Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103007686/ty1000sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007686/ty1000Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007686/ty1000IIsup3.hkl |
CCDC references: 214390; 214391
3,6-Bis(pyrazol-1-yl)-4-[2-(thiomorpholino)ethanethiolato]pyridazine
Sodium hydride (0.071 g, 2.96 mmol) was added to a solution of pyrazole (0.120 g, 1.76 mmol) in pre-dried tetrahydrofuran (50 cm3). After stirring the mixture for 20 min, 3,6-dichloro-4-[2-(thiomorpholino)ethanethiolato]pyridazine (0.275 g, 0.89 mmol) was added to the solution and the mixture was heated at reflux for 4 h. After cooling to room temperature, the solvent was removed, and the resultant solid was dissolved in dichloromethane (50 cm3) and washed with water (3 x 50 cm3). The organic layer was dried over magnesium sulfate and the solvent was removed to give a thick pale-brown oil, which was recrystallized from ethanol to yield pale-brown needles (yield 0.070 g, 0.187 mmol, 21%). Analysis found: C 50.95, H 5.00, N 25.85%; calculated for C16H19N7S2: C 51.45, H 5.15, N 26.25%. IR (KBr disc, ν / cm−1): 2899 m, 1561 s, 1518 s, 1449 s, 1392 s, 1262 m, 1200 m, 1108 s, 1091 s, 1034 s, 1018 s, 950 m, 932 s, 875 m, 825 s, 805 s, 765 s, 634 m, 606 m, 534 m. 1H-NMR (CDCl3, p.p.m.): 2.69–2.86 (m, 10H), 3.18 (t, 2H), 6.57 (m, 2H) 7.81 (q, 1H), 7.88 (q, 1H), 8.23 (s, 1H), 8.49 (q, 1H), 8.74 (q, 1H). FAB-MS (m/z) 374 [C16H19N7S2+H]+.
3,6-Dichloro-4-[2-(thiomorpholino)ethanethiolato]pyridazine
Potassium carbonate (0.21 g, 1.54 mmol) was added to a stirred solution of 2-(thiomorpholino)ethanethiol (0.5 g, 3.07 mmol), which was previously synthesized by treatment of ethylene sulfide with thiomorpholine, in degassed MeCN (50 cm3). After 15 min, 3,4,6-trichloropyridazine (0.56 g, 3.07 mmol) was added and the mixture was heated at reflux for 20 h. The white precipitate that appeared on cooling was removed by filtration, washed with water and recrystallized from ethanol as pale-brown needles (yield 0.69 g, 2.22 mmol, 72%). Analysis found: C 38.20, H 4.05, N 13.10%; calculated for C10H13Cl2N3S2: C 38.70, H 4.20, N 13.55%. IR (KBr disc, ν / cm−1): 3069 m, 2929 m, 2808 s, 2772 m, 1518 s, 1420 m, 1373 s, 1339 s, 1319 s, 1296 s, 1289 s, 1227 m, 1201 m, 1164 m, 1138 s, 1115 s, 1076 m, 1048 m, 981 s, 963 m, 943 m, 886 m, 868 m, 840 s, 748 m, 662 m, 579 s, 424 m. 1H-NMR (CDCl3, p.p.m.): 2.67–2.84 (m, 10H), 3.10 (t, 2H), 7.29 (s, 1H). EI—MS (m/z) 309 [C10H13Cl2N3S2]+.
In (I), H atoms were located from ΔF syntheses and refined positionally but with Uiso values of 1.2Ueq(C). In (II), H atoms were first located from ΔF syntheses, then placed in idealized positions and refined using a riding model, with aromatic and aliphatic C—H distances constrained to be 0.96 and 0.99 Å, respectively, and with Uiso(H) values of 1.2Ueq(C).
For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT and SHELXTL (Bruker, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: CAMERON (Watkin et al., 1993) for (I); CAMERON (Watkin et al., 1996) for (II). For both compounds, software used to prepare material for publication: SHELXL97; PLATON (Spek, 2003).
