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The title compound, C9H7NS, crystallizes as the thione tautomer with Z′ = 8 (four independent dimers with local inversion symmetry via two N—H...S=C hydrogen-bond systems). The dimers are arranged in chains parallel to [\overline 110], each chain being crystallographically independent. These chains are associated into layers via stacking of ring systems. The Z′ value can be rationalized in terms of a factor 2 for dimer formation without crystallographic symmetry and an additional factor 4 for differing stacking environments.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104025636/bm1582sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104025636/bm1582Isup2.hkl
Contains datablock I

CCDC reference: 259034

Comment top

We are interested in the structures and optical properties of formal `mercaptans' of aromatic N-heterocycles, in which, however, the usual tautomer is the thione form, with a double bond to the S atom and a protonated N atom. We have published studies of 2-mercaptothiazoline (thiazoline-2-thione; Flakus Tyl & Jones, 2002) and 4-mercaptopyridine (pyridine-4-thione; Flakus Miros & Jones, 2002); the former consists of inversion-symmetric dimers, hydrogen-bonded by N—H···SC systems, whereas the latter forms zigzag chains, also via N—H···SC hydrogen bonds. Pyridine-2-thione (Reynolds et al., 1995) also forms inversion-symmetric dimers, and it has found use as a ligand in transition metal chemistry (Reynolds et al., 1995; Usón et al., 1990).

Here, we report the structure of quinoline-2(1H)-thione (I), an important reagent in analytical chemistry (Karagiannidis et al., 1990; Paneli & Voulgaropoulos, 1991; Steed & Tocher, 1992; Leeaphon et al., 1993; Kitagawa et al., 1993; Aslanidis et al., 1998). Solution IR spectra (Flakus, 1994) indicated the presence of inversion-symmetric hydrogen-bonded dimers. Both the thione and the mercaptan forms have been found in low-temperature matrices by IR spectroscopy (Prusinowska et al., 1995). \sch

The structure determination of (I) establishes the presence of the expected thione form of the molecule, but the most striking feature is the presence of eight independent molecules (Fig. 1). The Cambridge Structural Database (CSD, Version 7/04; Allen, 2002) contains only 61 hits with Z' 8, out of a total of 322421 entries. We can see no evidence that unrecognized twinning or structure modulation has led to an inappropriate cell, and a variety of programs have failed to indicate any overlooked symmetry. Together with the Flack parameter (Flack, 1983) of 0.03 (3), this is good evidence for the absence of a global inversion centre, despite the rather high mean (E2-1) value of 0.869.

All eight molecules of (I) are closely similar and essentially planar (all mean deviations of non-H atoms from planarity are less than 0.03 Å). The molecular dimensions may be regarded as normal, e.g. the short N—C1 and longer N—C9 bonds, the short C2—C3 and long C3—C4 bonds consistent with the thione tautomer, the CS bond lengths, and the widened angle at N typical of protonated pyridinic systems (Table 1). Note that the numbering is chosen to allow an easy comparison of the independent molecules (the first digit of each atom label is the molecule number) and does not correspond to the IUPAC numbering. Rigid-body libration corrections (Schomaker & Trueblood, 1968) can be applied successfully because of the lack of torsional degrees of freedom, and lie in the range 0.002–0.005 Å (Table 3).

The molecules form the expected inversion-symmetric pairs via N—H···S hydrogen bonding (Fig. 1, Table 2), although the symmetry is only approximate rather than exact. Thus, the ring systems within each pair are not exactly parallel [interplanar angles: molecule 1/molecule 2 2.54 (6), 2/3 6.51 (6), 5/6 6.17 (6), 7/8 1.45 (6)°, with planes calculated through all non-H atoms]. The H···SC angles are in the range 109.7 (5)–111.5 (5)°. Each H atom at C8 is forced into proximity with the S atom of the hydrogen-bonded partner, but these contacts (one of which is given as an example in Table 2) should not necessarily be regarded as hydrogen bonds. Similarly, the other C—H···S contacts given for completeness in Table 2 may not be of great structural significance.

The extended packing in the region z 0 involves chains of hydrogen-bonded pairs parallel to [110] (Fig. 2), or to [110] in the region z 1/2. Each chain consists of only one type of pair, e.g. only molecules 1 and 2. The chains lie in common layers in which only translational symmetry is involved. In Fig. 2, successive pairs in the chain are related by the C-centring operator (x − 1/2, 1/2 + y, z), while the operator (1/2 + x, 1/2 + y, z) transforms one chain into its counterpart four chains lower.

The current interest in crystal packing and `engineering' extends to structures with high Z' [see, for example, Steed (2003), and references therein]. Why should such effects arise? There seems, at first, to be little reason why compound (I) should have Z' = 8, when its smaller analogue pyridine-2-thione has Z' = 1 (Reynolds et al., 1995), although the lack of global symmetry in the hydrogen-bonded pairs could easily lead to Z' = 2. A rationalization may be sought in the stacking geometry within the layers of (I). As can be seen from Fig. 1, molecules 2, 3, 6 and 7 (with coordinates as chosen for the asymmetric unit) are stacked above each other. This is confirmed in Fig. 2, which shows two stacks, the second being composed of molecules 1, 4, 5 and 8 in that order. All the rings are approximately parallel (maximum interplanar angles 10°), but are offset, as is expected for stable packing (Hunter & Sanders, 1990). The offsetting is such that the central C4—C9 bond, common to both rings, lies above the centre of the pyridine ring of the neighbouring molecule in the stack. However, a closer inspection shows that the molecules thereby acquire different environments. If we denote the interaction of C4—C9 lying over the ring centre as , then the four independent interactions in one stack are: molecule 7 molecule 6 molecule 3 molecule 2 molecule 7' (generated by stack translation). This can be seen in Fig. 3. Thus the stacking is such that there are three interactions in one direction, but the fourth is in the opposite direction. This explains the factor 4 that changes Z' from 2 to 8. In the second independent stack, the interactions are analogous: molecule 1 molecule 4 molecule 5 molecule 8 molecule 1'.

Thus one can, at least phenomenologically, explain the Z' value, although it would presumably be impossible, given the current state of knowledge, to predict the packing or explain the detailed causes. It would clearly be a worthwhile exercise to attempt to grow crystals of alternative polymorphs of (I), but in our hands the compound was most unwilling to crystallize adequately from any solvent.

Experimental top

Compound (I) was prepared by the method of Rosenhauer et al. (1929), but is now commercially available from Aldrich. Crystals of (I) were grown by slow evaporation of ethanol solutions, although good single crystals were extremely rare.

