Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006250/bt6031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006250/bt6031Isup2.hkl |
CCDC reference: 165660
The preparation of (I) followed the general procedure previously reported by Cho, Park, Kim et al. (1999). Details will be reported elsewhere.
Atoms C5 and C6 were disordered over two positions and their coordinates together with site-occupation factors were refined anisotropically using the PART command of SHELXL97 (Sheldrick, 1997). All H atoms were located geometrically with Uiso constrained to be 1.2 times the equivalent isotropic displacement of the parent atoms. The highest peak and deepest holes in the final difference density map are at 0.85 Å from H6A and 0.91 Å from S1, respectively.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C12H16N4O4S4 | F(000) = 848 |
Mr = 408.53 | Dx = 1.517 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 8.7369 (8) Å | Cell parameters from 25 reflections |
b = 15.741 (3) Å | θ = 11.4–13.7° |
c = 13.3967 (12) Å | µ = 0.56 mm−1 |
β = 103.833 (8)° | T = 293 K |
V = 1788.9 (4) Å3 | Block, colorless |
Z = 4 | 0.53 × 0.43 × 0.26 mm |
Enraf Nonius CAD4 diffractometer | 1201 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 25.0°, θmin = 2.6° |
non–profiled ω/2θ scans | h = −10→10 |
Absorption correction: ψ scan (North et al., 1968) | k = −18→18 |
Tmin = 0.745, Tmax = 0.861 | l = −15→0 |
3139 measured reflections | 3 standard reflections every 300 min |
1573 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0409P)2 + 0.708P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
1573 reflections | Δρmax = 0.16 e Å−3 |
130 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0028 (6) |
C12H16N4O4S4 | V = 1788.9 (4) Å3 |
Mr = 408.53 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 8.7369 (8) Å | µ = 0.56 mm−1 |
b = 15.741 (3) Å | T = 293 K |
c = 13.3967 (12) Å | 0.53 × 0.43 × 0.26 mm |
β = 103.833 (8)° |
Enraf Nonius CAD4 diffractometer | 1201 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.026 |
Tmin = 0.745, Tmax = 0.861 | 3 standard reflections every 300 min |
3139 measured reflections | intensity decay: none |
1573 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.16 e Å−3 |
1573 reflections | Δρmin = −0.20 e Å−3 |
130 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.02169 (9) | 0.17999 (5) | 0.40152 (5) | 0.0665 (3) | |
S2 | −0.10009 (10) | 0.34446 (5) | 0.46857 (6) | 0.0777 (3) | |
N1 | 0.1523 (2) | 0.15102 (12) | 0.58796 (13) | 0.0493 (5) | |
N2 | 0.0813 (2) | 0.22914 (11) | 0.58945 (14) | 0.0509 (5) | |
O1 | 0.0000 | 0.10389 (13) | 0.7500 | 0.0572 (6) | |
O2 | 0.1839 (2) | 0.04098 (12) | 0.48204 (14) | 0.0735 (5) | |
O3 | 0.0000 | 0.44894 (14) | 0.7500 | 0.0717 (7) | |
C1 | 0.1209 (3) | 0.05431 (15) | 0.72579 (19) | 0.0631 (7) | |
H1A | 0.0758 | 0.0123 | 0.6741 | 0.076* | |
H1B | 0.1791 | 0.0248 | 0.7866 | 0.076* | |
C2 | 0.2287 (3) | 0.11229 (16) | 0.68591 (18) | 0.0585 (7) | |
H2A | 0.2657 | 0.1567 | 0.7360 | 0.070* | |
H2B | 0.3198 | 0.0803 | 0.6777 | 0.070* | |
C3 | 0.1338 (3) | 0.11066 (16) | 0.49686 (18) | 0.0529 (6) | |
C4 | 0.0094 (3) | 0.25109 (15) | 0.49841 (18) | 0.0514 (6) | |
C5' | −0.0748 (6) | 0.3878 (3) | 0.6839 (4) | 0.0534 (17) | 0.491 (6) |
H5'A | −0.0539 | 0.3294 | 0.7062 | 0.064* | 0.491 (6) |
H5'B | −0.1847 | 0.3983 | 0.6511 | 0.064* | 0.491 (6) |
C5 | −0.1169 (7) | 0.3735 (3) | 0.5857 (4) | 0.0545 (17) | 0.509 (6) |
