The crystal structures of three new structurally related drug-like bicyclo derivatives are correlated with measured thermodynamic quantities for their sublimation and melting processes. The sublimation thermodynamics are determined using the temperature dependencies of the vapour pressure, and the melting processes are examined using differential scanning calorimetry. The three compounds contain a common N-(3-thia-1-azabicyclo[3.3.1]non-2-ylidene)aniline core, with either a CH3, F or CF3 substituent at the 4-position of the aniline ring. Lattice energy calculations are made using both the PIXEL and Coulomb–London–Pauli (CLP) models, and the conformational flexibility of the molecules is examined using gas-phase density functional theory (DFT) calculations. The experimentally measured crystal lattice energies (ΔH0sub) decrease in the order: CH3 > F > CF3. The calculated lattice energies using the PIXEL approach are in good agreement with the experimental values, and the partitioned intermolecular interaction energies suggest that dispersion contributions dominate the crystal structures of all three compounds. The sublimation energies and melting points are inversely correlated for the three molecules, with the melting points increasing in the order CF3 < F < CH3.
Supporting information
CCDC references: 984997; 984998; 984999
Data collection: CAD-4 (Enraf-Nonius, 1993) for (1), (2); APEX2 (Bruker, 2008) for (3). Cell refinement: CAD-4 for (1), (2); APEX2 for (3). Data reduction: CAD-4 for (1), (2); APEX2 for (3). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Crystal data top
C14H15F3N2S | F(000) = 624 |
Mr = 300.34 | Dx = 1.391 Mg m−3 |
Monoclinic, P21/c | Melting point: 364 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 13.074 (8) Å | Cell parameters from 35 reflections |
b = 9.185 (5) Å | θ = 5–15° |
c = 12.652 (8) Å | µ = 0.25 mm−1 |
β = 109.33 (6)° | T = 298 K |
V = 1433.7 (15) Å3 | Block, colourless |
Z = 4 | 0.35 × 0.20 × 0.15 mm |
Data collection top
Nonius CAD-4 diffractometer | Rint = 0.060 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 3.5° |
Graphite monochromator | h = 0→15 |
ω–\2q scans | k = −10→0 |
2627 measured reflections | l = −15→14 |
2514 independent reflections | 3 standard reflections every 200 reflections |
852 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
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)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.221 | H-atom parameters constrained |
S = 0.87 | w = 1/[σ2(Fo2) + (0.1222P)2] where P = (Fo2 + 2Fc2)/3 |
2514 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.44 e Å−3 |
12 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C14H15F3N2S | V = 1433.7 (15) Å3 |
Mr = 300.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.074 (8) Å | µ = 0.25 mm−1 |
b = 9.185 (5) Å | T = 298 K |
c = 12.652 (8) Å | 0.35 × 0.20 × 0.15 mm |
β = 109.33 (6)° | |
Data collection top
Nonius CAD-4 diffractometer | Rint = 0.060 |
2627 measured reflections | 3 standard reflections every 200 reflections |
2514 independent reflections | intensity decay: none |
852 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.075 | 12 restraints |
wR(F2) = 0.221 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.44 e Å−3 |
2514 reflections | Δρmin = −0.35 e Å−3 |
210 parameters | |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.56653 (12) | 0.3174 (2) | 0.51108 (15) | 0.0775 (7) | |
F1 | 0.0434 (16) | 0.166 (2) | 0.573 (3) | 0.103 (9) | 0.46 (5) |
F2 | 0.0584 (12) | 0.294 (4) | 0.4449 (11) | 0.135 (10) | 0.46 (5) |
