 (3)0.039 (2)0.045 (3)0.031 (2)0.005 (2)0.020 (2)
C310.054 (3)0.025 (2)0.030 (2)0.021 (2)0.0037 (18)0.0006 (17)
C320.064 (3)0.056 (3)0.051 (3)0.033 (3)0.013 (2)0.036 (2)
C330.064 (3)0.076 (4)0.050 (3)0.042 (3)0.007 (2)0.035 (3)
N20.047 (2)0.050 (2)0.040 (2)0.0148 (19)0.0078 (17)0.0232 (18)
N30.054 (2)0.032 (2)0.053 (2)0.0109 (18)0.0062 (18)0.0188 (18)
C350.0224 (19)0.028 (2)0.031 (2)0.0045 (16)0.0000 (15)0.0123 (17)
C360.0204 (18)0.027 (2)0.027 (2)0.0035 (15)0.0013 (14)0.0105 (16)
C370.031 (2)0.031 (2)0.038 (2)0.0077 (18)0.0025 (18)0.0211 (19)
C380.029 (2)0.031 (2)0.034 (2)0.0020 (17)0.0048 (17)0.0173 (18)
C390.032 (2)0.025 (2)0.025 (2)0.0056 (17)0.0027 (16)0.0051 (16)
C400.031 (2)0.0209 (19)0.029 (2)0.0092 (16)0.0013 (16)0.0069 (16)
Cl10.0798 (11)0.0737 (10)0.0975 (12)0.0214 (9)0.0198 (9)0.0145 (9)
Cl20.1190 (14)0.0697 (10)0.0861 (12)0.0418 (10)0.0307 (10)0.0063 (9)
C410.070 (4)0.078 (4)0.062 (4)0.040 (3)0.009 (3)0.006 (3)
Geometric parameters (Å, º) top
S1—C11.750 (3)C16—H16B0.9700
S1—C31.762 (4)C17—C181.519 (5)
S2—C11.755 (3)C17—H17A0.9700
S2—C41.761 (3)C17—H17B0.9700
S3—C21.751 (3)C18—C191.527 (5)
S3—C51.761 (3)C18—H18A0.9700
S4—C21.759 (3)C18—H18B0.9700
S4—C61.762 (4)C19—C201.529 (5)
S5—C51.744 (4)C19—H19A0.9700
S5—C211.810 (4)C19—H19B0.9700
S6—C61.737 (3)C20—H20A0.9700
S6—C321.785 (4)C20—H20B0.9700
S7—C91.755 (3)C21—C221.493 (5)
S7—C71.757 (4)C21—H21A0.9700
S8—C101.755 (3)C21—H21B0.9700
S8—C71.757 (4)C22—H22A0.9700
S9—C81.757 (4)C22—H22B0.9700
S9—C111.763 (4)C23—C241.500 (5)
S10—C121.752 (3)C24—C251.387 (5)
S10—C81.759 (4)C25—C261.371 (5)
S11—C111.740 (4)C25—H250.9300
S11—C311.812 (4)C26—C271.384 (5)
S12—C121.756 (4)C26—H260.9300
S12—C331.802 (5)C27—C281.383 (5)
O1—C231.318 (4)C27—H270.9300
O1—C221.460 (4)C28—C291.508 (5)
O2—C231.197 (4)C30—C311.502 (6)
O3—C291.327 (5)C30—H30A0.9700
O3—C301.465 (4)C30—H30B0.9700
O4—C291.190 (5)C31—H31A0.9700
N1—C241.332 (4)C31—H31B0.9700
N1—C281.339 (5)C32—H32A0.9600
C1—C21.348 (5)C32—H32B0.9600
C3—C41.323 (5)C32—H32C0.9600
C3—C131.501 (5)C33—H33A0.9600
C4—C161.493 (5)C33—H33B0.9600
C5—C61.352 (5)C33—H33C0.9600
C7—C81.345 (5)N2—C371.140 (5)
C9—C101.332 (5)N3—C381.147 (5)
C9—C171.506 (5)C35—C361.371 (5)
C10—C201.501 (5)C35—C381.435 (5)
C11—C121.347 (5)C35—C371.441 (5)