H5A | −0.2103 | 0.4068 | 0.5854 | 0.065* | 0.509 (6) |
H5B | −0.1059 | 0.3269 | 0.6343 | 0.065* | 0.509 (6) |
C6 | 0.0284 (11) | 0.4232 (6) | 0.6411 (6) | 0.0555 (18) | 0.491 (6) |
H6A | −0.0094 | 0.4613 | 0.5836 | 0.067* | 0.491 (6) |
H6B | 0.1231 | 0.3916 | 0.6394 | 0.067* | 0.491 (6) |
C6' | −0.0104 (13) | 0.4112 (6) | 0.5932 (7) | 0.063 (2) | 0.509 (6) |
H6'A | 0.0858 | 0.3907 | 0.6391 | 0.076* | 0.509 (6) |
H6'B | −0.0211 | 0.4725 | 0.5891 | 0.076* | 0.509 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0779 (5) | 0.0815 (5) | 0.0381 (4) | −0.0132 (4) | 0.0099 (3) | −0.0048 (3) |
S2 | 0.0926 (6) | 0.0697 (5) | 0.0616 (5) | 0.0137 (4) | 0.0002 (4) | 0.0224 (4) |
N1 | 0.0549 (12) | 0.0526 (11) | 0.0406 (10) | 0.0094 (9) | 0.0120 (9) | −0.0051 (8) |
N2 | 0.0632 (12) | 0.0485 (11) | 0.0411 (11) | 0.0082 (10) | 0.0126 (9) | 0.0008 (9) |
O1 | 0.0811 (17) | 0.0388 (12) | 0.0541 (14) | 0.000 | 0.0206 (12) | 0.000 |
O2 | 0.0798 (13) | 0.0742 (12) | 0.0709 (12) | 0.0070 (10) | 0.0270 (10) | −0.0252 (10) |
O3 | 0.0890 (19) | 0.0428 (13) | 0.0758 (18) | 0.000 | 0.0051 (14) | 0.000 |
C1 | 0.0887 (19) | 0.0455 (13) | 0.0500 (14) | 0.0132 (13) | 0.0064 (13) | 0.0015 (11) |
C2 | 0.0636 (16) | 0.0573 (15) | 0.0491 (14) | 0.0180 (12) | 0.0028 (12) | −0.0026 (11) |
C3 | 0.0502 (14) | 0.0637 (16) | 0.0482 (13) | −0.0054 (12) | 0.0188 (11) | −0.0098 (12) |
C4 | 0.0529 (13) | 0.0573 (14) | 0.0430 (13) | −0.0060 (11) | 0.0094 (10) | 0.0054 (11) |
C5' | 0.058 (3) | 0.049 (3) | 0.056 (4) | −0.002 (2) | 0.020 (2) | 0.001 (2) |
C5 | 0.052 (3) | 0.043 (3) | 0.065 (4) | 0.005 (2) | 0.008 (3) | 0.004 (2) |
C6 | 0.065 (5) | 0.041 (3) | 0.063 (5) | 0.000 (3) | 0.019 (4) | 0.001 (4) |
C6' | 0.087 (7) | 0.036 (4) | 0.070 (6) | 0.004 (4) | 0.025 (5) | 0.009 (4) |
S1—C4 | 1.737 (2) | O1—C1 | 1.412 (3) |
S1—C3 | 1.784 (3) | O2—C3 | 1.215 (3) |
S2—C5 | 1.674 (5) | O3—C5' | 1.365 (5) |
S2—C4 | 1.747 (3) | O3—C5'i | 1.365 (5) |
S2—C6' | 1.970 (9) | O3—C6 | 1.590 (8) |
N1—C3 | 1.351 (3) | O3—C6i | 1.590 (8) |
N1—N2 | 1.380 (2) | C1—C2 | 1.499 (3) |
N1—C2 | 1.456 (3) | C5'—C6 | 1.304 (11) |
N2—C4 | 1.279 (3) | C5'—C5'i | 1.934 (11) |
O1—C1i | 1.412 (3) | C5—C6' | 1.088 (11) |
C4—S1—C3 | 88.89 (11) | O1—C1—C2 | 108.28 (18) |
C5—S2—C4 | 100.42 (18) | N1—C2—C1 | 112.6 (2) |
C5—S2—C6' | 33.5 (3) | O2—C3—N1 | 127.0 (2) |
C4—S2—C6' | 99.8 (3) | O2—C3—S1 | 126.36 (19) |
C3—N1—N2 | 118.37 (18) | N1—C3—S1 | 106.60 (17) |
C3—N1—C2 | 123.19 (19) | N2—C4—S1 | 115.76 (18) |
N2—N1—C2 | 118.09 (17) | N2—C4—S2 | 124.25 (18) |
C4—N2—N1 | 110.31 (18) | S1—C4—S2 | 119.97 (14) |
C1i—O1—C1 | 112.9 (3) | C6—C5'—O3 | 73.1 (4) |
C5'—O3—C5'i | 90.2 (4) | C6—C5'—C5'i | 90.9 (5) |
C5'—O3—C6 | 51.7 (4) | O3—C5'—C5'i | 44.9 (2) |
C5'i—O3—C6 | 105.1 (4) | C6'—C5—S2 | 88.3 (6) |
C5'—O3—C6i | 105.1 (4) | C5'—C6—O3 | 55.2 (4) |
C5'i—O3—C6i | 51.7 (4) | C5—C6'—S2 | 58.2 (5) |
C6—O3—C6i | 150.5 (7) | ||
C3—N1—N2—C4 | −1.4 (3) | C3—S1—C4—S2 | −176.91 (15) |
C2—N1—N2—C4 | −174.9 (2) | C5—S2—C4—N2 | −14.0 (3) |
C1i—O1—C1—C2 | 171.4 (2) | C6'—S2—C4—N2 | 20.1 (4) |
C3—N1—C2—C1 | −80.7 (3) | C5—S2—C4—S1 | 164.5 (2) |
N2—N1—C2—C1 | 92.4 (2) | C6'—S2—C4—S1 | −161.4 (3) |
O1—C1—C2—N1 | −66.3 (2) | C5'i—O3—C5'—C6 | −109.2 (5) |
N2—N1—C3—O2 | −177.7 (2) | C6i—O3—C5'—C6 | −159.3 (5) |
C2—N1—C3—O2 | −4.7 (4) | C6—O3—C5'—C5'i | 109.2 (5) |
N2—N1—C3—S1 | 2.6 (2) | C6i—O3—C5'—C5'i | −50.1 (4) |
C2—N1—C3—S1 | 175.63 (18) | C4—S2—C5—C6' | 92.0 (5) |
C4—S1—C3—O2 | 178.1 (2) | C5'i—C5'—C6—O3 | −41.8 (2) |
