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The title compound, C10H18N2S2, acts as an important precursor for the synthesis of the pharmaceutically important di­amine­di­thiol ligand system. The mol­ecule has a local twofold axis and the arrangement of the S2N2 donor atoms in the macrocycle is anticlinal.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104004688/ob1167sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104004688/ob1167Isup2.hkl
Contains datablock I

CCDC reference: 237947

Comment top

The diaminedithiol ligand system had been employed for complexation with 99mTc to produce significant radiopharmaceuticals (Lever et al., 1985; Cheesman et al., 1988; Kung et al., 1989; Scheffel et al., 1998). Diaminedithiol ligands have also been synthetically modified into bifunctional chelating agents for carrying 99mTc, as well as for coupling to bioactive molecules, such as proteins, antibodies and peptides (Baidoo & Lever, 1990; Baidoo et al., 1998). 99mTc-labeled biomolecules exhibit the potential for use in non-invasive in vivo imaging of cancers (Baidoo et al., 1998). In the synthesis of diaminedithiol ligands, or derivatives that are bifunctional chelating agents, the title compound, (I), is an important precursor. We describe here the preparation of (I) and its X-ray crystal structure, which may further support its identification by NMR and elemental analysis. The cyclic structure of (I) is different from the diaminedithiol compound with a linear structure ?that is obtained? from a reduction reaction of (I) (Baidoo & Lever, 1990; Baidoo et al., 1998).

In (I), two symmetrical aliphatic units (CMe2—C=N—C), of nearly identical geometry and connected by an S1—S2 [2.0201 (10) Å] bond, form a four-donor macrocycle (Fig. 1). The S1—S2 bond length is slightly shorter than that in 6-ethoxycarbonyl-3,3,10,10-tetramethyl-1,2- dithia-5,8-diazadeca-4,8-diene [2.025 (1) Å; Wrench et al., 1993]. This shorter length may be mainly due to the intermolecular interaction of the outward branched 6-ethoxycarbonyl gruop from the ring of the latter compound. The molecule contains two double bonds (C4=N5 and C9=N8), with essentially planar atomic arrangements, as indicated by the torsion angles [C3—C4=N5—C6 = −171.6 (2)° and C7—N8=C9—C10= −173.3 (2)°]. The torsion angles associated with donor atoms [N5=C4—C3—S2 = 123.8 (2)° and N8=C9—C10—S1 = 123.4 (2)°] show that the donor-atom arrangement is anticlinal. The bond distances (Table 1) are in good agreement with standard values. The crystal structure is mainly stabilized by van der Waals forces, and no hydrogen bonding or ππ interaction is observed.

Experimental top

The title compound was synthesized ?using a procedure similar to that reported by Merz et al. (1963), by condensation of 2,2-dithiobis(2-methylpropanal) with ethylenediamine in a molar ratio 1:5. The former compound was previously synthesized from the reaction of isobutylaldehyde with sulfur monochloride following the procedure reported by Baidoo (1988). The reaction was exothermic, so external cooling to keep the temperature lower than 298 K was needed. The resulting yellow solid was separated and washed successively with cold methanol and ether until the product became white. The white solid was then dissolved in ethyl acetate and the solution was filtered, yielding a clear solution. The solution was allowed to stand at room temperature for a few days, whereupon crystals of (I) suitable for X-ray structure analysis were formed (m.p. 437–438 K). 1H NMR (CDCl3): δ C(CH3)2 1.34, 1.42, 2 s, 12H C(CH3)2; =NCH2—CH2N= 3.20, 3.23, 4.11, 4.14, 2 d, 4H; N=CH, 6.84, s, 2H. 13C NMR (CDCl3): δ 21.49, 24.67, 53.09, 61.53, 78.04. Analysis calculated: C 52.11, H 7.87, N 12.20, S 27.82%; found: C 51.95, H 8.31, N 12.18, S 28.81%.

Refinement top

H atoms bonded to C atoms were positioned geometrically and treated as riding [Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms].

