Download citation
Download citation
link to html
The title compound, C13H11NS2, contains a C[triple bond]C—H...N hydrogen bond to a pyridine-type N atom, with a C...N distance of 3.305 (4) Å and an H...N distance of 2.28 Å. This is one of the shortest C—H...N hydrogen bonds known.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016297/de1124sup1.cif
Contains datablocks a083, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016297/de1124Isup2.hkl
Contains datablock I

CCDC reference: 142789

Comment top

We are studying acetylenic derivatives of thioquinolines as a new series of compounds which can be efficiently obtained from reactions of thioquinanthrene with alkoxides (Boryczka, 1999). Apart from the synthetic chemical interest, the title compound, (I), is of relevance in the context of intermolecular interactions. The terminal alkyne group is expected to form a C C—H···X hydrogen bond, with X being one of the potential hydrogen-bond acceptors of the molecule. This could be the N atom, but also the π systems of the benzyl group, the pyridine moiety and the CC bond (Desiraju & Steiner, 1999). The divalent S atoms in the configuration C—S—C are more or less non-polar, and are not expected to accept a hydrogen bond from CC—H (see Allen et al., 1997). Which of the relevant groups will actually form a hydrogen bond in the crystal cannot be predicted.

In the crystal structure of (I) (Fig. 1), the covalent geometry is found to be normal [relevant bond lengths: S1—C3 = 1.759 (3), S1—C11 = 1.808 (3), C2—C4 = 1.775 (2), S2—C12 = 1.825 (3), C13C14 = 1.181 (4) Å; angles at the S atoms: 103.8 (1)° at S1, 99.2 (1)° at S2] and is almost the same as in 3,4-dimethylthioquinoline (Maślankiewicz et al., 1991). The methyl group at S1 is almost exactly in the quinoline plane [C2—C3—S1—C11 = 0.7 (3)°]. At S2, the S2—C12 bond invoving the propynyl group is rotated perpendicularly out of the quinoline plane [C3—C4—S2—C12 = -86.9 (2)°], and the propargyl group itself is then oriented parallel to the C4—S2 bond [C4—S2—C12—C13 = 173.5 (2)°]. A similar situation occurs in 3,4-dimethylthioquinoline (Maślankiewicz et al., 1991).

In the crystal, the molecules form layers in which neighbouring molecules are related only by translation (Fig. 2). The inversion-related molecules form a separate layer. The CC—H group forms a clear hydrogen bond with the N atom of a neighbouring molecule (x, y - 1, z - 1), with C···N = 3.305 (4) Å. The interaction is directed at the electron lone-pair of N. If the C—H bond is normalized to 1.08 Å, an H···N distance of 2.28 Å and a C—H···N angle of 157° are obtained. This is a very short distance for a C—H···N hydrogen bond (Mascal, 1998); for hydrogen bonds from the acidic C—H donors in CC—H and CHCl3 to N acceptors, the mean H···N distances are reported to be 2.40 and 2.34 Å, respectively (Steiner, 1998). Only a few CC—H···N interactions have been found shorter than in (I) (Kumar et al., 1998); a classical example is cyanoacetylene with H···N = 2.21, C···N = 3.29 Å (Shallcross & Carpenter, 1958). Reasons for the short H···N distance in (I) might be the high basicity of the pyridyl N atom and the lack of competition with other hydrogen bonds.

Experimental top

The title compound, (I), was synthesized by reaction of 4-chloro-3-methylthioquinoline [obtained following procedures described by Maślankiewicz & Boryczka (1993)] with thiourea, as shown in the scheme above. A mixture of 0.42 g (2.4 mmol) of 4-chloro-3-methylthioquinoline, 0.18 g (2.4 mmol) of thiourea and 8 ml of 99.8% ethanol was stirred at 313–318 K for 30 min and then cooled to room temperature. The reaction mixture containing the isothiuronium salt was poured into 20 ml of 5% aqueous sodium hydroxide. Propargyl bromide (0.29 g, 2.4 mmol) was added dropwise to the aqueous layer, and the mixture was stirred for 15 min. The resultant solid was filtered off and air-dried to give a crude product, which was then crystallized from benzene–hexane to give 0.4 g (82%) of (I) with m.p. 375–376 K. 1H NMR (CDCl3, 300 MHz): δ 2.07 (t, J = 2.5 Hz, 1H, CH), 2.67 (s, 3H, SCH3), 3.69 (d, J = 2.5 Hz, 2H, SCH2), 7.59–7.69 (m, 2H, H-6 and H-7), 8.05–8.08 (m, 1H, H-8), 8.54–8.58 (m, 1H, H-5), 8.79 (s, 1H, H-2). In the NMR spectrum, we applied systematic atom numbering according to the IUPAC rules. MS EI (70 eV) m/z (relative intensity): 245 (M+, 25.6), 230 (M—CH3, 100). The melting point was determined on a Buchi 510 capillary apparatus. The 1H NMR spectrum was recorded on a Bruker 300 MSL instrument at 300 MHz. The mass spectrum was obtained on an LKB GC 2091 spectrometer at 70 eV.

