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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520613024384/bi5003sup1.cif
Contains datablocks 1, 2, 3, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520613024384/bi50031sup2.hkl
Contains datablock 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520613024384/bi50032sup3.hkl
Contains datablock 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520613024384/bi50033sup4.hkl
Contains datablock 3

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520613024384/bi5003sup5.pdf
Synthesis details and spectroscopic characterization

CCDC references: 984997; 984998; 984999

Computing details top

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.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
(1) top
Crystal data top
C14H15F3N2SF(000) = 624
Mr = 300.34Dx = 1.391 Mg m3
Monoclinic, P21/cMelting point: 364 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 13.074 (8) ÅCell parameters from 35 reflections
b = 9.185 (5) Åθ = 5–15°
c = 12.652 (8) ŵ = 0.25 mm1
β = 109.33 (6)°T = 298 K
V = 1433.7 (15) Å3Block, colourless
Z = 40.35 × 0.20 × 0.15 mm
Data collection top
Nonius CAD-4
diffractometer
Rint = 0.060
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 3.5°
Graphite monochromatorh = 015
ω–\2q scansk = 100
2627 measured reflectionsl = 1514
2514 independent reflections3 standard reflections every 200 reflections
852 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.075Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.221H-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 parametersΔρmax = 0.44 e Å3
12 restraintsΔρmin = 0.35 e Å3
Crystal data top
C14H15F3N2SV = 1433.7 (15) Å3
Mr = 300.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.074 (8) ŵ = 0.25 mm1
b = 9.185 (5) ÅT = 298 K
c = 12.652 (8) Å0.35 × 0.20 × 0.15 mm
β = 109.33 (6)°
Data collection top
Nonius CAD-4
diffractometer
Rint = 0.060
2627 measured reflections3 standard reflections every 200 reflections
2514 independent reflections intensity decay: none
852 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.07512 restraints
wR(F2) = 0.221H-atom parameters constrained
S = 0.87Δρmax = 0.44 e Å3
2514 reflectionsΔρmin = 0.35 e Å3
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
xyzUiso*/UeqOcc. (<1)
S10.56653 (12)0.3174 (2)0.51108 (15)0.0775 (7)
F10.0434 (16)0.166 (2)0.573 (3)0.103 (9)0.46 (5)
F20.0584 (12)0.294 (4)0.4449 (11)0.135 (10)0.46 (5)
F30.0797 (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)
N10.5501 (3)0.1450 (6)0.6764 (4)0.0659 (15)
N20.7223 (3)0.1656 (5)0.6649 (4)0.0545 (13)
C10.2181 (4)0.2400 (7)0.5837 (6)0.0640 (18)