C13—C141.515 (5)C36—C401.432 (5)
C13—H13A0.9700C36—C391.452 (5)
C13—H13B0.9700C39—C40i1.343 (5)
C14—C151.521 (5)C39—H390.9300
C14—H14A0.9700C40—C39i1.343 (5)
C14—H14B0.9700C40—H400.9300
C15—C161.517 (5)Cl1—C411.752 (6)
C15—H15A0.9700Cl2—C411.771 (5)
C15—H15B0.9700C41—H41A0.9700
C16—H16A0.9700C41—H41B0.9700
C1—S1—C394.91 (16)C18—C19—H19A109.4
C1—S2—C494.67 (16)C20—C19—H19A109.4
C2—S3—C594.12 (16)C18—C19—H19B109.4
C2—S4—C693.79 (16)C20—C19—H19B109.4
C5—S5—C21102.33 (17)H19A—C19—H19B108.0
C6—S6—C32103.10 (19)C10—C20—C19110.9 (3)
C9—S7—C795.22 (16)C10—C20—H20A109.5
C10—S8—C795.22 (16)C19—C20—H20A109.5
C8—S9—C1195.44 (17)C10—C20—H20B109.5
C12—S10—C895.59 (16)C19—C20—H20B109.5
C11—S11—C31103.01 (17)H20A—C20—H20B108.1
C12—S12—C33101.25 (19)C22—C21—S5113.5 (3)
C23—O1—C22118.7 (3)C22—C21—H21A108.9
C29—O3—C30116.1 (3)S5—C21—H21A108.9
C24—N1—C28116.5 (3)C22—C21—H21B108.9
C2—C1—S1122.8 (3)S5—C21—H21B108.9
C2—C1—S2122.4 (3)H21A—C21—H21B107.7
S1—C1—S2114.71 (19)O1—C22—C21106.8 (3)
C1—C2—S3123.6 (3)O1—C22—H22A110.4
C1—C2—S4122.7 (3)C21—C22—H22A110.4
S3—C2—S4113.69 (19)O1—C22—H22B110.4
C4—C3—C13123.9 (3)C21—C22—H22B110.4
C4—C3—S1117.3 (3)H22A—C22—H22B108.6
C13—C3—S1118.8 (3)O2—C23—O1123.7 (4)
C3—C4—C16124.4 (3)O2—C23—C24125.3 (4)
C3—C4—S2117.7 (3)O1—C23—C24111.0 (3)
C16—C4—S2117.9 (3)N1—C24—C25123.8 (3)
C6—C5—S5124.5 (3)N1—C24—C23115.6 (3)
C6—C5—S3116.8 (3)C25—C24—C23120.6 (3)
S5—C5—S3118.1 (2)C26—C25—C24118.8 (3)
C5—C6—S6124.0 (3)C26—C25—H25120.6
C5—C6—S4116.7 (3)C24—C25—H25120.6
S6—C6—S4118.8 (2)C25—C26—C27118.6 (3)
C8—C7—S8121.2 (3)C25—C26—H26120.7
C8—C7—S7124.3 (3)C27—C26—H26120.7
S8—C7—S7114.4 (2)C28—C27—C26118.5 (3)
C7—C8—S9124.0 (3)C28—C27—H27120.7
C7—C8—S10121.6 (3)C26—C27—H27120.7
S9—C8—S10114.4 (2)N1—C28—C27123.7 (3)
C10—C9—C17123.5 (3)N1—C28—C29119.1 (3)
C10—C9—S7117.5 (3)C27—C28—C29117.2 (3)
C17—C9—S7119.0 (3)O4—C29—O3124.4 (4)
C9—C10—C20124.4 (3)O4—C29—C28122.0 (4)
C9—C10—S8117.6 (3)O3—C29—C28113.6 (3)
C20—C10—S8118.0 (3)O3—C30—C31108.6 (3)
C12—C11—S11122.8 (3)O3—C30—H30A110.0
C12—C11—S9117.0 (3)C31—C30—H30A110.0
S11—C11—S9119.7 (2)O3—C30—H30B110.0
C11—C12—S10117.5 (3)C31—C30—H30B110.0
C11—C12—S12126.3 (3)H30A—C30—H30B108.4
S10—C12—S12116.2 (2)C30—C31—S11111.7 (3)
C3—C13—C14111.4 (3)C30—C31—H31A109.3
C3—C13—H13A109.4S11—C31—H31A109.3