C10H13Cl2N3S2 | Dx = 1.584 Mg m−3 |
Mr = 310.26 | Melting point: unknown K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.097 (3) Å | Cell parameters from 3123 reflections |
b = 7.021 (2) Å | θ = 2.7–28.1° |
c = 15.425 (4) Å | µ = 0.80 mm−1 |
β = 96.645 (5)° | T = 150 K |
V = 1301.2 (6) Å3 | Triangular plate, colourless |
Z = 4 | 0.27 × 0.25 × 0.06 mm |
F(000) = 640 |
Bruker SMART1000 CCD area detector diffractometer | 3042 independent reflections |
Radiation source: normal-focus sealed tube | 2250 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans | θmax = 28.7°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→15 |
Tmin = 0.721, Tmax = 0.928 | k = −9→9 |
8156 measured reflections | l = −20→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.054P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.001 |
3042 reflections | Δρmax = 0.38 e Å−3 |
154 parameters | Δρmin = −0.29 e Å−3 |
0 restraints |
C10H13Cl2N3S2 | V = 1301.2 (6) Å3 |
Mr = 310.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.097 (3) Å | µ = 0.80 mm−1 |
b = 7.021 (2) Å | T = 150 K |
c = 15.425 (4) Å | 0.27 × 0.25 × 0.06 mm |
β = 96.645 (5)° |
Bruker SMART1000 CCD area detector diffractometer | 3042 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2250 reflections with I > 2σ(I) |
Tmin = 0.721, Tmax = 0.928 | Rint = 0.046 |
8156 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.38 e Å−3 |
3042 reflections | Δρmin = −0.29 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 | ||
N1 | 0.49032 (15) | 0.2709 (2) | 1.17487 (11) | 0.0297 (4) | |
N2 | 0.39942 (15) | 0.2629 (2) | 1.11561 (12) | 0.0298 (4) | |
C3 | 0.41164 (16) | 0.2497 (2) | 1.03281 (14) | 0.0259 (4) | |
C4 | 0.51381 (16) | 0.2475 (2) | 0.99670 (13) | 0.0225 (4) | |
C5 | 0.60676 (17) | 0.2589 (2) | 1.05828 (12) | 0.0241 (4) | |
H5 | 0.6785 | 0.2608 | 1.0421 | 0.029* | |
C6 | 0.58765 (18) | 0.2675 (2) | 1.14509 (13) | 0.0256 (4) | |
Cl31 | 0.28779 (4) | 0.23419 (8) | 0.96341 (4) | 0.03605 (15) | |
Cl61 | 0.70171 (4) | 0.27187 (7) | 1.22518 (3) | 0.03215 (14) | |
S41 | 0.50956 (4) | 0.22526 (7) | 0.88406 (3) | 0.02329 (13) | |
C41 | 0.65532 (16) | 0.2452 (3) | 0.86664 (13) | 0.0257 (4) | |
H41A | 0.6773 | 0.3780 | 0.8655 | 0.031* | |
H41B | 0.7022 | 0.1813 | 0.9130 | 0.031* | |
C42 | 0.66641 (15) | 0.1511 (3) | 0.77915 (12) | 0.0244 (4) | |
H42A | 0.7329 | 0.1983 | 0.7567 | 0.029* | |
H42B | 0.6746 | 0.0147 | 0.7875 | 0.029* | |
N11 | 0.57023 (13) | 0.1888 (2) | 0.71576 (10) | 0.0222 (3) | |
C12 | 0.57247 (15) | 0.3798 (3) | 0.67809 (12) | 0.0247 (4) | |
H12A | 0.6279 | 0.3842 | 0.6374 | 0.030* | |
H12B | 0.5936 | 0.4714 | 0.7241 | 0.030* | |
C13 | 0.45981 (16) | 0.4335 (3) | 0.63099 (12) | 0.0278 (4) | |
H13A | 0.4627 | 0.5634 | 0.6099 | 0.033* | |
H13B | 0.4045 | 0.4283 | 0.6718 | 0.033* | |
S14 | 0.41816 (4) | 0.27758 (8) | 0.54026 (3) | 0.03046 (14) | |
C15 | 0.43974 (17) | 0.0551 (3) | 0.59848 (13) | 0.0288 (4) | |
H15A | 0.3841 | 0.0423 | 0.6386 | 0.035* | |
H15B | 0.4297 | −0.0493 | 0.5571 | 0.035* | |
C16 | 0.55399 (16) | 0.0408 (3) | 0.64895 (12) | 0.0253 (4) | |
H16A | 0.5628 | −0.0835 | 0.6764 | 0.030* | |
H16B | 0.6100 | 0.0537 | 0.6092 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0368 (10) | 0.0239 (8) | 0.0300 (9) | 0.0015 (7) | 0.0110 (8) | −0.0002 (7) |
N2 | 0.0317 (10) | 0.0266 (9) | 0.0331 (10) | 0.0046 (7) | 0.0122 (8) | 0.0031 (7) |