C20.2573 (5)0.1588 (8)0.5137 (6)0.079 (2)
H2A0.20960.12300.44680.095*
C30.3679 (5)0.1299 (7)0.5423 (6)0.073 (2)
H3A0.39340.07640.49380.087*
C40.4405 (4)0.1803 (7)0.6430 (5)0.0588 (16)
C50.4002 (4)0.2656 (8)0.7123 (5)0.0679 (19)
H5A0.44730.30320.77890.081*
C60.2914 (5)0.2936 (8)0.6819 (6)0.073 (2)
H6A0.26600.35040.72870.088*
C70.0983 (5)0.2706 (7)0.5522 (7)0.088 (2)
C80.6124 (4)0.2024 (6)0.6246 (5)0.0527 (15)
C90.7849 (4)0.2160 (7)0.5920 (5)0.0662 (18)
H9A0.85690.17360.61780.079*
H9B0.74880.18400.51560.079*
C100.7931 (4)0.3754 (7)0.5951 (6)0.0636 (17)
H10A0.83880.40450.55100.076*
C110.6792 (5)0.4441 (8)0.5405 (6)0.076 (2)
H11A0.67710.49040.47090.091*
H11B0.66930.51960.58980.091*
C120.7783 (4)0.2044 (8)0.7815 (5)0.0683 (19)
H12A0.84850.15690.80720.082*
H12B0.73660.16990.82730.082*
C130.7935 (5)0.3649 (8)0.7956 (5)0.075 (2)
H13A0.83870.38630.87180.090*
H13B0.72370.41120.78250.090*
C140.8467 (5)0.4272 (8)0.7135 (6)0.073 (2)
H14A0.84340.53270.71500.088*
H14B0.92250.39920.73820.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0481 (9)0.1032 (15)0.0784 (12)0.0034 (10)0.0172 (7)0.0294 (11)
F10.048 (7)0.102 (14)0.188 (18)0.001 (7)0.077 (10)0.052 (10)
F20.046 (7)0.21 (2)0.133 (17)0.053 (10)0.009 (7)0.083 (13)
F30.057 (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)
N10.033 (2)0.091 (4)0.079 (4)0.006 (3)0.025 (2)0.023 (3)
N20.039 (2)0.070 (3)0.066 (3)0.006 (2)0.031 (2)0.007 (3)
C10.034 (3)0.071 (5)0.093 (5)0.002 (3)0.030 (3)0.019 (4)
C20.045 (3)0.092 (5)0.094 (5)0.010 (4)0.013 (3)0.014 (5)
C30.049 (3)0.076 (5)0.099 (5)0.009 (3)0.034 (4)0.027 (4)
C40.042 (3)0.063 (4)0.078 (4)0.003 (3)0.030 (3)0.014 (4)
C50.045 (3)0.110 (5)0.058 (4)0.007 (3)0.030 (3)0.002 (4)
C60.056 (4)0.100 (6)0.080 (5)0.018 (4)0.046 (4)0.015 (4)
C70.052 (4)0.086 (7)0.130 (8)0.004 (5)0.038 (5)0.019 (6)
C80.035 (3)0.055 (4)0.069 (4)0.000 (3)0.018 (3)0.004 (3)
C90.039 (3)0.098 (6)0.080 (4)0.007 (3)0.045 (3)0.013 (4)
C100.049 (3)0.084 (5)0.076 (5)0.004 (3)0.045 (3)0.000 (4)
C110.062 (4)0.077 (5)0.096 (5)0.007 (4)0.036 (4)0.018 (4)
C120.041 (3)0.114 (6)0.057 (4)0.007 (3)0.025 (3)0.013 (4)
C130.063 (4)0.103 (6)0.065 (4)0.016 (4)0.029 (3)0.020 (4)
C140.053 (3)0.092 (5)0.088 (5)0.022 (3)0.041 (3)0.013 (4)
Geometric parameters (Å, º) top
S1—C81.723 (6)C4—C51.402 (8)
S1—C111.817 (6)C5—C61.369 (7)
F1—C71.281 (10)C5—H5A0.9300
F2—C71.302 (10)C6—H6A0.9300
F3—C71.282 (11)C9—C101.468 (9)
F1'—C71.295 (10)C9—H9A0.9700
F2'—C71.271 (10)C9—H9B0.9700
F3'—C71.300 (10)C10—C141.505 (8)
N1—C81.313 (7)C10—C111.553 (8)
N1—C41.391 (7)C10—H10A0.9800
N2—C81.398 (6)C11—H11A0.9700
N2—C121.458 (7)C11—H11B0.9700
N2—C91.494 (7)C12—C131.490 (9)
C1—C21.380 (9)C12—H12A0.9700
