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The title compound, 4,7-dioxa-10-thia-1,12,13-tri­aza­bi­cyclo­[9.3.0]­tetra­deca-11,13-diene, C8H13N3O2S, contains an 11-membered ring, which appears in a chair conformation and has approximate mirror symmetry. It may be used for the complexation of metal atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003814/qa0244sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003814/qa0244Isup2.hkl
Contains datablock I

CCDC reference: 144720

Comment top

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.

Experimental top

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.

Refinement top

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)].

Computing details top

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).

(I) top
Crystal data top
C8H13N3O2SF(000) = 456
Mr = 215.27Dx = 1.453 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.230 (1) ÅCell parameters from 1147 reflections
b = 15.423 (2) Åθ = 1–25°
c = 8.476 (1) ŵ = 0.31 mm1
β = 113.81 (3)°T = 173 K
V = 984.3 (2) Å3Block, colourless
Z = 40.50 × 0.30 × 0.20 mm
Data collection top
Siemens CCD three-circle
diffractometer
2257 independent reflections
Radiation source: fine-focus sealed tube1673 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.066
ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1010
Tmin = 0.862, Tmax = 0.941k = 2020
13240 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-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 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C8H13N3O2SV = 984.3 (2) Å3
Mr = 215.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.230 (1) ŵ = 0.31 mm1
b = 15.423 (2) ÅT = 173 K
c = 8.476 (1) Å0.50 × 0.30 × 0.20 mm
β = 113.81 (3)°
Data collection top
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 = 0.941Rint = 0.066
13240 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.03Δρmax = 0.25 e Å3
2257 reflectionsΔρmin = 0.26 e Å3
127 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.36894 (6)0.55201 (3)0.58082 (6)0.02181 (13)
C20.5649 (2)0.57450 (12)0.7772 (2)0.0228 (4)
H2A0.58080.52690.86040.027*
H2B0.67070.57530.74920.027*
C30.5549 (3)0.65922 (12)0.8612 (2)0.0236 (4)
H3A0.44240.66240.87730.028*
H3B0.65490.66360.97580.028*
O40.56322 (18)0.72852 (8)0.75360 (18)0.0295 (3)
C50.4895 (3)0.80816 (12)0.7808 (3)0.0263 (5)
H5A0.55390.85720.75700.032*
H5B0.50700.81190.90320.032*
C60.2946 (3)0.81638 (13)0.6681 (3)0.0291 (5)
H6A0.25870.87800.66100.035*
H6B0.27160.79610.55010.035*
O70.19210 (16)0.76585 (8)0.73710 (17)0.0249 (3)
C80.0167 (2)0.74784 (13)0.6145 (3)0.0251 (4)
H8A0.02590.79680.53250.030*
H8B0.06360.74230.67490.030*
C90.0098 (2)0.66511 (12)0.5154 (2)0.0236 (4)
H9A0.11320.65530.43010.028*
H9B0.08700.67130.45180.028*
N100.06809 (19)0.59058 (10)0.63076 (19)0.0199 (3)
C110.2143 (2)0.54079 (11)0.6724 (2)0.0180 (4)
N120.2205 (2)0.48144 (10)0.7890 (2)0.0247 (4)
C130.0707 (3)0.49935 (13)0.8135 (3)0.0273 (5)
