In the title salt, C
23H
27F
3N
2OS
+·2C
4H
3O
4−, a non-merohedral twin [ratio of the twin components = 0.402 (1):0.598 (1)], the –CF
3 group is disordered over two sets of sites with occupancy factors in the ratio 0.873 (2):0.127 (2). The dihedral angle between the two outer aromatic rings of the 9
H-thioxanthene unit, whose thiopyran ring has a screw-boat conformation, is 33.01 (9)°. The diprotonated piperazine ring adopts a chair conformation. In the crystal, intermolecular O—H
O, N—H
O and C—H
O hydrogen bonds between neighboring molecules form zigzag chains along the
a axis and contribute to the stabilization of the packing.
Supporting information
CCDC reference: 841203
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.003 Å
- Disorder in main residue
- R factor = 0.055
- wR factor = 0.162
- Data-to-parameter ratio = 27.0
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT924_ALERT_1_A The Reported and Calculated Rho(min) Differ by . 5.46 eA-3
| Author Response: Both cif and fcf files were generated during the last refinement.
This was refined as a non-merohedral twin and thus an unmerged hkl file in hklf
5 format had to be used. This is the source of the discrepancies between
what is contained in the cif and fcf files.
|
PLAT926_ALERT_1_A Reported and Calculated R1 Differ by ......... -0.3132
| Author Response: Both cif and fcf files were generated during the last refinement.
This was refined as a non-merohedral twin and thus an unmerged hkl file in hklf
5 format had to be used. This is the source of the discrepancies between
what is contained in the cif and fcf files.
|
PLAT927_ALERT_1_A Reported and Calculated wR2 Differ by ......... -0.7292
| Author Response: Both cif and fcf files were generated during the last refinement.
This was refined as a non-merohedral twin and thus an unmerged hkl file
in hklf 5 format had to be used. This is the source of the discrepancies betwee
what is contained in the cif and fcf files.
|
PLAT928_ALERT_1_A Reported and Calculated S value Differ by . -3.463
| Author Response: Both cif and fcf files were generated during the last refinement.
This was refined as a non-merohedral twin and thus an unmerged hkl file in hklf
5 format had to be used. This is the source of the discrepancies between
what is contained in the cif and fcf files.
|
Alert level B
PLAT021_ALERT_1_B Ratio Unique / Expected Reflections too High ... 1.805
Alert level C
PLAT213_ALERT_2_C Atom F3A has ADP max/min Ratio ..... 3.1 prola
PLAT213_ALERT_2_C Atom F3B has ADP max/min Ratio ..... 3.1 prola
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.9
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 3.0
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 103
Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 7
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ?
PLAT301_ALERT_3_G Note: Main Residue Disorder ................... 10 Perc.
PLAT432_ALERT_2_G Short Inter X...Y Contact C6 .. F2B .. 2.93 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact C10 .. F3B .. 2.79 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact C12 .. F1B .. 2.91 Ang.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 4
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 12
4 ALERT level A = Most likely a serious problem - resolve or explain
1 ALERT level B = A potentially serious problem, consider carefully
7 ALERT level C = Check. Ensure it is not caused by an omission or oversight
8 ALERT level G = General information/check it is not something unexpected
5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
9 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
1 ALERT type 5 Informative message, check
Flupenthixol base (2.0 g, 0.046 mol) was dissolved in 10 ml of ethyl acetate and
fumaric acid (1.067 g, 0.092 mol) was added at 323 K. The solution was stirred
in a round bottomed flask at 343 K for 30 min. The mixture was cooled to room
temperature and the product formed was filtered and dried. X-ray quality
crystals were obtained from a 1:1 mixture of dichloromethane and methanol by
slow evaporation (M.pt.: 431-433 K).
All H atoms were positioned geometrically and allowed to ride on their parent
atoms, with C—H = 0.93–0.97 Å, N–H = 0.91 Å and O–H = 0.82 Å, and
with Uiso(H) = 1.5Ueq(O) for hydroxyl H atoms and
1.2Ueq(C) for other H atoms. The CF3 group is disordered over two
sets of sites with occupations of 0.873 (2) and 0.127 (2), respectively. The
structure was refined as a non-merohedral twin (using HKLF 5 in SHELXL) with
the final ratio of the twin components being 0.402 (1):0.598 (1); as such
there is no value for Rint.
Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
1-(2-Hydroxyethyl)-4-{3-[(
E)-2-(trifluoromethyl)-9
H-thioxanthen-
9-ylidene]propyl}piperazine-1,4-diium bis(3-carboxyprop-2-enoate)
top
Crystal data top
C23H27F3N2OS2+·2C4H3O4− | Z = 2 |
Mr = 666.66 | F(000) = 696 |
Triclinic, P1 | Dx = 1.422 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54184 Å |
a = 6.4175 (2) Å | Cell parameters from 5369 reflections |
b = 9.6185 (4) Å | θ = 4.6–75.4° |
c = 25.5771 (10) Å | µ = 1.59 mm−1 |
α = 96.377 (4)° | T = 295 K |
β = 96.295 (3)° | Thick needle, colourless |
γ = 92.774 (3)° | 0.53 × 0.17 × 0.12 mm |
V = 1556.63 (10) Å3 | |
Data collection top
Oxford Diffraction Xcalibur Ruby Gemini diffractometer | 11625 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 9926 reflections with i > 2σ(i) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 10.5081 pixels mm-1 | θmax = 75.7°, θmin = 4.6° |
ω scans | h = −8→5 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) | k = −11→12 |
Tmin = 0.643, Tmax = 1.000 | l = −31→31 |
11625 measured reflections | |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0915P)2 + 0.2879P] where P = (Fo2 + 2Fc2)/3 |
11625 reflections | (Δ/σ)max = 0.001 |
430 parameters | Δρmax = 0.47 e Å−3 |
12 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C23H27F3N2OS2+·2C4H3O4− | γ = 92.774 (3)° |
Mr = 666.66 | V = 1556.63 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.4175 (2) Å | Cu Kα radiation |
b = 9.6185 (4) Å | µ = 1.59 mm−1 |
c = 25.5771 (10) Å | T = 295 K |
α = 96.377 (4)° | 0.53 × 0.17 × 0.12 mm |
β = 96.295 (3)° | |
Data collection top
Oxford Diffraction Xcalibur Ruby Gemini diffractometer | 11625 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) | 9926 reflections with i > 2σ(i) |
Tmin = 0.643, Tmax = 1.000 | Rint = 0.000 |
11625 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 12 restraints |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.47 e Å−3 |
11625 reflections | Δρmin = −0.27 e Å−3 |
430 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted R-factors wR and all
goodnesses of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The observed criterion of F2 > σ(F2)
is used only for calculating -R-factor-obs 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 | −0.28261 (7) | 0.43649 (6) | 0.60072 (2) | 0.0659 (2) | |
F1A | 0.4612 (4) | 0.9150 (2) | 0.57634 (7) | 0.1255 (9) | 0.873 (2) |
F2A | 0.4440 (3) | 0.8145 (2) | 0.49990 (8) | 0.0980 (7) | 0.873 (2) |
F3A | 0.2283 (3) | 0.9651 (2) | 0.51652 (13) | 0.1469 (15) | 0.873 (2) |
O1 | 1.32172 (19) | 0.39302 (13) | 0.98491 (5) | 0.0546 (4) | |
N1 | 0.66238 (16) | 0.39316 (11) | 0.79768 (4) | 0.0305 (3) | |
N2 | 0.91809 (17) | 0.37193 (11) | 0.89824 (4) | 0.0306 (3) | |
C1 | 0.1779 (2) | 0.48863 (17) | 0.64991 (6) | 0.0438 (4) | |
C2 | 0.1109 (3) | 0.56962 (18) | 0.60557 (6) | 0.0477 (5) | |
C3 | 0.2459 (3) | 0.66960 (18) | 0.58916 (7) | 0.0516 (5) | |
C4 | 0.1775 (3) | 0.7513 (2) | 0.55001 (8) | 0.0582 (6) | |
C5 | −0.0262 (3) | 0.7307 (2) | 0.52472 (8) | 0.0656 (7) | |
C6 | −0.1606 (3) | 0.6297 (2) | 0.53930 (8) | 0.0651 (7) | |
C7 | −0.0948 (3) | 0.55110 (19) | 0.58004 (7) | 0.0521 (5) | |
C8 | 0.3238 (3) | 0.8631 (2) | 0.53587 (8) | 0.0680 (7) | |
C9 | −0.1214 (3) | 0.3095 (2) | 0.62478 (7) | 0.0547 (5) | |