Refinement top

H atoms of the NH groups were clearly identified in difference syntheses and refined freely, but with N—H distances restrained equal (command SADI). Other H atoms were included using a riding model, with C—H bond lengths fixed at 0.95 Å, and with Uiso(H) = 1.2Ueq(C). The Flack parameter was refined on the basis of 7657 Friedel pairs.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) in the crystal. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines represent hydrogen bonds. The complete numbering of molecule 1 (bottom left) is given; the numbering of the other molecules can be completed analogously.
[Figure 2] Fig. 2. The packing of (I) in the crystal. H atoms (except those involved in hydrogen bonding) have been omitted for clarity. The view direction is approximately parallel to the c axis; the region at z 0 is shown. The molecules are numbered 1–8.
[Figure 3] Fig. 3. The stacking of molecules of (I) in the crystal. H atoms have been omitted for clarity. This is the stack involving molecules 6 (bonds as solid double lines), 3 (broken double lines), 2 (solid single lines) and 7 (broken single lines), in that order from top to bottom. The central C4—C9 bonds are drawn as thick solid bonds, to emphasize their positions with respect to the neighbouring pyridine rings (see text); that of molecule 7 is eclipsed. The view direction is perpendicular to best plane of molecule 3.
Quinoline-2(1H)-thione top
Crystal data top
C9H7NSF(000) = 2688
Mr = 161.22Dx = 1.374 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 19.9772 (14) ÅCell parameters from 5773 reflections
b = 19.9588 (14) Åθ = 2.8–29.6°
c = 15.6622 (11) ŵ = 0.34 mm1
β = 93.014 (4)°T = 133 K
V = 6236.2 (8) Å3Block, brown-yellow
Z = 320.28 × 0.24 × 0.24 mm
Data collection top
Bruker SMART1000 CCD area-detector
diffractometer
12944 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
Graphite monochromatorθmax = 28.7°, θmin = 1.4°
Detector resolution: 8.192 pixels mm-1h = 2626
ω and ϕ scansk = 2626
44742 measured reflectionsl = 2020
15776 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0429P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
15776 reflectionsΔρmax = 0.33 e Å3
825 parametersΔρmin = 0.18 e Å3
30 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (3)
Crystal data top
C9H7NSV = 6236.2 (8) Å3
Mr = 161.22Z = 32
Monoclinic, CcMo Kα radiation
a = 19.9772 (14) ŵ = 0.34 mm1
b = 19.9588 (14) ÅT = 133 K
c = 15.6622 (11) Å0.28 × 0.24 × 0.24 mm
β = 93.014 (4)°
Data collection top
Bruker SMART1000 CCD area-detector
diffractometer
12944 reflections with I > 2σ(I)
44742 measured reflectionsRint = 0.034
15776 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078Δρmax = 0.33 e Å3
S = 0.96Δρmin = 0.18 e Å3
15776 reflectionsAbsolute structure: Flack (1983)
825 parametersAbsolute structure parameter: 0.03 (3)
30 restraints
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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 13.0388 (0.0074) x + 14.7780 (0.0055) y − 1.9734 (0.0064) z = 3.8161 (0.0073)

* 0.0018 (0.0010) S7 * 0.0104 (0.0014) N7 * 0.0017 (0.0015) C71 * −0.0072 (0.0016) C72 * −0.0083 (0.0017) C73 * 0.0001 (0.0018) C74 * 0.0146 (0.0018) C75 * 0.0024 (0.0019) C76 * −0.0104 (0.0017) C77 * −0.0027 (0.0016) C78 * −0.0024 (0.0016) C79

Rms deviation of fitted atoms = 0.0072

15.3630 (0.0050) x − 12.1731 (0.0076) y + 2.3590 (0.0058) z = 3.3949 (0.0105)

Angle to previous plane (with approximate e.s.d.) = 10.19 (0.06)

* 0.0618 (0.0010) S6 * −0.0651 (0.0014) N6 * −0.0043 (0.0016) C61 * 0.0153 (0.0016) C62 * −0.0020 (0.0016) C63 * −0.0318 (0.0017) C64 * −0.0073 (0.0017) C65 * 0.0395 (0.0018) C66 * 0.0453 (0.0016) C67 * −0.0099 (0.0015) C68 * −0.0415 (0.0016) C69

Rms deviation of fitted atoms = 0.0367

13.9239 (0.0068) x − 13.8573 (0.0055) y + 2.2306 (0.0062) z = 4.4646 (0.0072)

Angle to previous plane (with approximate e.s.d.) = 6.40 (0.06)

* −0.0380 (0.0009) S3 * 0.0279 (0.0014) N3 * 0.0023 (0.0015) C31 * −0.0132 (0.0015) C32 * 0.0088 (0.0015) C33 * 0.0280 (0.0017) C34 * −0.0046 (0.0017) C35 * −0.0314 (0.0017) C36 * −0.0235 (0.0016) C37 * 0.0084 (0.0016) C38 * 0.0352 (0.0017) C39

Rms deviation of fitted atoms = 0.0236

14.9790 (0.0054) x − 12.6653 (0.0078) y + 2.3130 (0.0060) z = 9.5053 (0.0098)

Angle to previous plane (with approximate e.s.d.) = 4.59 (0.06)

* 0.0247 (0.0010) S2 * −0.0287 (0.0014) N2 * 0.0001 (0.0015) C21 * 0.0108 (0.0016) C22 * −0.0019 (0.0016) C23 * −0.0130 (0.0017) C24 * −0.0084 (0.0018) C25 * 0.0192 (0.0018) C26 * 0.0233 (0.0016) C27 * −0.0061 (0.0015) C28 * −0.0199 (0.0016) C29

Rms deviation of fitted atoms = 0.0169

14.1806 (0.0056) x − 13.7452 (0.0068) y + 1.7273 (0.0061) z = 1.5265 (0.0081)

Angle to previous plane (with approximate e.s.d.) = 4.47 (0.06)

* 0.0316 (0.0010) S5 * −0.0316 (0.0014) N5 * 0.0002 (0.0015) C51 * 0.0191 (0.0015) C52 * 0.0006 (0.0016) C53 * −0.0335 (0.0017) C54 * −0.0027 (0.0017) C55 * 0.0256 (0.0017) C56 * 0.0308 (0.0016) C57 * −0.0013 (0.0016) C58 * −0.0389 (0.0016) C59

Rms deviation of fitted atoms = 0.0245

12.2587 (0.0078) x − 15.3875 (0.0052) y + 2.1615 (0.0064) z = 1.8935 (0.0104)

Angle to previous plane (with approximate e.s.d.) = 7.37 (0.06)

* −0.0615 (0.0010) S4 * 0.0514 (0.0014) N4 * 0.0025 (0.0016) C41 * −0.0115 (0.0017) C42 * 0.0090 (0.0016) C43 * 0.0298 (0.0018) C44 * 0.0016 (0.0018) C45 * −0.0449 (0.0018) C46 * −0.0429 (0.0016) C47 * 0.0207 (0.0016) C48 * 0.0458 (0.0016) C49

Rms deviation of fitted atoms = 0.0355

14.7393 (0.0056) x − 13.1283 (0.0075) y + 1.7635 (0.0062) z = 8.9734 (0.0075)

Angle to previous plane (with approximate e.s.d.) = 9.70 (0.06)

* 0.0028 (0.0010) S1 * 0.0007 (0.0014) N1 * 0.0001 (0.0016) C11 * 0.0042 (0.0016) C12 * −0.0040 (0.0016) C13 * −0.0108 (0.0017) C14 * 0.0067 (0.0018) C15 * 0.0059 (0.0017) C16 * −0.0030 (0.0016) C17 * 0.0016 (0.0015) C18 * −0.0044 (0.0017) C19

Rms deviation of fitted atoms = 0.0050

− 12.7364 (0.0076) x + 15.0918 (0.0055) y − 1.7830 (0.0065) z = 4.3777 (0.0098)

Angle to previous plane (with approximate e.s.d.) = 8.06 (0.06)

* 0.0174 (0.0010) S8 * −0.0165 (0.0014) N8 * −0.0010 (0.0016) C81 * 0.0085 (0.0016) C82 * −0.0063 (0.0017) C83 * −0.0083 (0.0017) C84 * −0.0007 (0.0018) C85 * 0.0129 (0.0018) C86 * 0.0134 (0.0016) C87 * −0.0044 (0.0015) C88 * −0.0150 (0.0017) C89

Rms deviation of fitted atoms = 0.0111

=============================================================================

Hydrogen bond angles at sulfur:

111.49 (0.48) H01 - S2 - C21 109.96 (0.47) H02 - S1 - C11 110.55 (0.45) H03 - S4 - C41 109.69 (0.46) H04 - S3 - C31 110.22 (0.47) H05 - S6 - C61 110.47 (0.54) H06 - S5 - C51 111.40 (0.46) H07 - S8 - C81 111.38 (0.54) H08 - S7 - C71

