Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010302732X/sk1685sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010302732X/sk1685Isup2.hkl |
CCDC reference: 231093
A solution of 2-bromoacetyl bromide (2.84 g, 14.08 mmol) and pyridine (1.11 g, 14.08 mmol) in CHCl3 (20 ml) was added dropwise over 30 min to a solution of 1-thia-4,7-diazacyclononane (0.97 g, 6.64 mmol) in CHCl3 (15 ml) cooled to 273 K. The resulting reaction mixture was stirred at room temperaure for 12 h. The solvent was removed under reduced pressure and the residue was taken up in diethyl ether. On standing, a white crystalline solid separated. Crystals suitable for X-ray diffraction analysis were grown by diffusion of Et2O vapour into a DMF solution of the product. Analysis found: C 30.50, H 4.12, N 7.18 (7.22)%; calculated for C10H16Br2N2O2S: C 30.95, H 4.15, N 7.22%. 13C NMR (D2O, 75.47 MHz, 298 K): δ 27.2, 32.5, 38.8, 39.6, 44.4, 47.3, 47.8, 50.0, 166.6. 171.8.
H atoms were placed geometrically and thereafter treated as riding on their parent C atoms [C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C)].
Data collection: STADI4 (Stoe & Cie, 1997); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: enCIFer (CCDC, 2003) and PLATON (Spek, 2003).
C10H16BrN2O2S+·Br− | Z = 2 |
Mr = 388.13 | F(000) = 384 |
Triclinic, P1 | Dx = 1.929 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2655 (10) Å | Cell parameters from 56 reflections |
b = 9.5032 (13) Å | θ = 12.5–15° |
c = 10.0740 (15) Å | µ = 6.21 mm−1 |
α = 86.665 (12)° | T = 150 K |
β = 75.553 (13)° | Block, colourless |
γ = 83.068 (10)° | 0.52 × 0.25 × 0.19 mm |
V = 668.36 (17) Å3 |
Stoe Stadi-4 four-circle diffractometer | 2109 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.059 |
Graphite monochromator | θmax = 25.1°, θmin = 2.1° |
ω–θ scans | h = −8→8 |
Absorption correction: ψ scan (X-RED; Stoe & Cie, 1997) | k = −11→11 |
Tmin = 0.112, Tmax = 0.308 | l = −2→11 |
2374 measured reflections | 3 standard reflections every 60 min |
2360 independent reflections | intensity decay: none |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.082P)2 + 2.906P] where P = (Fo2 + 2Fc2)/3 |
2360 reflections | (Δ/σ)max = 0.002 |
154 parameters | Δρmax = 1.17 e Å−3 |
0 restraints | Δρmin = −1.48 e Å−3 |
C10H16BrN2O2S+·Br− | γ = 83.068 (10)° |
Mr = 388.13 | V = 668.36 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2655 (10) Å | Mo Kα radiation |
b = 9.5032 (13) Å | µ = 6.21 mm−1 |
c = 10.0740 (15) Å | T = 150 K |
α = 86.665 (12)° | 0.52 × 0.25 × 0.19 mm |
β = 75.553 (13)° |
Stoe Stadi-4 four-circle diffractometer | 2109 reflections with I > 2σ(I) |
Absorption correction: ψ scan (X-RED; Stoe & Cie, 1997) | Rint = 0.059 |