Refinement top

H atoms bonded to C were treated as riding using default parameters for C—H bond lengths at the temperature of measurement, with isotropic displacement parameters allowed to vary. The methyl groups were allowed to rotate. All H-atom displacement parameters refined to realistic values, in the range 0.021–0.065 Å2. By far the highest difference electron density peak is located 0.86 Å from S2. All attempts to refine disorder that could lead to this peak failed.

Structure description top

We are studying acetylenic derivatives of thioquinolines as a new series of compounds which can be efficiently obtained from reactions of thioquinanthrene with alkoxides (Boryczka, 1999). Apart from the synthetic chemical interest, the title compound, (I), is of relevance in the context of intermolecular interactions. The terminal alkyne group is expected to form a C C—H···X hydrogen bond, with X being one of the potential hydrogen-bond acceptors of the molecule. This could be the N atom, but also the π systems of the benzyl group, the pyridine moiety and the CC bond (Desiraju & Steiner, 1999). The divalent S atoms in the configuration C—S—C are more or less non-polar, and are not expected to accept a hydrogen bond from CC—H (see Allen et al., 1997). Which of the relevant groups will actually form a hydrogen bond in the crystal cannot be predicted.

In the crystal structure of (I) (Fig. 1), the covalent geometry is found to be normal [relevant bond lengths: S1—C3 = 1.759 (3), S1—C11 = 1.808 (3), C2—C4 = 1.775 (2), S2—C12 = 1.825 (3), C13C14 = 1.181 (4) Å; angles at the S atoms: 103.8 (1)° at S1, 99.2 (1)° at S2] and is almost the same as in 3,4-dimethylthioquinoline (Maślankiewicz et al., 1991). The methyl group at S1 is almost exactly in the quinoline plane [C2—C3—S1—C11 = 0.7 (3)°]. At S2, the S2—C12 bond invoving the propynyl group is rotated perpendicularly out of the quinoline plane [C3—C4—S2—C12 = -86.9 (2)°], and the propargyl group itself is then oriented parallel to the C4—S2 bond [C4—S2—C12—C13 = 173.5 (2)°]. A similar situation occurs in 3,4-dimethylthioquinoline (Maślankiewicz et al., 1991).

In the crystal, the molecules form layers in which neighbouring molecules are related only by translation (Fig. 2). The inversion-related molecules form a separate layer. The CC—H group forms a clear hydrogen bond with the N atom of a neighbouring molecule (x, y - 1, z - 1), with C···N = 3.305 (4) Å. The interaction is directed at the electron lone-pair of N. If the C—H bond is normalized to 1.08 Å, an H···N distance of 2.28 Å and a C—H···N angle of 157° are obtained. This is a very short distance for a C—H···N hydrogen bond (Mascal, 1998); for hydrogen bonds from the acidic C—H donors in CC—H and CHCl3 to N acceptors, the mean H···N distances are reported to be 2.40 and 2.34 Å, respectively (Steiner, 1998). Only a few CC—H···N interactions have been found shorter than in (I) (Kumar et al., 1998); a classical example is cyanoacetylene with H···N = 2.21, C···N = 3.29 Å (Shallcross & Carpenter, 1958). Reasons for the short H···N distance in (I) might be the high basicity of the pyridyl N atom and the lack of competition with other hydrogen bonds.