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.81085 (3)0.26931 (3)0.31781 (3)0.03204 (12)
N10.75907 (8)0.23079 (8)0.46264 (10)0.0231 (3)
H010.7824 (10)0.2618 (9)0.4885 (12)0.035 (6)*
C110.76132 (9)0.22192 (10)0.37739 (11)0.0240 (4)
C120.71963 (9)0.16987 (10)0.34070 (12)0.0270 (4)
H120.71990.16150.28100.032*
C130.67992 (10)0.13240 (10)0.38904 (12)0.0294 (4)
H130.65270.09840.36280.035*
C140.67824 (9)0.14319 (10)0.47954 (12)0.0264 (4)
C150.63920 (10)0.10531 (11)0.53378 (13)0.0337 (5)
H150.61160.07030.51070.040*
C160.64061 (10)0.11855 (11)0.62007 (13)0.0338 (5)
H160.61380.09290.65620.041*
C170.68125 (10)0.16948 (10)0.65451 (12)0.0308 (4)
H170.68160.17850.71410.037*
C180.72102 (9)0.20691 (10)0.60338 (12)0.0262 (4)
H180.74920.24120.62740.031*
C190.71938 (9)0.19374 (9)0.51567 (11)0.0233 (4)
S20.84232 (3)0.34881 (3)0.57529 (3)0.03542 (12)
N20.89341 (8)0.38688 (8)0.42980 (9)0.0228 (3)
H020.8702 (9)0.3537 (9)0.4088 (12)0.031 (6)*
C210.89075 (9)0.39699 (10)0.51483 (11)0.0241 (4)
C220.93113 (9)0.45038 (10)0.55032 (12)0.0275 (4)
H220.93080.45950.60980.033*
C230.96984 (9)0.48810 (11)0.50070 (13)0.0296 (4)
H230.99580.52350.52590.036*
C240.97233 (9)0.47553 (10)0.41094 (12)0.0261 (4)
C251.01215 (10)0.51221 (11)0.35582 (13)0.0336 (5)
H251.03850.54860.37770.040*
C261.01323 (10)0.49578 (12)0.27089 (14)0.0365 (5)
H261.04070.52030.23440.044*
C270.97375 (10)0.44276 (10)0.23793 (12)0.0303 (4)
H270.97500.43160.17910.036*
C280.93341 (9)0.40675 (10)0.28935 (11)0.0256 (4)
H280.90630.37130.26630.031*
C290.93272 (9)0.42295 (9)0.37648 (11)0.0227 (4)
S30.90866 (2)0.68809 (3)0.58709 (3)0.02978 (11)
N30.87004 (7)0.62185 (8)0.44621 (9)0.0232 (3)
H030.8979 (9)0.6489 (9)0.4222 (12)0.025 (5)*
C310.86325 (9)0.63043 (9)0.53037 (11)0.0222 (4)
C320.81453 (9)0.58886 (10)0.56935 (12)0.0253 (4)
H320.80770.59340.62860.030*
C330.77838 (9)0.54337 (10)0.52223 (12)0.0260 (4)
H330.74690.51600.54940.031*
C340.78643 (9)0.53560 (9)0.43234 (12)0.0248 (4)
C350.74858 (10)0.49143 (11)0.37956 (13)0.0318 (5)
H350.71630.46320.40380.038*
C360.75755 (10)0.48844 (11)0.29307 (13)0.0338 (5)
H360.73160.45840.25790.041*
C370.80522 (10)0.53001 (11)0.25725 (12)0.0311 (4)
H370.81140.52780.19760.037*
C380.84312 (9)0.57379 (10)0.30693 (12)0.0271 (4)
H380.87520.60180.28200.033*
C390.83393 (9)0.57676 (9)0.39479 (11)0.0219 (4)
S40.97719 (3)0.70611 (3)0.33231 (3)0.03334 (12)
N41.02633 (7)0.75843 (8)0.47826 (10)0.0232 (3)
H040.9934 (8)0.7362 (10)0.4982 (12)0.025 (5)*
C411.03125 (9)0.75353 (10)0.39287 (12)0.0254 (4)
C421.08412 (10)0.79153 (10)0.35709 (13)0.0299 (4)
H421.09010.78940.29740.036*
C431.12538 (10)0.83010 (10)0.40710 (13)0.0320 (5)
H431.16020.85420.38180.038*
C441.11820 (9)0.83569 (10)0.49729 (12)0.0275 (4)
C451.15751 (10)0.87664 (11)0.55275 (14)0.0353 (5)
H451.19350.90140.53100.042*
C461.14509 (11)0.88165 (11)0.63745 (14)0.0382 (5)
H461.17180.91020.67380.046*
C471.09273 (10)0.84451 (11)0.67087 (13)0.0333 (5)
H471.08390.84850.72970.040*
C481.05417 (9)0.80237 (10)0.61899 (12)0.0276 (4)
H481.01960.77640.64210.033*
C491.06625 (9)0.79813 (9)0.53189 (11)0.0236 (4)
S50.57183 (3)0.52639 (3)0.39626 (3)0.03448 (12)
N50.51569 (7)0.49100 (8)0.53906 (9)0.0228 (3)
H050.5417 (9)0.5211 (9)0.5629 (12)0.026 (5)*
C510.51897 (9)0.48144 (10)0.45433 (11)0.0235 (4)
C520.47582 (9)0.43085 (10)0.41698 (12)0.0273 (4)
H520.47650.42220.35740.033*
C530.43422 (9)0.39525 (10)0.46456 (12)0.0269 (4)
H530.40610.36210.43790.032*
C540.43171 (9)0.40644 (10)0.55450 (12)0.0254 (4)
C550.39140 (9)0.36942 (11)0.60863 (13)0.0309 (4)
H550.36200.33610.58490.037*
C560.39397 (10)0.38089 (11)0.69520 (14)0.0344 (5)
H560.36640.35580.73100.041*
C570.43750 (10)0.42987 (11)0.73055 (13)0.0328 (5)
H570.43940.43740.79050.039*
C580.47745 (9)0.46704 (10)0.67980 (12)0.0279 (4)
H580.50680.50010.70430.034*
C590.47437 (9)0.45552 (9)0.59156 (12)0.0233 (4)
S60.60393 (3)0.60492 (3)0.65385 (3)0.03778 (13)
N60.65100 (7)0.64641 (8)0.50756 (10)0.0236 (3)
H060.6290 (11)0.6126 (9)0.4857 (14)0.046 (7)*
C610.64934 (9)0.65580 (10)0.59262 (12)0.0266 (4)
C620.68848 (10)0.71035 (10)0.62751 (13)0.0300 (4)
H620.68810.71930.68700.036*
C630.72571 (10)0.74923 (11)0.57835 (13)0.0315 (4)
H630.75090.78520.60350.038*
C640.72779 (9)0.73684 (10)0.48816 (12)0.0256 (4)
C650.76722 (10)0.77391 (11)0.43312 (14)0.0332 (5)
H650.79240.81120.45480.040*
C660.76970 (11)0.75685 (11)0.34874 (13)0.0360 (5)
H660.79700.78190.31250.043*
C670.73214 (10)0.70255 (11)0.31564 (13)0.0318 (4)
H670.73450.69070.25710.038*