C10 | −0.2118 (4) | 0.1745 (2) | 0.62336 (9) | 0.0729 (7) | |
C11 | −0.0916 (4) | 0.0699 (2) | 0.64065 (10) | 0.0856 (9) | |
C12 | 0.1184 (4) | 0.0977 (2) | 0.65792 (9) | 0.0724 (8) | |
C13 | 0.2079 (3) | 0.23213 (19) | 0.66001 (7) | 0.0562 (6) | |
C14 | 0.0877 (3) | 0.34244 (18) | 0.64521 (6) | 0.0477 (5) | |
C15 | 0.3059 (2) | 0.54985 (16) | 0.69190 (6) | 0.0451 (5) | |
C16 | 0.3723 (2) | 0.49081 (16) | 0.74246 (6) | 0.0429 (4) | |
C17 | 0.6030 (2) | 0.45802 (15) | 0.74784 (5) | 0.0371 (4) | |
C18 | 0.8816 (2) | 0.34649 (14) | 0.79991 (5) | 0.0341 (3) | |
C19 | 0.9388 (2) | 0.27621 (13) | 0.84905 (5) | 0.0340 (4) | |
C20 | 0.6999 (2) | 0.42049 (14) | 0.89560 (5) | 0.0340 (3) | |
C21 | 0.6437 (2) | 0.49041 (13) | 0.84642 (5) | 0.0337 (4) | |
C22 | 0.9676 (2) | 0.30256 (14) | 0.94779 (6) | 0.0382 (4) | |
C23 | 1.1958 (3) | 0.27466 (16) | 0.95978 (6) | 0.0461 (5) | |
F3B | 0.268 (2) | 0.8830 (13) | 0.4868 (3) | 0.1469 (15) | 0.127 (2) |
F1B | 0.304 (2) | 0.9803 (8) | 0.5651 (4) | 0.1255 (9) | 0.127 (2) |
F2B | 0.5195 (10) | 0.8365 (13) | 0.5404 (5) | 0.0980 (7) | 0.127 (2) |
O1A | 0.35437 (16) | 0.18909 (10) | 0.79446 (5) | 0.0436 (3) | |
O2A | 0.60481 (16) | 0.05328 (11) | 0.77149 (6) | 0.0524 (4) | |
O3A | 0.02774 (18) | −0.30289 (11) | 0.78941 (6) | 0.0588 (4) | |
O4A | −0.25463 (17) | −0.18840 (12) | 0.77479 (7) | 0.0663 (5) | |
C1A | 0.4234 (2) | 0.07131 (14) | 0.78390 (6) | 0.0364 (4) | |
C2A | 0.2834 (2) | −0.05762 (14) | 0.78550 (6) | 0.0385 (4) | |
C3A | 0.0781 (2) | −0.06083 (14) | 0.78089 (6) | 0.0383 (4) | |
C4A | −0.0509 (2) | −0.19431 (14) | 0.78216 (7) | 0.0422 (4) | |
O1B | 0.24341 (15) | 0.57369 (10) | 0.90547 (4) | 0.0412 (3) | |
O2B | −0.01770 (15) | 0.70858 (11) | 0.92034 (5) | 0.0456 (3) | |
O3B | 0.55830 (18) | 1.06667 (11) | 0.90607 (7) | 0.0639 (5) | |
O4B | 0.84275 (17) | 0.95113 (12) | 0.91559 (7) | 0.0623 (5) | |
C1B | 0.1684 (2) | 0.69183 (13) | 0.91202 (5) | 0.0337 (4) | |
C2B | 0.3074 (2) | 0.82060 (14) | 0.91032 (6) | 0.0391 (4) | |
C3B | 0.5119 (2) | 0.82417 (13) | 0.91468 (6) | 0.0362 (4) | |
C4B | 0.6382 (2) | 0.95740 (14) | 0.91189 (7) | 0.0424 (4) | |
H1A | 0.57380 | 0.31640 | 0.79770 | 0.0370* | |
H5A | −0.07150 | 0.78460 | 0.49810 | 0.0790* | |
H2A | 1.00930 | 0.44800 | 0.89960 | 0.0370* | |
H3A | 0.38440 | 0.68180 | 0.60470 | 0.0620* | |
H1 | 1.32630 | 0.45270 | 0.96450 | 0.0820* | |
H12A | 0.20020 | 0.02600 | 0.66820 | 0.0870* | |
H13A | 0.35030 | 0.24980 | 0.67140 | 0.0670* | |
H15A | 0.36010 | 0.64000 | 0.68930 | 0.0540* | |
H16A | 0.28670 | 0.40570 | 0.74390 | 0.0510* | |
H6A | −0.29610 | 0.61380 | 0.52190 | 0.0780* | |
H10A | −0.35280 | 0.15480 | 0.61080 | 0.0870* | |
H11A | −0.15280 | −0.01970 | 0.64060 | 0.1030* | |
H18A | 0.97870 | 0.42690 | 0.79980 | 0.0410* | |
H18B | 0.89440 | 0.28150 | 0.76880 | 0.0410* | |
H19A | 0.84760 | 0.19230 | 0.84800 | 0.0410* | |
H19B | 1.08220 | 0.24840 | 0.84970 | 0.0410* | |
H20A | 0.68780 | 0.48600 | 0.92660 | 0.0410* | |
H20B | 0.60140 | 0.34090 | 0.89590 | 0.0410* | |
H21A | 0.50090 | 0.51950 | 0.84580 | 0.0400* | |
H21B | 0.73650 | 0.57340 | 0.84710 | 0.0400* | |
H22A | 0.92550 | 0.36180 | 0.97760 | 0.0460* | |
H22B | 0.88450 | 0.21440 | 0.94430 | 0.0460* | |
H23A | 1.20680 | 0.20010 | 0.98240 | 0.0550* | |
H23B | 1.25010 | 0.24220 | 0.92690 | 0.0550* | |
H16B | 0.34780 | 0.55750 | 0.77210 | 0.0510* | |
