Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019607/ob6015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019607/ob6015Isup2.hkl |
CCDC reference: 155886
The title compound, (I), was prepared by Spa Contract Synthesis. Crystals were grown from an aqueous solution.
All H atoms were included in the refinement at calculated positions as riding models with C—H set to 0.95 (Ar—H) and 0.98 Å (CH3), except for the amine H atom, which was located on difference syntheses and for which both positional and displacement parameters were refined. The higher than expected Rint value (>0.10) may be due to a slight missalignment of the crystal plate on the diffractometer with respect to the beam.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular configuration and atom numbering scheme for (I), showing 30% probability ellipsoids. |
C15H13N3S | Dx = 1.357 Mg m−3 |
Mr = 267.34 | Melting point: 432-434 K K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 10.148 (2) Å | Cell parameters from 46446 reflections |
b = 14.251 (3) Å | θ = 1.0–27.5° |
c = 18.103 (4) Å | µ = 0.24 mm−1 |
V = 2618.1 (9) Å3 | T = 150 K |
Z = 8 | Plate, orange |
F(000) = 1120 | 0.30 × 0.24 × 0.02 mm |
Enraf Nonius KappaCCD area-detector diffractometer | 2947 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1498 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.121 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
ϕ and ω scans | h = −11→13 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −18→18 |
Tmin = 0.933, Tmax = 0.995 | l = −23→21 |
20334 measured reflections |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.170 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0867P)2] where P = (Fo2 + 2Fc2)/3 |
2947 reflections | (Δ/σ)max < 0.001 |
177 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C15H13N3S | V = 2618.1 (9) Å3 |
Mr = 267.34 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.148 (2) Å | µ = 0.24 mm−1 |
b = 14.251 (3) Å | T = 150 K |
c = 18.103 (4) Å | 0.30 × 0.24 × 0.02 mm |
Enraf Nonius KappaCCD area-detector diffractometer | 2947 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1498 reflections with I > 2σ(I) |
Tmin = 0.933, Tmax = 0.995 | Rint = 0.121 |
20334 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.170 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.32 e Å−3 |
2947 reflections | Δρmin = −0.33 e Å−3 |
177 parameters |
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