C4—S1—C3—N1 | −2.22 (17) | C5'i—O3—C6—C5' | 78.0 (6) |
N1—N2—C4—S1 | −0.6 (3) | C6i—O3—C6—C5' | 43.8 (3) |
N1—N2—C4—S2 | 177.96 (16) | C4—S2—C6'—C5 | −94.2 (5) |
C3—S1—C4—N2 | 1.7 (2) |
Symmetry code: (i) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C12H16N4O4S4 |
Mr | 408.53 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.7369 (8), 15.741 (3), 13.3967 (12) |
β (°) | 103.833 (8) |
V (Å3) | 1788.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.56 |
Crystal size (mm) | 0.53 × 0.43 × 0.26 |
Data collection | |
Diffractometer | Enraf Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.745, 0.861 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3139, 1573, 1201 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.089, 1.02 |
No. of reflections | 1573 |
No. of parameters | 130 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.20 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
S1—C4 | 1.737 (2) | S2—C6' | 1.970 (9) |
S1—C3 | 1.784 (3) | N2—C4 | 1.279 (3) |
S2—C5 | 1.674 (5) | O2—C3 | 1.215 (3) |
S2—C4 | 1.747 (3) | ||
C4—S1—C3 | 88.89 (11) |
As a continuation of our studies of macrocyclic compounds containing 1,3,4-thiadiazole subunits (Cho, Park & Hwang, 1999; Cho, Park, Kim et al., 1999; Cho, Park, Hwang et al., 1999; Cho et al., 2000), we have turned our attention to macrocycles composed of two 5-mercapto-2,3-dihydro-1,3,4-thiadizole-2-one units. For the formation of macrocycle (I), these two heterocyclic rings are linked by ether chains. These compounds have been shown to be artificial receptors of transition metals (Cho, Park, Kim et al., 1999) and futhermore are potential hosts of small organic molecules. The determination of the structure of title compound, (I), is part a study of these macrocycles.
The title compound, (I), with the atom-labelling scheme is shown in Fig. 1. A half molecule belongs to an asymmetric unit and the other half molecule is generated by applying a twofold rotation [symmetry code: (i) -x, y, -z + 3/2] passing through O1 and O3. The S—C distances range from 1.674 (5) to 1.970 (9) Å, with a mean value of 1.782 (2) Å, and the N2—C4 and O2—C3 distances of 1.279 (3) and 1.215 (3) clearly show double-bond character. The remainder of the bonds are single bonds; in the five-membered ring, C3—S1—C4 = 88.89 (11)°. These values are comparable with those found in 4,17,25,26-tetraaza-6,9,12,15-tetraoxa-2,19,21,24-tetrathiatricyclo- [18.4.11,4.117,20]hexacosa-1(25),20 (26)-diene-3,5,16,18-tetraone (Cho et al., 2000) and 1,5-[5,5'-(1,3-phenylenedimethylenedithio)bis(2,3-dihydro-2-oxo- 1,3,4-thiadiazol-3-yl)]-3-oxapentane (Cho et al., 2001)
The five-membered ring, 5-mercapto-2,3-dihydro-1,3,4-thiadizole-2-one, is planar within 0.016 (1) Å and the ethyl ether linkage (atoms C2, C1, O1, C1i and C2i) is planar within 0.085 (2) Å. The dihedral angle between the five-membered ring and its own self-related by twofold symmetry is 52.59 (6)°, and the dihedral angle between the five-membered ring and the ethyl ether linkage is 79.02 (6)°. Therefore, the molecule has a twisted conformation with a C2—C1—O1—C1i torsion angle of 171.4 (2)°. The interatomic distances N1···N1i = 5.609 (4) Å, N2···N2i = 4.842 (4) Å, N2···O3 = 4.223 (3) Å, N2···S2i = 6.158 (2) Å, O1···O3 = 5.431 (3) Å and S2···S2i = 7.322 (2) Å appear to be sufficient to introduce a guest ion inside the molecule. The closest intermolecular distance is O2···H5A = 2.572 (5) Å.