C14—C13—H13A109.4C30—C31—H31B109.3
C3—C13—H13B109.4S11—C31—H31B109.3
C14—C13—H13B109.4H31A—C31—H31B107.9
H13A—C13—H13B108.0S6—C32—H32A109.5
C13—C14—C15111.9 (3)S6—C32—H32B109.5
C13—C14—H14A109.2H32A—C32—H32B109.5
C15—C14—H14A109.2S6—C32—H32C109.5
C13—C14—H14B109.2H32A—C32—H32C109.5
C15—C14—H14B109.2H32B—C32—H32C109.5
H14A—C14—H14B107.9S12—C33—H33A109.5
C16—C15—C14111.5 (3)S12—C33—H33B109.5
C16—C15—H15A109.3H33A—C33—H33B109.5
C14—C15—H15A109.3S12—C33—H33C109.5
C16—C15—H15B109.3H33A—C33—H33C109.5
C14—C15—H15B109.3H33B—C33—H33C109.5
H15A—C15—H15B108.0C36—C35—C38121.6 (3)
C4—C16—C15110.2 (3)C36—C35—C37120.9 (3)
C4—C16—H16A109.6C38—C35—C37117.5 (3)
C15—C16—H16A109.6C35—C36—C40122.0 (3)
C4—C16—H16B109.6C35—C36—C39120.9 (3)
C15—C16—H16B109.6C40—C36—C39117.1 (3)
H16A—C16—H16B108.1N2—C37—C35176.8 (4)
C9—C17—C18110.2 (3)N3—C38—C35176.9 (4)
C9—C17—H17A109.6C40i—C39—C36121.0 (3)
C18—C17—H17A109.6C40i—C39—H39119.5
C9—C17—H17B109.6C36—C39—H39119.5
C18—C17—H17B109.6C39i—C40—C36121.9 (3)
H17A—C17—H17B108.1C39i—C40—H40119.0
C17—C18—C19110.9 (3)C36—C40—H40119.0
C17—C18—H18A109.5Cl1—C41—Cl2110.0 (3)
C19—C18—H18A109.5Cl1—C41—H41A109.7
C17—C18—H18B109.5Cl2—C41—H41A109.7
C19—C18—H18B109.5Cl1—C41—H41B109.7
H18A—C18—H18B108.0Cl2—C41—H41B109.7
C18—C19—C20111.1 (3)H41A—C41—H41B108.2
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC33H33NO4S12·0.5C12H4N4·CH2Cl2
Mr1079.35
Crystal system, space groupTriclinic, P1
Temperature (K)180
a, b, c (Å)11.3220 (15), 12.9538 (16), 17.659 (2)
α, β, γ (°)71.165 (12), 84.364 (11), 71.257 (12)
V3)2321.2 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.73
Crystal size (mm)0.41 × 0.23 × 0.2
Data collection
DiffractometerOxford Xcalibur
diffractometer with a CCD detector
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.737, 0.907
No. of measured, independent and
observed [I > 2σ(I)] reflections
15734, 8164, 5879
Rint0.049
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.151, 1.01
No. of reflections8164
No. of parameters550
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.61, 0.91

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), CAMERON (Watkin et al., 1993) and ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

 

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