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organic compounds
Supramolecular structures of four (Z)-5-arylmethylene-2-thioxothiazolidin-4-ones: hydrogen-bonded dimers, chains of rings and sheets
aGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk
In each of the four title compounds, namely (Z)-5-benzylidene-2-thioxothiazolidin-4-one, C10H7NOS2, (I), which crystallizes with Z′ = 2 in P21/n, (Z)-5-(4-methylbenzylidene)-2-thioxothiazolidin-4-one, C11H9NOS2, (II), (Z)-2-thioxo-5-[4-(trifluoromethyl)benzylidene]thiazolidin-4-one, C11H6F3NOS2, (III), and (Z)-5-(4-methoxybenzylidene)-2-thioxothiazolidin-4-one, C11H9NO2S2, (IV), there is a very wide C—C—C angle (ca 130°) at the methine C atom linking the two rings. Pairs of N—H⋯O hydrogen bonds link the two independent molecules in (I) into a cyclic dimeric unit, and these units are further linked into complex sheets by three independent C—H⋯π(arene) hydrogen bonds. The molecules of (II) are linked by paired N—H⋯O hydrogen bonds into centrosymmetric R22(8) dimers; the molecules of (III) and (IV) are linked into chains of rings, which are constructed from a combination of N—H⋯S and C—H⋯O hydrogen bonds in (III), and from a combination of N—H⋯O and C—H⋯S hydrogen bonds in (IV).
Comment
As part of a programme for the synthesis of new fused heterocyclic systems of potential biological application, we have been evaluating the use of (Z)-5-arylmethylene-2-thioxothiazolidin-4-ones as intermediates for cyclocondensation reactions, and we report here the structures of four such compounds, (I)–(IV), which have themselves been prepared by condensation of rhodanine (2-thioxothiazolidin-4-one) with arylaldehydes using microwave irradiation in a solvent-free system.
The structure of (IV) has been reported previously (Okazaki et al., 1998
) using diffraction data collected at ambient temperature; however, no discussion of the supramolecular structure was given and there are no atomic coordinates deposited in the Cambridge Structural Database (Allen, 2002
; refcode GOVXIY). Compound (I)
crystallizes in P21/n with Z′ = 2, while compounds (II)–(IV)
all crystallize with Z′ = 1; a careful search for possible additional symmetry in (I)
revealed none.
In each of (I)–(IV) (Figs. 1
–4
), the molecules are nearly planar, as shown by the values of the torsion angle (Table 1
) defining the rotation of the aryl ring relative to the rest of the rigid skeleton. In addition, the methoxy C atom in (IV)
is virtually coplanar with the adjacent aryl ring. In each compound, there is a fairly short intramolecular C—H⋯S contact (Table 2
), whose dimensions appear at first sight to suggest an attractive hydrogen-bonding interaction forming an S(6) ring (Bernstein et al., 1995
). However, the bond angles associated with the central C—C—C fragment are all strongly indicative of a repulsive C—H⋯S interaction; thus, the angles at the methine C atom linking the two rings are all around 130°. Moreover, the two exocyclic angles at thiazolidine atom C5 consistently differ by ca 10°, and the exocyclic angles at benzene atom C61 consistently differ by ca 6°, always in the sense that the larger angle is that contained within the S(6) motif. All of these bond angles are thus consistent with a highly repulsive C—H⋯S contact, and it is noteworthy that the repulsive contact is accommodated by distortion of the angles in preference to a rotation about the C6—C61 bond, which might at first sight appear to be the less energy-costly solution. In this respect, the behaviour of compounds (I)–(IV)
resembles that of a series of 5-(arylmethylene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-triones, whose essentially planar molecular skeletons are characterized by very wide C—C—C angles (ca 137–139°) at the bridging methine C atom (Rezende et al., 2005
).
In each of (I)–(IV), the ring angle at atom S1 is little greater than 90°, while in (IV)
, the exocyclic bond angles at the ring C atom ipso to the methoxy substituent show the usual deviations from 120°.
The supramolecular structure of (I) is considerably more complex than those of (II)–(IV)
, and it is the only one of the series (I)–(IV)
in which C—H⋯π(arene) hydrogen bonds occur. For these reasons, we describe first (II)
, which has the simplest supramolecular structure, then (III)
and (IV)
, and finally (I)
.
The molecules of (II) are linked by paired N—H⋯O hydrogen bonds (Table 2
) into a centrosymmetric R22(8) dimer (Fig. 5
), but the only direction-specific interaction between these dimers is a dipolar carbonyl–carbonyl interaction involving the C4—O4 bonds in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z). The O4⋯C4i distance is 3.042 (2) Å and the C4—O4⋯C4i angle is 81.52 (9)° [symmetry code: (i) 1 − x, 1 − y, 1 − z], so that this interaction typifies the nearly rectangular antiparallel type II motif (Allen et al., 1998
). The effect of this interaction is to link, albeit weakly, the hydrogen-bonded dimers into a [100] chain. On the other hand, aromatic π–π stacking interactions and intermolecular C—H⋯O and C—H⋯π(arene) hydrogen bonds are all absent.
The notional replacement of the methyl group in (II) by a trifluoromethyl group in (III)
causes a marked change in the supramolecular aggregation. The molecules of (III)
are again linked into centrosymmetric R22(8) dimers, but now by means of paired N—H⋯S hydrogen bonds, as opposed to the N—H⋯O hydrogen bonds in (II)
. In addition, aryl atom C63 in the molecule at (x, y, z) acts as a hydrogen-bond donor to ketone atom O4 in the molecule at (−1 + x, −1 + y, z), so generating by translation a C(8) chain running parallel to the [110] direction. The combination of the two hydrogen bonds then generates a chain of edge-fused rings along [110], in which R22(8) rings centred at (n, n −
,
) (n = zero or integer) alternate with R44(26) rings centred at (n +
, n,
) (n = zero or integer) (Fig. 6
). The trifluoromethyl groups lie on the outer edges of this chain; there are no direction-specific interactions between adjacent chains.
The supramolecular structure of (IV) also consists of a chain of rings, but now constructed from a combination of N—H⋯O and C—H⋯S hydrogen bonds as opposed to the combination of N—H⋯S and C—H⋯O hydrogen bonds in (III)
. Pairs of molecules are linked by N—H⋯O hydrogen bonds into a centrosymmetric R22(8) dimer, just as in compound (II)
, and these dimers are linked by one component of a planar three-centre C—H⋯(S)2 interaction (Table 2
). The shorter component in this system is probably a repulsive contact as discussed above, but the longer component appears to be attractive. Aryl atoms C62 in the molecules at (x, y, z) and (2 − x, 1 − y, 1 − z), which form the R22(8) dimer centred at (1,
,
), act as hydrogen-bond donors, respectively, to thione atoms S2 in the molecules at (1 − x, −y, 1 − z) and (1 + x, 1 + y, z), which themselves form parts of the R22(8) dimers centred at (0, −
,
) and (2,
,
), respectively, so generating by inversion a complex chain of rings running parallel to the [110] direction and containing S(6), R22(8) and R24(8) rings (Fig. 7
).
In (I), where the two independent molecules are related by an approximate, but not exact, twofold rotation, the molecules are again linked by a pair of N—H⋯O hydrogen bonds (Table 2
) into a dimeric aggregate (Fig. 1
). These units are then linked into sheets by three independent C—H⋯π(arene) hydrogen bonds, and the formation of this sheet is very readily analysed in terms of two one-dimensional substructures, one generated by inversion and the other generated by a 21 screw axis.
In the first x, y, z) act as hydrogen-bond donors, respectively, to aryl rings C261–C266 at (1 − x, 1 − y, 1 − z) and C161–C166 at (1 − x, −y, 1 − z), so generating by inversion a chain along (, y,
) containing three types of ring, two of which are centrosymmetric (Fig. 8
). In the second which involves only one of the two independent molecules, aryl atom C166 at (x, y, z) acts as a hydrogen-bond donor to the C161–C166 aryl ring at (
− x, −
+ y,
− z), so forming another [010] chain, this time generated by the 21 screw axis along (
, y,
) (Fig. 9
). The molecule at (
− x, −
+ y,
− z) forms part of the inversion-generated chain lying along (1, y, 1), and hence the combination of these two types of [010] chain generates a sheet parallel to (10
).
![]() | Figure 1 The two independent molecules of (I) ![]() |
![]() | Figure 2 The molecule of (II) ![]() |
![]() | Figure 3 The molecule of (III) ![]() |
![]() | Figure 4 The molecule of (IV) ![]() |
![]() | Figure 5 Part of the crystal structure of (II) ![]() |
![]() | Figure 6 Part of the crystal structure of (III) ![]() |
![]() | Figure 7 Part of the crystal structure of (IV) ![]() |
![]() | Figure 8 A stereoview of part of the crystal structure of (I) ![]() |
![]() | Figure 9 Part of the crystal structure of (I) ![]() ![]() ![]() ![]() ![]() ![]() ![]() |
Experimental
Equimolar quantities (1 mmol of each component) of 2-thioxothiazolidin-4-one and the appropriate benzaldehyde 4-XC6H4CHO [where X = H for (I), CH3 for (II)
, CF3 for (III)
and CH3O for (IV)
] were placed in open Pyrex-glass vessels in the absence of any solvent and irradiated in a domestic microwave oven for 3 min (at 600 W); the reactions were monitored by The reaction mixtures were extracted with ethanol; after removal of this solvent, the products were recrystallized from dimethylformamide to give crystals suitable for single-crystal X-ray For (I)
(orange crystals, m.p. 478 K, yield 58%), MS (70 eV) m/z (%): 221 (23, M+), 134 (100), 108 (40), 89 (8), 51 (4), 77 (2). For (II)
(orange crystals, m.p. 504 K, yield 56%), MS (70 eV) m/z (%): 235 (39, M+), 148 (100), 115 (10), 91 (9), 77 (4), 59 (9). For (III)
(orange crystals, m.p. 488 K, yield 62%), MS (70 eV) m/z (%): 291 (10, M+2), 290 (10, M+1), 289 (100, M+), 152 (35), 138 (11). For (IV)
(orange crystals, m.p. 516 K, yield 87%), MS (70 eV) m/z (%): 164 (9), 149 (61), 121 (100), 89 (17), 77 (34), 63 (12).
