Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680100407X/cf6051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680100407X/cf6051Isup2.hkl |
CCDC reference: 162813
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.013 Å
- R factor = 0.041
- wR factor = 0.033
- Data-to-parameter ratio = 12.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N1 - H1NA ? PLAT_420 Alert C D-H Without Acceptor N1 - H1NB ? PLAT_703 Alert C Torsion Calc 80.3(11), Rep 79.0(10), Dev. 1.18 Sigma C1 -N2 -C4 -C5 1.555 1.555 1.555 1.555 General Notes
ABSTM_02 The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.330 0.768 Tmin and Tmax expected: 0.258 0.766 RR = 1.278 Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
6,6,9,9-Hexamethylhexahydroimidazo[2,1-d][1,2,5]dithiazepine (4.85 g) and methyl iodide (3.64 g, 1.3 molar equivalent, not distilled) in 20 ml of ethyl alcohol were refluxed for 3 h. After cooling, crystals were collected by filtration and washed with diethyl ether. Yield 6.17 g, m.p. 466–468 K.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1995); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976; Hall et al., 1999); software used to prepare material for publication: TEXSAN.
Fig. 1. A view of (I) with displacement ellipsoids shown at the 20% probability level. | |
Fig. 2. A depiction of the packing for (I). |
C10H20N2S2+·I3− | F(000) = 1140.00 |
Mr = 613.11 | Dx = 2.222 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
a = 8.3334 (9) Å | Cell parameters from 25 reflections |
b = 8.080 (2) Å | θ = 8.1–12.1° |
c = 27.274 (6) Å | µ = 5.33 mm−1 |
β = 93.57 (1)° | T = 294 K |
V = 1832.9 (5) Å3 | Prism, brown |
Z = 4 | 0.30 × 0.22 × 0.05 mm |
Enraf-Nonius CAD-4 diffractometer | 1918 reflections with I > 3σ(I) |
Radiation source: sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω–θ scans | h = −9→9 |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | k = −1→9 |
Tmin = 0.330, Tmax = 0.768 | l = −1→32 |
4236 measured reflections | 3 standard reflections every 100 reflections |
3218 independent reflections | intensity decay: 2.6% |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters not refined |
wR(F2) = 0.033 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00002|Fo|2] |
S = 1.60 | (Δ/σ)max = 0.001 |
1918 reflections | Δρmax = 0.82 e Å−3 |
154 parameters | Δρmin = −0.86 e Å−3 |
C10H20N2S2+·I3− | V = 1832.9 (5) Å3 |
Mr = 613.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3334 (9) Å | µ = 5.33 mm−1 |
b = 8.080 (2) Å | T = 294 K |
c = 27.274 (6) Å | 0.30 × 0.22 × 0.05 mm |
β = 93.57 (1)° |
Enraf-Nonius CAD-4 diffractometer | 1918 reflections with I > 3σ(I) |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | Rint = 0.024 |
Tmin = 0.330, Tmax = 0.768 | 3 standard reflections every 100 reflections |
4236 measured reflections | intensity decay: 2.6% |
3218 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.033 | H-atom parameters not refined |
S = 1.60 | Δρmax = 0.82 e Å−3 |
1918 reflections | Δρmin = −0.86 e Å−3 |
154 parameters |
x | y | z | Uiso*/Ueq | ||
I1 | −0.11874 (9) | 0.2624 (1) | 0.47403 (3) | 0.0638 (3) | |