Tmin = 0.112, Tmax = 0.308 | 3 standard reflections every 60 min |
2374 measured reflections | intensity decay: none |
2360 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.17 e Å−3 |
2360 reflections | Δρmin = −1.48 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.04277 (17) | 0.56457 (13) | 0.18159 (12) | 0.0178 (3) | |
C2 | 0.1873 (7) | 0.5085 (5) | 0.3044 (5) | 0.0210 (11) | |
H2A | 0.1004 | 0.5173 | 0.3971 | 0.025* | |
H2B | 0.2291 | 0.4060 | 0.2914 | 0.025* | |
C3 | 0.3633 (7) | 0.5786 (5) | 0.3068 (5) | 0.0207 (11) | |
H3A | 0.4518 | 0.5084 | 0.3434 | 0.025* | |
H3B | 0.4287 | 0.6029 | 0.2111 | 0.025* | |
N4 | 0.3297 (6) | 0.7078 (4) | 0.3878 (4) | 0.0159 (8) | |
C5 | 0.3902 (7) | 0.8409 (5) | 0.3181 (6) | 0.0206 (10) | |
H5A | 0.4859 | 0.8183 | 0.2311 | 0.025* | |
H5B | 0.4533 | 0.8890 | 0.3765 | 0.025* | |
C6 | 0.2260 (7) | 0.9432 (5) | 0.2867 (5) | 0.0197 (10) | |
H6A | 0.1539 | 0.9925 | 0.3710 | 0.024* | |
H6B | 0.2781 | 1.0156 | 0.2173 | 0.024* | |
N7 | 0.0977 (6) | 0.8651 (4) | 0.2351 (4) | 0.0179 (9) | |
C8 | −0.0452 (7) | 0.8072 (5) | 0.3281 (5) | 0.0192 (11) | |
O8 | −0.0952 (5) | 0.8348 (4) | 0.4496 (4) | 0.0232 (8) | |
C9 | −0.1375 (7) | 0.6999 (5) | 0.2703 (5) | 0.0196 (10) | |
H9A | −0.2091 | 0.7478 | 0.2057 | 0.024* | |
H9B | −0.2293 | 0.6549 | 0.3455 | 0.024* | |
C10 | 0.1368 (8) | 0.8354 (6) | 0.0883 (5) | 0.0224 (11) | |
H10A | 0.2463 | 0.8858 | 0.0380 | 0.027* | |
H10B | 0.0242 | 0.8743 | 0.0539 | 0.027* | |
C11 | 0.1824 (7) | 0.6772 (5) | 0.0554 (5) | 0.0208 (10) | |
H11A | 0.3198 | 0.6484 | 0.0491 | 0.025* | |
H11B | 0.1585 | 0.6631 | −0.0352 | 0.025* | |
C12 | 0.2591 (7) | 0.6925 (5) | 0.5239 (6) | 0.0208 (11) | |
O12 | 0.2272 (5) | 0.5752 (4) | 0.5793 (4) | 0.0234 (8) | |
C13 | 0.2144 (7) | 0.8203 (6) | 0.6135 (5) | 0.0218 (11) | |
H13A | 0.0864 | 0.8190 | 0.6771 | 0.026* | |
H13B | 0.2143 | 0.9084 | 0.5560 | 0.026* | |
Br | 0.41008 (8) | 0.81431 (5) | 0.71747 (5) | 0.0259 (2) | |
Br1 | 0.29938 (7) | 0.26367 (6) | 0.03575 (5) | 0.0253 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0175 (6) | 0.0153 (6) | 0.0212 (6) | 0.0009 (5) | −0.0069 (5) | −0.0021 (5) |
C2 | 0.025 (3) | 0.017 (2) | 0.024 (3) | 0.005 (2) | −0.015 (2) | −0.001 (2) |
C3 | 0.022 (3) | 0.016 (2) | 0.026 (3) | 0.003 (2) | −0.011 (2) | −0.007 (2) |
N4 | 0.016 (2) | 0.013 (2) | 0.017 (2) | 0.0030 (16) | −0.0039 (16) | −0.0056 (16) |
C5 | 0.017 (2) | 0.016 (2) | 0.029 (3) | −0.0020 (19) | −0.005 (2) | 0.000 (2) |
C6 | 0.022 (2) | 0.012 (2) | 0.028 (3) | −0.0020 (19) | −0.011 (2) | 0.001 (2) |
N7 | 0.017 (2) | 0.016 (2) | 0.020 (2) | 0.0009 (16) | −0.0055 (17) | 0.0002 (16) |
C8 | 0.015 (2) | 0.010 (2) | 0.031 (3) | 0.0057 (18) | −0.007 (2) | 0.002 (2) |