Compound (I)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Compound (II)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Compound (III)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Compound (IV)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
|
|
For compound (I), the P21/n was uniquely assigned from the Likewise, the P21/c was uniquely assigned for both (II)
and (IV)
. Although the unit cells for (II)
and (IV)
appear to have very different dimensions and shapes, with the b parameter for (II)
nearly double that for (IV)
, both cells have values of β close to 90°, so that not only are their reduced cells similar in dimensions but both are close to orthorhombic metrics. Crystals of (III)
are triclinic; the P
was selected and confirmed by the successful structure analysis. All H atoms were located from difference maps and then treated as riding atoms. H atoms bonded to C atoms were assigned C—H distances of 0.95 (aromatic and methine) or 0.98 Å (methyl) [with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl groups]. H atoms bonded to N atoms were allowed to ride at the N—H distances (0.90–0.93 Å) deduced from the difference maps [with Uiso(H) = 1.2Ueq(N)]. In (III)
, the displacement parameters for the F atoms indicated some libration of the CF3 group, but it was not found necessary to model this group with more than three F-atom sites.
For all compounds, data collection: COLLECT (Hooft, 1999); cell DENZO (Otwinowski & Minor, 1997
) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003
) and SHELXS97 (Sheldrick, 1997
); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997
); molecular graphics: PLATON (Spek, 2003
); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999
).
Supporting information
10.1107/S0108270105021888/sk1860sup1.cif
contains datablocks global, I, II, III, IV. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270105021888/sk1860Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S0108270105021888/sk1860IIsup3.hkl
Structure factors: contains datablock III. DOI: 10.1107/S0108270105021888/sk1860IIIsup4.hkl
Structure factors: contains datablock IV. DOI: 10.1107/S0108270105021888/sk1860IVsup5.hkl
Equimolar quantities (1 mmol of each component) of 2-thioxothiazolidin-4-one and the appropriate benzaldehyde 4-XC6H4CHO [where X = H for (I), CH3 for (II), CF3 for (III) and CH3O for (IV)] were placed in open Pyrex-glass vessels in the absence of any solvent and irradiated in a domestic microwave oven for 3 min (at 600 W); the reactions were monitored by
The reaction mixtures were extracted with ethanol; after removal of this solvent, the products were recrystallized from dimethylformamide to give crystals suitable for single-crystal X-ray diffraction. For (I) (orange crystals, m.p. 478 K, yield 58%): MS (70 eV) m/z (%), 221 (23, M+), 134 (100), 108 (40), 89 (8), 51 (4), 77 (2). For (II) (orange crystals, m.p. 504 K, yield 56%): MS (70 eV) m/z (%), 235 (39, M+), 148 (100), 115 (10), 91 (9), 77 (4), 59 (9). For (III) (orange crystals, m.p. 488 K, yield 62%): MS (70 eV) m/z (%), 291 (10, M+2), 290 (10, M+1), 289 (100, M+), 152 (35), 138 (11). For (IV) (orange crystals, m.p. 516 K, yield 87%): MS (70 eV) m/z (%), 164 (9), 149 (61), 121 (100), 89 (17), 77 (34), 63 (12).For compound (I), the β close to 90°, so that not only are their reduced cells similar in dimensions but both are close to orthorhombic metrics. Crystals of (III) are triclinic; the P1 was selected, and confirmed by the successful structure analysis. All H atoms were located from difference maps and then treated as riding atoms. H atoms bonded to C atoms were assigned C—H distances of 0.95 Å (aromatic and methine) or 0.98 Å (methyl) [with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl groups]. H atoms bonded to N atoms were allowed to ride at the N—H distances (0.90–0.93 Å) deduced from the difference maps [Uiso(H) = 1.2Ueq(N)]. In (III), the displacement parameters for the F atoms indicated some libration of the CF3 group, but it was not found necessary to model this group with more than three F-atom sites.
P21/n was uniquely assigned from the Likewise, the P21/c was uniquely assigned for both (II) and (IV). Although the unit cells for (II) and (IV) appear to have very different dimensions and shapes, with the b parameter for (II) nearly double that for (IV), both cells have values ofFor all compounds, data collection: COLLECT (Hooft, 1999); cell
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).C10H7NOS2 | F(000) = 912 |
Mr = 221.29 | Dx = 1.527 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4399 reflections |
a = 11.7286 (3) Å | θ = 3.0–27.5° |
b = 7.0215 (2) Å | µ = 0.51 mm−1 |
c = 23.7552 (6) Å | T = 120 K |
β = 100.2630 (12)° | Block, orange |
V = 1925.00 (9) Å3 | 0.38 × 0.20 × 0.10 mm |
Z = 8 |
Nonius KappaCCD diffractometer | 4399 independent reflections |
Radiation source: Bruker–Nonius FR91 rotating anode | 3154 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→9 |
Tmin = 0.888, Tmax = 0.950 | l = −30→30 |
20659 measured reflections |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.8482P] where P = (Fo2 + 2Fc2)/3 |
4399 reflections | (Δ/σ)max = 0.001 |
253 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C10H7NOS2 | V = 1925.00 (9) Å3 |
Mr = 221.29 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.7286 (3) Å | µ = 0.51 mm−1 |
b = 7.0215 (2) Å | T = 120 K |
c = 23.7552 (6) Å | 0.38 × 0.20 × 0.10 mm |
β = 100.2630 (12)° |
Nonius KappaCCD diffractometer | 4399 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3154 reflections with I > 2σ(I) |
Tmin = 0.888, Tmax = 0.950 | Rint = 0.048 |
20659 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.53 e Å−3 |
4399 reflections | Δρmin = −0.33 e Å−3 |
253 parameters |
x | y | z | Uiso*/Ueq | ||
S11 | 0.74536 (4) | 0.33315 (8) | 0.55716 (2) | 0.02152 (14) | |
S12 | 0.65140 (5) | 0.36072 (9) | 0.43209 (2) | 0.02960 (15) | |
O14 | 0.45534 (12) | 0.1532 (2) | 0.59074 (6) | 0.0241 (3) | |
N13 | 0.53612 (14) | 0.2455 (2) | 0.51378 (7) | 0.0201 (4) | |
C12 | 0.63481 (17) | 0.3097 (3) | 0.49728 (8) | 0.0199 (4) | |
C14 | 0.53896 (17) | 0.2108 (3) | 0.57132 (8) | 0.0197 (4) | |
C15 | 0.65520 (16) | 0.2546 (3) | 0.60411 (8) | 0.0173 (4) | |
C16 | 0.67851 (16) | 0.2270 (3) | 0.66127 (8) | 0.0175 (4) | |
C161 | 0.78423 (16) | 0.2566 (3) | 0.70271 (8) | 0.0165 (4) | |
C162 | 0.88665 (17) | 0.3321 (3) | 0.68943 (9) | 0.0186 (4) | |
C163 | 0.98160 (17) | 0.3654 (3) | 0.73215 (8) | 0.0194 (4) | |
C164 | 0.97650 (17) | 0.3249 (3) | 0.78885 (9) | 0.0207 (5) | |
C165 | 0.87648 (17) | 0.2462 (3) | 0.80264 (9) | 0.0212 (5) | |
C166 | 0.78146 (17) | 0.2127 (3) | 0.76022 (8) | 0.0188 (4) | |
