(7Z,7′Z)-2,2-Dimethyl-7,7′-(1,2,4-tri­thiol­ane-3,5-diyl­idene)bis­[quinolin-8(7H)-one] chloro­form disolvate

The title compound, C₂₂H₁₄N₂O₂S₃·2CHCl₃, was obtained unintentionally as the product of the reaction between the potassium salt of 8-hydr­oxy-2-methyl­quinoline-7-carbodithioic acid and M[OOCCF₃]₂ (M = Mg, Mn). Oxidation and sulfur elimination processes caused condensation of two acid mol­ecules with the formation of an aromatic five-membered heterocycle S₃C₂ (trithiol­ane). The mol­ecule shows local symmetry 2 (Schoenflies C₂) with the twofold rotation axis passing through the trithiol­ane ring. The two aromatic systems are essentially planar. The mol­ecules possess the 7Z,7′Z conformation with respect to the unsaturated vinyl groups. The compound cocrystallizes with CHCl₃, which is bound by weak bifurcated C—H...O(N) hydrogen bonds. The packing of mol­ecules in the structure is stabilized by π–π stacking inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.054
• wR factor = 0.127
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

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Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
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   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

The title compound, [C₂₂H₁₄N₂O₂S₃, 2(CHCl₃)], was obtained unintentionally as the product of the reactions between potassium salt of 8-hydroxy-2-methylquinoline-7-carbodithioic acid and M[OOCCF₃]₂ (M = Mg, Mn). Oxidation and sulfur elimination processes caused condensation of two acid molecules with the formation of aromatic five-membered heterocycle S₃C₂ (trithiolane). The mechanism of formation of the title compound is not fully recognized. Its structural novelty suggests considerable potential as functionalized ligand interesting in organometallic chemistry and it seems probable to be important as bioactive molecules. Naturally occurring trithiolanes (e.g. in garlic) significantly inhibited the formation of intracellular reactive oxygen species (Lee et al., 2005). The heterocycle is stabilized by extended delocalization of electrons in conjugated aromatic systems. Molecules possess the (7Z,7'Z) conformation with respect to the unsaturated vinyls (C2—C10). The same product was obtained using Mg and Mn salt. In the related derivative, 3,5-bis(2-tetralonyliden)-1,2,4-trithiole, also Z,Z' conformation was determined (Gonzalez-Castro et al., 2000). Valence angles on sulfur in (I) are close to the values reported there (99.74 ° for S—S—C and 103.02 ° for C—S—C). It seems that relatively acute angles on sulfur atoms (due to assumed lack of hybridization of sulfur orbitals) lead to the low tensed 5-membered ring, which explains the ease of formation of the central heterocycle.

C₂₂H₁₄N₂O₂S₃ molecule shows local symmetry 2 (Schoenflies C₂) with the twofold axis passing through the trithiolane ring. It is essentially planar, with root mean square deviation of atoms from the S1,S2,C1—C11,N1,O1 plane being only 0.0286 Å. Maximum deviation from the plane is shown by S2 atom and it is equal to -0.0594(0.0015) Å.

Packing of molecules in the structure is stabilized by π-π stacking interactions (see Table 2.). Compound cocrystallized with CHCl₃ which is bound by weak C—H···O(N) bifurcated hydrogen bonds.

Related literature

For the related structure 3,5-bis(2-tetralonyliden)-1,2,4-trithiole, see: Gonzalez-Castro et al. (2000). For related literature, see: Lee et al. (2005).

S2. Experimental

To the suspension of 8-hydroxy-2-methylquinoline-7-carbodithioic acid (2.350 g, 10.0 mmol) in H₂O (50 ml), K₂CO₃ (1.380 g, 10.0 mmol) was added and stirred up to the disappearance of the solid material. Subsequently, M[OOCCF₃] (M = Mg, Mn) (10.0 mmol) was slowly added. The reaction was carried out for 16 h at room temperature. Next the liquid reaction mixture was filtered off and the brown crude product was dryied over P₂O₅. Final purification by crystallization from CHCl₃ gave material suitable for the X-ray structural analysis.

S3. Refinement

All H atoms were treated as riding on their parent C atoms with methyl C–H = 0.96 Å, chloroform C–H = 0.98 Å, aromatic C–H = 0.93 Å and U_iso(H)=1.2 U_eq(C) for aromatic CH and CHCl₃ and 1.5 for methyl groups. No disorder has been found.

Computing details

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: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

Fig. 1. View of (I) including the solvent linked through C—H···O and C—H···N hydrogen bonds with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.