C3 | 0.0255 (10) | 0.0208 (10) | 0.0319 (11) | 0.0027 (7) | 0.0060 (8) | 0.0019 (7) |
C4 | 0.0249 (10) | 0.0172 (9) | 0.0257 (9) | 0.0019 (7) | 0.0047 (8) | 0.0019 (7) |
C5 | 0.0254 (10) | 0.0220 (9) | 0.0254 (10) | 0.0012 (7) | 0.0048 (8) | −0.0006 (7) |
C6 | 0.0330 (11) | 0.0194 (9) | 0.0250 (10) | 0.0013 (7) | 0.0055 (8) | −0.0015 (7) |
Cl31 | 0.0192 (3) | 0.0477 (3) | 0.0412 (3) | 0.0040 (2) | 0.0032 (2) | 0.0037 (2) |
Cl61 | 0.0354 (3) | 0.0400 (3) | 0.0206 (2) | 0.0005 (2) | 0.0012 (2) | −0.00433 (19) |
S41 | 0.0207 (2) | 0.0268 (2) | 0.0222 (2) | 0.00086 (18) | 0.00184 (18) | 0.00075 (18) |
C41 | 0.0192 (10) | 0.0339 (11) | 0.0237 (10) | −0.0013 (7) | 0.0013 (7) | −0.0009 (8) |
C42 | 0.0213 (10) | 0.0289 (10) | 0.0227 (9) | 0.0030 (8) | 0.0017 (8) | 0.0000 (8) |
N11 | 0.0224 (8) | 0.0224 (8) | 0.0213 (8) | 0.0012 (6) | 0.0004 (6) | −0.0012 (6) |
C12 | 0.0254 (11) | 0.0244 (10) | 0.0241 (9) | −0.0013 (8) | 0.0021 (8) | −0.0012 (7) |
C13 | 0.0284 (11) | 0.0260 (10) | 0.0289 (10) | 0.0029 (8) | 0.0031 (8) | 0.0001 (8) |
S14 | 0.0269 (3) | 0.0390 (3) | 0.0243 (3) | 0.0027 (2) | −0.0019 (2) | 0.0001 (2) |
C15 | 0.0289 (11) | 0.0317 (10) | 0.0261 (10) | −0.0049 (8) | 0.0049 (8) | −0.0055 (8) |
C16 | 0.0291 (11) | 0.0237 (9) | 0.0233 (9) | 0.0019 (8) | 0.0040 (8) | −0.0026 (7) |
N1—N2 | 1.347 (3) | C42—H42B | 0.9700 |
N1—C6 | 1.313 (3) | N11—C16 | 1.460 (2) |
N2—C3 | 1.306 (3) | N11—C12 | 1.463 (2) |
C3—C4 | 1.413 (3) | C12—C13 | 1.516 (3) |
C3—CL31 | 1.741 (2) | C12—H12A | 0.9700 |
C4—C5 | 1.388 (3) | C12—H12B | 0.9700 |
C4—S41 | 1.739 (2) | C13—S14 | 1.802 (2) |
C5—C6 | 1.386 (3) | C13—H13A | 0.9700 |
C5—H5 | 0.9300 | C13—H13B | 0.9700 |
C6—CL61 | 1.743 (2) | S14—C15 | 1.806 (2) |
S41—C41 | 1.820 (2) | C15—C16 | 1.509 (3) |
C41—C42 | 1.522 (3) | C15—H15A | 0.9700 |
C41—H41A | 0.9700 | C15—H15B | 0.9700 |
C41—H41B | 0.9700 | C16—H16A | 0.9700 |
C42—N11 | 1.455 (2) | C16—H16B | 0.9700 |
C42—H42A | 0.9700 | ||
C6—N1—N2 | 117.16 (17) | C42—N11—C12 | 112.55 (15) |
C3—N2—N1 | 119.38 (17) | C16—N11—C12 | 112.26 (15) |
N2—C3—C4 | 126.1 (2) | N11—C12—C13 | 111.19 (15) |
N2—C3—CL31 | 114.77 (15) | N11—C12—H12A | 109.4 |
C4—C3—CL31 | 119.11 (16) | C13—C12—H12A | 109.4 |
C5—C4—C3 | 113.95 (19) | N11—C12—H12B | 109.4 |
C5—C4—S41 | 128.09 (16) | C13—C12—H12B | 109.4 |
C3—C4—S41 | 117.94 (15) | H12A—C12—H12B | 108.0 |
C6—C5—C4 | 116.81 (19) | C12—C13—S14 | 112.09 (13) |
C6—C5—H5 | 121.6 | C12—C13—H13A | 109.2 |
C4—C5—H5 | 121.6 | S14—C13—H13A | 109.2 |
N1—C6—C5 | 126.55 (19) | C12—C13—H13B | 109.2 |
N1—C6—CL61 | 114.85 (15) | S14—C13—H13B | 109.2 |
C5—C6—CL61 | 118.60 (16) | H13A—C13—H13B | 107.9 |
C4—S41—C41 | 102.91 (9) | C13—S14—C15 | 97.35 (9) |
C42—C41—S41 | 106.48 (13) | C16—C15—S14 | 112.66 (14) |
C42—C41—H41A | 110.4 | C16—C15—H15A | 109.1 |
S41—C41—H41A | 110.4 | S14—C15—H15A | 109.1 |
C42—C41—H41B | 110.4 | C16—C15—H15B | 109.1 |
S41—C41—H41B | 110.4 | S14—C15—H15B | 109.1 |
H41A—C41—H41B | 108.6 | H15A—C15—H15B | 107.8 |
N11—C42—C41 | 111.79 (15) | N11—C16—C15 | 110.92 (15) |
N11—C42—H42A | 109.3 | N11—C16—H16A | 109.5 |
C41—C42—H42A | 109.3 | C15—C16—H16A | 109.5 |
N11—C42—H42B | 109.3 | N11—C16—H16B | 109.5 |
C41—C42—H42B | 109.3 | C15—C16—H16B | 109.5 |
H42A—C42—H42B | 107.9 | H16A—C16—H16B | 108.0 |
C42—N11—C16 | 112.14 (14) |
C16H19N7S2 | Dx = 1.439 Mg m−3 |
Mr = 373.50 | Melting point: unknown K |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0944 (8) Å | Cell parameters from 3172 reflections |