S21 | 0.01842 (4) | 0.24752 (8) | 0.47545 (2) | 0.02047 (13) | |
S22 | 0.10145 (5) | 0.25644 (9) | 0.60130 (2) | 0.02745 (15) | |
O24 | 0.32268 (11) | 0.14351 (19) | 0.44484 (6) | 0.0215 (3) | |
N23 | 0.22954 (14) | 0.1831 (2) | 0.52127 (7) | 0.0197 (4) | |
C22 | 0.12570 (17) | 0.2265 (3) | 0.53659 (8) | 0.0192 (4) | |
C24 | 0.23332 (17) | 0.1680 (3) | 0.46376 (8) | 0.0180 (4) | |
C25 | 0.11547 (16) | 0.1882 (3) | 0.42982 (8) | 0.0166 (4) | |
C26 | 0.09572 (17) | 0.1611 (3) | 0.37272 (8) | 0.0174 (4) | |
C261 | −0.01004 (17) | 0.1834 (3) | 0.33099 (8) | 0.0167 (4) | |
C262 | −0.11428 (17) | 0.2532 (3) | 0.34403 (9) | 0.0205 (4) | |
C263 | −0.20826 (17) | 0.2874 (3) | 0.30124 (9) | 0.0226 (5) | |
C264 | −0.20135 (18) | 0.2534 (3) | 0.24443 (9) | 0.0239 (5) | |
C265 | −0.10028 (18) | 0.1786 (3) | 0.23077 (9) | 0.0231 (5) | |
C266 | −0.00615 (18) | 0.1422 (3) | 0.27336 (8) | 0.0196 (4) | |
H13 | 0.4729 | 0.2179 | 0.4876 | 0.024* | |
H16 | 0.6150 | 0.1803 | 0.6771 | 0.021* | |
H162 | 0.8912 | 0.3608 | 0.6508 | 0.022* | |
H163 | 1.0507 | 0.4164 | 0.7226 | 0.023* | |
H164 | 1.0412 | 0.3508 | 0.8181 | 0.025* | |
H165 | 0.8733 | 0.2154 | 0.8413 | 0.025* | |
H166 | 0.7133 | 0.1592 | 0.7701 | 0.023* | |
H23 | 0.2936 | 0.1727 | 0.5483 | 0.024* | |
H26 | 0.1613 | 0.1212 | 0.3574 | 0.021* | |
H262 | −0.1203 | 0.2772 | 0.3827 | 0.025* | |
H263 | −0.2783 | 0.3346 | 0.3108 | 0.027* | |
H264 | −0.2654 | 0.2812 | 0.2151 | 0.029* | |
H265 | −0.0957 | 0.1522 | 0.1920 | 0.028* | |
H266 | 0.0621 | 0.0886 | 0.2636 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S11 | 0.0191 (3) | 0.0273 (3) | 0.0175 (3) | −0.0052 (2) | 0.0017 (2) | 0.0008 (2) |
S12 | 0.0322 (3) | 0.0395 (3) | 0.0171 (3) | −0.0055 (3) | 0.0043 (2) | 0.0013 (2) |
O14 | 0.0158 (7) | 0.0342 (9) | 0.0214 (8) | −0.0026 (6) | 0.0006 (6) | 0.0042 (7) |
N13 | 0.0175 (9) | 0.0259 (9) | 0.0152 (8) | −0.0014 (8) | −0.0014 (7) | 0.0006 (7) |
C12 | 0.0208 (11) | 0.0195 (11) | 0.0193 (10) | 0.0004 (9) | 0.0028 (9) | −0.0016 (8) |
C14 | 0.0195 (11) | 0.0200 (11) | 0.0185 (10) | 0.0021 (8) | 0.0006 (9) | 0.0005 (8) |
C15 | 0.0157 (10) | 0.0169 (10) | 0.0189 (10) | −0.0014 (8) | 0.0024 (8) | 0.0003 (8) |
C16 | 0.0141 (10) | 0.0183 (10) | 0.0201 (10) | −0.0003 (8) | 0.0032 (8) | −0.0009 (8) |
C161 | 0.0161 (10) | 0.0157 (10) | 0.0176 (10) | 0.0032 (8) | 0.0025 (8) | −0.0013 (8) |
C162 | 0.0205 (10) | 0.0195 (10) | 0.0161 (10) | 0.0000 (8) | 0.0040 (8) | −0.0011 (8) |
C163 | 0.0136 (10) | 0.0217 (11) | 0.0235 (11) | −0.0013 (8) | 0.0048 (9) | −0.0014 (9) |
C164 | 0.0164 (10) | 0.0229 (11) | 0.0205 (11) | 0.0015 (9) | −0.0029 (9) | −0.0041 (9) |
C165 | 0.0258 (11) | 0.0220 (11) | 0.0154 (10) | 0.0037 (9) | 0.0023 (9) | −0.0007 (9) |
C166 | 0.0194 (10) | 0.0171 (10) | 0.0207 (11) | 0.0007 (8) | 0.0056 (9) | 0.0002 (8) |
S21 | 0.0166 (3) | 0.0297 (3) | 0.0145 (3) | 0.0020 (2) | 0.0013 (2) | −0.0009 (2) |
S22 | 0.0253 (3) | 0.0428 (4) | 0.0141 (3) | −0.0009 (3) | 0.0033 (2) | −0.0007 (2) |
O24 | 0.0151 (7) | 0.0287 (8) | 0.0202 (7) | 0.0026 (6) | 0.0021 (6) | −0.0041 (6) |
N23 | 0.0151 (8) | 0.0260 (9) | 0.0161 (9) | 0.0004 (7) | −0.0023 (7) | −0.0004 (7) |
C22 | 0.0187 (10) | 0.0209 (11) | 0.0170 (10) | −0.0026 (8) | 0.0001 (8) | −0.0001 (8) |
C24 | 0.0184 (10) | 0.0166 (10) | 0.0180 (10) | 0.0005 (8) | 0.0002 (8) | −0.0020 (8) |
C25 | 0.0168 (10) | 0.0161 (10) | 0.0167 (10) | 0.0011 (8) | 0.0022 (8) | 0.0009 (8) |
C26 | 0.0161 (10) | 0.0182 (10) | 0.0178 (10) | 0.0006 (8) | 0.0028 (8) | −0.0003 (8) |
C261 | 0.0182 (10) | 0.0161 (10) | 0.0150 (10) | −0.0020 (8) | 0.0002 (8) | −0.0002 (8) |
C262 | 0.0223 (11) | 0.0233 (11) | 0.0154 (10) | −0.0011 (9) | 0.0020 (8) | 0.0006 (9) |
C263 | 0.0135 (10) | 0.0282 (12) | 0.0255 (11) | 0.0002 (9) | 0.0015 (9) | 0.0014 (9) |
C264 | 0.0206 (11) | 0.0277 (12) | 0.0202 (11) | −0.0043 (9) | −0.0055 (9) | 0.0028 (9) |
C265 | 0.0268 (11) | 0.0260 (11) | 0.0154 (10) | −0.0082 (9) | 0.0004 (9) | −0.0029 (9) |
C266 | 0.0208 (10) | 0.0202 (10) | 0.0178 (10) | −0.0026 (9) | 0.0033 (8) | −0.0023 (8) |
S11—C12 | 1.753 (2) | S21—C22 | 1.7502 (19) |
S11—C15 | 1.757 (2) | S21—C25 | 1.756 (2) |
C12—N13 | 1.363 (3) | C22—N23 | 1.366 (3) |
C12—S12 | 1.635 (2) | C22—S22 | 1.626 (2) |
N13—C14 | 1.383 (3) | N23—C24 | 1.379 (3) |
N13—H13 | 0.8999 | N23—H23 | 0.8999 |
C14—O14 | 1.225 (2) | C24—O24 | 1.224 (2) |
C14—C15 | 1.477 (3) | C24—C25 | 1.478 (3) |
C15—C16 | 1.351 (3) | C25—C26 | 1.348 (3) |
C16—C161 | 1.454 (3) | C26—C261 | 1.452 (3) |
C16—H16 | 0.95 | C26—H26 | 0.95 |
C161—C162 | 1.400 (3) | C261—C262 | 1.402 (3) |
C161—C166 | 1.406 (3) | C261—C266 | 1.408 (3) |
C162—C163 | 1.386 (3) | C262—C263 | 1.381 (3) |
C162—H162 | 0.95 | C262—H262 | 0.95 |
C163—C164 | 1.388 (3) | C263—C264 | 1.387 (3) |
C163—H163 | 0.95 | C263—H263 | 0.95 |
C164—C165 | 1.387 (3) | C264—C265 | 1.387 (3) |
C164—H164 | 0.95 | C264—H264 | 0.95 |
C165—C166 | 1.383 (3) | C265—C266 | 1.382 (3) |
C165—H165 | 0.95 | C265—H265 | 0.95 |
C166—H166 | 0.95 | C266—H266 | 0.95 |
C12—S11—C15 | 92.51 (9) | C22—S21—C25 | 92.47 (9) |
N13—C12—S12 | 126.53 (15) | N23—C22—S22 | 126.52 (15) |
N13—C12—S11 | 109.93 (14) | N23—C22—S21 | 109.93 (14) |
S12—C12—S11 | 123.54 (12) | S22—C22—S21 | 123.55 (12) |
C12—N13—C14 | 118.05 (17) | C22—N23—C24 | 117.95 (16) |
C12—N13—H13 | 120.7 | C22—N23—H23 | 119.9 |
C14—N13—H13 | 121.1 | C24—N23—H23 | 122.0 |
O14—C14—N13 | 123.42 (18) | O24—C24—N23 | 123.75 (17) |
O14—C14—C15 | 126.59 (18) | O24—C24—C25 | 126.30 (18) |
N13—C14—C15 | 109.99 (17) | N23—C24—C25 | 109.95 (17) |
C16—C15—C14 | 120.19 (18) | C26—C25—C24 | 120.79 (18) |
C16—C15—S11 | 130.27 (16) | C26—C25—S21 | 129.82 (16) |
C14—C15—S11 | 109.52 (14) | C24—C25—S21 | 109.39 (14) |
C15—C16—C161 | 130.97 (19) | C25—C26—C261 | 130.13 (19) |
C15—C16—H16 | 114.5 | C25—C26—H26 | 114.9 |
C161—C16—H16 | 114.5 | C261—C26—H26 | 114.9 |
C162—C161—C166 | 118.11 (17) | C262—C261—C266 | 117.85 (18) |
C162—C161—C16 | 124.34 (18) | C262—C261—C26 | 124.02 (18) |
C166—C161—C16 | 117.51 (18) | C266—C261—C26 | 118.04 (18) |
C163—C162—C161 | 120.58 (19) | C263—C262—C261 | 120.76 (19) |
C163—C162—H162 | 119.7 | C263—C262—H262 | 119.6 |
C161—C162—H162 | 119.7 | C261—C262—H262 | 119.6 |
C162—C163—C164 | 120.51 (18) | C262—C263—C264 | 120.6 (2) |
C162—C163—H163 | 119.7 | C262—C263—H263 | 119.7 |
C164—C163—H163 | 119.7 | C264—C263—H263 | 119.7 |
C165—C164—C163 | 119.67 (18) | C265—C264—C263 | 119.57 (19) |
C165—C164—H164 | 120.2 | C265—C264—H264 | 120.2 |
C163—C164—H164 | 120.2 | C263—C264—H264 | 120.2 |
C166—C165—C164 | 120.08 (19) | C266—C265—C264 | 120.22 (19) |
C166—C165—H165 | 120.0 | C266—C265—H265 | 119.9 |
C164—C165—H165 | 120.0 | C264—C265—H265 | 119.9 |