F3 | 0.0797 (18) | 0.385 (3) | 0.601 (3) | 0.185 (16) | 0.46 (5) |
F1' | 0.0448 (14) | 0.1507 (13) | 0.521 (4) | 0.131 (9) | 0.54 (5) |
F2' | 0.0591 (15) | 0.364 (4) | 0.475 (3) | 0.242 (19) | 0.54 (5) |
F3' | 0.0757 (15) | 0.313 (6) | 0.6401 (19) | 0.253 (15) | 0.54 (5) |
N1 | 0.5501 (3) | 0.1450 (6) | 0.6764 (4) | 0.0659 (15) | |
N2 | 0.7223 (3) | 0.1656 (5) | 0.6649 (4) | 0.0545 (13) | |
C1 | 0.2181 (4) | 0.2400 (7) | 0.5837 (6) | 0.0640 (18) | |
C2 | 0.2573 (5) | 0.1588 (8) | 0.5137 (6) | 0.079 (2) | |
H2A | 0.2096 | 0.1230 | 0.4468 | 0.095* | |
C3 | 0.3679 (5) | 0.1299 (7) | 0.5423 (6) | 0.073 (2) | |
H3A | 0.3934 | 0.0764 | 0.4938 | 0.087* | |
C4 | 0.4405 (4) | 0.1803 (7) | 0.6430 (5) | 0.0588 (16) | |
C5 | 0.4002 (4) | 0.2656 (8) | 0.7123 (5) | 0.0679 (19) | |
H5A | 0.4473 | 0.3032 | 0.7789 | 0.081* | |
C6 | 0.2914 (5) | 0.2936 (8) | 0.6819 (6) | 0.073 (2) | |
H6A | 0.2660 | 0.3504 | 0.7287 | 0.088* | |
C7 | 0.0983 (5) | 0.2706 (7) | 0.5522 (7) | 0.088 (2) | |
C8 | 0.6124 (4) | 0.2024 (6) | 0.6246 (5) | 0.0527 (15) | |
C9 | 0.7849 (4) | 0.2160 (7) | 0.5920 (5) | 0.0662 (18) | |
H9A | 0.8569 | 0.1736 | 0.6178 | 0.079* | |
H9B | 0.7488 | 0.1840 | 0.5156 | 0.079* | |
C10 | 0.7931 (4) | 0.3754 (7) | 0.5951 (6) | 0.0636 (17) | |
H10A | 0.8388 | 0.4045 | 0.5510 | 0.076* | |
C11 | 0.6792 (5) | 0.4441 (8) | 0.5405 (6) | 0.076 (2) | |
H11A | 0.6771 | 0.4904 | 0.4709 | 0.091* | |
H11B | 0.6693 | 0.5196 | 0.5898 | 0.091* | |
C12 | 0.7783 (4) | 0.2044 (8) | 0.7815 (5) | 0.0683 (19) | |
H12A | 0.8485 | 0.1569 | 0.8072 | 0.082* | |
H12B | 0.7366 | 0.1699 | 0.8273 | 0.082* | |
C13 | 0.7935 (5) | 0.3649 (8) | 0.7956 (5) | 0.075 (2) | |
H13A | 0.8387 | 0.3863 | 0.8718 | 0.090* | |
H13B | 0.7237 | 0.4112 | 0.7825 | 0.090* | |
C14 | 0.8467 (5) | 0.4272 (8) | 0.7135 (6) | 0.073 (2) | |
H14A | 0.8434 | 0.5327 | 0.7150 | 0.088* | |
H14B | 0.9225 | 0.3992 | 0.7382 | 0.088* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0481 (9) | 0.1032 (15) | 0.0784 (12) | −0.0034 (10) | 0.0172 (7) | 0.0294 (11) |
F1 | 0.048 (7) | 0.102 (14) | 0.188 (18) | 0.001 (7) | 0.077 (10) | 0.052 (10) |
F2 | 0.046 (7) | 0.21 (2) | 0.133 (17) | 0.053 (10) | 0.009 (7) | 0.083 (13) |
F3 | 0.057 (10) | 0.141 (19) | 0.33 (4) | 0.026 (9) | 0.023 (19) | −0.083 (19) |
F1' | 0.032 (6) | 0.130 (12) | 0.23 (2) | −0.009 (6) | 0.034 (9) | 0.015 (11) |
F2' | 0.063 (10) | 0.16 (2) | 0.53 (5) | 0.061 (10) | 0.12 (2) | 0.21 (2) |
F3' | 0.064 (9) | 0.37 (4) | 0.36 (3) | 0.013 (18) | 0.122 (15) | −0.13 (3) |
N1 | 0.033 (2) | 0.091 (4) | 0.079 (4) | 0.006 (3) | 0.025 (2) | 0.023 (3) |
N2 | 0.039 (2) | 0.070 (3) | 0.066 (3) | 0.006 (2) | 0.031 (2) | 0.007 (3) |
C1 | 0.034 (3) | 0.071 (5) | 0.093 (5) | 0.002 (3) | 0.030 (3) | 0.019 (4) |
C2 | 0.045 (3) | 0.092 (5) | 0.094 (5) | −0.010 (4) | 0.013 (3) | −0.014 (5) |
C3 | 0.049 (3) | 0.076 (5) | 0.099 (5) | −0.009 (3) | 0.034 (4) | −0.027 (4) |
C4 | 0.042 (3) | 0.063 (4) | 0.078 (4) | 0.003 (3) | 0.030 (3) | 0.014 (4) |
C5 | 0.045 (3) | 0.110 (5) | 0.058 (4) | 0.007 (3) | 0.030 (3) | −0.002 (4) |
C6 | 0.056 (4) | 0.100 (6) | 0.080 (5) | 0.018 (4) | 0.046 (4) | 0.015 (4) |
C7 | 0.052 (4) | 0.086 (7) | 0.130 (8) | 0.004 (5) | 0.038 (5) | 0.019 (6) |
C8 | 0.035 (3) | 0.055 (4) | 0.069 (4) | 0.000 (3) | 0.018 (3) | −0.004 (3) |
C9 | 0.039 (3) | 0.098 (6) | 0.080 (4) | −0.007 (3) | 0.045 (3) | −0.013 (4) |
C10 | 0.049 (3) | 0.084 (5) | 0.076 (5) | −0.004 (3) | 0.045 (3) | 0.000 (4) |
C11 | 0.062 (4) | 0.077 (5) | 0.096 (5) | −0.007 (4) | 0.036 (4) | 0.018 (4) |
C12 | 0.041 (3) | 0.114 (6) | 0.057 (4) | 0.007 (3) | 0.025 (3) | 0.013 (4) |
C13 | 0.063 (4) | 0.103 (6) | 0.065 (4) | −0.016 (4) | 0.029 (3) | −0.020 (4) |
C14 | 0.053 (3) | 0.092 (5) | 0.088 (5) | −0.022 (3) | 0.041 (3) | −0.013 (4) |
Geometric parameters (Å, º) top
S1—C8 | 1.723 (6) | C4—C5 | 1.402 (8) |
S1—C11 | 1.817 (6) | C5—C6 | 1.369 (7) |
F1—C7 | 1.281 (10) | C5—H5A | 0.9300 |
F2—C7 | 1.302 (10) | C6—H6A | 0.9300 |
F3—C7 | 1.282 (11) | C9—C10 | 1.468 (9) |
F1'—C7 | 1.295 (10) | C9—H9A | 0.9700 |
F2'—C7 | 1.271 (10) | C9—H9B | 0.9700 |
F3'—C7 | 1.300 (10) | C10—C14 | 1.505 (8) |
N1—C8 | 1.313 (7) | C10—C11 | 1.553 (8) |
N1—C4 | 1.391 (7) | C10—H10A | 0.9800 |
N2—C8 | 1.398 (6) | C11—H11A | 0.9700 |
N2—C12 | 1.458 (7) | C11—H11B | 0.9700 |
N2—C9 | 1.494 (7) | C12—C13 | 1.490 (9) |
C1—C2 | 1.380 (9) | C12—H12A | 0.9700 |
C1—C6 | 1.385 (9) | C12—H12B | 0.9700 |
C1—C7 | 1.509 (8) | C13—C14 | 1.538 (8) |
C2—C3 | 1.395 (8) | C13—H13A | 0.9700 |
C2—H2A | 0.9300 | C13—H13B | 0.9700 |
C3—C4 | 1.392 (8) | C14—H14A | 0.9700 |
C3—H3A | 0.9300 | C14—H14B | 0.9700 |
| | | |
C8—S1—C11 | 100.8 (3) | N2—C8—S1 | 118.9 (4) |
C8—N1—C4 | 120.1 (5) | C10—C9—N2 | 110.0 (5) |
C8—N2—C12 | 114.9 (4) | C10—C9—H9A | 109.7 |
C8—N2—C9 | 114.0 (5) | N2—C9—H9A | 109.7 |
C12—N2—C9 | 110.8 (4) | C10—C9—H9B | 109.7 |
C2—C1—C6 | 118.3 (5) | N2—C9—H9B | 109.7 |
C2—C1—C7 | 120.4 (6) | H9A—C9—H9B | 108.2 |
C6—C1—C7 | 121.4 (6) | C9—C10—C14 | 110.4 (6) |
C1—C2—C3 | 120.7 (6) | C9—C10—C11 | 110.0 (5) |
C1—C2—H2A | 119.7 | C14—C10—C11 | 112.1 (5) |
C3—C2—H2A | 119.7 | C9—C10—H10A | 108.1 |
C4—C3—C2 | 120.6 (6) | C14—C10—H10A | 108.1 |
C4—C3—H3A | 119.7 | C11—C10—H10A | 108.1 |
C2—C3—H3A | 119.7 | C10—C11—S1 | 115.1 (5) |
N1—C4—C3 | 121.5 (6) | C10—C11—H11A | 108.5 |
N1—C4—C5 | 120.1 (6) | S1—C11—H11A | 108.5 |
C3—C4—C5 | 118.3 (5) | C10—C11—H11B | 108.5 |
C6—C5—C4 | 120.0 (6) | S1—C11—H11B | 108.5 |
C6—C5—H5A | 120.0 | H11A—C11—H11B | 107.5 |
C4—C5—H5A | 120.0 | N2—C12—C13 | 111.4 (5) |
C5—C6—C1 | 122.1 (6) | N2—C12—H12A | 109.3 |
C5—C6—H6A | 118.9 | C13—C12—H12A | 109.3 |
C1—C6—H6A | 118.9 | N2—C12—H12B | 109.3 |
F1—C7—F3 | 107.9 (9) | C13—C12—H12B | 109.3 |
F1—C7—F2 | 106.5 (9) | H12A—C12—H12B | 108.0 |
F3—C7—F2 | 106.8 (10) | C12—C13—C14 | 111.1 (5) |
F2'—C7—F1' | 107.7 (9) | C12—C13—H13A | 109.4 |
F2'—C7—F3' | 107.6 (9) | C14—C13—H13A | 109.4 |
F1'—C7—F3' | 105.0 (9) | C12—C13—H13B | 109.4 |
F2'—C7—C1 | 116.7 (10) | C14—C13—H13B | 109.4 |
F1—C7—C1 | 114.2 (11) | H13A—C13—H13B | 108.0 |
F3—C7—C1 | 111.8 (12) | C10—C14—C13 | 112.8 (5) |
F1'—C7—C1 | 109.3 (10) | C10—C14—H14A | 109.0 |
F3'—C7—C1 | 109.9 (10) | C13—C14—H14A | 109.0 |
F2—C7—C1 | 109.2 (9) | C10—C14—H14B | 109.0 |
N1—C8—N2 | 117.0 (5) | C13—C14—H14B | 109.0 |
N1—C8—S1 | 124.0 (4) | H14A—C14—H14B | 107.8 |
| | | |
C6—C1—C2—C3 | 1.0 (10) | C6—C1—C7—F2 | 140.8 (18) |
C7—C1—C2—C3 | −179.9 (6) | C4—N1—C8—N2 | 178.1 (5) |
C1—C2—C3—C4 | 1.1 (11) | C4—N1—C8—S1 | −2.4 (8) |
C8—N1—C4—C3 | 71.2 (8) | C12—N2—C8—N1 | −59.3 (7) |
C8—N1—C4—C5 | −110.3 (7) | C9—N2—C8—N1 | 171.2 (5) |
C2—C3—C4—N1 | 175.9 (6) | C12—N2—C8—S1 | 121.1 (5) |
C2—C3—C4—C5 | −2.6 (10) | C9—N2—C8—S1 | −8.4 (7) |
N1—C4—C5—C6 | −176.5 (6) | C11—S1—C8—N1 | 142.4 (5) |
C3—C4—C5—C6 | 2.0 (9) | C11—S1—C8—N2 | −38.1 (5) |
C4—C5—C6—C1 | 0.1 (10) | C8—N2—C9—C10 | 68.6 (7) |
C2—C1—C6—C5 | −1.5 (10) | C12—N2—C9—C10 | −62.9 (7) |
C7—C1—C6—C5 | 179.3 (6) | N2—C9—C10—C14 | 58.0 (6) |
C2—C1—C7—F2' | −74 (3) | N2—C9—C10—C11 | −66.2 (7) |
C6—C1—C7—F2' | 105 (2) | C9—C10—C11—S1 | 10.4 (7) |
C2—C1—C7—F1 | 80.8 (19) | C14—C10—C11—S1 | −112.8 (6) |
C6—C1—C7—F1 | −100.1 (18) | C8—S1—C11—C10 | 36.3 (5) |