Computing details top

Data collection: EVAL14 (Duisenberg, 1998); cell refinement: EVAL14; data reduction: EVAL14; program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97, ORTEPII (Johnson, 1976), PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), showing 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Crystal packing of (I). CC—H···N hydrogen bonds are indicated as dashed lines.
3-methylthio-4-propargylthioquinoline top
Crystal data top
C13H11NS2Z = 2
Mr = 245.35F(000) = 256
Triclinic, P1Dx = 1.418 Mg m3
a = 7.448 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.514 (3) ÅCell parameters from 37 reflections
c = 9.786 (3) Åθ = 3.8–18.0°
α = 107.57 (3)°µ = 0.43 mm1
β = 100.99 (3)°T = 125 K
γ = 94.57 (3)°Block, yellow
V = 574.4 (4) Å30.25 × 0.20 × 0.10 mm
Data collection top
Nonius Kappa CCD
diffractometer
2315 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.036
Graphite monochromatorθmax = 27.5°, θmin = 2.2°
ω scansh = 97
3618 measured reflectionsk = 1110
2616 independent reflectionsl = 1210
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0387P)2 + 1.319P]
where P = (Fo2 + 2Fc2)/3
2616 reflections(Δ/σ)max < 0.001
157 parametersΔρmax = 0.93 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
C13H11NS2γ = 94.57 (3)°
Mr = 245.35V = 574.4 (4) Å3
Triclinic, P1Z = 2
a = 7.448 (3) ÅMo Kα radiation
b = 8.514 (3) ŵ = 0.43 mm1
c = 9.786 (3) ÅT = 125 K
α = 107.57 (3)°0.25 × 0.20 × 0.10 mm
β = 100.99 (3)°
Data collection top
Nonius Kappa CCD
diffractometer
2315 reflections with I > 2σ(I)
3618 measured reflectionsRint = 0.036
2616 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.93 e Å3
2616 reflectionsΔρmin = 0.46 e Å3
157 parameters
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.

