Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029522/lh2431sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029522/lh2431Isup2.hkl |
CCDC reference: 655012
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.007 Å
- Disorder in main residue
- R factor = 0.062
- wR factor = 0.187
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C18 PLAT431_ALERT_2_B Short Inter HL..A Contact F2 .. F2 .. 2.45 Ang.
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 43 Perc. PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.10 Ratio PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.84 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S1 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S2 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C32 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C14 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C34 PLAT301_ALERT_3_C Main Residue Disorder ......................... 11.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT410_ALERT_2_C Short Intra H...H Contact H9A .. H17A .. 1.94 Ang. PLAT410_ALERT_2_C Short Intra H...H Contact H10B .. H13A .. 1.94 Ang. PLAT410_ALERT_2_C Short Intra H...H Contact H27B .. H31A .. 1.93 Ang. PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 33.20 Deg. F1 -C18 -F1' 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 41.30 Deg. F2' -C18 -F2 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 41.00 Deg. F6' -C36 -F6 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 30.20 Deg. F5 -C36 -F5' 1.555 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 156
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 19 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 17 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of 2-acetothiophene 1.26 (10 mmol), 1-(3-Trifluoromethyl-phenyl)-piperazine 2.3 g (15 mmol) and concentrated hydrochloric acid (10 ml) in absolute ethanol(20 ml) was refluxed. Paraformaldehyde 0.9 g (45 mmol) was added over a period of 20 min. The reaction mixture was refluxed for another 12 h, cooled and the solid was precipitated. 20 ml acetone was added to the mixture and stirred for 30 min. The mixture was filtrated, washed with ethyl ether, dried in vacuum to give the title compound. The title compound was dissolved in absolute methanol; the solution was kept at ambient temperature for 15 d by natural evaporation to give single crystals suitable for X-ray analysis.
Carbon-bound H atoms were positioned geometrically, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 Ueq(C), The nitrogen-bound H atoms were refined freely.
Mannich bases can be used as anti-corrosion reagents or as a class of selective antidepressants with a low incidence of side effects (Oficialdegui et al., 2000; Martinez et al., 2001; Esparza et al., 2001; Orus et al., 2002). The title compound, was synthesized from 2-acetothiophene, 1-(3-Trifluoromethyl-phenyl)-piperazineand and paraformaldehyde. The molecular structure of the title compound is illustrated in Fig. 1. The asymmetric unit contains two independent molecules. Two intermolecular N—H···Cl hydrogen bonds help to consolidate the crystal packing. In each molecule, the piperazine ring has a chair conformation and the F atoms of the CF3 groups are disordered over two sites.