C1—C61.385 (9)C12—H12B0.9700
C1—C71.509 (8)C13—C141.538 (8)
C2—C31.395 (8)C13—H13A0.9700
C2—H2A0.9300C13—H13B0.9700
C3—C41.392 (8)C14—H14A0.9700
C3—H3A0.9300C14—H14B0.9700
C8—S1—C11100.8 (3)N2—C8—S1118.9 (4)
C8—N1—C4120.1 (5)C10—C9—N2110.0 (5)
C8—N2—C12114.9 (4)C10—C9—H9A109.7
C8—N2—C9114.0 (5)N2—C9—H9A109.7
C12—N2—C9110.8 (4)C10—C9—H9B109.7
C2—C1—C6118.3 (5)N2—C9—H9B109.7
C2—C1—C7120.4 (6)H9A—C9—H9B108.2
C6—C1—C7121.4 (6)C9—C10—C14110.4 (6)
C1—C2—C3120.7 (6)C9—C10—C11110.0 (5)
C1—C2—H2A119.7C14—C10—C11112.1 (5)
C3—C2—H2A119.7C9—C10—H10A108.1
C4—C3—C2120.6 (6)C14—C10—H10A108.1
C4—C3—H3A119.7C11—C10—H10A108.1
C2—C3—H3A119.7C10—C11—S1115.1 (5)
N1—C4—C3121.5 (6)C10—C11—H11A108.5
N1—C4—C5120.1 (6)S1—C11—H11A108.5
C3—C4—C5118.3 (5)C10—C11—H11B108.5
C6—C5—C4120.0 (6)S1—C11—H11B108.5
C6—C5—H5A120.0H11A—C11—H11B107.5
C4—C5—H5A120.0N2—C12—C13111.4 (5)
C5—C6—C1122.1 (6)N2—C12—H12A109.3
C5—C6—H6A118.9C13—C12—H12A109.3
C1—C6—H6A118.9N2—C12—H12B109.3
F1—C7—F3107.9 (9)C13—C12—H12B109.3
F1—C7—F2106.5 (9)H12A—C12—H12B108.0
F3—C7—F2106.8 (10)C12—C13—C14111.1 (5)
F2'—C7—F1'107.7 (9)C12—C13—H13A109.4
F2'—C7—F3'107.6 (9)C14—C13—H13A109.4
F1'—C7—F3'105.0 (9)C12—C13—H13B109.4
F2'—C7—C1116.7 (10)C14—C13—H13B109.4
F1—C7—C1114.2 (11)H13A—C13—H13B108.0
F3—C7—C1111.8 (12)C10—C14—C13112.8 (5)
F1'—C7—C1109.3 (10)C10—C14—H14A109.0
F3'—C7—C1109.9 (10)C13—C14—H14A109.0
F2—C7—C1109.2 (9)C10—C14—H14B109.0
N1—C8—N2117.0 (5)C13—C14—H14B109.0
N1—C8—S1124.0 (4)H14A—C14—H14B107.8
C6—C1—C2—C31.0 (10)C6—C1—C7—F2140.8 (18)
C7—C1—C2—C3179.9 (6)C4—N1—C8—N2178.1 (5)
C1—C2—C3—C41.1 (11)C4—N1—C8—S12.4 (8)
C8—N1—C4—C371.2 (8)C12—N2—C8—N159.3 (7)
C8—N1—C4—C5110.3 (7)C9—N2—C8—N1171.2 (5)
C2—C3—C4—N1175.9 (6)C12—N2—C8—S1121.1 (5)
C2—C3—C4—C52.6 (10)C9—N2—C8—S18.4 (7)
N1—C4—C5—C6176.5 (6)C11—S1—C8—N1142.4 (5)
C3—C4—C5—C62.0 (9)C11—S1—C8—N238.1 (5)
C4—C5—C6—C10.1 (10)C8—N2—C9—C1068.6 (7)
C2—C1—C6—C51.5 (10)C12—N2—C9—C1062.9 (7)
C7—C1—C6—C5179.3 (6)N2—C9—C10—C1458.0 (6)
C2—C1—C7—F2'74 (3)N2—C9—C10—C1166.2 (7)
C6—C1—C7—F2'105 (2)C9—C10—C11—S110.4 (7)
C2—C1—C7—F180.8 (19)C14—C10—C11—S1112.8 (6)
C6—C1—C7—F1100.1 (18)C8—S1—C11—C1036.3 (5)
C2—C1—C7—F3156 (2)C8—N2—C12—C1371.5 (6)
C6—C1—C7—F323 (2)C9—N2—C12—C1359.6 (6)
C2—C1—C7—F1'48 (2)N2—C12—C13—C1451.9 (6)
C6—C1—C7—F1'133 (2)C9—C10—C14—C1351.8 (7)
C2—C1—C7—F3'163 (3)C11—C10—C14—C1371.2 (7)
C6—C1—C7—F3'18 (3)C12—C13—C14—C1048.4 (8)
C2—C1—C7—F238 (2)
(2) top
Crystal data top
C13H15FN2SF(000) = 528
Mr = 250.33Dx = 1.312 Mg m3
Monoclinic, P21/cMelting point: 363 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.586 (1) ÅCell parameters from 35 reflections
b = 10.088 (2) Åθ = 5–15°
c = 16.566 (4) ŵ = 0.25 mm1
