1-(2-Hy­droxy­eth­yl)-4-{3-[(E)-2-(trifluoro­meth­yl)-9H-thioxanthen-9-yl­idene]prop­yl}piperazine-1,4-diium bis­(3-carb­oxy­prop-2-enoate)

Siddegowda, M.S.; Butcher, R.J.; Akkurt, M.; Yathirajan, H.S.; Ramesh, A.R.

doi:10.1107/S160053681102722X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages o2017-o2018

doi:10.1107/S160053681102722X

Open

access

1-(2-Hydroxyethyl)-4-{3-[(E)-2-(trifluoromethyl)-9H-thioxanthen-9-ylidene]propyl}piperazine-1,4-diium bis(3-carboxyprop-2-enoate)

M. S. Siddegowda,^a Ray J. Butcher,^b Mehmet Akkurt,^c ^* H. S. Yathirajan ^a and A. R. Ramesh ^d

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^dR. L. Fine Chem, Bangalore 560 064, India
^*Correspondence e-mail: akkurt@erciyes.edu.tr

(Received 6 July 2011; accepted 7 July 2011; online 13 July 2011)

In the title salt, C₂₃H₂₇F₃N₂OS⁺·2C₄H₃O₄⁻, a non-merohedral twin [ratio of the twin components = 0.402 (1):0.598 (1)], the –CF₃ 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 9H-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.

Related literature

The title compound was formed by the reaction of flupentixol (systematic name: 2-[4-[3-[(EZ)-2-(trifluoromethyl)-9H-thioxanthen-9-ylidene]propyl]piperazin-1-yl]ethanol and fumaric acid. For the antidepressant action of flupentixol, see: Robertson & Trimble, (1981 ). For related structures, see: Post et al. (1975a ,b ); Jones et al. (1977 ). For ring puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₃H₂₇F₃N₂OS²⁺·2C₄H₃O₄⁻
M_r = 666.66
Triclinic, $[P \overline 1]$
a = 6.4175 (2) Å
b = 9.6185 (4) Å
c = 25.5771 (10) Å
α = 96.377 (4)°
β = 96.295 (3)°
γ = 92.774 (3)°
V = 1556.63 (10) Å³
Z = 2
Cu Kα radiation
μ = 1.59 mm⁻¹
T = 295 K
0.53 × 0.17 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.643, T_max = 1.000
11625 measured reflections
11625 independent reflections
9926 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.162
S = 1.03
11625 reflections
430 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O4A^iv	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⋯O1^v	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⋯O3B^vi	0.97	2.51	3.3848 (18)	150
C22—H22B⋯O4B^vi	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.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681102722X/tk2763sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102722X/tk2763Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681102722X/tk2763Isup3.cml

checkCIF report

Comment top

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 Q_T = 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 Q_T = 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).

Related literature top

The title compound was formed by the reaction of flupentixol (systematic name: 2-[4-[3-[(EZ)-2-(trifluoromethyl)-9H-thioxanthen-9-ylidene]propyl]piperazin-1-yl]ethanol and fumaric acid. For the antidepressant action of flupentixol, see: Robertson & Trimble, (1981). For related structures, see: Post et al. (1975a,b); Jones et al. (1977). For ring puckering parameters, see: Cremer & Pople (1975).

Experimental top

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).

Computing details top

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).

Figures top

	Fig. 1. Molecular structure of (I) with the atom labeling scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level. Hydrogen bond connections between the components of the asymmetric unit are shown as dashed lines. Only the major orientation of the disordered CF₃ group is shown.
	Fig. 2. Perspective view of the crystal packing and hydrogen bonding (dashed lines) of (I) down the b axis.

1-(2-Hydroxyethyl)-4-{3-[(E)-2-(trifluoromethyl)-9H-thioxanthen- 9-ylidene]propyl}piperazine-1,4-diium bis(3-carboxyprop-2-enoate) top

Crystal data top

C₂₃H₂₇F₃N₂OS²⁺·2C₄H₃O₄⁻	Z = 2
M_r = 666.66	F(000) = 696
Triclinic, P1	D_x = 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	R_int = 0.000
Detector resolution: 10.5081 pixels mm^-1	θ_max = 75.7°, θ_min = 4.6°
ω scans	h = −8→5
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −11→12
T_min = 0.643, T_max = 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(F_o²) + (0.0915P)² + 0.2879P] where P = (F_o² + 2F_c²)/3
11625 reflections	(Δ/σ)_max = 0.001
430 parameters	Δρ_max = 0.47 e Å⁻³
12 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₃H₂₇F₃N₂OS²⁺·2C₄H₃O₄⁻	γ = 92.774 (3)°
M_r = 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)
T_min = 0.643, T_max = 1.000	R_int = 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	Δρ_max = 0.47 e Å⁻³
11625 reflections	Δρ_min = −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	U_iso*/U_eq	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···O4A^iv	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···O1^v	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···O3B^vi	0.97	2.51	3.3848 (18)	150
C22—H22B···O4B^vi	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⁻
M_r	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)
T_min, T_max	0.643, 1.000
No. of measured, independent and observed [i > 2σ(i)] reflections	11625, 11625, 9926
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.27

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

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···O4A^iv	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···O1^v	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···O3B^vi	0.97	2.51	3.3848 (18)	150
C22—H22B···O4B^vi	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.

Acknowledgements

MSS thanks the University of Mysore for the research facilities. RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer.

References

Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Jones, P. G., Kennard, O. & Horn, A. S. (1977). Acta Cryst. B33, 3744–3747. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Post, M. L., Kennard, O. & Horn, A. S. (1975a). Acta Cryst. B31, 2724–2726. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Post, M. L., Kennard, O., Sheldrick, G. M. & Horn, A. S. (1975b). Acta Cryst. B31, 2366–2368. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Robertson, M. M. & Trimble, M. R. (1981). Practitioner, 225, 761–763. CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages o2017-o2018

doi:10.1107/S160053681102722X

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1-(2-Hy­dr­oxy­eth­yl)-4-{3-[(E)-2-(tri­fluoro­meth­yl)-9H-thioxanthen-9-yl­­idene]prop­yl}piperazine-1,4-diium bis­­(3-carb­­oxy­prop-2-enoate)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-(2-Hydroxyethyl)-4-{3-[(E)-2-(trifluoromethyl)-9H-thioxanthen-9-ylidene]propyl}piperazine-1,4-diium bis(3-carboxyprop-2-enoate)