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
S10.12539 (10)0.17260 (9)0.12076 (7)0.02530 (18)
S20.16271 (9)0.18335 (8)0.14597 (7)0.02319 (18)
N10.2356 (3)0.2642 (3)0.5239 (2)0.0245 (5)
C20.2034 (4)0.2807 (3)0.4005 (3)0.0240 (5)
H20.19560.38880.39130.025 (8)*
C30.1797 (3)0.1457 (3)0.2803 (3)0.0207 (5)
C40.1955 (3)0.0125 (3)0.2920 (3)0.0197 (5)
C50.2320 (3)0.0356 (3)0.4233 (3)0.0207 (5)
C60.2505 (3)0.1939 (3)0.4467 (3)0.0255 (6)
H60.24080.29160.37120.036 (9)*
C70.2814 (4)0.2055 (4)0.5738 (3)0.0315 (6)
H70.29380.31160.58680.039 (10)*
C80.2957 (4)0.0640 (4)0.6881 (3)0.0321 (7)
H80.31630.07480.77800.048 (11)*
C90.2800 (4)0.0903 (4)0.6705 (3)0.0295 (6)
H90.29020.18550.74850.038 (9)*
C100.2489 (3)0.1092 (3)0.5375 (3)0.0220 (5)
C110.1089 (4)0.3950 (4)0.1561 (3)0.0310 (6)
H11A0.01500.45290.24650.065 (13)*
H11B0.22880.43030.16750.028 (8)*
H11C0.07390.42230.07340.063 (13)*
C120.3977 (4)0.2372 (4)0.0326 (3)0.0272 (6)
H12A0.48280.27900.08440.042 (10)*
H12B0.44080.13780.01200.033 (9)*
C130.3947 (4)0.3663 (3)0.1049 (3)0.0247 (5)
C140.3852 (4)0.4699 (4)0.2141 (3)0.0279 (6)
H140.37760.55320.30200.056 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0299 (4)0.0276 (4)0.0175 (3)0.0059 (3)0.0087 (3)0.0035 (2)
S20.0225 (3)0.0256 (3)0.0150 (3)0.0062 (2)0.0035 (2)0.0032 (2)
N10.0229 (11)0.0309 (12)0.0147 (10)0.0064 (9)0.0053 (8)0.0011 (9)
C20.0237 (13)0.0252 (13)0.0181 (12)0.0050 (10)0.0041 (10)0.0004 (10)
C30.0169 (11)0.0285 (13)0.0133 (11)0.0054 (9)0.0043 (9)0.0009 (10)
C40.0165 (11)0.0255 (12)0.0107 (10)0.0042 (9)0.0018 (8)0.0027 (9)
C50.0132 (11)0.0292 (13)0.0156 (11)0.0028 (9)0.0022 (9)0.0020 (10)
C60.0174 (12)0.0282 (14)0.0229 (13)0.0019 (10)0.0008 (10)0.0001 (11)
C70.0238 (13)0.0367 (16)0.0347 (15)0.0028 (11)0.0049 (11)0.0139 (13)
C80.0251 (14)0.0548 (19)0.0191 (12)0.0075 (13)0.0081 (10)0.0134 (13)
C90.0230 (13)0.0447 (17)0.0165 (12)0.0082 (12)0.0062 (10)0.0020 (11)
C100.0142 (11)0.0339 (14)0.0140 (11)0.0051 (10)0.0025 (9)0.0020 (10)
C110.0295 (14)0.0310 (15)0.0346 (15)0.0045 (11)0.0117 (12)0.0108 (12)
C120.0222 (13)0.0313 (14)0.0187 (12)0.0035 (10)0.0036 (10)0.0048 (11)
C130.0211 (12)0.0276 (14)0.0203 (12)0.0009 (10)0.0044 (10)0.0015 (11)
C140.0303 (14)0.0274 (14)0.0205 (13)0.0008 (11)0.0077 (11)0.0001 (11)
Geometric parameters (Å, º) top
S1—C31.759 (3)C7—C81.403 (4)
S1—C111.808 (3)C7—H70.9500
S2—C41.775 (2)C8—C91.374 (5)
S2—C121.825 (3)C8—H80.9500
N1—C21.320 (4)C9—C101.418 (4)
N1—C101.364 (4)C9—H90.9500
C2—C31.426 (3)C11—H11A0.9800
C2—H20.9500C11—H11B0.9800
C3—C41.383 (4)C11—H11C0.9800
C4—C51.429 (3)C12—C131.464 (3)
C5—C101.425 (3)C12—H12A0.9900
C5—C61.434 (4)C12—H12B0.9900
C6—C71.337 (4)C13—C141.181 (4)
C6—H60.9500C14—H140.9500
C3—S1—C11103.81 (13)C9—C8—H8119.9
C4—S2—C1299.24 (12)C7—C8—H8119.9
C2—N1—C10118.5 (2)C8—C9—C10120.8 (3)
N1—C2—C3123.8 (3)C8—C9—H9119.6
N1—C2—H2118.1C10—C9—H9119.6
C3—C2—H2118.1N1—C10—C9119.0 (2)
C4—C3—C2118.2 (2)N1—C10—C5122.7 (2)
C4—C3—S1118.90 (18)C9—C10—C5118.3 (3)
C2—C3—S1122.9 (2)S1—C11—H11A109.5
C3—C4—C5119.6 (2)S1—C11—H11B109.5
C3—C4—S2119.55 (19)H11A—C11—H11B109.5
C5—C4—S2120.8 (2)S1—C11—H11C109.5
C10—C5—C4117.1 (2)H11A—C11—H11C109.5
C10—C5—C6118.8 (2)H11B—C11—H11C109.5
C4—C5—C6124.1 (2)C13—C12—S2107.56 (19)
C7—C6—C5120.7 (3)C13—C12—H12A110.2
C7—C6—H6119.6S2—C12—H12A110.2
C5—C6—H6119.6C13—C12—H12B110.2
C6—C7—C8121.3 (3)S2—C12—H12B110.2
C6—C7—H7119.4H12A—C12—H12B108.5
C8—C7—H7119.4C14—C13—C12177.5 (3)
C9—C8—C7120.1 (3)C13—C14—H14180.0

Experimental details

Crystal data
Chemical formulaC13H11NS2
Mr245.35
Crystal system, space groupTriclinic, P1
Temperature (K)125
a, b, c (Å)7.448 (3), 8.514 (3), 9.786 (3)
α, β, γ (°)107.57 (3), 100.99 (3), 94.57 (3)
V3)574.4 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.43
Crystal size (mm)0.25 × 0.20 × 0.10
Data collection
DiffractometerNonius Kappa CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3618, 2616, 2315
Rint0.036
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.127, 1.10
No. of reflections2616
No. of parameters157
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.93, 0.46

Computer programs: EVAL14 (Duisenberg, 1998), EVAL14, SHELXS86 (Sheldrick, 1986), SHELXL97 (Sheldrick, 1997), SHELXL97, ORTEPII (Johnson, 1976), PLATON (Spek, 1990).

 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds