Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104004688/ob1167sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104004688/ob1167Isup2.hkl |
CCDC reference: 237947
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%.
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].
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.
Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. |
C10H18N2S2 | Dx = 1.233 Mg m−3 |
Mr = 230.38 | Melting point: 165 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8043 reflections |
a = 8.7393 (9) Å | θ = 2.6–28.2° |
b = 8.9284 (9) Å | µ = 0.40 mm−1 |
c = 15.9117 (17) Å | T = 294 K |
V = 1241.6 (2) Å3 | Parallelepiped, colourless |
Z = 4 | 0.28 × 0.20 × 0.15 mm |
F(000) = 496 |
Bruker SMART CCD area-detector diffractometer | 2963 independent reflections |
Radiation source: fine-focus sealed tube | 2057 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ϕ and ω scans | θmax = 28.2°, θmin = 2.6° |
Absorption correction: ψ scan (North et al., 1968) | h = −11→10 |
Tmin = 0.807, Tmax = 0.891 | k = −11→7 |
8043 measured reflections | l = −21→21 |
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) = 0.084 | w = 1/[σ2(Fo2) + (0.0315P)2 + 0.0808P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2963 reflections | Δρmax = 0.23 e Å−3 |
127 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1172 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (10) |
C10H18N2S2 | V = 1241.6 (2) Å3 |
Mr = 230.38 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.7393 (9) Å | µ = 0.40 mm−1 |
b = 8.9284 (9) Å | T = 294 K |
c = 15.9117 (17) Å | 0.28 × 0.20 × 0.15 mm |
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 = 0.891 | Rint = 0.046 |
8043 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.084 | Δρmax = 0.23 e Å−3 |
S = 1.03 | Δρmin = −0.21 e Å−3 |
2963 reflections | Absolute structure: Flack (1983), 1172 Friedel pairs |
127 parameters | Absolute structure parameter: 0.01 (10) |
0 restraints |
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 | 0.29986 (8) | 0.64572 (8) | 0.14156 (5) | 0.04935 (19) | |
S2 | 0.10285 (7) | 0.54753 (8) | 0.10449 (4) | 0.04719 (18) | |
C3 | 0.0667 (3) | 0.3789 (3) | 0.17070 (15) | 0.0410 (6) | |
C4 | 0.1645 (3) | 0.2562 (2) | 0.13549 (16) | 0.0384 (6) | |
H4 | 0.1527 | 0.2320 | 0.0790 | 0.046* | |
N5 | 0.2612 (2) | 0.1842 (2) | 0.17723 (13) | 0.0425 (5) | |
C6 | 0.3609 (3) | 0.0836 (3) | 0.13032 (18) | 0.0519 (7) | |
H6A | 0.3166 | 0.0625 | 0.0757 | 0.062* | |
H6B | 0.3721 | −0.0102 | 0.1604 | 0.062* | |
C7 | 0.5168 (3) | 0.1580 (3) | 0.11960 (16) | 0.0503 (7) | |
H7A | 0.5612 | 0.1789 | 0.1742 | 0.060* | |
H7B | 0.5853 | 0.0916 | 0.0894 | 0.060* | |