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids.
3,3,10,10-Tetramethyl-1,2-dithia-5,8-diazacyclodeca-4,8-diene top
Crystal data top
C10H18N2S2Dx = 1.233 Mg m3
Mr = 230.38Melting point: 165 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 8043 reflections
a = 8.7393 (9) Åθ = 2.6–28.2°
b = 8.9284 (9) ŵ = 0.40 mm1
c = 15.9117 (17) ÅT = 294 K
V = 1241.6 (2) Å3Parallelepiped, colourless
Z = 40.28 × 0.20 × 0.15 mm
F(000) = 496
Data collection top
Bruker SMART CCD area-detector
diffractometer
2963 independent reflections
Radiation source: fine-focus sealed tube2057 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
ϕ and ω scansθmax = 28.2°, θmin = 2.6°
Absorption correction: ψ scan
(North et al., 1968)
h = 1110
Tmin = 0.807, Tmax = 0.891k = 117
8043 measured reflectionsl = 2121
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.084 w = 1/[σ2(Fo2) + (0.0315P)2 + 0.0808P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
2963 reflectionsΔρmax = 0.23 e Å3
127 parametersΔρmin = 0.21 e Å3
0 restraintsAbsolute structure: Flack (1983), 1172 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (10)
Crystal data top
C10H18N2S2V = 1241.6 (2) Å3
Mr = 230.38Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.7393 (9) ŵ = 0.40 mm1
b = 8.9284 (9) ÅT = 294 K
c = 15.9117 (17) Å0.28 × 0.20 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2963 independent reflections
Absorption correction: ψ scan
(North et al., 1968)
2057 reflections with I > 2σ(I)
Tmin = 0.807, Tmax = 0.891Rint = 0.046
8043 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.084Δρmax = 0.23 e Å3
S = 1.03Δρmin = 0.21 e Å3
2963 reflectionsAbsolute structure: Flack (1983), 1172 Friedel pairs
127 parametersAbsolute structure parameter: 0.01 (10)
0 restraints
Special details top