For background information, see: Oficialdegui et al. (2000); Martinez et al. (2001); Esparza et al. (2001); Orus et al. (2002).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of one of the cations drawn with 30% probability ellipsoids. |
C18H20F3N2OS+·Cl− | F(000) = 1680 |
Mr = 404.89 | Dx = 1.386 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3440 reflections |
a = 10.5715 (14) Å | θ = 2.3–22.6° |
b = 10.4989 (14) Å | µ = 0.34 mm−1 |
c = 34.966 (8) Å | T = 294 K |
β = 90.040 (6)° | Block, colorless |
V = 3880.8 (12) Å3 | 0.20 × 0.14 × 0.12 mm |
Z = 8 |
Bruker SMART CCD diffractometer | 7997 independent reflections |
Radiation source: fine-focus sealed tube | 3476 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
φ and ω scans | θmax = 26.5°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −13→8 |
Tmin = 0.935, Tmax = 0.960 | k = −11→13 |
21590 measured reflections | l = −43→33 |
Refinement on F2 | 156 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.062 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.187 | (Δ/σ)max < 0.001 |
S = 1.00 | Δρmax = 0.42 e Å−3 |
7997 reflections | Δρmin = −0.29 e Å−3 |
533 parameters |
C18H20F3N2OS+·Cl− | V = 3880.8 (12) Å3 |
Mr = 404.89 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.5715 (14) Å | µ = 0.34 mm−1 |
b = 10.4989 (14) Å | T = 294 K |
c = 34.966 (8) Å | 0.20 × 0.14 × 0.12 mm |
β = 90.040 (6)° |
Bruker SMART CCD diffractometer | 7997 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 3476 reflections with I > 2σ(I) |
Tmin = 0.935, Tmax = 0.960 | Rint = 0.061 |
21590 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 156 restraints |
wR(F2) = 0.187 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.42 e Å−3 |
7997 reflections | Δρmin = −0.29 e Å−3 |
533 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. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.87631 (13) | 0.26060 (17) | 0.11320 (4) | 0.0945 (5) | |
S2 | 0.13158 (12) | 0.17445 (15) | 0.39331 (4) | 0.0845 (5) | |
Cl1 | 0.95342 (8) | 0.50699 (9) | 0.22049 (3) | 0.0532 (3) | |
Cl2 | 0.45144 (9) | 0.43229 (10) | 0.22268 (3) | 0.0567 (3) | |
F4 | 0.6149 (10) | 0.3307 (14) | 0.0024 (4) | 0.160 (5) | 0.59 (2) |
F5 | 0.4496 (17) | 0.2631 (12) | −0.0181 (4) | 0.154 (4) | 0.59 (2) |
F6 | 0.4203 (15) | 0.3934 (11) | 0.0185 (3) | 0.137 (5) | 0.59 (2) |
F4' | 0.570 (2) | 0.260 (2) | −0.0160 (5) | 0.160 (7) | 0.41 (2) |
F5' | 0.376 (2) | 0.2455 (18) | −0.0130 (5) | 0.152 (7) | 0.41 (2) |
F6' | 0.503 (2) | 0.3963 (16) | 0.0258 (4) | 0.129 (6) | 0.41 (2) |
O1 | 0.9179 (3) | 0.1508 (3) | 0.19011 (9) | 0.0654 (9) | |
O2 | 0.0775 (3) | 0.2832 (3) | 0.31653 (8) | 0.0616 (8) | |
N1 | 0.7286 (3) | 0.2251 (3) | 0.29390 (9) | 0.0439 (8) | |
H1A | 0.669 (3) | 0.163 (3) | 0.2889 (11) | 0.064 (13)* | |
N2 | 0.6407 (3) | 0.3079 (3) | 0.36817 (10) | 0.0554 (9) | |
N3 | 0.2638 (3) | 0.2183 (3) | 0.21098 (9) | 0.0397 (8) | |
H3A | 0.330 (3) | 0.276 (4) | 0.2164 (12) | 0.086 (16)* | |
N4 | 0.3515 (3) | 0.1331 (3) | 0.13693 (9) | 0.0492 (9) | |
C1 | 0.7761 (6) | 0.3490 (6) | 0.08685 (14) | 0.100 (2) | |
H1 | 0.7895 | 0.3684 | 0.0612 | 0.120* | |
C2 | 0.6737 (5) | 0.3892 (5) | 0.10693 (15) | 0.0781 (15) | |
H2 | 0.6084 | 0.4377 | 0.0966 | 0.094* | |
C3 | 0.6785 (4) | 0.3486 (4) | 0.14507 (12) | 0.0557 (11) | |
H3 | 0.6167 | 0.3681 | 0.1630 | 0.067* | |
C4 | 0.7836 (4) | 0.2773 (4) | 0.15315 (12) | 0.0538 (11) | |