I2 | 0.01726 (9) | 0.39447 (9) | 0.38661 (3) | 0.0540 (2) | |
I3 | 0.1433 (1) | 0.5323 (1) | 0.29796 (3) | 0.0779 (3) | |
S1 | 0.4436 (4) | 0.0882 (4) | 0.3916 (1) | 0.069 (1) | |
S2 | 0.3792 (3) | −0.1334 (4) | 0.4146 (1) | 0.075 (1) | |
N1 | 0.8474 (10) | −0.1786 (10) | 0.4202 (3) | 0.050 (3) | |
N2 | 0.6997 (9) | −0.1354 (10) | 0.3544 (3) | 0.043 (3) | |
C1 | 0.702 (1) | −0.185 (1) | 0.4010 (4) | 0.038 (3) | |
C2 | 0.965 (1) | −0.122 (1) | 0.3877 (4) | 0.050 (3) | |
C3 | 0.866 (1) | −0.091 (1) | 0.3409 (4) | 0.063 (4) | |
C4 | 0.561 (1) | −0.110 (1) | 0.3210 (4) | 0.047 (3) | |
C5 | 0.473 (1) | 0.052 (1) | 0.3264 (4) | 0.045 (3) | |
C6 | 0.564 (1) | −0.251 (1) | 0.4288 (4) | 0.045 (3) | |
C7 | 0.526 (1) | −0.427 (1) | 0.4110 (5) | 0.088 (5) | |
C8 | 0.607 (1) | −0.246 (2) | 0.4835 (5) | 0.073 (4) | |
C9 | 0.570 (1) | 0.202 (1) | 0.3125 (5) | 0.071 (4) | |
C10 | 0.313 (1) | 0.039 (1) | 0.2948 (5) | 0.079 (5) | |
H1Na | 0.8770 | −0.2866 | 0.4312 | 0.060* | |
H1Nb | 0.8491 | −0.1057 | 0.4476 | 0.060* | |
H2a | 1.0464 | −0.2061 | 0.3833 | 0.060* | |
H2b | 1.0171 | −0.0212 | 0.3998 | 0.060* | |
H3a | 0.9004 | −0.1618 | 0.3146 | 0.076* | |
H3b | 0.8724 | 0.0235 | 0.3309 | 0.076* | |
H4a | 0.4862 | −0.1995 | 0.3258 | 0.057* | |
H4b | 0.5969 | −0.1149 | 0.2878 | 0.057* | |
H7b | 0.4142 | −0.4532 | 0.4162 | 0.105* | |
H7c | 0.5434 | −0.4359 | 0.3763 | 0.105* | |
H7a | 0.5951 | −0.5052 | 0.4292 | 0.105* | |
H8b | 0.6918 | −0.3247 | 0.4917 | 0.088* | |
H8c | 0.5128 | −0.2738 | 0.5011 | 0.088* | |
H8a | 0.6429 | −0.1354 | 0.4927 | 0.088* | |
H9b | 0.5220 | 0.3008 | 0.3252 | 0.085* | |
H9c | 0.6792 | 0.1905 | 0.3263 | 0.085* | |
H9a | 0.5699 | 0.2090 | 0.2770 | 0.085* | |
H10b | 0.2460 | 0.1339 | 0.3012 | 0.095* | |
H10c | 0.2572 | −0.0617 | 0.3031 | 0.095* | |
H10a | 0.3349 | 0.0368 | 0.2603 | 0.095* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0557 (5) | 0.0717 (6) | 0.0633 (6) | −0.0001 (4) | −0.0016 (4) | 0.0127 (5) |
I2 | 0.0532 (4) | 0.0457 (4) | 0.0628 (5) | 0.0049 (4) | 0.0029 (4) | −0.0048 (4) |
I3 | 0.1032 (7) | 0.0692 (6) | 0.0640 (6) | 0.0076 (5) | 0.0267 (6) | −0.0036 (5) |
S1 | 0.075 (2) | 0.066 (2) | 0.067 (2) | 0.026 (2) | 0.007 (2) | −0.009 (2) |
S2 | 0.040 (2) | 0.101 (3) | 0.088 (3) | 0.017 (2) | 0.018 (2) | 0.029 (2) |
N1 | 0.043 (5) | 0.054 (6) | 0.054 (6) | 0.002 (5) | −0.004 (5) | −0.007 (5) |
N2 | 0.039 (5) | 0.048 (6) | 0.041 (6) | 0.012 (4) | 0.000 (5) | 0.001 (5) |
C1 | 0.031 (6) | 0.045 (6) | 0.036 (7) | 0.011 (5) | −0.010 (5) | −0.011 (6) |
C2 | 0.039 (6) | 0.044 (7) | 0.068 (8) | 0.003 (5) | 0.015 (6) | −0.005 (6) |
C3 | 0.042 (6) | 0.085 (9) | 0.065 (9) | 0.012 (7) | 0.016 (6) | 0.019 (8) |
C4 | 0.042 (6) | 0.064 (7) | 0.034 (6) | 0.008 (6) | −0.012 (5) | −0.004 (6) |
C5 | 0.042 (6) | 0.045 (7) | 0.048 (7) | 0.012 (5) | 0.000 (6) | −0.007 (6) |
C6 | 0.032 (6) | 0.056 (7) | 0.049 (7) | 0.003 (5) | 0.005 (5) | 0.009 (6) |
C7 | 0.079 (9) | 0.067 (10) | 0.12 (1) | −0.025 (7) | −0.012 (9) | 0.021 (9) |
C8 | 0.052 (7) | 0.11 (1) | 0.059 (9) | −0.005 (7) | 0.015 (7) | 0.015 (9) |
C9 | 0.071 (8) | 0.058 (8) | 0.083 (10) | 0.010 (7) | −0.011 (7) | 0.015 (7) |