H17A | 0.62940 | 0.39420 | 0.71750 | 0.0450* | |
H17B | 0.68950 | 0.54370 | 0.74820 | 0.0450* | |
H2AA | 0.34710 | −0.14090 | 0.79010 | 0.0460* | |
H3AA | 0.01080 | 0.02140 | 0.77670 | 0.0460* | |
H4A | −0.28400 | −0.10740 | 0.77180 | 0.0990* | |
H2BA | 0.24320 | 0.90380 | 0.90580 | 0.0470* | |
H3BA | 0.58020 | 0.74270 | 0.91960 | 0.0430* | |
H4B | 0.87370 | 0.87110 | 0.91980 | 0.0930* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0438 (2) | 0.0814 (3) | 0.0728 (3) | −0.0019 (2) | 0.0006 (2) | 0.0191 (2) |
F1A | 0.170 (2) | 0.1107 (15) | 0.0830 (12) | −0.0800 (15) | −0.0226 (12) | 0.0305 (11) |
F2A | 0.1009 (13) | 0.0998 (12) | 0.0986 (13) | −0.0100 (10) | 0.0312 (10) | 0.0223 (11) |
F3A | 0.1041 (14) | 0.0976 (15) | 0.267 (4) | 0.0260 (11) | 0.0317 (17) | 0.126 (2) |
O1 | 0.0495 (6) | 0.0579 (7) | 0.0531 (6) | −0.0124 (5) | −0.0078 (5) | 0.0118 (5) |
N1 | 0.0287 (5) | 0.0269 (5) | 0.0353 (5) | −0.0042 (4) | 0.0045 (4) | 0.0035 (4) |
N2 | 0.0294 (5) | 0.0255 (5) | 0.0361 (5) | −0.0052 (4) | 0.0029 (4) | 0.0036 (4) |
C1 | 0.0413 (8) | 0.0470 (8) | 0.0442 (7) | 0.0051 (6) | 0.0033 (6) | 0.0112 (6) |
C2 | 0.0482 (9) | 0.0500 (8) | 0.0446 (8) | 0.0046 (7) | −0.0014 (6) | 0.0097 (6) |
C3 | 0.0498 (9) | 0.0530 (9) | 0.0525 (9) | 0.0025 (7) | −0.0012 (7) | 0.0155 (7) |
C4 | 0.0674 (11) | 0.0531 (10) | 0.0563 (10) | 0.0080 (8) | 0.0036 (8) | 0.0175 (8) |
C5 | 0.0748 (13) | 0.0643 (11) | 0.0585 (10) | 0.0112 (9) | −0.0086 (9) | 0.0239 (9) |
C6 | 0.0575 (11) | 0.0723 (12) | 0.0632 (11) | 0.0093 (9) | −0.0139 (8) | 0.0161 (9) |
C7 | 0.0477 (9) | 0.0575 (9) | 0.0508 (9) | 0.0049 (7) | −0.0001 (7) | 0.0096 (7) |
C8 | 0.0813 (14) | 0.0591 (11) | 0.0668 (12) | 0.0025 (10) | 0.0049 (10) | 0.0258 (9) |
C9 | 0.0535 (10) | 0.0628 (10) | 0.0470 (8) | −0.0071 (8) | 0.0020 (7) | 0.0115 (7) |
C10 | 0.0738 (13) | 0.0746 (13) | 0.0660 (12) | −0.0245 (11) | −0.0044 (10) | 0.0145 (10) |
C11 | 0.112 (2) | 0.0604 (12) | 0.0783 (14) | −0.0293 (12) | −0.0090 (13) | 0.0156 (11) |
C12 | 0.0983 (17) | 0.0516 (10) | 0.0644 (12) | −0.0033 (10) | −0.0059 (11) | 0.0127 (9) |
C13 | 0.0656 (11) | 0.0499 (9) | 0.0516 (9) | 0.0005 (8) | −0.0009 (8) | 0.0088 (7) |
C14 | 0.0534 (9) | 0.0508 (9) | 0.0386 (7) | −0.0028 (7) | 0.0030 (6) | 0.0084 (6) |
C15 | 0.0456 (8) | 0.0420 (8) | 0.0477 (8) | 0.0038 (6) | −0.0003 (6) | 0.0109 (6) |
C16 | 0.0417 (8) | 0.0444 (8) | 0.0425 (7) | 0.0044 (6) | 0.0009 (6) | 0.0081 (6) |
C17 | 0.0380 (7) | 0.0363 (7) | 0.0372 (7) | −0.0030 (5) | 0.0030 (5) | 0.0086 (5) |
C18 | 0.0300 (6) | 0.0335 (6) | 0.0390 (6) | −0.0002 (5) | 0.0084 (5) | 0.0020 (5) |
C19 | 0.0322 (7) | 0.0283 (6) | 0.0407 (7) | 0.0011 (5) | 0.0048 (5) | 0.0003 (5) |
C20 | 0.0301 (6) | 0.0337 (6) | 0.0382 (6) | −0.0014 (5) | 0.0078 (5) | 0.0021 (5) |
C21 | 0.0320 (7) | 0.0287 (6) | 0.0396 (7) | 0.0015 (5) | 0.0045 (5) | 0.0010 (5) |
C22 | 0.0410 (8) | 0.0324 (6) | 0.0406 (7) | −0.0061 (5) | 0.0016 (5) | 0.0085 (5) |
C23 | 0.0504 (9) | 0.0390 (7) | 0.0479 (8) | 0.0036 (6) | −0.0044 (6) | 0.0099 (6) |
F3B | 0.1041 (14) | 0.0976 (15) | 0.267 (4) | 0.0260 (11) | 0.0317 (17) | 0.126 (2) |
F1B | 0.170 (2) | 0.1107 (15) | 0.0830 (12) | −0.0800 (15) | −0.0226 (12) | 0.0305 (11) |
F2B | 0.1009 (13) | 0.0998 (12) | 0.0986 (13) | −0.0100 (10) | 0.0312 (10) | 0.0223 (11) |