C680.69176 (9)0.66616 (10)0.36743 (12)0.0257 (4)
H680.66560.63000.34460.031*
C690.68985 (9)0.68310 (9)0.45388 (12)0.0240 (4)
S70.66694 (2)0.93520 (3)0.66205 (3)0.02775 (11)
N70.62177 (8)0.87677 (8)0.51856 (9)0.0228 (3)
H070.6499 (9)0.9015 (9)0.4944 (12)0.024 (5)*
C710.61644 (9)0.88288 (9)0.60385 (11)0.0222 (4)
C720.56614 (9)0.84280 (10)0.64061 (12)0.0274 (4)
H720.56050.84540.70040.033*
C730.52649 (10)0.80128 (10)0.59220 (12)0.0301 (4)
H730.49350.77530.61850.036*
C740.53331 (9)0.79582 (10)0.50207 (12)0.0275 (4)
C750.49344 (11)0.75431 (11)0.44726 (14)0.0358 (5)
H750.45890.72810.47010.043*
C760.50372 (11)0.75112 (12)0.36161 (14)0.0384 (5)
H760.47670.72250.32560.046*
C770.55386 (10)0.78990 (11)0.32725 (13)0.0336 (5)
H770.56090.78720.26780.040*
C780.59316 (9)0.83191 (10)0.37827 (12)0.0278 (4)
H780.62670.85870.35430.033*
C790.58307 (9)0.83475 (9)0.46602 (11)0.0234 (4)
S80.73176 (3)0.95669 (3)0.40555 (3)0.03450 (12)
N80.77999 (8)1.01220 (8)0.54994 (9)0.0235 (3)
H080.7496 (10)0.9872 (11)0.5746 (14)0.045 (7)*
C810.78417 (9)1.00670 (10)0.46482 (11)0.0242 (4)
C820.83538 (10)1.04614 (10)0.42755 (12)0.0289 (4)
H820.84021.04420.36760.035*
C830.87674 (10)1.08580 (10)0.47606 (13)0.0304 (4)
H830.91061.11060.44970.037*
C840.87061 (9)1.09114 (10)0.56624 (12)0.0267 (4)
C850.91119 (11)1.13227 (11)0.62019 (13)0.0339 (5)
H850.94561.15830.59690.041*
C860.90156 (11)1.13525 (11)0.70658 (13)0.0356 (5)
H860.92911.16340.74250.043*
C870.85107 (10)1.09678 (10)0.74129 (12)0.0303 (4)
H870.84461.09920.80090.036*
C880.81064 (9)1.05550 (10)0.69065 (11)0.0263 (4)
H880.77671.02940.71490.032*
C890.82024 (9)1.05250 (9)0.60269 (11)0.0230 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0369 (3)0.0363 (3)0.0234 (2)0.0121 (2)0.0056 (2)0.0032 (2)
N10.0251 (8)0.0217 (9)0.0225 (8)0.0034 (7)0.0017 (6)0.0024 (6)
C110.0231 (9)0.0242 (10)0.0247 (9)0.0023 (8)0.0014 (7)0.0019 (7)
C120.0289 (10)0.0277 (11)0.0241 (9)0.0014 (8)0.0009 (8)0.0042 (8)
C130.0275 (10)0.0284 (11)0.0318 (10)0.0041 (8)0.0027 (8)0.0054 (8)
C140.0234 (9)0.0249 (10)0.0307 (10)0.0000 (8)0.0003 (8)0.0000 (8)
C150.0304 (10)0.0334 (12)0.0374 (11)0.0086 (9)0.0028 (9)0.0007 (9)
C160.0305 (11)0.0356 (12)0.0362 (11)0.0033 (9)0.0095 (9)0.0061 (9)
C170.0330 (10)0.0339 (12)0.0261 (10)0.0010 (9)0.0061 (8)0.0007 (8)
C180.0269 (10)0.0242 (10)0.0276 (10)0.0024 (8)0.0022 (8)0.0025 (8)
C190.0211 (9)0.0230 (10)0.0260 (9)0.0012 (7)0.0027 (7)0.0008 (7)
S20.0395 (3)0.0430 (3)0.0246 (2)0.0177 (2)0.0095 (2)0.0066 (2)
N20.0242 (8)0.0221 (8)0.0222 (8)0.0034 (7)0.0024 (6)0.0029 (6)
C210.0225 (9)0.0266 (11)0.0233 (9)0.0008 (8)0.0013 (7)0.0025 (7)
C220.0277 (10)0.0307 (11)0.0242 (9)0.0017 (8)0.0013 (7)0.0056 (8)
C230.0241 (9)0.0312 (11)0.0331 (10)0.0048 (8)0.0021 (8)0.0059 (8)
C240.0230 (9)0.0253 (11)0.0298 (10)0.0005 (8)0.0000 (7)0.0026 (8)
C250.0293 (10)0.0328 (12)0.0384 (11)0.0103 (9)0.0002 (9)0.0052 (9)
C260.0330 (11)0.0387 (13)0.0384 (11)0.0045 (9)0.0073 (9)0.0123 (10)
C270.0331 (11)0.0333 (11)0.0247 (9)0.0026 (9)0.0042 (8)0.0033 (8)
C280.0264 (9)0.0241 (10)0.0261 (9)0.0011 (8)0.0006 (7)0.0017 (7)
C290.0204 (9)0.0219 (10)0.0257 (9)0.0025 (7)0.0013 (7)0.0034 (7)
S30.0349 (3)0.0326 (3)0.0222 (2)0.0104 (2)0.0045 (2)0.00193 (19)
N30.0237 (8)0.0226 (9)0.0237 (8)0.0038 (6)0.0048 (6)0.0008 (6)
C310.0223 (9)0.0210 (9)0.0236 (9)0.0012 (7)0.0030 (7)0.0027 (7)
C320.0285 (10)0.0248 (10)0.0231 (9)0.0021 (8)0.0056 (7)0.0054 (7)
C330.0272 (9)0.0224 (10)0.0289 (10)0.0026 (8)0.0053 (8)0.0072 (8)
C340.0249 (9)0.0196 (9)0.0300 (10)0.0011 (7)0.0011 (7)0.0027 (7)
C350.0316 (10)0.0259 (11)0.0377 (12)0.0059 (9)0.0006 (9)0.0028 (9)
C360.0343 (11)0.0305 (12)0.0357 (11)0.0053 (9)0.0058 (9)0.0046 (9)
C370.0341 (10)0.0333 (12)0.0258 (10)0.0025 (9)0.0009 (8)0.0051 (8)
C380.0255 (9)0.0275 (11)0.0290 (10)0.0002 (8)0.0063 (8)0.0002 (8)
C390.0229 (9)0.0195 (9)0.0233 (9)0.0011 (7)0.0007 (7)0.0002 (7)
S40.0414 (3)0.0351 (3)0.0243 (2)0.0125 (2)0.0095 (2)0.0045 (2)
N40.0230 (8)0.0227 (8)0.0244 (8)0.0012 (7)0.0059 (6)0.0017 (6)
C410.0299 (10)0.0214 (10)0.0257 (10)0.0012 (8)0.0084 (8)0.0026 (7)
C420.0339 (10)0.0257 (11)0.0317 (10)0.0021 (8)0.0153 (8)0.0017 (8)
C430.0284 (10)0.0271 (11)0.0414 (12)0.0018 (8)0.0114 (9)0.0064 (9)
C440.0247 (9)0.0226 (10)0.0350 (10)0.0008 (8)0.0009 (8)0.0072 (8)
C450.0304 (11)0.0275 (12)0.0472 (13)0.0065 (9)0.0056 (9)0.0098 (9)
C460.0410 (12)0.0311 (12)0.0404 (12)0.0053 (10)0.0174 (10)0.0033 (9)
C470.0343 (11)0.0350 (12)0.0297 (10)0.0027 (9)0.0061 (9)0.0020 (9)