C5 | 0.8246 (4) | 0.2186 (4) | 0.18879 (12) | 0.0492 (11) | |
C6 | 0.7438 (4) | 0.2431 (4) | 0.22355 (11) | 0.0540 (11) | |
H6A | 0.7150 | 0.3308 | 0.2232 | 0.065* | |
H6B | 0.6699 | 0.1885 | 0.2227 | 0.065* | |
C7 | 0.8153 (3) | 0.2185 (4) | 0.26006 (11) | 0.0489 (11) | |
H7A | 0.8542 | 0.1350 | 0.2589 | 0.059* | |
H7B | 0.8820 | 0.2813 | 0.2629 | 0.059* | |
C8 | 0.6711 (4) | 0.3527 (4) | 0.29960 (12) | 0.0545 (11) | |
H8A | 0.6261 | 0.3777 | 0.2766 | 0.065* | |
H8B | 0.7372 | 0.4148 | 0.3043 | 0.065* | |
C9 | 0.5804 (4) | 0.3512 (4) | 0.33305 (12) | 0.0583 (12) | |
H9A | 0.5472 | 0.4363 | 0.3369 | 0.070* | |
H9B | 0.5098 | 0.2955 | 0.3271 | 0.070* | |
C10 | 0.7027 (4) | 0.1857 (4) | 0.36287 (12) | 0.0602 (12) | |
H10A | 0.6392 | 0.1208 | 0.3583 | 0.072* | |
H10B | 0.7479 | 0.1634 | 0.3861 | 0.072* | |
C11 | 0.7940 (4) | 0.1878 (4) | 0.32990 (12) | 0.0551 (11) | |
H11A | 0.8616 | 0.2478 | 0.3353 | 0.066* | |
H11B | 0.8314 | 0.1040 | 0.3268 | 0.066* | |
C12 | 0.5690 (4) | 0.3231 (5) | 0.40204 (14) | 0.0648 (13) | |
C13 | 0.6025 (5) | 0.2608 (5) | 0.43516 (15) | 0.0832 (16) | |
H13A | 0.6717 | 0.2062 | 0.4350 | 0.100* | |
C14 | 0.5359 (6) | 0.2777 (7) | 0.46829 (18) | 0.102 (2) | |
C15 | 0.4349 (7) | 0.3582 (8) | 0.4698 (2) | 0.131 (3) | |
H15A | 0.3931 | 0.3724 | 0.4927 | 0.157* | |
C16 | 0.3960 (6) | 0.4176 (7) | 0.4372 (2) | 0.133 (3) | |
H16A | 0.3242 | 0.4688 | 0.4375 | 0.159* | |
C17 | 0.4637 (6) | 0.4017 (6) | 0.40344 (18) | 0.108 (2) | |
H17A | 0.4379 | 0.4445 | 0.3815 | 0.129* | |
C18 | 0.5752 (7) | 0.2091 (8) | 0.5042 (3) | 0.152 (3) | |
F1 | 0.6814 (12) | 0.1474 (16) | 0.5034 (5) | 0.212 (10) | 0.40 |
F2 | 0.4798 (13) | 0.1113 (12) | 0.5086 (4) | 0.222 (8) | 0.40 |
F3 | 0.5516 (15) | 0.2816 (12) | 0.5349 (3) | 0.191 (6) | 0.40 |
F1' | 0.6351 (9) | 0.0965 (7) | 0.4965 (2) | 0.139 (3) | 0.60 |
F2' | 0.4833 (10) | 0.1807 (13) | 0.5273 (3) | 0.231 (5) | 0.60 |
F3' | 0.6644 (7) | 0.2900 (8) | 0.5220 (2) | 0.184 (4) | 0.60 |
C19 | 0.2390 (5) | 0.0884 (5) | 0.41821 (14) | 0.0835 (16) | |
H19 | 0.2303 | 0.0700 | 0.4441 | 0.100* | |
C20 | 0.3376 (4) | 0.0491 (4) | 0.39733 (13) | 0.0668 (13) | |
H20 | 0.4048 | 0.0012 | 0.4067 | 0.080* | |
C21 | 0.3257 (4) | 0.0905 (4) | 0.35889 (12) | 0.0516 (11) | |
H21 | 0.3852 | 0.0728 | 0.3400 | 0.062* | |
C22 | 0.2179 (4) | 0.1591 (4) | 0.35233 (11) | 0.0476 (10) | |
C23 | 0.1737 (4) | 0.2176 (4) | 0.31697 (11) | 0.0460 (10) | |
C24 | 0.2519 (3) | 0.1999 (4) | 0.28165 (11) | 0.0505 (11) | |
H24A | 0.2840 | 0.1134 | 0.2811 | 0.061* | |
H24B | 0.3239 | 0.2570 | 0.2827 | 0.061* | |
C25 | 0.1788 (3) | 0.2249 (4) | 0.24523 (11) | 0.0442 (10) | |
H25A | 0.1118 | 0.1624 | 0.2427 | 0.053* | |
H25B | 0.1401 | 0.3086 | 0.2465 | 0.053* | |
C26 | 0.3225 (4) | 0.0914 (4) | 0.20559 (11) | 0.0498 (11) | |
H26A | 0.2571 | 0.0285 | 0.2010 | 0.060* | |
H26B | 0.3676 | 0.0673 | 0.2286 | 0.060* | |
C27 | 0.4123 (4) | 0.0936 (4) | 0.17252 (11) | 0.0532 (11) | |
H27A | 0.4812 | 0.1516 | 0.1782 | 0.064* | |
H27B | 0.4480 | 0.0092 | 0.1692 | 0.064* | |
C28 | 0.2864 (4) | 0.2552 (4) | 0.14174 (12) | 0.0530 (11) | |
H28A | 0.2398 | 0.2750 | 0.1186 | 0.064* | |
H28B | 0.3486 | 0.3219 | 0.1457 | 0.064* | |
C29 | 0.1965 (4) | 0.2530 (4) | 0.17514 (11) | 0.0532 (11) | |
H29A | 0.1579 | 0.3363 | 0.1781 | 0.064* | |
H29B | 0.1297 | 0.1918 | 0.1703 | 0.064* | |