Geometry. Mean plane data ex SHELXL97 ########################### Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 7.2482 (0.0081) x - 6.6174 (0.0154) y + 9.4806 (0.0175) z = 3.4205 (0.0145) * -0.0012 (0.0019) N1 * 0.0030 (0.0021) C2 * -0.0025 (0.0021) C3 * 0.0006 (0.0021) C4 * 0.0011 (0.0019) C10 * -0.0009 (0.0020) C9 0.0028 (0.0047) C5 0.0120 (0.0054) C6 0.0109 (0.0051) C7 0.0108 (0.0041) C8 Rms deviation of fitted atoms = 0.0018 7.3426 (0.0092) x - 6.9706 (0.0171) y + 8.8178 (0.0181) z = 2.7969 (0.0120) Angle to previous plane (with approximate e.s.d.) = 2.59 (0.19) * -0.0022 (0.0014) S15 * 0.0044 (0.0016) C16 * -0.0051 (0.0019) C17 * 0.0031 (0.0020) C18 * -0.0002 (0.0018) C19 Rms deviation of fitted atoms = 0.0035 |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5693 (2) | 0.64109 (18) | 0.37293 (13) | 0.0418 (7) | |
C2 | 0.6529 (3) | 0.7026 (2) | 0.35234 (16) | 0.0381 (8) | |
H2 | 0.6626 | 0.7562 | 0.3831 | 0.048* | |
C3 | 0.7324 (3) | 0.6993 (2) | 0.28868 (19) | 0.0494 (9) | |
H3 | 0.7920 | 0.7485 | 0.2768 | 0.062* | |
C4 | 0.7195 (3) | 0.6214 (2) | 0.24448 (17) | 0.0471 (9) | |
H4 | 0.7712 | 0.6154 | 0.2010 | 0.059* | |
C5 | 0.6099 (3) | 0.4681 (2) | 0.22149 (17) | 0.0433 (8) | |
H5 | 0.6582 | 0.4583 | 0.1772 | 0.054* | |
C6 | 0.5212 (3) | 0.4034 (2) | 0.24518 (18) | 0.0462 (8) | |
H6 | 0.5088 | 0.3480 | 0.2168 | 0.058* | |
C7 | 0.4480 (3) | 0.4150 (2) | 0.30912 (16) | 0.0403 (8) | |
H7 | 0.3864 | 0.3683 | 0.3235 | 0.050* | |
C8 | 0.4644 (3) | 0.4946 (2) | 0.35212 (15) | 0.0357 (7) | |
C9 | 0.5564 (3) | 0.5637 (2) | 0.32874 (16) | 0.0369 (7) | |
C10 | 0.6294 (3) | 0.5505 (2) | 0.26396 (16) | 0.0387 (8) | |
N11 | 0.3944 (3) | 0.5114 (2) | 0.41531 (14) | 0.0417 (7) | |
H11 | 0.414 (3) | 0.564 (3) | 0.4480 (18) | 0.065 (11)* | |
N12 | 0.3027 (2) | 0.44926 (17) | 0.43975 (14) | 0.0371 (6) | |
C13 | 0.2338 (3) | 0.4690 (2) | 0.49707 (16) | 0.0354 (7) | |
C14 | 0.2482 (3) | 0.5580 (2) | 0.54076 (16) | 0.0417 (8) | |
H141 | 0.3407 | 0.5664 | 0.5548 | 0.052* | |
H142 | 0.1936 | 0.5542 | 0.5853 | 0.052* | |
H143 | 0.2196 | 0.6113 | 0.5106 | 0.052* | |
S15 | 0.10862 (8) | 0.30193 (6) | 0.46517 (4) | 0.0436 (3) | |
C16 | 0.1370 (3) | 0.4000 (2) | 0.51981 (15) | 0.0333 (7) | |
C17 | 0.0599 (3) | 0.3978 (2) | 0.58123 (17) | 0.0448 (8) | |
H17 | 0.0597 | 0.4455 | 0.6179 | 0.056* | |
C18 | −0.0204 (3) | 0.3163 (2) | 0.58454 (18) | 0.0475 (9) | |
H18 | −0.0793 | 0.3032 | 0.6240 | 0.059* | |
C19 | −0.0041 (3) | 0.2597 (2) | 0.52583 (16) | 0.0432 (8) | |
H19 | −0.0505 | 0.2024 | 0.5191 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0371 (16) | 0.0437 (17) | 0.0447 (15) | 0.0006 (13) | −0.0044 (12) | −0.0032 (13) |
C2 | 0.0367 (18) | 0.0368 (19) | 0.0409 (18) | 0.0009 (15) | 0.0032 (15) | 0.0027 (13) |
C3 | 0.0344 (19) | 0.051 (2) | 0.063 (2) | −0.0020 (16) | −0.0026 (17) | 0.0130 (17) |
C4 | 0.0285 (18) | 0.067 (3) | 0.0457 (19) | 0.0109 (17) | 0.0083 (15) | 0.0128 (17) |
C5 | 0.0369 (19) | 0.055 (2) | 0.0381 (18) | 0.0110 (16) | 0.0035 (15) | 0.0017 (15) |
C6 | 0.0389 (19) | 0.048 (2) | 0.051 (2) | 0.0077 (17) | −0.0023 (16) | −0.0037 (16) |
C7 | 0.0333 (18) | 0.046 (2) | 0.0420 (18) | 0.0024 (15) | −0.0013 (15) | 0.0016 (15) |