C480.0229 (9)0.0305 (11)0.0288 (10)0.0014 (8)0.0041 (8)0.0047 (8)
C490.0211 (9)0.0208 (10)0.0286 (9)0.0040 (7)0.0012 (7)0.0016 (7)
S50.0383 (3)0.0408 (3)0.0246 (2)0.0157 (2)0.0043 (2)0.0019 (2)
N50.0210 (8)0.0238 (9)0.0237 (8)0.0037 (6)0.0012 (6)0.0029 (6)
C510.0218 (9)0.0245 (10)0.0240 (9)0.0011 (7)0.0003 (7)0.0002 (7)
C520.0278 (9)0.0266 (11)0.0266 (9)0.0006 (8)0.0058 (8)0.0035 (8)
C530.0239 (9)0.0238 (10)0.0321 (10)0.0035 (8)0.0067 (8)0.0015 (8)
C540.0194 (8)0.0233 (10)0.0332 (10)0.0028 (7)0.0013 (7)0.0018 (8)
C550.0240 (10)0.0279 (11)0.0407 (12)0.0055 (8)0.0014 (8)0.0034 (9)
C560.0296 (10)0.0328 (12)0.0415 (12)0.0035 (9)0.0103 (9)0.0083 (9)
C570.0339 (11)0.0372 (12)0.0282 (10)0.0013 (9)0.0086 (8)0.0011 (9)
C580.0269 (9)0.0262 (11)0.0310 (10)0.0018 (8)0.0048 (8)0.0022 (8)
C590.0205 (9)0.0220 (10)0.0276 (9)0.0030 (7)0.0021 (7)0.0025 (7)
S60.0407 (3)0.0466 (3)0.0269 (3)0.0182 (3)0.0089 (2)0.0082 (2)
N60.0219 (8)0.0225 (9)0.0260 (8)0.0040 (7)0.0011 (6)0.0017 (7)
C610.0205 (9)0.0299 (11)0.0292 (10)0.0008 (8)0.0006 (7)0.0039 (8)
C620.0262 (9)0.0322 (11)0.0316 (10)0.0017 (8)0.0014 (8)0.0097 (8)
C630.0235 (9)0.0286 (11)0.0421 (11)0.0045 (8)0.0014 (8)0.0097 (9)
C640.0206 (9)0.0230 (10)0.0328 (10)0.0011 (7)0.0030 (7)0.0012 (8)
C650.0278 (10)0.0267 (11)0.0444 (12)0.0058 (8)0.0046 (9)0.0035 (9)
C660.0330 (11)0.0364 (12)0.0383 (12)0.0074 (9)0.0004 (9)0.0155 (9)
C670.0350 (11)0.0319 (12)0.0281 (10)0.0019 (9)0.0019 (8)0.0081 (8)
C680.0273 (9)0.0228 (10)0.0265 (9)0.0011 (8)0.0033 (7)0.0034 (7)
C690.0194 (9)0.0209 (9)0.0315 (10)0.0031 (7)0.0002 (7)0.0039 (7)
S70.0325 (3)0.0303 (3)0.0207 (2)0.0059 (2)0.00357 (18)0.00005 (19)
N70.0231 (8)0.0241 (9)0.0213 (8)0.0017 (7)0.0038 (6)0.0013 (6)
C710.0234 (9)0.0198 (10)0.0236 (9)0.0051 (7)0.0040 (7)0.0017 (7)
C720.0297 (10)0.0263 (10)0.0267 (9)0.0019 (8)0.0081 (8)0.0051 (8)
C730.0313 (10)0.0253 (11)0.0341 (11)0.0039 (8)0.0067 (8)0.0056 (8)
C740.0263 (10)0.0228 (10)0.0335 (10)0.0008 (8)0.0028 (8)0.0009 (8)
C750.0365 (11)0.0286 (12)0.0423 (12)0.0082 (9)0.0014 (9)0.0024 (9)
C760.0377 (12)0.0309 (12)0.0459 (13)0.0061 (10)0.0050 (10)0.0097 (10)
C770.0353 (11)0.0364 (12)0.0290 (10)0.0012 (9)0.0008 (8)0.0060 (9)
C780.0257 (9)0.0296 (11)0.0281 (10)0.0007 (8)0.0030 (8)0.0034 (8)
C790.0223 (9)0.0221 (10)0.0257 (9)0.0024 (7)0.0003 (7)0.0003 (7)
S80.0436 (3)0.0377 (3)0.0229 (2)0.0159 (2)0.0082 (2)0.0056 (2)
N80.0239 (8)0.0239 (9)0.0230 (8)0.0025 (7)0.0042 (6)0.0002 (6)
C810.0278 (9)0.0227 (10)0.0225 (9)0.0006 (8)0.0057 (7)0.0005 (7)
C820.0324 (10)0.0292 (11)0.0259 (10)0.0032 (8)0.0094 (8)0.0016 (8)
C830.0316 (10)0.0271 (11)0.0332 (11)0.0038 (8)0.0080 (8)0.0052 (8)
C840.0267 (9)0.0230 (10)0.0305 (10)0.0017 (8)0.0013 (8)0.0027 (8)
C850.0357 (11)0.0275 (11)0.0382 (11)0.0070 (9)0.0018 (9)0.0039 (9)
C860.0408 (12)0.0288 (12)0.0359 (11)0.0018 (9)0.0108 (9)0.0022 (9)
C870.0358 (10)0.0312 (11)0.0232 (9)0.0052 (9)0.0045 (8)0.0016 (8)
C880.0253 (9)0.0268 (11)0.0267 (9)0.0032 (8)0.0009 (7)0.0010 (8)
C890.0220 (9)0.0221 (10)0.0248 (9)0.0036 (7)0.0002 (7)0.0006 (7)
Geometric parameters (Å, º) top
S1—C111.6856 (19)C72—C731.351 (3)
N1—C111.350 (2)C73—C741.429 (3)
N1—C191.391 (2)C74—C791.403 (3)
C11—C121.433 (3)C74—C751.409 (3)
C12—C131.351 (3)C75—C761.369 (3)
C13—C141.436 (3)C76—C771.396 (3)
C14—C191.402 (3)C77—C781.375 (3)
C14—C151.404 (3)C78—C791.401 (2)
C15—C161.376 (3)S8—C811.689 (2)
C16—C171.392 (3)N8—C811.345 (2)
C17—C181.378 (3)N8—C891.381 (2)
C18—C191.397 (3)C81—C821.439 (3)
S2—C211.6892 (19)C82—C831.349 (3)
N2—C211.351 (2)C83—C841.428 (3)
N2—C291.379 (2)C84—C851.405 (3)
C21—C221.431 (3)C84—C891.412 (3)
C22—C231.353 (3)C85—C861.378 (3)
C23—C241.432 (3)C86—C871.400 (3)
C24—C291.405 (3)C87—C881.376 (3)
C24—C251.409 (3)C88—C891.402 (3)
C25—C261.371 (3)N1—H010.863 (14)
C26—C271.402 (3)C12—H120.9500
C27—C281.372 (3)C13—H130.9500
C28—C291.403 (2)C15—H150.9500
S3—C311.6887 (19)C16—H160.9500
N3—C311.343 (2)C17—H170.9500
N3—C391.385 (2)C18—H180.9500
C31—C321.439 (2)N2—H020.864 (14)
C32—C331.354 (3)C22—H220.9500
C33—C341.434 (3)C23—H230.9500
C34—C351.402 (3)C25—H250.9500
C34—C391.407 (3)C26—H260.9500
C35—C361.377 (3)C27—H270.9500
C36—C371.402 (3)C28—H280.9500
C37—C381.371 (3)N3—H030.874 (13)
C38—C391.399 (2)C32—H320.9500
S4—C411.689 (2)C33—H330.9500
N4—C411.350 (2)C35—H350.9500
N4—C491.378 (2)C36—H360.9500
C41—C421.438 (3)C37—H370.9500
C42—C431.348 (3)C38—H380.9500
C43—C441.432 (3)N4—H040.866 (13)
C44—C451.403 (3)C42—H420.9500
C44—C491.411 (3)C43—H430.9500