O1A | 0.0335 (5) | 0.0286 (5) | 0.0689 (7) | −0.0024 (4) | 0.0080 (4) | 0.0069 (4) |
O2A | 0.0296 (5) | 0.0373 (5) | 0.0908 (9) | −0.0036 (4) | 0.0150 (5) | 0.0038 (5) |
O3A | 0.0432 (6) | 0.0316 (5) | 0.1042 (10) | −0.0014 (4) | 0.0123 (6) | 0.0179 (6) |
O4A | 0.0322 (6) | 0.0350 (5) | 0.1307 (13) | −0.0056 (4) | 0.0127 (6) | 0.0059 (7) |
C1A | 0.0283 (7) | 0.0299 (6) | 0.0501 (7) | −0.0038 (5) | 0.0012 (5) | 0.0071 (5) |
C2A | 0.0328 (7) | 0.0274 (6) | 0.0561 (8) | −0.0006 (5) | 0.0046 (6) | 0.0101 (5) |
C3A | 0.0327 (7) | 0.0264 (6) | 0.0558 (8) | −0.0015 (5) | 0.0062 (6) | 0.0055 (5) |
C4A | 0.0343 (7) | 0.0295 (6) | 0.0630 (9) | −0.0034 (5) | 0.0104 (6) | 0.0046 (6) |
O1B | 0.0353 (5) | 0.0274 (4) | 0.0616 (6) | −0.0028 (4) | 0.0073 (4) | 0.0085 (4) |
O2B | 0.0287 (5) | 0.0359 (5) | 0.0730 (7) | −0.0039 (4) | 0.0117 (4) | 0.0066 (5) |
O3B | 0.0389 (6) | 0.0322 (5) | 0.1227 (12) | −0.0019 (4) | 0.0075 (6) | 0.0216 (6) |
O4B | 0.0291 (6) | 0.0342 (5) | 0.1242 (12) | −0.0051 (4) | 0.0110 (6) | 0.0134 (6) |
C1B | 0.0293 (7) | 0.0292 (6) | 0.0423 (7) | −0.0045 (5) | 0.0024 (5) | 0.0076 (5) |
C2B | 0.0318 (7) | 0.0266 (6) | 0.0599 (8) | −0.0007 (5) | 0.0047 (6) | 0.0113 (6) |
C3B | 0.0301 (7) | 0.0260 (6) | 0.0522 (8) | −0.0024 (5) | 0.0029 (5) | 0.0071 (5) |
C4B | 0.0305 (7) | 0.0296 (6) | 0.0671 (9) | −0.0037 (5) | 0.0051 (6) | 0.0087 (6) |
Geometric parameters (Å, º) top
S1—C7 | 1.757 (2) | C12—C13 | 1.382 (3) |
S1—C9 | 1.758 (2) | C13—C14 | 1.403 (3) |
F1A—C8 | 1.319 (3) | C15—C16 | 1.497 (2) |
F1B—C8 | 1.301 (9) | C16—C17 | 1.5233 (18) |
F2A—C8 | 1.325 (3) | C18—C19 | 1.5110 (18) |
F2B—C8 | 1.289 (7) | C20—C21 | 1.5088 (18) |
F3A—C8 | 1.297 (3) | C22—C23 | 1.506 (2) |
F3B—C8 | 1.304 (8) | C3—H3A | 0.9300 |
O1—C23 | 1.413 (2) | C5—H5A | 0.9300 |
O1—H1 | 0.8200 | C6—H6A | 0.9300 |
O1A—C1A | 1.2488 (17) | C10—H10A | 0.9300 |
O2A—C1A | 1.2548 (17) | C11—H11A | 0.9300 |
O3A—C4A | 1.2055 (18) | C12—H12A | 0.9300 |
O4A—C4A | 1.3053 (17) | C13—H13A | 0.9300 |
O4A—H4A | 0.8200 | C15—H15A | 0.9300 |
O1B—C1B | 1.2567 (16) | C16—H16B | 0.9700 |
O2B—C1B | 1.2507 (16) | C16—H16A | 0.9700 |
O3B—C4B | 1.2083 (18) | C17—H17A | 0.9700 |
O4B—C4B | 1.3105 (17) | C17—H17B | 0.9700 |
O4B—H4B | 0.8200 | C18—H18B | 0.9700 |
N1—C21 | 1.4927 (16) | C18—H18A | 0.9700 |
N1—C18 | 1.4944 (17) | C19—H19A | 0.9700 |
N1—C17 | 1.5009 (17) | C19—H19B | 0.9700 |
N2—C22 | 1.5074 (18) | C20—H20B | 0.9700 |
N2—C20 | 1.4943 (17) | C20—H20A | 0.9700 |
N2—C19 | 1.4965 (16) | C21—H21B | 0.9700 |
N1—H1A | 0.9100 | C21—H21A | 0.9700 |
N2—H2A | 0.9100 | C22—H22B | 0.9700 |
C1—C14 | 1.482 (2) | C22—H22A | 0.9700 |
C1—C15 | 1.340 (2) | C23—H23A | 0.9700 |
C1—C2 | 1.483 (2) | C23—H23B | 0.9700 |
C2—C7 | 1.401 (3) | C1A—C2A | 1.5028 (19) |
C2—C3 | 1.393 (3) | C2A—C3A | 1.3084 (18) |
C3—C4 | 1.387 (3) | C3A—C4A | 1.4990 (19) |
C4—C5 | 1.388 (3) | C2A—H2AA | 0.9300 |
C4—C8 | 1.494 (3) | C3A—H3AA | 0.9300 |
C5—C6 | 1.377 (3) | C1B—C2B | 1.4984 (18) |
C6—C7 | 1.395 (3) | C2B—C3B | 1.3033 (18) |
C9—C10 | 1.391 (3) | C3B—C4B | 1.4956 (19) |
C9—C14 | 1.394 (3) | C2B—H2BA | 0.9300 |
C10—C11 | 1.379 (3) | C3B—H3BA | 0.9300 |
C11—C12 | 1.375 (4) | | |
| | | |
C7—S1—C9 | 100.77 (9) | C10—C11—H11A | 120.00 |
C23—O1—H1 | 110.00 | C11—C12—H12A | 120.00 |
C4A—O4A—H4A | 109.00 | C13—C12—H12A | 120.00 |
C4B—O4B—H4B | 109.00 | C14—C13—H13A | 119.00 |