β = 91.41 (3)°T = 293 K
V = 1267.4 (4) Å3Block, colourless
Z = 40.45 × 0.30 × 0.15 mm
Data collection top
Nonius CAD-4
diffractometer
Rint = 0.018
Radiation source: fine-focus sealed tubeθmax = 30.0°, θmin = 2.4°
Graphite monochromatorh = 1010
ω–\2q scansk = 014
3814 measured reflectionsl = 023
3698 independent reflections3 standard reflections every 200 reflections
2094 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-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 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C13H15FN2SV = 1267.4 (4) Å3
Mr = 250.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.586 (1) ŵ = 0.25 mm1
b = 10.088 (2) ÅT = 293 K
c = 16.566 (4) Å0.45 × 0.30 × 0.15 mm
β = 91.41 (3)°
Data collection top
Nonius CAD-4
diffractometer
Rint = 0.018
3814 measured reflections3 standard reflections every 200 reflections
3698 independent reflections intensity decay: none
2094 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 0.98Δρmax = 0.27 e Å3
3698 reflectionsΔρmin = 0.25 e Å3
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
xyzUiso*/Ueq
S11.14718 (5)0.27372 (5)0.50016 (2)0.05899 (15)
F11.49014 (18)0.44604 (13)0.17884 (8)0.0973 (4)
N10.96747 (16)0.22477 (14)0.36082 (8)0.0548 (3)
N20.83473 (16)0.15279 (12)0.47580 (8)0.0528 (3)
C11.3612 (2)0.39195 (18)0.22469 (9)0.0630 (4)
C21.3985 (3)0.2779 (2)0.26612 (12)0.0724 (5)
H2A1.50840.23770.26300.087*
C31.2678 (2)0.22395 (18)0.31296 (11)0.0648 (4)
H3A1.29040.14620.34160.078*
C41.10529 (19)0.28343 (15)0.31780 (8)0.0472 (3)
C51.0731 (2)0.39711 (16)0.27303 (9)0.0553 (4)
H5A0.96250.43680.27430.066*
C61.2024 (2)0.45265 (16)0.22644 (9)0.0627 (4)
H6A1.18070.52980.19710.075*
C80.97345 (17)0.21325 (13)0.43688 (8)0.0430 (3)
C90.8515 (2)0.13495 (17)0.56284 (11)0.0649 (5)
H9A0.96010.08840.57620.078*
H9B0.75370.08240.58180.078*
C100.8520 (2)0.26987 (17)0.60370 (9)0.0602 (4)
H10A0.85180.25600.66230.072*
C111.0214 (2)0.34300 (19)0.58300 (10)0.0627 (4)
H11A1.09730.34520.63100.075*
H11B0.99120.43390.56950.075*
C120.66026 (19)0.20752 (18)0.45292 (12)0.0637 (4)
H12A0.56810.15060.47300.076*
H12B0.64750.21210.39460.076*
C130.64368 (19)0.34508 (17)0.48880 (10)0.0588 (4)
H13A0.52520.37810.47840.071*
H13B0.72530.40440.46280.071*
C140.6820 (2)0.34457 (19)0.57883 (10)0.0627 (4)
H14A0.58340.30420.60570.075*
H14B0.69160.43550.59750.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.04262 (19)0.0797 (3)0.0546 (2)0.00286 (18)0.00027 (14)0.00468 (19)
F10.1085 (9)0.0946 (9)0.0910 (8)0.0154 (7)0.0453 (7)0.0185 (7)
N10.0522 (7)0.0598 (8)0.0524 (7)0.0087 (6)0.0021 (5)0.0067 (6)
N20.0480 (6)0.0403 (6)0.0709 (8)0.0035 (5)0.0149 (5)0.0020 (6)
C10.0781 (11)0.0609 (10)0.0508 (8)0.0039 (9)0.0185 (7)0.0057 (7)
C20.0672 (10)0.0840 (13)0.0671 (10)0.0183 (9)0.0231 (8)0.0168 (10)
C30.0675 (9)0.0649 (10)0.0627 (9)0.0146 (8)0.0163 (7)0.0226 (8)
C40.0539 (7)0.0494 (8)0.0384 (6)0.0025 (6)0.0007 (5)0.0051 (6)
C50.0625 (8)0.0505 (8)0.0528 (8)0.0076 (7)0.0021 (6)0.0040 (7)
C60.0888 (12)0.0452 (8)0.0542 (8)0.0014 (8)0.0032 (8)0.0057 (7)
C80.0404 (6)0.0356 (6)0.0533 (7)0.0013 (5)0.0055 (5)0.0028 (5)
C90.0704 (10)0.0496 (9)0.0757 (11)0.0080 (7)0.0264 (8)0.0201 (8)
C100.0718 (10)0.0635 (10)0.0459 (8)0.0136 (8)0.0143 (7)0.0109 (7)
C110.0653 (9)0.0732 (11)0.0495 (8)0.0065 (8)0.0017 (6)0.0064 (8)
C120.0406 (7)0.0676 (11)0.0831 (11)0.0097 (7)0.0068 (7)0.0131 (9)
C130.0444 (7)0.0587 (9)0.0734 (10)0.0069 (7)0.0039 (6)0.0008 (8)
C140.0624 (9)0.0613 (10)0.0654 (9)0.0107 (8)0.0175 (7)0.0026 (8)
Geometric parameters (Å, º) top
S1—C81.7720 (15)C6—H6A0.9300
S1—C111.8296 (17)C9—C101.520 (3)
F1—C11.3665 (18)C9—H9A0.9700
N1—C81.2650 (19)C9—H9B0.9700
N1—C41.4098 (19)C10—C111.528 (2)
N2—C81.3887 (17)C10—C141.541 (2)
N2—C91.455 (2)C10—H10A0.9800
N2—C121.475 (2)C11—H11A0.9700
C1—C21.365 (3)C11—H11B0.9700
C1—C61.353 (2)C12—C131.516 (3)
C2—C31.385 (2)C12—H12A0.9700
C2—H2A0.9300C12—H12B0.9700
C3—C41.375 (2)C13—C141.512 (2)
C3—H3A0.9300C13—H13A0.9700
C4—C51.384 (2)C13—H13B0.9700
C5—C61.382 (2)C14—H14A0.9700
C5—H5A0.9300C14—H14B0.9700
C8—S1—C11100.43 (7)H9A—C9—H9B108.3
C8—N1—C4122.22 (12)C9—C10—C11108.99 (13)
C8—N2—C9117.76 (13)C9—C10—C14109.02 (15)
C8—N2—C12113.68 (13)C11—C10—C14113.99 (14)
C9—N2—C12110.89 (13)C9—C10—H10A108.2
F1—C1—C2118.29 (17)C11—C10—H10A108.2
F1—C1—C6118.77 (16)C14—C10—H10A108.2
C2—C1—C6122.94 (16)C10—C11—S1116.17 (12)
C1—C2—C3118.09 (17)C10—C11—H11A108.2
C1—C2—H2A121.0S1—C11—H11A108.2
C3—C2—H2A121.0C10—C11—H11B108.2
C2—C3—C4121.06 (15)S1—C11—H11B108.2
C2—C3—H3A119.5H11A—C11—H11B107.4
C4—C3—H3A119.5N2—C12—C13108.93 (13)
C5—C4—C3118.48 (14)N2—C12—H12A109.9
C5—C4—N1119.69 (14)C13—C12—H12A109.9
C3—C4—N1121.56 (14)N2—C12—H12B109.9
C4—C5—C6121.13 (15)C13—C12—H12B109.9
C4—C5—H5A119.4H12A—C12—H12B108.3
C6—C5—H5A119.4C12—C13—C14111.58 (15)
C1—C6—C5118.26 (15)C12—C13—H13A109.3
C1—C6—H6A120.9C14—C13—H13A109.3
C5—C6—H6A120.9C12—C13—H13B109.3
N1—C8—N2119.59 (13)C14—C13—H13B109.3
N1—C8—S1124.44 (11)H13A—C13—H13B108.0
N2—C8—S1115.95 (11)C13—C14—C10113.88 (13)
N2—C9—C10109.25 (12)C13—C14—H14A108.8
N2—C9—H9A109.8C10—C14—H14A108.8
C10—C9—H9A109.8C13—C14—H14B108.8
N2—C9—H9B109.8C10—C14—H14B108.8
C10—C9—H9B109.8H14A—C14—H14B107.7
F1—C1—C2—C3179.57 (17)C12—N2—C8—S1127.13 (12)
C6—C1—C2—C31.1 (3)C11—S1—C8—N1138.02 (14)
C1—C2—C3—C40.1 (3)C11—S1—C8—N240.24 (13)
C2—C3—C4—C51.7 (3)C8—N2—C9—C1066.46 (17)