C45—C461.366 (3)C45—H450.9500
C46—C471.405 (3)C46—H460.9500
C47—C481.377 (3)C47—H470.9500
C48—C491.400 (3)C48—H480.9500
S5—C511.6876 (19)N5—H050.865 (14)
N5—C511.346 (2)C52—H520.9500
N5—C591.389 (2)C53—H530.9500
C51—C521.432 (3)C55—H550.9500
C52—C531.348 (3)C56—H560.9500
C53—C541.430 (3)C57—H570.9500
C54—C591.404 (3)C58—H580.9500
C54—C551.409 (3)N6—H060.867 (14)
C55—C561.373 (3)C62—H620.9500
C56—C571.403 (3)C63—H630.9500
C57—C581.373 (3)C65—H650.9500
C58—C591.399 (3)C66—H660.9500
S6—C611.693 (2)C67—H670.9500
N6—C611.347 (2)C68—H680.9500
N6—C691.384 (2)N7—H070.851 (13)
C61—C621.432 (3)C72—H720.9500
C62—C631.345 (3)C73—H730.9500
C63—C641.437 (3)C75—H750.9500
C64—C691.404 (3)C76—H760.9500
C64—C651.408 (3)C77—H770.9500
C65—C661.368 (3)C78—H780.9500
C66—C671.402 (3)N8—H080.888 (14)
C67—C681.380 (3)C82—H820.9500
C68—C691.398 (3)C83—H830.9500
S7—C711.6859 (19)C85—H850.9500
N7—C711.351 (2)C86—H860.9500
N7—C791.383 (2)C87—H870.9500
C71—C721.429 (3)C88—H880.9500
C11—N1—C19124.79 (16)C89—C84—C83117.33 (17)
N1—C11—C12116.29 (17)C86—C85—C84120.7 (2)
N1—C11—S1121.67 (14)C85—C86—C87119.88 (19)
C12—C11—S1122.04 (14)C88—C87—C86121.18 (18)
C13—C12—C11121.51 (17)C87—C88—C89119.04 (18)
C12—C13—C14121.00 (18)N8—C89—C88120.48 (17)
C19—C14—C15118.41 (18)N8—C89—C84118.77 (16)
C19—C14—C13117.58 (17)C88—C89—C84120.74 (17)
C15—C14—C13123.99 (18)C11—N1—H01120.9 (14)
C16—C15—C14120.50 (19)C19—N1—H01114.3 (14)
C15—C16—C17120.16 (19)C13—C12—H12119.2
C18—C17—C16120.88 (18)C11—C12—H12119.2
C17—C18—C19119.01 (18)C12—C13—H13119.5
N1—C19—C18120.16 (17)C14—C13—H13119.5
N1—C19—C14118.82 (16)C16—C15—H15119.7
C18—C19—C14121.02 (17)C14—C15—H15119.7
C21—N2—C29124.91 (16)C15—C16—H16119.9
N2—C21—C22116.33 (16)C17—C16—H16119.9
N2—C21—S2121.40 (14)C18—C17—H17119.6
C22—C21—S2122.27 (14)C16—C17—H17119.6
C23—C22—C21121.23 (17)C17—C18—H18120.5
C22—C23—C24121.12 (18)C19—C18—H18120.5
C29—C24—C25118.52 (18)C21—N2—H02116.2 (14)
C29—C24—C23117.40 (17)C29—N2—H02118.8 (14)
C25—C24—C23124.08 (19)C23—C22—H22119.4
C26—C25—C24120.5 (2)C21—C22—H22119.4
C25—C26—C27120.02 (19)C22—C23—H23119.4
C28—C27—C26121.05 (18)C24—C23—H23119.4
C27—C28—C29119.09 (18)C26—C25—H25119.7
N2—C29—C28120.25 (17)C24—C25—H25119.7
N2—C29—C24118.98 (16)C25—C26—H26120.0
C28—C29—C24120.77 (17)C27—C26—H26120.0
C31—N3—C39125.25 (16)C28—C27—H27119.5
N3—C31—C32116.63 (16)C26—C27—H27119.5
N3—C31—S3121.60 (14)C27—C28—H28120.5
C32—C31—S3121.76 (14)C29—C28—H28120.5
C33—C32—C31120.56 (17)C31—N3—H03116.3 (13)
C32—C33—C34121.56 (17)C39—N3—H03118.4 (13)
C35—C34—C39118.38 (17)C33—C32—H32119.7
C35—C34—C33124.19 (17)C31—C32—H32119.7
C39—C34—C33117.40 (17)C32—C33—H33119.2
C36—C35—C34120.87 (19)C34—C33—H33119.2
C35—C36—C37119.62 (19)C36—C35—H35119.6
C38—C37—C36121.09 (18)C34—C35—H35119.6
C37—C38—C39119.21 (18)C35—C36—H36120.2
N3—C39—C38120.55 (17)C37—C36—H36120.2
N3—C39—C34118.58 (16)C38—C37—H37119.5
C38—C39—C34120.84 (17)C36—C37—H37119.5
C41—N4—C49125.14 (16)C37—C38—H38120.4
N4—C41—C42116.19 (17)C39—C38—H38120.4
N4—C41—S4121.27 (14)C41—N4—H04114.6 (13)
C42—C41—S4122.53 (14)C49—N4—H04120.1 (13)
C43—C42—C41120.94 (18)C43—C42—H42119.5
C42—C43—C44121.85 (18)C41—C42—H42119.5
C45—C44—C49118.08 (18)C42—C43—H43119.1
C45—C44—C43125.07 (18)C44—C43—H43119.1
C49—C44—C43116.82 (18)C46—C45—H45119.3
C46—C45—C44121.3 (2)C44—C45—H45119.3
C45—C46—C47120.0 (2)C45—C46—H46120.0
C48—C47—C46120.45 (19)C47—C46—H46120.0
C47—C48—C49119.49 (18)C48—C47—H47119.8
N4—C49—C48120.31 (17)C46—C47—H47119.8
N4—C49—C44119.02 (16)C47—C48—H48120.3
C48—C49—C44120.65 (18)C49—C48—H48120.3
C51—N5—C59124.93 (16)C51—N5—H05117.6 (14)
N5—C51—C52116.31 (17)C59—N5—H05117.4 (14)
N5—C51—S5121.36 (14)C53—C52—H52119.3
C52—C51—S5122.33 (14)C51—C52—H52119.3
C53—C52—C51121.41 (17)C52—C53—H53119.4
C52—C53—C54121.14 (17)C54—C53—H53119.4
C59—C54—C55118.09 (17)C56—C55—H55119.5
C59—C54—C53117.67 (17)C54—C55—H55119.5
C55—C54—C53124.18 (18)C55—C56—H56120.1
C56—C55—C54120.92 (19)C57—C56—H56120.1
C55—C56—C57119.74 (18)C58—C57—H57119.5
C58—C57—C56121.00 (19)C56—C57—H57119.5
C57—C58—C59119.10 (18)C57—C58—H58120.5
N5—C59—C58120.28 (17)C59—C58—H58120.5
N5—C59—C54118.53 (17)C61—N6—H06117.5 (16)
C58—C59—C54121.14 (17)C69—N6—H06117.5 (16)
C61—N6—C69124.82 (16)C63—C62—H62119.1
N6—C61—C62116.21 (17)C61—C62—H62119.1
N6—C61—S6121.23 (15)C62—C63—H63119.7
C62—C61—S6122.55 (15)C64—C63—H63119.7
C63—C62—C61121.84 (18)C66—C65—H65119.7
C62—C63—C64120.60 (18)C64—C65—H65119.7
C69—C64—C65118.40 (17)C65—C66—H66119.9
C69—C64—C63117.68 (17)C67—C66—H66119.9