O8 | 0.0257 (19) | 0.0190 (18) | 0.0212 (19) | 0.0033 (15) | 0.0001 (15) | −0.0078 (14) |
C9 | 0.014 (2) | 0.016 (2) | 0.027 (3) | 0.0044 (19) | −0.003 (2) | −0.005 (2) |
C10 | 0.024 (3) | 0.022 (3) | 0.023 (3) | −0.003 (2) | −0.008 (2) | 0.006 (2) |
C11 | 0.021 (2) | 0.024 (3) | 0.016 (2) | 0.003 (2) | −0.004 (2) | −0.002 (2) |
C12 | 0.021 (2) | 0.017 (3) | 0.030 (3) | 0.0045 (19) | −0.016 (2) | −0.004 (2) |
O12 | 0.031 (2) | 0.0144 (17) | 0.0274 (19) | −0.0011 (15) | −0.0130 (16) | 0.0039 (15) |
C13 | 0.024 (3) | 0.021 (3) | 0.021 (3) | 0.005 (2) | −0.008 (2) | −0.008 (2) |
Br | 0.0280 (3) | 0.0230 (3) | 0.0301 (3) | −0.0031 (2) | −0.0123 (2) | −0.0044 (2) |
Br1 | 0.0222 (3) | 0.0301 (3) | 0.0234 (3) | 0.0017 (2) | −0.0073 (2) | −0.0024 (2) |
S1—C2 | 1.831 (5) | C2—H2A | 0.9900 |
S1—C9 | 1.819 (5) | C2—H2B | 0.9900 |
S1—C11 | 1.803 (5) | C3—H3A | 0.9900 |
C2—C3 | 1.518 (7) | C3—H3B | 0.9900 |
C3—N4 | 1.476 (6) | C5—H5A | 0.9900 |
N4—C12 | 1.345 (7) | C5—H5B | 0.9900 |
N4—C5 | 1.471 (6) | C6—H6A | 0.9900 |
C5—C6 | 1.530 (7) | C6—H6B | 0.9900 |
C6—N7 | 1.464 (6) | C9—H9A | 0.9900 |
N7—C8 | 1.361 (7) | C9—H9B | 0.9900 |
N7—C10 | 1.472 (7) | C10—H10A | 0.9900 |
C10—C11 | 1.537 (7) | C10—H10B | 0.9900 |
C8—O8 | 1.221 (6) | C11—H11A | 0.9900 |
C8—C9 | 1.502 (7) | C11—H11B | 0.9900 |
C12—O12 | 1.238 (6) | C13—H13A | 0.9900 |
C12—C13 | 1.511 (7) | C13—H13B | 0.9900 |
C13—Br | 1.959 (5) | ||
C2—S1—C9 | 104.1 (2) | H3A—C3—H3B | 107.4 |
C2—S1—C11 | 106.0 (2) | N4—C5—H5A | 108.8 |
C9—S1—C11 | 98.7 (2) | C6—C5—H5A | 108.8 |
C3—C2—S1 | 121.9 (4) | N4—C5—H5B | 108.8 |
N4—C3—C2 | 116.2 (4) | C6—C5—H5B | 108.8 |
C12—N4—C5 | 124.2 (4) | H5A—C5—H5B | 107.7 |
C12—N4—C3 | 116.9 (4) | N7—C6—H6A | 109.7 |
C5—N4—C3 | 118.7 (4) | C5—C6—H6A | 109.7 |
N4—C5—C6 | 113.8 (4) | N7—C6—H6B | 109.7 |
N7—C6—C5 | 110.0 (4) | C5—C6—H6B | 109.7 |
C8—N7—C6 | 118.0 (4) | H6A—C6—H6B | 108.2 |
C8—N7—C8 | 120.9 (4) | C8—C9—H9A | 109.6 |
C6—N7—C10 | 120.7 (4) | S1—C9—H9A | 109.6 |
N7—C10—C11 | 114.4 (4) | C8—C9—H9B | 109.6 |
C10—C11—S1 | 113.2 (3) | S1—C9—H9B | 109.6 |
O8—C8—N7 | 124.6 (5) | H9A—C9—H9B | 108.1 |
O8—C8—C9 | 121.1 (5) | N7—C10—H10A | 108.7 |
N7—C8—C9 | 114.3 (4) | C11—C10—H10A | 108.7 |
C8—C9—S1 | 110.4 (3) | N7—C10—H10B | 108.7 |
O12—C12—N4 | 121.7 (5) | C11—C10—H10B | 108.7 |
O12—C12—C13 | 118.1 (5) | H10A—C10—H10B | 107.6 |
N4—C12—C13 | 120.1 (5) | C10—C11—H11A | 108.9 |
C12—C13—Br | 108.4 (3) | S1—C11—H11A | 108.9 |
C3—C2—H2A | 106.9 | C10—C11—H11B | 108.9 |
S1—C2—H2A | 106.9 | S1—C11—H11B | 108.9 |
C3—C2—H2B | 106.9 | H11A—C11—H11B | 107.7 |
S1—C2—H2B | 106.9 | C12—C13—H13A | 110.0 |
H2A—C2—H2B | 106.7 | Br—C13—H13A | 110.0 |
N4—C3—H3A | 108.2 | C12—C13—H13B | 110.0 |
C2—C3—H3A | 108.2 | Br—C13—H13B | 110.0 |
N4—C3—H3B | 108.2 | H13A—C13—H13B | 108.4 |