C2—C3—C4—N1175.64 (17)C12—N2—C9—C1066.91 (17)
C8—N1—C4—C5118.20 (17)N2—C9—C10—C1167.89 (18)
C8—N1—C4—C367.9 (2)N2—C9—C10—C1457.09 (17)
C3—C4—C5—C62.1 (2)C9—C10—C11—S113.87 (18)
N1—C4—C5—C6176.18 (13)C14—C10—C11—S1108.15 (15)
F1—C1—C6—C5179.98 (14)C8—S1—C11—C1034.13 (14)
C2—C1—C6—C50.7 (3)C8—N2—C12—C1371.20 (18)
C4—C5—C6—C10.9 (2)C9—N2—C12—C1364.18 (17)
C4—N1—C8—N2179.05 (13)N2—C12—C13—C1453.47 (18)
C4—N1—C8—S12.7 (2)C12—C13—C14—C1048.0 (2)
C9—N2—C8—N1176.64 (14)C9—C10—C14—C1349.07 (19)
C12—N2—C8—N151.23 (18)C11—C10—C14—C1372.9 (2)
C9—N2—C8—S15.01 (16)
(3) top
Crystal data top
C14H18N2SDx = 1.275 Mg m3
Mr = 246.36Melting point: 348 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 9634 reflections
a = 8.7377 (2) Åθ = 3.8–25.0°
b = 14.1088 (3) ŵ = 0.23 mm1
c = 20.8300 (5) ÅT = 100 K
V = 2567.89 (10) Å3Block, colourless
Z = 80.20 × 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 tube2100 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
φ and ω scansθmax = 25.0°, θmin = 3.8°
Absorption correction: multi-scan
SADABS (Bruker, 2008)
h = 1010
Tmin = 0.932, Tmax = 0.955k = 1616
38126 measured reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-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 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C14H18N2SV = 2567.89 (10) Å3
Mr = 246.36Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.7377 (2) ŵ = 0.23 mm1
b = 14.1088 (3) ÅT = 100 K
c = 20.8300 (5) Å0.20 × 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 = 0.955Rint = 0.033
38126 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 1.08Δρmax = 0.51 e Å3
2265 reflectionsΔρmin = 0.19 e Å3
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
xyzUiso*/Ueq
S10.84809 (4)0.03355 (3)0.587973 (19)0.02182 (13)
N11.07226 (15)0.16743 (9)0.60206 (6)0.0223 (3)
N20.85825 (14)0.21315 (9)0.54478 (6)0.0201 (3)
C11.36591 (17)0.01997 (11)0.70237 (7)0.0220 (3)
C21.29254 (18)0.04956 (12)0.64613 (7)0.0237 (3)
H2A1.30990.11190.63040.028*
C31.19474 (18)0.01057 (12)0.61279 (7)0.0231 (3)
H3A1.14790.01070.57420.028*
C41.16451 (16)0.10184 (11)0.63523 (7)0.0210 (3)
C51.23839 (18)0.13171 (11)0.69139 (7)0.0237 (3)
H5A1.22080.19390.70730.028*
C61.33678 (17)0.07165 (12)0.72402 (7)0.0238 (3)
H6A1.38550.09350.76200.029*
C71.47929 (18)0.08305 (12)0.73623 (7)0.0273 (4)
H7A1.47880.06870.78230.041*
H7B1.58190.07190.71880.041*
H7C1.45090.14950.72960.041*
C80.94182 (17)0.14545 (10)0.57877 (7)0.0188 (3)
C90.71237 (18)0.18388 (11)0.51623 (7)0.0243 (3)
H9A0.72800.12680.48940.029*
H9B0.67240.23510.48840.029*
C100.59763 (18)0.16229 (11)0.56934 (8)0.0240 (3)
H10A0.49710.14580.54930.029*
C110.65509 (17)0.07612 (11)0.60859 (8)0.0246 (4)