C165—C166—C161 | 121.02 (19) | C265—C266—C261 | 120.92 (19) |
C165—C166—H166 | 119.5 | C265—C266—H266 | 119.5 |
C161—C166—H166 | 119.5 | C261—C266—H266 | 119.5 |
C15—S11—C12—N13 | 0.03 (15) | C25—S21—C22—N23 | 2.02 (15) |
C15—S11—C12—S12 | 179.61 (14) | C25—S21—C22—S22 | −178.22 (14) |
S12—C12—N13—C14 | −179.77 (16) | S22—C22—N23—C24 | −178.43 (15) |
S11—C12—N13—C14 | −0.2 (2) | S21—C22—N23—C24 | 1.3 (2) |
C12—N13—C14—O14 | 179.92 (19) | C22—N23—C24—O24 | 174.54 (18) |
C12—N13—C14—C15 | 0.3 (2) | C22—N23—C24—C25 | −4.8 (2) |
O14—C14—C15—C16 | 1.8 (3) | O24—C24—C25—C26 | 6.8 (3) |
N13—C14—C15—C16 | −178.56 (18) | N23—C24—C25—C26 | −173.88 (18) |
O14—C14—C15—S11 | −179.86 (17) | O24—C24—C25—S21 | −173.38 (17) |
N13—C14—C15—S11 | −0.3 (2) | N23—C24—C25—S21 | 5.9 (2) |
C12—S11—C15—C16 | 178.2 (2) | C22—S21—C25—C26 | 175.2 (2) |
C12—S11—C15—C14 | 0.13 (15) | C22—S21—C25—C24 | −4.51 (15) |
C14—C15—C16—C161 | 179.35 (19) | C24—C25—C26—C261 | −176.19 (19) |
S11—C15—C16—C161 | 1.4 (3) | S21—C25—C26—C261 | 4.1 (3) |
C15—C16—C161—C162 | 2.9 (3) | C25—C26—C261—C262 | 4.5 (3) |
C15—C16—C161—C166 | −179.6 (2) | C25—C26—C261—C266 | −179.1 (2) |
C166—C161—C162—C163 | −1.1 (3) | C266—C261—C262—C263 | −2.6 (3) |
C16—C161—C162—C163 | 176.41 (18) | C26—C261—C262—C263 | 173.85 (19) |
C161—C162—C163—C164 | −0.2 (3) | C261—C262—C263—C264 | 0.0 (3) |
C162—C163—C164—C165 | 1.5 (3) | C262—C263—C264—C265 | 2.1 (3) |
C163—C164—C165—C166 | −1.5 (3) | C263—C264—C265—C266 | −1.5 (3) |
C164—C165—C166—C161 | 0.2 (3) | C264—C265—C266—C261 | −1.2 (3) |
C162—C161—C166—C165 | 1.1 (3) | C262—C261—C266—C265 | 3.2 (3) |
C16—C161—C166—C165 | −176.59 (18) | C26—C261—C266—C265 | −173.44 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O24 | 0.90 | 1.94 | 2.829 (2) | 168 |
N23—H23···O14 | 0.90 | 1.99 | 2.868 (2) | 165 |
C162—H162···S11 | 0.95 | 2.56 | 3.281 (2) | 133 |
C262—H262···S21 | 0.95 | 2.50 | 3.231 (2) | 134 |
C163—H163···Cg2i | 0.95 | 2.68 | 3.352 (2) | 128 |
C166—H166···Cg1ii | 0.95 | 2.82 | 3.519 (2) | 131 |
C266—H266···Cg1iii | 0.95 | 2.76 | 3.435 (2) | 129 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+1, −y, −z+1. |
C11H9NOS2 | F(000) = 488 |
Mr = 235.31 | Dx = 1.463 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2450 reflections |
a = 4.9428 (1) Å | θ = 3.6–27.5° |
b = 20.0473 (8) Å | µ = 0.47 mm−1 |
c = 10.7834 (4) Å | T = 120 K |
β = 90.753 (2)° | Lath, orange |
V = 1068.43 (6) Å3 | 0.56 × 0.10 × 0.08 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 2450 independent reflections |
Radiation source: Bruker-Nonius FR91 rotating anode | 2092 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
ϕ and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −26→26 |
Tmin = 0.780, Tmax = 0.964 | l = −13→14 |
11502 measured reflections |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0356P)2 + 0.7076P] where P = (Fo2 + 2Fc2)/3 |
2450 reflections | (Δ/σ)max = 0.001 |
137 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C11H9NOS2 | V = 1068.43 (6) Å3 |
Mr = 235.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.9428 (1) Å | µ = 0.47 mm−1 |
b = 20.0473 (8) Å | T = 120 K |
c = 10.7834 (4) Å | 0.56 × 0.10 × 0.08 mm |
β = 90.753 (2)° |
Nonius KappaCCD diffractometer | 2450 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2092 reflections with I > 2σ(I) |
Tmin = 0.780, Tmax = 0.964 | Rint = 0.041 |
11502 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.33 e Å−3 |
2450 reflections | Δρmin = −0.29 e Å−3 |
137 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.43222 (8) | 0.49870 (2) | 0.19002 (4) | 0.01788 (12) | |
S2 | 0.80868 (9) | 0.38256 (2) | 0.17942 (4) | 0.02516 (14) | |
O4 | 0.7435 (2) | 0.56134 (6) | 0.49671 (10) | 0.0172 (3) | |
N3 | 0.8034 (3) | 0.47772 (7) | 0.35398 (12) | 0.0162 (3) | |
C2 | 0.7003 (3) | 0.45019 (8) | 0.24715 (15) | 0.0174 (3) | |
C4 | 0.6772 (3) | 0.53365 (8) | 0.39983 (14) | 0.0153 (3) | |
C5 | 0.4536 (3) | 0.55446 (8) | 0.31527 (14) | 0.0153 (3) | |
C6 | 0.3055 (3) | 0.60879 (8) | 0.34116 (15) | 0.0155 (3) | |
C61 | 0.0870 (3) | 0.64100 (8) | 0.27200 (15) | 0.0150 (3) | |
C62 | −0.0063 (3) | 0.62099 (8) | 0.15479 (15) | 0.0181 (3) | |
C63 | −0.2085 (3) | 0.65641 (9) | 0.09334 (15) | 0.0189 (3) | |
C64 | −0.3221 (3) | 0.71325 (8) | 0.14549 (15) | 0.0177 (3) | |
C65 | −0.2310 (3) | 0.73321 (8) | 0.26285 (15) | 0.0183 (3) | |
C66 | −0.0321 (3) | 0.69774 (8) | 0.32516 (15) | 0.0181 (3) | |
C641 | −0.5343 (4) | 0.75339 (9) | 0.07758 (16) | 0.0233 (4) | |
H3 | 0.9521 | 0.4598 | 0.3957 | 0.019* | |
H6 | 0.3511 | 0.6297 | 0.4176 | 0.019* | |
H62 | 0.0697 | 0.5827 | 0.1168 | 0.022* | |
H63 | −0.2705 | 0.6416 | 0.0142 | 0.023* | |
H64A | −0.6891 | 0.7607 | 0.1318 | 0.035* | |
H64B | −0.5940 | 0.7291 | 0.0032 | 0.035* | |
H64C | −0.4581 | 0.7965 | 0.0534 | 0.035* | |
H65 | −0.3068 | 0.7717 | 0.3003 | 0.022* | |
H66 | 0.0253 | 0.7119 | 0.4053 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0186 (2) | 0.0177 (2) | 0.0173 (2) | 0.00201 (16) | −0.00356 (16) | −0.00289 (15) |
S2 | 0.0261 (3) | 0.0201 (2) | 0.0294 (3) | 0.00441 (18) | −0.00011 (18) | −0.00732 (17) |
O4 | 0.0173 (6) | 0.0187 (6) | 0.0155 (5) | 0.0020 (5) | −0.0020 (4) | −0.0007 (5) |
N3 | 0.0153 (7) | 0.0167 (7) | 0.0166 (7) | 0.0026 (5) | −0.0009 (5) | 0.0009 (5) |
C2 | 0.0163 (8) | 0.0167 (8) | 0.0193 (8) | −0.0022 (6) | 0.0014 (6) | 0.0017 (6) |
C4 | 0.0145 (7) | 0.0159 (8) | 0.0157 (7) | −0.0016 (6) | 0.0023 (6) | 0.0031 (6) |
C5 | 0.0152 (8) | 0.0161 (8) | 0.0146 (7) | −0.0019 (6) | −0.0010 (6) | 0.0001 (6) |
C6 | 0.0155 (8) | 0.0172 (8) | 0.0140 (7) | −0.0026 (6) | −0.0010 (6) | 0.0007 (6) |
C61 | 0.0133 (7) | 0.0145 (8) | 0.0171 (7) | −0.0012 (6) | 0.0005 (6) | 0.0014 (6) |
C62 | 0.0193 (8) | 0.0173 (8) | 0.0179 (8) | 0.0036 (7) | 0.0000 (6) | −0.0007 (6) |
C63 | 0.0192 (8) | 0.0222 (9) | 0.0153 (8) | 0.0007 (7) | −0.0019 (6) | 0.0006 (6) |
C64 | 0.0146 (8) | 0.0190 (8) | 0.0196 (8) | −0.0001 (6) | 0.0018 (6) | 0.0061 (6) |
C65 | 0.0173 (8) | 0.0148 (8) | 0.0227 (8) | 0.0002 (6) | 0.0011 (7) | 0.0004 (6) |
C66 | 0.0185 (8) | 0.0188 (8) | 0.0170 (8) | −0.0020 (7) | −0.0007 (6) | −0.0009 (6) |
C641 | 0.0212 (9) | 0.0265 (9) | 0.0224 (9) | 0.0074 (7) | −0.0003 (7) | 0.0066 (7) |
S1—C2 | 1.7494 (17) | C62—C63 | 1.387 (2) |
S1—C5 | 1.7553 (16) | C62—H62 | 0.95 |
C2—N3 | 1.370 (2) | C63—C64 | 1.392 (2) |
C2—S2 | 1.6337 (17) | C63—H63 | 0.95 |
N3—C4 | 1.378 (2) | C64—C65 | 1.396 (2) |
N3—H3 | 0.9293 | C64—C641 | 1.505 (2) |
C4—O4 | 1.2238 (19) | C641—H64A | 0.98 |
C4—C5 | 1.483 (2) | C641—H64B | 0.98 |
C5—C6 | 1.344 (2) | C641—H64C | 0.98 |
C6—C61 | 1.455 (2) | C65—C66 | 1.381 (2) |
C6—H6 | 0.95 | C65—H65 | 0.95 |
C61—C62 | 1.398 (2) | C66—H66 | 0.95 |