N8 | 0.4971 (2) | 0.2973 (2) | 0.07275 (13) | 0.0437 (5) | |
C9 | 0.4970 (3) | 0.4165 (3) | 0.11454 (15) | 0.0395 (6) | |
H9 | 0.5201 | 0.4103 | 0.1715 | 0.047* | |
C10 | 0.4620 (3) | 0.5683 (3) | 0.07895 (15) | 0.0401 (6) | |
C11 | 0.0938 (3) | 0.4080 (3) | 0.26331 (15) | 0.0545 (7) | |
H11A | 0.0285 | 0.4880 | 0.2818 | 0.082* | |
H11B | 0.1988 | 0.4356 | 0.2720 | 0.082* | |
H11C | 0.0712 | 0.3190 | 0.2948 | 0.082* | |
C12 | −0.1026 (3) | 0.3459 (4) | 0.1517 (2) | 0.0666 (8) | |
H12A | −0.1651 | 0.4246 | 0.1744 | 0.100* | |
H12B | −0.1310 | 0.2522 | 0.1769 | 0.100* | |
H12C | −0.1174 | 0.3405 | 0.0920 | 0.100* | |
C13 | 0.5927 (3) | 0.6772 (3) | 0.09900 (18) | 0.0599 (8) | |
H13A | 0.5697 | 0.7738 | 0.0757 | 0.090* | |
H13B | 0.6862 | 0.6402 | 0.0750 | 0.090* | |
H13C | 0.6040 | 0.6857 | 0.1588 | 0.090* | |
C14 | 0.4272 (3) | 0.5642 (3) | −0.01436 (14) | 0.0519 (7) | |
H14A | 0.4049 | 0.6637 | −0.0338 | 0.078* | |
H14B | 0.3403 | 0.5007 | −0.0242 | 0.078* | |
H14C | 0.5142 | 0.5257 | −0.0442 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0535 (4) | 0.0368 (3) | 0.0577 (4) | −0.0054 (3) | 0.0111 (3) | −0.0084 (3) |
S2 | 0.0402 (3) | 0.0447 (4) | 0.0567 (4) | 0.0059 (3) | 0.0016 (3) | 0.0124 (3) |
C3 | 0.0366 (14) | 0.0420 (15) | 0.0445 (14) | 0.0014 (11) | 0.0064 (10) | 0.0056 (11) |
C4 | 0.0376 (13) | 0.0379 (13) | 0.0398 (13) | −0.0067 (11) | −0.0008 (11) | 0.0005 (12) |
N5 | 0.0426 (12) | 0.0354 (12) | 0.0495 (12) | 0.0011 (10) | 0.0036 (10) | 0.0061 (10) |
C6 | 0.0574 (16) | 0.0335 (13) | 0.0646 (18) | 0.0066 (12) | 0.0075 (14) | 0.0032 (13) |
C7 | 0.0503 (15) | 0.0426 (15) | 0.0581 (17) | 0.0139 (13) | 0.0057 (13) | 0.0017 (15) |
N8 | 0.0427 (12) | 0.0426 (13) | 0.0459 (12) | 0.0035 (11) | 0.0074 (11) | 0.0003 (11) |
C9 | 0.0322 (12) | 0.0492 (16) | 0.0372 (13) | −0.0004 (12) | −0.0001 (11) | 0.0047 (13) |
C10 | 0.0370 (13) | 0.0406 (15) | 0.0427 (13) | −0.0024 (12) | 0.0045 (10) | 0.0042 (12) |
C11 | 0.0613 (18) | 0.0558 (17) | 0.0464 (15) | 0.0055 (15) | 0.0145 (14) | 0.0017 (13) |
C12 | 0.0355 (14) | 0.0715 (19) | 0.093 (2) | −0.0029 (16) | 0.0048 (16) | 0.0128 (19) |
C13 | 0.0522 (16) | 0.0520 (18) | 0.0756 (19) | −0.0157 (15) | 0.0036 (17) | 0.0046 (15) |
C14 | 0.0538 (16) | 0.0579 (18) | 0.0440 (14) | 0.0057 (15) | 0.0036 (12) | 0.0094 (14) |
S1—C10 | 1.865 (2) | C9—C10 | 1.501 (3) |
S1—S2 | 2.0201 (10) | C9—H9 | 0.9300 |
S2—C3 | 1.865 (2) | C10—C14 | 1.516 (3) |
C3—C4 | 1.498 (3) | C10—C13 | 1.533 (3) |
C3—C11 | 1.515 (3) | C11—H11A | 0.9600 |
C3—C12 | 1.539 (3) | C11—H11B | 0.9600 |
C4—N5 | 1.252 (3) | C11—H11C | 0.9600 |
C4—H4 | 0.9300 | C12—H12A | 0.9600 |
N5—C6 | 1.457 (3) | C12—H12B | 0.9600 |
C6—C7 | 1.525 (3) | C12—H12C | 0.9600 |
C6—H6A | 0.9700 | C13—H13A | 0.9600 |
