Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003814/qa0244sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003814/qa0244Isup2.hkl |
CCDC reference: 144720
To a solution of 1,2,4-triazole-5-thione (1.01 g, 0.01 mol) and dichlorotriethylene glycol (1.87 g, 0.01 mol) in dimethylformamide (60 ml), potassium carbonate (4.15 g, 0.03 mol) were added. The mixture was stirred for 24 h at 303 K, then filtred and dried. The residue was extracted, dried and recrystallized from ethyl acetate.
All H atoms were initially located by difference Fourier synthesis. Their positions were subsequently idealized and constrained to ride on their parent atoms with aromatic C—H = 0.95 Å or secondary C—H = 0.99 Å, respectively, and fixed individual displacement parameters [U(H) = 1.2Ueq(C)].
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
C8H13N3O2S | F(000) = 456 |
Mr = 215.27 | Dx = 1.453 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.230 (1) Å | Cell parameters from 1147 reflections |
b = 15.423 (2) Å | θ = 1–25° |
c = 8.476 (1) Å | µ = 0.31 mm−1 |
β = 113.81 (3)° | T = 173 K |
V = 984.3 (2) Å3 | Block, colourless |
Z = 4 | 0.50 × 0.30 × 0.20 mm |
Siemens CCD three-circle diffractometer | 2257 independent reflections |
Radiation source: fine-focus sealed tube | 1673 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.862, Tmax = 0.941 | k = −20→20 |
13240 measured reflections | l = −11→11 |
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) = 0.081 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0314P)2 + 0.3771P] where P = (Fo2 + 2Fc2)/3 |
2257 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C8H13N3O2S | V = 984.3 (2) Å3 |
Mr = 215.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.230 (1) Å | µ = 0.31 mm−1 |
b = 15.423 (2) Å | T = 173 K |
c = 8.476 (1) Å | 0.50 × 0.30 × 0.20 mm |
β = 113.81 (3)° |
Siemens CCD three-circle diffractometer | 2257 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1673 reflections with I > 2σ(I) |
Tmin = 0.862, Tmax = 0.941 | Rint = 0.066 |
13240 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.25 e Å−3 |
2257 reflections | Δρmin = −0.26 e Å−3 |
127 parameters |
Experimental. The data collection nominally covered a sphere of reciprocal space, by a combination of three sets of exposures; each set had a different ϕ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 4.0 cm. Coverage of the unique set is complete to at least 27° in θ. Crystal decay was monitored by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.36894 (6) | 0.55201 (3) | 0.58082 (6) | 0.02181 (13) | |
C2 | 0.5649 (2) | 0.57450 (12) | 0.7772 (2) | 0.0228 (4) | |
H2A | 0.5808 | 0.5269 | 0.8604 | 0.027* | |
H2B | 0.6707 | 0.5753 | 0.7492 | 0.027* | |
C3 | 0.5549 (3) | 0.65922 (12) | 0.8612 (2) | 0.0236 (4) | |
H3A | 0.4424 | 0.6624 | 0.8773 | 0.028* | |