C17—N1—C21 | 112.51 (10) | C12—C13—H13A | 119.00 |
C17—N1—C18 | 111.12 (10) | C1—C15—H15A | 116.00 |
C18—N1—C21 | 108.81 (9) | C16—C15—H15A | 116.00 |
C20—N2—C22 | 109.94 (10) | C15—C16—H16B | 109.00 |
C19—N2—C22 | 112.35 (10) | C17—C16—H16B | 109.00 |
C19—N2—C20 | 109.06 (10) | H16A—C16—H16B | 108.00 |
C18—N1—H1A | 108.00 | C15—C16—H16A | 109.00 |
C21—N1—H1A | 108.00 | C17—C16—H16A | 109.00 |
C17—N1—H1A | 108.00 | N1—C17—H17B | 109.00 |
C22—N2—H2A | 108.00 | N1—C17—H17A | 109.00 |
C20—N2—H2A | 108.00 | H17A—C17—H17B | 108.00 |
C19—N2—H2A | 109.00 | C16—C17—H17A | 109.00 |
C14—C1—C15 | 123.86 (14) | C16—C17—H17B | 109.00 |
C2—C1—C15 | 120.13 (15) | N1—C18—H18B | 109.00 |
C2—C1—C14 | 115.96 (13) | C19—C18—H18B | 109.00 |
C1—C2—C3 | 121.69 (16) | H18A—C18—H18B | 108.00 |
C3—C2—C7 | 117.77 (16) | C19—C18—H18A | 109.00 |
C1—C2—C7 | 120.50 (15) | N1—C18—H18A | 109.00 |
C2—C3—C4 | 121.22 (17) | N2—C19—H19B | 109.00 |
C3—C4—C5 | 120.28 (18) | C18—C19—H19B | 109.00 |
C3—C4—C8 | 119.45 (17) | H19A—C19—H19B | 108.00 |
C5—C4—C8 | 120.27 (18) | N2—C19—H19A | 109.00 |
C4—C5—C6 | 119.44 (18) | C18—C19—H19A | 109.00 |
C5—C6—C7 | 120.41 (18) | N2—C20—H20B | 109.00 |
C2—C7—C6 | 120.82 (17) | C21—C20—H20A | 109.00 |
S1—C7—C2 | 121.38 (14) | H20A—C20—H20B | 108.00 |
S1—C7—C6 | 117.70 (15) | N2—C20—H20A | 109.00 |
F1B—C8—F2B | 108.3 (8) | C21—C20—H20B | 109.00 |
F1B—C8—F3B | 107.2 (7) | N1—C21—H21A | 109.00 |
F2B—C8—F3B | 108.1 (8) | C20—C21—H21B | 109.00 |
F2A—C8—F3A | 105.9 (2) | H21A—C21—H21B | 108.00 |
F2A—C8—C4 | 112.33 (17) | C20—C21—H21A | 109.00 |
F2B—C8—C4 | 115.3 (6) | N1—C21—H21B | 109.00 |
F1B—C8—C4 | 109.6 (5) | N2—C22—H22B | 109.00 |
F1A—C8—F2A | 103.16 (19) | C23—C22—H22A | 109.00 |
F1A—C8—F3A | 109.0 (2) | H22A—C22—H22B | 108.00 |
F1A—C8—C4 | 112.26 (18) | C23—C22—H22B | 109.00 |
F3A—C8—C4 | 113.45 (18) | N2—C22—H22A | 109.00 |
F3B—C8—C4 | 108.1 (6) | C22—C23—H23A | 109.00 |
S1—C9—C14 | 121.65 (14) | O1—C23—H23A | 109.00 |
S1—C9—C10 | 117.29 (16) | O1—C23—H23B | 109.00 |
C10—C9—C14 | 121.06 (18) | H23A—C23—H23B | 108.00 |
C9—C10—C11 | 119.8 (2) | C22—C23—H23B | 109.00 |
C10—C11—C12 | 120.24 (19) | O2A—C1A—C2A | 117.17 (12) |
C11—C12—C13 | 120.02 (19) | O1A—C1A—O2A | 123.74 (13) |
C12—C13—C14 | 121.17 (19) | O1A—C1A—C2A | 119.10 (12) |
C1—C14—C9 | 120.51 (16) | C1A—C2A—C3A | 124.55 (13) |
C9—C14—C13 | 117.48 (17) | C2A—C3A—C4A | 121.36 (12) |
C1—C14—C13 | 122.01 (16) | O4A—C4A—C3A | 116.89 (12) |
C1—C15—C16 | 127.88 (14) | O3A—C4A—O4A | 120.88 (13) |
C15—C16—C17 | 112.50 (11) | O3A—C4A—C3A | 122.23 (12) |
N1—C17—C16 | 111.24 (11) | C1A—C2A—H2AA | 118.00 |
N1—C18—C19 | 111.20 (10) | C3A—C2A—H2AA | 118.00 |
N2—C19—C18 | 111.35 (10) | C4A—C3A—H3AA | 119.00 |
N2—C20—C21 | 111.66 (10) | C2A—C3A—H3AA | 119.00 |
N1—C21—C20 | 110.95 (10) | O1B—C1B—O2B | 123.45 (12) |
N2—C22—C23 | 114.20 (11) | O2B—C1B—C2B | 117.50 (11) |
O1—C23—C22 | 113.68 (13) | O1B—C1B—C2B | 119.05 (12) |
C4—C3—H3A | 119.00 | C1B—C2B—C3B | 124.58 (12) |
C2—C3—H3A | 119.00 | C2B—C3B—C4B | 120.93 (12) |
C6—C5—H5A | 120.00 | O3B—C4B—C3B | 122.51 (12) |
C4—C5—H5A | 120.00 | O4B—C4B—C3B | 116.97 (12) |
C7—C6—H6A | 120.00 | O3B—C4B—O4B | 120.52 (13) |
C5—C6—H6A | 120.00 | C1B—C2B—H2BA | 118.00 |
C9—C10—H10A | 120.00 | C3B—C2B—H2BA | 118.00 |
C11—C10—H10A | 120.00 | C2B—C3B—H3BA | 120.00 |
C12—C11—H11A | 120.00 | C4B—C3B—H3BA | 120.00 |
| | | |
C9—S1—C7—C2 | −30.94 (17) | C3—C4—C8—F1A | −29.5 (3) |
C9—S1—C7—C6 | 152.85 (15) | C3—C4—C8—F2A | 86.2 (2) |
C7—S1—C9—C10 | −152.63 (16) | C3—C4—C8—F3A | −153.7 (2) |
C7—S1—C9—C14 | 28.28 (17) | C5—C4—C8—F1A | 149.5 (2) |
C18—N1—C17—C16 | 173.66 (11) | C5—C4—C8—F2A | −94.8 (2) |
C21—N1—C17—C16 | −64.06 (14) | C5—C4—C8—F3A | 25.4 (3) |
C17—N1—C18—C19 | −177.84 (10) | C4—C5—C6—C7 | 1.7 (3) |
C21—N1—C18—C19 | 57.75 (13) | C5—C6—C7—S1 | 173.90 (15) |
C17—N1—C21—C20 | 178.72 (10) | C5—C6—C7—C2 | −2.3 (3) |
C18—N1—C21—C20 | −57.70 (13) | S1—C9—C10—C11 | 178.60 (18) |
C20—N2—C19—C18 | 55.99 (13) | C14—C9—C10—C11 | −2.3 (3) |
C22—N2—C19—C18 | 178.15 (10) | S1—C9—C14—C1 | 3.3 (2) |
C19—N2—C20—C21 | −56.27 (13) | S1—C9—C14—C13 | −175.63 (13) |
C22—N2—C20—C21 | −179.87 (11) | C10—C9—C14—C1 | −175.76 (17) |
C19—N2—C22—C23 | 69.51 (14) | C10—C9—C14—C13 | 5.3 (3) |
C20—N2—C22—C23 | −168.83 (11) | C9—C10—C11—C12 | −1.8 (4) |
C14—C1—C2—C3 | −146.11 (16) | C10—C11—C12—C13 | 2.6 (4) |
C14—C1—C2—C7 | 36.3 (2) | C11—C12—C13—C14 | 0.6 (3) |
C15—C1—C2—C3 | 36.4 (2) | C12—C13—C14—C1 | 176.62 (17) |
C15—C1—C2—C7 | −141.17 (16) | C12—C13—C14—C9 | −4.5 (3) |
C2—C1—C14—C9 | −39.3 (2) | C1—C15—C16—C17 | 110.09 (16) |
C2—C1—C14—C13 | 139.62 (16) | C15—C16—C17—N1 | −177.47 (12) |
C15—C1—C14—C9 | 138.10 (16) | N1—C18—C19—N2 | −58.15 (14) |
C15—C1—C14—C13 | −43.0 (2) | N2—C20—C21—N1 | 58.42 (13) |
C2—C1—C15—C16 | 173.11 (14) | N2—C22—C23—O1 | 81.02 (15) |
C14—C1—C15—C16 | −4.1 (2) | O1A—C1A—C2A—C3A | 22.3 (2) |
C1—C2—C3—C4 | −175.68 (17) | O2A—C1A—C2A—C3A | −157.25 (16) |
C7—C2—C3—C4 | 2.0 (3) | C1A—C2A—C3A—C4A | 179.16 (14) |
C1—C2—C7—S1 | 2.1 (2) | C2A—C3A—C4A—O3A | 2.8 (3) |
C1—C2—C7—C6 | 178.20 (16) | C2A—C3A—C4A—O4A | −176.90 (16) |
C3—C2—C7—S1 | −175.58 (14) | O1B—C1B—C2B—C3B | −16.6 (2) |
C3—C2—C7—C6 | 0.5 (3) | O2B—C1B—C2B—C3B | 162.92 (15) |
C2—C3—C4—C5 | −2.7 (3) | C1B—C2B—C3B—C4B | 179.28 (14) |
C2—C3—C4—C8 | 176.38 (17) | C2B—C3B—C4B—O3B | 0.7 (3) |
C3—C4—C5—C6 | 0.8 (3) | C2B—C3B—C4B—O4B | −178.69 (16) |
C8—C4—C5—C6 | −178.23 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1Bi | 0.82 | 2.05 | 2.8365 (16) | 162 |
N1—H1A···O1A | 0.91 | 1.81 | 2.7055 (15) | 168 |
N1—H1A···O2A | 0.91 | 2.57 | 3.2580 (15) | 133 |
N2—H2A···O1Bi | 0.91 | 1.86 | 2.7572 (15) | 167 |
N2—H2A···O2Bi | 0.91 | 2.52 | 3.2230 (15) | 134 |
O4A—H4A···O2Aii | 0.82 | 1.73 | 2.5406 (16) | 167 |
O4B—H4B···O2Bi | 0.82 | 1.74 | 2.5497 (16) | 168 |
C2A—H2AA···O3A | 0.93 | 2.51 | 2.8251 (17) | 100 |
C2B—H2BA···O3B | 0.93 | 2.50 | 2.8165 (17) | 100 |
C16—H16B···O3Aiii | 0.97 | 2.56 | 3.2782 (19) | 131 |
C17—H17B···O4Aiv | 0.97 | 2.59 | 3.4520 (19) | 148 |
C19—H19A···O2A | 0.97 | 2.57 | 3.2871 (18) | 131 |
C19—H19B···O1Ai | 0.97 | 2.41 | 3.2461 (17) | 144 |
C20—H20A···O1v | 0.97 | 2.44 | 3.3877 (18) | 167 |
C21—H21A···O1B | 0.97 | 2.41 | 3.2098 (16) | 140 |
C21—H21B···O2Bi | 0.97 | 2.51 | 3.2367 (17) | 132 |
C22—H22B···O3Bvi | 0.97 | 2.51 | 3.3848 (18) | 150 |
C22—H22B···O4Bvi | 0.97 | 2.55 | 3.4236 (18) | 150 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, y+1, z; (iv) x+1, y+1, z; (v) −x+2, −y+1, −z+2; (vi) x, y−1, z. |
Experimental details
Crystal data |
Chemical formula | C23H27F3N2OS2+·2C4H3O4− |