C2—C1—C7—F3 | −156 (2) | C8—N2—C12—C13 | −71.5 (6) |
C6—C1—C7—F3 | 23 (2) | C9—N2—C12—C13 | 59.6 (6) |
C2—C1—C7—F1' | 48 (2) | N2—C12—C13—C14 | −51.9 (6) |
C6—C1—C7—F1' | −133 (2) | C9—C10—C14—C13 | −51.8 (7) |
C2—C1—C7—F3' | 163 (3) | C11—C10—C14—C13 | 71.2 (7) |
C6—C1—C7—F3' | −18 (3) | C12—C13—C14—C10 | 48.4 (8) |
C2—C1—C7—F2 | −38 (2) | | |
Crystal data top
C13H15FN2S | F(000) = 528 |
Mr = 250.33 | Dx = 1.312 Mg m−3 |
Monoclinic, P21/c | Melting point: 363 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 7.586 (1) Å | Cell parameters from 35 reflections |
b = 10.088 (2) Å | θ = 5–15° |
c = 16.566 (4) Å | µ = 0.25 mm−1 |
β = 91.41 (3)° | T = 293 K |
V = 1267.4 (4) Å3 | Block, colourless |
Z = 4 | 0.45 × 0.30 × 0.15 mm |
Data collection top
Nonius CAD-4 diffractometer | Rint = 0.018 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 2.4° |
Graphite monochromator | h = −10→10 |
ω–\2q scans | k = 0→14 |
3814 measured reflections | l = 0→23 |
3698 independent reflections | 3 standard reflections every 200 reflections |
2094 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0757P)2] where P = (Fo2 + 2Fc2)/3 |
3698 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C13H15FN2S | V = 1267.4 (4) Å3 |
Mr = 250.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.586 (1) Å | µ = 0.25 mm−1 |
b = 10.088 (2) Å | T = 293 K |
c = 16.566 (4) Å | 0.45 × 0.30 × 0.15 mm |
β = 91.41 (3)° | |
Data collection top
Nonius CAD-4 diffractometer | Rint = 0.018 |
3814 measured reflections | 3 standard reflections every 200 reflections |
3698 independent reflections | intensity decay: none |
2094 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.27 e Å−3 |
3698 reflections | Δρmin = −0.25 e Å−3 |
154 parameters | |
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 | x | y | z | Uiso*/Ueq | |
S1 | 1.14718 (5) | 0.27372 (5) | 0.50016 (2) | 0.05899 (15) | |
F1 | 1.49014 (18) | 0.44604 (13) | 0.17884 (8) | 0.0973 (4) | |
N1 | 0.96747 (16) | 0.22477 (14) | 0.36082 (8) | 0.0548 (3) | |
N2 | 0.83473 (16) | 0.15279 (12) | 0.47580 (8) | 0.0528 (3) | |
C1 | 1.3612 (2) | 0.39195 (18) | 0.22469 (9) | 0.0630 (4) | |
C2 | 1.3985 (3) | 0.2779 (2) | 0.26612 (12) | 0.0724 (5) | |
H2A | 1.5084 | 0.2377 | 0.2630 | 0.087* | |
C3 | 1.2678 (2) | 0.22395 (18) | 0.31296 (11) | 0.0648 (4) | |
H3A | 1.2904 | 0.1462 | 0.3416 | 0.078* | |
C4 | 1.10529 (19) | 0.28343 (15) | 0.31780 (8) | 0.0472 (3) | |
C5 | 1.0731 (2) | 0.39711 (16) | 0.27303 (9) | 0.0553 (4) | |
H5A | 0.9625 | 0.4368 | 0.2743 | 0.066* | |
C6 | 1.2024 (2) | 0.45265 (16) | 0.22644 (9) | 0.0627 (4) | |
H6A | 1.1807 | 0.5298 | 0.1971 | 0.075* | |
C8 | 0.97345 (17) | 0.21325 (13) | 0.43688 (8) | 0.0430 (3) | |
C9 | 0.8515 (2) | 0.13495 (17) | 0.56284 (11) | 0.0649 (5) | |
H9A | 0.9601 | 0.0884 | 0.5762 | 0.078* | |
H9B | 0.7537 | 0.0824 | 0.5818 | 0.078* | |
C10 | 0.8520 (2) | 0.26987 (17) | 0.60370 (9) | 0.0602 (4) | |
H10A | 0.8518 | 0.2560 | 0.6623 | 0.072* | |
C11 | 1.0214 (2) | 0.34300 (19) | 0.58300 (10) | 0.0627 (4) | |
H11A | 1.0973 | 0.3452 | 0.6310 | 0.075* | |
H11B | 0.9912 | 0.4339 | 0.5695 | 0.075* | |
C12 | 0.66026 (19) | 0.20752 (18) | 0.45292 (12) | 0.0637 (4) | |
H12A | 0.5681 | 0.1506 | 0.4730 | 0.076* | |
H12B | 0.6475 | 0.2121 | 0.3946 | 0.076* | |
C13 | 0.64368 (19) | 0.34508 (17) | 0.48880 (10) | 0.0588 (4) | |
H13A | 0.5252 | 0.3781 | 0.4784 | 0.071* | |
H13B | 0.7253 | 0.4044 | 0.4628 | 0.071* | |
C14 | 0.6820 (2) | 0.34457 (19) | 0.57883 (10) | 0.0627 (4) | |
H14A | 0.5834 | 0.3042 | 0.6057 | 0.075* | |