H3B | 0.6549 | 0.6636 | 0.9758 | 0.028* | |
O4 | 0.56322 (18) | 0.72852 (8) | 0.75360 (18) | 0.0295 (3) | |
C5 | 0.4895 (3) | 0.80816 (12) | 0.7808 (3) | 0.0263 (5) | |
H5A | 0.5539 | 0.8572 | 0.7570 | 0.032* | |
H5B | 0.5070 | 0.8119 | 0.9032 | 0.032* | |
C6 | 0.2946 (3) | 0.81638 (13) | 0.6681 (3) | 0.0291 (5) | |
H6A | 0.2587 | 0.8780 | 0.6610 | 0.035* | |
H6B | 0.2716 | 0.7961 | 0.5501 | 0.035* | |
O7 | 0.19210 (16) | 0.76585 (8) | 0.73710 (17) | 0.0249 (3) | |
C8 | 0.0167 (2) | 0.74784 (13) | 0.6145 (3) | 0.0251 (4) | |
H8A | −0.0259 | 0.7968 | 0.5325 | 0.030* | |
H8B | −0.0636 | 0.7423 | 0.6749 | 0.030* | |
C9 | 0.0098 (2) | 0.66511 (12) | 0.5154 (2) | 0.0236 (4) | |
H9A | −0.1132 | 0.6553 | 0.4301 | 0.028* | |
H9B | 0.0870 | 0.6713 | 0.4518 | 0.028* | |
N10 | 0.06809 (19) | 0.59058 (10) | 0.63076 (19) | 0.0199 (3) | |
C11 | 0.2143 (2) | 0.54079 (11) | 0.6724 (2) | 0.0180 (4) | |
N12 | 0.2205 (2) | 0.48144 (10) | 0.7890 (2) | 0.0247 (4) | |
C13 | 0.0707 (3) | 0.49935 (13) | 0.8135 (3) | 0.0273 (5) | |
H13 | 0.0385 | 0.4673 | 0.8922 | 0.033* | |
N14 | −0.0272 (2) | 0.56389 (11) | 0.7215 (2) | 0.0274 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0195 (2) | 0.0273 (3) | 0.0218 (2) | 0.0002 (2) | 0.01158 (19) | −0.0013 (2) |
C2 | 0.0167 (9) | 0.0257 (10) | 0.0247 (10) | 0.0017 (8) | 0.0070 (8) | 0.0021 (8) |
C3 | 0.0220 (10) | 0.0245 (10) | 0.0248 (11) | −0.0019 (8) | 0.0097 (8) | −0.0006 (8) |
O4 | 0.0375 (8) | 0.0209 (7) | 0.0395 (9) | 0.0010 (6) | 0.0254 (7) | 0.0002 (6) |
C5 | 0.0272 (11) | 0.0199 (10) | 0.0328 (12) | −0.0040 (8) | 0.0132 (9) | −0.0054 (9) |
C6 | 0.0298 (11) | 0.0257 (11) | 0.0332 (12) | −0.0035 (9) | 0.0140 (9) | 0.0015 (9) |
O7 | 0.0210 (7) | 0.0289 (8) | 0.0237 (7) | −0.0041 (6) | 0.0080 (6) | −0.0034 (6) |
C8 | 0.0180 (10) | 0.0247 (10) | 0.0310 (11) | 0.0016 (8) | 0.0083 (8) | −0.0039 (9) |
C9 | 0.0194 (9) | 0.0257 (11) | 0.0217 (10) | 0.0040 (8) | 0.0041 (8) | −0.0002 (8) |
N10 | 0.0170 (8) | 0.0219 (8) | 0.0221 (8) | −0.0010 (6) | 0.0094 (7) | −0.0023 (7) |
C11 | 0.0176 (9) | 0.0191 (9) | 0.0175 (9) | −0.0026 (7) | 0.0074 (7) | −0.0046 (7) |
N12 | 0.0294 (9) | 0.0215 (8) | 0.0258 (9) | −0.0013 (7) | 0.0139 (7) | 0.0005 (7) |
C13 | 0.0322 (11) | 0.0273 (11) | 0.0294 (11) | −0.0077 (9) | 0.0197 (9) | −0.0029 (9) |
N14 | 0.0236 (8) | 0.0316 (10) | 0.0329 (10) | −0.0068 (7) | 0.0175 (8) | −0.0062 (8) |
S1—C11 | 1.7463 (17) | C8—C9 | 1.516 (3) |
S1—C2 | 1.823 (2) | C9—N10 | 1.459 (2) |
C2—C3 | 1.506 (3) | N10—C11 | 1.349 (2) |
C3—O4 | 1.424 (2) | N10—N14 | 1.365 (2) |
O4—C5 | 1.429 (2) | C11—N12 | 1.333 (2) |
C5—C6 | 1.505 (3) | N12—C13 | 1.358 (2) |
C6—O7 | 1.435 (2) | C13—N14 | 1.319 (3) |
O7—C8 | 1.425 (2) | ||
C11—S1—C2 | 98.51 (8) | C11—N10—N14 | 109.60 (15) |
C3—C2—S1 | 113.54 (13) | C11—N10—C9 | 129.87 (15) |
O4—C3—C2 | 108.81 (15) | N14—N10—C9 | 120.48 (14) |