C30 | 0.4274 (4) | 0.1209 (4) | 0.10424 (12) | 0.0562 (11) | |
C31 | 0.5111 (5) | 0.0189 (5) | 0.10076 (15) | 0.0978 (19) | |
H31A | 0.5173 | −0.0409 | 0.1203 | 0.117* | |
C32 | 0.5852 (6) | 0.0065 (7) | 0.0684 (2) | 0.126 (2) | |
H32A | 0.6419 | −0.0610 | 0.0669 | 0.152* | |
C33 | 0.5778 (6) | 0.0897 (7) | 0.03866 (17) | 0.104 (2) | |
H33A | 0.6267 | 0.0794 | 0.0168 | 0.125* | |
C34 | 0.4960 (5) | 0.1886 (6) | 0.04236 (15) | 0.0806 (15) | |
C35 | 0.4210 (4) | 0.2047 (5) | 0.07409 (13) | 0.0644 (13) | |
H35A | 0.3653 | 0.2731 | 0.0752 | 0.077* | |
C36 | 0.4935 (10) | 0.2888 (9) | 0.0119 (2) | 0.124 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0841 (10) | 0.1419 (15) | 0.0576 (9) | 0.0016 (9) | 0.0215 (7) | −0.0117 (9) |
S2 | 0.0848 (10) | 0.1166 (12) | 0.0520 (8) | 0.0144 (8) | 0.0242 (7) | −0.0045 (8) |
Cl1 | 0.0477 (6) | 0.0448 (7) | 0.0672 (8) | 0.0020 (5) | 0.0027 (5) | 0.0029 (5) |
Cl2 | 0.0492 (6) | 0.0460 (7) | 0.0749 (8) | −0.0021 (5) | 0.0017 (5) | −0.0066 (6) |
F4 | 0.144 (7) | 0.195 (8) | 0.142 (8) | −0.050 (6) | 0.040 (6) | 0.054 (6) |
F5 | 0.176 (10) | 0.189 (7) | 0.097 (6) | −0.023 (8) | −0.038 (7) | 0.022 (5) |
F6 | 0.173 (9) | 0.129 (6) | 0.108 (6) | 0.029 (6) | 0.059 (6) | 0.047 (5) |
F4' | 0.167 (10) | 0.201 (11) | 0.111 (9) | −0.018 (8) | 0.069 (8) | 0.027 (7) |
F5' | 0.152 (10) | 0.177 (10) | 0.127 (9) | 0.019 (8) | −0.020 (8) | 0.025 (7) |
F6' | 0.169 (11) | 0.117 (8) | 0.100 (7) | −0.012 (8) | 0.004 (8) | 0.035 (6) |
O1 | 0.0550 (18) | 0.066 (2) | 0.075 (2) | 0.0076 (16) | 0.0098 (16) | −0.0073 (17) |
O2 | 0.0543 (18) | 0.064 (2) | 0.066 (2) | 0.0113 (16) | 0.0070 (15) | −0.0064 (16) |
N1 | 0.0398 (19) | 0.039 (2) | 0.053 (2) | −0.0027 (17) | 0.0023 (16) | 0.0015 (17) |
N2 | 0.056 (2) | 0.057 (2) | 0.053 (2) | 0.0002 (18) | 0.0019 (18) | −0.0038 (19) |
N3 | 0.0378 (18) | 0.039 (2) | 0.042 (2) | 0.0011 (16) | 0.0020 (15) | 0.0046 (15) |
N4 | 0.059 (2) | 0.050 (2) | 0.038 (2) | 0.0023 (17) | 0.0003 (17) | 0.0005 (16) |
C1 | 0.119 (5) | 0.144 (6) | 0.037 (3) | −0.031 (4) | 0.010 (3) | 0.002 (3) |
C2 | 0.087 (4) | 0.086 (4) | 0.061 (4) | −0.018 (3) | −0.008 (3) | 0.005 (3) |
C3 | 0.063 (3) | 0.055 (3) | 0.049 (3) | −0.013 (2) | 0.007 (2) | 0.000 (2) |
C4 | 0.049 (3) | 0.064 (3) | 0.048 (3) | −0.014 (2) | 0.007 (2) | −0.009 (2) |
C5 | 0.043 (2) | 0.048 (3) | 0.057 (3) | −0.012 (2) | 0.005 (2) | −0.010 (2) |
C6 | 0.046 (2) | 0.063 (3) | 0.054 (3) | 0.000 (2) | 0.009 (2) | 0.001 (2) |
C7 | 0.040 (2) | 0.050 (3) | 0.057 (3) | 0.0002 (19) | 0.002 (2) | 0.004 (2) |
C8 | 0.060 (3) | 0.038 (3) | 0.066 (3) | 0.005 (2) | 0.006 (2) | 0.002 (2) |
C9 | 0.063 (3) | 0.047 (3) | 0.065 (3) | 0.009 (2) | 0.007 (2) | 0.006 (2) |
C10 | 0.066 (3) | 0.070 (3) | 0.045 (3) | 0.010 (2) | −0.002 (2) | 0.011 (2) |
C11 | 0.055 (2) | 0.062 (3) | 0.048 (3) | 0.010 (2) | −0.006 (2) | 0.011 (2) |
C12 | 0.057 (3) | 0.075 (3) | 0.062 (3) | −0.012 (2) | 0.006 (2) | −0.015 (3) |
C13 | 0.072 (3) | 0.122 (4) | 0.056 (3) | −0.004 (3) | 0.008 (3) | 0.001 (3) |
C14 | 0.094 (4) | 0.153 (6) | 0.061 (4) | −0.004 (4) | 0.009 (3) | −0.003 (4) |
C15 | 0.125 (5) | 0.179 (7) | 0.088 (5) | 0.010 (5) | 0.029 (4) | −0.033 (5) |
C16 | 0.117 (5) | 0.161 (6) | 0.120 (6) | 0.040 (4) | 0.031 (5) | −0.021 (5) |
C17 | 0.116 (4) | 0.119 (5) | 0.088 (4) | 0.039 (4) | 0.023 (3) | −0.013 (4) |
C18 | 0.120 (6) | 0.194 (8) | 0.142 (7) | 0.012 (6) | 0.045 (6) | −0.013 (6) |