H14B | 0.6916 | 0.4355 | 0.5975 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.04262 (19) | 0.0797 (3) | 0.0546 (2) | −0.00286 (18) | 0.00027 (14) | −0.00468 (19) |
F1 | 0.1085 (9) | 0.0946 (9) | 0.0910 (8) | −0.0154 (7) | 0.0453 (7) | 0.0185 (7) |
N1 | 0.0522 (7) | 0.0598 (8) | 0.0524 (7) | −0.0087 (6) | 0.0021 (5) | −0.0067 (6) |
N2 | 0.0480 (6) | 0.0403 (6) | 0.0709 (8) | −0.0035 (5) | 0.0149 (5) | −0.0020 (6) |
C1 | 0.0781 (11) | 0.0609 (10) | 0.0508 (8) | −0.0039 (9) | 0.0185 (7) | 0.0057 (7) |
C2 | 0.0672 (10) | 0.0840 (13) | 0.0671 (10) | 0.0183 (9) | 0.0231 (8) | 0.0168 (10) |
C3 | 0.0675 (9) | 0.0649 (10) | 0.0627 (9) | 0.0146 (8) | 0.0163 (7) | 0.0226 (8) |
C4 | 0.0539 (7) | 0.0494 (8) | 0.0384 (6) | −0.0025 (6) | 0.0007 (5) | −0.0051 (6) |
C5 | 0.0625 (8) | 0.0505 (8) | 0.0528 (8) | 0.0076 (7) | −0.0021 (6) | −0.0040 (7) |
C6 | 0.0888 (12) | 0.0452 (8) | 0.0542 (8) | 0.0014 (8) | 0.0032 (8) | 0.0057 (7) |
C8 | 0.0404 (6) | 0.0356 (6) | 0.0533 (7) | 0.0013 (5) | 0.0055 (5) | −0.0028 (5) |
C9 | 0.0704 (10) | 0.0496 (9) | 0.0757 (11) | 0.0080 (7) | 0.0264 (8) | 0.0201 (8) |
C10 | 0.0718 (10) | 0.0635 (10) | 0.0459 (8) | 0.0136 (8) | 0.0143 (7) | 0.0109 (7) |
C11 | 0.0653 (9) | 0.0732 (11) | 0.0495 (8) | 0.0065 (8) | −0.0017 (6) | −0.0064 (8) |
C12 | 0.0406 (7) | 0.0676 (11) | 0.0831 (11) | −0.0097 (7) | 0.0068 (7) | −0.0131 (9) |
C13 | 0.0444 (7) | 0.0587 (9) | 0.0734 (10) | 0.0069 (7) | 0.0039 (6) | 0.0008 (8) |
C14 | 0.0624 (9) | 0.0613 (10) | 0.0654 (9) | 0.0107 (8) | 0.0175 (7) | −0.0026 (8) |
Geometric parameters (Å, º) top
S1—C8 | 1.7720 (15) | C6—H6A | 0.9300 |
S1—C11 | 1.8296 (17) | C9—C10 | 1.520 (3) |
F1—C1 | 1.3665 (18) | C9—H9A | 0.9700 |
N1—C8 | 1.2650 (19) | C9—H9B | 0.9700 |
N1—C4 | 1.4098 (19) | C10—C11 | 1.528 (2) |
N2—C8 | 1.3887 (17) | C10—C14 | 1.541 (2) |
N2—C9 | 1.455 (2) | C10—H10A | 0.9800 |
N2—C12 | 1.475 (2) | C11—H11A | 0.9700 |
C1—C2 | 1.365 (3) | C11—H11B | 0.9700 |
C1—C6 | 1.353 (2) | C12—C13 | 1.516 (3) |
C2—C3 | 1.385 (2) | C12—H12A | 0.9700 |
C2—H2A | 0.9300 | C12—H12B | 0.9700 |
C3—C4 | 1.375 (2) | C13—C14 | 1.512 (2) |
C3—H3A | 0.9300 | C13—H13A | 0.9700 |
C4—C5 | 1.384 (2) | C13—H13B | 0.9700 |
C5—C6 | 1.382 (2) | C14—H14A | 0.9700 |
C5—H5A | 0.9300 | C14—H14B | 0.9700 |
| | | |
C8—S1—C11 | 100.43 (7) | H9A—C9—H9B | 108.3 |
C8—N1—C4 | 122.22 (12) | C9—C10—C11 | 108.99 (13) |
C8—N2—C9 | 117.76 (13) | C9—C10—C14 | 109.02 (15) |
C8—N2—C12 | 113.68 (13) | C11—C10—C14 | 113.99 (14) |
C9—N2—C12 | 110.89 (13) | C9—C10—H10A | 108.2 |
F1—C1—C2 | 118.29 (17) | C11—C10—H10A | 108.2 |
F1—C1—C6 | 118.77 (16) | C14—C10—H10A | 108.2 |
C2—C1—C6 | 122.94 (16) | C10—C11—S1 | 116.17 (12) |
C1—C2—C3 | 118.09 (17) | C10—C11—H11A | 108.2 |
C1—C2—H2A | 121.0 | S1—C11—H11A | 108.2 |
C3—C2—H2A | 121.0 | C10—C11—H11B | 108.2 |
C2—C3—C4 | 121.06 (15) | S1—C11—H11B | 108.2 |
C2—C3—H3A | 119.5 | H11A—C11—H11B | 107.4 |
C4—C3—H3A | 119.5 | N2—C12—C13 | 108.93 (13) |
C5—C4—C3 | 118.48 (14) | N2—C12—H12A | 109.9 |
C5—C4—N1 | 119.69 (14) | C13—C12—H12A | 109.9 |
C3—C4—N1 | 121.56 (14) | N2—C12—H12B | 109.9 |
C4—C5—C6 | 121.13 (15) | C13—C12—H12B | 109.9 |
C4—C5—H5A | 119.4 | H12A—C12—H12B | 108.3 |
C6—C5—H5A | 119.4 | C12—C13—C14 | 111.58 (15) |
C1—C6—C5 | 118.26 (15) | C12—C13—H13A | 109.3 |
C1—C6—H6A | 120.9 | C14—C13—H13A | 109.3 |
C5—C6—H6A | 120.9 | C12—C13—H13B | 109.3 |
N1—C8—N2 | 119.59 (13) | C14—C13—H13B | 109.3 |
N1—C8—S1 | 124.44 (11) | H13A—C13—H13B | 108.0 |
N2—C8—S1 | 115.95 (11) | C13—C14—C10 | 113.88 (13) |
N2—C9—C10 | 109.25 (12) | C13—C14—H14A | 108.8 |
N2—C9—H9A | 109.8 | C10—C14—H14A | 108.8 |