(7Z,7'Z)-2,2-Dimethyl-7,7'-(1,2,4-trithiolane-3,5-diylidene)bis[quinolin- 8(7H)-one] chloroform disolvate

Crystal data

C22H14N2O2S3·2CHCl3	F(000) = 1360
Mr = 673.27	Dx = 1.638 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6056 reflections
a = 23.7359 (13) Å	θ = 30.6–1.5°
b = 10.6749 (6) Å	µ = 0.89 mm^−1
c = 11.1128 (6) Å	T = 120 K
β = 104.149 (5)°	Prism, red
V = 2730.3 (3) Å^3	0.23 × 0.11 × 0.05 mm
Z = 4

Data collection

KM4CCD, Oxford Diffraction diffractometer	2357 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
0.75° ω scans	θmax = 26°, θmin = 2.1°
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006)	h = −29→29
Tmin = 0.867, Tmax = 0.963	k = −13→12
9483 measured reflections	l = −13→12
2682 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 10.8805P] where P = (Fo^2 + 2Fc^2)/3
2682 reflections	(Δ/σ)max = 0.005
169 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.5000	−0.02872 (10)	0.2500	0.0174 (3)
S2	0.46838 (4)	0.23246 (7)	0.30370 (8)	0.0183 (2)
N1	0.32997 (13)	0.1448 (3)	0.5839 (3)	0.0188 (6)
O1	0.39897 (11)	0.2266 (2)	0.4329 (2)	0.0222 (5)
C1	0.39538 (15)	0.1118 (3)	0.4513 (3)	0.0172 (7)
C2	0.42747 (15)	0.0229 (3)	0.3960 (3)	0.0161 (7)
C3	0.42230 (15)	−0.1102 (3)	0.4154 (3)	0.0192 (7)
H3	0.4425	−0.1664	0.3776	0.023*
C4	0.38870 (15)	−0.1536 (3)	0.4873 (3)	0.0190 (7)
H4	0.3863	−0.2395	0.4988	0.023*
C5	0.35623 (14)	−0.0699 (3)	0.5473 (3)	0.0164 (7)
C6	0.32260 (15)	−0.1123 (3)	0.6273 (3)	0.0209 (7)
H6	0.3204	−0.1973	0.6437	0.025*
C7	0.29310 (15)	−0.0268 (3)	0.6809 (3)	0.0203 (7)
H7	0.2703	−0.0539	0.7329	0.024*
C8	0.29742 (15)	0.1021 (3)	0.6570 (3)	0.0201 (7)
C9	0.35899 (14)	0.0610 (3)	0.5305 (3)	0.0162 (7)
C10	0.46249 (14)	0.0732 (3)	0.3239 (3)	0.0160 (6)
C11	0.26353 (17)	0.1970 (3)	0.7105 (4)	0.0282 (8)
H11A	0.2813	0.2779	0.7113	0.042*
H11B	0.2633	0.1734	0.7937	0.042*
H11C	0.2243	0.2004	0.6606	0.042*
C12	0.38385 (16)	0.4303 (3)	0.6259 (3)	0.0219 (7)
H12	0.3788	0.3427	0.5991	0.026*
Cl1	0.32240 (4)	0.51737 (9)	0.54728 (9)	0.0323 (3)
Cl2	0.39044 (5)	0.43802 (10)	0.78724 (8)	0.0365 (3)
Cl3	0.44742 (4)	0.49030 (9)	0.59141 (8)	0.0295 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0206 (6)	0.0128 (5)	0.0219 (6)	0.000	0.0114 (5)	0.000
S2	0.0218 (4)	0.0134 (4)	0.0231 (4)	0.0000 (3)	0.0118 (3)	0.0000 (3)
N1	0.0201 (15)	0.0185 (14)	0.0187 (14)	−0.0012 (12)	0.0069 (12)	−0.0015 (11)
O1	0.0299 (14)	0.0155 (11)	0.0253 (13)	−0.0025 (10)	0.0144 (11)	−0.0007 (10)
C1	0.0178 (17)	0.0157 (15)	0.0173 (16)	0.0004 (13)	0.0028 (13)	0.0009 (12)
C2	0.0141 (16)	0.0183 (15)	0.0164 (15)	−0.0018 (13)	0.0048 (13)	−0.0015 (12)
C3	0.0204 (18)	0.0174 (16)	0.0217 (17)	−0.0004 (13)	0.0089 (14)	−0.0005 (13)
C4	0.0183 (17)	0.0142 (15)	0.0254 (17)	−0.0005 (13)	0.0074 (14)	0.0003 (13)
C5	0.0148 (16)	0.0175 (15)	0.0157 (15)	−0.0020 (13)	0.0015 (13)	0.0009 (12)
C6	0.0211 (18)	0.0183 (16)	0.0234 (17)	−0.0016 (13)	0.0060 (14)	0.0026 (14)
C7	0.0160 (17)	0.0256 (17)	0.0208 (17)	−0.0018 (14)	0.0076 (14)	0.0030 (14)
C8	0.0176 (17)	0.0227 (17)	0.0204 (16)	0.0004 (14)	0.0056 (14)	−0.0026 (14)
C9	0.0145 (16)	0.0177 (15)	0.0162 (15)	−0.0003 (13)	0.0032 (13)	−0.0010 (13)
C10	0.0155 (16)	0.0149 (15)	0.0178 (15)	−0.0008 (13)	0.0046 (13)	−0.0009 (12)
C11	0.031 (2)	0.0263 (18)	0.034 (2)	0.0012 (16)	0.0195 (17)	−0.0018 (16)
C12	0.029 (2)	0.0193 (17)	0.0181 (16)	−0.0035 (14)	0.0078 (14)	−0.0009 (13)
Cl1	0.0272 (5)	0.0319 (5)	0.0356 (5)	0.0022 (4)	0.0036 (4)	0.0045 (4)
Cl2	0.0503 (7)	0.0422 (6)	0.0191 (4)	−0.0079 (5)	0.0125 (4)	0.0023 (4)
Cl3	0.0260 (5)	0.0393 (5)	0.0240 (5)	−0.0087 (4)	0.0075 (4)	−0.0044 (4)