F1 | 0.210 (12) | 0.231 (13) | 0.194 (12) | −0.015 (9) | −0.021 (8) | 0.046 (9) |
F2 | 0.255 (12) | 0.207 (11) | 0.205 (12) | 0.011 (9) | 0.029 (9) | −0.011 (9) |
F3 | 0.234 (10) | 0.224 (10) | 0.114 (8) | −0.061 (9) | 0.019 (8) | 0.005 (7) |
F1' | 0.169 (6) | 0.177 (7) | 0.070 (4) | −0.007 (6) | 0.020 (4) | 0.049 (4) |
F2' | 0.253 (8) | 0.299 (10) | 0.141 (7) | 0.016 (8) | 0.117 (6) | 0.045 (7) |
F3' | 0.177 (6) | 0.250 (8) | 0.126 (6) | 0.073 (6) | −0.054 (5) | −0.071 (5) |
C19 | 0.111 (4) | 0.099 (4) | 0.040 (3) | −0.001 (3) | 0.001 (3) | 0.003 (3) |
C20 | 0.078 (3) | 0.069 (3) | 0.054 (3) | 0.001 (3) | −0.006 (3) | 0.000 (3) |
C21 | 0.057 (3) | 0.052 (3) | 0.045 (3) | −0.010 (2) | 0.006 (2) | −0.004 (2) |
C22 | 0.048 (2) | 0.050 (3) | 0.045 (3) | −0.003 (2) | 0.0085 (19) | −0.004 (2) |
C23 | 0.044 (2) | 0.042 (3) | 0.052 (3) | −0.006 (2) | 0.004 (2) | −0.004 (2) |
C24 | 0.043 (2) | 0.066 (3) | 0.042 (3) | 0.004 (2) | 0.0051 (19) | 0.005 (2) |
C25 | 0.041 (2) | 0.045 (3) | 0.047 (3) | 0.0006 (18) | 0.0030 (19) | 0.0085 (19) |
C26 | 0.062 (3) | 0.045 (3) | 0.042 (3) | 0.008 (2) | 0.003 (2) | 0.009 (2) |
C27 | 0.061 (3) | 0.050 (3) | 0.048 (3) | 0.013 (2) | 0.002 (2) | 0.002 (2) |
C28 | 0.056 (3) | 0.056 (3) | 0.047 (3) | 0.008 (2) | −0.001 (2) | 0.010 (2) |
C29 | 0.048 (2) | 0.062 (3) | 0.050 (3) | 0.008 (2) | −0.006 (2) | 0.011 (2) |
C30 | 0.067 (3) | 0.056 (3) | 0.046 (3) | −0.004 (2) | 0.004 (2) | −0.008 (2) |
C31 | 0.140 (5) | 0.089 (4) | 0.064 (4) | 0.036 (4) | 0.034 (3) | 0.004 (3) |
C32 | 0.147 (6) | 0.146 (7) | 0.086 (5) | 0.052 (5) | 0.033 (4) | −0.014 (5) |
C33 | 0.118 (5) | 0.131 (6) | 0.063 (4) | 0.009 (4) | 0.037 (4) | −0.013 (4) |
C34 | 0.093 (4) | 0.095 (4) | 0.053 (4) | −0.012 (3) | 0.019 (3) | −0.003 (3) |
C35 | 0.072 (3) | 0.074 (3) | 0.047 (3) | −0.002 (2) | 0.007 (2) | 0.003 (3) |
C36 | 0.169 (9) | 0.149 (8) | 0.054 (5) | −0.003 (7) | 0.031 (5) | −0.002 (5) |
S1—C1 | 1.683 (6) | C12—C17 | 1.387 (6) |
S1—C4 | 1.716 (4) | C13—C14 | 1.367 (7) |
S2—C19 | 1.692 (5) | C13—H13A | 0.9300 |
S2—C22 | 1.707 (4) | C14—C15 | 1.363 (8) |
F4—C36 | 1.397 (14) | C14—C18 | 1.505 (10) |
F5—C36 | 1.178 (13) | C15—C16 | 1.363 (9) |
F6—C36 | 1.363 (13) | C15—H15A | 0.9300 |
F4'—C36 | 1.303 (15) | C16—C17 | 1.389 (8) |
F5'—C36 | 1.58 (2) | C16—H16A | 0.9300 |
F6'—C36 | 1.234 (17) | C17—H17A | 0.9300 |
O1—C5 | 1.218 (4) | C18—F1 | 1.296 (9) |
O2—C23 | 1.228 (4) | C18—F2' | 1.298 (8) |
N1—C8 | 1.484 (5) | C18—F3 | 1.340 (9) |
N1—C11 | 1.488 (5) | C18—F1' | 1.368 (8) |
N1—C7 | 1.499 (5) | C18—F3' | 1.413 (8) |
N1—H1A | 0.93 (3) | C18—F2 | 1.448 (9) |
N2—C12 | 1.416 (5) | C19—C20 | 1.339 (6) |
N2—C10 | 1.452 (5) | C19—H19 | 0.9300 |
N2—C9 | 1.456 (5) | C20—C21 | 1.418 (6) |
N3—C26 | 1.482 (5) | C20—H20 | 0.9300 |
N3—C29 | 1.486 (5) | C21—C22 | 1.367 (5) |
N3—C25 | 1.499 (4) | C21—H21 | 0.9300 |
N3—H3A | 0.94 (3) | C22—C23 | 1.458 (5) |
N4—C30 | 1.403 (5) | C23—C24 | 1.498 (5) |
N4—C27 | 1.461 (5) | C24—C25 | 1.512 (5) |
N4—C28 | 1.465 (5) | C24—H24A | 0.9700 |
C1—C2 | 1.358 (6) | C24—H24B | 0.9700 |
C1—H1 | 0.9300 | C25—H25A | 0.9700 |
C2—C3 | 1.401 (6) | C25—H25B | 0.9700 |
C2—H2 | 0.9300 | C26—C27 | 1.497 (5) |
C3—C4 | 1.369 (5) | C26—H26A | 0.9700 |
C3—H3 | 0.9300 | C26—H26B | 0.9700 |
C4—C5 | 1.456 (6) | C27—H27A | 0.9700 |
C5—C6 | 1.508 (5) | C27—H27B | 0.9700 |