C6—H6B | 0.9700 | C13—H13B | 0.9600 |
C7—N8 | 1.460 (3) | C13—H13C | 0.9600 |
C7—H7A | 0.9700 | C14—H14A | 0.9600 |
C7—H7B | 0.9700 | C14—H14B | 0.9600 |
N8—C9 | 1.255 (3) | C14—H14C | 0.9600 |
C10—S1—S2 | 109.32 (8) | C9—C10—C13 | 110.1 (2) |
C3—S2—S1 | 109.26 (8) | C14—C10—C13 | 111.6 (2) |
C4—C3—C11 | 113.6 (2) | C9—C10—S1 | 106.72 (16) |
C4—C3—C12 | 109.6 (2) | C14—C10—S1 | 112.28 (17) |
C11—C3—C12 | 112.0 (2) | C13—C10—S1 | 102.69 (18) |
C4—C3—S2 | 106.40 (15) | C3—C11—H11A | 109.5 |
C11—C3—S2 | 112.61 (19) | C3—C11—H11B | 109.5 |
C12—C3—S2 | 101.91 (17) | H11A—C11—H11B | 109.5 |
N5—C4—C3 | 124.2 (2) | C3—C11—H11C | 109.5 |
N5—C4—H4 | 117.9 | H11A—C11—H11C | 109.5 |
C3—C4—H4 | 117.9 | H11B—C11—H11C | 109.5 |
C4—N5—C6 | 116.6 (2) | C3—C12—H12A | 109.5 |
N5—C6—C7 | 108.9 (2) | C3—C12—H12B | 109.5 |
N5—C6—H6A | 109.9 | H12A—C12—H12B | 109.5 |
C7—C6—H6A | 109.9 | C3—C12—H12C | 109.5 |
N5—C6—H6B | 109.9 | H12A—C12—H12C | 109.5 |
C7—C6—H6B | 109.9 | H12B—C12—H12C | 109.5 |
H6A—C6—H6B | 108.3 | C10—C13—H13A | 109.5 |
N8—C7—C6 | 108.8 (2) | C10—C13—H13B | 109.5 |
N8—C7—H7A | 109.9 | H13A—C13—H13B | 109.5 |
C6—C7—H7A | 109.9 | C10—C13—H13C | 109.5 |
N8—C7—H7B | 109.9 | H13A—C13—H13C | 109.5 |
C6—C7—H7B | 109.9 | H13B—C13—H13C | 109.5 |
H7A—C7—H7B | 108.3 | C10—C14—H14A | 109.5 |
C9—N8—C7 | 116.9 (2) | C10—C14—H14B | 109.5 |
N8—C9—C10 | 124.5 (2) | H14A—C14—H14B | 109.5 |
N8—C9—H9 | 117.8 | C10—C14—H14C | 109.5 |
C10—C9—H9 | 117.8 | H14A—C14—H14C | 109.5 |
C9—C10—C14 | 112.9 (2) | H14B—C14—H14C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C10H18N2S2 |
Mr | 230.38 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 294 |
a, b, c (Å) | 8.7393 (9), 8.9284 (9), 15.9117 (17) |
V (Å3) | 1241.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.28 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.807, 0.891 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8043, 2963, 2057 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.084, 1.03 |
No. of reflections | 2963 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
Absolute structure | Flack (1983), 1172 Friedel pairs |
Absolute structure parameter | 0.01 (10) |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
S1—C10 | 1.865 (2) | N5—C6 | 1.457 (3) |
S1—S2 | 2.0201 (10) | C6—C7 | 1.525 (3) |
S2—C3 | 1.865 (2) | C7—N8 | 1.460 (3) |
C3—C4 | 1.498 (3) | N8—C9 | 1.255 (3) |
C4—N5 | 1.252 (3) | C9—C10 | 1.501 (3) |
C10—S1—S2 | 109.32 (8) | C11—C3—C12 | 112.0 (2) |
C3—S2—S1 | 109.26 (8) | C4—C3—S2 | 106.40 (15) |
C4—C3—C11 | 113.6 (2) | C11—C3—S2 | 112.61 (19) |
C4—C3—C12 | 109.6 (2) | C12—C3—S2 | 101.91 (17) |
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 π–π interaction is observed.