b = 13.9838 (14) Å | θ = 2.5–26.7° |
c = 30.482 (3) Å | µ = 0.32 mm−1 |
β = 92.292 (2)° | T = 150 K |
V = 3447.5 (6) Å3 | Column, pale yellow |
Z = 8 | 0.30 × 0.11 × 0.09 mm |
F(000) = 1568 |
Bruker SMART1000 CCD area detector diffractometer | 2588 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.056 |
Graphite monochromator | θmax = 28.8°, θmin = 1.3° |
ω scans | h = −10→10 |
13401 measured reflections | k = −18→17 |
4084 independent reflections | l = −40→35 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | Only H-atom coordinates refined |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.059P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
4084 reflections | Δρmax = 0.35 e Å−3 |
226 parameters | Δρmin = −0.31 e Å−3 |
0 restraints |
C16H19N7S2 | V = 3447.5 (6) Å3 |
Mr = 373.50 | Z = 8 |
Monoclinic, I2/a | Mo Kα radiation |
a = 8.0944 (8) Å | µ = 0.32 mm−1 |
b = 13.9838 (14) Å | T = 150 K |
c = 30.482 (3) Å | 0.30 × 0.11 × 0.09 mm |
β = 92.292 (2)° |
Bruker SMART1000 CCD area detector diffractometer | 2588 reflections with I > 2σ(I) |
13401 measured reflections | Rint = 0.056 |
4084 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.119 | Only H-atom coordinates refined |
S = 0.99 | Δρmax = 0.35 e Å−3 |
4084 reflections | Δρmin = −0.31 e Å−3 |
226 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 | ||
N1 | 0.6358 (3) | −0.14161 (13) | 0.33692 (7) | 0.0269 (5) | |
N2 | 0.7077 (3) | −0.13226 (13) | 0.29803 (7) | 0.0254 (5) | |
C3 | 0.7233 (3) | −0.04727 (15) | 0.27946 (8) | 0.0207 (5) | |
C4 | 0.6715 (3) | 0.04010 (15) | 0.29862 (8) | 0.0197 (5) | |
C5 | 0.5979 (3) | 0.02917 (16) | 0.33822 (8) | 0.0232 (5) | |
H5 | 0.559 (3) | 0.0816 (18) | 0.3564 (8) | 0.028* | |
C6 | 0.5845 (3) | −0.06270 (16) | 0.35560 (8) | 0.0220 (5) | |
N31 | 0.7959 (2) | −0.05210 (13) | 0.23826 (7) | 0.0215 (4) | |
N32 | 0.8760 (3) | 0.02485 (13) | 0.22162 (7) | 0.0254 (5) | |
C33 | 0.9317 (3) | −0.00640 (17) | 0.18392 (9) | 0.0271 (6) | |
H33 | 0.993 (3) | 0.0356 (18) | 0.1638 (8) | 0.032* | |
C34 | 0.8877 (3) | −0.10204 (17) | 0.17580 (9) | 0.0269 (6) | |
H34 | 0.912 (3) | −0.1371 (18) | 0.1505 (9) | 0.032* | |
C35 | 0.8023 (3) | −0.12977 (17) | 0.21110 (9) | 0.0251 (6) | |
H35 | 0.749 (3) | −0.1838 (19) | 0.2181 (8) | 0.030* | |
S41 | 0.69371 (8) | 0.15170 (4) | 0.27344 (2) | 0.02365 (17) | |
C41 | 0.5871 (3) | 0.23185 (17) | 0.30996 (8) | 0.0234 (6) | |
H41A | 0.564 (3) | 0.2891 (18) | 0.2918 (8) | 0.028* | |
H41B | 0.484 (3) | 0.2072 (18) | 0.3165 (8) | 0.028* | |
C42 | 0.6941 (3) | 0.26188 (18) | 0.34964 (9) | 0.0260 (6) | |
H42A | 0.779 (3) | 0.3025 (19) | 0.3383 (8) | 0.031* | |
H42B | 0.749 (3) | 0.2085 (19) | 0.3634 (9) | 0.031* | |
N61 | 0.5115 (3) | −0.07501 (14) | 0.39654 (7) | 0.0264 (5) | |
N62 | 0.4272 (3) | −0.00125 (16) | 0.41421 (8) | 0.0402 (6) | |
C63 | 0.3784 (5) | −0.0364 (2) | 0.45172 (11) | 0.0508 (9) | |
H63 | 0.322 (4) | 0.003 (2) | 0.4695 (10) | 0.061* | |
C64 | 0.4307 (4) | −0.1306 (2) | 0.45905 (10) | 0.0421 (8) | |
H64 | 0.410 (4) | −0.175 (2) | 0.4833 (10) | 0.051* | |
C65 | 0.5154 (4) | −0.15299 (19) | 0.42305 (9) | 0.0327 (6) | |
H65 | 0.567 (3) | −0.215 (2) | 0.4148 (9) | 0.039* | |
S11 | 0.49668 (9) | 0.38125 (5) | 0.47735 (2) | 0.0350 (2) | |
C12 | 0.3863 (4) | 0.3075 (2) | 0.43741 (10) | 0.0335 (6) | |
H12A | 0.309 (4) | 0.350 (2) | 0.4197 (10) | 0.040* | |