C10 | 0.052 (7) | 0.071 (9) | 0.11 (1) | 0.012 (7) | −0.006 (8) | 0.000 (8) |
I1—I2 | 2.906 (1) | C4—H4a | 0.97 |
I2—I3 | 2.916 (1) | C4—H4b | 0.97 |
S1—S2 | 1.983 (4) | C5—C9 | 1.52 (1) |
S1—C5 | 1.83 (1) | C5—C10 | 1.54 (1) |
S2—C6 | 1.830 (10) | C6—C7 | 1.53 (1) |
N1—C1 | 1.29 (1) | C6—C8 | 1.51 (1) |
N1—C2 | 1.44 (1) | C7—H7b | 0.97 |
N1—H1Na | 0.95 | C7—H7c | 0.97 |
N1—H1Nb | 0.95 | C7—H7a | 0.97 |
N2—C1 | 1.33 (1) | C8—H8b | 0.97 |
N2—C3 | 1.50 (1) | C8—H8c | 0.97 |
N2—C4 | 1.44 (1) | C8—H8a | 0.97 |
C1—C6 | 1.51 (1) | C9—H9b | 0.97 |
C2—C3 | 1.50 (1) | C9—H9c | 0.97 |
C2—H2a | 0.97 | C9—H9a | 0.97 |
C2—H2b | 0.97 | C10—H10b | 0.97 |
C3—H3a | 0.97 | C10—H10c | 0.97 |
C3—H3b | 0.97 | C10—H10a | 0.97 |
C4—C5 | 1.51 (1) | ||
S2···C2i | 3.481 (10) | I1···S2iii | 3.981 (3) |
I1···N1ii | 3.617 (8) | I2···N1iv | 3.861 (8) |
I1···N1i | 3.858 (8) | I2···C2iv | 3.931 (8) |
I1···C2i | 3.985 (9) | I3···C3v | 3.912 (10) |
I1—I2—I3 | 178.05 (4) | S1—C5—C10 | 113.0 (8) |
S2—S1—C5 | 102.5 (4) | C4—C5—C9 | 113.1 (8) |
S1—S2—C6 | 107.2 (4) | C4—C5—C10 | 107.4 (8) |
C1—N1—C2 | 115.0 (9) | C9—C5—C10 | 111.6 (9) |
C1—N1—H1Na | 108.1 | S2—C6—C1 | 111.3 (7) |
C1—N1—H1Nb | 108.1 | S2—C6—C7 | 105.2 (7) |
C2—N1—H1Na | 108.1 | S2—C6—C8 | 109.7 (8) |
C2—N1—H1Nb | 108.1 | C1—C6—C7 | 108.7 (9) |
H1Na—N1—H1Nb | 109.5 | C1—C6—C8 | 110.1 (9) |
C1—N2—C3 | 110.4 (9) | C7—C6—C8 | 111.8 (10) |
C1—N2—C4 | 127.6 (9) | C6—C7—H7b | 109.5 |
C3—N2—C4 | 121.8 (9) | C6—C7—H7c | 109.5 |
N1—C1—N2 | 109.4 (9) | C6—C7—H7a | 109.5 |
N1—C1—C6 | 122.2 (10) | H7b—C7—H7c | 109.5 |
N2—C1—C6 | 128.3 (9) | H7b—C7—H7a | 109.4 |
N1—C2—C3 | 102.5 (8) | H7c—C7—H7a | 109.4 |
N1—C2—H2a | 111.2 | C6—C8—H8b | 109.5 |
N1—C2—H2b | 111.2 | C6—C8—H8c | 109.5 |
C3—C2—H2a | 111.2 | C6—C8—H8a | 109.5 |
C3—C2—H2b | 111.2 | H8b—C8—H8c | 109.5 |
H2a—C2—H2b | 109.5 | H8b—C8—H8a | 109.4 |
N2—C3—C2 | 102.7 (8) | H8c—C8—H8a | 109.4 |
N2—C3—H3a | 111.1 | C5—C9—H9b | 109.5 |
N2—C3—H3b | 111.2 | C5—C9—H9c | 109.5 |
C2—C3—H3a | 111.1 | C5—C9—H9a | 109.5 |
C2—C3—H3b | 111.1 | H9b—C9—H9c | 109.5 |
H3a—C3—H3b | 109.5 | H9b—C9—H9a | 109.5 |
N2—C4—C5 | 116.0 (9) | H9c—C9—H9a | 109.5 |
N2—C4—H4a | 107.8 | C5—C10—H10b | 109.4 |
N2—C4—H4b | 107.8 | C5—C10—H10c | 109.4 |
C5—C4—H4a | 107.8 | C5—C10—H10a | 109.5 |
C5—C4—H4b | 107.8 | H10b—C10—H10c | 109.4 |
H4a—C4—H4b | 109.5 | H10b—C10—H10a | 109.5 |
S1—C5—C4 | 109.2 (7) | H10c—C10—H10a | 109.5 |
S1—C5—C9 | 102.6 (8) | ||
S1—S2—C6—C1 | −23.5 (8) | N2—C1—N1—C2 | 0 (1) |
S1—S2—C6—C7 | −141.0 (7) | N2—C1—C6—C7 | 73 (1) |
S1—S2—C6—C8 | 98.6 (8) | N2—C1—C6—C8 | −163 (1) |
S1—C5—C4—N2 | −46 (1) | N2—C4—C5—C9 | 67 (1) |
S2—S1—C5—C4 | −42.9 (7) | N2—C4—C5—C10 | −169.1 (9) |
S2—S1—C5—C9 | −163.1 (6) | C1—N1—C2—C3 | 0 (1) |
S2—S1—C5—C10 | 76.6 (8) | C1—N2—C3—C2 | 0 (1) |
S2—C6—C1—N1 | 142.7 (8) | C1—N2—C4—C5 | 79 (1) |
S2—C6—C1—N2 | −42 (1) | C2—N1—C1—C6 | 176.1 (9) |
N1—C1—N2—C3 | 0 (1) | C2—C3—N2—C4 | 174.4 (9) |
N1—C1—N2—C4 | −174.2 (9) | C3—N2—C1—C6 | −175.4 (9) |
N1—C1—C6—C7 | −101 (1) | C3—N2—C4—C5 | −94 (1) |
N1—C1—C6—C8 | 20 (1) | C4—N2—C1—C6 | 10 (1) |
