Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199014353/ja1010sup1.cif | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108270199014353/ja1010Isup2.sft |
CCDC reference: 142768
The macrocycle is derived from α,α'-bis[(5-oxa-2,3-dihydro-1,3,4-thiadiazol-2-yl)thio]ethane (Cho et al., 1999). The details of the synthesis will be reported elsewhere.
All H atoms were placed in calculated positions and allowed to ride upon their parent C atom with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: CAD-4 EXPRESS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1998); molecular graphics: ORTEP-3 for Windows (Farrugia, 1998); software used to prepare material for publication: WinGX publication routines (Farrugia, 1998).
C14H16N4O8S4 | F(000) = 1024 |
Mr = 496.55 | Dx = 1.635 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 15.151 (3) Å | Cell parameters from 25 reflections |
b = 12.739 (3) Å | θ = 9.9–14.1° |
c = 10.5509 (13) Å | µ = 0.52 mm−1 |
β = 97.888 (13)° | T = 291 K |
V = 2017.1 (7) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.17 × 0.12 mm |
Enraf-Nonius CAD-4 diffractometer | 1059 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.054 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
non–profiled ω/2θ scans | h = −17→17 |
Absorption correction: empirical (using intensity measurements) (Harms & Wocadlo, 1995) | k = −15→15 |
Tmin = 0.904, Tmax = 0.942 | l = 0→12 |
3616 measured reflections | 3 standard reflections every 624 reflections |
1772 independent reflections | intensity decay: 2% |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0299P)2] where P = (Fo2 + 2Fc2)/3 |
1772 reflections | (Δ/σ)max < 0.001 |
136 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C14H16N4O8S4 | V = 2017.1 (7) Å3 |
Mr = 496.55 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.151 (3) Å | µ = 0.52 mm−1 |
b = 12.739 (3) Å | T = 291 K |
c = 10.5509 (13) Å | 0.20 × 0.17 × 0.12 mm |
β = 97.888 (13)° |
Enraf-Nonius CAD-4 diffractometer | 1059 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (Harms & Wocadlo, 1995) | Rint = 0.054 |
Tmin = 0.904, Tmax = 0.942 | 3 standard reflections every 624 reflections |
3616 measured reflections | intensity decay: 2% |
1772 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.24 e Å−3 |
1772 reflections | Δρmin = −0.20 e Å−3 |
136 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 10.6361 (0.0167) x + 6.2429 (0.0119) y − 6.4170 (0.0112) z = 2.6608 (0.0095) * 0.0069 (0.0015) S2 * 0.0038 (0.0021) N1 * 0.0033 (0.0020) N2 * −0.0075 (0.0020) C2 * −0.0064 (0.0018) C3 − 0.0455 (0.0048) S1 − 0.0181 (0.0050) O4 0.1365 (0.0051) C4 0.1197 (0.0057) O2 0.2698 (0.0047) O3 Rms deviation of fitted atoms = 0.0058 − 10.6361 (0.0167) x + 6.2429 (0.0119) y + 6.4170 (0.0112) z = 1.6503 (0.0219) Angle to previous plane (with approximate e.s.d.) = 58.69 (0.10) * 0.0069 (0.0015) S2_$1 * 0.0038 (0.0021) N1_$1 * 0.0033 (0.0020) N2_$1 * −0.0075 (0.0020) C2_$1 * −0.0064 (0.0018) C3_$1 Rms deviation of fitted atoms = 0.0058 9.1286 (0.0142) x + 3.8048 (0.0064) y − 8.6075 (0.0081) z = 0.2685 (0.0120) Angle to previous plane (with approximate e.s.d.) = 48.77 (0.10) * −0.0150 (0.0009) S1 * 0.0329 (0.0020) N1 * −0.0241 (0.0015) O3 * 0.0062 (0.0004) O1 0.7801 (0.0038) S2 0.2924 (0.0043) N2 − 0.6045 (0.0039) C1 0.1923 (0.0054) C7 Rms deviation of fitted atoms = 0.0220 − 9.1286 (0.0142) x + 3.8048 (0.0064) y + 8.6075 (0.0081) z = 4.0512 (0.0138) Angle to previous plane (with approximate e.s.d.) = 34.76 (0.10) * −0.0150 (0.0009) S1_$1 * 0.0329 (0.0020) N1_$1 * −0.0241 (0.0015) O3_$1 * 0.0062 (0.0004) O1_$1 Rms deviation of fitted atoms = 0.0220 |