C10—C9—H9A | 109.8 | C13—C14—H14B | 108.8 |
N2—C9—H9B | 109.8 | C10—C14—H14B | 108.8 |
C10—C9—H9B | 109.8 | H14A—C14—H14B | 107.7 |
| | | |
F1—C1—C2—C3 | 179.57 (17) | C12—N2—C8—S1 | 127.13 (12) |
C6—C1—C2—C3 | −1.1 (3) | C11—S1—C8—N1 | 138.02 (14) |
C1—C2—C3—C4 | −0.1 (3) | C11—S1—C8—N2 | −40.24 (13) |
C2—C3—C4—C5 | 1.7 (3) | C8—N2—C9—C10 | 66.46 (17) |
C2—C3—C4—N1 | 175.64 (17) | C12—N2—C9—C10 | −66.91 (17) |
C8—N1—C4—C5 | −118.20 (17) | N2—C9—C10—C11 | −67.89 (18) |
C8—N1—C4—C3 | 67.9 (2) | N2—C9—C10—C14 | 57.09 (17) |
C3—C4—C5—C6 | −2.1 (2) | C9—C10—C11—S1 | 13.87 (18) |
N1—C4—C5—C6 | −176.18 (13) | C14—C10—C11—S1 | −108.15 (15) |
F1—C1—C6—C5 | −179.98 (14) | C8—S1—C11—C10 | 34.13 (14) |
C2—C1—C6—C5 | 0.7 (3) | C8—N2—C12—C13 | −71.20 (18) |
C4—C5—C6—C1 | 0.9 (2) | C9—N2—C12—C13 | 64.18 (17) |
C4—N1—C8—N2 | −179.05 (13) | N2—C12—C13—C14 | −53.47 (18) |
C4—N1—C8—S1 | 2.7 (2) | C12—C13—C14—C10 | 48.0 (2) |
C9—N2—C8—N1 | 176.64 (14) | C9—C10—C14—C13 | −49.07 (19) |
C12—N2—C8—N1 | −51.23 (18) | C11—C10—C14—C13 | 72.9 (2) |
C9—N2—C8—S1 | −5.01 (16) | | |
Crystal data top
C14H18N2S | Dx = 1.275 Mg m−3 |
Mr = 246.36 | Melting point: 348 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9634 reflections |
a = 8.7377 (2) Å | θ = 3.8–25.0° |
b = 14.1088 (3) Å | µ = 0.23 mm−1 |
c = 20.8300 (5) Å | T = 100 K |
V = 2567.89 (10) Å3 | Block, colourless |
Z = 8 | 0.20 × 0.20 × 0.20 mm |
F(000) = 1056 | |
Data collection top
Bruker Kappa APEX-II CCD diffractometer | 2265 independent reflections |
Radiation source: fine-focus sealed tube | 2100 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
φ and ω scans | θmax = 25.0°, θmin = 3.8° |
Absorption correction: multi-scan SADABS (Bruker, 2008) | h = −10→10 |
Tmin = 0.932, Tmax = 0.955 | k = −16→16 |
38126 measured reflections | l = −24→24 |
Refinement top
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0376P)2 + 1.8178P] where P = (Fo2 + 2Fc2)/3 |
2265 reflections | (Δ/σ)max = 0.002 |
155 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C14H18N2S | V = 2567.89 (10) Å3 |
Mr = 246.36 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.7377 (2) Å | µ = 0.23 mm−1 |
b = 14.1088 (3) Å | T = 100 K |
c = 20.8300 (5) Å | 0.20 × 0.20 × 0.20 mm |
Data collection top
Bruker Kappa APEX-II CCD diffractometer | 2265 independent reflections |
Absorption correction: multi-scan SADABS (Bruker, 2008) | 2100 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.955 | Rint = 0.033 |
38126 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.51 e Å−3 |
2265 reflections | Δρmin = −0.19 e Å−3 |
155 parameters | |
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 | x | y | z | Uiso*/Ueq | |
S1 | 0.84809 (4) | 0.03355 (3) | 0.587973 (19) | 0.02182 (13) | |
N1 | 1.07226 (15) | 0.16743 (9) | 0.60206 (6) | 0.0223 (3) | |
N2 | 0.85825 (14) | 0.21315 (9) | 0.54478 (6) | 0.0201 (3) | |
C1 | 1.36591 (17) | −0.01997 (11) | 0.70237 (7) | 0.0220 (3) | |
C2 | 1.29254 (18) | −0.04956 (12) | 0.64613 (7) | 0.0237 (3) | |
H2A | 1.3099 | −0.1119 | 0.6304 | 0.028* | |
C3 | 1.19474 (18) | 0.01057 (12) | 0.61279 (7) | 0.0231 (3) | |
H3A | 1.1479 | −0.0107 | 0.5742 | 0.028* | |
C4 | 1.16451 (16) | 0.10184 (11) | 0.63523 (7) | 0.0210 (3) | |
C5 | 1.23839 (18) | 0.13171 (11) | 0.69139 (7) | 0.0237 (3) | |
H5A | 1.2208 | 0.1939 | 0.7073 | 0.028* | |
C6 | 1.33678 (17) | 0.07165 (12) | 0.72402 (7) | 0.0238 (3) | |
H6A | 1.3855 | 0.0935 | 0.7620 | 0.029* | |
C7 | 1.47929 (18) | −0.08305 (12) | 0.73623 (7) | 0.0273 (4) | |
H7A | 1.4788 | −0.0687 | 0.7823 | 0.041* | |
H7B | 1.5819 | −0.0719 | 0.7188 | 0.041* | |
