Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100008611/da1140sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008611/da1140Isup2.hkl |
CCDC reference: 152611
Bis(4-propargyloxy-3-quinolinylthio)methane, (I), was prepared following published procedures (Boryczka, 1999) and crystallized from ethanol. 1H NMR and MS spectra have also been given by Boryczka (1999).
H-atoms bonded to C were treated with the riding model using the default parameters for C—H bond lengths at RT, with isotropic displacement parameters allowed to vary. All H-atom displacement parameters refined to realistic values in the range 0.045–0.096 Å2.
Alkynylquinolines comprise an important class of biologically active compounds which have been considered as bactericides, fungicides and analgesics (Smith, 1950; Blumenthal, 1959; Burckhardt & Zimmermann, 1972). Synthetic methods for preparation of alkynylquinolines are of interest with regard to synthesis of enediyne antitumor antibiotics or similar structural models (Nicolaou & Dai, 1991; Maier et al., 1999). A simple and efficient method for synthesis of propargyl thioquinolines by reaction of thioquinanthrene with alkoxides has been reported recently (Boryczka, 1999). Furthermore, the intermolecular interactions of alkynylquinolinesmay exhibit non-conventional hydrogen-bonding effects (Desiraju & Steiner, 1999). Recently, we have reported the crystal structures of 3-methylthio-4-propargylthioquinoline and two salts of this molecule, and find short C≡C—H···N and C≡C—H···O hydrogen bonds (Boryczka et al., 2000; Boryczka & Steiner, 2000). We have now prepared the larger molecule bis(4-propargyloxy-3-quinolinylthio)methane, (I), and report here its molecular and crystal structure. \sch
The molecular structure of (I) is shown in Fig. 1. A l l bond lengths and angles are normal (relevant values are given in Table 2). The conformation has close to twofold symmetry. The –S—CH2—S– link between the quinoline moieties is almost perpendicular to the quinoline planes [torsion angles C21—C31—S1···S2 = -93.8 (2), C22—C32—S2···S1 = -83.1 (2) and C31—S1···S2—C32 = 116.88°]. The two aromatic planes are roughly parallel with an interplanar angle of 7.9 (1)°. The offset between the thioquinoline planes is 3.067 (1) Å at the S atoms. The intramolecular S···O distances are S1···O1 = 3.189 (1) and O2···S2 = 3.160 (1) Å, respectively. This parallels the molecular structure of bis(4-bromophenylthio)methane (Berthon et al., 1970) and 4-methoxy-3'-methylthio-3,4'-diqionolinyl sulfide (Boryczka et al., 1990). Further short intramolecular distances are C111···S1 = 3.291 (2) and C112···S2 = 3.338 (2) Å, associated with C—H···S contacts of H···S = 2.53 and 2.61 Å (for C—H normalized to 1.08 Å) and C—H···S angles of 127 and 124°, respectively. The propargyl groups are pointing out of the quinoline planes (Table 2). The C≡C—H groups are antiparallel and far separate from each other (C131···C132 = 12.529 Å).
In the crystal lattice, the pseudo twofold axis running through C1 is oriented almost parallel with the crystallographic y axis, and is displaced at C1 by only 0.412 Å from a screw axis of space group P21/n. This leads to the formation of molecular ribbons as shown in Fig. 2. The displacement of the molecular axis from the crystallographic axis is sufficiently large to generate substantial differences in the intermolecular interactions of the two halves of the molecule. In particular, the pyridyl N atom N2 accepts a short and linear C—H···N hydrogen bond, whereas N1 does not [C111—H···N2(1/2 - x, y - 1/2, 3/2 - z) with H···N = 2.30, C···N = 3.327 (3) Å, angle = 158°, for normalized C—H]. The lateral interactions of the molecular ribbons are dominated by aromatic stacking. The two C≡C—H groups are involved only in hydrogen bonds of poor geometries directed at N atoms of neighbouring ribbons [C131—H···N1(1/2 + x, 1/2 - y, 1/2 + z) and C132—H···N2(-1/2 + x, 1/2 - y, -1/2 + z) with H···N = 2.58 and 2.71 Å, and angles of 135 and 131°, respectively]. For comparison, the C≡C—H···N hydrogen bond in 3-methylthio-4-propargylthioquinoline has a H···N distance of 2.28 Å (Boryczka et al., 2000), and in a set of 12 C≡C—H···N hydrogen bonds in terminal alkynes, a mean distance of H···N = 2.40 Å has been found (Steiner, 1998). This means that in the present compound, the most favourable C—H···N hydrogen bond is not donated by the most acidic C—H group, but by a less activated one. We assume that this circumstance is due to the awkward shape of the molecule that, unlike in the much simpler 3-methylthio-4-propargylthioquinoline, does not show efficient crystal packing and favourable hydrogen bonding at the same time.
Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT; data reduction: COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C25H18N2O2S2 | F(000) = 920 |
Mr = 442.53 | Dx = 1.374 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7358 (10) Å | Cell parameters from 50 reflections |
b = 15.8301 (12) Å | θ = 4.2–18.2° |
c = 13.4377 (8) Å | µ = 0.27 mm−1 |
β = 110.482 (6)° | T = 293 K |
V = 2139.3 (3) Å3 | Block, yellow |
Z = 4 | 0.30 × 0.23 × 0.18 mm |
Nonius KappaCCD diffractometer | 3692 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 27.5°, θmin = 2.1° |
ω–scans | h = −12→13 |
11444 measured reflections | k = −20→16 |
4887 independent reflections | l = −17→13 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0274P)2 + 1.1015P] where P = (Fo2 + 2Fc2)/3 |
4887 reflections | (Δ/σ)max = 0.001 |
298 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C25H18N2O2S2 | V = 2139.3 (3) Å3 |
Mr = 442.53 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.7358 (10) Å | µ = 0.27 mm−1 |
b = 15.8301 (12) Å | T = 293 K |
c = 13.4377 (8) Å | 0.30 × 0.23 × 0.18 mm |
β = 110.482 (6)° |
Nonius KappaCCD diffractometer | 3692 reflections with I > 2σ(I) |
11444 measured reflections | Rint = 0.033 |
4887 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.23 e Å−3 |
4887 reflections | Δρmin = −0.24 e Å−3 |
298 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.37344 (5) | 0.16974 (4) | 0.79461 (4) | 0.04885 (15) | |
S2 | 0.09240 (5) | 0.15249 (4) | 0.62985 (4) | 0.04842 (15) | |
O1 | 0.23640 (13) | 0.10721 (8) | 0.95721 (11) | 0.0426 (3) | |
O2 | 0.22108 (12) | 0.09232 (8) | 0.46331 (10) | 0.0386 (3) | |
N1 | 0.24693 (18) | 0.36938 (11) | 0.91429 (14) | 0.0524 (5) | |
C21 | 0.2973 (2) | 0.31620 (14) | 0.86316 (17) | 0.0506 (5) | |
H21 | 0.3342 | 0.3393 | 0.8161 | 0.078 (8)* | |
C31 | 0.30048 (18) | 0.22715 (12) | 0.87320 (15) | 0.0386 (4) | |
C41 | 0.24696 (17) | 0.19239 (12) | 0.94384 (14) | 0.0345 (4) | |
C51 | 0.12595 (19) | 0.21609 (15) | 1.06925 (16) | 0.0455 (5) | |
H51 | 0.1241 | 0.1583 | 1.0814 | 0.050 (6)* | |
C61 | 0.0687 (2) | 0.27098 (17) | 1.11916 (18) | 0.0566 (6) | |
H61 | 0.0278 | 0.2503 | 1.1647 | 0.063 (7)* | |
C71 | 0.0714 (2) | 0.35789 (17) | 1.1022 (2) | 0.0620 (7) | |
H71 | 0.0322 | 0.3944 | 1.1369 | 0.069 (7)* | |
C81 | 0.1305 (2) | 0.39011 (15) | 1.03572 (19) | 0.0576 (6) | |
H81 | 0.1317 | 0.4482 | 1.0254 | 0.076 (8)* | |
C91 | 0.19035 (19) | 0.33479 (13) | 0.98208 (16) | 0.0437 (5) | |
C101 | 0.18797 (17) | 0.24670 (12) | 0.99910 (14) | 0.0365 (4) | |
C111 | 0.3584 (2) | 0.05890 (13) | 0.99732 (16) | 0.0458 (5) | |
H11A | 0.4204 | 0.0796 | 0.9650 | 0.056 (6)* | |
H11B | 0.3395 | 0.0002 | 0.9769 | 0.059 (7)* | |
C121 | 0.4203 (2) | 0.06417 (13) | 1.11268 (18) | 0.0469 (5) | |
C131 | 0.4765 (3) | 0.06462 (17) | 1.2043 (2) | 0.0668 (7) | |
H131 | 0.5212 | 0.0650 | 1.2774 | 0.096 (10)* | |
N2 | 0.21126 (19) | 0.35383 (11) | 0.50801 (14) | 0.0516 (4) | |
C22 | 0.1622 (2) | 0.30045 (14) | 0.55933 (17) | 0.0486 (5) | |
H22 | 0.1271 | 0.3231 | 0.6077 | 0.055 (6)* | |
C32 | 0.15793 (18) | 0.21179 (12) | 0.54783 (15) | 0.0384 (4) | |
C42 | 0.21006 (16) | 0.17761 (11) | 0.47611 (13) | 0.0318 (4) | |
C52 | 0.32776 (18) | 0.20219 (13) | 0.34830 (15) | 0.0407 (4) | |
H52 | 0.3294 | 0.1446 | 0.3353 | 0.045 (6)* | |
C62 | 0.3844 (2) | 0.25785 (15) | 0.29876 (17) | 0.0501 (5) | |
H62 | 0.4256 | 0.2376 | 0.2531 | 0.060 (7)* | |
C72 | 0.3810 (2) | 0.34484 (15) | 0.31587 (18) | 0.0560 (6) | |
H72 | 0.4194 | 0.3818 | 0.2811 | 0.066 (7)* | |
C82 | 0.3219 (2) | 0.37585 (14) | 0.38300 (18) | 0.0541 (6) | |
H82 | 0.3192 | 0.4339 | 0.3930 | 0.070 (8)* | |
C92 | 0.26454 (19) | 0.32021 (12) | 0.43764 (16) | 0.0420 (4) | |
C102 | 0.26665 (17) | 0.23224 (11) | 0.41930 (14) | 0.0350 (4) | |
C112 | 0.09862 (19) | 0.04592 (12) | 0.41725 (15) | 0.0417 (4) | |
H11C | 0.0350 | 0.0655 | 0.4486 | 0.046 (6)* | |
H11D | 0.1154 | −0.0135 | 0.4345 | 0.055 (6)* | |
C122 | 0.0410 (2) | 0.05526 (13) | 0.30203 (17) | 0.0426 (5) | |
C132 | −0.0122 (3) | 0.06131 (17) | 0.2100 (2) | 0.0635 (6) | |
H132 | −0.0545 | 0.0661 | 0.1369 | 0.092 (10)* | |
C1 | 0.2405 (2) | 0.10105 (14) | 0.71750 (15) | 0.0472 (5) | |
H1A | 0.2155 | 0.0654 | 0.7662 | 0.062 (7)* | |
H1B | 0.2745 | 0.0644 | 0.6751 | 0.065 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0426 (3) | 0.0661 (4) | 0.0443 (3) | −0.0052 (2) | 0.0232 (2) | 0.0008 (2) |
S2 | 0.0428 (3) | 0.0634 (4) | 0.0450 (3) | −0.0080 (2) | 0.0229 (2) | −0.0060 (2) |
O1 | 0.0420 (7) | 0.0364 (7) | 0.0530 (8) | −0.0051 (6) | 0.0211 (6) | 0.0032 (6) |
O2 | 0.0369 (7) | 0.0286 (7) | 0.0500 (8) | −0.0005 (5) | 0.0149 (6) | −0.0027 (6) |
N1 | 0.0577 (11) | 0.0395 (10) | 0.0549 (11) | −0.0095 (9) | 0.0134 (9) | 0.0004 (8) |
C21 | 0.0533 (12) | 0.0503 (13) | 0.0455 (11) | −0.0165 (10) | 0.0141 (10) | 0.0049 (10) |
C31 | 0.0345 (9) | 0.0442 (11) | 0.0363 (10) | −0.0091 (8) | 0.0113 (8) | −0.0006 (8) |
C41 | 0.0310 (9) | 0.0358 (10) | 0.0346 (9) | −0.0054 (7) | 0.0089 (7) | 0.0011 (7) |
C51 | 0.0384 (10) | 0.0553 (14) | 0.0435 (11) | −0.0016 (9) | 0.0151 (9) | −0.0004 (9) |
C61 | 0.0467 (12) | 0.0761 (18) | 0.0513 (13) | 0.0015 (11) | 0.0224 (10) | −0.0091 (11) |
C71 | 0.0486 (13) | 0.0714 (17) | 0.0658 (15) | 0.0050 (12) | 0.0199 (12) | −0.0236 (13) |
C81 | 0.0503 (13) | 0.0423 (13) | 0.0695 (15) | 0.0021 (10) | 0.0074 (11) | −0.0137 (11) |
C91 | 0.0363 (10) | 0.0433 (12) | 0.0436 (11) | −0.0048 (8) | 0.0042 (8) | −0.0041 (9) |
C101 | 0.0296 (9) | 0.0418 (11) | 0.0339 (9) | −0.0017 (8) | 0.0056 (7) | −0.0026 (8) |
C111 | 0.0558 (12) | 0.0355 (11) | 0.0523 (12) | 0.0051 (9) | 0.0267 (10) | 0.0011 (9) |
C121 | 0.0533 (12) | 0.0351 (11) | 0.0556 (13) | 0.0007 (9) | 0.0231 (11) | 0.0039 (9) |
C131 | 0.0763 (17) | 0.0613 (16) | 0.0559 (16) | 0.0054 (13) | 0.0145 (13) | 0.0015 (12) |
N2 | 0.0632 (12) | 0.0330 (9) | 0.0551 (11) | 0.0065 (8) | 0.0162 (9) | −0.0022 (8) |
C22 | 0.0538 (13) | 0.0440 (12) | 0.0477 (12) | 0.0115 (10) | 0.0173 (10) | −0.0073 (9) |
C32 | 0.0360 (9) | 0.0405 (11) | 0.0385 (10) | 0.0014 (8) | 0.0127 (8) | −0.0013 (8) |
C42 | 0.0282 (8) | 0.0314 (9) | 0.0326 (9) | 0.0018 (7) | 0.0065 (7) | −0.0003 (7) |
C52 | 0.0395 (10) | 0.0412 (11) | 0.0417 (10) | −0.0022 (8) | 0.0148 (8) | −0.0002 (8) |
C62 | 0.0461 (11) | 0.0618 (14) | 0.0447 (12) | −0.0032 (10) | 0.0188 (9) | 0.0065 (10) |
C72 | 0.0562 (13) | 0.0546 (14) | 0.0569 (13) | −0.0092 (11) | 0.0196 (11) | 0.0181 (11) |
C82 | 0.0583 (13) | 0.0331 (11) | 0.0639 (14) | −0.0047 (10) | 0.0126 (11) | 0.0095 (10) |
C92 | 0.0416 (10) | 0.0343 (10) | 0.0437 (11) | 0.0029 (8) | 0.0067 (8) | 0.0025 (8) |
C102 | 0.0310 (9) | 0.0349 (10) | 0.0348 (9) | −0.0004 (7) | 0.0059 (7) | 0.0005 (7) |
C112 | 0.0446 (11) | 0.0345 (10) | 0.0474 (11) | −0.0075 (8) | 0.0176 (9) | −0.0015 (8) |
C122 | 0.0436 (11) | 0.0360 (11) | 0.0501 (12) | −0.0013 (8) | 0.0187 (9) | −0.0062 (9) |
C132 | 0.0698 (16) | 0.0679 (17) | 0.0487 (15) | −0.0062 (13) | 0.0157 (12) | −0.0013 (11) |
C1 | 0.0615 (13) | 0.0450 (12) | 0.0397 (10) | −0.0032 (10) | 0.0236 (10) | −0.0011 (9) |
S1—C31 | 1.770 (2) | C81—C91 | 1.422 (3) |
S1—C1 | 1.805 (2) | C91—C101 | 1.415 (3) |
S2—C32 | 1.770 (2) | C111—C121 | 1.460 (3) |
S2—C1 | 1.808 (2) | C121—C131 | 1.166 (3) |
O1—C41 | 1.370 (2) | N2—C22 | 1.312 (3) |
O1—C111 | 1.448 (2) | N2—C92 | 1.372 (3) |
O2—C42 | 1.371 (2) | C22—C32 | 1.411 (3) |
O2—C112 | 1.443 (2) | C32—C42 | 1.383 (2) |
N1—C21 | 1.316 (3) | C42—C102 | 1.423 (2) |
N1—C91 | 1.373 (3) | C52—C62 | 1.368 (3) |
C21—C31 | 1.415 (3) | C52—C102 | 1.416 (3) |
C31—C41 | 1.384 (2) | C62—C72 | 1.399 (3) |
C41—C101 | 1.422 (3) | C72—C82 | 1.363 (3) |
C51—C61 | 1.368 (3) | C82—C92 | 1.418 (3) |
C51—C101 | 1.416 (3) | C92—C102 | 1.416 (3) |
C61—C71 | 1.396 (4) | C112—C122 | 1.460 (3) |
C71—C81 | 1.363 (4) | C122—C132 | 1.170 (3) |
C31—S1—C1 | 103.04 (9) | C131—C121—C111 | 175.3 (2) |
C32—S2—C1 | 101.18 (9) | C22—N2—C92 | 116.94 (18) |
C41—O1—C111 | 117.56 (14) | N2—C22—C32 | 125.95 (19) |
C42—O2—C112 | 116.70 (14) | C42—C32—C22 | 117.37 (18) |
C21—N1—C91 | 116.69 (19) | C42—C32—S2 | 124.92 (15) |
N1—C21—C31 | 126.0 (2) | C22—C32—S2 | 117.66 (15) |
C41—C31—C21 | 117.35 (19) | O2—C42—C32 | 123.12 (16) |
C41—C31—S1 | 125.56 (15) | O2—C42—C102 | 117.34 (15) |
C21—C31—S1 | 117.09 (15) | C32—C42—C102 | 119.28 (17) |
O1—C41—C31 | 123.67 (17) | C62—C52—C102 | 120.1 (2) |
O1—C41—C101 | 117.02 (16) | C52—C62—C72 | 120.8 (2) |
C31—C41—C101 | 119.05 (17) | C82—C72—C62 | 120.6 (2) |
C61—C51—C101 | 120.4 (2) | C72—C82—C92 | 120.4 (2) |
C51—C61—C71 | 120.5 (2) | N2—C92—C102 | 122.50 (18) |
C81—C71—C61 | 121.1 (2) | N2—C92—C82 | 118.50 (19) |
C71—C81—C91 | 119.9 (2) | C102—C92—C82 | 119.0 (2) |
N1—C91—C101 | 122.51 (19) | C92—C102—C52 | 119.15 (18) |
N1—C91—C81 | 118.3 (2) | C92—C102—C42 | 117.94 (17) |
C101—C91—C81 | 119.2 (2) | C52—C102—C42 | 122.88 (17) |
C91—C101—C51 | 118.96 (18) | O2—C112—C122 | 112.83 (16) |
C91—C101—C41 | 118.37 (17) | C132—C122—C112 | 176.1 (2) |
C51—C101—C41 | 122.67 (18) | S1—C1—S2 | 116.18 (12) |
O1—C111—C121 | 112.42 (16) | ||
C91—N1—C21—C31 | −1.2 (3) | N2—C22—C32—C42 | 0.1 (3) |
N1—C21—C31—C41 | −0.6 (3) | N2—C22—C32—S2 | 177.62 (17) |
N1—C21—C31—S1 | 179.67 (17) | C1—S2—C32—C42 | 67.22 (18) |