H12B | 0.323 (4) | 0.271 (2) | 0.4533 (9) | 0.040* | |
C13 | 0.5004 (4) | 0.25285 (18) | 0.40799 (10) | 0.0294 (6) | |
H13A | 0.430 (3) | 0.2189 (19) | 0.3888 (9) | 0.035* | |
H13B | 0.571 (3) | 0.216 (2) | 0.4275 (9) | 0.035* | |
N14 | 0.6000 (2) | 0.31666 (13) | 0.38155 (7) | 0.0234 (5) | |
C15 | 0.7128 (3) | 0.37557 (18) | 0.40930 (9) | 0.0274 (6) | |
H15A | 0.791 (3) | 0.3385 (18) | 0.4281 (9) | 0.033* | |
H15B | 0.778 (3) | 0.4130 (19) | 0.3908 (9) | 0.033* | |
C16 | 0.6216 (4) | 0.44340 (18) | 0.43871 (9) | 0.0311 (6) | |
H16A | 0.700 (3) | 0.4824 (19) | 0.4557 (9) | 0.037* | |
H16B | 0.554 (3) | 0.485 (2) | 0.4204 (9) | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0309 (12) | 0.0192 (10) | 0.0309 (12) | 0.0003 (8) | 0.0037 (10) | 0.0024 (9) |
N2 | 0.0290 (12) | 0.0168 (10) | 0.0305 (13) | 0.0028 (8) | 0.0037 (10) | 0.0015 (8) |
C3 | 0.0199 (13) | 0.0181 (11) | 0.0241 (13) | −0.0007 (9) | 0.0002 (10) | −0.0003 (9) |
C4 | 0.0189 (12) | 0.0150 (11) | 0.0250 (14) | −0.0006 (9) | −0.0015 (10) | 0.0003 (9) |
C5 | 0.0269 (14) | 0.0186 (12) | 0.0238 (14) | 0.0005 (10) | −0.0004 (11) | −0.0014 (10) |
C6 | 0.0202 (13) | 0.0226 (12) | 0.0230 (14) | −0.0011 (10) | 0.0001 (10) | 0.0028 (10) |
N31 | 0.0224 (11) | 0.0163 (9) | 0.0258 (12) | 0.0008 (8) | 0.0018 (9) | −0.0032 (8) |
N32 | 0.0319 (12) | 0.0176 (10) | 0.0273 (12) | −0.0022 (8) | 0.0065 (10) | −0.0008 (8) |
C33 | 0.0313 (14) | 0.0234 (12) | 0.0269 (15) | 0.0011 (11) | 0.0051 (12) | −0.0005 (11) |
C34 | 0.0292 (14) | 0.0247 (13) | 0.0266 (14) | 0.0044 (11) | −0.0008 (11) | −0.0071 (11) |
C35 | 0.0268 (14) | 0.0164 (11) | 0.0319 (15) | 0.0009 (10) | −0.0017 (11) | −0.0052 (10) |
S41 | 0.0346 (4) | 0.0137 (3) | 0.0231 (3) | 0.0003 (2) | 0.0066 (3) | −0.0006 (2) |
C41 | 0.0284 (14) | 0.0155 (11) | 0.0268 (14) | 0.0004 (10) | 0.0066 (11) | −0.0005 (10) |
C42 | 0.0259 (14) | 0.0226 (13) | 0.0298 (15) | −0.0007 (11) | 0.0053 (12) | −0.0055 (10) |
N61 | 0.0282 (12) | 0.0245 (11) | 0.0268 (12) | −0.0025 (9) | 0.0031 (10) | 0.0034 (9) |
N62 | 0.0520 (16) | 0.0337 (13) | 0.0364 (15) | 0.0066 (11) | 0.0193 (12) | 0.0046 (11) |
C63 | 0.066 (2) | 0.0486 (19) | 0.040 (2) | 0.0030 (16) | 0.0261 (17) | 0.0036 (14) |
C64 | 0.052 (2) | 0.0460 (18) | 0.0288 (16) | −0.0103 (14) | 0.0053 (14) | 0.0120 (13) |
C65 | 0.0366 (16) | 0.0298 (14) | 0.0313 (16) | −0.0038 (12) | −0.0032 (13) | 0.0092 (12) |
S11 | 0.0411 (4) | 0.0366 (4) | 0.0278 (4) | −0.0032 (3) | 0.0071 (3) | −0.0093 (3) |
C12 | 0.0348 (16) | 0.0348 (15) | 0.0315 (16) | −0.0067 (12) | 0.0097 (13) | −0.0058 (12) |
C13 | 0.0340 (16) | 0.0247 (13) | 0.0297 (16) | −0.0058 (11) | 0.0034 (13) | −0.0046 (11) |
N14 | 0.0264 (12) | 0.0193 (9) | 0.0247 (11) | −0.0027 (8) | 0.0051 (9) | −0.0052 (8) |
C15 | 0.0294 (15) | 0.0250 (13) | 0.0277 (15) | −0.0049 (11) | 0.0015 (12) | −0.0054 (11) |
C16 | 0.0405 (17) | 0.0229 (13) | 0.0300 (16) | −0.0027 (12) | 0.0015 (13) | −0.0090 (11) |
N1—C6 | 1.316 (3) | C42—H42B | 0.96 (3) |
N1—N2 | 1.348 (3) | N61—C65 | 1.357 (3) |
N2—C3 | 1.325 (3) | N61—N62 | 1.360 (3) |
C3—N31 | 1.410 (3) | N62—C63 | 1.319 (4) |
C3—C4 | 1.424 (3) | C63—C64 | 1.400 (4) |
C4—C5 | 1.376 (3) | C63—H63 | 0.91 (3) |
C4—S41 | 1.751 (2) | C64—C65 | 1.354 (4) |
C5—C6 | 1.396 (3) | C64—H64 | 0.99 (3) |
C5—H5 | 0.98 (3) | C65—H65 | 0.99 (3) |
C6—N61 | 1.412 (3) | S11—C12 | 1.805 (3) |
N31—N32 | 1.365 (3) | S11—C16 | 1.806 (3) |
N31—C35 | 1.368 (3) | C12—C13 | 1.519 (4) |