H7C | 1.4509 | −0.1495 | 0.7296 | 0.041* | |
C8 | 0.94182 (17) | 0.14545 (10) | 0.57877 (7) | 0.0188 (3) | |
C9 | 0.71237 (18) | 0.18388 (11) | 0.51623 (7) | 0.0243 (3) | |
H9A | 0.7280 | 0.1268 | 0.4894 | 0.029* | |
H9B | 0.6724 | 0.2351 | 0.4884 | 0.029* | |
C10 | 0.59763 (18) | 0.16229 (11) | 0.56934 (8) | 0.0240 (3) | |
H10A | 0.4971 | 0.1458 | 0.5493 | 0.029* | |
C11 | 0.65509 (17) | 0.07612 (11) | 0.60859 (8) | 0.0246 (4) | |
H11A | 0.5820 | 0.0232 | 0.6026 | 0.029* | |
H11B | 0.6539 | 0.0933 | 0.6547 | 0.029* | |
C12 | 0.84231 (18) | 0.30482 (11) | 0.57798 (8) | 0.0236 (3) | |
H12A | 0.8042 | 0.3534 | 0.5477 | 0.028* | |
H12B | 0.9430 | 0.3257 | 0.5945 | 0.028* | |
C13 | 0.72977 (18) | 0.29317 (11) | 0.63354 (8) | 0.0247 (3) | |
H13A | 0.7113 | 0.3556 | 0.6538 | 0.030* | |
H13B | 0.7749 | 0.2508 | 0.6664 | 0.030* | |
C14 | 0.57725 (18) | 0.25165 (12) | 0.61055 (8) | 0.0260 (4) | |
H14A | 0.5221 | 0.3002 | 0.5852 | 0.031* | |
H14B | 0.5135 | 0.2359 | 0.6484 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0222 (2) | 0.0174 (2) | 0.0258 (2) | 0.00021 (14) | −0.00289 (15) | 0.00246 (15) |
N1 | 0.0196 (7) | 0.0243 (7) | 0.0230 (7) | −0.0010 (5) | 0.0034 (5) | 0.0046 (5) |
N2 | 0.0240 (7) | 0.0188 (6) | 0.0174 (6) | 0.0025 (5) | 0.0015 (5) | 0.0040 (5) |
C1 | 0.0166 (7) | 0.0321 (8) | 0.0173 (7) | −0.0012 (6) | 0.0032 (6) | 0.0039 (6) |
C2 | 0.0215 (8) | 0.0279 (8) | 0.0217 (8) | 0.0034 (6) | 0.0031 (6) | −0.0017 (6) |
C3 | 0.0201 (7) | 0.0328 (8) | 0.0164 (7) | 0.0022 (7) | 0.0008 (6) | −0.0019 (6) |
C4 | 0.0164 (7) | 0.0264 (8) | 0.0201 (7) | −0.0003 (6) | 0.0053 (6) | 0.0056 (6) |
C5 | 0.0213 (8) | 0.0250 (8) | 0.0247 (8) | −0.0040 (6) | 0.0032 (6) | −0.0024 (6) |
C6 | 0.0200 (7) | 0.0335 (9) | 0.0181 (7) | −0.0046 (7) | 0.0013 (6) | −0.0014 (7) |
C7 | 0.0246 (8) | 0.0349 (9) | 0.0224 (8) | 0.0006 (7) | −0.0007 (7) | 0.0046 (7) |
C8 | 0.0225 (8) | 0.0195 (7) | 0.0145 (7) | 0.0006 (6) | 0.0043 (6) | 0.0017 (6) |
C9 | 0.0309 (9) | 0.0238 (8) | 0.0182 (7) | 0.0061 (7) | −0.0066 (6) | 0.0006 (6) |
C10 | 0.0210 (8) | 0.0235 (8) | 0.0276 (8) | 0.0019 (6) | −0.0059 (7) | 0.0002 (6) |
C11 | 0.0192 (8) | 0.0237 (8) | 0.0308 (9) | −0.0025 (6) | −0.0008 (6) | 0.0018 (7) |
C12 | 0.0259 (8) | 0.0164 (7) | 0.0286 (8) | 0.0013 (6) | 0.0030 (7) | 0.0018 (6) |
C13 | 0.0286 (9) | 0.0211 (7) | 0.0243 (8) | 0.0020 (6) | 0.0023 (7) | −0.0016 (6) |
C14 | 0.0223 (8) | 0.0264 (8) | 0.0292 (8) | 0.0040 (7) | 0.0034 (7) | 0.0012 (7) |
Geometric parameters (Å, º) top
S1—C8 | 1.7888 (15) | C7—H7B | 0.9800 |
S1—C11 | 1.8410 (16) | C7—H7C | 0.9800 |
N1—C8 | 1.277 (2) | C9—C10 | 1.524 (2) |
N1—C4 | 1.408 (2) | C9—H9A | 0.9900 |
N2—C8 | 1.3953 (19) | C9—H9B | 0.9900 |
N2—C9 | 1.466 (2) | C10—C14 | 1.535 (2) |
N2—C12 | 1.473 (2) | C10—C11 | 1.549 (2) |
C1—C6 | 1.393 (2) | C10—H10A | 1.0000 |
C1—C2 | 1.399 (2) | C11—H11A | 0.9900 |
C1—C7 | 1.507 (2) | C11—H11B | 0.9900 |
C2—C3 | 1.390 (2) | C12—C13 | 1.528 (2) |
C2—H2A | 0.9500 | C12—H12A | 0.9900 |
C3—C4 | 1.395 (2) | C12—H12B | 0.9900 |
C3—H3A | 0.9500 | C13—C14 | 1.533 (2) |
C4—C5 | 1.401 (2) | C13—H13A | 0.9900 |
C5—C6 | 1.385 (2) | C13—H13B | 0.9900 |
C5—H5A | 0.9500 | C14—H14A | 0.9900 |
C6—H6A | 0.9500 | C14—H14B | 0.9900 |
C7—H7A | 0.9800 | | |
| | | |
C8—S1—C11 | 99.00 (7) | C10—C9—H9A | 109.8 |
C8—N1—C4 | 122.53 (13) | N2—C9—H9B | 109.8 |
C8—N2—C9 | 117.91 (12) | C10—C9—H9B | 109.8 |
C8—N2—C12 | 114.34 (12) | H9A—C9—H9B | 108.2 |
C9—N2—C12 | 110.83 (12) | C9—C10—C14 | 108.54 (13) |
C6—C1—C2 | 117.67 (14) | C9—C10—C11 | 109.08 (13) |
