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The title compound, C
22H
14N
2O
2S
3·2CHCl
3, was obtained unintentionally as the product of the reaction between the potassium salt of 8-hydroxy-2-methylquinoline-7-carbodithioic acid and
M[OOCCF
3]
2 (
M = Mg, Mn). Oxidation and sulfur elimination processes caused condensation of two acid molecules with the formation of an aromatic five-membered heterocycle S
3C
2 (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 7
Z,7′
Z conformation with respect to the unsaturated vinyl groups. The compound cocrystallizes with CHCl
3, 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.
Supporting information
CCDC reference: 672989
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.005 Å
- R factor = 0.054
- wR factor = 0.127
- Data-to-parameter ratio = 15.9
checkCIF/PLATON results
No syntax errors found
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
1 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
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.
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
Uiso(H)=1.2 Ueq(C) for aromatic CH and CHCl3 and 1.5 for
methyl groups. No disorder has been found.
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).
(7
Z,7'
Z)-2,2-Dimethyl-7,7'-(1,2,4-trithiolane-3,5-diylidene)bis[quinolin- 8(7
H)-one] chloroform disolvate
top
Crystal data top
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) Å3 | 0.23 × 0.11 × 0.05 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.053P)2 + 10.8805P] where P = (Fo2 + 2Fc2)/3 |
2682 reflections | (Δ/σ)max = 0.005 |
169 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
C22H14N2O2S3·2CHCl3 | V = 2730.3 (3) Å3 |
Mr = 673.27 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.7359 (13) Å | µ = 0.89 mm−1 |
b = 10.6749 (6) Å | T = 120 K |
c = 11.1128 (6) Å | 0.23 × 0.11 × 0.05 mm |
β = 104.149 (5)° | |
Data collection top
KM4CCD, Oxford Diffraction diffractometer | 2682 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | 2357 reflections with I > 2σ(I) |
Tmin = 0.867, Tmax = 0.963 | Rint = 0.055 |
9483 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.053P)2 + 10.8805P] where P = (Fo2 + 2Fc2)/3 |
2682 reflections | Δρmax = 0.59 e Å−3 |
169 parameters | Δρmin = −0.40 e Å−3 |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
S1—C10i | 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—S2i | 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 | | |
| | | |
C10i—S1—C10 | 102.3 (2) | C8—C7—H7 | 120.0 |
C10—S2—S2i | 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) top
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 |
Experimental details
Crystal data |
Chemical formula | C22H14N2O2S3·2CHCl3 |
Mr | 673.27 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 23.7359 (13), 10.6749 (6), 11.1128 (6) |
β (°) | 104.149 (5) |
V (Å3) | 2730.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.89 |
Crystal size (mm) | 0.23 × 0.11 × 0.05 |
|
Data collection |
Diffractometer | KM4CCD, Oxford Diffraction diffractometer |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.867, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9483, 2682, 2357 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.127, 1.12 |
No. of reflections | 2682 |
No. of parameters | 169 |
H-atom treatment | H-atom parameters constrained |
| w = 1/[σ2(Fo2) + (0.053P)2 + 10.8805P] where P = (Fo2 + 2Fc2)/3 |
Δρmax, Δρmin (e Å−3) | 0.59, −0.40 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···S1 | 0.93 | 2.64 | 3.032 (3) | 106.0 |
C12—H12···O1 | 0.98 | 2.37 | 3.136 (4) | 134.7 |
C12—H12···N1 | 0.98 | 2.40 | 3.294 (4) | 152.1 |
Main π–π interactions in (I) (Å,°)
DA is dihedral angle between the planes, DCC is the length of the CC vector
(centroid to centroid),
τ is the angle(s) subtended by the plane normal(s) to CC. Cg1 is the centroid
of ring S1-C10-S2-S2i-C10i, Cg2 of ring C1–C5/C9. topGroup 1 | Group 2 | DA | DCC | τ |
Cg1 | Cg2i | 3.62 | 3.650 (2) | 16.31 |
Cg1 | Cg2ii | 3.62 | 3.650 (2) | 16.31 |
Symmetry codes: (i) -x, 1-y, 1-z; (ii) x, 1-y, 1/2+z |
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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.