C3—O4—C5 | 114.10 (14) | N12—C11—N10 | 110.37 (15) |
O4—C5—C6 | 112.52 (16) | N12—C11—S1 | 125.53 (14) |
O7—C6—C5 | 110.29 (16) | N10—C11—S1 | 124.08 (13) |
C8—O7—C6 | 113.43 (15) | C11—N12—C13 | 102.03 (16) |
O7—C8—C9 | 111.62 (15) | N14—C13—N12 | 116.01 (17) |
N10—C9—C8 | 111.30 (15) | C13—N14—N10 | 101.99 (15) |
C11—S1—C2—C3 | −65.77 (15) | C9—N10—C11—N12 | 177.28 (16) |
S1—C2—C3—O4 | −68.59 (18) | N14—N10—C11—S1 | 178.39 (12) |
C2—C3—O4—C5 | 157.45 (15) | C9—N10—C11—S1 | −4.2 (3) |
C3—O4—C5—C6 | −89.92 (19) | C2—S1—C11—N12 | −61.28 (17) |
O4—C5—C6—O7 | 78.3 (2) | C2—S1—C11—N10 | 120.42 (15) |
C5—C6—O7—C8 | −161.31 (15) | N10—C11—N12—C13 | −0.19 (19) |
C6—O7—C8—C9 | 88.75 (19) | S1—C11—N12—C13 | −178.69 (14) |
O7—C8—C9—N10 | 60.1 (2) | C11—N12—C13—N14 | 0.5 (2) |
C8—C9—N10—C11 | −112.3 (2) | N12—C13—N14—N10 | −0.6 (2) |
C8—C9—N10—N14 | 64.9 (2) | C11—N10—N14—C13 | 0.40 (19) |
N14—N10—C11—N12 | −0.1 (2) | C9—N10—N14—C13 | −177.29 (16) |
Experimental details
Crystal data | |
Chemical formula | C8H13N3O2S |
Mr | 215.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 8.230 (1), 15.423 (2), 8.476 (1) |
β (°) | 113.81 (3) |
V (Å3) | 984.3 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.50 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Siemens CCD three-circle diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.862, 0.941 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13240, 2257, 1673 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.081, 1.03 |
No. of reflections | 2257 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.26 |
Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
The elaboration of new molecular models for the recognition and the transport of metal atoms constitutes a field of research which has developed rapidly during recent years (Pedersen, 1967; Reinhouldt et al., 1976; Cram & Ho, 1986; Bradshaw et al., 1986; Kumar et al., 1992). The title compound, (I), had been synthesized with the aim to study its complexing properties. Since the condensation of dichlorotriethylene glycol with 1,2,4-triazol-5-thione could lead to two different constitutional isomers, which could not be distinguished by NMR spectroscopy, we have carried out an X-ray structure analysis to establish unambiguously the constitution of the reaction product.
The geometry of the title compound shows no unusual features. The conformation of the crown ether can be described as a chair, with C5 and the bond N10—C11 being the two end points. The torsion-angle pattern in the ring shows an approximate mirror symmetry with the mirror plane running through C5 and the centre of the N10—C11 bond. Only the torsion angles C2—C3—O4—C5 and C5—C6—O7—C8 are close to an antiperiplanar conformation, while apart from C9—N10—C11—S1, which is synperiplanar, all other torsion angles are more or less anti- or synclinal, respectively.