C65—C64—C63123.89 (18)C68—C67—H67119.8
C66—C65—C64120.70 (19)C66—C67—H67119.8
C65—C66—C67120.24 (19)C67—C68—H68120.4
C68—C67—C66120.49 (19)C69—C68—H68120.4
C67—C68—C69119.24 (18)C71—N7—H07118.4 (14)
N6—C69—C68120.36 (17)C79—N7—H07116.6 (13)
N6—C69—C64118.74 (17)C73—C72—H72119.3
C68—C69—C64120.90 (17)C71—C72—H72119.3
C71—N7—C79124.93 (16)C72—C73—H73119.4
N7—C71—C72116.20 (17)C74—C73—H73119.4
N7—C71—S7120.96 (14)C76—C75—H75119.5
C72—C71—S7122.84 (14)C74—C75—H75119.5
C73—C72—C71121.41 (17)C75—C76—H76120.0
C72—C73—C74121.16 (18)C77—C76—H76120.0
C79—C74—C75118.03 (18)C78—C77—H77119.6
C79—C74—C73117.48 (18)C76—C77—H77119.6
C75—C74—C73124.49 (18)C77—C78—H78120.4
C76—C75—C74121.0 (2)C79—C78—H78120.4
C75—C76—C77120.0 (2)C81—N8—H08117.6 (15)
C78—C77—C76120.88 (19)C89—N8—H08117.2 (15)
C77—C78—C79119.18 (19)C83—C82—H82119.3
N7—C79—C78120.25 (17)C81—C82—H82119.3
N7—C79—C74118.82 (16)C82—C83—H83119.4
C78—C79—C74120.92 (17)C84—C83—H83119.4
C81—N8—C89125.18 (16)C86—C85—H85119.7
N8—C81—C82116.12 (17)C84—C85—H85119.7
N8—C81—S8121.62 (14)C85—C86—H86120.1
C82—C81—S8122.27 (14)C87—C86—H86120.1
C83—C82—C81121.33 (17)C88—C87—H87119.4
C82—C83—C84121.26 (18)C86—C87—H87119.4
C85—C84—C89118.49 (17)C87—C88—H88120.5
C85—C84—C83124.18 (18)C89—C88—H88120.5
C19—N1—C11—C120.5 (3)C59—N5—C51—C520.4 (3)
C19—N1—C11—S1179.85 (14)C59—N5—C51—S5179.00 (14)
N1—C11—C12—C130.6 (3)N5—C51—C52—C530.2 (3)
S1—C11—C12—C13179.70 (16)S5—C51—C52—C53179.64 (15)
C11—C12—C13—C140.3 (3)C51—C52—C53—C540.2 (3)
C12—C13—C14—C190.2 (3)C52—C53—C54—C590.4 (3)
C12—C13—C14—C15178.7 (2)C52—C53—C54—C55177.47 (19)
C19—C14—C15—C161.1 (3)C59—C54—C55—C560.2 (3)
C13—C14—C15—C16179.7 (2)C53—C54—C55—C56176.87 (19)
C14—C15—C16—C170.4 (3)C54—C55—C56—C570.3 (3)
C15—C16—C17—C180.6 (3)C55—C56—C57—C580.4 (3)
C16—C17—C18—C190.9 (3)C56—C57—C58—C590.0 (3)
C11—N1—C19—C18179.77 (18)C51—N5—C59—C58176.60 (18)
C11—N1—C19—C140.0 (3)C51—N5—C59—C541.0 (3)
C17—C18—C19—N1179.97 (17)C57—C58—C59—N5178.07 (17)
C17—C18—C19—C140.2 (3)C57—C58—C59—C540.5 (3)
C15—C14—C19—N1178.95 (17)C55—C54—C59—N5178.23 (16)
C13—C14—C19—N10.3 (3)C53—C54—C59—N51.0 (2)
C15—C14—C19—C180.8 (3)C55—C54—C59—C580.6 (3)
C13—C14—C19—C18179.43 (17)C53—C54—C59—C58176.64 (17)
C29—N2—C21—C221.4 (3)C69—N6—C61—C623.4 (3)
C29—N2—C21—S2178.47 (14)C69—N6—C61—S6175.96 (14)
N2—C21—C22—C230.3 (3)N6—C61—C62—C631.1 (3)
S2—C21—C22—C23179.63 (16)S6—C61—C62—C63178.20 (16)
C21—C22—C23—C240.6 (3)C61—C62—C63—C640.4 (3)
C22—C23—C24—C290.5 (3)C62—C63—C64—C690.0 (3)
C22—C23—C24—C25179.11 (19)C62—C63—C64—C65177.84 (19)
C29—C24—C25—C261.5 (3)C69—C64—C65—C661.6 (3)
C23—C24—C25—C26178.1 (2)C63—C64—C65—C66176.2 (2)
C24—C25—C26—C270.9 (3)C64—C65—C66—C670.9 (3)
C25—C26—C27—C280.3 (3)C65—C66—C67—C680.7 (3)
C26—C27—C28—C291.0 (3)C66—C67—C68—C691.4 (3)
C21—N2—C29—C28177.81 (17)C61—N6—C69—C68175.23 (17)
C21—N2—C29—C241.6 (3)C61—N6—C69—C643.9 (3)
C27—C28—C29—N2179.01 (17)C67—C68—C69—N6178.47 (17)
C27—C28—C29—C240.4 (3)C67—C68—C69—C640.7 (3)
C25—C24—C29—N2179.79 (17)C65—C64—C69—N6179.97 (17)
C23—C24—C29—N20.6 (3)C63—C64—C69—N62.0 (3)
C25—C24—C29—C280.8 (3)C65—C64—C69—C680.8 (3)
C23—C24—C29—C28178.82 (17)C63—C64—C69—C68177.12 (17)
C39—N3—C31—C320.3 (3)C79—N7—C71—C720.7 (3)
C39—N3—C31—S3178.66 (14)C79—N7—C71—S7179.32 (14)
N3—C31—C32—C330.5 (3)N7—C71—C72—C730.1 (3)
S3—C31—C32—C33179.45 (15)S7—C71—C72—C73179.94 (16)
C31—C32—C33—C340.9 (3)C71—C72—C73—C740.0 (3)
C32—C33—C34—C35177.25 (19)C72—C73—C74—C790.5 (3)
C32—C33—C34—C390.6 (3)C72—C73—C74—C75179.3 (2)
C39—C34—C35—C360.1 (3)C79—C74—C75—C761.2 (3)
C33—C34—C35—C36177.67 (19)C73—C74—C75—C76179.0 (2)
C34—C35—C36—C370.1 (3)C74—C75—C76—C770.7 (3)
C35—C36—C37—C380.1 (3)C75—C76—C77—C780.4 (3)
C36—C37—C38—C390.1 (3)C76—C77—C78—C791.0 (3)
C31—N3—C39—C38177.42 (18)C71—N7—C79—C78179.48 (17)
C31—N3—C39—C340.6 (3)C71—N7—C79—C741.2 (3)
C37—C38—C39—N3178.09 (17)C77—C78—C79—N7179.76 (18)
C37—C38—C39—C340.1 (3)C77—C78—C79—C740.5 (3)
C35—C34—C39—N3178.14 (17)C75—C74—C79—N7178.72 (17)
C33—C34—C39—N30.2 (3)C73—C74—C79—N71.1 (3)
C35—C34—C39—C380.1 (3)C75—C74—C79—C780.6 (3)
C33—C34—C39—C38177.84 (17)C73—C74—C79—C78179.62 (18)
C49—N4—C41—C422.1 (3)C89—N8—C81—C820.4 (3)
C49—N4—C41—S4176.98 (14)C89—N8—C81—S8179.13 (14)
N4—C41—C42—C430.7 (3)N8—C81—C82—C830.4 (3)
S4—C41—C42—C43178.42 (16)S8—C81—C82—C83179.99 (17)
C41—C42—C43—C440.7 (3)C81—C82—C83—C841.1 (3)
C42—C43—C44—C45177.5 (2)C82—C83—C84—C85178.9 (2)
C42—C43—C44—C490.8 (3)C82—C83—C84—C891.0 (3)
C49—C44—C45—C461.7 (3)C89—C84—C85—C860.6 (3)