H130.03850.46730.89220.033*
N140.0272 (2)0.56389 (11)0.7215 (2)0.0274 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0195 (2)0.0273 (3)0.0218 (2)0.0002 (2)0.01158 (19)0.0013 (2)
C20.0167 (9)0.0257 (10)0.0247 (10)0.0017 (8)0.0070 (8)0.0021 (8)
C30.0220 (10)0.0245 (10)0.0248 (11)0.0019 (8)0.0097 (8)0.0006 (8)
O40.0375 (8)0.0209 (7)0.0395 (9)0.0010 (6)0.0254 (7)0.0002 (6)
C50.0272 (11)0.0199 (10)0.0328 (12)0.0040 (8)0.0132 (9)0.0054 (9)
C60.0298 (11)0.0257 (11)0.0332 (12)0.0035 (9)0.0140 (9)0.0015 (9)
O70.0210 (7)0.0289 (8)0.0237 (7)0.0041 (6)0.0080 (6)0.0034 (6)
C80.0180 (10)0.0247 (10)0.0310 (11)0.0016 (8)0.0083 (8)0.0039 (9)
C90.0194 (9)0.0257 (11)0.0217 (10)0.0040 (8)0.0041 (8)0.0002 (8)
N100.0170 (8)0.0219 (8)0.0221 (8)0.0010 (6)0.0094 (7)0.0023 (7)
C110.0176 (9)0.0191 (9)0.0175 (9)0.0026 (7)0.0074 (7)0.0046 (7)
N120.0294 (9)0.0215 (8)0.0258 (9)0.0013 (7)0.0139 (7)0.0005 (7)
C130.0322 (11)0.0273 (11)0.0294 (11)0.0077 (9)0.0197 (9)0.0029 (9)
N140.0236 (8)0.0316 (10)0.0329 (10)0.0068 (7)0.0175 (8)0.0062 (8)
Geometric parameters (Å, º) top
S1—C111.7463 (17)C8—C91.516 (3)
S1—C21.823 (2)C9—N101.459 (2)
C2—C31.506 (3)N10—C111.349 (2)
C3—O41.424 (2)N10—N141.365 (2)
O4—C51.429 (2)C11—N121.333 (2)
C5—C61.505 (3)N12—C131.358 (2)
C6—O71.435 (2)C13—N141.319 (3)
O7—C81.425 (2)
C11—S1—C298.51 (8)C11—N10—N14109.60 (15)
C3—C2—S1113.54 (13)C11—N10—C9129.87 (15)
O4—C3—C2108.81 (15)N14—N10—C9120.48 (14)
C3—O4—C5114.10 (14)N12—C11—N10110.37 (15)
O4—C5—C6112.52 (16)N12—C11—S1125.53 (14)
O7—C6—C5110.29 (16)N10—C11—S1124.08 (13)
C8—O7—C6113.43 (15)C11—N12—C13102.03 (16)
O7—C8—C9111.62 (15)N14—C13—N12116.01 (17)
N10—C9—C8111.30 (15)C13—N14—N10101.99 (15)
C11—S1—C2—C365.77 (15)C9—N10—C11—N12177.28 (16)
S1—C2—C3—O468.59 (18)N14—N10—C11—S1178.39 (12)
C2—C3—O4—C5157.45 (15)C9—N10—C11—S14.2 (3)
C3—O4—C5—C689.92 (19)C2—S1—C11—N1261.28 (17)
O4—C5—C6—O778.3 (2)C2—S1—C11—N10120.42 (15)
C5—C6—O7—C8161.31 (15)N10—C11—N12—C130.19 (19)
C6—O7—C8—C988.75 (19)S1—C11—N12—C13178.69 (14)
O7—C8—C9—N1060.1 (2)C11—N12—C13—N140.5 (2)
C8—C9—N10—C11112.3 (2)N12—C13—N14—N100.6 (2)
C8—C9—N10—N1464.9 (2)C11—N10—N14—C130.40 (19)
N14—N10—C11—N120.1 (2)C9—N10—N14—C13177.29 (16)

Experimental details

Crystal data
Chemical formulaC8H13N3O2S
Mr215.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)8.230 (1), 15.423 (2), 8.476 (1)
β (°) 113.81 (3)
V3)984.3 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.31
Crystal size (mm)0.50 × 0.30 × 0.20
Data collection
DiffractometerSiemens CCD three-circle
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.862, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections
13240, 2257, 1673
Rint0.066
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.081, 1.03
No. of reflections2257
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.26

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).

 

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