C2—C3—H3B | 108.2 | ||
C11—S1—C2—C3 | 12.7 (5) | C6—N7—C8—O8 | 13.0 (7) |
C9—S1—C2—C3 | −90.9 (4) | C10—N7—C8—O8 | −174.4 (5) |
S1—C2—C3—N4 | 85.6 (5) | C6—N7—C8—C9 | −165.3 (4) |
C2—C3—N4—C12 | 64.5 (6) | C10—N7—C8—C9 | 7.2 (6) |
C2—C3—N4—C5 | −120.8 (5) | O8—C8—C9—S1 | −125.4 (4) |
C12—N4—C5—C6 | −83.5 (6) | N7—C8—C9—S1 | 53.0 (5) |
C3—N4—C5—C6 | 102.2 (5) | C11—S1—C9—C8 | −59.3 (4) |
N4—C5—C6—N7 | −42.6 (6) | C2—S1—C9—C8 | 49.8 (4) |
C5—C6—N7—C8 | 86.5 (5) | C5—N4—C12—O12 | −173.0 (4) |
C5—C6—N7—C10 | −86.1 (5) | C3—N4—C12—O12 | 1.4 (7) |
C8—N7—C10—C11 | −57.6 (6) | C5—N4—C12—C13 | 7.6 (7) |
C6—N7—C10—C11 | 114.8 (5) | C3—N4—C12—C13 | −178.0 (4) |
N7—C10—C11—S1 | 37.4 (5) | O12—C12—C13—Br | 74.1 (5) |
C9—S1—C11—C10 | 14.3 (4) | N4—C12—C13—Br | −106.5 (5) |
C2—S1—C11—C10 | −93.2 (4) |
Experimental details
Crystal data | |
Chemical formula | C10H16BrN2O2S+·Br− |
Mr | 388.13 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 7.2655 (10), 9.5032 (13), 10.0740 (15) |
α, β, γ (°) | 86.665 (12), 75.553 (13), 83.068 (10) |
V (Å3) | 668.36 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.21 |
Crystal size (mm) | 0.52 × 0.25 × 0.19 |
Data collection | |
Diffractometer | Stoe Stadi-4 four-circle diffractometer |
Absorption correction | ψ scan (X-RED; Stoe & Cie, 1997) |
Tmin, Tmax | 0.112, 0.308 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2374, 2360, 2109 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.126, 1.05 |
No. of reflections | 2360 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.17, −1.48 |
Computer programs: STADI4 (Stoe & Cie, 1997), STADI4, X-RED (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), enCIFer (CCDC, 2003) and PLATON (Spek, 2003).
S1—C2 | 1.831 (5) | S1—C11 | 1.803 (5) |
S1—C9 | 1.819 (5) | ||
C2—S1—C9 | 104.1 (2) | C9—S1—C11 | 98.7 (2) |
C2—S1—C11 | 106.0 (2) |
The design and synthesis of macrobicyclic and macrotricyclic ligands, including cages and cryptands, and the preparation of their metal complexes are topics of current interest (Sargeson, 1996; Ingham et al., 2002). Many of the polymacrocyclic ligands described so far, some of them based on a cyclam framework, have been used extensively for the preparation of metal complexes of high kinetic and thermodynamic stability, such complexes often exhibiting specific coordination and redox properties. Two major synthetic approaches are normally used in the preparation of these types of macrocyclic systems, viz. direct synthesis based on conventional organic reactions and metal-ion template synthesis (Ingham et al., 2002). The second procedure involves the preparation of a complexed metal ion within which the coordinated ligand can undergo further reaction.