C43—C44—C45—C46176.6 (2)C83—C84—C85—C86179.2 (2)
C44—C45—C46—C471.1 (3)C84—C85—C86—C870.3 (3)
C45—C46—C47—C480.7 (3)C85—C86—C87—C880.2 (3)
C46—C47—C48—C491.8 (3)C86—C87—C88—C890.4 (3)
C41—N4—C49—C48176.25 (18)C81—N8—C89—C88178.68 (17)
C41—N4—C49—C442.1 (3)C81—N8—C89—C840.6 (3)
C47—C48—C49—N4177.21 (17)C87—C88—C89—N8179.21 (17)
C47—C48—C49—C441.1 (3)C87—C88—C89—C840.0 (3)
C45—C44—C49—N4178.94 (17)C85—C84—C89—N8179.72 (17)
C43—C44—C49—N40.5 (3)C83—C84—C89—N80.1 (3)
C45—C44—C49—C480.6 (3)C85—C84—C89—C880.5 (3)
C43—C44—C49—C48177.82 (17)C83—C84—C89—C88179.39 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H01···S20.86 (1)2.48 (1)3.3345 (17)174 (2)
N2—H02···S10.86 (1)2.47 (1)3.3166 (16)167 (2)
N3—H03···S40.87 (1)2.46 (1)3.3156 (16)168 (2)
N4—H04···S30.87 (1)2.44 (1)3.2898 (16)166 (2)
N5—H05···S60.87 (1)2.49 (1)3.3431 (17)170 (2)
N6—H06···S50.87 (1)2.46 (2)3.3149 (16)169 (2)
N7—H07···S80.85 (1)2.46 (1)3.3037 (16)170 (2)
N8—H08···S70.89 (1)2.43 (1)3.3109 (16)169 (2)
C18—H18···S20.952.983.768 (2)141
C28—H28···S10.952.933.719 (2)141
C38—H38···S40.952.993.767 (2)140
C48—H48···S30.952.933.708 (2)140
C58—H58···S60.952.993.772 (2)141
C68—H68···S50.952.933.720 (2)141
C78—H78···S80.952.953.732 (2)141
C88—H88···S70.952.973.751 (2)140
C28—H28···S3i0.953.053.701 (2)127
C72—H72···S4ii0.952.913.6996 (19)142
C12—H12···S7i0.952.853.6091 (19)138
C26—H26···S7iii0.952.953.845 (2)157
Symmetry codes: (i) x, y+1, z1/2; (ii) x1/2, y+3/2, z+1/2; (iii) x+1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC9H7NS
Mr161.22
Crystal system, space groupMonoclinic, Cc
Temperature (K)133
a, b, c (Å)19.9772 (14), 19.9588 (14), 15.6622 (11)
β (°) 93.014 (4)
V3)6236.2 (8)
Z32
Radiation typeMo Kα
µ (mm1)0.34
Crystal size (mm)0.28 × 0.24 × 0.24
Data collection
DiffractometerBruker SMART1000 CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
44742, 15776, 12944
Rint0.034
(sin θ/λ)max1)0.676
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.078, 0.96
No. of reflections15776
No. of parameters825
No. of restraints30
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.33, 0.18
Absolute structureFlack (1983)
Absolute structure parameter0.03 (3)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) top
S1—C111.6856 (19)S5—C511.6876 (19)
N1—C111.350 (2)N5—C511.346 (2)
N1—C191.391 (2)N5—C591.389 (2)
C12—C131.351 (3)C52—C531.348 (3)
C13—C141.436 (3)C53—C541.430 (3)
S2—C211.6892 (19)S6—C611.693 (2)
N2—C211.351 (2)N6—C611.347 (2)
N2—C291.379 (2)N6—C691.384 (2)
C22—C231.353 (3)C62—C631.345 (3)
C23—C241.432 (3)C63—C641.437 (3)
S3—C311.6887 (19)S7—C711.6859 (19)
N3—C311.343 (2)N7—C711.351 (2)
N3—C391.385 (2)N7—C791.383 (2)
C32—C331.354 (3)C72—C731.351 (3)
C33—C341.434 (3)C73—C741.429 (3)
S4—C411.689 (2)S8—C811.689 (2)
N4—C411.350 (2)N8—C811.345 (2)
N4—C491.378 (2)N8—C891.381 (2)
C42—C431.348 (3)C82—C831.349 (3)
C43—C441.432 (3)C83—C841.428 (3)
C11—N1—C19124.79 (16)C51—N5—C59124.93 (16)
C21—N2—C29124.91 (16)C61—N6—C69124.82 (16)
C31—N3—C39125.25 (16)C71—N7—C79124.93 (16)
C41—N4—C49125.14 (16)C81—N8—C89125.18 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H01···S20.863 (14)2.475 (14)3.3345 (17)174.2 (19)
N2—H02···S10.864 (14)2.468 (14)3.3166 (16)167.2 (19)
N3—H03···S40.874 (13)2.456 (14)3.3156 (16)168.0 (18)
N4—H04···S30.866 (13)2.444 (14)3.2898 (16)165.8 (18)
N5—H05···S60.865 (14)2.488 (14)3.3431 (17)169.7 (18)
N6—H06···S50.867 (14)2.461 (15)3.3149 (16)169 (2)
N7—H07···S80.851 (13)2.463 (14)3.3037 (16)169.7 (18)
N8—H08···S70.888 (14)2.434 (14)3.3109 (16)169 (2)
C18—H18···S20.952.983.768 (2)141
C28—H28···S3i0.953.053.701 (2)127
C72—H72···S4ii0.952.913.6996 (19)142
C12—H12···S7i0.952.853.6091 (19)138
C26—H26···S7iii0.952.953.845 (2)157
Symmetry codes: (i) x, y+1, z1/2; (ii) x1/2, y+3/2, z+1/2; (iii) x+1/2, y+3/2, z1/2.
Librationally corrected bond lengths (Å) top
Bondmol. 1mol. 2mol. 3mol. 4mol. 5mol. 6mol. 7mol. 8
SC11.6891.6931.6921.6931.6911.6971.6891.692
N—C11.3521.3531.3451.3521.3481.3501.3531.347
C1—C21.4371.4361.4431.4411.4371.4361.4331.443
C2—C31.3541.3571.3571.3511.3501.3481.3541.352
C3—C41.4381.4341.4361.4341.4331.4401.4321.430
C4—C51.4071.4121.4051.4051.4121.4111.4121.407
C5—C61.3781.3741.3791.3691.3761.3711.3721.380
C6—C71.3961.4061.4061.4091.4071.4061.4001.404
C7—C81.3801.3751.3741.3791.3761.3831.3781.379
N—C91.3931.3821.3871.3811.3921.3871.3851.383
C4—C91.4061.4091.4111.4151.4081.4081.4081.416
C8—C91.4001.4081.4011.4031.4021.4011.4031.405
 

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