H11A0.58200.02320.60260.029*
H11B0.65390.09330.65470.029*
C120.84231 (18)0.30482 (11)0.57798 (8)0.0236 (3)
H12A0.80420.35340.54770.028*
H12B0.94300.32570.59450.028*
C130.72977 (18)0.29317 (11)0.63354 (8)0.0247 (3)
H13A0.71130.35560.65380.030*
H13B0.77490.25080.66640.030*
C140.57725 (18)0.25165 (12)0.61055 (8)0.0260 (4)
H14A0.52210.30020.58520.031*
H14B0.51350.23590.64840.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0222 (2)0.0174 (2)0.0258 (2)0.00021 (14)0.00289 (15)0.00246 (15)
N10.0196 (7)0.0243 (7)0.0230 (7)0.0010 (5)0.0034 (5)0.0046 (5)
N20.0240 (7)0.0188 (6)0.0174 (6)0.0025 (5)0.0015 (5)0.0040 (5)
C10.0166 (7)0.0321 (8)0.0173 (7)0.0012 (6)0.0032 (6)0.0039 (6)
C20.0215 (8)0.0279 (8)0.0217 (8)0.0034 (6)0.0031 (6)0.0017 (6)
C30.0201 (7)0.0328 (8)0.0164 (7)0.0022 (7)0.0008 (6)0.0019 (6)
C40.0164 (7)0.0264 (8)0.0201 (7)0.0003 (6)0.0053 (6)0.0056 (6)
C50.0213 (8)0.0250 (8)0.0247 (8)0.0040 (6)0.0032 (6)0.0024 (6)
C60.0200 (7)0.0335 (9)0.0181 (7)0.0046 (7)0.0013 (6)0.0014 (7)
C70.0246 (8)0.0349 (9)0.0224 (8)0.0006 (7)0.0007 (7)0.0046 (7)
C80.0225 (8)0.0195 (7)0.0145 (7)0.0006 (6)0.0043 (6)0.0017 (6)
C90.0309 (9)0.0238 (8)0.0182 (7)0.0061 (7)0.0066 (6)0.0006 (6)
C100.0210 (8)0.0235 (8)0.0276 (8)0.0019 (6)0.0059 (7)0.0002 (6)
C110.0192 (8)0.0237 (8)0.0308 (9)0.0025 (6)0.0008 (6)0.0018 (7)
C120.0259 (8)0.0164 (7)0.0286 (8)0.0013 (6)0.0030 (7)0.0018 (6)
C130.0286 (9)0.0211 (7)0.0243 (8)0.0020 (6)0.0023 (7)0.0016 (6)
C140.0223 (8)0.0264 (8)0.0292 (8)0.0040 (7)0.0034 (7)0.0012 (7)
Geometric parameters (Å, º) top
S1—C81.7888 (15)C7—H7B0.9800
S1—C111.8410 (16)C7—H7C0.9800
N1—C81.277 (2)C9—C101.524 (2)
N1—C41.408 (2)C9—H9A0.9900
N2—C81.3953 (19)C9—H9B0.9900
N2—C91.466 (2)C10—C141.535 (2)
N2—C121.473 (2)C10—C111.549 (2)
C1—C61.393 (2)C10—H10A1.0000
C1—C21.399 (2)C11—H11A0.9900
C1—C71.507 (2)C11—H11B0.9900
C2—C31.390 (2)C12—C131.528 (2)
C2—H2A0.9500C12—H12A0.9900
C3—C41.395 (2)C12—H12B0.9900
C3—H3A0.9500C13—C141.533 (2)
C4—C51.401 (2)C13—H13A0.9900
C5—C61.385 (2)C13—H13B0.9900
C5—H5A0.9500C14—H14A0.9900
C6—H6A0.9500C14—H14B0.9900
C7—H7A0.9800
C8—S1—C1199.00 (7)C10—C9—H9A109.8
C8—N1—C4122.53 (13)N2—C9—H9B109.8
C8—N2—C9117.91 (12)C10—C9—H9B109.8
C8—N2—C12114.34 (12)H9A—C9—H9B108.2
C9—N2—C12110.83 (12)C9—C10—C14108.54 (13)
C6—C1—C2117.67 (14)C9—C10—C11109.08 (13)
C6—C1—C7121.13 (14)C14—C10—C11112.78 (13)
C2—C1—C7121.12 (14)C9—C10—H10A108.8
C3—C2—C1121.18 (15)C14—C10—H10A108.8
C3—C2—H2A119.4C11—C10—H10A108.8
C1—C2—H2A119.4C10—C11—S1115.47 (11)
C2—C3—C4120.82 (14)C10—C11—H11A108.4
C2—C3—H3A119.6S1—C11—H11A108.4
C4—C3—H3A119.6C10—C11—H11B108.4
C3—C4—C5118.05 (14)S1—C11—H11B108.4