Geometric parameters (Å, º)

S1—C10^i	1.735 (3)	C5—C6	1.406 (5)
S1—C10	1.735 (3)	C5—C9	1.414 (5)
S2—C10	1.725 (3)	C6—C7	1.371 (5)
S2—S2^i	2.1338 (16)	C6—H6	0.9300
N1—C8	1.331 (4)	C7—C8	1.410 (5)
N1—C9	1.351 (4)	C7—H7	0.9300
O1—C1	1.248 (4)	C8—C11	1.503 (5)
C1—C2	1.445 (5)	C11—H11A	0.9600
C1—C9	1.479 (5)	C11—H11B	0.9600
C2—C10	1.395 (5)	C11—H11C	0.9600
C2—C3	1.447 (4)	C12—Cl2	1.763 (3)
C3—C4	1.342 (5)	C12—Cl3	1.765 (4)
C3—H3	0.9300	C12—Cl1	1.769 (4)
C4—C5	1.445 (5)	C12—H12	0.9800
C4—H4	0.9300
C10^i—S1—C10	102.3 (2)	C8—C7—H7	120.0
C10—S2—S2^i	99.41 (11)	N1—C8—C7	121.9 (3)
C8—N1—C9	118.4 (3)	N1—C8—C11	117.2 (3)
O1—C1—C2	120.8 (3)	C7—C8—C11	120.8 (3)
O1—C1—C9	122.0 (3)	N1—C9—C5	123.5 (3)
C2—C1—C9	117.2 (3)	N1—C9—C1	117.0 (3)
C10—C2—C1	116.2 (3)	C5—C9—C1	119.6 (3)
C10—C2—C3	123.2 (3)	C2—C10—S2	122.2 (2)
C1—C2—C3	120.6 (3)	C2—C10—S1	118.5 (2)
C4—C3—C2	120.8 (3)	S2—C10—S1	119.27 (19)
C4—C3—H3	119.6	C8—C11—H11A	109.5
C2—C3—H3	119.6	C8—C11—H11B	109.5
C3—C4—C5	121.6 (3)	H11A—C11—H11B	109.5
C3—C4—H4	119.2	C8—C11—H11C	109.5
C5—C4—H4	119.2	H11A—C11—H11C	109.5
C6—C5—C9	116.9 (3)	H11B—C11—H11C	109.5
C6—C5—C4	122.8 (3)	Cl2—C12—Cl3	109.62 (19)
C9—C5—C4	120.2 (3)	Cl2—C12—Cl1	109.6 (2)
C7—C6—C5	119.3 (3)	Cl3—C12—Cl1	110.34 (19)
C7—C6—H6	120.3	Cl2—C12—H12	109.1
C5—C6—H6	120.3	Cl3—C12—H12	109.1
C6—C7—C8	119.9 (3)	Cl1—C12—H12	109.1
C6—C7—H7	120.0

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···S1	0.93	2.64	3.032 (3)	106
C12—H12···O1	0.98	2.37	3.136 (4)	135
C12—H12···N1	0.98	2.40	3.294 (4)	152