C6—C7 | 1.505 (5) | C28—C29 | 1.507 (5) |
C6—H6A | 0.9700 | C28—H28A | 0.9700 |
C6—H6B | 0.9700 | C28—H28B | 0.9700 |
C7—H7A | 0.9700 | C29—H29A | 0.9700 |
C7—H7B | 0.9700 | C29—H29B | 0.9700 |
C8—C9 | 1.513 (5) | C30—C35 | 1.375 (6) |
C8—H8A | 0.9700 | C30—C31 | 1.395 (6) |
C8—H8B | 0.9700 | C31—C32 | 1.384 (7) |
C9—H9A | 0.9700 | C31—H31A | 0.9300 |
C9—H9B | 0.9700 | C32—C33 | 1.359 (8) |
C10—C11 | 1.504 (5) | C32—H32A | 0.9300 |
C10—H10A | 0.9700 | C33—C34 | 1.357 (7) |
C10—H10B | 0.9700 | C33—H33A | 0.9300 |
C11—H11A | 0.9700 | C34—C35 | 1.375 (6) |
C11—H11B | 0.9700 | C34—C36 | 1.498 (9) |
C12—C13 | 1.376 (6) | C35—H35A | 0.9300 |
C1—S1—C4 | 91.7 (3) | F2'—C18—F2 | 41.3 (7) |
C19—S2—C22 | 91.3 (2) | F3—C18—F2 | 100.7 (9) |
C8—N1—C11 | 108.3 (3) | F1'—C18—F2 | 74.4 (8) |
C8—N1—C7 | 113.5 (3) | F3'—C18—F2 | 147.5 (11) |
C11—N1—C7 | 111.8 (3) | F1—C18—C14 | 117.4 (9) |
C8—N1—H1A | 112 (2) | F2'—C18—C14 | 115.0 (8) |
C11—N1—H1A | 107 (2) | F3—C18—C14 | 110.2 (8) |
C7—N1—H1A | 104 (2) | F1'—C18—C14 | 112.1 (7) |
C12—N2—C10 | 116.7 (4) | F3'—C18—C14 | 105.2 (7) |
C12—N2—C9 | 115.8 (4) | F2—C18—C14 | 103.7 (8) |
C10—N2—C9 | 111.5 (3) | C20—C19—S2 | 114.0 (4) |
C26—N3—C29 | 108.3 (3) | C20—C19—H19 | 123.0 |
C26—N3—C25 | 113.3 (3) | S2—C19—H19 | 123.0 |
C29—N3—C25 | 112.0 (3) | C19—C20—C21 | 110.7 (4) |
C26—N3—H3A | 107 (3) | C19—C20—H20 | 124.6 |
C29—N3—H3A | 111 (3) | C21—C20—H20 | 124.6 |
C25—N3—H3A | 105 (3) | C22—C21—C20 | 113.2 (4) |
C30—N4—C27 | 114.6 (3) | C22—C21—H21 | 123.4 |
C30—N4—C28 | 116.3 (3) | C20—C21—H21 | 123.4 |
C27—N4—C28 | 110.9 (3) | C21—C22—C23 | 129.1 (4) |
C2—C1—S1 | 112.9 (4) | C21—C22—S2 | 110.8 (3) |
C2—C1—H1 | 123.5 | C23—C22—S2 | 120.1 (3) |
S1—C1—H1 | 123.5 | O2—C23—C22 | 120.8 (4) |
C1—C2—C3 | 111.7 (5) | O2—C23—C24 | 121.1 (4) |
C1—C2—H2 | 124.2 | C22—C23—C24 | 118.1 (4) |
C3—C2—H2 | 124.2 | C23—C24—C25 | 113.0 (3) |
C4—C3—C2 | 113.1 (4) | C23—C24—H24A | 109.0 |
C4—C3—H3 | 123.5 | C25—C24—H24A | 109.0 |
C2—C3—H3 | 123.5 | C23—C24—H24B | 109.0 |
C3—C4—C5 | 130.5 (4) | C25—C24—H24B | 109.0 |
C3—C4—S1 | 110.6 (3) | H24A—C24—H24B | 107.8 |
C5—C4—S1 | 118.9 (3) | N3—C25—C24 | 111.0 (3) |
O1—C5—C4 | 121.4 (4) | N3—C25—H25A | 109.4 |
O1—C5—C6 | 121.9 (4) | C24—C25—H25A | 109.4 |
C4—C5—C6 | 116.7 (4) | N3—C25—H25B | 109.4 |
C7—C6—C5 | 111.7 (3) | C24—C25—H25B | 109.4 |
C7—C6—H6A | 109.3 | H25A—C25—H25B | 108.0 |
C5—C6—H6A | 109.3 | N3—C26—C27 | 110.5 (3) |
C7—C6—H6B | 109.3 | N3—C26—H26A | 109.5 |
C5—C6—H6B | 109.3 | C27—C26—H26A | 109.5 |
H6A—C6—H6B | 107.9 | N3—C26—H26B | 109.5 |
N1—C7—C6 | 110.8 (3) | C27—C26—H26B | 109.5 |
N1—C7—H7A | 109.5 | H26A—C26—H26B | 108.1 |
C6—C7—H7A | 109.5 | N4—C27—C26 | 112.5 (3) |
N1—C7—H7B | 109.5 | N4—C27—H27A | 109.1 |
C6—C7—H7B | 109.5 | C26—C27—H27A | 109.1 |
H7A—C7—H7B | 108.1 | N4—C27—H27B | 109.1 |
N1—C8—C9 | 110.7 (3) | C26—C27—H27B | 109.1 |
N1—C8—H8A | 109.5 | H27A—C27—H27B | 107.8 |
C9—C8—H8A | 109.5 | N4—C28—C29 | 111.9 (3) |
N1—C8—H8B | 109.5 | N4—C28—H28A | 109.2 |
C9—C8—H8B | 109.5 | C29—C28—H28A | 109.2 |
H8A—C8—H8B | 108.1 | N4—C28—H28B | 109.2 |
N2—C9—C8 | 112.2 (3) | C29—C28—H28B | 109.2 |
N2—C9—H9A | 109.2 | H28A—C28—H28B | 107.9 |
C8—C9—H9A | 109.2 | N3—C29—C28 | 110.8 (3) |
N2—C9—H9B | 109.2 | N3—C29—H29A | 109.5 |
C8—C9—H9B | 109.2 | C28—C29—H29A | 109.5 |
H9A—C9—H9B | 107.9 | N3—C29—H29B | 109.5 |