C1—S1—C31—C41 | 58.71 (18) | C1—S2—C32—C22 | −110.13 (17) |
C1—S1—C31—C21 | −121.61 (16) | C112—O2—C42—C32 | 68.2 (2) |
C111—O1—C41—C31 | 63.4 (2) | C112—O2—C42—C102 | −117.71 (17) |
C111—O1—C41—C101 | −122.57 (17) | C22—C32—C42—O2 | 174.93 (17) |
C21—C31—C41—O1 | 176.13 (17) | S2—C32—C42—O2 | −2.4 (3) |
S1—C31—C41—O1 | −4.2 (3) | C22—C32—C42—C102 | 1.0 (3) |
C21—C31—C41—C101 | 2.2 (3) | S2—C32—C42—C102 | −176.39 (13) |
S1—C31—C41—C101 | −178.07 (13) | C102—C52—C62—C72 | −1.0 (3) |
C101—C51—C61—C71 | −0.4 (3) | C52—C62—C72—C82 | 0.5 (3) |
C51—C61—C71—C81 | 0.1 (4) | C62—C72—C82—C92 | 0.9 (3) |
C61—C71—C81—C91 | 0.2 (3) | C22—N2—C92—C102 | 0.5 (3) |
C21—N1—C91—C101 | 1.4 (3) | C22—N2—C92—C82 | −178.21 (19) |
C21—N1—C91—C81 | −177.70 (19) | C72—C82—C92—N2 | 177.2 (2) |
C71—C81—C91—N1 | 178.9 (2) | C72—C82—C92—C102 | −1.6 (3) |
C71—C81—C91—C101 | −0.3 (3) | N2—C92—C102—C52 | −177.72 (17) |
N1—C91—C101—C51 | −179.12 (17) | C82—C92—C102—C52 | 1.0 (3) |
C81—C91—C101—C51 | 0.0 (3) | N2—C92—C102—C42 | 0.5 (3) |
N1—C91—C101—C41 | 0.2 (3) | C82—C92—C102—C42 | 179.18 (17) |
C81—C91—C101—C41 | 179.30 (17) | C62—C52—C102—C92 | 0.3 (3) |
C61—C51—C101—C91 | 0.4 (3) | C62—C52—C102—C42 | −177.79 (18) |
C61—C51—C101—C41 | −178.93 (18) | O2—C42—C102—C92 | −175.51 (15) |
O1—C41—C101—C91 | −176.35 (16) | C32—C42—C102—C92 | −1.2 (2) |
C31—C41—C101—C91 | −2.1 (3) | O2—C42—C102—C52 | 2.6 (3) |
O1—C41—C101—C51 | 2.9 (3) | C32—C42—C102—C52 | 176.90 (17) |
C31—C41—C101—C51 | 177.23 (17) | C42—O2—C112—C122 | 78.5 (2) |
C41—O1—C111—C121 | 81.5 (2) | O2—C112—C122—C132 | −160 (3) |
O1—C111—C121—C131 | 178 (100) | C31—S1—C1—S2 | 61.73 (13) |
C92—N2—C22—C32 | −0.8 (3) | C32—S2—C1—S1 | 58.94 (13) |
Experimental details
Crystal data | |
Chemical formula | C25H18N2O2S2 |
Mr | 442.53 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.7358 (10), 15.8301 (12), 13.4377 (8) |
β (°) | 110.482 (6) |
V (Å3) | 2139.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.30 × 0.23 × 0.18 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11444, 4887, 3692 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.105, 1.10 |
No. of reflections | 4887 |
No. of parameters | 298 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.24 |
Computer programs: COLLECT (Nonius, 1998), COLLECT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990).