C61—C66 | 1.406 (2) | ||
C2—S1—C5 | 92.60 (8) | C63—C62—H62 | 119.6 |
N3—C2—S2 | 126.16 (13) | C61—C62—H62 | 119.6 |
N3—C2—S1 | 110.11 (12) | C62—C63—C64 | 121.18 (15) |
S2—C2—S1 | 123.73 (10) | C62—C63—H63 | 119.4 |
C2—N3—C4 | 117.68 (13) | C64—C63—H63 | 119.4 |
C2—N3—H3 | 122.3 | C63—C64—C65 | 118.28 (15) |
C4—N3—H3 | 120.0 | C63—C64—C641 | 121.56 (15) |
O4—C4—N3 | 123.90 (14) | C65—C64—C641 | 120.16 (15) |
O4—C4—C5 | 125.89 (15) | C64—C641—H64A | 109.5 |
N3—C4—C5 | 110.21 (13) | C64—C641—H64B | 109.5 |
C6—C5—C4 | 120.26 (14) | H64A—C641—H64B | 109.5 |
C6—C5—S1 | 130.43 (13) | C64—C641—H64C | 109.5 |
C4—C5—S1 | 109.31 (11) | H64A—C641—H64C | 109.5 |
C5—C6—C61 | 130.98 (15) | H64B—C641—H64C | 109.5 |
C5—C6—H6 | 114.5 | C66—C65—C64 | 120.84 (15) |
C61—C6—H6 | 114.5 | C66—C65—H65 | 119.6 |
C62—C61—C66 | 117.75 (14) | C64—C65—H65 | 119.6 |
C62—C61—C6 | 124.71 (15) | C65—C66—C61 | 121.16 (15) |
C66—C61—C6 | 117.50 (14) | C65—C66—H66 | 119.4 |
C63—C62—C61 | 120.78 (15) | C61—C66—H66 | 119.4 |
C5—S1—C2—N3 | −2.13 (12) | S1—C5—C6—C61 | −3.0 (3) |
C5—S1—C2—S2 | 178.49 (12) | C5—C6—C61—C62 | −3.1 (3) |
S2—C2—N3—C4 | −177.35 (12) | C5—C6—C61—C66 | 179.27 (17) |
S1—C2—N3—C4 | 3.30 (18) | C66—C61—C62—C63 | 0.4 (2) |
C2—N3—C4—O4 | 177.18 (15) | C6—C61—C62—C63 | −177.27 (16) |
C2—N3—C4—C5 | −2.8 (2) | C61—C62—C63—C64 | 0.8 (3) |
O4—C4—C5—C6 | 1.1 (3) | C62—C63—C64—C65 | −1.2 (3) |
N3—C4—C5—C6 | −178.92 (14) | C62—C63—C64—C641 | 177.76 (16) |
O4—C4—C5—S1 | −179.00 (13) | C63—C64—C65—C66 | 0.4 (2) |
N3—C4—C5—S1 | 0.99 (16) | C641—C64—C65—C66 | −178.56 (16) |
C2—S1—C5—C6 | −179.46 (17) | C64—C65—C66—C61 | 0.7 (3) |
C2—S1—C5—C4 | 0.64 (12) | C62—C61—C66—C65 | −1.1 (2) |
C4—C5—C6—C61 | 176.92 (16) | C6—C61—C66—C65 | 176.67 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.93 | 1.93 | 2.8507 (18) | 168 |
C62—H62···S1 | 0.95 | 2.58 | 3.2911 (16) | 132 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
C11H6F3NOS2 | Z = 2 |
Mr = 289.29 | F(000) = 292 |
Triclinic, P1 | Dx = 1.707 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.2859 (2) Å | Cell parameters from 2566 reflections |
b = 6.2263 (3) Å | θ = 3.5–27.7° |
c = 17.1885 (8) Å | µ = 0.50 mm−1 |
α = 91.753 (2)° | T = 120 K |
β = 95.326 (3)° | Lath, orange |
γ = 90.129 (3)° | 0.34 × 0.18 × 0.09 mm |
V = 562.99 (4) Å3 |
Nonius KappaCCD diffractometer | 2566 independent reflections |
Radiation source: Bruker-Nonius FR91 rotating anode | 2144 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.7°, θmin = 3.5° |
ϕ and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→8 |
Tmin = 0.849, Tmax = 0.957 | l = −22→22 |
10662 measured reflections |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0459P)2 + 0.5642P] where P = (Fo2 + 2Fc2)/3 |
2566 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
C11H6F3NOS2 | γ = 90.129 (3)° |
Mr = 289.29 | V = 562.99 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.2859 (2) Å | Mo Kα radiation |
b = 6.2263 (3) Å | µ = 0.50 mm−1 |
c = 17.1885 (8) Å | T = 120 K |
α = 91.753 (2)° | 0.34 × 0.18 × 0.09 mm |
β = 95.326 (3)° |
Nonius KappaCCD diffractometer | 2566 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2144 reflections with I > 2σ(I) |
Tmin = 0.849, Tmax = 0.957 | Rint = 0.035 |
10662 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.50 e Å−3 |
2566 reflections | Δρmin = −0.54 e Å−3 |
163 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.43385 (10) | 0.28905 (8) | 0.62212 (3) | 0.01865 (15) | |
S2 | 0.77871 (10) | 0.19479 (8) | 0.49752 (3) | 0.01955 (15) | |
F641 | −0.2392 (3) | 0.1034 (4) | 0.97742 (11) | 0.0727 (7) | |
F642 | −0.5366 (4) | 0.3184 (3) | 0.94816 (12) | 0.0588 (5) | |
F643 | −0.5061 (4) | 0.0363 (3) | 0.88042 (10) | 0.0666 (6) | |
O4 | 0.7418 (3) | 0.8410 (2) | 0.67254 (9) | 0.0235 (3) | |
N3 | 0.7787 (3) | 0.5519 (3) | 0.58861 (10) | 0.0176 (4) | |
C2 | 0.6815 (4) | 0.3552 (3) | 0.56624 (12) | 0.0173 (4) | |
C4 | 0.6696 (4) | 0.6646 (3) | 0.64794 (11) | 0.0180 (4) | |
C5 | 0.4632 (4) | 0.5330 (3) | 0.67591 (12) | 0.0177 (4) | |
C6 | 0.3369 (4) | 0.6045 (3) | 0.73604 (12) | 0.0186 (4) | |
C61 | 0.1441 (4) | 0.4990 (3) | 0.77699 (11) | 0.0181 (4) | |
C62 | 0.0433 (4) | 0.2955 (3) | 0.75600 (12) | 0.0213 (4) | |
C63 | −0.1268 (4) | 0.1981 (3) | 0.80082 (12) | 0.0208 (4) | |
C64 | −0.2014 (4) | 0.3051 (3) | 0.86700 (12) | 0.0191 (4) | |
C65 | −0.1107 (4) | 0.5108 (4) | 0.88746 (12) | 0.0227 (5) | |
C66 | 0.0591 (4) | 0.6055 (3) | 0.84304 (12) | 0.0219 (4) | |
C641 | −0.3695 (4) | 0.1919 (4) | 0.91817 (13) | 0.0232 (5) | |
H3 | 0.9033 | 0.6076 | 0.5632 | 0.021* | |
H6 | 0.3804 | 0.7462 | 0.7547 | 0.022* | |
H62 | 0.0921 | 0.2227 | 0.7104 | 0.026* | |
H63 | −0.1921 | 0.0588 | 0.7863 | 0.025* | |
H65 | −0.1657 | 0.5853 | 0.9319 | 0.027* | |
H66 | 0.1205 | 0.7461 | 0.8572 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0200 (3) | 0.0156 (3) | 0.0211 (3) | −0.00289 (19) | 0.00654 (19) | −0.00288 (19) |
S2 | 0.0196 (3) | 0.0165 (3) | 0.0232 (3) | −0.00173 (19) | 0.0072 (2) | −0.0044 (2) |
F641 | 0.0348 (10) | 0.1186 (18) | 0.0683 (13) | −0.0058 (10) | 0.0024 (9) | 0.0704 (13) |
F642 | 0.0644 (12) | 0.0391 (9) | 0.0827 (13) | 0.0062 (8) | 0.0564 (10) | 0.0087 (9) |
F643 | 0.0849 (14) | 0.0745 (13) | 0.0436 (10) | −0.0599 (11) | 0.0329 (9) | −0.0223 (9) |
O4 | 0.0303 (9) | 0.0174 (8) | 0.0234 (8) | −0.0051 (6) | 0.0063 (6) | −0.0034 (6) |
N3 | 0.0172 (8) | 0.0156 (8) | 0.0206 (9) | −0.0026 (6) | 0.0055 (7) | −0.0007 (7) |
C2 | 0.0174 (10) | 0.0163 (10) | 0.0184 (9) | 0.0004 (8) | 0.0021 (8) | 0.0012 (8) |
C4 | 0.0203 (10) | 0.0163 (10) | 0.0174 (10) | 0.0002 (8) | 0.0021 (8) | 0.0005 (8) |
C5 | 0.0201 (10) | 0.0145 (9) | 0.0185 (10) | −0.0006 (8) | 0.0011 (8) | 0.0010 (8) |
C6 | 0.0241 (11) | 0.0138 (9) | 0.0177 (10) | −0.0004 (8) | 0.0018 (8) | −0.0008 (7) |
C61 | 0.0198 (10) | 0.0171 (10) | 0.0175 (10) | 0.0006 (8) | 0.0023 (8) | 0.0016 (8) |
C62 | 0.0246 (11) | 0.0223 (11) | 0.0175 (10) | −0.0015 (8) | 0.0055 (8) | −0.0035 (8) |
C63 | 0.0249 (11) | 0.0174 (10) | 0.0199 (10) | −0.0039 (8) | 0.0015 (8) | −0.0009 (8) |
C64 | 0.0188 (10) | 0.0206 (10) | 0.0183 (10) | 0.0001 (8) | 0.0032 (8) | 0.0014 (8) |
C641 | 0.0244 (11) | 0.0230 (11) | 0.0225 (11) | −0.0022 (9) | 0.0039 (9) | 0.0006 (9) |
C65 | 0.0282 (12) | 0.0215 (11) | 0.0190 (10) | −0.0015 (9) | 0.0071 (9) | −0.0040 (8) |
C66 | 0.0264 (11) | 0.0174 (10) | 0.0224 (10) | −0.0020 (8) | 0.0056 (9) | −0.0031 (8) |
S1—C2 | 1.750 (2) | C62—C63 | 1.387 (3) |
S1—C5 | 1.753 (2) | C62—H62 | 0.95 |
C2—N3 | 1.358 (3) | C63—C64 | 1.390 (3) |
C2—S2 | 1.643 (2) | C63—H63 | 0.95 |
N3—C4 | 1.390 (3) | C64—C65 | 1.390 (3) |
N3—H3 | 0.90 | C64—C641 | 1.496 (3) |
C4—O4 | 1.212 (2) | C641—F641 | 1.312 (3) |