C6—C1—C7 | 121.13 (14) | C14—C10—C11 | 112.78 (13) |
C2—C1—C7 | 121.12 (14) | C9—C10—H10A | 108.8 |
C3—C2—C1 | 121.18 (15) | C14—C10—H10A | 108.8 |
C3—C2—H2A | 119.4 | C11—C10—H10A | 108.8 |
C1—C2—H2A | 119.4 | C10—C11—S1 | 115.47 (11) |
C2—C3—C4 | 120.82 (14) | C10—C11—H11A | 108.4 |
C2—C3—H3A | 119.6 | S1—C11—H11A | 108.4 |
C4—C3—H3A | 119.6 | C10—C11—H11B | 108.4 |
C3—C4—C5 | 118.05 (14) | S1—C11—H11B | 108.4 |
C3—C4—N1 | 123.39 (14) | H11A—C11—H11B | 107.5 |
C5—C4—N1 | 118.41 (14) | N2—C12—C13 | 108.79 (12) |
C6—C5—C4 | 120.77 (15) | N2—C12—H12A | 109.9 |
C6—C5—H5A | 119.6 | C13—C12—H12A | 109.9 |
C4—C5—H5A | 119.6 | N2—C12—H12B | 109.9 |
C5—C6—C1 | 121.49 (15) | C13—C12—H12B | 109.9 |
C5—C6—H6A | 119.3 | H12A—C12—H12B | 108.3 |
C1—C6—H6A | 119.3 | C12—C13—C14 | 111.35 (13) |
C1—C7—H7A | 109.5 | C12—C13—H13A | 109.4 |
C1—C7—H7B | 109.5 | C14—C13—H13A | 109.4 |
H7A—C7—H7B | 109.5 | C12—C13—H13B | 109.4 |
C1—C7—H7C | 109.5 | C14—C13—H13B | 109.4 |
H7A—C7—H7C | 109.5 | H13A—C13—H13B | 108.0 |
H7B—C7—H7C | 109.5 | C13—C14—C10 | 112.81 (13) |
N1—C8—N2 | 119.58 (13) | C13—C14—H14A | 109.0 |
N1—C8—S1 | 125.60 (12) | C10—C14—H14A | 109.0 |
N2—C8—S1 | 114.77 (11) | C13—C14—H14B | 109.0 |
N2—C9—C10 | 109.51 (12) | C10—C14—H14B | 109.0 |
N2—C9—H9A | 109.8 | H14A—C14—H14B | 107.8 |
| | | |
C6—C1—C2—C3 | 0.4 (2) | C12—N2—C8—S1 | 127.93 (11) |
C7—C1—C2—C3 | −176.21 (15) | C11—S1—C8—N1 | 134.09 (14) |
C1—C2—C3—C4 | −1.3 (2) | C11—S1—C8—N2 | −43.56 (12) |
C2—C3—C4—C5 | 1.5 (2) | C8—N2—C9—C10 | 67.61 (16) |
C2—C3—C4—N1 | 176.94 (14) | C12—N2—C9—C10 | −66.85 (15) |
C8—N1—C4—C3 | 47.2 (2) | N2—C9—C10—C14 | 58.77 (16) |
C8—N1—C4—C5 | −137.39 (15) | N2—C9—C10—C11 | −64.46 (16) |
C3—C4—C5—C6 | −0.9 (2) | C9—C10—C11—S1 | 6.71 (17) |
N1—C4—C5—C6 | −176.58 (14) | C14—C10—C11—S1 | −113.95 (14) |
C4—C5—C6—C1 | 0.1 (2) | C8—S1—C11—C10 | 41.46 (13) |
C2—C1—C6—C5 | 0.2 (2) | C8—N2—C12—C13 | −72.88 (16) |
C7—C1—C6—C5 | 176.81 (14) | C9—N2—C12—C13 | 63.31 (16) |
C4—N1—C8—N2 | −178.11 (13) | N2—C12—C13—C14 | −54.07 (17) |
C4—N1—C8—S1 | 4.3 (2) | C12—C13—C14—C10 | 50.08 (18) |
C9—N2—C8—N1 | 177.19 (13) | C9—C10—C14—C13 | −51.43 (17) |
C12—N2—C8—N1 | −49.87 (18) | C11—C10—C14—C13 | 69.55 (17) |
C9—N2—C8—S1 | −5.01 (16) | | |
Experimental details
| (1) | (2) | (3) |
Crystal data |
Chemical formula | C14H15F3N2S | C13H15FN2S | C14H18N2S |
Mr | 300.34 | 250.33 | 246.36 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 298 | 293 | 100 |
a, b, c (Å) | 13.074 (8), 9.185 (5), 12.652 (8) | 7.586 (1), 10.088 (2), 16.566 (4) | 8.7377 (2), 14.1088 (3), 20.8300 (5) |
α, β, γ (°) | 90, 109.33 (6), 90 | 90, 91.41 (3), 90 | 90, 90, 90 |
V (Å3) | 1433.7 (15) | 1267.4 (4) | 2567.89 (10) |
Z | 4 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.25 | 0.23 |
Crystal size (mm) | 0.35 × 0.20 × 0.15 | 0.45 × 0.30 × 0.15 | 0.20 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Nonius CAD-4 diffractometer | Nonius CAD-4 diffractometer | Bruker Kappa APEX-II CCD diffractometer |
Absorption correction | – | – | Multi-scan SADABS (Bruker, 2008) |
Tmin, Tmax | – | – | 0.932, 0.955 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2627, 2514, 852 | 3814, 3698, 2094 | 38126, 2265, 2100 |
Rint | 0.060 | 0.018 | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 | 0.703 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.075, 0.221, 0.87 | 0.040, 0.127, 0.98 | 0.033, 0.085, 1.08 |
No. of reflections | 2514 | 3698 | 2265 |
No. of parameters | 210 | 154 | 155 |
No. of restraints | 12 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.35 | 0.27, −0.25 | 0.51, −0.19 |