x | y | z | Uiso*/Ueq | ||
S1 | 0.51955 (6) | 0.12805 (8) | 0.57815 (9) | 0.0524 (3) | |
S2 | 0.38530 (6) | 0.12037 (8) | 0.34000 (10) | 0.0529 (3) | |
O1 | 0.40995 (16) | 0.6166 (2) | 0.6754 (2) | 0.0572 (8) | |
O2 | 0.21839 (16) | 0.4178 (2) | 0.3351 (3) | 0.0577 (8) | |
O3 | 0.31823 (17) | 0.4490 (2) | 0.5076 (2) | 0.0604 (8) | |
O4 | 0.24763 (17) | 0.2271 (2) | 0.2195 (2) | 0.0576 (8) | |
N1 | 0.39481 (18) | 0.2723 (2) | 0.5040 (3) | 0.0392 (7) | |
N2 | 0.32378 (17) | 0.2952 (2) | 0.4087 (3) | 0.0375 (7) | |
C1 | 0.5349 (2) | 0.2234 (3) | 0.7051 (3) | 0.0416 (9) | |
HC1A | 0.5927 | 0.2115 | 0.7553 | 0.050* | |
HC1B | 0.5363 | 0.2927 | 0.6672 | 0.050* | |
C2 | 0.4306 (2) | 0.1844 (3) | 0.4797 (3) | 0.0390 (9) | |
C3 | 0.3050 (2) | 0.2230 (3) | 0.3089 (3) | 0.0425 (9) | |
C4 | 0.2802 (2) | 0.3933 (3) | 0.4111 (3) | 0.0386 (9) | |
C5 | 0.2846 (3) | 0.5552 (3) | 0.5240 (4) | 0.0576 (12) | |
HC5A | 0.2494 | 0.5565 | 0.5942 | 0.069* | |
HC5B | 0.2469 | 0.5773 | 0.4468 | 0.069* | |
C6 | 0.3618 (3) | 0.6269 (3) | 0.5513 (4) | 0.0566 (11) | |
HC6A | 0.4021 | 0.6142 | 0.4891 | 0.068* | |
HC6B | 0.3408 | 0.6986 | 0.5401 | 0.068* | |
C7 | 0.4731 (2) | 0.5348 (3) | 0.6846 (4) | 0.0712 (14) | |
HC7A | 0.5123 | 0.5441 | 0.6201 | 0.085* | |
HC7B | 0.4428 | 0.4680 | 0.6693 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0551 (6) | 0.0481 (6) | 0.0490 (6) | 0.0168 (5) | −0.0103 (5) | −0.0080 (5) |
S2 | 0.0571 (6) | 0.0518 (6) | 0.0450 (6) | 0.0069 (5) | −0.0095 (5) | −0.0132 (5) |
O1 | 0.0581 (17) | 0.0623 (18) | 0.0487 (17) | 0.0159 (15) | −0.0017 (13) | −0.0079 (15) |
O2 | 0.0470 (15) | 0.0624 (18) | 0.0571 (17) | 0.0122 (14) | −0.0161 (14) | −0.0027 (15) |
O3 | 0.0771 (19) | 0.0434 (16) | 0.0512 (17) | 0.0204 (14) | −0.0246 (15) | −0.0107 (15) |
O4 | 0.0494 (15) | 0.073 (2) | 0.0438 (16) | 0.0020 (14) | −0.0159 (13) | −0.0128 (15) |
N1 | 0.0410 (17) | 0.0422 (19) | 0.0308 (16) | 0.0049 (15) | −0.0082 (14) | 0.0006 (14) |
N2 | 0.0396 (17) | 0.0386 (18) | 0.0313 (17) | 0.0022 (13) | −0.0057 (14) | −0.0009 (14) |
C1 | 0.038 (2) | 0.046 (2) | 0.037 (2) | −0.0015 (16) | −0.0079 (16) | −0.0027 (18) |
C2 | 0.041 (2) | 0.042 (2) | 0.032 (2) | 0.0019 (18) | −0.0004 (17) | 0.0007 (18) |
C3 | 0.043 (2) | 0.047 (2) | 0.037 (2) | −0.0035 (18) | 0.0051 (19) | −0.0012 (19) |
C4 | 0.039 (2) | 0.044 (2) | 0.032 (2) | 0.0010 (18) | 0.0026 (18) | 0.0034 (19) |
C5 | 0.068 (3) | 0.049 (3) | 0.050 (3) | 0.019 (2) | −0.011 (2) | −0.003 (2) |
C6 | 0.079 (3) | 0.044 (2) | 0.046 (2) | 0.014 (2) | 0.007 (2) | 0.006 (2) |
C7 | 0.058 (3) | 0.065 (3) | 0.083 (4) | 0.007 (2) | −0.020 (2) | −0.011 (3) |
S1—C2 | 1.739 (3) | O4—C3 | 1.193 (4) |
S1—C1 | 1.800 (3) | N1—C2 | 1.285 (4) |
S2—C2 | 1.741 (3) | N1—N2 | 1.399 (3) |
S2—C3 | 1.785 (4) | N2—C3 | 1.398 (4) |
O1—C7 | 1.408 (4) | N2—C4 | 1.415 (4) |
O1—C6 | 1.414 (4) | C1—C1i | 1.514 (6) |
O2—C4 | 1.188 (4) | C5—C6 | 1.482 (5) |
O3—C4 | 1.307 (4) | C7—C7i | 1.504 (7) |
O3—C5 | 1.465 (4) | ||
C2—S1—C1 | 100.16 (17) | S1—C2—S2 | 119.7 (2) |
C2—S2—C3 | 89.55 (17) | O4—C3—N2 | 128.2 (3) |
C7—O1—C6 | 113.0 (3) | O4—C3—S2 | 125.5 (3) |
C4—O3—C5 | 118.0 (3) | N2—C3—S2 | 106.3 (2) |
C2—N1—N2 | 110.0 (3) | O2—C4—O3 | 127.3 (3) |
C3—N2—N1 | 117.4 (3) | O2—C4—N2 | 123.1 (3) |