C4—C5 | 1.487 (3) | C641—F642 | 1.315 (3) |
C5—C6 | 1.347 (3) | C641—F643 | 1.324 (3) |
C6—C61 | 1.457 (3) | C65—C66 | 1.375 (3) |
C6—H6 | 0.95 | C65—H65 | 0.95 |
C61—C62 | 1.398 (3) | C66—H66 | 0.95 |
C61—C66 | 1.407 (3) | ||
C2—S1—C5 | 92.42 (10) | C63—C62—H62 | 119.5 |
N3—C2—S2 | 126.28 (16) | C61—C62—H62 | 119.5 |
N3—C2—S1 | 110.54 (14) | C62—C63—C64 | 119.74 (19) |
S2—C2—S1 | 123.18 (12) | C62—C63—H63 | 120.1 |
C2—N3—C4 | 117.87 (17) | C64—C63—H63 | 120.1 |
C2—N3—H3 | 119.6 | C63—C64—C65 | 120.3 (2) |
C4—N3—H3 | 122.4 | C63—C64—C641 | 119.20 (19) |
O4—C4—N3 | 123.34 (19) | C65—C64—C641 | 120.40 (19) |
O4—C4—C5 | 127.18 (19) | F641—C641—F642 | 106.3 (2) |
N3—C4—C5 | 109.46 (17) | F641—C641—F643 | 106.5 (2) |
C6—C5—C4 | 120.43 (18) | F642—C641—F643 | 104.9 (2) |
C6—C5—S1 | 129.84 (17) | F641—C641—C64 | 112.04 (19) |
C4—C5—S1 | 109.70 (14) | F642—C641—C64 | 113.62 (19) |
C5—C6—C61 | 130.25 (19) | F643—C641—C64 | 112.81 (18) |
C5—C6—H6 | 114.9 | C66—C65—C64 | 119.56 (19) |
C61—C6—H6 | 114.9 | C66—C65—H65 | 120.2 |
C62—C61—C66 | 117.86 (19) | C64—C65—H65 | 120.2 |
C62—C61—C6 | 123.97 (19) | C65—C66—C61 | 121.5 (2) |
C66—C61—C6 | 118.14 (19) | C65—C66—H66 | 119.2 |
C63—C62—C61 | 120.95 (19) | C61—C66—H66 | 119.2 |
C5—S1—C2—N3 | 0.28 (16) | C66—C61—C62—C63 | −2.7 (3) |
C5—S1—C2—S2 | 179.59 (14) | C6—C61—C62—C63 | 175.4 (2) |
S2—C2—N3—C4 | 179.68 (15) | C61—C62—C63—C64 | 0.9 (3) |
S1—C2—N3—C4 | −1.0 (2) | C62—C63—C64—C65 | 1.4 (3) |
C2—N3—C4—O4 | 179.80 (19) | C62—C63—C64—C641 | −175.4 (2) |
C2—N3—C4—C5 | 1.4 (2) | C63—C64—C641—F641 | 95.7 (3) |
O4—C4—C5—C6 | −1.5 (3) | C65—C64—C641—F641 | −81.1 (3) |
N3—C4—C5—C6 | 176.87 (19) | C63—C64—C641—F642 | −143.7 (2) |
O4—C4—C5—S1 | −179.41 (18) | C65—C64—C641—F642 | 39.4 (3) |
N3—C4—C5—S1 | −1.0 (2) | C63—C64—C641—F643 | −24.5 (3) |
C2—S1—C5—C6 | −177.2 (2) | C65—C64—C641—F643 | 158.7 (2) |
C2—S1—C5—C4 | 0.45 (15) | C63—C64—C65—C66 | −1.8 (3) |
C4—C5—C6—C61 | −174.8 (2) | C641—C64—C65—C66 | 175.0 (2) |
S1—C5—C6—C61 | 2.6 (4) | C64—C65—C66—C61 | 0.0 (3) |
C5—C6—C61—C62 | −3.6 (4) | C62—C61—C66—C65 | 2.2 (3) |
C5—C6—C61—C66 | 174.4 (2) | C6—C61—C66—C65 | −176.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···S2i | 0.90 | 2.41 | 3.3048 (18) | 172 |
C62—H62···S1 | 0.95 | 2.51 | 3.230 (2) | 133 |
C63—H63···O4ii | 0.95 | 2.34 | 3.114 (2) | 138 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y−1, z. |
C11H9NO2S2 | F(000) = 520 |
Mr = 251.31 | Dx = 1.516 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2515 reflections |
a = 5.1314 (2) Å | θ = 3.6–27.5° |
b = 10.4543 (5) Å | µ = 0.47 mm−1 |
c = 20.5324 (9) Å | T = 120 K |
β = 91.702 (2)° | Plate, orange |
V = 1100.98 (8) Å3 | 0.44 × 0.18 × 0.08 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 2515 independent reflections |
Radiation source: Bruker-Nonius FR91 rotating anode | 1958 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
ϕ and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.820, Tmax = 0.963 | l = −26→26 |
11472 measured reflections |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0494P)2 + 0.5614P] where P = (Fo2 + 2Fc2)/3 |
2515 reflections | (Δ/σ)max = 0.001 |
146 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
C11H9NO2S2 | V = 1100.98 (8) Å3 |
Mr = 251.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.1314 (2) Å | µ = 0.47 mm−1 |
b = 10.4543 (5) Å | T = 120 K |
c = 20.5324 (9) Å | 0.44 × 0.18 × 0.08 mm |
β = 91.702 (2)° |
Nonius KappaCCD diffractometer | 2515 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1958 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 0.963 | Rint = 0.041 |
11472 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.33 e Å−3 |
2515 reflections | Δρmin = −0.40 e Å−3 |
146 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.49040 (10) | 0.17896 (5) | 0.47167 (2) | 0.02484 (16) | |
S2 | 0.89918 (11) | 0.13208 (6) | 0.57546 (3) | 0.03460 (18) | |
O4 | 0.7371 (3) | 0.52015 (13) | 0.44266 (6) | 0.0243 (3) | |
O41 | −0.4757 (3) | 0.13838 (14) | 0.23331 (7) | 0.0289 (4) | |
N3 | 0.8353 (3) | 0.34500 (16) | 0.50587 (8) | 0.0217 (4) | |
C2 | 0.7597 (4) | 0.2233 (2) | 0.52071 (9) | 0.0236 (4) | |
C4 | 0.6926 (4) | 0.4095 (2) | 0.45883 (9) | 0.0209 (4) | |
C5 | 0.4813 (4) | 0.32790 (19) | 0.43189 (9) | 0.0206 (4) | |
C6 | 0.3223 (4) | 0.3718 (2) | 0.38385 (9) | 0.0214 (4) | |
C61 | 0.1093 (4) | 0.31024 (19) | 0.34746 (9) | 0.0201 (4) | |
C62 | 0.0401 (4) | 0.1812 (2) | 0.35433 (10) | 0.0250 (5) | |
C63 | −0.1566 (4) | 0.1284 (2) | 0.31633 (10) | 0.0259 (5) | |
C64 | −0.2914 (4) | 0.2021 (2) | 0.26983 (10) | 0.0232 (4) | |
C41 | −0.6230 (4) | 0.2108 (2) | 0.18543 (10) | 0.0285 (5) | |
C65 | −0.2320 (4) | 0.3311 (2) | 0.26308 (10) | 0.0230 (4) | |
C66 | −0.0328 (4) | 0.3832 (2) | 0.30149 (9) | 0.0215 (4) | |
H3 | 0.9755 | 0.3802 | 0.5266 | 0.026* | |
H6 | 0.3542 | 0.4578 | 0.3715 | 0.026* | |
H41A | −0.7233 | 0.2772 | 0.2072 | 0.043* | |
H41B | −0.7424 | 0.1537 | 0.1613 | 0.043* | |
H41C | −0.5035 | 0.2509 | 0.1552 | 0.043* | |
H62 | 0.1306 | 0.1297 | 0.3857 | 0.030* | |
H63 | −0.2012 | 0.0410 | 0.3218 | 0.031* | |
H65 | −0.3268 | 0.3827 | 0.2326 | 0.028* | |
H66 | 0.0089 | 0.4711 | 0.2965 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0261 (3) | 0.0233 (3) | 0.0248 (3) | −0.0072 (2) | −0.0057 (2) | 0.0024 (2) |
S2 | 0.0380 (3) | 0.0304 (3) | 0.0348 (3) | −0.0062 (2) | −0.0090 (2) | 0.0080 (3) |
O4 | 0.0291 (8) | 0.0212 (8) | 0.0223 (7) | −0.0057 (6) | −0.0054 (6) | 0.0014 (6) |
O41 | 0.0276 (8) | 0.0265 (8) | 0.0317 (8) | −0.0030 (6) | −0.0121 (6) | −0.0050 (7) |
N3 | 0.0216 (8) | 0.0225 (9) | 0.0206 (8) | −0.0059 (7) | −0.0047 (7) | 0.0002 (7) |
C2 | 0.0231 (10) | 0.0260 (11) | 0.0217 (10) | −0.0032 (8) | 0.0005 (8) | −0.0013 (8) |
C4 | 0.0206 (10) | 0.0241 (11) | 0.0181 (9) | −0.0012 (8) | 0.0005 (8) | −0.0034 (8) |
C5 | 0.0219 (10) | 0.0200 (10) | 0.0198 (9) | −0.0042 (8) | 0.0014 (8) | −0.0013 (8) |
C6 | 0.0223 (10) | 0.0199 (10) | 0.0220 (10) | −0.0020 (8) | 0.0011 (8) | −0.0033 (8) |
C61 | 0.0205 (9) | 0.0203 (10) | 0.0195 (9) | −0.0012 (8) | 0.0009 (7) | −0.0033 (8) |
C62 | 0.0269 (10) | 0.0243 (11) | 0.0234 (10) | −0.0002 (9) | −0.0060 (8) | −0.0004 (8) |
C63 | 0.0286 (11) | 0.0187 (10) | 0.0299 (11) | −0.0029 (9) | −0.0051 (9) | −0.0031 (9) |
C64 | 0.0205 (10) | 0.0262 (11) | 0.0226 (10) | −0.0014 (8) | −0.0018 (8) | −0.0072 (8) |
C41 | 0.0267 (11) | 0.0342 (13) | 0.0240 (10) | −0.0019 (9) | −0.0081 (9) | −0.0045 (9) |
C65 | 0.0218 (10) | 0.0264 (11) | 0.0206 (10) | 0.0022 (8) | −0.0017 (8) | −0.0001 (8) |
C66 | 0.0244 (10) | 0.0193 (10) | 0.0208 (10) | −0.0017 (8) | 0.0001 (8) | −0.0023 (8) |
S1—C2 | 1.748 (2) | C62—C63 | 1.373 (3) |
S1—C5 | 1.758 (2) | C62—H62 | 0.95 |