S1—C31 | 1.770 (2) | N1—C91 | 1.373 (3) |
S1—C1 | 1.805 (2) | C121—C131 | 1.166 (3) |
S2—C32 | 1.770 (2) | N2—C22 | 1.312 (3) |
S2—C1 | 1.808 (2) | N2—C92 | 1.372 (3) |
N1—C21 | 1.316 (3) | C122—C132 | 1.170 (3) |
C31—S1—C1 | 103.04 (9) | C21—N1—C91 | 116.69 (19) |
C32—S2—C1 | 101.18 (9) | C22—N2—C92 | 116.94 (18) |
C41—O1—C111 | 117.56 (14) | S1—C1—S2 | 116.18 (12) |
C42—O2—C112 | 116.70 (14) | ||
C1—S1—C31—C21 | −121.61 (16) | C112—O2—C42—C32 | 68.2 (2) |
C111—O1—C41—C31 | 63.4 (2) | C42—O2—C112—C122 | 78.5 (2) |
C41—O1—C111—C121 | 81.5 (2) | C31—S1—C1—S2 | 61.73 (13) |
C1—S2—C32—C22 | −110.13 (17) | C32—S2—C1—S1 | 58.94 (13) |
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Alkynylquinolines comprise an important class of biologically active compounds which have been considered as bactericides, fungicides and analgesics (Smith, 1950; Blumenthal, 1959; Burckhardt & Zimmermann, 1972). Synthetic methods for preparation of alkynylquinolines are of interest with regard to synthesis of enediyne antitumor antibiotics or similar structural models (Nicolaou & Dai, 1991; Maier et al., 1999). A simple and efficient method for synthesis of propargyl thioquinolines by reaction of thioquinanthrene with alkoxides has been reported recently (Boryczka, 1999). Furthermore, the intermolecular interactions of alkynylquinolinesmay exhibit non-conventional hydrogen-bonding effects (Desiraju & Steiner, 1999). Recently, we have reported the crystal structures of 3-methylthio-4-propargylthioquinoline and two salts of this molecule, and find short C≡C—H···N and C≡C—H···O hydrogen bonds (Boryczka et al., 2000; Boryczka & Steiner, 2000). We have now prepared the larger molecule bis(4-propargyloxy-3-quinolinylthio)methane, (I), and report here its molecular and crystal structure. \sch
The molecular structure of (I) is shown in Fig. 1. A l l bond lengths and angles are normal (relevant values are given in Table 2). The conformation has close to twofold symmetry. The –S—CH2—S– link between the quinoline moieties is almost perpendicular to the quinoline planes [torsion angles C21—C31—S1···S2 = -93.8 (2), C22—C32—S2···S1 = -83.1 (2) and C31—S1···S2—C32 = 116.88°]. The two aromatic planes are roughly parallel with an interplanar angle of 7.9 (1)°. The offset between the thioquinoline planes is 3.067 (1) Å at the S atoms. The intramolecular S···O distances are S1···O1 = 3.189 (1) and O2···S2 = 3.160 (1) Å, respectively. This parallels the molecular structure of bis(4-bromophenylthio)methane (Berthon et al., 1970) and 4-methoxy-3'-methylthio-3,4'-diqionolinyl sulfide (Boryczka et al., 1990). Further short intramolecular distances are C111···S1 = 3.291 (2) and C112···S2 = 3.338 (2) Å, associated with C—H···S contacts of H···S = 2.53 and 2.61 Å (for C—H normalized to 1.08 Å) and C—H···S angles of 127 and 124°, respectively. The propargyl groups are pointing out of the quinoline planes (Table 2). The C≡C—H groups are antiparallel and far separate from each other (C131···C132 = 12.529 Å).
In the crystal lattice, the pseudo twofold axis running through C1 is oriented almost parallel with the crystallographic y axis, and is displaced at C1 by only 0.412 Å from a screw axis of space group P21/n. This leads to the formation of molecular ribbons as shown in Fig. 2. The displacement of the molecular axis from the crystallographic axis is sufficiently large to generate substantial differences in the intermolecular interactions of the two halves of the molecule. In particular, the pyridyl N atom N2 accepts a short and linear C—H···N hydrogen bond, whereas N1 does not [C111—H···N2(1/2 - x, y - 1/2, 3/2 - z) with H···N = 2.30, C···N = 3.327 (3) Å, angle = 158°, for normalized C—H]. The lateral interactions of the molecular ribbons are dominated by aromatic stacking. The two C≡C—H groups are involved only in hydrogen bonds of poor geometries directed at N atoms of neighbouring ribbons [C131—H···N1(1/2 + x, 1/2 - y, 1/2 + z) and C132—H···N2(-1/2 + x, 1/2 - y, -1/2 + z) with H···N = 2.58 and 2.71 Å, and angles of 135 and 131°, respectively]. For comparison, the C≡C—H···N hydrogen bond in 3-methylthio-4-propargylthioquinoline has a H···N distance of 2.28 Å (Boryczka et al., 2000), and in a set of 12 C≡C—H···N hydrogen bonds in terminal alkynes, a mean distance of H···N = 2.40 Å has been found (Steiner, 1998). This means that in the present compound, the most favourable C—H···N hydrogen bond is not donated by the most acidic C—H group, but by a less activated one. We assume that this circumstance is due to the awkward shape of the molecule that, unlike in the much simpler 3-methylthio-4-propargylthioquinoline, does not show efficient crystal packing and favourable hydrogen bonding at the same time.