N32—C33 | 1.325 (3) | C12—H12A | 1.00 (3) |
C33—C34 | 1.403 (3) | C12—H12B | 0.88 (3) |
C33—H33 | 0.99 (3) | C13—N14 | 1.465 (3) |
C34—C35 | 1.358 (4) | C13—H13A | 0.93 (3) |
C34—H34 | 0.94 (3) | C13—H13B | 0.96 (3) |
C35—H35 | 0.90 (3) | N14—C15 | 1.471 (3) |
S41—C41 | 1.821 (2) | C15—C16 | 1.517 (4) |
C41—C42 | 1.518 (4) | C15—H15A | 0.98 (3) |
C41—H41A | 0.99 (3) | C15—H15B | 0.95 (3) |
C41—H41B | 0.93 (3) | C16—H16A | 0.97 (3) |
C42—N14 | 1.474 (3) | C16—H16B | 0.96 (3) |
C42—H42A | 0.97 (3) | ||
C6—N1—N2 | 116.99 (19) | C65—N61—C6 | 128.6 (2) |
C3—N2—N1 | 120.98 (19) | N62—N61—C6 | 119.47 (19) |
N2—C3—N31 | 112.83 (19) | C63—N62—N61 | 103.5 (2) |
N2—C3—C4 | 124.0 (2) | N62—C63—C64 | 112.9 (3) |
N31—C3—C4 | 123.1 (2) | N62—C63—H63 | 118 (2) |
C5—C4—C3 | 114.2 (2) | C64—C63—H63 | 129 (2) |
C5—C4—S41 | 122.61 (17) | C65—C64—C63 | 104.4 (3) |
C3—C4—S41 | 123.20 (18) | C65—C64—H64 | 124.7 (18) |
C4—C5—C6 | 118.6 (2) | C63—C64—H64 | 130.9 (17) |
C4—C5—H5 | 125.0 (15) | C64—C65—N61 | 107.3 (2) |
C6—C5—H5 | 116.3 (15) | C64—C65—H65 | 129.6 (16) |
N1—C6—C5 | 125.2 (2) | N61—C65—H65 | 123.1 (16) |
N1—C6—N61 | 115.5 (2) | C12—S11—C16 | 96.31 (13) |
C5—C6—N61 | 119.3 (2) | C13—C12—S11 | 112.9 (2) |
N32—N31—C35 | 111.79 (19) | C13—C12—H12A | 111.0 (16) |
N32—N31—C3 | 120.99 (18) | S11—C12—H12A | 107.9 (17) |
C35—N31—C3 | 127.2 (2) | C13—C12—H12B | 114.5 (18) |
C33—N32—N31 | 104.19 (19) | S11—C12—H12B | 104.0 (19) |
N32—C33—C34 | 112.0 (2) | H12A—C12—H12B | 106 (2) |
N32—C33—H33 | 122.3 (15) | N14—C13—C12 | 112.3 (2) |
C34—C33—H33 | 125.6 (15) | N14—C13—H13A | 107.7 (17) |
C35—C34—C33 | 105.4 (2) | C12—C13—H13A | 104.7 (17) |
C35—C34—H34 | 129.1 (16) | N14—C13—H13B | 110.1 (16) |
C33—C34—H34 | 125.5 (16) | C12—C13—H13B | 105.5 (16) |
C34—C35—N31 | 106.6 (2) | H13A—C13—H13B | 117 (2) |
C34—C35—H35 | 133.8 (17) | C13—N14—C15 | 111.5 (2) |
N31—C35—H35 | 119.5 (17) | C13—N14—C42 | 110.88 (19) |
C4—S41—C41 | 102.77 (11) | C15—N14—C42 | 110.21 (19) |
C42—C41—S41 | 112.82 (18) | N14—C15—C16 | 112.6 (2) |
C42—C41—H41A | 108.1 (15) | N14—C15—H15A | 114.1 (16) |
S41—C41—H41A | 103.8 (14) | C16—C15—H15A | 107.5 (15) |
C42—C41—H41B | 114.7 (16) | N14—C15—H15B | 108.4 (16) |
S41—C41—H41B | 110.7 (15) | C16—C15—H15B | 107.6 (16) |
H41A—C41—H41B | 106 (2) | H15A—C15—H15B | 106 (2) |
N14—C42—C41 | 112.1 (2) | C15—C16—S11 | 112.52 (18) |
N14—C42—H42A | 108.9 (15) | C15—C16—H16A | 110.0 (16) |
C41—C42—H42A | 105.7 (16) | S11—C16—H16A | 107.2 (16) |
N14—C42—H42B | 111.0 (16) | C15—C16—H16B | 108.5 (16) |
C41—C42—H42B | 112.0 (16) | S11—C16—H16B | 110.4 (16) |
H42A—C42—H42B | 107 (2) | H16A—C16—H16B | 108 (2) |
C65—N61—N62 | 111.9 (2) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C10H13Cl2N3S2 | C16H19N7S2 |
Mr | 310.26 | 373.50 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, I2/a |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 12.097 (3), 7.021 (2), 15.425 (4) | 8.0944 (8), 13.9838 (14), 30.482 (3) |
β (°) | 96.645 (5) | 92.292 (2) |
V (Å3) | 1301.2 (6) | 3447.5 (6) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.80 | 0.32 |
Crystal size (mm) | 0.27 × 0.25 × 0.06 | 0.30 × 0.11 × 0.09 |
Data collection | ||
Diffractometer | Bruker SMART1000 CCD area detector diffractometer | Bruker SMART1000 CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | – |
Tmin, Tmax | 0.721, 0.928 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8156, 3042, 2250 | 13401, 4084, 2588 |