C2—N3 | 1.367 (3) | C63—C64 | 1.394 (3) |
C2—S2 | 1.624 (2) | C63—H63 | 0.95 |
N3—C4 | 1.372 (2) | C64—O41 | 1.363 (2) |
N3—H3 | 0.9034 | C64—C65 | 1.391 (3) |
C4—O4 | 1.227 (2) | O41—C41 | 1.438 (2) |
C4—C5 | 1.474 (3) | C41—H41A | 0.98 |
C5—C6 | 1.342 (3) | C41—H41B | 0.98 |
C6—C61 | 1.455 (3) | C41—H41C | 0.98 |
C6—H6 | 0.95 | C65—C66 | 1.384 (3) |
C61—C66 | 1.401 (3) | C65—H65 | 0.95 |
C61—C62 | 1.403 (3) | C66—H66 | 0.95 |
C2—S1—C5 | 92.42 (10) | C61—C62—H62 | 119.6 |
N3—C2—S2 | 125.36 (15) | C62—C63—C64 | 120.6 (2) |
N3—C2—S1 | 110.07 (14) | C62—C63—H63 | 119.7 |
S2—C2—S1 | 124.57 (13) | C64—C63—H63 | 119.7 |
C2—N3—C4 | 117.73 (16) | O41—C64—C65 | 124.70 (19) |
C2—N3—H3 | 120.0 | O41—C64—C63 | 115.42 (18) |
C4—N3—H3 | 122.2 | C65—C64—C63 | 119.87 (18) |
O4—C4—N3 | 123.68 (18) | C64—O41—C41 | 117.45 (16) |
O4—C4—C5 | 125.78 (18) | O41—C41—H41A | 109.5 |
N3—C4—C5 | 110.54 (17) | O41—C41—H41B | 109.5 |
C6—C5—C4 | 120.14 (18) | H41A—C41—H41B | 109.5 |
C6—C5—S1 | 130.64 (16) | O41—C41—H41C | 109.5 |
C4—C5—S1 | 109.21 (14) | H41A—C41—H41C | 109.5 |
C5—C6—C61 | 131.07 (19) | H41B—C41—H41C | 109.5 |
C5—C6—H6 | 114.5 | C66—C65—C64 | 119.02 (19) |
C61—C6—H6 | 114.5 | C66—C65—H65 | 120.5 |
C66—C61—C62 | 117.57 (18) | C64—C65—H65 | 120.5 |
C66—C61—C6 | 118.22 (18) | C65—C66—C61 | 122.03 (19) |
C62—C61—C6 | 124.19 (18) | C65—C66—H66 | 119.0 |
C63—C62—C61 | 120.88 (19) | C61—C66—H66 | 119.0 |
C63—C62—H62 | 119.6 | ||
C5—S1—C2—N3 | −0.60 (15) | C5—C6—C61—C66 | 176.8 (2) |
C5—S1—C2—S2 | 179.75 (14) | C5—C6—C61—C62 | −4.7 (3) |
S2—C2—N3—C4 | −178.99 (15) | C66—C61—C62—C63 | 1.2 (3) |
S1—C2—N3—C4 | 1.4 (2) | C6—C61—C62—C63 | −177.29 (19) |
C2—N3—C4—O4 | 177.91 (18) | C61—C62—C63—C64 | 0.2 (3) |
C2—N3—C4—C5 | −1.5 (2) | C62—C63—C64—O41 | 177.61 (19) |
O4—C4—C5—C6 | 2.3 (3) | C62—C63—C64—C65 | −1.9 (3) |
N3—C4—C5—C6 | −178.28 (17) | C65—C64—O41—C41 | −1.5 (3) |
O4—C4—C5—S1 | −178.47 (16) | C63—C64—O41—C41 | 178.99 (17) |
N3—C4—C5—S1 | 1.0 (2) | O41—C64—C65—C66 | −177.37 (18) |
C2—S1—C5—C6 | 178.9 (2) | C63—C64—C65—C66 | 2.1 (3) |
C2—S1—C5—C4 | −0.20 (15) | C64—C65—C66—C61 | −0.7 (3) |
C4—C5—C6—C61 | 177.17 (18) | C62—C61—C66—C65 | −1.0 (3) |
S1—C5—C6—C61 | −1.9 (3) | C6—C61—C66—C65 | 177.59 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.90 | 1.90 | 2.789 (2) | 169 |
C62—H62···S1 | 0.95 | 2.57 | 3.288 (2) | 133 |
C62—H62···S2ii | 0.95 | 2.86 | 3.588 (2) | 135 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C10H7NOS2 | C11H9NOS2 | C11H6F3NOS2 | C11H9NO2S2 |
Mr | 221.29 | 235.31 | 289.29 | 251.31 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 11.7286 (3), 7.0215 (2), 23.7552 (6) | 4.9428 (1), 20.0473 (8), 10.7834 (4) | 5.2859 (2), 6.2263 (3), 17.1885 (8) | 5.1314 (2), 10.4543 (5), 20.5324 (9) |
α, β, γ (°) | 90, 100.2630 (12), 90 | 90, 90.753 (2), 90 | 91.753 (2), 95.326 (3), 90.129 (3) | 90, 91.702 (2), 90 |
V (Å3) | 1925.00 (9) | 1068.43 (6) | 562.99 (4) | 1100.98 (8) |
Z | 8 | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.51 | 0.47 | 0.50 | 0.47 |
Crystal size (mm) | 0.38 × 0.20 × 0.10 | 0.56 × 0.10 × 0.08 | 0.34 × 0.18 × 0.09 | 0.44 × 0.18 × 0.08 |
Data collection | ||||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.888, 0.950 | 0.780, 0.964 | 0.849, 0.957 | 0.820, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20659, 4399, 3154 | 11502, 2450, 2092 | 10662, 2566, 2144 | 11472, 2515, 1958 |
Rint | 0.048 | 0.041 | 0.035 | 0.041 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.654 | 0.649 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.095, 1.03 | 0.033, 0.086, 1.05 | 0.038, 0.103, 1.07 | 0.038, 0.103, 1.04 |
No. of reflections | 4399 | 2450 | 2566 | 2515 |
No. of parameters | 253 | 137 | 163 | 146 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.33 | 0.33, −0.29 | 0.50, −0.54 | 0.33, −0.40 |
Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
Parameter | (I, mol1) | (I, mol2) | (II) | (III) | (IV) |
x = | 1 | 2 | nil | nil | nil |
Sx1—Cx2 | 1.753 (2) | 1.7502 (19) | 1.7494 (17) | 1.750 (2) | 1.748 (2) |
Cx2—Nx3 | 1.363 (3) | 1.366 (3) | 1.370 (2) | 1.358 (3) | 1.367 (3) |
Nx3—Cx4 | 1.383 (3) | 1.379 (3) | 1.378 (2) | 1.390 (3) | 1.372 (2) |
Cx4—Cx5 | 1.477 (3) | 1.478 (3) | 1.483 (2) | 1.487 (3) | 1.474 (3) |
Cx5—Sx1 | 1.757 (2) | 1.756 (2) | 1.7553 (16) | 1.753 (2) | 1.758 (2) |
Cx2—Sx2 | 1.635 (2) | 1.626 (2) | 1.6337 (17) | 1.643 (2) | 1.624 (2) |
Cx4—Ox4 | 1.225 (2) | 1.224 (2) | 1.2238 (19) | 1.212 (2) | 1.227 (2) |
Cx5—Cx6 | 1.351 (3) | 1.348 (3) | 1.344 (2) | 1.347 (3) | 1.342 (3) |
Cx6—Cx61 | 1.454 (3) | 1.452 (3) | 1.455 (2) | 1.457 (3) | 1.455 (3) |
Cx5—Sx1—Cx2 | |||||
92.51 (9) | 92.47 (15) | 92.60 (8) | 92.42 (10) | 92.42 (10) | |
Sx1—Cx5—Cx6 | |||||
130.27 (16) | 129.82 (16) | 130.43 (13) | 129.84 (17) | 130.64 (16) | |
Cx4—Cx5—Cx6 | |||||
120.19 (18) | 120.79 (18) | 120.26 (14) | 120.43 (18) | 120.14 (18) | |
Cx5—Cx6—Cx61 | |||||
130.97 (19) | 130.13 (19) | 130.98 (15) | 130.25 (19) | 131.07 (19) | |
Cx6—Cx61—Cx62 | |||||
124.34 (18) | 124.02 (18) | 124.71 (15) | 123.97 (19) | 124.19 (18) | |
Cx6—Cx61—Cx66 | |||||
117.51 (18) | 118.04 (18) | 117.50 (14) | 118.14 (19) | 118.22 (18) | |
Cx63—Cx64—Ox41 | 115.42 (18) | ||||
Cx65—Cx64—Ox41 | 124.70 (19) | ||||
Cx64—Ox41—Cx41 | 117.45 (16) | ||||
Cx5—Cx6—Cx61—Cx62 | |||||
2.9 (3) | 4.5 (3) | -3.1 (3) | -3.6 (4) | -4.7 (3) | |
Cx63—Cx64—Ox41—Cx41 | 178.99 (17) |
Compound | D—H···A | D—H | H···A | D···A | D—H···A | |
(I) | N13—H13···O24 | 0.95 | 1.94 | 2.829 (2) | 168 | |
N23—H23···O14 | 0.95 | 1.99 | 2.868 (2) | 165 | ||
C162—H162···S11 | 0.95 | 2.56 | 3.281 (2) | 133 | ||
C262—H262···S21 | 0.95 | 2.50 | 3.231 (2) | 134 | ||
C163—H163···Cg2i | 0.95 | 2.68 | 3.352 (2) | 128 | ||
C166—H166···Cg1ii | 0.95 | 2.82 | 3.519 (2) | 131 | ||
C266—H266···Cg1iii | 0.95 | 2.76 | 3.435 (2) | 129 | ||
(II) | N3—H3···O4iv | 0.93 | 1.93 | 2.8507 (18) | 168 | |
C62—H62···S1 | 0.95 | 2.58 | 3.2911 (16) | 132 | ||
(III) | N3—H3···S2iv | 0.90 | 2.41 | 3.3048 (18) | 172 | |
C62—H62···S1 | 0.95 | 2.51 | 3.230 (2) | 133 | ||
C63—H63···O4v | 0.95 | 2.34 | 3.114 (2) | 138 | ||
(IV) | N3—H3···O4iv | 0.90 | 1.90 | 2.789 (2) | 169 | |
C62—H62···S1 | 0.95 | 2.57 | 3.288 (2) | 133 | ||
C62—H62···S2iii | 0.95 | 2.86 | 3.588 (2) | 135 |
Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1.5 − x, −0.5 + y, 1.5 − z; (iii) 1 − x, −y, 1 − z; (iv) 2 − x, 1 − y, 1 − z; (v) −1 + x, −1 + y, z. Cg1 and Cg2 are the centroids of the C161–C166 and C261–C266 rings, respectively |
Acknowledgements
X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton. JC thanks the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. PD and JQ thank COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.