C3—C4—N1123.39 (14)H11A—C11—H11B107.5
C5—C4—N1118.41 (14)N2—C12—C13108.79 (12)
C6—C5—C4120.77 (15)N2—C12—H12A109.9
C6—C5—H5A119.6C13—C12—H12A109.9
C4—C5—H5A119.6N2—C12—H12B109.9
C5—C6—C1121.49 (15)C13—C12—H12B109.9
C5—C6—H6A119.3H12A—C12—H12B108.3
C1—C6—H6A119.3C12—C13—C14111.35 (13)
C1—C7—H7A109.5C12—C13—H13A109.4
C1—C7—H7B109.5C14—C13—H13A109.4
H7A—C7—H7B109.5C12—C13—H13B109.4
C1—C7—H7C109.5C14—C13—H13B109.4
H7A—C7—H7C109.5H13A—C13—H13B108.0
H7B—C7—H7C109.5C13—C14—C10112.81 (13)
N1—C8—N2119.58 (13)C13—C14—H14A109.0
N1—C8—S1125.60 (12)C10—C14—H14A109.0
N2—C8—S1114.77 (11)C13—C14—H14B109.0
N2—C9—C10109.51 (12)C10—C14—H14B109.0
N2—C9—H9A109.8H14A—C14—H14B107.8
C6—C1—C2—C30.4 (2)C12—N2—C8—S1127.93 (11)
C7—C1—C2—C3176.21 (15)C11—S1—C8—N1134.09 (14)
C1—C2—C3—C41.3 (2)C11—S1—C8—N243.56 (12)
C2—C3—C4—C51.5 (2)C8—N2—C9—C1067.61 (16)
C2—C3—C4—N1176.94 (14)C12—N2—C9—C1066.85 (15)
C8—N1—C4—C347.2 (2)N2—C9—C10—C1458.77 (16)
C8—N1—C4—C5137.39 (15)N2—C9—C10—C1164.46 (16)
C3—C4—C5—C60.9 (2)C9—C10—C11—S16.71 (17)
N1—C4—C5—C6176.58 (14)C14—C10—C11—S1113.95 (14)
C4—C5—C6—C10.1 (2)C8—S1—C11—C1041.46 (13)
C2—C1—C6—C50.2 (2)C8—N2—C12—C1372.88 (16)
C7—C1—C6—C5176.81 (14)C9—N2—C12—C1363.31 (16)
C4—N1—C8—N2178.11 (13)N2—C12—C13—C1454.07 (17)
C4—N1—C8—S14.3 (2)C12—C13—C14—C1050.08 (18)
C9—N2—C8—N1177.19 (13)C9—C10—C14—C1351.43 (17)
C12—N2—C8—N149.87 (18)C11—C10—C14—C1369.55 (17)
C9—N2—C8—S15.01 (16)

Experimental details

(1)(2)(3)
Crystal data
Chemical formulaC14H15F3N2SC13H15FN2SC14H18N2S
Mr300.34250.33246.36
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cOrthorhombic, Pbca
Temperature (K)298293100
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), 9090, 91.41 (3), 9090, 90, 90
V3)1433.7 (15)1267.4 (4)2567.89 (10)
Z448
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.250.250.23
Crystal size (mm)0.35 × 0.20 × 0.150.45 × 0.30 × 0.150.20 × 0.20 × 0.20
Data collection
DiffractometerNonius CAD-4
diffractometer
Nonius CAD-4
diffractometer
Bruker Kappa APEX-II CCD
diffractometer
Absorption correctionMulti-scan
SADABS (Bruker, 2008)
Tmin, Tmax0.932, 0.955
No. of measured, independent and
observed [I > 2σ(I)] reflections
2627, 2514, 852 3814, 3698, 2094 38126, 2265, 2100
Rint0.0600.0180.033
(sin θ/λ)max1)0.5950.7030.595
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 reflections251436982265
No. of parameters210154155
No. of restraints1200
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.44, 0.350.27, 0.250.51, 0.19

Computer programs: CAD-4 (Enraf-Nonius, 1993), APEX2 (Bruker, 2008), CAD-4, APEX2, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXL97.

 

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