Rint | 0.046 | 0.056 |
(sin θ/λ)max (Å−1) | 0.675 | 0.678 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.089, 0.96 | 0.040, 0.119, 0.99 |
No. of reflections | 3042 | 4084 |
No. of parameters | 154 | 226 |
H-atom treatment | H-atom parameters constrained | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.38, −0.29 | 0.35, −0.31 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2001), SAINT and SHELXTL (Bruker, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1993), CAMERON (Watkin et al., 1996), SHELXL97; PLATON (Spek, 2003).
Conformer | IV | V |
Cis-cis | 0.00 | 0.00 |
Cis-trans | -17.07 | +4.60 |
Trans-trans | -32.01 | +9.25 |
Pyridazines substituted in the 3- and 6-positions with N-donor ligands (e.g. pyrazole, 2-pyridine, 2-aminopyridine and 2-mercaptopyridine) can act as tetradentate N4-donor ligands in a bis(bidentate) chelating fashion. These compounds are ideal for the generation of multinuclear coordination complexes with relatively short internuclear separations [d(M···M) ca 3.6 Å]. Many dinuclear copper(II) complexes, often with ancillary hydroxide or halide bridges, have been prepared (Chen et al., 1993a,b; Tandon et al., 1995, 1992; Thompson et al., 1985; Xu et al., 2000; Zhang et al., 1995) because of interest in their magnetic behaviour. By using metal centres predisposed to tetrahedral geometries, diverse molecular grids (2 × 2 and 2 × 3) have also been generated (Baxter et al., 1997; Youinou et al., 1992). Our own work with these ligands (Hubberstey & Russell, 1995) has concentrated on their use to generate trinuclear copper(I) complexes as small-molecule analogues of the trinuclear active sites in copper proteins such as ascorbate oxidases and laccases.
In an effort to develop this chemistry and generate molecules with linked mononuclear and trinuclear sites, as is the case in ascorbate oxidases (Messerschmidt et al., 1989, 1992, 1993) and laccases (Bertrand et al., 2002; Ducros et al., 1998, 2001; Hakulinen et al., 2002), we have attempted to attach to the pyridazine backbone potential mononuclear ligating centres, which can be either mono- or multidentate.
Following Hiller et al. (1968), who reported that the 4-position of 3,4,6-trichloropyridazine was much more sensitive to nucleophilic substitution than the 3- or 6-positions, we have been able to selectively add the potentially tridentate chelating moiety 2-(thiomorpholino)ethanethiol to the 4-position of the pyridazine ring and subsequently replace the remaining Cl atoms with pyrazole moieties, forming first 3,6-dichloro-4-[2-(thiomorpholino)ethanethiolato]pyridazine, (I), and secondly 3,6-bis(pyrazol-1-yl)-4-[2-(thiomorpholino)ethanethiolato]pyridazine, (II).
The molecular structures of (I) and (II) [Figs. 1(a) and 1(b), respectively] can be compared with that of the tris(pyrazole)-substituted molecule 3,4,6-tris(pyrazol-1-yl)pyridazine [(III); Fig. 1c; Blake et al., 2002]. It is clear that (I), an intermediate in the synthesis of (II), is not a potential ligand, unlike (II) and (III), for which two noteworthy points emerge. Firstly, the pyridazine and pyrazole rings are not coplanar, giving buckled molecules and, secondly, the rings adopt a trans–trans conformation, which contrasts with the cis–cis conformation adopted when the rings act? as tetradentate N4-donor ligands in a bis(bidentate) chelating fashion.