References
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Allen, F. H., Baalham, C. A., Lommerse, J. P. M. & Raithby, P. R. (1998). Acta Cryst. B54, 320–329. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Okazaki, M., Uchino, N., Ishihara, M. & Fukunaga, H. (1998). Bull. Chem. Soc. Jpn, 71, 1713–1718. Web of Science CrossRef CAS Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Rezende, M. C., Dominguez, M., Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o306–o311. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
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As part of a programme for the synthesis of new fused heterocyclic systems of potential biological application, we have been evaluating the use of (Z)-5-arylmethylene-2-thioxothiazolidin-4-ones as intermediates for cyclocondensation reactions, and we report here the structures of four such compounds, which have themselves been prepared by condensation of rhodanine (2-thioxothiazolidin-4-one) with aryl aldehydes using microwave irradiation in a solvent-free system.
We report here the molecular and supramolecular structures of four (Z)-5-arylmethylene-2-thioxo-4-thiazolidines, compounds (I)–(IV). The structure of compound (IV) has been reported previously (Okazaki et al., 1998) using diffraction data collected at ambient temperature; however, no discussion of the supramolecular structure was given and there are no atomic coordinates deposited in the Cambridge Structural Database (CSD; Allen, 2002; refcode GOVXIY). Compound (I) crystallizes in space group P21/n with Z' = 2, while compounds (II)–(IV) all crystallize with Z' = 1; a careful search for possible additional symmetry in (I) revealed none.
In each of (I)–(IV) (Figs 1–4), the molecules are nearly planar, as shown by the values of the torsion angle (Table 1) defining the rotation of the aryl ring relative to the rest of the rigid skeleton. In addition, the methoxy C atom in (IV) is also virtually coplanar with the adjacent aryl ring. In each compound, there is a fairly short intramolecular C—H···S contact (Table 2), whose dimensions appear at first sight to suggest an attractive hydrogen-bonding interaction forming an S(6) ring (Bernstein et al., 1995). However, the bond angles associated with the central C—C—C fragment are all strongly indicative of a repulsive C—H···S interaction; thus, the angles at the methine C atom linking the two rings are all around 130°. Secondly, the two exocyclic angles at thiazolidine atom C5 consistently differ by ca 10°, and the exocyclic angles at phenyl atom C61 consistently differ by ca 6°, always in the sense that the larger angle is that contained within the S(6) motif. All of these bond angles are thus consistent with a highly repulsive C—H···S contact, and it is noteworthy that the repulsive contact is accommodated by distortion of the skeletal bond angles in preference to a rotation about the C6—C61 bond, which might at first sight appear to be the less energy-costly solution. In this respect, the behaviour of compounds (I)–(IV) resembles that of a series of 5-(arylmethylene)-1,3-dimethyl-pyrimidine-2,4,6(1H,3H,5H)-triones, whose essentially planar molecular skeletons are characterized by very wide C—C—C angles (ca 137–139°) at the bridging methine C atom (Rezende et al., 2005).
In each of (I)–(IV), the ring angle at atom S1 is little greater than 90°, while in (IV), the exocyclic bond angles at the ring C atom ipso to the methoxy substituent show the usual deviations from 120°.
The supramolecular structure of (I) is considerably more complex than those of (II)–(IV), and it is the only one of the series (I)–(IV) in which C—H···π(arene) hydrogen bonds occur. For these reasons, we describe first (II), which has the simplest supramolecular structure, then (III) and (IV), and finally (I).
The molecules of (II) are linked by paired N—H···O hydrogen bonds (Table 2) into a centrosymmetric R22(8) dimer (Fig. 5), but the only direction-specific interaction between these dimers is a dipolar carbonyl–carbonyl interaction involving the C4—O4 bonds in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z). The O4···C4i distance is 3.042 (2) Å and the C4—O4···C4i angle is 81.52 (9)° [symmetry code: (i) 1 − x, 1 − y, 1 − z], so that this interaction typifies the nearly rectangular antiparallel type II motif (Allen et al., 1998). The effect of this interaction is to link, albeit weakly, the hydrogen-bonded dimers into a [100] chain. On the other hand, aromatic π–π stacking interactions, and intermolecular C—H···O and C—H···π(arene) hydrogen bonds, are all absent.
The notional replacement of the methyl group in (II) by a trifluoromethyl group in (III) causes a marked change in the supramolecular aggregation. The molecules of (III) are again linked into centrosymmetric R22(8) dimers, but now by means of paired N—H···S hydrogen bonds, as opposed to the N—H···O hydrogen bonds in (II). In addition, aryl atom C63 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the ketonic atom O4 in the molecule at (−1 + x, −1 + y, z), so generating by translation a C(8) chain running parallel to the [110] direction. The combination of the two hydrogen bonds then generates a chain of edge-fused rings along [110], in which R22(8) rings centred at (n, n − 1/2, 1/2) (n = zero or integer) alternate with R44(26) rings centred at (n + 1/2, n,1/2) (n = zero or integer) (Fig. 6). The trifluoromethyl groups lie on the outer edges of this chain; there are no direction-specific interactions between adjacent chains.
The supramolecular structure of (IV) also consists of a chain of rings, but now constructed from a combination of N—H···O and C—H···S hydrogen bonds as opposed to the combination of N—H···S and C—H···O hydrogen bonds in (III). Pairs of molecules are linked by N—H···O hydrogen bonds into a centrosymmetric R22(8) dimer, just as in compound (II), and these dimers are linked by one component of a planar three-centre C—H···(S)2 interaction (Table 2). The shorter component in this system is probably a repulsive contact as discussed above, but the longer component appears to be attractive. Aryl atoms C62 in the molecules at (x, y, z) and (2 − x, 1 − y, 1 − z), which form the R22(8) dimer centred at (1,1/2, 1/2), act as hydrogen-bond donors, respectively, to thione atoms S2 in the molecules at (1 − x, −y, 1 − z) and (1 + x, 1 + y, z), which themselves form parts of the R22(8) dimers centred at (0, −0.5,1/2) and (2, 1.5,1/2), respectively, so generating by inversion a complex chain of rings running parallel to the [110] direction and containing S(6), R22(8) and R42(8) rings (Fig. 7).
In (I), where the two independent molecules are related by an approximate, but not exact, twofold rotation, the molecules are again linked by a pair of N—H···O hydrogen bonds (Table 2) into a dimeric aggregate (Fig. 1). These units are then linked into sheets by three independent C—H···π(arene) hydrogen bonds, and the formation of this sheet is very readily analysed in terms of two one-dimensional substructures, one generated by inversion and the other generated by a 21 screw axis.
In the first substructure, aryl atoms C163 and C266 at (x, y, z) act as hydrogen-bond donors, respectively, to the aryl rings C261–C266 at (1 − x, 1 − y, 1 − z) and C161–C166 at (1 − x, −y, 1 − z), so generating by inversion a chain along (1/2, y,1/2) containing three types of ring, two of them centrosymmetric (Fig. 8). In the second substructure, which involves only one of the two independent molecules, aryl atom C166 at (x, y, z) acts as a hydrogen-bond donor to the C161–C166 aryl ring at (3/2 − x, −1/2 + y, 3/2 − z), so forming another [010] chain this time generated by the 21 screw axis along (3/4, y, 3/4) (Fig. 9). The molecule at (3/2 − x, −1/2 + y, 3/2 − z) forms part of the inversion-generated chain lying along (1, y, 1), and hence the combination of these two types of [010] chain generates a sheet parallel to (10–1).