Mr | 666.66 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 6.4175 (2), 9.6185 (4), 25.5771 (10) |
α, β, γ (°) | 96.377 (4), 96.295 (3), 92.774 (3) |
V (Å3) | 1556.63 (10) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.53 × 0.17 × 0.12 |
|
Data collection |
Diffractometer | Oxford Diffraction Xcalibur Ruby Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) |
Tmin, Tmax | 0.643, 1.000 |
No. of measured, independent and observed [i > 2σ(i)] reflections | 11625, 11625, 9926 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.628 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.162, 1.03 |
No. of reflections | 11625 |
No. of parameters | 430 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.27 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1Bi | 0.82 | 2.05 | 2.8365 (16) | 162 |
N1—H1A···O1A | 0.91 | 1.81 | 2.7055 (15) | 168 |
N1—H1A···O2A | 0.91 | 2.57 | 3.2580 (15) | 133 |
N2—H2A···O1Bi | 0.91 | 1.86 | 2.7572 (15) | 167 |
N2—H2A···O2Bi | 0.91 | 2.52 | 3.2230 (15) | 134 |
O4A—H4A···O2Aii | 0.82 | 1.73 | 2.5406 (16) | 167 |
O4B—H4B···O2Bi | 0.82 | 1.74 | 2.5497 (16) | 168 |
C2A—H2AA···O3A | 0.93 | 2.51 | 2.8251 (17) | 100 |
C2B—H2BA···O3B | 0.93 | 2.50 | 2.8165 (17) | 100 |
C16—H16B···O3Aiii | 0.97 | 2.56 | 3.2782 (19) | 131 |
C17—H17B···O4Aiv | 0.97 | 2.59 | 3.4520 (19) | 148 |
C19—H19A···O2A | 0.97 | 2.57 | 3.2871 (18) | 131 |
C19—H19B···O1Ai | 0.97 | 2.41 | 3.2461 (17) | 144 |
C20—H20A···O1v | 0.97 | 2.44 | 3.3877 (18) | 167 |
C21—H21A···O1B | 0.97 | 2.41 | 3.2098 (16) | 140 |
C21—H21B···O2Bi | 0.97 | 2.51 | 3.2367 (17) | 132 |
C22—H22B···O3Bvi | 0.97 | 2.51 | 3.3848 (18) | 150 |
C22—H22B···O4Bvi | 0.97 | 2.55 | 3.4236 (18) | 150 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, y+1, z; (iv) x+1, y+1, z; (v) −x+2, −y+1, −z+2; (vi) x, y−1, z. |
Flupentixol (systematic IUPAC name: 2-[4-[3-[(EZ)-2-(trifluoromethyl)-9H-thioxanthen-9-ylidene] propyl]piperazin-1-yl]ethanol is a typical antipsychotic drug of the thioxanthene class. In addition to pure drug preparations, it is also available as deanxit, a combination product containing both melitracen and flupentixol.The antidepressant action of flupentixol has been described (Robertson & Trimble, 1981). The crystal structures of α-flupenthixol (Post et al., 1975b), β-flupenthixol (Post et al., 1975a) and piflutixol (Jones et al., 1977) have been reported. In view of the importance of flupentixol, this paper reports the crystal structure of the title salt, (I), C23H27F3N2+OS2.2[C4H3O4-], formed by the reaction of flupentixol and fumaric acid.
The crystal studied was a non-merohedral twin, the ratio of the twin components being 0.402 (1): 0.598 (1). In (I), Fig. 1, the thiopyran ring of the 9H-thioxanthene ring system (S1/C1/C2/C7C9/C14) has a screw-boat conformation: the puckering parameters (Cremer & Pople, 1975) of QT = 0.5118 (15) Å, θ = 87.53 (19)° and ϕ = 3.2 (2) °. The dihedral angle between the two outer aromatic rings of the 9H-thioxanthene unit is 33.01 (9) °. The diprotonated piperazine ring (N1/N2/C18–C21) adopts a chair conformation with puckering parameters QT = 0.580 (13) Å, θ = 178.76 (12) ° and ϕ = 177 (7) °.
In the crystal structure, intermolecular O—H···O, N—H···O and C—H···O hydrogen bonds (Table 1) contributes to crystal packing forming the zigzag chains parallel to the [100] direction (Fig. 2).