N2—C10—C11 | 112.0 (3) | C28—C29—H29B | 109.5 |
N2—C10—H10A | 109.2 | H29A—C29—H29B | 108.1 |
C11—C10—H10A | 109.2 | C35—C30—C31 | 117.1 (4) |
N2—C10—H10B | 109.2 | C35—C30—N4 | 122.6 (4) |
C11—C10—H10B | 109.2 | C31—C30—N4 | 120.3 (4) |
H10A—C10—H10B | 107.9 | C32—C31—C30 | 120.2 (5) |
N1—C11—C10 | 110.7 (3) | C32—C31—H31A | 119.9 |
N1—C11—H11A | 109.5 | C30—C31—H31A | 119.9 |
C10—C11—H11A | 109.5 | C33—C32—C31 | 122.2 (6) |
N1—C11—H11B | 109.5 | C33—C32—H32A | 118.9 |
C10—C11—H11B | 109.5 | C31—C32—H32A | 118.9 |
H11A—C11—H11B | 108.1 | C34—C33—C32 | 117.1 (5) |
C13—C12—C17 | 117.3 (5) | C34—C33—H33A | 121.5 |
C13—C12—N2 | 120.8 (5) | C32—C33—H33A | 121.5 |
C17—C12—N2 | 121.8 (5) | C33—C34—C35 | 122.6 (5) |
C14—C13—C12 | 121.3 (6) | C33—C34—C36 | 118.7 (6) |
C14—C13—H13A | 119.4 | C35—C34—C36 | 118.5 (6) |
C12—C13—H13A | 119.4 | C30—C35—C34 | 120.8 (5) |
C15—C14—C13 | 121.1 (7) | C30—C35—H35A | 119.6 |
C15—C14—C18 | 118.7 (6) | C34—C35—H35A | 119.6 |
C13—C14—C18 | 120.2 (6) | F5—C36—F6' | 126.5 (13) |
C14—C15—C16 | 119.2 (7) | F5—C36—F4' | 61.7 (9) |
C14—C15—H15A | 120.4 | F6'—C36—F4' | 117.1 (15) |
C16—C15—H15A | 120.4 | F5—C36—F6 | 96.4 (12) |
C15—C16—C17 | 120.0 (7) | F6'—C36—F6 | 41.0 (7) |
C15—C16—H16A | 120.0 | F4'—C36—F6 | 131.8 (10) |
C17—C16—H16A | 120.0 | F5—C36—F4 | 102.9 (9) |
C12—C17—C16 | 121.0 (6) | F6'—C36—F4 | 74.2 (12) |
C12—C17—H17A | 119.5 | F4'—C36—F4 | 47.5 (9) |
C16—C17—H17A | 119.5 | F6—C36—F4 | 108.0 (11) |
F1—C18—F2' | 123.1 (13) | F5—C36—C34 | 118.6 (11) |
F1—C18—F3 | 117.5 (11) | F6'—C36—C34 | 111.1 (9) |
F2'—C18—F3 | 59.5 (7) | F4'—C36—C34 | 111.0 (10) |
F1—C18—F1' | 33.2 (9) | F6—C36—C34 | 117.1 (7) |
F2'—C18—F1' | 105.7 (8) | F4—C36—C34 | 111.9 (8) |
F3—C18—F1' | 137.3 (11) | F5—C36—F5' | 30.2 (10) |
F1—C18—F3' | 74.4 (9) | F6'—C36—F5' | 123.2 (15) |
F2'—C18—F3' | 111.4 (10) | F4'—C36—F5' | 90.5 (14) |
F3—C18—F3' | 55.3 (7) | F6—C36—F5' | 83.0 (12) |
F1'—C18—F3' | 107.3 (8) | F4—C36—F5' | 133.0 (10) |
F1—C18—F2 | 104.5 (10) | C34—C36—F5' | 101.7 (10) |
C4—S1—C1—C2 | −1.0 (4) | C22—S2—C19—C20 | 0.5 (4) |
S1—C1—C2—C3 | 1.1 (6) | S2—C19—C20—C21 | −0.2 (6) |
C1—C2—C3—C4 | −0.7 (6) | C19—C20—C21—C22 | −0.3 (6) |
C2—C3—C4—C5 | 179.4 (4) | C20—C21—C22—C23 | 179.5 (4) |
C2—C3—C4—S1 | −0.1 (5) | C20—C21—C22—S2 | 0.6 (4) |
C1—S1—C4—C3 | 0.6 (4) | C19—S2—C22—C21 | −0.6 (3) |
C1—S1—C4—C5 | −178.9 (4) | C19—S2—C22—C23 | −179.6 (3) |
C3—C4—C5—O1 | 175.2 (4) | C21—C22—C23—O2 | −175.4 (4) |
S1—C4—C5—O1 | −5.4 (5) | S2—C22—C23—O2 | 3.3 (5) |
C3—C4—C5—C6 | −3.2 (6) | C21—C22—C23—C24 | 2.1 (6) |
S1—C4—C5—C6 | 176.3 (3) | S2—C22—C23—C24 | −179.2 (3) |
O1—C5—C6—C7 | 21.4 (6) | O2—C23—C24—C25 | −21.7 (5) |
C4—C5—C6—C7 | −160.3 (3) | C22—C23—C24—C25 | 160.8 (3) |
C8—N1—C7—C6 | −63.1 (4) | C26—N3—C25—C24 | 61.9 (4) |
C11—N1—C7—C6 | 174.0 (3) | C29—N3—C25—C24 | −175.3 (3) |
C5—C6—C7—N1 | −171.9 (3) | C23—C24—C25—N3 | 174.6 (3) |
C11—N1—C8—C9 | −57.8 (4) | C29—N3—C26—C27 | 58.7 (4) |
C7—N1—C8—C9 | 177.5 (3) | C25—N3—C26—C27 | −176.4 (3) |
C12—N2—C9—C8 | 170.1 (3) | C30—N4—C27—C26 | −172.1 (3) |
C10—N2—C9—C8 | −53.4 (5) | C28—N4—C27—C26 | 53.7 (4) |
N1—C8—C9—N2 | 56.2 (5) | N3—C26—C27—N4 | −57.4 (4) |
C12—N2—C10—C11 | −169.9 (3) | C30—N4—C28—C29 | 173.5 (3) |
C9—N2—C10—C11 | 54.0 (5) | C27—N4—C28—C29 | −53.1 (4) |
C8—N1—C11—C10 | 58.5 (4) | C26—N3—C29—C28 | −58.7 (4) |