C8 | 0.0278 (17) | 0.0418 (19) | 0.0374 (17) | 0.0035 (14) | −0.0045 (14) | 0.0054 (14) |
C9 | 0.0267 (17) | 0.045 (2) | 0.0387 (17) | 0.0071 (15) | −0.0033 (14) | 0.0033 (14) |
C10 | 0.0291 (18) | 0.047 (2) | 0.0397 (19) | 0.0063 (14) | 0.0009 (14) | 0.0114 (14) |
N11 | 0.0401 (16) | 0.0489 (17) | 0.0361 (15) | −0.0052 (13) | 0.0044 (13) | −0.0028 (13) |
N12 | 0.0324 (14) | 0.0371 (15) | 0.0418 (15) | −0.0018 (12) | 0.0000 (12) | 0.0068 (11) |
C13 | 0.0315 (17) | 0.0408 (19) | 0.0337 (17) | 0.0046 (14) | −0.0046 (14) | 0.0041 (13) |
C14 | 0.0421 (19) | 0.0374 (18) | 0.0456 (19) | −0.0008 (14) | −0.0036 (15) | −0.0022 (14) |
S15 | 0.0419 (5) | 0.0418 (5) | 0.0470 (5) | −0.0019 (4) | 0.0060 (4) | −0.0015 (3) |
C16 | 0.0277 (17) | 0.0350 (17) | 0.0371 (17) | 0.0041 (13) | −0.0045 (13) | 0.0036 (12) |
C17 | 0.043 (2) | 0.048 (2) | 0.0434 (19) | 0.0026 (16) | 0.0062 (15) | 0.0001 (15) |
C18 | 0.040 (2) | 0.054 (2) | 0.048 (2) | −0.0023 (17) | 0.0051 (15) | 0.0054 (16) |
C19 | 0.0346 (18) | 0.0404 (19) | 0.055 (2) | 0.0003 (15) | 0.0046 (15) | 0.0030 (15) |
N1—C2 | 1.276 (4) | C9—C10 | 1.400 (4) |
N1—C9 | 1.369 (4) | N11—N12 | 1.359 (3) |
C2—C3 | 1.407 (4) | N11—H11 | 0.97 (4) |
C2—H2 | 0.9500 | N12—C13 | 1.283 (4) |
C3—C4 | 1.375 (5) | C13—C16 | 1.449 (4) |
C3—H3 | 0.9500 | C13—C14 | 1.501 (4) |
C4—C10 | 1.406 (4) | C14—H141 | 0.9800 |
C4—H4 | 0.9500 | C14—H142 | 0.9800 |
C5—C6 | 1.359 (4) | C14—H143 | 0.9800 |
C5—C10 | 1.418 (4) | S15—C19 | 1.696 (3) |
C5—H5 | 0.9500 | S15—C16 | 1.736 (3) |
C6—C7 | 1.385 (4) | C16—C17 | 1.360 (4) |
C6—H6 | 0.9500 | C17—C18 | 1.420 (4) |
C7—C8 | 1.386 (4) | C17—H17 | 0.9500 |
C7—H7 | 0.9500 | C18—C19 | 1.345 (4) |
C8—N11 | 1.368 (4) | C18—H18 | 0.9500 |
C8—C9 | 1.421 (4) | C19—H19 | 0.9500 |
C2—N1—C9 | 116.5 (3) | C4—C10—C5 | 123.3 (3) |
N1—C2—C3 | 126.7 (3) | N12—N11—C8 | 121.0 (3) |
N1—C2—H2 | 116.7 | N12—N11—H11 | 116 (2) |
C3—C2—H2 | 116.7 | C8—N11—H11 | 123 (2) |
C4—C3—C2 | 116.7 (3) | C13—N12—N11 | 119.6 (3) |
C4—C3—H3 | 121.7 | N12—C13—C16 | 116.7 (3) |
C2—C3—H3 | 121.7 | N12—C13—C14 | 124.0 (3) |
C3—C4—C10 | 119.7 (3) | C16—C13—C14 | 119.3 (3) |
C3—C4—H4 | 120.1 | C13—C14—H141 | 109.5 |
C10—C4—H4 | 120.1 | C13—C14—H142 | 109.5 |
C6—C5—C10 | 118.9 (3) | H141—C14—H142 | 109.5 |
C6—C5—H5 | 120.5 | C13—C14—H143 | 109.5 |
C10—C5—H5 | 120.5 | H141—C14—H143 | 109.5 |
C5—C6—C7 | 122.5 (3) | H142—C14—H143 | 109.5 |
C5—C6—H6 | 118.7 | C19—S15—C16 | 91.66 (15) |
C7—C6—H6 | 118.7 | C17—C16—C13 | 129.6 (3) |
C6—C7—C8 | 120.2 (3) | C17—C16—S15 | 110.6 (2) |
C6—C7—H7 | 119.9 | C13—C16—S15 | 119.8 (2) |
C8—C7—H7 | 119.9 | C16—C17—C18 | 112.6 (3) |
N11—C8—C7 | 123.4 (3) | C16—C17—H17 | 123.7 |
N11—C8—C9 | 118.0 (3) | C18—C17—H17 | 123.7 |
C7—C8—C9 | 118.6 (3) | C19—C18—C17 | 112.8 (3) |
N1—C9—C10 | 123.2 (3) | C19—C18—H18 | 123.6 |