N1—C2—C3—N2 | 0 (1) | C5—S1—S2—C6 | 83.7 (5) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+1; (iv) x−1, y+1, z; (v) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H20N2S2+·I3− |
Mr | 613.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 8.3334 (9), 8.080 (2), 27.274 (6) |
β (°) | 93.57 (1) |
V (Å3) | 1832.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.33 |
Crystal size (mm) | 0.30 × 0.22 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Analytical (de Meulenaer & Tompa, 1965) |
Tmin, Tmax | 0.330, 0.768 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 4236, 3218, 1918 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.033, 1.60 |
No. of reflections | 1918 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.82, −0.86 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1995), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1992), SHELXS86 (Sheldrick, 1985), TEXSAN, ORTEPII (Johnson, 1976; Hall et al., 1999).
I1—I2 | 2.906 (1) | N1—C1 | 1.29 (1) |
I2—I3 | 2.916 (1) | N1—C2 | 1.44 (1) |
S1—S2 | 1.983 (4) | N2—C1 | 1.33 (1) |
S1—C5 | 1.83 (1) | N2—C3 | 1.50 (1) |
S2—C6 | 1.830 (10) | N2—C4 | 1.44 (1) |
I1···N1i | 3.617 (8) | I2···N1iv | 3.861 (8) |
I1···N1ii | 3.858 (8) | I2···C2iv | 3.931 (8) |
I1···C2ii | 3.985 (9) | I3···C3v | 3.912 (10) |
I1···S2iii | 3.981 (3) | ||
I1—I2—I3 | 178.05 (4) | C1—N2—C3 | 110.4 (9) |
S2—S1—C5 | 102.5 (4) | C1—N2—C4 | 127.6 (9) |
S1—S2—C6 | 107.2 (4) | C3—N2—C4 | 121.8 (9) |
C1—N1—C2 | 115.0 (9) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) −x, −y, −z+1; (iv) x−1, y+1, z; (v) −x+1, y+1/2, −z+1/2. |
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Growing interest in the potential of radioisotopes 186Re and 188Re for tumour-targeting radiotherapy (Nicolini & Mazzi, 1999) has led to the investigation of suitable ligands for complexation. In previous papers (Jackson et al., 1993, 2001; Hambley et al., 1995), we have described the preparation of several lipophilic rhenium–diamino–dithiolate complexes and their crystal structures. We report here the crystal structure of the protonated form of a ligand suitable for complexation with Re isotopes. The ligand is 6,6,9,9-tetramethyl-1,2,5,6,9,9a-hexahydroimidazo[2,1-d][1,2,5]dithiazepine and is reported as the triiodide salt, (I).
The closest contact between the heterocyclic cation and its counter-ion is 3.617 (8) Å, i.e. between I1 and the protonated N1 atom. The Cambridge Structural Database (Allen & Kennard, 1993) has 13 contacts between iodine and a protonated secondary amine, for which the mean distance is 3.649 Å and the shortest is 3.437 Å. In addition to an electrostatic interaction, there may be weak hydrogen bonding between the triiodide and the protonated nitrogen site of the heterocyclic cation.
The disulfide S—S bond of 1.983 (4) Å in the title compound is significantly shorter then the mean length of 2.038 Å obtained from the Cambridge Structural Database. The shortest disulfide bond length in the Cambridge Structural Database is 1.950 Å.
As Fig. 2 indicates, the heterocyclic cation and its counter-ion pack in channels running parallel to the a axis of the unit cell and are separated by the length of that axis.