C7—N1—C11—C10 | −175.8 (3) | C25—N3—C29—C28 | 175.7 (3) |
N2—C10—C11—N1 | −57.4 (5) | N4—C28—C29—N3 | 56.8 (4) |
C10—N2—C12—C13 | 30.9 (6) | C27—N4—C30—C35 | −145.6 (4) |
C9—N2—C12—C13 | 165.2 (4) | C28—N4—C30—C35 | −14.0 (6) |
C10—N2—C12—C17 | −149.8 (5) | C27—N4—C30—C31 | 36.2 (6) |
C9—N2—C12—C17 | −15.5 (6) | C28—N4—C30—C31 | 167.8 (4) |
C17—C12—C13—C14 | −1.2 (8) | C35—C30—C31—C32 | 1.2 (8) |
N2—C12—C13—C14 | 178.1 (5) | N4—C30—C31—C32 | 179.5 (5) |
C12—C13—C14—C15 | −0.9 (9) | C30—C31—C32—C33 | −1.5 (11) |
C12—C13—C14—C18 | −179.6 (5) | C31—C32—C33—C34 | 1.5 (11) |
C13—C14—C15—C16 | 3.4 (11) | C32—C33—C34—C35 | −1.3 (9) |
C18—C14—C15—C16 | −177.9 (7) | C32—C33—C34—C36 | 174.6 (7) |
C14—C15—C16—C17 | −3.8 (12) | C31—C30—C35—C34 | −1.0 (7) |
C13—C12—C17—C16 | 0.7 (9) | N4—C30—C35—C34 | −179.3 (4) |
N2—C12—C17—C16 | −178.6 (5) | C33—C34—C35—C30 | 1.1 (8) |
C15—C16—C17—C12 | 1.8 (11) | C36—C34—C35—C30 | −174.8 (6) |
C15—C14—C18—F1 | −170.6 (11) | C33—C34—C36—F5 | 71.9 (16) |
C13—C14—C18—F1 | 8.2 (13) | C35—C34—C36—F5 | −112.1 (14) |
C15—C14—C18—F2' | 32.4 (12) | C33—C34—C36—F6' | −128.6 (14) |
C13—C14—C18—F2' | −148.8 (9) | C35—C34—C36—F6' | 47.5 (17) |
C15—C14—C18—F3 | −32.4 (11) | C33—C34—C36—F4' | 4 (2) |
C13—C14—C18—F3 | 146.4 (9) | C35—C34—C36—F4' | 179.6 (17) |
C15—C14—C18—F1' | 153.2 (8) | C33—C34—C36—F6 | −173.2 (12) |
C13—C14—C18—F1' | −28.0 (9) | C35—C34—C36—F6 | 2.9 (15) |
C15—C14—C18—F3' | −90.5 (8) | C33—C34—C36—F4 | −47.8 (14) |
C13—C14—C18—F3' | 88.3 (8) | C35—C34—C36—F4 | 128.3 (11) |
C15—C14—C18—F2 | 74.7 (10) | C33—C34—C36—F5' | 98.7 (10) |
C13—C14—C18—F2 | −106.5 (9) | C35—C34—C36—F5' | −85.3 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···Cl2 | 0.94 (3) | 2.10 (3) | 3.025 (3) | 168 (4) |
N1—H1A···Cl1i | 0.93 (3) | 2.11 (3) | 3.033 (3) | 174 (3) |
Symmetry code: (i) −x+3/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H20F3N2OS+·Cl− |
Mr | 404.89 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 10.5715 (14), 10.4989 (14), 34.966 (8) |
β (°) | 90.040 (6) |
V (Å3) | 3880.8 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.20 × 0.14 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.935, 0.960 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21590, 7997, 3476 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.187, 1.00 |
No. of reflections | 7997 |
No. of parameters | 533 |
No. of restraints | 156 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.29 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···Cl2 | 0.94 (3) | 2.10 (3) | 3.025 (3) | 168 (4) |
N1—H1A···Cl1i | 0.93 (3) | 2.11 (3) | 3.033 (3) | 174 (3) |
Symmetry code: (i) −x+3/2, y−1/2, −z+1/2. |
Mannich bases can be used as anti-corrosion reagents or as a class of selective antidepressants with a low incidence of side effects (Oficialdegui et al., 2000; Martinez et al., 2001; Esparza et al., 2001; Orus et al., 2002). The title compound, was synthesized from 2-acetothiophene, 1-(3-Trifluoromethyl-phenyl)-piperazineand and paraformaldehyde. The molecular structure of the title compound is illustrated in Fig. 1. The asymmetric unit contains two independent molecules. Two intermolecular N—H···Cl hydrogen bonds help to consolidate the crystal packing. In each molecule, the piperazine ring has a chair conformation and the F atoms of the CF3 groups are disordered over two sites.