N1—C9—C8 | 116.5 (3) | C17—C18—H18 | 123.6 |
C10—C9—C8 | 120.3 (3) | C18—C19—S15 | 112.4 (3) |
C9—C10—C4 | 117.3 (3) | C18—C19—H19 | 123.8 |
C9—C10—C5 | 119.4 (3) | S15—C19—H19 | 123.8 |
C9—N1—C2—C3 | 0.5 (5) | C6—C5—C10—C9 | −0.5 (4) |
N1—C2—C3—C4 | −0.7 (5) | C6—C5—C10—C4 | 179.6 (3) |
C2—C3—C4—C10 | 0.4 (4) | C7—C8—N11—N12 | 0.0 (4) |
C10—C5—C6—C7 | 0.4 (5) | C9—C8—N11—N12 | 178.5 (2) |
C5—C6—C7—C8 | −0.5 (5) | C8—N11—N12—C13 | −176.5 (3) |
C6—C7—C8—N11 | 179.1 (3) | N11—N12—C13—C16 | 179.5 (2) |
C6—C7—C8—C9 | 0.6 (4) | N11—N12—C13—C14 | −0.5 (4) |
C2—N1—C9—C10 | −0.1 (4) | N12—C13—C16—C17 | 173.2 (3) |
C2—N1—C9—C8 | 179.3 (3) | C14—C13—C16—C17 | −6.7 (4) |
N11—C8—C9—N1 | 1.4 (4) | N12—C13—C16—S15 | −5.9 (3) |
C7—C8—C9—N1 | 180.0 (3) | C14—C13—C16—S15 | 174.1 (2) |
N11—C8—C9—C10 | −179.2 (3) | C19—S15—C16—C17 | −0.6 (2) |
C7—C8—C9—C10 | −0.6 (4) | C19—S15—C16—C13 | 178.7 (2) |
N1—C9—C10—C4 | −0.1 (4) | C13—C16—C17—C18 | −178.3 (3) |
C8—C9—C10—C4 | −179.5 (2) | S15—C16—C17—C18 | 0.9 (3) |
N1—C9—C10—C5 | 179.9 (3) | C16—C17—C18—C19 | −0.9 (4) |
C8—C9—C10—C5 | 0.6 (4) | C17—C18—C19—S15 | 0.4 (4) |
C3—C4—C10—C9 | 0.0 (4) | C16—S15—C19—C18 | 0.1 (3) |
C3—C4—C10—C5 | 179.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N1 | 0.97 (4) | 2.36 (3) | 2.675 (4) | 98 (2) |
Experimental details
Crystal data | |
Chemical formula | C15H13N3S |
Mr | 267.34 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 150 |
a, b, c (Å) | 10.148 (2), 14.251 (3), 18.103 (4) |
V (Å3) | 2618.1 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.30 × 0.24 × 0.02 |
Data collection | |
Diffractometer | Enraf Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.933, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20334, 2947, 1498 |
Rint | 0.121 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.170, 0.98 |
No. of reflections | 2947 |
No. of parameters | 177 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.33 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N1 | 0.97 (4) | 2.36 (3) | 2.675 (4) | 98 (2) |
Two distinct crystal colours (orange and yellow) were observed in the bulk following crystallization of the title compound, (I). The molecular structures from both crystal types were determined and proved to be identical, as were the melting points. Both structures refined to approximately the same R value and the structure obtained from the orange crystals is reported here. The cell for the yellow crystals was determined as a = 10.1194 (9), b = 14.251 (1), c = 18.136 (2) Å and V = 2615.4 (4) Å3. The origin of the difference in colour is currently unknown and cannot be simply explained by crystal morphology because both crystal types were indistinguishable in size and shape. However, we cannot disguard the possibility of two different rates of crystallization; which we are currently investigating.