With the aim of preparing new mixed-donor macrobicyclic ligands containing the 1-thia-4,7-diazacyclononane ([9]aneN2S) framework, we sought to use the corresponding 2-bromo-acetyl derivative, (I), as a suitable claw-like precursor. Three macropolycyclic systems containing the [9]aneN2S framework have already been reported in the literature, namely (II), (III) and (IV). Compound (II) was synthesized by reaction of cyclam with four equivalents of chloroacetyl chloride, followed by ring closure with Na2S and subsequent reduction with BH3 (Ingham et al., 2002). Compound (III) was prepared by reacting [9]aneN2S with 1,3-bis(2-chloro-acetamido)propane, followed by reduction with BH3 and reaction of the resulting macrobicycle system with (BrCH2CH2)2S (Ingham et al., 2002). The alternative template method was employed in the preparation of (IV), starting from the CuII complex of 4,7-bis(3-aminopropyl)-1-thia-4,7-diaza-cyclononane (Fortier & McAuley, 1989). In order to prepare (I), we reacted [9]aneN2S with two equivalents of bromoacetyl bromide and pyridine in CHCl3 and the residue obtained after removal of the solvent was dissolved in diethyl ether. A white crystalline solid, having a good elemental analyis for (I), separated from the Et2O solution. Interestingly, this product was soluble in water and insoluble in CHCl3, suggesting that the compound isolated was not (I). Single crystals were grown by diffusion of Et2O vapour into a DMF solution of the product and X-ray diffraction analysis was undertaken to ascertain its nature.
The structure determination revealed the formation of the unexpected salt 4-(2-bromo-acetyl)-8-oxa-1-thionia-4,7-diaza-bicyclo[5.2.2]undecane bromide, (V) (Fig. 1), as the result of an intramolecular cyclization of (I), where a bromoacetyl pendant arm undergoes nucleophilic attack by the S-donor of the [9]aneN2S framework. The resulting bicyclic sulphonium cation in this salt incorporates fused six- and nine-membered rings, the former adopting a boat conformation with sulphonium atom S1 at the bridgehead. Atom S1 interacts with the bromide counterion in the same asymmetric unit [S1···Br1 = 3.4127 (14) Å; Fig. 1]. The acetyl bridge formed between atoms N7 and S1 causes the [9]aneN2S framework to assume a [234] conformation, in contrast to the [333] conformation normally observed for [9]aneN2S and its pendant-arm derivatives within their metal-ion complexes (Danks et al., 1998; Arca et al., 2003). The S1—C bond lengths and the C—S1—C angles (Table 1) are typical for this type of compound and are comparable to those observed for the bicyclic sulphonium salt [C6H11S3]BF4 obtained by oxidation of 1,4,7-trithiacyclononane ([9]aneS3) with AuIII, which proceeds via C—H bond cleavage and transannular S—C bond formation (Taylor et al., 1991).
Two units of salt (V) are linked about a crystallographic inversion centre, forming dimers via S···Br contacts [S1···Br1i = 3.8676 (14) Å]. These contacts are longer than the S1···Br1 contact within the asymmetric unit (Fig. 2), and thus two sulphonium cations and two bromide anions are located on the opposite corners of a parallelogram [S1···Br1···S1i = 68.94 (3)° and Br1···S1···Br1i = 111.06 (3)°]. Dimers of (V) are joined via Br···Br contacts of 3.6348 (9) Å between bromide anions and Br atoms belonging to unreacted bromoacetyl pendant arms [Brii···Br1···S1i = 167.77 (3)°], thus forming ribbons that run along the [101] direction. Ribbons of this type are joined via S···O contacts of 3.0512 (4) Å, forming two-dimensional sheets (Fig. 3). The use of (V) as an intermediate for the asymmetric functionalization of [9]aneS3 is under investigation in our laboratories.