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
S10.29986 (8)0.64572 (8)0.14156 (5)0.04935 (19)
S20.10285 (7)0.54753 (8)0.10449 (4)0.04719 (18)
C30.0667 (3)0.3789 (3)0.17070 (15)0.0410 (6)
C40.1645 (3)0.2562 (2)0.13549 (16)0.0384 (6)
H40.15270.23200.07900.046*
N50.2612 (2)0.1842 (2)0.17723 (13)0.0425 (5)
C60.3609 (3)0.0836 (3)0.13032 (18)0.0519 (7)
H6A0.31660.06250.07570.062*
H6B0.37210.01020.16040.062*
C70.5168 (3)0.1580 (3)0.11960 (16)0.0503 (7)
H7A0.56120.17890.17420.060*
H7B0.58530.09160.08940.060*
N80.4971 (2)0.2973 (2)0.07275 (13)0.0437 (5)
C90.4970 (3)0.4165 (3)0.11454 (15)0.0395 (6)
H90.52010.41030.17150.047*
C100.4620 (3)0.5683 (3)0.07895 (15)0.0401 (6)
C110.0938 (3)0.4080 (3)0.26331 (15)0.0545 (7)
H11A0.02850.48800.28180.082*
H11B0.19880.43560.27200.082*
H11C0.07120.31900.29480.082*
C120.1026 (3)0.3459 (4)0.1517 (2)0.0666 (8)
H12A0.16510.42460.17440.100*
H12B0.13100.25220.17690.100*
H12C0.11740.34050.09200.100*
C130.5927 (3)0.6772 (3)0.09900 (18)0.0599 (8)
H13A0.56970.77380.07570.090*
H13B0.68620.64020.07500.090*
H13C0.60400.68570.15880.090*
C140.4272 (3)0.5642 (3)0.01436 (14)0.0519 (7)
H14A0.40490.66370.03380.078*
H14B0.34030.50070.02420.078*
H14C0.51420.52570.04420.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0535 (4)0.0368 (3)0.0577 (4)0.0054 (3)0.0111 (3)0.0084 (3)
S20.0402 (3)0.0447 (4)0.0567 (4)0.0059 (3)0.0016 (3)0.0124 (3)
C30.0366 (14)0.0420 (15)0.0445 (14)0.0014 (11)0.0064 (10)0.0056 (11)
C40.0376 (13)0.0379 (13)0.0398 (13)0.0067 (11)0.0008 (11)0.0005 (12)
N50.0426 (12)0.0354 (12)0.0495 (12)0.0011 (10)0.0036 (10)0.0061 (10)
C60.0574 (16)0.0335 (13)0.0646 (18)0.0066 (12)0.0075 (14)0.0032 (13)
C70.0503 (15)0.0426 (15)0.0581 (17)0.0139 (13)0.0057 (13)0.0017 (15)
N80.0427 (12)0.0426 (13)0.0459 (12)0.0035 (11)0.0074 (11)0.0003 (11)
C90.0322 (12)0.0492 (16)0.0372 (13)0.0004 (12)0.0001 (11)0.0047 (13)
C100.0370 (13)0.0406 (15)0.0427 (13)0.0024 (12)0.0045 (10)0.0042 (12)
C110.0613 (18)0.0558 (17)0.0464 (15)0.0055 (15)0.0145 (14)0.0017 (13)
C120.0355 (14)0.0715 (19)0.093 (2)0.0029 (16)0.0048 (16)0.0128 (19)
C130.0522 (16)0.0520 (18)0.0756 (19)0.0157 (15)0.0036 (17)0.0046 (15)
C140.0538 (16)0.0579 (18)0.0440 (14)0.0057 (15)0.0036 (12)0.0094 (14)
Geometric parameters (Å, º) top
S1—C101.865 (2)C9—C101.501 (3)
S1—S22.0201 (10)C9—H90.9300
S2—C31.865 (2)C10—C141.516 (3)
C3—C41.498 (3)C10—C131.533 (3)
C3—C111.515 (3)C11—H11A0.9600
C3—C121.539 (3)C11—H11B0.9600
C4—N51.252 (3)C11—H11C0.9600
C4—H40.9300C12—H12A0.9600
N5—C61.457 (3)C12—H12B0.9600
C6—C71.525 (3)C12—H12C0.9600
C6—H6A0.9700C13—H13A0.9600
C6—H6B0.9700C13—H13B0.9600
C7—N81.460 (3)C13—H13C0.9600
C7—H7A0.9700C14—H14A0.9600
C7—H7B0.9700C14—H14B0.9600
N8—C91.255 (3)C14—H14C0.9600
C10—S1—S2109.32 (8)C9—C10—C13110.1 (2)
C3—S2—S1109.26 (8)C14—C10—C13111.6 (2)
C4—C3—C11113.6 (2)C9—C10—S1106.72 (16)
C4—C3—C12109.6 (2)C14—C10—S1112.28 (17)
C11—C3—C12112.0 (2)C13—C10—S1102.69 (18)
C4—C3—S2106.40 (15)C3—C11—H11A109.5
C11—C3—S2112.61 (19)C3—C11—H11B109.5
C12—C3—S2101.91 (17)H11A—C11—H11B109.5
N5—C4—C3124.2 (2)C3—C11—H11C109.5
N5—C4—H4117.9H11A—C11—H11C109.5
C3—C4—H4117.9H11B—C11—H11C109.5
C4—N5—C6116.6 (2)C3—C12—H12A109.5
N5—C6—C7108.9 (2)C3—C12—H12B109.5
N5—C6—H6A109.9H12A—C12—H12B109.5
C7—C6—H6A109.9C3—C12—H12C109.5
N5—C6—H6B109.9H12A—C12—H12C109.5
C7—C6—H6B109.9H12B—C12—H12C109.5
H6A—C6—H6B108.3C10—C13—H13A109.5
N8—C7—C6108.8 (2)C10—C13—H13B109.5
N8—C7—H7A109.9H13A—C13—H13B109.5
C6—C7—H7A109.9C10—C13—H13C109.5
N8—C7—H7B109.9H13A—C13—H13C109.5
C6—C7—H7B109.9H13B—C13—H13C109.5
H7A—C7—H7B108.3C10—C14—H14A109.5
C9—N8—C7116.9 (2)C10—C14—H14B109.5
N8—C9—C10124.5 (2)H14A—C14—H14B109.5
N8—C9—H9117.8C10—C14—H14C109.5
C10—C9—H9117.8H14A—C14—H14C109.5
C9—C10—C14112.9 (2)H14B—C14—H14C109.5

Experimental details

Crystal data
Chemical formulaC10H18N2S2
Mr230.38
Crystal system, space groupOrthorhombic, P212121
Temperature (K)294
a, b, c (Å)8.7393 (9), 8.9284 (9), 15.9117 (17)
V3)1241.6 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.40
Crystal size (mm)0.28 × 0.20 × 0.15
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.807, 0.891
No. of measured, independent and
observed [I > 2σ(I)] reflections
8043, 2963, 2057
Rint0.046
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.084, 1.03
No. of reflections2963
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.21
Absolute structureFlack (1983), 1172 Friedel pairs
Absolute structure parameter0.01 (10)

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
S1—C101.865 (2)N5—C61.457 (3)
S1—S22.0201 (10)C6—C71.525 (3)
S2—C31.865 (2)C7—N81.460 (3)
C3—C41.498 (3)N8—C91.255 (3)
C4—N51.252 (3)C9—C101.501 (3)
C10—S1—S2109.32 (8)C11—C3—C12112.0 (2)
C3—S2—S1109.26 (8)C4—C3—S2106.40 (15)
C4—C3—C11113.6 (2)C11—C3—S2112.61 (19)
C4—C3—C12109.6 (2)C12—C3—S2101.91 (17)
 

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