The deviation from planarity in (II) is relatively small, as illustrated by the dihedral angles between the pyridazine ring and the two substituent pyrazole rings [13.5 (2) and 23.3 (1)°]. The molecules of (III) are much more buckled. Although the 6-substituted pyrazole ring is almost coplanar with the pyridazine ring [dihedral angle 5.5 (2)°], the 3- and 4-substituted pyrazole rings are severely bent out of the plane of the pyridazine ring [dihedral angles 40.2 and 51.2°, respectively]. Although the molecular structure of 3,6-bis(pyrazol-1-yl)pyridazine, (IV), has yet to be investigated in the solid state, it is predicted to be planar by analogy with similar multi-ring species, including 3,6-bis(thiophen-2-yl)pyridazine (Ackers et al., 2002) and 2,2'-bipyridine (Howard, 1996). Since detailed calculations on isolated 2,2'-bipyridine molecules show the most stable arrangement to be that with a dihedral angle between the planes of the aromatic rings of 44.9° (Howard, 1996), the fact that it? adopts a planar trans-arrangement in the solid state can be attributed to the more favourable packing interactions associated with planar rather than non-planar molecules. Deviation from planarity in (II) and (III) is thus attributed to steric conflict. That in (III) can be attributed to the interactions between the adjacent pyrazole substituents on the 3- and 4-positions of the pyridazine ring. The substituent in the 3-position of (II), 2-(thiomorpholino)ethanethiol, although longer than pyrazole, is much less sterically demanding, leading to a much flatter molecular arrangement.
The trans–trans conformations adopted by (II) (Fig. 1 b) and (III) (Fig. 1c) contrast with that found for 3,6-bis(thiophen-2-yl)pyridazine, for which all four heteroatoms are located on the same side of the molecule, giving a cis–cis conformation (Ackers et al., 2002). These apparently conflicting arrangements are, however, consistent with the results of semi-empirical AM calculations using the PC Spartan Plus suite of programs (Wavefunction, 2002). These results confirm that the lowest energy conformations of (IV) and of 3,6-bis(thiophen-2-yl)pyridazine, (V), are the trans–trans and cis–cis conformers, respectively. Relative enthalpies of formation are given in Table 1. Interestingly, the stabilization of the trans–trans iosomer of (IV) over the cis–cis form (−32.01 kJ mol−1) is similar to the difference between the enthalpies of formation of the trans and cis versions of planar 2,2'-bipyridine (32.3 kJ mol−1), for which the trans conformer is the more stable (Howard, 1996; see Table 1).
The greater stability of the trans–trans conformer of (IV) relative to the cis–cis conformer may be attributed to (i) the presence of four intramolecular C—H···N hydrogen bonds in the former and (ii) steric repulsion between the H atoms attached to atoms C4 and C35 and attached to atoms C5 and C65 in the latter. Although an explanation for the different behaviour of (IV) and (V) is not immediately obvious, the fact that twice as many intramolecular C—H···N hydrogen bonds occur in the trans–trans version of (IV) (four) than in the corresponding conformer of (V) (two) may be significant.
The more favourable packing interactions associated with planar rather than non-planar molecules alluded to earlier may be traced to π–π-stacking forces, as the extended stuctures of both (I) and (II) involve offset face-to-face interactions (Hunter & Sanders, 1990; Hunter et al., 2001). An analysis of the extended structure of (I) reveals a columnar arrangement of molecules, stacked in the b direction and held together by π–π-stacking interactions between their aromatic moieties (Fig. 2). The perpendicular separations between the aromatic moieties, which are crystallographically constrained to be parallel, average 3.43 (3) Å (range 3.385–3.466 Å) and 3.58 (3) Å (range 3.539–3.620 Å). The columns are linked by very long S···S contacts, similar in length [3.973 (2) Å] to those linking the molecules in the extended structure of 3,6-bis(thiophen-2-yl)pyridazine [3.980 (2) Å, Ackers et al., 2002], to give a two-dimensional architecture parallel to the (001) plane (Fig. 3).
An analysis of the extended structure of (II) shows the formation of dimers through relatively short S···S interactions [3.246 (2) Å, Fig. 4]. The dimers, facing alternate directions, stack along the a direction (Fig. 5), utilizing weak offset face-to-face π–π interactions between pyridazine rings [perpendicular separation 3.7 (2) Å, range 3.43–3.95 Å].
As the three rings in the structure of (II) depart only marginally from coplanarity, it is anticipated that (II) will be able to act as a bis(bidentate) chelating ligand in much the same way as the non-derivatized species. However, owing to the severe buckling of the structure of (III), which results from steric repulsion between the 3- and 4-substituted pyrazole rings, it will probably not be possible for (III) to act similarly. Consequently, our future efforts to generate small-molecule analogues of multinuclear copper proteins will concentrate on the use of (II) rather than (III).