C3—N2—C4 | 123.2 (3) | O3—C4—N2 | 109.6 (3) |
N1—N2—C4 | 119.1 (3) | O3—C5—C6 | 108.3 (3) |
C1i—C1—S1 | 115.8 (2) | O1—C6—C5 | 114.6 (3) |
N1—C2—S1 | 123.6 (3) | O1—C7—C7i | 109.9 (3) |
N1—C2—S2 | 116.7 (3) | ||
C2—N1—N2—C3 | −0.1 (4) | C2—S2—C3—O4 | −179.1 (3) |
C2—N1—N2—C4 | −174.3 (3) | C2—S2—C3—N2 | 1.0 (2) |
C2—S1—C1—C1i | 73.3 (3) | C5—O3—C4—O2 | −2.3 (6) |
N2—N1—C2—S1 | −178.6 (2) | C5—O3—C4—N2 | 177.9 (3) |
N2—N1—C2—S2 | 1.0 (4) | C3—N2—C4—O2 | 7.6 (5) |
C1—S1—C2—N1 | 1.3 (3) | N1—N2—C4—O2 | −178.5 (3) |
C1—S1—C2—S2 | −178.3 (2) | C3—N2—C4—O3 | −172.6 (3) |
C3—S2—C2—N1 | −1.2 (3) | N1—N2—C4—O3 | 1.3 (4) |
C3—S2—C2—S1 | 178.4 (2) | C4—O3—C5—C6 | −134.8 (3) |
N1—N2—C3—O4 | 179.4 (3) | C7—O1—C6—C5 | 83.5 (4) |
C4—N2—C3—O4 | −6.6 (6) | O3—C5—C6—O1 | −73.2 (4) |
N1—N2—C3—S2 | −0.7 (4) | C6—O1—C7—C7i | 175.0 (3) |
C4—N2—C3—S2 | 173.2 (3) |
Symmetry code: (i) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C14H16N4O8S4 |
Mr | 496.55 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 291 |
a, b, c (Å) | 15.151 (3), 12.739 (3), 10.5509 (13) |
β (°) | 97.888 (13) |
V (Å3) | 2017.1 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.52 |
Crystal size (mm) | 0.20 × 0.17 × 0.12 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (Harms & Wocadlo, 1995) |
Tmin, Tmax | 0.904, 0.942 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3616, 1772, 1059 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.092, 1.02 |
No. of reflections | 1772 |
No. of parameters | 136 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.20 |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), CAD-4 EXPRESS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1998), ORTEP-3 for Windows (Farrugia, 1998), WinGX publication routines (Farrugia, 1998).
The determination of the structure of the title compound, (I), is part of our continuing study of the molecular structures of macrocycles containing 1,3,4-thiadiazole subunits (Cho, Park & Hwang, 1999; Cho et al., 1999). These compounds are of interest because of their potential activity as artificial receptors of transition metals and other small organic molecules.
Half a molecule of (I) belongs to the asymmetric unit and a molecule is completed by the crystallographic twofold axis (see Fig. 1). The S—C bond lengths range from 1.739 (3) to 1.800 (3) Å, with a mean value of 1.766 (2) Å, which is similar to that found in the International Tables for Crystallography (Vol. C). The C2—S2—C3 angle of 99.55 (17)° is similar to that found in (2S,4S,5R)-(-)-3,4-dimethyl-5-phenyl-2-(1,3-thiazol-2-yl)-1,3-oxazolidine (Fitzsimons & Gallagher, 1999). The bond lengths O2—C4 of 1.188 (4) Å, O4—C3 of 1.193 (4) Å and N1—C2 of 1.285 (4) Å all show clearly double-bond character; the remainder of the bonds are single bonds. The five-membered ring, 5-mercapto-3H-1,3,4-thiadiazolin-2-one, is planar to within 0.008 (2) Å. The dihedral angle between the two five-membered rings of the molecule is 58.7 (1)°. The two half molecules are twisted around the twofold axis with torsion angles S1—C1—C1i—S1i of 82.9 (3)° [symmetry code: (i) 1 − x, y, 1.5 − z] and O1—C7—C7i—O1i of −76.2 (5)°, so that O3···O3i = 6.984 (5), N1···N1i = 5.706 (6) Å and N1···O3i = 6.661 (4) Å. The atoms S1, N1, O3 and O1 in an asymmetric unit lie in a plane within 0.042 (4) Å, and C1 and C7 in ether groups deviate by −0.595 (4) and 0.194 (5) Å, respectively, from the best plane.